LMS Solutions Full Ebook

CHAPTER
1
1
The Nature of Physical Chemistry
and the Kinetic Theory of Gases

LAIDLER . MEISER . SANCTUARY
Physical Chemistry
Electronic Edition
Publisher: MCH Multimedia Inc.
Problems and Solutions

Chapter 1: The Nature of Physical Chemistry and Kinetic Theory of Gases Classical Mechanics and Thermal Equilibrium
1-2
Chapter 1
*problems with an asterisk are slightly more demanding
Classical Mechanics and Thermal Equilibrium
1.1. Calculate the amount of work required to accelerate a 1000-kg car (typical of a Honda Civic) to 88 km hr
1
(55 miles hr
1
). Compare
this value to the amount of work required for a 1600-kg car (typical of a Ford Taurus) under the same conditions.
Solution
1.2. Assume that a rod of copper is used to determine the temperature of some system. The rods length at 0 C is 27.5 cm, and at the
temperature of the system it is 28.1 cm. What is the temperature of the system? The linear expansion of copper is given by an
equation of the form l
t
= l
0
(1 +t +t
2
) where = 0.160 10
4
K
1
, =0.10 10
7
K
2
, l
0
is the length at 0 C, and l
t
is the length
at t C.
Solution
1.3. Atoms can transfer kinetic energy in a collision. If an atom has a mass of 1 10
24
g and travels with a velocity of 500 m s
1
, what is
the maximum kinetic energy that can be transferred from the moving atom in a head-on elastic collision to the stationary atom of
mass 1 10
23
g?
Solution
1.4. Power is defined as the rate at which work is done. The unit of power is the watt (W =1 J s
1
). What is the power that a man can
expend if all his food consumption of 8000 kJ a day ( 2000 kcal) is his only source of energy and it is used entirely for work?
Solution
1.5. State whether the following properties are intensive or extensive: (a) mass; (b) density; (c) temperature; (d) gravitational field.
Solution

Chapter 1: The Nature of Physical Chemistry and Kinetic Theory of Gases Gas Laws and Temperature
1-3
Gas Laws and Temperature
1.6. The mercury level in the left arm of the J -shaped tube in Fig. 1.6a is attached to a thermostat gas-containing bulb. The left arm is
10.83 cm and the right arm is 34.71 cm above the bottom of the manometer. If the barometric pressure reads 738.4 Torr, what is the
pressure of the gas? Assume that temperature-induced changes in the reading of the barometer and J tube are small enough to
neglect.
Solution
1.7. Vacuum technology has become increasingly more important in many scientific and industrial applications. The unit Torr, defined
as 1/760 atm, is commonly used in the measurement of low pressures.
a. Find the relation between the older unit mmHg and the Torr. The density of mercury is 13.5951 g cm
3
at 0.0 C. The standard
acceleration of gravity is defined as 9.806 65 m s
2
.
b. Calculate at 298.15 K the number of molecules present in 1.00 m
3
at 1.00 10
6
Torr and at 1.00 10
15
Torr (approximately the
best vacuum obtainable).
Solution
1.8. The standard atmosphere of pressure is the force per unit area exerted by a 760-mm column of mercury, the density of which is
13.595 11 g cm
3
at 0 C. If the gravitational acceleration is 9.806 65 m s
2
, calculate the pressure of 1 atm in kPa.
Solution
1.9. Dibutyl phthalate is often used as a manometer fluid. Its density is 1.047 g cm
3
. What is the relationship between 1.000 mm in
height of this fluid and the pressure in torr?
Solution
1.10. The volume of a vacuum manifold used to transfer gases is calibrated using Boyles law. A 0.251-dm
3
flask at a pressure of 697 Torr
is attached, and after system pumpdown, the manifold is at 10.4 Torr. The stopcock between the manifold and flask is opened and
the system reaches an equilibrium pressure of 287 Torr. Assuming isothermal conditions, what is the volume of the manifold?
Solution
1.11. An ideal gas occupies a volume of 0.300 dm
3
at a pressure of 1.80 10
5
Pa. What is the new volume of the gas maintained at the
same temperature if the pressure is reduced to 1.15 10
5
Pa?
Solution
1-4
1.12. If the gas in Problem 1.11 were initially at 330 K, what will be the final volume if the temperature were raised to 550 K at constant
pressure?
Solution
1.13. Calculate the concentration in mol dm
3
of an ideal gas at 298.15 K and at (a) 101.325 kPa (1 atm), and (b) 1.00 10
4
Pa
(=10
9
atm). In each case, determine the number of molecules in 1.00 dm
3
.
Solution
*1.14. A J -shaped tube is filled with air at 760 Torr and 22 C. The long arm is closed off at the top and is 100.0 cm long; the short arm is
40.00 cm high. Mercury is poured through a funnel into the open end. When the mercury spills over the top of the short arm, what is
the pressure on the trapped air? Let h be the length of mercury in the long arm.
Solution
1.15. A Dumas experiment to determine molar mass is conducted in which a gas samples P, , and V are determined. If a 1.08-g sample
is held in 0.250 dm
3
at 303 K and 101.3 kPa:
a. What would the samples volume be at 273.15 K, at constant pressure?
b. What is the molar mass of the sample?
Solution
1.16. A gas that behaves ideally has a density of 1.92 g dm
3
at 150 kPa and 298 K. What is the molar mass of the sample?
Solution
1.17. The density of air at 101.325 kPa and 298.15 K is 1.159 g dm
3
. Assuming that air behaves as an ideal gas, calculate its molar mass.
Solution
1.18. A 0.200-dm
3
sample of H
2
is collected over water at a temperature of 298.15 K and at a pressure of 99.99 kPa. What is the pressure
of hydrogen in the dry state at 298.15 K? The vapor pressure of water at 298.15 K is 3.17 kPa.
Solution

1-5
1.19. What are the mole fractions and partial pressures of each gas in a 2.50-L container into which 100.00 g of nitrogen and 100.00 g of
carbon dioxide are added at 25 C? What is the total pressure?
Solution
1.20. The decomposition of KClO
3
produces 27.8 cm
3
of O
2
collected over water at 27.5 C. The vapor pressure of water at this temperature
is 27.5 Torr. If the barometer reads 751.4 Torr, find the volume the dry gas would occupy at 25.0 C and 1.00 bar.
Solution
1.21. Balloons now are used to move huge trees from their cutting place on mountain slopes to conventional transportation. Calculate the
volume of a balloon needed if it is desired to have a lifting force of 1000 kg when the temperature is 290 K at 0.940 atm. The
balloon is to be filled with helium. Assume that air is 80 mol % N
2
and 20 mol % O
2
. Ignore the mass of the superstructure and
propulsion engines of the balloon.
Solution
*1.22. A gas mixture containing 5 mol % butane and 95 mol % argon (such as is used in Geiger-Mller counter tubes) is to be prepared by
allowing gaseous butane to fill an evacuated cylinder at 1 atm pressure. The 40.0-dm
3
cylinder is then weighed. Calculate the mass
of argon that gives the desired composition if the temperature is maintained at 25.0 C. Calculate the total pressure of the final
mixture. The molar mass of argon is 39.9 g mol
1
.
Solution
1.23. The gravitational constant g decreases by 0.010 m s
2
km
1
of altitude.
a. Modify the barometric equation to take this variation into account. Assume that the temperature remains constant.
b. Calculate the pressure of nitrogen at an altitude of 100 km assuming that sea-level pressure is exactly 1 atm and that the
temperature of 298.15 K is constant.
Solution

1.24. Suppose that on another planet where the atmosphere is ammonia that the pressure on the surface, at h =0, is 400 Torr at 250 K.
Calculate the pressure of ammonia at a height of 8000 metres. The planet has the same g value as the earth.
Solution
Chapter 1: The Nature of Physical Chemistry and Kinetic Theory of Gases Grahams Law, Molecular Collisions, and Kinetic Theory
1-6
1.25. Pilots are well aware that in the lower part of the atmosphere the temperature decreases linearly with altitude. This dependency may
be written as T =T
0
az, where a is a proportionality constant, z is the altitude, and T
0
and T are the temperatures at ground level
and at altitude z , respectively. Derive an expression for the barometric equation that takes this into account. Work to a form
involving ln P/P
0
.
Solution
1.26. An ideal gas thermometer and a mercury thermometer are calibrated at 0 C and at 100 C. The thermal expansion coefficient for
mercury is
0
4 9 10 2
1
( / )
1.817 10 5.90 10 3.45 10
P
V T
V

=
= + +

where is the value of the Celsius temperature and V
0
=V at =0. What temperature would appear on the mercury scale when the
ideal gas scale reads 50 C?
Solution
Grahams Law, Molecular Collisions, and Kinetic Theory
1.27. It takes gas A 2.3 times as long to effuse through an orifice as the same amount of nitrogen. What is the molar mass of gas A?
Solution
1.28. Exactly 1 dm
3
of nitrogen, under a pressure of 1 bar, takes 5.80 minutes to effuse through an orifice. How long will it take for helium
to effuse under the same conditions?
Solution
1.29. What is the total kinetic energy of 0.50 mol of an ideal monatomic gas confined to 8.0 dm
3
at 200 kPa?
Solution
1.30. Nitrogen gas is maintained at 152 kPa in a 2.00-dm
3
vessel at 298.15 K. If its molar mass is 28.0134 g mol
1
calculate:
a. The amount of N
2
present.
b. The number of molecules present.
Chapter 1: The Nature of Physical Chemistry and Kinetic Theory of Gases Grahams Law, Molecular Collisions, and Kinetic Theory
1-7
c. The root-mean-square speed of the molecules.
d. The average translational kinetic energy of each molecule.
e. The total translational kinetic energy in the system.
Solution
1.31. By what factor are the root-mean-square speeds changed if a gas is heated from 300 K to 400 K?
Solution
*1.32. The collision diameter of N
2
is 3.74 10
10
m at 298.15 K and 101.325 kPa. Its average speed is 474.6 m s
1
. Calculate the mean
free path, the average number of collisions Z
A
experienced by one molecule in unit time, and the average number of collisions Z
AA

per unit volume per unit time for N
2
.
Solution
*1.33. Express the mean free path of a gas in terms of the variables pressure and temperature, which are more easily measured than the
volume.
Solution
1.34. Calculate Z
A
and Z
AA
for argon at 25 C and a pressure of 1.00 bar using d =3.84 10
10
m obtained from X-ray crystallographic
measurements.
Solution
1.35. Calculate the mean free path of Ar at 20 C and 1.00 bar. The collision diameter d =3.84 10
10
m.
Solution
1.36. Hydrogen gas has a molecular collision diameter of 0.258 nm. Calculate the mean free path of hydrogen at 298.15 K and (a) 133.32
Pa, (b) 101.325 k Pa, and (c) 1.0 10
8
Pa.
Solution
1.37. In interstellar space it is estimated that atomic hydrogen exists at a concentration of one particle per cubic meter. If the collision
diameter is 2.5 10
10
m, calculate the mean free path . The temperature of interstellar space is 2.7 K.
Solution
Chapter 1: The Nature of Physical Chemistry and Kinetic Theory of Gases Distributions of Speeds and Energies
1-8
*1.38. Calculate the value of Avogadros constant from a study made by Perrin [Ann. Chem. Phys., 18, 1(1909)] in which he measured as a
function of height the distribution of bright yellow colloidal gamboge (a gum resin) particles suspended in water. Some data at 15
C are:
height, z/10
6
5 35
N, relative number of gamboge particles at height z 100 47

gamboge
=1.206 g cm
3

water
=0.999 g cm
-3
radius of gamboge particles, r =0.212 10
6
m

(Hint: Consider the particles to be gas molecules in a column of air and that the number of particles is proportional to the pressure.)
Solution
Distributions of Speeds and Energies
1.39. Refer to Table 1.3 (p. 32) and write expressions and values for (a) the ratio
2
/ u u , and (b) the ratio /u
mp
.

Note that these ratios are
independent of the mass and the temperature. How do the differences between them depend on these quantities?
Solution
1.40. The speed that a body of any mass must have to escape from the earth is 1.07 10
4
m s
1
. At what temperature would the average
speed of (a) an H
2
molecule, and (b) an O
2
molecule be equal to this escape speed?
Solution
1.41. a. For H
2
gas at 25 C, calculate the ratio of the fraction of molecules that have a speed 2u to the fraction that have the average
speed . How does this ratio depend on the mass of the molecules and the temperature?
b. Calculate the ratio of the fraction of the molecules that have the average speed
100C
at 100 C to the fraction that have the
average speed
25C
at 25 C. How does this ratio depend on the mass?
Solution

Chapter 1: The Nature of Physical Chemistry and Kinetic Theory of Gases Real Gases
1-9
1.42. Suppose that two ideal gases are heated to different temperatures such that their pressures and vapor densities are the same. What is
the relationship between their average molecular speeds?
Solution
1.43. a. If
25 C
is the average speed of the molecules in a gas at 25 C, calculate the ratio of the fraction that will have the speed
25 C
at
100 to the fraction that will have the same speed at 25 C.
b. Repeat this calculation for a speed of 10
25C
.
Solution
1.44. On the basis of Eq. 1.80 with =1/k
B
T, derive an expression for the fraction of molecules in a one-dimensional gas having speeds
between u
x
and u
x
+du
x
. What is the most probable speed?
Solution
*1.45. Derive an expression for the fraction of molecules in a one-dimensional gas having energies between
x
and
x x
d + .Also, obtain
an expression for the average energy x .
Solution
*1.46. Derive an expression for the fraction of molecules in a two-dimensional gas having speeds between u and u +du. (Hint: Proceed by
analogy with the derivation of Eq. 1.91.) Then obtain the expression for the fraction having energies between and d + . What
fraction will have energies in excess of
*
?
Solution
Real Gases
1.47. In Section 1.13 it was stated that the van der Waals constant b is approximately four times the volume occupied by the molecules
themselves. J ustify this relationship for a gas composed of spherical molecules.
Solution
1.48. Draw the van der Waals PV isotherm over the same range of P and V as in Figure 1.21 at 350 K and 450 K for Cl
2
using the values
in Table 1.4.
Solution
1-10
1.49. Compare the pressures predicted for 0.8 dm
3
of Cl
2
weighing 17.5 g at 273.15 K using (a) the ideal gas equation and (b) the van der
Waals equation.
Solution
1.50. A particular mass of N
2
occupies a volume of 1.00 L at 50 C and 800 bar. Determine the volume occupied by the same mass of
N
2
at 100 C and 200 bar using the compressibility factor for N
2
. At 50 C and 800 bar it is 1.95; at 100 C and 200 bar it is 1.10.
Compare this value to that obtained from the ideal gas law.
Solution
1.51. A gas is found to obey the equation of state
RT a
P
V b V
=

where a and b are constants not equal to zero. Determine whether this gas has a critical point; if it does, express the critical constants in
terms of a and b. If it does not, explain how you determined this and the implications for the statement of the problem.
Solution
1.52. Ethylene (C
2
H
4
) has a critical pressure of P
c
=61.659 atm and a critical temperature of T
c
=308.6 K. Calculate the molar volume of
the gas at T =97.2 C and 90.0 atm using Figure 1.22. Compare the value so found with that calculated from the ideal gas equation.
Solution
1.53. Assuming that methane is a perfectly spherical molecule, find the radius of one methane molecule using the value of b listed in
Table 1.5.
Solution
1.54. Determine the Boyle temperature in terms of constants for the equation of state:
PV
m
=RT{1 +8/57(P/P
c
)(T
c
/T)[1 4(T
c
/T)
2
]}
R, P
c
, and T
c
are constants.
Solution
1-11
1.55. Establish the relationships between van der Waals parameters a and b and the virial coefficients B and C of Eq. 1.117 by performing
the following steps:
a. Starting with Eq. 1.101, show that
1
m m
m m
PV V a
RT V b RT V
=
.
b. Since V
m
/(V
m
b) =(1 b/V
m
)
1
, and (1 x)
1
=1 +x +x
2
+,, expand (1 b/ V
m
)
1
to the quadratic term and substitute into the
result of part (a).
c. Group terms containing the same power of V
m
and compare to Eq. 1.117 for the case n =1.
d. What is the expression for the Boyle temperature in terms of van der Waals parameters?
Solution
*1.56. Determine the Boyle temperature of a van der Waals gas in terms of the constants a, b, and R.
Solution
1.57. The critical temperature T
c
of nitrous oxide (N
2
O) is 36.5 C, and its critical pressure P
c
is 71.7 atm. Suppose that 1 mol of N
2
O is
compressed to 54.0 atm at 356 K. Calculate the reduced temperature and pressure, and use Figure 1.22, interpolating as necessary, to
estimate the volume occupied by 1 mol of the gas at 54.0 atm and 356 K.
Solution
1.58. At what temperature and pressure will H
2
be in a corresponding state with CH
4
at 500.0 K and 2.00 bar pressure? Given T
c
=33.2 K
for H
2
, 190.6 K for CH
4
; P
c
=13.0 bar for H
2
, 46.0 bar for CH
4
.
Solution
*1.59. For the Dieterici equation, derive the relationship of a and b to the critical volume and temperature. [Hint: Remember that at the
critical point (P/V)
T
=0 and (
2
P/V
2
)
T
=0.]
Solution

1-12
1.60. In Eq. 1.103 a cubic equation has to be solved in order to find the volume of a van der Waals gas. However, reasonably accurate
estimates of volumes can be made by deriving an expression for the compression factor Z in terms of P from the result of the
previous problem. One simply substitutes for the terms V
m
on the right-hand side in terms of the ideal gas law expression V
m
=
RT/P. Derive this expression and use it to find the volume of CCl
2
F
2
at 30.0 C and 5.00 bar pressure. What will be the molar
volume computed using the ideal gas law under the same conditions?
Solution
*1.61. A general requirement of all equations of state for gases is that they reduce to the ideal gas equation (Eq. 1.28) in the limit of low
pressures. Show that this is true for the van der Waals equation.
Solution
1.62. The van der Waals constants for C
2
H
6
in the older literature are found to be
a =5.49 atm L
2
mol
2
and b =0.0638 L mol
1
Express these constants in SI units (L =liter =dm
3
).
Solution
*1.63. Compare the values obtained for the pressure of 3.00 mol CO
2
at 298.15 K held in a 8.25-dm
3
bulb using the ideal gas, van der
Waals, Dieterici, and Beattie-Bridgeman equations. For CO
2
the Dieterici equation constants are
a =0.462 Pa m
6
mol
2
,
b =4.63 10
5
m
3
mol
1
Solution
*1.64. A gas obeys the van der Waals equation with P
c
=3.040 10
6
Pa (=30 atm) and T
c
=473 K. Calculate the value of the van der
Waals constant b for this gas.
Solution
*1.65. Expand the Dieterici equation in powers of
1
m
V
in order to cast it into the virial form. Find the second and third virial coefficients.
Then show that at low densities the Dieterici and van der Waals equations give essentially the same result for P.
Solution
Chapter 1: The Nature of Physical Chemistry and Kinetic Theory of Gases Essay Questions
1-13
Essay Questions
1.66. In light of the van der Waals equation, explain the liquefaction of gases.
1.67. State the postulates of the kinetic molecular theory of gases.
1.68. Eq. 1.22 defines the ideal-gas thermometer. Describe how an actual measurement would be made using such a thermometer starting
with a fixed quantity of gas at a pressure of 150 Torr.

Chapter 1: The Nature of Physical Chemistry and Kinetic Theory of Gases Solutions
1-14
Solutions
1.1. Calculate the amount of work required to accelerate a 1000-kg car (typical of a Honda Civic) to 88 km hr
1
(55 miles hr
1
). Compare
this value to the amount of work required for a 1600-kg car (typical of a Ford Taurus) under the same conditions.
Solution:
Given: Car 1 (Civic):
1
1000 kg, 88 km hr m Speed = =

Car 2 (Taurus):
1
1600 kg, 88 km hr m Speed = =

Required: work required for the acceleration of each vehicle

Any type of work can be resolved through dimensional analysis as the application of a force through a distance;
( )
o
l
l
w F l dl =

Recall that bodies in motion possess kinetic energy defined by;
2
1
2
k
E mu = where u is the velocity of the moving body and m is its mass. It
is possible to determine the amount of work required for the acceleration of a moving body by applying Newtons Second Law to the work
integral given above.
0 0 0
( ) ( ) ( )
l t t
l t t
d
w d dt dt
dt
= = =

l
F l l F l F l u
Substitute;
d
m m
dt
= =
u
F a
0 0
t u
t u
d
w m dt m d
dt
= =

u
u u u
1 0
0
2 2
1 0
1 1
( )
2 2
l
k k
l
w d m m E E = = =
F l l u u
Conversion of speed from km hr
1
to m s
-1
:
Speed =88 km hr
1

km
88
h
1 h
3600
3
m
10
s km
-1
24.4 m s =
1-15
Using the equation for work derived from Newtons 2
nd
Law (Civic):
.
1 0
0
2 2
Civic 1 0
1 1
( )
2 2
l
k k
l
w d m m E E = = =
F l l u u
-1 2 -1 2
Civic
1 1
(1000 kg)(24.4 m s ) (1000 kg)(0 m s )
2 2
w =
Civic
297680 J w =
Civic
298 kJ w =
The same method can be applied to the second vehicle (Taurus):
1 0
0
2 2
Taurus 1 0
1 1
( )
2 2
l
k k
l
w d m m E E = = =
F l l u u
-1 2 -1 2
Taurus
1 1
(1600 kg)(24.4 m s ) (1600 kg)(0 m s )
2 2
w =
Taurus
476 288 J w =
Taurus
476 kJ w =
By comparing both values quantitatively, it is possible to see that the work required to accelerate a moving body is directly proportional to
its mass.

Back to Problem 1.1 Back to Top
1-16
1.2. Assume that a rod of copper is used to determine the temperature of some system. The rods length at 0 C is 27.5 cm, and at the
temperature of the system it is 28.1 cm. What is the temperature of the system? The linear expansion of copper is given by an
equation of the form l
t
= l
0
(1 +t +t
2
) where = 0.160 10
4
K
1
, =0.10 10
7
K
2
, l
0
t
is the length
at t C.
Solution:
Given: Copper Rod: 27.5cm, 0 C l T = =
Copper Rod in System: 28.1cm l =
Linear expansion of copper:
2
0
(1 )
t
l l t t = + + where = 0.16010
4
K
1
, =0.1010
7
K
2
, l
0
t
is the
length at t C
Required: temperature of the system when the rod length equals 28.1cm
Let us define the temperature as
u
t and make all of the appropriate substitutions into the equation for the linear expansion of copper (starting
temperature at zero degrees):
2
0
(1 )
t
l l t t = + +
4 7 2
28.1 27.5(1 0.160 10 0.100 10 )
u u
t t

= + +
Simplify and rearrange:
28.1 27.5
27.5
=
4 7 2
(1 0.160 10 0.100 10 )
27.5
u u
t t

+ +

1.0218 1 1 =
4 7 2
0.160 10 0.100 10 1
u u
t t

+ +
4 7 2
0.0218 0.160 10 0.100 10
u u
t t

= +
7 2 4
0 0.100 10 0.160 10 0.0218
u u
t t

= +
This can be rearranged to:
7 2 4
0.100 10 0.160 10 0.0218 0 x x

+ =
1-17
Where
u
x t = and the system can be solved using the quadratic equation:
2
4
2
b b ac
x
a

=
( ) ( )( )
( )
2
4 4 7
7
0.160 10 0.160 10 4 0.100 10 0.0218
2 0.100 10
x

o
879 C x =
o
879 C
u
t =

1-18
1.3. Atoms can transfer kinetic energy in a collision. If an atom has a mass of 1 10
24
g and travels with a velocity of 500 m s
1
, what is
the maximum kinetic energy that can be transferred from the moving atom in a head-on elastic collision to the stationary atom of
mass 1 10
23
g?
Solution:
Given: Atom 1:
24
1
1 10 g m

= ,
-1
1
500 m s u =
Atom 2:
23
2
1 10 g m

= ,
-1
2
0 m s u =
Required: Find E
k
(max) that can be transferred from atom 1 to atom 2
It is important to note that during elastic collisions, no energy is lost to the internal motion of the bodies involved. This means that the sums
of the kinetic energy in addition to the sums of momentum remain the same before and after the collision. Therefore, there is no potential
energy change of interaction between the bodies in collision.
Momentum: p mu =
Kinetic Energy=
2
1
2
k
E mu =
Conservation of Momentum:
' '
1 1 2 2 1 1 2 2
mu m u mu m u + = + (1)
Conservation of Energy:
2 2 2' 2'
1 1 2 2 1 1 2 2
1 1 1 1
2 2 2 2
mu m u mu m u + = + (2)
Since
1
2
0 m s u

= , then we can simplify equation (1) to get:
1 1 2 2
mu m u +
' '
1 1 2 2
mu m u = +

Rearrangement then gives:

'
' 2 2
1 1
1
m u
u u
m
= +
'
' 2 2
1 1
1
m u
u u
m
=
It is possible to substitute the above into equation (2) and solve for
'
2
u ;
1-19
' 1
2
2
1
2
1
u
u
m
m
=
+

1
'
2 23
24
2(500 m s )
1 10 g
1
1 10 g
u

' 1
2
90.9 m s u

=
Now this value can be used to find the kinetic energy of atom 2 after the collision. Remember to use SI units by converting grams to
kilograms;
'2
2 2
1
2
k
E m u =
26 1 2
1
(1 10 kg)(90.9 m s )
2
k
E

=
23
4.13 10 J
k
E

=

1-20
1.4. Power is defined as the rate at which work is done. The unit of power is the watt (W =1 J s
1
). What is the power that a man can
expend if all his food consumption of 8000 kJ a day ( 2000 kcal) is his only source of energy and it is used entirely for work?
Solution:
Given: Daily food consumption=8000 kJ ( 2000 kcal)
Required: P
one day

Remember that power is defined as the rate at which work can be done meaning that;
dw
P
dt
=
Since the mans entire caloric intake is going toward work, then we can say that;
3
8000 kJ 8000 10 J dw = =
We are only considering the power exerted in a single day;
1 day 24 hrs dt = =
24hrs dt =
60min
1hr
60 s
1min
| |
|
\ .
86400 s
| |
=
|
\ .

Power is measured by the Watt unit and 1 Watt =1J s
-1
(remember SI units!)
3
8000 10 J
86400 s
P

=
1
92.59 J s

92.6 W P =

1-21
1.5. State whether the following properties are intensive or extensive: (a) mass; (b) density; (c) temperature; (d) gravitational field.
Solution:

Given: (a) mass (b) density (c) temperature (d) gravitational field
Required: intensive or extensive?

It is first important to define the terms intensive and extensive in the context of physical chemistry.

Intensive properties (sometimes called bulk property) are considered to be physical properties of a system that do not depend on its size.
This means that their value will not change when the quantity of the matter in the system becomes subdivided.

Extensive properties are the physical properties of a system that DO depend on its size and content. The values of extensive properties
change with system subdivision. In addition, the ratio of two intensive properties yields an extensive one.
Now it is possible to classify the above properties:

Mass is extensive as it is a measure of how much is present in the system
Density is intensive
**note: mass and volume are extensive
Temperature is intensive
Gravitational Fieldis intensive

1-22
1.6. The mercury level in the left arm of the J -shaped tube in Fig. 1.6a is attached to a thermostat gas-containing bulb. The left arm is
10.83 cm and the right arm is 34.71 cm above the bottom of the manometer. If the barometric pressure reads 738.4 Torr, what is the
pressure of the gas? Assume that temperature-induced changes in the reading of the barometer and J tube are small enough to
neglect.
Solution:
Given: left arm =10.83 cm, right arm =34.71 cm, barometric pressure =738.4 Torr
Required: P
gas

First, we need to find the difference in heights between the two columns (left and right arms);
Right arm - Left arm =34.71 cm -10.83 cm =23.88 cm
It is important to note that since the arm is open to the atmosphere, this pressure must also be added to the barometric pressure.
1 mmHg =1 Torr and therefore 23.88 cmHg =238.8 Torr
The pressure of the gas is then found to be;
238.8 Torr +738.4 Torr =977.2 Torr
gas
977.2 Torr P =

1-23
1.7. Vacuum technology has become increasingly more important in many scientific and industrial applications. The unit Torr, defined
as 1/760 atm, is commonly used in the measurement of low pressures.
a. Find the relation between the older unit mmHg and the Torr. The density of mercury is 13.5951 g cm
3
at 0.0 C. The standard
acceleration of gravity is defined as 9.806 65 m s
2
.
b. Calculate at 298.15 K the number of molecules present in 1.00 m
3
at 1.00 10
6
Torr and at 1.00 10
15
Torr (approximately the
best vacuum obtainable).
Solution:
Given: Mercury:
3
13.5951 g cm , 0.0 C T = =

2
9.806 65 m s acceleration of gravity

=
Required: (a) State the relationship between mmHg and Torr
(b) N
A
in V =1.00 m
3

a) We should first define the system as a column of mercury with a 1m
2
cross-sectional area, 0.001 m in height, a volume of 0.001 m
3
. Since
we already have the density of mercury it is possible to determine the mass;
m
V
= m V =
-3
13.5951 kg m m =
3
0.001 m
Now for 1 mmHg in a column;
( )( )( ) 1 mmHg mass density acceleration of gravity =
3
1 mmHg 0.001m =
( )
-3
13.5951 kgm
( )( )
-2
9.80665 m s
-2
1 mmHg 0.1333 kg m s =
Now since 1 Torr =1 mmHg and 1 Torr =133.322 Pa then we can see that;
1-24
1 mmHg 133.322 387 4 Pa =
By definition, 1 atmosphere =101 325 Pa and 1 Torr =1/760 atm then;
1
1 Torr (101325 Pa) =133.3223684 Pa
760
=
Therefore;
133.3223874
1 mmHg 1.00000014 Torr
133.3223684
= =
The Torr is now defined as 1 mmHg.
b) Calculate the number of molecules present in a volume of 1.00 m
3
:
T =298.15 K, P
1
=1.0010
6
Torr and P
2
=1.0010
15
Torr
Using the ideal gas law: PV nRT = we define n as
N
n
L
= and rearrange to get;
PV nRT =
NRT
PV
L
= where L is Avogadros number and N is the number of particles
L =6.02210
23
mol
-1

And the number density is defined as
N PL
V RT
=
Remember to make the conversion for pressure! P
1
=1.0010
6
Torr;
1 1
N PL
V RT
=
1-25
6
1
1 10 Torr
N
V
=
( )
1atm
760Torr
1
8.3145 J K
| |
|
\ .
1
mol
( )
298.15K
( )
1
101325 Paatm
( )
23 1
6.022 10 mol
( )

16 3 1
3.24 10 m
N
V
=
16 3
1
3.24 10 m N

=
( )
3
1.00 m
( )
16
3.24 10 particles =
16
1
3.24 10 N =
P
2
=1.0010
15
Torr using the same method as outlined above;
2 2
N P L
V RT
=
15
2
1 10 Torr
N
V
=
( )
1atm
760Torr
1
8.3145 J K
| |
|
\ .
1
mol
( )
298.15K
( )
1
101325 Paatm
( )
23 1
6.022 10 mol
( )

7 3
2
3.24 10 m N

=
( )
3
1.00 m
( )
7
3.24 10 particles =
7
2
3.24 10 N =

This is still a substantial number!

1-26
1.8. The standard atmosphere of pressure is the force per unit area exerted by a 760-mm column of mercury, the density of which is
13.595 11 g cm
3
at 0 C. If the gravitational acceleration is 9.806 65 m s
2
, calculate the pressure of 1 atm in kPa.
Solution:
Given: Mercury:
3 2
13.595 11 g cm , 0 C, 9.806 65 m s T acceleration of gravity = = =

Required:
column
P (kPa)
Let us define the system as a column of mercury with a cross-sectional area of 1 m
2
, 0.760 m in height and a volume of 0.760 m
3
. Since we
have the density, it is possible to find the mass of mercury occupying the column;
m
V
=
3
13595.1 kgm m V

= =
( )
3
0.760m
( )

10332 kg m =
Mass multiplied by the gravitational acceleration produces a force (or weight) F ma = according to Newtons Law of Motion. The
columns weight on the unit area then gives a pressure;
column
(density)(volume)(acceleration of gravity) P =
3
column
13595.1 kgm P

=
( )
3
0.760m
( )( )
2
9.80665 m s

2
column
101325 kg m s P

=
Since 1 Pa =1kg m s
-2
then the pressure is 101.325 kPa.
column
101.325 kPa P =

1-27
1.9. Dibutyl phthalate is often used as a manometer fluid. Its density is 1.047 g cm
3
. What is the relationship between 1.000 mm in
height of this fluid and the pressure in torr?
Solution:
Given: Dibutyl phthalate:
3
1.047 g cm =
Required: The relationship between 1.000 mm of this manometer fluid and pressure (Torr)
When two different liquids are being compared at constant volume and temperature, it is important to note that their pressures will be
proportional to their densities.
Therefore, it is possible to take the ratio of DBP and Hg densities in order to calculate the pressure associated with 1mm of DBP.
1mmDBP
l mmHg

3
DBP DBP DBP
3
Hg Hg Hg
1.047 g cm
13.595 g cm
P P
P P
=
DBP
Hg
0.077
P
P
=
DBP
0.077 Torr P =
Thus, 1mm DBP is equivalent to 0.077 Torr using the fact that 1mmHg is equivalent to 1 Torr. We can also state that;
1
1 Torr
12.98 mmDBP
0.077 Torr mm
=
1 mm DBP 0.077 Torr =

1-28
1.10. The volume of a vacuum manifold used to transfer gases is calibrated using Boyles law. A 0.251-dm
3
flask at a pressure of 697 Torr
is attached, and after system pumpdown, the manifold is at 10.4 mTorr. The stopcock between the manifold and flask is opened and
the system reaches an equilibrium pressure of 287 Torr. Assuming isothermal conditions, what is the volume of the manifold?
Solution:

Given:
3
1 1 pumpdown eq
0.251 dm , 697 Torr , 10.4 mTorr, 287 Torr V P P P = = = =
Required:
manifold
V

Since we are working under isothermal conditions, Boyles Law will apply. This law describes the product of pressure and volume for a
closed system. In a closed system, the temperature and moles are constant, thus;
1 1 2 2
PV PV =

1 1 pumpdown 2 eq 2 1
( ) PV P V P V V + = +
( )( ) ( ) ( )
3 3
2 2
697 Torr 0.251 dm 0.0104 Torr V 287 Torr V 0.251 dm + = +
( ) ( )
3 3
2 2
174.947 Torr dm 0.0104 Torr 287 Torr 72.037 Torr dm V V + = +
Now the above can be simplified on both sides to obtain,
( )
3
2
102.91 Torr dm 286.9896 Torr V =
2 manifold
102.91Torr
V V = =
3
dm
286.9896Torr

3
manifold
0.359 dm V =

1-29
1.11. An ideal gas occupies a volume of 0.300 dm
3
at a pressure of 1.80 10
5
Pa. What is the new volume of the gas maintained at the
same temperature if the pressure is reduced to 1.15 10
5
Pa?
Solution:
Given: Ideal Gas:
3 5
1 1
0.300 dm, 1.80 10 Pa V P = =
Required:
2
V
In this particular situation, Boyles Law will apply. This law describes the product of pressure and volume for a closed system. In a closed
system, the temperature and moles are constant, thus;
1 1 2 2
PV PV =
Simply rearrange for the final volume (V
2
);
1 1
2
2
PV
V
P
=
5
2
1.80 10 Pa
V

=
( )( )
3
5
0.300 dm
1.15 10 Pa
( )

3
2
0.470 dm V =


1-30
1.12. If the gas in Problem 1.11 were initially at 330 K, what will be the final volume if the temperature were raised to 550 K at constant
pressure?
Solution:
Given: same gas as in problem 1.11:
3
1
0.300 dm V =

1 2
330 K, 550 K T T = = (constant pressure)
Required:
2
V
In this particular situation, Charles Law will apply. This law states that under constant pressure, the volume of an ideal gas will vary
proportionately (by the same factor) with changes in temperature, thus;
1 2
1 2
V V
T T
=
Simply rearrange for the final volume (V
2
);
1 2
2
1
VT
V
T
=
( )
3
2
0.300 dm 500K
V =
( )
300K

3
2
0.500 dm V =

1-31
1.13. Calculate the concentration in mol dm
3
of an ideal gas at 298.15 K and at (a) 101.325 kPa (1 atm), and (b) 1.00 10
4
Pa (=10
9
atm). In each case, determine the number of molecules in 1.00 dm
3
.
Solution:
Given: Ideal Gas: ( ) ( )
4 9
1 2
298.15 K, 101.325 kPa 1 atm , 1.00 10 Pa 10 atm T P P = = =
Required: C (in mol dm
3
)

A
N (in V =1.00 dm
3
)
Knowing that concentration is equal to:
n
C
V
=
we can make the substitution into the Ideal Gas Law.
n P
C
V RT
= =
For pressure (a) and using the fact that m
3
=J Pa
-1
:
1
1
P n
C
V RT
= =
5
1
1
1.01325 10 Pa
8.3145 J K
C
=
( )
1
mol (298.15K
)

3
1
40.87 mol m C

=
Now convert units into mol dm
-3
:
3
3
1 3
40.87 mol m
0.0409 mol dm
10
C
= =
1-32
3
1
0.0409 mol dm C

=
Number of molecules per unit volume;
( )( )
3
0.0409 mol dm 0.0409 mol L
=
( )
3 23 1
dm 6.022 10 moleculesmol

( )

22 3
1
2.46 10 moleculesdm
N

=
3
1.00dm
22
2.46 10 molecules =
22
1
2.46 10 molecules N =
For pressure (b) using the same method:
2
2
P n
C
V RT
= =
4
2
1
1.00 10 Pa
8.3145 J K
C
=
( )
1
mol (298.15K
)

8 3
2
4.03 10 mol m C

=
Now convert units into mol dm
-3
;
8 3
11 3
2 3
4.03 10 mol m
4.03 10 mol dm
10
C

= =
11 3
2
4.03 10 mol dm C

=
Number of molecules per unit volume;
( )( )
11 3 11
4.03 10 mol dm 4.03 10 mol L

=
( )
3 23 1
dm 6.022 10 molecules mol

( )

1-33
13 3
2
2.43 10 moleculesdm
N

=
3
1.00dm
13
2.43 10 molecules =
13
2
2.43 10 molecules N =

1-34
1.14. A J -shaped tube is filled with air at 760 Torr and 22 C. The long arm is closed off at the top and is 100.0 cm long; the short arm is
40.00 cm high. Mercury is poured through a funnel into the open end. When the mercury spills over the top of the short arm, what is
the pressure on the trapped air? Let h be the length of mercury in the long arm.

Solution:

Given: J -Tube: 760 Torr, 22 C, long arm 100 cm, short arm 40 cm P T h l = = = =
Required: P of trapped air

The temperature is again held constant (same as in problems 1.10 and 1.11) so Boyles Law will apply;

1 1 2 2
PV PV =

We are given the initial pressure, so we can rearrange this equation to solve for
2
P ;
1 1
2
2
PV
P
V
=

Since h, the height of the mercury column on the trapped air side (long arm) is proportional to the volume of a uniform tube then we can
write;

1
2
100 cmHg
(100 ) cmHg
P
P
h

where h is the final height in centimeters of mercury in the long arm. In the short arm;

2 1
40 P h P = +

Substituting this into the above equation in order to eliminate
2
P gives;

1
1
100 cmHg
40
(100 ) cmHg
P
h P
h
+ =

1-35
Recall that 1mmHg =1 Torr and we therefore can make the substitution for
1
P ;

1
1
(100)
40
(100 )
P
h P
h
= +

( )
1 1
(100) (100 ) 40 P h h P = +

This can be expanded to obtain;
1
(100) P 4000 100 100 h P = +
2
1 1
40h h Ph +
2
140 76 4000 0 h h h + =
2
216 4000 0 h h + =

Using the quadratic equation then yields:

195.5 cmHg h = or 20.5 cmHg h =

The first value of h cannot be this large since the tube length is only 100 cm. Therefore,

20.5 cmHg h = is the correct value.

The final pressure can now be found;
1
2
(100) 76 cmHg(100cm
(100 )
P
P
h
=
)
(100 20.5) cm
95.6 cmHg =
2
956 Torr P =


1-36
1.15. A Dumas experiment to determine molar mass is conducted in which a gas samples P, , and V are determined. If a 1.08-g sample
is held in 0.250 dm
3
at 303 K and 101.3 kPa:
a. What would the samples volume be at 273.15 K, at constant pressure?
b. What is the molar mass of the sample?

Solution:

Given:
3
1.08 g, 0.250 dm , 303 K, 101.3 kPa m V T P = = = =
Required:
sample sample
and V M

Since we are working under constant pressure, Charles Law can be applied. This law states that

1 2
1 2
constant
V V
T T
= =

Solving for
2
V , we obtain
1 2
2
1
VT
V
T
=

Remember that the initial temperature is T =303 K so by making the appropriate substitutions we will have;

( )
3
2
0.250 dm 273.15K
V =
( )
303K

3
2
0.225 dm V =

Now that we have the final volume, it is possible to find the molar mass according to the equation;
mRT
M
PV
=

Recall that in order to derive this equation we must start with the ideal gas law;
1-37
PV nRT = and
m
n
M
= so we obtain
m
PV RT
M
=
mRT
M
PV
=
( )
3 1
1.08 10 kg (8.3145 J K
M

=
1
mol )(273.15K)
3 3
(101.3 10 Pa)(0.225dm
3 3 3
)(10 m dm

)

-1
0.1076 kg mol M =
1
108 g mol M

=

1-38
1.16. A gas that behaves ideally has a density of 1.92 g dm
3
at 150 kPa and 298 K. What is the molar mass of the sample?
Solution:
Given: Ideal Gas:

=1.92 g dm
3
, P =150 kPa, T =298 K
Required:
sample
M
Starting with the Ideal Gas Law is it possible to make substitutions and rearrangements in order to solve for the molar mass.
PV nRT =
nRT
P
V
=

Now, using the fact that
m
n
M
= we can make the next substitution;
m
RT
M
P
V
=
Since density is defined as
m
V
= then we can write;
RT
P
M
= and now solve for M

RT
M
P
=
3 1
1.92 kg m 8.3145 J K RT
M
P
= =
1
mol 298.15K
3
150 10 Pa

1
0.0317 kg mol M

=
1
31.7 g mol M

=
1-39
1.17. The density of air at 101.325 kPa and 298.15 K is 1.159 g dm
3
. Assuming that air behaves as an ideal gas, calculate its molar mass.
Solution:
Given: Air:
3
1.159 g dm , 298.15 K, 101.325 kPa T P = = =
Required:
air
M
Use the same method as the previous problem (1.16);
RT
M
P
=
3 1
1.159 kg m 8.3145 J K RT
M
P
= =
1
mol 298.15K
101325 Pa

1
0.0284 kg mol M

=
1
28.36 g mol M

=

1-40
1.18. A 0.200-dm
3
sample of H
2
is collected over water at a temperature of 298.15 K and at a pressure of 99.99 kPa. What is the pressure
of hydrogen in the dry state at 298.15 K? The vapor pressure of water at 298.15 K is 3.17 kPa.
Solution:
Given: H
2
(over water):
3
0.200 dm, 298.15 K, 99.99 kPa
t
V T P = = =
Vapor pressure of water: 3.17 kPa at T =298.15 K
Required:
2
H
P in the dry state
This problem makes use of Daltons Law of Partial Pressures which states:
The total pressure observed for a mixture of gases is equal to the sum of the pressure that each individual gas would exert had it been alone
occupying the container and at the same temperature.
P
i
=x
i
P
t

Partial pressure is defined as the total pressure multiplied by the mole fraction of a particular gas in the mixture. For this particular
hydrogen/water system, we can then write;
2 2
H H O t
P P P = + and solve for the pressure of hydrogen;
2 2
H O H t
P P P =
2
H
99.99 kPa 3.17 kPa P =
2
H
96.82 kPa P =


1-41
1.19. What are the mole fractions and partial pressures of each gas in a 2.50-L container into which 100.00 g of nitrogen and 100.00 g of
carbon dioxide are added at 25 C? What is the total pressure?
Solution:
Given: Container:
o
2.50 L, 25 C V T = =
Add 100.00 g of nitrogen and carbon dioxide
Required: , for each and
i i t
x P P
First find the amount of each gas in terms of moles because we are provided with their mass and can easily find their molar mass;
2
N
100.00g
m
n
M
=
28.012g
1
mol

2
N
3.5699 mol n =
2
CO
100.00g
m
n
M
=
44.010g
1
mol

2
CO
2.2722 mol n =
Now we can find the mole fractions associated with each gas using the individual and combined number of moles;
2
2
N
N
tot
3.5699mol
n
x
n
=
(3.5699 2.2722) mol +

2
N
0.6111 x =
2
2
CO
CO
tot
2.2722mol
n
x
n
=
(3.5699 2.2722) mol +

2
CO
0.3889 x =
1-42
Knowing the container volume and temperature of the system, the partial pressures can be calculated using the ideal gas law;
2
2
N
N
cont
3.5699mol
n RT
P
V
=
( )
1
8.3145 J K
1
mol
( )
298.15K
( )
3
2.50 dm

2
N
35.4 bar P =
2
2
CO
CO
cont
2.2722mol
n RT
P
V
=
( )
1
8.3145 J K
1
mol
( )
298.15K
( )
3
2.50 dm

2
CO
22.5 bar P =
The total pressure is now found using Daltons Law for Partial Pressures;
1 2 3 t i
P P P P P = + + + +
1 2 3 t t t t i t
P x P x P x P x P = + + + + (Eq. 1.53)
1 2 i
t
n RT n RT n RT
P
V V V
= + + +
1 2
( )
t i
RT
P n n n
V
= + + + (Eq. 1.54)
Any of the above forms can be used but for simplicity, we shall use Eq. 1.54;
(3.5699 2.2722) mol
t
P = +
1
(8.3145 J K
1
mol
)(298.15K
3
)
2.50 dm

57.9 bar
t
P =
Notice, once you take the pressure, you need to divide by 10
2
in order to get the pressure in units bar.
1-43
1.20. The decomposition of KClO
3
produces 27.8 cm
3
of O
2
collected over water at 27.5 C. The vapor pressure of water at this
temperature is 27.5 Torr. If the barometer reads 751.4 Torr, find the volume the dry gas would occupy at 25.0 C and 1.00 bar.
Solution:
Given: KClO
3
:
2
3
O
27.8 cm, 27.5 C V T = =
Vapor pressure of water: P =27.5 Torr
Barometer reading: P =751.4 Torr
Required:
dry gas
V
First it is possible to find the pressure of the dry gas at T =27.5 C by making use of the barometer reading and the vapor pressure of water;
gas barometer water
P P P =
gas
751.4 Torr 27.5 Torr P =
gas
723.9 Torr P = (Remember that this is at 27.5 C)
Since there is also a temperature change the following equality should be used to find the final volume of the system;
1 1 2 2
1 2
PV PV
T T
=
1 1 2
2
1 2
PVT
V
T P
=
Recall that 1 bar =750.06 Torr. Also, when making temperature conversions between Celsius to Kelvin: 27.5 C =273.15 +27.5 =300.65
K.
It is important to remember the initial conditions of the system (Dont mix up the temperatures!);
1 1 2
2
1 2
(723.9Torr PVT
V
T P
=
3
)(27.8 cm)(298.15K )
(300.65K )(750.06Torr )

1-44
3
2 dry gas
26.6 cm V V = =


1-45
1.21. Balloons now are used to move huge trees from their cutting place on mountain slopes to conventional transportation. Calculate the
volume of a balloon needed if it is desired to have a lifting force of 1000 kg when the temperature is 290 K at 0.940 atm. The
balloon is to be filled with helium. Assume that air is 80 mol % N
2
and 20 mol % O
2
. Ignore the mass of the superstructure and
propulsion engines of the balloon.
Solution:
Given: Balloon lifting force: m =1000 kg, T =290 K, P =0.940 atm
Required:
balloon
V
The lifting force comes from the difference between the mass of air displaced and the mass of the helium that replaces the air. We can work
under the assumption that the molar mass for air is 28.8 g mol
-1
. This is true if we consider the fact that air (in the problem) is composed 80
percent of nitrogen and 20 percent of oxygen.
2
1
N
14(2) 28 g mol M

=
But we will only consider 80 percent and therefore;
2
1 1
N
28 g mol (0.80) 22.4 g mol M

= = (in air)
2
1
O
16(2) 32 g mol M

=
But we will only consider 20 percent and therefore;
2
1 1
O
32 g mol (0.20) 6.4 g mol M

= =
Lifting force
air helium
( ) 1000 kg V =
And recall that we can use the ideal gas law to solve for the density of a gas (density is mass divided by volume);
PV nRT =
m
RT
nRT
M
P RT
V V M
= = = and solve for density

1-46
PM
RT
=
air
0.940atm
=
( )
1
101325 Paatm
( )
28.8g
1
mol
( )
1
8.3145 J K
1
mol
( )
290K
( )
3
10 g
( )
1
kg

3
air
helium
1.138 kg m
0.940atm
=
=
( )
1
101325 Paatm
( )
4.003g
1
mol
( )
1
8.3145 J K
1
mol
( )
290K
( )
3
10 g
( )
1
3
helium
kg
0.158 kg m
=

Now these values can be substituted into the equation for the volume of the balloon;
balloon
air helium
1000 kg
( )
V

=

balloon
1000kg
V =
(1.138 0.158) kg
3
m

3
balloon
1021 m V =


1-47
1.22. A gas mixture containing 5 mol % butane and 95 mol % argon (such as is used in Geiger-Mller counter tubes) is to be prepared by
allowing gaseous butane to fill an evacuated cylinder at 1 atm pressure. The 40.0-dm
3
cylinder is then weighed. Calculate the mass
of argon that gives the desired composition if the temperature is maintained at 25.0 C. Calculate the total pressure of the final
mixture. The molar mass of argon is 39.9 g mol
1
.
Solution:
Given: Gas mixture: 5 mol % butane and 95 mol % argon
3 1
cyl argon
1 atm, 40.0 dm, 39.9 g mol P V M = = =
Required:
argon
m and
t
P
By using the information given above, it is possible to find the mole fractions for each of the gases in the mixture;
PV nRT =
PV
n
RT
=
( )( )
3
butane
1
101325 Pa 40.0 dm
8.3145 J K
n
=
( )
1
mol 298.15 K
( )

butane
1.63 mol n =
Since the mixture contains 95 parts argon to 5 parts of butane, the ratio is then 95/5 =19:1 and we can determine the number of moles for
argon;
argon butane
19 n n =
argon
19(1.63) mol 30.97 mol n = =
Now that we have both the number of moles and molar mass, we can find the mass of argon;
argon argon argon
m n M =
1-48
argon
30.97mol m =
( )
1
39.9 gmol
( )

argon
1236.7 g m =
The total pressure can then be found by taking the sum of the partial pressures;
butane argon
( )
t
RT
P n n
V
= +
Remember that once you find the pressure, you must divide by 10
2
in order to convert to bar.
( ) 1.63 30.97 mol
t
P = +
1
8.3145 J K
1
mol
( )
298.15K
( )
3
40.0 dm

20.2 bar
t
P =
Since 1 bar =0.986 92 atm, then we can say that;
20.2(0.98692)
t
P =
19.9 atm
t
P =


1-49
1.23. The gravitational constant g decreases by 0.010 m s
2
km
1
of altitude.
a. Modify the barometric equation to take this variation into account. Assume that the temperature remains constant.
b. Calculate the pressure of nitrogen at an altitude of 100 km assuming that sea-level pressure is exactly 1 atm and that the
temperature of 298.15 K is constant.
Solution:
Given: gravitational constant g decreases by 0.010 m s
2
km
1
of altitude
Required: (a) modify
dP Mg
dz
P RT
| |
=
|
\ .

(b)
2
N
P at z =100 km, P =1 atm, T =298.15 K
a) The standard gravitational acceleration is defined as 9.807 m s
-2
. If g were to decrease by 0.010 m s
-2
per each kilometer in height, this
would be equivalent to a change of:
0.010m
2
3
s
10 m
5 2
10 s z

=
where z is the altitude. The new gravitational constant expression would be as follows:
2 5 2
9.807 m s 10 s g z

=
This can then be substituted into the Barometric Distribution Law equation,
dP Mg
dz
P RT
| |
=
|
\ .
(Eq. 1.74)
To give:
( )
2 5 2
9.807 m s 10 s
dP M
z dz
P RT

=
This can also be expressed in the following manner:
1-50
( )
2 6 2 2
0
ln 9.807 m s 5 10 s
P M
z z
P RT

| |
=
|
\ .

b) The second version of this equation can then be used to calculate the pressure of nitrogen gas at an altitude of 100 km.
0
28.0g
ln
P
P
| |
=
|
\ .
1
mol
( )
3 1
10 kgg

( )
1
8.3145 J K
1
mol
( )
298.15K
( )
( ) ( )
( )
2
5 2 6 5 2 2
9.807 10 m s 5 10 10 s z z

0
ln 10.51
P
P
| |
=
|
\ .

10.51 5
0
2.73 10
P
e
P

| |
= =
|
\ .

( )
5
0
2.73 10 1 atm P P
= =
5
2.73 10 atm P

=


1-51
1.24. Suppose that on another planet where the atmosphere is ammonia that the pressure on the surface, at h =0, is 400 Torr at 250 K.
Calculate the pressure of ammonia at a height of 8000 metres. The planet has the same g value as the earth.
Solution:
Given: Planet with ammonia atmosphere: h =0, P =400 Torr, T =250 K
Required:
3
NH
P at h =8000 m
We may begin as we did in the previous problem with the Barometric Distribution Law:
dP Mg
dz
P RT
| |
=
|
\ .
(Eq. 1.74)
We can then integrate this expression, with the boundary condition that P =P
0
when z =0, which yields;
0
ln
P Mgz
P RT
= (Eq. 1.75)
We can further manipulate the equation by exponentiating each side:
lne
0
Mgz
RT
P
e
P
= and solve for P

0
Mgz
RT
P Pe
=
Assume that the temperature remains constant at T =250 K and the molar mass of ammonia is M =0.017 kg mol
-1
. These values can be
substituted into the above equation.
( 0.017)(9.807)(8000)
(8.3145)(250)
(400 Torr) P e
=
0.642
(400 Torr) P e
=
210 Torr P =
1-52
1.25. Pilots are well aware that in the lower part of the atmosphere the temperature decreases linearly with altitude. This dependency may
be written as T =T
0
az, where a is a proportionality constant, z is the altitude, and T
0
and T are the temperatures at ground level
and at altitude z, respectively. Derive an expression for the barometric equation that takes this into account. Work to a form
involving ln (P/P
0
).
Solution:
Given: linear dependency of temperature on altitude: T =T
0
az
Required: Derive an expression for the barometric equation taking linearity of temperature increase into account.
Beginning with the Barometric Distribution Law equation (Eq. 1.74), and substituting for T from the linear dependency of temperature on
altitude equation;
dP Mg
dz
P RT
| |
=
|
\ .

( )
0
dP Mg
dz
P R T az
=

This is a differential equation. In order to solve this, let ( )
0
x T az = then we have:
dx adz = and rearrangement gives
dx
dz
a
=
Integration of the expression is then as follows (and with the proper substitutions):
0
1
ln
o
x
x
dx x
ax a x
| |
=
|
\ .

0
0
1
ln
o
x
x
T dx
ax a T az
| |
=
|
\ .

1-53
Integration of the LHS between the values
0
P and P (with the final substitution) gives:
0
0 0
ln ln
T az P Mg
P Ra T
| | | |
=
| |
\ . \ .


1-54
1.26. An ideal gas thermometer and a mercury thermometer are calibrated at 0 C and at 100 C. The thermal expansion coefficient for
mercury is:
0
4 9 10 2
1
( / )
1.817 10 5.90 10 3.45 10
P
V T
V

=
= + +

where is the value of the Celsius temperature and V
0
=V at =0. What temperature would appear on the mercury scale when the
ideal gas scale reads 50 C?
Solution:
Given: Thermometers:
1 2
0 C, 100 C T T = =
Thermal expansion coefficient for mercury:
4 9 10 2
0
1
( / ) 1.817 10 5.90 10 3.45 10
P
V T
V

= = + +

Required:
Hg
when ideal gas scale reads 50 C
In the case of a mercury column, we assign its length the value
100
l when it is at thermal equilibrium with boiling water vapor at 1atm
pressure. The achievement of equilibrium with melting ice exposed to 1atm pressure establishes the length,
0
l . Assuming a linear
relationship between the temperature and the thermometric property (length) we can write;
( )
( )
0
100 0
(100 C)
l l
l l
(Eq. 1.15)
This expression can be tailored to the situation given above by;
( )
( )
50 0
Hg
Hg
100 0
Hg
(100 C)
V V
V V

Since
0
1
( / )
P
V T
V
= then we can integrate the expression with respect to to get;
1-55
50
50 0 0
0
V V V d =

which can be evaluated as follows (divide the second and third terms by 2 and 3 respectively)
50 50
50
4 9 2 10 3
0
0
0 0
1.817 10 2.95 10 1.15 10 V

(
+ +
(

0
0.009 107V =
The same can be done for the denominator in the equation
( )
( )
50 0
Hg
Hg
100 0
Hg
(100 C)
V V
V V

100 100
100
4 9 2 10 3
0
0
0 0
1.817 10 2.95 10 1.15 10 x V

(
+ +
(

0
0.018 31V =
Now these two values can be substituted into the above equation to get;
0
Hg
0
0.009 107
(100 C)
0.018 31
V
V
=
Hg
49.7 C =


1-56
1.27. It takes gas A 2.3 times as long to effuse through an orifice as the same amount of nitrogen. What is the molar mass of gas A?
Solution:

Given: Gas A: t
effusion
=2.3 times longer than nitrogen
Required:
GasA
M

This particular problem makes use of Grahams Law of Effusion which states that the rate of effusion of a gas is inversely proportional to
the square root of the mass of its particles:

rate(gas 1) (gas 2) (gas 2) (gas 2)
rate(gas 2) (gas 1) (gas 1) (gas 1)
t M
t M
= = =

Since we can easily determine the molar mass of nitrogen (N
2
), we can make the appropriate substitutions and solve for the molar mass of
Gas A.
-1
nitrogen
28 g mol M =
nitrogen
A
nitrogen A
(gas 2)
(gas 1)
t
v M
v t M
= =
1
A
nitrogen A
1 28 g mol
2.3
v
v M
= =
2
2
1
A
1 28 g mol
2.3 M
| |
| |
= |
|
|
\ .
\ .

2
1
A
1 28 g mol
2.3 M
| |
=
|
\ .

1
A 2
28 g mol
1
2.3
M
=
| |
|
\ .

2 1
A
1.5 10 g mol M

=


1-57
1.28. Exactly 1 dm
3
of nitrogen, under a pressure of 1 bar, takes 5.80 minutes to effuse through an orifice. How long will it take for helium
to effuse under the same conditions?
Solution:

Given:
3
nitrogen
1 dm, 1 bar, 5.8 min V P t = = =
Required:
He
t

Using Grahams Law of effusion (as in previous problem 1.27) recall that effusion time is inversely proportional to the rate of effusion.

2 2
He He 2
N N
rate(N )
rate(He)
t M
t M
= =

Rearrange the above equation to isolate for the wanted variable,
He
t ;
2
2
He
He N
N
M
t t
M
=
We can determine the molar masses of both helium and nitrogen to get;
1
He
4g mol
5.80min t
=
1
28g mol

He
2.19 min t =


1-58
1.29. What is the total kinetic energy of 0.50 mol of an ideal monatomic gas confined to 8.0 dm
3
at 200 kPa?

Solution:

Given: Ideal monatomic gas: 0.50mol n = ,
3
8.0dm V = , 200kPa P =
Required:
tot
k
E

This particular problem refers to the section of Kinetic Theory of Gases. Here, we are trying to determine the relationship between
2
u and
T, the mechanical variable of u of Eq. 1.41:
2
3
Nmu
P
V
=

which is the fundamental equation derived from the simple kinetic theory of gases. For our purpose of determining this relationship (kinetic
energy and temperature), Eq. 1.41 may be converted into another useful form by recognizing that the average kinetic energy per molecule is
defined as;
2
1
2
k mu =
Substitution of this expression into Eq. 1.41 then gives;

1 2
2
3 3
k k PV N N = =

At constant pressure, the volume of a gas is proportional to the number of molecules and the average kinetic energy of the molecules. Since
N nL = then we can write;

2
3
k PV nL = and since k L is the total kinetic energy per mole of gas, then
2
3
k
PV nE =
3
2
k
PV
E
n
=

1-59
The data given above can be substituted into the above equation to yield;

3
3(200 kPa)(8.0 dm)
2 0.5 mol
k
E =
1
4800 J mol
k
E

=

So for half a mole, the kinetic energy will be:

2400 J
k
nE =

1-60
1.30. Nitrogen gas is maintained at 152 kPa in a 2.00-dm
3
vessel at 298.15 K. If its molar mass is 28.0134 g mol
1
calculate:
a. The amount of N
2
present.
b. The number of molecules present.
c. The root-mean-square speed of the molecules.
d. The average translational kinetic energy of each molecule.
e. The total translational kinetic energy in the system.

Solution:

Given: Nitrogen: P =152 kPa, V =2.00 dm
3
, T =298.15 K, M =28.0134 g mol
1
Required: see above a through e

Using the ideal gas law, PV nRT = we can solve for the number of moles present.
PV
n
RT
=
( )
3
152000 Pa (2.00dm
3 3 3
)(10 m dm

1
)
(8.3145 J K
1
mol )(298.15K
)

0.1226 mol n =

We can now use Avogadros number in order to find the number of molecules present;
( )( ) number molecules number of moles L =
0.1226 mol N nL = =
23 1
(6.022 10 mol
)
22
7.38 10 N =

We can take the square root of Eq. 1.43 in order to find the root mean square speed of the molecules;
2
3RT
u
M
= (Eq. 1.43)
2
3RT
u
M
=
2
3(8.3145 J K
u =
1
mol
)(298.15K
1
)
0.028 0134 kg mol

2 1
515.2 m s u

=
1-61

The average translational energy (for each molecule) is given by Eq. 1.44;
2
1
2
k mu =
1
0.0280134 kg mol
1
2
( )
1 2
23 1
(515.2 m s )
6.022 10 mol

21
6.175 10 J k

=

It is possible to find the total translational kinetic energy in the system by using the equation;
tot
3
2
k
E nRT = (Eq. 1.49)
tot
3
(0.1226mol
2
k
E =
1
)(8.3145 J K
1
mol
)(298.15K)
tot
456 J
k
E =


1-62
1.31. By what factor are the root-mean-square speeds changed if a gas is heated from 300 K to 400 K?
Solution:

Given: T
1
=300 K, T
2
=400 K
Required: change in root-mean-square speeds

Recall Eq. 1.43
2
3RT
u
M
=

Remember that in problem 1.29 we outlined the relationship between
2
u and T. Using this information, it is possible to see that the
following ratios are equivalent;
2
2 2
2
1
1
u T
T
u
=

Now we can determine the magnitude of change in root-mean-square speed when moving from a lower to a higher temperature.
2
1
400
1.33
300
T
T
= =
2
1
1.15
T
T
=


1-63
1.32. The collision diameter of N
2
is 3.74 10
10
m at 298.15 K and 101.325 kPa. Its average speed is 474.6 m s
1
. Calculate the mean
free path, the average number of collisions Z
A
experienced by one molecule in unit time, and the average number of collisions Z
AA

2
.
Solution:
Given:
1
A
-1
A
0
298.15 K, 101.3 3.74 1 25 kP 0 m a, 474.6 m s , T P d u
= = = =
Required:
A AA
, , Z Z
The mean free path is given by Eq. 1.68;
2
2
A A
V
d N

Using the ideal gas law, PV nRT
,
and solving for V, a useful expression for the mean free path can be obtained;
nRT
V
P

Giving the mean free path as,

2
2
A A
nRT
P
d N

A
N
L
n
, where
A
N is the number of particles
2
2
A
RT
d LP

1-64
1
8.3145 J K

=
1
mol
( )
298.15K
( )
( )
1 23 1
2
0
2 6.022 1 3.74 10 0 m m ol

( )
( )
8 2 1
2 2 1 2
10 J m Pa
where 1 J kg m s and 1 Pa 1kg m s
1
101325 Pa
6.53
kg
1 J
a
7
=
1 P
= =
=
2 2
m s
1kg
1 2
m s

3
8 2 3
6.537
1 m
10 m m

=
=

8
6.54 10 m

=

The average number of collisions Z
A
experienced by one molecule in unit time, also known as the collision frequency for one molecule is
given by Eq. 1.66;
2
A
1 A A
A
2
(SI unit:s )
d u N
Z
V

=
Using the ideal gas lawPV nRT and solving for V, a useful expression for Z
A
can be obtained.
nRT
V
P

2
A
A A
A
2 d u N P
Z
nRT
=
A
N
L
n
, where
A
1-65
( ) ( )
2
A
2
10
A
A
1 23 1
A
3.74 10
2
2 474.6 m s 6.022 10 ml m o
d u LP
Z
RT
Z

=

=
( )
( )
1
101325 Pa
8.3145 J K
1
mol
( )
298.15K
( )
3 1
2 2 1 2
1
A
where 1 J 1kg m s and 1
7259759289 m
Pa 1kg
s P

a
m s
1kg
1 Pa
J
J
1
Z

=
= =
=
1 2
m s

1kg
2 2
m s
3
9 3
A
7.26 0
1m
1 m

Z
=
=
1 3
s m

9 1
A
7.26 10 s Z

=
The average number of collisions Z
AA
2
, also known as the collision density is given by Eq. 1.65;
2 2
A
3 1 A A
AA 2
2
(SI unit:m s )
2
d u N
Z
V

=
AA
can be obtained;
nRT
V
P

( )
2 2 2
A
A A
AA 2
2
2
d u N P
Z
nRT
=
A
N
L
n
, where
A
( )
2 2 2
A
A
AA 2
2
d u L P
Z
RT
=
Solving for Z
AA
,
1-66
( ) ( )
1
2
1 23 1
A
0
A
474.6 m s 6.022 10 mo 3.74 10 m l
Z

=
( )
( )
2
2
1
101325 Pa
2 8.3145 J K
1
mol
( )
2
298.15K
( )
34
2
3 2 2
2 2 1 2
2
2
1
AA
2
10 m Pa J
where 1 J kg m s and 1 Pa 1kg m
8.93467 s
s
1kg
Pa
1J

1
Z

= =
=
=
2 4
m s

2
1kg
4 -4
m s
1
AA
6
34 3 6
8.9346
1m
10 m m 7 s Z

=
=

-1
AA
34 -3
10 8.9 m 3 s Z =


1-67
1.33. Express the mean free path of a gas in terms of the variables pressure and temperature, which are more easily measured than the
volume.
Solution:
Given:
2
2
A A
V
d N

Required: mean free path in terms of P and T
The mean free path is given by;
2
2
A A
V
d N

(Eq. 1.68)
Using the ideal gas law PV nRT and solving for V, a useful expression for the mean free path can be obtained;
nRT
V
P

2
2
A A
nRT
P
d N

A
N
L
n
, where
A
2
2
A
RT
d LP

1-68
1.34. Calculate Z
A
and Z
AA
for argon at 25 C and a pressure of 1.00 bar using
d =3.84 10
10
m obtained from X-ray crystallographic measurements.
Solution:
Given:
1 5 0
298. 3.84 15 K 10 m, , 10 Pa
A
T P d

= = =
Required:
A AA
, Z Z
Z
A
is given by Eq. 1.66;
2
A
1 A A
A
2
(SI unit:s )
d u N
Z
V

=
A
can be obtained.
nRT
V
P

2
A
A A
A
2 d u N P
Z
nRT
=
A
N
L
n
, where
A
2
A
A
A
2 d u LP
Z
RT
=
To solve for Z
A
the speed must first be found. The average speed is given in the Key Equations section of the chapter;
1-69
-1
8
8 8.3145 J K
RT
u
M
u
=
=
1
mol
( )
298.15K
( )
39.948g
1
mol
3 1
10 kg g

( )
1
2 2
since 1 J 1kg
1
m s
58021.4434 J kg
158021.443 kg 4
u
u
=
=
=
( )
2 1 2
m s kg

1
397.519 m s u

=

Solving for Z
A
gives;
( ) ( )
2
A
1 23
2
1 1
A
0
3.84 10 m
2
2 397.519 m s 6.022 10 mol
A
A
d u LP
Z
RT
Z
=

=
( )
( )
1
10000 Pa
8.3145 J K
1
mol
( )
298.15K
( )
1
A
2 2 1 2
3 1
where 1 J 1kg m s and 1 Pa
632637614
1kg
9 m s Pa
m s
1kg
1 Pa
1 J
J Z

=
= =
=
1 2
m s

1kg
2 2
m s
3
9 3
A
6.33 0
1m
1 m

Z
=
=
1 3
s m

9 1
A
6.33 10 s Z

=

Z
AA
is given by Eq. 1.65;
1-70
2 2
A
3 1 A A
AA 2
2
(SI unit:m s )
2
d u N
Z
V

=
Using the ideal gas lawPV nRT and solving for V, an expression for Z
AA
is as follows;
nRT
V
P

( )
2 2 2
A
A A
AA 2
2
2
d u N P
Z
nRT
=
A
N
L
n
, where
A
( )
2 2 2
A
A
AA 2
2
d u L P
Z
RT
=
Solving for Z
AA
to get;
( ) ( )
1
2
23 -1
A
0
A
1
397.519 m s 6.022 3.8410 10 mol m
Z

=
( )
( )
2
2
1
10000 Pa
2 8.3145 J K
1
mol
( )
2
298.15K
( )
2

34 3 2 2
2 2 1 2
2
2
2
1
AA
10 m Pa J
since 1 J 1kg m s and 1 Pa 1kg m
7.68
s
413 s
1kg
1 Pa
1 J
Z

= =
=
=
2 4
m s

2
1kg
4 4
m s
1
AA
6
34 3 6
7.68413
1 m
10 m m s Z

=
=

3 1
AA
4 3
10 m 7.68 s Z

=

1-71
1.35. Calculate the mean free path of Ar at 20 C and 1.00 bar. The collision diameter
d =3.84 10
10
m.
Solution:
Given:
10 5
20C 293.15 K, 1.00 bar 10 Pa, 3.84 10 m
A
P d T

= = = = =
Required:
2
2
A A
V
d N

Using the ideal gas lawPV nRT and solving for V, a useful expression for the mean free path can be obtained.
nRT
V
P

2
2
A A
nRT
P
d N

A
N
L
n
, where
A
2
2
A
RT
d LP

1-72
-1
8.3145 J K
=
1
mol
( )
293.15K
( )
( )
1 23 -1
2
0
2 6.022 10 3.84 10 m mol

( )
( )
8 2 1
2 2 1 2
10 J m Pa
since 1 J 1kg m s and 1 P
10000
a 1kg m s
1kg
1 J
1 Pa
Pa
6.1781

= =
=
=
2 2
m s
1kg
1 2
m s

3
8 2 3
6.1781
1 m
10 m m

=
=

8
6.18 10 m

=

1-73
1.36. Hydrogen gas has a molecular collision diameter of 0.258 nm. Calculate the mean free path of hydrogen at 298.15 K and (a) 133.32
Pa, (b) 101.325 k Pa, and (c) 1.0 10
8
Pa.
Solution:
Given:
10
0.258 nm 2.58 10 m, 298.15 K
A
d T
= = =
Required:
2
A
2
A
V
d N

Using the ideal gas lawPV nRT and solving for V, a useful expression for the mean free path can be obtained.
nRT
V
P

2
A
2
A
nRT
P
d N

A
N
L
n
, where
A
2
2
A
RT
d LP

Now using the fact that P =133.32 Pa we can make the appropriate substitutions to get;
1-74
1
8.3145 J K

=
1
mol
( )
298.15K
( )
( )
1 23 1
2
0
2 6.022 1 2.58 10 0 m m ol

( )
( )
4 2 1
2 2 1 2
10 J m Pa
where 1 J 1kg m s and 1 P
133.32
a 1kg m s
1kg
1 J
1 P
Pa
1. 4
a
04

= =
=
=
2 2
m s
1kg
1 2
m s

3
4 2 3
1.044
1 m
10 m m

=
=

4
1.044 10 m

=

With the next pressure (P =101.325 kPa) we can use the same method as outlined above;

1
8.3145 J K

=
1
mol
( )
298.15K
( )
( )
1 23 1
2
0
2 6.022 1 2.58 10 0 m m ol

( )
( )
7 2 1
2 2 1 2
10 J m Pa
where 1 J 1kg m s and 1 Pa
101325 Pa
1
1kg m s
1kg
1 J
1
.
Pa
37

= =
=
=
2 2
m s
1kg
1 2
m s

3
7 2 3
1.37
1 m
10 m m

=
=

7
1.37 10 m

=

For the final pressure
8
1.0 10 Pa P =
;

1-75
-1
8.3145 J K
=
1
mol
( )
298.15K
( )
( )
1 23 1
2
0
2 6.022 1 2.58 10 0 m m ol

( )( )
8
10 2 1
2 2 1 2
10 J m Pa
where 1 J 1kg m s and 1 Pa 1k
1.0 10 Pa
g m s
1kg
1 J
1
.39
P
1
a
=
=
=
=
2 2
m s
1kg
1 2
m s

3
10 2 3
1 m
1 1 0 m m .39

=
=

10
10 9 m 1.3

=


1-76
1.37. In interstellar space it is estimated that atomic hydrogen exists at a concentration of one particle per cubic meter. If the collision
diameter is 2.5 10
10
m, calculate the mean free path . The temperature of interstellar space is 2.7 K.
Solution:
Given:
1
A
3 0
2.7 K, 2.50 10 m, 1 particle m T C d

= = =
Required:
2
A A
2
V
d N

Concentration is given by;
A
N
C
V
= , where
A
Now it is possible to solve for
( ) ( )
2
3
2
10
18
1
2
1
2 1 particle m 2.50 10 m
10 . m 360
A
d C

=

=
=

18
3.60 10 m =
This is about a hundred times greater than the distance between the earth and the nearest star (Proxima Centauri)!


1-77
1.38. Calculate the value of Avogadros constant from a study made by Perrin [Ann. Chem. Phys., 18, 1(1909)] in which he measured as a
function of height the distribution of bright yellow colloidal gamboge (a gum resin) particles suspended in water. Some data at 15
C are:
height, z/10
6
5 35
N, relative number of gamboge particles at height z 100 47

gamboge
=1.206 g cm
3

water
=0.999 g cm
-3
radius of gamboge particles, r =0.212 10
6
m
(Hint: Consider the particles to be gas molecules in a column of air and that the number of particles is proportional to the pressure.)
Solution:
Given: see above
Required: Avogadros number, L
Since we consider the gamboges particles to be proportional to the pressure, we can write;
dP Mg
dz
P RT
| |
=
|
\ .
(Eq. 1.74)

Here, g is the acceleration due to gravity. Taking the integral of both sides and simplifying gives;
0
ln
N Mg
z
N RT
= where M mL =

This can then be substituted into the above equation to get;

0
ln
N mLg
z
N RT
=
Solving for L;
0
ln
RT N
L
mg z N
=

1-78
Density is given by
m
V
=
Rearranging for the mass of the gamboges particle then gives;
m V =

Where V is the volume of the gamboges particle. Since we know that volume is given by;
3
4
3
r
V

=

We can then define mass as follows;
3
4
3
r
m

=
Now Avogadros number can be expressed as;
3
0
ln
4
3
RT N
L
N
r g z

=
| |

|
\ .

Solving for Avogadros number,
1
8.3145 J K
L
=
( )
1
mol 288.15K
( )
3
4
(1.206 g cm
3
3
0.999 g cm
3
3
kg m
) 10
3
g cm
6
0.212 10 m
| |
|
|
\ .
( ) ( )
( )
3
2
6 6
9.81 m s
1 100
ln
47 35 10 m 5 10 m
| |
|
|
\ .

23 1
7.43974 10 mol L

=
23 1
7.44 10 mol L

=

1-79
1.39. Refer to Table 1.3 (p. 32) and write expressions and values for (a) the ratio
2
/ u u , and (b) the ratio /u
mp
.

Note that these ratios are
independent of the mass and the temperature. How do the differences between them depend on these quantities?
Solution:
Given: Table 1.3
Required:
2
/ u u
and
/
mp
u
From Table 1.3 the root mean speed is
2 B
3k T
u
m
= , and the average speed is
B
8k T
u
m
=
2
B B
2
B
3 8
3
k T k T u
m m u
k T
u
u
=
=
m
m
B
8k T
2
3
8
u
u
=

2
1.085
u
u
=

From Table 1.3 the average speed is
B
8k T
u
m
= and the most probable speed is
B
mp
2k T
u
m
=
1-80
B B
mp
B
mp
8 2
8
k T k T
u m m
k T
=
=
m
m
B
2k T
mp
mp
4
2
=
=

mp
1.128
u
=
The differences between
2
and u u

and between
mp
and u increase with T and decrease with m.


1-81
1.40. The speed that a body of any mass must have to escape from the earth is 1.07 10
4
m s
1
. At what temperature would the average
speed of (a) a H
2
molecule, and (b) an O
2
molecule be equal to this escape speed?
Solution:
Given:
4 -1
1.07 10 m s u =
Required:
2
H
T
,

2
O
T
Average speed, as listed in Table 1.3, is given by
B
8k T
u
m
=

By rearranging this equation, temperature can be described as;

2
B
8
mu
T
k
=
The mass is given by
M
m
L
= and by using this expression, the temperature can be simplified to;
2
B
8
u M
T
k L
= where,
B
R
k
L
=
2
8
u M
T
R
=
a. Solving for
2
H
T
;

1-82
( )
2
2
4 1
H
1.07 10 m s 2 1.00794g
T

=
1
mol
( )
3 1
10 kgg

1 1
8 8.3145 J K mol

( )
2
2
2
2
H
2
H
2
2 1
2
where 1J 1kg m
10898 m s kg J K
10898m s kg
s
T
T
=
=
=
1 2 2
kg m s

( )
2
H
K
10898 K T =

2
4
H
1.09 10 K T =
b. Solving for
2
O
T
;

( )
2
2
4 -1
O
1.07 10 m s 2 15.9994g
T

=
-1
mol
( )
3 -1
10 kg g
-1 -1
8 8.3145 J K mol
( )
2
2
2
2 -2 -1
O
2 -2
O
2
where 1 J 1kg m s
172992 m s kg J K
172992m s kg
T
T
=
=
=
1 2 2
kg m s

( )
2
O
K
172992 K T =

2
5
O
1.73 10 K T =


1-83
1.41. a. For H
2
gas at 25 C, calculate the ratio of the fraction of molecules that have a speed 2u to the fraction that have the average
speed . How does this ratio depend on the mass of the molecules and the temperature?
b. Calculate the ratio of the fraction of the molecules that have the average speed
100 C
at 100 C to the fraction that have the
average speed
25 C
at 25 C. How does this ratio depend on the mass?
Solution:
Given: 25 C 298.15K T = =
Required: a.
1 2
1 2
u u
u u
dN dN
N N
, where 1 2 2 , u u u u = = ,
B
8k T
u
m
=
b.
1 2
1 2
u u
u u
dN dN
N N
where 1 100 C 2 25 C , u u u u = = ,
B
8k T
u
m
=
a) The key words in this problem are ratio of the fractions, therefore we use the Boltzmann distribution. The Boltzmann distribution is
given by Eq. 1.91;
2
B
3/2
/2 2
B
4 e
2
mu k T
dN m
u du
N k T

| |
=
|
\ .

Solving for the ratio;
1 2
1 2
3/2
B
4
2
u u
u u
m
k T dN dN
N N
| |
|
\ .
=
2
1 B
2
/2
1 e
mu k T
u du
3/2
B
4
2
m
k T
| |
|
\ .
2
2 B
2
/2
2 e
mu k T
u du
( )
2 2
1 2 B
1 2
1 2
2
/2
1
2
2
e
m u u k T
u u
u u
dN dN
u
N N
u

| |
| =
|
\ .

1-84
( ) ( )
2 2
B
1 2
1 2
1 2
2
2 /2
2
where 2 ,
2
e
m u u k T
u u
u u
u u u u
u
dN dN
N N
u
| |
|
\ .
= =
| |
|
=
|
|
\ .

( )
2 2
B
1 2
1 2
2
4 /2
4
e
m u u k T
u u
u u
dN dN
u
N N

=
2
u
| |
|
|
\ .

( )
2
B
1 2
1 2
2
B
B
1 2
1 2
1 2
1 2
3 /2
B
8
3 /2
4e
8
since , we can substitute for the average speed;
4e
4e
m u k T
u u
u u
k T
m k T
m
u u
u u
m
u u
u u
dN dN
N N
k T
u
m
dN dN
N N
dN dN
N N
| |
| |
|
|
| |
\ .
\ .
=
=
=
=
B
24k T
m
B
1
2k T
| | | |
| |
| |
\ . \ .
1 2
1 2
1 2
1 2
12
4e
0.087735885
u u
u u
u u
u u
dN dN
N N
dN dN
N N
| |
|
|
\ .
=
=

1 2
1 2
2
8.77 10
u u
u u
dN dN
N N
=
It is now possible to see that the ratio is independent of mass and temperature of the molecules.

1-85
b)
1 2
1 2
3/2
B
4
2
u u
u u
m
k dN dN
N N
| |
|
\ .
=
2
1 B 100 C
3/2
2
/2
1
100 C
1
e
mu k T
u du
T
| |
|
|
\ .
3/2
B
4
2
m
k
| |
|
\ .
2
2 B 25 C
3/2
2
/2
2
25 C
1
e
mu k T
u du
T
| |
|
|
\ .
2 2
1 2
B 100 C 25 C
1 2
1 2
2 2
1 2
B 100 C 25 C
1 2
1 2
3/2
2
2 100 C 1
3/2 2
2
25 C
3/2
2
2 1 100 C
2
25 C 2
B
1
e
1
e
8
where
m u u
k T T
u u
u u
m u u
k T T
u u
u u
T dN dN
u
N N
u
T
dN dN T
u
N N T
u
k T
u
m

| |
|
|
\ .
| |

|
|
\ .
| |
|
|
| |
\ .
| =
|
| |
\ .
|
|
\ .
| | | |
| = |
| |
\ . \ .
=

2 2
B 100 C B 25 C
100 C 25 C
1 2
1 2
8 8
2
B 100 C
2
3/2
100 C
2
25 C
B 25 C
8
e
8
B
k T k T
m m
m
k T T
u u
u u
k T
m
dN dN T
N N T
k T
m

| |
| | | |
|
| |
| | |
\ . \ . |

|
|
|
|
\ .

| |
| |
|
|
| |
| |
\ .
| = |
|
| | |
\ .
| |
| |
\ . \ .

1-86

B 100 C B 25 C
100 C 25 C
1 2
1 2
B
1 2
1 2
8 8
3/2 2
100 C 100 C
25 C 25 C
1 1/2
2
100 C
25 C
e
e
B
k T k T
m m m
k T T
u u
u u
m
k
u u
u u
dN dN T T
N N T T
dN dN T
N N T

| | | | | |
| | |
| |
| \ . \ .
|
|

\ .

| | | |
= | |
| |
\ . \ .
| |
= |
|
\ .
B
8 k
m
| |
|
|
\ .
100 C
100 C
T
T
| |
|
|
\ .
25 C
25 C
T
T
| |
|
|
\ .
( )
1 2
1 2
1 2
1 2
1 2
1 2
1/2
4
0
100 C
25 C
1/2
100 C
25 C
e
373.15 K
u u
u u
u u
u u
u u
u u
dN dN T
N N T
dN dN T
N N T
dN dN
N N
| | | |
| |
| |
\ . \ .
| |
|
\ .
| |
= |
|
\ .
| |
= |
|
\ .
=
298.15 K
1 2
1 2
1/2
0.8938727
u u
u u
dN dN
N N
| |
|
\ .
=

1 2
1 2
0.894
u u
u u
dN dN
N N
=


1-87
1.42. Suppose that two ideal gases are heated to different temperatures such that their pressures and vapor densities are the same. What is
the relationship between their average molecular speeds?
Solution:
Given: Two Ideal Gases, , and P T

Required: the relationship between the average speeds of two ideal gases
To solve this problem, we use the Ideal Gas Law to eliminate the temperature dependence from the equation for average speed. This is true
because for
1 2 1 2 1 2
and , and T T P P P = =
;

B
B
where
PV nRT
PV
T
nR
R k L
PV
T
nk L
=
=
=
=

Substituting the above expression into the equation for average speed, as given in Table 1.3, and simplifying, gives the relationship between
the average speed of two ideal gases that are heated to different temperatures such that their pressures and vapor densities are the same.
B
B
8
8
k T
u
m
k
u
=
=
B
PV
mn k
8
where
8
L
PV
u
mnL
N nmL
V V
P
u
=
= =
=

1-88
Since P and are the same, the average speed is the same for both gases.


1-89
1.43. a. If
25 C
is the average speed of the molecules in a gas at 25 C, calculate the ratio of the fraction that will have the speed
25 C
at
100 C to the fraction that will have the same speed at 25 C.
b. Repeat this calculation for a speed of 10
25 C
.

Solution:
Given:
100 C 25 C
373.15 K, 298.15 K T T

= =
Required: a)
100 C C
100 C C
T T
T T
dN dN
N N
25
25

b)
100 C C
100 C C
T T
T T
dN dN
N N
25
25

The key words in this problem are ratio of the fractions, therefore we use the Boltzmann distribution. The Boltzmann distribution is given
by Eq. 1.91;
2
B
3/2
/2 2
B
4 e
2
mu k T
dN m
u du
N k T

| |
=
|
\ .
, where the average speed of molecules is given in Table 1.3 as
B
8k T
u
m
=
Solving for the ratio we get;
100 C C
100 C C
3/2
B
4
2
T T
T T
m
k dN dN
N N
25
25
| |
|
\ .
=
( )
( )
2
B 100 C 25 C
100 C
3/2
2
/2
100 C
1
e
m u k T
u du
T

| |
|
|
\ .
3/2
B
4
2
m
k
| |
|
\ .
( )
( )
2
B 25 C 25 C
25 C
3/2
2
/2
25 C
1
e
m u k T
u du
T

| |
|
|
\ .
( ) ( )
( )
( )
2 2
25 C 25 C
B 100 C 25 C 100 C
100 C C
100 C C
25 C
3/2
2
2
100 C
3/2 2
25 C
1
e
1
u u
m
k T T
T T
T T
u dN dN T
N N
u
T

25
25

| |
|
|
|
\ .
| |
|
|
\ .
=
| |
|
|
\ .

1-90
B
8
where
k T
u
m
=
2 2
B 25 C B 25 C
B 100 C 25 C
100 C C
100 C C
100 C C
100 C C
8 8
2
B C
2
3/2
100 C
2
25 C
B 25 C
100 C
8
e
8
k T k T
m m
m
k T T
T T
T T
T T
T T
k T
m dN dN T
N N T
k T
m
dN dN T
N N

25
25
25
25
| |
| | | |
|
| |
| | |
\ . \ . |
100
|
|
|
|
\ .
| |
|
|
| |
\ .
= |
|
| |
\ .
|
|
\ .
=
B 25 C B 25 C
B 100 C 25 C
B 100 C C
100 C C
8 8
3/2 2
100 C
25 C 25 C
1/2 1
2
100 C
25 C
e
e
k T k T
m m m
k T T
m
k T T
T T
T
T T
dN dN T
N N T

25
25
| | | | | |
| | |
| |
| \ . \ .
|
|

\ .

| | | |
| |
| |
\ . \ .
| |
= |
|
\ .
B
8 k
m
| |
|
|
\ .
25 C 25 C
100 C 25 C
T T
T T

| |
|
|
\ .
25 C
100 C C 100 C
100 C C
100 C C
100 C C
1/2 4
1
100 C
25 C
e
373.15 K
T
T T T
T T
T T
T T
dN dN T
N N T
dN dN
N N

25
25
25
25
| |
|
|
\ .
| | | |
|
|
|
\ .
\ .
| |
= |
|
\ .
=
298.15 K
1/2 4 298.15K
e

| |
|
\ .
| |
|
\ .
373.15K
100 C C
100 C C
1
1.154559
T T
T T
dN dN
N N
25
25
| |
|
\ .
=

100 C C
100 C C
1.155
T T
T T
dN dN
N N
25
25
=
At a speed of 10
25 C
;
1-91
100 C C
100 C C
3/2
B
4
2
T T
T T
m
k dN dN
N N
25
25
| |
|
\ .
=
( )
( )
2
B 100 C 25 C
100 C
3/2
2
10 /2
100 C
3/2
B
1
e
4
2
m u k T
u du
T
m
k
| |
|
|
\ .
| |
|
\ .
( )
( )
( ) ( )
( )
( )
2
B 25 C 25 C
25 C
2 2
25 C 25 C
B 100 C 25 C 100 C
100 C C
100 C C
25 C
3/2
2
/2
25 C
3/2
10
2
2
100 C
3/2 2
25 C
B
1
e
1
e
1
8
where
m u k T
u u
m
k T T
T T
T T
u du
T
u dN dN T
N N
u
T
k T
u
m

25
25

| |
|
|
|
\ .
| |
|
|
\ .
| |
|
|
\ .
=
| |
|
|
\ .
=

1-92
2 2
B 25 C B 25 C
B 100 C 25 C
100 C C
100 C C
100 C C
100 C C
8 8
10 2
B C
2
3/2
100 C
2
25 C
B 25 C
100
8
e
8
k T k T
m m
m
k T T
T T
T T
T T
T T
k T
m dN dN T
N N T
k T
m
dN dN T
N N

25
25
25
25
| |
| | | |
|
| |
| | |
\ . \ . |
100
|
|
|
|
\ .

| |
|
|
| |
\ .
= |
|
| |
\ .
|
|
\ .
=
B 25 C B 25 C
B 100 C 25 C
100 C C B
100 C C
8 8
100
3/2 2
C 100 C
25 C 25 C
1/2 1
2 100 C
25 C
e
e
k T k T
m m m
k T T
m
T T k
T T
T
T T
dN dN T
N N T

25
25
| | | | | |
| | |
| |
| \ . \ .
|
|

\ .

| | | |
| |
| |
\ . \ .
| |
= |
|
\ .
B
8 k
m
| |
|
|
\ .
25 C 25 C
100 C 25 C
25 C
100 C C 100 C
100 C C
100 C C
100 C C
100
100 1/2 4
1
100 C
25 C
e
373.15 K
T T
T T
T
T T T
T T
T T
T T
dN dN T
N N T
dN dN
N N
25
25
25
25
| | | |
| |
| |
\ .\ .
| | | |
|
|
|
\ .
\ .
| |
= |
|
\ .
=
298.15 K
1/2 4 100 298.15K
e

| |
|
\ .
| |
|
\ .
373.15K
100 C C
100 C C
1
44
2.09987 10
T T
T T
dN dN
N N
25
25
| |
|
\ .
=

100 C C
100 C C
44
2.10 10
T T
T T
dN dN
N N
25
25
=


1-93
1.44. On the basis of Eq. 1.80 with =1/k
B
T, derive an expression for the fraction of molecules in a one-dimensional gas having speeds
between u
x
and u
x
+du
x
. What is the most probable speed?
Solution:
Given: =1/k
B
T,
2
/2
= e
x
mu
x x
dP B du

Required:
dN
N
, the fraction of molecules in a one-dimensional gas
Using Eq. 1.80, the fraction of molecules in a one-dimensional gas having speeds between u
x
and u
x
+du
x
can be written as;
2
2
/2
/2
0
e
e
x
x
mu
x x
mu
x
dP B du dN
N P
B du
= =

Using
2
1/2
0
1
2
ax
e dx
a

| |
=
|
\ .
from the appendix in Chapter 1, the denominator can be simplified.

2
1/2
/2
0
2
e
2
x
mu
x
B
B du
m
| |
=
|
\ .

1-94
2
2
2
2
B
/2
1/2
1/2
/2
1/2
/2
B
1/2 1
2
B
e
=
2
2
2 e 2
=
=2e
2
1
where
=2e
2
x
x
x
x
mu
x
mu
x
mu
x
mu
k T
x
B du dN
N
B
m
dN B
du
N B m
dN m
du
N
k T
dN m
du
N k T
| |
|
\ .
| |
|
\ .
| |
|
\ .
=
| |
|
\ .

2
B
1/2 1
2
B
2
=e
x
mu
k T
x
dN m
du
N k T
| |
|
\ .

1-95
1.45. Derive an expression for the fraction of molecules in a one-dimensional gas having energies between
x
and
x x
d + .Also, obtain
an expression for the average energy x .
Solution:
Given:
2
B
1/2 1
2
B
2
=e
x
mu
k T
x
dN m
du
N k T
| |
|
\ .
(from problem 1.44)
Required:
dN
N
, the fraction of molecules in a one-dimensional gas
Using Eq. 1.93,
2
1
2
x
mu = , the fraction of molecules in a one-dimensional gas having speeds between u
x
and u
x
+du
x

,
2
B
1/2 1
2
B
2
=e
x
mu
k T
x
dN m
du
N k T
| |
|
\ .
(from problem 1.44), can be converted into the fraction molecules having energies between
x
and
x x
d +
;
1-96
( )
( )
( )
( )
2
1
2
1
2
1
1
2
2
1
1
2
2
1
2
1
2
1
2
2
2 1 2
2
2 1
1 1
2
1
2
2
2
x x
x
x
x x
x
x x
x
x
x
x
x
x
x
x
x
x
x x x
mu
u
m
du
d m m
du
d m m
du
d m m
du
d m
du
m
d
du m d
=
=
| | | |
=
| |
\ . \ .
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
=
=

B
1/2
B
1
e
x
k T
x
x
dN
d
N k T
| |
=
|
\ .

The average energy is given by;
0
dN
N

(Eq. 1.97)

Tailoring the above equation to this particular situation, we get;

1-97
B
B
0
1/2
0
B
1/2
12
0
B
1
e
1
e
x
x
x
x x
k T
x x x
x
k T
x x x
dN
N
d
k T
d
k T
=
| |
| |
| =
|
|
\ .
\ .
| |
=
|
\ .

Using
1/2
1/2
0
1
2
ax
e x dx
a a

| |
=
|
\ .
from the appendix in Chapter 1, the expression can be simplified.

( )
( )
B
1
12
2
B B
0
1
1 2
2
B B
B
B
1
e
2
1 1
2
1
2
x
k T
x x
x
x
d k T k T
k T k T
k T
k T
=
| |
=
|
\ .
=

Solvingfor the fraction of energies we get;

( )
B
B
B
1/2 2 1
1
2
2
B
1/2
B
1/2
B
2
e 2
2 1
e
2
1
e
x
x
x
m
m k T
x x
k T
x
x
k T
x
x
dN m
m d
N k T
dN m
d
N k T m
dN
d
N k T

| |
|

\ .
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .

B
1
2
x
k T =

1-98
1.46. Derive an expression for the fraction of molecules in a two-dimensional gas having speeds between u and u +du. (Hint: Proceed by
analogy with the derivation of Eq. 1.91.) Then obtain the expression for the fraction having energies between and d + . What
fraction will have energies in excess of
*
?
Solution:
Given: Two dimensional gas:
2
3/2
/2 2
4 e
2
B
mu k T
B
dN m
u du
N k T

| |
=
|
\ .

Required:
dN
N
, the fraction of molecules in a two-dimensional gas

The following equations:
2
/2
= e
x
mu
x x
dP B du

(Eq. 1.80)

2
/2
= e
y
mu
y y
dP B du

(Eq. 1.81)

can be combined to give an expression reflecting the probability that the two components of speed have values between u
x
and u
x
+du
x
, u
y

and u
y
+du
y
.

( )( )
( )
2 2
2 2
/2 /2
/2
2
= e e
e
y x
x y
mu mu
x y x y
m u u
x y x y
dP dP B du B du
dP dP B du du

+
=

Using polar coordinates, we consider a circular shell of radius u and replace
x y
du du by2 udu , and take
2 2 2
x y
u u u = +
We can then rewrite
( )
2 2
2 /2
2 2 /2
e as 2 e
x y
m u u
mu
x y x y
dP dP B du du dP B udu
+

= =
Using Eq. 1.91, an expression for the speed can be obtained;
1-99
2
2
2
2
2
2
2 /2
2 /2
0
2 /2
2 /2
0
/2
/2
0
2 e
2 e
2 e
2 e
e
e
mu
mu
mu
mu
mu
mu
dN dP B udu
N P
B udu
dN B udu
N
B udu
dN udu
N
udu
= =
=
=

Using
2
0
1
2
ax
e x dx
a
from the appendix to Chapter 1, the denominator can be simplified.

2
2
2
2
2
B
/2
0
/2
0
/2
/2
B
2
B
1 2
e
2
1
e
e
1
e
1
where
e
mu
mu
mu
mu
mu
k T
udu
m
udu
m
dN udu
N
m
dN
m udu
N
k T
dN m
udu
N k T
| |
=
|
\ .
=
=
=
=
=

1-100
2
B
2
B
e
mu
k T
dN m
udu
N k T
=
Using Eq. 1.93,
2
1
2
mu = , the fraction of molecules in two dimensional gas having speeds between u and u +du., can be converted into the
fraction molecules having energies between and d +
;
( )
2
1
2
1
2
1
2
1
1
2
2
1
2
2
1 2 2
2
1 2
1 1
2
mu
u
m
du
d m m
du
d m m
du
d m m
=
| |
=
|
\ .
| | | |
=
| |
\ . \ .
| |
=
|
\ .
| |
=
|
\ .

( )
( )
( )
1
1
2
2
1
2
1
2
1
2
2
2
du
d m
du
m
d
du m d
| |
=
|
\ .
=
=

We can now solve for the fraction of energies;
1-101
( )
( )
2
B
B
B
B
2
B
1
2 1
1
2
2
2
B
1
1
2
2
B
1
2
B
e
2
e 2
2
e 2
e
mu
k T
m
m k T
k T
k T
dN m
udu
N k T
dN m
m d
N k T m
dN m
m d
N k T m
dN m
m
N k T
| |
|

\ .

=
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
1
2
m
| |
|
\ .
B
B
1
e
k T
d
dN
d
N k T
=

B
B
1
e
k T
dN
d
N k T
=
The fraction of molecules with energy greater than
*
can be obtained from the expression
B
B
*
B
*
*
*
*
*
e
e
e
k T
k T
k T
N
d
N
N
N
N
N
=
=
=

1-102
1.47. In Section 1.13 it was stated that the van der Waals constant b is approximately four times the volume occupied by the molecules
themselves. J ustify this relationship for a gas composed of spherical molecules.
Solution:
The Van der Waals constant b represents the excluded volume occupied by the volume of the colliding molecules. When two molecules
collide, the closest they can come to one another is a distance of 2r, therefore the excluded volume per molecule can be represented as a
sphere with a radius of no less than 2r.

b can be calculated using the volume of a sphere, taking the radius as 2r.
( )
( )
3
3
3
4
3
where 2
4 2
3
4 8
8
3
4
r
V
r r
r
V
r
V V
b V
=
=
=
= =
=

Since we only consider the volume occupied by one molecule of radius r, b=4V.


2r
1-103
1.48. Draw the van der Waals PV isotherm over the same range of P and V as in Figure 1.21 at 350 K and 450 K for Cl
2
using the values
in Table 1.4.
Solution:
Given: Figure 1.21 T=350K, T=450K
Required: draw the Van der Waals isotherms
The curves are similar to those in Figure 1.21


1-104
1.49. Compare the pressures predicted for 0.8 dm
3
of Cl
2
weighing 17.5 g at 273.15 K using (a) the ideal gas equation and (b) the van der
Waals equation.
Solution:
Given:
2
3
Cl
0.8 dm, 17.5 g, 273.15 K V m T = = =
Required:
Ideal
P and
vdw
P
From the ideal gas equation;
Ideal
nRT
P
V
=
Ideal
mRT
P
MV
= , where
m
n
M
=
Solving for
Ideal
P yields;
Ideal
17.5 g
P =
( )
1
8.3145 J K
1
mol
( )
273.15K
( )
2 35.4527g
1
mol
( )
3
0.8 dm
-3 3 3
10 m dm
( )
2 2 1
3
Ideal
3
Ideal
Ide
2 2
1 2
al
2
where 1 J 1kg m s and 1 Pa 1kg m s
kg m s
kg m s

700658 J m
700658 m
700658
P
P
P

= =
=
=
=

Ideal
700. Pa 7 P =

Using the van der waals equation;
2
vdw 2
nRT an
P
V nb V
=

2
vdw 2 2
mRT am
P
m M V
M V b
M
=
| |
|
\ .
, where
m
n
M
=
1-105
Solving for
vdw
P with
6 2 3 3 1
0.6579 Pa m mol and 0.0562 10 m mol a b

= = we get;
vdw
17.5g
P =
( )
1
8.3145 J K
1
mol
( )
273.15K
( )
2 35.4527g
1
mol
( )
3
0.8dm
3 3 3
10 m dm

17.5g
( )
2 35.4527g
1
mol
( )
3 3 1
0.0562 10 m mol
( )
| |
|
|
|
\ .

( )
6 2
0.6579 Pa m mol 17.5g
( )
2
2 35.4527g
( )
2
1 3
mol 0.8 dm
3 3 3
10 m dm

( )
2
vdw
vdw
vdw
712997.84 Pa 62613.8233 Pa
650384.0167 Pa
650 kPa
P
P
P
=
=
=


1-106
1.50. A particular mass of N
2
occupies a volume of 1.00 L at 50 C and 800 bar. Determine the volume occupied by the same mass of
N
2
at 100 C and 200 bar using the compressibility factor for N
2
. At 50 C and 800 bar it is 1.95; at 100 C and 200 bar it is 1.10.
Compare this value to that obtained from the ideal gas law.
Solution:
Given:
1 1 1 1
1.00L, 50 223.15K, 800 bar, 1.95 V T C P Z = = = = =
2 2 2
100C 373.15 K, 200 bar, 1.10 T P Z = = = =
Required: V
2
and compare to V
ideal
To determine V
2
, we can use Eq. 1.98 for a real gas and rearrange for n, the number of moles of N
2
;
PV
Z
nRT
ZPV
n
RT
=
=

The number of moles at V
2
is the same as the number of moles at V
1
since we know that the same mass is used.
1 1 1 2 2 2
1 2
1 2
1 2
1 1 1
,
where ,
Z PV Z PV
n n
RT RT
n n
Z PV
R
= =
=
2 2 2
1
Z PV
T R
=
2
T

Solving for V
2
to get;
( )
1 1 1 2
2
2 2 1
2
1.95 800bar
Z PVT
V
Z PT
V
=
=
( )( ) 1.00 L 223.15 K
( )
( ) 1.10 200bar
( )
373.15 K
( )
2
3.7747 L V =

2
3.77 L V =
1-107
To determine V
ideal
, we can use Eq. 1.98 for an ideal gas, with Z =1 and rearrange for n, the number of moles of N
2
;
2 ideal 1 1
1 2
1 2
1 2
1 1
, 1
,
where ,
PV
Z Z
nRT
PV
n
RT
PV PV
n n
RT RT
n n
PV
R
= =
=
= =
=
2 ideal
1
PV
T R
=
2
T

Now solving for V
ideal
;
1 1 2
ideal
2 1
ideal
800bar
PVT
V
PT
V
=
=
( )( ) 1.00 L 223.15K
( )
200bar
( )
373.15K
( )
ideal
6.68877 L V =

ideal
6.69 L V =
We can now compare V
2
and V
ideal
by determining the error on V
ideal
.
ideal 2
2

error 100%
6.69 3.77
error 100%
3.77
error 0.7745 100%
V V
V
=
=

error 77.5% =
1-108
1.51. A gas is found to obey the equation of state:
RT a
P
V b V
=

where a and b are constants not equal to zero. Determine whether this gas has a critical point; if it does, express the critical constants in
terms of a and b. If it does not, explain how you determined this and the implications for the statement of the problem.
Solution:
Given:

RT a
P
V b V
=
where a and b are constants not equal to zero

Required: critical point in terms of a and b, if it exists
According to Eq. 1.99, a gas has a critical point if
2
2
0 and 0
c
c
T
T
P P
V V
| | | |
= =
| |

\ .
\ .

( )
( )
( )
( )
( )
( )
2 2
2 2
2
3 2 3
3 3
0
1
2 2
0
2 2
2
c
c
T
T
P RT a
V V
V b
a RT
V
V b
P RT a
V V
V b
a RT
V
V b
| |
= + =
|
\ .
=
| |
= =
|
\ .
=

If
2
2
0 and 0
c
c
T
T
P P
V V
| | | |
= =
| |

\ .
\ .
, then
( )
( )
2
1
should not exist.
1-109
2a
3
V
a
| |
|
\ .
2
2RT
V
=
| |
|
\ .
( )
3
V b
RT
| |
|
\ .
( )
( )
( )
2
2
2
3 3
2 2
2 2
1 1
V b
V b V
V
V b
V V b
V V b
| |
|
\ .

This last line
1 1
V V b
=
is only true if b = 0, however b 0 from the statement of the problem. Therefore the gas does not have a critical
point.


1-110
1.52. Ethylene (C
2
H
4
) has a critical pressure of P
c
=61.659 atm and a critical temperature of T
c
=308.6 K. Calculate the molar volume
of the gas at T =97.2 C and 90.0 atm using Figure 1.22. Compare the value so found with that calculated from the ideal gas
equation.
Solution:
Given:

Ethylene (C
2
H
4
): Figure 1.22, 61.659 atm,
c
P = 308.6 K, 90.0 atm,
c
T P = =

97.2 C 370.35K T = =

Required: V
m,
and V
ideal

First the reduced temperature and pressure of the gas can be obtained using the following ratios; and
r r
c c
T P
T P
T P
= =
308.6K
r
T =
370.35K
1.20
90.0atm
r
P
=
=
61.659atm
1.46 =

Using Figure 1.22, the compressibility factor for a gas of T
r
=1.20 and P
r
=1.46 is found to be approximately 0.7. Eq. 1.98 gives the
compressibility in terms of molar volume. Rearranging this expression for V
m
will allow us to calculate the molar volume.
0.7 0.08206atm
m
m
m
PV
Z
RT
ZRT
V
P
V
=
=
=
3 1
dm K
( )
1
mol 370.35K
( )
90.0atm
( )
3 1
0.23637 dm mol
m
V

=

3 1
0.236 dm mol
m
V

=

1-111
The molar volume obtained from the ideal gas equation is given by;
m
m
V RT
V
n P
RT
V
P

0.08206atm
m
V =
3 1
dm K
( )
1
mol 370.35K
( )
90.0atm
( )
3 1
3 1
0.33767 dm mol
0.338 dm mol
m
m
V
V
=
=

A comparison with the ideal molar volume shows that the real molar volume obtained from the law of corresponding states is much smaller.


1-112
1.53. Assuming that methane is a perfectly spherical molecule, find the radius of one methane molecule using the value of b listed in
Table 1.5.
Solution:
Given: methane (CH
4
): Table 1.5
Required:
4
CH
r
Using Table 1.5,
3 3 -1
0.0428 10 m mol b

= and 4
m
b V = , as stated in section 1.13, the volume of methane is treated as a sphere;
4
4
3
CH
3
CH
4
3
4
4 3
r
V
b r
V
L
=
= =

We can divide by L, Avogadros number, since we are considering only one molecule of methane.
3
3 3 1
3
4 4
0.0428 10 m mol
3
16
b
r
L
r
=
( )
23 1
6.022 10 mol
( )
3
10
10
1.61877 10 m
1.62 10 m
r
r
=
=

The actual radius, i.e. the C-H distance in CH
4
is
10
1.09 10 m
.


1-113
1.54. Determine the Boyle temperature in terms of constants for the equation of state:
PV
m
=RT{1 +8/57(P/P
c
)(T
c
/T)[1 4(T
c
/T)
2
]}
R, P
c
, and T
c
are constants.
Solution:
Given:
2
8
1 1 4
57
c c
m
c
T T P
PV RT
P T T
(
| |
| | | |
= + ( ` | | |
\ . \ .
( \ . )

Required: T
B
, Boyle temperature
The Boyle Temperature occurs when the second virial coefficient, B(T) =0 and the partial derivative
( )
T
PV
P
| |
|
\ .
becomes zero as P0.
This is fulfilled when
2
1 4 0
c
T
T
| |
=
|
\ .
, therefore;
2
2
1 4 0
1
4
1
2
c
B
c
B
c
B
T
T
T
T
T
T
| |
=
|
\ .
| |
=
|
\ .
=

2
B c
T T =


1-114
1.55. Establish the relationships between van der Waals parameters a and b and the virial coefficients B and C of Eq. 1.117 by performing
the following steps:
a. Starting with Eq. 1.101, show that
1
m m
m m
PV V a
RT V b RT V
=
.
b. Since V
m
/(V
m
b) =(1 b/V
m
)
1
, and (1 x)
1
=1 +x +x
2
+,, expand (1 b/ V
m
)
1
to the quadratic term and substitute into the
result of part (a).
c. Group terms containing the same power of V
m
and compare to Eq. 1.117 for the case n =1.
d. What is the expression for the Boyle temperature in terms of van der Waals parameters?
Solution:
Starting with equation 1.101
2
m m
RT a
P
V b V
=
, we can multiply by
m
V
RT
to get;
m m
PV V
RT RT
=
RT | |
|
\ .
m
m
V
V b

2
m
a
RT V
| |
|
|
\ .
1
m m
m m
PV V a
RT V b RT V
=

Since V
m
/(V
m
b) =(1 b/V
m
)
1
, and (1 x)
1
=1 +x +x
2
+, therefore we can write;
1 2
1 1
m m m
b b b
V V V
| | | |
= + + +
| |
\ . \ .

Using the expression derived above;
2
1
1
m
m m m
PV b b a
RT V V RT V
| |
= + + +
|
\ .

1-115
Grouping the terms containing the same power of V
m
gives;
2
1
1
m
m m
PV a b
b
RT V RT V
| |
| |
= + + +
| |
\ .
\ .

Equation 1.117 is
2 4
2 4
( ) ( ) ( )
1
PV B T n C T n D T n
nRT V V V
= + + + +. For the case n =1, this becomes,
( ) ( ) ( )
2 4
1
m
B T C T D T PV
RT V V V
= + + + +
Comparing to the expression we obtained in part c, we can see that: ( ) ( ) ( )
2
, and 0
a
B T b C T b D T
RT
| |
= = =
|
\ .

The expression for the Boyle temperature in terms of van der Waals parameters is determined when ( ) 0 B T = ;
0
B
B
a
b
RT
a
b
RT
| |
=
|
\ .
=

B
a
T
bR
=


1-116
1.56. Determine the Boyle temperature of a van der Waals gas in terms of the constants a, b, and R.
Solution:
Given: A van der Waals gas
Required: T
B
of the constants a, b, and R
The temperature can be obtained by rearranging the van der Waals equation;
( )
2
2
an
P V nb nRT
V
| |
+ =
|
\ .
(Eq. 1.100)
2
RT a
P
V b V
=

We can then multiply through by
V
RT
to change the form of the equation;
PV V
RT RT
=
RT | |
|
\ .
V
V b

2
a
RT
V
| |
|
\ .
PV V a
RT V b RTV
V a
Z
V b RTV
=

1-117
Since V/(V b) =(1 b/V)
1
, and (1 x)
1
=1 +x +x
2
+, therefore;
1 2
1 1
b b b
V V V
| | | |
= + + +
| |
\ . \ .

2
1
1
b b a
Z
V V RT V
| |
= + + +
|
\ .

Grouping the terms containing the same power of V gives,
2
1
1
a b
Z b
V RT V
| | | |
= + + +
| |
\ . \ .

The Boyle Temperature occurs when the second virial coefficient, B(T) =0 and the partial derivative
T
Z
P
| |
|
\ .
becomes zero as P0, i.e.:
0
lim 0
P
T
Z
P
| |
=
|
\ .

By changing the variable into
RT
V
P
we can get;
1-118
( )
( )
2
2
2
0
0
1
1
2
lim 0
1
lim 0
where 0
1
0
0
T
P
T
P
T
B
B B
B
B
B
P a b
Z b P
RT RT RT
Z a b
b P
P RT RT RT
Z
P
Z a
b
P RT RT
B T
a
B T b
RT RT
a
b
RT
a
b
RT
a
T
Rb
| | | |
= + + +
| |
\ . \ .
| | | | | |
= +
| | |
\ . \ . \ .
| |
=
|
\ .
| | | |
= =
| |
\ . \ .
=
| |
= =
|
\ .
=
=
=

1-119
1.57. The critical temperature T
c
of nitrous oxide (N
2
O) is 36.5 C, and its critical pressure P
c
is 71.7 atm. Suppose that 1 mol of N
2
O is
compressed to 54.0 atm at 356 K. Calculate the reduced temperature and pressure, and use Figure 1.22, interpolating as necessary, to
estimate the volume occupied by 1 mol of the gas at 54.0 atm and 356 K.
Solution:
The reduced temperature and pressure of the gas can be obtained using the ratios and
r r
c c
T P
T P
T P
= =
Using the values above, we obtain
356 K
=
r
T
( ) 273.15 36.5 K +
1.14969
1.15
54.0 atm
=
=
=
r
r
r
T
T
P
71.7 atm
0.753138
0.753
=
=
r
r
P
P


1-120
1.58. At what temperature and pressure will H
2
be in a corresponding state with CH
4
at 500.0 K and 2.00 bar pressure? Given T
c
=33.2 K
for H
2
, 190.6 K for CH
4
; P
c
=13.0 bar for H
2
, 46.0 bar for CH
4
.
Solution:
Given:
4 4 H
2
CH CH
500.0K, 2.00bar, 33.2K,
c
T P T = = =
CH H CH
4 2 4
190.6K, 13.0bar, 46.0bar
c c c
T P P = =
Required:
2 2
H H
and T P
In order for hydrogen to be in the corresponding state as methane, they must have the same reduced temperature and reduced pressure. The
reduced temperature and pressure of the gas can be obtained using the ratios and
r r
c c
T P
T P
T P
= =
4
CH
4
CH
500.0K
r
c
r
T
T
T
T
=
=
190.6K
4
CH
4
CH
2.623
2.00bar
r
r
c
r
T
P
P
P
P
=
=
=
46.0bar
2
4.35 10
r
P

=

2 2
H H
and T P are given by rearranging the ratios for reduced temperature and pressure.
2 H 2 H
2 2
H H
and
r c r c
T T T P P P = =
Solving for
2 2
H H
and T P gives;
1-121
( )( )
( )( )
2
2
2
2
H
H
2
H
H
2.623 33.2 K
87.0836 K
4.35 10 13.0 bar
0.5655 bar
T
T
P
P
=
=
=
=

4
CH
4
CH
500.0K
r
c
r
T
T
T
T
=
=
190.6K
4
CH
4
CH
2.623
2.00bar
r
r
c
r
T
P
P
P
P
=
=
=
46.0bar
H
2
H
2
2
4.35 10
33.2 K
13.0 bar
r
c
c
P
T
P
=
=
=

2
2
H
H
87.1 K
0.566 bar
T
P
=
=


1-122
1.59. For the Dieterici equation, derive the relationship of a and b to the critical volume and temperature.
[Hint: Remember that at the critical point (P/V)
T
=0 and (
2
P/V
2
)
T
=0.]
Solution:
Given: Dieterici equation:
/
( e )( )
m
a V RT
m
P V b RT =
Required: Tthe relationship of a and b to V
c
and T
c

By rearranging for P and using Eq.1.114, (P/V)
T
and (
2
P/V
2
)
T
can be determined.
( )
( )
( )
( ) ( )
( )
/
/ /
2 2
/
2
2
e
1
e e
1
e
1

m
m m
m
a V RT
m
a V RT a V RT
m m m
T m
a V RT
m m m m
T
m m m
T
RT
P
V b
P RT a RT
V RT V V b
V b
P RT a
V V b RTV V b
P a
P
V RTV V b
| | | | | |
= +
| | |
|

\ . \ . \ .
| | | |
=
| |
|

\ . \ .
| | | |
=
| |
|

\ . \ .

( )
( )
( )
( )
( )
( )
2
2 2 2 3
2
2
2 2 2 3
2
2
2 2 2 3
1 2 1
1 2 1
1 2 1
m m m m m
T T m
m m m m
T m
m m m m
T m
P P a a
P
V V RTV V b RTV
V b
P a a
P P
V RTV V b RTV
V b
P a a
P
V RTV V b RTV
V b
| |
| | | | | |
= + + |
| | |
|
|

\ . \ . \ .
\ .
| |
| | | |
= + + |
| |
|
|

\ . \ .
\ .
(
| | | |
( = +
| |
|
(
\ . \ .

1-123
Solving for (P/V)
T
=0 and (
2
P/V
2
)
T
=0, the condition of the critical point, The relationship of a and b to V
c
and T
c
can then be
obtained;
( )
2
1
0
c
m m m
T
P a
P
V RTV V b
| | | |
= =
| |
|

\ . \ .

( )
2
1
0
c c c
a
P
RTV V b
| |
=
|
|
\ .

( )
2
c c
c
RTV
a
V b
=

( )
( )
2
2
2 2 2 3
1 2 1
0
m m m m
T m
P a a
P
V RTV V b RTV
V b
(
| | | |
( = + =
| |
|
(
\ . \ .

( )
( )
2
2 2 3
1 2 1
0
c c c c c
c
a a
P
RTV V b RTV
V b
(
| |
( + =
|
|
(
\ .

( )
( )
2
2 2 3
1 2 1
0
c c c c c
c
a a
RTV V b RTV
V b
| |
+ =
|
|

\ .

Substituting the expression for a into the above can further simplify the problem;
1-124
2
1
c c
RTV
2
c c
RTV
( ) ( )
2
1 2
c c c
V b V b RT
| | | |
| |
| |
\ . \ .
3
c
V
2
c c
RTV
( )
( )
( )
2
1
0
1
c
c
c
V b
V b
V b
| |
| + =
|

\ .
( )
1
c
V b
( )
( )
( )
( )
2
2
2 1
0
2 1
2
2
2
c c
c
c c
c c
c
c
c
V V b
V b
V V b
V b V
V
b V
V
b
| |
| + =
|

\ .
=
=
=
=

The Dieterici constant a then becomes,
2
2
2
2
2
c c
c
c
c c
c
c c
RTV
a
V
V
RTV
a
V
a RTV
=
| |
|
\ .
=
| |
|
\ .
=

Substitution back into the Dieterici equation, the critical point becomes,
( )
/
e , 2 and
2
m
a V RT c
c c
m
V RT
P a RTV b
V b
= = =

1-125
2
e
2
c
RT V
c
c
c
c
RT
P
V
V
=
| |
|
\ .
c
c
V RT
2
e
2
c
c
c
c
RT
P
V
=
| |
|
\ .

2
2
e
c
c
c
RT
P
V
=


1-126
1.60. In Eq. 1.103 a cubic equation has to be solved in order to find the volume of a van der Waals gas. However, reasonably accurate
estimates of volumes can be made by deriving an expression for the compression factor Z in terms of P from the result of the
previous problem. One simply substitutes for the terms V
m
on the right-hand side in terms of the ideal gas law expression V
m
=
RT/P. Derive this expression and use it to find the volume of CCl
2
F
2
at 30.0 C and 5.00 bar pressure. What will be the molar
volume computed using the ideal gas law under the same conditions?
Solution:
Given: (from problem 1.59): CCl
2
F
2
at 30.0 C =303.15 K T = and =5.00 bar P
Required: V
m and

ideal
m
V
The compression factor ;
m
PV PV
Z
nRT RT
= = can be used with Eq. 1.101 to obtain an expression for Z;
2
m m
m m
RT a
P
V b V
PV V
Z
RT RT
=
= =
RT | |
|
\ .
m
m
V
V b

2
m
a
RT V
| |
|
|
\ .
m
m m
V a
Z
V b RTV
=

Since V
m
/(V
m
b) =(1 b/V
m
)
1
, and (1 x)
1
=1 +x +x
2
+, therefore;
1 2
1 1
m m m
b b b
V V V
| | | |
= + + +
| |
\ . \ .

2
2
1
1
1
1
m m m
m m
b b a
Z
V V RT V
a b
Z b
V RT V
| |
= + + +
|
\ .
| |
| |
= + + +
| |
\ .
\ .

Using V
m
= RT/P, we obtain;
1-127
2
1
P a b
Z b P
RT RT RT
| | | |
= + +
| |
\ . \ .

Table 1.5 gives the van der Waals constants for CCl
2
F
2
:
3 2
1.066 dm bar mol , a

=
3 1
0.0973 dm mol b

=
5.00 bar
1 Z = +
( )
0.083 15 bar
3 1
dm K
( )
1
mol 303.15 K
( )
3
3 1

1.066 dm
0.0973 dm mol
bar
2
mol
0.083 15 bar
3
dm
1
K
( )
1
mol 303.15 K
( )
3
0.0973 dm
| |
|
|
|
\ .
+
1
mol
0.083 15 bar
3
dm
1
K
1
mol
( )
303.15 K
( )
2
5.00 bar
| |
|
|
|
\ .
( )
2
1.01167
1.01
Z
Z
=
=

We can then solve for V
m
by rearranging the expression for the compression factor;
1.01 0.083 15 bar
m
m
m
PV
Z
RT
Z RT
V
P
V
=
=
=
3 1
dm K
( )
1
mol 303.15 K
( )
5.00 bar
( )
3 1
5.0918dm mol
m
V =

3 1
5.09dm mol
m
V =
1-128
ideal
m
V can also be obtained using the ideal gas, PV nRT
,
and solving for V
m
,
ideal
ideal
0.083 15 bar
m
m
RT
V
P
V
=
=
3 1
dm K
( )
1
mol 303.15 K
( )
5.00 bar
( )
ideal
3 1
5.04138 dm mol
m
V =

ideal
3 1
5.04 dm mol
m
V =


1-129
1.61. A general requirement of all equations of state for gases is that they reduce to the ideal gas equation (Eq. 1.28) in the limit of low
pressures. Show that this is true for the van der Waals equation.
Solution:
Given: PV =nRT, low P
Required: show that the van der Waals equation reduces to Eq. 1.28
The Van der Waals equation is given by;
2
2
( )
an
P V nb nRT
V
| |
+ =
|
\ .
(Eq. 1.100)
Using the compression factor,
m
PV PV
Z
nRT RT
= = , Eq. 1.100 can be recast in a form of Z in terms of P.
2
m m
m m
RT a
P
V b V
PV V
Z
RT RT
=
= =
RT | |
|
\ .
m
m
V
V b

2
m
a
RT V
| |
|
|
\ .
m
m m
V a
Z
V b RTV
=

Since V
m
/(V
m
b) =(1 b/V
m
)
1
, and (1 x)
1
=1 +x +x
2
+, therefore;
1 2
1 1
m m m
b b b
V V V
| | | |
= + + +
| |
\ . \ .

2
2
1
1
1
1
m m m
m m
b b a
Z
V V RT V
a b
Z b
V RT V
| |
= + + +
|
\ .
| |
| |
= + + +
| |
\ .
\ .

1-130
Using V
m
= RT/P we obtain;
2
1
P a b
Z b P
RT RT RT
| | | |
= + +
| |
\ . \ .

Taking the limit of Z as P approaches 0 becomes,
0
lim 1
P
P a
b
RT RT
| |
+
|
\ .
2
b
P
RT
| |
+
|
\ .
0
lim 1
P
| |
|
|
\ .
=

1 Z =
Which is true for an ideal gas, and therefore the van der Waals equation reduces to the ideal gas equation.

1-131
1.62. The van der Waals constants for C
2
H
6
in the older literature are found to be
a =5.49 atm L
2
mol
2
and b =0.0638 L mol
1
Express these constants in SI units (L =liter =dm
3
).
Solution:
Given: PV =nRT, low P, a =5.49 atm L
2
mol
2
and b =0.0638 L mol
1
Required: express a and b in SI units
( ) ( )
( ) ( )
6 6
2 6 6
6 6
2 2
2
1 6 2
3 3
3 3
3 3
1
5 3 1
1atm 101325 Pa
1 L 1 dm 0.1 m 1 10 m
101325 Pa 1 10 m
5.49 atm L mol
1atm 1 L
5.56 10 Pa m mol
1 L 1 dm 0.1 m 1 10 m
1 10 m
0.0638 L mol
1 L
6.38 10 m mol
a
a
b
b
=
= = =
=
=
= = =
=
=


1-132
1.63. Compare the values obtained for the pressure of 3.00 mol CO
2
at 298.15 K held in a 8.25-dm
3
bulb using the ideal gas, van der
Waals, Dieterici, and Beattie-Bridgeman equations. For CO
2
the Dieterici equation constants are
a =0.462 Pa m
6
mol
2
,
b =4.63 10
5
m
3
mol
1
Solution:
Given:
2 2
3
CO CO
3.00 mol, 298.15 K, 8.25dm n T V = = =

6 2 5 3 1
Dieterici Dieterici
0.462 Pa m mol , 4.63 10 m mol a b = =
Required:
ideal vdw Dieterici BB
, , and P P P P
The Ideal Gas equation is given by;
ideal
ideal
3.00mol
nRT
P
V
P
=
=
( )
1
8.3145 J K
1
mol
( )
298.15K
( )
3
8.25dm
3 3
3
1 10 m
1 dm
-3
ideal
3
ideal
ideal
idea
2
l
2 2 1
2 2
901400 J m
901400 m
where 1 J 1kg m s , 1 Pa 1 kg m s
kg m
901400
s
Pa
where 1 bar 100000
9.
Pa
bar 01
P
P
P
P

| |
|
|
\ .
=
=
=
=
=
= =

The Van der Waals equation is defined as;
1-133
vdw 2
3
8.25dm
m m
m
RT a
P
V b V
V
V
n
=
= =
3 3
3
1 10 m
1 dm
( )
3 3 1
1
3.00 mol
2.75 10 m mol
m
V

| |
|
|
\ .
=

From Table 1.5,
6 2 3 3 1
0.3640 Pa m mol , 0.0427 10 m mol a b = =
-1
vdw
8.3145 J K
P =
-1
mol
( )
298.15K
( )
3 3 1
2.75 10 m mol

( )
3 3 1
0.0427 10 m mol
( )
6
0.3640 Pa m
2
mol
( )
3 3
2.75 10 m
1
mol
( )
2

1
3
vdw
vdw
w
dw
2
vd
v
915661 J m 48132 Pa
915661 Pa 48132
867528 Pa
k
8
g m
68 bar
s
.
P
P
P
P

=
=
=
=

The Dieterici Equation is as follows;
( )
/
Dieterici
6 2 5 3 1 3 3 1
Dieterici Dieterici
1
Dieterici
e
0.462 Pa m mol , 4.63 10 m mol , 2.75 10 m mol
8.3145 J K
m
a V RT
m
m
RT
P
V b
a b V
P
= = =
=
1
mol
( )
298.15K
( )
3 3 -1
2.75 10 m mol
5 3 1
4.63 10 m mol
( ) ( )
6 2
0.462Pam mol
e
( )
3 3 1
2.75 10 m mol

( )
1
8.3145J K
1
mol
( )
298.15K ( )
Dieterici
Dieterici
856801 Pa
8.57 bar
P
P
=
=

The Beattie-Bridgeman equation;
1-134
( )
BB 2 3 2
0 0
1
where 1 , 1
m
m m m
m m
RT c A
P V B
V V T V
a b
A A B B
V V
( | |
= +
( |
( \ .
| | | |
= =
| |
\ . \ .

From Table 1.6:
6 2 6 3 1 6 3 1
0
0.50728Pa mmol , 71.32 10 m mol , 104.76 10 m mol , A a B = = =
0
6 3 1 3 3 1
72.35 10 m mol , c 66.00 10 m K mol b = =
6 3
6 2
71.32 10 m
0.50728 Pa m mol 1 A

=
1
mol
3 3
2.75 10 m
1
mol
6 2
0.494124 Pa m mol A
| |
|
|
\ .
=

( )
6 3
6 3 1
72.35 10 m
104.76 10 m mol 1 B

=
1
mol
3 3
2.75 10 m
1
mol
4 3 1
1.02004 10 m mol B
| |
|
|
\ .
=

Solving for P
BB
gives,
1
BB
8.3145 J K
P
=
( )
1
mol 298.15K
( )
( )
3
2
3 3 1
66.00 10 m
1
2.75 10 m mol
3
K
1
mol
3 3
2.75 10 m
1
mol
( )
298.15K
( )
( ) ( )
( )
( )
3
6 2
3 3 1 4 3 1
2
3 3 1
BB
BB
0.013156 Pa m mol
2.75 10 m mol 1.02004 10 m mol
2.75 10 m mol
861075 Pa
8.61 bar
P
P
( | |
( |
( |
|
(
\ .
+
=
=

1-135
1.64. A gas obeys the van der Waals equation with P
c
=3.040 10
6
Pa (=30 atm) and T
c
=473 K. Calculate the value of the van der
Waals constant b for this gas.
Solution:
Given: P
c
=3.040 10
6
Pa (=30 atm) and T
c
=473 K
Required: b
From Eq. 1.109;
3
c
V
b= and
8
3
c c
c
PV
R
T
=
It is possible to rearrange the expression for the gas constant to express it in terms of V
c
,

so that we can isolate for b.
3
8
1
3
c
c
c
RT
V
P
b
=
=
3
1
8
8
8.3145 J K
c
c
c
c
RT
P
RT
b
P
b
=
=
( )
1
mol 473 K
( )
2 2 1 2
6
where 1 J 1kg m s and 1 Pa 1kg m s
1kg
1 J
1

8 3.040 10
P
P
a
a

= =
=
2 2
m s
1kg
1 2
m s

4
1 3
1
4
3
3
1.61709 10 mol
1.62 10
1 m
m
m mol
b
b

=
=
=

1-136
1.65. Expand the Dieterici equation in powers of
1
m
V
in order to cast it into the virial form. Find the second and third virial coefficients.
Then show that at low densities the Dieterici and van der Waals equations give essentially the same result for P.
Solution:
Given:
/
( e )( )
m
a V RT
m
P V b RT =
Required: second and third virial coefficients
First, the Dieterici equation can be rewritten in terms of P as;
( )
/
Dieterici
e
m
a V RT
m
RT
P
V b

The series expansion for e
x
is given by
2 3
1 ...
2! 3!
x
x x
e x = + + + + can be used to expand the Dieterici equation.
( )
( ) ( ) ( )
( ) ( ) ( )
2
Dieterici
2
Dieterici
2
Dieterici 2
1 ...
2!
...
2!
...
2
m
m m
m
m m m m
m m m m m
a
V RT RT a
P
V b V RT
a
V RT RT RT a RT
P
V b V b V RT V b
RT a a
P
V b V V b RTV V b

| |

|
| |
\ .
= + + +
` |
\ .

)
| |
|
| | | | | |
\ .
= + + +
| | |
| |

\ . \ . \ .
= +

Expanding
1
m
V b
and collecting terms in powers of V
m
gives coefficients that are independent of V
m.
:
1-137
1 2
1 1 1
1 1
m m m m m m
b b b
V b V V V V V
| |
| | | |
| = = +
| |
|
\ . \ .
\ .

Substitution into the Dieterici equation leads to;
2
2
2 3
1
...
2
m m m
RT a RTb a
P ab RTb
V V V RT
| | +
= + + +
|
\ .

The second coefficient is ( ) a RTb + and the third coefficient is
2
2
2
a
ab RTb
RT
| |
+ +
|
\ .
.
At low densities, the third and higher terms are negligible. Dropping the third and higher terms, and substituting, we obtain
2
m m
RT a RTb
P
V V
+
=
This is in the same form as the van der Waals equation.


CHAPTER
2
2
The First Law of Thermodynamics

Physical Chemistry
Electronic Edition

Chapter 2: The First Law of Thermodynamics Energy, Heat, and Work
2-2
Chapter 2
Energy, Heat, and Work
2.1. A bird weighing 1.5 kg leaves the ground and flies to a height of 75 metres, where it attains a velocity of 20 m s
1
. What change in
energy is involved in the process? (Acceleration of gravity =9.81 m s
2
.)

Solution

2.2. The densities of ice and water at 0 C are 0.9168 and 0.9998 g cm
3
, respectively. If H for the fusion process at atmospheric
pressure is 6.025 kJ mol
1
, what is U? How much work is done on the system?

Solution

2.3. The density of liquid water at 100 C is 0.9584 g cm
3
, and that of steam at the same temperature is 0.000 596 g cm
3
. If the enthalpy
of evaporation of water at atmospheric pressure is 40.63 kJ mol
1
, what is U? How much work is done by the system during the
evaporation process?

Solution

2.4. The latent heat of fusion of water at 0 C is 6.025 kJ mol
1
and the molar heat capacities (C
P, m
) of water and ice are 75.3 and 37.7 J
K
1
mol
1
, respectively. The C
P
values can be taken to be independent of temperature. Calculate H for the freezing of 1 mol of
supercooled water at 10.0 C.

Solution

2.5. A sample of liquid acetone weighing 0.700 g was burned in a bomb calorimeter for which the heat capacity (including the sample) is
6937 J K
1
. The observed temperature rise was from 25.00 C to 26.69 C.
a. Calculate U for the combustion of 1 mol of acetone.
b. Calculate H for the combustion of 1 mol of acetone.

Solution

Chapter 2: The First Law of Thermodynamics Energy, Heat, and Work
2-3
2.6. An average man weighs about 70 kg and produces about 10 460 kJ of heat per day.
a. Suppose that a man were an isolated system and that his heat capacity were 4.18 J K
1
g
1
; if his temperature were 37 C at a given
time, what would be his temperature 24 h later?
b. A man is in fact an open system, and the main mechanism for maintaining his temperature constant is evaporation of water. If the
enthalpy of vaporization of water at 37 C is 43.4 kJ mol
1
, how much water needs to be evaporated per day to keep the temperature
constant?

Solution

2.7. In an open beaker at 25 C and 1 atm pressure, 100 g of zinc are caused to react with dilute sulfuric acid. Calculate the work done by
the liberated hydrogen gas, assuming it behaves ideally. What would be the work done if the reaction took place in a sealed vessel?

Solution

2.8. A balloon is 0.50 m in diameter and contains air at 25 C and 1 bar pressure. It is then filled with air isothermally and reversibly
until the pressure reaches 5 bar. Assume that the pressure is proportional to the diameter of the balloon and calculate (a) the final
diameter of the balloon and (b) the work done in the process.

Solution

2.9. When 1 cal of heat is given to 1 g of water at 14.5 C, the temperature rises to 15.5 C. Calculate the molar heat capacity of water at
15 C.

Solution

2.10. A vessel containing 1.000 kg of water at 25.00 C is heated until it boils. How much heat is supplied? How long would it take a one-
kilowatt heater to supply this amount of heat? Assume the heat capacity calculated in Problem 2.9 to apply over the temperature
range.

Solution

2.11. A nonporous ceramic of volume V m
3
and mass M kg is immersed in a liquid of density d kg m
3
. What is the work done on the
ceramic if it is slowly raised a height h m through the liquid? Neglect any resistance caused by viscosity. What is the change in the
potential energy of the ceramic?

Solution
Chapter 2: The First Law of Thermodynamics Thermochemistry
2-4
2.12. Show that the differential dP of the pressure of an ideal gas is an exact differential.

Solution

2.13. Determine whether dU =xy
2
dx +x
2
ydy is an exact differential. If it is find the function U of which dU is the differential. Do this by
integrating over suitable paths. In a plot of y against x, show a plot of the paths that you chose.

Solution

Thermochemistry
2.14. Using the data given in Table 2.1 and Appendix D, find the enthalpy change for the reaction 2H
2
(g) +O
2
(g) 2H
2
O(g) at 800 K.

Solution

2.15. A sample of liquid benzene weighing 0.633 g is burned in a bomb calorimeter at 25.00 C, and 26.54 kJ of heat are evolved.
a. Calculate U per mole of benzene.
b. Calculate H per mole of benzene.

Solution

2.16. Deduce the standard enthalpy change for the process
2CH
4
(g) C
2
H
6
(g) +H
2
(g)
from the data in Appendix D.

Solution

2.17. A sample of liquid methanol weighing 5.27 g was burned in a bomb calorimeter at 25.00 C, and 119.50 kJ of heat was evolved
(after correction for standard conditions).
a. Calculate
c
H for the combustion of 1 mol of methanol.
b. Use this value and the data in Appendix D for H
2
O(l) and CO
2
(g) to obtain a value for
f
H(CH
3
OH,l), and compare with the
value given in the table.
c. If the enthalpy of vaporization of methanol is 35.27 kJ mol
1
, calculate
f
H for CH
3
OH(g).

Solution
2-5

2.18. Calculate the heat of combustion (
c
H) of ethane from the data given in Appendix D.

Solution

2.19. The model used to describe the temperature dependence of heat capacities (Eq. 2.48; Table 2.1) cannot remain valid as the
temperature approaches absolute zero because of the 1/T
2
term. In some cases, the model starts to break down at temperatures
significantly higher than absolute zero. The following data for nickel are taken from a very old textbook (Numerical Problems in
Advanced Physical Chemistry, J . H. Wolfenden, London: Oxford, 1938, p. 45). Fit these data to the model and find the optimum
values of the parameters.

T/K 15.05 25.20 47.10 67.13 82.11 133.4 204.05 256.5 283.0
CP/J K
1

mol
1

0.1943 0.5987 3.5333 7.6360 10.0953 17.8780 22.7202 24.8038 26.0833

Examine the behavior of the fit in the range 10 T 25 and comment on this.

Solution

2.20. Suggest a practicable method for determining the enthalpy of formation
f
H of gaseous carbon monoxide at 25 C. (Note: Burning
graphite in a limited supply of oxygen is not satisfactory, since the product will be a mixture of unburned graphite, CO, and CO
2
.)

Solution

2.21. If the enthalpy of combustion
c
H of gaseous cyclopropane, C
3
H
6
, is 2091.2 kJ mol
1
at 25 C, calculate the standard enthalpy of
formation
f
H.

Solution

2.22. The parameters for expressing the temperature dependence of molar heat capacities for various substances listed in Table 2.1 are
obtained by fitting the model C
P, m
=d +eT +f/T
2
to experimental data at various temperatures and finding the values of the
parameters d, e, and f that yield the best fit. Several mathematical software packages (Mathematica, Mathcad, Macsyma, etc.) and
several scientific plotting packages (Axum, Origin, PSIPlot, etc.) can perform these fits very quickly. Fit the following data given
the temperature dependence of C
P,m
for n-butane to the model and obtain the optimum values of the parameters.

2-6

T/K 220 250 275 300 325 350 380 400
CP/J K
1
mol
1
0.642 0.759 0.861 0.952 1.025 1.085 1.142 1.177

Solution

2.23. From the data in Appendix D, calculate H for the reaction (at 25 C):
C
2
H
4
(g) +H
2
O(l) C
2
H
5
OH(l)

Solution

2.24. The bacterium Acetobacter suboxydans obtains energy for growth by oxidizing ethanol in two stages, as follows:
a.
2 5 2 3 2
1
C H OH(l) O (g) CH CHO(l) H O(l)
2
+ +
b.
3 2 3
1
CH CHO(l) O (g) CH COOH(l)
2
+
The enthalpy increases in the complete combustion (to CO
2
and liquid H
2
O) of the three compounds are

c
H/kJ mol
1

Ethanol (l) 1370.7
Acetaldehyde (l) 1167.3
Acetic acid (l) 876.1

Calculate the H values for reactions (a) and (b).

Solution

2.25. The enthalpy of combustion of acrylonitrile (C
3
H
3
N) at 25 C and 1 atm pressure is 1760.9 kJ mol
1
[Stamm, Halverson, and
Whalen, J. Chem. Phys., 17, 105(1949)]. Under the same conditions, the heats of formation of HCN(g) and C
2
H
2
(g) from the
elements are 135.1 and 226.73 kJ mol
1
, respectively [The NBS Tables of Chemical and Thermodynamic Properties, Supp. 2 to Vol.
11 of J. Phys. Chem. Ref. Data]. Combining these data with the standard enthalpies of formation of CO
2
(g) and H
2
O(g), calculate
2-7
the enthalpy change in the reaction HCN(g) +C
2
H
2
(g) H
2
C=CHCN(g). [Notes: (a) Assume that the nitrogen present in
acrylonitrile is converted into nitrogen gas during combustion. (b) Assume that all substances except for graphite (for the formation
of CO
2
) are gases, i.e., ignore the fact that acrylonitrile and water will be liquids under the conditions given here.]

Solution

2.26. Calculate H for the reaction;
C
2
H
5
OH(l) +O
2
(g) CH
3
COOH(l) +H
2
O(l)
making use of the enthalpies of formation given in Appendix D. Is the result consistent with the results obtained for Problem 2.24?

Solution

2.27. The disaccharide -maltose can be hydrolyzed to glucose according to the equation
C
12
H
22
O
11
(aq) +H
2
O(l) 2C
6
H
12
O
6
(aq)
Using data in Appendix D and the following values, calculate the standard enthalpy change in this reaction:

f
H/kJ mol
1

C
6
H
12
O
6
(aq) 1263.1
C
12
H
22
O
11
(aq) 2238.3

Solution
2.28. The standard enthalpy of formation of the fumarate ion is 777.4 kJ mol
1
. If the standard enthalpy change of the reaction:
fumarate
2
(aq) +H
2
(g) succinate
2

(aq)
is 131.4 kJ mol
1
, calculate the enthalpy of formation of the succinate ion.

Solution

2.29. The H for the mutarotation of glucose in aqueous solution,
-D-glucose(aq) -D-glucose(aq)
has been measured in a microcalorimeter and found to be 1.16 kJ mol
1
. The enthalpies of solution of the two forms of glucose
have been determined to be
-D-glucose(s) -D-glucose(aq)
H =10.72 kJ mol
1
2-8
H =4.68 kJ mol
1
Calculate H for the mutarotation of solid -D-glucose to solid -D-glucose.

Solution

2.30. Use the data in Appendix D to calculate H for the hydrolysis of urea into carbon dioxide and ammonia at 25 C.

Solution

2.31. Here is a problem with a chemical engineering flavor: Ethanol is oxidized to acetic acid in a catalyst chamber at 25 C. Calculate the
rate at which heat will have to be removed (in J h
1
) from the chamber in order to maintain the reaction chamber at 25 C, if the feed
rate is 45.00 kg h
1
of ethanol and the conversion rate is 42 mole % of ethanol. Excess oxygen is assumed to be available.

Solution

2.32. a. An ice cube at 0 C weighing 100.0 g is dropped into 1 kg of water at 20 C. Does all of the ice melt? If not, how much of it
remains? What is the final temperature? The latent heat of fusion of ice at 0 C is 6.025 kJ mol
1
, and the molar heat capacity of
water, C
P,m
is 75.3 J K
1
mol
1
.
b. Perform the same calculations with 10 ice cubes of the same size dropped into the water. (See Problem 3.33 of Chapter 3 for the
calculation of the corresponding entropy changes.)

Solution

*2.33. From the data in Table 2.1 and Appendix D, calculate the enthalpy change in the reaction
C(graphite) +O
2
(g) CO
2
(g)
at 1000 K.
Solution
2.34. From the bond strengths in Table 2.2, estimate the enthalpy of formation of gaseous propane, C
3
H
8
, using the following additional
data:

f
H/kJ mol
1

C(graphite) C(g) 716.7
H
2
(g) 2H(g) 436.0

Chapter 2: The First Law of Thermodynamics Ideal Gases
2-9
Solution

2.35. A sample of sucrose, C
12
H
22
O
11
weighing 0.1328 g, was burned to completion in a bomb calorimeter at 25 C, and the heat evolved
was measured to be 2186.0 J .
a. Calculate
c
U
m
and
c
H
m
for the combustion of sucrose.
b. Use data in Appendix D to calculate
f
H
m
for the formation of sucrose.

Solution

2.36. The value of H for the reaction
2 2
1
CO(g) + O (g) CO (g)
2

is 282.97 kJ mol
1
at 298 K. Calculate U for the reaction.

Solution

Ideal Gases
2.37. One mole of an ideal gas initially at 10.00 bar and 298.0 K is allowed to expand against a constant external pressure of 2.000 bar to
a final pressure of 2.000 bar. During this process, the temperature of the gas falls to 253.2 K. We wish to construct a reversible path
connecting these initial and final steps as a combination of a reversible isothermal expansion followed by a reversible adiabatic
expansion. To what volume should we allow the gas to expand isothermally so that subsequent adiabatic expansion is guaranteed to
take the gas to the final state? Assume that
,
3
2
V m
C R = .

Solution

2.38. Two moles of oxygen gas, which can be regarded as ideal with C
P
=29.4 J K
1
mol
1
(independent of temperature), are maintained
at 273 K in a volume of 11.35 dm
3
.
a. What is the pressure of the gas?
b. What is PV?
c. What is C
V
?

Solution

2-10
2.39. Suppose that the gas in Problem 2.38 is heated reversibly to 373 K at constant volume:
a. How much work is done on the system?
b. What is the increase in internal energy, U?
c. How much heat was added to the system?
d. What is the final pressure?
e. What is the final value of PV?
f. What is the increase in enthalpy, H?

Solution

2.40. Suppose that the gas in Problem 2.38 is heated reversibly to 373 K at constant pressure.
a. What is the final volume?
b. How much work is done on the system?
c. How much heat is supplied to the system?
d. What is the increase in enthalpy?
e. What is the increase in internal energy?

Solution

2.41. Suppose that the gas in Problem 2.38 is reversibly compressed to half its volume at constant temperature (273 K).
a. What is the change in U?
b. What is the final pressure?
c. How much work is done on the system?
d. How much heat flows out of the system?
e. What is the change in H?

Solution

2.42. With the temperature maintained at 0 C, 2 mol of an ideal gas are allowed to expand against a piston that supports 2 bar pressure.
The initial pressure of the gas is 10 bar and the final pressure 2 bar.
a. How much energy is transferred to the surroundings during the expansion?
b. What is the change in the internal energy and the enthalpy of the gas?
c. How much heat has been absorbed by the gas?

Solution

2-11

2.43. Suppose that the gas in Problem 2.42 is allowed to expand reversibly and isothermally from the initial pressure of 10 bar to the final
pressure of 2 bar.
a. How much work is done by the gas?
b. What are U and H?
c. How much heat is absorbed by the gas?

Solution

2.44. A sample of hydrogen gas, which may be assumed to be ideal, is initially at 3.0 bar pressure and a temperature of 25.0 C, and has a
volume of 1.5 dm
3
. It is expanded reversibly and adiabatically until the volume is 5.0 dm
3
. The heat capacity C
P
of H
2
is 28.80 J K
1

mol
1
and may be assumed to be independent of temperature.
a. Calculate the final pressure and temperature after the expansion.
b. Calculate U and H for the process.

Solution

*2.45. Initially 0.1 mol of methane is at 1 bar pressure and 80 C. The gas behaves ideally and the value of C
P
/C
V
is 1.31. The gas is
allowed to expand reversibly and adiabatically to a pressure of 0.1 bar.
a. What are the initial and final volumes of the gas?
b. What is the final temperature?
c. Calculate U and H for the process.

Solution

2.46. A gas behaves ideally and its C
V
is given by
C
V
/J K
1
mol
1
=21.52 +8.2 10
3
T/K
a. What is C
P,m
as a function of T?
b. A sample of this gas is initially at T
1
=300 K, P
1
=10 bar, and V
1
=1 dm
3
. It is allowed to expand until P
2
=1 bar and V
2
=10
dm
3
. What are U and H for this process? Could the process be carried out adiabatically?

Solution

2.47. Prove that for an ideal gas two reversible adiabatic curves on a P-V diagram cannot intersect.

2-12
Solution

2.48. An ideal gas is defined as one that obeys the relationship PV =nRT. We showed in Section 2.7 that for such gases
(U/V)
T
=0 and (H/P)
T
=0
Prove that for an ideal gas C
V
and C
P
are independent of volume and pressure.

Solution

2.49. One mole of an ideal gas underwent a reversible isothermal expansion until its volume was doubled. If the gas performed 1 kJ of
work, what was its temperature?

Solution

2.50. A gas that behaves ideally was allowed to expand reversibly and adiabatically to twice its volume. Its initial temperature was 25.00
C, and C
V,m
=(5/2)R. Calculate U
m
and H
m
for the expansion process.
Solution
2.51. With C
V,m
=(3/2)R, 1 mol of an ideal monatomic gas undergoes a reversible process in which the volume is doubled and in which 1
kJ of heat is absorbed by the gas. The initial pressure is 1 bar and the initial temperature is 300 K. The enthalpy change is 1.50 kJ .
a. Calculate the final pressure and temperature.
b. Calculate U and w for the process.

Solution

*2.52. Prove that
V
T U
U V
C
V T
| | | |
=
| |

\ . \ .

Solution

*2.53. Prove that for an ideal gas the rate of change of the pressure dP/dt is related to the rates of change of the volume and temperature by
1 1 1
dP dV dT
P dt V dt T dt
= +

Solution

2-13
*2.54. Initially 5 mol of nitrogen are at a temperature of 25 C and a pressure of 10 bar. The gas may be assumed to be ideal; C
V,m
=20.8 J
K
1
mol
1
and is independent of temperature. Suppose that the pressure is suddenly dropped to 1 bar; calculate the final temperature,
U, and H.

Solution

2.55. A chemical reaction occurs at 300 K in a gas mixture that behaves ideally, and the total amount of gas increases by 0.27 mol. If U
= 9.4 kJ, what is H?

Solution

2.56. Suppose that 1.00 mol of an ideal monatomic gas (C
V
=(3/2)R) at 1 bar is adiabatically and reversibly compressed starting at 25.0
C from 0.1000 m
3
to 0.0100 m
3
. Calculate q, w, U, and H.

Solution

2.57. Suppose that an ideal gas undergoes an irreversible isobaric adiabatic process. Derive expressions for q, w, U, and H and the final
temperature of the gas undergoing the process.

Solution

2.58. Exactly one mole of an ideal monatomic gas at 25.0 C is cooled and allowed to expand from 1.00 dm
3
to 10.00 dm
3
against an
external pressure of 1.00 bar. Calculate the final temperature, and q, w, U, and H.

Solution

2.59. A balloon 15 m in diameter is inflated with helium at 20 C.
a. What is the mass of helium in the balloon, assuming the gas to be ideal?
b. How much work is done by the balloon during the process of inflation against an external pressure of 1 atm (101.315 kPa), from
an initial volume of zero to the final volume?

Solution

Chapter 2: The First Law of Thermodynamics Real Gases
2-14
2.60. a. Calculate the work done when 1 mol of an ideal gas at 2 bar pressure and 300 K is expanded isothermally to a volume of 1.5 L,
with the external pressure held constant at 1.5 bar.
b. Suppose instead that the gas is expanded isothermally and reversibly to the same final volume; calculate the work done.

Solution

2.61. The heat capacity difference can be determined experimentally in terms of the two variables and in the equation for an ideal gas.
Determine the value of C
P
and C
V
for an ideal gas in the equation C
P
C
V
=TV
2
/ where
1 1
and
P T
V V
V T V P

| | | |
= =
| |

\ . \ .

Solution

Real Gases
2.62. For an ideal gas, PV
m
=RT and therefore (dT/dP)
V
=V
m
/R. Derive the corresponding relationship for a van der Waals gas.

Solution

*2.63. One mole of a gas at 300 K is compressed isothermally and reversibly from an initial volume of 10 dm
3
to a final volume of 0.2 dm
3
.
Calculate the work done on the system if
a. the gas is ideal.
b. the equation of state of the gas is P(V
m
b) =RT, with b =0.03 dm
3
mol
1
.
Explain the difference between the two values.

Solution

Chapter 2: The First Law of Thermodynamics Real Gases
2-15
*2.64. One mole of a gas at 100 K is compressed isothermally from an initial volume of 20 dm
3
to a final volume of 5 dm
3
. Calculate the
work done on the system if
b. the equation of state is
6 1
2
where 0.384m Pamol
m
m
a
P V RT a
V
| |
+ = =
|
\ .

[This equation is obeyed approximately at low temperatures, whereas P(V
m
b) =RT (see Problem 2.63) is obeyed more closely at
higher temperatures.] Account for the difference between the values in (a) and (b).

Solution

2.65. Derive the expression
3 2
( )
m
m
m m m m
PdV ab PdT a dT
dP dV
V b V V b T V T
= + +
for 1 mol of a van der Waals gas.

Solution

2.66. If a substance is burned at constant volume with no heat loss, so that the heat evolved is all used to heat the product gases, the
temperature attained is known as the adiabatic flame temperature. Calculate this quantity for methane burned at 25 C in the amount
of oxygen required to give complete combustion to CO
2
and H
2
O. Use the data in Appendix D and the following approximate
expressions for the heat capacities:
C
P,m
(CO
2
)/J K
1
mol
1
=44.22 +8.79 10
3
T/K
C
P,m
(H
2
O)/J K
1
mol
1
=30.54 +1.03 10
2
T/K

Solution

*2.67. Two moles of a gas are compressed isothermally and reversibly, at 300 K, from an initial volume of 10 dm
3
to a final volume of 1
dm
3
. If the equation of state of the gas is P(V
m
3
mol
1
, calculate the work done on the system, U, and
H.

Solution

Chapter 2: The First Law of Thermodynamics Essay Questions
2-16
*2.68. Three moles of a gas are compressed isothermally and reversibly, at 300 K, from an initial volume of 20 dm
3
dm
3
. If the equation of state of the gas is
2
2 m
m
n a
P V nRT
V
| |
+ =
|
\ .

with a =0.55 Pa m
6
mol
1
, calculate the work done, U, and H.

Solution

*2.69. One mole of a van der Waals gas at 300 K is compressed isothermally and reversibly from 60 dm
3
to 20 dm
3
. If the constants in the
van der Waals equation are
a =0.556 Pa m
6
mol
1
and b =0.064 dm
3
mol
1
calculate w
rev
, U, and H.

Solution

*2.70. Show that the J oule-Thomson coefficient can be written as:
1
T P
H
C P
| |
=
|
\ .

Then, for a van der Waals gas for which can be written as:
2 /
P
a RT b
C
=
calculate H for the isothermal compression of 1.00 mol of the gas at 300 K from 1 bar to 100 bar.

Solution

Essay Questions
2.71. Explain clearly what is meant by a thermodynamically reversible process. Why is the reversible work done by a system the
maximum work?
2.72. Explain the thermodynamic meaning of a system, distinguishing between open, closed, and isolated systems. Which one of these
systems is (a) a fish swimming in the sea or (b) an egg?

Chapter 2: The First Law of Thermodynamics Solutions
2-17
Solutions
2.1. A bird weighing 1.5 kg leaves the ground and flies to a height of 75 metres, where it attains a velocity of 20 m s
1
. What change in
energy is involved in the process? (Acceleration of gravity =9.81 m s
2
.)

Solution:
Given:
1
bird
1.5 kg, 75 m, 20 m s m h u

= = =
Required: E
Since in this particular system, a bird is starting from rest and moving to a height of 75 meters, there are both potential and kinetic energies
that must be considered. First we can find the potential energy which is equivalent to the work required to raise the bird to the given height.
Potential energy;
( ) ( )( )
2
2 2
2 2
1.5 kg 9.81 ms 75 m
1 103.625 kg m s
recall that 1 J 1 kg m s and therefore
1 103.6 J
w mgh
w
w
w
=
=
=
=
=

Kinetic energy;
( )( )
2
2
1
2 2
2 2
1
2
1
1.5 kg 20 m s
2
300 kg m s
just as above, 1 J 1 kg m s and therefore
300 J
k
k
k
k
E mu
E
E
E
=
=
=
=
=

The energy change of the system can be taken as the sum of both the potential and kinetic energies.
2-18
( ) 1 103.6 300 J
1 403.6 J
1.40 kJ
k p
E E E
E
E
E
= +
= +
=
=


2-19
2.2. The densities of ice and water at 0 C are 0.9168 and 0.9998 g cm
3
, respectively. If H for the fusion process at atmospheric
pressure is 6.025 kJ mol
1
, what is U? How much work is done on the system?

Solution:

Given:
3 3 1
ice water fus
0 C, 0.9168 g cm , 0.9998 g cm , 6.025 kJ mol T H
= = = =

Required: , U w

Since we are given the densities of both ice and water in this system, it is possible to determine the corresponding volumes. Knowing that
water and ice are composed of H
2
O we can say that in one mole, the corresponding mass would be approximately 18.0152 g (15.9994 +
2(1.0079)).
ice
ice
ice
ice
ice
ice
ice
one mole of ice has volume;
18.015 2 g
m
V
m
V
V
=
=
=
0.9168 g
3
3
ice
cm
19.65 cm V
=

One mole of water has volume;
2
2
2
2
2
2
2
H O
H O
H O
H O
H O
H O
H O
18.015 2 g
m
V
m
V
V
=
=
=
0.999 8 g
2
3
3
H O
cm
18.02 cm V
=

2-20
Now find the change in volume due to H fusion when moving from ice to water:
( )
2
H O ice
3
3
18.02 19.65 cm
1.63 cm
V V V
V
V
=
=
=

Since we are working with a single mole of ice and water, we can express the volume as
3 1
1.63 cm mol V

=
We are given the value of the enthalpy of fusion. Enthalpy may be defined by Eq. 2.23;
H U PV = +
Since the system is under atmospheric pressure, it is possible to determine the amount of PV work done in this process.
Since
3
1 atm dm 101.325 J = , we first change the volume into
3
dm ;
3
1.63 cm V =
3 3 3
10 dm cm

( )
3
0.00163 dm V =

Now the PV work can be found;
3
3
(1 atm)( 0.001 63 dm)
0.001 63 atm dm
0.163 J
PV
PV
PV
=
=
=

Which can then be expressed as,
1
1
0.163 J mol
0.163 J mol
PV
w PV
=
= =

2-21
Now Eq. 2.23 can be rearranged to solve for the internal energy, U;
( )
( )
( )
1 1
1 1
6.025 kJ mol 6 025 J mol
6 025 J mol 0.163 J mol
H U PV
U H PV
H
U

= +
=
= =
=

Since this is a very small difference and the value of H is uncertain in the tenths unit, we can make the approximation,
1
6.025 kJ mol
H U
U

=


2-22
2.3. The density of liquid water at 100 C is 0.9584 g cm
3
, and that of steam at the same temperature is 0.000 596 g cm
3
. If the enthalpy
of evaporation of water at atmospheric pressure is 40.63 kJ mol
1
, what is U? How much work is done by the system during the
evaporation process?

Solution:
Given:
3 3 1
water steam evap
100 C, 0.9584 g cm , 0.000 596 g cm , 40.63 kJ mol T H = = = =
Required: , U w
This problem can be solved in the manner used to solve Problem 2.2. First, calculate the change in volume when moving between states
then find the amount of pressure-volume work done on or by the system. Recall that a single mole of H
2
O has an approximate mass of
18.0152 g. The volume of one mole of liquid water at 100 C is found,
water
water
water
water
water
water
ice
18.015 2 g
m
V
m
V
V
=
=
=
0.958 4 g
3
3
ice
cm
18.797 2 cm V
=

The volume of one mole of steam has a volume of,
steam
steam
steam
steam
steam
steam
steam
18.015 2 g
m
V
m
V
V
=
=
=
0.000 596 g
3
3
steam
cm
30 226.845 6 cm V
=

2-23
( )
steam water
3
3
30 226.845 6 18.797 2 cm
30 208 cm
V V V
V
V
=
=
=

Which can then be expressed as,
3 1
30.208 dm mol V

=
Since
3
1 atm dm 101.325 J = , the PV work can be found;
( ) ( )
3
3
1 atm 30.208 dm
30.208 atmdm
3 060.825 6 J
PV
PV
PV
=
=
=

Rounding to the proper number of significant figures gives 3.06 kJ . Expressed in terms of
1
mol
gives,
1
1
3 060.825 6 J mol
3.06 kJ mol
PV
w PV
=
= =

Now Eq. 2.23 can be rearranged to solve for the internal energy, U;
( )
( )
H U PV
U H PV
= +
=

Since
1
40.63 kJ mol H =
( )
1 1
1
40.63 kJ mol 3.06 kJ mol
37.57 kJ mol
U
U

=
=


2-24
2.4. The latent heat of fusion of water at 0 C is 6.025 kJ mol
1
and the molar heat capacities (C
P,m
) of water and ice are 75.3 and 37.7 J
K
1
mol
1
, respectively. The C
P
values can be taken to be independent of temperature. Calculate H for the freezing of 1 mol of
supercooled water at 10.0 C.

Solution:
Given:
water ice
1 1 1 1 1
fus
0 C, 6.025 kJ mol , 75.3 J K mol , 37.7 J K mol
P P
T q C C = = = =
Required:
freeze
H
Because the latent heat of fusion of water is given at at 0 C and we start with supercooled water at 10.0 C. We will first heat up the
supercooled water to 0 C, go through a state change from water to ice, and then cool down the ice from 0 C to 10.0 C.
The amount of heat that needs to be supplied to increase the temperature of 1 mole of substance from
lower higher
to T T at constant pressure is
given by,
higher
lower
, ,
T
P m P m
T
q C dT =

If
, P m
C is independent of temperature, then the integral will reduce to;
( )
, , higher lower P m P m m
q C T T H = =
Therefore, when heating water from
O O
10 C to 0 C , we will get:
( )
1 higher lower
1
1
75.3 J K
P
q C T T
q

=
= ( )
1
mol 273.15 263.15 K
1
1
753 J mol q

=

The latent heat of fusion of water is given at 0 C. Therefore, the latent heat for the change of state from water to ice is:

1
2
6 025 J mol q

=
Cooling the ice from 0
o
C to -10
o
C we obtain,
2-25
( )
3 2 1
1
3
37.7 J K
P
q C T T
q

=
= ( )
1
mol 273.15 263.15 K
1
3
377 J mol q

=

Now finding the net heat;
( )
net 1 2 3
1
net
1
net
net freeze
1
freeze
753 6 025 377 J mol
5 649 J mol
5.65 kJ mol
q q q q
q
q
q H
H
= + +
=
=
=
=

2-26
2.5. A sample of liquid acetone weighing 0.700 g was burned in a bomb calorimeter for which the heat capacity (including the sample) is
6937 J K
1
. The observed temperature rise was from 25.00 C to 26.69 C.
a. Calculate U for the combustion of 1 mol of acetone.
b. Calculate H for the combustion of 1 mol of acetone.

Solution:
Given:
1
acetone ,
0.700 g, 6 937 J K , 25.00 C, 26.69 C
V m f
m C T T = = = =
Required: and U H
Acetone has a molar mass of
1
acetone
58.08 g mol M

= therefore it is possible to determine the number of moles of acetone present as well as
the amount of heat evolved per mole of acetone burned. It is important to note that bomb calorimeters work under conditions of constant
volume and therefore Eq. 2.28 applies:
The heat required to raise the temperature of 1 mole of material from
1 2
to T T at constant volume is given by;
( )
2
1
, ,
, , 2 1
1
,
6937 J K
T
V m V m
T
V m V m
V m
q C dT
q C T T
q

=
=
=
( )
( ) 299.84 298.15 K
,
,
11 723.53 J
11.72 kJ
V m
V m
q
q
=
=

Again, using the fact that the bomb calorimeter operates at constant volume, it can be simply stated that;
,
11.72 kJ
V m
U q
U
=
=

The heat evolved during the combustion of a single mole is given by;
2-27
( )
,
58.08 g
11 723.53 J
m V m
m
M
U q
m
U
=
=
1
mol
0.700 g
1
972 718 J mol
m
U

=

1
972.72 kJ mol
m
U

=
Assuming that the Ideal Gas Law applies,
( ) PV nRT =
Since the balanced reaction may be written as follows;
3 3 2 2 2
CH COCH (l) 4O 3CO (g) 3H O(l) + +
The change in moles for the gaseous species is;
products reactants
3 4
1
n n n
n
n
=
=
=

Now the enthalpy can be found using the assumption above:
( ) ( )
1
1 8.3145 J K PV

=
( )
1
mol 299.84 K
( )
( )
1
2 493.02 J mol PV

=

Recall that we can now solve for the enthalpy from Eq. 2.41,
2-28
( )
( )
1 1
1
1
972 718 J mol 2493.02 J mol
975 211 J mol
975.21 kJ mol
H U PV
H
H
H

= +
= +
=
=


2-29
2.6. An average man weighs about 70 kg and produces about 10 460 kJ of heat per day.
a. Suppose that a man were an isolated system and that his heat capacity were
4.18 J K
1
g
1
; if his temperature were 37 C at a given time, what would be his temperature 24 h later?
b. A man is in fact an open system, and the main mechanism for maintaining his temperature constant is evaporation of water. If the
enthalpy of vaporization of water at 37 C is 43.4 kJ mol
1
, how much water needs to be evaporated per day to keep the temperature
constant?

Solution:
Given:
1 1 1
man vap
70 kg, heat 10460 kJ , 4.18 J K g , 37 C, 43.4 kJ mol
P
m q C T H = = = = = =
Required:
water
at 24hrs, T m
a. First, we start by putting the heat capacity in terms of J K
-1
by using the mans mass.
1 1
4.18 J K g
P
C

=
( )
70000 g
( )
1
292 600 J K
P
C

=

The rise in temperature can then be found using the specific heat (heat capacity) as well as the amount of heat produced by the man per day.
10 460 000 J
P
q
T
C
T
=
=
292 600 J
1
K
35.75 K T
=

And using the initial temperature, the temperature at 24 hours can be found,
2-30
24hrs 0
24hrs 0
24hrs
24hrs
24hrs
35.75 K 310.15 K
345.9 K
72.8 C
T T T
T T T
T
T
T
=
= +
= +
=
=

b. We can use the enthalpy of vaporization of water as well as its molar mass (18.0152 g mol
-1
) in order to determine the
amount of water required to keep the mans temperature constant;
1
43 400 J mol
H
=
1
18.0152 g mol
1
water
water
2 409.08 J g
10 460 000 J
H
q
m
H
m
=
=
=
2 409.08 J
1
water
water
g
4 341.9 g
4.34 kg
m
m
=
=


2-31
2.7. In an open beaker at 25 C and 1 atm pressure, 100 g of zinc are caused to react with dilute sulfuric acid. Calculate the work done by
the liberated hydrogen gas, assuming it behaves ideally. What would be the work done if the reaction took place in a sealed vessel?

Solution:
Given:
Zn
25 C, 1 atm, 100 g T P m = = =
Required:
2
H
w
The balanced equation for this reaction is given by;
2 4 4 2
Zn +H SO ZnSO +H ( ) g
We can see that for each mole of zinc reacted, one mole of hydrogen gas is produced. One hundred grams of zinc (molar mass 65.39 g mol
-
1
) will then produce;
Zn
Zn
100 g
m
n
M
n
=
=
65.39 g
2
2
1
Zn
Zn H
H
mol
1.529 mol
and since
1.529 mol
n
n n
n
=
=
=

The work done by the open system is PV work and can be expressed as;
( )
2
H
w PV n RT = =
Remember that when the system DOES work, you need to include the negative sign!
2-32
1.529 mol w =
( )
1
8.3145 J K
1
mol
( )
( ) 273.15 25 K +
3 791 J
3.79 kJ
w
w
=
=

In a sealed vessel, the conditions would be such that there was no change in volume meaning that there would be no work done.
In a closed vessel;
0 kJ w =


2-33
2.8. A balloon is 0.50 m in diameter and contains air at 25 C and 1 bar pressure. It is then filled with air isothermally and reversibly
until the pressure reaches 5 bar. Assume that the pressure is proportional to the diameter of the balloon and calculate (a) the final
diameter of the balloon and (b) the work done in the process.

Solution:
Given:
balloon 1 2
0.50 m, 25 C, 1 bar, 5 bar d T P P = = = =
Required:
balloon balloon
final, d w
a) If we make the assumption that the pressure is proportional to the diameter of the balloon and D
i
and D
f
are the diameters in the
initial and final case, then we can write;
1 1
D P k =
Where k is then expressed as;
1
1
1
D
1 bar
0.50 m
2 bar m
P
k
k
k

=
=
=

At the final pressure,
2
P we can see that:
2 2
2
2
2
D
D
5 bar
D
P k
P
k
=
=
=
2 bar
1
2
m
D 2.5 m
=

The final diameter of the balloon is
2-34
balloon
2.5 m d =
b) The work done in the process of filling the balloon with air isothermally and reversibly is defined by Eq. 2.11;
2
1
rev
V
V
w PdV =

Using geometry, we can show the relationship between volume and diameter in order to solve the above equation.
The balloon will be treated as a sphere:
3
sphere
4
3
V r =
Remember that the radius is defined as half of the diameter, thus;
3
sphere
4
3 2
D
V
| |
=
|
\ .

Now we can differentiate both sides to get:
2
sphere
2
sphere
4 3
D D
3 8
1
D D
2
dV d
dV d
=
=

Now we can make this substitution into Eq. 2.11 in order to solve for the work done.
2
1
rev
V
V
w PdV =

And because of the volume proportionality to the diameter,
2
1
D
rev
D
w PdV =

Let us now use D P k = and substitute
2-35
2
1
2
1
D
rev
D
D
2
rev
D
D
1
D D D
2
w k dV
w k d
=
=

Which can be simplified to:
2
1
3
rev
1

2
D
D
w k D dD =

This expression can now be solved by integrating from
1 2
to , D D
{ }
4 4
rev 2 1
4 4 -1 4
rev
3
rev
1 1
( )
2 4
1
(2.5 0.5 ) bar m m
8
30.6 bar m
w k D D
w
w
| |
=
|
\ .
| |
=
|
\ .
=

Since 1 bar =10
5
Pa, 1 Pa =kg m
-1
s
-2
and 1 J =kg m
-2
s
-2
then we get;
rev
30.6 bar w =
( )
3 5 1
m 10 Pa bar
( )
3
rev
1 2 3
rev
2 2
rev
rev
balloon
3 063 052 Pa m
3 063 052 kg m s m
3 063 052 kg m s
3 063 052 J
3 063 kJ
w
w
w
w
w

=
=
=
=
=


2-36
2.9. When 1 cal of heat is given to 1 g of water at 14.5 C, the temperature rises to 15.5 C. Calculate the molar heat capacity of water at
15 C.

Solution:
Given:
water 1 2
1 cal, 1 g, 14.5 C, 15.5 C q m T T = = = =
Required: at 15 C
P
C
Using the mass and known molar mass for water (18.0152 g mol
-1
), we can find the number of moles that will absorb 1 cal of heat;
water
water
1.00 g
m
n
M
n
=
=
18.0152 g
1
water
mol
0.0555 mol n
=

Since 1 cal =4.184 J we can then find the heat capacity according to Eq. 2.25 or Eq. 2.27 depending on the conditions;
V
V
dq
C
dT
= (Eq. 2.25)
p
p
p
dq
H
C
dT T
| |
= =
|
\ .
(Eq. 2.27)
More generally, because we have not been given the systems conditions;
( ) ( )
1
1 cal 4.184 J
or
15.5 273.15 14.5 273.15 K 1 K
4.184 J K
q
C
T
C C
C

=
= =
+ + (

=

The molar heat capacity would then be;
2-37
m
q C
C
n T n
= =

1
1 1 1 1
4.184 J K
75.387 387 39J K mol 75.4 J K mol
0.0555 mol
m m
C C

= = =
2-38
2.10. A vessel containing 1.000 kg of water at 25.00 C is heated until it boils. How much heat is supplied? How long would it take a one-
kilowatt heater to supply this amount of heat? Assume the heat capacity calculated in Problem 2.9 to apply over the temperature
range.

Solution:

Given:
water
1.000 kg, 25.00 C m T = = ,
1 1
75.387 J K mol (calculated in problem2.9)
m
C

=

Required:
heater operation
, q t

Recall that the boiling point for water is 100 C so this will be our final temperature which will yield a change in temperature of 75.0 C (or
75 K). In order to determine the amount of heat required to heat the water from one temperature to the next, we must first find the number
of moles of water heated. The molar mass for water is 18.0152 g mol
-1
.

water
water
1000 g
m
n
M
n
=
=
18.0152 g
1
water
mol
55.5087 mol n
=

Remember that:
m
q
C
n T
=

So we can rearrange this and solve for the heat:
1
75.387 J K
m
q C n T
q

=
=
1
mol
( )
55.5087 mol
( )
75.0 K
( )
313 849 J
314 kJ
q
q
=
=

2-39
A 1 kW heater can supply the heat in 314 seconds since 1 kW=1000 W and one 1 J =1 W s and 1 kJ =1 kW s;
heater
314 s t =


2-40
2.11. A nonporous ceramic of volume V m
3
and mass M kg is immersed in a liquid of density d kg m
3
. What is the work done on the
ceramic if it is slowly raised a height h m through the liquid? Neglect any resistance caused by viscosity. What is the change in the
potential energy of the ceramic?

Solution:
Given:
3 3
m, kg, kg m V M d = = =
Required: ,
p
w E
Since we can neglect any resistance caused by the viscosity of the liquid, we can say that the apparent mass of the ceramic decreases by the
mass of liquid that is displaced when it is raised.
The mass of the liquid can be defined as;
kg
l
M Vd =
While the apparent mass of the ceramic can be defined as;
( )
c
c
kg
l
M M M
M M Vd
=
=

The work done when raising a mass is given by;
w mgh =
Where g is the earths gravitational constant and making the correct substitutions;
( )
( )
2
2 2
kg m s m
kg m s
w M Vd gh
w M Vd gh
=
=

Since
2 2
1 J 1 kg m s
= , we write,
( ) J w M Vd gh =
2-41
When moving a mass from rest to a certain height, the work done on the mass also represents the potential energy change.
( ) J
p
E M Vd gh =
2-42
2.12. Show that the differential dP of the pressure of an ideal gas is an exact differential.

Solution:

We have already learned that variables such as internal energy and volume (U and V) are state functions. This means that these functions
are independent of the path taken.

Since the path of the integral for the differential is not important; meaning, you can take any path to get to the same result, the differential is
called exact. Variables such as q and w have differentials which are path dependent; and are thus inexact. Integrating over these paths is
more difficult since the integrals do not reduce to a simple difference of two boundary values. They represent areas over which we must
integrate.

Eulers Criterion for Exactness states that if;

( , ) ( , ) dz M x y dx N x y dy = + (Eq. 2.17)

where M and N are functions of the independent variables x and y. We must then take the mixed partials of M and N and determine whether
they are equal to one another or not.

If:
( , ) and ( , )
we need to show that the mixed partial derivatives are equivalent:

Thus we can say that:

y x
y x
y x
x
z z
M x y N x y
x y
z z
y x x y
M
y
| | | |
= =
| |

\ . \ .
( (
| | | |
=
( ( | |

\ . ( \ .

| |
|
\ .

y
N
x
| |
=
|
\ .

This relationship must be satisfied if dz is an exact differential (i.e. it meets Euler Criterion for Exactness). These equations can be found in
the textbook, Eq.2.17 to Eq.2.22.
2-43

From the Ideal Gas Law we know that PV nRT = . From Appendix C, the total derivative of P is a function of both T and V. Thus, for a
single mole of gas:
RT
P
V
= .
Differentiating both sides, we get:
2
RT R
dP dV dT
V V
= +

Applying Eulers theorem gives
2 2
2
LHS:
RHS:
RT R
T V V
R R
V V V
| |
=
|
\ .
| |
=
|
\ .

LHS =RHS and therefore, the differential is exact and P is a state function.
2
exact
RT R
T V V V
dP
| | | |
=
| |

\ . \ .
=

2-44
2.13. Determine whether dU =xy
2
dx +x
2
ydy is an exact differential. If it is find the function U of which dU is the differential. Do this by
integrating over suitable paths. In a plot of y against x, show a plot of the paths that you chose.

Solution:
Given: dU =xy
2
dx +x
2
ydy
Required: exact or inexact? plot y vs x.
In order to test for the exactness of the differential dU, we will again use the Euler test for exactness described in problem 2.14.
Differentiating both sides we can then say that dz is equal to dU and,
2 2

( , ) and ( , )
y x
dU xy dx x ydy
U U
M x y N x y
x y
= +
| | | |
= =
| |

\ . \ .

Now taking the mixed partial derivatives yields;
2 and 2
y x
y x
M N
xy xy
y x
M N
y x
dU exact
| | | |
= =
| |

\ . \ .
| | | |
=
| |

\ . \ .
=

dU, because it is exact, it also describes a state function.
Since the mixed partials are equivalent, we know that taking the integral of dU will result in a simple difference between the beginning and
end points (ie. the path to a single result is not important). The integral can be given by;
,
2 2
x y
A B
dU xy dx x ydy = +

Let A and B be two segments which lead to the final position (x,y). We can use a path which simplifies the integration by choosing the
origin (0,0) to x on the A segment. Here, y=0 so this integral will equal zero. In the second segment, segment B, x has a specific value and
y varies from (0,0) to y.
2-45

2
0
2 2
The integral reduces to:
1
2
y
dU x ydy
dU x y C
=
= +

2-46
2.14. Using the data given in Table 2.1 and Appendix D, find the enthalpy change for the reaction 2H
2
(g) +O
2
(g) 2H
2
O(g) at 800 K.

Solution:

Given: Table 2.1 and Appendix D
Required:
2
( )
m
H T
From Table 2.1 we are given the following information regarding the reaction
2H
2
(g) +O
2
(g) 2H
2
O(g)
All of the values given in Appendix D correspond to the standard states: 25.00 C and 1 bar pressure.
2
1
1
1 1
H O(g):
241.826 kJ mol
237.2 kJ mol
188.8 J K mol
f
f
H
G
S

=
=
=

At a temperature of 800 K and using equations 2.50 through 2.52 we obtain;
2
1
2 1
( ) ( )
T
m m p
T
H T H T C dT =
(Eq. 2.50)
If
1
( )
m
H T is known for T
1
=25.00 C, the value of
2
( )
m
H T at any temperature T
2
can be found.
2
1
2 1
( ) ( )
T
m m p
T
H T H T C dT = +

Now we can make a substitution for using Eq. 2.49
p
C ;
( )
2
1
2
2 1
( ) ( )
T
m m
T
H T H T d eT fT dT
= + + +
(Eq. 2.51)
( )
2 2
2 1 2 1 2 1
2 1
1 1 1
( ) ( ) ( )
2
m m
H T H T d T T e T T f
T T
| |
= + +
|
\ .
(Eq. 2.52)
2-47
From the values in Table 2.1 we obtain,
( )
( ) ( )
2 2 2
products reactants
H O H O
1 1 1 1
2 2
2 30.54 J K mol 2 27.28 29.96 J K mol
d d d
d d d d
d

=
= +
= +

( )
1 1
1 1
61.08 84.52 J K mol
23.44 J K mol
d
d

=
=

( )
( ) ( )
( )
2 2 2
products reactants
H O H O
3 2 1 3 3 2 1
2 1
3 2 1
2 2
2 10.29 10 J K mol 2 3.26 10 4.18 10 J K mol
0.020 58 0.0107 J K mol
9.88 10 J K mol
e e e
e e e e
e
e
e

=
= +
= +
=
=

( )
( ) ( )
2 2 2
products reactants
H O H O
4 5 1
1
4 1
2 2
2 0 2 5.0 10 1.67 10 J K mol
67 000 J K mol
6.7 10 J K mol
f f f
f f f f
f
f
f
=
= +
=
=
=

First we need to calculate the enthalpy for this reaction at 298.15 K (for 2 moles);
1
1
(298.15 K) 2 2( 241.826 kJ mol )
(298.15 K) 483.652 kJ mol
f
H H
H
= =
=

And making all substitutions into Eq. 2.52 we obtain,
2-48
( )
1 -1
800 K 483 652 J mol 23.44 J K H
m
= + ( )
-1
mol 800-298.15 K
| |
|
\ .
1
3 -2
9.88 10 J K
2

+
( )
2 2 2 -1
mol 800 298.15 K
| |

|
\ .
4
6.7 10 J K
( )
1
1 1
-1
mol - K
800 298.15
| |
|
\ .
( ) ( )
( )
( )
1
800 K 483 652 11 763.364 2 722.466 493 141.969 101 1 J mol
800 K 492 550.928 4
-1
800 K 492.55 kJ mol
H
m
H
m
H
m
= + +
=
=


2-49
2.15. A sample of liquid benzene weighing 0.633 g is burned in a bomb calorimeter at 25.00 C, and 26.54 kJ of heat are evolved.
a. Calculate U
m

b. Calculate H
m

Solution:
Given:
benzene
0.633 g, 25 C, 26.54 kJ m T q = = =
Required: and
m m
U H
a. First, it is important to remember that when using a bomb calorimeter, we are working with a constant volume. Also, the water
surrounding the bomb increases in temperature but gradually loses heat to the surroundings. Second, since benzene has the
molecular formula C
6
H
6
, it has a molar mass of approximately 78.1121 g mol
-1
. With this latter information, the number of moles
of benzene can be found.
benzene
benzene
0.633 g
m
n
M
n
=
=
78.1121 g
1
benzene
mol
0.008 104 mol n
=

The heat evolved in the combustion of 1 mole of benzene is given by,
1
26.54 kJ
0.008 104 mol
3 275 kJ mol
m
m
q
q

=
=

Recall that when working with a bomb calorimeter as described earlier, the internal energy is
1
and therefore,
3 275 kJ mol
m m
m
U q
U

=
=

b. The balanced equation for this reaction is:
2-50
6 6 2 2 2
15
C H (l) O (g) 6CO (g) 3H O(l)
2
+ +

We have already seen Eq. 2.41, ( ) H U PV = + many times. However, in this case, we can work under the assumption that
( ) ( ) PV n RT = which gives;
( )
( )
1 1
15
where 6 1.5
2
Making the appropriate substitutions;
3 274 900 kJ mol 1.5 8.3145 J K
m m
m
H U n RT
n
H

= +
= =
= +
( )
1
mol 298.15 K
( )
1
1
3 278 618.452 J mol
3 279 kJ mol
m
m
H
H
=
=


2-51
2.16. Deduce the standard enthalpy change for the process:
2CH
4
(g) C
2
H
6
(g) +H
2
(g)
(data in Appendix D)

Solution:

Given: Appendix D

Required: H

All information given in the tables of Appendix D correspond to the standard states T =25.00C and 1 bar pressure. Enthalpies of
formation allow us to calculate enthalpies of any reaction provided that we know the
O
f
H values for all reactants and all products. The
standard enthalpy change may be found using Eq. 2.53:
( ) ( ) products reactants
f f
H H H =

Using the information provided in Appendix D for the reaction:
2CH
4
(g) C
2
H
6
(g) +H
2
(g)

( ) ( )
( ) ( ) ( )
( )( )
2 6 2 4
1
1
products reactants
C H , g H , g 2 CH , g
84.0 0 2 74.6 kJ mol
65.2 kJ mol
f f
H H H
H H H H
H
H
=
= + (

= + (

=


2-52
2.17. A sample of liquid methanol weighing 5.27 g was burned in a bomb calorimeter at 25.00 C, and 119.50 kJ of heat was evolved
(after correction for standard conditions).
a. Calculate
c
H for the combustion of 1 mol of methanol.
b. Use this value and the data in Appendix D for H
2
O(l) and CO
2
(g) to obtain a value for
f
H(CH
3
OH,l), and compare with the
value given in the table.
c. If the enthalpy of vaporization of methanol is 35.27 kJ mol
1
, calculate
f
H for CH
3
OH(g).

Solution:
Given:
methanol
5.27 g, 25 C, 119.50 kJ m T q = = =
Required: ( ) ( )
3 3
, CH OH, l , CH OH, g
c f f
H H H
a. Remember that when we are working with bomb calorimeters, the conditions are such that volume remains constant. Knowing that
methanol has the molecular formula CH
3
OH, we can determine the molar mass: approximately 32.04 g mol
-1
. With this, we can
determine the number of moles burned in the reaction.
methanol
methanol
5.27 g
m
n
M
n
=
=
32.04 g
1
methanol
mol
0.164 481 897 mol n
=

Using the heat evolved during the reaction, it is possible to determine the change in internal energy if you remember that: U q = at
constant volume.
2-53
,
,
1
,
O
,
O 1
119.50 kJ
0.164 481 897 mol
726.523 7192 kJ mol
726 523.7192 J mol
V m
methanol
V m
V m
c V m
c
q
q
n
q
q
U q
U
=
=
=
=
=

In this case, we can work under the assumption that ( ) PV nRT = so we can use the following equation to solve for the enthalpy of
combustion:
( ) H U PV = +
( )
( )
1
726 523.7192 J mol
c c
c
H U n RT
H n RT
= +
= +

The balanced reaction is written as;
3 2 2 2
3
CH OH(l) O ( ) CO (g) 2H O
2
3
(for gaseous species) 1
2
0.5
g
n
n
+ +
=
=

And by making the appropriate substitutions we obtain,
( )
( )
1
1 1
726 523.7192 J mol
726 523.7192 J mol 0.5 8.3145 J K
c
c
H n RT
H

= +
= +
( )
1
mol 298.15 K
( )
1
1
727 763.2033 J mol
727.8 kJ mol
c
c
H
H
=
=

2-54
b. The balanced reaction is as follows,
3 2 2 2
1
3
(1) CH OH (l) O (g) CO (g) 2H O
2
where 727.8 kJ mol
c
H

+ +
=

Using data from Appendix D, for H
2
O and CO
2
, we have the following reactions:
2 2 2
1
2 2
1
1
(2) H (g) O (g) H O(l)
2
where 285.830 kJ mol
(3) C(s) O (g) CO (g)
where 393.51 kJ mol
f
f
H
H
+
=
+
=

Both of these reactions can be coupled in order to produce methanol:
2 2 3
1
(4) C(s) 2H (g) O (g) CH OH(l)
2
+ +
This is done by multiplying the second equation (2) by 2 and adding it to the third equation (3) and subtracting equation one (1).
( )
2 2 2
1
1
2 (H O) (CO ) (2H O)
2 285.830 393.51 727.8 kJ mol
237.4 kJ mol
f f f f
f
f
H H H H
H
H
= +
= + (

=

c. The value given in Appendix D is
1
239.2 kJ mol
f
H

= , which differs only very slightly from the value found through the
coupling of the three equations. They might have used different data which would account for the disparity.

The reaction for the vaporization of methanol is as follows:
3 3
(5) CH OH(l) CH OH(g)
Where we are given that
1
32.27 kJ mol
v
H

=
2-55
We can now couple equations 4 and 5 in order to get
( )
( ) ( )
( )
2 2 3
3
1
3
1
3
1
C(s) 2H (g) O (g) CH OH(g)
2
CH OH, g (Eq.4) (Eq.5)
CH OH, g 237.5 35.27 kJ mol
CH OH, g 202.2 kJ mol
f f v
f
f
H H H
H
H
+ +
= +
= +
=


2-56
2.18. Calculate the heat of combustion (
c
H ) of ethane from the data given in Appendix D.
Solution:
Given: Appendix D
Required:
c
H
All of the values given in Appendix D were taken under the standard conditions of T=25.00C and 1 bar pressure. The reaction for the
combustion of ethane can be found by coupling equations 1 through 3 in the following manner (all enthalpies from Appendix D):

graphite 2 2 6
(1) 2C 3H (g) C H (g) +
where
1
84.0 kJ mol
f
H

=
graphite 2 2
(2) C O (g) CO (g) +
where
1
393.51 kJ mol
f
H

=
2 2 2
1
(3) H (g) O (g) H O(l)
2
+
where
1
285.830 kJ mol
f
H

=

In order to get the reaction for the combustion of ethane, we need to multiply Eq. 3 by 3, add it to Eq. 2 multiplied by 2 then subtract Eq.1
from the mix. This series of operations yields;
( ) ( ) ( )
2 6 2 2 2
1
1
7
C H (g) O (g) 2CO (g) 3H O(l)
2
3 (Eq.3) 2 (Eq. 2) (Eq.1)
3 285.830 2 393.51 84.0 kJ mol
1560.5 kJ mol
c f f f
c
c
H H H H
H
H
+ +
= +
= + (

=

2-57
2.19. The model used to describe the temperature dependence of heat capacities (Eq. 2.48; Table 2.1) cannot remain valid as the
temperature approaches absolute zero because of the 1/T
2
term. In some cases, the model starts to break down at temperatures
significantly higher than absolute zero. The following data for nickel are taken from a very old textbook (Numerical Problems in
Advanced Physical Chemistry, J . H. Wolfenden, London: Oxford, 1938, p. 45). Fit these data to the model and find the optimum
values of the parameters.
T/K 15.05 25.20 47.10 67.13 82.11 133.4 204.05 256.5 283.0
CP/J K
1

mol
1

0.1943 0.5987 3.5333 7.6360 10.0953 17.8780 22.7202 24.8038 26.0833

Examine the behavior of the fit in the range 10 T 25 and comment on this.
Solution:
First we need to perform a multiple regression on the equation z = d+ex+fy using the following definitions:
,
2
1
P m
z C
x T
y
T
=
=
=

Once we have finished making all the appropriate substitutions, we will obtain the following expression;
2
1.7267 9.3424 10 871.4 z x y
= +
In other words, we find that,
1 1
2 2 1
2 1
1.7267 J K mol
9.3424 10 J K mol
871.4 10 J K mol
d
e
f

=
=
=

Below, we have presented two plots of this function. One is in the range of 15 T 275 and the other is in the range of 10 T 25. It can
be seen that the function becomes negative at T 16.1 K. It is important to realize that a negative heat capacity is not physically
possible. This is therefore an indication that the temperature dependence of heat capacities of solids at low temperature cannot be expressed
using the model that we have implemented here. Check out Chapter 16 Section 5 for more information on this subject.
2-58

2-59
2.20. Suggest a practicable method for determining the enthalpy of formation
f
H of gaseous carbon monoxide at 25 C. (Note: Burning
graphite in a limited supply of oxygen is not satisfactory, since the product will be a mixture of unburned graphite, CO, and CO
2
.)

Solution:

In order to determine the enthalpy of formation for gaseous carbon monoxide, we can measure the heat of combustion of graphite, gaseous
carbon monoxide and gaseous carbon dioxide. With this information it will then be possible to determine the enthalpy of formation by
using Hess Law which states that:

f f
H H H =

This can be rewritten using the enthalpies of combustion and solving for the enthalpy of formation for carbon monoxide.


2-60
2.21. If the enthalpy of combustion
c
H of gaseous cyclopropane, C
3
H
6
, is 2091.2 kJ mol
1
at 25 C, calculate the standard enthalpy of
formation
f
H.

Solution:
Given:
1
2091.2 kJ mol , 25 C
c
H T = =
Required: ( ) cyclopropane
f
H
This problem can be solved in the same manner as was done in problem 2.18. However, this time we will be working in reverse as we are
given the enthalpy of combustion and we must find the enthalpy of formation. We will start with the reaction for the combustion of
cyclopropane.
3 6 2 2 2
9
(1) C H (g) O (g) 3CO (g) 3H O(l)
2
+ +
We are given the enthalpy of combustion in the problem, so now we need to consider the reaction for the formation of both
2 2
CO (g) and H O(l)
graphite 2 2
(2) C O (g) CO (g) +
Which has
1
393.51 kJ mol
f
H

= according to Appendix D
2 2 2
1
(3) H (g) O (g) H O(l)
2
+
Which has
1
285.830 kJ mol
f
H

In order to formulate the correct balanced reaction for the formation of cyclopropane, we must multiply Eq. 2 by 3, add it to Eq. 3
multiplied by 3 and then subtract Eq. 1 from the result.
graphite 2 3 6
3C 3H (g) C H (g) +
We must now perform the same operations on the enthalpies of formation and combustion for each reaction, which yields:
2-61
( ) ( ) ( ) ( )
( )
2 2
1
cyclopropane 3 CO 3 H O cyclopropane
cyclopropane 53.2 kJ mol
f f f c
f
H H H H
H

= +
=

2-62
2.22. The parameters for expressing the temperature dependence of molar heat capacities for various substances listed in Table 2.1 are
obtained by fitting the model C
P,m
=d +eT +f/T
2
to experimental data at various temperatures and finding the values of the
parameters d, e, and f that yield the best fit. Several mathematical software packages (Mathematica, Mathcad, Macsyma, etc.) and
several scientific plotting packages (Axum, Origin, PSIPlot, etc.) can perform these fits very quickly. Fit the following data given
the temperature dependence of C
P,m
for n-butane to the model and obtain the optimum values of the parameters.
T/K 220 250 275 300 325 350 380 400
CP/J K
1
mol
1
0.642 0.759 0.861 0.952 1.025 1.085 1.142 1.177

Solution:
J ust as we have already done in problem 2.19 we must perform a multiple regression on the following expression:
z = d+ex+fy
Using the same definitions as before, we have,
,
2
3
1 1
3 2 1
4 1
1
0.800 53 1.303 10 21991.0
0.801 J K mol
1.303 10 J K mol
2.199 10 J K mol
P m
z C
x T
y
T
z x y
d
e
f
=
=
=
= +
=
=
=

2-63

2-64
2.23. From the data in Appendix D, calculate H for the reaction (at 25 C):
C
2
H
4
(g) +H
2
O(l) C
2
H
5
OH(l)
Solution:
Given: Appendix D
Required: H
This problem can be solved in the same way as Problem 2.21. It is always important to outline all of the reactions that can be used to build
the final reaction given above. We will need the reactions and enthalpies for the formation of H
2
O(l) and C
2
H
4
(g). Since we are already
given the reaction for the formation of ethanol, all we need to do is take its enthalpy of formation from Appendix D.
Remember that all values reported in Appendix D were taken under the standard conditions of
T =25.00 C and 1 bar pressure.
2 2 2
1
(1) H (g) O (g) H O(l)
2
+
Which has
1
285.830 kJ mol
f
H

graphite 2 2 4
(2) 2C 2H (g) C H (g) +
Which has
1
52.4 kJ mol
f
H

( ) ( ) ( )
2 4 2 2 5
(3) C H g H O l C H OH l +
Which has
1
277.6 kJ mol
f
H

Since we need the reverse of reactions for Eqs. 1 and 2, we can simply reverse the signs of H to get;
( ) ( ) ( ) ( )
2 2 4 2 5
H O C H C H OH
f f f
H H H H = + +
Rather than using this simply logic, we may use Eq. 2.53 which states that:
2-65
( ) ( )
( ) ( ) ( )
2 5 2 2 4
products reactants
C H OH H O C H
f f
f f f
H H H
H H H H
=
( = +

Both procedures give the same value:
( )
| |
1
1
277.6 285.830 52.4 kJ mol
277.6 285.830 52.4 kJ mol
H
H
= +
= +

1
44.2 kJ mol H

=
2-66
2.24. The bacterium Acetobacter suboxydans obtains energy for growth by oxidizing ethanol in two stages, as follows:
a.
2 5 2 3 2
1
C H OH(l) O (g) CH CHO(l) H O(l)
2
+ +
b.
3 2 3
1
CH CHO(l) O (g) CH COOH(l)
2
+
The enthalpy increases in the complete combustion (to CO
2
and liquid H
2
O) of the three compounds are

c
H/kJ mol
1

Ethanol (l) 1370.7
Acetaldehyde (l) 1167.3
Acetic acid (l) 876.1

Calculate the H values for reactions (a) and (b).

Solution:

Given: See statement of problem

Required: H

a. This problem can be solved in the same way as problem 2.23. It is always important to outline all of the reactions that can be used
to build the final two reactions given above. The pertinent reactions are as follows:
2 5 2 2 2
(1) C H OH 3O 2CO 3H O + +
This is for the combustion of ethanol and we are given the enthalpy of combustion.
1
3 2 2 2
1370.7 kJ mol
5
(2) CH CHO O 2CO 2H O
2
c
H

=
+ +

This is for the combustion of acetaldehyde and we are given the enthalpy of combustion.
2-67
1
3 2 2 2
1167.3 kJ mol
(3) CH COOH 2O 2CO 2H O
c
H

=
+ +

This is for the combustion of acetic acid and we are given the enthalpy of combustion.
1
876.1 kJ mol
c
H

=

Using Eq. 2.53, we can determine the enthalpies for reactions A and B:
(products) (reactants)
f f
H H H =

Reaction A:
3 2 5
(CH CHO) (C H OH)
f f
H H H =
Remember that we are given the COMBUSTION enthalpies, so the enthalpies of FORMATION will be equal in magnitude but opposite in
sign. This is very important!
( )
3 2 5
1
1
(CH CHO) ( (C H OH))
1370.7 1167.3 kJ mol
203.4 kJ mol
c c
H H H
H
H
=
= +
=

b. Reaction B:
3 3
(CH COOH) (CH CHO)
f f
H H H =
Using the same logic behind whether we are given the enthalpies of combustion or formation and based on the direction of the reactions, we
determine that:
2-68
| |
( )
3 3
1
1
1
(CH COOH) ( (CH CHO))
( 876.1) ( 1167.3) kJ mol
876.1 1167.3 kJ mol
291.2 kJ mol
c c
H H H
H
H
H
= +
= +
=
=

2-69
2.25. The enthalpy of combustion of acrylonitrile (C
3
H
3
N) at 25 C and 1 atm pressure is 1760.9 kJ mol
1
[Stamm, Halverson, and
Whalen, J. Chem. Phys., 17, 105(1949)]. Under the same conditions, the heats of formation of HCN(g) and C
2
H
2
(g) from the
elements are 135.1 and 226.73 kJ mol
1
, respectively [The NBS Tables of Chemical and Thermodynamic Properties, Supp. 2 to Vol.
11 of J. Phys. Chem. Ref. Data]. Combining these data with the standard enthalpies of formation of CO
2
(g) and H
2
O(g), calculate
the enthalpy change in the reaction HCN(g) +C
2
H
2
(g) H
2
C=CHCN(g). [Notes: (a) Assume that the nitrogen present in
acrylonitrile is converted into nitrogen gas during combustion. (b) Assume that all substances except for graphite (for the formation
of CO
2
) are gases, i.e., ignore the fact that acrylonitrile and water will be liquids under the conditions given here.]

Solution:
Given: see above
Required: H
We will be using the same principles for many of these problems so it is always important to compile a list of all relevant reactions so that
they can be easily manipulated and used for reference when trying to see where a particular reaction came from (ie. coupling to form new
products). Here is a list of all of the reactions involved:
2 2 2 2 2
1 3 1
(1) CH CHCN 7 O (g) 3CO (g) H O(g) N
2 2 2
+ + +
we are given that
1
1760.9 kJ mol
c
H

=
graphite 2 2
(2) C O (g) CO (g) +
from Appendix D, we know that
1
393.51 kJ mol
f
H

=
2 2 2
1
(3) H (g) O (g) H O(g)
2
+
from Appendix D, we know that
1
241.83 kJ mol
f
H

=
graphite 2 2 2
(4) 2C H (g) C H (g) +
we are given that
1
226.73 kJ mol
f
H

=
2-70
graphite 2 2
1 1
(5) C H (g) N HCN(g)
2 2
+ +
we are given that
O 1
135.10 kJ mol
f
H

=
In order to generate the desired reaction; HCN(g) +C
2
H
2
(g) H
2
C=CHCN(g) the following manipulations need to made to the above
five equations.
3
3(Eq.2) (Eq.3) (Eq.1) (Eq.4) (Eq.5)
2
+
Remember that we need to perform these manipulations on the enthalpies as well which yields;
( ) ( )
2 2 2 2 2
1
1
3
3(Eq.2) (Eq.3) (Eq.1) (Eq.4) (Eq.5)
2
3
3 (CO ) (H O) (CH CHCN) (C H ) (HCN)
2
3
3 393.51 241.83 1 760.9 226.73 135.10 kJ mol
2
144.2 kJ mol
f f c f f
H H H H H H
H
H
+
= +
( | |
= +
| (
\ .
=

2-71
2.26. Calculate H for the reaction;
C
2
H
5
OH(l) +O
2
(g) CH
3
COOH(l) +H
2
O(l)
making use of the enthalpies of formation given in Appendix D. Is the result consistent with the results obtained for Problem 2.24?

Solution:
Given: Appendix D
Required: H for the reaction
We will begin by defining the reactions that involve the formation of methanol, acetic acid and water. Recall that all values given in
Appendix D were taken at the standard temperature of 25.00C and 1 bar pressure. From Appendix D, we have;
2 2 2 5
1
1
(1) 2C(s) 3H (g) O (g) C H OH(l)
2
277.6 kJ mol
f
H

+ +
=

2 2 3
1
(2) 2C(s) 2H (g) O (g) CH COOH(l)
484.3 kJ mol
f
H

+ +
=

2 2 2
1
1
(3) H (g) O (g) H O(l)
2
285.830 kJ mol
f
H

+
=

In order to formulate the wanted reaction;
( ) ( ) ( ) ( )
2 5 2 3 2
C H OH l O g CH COOH l H O l + +
We must add Eq. 3 to Eq. 2 then subtract Eq. 1 from the sum which yields;
2-72
2 2 3
2 2 2
(2) 2C(s) 2H (g) O (g) CH COOH(l)
1
(3) H (g) O (g) H O(l)
2
2C(s)
+ +
+ +
2
3H (g) +
2 3 2
2 5
3
O (g)CH COOH(l) H O(l)
2
(1) C H OH(l) 2C(s)
+ +

2
3H (g) +
2
2 5 2 3 2
1
O (g)
2
C H OH(l) O (g) CH COOH(l) H O(l)
+
+ +

Making the same manipulations on the enthalpies, we obtain,
( ) ( ) ( )
( ) ( ) ( )
( )
1
1
1
Eq.2 Eq.3 Eq.1
484.3 285.83 277.6 kJ mol
484.3 285.83 277.6 kJ mol
492.53 kJ mol
f f f
H H H H
H
H
H
= +
= + (

= +
=

Recall that from problem 2.24 we come to the conclusion that:
Reaction A:
3 2 5
(CH CHO) (C H OH)
f f
H H H =
1
203.4 kJ mol H

=
Reaction B:
3 3
(CH COOH) (CH CHO)
f f
H H H =
1
291.2 kJ mol H

=
2-73
This will produce a slightly different answer than the one we have obtained.
| |
1
1
(reaction A) (reaction B)
203.4 ( 291.2) kJ mol
494.6 kJ mol
H H H
H
H
= +
= +
=

2-74
2.27. The disaccharide -maltose can be hydrolyzed to glucose according to the equation
C
12
H
22
O
11
(aq) +H
2
O(l) 2C
6
H
12
O
6
(aq)
Using data in Appendix D and the following values, calculate the standard enthalpy change in this reaction:

f
H/kJ mol
1

C
6
H
12
O
6
(aq) 1263.1
C
12
H
22
O
11
(aq) 2238.3

Solution:
Given: Appendix D
Required: H
This problem will be solved in the same way that we have solved all similar problems. Let us first make a list of the important reactions
involved in the process. From Appendix D we have:
2 2 2
1
1
(1) H (g) O H O(l)
2
285.83 kJ mol
f
H

+
=

2 2 6 12 6 2
(2) 6CO 6H O C H O 6O + +
We are given that
1
1263.1 kJ mol
f
H

=
( )
2 2 12 22 11 2
(3) 2 6CO 6H O C H O H O + +
We are given that
1
2238.3 kJ mol
f
H

=
In order to create the wanted reaction: ( ) ( ) ( )
12 22 11 2 6 12 6
C H O aq H O l 2C H O aq +
We must multiply Eq. 2 by two then subtract Eq. 3 and Eq. 1 which yields:
2-75
2
2 (2) 12CO =
2
12H O +
6 12 6 2
2C H O 12O
(3) 2
+
=
2
6CO
2
6H O +
( )
( ) ( ) ( )
12 22 11 2
2 2 2
12 22 11 2 6 12 6
C H O H O(l)
1
(1) H ( ) O H O(l)
2
C H O aq H O l 2C H O aq
g
+
= +
+

This must then be done for the enthalpies of formation which gives,
( ) ( ) ( )
| |
O O
1
1
1
2 Eq.2 Eq.3 Eq.1
(2 1263.1) ( 2238.3) ( 285.83) kJ mol
2.07 kJ mol
2.1 kJ mol
H H H H
H
H
H
=
=
=
=


2-76
2.28. The standard enthalpy of formation of the fumarate ion is 777.4 kJ mol
1
. If the standard enthalpy change of the reaction:
fumarate
2
(aq) +H
2
(g) succinate
2

(aq)
is 131.4 kJ mol
1
, calculate the enthalpy of formation of the succinate ion.

Solution:
Given:
1 1
(fumarate) 777.4 kJ mol , 131.4 kJ mol
f
H H = =
Required: (succinate)
f
H
Now we are given the standard enthalpy change for a reaction and we are asked to calculate the enthalpy of formation for the succinate ion.
We can do this by rearranging what we already know and solving for the unknown. This is based on the same method that we have been
practicing for many of the problems throughout this chapter.
(succinate) (fumarate)
f f
f f
H H H
H H H
=
=

Given that:
1
1
(fumarate) 777.4 kJ mol
(rxn) 131.4 kJ mol
f
H
H
=
=

Then we can say that:
( )
( )
1 1
1 1
1
1
(succinate) (fumarate)
131.4 kJ mol (succinate) 777.4 kJ mol
131.4 kJ mol (succinate) 777.4 kJ mol
(succinate) 131.4 777.4 kJ mol
(succinate) 646.0 kJ mol
f f
f
f
f
f
H H H
H
H
H
H

=
=
= +
=
=

2-77
2.29. The H for the mutarotation of glucose in aqueous solution,
-D-glucose(aq) -D-glucose(aq)
has been measured in a microcalorimeter and found to be 1.16 kJ mol
1
. The enthalpies of solution of the two forms of glucose
have been determined to be
H =10.72 kJ mol
1
H =4.68 kJ mol
1
Calculate H for the mutarotation of solid -D-glucose to solid -D-glucose.

Solution:
Given:
1 1 1
1.16 kJ mol , 10.72 kJ mol , 4.68 kJ mol H H H

= = =
Required: (mutarotation) H in solid state
We are given that;
( ) ( )
( ) ( )
1
1
(1) D glucose s D glucose aq
10.72 kJ mol
(2) D glucose s D glucose aq
4.68 kJ mol
H
H

=

=

And for the mutarotation in the aqueous state we have;
( ) ( )
1
(3) D glucose aq D glucose aq
1.16 kJ mol H

=

Therefore we obtain ( ) ( ) D glucose s D glucose s by adding Eqs. 1, 2 and 3.
2-78
( ) ( ) (1) D glucose s D glucose aq
( ) (2) D glucose aq ( )
( )
D glucose s
(3) D glucose aq

+ ( ) D glucose aq
( ) ( ) D glucose s D glucose s

Now we can perform the same operations on the enthalpies of solution in order to obtain,
( ) ( ) ( )
O O
Eq.1 Eq.2 Eq.3
s s s
H H H H = +
It is important to note that we use the reversed sign on Eq. 2 because we need to use the reverse reaction. Always keep this in mind when
doing problems like this; otherwise it can become confusing!
( ) ( ) ( )
( )
1
1
Eq.1 Eq.2 Eq.3
10.72 4.68 1.16 kJ mol
(mutarotation) 4.88 kJ mol
s s s
H H H H
H
H
= +
=
=

2-79
2.30. Use the data in Appendix D to calculate H for the hydrolysis of urea into carbon dioxide and ammonia at 25 C.

Solution:
Given: Appendix D, 25 C T =
Required: H
Remember that all values given in Appendix D were taken at the standard temperature and pressure of 25.00 C and 1 bar pressure. The
reaction for the hydrolysis of urea is as follows:
2 2 2 2 3
(1) H NCONH (s) H O(l) CO (g) 2NH (g) + +
Let us now list the reactions needed in order to generate Eq.1.
2 2
1
1
(2) H (g) O (g) H2O(l)
2
285.830 kJ mol from Appendix D
f
H

+
=

graphite 2 2
1
(3) C (s) O (g) CO (aq)
413.26 kJ mol from Appendix D
f
H

+
=

2 2 3
1
3 1
(4) H (g) N (g) NH (aq)
2 2
80.29 kJ mol fromAppendix D
f
H

+
=

3 2 2 2 2
1
(5) 2NH (g) CO (g) H NCONH (s) H O(l)
333.1 kJ mol
f
H

+ +
=

In order to obtain reaction (1), we need to multiply both Eqs. 2 and 5 by -1 then add them to Eq. 3 and Eq. 4 multiplied by 2.
2-80
2 2 2
graphite 2 2
2 2 3
2 2 2 3 2
1
(2) H O(l) H (g) O (g)
2
(3) C (s) O (g) CO (aq)
3 1
2 (4) 2 H (g) N (g) NH (aq)
2 2
(5) H NCONH (s) H O(l) 2NH (g) CO (g)
+
+ +
(
+ +
(

+ +

Making the same operations on the enthalpies of formation we obtain,
(Eq.2) (Eq.3) 2 (Eq.4) (Eq.5)
f f f f
H H H H H = + +
| |
1
1
( 285.83) ( 413.26) (2 80.29) ( 333.1) kJ mol
45.09 kJ mol
H
H
= + +
=

2-81
2.31. Here is a problem with a chemical engineering flavor: Ethanol is oxidized to acetic acid in a catalyst chamber at 25 C. Calculate the
rate at which heat will have to be removed (in J h
1
) from the chamber in order to maintain the reaction chamber at 25 C, if the feed
rate is 45.00 kg h
1
of ethanol and the conversion rate is 42 mole % of ethanol. Excess oxygen is assumed to be available.

Solution:
Given:
1
feed conversion
25 C, 45.00 kg h , 42 mole % of ethanol T v v = = =
Required:
heat
v
From Appendix D, we are given the enthalpies of formation for both ethanol and acetic acid.
1
1
1
277.6 kJ mol ethanol(l)
484.3 kJ mol acetic acid(l)
285.83 kJ mol water(l)
f
f
f
H
H
H
=
=
=

We can then determine the standard enthalpy change for the reaction:
2 5 2 3 2
C H OH(l) O (g) CH COOH(l) H O(l) + +
Note that we also need to use the enthalpy of formation for water which yields;
| |
( )
2
1
1
1
(acetic acid) (H O) (ethanol)
( 484.3) ( 285.83) ( 277.6) kJ mol
484.3 285.83 277.6 kJ mol
492.53 kJ mol
f f f
H H H H
H
H
H
= +
= +
= +
=

Since the ethanol is fed at a rate of 45.00 kg h
-1
, and only 42% of ethanol is converted, the actual heat evolved during the reaction per hour
is defined by (molar mass ethanol is approximately 46.069 g mol
-1
):
2-82
feed
heat conversion
45.00 kg
v
v v H
M
= =
1
h
0.046 069 kg
1
mol
1
(0.42) 492.53 kJ mol

( )
1
heat
202 062.49 kJ h v

=

This means that the heat will have to be removed at a rate of 202 MJ h
-1
.
2-83
2.32. a. An ice cube at 0 C weighing 100.0 g is dropped into 1 kg of water at 20 C. Does all of the ice melt? If not, how much of it
remains? What is the final temperature? The latent heat of fusion of ice at 0 C is 6.025 kJ mol
1
, and the molar heat capacity of
water, C
P,m
, is 75.3 J K
1
mol
1
.
b. Perform the same calculations with 10 ice cubes of the same size dropped into the water. (See Problem 3.33 of Chapter 3 for the
calculation of the corresponding entropy changes.)

Solution:
Given:
ice water water
0 C, 100.0 g, 1000 g, 20 C T m m T = = = =

1 1 1
0 C, 6.025 kJ mol , 75.3 J K mol
fus P
T H C = = =
Required: see above
a. Assume that all of the ice melts. The process would then absorb;
ice
ice
100.0 g
fus
m H
M
=
( )
1
6.025 kJ mol
( )
18.02 g
1
mol
33.435 072 214 kJ absorbed q = =

Let the final temperature be C T , then we can use the following expression to solve for t.
P
q mC T =
However, since we are determining the value for ten ice cubes, we will use the following:
2-84
( )
water
water water
1000 g
33 435.072 214 J
P
P
P i
q mC T
q m C T
q m C T T
=
=
=
=
( )
1
75.3 J K
1
mol
( ) 20 K T
18.02g
1
mol
33 435.072 214 J
( ) ( )
( )
18.02
1000 75.3 J
( )
( )
( )
20
20 8.001 328 038
20 8.001 328 038
11.998 671 96 12 C
T
T
T
T T
=
=
=
= =

Since this value is not below 0 C, it means that all of the ice does indeed melt. The final temperature is 12 C.
b. It is obvious that not all of the ice will melt. (If we assumed that it all melted, we would find that the final temperature would be below
0 C.) The final temperature of the water is now 0 C, and if we suppose that x g of the ice melts, we can determine how much ice will
remain solid in the water.
( )
ice water
water
ice
ice
(molecular weight will cancel on both sides)
1000 g 75.3 J
fus P
P
fus
m H m C t
m C t
m
H
m
=
=
=
1
K
1
mol
( )
20 K
( )
6 025 J
1
mol
ice
ice
249.958 506 2 g
250 g
10 100g 250 750 grams of ice will remain solid.
m
m
=
=
=

2-85
2.33. From the data in Table 2.1 and Appendix D, calculate the enthalpy change in the reaction
C(graphite) +O
2
(g) CO
2
(g)
at 1000 K.

Solution:
Given: Appendix D, Table 2.1, T=1000 K
Required: H for the reaction
All of the values given in Appendix D were taken under the standard conditions of 25 degrees Celsius and 1 bar pressure. For this
particular reaction we can see that the enthalpy of formation for carbon dioxide is given by,
1
393.51 kJ mol
f
H

=
According to the values given in Table 2.1 and using Eq. 2.49 we have the following;
2
, p m
C d eT fT
= + +
| |
2 2
1 1
(CO ) (O ) (C)
44.22 (29.96 16.86)
44.22 29.96 16.86
2.60 J K mol
d d d
d d d d
d
d
d

=
= +
= +
=
=

( )
( )
2 2
3 2 1
3 2 1
(CO ) (O ) (C)
8.79 4.18 4.77 10 J K mol
0.16 10 J K mol
e e e
e e e e
e
e

=
= +
= + (

=

2-86
( )
( )
2 2
5 1
5 1
(CO ) (O ) (C)
8.62 1.67 8.54 10 J K mol
1.59 10 J K mol
f f f
f f f f
f
f
=
= +
= (

=

Putting all of these values into Eq. 2.52 we can determine the enthalpy change at 1000 K.
( ) ( )
2 2
2 1 2 1 2 1
2 1
3 2 2
2
5
1
2
1 1 1
( ) ( )
2
1
( ) 393 510 2.6(1000 298.15) ( 0.16 10 )(1000 298.15 )
2
1 1
(1.59 10 )
1000 298.15
( ) 395 781.9871 J mol
(1000 K)
m m
m
m
m
H T H T d T T e T T f
T T
H T
H T
H
| |
= + + +
|
\ .
= +
| |
+
|
\ .
=
1
395.78 kJ mol
=

2-87
3.34. From the bond strengths in Table 2.2, estimate the enthalpy of formation of gaseous propane, C
3
H
8
, using the following additional
data:

f
H/kJ mol
1

C(graphite) C(g) 716.7
H
2
(g) 2H(g) 436.0

Solution:
Given: Table 2.2, see above
Required:
f
H
Propane has the molecular formula C
3
H
8
which means that it contains two carbon-carbon bonds and eight carbon-hydrogen bonds. We can
therefore determine the heat of ionization by using the following;
( )( )
( ) ( )
atomization
1
atomization
1
atomization
#bonds of type n bond enthalpy of type n
2 348 8 413 kJ mol
4000 kJ mol
q
q
q
=
= + (

=

Now we need to determine the correct and balanced equation for the reaction which forms propane. After this, we must also determine the
reactions for the formation of each species involved.
2-88
3 8
1
graphite
1
graphite
1
2
(1) 3C(g) 8H(g) C H (g)
4000 kJ mol
(2) C C(g)
given that 716.7 kJ mol therefore,
(3) 3C 3C(g)
2150.1 kJ mol
(4) H (g) 2H(g)
given that 436.0 kJ mol
f
f
f
f
H
H
H
H
+
=
=
1
2
1
therefore,
(5) 4H (g) 8H(g)
1744 kJ mol
f
H
=

When we add equations 1, 3 and 5, we obtain the desired reaction:
(1) 3C(g) 8H(g) +
3 8
C H (g)
graphite
(3) 3C 3C(g)
2
(5) 4H (g) 8H(g)
graphite 2 3 8
3C 4H (g) C H (g) +

Doing the same thing for the enthalpies of formation we obtain,
2-89
( )
( )
1
1
(Eq.1) (Eq.3) (Eq.5)
4000 2150.1 1744 kJ mol
graphite 105.9 kJ mol
f f
f f f
H H H
H H H H
H
H
=
= + +
= + +
=

The agreement with experiment,
1
103.8 kJ mol
is relatively good.

2-90
2.35. A sample of sucrose, C
12
H
22
O
11
weighing 0.1328 g, was burned to completion in a bomb calorimeter at 25 C, and the heat evolved
was measured to be 2186.0 J .
a. Calculate
c
U
m
and
c
H
m
for the combustion of sucrose.
b. Use data in Appendix D to calculate
f
H
m
for the formation of sucrose.

Solution:
Given:
sucrose ,
0.1328 g, 25 C, heat 2186.0 J
V m
m T q = = = = , Appendix D
Required: , ,
c m c m f m
U H H
a. Remember that when using a bomb calorimeter, we are working under constant volume. With that said, the heat evolved per gram
will be;
,
,
1
,
2186.0 J
0.1328 g
16 460.843 37 J g
V
V m
V m
V m
q
q
m
q
q

=
=
=

We can now use this information in order to determine the change in internal energy which is given by;
, c V m
U q =
when working under constant volume conditions. Using the molar mass for sucrose (approximately 342.3 g mol
-1
) we can determine the
change in internal energy per mole of substance combusted.
, sucrose
1
( 16 460.843 37 J g
c m V m
c m
U q M
U

=
= )(342.3 g
1
1
mol )
5 635 kJ mol
c m
U
=

The balanced reaction for the combustion of sucrose is given by,
2-91
12 22 11 2 2 2
C H O (s) 12O (g) 12CO (g) 11H O(l) + +
The change in the number of moles for the gaseous species is therefore
products reactants
n n n =

12 12
0
n
n
=
=

According to Eq. 2.41 we can then say that;
1
( )
( )
since 0 then ( ) 0
5 635 kJ mol
H U PV
nRT PV
nRT PV
H U
H

= +
=
= =
=
=

b. For the formation of sucrose, we can use the same reaction given above for combustion but in reverse. Using Hess Law which
states:
f m f m f m
H H H =

We can rearrange and make the appropriate substitutions using information given in Appendix D to obtain,
( ) ( )
2 2
1
1
12 (CO ,g) 11 (H O,l) (sucrose)
(12 393.51) 11 285.83 5 635 kJ mol
2 231 kJ mol
f m f m f m
f m f m f m f m
f m
f m
H H H
H H H H
H
H
=
= +
= + (

=

2-92
2.36. The value of H for the reaction
2 2
1
CO(g) + O (g) CO (g)
2

is 282.97 kJ mol
1
at 298 K. Calculate U for the reaction.

Solution:
Given:
1
282.97 kJ mol , 298K H T = =
Required: U
Since we have been given the standard change in enthalpy, we can simply use Eq. 2.41 and rearrange in order to determine the standard
change in internal energy. First, we must determine the change in moles for the gaseous species.
2 2
1
1CO (1CO O )
2
1 1.5
1
2
n n n
n
n
n
=
= +
=
=

According to Eq. 2.41:
O
1 1
( )
( ) and therefore
( 282970 J mol ) ( 0.5 8.3145 J K
H U PV
nRT PV
H U nRT
U H nRT
U

= +
=
= +
=
=
1
mol 298.15 K
1
1
)
281 730.5159 J mol
281.73 kJ mol
U
U
=
=

2-93
2.37. One mole of an ideal gas initially at 10.00 bar and 298.0 K is allowed to expand against a constant external pressure of 2.000 bar to
a final pressure of 2.000 bar. During this process, the temperature of the gas falls to 253.2 K. We wish to construct a reversible path
connecting these initial and final steps as a combination of a reversible isothermal expansion followed by a reversible adiabatic
expansion. To what volume should we allow the gas to expand isothermally so that subsequent adiabatic expansion is guaranteed to
take the gas to the final state? Assume that
,
3
2
V m
C R = .

Solution:

Given: Ideal Gas: 10.00 bar, 298.0 K, 2.00 bar, 2.00 bar, 253.2 K
i i ext f f
P T P P T = = = = =

Required:
i
V

It should be noted that we are required to find the intersection of the isotherm that passes through the initial state and the adiabat that passes
through the final state. We will call this point ( ) ,
i i
P V and the temperature of the isotherm will be
i
T .

Recall that for adiabatic processes we use Eq. 290 which states that:
1
f
i
i f
T
V
T V

| |
= |
|
\ .

We must first determine the value for in order to solve the above expression. Remember that it can be found using Eq. 2.88 and knowing
that for an Ideal Gas,

2-94
,
,
, ,
,
,
3
and therefore,
2
3
2
3
5
2
2
3
2
P m
V m
P m V m
V m
P m
C
C
C C R
C R
C R R
R R
R
R
=
=
=
= +
| |
+
|
\ .
= =
| |
|
\ .
3
2
R
5
2
=
2
3

5
3
2
1
3
=
=

The final volume can be solved for using the Ideal Gas Law.

3
0.08315 dm bar
f
f
f
f
PV nRT
RT
V
P
V
=
=
=
1
K
( )
1
mol 253.2 K
( )
2.0 bar
3
10.526 79 dm
f
V =

Now we are able to rearrange Eq. 2.90 in order to solve for the initial volume.
2-95
( )
1
2
3
3
2
3
2
3
253.2 K
10.52 679 dm
f
i
i f
f f
i i
i f i f
f
i f
i
i
T
V
T V
T T
V V
T V T V
T
V V
T
V

| |
=
|
|
\ .
| |
| |
= =
|
|
|
\ .
\ .
| |
=
|
\ .
=
298.0 K
3
2
3
3
8.244 553 018 dm
8.245 dm
i
i
V
V
| |
|
\ .
=
=


2-96
2.38. Two moles of oxygen gas, which can be regarded as ideal with C
P
=29.4 J K
1
mol
1
(independent of temperature), are maintained
at 273 K in a volume of 11.35 dm
3
.
a. What is the pressure of the gas?
b. What is PV?
c. What is C
V
?

Solution:
Given: Oxygen Gas:
1 1 3
29.4 J K mol , 273 K, 11.35 dm
P
C T V = = =
Required:
2
O
, ,
V
P PV C
a. One mole of oxygen gas in a volume of 22.7 dm
3
and at 273 K exerts a pressure of 1 bar. If we make the necessary adjustments to
account for the difference in volume (one half the volume means twice the pressure) the gas would exert a 2 bar pressure. We must
now account for the number of moles of gas (of which there are two) which would bring the pressure up to 4 bar.
2
O
4 bar P =
b. Now we can determine the amount of PV work done in addition to the heat capacity under constant volume.
( )( )
3
3
3
3
4 bar 11.35 dm
45.4 bar dm
since 1 bar dm 100 J
45.4 bar dm 4540 J 4.540 kJ
4.540 kJ
PV
PV
PV
=
=
=
= =
=

c. For an ideal gas we know that,
P V
T P
U V
C C P
V T
( | | | |
= +
| | (

\ . \ .

(Eq. 2.117)
Since, for an ideal gas 0
T
U
V
| |
=
|
\ .
, this can be simplified to Eq. 2.118:
2-97
P V
P
V
C C P
T
| |
=
|
\ .

For 1 mole of an ideal gas, we already know that
m
PV RT = and therefore,
P
V R
T P
| |
=
|
\ .

which produces the following expression:
, , P m V m
C C R = (Eq. 2.119)
And rearranging for C
V
we get,
, ,
, ,
1 1 1 1
,
1 1
,
1 1
,
29.4 J K mol 8.3145 J K mol
21.0855 J K mol
21.1 J K mol
P m V m
V m P m
V m
V m
V m
C C R
C C R
C
C
C
=
=
=
=
=

2-98
2.39. Suppose that the gas in Problem 2.38 is heated reversibly to 373 K at constant volume:
a. How much work is done on the system?
b. What is the increase in internal energy, U?
c. How much heat was added to the system?
d. What is the final pressure?
e. What is the final value of PV?
f. What is the increase in enthalpy, H?

Solution:
Given: Oxygen (Problem 2.38): 273 K, 373 K
i f
T T = =
Required: , , , , ,
m added f m
w U q P PV H
a. A very important process is the compression of an ideal gas (such as the oxygen in Problem 2.38) under constant volume. This process
is illustrated in Figure 2.6b.
It is important to remember that for an ideal gas at constant volume,
( )
2
1
, ,
, , 2 1
T
V m V m
T
V m V m
q C dT
q C T T
=
=

This also means that for an ideal gas,
, 2 1
, 2 1
( )
( )
m V m
m P m
U C T T
H C T T
=
=

The work done on the system in a reversible compression of one mole of gas is given by the following,
,2
,1
m
m
V
rev
V
w PdV =
(Eq. 2.70)
Since the pressure is varying, we must express this in terms of V
m
by using the Ideal Gas Law for a single mole.
2-99
,2
,1
,2
,1
,2
,1
rev
rev
rev
ln( )
m
m
m
m
m
m
V
V
m
V
V
m
V
V
w PdV
PV RT
RT
w dV
V
w RT V
=
=
=
=

,2
rev
,1
ln
m
m
V
w RT
V
| |
=
|
|
\ .

This can also be written as;
,1
rev
,2
ln
m
m
V
w RT
V
| |
=
|
|
\ .
which then gives,
1
rev
(8.3145 J K w

=
1
mol )(273 K
1
) ln
1
| |
|
\ .
rev
0 w =

b. Now we can use the first two expressions given above in order to determine the change in internal energy and change in enthalpy.
, 2 1
( )
(2 mol
m V m
m
U nC T T
U
=
=
1
)21.1 J K
1
mol
( ) 373 273 K
4220 J
4.22 kJ
m
m
U
U
=
=

c. Recall that at constant volume, the change in internal energy is equivalent to the amount of heat added to the system and therefore,
added
added
4.22 kJ
m
q U
q
=
=

2-100
d. Knowing that
0 2 2
1 0 1
lim ( )
lim ( )
P
P
PV T
T PV
= from Chapter 1 (Eq. 1.22), we can solve for the final pressure.
1 2
2
1
2
4 bar 373.15 K
PT
P
T
P
=
=
273.15 K
2
5.464 396 852 bar P =

Since 1 bar=10
5
Pa then we can say that,
5.464 396 852 bar
f
P =
5 1
10 Pa bar
( )

546 439.6852 Pa
5.46 kPa
f
f
P
P
=
=

2-101
e.
( )
2 2
3
3
5 5
(5.464 396 852 bar) 11.35 dm
62.020 904 27 bar dm
1 bar 10 Pa and 1 atm 1.01325 10 Pa
62.020 904 27bar
PV PV
PV
PV
PV
=
=
=
= =
=
( )
3 5
dm 10 Pa
1
bar
( )
5
1 atm
1.01325 10 Pa
3
3
3
61.209 873 45 atmdm
and since, 1 atmdm 101.325 J then,
61.209 873 45 atmdm
PV
PV
| |
|
\ .
=
=
=
3
101.325 J
1 atmdm
6202.090 427 J
6.20 kJ
PV
PV
| |
|
\ .
=
=

f. The change in enthalpy can now be determined.
, 2 1
( )
(2 mol
m P m
m
H nC T T
H
=
=
1
)(29.4 J K
1
mol )(373.15 273.15) K
5880 J
5.88 kJ
m
m
H
H
=
=

Alternately, we can determine the enthalpy change using Eq. 2.41 which yields approximately the same answer.
2-102
2.40. Suppose that the gas in Problem 2.38 is heated reversibly to 373 K at constant pressure.
a. What is the final volume?
b. How much work is done on the system?
c. How much heat is supplied to the system?
d. What is the increase in enthalpy?
e. What is the increase in internal energy?

Solution:
Given: Oxygen (problem 2.38): 273 K, 373 K
i f
T T = =
Required:
rev , , ,
, (on system), , ,
f P m P m P m
V w q H U
a. The pressure-volume relationship for the reversible compression of an ideal gas at constant pressure can be found in Figure 2.6a.
Remember from Chapter 1 that we have,
0 2 2
1 0 1
2 2
1 1
1 2
2
1
3
lim ( )
lim ( )
11.35 dm 373.15 K
P
P
f
PV T
T PV
T V
T V
VT
V
T
V
=
=
=
=
273.15 K
3
15.5 dm
f
V =

b. The work done on the system for one mole can be defined by,
,2
,1
rev 1 1 ,2 ,1
rev 1 ,1 ,2
( )
( )
m
m
V
m m
V
m m
w PdV P V V
w P V V
= =
=

This expression is true whether the gas we are working with is ideal or not. If we use the Ideal Gas Law, we can get,
2-103
1 2
rev 1
1 1
RT RT
w P
P P
| |
=
|
\ .

Which simplifies to the following;
rev 1 2
( ) w R T T =

For two moles of oxygen:
rev
(2 mol w =
1
)(8.3145 J K
1
mol
)(273.15 373.15) K
rev
1662.9 J w =

However, since the work is being done ON the system, the value will be positive.
rev
1.66 kJ w =
c. The heat absorbed by the system during such as process is given by;
2
1
, ,
T
P m P m
T
q C dT =

(Eq. 2.57)
Now, since the pressure is constant, the heat capacity will be independent of temperature and this integral will simplify to:
( )
( )
, , 2 1
, , 2 1
,
For two moles of oxygen:
(2 mol
P m P m
P m P m
P m
q C T T
q nC T T
q
=
=
=
1
) 29.4 J K
1
mol
( )
(373.15 273.15) K
,
,
5880 J
5.88 kJ
P m
P m
q
q
=
=

2-104
d. According to Eq. 2.59, the change in enthalpy is equal to the amount of heat supplied to the system when the work is done under
constant pressure.
, , 2 1
, ,
,
( )
5.88 kJ
P m P m
P m P m
P m
H C T T
H q
H
=
=
=

e. We can now use Eq. 2.41 and rearrange it in order to solve for the change in internal energy.
( )
, ,
, ,
, ,
,
,
( )
5.88 1.66 kJ
4.22 kJ
P m P m
P m P m rev
P m P m rev
P m
P m
H U PV
H U w
U H w
U
U
= +
= +
=
=
=

2-105
2.41. Suppose that the gas in Problem 2.38 is reversibly compressed to half its volume at constant temperature (273 K).
a. What is the change in U?
b. What is the final pressure?
c. How much work is done on the system?
d. How much heat flows out of the system?
e. What is the change in H?

Solution:
Given: Oxygen (Problem 2.38): 273 K, 373 K
i f
T T = =
Required:
rev outflow
, , , ,
m f m
U P w q H
a. Another process of great importance is the compression of an ideal gas along an isotherm. This means that the process is occurring
at constant temperature. An illustration of such a process is given in Figure 2.6c. We should note that for an ideal gas undergoing
compression at constant temperature,
0 and
0
m
m
H
U
=
=

b. The final pressure can be found using
1 1 2 2
PV PV = and rearranging to get,
1 1
2
2
3
(4 bar)(11.35 dm
f
PV
P
V
P
=
=
3
)
5.675 dm
8 bar
f
P =

c. The work done on the system in a reversible compression is given by,
,2
,1
rev
m
m
V
V
w PdV =

2-106
Since the pressure is varying, we must express this equation in terms of V
m
by making use of the Ideal Gas Law.
,2
,1
rev
m
m
V
V
m
nRT
w dV
V
=

,2
,1
rev
,2
rev
,1
,1
rev
,2
rev
ln( )
ln
ln
2 mol
m
m
V
V
m
m
m
m
w nRT V
V
w nRT
V
V
w nRT
V
w
=
| |
=
|
|
\ .
| |
=
|
|
\ .
=
( )
1
8.3145 J K
1
mol
( )
273 K
( )
rev
rev
11.35
ln
5.675
3146.69 J
3.15 kJ
w
w
| |
|
\ .
=
=

d. The amount of heat flowing out of the system is equal in magnitude but opposite in sign to the amount of work done ON the system.
This is true because this is the only way to keep the temperature of the system constant.
rev outflow
outflow
3.15 kJ
w q
q
=
=

e. Since there is no temperature change, 0 H =
2-107
2.42. With the temperature maintained at 0 C, 2 mol of an ideal gas are allowed to expand against a piston that supports 2 bar pressure.
The initial pressure of the gas is 10 bar and the final pressure 2 bar.
a. How much energy is transferred to the surroundings during the expansion?
b. What is the change in the internal energy and the enthalpy of the gas?
c. How much heat has been absorbed by the gas?

Solution:
Given: Ideal Gas:
piston
0 C, 2 mol, 2.0 bar, 10 bar, 2 bar
i f
T n P P P = = = = =
Required: (by gas), , , (absorbed) w U H q
a. We are given that we are making changes to a system under constant temperature. It is first important to determine the change in
volume because we know that there is only PV work involved.
2 mol
i
i
i
PV nRT
nRT
V
P
V
=
=
=
( )
0.083 144 72 bar
3 1
dm K
1
mol
( )
273.15 K
( )
10 bar
3
4.54 dm
i
V =

Now we can find the final volume and hence, the volume change.
2-108
10 bar
i i f f
i i
f
f
f
PV P V
PV
V
P
V
=
=
=
( )( )
3
4.54 dm
2 bar
( )
3
3
3
22.71 dm
22.70 4.54 dm
18.16 dm
f
f i
V
V V V
V
V
=
=
=
=

Now the work done by the gas is given by pressure multiplied by the change in volume;
w P V =
( )( )
3
3
2 bar 18.16 dm
36.32 bar dm
36.32 bar
w
w
w
=
=
=
( )
3 5
dm 10 Pa
1
bar
( )
5
1 atm
1.01325 10 Pa
3
3
3
35.845 atm dm
Since 1 atm dm 101.325 J then,
35.845 atm dm
w
w
| |
|
\ .
=
=
=
( )
3
101.325 J
1 atm dm
3632 J w
| |
|
|
\ .
=

The amount of work done by the gas will be equal to the amount of heat transferred to the surroundings because the temperature of the
system needs to remain constant.

2-109
b. Remember that at constant temperature,
0
0
m
m
U
H
=
=

c. The amount of heat absorbed by the gas will be equal to the amount of work done.
absorbed
3632 J q =

2-110
2.43. Suppose that the gas in Problem 2.42 is allowed to expand reversibly and isothermally from the initial pressure of 10 bar to the final
pressure of 2 bar.
a. How much work is done by the gas?
b. What are U and H?
c. How much heat is absorbed by the gas?
Solution:
Given: (problem 2.42): 10 bar, 2 bar
i f
P P = =
Required:
absorbed
(by gas), , , w U H q
a. We are again working under conditions of constant temperature so we can solve this problem in the same way that we have done
before. We can determine the amount of work done by the gas by using the volume change found in the previous problem.
3
3
rev
rev
22.71 dm
4.54 dm
ln
2 mol
f
i
f
i
V
V
V
w nRT
V
w
=
=
=
=
( )
1
8.3145 J K
1
mol
( )
273.15 K
( )
rev
rev
22.71
ln
4.54
7312.407 687 J
7.31 kJ
w
w
| |
|
\ .
=
=

b. Remember we are still working under constant temperature which means that,
0
0
m
m
U
H
=
=

c. The amount of heat absorbed by the gas will be equal to the amount of work done in order to keep the temperature constant.
7.31 kJ q =
2-111
2.44. A sample of hydrogen gas, which may be assumed to be ideal, is initially at 3.0 bar pressure and a temperature of 25.0 C, and has a
volume of 1.5 dm
3
. It is expanded reversibly and adiabatically until the volume is 5.0 dm
3
. The heat capacity C
P
of H
2
is 28.80 J K
1

mol
1
and may be assumed to be independent of temperature.
a. Calculate the final pressure and temperature after the expansion.
b. Calculate U and H for the process.

Solution:
Given: Hydrogen gas:
3 3
3.0 bar, 25 C, 1.5 dm, 5.0 dm,
i i i f
P T V V = = = =

1 1
28.80 J K mol
p
C =
Required: , , ,
f f
P T U H
Another process to consider is the compression or expansion of an ideal gas contained in a vessel whose walls are perfectly insulated. This
means that heat cannot pass through them. Such processes are called adiabatic. The pressure-volume relationship for this type of process is
given in Figure 2.6d.
a. Since the work is performed on the gas in order to compress it and no heat can leave the system, the final temperature must be
higher than the initial temperature.
Using the value of C
P
, we can determine C
V
according to Eq. 2.119,
, ,
, ,
1 1 1 1
,
1 1
,
28.80 J K mol 8.3145 J K mol
20.4855 J K mol
P m V m
V m P m
V m
V m
C C R
C C R
C
C

=
=
=
=

Note that the ratio of C
P
to C
V
is often written as,
,
,
P m
V m
C
C
=
We can now derive a version of Boyles Law for this adiabatic process.
2-112
i i f f
PV P V

=
We can use this first to determine the final pressure for the system.
i i
f
f
PV
P
V
=

( )
3
1.5 dm
3.0 bar
i
f i
f
f
V
P P
V
P
| |
=
|
|
\ .
=
3
5 dm
1 1
,
,
28.80 J K mol
P m
V m
C
C

| |
|
|
\ .
= =
1 1
20.4 855 J K mol

( )
3
1.405 872 446
1.5 dm
3.0 bar
f
P
=
=
3
5 dm
1.405 872446
0.552 103 415
0.552 bar
f
f
P
P
| |
|
|
\ .
=
=

Using Eq. 2.90 it is possible to determine the final temperature.
1
2 1
1 2
T V
T V

| |
=
|
\ .

Now rearrange to get,
2-113
( )
1
1
2 1
2
3
2
1.5 dm
298.15 K
V
T T
V
T

| |
=
|
\ .
=
3
5 dm
( )
1
3
2
1.405 87
1.5 dm
298.15 K T
| |
|
|
\ .
=
=
3
5 dm
0.405 872 446
2
2
182.962 406 6 K
183.0 K
T
T
| |
|
|
\ .
=
=

b. Both and U H remain unchanged as we move alone the T
1
isothermal and the same is true for the T
2
isothermal. The changes in U
and H can be found using Eq. 2.29 and Eq. 2.31 respectively.
( )
, 2 1 m V m
U C T T =
1
20.49 J K
m
U

=
( )
( )
1
mol 182.9 624 066 298.15 K
1
2360.193 789 J mol
m
U

=

Now we need to determine the number of moles of hydrogen using the Ideal Gas Law.
2
2
H
H
3.0 bar
PV nRT
PV
n
RT
n
=
=
=
( )
3
1.5 dm
( )
0.083 144 72 bar
3
dm
1
K
( )
1
mol 298.15 K
( )
2
H
0.181 527 75 mol n =

2-114
0.181 527 75 mol
m
U =
( )
1
2360.193 789 J mol
( )
428.440 668 4
428.4 J
m
m
U
U
=
=

Likewise, for the change in enthalpy we get,
( )
, 2 1
1
28.80 J K
m P m
m
H C T T
H

=
=
( )
1
mol 182.962 406 6 298.15 K
( )
1
3317.402 69 J mol
0.181 527 75 mol
m
m
H
H
=
=
( )
1
3317.402 69 J mol
( )
602.200 646 1 J
602.2 J
m
m
H
H
=
=


2-115
2.45. Initially 0.1 mol of methane is at 1 bar pressure and 80 C. The gas behaves ideally and the value of C
P
/C
V
is 1.31. The gas is
allowed to expand reversibly and adiabatically to a pressure of 0.1 bar.
a. What are the initial and final volumes of the gas?
b. What is the final temperature?
c. Calculate U and H for the process.

Solution:
Given: Ideal Gas:
methane
0.1 mol, 1 bar, 80 C, 1.31, 0.1 bar
p
i f
v
C
n P T P
C
= = = = =
Required: , , , ,
i f f
V V T U H
Another process to consider is the compression or expansion of an ideal gas contained in a vessel whose walls are perfectly insulated. This
means that heat cannot pass through them. These processes are called adiabatic. The pressure-volume relationship for this type of process
is given in Figure 2.6d.
We may start by finding the initial volume by using the Ideal Gas Law:
0.1 mol
i i
i
i
i
PV nRT
nRT
V
P
V
=
=
=
( )
0.083 144 72 bar
3 1
dm K
1
mol
( )
353.15 K
( )
1 bar
3
3
2.936 255 787 dm
2.936 dm
i
i
V
V
=
=

We can now make use of Eq. 2.92 which states that,
f f
i i
P V
P V
| |
=
|
\ .

2-116
This can easily be rearranged in order to solve for the final volume since we are given both the initial and final pressures in addition to .
1
i
f i
f
P
V V
P
| |
= |
|
\ .

( )
3
1 bar
2.936 255 787 dm
f
V =
0.1 bar
( )
1
,
,
3
1.31
1 1
0.763 358 778
1.31
1 bar
2.936 dm
P m
V m
f
C
C
V
| |
|
\ .
= =
= =
=
0.1 bar
0.763 358 778
3
3
17.027 569 61 dm
17.026 dm
f
f
V
V
| |
|
\ .
=
=

Using Eq. 2.91 it is possible to solve for the final temperature of the system,
f f f
i i i
T P V
T PV
= (Eq. 2.91)
2-117
( ) 353.15 K 0.1 bar
i f f
f
i i
f
T P V
T
PV
T
=
=
( )
3
17.027 569 61 dm
( )
1 bar
( )
3
2.936 255 787 dm
( )
204.794 334 6 K
204.8 K
f
f
T
T
=
=

Since we are given both C
P,m
and C
V,m
(in ratio form) for the system, and and U H are defined in the following manner,
( )
( )
V f i
P f i
U C T T
H C T T
=
=

We can use these equations (Eq.2.95 and 2.96) in order to solve for the final wanted variables. However, since we are only given then ratio,
we need to use Eq. 2.119 (to determine each unique value) which states that,
, , P m V m
C C R = and therefore,
1 1
, ,
,
,
8.3145 J K mol
1.31
P m V m
P m
V m
C C
C
C

=
=

2-118
( )
( )
,
,
, , ,
1 1
, ,
1 1
1 1
,
1 1
, , ,
,
1 0.31
therefore, 0.31
since 8.3145 J K mol
then we get:
8.3145 J K mol
26.820 967 74 J K mol
0.31
0.31 35.135 467 74 J K mol
P m
V m
P m V m V m
P m V m
V m
P m V m V m
m V m f i
C
C
C C C
C C
C
C C C
U C T T

=
=
=
= =
= + =
=
1
26.820 967 74 J K
m
U

=
( )
1
mol 204.794 334 6 K
353.15 K
( )
1
3979.042 516 J mol
0.1 mol
m
m
U
U n U
U
=
=
=
( )
1
3979.042 516 J mol
( )
( )
( )
,
1 1
397.904 251 6 J
397.9 J
35.135 467 74 J K mol 204.794 334 6 K
m P m f i
m
U
U
H C T T
H

=
=
=
= 353.15 K
( )
1
5212.545 696 J mol
0.1 mol
m
m
H
H n H
H
=
=
=
( )
1
5212.545 696 J mol
( )
521.2 545 696 J
521.15 J
H
H
=
=

2-119
2.46. A gas behaves ideally and its C
V
is given by
C
V
/J K
1
mol
1
=21.52 +8.2 10
3
T/K
a. What is C
P,m
as a function of T?
b. A sample of this gas is initially at T
1
=300 K, P
1
=10 bar, and V
1
=1 dm
3
. It is allowed to expand until P
2
=1 bar and V
2
=10
dm
3
. What are U and H for this process? Could the process be carried out adiabatically?

Solution:
Given: Ideal Gas:
3 3
1 1 1
21.52 8.2 10 / K, 300 K, 10 bar, 1 dm
V
C T T P V = + = = =

3
2 2
1 bar , 10 dm P V = =
Required:
,
, ,
P m
C U H
a. J ust as in Problem 2.45, we can use Eq. 2.119 in order to determine C
P,m
given the value (or the equation for the value) of C
V,m
.
{ } ( )
{ }
, ,
1 1
, ,
3 1 1
,
1 1 3
,
8.3145 J K mol
21.52 8.2 10 / K 8.3145 J K mol
29.8345 J K mol 8.2 10 / K
P m V m
P m V m
P m
P m
C C R
C C
C T
C T

=
=
+ =
= +

Recall that both the increase in internal energy and in enthalpy are given by Eqs. 2.95 and 2.96;
( )
( )
,
,
m V m f i
m P m f i
U C T T
H C T T
=
=

However, we first need to determine the final temperature by using Eq. 2.91 and the information given above.
2-120
( ) 300 K 1 bar
f f f
i i i
i f f
f
i i
f
T P V
T PV
T P V
T
PV
T
=
=
=
( )
3
10 dm
( )
10 bar
( )
3
1 dm
( )
300 K
f
T =

b. Since there is no change in temperature, then we find that:
( )
( )
,
,
,
,
(0)
0
therefore, 0
(0)
0
therefore, 0
m V m f i
m V m
m
m P m f i
m P m
m
U C T T
U C
U
U
H C T T
H C
H
H
=
=
=
=
=
=
=
=

Recall that adiabatic processes take place in vessels whose walls are perfectly insulated. This means that no heat can be transferred to or
from the control volume. We indeed could perform this process under adiabatic conditions by allowing free expansion which means that
0 w q = = .
2-121
2.47. Prove that for an ideal gas two reversible adiabatic curves on a P-V diagram cannot intersect.

Solution:
The diagram given below displays two adiabatic pathways for an ideal gas. These adiabatic pathways are intersected by two isotherms
corresponding to the temperatures T
h
and T
c
. Take careful note to compare this diagram with Figure 3.2a.

To show mathematically that for an ideal gas, two reversible adiabatic curves on a P-V diagram cannot intersect, we will use Eq. 2.90 which
gives,
1
3 4
1 2
as well as
f
i
i f
h h
c c
T
V
T V
T T V V
T V T V
| |
= |
|
\ .
| | | |
= =
| |
\ . \ .

From this we can deduce that:
2-122
3 4
1 2
3 3 4 2
1 2 1 4
or
V V
V V
V V V V
V V V V

| | | |
=
| |
\ . \ .
| | | | | | | |
= =
| | | |
\ . \ . \ . \ .

Thus, if any isotherm is drawn to intersect the two adiabatic pathways, the ration of the volume at the intersection points is always the same.
This means that it is not possible for the adiabatic pathways to intersect.
2-123
2.48. An ideal gas is defined as one that obeys the relationship PV =nRT. We showed in Section 2.7 that for such gases
(U/V)
T
=0 and (H/P)
T
=0
Prove that for an ideal gas C
V
and C
P
are independent of volume and pressure.

Solution:

Recall that C
V
is defined by Eq. 2.45 which states that,
V
V
U
C
T
| |
=
|
\ .

From this, we can say that,
V
V T T
C U U
V V T T V
| | | | | |
= =
| | |

\ . \ . \ .

Since we are given that (U/V)
T
=0 for an ideal gas, then it is possible to see that from the above, (C
V
/V)
T
is also equal to zero. This
means that C
V
is independent of both volume and pressure as only temperature is being held constant. Similarly, for C
P
we have:
P
P
V
V T T
H
C
T
C H H
P P T T P
| |
=
|
\ .
| | | | | |
= =
| | |

\ . \ . \ .

Since we are given that (H/P)
T
=0 for an Ideal Gas, thus it is possible to see that from the above, (C
P
/P)
T
is also equal to zero. This
means that C
P
is independent of both volume and pressure as only temperature is being held constant.
2-124
2.49. One mole of an ideal gas underwent a reversible isothermal expansion until its volume was doubled. If the gas performed 1 kJ of
work, what was its temperature?

Solution:

Given: Ideal Gas: 1 mole, reversible isothermal expansion, w =1kJ

Required: T

Remember that a reversible isothermal expansion or compression of an ideal gas occurs along an isotherm (which means at constant
temperature!). Such a process is illustrated in Figure 2.6c. We have already seen the equations corresponding to this type of process. We
have also gone through the derivation for Eq. 2.72 which gives the work done ON the system in a reversible compression or expansion;

,1
rev
,2
ln
m
m
V
w RT
V
| |
=
|
|
\ .

However, since we are being asked for the work done by the gas, we must take the negative of this value (same magnitude, just opposite
sign).

,2
rev
,1
ln
m
m
V
w RT
V
| |
=
|
|
\ .
(Eq. 2.74)
In this particular case, we are given that, n =1 mol, -w =1000 J and
,2
,1
2
m
m
V
V
= . Thus,
( ) ( )
1 1
1000 J 1mol 8.3145 J K mol ln(2)
1000 J
T
T

=
=
1
mol
8.3145 J
1 1
K mol

ln(2)
173.5 155 501 K
173.5 K
T
T
=
=


2-125
2.50. A gas that behaves ideally was allowed to expand reversibly and adiabatically to twice its volume. Its initial temperature was 25.00
C, and C
V,m
=(5/2)R. Calculate U
m
and H
m
for the expansion process.

Solution:
Given: Ideal Gas:
,
5
25.00 C,
2
i V m
T C R = =
Required: ,
m m
U H
Since we already know that C
V,m
=(5/2) R we can determine C
P,m
by rearranging Eq. 2.119,
, ,
,
,
5
2
7
2
P m V m
P m
P m
C C R
C R R
C R
= +
= +
=

We can now determine the ratio of the two heat capacities, ;
,
,
7
7
2
5
2
2
P m
V m
C
C
=
= =
2
7
5 5
=

We have been given the initial temperature as well as the ratio between the final and initial volumes so that we can use Eq. 2.90 in order to
solve for the final temperature.
2-126
( )
( )
1
1
7
1
5
2
5
1
298.15 K
2
1
298.15 K
2
f
i
i f
i
f i
f
f
f
T
V
T V
V
T T
V
T
T
| |
= |
|
\ .
| |
= |
|
\ .
| |
=
|
\ .
| |
=
|
\ .

225.955 447 2 K
f
T =
We can again (as in the last few previous problems) use Eq. 2.95 and Eq. 2.96 in order to solve for and
m m
U H .
,
1
5
8.3145 J K
2
m V m
m
U C T
U

=
=
( )
( )
1
mol 225.9 554 472 298.15 K
1
1
1
,
1
1500.654 024 J mol
1500 J mol
1.5 kJ mol
7
8.3145 J K
2
m
m
m
m P m
m
U
U
U
H C T
H
=
=
=
=
=
( )
( )
1
mol 225.9 554 472 298.15 K
1
1
1
2100.915 632 J mol
2100 J mol
2.1 kJ mol
m
m
m
H
H
H
=
=
=

2-127
2.51. With C
V,m
=(3/2)R, 1 mol of an ideal monatomic gas undergoes a reversible process in which the volume is doubled and in which 1
kJ of heat is absorbed by the gas. The initial pressure is 1 bar and the initial temperature is 300 K. The enthalpy change is 1.50 kJ .
a. Calculate the final pressure and temperature.
b. Calculate U and w for the process.

Solution:
Given: Ideal Gas:
,
3
, 1 mol, 1 kJ , 1 bar, 300 K, 1.50 kJ
2
V m i i
C R n heat P T H = = = = = =
Required: , , ,
f f m
P T U w
a. Since we have already been given the enthalpy change and the value for the molar heat capacity at constant volume, we can find the
value for the molar heat capacity at constant pressure.
, ,
, ,
,
,
3
2
5
2
P m V m
P m V m
P m
P m
C C R
C C R
C R R
C R
=
= +
= +
=

Since we know that
P
H C T = , we can get the expression;
1 1
1500 J mol 20.79 J K

=
( )( )
1
mol 300 K
f
T

Solving first for the final temperature we get,
2-128
( )
1500 J
300 K
f
T =
1
mol
( )
20.79 J
1 1
K mol

( )
1500 J
f
T =
1
mol
( )
20.79 J
1 1
K mol

( )
300 K
372.150 072 2 K
372.15 K
f
f
T
T
+
=
=

The final pressure can be found using a rearrangement of Eq. 2.91,
372.1 500 722 K
f f f
i i i
f f
i
i i f
f
i
T P V
T PV
P T
V
P T V
P
P
=
=
=
300 K
( )
( ) ( )
1
2
0.620 250 12
0.620 250 12
1 bar 0.620 250 12
0.620 250 12 bar
0.62 bar
f
i
f i
f
f
f
P
P
P P
P
P
P
=
=
=
=
=

b. It follows that the change in internal energy would be,
2-129
,
1
3
8.3145 J K
2
m V m
m
U C T
U

=
=
( )
( )
1
mol 372.150 072 2 300 K
1
1
899.837 663 J mol
900 J mol
m
m
U
U
=
=

Since the heat is absorbed BY the gas, work is defined as w U q = , which, when making the appropriate substitutions, will yield:
1 1
1
1
899.837 663 J mol 1000 J mol
100.162 337 J mol
100 J mol
w
w
w

=
=
=

2-130
2.52. Prove that:
V
T U
U V
C
V T
| | | |
=
| |

\ . \ .

Solution:
Remember again that
V
C is defined as (according to Eq. 2.25):
V
V
U
C
T
| |
=
|
\ .

Flip to Appendix C or try to remember Eulers Chain Rule from calculus. We will see that, if a function depends on two or more variables,
the partial derivative relates to the dependence of say, z on one variable with all other variables held constant. This would be if we were
working with the differential,
y
z
x
| |
|
\ .
which expresses the dependence of z on x when y is held constant.
If z is a function of x and y, Eq. C.6 (from Appendix C) will apply and we can then hold z constant and divide by dx to get the following:
0
y x
y z x
z z
dz dx dy
x y
z z y
x y x
| | | |
= +
| |

\ . \ .
| | | | | |
= +
| | |

\ . \ . \ .

We must then apply Eq. C.9 which will yield,
( )
1
/
1
or
y
y
x y z
y z x
z
x x z
x y z
y z x
z z y
x y x
| |
=
|

\ .
| | | | | |
=
| | |

\ . \ . \ .
| | | | | |
=
| | |

\ . \ . \ .

2-131
The last expression above is called Eulers Chain Rule. Let us now apply this logic to the current system.
We can equate
y
z
x
| |
|
\ .
with
V
U
T
| |
|
\ .
which means that we can also equate
y z x
z z y
x y x
| | | | | |
=
| | |

\ . \ . \ .
with
V T U
U U V
T V T
| | | | | |
=
| | |

\ . \ . \ .
. This
would then mean that,
V
V T U
U U V
C
T V T
| | | | | |
= =
| | |

\ . \ . \ .


2-132
2.53. Prove that for an ideal gas the rate of change of the pressure dP/dt is related to the rates of change of the volume and temperature by
1 1 1
dP dV dT
P dt V dt T dt
= +

Solution:
Given: Ideal Gas
Required:
dP
dt
as it relates to
dV
dt
and
dT
dt

From Appendix C, we are given the general relationship between pressure, volume and temperature by again making use of Eq. C.6 and
then applying the partial derivative
y
z
x
| |
|
\ .
. Then the total derivative becomes,
V T
P P
dP dT dV
T V
| | | |
= +
| |

\ . \ .

From the Ideal Gas Law, PV nRT = in the form
nRT
P
V
= we can find the two required partial derivatives that appear in the differential
equation.

2
V
T
P nR P
T V T
P nRT P
V V V
| |
= =
|
\ .
| |
= =
|
\ .

Substitution gives,
P P
dP dT dV
T V
=
and upon rearrangement and differentiation with respect to t , gives
2-133
1 1 1 dP dT dV
P dt T dt V dt
=

2-134
2.54. Initially 5 mol of nitrogen are at a temperature of 25 C and a pressure of 10 bar. The gas may be assumed to be ideal; C
V,m
=20.8 J
K
1
mol
1
and is independent of temperature. Suppose that the pressure is suddenly dropped to 1 bar; calculate the final temperature,
U, and H.

Solution:
Given: Nitrogen:
1 1
nitrogen ,
5 mol, 25 C, 10 bar, 20.8 J K mol , 1 bar
i i V m f
n T P C P = = = = =
Required: , ,
f
T U H
From Eq. 2.95 written for one mole,
( )
, 2 1 m V m
U C T T =
For n moles,
, m V m
U nC T =
Taking the differentials we have,
, V m
dU nC dT =
From Eq. 2.74,
we may also write,
where
m rev rev
U q w
nRT
dU dq dw dw PdV dV
V
= +
= + = =

Since dq=0
, V m
nRT
nC dT dV
V
=
Rearranging and integrating yields
2-135
( )
,
,
,
,
ln ln
ln ln ln ln
ln ln ln ln
ln ln ln ln ln
Rearranging yields,
ln ln ln
ln
1
8.3145
20.8
ln
f f
V m
i i
f i f i
V m
f
i
f i
V m f i
i
f i f
V m f i
i
i
v f i
f
v
f
T V
C R
T V
R
T T V V
C
RT
R RT
T T
C P P
R R RT
T T T
C P P
R R RT
T
C P P
T
R
C
T
=
=
| |
=
|
|
\ .
| |
= +
|
|
\ .
| |
+
|
|
\ .
=
+
=
( )
( )
1 1 1 1
8.3145 J K mol 8.3145 J K mol 298.15 K
ln ln ln 298.15 K
100000 Pa 1000000 Pa
8.3145
1
20.8
ln 5.040 025 96
exp 5.040 025 96
154.474 025 2 K
155 K
f
f
f
f
T
T
T
T

| |
+
|
\ .
+
=
=
=
=

Solving for the energy we obtain,
2-136
( )
( ) ( )
1 1
1 1
5 mol 20.8 J K mol 154.474 025 2 K 298.15 K
14 942.301 38 J
14 942 J
5 mol 20.8 8.3145 J K mol 154.474 025 2 K 298.15 K
20 915.270 87 J
20 915 J
V
P
U nC T
U
U
U
H nC T
H
H
H
=
=
=
=
=
= +
=
=

2-137
2.55. A chemical reaction occurs at 300 K in a gas mixture that behaves ideally, and the total amount of gas increases by 0.27 mol. If U
= 9.4 kJ, what is H?

Solution:
Given: Ideal Gas: 300 K, 0.27 mol, 9.4 kJ
i
T n U = = =
Required: H
We know that the system initially contains n moles. When the reaction has occurred an extra 0.27 moles has been formed. So the extra 0.27
moles has caused a PV change since the temperature remains constant. The relationship is,
( )
( )
( ) 0.27 mol
PV nRT
PV RT
=
=

Since in Eq. 2.41 we have
( ) H U PV = + ,
substitution of the value of 0.27RT for PV and the given value of U gives,
( ) 0.27 mol PV =
( )
1
8.3145 J K
1
mol
( )
300 K
( )
( ) 673.4745 J
( )
9400 J 673.4745 J
10 073.4745 J
10.07 kJ
PV
H U PV
H
H
H
=
= +
= +
=
=

2-138
2.56. Suppose that 1.00 mol of an ideal monatomic gas (C
V
=(3/2)R) at 1 bar is adiabatically and reversibly compressed starting at 25.0
C from 0.1000 m
3
to 0.0100 m
3
. Calculate q, w, U, and H.

Solution:

Given: Ideal Monatomic Gas:
3 3
3
, 1 bar, 25 C, 0.1000 m, 0.0100 m
2
V i i f
C R P T V V = = = = =

Required: , , , q w U H

In this problem, we are considering an ideal gas contained in a vessel whose walls are perfectly insulating (no heat exchange), this is called
an adiabatic process. Since work is performed ON the gas in order to compress it and no heat can leave the system, the final temperature
must be higher than the initial one.
By now we have seen Eq. 2.95 and Eq. 2.96 many times and we also know that both U and H remain unchanged as we move along an
isothermal pathway. Since we know that;

and
V P
U C T H C T = =

And from Eq. 2.41 { } ( ) H U PV = + as well as { } U q w = + from Chapter 1, we can formulate a pertinent expression for the work
done on the gas during the compression. It is extremely important to note that since we are working under adiabatic conditions, this implies
that q =0. This helps to simplify the expression for work.

The fact is that the gas is undergoing a compression so P-V work is being done, thus

( )
( )( )
( )( )
3 3
3
1 bar 0.0100 m 0.1000 m
1 bar 0.09 m
f i
w P V P V V
w
w
= =
=
=

Now we should change the units in order to express this in joules. Therefore, we must make all the appropriate substitutions.

2-139
( ) ( )
5
5 3
3
2
3
2 2
1 bar 10 Pa, therefore,
10 Pa 0.09 m
9000 Pa m
kg kg m
since 1 Pa 1 and 1 J , 1 J m Pa
ms s
9000 J
w
w
w
=
=
=
= = =
=

Now we can find the final temperature using the Ideal Gas Law. This will enable us to determine the change in enthalpy and internal
energy.

5
10 Pa
f f
f
f
f
PV nRT
PV
T
nR
T
=
=
=
( )
3
0.0100 m
( )
1 mol
( )
0.083145 J
1 1
K mol

( )
120.264 582 1 K
f
T =

,
for moles,
1 mol
m V m
m
n
U nC T
U
=
=
( )
1
3
8.3145 J K
2

1
mol
( ) 120.264 582 1 298.15 K

| |

|
\ .
2 218.542 461 J
2.22 kJ
m
m
U
U
=
=

We can solve for the enthalpy change by using Eq. 2.96 which yields,

2-140
, ,
, ,
,
,
3 5
2 2
for moles,
1 mol
P m V m
P m V m
P m
m P m
m
C C R
C C R
C R R R
n
H nC T
H
=
= +
= + =
=
=
( )
1 1
5
8.3145 J K mol
2

( ) 120.2 645 821 298.15 K
| |

|
\ .
3 697.570 768 J
3.70 kJ
m
m
H
H
=
=

Lastly, we will make use of the fact that { } U q w = + in order to solve for the amount of heat generated by the compression.
U q w
q U w
= +
=

( ) 2 218.542 461 9000 J
6 781.457 539 J
6.78 kJ
q
q
q
= (

=
=


2-141
2.57. Suppose that an ideal gas undergoes an irreversible isobaric adiabatic process. Derive expressions for q, w, U, and H and the final
temperature of the gas undergoing the process.

Solution:
Given: Ideal Gas: irreversible isobaric process
Required: expressions for , , , ,
f
q w U H T
It is important to note the conditions of this problem! The term isobaric means that the process is executed under constant pressure. We
also remember that adiabatic means that there is no heat exchange between the material inside the vessel and the surroundings (the vessel
walls are impermeable). In addition, we need to account for the fact that this process is an irreversible one. Mathematically, this all
generates the following;
1 2
Isobaric
Adiabatic 0 and
P P P
q w P V
= =
= =

Therefore,
U q =
f f
f
f
w
U w
U P V
PV nRT
PV
T
nR
+
=
=
=
=

As for the enthalpy change, there are a couple of different ways that it can be found. We will use the fact that for an ideal monatomic gas,
C
P
=5/2R:
2-142
( )
,
5
2
5
2
m P m
f i
f
i
H C T
H R T T
PV
H R T
nR
=
=
| |
=
|
\ .

Or, we can use Eq. 2.41 which gives, ( ) H U PV = + and if the correct values are used throughout the exercise, this should still be valid
for an ideal monatomic gas.

2-143
2.58. Exactly one mole of an ideal monatomic gas at 25.0 C is cooled and allowed to expand from 1.00 dm
3
to 10.00 dm
3
against an
external pressure of 1.00 bar. Calculate the final temperature, and q, w, U, and H.

Solution:
Given: Ideal Monatomic Gas:
3 3
25 C, 1.00 dm, 10.00 dm, 1.00 bar
i i f ext
T V V P = = = =
Required: , , , ,
f
q w U H T
Given the pressure as well as the final and initial volumes, we can determine the final temperature by using the same method as we did in
previous problems.
1.00 bar
ext f f
ext f
f
f
P V nRT
P V
T
nR
T
=
=
=
( )
3
10.00 dm
( )
1.00 mol
( )
0.083 15 bar
3
dm
1 1
K mol

( )
120.2 645 821 K
120.3 K
f
f
T
T
=
=

In this process, it is the gas that is doing the work while expanding against a constant external pressure. Knowing that the work done ON
the system in a reversible compression is:
,2
,1
m
m
V
V
w PdV =

We can determine the work done by the gas against the external pressure by doing the integration and making a substitution.
2-144
,2
,1
,2
,1
,2
,1
ln
ln
m
m
m
m
m
m
V
V
m
V
m
V
m
m
PV nRT
nRT
P
V
nRT
w dV
V
w nRT V
V
w nRT
V
=
=
=
=
| |
=
|
|
\ .

,1
,2
ln
1.00 mol
m
m
V
w nRT
V
w
| |
=
|
\ .
=
( )
1
8.3145 J K
1
mol
( )
120.264 582 1 K
( )
1.00
ln
10.00
2 302.446 633 J
2.30 kJ
w
w
| |
|
\ .
=
=

We will solve for , and q U H in the same way as we have been doing for the past few problems.
ideal monatomic gas;
5
2
1.00 mol
P
H nC T
H n R T
H
=
=
=
( )
1
5
8.3145 J K
2

1
mol
( ) 120.264 582 1 298.15 K

| |

|
\ .
3 697.570 768 J
3.70 kJ
H
H
=
=

2-145
ideal monatomic gas;
3
2
1.00 mol
V
U nC T
U n R T
U
=
=
=
( )
1
3
8.3145 J K
2

1
mol
( ) 120.264 582 1 298.15 K

| |

|
\ .
2 218.542 461 J
2.22 kJ
U
U
=
=

Finally, we can solve for the amount of heat generated during this reaction.
( ) ( )
2
2 218.542 461 2 302.446 633 J
83.90 417 231 J
8.39 10 kJ
U q w
q U w
q
q
q

= +
=
= (

=
=

2-146
2.59. A balloon 15 m in diameter is inflated with helium at 20 C.
a. What is the mass of helium in the balloon, assuming the gas to be ideal?
b. How much work is done by the balloon during the process of inflation against an external pressure of 1 atm (101.315 kPa), from
an initial volume of zero to the final volume?

Solution:
Given: Helium:
3
balloon ext
15 m, 20 C, 1.00 atm, 0 dm
i i
d T P V = = = =
Required:
balloon
, (by balloon) m w
a. Assuming the balloon is a perfect sphere,
3
sphere
4
3
V r =
Remembering that the diameter is twice the radius, we can write;
( )
3
balloon
3
balloon
3
balloon
3
balloon
4
3 2
4 15
3 2
4
7.5
3
1 767.145 868 m
d
V
V
V
V
| |
=
|
\ .
| |
=
|
\ .
=
=

We are now able to determine the amount of helium present in the inflated balloon (the number of moles) by using the Ideal Gas Law.
2-147
5
5
1 atm 1.013 25 10 Pa
1.013 25 10 Pa
PV nRT
PV
n
RT
n
=
=
=
=
( )
3
1 767.145 868 m
( )
8.3145 J
1
K
( )
1
mol 293.15 K
( )
73 462.038 55 mol n =

From the periodic table of the elements, we can approximate that the molar mass of helium is 4.026 g mol
-1
. We now have enough
information to find the mass of the balloon.
balloon
balloon
73 462.03 855 mol
m n M
m
=
=
( )
1
4.026 g mol
( )
balloon
balloon
295 758.167 2 g
295.8 kg
m
m
=
=

b. The work done by the balloon in question during an expansion against a constant external pressure is given by Eq. 2.12:
( )
2
1
2 1
V
V
w P dV
w P V V
w P V
=
=
=

Remember that when the system is doing work, we must switch the signs to get;
2-148
( )
( )( )
2
1
5 3
5
note that 0
1.01 325 10 Pa 1 767.145 868 m
179 056 055.1 J
1.79 10 kJ
V
V
f i
i
w P dV
w P V V
w P V
w P V
V
w
w
w
=
=
=
=
=
=
=
=

2-149
2.60. a. Calculate the work done when 1 mol of an ideal gas at 2 bar pressure and 300 K is expanded isothermally to a volume of 1.5 L,
with the external pressure held constant at 1.5 bar.
b. Suppose instead that the gas is expanded isothermally and reversibly to the same final volume; calculate the work done.

Solution:
Given: Ideal Gas:
ext
1 mol, 2 bar, 300 K, 1.5 L, 1.5 bar
i i f
n P T V P = = = = =
Required: done in both cases w
a. Under isothermal conditions, we already know that the temperature is being held constant. We also need to consider that this expansion
is occurring against an external pressure just like in Problem 2.59. With the information that we have, we should start by trying to find
the initial volume for the gas using the Ideal Gas Law.
1.0 mol
i
i
i
i
PV nRT
nRT
V
P
V
=
=
=
( )
0.083 15 bar
3 1
dm K
1
mol
( )
300 K
( )
2 bar
3
12.4725 dm
i
V =

By combining the gas laws for both the initial and final reaction conditions, we will be able to determine the final volume in cubic
decimeters. Take note that the final pressure is equal to the constant external pressure value.
2.0 bar
i i
f
f
f
PV
V
P
V
=
=
( ) ( )
3
12.4725 dm
1.5 bar
( )
3
16.63 dm
f
V =

The system exerts pressure-volume work, so we can say that:
2-150
( ) ( )
3
3
1.5 bar 16.63 12.4725 dm
6.236 25 bar dm
ext
w P V
w
w
=
=
=

5 5
1 bar 10 Pa, 1 atm 1.013 25 10 Pa
6.236 25 bar w
= =
=
( )
3 5
dm 10 Pa
1
bar
( )
5
1 atm
1.013 25 10 Pa
3
3
3
6.154 700 222 atmdm
1 atmdm 101.325 J therefore,
6.154 700 222 atmdm
w
w
| |
|
\ .
=
=
=
( )
3
101.325 J
1 atmdm
623.625 J
624 J
w
w
=
=

Remember that when the work provides a negative number, it means that the gas itself is the component doing the work. This is obvious
when we consider the fact that the process is an expansion against constant pressure.
b. Now we will imagine that the gas is being expanded isothermally and reversibly to the same final volume. This means that the process
is occurring at constant temperature. This process is called reversible isothermal expansion. Note that since there is no change in
temperature throughout the reaction, the changes in internal energy and enthalpy will also be equal to zero due to their dependence on
temperature change.
The work done on the system in a reversible compression is given by Eq. 2.70:
2-151
,2
,1
,2
,1
rev
rev
,2
rev
,1
rev
ln
ln
1.0 mol
m
m
m
m
V
V
V
V
m
m
w PdV
nRT
P
V
w nRT V
V
w nRT
V
w
=
=
=
| |
=
|
\ .
=
( )
1
8.3145 J K
1
mol
( )
300 K
( )
rev
rev
16.63
ln
12.4725
717.579 777 4 J
718 J
w
w
| |
|
\ .
=
=

As we have just observed, the gas is actually doing more work in the reversible isothermal pathway. The difference in work done is 94 J .
2-152
2.61. The heat capacity difference can be determined experimentally in terms of the two variables and in the equation for an ideal gas.
Determine the value of C
P
and C
V
for an ideal gas in the equation C
P
C
V
=TV
2
/ where
1 1
and
P T
V V
V T V P

| | | |
= =
| |

\ . \ .

Solution:
Given: see above
Required: C
P
and C
V
For an Ideal Gas, we know that PV nRT = . This equation can be rearranged to solve for any missing variable. From the two equations
given, we see that we must differentiate volume as our known with respect to P and also with respect to T, holding the other variables
constant. We rearrange the expression so that the volume can be isolated.
this expression is for one mole of substance
RT
V
P
=
We now can evaluate the two given differentials in the problem for one mole of gas.
2
2
1
P
T
T
V R
T P
V
RT
P P
V RT
P P
| |
=
|
\ .
| | | |
=
| |
\ . \ .
| | | |
=
| |
\ . \ .

Now substitute these values into
1 1
and
P T
V V
V T V P

| | | |
= =
| |

\ . \ .
.
Substituting these values for and into the given equation
2

P V
C C TV

= , we obtain,
2-153
2 2
2
1
P V
R
V P
C C TV
RT
V P
| | | |
| |
\ . \ .
=
| || |
| |
\ .\ .

2
2 2
2
P V
R
V P
C C TV
RT
VP
| |
|
\ .
=
| |
|
\ .

Now we simplify to obtain,
P V
C C T = V
( )
2
R
V
2
2
P
V
| |
|
|
\ .
2
P
R T
1 1
8.3145 J K mol
P V
P V
C C R
C C

| |
|
|
\ .
=
=

2-154
2.62. For an ideal gas, PV
m
=RT and therefore (dT/dP)
V
=V
m
/R. Derive the corresponding relationship for a van der Waals gas.

Solution:

Given: Ideal Gas: ,
m
V
dT V
PV RT
dP R
| |
= =
|
\ .

Required: same relationship for a van der Waals gas

This last section of problems for Chapter 2 concern Real Gases. It is important that you are familiar with all of the material regarding Real
Gases from Chapter 1. We were given that for a single mole of a real gas, the Van der Waals Equation is written;

( )
2 m
m
a
P V b RT
V
| |
+ =
|
\ .
(Eq. 2.100)
We came to this expression by starting with the Ideal Gas Law then making small adjustments to compensate for the non-ideal nature of
real gases. This is why there are two new constants a and b.

The information provided to us indicates that since PV nRT = solving the differential
V
dT
dP
| |
|
\ .
will produce the following;

and therefore,
V
PV
T
R
dT V
dP R
=
| |
=
|
\ .

Our task now is to carry out the same procedure on the modified van der Waals Equation. First let us expand the expression to isolate for T.

( )
( ) ( )
2
2
m
m
m m
m
a
P V b RT
V
a
P V b V b RT
V
| |
+ =
|
\ .
| |
+ =
|
\ .

Now we will isolate temperature which gives,
2-155
( )
( )
2
m
m
m
P V b a
T V b
R RV
| |
= +
|
\ .

Now we must determine the value of the differential,
V
dT
dP
| |
|
\ .
.
( )
( )
2
m
m
m
m
V
P V b a
T V b
R RV
dT V b
dP R
| |
= +
|
\ .
| |
=
|
\ .

Note that the far right hand side of the expression completely cancels out because there is no P dependence involved there while V is being
held constant.


2-156
2.63. One mole of a gas at 300 K is compressed isothermally and reversibly from an initial volume of 10 dm
3
to a final volume of 0.2 dm
3
.
Calculate the work done on the system if
b. the equation of state of the gas is P(V
m
3
mol
1
.
Explain the difference between the two values.

Solution:
Given:
3 3
1 mol, 300 K, 10 dm, 0.2 dm
i f
n T V V = = = =
Required:
ideal
w and see above
This problem will be solved without extensive explanation because we have covered a number of these types of problems already.
a. For an Ideal Gas under isothermal and reversible conditions:
2
1
2
1
2
1
ln
ln
V
V
V
V
w PdV
nRT
P
V
w nRT V
V
w nRT
V
=
=
=
=

Since the process involves a compression, the work will be doneon the gas and the work done by the system should be a positive quantity.
1.0 mol w =
( )
1
8.3145 J K
1
mol
( )
300 K
( )
0.2
ln
10
9 757.954 584 J
9.76 kJ
w
w
| |
|
\ .
=
=

b. For a Real Gas under the same isothermal and reversible conditions, we will solve the problem using the equation of state for the
particular gas. We need to express the work done while using the equation of state. This means that we should first expand and
simplify the equation of state if possible.
2-157
( )
( )
m
m
P V b nRT
nRT
P
V b
=
=

( )
2
1
2
1
V
V
V
V
m
w PdV
dV
w nRT
V b
=
=

Let ( )
m
V b x = and dV dx = to simplify the integration. Making these substitutions gives,
( )
2
1
2
1
ln
ln
1.0 mol
V
V
V
m
V
f
i
dx
w nRT
x
w nRT V b
V b
w nRT
V b
w
=
=
| |
=
|
\ .
=
( )
1
8.3145 J K
1
mol
( )
300 K
( )
3 3
3 3
0.2 dm 0.03dm
ln
10.0 dm 0.03dm
1.0 mol w
| |
|
\ .
=
( )
1
8.3145 J K
1
mol
( )
300 K
( )
3
0.17 dm
ln
3
9.97 dm
10 155.839 38 J
10.16 kJ
w
w
| |
|
|
\ .
=
=

It should be noted that the reason why there is more work done when working with a real gas (as compared to an ideal gas), is because of
the larger absolute value of the ratio of free volumes.

2-158
2.64. One mole of a gas at 100 K is compressed isothermally from an initial volume of 20 dm
3
to a final volume of 5 dm
3
. Calculate the
work done on the system if
b. the equation of state is
6 1
2
where 0.384m Pamol
m
m
a
P V RT a
V
| |
+ = =
|
\ .

[This equation is obeyed approximately at low temperatures, whereas P(V
m
b) =RT (see Problem 2.63) is obeyed more closely at
higher temperatures.] Account for the difference between the values in (a) and (b).

Solution:
Given:
3 3
1 mol, 100 K, 20 dm, 5 dm
i f
n T V V = = = =
Required:
ideal
w and
real
w
a. This situation is similar to the last problem in that, the gas is being compressed and the system is the component doing the work. This
means that the value obtained for work should be positive. We are still working under isothermal conditions!
For the Ideal Gas (please note that we have been solving all problems according to the single mole assumption):
2-159
ln
ln
1.0 mol
f
i
f
i
f
i
V
V
V
V
V
V
f
i
PV nRT
nRT
P
V
w PdV
dV
w nRT
V
w nRT V
V
w nRT
V
w
=
=
=
=
=
=
=
( )
1
8.3145 J K
1
mol
( )
100 K
( )
ideal
5
ln
20
1 152.634 447 J
1.15 kJ
w
w
| |
|
\ .
=
=

b. For the Real Gas:
2 m
m
a
P V RT
V
| |
+ =
|
\ .
should be expanded and simplified so that we can execute the same kind of procedure as was done
in the first part of this problem.
2-160
2
2
2
2
1
ln
1 1
ln
1.0 mol
f
i
f f
i i
f
f
i
i
m
m
m m
m m
V
V
V V
V V
V
V
V
V
f
i f i
a
P V nRT
V
a nRT
P
V V
nRT a
P
V V
w PdV
dV dV
w nRT a
V V
w nRT V a
V
V
w nRT a
V V V
w
| |
+ =
|
\ .
+ =
=
=
= +
| |
= +
|
\ .
| |
| |
=
|
|
|
\ .
\ .
=

( )
1
8.3145 J K
1
mol
( )
100 K
( )
( )
( )
( )
6
3 3
2
3 3 6 3 5 3
6
5
ln
20
1 1
0.384 m Pa
5 dm 20 dm
1000 dm 1 m, m 1 m , 1 atm 1.013 25 10 Pa, 1 atmdm 101.325 J
m
1 152.634 447 J 0.0576 w
| |
|
\ .
| |

|
\ .
= = = =
=
3
Pa
dm
3
1000 dm
| |
|
|
\ .
3
1 m

( ) 1 152.634 447 J 57.6 Pa w =
( )
( )
3
real
m
1 152.634 447 57.6 J
1 095.034 447 J
1.10 kJ
w
w
w
=
=
=

2-161
2.65. Derive the expression
3 2
( )
m
m
m m m m
PdV ab PdT a dT
dP dV
V b V V b T V T
= + +
for 1 mol of a van der Waals gas.

Solution:
We are already familiar with the van der Waals expression for a single mole of gas. Now, we will need to use the partial derivatives section
of Appendix C in order to generate the corresponding relationship.
Starting with the van der Waals Equation for 1 mole of gas:
( )
( )
( )
2
2
2
Expand to form,
m
m
m m
m m
a
P V b RT
V
a RT
P
V V b
RT a
P
V b V
| |
+ =
|
\ .
| |
+ =
|

\ .
=

The total differential can be written from Appendix C as,
m
m
V m
T
P P
dP dV dT
V T
| | | |
= +
| |

\ .
\ .

Since we have already found the total differential for the pressure, we can determine the values of these two partial derivatives.
( )
( )
2 3
1 2
m
V m
m m
m T
P R
T V b
P a
RT
V V
V b
| |
=
|

\ .
| | | |
= +
| |

\ . \ .

2-162
( )
2 3
2
m m
T m
P RT a
V V
V b
| | | |
= +
| |

\ . \ .

Now we can substitute these values into the total derivative to reproduce the derived equation given above.
( )
( )
( )
( )
2 3
2 3
2
and
Substitution of these into
gives,
2
m
m
V m m m
T m
m
V m
T
m m
m m
m
P RT a P R
V V T V b
V b
P P
dP dV dT
V T
RT a R
dP dV dV dT
V V b
V b
| | | | | |
= + =
| | |

\ .
\ . \ .
| | | |
= +
| |

\ .
\ .
| |
| | | |
= + + |
| |
|
|

\ . \ .
\ .

Remember that:
( )
2 m
m
a
P V b RT
V
| |
+ =
|
\ .
so we can actually add back in the pressure term.
For the first two segments of the expression above, the substitution will be as follows;
( )
2 m
m
a
P V b
V
dP
| |
+
|
\ .
=
( )
2
m
V b
3
2
3
2
2
m m
m
m
m m
m m
a
dV dV
V
a
P
V a
dP dV dV
V b V
| |
|
| |
|
+
|
|
\ .
|
|
\ .
| |
+
|
| |
| = +
|
|
\ .
|
\ .

2-163
The last segment is slightly tricky because we need to separate the equation again and this will create four segments rather than the original
three. Lets try!
( )
( )
2
2
m m
m m
RT a
P
V b V
P R a
T V b TV
| |
=
|
\ .
| |
=
|
\ .

( )
( )
2
2
......... .........
......... .........
m m
m
m
R P a
V b T TV
R
dP dT
V b
P a
dP dT
T TV
= +
| |
= + +
|
\ .
| |
= + + +
|
\ .

Now everything can be put together to get:
2
3 2
2
m
m m
m m m
a
P
a P a V
dP dV dV dT dT
V b V T TV
| |
+
|
| | | |
| |
= + + + |
| | |
\ . | \ . \ .
|
\ .

We can now expand a bit;
( )
( )
( )
2
3 2
3 2
3 2
2
2
2
m
m m m
m m m m
m m
m m m m
m
m m m m
a
P a P a V
dP dV dV dV dT dT
V b V b V T V T
aV a V b P P a
dP dV dT dT
V b V V b T V T
P ab aV PdT a dT
dP dV
V b V V b T V T
= + + +

= + +

= + +

2-164
2.66. If a substance is burned at constant volume with no heat loss, so that the heat evolved is all used to heat the product gases, the
temperature attained is known as the adiabatic flame temperature. Calculate this quantity for methane burned at 25 C in the amount
of oxygen required to give complete combustion to CO
2
and H
2
O. Use the data in Appendix D and the following approximate
expressions for the heat capacities:
C
P,m
(CO
2
)/J K
1
mol
1
=44.22 +8.79 10
3
T/K
C
P,m
(H
2
O)/J K
1
mol
1
=30.54 +1.03 10
2
T/K

Solution:
Given: Appendix D, C
P,m
(CO
2
)/J K
1
mol
1
=44.22 +8.79 10
3
T/K
C
P,m
(H
2
O)/J K
1
mol
1
=30.54 +1.03 10
2
T/K

Required: T adiabatic flame temperature
With any problem of this type, it is always important to begin by writing down all of the reactions that will be useful. The balanced reaction
for the complete combustion of methane gas is as follows:
4 2 2 2
CH (g) 2O (g) CO (g) 2H O(g) + +
Remember from previous problems that we can determine the standard enthalpy change by using the enthalpies of formation for all species
involved.
O
2 2 4
(CO , g) 2 (H O, g) (CH , g)
f f
f f f
H H H
H H H H
=
= +

By using the enthalpies of formation found in Appendix D, we can calculate this value.
( ) ( ) ( )
1 1 1
1
393.51 kJ mol 2 241.826 kJ mol 74.6 kJ mol
802.562 kJ mol
H
H

= +
=

We have been given the expressions for the heat capacities for both carbon dioxide and gaseous water so we can combine them in order to
get the total heat capacity for the products.
2-165
( ) ( )
( ) ( )
( ) ( )
( )
1 1 3
, 2
1 1 2
, 2
1 1
, 2 , 2
1 1 2
CO / J K mol 44.22 8.79 10 / K
H O / J K mol 30.54 1.03 10 / K
(products) / J K mol CO 2 H O
(products) / J K mol 105.30 2.939 10 / K
P m
P m
P P m P m
P
C T
C T
C C C
C T
= +
= +
= +
= +

Since we are working under constant volume, we will need to determine the appropriate values for the heat capacity. Recall that:
, , P m V m
C C R =
, , V m P m
C C R =
We can use the expression for the heat absorbed in order to determine the final temperature. Remember that under these conditions, the
heat absorbed by the gas will be equal to the standard internal energy change for the reaction. Since we are using the heat capacity given in
terms of constant pressure conditions, we will be making the appropriate arrangements to involve the value we solved for initially.
( )
( ) ( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
2
1
2
2
2
2
, , , 2 1
/
, ,
298.15
/K
1 2
298.15
/K
2
298.15
2 /K
2
298.15
2
/K
802 562 J mol 105.30 8.3145 2.939 10 / K / K
802 562 96.9855 2.939 10 / K / K
1
802 562 96.9855 2.939 10 / K
2
T
V m V m V m
T
T K
V m P m
T
T
T
q C dT C T T
q C R d T
T d T
T d T
T
= =
=
= +
= +
= +
( )
2
/K
98.15
2
2 2 2
2
2
2
2 2 2
2
2 2 2
802 562 96.9855 298.15 1.4695 10 88 893.422 5
K K
802 562 96.9855 28 916.226 83 1.4695 10 1306.288 844
1.4695 10 96.9855 832 784.
T
T T
T T
K K
T T
K K
| |
| |
= +
| |
\ .
\ .
| | | |
= +
| |
\ . \ .
| | | |
+
| |
\ . \ .
515 7 0 =

2-166
This forms a quadratic equation which can then be solved to determine the adiabatic flame temperature for methane. Let each term
correspond to the general quadratic equation given by
2
0 ax bx c + + = . This means that
2
K
T
x = which leads to;
( ) ( )( )
( )
( )
2
2
2
2
2
2
2
4
2
96.9855 96.9855 4 1.4695 10 832 784.515 7
K 2 1.4695 10
96.9855 58 357.261 04
K 2.939 10
b b ac
x
a
T
T

=

=

Using the positive value for the square root we obtain,
2
2
2
96.9855 58 357.261 04
2.939 10
4 919.597 678
T
K
T
K
+
=
=

2
flame
4 920 K
4 920 K
T
T
=
=

The value as calculated may vary by about 20 K lower depending upon how many significant figures we used in the calculation. This value
may be reduced by about 170 K under constant pressure condition.

2-167
2.67. Two moles of a gas are compressed isothermally and reversibly, at 300 K, from an initial volume of 10 dm
3
dm
3
. If the equation of state of the gas is P(V
m
3
mol
1
, calculate the work done on the system, U,
and H.

Solution:
Given:
3 3
2 mol, 300 K, 10 dm, 1 dm
i f
n T V V = = = =
( )
3 1
,with 0.04 dm mol
m
P V b RT b = =
Required: , , w U H
We have seen many problems like this one already. Remember that under isothermal conditions, there is no change in temperature. It is
also important to note that the process is reversible. Lastly, we are working with a Real Gas which means that we cannot use the Ideal Gas
Law.
Since the gas is undergoing a compression, the reversible work done on the system is given by:
2-168
( )
( )
( )
( )
rev
rev
rev
rev
rev
using Eq. of state:
then and so,
ln
ln
2.0 mol
f
i
f
i
f
i
V
V
V
V
V
V
f
i
w PdV
P V nb nRT
nRT
P
V nb
dV
w nRT
V nb
w nRT V nb
V nb
w nRT
V nb
w
=
=
=
=
| |
=
|
\ .
=
( )
1
8.3145 J K
1
mol
( )
300 K
( )
3
1 dm
ln
(2.0 mol
3
)0.04dm
1
mol
3

10 dm (2.0 mol
3
)0.04dm
1
mol
rev
2.0 mol w
| |
|
|
\ .
=
( )
1
8.3145 J K
1
mol
( )
300 K
( )
rev
rev
0.92
ln
9.92
11 862.801 99 J
11.86 kJ
w
w
| |
|
\ .
=
=

The change in internal energy for a Real Gas is given by Eq. 2.124 and Eq. 2.125:
2
2
T
U n a
dU dV dV
V V
| |
= =
|
\ .

2
1
2
2
2
2
1
1 1
f
i
V
V
V
V
i f
n a
U dV n a
V V
U n a
V V
| |
= =
|
\ .
| |
=
|
|
\ .

2-169
Since the constant a is not involved in the equation of state for this unknown real gas, there will be no change in the internal energy
throughout the reaction.
0 U =
Eq. 2.127 will then enable us to determine the change in enthalpy.
( ) H U PV = +
We have not been given the pressures corresponding to the system so they must be calculated using the equation of state.
( )
( ) ( )
1 2
and
2.0 mol
i f
i
P V nb nRT
nRT nRT
P P
V nb V nb
P
=
= =

=
( )
3 1
0.083 15 bar dm K
1
mol
( )
300 K
( )
3
10 dm 2.0 mol
( )
3 1
0.04 dm mol
3
49.89 bar dm
i
P
(

=
3
9.92 dm
( )
5.029 233 871 bar
2.0 mol
i
f
P
P
=
=
( )
3 1
0.083 15 bar dm K
1
mol
( )
300 K
( )
3
10 dm 2.0 mol
( )
3 1
0.04 dm mol
3
49.89 bar dm
f
P
(

=
3
0.92 dm
( )
54.228 260 87 bar
f
P =

We can now find the value for the P-V work done and subsequently the change in enthalpy for the reaction.
( ) ( )
3
3
5.029 233 871 bar 10.0 dm
50.292 338 71 bar dm
i i
i i
PV
PV
=
=

2-170
5 5 3
1 bar 10 Pa, 1 atm 1.01325 10 Pa, 1 atmdm 101.325 J
50.292 338 71 bar
i i
PV
= = =
=
5
3
10 Pa
dm
1 bar
5
1 atm
1.01325 10 Pa
3
49.634 679 21 atmdm
i i
PV =
3
101.325 J
1 atmdm
( ) ( )
3
3
5029.233 871 J
54.228 260 87 bar 1.0 dm
54.228 260 87 bar dm
54.228 260 87 bar
i i
f f
f f
f f
PV
P V
P V
P V
=
=
=
=
5
3
10 Pa
dm
1 bar
5
1 atm
1.01325 10 Pa
3
53.519 132 37 atmdm
f f
P V =
3
101.325 J
1 atmdm
( )
5422.826 087 J
( )
( ) 5422.826 087 5029.233 871 J
( ) 393.592 216 J
f f
f f i i
P V
PV P V PV
PV
PV
H U
=
=
=
=
= ( )
394 J
PV
H
+
=

The application of the correct number of significant figures gives,
2
4 10 J H =

2-171
2.68. Three moles of a gas are compressed isothermally and reversibly, at 300 K, from an initial volume of 20 dm
3
dm
3
. If the equation of state of the gas is
2
2 m
m
n a
P V nRT
V
| |
+ =
|
\ .

with a =0.55 Pa m
6
mol
1
, calculate the work done, U, and H.

Solution:
Given:
2
3 3
2
3 mol, 300 K, 20 dm, 1 dm,
i f m
m
n a
n T V V P V nRT
V
| |
= = = = + =
|
\ .

Required: , , w U H
We will solve this problem in the exact same way as problem 2.67 was done. Since the two problems are extremely similar, no additional
explanation will be provided.
2-172
rev
2
2
2 2
2
2
rev 2
2
rev
2
rev
rev
using Eq. of state:
then and so
1
ln
1 1
ln
f
i
f
i
f
f
i
i
V
V
m
m
m
m m m
V
m
V
m m
V
V
m
V
m
V
f
i i f
w PdV
n a
P V nRT
V
n a nRT n a
PV nRT P
V V V
nRT n a
w dV
V V
w nRT V n a
V
V
w nRT n a
V V V
w
=
| |
+ =
|
\ .
+ = =
| |
=
|
\ .
| |
= +
|
\ .
| |
= +
|
|
\ .
=
3.0 mol
( )
1
8.3145 J K
1
mol
( )
300 K
( )
1
ln
20
3.0 mol
| |
|
\ .
+
( )
2
6
0.55 Pa m
1
mol
( )
3 3 3 3
3
rev
rev
rev
rev
1 1
20 10 m 10 m
22 417.21439 J 4702.5 Pa m
22 417.21439 J 4702.5 J
17 714.714 39 J
17.71 kJ
w
w
w
w

| |
\ .
=
=
=
=

2-173
2
1
2
2
2
2
2
2
1
1 1
3.00 mol
f
i
T
V
V
V
V
i f
U n a
dU dV dV
V V
n a
U dV n a
V V
U n a
V V
U
| |
= =
|
\ .
| |
= =
|
\ .
| |
=
|
|
\ .
=
( )
2
6
0.55 Pa m
1
mol
( )
3 3 3 3
3
1 1
20 10 m 10 m
4702.5 Pa m
4702.5 J
4.70 kJ
U
U
U

| |
\ .
=
=
=

2
2
2
2
2 2
2 2
and
3.0mol
m
m
m m
i f
i i f f
i
n a
P V nRT
V
nRT n a
P
V V
nRT n a nRT n a
P P
V V V V
P
| |
+ =
|
\ .
=
= =
=
( )
3
8.3145 Pam
1
K
1
mol
( )
300K
( )
3 3
20 10 dm
( )
2
3.0 mol
( )
6
0.55 Pam
1
mol
( )
3 3
20 10 m
( )
2
374 152.5 Pa 12 375 Pa
361 777.5 Pa
i
i
P
P
=
=

2-174
3.0 mol
f
P =
( )
3
8.3145 Pam
1
K
1
mol
( )
300K
( )
3 3
1.0 10 dm
( )
2
3.0 mol
( )
6
0.55 Pam
1
mol
( )
3 3
1.0 10 m
( )
( ) ( )
( ) ( )
2
3 3
3
3 3
3
7 483 050 Pa 4 950 000 Pa
2 533 050 Pa
361 777.5 Pa 20 10 m
7 235.55 Pa m
7 235.55 J
2 533 050 Pa 1.0 10 dm
2 533. 05 Pa m
f
f
i i
i i
i i
f f
f f
P
P
PV
PV
PV
P V
P V
=
=
=
=
=
=
=

( )
( )
2 533. 05 J
( )
( ) 2 533. 05 7 235.55 J
( ) 4702.5 J
( )
4702.5 4702.5 J
9405 J
9.41 kJ
f f
f f i i
P V
PV P V PV
PV
PV
H U PV
H
H
H
=
=
=
=
= +
=
=
=

2-175
2.69. One mole of a van der Waals gas at 300 K is compressed isothermally and reversibly from 60 dm
3
to 20 dm
3
. If the constants in the
van der Waals equation are
a =0.556 Pa m
6
mol
1
and b =0.064 dm
3
mol
1
calculate w
rev
, U, and H.

Solution:
Given: van der Waals gas:
3 3
1 mol, 300 K, 60 dm, 20 dm
i f
n T V V = = = =

6 1 3 1
0.556 Pa m mol , 0.064 dm mol a b = =
Required:
rev
, , w U H
The reversible work for a van der Waals gas is given by Eq. 2.122 and Eq. 2.123:
2-176
( )
( )
rev
2
2
2
rev 2
2
rev
2
rev
rev
using Van der Waals Eq:
1
ln
1 1
ln
1.0 mol
f
i
f
i
f
f
i
i
V
V
V
V
V
V
V
V
f
i i f
w PdV
n a
P V nb nRT
V
nRT n a
w dV
V nb V
w nRT V nb n a
V
V nb
w nRT n a
V nb V V
w
=
| |
+ =
|
\ .
| |
=
|
\ .
| |
= +
|
\ .
| | | |
= +
|
|
|
\ .
\ .
=
( )
1
8.3145 J K
1
mol
( )
300 K
( )
20 0.064
ln
60 0.064
1.0 mol
| |
|
\ .
+
( )
2
6
0.556 Pa m
1
mol
( )
3 3
1
60 10 m
3 3
1
20 10 m
rev
rev
2 727.122 887 J
2.73 kJ
w
w
| |
|
\ .
=
=

Recall that from Eq. 2.124 and Eq. 2.125 we can solve for the change in internal energy:
2
1
2
2
2
2
2
1
f
i
T
V
V
V
V
U n a
dU dV dV
V V
n a
U dV n a
V V
| |
= =
|
\ .
| |
= =
|
\ .

2-177
2
1 1
1.00 mol
i f
U n a
V V
U
| |
=
|
|
\ .
=
( )
2
6
0.556 Pa m
1
mol
( )
3 3
1
60 10 m
3 3
1
20 10 m
3
18.533 3 Pa m
18.533 3 J
18.5 J
U
U
U
| |
|
\ .
=
=
=

( )
( )
( ) ( )
2
2
2
2
2 2
2 2
and
1.0 mol
i f
i i f f
i
n a
P V nb nRT
V
nRT n a
P
V nb V
nRT n a nRT n a
P P
V nb V V V nb
P
| |
+ =
|
\ .
=
= =

=
( )
3
8.3145 Pam
1
K
1
mol
( )
300K
( )
( )
3 3
60 0.064 10 m
(

2
1.0 mol
( )
6
0.556 Pa m
1
mol
( )
3 3
60 10 m
( )
2
41 459.669 13 Pa
1.0 mol
i
f
P
P
=
=
( )
3
8.3145 Pam
1
K
1
mol
( )
300 K
( )
( )
2
3 3
1.0 mol
20 0.064 10 m

(

( )
6
0.556 Pa m
1
mol
( )
3 3
20 10 m
( )
2
123 727.877 2 Pa
f
P =

2-178
( ) ( )
( ) ( )
3 3
3
3 3
3
41 459.669 13 Pa 60 10 m
2 487.580 148 Pa m
2 487.580 148 J
123 727.877 2 Pa 20 10 m
2 474.557 544 Pa m
2 474.557 544 J
i i
i i
i i
f f
f f
f f
PV
PV
PV
P V
P V
P V
=
=
=
=
=
=

( )
( )
( ) 2 474.557 544 2 487.580 148 J
( ) 13.022 604 J
f f i i
PV P V PV
PV
PV
=
=
=

( )
( )
18.533 3 13.022 6047 J
31.555 904 J
31.56 J
H U PV
H
H
H
= +
=
=
=


2-179
2.70. Show that the J oule-Thomson coefficient can be written as:
1
T P
H
C P
| |
=
|
\ .

Then, for a van der Waals gas for which can be written as:
2 /
P
a RT b
C
=
calculate H for the isothermal compression of 1.00 mol of the gas at 300 K from 1 bar to 100 bar.

Solution:
Given: 1.00 mol, 300 K, 1 bar, 100 bar
i f
n T P P = = = =
Required: , H
From Eqs. 2.108 and 2.110 we can see that;
H
T T
P P
| |
=
|

\ .

This value is equal to zero for an Ideal Gas but it may be either positive or negative for a Real Gas. When there is expansion taking place,
the change in pressure will be negative (cooling expansion: here the change in temperature is also negative allowing the J oule-Thomson
coefficient to be positive).
Conversely, a negative corresponds to a rise in temperature upon expansion. This is interesting to note because most gases under regular
temperatures will cool when they are able to expand. Since the J oule-Thomson expansion occurs at constant enthalpy, the total differential
will be:
0
T P
H H
dH dP dT
P T
| | | |
= + =
| |

\ . \ .

It follows that:
, P
T P H
H H T
C
P T P

| | | | | |
= =
| | |

\ . \ . \ .

2-180
We have seen previously that for an ideal gas, the J oule-Thomson coefficient is equal to zero. This also indicates that the enthalpy is
independent of pressure. For real gases, we will see that the enthalpy shows some variation with pressure.
Since
H
T
P
| |
=
|
\ .
, we can use this in order to rearrange the expression given above.
,
1
it follows that,
P
T P H
T
H T P
P
H T P
H H T
C
P T P
H
T H T P
H P P H
T
T H
P P C
| | | | | |
= =
| | |

\ . \ . \ .
| |
|
| | | | | | \ .
= = =
| | |
| | \ . \ . \ .
|
\ .
| | | | | |
= =
| | |

\ . \ .
\ .

We are given that:
1 2 /
T P P
H a RT b
C P C
| |
= =
|
\ .
which then means that we determine the enthalpy change for the isothermal compression
by using the expression for the total differential. Take note that in Chapter 1 there is a table (Table 1.5) which provides the Van der Waals
constants for many gases. For simplicity, we will assume that we are working with hydrogen gas. (This is a good choice since for H
2
is
positive.)
2-181
6 2
3 3 1

0.0248 Pa m mol
0.0266 10 m mol
0
2 1
0
Assuming to be independent of temperature,
2
2
2
f
i
T P
P
p
P
P
a
b
H H
dH dP dT
P T
a
dH b dP dT
RT C
C
a
dH b dP
RT
a
dH b dP
RT
a
H b
RT

=
=
| | | |
= + =
| |

\ . \ .
| |
= + =
|
\ .
| |
=
|
\ .
| |
=
|
\ .
| |
=
\ .

( )
( )
2
f i
f i
P P
a
H b P P
RT
|
| |
=
|
\ .

6 2
3 3 1
2 0.0248 Pa m mol
0.0266 10 m mol H

=
( )
1
8.3145 J K
1
mol
( )
300 K
( )
( )
5 3
100 1 bar
1 bar 10 Pa, 1 Pa m 1 J
| |
|

|
\ .
= =

3 3 1
2 0.0248 J
0.0266 10 m mol H

=
( )
3 1
m mol
8.3145 J
1 1
K mol

( )
300 K
( )
( )
( )
5
6 3 1 5
1
1
100 1 10 Pa
6.715 060 036 10 m mol 99 10 Pa
66.479 094 35 J mol
66.5 J mol
H
H
H

| |
|

|
\ .
=
=
=


CHAPTER
3
3
The Second and Third Laws of
Thermodynamics

Physical Chemistry
Electronic Edition

Chapter 3: The Second and Third Laws of Thermodynamics The Carnot Cycle (see also Section 3.1)
3-2
Chapter 3
The Carnot Cycle (see also Section 3.1)
3.1. The accompanying diagram represents a reversible Carnot cycle for an ideal gas:

a. What is the thermodynamic efficiency of the engine?
b. How much heat is rejected at the lower temperature, 200 K, during the isothermal compression?
c. What is the entropy increase during the isothermal expansion at 1000 K?
d. What is the entropy decrease during the isothermal compression at 200 K?
e. What is the overall entropy change for the entire cycle?
f. What is the increase in Gibbs energy during the process A B?

Solution

3.2. An engine operates between 125 C and 40 C. What is the minimum amount of heat that must be withdrawn from the reservoir to
obtain 1500 J of work?

Solution
Chapter 3: The Second and Third Laws of Thermodynamics The Carnot Cycle (see also Section 3.1)
3-3

3.3. a. Figure 3.2 shows a Carnot cycle in the form of a pressure-volume diagram. Sketch the corresponding entropy-temperature
diagram, labeling the individual steps A B (isotherm at T
h
), B C (adiabatic), C D (isotherm at T
c
), and D A (adiabatic).
b. Suppose that a reversible Carnot engine operates between 300 K and a higher temperature T
h
. If the engine produces 10 kJ of
work per cycle and the entropy change in the isothermal expansion at T
h
is 100 J K
1
, what are q
h
, q
c
, and T
h
?

Solution

3.4. The following diagram represents a reversible Carnot cycle for an ideal gas:

b. How much heat is absorbed at 400 K?
c. How much heat is rejected at 300 K?
d. What is the entropy change in the process A B?
e. What is the entropy change in the entire cycle?
f. What is the Gibbs energy change in the process A B?
g. In order for the engine to perform 2 kJ of work, how much heat must be absorbed?

Solution

Chapter 3: The Second and Third Laws of Thermodynamics Entropy Changes
3-4
3.5. Suppose that an iceberg weighing 10
9
kg were to drift into a part of the ocean where the temperature is 20 C. What is the maximum
amount of work that could be generated while the iceberg is melting? Assume the temperature of the iceberg to be 0 C. The latent
heat of fusion of ice is 6.025 kJ mol
1
.

If the process occurred in one day, what would be the power produced?

Solution

3.6. Show that the change in the internal energy of an ideal gas during an isothermal expansion is zero, i.e., 0.
T
U
V
| |
=
|
\ .

Compare this result to Eq. 3.148 for a van der Waals gas.

Solution

Entropy Changes
3.7. Calculate the entropies of vaporization in J K
1
mol
1
of the following substances, from their boiling points and enthalpies of
vaporization:
Boiling Point/K v
ap
H/kJ mol
1

C
6
H
6
353 30.8
CHCl
3
334 29.4
H
2
O 373 40.6
C
2
H
5
OH 351 38.5

In terms of the structures of the liquids, suggest reasons for the higher values observed for H
2
O and C
2
H
5
OH.

Solution

3.8. Calculate the standard entropies of formation of (a) liquid methanol and (b) solid urea, making use of the absolute entropies listed in
Table 3.2 (p. 120).

Solution

3-5
3.9. Calculate the standard entropies for the following reactions at 25 C:
a. N
2
(g) +3H
2
(g) 2NH
3
(g)
b. N
2
O
4
(g) 2NO
2
(g)

Solution

3.10. Calculate the standard entropy for the dissociation of H
2
(g) into atomic hydrogen 2[H(g)] at 298.15 K and 1273.15 K.
1 1
/J K mol :
P
C
H
2
(g), 28.824; H(g), 20.784.

Solution

3.11. One mole of an ideal gas, with
,
3
,
2
V m
C R = is heated (a) at constant pressure and (b) at constant volume, from 298 K to 353 K.
Calculate S for the system in each case.

Solution

3.12. One mole each of N
2
and O
2
and
1
2
mol of H
2
, at 25 C and 1 atm pressure, are mixed isothermally; the final total pressure is 1 atm.
Calculate S, on the assumption of ideal behavior.

Solution

3.13. Initially 1 mol of O
2
is contained in a 1-liter vessel, and 5 mol of N
2
are in a 2-liter vessel; the two vessels are connected by a tube
with a stopcock. If the stopcock is opened and the gases mix, what is the entropy change?

Solution

3.14. Calculate the entropy of mixing per mole of air, taking the composition by volume to be 79% N
2
, 20% O
2
, and 1% Ar.

Solution

3.15. From the data given in Table 3.2 (p. 120), calculate the standard entropy of formation
f
S of liquid ethanol at 25 C.

Solution
3-6

3.16. a. One mole of an ideal gas at 25 C is allowed to expand reversibly and isothermally from 1 dm
3
to 10 dm
3
. What is S for the gas,
and what is S for its surroundings?
b. The same gas is expanded adiabatically and irreversibly from 1 dm
3
to 10 dm
3
with no work done. What is the final temperature
of the gas? What is S for the gas, and what is S for the surroundings? What is the net S?

Solution

3.17. One mole of liquid water at 0.00 C and 1 atm pressure is turned into steam at 100.0 C and 1 atm pressure by the following two
paths:
a. Heated at constant pressure to 100.0C, and allowed to boil into steam (
vap
H =40.67 J mol
1
at this temperature).
b. Pressure lowered to 0.006 02 atm so that water evaporates to steam at 0 C (
vap
H =44.92 J mol
1
at this temperature), heated at
the constant pressure of 0.006 02 atm to 100.0 C, and compressed at 100.0 C to 1 atm pressure.
Calculate the entropy change along each path and verify that they are the same, thus proving that S is a state property. The C
P,m

for liquid water and water vapor can be found in Table 2.1. [The paths and the enthalpies of vaporization are adapted from Table
6.1, Gordon M. Barrow, Physical Chemistry, 5th Ed., New York: McGraw-Hill, 1988.]

Solution

3.18. Predict the signs of the entropy changes in the following reactions when they occur in aqueous solution.
a. Hydrolysis of urea: H
2
NCONH
2
+H
2
O CO
2
+2NH
3

b. H
+
+OH

H
2
O
c. CH
3
COOH CH
3
COO
+H
+

d.
2
2 3 2 3 2 2 3 3
CH BrCOOCH +S O CH (S O )COOCH +Br
Solution

3.19. Obtain a general expression, in terms of the molar heat capacity C
P,m
and temperature T
1
and T
2
, for the entropy increase of n mol of
a gas (not necessarily ideal) that is heated at constant pressure so that its temperature changes from T
1
to T
2
. To what does your
expression reduce if the gas is ideal?

Solution

3.20. Initially 5 mol of an ideal gas, with C
V,m
=12.5 J K
1
mol
1
, are at a volume of 5 dm
3
and a temperature of 300 K. If the gas is
heated to 373 K and the volume changed to 10 dm
3
, what is the entropy change?

Solution
3-7

*3.21. At 100 C 200 g of mercury are added to 80 g of water at 20 C in a vessel that has a water equivalent of 20 g. The specific heat
capacities of water and mercury may be taken as constant at 4.18 and 0.140 J K
1
g
1
, respectively. Calculate the entropy change of
(a) the mercury; (b) the water and vessel; (c) the mercury, water, and vessel together.

Solution

*3.22. At 0 C 20 g of ice are added to 50 g of water at 30C in a vessel that has a water equivalent of 20 g. Calculate the entropy changes
in the system and in the surroundings. The heat of fusion of ice at 0 C is 6.02 kJ mol
1
, and the specific heat capacities of water and
ice may be taken as constant at 4.184 and 2.094 J K
1
g
1
, respectively, and independent of temperature.

Solution

*3.23. Calculate the increase in entropy of 1 mol of nitrogen if it is heated from 300 K to 1000 K at a constant pressure of 1 atm; use the
C
P
data in Table 2.1.

Solution

*3.24. The entropy change for the isothermal expansion of an ideal gas at 300 K from a particular state A to a state B is 50 J K
1
. When an
expansion was performed, the work done by the system was 6 kJ . Was the process reversible or irreversible? If the latter, calculate
the degree of irreversibility (i.e., the ratio of the work done to the reversible work).

Solution

3.25. One mole of water is placed in surroundings at 3 C, but at first it does not freeze (it remains as supercooled water). Suddenly it
freezes. Calculate the entropy change in the system during the freezing, making use of the following data:
1 1
,
1 1
,
(water) 75.3J K mol
(ice) 37.7J K mol
P m
P m
C
C
=
=

1
(ice water) 6.01kJ mol at0C
f
H =

The two C
P
values can be assumed to be independent of temperature. Also, calculate the entropy change in the surroundings, and the
net entropy change in the system and surroundings.

Solution
3-8

3.26. 200 cm
3
of a 0.5 m solution of sucrose is diluted to 1 dm
3
by the addition of 800 cm
3
of water. Assume ideal behavior and calculate
the entropy change.

Solution

3.27. One liter of a 0.1 M solution of a substance A is added to 3 liters of a 0.05 M solution of a substance B. Assume ideal behavior and
calculate the entropy of mixing.

Solution

3.28. Ten moles of water at 60 C are mixed with an equal amount of water at 20 C. Neglect any heat exchange with the surroundings
and calculate the entropy change. The heat capacity of water may be taken to be 75.3 J K
1
mol
1
and independent of temperature.

Solution

3.29. A vessel is divided by a partition into two compartments. One side contains 5 moles O
2
at 1 atm pressure; the other, 5 moles N
2
at 1
atm pressure. Calculate the entropy change when the partition is removed.

Solution

3.30. One mole of liquid water at 0 C is placed in a freezer having a temperature of 12 C. The water freezes and the ice cools to 12
C. Making use of the data given in Problem 3.25, calculate the change in entropy in the system and in surroundings (the freezer),
and the net entropy change.

Solution

3.31. One mole of liquid water at 0 C is placed in a freezer which is maintained at 10 C. Carry out the same calculations as for Problem
3.30.

Solution

3.32. Two moles of water at 60 C are added to 4 mol of water at 20 C. Calculate the entropy change, assuming that there is no loss of
heat to the surroundings. The heat capacity of water is 75.3 J K
1
mol
1
.

Solution
Chapter 3: The Second and Third Laws of Thermodynamics Gibbs and Helmholtz Energies
3-9

3.33. One mole of an ideal gas is initially at 10 bar and 298 K. It is allowed to expand against a constant external pressure of 2 bar to a
final pressure of 2 bar. During this process, the temperature of the gas falls to 253.2 K. Find U, H, S, S
therm
, and S
univ
for the
process. Assume that the thermal surroundings remain at 298 K throughout. Devise at least three different paths to accomplish this
change and show that no matter which path is used, the desired values are the same.

Solution

3.34. Five moles of water at 50 C are placed in a refrigerator maintained at 3 C. Calculate S for the system and for the environment,
and the net entropy change, taking C
P
for water at 75.3 J K
1
mol
1

Solution

3.35. Problem 2.32 of Chapter 2 was concerned with dropping (a) one ice cube, (b) 10 ice cubes, each weighing 100 g, into 1 kg of water
at 20 C. Calculate the entropy change in each case. (H
fus
of ice at 0 C is 6.026 kJ mol
1
; C
P,m
for water is 75.3 J K
1
mol
1
.)

Solution

3.36. The absolute entropy of nitrogen at its vaporization point of 77.32 K and exactly 1 bar is 151.94 J K
1
mol
1
. Using the expression
for C
P,m
for nitrogen given in Table 2.1, find the entropy of the gas at 800.0 K and 1 bar.

Solution
Gibbs and Helmholtz Energies
3.37. Calculate G at 25 C for the following fermentation reaction:
6 12 6 2 5 2
glucose ethanol
C H O (aq) 2C H OH(aq) 2CO (g) +
The standard Gibbs energies of formation of glucose, ethanol, and carbon dioxide are given in Appendix D.
Also use the data in Appendix D to calculate S for the fermentation reaction.

Solution

3.38. The latent heat of vaporization of water at 100 C is 40.6 kJ mol
1
and when 1 mol of water is vaporized at 100 C and 1 atm
pressure, the volume increase is 30.19 dm
3
. Calculate the work done by the system, the change in internal energy U, the change in
Gibbs energy G and the entropy change S.
Solution
3-10

3.39. On pages 115116 we worked out the S values for the freezing of water at 0 C and at 10 C. What are the corresponding G
values?

Solution

3.40. At 25 C 1 mol of an ideal gas is expanded isothermally from 2 to 20 dm
3
. Calculate U, H, S, A, and G. Do the values depend
on whether the process is reversible or irreversible?

Solution

3.41. The values of H and S for a chemical reaction are 85.2 kJ mol
1
and 170.2 J K
1
mol
1
, respectively, and the
values can be taken to be independent of temperature.
a. Calculate G for the reaction at (a) 300 K, (b) 600 K, and (c) 1000 K.
b. At what temperature would G be zero?

Solution

3.42. The standard Gibbs energy for the combustion,
c
G, of methane has been measured as 815.04 kJ mol
1
at 25.0 C and 802.57
kJ mol
1
at 75.0 C. Assuming that Eq. 3.169 applies and that
c
G changes linearly with temperature in this range, estimate the
enthalpy of combustion at the midpoint of this temperature range, i.e., 50.0 C.

Solution

3.43. The heat of vaporization of water at 25 C is 44.01 kJ mol
1
, and the equilibrium vapor pressure at that temperature is 0.0313 atm.
Calculate S, H, and G when 1 mol of liquid water at 25 C is converted into vapor at 25 C and a pressure of 10
5
atm, assuming
the vapor to behave ideally.
Solution

3.44. For each of the following processes, state which of the quantities U, H, S, A, and G are equal to zero:
a. Isothermal reversible expansion of an ideal gas.
b. Adiabatic reversible expansion of a nonideal gas.
c. Adiabatic expansion of an ideal gas through a throttling valve.
3-11
d. Adiabatic expansion of a nonideal gas through a throttling valve.
e. Vaporization of liquid water at 80 C and 1 bar pressure.
f. Vaporization of liquid water at 100 C and 1 bar pressure.
g. Reaction between H
2
and O
2
in a thermally insulated bomb.
h. Reaction between H
2
SO
4
and NaOH in dilute aqueous solution at constant temperature and pressure.

Solution

3.45. Calculate the change G
m
in the Gibbs energy of 1 mol of liquid mercury initially at 1 bar pressure if a pressure of 1000 bar is
applied to it. The process occurs at the constant temperature of 25 C, and the mercury may be assumed to be incompressible and to
have a density of 13.5 g cm
3
.

Solution

3.46. The entropy of argon is given to a good approximation by the expression
S
m
/J K
1
mol
1
=36.36 +20.79 ln(T/K)
Calculate the change in Gibbs energy of 1 mol of argon if it is heated at constant pressure from 25 C to 50 C.

Solution

3.47. Calculate the absolute entropy of SO
2
(g) at 300.0 K and 1 bar given the following information: S(15.0 K) =1.26 J K
1
mol
1
,
C
P,m
(s) =32.65 J K
1
mol
1
, T
fus
= 197.64 K,
fus
H =7 402 J mol
1
, C
P,m
(l) =87.20 J K
1
mol
1
, T
vap
= 263.08 K,
vap
H =24 937
J mol
1
, C
P,m
(g) =39.88 J K
1
mol
1
.

Solution

3.48. Initially at 300 K and 1 bar pressure, 1 mol of an ideal gas undergoes an irreversible isothermal expansion in which its volume is
doubled, and the work it performs is 500 J mol
1
. What are the values of q, U, H, G, and S? What would q and w be if the
expansion occurred reversibly?
Solution

*3.49. At 100 C 1 mol of liquid water is allowed to expand isothermally into an evacuated vessel of such a volume that the final pressure
is 0.5 atm. The amount of heat absorbed in the process was found to be 30 kJ mol
1
. What are w, U, H, S, and G?

Solution

3-12
*3.50. Water vapor can be maintained at 100 C and 2 atm pressure for a time, but it is in a state of metastable equilibrium and is said to be
supersaturated. Such a system will undergo spontaneous condensation; the process is:
H
2
O(g, 100 C, 2 atm) H
2
O(l, 100 C, 2 atm)
Calculate H
m
, S
m
, and G
m
. The molar enthalpy of vaporization
vap
H
m
is 40.60 kJ mol
1
; assume the vapor to behave ideally
and liquid water to be incompressible.

Solution

*3.51. Initially at 300 K and 10 atm pressure, 1 mol of a gas is allowed to expand adiabatically against a constant pressure of 4 atm until
equilibrium is reached. Assume the gas to be ideal with:
C
P,m
/J K
1
mol
1
=28.58 +1.76 10
2
T/K
and calculate U, H, and S.

Solution

3.52. Calculate H, G, and S for the reaction
CH
4
(g) +2O
2
(g) O
2
(g) +2H
2
O(l)
making use of the data in Appendix D.

Solution

3.53. The following is a set of special conditions:
a. True only for an ideal gas.
b. True only for a reversible process.
c. True only if S is the total entropy (system +surroundings).
d. True only for an isothermal process occurring at constant pressure.
e. True only for an isothermal process occurring at constant volume.
Consider each of the following statements, and indicate which of the above conditions must apply in order for the statement to be
true:
a. U =0 for an isothermal process.
b. H =0 for an isothermal process.
c. The total S =0 for an adiabatic process.
d. S > 0 for a spontaneous process.
e. G < 0 for a spontaneous process.

Solution
Chapter 3: The Second and Third Laws of Thermodynamics Energy Conversion
3-13

3.54. Calculate the entropy and Gibbs energy changes for the conversion of 1 mol of liquid water at 100 C and 1 bar pressure into vapor
at the same temperature and a pressure of 0.1 bar. Assume ideal behavior. The heat of vaporization of water at 100 C is 40.6
kJ mol
1
.

Solution

3.55. In the bacterium nitrobacter the following reaction occurs:

2 2 3
1
NO + O NO
2

Use the data in Appendix D to calculate H, G, and S for the reaction.

Solution

Energy Conversion
3.56. At 100 atm pressure water boils at 312 C, while at 5 atm it boils at 152 C. Compare the Carnot efficiencies of 100-atm and 5-atm
steam engines, if T
c
is 30 C.

Solution

3.57. A cooling system is designed to maintain a refrigerator at 4 C in a room at 20 C. If 10
4
J of heat leaks into the refrigerator each
minute, and the system works at 40% of its maximum thermodynamic efficiency, what is the power requirement in watts? [1 watt
(W) =1 J s
1
.]

Solution

3.58. A heat pump is employed to maintain the temperature of a house at 25 C. Calculate the maximum performance factor of the pump
when the external temperature is (a) 20 C, (b) 0 C, and (c) 20 C.

Solution

Chapter 3: The Second and Third Laws of Thermodynamics Thermodynamic Relationships
3-14
3.59. A typical automobile engine works with a cylinder temperature of 2000 C and an exit temperature of 800 C. A typical octane fuel
(molar mass =114.2 g mol
1
) has an enthalpy of combustion of 5500 kJ mol
1
and 1 dm
3
(0.264 U.S. gal) has a mass of 0.80 kg.
Calculate the maximum amount of work that could be performed by the combustion of 10 dm
3
of the fuel.

Solution

3.60. The temperature of a building is maintained at 20 C by means of a heat pump, and on a particular day the external temperature is 10
C. The work is supplied to the heat pump by a heat engine that burns fuel at 1000 C and operates at 20 C. Calculate the
performance factor for the system (i.e., the ratio of the heat delivered to the building to the heat produced by the fuel in the heat
engine). Assume perfect efficiencies of the pump and the engine.

Solution

3.61. Suppose that a refrigerator cools to 0 C, discharges heat at 25 C, and operates with 40% efficiency.
a. How much work would be required to freeze 1 kg of water (
f
H =6.02 kJ mol
1
)?
b. How much heat would be discharged during the process?

Solution
Thermodynamic Relationships
3.62. Show that (a)
,
T
U T P
V

| |
=
|
\ .
and (b) ( ),
T
U
V P T
P

| |
=
|
\ .
where
1
,
T
V
V P
| |
=
|
\ .
is called the isothermal compressibility
coefficient.
Usetherelationship .
V T P
P P V
T V T
( | | | | | |
=
| | | (
\ . \ . \ .

Solution

3.63. Derive an equation of state from
dH =T dS +V dP
by taking the partial derivative with respect to P at constant temperature. Then use the appropriate Maxwell relation and the
definition of to express the partial in terms of easily measured quantities.

Solution
3-15

3.64. Derive expressions for (a) and (b) for an ideal gas.

Solution

*3.65. Suppose that a gas obeys the van der Waals equation
2
)
m
m
a
P V b RT
V
| |
+ =
|
\ .

Prove that:
2
m m
T
U a
V V
| |
=
|
\ .

Solution

*3.66. Obtain an expression for the J oule-Thomson coefficient for a gas obeying the equation of state:
P(V
m
b) =RT
in terms of R, T, P, V
m
, and C
P,m
.

Solution

*3.67. Derive the following equations:
a.
2
2
P
G
C T
T
| |
=
|
\ .

b.
2
2
P
T
P
C V
T
P T
| | | |
=
| |

\ .
\ .

Solution

*3.68. Starting with the definition of the Helmholtz energy, A =U TS, prove that the change in Helmholtz energy for a process at constant
temperature is the total work (PV and non-PV). (This relationship holds without any restriction as to volume or pressure changes.)

Solution

3-16
*3.69. Prove that if a gas obeys Boyles law and if in addition (U/V)
T
=0, it must obey the equation of state PV =constant T.

Solution

*3.70. Derive the relationship
U
S P
V T
| |
=
|
\ .

and confirm that it applies to an ideal gas.

Solution

3.71. Starting from Eq. 3.160,
a. Show that
2
1
2
2
1
In ,where .
P
m
P
PV f Z
dP Z
P P RT
| |
| |
= =
| |
\ .
\ .

b. For a nonideal gas, the equation of state is given as PV
m
=RT +(b A/RT
2/3
)P (see Example 1.6, p. 42). Derive an expression to
find the fugacity of the gas at a given temperature and pressure when the constants b and A are given.

Solution

3.72. The van der Waals constants for methane in older units are a =2.283 L
2
bar mol
2
and b =0.0428 L mol
1
. Expressing the
compression factor as (see Problem 1.52 in Chapter 1):
2
2
1
1 ,
a b
Z b P P
RT RT RT
| | | |
= + +
| |
\ . \ .

Find the fugacity of methane at 500 bar and 298 K.

Solution

Chapter 3: The Second and Third Laws of Thermodynamics Essay Questions
3-17
Essay Questions
3.73. The frying of a hens egg is a spontaneous reaction and has a negative Gibbs energy change. The process can apparently be reversed
by feeding the fried egg to a hen and waiting for it to lay another egg. Does this constitute a violation of the second law? Discuss.
10

3.74. Consider the following statements:
a. In a reversible process there is no change in the entropy.
b. In a reversible process the entropy change is dq
rev
/T. How must these statements be qualified so that they are correct and not
contradictory?

3.75. Consider the following statements:
a. The solution of certain salts in water involves a decrease in entropy.
b. For any process to occur spontaneously there must be an increase in entropy.
Qualify these statements so that they are correct and not contradictory, and suggest a molecular explanation for the behavior.

3.76. A phase transition, such as the melting of a solid, can occur reversibly and, therefore, S =0. But it is often stated that melting
involves an entropy increase. Reconcile these two statements.

10
In answering this question, a student commented that a hen would never eat a fried egg. We suspect she would if she were hungry and had no alternative. In any case,
let us postulate a hen sufficiently eccentric to eat a fried egg.
Chapter 3: The Second and Third Laws of Thermodynamics Solutions
3-18
Solutions
3.1. The accompanying diagram represents a reversible Carnot cycle for an ideal gas:

b. How much heat is rejected at the lower temperature, 200 K, during the isothermal compression?

c. What is the entropy increase during the isothermal expansion at 1000 K?
d. What is the entropy decrease during the isothermal compression at 200 K?
e. What is the overall entropy change for the entire cycle?
f. What is the increase in Gibbs energy during the process A B?

Solution:
Given: Carnot Cycle Diagram for Ideal Gas
3-19
Required: see above
a) The efficiency for an engine is given by Eq. 3.21 which states that:
e
h
R
w
q
= =
( )
2
1
ln
h c
V
T T
V
| |
|
\ .
R
2
1
ln
h
V
T
V
| |
|
\ .
( )
e
1000 200
e 0.8
1000
e 80%
h c
h
T T
T
= =
=

b) We can determine the amount of heat rejected at the lower temperature by making use of Eq. 3.23 which is that of a reversible engine.
e and therefore,
200 K
150 kJ
h c
h
h c h c h h
h h c c
c
c h
h
c
q q
q
T T q q T q
T q T q
T
q q
T
q
+
=
+
= =
| |
=
|
\ .
=
1000 K
heat rejected 30 kJ =

c) The increase in entropy for the system throughout this process can be defined by Eq. 3.55 which gives,
3-20
rev
inc
inc
1
inc
150 000 J
1000 K
150 J K
h
h
dq
S
T
q
S
T
S
S

=
=
=
=

d) We may use the same expression given in part C in order to determine the entropy decrease.
rev
decr
decr
1
decr
30 000 J
200 K
150 J K
c
c
dq
S
T
q
S
T
S
S

=
=
=
=

e) We must simply take the difference between the entropies calculated in parts C and D.
( )
inc decr
1
150 150 J K
0
S S S
S
S
=
=
=

f) Using the well known equation for the Gibbs Free Energy:
3-21

1
150 J K and 0
0 1000 K
S H
G H T S
G
= =
=
=
( )
1
150 J K
( )
150 000 J
150 kJ
G
G
=
=


3-22
3.2. An engine operates between 125 C and 40 C. What is the minimum amount of heat that must be withdrawn from the reservoir to
obtain 1500 J of work?

Solution:
Given:
o o
1 2
40 C, 125 C, 1500 J T T w = = =
Required:
min
q
For this problem, we should start by determining the efficiency of the engine. Efficiency is given by Eq. 3.20:
( ) ( )
( )
( )
e
125 273.15 40 273.15 K
e
125 273.15 K
398.15 313.15 K
e
h c
h h
w T T
q T
= =
+ + (

=
+
=
398.15 K
e 0.213 487 379 =

Now that we have the efficiency we will be able to determine the minimum amount of heat that must be withdrawn from the reservoir to
obtain 1500 J of work.
min
min
min
min
min
e
1500 J
0.213 487 379
1500 J
0.213 487 379
7026.176 471 J
7.03 kJ
w
q
q
q
q
q
=
=
=
=
=

3-23
3.3. a. Figure 3.2 shows a Carnot cycle in the form of a pressure-volume diagram. Sketch the corresponding entropy-temperature
diagram, labeling the individual steps A B (isotherm at T
h
), B C (adiabatic), C D (isotherm at T
c
), and D A (adiabatic).
b. Suppose that a reversible Carnot engine operates between 300 K and a higher temperature T
h
. If the engine produces 10 kJ of
work per cycle and the entropy change in the isothermal expansion at T
h
is 100 J K
1
, what are q
h
, q
c
, and T
h
?

Solution:
Given: Figure 3.2,
1
1 2
300 K, , 10 kJ , 100 J K
h
T T T w S

= = = =
Required: , , and
h c h
q q T S-T diagram
a)

b) From Eq. 3.23 we are given,
3-24
or
0
0
300 K
h c h c h h
h h c c
h c
h c
h c
h
T T q q T q
T q T q
q q
T T
q q
T

= =
+ =
+ =

We know that the work performed by the system is equal to:
10 kJ
h c
w q q = + =
We can determine the change in entropy which will then enable us to find q
c
and q
h
.
1
1
10 kJ
thus,
100 J K
100 J K 0
300 K
300 K
h c
h
h
h
h
h
h
c
c
w q q
q q
S S
T T
q
S
T
q
q
= + =
= =
= =
+ =
1
100 J K
=
( )
30 000 J
30 kJ
10 kJ 10 kJ 30 kJ
c
c
h c h
q
q
q q q
=
=
+ = =

( )
40 kJ
40 kJ
300 K
h
h
h c
c
q
q
T T
q
=
= =
30 kJ
400 K
h
T =

3-25
3.4. The following diagram represents a reversible Carnot cycle for an ideal gas:
b. How much heat is absorbed at 400 K?
c. How much heat is rejected at 300 K?
d. What is the entropy change in the process A B?
e. What is the entropy change in the entire cycle?
f. What is the Gibbs energy change in the process A B?
g. In order for the engine to perform 2 kJ of work, how much heat must be absorbed?

Solution:
Given: Carnot Cycle for Ideal Gas
Required: see above
a) According to Eq. 3.21:
3-26
( )
e
400 300 K
e
h c
h
T T
T
=
400 K
e 0.25
e 25%
=
=

b) The heat absorbed can also be found using a rearrangement of the previously given equation.
( )
( )
( )
e
800 J
400 K
e 0.25
400 K 3200 J
400 K 3.2 kJ
h c
h h
h
h
h
T T w
T q
w
q
q
q
= =
= =
=
=

c) The heat rejected can be found by the following:

rejected
rejected
rejected
rejected
3200 J 800 J
2400 J
2.4 kJ
h c
q q q
q
q
q
=
=
=
=

d) The entropy change from AB can be determined by:
A B
A B
1
A B
3200 J
400 K
8 J K
h
h
q
S
T
S
S
=
=
=

3-27
e) We can say that
( ) 1
A B
S

denotes the change in entropy in going from A to B by path 1. Conversely,
( ) 2
B A
S

denotes the change in entropy
in going from B to A along path 2. The change in entropy of the second case/path is identical in magnitude but opposite in sign to the
entropy change in the first case/path. This would mean that,
( ) ( ) 2 1
B A A B
S S

= which is given by Eq. 3.35.
The total change in entropy for the system is therefore,
0 S =
f) Since we know that 0 H = , we can therefore use the equation that describes the Gibbs Free Energy in order to find the answer.
( ) ( )
1
0 400 K 8.0 J K
3200 J
3.2 kJ
G H T S
G
G
G
=
=
=
=

g) We can use the expression which defines the efficiency calculated in the first part of this question in order to determine the amount of
heat which must be absorbed.
e
e
2000 J
0.25
8000 J
8.0 kJ
h c
h h
h
h
h
h
T T w
T q
w
q
q
q
q
= =
=
=
=
=


3-28
3.5. Suppose that an iceberg weighing 10
9
kg were to drift into a part of the ocean where the temperature is 20 C. What is the maximum
amount of work that could be generated while the iceberg is melting? Assume the temperature of the iceberg to be 0 C. The latent
heat of fusion of ice is 6.025 kJ mol
1
.]]
If the process occurred in one day, what would be the power produced?

Solution:
Given: Iceberg:
9 o o 1
iceberg ocean iceberg ice
10 kg, 20 C 293.15 K, 0 C, 6.025 kJ mol
f
m T T H

= = = = =
Required: ( )
max
, 1 day w P
The heat that is transferred from the water to the melting iceberg is given by;
( )
12
1
1
11
10 g
6.025 kJ mol
18 g mol
3.347 222 222 10 kJ
fusion
m
q H
M
q
q
=
=
=

The fraction of this that can be converted into work can be determined by Eq. 3.21;
( ) ( )
( )
( )
e
20 273.15 0 273.15 K
e
20 273.15 K
293.15 273.15 K
e
h c
h
T T
T
=
+ + (

=
+
=
293.15 K
e 0.068 224 458 =

Using a different version of Eq. 2.21 we can not determine the amount of work available.
3-29
( ) ( )
11
10
10
e
e
0.068 224 458 3.347 222 222 10 kJ
2.283 624 219 10 kJ
w=2.284 10 kJ
h
h
w
q
w q
w
w
=
=
=
=

Power is simply defined as the amount of work done in a unit time. This can be easily found for a single day.
60 s 60 min 24 hrs
1 min 1 hour 1 day

10
1
5 1
86 400 s
2.283 624 219 10 kJ
86 400 s
264 308.3587 kJ s
2.643 10 kJ s
t
w
P
t
P
P
P
=
=
=
=
=


3-30
3.6. Show that the change in the internal energy of an ideal gas during an isothermal expansion is zero, i.e., 0.
T
U
V
| |
=
|
\ .

Compare this result to Eq. 3.148 for a van der Waals gas.

Solution:
Given:

0.
T
U
V
| |
=
|
\ .

Required: prove it
Let us use the thermodynamic equation of state given by Eq. 3.128 which states that:
T V
U P
P T
V T
| | | |
= +
| |

\ . \ .

From the Ideal Gas Law, we know that PV nRT = which can be slightly altered to get:
m
nRT
P
V
RT
P
V
=
=

Now taking the partial derivative of this expression with respect to temperature and keeping volume constant,
m
V m
RT
P
V
P R
T V
=
| |
=
|
\ .

This can now be substituted into Eq. 3.128 to obtain,
3-31
0
T V
T m
T T T m
U P
P T
V T
U R
P T
V V
U RT U U
P P P
V V V V
| | | |
= +
| |

\ . \ .
| | | |
= +
| |
\ .
\ .
| | | | | | | |
= + = + =
| | | |

\ . \ . \ .
\ .

3-32
3.7. Calculate the entropies of vaporization in J K
1
mol
1
of the following substances, from their boiling points and enthalpies of
vaporization:
Boiling Point/K v
ap
H/kJ mol
1

C
6
H
6
353 30.8
CHCl
3
334 29.4
H
2
O 373 40.6
C
2
H
5
OH 351 38.5

In terms of the structures of the liquids, suggest reasons for the higher values observed for H
2
O and C
2
H
5
OH.

Solution:
Given: see table above
Required:
vap
S for all species in the above table
It is possible to heat a solid sufficiently slowly at its melting point such that the equilibrium between the liquid and solid phases is hardly
disturbed. This means that the process is reversible (ie. it follows a path of successive equilibrium states) and the latent heat of melting is
also reversible.
The entropy of melting (ie. fusion) is given by Eq. 3.49:
fus
fus
fus
H
S
T
=
Given the data in the table above, we obtain:
Benzene:
3-33

fus
fus
fus
1
fus
1
fus
1 1
fus
30.8 kJ mol
353 K
30 800 J mol
353 K
87.3 J K mol
H
S
T
S
S
S
=
=
=
=

Trichloromethane:
fus
fus
fus
H
S
T
=
1
fus
1
fus
1 1
fus
29.4 kJ mol
334 K
29 400 J mol
334 K
88.0 J K mol
S
S
S

=
=
=

Water:
fus
fus
fus
1
fus
1
fus
1 1
fus
40.6 kJ mol
373 K
40 600 J mol
373 K
109 J K mol
H
S
T
S
S
S
=
=
=
=

Ethanol:
3-34
fus
fus
fus
1
fus
1
fus
1 1
fus
38.5 kJ mol
351 K
38 500 J mol
351 K
110 J K mol
H
S
T
S
S
S
=
=
=
=

A higher value for entropy is correlated to the nature of the hydrogen bonding in the latter two species.

3-35
3.8. Calculate the standard entropies of formation of (a) liquid methanol and (b) solid urea, making use of the absolute entropies listed in
Table 3.2 (p. 120).

Solution:
Given: Table 3.2
Required:
o
f
S for methanol and urea
We have to first write down the complete and balanced equations required for the individual equation. We have seen in previous chapters
that,
a) For liquid methanol:
( ) ( ) ( ) ( )
graphite 2 2 3
1
1 C 2H g O g CH OH l
2
+ +
According to Eq. 3.69 and Table 3.2;
( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
( ) ( )
o o o
o o o o o
3 2 2 graphite
o o o o o
3 2 2 graphite
o 1
products reactants
1
CH OH, l 2 H , g O , g C
2
1
CH OH, l 2 H , g O , g C
2
1
126.80 2 130.68 205.14 5.74 J K
2
f f f
f f f f f
f f f f f
f
S S S
S S S S S
S S S S S
S

=
| |
= + +
|
\ .
=
( | |
=
| (
\ .

1
o 1 1
mol
242.87 J K mol
f
S

=

b) For the formation of solid urea:
( ) ( ) ( ) ( ) ( )
graphite 2 2 2 2 2
1
2 C 2H g O g N g H NCONH s
2
+ + +
According to Eq. 3.69 and Table 3.2;
3-36
( ) ( )
( ) ( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) ( )
o o o
o o o o o o
2 2 2 2 2 graphite
o o o o o o
2 2 2 2 2 graphite
products reactants
1
H NCONH , s N , g O , g 2 H , g C
2
1
H NCONH , s N , g O , g 2 H , g C
2
f f f
f f f f f f
f f f f f f
S S S
S S S S S S
S S S S S S
=
| |
= + + +
|
\ .
=

( ) ( ) ( )
o 1 1
o 1 1
1
104.60 191.61 205.14 2 130.68 5.74 J K mol
2
456.68 J K mol
f
f
S
S

( | |
=
| (
\ .
=

3-37
3.9. Calculate the standard entropies for the following reactions at 25 C:
a. N
2
(g) +3H
2
(g) 2NH
3
(g)
b. N
2
O
4
(g) 2NO
2
(g)

Solution:
Given: N
2
(g) +3H
2
(g) 2NH
3
(g)
N
2
O
4
(g) 2NO
2
(g)
Required:
o
S for both reactions
We will first write the balanced equations for each reaction. Then apply Eq. 3.69 in order to determine the standard entropy changes for
both A and B.
a) ( ) ( ) ( ) ( )
2 2 3
1 N g 3H g 2NH g +
Using Eq. 3.69 together with data from Table 3.2 we obtain,
( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
o o o
o o o o
3 2 2
o o o o
3 2 2
o 1 1
o 1 1
products reactants
2 NH , g 3 H , g N , g
2 NH , g 3 H , g N , g
2 192.45 3 130.68 191.61 J K mol
198.75 J K mol
S S S
S S S S
S S S S
S
S

=
= +
=
= (

=

b) ( ) ( ) ( )
2 4 2
2 N O g 2NO g
Using Eq. 3.69 together with data from Appendix D we obtain,
3-38
( ) ( )
( ) ( )
( )
2 2 4
1 1
1 1
products reactants
2 NO , g N O , g
2 240.1 304.2 J K mol
176 J K mol
o o o
o o o
o
o
S S S
S S S
S
S

=
=
=
=


3-39
3.10. Calculate the standard entropy for the dissociation of H
2
(g) into atomic hydrogen 2[H(g)] at 298.15 K and 1273.15 K.
1 1
/J K mol :
P
C
H
2
(g), 28.824; H(g), 20.784.

Solution:
Given: dissociation of Hydrogen: ( ) ( )
1 1
1 2 2
298.15 K 1273.15 K, /J K mol :H g ,28.824; H g , 20.784
P
T T C
= =
Required:
o
r
S
As in the last few problems, we will first write the balanced equation for the reaction.
( ) ( ) ( )
2
1 H g 2H g
First, it is important that we determine the entropy change at the initial temperature for the dissociation of hydrogen gas. Using this value,
we can calculate the increase in entropy for the overall increase in temperature (ie. to 1273.15K ). Assuming that the heat capacity is
constant throughout this temperature range and using the data given in Appendix D;
( ) ( )
( ) ( )
( ) ( )
o o o
o o o
2
o 1 1
o 1 1
products reactants
2 H, g H , g
2 114.717 130.680 J K mol
98.754 J K mol
S S S
S S S
S
S

=
=
= (

=

Beginning with Eq. 3.55, it can be integrated to yield:
2 2
1 1
rev
,
2 1 ,
V m
T V
V m
T V
dq dT dV
dS nC nR
T T V
dT dV
S S S n C nR
T V
= = +
= = +

However, we are working under constant pressure, not constant volume so we need formulate an expression in terms of C
P,m
. When the
heat capacity is independent of temperature, we may further simplify to:
3-40
2 2
,
1 1
ln ln
V m
T V
S nC nR
T V
= +
An easier way to do this is to take Eq. 2.50 (Chapter 2) and instead of writing it in terms of enthalpy, we switch the units to entropy of
dissociation. This substitution leads to determine the entropy changes at different temperatures providing that the first has already been
found.
( ) ( )
( ) ( )
( ) ( )
2
1
2
1
2
1
2 1
o
o o r
r 2 r 1
o
o o r
r r
1273.15 K 298.15 K
T
m m P
T
T
P
T
T
P
T
H T H T C dT
C
S T S T dT
T
C
S S dT
T
=
= +

Where,
o o
r , P i P i
i
C v C =
for the reaction. Again, the heat capacity is independent of temperature therefore;
( ) ( )
( ) ( ) ( )
( )
( )
2
1
o o
r r ,
o 1 1 1 1
r
o 1 1
r
o
r
1273.15 K 298.15 K
1273.15
1273.15 K 98.754 J K mol 2 20.784 28.824 J K mol ln
298.15
1273.15
1273.15 K 98.754 12.744ln J K mol
298.15
1273.15 K 98.7
T
i P i
i
T
dT
S S v C
T
S
S
S

= +
( = +

(
= +
(

=

| |
( )
1 1
o 1 1
r
54 18.499 862 J K mol
1273.15 K 117.25 J K mol S

+
=


3-41
3.11. One mole of an ideal gas, with
,
3
,
2
V m
C R = is heated (a) at constant pressure and (b) at constant volume, from 298 K to 353 K.
Calculate S for the system in each case.

Solution:
Given: Ideal Gas:
, 1 2
3
1 mol, , 298 K, 353 K
2
V m
n C R T T = = = =
Required:
m
S in each case
a) For one mole of Ideal Gas at constant pressure and using Eq. 3.55:
rev
, V m
dq dT dV
dS nC nR
T T V
= = +
It can then be integrated to yield,
2 2
1 1
rev
,
2 1 ,
V m
T V
V m
T V
dq dT dV
dS nC nR
T T V
dT dV
S S S n C nR
T V
= = +
= = +

Since we are working at constant pressure, we will find that;
3-42
2 2
1 1
2 2
1 1
2
1
,
, ,
, , ,
, , ,
,
353
,
298
1 1
or
3
given that and ;
2
3 5
2 2
ln
5 353
ln
2 298
3.52 J K mol
T V
V m
T V
T T
V m P m
m m
T T
V m P m V m
V m P m P m
T
P m
m
T
m P m
m
m
dT dV
S n C nR
T V
C C
S dT S dT
T T
C R C C R
C C R C R R R
C
S dT
T
S C T
S R
S

= +
= =
= =
= = + =
=
=
=
=

b) Using the same method for one mole of Ideal Gas at constant volume:
2
1
,
,
353
,
298
1 1

3
given that
2
ln
3 353
ln
2 298
2.11 J K mol
T
V m
m
T
V m
m V m
m
m
C
S dT
T
C R
S C T
S R
S

=
=
=
=
=


3-43
3.12. One mole each of N
2
and O
2
and
1
2
mol of H
2
, at 25 C and 1 atm pressure, are mixed isothermally; the final total pressure is 1 atm.
Calculate S, on the assumption of ideal behavior.

Solution:
Given:
2 2 2
o
H N O tot
1
mol, 1 mol, 1 mol, 25 C, 1 atm, 1 atm
2
n n n T P P = = = = = =
Required: ln
MIX i i
i
S R x x =

Total number of moles: 1+1+0.5 =5/2

Mole fractions are

2 2 2
H N O
0.5 1 1
; ; ;
2.5 2.5 2.5
n n n = = =

| |
1 1 2 2 2 2
ln ln ln ln
5 5 5 5 5 5
8.314 0.3219 0.3665 0.3665 8.77 e.u.
MIX i i
i
MIX
S R x x R
S
(
= = + +
(

= =

This is the molar entropy of mixing. For 2,5 moles,

-1
8.77 e.u. 2.5 moles 21.93 J K
MIX
S = =


3-44
3.13. Initially 1 mol of O
2
is contained in a 1-liter vessel, and 5 mol of N
2
are in a 2-liter vessel; the two vessels are connected by a tube
with a stopcock. If the stopcock is opened and the gases mix, what is the entropy change?

Solution:
Given:
2 2 2 2
O O N N
1 mol, 1 litre, 5 mol, 2 litre n V n V = = = =
Required:
mix
S
In this instance we will assume that both the oxygen and nitrogen behave ideally and are initially at equal pressure. When we allow the
gases to mix reversibly, the volume will eventually come to equilibrium and we will be able to determine the entropy changes for either
species according to Eq. 3.58 and Eq. 3.59:
( )
2 2
2 2
2
2
O N
O O
O
O
1 ln
1.0 mol
V V
S n R
V
S
+
=
=
( )
1 1
8.3145 J K mol

( )
( ) 1 2 L
ln
+
1 L
2
1
O
9.134 411 874 J K S

=

( )
2 2
N O
1
1
1
16.856 198 21 9.134 411 874 J K
25.990 610 08 J K
25.99 J K
S S S
S
S
S
= +
= +
=
=

( )
2 2
2 2
2
2
N O
N N
N
N
1 ln
5.0 mol
V V
S n R
V
S
+
=
=
( )
1 1
8.3145 J K mol

( )
( ) 2 1 L
ln
+
2 L
2
1
N
16.856 198 21 J K S

=
3-45
3.14. Calculate the entropy of mixing per mole of air, taking the composition by volume to be 79% N
2
, 20% O
2
, and 1% Ar.

Solution:
Given: Air: Composition 79% N
2
, 20% O
2
, and 1% Ar
Required:
mix
S for air
Since we are given the relative approximations for each of the species in air, we can start off by calculating the respective mole fractions.
This concept was seen in Chapter 1.
i
i
n
x
n
=
Where,
i
x is the mole fraction,
i
n is the number of moles per species and n is the total number of moles for the system.
Nitrogen:

2
2
2
2
N
N
N
N
79
100
0.79
n
x
n
x
x
=
=
=

Oxygen:

2
2
2
2
O
O
O
O
20
100
0.20
n
x
n
x
x
=
=
=

Argon:
3-46

Ar
Ar
Ar
Ar
1
100
0.01
n
x
n
x
x
=
=
=

Since we have seen that
mix 1 2 3
S S S S = + + then we can re-write the expression to get Eq. 3.65:
( )
( ) ( ) ( )
2 2
2 2
2 2 2 2
mix 1 2 3
1
1
1 2 3
mix 1 2 3
1 2 3
mix N O Ar
N O Ar
mix N N O O Ar Ar
1 1
mix
...
1 1 1
ln ln ln
1 1 1
ln ln ln
ln ln ln
8.3145 J K mol 0.79ln0.79 0.20ln0.20 0.01ln0.01
S S S S
n
x
n n n
S n R n R n R
x x x
S n R n R n R
x x x
S R x x x x x x
S
S

= + +
=
+ +
= + +
= + +
= + +
= + + (

( )
1 1
mix
1 1
mix
4.607 562 72 J K mol
air 4.61 J K mol S

=
=


3-47
3.15. From the data given in Table 3.2 (p. 120), calculate the standard entropy of formation
f
S of liquid ethanol at 25 C.

Solution:
Given: Table 3.2
Required:
f
S ethanol
Remember that we have already completed this exercise for methanol! This should be a very quick review and makes use of Eq. 3.69. Let
us first give the balanced reaction:
( ) ( ) ( ) ( )
graphite 2 2 2 5
1
1 2C 3H g O g C H OH l
2
+ +
Let us use the data given in Table 3.2 to obtain,
( ) ( )
( ) ( ) ( ) ( )
( ) ( )
( )
o o o
o o o o o
2 5 2 2 graphite
o 1 1
o 1 1
2 5
products reactants
1
C H OH, l O , g 3 H , g 2 C
2
1
160.70 205.14 3 130.68 2 5.74 J K mol
2
C H OH 345.40 J K mol
f
f
f
f
S S S
S S S S S
S
S

=
(
= + +
(

( | |
=
| (
\ .
=


3-48
3.16. a. One mole of an ideal gas at 25 C is allowed to expand reversibly and isothermally from 1 dm
3
to 10 dm
3
. What is S for the gas,
and what is S for its surroundings?
b. The same gas is expanded adiabatically and irreversibly from 1 dm
3
to 10 dm
3
with no work done. What is the final temperature
of the gas? What is S for the gas, and what is S for the surroundings? What is the net S?

Solution:
Given: Ideal Gas:
o 3 3
1 mol, 25 C, 1 dm, 10 dm
i f
n T V V = = = =
Required: see above (there are two different conditions here)
a) Ideal Gas undergoing a reversible and isothermal expansion.
Since we are working at constant temperature, Eq. 3.51 will hold true. We will use it to calculate the entropy change for both the gas and
the surroundings.
2
1
gas
ln
1.0 mol
V
S nR
V
S
=
=
( )
1 1
8.3145 J K mol

( )
1
gas
1
gas
10
ln
1
19.144 844 J K
19.14 J K
S
S
=
=

Let us now consider Eq. 3.70 which gives the condition for equilibrium in such a system.
total syst surr
syst gas
tot gas surr
surr gas
1 1
surr
0
here, therefore,
0
19.14 J K mol
dS dS dS
dS dS
S S S
S S
S

= + =
=
= + =
=
=

b) Ideal Gas undergoing an adiabatic, irreversible expansion.
3-49
Remember from Chapter 3 that for an adiabatic process, 0, 0 U H = = (due to their temperature change dependence) and we are told that
no work is done. Since we have shown that 0 U = , we also know that there is no change in temperature throughout the reaction.
( )
0
0 therefore, 298.15 K
f i
f i
U
U mC T mC T T
U
T T
mC
=
= =
= = =

Due to the fact that
gas
S can only be calculated from the reversible process it would follow:
1 1
gas
tot gas surr
surr rev rev
surr surr
surr
net gas surr
1 1
net
19.14 J K mol
0
0
0
19.14 J K mol
S
S S S
dS dq dU
S
S S S
S

=
= + =
= = =
=
=
=


3-50
3.17. One mole of liquid water at 0.00 C and 1 atm pressure is turned into steam at 100.0 C and 1 atm pressure by the following two
paths:
a. Heated at constant pressure to 100.0C, and allowed to boil into steam (
vap
H =40.67 J mol
1
at this temperature).
b. Pressure lowered to 0.006 02 atm so that water evaporates to steam at 0 C (
vap
H =44.92 J mol
1
at this temperature), heated at
the constant pressure of 0.006 02 atm to 100.0 C, and compressed at 100.0 C to 1 atm pressure.
Calculate the entropy change along each path and verify that they are the same, thus proving that S is a state property. The C
P,m

for liquid water and water vapor can be found in Table 2.1. [The paths and the enthalpies of vaporization are adapted from Table
6.1, Gordon M. Barrow, Physical Chemistry, 5th Ed., New York: McGraw-Hill, 1988.]

Solution:
Given: see above, Table 2.1
Required: S
Since we are beginning with water at 0.00 C and 1 atm pressure and we are turning it into steam in the process, we need to consider the
entropy changes that occur when moving between states.
a) Heated at constant pressure to 100.0C, and allowed to boil into steam
( ) ( )
( )
( ) ( )
( )
( )
, l vap 1 1
1
373.15
, l
1 1
273.15
1 1
373.15 K / J K mol
40.67 J mol
373.15 K / J K mol
373.15 K
373.15 K
373.15 K 75.48 J K mol ln
f
i
T
P m
T
P m
C
H
S dT
T T
C
S dT
T
S

= +
= +
=
273.15 K
( )
1 1
1 1
0.108 991 J K mol
373.15 K 23.66 J K mol S

+
=

b) Pressure lowered to 0.006 02 atm so that water evaporates to steam at 0 C, heated at the constant pressure of 0.006 02 atm to 100.0 C
and compressed at 100.0 C to 1 atm pressure.

One should recognize that changing the pressure on the surface of a liquid does not affect the entropy of the system. We must therefore
consider the entropy changes for the vaporization process (heating the vapor at constant pressure and compressing the vapor at constant
temperature).
3-51
( ) ( )
( )
( ) ( )
( )
( )
( )
, g vap 1 1
1
373.15
, g
1 1 1 1 1
273.15
2
3
, g
373.15 K / J K mol ln
44.92 J mol
373.15 K / J K mol 8.3145 J K mol ln
373.15 K
30.54 10.29 10
f
i
T
P m f
T
i
P m
P m
C
H V
S dT R
T T V
C
P
S dT
T P
C T

= + +
= + +
= +

( )
( )
1 3
373.15
o
273.15
1 1
44.92 J mol 30.54 10.29 10
373.15
373.15 K
0.00602 atm
8.3145 J K mol ln
T
S dT
T

+
= +
+
1.00 atm
( )
o 1 1
373.15 K
373.15 0.120 380 544 J K mol 30.54ln S

= +
273.15 K
( ) ( )
( ) ( )
( )
( )
3 1 1
o 1 1
o 1 1
o
10.29 10 373.15 273.15 K 8.3145 J K mol ln0.00602
373.15 0.120 380 544 9.527 239 732 1.029 42.509 278 25 J K mol
373.15 31.832 657 97 J K mol
373.15 31.83 J
S
S
S

+ +
= + +
=
=
1 1
K mol

3-52
3.18. Predict the signs of the entropy changes in the following reactions when they occur in aqueous solution.
a. Hydrolysis of urea: H
2
NCONH
2
+H
2
O CO
2
+2NH
3

b. H
+
+OH

H
2
O
c. CH
3
COOH CH
3
COO
+H
+

d.
2
2 3 2 3 2 2 3 3

Solution:
Given: a. Hydrolysis of urea: H
2
NCONH
2
+H
2
O CO
2
+2NH
3

b. H
+
+OH

H
2
O
c. CH
3
COOH CH
3
COO
+H
+

d.
2
2 3 2 3 2 2 3 3
Required: signs of S
a) For the hydrolysis of urea:
Simply by counting the number of molecules (or moles of each species) on either side of the reaction, it is evident that there is a positive
entropy change. The system becomes more disordered with an increase in the number of components on the product side.
S = +
b) For the formation of water:
Here, we are taking two molecules and putting them together. However, we must also consider the fact that initially, we are working with
ions. These ions have electrostatic interactions with one another. Electrostriction is a property that dielectric materials possess. It is caused
by the random alignment of electrical domains. Since the water molecule has less electrostatic interactions, the system becomes more
ordered and there is a decrease in entropy.
S =
c) For the decomposition of acetic acid:
We can use the same logic as we did in the previous example in order to answer part C. Since it is the reverse reaction, thus forming
species with an increased amount of electrostriction; the system will become more disordered. This means that the change in entropy
would be positive.
3-53
S = +
d) There is a decrease in electrostriction. Therefore, the the change in entropy is positive.
S = +
3-54
3.19. Obtain a general expression, in terms of the molar heat capacity C
P,m
and temperature T
1
and T
2
, for the entropy increase of n mol of
a gas (not necessarily ideal) that is heated at constant pressure so that its temperature changes from T
1
to T
2
. To what does your
expression reduce if the gas is ideal?

Solution:
Given:
1 2
mol, , n n T T =
Required: general expression in terms of C
P,m
and temperature
In Chapter 2, we saw Eq. 2.96 which states that:
, P m
H C T =
However, we know that under constant pressure, we can make the following substitution;
,
,
or
P m
P m P
H C T
q H
q C T dq C dT
=
=
= =

The corresponding entropy change is given by Eq. 3.68;
2
1
2
1
rev
,
P
T
P
T
T
P m
T
q
S dT
T
C
S dT
T
C
S dT
T
C
S n dT
T
=
=
=
=

If we are assuming that the gas is ideal, then we can say that the heat capacity is independent of temperature (ie. it is constant) and the
above expression reduces to;
3-55
2
1
,
2
1
2
,
1
ln
ln
T
P m
T
P
P m
C
S n dT
T
T
S C
T
T
S nC
T
=
=
=

3-56
3.20. Initially 5 mol of an ideal gas, with C
V,m
=12.5 J K
1
mol
1
, are at a volume of 5 dm
3
and a temperature of 300 K. If the gas is
heated to 373 K and the volume changed to 10 dm
3
, what is the entropy change?

Solution:
Given: Ideal Gas:
1 1 3 3
, 1 2 1 2
5 mol, 12.5 J K mol , 5 dm, 10 dm, 300 K, 373 K
V m
n C V V T T = = = = = =
Required: S
We have already seen Eq. 3.55 which states:
rev
, V m
dq dT dV
dS nC nR
T T V
= = +
Upon integration and the assumption that C
V,m
is independent of temperature we obtain Eq. 3.57,
2 2
,
1 1
ln ln
5.0 mol
V m
T V
S nC nR
T V
S
= +
=
( )
1 1
12.5 J K mol

( )
373 K
ln
300 K
5.0 mol +
( )
1 1
8.3145 J K mol

( )
3
10 dm
ln
3
5 dm
( )
1
1
13.612 247 28.815 861 J K
42.4 J K
S
S
= +
=


3-57
*3.21. At 100 C 200 g of mercury are added to 80 g of water at 20 C in a vessel that has a water equivalent of 20 g. The specific heat
capacities of water and mercury may be taken as constant at 4.18 and 0.140 J K
1
g
1
, respectively. Calculate the entropy change of
(a) the mercury; (b) the water and vessel; (c) the mercury, water, and vessel together.

Solution:
Given:
o 1 1 1 1
Hg water/vessel water Hg
100 C, 200 g, 100 g, 4.18 J K g , 0.140 J K g T m m C C = = = = =
Required: S for a, b, c
We are told that the heat capacities for water and mercury are constant. This is like saying that they are independent of temperature and we
will be able to use a form of Eq. 3.57 as we have done in the previous problem. First, let us determine the final temperature of the system;
T
u
.
( ) ( )
water Hg
100 g
P
u u
P P
mC T
m C T T m C T T
=
( )
1 1
4.18 J K g

( )( )
o
20 C 200 g
u
T =
( )
1 1
0.140 J K g

( )( )
( )( ) ( )( )
( )( ) ( )
o
1 o 1 o
o o
o o
o
o
100 C
418 J K 20 C 28 J K 100 C
14.928 571 20 C 100 C
14.928 571 298.571 429 C 100 C
15.928 571 398.571 429 C
25.02 C
u
u u
u u
u u
u
u
T
T T
T T
T T
T
T

=
=
=
=
=

a) Mercury: using a form of Eq. 3.55
3-58
2
1
2
1
,
200 g
T
P
T
T
P m
T
C
S dT
T
dT
S mC
T
S
=
=
=
( )
1 1
0.140 J K g

( )
( )
298.17
373.15
1
298.17 K
28 J K ln
dT
T
S

=
373.15 K
1
6.28 J K S

=

b) Water and vessel: using a form of Eq. 3.55
2
1
T
P
T
C
S dT
T
=

2
1
,
100 g
T
P m
T
dT
S mC
T
S
=
=
( )
1 1
4.18 J K g

( )
( )
298.17
293.15
1
298.17 K
418 J K ln
dT
T
S

=
293.15 K
1
7.10 J K S

=

c) Water, vessel and mercury:
( )
net Hg water/vessel
1
net
1
net
6.28 7.10 J K
0.82 J K
S S S
S
S
= +
= +
=

3-59
*3.22. At 0 C 20 g of ice are added to 50 g of water at 30C in a vessel that has a water equivalent of 20 g. Calculate the entropy changes
in the system and in the surroundings. The heat of fusion of ice at 0 C is 6.02 kJ mol
1
, and the specific heat capacities of water and
ice may be taken as constant at 4.184 and 2.094 J K
1
g
1
, respectively, and independent of temperature.

Solution:
Given:
o o
ice ice water water vessel
0 C, 20 g, 50 g, 30 C, 20 g, T m m T m = = = = =

1 1 1 1 1
fus ice ice water
6.02 kJ mol , 2.094 J K g , 4.184 J K g H C C = = =
Required: S for the system
In this particular problem, we will be dealing with different temperature ranges so it is important to first determine the amount of heat
required to melt the ice or heat the water.
The heat required to melt 20 g of ice can be found by using the heat of fusion;
fus
1
at constant ,
, 18.0152 g mol
20 g
q mC T
T
q n H
m
n M
M
q
=
=
= =
=
18.0152 g
1
mol
1
6020 J mol
( )
6683.245 J q =

The heat required to warm up 20 g of water over a temperature range (use heat capacity);
water
20 g
q mC T
q mC T
q
=
=
=
( )
1
4.18 J K
1
g
( )
( ) 0 K T
83.6 J q T =

3-60
The heat required to cool 70 g of water from 30 C in the vessel to T C (use heat capacity);
water
70 g
q mC T
q mC T
q
=
=
=
( )
1
4.18 J K
1
g
( )
( ) 30 K T
( ) 292.6 J 30 q T =

8778 J 292.6 q T =
Now, we can balance out the reaction by writing:
( ) ( )
( ) ( )
fus water water
0 30
6683.245 J 83.6 J 8778 J 292.6 J
n H mC T mC T
T T
+ =
+ =

Which can then be solved for T, we obtain;
( ) ( )
( ) ( )
fus water water
0 30
6683.245 J 83.6 J 8778 J 292.6 J
83.6 J 2094.755 J 292.6 J
376.2 J
n H mC T mC T
T T
T T
T
+ =
+ =
=
2094.755 J =
o
2094.755
376.2
5.57 C
T
T
=
=

All of these processes are considered to be reversible and the heat capacities are independent of temperature (when working over a range).
Melting 20 g of ice at constant temperature:
3-61
syst
fus
fus fus
syst
syst
and therefore,
20 g
q
S
T
q n H
n H m H
S
T MT
S
=
=

= =
=
( )
1
6020 J mol
( )
18.0152 g
1
mol
( )
( )
1
syst
273.15 K
24.47 J K S

=

Due to the law of equilibrium,
total syst surr
surr syst
1
surr
0
24.47 J K
dS dS dS
dS dS
S

= + =
=
=

Cooling 70 g of water to 0 C:
2
1
T
P
T
C
S dT
T
=

2
1
syst ,
syst
70 g
T
P m
T
dT
S mC
T
S
=
=
( )
1 1
4.184 J K g

( )
( )
273.15
303.15
1
syst
273.15 K
292.88 J K ln
dT
T
S

=
303.15 K
1
syst
1
surr
30.52 J K
30.52 J K
S
S
=
=

3-62
Heating the total amount of water (90 g) to the final temperature of the system:
2
1
2
1
syst ,
syst
90 g
T
P
T
T
P m
T
C
S dT
T
dT
S mC
T
S
=
=
=
( )
1 1
4.184 J K g

( )
( )
278.72
273.15
1
syst
278.72 K
376.56 J K ln
dT
T
S

=
273.15 K
1
syst
1
surr
7.60 J K
7.60 J K
S
S
=
=

The net entropy change for this system will then be:
( )
( )
( )
net 1 2 3
1
net
1
net
1
net
24.47 30.52 7.60 J K
syst 1.55 J K
surr 1.55 J K
S S S S
S
S
S
= + +
= +
=
=


3-63
*3.23. Calculate the increase in entropy of 1 mol of nitrogen if it is heated from 300 K to 1000 K at a constant pressure of 1 atm; use the
C
P
data in Table 2.1.

Solution:
Given:
2
N 1 2
1 mol, 300 K, 1000 K, 1 atm n T T P = = = = , Table 2.1
Required:
m
S
The increase in entropy can be calculated by using Eq. 3.55, as well as information given in Chapter 2.
( )
( )
( )
( ) ( )
2
1
2
1
2 2 2
1 1 1
,
2
,
2
2
2 2
2 2
Eq. 2.48
1000 1 1 1
ln 1000 300
300 2 1000 300
1000 50 000 1 1
28.58 ln 0.003 76 700
300 2 1000 300
T
P m
m
T
P m
T
m
T
T T T
m
T T T
m
m
C
S dT
T
C d eT fT
d eT fT
S dT
T
d eT fT
S dT dT dT
T T T
S d e f
S
=
= + +
+ +
=
= + +
| |
= + +
|
\ .
|
= + +
\

1 1
1 1
J K mol
36.79 J K mol
m
S

( |
| (
.
=

3-64
*3.24. The entropy change for the isothermal expansion of an ideal gas at 300 K from a particular state A to a state B is 50 J K
1
. When an
expansion was performed, the work done by the system was 6 kJ . Was the process reversible or irreversible? If the latter, calculate
the degree of irreversibility (i.e., the ratio of the work done to the reversible work).

Solution:
Given: Ideal Gas: ( )
1
300 K state A, state B is 50 J K , by system 6 kJ T w = =
Required: reversible or irreversible?
From Chapter 2, we have seen that for isothermal processes both the change in internal energy and enthalpy are equal to zero because they
are dependent on temperature change. Let us first start by describing a reversible isothermal expansion.
rev rev
rev rev
rev
rev
rev
0
since then,
300 K
U q w
U
q w
q
S
T
q T S
w T S
= +
=
=
=
=
= =
( )
1
50 J K
( )
( )
rev rev
by system 15 000 J or 15 000 J w w = =

Given that the actual work done by the system is -6000 J which is less than the value we calculated above, we know that the process is an
irreversible one.
The degree of irreversibility is therefore:
irr
rev
6 kJ w
w
=
15 kJ
irr
rev
0.4
w
w
=

3-65
3.25. One mole of water is placed in surroundings at 3 C, but at first it does not freeze (it remains as supercooled water). Suddenly it
freezes. Calculate the entropy change in the system during the freezing, making use of the following data:
1 1
,
1 1
,
(water) 75.3J K mol
(ice) 37.7J K mol
P m
P m
C
C
=
=

1
(ice water) 6.02kJ mol at0 C
f
H =

The two C
P
values can be assumed to be independent of temperature. Also, calculate the entropy change in the surroundings, and the
net entropy change in the system and surroundings.

Solution:
Given:
water surr
1 mol, 3 C, values
P
n T C = =
Required: S
In order to solve this problem, it is necessary to devise a process in which we can describe the freezing of water reversibly. This will take
three steps;
(1) Heat the supercooled water reversibly from -3 C to 0 C:
2
1
1
2
1 ,
1
1
ln
1.0 mol
T
P
T
P m
C
S dT
T
T
S nC
T
S
=
=
=
( )
1 1
75.3 J K mol

( )
273.15 K
ln
270.15 K
1
1
0.831 593 J K S

=

(2) Freeze the water at 0 C (use the enthalpy of formation):
3-66
2
fus
2
1
2
6020 J mol
f
f
q
S
T
q H H
H
S
T
S
=
= =
= 1 mol
273.15 K

1
2
22.04 J K S

=

(3) Cool the ice reversibly from 0 C to -3 C:
2
1
3
2
3 ,
1
3
ln
1.0 mol
T
P
T
P m
C
S dT
T
T
S nC
T
S
=
=
=
( )
1 1
37.7 J K mol

( )
270.15 K
ln
273.15 K
1
3
0.416 349 J K S

=

The net entropy change is therefore:
( )
( )
net 1 2 3
1
net
1
net
0.831 593 22.04 0.416 349 J K
syst 21.62 J K
S S S S
S
S
= + +
=
=

In order to determine the entropy change in the surroundings, we must first calculate all of the heat that has been gained by the environment
in each step.
(1) Heat the supercooled water reversibly from -3 C to 0 C:
3-67
1 ,
1
1.0 mol
P m
q nC T
q
=
=
( )
1
75.3 J K
1
mol
( )
( )
1
3 0
225.9 J q

=

(2) Freeze the water at 0 C (use the enthalpy of formation):
1
2
2
(ice water) 6.01kJ mol
6020 J
f
f
H
q n H
q
=
=
=

(3) Cool the ice reversibly from 0 C to -3 C:
3 ,
3
1.0 mol
P m
q nC T
q
=
=
( )
1
37.7 J K
1
mol
( )
( ) ( )
3
0 3
113.1 J q

=

The net heat gained by the surroundings is thus:
( )
( )
net 1 2 3
net
net
225.9 6020 113.1 J
surr 5907.2 J
q q q q
q
q
= + +
= + +
=

The heat was gained by the surroundings at -3 C and the entropy change is therefore given by:
3-68
surr
surr
1
surr
1 1
surr
5907.2 J
mol
270.15 K
21.87 J K mol
q
S
T
S
S

=
=
=

The net entropy change in the system and the surroundings is therefore:
( ) ( )
net net net
1 1
net
1
net
1 1
net
syst surr
21.62 J K 21.87 J K
0.25 J K
0.25 J K mol
S S S
S
S
S

= +
= +
=
=

3-69
3.26. 200 cm
3
of a 0.5 mol solution of sucrose is diluted to 1 dm
3
by the addition of 800 cm
3
of water. Assume ideal behavior and
calculate the entropy change.

Solution:
Given: Ideal:
3 3 3
sucrose sucrose water
200 cm, 0.5 mol, 1 dm, 800 cm
f
V n V V = = = =
Required: S
In the Ideal Gas section of Chapter 3, we have been given Eq. 3.51 which applies at constant temperature. Let us assume that this is true.
2
1
ln
V
S nR
V
=
This means that we must first determine the number of moles and knowing that the total volume is 1000 cm
3
we can determine the entropy
change.
mol
0.5
L
n =
L
1
3
dm
3
200 cm
3
1 dm
3 3
10 cm
0.1 mol n =

3
1000 cm
f
i
V
V
=
3
200 cm
5
ln
0.1 mol
f
i
V
S nR
V
S
=
=
=
( )
1 1
8.3145 J K mol

( )
1
1
ln5
1.338 167 152 J K
1.34 J K
S
S
=
=


3-70
3.27. One liter of a 0.1 M solution of a substance A is added to 3 liters of a 0.05 M solution of a substance B. Assume ideal behavior and
calculate the entropy of mixing.

Solution:
Given: Ideal:
A A B B
1 litre, C 0.1 M, 3 litres, C 0.05 M V V = = = =
Required:
mix
S
Since we are working with liters and solution in Molar concentrations, we know that there are 0.1 moles of substance A and 0.15 moles of
substance B. For substance A, the volume increases by a factor of 4. Let us again use Eq. 3.51 in order to calculate the entropy change.
A
A
A
ln
0.1 mol
f
V
S nR
V
S
=
=
( )
1 1
8.3145 J K mol

( )
4 L
ln
1 L
1
A
1.153 J K S

=

For substance B, the volume increases by a factor of 4/3. This will give the following entropy change:
B
B
B
ln
0.15 mol
f
V
S nR
V
S
=
=
( )
1 1
8.3145 J K mol

( )
4 L
ln
3 L
1
B
0.359 J K S

=

The entropy of mixing will therefore be given by the total entropy change for both substances A and B.
( )
mix A B
1
mix
1
mix
1.153 0.359 J K
1.151 J K
S S S
S
S
= +
= +
=

3-71
3.28. Ten moles of water at 60 C are mixed with an equal amount of water at 20 C. Neglect any heat exchange with the surroundings
and calculate the entropy change. The heat capacity of water may be taken to be 75.3 J K
1
mol
1

Solution:
Given:
1 1
water water2
10 mol, 60 C, 10 mol, 20 C, 75.3J K mol
P
n T n T C = = = = =
Required: S
First it is important to determine the final temperature of the system. Since we are told that there is no heat exchange with the surroundings,
we can simply take the average of the two temperatures which yields:
( )
o
o
avg
20 60 C
40 C
2
f
T T
+
= = =
The water at 60 C can be cooled in a reversible manner to 40 C while the water at 20 C can be heated reversibly to the same final
temperature. Since these processes are reversible, and the heat capacity is taken to be independent of temperature, we can use a form of Eq.
3.57 to determine the entropy change in either case.
o
60 C
ln
10 mol
f
P
i
T
S nC
T
S
=
=
( )
1 1
75.3 J K mol

( )
o
o
1
60 C
20 C
313.15
ln
333.15
46.618 629 J K
10 mol
S
S
=
=
( )
1 1
75.3 J K mol

( )
o
1
20 C
313.15
ln
293.15
49.696 408 J K S

=

As we have previously seen, the net entropy change for the system is simply the addition of both entropy changes calculated above.
3-72
( )
o o
net
60 C 40 C
1
1
46.618 629 49.696 408 J K
3.08 J K
S S S S
S
S
= = +
= +
=

3-73
3.29. A vessel is divided by a partition into two compartments. One side contains 5 moles O
2
at 1 atm pressure; the other, 5 moles N
2
at 1
atm pressure. Calculate the entropy change when the partition is removed.

Solution:
Given: Side 1: n =5 mole O
2
, P =1 atm
Side 2: n =5 mole N
2
, P =1 atm
Required: ln
MIX i i
i
S nR x x =

Treat the gases as Ideal Gases and since they are in contact the have the same temperature.
2 2
5
5
1
O N
nRT RT
V RT V V
P
= = = =

So both volumes are equal. Mole fractions,
2 2
5 1
10 2
O N
x x = = =

-1
1 1 1 1
ln ln ln ln2
2 2 2 2
5.76 e.u. per mole
10 5.76 =57.6 J K
MIX i i
i
MIX
MIX
S R x x R R R
S
S
= = =
=
=

3-74
3.30. One mole of liquid water at 0 C is placed in a freezer having a temperature of 12 C. The water freezes and the ice cools to 12
C. Making use of the data given in Problem 3.25, calculate the change in entropy in the system and in surroundings (the freezer),
and the net entropy change.

Solution:
Given: data from 3.25,
o o
water freezer
1 mol, 0.00 C, 12 C n T T = = =
Required:
net
S
J ust as was done in problem 3.25, we will consider this system as two reversible processes.
(1) The liquid water will freeze to become ice at 0 C
1
1
1
1 1
1
6020 J mol
273.15 K
22.039173 J K mol
f
H
S
T
S
S
=
=
=

(2) The ice is cooled reversibly to -12 C
2
1
2
2
2 ,
1
2
ln
1.0 mol
T
P
T
P m
C
S dT
T
T
S nC
T
S
=
=
=
( )
1 1
37.7 J K mol

( )
261.15 K
ln
273.15 K
1
2
1.693715 J K S

=

(3) Combine these values in order to determine the entropy change for the system
3-75
( )
( ) ( )
( )
1 2
1
1
system
system 22.039173 1.693715 J K
system 23.73 J K
S S S
S
S
= +
=
=

It is important to calculate the amount of heat gained by the freezer.
1 ice
2 ,
6020 J
1.0 mol
f
P m
q n H
q nC T
= =
= =
( )
1
37.7 J K
1
mol
( )
( ) 0 12 K +

( )
2
freezer 1 2
freezer
freezer
452.4 J
6020 152.4 J
6472.4 J
q
q q q
q
q
=
= +
= +
=

Since this heat was gained at -12 C, we can define the entropy change as:
( )
( )
( )
freezer
freezer
freezer
1
freezer
surr
6472.4 J
surr
261.15 K
surr 24.78 J K
q
S
T
S
S

=
=
=

The net entropy change occurring in the system and surrounding is therefore,
( ) ( ) ( )
( ) ( )
( )
net net net
1
net
1
net
total system surr
total 23.73 24.78 J K
total 1.05 J K
S S S
S
S
= +
= +
=


3-76
3.31. One mole of liquid water at 0 C is placed in a freezer which is maintained at 10 C. Carry out the same calculations as for Problem
3.30.

Solution:
Given:
o o
water freezer
1 mol, 0.00 C, 10 C n T T = = =
Required:
net
S
J ust as was done in problem 3.25, we will consider this system as two reversible processes.
(1) The liquid water will freeze to become ice at 0 C
1
1
1
1 1
1
6020 J mol
273.15 K
22.039173 J K mol
f
H
S
T
S
S
=
=
=

(2) The ice is cooled reversibly to -10 C
2
1
2
2
2 ,
1
2
ln
1.0 mol
T
P
T
P m
C
S dT
T
T
S nC
T
S
=
=
=
( )
1 1
37.7 J K mol

( )
263.15 K
ln
273.15 K
1
2
1.406092 J K S

=

(3) Combine these values in order to determine the entropy change for the system
3-77
( )
( ) ( )
( )
1 2
1
1
system
system 22.039173 1.406092 J K
system 23.45 J K
S S S
S
S
= +
=
=

It is important to calculate the amount of heat gained by the freezer.
1 ice
2 ,
6020 J
1.0 mol
f
P m
q n H
q nC T
= =
= =
( )
1
37.7 J K
1
mol
( )
( ) 0 10 K +

( )
2
freezer 1 2
freezer
freezer
377 J
6020 377 J
6397 J
q
q q q
q
q
=
= +
= +
=

Since this heat was gained at -10 C, we can define the entropy change as:
( )
( )
( )
freezer
freezer
freezer
1
freezer
surr
6397 J
surr
263.15 K
surr 24.31 J K
q
S
T
S
S

=
=
=

The net entropy change occurring in the system and surrounding is therefore,
( ) ( ) ( )
( ) ( )
( )
net net net
1
net
1
net
total system surr
total 23.45 24.31 J K
total 0.86 J K
S S S
S
S
= +
= +
=

3-78
3.32. Two moles of water at 60 C are added to 4 mol of water at 20 C. Calculate the entropy change, assuming that there is no loss of
heat to the surroundings. The heat capacity of water is 75.3 J K
1
mol
1
.

Solution:
Given:
o o 1 1
water water water2 water2
2 mol, 60 C, 4 mol, 20 C, 75.3 J K mol
P
n T n T C = = = = =
Required: S
This problem may be solved by using a similar method to problem 3.21. It is important to determine the final temperature of the system
after the mixing occurs. Since we are not neglecting the heat exchange between the system and the surroundings, we cannot use the same
method as in problem 3.28.
( ) ( )
water1 1 water2 2
2.0 mol
p
p p
nC T
n C T T n C T T
=
( )
1 1
75.3 J K mol

( )
( ) ( ) ( )( )
( )( ) ( )( )
( ) ( )
o o
1 1
1 1
o
60 C 4.0 mol 75.3 J K mol 20 C
150.6 J K 60 301.2 J K 20
60 2 20
60 2 40
100 3
33.333 333 33 C
306.483 333 3 K
306.48 K
T T
T T
T T
T T
T
T
T
T

=
=
=
=
=
=
=
=

Since the heat capacity is taken to be independent of temperature, we can use a form of Eq. 3.57 to determine the entropy change.
3-79
o
60 C
ln
2.0 mol
f
p
i
T
S nC
T
S
=
=
( )
1 1
75.3 J K mol

( )
306.48 K
ln
333.15 K
o
1
60 C
12.566 115 J K S

=

o
20 C
4.0 mol S =
( )
1 1
75.3 J K mol

( )
306.48 K
ln
293.15 K
o
1
20 C
13.393 784 79 J K S

=

As we have previously seen, the net entropy change for the system is simply the addition of both entropy changes calculated above.
( )
o o
net
60 C 20 C
1
1
1
12.566 115 13.393 784 79 J K
0.827 669 794 J K
0.828 J K
S S S S
S
S
S
= = +
= +
=
=


3-80
3.33. One mole of an ideal gas is initially at 10 bar and 298 K. It is allowed to expand against a constant external pressure of 2 bar to a
final pressure of 2 bar. During this process, the temperature of the gas falls to 253.2 K. Find U, H, S, S
therm
, and S
univ
for the
process. Assume that the thermal surroundings remain at 298 K throughout. Devise at least three different paths to accomplish this
change and show that no matter which path is used, the desired values are the same.
.
Solution:
Given: Ideal Gas:
ext
1 mol, 10 bar, 298 K, 2 bar, 2 bar, 253.2 K
i i f f
n P T P P T = = = = = =

surr
298 K T =
Required: U, H, S, S
therm
, and S
univ
, devise three different paths
It is important to consider the fact that there are many reversible paths that can be taken in order to move from the initial to final state. We
will consider four of them.
1. It is possible to perform an isothermal expansion to the final volume. After this, we should cool the gas at constant volume until we
reach the final temperature.
0 U = we know that this is true because there is neither a change in internal energy or enthalpy when an ideal gas is subject to isothermal
conditions.
( )
, V m f i
U C T T = is also true for the second part of this process (under constant volume).
By putting these two expressions together we can generate the change in internal energy for this pathway.
( )
,
,
1
0
3
2
3
8.3145 J K
2
V m f i
V m
U C T T
C R
U

= +
=
=
( )
( )
1
mol 253.2 298 K
1
558.7 J mol U

=

3-81
( )
,
,
1
0
5
2
5
8.3145 J K
2
P m f i
P m
H C T T
C R
H

= +
=
=
( )
( )
1
mol 253.2 298 K
1
931.2 J mol H

=

Under constant temperature, we have seen (from Eq. 3.94) that the entropy is given as:
ln
f
i
V
S nR
V
=
Similarly, at constant volume, the following expression holds true;
,
ln
f
V m
i
T
S C
T
=
3-82
,
ln ln
1 mol
f f
V m
i i
i
i
i
V T
S R C
V T
PV nRT
nRT
V
P
= +
=
= =
( )
1
8.3145 J K
1
mol
( )
298 K
( )
1
5 5 3
247.7721 J bar
10 bar
1 bar 10 Pa, 1 atm 1.01325 10 Pa, 1 atm dm 101.325 J
247.7721 J
i
V
=
= = =
=
1
bar
1 bar
5
10 Pa
5
1.01325 10 Pa
1 atm
1 atm
3
dm
101.325 J
3
2.477 721 dm
1 mol
i
f
f
f
V
nRT
V
P
=
= =
( )
1
8.3145 J K
1
mol
( )
253.2 K
( )
1
1052.6157 J bar
2 bar
1052.6157 J
f
V
=
=
1
bar
1 bar
5
10 Pa
5
1.01325 10 Pa
1 atm
1 atm
3
dm
101.325 J
( ) ( )
3
1 1 1 1
1 1 1 1
1 1
10.526 157 dm
10.526 157 3 253.2
8.3145 J K mol ln 8.3145 J K mol ln
2.477 721 2 298
12.027 125 J K mol 2.031 820 J K mol
9.995 J K mol
f
V
S
S
S

=
= +
=
=

2. The second method to arrive at the final state entails an isothermal expansion to the final pressure. We can then employ constant
pressure cooling in order to attain the final temperature.
0 U = we know that this is true because there is neither a change in internal energy or enthalpy when an ideal gas is subject to isothermal
conditions.
( )
, V m f i
U C T T = is also true for the second part of this process (just as we have seen for constant volume!)
By putting these two expressions together we can generate the change in internal energy for this pathway.
3-83
( )
,
,
1
0
3
2
3
8.3145 J K
2
V m f i
V m
U C T T
C R
U

= +
=
=
( )
( )
1
mol 253.2 298 K
1
558.7 J mol U

=

( )
,
,
1
0
5
2
5
8.3145 J K
2
P m f i
P m
H C T T
C R
H

= +
=
=
( )
( )
1
mol 253.2 298 K
1
931.2 J mol H

=

Since we know that pressure and volume have an inverse relationship, we can simply write:
ln
i
f
P
S R
P
= when we are carrying out the expansion under constant pressure (rather than constant volume). The second part of the
pathway will remain the same aside from the fact that we will be using
, P m
C .
( ) ( )
,
,
1 1 1 1
1 1
ln ln
5
2
10 5 253.2
8.3145 J K mol ln 8.3145 J K mol ln
2 2 298
9.995 J K mol
f
i
P m
f i
P m
T
P
S R C
P T
C R
S
S

= +
=
= +
=

3. The third path will involve an isothermal expansion from ( )
0 0
, P V followed by an adiabatic expansion to the final state.
3-84
It is important to note that we need to find the intersection of the isotherm that passes through the initial state and the adiabat that passes
through the final state. This intersection is ( )
0 0
, P V at T
i
. Using the relationships for adiabatic processes (Eq. 2.90);
1
0
f
i f
T
V
T V

| |
= |
|
\ .

,
, ,
,
5 3
and ,
2 2
5
2
P m
P m V m
V m
C
C R C R
C
R
= = =
=
3
2
R
5
2
2
3
3
2
0 0
3
2
3
0
5
3 3
253.2 K
10.526 dm
f f
i f i f
f
f
i
T T
V V
T V T V
T
V V
T
| | | |
| |
= = | |
|
| |
\ .
\ . \ .
| |
= =
|
\ .
298 K
3
2
3
0
8.243 934 dm V
| |
|
\ .
=

( )
,
,
1
0
3
2
3
8.3145 J K
2
V m f i
V m
U C T T
C R
U

= +
=
=
( )
( )
1
mol 253.2 298 K
1
558.7 J mol U

=

3-85
( )
,
,
1
0
5
2
5
8.3145 J K
2
P m f i
P m
H C T T
C R
H

= +
=
=
( )
( )
1
mol 253.2 298 K
1
931.2 J mol H

=

When determining the change in entropy, we can use the first part of the equation given in the first method, however, during the adiabatic
expansion, there will be no change in entropy.
( )
0
3
1 1
ln 0
8.243 934 dm
8.3145 J K mol ln
i
V
S R
V
S

= +
=
3
2.477 721 dm
1 1
9.995 J K mol S

=

4. Constant pressure heating to the final volume followed by constant volume cooling to the final pressure.
The gas will have to be heated to
o
1266.0 K T = in order for it to reach the volume of 10.526 dm
3
at 10.0 bar pressure. Therefore;
( ) ( ) ( )
( ) ( ) ( )
, ,
1
, ,
1
, ,
3
1266.0 298.1 253.2 1266.0
2
558.7 J mol
5
1266.0 298.1 253.2 1266.0
2
931.2 J mol
5 1266.0 3
ln ln ln l
2 298.0 2
V m o i V m f o
P m o i P m f o
f
o
P m V m
i o
U C T T C T T R
U
H C T T C T T R
H
T
T
S C C R R
T T
= + = +
=
= + = +
=
| | | |
| |
= + = +
| | |
\ .
\ . \ .
1 1
253.2
n
1266.0
9.995 J K mol S

| |
|
\ .
=

3-86
Yet another path we can try is constant volume cooling to the final pressure followed by constant pressure heating to the final temperature.
In each of these cases, we have verified that , and U H S are the same, thus proving that they are independent of the path taken, as any
state property should be. We now have to find the entropy change of the surroundings.
The actual process is the expansion of the gas against a constant external pressure of 2 bar. For this process, according to the first law,
( )
( )
( )
1
; Therefore,
558.7 J mol 2.0 bar
act ext f i
act ext f i
act
U q P V V
q U P V V
q

=
= +
= +
( ) ( )
3
dm
10.526 2.478
1 1
8.3145 J K mol
mol

0.083145 bar
3
dm
1 1
K mol

( )
1
1
surr
surr
1 1
surr
1 1
surr
1 1
univ surr
1 1
univ
1050.9 J mol
1050.9 J mol
298 K
3.526 510 067 J K mol
3.527 J K mol
9.995 3.527 J K mol
6.468 J K mol
act
act
q
q
S
T
S
S
S S S
S

=

= =
=
=
= + =
=

3-87
3.34. Five moles of water at 50 C are placed in a refrigerator maintained at 3 C. Calculate S for the system and for the environment,
and the net entropy change, taking C
P
for water at 75.3 J K
1
mol
1

Solution:
Given:
o o 1 1
water water fridge
5 mol, 50 C, 3 C, 75.3 J K mol
P
n T T C = = = =
Required:
sys
S , ( )
fridge
surr S ,
net
S
(1) Since the heat capacity is independent of temperature, the entropy change for the system can be defined by,
( ) ( )
fridge
sys
1 1
sys
1
sys
1
sys
ln
276.15
5.0 mol 75.3 J K mol ln
323.15
59.175 414 38 J K
59.18 J K
p
water
T
S nC
T
S
S
S

=
=
=
=

(2) The heat accepted by the fridge can now be found.
( ) ( )( )
fridge ,
1 1
fridge
fridge
5.0 mol 75.3 J K mol 323.15 276.15 K
17695.5 J
P m
q nC T
q
q

=
=
=

(3) Since this heat was gained at 3 C, we can define the entropy change as:
3-88
( )
( )
( )
( )
fridge
fridge
fridge
1
fridge
1
fridge
surr
19695.5 J
surr
276.15 K
surr 64.079 304 73 J K
surr 64.08 J K
q
S
T
S
S
S
=
=
=
=

The net entropy change between the system and surroundings is therefore,
( ) ( )
( ) ( )
( )
( )
sys fridge
net
1
net
1
net
1
net
total surr
total 59.175 414 38 64.079 304 73 J K
total 4.903 890 346 J K
total 4.90 J K
S S S
S
S
S
= +
= +
=
=

3-89
3.35. Problem 2.32 of Chapter 2 was concerned with dropping (a) one ice cube, (b) 10 ice cubes, each weighing 100 g, into 1 kg of water
at 20 C. Calculate the entropy change in each case. (H
fus
of ice at 0 C is 6.026 kJ mol
1
; C
P,m
for water is 75.3 J K
1
mol
1
.)

Solution:
Given: Problem 2.32
Required: S in each case
a) Recall that in the first case (only one ice cube), all of the ice melts and the final temperature was 12 C (see solution to problem 2.32).
The entropy change associated with this process can be broken down into three reversible processes.
(1) The ice melts reversibly at 0 C
ice
1
100 g
f
n H
S
T
m
n
M
=
= =
18.0152 g
1
1
5.550 868 mol
mol
5.550 868 mol
S
=
=
( )
1
6025 J mol
( )
1
1
273.15 K
122.438150 J K S

=

(2) The water is heated reversibly from 0 C to 12 C
2
2
ln
5.550868 mol
f
P
i
T
S nC
T
S
=
=
( )
1 1
75.3 J K mol

( )
1
2
285.15
ln
273.15
17.970757 J K S

=

(3) 1 kg of water is cooled reversibly from 20 C to 12 C
3-90
3
3
ln
55.508682 mol
f
P
i
T
S nC
T
S
=
=
( )
1 1
75.3 J K mol

( )
1
3
285.15
ln
293.15
115.651264 J K S

=

The net entropy change is therefore given by the sum of the entropies calculated above.
net 1 2 3
S S S S = + +
( )
1
net
1
net
122.438150 17.970757 115.651264 J K
24.76 J K
S
S
= +
=

b) In the second situation, only 250 g of the ice melts and the final temperature of the water ends up being 0 C (see solution to problem
2.32). Using the same method as above, we will break the system down into two reversible processes.
(1) 250 g of ice melts reversibly at 0 C
ice
1
250 g
f
n H
S
T
m
n
M
=
= =
18.0152 g
1
1
13.877170 mol
mol
13.877170 mol
S
=
=
( )
1
6025 J mol
( )
1
1
273.15 K
306.095375 J K S

=

(2) 1 kg of water is cooled reversibly from 20 C to 0 C
3-91
2
2
ln
55.508682 mol
f
P
i
T
S nC
T
S
=
=
( )
1 1
75.3 J K mol

( )
1
2
273.15
ln
293.15
295.358845 J K S

=

The net entropy change is therefore given by the sum of the entropies calculated above.
( )
net 1 2
1 1
net
1
net
306.095375 295.358845 J K J K
10.74 J K
S S S
S
S

= +
=
=

3-92
3.36. The absolute entropy of nitrogen at its vaporization point of 77.32 K and exactly 1 bar is 151.94 J K
1
mol
1
. Using the expression
for C
P,m
for nitrogen given in Table 2.1, find the entropy of the gas at 800.0 K and 1 bar.

Solution:
Given:
2
1 1
abs N vap
151.94 J K mol , 77.32 K, 1 bar S T P = = = , Table 2.1
Required: S of gas
In Eq. 2.48 we are given the following expression for C
P,m
:
2
, P m
C d eT fT
= + +
For nitrogen at 800 K and 1 bar, we are given that;
1 1
3 2 1
4 1
28.58 J K mol
3.76 10 J K mol
5.0 10 J K mol
d
e
f

=
=
=

We can substitute the expression for C
P,m
into the equation that produces the value for entropy at a single given temperature.
( ) ( )
( ) ( )
( )
( )
( ) ( ) ( )
, 1 1
abs
3 4 2
800 K
1 1
77.32 K
3 4 2
800 K 800 K 800 K
77.32 K 77.32 K 77.32 K
800 K / J K mol
28.58 3.76 10 5.0 10 /
800 K / J K mol 151.94
3.76 10 5.0 10 /
28.58
800 K 151.94
f
i
T
P m
T
C
S S dT
T
T T
S dT
T
T T
S dT dT dT
T T T

= +
+
= +

= + +

( )
1 1
800 K 217.3 J K mol S

`

)
=

3-93
3.37. Calculate G at 25 C for the following fermentation reaction:
6 12 6 2 5 2
glucose ethanol
C H O (aq) 2C H OH(aq) 2CO (g) +
The standard Gibbs energies of formation of glucose, ethanol, and carbon dioxide are given in Appendix D.
Also use the data in Appendix D to calculate S for the fermentation reaction.

Solution:
Given: Appendix D
Required: G, S
By using Appendix D and Eq. 3.91, we will be able to determine the standard change in Gibbs Energy. Given that;
( )
( )
( )
( ) ( )
( ) ( )
6 12 6 2 5 2
glucose ethanol
1
6 12 6
1
2 5
1
2
o
o
2 2 5 6 12
C H O (aq) 2C H OH(aq) 2CO (g)
C H O , aq 910.4 kJ mol
C H OH, aq 181.64 kJ mol
CO , g 394.36 kJ mol
products reactants
2 CO , g 2 C H OH, aq C H O
f
f
f
f f
f f f
G
G
G
G G G
G G G G
+
=
=
=
=
= +

( )
( ) ( ) ( )
6
o 1 1 1
o 1
, aq
2 394.36 kJ mol 2 181.64 kJ mol 910.4 kJ mol
241.6 kJ mol
G
G

= +
=

We may also use Appendix D and a similar equation for the standard enthalpy change in order to determine the standard entropy change.
3-94
( )
( )
( )
( ) ( )
( ) ( )
6 12 6 2 5 2
glucose ethanol
1
6 12 6
1
2 5
1
2
o
o
2 2 5 6 12
C H O (aq) 2C H OH(aq) 2CO (g)
C H O , aq 1273.3 kJ mol
C H OH, aq 288.3 kJ mol
CO , g 393.51 kJ mol
products reactants
2 CO , g 2 C H OH, aq C H O
f
f
f
f f
f f f
H
H
H
H H H
H H H H
+
=
=
=
=
= +

( )
( ) ( ) ( )
6
o 1 1 1
o 1
, aq
2 393.51 kJ mol 2 288.3 kJ mol 1273.3 kJ mol
90.32 kJ mol
H
H

= +
=

Rearranging the Gibbs Free Energy equation, we obtain,
( )
o o o
o o
o
1
o
o 1 1
90.32 241.6 kJ mol
298.15 K
507.4 J K mol
G H T S
G H T S
H G
S
T
S
S

=
=

=
(

=
=

3-95
3.38. The latent heat of vaporization of water at 100 C is 40.6 kJ mol
1
and when 1 mol of water is vaporized at 100 C and 1 atm
pressure, the volume increase is 30.19 dm
3
. Calculate the work done by the system, the change in internal energy U, the change in
Gibbs energy G and the entropy change S.

Solution:
Given:
1 o 3
vap water
40.6 kJ mol , 100 C, 1 mol, 1 atm, 30.19 dm H T n P V = = = = =
Required: w, U, G, S
Since there is pressure-volume work done on the system, we can determine the work done according to;
( )( )
3
3
3
3
1 atm 30.19 dm
30.19 atm dm
1 atm dm 101.325 J therefore,
30.19 atm dm
w P V
w
w
w
=
=
=
=
=
3
101.325 J
1 atm dm
3059 J w =

Since it is already for 1 mole of water then we can say that,
1
3059 J mol w

=
Recall from Chapter 2 the following equation,
( )
( )
1 1
1
40 600 J mol 3059 J mol
37 541 J mol
H U PV
U H PV
U
U

= +
=
=
=

3-96

Let us now use the Gibbs Free Energy equation:
1
1 1
0
40 600 J mol
108.8 J K mol
373.15 K
G H T S
G
H G
S
T
S S

=
=

=
= =

3-97
3.39. On pages 115116 we worked out the S values for the freezing of water at 0 C and at 10 C. What are the corresponding G
values?

Solution:
Given: pages 115-116
Required: G values
Using Example 3.6 on page 115, we can see that the enthalpy and entropy values have already been worked out. We can therefore
determine the change in Gibbs Free Energy by using our well known equation which will be given below. From the text we have;
a) The entropy change in the reversible freezing water at
o
0 C:
( )
( )
1
fus
2
1 1
2
fus fus
1
fus
1
1
6020 J mol
273.15 K
22.039 172 62 J K mol
6.02 kJ mol
freezing 6.02 kJ mol
6020 J mol 273.15 K
q
S
T
S
H q
H
H
G H T S
G
= =
=
=
=
=
=
=
( )
1
22.039 172 62 J K
( )
1
1
mol
0 J mol G
=

b) The net heat transferred to the surroundings at the constant temperature of
o
10 C :
3-98
( )
( )
( )
1
surr fus gained
surr fus gained
1
1
1 1
sys
1
753 6020 377 J mol
5644 J mol
freezing 5644 J mol
20.64 J K mol
5644 J mol 263.15 K
q q q
H q q q
H
H
S
G H T S
G
+ + = + +
= + +
=
=
=
=
=
( )
1
20.64 J K
( )
1
1
mol
212.58 J mol G
=


3-99
3.40. At 25 C 1 mol of an ideal gas is expanded isothermally from 2 to 20 dm
3
. Calculate U, H, S, A, and G. Do the values depend
on whether the process is reversible or irreversible?

Solution:
Given: Ideal Gas:
o 3 3
1 mol, 25 C, 2 dm, 20 dm
i f
n T V V = = = =
Required: U, H, S, A, and G
It is important that you remember from Chapter 2 that during an isothermal compression or expansion, the change in both the internal
energy and enthalpy are equal to zero due to their temperature dependence.
0 and therefore,
0
m
m
m m
U C T
T
U
H U
=
=
=
= ( ) PV +
0
m
H =

From Eq. 3.45 we are given that,
B
rev
A B
A
dq
S
T

The process is an isothermal expansion so the gas is being taken from state A to state B. We can now solve the integral but A and B will
represent the change in volume which means that a new expression must be formulated. For an Ideal Gas, we will use Eq. 3.50;
2
rev
1
ln
V
q nRT
V
| |
=
|
\ .

Since the temperature is constant, the entropy change is simply the reversible heat absorbed divided by the temperature which leads to,
3-100
2
1
ln
1 mol
V
S nR
V
S
| |
=
|
\ .
=
( )
1 1
8.3145 J K mol

( )
1
1 1
20
ln
2
19.14 J K
19.14 J K mol
m
S
S

| |
|
\ .
=
=

The equation of state (Eq. 3.86) defines the Helmholtz energy and states that:
A U TS
A U T S
=
=

Since we have already determined that the internal energy is equal to zero,
298.15 K
A T S
A
=
=
( )
1
19.14 J K
( )
1
1
1
mol
5708 J mol
5.71 kJ mol
A
A
=
=

The Gibbs energy can now be found using Eq. 3.80,
G H T S =
Remember that the change in enthalpy is also equal to zero.
G H =
298.15 K
T S
G T S
G

=
=
( )
1
19.14 J K
( )
1
1
mol
5.71 kJ mol G
=

3-101
All of the quantities calculated above are state functions. This means that the values are not determined by the way in which the process is
carried out.

3-102
3.41. The values of H and S for a chemical reaction are 85.2 kJ mol
1
and 170.2 J K
1
mol
1
, respectively, and the
values can be taken to be independent of temperature.
a. Calculate G for the reaction at (a) 300 K, (b) 600 K, and (c) 1000 K.
b. At what temperature would G be zero?

Solution:
Given:
1 1
85.2 kJ mol , 170.2 J K H S = =
Required: G, at a, b, c and G=0 where?
a) Using Eq. 3.80 at 300 K,
( )
1
85 200 J mol 300 K
G H TS
G H T S
G
=
=
=
( )
1
170.2 J K
( )
1
1
1
mol
34 140J mol
34.14kJ mol
G
G
=
=

b) Using Eq. 3.80 at 600 K,
( )
1
85 200 J mol 600 K
G H TS
G H T S
G
=
=
=
( )
1
170.2 J K
( )
1
1
1
mol
16 920J mol
16.92kJ mol
G
G
=
=

c) Using Eq. 3.80 at 1000 K,
3-103
( )
1
85 200 J mol 1000 K
G H TS
G H T S
G
=
=
=
( )
1
170.2 J K
( )
1
1
1
mol
85 000 J mol
85.00kJ mol
G
G
=
=

The change in Gibbs energy will be equal to zero when,
G H T S =
1
1 1
0
85 200 J mol
170.2 J K mol
500.6 K
H T S
H T S
H
T
S
T
T

=
=
=

3-104
3.42. The standard Gibbs energy for the combustion,
c
G, of methane has been measured as 815.04 kJ mol
1
at 25.0 C and 802.57
kJ mol
1
at 75.0 C. Assuming that Eq. 3.169 applies and that
c
G changes linearly with temperature in this range, estimate the
enthalpy of combustion at the midpoint of this temperature range, i.e., 50.0 C.

Solution:
Given: methane:
1 o 1 o
815.04 kJ mol , 25 C, 802.57 kJ mol , 75 C, Eq. 3.169
c c
G T G T = = = =
Required:
c
H
Eq. 3.166 gives us an important thermodynamic relationship which is called the Gibbs-Helmholtz Equation.
2
P
G H
T T T
( | |
=
| (
\ .

We can write,

T is the midpoint of the temperature range (50.0 C). In the limit 0 T we will obtain the following;
2
o o o
2 1
2
2 1 2 1
1
P
c c c
P
G H
T T T
G G H G
T T T T T T T
( | |
=
| (
\ .
| | ( | |
=
| | (

\ . \ .
3-105
o o o
2 1
2
2 1 2 1
1 1
o
3 1 1
2
o
1
1 802.57 kJ mol 815.04 kJ mol
348.0 K 298.0 K 348.0 K 298.0 K
8.576 10 kJ K mol
c c c
P
P
c
P
c
G G H G
T T T T T T T
G
T T
H G
T T T
H

| | ( | |
=
| | (

\ . \ .
| | ( | |

| | (

\ . \ .
( | |
=
| (
\ .
=
( )
3 1 1 2
o 3 1
8.576 10 kJ K mol
8.576 10 kJ K
c
T
H

=
( )
1
mol 323.0 K
( )
2
o 1
894.72 kJ mol
c
H

=

3-106
3.43. The heat of vaporization of water at 25 C is 44.01 kJ mol
1
, and the equilibrium vapor pressure at that temperature is 0.0313 atm.
Calculate S, H, and G when 1 mol of liquid water at 25 C is converted into vapor at 25 C and a pressure of 10
5
atm, assuming
the vapor to behave ideally.

Solution:
Given:
1 o 5
vap water eq water
44.01 kJ mol , 25 C, 0.0313 atm, 1 mol, 10 atm H T P n P

= = = = =
Required: S, H, and G
For the conversion of water to vapor at 25 C and 0.0313 atm,
( )
( )
1
vap
vap vap
1
1 1
1 1
1
water 44.01 kJ mol
44 010 J mol
298.15 K
147.610 263 3 J K mol
147.61 J K mol
44 010 J mol 298.15 K
H
q H
S
T T
S
S
S
G H T S
G
= =
=
=
=
=
=
( )
1
147.610 263 3 J K
( )
1
mol
0 G
=

However, under a reversible isothermal expansion from 0.0313 atm to 10
-5
atm we will obtain,
3-107
( )
B
vap
rev
A
1
2
1
rev
2
1 1
rev 5
1 1
rev
1 1
rev
0
ln
ln
0.0313
8.3145 J K mol ln
10
66.921 650 18 J K mol
66.9 J K mol
H
dq
S
T
P
q nRT
P
P
S R
P
S
S
S

=
=
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
=
=

However, for the entire entropy change in the system, we will have to add up the last two entropies calculated to get,
( ) ( )
( )
1 1 1 1
tot
1 1
tot
1 1
tot
1
66.921 650 18 J K mol 147.610 263 3 J K mol
214.531 913 5 J K mol
214.5 J K mol
44 010 J mol 298.15 K
S
S
S
G H T S
G

= +
=
=
=
=
( )
1
214.531 913 5 J K
( )
1
1
1
mol
19 952.690 01 J mol
19.95 kJ mol
G
G
=
=


3-108
3.44. For each of the following processes, state which of the quantities U, H, S, A, and G are equal to zero:
a. Isothermal reversible expansion of an ideal gas.
2
and O
2
2
SO
4

Solution:
Given: see above
Required: U, H, S, A, and G are equal to zero where?
a. Isothermal reversible expansion of an ideal gas
and U H since they are temperature dependent and if there is no change in temperature, then they must be equal to zero.

S will be equal to zero due to the nature of the expansion.

H will be equal to zero

H will be equal to zero

None of the above will be equal to zero.

G due to the fact that here, the system will be at equilibrium

3-109
2
and O
2
U will be equal to zero

2
SO
4
None of the above will be equal to zero.
3-110
3.45. Calculate the change G
m
in the Gibbs energy of 1 mol of liquid mercury initially at 1 bar pressure if a pressure of 1000 bar is
applied to it. The process occurs at the constant temperature of 25 C, and the mercury may be assumed to be incompressible and to
have a density of 13.5 g cm
3
.

Solution:
Given:
o 3
Hg ext Hg
1 mol, 1 bar, 1000 bar, 25 C, 13.5 g cm
i
n P P T = = = = =
Required: G
m

Eq. 3.154 states that,
m
dG V dP =
This means that under the isothermal conditions, we can write;
( )
( )
ext
ext
ext
ext
i
i
T
P
P
m m
P
P
m m i
m m i
G
V
P
G VdP
G V dP V
G V P P
G V P P
| |
=
|
\ .
=
= =
=
=

We must first determine the molar volume for the liquid mercury. Since we are given the density, this can be easily determined.
3-111
3
Hg
Hg
Hg
13.5 g cm
200.6 g
m
m
V
m nM
M
V
=
=
=
= =
( )
1
mol
13.5 g
( )
3
3 1
3 6 3
3
cm
14.859 259 cm mol
since 1 cm 1.0 10 m
14.859 259 cm
m
m
V
V
=
=
=
6 3
1
3
1.0 10 m
mol
1 cm
5 3 1
1.486 10 m mol
m
V

=

Now substituting all the appropriate values into the expression derived above we obtain,
( )
( )( )
( )( )
ext
5 3 1
5 3 1
3 1
5 3
3
1.486 10 m mol 1000 1 bar
1.486 10 m mol 999 bar
0.014 844 4 m bar mol
1 bar 10 Pa, 1 Pa m 1 J
0.014 844 4 m bar
m m i
m
m
m
m
G V P P
G
G
G
G

=
=
=
=
= =
=
( )
1 5 1
mol 10 Pa bar

( )
3 1
1
1
1 484.44 Pa m mol
1 484.44 J mol
1.485 kJ mol
m
m
m
G
G
G
=
=
=


3-112
3.46. The entropy of argon is given to a good approximation by the expression
S
m
/J K
1
mol
1
=36.36 +20.79 ln(T/K)
Calculate the change in Gibbs energy of 1 mol of argon if it is heated at constant pressure from 25 C to 50 C.

Solution:
Given: S
m
/J K
1
mol
1
=36.36 +20.79 ln(T/K)

o o
argon
1 mol, 25 C, 50 C
i f
n T T = = =
Required: G
J ust like in the previous problem which dealt with mercury at constant temperature, we will begin by defining the Gibbs energy as a partial
differential. Eq. 3.161 describes Gibbs energy at constant pressure.
m
m
P
G
S
T
| |
=
|
\ .

Since we have been given an approximation for entropy, let us say:
( )
1 1
1 1
1 1
/ J K mol 36.36 20.79 ln / K
A 36.36 J K mol
B 20.79 J K mol
m
S T

= +
=
=

We can now take the integral of both side of Eq. 3.161 in order to obtain,
3-113
( )
( )
| |
( )
( )
323.15
298.15
323.15
298.15
323.15
298.15
323.15
298.15
323.15
298.15
1

ln
ln
ln
ln
ln
36.36 20.79 J K
m
m
P
m m
m
m
m
m
m
m
G
S
T
G S dT
G A B T dT
G AT B T T T
G AT BT T BT
G AT BT T BT
G A B T BT T
G

| |
=
|
\ .
=
= +
= + (

= +
= +
=
=
( )
1
mol 323.15 298.15 K

1
20.79 J K
( )
( ) ( ) ( )
1
mol 323.15 ln 323.15 298.15 ln 298.15 K

1 1
1
1
389.25 J mol 3 502.281 785 J mol
3 891.531 785 J mol
3.89 kJ mol
m
m
m
G
G
G

=
=
=


3-114
3.47. Calculate the absolute entropy of SO
2
(g) at 300.0 K and 1 bar given the following information: S(15.0 K) =1.26 J K
1
mol
1
,
C
P,m
(s) =32.65 J K
1
mol
1
, T
fus
= 197.64 K,
fus
H =7 402 J mol
1
, C
P,m
(l) =87.20 J K
1
mol
1
, T
vap
= 263.08 K,
vap
H =24 937
J mol
1
, C
P,m
(g) =39.88 J K
1
mol
1
.

Solution:
Given: see above
Required:
abs
S
The absolute entropy of SO
2
(g) at 300.0 K and 1 bar can be calculated using the following:
( ) ( ) ( )
( ) ( )
( )
fus vap
fus
vap
fus
, , 1 1 fus
15.0 K
vap ,
s l
300 K / J K mol 15.0 K
g

T T
P m P m
T
T
P m
T
C C H
S S dT dT
T T T
H C
dT
T T

= + + +

+ +

Now we can simply substitute all of the values given in the problem into the equation stated above. Since we are asking for the absolute
entropy of this compound in the gaseous phase, we must consider the changes that accompany each phase that comes before it. This is why
all of the information given above is important.
3-115
( ) ( )
( ) ( )
197.64 263.08
o 1 1
15.0 197.64
300.0
263.08
o 1 1
32.65 7 402 87.20
300.0 K / J K mol 1.26
197.64
24 937 39.88
+
263.08
300.0 K / J K mol 1.26 32.65 ln
S dT dT
T T
dT
T
S

= + + +
+
= +

( ) ( )
o 1 1
197.64 263.08
37.451 932 81 87.20 ln
15.0 197.64
300.0
+94.788 657 44 39.88 ln
263.08
300.0 K / J K mol 1.26 84.184 661 82 37.451 932 S

| | | |
+ +
| |
\ . \ .
| |
+
|
\ .
= + +
( ) ( )
( )
o 1 1
o 1 1
81 24.940 156 97
+94.788 657 44 5.237 213 332
300.0 K / J K mol 247.862 622 4
300.0 K 247.86 J K mol
S
S

+
+
=
=


3-116
3.48. Initially at 300 K and 1 bar pressure, 1 mol of an ideal gas undergoes an irreversible isothermal expansion in which its volume is
doubled, and the work it performs is 500 J mol
1
. What are the values of q, U, H, G, and S? What would q and w be if
the expansion occurred reversibly?

Solution:
Given: Ideal Gas:
1
1 mol, 1 bar, 300 K, 2, 500 J mol n P T V w

= = = = =
Required: q, U, H, G, and S and q & w (reversible)
Under the irreversible isothermal conditions:
Remember that we have seen numerous times that U and H are equal to zero due to the fact that and
V P
U C T H C T = = . Since
they are dependent on temperature change, it is obvious that these will be equal to zero under isothermal conditions whether they be
reversible or irreversible.
0
0
U
H
=
=

From the equation which describes the change in internal energy, we can determine the work and heat.
1
0 therefore,
500 J mol
U w q
U
q w
q

= +
=
=
=

Remember to read carefully and understand that the system is doing work and therefore, that would mean that the value they give us should
actually have the opposite sign. This is why the heat has a positive value.
ln
dq
S
T
q nRT V
=
=

For a single mole and at constant temperature this expression comes down to,
3-117
2
1
ln
ln
V
V
dq
S
T
q nRT V
S R V
=
=
=

( ) ( )
1 1
1 1
8.3145 J K mol ln 2
5.763 J K mol
S
S

=
=

With all of the above information we are now able to calculate the change in Gibbs energy according to Eq. 3.80.
G H TS
G H
=
=
0
300 K
T S
H
G T S
G

=
=
=
( )
1
5.736 J K
( )
1
1
1
mol
1728.95 J mol
1.73 kJ mol
G
G
=
=

Under reversible conditions, we can assume the following;
( )
rev
H U PV
H U w
G H T S H G T S
G
= +
= +
= = +
T S U + =
rev
rev
1
rev
1.73 kJ mol
w
w T S
w

+
=
=

And using the expression we originally found between work and heat,
3-118
1
rev
rev rev
1
rev
1.73 kJ mol
1.73 kJ mol
w
q w
q
=
=
=


3-119
*3.49. At 100 C 1 mol of liquid water is allowed to expand isothermally into an evacuated vessel of such a volume that the final pressure
is 0.5 atm. The amount of heat absorbed in the process was found to be 30 kJ mol
1
. What are w, U, H, S, and G?

Solution:
Given:
o 1
water
1 mol, 100 C, 0, 0.5 atm, 30 kJ mol
i f
n T P P q = = = = =
Required: w, U, H, S, and G
In an evacuated vessel,
ext
0 P = , which implies that no work is done.
0 w =
We can use a very familiar equation from Chapter 2 to determine the change in internal energy.
1
since 0 then,
30 kJ mol
U w q
w
U q
U

= +
=
=
=

At 100 C, liquid water will begin to go into the vapor phase. When we are working under these conditions, we can make the following
approximation:
3-120
( ) ( )
( )
( )
( )
o o
2 2
1 1
(1) H O l, 100 C H O g, 100 C, 1 atm
1
30 000 J mol 8.3145 J K
H U PV
PV nRT
H U nRT
n
H

= +
=
= +
=
= +
( )
1
mol 373.15 K
( )
1
1
33 102.555 68 J mol
33.10 kJ mol
H
H
=
=

In order to determine the change in entropy, we should consider this process to be both isothermal and reversible. This will enable us to use
the following expression:
( ) ( ) ( )
( )
o o
2 2
1
1 H O l, 100C, 1 atm H O g, 100C, 1 atm
evaporation
fus
H
S
T
=

( )
( )
1
1
1 1
1
40 600 J mol
evaporation
373.15 K
evaporation 108.8 J K mol
S
S

=
=

( ) ( )
( ) ( )
o o
2 2
rev
2
rev
2
2
1
1 1
2
1 1
2
(2) H O g, 100 C, 1 atm H O l, 100 C, 0.5 atm
ln
ln
8.3145 J K mol ln 2
5.76 J K mol
q
S
T
q nRT V
V
S R
V
S
S

=
=
=
=
=

3-121
Since the pressure is decreasing by one half, it would follow that the volume would double during the process, this is why we are not
directly using the pressure values. Now we can determine the net change in entropy.
( )
net 1 2
1 1
net
1 1
net
108.8 5.76 J K mol
114.6 J K mol
S S S
S
S

= +
= +
=

The Gibbs energy can be found according to Eq. 3.80:
( )
1
33 100 J mol 373.15 K
G H TS
G H T S
G

=
=
=
( )
1
86.16 J K
( )
1
1
mol
949.396 J mol G
=

3-122
*3.50. Water vapor can be maintained at 100 C and 2 atm pressure for a time, but it is in a state of metastable equilibrium and is said to be
supersaturated. Such a system will undergo spontaneous condensation; the process is:
H
2
O(g, 100 C, 2 atm) H
2
O(l, 100 C, 2 atm)
Calculate H
m
, S
m
, and G
m
. The molar enthalpy of vaporization
vap
H
m
is 40.60 kJ mol
1
; assume the vapor to behave ideally
and liquid water to be incompressible.

Solution:
Given: see above
Required: H
m
, S
m
, and G
m

In order to solve this problem, we must break down the process into three distinct and reversible steps.
( ) ( ) ( )
( )
( )
2 2
1
2
1
1
1 1
1
1 H O g, 100 C, 2 atm H O g, 100 C, 1 atm
0
ln Eq. 3.94
2 atm
8.3145 J K mol ln
H
V
S R
V
S

=
=
=
1 atm
1 1
1
1 1
5.763 172J K mol S
G H

=
=
1
1
373.15 K
T S
G

=
( )
1
5.763 172J K
( )
1
1
1
mol
2150 J mol G
=

Recall that for an isothermal process, there is no change in enthalpy.
3-123
( ) ( ) ( )
( )
( )
( )
o o
2 2
1
2 vap
vap
2
1
2
1 1
2
2
2 H O g, 100C, 1 atm H O l, 100C, 1 atm
40 600 J mol
condensation
40 600 J mol
condensation
373.15 K
condensation 108.803 430 J K mol
0
m
m
H H
H
S
T
S
S
G
= =
=
=
=
=

For a reversible process at constant T and P, there is no change in Gibbs energy.
( ) ( ) ( )
2 2
3 H O l, 100 C, 1 atm H O l, 100 C, 2 atm
The enthalpy, entropy and Gibbs energy changes are negligible for this particular step of the process. We can now sum up all of the values
in order to determine the H
m
, S
m
, and G
m
.
1 m
H H =
2 3
H H + +
3
40.6kJ
5.763 172 108.803 430
m
m
H
S S
=
= +
( )
1
1
1 2
J K
103 J K
m
m
S
G G G
=
= +
3
G +
2150 J
2.15 kJ
m
m
G
G
=
=

3-124
*3.51. Initially at 300 K and 10 atm pressure, 1 mol of a gas is allowed to expand adiabatically against a constant pressure of 4 atm until
equilibrium is reached. Assume the gas to be ideal with:
C
P,m
/J K
1
mol
1
=28.58 +1.76 10
2
T/K
and calculate U, H, and S.

Solution:
Given: 300 K, 10 atm, 1 mol, 4 atm
i i f
T P n P = = = =
Required: U, H, and S
Remember from Chapter 2, that an adiabatic process is one that occurs in a vessel whose walls are perfectly insulating so that no heat can
pass through them. In short, there is no heat exchange between the system and the surroundings. Normally, we know that,
dU dq PdV = however, since 0 dq = then we can determine the change in internal energy according to the following:
( )
( )
,
, ,
, ,
2 1 1
,
2 1 1
,
28.58 1.76 10 / K 8.3145 J K mol
20.2655 1.76 10 / K J K mol
f
i
T
V m
T
P m V m
V m P m
V m
V m
U C dT
C C R
C C R
C T
C T

=
=
=
(
= +

= +

Since we have only been given the initial temperature, we can rearrange the expression using Eq. 2.81 in order to make use of the pressure
values stated above.
( )
( )
,
,
2
0
1 mol
20.2655 1.76 10 / K
f
i
f
i
f
i
V m
V m f
T
m
T
V
m f
V
V
m f
V
nC dT PdV
C dT P dV dw
U T dT
U P dV
U P dV
+ =
= =
= +
=
=

3-125
Assuming that the gas is ideal, we can use the Ideal Gas Law in order to finish solving this integration.
i
PV nRT
n
V
=
= ,
i
f
i
n
RT
V
P
=
f
f
RT
P

1 1
1 1
300 K
4 atm 8.3145 J K mol
4 atm 10 atm
30 K
4 atm 8.3145 J K mol
4 atm 1 atm
f
i
m f
f i
f
m
f
m
RT
RT
U P
P P
T
U
T
U

| |
= |
|
\ .
| |
=
|
\ .
| |
=
|
\ .

Now we can use the initial expression found for the change in internal energy. We can set both equations equal to one another in order to
solve for the final temperature.
( )
( ) ( )
( ) ( )
( ) ( )
2
1
2
2 2 2
2 2
2 2
20.2655 1.76 10 / K
1
20.2655 1.76 10
2
20.2655 300 0.008 98 300
20.2655 300 0.008 98 300 4 atm
f i
f
f
T
m
T
m f i
m f
f
U T dT
U T T T T
U T T
T T
= +
= +
= +
+ =
1
8.3145 J K
1
mol
4 atm
f
T
30 K
1 atm
2
2
20.2655 6079.65 0.008 98 808.2 8.3145 997.74
0.008 98 28.58 7885.59 0
f
f
f f
f
T T T
T T
| |
|
\ .
+ = +
+ =

This can be solved using the quadratic equation.
3-126
( )
2
2
4
2
28.58 28.58 4 0.008 98 7 885.59
2 0.008 98
28.58 33.167 254 83
0.017 96
taking the positive root,
255.415 079 6 K
f
f
f
b b ac
x
a
T
T
T

=

=

=
=

( ) ( )
2 2
1
1
20.2655 255.415 079 6 300 0.008 98 255.415 079 6 300
1 125.908 676 J mol
1 125.9 J mol
m
m
m
U
U
U
= +
=
=

( ) ( )
2 2
1
1
28.58 255.415 079 6 300 0.008 98 255.415 079 6 300
1496.609 996 J mol
1496.6 J mol
m
m
m
H
H
H
= +
=
=

3-127
( )
,
255.3
1 1
300
1 1
For 1 mol of ideal gas,
28.58 0.0176 4
/ J K mol 8.3145ln
10
255.3
/ J K mol 28.58ln 0
300
m
m m m
m m
m
P m
m
m
m
PV RT
d PV RdT PdV V dP
RT
PdV RdT V dP RdT dP
P
RTdP
dU RdT
C R
P
dS dT dP
T T P
T
S dT
T
S

=
= = +
= =
+
= =
+ | |
=
|
\ .
| |
= +
|
\ .
( )
1 1
1 1
.0176 255.3 300 7.618 499 29
/ J K mol 2.220 592 051
2.22 J K mol
m
m
S
S

+
=
=

3-128
3.52. Calculate H, G, and S for the reaction
CH
4
(g) +2O
2
(g) O
2
(g) +2H
2
O(l)
making use of the data in Appendix D.

Solution:
Given: Appendix D
Required: H, G, S
It is possible to use the enthalpies and free energies of formation in conjunction with a form of Eq. 2.53 in order to solve for the standard
enthalpy and standard Gibbs energy for the reaction given above. Recall that all of the values given in Appendix D were taken at 298.15 K.
( ) ( )
( ) ( ) ( )
2 4 2
products reactants
2 H O, l CH , g 2 O , g
f f
f f f
H H H
H H H H
=
= +

( ) ( )
( ) ( )
( ) ( ) ( )
1
1
2 4 2
2 285.830 74.6 kJ mol
497 kJ mol
products reactants
2 H O, l CH , g 2 O , g
f f
f f f
H
H
G G G
G G G G
(

= (

=
=
= +

( ) ( )
( )
1
1
1
1 1
2 237.1 50.5 kJ mol
424 kJ mol
497 424 kJ mol
298.15 K
245 J K mol
G
G
G H T S
T S H G
H G
S
T
S
S

(

= (

=
=
=

=
+
=
=

3-129
3.53. The following is a set of special conditions:
a. True only for an ideal gas.
b. True only for a reversible process.
c. True only if S is the total entropy (system +surroundings).
d. True only for an isothermal process occurring at constant pressure.
e. True only for an isothermal process occurring at constant volume.

Consider each of the following statements, and indicate which of the above conditions must apply in order for the statement to be
true:

a. U =0 for an isothermal process.
b. H =0 for an isothermal process.
c. The total S =0 for an adiabatic process.
d. S > 0 for a spontaneous process.
e. G < 0 for a spontaneous process.

Solution:

a) U =0 for an isothermal process only when the gas is an Ideal Gas
b) H =0 for an isothermal process only when the gas is an Ideal Gas
c) The total S =0 for an adiabatic process when this process is a reversible one
d) S > 0 for a spontaneous process but only when considering the total entropy change occurring in the system
e) G < 0 for a spontaneous proce


3-130
3.54. Calculate the entropy and Gibbs energy changes for the conversion of 1 mol of liquid water at 100 C and 1 bar pressure into vapor
at the same temperature and a pressure of 0.1 bar. Assume ideal behavior. The heat of vaporization of water at 100 C is 40.6
kJ mol
1
.

Solution:
Given:
o 1
water water vap vap water
1 mol, 100 C, 1 bar, 0.1 bar, 40.6 kJ mol n T P P H = = = = =
Required: , S G
There are two stages to this process. First we must determine the entropy change when heating the liquid water to bring it to the vapor
phase. After this, we must expand the gas from the initial pressure to the final pressure of 0.1 bar. This will yield the following:
( )
( )
( )
vap
1
1
1
1 1
1
2 1
2
1 2
1 1
2
1
2
1 Vaporize water at 1 bar
40600 J mol
373.15 K
108.803 430 J K mol
2 Expansion from 1 bar to 0.1 bar
ln ln
1
8.3145 J K mol ln
0.1
19.144 844 J K mol
m
H
S
T
S
S
V P
S R R
V P
S
S
=
=
=
= =
=
=
1

The net entropy change is therefore;
net 1 2
1 1
net
127.9 J K mol
S S S
S

= +
=

3-131
1
40 600 J mol 373.15 K
G H T S
G

=
=
1
127.9 J K
( )
1
1
1
mol
7143.898 J mol
7.144 kJ mol
G
G
=
=


3-132
3.55. In the bacterium nitrobacter the following reaction occurs:

2 2 3
1
NO + O NO
2

Use the data in Appendix D to calculate H, G, and S for the reaction.

Solution:
Given: Appendix D
Required: H, G, S
We will use the same method as previously done for this type of question.
( ) ( )
( ) ( )
( )
o o o
o o o
3 2
o 1
o 1
o 1
products reactants
NO NO
206.85 104.6 kJ mol
102.25 kJ mol
102.3 kJ mol
f f
f f
H H H
H H H
H
H
H

=
=
= +
=
=

( ) ( )
( ) ( )
( )
o o o
o o o
3 2
o 1
o 1
o 1
products reactants
NO NO
108.74 32.2 kJ mol
76.54 kJ mol
76.5 kJ mol
f f
f f
H H H
G G G
G
G
G

=
=
= +
=
=

( ) ( )
( ) ( )
o o o
o o o
o o o
o o
o
1
o
o 1 1
o 1
products reactants
102.3 76.5 kJ mol
298.15 K
0.086533624 kJ K mol
86.5 J mol
f f
H H H
G H T S
T S H G
H G
S
T
S
S
S
=
=
=

=

=
=
=

3-133
3.56. At 100 atm pressure water boils at 312 C, while at 5 atm it boils at 152 C. Compare the Carnot efficiencies of 100-atm and 5-atm
steam engines, if T
c
is 30 C.

Solution:
Given: water:
o o o
1 1 2 2
100 atm, 312 C, 5 atm, 152 C, 30 C
c
P T P T T = = = = =
Required: Carnot efficiencies for steam engines
Recall that the efficiency is given by Eq. 3.21 which states:
e
h c
h
T T
T
=

For the 100-atm steam engine:
( )
585.15 K, 303.15 K
585.15 303.15 K
e
h c
T T = =
=
585.15 K
e 0.48
e 48%
=
=

For the 5-atm steam engine:
( )
425.15 K, 303.15 K
425.15 303.15 K
e
h c
T T = =
=
425.15 K
e 0.29
e 29%
=
=

3-134
3.57. A cooling system is designed to maintain a refrigerator at 4 C in a room at 20 C. If 10
4
J of heat leaks into the refrigerator each
minute, and the system works at 40% of its maximum thermodynamic efficiency, what is the power requirement in watts? [1 watt
(W) =1 J s
1
.]

Solution:
Given:
o o 4 1
system room
4 C, 20 C, 10 J min T T q

= = =
Required: ( ) 40% P
Eq. 3.21 gives the efficiency for this cooling system.
( )
room system
room
e
e
293.15 269.15 K
e
h c
h
T T
T
T T
T
=
293.15 K
( )( )
4 1
1
e 0.082
e
e 0.082 10 J min
818.69 J min
h c
c h
c
T T w
q T
w q
w
= =
= =
=

3-135
1
818.69 J min w

=
1 min
1
1
60 sec
13.64 J s
(40%)
e
13.64 J s
(40%)
0.4
(40%) 34.1 W
w
w
P
P
P
=
=
=
=


3-136
3.58. A heat pump is employed to maintain the temperature of a house at 25 C. Calculate the maximum performance factor of the pump
when the external temperature is (a) 20 C, (b) 0 C, and (c) 20 C.

Solution:
Given:
o
house
25 C T =
Required: performance factor for a, b, c
a) at 20 C;
1
e
298.15 K
h
h c
Pf
T
Pf
T T
Pf
=
=
=
( ) 298.15 293.15 K
59.63% Pf =

b) at 0 C;
1
e
298.15 K
h
h c
Pf
T
Pf
T T
Pf
=
=
=
( ) 298.15 273.15 K
11.93% Pf =

c) at -20 C;
3-137
1
e
298.15 K
h
h c
Pf
T
Pf
T T
Pf
=
=
=
( ) 298.15 253.15 K
6.63% Pf =

3-138
3.59. A typical automobile engine works with a cylinder temperature of 2000 C and an exit temperature of 800 C. A typical octane fuel
(molar mass =114.2 g mol
1
) has an enthalpy of combustion of 5500 kJ mol
1
and 1 dm
3
(0.264 U.S. gal) has a mass of 0.80 kg.
Calculate the maximum amount of work that could be performed by the combustion of 10 dm
3
of the fuel.

Solution:
Given:
o o 1 1
cyl exit fuel
2000 C, 800 C, 114.2 g mol , 5500 kJ mol
c
T T M H = = = =

3
1 dm, 0.80 kg V m = =
Required:
3
max
such that 10 dm w V =
We can first determine the efficiency of this automobile engine due to the fact that we are given both the exit and cylinder temperatures.
Eq. 3.21 gives the efficiency for this system.
( )
cyl exit
cyl
e
e
2273.15 1073.15 K
e
h c
h
T T
T
T T
T
=
2273.15 K
e 0.528 =

Given the fuels mass and molar mass, we can determine the number of moles involved in the reaction. We are initially told that 1 dm
3

(0.264 U.S. gal) has a mass of 0.80 kg. Since 1 dm
3
can be described as
3
1 dm 1 dm 1 dm 1 dm 10 cm 10 cm 10 cm 1000 mL 1 L = = = = it follows that 1 liter of fuel is equivalent to 0.80 kg.

for 1 liter
800 g
m
n
M
n
=
=
114.2 g
1
mol
7.005 254 mol n =

3-139
Using the enthalpy of combustion for the reaction, it is possible to determine the amount of energy produced (ie. the heat).
o
7.005 254 mol
c
q n H
q
=
=
( )
1
5500 kJ mol
( )
4
38 528.8967 kJ 3.85 10 kJ q q = =

Eq. 3.20 gives a modified version of the efficiency which can be used in conjunction with the value calculated in the first part of the
problem in order to determine the work done during the combustion of the fuel.
( )( )
4
e
e
0.528 38 528.8967 kJ
20 343.257 kJ
2.03 10 kJ
h
h
w
q
w q
w
w
w
=
=
=
=
=


3-140
3.60. The temperature of a building is maintained at 20 C by means of a heat pump, and on a particular day the external temperature is 10
C. The work is supplied to the heat pump by a heat engine that burns fuel at 1000 C and operates at 20 C. Calculate the
performance factor for the system (i.e., the ratio of the heat delivered to the building to the heat produced by the fuel in the heat
engine). Assume perfect efficiencies of the pump and the engine.

Solution:
Given:
o o o o
building ext burn operate
20 C, 10 C, 1000 C, 20 C T T T T = = = =
Required: performance factor
The efficiency of the reversible Carnot engine can be defined as the work done by the system during the cycle divided by the work that
would have been done if all the heat absorbed at the higher temperature had been converted to work. From this statement, we can extract
Eq. 3.20. We say that efficiency is unity (100% efficiency) only if the lower temperature is zero. Here, we are assuming that the
efficiencies of the pump and the engine are perfect. This yields the following expression.
Eq. 3.22:
or
h c h c h h
h h c c
T T q q T q
T q T q
+
= =

Let the heat being supplied to the building be q
h
at 20 C. At the same time, q
c
will be the heat taken in by the heat pump at 10 C. With
this information, it is possible to determine the amount of work supplied to the heat pump.
293.15 K
h h
c c
h
c
q T
q T
q
q
=
=
283.15 K
( )
293.15 K
h
c
q
q
=
283.15 K
1.035 317
h
c
q
q
=

From Eq. 3.20 and Eq. 3.21 we get,
3-141
e
since
h c h c
h h h
h h
c c
T T q q w
q T q
T q
T q

= = =
=

1
0.034 112
h c
c
h
h
h
w q q
q
w q
q
w q
=
| |
=
|
\ .
=

We must now consider the heat that is produced as a result of fuel combustion. Let q
h
be the heat produced by the fuel at 1000C. On the
other hand, q
c
will be equivalent to the heat being rejected at 20C.
1273.15 K
h h
c c
h
c
q ' T '
q ' T'
q '
q '
=
=
293.15 K
( )
1273.15 K
h
c
q '
q '
=
293.15 K
4.342 998
h
c
q '
q '
=

From Eq. 3.20 and Eq. 3.21 we get,
3-142
e
since
1
0.769 744
h c h c
h h h
h h
c c
h c
c
h
h
h
T T q ' q ' w
q ' T q '
T ' q '
T' q '
w q ' q '
q '
w q '
q '
w q '

= = =
=
=
| |
=
|
\ .
=

Setting both values for work equal to one another, it will be possible to solve for the performance factor.
0.034 112 0.769 744
1
e
0.769 744
0.034 112
22.57%
h h
h h h
h c h c h
w q q '
T q q
Pf
T T q q q '
Pf
Pf
= =
= = = =
+
=
=

3-143
3.61. Suppose that a refrigerator cools to 0 C, discharges heat at 25 C, and operates with 40% efficiency.
a. How much work would be required to freeze 1 kg of water (
f
H =6.02 kJ mol
1
)?
b. How much heat would be discharged during the process?

Solution:
Given:
o o
cools discharges
0 C, 25 C, e 40% T T = = =
Required:
freeze discharge
, w q
First we should determine the amount of heat that must be removed from 1 kg of water in order to freeze it. This can be done using the
number of moles in 1 kg (water) and the enthalpy of formation given above.
a) This yields,
o
1000 g
c f
q n H
m
n
M
=
= =
18.0152 g
1
mol
55.508 682 mol
55.508 682 mol
c
n
q
=
=
( )
1
6.02 kJ mol
( )
2
freeze
334.16 kJ
3.34 10 kJ
c
q
q
=
=

The value for heat that we just calculated will be the amount of heat gained by the refrigerator during the cooling process. Assuming that
we were able to work under 100% efficiency, we would have the following from Eq. 3.22;
3-144
or
298.15 K
h c h c h h
h h c c
h h
c c
h
c
T T q q T q
T q T q
q T
q T
q
q
+
= =
=
=
273.15 K
298.15 K
h c
q q =
273.15 K
334.16 kJ 1.091 525
364.74 kJ
h
q
| |
=
|
\ .
=

The amount of heat discharged at 25 C is therefore expressed as,
discharged
365 kJ 365 kJ
h
q q = =
The work required to be supplied to the refrigerator can then be found by subtracting the amount of heat that must be removed from 1 kg of
water in order to freeze it from the amount of heat discharged. We obtain,
supplied discharge freeze
supplied
supplied
364.74 334.16 kJ
30.58 kJ
w q q
w
w
=
=
=

We will now work under the given conditions (ie. efficiency is equal to 40%) in order to determine the amount of work required to freeze 1
kg of water. By inspection:
( )
supplied
freeze
freeze
freeze
e
40
e 0.40
100
100
30.58 kJ
40
76.45 kJ
w
w
w
w
=
= =
=
=

3-145
b) The amount of heat discharged at 25 C at 40 percent efficiency is therefore given by the expression which defines the change in internal
energy of a system:
( )
freeze freeze
discharged
o
discharged
334.15 kJ 76.45 kJ
25 C 411 kJ
U q w
U q w
U
U q
q
= +
= +
= +
=
=

3-146
3.62. Show that (a)
,
T
U T P
V

| |
=
|
\ .
and (b) ( ),
T
U
V P T
P

| |
=
|
\ .
where
1
,
T
V
V P
| |
=
|
\ .
is called the isothermal compressibility
coefficient.
Usetherelationship .
V T P
P P V
T V T
( | | | | | |
=
| | | (
\ . \ . \ .

Solution:

On the basis of principles that have been developed and explored in the previous problems (Chapter 3), it is possible to derive a number of
relationships between different thermodynamic quantities. We can derive equations that give the internal energy and the enthalpy in terms
of pressure, volume and temperature.
a) Using the relationship ship given above and knowing that
1
,
T T
V U T P
V P V

| | | |
= =
| |

\ . \ .

we have;

P
T
T
V
P T
V T
P
| |
|
| | \ .
= =
|
| | \ .
|
\ .

Which can then be substituted into Eq. 3.128 in order to get,

expanding to obtain,
T V
T
T
U P
P T
V T
U
P T
V
U T P
V
| | | |
= +
| |

\ . \ .
| | | |
= +
| |
\ . \ .
| |
=
|
\ .

b) Using the chain rule for partial differentiation given in Appendix C we can then say that:
3-147

if we have then,
y
y x
z
x
z z
dz dx dy
x y
| |
|
\ .
| | | |
= +
| |

\ . \ .

Then according to Eulers Reciprocity Theorem, we will get the following:

1
0
1
y x
y x
y
y
y z x
y z x
y z x
z z
x y y x
z
x x
z
z z y
x y x
x z z
y y x
z z y
x y x
( (
| | | |
=
( ( | |

\ . ( \ .

| |
=
|
| | \ .
|
\ .
| | | | | |
= +
| | |

\ . \ . \ .
| | | | | |
=
| | |

\ . \ . \ .
| | | | | |
=
| | |

\ . \ . \ .

We can now use what we have been given above in order to prove the given relationship.

3-148
therefore,
since;
and
V T P
T T T
T T
T
P P V
T V T
U U V
P V P
U T P V
V
V P
U T P
P

| | | | | |
=
| | |

\ . \ . \ .
| | | | | |
=
| | |

\ . \ . \ .
| | | |
= =
| |

\ . \ .
| |
=
|
\ .

| |

|
\ .
( )
( )
simplify to get,
T
V
U
V P T
P

| |
=
|
\ .

3-149
3.63. Derive an equation of state from
dH =T dS +V dP
by taking the partial derivative with respect to P at constant temperature. Then use the appropriate Maxwell relation and the
definition of to express the partial in terms of easily measured quantities.

Solution:
Recall that for Maxwell Relations, they are used to describe an infinitesimal process involving only PV work. This means that we are able
to combine the First and Second Laws of Thermodynamics. This is shown by Eq. 3.105:

dU dw dq PdV TdS = + = +

Since we are already given the expression above for enthalpy let us find the partial derivative.

T T T
dH T dS V dP
H S P
T V
P P P
= +
| | | | | |
= +
| | |

\ . \ . \ .
T T
H S
T V
P P
| | | |
= +
| |

\ . \ .

Knowing that
T P
S V
P T
| | | |
=
| |

\ . \ .
,

T P
T P
S V
P T
H V
V T
P T
| | | |
=
| |

\ . \ .
| | | |
=
| |

\ . \ .

From Eq. 3.139 we are given the following:

1
P
V
V T
| |
=
|
\ .
which then rearranges to
P
V
V
T

| |
=
|
\ .
and making the last substitution we obtain,
3-150

( )
( ) 1
T
T
H
V T V
P
H
V T
P
| |
=
|
\ .
| |
=
|
\ .

3-151
3.64. Derive expressions for (a) and (b) for an ideal gas.

Solution:
We have seen many times by now that the Ideal Gas Law is given by, PV=nRT. Remember from the previous problem that we are given the
value of in Eq. 3.139 which states that:

1
P
V
V T
| |
=
|
\ .

We can also determine the relationship for by Eq. 3.142 which gives:

1
T
V
V P
| |
=
|
\ .

a) Since the volume is the important variable in this case, let us rearrange the Ideal Gas Law to isolate for it.

therefore,
m
m
P
PV nRT
nRT
V
P
RT
V
P
V R
T P
=
=
=
| |
=
|
\ .

Let us make the appropriate substitution into the equation for the cubic expansion coefficient to get,
3-152
1
1
1
1
P
m
P m
m
P
m
m
V
V T
V
V T
V R
T P
R
V P
R
V P
T
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
=
=

b) For the second part of this problem, we will use the same rearrangement of the Ideal Gas Law, however, we will take the partial
derivative with respect to the pressure while keeping the temperature constant. This will yield the following:

3-153
2
2
2
1
1
1
m
m
T
m
T m
m
PV nRT
nRT
V
P
RT
V
P
V RT
P P
V
V P
RT
V P
RT P
RT P
P
=
=
=
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
| | \ .
|
\ .
RT
RT | |
|
\ .
2
P
1
P
| |
|
\ .
=

3-154
*3.65. Suppose that a gas obeys the van der Waals equation
( )
2
m
m
a
P V b RT
V
| |
+ =
|
\ .

Prove that:
2
m m
T
U a
V V
| |
=
|
\ .

Solution:
Remember that Eq. 3.105 represents a process which is infinitesimal and involves only PV work. We have combined both the First and
Second Laws of Thermodynamics.

dU dw dq PdV TdS = + = +

We will continue by using the second part of this expression as it relates back to the Van der Waals equation. Let us take the partial
derivative with respect to the volume while keeping the temperature constant.

m
m m m
T T T
dU TdS PdV
V U S
T P
V V V
=
| | | | | |
=
| | |

\ . \ . \ .
m m
T T
U S
T P
V V
| | | |
=
| |

\ . \ .

Now since we know that and
V m
T
P S
PdV TdS
T V
| | | |
+ =
| |

\ .
\ .
then we can make this substitution into the above (this is given by Eq. 3.124):

m m
T T
V m
T
U S
T P
V V
U P
T P
V T
| | | |
=
| |

\ . \ .
| | | |
=
| |

\ .
\ .

3-155
From the Van der Waals equation given in the problem,

( )
( )
2
2
m
m
V m m
a
P V b RT
V
P P a
P
T V b T V
| |
+ =
|
\ .
| | | |
= = +
| |
\ .
\ .

We can now substitute this into the above and simplify which will yield:
( )
2
1
V m
T
V m m
m
T
U P
T P
V T
P P a
P
T V b T V
U
T
V
| | | |
=
| |

\ .
\ .
| | | |
= = +
| |
\ .
\ .
| |
=
|
\ .
1
T
2
m
m
T
a
P P
V
U
P
V
( | |
+
( |
\ .
| |
=
|
\ .
2
m
a
P
V
| |
+
|
\ .
2
m m
T
U a
V V
| |
=
|
\ .

3-156
*3.66. Obtain an expression for the J oule-Thomson coefficient for a gas obeying the equation of state:
P(V
m
b) =RT
in terms of R, T, P, V
m
, and C
P,m
.

Solution:
From Chapter 2 we have seen that the J oule-Thomson coefficient is given by Eq. 2.108:

H
T T
P P
| |
=
|

\ .

We must also realize that the enthalpy is given by dH TdS VdP = + so we need to take the partial derivative of dH both with respect to T and
P in order to solve for the final expression. Recall that from Eq. 2.109 and Eq. 2.110:

0
T P
P
T P T
H H
dH dP dT
P T
H H T
C
P T P

| | | |
= + =
| |

\ . \ .
| | | | | |
= =
| | |

\ . \ . \ .

Using Eulers Chain Rule, we can redefine the expression given above for the J oule-Thomson coefficient.

H
T
H
P
T T
P P
H
T H P
H P
T
| |
=
|

\ .
| |
|
| | \ .
= =
|
| | \ .
|
\ .
T
P
| |
|
\ .
T
H
P
| |
|
\ .
,
1
H T P
T H
P C P
| | | |
=
| |

\ . \ .

Let us now define
T
H
P
| |
|
\ .
using the relationship between T, P and V and enthalpy.
3-157
T T T
H S P
T V
P P P
| | | | | |
= +
| | |

\ . \ . \ .
T T
H S
T V
P P
| | | |
= +
| |

\ . \ .

Since we know that according to Eq. 3.125:
T P
S V
P T
| | | |
=
| |

\ . \ .

We can make this substitution into the above equation to get,

T T
T P
T P
H S
T V
P P
S V
P T
H V
V T
P T
| | | |
= +
| |

\ . \ .
| | | |
=
| |

\ . \ .
| | | |
=
| |

\ . \ .

Let us now substitute this expression into that of the J oule-Thomson coefficient to obtain,

3-158
1
1
H
T P
T P
P P
P
P
T T
P P
H
C P
H V
V T
P T
V
V T
C T
V
T V
T
C
| |
=
|

\ .
| |
=
|
\ .
| | | |
=
| |

\ . \ .
( | |
=
| (
\ .

| |

|
\ .
=

For a single mole of this gas (as was given by the equation of state) we can then write,

( )
,
P
P
m
m
P
P m
m
V
T V
T
C
V
T V
T
C
P V b RT
| |

|
\ .
=
| |

|
\ .
=
=

3-159
,
,
,
m
P
m
m
P
P m
m
P m
m
P m
V R
T P
V
T V
T
C
R
T V
P
C
RT
V
P
C
| |
=
|
\ .
| |

|
\ .
=
| |
|
\ .
=
=


3-160
*3.67. Derive the following equations:
a.
2
2
P
G
C T
T
| |
=
|
\ .

b.
2
2
P
T
P
C V
T
P T
| | | |
=
| |

\ .
\ .

Solution:
a) Using Eq. 3.119 we can see that,

and
T P
G G
V S
P T
| | | |
= =
| |

\ . \ .

We will use the second expression and differentiate each side (with respect to T while keeping P constant) in order to obtain the desired
equation.

2
2
P
P
P
G
S
T
G S
T T
| |
=
|
\ .
| | | |
=
| |

\ .
\ .

Eq. 3.55 gives us
rev
q
dS
T
= and we can also say that
P
C dT
dS
T
= at constant pressure. Therefore, we can make this substitution into the
above expression to obtain,

2
2
2
2
2
2
P
P
P
P
P
P
G S
T T
C G
T T
G
C T
T
| | | |
=
| |

\ .
\ .
| |
=
|
\ .
| |
=
|
\ .

3-161

b) C
P
is defined by Eq. 2.27 which states that:

P
P
H
C
T
| |
=
|
\ .

Using the Euler Reciprocity Theorem we can write,
P
P T T
T P
C H H
P P T T P
( ( | | | | | |
= =
| | | ( (

\ . \ . \ .

From problem 3.66 we have the following:

T T
dH VdP TdS
H P
V
P P
= +
| | | |
=
| |

\ . \ .
since
T
T T
P T
T P
S
T
P
H S
V T
P P
VdP TdS
V S
T P
H V
V T
P T
| |
+
|
\ .
| | | |
= +
| |

\ . \ .
=
| | | |
=
| |

\ . \ .
| | | |
=
| |

\ . \ .

This can now be substituted into the expression derived from Eq. 2.27.

3-162
P
P T T
T P
T P
P
T P
P
C H H
P P T T P
H V
V T
T P T T
H V
T P T
( ( | | | | | |
= =
| | | ( (

\ . \ . \ .

( | | | | | |
=
| | | (

\ . \ .
\ .
( | | | |
=
| | (

\ . \ .

2
2
P
P
V V
T
T T
| | | |

| |

\ .
\ .
2
2
P
T
P
C V
T
P T
| | | |
=
| |

\ .
\ .

3-163
*3.68. Starting with the definition of the Helmholtz energy, A =U TS, prove that the change in Helmholtz energy for a process at constant
temperature is the total work (PV and non-PV). (This relationship holds without any restriction as to volume or pressure changes.)

Solution:

We have already been given the equation that defines the Helmholtz energy. Now let us define it for an infinitesimal process.

A U TS
dA dU TdS SdT
=
=

At constant temperature then the above becomes:

since then;
dA dU TdS SdT
dU dw dq
dA dw dq SdT
=
= +
= +

However, knowing that dq TdS = so we can say that:

dA dU TdS SdT
dU dw dq
dA dw dq
=
= +
= + TdS SdT
dA dw SdT
=

Using the First Law of Thermodynamics which states that: dU TdS PdV = we can change the work so that it only considers pressure-
volume work in order to obtain,

dA dU TdS SdT
dU TdS PdV
dA TdS
=
=
= PdV TdS SdT
dA PdV SdT
=

3-164
*3.69. Prove that if a gas obeys Boyles law and if in addition (U/V)
T
=0, it must obey the equation of state PV =constant T.

Solution:

From the previous problem and the First Law of Thermodynamics, recall that (Eq. 3.105):

dU dw dq TdS PdV = + =

Let us take the partial differential with respect to volume while keeping temperature constant.
T T T
U S V
T P
V V V
| | | | | |
=
| | |

\ . \ . \ .
0
0
T T
U S
T P
V V
=
| | | |
= =
| |

\ . \ .

We can make the following substitution into the above equation to obtain,
0
0
V T
T T
T V
TdS PdV
P S
T V
U S
T P
V V
U P
T P
V T
=
| | | |
=
| |

\ . \ .
| | | |
= =
| |

\ . \ .
| | | |
= =
| |

\ . \ .

This means that
V
P P
T T
| |
=
|
\ .
and this can be integrated to get,
ln
V
P P
T T
P P
T T
| |
=
|
\ .
| |
=
|
\ .

And using the rules for logarithms,

3-165
( ) ( )
( ) ( )
ln ln ln 0
ln ln
P
P T
T
P T C
| |
= =
|
\ .
= +

Thus, PV C T = when taking the exponential for the expression.

3-166
*3.70. Derive the relationship
U
S P
V T
| |
=
|
\ .

and confirm that it applies to an ideal gas.

Solution:

We will again use Eulers Chain Rule and Reciprocity Theorem for this problem. This will give us the following,

S
U
V
U
S U V
U V
S
| |
|
| | \ .
=
|
| | \ .
|
\ .
S
S
V U
| |
|

\ . V
| |
|
\ .

Using the Maxwell Relation given by Eq. 3.116, we observe,

and
S V
U U
P T
V S
| | | |
= =
| |

\ . \ .

Which proves that:
S
U
V
U
U
U
S V
U V
S
S P
V T
S P
V T
| |
|
| | \ .
=
|
| | \ .
|
\ .
| | | |
=
| |
\ . \ .
| | | |
=
| |
\ . \ .

For an Ideal Gas, we should note that the internal energy only depends on the temperature. This will allow us to write,

3-167
U T
S S
V V
| | | |
=
| |

\ . \ .

For an Isothermal Process involving n moles of Ideal Gas,

ln dS nRd V
nRdV
dS
V
=
=

and since
P nR
PV nRT
T V
PdV
dS
T
= =
=

Thus,

and therefore
T U
PdV
dS
T
S P S P
V T V T
=
| | | |
= =
| |

\ . \ .

3-168
3.71. Starting from Eq. 3.160,
a. Show that
2
1
2
2
1
In ,where .
P
m
P
PV f Z
dP Z
P P RT
| |
| |
= =
| |
\ .
\ .

b. For a nonideal gas, the equation of state is given as PV
m
=RT +(b A/RT
2/3
)P (see Example 1.6, p. 42). Derive an expression to
find the fugacity of the gas at a given temperature and pressure when the constants b and A are given.

Solution:

a) If P
1
is a sufficiently low pressure, Eq. 3.160 states that:
2
1
2
1
ln
P
m
P
f RT
RT V dP
f P
| |
=
|
\ .

This relationship describes the fugacity for a gas. Let us divide both sides by RT and using the definition of the compression factor (given
in Chapter 1, Eq. 1.98) Z, we will obtain the following:

2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
ln
ln
1
ln
1
ln
P
m
P
m
m
P
P
m
P
P
P
P
f PV RT
RT dP
f P
PV PV
Z
nRT RT
PV RT
f
RT
dP
f P
PV
f
RT
dP
f P
f Z
dP
f P
| |
=
|
\ .
= =
| |
|
=
|
|
\ .
| |
|
=
|
|
\ .
| |
=
|
\ .

3-169

b) Lets first substitute the equation of state into the expression for the compression factor.

( )
2/3
/
m
m
PV
Z
RT
PV RT b A RT P
RT
Z
=
= +
=
( )
2/3
/ b A RT P
RT
(
+

( )
( )
( )
( )
( )
2/3
5/3
5/3
1 /
1
1
P
Z b A RT
RT
b A
Z P
RT RT
Z b A
P RT RT
| |
= +
|
\ .
(
( = +
(

=

Now we can set P
1
=0 and integrate the expression to obtain,
3-170
( )
2
2
0
2
5/3
2 0
2 5/3
2
2 5/3
2
1
ln
ln
ln 0
ln
P
P
f Z
dP
P P
f b A
P RT RT
f b A
P
P RT RT
f b A
P
P RT RT
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .

3-171
3.72. The van der Waals constants for methane in older units are a =2.283 L
2
bar mol
2
and b =0.0428 L mol
1
. Expressing the
compression factor as (see Problem 1.52 in Chapter 1):
2
2
1
1 ,
a b
Z b P P
RT RT RT
| | | |
= + +
| |
\ . \ .

Find the fugacity of methane at 500 bar and 298 K.

Solution:
We are able to use the same expression (for fugacity) we have just derived in the previous problem. This yields the following:

0
5
3
5
3
2
2
0
2
0 0
1
ln
1
1
1 1
1
ln
1
ln
ln
P
P
P P
f Z
dP
P P
b A
Z P
RT
RT
Z b A
P RT
RT
Z a b
b P
P RT RT RT
f a b
b P dP
P RT RT RT
f a b
b dP PdP
P RT RT RT
f
P
| | | |
=
| |
\ . \ .
| |
= +
|
\ .
=
| | | |
= +
| |
\ . \ .
(
| | | | | |
= +
( | | |
\ . \ . \ . (

( | | | | | |
= +
| | | (
\ . \ . \ .
|
\

2
2
1 1
0.622 84
2
a b
b P P
RT RT RT
| | | | |
= + =
| | |
. \ . \ .

The fugacity of the gas can then be found.

3-172
ln 0.622 84
lne
f
P
| |
=
|
\ .
( )
( )
( )
( )
0.622 84
0.622 84
0.622 84
e
e
500 e
268 bar
f
P
f P
f
f
| |
=
|
\ .
=
=
=


CHAPTER
4
4
Chemical Equilibrium

Physical Chemistry
Electronic Edition

Chapter 4: Chemical Equilibrium Equilibrium Constants
4-2
Chapter 4
Equilibrium Constants
4.1. A reaction occurs according to the equation:
2A Y +2Z
If in a volume of 5 dm
3
we start with 4 mol of pure A and find that 1 mol of A remains at equilibrium, what is the equilibrium
constant K
c
?
Solution
4.2. The equilibrium constant for a reaction below is 0.1:
A +B Y +Z
What amount of A must be mixed with 3 mol of B to yield, at equilibrium, 2 mol of Y?
Solution
4.3. The equilibrium constant for the reaction below is 0.25 dm
6
mol
2

A +2B Z
In a volume of 5 dm
3
, what amount of A must be mixed with 4 mol of B to yield 1 mol of Z at equilibrium?
Solution
4.4. The equilibrium constant K
c
for the reaction:
2SO
3
(g) 2SO
2
(g) +O
2
(g)
is 0.0271 mol dm
3
at 1100 K. Calculate K
P
at that temperature.
Solution
4-3
4.5. When gaseous iodine is heated, dissociation occurs:
I
2
2I
It was found that when 0.0061 mol of iodine was placed in a volume of 0.5 dm
3
at 900 K, the degree of dissociation (the fraction of
the iodine that is dissociated) was 0.0274. Calculate K
c
and K
P
Solution

4.6. It has been observed with the ammonia equilibrium:
N
2
+3H
2
2NH
3

that under certain conditions the addition of nitrogen to an equilibrium mixture, with the temperature and pressure held constant,
causes further dissociation of ammonia. Explain how this is possible. Under what particular conditions would you expect this to
occur? Would it be possible for added hydrogen to produce the same effect?
Solution
4.7. Nitrogen dioxide, NO
2
, exists in equilibrium with dinitrogen tetroxide, N
2
O
4
:
N
2
O
4
(g) 2NO
2
(g)
At 25.0 C and a pressure of 0.597 bar the density of the gas is 1.477 g dm
3
. Calculate the degree of dissociation under those
conditions, and the equilibrium constants K
c
, K
P
, and K
x
. What shift in equilibrium would occur if the pressure were increased by
the addition of helium gas?
Solution
4-4
4.8. At 25.0 C the equilibrium:
2NOBr(g) 2NO(g) +Br
2
(g)
is rapidly established. When 1.10 g of NOBr is present in a 1.0-dm
3
vessel at 25.0 C the pressure is 0.355 bar. Calculate the
equilibrium constants K
P
, K
c
, and K
x
.
Solution
4.9. At 100 C and 2 bar pressure the degree of dissociation of phosgene is 6.30 10
5
. Calculate K
P
, K
c
, and K
x
for the dissociation:
COCl
2
(g) CO(g) +Cl
2
(g)
Solution
4.10. In a study of the equilibrium
H
2
+I
2
2HI
1 mol of H
2
and 3 mol of I
2
gave rise at equilibrium to x mol of HI. Addition of a further 2 mol of H
2
gave an additional x mol of
HI. What is x? What is K at the temperature of the experiment?
Solution

*4.11. The equilibrium constant for the reaction below is 20.0 at 40.0 C:
H
2
(g) +I
2
(g) 2HI(g)
The vapor pressure of solid iodine is 0.10 bar at that temperature. If 12.7 g of solid iodine are placed in a 10-dm
3
vessel at 40.0 C,
what is the minimum amount of hydrogen gas that must be introduced in order to remove all the solid iodine?
Solution
4-5
4.12. The degree of dissociation of N
2
O
4
(g) is 0.483 at 0.597 bar and 0.174 at 6.18 bar. The temperature is 298 K for both
measurements. Calculate K
P
, K
c
, and K
x
in each case.
(Hint: See Example 4.1.)
Solution
4.13. One mole of HCl mixed with oxygen is brought into contact with a catalyst until the following equilibrium has been established:
4HCl(g) +O
2
(g) 2Cl
2
(g) +2H
2
O(g).
If y mol of HCl is formed, derive an expression for K
P
interms of y and the partial pressure of oxygen.
(Hint: First develop expressions for the ratios
2 2 2
Cl HCl H O Cl
/ and / x x x x in terms of y and
2
O
P )
Solution
4.14. Using the result of Problem 4.13, evaluate K
P
for an experiment in which 49% HCl and 51% O
2
are brought into contact with a
catalyst until the reaction is complete at 1 bar and 480 C. The fraction of HCl converted per mole is found to be 0.76.
Solution
4.15. 10.0 g of HI is introduced into an evacuated vessel at 731 K and allowed to reach equilibrium. Find the mole fractions of H
2
, I
2
, and
HI present at equilibrium. K
P
=K
c
=K
x
=65.0 for the reaction H
2
(g) +I
2
(g) 2HI(g).
(Hint: see Example 4.2)
Solution
Chapter 4: Chemical Equilibrium Equilibrium Constants and Gibbs Energy Changes
4-6
Equilibrium Constants and Gibbs Energy Changes
4.16. The equilibrium constant for the reaction
(C
6
H
5
COOH)
2
2C
6
H
5
COOH
in benzene solution at 10 C is 2.19 10
3
mol dm
3
.
a. Calculate G for the dissociation of the dimer.
b. If 0.1 mol of benzoic acid is present in 1 dm
3
of benzene at 10 C, what are the concentrations of the monomer and of the dimer?
Solution
4.17. At 3000 K the equilibrium partial pressures of CO
2
,
CO, and O
2
are 0.6, 0.4, and 0.2 atm, respectively. Calculate G at 3000 K for the reaction:
2CO
2
(g) 2CO(g) +O
2
(g)
Solution
4.18. The conversion of malate into fumarate:
1. malate(aq) fumarate(aq) +H
2
O(l)
is endergonic at body temperature, 37 C; G is 2.93 kJ mol
1
. In metabolism the reaction is coupled with
2. fumarate(aq) aspartate(aq)
for which G is 15.5 kJ mol
1
at 37 C.
a. Calculate K
c
for reaction 1.
b. Calculate K
c
for reaction 2.
c. Calculate K
c
and G for the coupled reaction 1 +2.
Solution
Chapter 4: Chemical Equilibrium Equilibrium Constants and Gibbs Energy Changes
4-7
4.19. From the data in Appendix D, deduce the G and K
P
values for the following reactions at 25.0 C:
a. N
2
(g) +3H
2
(g)
2NH
3
(g)
b. 2H
2
(g) +C
2
H
2
(g) C
2
H
6
(g)
c. H
2
(g) +C
2
H
4
(g)
C
2
H
6
(g)
d. 2CH
4
(g)
C
2
H
6
(g) +H
2
(g)
Solution

4.20. Calculate K
c
and K
x
for each of the reactions in Problem 4.19 assuming total pressures of 1 bar in each case.
Solution
4.21. At 25.0 C the equilibrium constant for the reaction:
CO(g) +H
2
O(g) CO
2
(g) +H
2
(g)
is 1.00 10
5
, and S is 41.8 J K
1
mol
1
.
a. Calculate G and H at 25.0 C.
b. Suppose that 2 mol of CO and 2 mol of H
2
O are introduced into a 10-dm
3
vessel at 25.0 C. What are the amounts of CO, H
2
O,
CO
2
, and H
2
at equilibrium?
Solution
4.22. Suppose that there is a biological reaction:
1. A +B Z
for which the G value at 37.0 C is 23.8 kJ mol
1
. (Standard state =1 mol dm
3
.) Suppose that an enzyme couples this reaction
with
2. ATP ADP +phosphate
for which G =31.0 kJ mol
1
. Calculate the equilibrium constant at 37.0 C for these two reactions and for the coupled reaction
3. A +B +ATP Z +ADP +phosphate
Solution
Chapter 4: Chemical Equilibrium Temperature Dependence of Equilibrium Constants
4-8
4.23. The equilibrium between citrate and isocitrate involves cis-aconitate as an intermediate:
citrate cis-aconitate +H
2
O isocitrate
At 25 C and pH 7.4 it was found that the molar composition of the mixture was:
90.9% Citrate
2.9% cis-aconitate
6.2% Isocitrate

Calculate the equilibrium constants for the individual reactions, and for the overall reaction, and G for the citrate-isocitrate
system.
Solution
4.24. The solubility product of Cr(OH)
3
is 3.0 10
29
mol
4
dm
12
at 25 C. What is the solubility of Cr(OH)
3
in water at this temperature?
Solution
Temperature Dependence of Equilibrium Constants
4.25. A gas reaction:
A B +C
is endothermic and its equilibrium constant K
P
is 1 bar at 25 C.
a. What is G at 25 C (standard state: 1 bar)?
b. Is S, with the same standard state, positive or negative?
c. For the standard state of 1 M, what are K
c
and G?
d. Will K
P
at 40 C be greater than or less than 1 bar?
e. Will G at 40 C (standard state: 1 bar) be positive or negative?
Solution
4-9
4.26. A solution reaction:
A +B X +Y
is endothermic, and K
c
at 25 C is 10.
a. Is the formation of X +Y exergonic at 25 C?
b. Will raising the temperature increase the equilibrium yield of X +Y?
c. Is S positive or negative?
Solution
4.27. From the data given in Appendix D, for the reaction:
C
2
H
4
(g) +H
2
(g) C
2
H
6
(g)
Calculate the following:
a. G, H, and S at 25 C; what is the standard state?
b. K
P
at 25 C.
c. K
c
at 25 C (standard state: 1 M).
d. G at 25 C (standard state: 1 M).
e. S at 25 C (standard state: 1 M).
f. K
P
at 100 C, on the assumption that H and S are temperature independent.
Solution
4.28. From the data in Appendix D, for the reaction:
2H
2
(g) +O
2
(g) 2H
2
O(g)
a. G, H, and S at 25 C (standard state: 1 bar).
b. K
P
at 25 C.
c. G and K
P
Solution
4-10
4.29. Calculate the equilibrium constant at 400 K for the reaction:
3O
2
(g) 2O
3
(g).
where
f
G(O
3
, g) =163.2 kJ mol
1
.
Solution
4.30. The hydrolysis of adenosine triphosphate to give adenosine diphosphate and phosphate can be represented by:
ATP ADP +P
The following values have been obtained for the reaction at 37 C (standard state: 1 M):
1
1
31.0kJ mol
20.1kJ mol
G
H
=
=

a. Calculate S.
b. Calculate K
c
at 37 C.
c. On the assumption that H and S are temperature independent, calculate G and K
c
at 25 C.
Solution
4.31. Thermodynamic data for n-pentane(g) and neo-pentane(g) (standard state: 1 bar and 25 C) are as follows:
Compound
Enthalpy of Formation,
f
H kJ mol
1

Entropy, S J K
1

mol
1

n-Pertane(g) 146.44 349.0
Neopentane(g) 165.98 306.4

a. Calculate G for n-pentane neopentane.
b. Pure n-pentane is in a vessel at 1 bar and 25 C, and a catalyst is added to bring about the equilibrium between n-pentane and
neopentane. Calculate the final partial pressures of the two isomers.
Solution
4-11
4.32. a. An equilibrium constant K
c
is increased by a factor of 3 when the temperature is raised from 25.0 C to 40.0 C. Calculate the
standard enthalpy change.
b. What is the standard enthalpy change if instead K
c
is decreased by a factor of 3 under the same conditions?
Solution
4.33. a. The ionic product [H
+
] [OH
], which is the equilibrium constant for the dissociation of water;

H
2
O H
+
+OH

is 1.00 10
14
mol
2
dm
6
at 25.0 C and 1.45 10
14
mol
2
dm
6
at 30.0 C. Deduce H and S for the process.
b. Calculate the value of the ionic product at body temperature (37 C).
Solution
P
for the reaction I
2
(g) +cyclopentane(g) 2 HI(g) +cyclopentadiene(g) varies with temperatures
according to the equation:
log
10
(K
P
/bar) =7.55 4844/(T/K)
a. Calculate K
P
, G, H, S (standard state: 1 bar) at 400 C.
b. Calculate K
c
and G (standard state: 1 M) at 400 C.
c. If I
2
and cyclopentane are initially at 400 C and at concentrations of 0.1 M, calculate the final equilibrium concentrations of I
2
,
cyclopentane, HI, and cyclopentadiene.
Solution
4.35. From the data in Appendix D, for the synthesis of methanol,
CO(g) +2H
2
(g) CH
3
OH(l)
Calculate H, G, and S and the equilibrium constant at 25 C.
Solution
4-12
4.36. The bacterium nitrobacter plays an important role in the nitrogen cycle by oxidizing nitrite to nitrate. It obtains the energy it
requires for growth from the reaction

2 2 3
1
NO (aq) O (g) NO (aq)
2
+
Calculate H, G, and S for this reaction from the following data, at 25 C:
Ion
1
kJ mol
f
H

1
kJ mol
f
G

2
NO 104.6 37.2

3
NO 207.4 111.3
Solution
4.37. When the reaction:
glucose-1-phosphate(aq) glucose-6-phosphate(aq)
is at equilibrium at 25 C, the amount of glucose-6-phosphate present is 95% of the total.
a. Calculate G at 25 C.
b. Calculate G for reaction in the presence of 10
2
M glucose-1-phosphate and 10
4
M glucose-6-phosphate. In which direction
does reaction occur under these conditions?
Solution
4.38. From the data in Appendix D, for the reaction
CO
2
(g) +H
2
(g) CO(g) +H
2
O(g)
a. H, G, and S (standard state: 1 bar and 25 C).
b. The equilibrium constant at 25 C.
c. From the heat capacity data in Table 2.1, obtain an expression for H as a function of temperature.
d. Obtain an expression for ln K
P
as a function of temperature.
e. Calculate K
P
at 1000 K.
Solution
4-13
4.39. Irving Langmuir [J. Amer. Chem. Soc., 28, 1357 (1906)] studied the dissociation of CO
2
into CO and O
2
by bringing the gas at 1
atm pressure into contact with a heated platinum wire. He obtained the following results:
T/K Percent Dissociation
1395 0.0140
1443 0.0250
1498 0.0471

Calculate K
P
for 2CO
2
(g) =2CO(g) +O
2
(g) at each temperature, and estimate H, G, and S at 1395 K.
Solution
4.40. G. Stark and M. Bodenstein [Z. Electrochem.,16, 961(1910)] carried out experiments in which they sealed iodine in a glass bulb and
measured the vapor pressure. The following are some of the results they obtained:
3
volume of bulb=249.8 cm
amount of iodine =1.958 mmol

Temperature/C Pressure/Torr
800 558.0
1000 748.0
1200 1019.2
a. Calculate the degree of dissociation at each temperature.
b. Calculate K
c
at each temperature, for the process I
2
2I.
c. Calculate K
P
at each temperature.
d. Obtain values for H and U at 1000 C.
e. Calculate G and S at 1000 C.
Solution
4-14
4.41. The following diagram shows the variation with temperature of the equilibrium constant K
c
for a reaction. Calculate G, H, and
S at 300 K.

Solution
4.42. The following values apply to a chemical reaction A Z:
1
1 1
85.2 kJ mol
170.2 J K mol
H
S
=
=

Assuming these values to be temperature independent, calculate the equilibrium constant for the reaction at 300 K. At what
temperature is the equilibrium constant equal to unity?
Solution
c
for the hydrolysis of adenosine triphosphate (ATP) to adenosine diphosphate (ADP) and phosphate is
1.66 10
5
mol dm
3
at 37 C, and H is 20.1 kJ mol
1
. Calculate S for the hydrolysis at 37 C. On the assumption that H and
S are temperature independent, calculate K
c
at 25 C.
Solution
4-15
4.44. A dissociation A
2
2A has an equilibrium constant of 7.2 10
5
mol dm
3
at 300 K, and a H value of 40.0 kJ mol
1
. Calculate
the standard entropy change for the reaction at 300 K. (What is its standard state?) If the H and S values for this reaction are
temperature independent, at what temperature is the equilibrium constant equal to unity?
Solution
4.45. A reaction A +B Z has an equilibrium constant of 4.5 10
4
dm
3
mol
1
1
. Calculate
the entropy change for the reaction at 300 K. If the H and S values are temperature independent, at what temperature is the
equilibrium constant equal to unity?
Solution
4.46. At 1 bar pressure liquid bromine boils at 58.2 C, and at 9.3 C its vapor pressure is 0.1334 bar. Assuming H and S to be
temperature independent, calculate their values, and calculate the vapor pressure and G at 25 C.
Solution
4.47. The standard Gibbs energy of formation of gaseous ozone at 25 C,
f
G , is 162.3 kJ mol
1
,

for a standard state of 1 bar. Calculate
the equilibrium constants K
P
, K
c
, and K
x
for the process:
3O
2
(g) 2O
3
(g)
What is the mole fraction of O
3
present at 25 C at 2 bar pressure?
Solution
4.48. For the equilibrium:
H
2
(g) +I
2
(g) 2HI(g)
The following data apply:
1
1 1
1 1
(300K)=9.6 kJ mol
(300K)=22.18 J K mol
(500K)=7.11 J K mol
p
H
S
C

The latter value can be taken to be the average value between 300 K and 500 K.
Chapter 4: Chemical Equilibrium Binding to Protein Molecules
4-16
Calculate the equilibrium constants K
P
, K
c
, and K
x
at 500 K. What would be the mole fraction of HI present at equilibrium if HI is
introduced into a vessel at 10 atm pressure; how would the mole fraction change with pressure?
Solution
*4.49. Protein denaturations are usually irreversible but may be reversible under a narrow range of conditions. At pH 2.0, at temperatures ranging
fromabout 40 C to 50 C, there is an equilibriumbetween the active formP and the deactivated formD of the enzyme trypsin:
P D
Thermodynamic values are H =283 kJ mol
1
and S =891 J K
1
mol
1
. Assume these values to be temperature independent over
this narrow range, and calculate G and K
c
values at 40.0 C, 42.0 C, 44.0 C, 46.0 C, 48.0 C, and 50.0 C. At what temperature
will there be equal concentrations of P and D?
**Note that the high thermodynamic values lead to a considerable change in K over this 10 C range.
Solution
Binding to Protein Molecules
*4.50. Suppose that a large molecule, such as a protein, contains n sites to which a molecule A (a ligand) can become attached. Assume
that the sites are equivalent and independent, so that the reactions M +A =MA, MA +A =MA
2
, etc., all have the same equilibrium
constant K
s
. Show that the average number of occupied sites per molecule is:
[A]
1 [ ]
s
s
nK
v
K A
=
+

Solution
*4.51. Modify the derivation in Problem 4.50 so as to deal with sites that are not all equivalent; the equilibrium constants for the
attachments of successive ligands are each different:
1
[MA]
M A MA
[M][A]
K + =
2
2 2
[MA ]
MA A MA
[MA][A]
K + =
Chapter 4: Chemical Equilibrium Binding to Protein Molecules
4-17
1
1
[MA ]
MA A MA
[MA ][A]
n
n n n
n
K + =
Show that the average number of molecules of A bound per molecule M is:
2
1 1 2 1 2 3
2
1 1 2 1 2 3
[A] 2 [A] ( )[A]
1 [A] [A] ( )[ ]
n
n
n
n
K K K n K K K K
v
K K K K K K K A
+ + +
=
+ + + +

This equation is important in biology and biochemistry and is often called the Adair equation, after the British biophysical chemist
G. S. Adair.
Solution
*4.52. Now show that the Adair equation, derived in Problem 4.51, reduces to the equation obtained in Problem 4.50 when the sites are
equivalent and independent. [It is not correct simply to put K
1
=K
2
=K
3
=K
n
; certain statistical factors must be introduced.
Thus, if K
s
is the equilibrium constant for the binding at a given site, K
1
=nK
s
, since there are n ways for A to become attached to a
given molecule and one way for it to come off. Similarly K
2
=(n 1)K
s
/2; n 1 ways on and 2 ways off. Continue this argument
and develop an expression for v that will factorize into nK
s
[A]/(1 +K
s
[A]). Suggest a method of testing the equilibrium obtained
and arriving at a value of n from experimental data.]
Solution
*4.53. Another special case of the equation derived in Problem 4.51 is if the binding on one site affects that on another. An extreme case is
highly cooperative binding, in which the binding of A on one site influences the other sites so that they fill up immediately. This
means that K
n
is much greater than K
1
, K
2
, etc. Show that now:
[A]
1 [A]
n
n
nK
v
K
=
+

Where K is the product of K
1
, K
2
, K
n
. The British physiologist A. V. Hill suggested that binding problems can be treated by plotting:
ln against ln[A]
1

Where is the fraction of sites that are occupied. Consider the significance of such Hill plots, especially their shapes and slopes,
with reference to the equations obtained in Problems 4.50 to 4.53.
Solution
Chapter 4: Chemical Equilibrium Essay Questions
4-18
Essay Questions
4.54. Give an account of the effect of temperature on equilibrium constants, and explain how such experimental studies lead to
thermodynamic data.
4.55. Give an account of the effect of pressure on (a) the position of equilibrium and (b) the equilibrium constant.
4.56. Explain what experimental studies might be made to decide whether a chemical system is at equilibrium or not.
4.57. Give an account of the coupling of chemical reactions.
4.58. State the Le Chatelier principle, and give several examples.

**SUGGESTED READING**
See the listing at the end of Chapter 3. For a discussion of binding problems relating to Problems 4.504.53 see:
K. J . Laidler, Physical Chemistry with Biological Applications, Menlo Park, California: Benjamin/Cummings, 1978; especially Section
11.2, Multiple Equilibria.
J . Steinhart, and J . A. Reynolds, Multiple Equilibria in Proteins, New York: Academic Press, 1969, especially Chapter 2,
Thermodynamics and Model Systems.
C. Tanford, Physical Chemistry of Macromolecules, New York: Wiley, 1961, especially Chapter 8, Multiple Equilibria.

Chapter 4: Chemical Equilibrium Solutions
4-19
Solutions
4.1. A reaction occurs according to the equation
2A Y +2Z
If in a volume of 5 dm
3
we start with 4 mol of pure A and find that 1 mol of A remains at equilibrium, what is the equilibrium
constant K
c
?
Solution:
Given:
3
initial equilibrium
5 dm, 4 mol, 1 mol V n n = = =
Required: K
c
This equilibrium problem can be solved using a table:
2A Y + 2Z
n
initial
4 0 0 mol
n
equilibrium
1 1.5 3.0 mol
C
equilibrium
1
5

1.5
5

3.0
5

mol dm
-3

For this reaction, K
c
is given by the equation
| || |
| |
2
2
Y Z
A
c
K = . Solving using the concentrations at equilibrium gives the following,
3
1.5 3.0
mol dm mol
5 5
c
K
| |
|
\ .
=
3
dm
2
1.0
mol
5
| |
|
\ .
3
dm
2
3
2.7 mol dm
c
K

| |
|
\ .
=

4-20
4.2. The equilibrium constant for a reaction
A +B Y +Z
is 0.1 What amount of A must be mixed with 3 mol of B to yield, at equilibrium, 2 mol of Y?
Solution:
Given: K
c
=0.1,
initial
B
3 mol n = ,
equilibrium
Y
2 mol n =
Required:
initial
A
n
A + B Y + Z
n
initial

initial
A
n 3 0 0 mol
n
equilibrium
initial
A
2 n 1 2 2 mol

c
| || |
| || |
Y Z
A B
c
K = . Assuming the total volume is constant for the reaction,
Y Z
A B
c
n n
K
n n
= .
Rearranging for, n
A
gives,
Y Z
A
B c
n n
n
K n
= and therefore
initial
A
n can be determined.
( )
initial
A
2 mol 2mol
2 mol n =
( )
0.11 mol
( )
( )
initial
A
2 mol 2 mol
n =
( )
0.11 mol
( )
initial
A
2 mol
42 mol n
+
=

4-21
A +2B Z
is 0.25 dm
6
mol
2
. In a volume of 5 dm
3
, what amount of A must be mixed with 4 mol of B to yield 1 mol of Z at equilibrium?
Solution:
Given: K
c
=0.25 dm
6
mol
2
, V=5 dm
3
,
initial
B
4 mol n = ,
equilibrium
Z
1 mol n =
Required:
initial
A
n
A + 2B Z
n
initial

initial
A
n 4 0 mol
n
equilibrium
initial
A
1 n 2 1 mol
C
equilibrium

initial
A
1
5
n | |
|
\ .

2
5

1
5

mol dm
-3

c
| |
| || |
2
Z
A B
c
K = . Rearranging for| | A , gives, | |
| |
| |
2
c
Z
A =
K B
and
initial
A
n can be determined from
this expression.
( )
( )
( )
initial
initial
initial
3
A
2 3
6 2 3
A
3
3
A
1
mol dm
1 mol
5
5 dm
2
0.25 dm mol mol dm
5
1 mol
5 mol dm
5 dm
26 mol
n
n
n
| |
|
\ .
=
| |
|
\ .
=
=

4-22
c
for the reaction
2SO
3
(g) 2SO
2
(g) +O
2
(g)
is 0.0271 mol dm
3
at 1100 K. Calculate K
P
Solution:
Given: K
c
=0.0271 mol dm
3
, T =1100 K

Required: K
P
The relationship between K
c
and K
P
is given by Eq. 4.26,
K
P
=K
c
(RT)
v
wherev is the difference between the moles of products to the moles of products.
Since there are three moles of gas produced from two moles of SO
3
,
v =+1 mol.
Solving for K
P
gives,
0.0271 mol
P
K =
( )
3 3
dm 0.083 145 bar dm
-1
K
1
mol
1100 K
( )
( ) 1
2.478 55bar
2.48 bar
P
P
K
K
+
=
=

4-23
4.5. When gaseous iodine is heated, dissociation occurs:
I
2
2I
It was found that when 0.0061 mol of iodine was placed in a volume of 0.5 dm
3
at 900 K, the degree of dissociation (the fraction of
the iodine that is dissociated) was 0.0274. Calculate K
c
and K
P
Solution:
Given:
2
I initial
0.0061 mol n = , V =0.5 dm
3
, T =900 K,

, degree of dissociation =0.0274
Required: K
c
and K
P

I
2
2I
n
initial
0.0061 0 mol
n
equilibrium ( )
3
0.00611 0.0274
5.9329 10
=

4
0.0061 0.0274 2
3.3428 10

=

mol
c
| |
| |
2
2
I
I
c
K = . Solving using the concentrations at equilibrium gives the following,
2
4
3
3
3
5 3
5 3
3.3428 10
mol dm
0.5
5.9329 10
mol dm
0.5
3.7669 10 mol dm
3.77 10 mol dm
c
c
c
K
K
K

| |
|
\ .
=
| |
|
\ .
=
=

c
and K
P
K
P
=K
c
(RT)
v
, wherev is the difference between the moles of products to the moles of products.
Since there are two moles of iodine produced from one mole of iodine gas,
4-24
v =+1 mol.
Solving for K
P
gives,
5
3.77 10 mol
P
K

=
3
dm
( )
3
0.083 145 bar dm
-1
K
1
mol
900K
( )
( ) 1 +

3
0.002 821 bar
2.82 10 bar
P
P
K
K

=
=

4-25
4.6. It has been observed with the ammonia equilibrium:
N
2
+3H
2
2NH
3

that under certain conditions the addition of nitrogen to an equilibrium mixture, with the temperature and pressure held constant,
causes further dissociation of ammonia. Explain how this is possible. Under what particular conditions would you expect this to
occur? Would it be possible for added hydrogen to produce the same effect?
Solution:
The equilibrium constant for this reaction is given by,
| |
| || |
3
2 2
2 2
NH 3
3 3
N H
2 2
NH
N H
c
n
K
n n
= =
If
2
N
n is increased at constant V, the equilibrium must shift to the right, so as to produce more ammonia. If the pressure (as well as the
temperature) is kept constant, however, addition of N
2
requires that V is increased. If the proportional increase in V
2
is greater than the
increase in
2
N
n , the equilibrium will shift to the left when N
2
is added.
The volume is proportional to
3 2 2
NH N H
n n n + + and V
2
is proportional to
( )
3 2 2
2
NH N H
n n n + + . If
2
N
n is much larger than
3 2
NH H
n n + , V
2
will
increase approximately with
2
2
N
n and therefore increases more strongly than
2
N
n . If
2
N
n is not much larger than
3 2
NH H
n n + , an increase
in
2
N
n will have a relatively small effect on V
2
. The increase in ammonia dissociation when N
2
is added is therefore expected when N
2
is in
excess, but not otherwise.
On the other hand,
2
3
H
n appears in the equilibrium expression; this varies more strongly than V
2
, and added H
2
therefore cannot lead to the
dissociation of ammonia.

4-26
4.7. Nitrogen dioxide, NO
2
, exists in equilibrium with dinitrogen tetroxide, N
2
O
4
:
N
2
O
4
(g) 2NO
2
(g)
At 25.0 C and a pressure of 0.597 bar the density of the gas is 1.477 g dm
3
. Calculate the degree of dissociation under those
conditions, and the equilibrium constants K
c
, K
P
, and K
x
. What shift in equilibrium would occur if the pressure were increased by
the addition of helium gas?
Solution:
Given:
3
25 C 298.15K, 0.597 bar, =1.477 g dm T P = = =
Required: , degree of dissociation, K
c
, K
P
, and K
x
. the shift in equilibrium that would occur if the pressure were increased by the addition
of helium gas.
To determine the degree of dissociation, we need to first obtain the mole fractions of each gas. First we assume that in 1 dm
3
there
are
2 4
N O
n moles of N
2
O
4
and
2
NO
n moles of NO
2
. Therefore the total number of moles is given by
2 4 2
N O NO
n n n = + .
,
and solving for n,
2 4 2
N O NO
and n n can be obtained.
0.597 bar
PV
n
RT
n

3
1 dm

0.083 145 bar
3
dm
-1
K

-1
mol 298.15 K

2 4 2
N O NO
0.024 083 mol
0.024 083 mol
n
n n

The mole fractions can also be determined using the density of the gas given in the problem.
4-27
( ) ( )
( ) ( )
( )
2 4 2 4 2 2
2 4 2
2 4 2
N O N O NO NO
-1 -1 -1 -1
N O NO
3
-1 -1
N O NO
3
-1
, where
2 14.006 74 g mol 4 15.9994 g mol 14.006 74 g mol 2 15.9994 g mol
1 dm
92.011 08 g mol 46.005 54 g mol
1 dm
46.005 54 g mol 2
M n M n
m
m Mn
V V
n n
n n
n
+
= = =
+ + +
=
+
=
=
( )
2 4 2
N O NO
3

1 dm
n +
( )
2 4 2
N O NO
1.477 g
2 n n + =
3
dm
( )
3
1 dm
( )
46.005 54 g
( )
-1
mol

( )
2 4 2
N O NO
2 0.032 105 mol n n + =

Now we have two equations and two unknowns, and therefore we can solve for the mole fractions.
(1)
(2)
Subtracting (1) from (2) gives,
2 4
2 4
2
2
2
N O
3
N O
NO
NO
2
NO
0.008 022 mol
8.02 10 mol
0.024 083 mol 0.008 022 mol
0.016 061 mol
1.61 10 mol
n
n
n
n
n
=
=
=
=
=

If the degree of dissociation is , the amounts of N
2
O
4
and NO
2
present are:
2 4 2
2 4 2
N O NO
N O NO
0.024 083 mol
2 0.032 105 mol
n n
n n
+ =
+ =
4-28
( )
( )
2 4
2
N O : 1
NO :2
P
P

Since partial pressures are proportional to the number of moles of each species present,
( )
( )
( )
( )
2 4
2
2
2 4
N O
NO
NO
N O
1
2
2
therefore,
1
n P
n P
n P
n P

Solving for gives,
( )
( )
2 1 P
=
2 4
N O
n
P
2
2 4
2
2 4
2
NO
N O
NO
N O
NO
2
1
1
2
1
1
n
n
n
n
n
=
= +

( ) ( )
2 4 2
2
2
2 4 2
N O NO
NO
NO
N O NO
2
1
2
0.016 061 mol
2 0.008 022 mol 0.016 061 mol
0.500 265
0.500
n n
n
n
n n
+
=
=
+
=
+
=
=

4-29
The equilibrium constant for this reaction is given by
| |
| |
2
2
2 4
NO
N O
c
K = . From our assumption that in 1 dm
3
there are
2 4
N O
n moles of N
2
O
4
and
2
NO
n moles of NO
2
, we can solve for K
c
.
2
3
3
3
3
0.016 061 mol
1 dm
0.008 022 mol
1 dm
0.032 156 mol dm
0.0322 mol dm
c
c
c
K
K
K
| |
|
\ .
=
| |
|
\ .
=
=

c
and K
P
K
P
=K
c
(RT)
v
Since there are two moles of nitrogen dioxide produced from one mole of dinitrogen tetroxide,
v =+1 mol.
Solving for K
P
gives,
0.032 156 mol
P
K =
3
dm
( )
3
0.083145 bar dm
-1
K
1
mol
298.15K
( )
( ) 1
0.797 137 bar
0.797 bar
P
P
K
K
+
=
=

x
and K
P
K
P
=K
x
P
v
Rearranging for K
x
gives,

v
x P
K K P
=
4-30
v =+1 mol.
K
x
can therefore be solved, giving,
( )( )
1
0.797 137 bar 0.597 bar
1.335238
1.34
x
x
x
K
K
K
=
=
=

The addition of helium gas would have no effect on the equilibrium since the concentrations, partial pressures, and mole fractions would
remain unchanged.


4-31
4.8. At 25.0 C the equilibrium:
2NOBr(g) 2NO(g) +Br
2
(g)
is rapidly established. When 1.10 g of NOBr is present in a 1.0-dm
3
vessel at 25.0 C the pressure is 0.355 bar. Calculate the
equilibrium constants K
P
, K
c
, and K
x
.
Solution:
Given:
3
1.10 g, 1 dm 25 C 298.15K, 0.355 bar m V T P = = = = =
Required: K
P
, K
c
, and K
x
| | | |
| |
2
2
2
NO Br
NOBr
c
K = .To calculateK
c
, we must first determine n
NOBr
, the number of moles
initially present of NOBr,
( )
NOBr
NOBr
NOBr
NOBr
-1 -1 -1
NOBr
NOBr
1.10 g
14.006 74 g mol 15.9994 g mol 79.904 g mol
0.010 008 mol
0.01 mol
m
n
M
n
n
n
=
=
+ +
=
=

If is the degree of dissociation, then the number of moles of each gas at equilibrium is given in the following table:
2NOBr 2NO + Br
2

n
initial
0.01 0 0 mol
n
equilibrium
( ) 0.011
0.01
0.01
2
| |
|
\ .

mol

The total number of moles is given by
2
NOBr NO Br
n n n n = + +

4-32
( ) 0.011 0.01 0.01
2
0.01 0.01
2
0.01 0.005
n
n
n
| |
= + +
|
\ .
| |
= +
|
\ .
= +

,
and solving for n, can be obtained

0.355 bar
PV
n
RT
n

3
1 dm

0.083 145 bar
3
dm
-1
K

-1
mol 298.15 K

0.014 32 mol
where 0.01 0.005
0.01
0.005
0.014 32 mol 0.01
0.005
0.864
n
n
n

From ,
2
NOBr NO Br
, , and n n n can be obtained.
( )
( )
NOBr
NOBr
3
NOBr
0.01 mol 1
0.01 mol 1 0.864
1.36 10 mol
n
n
n
=
=
=

( )
( )
NO
NO
3
NO
0.01 mol
0.01 mol 0.864
8.64 10 mol
n
n
n
=
=
=

( )
( )
2
2
2
Br
Br
3
Br
0.005 mol
0.005 mol 0.864
4.32 10 mol
n
n
n
=
=
=

Solving for K
c
gives,
4-33
3
8.64 10 mol
c
K
=
3
1 dm
2
3
3
3
4.32 10 mol
1 dm
1.36 10 mol
| | | |
| |
|
\ . \ .
3
1 dm
2
-3
-3
0.174 35 mol dm
0.174 mol dm
c
c
K
K
| |
|
|
\ .
=
=

c
and K
P
K
P
=K
c
(RT)
v
Since there are three moles of total gas produced from two moles of NOBr,
v =+1 mol.
Solving for K
P
gives,
0.174 35mol
P
K =
3
dm
( )
3
0.083145 bar dm
-1
K
1
mol
298.15K
( )
( ) 1
bar 4.322 08
4.32 bar
P
P
K
K
+
=
=

x
and K
P
K
P
=K
x
P
v
Rearranging for K
x
gives,

v
x P
K K P
=
Since there are three moles of total gas produced from two moles of NOBr,
v =+1 mol.
K
x
4-34
( )( )
1
4.322 08 bar 0.355 bar
12.174 87
12.2
x
x
x
K
K
K
=
=
=

4-35
4.9. At 100 C and 2 bar pressure the degree of dissociation of phosgene is 6.30 10
5
. Calculate K
P
, K
c
, and K
x
for the dissociation:
COCl
2
(g) CO(g) +Cl
2
(g)
Solution:
Given:
5
100 C 373.15 K, 2 bar, 6.30 10 T P

= = = =
Required: K
P
, K
c
, and K
x
The equilibrium constant in terms of partial pressures is given by
2
2
CO Cl
COCl
P
P P
K
P
= To calculateK
P
, we must first determine the partial pressures
of each gas present.
If is the degree of dissociation, then the partial pressures of each gas at equilibrium is given in the following table:
COCl
2
CO + Cl
2

( ) 1 P
P P bar

The total number pressure is given by
2 2
total COCl CO Cl
P P P P = + +

( )
( )
( )
( )
total
total
5
1
1 2 bar
2 bar
1
2 bar
1 6.30 10
1.999 87 bar
2 bar
P P P P
P P P
P
P
P
P
P

= + +
= +
+ =
=
+
=
+
=
=

Solving for K
P
, we obtain,
4-36
P
P
K =
( )( ) P
P

( )
( )
( )( )
( )
2
2
5
5
1
1
2 bar 6.30 10
1 6.30 10
P
P
P
K
K
=

9
9
7.9385 10 bar
7.94 10 bar
P
P
K
K
=
=

c
and K
P
K
P
=K
c
(RT)
v
, wherev is the difference between the moles of products to the moles of products. Rearranging for K
c
gives,
K
c
=K
P
(RT)
-v

Since there are two moles of gas produced from one moles of COCl
2
,
v =+1 mol
Solving for K
c
gives,
9
7.9385 10 bar
c
K

=
( )
0.083 145 bar
3 1
dm K
1
mol 373.15K
( )
( ) 1
10 3
10 3
2.558697 10 mol dm
2.56 10 mol dm
c
c
K
K
=
=

x
and K
P
K
P
=K
x
P
v
Rearranging for K
x
gives,
4-37

v
x P
K K P
=

Since there are two moles of gas produced from one moles of COCl
2
,
v =+1 mol
K
x
9
7.9385 10 bar
x
K

=
( )
2 bar
( )
1
9
9

3.969 25 10
3.97 10
x
x
K
K
=
=


4-38
4.10. In a study of the equilibrium
H
2
+I
2
2HI
1 mol of H
2
and 3 mol of I
2
gave rise at equilibrium to x mol of HI. Addition of a further 2 mol of H
2
gave an additional x mol of
HI. What is x? What is K at the temperature of the experiment?
Solution:
Given:
2 2 2
H I H added
1 mol, 3 mol, 2 mol n n n = = =
Required: x, K
H
2
+ I
2
2HI
n
initial
1 3 0 mol
n
equilibrium
1
2
x
3
2
x

x mol
2
after H added
n 3 x 3 x 2x

mol

For this reaction, K is given by the equation
| |
| || |
2
2 2
HI
H I
K = . Assuming the volume is constant, the expression for K becomes,
2 2
2
HI
H I
n
K
n n
=
K is always constant, therefore the two expressions obtained at equilibrium and after H
2
is added can be used to solve for x.
4-39
( ) x
K =
2
2
4
1 3
2 2
x
x x
=
| || |

| |
\ .\ .
( )( )
( )
2
2
3 3
3 4 1 3
2 2
9 6
x x
x x
x
x x

| || |
=
| |
\ .\ .
+
2
12 8x x = +
2 3
3
2
x
x
=
=

Substituting for x, K can be solved.
2
2
2
3
4
2
3
3
2
9
3
2
9
9
4
4
K
K
K
K
| |
|
\ .
=
| |
|
\ .
=
| |
|
\ .
=
| |
|
\ .
=


4-40
4.11. The equilibrium constant for the reaction below is 20.0 at 40.0 C:
H
2
(g) +I
2
(g) 2HI(g)
The vapor pressure of solid iodine is 0.10 bar at that temperature. If 12.7 g of solid iodine are placed in a 10-dm
3
vessel at 40.0 C,
what is the minimum amount of hydrogen gas that must be introduced in order to remove all the solid iodine?
Solution:
Given:
3
20.0, 40.0 C 313.15 K, 0.10 bar, 12.7 g, 10 dm K T P m V = = = = = =
Required:
2
H
n
First, the number of moles of I
2
is given by,
2
2
I
I
12.7 g
m
n
M
n
=
=
2 126.904 47 g
( )
2
2
-1
I
I
mol
0.050 037 6mol
0.050mol
n
n
=
=

By examining the reaction, the consumption of 0.050 mol of I
2
leads to the formation of 0.10 mol of HI.
The equilibrium constant for this reaction in terms of partial pressures is given by,
2 2
2
HI
H I
P
P
K
P P
= , where
HI
P is obtained from the ideal gas law.
4-41
HI
HI
0.10 mol
nRT
P
V
P
=
=
( )
3
0.083 145 bar dm
-1
K
-1
mol
( )
313.15 K
( )
3
10 dm
HI
0.26037 bar P =

Rearranging and solving for
2
H
P gives,
( )
( )
2
2
2
H
H
0.260 37 bar
20 0.1 bar
0.033 896 bar
P
P
=
=

Then, if
2
H
P is the partial pressure of H
2
after equilibrium is established,
2
equilibrium H
n can be obtained using the ideal gas law.
2
2
2
H equilibrium
H equilibrium
0.033 896 bar
H
P V
n
RT
n
=
=
( )
3
10 dm
0.083 145 bar
3
dm
-1
K
( )
-1
mol 313.15 K
2
H equilibrium
0.013 018 mol n =

This means 0.013 018 mol of H
2
is produced in the equilibrium mixture, and 0.05 mol of H
2
is required to remove the 0.05 mol of I
2
.
2
H
n is
therefore equal to 0.013018 mol +0.05 mol.
2
2
2
H
H
H
0.013 018 mol 0.05 mol
0.063 018 mol
0.063 mol
n
n
n
= +
=
=

4-42
4.12. The degree of dissociation of N
2
O
4
(g) is 0.483 at 0.597 bar and 0.174 at 6.18 bar. The temperature is 298 K for both
measurements. Calculate K
P
, K
c
, and K
x
in each case.
(Hint: See Example 4.1.)
Solution:
Given:
0.597 bar 6.18 bar
0.483, 0.174, 25 C 298.15 K
P P
T
= =
= = = =
Required: K
P
, K
c
, and K
x
in each case
Suppose that we start with 1 mol of N
2
O
4
and that mol have become converted into NO
2
; the amounts at equilibrium are
2 4 2
N O 2NO
1 2

The total amount is given by, 1 2 1 + = + . If P is the total pressure, the partial pressures are
2 4
1
N O :
1
P
+
and
2
2
NO :
1
P
+

The equilibrium constant in terms of partial pressures is given by
2
2 4
2
NO
P
N O
P
K
P
=

Solving for K
P
, we obtain,
4-43
2
2
2
1
P
P
K
| |
|
+
\ .
=
1
1
P
| |
|
+
\ .
( )
2
2
4
1
P
K P

=
+
1 +
( )( )
2
2
2
1
4
1 1
4
1
P
P
K P
K P
| |
|
|
\ .
=
+
=

At 0.597 bar P = ,
( )
( )
( )
2
2
4 0.483
0.597 bar
1 0.483
0.726 60 bar
0.727 bar
P
P
P
K
K
K
=
=
=

At 6.18 bar P = ,
( )
( )
( )
2
2
4 0.174
6.18 bar
1 0.174
0.771 79 bar
0.772 bar
P
P
P
K
K
K
=
=
=

c
and K
P
K
P
=K
c
(RT)
v
c
gives,
K
c
=K
P
(RT)
-v

4-44
v =+1 mol.
Solving for K
c
at 0.597 bar P = gives,
( ) 0.726 60 bar 0.083 145 bar
c
K =
3 1
dm K
1
mol 298.15K
( )
( ) 1
3
2 3
0.029 31 mol dm
2.93 10 mol dm
c
c
K
K
=
=

Solving for K
c
( ) 0.771 79 bar 0.083 145 bar
c
K =
3 1
dm K
1
mol 298.15K
( )
( ) 1
3
2 3
0.031 13 mol dm
3.11 10 mol dm
c
c
K
K
=
=

x
and K
P
K
P
=K
x
P
v
Rearranging for K
x
gives,

v
x P
K K P
=

v =+1 mol.
Solving for K
x
4-45
0.726 60 bar
x
K =
( )
0.597 bar
( )
1

1.217 09
1.22
x
x
K
K
=
=

Solving for K
x
0.771 79 bar
x
K =
( )
6.18 bar
( )
1

0.124 89
0.125
x
x
K
K
=
=

4-46
4.13. One mole of HCl mixed with oxygen is brought into contact with a catalyst until the following equilibrium has been established:
4HCl(g) +O
2
(g) 2Cl
2
(g) +2H
2
O(g).
If y mol of HCl is formed, derive an expression for K
P
interms of y and the partial pressure of oxygen.
(Hint: First develop expressions for the ratios
2 2 2
Cl HCl H O Cl
/ and / x x x x in terms of y and
2
O
P )
Solution:
Given:
HCl
1 mol n =
Required: K
P
interms of y and
2
O
P
Rewriting the reaction in terms of one mole of HCl gives,
HCl + O
2

Cl
2
H
2
O
1-y 2
O
P
y/2 y/2

From examining the equation above, it is possible to establish the following relationships:
( )
2 2
2
Cl H O
HCl Cl
, and 1
2 1
x x
y
x y x
= =

These ratios also hold for partial pressures and solving for K
P
,
4-47
( ) ( )
( )( )
( )
( )
( )
2 2
2
2
2
2
1 1
2 2
Cl H O
1
4
HCl O
Cl
1
4
HCl O
1
4
O
1
2 1
P
P
P
P P
K
P P
P
K
P P
y
K
y
P
=
=
=


4-48
4.14. Using the result of Problem 4.13, evaluate K
P
for an experiment in which 49% HCl and 51% O
2
are brought into contact with a
catalyst until the reaction is complete at 1 bar and 480 C. The fraction of HCl converted per mole is found to be 0.76.
Solution:
Given: 49% HCl, 51% O
2
, P =1 bar, T =480 C =753.15 K, y =0.76
Required: K
P

The result from problem 4.13 gives K
P
as.
( )
( )
2
1
4
O
1
2 1
P
y
K
y
P
=

Solving using
2
O
0.51 1 bar P =
( )
( )
1
4
1
4
1
4
0.76 1
2 1 0.76
0.51 bar
1.873 61 bar
1.9 bar
P
P
P
K
K
K
=
=


4-49
4.15. 10.0 g of HI is introduced into an evacuated vessel at 731 K and allowed to reach equilibrium. Find the mole fractions of H
2
, I
2
, and
HI present at equilibrium. K
P
=K
c
=K
x
=65.0 for the reaction
H
2
(g) +I
2
(g) 2HI(g).
(Hint: see Example 4.2)
Solution:
Given:
HI
10.0 g, =731 K, m T = K
P
=K
c
=K
x
=65.0
Required:
2 2
H I HI
, , x x x
Note first that because the reaction involves no change in the number of molecules, the volume of the vessel is irrelevant, since it cancels
out in the equilibrium equation. Note also that from Eq. 4.26 and Eq. 4.32 the equilibrium constants K
P
, K
c
, and K
x
are all the same and that
they are dimensionless.
Since there are no reactants present initially, we can write,
H
2
(g) + I
2
(g) 2HI(g)
x x n-2x
Where n is the initial amount of HI present,
HI
HI
10.0 g
m
n
M
n
=
=
1.007 94g
1
mol 126.904 47 g
+
( )
1
HI
2
HI
mol
0.078 178mol
7.8179 10 mol
n
n
=
=

The equilibrium constant for this reaction in terms of partial pressures is given by,
2 2
2
HI
H I
P
P
K
P P
= , which can be written in terms of moles as,
4-50
2 2
2
HI
H I
P
n
K
n n
=
Solving for the x, the mole fractions
2 2
H I HI
, , x x x can be obtained.
( )
( )( )
2
2
P
n x
K
x x
=
( )
( )
2
2
2
2
3
2
65.0
2
65.0
65.0 2
7.8179 10 mol
8.062 26 2
7.8179 10 mol
10.062 26
7.7695 10 mol
n x
x
n x
x
n
x
x
x
x
=
=
+ =
=
=

The mole fractions are given by the expressions,
2 2
H I HI
2
, and
x n x
x x x
n n
= = =
Solving for
2 2
H I HI
, , and x x x gives,
4-51
2 2
3
H I
7.7695 10 mol
x x
= =
2
7.8179 10 mol
2 2
2 2
H I
2
H I
2
HI

0.099 381
9.94 10
7.8179 10 mol

x x
x x
x
= =
= =
=
3
2 7.7695 10 mol

2
7.8179 10 mol
HI
2
HI
0.080 124
8.01 10
x
x

=
=


4-52
(C
6
H
5
COOH)
2
2C
6
H
5
COOH
in benzene solution at 10 C is 2.19 10
3
mol dm
3
.
a. Calculate G for the dissociation of the dimer.
b. If 0.1 mol of benzoic acid is present in 1 dm
3
of benzene at 10 C, what are the concentrations of the monomer and of the dimer?
Solution:
Given:
3 3
10.0 C 283.15 K, 2.19 10 mol dm , T K = = =
3
0.1 mol, 1 dm n V = =
Required: G, C
monomer,
C
dimer

a. Solving for G , given by Eq. 4.27,
ln
c
G RT K =
8.3145 J K G =
( )
1
mol 283.15 K
( ) ( )
3 3
1
1
ln 2.19 10 mol dm
14 417 J mol
14.4 kJ mol
G
G
=
=

b. This equilibrium problem can be solved using a table:
(C
6
H
5
COOH)
2
2C
6
H
5
COOH
C
initial
0 0.1 mol dm
-3

C
equilibrium
x 0.1-2x mol dm
-3

The equilibrium constant for this reaction is given by,
| |
( )
2
6 5
6 5
2
C H COOH
C H COOH
c
K =
(

Using the concentrations at equilibrium given in the table, x can be obtained.
4-53
( )
2
3
2
0.1 2
2.19 10
0.01 0.40219 4 0
x
x
x x
=
+ =

Using the quadratic formula, the expression can be further simplified.
2
4
2
b b ac
x
a

=
( ) ( )( )
( )
2
3 3
0.40219 0.40219 4 4 0.01
2 4
0.40219 0.041914
8
0.055513 mol dm or 0.0450345 mol dm
x
x
x x

=
=
= =

From the equilibrium concentrations, we know that there are (0.1-2x) mol dm
-3
of C
6
H
5
COOH, therefore, we take 0.0450345 x = since 2x
cannot be greater than 0.1.
Therefore,
( )
3
monomer
2 3
monomer
3 3
dimer
3
dimer
2 3
dimer
0.045 034 5 mol dm
5 10 mol dm
0.1 mol dm 2 0.045 034 5 mol dm
0.009 931 mol dm
1 10 mol dm
C
C
C
C
C

=
=
=
=
=

4-54
4.17. At 3000 K the equilibrium partial pressures of CO
2
,
CO, and O
2
are 0.6, 0.4, and 0.2 atm, respectively. Calculate G at 3000 K for the reaction:
2CO
2
(g) 2CO(g) +O
2
(g)
Solution:
Given:
2 2
CO CO O
3000 K, 0.6atm, 0.4atm, 0.2atm T P P P = = = =
Required: G
G is given by Eq. 4.20 as
ln
P
G RT K =
2
2
2
CO O
2
CO
P
P P
K
P
=

Solving for G gives,
2
2
2
CO O
2
CO
ln
8.3145 J K
P P
G RT
P
G
| |
= |
|
\ .
=
( )
1
mol 3000 K
( )
( ) ( )
( )
2
2
1
1
0.4atm 0.2atm
ln
0.6atm
60 372.45 J mol
6 10 kJ mol
G
G
| |
|
|
\ .
=
=

4-55
4.18. The conversion of malate into fumarate:
1. malate(aq) fumarate(aq) +H
2
O(l)
is endergonic at body temperature, 37 C; G is 2.93 kJ mol
1
. In metabolism the reaction is coupled with
2. fumarate(aq) aspartate(aq)
for which G is 15.5 kJ mol
1
at 37 C.
a. Calculate K
c
for reaction 1.
b. Calculate K
c
for reaction 2.
c. Calculate K
c
and G for the coupled reaction 1 +2.
Solution:
Given:
1
1 1
37 C =310.15 K, 2.93 kJ mol T G = =

1
2 2
37 C =310.15 K, 15.5 kJ mol T G = =
Required K
c1
,

K
c2
, K
c1+2
, G
1+2

a. The relationship between G and K
c
ln
c
G RT K =
Rearranging and solving for K
c
gives,
3
2.93 10 J
1
ln
c
G
RT
c
c
G
K
RT
K e
K e

=
=
=
1
mol
8.3145 J
1
K
1
mol
( )
310.15 K ( )
1
1
0.321 03
0.321
c
c
K
K
=
=

4-56
b. Using the procedure in part a, K
c2
can be obtained.
3
15.5 10 J
2 c
K e

=
1
mol
( )
8.3145 J
1
K
1
mol
( )
310.15 K ( )
2
2
407.761
408
c
c
K
K
=
=

c. The coupled reaction of 1 +2 is given by,
malate(aq) aspartate(aq) +H
2
O(l)
K
c1+2
1 2 3
K K K =
Therefore solving for K
c1+2
gives,
1+2 1 2
1+2
1+2
1+2

0.321 408
130.968
131
c c c
c
c
c
K K K
K
K
K
=
=
=
=

G
1+2
is given by Eq. 4.67, the sum of the free energies of each reaction

3 1 2
G G G = +
Solving for G
1+2
gives,
1 1
1 2
1
1 2
1
1 2
12.57 kJ mol
12.6 kJ mol
G
G
G
+
+
+
=
=
=

4-57
4.19. From the data in Appendix D, deduce the G and K
P
values for the following reactions at 25.0 C:
a. N
2
(g) +3H
2
(g) 2NH
3
(g)
b. 2H
2
(g) +C
2
H
2
(g) C
2
H
6
(g)
c. H
2
(g) +C
2
H
4
(g) C
2
H
6
(g)
d. 2CH
4
(g) C
2
H
6
(g) +H
2
(g)
Solution:
Given: 25 C =298.15 K T = , Appendix D
Required: G and K
P
for a-d
a. From Eq. 3.91 the Gibbs energies of formation can be used to obtain G for each reaction.
f f
G G G =
( ) ( ) ( )
1
1
2 16.4 kJ mol 0 3 0
32.8 kJ mol
G
G
= +
=

The relationship between G and K
P
ln
P
G RT K =
P
gives,
3
32.8 10 J
ln
P
G
RT
P
P
G
K
RT
K e
K e

=
=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
298.15 K ( )
2
5 2
557 552 bar
5.58 10 bar
P
P
K
K
=
=

4-58
b. Using the same procedure as part a,
( ) ( ) ( )
1 1
1
1
32.0kJ mol 2 0 209.9 kJ mol
241.9 kJ mol
242 kJ mol
G
G
G

= +
=
=

3
241.9 10 J
P
K e

=
1
mol
( )
8.3145 J
1
K
1
mol
( )
298.15 K ( )
42 2
42 2
2.392 522 10 bar
2.39 10 bar
P
P
K
K
=
=

c. Using the same procedure as part a,
( ) ( ) ( )
1 1
1
1
32.0kJ mol 0 68.4 kJ mol
100.4 kJ mol
100 kJ mol
G
G
G

= +
=
=

3
100 10 J
P
K e

=
1
mol
( )
8.3145 J
1
K
1
mol
( )
298.15 K ( )
17 1
17 1
3.304 94 10 bar
3.30 10 bar
P
P
K
K
=
=

d. Using the same procedure as part a,
( ) ( ) ( )
1 1
1
32.0kJ mol 0 2 50.5 kJ mol
69 kJ mol
G
G

= +
=

4-59
3
69 10 J
P
K e
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
298.15 K ( )
13
13
8.161 64 10
8.2 10
P
P
K
K
=
=


4-60
4.20. Calculate K
c
and K
x
for each of the reactions in Problem 4.19 assuming total pressures of 1 bar in each case.
Solution:
Given: P =1 bar, Problem 4.19
Required: K
c
, and K
x
in each case
c
and K
P
is given by Eq. 4.26, K
P
=K
c
(RT)
v
, wherev is the difference between the moles of products to the
moles of products. Rearranging for K
c
gives,
K
c
=K
P
(RT)
-v

Since there are two moles of ammonia produced from one mole of nitrogen gas and three moles of hydrogen gas,
v =-2 mol.
Solving for K
c
,

5 2
5.58 10 bar
c
K

=
( )
0.083 145 bar
3 1
dm K
1
mol 298.15K
( )
( ) 2
2 6
2 2 6
908.013 mol dm
9.08 10 mol dm
c
c
K
K
=
=

x
and K
P
K
P
=K
x
P
v
Rearranging for K
x
gives,

v
x P
K K P
=

Since there are two moles of ammonia produced from one mole of nitrogen gas and three moles of hydrogen gas,
v =-2 mol.
Solving for K
x
4-61
5 2
5.58 10 bar
x
K

=
( )
1 bar
( )
2
5

5.58 10
x
K =
\
Repeating this procedure for each reaction gives the following results:

K
P
v K
c
=K
P
(RT)
-v

v
x P
K K P
=
a.
5 2
5.58 10 bar
2
2 2 6
9.08 10 mol dm
5
5.58 10
b.
42 2
2.39 10 bar
2
39 2 6
3.89 10 mol dm
42
2.39 10
c.
17 1
3.30 10 bar
1
16 3
1.33 10 mol dm
17
3.30 10
d.
13
8.2 10

0
13
8.2 10

13
8.2 10


4-62
4.21. At 25.0 C the equilibrium constant for the reaction:
CO(g) +H
2
O(g) CO
2
(g) +H
2
(g)
is 1.00 10
5
, and S is 41.8 J K
1
mol
1
.
a. Calculate G and H at 25.0 C.
b. Suppose that 2 mol of CO and 2 mol of H
2
O are introduced into a 10-dm
3
vessel at 25.0 C. What are the amounts of CO, H
2
O,
CO
2
, and H
2
at equilibrium?
Solution:
Given:
5 1 1
25 C =298.15 K, 1.00 10 , 41.8 J K mol T K S = = =

2
3
CO H O
2 mol, 2 mol, 10 dm n n V = = =
Required: G, H at 25.0 C and,
2 2 2
CO equilibrium H O equilibrium CO equilibrium H equilibrium
, , , n n n n

a. The relationship between G and K is given by

ln G RT K =
1
8.3145 J K G

=
( )
1
mol 298.15 K
( ) ( )
5
1
1
ln 1.00 10
28 540 J mol
2.85 kJ mol
G
G
=
=

The relationship between G and H is given by Eq. 3.90,
G = H TS,
Hence, G = H TS
Rearranging and solving for H gives,
4-63
1

28 540 J mol 298.15 K
H G T S
H

= +
= +
( )
1
41.8 J K
( )
1
1
1
mol
41 002 J mol
41.0 kJ mol
H
H
=
=

b. This equilibrium problem can be solved using a table:

CO(g) +
H
2
O(g)

CO
2
(g) + H
2
(g)
n
initial
2

2 0 0 mol
n
equilibrium
2 x 2 x x x

mol

For this reaction,

the equilibrium constant is given by the equation
| || |
| || |
2 2
2
CO H
CO H O
c P
K K = = .
The total volume is constant for the reaction, and cancels out, therefore we can write,
2 2
2
CO H
CO H O
c P
n n
K K
n n
= =
Solving for x, we can then obtain
2 2 2
CO equilibrium H O equilibrium CO equilibrium H equilibrium
, , , and n n n n

4-64
( )( )
( )( )
( )
( )
( )
( )
2
5
2
5
5 5
5 5
5
5
2 2
1.00 10
2
10 2
2 10 10
2 10 1 10
2 10
1 10
0.006 304 6
c P
x x
K K
x x
x
x
x x
x x
x
x
x
= =

=
=
= +
= +
=
+
=

Therefore,

2 2
2 2
2 2
2
2
CO equilibrium H equilibrium
3
CO equilibrium H O equilibrium
0.006 304 6
6.30 10
2
2 0.006 304
n n x
n n
n n
n n x
n n
= =
= =
= =
= =
= =
2
2
6
1.993 695 4
1.99
n n
n n
= =
= =

4-65
4.22. Suppose that there is a biological reaction:
1. A +B Z
for which the G value at 37.0 C is 23.8 kJ mol
1
. (Standard state =1 mol dm
3
.) Suppose that an enzyme couples this reaction
with
2. ATP ADP +phosphate
for which G =31.0 kJ mol
1
. Calculate the equilibrium constant at 37.0 C for these two reactions and for the coupled reaction
3. A +B +ATP Z +ADP +phosphate
Solution:
Given:
1 1
1 2
23.8 kJ mol , 31.0 kJ mol , G G = =

3
37.0 C =310.15 K, 1 mol, 1 dm T n V = = =
Required:
1 2 3
, , K K K

c
| |
| || |
Z
A B
c
K = . Therefore the units of K
c
will be in
1 3
mol dm
. The relationship between G

and K
c
ln
c
G RT K =
c
gives,
4-66
3
23.8 10 J
1
ln
c
G
RT
c
G
K
RT
K e
K e

=
=
=
1
mol
8.3145 J
1
K
1
mol
( )
310.15 K ( )
5 3
1
5 3
1
9.812 13 10 mol dm
9.81 10 mol dm
K
K

=
=

K
2
can be obtained by following the same procedure. K
c
is given by
| || |
| |
ADP phosphate
ATP
c
K = . Therefore the units of K
c
will be in
3
mol dm

3
31.0 10 J
2
K e

=
1
mol
( )
8.3145 J
1
K
1
mol
( )
310.15 K ( )
3
2
166 269 mol dm K

=

5 3
2
1.66 10 mol dm K

=
For the coupled reaction, K
3
1 2 3
K K K =
Solving for K
3
gives,
5 1
3
9.81 10 mol K

=
3
dm
( )
5
1.66 10 mol
3
dm
( )
3
3
16.2846
16.3
K
K
=
=

4-67
4-68
4.23. The equilibrium between citrate and isocitrate involves cis-aconitate as an intermediate:
citrate cis-aconitate +H
2
O isocitrate
At 25 C and pH 7.4 it was found that the molar composition of the mixture was:
90.9% citrate
2.9% cis-aconitate
6.2% isocitrate

Calculate the equilibrium constants for the individual reactions, and for the overall reaction, and G for the citrate-isocitrate system.
Solution:
Given: 25 C =298.15 K, pH =7.4, T =
citrate aconitate isocitrate
0.909, 0.029, 0.062
cis
x x x
= = =
Required:

1 2 3
, , , K K K G
The individual reactions are given by,
1. citrate cis-aconitate +H
2
O
2. cis-aconitate +H
2
O isocitrate
3. citrate cis-aconitate +H
2
O isocitrate
K
1
2
aconitate H O
1
citrate
cis
x x
K
x
= .
Solving for K
1
gives,
4-69
2
2
aconitate H O
1
citrate
H O
1
2
1
where 1
0.029
0.031 903 2
0.909
3.19 10
cis
x x
K
x
x
K
K
=
=
= =
=

K
2
2
isocitrate
2
aconitate H O cis
x
K
x x
=
Solving for K
2
gives,
2
aconitate H O
1
citrate
cis
x x
K
x
=
2
H O
2
2
where 1
0.062
2.137 93
0.029
2.14
x
K
K
=
= =
=

K
3
is the overall rate constant and is given by Eq. 4.65,
1 2 3
K K K =
Solving for K
3
gives,
( )( )
2
3
3
2
3
3.190 32 10 2.137 92
0.068 207
6.82 10
K
K
K
=
=
=

The relationship between G and K is given by,
4-70
ln G RT K =
1
8.3145 J K G =
( )
1
mol 298.15 K
( ) ( )
1
1
ln 0.068 207
6656.545 J mol
6.66 kJ mol
G
G
=
=


4-71
4.24. The solubility product of Cr(OH)
3
is 3.0 10
29
mol
4
dm
12
at 25 C. What is the solubility of Cr(OH)
3
in water at this temperature?
Solution:
Given:
29 4 12
sp
=3.0 10 mol dm K 25 C =298.15 K T =
Required: solubility of Cr(OH)
3

When Cr(OH)
3
dissolves, the reaction becomes
( ) ( )
3
Cr OH s

3
Cr
+
+
3OH

A 3a
Where a is the solubility in mol dm
3
K
sp
is given by the ( )
3
4
sp
3 27 K a a a = = .
Solving for a,
( )
sp
4
29 4 12
4
8 3
8 3
27
3.0 10 mol dm
27
3.246 68 10 mol dm
3.2 10 mol dm
K
a
a
a
a
=
=
=
=

4-72
4.25. A gas reaction:
A B +C
is endothermic and its equilibrium constant K
P
is 1 bar at 25 C.
a. What is G at 25 C (standard state: 1 bar)?
b. Is S, with the same standard state, positive or negative?
c. For the standard state of 1 M, what are K
c
and G?
d. Will K
P
at 40 C be greater than or less than 1 bar?
e. Will G at 40 C (standard state: 1 bar) be positive or negative?

Solution:
Given: =1 bar, 25 C =298.15 K
P
K T =
Required:
a. G is given by Eq. 4.20,
ln
P
G RT K =
1
8.3145 J K G =
( )
1
mol 298.15 K
( ) ( )
1
ln 1 bar
0 J mol G =

b. The relationship between G and H is given by Eq. 3.90,
G = H TS, hence, G = H TS
Rearranging and solving for S gives,
0
H G
S
T
G
H
S
T

=
=

=

4-73
Since the reaction is endothermic,
0
0
H
S
>
>

c. The relationship between K
c
and K
P
K
P
=K
c
(RT)
v
c
gives,
K
c
=K
P
(RT)
-v

Since there are two moles of gas produced from one mole of A,
v =+1 mol.
Solving for K
c
at 1 bar P = gives,
1 bar
c
K =
( )
0.083 145 bar
3 1
dm K
1
mol 298.15K
( )
( ) 1
3
2 3
m 0.040 339 4 mol d
4.03 10 mol dm
c
c
K
K
=
=

G is given by Eq. 4.27,
ln
c
G RT K =
-1
ln
8.3145 J K
c
G RT K
G
=
=
1
mol 298.15K
( ) ( )
2 3
1
1
ln 4.033 94 10 mol dm
7958.545 J mol
7.96 kJ mol
G
G
=
=

d. Since the reaction is endothermic, increasing the temperature to 40 C, will shift the equilibrium to the right, making the forward reaction
more likely to occur, and the equilibrium constant, K
P
, will increase.
1 bar
P
K >
4-74
e. Since the reaction is endothermic, increasing the temperature to 40 C, will shift the equilibrium to the right, making the forward reaction
more likely to occur.
0 G <


4-75
4.26. A solution reaction:
A +B X +Y
is endothermic, and K
c
at 25 C is 10.
a. Is the formation of X +Y exergonic at 25 C?
b. Will raising the temperature increase the equilibrium yield of X +Y?
c. Is S positive or negative?
Solution:
Given: =10, 25 C =298.15 K
c
K T =
Required:
a. An exergonic reaction is one that releases energy, i.e., 0 G <
G is given by Eq. 4.27,
-1
ln
8.3145 J K
c
G RT K
G
=
=
1
mol 298.15K
( )
( )
1
1
ln 10
5708.035 J mol
5.7 kJ mol
G
G
=
=

Therefore G is less than zero, and the formation of X +Y is exergonic at 25 C.
b. Since the reaction is endothermic, increasing the temperature will shift the equilibrium to the right, making the forward reaction more
likely to occur, and the equilibrium yield will increase.
c. The relationship between G and H is given by Eq. 3.90,
4-76
where 0 and H 0 for an endothermic process,
0
H G
S
T
G
S

=
< <
>

4-77
4.27. From the data given in Appendix D, for the reaction:
C
2
H
4
(g) +H
2
(g) C
2
H
6
(g)
a. G, H, and S at 25 C; what is the standard state?
b. K
P
at 25 C.
c. K
c
at 25 C (standard state: 1 M).
d. G at 25 C (standard state: 1 M).
e. S at 25 C (standard state: 1 M).
f. K
P
Solution:
Given: Appendix D, 25 C 298.15 K T = =
Required:
a. From Eq. 3.91 the Gibbs energies of formation can be used to obtain G for each reaction.
f f
G G G =
( ) ( ) ( )
1 1
1
1
32.0 kJ mol 68.4 kJ mol 0
100.4 kJ mol
100 kJ mol
G
G
G

= +
=
=

From Eq. 2.53 the enthalpies of formation can be used to obtain H for each reaction.
( ) ( )
( ) ( ) ( )
1 1
1
1
products reactants
84.0 kJ mol 52.4 kJ mol 0
136.4 kJ mol
136 kJ mol
f f
H H H
H
H
H

=
= +
=
=

The relationship between G, H and S is given by Eq. 3.90,
4-78
H G
S
T

=
( )
3 1 3 1
136.4 10 J mol 100.4 10 J mol
298.15 K
S

=
1
1
120.744 59 J mol K
121 J mol K
S
S
=
=

b. The relationship between K
P
and G is given by Eq. 4.20,
ln
P
G RT K = . Rearranging and solving for K
P
gives,
3
100.4 10 J
ln
P
G
RT
P
P
G
K
RT
K e
K e

=
=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
298.15 K ( )
17 1
17 1
3.883 65 10 bar
3.88 10 bar
P
P
K
K
=
=

c
and K
P
K
P
=K
c
(RT)
v
c
gives,
K
c
=K
P
(RT)
-v

Since there is one mole of gas produced from two moles of gas reactants,
v =-1 mol.
Solving for K
c
gives,
4-79
( )
17 1 3 -1
3.883 65 10 bar 0.083 145 bar dm K
c
K

=
1
mol 298.15K
( )
( ) 1
18 3 1
18 3 1
9.627 44 10 dm mol
9.63 10 dm mol
c
c
K
K

=
=

d. The relationship between K
c
ln
c
G RT K =
1
8.3145 J K G =
( )
1
mol 298.15 K
( ) ( )
18 3 1
1
1
ln 9.627 44 10 dm mol
108 358 J mol
108 kJ mol
G
G
=
=

e. Solving for S using the expression obtained in part a. gives,
( )
3 1 1
1 1
1 1
136.4 10 J mol 108 358 J mol
298.15 K
94.051 49 J mol K
94.1 J mol K
S
S
S

=
=
=

f. Assuming that H and S are temperature independent, we solve for K
P
,
4-80
( )
3 1
100 C 136.4 10 J mol 373.15 K
G H T S
G

=
=
( )
1 1
120.744 59 J mol K

( )
( )
1
91 462.268 J
91 462.268 J mol
100 C
G
RT
P
P
G
K e
K e

=
=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
373.15 K ( )
12 1
12 1
6.351 13 10 bar
6.35 10 bar
P
P
K
K
=
=

4-81
4.28. From the data in Appendix D, for the reaction:
2H
2
(g) +O
2
(g) 2H
2
O(g)
a. G, H, and S at 25 C (standard state: 1 bar).
b. K
P
at 25 C.
c. G and K
P
Solution:
Required:
a. From Eq. 3.91 the Gibbs energies of formation can be used to obtain G for the reaction.
f f
G G G =
( ) ( ) ( ) ( )
1
1
2 228.6 kJ mol 2 0 0
457.2 kJ mol
G
G
= +
=

( ) ( )
( ) ( ) ( ) ( )
1
1
products reactants
2 241.826 kJ mol 2 0 0
483.652 kJ mol
f f
H H H
H
H
=
= +
=

The relationship between G and H is given by Eq. 3.90,
4-82
( )
3 1 3 1
1 1
1 1

483.652 10 J mol 457.2 10 J mol
=
298.15 K
= 88.72044 J mol K
= 88.72 J mol K
H G
S
T
S
S
S

=

P
ln
P
P
gives,
3
457.2 10 J
ln
P
G
RT
P
P
G
K
RT
K e
K e

=
=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
298.15 K ( )
80 1
80 1
1.25203 10 bar
1.252 10 bar
P
P
K
K
=
=

c. Assuming that H and S are temperature independent, we solve for G and K
P
at 2000 C.
4-83
( )
3 1

2000 C 483.652 10 J mol 2273.15 K
G H T S
G

=
=
( )
1 1
88.72044 J mol K

( )
( )

1
1
281977.1318 J
281977.1318 J mol
282.0 kJ mol
2000 C
G
RT
P
P
G
G
K e
K e

=
=
=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
2273.15 K ( )
1
6 1
3015697.02 bar
3.016 10 bar
P
P
K
K
=
=

4-84
4.29. Calculate the equilibrium constant at 400 K for the reaction:
3O
2
(g) 2O
3
(g).
where
f
G(O
3
, g) =163.2 kJ mol
1
.
Solution:
Given: 400 K T = ,
f
G(O
3
, g) =163.2 kJ mol
1

Required: K
From Eq. 3.91 the Gibbs energies of formation can be used to obtain G for the reaction.
f f
G G G =
( ) ( )
1
1
2 163.2 kJ mol 3 0
326.4 kJ mol
G
G
=
=


and G is given by
ln
P

gives,
3
326.4 10 J
ln
G
RT
G
K
RT
K e
K e

=
=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
400 K ( )
43
43
2.38538 10
2.39 10
K
K
=
=

4-85
4.30. The hydrolysis of adenosine triphosphate to give adenosine diphosphate and phosphate can be represented by:
ATP ADP +P
The following values have been obtained for the reaction at 37 C (standard state: 1 M):
1
1
31.0kJ mol
20.1kJ mol
G
H
=
=

a. Calculate S.
b. Calculate K
c
at 37 C.
c. On the assumption that H and S are temperature independent, calculate G and K
c
at 25 C.
Solution:
Given:
1 1
37 C 313.15 K, 31.0 kJ mol , 20.1 kJ mol T G H = = = =
Required:
a. The relationship between G and H is given by Eq. 3.90,
( )
3 1 3 1
1 1
1 1

20.1 10 J mol 31.0 10 J mol
310.15 K
35.14429 J mol K
35.1 J mol K
H G
S
T
S
S
S

=

=
=
=

c
ln
c
c
gives,
4-86
3
31.0 10 J
ln
c
G
RT
c
c
G
K
RT
K e
K e

=
=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
310.15 K ( )

3
5 3
166269.3995 mol dm
1.66 10 mol dm
c
c
K
K
=
=

c. Assuming that H and S are temperature independent, we solve for G and K
c
at 25 C.
( )
3 1

25 C 20.1 10 J mol 298.15 K
G H T S
G

=
=
( )
1 1
35.14429 J mol K

( )
( )

1
1
30578.27006 J
30578.27006 J mol
30.6 kJ mol
25 C
G
RT
c
c
G
G
K e
K e

=
=
=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
298.15 K ( )
3
5 3
227539.635 mol dm
2.28 10 mol dm
c
c
K
K
=
=


4-87
4.31. Thermodynamic data for n-pentane(g) and neo-pentane(g) (standard state: 1 bar and 25 C) are as follows:

Compound
Enthalpy of Formation,
f
H kJ mol
1

Entropy, S J K
1

mol
1

n-Pertane(g) 146.44 349.0
Neopentane(g) 165.98 306.4

a. Calculate G for n-pentane neopentane.
b. Pure n-pentane is in a vessel at 1 bar and 25 C, and a catalyst is added to bring about the equilibrium between n-pentane and
neopentane. Calculate the final partial pressures of the two isomers.
Solution:
a. The relationship between G, H and S is given by Eq. 3.90,
To obtain G we must first determine H and S.
( ) ( )
( ) ( )
1 1
1
products reactants
165.98 kJ mol 146.44 kJ mol
19.54 kJ mol
f f
H H H
H
H

=
=
=

From Eq. 3.69 the absolute entropies can be used to obtain H for each reaction.
( ) ( )
1 1 1 1
1 1
products reactants
306.4 J K mol 349.0 J K mol
42.6J K mol
S S S
S
S
=
=
=

Solving for G,
4-88
( )
3 1

100 C 19.54 10 J mol 298.15 K
G H T S
G

=
=
( )
1 1
42.6 J mol K

( )
1
1
6838.81 J mol
6.84 kJ mol
G
G
=
=

b. To calculate the partial pressures, we need to obtain the equilibrium constant K
P.
P
and G is given by Eq.
4.20,
ln
P
P
gives,
( )
6838.81 J
100 C
G
RT
P
P
K e
K e

=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
298.15 K ( )
1
15.77983 bar
P
K =

The expression for
P
K is given by,
neopentane
pentane
P
n
P
K
P
=
At equilibrium, we have
n-pentane neopentane
1-x x
Therefore
P
K becomes,
1
P
x
K
x
=
. Solving for x, we can obtain the partial pressures.

4-89
( )
( )
( )
( )
( )
( )

neopentane

pentane

pentane

pentane
1
0
1 0
1
1
15.77983
15.77983 1
0.940405 bar
0.940 bar
1 1bar 0.940405 bar
0.059595 bar
0.060 bar
P
P P
P P
P P
P
P
n
n
n
K x x
K K x x
K x K
x K K
K
x
K
x
x
P x
P x
P
P
=
=
+ =
+ =
=
+
=
+
=
= =
= =
=
=


4-90
4.32. a. An equilibrium constant K
c
is increased by a factor of 3 when the temperature is raised from 25.0 C to 40.0 C. Calculate the
standard enthalpy change.
b. What is the standard enthalpy change if instead K
c
is decreased by a factor of 3 under the same conditions?
Solution:
Given:
1 2
25.0 C 298.15 K, 40.0 C 313.15 K T T = = = =
Required: H
a. The problem states that ( )
2 1
3
c c
K K = . To obtain H , the standard enthalpy change, we use Eq.4.83.
ln
(1/ )
c
d K U
d T R

=
This can be written as,
ln
(1/ )
c
d K H
d T R

= since U and H are very close in solution.
2
1 2 1
1
ln
(1/ )
1 1
ln
8.3145 J K
c
c
c
d K
H R
d T
K
H R
K T T
H
| |
=
|
\ .
| | | | | |
=
| | |
|
\ . \ . \ .
=
( )
1 1
3
mol ln
c
K
1 c
K
1
313.15K
| |
|
|
\ .
1
298.15K
( ) ( ) ( ) ( )
1 4
1
1
8.3145 J mol ln 3 1.60658619 10
56 856.03383 J mol
56.9 kJ mol
H
H
H
| |
| |
|
|
|
\ .
\ .
=
=
=

4-91
b. The problem states that
2 1
1
3
c c
K K
| |
=
|
\ .
. Using the same procedure as part a., H can be obtained.
2
1 2 1
1 1
ln
c
c
K
H R
K T T
| | | | | |
=
| | |
|
\ . \ . \ .

1
8.3145 J K H =
( )
1 1
mol ln
c
K
1
3
c
K
1
313.15K
| |
|
|
\ .
1
298.15K
| |
| |
|
|
|
\ .
\ .

( ) ( )
1 4
1
1
1
8.3145 J mol ln 1.60658619 10
3
56 856.03383 J mol
56.9 kJ mol
H
H
H
| | | |
=
| |
\ . \ .
=
=


4-92
4.33. a. The ionic product [H
+
] [OH
], which is the equilibrium constant for the dissociation of water;

H
2
O H
+
+OH

is 1.00 10
14
mol
2
dm
6
at 25.0 C and 1.45 10
14
mol
2
dm
6
at 30.0 C. Deduce H and S for the process.
b. Calculate the value of the ionic product at body temperature (37 C).
Solution:
Given:
14 2 6
1 1
1.00 10 mol dm , 25.0 C 298.15 K K T = = =
14 2 6
2 2
1.45 10 mol dm , 30.0 C 303.15 K K T = = =
Required:
a. To obtain H , the standard enthalpy change, we use Eq.4.83.
ln
(1/ )
c
d K U
d T R

=
ln
(1/ )
c
d K H
d T R

2
1 2 1
1
ln
(1/ )
1 1
ln
8.3145 J K
c
d K
H R
d T
K
H R
K T T
H
| |
=
|
\ .
| | | | | |
=
| | |
|
\ . \ . \ .
=
( )
14 2
1
1.45 10 mol
mol ln

6
dm
14 2
1.00 10 mol
6
dm
1
303.15K
| |
|
|
\ .
1
298.15K
( ) ( ) ( ) ( )
1 5
1
1
8.3145 J mol ln 1.45 5.531942 10
55 845.94325 J mol
55.8 kJ mol
H
H
H
| |
| |
|
|
|
\ .
\ .
=
=
=

To obtain S we use the relationship between G, H and S given by Eq. 3.90,
4-93
To continue to solve, we must determine G. The relationship between K

and G is given by ln G RT K = .
1
8.3145 J K G =
( )
1
mol 298.15 K
( ) ( )
14 2 6
1
ln 1.00 10 mol dm
79 912.49232 J mol G
=

Solving for S gives,
( )
1 1
1 1
1 1
55845.94325 J mol 79 912.49232 J mol
298.15 K
80.71960 J mol K
80.7 J mol K
H G
S
T
S
S
S

=
=
=
=

b. To obtain K at 37C we use Eq.4.83.
ln
(1/ )
c
d K U
d T R

=
ln
(1/ )
c
d K H
d T R

2
, the solubility product at37C, gives,
4-94
1
2 1
2
1 2 1
2
1 2 1
2 1
2 1
2 1
2 1
1 1
ln
2
1 1
ln
1 1
ln
1 1
ln ln
1 1
ln ln
H
K
R T T
K H
K T T R
K H
K R T T
H
K K
R T T
H
K K
R T T
K e
| | | |
+ | |
|
\ . \ .
| | | |
=
| |
\ . \ .
| | | |
=
| |
\ . \ .
| |
=
|
\ .
| |
= +
|
\ .
=

Solving for K
2
,

55845.94325 J
2
K e =
1
mol
( )
8.3145 J
1
K
1
mol
( )
1
310.15K
1
298.15K
( )
( )( ) ( ) ( )
( )
14 2 6
-4

ln 1.00 10 mol dm
6716.692916 1.297701 10 32.23619
2
31.36456409
2
K e
K e
| |
| | |
+ | |
\ . |
\ .
+
=
=

14 2 6
2
14 2 6
2
2.390798 10 mol dm
2.39 10 mol dm
K
K
=
=


4-95
P
for the reaction I
2
(g) +cyclopentane(g) 2 HI(g) +cyclopentadiene(g) varies with temperatures
according to the equation:
log
10
(K
P
/bar) =7.55 4844/(T/K)
a. Calculate K
P
, G, H, S (standard state: 1 bar) at 400 C.
b. Calculate K
c
and G (standard state: 1 M) at 400 C.
c. If I
2
and cyclopentane are initially at 400 C and at concentrations of 0.1 M, calculate the final equilibrium concentrations of I
2
,
cyclopentane, HI, and cyclopentadiene.
Solution:
Given: 400 C 673.15 K T = =
Required:
a. K
P
can be obtained from the equation log
10
(K
P
/bar) =7.55 4844/(T/K).
( )
( )
10
4844
7.55
4844
7.55
673.15
1
1
4844
log / bar 7.55
/ K
10
10
2.25934 bar
2.26 bar
P
T
P
P
P
P
K
T
K
K
K
K
| |
|
\ .
| |
|
\ .
=
=
=
=
=

P
ln
P
G RT K =
1
8.3145 J K G =
( )
1
mol 673.15 K
( ) ( )
1
1
1
ln 2.25934 bar
4561.885 J mol
4.56 kJ mol
G
G
=
=

4-96
The temperature dependence of the equilibrium constant is given by the equation
log
10
(K
P
/bar) =7.55 4844/(T/K). From this equation, H, by converting it into Eq. 4.75,
ln
P
H
K I
RT

= + .
To convert log
10
K
P
to ln K
P
, we use the law of logarithm that states
( )
log
log log
b
x
a a
b x =
( )
10
log
10
10
ln 10 ln
ln 2.303log
4844
2.303log 2.303+7.55
P
K
P
P P
P
K
K K
K
T
=
=
| |
=
|
\ .

To solve for H, we drop the 7.55 term and multiply by R
10
1
2.303 log
2.303 8.3145 J K
P
H R K
H
=
=
( )
1
mol 4844 K
( )
1
1
927 54.334 J mol
92.75 kJ mol
H
H
=
=

H G
S
T

=
( )
1 1
927 54.334 J mol 4561.885 J mol
673.15 K
S

=
1
1
144.568 J mol K
145 J mol K
S
S
=
=

4-97
c
and K
P
K
P
=K
c
(RT)
v
c
gives,
K
c
=K
P
(RT)
-v

Since there are three moles produced from two moles of gas reactants,
v =+1 mol.
Solving for K
c
gives,
( )
1 3 -1
2.25934 bar 0.083145 bar dm K
c
K

=
1
mol 673.15K
( )
( ) 1
3 1
2 3 1
0.040368 dm mol
4.04 10 dm mol
c
c
K
K
+

=
=

c
ln
c
G RT K =
1
8.3145 J K G =
( )
1
mol 673.15 K
( ) ( )
3 1
1
1
ln 0.040368 dm mol
17964.48826 J mol
18.0 kJ mol
G
G
=
=

c. To calculate the equilibrium concentrations, we need to obtain the expression for the equilibrium constant K
c
.
| | | |
| || |
2
2
HI cyclopentadiene
I cyclopentane
c
K =
At equilibrium, we have
I
2
(g) + cyclopentane(g) 2 HI(g) + cyclopentadiene(g)

0.1 x

0.1 x

2x

x
4-98

Therefore
c
K becomes,
( )
( )( )
( )
2
3
2
2
0.1 0.1
4
0.1
c
c
x x
K
x x
x
K
x
=

=
.
Solving for x, we can obtain the equilibrium concentrations.
( )
( )
( )
( ) ( )
3
3 1
2
2
3 1 3
3 1 2 3
4 3 1 2 3 1 2 3 1 2 3
4
0.040368 dm mol
0.1
0.040368 dm mol 0.1 4
0.040368 dm mol 0.01 0.2 4
4.0368 10 dm mol 8.0736 10 dm mol 4.0368 10 dm mol 4 0
x
x
x x
x x x
x x x
=
+ =
+ =

To obtain x we can graph the equation and find the solution.
3
0.00500632 mol dm x

=
4-99
| |
| |
| | ( )
| |
| |
| | | |
| | | |
3
3 3
3
3
2 3
2
2
cyclopentadiene 0.00500632 mol dm
cyclopentadiene 5.01 10 mol dm
HI 2 2 0.00500632 mol dm
HI 0.01001264 mol dm
HI 1.00 10 mol dm
I cyclopentane 0.1
I cyclopentane 0.09499368 mol dm
x
x
x

= =
=
= =
=
=
= =
= =
| | | |
3
2 3
2
I cyclopentane 9.50 10 mol dm

= =

4-100
4.35. From the data in Appendix D, for the synthesis of methanol,
CO(g) +2H
2
(g) CH
3
OH(l)
Calculate H, G, and S and the equilibrium constant at 25 C.
Solution:
Required: H, G, S, K
( ) ( )
( ) ( ) ( )
1 1
1
1
products reactants
239.2 kJ mol 110.53 kJ mol 2 0
128.67 kJ mol
128.7 kJ mol
f f
H H H
H
H
H

=
= +
=
=

From Eq. 3.91 the Gibbs energies of formation can be used to obtain G for each reaction.
f f
G G G =
( ) ( ) ( )
1 1
1
1
166.6 kJ mol kJ mol 2 0
kJ mol
kJ mol
G
G
G

= +
=
=

4-101
( )
1 1

J mol J mol
=
298.15 K
H G
S
T
S

=

1
1
= J mol K
= J mol K
S
S

4-102
4.36. The bacterium nitrobacter plays an important role in the nitrogen cycle by oxidizing nitrite to nitrate. It obtains the energy it
requires for growth from the reaction

2 2 3
1
NO (aq) O (g) NO (aq)
2
+
Calculate H, G, and S for this reaction from the following data, at 25 C:
Ion
1
kJ mol
f
H

1
kJ mol
f
G

2
NO 104.6 37.2

3
NO 207.4 111.3
Solution:
Given: 25 C 298.15 K T = =
Required: H, G, S
( ) ( )
( ) ( )
1 1
1
products reactants
1
207.4 kJ mol 104.6 kJ mol 0
2
102.8 kJ mol
f f
H H H
H
H

=
| |
= +
|
\ .
=

f f
G G G =
( ) ( )
1 1
1
1
111.3 kJ mol 37.2 kJ mol 0
2
74.1 kJ mol
G
G

| |
= +
|
\ .
=

4-103
( )
3 1 3 1

102.8 10 J mol 74.1 10 J mol
=
298.15 K
H G
S
T
S

=

1 1
1 1
96.26027 J mol K
96.26 J K mol
S
S

=
=

4-104
4.37. When the reaction:
glucose-1-phosphate(aq) glucose-6-phosphate(aq)
is at equilibrium at 25 C, the amount of glucose-6-phosphate present is 95% of the total.
a. Calculate G at 25 C.
b. Calculate G for reaction in the presence of 10
2
M glucose-1-phosphate and 10
4
M glucose-6-phosphate. In which direction
does reaction occur under these conditions?
Solution:
Given: 25 C 298.15 K T = = ,
glucose 6 phosphate
0.95 x

=
Required:
a. To calculate G, we first find the equilibrium constant for the reaction.
| |
| |
glucose 6 phosphate
glucose 6 phosphate
glucose 6 phosphate
glucose 1 phosphate
1
solving for gives,
0.95
1 0.95
19
K
x
K
x
K
K
K

=

=
=


and G is given by, ln G RT K =
4-105
1
8.3145 J K G =
( )
1
mol 298.15 K
( ) ( )
1
1
ln 19
7299.17052 J mol
7.3 kJ mol
G
G
=
=

b. To calculate G, we follow the same procedure as part a, and first find the equilibrium constant for the reaction. The G will be the
difference in standard Gibbs energy, G and the Gibbs energy for K =10
-2
.
| |
| |
4
2
2
glucose 6 phosphate 10
10
glucose 1 phosphate 10
K

= = =

2
1
10
8.3145 J K
K
G

=
=
( )
1
mol 298.15 K
( ) ( )
2
2
2
1
10
10
1 1
1
1
ln 10
11416.07033 J mol
7299.17052 J mol 11416.07033 J mol
18715.24535 J mol
19 kJ mol
K
K
G
G G G
G
G
G
=
=
=
=
=
=
=


4-106
4.38. From the data in Appendix D, for the reaction
CO
2
(g) +H
2
(g) CO(g) +H
2
O(g)
a. H, G, and S (standard state: 1 bar and 25 C).
b. The equilibrium constant at 25 C.
c. From the heat capacity data in Table 2.1, obtain an expression for H as a function of temperature.
d. Obtain an expression for ln K
P
as a function of temperature.
e. Calculate K
P
at 1000 K.
Solution:
Required:
a. From Eq. 2.53 the enthalpies of formation can be used to obtain H for each reaction.
( ) ( )
( ) ( ) ( )
1 1 1
1
products reactants
110.53 kJ mol 241.826 kJ mol 393.51 kJ mol 0
41.154 kJ mol
f f
H H H
H
H

=
= + +
=

f f
G G G =
( ) ( )
1 1 1
1
111.3 kJ mol kJ mol 228.6 kJ mol
kJ mol
G
G

= +
=

4-107
( )
3 1 3 1

102.8 10 J mol 74.1 10 J mol
=
298.15 K
H G
S
T
S

=

1 1
1 1
96.26027 J mol K
96.26 J K mol
S
S

=
=

b. The relationship between K and

c. Heat capacity is given by equation 2.52 as,
2 2
2 1 2 2 1
2 1
1 1 1
( ) ( ) ( ) ( )
2
m m
H T H T d T e T T f
T T
| |
= + +
|
\ .

From the values in Table 2.1 we can obtain d, e and f.
( ) ( )
1 1
28.41 30.54 44.22 27.28
12.55 J K mol
d d d
d
d
=
= + +
=

( ) ( )
3 3
3 2 1
4.10 10.29 10 8.79 3.26 10
2.34 10 J K mol
e e e
e
e
=
= + +
=

4-108
( ) ( )
4 4
4 1
4.6 0 10 86.2 5.0 10
76.6 10 J K mol
f f f
f
f
=
= + +
=

Solving for an expression for H as a function of temperature gives,
( ) ( ) ( ) ( )
( )
2
1 1 1 3 2 1 2
2 2 2
4 1
2
1
41 154J mol 12.55 J K mol 2.34 10 J K mol 298.15 K
2
1 1
76.6 10 J K mol
298.15 K
H T T T
T
= +
| |
|
\ .

Simplifying we obtain,
( ) ( ) ( )
( )
( ) ( )( )
( )
2
3 2 4
2 2 2
2
4 4
2
3 2 3
2 2 2
2
4
3 2
2 2 2
2
1 1
41 154 12.55 1.17 10 298.15 76.6 10
298.15
76.6 10 76.6 10
41 154 12.55 1.17 10 1.17 10 298.15
298.15
76.6 10
41 154 12.55 1.17 10 104.005 2569
H T T T
T
H T T T
T
H T T T
T
| |
= +
|
\ .

= + +
= + + .177

( )
( )
4
3 2
2 2 2
2
4 1
1 3 2 1 2 1 1
76.6 10
43 619.172 12.55 1.17 10
76.6 10 J K mol
43 619J mol 1.17 10 J K mol 12.55 J K mol
H T T T
T
H T T T
T
= +
= +

d. To obtain an expression for lnK
P
, we use Eq. 4.72,
2
ln
P
d K H
dT RT

=
Rearranging for lnK
P
gives,
4-109
2
2
ln
ln
P
P
H
d K dT
RT
H
K dT
RT

=

=

Substituting the expression obtained in part c., we obtain,
To obtain I, we use the result from part b.

3 1
1
1 1
1.17 10 J K mo
1
ln
43 619J mol
8.3145 J K mol
P
K
T
=

+

e. To calculate K
P
at 1000 K, we use the
expression obtained in part d.
3 1
1 1
1
ln 1.17 10 K
8.3145 J K mol
P
K

= 1000 K
( ) ( )
( )
4
43 619 38.3 10 K
12.55ln 1000 K
1000 K

+
2
1000 K
( )
2
3 1
1 1
1
ln 1.17 10 K
8.3145 J K mol
P
K

(
(
(

= 1000 K
( ) ( )
( )
4
43 619 38.3 10 K
12.55ln 1000 K
1000 K

+
2
1000 K
( )
2
(
(
(


( )
4
3 2
2
3 2
2
76.6 10
43 619 1.17 10 12.55
ln
43 619 1.17 10
ln
P
P
H T T T
T
H
K dT
RT
T
K
RT
= +

=
= +
2
RT
12.55T
2
RT
4
2
3 4
2 3
4
3
2 3
4
3
2
76.6 10 1
43 619 1.17 10 12.55 76.6 10
ln
1 12.55 43 619 76.6 10
ln 1.17 10
1 43 619 76.6 10
ln 1.17 10 12.55ln , where is an integration factor
2
P
P
P
dT
T RT
K dT
RT R RT RT
K dT
R T T T
K T T I I
R T T

= +
= +
(
= + +
(


4-110
4.39. Irving Langmuir [J. Amer. Chem. Soc., 28, 1357 (1906)] studied the dissociation of CO
2
into CO and O
2
by bringing the gas at 1
atm pressure into contact with a heated platinum wire. He obtained the following results:
T/K Percent Dissociation
1395 0.0140
1443 0.0250
1498 0.0471

Calculate K
P
for 2CO
2
(g) =2CO(g) +O
2
(g) at each temperature, and estimate H, G, and S at 1395 K.
Solution:
Given: P =1atm, percent dissociation
Required:
at =1395 at =1443 at =1498
, ,
P T P T P T
K K K , =1395 =1395 =1395 , , T T T H G S
To determine K
P
we find an expression in terms of the amounts of CO
2
, CO and O
2
.

2CO
2
2CO + 0
2

1-x x x/2
( )
( )
( )
( )
( )
2
2
2
CO O
2
CO
2
2
3
2
2
1
1
2
1
P
P
P
x x
K
x
x
x
K
x
x
K
x
=
| |
|
\ .
=

Solving for K
P
at each temperature gives,
4-111
( )
( )
3
2
at =1395 2
2
12
at =1395
12
at =1395
0.0140 10
1
2
1 0.0140 10
1.372 38 10 atm
where 1 atm 1.01325 bar
1.390 57 10 bar
P T
P T
P T
K
K
K
=

=
=
=

12
at =1395
1.39 10 bar
P T
K

=
( )
( )
3
2
at =1443 2
2
12
at =1443
12
at =1443
12
at =1443
0.0250 10
1
2
1 0.0250 10
7.816 41 10 atm
7.919 98 10 bar
1.39 10 bar
P T
P T
P T
P T
K
K
K
K
=

=
=
=
=

( )
( )
3
2
at =1498 2
2
11
at =1498
11
at =1498
11
at =1498
0.0471 10
1
2
1 0.0471 10
5.229 28 10 atm
5.298 57 10 bar
5.30 10 bar
P T
P T
P T
P T
K
K
K
K
=

=
=
=
=


4-112
4.40. G. Stark and M. Bodenstein [Z. Electrochem.,16, 961(1910)] carried out experiments in which they sealed iodine in a glass bulb and
measured the vapor pressure. The following are some of the results they obtained:
3
volume of bulb=249.8 cm
amount of iodine =1.958 mmol

Temperature/C Pressure/Torr
800 558.0
1000 748.0
1200 1019.2

a. Calculate the degree of dissociation at each temperature.
b. Calculate K
c
at each temperature, for the process I
2
2I.
c. Calculate K
P
at each temperature.
d. Obtain values for H and U at 1000 C.
e. Calculate G and S at 1000 C.
Solution:
Given:
3 3 3
1.958 10 mol, 249.8 10 dm n V

= =
Required:
a. The reaction in this problem is given by
I
2
2I
x y/2 mol
The degree of dissociation, , can be obtained by first determining the number of moles of I
2
and I present.
The total number of moles present at equilibrium is given by,
4-113
3
1.958 10 mol
2
y
x

+ = (1)
To obtain a second expression involving x and y, we rearrange the ideal gas law, and solve for x and y.
PV nRT
PV
n
RT
=
=

558.0 torr
PV
x y
RT
x y
+ =
+ =
1 atm
760.0 torr
3 3
249.8 10 dm
| |
|
\ .
( )
0.082 06 atm
3
dm
1
K
( )
1
mol 1073.15 K
( )

3
2.082 67 10 mol x y

+ = (2)
Now we have two equations and two unknowns, and subtracting (1) from (2), we can obtain y.
4
4
3 4
3
1.2467 10 mol
2
2.4934 10 mol
2.082 67 10 mol 2.4934 10 mol
1.8333 10 mol
y
y
x
x
=
=
=
=

Solving for the degree of dissociation,
4-114
1073.15 K
total
3
1073.15 K 3
1073.15 K
2
1073.15 K
1 1
2
1.8333 10 mol
1
1.958 10 mol
0.063 874
6.39 10
T
T
T
T
x x
y n
x
=
=
=
= =
| |
+
|
\ .
=
=

Repeating this procedure, we can determine at 1273.15 K,
748.0 torr
PV
x y
RT
x y
+ =
+ =
1 atm
760.0 torr
3 3
249.8 10 dm
| |
|
\ .
( )
0.082 06 atm
3
dm
1
K
( )
1
mol 1273.15 K
( )

3
2.353 25 10 mol x y

+ = (3)
4
4
3 4
3
3.9525 10 mol
2
7.905 10 mol
2.353 25 10 mol 7.905 10 mol
1.562 75 10 mol
y
y
x
x
=
=
=
=

4-115
1273.15 K
total
3
1273.15 K 3
1273.15 K
1273.15 K
1 1
2
1.562 75 10 mol
1
1.958 10 mol
0.201 86
0.202
T
T
T
T
x x
y n
x
=
=
=
= =
| |
+
|
\ .
=
=

Repeating this procedure, we can determine at 1473.15,
1019.2 torr
PV
x y
RT
x y
+ =
+ =
1 atm
760.0 torr
3 3
249.8 10 dm
| |
|
\ .
( )
0.082 06 atm
3
dm
1
K
( )
1
mol 1473.15 K
( )

3
2.771 15 10 mol x y

+ = (4)
4
3
3 4
3
8.1315 10 mol
2
1.6263 10 mol
2.771 15 10 mol 7.905 10 mol
1.144 85 10 mol
y
y
x
x
=
=
=
=

4-116
1473.15 K
total
3
1473.15 K 3
1473.15 K
1473.15 K
1 1
2
1.144 85 10 mol
1
1.958 10 mol
0.415 30
0.415
T
T
T
T
x x
y n
x
=
=
=
= =
| |
+
|
\ .
=
=

b. To determine the value of K
c
at each temperature, we use the number of moles of I
2
and I, i.e. the values of x and y obtained in part a.
The expression for the equilibrium constant is given by,
| |
| |
2
2
2
2
I
, where
I
1
c
c
c
n
K C
V
y
V
K
x
V
y
K
x V
= =
| |
|
\ .
=
| |
|
\ .
=

At T =1073.15 K,
( )
( ) ( )
2
4
3 3 3
4 3
4 3
2.4934 10 mol
1
1.8333 10 mol 249.8 10 dm
1.357 56 10 mol dm
1.358 10 mol dm
c
c
c
K
K
K
=

=
=

At T =1273.15 K,
4-117
( )
( ) ( )
2
4
3 3 3
3 3
3 3
7.905 10 mol
1
1.562 75 10 mol 249.8 10 dm
1.600 74 10 mol dm
1.601 10 mol dm
c
c
c
K
K
K
=

=
=

At T =1473.15 K,
( )
( ) ( )
2
3
3 3 3
3 3
3 3
1.6263 10 mol
1
1.144 85 10 mol 249.8 10 dm
9.248 27 10 mol dm
9.248 10 mol dm
c
c
c
K
K
K
=

=
=

c
and K
P
K
P
=K
c
(RT)
v
Since there are two moles of I produced from one mole of I
2
,
v =+1 mol.
Solving for K
P
at T =1073.15 K gives,
4
1.357 56 10 mol
P
K

=
3
dm
( )
3
0.083 145 bar dm
-1
K
1
mol
1073.15K
( )
( ) 1
0.012 113 bar
0.0121 bar
P
P
K
K
+
=
=

At T =1273.15 K,
4-118
3
1.60 074 10 mol
P
K

=
3
dm
( )
3
0.083 145 bar dm
-1
K
1
mol
1273.15K
( )
( ) 1
0.169 448 bar
0.1694 bar
P
P
K
K
+
=
=

At T =1473.15 K,
3
9.248 27 10 mol
P
K

=
3
dm
( )
3
0.083 145 bar dm
-1
K
1
mol
1473.15K
( )
( ) 1
1.132 77 bar
1.133 bar
P
P
K
K
+
=
=

d.
e. The relationship between K
P
ln
P
G RT K =
1
8.3145 J K G =
( )
1
mol 1273.15 K
( ) ( )
1
1
ln 0.169 448 bar
18 791.664 J mol
18.79 kJ mol
G
G
=
=

H G
S
T

=
( )
1 1
J mol 18 791.664 J mol
=
1273.15 K
S

4-119
1
1
=J mol K
=J mol K
S
S


4-120
4.41. The following diagram shows the variation with temperature of the equilibrium constant K
c
for a reaction. Calculate G, H, and
S at 300 K.

Solution:
Given: Graph
Required: G, H, and S at 300 K
c
ln
c
G RT K =
1
8.3145 J K G =
( )
1
mol 300 K
( ) ( )
3
1
1
ln 5.7 10
12 889.028 J mol
12.9 kJ mol
G
G
=
=

The temperature dependence of equilibrium constants is given by Eq. 4.83 as
4-121
ln
(1/ )
c
d K U
d T R

= .
ln
(1/ )
c
d K H
d T R

2
1 2 1
1
ln
(1/ )
1 1
ln
8.3145 J K
c
c
c
d K
H R
d T
K
H R
K T T
H
| |
=
|
\ .
| | | | | |
=
| | |
|
\ . \ . \ .
=
( )
3
1
4
5.7 10 1
mol ln
7.8 10 300K
| |

|
\ .
1
340K
( ) ( )
3
1 4
4
1
1
5.7 10
8.3145 J mol ln 3.921 57 10
7.8 10
42 169.192 J mol
42.2 kJ mol
H
H
H
| | | |
| |
|
\ . \ .
| | | |
=
| |
\ . \ .
=
=

H G
S
T

=
( )
1 1
42 169.192 J mol 12 889.028 J mol
300 K
S

=
4-122
1
1
183.5274 J mol K
184 J mol K
S
S
=
=

4-123
4.42. The following values apply to a chemical reaction A Z:
1
1 1
85.2 kJ mol
170.2 J K mol
H
S
=
=

Assuming these values to be temperature independent, calculate the equilibrium constant for the reaction at 300 K. At what temperature is
the equilibrium constant equal to unity?
Solution:
Given:
1 1 1
85.2 kJ mol , 170.2 J K mol , 300 K H S T = = =
Required: K
c
, T where K =1
3 1
85.2 10 J mol 300 K G =
( )
1
170.2 J K
( )
1
1
mol
341 40 J mol G =

c
ln
c
c
gives,
34 140 J
ln
c
G
RT
c
c
G
K
RT
K e
K e

=
=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
300 K ( )
5
879 344.891 2
8.79 10
c
c
K
K
=
=

4-124
The equilibrium constant is equal to unity when G is equal to zero.
( )
( )
ln 1
0
0
G RT
G RT
G
=
=
=

Rearranging Eq. 3.90 we can obtain the temperature at which this occurs.

, where 0

G H T S
H G
T G
S
H
T
S
=

= =

=

3
85.2 10 J
T

=
1
mol
170.2 J
1 1
K mol

500.587 54 K
501 K
T
T
=
=


4-125
c
for the hydrolysis of adenosine triphosphate (ATP) to adenosine diphosphate (ADP) and phosphate is
1.66 10
5
mol dm
3
at 37 C, and H is 20.1 kJ mol
1
. Calculate S for the hydrolysis at 37 C. On the assumption that H and
S are temperature independent, calculate K
c
at 25 C.
Solution:
Given: K
c
=1.66 10
5
mol dm
3
, H =20.1 kJ mol
1
37 C 303.15 K T = =
Required: S where 37 C 303.15 K T = = , K
c
where 25 C 298.15 K T = =
The equilibrium in this problem is given by
ATP ADP +phosphate
Rearranging gives,
H G
S
T

=
To obtain G, we use the relationship between K
c
and G, given by Eq. 4.27,
ln
c
G RT K =
1
8.3145 J K G =
( )
1
mol 310.15 K
( ) ( )
5 1 3
1
ln 1.66 10 mol dm
30 995.818 38 J mol G
=

( )
3 1 1
1 1
1 1
20.1 10 J mol 30 995.818 38 J mol
303.15 K
35.130802J K mol
35.1J K mol
S
S
S

=
=
=

4-126
Assuming H and S are temperature independent, we can calculate K
c
from Eq. 4.27 by first obtaining G from Eq. 3.90 at 25 C
3 1
20.1 10 J mol 298.15 K
G H T S
G
=
=
( )
1
35.130802J K
( )
1
1
mol
30 574.248 62 J mol G =

30 574.24862 J
ln
c
G
RT
c
c
G RT K
K e
K e

=
=
=
1
mol
( )
8.3145 J
1
K
1
mol
( )
298.15 K ( )
3
5 3
227 170.8135 mol dm
2.27 10 mol dm
c
c
K
K
=
=


4-127
4.44. A dissociation A
2
2A has an equilibrium constant of 7.2 10
5
mol dm
3
1
. Calculate
the standard entropy change for the reaction at 300 K. (What is its standard state?) If the H and S values for this reaction are
temperature independent, at what temperature is the equilibrium constant equal to unity?
Solution:
Given:
5 3
7.2 10 mol dm
c
K =
1
300 K, 40.0 kJ mol T H = =
Required: , where 1 S T K =
Rearranging gives,
H G
S
T

=
c
ln
c
G RT K =
1
8.3145 J K G =
( )
1
mol 300 K
( ) ( )
5 3
1
ln 7.2 10 mol dm
23 793.216 63 J mol G
=

( )
3 1 1
1 1
1 1
40.0 10 J mol 23 793.216 63 J mol
300 K
54.022611J K mol
54J K mol
S
S
S

=
=
=

4-128
( )
( )
ln 1
0
0
G RT
G RT
G
=
=
=

G H T S =

, where 0

H G
T G
S
H
T
S

= =

=

3
40.0 10 J
T

=
1
mol
54.022611 J
1 1
K mol

740.430 706 K
740 K
T
T
=
=

4-129
4.45. A reaction A +B Z has an equilibrium constant of 4.5 10
4
dm
3
mol
1
1
. Calculate
the entropy change for the reaction at 300 K. If the H and S values are temperature independent, at what temperature is the
equilibrium constant equal to unity?
Solution:
Given:
4 3 1
4.5 10 dmmol
c
K =
1
300 K, 40.2 kJ mol T H = =
Required: , where 1 S T K =
Rearranging gives,
H G
S
T

=
c
ln
c
G RT K =
1
8.3145 J K G =
( )
1
mol 300 K
( ) ( )
4 3 1
1
ln 4.5 10 dmmol
26 725.507 96 J mol G
=

( )
3 1 1
1 1
1 1
40.2 10 J mol 26 725.507 96 J mol
300 K
44.914 973J K mol
44.9J K mol
S
S
S

=
=
=

4-130
( )
( )
ln 1
0
0
G RT
G RT
G
=
=
=

G H T S =

, where 0

H G
T G
S
H
T
S

= =

=

3
40.2 10 J
T

=
1
mol
44.914 973 J
1 1
K mol

895.024 472 K
895 K
T
T
=
=

4-131
4.46. At 1 bar pressure liquid bromine boils at 58.2 C, and at 9.3 C its vapor pressure is 0.1334 bar. Assuming H and S to be
temperature independent, calculate their values, and calculate the vapor pressure and G at 25 C.
Solution:
Given:
9.3 C
58.2 C, 0.1334bar, 25 C
b T
T P T
=
= = =
Required: , , H S G
First of all, the equilibrium represented in this problem is given by
2 2
Br (l) Br (g)

To solve for G we can use Eq. 4.20
ln
P
G RT K =

We use the vapour pressure as a measure of the equilibrium constant and under the equilibrium conditions, ( ) 58.2 C 331.35K
b
T = = we
obtain,
( )
1
331.35K 8.3145J K G T

= =
( )
1
mol 331.35 K
( ) ( )
( )
1
ln 1bar
331.35K 0J mol G

=

Where 9.3 C 282.45 K T = = , we obtain
( )
1
282.45K 8.3145J K G

=
( )
1
mol 282.45 K
( ) ( )
( )
( )
1
1
ln 0.1334bar
282.45K 4730.685837J mol
282.45K 4731J mol
G
G
=
=

To solve for H and S we use Eq. 3.90, G H T S = . This method is applicable because the problem states that enthalpy and
entropy are temperature independent.
4-132
( )
( )
1
1
4731J mol 282.45K (1)
0J mol 331.35K (2)
G H T S
H S
H S
=
=
=

Subtracting (2) from (1) and then solving gives,
( )
1
1
1 1
1 1
4730.685837J mol 48.9K
4730.685837J mol
48.9K
96.742042 J K mol
96.74J K mol
0
331.35 K
S
S
S
S
G H T S
H T S
H

=
=
=
=
= =
=
=
( )
1
96.742042J K
( )
1
1
1
mol
32055.4755J mol
32055J mol
H
H
=
=

To solve for the vapour pressure at 25 C 298.15K T = = , first we find the value for G, and solve for vapour pressure using Eq. 4.20.
4-133
1
32055J mol 298.15 K
G H T S
G

=
=
( )
1
96.74J K
( )
1
1
3211.969 J
mol
3211.969 J mol
ln
G
RT
G
G RT P
P e
P e
| |
|
\ .
=
=
=
=
1
mol
8.3145 J
1
K
1
mol
298.15 K
0.273709522bar
0.2737bar
P
P
| |
|
|
\ .
=
=

4-134
4.47. The standard Gibbs energy of formation of gaseous ozone at 25 C,
f
G , is 162.3 kJ mol
1
,

for a standard state of 1 bar. Calculate
the equilibrium constants K
P
, K
c
, and K
x
for the process:
3O
2
(g) 2O
3
(g)
What is the mole fraction of O
3
present at 25 C at 2 bar pressure?
Solution:
Given:
1
25 C 298.15 K, 162.3kJ mol , 2bar
f
T G P

= = = =
Required: K
P
, K
c
, and K
x

First of all, the G for the reaction can be calculated from the standard Gibbs energy of formation for gaseous ozone as,
1
1
2 2 162.3kJ mol
324.6kJ mol
f
G G
G

= =
=

Rearranging Eq. 4.20, as shown in Problem 4.46, gives an expression for the K
P

324600 J
ln
P
G
RT
P
P
G RT K
K e
K e
| |
|
\ .
=
=
=
1
mol
8.3145 J
1
K
1
mol
298.15 K
57 1
57 1
1.35768 10 bar
1.36 10 bar
P
P
K
K
| |
|
|
\ .

=
=

The unit of bar
-1
appears because the standard state is 1 bar.
c
and K
P
K
P
=K
c
(RT)
v
c
gives,
K
c
=K
P
(RT)
-v

4-135
Since there are two moles of ozone produced from three moles of oxygen, v =-1 mol.
Solving for K
c
gives,
( )
( )
57 1 1

1.35768 10 bar 8.3145J K
v
c P
c
K K RT
K

=
=
1
mol 298.15 K
( )
( ) 1
54 1 1
5
54 1 1
3.36563 10 J mol bar
where1bar 10 Pa
3.36563 10 J mol bar
c
c
K
K

=
=
=
5 1
10 Pa bar

59 1 1
1 3 3 1 3
56 3 1
3.36563 10 J mol Pa
where1J Pa 1m and therefore 10 J Pa 1dm
3.37 10 dm mol
c
c
K
K

=
= =
=

x
and K
P
K
P
=K
x
P
v
Rearranging for K
x
gives,

v
x P
K K P
=

Since there are two moles of ozone produced from three moles of oxygen, v =-1 mol.
Solving for K
x
at P =2 bar gives,
57 1

1.35768 10 bar
v
x P
x
K K P
K

=
=
( )
1
2 bar
( )
( ) 1
57
57
2.71535 10
2.72 10
x
x
K
K

=
=

4-136
4.48. For the equilibrium:
H
2
(g) +I
2
(g) 2HI(g)
The following data apply:
1
1 1
1 1
(300K)=9.6 kJ mol
(300K)=22.18 J K mol
(500K)=7.11 J K mol
p
H
S
C

The latter value can be taken to be the average value between 300 K and 500 K.
Calculate the equilibrium constants K
P
, K
c
, and K
x
at 500 K. What would be the mole fraction of HI present at equilibrium if HI is
introduced into a vessel at 10 atm pressure; how would the mole fraction change with pressure?
Solution:
Given:
1 1 1
(300 K) 9.6kJ mol , (300 K) 22.18 J K mol , H S

= =
1 1
(500 K) 7.11J K mol , 10atm
P
C P

= =
Required: K
P
, K
c
, and K
x
at 500 K, x
The relationship between enthalpy and heat capacity for changes in temperature is given by Eq. 2.46.
( ) ( )
2 1 2 1 P
H H H C T T = =
Therefore at T =500 K, the enthalpy for the equilibrium becomes,
( )
( )
2 1 2 1
1 1 1
500K
1 1
500K
9600J mol 7.11J K mol 500 K 300 K
9600J mol 7.11J K
P
H H C T T
H
H

= +
=
=
1
mol 200 K
( )
1
500K
11022 J mol H

=

4-137
To determine the entropy change at T =500 K, we derive an equation for the temperature dependence of entropy and heat capacity from the
relationship between entropy and enthalpy at equilibrium.
at equilibrium, 0 H T S
H T S
=
=

Using Eq. 2.46 and integrating we then obtain,
( )
2
1
2 1 2 1
2 1
2
2 1
1
1 1 1 1
500 K
( ) ( )
( ) ( ) ln
500 K
( ) 22.18 J K mol 7.11J K mol ln
P
T
P
T
P
H H C T T
H T S
C dT
S T S T
T
T
S T S T C
T
S T

=
=
= +
= +
=
300 K
1 1
500 K
( ) 18.54802982J K mol S T

| |
|
\ .
=

The Gibbs free energy at T =500 K is,
( )
1
(500 K)
(500 K) 11022 J mol 500K
G H T S
G

=
=
( )
1
18.54802982J K
( )
1
1
mol
(500 K) 20296.01491 J mol G
=

The relationship between Gibbs free energy and K
P
is given by Eq. 4.20. Rearranging as shown in Problem 4.46, gives an expression for the
K
P

4-138
20296.01491J
ln
P
G
RT
P
P
G RT K
K e
K e
| |
|
\ .
=
=
=
1
mol
8.3145 J
1
K
1
mol
500 K
131.9043544
132
P
P
K
K
| |
|
|
\ .
=
=

c
and K
P
K
P
=K
c
(RT)
v
,
x
and K
P
K
P
=K
x
P
v
, wherev is the difference between the moles of products to the moles of products. Since there is no change in the number of
moles of products and reactants, K
c
and K
x
have the same value as K
P
and therefore,
132
P c x
K K K = = =

To find the mole fraction, we determine the expression for K
x
based on the equilibrium.
4-139
( )
( ) ( )
( )
( )( )
2 2
initial
equilibrium
final
2
2
2 2
2
2
H (g) I (g) 2HI (g)
1 1 0
2
1 1 2
2 4
1 1
solving for , we obtain
4
132
1
2
132
1
2 11.48912529 1
11.48912529
13.48912529
0.851732417
0.852
x
n
n x x x
n x x x
x x
K
x x
x
x
x
x
x
x x
x
x
x
+
+

= =

=
=
=
=
=

Pressure has no effect on the mole fraction.

4-140
*4.49. Protein denaturations are usually irreversible but may be reversible under a narrow range of conditions. At pH 2.0, at temperatures
ranging from about 40 C to 50 C, there is an equilibrium between the active form P and the deactivated form D of the enzyme
trypsin:
P D
Thermodynamic values are H =283 kJ mol
1
and S =891 J K
1
mol
1
. Assume these values to be temperature independent over
this narrow range, and calculate G and K
c
values at 40.0 C, 42.0 C, 44.0 C, 46.0 C, 48.0 C, and 50.0 C. At what temperature
will there be equal concentrations of P and D?
**Note that the high thermodynamic values lead to a considerable change in K over this 10 C range.
Solution:
Given: pH = 2.0, H =283 kJ mol
1
and S =891 J K
1
mol
1
, T =40.0 C, 42.0 C, 44.0 C, 46.0 C, 48.0 C, and 50.0 C
Required: G and K
c
at T given, T
equilibrium
To solve for G we use Eq. 3.90, G H T S =

For T =40.0 C,
1
283000J mol 313.15K G =
( )
1
891J K
( )
1
1
1
mol
3983.35J mol
398kJ mol
G
G
=
=

The relationship between Gibbs free energy and K
c
is given by Eq. 4.27. Rearranging gives an expression for the K
c

ln
c
G
RT
c
G RT K
K e
| |
|
\ .
=
=

For T =40.0 C,
4-141
3983.35 J
c
K e
=
1
mol
8.3145 J
1
K
1
mol
313.5 K
0.21656
0.217
c
c
K
K
| |
|
|
\ .
=
=

Applying the same method to each temperature, we then obtain,
Temperature G kJ mol
-1
K
313.15 3.98 0.217
315.15 2.20 0.432
317.15 0.419 0.853
319.15 -1.362 1.67
321.15 -3.14 3.25
323.15 -4.93 6.26

The T
equilibrium
occurs when
4-142
equilibrium
equilibrium
0
283000 J
G H T S
H
T
S
T
= =

=

=
1
mol
891J
1 1
K mol
equilibrium
equilibrium
317.620651 K
317.6 K 44.47 C
T
T
=
= =

4-143
*4.50. Suppose that a large molecule, such as a protein, contains n sites to which a molecule A (a ligand) can become attached. Assume
that the sites are equivalent and independent, so that the reactions M +A =MA, MA +A =MA
2
, etc., all have the same equilibrium
constant K
s
. Show that the average number of occupied sites per molecule is:
[A]
1 [ ]
s
s
nK
v
K A
=
+

Solution:
Given: above
Required: proof
If the concentration of M is [M], then the total number of sites occupied and unoccupied is n[M]. The association of reactions may be
formulated in terms of S, the number of sites.
S A SA
s
K
+

The equilibrium constant becomes
[SA]
[S][A]
s
K = , where [S] is the concentration of unoccupied sites and [SA] in the concentration of occupied sites.
Rearranging the equilibrium constant in terms of [S] gives,
| |
| |
| |
SA
S
A
s
K
=
The total concentration of sites, n[M], upon rearrangement, becomes,
| | | | | |
| |
| |
| |
| |
| | | |
| |
M S SA
SA
M SA
A
1
M SA 1
A
s
s
n
n
K
n
K
= +
= +

= +
`

)

4-144
The average number of sites occupied per molecule is the total concentration of occupied sites divided by the total concentration of M.
| |
| |
| |
| |
| |
SA
M
1
1
A
A
1 A
s
s
s
v
n
v
K
nK
v
K
= =
=
+
=
+

4-145
*4.51. Modify the derivation in Problem 4.50 so as to deal with sites that are not all equivalent; the equilibrium constants for the
attachments of successive ligands are each different:
1
[MA]
M A MA
[M][A]
K + =
2
2 2
[MA ]
MA A MA
[MA][A]
K + =
1
1
[MA ]
MA A MA
[MA ][A]
n
n n n
n
K + =
Show that the average number of molecules of A bound per molecule M is:
2
1 1 2 1 2 3
2
1 1 2 1 2 3
[A] 2 [A] ( )[A]
1 [A] [A] ( )[ ]
n
n
n
n
K K K n K K K K
v
K K K K K K K A
+ + +
=
+ + + +

This equation is important in biology and biochemistry and is often called the Adair equation, after the British biophysical chemist
G. S. Adair.
Solution:
Given: above
Required: proof
The total concentration of the molecule M is
| | | | | | | | | |
2
0
M M MA MA ... MA
n
= + + + +
The total concentration of the occupied sites is the total concentration of the bound A molecules,
| | | | | | | |
2
A MA 2 MA ... MA
n
b
n = + + +
The first few equilibrium constants are given above as,
4-146
| |
| || |
| |
| || |
| |
| || |
2 3
1 2 3
2
MA MA MA
, ,
M A MA A MA A
K K K = = =
Rearranging the equilibrium constants in terms of [A] gives,
| | | || |
| | | || | | || |
| | | || | | || |
1
2
2 2 1 2
3
3 3 2 1 2 3
MA M A
MA MA A M A
MA MA A M A
K
K K K
K K K K
=
= =
= =

Expressing every term in terms of [A] gives,
| | | | | | | |
| | | | | | | | ( )| |
{ }
| | | | | | | | | |
| | | | | | | | ( )| |
{ }
2
2
1 1 2 1 2
2
0
2
1 1 2 1 2
0
A MA 2 MA ... MA
A M A 2 A ... ... A
similarly,
M M MA MA ... MA
M M 1 A A ... ... A
n
b
n
n
b
n
n
n
n
K K K n K K K
K K K K K K
= + + +
= + + +
= + + + +
= + + + +

The average number of molecules of A bound per molecule M is then given by
| |
| |
| |
0
A
M
M
b
v
v
=
=
| | | | ( )| |
{ }
| |
2
1 1 2 1 2
A 2 A ... ... A
M
n
n
K K K n K K K + + +
| | | | ( )| |
{ }
| | | | ( )| |
| | | | ( )| |
2
1 1 2 1 2
2
1 1 2 1 2
2
1 1 2 1 2
1 A A ... ... A
A 2 A ... ... A
1 A A ... ... A
n
n
n
n
n
n
K K K K K K
K K K n K K K
v
K K K K K K
+ + + +
+ + +
=
+ + + +

4-147
*4.52. Now show that the Adair equation, derived in Problem 4.51, reduces to the equation obtained in Problem 4.50 when the sites are
equivalent and independent. [It is not correct simply to put K
1
=K
2
=K
3
=K
n
; certain statistical factors must be introduced.
Thus, if K
s
is the equilibrium constant for the binding at a given site, K
1
=nK
s
, since there are n ways for A to become attached to a
given molecule and one way for it to come off. Similarly K
2
=(n 1)K
s
/2; n 1 ways on and 2 ways off. Continue this argument
and develop an expression for v that will factorize into nK
s
[A]/(1 +K
s
[A]). Suggest a method of testing the equilibrium obtained
and arriving at a value of n from experimental data.]
Solution:
Given: Problems 4.50 and 4.51, information above
Required: prove that the Adair equation reduces to the equation in Problem 4.50
Using the above argument,
( )
( )
1
2
3
1
2
2
3
and therefore,
s
s
s
s
n
K nK
K
K n
K
K n
K
K
n
=
=
=
=

Substituting this into the Adair equation we get,
| | | | ( )| |
| | | | ( )| |
| | ( ) | | | |
| | ( ) | | | |
2
1 1 2 1 2
2
1 1 2 1 2
2
2
2
2
A 2 A ... ... A
1 A A ... ... A
A 1 A ... A
1 A 1 A ... A
n
n
n
n
n
n
s s s
n
n
s s s
K K K n K K K
v
K K K K K K
nK n n K nK
v
nK n n K K
+ + +
=
+ + + +
+ + +
=
+ + + +

The coefficients are the binomial coefficients and therefore the expression reduces to,
4-148
| | ( ) | | | |
( )
| | ( ) | | | |
| | | | ( )
| | ( )
| | | | ( )
1
1
2
2
1
A 1 1 A ... A
1 A 1 A ... A
A 1 A
1 A
A 1 A
n
n
s s s
n
n
s s s
n
s s
n
s
n
s s
nK n K K
v
nK n n K K
nK K
v
K
nK K
v
+ + +
=
+ + + +
+
=
+
+
=
| | ( ) | | ( )
1 A 1 A
n
s s
K K + +

| |
| |
A
which is the expression obtained in Problem 4.50.
1 A
s
s
nK
v
K
=
+

A method to test the equilibrium would be to plot
| |
1 1
against
A v
Rearranging the above equation gives,
| |
| |
| |
| |
| |
A
1 A
1 A 1
A
1 1
A
s
s
s
s
s
s
nK
v
K
K
v nK
K
v nK
=
+
+
=
= +
| | A
s
n K | | A
| |
1 1 1
A
s
v n nK
= +

One of the intercepts will be
1
n
.
4-149
Alternatively,
| |
canbe plotted against
A
v
v
| |
| |
| | | |
| | | |
| |
| |
A
1 A
A A
A A
A
A
s
s
s s
s s
s
s
nK
v
K
v vK nK
v nK vK
v
n v
K
v
v n
K
=
+
+ =
=
=
=

4-150
*4.53. Another special case of the equation derived in Problem 4.51 is if the binding on one site affects that on another. An extreme case is
highly cooperative binding, in which the binding of A on one site influences the other sites so that they fill up immediately. This
means that K
n
1
, K
2
, etc. Show that now:
[A]
1 [A]
n
n
nK
v
K
=
+

Where K is the product of K
1
, K
2
, K
n
. The British physiologist A. V. Hill suggested that binding problems can be treated by
plotting:
ln against ln[A]
1

Where is the fraction of sites that are occupied. Consider the significance of such Hill plots, especially their shapes and slopes,
with reference to the equations obtained in Problems 4.50 to 4.53.
Solution:
Given: above
Required: proof
If K
n
1
, K
2
, and so on, then the equation obtained in Problem 4.51 reduces to the following
| | | | ( )| |
| | | | ( )| |
( )| |
( )| |
| |
| |
2
1 1 2 1 2
2
1 1 2 1 2
1 2
1 2
A 2 A ... ... A
1 A A ... ... A
... A
1 ... A
A
1 A
n
n
n
n
n
n
n
n
n
n
K K K n K K K
v
K K K K K K
n K K K
v
K K K
nK
v
K
+ + +
=
+ + + +
=
+
=
+

Where
1 2
...
n
K K K K = is the overall equilibrium constant for the binding of n molecules, we then obtain
4-151
A M MA
K
n
n

+

The fraction of sites occupied,
| |
| |
| | ,
A
or A
1
1 A
n
n
n
K
K
K
= =
+

The slope of the plot of | | ln against A
1

is therefore n. If the sites are identical and independent (Problem 4.50), then the slope is 1.
Intermediate behaviour can give nonlinear plots; the maximum slope of a Hill plot cannot be greater than n.


CHAPTER
5
5
Phases and Solutions

Physical Chemistry
Electronic Edition

Chapter 5: Phases and Solutions Thermodynamics of Vapor Pressure
5-2
Chapter 5
Thermodynamics of Vapor Pressure
5.1. Diamonds have successfully been prepared by submitting graphite to high pressure. Calculate the approximate minimum pressure
needed using
f
G = 0 for graphite and
f
G =2.90 10
3
J mol
1
for diamond. The densities of the two forms may be taken as
independent of pressure and are 2.25 and 3.51 g cm
3
, respectively.
Solution
5.2. The molar entropy of vaporization of water is 108.72 J K
1
at 760 Torr. The corresponding densities of liquid water and water vapor
are 0.958 kg dm
3
and 5.98 10
4
kg dm
3
, respectively. Calculate the change of pressure for a one-degree change in temperature.
Solution
5.3. Calculate the heat of vaporization of water at 373.15 K and 101.325 kPa using the Clausius-Clapeyron equation. The vapor pressure
of water is 3.17 kPa at 298.15 K. Compare your answer to the CRC Handbook
1
value.
Solution
5.4. Liquid water and vapor are in equilibrium at the triple point of water (0.00603 atm and 273.16 K). Assuming that the enthalpy of
vaporization of water does not change over the temperature range considered, calculate the equilibrium vapor pressure of water at
373.15 K. Comment on the assumption made here. (
vap
H =40 656 J mol
1
at 1 atm.)
Solution
5.5. Estimate the vapor pressure of iodine under an external pressure of 101.3 10
6
Pa at 313.15 K. The density of iodine is 4.93 g cm
3
.
The vapor pressure at 101.3 kPa is 133 Pa.
Solution
5.6. The cubic expansion coefficient is given by =1/V (V/T)
P
. According to Ehrenfests or Tiszas theory, find the order of the
transition. Suggest what a plot of against T would look like near the transition point.
Solution

1
Handbook of Chemistry and Physics, 82nd ed., D. R. Lide, Ed., Boca Raton, FL: CRC Press, 2001.
5-3
5.7. The vapor pressure of n-propanol is 1.94 kPa at 293 K and 31.86 kPa at 343 K. What is the enthalpy of vaporization?
Solution
5.8. The compound 2-hydroxybiphenyl (o-phenylphenol) boils at 286 C under 101.325 kPa and at 145 C under a reduced pressure of
14 Torr. Calculate the value of the molar enthalpy of vaporization. Compare this value to that given in the CRC Handbook.
Solution
5.9. Using Troutons rule, estimate the molar enthalpy of vaporization of n-hexane, the normal boiling point of which is 342.10 K.
Compare the value obtained to the value 31.912 kJ mol
1
obtained in vapor pressure studies.
Solution
5.10. The normal boiling point of toluene is 110.62 C. Estimate its vapor pressure at 80.00 C assuming that toluene obeys Troutons
rule.
Solution
5.11. 2-Propanone (acetone) boils at 329.35 K at 1 atm of pressure. Estimate its boiling point at 98.5 kPa using Crafts rule.
Solution
5.12. The variation of the equilibrium vapor pressure with temperature for liquid and solid chlorine in the vicinity of the triple point is
given by
1
2661
ln 22.76,
3755
ln 26.88.
s
P
T
P
T
= +
= +

Use P/pascal in the equations. Calculate the triple point pressure and temperature.
Solution
5.13. The boiling point of water at 102.7 kPa is 373.52 K. Calculate the value at 101.325 kPa (1 atm) using Crafts rule.
Solution
5-4
5.14. The vapor pressure of water at 27.5 C, a calibration temperature for glassware used in warmer climates, is 27.536 Torr under its
own vapor pressure. Calculate the vapor pressure of water under an air pressure of 1.00 atm. Assume that air is inert. The density of
water at 27.5 C is 996.374 g dm
3
.
Solution
5.15. Following the derivation of the expression for S in terms of G in Eq. 3.161, derive an expression for V, the volume change
accompanying a transition from one state to another, in terms of G starting with the definition given in Eq. 3.115.
Solution
5.16. Derive an equation for the temperature dependence of the vapor pressure of a liquid (analogous to the integrated form of the
Clausius-Clapeyron equation) assuming that the vapor has the equation of state PV =RT +M where M is a constant.
Solution
5.17. Calculate the vapor pressure above liquid ethanol at 35.0 C when Ar is added until the total pressure is 100 bar. The density of
liquid ethanol at this temperature is 0.7767 kg dm
3
and the true vapor pressure is 100.0 Torr.
Solution
5.18. A solid exists in two forms, A and B, whose densities are 3.5155 g cm
3
and 2.2670g cm
3
, respectively. If the standard Gibbs
energy change for the reaction A B is 240 kJ kg
1
, find the pressure at which the two forms of the solid are in equilibrium at 25
C. Assume that the volume change in going from A to B is independent of the pressure.
Solution
5.19. What are the partial pressures of toluene (0.60 mole fraction) and benzene (mole fraction) in a solution at 60 C? What is the total
pressure in the vapor? The vapor pressures of the pure substances at 60 C are as follows: toluene, 0.185 bar; benzene, 0.513 bar.
Solution
5.20. The normal boiling point of ethylene glycol (C
2
H
6
O
2
) is 197 C; its enthalpy of vaporization is 801 J mol
1
. Estimate the
temperature at which ethylene glycol will boil in a vacuum distillation if the system were maintained at 50 Torr.
Solution
Chapter 5: Phases and Solutions Raoults Law, Equivalence of Units, and Partial Molar Quantities
5-5
Raoults Law, Equivalence of Units, and Partial Molar Quantities
5.21. Benzene and toluene form nearly ideal solutions. If, at 300 K, P* (toluene) =3.572 kPa and P* (benzene) =9.657 kPa, compute the
vapor pressure of a solution containing 0.60 mol fraction of toluene. What is the mole fraction of toluene in the vapor over this
liquid?
Solution
5.22. Often it is important to express one unit of concentration in terms of another. Derive a general expression to find the mole fraction
x
2
in a two-component system where the molality is given as m
2
.
Solution
5.23. Assuming that commercially available automotive antifreeze is pure ethylene glycol (it actually also contains relatively small
amounts of added rust inhibitors and a fluorescent dye that helps to differentiate a radiator leak from condensation from the air
conditioner), in what ratio by volume will antifreeze and water have to be mixed in order to have a solution that freezes at 20.0 C?
What will be the boiling point of this solution at 1 atm pressure? (MW =62.02 g mol
1
, density =1.1088 g cm
3
.)
Solution
*5.24. The familiar term molarity is now discouraged by IUPAC because of the danger of confusion with molality. In its place,
concentration is defined as the amount of substance 2, n
2
, dissolved in unit volume of solution. Derive a general relation to find x
2

from the concentration c
2
. Let the solution density be .
Solution
5.25. Show that if a solute follows Henrys law in the form of P
2
=kx
2
, then the solvent must follow Raoults law. (Hint: The use of the
Gibbs-Duhem equation might prove useful.)
Solution
5.26. A 1.0 m solution of NaCl in water produces a freezing point depression of approximately 3.7 K. How can we account for this
observation?
Solution
5.27. Derive a general expression to relate the molality m to concentration c
2
.

Solution
5-6
5.28. An amalgam of 1.152 g of a metal dissolved in 100.0 g of mercury is heated to boiling. The partial pressure of mercury vapor over
the boiling mixture is 754.1 Torr and the total pressure is 768.8 Torr. Find the atomic weight of the metal and, therefore, its identity.
Solution
*5.29. The volume of a solution of NaCl in water is given by the expression
V/cm
3
=1002.874 +17.8213 m +0.873 91 m
2
0.047 225 m
3
where m is the molality. Assume that m n
NaCl
and that
2
H O
n =55.508 mol, where
2
*
H O
V =18.068 cm
3
. Derive an analytical
expression for the partial molar volume of H
2
O in the solution.
Solution
*5.30. The partial molar volume of component 2 in a solution may be written as
1
1
2
2
2
1 1 2 2 2
2
1
( )
n
n
V
V
n
M
M n M n
n

| |
=
|
\ .
| |
= +
|
\ .

where n
1
and M
1
are amount and molar mass of component 1 and n
2
and M
2
represent the same quantities for component 2. The
density is . Rewrite the expression in terms of the mole fractions x
1
and x
2
.
Solution
*5.31. Mikhail and Kimel, J. Chem. Eng. Data, 6, 533(1961), give the density of a water-methanol solution in g cm
3
at 298 K related to
the mole fraction x
2
of the methanol through the equation
3 2
2 2
3 4 5
2 2 2
/gcm 0.9971 0.28930 0.29907
0.60876 0.59438 0.20581
x x
x x x
= +
+

Using the equation developed in Problem 5.30, calculate V
2
at 298 K when x
2
=0.100.
Solution
5-7
5.32. Beckmann and Faust [Z. Physik. Chemie, 89, 235(1915)] found that a solution of chloroform in acetone in which the mole fraction
of the latter is 0.713 has a total vapor pressure of 220.5 Torr at 28.15 C. The mole fraction of acetone in the vapor is 0.818. The
vapor pressure of pure chloroform at this temperature is 221.8 Torr. Assuming that the vapor behaves ideally, calculate the activity
and the activity coefficient of chloroform.
Solution
5.33. When 12.5 g of A, a nonvolatile compound, is dissolved in 520.8 g of ethanol, the vapor pressure of the pure solvent, 56.18 Torr, is
reduced to 55.24 Torr. Calculate the molar mass of compound A.
Solution
5.34. The following data are for mixtures of isopropanol (I) in benzene (B) at 25 C.
x
I
0 0.059 0.146 0.362
P
I
(Torr) 0 12.9 22.4 27.6
P
tot
94.4 104.5 109.0 108.4
0.521 0.700 0.836 0.924 1.0
30.5 36.4 39.5 42.2 44.0
105.8 99.8 84.0 66.4 44.0

Does this solution exhibit positive or negative deviation fromRaoults law? Froma pressure-composition plot, estimate the activities a
I

and a
B
and activity coefficients f
I
and f
B
at x
I
=0.20, 0.50, and 0.80. [Data fromOlsen and Washburn, J. Phys. Chem., 41, 457(1937).]
Solution
Chapter 5: Phases and Solutions Thermodynamics of Solutions
5-8
5.35. The vapor pressure of pure ethylene dibromide is 172 Torr and that of pure propylene dibromide is 128 Torr both at 358 K and 1
atm pressure. If these two components follow Raoults law, estimate the total vapor pressure in kPa and the vapor composition in
equilibrium with a solution that is 0.600 mol fraction propylene dibromide.
Solution
5.36. Calculate Henrys law constant and the vapor pressure of pure liquid A (molar mass =89.5 g mol
1
) and that of 75.0 g of liquid A in
solution with 1000 g of liquid B. Liquid B (molar mass =185 g mol
1
) has a pressure in this solution of 430 Torr and the total
solution pressure is 520 Torr.
Solution
*5.37. Henrys law constants k for N
2
and O
2
in water at 20.0 C and 1 atm pressure are 7.58 10
4
atm and 3.88 10
4
atm, respectively.
If the density of water at 20.0 C is 0.9982 g cm
3
, calculate (a) the equilibrium mole fraction and (b) the concentration of N
2
and O
2

in water exposed to air at 20.0 C and 1 atm total pressure. Assume in this case that air is 80.0 mol % N
2
and 20.0 mol % O
2
.
Solution
5.38. Methane dissolves in benzene with a Henrys law constant of 4.27 10
5
Torr. Calculate methanes molal solubility in benzene at 25
C if the pressure above benzene is 750 Torr. The vapor pressure of benzene is 94.6 Torr at 25 C.
Solution
Thermodynamics of Solutions
5.39. In a molar mass determination, 18.04 g of the sugar mannitol was dissolved in 100.0 g of water. The vapor pressure of the solution
at 298 K was 2.291 kPa, having been lowered by 0.0410 kPa from the value for pure water. Calculate the molar mass of mannitol.
Solution
5.40. A liquid has a vapor pressure of 40.00 kPa at 298.15 K. When 0.080 kg of an involatile solute is dissolved in 1 mol of the liquid, the
new vapor pressure is 26.66 kPa. What is the molar mass of the solute? Assume that the solution is ideal.
Solution
*5.41. Components 1 and 2 form an ideal solution. The pressure of pure component 1 is 13.3 kPa at 298 K, and the corresponding vapor
pressure of component 2 is approximately zero. If the addition of 1.00 g of component 2 to 10.00 g of component 1 reduces the total
vapor pressure to 12.6 kPa, find the ratio of the molar mass of component 2 to that of component 1.
Solution
Chapter 5: Phases and Solutions Thermodynamics of Solutions
5-9
5.42. Pure naphthalene has a melting point of 353.35 K. Estimate the purity of a sample of naphthalene in mol %, if its freezing point is
351.85 K (K
f
=7.0 K kg mol
1
).
Solution
5.43. Calculate the activity and activity coefficients for 0.330 mol fraction toluene in benzene. The vapor pressure of pure benzene is
9.657 kPa at 298 K.
*
2
P =3.572 kPa for toluene. The vapor pressure for benzene above the solution is P
1
=6.677 kPa and for
toluene P
2
=1.214 kPa.
Solution
5.44. Calculate the mole fraction, activity, and activity coefficients for water when 11.5 g NaCl are dissolved in 100 g water at 298 K. The
vapor pressure is 95.325 kPa.
Solution
5.45. Determine the range for the Gibbs energy of mixing for an ideal 50/50 mixture at 300 K. How does this value limit
mix
H?

Solution
5.46. The mole fraction of a nonvolatile solute dissolved in water is 0.010. If the vapor pressure of pure water at 293 K is 2.339 kPa and
that of the solution is 2.269 kPa, calculate the activity and activity coefficient of water.
Solution
*5.47. A nonideal solution contains n
A
of substance A and n
B
of substance B and the mole fractions of A and B are x
A
and x
B
. The Gibbs
energy of the solution is given by the equation
o o
A A B B A A B B
A B A B
( ln ln )
/( )
G n n RT n x n x
Cn n n n
= + + +
+ +

where C is a constant and describes the pair interaction.
a. Derive an equation for
A
in the solution in terms of the quantities on the right-hand side. {Hint:
B
A A A A B
( ln / ) (1/ )[1/( )].
n
x n n n n = + }
b. Derive a similar expression for the activity coefficient of A. Specify the conditions when the activity coefficient equals unity.
Solution
Chapter 5: Phases and Solutions Colligative Properties
5-10
Colligative Properties
5.48. Calculate the mole fraction solubility of naphthalene at 25 C in a liquid with which it forms an ideal solution. The
fus
H =19.0 kJ
mol
1
for naphthalene at 25 C. Its normal melting point is 80.2 C.
Solution
5.49. Using Henrys law, determine the difference between the freezing point of pure water and water saturated with air at 1 atm. For N
2

at 298.15 K,
(k)
1
=2.17 10
8
mol dm
3
Pa
1

For O
2
at 298.15 K,
(k)
1
=1.02 10
8
mol dm
3
Pa
1

Solution
5.50. Using vant Hoffs equation, calculate the osmotic pressure developed if 6.00 g of urea, (NH
2
)
2
CO, is dissolved in 1.00 dm
3
of
solution at 27 C.
Solution
5.51. The apparent value of K
f
in 1.50-molal aqueous sucrose (C
12
H
22
O
11
) solution is 2.17 K kg mol
1
. The solution does not behave
ideally; calculate its activity and activity coefficient (
fus
H =6009.5 J mol
1
).
Solution
5.52. A 0.85-g sample is dissolved in 0.150 kg of bromobenzene. Determine the molar mass of the solute if the solution boils at 429.0 K at
1 atm pressure. The normal boiling point of bromobenzene is 428.1 K and the boiling point elevation constant is 6.26 K kg mol
1
.
Solution
*5.53. If in a colligative properties experiment a solute dissociates, a term i known as vant Hoffs factor, which is the total concentration
of ions divided by the nominal concentration, must be included as a factor. Thus, for the lowering of the freezing point,
fus
T =
imK
f
. Derive an expression that relates to the degree of dissociation and to , the number of particles that would be produced if the
solute were completely dissociated. Then calculate vant Hoffs i factor and for a 0.010-m solution of HCl that freezes at 273.114
K.
Solution
Chapter 5: Phases and Solutions Essay Questions
5-11
5.54. In an osmotic pressure experiment to determine the molar mass of a sugar, the following data were taken at 20 C:
/atm 2.59 5.06 7.61 12.75 18.13 23.72
m
2
V
1
/g dm
3
33.5 65.7 96.5 155 209 259

Estimate the molar mass of the sugar. If the sugar is sucrose, what is the percentage error and why?
Solution
5.55. When 3.78 g of a nonvolatile solute is dissolved in 300.0 g of water, the freezing point depression is 0.646 C. Calculate the molar
mass of the compound. K
f
=1.856 K kg mol
1
.
Solution
5.56. Calculate the elevation in the boiling point of water if 6.09 g of a nonvolatile compound with molar mass of 187.4 g mol
1
is
dissolved in 250.0 g of water. Compare the values obtained using Eq. 5.125 and Eq. 5.126. The value of K
b
=0.541 K kg mol
1
;
vap
H =40.66 kJ mol
1
.
Solution
5.57. Suppose that you find in the older literature the vapor pressure P of a liquid with molar mass of 63.9 10
3
kg mol
1
listed with P in
mmHg as
log P =5.4672 1427.3 T
1
3169.3 T
2

The densities of the liquid and vapor phases are 0.819 kg dm
3
and 3.15 10
4
kg dm
3
, respectively. Calculate the
vap
H at the
normal boiling point, 398.4 K. How do you handle the fact that P is listed in mmHg?
Solution
5.58. Calculate the osmotic pressure of seawater using the data of Table 5.5. Assume a temperature of 298 K and that the concentration of
the additional salts not listed does not substantially contribute to the osmotic pressure.
Solution
Essay Questions
5.59. Describe the form of a typical P diagram and how the Gibbs-energy diagram may be generated for a one-component system. What
is the requirement of stability for each region in the P diagram?
Chapter 5: Phases and Solutions Essay Questions
5-12
5.60. Detail the steps in going from the Clapeyron equation to the Clausius-Clapeyron equation. What specific assumptions are made?
5.61. Explain why Troutons rule, according to which the entropy of vaporization is 88 J K
1
mol
1
, holds fairly closely for normal liquids.
5.62. Describe three colligative properties and comment on their relative merits for the determination of molar masses of proteins.
5.63. Show mathematically how the chemical potential is the driving force of diffusion for component A between two phases and .
5.64. Why do positive and negative deviations from Raoults law occur?
Chapter 5: Phases and Solutions Solutions
5-13
Solutions
5.1. Diamonds have successfully been prepared by submitting graphite to high pressure. Calculate the approximate minimum pressure
needed using
f
G =0 for graphite and
f
G =2.90 10
3
J mol
1
for diamond. The densities of the two forms may be taken as
independent of pressure and are 2.25 and 3.51 g cm
3
, respectively.
Solution:
Given:
3 1 3 3
graphite diamond
0, 2.90 10 J mol , 2.25 g cm , 3.51 g cm
f f
G G = = = =
Required: P
diamond
The equilibrium presented in this problem is given by,
graphite diamond
C C
Using equation 3.119 we can obtain V and further solve to obtain P.
, hence
T T
G G
V V
P P
| | | |
= =
| |

\ . \ .

V can be obtained using the densities given in the problem.
n
V
n
V
=
=

To convert from molar volume, we multiply by the molar mass of carbon.
5-14
graphite diamond
, let 1 mol
1 1
12.011 g
n
V M n
V Mn
V

= =
| |
= |
|
\ .
=
1
mol
( )
1 mol
( )
1
2.25 g
3
1
cm 3.51 g
3
3
cm
1.916 285 cm V
| |
|
|
\ .
=
3
6
3
m
10
cm
6 3
1.916 285 10 m V

=

Using equation 3.119 we obtain,
T
G
V
P
| |
=
|
\ .

( )
( )
2 2
1 1
2 1 2 1
2 1
2 1
2 1
2 1
2
3 1
2 1 6 3

,
0 at equilibrium
0 2.90 10 J mol
1.916 285 10 m
G V P
G G V P P
G G
P P
V
G G
P P
V
G
P P
=
=

=

= +
=

= +

Under standard conditions, we use P
1
as 10
5
Pa.
5-15
3 1
5
2 6 3
2
9 4
2
0 2.90 10 J mol
10 Pa
1.916 285 10 m
1 513 444 831 Pa
1.51 10 Pa 1.51 10 bar
P
P
P

= +
=
= =

5-16
5.2. The molar entropy of vaporization of water is 108.72 J K
1
at 760 Torr. The corresponding densities of liquid water and water vapor
are 0.958 kg dm
3
and 5.98 10
4
kg dm
3
, respectively. Calculate the change of pressure for a one-degree change in temperature.
Solution:
Given:
1 3 4 3
liquid vapor
108.72 J K , 760 Torr, 0.958 kg dm , 5.98 10 kg dm , S P

= = = =
1 C 1 K T = =
Required: P
To solve this problem we can use Eq. 5.8 which defines the change in pressure over time.
(v) (l)
(v) (l)
m m m
m m m
S S S dP
dT V V V

= =

This can also be rewritten as,
vaporization
v l
S
dP P
dT T V V
= =

To solve for P, we first need to obtain the values of V
v
and V
l
. These can be determined by using the densities given in the problem.
n
V
n
V
=
=

To convert from molar volume, we multiply by the molar mass of water.
5-17
3
, let 1 mol
2 1.007 94 10 kg
l
n
V M n
V
= =
=
1
mol
( )
3
15.9994 10 kg
+
1
mol
( ) ( )
1 mol
0.958 kg
3
2 3
3
dm
18.805 10 dm
2 1.007 94 10 kg
l
v
V
V
| |
|
|
\ .
=
=
1
mol
( )
3
15.9994 10 kg
+
1
mol
( ) ( )
1 mol
4
5.98 10 kg
3
3
dm
30.126 dm
v
V
| |
|
|
\ .
=

Rearranging Eq. 5.8 we can solve for P which yields:
vaporization
1
108.72 J K
v l
S
P T
V V
P
=
3 2 3
1 K
30.126 dm 18.805 10 dm

( )
3 3 3
3.6111 10 m dm P

=
( )
3
J dm
( )
3 3
2 2 1 2
3 2 2 3
3 1 2
3
3.6111 10 J m
where 1 J 1 kg m s and 1 Pa 1 kg m s
3.6111 10 kg m s m
3.6111 10 kg m s
3.61 10 Pa
P
P
P
P

=
= =
=
=
=

5-18
5.3. Calculate the heat of vaporization of water at 373.15 K and 101.325 kPa using the Clausius-Clapeyron equation. The vapor pressure
of water is 3.17 kPa at 298.15 K. Compare your answer to the CRC Handbook
2
value.
Solution:
Given: 373.15 K, 101.325 kPa, 3.17 kPa at 298.15 K
vap
T P P T = = = =
Required:
vap m
H
The Clausius-Clapeyron equation is given by Eq. 5.16,
vap
2
1 1 2
1 1
ln
m
H
P
P R T T
| |
=
|
\ .

Rearranging and solving for
vap m
H gives,
2 2 1
1 2 1
2 2 1
1 2 1
1
ln
ln
8.3145 J K
vap m
vap m
vap m
H
P T T
P R T T
P T T
H R
P T T
H

| |
=
|
\ .
| |
=
|
\ .
=
( )
1
101.325 kPa
mol ln
3.17 kPa
373.15 K
| |
|
\ .
( )
298.15 K
( )
373.15 K 298.15 K
1
1
42 731.332 J mol
42.7 kJ mol
vap m
vap m
H
H
| |
|
|
\ .
=
=

The CRC Handbook value is
1
40.57 kJ mol
.

2
Handbook of Chemistry and Physics, 82nd ed., D. R. Lide, Ed., Boca Raton, FL: CRC Press, 2001.
5-19
5.4. Liquid water and vapor are in equilibrium at the triple point of water (0.00603 atm and 273.16 K). Assuming that the enthalpy of
vaporization of water does not change over the temperature range considered, calculate the equilibrium vapor pressure of water at
373.15 K. Comment on the assumption made here. (
vap
H =40 656 J mol
1
at 1 atm.)
Solution:
Given:
1
triple triple
0.00603 atm, 273.16 K, 40 656 J mol at 1 atm
vap
P T H = = =
Required:
vap
at 373.15 K P T =
The equilibrium presented in this problem is given by,
2 2
H O(l) H O(g)
The Clausius-Clapeyron equation is given by Eq. 5.16,
vap
2
1 1 2
1 1
ln
m
H
P
P R T T
| |
=
|
\ .

Rearranging and solving for P
vap
gives,
( )
vap
1 2
1 2
vap
2
1 1 2
1 1
2
1
1 1
vap triple
40 656 J
vap
1 1
ln
0.00603 atm
m
vap m
m
H
R T T
H
R T T
H
P
P R T T
P
e
P
P P e
P e
| |
|
\ .
| |
|
\ .
| |
=
|
\ .
=
=
=
1
mol
8.3145 J
1
K
1
mol
1
273.16 K
1
373.15 K
( )
4.796 721 772
vap
vap
vap
0.00603 atm
0.730 309 767 atm
0.730 atm
P e
P
P
| |
|
\ .
=
=
=

5-20
5.5. Estimate the vapor pressure of iodine under an external pressure of 101.3 10
6
Pa at 313.15 K. The density of iodine is 4.93 g cm
3
.
The vapor pressure at 101.3 kPa is 133 Pa.
Solution:
Given:
3
vap
313.15 K, 4.93 g cm , 101.3 kPa, 133 Pa
ext
T P P = = = =
Required:
6
vap ext
at 101.3 10 Pa P P =
Since the vapor pressure varies with external pressure, we use Eq. 5.23 to solve this problem.
( )
ln ( )
t m
t v
v
P V l
P P
P RT
=
This can be rewritten as,
1
1 2
2
( )
ln ( )
g
m
g
V l P
P P
P RT
=
To obtain V
m
we use the density given in the problem.
n
V
n
V
=
=

To convert from molar volume, we need to multiply by the molar mass of water.
5-21
, let 1 mol
2 126.904 47 g
m
n
V M n
V
= =
=
1
mol
( ) ( )
1 mol
4.93 g
3
3
cm
51.482 543 61 cm
m
V
| |
|
|
\ .
=
3
6
3
m
10
cm
5 3
5.148 254 361 10 m
m
V

=

From Eq. 5.23 we can solve for P
vap
5 3
1
2
5.148 254 361 10 m
ln
g
g
P
P
=
8.3145 J
1
K
( )
1
mol 313.15 K
( )
6
101.3 10 Pa
3
101.3 10 Pa
( )

2.000 996716 1
2
1
2
7.396 424 563
g
g
g
g
P
e
P
P
P
=
=

At 101.3 kPa, the pressure is 133 Pa. Therefore at 101.310
3
kPa the vapor pressure is 7.396 424 563 133 Pa
vap
vap
vap
7.396 424 563 133 Pa
983.724 467 Pa
984 Pa
P
P
P
=
=
=

5-22
5.6. The cubic expansion coefficient is given by =1/V (V/T)
P
. According to Ehrenfests or Tiszas theory, find the order of the
transition. Suggest what a plot of against T would look like near the transition point.
Solution:
The cubic expansion coefficient is a second order transition since it can be expressed as
1

T
P
G
V T P
( | |
=
( |

\ .

5-23
5.7. The vapor pressure of n-propanol is 1.94 kPa at 293 K and 31.86 kPa at 343 K. What is the enthalpy of vaporization?
Solution:
Given:
1 1 2 2
1.94 kPa, 293 K, 31.86 kPa, 343 K P T P T = = = =
Required:
vap m
H
To obtain the enthalpy of vaporization, we must use the Clausius-Clapeyron equation, in the form of Eq. 5.16:
vap
2
1 1 2
1 1
ln
m
H
P
P R T T
| |
=
|
\ .

Rearranging, we can solve for
vap m
H ,
( )( )
( )
vap
2 2 1
1 1 2
1 2 2
vap
2 1 1
1 1
vap
ln
ln
293 K 343 K 31.86 kPa
8.3145J K mol ln
343 K 293 K
m
m
m
H
P T T
P R TT
TT P
H R
T T P
H

| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
1.94 kPa
1
vap
1
vap
46 771.20201 J mol
46.8 kJ mol
m
m
H
H
| |
|
\ .
=
=

5-24
5.8. The compound 2-hydroxybiphenyl (o-phenylphenol) boils at 286 C under 101.325 kPa and at 145 C under a reduced pressure of
14 Torr. Calculate the value of the molar enthalpy of vaporization. Compare this value to that given in the CRC Handbook.
Solution:
Given:
1 1 2 2
286 C 559.15 K, 101.325 kPa, 145 C 418.15 K, 14 Torr T P T P = = = = = =
Required:
vap m
H
To obtain the enthalpy of vaporization, we must use the Clausius-Clapeyron equation, in the form of Eq. 5.16:
vap
2
1 1 2
1 1
ln
m
H
P
P R T T
| |
=
|
\ .

vap m
H ,
( )( )
( )
vap
2 2 1
1 1 2
1 2 2
vap
2 1 1
1 1
vap
ln
ln
559.15 K 418.15 K
8.3145J K mol
418.15 K 559.15 K
14 Torr
ln
m
m
m
H
P T T
P R TT
TT P
H R
T T P
H

| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
760 Torr
1
atm
101 325 Pa
1
atm
1
101 325 Pa
1
vap
1
vap

55 069.85164 J mol
55 kJ mol
m
m
H
H
| |
|
|
\ .
=
=

The value for
vap m
H in the CRC Handbook is 71.02 kJ mol
-1
. The error is large, but considering the relative molecular mass of the
compound, its high boiling point, and the wide range of T and P involved in the calculation, it is not surprising that the error is so large.
5-25
5.9. Using Troutons rule, estimate the molar enthalpy of vaporization of n-hexane, the normal boiling point of which is 342.10 K.
Compare the value obtained to the value 31.912 kJ mol
1
obtained in vapor pressure studies.
Solution:
Given:
1
vap
342.10 K, 31.912 kJ mol
m
T H

= =
Required:
vap m
H
Troutons rule is given by Eq. 5.18:
vap 1 1
vap
88J K mol
m
m
b
H
S
T
=
vap m
H ,
1
vap
110.62 C 383.77 K, 31.912 kJ mol
m
T H

= = =
We can compare this value with the value obtained in vapor pressure studies by calculating the percent error.
3 1 1
3 1
31.912 10 J mol 30104.8 J mol
% error 100%
31.912 10 J mol
% error 5.663 073%
% error 5.6631%
=
=

5-26
5.10. The normal boiling point of toluene is 110.62 C. Estimate its vapor pressure at 80.00 C assuming that toluene obeys Troutons
rule.
Solution:
Given: 110.62 C 383.77 K, 80.00 C 353.15 K
B
T T = = = =
Required: P
vap

Troutons rule is given by Eq. 5.18:
vap 1 1
vap
88J K mol
m
m
b
H
S
T
=
vap m
H at T
B
=110.62 C,
( )
1 1
vap
1
vap
88J K mol
88J K
m B
m
H T
H
=
=
( )
1
mol 383.77 K
( )
1
vap
33771.76 J mol
m
H =

Using this value for
vap m
H , we can obtain P
vap
from Eq. 5.16 the Clausius-Clapeyron equation. This can then be rearranged to obtain,
vap
1 2
vap
2
1 1 2
1 1
2 1
1 1
ln
m
m
H
R T T
H
P
P R T T
P Pe
| |
|
\ .
| |
=
|
\ .
=

Where P
1
=1 atm under standard conditions.
5-27
( )
33771.76 J
2
1 atm P e =
1
mol
8.3145 J
1 1
K mol

( )
1 1
383.77 K 353.15 K
2
2
0.399 444 atm
0.3994 atm
P
P
| |
|
\ .
=
=

5-28
5.11. 2-Propanone (acetone) boils at 329.35 K at 1 atm of pressure. Estimate its boiling point at 98.5 kPa using Crafts rule.
Solution:
Given: 329.35 K, 1 atm 101.325 kPa, 98.5 kPa
B
T P P = = = =
Required: T
Crafts rule is given by Eq. 5.19,
vap m
B B
H
P P
T T RT

First we can solve for T then we will be able to obtain T.
vap
329.35 K
B B
m
RT T
T P
P H
T
| |
| |
= |
|
|
\ .
\ .
=
( )
8.3145 J
1
K
( )
1
3
mol
98.5 10 Pa
1
88 J
| |
|
|
|
\ .
1 1
K mol

98 500 Pa
| |
|
|
\ .
101 325 Pa
( )
0.892469 K T =

T is given by,
329.35 K 0.892469 K
328.457 531 K
328 K
T
T
T
=
=
=

5-29
5.12. The variation of the equilibrium vapor pressure with temperature for liquid and solid chlorine in the vicinity of the triple point is
given by
2661
ln 22.76,
3755
ln 26.88.
l
s
P
T
P
T
= +
= +

Use P/pascal in the equations. Calculate the triple point pressure and temperature.
Solution:
Given:
Required: P
triple
, T
triple

At the triple point, the two vapor pressures must be equal since the liquid, solid, and vapor are all in equilibrium with each other. Therefore
we can say that,
triple triple
2661 3755
22.76 26.88
T T
+ = +
Solving the above expression for T
triple
we obtain;
triple triple
triple triple
triple
triple
triple
2661 3755
22.76 26.88
2661 3755
4.12
2661 3775 4.12
270.388 3495K
270.4K
T T
T T
T
T
T

+ = +
+ =
+ =
=
=

To obtain P
triple
, we use the value for T
triple
and one of the equations given in the problem. Both will give the same answer.
5-30
triple
2661
22.76
270.388 3495K
triple
triple
2661
ln 22.76
270.388 3495K
407 827.529 Pa
P
P e
P
= +
=
=

Similarly,
triple
triple
triple
3755
ln 26.88
270.388 3495K
407 827.529 Pa
407.8 kPa
P
P
P
= +
=
=

5-31
5.13. The boiling point of water at 102.7 kPa is 373.52 K. Calculate the value at 101.325 kPa (1 atm) using Crafts rule.
Solution:
Given: 102.7 kPa, 373.52 K, , 101.325 kPa
B
P T P = = =
Required: T
Crafts rule is given by Eq. 5.19:
vap m
B B
H
P P
T T RT

First we can solve for T which will then enable us to determine the value of T.
vap
373.52 K
B B
m
RT T
T P
P H
T
| |
| |
= |
|
|
\ .
\ .
=
( )
8.3145 J
1
K
( )
1
3
mol
102.7 10 Pa
1
88 J
| |
|
|
|
\ .
1 1
K mol

101 325Pa
| |
|
|
\ .
3
102.7 10 Pa
( )
0.472498 K T =

T is given by,
373.52 K 0.472498 K
373.047 502 K
373.05 K
T
T
T
=
=
=

5-32
5.14. The vapor pressure of water at 27.5 C, a calibration temperature for glassware used in warmer climates, is 27.536 Torr under its
own vapor pressure. Calculate the vapor pressure of water under an air pressure of 1.00 atm. Assume that air is inert. The density of
water at 27.5 C is 996.374 g dm
3
.
Solution:
Given:
3
27.5 C 300.65 K, 27.536 Torr, 1.00 atm, 996.374 g dm T P P

= = = = =
Required: P
vap

To calculate P
vap
we may use Eq. 5.23 which states that:
(l)
ln ( )
m
t v
v
V P
P P
P RT
=
Rearranging this expression to isolate for the vapour pressure gives,
(l)
( )
vap
where
2 1.007 94 g

m
t v
V
P P
RT
v
m
m
P Pe
M
V
V
=
=
=
( )
1
mol 15.9994 g
+
( ) ( )
1
mol
996.374 g
( )
3
3
3 1
0.018 0808411 dm

vap
dm
0.018 080841 1 dm mol
27.536 Torr
m
V
P e
=
=
1
mol
0.082 06 atm
3
dm
1
K
1
mol 760 Torr
1
atm
300.65 K ( ) ( )
760 Torr 27.536 Torr ( )
( )
4
7.063152747 10
vap
vap
vap
27.536 Torr
27.555 455 97 Torr
27.555 Torr
P e
P
P
=
=
=

This is a small correction, but may be necessary for accurate work.
5-33
5.15. Following the derivation of the expression for S in terms of G in Eq. 3.161, derive an expression for V, the volume change
accompanying a transition from one state to another, in terms of G starting with the definition given in Eq. 3.115.
Solution:
Given: Eq. 3.161, Eq. 3.115
Required: an expression for V
Eq. 3.115 is given by the following expression:
T P
G G
dG V dP S dT dP dT
P T
| | | |
= = +
| |
\ . \ .

Recognize that a change of state occurs at constant temperature. Therefore, differentiating Eq. 3.115 with respect to P at constant
temperature, we obtain the following from Eq. 3.119.
T
G
V
P
| |
=
|
\ .

Now for a change of state, where
f i
G G G = , there will be a corresponding change in volume,
T
G
V
P
| |
=
|
\ .

5-34
5.16. Derive an equation for the temperature dependence of the vapor pressure of a liquid (analogous to the integrated form of the
Clausius-Clapeyron equation) assuming that the vapor has the equation of state PV =RT +M where M is a constant.
Solution:
Given: PV =RT +M where M is a constant
Required: expression for temperature dependence of the vapor pressure of a liquid
The general Clausius-Clapeyron equation, is given by Eq. 5.9 which states that:
m
m
H dP
dT T V

Rearranging the equation of state for vapor and substituting gives,
( )
( )
vap
vap
vap
m
m
m
PV RT M
RT M
V
P
H
dP
RT M dT
T
P
H P
dP
dT T RT M
H dT
dP
P T RT M
= +
+
=
=
+ | |
|
\ .
=
+
=
+

Expanding the denominator yields,
( ) ( )
1 1 R
T RT M MT M RT M
=
+ +

Therefore we obtain,
5-35
( )
( )
vap
vap vap
1
m
m m
dP R
H dT
P MT M RT M
H dT H dT
dP R
P MT M RT M
| |
=
|
|
+
\ .

=
+

Integrating the above expression, and cancelling terms as necessary, gives,
vap
2 2
1 1
ln ln
m
H
P T R
P M T
=
vap m
H
M R
2
1
vap
2 2 1
1 1 2
ln
ln ln
m
RT M
RT M
H
P T RT M
P M T RT M
+
+
| | +
=
|
+
\ .


5-36
5.17. Calculate the vapor pressure above liquid ethanol at 35.0 C when Ar is added until the total pressure is 100 bar. The density of
liquid ethanol at this temperature is 0.7767 kg dm
3
and the true vapor pressure is 100.0 Torr.
Solution:
Given: Ethanol, C
2
H
5
OH,
3
total true
100 bar, 0.7767 kg dm , 100.0 Torr P P = = =
Required:
vap ext
at 35 C 308.15 K P T = =
To calculate P
vap
we must use Eq. 5.23 which states that:
(l)
ln ( )
m
t v
v
V P
P P
P RT
=
Rearranging the above to isolate for the vapor pressure yields;
(l)
( )
vap
where
2 12.011g

m
t v
V
P P
RT
v
m
m
P Pe
M
V
V
=
=
=
( )
1
mol 6 1.007 94 g
+
( )
1
mol 15.9994 g
+
( ) ( )
1
mol
776.7 g
3
3
dm
0.059 313814 9 dm
m
V =
3
1 3
3
m
mol 10
dm

( )
5 3
5 3 1
5.93138149 10 m

vap

5.931 381 49 10 m mol
100 Torr
m
V
P e
=
=
1
mol
1
8.3145 J K
1
mol 308.15 K ( ) ( )
5
10 Pa
100bar
1 bar
100 Torr
101325Pa
760 Torr
( )
0.231 1948469
vap
vap
vap
100 Torr
126.010 474 3 Torr
126 Torr
P e
P
P
| |
|
|
\ .
=
=
=

5-37
5.18. A solid exists in two forms, A and B, whose densities are 3.5155 g cm
3
and 2.2670 g cm
3
, respectively. If the standard Gibbs
energy change for the reaction A B is 240 kJ kg
1
, find the pressure at which the two forms of the solid are in equilibrium at 25
C. Assume that the volume change in going from A to B is independent of the pressure.
Solution:
Given:
3 3 1
A B
3.5155 g cm , 2.2670 g cm , 240 kJ kg , 25 C 298.15 K G T = = = = =
Required: P at equilibrium
We can use the result obtained in problem 5.15 to solve this problem.
T
G
V
P
| |
=
|
\ .

The change in volume can be calculated from the densities given above.
3 3
1
1
1 1
3.5155 g cm 2.2670 g cm
0.156 657 042 9 g
V
V
V
| |
=
|
\ .
=
3
cm
3 1
3
3
m kg
10
cm
1
g
3 3 1
0.156 657 042 9 10 m kg V

=

Solving for P we obtain;
( )
2
1
2
1
2 1 2 1
P
P
d G VdP
G G V P P
=
=

Let state 1 be the standard state, and state 2 be the equilibrium state. At equilibrium, G=0, therefore the expression becomes,
5-38
G ( )
( )
3 1
240 10 J kg
G V P P
G
P P
V
G
P P
V
P
=

=

= +

=
( )
3 3 1
0.156 657 042 9 10 m kg

( )
5
10 Pa +

2 2 1 2
2
3 5
5
2
1 2
3 3
9
where 1 J kg m s and 1 Pa kg m s
1 J kg m s
kg m
1532009002 J m 10 Pa
1532009002 Pa 10 Pa
1532109002 P
s 1 Pa
1 m m
a
1.53 10 Pa
P
P
P
P

= =
= =
=
=
=
= +
= +


5-39
5.19. What are the partial pressures of toluene (0.60 mole fraction) and benzene (mole fraction) in a solution at 60 C? What is the total
pressure in the vapor? The vapor pressures of the pure substances at 60 C are as follows: toluene, 0.185 bar; benzene, 0.513 bar.
Solution:
Given:
* *
toluene benzene toluene benzene
0.60, 0.40, 60 C 333.15 K, 0.185 bar, 0.513bar x x T P P = = = = = =
Required:
total
P
The total pressure is given by the sum of partial pressures of each of the components in a mixture:
total toluene benzene
P P P = +
Raoults Law is given by Eq. 5.26, and can be used to solve for
total
P .
* *
1 1 1 2 2 2
; P x P P x P = =
( )
( )
toluene
toluene
benzene
benzene
total
total
total
0.60 0.185 bar
0.111 bar
0.40 0.513bar
0.2052bar
0.111 bar 0.2052bar
0.3162 bar
0.316 bar
P
P
P
P
P
P
P
=
=
=
=
= +
=
=

5-40
5.20. The normal boiling point of ethylene glycol (C
2
H
6
O
2
) is 197 C; its enthalpy of vaporization is 801 J mol
1
. Estimate the
temperature at which ethylene glycol will boil in a vacuum distillation if the system were maintained at 50 Torr.
Solution:
Given: ethylene glycol (C
2
H
6
O
2
),
1
vap
197 C 470 K, 801 J mol
B
T H = = =
Required: at 50 Torr
B
T P =
To obtain the temperature, we must use the Clausius-Clapeyron equation, in the form of Eq. 5.16 which states that:
vap
2
1 1 2
1 1
ln
m
H
P
P R T T
| |
=
|
\ .

First, we can determine the molar enthalpy of vaporization by multiplying the enthalpy of vaporization by the molar mass of ethylene
glycol.
vap vap
1
vap
801 J g
m
m
H H M
H
=
=
( )
2 12.011g
( )
1
mol 6 1.007 94 g
+
( )
1
mol 2 15.9994 g
+
( ) ( ) ( )
1
1
vap
mol
49 716.820 44 J mol
m
H
=

By making the appropriate substitutions into Eq. 5.16 we obtain,
5-41
760 Torr
ln
50 Torr
49 716.820 44 J
=
1
mol
( )

8.3145 J
1 1
K mol

( )
( )
( )
1
1
1
1
1
1
1
1 1

470 K
8.3145 K
760 1 1
ln
50 49 716.820 44 470 K
1
0.002 582 761 3 K
387.182 5087 K
387 K
T
T
T
T
T
| |
|
\ .
| |
| + =
|
\ .
=
=
=

5-42
5.21. Benzene and toluene form nearly ideal solutions. If, at 300 K, P* (toluene) =3.572 kPa and P* (benzene) =9.657 kPa, compute the
vapor pressure of a solution containing 0.60 mol fraction of toluene. What is the mole fraction of toluene in the vapor over this
liquid?
Solution:
Given:
* *
toluene benzene toluene benzene
0.60, 0.40, 300 K, 3.572 kPa, 9.657kPa x x T P P = = = = =
Required:
vapor
total toluene
, P x
The total pressure is given by the sum of partial pressures of each of the components in a mixture:
total toluene benzene
P P P = +
Raoults Law is given by Eq. 5.26, and can be used to solve for
total
P .
* *
1 1 1 2 2 2
; P x P P x P = =
( )
( )
toluene
toluene
benzene
benzene
total
total
0.60 3.572 kPa
2.1432 kPa
0.40 9.657kPa
3.8628kPa
2.1432 kPa 3.8628kPa
6.006 kPa
P
P
P
P
P
P
=
=
=
=
= +
=

The mole fraction of toluene in the vapor over the liquid is given by the partial pressure of toluene divided by the total pressure of the
vapor.
5-43
vapor toluene
toluene
total
vapor
toluene
2.1432 kPa
P
x
P
x
=
=
6.006 kPa
vapor
toluene
vapor
toluene
0.356 843
0.3568
x
x
=
=

5-44
5.22. Often it is important to express one unit of concentration in terms of another. Derive a general expression to find the mole fraction
x
2
in a two-component system where the molality is given as m
2
.
Solution:
The molality, m
2
, is the amount of solute divided by the mass of solvent. If W
1
is the mass of solvent, the solution contains
2 1
m W moles of
solute and
1
1
W
M
moles of solvent. The mole fraction is thus:
2 1
2
1
2 1
1
2 1
2
m W
x
W
m W
M
m W
x
=
+
=
1
W
2
1
2
2
2
1
1
1
m
M
m
x
m
M
| |
+
|
\ .
=
| |
+
|
\ .

Multiplying through by
1
1
M
M
gives,
( )
2 1
2
1 2
1
m M
x
M m
=
+

Dividing each term by its SI unit yields;
2 1
1 1
2
2 1
1 1
mol kg kg mol
1
mol kg kg mol
m M
x
m M

| || |
| |
\ .\ .
=
| || |
+
| |
\ .\ .

However, the customary unit for molar mass M
1
, is g mol
-1
, therefore we obtain,
5-45
2 1
1 1
2
2 1
1 1
mol kg 1000 g mol
1
mol kg 1000 g mol
m M
x
m M

| || |
| |
\ .\ .
=
| || |
+
| |
\ .\ .

1000
1000
gives,
2 1
1 1
2
2 1
1 1
mol kg g mol
1000
mol kg g mol
m M
x
m M

| || |
| |
\ .\ .
=
| || |
+
| |
\ .\ .

For sufficiently dilute solutions, the expression approximates to the following:
2 1
1 1
2
mol kg g mol
1000
m M
x

| || |
| |
\ .\ .

Therefore the general expression for mole fraction, x
2
, in a two-component system is:
2 1
1 1
2
mol kg g mol
1000
m M
x

| || |
| |
\ .\ .
=


5-46
5.23. Assuming that commercially available automotive antifreeze is pure ethylene glycol (it actually also contains relatively small
amounts of added rust inhibitors and a fluorescent dye that helps to differentiate a radiator leak from condensation from the air
conditioner), in what ratio by volume will antifreeze and water have to be mixed in order to have a solution that freezes at 20.0 C?
What will be the boiling point of this solution at 1 atm pressure? (MW =62.02 g mol
1
, density =1.1088 g cm
3
.)
Solution:
Given:
1 3
fus 2
20.0 C 20.0 K, 62.02 g mol , 1.1088 g cm , 1 atm T M P = = = = =
Required: V ratio, T
To solve for the volume ratio, we must first determine the mass of antifreeze present by using Eq. 5.122:
2
2
fus 1
f
K W
M
TW
=

Rearranging for W
2
gives,
2 fus 1
2
f
M TW
W
K
=
Where W
1
is 1.00 kg since we are solving for the ratio and K
f
is the freezing point depression constant for water given in Table 5.2. Given
that,
3
fus 2
2
20.0 C , , 1.1088 g cm , 1 atm
0.06202 kg
T M P
W
= = = = =
=
1
mol
( )
20.0 K
( )( ) 1.00 kg
1.86 K kg
1
mol
2
0.666 881 7204 kg W =

Using the definition of density, we can convert the mass of antifreeze into the volume of antifreeze.
5-47
3 3
2
2
1.1088 g cm 1.1088 kg dm
0.666 881 7204 kg
W
V
W
V
V
= =
=
=
=
1.1088 kg
3
dm

3
3
0.601 444 5531 dm
0.601 dm
V
V
=
=

Therefore the volume ratio is 0.601 dm
3

antifreeze to 1.0 dm
3
of water. (Or approximately 3:5)
The elevation of boiling point for this solution is given by Eq. 5.126 which states that:
vap 2 b
T K m =
Where
*
vap b
T T T = and K
b
is the boiling point depression constant given in Table 5.4. Solving for T, we obtain,
2
2
2
*
0.51K kg
b
W
m
M
T T
=
=
1
mol
( )
0.666 881 7204 kg
0.06202 kg
1
mol
( )
*
*
5.483870968K
5.483870968K
b
b
T T
T T
=
= +

*
373.15K
b
T = note that this is typically the boiling point of water!
5-48
5.483870968K 373.15K
378.633870968K
378.6K
T
T
T
= +
=
=

This means the solution will boil at 378.6 K.


5-49
5.24. The familiar term molarity is now discouraged by IUPAC because of the danger of confusion with molality. In its place,
concentration is defined as the amount of substance 2, n
2
, dissolved in unit volume of solution. Derive a general relation to find x
2

from the concentration c
2
. Let the solution density be .
Solution:
Let component 1 be the solvent and component 2 be the solute in the solution. The concentration, c
2
, is the number of moles of solute
divided by the volume of the solution.
2
2
n
c
V
=
From this expression, the amount in moles of solute is,
2 2
n Vc =
The mass of the solute is given bym nM = , hence,
2 2 2
m Vc M =
Density is given by
m
V
= , therefore the total mass of the solution is given by:
m V =
The mass of the solvent is then given by the difference in mass of solution and solute,
1 2 2
m V Vc M =
The amount in moles of solvent can then be found according to the following expression.
1 2 2
1
1 1
m V Vc M
n
M M

= =
The mole fraction of the solute is the number of moles of the solute divided by the total number of moles present in the solution.
5-50
2
2
2 2
2
1
2
Vc
x
V Vc M
Vc
M
V
x
=

+
=
2
c
V
2 2
2
1
c M
c
M
| |
+
|
\ .

2
2
2 2 2 1
1
c
x
c M c M
M
=
| | +
|
\ .

1
1
M
M
yields the following;
( )
2 1
2
2 1 2
c M
x
c M M
=
+

Dividing each term by its SI unit gives:
2 1
3 1
2
2 1 2
3 3 1 1
mol m kg mol
kg m mol m kg mol kg mol
c M
x
c M M

| | | |
| |
\ .\ .
=
| | | | | |
+
| | |
\ . \ . \ .

However, the customary units are, for concentration c
2
, is mol dm
-3
, for molar mass M
1
, is
g mol
-1
, for density , is kg dm
-3
g cm
-3
therefore we obtain,
2 1
3 1
2
2 1 2
3 3 1 1
1000
mol dm 1000 g mol
1000 1000
g cm mol dm 1000 g mol 1000 g mol
c M
x
c M M

| | | |
| |
\ .\ .
=
| | | | | |
+
| | |
\ . \ . \ .

5-51
Further simplification gives,
2 1
3 1
2
2 1 2
3 3 1 1
mol dm g mol
1000
g cm mol dm g mol g mol
c M
x
c M M

| | | |
| |
\ .\ .
=
| | | | | |
+
| | |
\ . \ . \ .

For sufficiently dilute solutions, the density of the solution is approximately that of the pure solvent,
1
, and the expression approximates to:
2 1
3 1
2
1
3
mol dm g mol
1000
g cm
c M
x
| | | |
| |
\ .\ .
| |
|
\ .

Therefore the general expression for mole fraction, x
2
, in solution is:
2 1
3 1
2
1
3
mol dm g mol
1000
g cm
c M
x
| | | |
| |
\ .\ .
=
| |
|
\ .

5-52
5.25. Show that if a solute follows Henrys law in the form of P
2
=kx
2
, then the solvent must follow Raoults law. (Hint: The use of the
Gibbs-Duhem equation might prove useful.)
Solution:
Henrys law is given by Eq. 5.27 as
1 2
, P k x = or
2 2
P k c = and Raoults law is given by,
Eq. 5.26 as
* *
1 1 1 2 2 2
; P x P P x P = = .
It is found that in the limit of infinite dilution most liquid solvents obey Raoults law but that under the same conditions the solute obeys
Henrys law.

Eq. 5.101,
*
,id
ln
i i i
RT x = +

5-53
5.26. A 1.0 m solution of NaCl in water produces a freezing point depression of approximately 3.7 K. How can we account for this
observation?
Solution:
Given:
fus
1.0 M, 3.7 K c T = =
Required: account for the observation.
The freezing point depression is given by Eq. 5.121, where K
f
is the freezing point depression constant for water provided by Table 5.2.
fus 2
fus
1.86 K kg
f
T K m
T
=
=
1
mol
( )
1.0 mol
1
kg
( )
fus
1.86 K T =

However, this is not what is observed.
Colligative properties are, to a large extent, determined by the number of particles in solution, rather than the actual identity of the species.
Since NaCl completely ionizes in solution, the resulting solution contains 2.0 moles of particles. Therefore we can calculate the temperature
change using;
fus
1.86 K kg T =
1
mol
( )
2.0 mol
1
kg
( )
fus
3.72 K 3.7 K T =

The ionization of NaCl accounts for the observed temperature change.


5-54
5.27. Derive a general expression to relate the molality m to concentration c
2
.

Solution:
Let component 1 be the solvent and component 2 be the solute in the solution. The molality, m
2
, is the amount of solute divided by the mass
of solvent. Using what we have done in problem 5.24, we can say that;
solute 2
n Vc = and
solvent 2 2
m V Vc M =
Therefore, molality can be expressed as,
2
2
2 2
2
2
2 2
Vc
m
V Vc M
c
m
c M

Rearranging the above, we can write concentration in terms of molality.
( )
( )
( )
2 2 2 2
2 2 2 2 2
2 2 2 2 2
2 2 2 2
2
2
2 2
1
1
m c M c
m c m M c
m c c m M
m c m M
m
c
m M
=
=
= +
= +
=
+

Dividing each term by its SI unit yields the following:
2
3 1
2
3
2 2
1 1
kg m mol kg
mol m
1
mol kg kg mol
m
c
m M

| || |
| |
| | \ .\ .
=
|
| | | || | \ .
+
| | |
\ .\ . \ .

However, the customary units are, for concentration c
2
, is mol dm
-3
, for molar mass M
1
, is
g mol
-1
, for density , is kg dm
-3
g cm
-3
therefore we obtain,
5-55
1000
2
3
1000
mol dm
c
| |
=
|
\ .
2
3 1
2 2
1 1
g cm mol kg
1
mol kg 1000 g mol
m
m M

| || |
| |
\ . \ .
| | | || |
+
| | |
\ .\ . \ .

1000
1000
gives,
2
3 1
2
3
2 2
1 1
1000
g cm mol kg
mol dm
1000
mol kg g mol
m
c
m M

| || |
| |
| | \ .\ .
=
|
| || | \ .
+
| |
\ .\ .

For sufficiently dilute solutions, the expression approximates to:
2
3
1000
mol dm
c

2
3 1
g cm mol kg
1000
m

| || |
| |
\ .\ .

Therefore the general expression for concentration in terms of molality is given by;
2 2
3 3 1
mol dm g cm mol kg
c m

| || |
=
| |
\ .\ .

Where
1
is the density of the solvent. For aqueous solutions
1
1 g cm
-3
, and therefore the numerical values of concentration and the
molality, in the above units, are very similar.

5-56
5.28. An amalgam of 1.152 g of a metal dissolved in 100.0 g of mercury is heated to boiling. The partial pressure of mercury vapor over
the boiling mixture is 754.1 Torr and the total pressure is 768.8 Torr. Find the atomic weight of the metal and, therefore, its identity.
Solution:
Given:
*
metal Hg Hg Hg
1.152 g, 100.0 g, 754.1 Torr, 768.8 Torr m m P P = = = =
Required: M
metal

Raoults Law is given by Eq. 5.26. It can be rearranged so that we can solve for x
Hg
and hence x
metal
since
metal Hg
1 x x + = .
*
1 1 1
1
1 *
1
Hg
Hg *
Hg
metal Hg
metal
1
754.1 Torr
1
P x P
P
x
P
P
x
P
x x
x
=
=
=
=
=
768.8 Torr
metal
0.0191207076 x =

The mole fraction is given by,
metal
metal
metal Hg
n
x
n n
=
+

Rearranging the above in order to isolate for the number of moles for the metal gives,
5-57
( )
( )
( )
( )
metal metal Hg metal
metal metal Hg metal metal
metal metal metal Hg metal
metal metal Hg metal
Hg metal
metal
metal
Hg metal
metal
metal
1
1
, where
1
x n n n
n x n x n
n x n n x
n x n x
n x
n
x
n x
m
n n
x M
+ =
+ =
=
=
= =

Once we have determined this value, we can easily find the molar mass for the metal.
( )
( )
Hg
metal
metal
metal Hg
metal
1
100.0 g
0.0191207076
1 0.0191207076
m
x
n
x M
n
=
=
200.59 g
1
metal
metal
metal
metal
1
metal
1
metal
mol
0.0097180497 mol
0.0097180497 mol
1.152 g
0.0097180497 mol
118.5423039 g mol
118.54 g mol
n
m
M
M
M
M
| |
|
|
\ .
=
=
=
=
=

The molar mass is 118.54 g mol
-1
which is approximately the same at the molar mass of tin, 118.710 g mol
-1
, therefore we can assume that
the identity of the metal is tin.

5-58
5.29. The volume of a solution of NaCl in water is given by the expression
V/cm
3
=1002.874 +17.8213 m +0.873 91 m
2
0.047 225 m
3
where m is the molality. Assume that m n
NaCl
and that
2
H O
n =55.508 mol, where
2
*
H O
V =18.068 cm
3
. Derive an analytical
expression for the partial molar volume of H
2
O in the solution.
Solution:
The partial derivative for the molar volume of a solution is given by Eq. 5.31 which states that;
2 3
1
1
, , , , T P n n
V
V
n
| |
|
\ .

When can applying this general equation to the expression given in the problem which gives;
H O
2
NaCl
NaCl
3 2
NaCl
/ cm 17.8213 1.74782 0.141 675
n
V V
V
n m
V m m
| | | |
= =
| |

\ .
\ .
= +

We can now use Eq. 5.37, the Gibbs-Duhem equation, to obtain an expression for
2
H O
dV .
( )
2
2
2
2
2
1 2
1
NaCl
H O NaCl
H O
NaCl
NaCl
H O
H O
1.74782 0.283 35
1.74782 0.283 35
n
dV dV
n
n
dV dV
n
dV
m
dm
n
dV m
n
=
=
=
=

We are working under the assumption that ; m n
NaCl
and since
2
H O
n =55.508 mol. It is now possible to integrate the above expression in
order to solve for
2
H O
V , the partial molar volume of H
2
O.
5-59
( )
( )
( )
2
2
2
H O
2
H O
2
H O
1.74782 0.283 35
55.508mol
1
1.74782 0.283 35
55.508mol
1
1.74782 0.283 35
55.508mol
m
dV m
dV m m
dV m m dm
=
=
=

( )
( )
( )
( )
2 2
2 2
2 2
2
* 2
H O H O
* 2 3
H O H O
2 3 *
H O H O
3 1 3 2 3
H O
1
1.74782 0.283 35
55.508mol
1
0.87391 0.09445
55.508mol
1
0.87391 0.09445
55.508mol
1
/cm mol 18.068 cm 0.87391 0.09445
55.508mol
V V m m dm
V V m m
V m m V
V m m
=
=
= +
=

5-60
5.30. The partial molar volume of component 2 in a solution may be written as
1
1
2
2
2
1 1 2 2 2
2
1
( )
n
n
V
V
n
M
M n M n
n

| |
=
|
\ .
| |
= +
|
\ .

where n
1
and M
1
are amount and molar mass of component 1 and n
2
and M
2
represent the same quantities for component 2. The
density is . Rewrite the expression in terms of the mole fractions x
1
and x
2
.
Solution:
Recall that the mole fraction for a species is given by ;
2 1
2 1
1 2 1 2
,
n n
x x
n n n n
= =
+ +

Therefore we must first develop an expression for
1
2
n
n
| |
|
\ .
using this definition.
( )
( )
( )
1
1
1 2 2 2
2
2
1 2
2 1
2
2
1 2
1
n
n
n n n x
n
n n
x n
n
n n
+ | |
=
|
+
\ .
| |
=
|
+
\ .

By using Eulers Chain Rule outlined in Appendix C we can formulate the appropriate expression.
( )
1 1
1
2
2 2 2
1
2
2 2
1 2
n n
n
x d
n dx n
n d
n dx
n n

| | | |
=
| |

\ . \ .
| |
=
|
+
\ .

5-61
We can now substitute the above into the expression for V
2
given in the problem to produce,
( )
2 1
2 1 1 2 2 2 2
2
1 2
1
( )
M n d
V M n M n
dx
n n

| |
| = +
|
+
\ .

Since we know that
2 1
2 1
1 2 1 2
,
n n
x x
n n n n
= =
+ +
, it follows that the expression becomes,
( ) ( )
( ) ( )
( )
2 1
2 1 1 2 2 2
1 2 1 2 2
2 1 1 2 2
2 1 2
1 2 1 2 2
2 1
2 1 1 2 2 2
2
1 1
( )
1
M n d
V M n M n
n n n n dx
M M n M n d
V x
n n n n dx
M x d
V M x M x
dx

| |
= +
|
|
+ +
\ .
| | | |
= +
| |
|
+ +
\ . \ .
| |
= +
|
\ .

5-62
5.31. Mikhail and Kimel, J. Chem. Eng. Data, 6, 533(1961), give the density of a water-methanol solution in g cm
3
at 298 K related to
the mole fraction x
2
of the methanol through the equation
3 2
2 2
3 4 5
2 2 2
/gcm 0.9971 0.28930 0.29907
0.60876 0.59438 0.20581
x x
x x x
= +
+

Using the equation developed in Problem 5.30, calculate V
2
at 298 K when x
2
=0.100.
Solution:
Given:
2
298 K, 0.100 T x = =
Required: V
2
We can make use of the equation developed for V
2
in the previous problem (5.30).
( )
2 1
2 1 1 2 2 2
2
M x d
V M x M x
dx

| |
= +
|
\ .

In this particular problem, M
1
is the molar mass of water, M
2
is the molar mass of methanol, and x
1
is the mole fraction of water.
( )
( )
1 2
1
1
1 1
1
1
1
1 1 1
2
1
2
1
1 0.100
0.900
2 1.007 94 g mol 15.9994 g mol
18.01528 g mol
12.011 g mol 4 1.007 94 g mol 15.9994 g mol
32.04216 g mol
x x
x
x
M
M
M
M

=
=
=
= +
=
= + +
=

5-63
Solving for , where
2
0.100 x = gives,
( ) ( ) ( ) ( ) ( )
2 3 4 5
3
2 2 6
0.9971 0.28930 0.100 0.29907 0.100 0.60876 0.100 0.59438 0.100 0.20581 0.100
0.9706093199 g cm
0.9420824519g cm
= + +
=
=
We can now take the derivative of
with respect to x
2
,
( ) ( ) ( ) ( )
2 3 4
2 2 2 2
2
2 3 4
2
0.289 30 0.598 14 1.826 28 2.377 52 1.02905
0.289 30 0.598 14 0.100 1.826 28 0.100 2.377 52 0.100 1.02905 0.100
d
x x x x
dx
d
dx
= + +
= + +

3
2
0.245474 185 g cm
d
dx

=
Now that we have found all of the required values, we can make the appropriate substitutions into the expression we found for V
2
to obtain,
2
32.04216 g
V =
1
mol
0.9706093199 g
3
18.01528 g
cm

( )( )
1
mol 0.900 32.04216 g
+
( )( )
( )
1
2
mol 0.100
0.900
0.9420824519 g
6
0.245474 185 g
cm

( )
3
3
2
cm
37.566 10468 cm V
=
3
1 3
3
dm
mol 10
cm

3 1
2
2 3 1
2
0.037566 10468 dm mol
3.76 10 dm mol
V
V

=
=

5-64
5.32. Beckmann and Faust [Z. Physik. Chemie, 89, 235(1915)] found that a solution of chloroform in acetone in which the mole fraction
of the latter is 0.713 has a total vapor pressure of 220.5 Torr at 28.15 C. The mole fraction of acetone in the vapor is 0.818. The
vapor pressure of pure chloroform at this temperature is 221.8 Torr. Assuming that the vapor behaves ideally, calculate the activity
and the activity coefficient of chloroform.
Solution:
Given: in solution,
acetone total
0.713, 220.5 Torr, 28.15 C 301.3 K, x P T = = = =
in vapor phase,
*
acetone chloroform
0.818, 221.8 Torr x P = =
Required:
chloroform chloroform
, a f
This problem makes use of Raoults Law which defines the chemical potential for a pure component i in terms of a dimensionless activity,
a. The activity is given by Eq. 5.75:
o *
i i
i
i i
f P
a
f P
= =
Therefore the activity of chloroform is given by,
chloroform
chloroform *
chloroform
P
a
P
=
To solve for
chloroform
P we may use Daltons Law of Partial Pressures with the mole fraction of pure chloroform in the vapor phase. This will
yield the following:
( )
chloroform acetone
chloroform
chloroform
chloroform
1
1 0.818 220.5 Torr
40.131 Torr
40.131 Torr
x x
P
P
a
=
=
=
=
221.8 Torr
chloroform
chloroform
0.1809332732
0.181
a
a
=
=

5-65
The usual procedure in dealing with solvent species (as we have already seen) is to use the mole fraction. In chapter 4 (specifically section
4.3) we defined the Gibbs Free Energy by Eq. 4.48 which states that:
( )
O
1 1
ln G G RT x f = +
Since we know that when using Raoults Law
i
i
i
G
n
= which subsequently allows us to write;
* *
ln ln
u
i i i i i
RT f RT a = + = +
With this, we can say that the activity coefficient is given by f
i
=a
i
/x
i
.
chloroform
chloroform
acetone
chloroform
chloroform
chloroform
1
0.1809332732
1 0.713
0.630429 5234
0.630
a
f
x
f
f
f
=
=
=

5-66
5.33. When 12.5 g of A, a nonvolatile compound, is dissolved in 520.8 g of ethanol, the vapor pressure of the pure solvent, 56.18 Torr, is
reduced to 55.24 Torr. Calculate the molar mass of compound A.
Solution:
Given:
*
A ethanol ethanol ethanol
12.5 g, 520.8g, 56.18 Torr, 55.24 Torr m m P P = = = =
Required: M
A
This problem again refers to Raoults Law (for ideal solutions). The following form of Raoults Law (Eq. 5.78) is especially useful for
solutions of relatively involatile solutes in a volatile solvent.
*
1 1 1
1 2 * *
1 1
1 1 or rather
P P P
x x
P P
| | | |
= =
| |
\ . \ .

Eq. 5.78 may be written so that the molar mass of the solute 2 may be determined. For a dilute solution, n
2
may be neglected in the
denominator (Eq. 5.79) and we obtain Eq. 5.80;
*
1 1 2 2 1
*
1 1 2 1
P P n W M
P n M W
= =
Rearranging the above in order to isolate for M
2
gives,
( ) ( ) ( )
*
1 1
2 2 *
1 1 1
1 1 1
1
1
1
A
2 12.011g mol 6 1.007 94 g mol 15.9994 g mol
46.06904g mol
12.5 g
M P
M W
W P P
M
M
M

= + +
=
=
( )
1
46.06904g mol
520.8 g
56.18 Torr
56.18 Torr 55.24 Torr
1
A
1
A
66.08487625 g mol
66.1 g mol
M
M
=
=

5-67
5.34. The following data are for mixtures of isopropanol (I) in benzene (B) at 25 C.
x
I
0 0.059 0.146 0.362
P
I
(Torr) 0 12.9 22.4 27.6
P
tot
94.4 104.5 109.0 108.4
0.521 0.700 0.836 0.924 1.0
30.5 36.4 39.5 42.2 44.0
105.8 99.8 84.0 66.4 44.0

Does this solution exhibit positive or negative deviation from Raoults law? From a pressure-composition plot, estimate the
activities a
I
and a
B
and activity coefficients f
I
and f
B
at x
I
=0.20, 0.50, and 0.80. [Data from Olsen and Washburn, J. Phys. Chem.,
41, 457(1937).]
Solution:
Given:
Required:

5-68

5-69
5.35. The vapor pressure of pure ethylene dibromide is 172 Torr and that of pure propylene dibromide is 128 Torr both at 358 K and 1
atm pressure. If these two components follow Raoults law, estimate the total vapor pressure in kPa and the vapor composition in
equilibrium with a solution that is 0.600 mol fraction propylene dibromide.
Solution:
Given:
* *
e p p
172 Torr, 128 Torr, 358 K, 1 atm, 0.600 P P T P x = = = = =
Required:
total e p
, , P x x in vapor
The total pressure is given by the sum of partial pressures for each of the components in a mixture.
total e p
P P P = +
Raoults Law is given by Eq. 5.26, therefore we can use it solve for
total
P .
* *
1 1 1 2 2 2
; P x P P x P = =
( )
( )
e
e
p
p
total
total
0.400 172 Torr
68.8 Torr
0.600 128 Torr
76.8 Torr
68.8 Torr 76.8 Torr
145.6 Torr
P
P
P
P
P
P
=
=
=
=
= +
=
101325Pa
760 Torr
total
total
19411.73684Pa
19.4kPa
P
P
=
=

The vapor composition is given by the mole fractions in the vapor over the solution. The mole fraction for a species is given by the partial
pressure divided by the total pressure of the vapor.
5-70
e
e
total
e
68.8 Torr
P
x
P
x
=
=
145.6 Torr
e
e
0.472 5274725
0.473
x
x
=
=

p
p
total
p
76.8 Torr
P
x
P
x
=
=
145.6 Torr
p
p
0.527 4725275
0.527
x
x
=
=


5-71
5.36. Calculate Henrys law constant and the vapor pressure of pure liquid A (molar mass =89.5 g mol
1
) and that of 75.0 g of liquid A in
solution with 1000 g of liquid B. Liquid B (molar mass =185 g mol
1
) has a pressure in this solution of 430 Torr and the total
solution pressure is 520 Torr.
Solution:
Given:
1 1
A A B
89.5 g mol , 75.0 g, 185 g mol , 1000 g,
B
M m M m = = = =
B total
430Torr, 520Torr P P = =
Required: k, P
A
total A B
P P P = +
Solving for P
A
gives,
A total B
A
A
520Torr 430Torr
90Torr
P P P
P
P
=
=
=

Henrys Law is given by Eq. 5.27 which states that:
1 2
P k x =
To solve for Henrys Law constant, we first need to obtain the mole fraction of species A.
5-72
A
A
A B
A
where
75.0 g
n
x
n n
m
n
M
x
=
+
=
=
89.5 g
1
mol
75.0 g
89.5 g
1
mol
1000 g
+
185 g
1
mol
A
0.1342200726 x =

We can now rearrange Henrys Law (given above) to isolate for k which gives,
1
2
P
k
x
=
90Torr
0.1342200726
670.5405403Torr
671Torr
k
k
k
=
=
=


5-73
5.37. Henrys law constants k for N
2
and O
2
in water at 20.0 C and 1 atm pressure are 7.58 10
4
atm and 3.88 10
4
atm, respectively.
If the density of water at 20.0 C is 0.9982 g cm
3
, calculate (a) the equilibrium mole fraction and (b) the concentration of N
2
and O
2

in water exposed to air at 20.0 C and 1 atm total pressure. Assume in this case that air is 80.0 mol % N
2
and 20.0 mol % O
2
.
Solution:
Given:
2 2
4 4 3
N O
20.0 C 293.15K, 1 atm, 7.58 10 atm, 3.88 10 atm, 0.9982 gcm T P k k

= = = = = =
2 2
N O
0.800, 0.200 x x = =
Required:
a)
2 2
N O
, x x at equilibrium
b)
2 2
N O
, c c
Recall that Henrys Law is given by Eq. 5.27 which states that:
1 2
P k x =
To solve for the mole fraction of a species at equilibrium, we first need to obtain
2
N
P and
2
O
P . The partial pressures,
2
N
P and
2
O
P , are given
by the mole fraction multiplied by the total pressure.
( )( )
( )( )
2 2
2
2
2
2
N N total
N
N
O
O
0.800 1atm
0.800atm
0.200 1atm
0.200atm
P x P
P
P
P
P
=
=
=
=
=

Now we can determine the values for
2 2
N O
and x x according to:
5-74
2
2
2
2
N
N
N
N
0.800 atm
P
x
k
x
=
=
4
7.58 10 atm
2
2
5
N
5
N
1.055408971 10
1.06 10
x
x
=
=

2
O
0.200 atm
x =
4
3.88 10 atm
2
2
6
O
6
N
5.154639175 10
5.15 10
x
x
=
=

We can use 1 mole of water as a reference, and therefore obtain:
2
5
N
1.055408971 10 mol n

= and
2
6
O
5.154639175 10 mol n

=
By using the density of water, we are able to solve for the concentration.
5-75
( ) ( )
2 2
2 2
2
2
H O H O
H O H O
1 1
H O
H O
2 1.007 94 g mol 15.9994 g mol
18.01528 g
n
c
V
m
V
n M
m
V
n
c
n M
M
M

=
=
= =
=
= +
=
1 3
kg
mol 10
g

( )
2
2
2 1
H O
5
N
1.801528 10 kg mol
1.055408971 10 mol 0.9982 kg
M
c

=
( )
3
dm
1mol
2
1.801528 10 kg
1
mol
( )
( )
2
2
2
4 3
N
4 3
N
6
O
5.847864895 10 mol dm
5.85 10 mol dm
5.154639175 10 mol 0.9982 kg
c
c
c

=
=
=
( )
3
dm
1mol
2
1.801528 10 kg
1
mol
( )
2
2
4 3
O
4 3
O
2.856109272 10 mol dm
2.86 10 mol dm
c
c

=
=

5-76
5.38. Methane dissolves in benzene with a Henrys law constant of 4.27 10
5
Torr. Calculate methanes molal solubility in benzene at 25
C if the pressure above benzene is 750 Torr. The vapor pressure of benzene is 94.6 Torr at 25 C.
Solution:
Given:
5 *
benzene benzene
25.0 C 298.15K, 4.27 10 Torr, 750 Torr, P 94.6 Torr T k P = = = = =
Required: methanes molal solubility
To solve this problem, we assume that the total vapor pressure of pure benzene is present in the total pressure of 750.0 Torr.
total methane benzene
P P P = +
Solving for
methane
P gives,
methane total benzene
methane
methane
750 Torr 94.6 Torr
655.4 Torr
P P P
P
P
=
=
=

Using Henrys Law, we can obtain the mole fractions of methane and benzene.
1 2
P k x =
methane
methane
methane
methane
655.4 Torr
P
x
k
x
=
=
5
4.27 10 Torr
methane
benzene methane
benzene
0.0015348946
1
0.9984651054
x
x x
x
=
=
=

The mole fraction is given by the expression,
5-77
methane
methane
methane benzene
n
x
n n
=
+

Where,
benzene
benzene
benzene
m
n
M
=
In 1000 g of benzene,
benzene
1000 g
n =
6 1.00794 g
( )
1
mol 6 12.011 g
+
( )
1
benzene
mol
12.80186149 mol n
=

Solving for n
methane
gives the molality of methane,
( )
( )
( )( )
methane methane benzene methane
benzene methane methane methane methane
benzene methane methane methane
benzene methane
methane
methane
methane
metha
1
1
12.80186149 mol 0.0015348946
0.9984651054
x n n n
n x n n x
n x n x
n x
n
x
n
n
+ =
=
=
=
=
ne
2
methane
0.0196797144 mol
1.97 10 molality m
=
=


5-78
5.39. In a molar mass determination, 18.04 g of the sugar mannitol was dissolved in 100.0 g of water. The vapor pressure of the solution
at 298 K was 2.291 kPa, having been lowered by 0.0410 kPa from the value for pure water. Calculate the molar mass of mannitol.
Solution:
Given:
2
*
mannitol H O 1 1 1
18.04g, 100.0g, 298K, 2.291kPa, 0.0410kPa m m T P P P = = = = =
Required:
mannitol
M
We can use the expression for lowering the vapor pressure in solution, given by Eq. 5.79 to solve this problem.
*
1 1 2 2 2
*
1 1 2 1 1 2 2
/
( / ) ( / )
P P n W M
P n n W M W M
= =
+ +

The above expression can then be rearranged to isolate for M
2
,
5-79
( ) ( ) ( )
( ) ( )
( )
( )
2
*
1 1 1 2 2
*
1 1 2 2
*
1
2 2 1 1 2 2 *
1 1
*
1
2 2 1 1 *
1 1
*
1
2 2 1 1 *
1 1
*
1
2 *
1 1
2
1 1
*
1
1 2 *
1 1
2
1
*
1
H O mannitol *
1 1
mannitol
( / ) ( / )
/
/ / /
/ 1 /
1 /
/
1
P W M W M
P P W M
P
W M W M W M
P P
P
W M W M
P P
P
W M W M
P P
P
W
P P
M
W M
P
M W
P P
M
W
P
M W
P P
M
+
=
= +
| |
=
|
\ .
| |
=
|
\ .
| |
|
\ .
=
| |
|
\ .
=
|
\
=
( ) ( )
2
2
2
H O
* *
1 1 1 1
1 1
H O
1
H O
where,
2 1.007 94 g mol 15.9994 g mol
18.01528 g mol
W
P P P P
M
M

|
|
.
= +
= +
=

( )
1
mannitol
18.01528 g mol 18.04 g
M
=
( )
0.0410 kPa 2.291kPa +
0.0410 kPa
1
100.0 g
| |
|
\ .
1
mannitol
1
mannitol
181.6012285 g mol
181.6 g mol
M
M
=
=

5-80
The molecular formula for mannitol is C
6
H
8
(OH)
6
, therefore the actual molar mass is found to be:
( ) ( ) ( )
1 1 1
1
14 1.007 94 g mol 6 15.9994 g mol 6 12.011 g mol
182.17356g mol
M
M

= + +
=

5-81
5.40. A liquid has a vapor pressure of 40.00 kPa at 298.15 K. When 0.080 kg of an involatile solute is dissolved in 1 mol of the liquid, the
new vapor pressure is 26.66 kPa. What is the molar mass of the solute? Assume that the solution is ideal.
Solution:
Given:
*
1 solute solvent 1
40.00kPa, 298.15K, 0.080g, 1mol, 26.66kPa P T m n P = = = = =
Required:
solute
M
This problem makes use of Raoults Law which is given by Eq. 5.26. We can use it solve for
solute
x .
* *
1 1 1 2 2 2
1
1 *
1
1
;
26.66kPa
P x P P x P
P
x
P
x
= =
=
=
40.00 kPa
1
solvent 1
0.6665
0.6665
x
x x
=
= =

The mole fraction of the solute is given by:
( )
( )
solvent
solvent
solute solvent
solute solvent solvent solvent solvent
solvent solvent
solute
solvent
solute
solute
1
1mol 1 0.6665
0.6665
0.5003750938mol
n
x
n n
n x n x n
n x
n
x
n
n
=
+
+ =
=
=

Solving for the molar mass of the solute produces the following;
5-82
solute
solute
solute
solute
solute
solute
solute
1
solute
0.080g
0.5003750938mol
0.15988006 gmol
m
n
M
m
M
n
M
M

=
=
=
=

1
solute
0.160 gmol M

=

5-83
5.41. Components 1 and 2 form an ideal solution. The pressure of pure component 1 is 13.3 kPa at 298 K, and the corresponding vapor
pressure of component 2 is approximately zero. If the addition of 1.00 g of component 2 to 10.00 g of component 1 reduces the total
vapor pressure to 12.6 kPa, find the ratio of the molar mass of component 2 to that of component 1.
Solution:
Given:
1 2 1 2 total
13.3 kPa, 0 kPa, 298K, 10.00 g, 1.00g, 12.6kPa P P T m m P = = = = = =
Required:
2
1
M
M

For a two-component system, we can use the second form of Eq. 5.78 to obtain x
2
,
*
1 1
2 *
1
2
13.3 kPa
P P
x
P
x
=
=
12.6 kPa
13.3 kPa
2
0.052 6315789 x =

We can now use the expression for lowering the vapor pressure in solution, given by Eq. 5.79, to solve this problem.
*
1 1 2 2 2
*
1 1 2 1 1 2 2
/
( / ) ( / )
P P n W M
P n n W M W M
= =
+ +

The above may be rearranged to isolate for
2
1
M
M
which gives,
( ) ( )
( ) ( )
( ) ( )( )
2 2
2
1 1 2 2
2 1 1 2 2 2 2 2
2 1 1 2 2 2
/
/ /
/ / /
/ / 1
W M
x
W M W M
x W M x W M W M
x W M W M x
=
+
+ =
=

Multiplying through by M
2
we obtain the following:
5-84
( )
( )
2
2 1 2 2
1
2 2 2
1 1 2
1
1
M
x W W x
M
W x M
M W x
| |
=
|
\ .
=

2
1
1.00 g
M
M
=
( )( ) 1 0.052 6315789
10.00 g

( )( )
2
1
0.052 6315789
1.8
M
M
=


5-85
5.42. Pure naphthalene has a melting point of 353.35 K. Estimate the purity of a sample of naphthalene in mol %, if its freezing point is
351.85 K (K
f
=7.0 K kg mol
1
).
Solution:
Given:
1
353.35K, 351.85 K, 7.0 K kg mol
m f f
T T K = = =
Required: purity of naphthalene
To determine the purity of naphthalene, we first determine the mass of naphthalene present, m
2
from Eq. 5.121.
fus 2
fus
2
2
353.35 K
f
f
T K m
T
m
K
m
=
=
=
351.85 K
7.0 K
1
1
2
kg mol
0.2142857143 mol kg m =

The molecular formula for naphthalene is C
10
H
8
, therefore the molar mass found from the periodic table of the elements is:
( ) ( )
1 1
1
10 12.011 g mol 8 1.007 94 g mol
128.17352g mol
M
M

= +
=

To determine the molar purity, we can use;
5-86
2
total
molar impurity 100%
0.2142857143 mol
molar impurity
m
m
=
=
1
kg
0.2142857143 mol
1
kg 128.17352 g +
1
mol
3
10 kg
1
g
( )
1
100%
molar impurity 2.673155205%
molar purity 100 % 2.673155205%
molar purity 97.3268448%
molar purity 97%
=
=
=
=


5-87
5.43. Calculate the activity and activity coefficients for 0.330 mol fraction toluene in benzene. The vapor pressure of pure benzene is
9.657 kPa at 298 K.
*
2
P =3.572 kPa for toluene. The vapor pressure for benzene above the solution is P
1
=6.677 kPa and for
toluene P
2
=1.214 kPa.
Solution:
Given
* *
toluene benzene toluene
0.330, 9.657 kPa, 298 K, 3.572 kPa x P T P = = = =
benzene toluene
6.677 kPa, 1.214 kPa. P P = =
Required:
toluene benzene benzene toluene
, , , a a f f
The activity is given by Eq. 5.75,
o *
toluene
1.214 kPa
i i
i
i i
f P
a
f P
a
= =
=
3.572 kPa
toluene
toluene
benzene
0.3398656215
0.3399
6.677 kPa
a
a
a
=
=
=
9.657 kPa
benzene
benzene
0.6914155535
0.6914
a
a
=
=

The activity coefficient is determined from the definition f
i
=a
i
/x
i
where f
i
is the activity coefficient (Recall that we can relate this to the
expression for the Gibbs Free Energy given in Section 4.3.) .
5-88
toluene
toluene
toluene
toluene
toluene
toluene
benzene
benzene
benzene
benzene
0.3398656215
0.330
1.029895823
1.03
0.6914155535
1 0.330
a
f
x
f
f
f
a
f
x
f
=
=
=
=
=
=

benzene
benzene
1.031963513
1.03
f
f
=
=

5-89
5.44. Calculate the mole fraction, activity, and activity coefficients for water when 11.5 g NaCl are dissolved in 100 g water at 298 K. The
vapor pressure is 95.325 kPa.
Solution:
Given:
2
NaCl H O
11.5g, 100 g, 298 K, 95.325 kPa m m T P = = = =
Required:
2 2 2
H O H O H O
, , x a f
The mole fraction of water can be obtained from Eq. 5.79 which states that:
( ) ( )
( ) ( )
( ) ( )
2
2
2
2 2
2
1 1 2 2
1 1
H O
1
H O
1 1
NaCl
1
NaCl
H O
/
/ /
where
2 1.007 94 g mol 15.9994 g mol
18.01528 g mol
22.989 768 g mol 35.4527 g mol
58.442468 g mol
100 g
W M
x
W M W M
M
M
M
M
x

=
+
= +
=
= +
=
=
18.01528 g
1
mol
11.5 g
58.442468 g
1
mol
100 g
+
18.01528 g
1
mol
2
2
H O
H O
0.9657641291
0.966
x
x
=
=

As we have previously seen, the activity is given by Eq. 5.75;
5-90
2
o *
H O
95.325 kPa
i i
i
i i
f P
a
f P
a
= =
=
101.325 kPa
2
2
H O
H O
0.940784604
0.94078
a
a
=
=

i
=a
i
/x
i
where f
i
is the activity coefficient (Recall that we may relate this to the
expression for Gibbs Free Energy from section 4.3.).
2
2
2
2
2
2
H O
H O
H O
H O
H O
H O
0.940784604
0.9657641291
0.9741349628
0.974
a
f
x
f
f
f
=
=
=
=

5-91
5.45. Determine the range for the Gibbs energy of mixing for an ideal 50/50 mixture at 300 K. How does this value limit
mix
H?
Solution:

Figure 5.13 gives
mix
S of 1 mol of an ideal solution from the pure components. For an ideal 50/50 mixture,
1 2
0.5 x x = = , therefore by
observing the figure, the maximum
mix
S is approximately 5.76 J K
-1
mol
-1
. The maximum Gibbs energy would then be then be given by
Eq. 5.97 which states that:
id id
mix mix
id
mix
300 K
G T S
G
=
=
( )
1
5.76 J K
( )
1
id 1
mix
mol
1728 J mol G
=

The range of Gibbs energy in an ideal 50/50 mixture would then be from
1
0 to 1.73 kJ mol
.
This limits
mix
H since the Gibbs Energy is a rather small driving force. In a non-ideal solution where
mix
H=0, the value of
mix
H must be
negative or only slightly positive for mixing to occur.


5-92
5.46. The mole fraction of a nonvolatile solute dissolved in water is 0.010. If the vapor pressure of pure water at 293 K is 2.339 kPa and
that of the solution is 2.269 kPa, calculate the activity and activity coefficient of water.
Solution:
Given:
2 2
*
solute H O H O
0.010, 293 K, 2.339 kPa, 2.269kPa x T P P = = = =
Required:
2 2
H O H O
, a f
Recall that the activity is given by Eq. 5.75:
2
o *
H O
2.269 kPa
i i
i
i i
f P
a
f P
a
= =
=
2.339 kPa
2
2
H O
H O
0.9700726806
0.9701
a
a
=
=

i
=a
i
/x
i
where f
i
is the activity coefficient (In chapter 4, we were given an
expression for the Gibbs Free Energy which can be related back to the activity). Therefore,
2
2
2
2
2
2
H O
H O
H O
H O
H O
H O
0.9700726806
1 0.010
0.9798713946
0.980
a
f
x
f
f
f
=
=
=
=

5-93
5.47. A nonideal solution contains n
A
of substance A and n
B
of substance B and the mole fractions of A and B are x
A
and x
B
. The Gibbs
energy of the solution is given by the equation
o o
A A B B A A B B
A B A B
( ln ln )
/( )
G n n RT n x n x
Cn n n n
= + + +
+ +

where C is a constant and describes the pair interaction.
a. Derive an equation for
A
in the solution in terms of the quantities on the right-hand side. {Hint:
B
A A A A B
( ln / ) (1/ )[1/( )].
n
x n n n n = + }
b. Derive a similar expression for the activity coefficient of A. Specify the conditions when the activity coefficient equals unity.
Solution:
Find the value of
A
such that
A B
G + = is equal to the expression given in the problem. First we can start by outlining the partial
derivative for
A
;
( )
( )
B
A
B B
A
A
, ,
B A B A B * A B
A A A B 2
A A
A B
ln ln
ln
n T P
n n
G
n
n n n n n x x
RT x n n C
n n
n n

| |
=
|
\ .
| | | |
+ | | | |
| | = + + + +
| |
| |
+
\ . \ .
\ . \ .

Using the hint given in the problem, we recognize that the derivative of lnx
A
is:
( ) ( )
B B
B
B
A
A B A
A A B
A A A
A
A A A B
ln
ln
ln ln
ln 1 1
n n
n
n
n
n n x
n n n
n n n
x
n n n n
| | | |
| |
+ | | | |
\ . |
= = +
| |
|

\ . \ .
|
|
\ .
| |
=
|
+
\ .

Therefore, the expression for lnx
B
is:
5-94
( ) ( )
B B
B
B
A B B
B A B
A A A
ln
ln
ln ln
n n
n
n
n n x
n n n
n n n
| | | |
| |
+ | | | |
\ . |
= = +
| |
|

\ . \ .
|
|
\ .

B
B
A A B
ln 1
n
x
n n n
| |
=
|
+
\ .

Substituting the above into the initial equation and simplifying, we can obtain an equation for
A
.
( )
( )
A
A
B A B A B *
A A A B 2
A A B A B
A B
A *
A A
1 1 1
ln
ln
n n n n n
RT x n n C
n n n n n
n n
n
RT x

| |
| | + | | | |
| = + + + +
| | |
|
|
+ +
+
\ . \ . \ .
\ .
= + +
A
n
A B
A B
A B A B
n n
n n
C
n n n n
| |
+ |
|
+ +
\ .
2
B A B
n n n +
( )
( )
A
A
2
A B
2
* A B B
A A 2
A B
A B
A B *
A A
ln 1
ln 1
n n
n n Cn
RT x
n n
n n
n n
RT x

| |
|
|
+
\ .
| |
= + + +
|
+
+
\ .
+
= + +
A B
n n +
( )
A
2
B
2
A B
* 2
A A B
ln
Cn
n n
RT x Cx
| | | |
| + |
| |
+
\ . \ .
= + +

To obtain an expression for the activity coefficient of A we can compare the expression in part a with Eq. 5.102 which states that:
,id
ln
i
i i
i
a
RT
x
=
From Eq. 5.103 we can see that,
and 1 as 1
i
i i i
i
a
f f x
x
=
5-95
,id
,id
*
A A A
ln
ln
ln
i i i
i i i
RT f
RT f
RT f

=
= +
= +

By comparison,
2
B
2
A B
A
A B
ln
1, as 0
Cx
RT
RT f Cx
f e
f x
=
=
=

This corresponds to pure A. In a very dilute solution of A in B, we also expect
A
1 f . In that case,
( )
A
*
A A A
0
lim ln
x
RT x
=
Substitution of the expression above into the previous yields;
( )
B
* * 2 *
A A B A
1
lim
x
Cx C
= + = +
Therefore,
( )
( )
* 2 *
A A B A A A
2
B
A B
, when
ln 1 ln ln
1
ln 0 1
RT x C x RT x RT f
C x
f x
RT

= + + = + +
= =


5-96
5.48. Calculate the mole fraction solubility of naphthalene at 25 C in a liquid with which it forms an ideal solution. The
fus
H =19.0 kJ
mol
1
for naphthalene at 25 C. Its normal melting point is 80.2 C.
Solution:
Given:
1
fus m
298.15 K, 19.0 kJ mol , 80.2 C 353.35K T H T = = = =
Required:
n
x
To solve this problem, we must use the expression for the mole fraction of a solvent in relation to the freezing point of an ideal solution and
to the freezing point of the pure solvent. This is given by Eq. 5.115:
fus
1 *
1 1
ln
m
f
H
x
R T T
| |
= |
|
\ .

Solving for
n
x , we obtain,
*
3
1 1
n
19.0 10 J
n
fus m
f
H
R T T
x e
x e
| |
|
|
\ .
=
=
1
mol
8.3145 J
1
K
1
mol
1
353.35 K
1
298.15 K
1.19733763
n
n
n
0.301997 1708
0.302
x e
x
x
| |
|
\ .
=
=
=


5-97
5.49. Using Henrys law, determine the difference between the freezing point of pure water and water saturated with air at 1 atm. For N
2

at 298.15 K,
(k)
1
=2.17 10
8
mol dm
3
Pa
1

For O
2
at 298.15 K,
(k)
1
=1.02 10
8
mol dm
3
Pa
1
Solution:
Given: 298.15 K, 1 atm, T P = =
( ) ( )
2 2
1 1
8 3 1 8 3 1
N O
2.17 10 mol dm Pa , 1.02 10 mol dm Pa k k = =
Required:
fus
T
We have previously seen that Henrys Law is given by Eq. 5.27 stating that:
2 2
P k c =
We can use Henrys Law to determine the concentrations of N
2
and O
2
in water. Rearranging, we obtain,
( )
1
2 2
c P k

=
The partial pressures for N
2
and O
2
are found under the assumption that N
2
gives rise to a 80% rise of the pressure and that O
2
gives rise to
a 20% rise of the pressure. These are the fractions most commonly used for the composition of air.
2
N
0.80 101325 Pa c =
( )
8 3 1
2.17 10 mol dm Pa
( )
2
2
3 3
N
O
1.759002 10 mol dm
0.20 101325 Pa
c
c
=
=
( )
8 3 1
1.02 10 mol dm Pa
( )
2
4 3
O
2.06703 10 mol dm c =

The total concentration of air in water will approach m
2
, the value for molality.
5-98
2 2
N O
3 3 4 3
3 3
2
1.759002 10 mol dm 2.06703 10 mol dm
1.965705 10 mol dm
c c c
c
c
c m
= +
= +
=

The freezing point depression is given by Eq. 5.121, where K
f
is the freezing point depression constant for water provided by Table 5.2.
fus 2
fus
1.86 K kg
f
T K m
T
=
=
1
mol
( )
3
1.965705 10 mol
1
kg
( )
3
fus
3
fus
3.6562113 10 K
3.66 10 K
T
T
=
=

The freezing point is decreased by 3.6610
-3
K.


5-99
5.50. Using vant Hoffs equation, calculate the osmotic pressure developed if 6.00 g of urea, (NH
2
)
2
CO, is dissolved in 1.00 dm
3
of
solution at 27 C.
Solution:
Given:
3
6.00g, 1.00dm, 300.15 K m V T = = =
Required:
The vant Hoffs Equation for osmotic pressure is given by Eq. 5.134:
( ) ( ) ( ) ( )
2
1 1 1 1
1
or =
where,
2 14.00674 g mol 4 1.007 94 g mol 12.011 g mol 15.9994 g mol
60.05564 g mol
6.00 g
n RT
cRT
V
m
n
M
mRT
MV
M
M

=
=
=
= + + +
=
=
( )
1
8.3145J K
1
mol
( )
300.15 K
( )
60.05564 g
1
mol
( )
3
1.00 dm
3
3
3
m
10
dm
2 2 1 2
2 2 3 3 1 2
3
1 J 1 kg m s
249 203.9049 J m
m m 1 kg m
249 203.9049
249
s 1 Pa
Pa
Pa k

| |
=
|
\ .
=
=
= = =
=
=

5-100
5.51. The apparent value of K
f
in 1.50-molal aqueous sucrose (C
12
H
22
O
11
) solution is 2.17 K kg mol
1
. The solution does not behave
ideally; calculate its activity and activity coefficient (
fus
H =6009.5 J mol
1
).
Solution:
Given:
1 1 1
fus
2.17 K kg mol , 1.50mol kg , 6009.5 J mol
f
K m H

= = =
Required: , a f
To solve for the activity and activity coefficient we start by obtaining
fus
T . We know that the freezing point depression is given by Eq.
5.121:
fus 2
fus
2.17 K kg
f
T K m
T
=
=
1
mol
( )
1.50 mol
1
kg
( )
fus
3.255 K T =

The freezing point depression is
*
.
f fus
T T T = Since
fus
T is small in comparison to
*
,
f
T we may set the product
* *2
.
f f
TT T Substituting the
value of
fus
T into Eq. 5.115, and replacing a
1
for x
1
, we can solve for the activity.
5-101
fus fus
*2
fus
1 *
*
fus
1 *
fus fus
1 *2
1
6009.5 J
1
1 1
ln
ln
ln
m
f
m
f
f
m
f
m
f
H T
R T
H
x
R T T
T T
H
a
R T T
H T
a
R T
a e
a e

| |
= |
|
\ .
| |
= |
|
\ .
| |

= |
|
\ .
=
=
1
mol
8.3145 J
1
K
1
mol
3.255 K
273.15 K ( )
2
0.0315 319 468
1
1
1
0.9689600008
0.969
a e
a
a
=
=
=

5-102
i
=a
i
/x
i
where f
i
is the activity coefficient. (See Section 4.3)
( ) ( ) ( )
( ) ( )
2
2
1
1
1 2
1 1 1
sucrose
1
sucrose
1 1
H O
1
H O
1
12 12.011 gmol 22 1.007 94 g mol 1115.9994 g mol
343.30008 gmol
2 1.007 94 g mol 15.9994 g mol
18.01528 g mol
18.01528 g
m
x
m m
M
M
M
M
x

=
+
= + +
=
= +
=
=
1
mol
343.30008 g
1
mol
18.01528 g
1
mol
343.30008 g
1
mol
3
1.50 10 mol +
1
g
( )
1
1
1
1

0.9874553344
0.9689600008
0.9874553344
0.9812697011
0.981
x
a
f
x
f
f
f
=
=
=
=
=


5-103
5.52. A 0.85-g sample is dissolved in 0.150 kg of bromobenzene. Determine the molar mass of the solute if the solution boils at 429.0 K at
1 atm pressure. The normal boiling point of bromobenzene is 428.1 K and the boiling point elevation constant is 6.26 K kg mol
1
.
Solution:
Given:
bromobenzene ,solution
0.85 g, 0.150 kg, 429.0 K, 1 atm,
b
m m T P = = = =
1
,bromobenzene
428.1 K, 6.26 K kg mol
b b
T K

= =
Required: M
solute

To solve for the molar mass of the solute, we start by obtaining the molality, m
2
, from the expression for the boiling point elevation, given
by Eq. 5.126:
vap 2
vap
2
2
429.0 K
b
b
T K m
T
m
K
m
=
=
=
428.1 K
6.26 K
1
1
2
kg mol
0.1437699681 mol kg m
=

The mass of the solute per kilogram of solvent can be found using the following expression.
3
solute
bromobenzene
0.85 10 kg
m
m
=
0.150 kg
3 solute
bromobenzene
5.666667 10
m
m
=

Solving for the molar mass by using the ratio of solute to solvent, we obtain,
5-104
3
1
5.666667 10
0.1437699681 mol kg
0.0394148148 kg
M
M
=
=
1 3
g
mol 10
kg
1
1
39.4148148 g mol
39 g mol
M
M
=
=


5-105
5.53. If in a colligative properties experiment a solute dissociates, a term i known as vant Hoffs factor, which is the total concentration
of ions divided by the nominal concentration, must be included as a factor. Thus, for the lowering of the freezing point,
fus
T =
imK
f
. Derive an expression that relates to the degree of dissociation and to , the number of particles that would be produced if the
solute were completely dissociated. Then calculate vant Hoffs i factor and for a 0.010-m solution of HCl that freezes at 273.114
K.
Solution:
Given:
fus
T =imK
f
,
HCl
0.010 , 273.114 K
f
m m T = =
Required: expression that relates to the degree of dissociation and to , calculate i, for HCl
For this particular problem, we consider the dissociation of any general compoundA B
x y
to be given by:
A B
x y
xA
z+
+ yB
z-

m
initial
m 0 0 mol kg
-1

m
dissociation
m-m xm ym mol kg
-1

The total molality can therefore be expressed as,
( )
total
1
total
1 mol kg
m m m x m y m
m m x y

= + +
= + +

The term i known as vant Hoffs factor, is the total concentration of ions divided by the nominal concentration. Solving for i, we obtain,
total
initial
m
i
m
m
i
=
=
( ) 1 mol x y + +
1
kg
m mol
1
kg
1 i x y = + +

v is the total number of moles of reactants present, v x y = + , therefore we can obtain an expression of in terms of v.
5-106
( )
1
1 1
1
1
i v
i v
i
v

= +
= +

In the case of HCl, we use K
f
for water, provided by table 5.2.
273.15 K
fus
f
T
i
mK
i
=
=
273.114 K
0.010 mol
1
kg
( )
1.86 K kg
1
mol
1.935483871
1.94
i
i
=
=

The dissociation of HCl is complete and gives v =2,
1.935483871 1
2 1
0.935483871
0.935
=
=

5-107
5.54. In an osmotic pressure experiment to determine the molar mass of a sugar, the following data were taken at 20 C:
/atm 2.59 5.06 7.61 12.75 18.13 23.72
m
2
V
1
/g dm
3
33.5 65.7 96.5 155 209 259

Estimate the molar mass of the sugar. If the sugar is sucrose, what is the percentage error and why?

Solution:

Given: 293.15K T =

Required: M, percent error

The vant Hoffs equation for osmotic pressure is given by Eq. 5.134 which states that:
2
2
2
or =
where,
n RT
cRT
V
m
n
M
m RT
M V

=
=
=

We can rearrange the above expression to isolate for M
2
,
2
2
m RT
M
V
=
Plotting

5-108
5.55. When 3.78 g of a nonvolatile solute is dissolved in 300.0 g of water, the freezing point depression is 0.646 C. Calculate the molar
mass of the compound. K
f
=1.856 K kg mol
1
.
Solution:
Given:
2
1
H O fus
3.78 g, 300.0g, 0.646 C 0.646 K, 1.856 K kg mol
f
m m T K = = = = =
Required: M
To solve this problem, we must simply use Eq. 5.122:
2
2
fus 1
2
1.856 K
f
K W
M
TW
M
=
=
( )
1
kg mol 3.78 g
( )
0.646 K
( )
300.0 g
( )
2
0.0362006192 kg M =
1 3
g
mol 10
kg
1
2
1
2
36.2006192 g mol
36.2 g mol
M
M
=
=

5-109
5.56. Calculate the elevation in the boiling point of water if 6.09 g of a nonvolatile compound with molar mass of 187.4 g mol
1
is
dissolved in 250.0 g of water. Compare the values obtained using Eq. 5.125 and Eq. 5.126. The value of K
b
=0.541 K kg mol
1
;
vap
H =40.66 kJ mol
1
.
Solution:
Given:
2
1
H O
6.09 g, 250.0g, 187.4g mol , m m M

= = =

1 1
vap
0.541 K kg mol , 40.66 kJ mol
b
K H = =
Required:
vap
T
To obtain
vap
T from Eq. 5.125, we first need to find the value for x
1
,
vap
1 *
1 1
ln
m
b
H
x
R T T
| |
=
|
\ .

The mole fraction of water can be determined by using,
( ) ( )
( ) ( )
2
2
2
1 1
1
1 1 2 2
1 1
H O
1
H O
H O
/
/ /
where
2 1.007 94 g mol 15.9994 g mol
18.01528 g mol
250.0 g
m M
x
m M m M
M
M
x

=
+
= +
=
=
18.01528 g
1
mol
250.0 g
18.01528 g
1
mol
6.09g
+
187.4 g
1
mol
2
H O
0.9976640264 x =

Solving for
vap
T , we obtain,
5-110
1 *
vap
1 1
ln
1 8.3145 J
m b
R
x
T H T
T
= +
= ( )
1 1
3 1
1
K mol 1
ln 0.9976640264
40.66 10 J mol 373.15K
1
0.0026794092 K
373.2166022K
T
T

=
=

vap
vap
2
vap
373.2166022K 373.15K
0.0666022K
6.66 10 K
T
T
T

=
=
=

We can also obtain
vap
T from Eq. 5.126. However, we first need to find the value for m
2
,
vap 2 b
T K m =
The molality can be obtained using,
2
2
2
6.09g
n
m
m
m
=
=
187.4 g
1
3
1
2
mol
250.0 10 kg
0.129989327 6 mol kg m
=

Solving for
vap
T , we obtain,
5-111
vap
0.541 K kg T =
1
mol
( )
0.129989327 6 mol
1
kg
( )
vap
vap
0.0703242263 K
7.03 K
T
T
=
=


5-112
5.57. Suppose that you find in the older literature the vapor pressure P of a liquid with molar mass of 63.9 10
3
kg mol
1
listed with P in
mmHg as
log P =5.4672 1427.3 T
1
3169.3 T
2

The densities of the liquid and vapor phases are 0.819 kg dm
3
and 3.15 10
4
kg dm
3
vap
H at the
normal boiling point, 398.4 K. How do you handle the fact that P is listed in mmHg?
Solution:
Given:
3 1 3 4 3
liquid vapor
63.9 10 kg mol , 0.819 kg dm , 3.15 10 kg dm , 398.4 K
b
M T = = = =
Required:
vap
H
We can use the Clapeyron equation to solve this problem, given by Eq. 5.9:
m
m
H dP
dT T V

Since the boiling point is given at 1 atm, it is appropriate for us to express pressure in terms of atmospheres. Since 1 mmHg =1 Torr, then;
( )
( ) ( )
1atm
log / Torr log / atm
760Torr
1atm
log / Torr log / atm log
760Torr
P P
P P
| |
=
|
\ .
| |
= +
|
\ .

The derivative of this expression shows that is does not matter how pressure is expressed as long as we are only considering the ultimate
CHANGE in pressure.
5-113
( )
( ) ( )
( )
( )
10
10
1 2
10
2 3
10
2 2 3
log 1
log
log
log
5.4672 1427.3 3169.3
log
1427.3 2 3169.3
log
1427.3K 6338.6K
0.4342944819
d P dP
e
dT P dT
dP P d P
dT e dT
dP P d
T T
dT e dT
dP P
T T
dT e
dP P
T T
dT
=
=
=
= +
= +

We can now use the Clapeyron equation at T
b
where P =1 atm to solve.
( )
( ) ( )
( )
2 3
2
1
1atm
1427.3 K 398.4K 6338.6K 398.4K
0.4342944819
0.0209366215atmK
dP
dT
dP
dT
= +
=

We can solve for V
m
using the densities given in the problem above to get;
5-114
liquid
liquid
3
liquid
63.9 10 kg
m
m
m
M
V
M
V
V
=
=
=
1
mol
0.819 kg
3
3 1
liquid
vapor
vapor
3
vapor
dm
0.078021978 dm mol
63.9 10 kg
m
m
m
m
V
M
V
V
=
=
=
1
4
mol
3.15 10 kg
3
3 1
vapor
vapor liquid
3 1 3 1
3 1
dm
202.8571429 dm mol
202.8571429 dm mol 0.078021978 dm mol
202.7791209 dm mol
m
m m m
m
m
V
V V V
V
V
=
=
=
=

Rearranging Eq. 5.9, we can solve for
vap
H which yields,
5-115
398.4 K
m
m
m m
m
H dP
dT T V
dP
H T V
dT
H
=
=
( )( )
3 1 1
202.7791209 dm mol 0.0209366215atmK
( )
3 1
3
1691.411065atmdm mol
1 atm dm 101.325 J
101.325 J
1691.411065
atm
m
m
H
H
=
=
=
3
dm
atm
3
dm
1
1
1
mol
171382.2262 J mol
171.4 kJ mol
m
m
H
H
=
=


5-116
5.58. Calculate the osmotic pressure of seawater using the data of Table 5.5. Assume a temperature of 298 K and that the concentration of
the additional salts not listed does not substantially contribute to the osmotic pressure.
Solution:
Given: Table 5.5, T=298 K
Required:
The vant Hoffs Equation for osmotic pressure is given by Eq. 5.134 which states that:
2
or
n RT
cRT
V
= =
To solve for the osmotic pressure of seawater, we must first begin by determining the total molar concentration using data given in Table
5.5.
( )
Cl Na Mg S Ca K Br C
3
3
0.536 0.457 0.0555 0.0276 0.010 0.0097 0.00081 0.0023 mol dm
1.098 91 mol dm
1.098 91 mol
c c c c c c c c c
c
c
= + + + + + + +
= + + + + + + +
=
=
( )
3 1
dm 8.3145 J K
1
mol
( )
298 K
( )
3
2722.792384 J dm

=
3
3
3
m
10
dm
3 3
2 2 1 2
2 2 2
3
1
1 J 1 kg m s 1 m m
2722 792.384 Pa
kg m s
2722.792 384 kPa
2.72 10 Pa
a
k
1 P

=
=
=
= =
= = =


CHAPTER
6
6
Phase Equilibria

Physical Chemistry
Electronic Edition

Chapter 6: Phase Equilibria Number of Components and Degrees of Freedom
6-2
Chapter 6
Number of Components and Degrees of Freedom
6.1. In Figure 6.1, in the region marked orthorhombic, how many degrees of freedom exist? How many components are present? How
many phases? How many phases exist in the region marked monoclinic?
Solution
6.2. What is the composition of the two-phase region in Figure 6.14? How many degrees of freedom exist in this region?
Solution
6.3. Determine the number of degrees of freedom for the following systems:
a. A solution of potassium chloride in water at the equilibrium pressure.
b. A solution of potassium chloride and sodium chloride at 298 K at 1 atm pressure.
c. Ice in a solution of water and alcohol.
Solution
6.4. How many components are present in a water solution of sodium acetate?
Solution
6.5. How many components are present in the system CaCO
3
CaOCO
2
?
Solution
6.6. How many components are present in the following system?
CO(g) +3H
2
(g) CH
4
(g) +H
2
O(g)
Solution
Chapter 6: Phase Equilibria Use of the Lever Rule; Distillation
6-3
6.7. A certain substance exists in two solid phases A and B and also in the liquid and gaseous states. Construct a P-T phase diagram
indicating the regions of stable existence for each phase from the following triple-point data:
T/K P/kPa Phase in Equilibrium
200 100 A, B, gas
300 300 A, B, liquid
400 400 B, liquid, gas
Solution
Use of the Lever Rule; Distillation
6.8. Answer the following questions, using the accompanying figure.
a. A liquid mixture consists of 33 g of component A and 99 g of component B. At what temperature would the mixture begin to
boil?
b. Under the conditions in (a), what is the composition of the vapor when boiling first occurs?
c. If the distillation is continued until the boiling point is raised by 5.0 C, what would be the composition of the liquid left in the
still?
d. Under the conditions in (c), what are the composition and mass of the two components collected over the initial 5.0 C interval?
Solution
Chapter 6: Phase Equilibria Use of the Lever Rule; Distillation
6-4
6.9. From the data of Figure 6.14, calculate the ratio of the mass of the water-rich layer to that of the nicotine-rich layer, for a 40 wt %
waternicotine mixture at 350 K.
Solution
6.10. The ratio of the mass of chlorobenzene to that of water collected in a steam distillation is 1.93 when the mixture was boiled at
343.85 K and 56.434 kPa. If the vapor pressure of water at this temperature is 43.102 kPa, calculate the molar mass of
chlorobenzene.
Solution
6.11. a. Do the actual derivation of Eq. 6.11 from Eq. 6.8.
b. From Eq. 6.8 derive an expression that gives you the ratio of the mass of two volatile components, 1 and 2, in terms of their mole
fractions in the vapor and their molar masses.
Solution
6.12. Obtain an expression for the ratio of masses of the materials distilled in a steam distillation in terms of the molar masses and the
partial pressures of the two components.
Solution
6.13. Under atmospheric pressure 1 kg of pure naphthalene is to be prepared by steam distillation at 372.4 K. What mass of steam is
required to perform this purification? The vapor pressure of pure water at 372.4 K is 98.805 kPa.
Solution
6.14. The vapor pressure of water at 343.85 K is 43.102 kPa. A certain mixture of chlorobenzene and water boils at 343.85 K under a
reduced pressure of 56.434 kPa. What is the composition of the distillate?
Solution
6.15. Calculate the composition of the vapor in equilibrium at 323 K with a liquid solution of 0.600 mol fraction 2-methyl-1-propanol
(isobutyl alcohol) and 0.400 mol fraction 3-methyl-1-butanol (isoamyl alcohol). The vapor pressure of pure isobutyl alcohol is
7.46 kPa and that of pure isoamyl alcohol is 2.33 kPa both at 323 K.
Solution
Chapter 6: Phase Equilibria Construction of Phase Diagrams from Physical Data
6-5
6.16. The thermal expansion coefficient =(1/V) ( / )
P
V T is often used when predicting changes in vapor pressure induced by
temperature changes. From the relation =m/V, show that ( ln / ) .
P
T =

Solution
6.17. At 293.15 K the density of water is 0.998 234 g cm
3
and at 294.15 K it is 0.998 022 g cm
3
under 1 atm of pressure.
Estimate the value of for water at 1 atm.
Solution
6.18. How many theoretical plates are required to separate the mixture shown in Fig. 6.7?
Solution
*6.19. A sealed reaction vessel is completely filled with liquid water at 293.15 K and 1.00 atm. If the temperature is raised exactly 6 K and
the walls of the vessel remain rigid, what is the pressure in the container if the average value of =2.85 10
4
K
1
and the
compressibility coefficient [ (1/ )( / ) ]
T
V V P = is 4.49 10
5
atm
1
?
Solution
Construction of Phase Diagrams from Physical Data
6.20. In Figure 6.16, a solution having composition p is cooled to just above the eutectic temperature (point s is about 0.18 x
Si
, and x
e
is
0.31 x
Si
); calculate the composition of the solid that separates and that of the liquid that remains.
Solution
*6.21. The melting points and heats of fusion of gold and silicon are
Au Si
T/K 1337 1683

fus
H/J mol
1
12 677.5 39 622.5

For the data, calculate the solid-liquid equilibrium lines and estimate the eutectic composition graphically. Compare the result with the
values given by Figure 6.16.
6-6
Solution
6.22. Use the following data to construct a phase diagram of the phenolwater system and answer the following questions (the
compositions are given in grams of phenol in 100 grams of solution):
t/C 20 25 30 35 40
Aqueous layer 8.40 8.71 8.92 9.34 9.78
Phenol layer 72.24 71.38 69.95 68.28 66.81

45 50 55 60 65 68.8
10.62 12.08 13.88 17.10 22.26 35.90
65.02 62.83 60.18 56.10 49.34 35.90

a. What will be the compositions of the layers formed from a solution of 30 g phenol and 70 g water maintained at 30 C?
b. A solution of 20 g phenol and 80 g water is prepared at 70 C. How many phases will be present?
c. At what temperature will two phases appear if the solution in part (b) is cooled gradually? What will be the compositions of the
two phases?
Solution
6-7
6.23. The following information is obtained from cooling curve data on the partial system Fe
2
O
3
Y
2
O
3
[J . W. Nielsen and E. F.
Dearborn, Phys. Chem. Solids, 5, 203(1958)]:
Composition of
Melt/mol % Y
2
O
3

Temperature of Break/C Temperature of Halt/C
0 1550
5 1540 1440
10 1515 1440
15 1450 1440
20 1520 1440
25 1560 1440
30 1620 1575/1440
40 1705 1575
50 1720

Sketch the simplest melting point diagram consistent with these data. Label the phase regions and give the composition of any
compounds formed.
Solution
6.24. The study of cooling curves for the thalliumgold system yields the following data. Construct the phase diagram and identify the
eutectic composition and temperature. Pure gold melts at 1063 C and pure thallium melts at 302 C. In each region, identify the
number of phases and the solid that separates out, if any.
Wt % Au 10 20 30 40 60 80 90
First break (C) 272 204 200 400 686 910 998
Eutectic halt (C) 128 128 128 128 128 128 128

[Data adapted from A. C. K. Smith, Applied Physical Chemistry Problems, London: McGraw-Hill, 1968, p. 13.]
Solution
6-8
6.25. a. From the following information, draw the binary phase diagram for the system FeO (mp. 1370 C)MnO (mp. 1785 C). A
peritectic reaction occurs at 1430 C between solid solution containing 30 mass % MnO and solid solution containing 60 mass %
MnO. These are in equilibrium with melt that contains 15 mass % MnO. At 1200 C the composition of and solution is 28 mass
% and 63 mass %, respectively.
b. Describe what happens as a liquid containing 28 mass % MnO is cooled to 1200 C.
Solution
6.26. The following data for the magnesiumcopper system is the result of analyzing cooling curves. Pure copper melts at 1085 C while
pure magnesium melts at 659 C. Two compounds are formed, one at 16.05 wt % Mg with a melting point of 800 C, and the other
at 43.44 wt % Mg with a melting point of 583 C, respectively. Construct the phase diagram from this information and identify the
compositions of the eutectics. [Data adapted from A. C. K. Smith, Applied Physical Chemistry Problems, London: McGraw-Hill,
1968, p. 14.]
Wt % Mg 5 10 15 20 30 35
First break (C) 900 702 785 765 636 565
Eutectic halt (C) 680 680 680 560 560 560

40 45 50 60 70 80 90
581 575 546 448 423 525 600
560 360 360 360 360 360 360

Solution
6.27. What are the empirical formulae of the compounds represented by the vertical lines formed in the magnesiumcopper system
described in Problem 6.26?
Solution
6-9
6.28. A preliminary thermal analysis of the FeAu system showed two solid phases of composition 8.1 mol % Au and 25.5 mol % Au in
equilibrium at 1168 C with liquid of composition 43 mol % Au. Construct the simplest melting point diagram consistent with this
information and label all the phase regions. Sketch the cooling curves for the composition 10 mol % Au, 30 mol % A, and 60 mol %
Au, and make them consistent with the fact that there is an - phase transition in iron at 903 C and that the -phase field extends to
45 mol % Au at this temperature. Iron melts at 1536 C and gold at 1063 C.
Solution
6.29. The aluminumselenium system was determined from thermal analysis. Al
2
Se
3
melts congruently at approximately 950 C and
forms a eutectic both with aluminum and with selenium at a very low concentration of the alloying element and at a temperature
close to the melting point of the base elements. Draw a diagram from this information and give the composition of the phases.
Aluminum melts at 659.7 C and selenium melts at approximately 217 C.
Solution
*6.30. The metals Al and Ca form the compounds Al
4
Ca and Al
2
Ca. The solids Al, Ca, Al
4
Ca, and Al
2
Ca essentially are immiscible in
each other but are completely miscible as liquids. Maximum Ca solubility in Al is about 2% and occurs at 616 C. Al melts at 659.7
C and Ca melts at 848 C. Compound Al
2
Ca melts congruently at 1079 C and gives a simple eutectic with Ca at 545C.
Compound Al
4
Ca decomposes at 700 C to give Al
2
Ca and a melt, the peritectic lying at 10 mol %. A monotectic exists at 616 C.
At approximately 450 C a transition occurs between -Ca and -Ca.
a. Draw the simplest phase diagram consistent with this information and label all phase regions.
b. Sketch cooling curves for melts of composition 15 mol % Ca and 80 mol % Ca.
Solution
6-10
*6.31. The extent of dehydration of a salt such as CuSO
4
can often be followed by measuring the vapor pressure over the hydrated salt. The
system H
2
OCuSO
4
is shown in the accompanying figure as an example of such a system. Label the areas as to the phase(s) present.
Then describe the sequence of phase changes if a dilute solution of copper sulfate is dehydrated at 275 K, ending with anhydrous
copper sulfate. What would a vacuum gauge read starting with pure water during the dehydration process at 298.15 K? Sketch a plot
of P/Torr against CuSO
4
/wt %. Relevant data are:
The Vapor Pressure of CuSO
4
H
2
O at 298.15 K P/Torr
Vapor +saturated solution +CuSO
4
5H
2
O 16
Vapor CuSO
4
5H
2
O +CuSO
4
3H
2
O 7.85
Vapor +CuSO
4
3H
2
O +CuSO
4
H
2
O 4.32
Vapor +CuSO
4
H
2
O +CuSO
4
0.017
Vapor pressure of water 23.8

Solution
6-11
*6.32. The data in the accompanying table are approximate for the isobaric-isothermal system SnO
2
CaOMgO at 298.15 K and 1 atm.
Sketch a reasonable phase diagram in mol % with SnO
2
at the apex of the triangle. Label all phase regions; the results are known as
composition triangles.
Material In Equilibrium with Solid Phases
SnO
2
(MgO)
2
SnO
2
, CaOSnO
2

(MgO)
2
SnO
2
SnO
2
, (CaO)SnO
2
, MgO
MgO CaO, (CaO)
2
SnO
2

CaO MgO, (CaO)
2
SnO
2

(CaO)
2
SnO
2
CaO, MgO, CaOSnO
2

CaOSnO
2
(CaO)
2
SnO
2
, MgO, (MgO)
2
SnO
2
, SnO
2

Solution
6.33. Sketch the P against T diagram for phosphorous from the following information. White phosphorous melts at 311 K and 0.2 Torr;
red phosphorous melts at 763 K and 43 atm. The white form is more dense than the liquid and the red form is less dense than the
liquid. The vapor pressure of the white form is everywhere greater than that of the red form. Label each area on the plot, and explain
which triple point(s) is (are) stable or metastable.
Solution
6.34. Gigure and Turrell, J. Am. Chem. Soc., 102, 5476(1980), describe three ionic hydrates formed between HF and H
2
O. Sketch the
H
2
O-HF phase diagram in mol % HF from the following information. HF H
2
O melts at 35.2 C, 2HF H
2
O decomposes by a
peritectic reaction at 75 C, and 4HF H
2
O melts at 98.2 C. HF melts at 83.1 C. Label the composition of all regions. The
eutectic occurs at 111 C with monotectics at 71 C, 77 C, and 102 C.
Solution
6.35. In the system AB a line of three-phase equilibrium occurs at 900 K as determined by thermal analysis. A second three-phase
equilibrium occurs at 500 K. Only one halt is observed for any one cooling curve. The compound AB
2
is known and melts at 600 K.
If A melts at 1200 K and B at 700 K, sketch the simplest phase diagram consistent with the given data. Label each region.
Solution
Chapter 6: Phase Equilibria Data Derived from Phase Diagrams of Condensed Systems
6-12
Data Derived from Phase Diagrams of Condensed Systems
6.36. The following questions refer to Figure 6.28:
a. If liquid C were added to the system, what changes would occur if the system originally contained 80% salt A and 20% salt B?
b. What changes would occur if the system originally contained 50% salt A and 50% salt B upon the addition of liquid?
c. If liquid is added to an unsaturated solution of salt A and salt B in solution of composition lying at e, what changes would occur?
Solution
6.37. In the accompanying diagram, due to B. S. R. Sastry and F. A. Hammel, J. Am. Ceramic Soc., 42; 218(1959), identify the
composition of all the areas. Identify the phenomenon associated with each lettered position.

[[Diagram for Problem 6.37. Reprinted with permission of The American Ceramic Society, Post Office Box 6136, Westerville, OH 43086-
6136, Copyright 1964 by the American Ceramic Society. All rights reserved.]]
6-13
Solution
6.38. Describe what happens within the system Mn
2
O
3
Al
2
O
3
in Fig. 6.21 when a liquid of
2 3
A1 O
x =0.2 is cooled from 2100 K to 1200
K.
Solution
6.39. The isobaric solubility diagram for the system acetic acidtoluenewater is shown in Figure 6.27. What phase(s) and their
composition(s) will be present if 0.2 mol of toluene is added to a system consisting of 0.5 mol of water and 0.3 mol of acetic acid?
Give the relative amounts of each phase.
Solution
6.40. A fictitious ternary system composed of liquids A, B, and C was constructed by adding the component B to various binary AC
mixtures and noting the point at which complete miscibility occurred. The following are the mole-percents of A and B at which
complete miscibility was observed. Construct the phase diagram on a triangular graph paper.
x
A
(%) 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0
x
B
(%) 20.0 27.0 30.0 28.0 26.0 22.0 17.0 12.0 7.0

Comment on the variation of the mutual solubility of A and C as B is added.
Solution
6-14
6.41. In organic chemistry it is a common procedure to separate a mixture of an organic liquid in water by adding a salt to it. This is
known as salting out. The ternary system K
2
CO
3
H
2
OCH
3
OH is typical. The system is distinguished by the appearance of the
two-liquid region abc.

a. Describe the phase(s) present in each region of the diagram.
b. What would occur as solid K
2
CO
3
is added to a solution of H
2
O and CH
3
OH of composition x?
c. How can the organic-rich phase in (b) be separated?
d. How can K
2
CO
3
be precipitated from a solution having composition y?
e. Describe in detail the sequence of events when a solution of composition F is evaporated.
Solution
Chapter 6: Phase Equilibria Essay Questions
6-15
Essay Questions
6.42. How is thermal analysis used to determine the liquid-solid equilibria and the eutectic temperature?
6.43. Explain what is meant by a metastable system.
6.44. Outline how isothermal distillation may be used to prepare a pure sample.
6.45. Detail the process by which a pure sample is obtained using a fractionating column.
6.46. What is the difference on a molecular level between a maximum and minimum boiling azeotrope? How do the plots of P against x
and T against x differ?
6.47. How would you distinguish between an azeotrope and a pure compound?
6.48. A synthetic chemist has prepared several zwitterionic compounds in a homogeneous series. With each compound a reproducible
melting point is determined using different samples from a fresh batch of material. If, however, the same sample is used in repeating
the determination, a progressively lower melting-point temperature is obtained. Explain what is happening.
SUGGESTED READING
A. Findlay, Phase Rule (revised and enlarged 9th ed., by A. N. Campbell and N. O. Smith), New York: Dover, 1951.
R. J . Forbes, A Short History of the Art of Distillation, Leiden: E. J . Brill, 1970.
J . H. Hildebrand, J . M. Prausnits, and R. L. Scott, Regular and Related Solutions, New York: Van Nostrand Reinhold, 1970.
W. Hume-Rothery, R. E. Smallman, and C. W. Haworth, The Structure of Metals and Alloys, The Metals and Metallurgy Trust of the
Institute of Metals and the Institution of Metallurgists, London, 1969.
R. G. Laughlin, The Aqueous Phase Behavior of Surfactants, New York: Academic Press, 1994.
C. S. Robinson and E. R. Gilliland, Fractional Distillation, New York: McGraw-Hill, 1950.
B. D. Smith, Design of Equilibrium Stage Processes, New York: McGraw-Hill, 1963.
Specifically on miscibility:
J . S. Walker and C. A. Vance. Scientific American, May 1987, p. 98.
Much of the literature has been reviewed and compiled in several areas. The following are convenient sources of much of the work.
Chapter 6: Phase Equilibria Suggested Reading
6-16
Azeotropic Data, Advances in Chemistry Series No. 35, American Chemical Society, Washington, DC, 1962.
R. P. Elliott, Constitution of Binary Alloys (1st Suppl.), New York: McGraw-Hill, 1965.
M. Hansen, Constitution of Binary Alloys (2nd ed.), New York: McGraw-Hill, 1958.
M. Hirata, S. One, and K. Nagahama, Computer Aided Data Book of Vapor-Liquid Equilibria, New York: Kodansha Limited, Elsevier,
Scientific Publishing Co., 1990.
E. M. Levin, R. Robbins, and H. F. McMurdie, Phase Diagrams for Ceramists, The American Ceramic Society, Inc., 1964; 1969
Supplement (Figures 20674149); E. M. Levin and H. F. McMurdie, 1975 Supplement (Figures 41504999). (Series through 1992.)
T. B. Massalski, Ed. Binary Alloy Phase Diagrams, ASM/NIST Data Program for Alloy Phase Diagrams, ASM International, Materials
Park, Ohio 44073. 2nd Ed., 1990, in three volumes.
W. G. Moffatt, Ed., The Handbook of Binary Phase Diagrams, Genium Publishing Corporation, Schenectady, NY: 1994. (In five volumes.)
G. Petzow and G. Effenberg, Eds., Ternary Alloys, A Comprehensive Compendium of Evaluated Constitutional Data and Phase Diagrams,
Materials Science; International Services GmbH and the Max Planck-Institut fur Metallforschung, Stuttgart, VCH Verlagsgesellschaft mbH,
Weinheim, Germany, 1992. (In five volumes.)
F. A. Shunk, Constitution of Binary Alloys (2nd Suppl.), New York: McGraw-Hill, 1969.
I. Wichterle, J . Linek, and E. Hala, Vapor-Liquid Equilibrium Data Bibliography, New York: Elsevier Science Publishers, 1985. Covers the
literature with four supplements to 1985.

Chapter 6: Phase Equilibria Solutions
6-17
Solutions
6.1. In Figure 6.1, in the region marked orthorhombic, how many degrees of freedom exist? How many components are present? How
many phases? How many phases exist in the region marked monoclinic?
Solution:
The region marked orthorhombic is a single phase region. Since this is the phase diagram for pure sulfur, there is only one component.
From the phase rule, given by Eq. 6.2, 2 f c p = + , with 1 c = and 1 p = , 1 1 2 2 f = + = . The two degrees of freedom are pressure and
temperature.
There is only one phase in the region marked monoclinic.


6-18
6.2. What is the composition of the two-phase region in Figure 6.14? How many degrees of freedom exist in this region?
Solution:
The compositions of the two phases at a particular temperature are:
i. Water saturated with nicotine
ii. Nicotine saturated with water
The number of degrees of freedom is given by Eq . 6.2,
2
2 2 2
2
f c p
f
f
= +
= +
=

6-19
6.3. Determine the number of degrees of freedom for the following systems:
a. A solution of potassium chloride in water at the equilibrium pressure.
b. A solution of potassium chloride and sodium chloride at 298 K at 1 atm pressure.
c. Ice in a solution of water and alcohol.
Solution:
The number of degrees of freedom is given by Eq. 6.2,
2 f c p = +
a. For KCl solution, 2 c = since it completely dissociates into two ions in water, and 1 p = since there is only one phase.
2 1 2
3
f
f
= +
=

However, since equilibrium pressure has been specified, the degrees of freedom drops by one, and
2 f =
b. For KCl and NaCl solution, 3 c = since there are three ions present,
+ - +
K , Cl and Na , and 1 p = since there is only one phase.
3 1 2
4
f
f
= +
=

However, since the restriction of constant pressure has been specified, the degrees of freedom drops by one, and
3 f =
c. For ice, water and alcohol, 2 c = since water and ice are considered one component. 2 p = since there is a solid and a liquid phase.
2 2 2
2
f
f
= +
=

6-20
6.4. How many components are present in a water solution of sodium acetate?
Solution:
The system is given by
2
Ac + H O OH + HAc

Aqueous sodium acetate is a two-component system even though the above hydrolysis takes place, since the equilibrium constant defines
the concentration of OH
-
and HAc if the concentration of sodium acetate is given.


6-21
6.5. How many components are present in the system CaCO
3
CaOCO
2
?
Solution:
There are three components in the system CaCO
3
CaOCO
2
. However, since a chemical reaction can take place in the given system, the
number of components is reduced by the number of equilibrium conditions, in this case 1. Therefore 2 c = .

6-22
6.6. How many components are present in the following system?
CO(g) +3H
2
(g) CH
4
(g) +H
2
O(g)
Solution:
There are four different gases, or components in the above system. However, since a chemical reaction can take place in the given system,
the number of components is reduced by the number of equilibrium conditions, in this case 1. Therefore 3 c = .

6-23
6.7. A certain substance exists in two solid phases A and B and also in the liquid and gaseous states. Construct a P-T phase diagram
indicating the regions of stable existence for each phase from the following triple-point data:
T/K P/kPa Phase in Equilibrium
200 100 A, B, gas
300 300 A, B, liquid
400 400 B, liquid, gas
Solution:

6-24
6.8. Answer the following questions, using the accompanying figure.
a. A liquid mixture consists of 33 g of component A and 99 g of component B. At what temperature would the mixture begin to
boil?
b. Under the conditions in (a), what is the composition of the vapor when boiling first occurs?
c. If the distillation is continued until the boiling point is raised by 5.0 C, what would be the composition of the liquid left in the
still?

d. Under the conditions in (c), what are the composition and mass of the two components collected over the initial 5.0 C interval?
Solution:
a. To calculate the temperature at which the mixture would begin to boil, we need to find the weight percent of the component B.
B
A B
weight % B 100%
99g
weight % B 100%
33g 99g
weight % B 75%
m
m m
=
+
=
+
=

The temperature corresponding to 75% B is approximately 60 C, where the mixture first begins to boil.
6-25
60 C T
b. The composition of the vapor is given by the intersection of the tie line at the vapor curve. In this case, the vapor has a composition of
approximately 88% B
weight % B 88%
c. The boiling temperature becomes 65.0 C. The composition of the vapor is approximately 53% B
weight % B 53%

d. using the average composition of the distillates as the value halfway between the initial and final composition of the distillates, we obtain,
( )
1
weight % B 88% 70%
2
weight % B 79%
= +
=

Let W
R
=mass of residue and W
D
=mass of distillate
total R D
132g W W W = + =
Then, applying the condition that B is distributed through the residue and distillate, we obtain
6-26
( )
B inresidue B indistillate
R D
D D
D D
D
D
D
R
R
99 g
0.53 0.79 99 g
0.53 132g 0.79 99 g
69.96 g 0.53 0.79 99 g
69.96 g 0.26 99 g
99 g 69.96 g
0.26
111.6923077g
132 g 111.6923077g
20.30769231g
m m
W W
W W
W W
W
W
W
W
W
+ =
+ =
+ =
+ =
+ =
=
=
=
=

The distillate is therefore 79% of the value of W
D
,
( )
B indistillate D
B indistillate
B indistillate
B indistillate
A indistillate
A indistillate
A indistillate
0.79
0.79 111.6923077g
88.23692308g
88.2g
111.6923077g 88.23692308g
23.45538462g
23.5g
m W
m
m
m
m
m
m
=
=
=
=
=
=
=


6-27
6.9. From the data of Figure 6.14, calculate the ratio of the mass of the water-rich layer to that of the nicotine-rich layer, for a 40 wt %
waternicotine mixture at 350 K.
Solution:
Given: Figure 6.14, 40wt % water nicotine, 350 K T =
Required:
water
nicotine
m
m

From Figure 6.14, the composition at 350 K at equilibrium between the single-phase water-rich layer and the two-phase region is
approximately 10% nicotine. For the equilibrium value on the nicotine-rich side, the value is approximately 75% nicotine.
Using the lever rule, given by Eq. 6.16, we can solve for the ratio,
1 1
1
T
v T
n y x pv
n x x lp
= =
water
nicotine
water
nicotine
water
nicotine
water
nicotine
75 40
4010
35
30
1.166666667
1.2
m
m
m
m
m
m
m
m
=
=
=
=

6-28
6.10. The ratio of the mass of chlorobenzene to that of water collected in a steam distillation is 1.93 when the mixture was boiled at
343.85 K and 56.434 kPa. If the vapor pressure of water at this temperature is 43.102 kPa, calculate the molar mass of
chlorobenzene.
Solution:
Given:
chlorobenzene
water
water
1.93, 343.85K, 56.434kPa, 43.102kPa
m
T P P
m
= = = =
Required:
chlorobenzene
M
Using Eq. 6.21,
*
*
A A
B B
n P
n P
=
Using,
m
n
M
= we can rearrange and solve for
chlorobenzene
M ,
( ) ( )
*
chlorobenzene water chlorobenzene
*
water chlorobenzene water
*
chlorobenzene water water
chlorobenzene *
water chlorobenzene
1 1
water
1
water
2 1.007 94 g mol 15.9994 g mol
18.01528 g mol
m M P
m M P
m M P
M
m P
M
M

=
=
= +
=

The vapor pressure of pure chlorobenzene is obtained using Daltons law of partial pressures,
6-29
( )
* *
chlorobenzene water
*
chlorobenzene
*
chlorobenzene
1
chlorobenzene
56.434kPa 43.102kPa
13.332kPa
43.102 kPa
1.93 18.01528 g mol
P P P
P
P
M

=
=
=
=
13.332 kPa
1
chlorobenzene
1
chlorobenzene
112.408834g mol
112.41g mol
M
M
=
=

The actual molar mass of chlorobenzene, C
6
H
5
Cl is
( ) ( ) ( )
1 1 1
chlorobenzene
1
chlorobenzene
6 12.011 g mol 5 1.007 94 g mol 35.4527 g mol
112.5584 g mol
M
M

= + +
=

6-30
6.11. a. Do the actual derivation of Eq. 6.11 from Eq. 6.8.
b. From Eq. 6.8 derive an expression that gives you the ratio of the mass of two volatile components, 1 and 2, in terms of their mole
fractions in the vapor and their molar masses.
Solution:
a. Equation 6.11 is given by
* *
1 2
* * *
1 2 1 1
( )
P P
P
P P P y
=
+

We can manipulate Eq. 6.8 to obtain the same result.
1
1
P
y
P
=
The total pressure is given by the sum of partial pressures of each of the components in a mixture, hence,
1 2
P P P = +
Raoults Law is given by Eq. 5.26, therefore we can use it solve for P
* *
1 1 1 2 2 2
; P x P P x P = =
( )
( )
1 2
* *
1 1 2 2
* *
1 1 1 2
* * *
1 1 2 1 2
* * *
1 2 1 2
1
P P P
P x P x P
P x P x P
P x P P x P
P P P x P
= +
= +
= +
= +
= +

b. Using Eq. 6.8, we can obtain an expression for x
1
,
6-31
( )
1
1
*
1 1
1
* * *
2 1 1 2
P
y
P
x P
y
P x P P
=
=
+

Solving for x
1
gives
( )
( )
( )
* * * *
1 1 1 2 1 1 1 2
* * * *
1 1 1 1 2 1 2
*
1 2
1
* * *
1 1 1 2
x P y P y x P P
x P y P P y P
y P
x
P y P P
= +
( =

=

This expression may now be substituted back into Eq. 6.9 with the elimination of x
1
. The result is
( )
( )
( ) ( ) ( )
( )
( )
*
* * * 1 2
1 2 2
* * *
1 1 2 1
* * * * * * *
1 2 1 2 2 1 1 2 1
* * *
1 1 2 1
* * *
1 2 1 2
y P
P P P P
y P P P
y P P P P y P P P
P
y P P P
y P P P
P
= +

+
=

=
( )
* * *
1 2 1 2
y P P P +
( )
( )
* *
1 2
* * *
1 1 2 1
* *
1 2
* * *
1 1 2 1
P P
y P P P
P P
P
y P P P
=

6-32
Multiplying by
1
1
to remove the negative sign, we obtain,

( )
* *
1 2
* * *
1 1 1 2
P P
P
P y P P
=

Which is the same equation as Eq. 6.11.


6-33
6.12. Obtain an expression for the ratio of masses of the materials distilled in a steam distillation in terms of the molar masses and the
partial pressures of the two components.
Solution:
To solve this problem, we can use the expression for the composition of vapor, given by Eq. 6.21,
*
*
A A
B B
n P
n P
=
Using,
m
n
M
= we can rearrange and solve for the masses of the materials distilled
*
A B A
*
B A B
*
A A A
*
B B B
m M P
m M P
m P M
m P M
=
=


6-34
6.13. Under atmospheric pressure 1 kg of pure naphthalene is to be prepared by steam distillation at 372.4 K. What mass of steam is
required to perform this purification? The vapor pressure of pure water at 372.4 K is 98.805 kPa.
Solution:
Given:
*
naphthalene water
101.325kPa, 1kg, 372.4K, 98.805kPa P m T P = = = =
Required:
steam
m
*
*
A A
B B
n P
n P
=
Using,
m
n
M
*
A B A
*
B A B
*
A A A
*
B B B
*
steam steam naphthalene
steam *
naphthalene naphthalene
m M P
m M P
m P M
m P M
P M m
m
P M
=
=
=

The vapor pressure of pure naphthalene is obtained using Daltons law of partial pressures,
( ) ( )
2
* *
naphthalene water
*
naphthalene
*
naphthalene
1 1
steam H O
1
steam
101.325kPa 98.805kPa
2.52kPa
2 1.007 94 g mol 15.9994 g mol
18.01528 g mol
P P P
P
P
M M
M

=
=
=
= = +
=

6-35
The formula for naphthalene is C
10
H
8
, therefore the molar mass is
( ) ( )
1 1
naphthalene
1
naphthalene
10 12.011 g mol 8 1.007 94 g mol
128.17352g mol
M
M

= +
=

Solving for the mass of steam, we obtain
steam
98.805 kPa
m =
( )
18.01528 g
1
mol
( )
( ) 1kg
2.52 kPa
( )
128.17352 g
1
mol
( )
steam
steam
5.510809449kg
5.5108kg
m
m
=
=


6-36
6.14. The vapor pressure of water at 343.85 K is 43.102 kPa. A certain mixture of chlorobenzene and water boils at 343.85 K under a
reduced pressure of 56.434 kPa. What is the composition of the distillate?
Solution:
Given:
*
water
343.85K, 43.102kPa, 56.434kPa T P P = = =
Required:
chlorobenzene
water
m
m

*
*
A A
B B
n P
n P
=
Using,
m
n
M
*
A B A
*
B A B
*
A A A
*
B B B
*
chlorobenzene chlorobenzene chlorobenzene
*
water water water
m M P
m M P
m P M
m P M
m P M
m P M
=
=
=

The vapor pressure of pure chlorobenzene is obtained using Daltons law of partial pressures,
* *
chlorobenzene water
*
chlorobenzene
*
chlorobenzene
56.434kPa 43.102kPa
13.332kPa
P P P
P
P
=
=
=

The formula for chlorobenzene is C
6
H
5
Cl therefore the molar mass is
6-37
( ) ( ) ( )
( ) ( )
1 1 1
chlorobenzene
1
chlorobenzene
1 1
water
1
water
chlorobenzene
water
6 12.011 g mol 5 1.007 94 g mol 35.4527 g mol
112.5584 g mol
2 1.007 94 g mol 15.9994 g mol
18.01528 g mol
13.332 kPa
M
M
M
M
m
m

= + +
=
= +
=
=
( )
112.5584 g
1
mol
( )
43.102 kPa
( )
18.01528 g
1
mol
( )

chlorobenzene
water
chlorobenzene
water
1.932567968
1.9326
m
m
m
m
=
=

The sample contains 1.9326 g of chlorobenzene for each 1.000 g of water.


6-38
6.15. Calculate the composition of the vapor in equilibrium at 323 K with a liquid solution of 0.600 mol fraction 2-methyl-1-propanol
(isobutyl alcohol) and 0.400 mol fraction 3-methyl-1-butanol (isoamyl alcohol). The vapor pressure of pure isobutyl alcohol is
7.46 kPa and that of pure isoamyl alcohol is 2.33 kPa both at 323 K.
Solution:
Given:
* *
isobutyl alcohol isoamyl alcohol isobutyl alcohol isoamyl alcohol
323K, 0.600, 0.400, 7.46kPa, 2.33kPa T x x P P = = = = =
Required:
isoamyl alcohol isobutyl alcohol
, y y
To determine the composition of the vapor in equilibrium, we can use Eq. 6.18,
( )( )
( )( ) ( )( )
*
1 1
1 * *
1 1 2 2
*
a a
a * *
a a b b
a
a
a
b a
b
b
b
0.600 7.46kPa
0.600 7.46kPa 0.400 2.33kPa
0.827 6627219
0.828
1
1 0.827 6627219
0.1723372781
0.172
x P
y
x P x P
x P
y
x P x P
y
y
y
y y
y
y
y
=
+
=
+
=
+
=
=
=
=
=
=

6-39
6.16. The thermal expansion coefficient =(1/V) ( / )
P
V T is often used when predicting changes in vapor pressure induced by
temperature changes. From the relation =m/V, show that ( ln / ) .
P
T =

Solution:
To solve this problem, we first take the natural logarithm of the density expression to cast it into a more useful form.
ln ln ln ln
m
V
m
m V
V
=
| |
= =
|
\ .

Taking the partial derivative with respect to T gives,
ln ln
P
m
T T
| |
=
|

\ .
ln
ln ln
ln 1
P
P P
P P
V
T
V
T T
V
T V T
| |
\ .
| | | |
=
| |

\ . \ .
| | | |
=
| |

\ . \ .

The thermal expansion coefficient is given by =(1/V) ( / )
P
V T , hence,
ln 1
ln
P P
P
V
T V T
T
| | | |
= =
| |

\ . \ .
| |
=
|
\ .

6-40
6.17. At 293.15 K the density of water is 0.998 234 g cm
3
and at 294.15 K it is 0.998 022 g cm
3
under 1 atm of pressure.
Estimate the value of for water at 1 atm.
Solution:
Given:
3 3
water water
293.15K, 0.998234 g cm , 294.15 K, 0.998022 g cm , 1atm T T P = = = = =
Required:
To solve this problem, we can use the expression for obtained in problem 6.16
1 1
P
V V
V T V T
| |
=
|

\ .

We make the approximation since we are considering small changes in T and V.
Density is given by,
m
V
= , and can be rearranged to solve for V. Therefore we obtain the expression,
2 1
1 2 1
1 2 1
2 1
1 V V
V T T
m m
m T T
| |
=
|
\ .
| |
|
| =
|
|
\ .

We can set m, the mass of water, equal to 1 gram and solve for
6-41
0.998234 g
=
3
cm
1g
1g
0.998022 g
3
cm
1g
0.998234 g
3
cm
4 1
4 1
294.15 K 293.15 K
2.12420167 10 K
2.1242 10 K

| |
|
|
|
|
|
\ .
=
=


6-42
6.18. How many theoretical plates are required to separate the mixture shown in Fig. 6.7?
Solution:
There are six full horizontal steps and two fractional steps in Figure 6.7. There are therefore approximately six theoretical plates required to
separate the mixture.


6-43
6.19. A sealed reaction vessel is completely filled with liquid water at 293.15 K and 1.00 atm. If the temperature is raised exactly 6 K and
the walls of the vessel remain rigid, what is the pressure in the container if the average value of =2.85 10
4
K
1
and the
compressibility coefficient [ (1/ )( / ) ]
T
V V P = is 4.49 10
5
atm
1
?
Solution:
Given:
4 1 5 1
293.15K, 1atm, 6 K, 2.85 10 K , 4.49 10 atm T P T = = = = =
Required: P
From chapter 3, Eq. 3.139 defines the expansion coefficient as
1
P
V
V T
| |
\ .

To solve for P we rearrange the two expressions for and in the following manner,
From 1
1
V P T
P T V
T V P
V
| | | | | |
=
| | |

\ . \ . \ .
=
V
P
V
T
(
| |
( |
( \ .

P
V
4 1
Therefore
2.85 10 K
T
V
P
T
P T

(
| |
( |
\ .

| |
=
|
\ .
=
5 1
6 K
4.49 10 atm

38.084 632 52 atm

38.1 atm
P
P
=
=

6-44
6.20. In Figure 6.16, a solution having composition p is cooled to just above the eutectic temperature (point s is about 0.18 x
Si
, and x
e
is
0.31 x
Si
); calculate the composition of the solid that separates and that of the liquid that remains.
Solution:
Given: Figure 6.16,
Si Si
0.18 , 0.31
s e
x x x x = =
Required: p
Using the lever rule, given by Eq. 6.16, we can solve for the ratio,
solidlayer
solidlayer liquidlayer
0.18
0.31
0.5806451613
0.58
m
p
m m
p
p
p
=
+
=
=
=

This means that there is 58% solid and 42% liquid in the two-phase region. The overall composition of the liquid above the liquid line is x
Si

=0.31.

6-45
6.21. The melting points and heats of fusion of gold and silicon are
Au Si
T/K 1337 1683

fus
H/J mol
1
12 677.5 39 622.5

For the data, calculate the solid-liquid equilibrium lines and estimate the eutectic composition graphically. Compare the result with the
values given by Figure 6.16.
Solution:
The temperature at which solid solvent is in equilibrium with liquid solvent, with mole fraction x
1
fus
1 *
1 1
ln
m
f
H
x
R T T
| |
=
|
\ .

Values of x
1
and T determined from this equation for each component give the desired liquidus lines in the regions near large values of x
1
.
Several values are:
x
1

T (K)
x
1

T (K)
0.945 1650 0.969 1300
0.863 1600 0.924 1250
0.784 1550 0.879 1200
0.708 1500 0.783 1100
0.564 1400 0.681 1000
6-46

A plot is shown on which the points represent data points and the solid curves are experimental curves of Figure 6.16. The dotted lines
intersect at about x
Si
=0.28, compared to the actual about x
Si
=0.31. However, the eutectic temperature is approximately 400 K too high.
6-47
6.22. Use the following data to construct a phase diagram of the phenolwater system and answer the following questions (the
compositions are given in grams of phenol in 100 grams of solution):
t/C 20 25 30 35 40
Aqueous layer 8.40 8.71 8.92 9.34 9.78
Phenol layer 72.24 71.38 69.95 68.28 66.81

45 50 55 60 65 68.8
10.62 12.08 13.88 17.10 22.26 35.90
65.02 62.83 60.18 56.10 49.34 35.90

a. What will be the compositions of the layers formed from a solution of 30 g phenol and 70 g water maintained at 30 C?
b. A solution of 20 g phenol and 80 g water is prepared at 70 C. How many phases will be present?
c. At what temperature will two phases appear if the solution in part (b) is cooled gradually? What will be the compositions of the
two phases?
Solution:
6-48
Graphing the data, we generate a phase diagram of the phenol-water system.
a. The tie lines drawn through the point (a) indicate that the two layers will have compositions of approximately 8.92% phenol by mass
in the aqueous layer, and 69.95% phenol by mass in the phenol layer at 30 C.
b. The point (b) lies in the region of the diagram where only one phase is present.
c. Two phases appear at approximately 63.0 C. The composition of the two layers will be 19.6% phenol by mass in the aqueous layer
and 52.5% phenol by mass in the phenol layer.


6-49
6.23. The following information is obtained from cooling curve data on the partial system Fe
2
O
3
Y
2
O
3
[J . W. Nielsen and E. F.
Dearborn, Phys. Chem. Solids, 5, 203(1958)]:
Composition of
Melt/mol % Y
2
O
3

Temperature of Break/C Temperature of Halt/C
0 1550
5 1540 1440
10 1515 1440
15 1450 1440
20 1520 1440
25 1560 1440
30 1620 1575/1440
40 1705 1575
50 1720

Sketch the simplest melting point diagram consistent with these data. Label the phase regions and give the composition of any
compounds formed.
Solution:
Each halt corresponds to a line of three-phase equilibrium and each break to a boundary between a one- and two-phase region. At 50%
Y
2
O
3
, a compound is formed and may be written as Fe
2
O
3
Y
2
O
3
or YFeO
3
.
6-50

A compound unstable above 1575 C is indicated between 30% and 40% Y
2
O
3
. This might be taken to be 2Fe
2
O
3
Y
2
O
3
at 33% Y
2
O
3
, but
actually, the formula is Y
3
Fe
5
O
12
, corresponding to 3 Y
2
O
3
+5 Fe
2
O
3
at 37% Y
2
O
3
.

6-51
6.24. The study of cooling curves for the thalliumgold system yields the following data. Construct the phase diagram and identify the
eutectic composition and temperature. Pure gold melts at 1063 C and pure thallium melts at 302 C. In each region, identify the
number of phases and the solid that separates out, if any.
Wt % Au 10 20 30 40 60 80 90
First break (C) 272 204 200 400 686 910 998
Eutectic halt (C) 128 128 128 128 128 128 128

[Data adapted from A. C. K. Smith, Applied Physical Chemistry Problems, London: McGraw-Hill, 1968, p. 13.]
Solution:

By extending the smooth curves drawn through the given data points to the eutectic temperature, the composition of the eutectic is
identified as 26 wt. % Au.


6-52
6.25. a. From the following information, draw the binary phase diagram for the system FeO (mp. 1370 C)MnO (mp. 1785 C). A
peritectic reaction occurs at 1430 C between solid solution containing 30 mass % MnO and solid solution containing 60 mass %
MnO. These are in equilibrium with melt that contains 15 mass % MnO. At 1200 C the composition of and solution is 28 mass
% and 63 mass %, respectively.
b. Describe what happens as a liquid containing 28 mass % MnO is cooled to 1200 C.
Solution:
a.

b. As liquid of 28 mass % MnO cools, first forms along with liquid. At 1430 C, converts to and +L remains only briefly at
the temperature is lowered about 50 C, at which point all the liquid is reconverted to the phase. The compositions are given by
the lever rule. As 1200 C is approached, some may again make an appearance.


6-53
6.26. The following data for the magnesiumcopper system is the result of analyzing cooling curves. Pure copper melts at 1085 C while
pure magnesium melts at 659 C. Two compounds are formed, one at 16.05 wt % Mg with a melting point of 800 C, and the other
at 43.44 wt % Mg with a melting point of 583 C, respectively. Construct the phase diagram from this information and identify the
compositions of the eutectics. [Data adapted from A. C. K. Smith, Applied Physical Chemistry Problems, London: McGraw-Hill,
1968, p. 14.]
Wt % Mg 5 10 15 20 30 35
First break (C) 900 702 785 765 636 565
Eutectic halt (C) 680 680 680 560 560 560

40 45 50 60 70 80 90
581 575 546 448 423 525 600
560 360 360 360 360 360 360

6-54
Solution:

From the graph, the first eutectic temperature, 680 C, has a composition of 10.5 wt. % Mg, the second eutectic temperature, 560 C, has a
composition of 35.0 wt. % Mg, while the third eutectic temperature, 360 C has a composition of 65 wt. % Mg.

6-55
6.27. What are the empirical formulae of the compounds represented by the vertical lines formed in the magnesiumcopper system
described in Problem 6.26?
Solution:
Assuming that there are 100 g of the first compound, we have 16.05 g of Mg and 100g 16.05g 83.95g = Cu. The mole ratios of Mg : Cu
are,
Mg Mg Cu
Cu Cu Mg
Mg
Cu
16.05 g
n m M
n m M
n
n
=
=
( )
63.546 g
1
mol
( )
83.95 g
( )
24.3050 g
1
mol
( )
Mg
Cu
Mg
Cu
0.4998583247
1
2
n
n
n
n
=

Therefore the empirical formula of the first compound is MgCu
2
.
Assuming that there are 100 g of the second compound, we have 43.44 g of Mg and 100g 43.44g 56.56g = Cu. The mole ratios of Mg :
Cu are,
Mg Mg Cu
Cu Cu Mg
Mg
Cu
43.44 g
n m M
n m M
n
n
=
=
( )
63.546 g
1
mol
( )
56.56 g
( )
24.3050 g
1
mol
( )
Mg
Cu
Mg
Cu
2.008043001
2
n
n
n
n
=

6-56
Therefore the empirical formula of the second compound is Mg
2
Cu.

6-57
6.28. A preliminary thermal analysis of the FeAu system showed two solid phases of composition 8.1 mol % Au and 25.5 mol % Au in
equilibrium at 1168 C with liquid of composition 43 mol % Au. Construct the simplest melting point diagram consistent with this
information and label all the phase regions. Sketch the cooling curves for the composition 10 mol % Au, 30 mol % A, and 60 mol %
Au, and make them consistent with the fact that there is an - phase transition in iron at 903 C and that the -phase field extends to
45 mol % Au at this temperature. Iron melts at 1536 C and gold at 1063 C.
Solution:
The coexistence of the three phases is a clear indication of a peritectic-type diagram. A note of caution is in order here: In the range 0-
10mol% Au at 1430 C to 1536 C, still another phase, called exists. This would not be detected using only the compositions listed. One
must be careful to use enough composition to ensure that all phases are identified. Also, the equilibrium between liquid and is not a simple
curve and must be determined by careful experimentation.
6-58


6-59
6.29. The aluminumselenium system was determined from thermal analysis. Al
2
Se
3
melts congruently at approximately 950 C and
forms a eutectic both with aluminum and with selenium at a very low concentration of the alloying element and at a temperature
close to the melting point of the base elements. Draw a diagram from this information and give the composition of the phases.
Aluminum melts at 659.7 C and selenium melts at approximately 217 C.
Solution:


6-60
*6.30. The metals Al and Ca form the compounds Al
4
Ca and Al
2
Ca. The solids Al, Ca, Al
4
Ca, and Al
2
Ca essentially are immiscible in
each other but are completely miscible as liquids. Maximum Ca solubility in Al is about 2% and occurs at 616 C. Al melts at 659.7
C and Ca melts at 848 C. Compound Al
2
Ca melts congruently at 1079 C and gives a simple eutectic with Ca at 545C.
Compound Al
4
Ca decomposes at 700 C to give Al
2
Ca and a melt, the peritectic lying at 10 mol %. A monotectic exists at 616 C.
At approximately 450 C a transition occurs between -Ca and -Ca.
a. Draw the simplest phase diagram consistent with this information and label all phase regions.
b. Sketch cooling curves for melts of composition 15 mol % Ca and 80 mol % Ca.
Solution:
a. The lower phase field of the -phase is less than 1%

6-61
b.

6-62
6.31. The extent of dehydration of a salt such as CuSO
4
can often be followed by measuring the vapor pressure over the hydrated salt. The
system H
2
OCuSO
4
is shown in the accompanying figure as an example of such a system. Label the areas as to the phase(s) present.
Then describe the sequence of phase changes if a dilute solution of copper sulfate is dehydrated at 275 K, ending with anhydrous
copper sulfate. What would a vacuum gauge read starting with pure water during the dehydration process at 298.15 K? Sketch a plot
of P/Torr against CuSO
4
/wt %. Relevant data are:
The Vapor Pressure of CuSO
4
H
2
O at 298.15 K P/Torr
Vapor +saturated solution +CuSO
4
5H
2
O 16
Vapor CuSO
4
5H
2
O +CuSO
4
3H
2
O 7.85
Vapor +CuSO
4
3H
2
O +CuSO
4
H
2
O 4.32
Vapor +CuSO
4
H
2
O +CuSO
4
0.017
Vapor pressure of water 23.8
6-63

Solution:
6-64

In the upper figure, CuSO
4
begins in a solution single-phase region. Pure CuSO
4
5H
2
O precipitates out as the first phase boundary at a is
crossed. Water continues to be removed as more CuSO
4
5H
2
O precipitates until only pure CuSO
4
5H
2
O is present at b. In the next two-
phase region, CuSO
4
5H
2
O dehydrates, forming progressively more CuSO
4
3H
2
O, until all of the pentahydrate is gone at c. The process
repeats, the trihydrate forming the monohydrate, until only monohydrate is present at d. The monohydrate dehydrates until at e only pure
CuSO
4
is present.

6-65
In the lower figure, the vapor pressure of water drops as the amount of CuSO
4
increases, (according to Raoults Law), until the solution is
saturated with respect to the pentahydrate. The system is invariant since three phases, vapor, saturated solution and solid CuSO
4
5H
2
O, are
present at the constant temperature of 298.15 K. As the concentration of CuSO
4
increases, (water is removed), the pressure remains
constant until only CuSO
4
5H
2
O is present. Removal of additional water causes some trihydrate to form, and the pressure drops. Again the
system is invariant; three phases are present, vapor CuSO
4
5H
2
O, and CuSO
4
3H
2
O. The process is continued as before at the other stages.

6-66
6.32. The data in the accompanying table are approximate for the isobaric-isothermal system SnO
2
CaOMgO at 298.15 K and 1 atm.
Sketch a reasonable phase diagram in mol % with SnO
2
at the apex of the triangle. Label all phase regions; the results are known as
composition triangles.
Material In Equilibrium with Solid Phases
SnO
2
(MgO)
2
SnO
2
, CaOSnO
2

(MgO)
2
SnO
2
SnO
2
, (CaO)SnO
2
, MgO
MgO CaO, (CaO)
2
SnO
2

CaO MgO, (CaO)
2
SnO
2

(CaO)
2
SnO
2
CaO, MgO, CaOSnO
2

CaOSnO
2
(CaO)
2
SnO
2
, MgO, (MgO)
2
SnO
2
, SnO
2

Solution:
The system SnO
2
CaOMgO is given by,

6-67
6.33. Sketch the P against T diagram for phosphorous from the following information. White phosphorous melts at 311 K and 0.2 Torr;
red phosphorous melts at 763 K and 43 atm. The white form is more dense than the liquid and the red form is less dense than the
liquid. The vapor pressure of the white form is everywhere greater than that of the red form. Label each area on the plot, and explain
which triple point(s) is (are) stable or metastable.
Solution:

a. Stable triple point R (red phosphorus, solid), liquid (L), vapor (V).
b. Metastable triple point W (white phosphorus, solid), L, V. The vapor pressure of white phosphorus is greater than that of the red.
c. Stable triple point W, R, L. If we assumes that a solid cannot be superheated, the triple point W, R, L is totally unstable since it
probably lies above the melting point of the liquid.

6-68
6.34. Gigure and Turrell, J. Am. Chem. Soc., 102, 5476(1980), describe three ionic hydrates formed between HF and H
2
O. Sketch the
H
2
O-HF phase diagram in mol % HF from the following information. HF H
2
O melts at 35.2 C, 2HF H
2
O decomposes by a
peritectic reaction at 75 C, and 4HF H
2
O melts at 98.2 C. HF melts at 83.1 C. Label the composition of all regions. The
eutectic occurs at 111 C with monotectics at 71 C, 77 C, and 102 C.
Solution:

6-69
6.35. In the system AB a line of three-phase equilibrium occurs at 900 K as determined by thermal analysis. A second three-phase
equilibrium occurs at 500 K. Only one halt is observed for any one cooling curve. The compound AB
2
is known and melts at 600 K.
If A melts at 1200 K and B at 700 K, sketch the simplest phase diagram consistent with the given data. Label each region.
Solution:
The 500 K equilibrium line probably contains a eutectic since the temperature is below the melting points of both AB
2
and B. An unstable
compound is rules out because such a reaction would require cooling halts of both 900 K and 500 K. Instead, a peritectic reaction shown is
the simplest explanation.

6-70
6.36. The following questions refer to Figure 6.28:
a. If liquid C were added to the system, what changes would occur if the system originally contained 80% salt A and 20% salt B?
b. What changes would occur if the system originally contained 50% salt A and 50% salt B upon the addition of liquid?
c. If liquid is added to an unsaturated solution of salt A and salt B in solution of composition lying at e, what changes would occur?
Solution:
a. As liquid C is added, the saturated liquid of composition b would be in equilibrium with the two solids A and B. At approximately
20% C, when the composition crosses the line bB, the solid A disappears and only solid B will be present in equilibrium with liquid
of composition b.
b. The two solid phases would not disappear until b is passed at approximately 50% liquid C.
c. Added liquid would cause dilution and the solid salt will no longer exist.

6-71
6.37. In the accompanying diagram, due to B. S. R. Sastry and F. A. Hammel, J. Am. Ceramic Soc., 42; 218(1959), identify the
composition of all the areas. Identify the phenomenon associated with each lettered position.

[[Diagram for Problem 6.37. Reprinted with permission of The American Ceramic Society, Post Office Box 6136, Westerville, OH 43086-
6136, Copyright 1964 by the American Ceramic Society. All rights reserved.]]
6-72
Solution:

a. Peritectic point
b. Eutectic point
c. Melting point
d. Incongruent melting
e. Phase transition

6-73
6.38. Describe what happens within the system Mn
2
O
3
Al
2
O
3
in Fig. 6.21 when a liquid of
2 3
A1 O
x =0.2 is cooled from 2100 K to 1200
K.
Solution:
At 2100 K, the mixture is in the liquid state. As the liquid is cooled, solid spinel first appears at about 1950 K in equilibrium with liquid. At
approximately 1875 K, all of the liquid converts to solid spinel, the composition of which varies according to the lever rule.
As the temperature falls to about 1400 K, a two-phase region appears that is Mn
3
O
4
+
spinel. Below about 1285 K, the spinel converts to
corundum and Mn
3
O
4
+
corundum coexist.

6-74
6.39. The isobaric solubility diagram for the system acetic acidtoluenewater is shown in Figure 6.27. What phase(s) and their
composition(s) will be present if 0.2 mol of toluene is added to a system consisting of 0.5 mol of water and 0.3 mol of acetic acid?
Give the relative amounts of each phase.
Solution:
Given: Figure 6.27,
toluene water acetic acid
0.2 mol, 0.5 mol, 0.3 mol n n n = = =
Required: phases, composition, relative amounts
Using the number of moles present, the composition of the system is 20% toluene, 50% water and 30% acetic acid.
The system point is practically on the p q tie line, and there are therefore two liquids present. The ends of this line, and thus the
concentrations of the two liquids are approximately,
a. 95.5% toluene, 4% acetic acid, 0.5% water
b. 1% toluene, 37% acetic acid, 62% water

To calculate the relative amounts of the two liquids, we can use the lever rule, given by Eq. 6.16,
1 1
1
T
v T
n y x pv
n x x lp
= =
15.4
or 4 to 1
3.8
B
B A
A

6-75
6.40. A fictitious ternary system composed of liquids A, B, and C was constructed by adding the component B to various binary AC
mixtures and noting the point at which complete miscibility occurred. The following are the mole-percents of A and B at which
complete miscibility was observed. Construct the phase diagram on a triangular graph paper.
x
A
(%) 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0
x
B
(%) 20.0 27.0 30.0 28.0 26.0 22.0 17.0 12.0 7.0

Comment on the variation of the mutual solubility of A and C as B is added.
Solution:

It is clear from the phase diagram that A and C are only slightly soluble in each other in the absence of B. As B is added, two layers are
formed; one rich in A, and the other rich in C. As B is added, the mutual solubility of A and C increases until at 30 mole % in B, the three
liquids become miscible in all proportions.

6-76
6.41. In organic chemistry it is a common procedure to separate a mixture of an organic liquid in water by adding a salt to it. This is
known as salting out. The ternary system K
2
CO
3
H
2
OCH
3
OH is typical. The system is distinguished by the appearance of the
two-liquid region abc.

a. Describe the phase(s) present in each region of the diagram.
b. What would occur as solid K
2
CO
3
is added to a solution of H
2
O and CH
3
OH of composition x?
c. How can the organic-rich phase in (b) be separated?
d. How can K
2
CO
3
be precipitated from a solution having composition y?
e. Describe in detail the sequence of events when a solution of composition F is evaporated.
Solution:
6-77

a.
Region System
AEa K
2
CO
3
in equilibrium with water-rich saturated solution
Aac K
2
CO
3
in equilibrium with conjugate liquids a and c
abc Two conjugate liquids joined by tie lines
AcB K
2
CO
3
in equilibrium with alcohol-rich saturated solution

b. The state of the system will move along a line joining x and A. Initially solution is formed; as more K
2
CO
3
is added, two layers, a
and c form, and once beyond point z, K
2
CO
3
ceases to dissolve so that solid K
2
CO
3
and the two liquids a and c coexist.

c. As long as two liquids exist, liquid with composition in the region AcB is the alcohol-rich layer and may be separated from the
water-rich later by separatory funnel.

d. When water is added to an unsaturated solution of K
2
CO
3
in alcohol, the state of the system moves along the line joining y and D.
Some K
2
CO
3
will precipitate as the state moves into the ABc region and then redissolves as it moves into the solution region again.

e. On evaporation of F, the system composition follows a line drawn from the water corner through F to the Ac line. At the first
composition line, two liquids form and the compositions of the solutions of the solutions move toward a and c. When the system
composition reaches the ac line, K
2
CO
3
begins to precipitate and is in equilibrium with the conjugate liquids a and c. Further
reduction of water moves the ratio of liquid a to liquid c in favor of c until the line Ac is crossed, at which time solid K
2
CO
3
is in
equilibrium with a single solution.


CHAPTER
7
7
Solutions of Electrolytes

Physical Chemistry
Electronic Edition

Chapter 7: Solutions of Electrolytes Faradays Laws, Molar Conductivity, and Weak Electrolytes
7-2
Chapter 7
Faradays Laws, Molar Conductivity, and Weak Electrolytes
7.1. A constant current was passed through a solution of cupric sulfate, CuSO
4
, for 1 h, and 0.040 g of copper was deposited. Calculate
the current (atomic weight of Cu =63.5).
Solution
7.2. After passage of a constant current for 45 min, 7.19 mg of silver (atomic weight =107.9) was deposited from a solution of silver
nitrate. Calculate the current.
Solution
7.3. Electrolysis of molten KBr generates bromine gas, which can be used in industrial bromination processes. How long will it take to
convert a 500.00-kg batch of phenol (C
6
H
5
OH) to monobromophenol using a current of 20 000 A?
Solution
7.4. The following are the molar conductivities of chloroacetic acid in aqueous solution at 25 C and at various concentrations c:
4
10
c
M

625 312.5 156.3 78.1 39.1 19.6 9.8
1 2 1
cm mol

53.1 72.4 96.8 127.7 164.0 205.8 249.2

Plot against c. If = 362
1
cm
2
mol
1
, are these values in accord with the Ostwald dilution law? What is the value of the
dissociation constant? (See also Problem 7.11.)
Solution
7.5. The electrolytic conductivity of a saturated solution of silver chloride, AgCl, in pure water at 25 C is 1.26 10
6

1
cm
1
higher
than that for the water used. Calculate the solubility of AgCl in water if the molar ionic conductivities are Ag
+
, 61.9
1
cm
2
mol
1
;
Cl
, 76.4
1
cm
2
mol
1
.
Solution
Chapter 7: Solutions of Electrolytes Faradays Laws, Molar Conductivity, and Weak Electrolytes
7-3
*7.6. The electrolytic conductivity of a 0.001 M solution of Na
2
SO
4
is 2.6 10
4

1
cm
1
. If the solution is saturated with CaSO
4
, the
conductivity becomes 7.0 10
4
1
cm
1
. Calculate the solubility product for CaSO
4
using the following molar conductivities at
these concentrations: (Na
+
) = 50.1
1
cm
2
mol
1
;
2 1 2 1
1
Ca 59.5 cm mol .
2
+ | |
=
|
\ .

Solution
7.7. The quantity l/A of a conductance cell (see Eq. 7.8) is called the cell constant. Find the cell constant for a conductance cell in which
the conductance, G, of a 0.100 M KCl solution is 0.01178 S at 25 C. The equivalent conductance for 0.100 M KCl at 25 C is
128.96 S cm
2
mol
1
. If a 0.0500 M solution of an electrolyte has a measured conductance of 0.00824 S using this cell, what is the
equivalent conductance of the electrolyte?
Solution
*7.8. A conductivity cell when standardized with 0.01 M KCl was found to have a resistance of 189 . With 0.01 M ammonia solution the
resistance was 2460 . Calculate the base dissociation constant of ammonia, given the following molar conductivities at these
concentrations: (K
+
) = 73.5
1
cm
2
mol
1
; (Cl
) = 76.4
1
cm
2
mol
1
;
4
(NH )
+
= 73.4
1
cm
2
mol
1
; (OH
) = 198.6
1
cm
2

mol
1
.
Solution
7.9. The conductivity of a 0.0312 M solution of a weak base is 1.53 10
4
S cm
1
. If the sum of the limiting ionic conductances for BH
+

and OH
is 237.0 S cm
2
mol
1
, what is the value of the base constant K
b
?
Solution
7.10. The equivalent conductance of KBr solutions as a function of concentration at 25 C is given in the following table. By a linear
regression analysis of suitable variables, find the value of for KBr.
c/10
3
M 0.25 0.36 0.50 0.75 1.00 1.60 2.00 5.00 10.00
/S cm
2
mol
1
150.16 149.87 149.55 149.12 148.78 148.02 147.64 145.47 143.15

Solution
Chapter 7: Solutions of Electrolytes Debye-Hckel Theory and Transport of Electrolytes
7-4
7.11. Equation 7.20 is one form of Ostwalds dilution law. Show how it can be linearized (i.e., convert it into a form that will allow
experimental values of at various concentrations to be tested by means of a straight-line plot). Explain how and K can be
obtained from the plot.
Kraus and Callis, J. Amer. Chem. Soc., 45, 2624(1923), obtained the following electrolytic conductivities for the dissociation of
tetramethyl tin chloride, (CH
3
)
4
SnCl, in ethyl alcohol solution at 25.0 C and at various concentrations c:
c/10
4
mol dm
3
1.566 2.600 6.219 10.441
/10
6

1
cm
1
1.788 2.418 4.009 5.336

By the use of the linear plot you have devised, determine and K.
Solution
7.12. A certain chemical company wishes to dispose of its acetic acid waste into a local river by first diluting it with water to meet the
regulation that the total acetic acid concentration cannot exceed 1500 ppm by weight. You are asked to design a system using
conductance to continuously monitor the acid concentration in the water and trigger an alarm if the 1500 ppm limit is exceeded.
What is the maximum conductance at which the system should trigger an alarm at a constant temperature of 25 C? (Assume that the
cell constant is 1.0 cm
1
and that the density of 1500 ppm acetic acid solution is not appreciably different from that of pure water.
The for acetic acid is 390.7 S cm
2
mol
1
and K
a
=1.81 10
5
mol dm
3
at 25 C. Ignore the conductance of water.)
Solution
7.13. How far can the conductivity of water at 25 C be lowered in theory by removing impurities? The (in S cm
2
mol
1
) for KOH,
HCl, and KCl are, respectively, 274.4, 426.04, and 149.86. K
w
=1.008 10
14
. Compare your answer to the experimental value of
5.8 10
8
S cm
1
obtained by Kohlrausch and Heydweiller, Z. phys. Chem. 14, 317(1894).
Solution
Debye-Hckel Theory and Transport of Electrolytes
7.14. The radius of the ionic atmosphere (1/) for a univalent electrolyte is 0.964 nm at a concentration of 0.10 M in water at 25 C
( 78). = Estimate the radius (a) in water at a concentration of 0.0001 M and (b) in a solvent of 38 = at a concentration of 0.10 M.
Solution
7-5
7.15. The molar conductivities of 0.001 M solutions of potassium chloride, sodium chloride, and potassium sulfate
2 4
1
K SO
2
| |
|
\ .
are 149.9,
126.5, and 153.3
1
cm
2
mol
1
, respectively. Calculate an approximate value for the molar conductivity of a solution of sodium
sulfate of the same concentration.
Solution
7.16. The molar conductivity at 18 C of a 0.0100 M aqueous solution of ammonia is 9.6
1
cm
2
mol
1
. For NH
4
Cl, = 129.8
1
cm
2

mol
1
and the molar ionic conductivities of OH
and Cl
are 174.0 and 65.6

1
cm
2
mol
1
, respectively. Calculate for NH
3
and
the degree of ionization in 0.01 M solution.
Solution
7.17. A solution of LiCl was electrolyzed in a Hittorf cell. After a current of 0.79 A had been passed for 2 h, the mass of LiCl in the anode
compartment had decreased by 0.793 g.
a. Calculate the transport numbers of the Li
+
and Cl
ions.
b. If (LiCl) is 115.0
1
cm
2
mol
1
, what are the molar ionic conductivities and the ionic mobilities?
Solution
7.18. A solution of cadmium iodide, CdI
2
, having a molality of 7.545 10
3
mol kg
1
, was electrolyzed in a Hittorf cell. The mass of
cadmium deposited at the cathode was 0.03462 g. Solution weighing 152.64 g was withdrawn from the anode compartment and was
found to contain 0.3718 g of cadmium iodide. Calculate the transport numbers of Cd
2+
and I
.
Solution
7.19. The transport numbers for HCl at infinite dilution are estimated to be t
+
=0.821 and t
=0.179 and the molar conductivity is 426.16
1
cm
2
mol
1
. Calculate the mobilities of the hydrogen and chloride ions.
Solution
7.20. If a potential gradient of 100 V cm
1
is applied to a 0.01 M solution of NaCl, what are the speeds of the Na
+
and Cl
ions? Take the

ionic conductivities to be those listed in Table 7.3 on p. 291.
Solution
7-6
*7.21. A solution of LiCl at a concentration of 0.01 M is contained in a tube having a cross-sectional area of 5 cm
2
. Calculate the speeds of
the Li
+
and Cl
ions if a current of 1 A is passed. Use the ion conductivities listed in Table 7.3.
Solution
7.22. What is the work required to separate in vacuum two particles, one with the charge of the proton, from another particle with the
same charge of opposite sign? Carry out the calculations for an initial distance of (a) 1.0 nm to an infinite distance apart and (b)
from 1.0 mm to an infinite distance apart. (c) In (a) how much work would be required if the charge is moved to a distance of 0.1 m?
The charge on a proton is 1.6 10
19
C.
Solution
*7.23. According to Bjerrums theory of ion association, the number of ions of type i present in a spherical shell of thickness dr and
distance r from a central ion is
2 2
0 B
exp( /4 )4
i i i c
dN N z z e rk T r dr =
where z
i
and z
c
are the charge numbers of the ion of type i and of the central ion and e,
0
, , and k
B
have their usual significance.
Plot the exponential in this expression and also 4r
2
against r for a uni-univalent electrolyte in water at 25.0 C ( 78.3). = Allow r
to have values from 0 to 1 nm. Plot also the product of these functions, which is (dN
1
/N
1
)dr and is the probability of finding an ion
of type i at a distance between r and r +dr of the central ion.
By differentiation, obtain a value r* for which the probability is a minimum, and calculate the value for water at 25.0 C. The
electrostatic potential is given to a good approximation by the first term in Eq. 7.47 on p. 280. Obtain an expression, in terms of k
B
T,
for the electrostatic energy between the two univalent ions at this minimum distance, and evaluate this energy at 25 C.
Solution
Chapter 7: Solutions of Electrolytes Thermodynamics of Ions
7-7
Thermodynamics of Ions
7.24. The following are some conventional standard enthalpies of ions in aqueous solution at 25 C:
Ion
f
H/kJ mol
1

H
+
0
Na
+
239.7
Ca
2+
543.1
Zn
2+
152.3
Cl
167.4
Br
120.9

Calculate the enthalpy of formation in aqueous solution of 1 mol of NaCl, CaCl
2
, and ZnBr
2
, assuming complete dissociation.
Solution
7.25. One estimate for the absolute Gibbs energy of hydration of the H
+
ion in aqueous solution is 1051.4 kJ mol
1
. On this basis,
calculate the absolute Gibbs energies of hydration of the following ions, whose conventional standard Gibbs energies of hydration
are as follows:
Ion
hyd
G k J mol
1

H
+
0
Na
+
679.1
Mg
2+
274.1
Al
3+
1346.4
Cl
1407.1
Br
1393.3

Solution
7-8
7.26. Calculate the ionic strengths of 0.1 M solutions of KNO
3
, K
2
SO
4
, ZnSO
4
, ZnCl
2
, and K
4
Fe(CN)
6
; assume complete dissociation
and neglect hydrolysis.
Solution
7.27. Calculate the mean activity coefficient
for the Ba
2+
and
2
4
SO

ions in a saturated solution of BaSO
4
(K
sp
=9.2 10
11
mol
2
dm
6
)
in 0.2 M K
2
SO
4
, assuming the Debye-Hckel limiting law to apply.
Solution
7.28. The solubility of AgCl in water at 25 C is 1.274 10
5
mol dm
3
. On the assumption t hat the Debye-Hckel limiting law applies,
a. Calculate G for the process AgCl(s) Ag
+
(aq) +Cl
(aq).
b. Calculate the solubility of AgCl in an 0.005 M solution of K
2
SO
4
.
Solution
7.29. Employ Eq. 7.114 to make plots of log
against I for a uni-univalent electrolyte in water at 25 C, with B =0.51 mol

1
dm
3/2

and B =0.33 10
10
mol
1
dm
3/2
m
1
, and for the following values of the interionic distance a:
a = 0, 0.1, 0.2, 0.4, and 0.8 nm
Solution
7.30. Estimate the change in Gibbs energy G when 1 mol of K
+
ions (radius 0.133 nm) is transported from aqueous solution ( =78) to
the lipid environment of a cell membrane ( = 4) at 25 C.
Solution
7.31. At 18 C the electrolytic conductivity of a saturated solution of CaF
2
is 3.86 10
5

1
cm
1
, and that of pure water is 1.5 10
6

1
cm
1
.
The molar ionic conductivities of
2
1
Ca
2
+
and F
are 51.1
1
cm
2
mol
1
and 47.0
1
cm
2
mol
1
, respectively. Calculate the solubility of
CaF
2
in pure water at 18 C and the solubility product.
Solution
7-9
7.32. What concentrations of the following have the same ionic strength as 0.1 M NaCl?
CuSO
4
, Ni(NO
3
)
2
, Al
2
(SO
4
)
3
, Na
3
PO
4

Assume complete dissociation and neglect hydrolysis.
Solution
7.33. The solubility product of PbF
2
at 25.0 C is 4.0 10
9
mol
3
dm
9
. Assuming the Debye-Hckel limiting law to apply, calculate the
solubility of PbF
2
in (a) pure water and (b) 0.01 M NaF.
Solution
7.34. Calculate the solubility of silver acetate in water at 25 C, assuming the DHLL to apply; the solubility product is 4.0 10
3
mol
2

dm
6
.
Solution
*7.35. Problem 7.30 was concerned with the Gibbs energy change when 1 mol of K
+
ions are transported from water to a lipid. Estimate
the electrostatic contribution to the entropy change when this occurs, assuming the dielectric constant of the lipid to be temperature
independent, and the following values for water at 25 C: 78; = ln /T = 0.0046 K
1
. Suggest a qualitative explanation for the
sign of the value you obtain.
Solution
*7.36. Assuming the Born equation (Eq. 7.86) to apply, make an estimate of the reversible work of charging 1 mol of Na
+
Cl
in aqueous
solution at 25 C ( =78), under the following conditions:
a. The electrolyte is present at infinite dilution.
b. The electrolyte is present at such a concentration that the mean activity coefficient is 0.70.
The ionic radii are 95 pm for Na
+
and 181 pm for Cl
.
Solution
7.37. If the solubility product of barium sulfate is 9.2 10
11
mol
2
dm
6
, calculate the solubility of BaSO
4
in a solution that is 0.10 M in
NaNO
3
and 0.20 M in Zn(NO
3
)
2
; assume the DHLL to apply.
Solution
Chapter 7: Solutions of Electrolytes Ionic Equilibria
7-10
7.38. Silver chloride, AgCl, is found to have a solubility of 1.561 10
5
M in a solution that is 0.01 M in K
2
SO
4
. Assume the DHLL to
apply and calculate the solubility in pure water.
Solution
7.39. The enthalpy of neutralization of a strong acid by a strong base, corresponding to the process
H
+
(aq) +OH
(aq) H
2
O
is 55.90 kJ mol
1
. The enthalpy of neutralization of HCN by NaOH is 12.13 kJ mol
1
. Make an estimate of the enthalpy of
dissociation of HCN.
Solution
7.40. Make use of the Debye-Hckel limiting law to estimate the activity coefficients of the ions in an aqueous 0.004 M solution of
sodium sulfate at 298 K. Estimate also the mean activity coefficient.
Solution
Ionic Equilibria
7.41. A 0.1 M solution of sodium palmitate, C
15
H
31
COONa, is separated from a 0.2 M solution of sodium chloride by a membrane that is
permeable to Na
+
and Cl
ions but not to palmitate ions. Calculate the concentrations of Na

+
and Cl
ions on the two sides of the

membrane after equilibrium has become established. (For a calculation of the Nernst potential, see Problem 8.18.)
Solution
7.42. Consider the ionizations
3 2 3 2 2 2
H H N CH COO H N CH COOH H NCH COOH H
+ + + +
+ +
Assume that the following acid dissociation constants apply to the ionizations:
10
3 2 a
3
a
NH NH H ; 1.5 10
COOH COO H ; 4.0 10
K M
K M
+ +
+
+ =
+ =

Estimate a value for the equilibrium constant for the process
3 3 2 2
H N CH COO H NCH COOH
+

Solution
Chapter 7: Solutions of Electrolytes Essay Questions
7-11
7.43. The pK values for the successive ionizations of phosphoric acid are given on p. 308. Which of the four species is predominant at the
following values of the hydrogen or hydroxide concentration?
a. [H
+
] =0.1 M.
b. [H
+
] =2 10
3
M.
c. [H
+
] =5 10
5
M.
d. [OH
] =2 10
3
M.
e. [OH
] =1 M.
Solution
7.44. Two solutions of equal volume are separated by a membrane which is permeable to K
+
and Cl
ions but not to P
ions. The initial

concentrations are as shown below.
[K
+
] =0.05 M [K
+
] =0.15 M
[Cl
] =0.05 M [P
] =0.15 M

Calculate the concentrations on each side of the membrane after equilibrium has become established. (See Problem 8.26 in Chapter
8 for the calculation of the Nernst potential for this system.)
Solution
Essay Questions
7.45. State Faradays two laws of electrolysis and discuss their significance in connection with the electrical nature of matter.
7.46. Discuss the main ideas that lie behind the Debye-Hckel theory, as applied to the conductivities of solutions of strong electrolytes.
7.47. Outline two important methods for determining transport numbers of ions.
7.48. Explain why Li
+
has a lower ionic conductivity than Na
+
and why the value for H
+
is so much higher than the values for both of
these ions.
7.49. Describe briefly the type of hydration found with the following ions in aqueous solution: Li
+
, Br
, H
+
, OH
.
7.50. What modifications to the Debye-Hckel limiting law are required to explain the influence of ionic strength on solubilities?

Chapter 7: Solutions of Electrolytes Solutions
7-12
Solutions
7.1. A constant current was passed through a solution of cupric sulfate, CuSO
4
, for 1 h, and 0.040 g of copper was deposited. Calculate
the current (atomic weight of Cu =63.5 g mol
-1
).
Solution:
Given:
1
1 h 3600s, 0.040 g, 63.5 gmol t m M

= = = =
Required: I
To solve this problem we must use Eq. 7.6 and apply Faradays Laws of Electrolysis. Eq. 7.6 is given by,
Q It =
Rearranging to solve for I we obtain,
Q
I
t
=
where Q, is the quantity of electricity.
Q is proportional to the mass of the element produced at the electrode. Faradays constant, given by the symbol F, relates the amount of
substance deposited to the quantity of electricity, Q, passed through the solution. The charge carried by 1 mol of ions bearing z unit charges
is zF, where1 F =96 485 C mol
-1
.

Hence,
m
Q zF
M
| |
=
|
\ .

Using the expression above, we can solve for the current through the solution.
zF m
I
t M
| |
=
|
\ .

The charge on copper in CuSO
4
is Cu
2+
, therefore z =2
7-13
1
2 96485C mol
I
=
0.040g
3600s
63.5g
1
mol
1
1
0.0337655293C s
where1C s 1A
33.8mA
I
I
| |
|
|
\ .
=
=
=

7-14
7.2. After passage of a constant current for 45 min, 7.19 mg of silver (atomic weight =107.9 g mol
-1
) was deposited from a solution of
silver nitrate. Calculate the current.
Solution:
Given:
1
45 min 2700s, 7.19 mg 0.00719 g, 107.9 gmol t m M

= = = = =
Required: I
This problem can be solved in a similar manner as problem 7.1, using the expression for current as,
zF m
I
t M
| |
=
|
\ .
.
The charge on silver in AgNO
3
is Ag
+
, therefore z =1
1
1 96485C mol
I
=
0.00719 g
2700s
107.9 g
1
mol
1
1
0.0023812417C s
where1C s 1A
2.4mA
I
I
| |
|
|
\ .
=
=
=


7-15
7.3. Electrolysis of molten KBr generates bromine gas, which can be used in industrial bromination processes. How long will it take to
convert a 500.00-kg batch of phenol (C
6
H
5
OH) to monobromophenol using a current of 20 000 A?
Solution:
Given: 500.00 kg, 20000 A m I = =
Required: t
To solve this problem, we must first outline the chemical reactions that are taking place.
( )
( )
( )
2
6 5 2 6 4
1 2Br Br (g) 2
2 2K 2 2K(s)
3 C H OH Br (g) C H (Br)OH HBr
e
e

+
+
+
+ +

Two moles of electrons are involved in the generation of each mole of bromine gas, which reacts with one mole of phenol, therefore z =2.
Each batch consists of 500.00 kg of phenol therefore converting to the number of moles and we can determine the time required to convert
all 500.00 kg of phenol into monobromophenol.
Using Eq. 7.6 and
m
Q zF
M
| |
=
|
\ .
from problem 6.1, we can solve for t,
7-16
( ) ( )
6 5
6 5
1 1 1
C H OH
1
C H OH
1
6 12.011gmol 6 1.00794gmol 15.9994gmol
94.11304gmol
2 96485C mol
Q
t
I
zF m
t
I M
M
M
t

=
| |
=
|
\ .
= + +
=
=
3
500.00 10 g
20000A

94.11304 g
1
mol
1
where1C s 1A
1h
51260.16544s
3600s
14.23893484h
14.239h
t
t
t
| |
|
|
\ .
=
=
=
=

7-17
7.4. The following are the molar conductivities of chloroacetic acid in aqueous solution at 25 C and at various concentrations c:
4
10
c
M

625 312.5 156.3 78.1 39.1 19.6 9.8
1 2 1
cm mol

53.1 72.4 96.8 127.7 164.0 205.8 249.2

Plot against c. If = 362
1
cm
2
mol
1
, are these values in accord with the Ostwald Dilution Law? What is the value of the
dissociation constant? (See also Problem 7.11.)
Solution:
Given:
1 2 1
, , 362 cm mol c =
Required: plot of against c, are these values in accord with the Ostwald Dilution Law, K
Using the data above, we can create the following plot of against c.

7-18
The Ostwald dilution law is given by Eq. 7.20 as:
2
( / )
1 ( / )
c
K

=

To determine if the data given above follows the Ostwald Dilution Law, we see if we can calculate a fixed value for K, the dissociation
constant of the solution.
The results are plotted in the table below.
c
10
-4
M

1
cm
2
mol
1

K
M
625 53.1 0.001575951
312.5 72.4 0.0015625
156.3 96.8 0.001525554
78.1 127.7 0.001501592
39.1 164 0.001467205
19.6 205.8 0.001468105
9.8 249.2 0.001490406
Since the values of K are reasonably constant, we can say that data given above follows the Ostwald Dilution Law.
The value of the dissociation constant, K, can be calculated from the average of the K values obtained above.
average
3
average
0.001513045
1.5 10
K M
K M
=
=

7-19
7.5. The electrolytic conductivity of a saturated solution of silver chloride, AgCl, in pure water at 25 C is 1.26 10
6

1
cm
1
higher
than that for the water used. Calculate the solubility of AgCl in water if the molar ionic conductivities are Ag
+
, 61.9
1
cm
2
mol
1
;
Cl
, 76.4
1
cm
2
mol
1
.
Solution:
Given:
+ -
6 1 1 1 2 1 1 2 1
Ag Cl
1.26 10 cm , 61.9 cm mol , 76.4 cm mol = = =
Required: solubility
The expression for molar conductivity is given by Eq. 7.9.
c
=
In order to solve this problem we can use the concentration as a measure of solubility.
+ -
+ -
AgCl
AgCl
Ag Cl
Ag Cl
6 1
solubility
solubility
1.26 10
solubility
= +
=
+

=
1
1
cm
61.9
2 1 1
cm mol 76.4 +
2 1
9 3
6 3
6 3
cm mol
solubility 9.110629067 10 mol cm
solubility 9.110629067 10 mol dm
solubility 9.11 10 mol dm
=
=
=

7-20
7.6. The electrolytic conductivity of a 0.001 M solution of Na
2
SO
4
is 2.6 10
4

1
cm
1
. If the solution is saturated with CaSO
4
, the
conductivity becomes 7.0 10
4
1
cm
1
. Calculate the solubility product for CaSO
4
using the following molar conductivities at
these concentrations:
(Na
+
) = 50.1
1
cm
2
mol
1
;
2 1 2 1
1
Ca 59.5 cm mol .
2
+ | |
=
|
\ .

Solution:
Given:
2 4
2 4 4
4 1 1 4 1 1
Na SO 1 1
Na SO CaSO
2 2
0.001 , 2.6 10 cm , 7.0 10 cm c M

= = =
( )
1 2 1 2 1 2 1
1
Na 50.1 cm mol , Ca 59.5 cm mol
2

+ +
| |
= =
|
\ .

Required:
4
for CaSO
s
K
To determine the base dissociation constant for CaSO
4
, we must first realize which chemical reactions are taking place.
( )
( )
2
2 4 4
2 2
4 4
1 Na SO 2Na SO
2 CaSO Ca SO
+
+
+
+

The solubility product is therefore given by:
2 2
4
Ca SO
s
K
+
( ( =

,
To determine the concentrations of the species in the solution, we will determine the electrolytic and molar conductivities.
We are given that the initial electrolytic conductivity of the Na
2
SO
4
solution is 2.6 10
4

1
cm
1
which is raised to 7.0 10
4
1
cm
1

upon saturation with CaSO
4
.This means the increase in electrolytic conductivity is:
4 1 1 4 1 1
4 1 1
7.0 10 cm 2.6 10 cm
4.4 10 cm
=
=

The molar conductivity of the CaSO
4
solution can be calculated using Eq. 7.9.
7-21
4
1
CaSO
2
2
c
c
=

where c is the concentration of CaSO
4
and 2c is the concentration of CaSO
4
.
The molar conductivity of the Na
2
SO
4
solution is:
2 4
2 4
2 4
1
Na SO
2
1
Na SO
2
4 1 1
1
Na SO
2
2
2.6 10 cm
c
=

=
3 3
2 0.001 10 mol cm
( )
2 4
1 2 1
1
Na SO
2
130 cm mol
=

The molar conductivity of the Na
2
SO
4
is the same as,
2
2 4 4
1 1
Na
Na SO SO
2 2

+

= +
Therefore we can solve for
2
4
1
SO
2

to calculate the molar conductivity of the CaSO
4
.
7-22
2
4 2 4
2
4
2
4
2
2
4 4
4
4
1 1
Na
SO Na SO
2 2
1 2 1 1 2 1
1
SO
2
1 2 1
1
SO
2
1 1
Ca
CaSO SO
2 2
1 2 1 1 2 1
1
CaSO
2
1 2 1
1
CaSO
2
130 cm mol 50.1 cm mol
79.9 cm mol
59.5 cm mol 79.9 cm mol
139.4 cm mol

+

=
=
=
= +
= +
=

The concentration of CaSO
4
is therefore given by:
4
1
CaSO
2
4 1
2
4.4 10
c
c

=

=
1
1
cm
2 139.4
( )
2 1
6 3
3 3
cm mol
1.578192253 10 mol cm
1.578192253 10 mol dm
c
c
=
=

Solving for K
s
,
2
2 3 3
4
Ca
SO 1.0 10 mol dm
c
c
+

( =

( = +

The concentration of SO
4
2-
is influenced by the contributions of CaSO
4
and Na
2
SO
4
.
7-23
( )
3 3
6 2 6
6 2 6
1.0 10 mol dm
4.068883038 10 mol dm
4.07 10 mol dm
s
s
s
K c c
K
K

= +
=
=


7-24
7.7. The quantity l/A of a conductance cell (see Eq. 7.8) is called the cell constant. Find the cell constant for a conductance cell in which
the conductance, G, of a 0.100 M KCl solution is 0.01178 S at 25 C. The equivalent conductance for 0.100 M KCl at 25 C is
128.96 S cm
2
mol
1
. If a 0.0500 M solution of an electrolyte has a measured conductance of 0.00824 S using this cell, what is the
equivalent conductance of the electrolyte?
Solution:
Given:
2 1
KCl
0.01178 S, 25 C, 128.96 S cm mol at 0.100 G T c M = = = =
electrolyte
0.00824 S, 0.0500 G c M = =
Required: l/A,
electrolyte

In order to determine the cell constant, we must first calculate the value for the electrolytic conductance. As we know, this can be obtained
using Eq. 7.9.
3
0.100 10 mol
c
c

=
=
=
( )
3 2 1
cm 128.96 S cm mol
( )
1
0.012896 S cm

=

We can now use Eq. 7.8 to solve for the cell constant, l/A.
7-25
(conductance)
0.012896 S
A
G
l
l
A G
l
A
=
=
=
1
cm
0.01178 S
1
1
1.094736842 cm
1.09 cm
l
A
l
A
=
=

The equivalent conductance of the electrolyte in this same cell can be found using the cell constant calculated above and solve for from
Eq. 7.9.
c
l
G
A
=
=

( )
electrolyte
electrolyte
1
electrolyte
0.00824 S 1.094736842cm
l
G
A
c
=
=
( )
3 3
0.0500 10 mol cm

2 1
electrolyte
2 1
electrolyte
180.4126316S cm mol
180S cm mol
=
=

7-26
7.8. A conductivity cell when standardized with 0.01 M KCl was found to have a resistance of 189 . With 0.01 M ammonia solution the
resistance was 2460 . Calculate the base dissociation constant of ammonia, given the following molar conductivities at these
concentrations: (K
+
) = 73.5
1
cm
2
mol
1
; (Cl
) = 76.4
1
cm
2
mol
1
;
4
(NH )
+
= 73.4
1
cm
2
mol
1
; (OH
) = 198.6
1
cm
2

mol
1
.
Solution:
Given:
3
KCl NH
0.01 , 189 , 0.01 , 2460 c M R c M R = = = =
( ) ( )
1 2 1 1 2 1
K 73.5 cm mol , Cl 76.4 cm mol ,
+
= =
( ) ( )
1 2 1 1 2 1
4
NH 73.4 cm mol , OH 198.6 cm mol
+
= =
Required: K
b

In order to determine the base dissociation constant for ammonia, we must first outline which chemical reactions are taking place.
( )
( )
3 2 4
4 4
1 NH H O NH OH
2 NH OH NH OH
b
K
+
+
+

The base dissociation constant is therefore given by:

| |
4
4
NH OH
NH OH
b
K
+
( (

=
To solve for the concentrations of each species, we may begin by calculating the value for the electrolytic conductance of the standard KCl
solution in the cell.
+ -
KCl
K Cl
1 2 1 1 2 1
KCl
1 2 1
KCl
3
KCl
149.9 cm mol
0.01 10 mol
c
c

=
=
= +
= +
=
=
( )
3 1 2 1
cm 149.9 cm mol
( )
1 1
KCl
0.001499 cm

=

7-27
Recall that the resistance is inversely proportional to the conductance. The electrolytic conductivity of the ammonia solution is therefore,
3
3
3
KCl
NH KCl
NH
1 1
NH
189
0.001499 cm
R
R

=
2460
3
4 1 1
NH
1.151670732 10 cm

=

The molar conductivity of
4
NH OH
+
+ is:
+ -
4
4
4
4
NH OH
NH OH
1 2 1 1 2 1
NH OH
1 2 1
NH OH
73.4 cmmol 198.6 cm mol
272 cmmol
= +
= +
=

Using Eq. 7.9, we can calculate the concentrations of
4
NH and OH
+
.
3
4
NH
NH OH
4 1
1.151670732 10
c
c
c
=
=

=
1
1
cm
272
2 1
7 3
4 3
cm mol
4.234083572 10 mol cm
4.234083572 10 mol dm
c
c
=
=

Knowing that;
4
NH OH c
+
( ( = =

, we can solve for K
b
.

4
NH OH

4
NH
+

+
OH

C
initial
0.01 0 0 mol dm
-3

C
equilibrium
0.01 c c c mol dm
-3

7-28

| |
( )
2
4
4
2
4 3
4 3
NH OH
NH OH 0.01
4.234083572 10 mol dm
0.01 4.234083572 10 mol dm
b
b
c
K
c
K
+
( (

= =
=

5 3
5 3
1.872008786 10 mol dm
1.9 10 mol dm
b
b
K
K
=
=

7-29
7.9. The conductivity of a 0.0312 M solution of a weak base is 1.53 10
4
S cm
1
. If the sum of the limiting ionic conductances for BH
+

and OH
is 237.0 S cm
2
mol
1
, what is the value of the base constant K
b
?
Solution:
Given:
4 1 2 1
0.0312M, 1.53 10 S cm , 237.0 S cm mol c = = =
Required: K
b
In order to determine the base dissociation constant for the solution, we must write out the chemical reaction that is taking place.
2
B H O BH OH
b
K
+
+ +

Since we are told we have a weak base, it is possible to apply Ostwalds Dilution Law and introduce the degree of dissociation, , given by
Eq. 7.11.

B +
2
H O

BH
+

+
OH

( ) 1 c

c c
The base dissociation constant is therefore given by Eq. 7.18.

2
1
b
c
K

And the degree of dissociation is determined by calculating the molar conductivity of
2
B H O + using Eq. 7.9.
4 1
1.53 10 S cm
c
=
3 3
0.0312 10 mol cm
2 1
4.903846154S cm mol =

7-30
The degree of dissociation is therefore,
4.903846154 S
=
2
cm
1
mol
237.0 S
2
cm
1
mol
0.020691334 =

Solving for K
b
, we obtain the following:
( )( )
2
3
5 3
5 3
0.0312mol dm 0.020691334
1 0.020691334
1.363992486 10 mol dm
1.36 10 mol dm
b
b
b
K
K
K
=
=

7-31
7.10. The equivalent conductance of KBr solutions as a function of concentration at 25 C is given in the following table. By a linear
regression analysis of suitable variables, find the value of for KBr.
c/10
3
M 0.25 0.36 0.50 0.75 1.00 1.60 2.00 5.00 10.00
/S cm
2
mol
1
150.16 149.87 149.55 149.12 148.78 148.02 147.64 145.47 143.15

Solution:
Given: 25 C T = , data given above
Required:
KBr

The relationship between and c is given by the Debye-Hckel-Onsager Equation, Eq. 7.53.
( ) P Q c

= +
In order to solve for
KBr
, we can plot c against , where
3
10 c c

=
( )
c M
( )
2 1
S cm mol
0.01581139 150.16
0.01897367 149.87
0.02236068 149.55
0.02738613 149.12
0.03162278 148.78
0.04 148.02
0.04472136 147.64
0.07071068 145.47
7-32
0.1 143.15

From the linear regression, the y- intercept will be the value of
KBr

2 1
KBr
2 1
KBr
151.41268S cm mol
151.41S cm mol
=
=

7-33
7.11. Equation 7.20 is one form of Ostwalds dilution law. Show how it can be linearized (i.e., convert it into a form that will allow
experimental values of at various concentrations to be tested by means of a straight-line plot). Explain how and K can be
obtained from the plot.
Kraus and Callis, J. Amer. Chem. Soc., 45, 2624(1923), obtained the following electrolytic conductivities for the dissociation of
tetramethyl tin chloride, (CH
3
)
4
SnCl, in ethyl alcohol solution at 25.0 C and at various concentrations c:
c/10
4
mol dm
3
1.566 2.600 6.219 10.441
/10
6

1
cm
1
1.788 2.418 4.009 5.336

By the use of the linear plot you have devised, determine and K.

Solution:
Given: 25 C T = , data above
Required: , K
Ostwalds dilution law, given by Eq. 7.20 can be linearized in the following manner:
7-34
( ) ( ) ( )
( )
( )
( ) ( )
2
2
2
2
2
2
2
2
( / )
1 ( / )
1 / /
/
/
/
c
K
K c
K K
c
K K
c
K K
c
K
c K

=

=

=

=

From here, we can plot c against
1
and determine and K.

We can calculate from Eq. 7.9 at each concentration given.
c
= . This leads to a table of values with the following:

c
10
4
mol dm
3

10
6

1
cm
1

1
cm
2
mol
-1

c
-1
cm
-1

1/

cm
-2
mol
1.566 1.788 11.417625 1.78810
-6
0.087584
2.6 2.418 9.3 2.41810
-6
0.107527
6.219 4.009 6.446374 4.00910
-6
0.155126
10.441 5.336 5.1106216 5.33610
-6
0.195671

Now we obtain the following graph:
7-35

From the linear regression, the y- intercept will be K and the slope will be
2
K
7-36
1 1
2 2 1
2
2 1
1 1
1 2 1
1 2 1
1 1
1
0.00111 cm
0.03294 cm mol
0.03294 cm mol
0.00111 cm
29.67567568 cm mol
30 cm mol
0.00111 cm
0.00111
K
K
K
K
K
K

=
=
=
=
=
1
1
cm
29.67567568
2 1
5 3
2 3
cm mol
3.740437158 10 mol cm
3.7 10 mol dm
K
K

=
=

7-37
7.12. A certain chemical company wishes to dispose of its acetic acid waste into a local river by first diluting it with water to meet the
regulation that the total acetic acid concentration cannot exceed 1500 ppm by weight. You are asked to design a system using
conductance to continuously monitor the acid concentration in the water and trigger an alarm if the 1500 ppm limit is exceeded.
What is the maximum conductance at which the system should trigger an alarm at a constant temperature of 25 C? (Assume that the
cell constant is 1.0 cm
1
and that the density of 1500 ppm acetic acid solution is not appreciably different from that of pure water.
The for acetic acid is 390.7 S cm
2
mol
1
and K
a
=1.81 10
5
mol dm
3
at 25 C. Ignore the conductance of water.)
Solution:
Given:
1 2 1 5 3
max aceticacid water a
1500ppm, 1.0cm , , 390.7 S cmmol , 1.81 10 mol dm
A
c K
l

= = = =

25 C T =
Required: G
In order to solve this problem, we must first convert the concentration from parts per million to SI units.
( ) ( ) ( )
6
1 1 1
aceticacid
1
aceticacid
1500gacid
1500 ppm
10 g solution
1.500gacid
1000g solution
2 12.011gmol 4 1.00794gmol 2 15.9994gmol
60.05256gmol
1.500 g
c
c
M
M
c

= =
=
= + +
=
=
acid
60.05256 g
1
1
1
1kg solution mol
0.0249781192mol kg c
=

Since the solution has the same density as water, 1.00 kg of solution has a volume of 1.0 dm
3
. Therefore we can assume the solution has
concentration, 0.0249781192M. c =
The conductance of a solution is given by Eq. 7.8.
7-38
(conductance)
A
G
l
=
Since acetic acid is a weak acid, we may we use the Ostwalds Dilution Law, Eq. 7.20, to solve for .
( ) ( )
( ) ( )
2
2
2
( / )
1 ( / )
/ /
/ / 0
c
K
K K c
K K c

=

=
=

To solve for /

, we use the quadratic equation.
( )
( )
2
2
2
4
2
4
/
2
4
/
2
b b ac
x
a
K K c K
c
K K cK
c

=

=
+
=

( ) ( )( )
( )
2
5 5 5
1.81 10 1.81 10 4 0.0249781192 1.81 10
/
2 0.0249781192
/ 0.0269395691and 0.0269033691
M M M M
M
+
=
=

We will disregard the negative value and take / 0.0269395691
= to solve for .
( )( )
( )( )
2 1
2 1
0.0269395691
0.0269395691 390.7 S cmmol
10.52528964S cmmol
=
=
=

7-39
Using Eq. 7.9, we can substitute for the value of and determine the conductance of the solution.
( )
0.0249781192 mol
c
c
A
G
l
A
G c
l
G
=
=
=
=
=
( )
3 2
dm 10.52528964S cm
1
mol
( )
1
1.0 cm
( )

3
3 3
4 2
4 2
0.2629019389dm Scm
0.2629019389 10 cm Scm
2.629019389 10 Scm
2.63 10 Scm
G
G
G
G

=
=
=
=

7-40
7.13. How far can the conductivity of water at 25 C be lowered in theory by removing impurities? The (in S cm
2
mol
1
) for KOH,
HCl, and KCl are, respectively, 274.4, 426.04, and 149.86. K
w
=1.008 10
14
. Compare your answer to the experimental value of
5.8 10
8
S cm
1
obtained by Kohlrausch and Heydweiller, Z. phys. Chem. 14, 317(1894).
Solution:
Given:
2 1 2 1 2 1
KOH HCl KCl
274.4S cm mol , 426.04S cm mol , 149.86S cm mol

= = =

14 8 1
w exp
, 25 C, 1.008 10 5.8 10 S cm T K = = =
Required:
The dissociations of each salt in water are given by:
( )
( )
( )
1 KOH K OH
2 HCl H Cl
3 KCl K Cl
+
+
+
+
+
+

By rearranging we find that,
2
2
2
H O KOH HCl KCl
2 1 2 1 2 1
H O
2 1
H O
274.4S cm mol 426.04S cm mol 149.86S cm mol
550.58S cm mol

= +
= +
=

In pure water, the only species that conduct electricity are H andOH
+
ions. According to H OH
w
K
+
( ( =

, each have a concentration of
;
14 3 7 3
1.008 10 mol dm 1.0039992032 10 mol dm
w
K

= = .
Since this concentration is very low, we can assume that
2 2
H O H O
.
7-41
10
1.0039992032 10 mol
c

=
=
( )
3 2 1
cm 550.58Scm mol

( )
8 1
8 1
5.527779329 10 Scm
5.528 10 Scm

=
=

Compared to the experimental value of
8 1
5.8 10 S cm , the conductivity determined through this process produces a very similar result.
7-42
7.14. The radius of the ionic atmosphere (1/) for a univalent electrolyte is 0.964 nm at a concentration of 0.10 M in water at 25 C
( 78). = Estimate the radius (a) in water at a concentration of 0.0001 M and (b) in a solvent of 38 = at a concentration of 0.10 M.
Solution:
Given:
1
0.964nm, 0.10M, 25 C, 78 c T
= = = =
Required: see above
a) Eq. 7.50 indicates that the thickness of the ionic atmosphere is inversely proportional to the square root of the concentration.
1/2
0 B
2 2
1
i i
i
k T
e c z L

| |
|
=
|
|
\ .

1 1
c
| |
|
\ .

Therefore the radius in water, where the electrolyte has c = 0.0001 M, can be obtained from the ratio of proportions.
7-43
1 2
2 1
1
1
2 2
1
2 1 2
2
1 1
1
1
1 1
1 0.1
c c
c
c
c
c
M

| | | |
| |
\ . \ .
=
| |
|
| | \ .
=
|
\ .
| | | |
=
| |
\ . \ .
| |
=
|
\ . 0.0001M
( )
2
2
0.964nm
1
30.48435664nm
1
30.5nm
| |
=
|
\ .
| |
=
|
\ .

b) Similarly, we see from Eq. 7.50 that the thickness of the ionic atmosphere is proportional to the square root of the permittivity
1
| |

|
\ .

The radius in water where 38 = , can be obtained from the ratio of proportions.
7-44
( )
2
2 1 1
2
2
2
1 1
1 38
0.964nm
78
1
0.6728550726 nm
1
0.673 nm

| | | |
=
| |
\ . \ .
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .

7-45
7.15. The molar conductivities of 0.001 M solutions of potassium chloride, sodium chloride, and potassium sulfate
2 4
1
K SO
2
| |
|
\ .
are 149.9,
126.5, and 153.3
1
cm
2
mol
1
, respectively. Calculate an approximate value for the molar conductivity of a solution of sodium
sulfate of the same concentration.
Solution:
Given: 0.001M c =

2 4
1 2 1 1 2 1 1 2 1
KCl NaCl 1
K SO
2
149.9 cm mol , 126.5 cm mol , 153.3 cm mol = = =
Required:
2 4
1
Na SO
2

The molar conductivity of
2 4
1
Na SO
2
is given by the combination of the molar conductivities of each salt. We must also subtract the molar
conductivity of KCl since we are considering the solution containing only sodium and sulfate ions.
2 4 2 4
2 4
2 4
1 NaCl 1 KCl
Na SO K SO
2 2
1 2 1 1 2 1 1 2 1
1
Na SO
2
1 2 1
1
Na SO
2
126.5 cm mol 153.3 cm mol 149.9 cm mol
129.9 cm mol
= +
= +
=

7-46
7.16. The molar conductivity at 18 C of a 0.0100 M aqueous solution of ammonia is 9.6
1
cm
2
mol
1
. For NH
4
Cl, = 129.8
1
cm
2

mol
1
and the molar ionic conductivities of OH
and Cl
are 174.0 and 65.6

1
cm
2
mol
1
, respectively. Calculate for NH
3
and
the degree of ionization in 0.01 M solution.
Solution:
Given:
3 3 4
1 2 1 1 2 1
NH NH NH Cl
18 C, 0.0100M, 9.6 cm mol , 129.8 cm mol , T c

= = = =

1 2 1 1 2 1
OH Cl
174.0 cm mol , 65.6 cm mol , 0.01M c

= = =
Required:
3
NH
,

In solution, ammonia reacts in following manner,
3 2 4
4 4
NH H O NH OH
NH OH NH OH
+
+
+

As a result, we can obtain
3
NH
from the molar conductivity of NH

4
OH.
4 4
4
4
4
NH OH NH Cl
OH Cl
1 2 1 1 2 1 1 2 1
NH OH
1 2 1
NH OH
1 2 1
NH OH
129.8 cm mol 174.0 cm mol 65.6 cm mol
238.2 cm mol
238 cm mol

= +
= +
=
=

The degree of dissociation is defined by Eq. 7.11 which states,
7-47
1
9.6
=
2
cm
1
mol
1
238.2
2
cm
1
mol
2
0.040302267
4.0 10

=
=

7-48
7.17. A solution of LiCl was electrolyzed in a Hittorf cell. After a current of 0.79 A had been passed for 2 h, the mass of LiCl in the anode
compartment had decreased by 0.793 g.
a. Calculate the transport numbers of the Li
+
and Cl
ions.
b. If (LiCl) is 115.0
1
cm
2
mol
1
, what are the molar ionic conductivities and the ionic mobilities?
Solution:
Given:
LiCl
1 2 1
0.79A, 2h, 0.793g, 115.0 cmmol I t m

= = = =
Required: see above
a) To solve this problem, we can use the Hittorf method. This method gives the transport numbers according to Eq. 7.75 and Eq.7.76.
amountlostfromanodecompartment
amountdeposited
t
+
= And
amountlostfromcathodecompartment
amountdeposited
t
=
We will use the number of moles to measure the amounts of the Li
+
and Cl
ions. To determine the total amount deposited, we use Eq. 7.6.

( ) 0.79A 2 h
Q It
Q
=
=
s
3600
h
5688A s
5688C
Q
Q
| |
|
\ .
=
=

In problem 7.1 we found that Q zFn = since the charge carried by 1 mol of ions bearing z unit charges is zF, where1 F =96 485 C mol
-1
.

Solving for n, we can determine the total amount deposited.
5688 C
amount deposited
Q
n
zF
=
=
( ) 1 96485 C
( )
1
mol
amount deposited 0.0589521687 mol
=

The amount lost of LiCl lost in the anode compartment is given by n
Cl
.
7-49
LiCl
LiCl
LiCl
1 1
LiCl
6.941g mol 35.4527g mol
m
n
M
M

=
= +

1
LiCl
LiCl
42.3927g mol
0.793 g
M
n
=
=
42.3927 g
1
LiCl
mol
0.0187056096mol n
=

The anode reaction that is occurring is
2
1
Cl Cl
2
e

+ , therefore 0.0589521687 mol of Cl
-
are removed by electrolysis. The amount lost
from the anode compartment is given by,
net total LiCl
n n n =
net
net
0.0589521687 mol 0.0187056096mol
0.0402465592mol
n
n
=
=

Solving for t
Cl
-
we obtain,
Cl
0.0402465592 mol
t t

+
= =
0.0589521687 mol
Cl
Cl
0.682698534
0.68
t
t
=
=

The second transport number is given by1 t
+
,
Li
Li
Li
Li
1
1 0.682698534
0.317301466
0.32
t t t
t
t
t
+
+
+
+
+
= =
=
=
=

7-50
b) In order to determine the molar ionic conductivities we will use Eq. 7.79 which states,
and t t

+
+
= =

To solve, we rearrange and use
LiCl
1 2 1
115.0 cmmol
= .
( )( )
Cl Cl
1 2 1
Cl
1 2 1
Cl
1 2 1
Cl
115.0 cm mol 0.682698534
78.51033141 cm mol
79 cm mol
t
=
=
=
=

( )( )
Li Li
1 2 1
Li
1 2 1
Li
1 2 1
Li
115.0 cm mol 0.317301466
36.48966859 cm mol
36 cm mol
t
+ +
+
+
+

=
=
=
=

The ionic mobility is given in terms of molar ionic conductivity by Eq. 7.64.
7-51
1 2 1
Cl
4 1 2 1 1
Cl
1 1 1
1 1 1
4
Cl
78.51033141 cm mol
96485C
8.137050465 10 cm mol C
where1 1A V and 1 A 1C s
therefore,1 1C s V
8.137050465 10 C
Fu
c
u
F
u
u
u
+
+ +
+
+
+

= =
=
=
=
= =
=
=
( )
1 1 2 1 1
s V cm mol C

4 2 1 1 1
Cl
4 2 1 1 1
Cl
1 2 1
Li
4 2 1 1 1
Li
4 2 1 1 1
Li
8.137050465 10 cm mol V s
8.1 10 cm mol V s
36.48966859 cm mol
96485C
3.781900667 10 cm mol V s
3.8 10 cm mol V s
u
u
u
u
u
+
+
+

=
=
=
=
=

7-52
7.18. A solution of cadmium iodide, CdI
2
, having a molality of 7.545 10
3
mol kg
1
, was electrolyzed in a Hittorf cell. The mass of
cadmium deposited at the cathode was 0.03462 g. Solution weighing 152.64 g was withdrawn from the anode compartment and was
found to contain 0.3718 g of cadmium iodide. Calculate the transport numbers of Cd
2+
and I
.
Solution:
Given:
2+
3 1
anode
Cd
7.545 10 mol kg , 0.03462 g, 152.64 g, molality m m = = =

2
CdI inanode
0.3718 g m =
Required:
2+
Cd I
, t t

When working with a Hittorf cell, we must use Eq. 7.75 and Eq. 7.76 to solve for
2+
Cd I
and t t

.
amountlostfromanodecompartment
amountdeposited
t
+
= And
amountlostfromcathodecompartment
amountdeposited
t
=
The number of coulombs of charge will be used as a measure of each amount.
The anode compartment initially contained the following number of moles:
anode
3 1
7.545 10 mol kg
i
i
n molality m
n
=
=
( )
152.64 g
3
kg
10
g
0.001151669mol
i
n
| |
|
|
\ .
=

The anode compartment finally contained,
7-53
( )
2
2
2
2
CdI inanode
CdI
1 1
CdI
1
CdI
112.411gmol 2 126.90447gmol
366.21994gmol
0.3718 g
f
f
m
n
M
M
M
n

=
= +
=
=
366.21994 g
1
mol
0.0010152369mol
f
n
=

The number of moles lost from the anode compartment is therefore,
4
0.001151669mol 0.0010152369mol
1.364318907 10 mol
i f
n n n
n
n

=
=
=

The total amount of Cd
2+
deposited is calculated by,
2
2
2
2
2
Cd
Cd
Cd
1
Cd
Cd
112.411gmol
0.03462 g
m
n
M
M
n
+
+
+
+
+
=
=
=
112.411g
2
1
4
Cd
mol
3.079769773 10 mol n
+
=

Now it is possible to determine the transport number at the anode.
4
4
1.364318907 10 mol
3.079769773 10 mol
0.4429937974
0.4430
t
t
t
=
=

7-54
The second transport number is given by1 t
.
t 1 0.4429937974
t 0.5570062026
t 0.5570
+
+
+
=
=
=

7-55
7.19. The transport numbers for HCl at infinite dilution are estimated to be t
+
=0.821 and t
=0.179 and the molar conductivity is 426.16
1
cm
2
mol
1
. Calculate the mobilities of the hydrogen and chloride ions.
Solution:
Given:
HCl
1 2 1
0.821, 0.179, 426.16 cm mol t t

+
= = =
Required: , u u
+

The ionic mobility is given in terms of molar ionic conductivity by Eq. 7.64.
Fu
c
+
+ +
+
= =
The molar ionic conductivities are given by Eq. 7.79.
and t t

+
+
= =

By rearranging and substituting equations 7.64 and 7.79, we can obtain an expression for the ionic mobility.

u
F
t
u
F
=

Now it is possible to solve for and u u
+
.
7-56
( )( )
1 2 1
1 2 1 1
1 1 1
1 1 1
426.16 cm mol 0.821
96485C
0.003626236 cm mol C
where1 1A V and 1 A 1C s
therefore,1 1C s V
0.003626236 C
u
u
u
+
+

+
=
=
= =
=
=
( )
1 1 2 1 1
s V cm mol C

( )( )
3 1 2 1 1
1 2 1
4 1 2 1 1
4 1 2 1 1
3.63 10 V cm mol s
426.16 cm mol 0.179
96485C
7.906165725 10 V cm mol s
7.91 10 V cm mol s
u
u
u
u

+
=
=
=

7-57
7.20. If a potential gradient of 100 V cm
1
is applied to a 0.01 M solution of NaCl, what are the speeds of the Na
+
and Cl
ions? Take the

ionic conductivities to be those listed in Table 7.3 on p. 291.
Solution:
Given:
1
NaCl
100 V cm , 0.01M, Table 7.3 V c = =
Required:
Na Cl
, v v
+

The ionic mobility is given in terms of the molar ionic conductivity by Eq. 7.64.
Fu
c
u
F
+
+ +
+
+
+
= =
=

From Table 7.3 we are given that,
2 1 2 1
Na Cl
50.08Scm mol and 76.31Scm mol
+

= =
2 1
Na
50.08Scm mol
u
+
=
1
96485C mol
4 2 1
Na
1 1 1 1
1 1
4
Na
5.19044411 10 Scm C
where1 S 1 and1 1A V and 1 A 1C s
therefore,1S 1C s V
5.19044411 10 C
u
u
+
+

=
= = =
=
=
( )
1 1 2 1
s V cm C

4 1 2 1
Na
2 1
Cl
5.19044411 10 V cm s
76.31Scm mol
u
u
+
=
=
1
96485C mol
4 1 2 1
Cl
7.909001399 10 V cm s u

=

7-58
From section 7.5 we know that, speed =uV. The velocities in a gradient of 100 V cm
1
are thus,
4 1
Na
5.19044411 10 V v
+

=
2
cm
( )
1
s 100 V
1
cm
( )
2 1
Na
2 1
Na
4 1
Cl
5.19044411 10 cms
5.19 10 cms
7.909001399 10 V
v
v
v
+
+

=
=
=
2
cm
( )
1
s 100 V
1
cm
( )

2 1
Cl
2 1
Cl
7.909001399 10 cms
7.91 10 cms
v
v

=
=

7-59
7.21. A solution of LiCl at a concentration of 0.01 M is contained in a tube having a cross-sectional area of 5 cm
2
. Calculate the speeds of
the Li
+
and Cl
ions if a current of 1 A is passed. Use the ion conductivities listed in Table 7.3.
Solution:
Given:
2
LiCl
0.01M, 5cm, 1A c A I = = = , Table 7.3
Required:
Li Cl
, v v
+

In order to determine the speeds of the ions, we must find the potential gradient. Once we have this information, we can proceed in a similar
manner as was done in problem 7.20.
The potential gradient can be calculated using Ohms Law (Eq.7.7) in conjunction with Eq. 7.9.
V
R
I
= and
c
=
The specific conductivity of a 0.01 M solution is calculated according to:
c =
We determine the molar conductivity of LiCl using the data for the ionic conductivities of Li
+
and Cl
-
found in Table 7.3.
LiCl
Li Cl
2 1 2 1
LiCl
2 1
LiCl
38.66Scm mol 76.31Scm mol
114.97Scm mol

+

= +
= +
=

Hence,
3
0.01 10 mol

=
( )
3 2 1
cm 114.97Scm mol

( )
3 1
1.1497 10 Scm

=

Let us consider the fact that the resistance is inversely proportional to , and we must factor in the 5 cm
2
of surface area.
7-60
3 1
1
1.1497 10 Scm
R

=
2
5 cm
1
173.9584239 cm R

=

The potential gradient required to produce a current of 1 A is therefore,
( )( )
1
1
1 A 173.9584239 cm
where1 1V A
V

=
=

1
173.9584239V cm V

=
The ionic mobilities can be calculated using Eq. 7.64.
Fu
c
u
F
+
+ +
+
+
+
= =
=

From Table 7.3 we know that,
7-61
2 1 2 1
Li Cl
38.66Scm mol and 76.31Scm mol
+

= =
2 1
Li
38.66Scm mol
u
+
=
1
96485C mol
4 2 1
Li
1 1 1 1
1 1
4
Li
4.006840442 10 Scm C
where1 S 1 and1 1A V and 1 A 1C s
therefore,1S 1C s V
4.006840442 10 C
u
u
+
+

=
= = =
=
=
( )
1 1 2 1
s V cm C

4 1 2 1
Li
2 1
Cl
4.006840442 10 V cm s
76.31Scm mol
u
u
+
=
=
1
96485C mol
4 1 2 1
Cl
7.909001399 10 V cm s u

=

From section 7.5 we are given that, speed =uV.
4 1 2 1 1
Li
4.006840442 10 V cm s V v
+

=
2
cm
( )
1
s 173.9584239 V
1
cm
( )
1
Li
2 1
Li
0.0697023648cms
7.0 10 cms
v
v
+
+

=
=

4 1
Cl
7.909001399 10 V v

=
2
cm
( )
1
s 173.9584239 V
1
cm
( )
1
Cl
1
Cl
0.1375837418cms
0.14cms
v
v
=
=

7-62
7.22. What is the work required to separate in vacuum two particles, one with the charge of the proton, from another particle with the
same charge of opposite sign? Carry out the calculations for an initial distance of (a) 1.0 nm to an infinite distance apart and (b)
from 1.0 mm to an infinite distance apart. (c) In (a) how much work would be required if the charge is moved to a distance of 0.1 m?
The charge on a proton is 1.6 10
19
C.
Solution:
Given: vacuum:
1 2
Q Q = , e =1.6 10
19
C
Required: see above
Recall that work is defined as the application of a force through a distance. This definition is given by Eq. 1.1, dw =F dl. In this case, the
force we are concerned with is an electrostatic force, and the distance in a vacuum we use as r.
From Eq. 7.1, the electrostatic force is given by:
1 2
2
0
4
QQ
F
r
=
To determine the amount of work done, we will take the integral of F with respect to r.
2
1
2
1
1 2
2
0
4
r
r
r
r
w Fdr
QQ
w dr
r
=
=

Since the particles have opposite charges, we will introduce a negative sign.
2
1
1 2
2
0
1 2
0 2 1
4
1 1
4
r
r
QQ
w dr
r
QQ
w
r r

=
| |
=
|
\ .

The permittivity of a vacuum has the value,
12 2 1 1
0
8.854 10 C J m

= . This will be used when solving parts a, b and c.
7-63
a)

9
1 2
19
1.0 10 m, m
1.6 10 C
r r
w
= =
=
( )
2
12 2
4 8.854 10 C

1 1
J m

( )
1
9
1
1.0 10 m
19
2.3008621 10 J w
| |
|
\ .
=

19
2.3 10 J w =
b)
3
1 2
19
1.0 10 m, m
1.6 10 C
r r
w
= =
=
( )
2
12 2
4 8.854 10 C

1 1
J m

( )
1
3
1
1.0 10 m
25
25
2.3008621 10 J
2.3 10 J
w
w
| |
|
\ .
=
=

c)
9
1 2
19
1.0 10 m, 0.10 m
1.6 10 C
r r
w
= =
=
( )
2
12 2
4 8.854 10 C

1 1
J m

( )
9
1 1
0.10 m 1.0 10 m
19
19
2.3008621 10 J
2.3 10 J
w
w
| |
|
\ .
=
=

7-64
7.23. According to Bjerrums theory of ion association, the number of ions of type i present in a spherical shell of thickness dr and
distance r from a central ion is
2 2
0 B
exp( /4 )4
i i i c
dN N z z e rk T r dr =
where z
i
and z
c
are the charge numbers of the ion of type i and of the central ion and e,
0
, , and k
B
have their usual significance.
Plot the exponential in this expression and also 4r
2
against r for a uni-univalent electrolyte in water at 25.0 C ( 78.3). = Allow r
to have values from 0 to 1 nm. Plot also the product of these functions, which is (dN
1
/N
1
)dr and is the probability of finding an ion
of type i at a distance between r and r +dr of the central ion.
By differentiation, obtain a value r* for which the probability is a minimum, and calculate the value for water at 25.0 C. The electrostatic
potential is given to a good approximation by the first term in Eq. 7.47 on p. 280. Obtain an expression, in terms of k
B
T, for the electrostatic
energy between the two univalent ions at this minimum distance, and evaluate this energy at 25 C.
Solution:
7-65
7.24. The following are some conventional standard enthalpies of ions in aqueous solution at 25 C:
Ion
f
H/kJ mol
1

H
+
0
Na
+
239.7
Ca
2+
543.1
Zn
2+
152.3
Cl
167.4
Br
120.9

Calculate the enthalpy of formation in aqueous solution of 1 mol of NaCl, CaCl
2
, and ZnBr
2
, assuming complete dissociation.
Solution:
Given: standard enthalpies
Required: enthalpies of formation
In order to calculate the enthalpies of formation, we will simply sum up the standard enthalpies of the ions present in the solution.
7-66
( )
Na Cl
2 Ca Cl
2
2
2 Zn Br
2
NaCl
1 1
NaCl
1
NaCl
CaCl
1 1
CaCl
1
CaCl
ZnBr
ZnBr
407.1 kJ mol
2
543.1 kJ mol 2 167.4 kJ mol
877.9 kJ mol
2
f f f
f
f
f f f
f
f
f f f
f
H H H
H
H
H H H
H
H
H H H
H

= +
=
=
= +
=
=
= +
( )
2
1 1
1
ZnBr
152.3 kJ mol 2 120.9 kJ mol
394.1 kJ mol
f
H

=
=


7-67
7.25. One estimate for the absolute Gibbs energy of hydration of the H
+
ion in aqueous solution is 1051.4 kJ mol
1
. On this basis,
calculate the absolute Gibbs energies of hydration of the following ions, whose conventional standard Gibbs energies of hydration
are as follows:
Ion
hyd
G k J mol
1

H
+
0
Na
+
679.1
Mg
2+
274.1
Al
3+
1346.4
Cl
1407.1
Br
1393.3
Solution:
Given: ( )
H
1
hyd
absolute 1051.4 kJ mol G
+
=
Required: ( )
hyd
absolute G
for each ion

In order to find the absolute Gibbs energies of hydration, we can either lower the cations standard Gibbs energies of hydration, or raise the
anions absolute Gibbs energies of hydration by1051.4 kJ mol
1
(per charge).
7-68
( )
( )
( )
( )
( ) ( )
( )
H
H
Na
Na
2
Mg
2
Mg
1
hyd
1
hyd
1 1
hyd
1
hyd
1
hyd
hyd
absolute 0 1051.4kJ mol
absolute 1051.4kJ mol
absolute 679.1kJ mol 1051.4kJ mol
absolute 274.1kJ mol 2 1051.4kJ mol
absolute
G
G
G
G
G
G
+
+
+
+
+
+

=
=
=
=
=
( ) ( )
( )
( )
( )
3
Al
3
Al
Cl
Cl
1
1 1
hyd
1
hyd
1 1
hyd
1
hyd
1828.7kJ mol
absolute 1346.4kJ mol 3 1051.4kJ mol
G
G
G
G
+
+

=
=
=
= +
=

( )
( )
Br
Br
1 1
hyd
1
hyd
G
G

= +
=

7-69
7.26. Calculate the ionic strengths of 0.1 M solutions of KNO
3
, K
2
SO
4
, ZnSO
4
, ZnCl
2
, and K
4
Fe(CN)
6
; assume complete dissociation
and neglect hydrolysis.
Solution:
Given: 0.1M c =
Required: I
The ionic strength of a solution is given by Eq. 7.103:
2
1
2
i i
i
I c z =

where z
i
is the valency of each ion present.
7-70

( )
( )
( )
( )
3
3
2 4
2 4
4
4
2
2
3 3
2 2
KNO
KNO
2
2 4 4
2 2
K SO
K SO
2 2
4 4
2 2
ZnSO
ZnSO
2
2
2 2
ZnCl
ZnCl
4
KNO K NO
1
0.1M 1 0.1M 1
2
0.1M
K SO 2K SO
1
0.2M 1 0.1M 2
2
0.3M
ZnSO Zn SO
1
0.1M 2 0.1M 2
2
0.4M
ZnCl Zn 2Cl
1
0.1M 2 0.2M 1
2
0.3M
K Fe
I
I
I
I
I
I
I
I
+
+
+
+
+
= +
=
+
= +
=
+
= +
=
+
= +
=
( ) ( )
( )
( )
( )
4 6
4 6
4
6 6
2 4
K Fe CN
K Fe CN
CN 4K Fe CN
1
0.4M 1 0.1M 4
2
1.0M
I
I
+
+
= +
=

7-71
7.27. Calculate the mean activity coefficient
for the Ba
2+
and
2
4
SO

ions in a saturated solution of BaSO
4
(K
sp
=9.2 10
11
mol
2
dm
6
)
in 0.2 M K
2
SO
4
, assuming the Debye-Hckel limiting law to apply.
Solution:
Given: BaSO
4
: K
sp
=9.210
11
mol
2
dm
6
,
2 4
K SO
0.2 M c =
Required:

When determining the mean activity coefficient, we use the Debye-Hckel limiting law given in Eq. 7.111:
3
10
log 0.51 /mol dm z z I

+
=
We may then calculate the ionic strength from Eq. 7.103 in the following manner,
2
1
2
i i
i
I c z =

( )
2 4
2 4
2
2 4 4
2 2
K SO
K SO
K SO 2K SO
1
0.4M 1 0.2M 2
2
0.6M
I
I
+
+
= +
=

Finally we can solve for the mean activity coefficient which produces;
( )
( )
10
0.51 2 2 0.6
2
log 0.51 2 2 0.6
10
0.0262919498
2.6 10
=
=
=
=

7-72
7.28. The solubility of AgCl in water at 25 C is 1.274 10
5
mol dm
3
. On the assumption t hat the Debye-Hckel limiting law applies,
a. Calculate G for the process AgCl(s) Ag
+
(aq) +Cl
(aq).
b. Calculate the solubility of AgCl in an 0.005 M solution of K
2
SO
4
.
Solution:
Given:
5 3
1.274 10 mol dm , 25 C s T = =
Required: see above
a. To calculate the Gibbs energy, we first need to determine the solubility product of AgCl in water.
Eq. 7.121 shows that
2
[Ag ][Cl ]
s
K
+
= , and since [Ag ] [Cl ]

+
= , we can write
2 2
s
K s
= .
We solve for the mean activity coefficient from Eq. 7.111, using the solubility as a measure of ionic strength.
( )
( )
5
3
10
5
10
0.511 1 1.274 10
log 0.51 /mol dm
log 0.511 1 1.274 10
10
0.9958172614
z z I
=
=
=
=

The solubility product is then,
( ) ( )
2
2
5
10 2
1.274 10 0.9958172614
1.60952659 10
s
s
K M
K M
=
=

Solving for Gibbs energy, using ln
s
G RT K = , we obtain
7-73
1
8.3145J K G

=
( )
1
mol 298.15 K
( ) ( )
10 2
1
1
ln 1.60952659 10
55900.51131J mol
55.90kJ mol
M
G
G
=
=

b. To solve for the solubility in asolution of 0.005 c M = K
2
SO
4
, we need to calculate the ionic strength since we have a common ion
present.

We can calculate the ionic strength from Eq. 7.103 in the following manner,
( )
2
2 2
1
2
1
0.01M 1 0.005 M 2
2
0.015 M
i i
i
I c z
I
I
=
= +
=

We solve for the mean activity coefficient from Eq. 7.111, using the solubility as a measure of ionic strength.
( )
3
10
10
10
0.062461988
log 0.51 / mol dm
log 0.511 1 0.015
log 0.062461988
10
0.86604012
z z I
=
=
=
=
=

Solving for the solubility by rearranging Eq. 7.121,
7-74
2 2
10 2
5
5
M
M
M
1.60952659 10
0.86604012
1.46491 10
1.46 10
s
s
K s
K
s
s
s
s
=
=
=
=
=

7-75
7.29. Employ Eq. 7.114 to make plots of log
against I for a uni-univalent electrolyte in water at 25 C, with B =0.51 mol

1
dm
3/2

and B =0.33 10
10
mol
1
dm
3/2
m
1
, and for the following values of the interionic distance a:
a = 0, 0.1, 0.2, 0.4, and 0.8 nm
Solution:


7-76
7.30. Estimate the change in Gibbs energy G when 1 mol of K
+
ions (radius 0.133 nm) is transported from aqueous solution ( =78) to
the lipid environment of a cell membrane ( = 4) at 25 C.
Solution:
Given:
water membrane
K
1 mol, 0.133 nm, 78, 4, 25 C n r T
+
= = = = =
Required: G
Eq. 7.87 (given below) may be used to estimate the change in Gibbs energy.
2 2
es
0
8
z e
G
r
=
Since we are given 1 mol of K
+
, we will multiply the expression above by L, Avogadros number.
7-77
( )
2 2
es
0
2
19
es
8
1 1.602 10 C
z e L
G
r
G

=
+
=
( )
2
( )
23 1
12 2
6.022 10 mol
8 8.854 10 C
1 2
N m

( )
9
0.133 10 m
( )
1
es
1
es
1
water
1
water
1
membrane
1
membrane
es membrane water
e
5222197.4616Nmmol
where1Nm 1 J
5222197.4616J mol
5222197.4616J mol
78
6694.839251J mol
5222197.4616J mol
4
130549.3654J mol
G
G
G
G
G
G
G G G
G

=
=
=
=
=
=
=
=
1 1
s
1
es
1
es
130549.3654J mol 6694.839251J mol
123854.5261J mol
124kJ mol
G
G

=
=
=

7-78
7.31. At 18 C the electrolytic conductivity of a saturated solution of CaF
2
is 3.86 10
5

1
cm
1
, and that of pure water is 1.5 10
6

1

cm
1
. The molar ionic conductivities of
2
1
Ca
2
+
and F
are 51.1
1
cm
2
mol
1
and 47.0
1
cm
2
mol
1
solubility of CaF
2
in pure water at 18 C and the solubility product.
Solution:
Given:
2 2
5 1 1 6 1 1
CaF H O
18 C, 3.86 10 cm , 1.5 10 cm , T = = =

2+
1 2 1 1 2 1
1
F
Ca
2
51.1 cm mol , 47.0 cm mol

= =
Required: ,
s
s K
The expression for the molar conductivity is given by Eq. 7.9:
c
=
It is possible to use the concentration to determine the solubility.
2
-
2+
2
2
2
1
CaF
2
1 1
F
CaF Ca
2 2
1 2 1 1 2 1
1
CaF
2
1 2 1
1
CaF
2
98.1 cm mol
c

=
= +
= +
=

The observed due to the salt is therefore,
7-79
5 1 1 6 1 1
5 1 1
5 1
3.86 10 cm 1.5 10 cm
3.71 10 cm
3.71 10
c
=
=

=
1
1
cm
98.1
2 1
7 3
4 3
cm mol
3.78185525 10 mol cm
3.78185525 10 mol dm
c
c
=
=

2
1
CaF
2
has the molar mass,
( )
2
2
1 1
1
CaF
2
1
CaF
1
40.078 g mol 18.9984032 g mol
2
39.0374032 g mol
M
M

= +
=

The solubility can now be determined.
1
39.0374032 g mol s

=
( )
4
3.78185525 10 mol
( )
3
3
2 3
dm
0.0147633808 gdm
1.48 10 gdm
s
s
=
=

The solubility product is given by,
( ) ( )
2
2
2
4 3 4 3
11 3
11 3
Ca F
1
3.78185525 10 mol dm 3.78185525 10 mol dm
2
2.70448584 10 mol dm
2.70 10 mol dm
s
s
s
s
K
K
K
K
+

( ( =

| |
=
|
\ .
=
=

7-80
7.32. What concentrations of the following have the same ionic strength as 0.1 M NaCl?
CuSO
4
, Ni(NO
3
)
2
, Al
2
(SO
4
)
3
, Na
3
PO
4

Assume complete dissociation and neglect hydrolysis.
Solution:
Given:
NaCl
0.1 M c =
Required:
( ) ( ) 4 3 4 2 4 3 3 2
CuSO Na PO Al SO Ni NO
, , , c c c c
As we have previously seen, the ionic strength of a compound may be determined using Eq. 7.103.
( )
2
2 2
NaCl
NaCl
1
2
1
0.1M 1 0.1M 1
2
0.1M
i i
i
I c z
I
I
=
= +
=

For each salt, we set
NaCl
0.1M I I = = to solve forc .
7-81
( )
( ) ( )
( )
( )
( )
( ) ( )
( )
( )
( )
4 4
4
4
3 3 2 2
3 2
3 2
2 4 2 4 3 3
2 4 3
2 4 3
3 4
2 2
CuSO CuSO
CuSO
2
CuSO
2 2
Ni NO Ni NO
Ni NO
2
Ni NO
2 2
Al SO Al SO
Al SO
3
Al SO
2
Na PO Na
1
0.1M 2 2
2
0.1M 4
2.5 10 M
1
0.1M 2 2 1
2
0.1M 3
3.3 10 M
1
0.1M 2 3 3 2
2
0.1M 15
6.7 10 M
1
0.1M 3 1
2
c c
c
c
c c
c
c
c c
c
c
c c
= +
=
=
= +
=
=
= +
=
=
= +
( )
3 4
3 4
3 4
2
PO
Na PO
2
Na PO
3
0.1M 6
1.7 10 M
c
c

=
=


7-82
7.33. The solubility product of PbF
2
at 25.0 C is 4.0 10
9
mol
3
dm
9
. Assuming the Debye-Hckel limiting law to apply, calculate the
solubility of PbF
2
in (a) pure water and (b) 0.01 M NaF.
Solution:
Given:
9 3 9
4.0 10 mol dm , 25 C
s
K T = =
Required: see above
a) The dissolution of PbF
2
is written as:
2
2
PbF Pb 2F
+
+ , hence the solubility product is given by:
2
2
Pb F
s
K
+
( ( =

.
In order to solve for solubility, we must first neglect the effect of the activity coefficients and write, | || |
2
3
2 4
s
K s s s = = .
Solving for s, we obtain,
3 9 3 9
3 3
4 4.0 10 mol dm
1.0 10 mol dm
s
s
=
=

We will determine the activity coefficients of Pb
2+
and F
-
by applying the Debye-Hckel limiting law. To solve, we must first calculate the
ionic strength of PbF
2
from Eq. 7.103.
( )
2
2 2
3 3
1
2
1
2 2 1
2
3
3.0 10 mol dm
i i
i
I c z
I s s
I s
I

=
= +
=
=

According to the Debye-Hckel limiting law, Eq. 7.111,
7-83
( )
3
3
3
10
0.51 /mol dm
0.51 2 1 3.0 10
log 0.51 /mol dm
10
10
0.8792903343
z z I
z z I
=
=
=
=

In order to find the true solubility, we must factor in the activity coefficients.
| || |
2
3
3
2
2 4
4
s
s
K s s s
K
s

+
+
= =
=

( )
9 3 9
3
3
3 3
3 3
4.0 10 mol dm
4 0.8792903343
1.1372808 10 mol dm
1.1 10 mol dm
s
s
s
=
=
=

b) In 0.01 M NaF, the ionic strength is essentially 0.01 mol dm
-3
. Calculating the activity coefficients, we obtain,
( )
3
0.51 /mol dm
0.51 2 1 0.01
10
10
0.790678628
z z I
=
=
=

If s is the solubility then,
7-84
| |
( )
( )
2
2
2
3
2
3
2 2 6
2 2 6
9 3
Pb F
Pb
F 0.01mol dm
0.01mol dm
0.0001mol dm
0.0001mol dm
4.0 10 mol
s
s
s
s
K
s
K s
K s
K
s
s

+
+
+
+
+
( ( =

( =

( =

( =

=
=
=
9
dm
( )
3
2
0.790678628 0.0001mol
6
dm
5 3
5 3
8.092076715 10 mol dm
8.1 10 mol dm
s
s
=
=

7-85
7.34. Calculate the solubility of silver acetate in water at 25 C, assuming the DHLL to apply; the solubility product is 4.0 10
3
mol
2

dm
6
.
Solution:
Given:
3 2 6
4.0 10 mol dm , 25 C
s
K T = =
Required: s
We will solve this problem in a similar manner as the previous question. We may start by neglecting the activity coefficients to find the first
approximation of s.
The dissolution of silver acetate is given by the following:
2 3 2 3
AgC H O Ag CH COO
+
+
| || |
2
3 2 6
3
4.0 10 mol dm
0.0632455532mol dm
s
s
K s s s
s K
s
s
= =
=
=
=

The ionic strength is thus,
( )
2 2
3
1
1 1
2
0.0632455532mol dm
I s s
I s
= +
= =

According to the Debye-Hckel limiting law, Eq. 7.111,
( )
3
10
0.511 1 0.0632455532
log 0.51 /mol dm
10
0.744289325
z z I
=
=
=

The second approximation of the solubility is therefore,
7-86
| || |
2
s
s
K s s s
K
s

+ +
+
= =
=

( )
3 2 6
2
3
2 3
4.0 10 mol dm
0.744289325
0.0849744193mol dm
8.5 10 mol dm
s
s
s
=
=
=

We may continue to take third and fourth approximations by repeating the above steps.
( )
( )
0.511 1 0.0849744193
3 2 6
2
3
10
0.7101222204
4.0 10 mol dm
0.7101222204
0.0890629125mol dm
s
K
s
s
s
+
=
=
=
=
=

The third approximation is then;
2 3
8.9 10 mol dm s = .
( )
( )
0.511 1 0.0890629125
3 2 6
2
3
10
0.7043663638
4.0 10 mol dm
0.7043663638
0.0897907062mol dm
s
K
s
s
s
+
=
=
=
=
=

7-87
The fourth approximation is then;
2 3
9.0 10 mol dm s = .

7-88
7.35. Problem 7.30 was concerned with the Gibbs energy change when 1 mol of K
+
ions are transported from water to a lipid. Estimate
the electrostatic contribution to the entropy change when this occurs, assuming the dielectric constant of the lipid to be temperature
independent, and the following values for water at 25 C: 78; = ln /T = 0.0046 K
1
. Suggest a qualitative explanation for the
sign of the value you obtain.
Solution:
Given: Problem 7.30:
ln
25 C, 78, 0.0046 T
T

= = =

Required:
es
S
, explain the sign

From Problem 7.30, we found the expression for the estimated Gibbs energy,
1
es
5222197.4616J mol
G
=
For the transfer from water to lipid we can say that,
1
es
lipid water
1 1
/J mol 5222197.4616 G

| |
= |
|
\ .

From Eq. 3.119:
es
es
1 1
es
lipid water
hence,
1 1
/ J K mol 5222197.4616
P
P
G
S
T
G
S
T
S
T

| |
=
|
\ .
| |
=
|
\ .
| |
= |
|
\ .

Since
lipid
is temperature independent, this leads to:
7-89
water
water
1 1
es
water
1 1
es 2
2
water
1
/ J K mol 5222197.4616
1
/ J K mol 5222197.4616
1 1 ln
since
S
T
S
T
T T

| |
=
|
\ .

=

( )
1 1
es
water
1 1
es
1 1
es
1 1
es
1 ln
/ J K mol 5222197.4616
1
/ J K mol 5222197.4616 0.0046
78
30.79626056J K mol
31J K mol
S
T
S
S
S
| |
=
|
\ .
=
=

The entropy increases due to the release of bound water molecules when the K
+
ions pass into the lipid.


7-90
7.36. Assuming the Born equation (Eq. 7.86) to apply, make an estimate of the reversible work of charging 1 mol of Na
+
Cl
in aqueous
solution at 25 C ( =78), under the following conditions:
a. The electrolyte is present at infinite dilution.
b. The electrolyte is present at such a concentration that the mean activity coefficient is 0.70.
The ionic radii are 95 pm for Na
+
and 181 pm for Cl
.
Solution:
Given: Eq. 7.86, 1mol, 25 C, 78 n T = = =
Required: see above
a) At infinite dilution, the work of charging an ion is given by Eq.7.86 which states,
2 2
rev
0
8
z e
w
r
=
For one mole of Na
+
, we multiply by Avogadros number, L and use the ionic radius of r =95 pm.
( )
+
+
2 2
Na
0
2
19
Na
8
1 1.602 10 C
z e L
w
r
w

=
+
=
( )
2
( )
23 1
12 2
6.022 10 mol
8 8.854 10 C
1 2
N m

( )
( )
12
78 95 10 m
( )
+
+
1
Na
1
Na
9372.774952Nmmol
9372.774952J mol
w
w
=
=

For one mole of Cl
-
, we will multiply by Avogadros number, L and use the ionic radius of r = 181 pm.
7-91
( )
-
2
19
Cl
1 1.602 10 C
w

=
( )
2
( )
23 1
12 2
6.022 10 mol
8 8.854 10 C
1 2
N m

( )
( )
12
78 181 10 m
( )
-
1
Cl
4919.412267J mol w

=

One mole of Na
+
Cl
-
at infinite dilution is thus,
+ -
rev
Na Cl
1 1
rev
9372.774952J mol 4919.412267J mol
w w w
w

= +
= +

1
rev
1
rev
14292.18722J mol
14kJ mol
w
w
=
=

b) These values are reduced when the electrolyte is at a higher concentration. The work of charging the ionic atmosphere is negative and
equal to ln
i
kT . Thus for one mol of Na
+
ions, of activity
+
, the work of charging the atmosphere is ln RT
+
. Similarly, for the chloride ion,
the work per mole is ln RT
.
For one mole of Na
+
Cl
-
( )
( )
rev
rev
rev
1
rev
ln ln
ln
2 ln
where 0.70
2 8.3145J K
w RT
w RT
w RT
w

+
+
= +
=
=
=
=
( )
1
mol 298.15 K
( )
1
rev
ln0.70
1768.37167J mol w

=

The net work done is given by,
1 1
rev
1
rev
1
rev
14292.18722J mol 1768.37167J mol
12523.81555J mol
13kJ mol
w
w
w

=
=
=

7-92

7-93
7.37. If the solubility product of barium sulfate is 9.2 10
11
mol
2
dm
6
, calculate the solubility of BaSO
4
in a solution that is 0.10 M in
NaNO
3
and 0.20 M in Zn(NO
3
)
2
; assume the DHLL to apply.
Solution:
Given:
( ) 3 3 2
11 2 6
inNaNO inZn NO
9.2 10 mol dm , 0.10M, 0.20M
s
K c c = = =
Required: s
The expression for the solubility product is given by,
| || |
2 2
4
2 2
Ba SO
s
s
s
K
K s s
K s

+
+
( ( =

=
=

The ionic strength of the solution is calculated according to Eq.7.103.
( )
2
2 2 2 2
1
2
1
1 0.1M 1 0.1M 2 0.2M 1 0.4M
2
0.70M
i i
i
I c z
I
I
=
= + + +
=

To find the activity coefficient, we will use the Debye-Hckel limiting law given by Eq. 7.111.
( )
3
3
10
0.51 /mol dm
0.51 2 2 0.70
log 0.51 /mol dm
10
10
0.0196432591
z z I
z z I
=
=
=
=

If the solubility s is therefore,
7-94
( )
2
11 2 6
2
4
4
9.2 10 mol dm
0.0196432591
4.882928531 10 M
4.9 10 M
s
K
s
s
s
s
=
=
=

7-95
7.38. Silver chloride, AgCl, is found to have a solubility of 1.561 10
5
M in a solution that is 0.01 M in K
2
SO
4
. Assume the DHLL to
apply and calculate the solubility in pure water.
Solution:
Given:
5
1.561 10 M, 0.01M s c = =
Required: s

The expression for the solubility product is given by,
| || |
2 2
Ag Cl
s
s
s
K
K s s
K s

+
+
( ( =

=
=

The ionic strength of the solution is calculated according to Eq.7.103.
( )
2
2 2
1
2
1
1 0.02M 2 0.01M
2
0.03M
i i
i
I c z
I
I
=
= +
=

To determine the activity coefficient, we will use the Debye-Hckel limiting law, Eq. 7.111.
( )
3
3
10
0.51 /mol dm
0.511 1 0.03
log 0.51 /mol dm
10
10
0.8159534984
z z I
z z I
=
=
=
=

If the solubility product is K
s
,
7-96
( ) ( )
2
2
5
10 2
0.8159534984 1.561 10 M
1.62232038 10 M
s
s
K
K
=
=

Finally, the solubility in pure water is given by;
10 2
5
5
1.62232038 10 M
1.273703411 10 M
1.3 10 M
s
s K
s
s
s
=
=
=
=


7-97
7.39. The enthalpy of neutralization of a strong acid by a strong base, corresponding to the process
H
+
(aq) +OH
(aq) H
2
O
is 55.90 kJ mol
1
. The enthalpy of neutralization of HCN by NaOH is 12.13 kJ mol
1
. Make an estimate of the enthalpy of
dissociation of HCN.
Solution:
Given:
1 1
neut
55.90kJ mol , 12.13kJ mol H H

= =
Required:
diss
H
The enthalpy change for the neutralization of HCN by NaOH is less than the value of the 55.90 kJ mol
-1
because the energy required for the
dissociation of HCN,
diss
H is given by:
neut diss
diss neut
1 1
diss
1
diss
, hence,
55.90kJ mol 12.13kJ mol
43.77kJ mol
H H H
H H H
H
H

=
=
=
=

7-98
7.40. Make use of the Debye-Hckel limiting law to estimate the activity coefficients of the ions in an aqueous 0.004 M solution of
sodium sulfate at 298 K. Estimate also the mean activity coefficient.
Solution:
Given:
2 4
Na SO
0.004M, 298K c T = =
Required:
2
4
Na SO
, ,
+

From Eq. 7.104 we can calculate the activity coefficients for each ion.
2
10
log
i i
z B I =
As we know, the ionic strength of the solution is calculated using Eq.7.103.
( )
2
2 2
1
2
1
1 0.008M 2 0.004M
2
0.012M
i i
i
I c z
I
I
=
= +
=

The activity coefficients are therefore,
( )
( )
2
2
2
4
2
4
2
4
1 0.51 0.012
Na
Na
Na
2 0.51 0.012
SO
SO
SO
10
0.8792903343
0.879
10
0.5977632295
0.598
+
+
+
+

=
=
=
=
=
=

The mean activity coefficient can be determined by using Eq. 7.111 which produces,
7-99
( )
3
3
10
0.51 /mol dm
0.511 2 0.012
log 0.51 /mol dm
10
10
0.7731514919
0.773
z z I
z z I
=
=
=
=
=

7-100
7.41. A 0.1 M solution of sodium palmitate, C
15
H
31
COONa, is separated from a 0.2 M solution of sodium chloride by a membrane that is
permeable to Na
+
and Cl
ions but not to palmitate ions. Calculate the concentrations of Na

+
and Cl
ions on the two sides of the

membrane after equilibrium has become established. (For a calculation of the Nernst potential, see Problem 8.18.)
Solution:
Given:
NaP NaCl
0.1M, 0.2M c c = =
Required:
Na Cl
, c c
+
on each side of the membrane at equilibrium
Palmitate Side Other Side
Initial concentrations
Na 0.1M
P 0.1M
+
( =

( =

Na 0.2M
Cl 0.2M
+
( =

( =

Final concentrations
( ) Na 0.1M
P 0.1M
Cl
x
x
+
( = +

( =

( =

( )
( )
Na 0.2M
Cl 0.2M
x
x
+
( =

( =

At equilibrium, the final concentration of NaCl on each side of the membrane will be the same. This allows us to solve for x.
( ) ( )
2
2
0.2M 0.1
0.04 0.4
x x x
x x
= +
+
2
0.1x x = +
0.04 0.5
0.08
x
x
=
=

7-101
The final concentrations are thus,
Palmitate Side Other Side
( ) Na 0.1M 0.08M
Na 0.18M
Cl 0.08M
+
+
( = +

( =

( =

( )
( )
Na Cl 0.2M
Na Cl 0.2M 0.08M
Na Cl 0.12M
x
+
+
+
( ( = =

( ( = =

( ( = =


7-102
7.42. Consider the ionizations
3 2 3 2 2 2
H H N CH COO H N CH COOH H NCH COOH H
+ + + +
+ +
Assume that the following acid dissociation constants apply to the ionizations:
10
3 2 a
3
a
NH NH H ; 1.5 10 M
COOH COO H ; 4.0 10 M
K
K
+ +
+
+ =
+ =

Estimate a value for the equilibrium constant for the process
3 3 2 2
H N CH COO H NCH COOH
+

Solution:
Given:
3
10 3
COOH
NH
1.5 10 M, 4.0 10 M K K
+

= =
Required:
3
3
NH CH COO
K
+

The equilibrium constant
3
NH
K
+
is given by,
| |
3
2 2
NH
3 2
H NCH COOH H
H N CH COOH
K
+
+
+
(

=
(

And
COOH
K
is given by,
3 2
COOH
3 2
H N CH COO H
H N CH COOH
K
+ +
+
( (

=
(

We can rearrange the two expressions to obtain an expression for
3
3
NH CH COO
K
+
, and solve for its value.
7-103
| |
3
3
3
3
3
3
3
NH
NH CH COO
COOH
2 2
NH CH COO
3 2
10
NH CH COO
H NCH COOH
H N CH COO
1.5 10 M
K
K
K
K
K
+
+
+
+
=
=
(

=
3
4.0 10 M
3
3
3
3
8
NH CH COO
8
NH CH COO
3.75 10
3.8 10
K
K
+
+
=
=


7-104
7.43. The pK values for the successive ionizations of phosphoric acid are given on p. 308. Which of the four species is predominant at the
following values of the hydrogen or hydroxide concentration?
a. [H
+
] =0.1 M.
b. [H
+
] =2 10
3
M.
c. [H
+
] =5 10
5
M.
d. [OH
] =2 10
3
M.
e. [OH
] =1 M.
Solution:
Given: p. 308
Required: see above
The successive ionizations of phosphoric acid are given by the following expression.
3 1 2
p 12.3 p 2.1 p 7.2
2 3
3 4 2 4 4 4
H PO H PO HPO PO
K K K = = =

In order to determine the pH we will use,
10
pH log H
+
( =

and pH 14 pOH = .
a.
( )
10
pH log 0.1
pH 1
=
=

3 4
H PO is predominant
b.
( )
3
10
pH log 2 10
pH 2.698
=
=

2
4
HPO

is predominant
c.
( )
5
10
pH log 5 10
pH 4.301
=
=

2
4
HPO

is predominant
d.
( )
3
10
pOH log 2 10
pOH 2.698
pH 14 2.698
pH 11.304
=
=
=
=

2
4
HPO

is predominant
7-105
e.
10
pOH log 1
pOH 0
pH 14
=
=
=

3
4
PO
is predominant


7-106
7.44. Two solutions of equal volume are separated by a membrane which is permeable to K
+
and Cl
ions but not to P
ions. The initial

concentrations are as shown below.
[K
+
] =0.05 M [K
+
] =0.15 M
[Cl
] =0.05 M [P
] =0.15 M

Calculate the concentrations on each side of the membrane after equilibrium has become established. (See Problem 8.26 in Chapter
8 for the calculation of the Nernst potential for this system.)
Solution:
Given: see above
Required:
K Cl
, c c
+
on each side of the membrane at equilibrium
We can solve this problem in a similar manner as problem 7.41.
Left-hand Side Right-hand Side
Initial concentrations
K 0.05M
Cl 0.05M
+
( =

( =

K 0.15M
P 0.15M
+
( =

( =

K 0.05M
Cl 0.05M
x
x
+
( =

( =

K 0.15M
Cl
P 0.1M
x
x
+
( = +

( =

( =

At equilibrium, the final concentration of KCl on each side of the membrane will be the same. This will allow us to solve for x.
( ) ( )
2
2
0.05M 0.15
0.0025 0.1
x x x
x x
= +
+
2
0.15x x = +
0.0025 0.25
0.01
x
x
=
=

7-107
The final concentrations are thus,
Left-hand Side Right-hand Side
K Cl 0.05M 0.01M
K Cl 0.04M
+
+
( ( = =

( ( = =

K 0.15M 0.01M
K 0.16M
Cl 0.01M
+
+
( = +

( =

( =


CHAPTER
8
8
Electrochemical Cells

Physical Chemistry
Electronic Edition

Chapter 8: Electrochemical Cells Electrode Reactions and Electrode Potentials
8-2
Chapter 8
Electrode Reactions and Electrode Potentials
8.1. Write the electrode reactions, the overall reaction, and the expression for the emf for each of the following reversible cells.
a. Pt, H
2
(1 bar)|HCl(aq)|Pt, Cl
2
(1 bar)
b. Hg|Hg
2
Cl
2
(s)|HCl(aq)|Pt, H
2
(1 bar)
c. Ag|AgCl(s)|KCl(aq)|Hg
2
Cl
2
(s)|Hg
d. Pt, H
2
(1 bar)|HI(aq)|AuI(s)|Au
e. Ag|AgCl(s)|KCl(c
1
) KCl(c
2
)|AgCl(s)|Ag
Solution
8.2. At 25 C and pH 7, a solution containing compound A and its reduced form AH
2
has a standard electrode potential of 0.60 V. A
solution containing B and BH
2
has a standard potential of 0.16 V. If a cell were constructed with these systems as half-cells,
a. Would AH
2
be oxidized by B or BH
2
oxidized by A under standard conditions?
b. What would be the reversible emf of the cell?
c. What would be the effect of pH on the equilibrium ratio [B][AH
2
]/[A][BH
2
]?
Solution
8.3. Calculate the standard electrode potential for the reaction Cr
2+
+2e

Cr at 298 K. The necessary E values are
a. Cr
3+
+3e
Cr E =0.74 V
b. Cr
3+
+e
Cr
2+
E =0.41 V
Solution
Chapter 8: Electrochemical Cells Thermodynamics of Electrochemical Cells
8-3
8.4. Write the individual electrode reactions and the overall cell reaction for the following cell:
Pt, H
2
|H
+
(1 m) F
2
, S
2
, H
+
(aq)|Pt
where F
2
represents the fumarate ion and S
2
the succinate ion. Write the expression for the emf of the cell.
Solution
8.5. Design electrochemical cells in which each of the following reactions occurs:
a. Ce
4+
(aq) +Fe
2+
(aq) Ce
3+
(aq) +Fe
3+
(aq)
b. Ag
+
(aq) +Cl
(aq) AgCl(s)
c. HgO(s) +H
2
(g) Hg(l) +H
2
O(l)
In each case, write the representation of the cell and the reactions at the two electrodes.
Solution
Thermodynamics of Electrochemical Cells
8.6. Calculate the equilibrium constant at 25 C for the reaction
2Fe
3+
(aq) +2I
(aq) 2Fe
2+
(aq) +I
2
(s)

using the standard electrode potentials given in Table 8.1.
Solution
8.7. From data in Table 8.1, calculate the equilibrium constant at 25 C for the reaction
Sn +Fe
2+
Sn
2+
+Fe
Solution
Chapter 8: Electrochemical Cells Thermodynamics of Electrochemical Cells
8-4
8.8. The standard electrode potential at 25 C for
cytochrome c (Fe
3+
) +e

cytochrome c (Fe
2+
)
is 0.25 V. Calculate G for the process
1
2
H
2
(g) +cytochrome c (Fe
3+
) H
+
+cytochrome c (Fe
2+
)
Solution
8.9. Using the values given in Table 8.1, calculate the standard Gibbs energy change G for the reaction
H
2
+
1
2
O
2
H
2
O
Solution
*8.10. From the data in Table 8.1, calculate the equilibrium constant at 25 C for the reaction
2Cu
+
Cu
2+
+Cu
What will be produced if Cu
2
O is dissolved in dilute H
2
SO
4
?
Solution
8.11. For the reaction 3H
2
(g, 1 atm) +Sb
2
O
3
(s, cubic) 2Sb(s) +3H
2
O(l), G =83.7 kJ [Roberts and Fenwick, J. Amer. Chem. Soc.,
50, 2146(1928)]. Calculate the potential developed by the cell
Pt|H
2
(g, 1 atm)|H
+
|Sb
2
O
3
(s, cubic)|Sb(s)
Which electrode will be positive?
Solution
Chapter 8: Electrochemical Cells Nernst Equation and Nernst Potentials
8-5
Nernst Equation and Nernst Potentials
8.12. Calculate the emf for the following cell at 25 C:
Pt, H
2
(1 bar)|HCl(0.5 m) HCl(1.0 m)|Pt, H
2
(1 bar)
Solution
8.13. The pyruvate-lactate system has an E value of 0.185 V at 25 C and pH 7.0. What will be the potential of this system if the
oxidation has gone to 90% completion?
Solution
8.14. a. From the data in Table 8.1, calculate the standard electrode potential for the half-reaction
Fe
3+
+3e

Fe
b. Calculate the emf at 25 C of the cell
Pt|Sn
2+
(0.1 m), Sn
4+
(0.01 m) Fe
3+
(0.5 m)|Fe
Solution
8.15. The cell Pt|H
2
(1 bar), H
+
KCl(saturated)|Hg
2
Cl
2
|Hg was used to measure the pH of a solution of 0.010 M acetic acid in 0.0358 M
sodium acetate. Calculate the cell potential expected at 25 C [K
a
=1.81 10
5
for acetic acid].
Solution
8.16. The voltage required to electrolyze certain solutions changes as the electrolysis proceeds because the concentrations in the solution
are changing. In an experiment, 500 dm
3
of a 0.0500 M solution of copper (II) bromide was electrolyzed until 2.872 g Cu was
deposited. Calculate the theoretical minimum voltage required to sustain the electrolysis reaction at the beginning and at the end of
the experiment.
Solution
8-6
8.17. Calculate the concentration of
3
I in a standard solution of iodine in 0.5 M KI, making use of the following standard electrode
potentials:

I
2
+2e
2I
E =0.5355 V

3
I
+2e
3I

E =0.5365 V

The molality of I

in the standard solution can be assumed to be 0.5 m.
Solution
8.18. Calculate the Nernst potential at 25 C arising from the equilibrium established in Problem 7.41.
Solution
8.19. It might seem plausible to separate lead and gold by making use of the great difference between their standard electrode potentials
(Table 8.1). In order to test this idea, one might electrolyze a solution containing 0.0100 M AuNO
3
and 0.0100 M Pb(NO
3
)
2
in a
well-stirred tank using platinum electrodes at low current density. As the potential difference is slowly increased from zero, which
metal will be deposited first? What will be the concentration of this metal ion in solution when the second metal begins to be
deposited? Do you think this is an acceptable method of separating the two metals?
Solution
8.20. Calculate the emf of the cell
Pt, H
2
2
(10 bar)
Solution
*8.21. Suppose that the cell in Problem 8.20 is set up but that the two solutions are separated by a membrane that is permeable to H
+
ions
but impermeable to Cl

ions. What will be the emf of the cell at 25 C?
Solution
8-7
*8.22. A typical biological cell has a volume of 10
9
cm
3
, a surface area of 10
6
cm
2
, and a membrane thickness of 10
6
cm; the dielectric
constant of the membrane may be taken as 3. Suppose that the concentration of K
+
ions inside the cell is 0.155 M and that the Nernst
potential across the cell wall is 0.085 V.
a. Calculate the net charge on either side of the wall, and
b. Calculate the fraction of the K
+
ions in the cell that are required to produce this charge.
Solution
*8.23. Calculate the emf at 25 C of the cell
Pt, H
2
(1 bar)|H
2
SO
4
(0.001 m)|CrSO
4
(s)|Cr
given the following standard electrode potential:
CrSO
4
(s) +2e
Cr +
2
4
SO E =0.40 V

a. First make the calculation neglecting activity coefficient corrections.
b. Then make the calculation using activity coefficients estimated on the basis of the Debye-Hckel limiting law.
Solution
*8.24. Write the individual electrode reactions and the overall reaction for
Cu|CuCl
2
(aq)|AgCl(s)|Ag
If the emf of the cell is 0.191 V when the concentration of CuCl
2
is 1.0 10
4
M and is 0.074 V when the concentration is 0.20 M,
make an estimate of the mean activity coefficient in the latter solution.
Solution
8-8
*8.25. a. Write both electrode reactions and the overall reaction for the cell
Tl|TlCl(s)|CdCl
2
(0.01 m)|Cd
b. Calculate E and E for this cell at 25 C from the following information:
Tl
+
+e
Tl E =0.34 V
Cd
2+
+2e
Cd E =0.40 V

The solubility product for TlCl is 1.6 10
3
mol
2
dm
6
at 25 C.
Solution
8.26. Problem 7.44 involved calculating the concentrations on each side of a membrane after a Donnan equilibrium had become
established. Which side of the membrane is positively charged? Calculate the Nernst potential across the membrane if the
temperature is 37 C.
Solution
8.27. The oxidation of lactate to pyruvate by the oxidized form of cytochrome crepresented as cytochrome c (Fe
3+
)is an important
biological reaction. The following are the relevant E values, relating to pH 7 and 25 C:
E/V
pyruvate
+2H
+
+2e
lactate
0.185
cytochrome c (Fe
3+
) +e
cytochrome c (Fe
2+
) 0.254

Calculate the equilibrium ratio
2+ 2
3+ 2
[cytochrome (Fe )] [pyruvate ]
[cytochrome (Fe )] [lactate ]
c
c

at pH 7 and 25 C. Also calculate the ratio at pH 6.
Solution
8-9
8.28. Suppose that the cell
Ag|AgCl(s)|HCl(0.10 m) HCl(0.01 m)|AgCl(s)|Ag
is set up and that the membrane separating the two solutions is permeable only to H
+
ions. What is the emf of the cell at 25 C?
Solution
8.29. a. Consider the cell
Pt, H
2
(1 bar)|HCl(m
1
) HCl(m
2
)|Pt, H
2
(1 bar)
in which the solutions are separated by a partition that is permeable to both H
+
and Cl
. The ratio of the speeds with which these ions

pass through the membrane is the ratio of their transport numbers t
+
and t
. Derive an expression for the emf of this cell.

b. If when m
1
=0.01 m and m
2
=0.01 m the emf is 0.0190 V, what are the transport numbers of the H
+
and Cl

ions?
Solution
8.30. The metal M forms a soluble nitrate and a very slightly soluble chloride. The cell
M|M
+
(0.1 m), HNO
3
(0.2 m)|H
2
(1 bar), Pt
has a measured E =0.40 V at 298.15 K. When sufficient solid KCl is added to make the solution of the cell 0.20 m in K
+
, the emf
changes to 0.15 V at 298.15 K as MCl precipitates. Calculate the K
sp
of MCl, taking all activity coefficients to be unity.
Solution
Chapter 8: Electrochemical Cells Temperature Dependence of Cell emfs
8-10
8.31. The substance nicotinamide adenine dinucleotide (NAD
+
) plays an important role in biological systems; under the action of certain
enzymes it can react with a reducing agent and release a proton to the solution to form its reduced form NADH. With pyruvate the
reduced form NADH undergoes the reaction
NADH +pyruvate

+H
+
NAD
+
+lactate

The appropriate E values, relating to 25 C and pH 7, are
pyruvate
+2H
+
+2e
lactate
E = 0.19 V
NAD
+
+H
+
+2e
NADH E = 0.34 V

Use these values to calculate G for the reaction, and also the equilibrium ratio
+
[lactate ][NAD ]
[pyruvate ][NADH]

(a) at pH 7, and (b) at pH 8.
Solution
Temperature Dependence of Cell emfs
8.32. a. Calculate the standard emf E for the reaction
fumarate
2
+lactate

succinate
2
+pyruvate

on the basis of the following information:
fumarate
2
+2H
+
+2e

succinate
2
E

=0.031 V
pyruvate

+2H
+
+2e

lactate
E =0.185 V

The E values relate to pH 7. The temperature coefficient / E T for this cell is 2.18 10
5
V K
1
.
b. Calculate G, H, and S at 25 C.
Solution
8-11
8.33. The Weston standard cell (see Figure 8.2b) is
Cd amalgam|CdSO
4

8
3
H
2
O(s)|Hg
2
SO
4
(s), Hg
(saturated solution)

a. Write the cell reaction.
b. At 25 C, the emf is 1.018 32 V and / E T =5.00 10
5
V K
1
. Calculate G, H, and S.
Solution
8.34. Salstrom and Hildebrand [J. Amer. Chem. Soc., 52, 4650(1930)] reported the following data for the cell
Ag(s)|AgBr(s)|HBr(aq)|Br
2
(g, 1 atm)|Pt
t/C 442.3 456.0 490.9 521.4 538.3 556.2
E/V 0.8031 0.7989 0.7887 0.7803 0.7751 0.7702

Find the temperature coefficient for this cell assuming a linear dependence of the cell potential with temperature. What is the
entropy change for the cell reaction?
Solution
8.35. The reaction taking place in the cell Mg(s)|Mg
2+
(aq), Cl
(aq)|Cl
2
(g,1 atm)|Pt is found to have an entropy change of 337.3 J K
1
mol
1
under standard conditions. What is the temperature coefficient for the cell?
Solution

8-12
*8.36. a. Estimate the Gibbs energy of formation of the fumarate ion, using data in Problem 8.32 and the following values.

f
G (succinate, aq) =690.44 kJ mol
1

f
G (acetaldehyde, aq) =139.08 kJ mol
1

f
G (ethanol, aq) =181.75 kJ mol
1

acetaldehyde +2H
+
+2e
ethanol E = 0.197 V

b. If the / E T value for the process
fumarate
2
+ethanol succinate
2
+acetaldehyde
is 1.45 10
4
V K
1
, estimate the enthalpy of formation of the fumarate ion from the following values.

f
H (succinate, aq) =908.68 kJ mol
1

f
H (acetaldehyde, aq) =210.66 kJ mol
1

f
H (ethanol, aq) =287.02 kJ mol
1

Solution
*8.37. a. Calculate the emf at 298.15 K for the cell
Tl|TlBr|HBr (unit activity)|H
2
(1 bar), Pt
b. Calculate H for the cell reaction in the following cell.
Tl|Tl
+
(unit activity), H
+
(unit activity)|H
2
(1 bar), Pt
For the half-cell
Tl
+
+e
Tl E =0.34 V
/ E T =0.003 V/K and
K
sp
(TlBr) =10
4
mol
2
dm
6

Solution
Chapter 8: Electrochemical Cells Applications of emf Measurements
8-13
Applications of emf Measurements
8.38. Calculate the solubility product and the solubility of AgBr at 25 C on the basis of the following standard electrode potentials:
AgBr(s) +e

Ag +Br
E =0.0713 V
Ag
+
+e

Ag E =0.7996 V
Solution
8.39. The emf of a cell
Pt, H
2
(1 bar)|HCl(aq)|AgCl(s)|Ag
was found to be 0.517 V at 25 C. Calculate the pH of the HCl solution.
Solution
8.40. The emf of the cell
Ag|AgI(s)I
(aq) Ag
+
(ag)|Ag
is 0.9509 V at 25 C. Calculate the solubility and the solubility product of AgI at that temperature.
Solution
8.41. An electrochemical cell M(s)|MCl(aq, 1.0 m)|AgCl(s)|Ag(s), where MCl is the chloride salt of the metal electrode M, yields a cell
potential of 0.2053 V at 25 C. What is the mean activity coefficient
of the electrolyte MCl? E for the M(s)|M

+
electrode is
0.0254 V.
Solution
8.42. The following thermodynamic data apply to the complete oxidation of butane at 25 C.
C
4
H
10
(g) +(13/2)O
2
(g) 4CO
2
(g) +5H
2
O(l)
1
1 1
=2877 kJ mol
=432.7 J K mol
H
S

Suppose that a completely efficient fuel cell could be set up utilizing this reaction. Calculate (a) the maximum electrical work and
(b) the maximum total work that could be obtained at 25 C.
Chapter 8: Electrochemical Cells Essay Questions
8-14
Solution
*8.43. At 298 K the emf of the cell
Cd, Hg|CdCl
2
(aq, 0.01 m), AgCl(s)|Ag
is 0.7585 V. The standard emf of the cell is 0.5732 V.
a. Calculate the mean activity coefficient for the Cd
2+
and Cl

ions.
b. Compare the value with that estimated from the Debye-Hckel limiting law, and comment on any difference.
Solution

*8.44. The following emf values were obtained by H. S. Harned and Copson [J. Amer. Chem. Soc., 55, 2206(1933)] at 25 C for the cell
Pt,H
2
(1 bar)|LiOH(0.01 m), LiCl(m)|AgCl(s)|Ag
at various molalities m of LiCl:
m/mol kg
1
0.01 0.02 0.05 0.10 0.20
E/V 1.0498 1.0318 1.0076 1.9888 0.9696

Obtain from these data the ionic product of water.
Solution

Essay Questions
8.45. Explain how emf measurements can be used to obtain G, H, and S for a reaction.
8.46. Suggest an additional example, giving details, for each of the electrochemical cells listed in Figure 8.8.

Chapter 8: Electrochemical Cells Solutions
8-15
Solutions
8.1. Write the electrode reactions, the overall reaction, and the expression for the emf for each of the following reversible cells.
a. Pt, H
2
(1 bar)|HCl(aq)|Pt, Cl
2
(1 bar)
b. Hg|Hg
2
Cl
2
(s)|HCl(aq)|Pt, H
2
(1 bar)
c. Ag|AgCl(s)|KCl(aq)|Hg
2
Cl
2
(s)|Hg
d. Pt, H
2
(1 bar)|HI(aq)|AuI(s)|Au
e. Ag|AgCl(s)|KCl(c
1
) KCl(c
2
)|AgCl(s)|Ag
Solution:
Given: see above
Required: electrode reactions, the overall reaction, and the expression for the emf
We calculate the emf, or electromotive force, from Eq. 8.13
[Y] [Z]
= ln
[A] [B]
u
y z
a b
RT
E E
zF
| |
|
\ .
where z is the number of electrons.

Electrode reactions Overall reaction EMF
2
2
H 2H 2
Cl 2 2Cl
e
e
+

+
+

2 2
H Cl 2H 2Cl
+
+ +
2 z =
( )
2 2
ln H Cl
2
u
RT
E E
F
+
( ( =

( )
2 2
2
2Hg l 2Cl Hg Cl 2
2H 2 H
e
e

+
+ +
+

( )
2 2 2
2Hg l 2Cl 2H Hg Cl H
+
+ + +
2 z =
( )
2 2
2 2
1
ln
2
H Cl
ln H Cl
2
u
u
RT
E E
F
RT
E E
F
+
+
| |
|
=
|
( (
\ .
( ( = +

8-16
( ) ( )
( ) ( )
2 2
Ag s Cl AgCl s
Hg Cl s 2 2Hg s 2Cl
e
e

+ +
+ +

( ) ( ) ( ) ( )
2 2
2Ag s Hg Cl s 2AgCl s 2Hg s + +
2 z =
No concentration dependence,
thereforeE E =
( )
( ) ( )
2
1
H g H
2
AuI s Au s I
e
e
+

+
+ +

( ) ( ) ( )
2
1
AuI s H g Au s H I
2
+
+ + +
1 z =
( )
ln H I
u
RT
E E
F
+
( ( =

( ) ( ) ( )
( ) ( ) ( )
1
2
Ag s Cl AgCl s
AgCl s Ag s Cl
c e
e c

+ +
+ +

( ) ( )
1 2
Cl Cl c c

1 z =
1
2
ln
u
c RT
E E
F c
| |
=
|
\ .

8-17
8.2. At 25 C and pH 7, a solution containing compound A and its reduced form AH
2
has a standard electrode potential of 0.60 V. A
solution containing B and BH
2
has a standard potential of 0.16 V. If a cell were constructed with these systems as half-cells,
a. Would AH
2
be oxidized by B or BH
2
oxidized by A under standard conditions?
b. What would be the reversible emf of the cell?
c. What would be the effect of pH on the equilibrium ratio [B][AH
2
]/[A][BH
2
]?
Solution:
Given:
A B
25 C, pH 7, 0.60V, 0.16 V T E E

= = = =
Required: see above
a. The reduction potential for each half reaction is:
2
2
A 2H 2 AH 0.60V
B 2H 2 BH 0.16V
e E
e E
+
+
+ + =
+ + =

We reverse the first reaction since we require a positive potential for the overall reaction to be spontaneous in the forward direction.
Therefore AH
2
is oxidized.
2 2
AH B A BH + +
b. The reversible emf would be
( )
B A
0.16V 0.60 V
0.44 V
E E E
E
E

=
=
=

c. The equilibrium ratio is given by
| || |
| || |
2
2
B AH
A BH
K = . There is no dependence of
3
[H O ]
+
in the equilibrium expression, and the hydrogen-
containing entities cancel in the numerator and denominator. As a result, there is no effect of pH on the equilibrium ratio.

8-18
8.3. Calculate the standard electrode potential for the reaction Cr
2+
+2e

Cr at 298 K. The necessary E values are
a. Cr
3+
+3e
Cr E =0.74 V
b. Cr
3+
+e
Cr
2+
E =0.41 V

Solution:

Given: see above

Required: E for Cr
2+

To solve this problem, we follow Example 8.3.
We first calculate the G values for these two reactions using Eq. 8.2
G zFE =
3 o 1 1
1
3 2 o 1 1
2
Cr 3 Cr 3 96 485 J mol ( 0.74V) =2.22 V 96 485 J mol (1)
Cr Cr 1 96 485 J mol ( 0.41V) =0.41 V 96 485 J mol (2)
e G
e G
+
+ +
+ =
+ = The reaction Cr
2+
+2e

Cr is obtained
by subtracting reaction (2) from reaction (1), and the G for this reaction is obtained from by subtracting
2
G from
1
G .

1 2
1 1
1
2.22 V 96485J mol 0.41 V 96485 J mol
1.81 V 96485J mol
1.81 V
G G G
G
G
G F
=
=
=
=

We solve for E by rearranging Eq. 8.2 and setting 2 z = .
1.81V
G
E
zF
F
E
=
2F
0.905V
0.91V
E
E
=
=

8-19
8.4. Write the individual electrode reactions and the overall cell reaction for the following cell:
Pt, H
2
|H
+
(1 m) F
2
, S
2
, H
+
(aq)|Pt
where F
2
represents the fumarate ion and S
2
the succinate ion. Write the expression for the emf of the cell.

Solution:

Given: see above

Required: E

We first write down the half reactions that are occurring in this cell.
( )
( )
2
2 2
LHSelectrode H 2H 1 2
RHSelectrode 2 2H aq F S
m e
e
+
+
+
+ +

The overall reaction is,
( ) ( )
2 2
2
2H aq F H 2H 1 S m
+ +
+ + +
The expression for the emf of the cell is determined from Eq. 8.13,
[Y] [Z]
= ln
[A] [B]
u
y z
a b
RT
E E
zF
| |
|
\ .

( )
| |
2
2
2
2
aq
2
2
2
2
S H
ln
2
F H
S 1
ln
2
F C
u
RT
E E
F
m
RT
E E
F
+
+
| |
( (

|
=
|
( (
\ .
| |
(

|
=
|
(
\ .

Where [H
+
]=C is the concentration of [H
+
] on the LHS.
We drop the superscript u since we have numerical values for the concentration.

8-20
8.5. Design electrochemical cells in which each of the following reactions occurs:
a. Ce
4+
(aq) +Fe
2+
(aq) Ce
3+
(aq) +Fe
3+
(aq)
b. Ag
+
(aq) +Cl
(aq) AgCl(s)
c. HgO(s) +H
2
(g) Hg(l) + H
2
O(l)
In each case, write the representation of the cell and the reactions at the two electrodes.
Solution:
Given: see above
Required: design the electrochemical cells
a. In writing the representation of the cell, the oxidation reaction always occurs at the anode, which is placed at the left-hand position of
the cell. In this case, Fe
2+
is losing electrons, and therefore the oxidation process is:

2 3
Fe Fe e
+ +
+
The cathode reaction is written on the right-hand side of the cell and is:
4 3
Ce Ce e
+ +
+
This is where reduction occurs. The overall reaction is the sum of these two reactions. The cell representation is:
Fe
3+
(aq) | Fe
2+
(aq) Ce
4+
(aq)| Ce
3+
(aq)
b. Upon examining the standard reduction potentials in Table 8.1, we see that the following half reactions can be combined to give the
cited reaction.
o
o
Ag (aq) + Ag 0.7996 V (1)
AgCl(s) + Ag +Cl (aq) 0.22233 V (2)
e E
e E
+

=
=

Reversal of equation (2), and then addition to equation (1) gives the overall desired equation:
Ag (aq) Cl (aq) AgCl(s)

+
+
8-21
Equation (1) is the reduction reaction and is placed on the right-hand side of the cell. The anode reaction is placed on the left-hand side of
the cell representation.
Ag|AgCl(s)|Cl
-
(aq) Ag
+
(aq)|Ag(s)
The voltage of this cell is the right-hand reduction potential minus the left-hand reduction potential.
1 2
0.7996 V 0.22233 V
0.57727V
E E E
E
E

=
=
=

c. HgO undergoes reduction to Hg and is the cathode. H
2
is oxidized and is the anode. The electrode potentials are obtained from Table
8.1 and the SRP Table.
o
2 2
o
2
2H O +2 H 2OH 0.8277 V (3)
HgO +H O +2 Hg +2OH 0.0977 V (4)
e E
e E

+ =
=

Reversing the sense of equation (3) and adding to (4) gives,
2 2
HgO(s) H (g) Hg(l) H O(l) + +
The cell is represented by
Pt, H
2
(g)|H
2
O(l),OH
-
(aq) HgO (s),H
2
O|OH
-
(aq) |Hg(l)
The cell potential is
( )
4 3
0.0977 V 0.8277 V
0.9254V
E E E
E
E

=
=
=

8-22
8.6. Calculate the equilibrium constant at 25 C for the reaction
2Fe
3+
(aq) +2I
(aq) 2Fe
2+
(aq) +I
2
(s)

using the standard electrode potentials given in Table 8.1.
Solution:
Given: Table 8.1
Required: K
We can calculate the equilibrium constant from Eq. 8.7
o o
0.0257
/ ln E V K
z
=
o
o
( / )
exp
0.0257
z E V
K
| |
=
|
\ .

The half cell reactions are
3 2 o
o
2
Fe Fe 0.771 V
I 2 2I 0.5355 V
e E
e E
+ +
+ =
+ =

And the overall emf is
0.771 V 0.5355 V
0.2355 V
E
E
=
=

We solve for K with 2 z = ,
8-23
( )
o
o
o
o 7
2(0.2355)
exp
0.0257
exp 18.32684825
91 043 525.2
9.10 10
K
K
K
K
| |
=
|
\ .
=
=
=

8-24
8.7. From data in Table 8.1, calculate the equilibrium constant at 25 C for the reaction
Sn +Fe
2+
Sn
2+
+Fe
Solution:
Given: Table 8.1
Required: K
We follow the same procedure as we did in problem 8.6 to solve for the equilibrium constant.
The half cell reactions are
2 o
2 o
Fe 2 Fe 0.447 V
Sn 2 Sn 0.1375 V
e E
e E
+
+
+ =
+ =

The overall emf is
( ) 0.447 V 0.1375 V
0.3095 V
E
E
=
=

Solving for K with 2 z = gives,
( )
o
o
o 11
o 11
2( 0.3095
exp
0.0257
exp 24.08560311
3.46 541 679 10
3.47 10
K
K
K
K
| |
=
|
\ .
=
=
=

8-25
8.8. The standard electrode potential at 25 C for
cytochrome c (Fe
3+
) +e

cytochrome c (Fe
2+
)
is 0.25 V. Calculate G for the process
1
2
H
2
(g) +cytochrome c (Fe
3+
) H
+
+cytochrome c (Fe
2+
)
Solution:
Given: E =0.25 V
Required: G
We calculate G for this reaction using Eq. 8.2,
G zFE = , where 1 z =
o 1
o 1
o 1
1 96 485 mol 0.25 J
24 121.25 J mol
24 kJ mol
G
G
G
=
=
=


8-26
8.9. Using the values given in Table 8.1, calculate the standard Gibbs energy change G for the reaction
H
2
+
1
2
O
2
H
2
O
Solution:
Given: Table 8.1
Required: G
From Table 8.1, we write the following half reactions:
2 2 1
2 2
O 4H 4 2H O 1.229V (1)
2H 2 H 0 (2)
e E
e E
+
+
+ + =
+ =

Subtracting (2) from of (1) gives the desired equation,
2 2 2
1
H O H O
2
+
The overall emf is
1.229 V 0
1.229 V
E
E
=
=

We calculate G for this reaction using Eq. 8.2,
o
o 1
o 1
o 1
, where z=2
2 96 485 mol 1.229 J
237 160.13 J mol
237.2 kJ mol
G zFE
G
G
G
=
=
=
=

8-27
*8.10. From the data in Table 8.1, calculate the equilibrium constant at 25 C for the reaction
2Cu
+
Cu
2+
+Cu
What will be produced if Cu
2
2
SO
4
?
Solution:
Given: Table 8.1
Required: K
We follow the same procedure as we did in problem 8.6 to solve for the equilibrium constant.
From Table 8.1, we write the following half reactions:
2 o
1
2 o
1
Cu +2 Cu 0.3419 V (1)
Cu + Cu 0.153 V
e E
e E
+
+ +
=
= (2)

To get the desired overall reaction, we subtract 2(2) from (1):
2
2Cu Cu Cu
+ +
+
1 2
0.3419V 0.153V
0.1889V
E E E
E
E

=
=
=

We solve for K from Eq. 8.7, with 2 z = ,
o
o
o 6
2(0.1889
exp
0.0257
2 422 690.131
2.42 10
K
K
K
| |
=
|
\ .
=
=

If Cu
2
2
SO
4
, then half will form Cu
2+
and half will form Cu.
8-28
8.11. For the reaction 3H
2
(g, 1 atm) +Sb
2
O
3
(s, cubic) 2Sb(s) +3H
2
O(l), G =83.7 kJ [Roberts and Fenwick, J. Amer. Chem. Soc.,
50, 2146(1928)]. Calculate the potential developed by the cell
Pt|H
2
(g, 1 atm)|H
+
|Sb
2
O
3
(s, cubic)|Sb(s)
Which electrode will be positive?
Solution:
Given: reaction above, G =83.7 kJ
Required: E, positive electrode
Note that the G given is for the reaction of 3 moles of H
2
to form 2 moles of Sb. The half cell reactions may be written as,
2
2 3 2
3H 6H 6
Sb O 6H 6 2Sb 3H O
e
e
+
+
+
+ + +

We can solve for E using Eq. 8.2,
o
o
o
3
o
o
o
83.7 10 J
6 96 485
0.1 445 820 594 V
0.145 V
G zFE
G
E
zF
E
E
E
=

=

=
=

For this reaction to be spontaneous, the electron flow is from the hydrogen electrode (oxidation) to the antimony electrode (reduction).

8-29
8.12. Calculate the emf for the following cell at 25 C:
Pt, H
2
2
(1 bar)
Solution:
Given: 25 C T = , cell above
Required: E
We calculate the emf for the cell from Eq. 8.27 where 1 z = ,
2
1
ln
1.0
0.0257ln
0.5
0.0178138825V
0.018V
m RT
E
F m
m
E
m
E
E
=
=
=
=

8-30
8.13. The pyruvate-lactate system has an E value of 0.185 V at 25 C and pH 7.0. What will be the potential of this system if the
oxidation has gone to 90% completion?
Solution:
Given: 0.185 V, pH 7.0, 90%completion E = =
Required: E
The process is,
pyruvate 2H 2 lactate e
+
+ +
And, the Nernst equation, given by Eq. 8.13
| | | |
| | | |
o
... Y Z
A B ...
u
y z
a b
RT
E E n
zF
| |
| =
|
\ .

For this process, this becomes
[lactate ]
ln
2 [pyruvate ]
RT
E E
F
| |
=
|
\ .

Solving for E we get,
0.0257 10
0.185V ln
2 90
0.1567656642V
0.157V
E
E
E
| |
=
|
\ .
=
=

8-31
8.14. a. From the data in Table 8.1, calculate the standard electrode potential for the half-reaction
Fe
3+
+3e

Fe
b. Calculate the emf at 25 C of the cell
Pt|Sn
2+
(0.1 m), Sn
4+
(0.01 m) Fe
3+
(0.5 m)|Fe
Solution:
Given: Table 8.1
Required: see above
a. To calculate the standard potential we follow example 8.3.
We first calculate the G values for these two reactions using Eq. 8.2
o
G zFE =

3 2 o 1 1
1
2 2 o 1 1
2
Fe Fe G 1 96 485 J mol (0.771 V)=-0.771 V 96 485 J mol (1)
Fe 2 Fe G 2 96 485 J mol ( 0.447 V)=0.894 V 96 485 J mol
e
e
+ +
+ +
+ =
+ =
3
(2)
Fe 3 Fe e
+
+

The half-reaction given above is the sum of (1) and (2). The G value for the given reaction is
o o o
1 2
o 1 1
o 1
o
-0.771 V 96 485 J mol 0.894 V 96 485 J mol
0.123 V 96 485 J mol
0.123 V
G G G
G
G
G F

= +
= +
=
=

We solve for E by rearranging Eq. 8.2 and setting 3 z = .
8-32
o
o
o
o
0.123 V
3
0.041 V
G
E
zF
F
E
F
E
=

b. The half cell reactions are:
3 o
2 4 o
Fe 3 Fe 0.041 V (3)
Sn Sn 2 0.151 V (4)
e E
e E
+
+ +
+ =
+ =

The overall reaction is obtained from the sum of 2(3) and 3(4)
3 2 4
2Fe 3Sn 2Fe 3Sn
+ + +
+ +
The electrical potential would be,
3 4
0.041V 0.151V
0.192 V
E E E
E
E

= +
=
=

From the Nernst equation, Eq. 8.13 we can calculate the emf using z =6.
( )
( ) ( )
3
3 2
[Y] [Z]
ln
[A] [B]
0.01 0.0257
0.192 ln
6
0.1 0.5
0.1683497424V
0.17V
u
y z
a b
RT
E E
zF
E
E
E
| |
=
|
\ .
| |
= |
|
\ .
=
=


8-33
8.15. The cell Pt|H
2
(1 bar), H
+
KCl(saturated)|Hg
2
Cl
2
|Hg was used to measure the pH of a solution of 0.010 M acetic acid in 0.0358 M
sodium acetate. Calculate the cell potential expected at 25 C [K
a
=1.81 10
5
for acetic acid].
Solution:
Given:
5
acetic acid sodiumacetate
0.010 , 0.0358 , 25 C, 1.81 10
a
c M c M T K = = = =
Required: E
The equilibrium constant, K
a
is given by,
| |
3
3
H CH COO
CH COOH
a
K
+
( (

=
Rearranging for [H
+
], we obtain
| |
( )
3
3
5
CH COOH
H
CH COO
1.81 10 0.010 M
H
a
K
+
+
( =

(

( =

( )
0.0358 M
( )
6
H 5.055865922 10
+
( =

From Table 8.1, the cell reactions are:
2

2 2
H 2H 2 0
Hg Cl 2 2Hg 2Cl 0.2412 V
e E
e E
+
+ =
+ + =

However, since the cathode reaction (the reduction reaction), is contained in the standard calomel (Hg
2
Cl
2(s)
) electrode, it is separated from
the oxidation of H
2
, and its concentrations are constant throughout the measurement. This is a pH meter, so the only concentration
that is relevant is [H
+
].
8-34
( )
2
2
6
ln H
2
0 0.2412V
0.0257
0.2412V ln 5.055865922 10
2
0.5546105085V
0.55V
RT
E E
F
E
E
E
E
+
( =

= +
=
=
=

8-35
8.16. The voltage required to electrolyze certain solutions changes as the electrolysis proceeds because the concentrations in the solution
are changing. In an experiment, 500 dm
3
of a 0.0500 M solution of copper (II) bromide was electrolyzed until 2.872 g Cu was
deposited. Calculate the theoretical minimum voltage required to sustain the electrolysis reaction at the beginning and at the end of
the experiment.
Solution:
Given: V = 500 dm3, [Cu
2+
] =0.0500 M, [Bi] =0.100 M, m
cu
=2.872 g
Required: E
i
, E
f

The reactions taking place during the electrolysis are:
2 o
o
2
Cu 2 Cu 0.34190 V
2Br Br +2 -1.80730 V
e E
e E
+

+ =
=

The overall reaction is:
2
2
Cu 2Br Cu Br
+
+ +
The electrical potential would be the sum of the two potentials,
o
o
0.34190 V 1.08730 V
0.74540 V
E
E
=
=

If the reverse reaction were taking place in a galvanic cell, the initial cell voltage would be:
( )( )
2
o 2
o
2
ln Cu Br
2
0.74540 V
0.0257
0.74540 V ln 0.0500 0.100
2
0.8 430 715 966 V
0.84 307 V
i
i
i
RT
E E
F
E
E
E
E
+
( ( =

=
=
=
=

8-36
Therefore a minimum voltage of 0.84 307 V would have to be applied at the beginning in order for the electrolysis reaction to occur.
At the end of the electrolysis, the concentrations are:
2 Cu
Cu
2
1
Cu 0.0500
2.872 g
Cu 0.0500
m
M
M V
M
+
+
| |
( =
|

\ .
( =

63.456 g
( )( )
1 3
2 5
2
5
mol 500 dm
Cu 0.0500 9.051941503 10
Cu 0.0499094806
Br 0.100 2 9.051941503 10
Br 0.0998189612
M M
M
M M
M
+
+

( =

( =

( =

( =

Therefore the final voltage required would be
( )( )
2 0.0257
0.74540 V ln 0.0 499 094 806 0.0 998 189 612
2
0.8 431 414 503 V
0.84 314 V
f
f
f
E M
E
E
=
=
=

The E
i
and E
f
are close because a small amount of Cu
2+
is plated out.

8-37
8.17. Calculate the concentration of
3
I in a standard solution of iodine in 0.5 M KI, making use of the following standard electrode
potentials:

I
2
+2e
2I
E =0.5355 V

3
I
+2e
3I

E =0.5365 V

The molality of I

in the standard solution can be assumed to be 0.5 m.
Solution:
Given:
KI
0.5 c M =
Required:
3
I
c
The overall reaction of interest is obtained by reversing the second equation and adding it to the first.
2 3
I I I
+
In this case, z

=2, and the standard electrode potential is
0.5355 V 0.5365V
0.0010 V
E
E
=
=

We can solve for the concentration of
3
I using Eq. 8.7, where the equilibrium constant for this process is given by,
8-38
( )
( )
( )
3
3
o o
o
o
o
3
o
I I
I

I
0.0257
/ ln
/
exp
0.0257
/ I
exp
0.0257 I
/
exp
0.0257
c
K
E V K
z
z E V
K
z E V
z E V
c c

(

=
(

=
| |
| =
|
\ .
| | (

| =
|
(
\ .
| |
| =
|
\ .

( )
( )
3
3
3
3
I
3
I
3
I
2 0.0010
0.5 mol dm exp
0.0257
0.4 625 649 996 mol dm
0.4 626 mol dm
c
c
c
| |
=
|
\ .
=
=

8-39
8.18. Calculate the Nernst potential at 25 C arising from the equilibrium established in Problem 7.41.
Solution:
Given: Problem 7.41, 25 C T =
Required: (=
o
E for concentration cells)
The Nernst potential is given by Eq. 8.19 as,
1
2
ln
c RT
zF c
=
From problem 7.41, we have the equilibrium concentrations of sodium and chloride as,
Palmitateside Other side
Na 0.18 Na 0.12
Cl 0.08 Cl 0.12
M M
M M
+ +

( ( = =

( ( = =

To calculate the Nernst potential, we only consider the Na
+
equilibrium, therefore,
0.18
0.0257ln
M
=
0.12M
0.0104204533V
10mV
=
=

8-40
8.19. It might seem plausible to separate lead and gold by making use of the great difference between their standard electrode potentials
(Table 8.1). In order to test this idea, one might electrolyze a solution containing 0.0100 M AuNO
3
and 0.0100 M Pb(NO
3
)
2
in a
well-stirred tank using platinum electrodes at low current density. As the potential difference is slowly increased from zero, which
metal will be deposited first? What will be the concentration of this metal ion in solution when the second metal begins to be
deposited? Do you think this is an acceptable method of separating the two metals?
Solution:
Given: Table 8.1,
( ) 3 3 2
AuNO Pb NO
0.0100 , 0.0100 c M c M = =
Required: see above
From Table 8.1 the two standard reduction potentials are given by,
2
Au Au 1.692V
Pb 2 Pb 0.1262V
e E
e E
+
+
+ =
+ =

We can see that Au
+
has a much higher reduction potential than Pb
2+
, therefore gold will be deposited first.
As the Au
+
concentration falls, the lead begins to be deposited. Therefore we have,
2
2Au(s) Pb 2Au Pb(s)
+ +
+ +
With z =2.
The potential for this reaction is given by,
1.692V 0.1262V
1.8182V
E
E
=
=

Following the procedure used in problem 8.17, we can calculate the concentration of Au
+
.
8-41
( )
( )
2
2
o o
o
o
2
o
2
Au

Pb
0.0257
/ ln
/
exp
0.0257
/ Au
exp
0.0257 Pb
c
K
E V K
z
z E V
K
z E V
+
+
+
+
(

=
(

=
| |
| =
|
\ .
| | (

| =
|
(
\ .

( )
Au
32
Au
32
Au
2 1.8182
0.0100 exp
0.0257
1.88 335 766 10
1.88 10
c M
c M
c M
+
+
+
| |
=
|
\ .
=
=

The conclusion is that only an infinitesimal amount of gold will be left in the solution by the time the lead starts to deposit at the electrode.
This is shown by the negligible concentration of gold. Therefore, this is an acceptable way to separate the two metals.

8-42
8.20. Calculate the emf of the cell
Pt, H
2
2
(10 bar)
Solution:
Given: see above
Required: E
At the right-hand electrode we have the reaction:
( ) ( )
2
1
H 0.2 H 10 bar
2
m e
+
+
And at the left-hand electrode we have,
( ) ( )
2
1
H 10 bar H 0.1
2
m e
+
+
The overall reaction, with z =1, is:
( ) ( ) ( ) ( )
2 2
1 1
H 0.2 H 1 bar H 10 bar H 0.1
2 2
m m
+ +
+ +
To calculate the cell emf, we use Eq. 8.7,
( )
( )
1
2
1
2
0.0257
ln , where 1
0.2 1 bar
0.0257ln
0.1 10 bar
0.0117743359V
11.8mV
E K z
z
E
E
E
= =
=
=

8-43
*8.21. Suppose that the cell in Problem 8.20 is set up but that the two solutions are separated by a membrane that is permeable to H
+
ions
but impermeable to Cl

ions. What will be the emf of the cell at 25 C?
Solution:
Given: Problem 8.20, a membrane that is only permeable to H
+

Required: E
From problem 8.20, we have the half reactions at each electrode as:
( ) ( )
( ) ( )
2
1
LHS: H 10 bar H 0.1
2
1
RHS: H 0.2 H 10 bar
2
m e
m e
+
+
+
+

Every H
+
ion produced in the LHS solution will have to pass through the membrane to preserve the electrical neutrality (ion gradient).
( ) ( ) H 0.1 H 0.2 m m
+ +

The net reaction is therefore,
( ) ( )
2 2
1 1
H 1 bar H 10 bar
2 2

The cell emf is calculated from Eq. 8.27,
2
1
ln , where 1
m RT
E z
F m
= =
We take the ratio of pressures as a measure of the ratio of molalities.
8-44
( )
( )
1
2
1
2
1 bar
0.0257ln
10 bar
0.0295882184V
29.6mV
E
E
E
=
=
=

8-45
*8.22. A typical biological cell has a volume of 10
9
cm
3
, a surface area of 10
6
cm
2
, and a membrane thickness of 10
6
cm; the dielectric
constant of the membrane may be taken as 3. Suppose that the concentration of K
+
ions inside the cell is 0.155 M and that the Nernst
potential across the cell wall is 0.085 V.
a. Calculate the net charge on either side of the wall, and
b. Calculate the fraction of the K
+
ions in the cell that are required to produce this charge.
Solution:
Given:
9 3 6 2 6
K
10 cm, 10 cm, 10 cm, 3, 0.155 , 0.085 V V A l c M
+
= = = = = =
Required: see above
a. The net charge on either side of the wall can be calculated using
Q CV = .
The capacitance is given by Eq. 8.20 as,
0
A
C
l

=
We solve for the net charge in the following expression,
0
12 2 1 2
8.854 10 C N m
A
Q V
l
Q

=
=
( )
( )
10 2
3 10 m
( )
( )
( )
8
14 2 1 1
14
1
14
0.085V
10 m
2.25777 10 C N m V
2.25777 10 F V
where1F 1CV
2.3 10 C
Q
Q
Q

=
=
=
=

b. The fraction of K
+
ions required to produce this charge is given by
8-46
14
19
2.25 777 10 C
1.602 10 C
140 900 ions
Q
e
Q
e
=

The number of ions inside the cell is,
12 23 10
0.155 10 6.022 10 9.3341 10
=
Therefore the fraction of ions at the surface is,
6
10
6
140934.4569
1.509888012 10
9.3341 10
1.51 10

8-47
*8.23. Calculate the emf at 25 C of the cell
Pt, H
2
(1 bar)|H
2
SO
4
(0.001 m)|CrSO
4
(s)|Cr
given the following standard electrode potential:
CrSO
4
(s) +2e
Cr +
2
4
SO E =0.40 V

a. First make the calculation neglecting activity coefficient corrections.
b. Then make the calculation using activity coefficients estimated on the basis of the Debye-Hckel limiting law.
Solution:
Given: see above
Required: see above
a. At the left-hand electrode we have,
2
1
H H
2
e
+
+
and the right-hand electrode, we have,
2
4 4
CrSO (s) 2 Cr(s) SO e + +
The overall reaction is given by,
2
4 2 4
CrSO (s) H 2H Cr(s) SO
+
+ + +
With 0.40 V and 2 E z = =
The emf, neglecting the activity coefficients, is given by Eq. 8.13
8-48
( )
( ) ( )
( )
2
2
4
2
[Y] [Z]
ln
[A] [B]
ln H SO
2
0.0257
0.40V ln 0.002 0.001
2
0.1515199165V
0.152V
u
y z
a b
u
RT
E E
zF
RT
E E
F
E
E
E
+
| |
=
|
\ .
( ( =

=
=
=

b. To calculate the activity coefficients, we first calculate the ionic strength of the solution from Eq. 7.103,
( )
2
2 2
1
2
1
1 0.002 2 0.001
2
0.003
i i
i
I c z
I
I M
=
= +
=

Now we rearrange the Debye-Hckel limiting law given by Eq. 7.111,
( )
3
3
10
0.51 /mol dm
0.51 2 1 0.003
log 0.51 /mol dm
10
10
0.8792903343
z z I
z z I
=
=
=
=

Substituting back into the expression for the emf obtained above we can solve for the true emf of the solution.
8-49
( )
( )
( ) ( )( )
( )
2
2 2
4
2
2 3
4
2 3
ln H SO
2
ln H SO
2
0.0257
0.40V ln 0.002 0.001 0.8792903343
2
0.1465608393V
0.147V
u
u
RT
E E
F
RT
E E
F
E
E
E

+

+
( ( =

( ( =

=
=
=

8-50
*8.24. Write the individual electrode reactions and the overall reaction for
Cu|CuCl
2
(aq)|AgCl(s)|Ag
If the emf of the cell is 0.191 V when the concentration of CuCl
2
is 1.0 10
4
M and is 0.074 V when the concentration is 0.20 M,
make an estimate of the mean activity coefficient in the latter solution.
Solution:
Given:
4
1 1 2 2
0.191 V, 1.0 10 , 0.074 V, 0.20 E c M E c M = = = =
Required:

At the left-hand electrode we have,
2
Cu Cu 2e
+
+
and the right-hand electrode, we have,

AgCl(s) Ag Cl e + +
2
2AgCl(s) Cu(s) 2Ag(s) 2Cl Cu
+
+ + + , where 2 z =
To a good approximation, it can be assumed that the activity coefficients at 10
-4
M are unity. (The DHLL gives 0.988
= ) Thus the
standard electrical potential is obtained by rearranging Eq. 8.13
( )
( )( )
( )
2
2
2
4 4
[Y] [Z]
ln
[A] [B]
ln Cu Cl
2
0.0257
0.191V ln 10 2 10
2
0.1462447388V
u
y z
a b
u
RT
E E
zF
RT
E E
F
E
E
+

| |
=
|
\ .
( ( = +

= +
=

8-51
Suppose that at 0.20 M the activity coefficients are and
+
, then we can solve for the mean activity coefficient from Eq. 8.40.
( )
( )
2
2
Cu Cl
2
2 2
ln
2
ln Cu Cl
2
u
u
RT
E E a a
F
RT
E E
F

+
+
+
=
( ( =

( )
( )( )
( )
2
2 3
2
3
3
3
ln Cu Cl
2
0.0257 0.0257
0.074V 0.1462447388V ln 0.20 0.40 ln
2 2
0.0257
0.0280147899 ln
2
ln 2.180139285
0.4834955852
0.48
RT
E E
F

( ( =

=
=
=
=
=

8-52
*8.25. a. Write both electrode reactions and the overall reaction for the cell
Tl|TlCl(s)|CdCl
2
(0.01 m)|Cd
b. Calculate E and E for this cell at 25 C from the following information:
Tl
+
+e
Tl E =0.34 V
Cd
2+
+2e
Cd E =0.40 V

The solubility product for TlCl is 1.6 10
3
mol
2
dm
6
at 25 C.
Solution:
Given: cell above,
3 2 6
sp
1.6 10 mol dm , 25 C K T = =
Required: see above
a. The left-hand or anode reaction is:
( )
Tl(s) Cl 0.02 TlCl(s) m e
+ +
The right-hand, or cathode reaction is:
( )
2
Cd 0.01 2 Cd(s) m e
+
+
The overall reaction is:
( ) ( )
2
Cd 0.01 2Tl(s) 2Cl 0.02 Cd(s) 2TlCl(s) where 2 m m z
+
+ + + =
b. To use the electrical potentials given above, we rewrite the overall equation as (Cl
-
is a spectator ion):
( ) ( )
2
2
Cd 0.01 2Tl(s) Cd(s) 2Tl in0.01 CdCl where 2 m m z
+ +
+ + =
The standard electrical potential is given by,
( ) 0.40V 0.34 V
0.06 V
E
E
=
=

8-53
To solve for the emf, we use Eq. 8.13,
2
2
sp
Ti
ln
2 Cd
where Ti Cl
u
RT
E E
F
K
+
+
+
| |
(

|
=
| (

\ .
( ( =

( )
( ) ( )
sp
2
sp
2
2
2
3
2
Ti
Cl
0.0257
ln
2
Cl Cd
1.6 10
0.0257
0.06V ln
2
0.02 0.01
0.0542652107V
0.054V
u
u
K
K
E E
E
E
E
+
+
( =

(

| |
|
=
|
( (
\ .
| |
|
=
|
\ .
=
=


8-54
8.26. Problem 7.44 involved calculating the concentrations on each side of a membrane after a Donnan equilibrium had become
established. Which side of the membrane is positively charged? Calculate the Nernst potential across the membrane if the
temperature is 37 C.
Solution:
Given: Problem 7.44, 37 C T =
Required: (used for concentration cells)
We follow the same procedure as problem 8.18 to solve for the Nernst potential.
From problem 7.44, we have the equilibrium concentrations of potassium and chloride as,
right-handside left-hand side
K 0.04 K 0.16
Cl 0.04 Cl 0.01
M M
M M
+ +

( ( = =

( ( = =

The diffusible K
+
ions are at a higher potential on the right-hand side of the membrane; there is thus a tendency for few of them to cross to
the left-hand side and create a positive potential there. The same conclusion can be made by considering the diffusible Cl
-
ions; they are at a
higher potential on the left-hand side, and few tend to cross to the right-hand side and create a negative potential.
The Nernst potential is given by Eq. 8.19 as,
1
2
ln
c RT
zF c
=
1
8.3145J K
=
1
mol
310.15 K
1
1 96485C mol
0.16
ln
M
0.04M
1
0.0370513109J C
where1 J 1CV
37mV
=
=
=

8-55
8.27. The oxidation of lactate to pyruvate by the oxidized form of cytochrome crepresented as cytochrome c (Fe
3+
)is an important
biological reaction. The following are the relevant E values, relating to pH 7 and 25 C:
o
'/V
pyruvate 2H 2 lactate
E
e
+
+ +
3 2
-0.185
cytochrome (Fe ) cytochrome (Fe ) 0.254 c e c
+ +
+

Calculate the equilibrium ratio
2 2
2
2
3
cytochrome (Fe ) pyruvate H
cytochrome (Fe ) lactate
c
c
+ +
+
( ( (

( (

at pH 7 and 25 C. Also calculate the ratio at pH 6.
Solution:
Given: pH 7, 25 C T = =
Required: equilibrium ratio at pH 7 and pH 6
We begin by first writing the overall reaction as:
( ) ( )
3 2
lactate 2cytochrome Fe 2cytochrome Fe pyruvate 2H c c
+ + +
+ + +
Where z =2 and
0.254V 0.185V
0.439V
E
E
= +
=

If K is the equilibrium constant given at pH 7, then
2+ 2 2
3+ 2
[cytochrome (Fe )] [pyruvate ][H ]
c
K
c
+
=
And the equilibrium ratio at pH 7 is justK (unitless).
8-56
From Eq. 8.6 we can obtainK ,
o o
o
ln
0.0257
' ln '
2
RT
E K
zF
E K
=
=

o
14
14
2
' exp '
0.0257
2
' exp (0.439)
0.0257
' 6.870 472 098 10
' 6.87 10
K E
K
K
K
| |
=
|
\ .
| |
=
|
\ .
=
=

At pH 6, the equilibrium ratio is K
( ) ( )
2+ 2
2
true 3+ 2
2 2
7 6
true
7
14
[cytochrome (Fe )] [pyruvate ]
[H ]
10 10
10
6.870472098 10
c
K K
c
K K M K M
M
K
+

= =
= =
=
( )
2
6
10 M
( )
2
12
12
6.870472098 10
6.87 10
K
K
=
=

8-57
8.28. Suppose that the cell
Ag|AgCl(s)|HCl(0.10 m) HCl(0.01 m)|AgCl(s)|Ag
is set up and that the membrane separating the two solutions is permeable only to H
+
ions. What is the emf of the cell at 25 C?
Solution:
Given: see above, a membrane that is only permeable to H
+

Required: E
We can solve this problem in a similar manner as problem 8.21.
The half reactions for each electrode are:
( )

LHS Ag Cl AgCl(s)
RHS Ag(s) Cl 0.01 AgCl(s)
e
m e
+ +
+ +

The electrical neutrality is maintained by the passage of H
+
ions from right to left:
( ) ( ) H 0.01 H 0.10 m m
+ +

The net reaction is therefore,
( ) ( ) ( ) ( ) H 0.01 Cl 0.01 H 0.10 Cl 0.10 m m m m
+ +
+ +
The cell emf is calculated from Eq. 8.13,
8-58
prod prod
react react
0.0257
ln , where 1and 0
H Cl
H Cl
0.10
0.0257ln
E E K z E
z
K
m
E
+
+
= = =
( (

=
( (

=
( )
0.10 m
( )
0.01m
( )
0.01m
( )
0.1183528738V
0.12V
E
E
=
=

8-59
8.29. a. Consider the cell
Pt, H
2
(1 bar)|HCl(m
1
) HCl(m
2
)|Pt, H
2
(1 bar)
in which the solutions are separated by a partition that is permeable to both H
+
and Cl
. The ratio of the speeds with which these ions

pass through the membrane is the ratio of their transport numbers t
+
and t
. Derive an expression for the emf of this cell.

b. If when m
1
=0.01 m and m
2
=0.01 m the emf is 0.0190 V, what are the transport numbers of the H
+
and Cl

ions?
Solution:
Given: see above
Required: see above
a. The half reactions for each electrode are:
( )
( )
2 1
2 2
1
LHS: H H
2
1
RHS: H H
2
m e
m e
+
+
+
+

To maintain electrical neutrality of the solutions, for every mole of H
+
produced in the LHS solution, t
+
mol of H
+
will cross the membrane
from the left to the right, and t
-
mol of Cl
-
ions will pass fromright to left. In the LHS solution, there is therefore a net gain of,
( ) 1 mol mol of H t t
+
+
= and of mol of Cl t

.
In the RHS solution, the net loss is
( ) 1 mol mol of H t t
+
+
= and of mol of Cl t

The overall process is thus,
( ) ( ) ( ) ( )
2 2 1 1
H Cl H Cl t m t m t m t m
+ +

+ +
The emf is given by Eq. 8.13,
8-60
1 1
2 2
2
2
1
0.0257
ln , where 1 and 0
0.0257ln
0.0257ln
t t
t t
t
t
E E K z E
z
m m
E
m m
m
E
m

= = =
=
| |
=
|
\ .

2
1
0.0257 2 ln
m
E t
m
=
b. To calculate the transport numbers we use the expression derived above with
1 2
0.01 , 0.10 m m m m = =
2
1
0.0257 2 ln
0.0190V 0.10
ln
0.0257 2
m
E t
m
m
t
=
=
0.01m
0.1605368707
0.161
1 0.1605368707
0.8394631293
0.839
t
t
t
t
t
+
+
+
=
=
=
=
=

8-61
8.30. The metal M forms a soluble nitrate and a very slightly soluble chloride. The cell
M|M
+
(0.1 m), HNO
3
(0.2 m)|H
2
(1 bar), Pt
has a measured E =0.40 V at 298.15 K. When sufficient solid KCl is added to make the solution of the cell 0.20 m in K
+
, the emf
changes to 0.15 V at 298.15 K as MCl precipitates. Calculate the K
sp
of MCl, taking all activity coefficients to be unity.
Solution:
Given:
1 2
K
0.40 V, 298.15 K, 0.20 , 0.15V, 1 E T c m E
+

= = = = =
Required: K
sp

( )
( ) ( )
2
LHS: M M 0.1
1
RHS: H 0.2 H 1bar
2
m e
m e
+
+
+
+

( ) ( ) ( )
2
1
M H 0.2 M 0.1 H 1 bar
2
m m
+ +
+ +
with 1 z = and
.
2
o o o
H |H M |M
o o
M |M
o o
M |M
0
E E E
E E
E E
+ +
+
+
=
=
=

Using Eq. 8.13,
8-62
M
H
M |M
[Y] [Z]
ln , where 1
[A] [B]
M
ln
H
0.1
0.40 V 0.0257ln
u
y z
a b
RT
E E z
zF
RT
E E
zF
m
E
+
+
+
+
+
| |
= =
|
\ .
| | (

| = +
|
(
\ .
= +
0.2 m
M |M
0.4178138825V E
+
=

Upon addition of KCl, almost all of the M
+
precipitates, and 0.10 m Cl
-
is in excess. The value of M
+
in solution is found from the K
sp
,
sp
sp
M Cl
M
Cl
K
K
+
+
( ( =

( =

(

Using the Nernst equation, we can solve for the solubility product,
o
o
o
7 2
ln
H Cl
ln
0.0257 H Cl
H Cl exp
0.0257
0.15 V-(-0.4 178 138 825 V)
(0.20 )(0.10 )exp
0.0257
5.961 362 163 10
sp
sp
sp
sp
sp
K
RT
E E
zF
K
E E
E E
K
K m m
K m
K
+
+
+
| |
| =
|
( (
\ .
| |
| =
| ( (
\ .
| |
( ( =
|

\ .
| |
=
|
\ .
=
7 2
6.0 10
sp
m
=

8-63
8.31. The substance nicotinamide adenine dinucleotide (NAD
+
) plays an important role in biological systems; under the action of certain
enzymes it can react with a reducing agent and release a proton to the solution to form its reduced form NADH. With pyruvate the
reduced form NADH undergoes the reaction
NADH +pyruvate

+H
+
NAD
+
+lactate

The appropriate E values, relating to 25 C and pH 7, are
pyruvate
+2H
+
+2e
lactate
E = 0.19 V
NAD
+
+H
+
+2e
NADH E = 0.34 V

Use these values to calculate G for the reaction, and also the equilibrium ratio
| |
lactate NAD
pyruvate NADH H

+
( (

( (

(a) at pH 7, and (b) at pH 8.

Solution:
Given: see above
Required: G, equilibrium ratio
a. The overall reaction that is obtained by reversing the second half reaction and summing the two together:

pyruvate H NADH lactate NAD
+ +
+ + + where 2 z = and,
( ) 0.19 V 0.34 V
0.15V
E
E
=
=

To find G we use Eq. 8.2,
G zFE =
8-64
1
1
1
1
2 96485Cmol 0.15V
28945.5CV mol
where1J 1CV
28945.5J mol
29kJ mol
G
G
G
G
=
=
=
=
=

To solve for the equilibrium ratio, we follow the thought process used in problem 8. 27. If K is the equilibrium constant given at pH 7, then
+
[lactate ][NAD ]
[pyruvate ][NADH][H ]
K
+
=
And the equilibrium ratio at pH 7 is justK (unitless)
From Eq. 8.5, we can solve forK .
o
o
1
1 1
3 1
5
' ln '
'
' exp( )
28945.5 J mol
' exp
( 8.3145 J K mol )(298.15 K)
' 117 763.1471 dm mol
' 1.2 10
G RT K
G
K
RT
K
K
K
| |
=
|
\ .
=
=

b. At pH 8, the equilibrium ratio is K
8-65
| |
( )
( )
true
7 8
true
7
8
6
lactate NAD
' H
pyruvate NADH
'(10 )= ''(10 )
10
''=117 763.1471
10
'' 1177 631.471
'' 1.2 10
K K
K K M K M
M
K
M
K
K

+
( (

( = =

(

=
=
=

8-66
8.32. a. Calculate the standard emf E for the reaction
fumarate
2
+lactate

succinate
2
+pyruvate

on the basis of the following information:
fumarate
2
+2H
+
+2e

succinate
2
E

=0.031 V
pyruvate

+2H
+
+2e

lactate
E = 0.185 V

The E values relate to pH 7. The temperature coefficient / E T for this cell is 2.18 10
5
V K
1
.
b. Calculate G, H, and S at 25 C.
Solution:
Given: pH 7,
5 1
/ 2.18 10 V K E T =
Required: see above
a. To find the standard emf, we first determine that the overall reaction is:
2 2
fumarate lactate succinate pyruvate + + where 2 z =
Therefore,
( ) 0.031 V 0.185 V
0.216V
E
E E
=
= =

(Note that this is alsoE , the hydrogen ions having cancelled out.)
b. To calculate G, we use E from above and substitute into Eq. 8.2
8-67
1
1
1

2 96485 C mol 0.216V
41681.52C V mol
where1 J 1 C V
41.7kJ mol
G zFE
G
G
G
=
=
=
=
=

The entropy change is obtained from Eq 8.23,
1 5 1
1 1
1 1
2 96485 C mol 2.18 10 V K
4.206746C V mol K
where1 J 1 C V
4.21J mol K
P
E
S zF
T
S
S
S
| |
=
|
\ .
=
=
=
=

To calculate enthalpy, we use the relationship between Gibbs energy and entropy we learned earlier as,
1
41681.52J mol 298.15 K
H G T S
H

= +
= +
( )
1 1
4.206746J mol K
( )
1
1
40427.27868J mol
40.4kJ mol
H
H
=
=

8-68
8.33. The Weston standard cell (see Figure 8.2b) is
Cd amalgam|CdSO
4

8
3
H
2
O(s)|Hg
2
SO
4
(s), Hg
(saturated solution)

a. Write the cell reaction.
b. At 25 C, the emf is 1.018 32 V and / E T =5.00 10
5
V K
1
. Calculate G, H, and S.
Solution:
Given:
5 1
25 C, 1.01832V, / 5.00 10 V K T E E T = = =
Required: see above
2
2
2
LHS: Cd(Hg) Cd 2
RHS: Hg 2 2Hg
e
e
+
+
+
+

2 2
2
Cd(Hg) Hg Cd 2Hg
+ +
+ + with 2 z =
Since the solution is saturated with
2 4 2
8
Hg SO H O
3
, the overall reaction can be written as,
2 4 2 4 2
8 8
Cd(Hg) Hg SO (s) H O(l) CdSO H O(s) 2Hg(l)
3 3
+ + +
b. We can calculate G, H, and S in a similar manner shown in problem 8.32.
From Eq. 8.2,
8-69
1
1
1

2 96845 C mol 1.01832V
196505.2104C V mol
where1 J 1 C V
196.5kJ mol
G zFE
G
G
G
=
=
=
=
=

The entropy change is obtained from Eq 8.23,
1 5 1
1 1
1 1
2 96845 C mol 5.00 10 V K
9.6485C V mol K
where1 J 1 C V
9.65J mol K
P
E
S zF
T
S
S
S
| |
=
|
\ .
=
=
=
=

1
196505.2104J mol 298.15 K
H G T S
H

= +
= +
( )
1 1
9.6485J mol K
( )
1
1
199381.9107J mol
199kJ mol
H
H
=
=

8-70
8.34. Salstrom and Hildebrand [J. Amer. Chem. Soc., 52, 4650(1930)] reported the following data for the cell
Ag(s)|AgBr(s)|HBr(aq)|Br
2
(g, 1 atm)|Pt
t/C 442.3 456.0 490.9 521.4 538.3 556.2
E/V 0.8031 0.7989 0.7887 0.7803 0.7751 0.7702

Find the temperature coefficient for this cell assuming a linear dependence of the cell potential with temperature. What is the
entropy change for the cell reaction?
Solution:
Given: data above
Required: S
To solve for S , we need to find the temperature coefficient,
P
E
T
| |
|
\ .
from the data above.
Since we are only interested in the slope of the line best fit, we do not need to convert the temperature data to Kelvin.
We can perform a linear regression analysis, using t as the independent variable and E as the dependent variable.
The result is:
4
0.93046355 2.88337 10 E t
=
Differentiation with respect to t gives,
4 1
4 1
2.88337 10 V C
2.88337 10 V K
P
P
E
T
E
T

| |
=
|
\ .
| |
=
|
\ .

Substituting this value into Eq. 8.23 gives the entropy change,
8-71
1 4 1
1 1
1 1
96485 C mol 2.88337 10 V K
27.82019545CV K mol
where1 J 1 C V
27.82J K mol
P
E
S zF
T
S
S
S

| |
=
|
\ .
=
=
=
=

8-72
8.35. The reaction taking place in the cell Mg(s)|Mg
2+
(aq), Cl
(aq)|Cl
2
(g,1 atm)|Pt is found to have an entropy change of 337.3 J K
1
mol
1
under standard conditions. What is the temperature coefficient for the cell?
Solution:
Given:
1 1
337.3J K mol S =
Required:
P
E
T
| |
|
\ .

The overall reaction we are concerned with is,
2
2
Mg(s) +Cl (g) Mg (aq) +2Cl (aq), with z=2
+

Rearranging Eq. 8.23, we can solve for the temperature coefficient,
1 1
337.3J K mol
P
P
P
E
S zF
T
E S
T zF
E
T
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
1
2 96485 C mol
3 1 1
3 1
1.7479401 10 J C K
where1 J 1 C V
1.748 10 V K
P
P
E
T
E
T

| |
=
|
\ .
=
| |
=
|
\ .

8-73
*8.36. a. Estimate the Gibbs energy of formation of the fumarate ion, using data in Problem 8.32 and the following values.

f
G (succinate, aq) =690.44 kJ mol
1

f
G (acetaldehyde, aq) =139.08 kJ mol
1

f
G (ethanol, aq) =181.75 kJ mol
1

acetaldehyde +2H
+
+2e
ethanol E = 0.197 V

b. If the / E T value for the process
fumarate
2
+ethanol succinate
2
+acetaldehyde
is 2.18 10
5
V K
1
, estimate the enthalpy of formation of the fumarate ion from the following values.

f
H (succinate, aq) =908.68 kJ mol
1

f
H (acetaldehyde, aq) =210.66 kJ mol
1

f
H (ethanol, aq) =287.02 kJ mol
1

Solution:
Given: problem 8.32,
f
G,
5 1
2.18 10 V K
P
E
T

| |
=
|
\ .
,
f
H
Required: see above
a. The two reactions of interest are,
2 2
fumarate 2H 2 succinate 0.031V (1)

acetaldehyde 2H 2 ethanol 0.197 V (2)
e E
e E
+
+
+ + =
+ + =

Subtracting (2) from (1) gives the desired reaction:
2 2
fumarate ethanol succinate acetaldehydewith 2 z + + =
And a standard electrical potential of,
8-74
0.031V 0.197 V
0.228 V
E
E
= +
=

The Gibbs energy for the reaction is calculated from Eq. 8.2
1
1
1

2 96845 C mol 0.228V
43997.16C V mol
where1 J 1 C V
43997.16J mol
G zFE
G
G
G
=
=
=
=
=

To find the Gibbs energy of formation of fumarate, we use Eq. 3.91
o o o
o o o o o
succinate acetaldehyde ethanol fumarate
o o o o o
fumarate succinate acetaldehyde ethanol
o 1
fumarate
( )
690.44 kJ mol 139.08 kJ mol
f f
f f f f
f f f f
f
G G G
G G G G G
G G G G G
G

=
= + +
= +
= +

1 1 1
o 1
fumarate
o 1
fumarate
( 181.74 kJ mol ) ( 43.99716 kJ mol )
325.61284 kJ mol
326 kJ mol
f
f
G
G

=
=

b. To find the enthalpy of formation of fumarate, we first need to find the enthalpy of the reaction.
From Eq. 8.23, we calculate the entropy, and then use it to find the enthalpy.
8-75
( )
1 5 1
1 1
1 1
1
2 96 485 C mol 2.18 10 V K
4.222 442 C V mol K
where 1 J =1 C V
4.222 442 J mol K
43 997.16 (298.15)( 4.222 442)
45 256.08 J mol
45.25 608 kJ m
P
E
S zF
T
S
S
S
H G T S
H
H
H

| |
=
|
\ .
=
=
=
= +
= +
=
=
1
ol

To find the enthalpy of formation of fumarate, we use Eq. 2.53
( ) ( )
( )
succinate acetaldehyde ethanol fumarate
products reactants
f f
f f f f
H H H
H H H H H

=
= + +

o o o o o
fumarate succinate acetaldehyde ethanol
o 1 1 1 1
fumarate
o 1
fumarate
o
fumarate
908.68 kJ mol 210.66 kJ mol ( 287.02 kJ mol ) ( 45.25 608 kJ mol )
787.06 392 kJ mol
787 kJ
f f f f
f
f
f
H H H H H
H
H
H

= +
=
=
=
1
mol

8-76
*8.37. a. Calculate the emf at 298.15 K for the cell
Tl|TlBr|HBr (unit activity)|H
2
(1 bar), Pt
b. Calculate H for the cell reaction in the following cell.
Tl|Tl
+
(unit activity), H
+
(unit activity)|H
2
(1 bar), Pt
For the half-cell
Tl
+
+e
Tl E =0.34 V
/ E T =0.003 V/K and
K
sp
(TlBr) =10
4
mol
2
dm
6
Solution:
Given: ( )
1 4 2 6
sp
298.15K, 0.34V, / 0.003V K , TlBr 10 mol dm T E E T K
= = = =
Required: see above,
( )
( ) ( )
2
LHS: Tl Tl inHBr; 1
1
RHS: H 1 H 1bar
2
a e
a e
+
+
= +
= +

( ) ( ) ( )
2
1
Tl H 1 M inHBr; 1 H 1 bar
2
a a
+ +
+ = = + with 1 z = and
2
o o o
H |H Tl |Tl
o o
Tl |Tl
o o
Tl |Tl
0
0.34 V
E E E
E E
E E
+ +
+
+
=
=
= =

The emf is given by Eq. 8.13,
8-77
sp
sp
Tl
0.0257ln
H
Tl Br
Tl
Br
u
E E
K
K
+
+
+
+
| | (

| =
|
(
\ .
( ( =

( =

(

o
4 2 6
0.0257ln
Br H
10 mol dm
0.34 0.0257ln
1 1
0.103 294 252 V
0.10 V
u
sp
u
K
E E
E
E
E
+

| |
| =
|
( (
\ .
| |
=
|
\ .
=
=

2
1
0.0257 2 ln
m
E t
m
=
b. We can calculate the enthalpy using Eq. 8.25 and the data given for the half cell reaction.

( )
1 1
1 96 485 C mol 0.34 V 298.25 K 0.003 V K
E
H zF E T
T
H

| |
=
|
\ .
=
( ) ( )
1
1
1

53 496.10825 C V mol
where 1J 1 C V
53 496.10825 J mol
535 kJ mol
H
H
H
=
=
=
=

8-78
8.38. Calculate the solubility product and the solubility of AgBr at 25 C on the basis of the following standard electrode potentials:
AgBr(s) +e

Ag +Br
E =0.0713 V
Ag
+
+e

Ag E =0.7996 V
Solution:
Given: 25 C T =
Required: K
sp
, s
The desired reaction is obtained by subtracting the second reaction from the first.
AgBr(s) Ag Br with 1 z
+
+ =
0.0713 V 0.7996 V
0.7283V
E
E
=
=

We can calculate the solubility product from Eq. 8.13,
( )
o
o
o
13 2 2
13 2 2
0.0257ln Ag Br
Ag Br
0.0257ln
exp
0.0257
0.7283
exp
0.0257
4.92 874 705 10 mol kg
4.929 10 mol kg
u
sp
sp
sp
sp
sp
sp
E
K
E K
E
K
K
K
K
+
+

( ( =

( ( =

=
| |
=
|
\ .
| |
=
|
\ .
=
=

The solubility is therefore,
8-79
2
sp
sp
13 2 2
7 1
7 1
Ag Br
4.92874705 10 mol kg
7.02050358 10 mol kg
7.021 10 mol kg
K s
s K
s
s
s
+

( ( = =

=
=
=
=

8-80
8.39. The emf of a cell
Pt, H
2
(1 bar)|HCl(aq)|AgCl(s)|Ag
was found to be 0.517 V at 25 C. Calculate the pH of the HCl solution.
Solution:
Given: 0.517 V, 25 C E T = =
Required: pH
From Table 8.1, the standard emf of the AgCl|Ag electrode is 0.222 33 V and the cell reaction is:
2
1
AgCl(s) H H Cl Ag(s) where 1
2
z
+
+ + + = ,
To calculate the pH, we first need to find the concentration of H
+
ions.
Using Eq. 8.13,
( )
( )
( )
( )
( )
o
o
o
2 6
ln H Cl
ln H Cl
0.0257
H Cl exp
0.0257
0.22 233 V 0.517 V
H Cl exp
0.0257
H Cl 95 392.83 548 mol dm
u
u
u
u
u
RT
E E
F
E E
E E
+
+
+
+
+
( ( =

( ( =

| |
( ( =
|

\ .
| |
( ( =
|

\ .
( ( =

Since the concentrations of H
+
and Cl
-
are the same,
8-81
2 6
3
H Cl
H 95392.83548mol dm
H 308.857306mol dm
+
+
+
( ( =

( =

( =

The pH is given by the logarithm of the hydrogen ion concentration
( )
3
pH log H
pH log 308.857306mol dm
pH 2.489757879
pH 2.48
+
( =

=
=
=

8-82
8.40. The emf of the cell
Ag|AgI(s)I
(aq) Ag
+
(aq)|Ag
is 0.9509 V at 25 C. Calculate the solubility and the solubility product of AgI at that temperature.
Solution:
Given: 0.9509 V, 25 C E T = =
Required: s, K
sp

To solve this problem, we follow the example set in problem 8.38
Ag(s) Ag
AgI(s) Ag(s) I
e
e
+
+
+ +

The reaction of interest is given by,
AgI(s) Ag I with 1 z
+
+ =
We can calculate the solubility product from Eq. 8.13,
8-83
( )
o
o
o
17 2 2
17 2 2
0.0257ln Ag I
Ag I
0.0257ln
exp
0.0257
0.9509
exp
0.0257
8.53 304 763 10 mol kg
8.533 10 mol kg
u
sp
sp
sp
sp
sp
sp
E
K
E K
E
K
K
K
K
+
+

( ( =

( ( =

=
| |
=
|
\ .
| |
=
|
\ .
=
=

The solubility is therefore,
2
sp
sp
Ag I K s
s K
+
( ( = =

=

17 2 2
9 1
9 1
8.53304763 10 mol kg
9.237449662 10 mol kg
9.237 10 mol kg
s
s
s

=
=
=


8-84
8.41. An electrochemical cell M(s)|MCl(aq, 1.0 m)|AgCl(s)|Ag(s), where MCl is the chloride salt of the metal electrode M, yields a cell
potential of 0.2053 V at 25 C. What is the mean activity coefficient
of the electrolyte MCl? E for the M(s)|M

+
electrode is
0.0254 V.
Solution:
Given: 0.2053 V, 25 C, 0.0254 V E T E = = =
Required:
M M
AgCl(s) Ag(s) Cl
e
e
+
+
+ +

And the overall reaction is given by,
AgCl(s) M Ag(s) Cl M
+
+ + +
0.22233V 0.0254 V
0.19693 V
E
E
=
=

To solve for the activity coefficient, we use Eq. 8.43
2 2
ln ln
u
RT RT
E m E
F F

+ =
Since the molality of MCl is exactly 1, this expression simplifies to,
2
ln1
RT
E
F
+
2
ln
2
ln
RT
E
F
RT
E E
F
=
=

Rearranging and solving for the mean activity coefficient, we obtain,
8-85
2 0.0257
0.2053 0.19693
2 0.0257
2 0.0257ln
0.8497267371
0.850
E E
E E
e
e
=
=
=
=
=

8-86
8.42. The following thermodynamic data apply to the complete oxidation of butane at 25 C.
C
4
H
10
(g) +(13/2)O
2
(g) 4CO
2
(g) +5H
2
O(l)
1
1 1
=2877 kJ mol
=432.7 J K mol
H
S

Suppose that a completely efficient fuel cell could be set up utilizing this reaction. Calculate (a) the maximum electrical work and
(b) the maximum total work that could be obtained at 25 C.
Solution:
Given:
1 1 1
2877 kJ mol , 432.7 J K mol , 25 C H S T = = =
Required: see above
a. The maximum electrical work for the fuel cell is G .
3 1
2877 10 J mol 298.15 K
G H T S
G
=
=
( )
1
432.7 J K
( )
1
1
1
1
mol
2747990.495J mol
2748kJ mol
electrical work
electrical work 2748kJ mol
G
G
G
=
=
=
=

b. The maximum total work that can be obtained is A
8-87
( )( )( )
o o
o o
o 1 1 1
o 1
o 1
o
1
13
4 1
2
3.5
2747 990.495 J mol 3.5 8.3145 J K mol 298.15 K
2756 666.884 J mol
2758 kJ mol
total work
total work 2758 kJ mol
G A vRT
A G vRT
v
v
A
A
A
A

=
= +
=
=
= +
=
=
=
=

8-88
*8.43. At 298 K the emf of the cell
Cd, Hg|CdCl
2
(aq, 0.01 m), AgCl(s)|Ag
is 0.7585 V. The standard emf of the cell is 0.5732 V.
a. Calculate the mean activity coefficient for the Cd
2+
and Cl

ions.
b. Compare the value with that estimated from the Debye-Hckel limiting law, and comment on any difference.
Solution:
Given: 0.7585 V, 0.5732V E E = =
Required: see above
a. To calculate the mean activity coefficients, we follow a similar process as used in problem 8.24.
The half reactions at each electrode are,
2

Cd(s) Cd 2
AgCl(s) Ag Cl
e
e
+
+
+ +

2
2AgCl(s) Cd(s) 2Ag(s) 2Cl Cd
+
+ + + , where 2 z =
Suppose that at 0. 01 m the activity coefficients are and
+
, then we can solve for the mean activity coefficient from Eq. 8.40.
8-89
( )
( )
( )
( )( )
( )
( )
( )
( )
2
o 2
Cd Cl
2
o 2 2
2
o 2 3
2
3
6 3
6 3
6 3
ln
2
ln Cd Cl
2
ln Cd Cl
2
0.0257
0.7585 V 0.5732 V ln 0.01 0.02
2
0.1853 0.01 285ln 4 10
ln 4 10 14.42 023 346
4 10 5.462 257 62
u
u
u
RT
E E a a
F
RT
E E
F
RT
E E
F

+
+
+
+
=
( ( =

( ( =

=
=
=
=
7
1 10
0.5 149 567 193
0.51
=
=

b. To calculate the activity coefficient according to the DHLL, we first calculate the ionic strength of the solution from Eq. 7.103,
( )
2
2 2
1
2
1
1 0.02 2 0.01
2
0.03
i i
i
I c z
I
I m
=
= +
=

Now we rearrange the Debye-Hckel limiting law given by Eq. 7.111,
( )
3
3
10
0.51 /mol dm
0.51 2 1 0.03
log 0.51 /mol dm
10
10
0.6657801116
0.67
z z I
z z I
=
=
=
=
=

8-90
There is a considerable difference between the two methods.

8-91
*8.44. The following emf values were obtained by H. S. Harned and Copson [J. Amer. Chem. Soc., 55, 2206(1933)] at 25 C for the cell
Pt,H
2
(1 bar)|LiOH(0.01 m), LiCl(m)|AgCl(s)|Ag
at various molalities m of LiCl:
m/mol kg
1
0.01 0.02 0.05 0.10 0.20
E/V 1.0498 1.0318 1.0076 1.9888 0.9696

Obtain from these data the ionic product of water.
Solution:
Given: emf values above
Required: K
w

In this cell, we see that the LiOH is required for the hydrogen electrode, and the LiCl salt is used to complete the AgCl electrode. Both the
Cl
-
ion and the H
+
ion will behave according to their activities in solution. We begin solving the problem by first determining the emf of the
cell:
2
cell AgCl H
cell AgCl
Cl H
ln ln
E E E
RT RT
E E a a
F F
+
=
=

Since
w
H OH
K a a
+
= , we can substitute this into the above expression and develop a relationship involvingK
w
.
w
cell AgCl
Cl
OH
cell AgCl w
Cl OH
Cl
cell AgCl w
OH
ln ln
ln ln ln
ln ln
K RT RT
E E a
F F a
RT RT RT
E E a K a
F F F
a
RT RT
E E K
F a F
=
= +
=

Rewriting this expression in terms of activity coefficients and molalities gives,
8-92
Cl Cl
cell AgCl w
OH OH
Cl Cl
cell AgCl w
OH OH
cell AgCl
Cl Cl
w
OH OH
ln ln
ln ln ln
ln ln ln
0.0257
m
RT RT
E E K
F m F
m
RT RT RT
E E K
F m F F
m E E
K
m
=
=
=

The molality of OH
-
is given as 0.01 m, and from Table 8.1,
AgCl
0.22233V E
= .
cell Cl Cl
w
OH
0.22233
ln ln ln
0.0257 0.01
m
E
K
+ =
We plot the left-hand side of the equation against the ionic strength, which varies with concentration, and extrapolate to zero ionic strength.
At zero ionic strength, the activity coefficients approach unity. Then the value of the curve is -lnK
w
.
cell Cl
w
0.22233
ln ln
0.0257 0.01
m
E
K

+ =
In the following data, I is based on 0.01 OH m m

+ , where 0.01m is constant.
1
/ mol kg m

0.01 0.02 0.05 0.10 0.20
1
/ mol kg I

0.02 0.03 0.06 0.11 0.21
cell
0.22233
0.0257
E

32.3086 31.5079 30.566 29.834 29.087
ln
0.01
m

0.000 0.693 1.609 2.303 2.996
cell
0.22233
ln
0.0257 0.01
E m
+
32.209 32.301 32.175 32.137 32.083

8-93
From the indicated plot shown, the value of -lnK
w
is 1.01010
-14
.


CHAPTER
9
9
Chemical Kinetics I.
The Basic Ideas

Physical Chemistry
Electronic Edition


Chapter 9: Chemical Kinetics I. The Basic Ideas Rate Constants and Order of Reaction
9-2
Chapter 9
Rate Constants and Order of Reaction
9.1. The stoichiometric equation for the oxidation of bromide ions by hydrogen peroxide in acid solution is:
2Br
+H2O2 +2H
+
Br2 +2H2O
Since the reaction does not occur in one stage, the rate equation does not correspond to this stoichiometric equation but is
=k[H2O2][H
+
][Br
]
a. If the concentration of H2O2 is increased by a factor of 3, by what factor is the rate of consumption of Br

ions increased?
b. If the rate of consumption of Br

ions is 7.2 10
3
mol dm
3
s
1
, what is the rate of consumption of hydrogen peroxide? What is
the rate of formation of bromine?
c. What is the effect on the rate constant k of increasing the concentration of bromide ions?
d. If by the addition of water to the reaction mixture the total volume were doubled, what would be the effect on the rate of change
of the concentration of Br
? What would be the effect on the rate constant k?

Solution
9.2. A reaction obeys the stoichiometric equation:
A +2B 2Z
Rates of formation of Z at various concentrations of A and B are as follows:
[A]/mol dm
3
[B]/mol dm
3
Rate/mol dm
3
s
1

3.5 10
2
2.3 10
2
5.0 10
7

7.0 10
2
4.6 10
2
2.0 10
6

7.0 10
2
9.2 10
2
4.0 10
6

9-3
What are and in the rate equation and what is the rate constant k?
=k[A]
[B]

Solution
9.3. Some results for the rate of a reaction between two substances A and B are shown in the following table. Deduce the order with
respect to A, the order with respect to B, and the rate constant.
[A]/mol dm
3
[B]/mol dm
3
Rate/mol dm
3
s
1

1.4 10
2
2.3 10
2
7.40 10
9

2.8 10
2
4.6 10
2
5.92 10
8

2.8 10
1
4.6 10
2
5.92 10
6

Solution
9.4. A substance decomposes at 600 K with a rate constant of 3.72 10
5
s
1
.
a. Calculate the half-life of the reaction.
b. What fraction will remain undecomposed if the substance is heated for 3 h at 600 K?
Solution
9.5. How does the time required for a first-order reaction to go to 99% completion relate to the half-life of the reaction?
Solution
9.6. The rate constant for the reaction H
+
+OH

H2O is 1.3 10
11
dm
3
mol
1
s
1
. Calculate the half-life for the neutralization process if
(a) [H]
+
=[OH
] =10
1
M and (b) [H
+
] =[OH
] =10
4
M.
Solution
9.7. The isotope
90
Sr emits radiation by a first-order process (as is always the case with radioactive decay) and has a half-life of 28.1
years. When ingested by mammals it becomes permanently incorporated in bone tissue. If 1 g is absorbed at birth, how much of
this isotope remains after (a) 25 years, (b) 50 years, (c) 70 years?
Solution
9-4
9.8. The first-order decomposition of nitramide in the presence of bases, NH2NO2 N2O(g) +H2O(l), is conveniently analyzed by
collecting the gas evolved during the reaction. During an experiment, 50.0 mg of nitramide was allowed to decompose at 15 C. The
volume of dry gas evolved after 70.0 min. was measured to be 6.59 cm
3
at 1 bar pressure. Find the rate constant and the half-life for
nitramide decomposition.
Solution
9.9. The reaction:
2NO(g) +Cl2(g) 2NOCl(g)
is second order in NO and first order in Cl2. In a volume of 2 dm
3
, 5 mol of nitric oxide and 2 mol of Cl2 were brought together, and
the initial rate was 2.4 10
3
mol dm
3
s
1
. What will be the rate when one-half of the chlorine has reacted?
Solution
9.10. Measuring the total pressure is a convenient way to monitor the gas phase reaction:
2NOCl(g) 2NO(g) +Cl2(g)
However, the rate depends on the concentration of the reactant, which is proportional to the partial pressure of the reactant. Derive
an expression relating the rate of this reaction to the initial pressure, P0, and the total pressure, Pt, at time t. Assume that the reaction
follows second-order kinetics.
Solution
9.11. The following results were obtained for the rate of decomposition of acetaldehyde:
% decomposed:
0 5 10 15 20 25 30 35 40 45 50

Rate/Torr min
1

8.53 7.49 6.74 5.90 5.14 4.69 4.31 3.75 3.11 2.67 2.29
Employ vant Hoffs differential method to obtain the order of reaction.
Solution
9-5
9.12. The isotope
32
15
P emits radiation and has a half-life of 14.3 days. Calculate the decay constant in s
1
. What percentage of the initial
activity remains after (a) 10 days, (b) 20 days, (c) 100 days?
Solution
9.13. The following counts per minute were recorded on a counter for the isotope
35
16
S at various times:

Time/d Counts/min
0 4280
1 4245
2 4212
3 4179
4 4146
5 4113
10 3952
15 3798

Determine the half-life in days and the decay constant in s
1
. How many counts per minute would be expected after (a) 60 days and (b) 365
days?
Solution
9.14. The reaction:
+ +
2 2 2 2
-Cr(en) (OH) -Cr(en) (OH) cis trans z
is first order in both directions. At 25 C the equilibriumconstant is 0.16 and the rate constant k1 is 3.3 10
4
s
1
. In an experiment
starting with the pure cis form, how long would it take for half the equilibriumamount of the trans isomer to be formed?
Solution
9-6
9.15. Suppose that a gas phase reaction 2A(g) 2B(g) +C(g) follows second-order kinetics and goes to completion. If the reaction is
allowed to proceed in a constant volume vessel at an initial pressure of 2 bar (only A is initially present), what will be the partial
pressures of A, B, and C and the total pressure at t =t1/2, 2t1/2, 3t1/2, and infinity?
Solution
9.16. Derive the following relationship for the half-life t1/2 of a reaction of order n, with all reactants having an initial concentration a0:
1
1/2 1
0
2 1
( 1)
n
n
t
ka n
=

Solution
9.17. Vaughan [J. Am. Chem. Soc. 54, 3867(1932)] reported the following pressure measurements as a function of time for the
dimerization of 1,3-butadiene (C4H6) under constant volume conditions at 326 C:
t/min 3.25 12.18 24.55 42.50 68.05
P/Torr 618.5 584.2 546.8 509.3 474.6

The initial amount of butadiene taken would have exerted a pressure of 632.0 Torr. Find whether the reaction follows first- or second-order
kinetics and evaluate the rate constant.
Solution
9.18. A drug administered to a patient is usually consumed by a first-order process. Suppose that a drug is administered in equal amounts
at regular intervals and that the interval between successive doses is equal to the (1/n)-life for the disappearance process (i.e., to the
time that it takes for the fraction 1/n to disappear). Prove that the limiting concentration of the drug in the patients body is equal to n
times the concentration produced by an individual dose.
Solution
9.19. Equation 9.45 applies to a second-order reaction of stoichiometry A +B Z. Derive the corresponding equation for a second-order
reaction of stoichiometry 2A +B Z.
Solution
9-7
9.20. Derive the integrated rate equation for an irreversible reaction of stoichiometry 2A +B Z, the rate being proportional to [A]
2
[B]
and the reactants present in stoichiometric proportions; take the initial concentration of A as 2a0 and that of B as a0. Obtain an
expression for the half-life of the reaction.
Solution
9.21. Prove that for two simultaneous (parallel) reactions

1
2
[Y]
at all times.
[Z]
k
k
=

Solution
*9.22. Prove that for two consecutive first-order reactions; A B C the rate of formation of C is given by:
1 2

2 1
0
1 2
e e
[C] [A] 1
k t k t
k k
k k
| |
= +
|
\ .

where [A]0 is the initial concentration of A.
(Hint: The solution of the differential equation):
bt
dx
abe cx
dt
=
where a, b, and c are constants, is

(e e )
bt ct
ab
x I
c b
= +

Solution
9-8
*9.23. a. Derive the integrated rate equation for a reversible reaction of stoichiometry:
1
1
A Y +Z
k
k
z
The reaction is first order fromleft to right and second order fromright to left. Take the initial concentration of A as a0 and the
concentration at time t as a0 x.
b. Obtain the integrated equation in terms of k, and the equilibriumconstant K =k1/k1.
c. A reaction to which this rate equation applies is the hydrolysis of methyl acetate. Newling and Hinshelwood, J. Chem. Soc., 1936,
1357(1936), obtained the following results for the hydrolysis of 0.05 M ester at 80.2 C in the presence of 0.05 M HCl, which
catalyzes the reaction:
Time, s 1350 2070 3060 5340 7740
Percent hydrolysis 21.2 30.7 43.4 59.5 73.45 90.0

Obtain values for the rate constants k1 and k1.
Solution
*9.24. The dissociation of a weak acid HA +H2O = H3O
+
+A

can be represented as:
A z Y +Z
The rate constants k1 and k1 cannot be measured by conventional methods but can be measured by the T-jump technique (Section
9.5). Prove that the relaxation time is given by:
1 1
1
*
2
e
t
k k x
=
+

where the concentration of the ions (Y and Z) is at equilibrium.
Solution
Chapter 9: Chemical Kinetics I. The Basic Ideas Temperature Dependence
9-9
Temperature Dependence
9.25. The rate constant for a reaction at 30 C is found to be exactly twice the value at 20 C. Calculate the activation energy.
Solution
Solution
9.27. The following data for a first-order decomposition reaction in aqueous mediumwas reported by E. O. Wiig [J. Phys. Chem. 34,
596(1930)].
t/C 0 20 40 60
k/10
5
min
1
2.46 43.5 575 5480

Find the activation energy and the preexponential factor.
Solution
9.28. Two second-order reactions have identical preexponential factors and activation energies differing by 20.0 kJ mol
1
. Calculate the
ratio of their rate constants (a) at 0 C and (b) at 1000 C.
Solution
9.29. The gas-phase reaction between nitric oxide and oxygen is third order. The following rate constants have been measured:
T/K 80.0 143.0 228.0 300.0 413.0 564.0
k 10
9
/cm
6
mol
1
s
1
41.8 20.2 10.1 7.1 4.0 2.8

The behavior is interpreted in terms of a temperature-dependent preexponential factor; the rate equation is of the form:
k =aT
n
e
E/RT

where a and n are constants. Assume the activation energy to be zero and determine n to the nearest half-integer.
Solution
9-10
9.30. The definition of activation energy Ea is generally considered to be given by an extension of Eq. 9.91:
2
ln
a
d k
E RT
dT
| |
=
|
\ .

Problem9.29 shows that for certain reactions, the temperature dependence of the reaction rate constant is better described by an
expression of the type
k =aT
n
e
E/RT

Using the definition for Ea given here, derive an expression for the activation energy fromthis expression.
Solution
9.31. The water flea Daphnia performs a constant number of heartbeats and then dies. The flea lives twice as long at 15 C as at 25 C.
Calculate the activation energy for the reaction that controls the rate of its heartbeat.
Solution
9.32. A sample of milk kept at 25 C is found to sour 40 times as rapidly as when it is kept at 4 C. Estimate the activation energy for the
souring process.
Solution
*9.33. Experimentally, the rate constant for the O(
3
P) +HCl reaction in the gas phase is found to have a temperature dependence given by:
k (cm
3
molecule
1
s
1
) =5.6 10
21
T
2.87
e
1766K/T
in the range 350 1480 K [Mahmud, Kim, and Fontijn, J. Phys. Chem. 94, 2994(1990)].
a. Using the results of Problem9.30, find the value of Ea at 900 K, which is approximately the middle of this range.
b. Using variational transition-state theory (an extension of the transition-state theory described in Section 9.9), the theoretical rate
constant for this reaction is found to behave according to the equation:
k (cm
3
molecule
1
s
1
) =6.9 10
20
T
2.60
e
2454K/T

in the same temperature range [T. C. Allison, B. Ramachandran, J . Senekowitsch, D. G. Truhlar, and R. E. Wyatt, J. Mol. Structure,
Theochem, 454, 307, 1998.] Compare the experimental and theoretical rate constants at 900 K.
Solution
9-11
9.34. The activation energy for the reaction:
H +CH4 H2 +CH3
has been measured to be 49.8 kJ mol
1
. Some estimates of enthalpies of formation, fH, are:
H 218.0 kJ mol
1

CH4 74.8 kJ mol
1

CH3 139.5 kJ mol
1

Estimate a value for the activation energy of the reverse reaction.
Solution
*9.35. By a treatment similar to that given for relaxation methods for the case A = Z, derive the rate equations for analyzing the reaction
A +B = Z by carrying out the steps below.
a. Show that at equilibrium, k1aebe =k1ze, where the subscript e indicates equilibriumconcentrations.
b. Show that
1 1
( )( ) ( )
e e e
dx
k a x b x k z x
dt
= + , where x represents a change fromequilibrium.
c. Show that for small x,
1 1
[ ( ) ]
e e
dx
k a b k x
dt
= + + . [Hint: Use the result of part (a).]
d. The displacement fromequilibriumx always follows the first-order process x =x0 exp(t/t*), where t* is the relaxation time.
Show that dx/dt =x/t*.
e. Comparing the results of parts (c) and (d), show that
1 1
1
2
*
e
k a k
t
= + if ae =be.
f. For the case ae =be, show that
1 1 1
1
2
*
e
k k z k
t
= + . [Hint: Use the result of part (e) and the fact that
1
1
.
e
e e
z k
k a b
= ]
Solution
Chapter 9: Chemical Kinetics I. The Basic Ideas Collision Theory and Transition-State Theory
9-12
9.36. A reaction of the type A +B = Z has been studied by relaxation methods. Some of the available data relating equilibrium
concentrations of the product to the relaxation times are given below.
ze/M 0.001 0.002 0.005 0.010 0.025 0.05 0.10
t*/ms 4.08 3.74 2.63 1.84 1.31 0.88 0.674

Determine k1, k1, and K =k1/k1.
Solution
9.37. The equilibriumH2O = H
+OH has a relaxation time of about 40 s at 25 C. Find the values of the forward and reverse rate
constants. Kw =[H
+
][OH
] =10
14
.
(Hint: For this case, using steps similar to those of Problem9.25, it can be shown that
+
1 1
1
([H ] [OH ] )
*
e e
k k
t
= + + .)
Solution
Collision Theory and Transition-State Theory
9.38. Two reactions of the same order have identical activation energies and their entropies of activation differ by 50 J K
1
mol
1
.
Calculate the ratio of their rate constants at any temperature.
Solution
9.39. The gas-phase reaction:
H2 +I2 2HI
is second order. Its rate constant at 400 C is 2.34 10
2
dm
3
mol
1
s
1
, and its activation energy is 150 kJ mol
1
. Calculate
H,
S, and
G at 400 C, and the preexponential factor.

Solution
Formatted: Heading 1, Left, Indent:
Left: 0", First line: 0"
Chapter 9: Chemical Kinetics I. The Basic Ideas Collision Theory and Transition-State Theory
9-13
9.40. A substance decomposes according to first-order kinetics; the rate constants at various temperatures are as follows:
Temperature/C Rate constant, k/s
1

15.0 4.18 10
6

20.0 7.62 10
6

25.0 1.37 10
5

30.0 2.41 10
5

37.0 5.15 10
5

Calculate the activation energy. Calculate also, at 25 C, the enthalpy of activation, the Gibbs energy of activation, the preexponential
factor, and the entropy of activation.
Solution
9.41. The following data have been obtained for the hydrolysis of adenosine triphosphate, catalyzed by hydrogen ions:
1

39.9 4.67 10
6

43.8 7.22 10
6

47.1 10.0 10
6

50.2 13.9 10
6

Calculate, at 40 C, the Gibbs energy of activation, the energy of activation, the enthalpy of activation, the preexponential factor, and the
entropy of activation.
Solution
9.42. The half-life of the thermal denaturation of hemoglobin, a first-order process, has been found to be 3460 s at 60 C and 530 s at 65
C. Calculate the enthalpy of activation and entropy of activation at 60 C, assuming the Arrhenius equation to apply.
Solution
Chapter 9: Chemical Kinetics I. The Basic Ideas Ionic-Strength Effects
9-14
*9.43. a. Using Eq. 9.73, calculate the collision density for 6.022 10
23
molecules of hydrogen iodide present in a volume 1 m
3
at 300 K.
Take dAA =0.35 nm.
b. If the activation energy for the decomposition of HI is 184 kJ mol
1
, what rate constant does kinetic theory predict at 300 C? To
what entropy of activation does this result correspond?
Solution
9.44. The rate constant for a first-order reaction is 7.40 10
9
s
1
at 25 C, and the activation energy is 112.0 kJ mol
1
. Calculate, at 25 C,
the preexponential factor A, the enthalpy of activation
H, the Gibbs energy of activation
G, and the entropy of activation
S.
Solution
9.45. The rate constant for a second-order reaction in solution is 3.95 10
4
dm
3
mol
1
s
1
at 25 C, and the activation energy is 120.0 kJ
mol
1
. Calculate, at 25 C, the preexponential factor A, the enthalpy of activation
G, and the
entropy of activation
S.
Solution
Ionic-Strength Effects
9.46. The rate constant k for the reaction between persulfate ions and iodide ions varies with ionic strength I as follows:
I/10
3
mol dm
3
2.45 3.65 4.45 6.45 8.45 12.4
k/dm
3
mol
1
s
1
1.05 1.12 1.16 1.18 1.26 1.39

Estimate the value of zAzB.
Solution
Formatted: Heading 1
Chapter 9: Chemical Kinetics I. The Basic Ideas Ionic-Strength Effects
9-15
9.47. The following constants were obtained by Brnsted and Livingstone [J. Amer. Chem. Soc., 49, 435(1927)] for the reaction:
[CoBr(NH3)5]
2+
+OH
[Co(NH3)5OH]
2+
+Br

under the following conditions:

Concentration/mol dm
1

3 1 1
dm mol s
k

[CoBr(NH3)5]
2+
NaOH NaCl
5.0 10
4
7.95 10
4
0 1.52
5.96 10
4
1.004 10
3
0 1.45
6.00 10
4
0.696 10
3
0.005 1.23
6.00 10
4
0.696 10
3
0.020 0.97
6.00 10
4
0.691 10
3
0.030 0.91

Make an estimate of the rate constant of the reaction at zero ionic strength. Are the results consistent with zAzB =2?
Solution
9.48. Suppose that the rates of ionic reactions in solution were proportional to the activity rather than the concentration of activated
complexes. Derive an equation relating the logarithmof the rate constant to the ionic strength and the charge numbers of the ions
and contrast it with Eq. 9.124. Can the results in Figure 9.22 be reconciled with the equation you have derived?
Solution
Chapter 9: Chemical Kinetics I. The Basic Ideas Pressure Effects
9-16
9.49. When the subatomic species muonium(Mu) was first discovered in 1960, it was not known whether it bore an electric charge. The
answer was provided by a kinetic study of the ionic strength effect on the reaction Mu +Cu
2+
in aqueous solution. The following
rate constants were measured at two ionic strengths:
I =0 k =6.50 10
9
dm
3
mol
1
s
1

I =0.9 M k =6.35 10
9
dm
3
mol
1
s
1

Suppose that muoniumhad a single negative charge; what would k be expected to be at an ionic strength of 0.9 M? What do you deduce
about the actual charge on muonium?
Solution
9.50. The rate constants of a second-order reaction in aqueous solution at 25 C had the following values at two ionic strengths:
I/mol dm
3
k/dm
3
mol
1
s
1

2.5 10
3
1.40 10
3

2.5 10
2
2.35 10
3

Make an estimate of the value of zAzB, the product of the charge numbers.
Solution
9.51. A reaction of the type:
A
+
+B
2
products
was found at 25 C to have a rate constant of 2.8 10
4
dm
3
mol
1
s
1
at an ionic strength of 1.0 10
3
M. Assume the Debye-Hckel
limiting law to apply and estimate the rate constant at zero ionic strength.
Solution
Pressure Effects
9.52. The rate of a reaction at 300 K is doubled when the pressure is increased from1 bar to 2000 bar. Calculate
V, assuming it to be
independent of pressure.
Formatted: Space After: 0 pt
Formatted: Heading 1, Left
Chapter 9: Chemical Kinetics I. The Basic Ideas Pressure Effects
9-17
Solution

9.53. The following results were obtained for the solvolysis of benzyl chloride in an acetone-water solution at 25 C:
P/10
2
kPa 1.00 345 689 1033
k/10
6
s
1
7.18 9.58 12.2 15.8

Make an appropriate plot and estimate
V.
Solution
9.54. The fading of bromphenol blue in alkaline solution is a second-order reaction between hydroxide ions and the quinoid formof the
dye:
quinoid form(blue) +OH

carbinol form(colorless)
The following results show the variation of the second-order rate constant k with the hydrostatic pressure P at 25 C:
P/10
4
kPa 101.3 2.76 5.51 8.27 11.02
k/10
4
M
1
s
1
9.30 11.13 13.1 15.3 17.9

Estimate
V.
Solution
9.55. Use Figure 9.23 to make approximate estimates of the volumes of activation for the alkaline hydrolyses of methyl acetate, ethyl
acetate, and propionamide, at 25 C.
Solution
Chapter 9: Chemical Kinetics I. The Basic Ideas Essay Questions
9-18
Essay Questions
9.56. Explain clearly the difference between the order and the molecularity of a reaction.
9.57. Give an account of experimental methods that might be used to study the kinetics of (a) a reaction having a half-life of about 10
1
s
and (b) a reaction having a half-life of about 10
7
s.
9.58. Predict the effects of (a) increasing the dielectric constant of the solvent, (b) increasing the ionic strength, and (c) increasing the
pressure on the reactions of the following types:
2
2+ 3
+
A B X
A B X
A B A B
+ +
+ +
+
+
+

Give a clear explanation in each case. What can you say about the entropy of activation to be expected in each case?
9.59. Vant Hoffs differential method can be applied to kinetic data in two different ways:
1. Rates can be determined at various stages of a single reaction.
2. Initial rates can be measured at a variety of initial concentrations, the reaction being run a number of times. In each case log10
(rate) can be plotted against log10 (concentration of a reactant). Can you suggest why a different order of reaction might be obtained
when these two different procedures are used?
Formatted: Heading 1, Indent: Left:
0", First line: 0"
Formatted: Heading 1
Chapter 9: Chemical Kinetics I. The Basic Ideas Solutions
9-19
Solutions
9.1. The stoichiometric equation for the oxidation of bromide ions by hydrogen peroxide in acid solution is:
2Br
+H2O2 +2H
+
Br2 +2H2O
Since the reaction does not occur in one stage, the rate equation does not correspond to this stoichiometric equation but is
=k[H2O2][H
+
][Br
]
a. If the concentration of H2O2 is increased by a factor of 3, by what factor is the rate of consumption of Br

ions increased?
b. If the rate of consumption of Br

ions is 7.2 10
3
mol dm
3
s
1
, what is the rate of consumption of hydrogen peroxide? What is
the rate of formation of bromine?
c. What is the effect on the rate constant k of increasing the concentration of bromide ions?
d. If by the addition of water to the reaction mixture the total volume were doubled, what would be the effect on the rate of change
of the concentration of Br
? What would be the effect on the rate constant k?

Solution:
It is important to note that rather than considering the species as themselves, we can make the rate equation more simple by introducing the
following substitutions.
2 2
H O A
H B
Br C
+
=
=
=

a) We can start off by writing down the rate of reaction for each species involved. Recall fromsection 9.2 that the rate of reaction is
independent of which reactant or product species is chosen. For the reaction: A B Y Z a b y z + + occurring at constant volume, the
rate of reaction is given as;
| | | | | | | | A B Y Z 1 1 1 1 d d d d
v
a dt b dt y dt z dt
= = = =
Let us now apply this to our particular case. This will yield;
9-20
| | | | | |
A B C
A B C 1 1
, ,
2 2
d d d
v v v
dt dt dt
= = =
If the concentration of H2O2 is increased by a factor of 3, then we can say that
B
v will remain fixed and
C
v will also increase by a
factor of three.
C
will by a factor of 3 v
b) We are given that
3 3 1
C
7.2 10 mol dm s v = (bromide ion). With this information, we are able to determine the rate of
consumption of species A and B. It is possible to also write the rate of reaction in a manner that expresses the rates of consumption
or formation for each species.
2
2
2
A B Y Z
Br
C A
3 3 1
Br
A
3 1
A
3 3 1
A
3 3 1
Br
1 2 1
7.2 10 mol dm s
1 2 1
0.0036 mol dm s
3.6 10 mol dm s
3.6 10 mol dm s
v v v v
v
a b y z
v
v v
v
v
v
v
v
v
v
= = = =
= = =
= = =
=
=
=

c) Recall fromsection 9.3 that the rate constant k, is independent of concentration (as well as time). This means that there will be no
change in its value if one increases the concentration of bromide ions.
no change in k
d) If we add enough water into the mixture to double the total volume, we will at the same time, be diluting all of the concentrations by
one half. Recall that for the bromide ion, we originally we have;
9-21
| |
C
C 1
2
d
v
dt
= multiplied by one half will produce
| | | |
C
C C 1 1 1
2 2 4
d d
v
dt dt
| |
= =
|
\ .

C
will have a rate of disappearance that is 4x slower v
no change in k

9-22
9.2. A reaction obeys the stoichiometric equation:
A +2B 2Z
Rates of formation of Z at various concentrations of A and B are as follows:
[A]/mol dm
3
[B]/mol dm
3
Rate/mol dm
3
s
1

3.5 10
2
2.3 10
2
5.0 10
7

7.0 10
2
4.6 10
2
2.0 10
6

7.0 10
2
9.2 10
2
4.0 10
6

What are and in the rate equation and what is the rate constant k?
=k[A]
[B]

Solution:
Let us begin by determining the total order of the reaction by using the rate at a variety of concentrations.
( )
( )
6 3 1
3
2
4.0 10 mol dm s v C
v
v C
= =
6 3 1
2.0 10 mol dm s
2 v =

This tells us that the overall order of the reaction will be 2
nd
order. Since both A and B are included in the rate equation, we can assume
that,
| | | |
1 1
1, 1
A B v k
= =
=

The rate constant may be determined by rearranging the above expression and simply substituting in experimental values given above at the
same concentration (for each species).
9-23
| | | |
( )
| | | |
1 1
7
1
1 1
A B
5.0 10 mol
A B
v
k
v C
k
= =
3
dm
( )
1
2 3 2
s
3.5 10 mol dm 2.3 10 mol
3
dm
( )
4 3 1 1
6.2 10 dm mol s k

=

9-24
9.3. Some results for the rate of a reaction between two substances A and B are shown in the following table. Deduce the order with
respect to A, the order with respect to B, and the rate constant.
[A]/mol dm
3
[B]/mol dm
3
Rate/mol dm
3
s
1

v1 1.4 10
2
2.3 10
2
7.40 10
9

v2 2.8 10
2
4.6 10
2
5.92 10
8

v3 2.8 10
1
4.6 10
2
5.92 10
6

Solution:
Given: see above
Required: , , k
We will solve this problemin the same way that problem9.2 was done.
Let us begin by determining the total order of the reaction by examining the concentrations of each species in conjunction with the change
in the rate (at each different concentration).
1 2
3
2 2
2
6
8
2
2 2
2
2 2
1
8
9
1.
2.8 10 4.6 10
2.8 10 4.6 10
5.92 10
10 100
5.92 10
2
2.
2.8 10 4.6 10
1.4 10 2.3 10
5.92 10
8 4 2
7.4 10
1
v
v
v
v

| | | |
=
| |

\ . \ .
| |
= =
|
\ .
=
| | | |
=
| |

\ . \ .
| |
= =
|
\ .
=

9-25

| | | |
2
2
9 2 2
1
3
1
2
8 2 2
2
3
2
2
6 1 2
3
3
3
1 2 3
3.
A B
7.4 10 1.4 10 2.3 10
1.641 526 176 10
5.92 10 2.8 10 4.6 10
1.641 526 176 10
5.92 10 2.8 10 4.6 10
1.641 526 176 10
3
1.642
v k
k
k
k
k
k
k
k k k
k
k

=
( ( =

=
( ( =

=
( ( =

=
+ +
=
=
3
10

9-26
9.4. A substance decomposes at 600 K with a rate constant of 3.72 10
5
s
1
.
a. Calculate the half-life of the reaction.
b. What fraction will remain undecomposed if the substance is heated for 3 h at 600 K?
Solution:
Given:
5 1
600 K, 3.72 10 s , 3hrs T k t = = =
Required:
1/2
,fraction undecomposed t
By looking at the units for the rate constant, it is often possible to determine the order of the reaction. This information will greatly
facilitate the calculation of the half life as there are different equations that should be used depending on the order of the reaction. Since the
units are in s
1
, we have seen in Table 9.1 that this corresponds to a 1
st
order reaction.
a) The half life will then be:
1/2
1/2 5 1
1/2 5 1
1/2
4
1/2
4
1/2
ln2
ln2
3.72 10 s
0.693 147
3.72 10 s
18 632.988 72 s
1.86 10 s
1.86 10 s
t
k
t
t
t
t
t
=
=
=
=
=
1 min
60 s
1 hr
60 min
1/2
5.18 hrs t =

b) The undecomposed fraction after three hours will be:
If
0
0
1
ln
a
k
t a x
=
then we can rearrange this expression in order to solve for the fraction of substance that is undecomposed.
9-27
( )
0
0
ln
exp lne
a
kt
a x
kt
=
=
( )
0
0
5 1 0
0
exp fraction undecomposed=exp 3.72 10 s
a
a x
a x
kt
a
| |
|
\ .
= = 3 hrs
60 min
1 hr
60 s
1 min
0.669
fraction undecomposed 0.669
| |
=
|
\ .
=


9-28
9.5. How does the time required for a first-order reaction to go to 99% completion relate to the half-life of the reaction?
Solution:
FromTable 9.1 we are given the following information,
st
0
1/2
0
1 order reaction:
1 ln2
ln ,
a
k t
t a x k
= =

With this we know that after the half life, there is only 50 percent of the substance left. This means that the fraction undecomposed is equal
to 0.5.
( )
0
1/2 1/2
0
At , 0.5 and 0.5 exp
a x
t kt
a
= =
If the reaction goes to 99 percent completion, this would mean that the fraction undecomposed will be equal to 0.01 and therefore,
( )
0
99 99
0
At , 0.01 and 0.01 exp
a x
t kt
a
= =
Let us now rearrange these expressions in order to isolate for the time variable.
( )
1/2
1
exp
0.5
ln2 lne
kt =
= ( )
( )
1/2
1/2
99
ln2
1
exp
0.01
ln100 lne
kt
t
k
kt
=
=
= ( )
99
99
ln100
kt
t
k
=

9-29

Taking the ratio of these two expressions will show us how the time required for a first-order reaction to go to 99% completion relates to the
half-life of the reaction.
99
1/2
ln100
ln100
ln2
t
k
t k
k
= =
k
99
1/2
ln100
6.64
ln2 ln2
t
t
= =

9-30
9.6. The rate constant for the reaction H
+
+OH

H2O is 1.3 10
11
dm
3
mol
1
s
1
. Calculate the half-life for the neutralization process if
(a) [H]
+
=[OH
] =10
1
M and (b) [H
+
] =[OH
] =10
4
M.
Solution:
Given: | |

11 3 1 1 1 4
1.3 10 dm mol s , H OH 10 M, H OH 10 M k
+
+
( ( ( = = = = =

Required:
1/2
t in each case
We will again look at the rate constant in order to determine the overall order of the reaction. Since the units are dm
3
mol
1
s
1
, fromTable
9.1 we can see that the reaction is 2
nd
order.
a) The half life for the neutralization process [H]
+
=[OH
] =10
1
M is therefore,
( )( )
1/2
0
1/2
11 3 1 1 1
1
3
1/2
11 3 1
1
1
1.3 10 dm mol s 10 M
1 M 1 mol L
1 L 1 dm
1
1.3 10 dm mol
t
ka
t
t

=
=
=
=
=
( )
1 1 3
s 10 mol dm

( )
11
1/2
7.7 10 s t

=

b) The half life for the neutralization process [H]
+
=[OH
] =10
4
M is therefore,
9-31
( )( )
1/2
0
1/2
11 3 1 1 4
1
3
1/2
11 3 1
1
1
1.3 10 dm mol s 10 M
1 M 1 mol L
1 L 1 dm
1
1.3 10 dm mol
t
ka
t
t

=
=
=
=
=
( )
1 4 3
s 10 mol dm

( )
8
1/2
7.7 10 s t

=

9-32
9.7. The isotope
90
Sr emits radiation by a first-order process (as is always the case with radioactive decay) and has a half-life of 28.1
years. When ingested by mammals it becomes permanently incorporated in bone tissue. If 1 g is absorbed at birth, how much of
this isotope remains after (a) 25 years, (b) 50 years, (c) 70 years?
Solution:
Given:
90
Sr:
1/2
28.1 years, 1 g t m = =
Required: fraction remaining in each case
It is first important to determine the rate constant. Since we are told that the radioactive decay is a 1
st
order process, we can use Table 9.1 in
order to calculate its value.
1/2
1/2
1/2
1
ln2
ln2
28.1 yrs
0.693147
28.1 yrs
0.024 667 yrs
t
k
k
t
t
k
k

=
=
=
=
=

Now we will use the integrated formin order to isolate for the fraction undecomposed after a certain period of time.
( )
0
0
0
0
1
ln
ln
exp lne
a
k
t a x
a
kt
a x
kt
=
=
( )
0
0
0
0
exp fraction undecomposed
a
a x
a x
kt
a
| |
|
\ .
= =

9-33

a) After 25 years,
1 0
0
exp 0.024 667 yrs
a x
a
= 25 yrs
( )
0
0
0.540 g
0.540 g remain after 25 years
a x
a

=
b) After 50 years
1 0
0
exp 0.024 667 yrs
a x
a
= 50 yrs
( )
0
0
0.291 g
a x
a

=
c) After 70 years,
1 0
0
exp 0.024 667 yrs
a x
a
= 70 yrs
( )
0
0
0.178 g
a x
a

=
9-34

9-35
9.8. The first-order decomposition of nitramide in the presence of bases, NH2NO2 N2O(g) +H2O(l), is conveniently analyzed by
collecting the gas evolved during the reaction. During an experiment, 50.0 mg of nitramide was allowed to decompose at 15 C. The
volume of dry gas evolved after 70.0 min. was measured to be 6.59 cm
3
at 1 bar pressure. Find the rate constant and the half-life for
nitramide decomposition.
Solution:
Given: Nitramide:
3
50.0 mg, 15 C, 6.59 cm, 1 bar, 70.0 min m T V P t = = = = =
Required:
1/2
, k t
When given this type of problem, it is essential that the number of moles of substance in found before the rate constant as well as the half
life can be determined. Let us begin by using the Ideal Gas Law in order to do this.
3
0
50 10 g
PV nRT
m
n
M
= =
62.023 g
( )
( )
1
4
0
reacted
reacted
mol
8.06 10 mol
70 min
1 bar
70 min
n
PV
n
RT
n
=
=
=
( )( )
3
3
6.59 cm
0.083145 dm bar
1
K
( )
1
mol 288 K
( )
( )
3 3
3
reacted
1 cm 0.001 dm
6.59 cm
70 min n
=
=
3
23.945 76 dm
3
1
0.001 dm
mol

3
1 cm
( )
4
reacted
70 min 2.75 10 mol n

=

Now that we have the initial number of moles and the number of moles reacted after 70 minutes, we can use this bit of information in the
integrated rate law as the fraction of undecomposed substance.
9-36
0 0
0 0 reacted
4
1 1
ln ln
1 8.06 10 mol
ln
70 min
a n
k
t a x t n n
k
= =

=
( )
4 4
8.06 10 2.75 10 mol

3 1
5.96 10 min k

=

The half life for the reaction may now be determined using the above value.
1/2
1/2 3 1
1/2
ln2
0.693147
5.96 10 min
116 min
t
k
t
t

=
=
=

9-37
9.9. The reaction:
2NO(g) +Cl2(g) 2NOCl(g)
is second order in NO and first order in Cl2. In a volume of 2 dm
3
, 5 mol of nitric oxide and 2 mol of Cl2 were brought together, and
the initial rate was 2.4 10
3
mol dm
3
s
1
. What will be the rate when one-half of the chlorine has reacted?
Solution:
Given: | | | |
2
2 1
3 3 3 1
2 NO Cl 0
NO , Cl , 2 dm, 5 mol, 2 mol, 2.4 10 mol dm s V n n k = = = =
Required: when half of chlorine reacted k
Let us first write out the rate law for this reaction (given that the reaction is second order in NO and first order in Cl2).
| | | |
2 1
2
NO Cl v k =
The easiest way to solve this problemis to construct a table which will enable us to examine the initial amounts of each species in addition
to the amount after half of the chlorine is reacted.
2
2NO Cl 2NOCl
initial 5 2 0 mol
reacted
+
1
final 3 1 2 mol

The rate of reaction is therefore equal to:
9-38
| | | |
| | | |
| | | |
2 1
1 1 2
2 1
3
1
3
5
1
2 1
2 1
5
2
4 3 1
2
NO Cl
2.4 10 5 2
2.4 10
4.8 10
50
When one-half of the chlorine has reacted:
3 1
4.8 10 9
4.32 10 mol dm s
rate k
k
k
rate k
rate
rate

=
=
= =
=
=
=

9-39
9.10. Measuring the total pressure is a convenient way to monitor the gas phase reaction:
2NOCl(g) 2NO(g) +Cl2(g)
However, the rate depends on the concentration of the reactant, which is proportional to the partial pressure of the reactant. Derive an
expression relating the rate of this reaction to the initial pressure, P0, and the total pressure, Pt, at time t. Assume that the reaction follows
second-order kinetics.
Solution:
Let us begin by mentioning that we will making reference to all quantities in terms of the number of moles. Let n0 denote the initial amount
of NOCl and we will say that 2x is the number of moles reacted after a period of time, t. We can again construct a table to facilitate our
problemsolving process.
( ) ( ) ( )
2
0
2NOCl g 2NO g Cl g
initial 0 0
reacted 2 2
n
x x
+
0

final 2 2
x
n x x x

We can see that the total amount of gas at any given time (t) is equal to:
0
2 n x 2x +
0
x n x + = +
With this information, we can now calculate the concentrations. We will make use of the Ideal Gas Law which states that,
0
0
0 0
initial concentration
PV nRT
n RT
P
V
n
V
n P
V RT
=
=
=

9-40

Let us now derive the expression for the concentration at the time t.
( )
0
0
0

t
t
t
total number of moles
RT
P n x
V
P n x
RT V V
P n x
V RT V
= +
= +
=

Substituting the original expression
0 0
n P
V RT
= into the expression for the concentration at time t, we get,
| | | |
0 0
0
2
Cl 2 NO
t t
t
P n P P x
V RT V RT RT
P P x
V RT
= =
= = =

And
| |
| |
| |
| |
0 0 0 0
2
2
0
2 2
2 P 2P 2P 3P 2P
NOCl
RT RT RT
NOCl 3P 2P
NOCl
R T
t t
t
n x
V
d k
rate k
dt
| |
= = =
|
\ .

= = =

9-41
9.11. The following results were obtained for the rate of decomposition of acetaldehyde:
% decomposed:
0 5 10 15 20 25 30 35 40 45 50

Rate/Torr min
1

8.53 7.49 6.74 5.90 5.14 4.69 4.31 3.75 3.11 2.67 2.29

Employ vant Hoffs differential method to obtain the order of reaction.
Solution:
It is best to solve this type of problemusing Microsoft Excel or any other math programthat will enable you to plot this curve. Employing
the Vant Hoff method, we obtain the following values:
%
decomposed
Torr
min
1

log10 (%
remaining)
log10 ( Torr
min
-1
)
0 8.53 2.00 0.931
5 7.49 1.98 0.874
10 6.74 1.95 0.829
15 5.9 1.93 0.771
20 5.14 1.90 0.711
25 4.69 1.88 0.671
30 4.31 1.85 0.634
35 3.75 1.81 0.574
40 3.11 1.78 0.493
45 2.67 1.74 0.427
50 2.29 1.70 0.360

We can now plot log10(/Torr min
-1
) versus log10(% remaining). The slope will then be the order of the reaction (with respect to time).
9-42

Using the slope function on Microsoft Excel we obtain,
slope 1.865272965
slope 2.0 to the nearest half integer
=
=

9-43
9.12. The isotope
32
15
P emits radiation and has a half-life of 14.3 days. Calculate the decay constant in s
1
. What percentage of the initial
activity remains after (a) 10 days, (b) 20 days, (c) 100 days?
Solution:
Given:
32
15 1/2
P: 14.3 days t =
Required: decay constant, percentage of initial activity
Let us begin by determining the rate constant. According to Table 9.1,
1/2
1/2
ln2
14.3 days
t
k
t
=
=
24 hrs
1 day
60 min
1 hr
60 s
1 min
1/2
7 1
1
1 235 520 s
0.693 147
1 235 520 s
5.61 10 s or,
0.693 147
14.3 days
0.0485 days
t
k
k
k
k

=
=
=
=
=

a) Percentage of initial activity remaining after 10 days
9-44
( )
0
0
0
0
1
ln
ln
exp lne
a
k
t a x
a
kt
a x
kt
=
=
( )
0
0
0
0
1 0
0
exp
exp 0.0485 days
a
a x
a x
kt
a
a x
a
| |
|
\ .
= 10 days
( )
0
0
0.615 697 100%
62% active
a x
a
=

b) Percentage of initial activity remaining after 20 days
9-45
( )
0
0
0
0
1
ln
ln
exp lne
a
k
t a x
a
kt
a x
kt
=
=
( )
0
0
0
0
1 0
0
exp
exp 0.0485 days
a
a x
a x
kt
a
a x
a
| |
|
\ .
= 20 days
( )
0
0
0.379 083 100%
38% active
a x
a
=

c) Percentage of initial activity remaining after 100 days
9-46
( )
0
0
0
0
1
ln
ln
exp lne
a
k
t a x
a
kt
a x
kt
=
=
( )
0
0
0
0
1 0
0
exp
exp 0.0485 days
a
a x
a x
kt
a
a x
a
| |
|
\ .
= 100 days
( )
0
0
0.007 828 100%
0.78% active
a x
a
=

9-47
9.13. The following counts per minute were recorded on a counter for the isotope
35
16
S at various times:

Time/d Counts/min
0 4280
1 4245
2 4212
3 4179
4 4146
5 4113
10 3952
15 3798

Determine the half-life in days and the decay constant in s
1
. How many counts per minute would be expected after (a) 60 days and (b) 365
days?
Solution:
Given:
35
16
S: see above
Required:
1/2
, decay constant in each case t
In order to plot this graph, we will use roughly the same method as we did in problem9.11.
t (days) n (min) ln(n0/n)
0 4280 0.00E+00
1 4245 8.21E-03
2 4212 1.60E-02
3 4179 2.39E-02
4 4146 3.18E-02
5 4113 3.98E-02
10 3952 7.97E-02
15 3798 1.19E-01
Formatted: Line spacing: Exactly 12
pt
pt
pt
pt
pt
pt
pt
pt
pt
9-48

We can plot ln(n0/n) against t in order to find the slope, k. It is equally possible to simply calculate the slope based on the rise over run principle.
3 1
3 1 8 1
rise 0.119
slope 7.93 10 days
run 15
7.93 10 days 9.18 10 s k k

= = =
= =

This plot indicates that the reaction is first order.
Now that we have determined the value of the decay constant, we can find the half life.
1/2 3 1
1/2
0.693 147
7.93 10 days
87 days
t
t

=
=

a) Thenumber of counts per minute expected after 60 days,
9-49
0
0.693
ln
( ) 87
n
kt t
n t
| |
= =
|
\ .

3 1
60
7.93 10 days kt

=
( )
60 days
( )
( )
0
60
0.4758 ln
exp 0.4758 lne
n
kt
n
= =
=
0
0
0
1.609 301
4280
2659.5
1.609 301 1.609 301
2660 counts
n
n
n
n
n
n
n
=
= = =
=

b) Thenumber of counts per minute expected after 365 days,
3 1
60
7.93 10 days kt

=
( )
365 days
( )

( )
0
60
2.894 45 ln
exp 2.894 45 lne
n
kt
n
= =
=
0
0
0
18.073 558
4280
236.8
18.073 558 18.073 558
237 counts
n
n
n
n
n
n
n
=
= = =
=

9-50
9.14. The reaction:
+ +
2 2 2 2
-Cr(en) (OH) -Cr(en) (OH) cis trans z
is first order in both directions. At 25 C the equilibriumconstant is 0.16 and the rate constant k1 is 3.3 10
4
s
1
. In an experiment
starting with the pure cis form, how long would it take for half the equilibriumamount of the trans isomer to be formed?
Solution:
Given:
4 1
eq 1
25 C, 0.16, 3.3 10 s T k k = = =
Required: see above
It is important to realize that these are two opposing reactions occurring at the same time. We are told that they are 1
st
order in both
directions therefore for the reaction
1
1
A Z
k
k
, if the experiment is starting with the pure cis formof the isomer of concentration a0 and if
after time t, the concentration of the trans formof the isomer has the concentration x, then that of the cis formwill be equal to a0-x.
If the forward reaction were to occur in isolation, its rate equation could be written as;
( )
1 1 0
v k a x =
While the rate of the reverse reaction would be written as;
1 1
v k x

=
Since these reactions are in opposite directions, we can define the net rate of change of concentration of the trans isomer as:
( )
1 0 1
dx
k a x k x
dt

=
If xe is the concentration of the trans isomer at equilibrium(this is when the net rate is zero), then we know that,
( )
( )
( )
1 0 1
1 0 1
1
eq
1 0
0
e
e
k a x k x
k a x k x
x k
k
k a x
=
=
= =

9-51
It is possible to eliminate
1
k
in order to obtain the following Eq. 9.47:

( )
1 0
e
e
k a dx
x x
dt x
=
Integration of this equation, subject to the boundary condition that x =0 when t =0 gives the rate equation corresponding to Eq. 9.48:
( )
( )
0 1
1
0
ln or ln ln
e e
e e
e e
x x a k t
k t x x x
a x x x
= =

For half of the equilibriumamount of product to be formed, it would mean that
2
e
x
x = . Making this substitution into the above will yield,
1 1/2
0
1 1/2
0
1 1/2
0
ln
2
ln
2
ln
e e
e
e
e e
e
e
e
x x
k t
x a
x
x x
k t
x a
x
k t x
a
=
| |
|
\ .
=
| |
|
\ .
=
2
e
x
1 1/2
0
ln2
e
x
k t
a
| |
|
|
\ .
=

Having been given the equilibriumconstant as well as the rate constant for the forward reaction, we can now do a few more calculations in
order to determine how long it would take for half the equilibriumamount of the trans isomer to be formed.
9-52
( )
( )
( )
eq
0
0
eq
0 0
0
0
1 1/2
0
0.16
1 1
0.16
1
1
0.16
1
1
0.16
7.25
ln2
e
e
e
e
e
e e
e
e
e
x
k
a x
a x
k x
a x a
x x
a
x
a
x
x
k t
a
= =
= =
= =
= +
=
=

( )
0
1/2
0
1
1
1/2
4 1
1/2
1/2
ln2
ln2
0.693147
7.25 3.3 10 s
289.7 s
290 s
e
e
x
a
t
a
k
k
x
t
t
t

= =
=

=
=

9-53
9.15. Suppose that a gas phase reaction 2A(g) 2B(g) +C(g) follows second-order kinetics and goes to completion. If the reaction is
allowed to proceed in a constant volume vessel at an initial pressure of 2 bar (only A is initially present), what will be the partial
pressures of A, B, and C and the total pressure at t =t1/2, 2t1/2, 3t1/2, and infinity?
Solution:
Given: 2A(g) 2B(g) +C(g) (second order),
0
2 bar P =
Required:
A B C tot
, , , P P P P at t =t1/2, 2t1/2, 3t1/2and infinity
Recall fromsection 9.4 that if we have a reaction of either of the following forms:
2A Z or A B Z +
We can write the rate equation in its differential formaccording to Eq. 9.31 and Eq. 9.32.
( )
( )
2
0
2
0
dx
k a x
dt
dx
kdt
a x
=
=

Eq. 9.32 can then be integrated in order to obtain the following:
( )
( )
( ) ( )
0
0
0 0 0 0
1
constant of integration
when 0, 0
1
1 1
2
kt I
a x
I
x t
I
a
x
kt kt
a a x a x a
+ =
=
= =
=
= =

Let us assume that 2x moles of substance A are consumed in each step. For a 2
nd
order reaction, we can check Table 9.1 or look at Eq. 9.40
in order to find the expression for the half life.
9-54
( )
1/2
0
1
t
a k
=
Since all of the times asked for are written in multiples of the half life, we can write,
( )
0 0 0
1 1
where 1,2,3,
2
n
kt n
a a x a
= = =

Further simplification of this expression gives,
( )
0 0 0
0 0
0
0
0
0
0
1 1
2
1 1
2
2
1
2
1
2 1
n
a a a x
n
a a x
a
a x
n
a
x a
n
a n
x
n
+ =
+
=
=
+
=
+
| |
=
|
+ \ .

Using simple stoichiometry, we can see that,
A 0
B
C
2
2
P a x
P x
P x

9-55
0
0
0
A
0
0
B 0
0
0
C
Since 2 , then
1
1
Since 2 then
1
1
Since then
2 1
2 1
a
a x
n
P
P
n
a
x a
n
n
P P
n
a n
x
n
P n
P
n
=
+
=
+
=
+
=
+
| |
=
|
+ \ .
| |
=
|
+ \ .

Using the above three expressions, we can construct a table which will give the partial pressures for each species in addition to the total
pressure at each temperature.
t PA (bar) PB (bar) PC (bar)
Ptot
(bar)
t0 2.000 0.000 0.000 2.000
t1/2 1.000 1.000 0.500 2.500
2t1/2 0.667 1.333 0.667 2.667
3t1/2 0.500 1.500 0.750 2.750
tinfinity 0.000 2.000 1.000 3.000

9-56

9-57
9.16. Derive the following relationship for the half-life t1/2 of a reaction of order n, with all reactants having an initial concentration a0:
1
1/2 1
0
2 1
( 1)
n
n
t
ka n
=
Solution:
FromTable 9.1, we are given the general expression for a reaction of the n
th
order. We can separate the variables and integrate this in order
to generate the above equation for the half life of an n
th
order reaction.
( )
( )
( )
( )
( )
( )
( )
0
1
1
0
0
1
0
0
1
1 1 1
1
n
n
n
n
n
n
a
dx
k a x
dt
x
dx
kdt
a x
dx
n
k
t n a
a
kdt
a x
kt
x
(
=
=
=
=
(

Recall that at the half life,
0
2
a
x = and therefore,
9-58
( )
( )
( )
0
0
0
1 1
1/2
0
0
1 1
1/2
0
1/2 1 1
0
1 1 1
1
2
1 1 1
1
2
1 1 1
1
2
n n
n n
n n
k
t n a
a
a
k
t n a
a
t
k n a
a

(
(
(
=
(
| |
(
|
\ .
(
(
(
=
(
| |
(
|
\ .
(
(
(
=
(
| |
(
|
\ .

Further simplification will yield,
( )
( )
( )
( )
0
0 0 0 0
0
1
1 0
1/2
1
1 1 1 1 1 1 0
1
1/2 1
1
1 2
2 2 1
2
2 1
1
n
n
n
n n n n n n
n
n
a
t a
k n
a
a a a a
t
ka n
(
| |
= (
|
\ . (

(
| |
= = (
|
\ . (

9-59
9.17. Vaughan [J. Am. Chem. Soc. 54, 3867(1932)] reported the following pressure measurements as a function of time for the
dimerization of 1,3-butadiene (C4H6) under constant volume conditions at 326 C:
t/min 3.25 12.18 24.55 42.50 68.05
P/Torr 618.5 584.2 546.8 509.3 474.6

The initial amount of butadiene taken would have exerted a pressure of 632.0 Torr. Find whether the reaction follows first- or second-order
kinetics and evaluate the rate constant.
Solution:
Given: see above
Required: first or second order kinetics? k
First we should write out the balanced reaction for this process.
4 6 8 12
0
0
2C H C H
initial 0
time 2
n
t n x x

We are again assuming that 2x moles are being consumed in each step (problem9.15). Fromthis, we can determine the number of moles at
any given time, t.
0 0
0
2
at time
n x x n x
n x t
+ =

Using the Ideal Gas Law, we can derive expressions for the number of moles in both instances.
9-60
( )
( )
0
0
0
0 0
0
0 0
t
t
t
PV nRT
n RT
P
V
n x RT
P
V
n x RT n RT
P P
V V
RT
P P n
V
=
=
=
=
0
n
( )
0 t
x
xRT
P P
V
(

=

The partial pressure of butadiene at a time t, can therefore be expressed as,
( )
4 6
0
C H 0
2
2
t
n x RT
P P P
V
= =
e.g. at time 3.25min, Pt=618.5 Torr
4 6
C H
(3.25) 2 618.5 632 605 P = = etc.
Re-tabulating the given data in terms of the partial pressure of butadiene will yield,
t/min 3.25 12.18 24.55 42.50 68.05

4 6
C H
P /Torr 2
t o
P P = 605.0 536.4 461.6 386.6

317.2

4 6
ln
C H
o
P
P
| |
|
\ .
-0.0437 -0.1640 -0.3142 -0.4915 -0.6894

9-61

In order to determine whether the reaction proceeds according to 1
st
or 2
nd
order kinetics, one should first plot
4 6
C H
vs. P t . This plot yields
curved line.

This means that the reaction does NOT proceed according to 1
st
order kinetics and therefore, we must now try to plot the inverse of the
pressure versus time.
9-62

This straight-line plot indicates that the reaction follows 2
nd
order kinetics. It is also possible to performa linear regression (using
Microsoft Excel Linest Function) in order to reveal the integrated rate law.
nd
2 order kinetics
linear regression statistics:
2.31869E-05 0.001586
2.66985E-07 1.01E-05
0.999602407 1.38E-05
7542.405387 3
4 6
5
C H
1
2.31869 10 0.001586 t
P
= +
Remember that the slope of this line will be equal to the rate constant, k.
5
2.31869 10 k

=

9-63
9-64
9.18. A drug administered to a patient is usually consumed by a first-order process. Suppose that a drug is administered in equal amounts
at regular intervals and that the interval between successive doses is equal to the (1/n)-life for the disappearance process (i.e., to the
time that it takes for the fraction 1/n to disappear). Prove that the limiting concentration of the drug in the patients body is equal to n
times the concentration produced by an individual dose.
Solution:
When the concentration has reached nc, where c is the concentration produced by a single dose, the concentration will fall to ( ) 1 n c during
the interval between successive doses. The next dose restores the concentration to ( ) 1 n c c + which when simplified is equal to nc. This
indicates that the steady state has been reached.

9-65
9.19. Equation 9.45 applies to a second-order reaction of stoichiometry A +B Z. Derive the corresponding equation for a second-order
reaction of stoichiometry 2A +B Z.
Solution:
0 0
0 0
2A B Z
0
2
a b
a x b x x
+

( )( )
( )( )
( )( ) ( ) ( )
( ) ( )
( ) ( )
0 0
0 0
0 0 0 0 0 0
0 0 0 0
0 0
0 0
0
0 0
2
2
1 1
2 2 2 2
1 1
2 2 2
1 1 1
ln 2 ln2
2 2 2
when 0, 0
1 1
ln 2
2 2
dx
k a x b x
dt
dx
kdt
a x b x
dx dx
kdt
a x b x a x b x b a
dx
kdt
a x b x b a
kt a x b x I
b a
x t
I a x
b a
=
=

(
= =
(

(
=
(

(
= + +
(

= =
=

( ) 0
1
ln2
2
b x +
( )
( )
0
0 0 0
2 1 1 1
ln ln
2 2 2 2
a
kt
b a a x
(
(

=

0
2
b
( )
( )
( )
( )
0
0 0
0 0 0 0
1
ln
2 2 2
b x
a b x
kt
b a b a x
(
(
=

9-66

9-67
9.20. Derive the integrated rate equation for an irreversible reaction of stoichiometry 2A +B Z, the rate being proportional to [A]
2
[B]
and the reactants present in stoichiometric proportions; take the initial concentration of A as 2a0 and that of B as a0. Obtain an
expression for the half-life of the reaction.
Solution:
0 0
0 0
2A B Z
2 0
2 2
a b
a x b x x
+

| | | |
| |
| |
( ) ( )
2
0
0
0
0
2
0 0
A B
A 2
B
2 2
v k
a
b
dx
k a x b x
dt
=
=
=
=

For simplicity, we will say that ( ) ( )
0 0
b x a x = . Making this substitution into the above yield,
9-68
( ) ( )( )
( ) ( )
( ) ( )
( )
( )
( )
( )
0 0
2
0 0 0
2
2 2 2 2
0 0 0 0
2 3
0 0
3
0
3
0
3
0
2
0
0
2 2 2 2 2 2
2 2 4 4 4 4 4 2
2 2 4
4
4
4
1
4
2
when 0, 0
1
2
a x a x a x
a x a a x a x x a a x x
a x a x
dx
k a x
dt
dx
kdt
a x
dx
kdt
a x
kt I
a x
x t
I
a x
=
= + = +
=
=
=
+ =
= =
=

( )
( )
0
0
2 2
2 2
0
0
1/2
1
2
1 1
4
2
2
at , hence,
2
a
kt
a
a x
a
t x
=
=
=

9-69
0
1/2 2 2
0
0
1 1 1
4
2
2 2
2
kt
a
a
a
= =
| |
|
\ .
0
0 0 0 0 0 0
0
0
0
0
2 2
0
1/2 2 2 2 2 2 2
1/2 2
2
1/2 2
1/2 2
1
2
2
1 1 2 1 4 1
4
2 2 2 2
2
3
4
2
3
2
3 1
4 2 4
3
8
a
a
kt
a a a a a a
kt
a
a
t
k a k
t
ka
| |
|
\ .
= = =
=
= =
=

9-70
9.21. Prove that for two simultaneous (parallel) reactions

1
2
[Y]
at all times.
[Z]
k
k
=

Solution:
Let us begin by writing out the rate equations for each individual reaction.
| |
| |
| |
| |
1 2
Y Z
A and A
d d
k k
dt dt
= =
Setting these expressions equal to one another it is possible to eliminate the concentration of A.
| |
| |
1
Y
A
d
k
dt
=
| |
| |
2
Z
A
d
k
dt
= =
| |
| |
1
2
Y
Z
d k
k d
=

Integrate both sides of the equation to obtain,
| | | |
| | | |
1
2
1
2
Z Y
Z Y
k
d d
k
k
I
k
=
+ =

Note that under the boundary condition t =0, then | | | | Y Z = therefore, I =0 hence;
9-71
| | | |
| | | |
| |
| |
1
2
1
2
1
2
Z Y
0
Z 0 Y
Y
Z
k
I
k
I
k
k
k
k
+ =
=
+ =
=

9-72
*9.22. Prove that for two consecutive first-order reactions; A B C the rate of formation of C is given by:
1 2

2 1
0
1 2
e e
[C] [A] 1
k t k t
k k
k k
| |
= +
|
\ .

where [A]0 is the initial concentration of A.
(Hint: The solution of the differential equation):
bt
dx
abe cx
dt
=
where a, b, and c are constants, is

(e e )
bt ct
ab
x I
c b
= +
Solution:
1 2
0
0
0
A B C
0 0
0

k k
a
a x x
b x x

Writing out the rates of consumption and formation for each species, we will obtain,
| |
| |
| |
| | | |
| |
| |
1
1 2
2
A
A
B
A B
C
B
d
k
dt
d
k k
dt
d
k
dt
=
=
=

Let us integrate the first expression after separating the variables.
9-73
| |
| |
| |
| | | |
| |
| |
t
0
t
0
A
1
A
A
1
A
1
t 0
t
1
0
A
A
ln A
ln A ln A
A
ln
A
lne
d
k dt
k t
k t
k t
=
=
=
=

| |
| |
( )
| | | | ( )
t
1
0
1
t 0
A
exp
A
A A exp
k t
k t
=
=

This expression can be substituted into the rate of formation for substance B. This will yield,
| |
| | ( ) | |
1 1 2
0
B
A exp B
d
k k t k
dt
=
With the boundary condition t =0, this means that | | B =0 which allows us to further simplify the above.
| |
| | ( ) | |
| | ( ) | |
| |
| | ( )
| | | |
( ) ( )
( )
1 2
1 1 2
0
1 1 2
0
1 1
0
2
1
0
2 1
B
A exp B 0
A exp B
A exp
B and integrate to obtain,
B A e e
k t k t
d
k k t k
dt
k k t k
k k t
k
k
k k

= =
=
=
=

9-74
| | | | | | | |
| | | | | | | |
| | | | | | ( ) | |
( ) ( )
( )
1 2
0
0
1
1
0 0 0
2 1
A A B C
C A A B
C A A exp A e e
k t k t
k
k t
k k

= + +
=
=

Simplify by method of factoring the above to get the appropriate expression (that which is sought after).
1 2

2 1
0
1 2
e e
[C] [A] 1
k t k t
k k
k k
| |
= +
|
\ .

9-75
*9.23. a. Derive the integrated rate equation for a reversible reaction of stoichiometry:
1
1
A Y +Z
k
k
z
The reaction is first order fromleft to right and second order fromright to left. Take the initial concentration of A as a0 and the
concentration at time t as a0 x.
b. Obtain the integrated equation in terms of k, and the equilibriumconstant K =k1/k1.
c. A reaction to which this rate equation applies is the hydrolysis of methyl acetate. Newling and Hinshelwood, J. Chem. Soc., 1936,
1357(1936), obtained the following results for the hydrolysis of 0.05 M ester at 80.2 C in the presence of 0.05 M HCl, which
catalyzes the reaction:
Time, s 1350 2070 3060 5340 7740
Percent hydrolysis 21.2 30.7 43.4 59.5 73.45 90.0

Obtain values for the rate constants k1 and k1.
Solution:
1
1
0
0
A Y Z
initial 0 0
time
k
k
a
t a x x x
+
z

a) We can write out the rate equation with respect to the rate of consumption of the concentration of A.
| |
| | | || |
1 1
A
A Y Z
d
k k
dt

=
At a time t, this can then be written in the following form:
( )
2
1 0 1
dx
k a x k x
dt

=
Recall that at equilibrium, 0
dx
dt
= therefore,
9-76
( )
( )
( )
( )
2
1 0 1
2
1 0 1
1 0
1 2
0

e
e
e
e
e
e
k a x k x
k a x k x
k a x
k
x
=
=
=

Insertion of this expression into the first equation yields,
( )
( )
1 0
1 0
2
e
e
k a x dx
k a x
dt
x
=
( ) ( )
( ) ( )
( ) ( )
2
2
2 2 2
1 0 1 0
2
2 2 2
1 0 0
2
1
2 2 2
0 0
e
e e
e
e e
e
e e
e
e
e
x
x dx
x k a x x k a x x
dt
x dx
k x a x x a x x
dt
x dx
k dt
x a x x a x x
| |
|
|
\ .
=
( =

=
(

Integration of the LHS of this expression can be carried out after resolution into partial fractions.
( )
0 0 0
0
0 0
LHS
and
2 2
e e
e e e
e e
p q
a x a x a x x x
x a x x
p q
a x a x
= +
+
= =

The integration is now straightforward although rather lengthy. We will use the boundary conditions t =0, x =0 which gives the
following result.
9-77
( )
( )
( )
( )
0 0
1
0 0
ln *
2
e e e
e e
a x x a x x
k
a x t a x x
+
=

Readers wishing further mathematical details/explanation are referred to C. Capellos and B.H.T Bielski, Kinetic Systems (New York:
Wiley, Interscience, 1972) pp.41-43.
b) Knowing that the equilibriumconstant is K =k1/k1, we may also write, from( )
( )
( )
2
1 0 1
1 1 0
1
0
e e
e
k a x k x
k k a x
k
=
2
1
e
x
k
( )
1 0 e
k a x
( )
1 0 e
k a x
( )
2
0
e
e
x
a x
=

( )
2
1
1 0
e
e
x
k
K
k a x
= =

c) In order to deal with the numerical data which are in terms of percent hydrolysis, it is convenient to define,
0 0
and
e
e
x x
r r
a a

Substituting this into the integrated rate law derived in part A, (*)
( )
( )
( )
1
1
ln
2
e e e
e e
r r r r
k
r t r r
+
=

9-78
Fromthe data given in the problem, we have 0.90
e
r = . We may now construct a table which will allow us to plot
( )
( )
1
ln
e e
e
r r r
r r
+
versus
time. Remember that the slope of this line will enable us to find the forward and reverse rate constant values.
1
(1 ) (2 )
ln
( )
e e e
e e
slope
r r r k r
t
r r r
( | | +
=
| (
\ .
_

time (s) r re +r(1-re) re-r ln(re+r(1-re))/(re-r)
1350 0.212 0.9212 0.688 0.2919
2070 0.307 0.9307 0.593 0.4507
3060 0.434 0.9434 0.466 0.7053
5340 0.595 0.9595 0.305 1.1461
7740 0.7345 0.97345 0.1655 1.7719

( )
1 4 1
2 1.64 0.35
slope 1.843 10 s
7000 s
e
e
k r
r

= = =
9-79
Solving for
1
k we obtain,
( ) ( )
( )
1
1
1 4 1
1
4 1
1
4 1
1
2 2 0.90
0.90
2
1.222 1.843 10 s
1.843 10 s
1.222
1.51 10 s
e
e
e
e
k r
k
r
k r
k
r
k
k

=
= =
=
=

This is done at constant catalyst concentration of 0.05 M HCl and makes k1[0.05] 1
st
order. The 2
nd
order rate constant is therefore,
( )
4 1
1 3
nd 3 3 1 1
1
1
1.51 10 s
0.05 mol dm
2 order 3.02 10 dm mol s
k
k

=
=

At equilibrium,
( ) ( ) ( )
1
1
A Y Z
0.05 0.1 0.05 0.9 0.05 0.9
k
k
+ z

9-80
| || |
| |
( ) ( )
( )
( )
( )
2
1
1
3
4 1
1
1 3
4 3 1 1
1
nd 4 3 1 1
1 3
nd 3 6 2 1
1
0.05 0.9 Y Z
A 0.05 0.1
0.405 mol dm
1.51 10 s
0.405 mol dm
3.73 10 dm mol s
1
0.05 mol dm
k
K
k
K
k
k
K
k
k
k
= = =
=
= =
=
=
=

9-81
*9.24. The dissociation of a weak acid HA +H2O = H3O
+
+A

can be represented as:
A z Y +Z
The rate constants k1 and k1 cannot be measured by conventional methods but can be measured by the T-jump technique (Section
9.5). Prove that the relaxation time is given by:
1 1
1
*
2
e
t
k k x
=
+

where the concentration of the ions (Y and Z) is at equilibrium.
Solution:
If a0 is the initial concentration of substance A and x is the concentration of ions at equilibrium, then the corresponding rate law is the same
one as we have seen in the previous problem.
( )
( )
2
1 0 1
2
1 0 1
At equilibrium, 0
0
e e
dx
k a x k x
dt
dx
dt
k a x k x
=
=
=

The deviation fromthe equilibriumcan be defined as:
e
x x x = and we may also write,
( )
2
1 0 1
d x dx
k a x k x
dt dt

= =
Subtraction of the second expression fromthe above yields
( )
2
1 1 1
2
e
d x
k x k x k x x
dt

=
Since x is very small, the termin the ( )
2
x may be ignored. This will omission will produce,
( )
1 1
1 1
2
2
e
e
d x
k x k x x
dt
d x
k k x x
dt
=

9-82
Integrate this expression to obtain,
( )
( )
1 1
1 1
2
ln 2
e
e
d x
k k x dt
x
x k k x t I
= +

Using the boundary condition t =0,
0
x x = ,
( )
( )
0
1 1
ln 2
e
x
k k x t
x

By definition, the relaxation time t
is the time that corresponds to,

( )
( )
( )
( )
0
1 1
1 1
e since ln e 1 then,
1 2
1
2
e
e
x
x
k k x t
t
k k x
= =
=
=
+

9-83
Solution:
Given:
30 C 20 C
2 k k

=
Required:
a
E
We are told that T1 =293.15 K and T2 =303.15 K. Let us take the inverse of these two temperatures in order to plot ln(k) versus 1/T. If
this plot yields a straight line, then we know that the slope of this line is equal to the activation energy divided by R. We know that this is
true according to the Arrhenius equation,
/
e
ln ln lne
a
E RT
k A
k A
=
=
/
20 C
30 C
ln ln
ln
ln
a
E RT
a
E
k A
RT
A
k
k
=
=
1
ln
a
E
RT
A
2
therefore, ln ln2
a
k
E
RT
=

9-84
( )
3 1
1
3 1
2
3 3 1
2 1
1
1 1
3.411 10 K
293.15 K
1 1
3.299 10 K
303.15 K
ln2 0.693147
m
1 1
3.299 10 3.411 10 K
m 6160 K
m= 8.3145 J K
a
a
T
T
T T
E
R
E R

= =
= =
= =

= =
=
1
mol 6160 K
1
1
51 217.32 J mol
51.2 kJ mol
a
a
E
E
=
=


9-85
Solution:
Given:
230 C 220 C
2 k k

=
Required:
a
E
/
e
ln ln lne
a
E RT
k A
k A
=
=
/
220 C
230 C
ln ln
ln
ln
a
E RT
a
E
k A
RT
A
k
k
=
=
1
ln
a
E
RT
A
2
therefore, ln ln2
a
k
E
RT
=

9-86
( )
3 1
1
3 1
2
3 3 1
2 1
1 1
2.028 10 K
493.15 K
1 1
1.987 10 K
503.15 K
ln2 0.693147
m
1 1
1.987 10 2.028 10 K
m 17196 K
17 196 K
a
a
T
T
T T
E
R
E

= =
= =
= =

= =
=
1
8.3145 J K
1
1
1
mol
142 976.142 J mol
143 kJ mol
a
a
E
E
=
=


9-87
9.27. The following data for a first-order decomposition reaction in aqueous mediumwas reported by E. O. Wiig [J. Phys. Chem. 34,
596(1930)].
t/C 0 20 40 60
k/10
5
min
1
2.46 43.5 575 5480

Find the activation energy and the preexponential factor.
Solution:
Given: see above
Required: ,
a
E A
Let us first change the temperature fromCelsius to Kelvin, then proceed by taking the inverse value of each temperature and the lnk for
each value given above. We will then plot lnk versus 1/T. Since we have been told that this is a 1
st
order decomposition, this straight line
will give us a slope which will enable us to determine the activation energy and in turn the pre-exponential factor.
T (K) 1/T (K
-1
) k (10
5
min
1
) lnk
273.15 0.003661 2.46 -10.6128
293.15 0.003411 43.5 -7.74016
313.15 0.003193 575 -5.15856
333.15 0.003002 5480 -2.90407

It is either possible to performa linear regression or simply add a trendline to the plot using Microsoft Excel in order to determine the
equation of the line. Either method will produce the same results.
9-88

/
e
ln ln lne
a
E RT
k A
k A
=
=
/
ln ln
a
E RT
a
E
k A
RT
=

When plotting lnk versus 1/T, you will find that lnAis the y-intercept and that
a
E
R
is the slope.
11 703
ln ln 32.217
11 703 K
a
a
E
k A
RT T
E
= =
=
1
8.3145 J K
1
1
1
mol
97 304.59 J mol
97.3 kJ mol
a
a
E
E
=
=

9-89
ln 32.217
lne
A =
32.217
13 1
12 1
e
9.81 10 min
1.63 10 s
A
A
A
=
=
=


9-90
9.28. Two second-order reactions have identical preexponential factors and activation energies differing by 20.0 kJ mol
1
. Calculate the
ratio of their rate constants (a) at 0 C and (b) at 1000 C.
Solution:
Given: two second order reactions:
1
1 2 2 1
, 20.00 kJ mol
a a
A A E E

= = +
Required:
1
2
in each case
k
k

a) The ratio of their rate constants at 0 C.
1 2
/ /
1 2
1
2
e and e
ratio
a a
E RT E RT
k A k A
k A
k

= =
= =
/
e
a
E RT
A
/
e
a
E RT
this is true since both pre-exponential factors are identical.
20 000 J
/ 1
2
e e
a
E RT
k
k
= =
1
mol
/ 8.3145 J
1
K
1
mol
( )
273.15 K ( )
( )
3 1
2
273.15 K 6.68 10
k
k
=

b) The ratio of their rate constants at 1000 C
1 2
/ /
1 2
1
2
e and e
ratio
a a
E RT E RT
k A k A
k A
k

= =
= =
/
e
a
E RT
A
/
e
a
E RT
this is true since both pre-exponential factors are identical.
20 000 J
/ 1
2
e e
a
E RT
k
k
= =
1
mol
/ 8.3145 J
1
K
1
mol
( )
1273.15 K ( )
( )
1
2
1273.15 K 6.62
k
k
=

9-91
9-92
9.29. The gas-phase reaction between nitric oxide and oxygen is third order. The following rate constants have been measured:
T/K 80.0 143.0 228.0 300.0 413.0 564.0
k 10
9
/cm
6
mol
1
s
1
41.8 20.2 10.1 7.1 4.0 2.8

The behavior is interpreted in terms of a temperature-dependent preexponential factor; the rate equation is of the form:
k =aT
n
e
E/RT

where a and n are constants. Assume the activation energy to be zero and determine n to the nearest half-integer.
Solution:
Given: see above
Required: n to the nearest half-integer
We will begin by calculating the ln(T) as well as the ln(k) for each value given above.
T (K) ln(T) k (cm
6
mol
1
s
1
) ln(k)
80 4.382 4.18E+10 24.4562
143 4.963 2.02E+10 23.7289
228 5.429 1.01E+10 23.0358
300 5.704 7.10E+09 22.6834
413 6.023 4.00E+09 22.1096
564 6.335 2.80E+09 21.7529

9-93

/
e
since and are constants and the activation energy is zero,
ln ln ln
n E RT
a
k aT
a n
E
k a n T
RT
=
= +
ln ln ln k a n T = +

This means that a plot of ln(k) versus ln(T) will create a line with a slope equal to n and the y-intercept is equal to lna.
ln 30.68 1.410
1.4
k x
n
=
=

9-94
9.30. The definition of activation energy Ea is generally considered to be given by an extension of Eq. 9.91:
2
ln
a
d k
E RT
dT
| |
=
|
\ .

Problem9.29 shows that for certain reactions, the temperature dependence of the reaction rate constant is better described by an
expression of the type
k =aT
n
e
E/RT

Using the definition for Ea given here, derive an expression for the activation energy fromthis expression.
Solution:
Given that
2
ln
a
d k
E RT
dT
| |
=
|
\ .
, we can write;
/
e
ln ln ln
n E RT
a
k aT
E
k a n T
RT
=
= +

Take the derivative with respect to the temperature to obtain,
ln ln d k d a
dT dT
=
2
2
2
2
2
2
ln
ln
ln ln
and then,
a
a
a
E
d
nd T RT
dT dT
d k n E
dT T RT
d k d k n E
E RT
dT dT T RT
n E
E RT
T RT
nRT
E
| |
|
\ .
+
= +
| |
= = +
|
\ .
| |
= +
|
\ .
=
T
2
E RT
+
2
RT
a
E nRT E = +

Formatted: Space After: 6 pt, Don't
adjust space between Latin and Asian
text
9-95

9-96
9.31. The water flea Daphnia performs a constant number of heartbeats and then dies. The flea lives twice as long at 15 C as at 25 C.
Calculate the activation energy for the reaction that controls the rate of its heartbeat.
Solution:
Given: Daphnia: lives twice as long at 15 C as at 25 C
Required:
a
E
/
e
ln ln lne
a
E RT
k A
k A
=
=
/
15 C
25 C
ln ln
ln
2
ln
a
E RT
a
E
k A
RT
A
k
k
=
=
1
ln
a
E
RT
A
2
a
E
RT

9-97
( )
3 1
1
3 1
2
25 C 15 C
3 3 1
2 1
1 1
3.470 10 K
288.15 K
1 1
3.354 10 K
298.15 K
2 therefore,
ln2 0.693147
m
1 1
3.354 10 3.470 10 K
m 5974 K
5974 K
a
a
T
T
k k
T T
E
R
E

= =
= =
=
= =

= =
=
1
8.3145 J K
1
1
1
mol
49 670.823 J mol
49.7 kJ mol
a
a
E
E
=
=

9-98
9.32. A sample of milk kept at 25 C is found to sour 40 times as rapidly as when it is kept at 4 C. Estimate the activation energy for the
souring process.
Solution:
Given: milk: see above
Required:
a
E
/
e
ln ln lne
a
E RT
k A
k A
=
=
/
4 C
25 C
ln ln
ln
ln
a
E RT
a
E
k A
RT
A
k
k
=
=
1
ln
a
E
RT
A
2
therefore, ln ln40
a
k
E
RT
=

9-99
( )
3 1
1
3 1
2
3 3 1
2 1
1 1
3.608 10 K
277.15 K
1 1
3.354 10 K
298.15 K
ln40 0.693147
m
1 1
3.354 10 3.608 10 K
m 14 500 K
14 500 K
a
a
T
T
T T
E
R
E

= =
= =
= =

= =
=
1
8.3145 J K
1
1
1
mol
120 560.25 J mol
121 kJ mol
a
a
E
E
=
=


9-100
*9.33. Experimentally, the rate constant for the O(
3
P) +HCl reaction in the gas phase is found to have a temperature dependence given by:
k (cm
3
molecule
1
s
1
) =5.6 10
21
T
2.87
e
1766K/T
in the range 350 1480 K [Mahmud, Kim, and Fontijn, J. Phys. Chem. 94, 2994(1990)].
a. Using the results of Problem9.30, find the value of Ea at 900 K, which is approximately the middle of this range.
b. Using variational transition-state theory (an extension of the transition-state theory described in Section 9.9), the theoretical rate
constant for this reaction is found to behave according to the equation:
k (cm
3
molecule
1
s
1
) =6.9 10
20
T
2.60
e
2454K/T

in the same temperature range [T. C. Allison, B. Ramachandran, J . Senekowitsch, D. G. Truhlar, and R. E. Wyatt, J. Mol. Structure,
Theochem, 454, 307, 1998.] Compare the experimental and theoretical rate constants at 900 K.
Solution:
Given: see above, problem9.30
Required: ( )
theoretical experimental
900 K , compare with
a
E k k
a) Fromthe equation obtained by Mahmud, et al.,
1766 K E =
1
8.3145 J K
1
1
mol
14 683.407 J mol E
=

Using the expression derived in problem9.30, we can determine the activation energy for this process at 900 K.
( )
( )
3 1 1 21 2.87 1766K/ /
1
since cm molecule s 5.6 10 e and e
2.87
2.87 8.3145 J K
a
T n E RT
a
E nRT E
k T k aT
n
E

= +
= =
=
=
( )
1
mol 900 K
( )
1
1
1
14 683.407 J mol
36 159.7605 J mol
36.2 kJ mol
a
a
E
E
+
=
=

9-101

b) Using variational transition-state theory in the same temperature range we find that,
( )
( ) ( )
3 1 1 21 2.87 1766K/
3 1 1 21 2.87 1766/900
cm molecule s 5.6 10 e
cm molecule s 5.6 10 900 e
T
k T
k
=
=

( )
( )
( ) ( )
( )
3 1 1 13
13 3 1 1
3 1 1 20 2.60 2454K/
3 1 1 20 2.60 2454/900
3 1 1 13
cm molecule s 2.37 10
2.37 10 cm molecule s experimental
cmmolecule s 6.9 10 e
cmmolecule s 6.9 10 900 e
cmmolecule s 2.17 10
2.17 10
T
k
k
k T
k
k
k
=
=
=
=
=
=
13 3 1 1
cmmolecule s theoretical

The theoretical value is slightly smaller than the experimental value. It is possible to performa statistical analysis in order to determine
the significance of this difference.

9-102
9.34. The activation energy for the reaction:
H +CH4 H2 +CH3
has been measured to be 49.8 kJ mol
1
. Some estimates of enthalpies of formation, fH, are:
H 218.0 kJ mol
1

CH4 74.8 kJ mol
1

CH3 139.5 kJ mol
1

Estimate a value for the activation energy of the reverse reaction.
Solution:
Given: see above
Required: ( ) reverse reaction
a
E
( )
4 2 3
1
H CH H CH
kJ mol 218 74.8 139.5
f
H

+ +

Let us begin by determining the standard enthalpy for the reaction.
( ) ( )
( ) ( ) ( )
( )
3 4
1
1
products reactants
CH CH H
139.5 74.8 218 kJ mol
3.7 kJ mol
f f
f f f
H H H
H H H H
H
H
=
( = +

= + (

=

FromFigure 9.11, we can see that E1 E1 =U (Eq. 9.70). In this particular instance it is possible to say that
A A
E E H = . Since we
have been given the value for the activation energy for the forward reaction, we can use this expression to determine the activation energy
for the reverse reaction.
Rearrange the above to obtain,
9-103
( )
49.8 3.7 kJ mol

53.5 kJ mol
A A
A A
A
A
E E H
E E H
E
E
=
=
= (

=

9-104
*9.35. By a treatment similar to that given for relaxation methods for the case A = Z, derive the rate equations for analyzing the reaction
A +B = Z by carrying out the steps below.
a. Show that at equilibrium, k1aebe =k1ze, where the subscript e indicates equilibriumconcentrations.
b. Show that
1 1
( )( ) ( )
e e e
dx
k a x b x k z x
dt
= + , where x represents a change fromequilibrium.
c. Show that for small x,
1 1
[ ( ) ]
e e
dx
k a b k x
dt
= + + . [Hint: Use the result of part (a).]
d. The displacement fromequilibriumx always follows the first-order process x =x0 exp(t/t*), where t* is the relaxation time.
Show that dx/dt =x/t*.
e. Comparing the results of parts (c) and (d), show that
1 1
1
2
*
e
k a k
t
= + if ae =be.
f. For the case ae =be, show that
1 1 1
1
2
*
e
k k z k
t
= + . [Hint: Use the result of part (e) and the fact that
1
1
.
e
e e
z k
k a b
= ]
Solution:
1
1
0 0
0 0
A B Z
0

k
k
a b
a x b x x

a) First write out the rate law with respect to the rate of consumption of substances A and B.
| || | | |
1 1
A B Z
dx
k k
dt

= and at a time t, we obtain:
( )( )
1 0 0 1
dx
k a x b x k x
dt

= however, at equilibrium,
9-105
( )( )
0 0
1 0 0 1
0 0
1 0 0 1
0 0
1 1
0 and , ,
2 2
0
2 2
2 2
e e
e
e
a b dx
x z
dt
dx
k a x b x k x
dt
a b
k a b k z
a b
k k z
= =
=
| || |
=
| |
\ .\ .
=

Let
0 0
and
2 2
e e
a b
a b = = to simplify this expression further
1 1 e e e
k a b k z
=
b) Since Z is formed as A and B are consumed, for a change in ae and be by an amount x, we obtain the following expression:
( )
( )( ) ( )
1 1
e
e e e
d z x dx
k a x b x k z x
dt dt

+
= = +
c) Show that for small x,
1 1
[ ( ) ]
e e
dx
k a b k x
dt
= + + .
We can multiply out the expression frompart B to obtain,
( )( ) ( )
( ) ( )
( ) ( ) ( )
1 1
2
1 1
2
1 1
e e e
e e e e e
e e e e e
dx
k a x b x k z x
dt
dx
k a b a x b x x k z x
dt
dx
k a b a b x x k z x
dt
= +
= + +
= + + +

Since we are working under the assumption that x is small, we are able to drop a termfromthis equation.
9-106
( )
2
1
small
e e e e
dx
x k a b a b x x
dt
= + +
( )
( )
( ) ( ) ( )
1
1 1
e
e e e e e
k z x
dx
k a b a b x k z x
dt
+
= + +

Using the results frompart A we find that,
( )
( )
1 1 1 1
1 1
1 1
therefore,
e e e e e
e e e
e e e e
dx
k a b k a b x k z k x
dt
k a b k z
dx
k a b x k a b
dt

= +
=
= +
1 1 e e
k x k a b
+
( )
1 1 e e
dx
k a b k x
dt

= + + (

d) Show that dx/dt =x/t*.
Since
0
exp
t
x x
t
| |
=
|
\ .
we can differentiate both sides to obtain
dx x
dt t
= .

e) When comparing this result to that found in part C, we observe that,
( )
1 1 e e
k a b k x
+ + (

x
=
( )
1 1
1
e e
t
k a b k
t

= + +

Let us assume for simplicity sake that
e e
b a = .
9-107
1 1
1
2
e
k a k
t

= +
f) Show that
1 1 1
1
2
*
e
k k z k
t
= + .
For the equilibriumconstant, we are told that
1
1
.
e
e e
z k
k a b
= We will use this fact in addition to the result obtained in part e) in order to
prove the above statement.
1
1
1
2
1
2
2 1 1 1
1 2
1 1 1 1
but when ,
and
e
e
e
e
e
e e
e e
e
e e e e
e
z k
K b a
k a b
z k
K
k a
a
z z k z k z k
a a k
k k k k a
= = =
= =
= = = =

Substituting this into the expression generated in the previous section,
1 1
1
1
1
1
1
1 1
1
1 1 1
1
2
1
2
1
2
e e
e
e
e
z k z k
k
z k
t k
k
z k
k k
t k
k k z k
t

= +
= +
= +


9-108
9.36. A reaction of the type A +B = Z has been studied by relaxation methods. Some of the available data relating equilibrium
concentrations of the product to the relaxation times are given below.
ze/M 0.001 0.002 0.005 0.010 0.025 0.05 0.10
t*/ms 4.08 3.74 2.63 1.84 1.31 0.88 0.674

Determine k1, k1, and K =k1/k1.
Solution:
Given: ze/M and t*/ms given above
Required: k1, k1, K =k1/k1
Recall fromthe previous problem,
1
1
1
2
1
2
2 1 1 1 1
1 2
1 1 1 1
but when ,
and
e
e
e
e
e
e e
e e
e
e e e e
e
z k
K b a
k a b
z k
K
k a
a
z k z k z k z k
a a k
k k k k a
= = =
= =
= = = =

1 1
1 2
1
1 1 1
1
2
1
2
e
e e
e
z k z k
k
t a k
k k z k
t

= +
= +

9-109
Fromthe above expression, we can see that the plot of
1
vs.
e
z
t
will generate a straight line.

ze t* (s) 1/t* (s
-1
) sqrt(ze)
0.001 4.08E-03 2.4510E+02 0.03162
0.002 3.74E-03 2.6738E+02 0.04472
0.005 2.63E-03 3.8023E+02 0.07071
0.010 1.84E-03 5.4348E+02 0.10000
0.025 1.31E-03 7.6336E+02 0.15811
0.050 8.80E-04 1.1364E+03 0.22361
0.100 6.74E-04 1.4837E+03 0.31623

It is possible to performa linear regression on the data above in order to generate the equation for this line or one may use Microsoft
Excels trendline option which will display the equation of the line on the chart.
9-110
Fromthe line equation, it can be observed that the y-intercept is equal to the rate constant for the reverse reaction (k-1).
1
1
81.3 s k

=
Linear Regression Statistics
m 4497.93 81.29022158 b
Sm 122.255 20.3000768 Sb
R
2
0.99632 31.27065583 Sy
F 1353.59 5 DF

Fromthe linear regression statistics, we find the that the rate constant for the forward reaction is equal to the regression error (third box
fromthe top in the second column).
1 1
1
32.3 M s k

=

Therefore,
1 1
1
1
32.3 M s k
K
k

= =
1
81.3 s
1
0.385 M K

=

9-111
9.37. The equilibriumH2O = H
+OH has a relaxation time of about 40 s at 25 C. Find the values of the forward and reverse rate
constants. Kw =[H
+
][OH
] =10
14
.
(Hint: For this case, using steps similar to those of Problem9.25, it can be shown that
+
1 1
1
([H ] [OH ] )
*
e e
k k
t
= + + .)
Solution:
Given: see above
Required:
1 1
, k k

Let us begin by writing down the rate of consumption of water for this reaction.
| |
| |
2
1 2 1
H O
H O H OH
d
k k
dt
+
( ( =

Fromthe equilibriumcondition we may write,
| |
| |
| |
| |
1 2 1
1 2 1
1
1 2
14
w
w
2
H O H OH 0
H O H OH
H OH
H O
H OH 10 therefore,
H O
e e e
e e e
e e
e
e e
e
k k
k k
k
K
k
K
K
K
+
+
( ( =

( ( =

( (

= =
( ( = =

=

For 1 L of pure water,
1000 g
,
n m
C n
V M
= = =
18.0152 g
| |
1
2
55.5087 mol
mol
55.5087 mol
H O 55.51 M
1 L
e
=
= =

9-112
| |
14 2
w
2
10 M
H O
e
K
K
= =
55.51 M
16
1.801 52 10 M
=
Since
1 1
k Kk
= , then the equation that relates the relaxation time to the concentration can be written in the following manner:
+
1 1
1
([H ] [OH ] )
*
e e
Kk k
t

= + +
Factor to obtain,
+
1
1
([H ] [OH ] )
*
e e
k K
t

( = + +

Using the fact that,
w
H OH
e e
K
+
( ( = =

we can further simplify to get,
1 w
1
2
*
k K K
t

(
= +

This expression will enable us to solve for the rate constant belonging to the reverse reaction.
1 w
1
w
1
6 16 14 2
1
2
*
1
* 2
1
40 10 s 1.801 52 10 M 2 10 M
k K K
t
k
t K K
k

(
= +

=
(
+

=
+
11 1 1
1
1.25 10 M s k

(
(

=

9-113
1
1
16
1 1
1.801 52 10 M
k
K
k
k Kk
=
= =
( )
11 1
1.25 10 M
( )
1
5 1
1
s
2.25 10 s k

=

Formatted: Space After: 6 pt, Don't
adjust space between Latin and Asian
text
9-114
9.38. Two reactions of the same order have identical activation energies and their entropies of activation differ by 50 J mol
1
. Calculate
the ratio of their rate constants at any temperature.
Solution:
Given:
1 1
1 2 2 1
, 50 J K mol
a a a a
E E S S = = +
Required:
1
2
at any temperature
k
k

Using the Arrhenius equation,
/
e
a
E RT
k A

= we can formulate an expression which will enable us to determine the ratio of the rate constants
at any temperature. For simplicity, we will allow the temperature to be 273.15 K.
o
2 B
o
2 B 1
1
o
2 B 2
2
2 B
1
2
e exp exp
e exp exp
e exp exp
e
a
a
a
E k T S
k
h R RT
E k T S
k
h R RT
E k T S
k
h R RT
k T
h k
k
| | | | | |
=
| | |
\ . \ . \ .
| | | | | |
=
| | |
\ . \ . \ .
| | | | | |
=
| | |
\ . \ . \ .
| |
|
\ .
=
o
1
exp exp
a
E S
R RT
| | | |
| |
\ . \ .
2 B
e
k T
h
| |
|
\ .
o
2
exp exp
a
E S
R RT
| | | |
| |
\ . \ .
o o
1 1 2
2
1 1
1
2
exp
50 J K mol
exp
k S S
k R
k
k

| |
=
|
\ .
=
1 1

8.3145 J K mol

3 1
2
2.445 10
k
k
| |
|
|
\ .
=

9-115
9-116
9.39. The gas-phase reaction:
H2 +I2 2HI
is second order. Its rate constant at 400 C is 2.34 10
2
dm
3
mol
1
s
1
, and its activation energy is 150 kJ mol
1
. Calculate
H,
S, and
G at 400 C, and the preexponential factor.

Solution:
Given: second order:
2 3 1 1 1
400 C, 2.34 10 dm mol s , 150 kJ mol
a
T k E = = =
Required:
H,
S,
G, A
It is easiest to determine the pre-exponential factor by using the given information in conjunction with the Arrhenius equation.
( )
/
2 3 1 1
e
ln ln
ln ln
150 000 J
ln ln 2.34 10 dm mol s
a
E RT
a
a
k A
E
k A
RT
E
A k
RT
A
=
=
= +
= +
1
mol
8.3145 J
1
K
1
mol
( )
673.15 K
( )
3 1 1
3 1 1
23.045 504 dm mol s
10 3 1 1
ln 23.045 504 dm mol s
e
1.02 10 dm mol s
A
A
A
(

( =

=
=

According to Eq. 9.100,
2
a
E H RT = +
Knowing the value for the activation energy, we can rearrange this expression in order to solve for
H .
9-117
1 1
2
150 000 J mol 2 8.3145 J K
a
H E RT
H
=
=
1
mol 673.15 K
( )
1
1
138 806.1887 J mol
138.8 kJ mol
H
H
=
=

FromEq. 9.100, it follows that the rate constant may be written as,
/ 2 / B
e e e
a
E RT S R
k T
k
h
| |
=
|
\ .
(Eq. 9.101)
This can be rearranged in order to solve for
S. This procedure yields,

9-118
1
/ 2 / B
2 / B
/
2 3 1 1
150 000 J mol
e e e
e e
e
2.34 10 dm mol s
e
a
a
E RT S R
S R
E RT
k T
k
h
k T k
h
| |
=
|
\ .
| |
=
|
\ .
( )
1 1
/ 8.3145 J K mol

( )
673.15 K ( )
23
2
1.381 10 J
e

=
1
K
673.15 K
( )
34
6.626 10 J
( )
/
10 3 1 1 1 /
10 3 1 1
/
e
s
1.019 847 10 dm mol s 1.036 676 s e
1.019 847 10 dm mol s
e
S R
S R
S R

| |
|
|
\ .
=
=
1
1.036 676 s
10 3 1 1
1.019 847 10 dm mol s
ln
S
R

=
1
1.036 676 s
1 1
1 1
9.226 707
9.226 707 8.3145 J K mol
76.72 J K mol
S
R
S
S

| |
|
|
\ .

=
=
=
Recall fromChapter 3 that

G H T S = therefore,
1
139 000 J mol 673.15 K G =
( )
1
76.72 J K
( )
1
1
mol
190 641 J mol
190.6 kJ mol
G
G
=
=

9-119
9.40. A substance decomposes according to first-order kinetics; the rate constants at various temperatures are as follows:
1

15.0 4.18 10
6

20.0 7.62 10
6

25.0 1.37 10
5

30.0 2.41 10
5

37.0 5.15 10
5

Calculate the activation energy. Calculate also, at 25 C, the enthalpy of activation, the Gibbs energy of activation, the preexponential
factor, and the entropy of activation.
Solution:
Given: see above
Required:

, , , , at 25 C
a
E H S G A T =
Since we are dealing with a substance that decomposes according to 1
st
order kinetics, we may use the method of plotting lnk versus 1/T in
order to generate a straight line curve.
T (K) k (s
-1
) 10
3
/T (K
-1
) ln(k)
288.15 4.18E-06 3.470415 -12.3852
293.15 7.62E-06 3.411223 -11.7847
298.15 1.37E-05 3.354016 -11.1981
303.15 2.41E-05 3.298697 -10.6333
310.15 5.15E-05 3.224246 -9.87393
9-120

A linear regression may be performed in order to generate the equation for the line.
m -10.2071 23.03635974 b
Sm 0.008403 0.028173779 Sb
R
2
0.999998 0.001609684 Sy
F 1475487 3 DF

The slope is therefore, m=-10.2071. Recall that fromthe Arrhenius equation, we are able to determine the activation energy once we
know the slope.
9-121
3
exp
ln ln
m
m 10.2071 10 K
a
a
a
a
E
k A
RT
E
k A
RT
E
R
E R
| |
=
|
\ .
=
=
= =
1
8.3145 J K
1
1
1
mol
84 866.933 J mol
84.9 kJ mol
a
a
E
E
=
=

We will use the same methods employed in the previous problemto solve for the remaining variables.
a
E H RT = + (Eq. 9.95)
1 1
84 867 J mol 8.3145 J K
a
H E RT
H

=
=
1
mol 298.15 K
( )
1
1
82 388.03 J mol
82.4 kJ mol
H
H
=
=

FromEq. 9.87 we know that,
B
exp
k T G
k
h RT
| | | |
=
| |
\ . \ .

Rearrange to obtain,
9-122
B
exp
k G
k T RT
h
| |
=
|
| |
\ .
|
\ .

5 1
1.37 10 s
exp
G
RT

| |
=
|
\ .
23
1.381 10 J
1
K
( )
298.15 K
( )
34
6.626 10 J
s
( )
18
18
1
exp 2.204 670 10
ln 2.204 670 10
8.3145 J K
G
RT
G
RT
G
| |
=
|
\ .

=
=
( )
1
mol 298.15 K
( ) ( )
18
1
1
ln 2.204 670 10
100 785 J mol
100.8 kJ mol
G
G
=
=

G H T S = can be rearranged to obtain,

1 1
1 1
82 388 J mol 100 785 J mol
298.15 K
61.7 J K mol
T S H G
H G
S
T
S

=

= =
=

For unimolecular gas reactions, the pre-exponential factor is given by Eq. 9.98.
9-123
( )
( )( )
B
23
34
12 4
10 1
e exp
1.381 10 313.15 61.7
e exp
6.626 10 8.3145
e 6.526 715 10 5.97 249 10
1.01 10 s
k T S
A
h R
A
A
A
| | | |
=
| |
\ . \ .
| | | |
=
| |
\ .
\ .
=
=

9-124
9.41. The following data have been obtained for the hydrolysis of adenosine triphosphate, catalyzed by hydrogen ions:
1

39.9 4.67 10
6

43.8 7.22 10
6

47.1 10.0 10
6

50.2 13.9 10
6

Calculate, at 40 C, the Gibbs energy of activation, the energy of activation, the enthalpy of activation, the preexponential factor, and the
entropy of activation.
Solution:
Given: see above
Required:

, , , , at 40 C
a
E H S G A T =
T (K) k (s
-1
) 10
3
/T (K
-1
) ln(k)
313.05 4.67E-06 3.194378
-
12.2744
316.95 7.22E-06 3.155072
-
11.8387
320.25 1.00E-05 3.12256
-
11.5129
323.35 1.39E-05 3.092624
-
11.1836

9-125

m -10.6571 21.77330432 b
Sm 0.14652 0.460276149 Sb
R
2
0.999622 0.011088537 Sy
F 5290.36 2 DF
9-126
3
exp
ln ln
m
m 10.6571 10 K
a
a
a
a
E
k A
RT
E
k A
RT
E
R
E R
| |
=
|
\ .
=
=
= =
1
8.3145 J K
1
1
1
mol
88 608.45 795 J mol
88.6 kJ mol
a
a
E
E
=
=

( )
1 1
Eq. 9.95
88 608 J mol 8.3145 J K
a
a
E H RT
H E RT
H

= +
=
=
1
mol 313.15 K
( )

1
1
86 003 J mol
86.0 kJ mol
H
H
=
=

FromEq. 9.87 we know that,
B
exp
k T G
k
h RT
| | | |
=
| |
\ . \ .

Rearrange to obtain,
B
exp
k G
k T RT
h
| |
=
|
| |
\ .
|
\ .

We will estimate the rate constant at 40 C by the rate constant given at 313.05 K.
9-127
6 1
4.67 10 s
exp
G
RT

| |
=
|
\ .
23
1.381 10 J
1
K
( )
313.15 K
( )
34
6.626 10 J
19
exp 7.155 207 10
G
RT
| |
=
|
\ .

( )
16
1
ln 7.155 207 10
8.3145 J K
G
RT
G

=
=
( )
1
mol 313.15 K
( ) ( )
16
1
1
ln 7.155 207 10
108 785 J mol
108.8 kJ mol
G
G
=
=


1 1
1 1
86 003 J mol 108 785 J mol
313.15 K
72.751 J K mol
T S H G
H G
S
T
S

=

= =
=

9-128
( )
( )( )
B
23
34
12 4
9 1
e exp
1.381 10 313.15 72.751
e exp
6.626 10 8.3145
e 6.526 715 10 1.584 780 021 10
2.81 10 s
k T S
A
h R
A
A
A
| | | |
=
| |
\ . \ .
| | | |
=
| |
\ .
\ .
=
=

9-129
9.42. The half-life of the thermal denaturation of hemoglobin, a first-order process, has been found to be 3460 s at 60 C and 530 s at 65
C. Calculate the enthalpy of activation and entropy of activation at 60 C, assuming the Arrhenius equation to apply.
Solution:
Given: first order: ( ) ( )
1/2 1/2
60 C 3460 s, 65 C 530 s t t = =
Required:

, at 60 C H S T =
Since this is a 1
st
order process, we know that
1/2
ln2
t
k
= . Let us determine the values of the rate constant at 60 C and 65 C.
( )
( )
( )
( )
( )
( )
1/2
4 1
1/2
3 1
ln2 0.693 147
60 C
60 C 3460 s
60 C 2.003 316 10 s
ln2 0.693 147
65 C
65 C 530 s
65 C 1.307 825 10 s
k
t
k
k
t
k

= =
=
= =
=

Taking the inverse of both temperatures will enable us to generate a straight line plot. As previously seen, the slope of this curve allows us
to calculate the activation energy.
T (K) 1/T (K
-1
) k1 (s
-1
) k2 (s
-1
) ln(k1) ln(k2) ln(k2/k1)
333.15 0.003002 2.00E-04 1.31E-03 -8.51554 -6.63939 1.876147
338.15 0.002957

9-130

( )
2 1
3 3 1
2 1
ln ln rise 1.876 147
m
run 1/ 1/ 2.957 10 3.002 10 K
m 42 271 K
42 271 K
a
a
k k
T T
E
R
E

= = =

= =
=
( )
1
8.3145 J K
( )
1
1
1
mol
351 444 J mol
351.4 kJ mol
a
a
E
E
=
=

a
E H RT = + (Eq. 9.95)
1 1
351 444 J mol 8.3145 J K
a
H E RT
H

=
=
1
mol 333.15 K
( )
1
1
348 674 J mol
348.7 kJ mol
H
H
=
=

9-131

B
B
4 1
exp exp
2.003 316 10 s
exp
k T G k G
k
k T h RT RT
h
G
RT

| | | | | |
= =
| | |
| | \ . \ . \ .
|
\ .
| |
=
|
\ .
23
1.381 10 J
1
K
( )
333.15 K
( )
34
6.626 10 J
s

( )
17
17
1
exp 2.885 143 10
ln 2.885 143 10
8.3145 J K
G
RT
G
RT
G
| |
=
|
\ .

=
=
( )
1
mol 333.15 K
( ) ( )
17
1
ln 2.885 143 10
105 493 J mol G
=


1 1
1 1
348 674 J mol 105 493 J mol
333.15 K
729.95 J K mol
T S H G
H G
S
T
S

=

= =
=

9-132
*9.43. a. Using Eq. 9.73, calculate the collision density for 6.022 10
23
molecules of hydrogen iodide present in a volume 1 m
3
at 300 K.
Take dAA =0.35 nm.
b. If the activation energy for the decomposition of HI is 184 kJ mol
1
, what rate constant does kinetic theory predict at 300 C? To
what entropy of activation does this result correspond?
Solution:
Given: Eq. 73, 6.022 10
23
molecules of HI, V =1 m
3
, T =300 K, dAA =0.35 nm
Ea =184 kJ mol
1
, T =300 C
Required:
AA
, Z S
Eq. 9.73 defines the collision density,
A
2 2 B
AA
Z 2
k T
d N
m
=
a) First we need to find the mass of hydrogen iodide.
1
A
127.904 g mol M
m
N
= =
23 1
6.022 10 mol
22
25
2.123 946 10 g
2.123 946 10 kg
m
m
=
=

Now we can simply substitute all appropriate values into Eq. 9.73 to obtain the collision density.
( ) ( )
23 1
2 2
9 23 3
AA
1.381 10 J K
Z 2 0.35 10 m 6.022 10 m

=
( )
573.15 K
( )
25
31 3 1
AA
2.123 946 10 kg
Z 3.040 10 m s
=

b) We can now use a version of Eq. 9.78 in order to determine the value of the rate constant.
9-133
( )
( )
/
AA
184 000/ 8.3145 573.15 31 3 1
14 3 1
22
Z e
3.040 10 m s e
5.179 10 m s
2.123 946 10 g
a
E RT
m
n
M
=
=
=
= =
127.904 g
1
mol
1.660 578 mol n
=

14 3 1
10 3 1
5.179 10 m s 1.660 578 mol
8.600 135 10 mol m s

=
=

According to the rate equation,
| |
| |
( )
2
10 3 1
2 2
3
10 3
HI
8.600 135 10 mol m s
HI 1 mol m
8.600 135 10 m
k
k
k
= =
=
3
1 1
3
1000 dm
mol s
1 m

7 3 1 1
8.600 135 10 dm mol s k

=

The collision frequency factor (ie. pre-exponential factor) is given by,
( )
7 3 1 1
/ 184 000/ 8.3145 573.15
10 3 1 1
8.600 135 10 dm mol s
e e
5.048 238 10 dm mol s
a
E RT
k
A
A

= =
=

In order to obtain the value for the entropy of activation we may use Eq. 9.98 but for a bimolecular molecule.
2 / B
e e
S R
k T
A
h
| |
=
|
\ .

Rearranging,
9-134
10 3 1 1
/
5.048 238 10 dm mol s
e
S R

=
23
2
1.381 10 J
e

1
K
( )
573.15 K
34
6.626 10 J
s
( ) ( )
/ 4 3 1
1 1 4
1 1
e 5.719 266 10 dm mol
8.3145 J K mol ln 5.719 266 10
62.1 J K mol
S R
S
S

| |
|
|
|
\ .
=
=
=

9-135
9.44. The rate constant for a first-order reaction is 7.40 10
9
s
1
at 25 C, and the activation energy is 112.0 kJ mol
1
. Calculate, at 25 C,
the preexponential factor A, the enthalpy of activation
G, and the entropy of activation
S.
Solution:
Given: first order:
9 1 1
7.40 10 s , 25 C, 112.0 kJ mol
a
k T E = = =
Required:

, , , at 25 C H S G A T =
Given the rate constant, we may first solve for the Gibbs energy of activation using Eq. 9.87.
/ B
e
G RT
k T
k
h
| |
=
|
\ .

9 1
/
7.40 10 s
e
G RT

=
23
1.381 10 J
1
K
( )
298.15 K
( )
34
6.626 10 J
s
( )
/ 21
21
1
e 1.190 843 10
ln 1.190 843 10
8.3145 J K
G RT
G
RT
G

=

=
=
( )
1
mol 298.15 K
( ) ( )
21
1
1
ln 1.190 843 10
119 436 J mol
119.4 kJ mol
G
G
=
=

Given the activation energy, we may first solve for the enthalpy of activation using Eq. 9.95.
a
E H RT = + (Eq. 9.95)
9-136
1 1
112 000 J mol 8.3145 J K
a
H E RT
H

=
=
1
mol 298.15 K
( )
1
1
109 521 J mol
109.5 kJ mol
H
H
=
=


1 1
1 1
109 521 J mol 119 436 J mol
298.15 K
33.25 J K mol
T S H G
H G
S
T
S

=

= =
=

( )
( ) ( )
( )( )
/ B
23
33.254 966 / 8.3145
34
12
11 1
e e
1.381 10 298.15
e e
6.626 10
e 6.214 083 10 0.018 322
3.09 10 s
S R
k T
A
h
A
A
A

| |
=
|
\ .
| |
=
|
\ .
=
=

9-137
9.45. The rate constant for a second-order reaction in solution is 3.95 10
4
dm
3
mol
1
s
1
at 25 C, and the activation energy is 120.0 kJ
mol
1
. Calculate, at 25 C, the preexponential factor A, the enthalpy of activation
G, and the
entropy of activation
S.
Solution:
Given: first order:
4 3 1 1 1
3.95 10 dm mol s , 25 C, 120.0 kJ mol
a
k T E = = =
Required:

, , , at 25 C H S G A T =
Given the rate constant, we may first solve for the Gibbs energy of activation using Eq. 9.87.
/ B
e
G RT
k T
k
h
| |
=
|
\ .

4 3 1 1
/
3.95 10 dm mol s
e
G RT

=
23
1.381 10 J
1
K
( )
298.15 K
( )
34
6.626 10 J
s
( )
/ 17
17
1
e 6.356 529 10
ln 6.356 529 10
8.3145 J K
G RT
G
RT
G

=

=
=
( )
1
mol 298.15 K
( ) ( )
17
1
1
ln 6.356 529 10
92 452 J mol
92.45 kJ mol
G
G
=
=

Given the activation energy, we may first solve for the enthalpy of activation using Eq. 9.95.
a
E H RT = + (Eq. 9.95)
9-138
1 1
120 000 J mol 8.3145 J K
a
H E RT
H

=
=
1
mol 298.15 K
( )
1
1
117 521 J mol
117.5 kJ mol
H
H
=
=


1 1
117 521 J mol 92 452 J mol

298.15 K
T S H G
H G
S
T

=

= =

1 1
84.08 J K mol S

=
( )
( ) ( )
( )( )
/ B
23
84.08 / 8.3145
34
12
17 3 1 1
e e
1.381 10 298.15
e e
6.626 10
e 6.214 083 10 24 654
4.16 10 dm mol s
S R
k T
A
h
A
A
A

| |
=
|
\ .
| |
=
|
\ .
=
=

9-139
9.46. The rate constant k for the reaction between persulfate ions and iodide ions varies with ionic strength I as follows:
I/10
3
mol dm
3
2.45 3.65 4.45 6.45 8.45 12.4
k/dm
3
mol
1
s
1
1.05 1.12 1.16 1.18 1.26 1.39

Estimate the value of zAzB.
Solution:
We know that this reaction follows 2
nd
order kinetics by examining the units associated with the rate constant. Recall that information
regarding the rate law, rate constant and half life are condensed in Table 9.1.
According to the Debye-Huckel limiting law (Section 7.10) the activity coefficient of an ion is related to its valency, z and the ionic
strength, I. By Eq. 7.104,
2
10
log Bz I = (Eq. 9.121)
Introduction of the above into the rate equation (Eq. 9.120) gives,
A B
10 10 0 10
log log log k k

= + (Eq. 9.120)
( ) A B
A
10 10 0 10 A 10 B 10
2
2 2
10 10 0 A B
2
10 10 0
log log log log log
log log
log log
k k
k k B z z z z I
k k B z
= + +
(
= + +

=
B
2
z +
A
2
z
B
2
A B
2z z z + +
( )
10 10 0 A B
log log 2
I
k k Bz z I
(
(

= +

The value of B is approximately 0.51 dm
-3/2
mol
-1/2
for aqueous solutions at 25 C. Therefore,

3
10 10 0 A B
log log 1.02 / mol dm k k z z I

= + (Eq. 9.125)
I (10
3
mol dm
3
) k (dm
3
mol
1
s
1
) sqrt(I) log10(k)
9-140
2.45 1.05 0.049497 0.021189
3.65 1.12 0.060415 0.049218
4.45 1.16 0.066708 0.064458
6.45 1.18 0.080312 0.071882
8.45 1.26 0.091924 0.100371
1.24 1.39 0.111355 0.143015

m 1.850795931 -0.066937665 b
Sm 0.144547247 0.011480668 Sb
R
2
0.976182639 0.007300432 Sy
F 163.9447163 4 DF

9-141
3
10 10 0 A B
log log / mol dm k k z z I

Therefore, a plot of
3
10
log against / mol dm k I

will yield a slope that is approximately equal to
A B
z z . Fromthe regression statistics, we
see that m=1.850 796
A B
A B
1.850 795 931
1.814 505 814
1.02
1.814
z z
z z
= =

9-142
9.47. The following constants were obtained by Brnsted and Livingstone [J. Amer. Chem. Soc., 49, 435(1927)] for the reaction:
[CoBr(NH3)5]
2+
+OH
[Co(NH3)5OH]
2+
+Br

under the following conditions:

1

3 1 1
dm mol s
k

[CoBr(NH3)5]
2+
NaOH NaCl
5.0 10
4
7.95 10
4
0 1.52
5.96 10
4
1.004 10
3
0 1.45
6.00 10
4
0.696 10
3
0.005 1.23
6.00 10
4
0.696 10
3
0.020 0.97
6.00 10
4
0.691 10
3
0.030 0.91

Make an estimate of the rate constant of the reaction at zero ionic strength. Are the results consistent with zAzB =2?
Solution:
Let us begin by determining the ionic strengths of each reaction mixture. Recall that the ionic strength of a solution represents a function of
all ions present into the given solution.
B
2
B
B 1
1
2
n
I c z
=
=

where cB =molar concentration of each ion and zB =charge number of that particular ion.
9-143
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
2 4 3 4
3
2 4 4 3
3
2 4 4 3
1
1 2 5.0 10 1.0 10 2 7.95 10
2
2.295 10 M
1
2 2 5.96 10 11.92 10 2 1.004 10
2
2.79 10 M
1
3 2 6.0 10 12.0 10 2 0.696 10 0.01
2
7.496 1
I
I
I
I
I
I
( = + +

=
( = + +

=
( = + + +

=
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
3
4 4 3
3
4 4 3
3
0 M
1
4 24.0 10 12.0 10 1.392 10 0.04
2
22.50 10 M
1
5 24.0 10 12.0 10 1.392 10 0.06
2
32.50 10 M
I
I
I
I
( = + + +

=
( = + + +

=

I (10
3
mol dm
3
) k (dm
3
mol
1
s
1
) sqrt(I) log10(k)
2.30E-03 1.52 0.047906 0.181844
2.79E-03 1.45 0.052820 0.161368
7.50E-03 1.23 0.086579 0.089905
2.25E-02 0.97 0.150000 -0.013228
3.25E-02 0.91 0.180278 -0.040959

9-144


-1.683623642 0.250069168
0.122806104 0.014277339
0.984289358 0.01453188
187.9533719 3
Fromthe regression statistics, we can see that the y-intercept is equal to
10 0
log 0.250069168 k = .
We may now make an estimate of the rate constant.
0.250069168
0
0
3 1 1
0
10
1.778562651
1.78 dm mol s
k
k
k

=
=
=

Again fromthe regression statistics, the slope was given to be m=-1.683 623 642. We already know that the slope is equal to
A B
1.02z z for
an aqueous solution at 25 C. Therefore,
9-145
A B
m 1.683623642 1.02z z = =
A B
A B
1.683623642
1.650611414
1.02
1.65
z z
z z
= =
=

When rounded to a single significant figure,
A B
2 z z = which is in fact consistent with the statement given in the question.

9-146
9.48. Suppose that the rates of ionic reactions in solution were proportional to the activity rather than the concentration of activated
complexes. Derive an equation relating the logarithmof the rate constant to the ionic strength and the charge numbers of the ions
and contrast it with Eq. 9.124. Can the results in Figure 9.22 be reconciled with the equation you have derived?
Solution:
Let the following reaction occur as follows,
A B X products +
The basis of the ionic strength treatment is that the rate of a reaction is proportional to the concentration of the activated complexes,
X and
NOT to their activity. The rate equation is thus,
X k ( =

The equilibriumbetween the activated complexes and the reactants A and B may then be expressed as,
| || |
A B A B
X
A B
a
K
a b

(

= = (Eq. 9.118)
Remember that a and b are the activities and represents the activity coefficient. We will now introduce Eq. 9.118 into a modified rate
equation (fromthe one given above). Suppose that,
| || |
| || |

A B
A B
X
X A B
A B
k
K
k K

( =

( =

=
| |
|
|
\ .
| || |
A B
A B kK =

Let
| || |
0 A B
and A B kK k k kK = =
9-147
Taking the logarithmof each part of the equation, we obtain,
10 10 0 10 A B
log log log k k = +
Using the fact that
2
10
log Bz I = we can make a substitution to get,
2 2
10 10 0 A B
log log k k B z z I ( = +

In this particular situation, plotting
10
log against k I will always yield a line with a negative slope. This conclusion is inconsistent with
the results presented in Figure 9.22.

9-148
9.49. When the subatomic species muonium(Mu) was first discovered in 1960, it was not known whether it bore an electric charge. The
answer was provided by a kinetic study of the ionic strength effect on the reaction Mu +Cu
2+
in aqueous solution. The following
rate constants were measured at two ionic strengths:
I =0 M k =6.50 10
9
dm
3
mol
1
s
1

I =0.9 M k =6.35 10
9
dm
3
mol
1
s
1

Suppose that muoniumhad a single negative charge; what would k be expected to be at an ionic strength of 0.9 M? What do you deduce
about the actual charge on muonium?
Solution:
If there were a single negative charge on the muoniumion, the slope of the plot of
10
log against k I would yield a slope of approximately -
2. Thus,
A B
2 z z = . According to Eq. 9.124,
10 10 0 A B
log log 2 k k Bz z I = + which can be rearranged to obtain,
( ) ( )
10 10 0 A B
1/2
10
0
6.12 7
0
log log 2
log 1.02 2 0.9 6.12
10 7.59 10 ????
k k Bz z I
k
k
k
k

=
| |
= =
|
\ .
| |
= =
|
\ .

I have no clue what the previous author did here. There is absolutely no explanation as to where he got his numbers from. I cannot finish
this problem.

9-149

9-150
9.50. The rate constants of a second-order reaction in aqueous solution at 25 C had the following values at two ionic strengths:
I/mol dm
3
k/dm
3
mol
1
s
1

2.5 10
3
1.40 10
3

2.5 10
2
2.35 10
3

Make an estimate of the value of zAzB, the product of the charge numbers.
Solution:
Given: see above
Required: estimate zAzB
Let us plot
10
log against k I .
I (10
3
mol dm
3
) k (dm
3
mol
1
s
1
) sqrt(I) log10(k)
2.50E-03 1.40E-03 0.05000 -2.8539
2.50E-02 2.35E-03 0.15811 -2.6289

9-151
m 2.080582256 -2.957901077 b
Sm 0 0 Sb
R
2
1 0 Sy
F NA 0 DF

The slope of the plot above is equal to m=2.080 582 256. This means that,

A B
A B
A B
2.080582256 1.02
2.080582256
1.02
2.04
z z
z z
z z
=
=
=

An approximation to one significant figure yields,
A B
2 z z .

9-152
9.51. A reaction of the type:
A
+
+B
2
products
was found at 25 C to have a rate constant of 2.8 10
4
dm
3
mol
1
s
1
at an ionic strength of 1.0 10
3
M. Assume the Debye-Hckel
limiting law to apply and estimate the rate constant at zero ionic strength.
Solution:
Given:
4 3 1 1 3
2.8 10 dm mol s , 25 C, 1.0 10 M k T I

= = =
Required: ( )
0 0
at k I k
The Debye-Hckel limiting law states that,
10 10 0 A B
log log 2 k k Bz z I = +
This can be rearranged to solve for k0 upon substitution of the appropriate values.
( ) ( )
10 10 0 A B
10 0 10 A B
4 3 1 1 3
10 0 10
10 0
10 0
3.488 332
0
4 3 1 1
0
log log 2
log log 2
log log 2.8 10 dm mol s 1.02 2 1.0 10 M
log 3.552 842 0.064 510
log 3.488 332
10
3.25 10 dm mol s
k k Bz z I
k k Bz z I
k
k
k
k
k
= +
=
=
= +
=
=
=


9-153
9.52. The rate of a reaction at 300 K is doubled when the pressure is increased from1 bar to 2000 bar. Calculate
V, assuming it to be
independent of pressure.
Solution:
Given:
0
300 K, 1 bar, 2000 bar
f
T P P = = =
Required:
V (pressure independent)
According to Eq. 9.129 we know that,
0
ln ln
V
k k P
RT

= .
We are told that the rate of the reaction increases 2-fold when the pressure is increased from1 bar to 2000 bar. This would mean that,
1 0
2
2
1 0
ln ln2 ln
ln2
k
k
k V
P
k RT
V
P
RT
=
=

= = =

=

Rearrange this expression to isolate
V ,
( )
ln2 RT
V
P
=
Substitution yields,
9-154
1
0.693147 8.3145 J K
V
=
( )
1
mol 300 K
( )
( )
1 1
5 5 3
2000 1 bar
0.864 908 J bar mol
1 bar 10 Pa, 1 atm 1.013 25 10 Pa, 1 atmdm 101.325 J
0.864 908 J
V
V

=
= = =
=
1
bar
1
1 bar
mol
5
10 Pa
5
1.013 25 10 Pa
1 atm
1 atm
3
dm
101.325 J
3 3 1
8.649081 10 dm mol V

=

9-155
3 3
3 3
1dm 0.001 m
8.649081 10 dm V

=
=
3
1
3
0.001 m
mol
1 dm
6 3 1
8.65 10 m mol V

=


9-156
9.53. The following results were obtained for the solvolysis of benzyl chloride in an acetone-water solution at 25 C:
P/10
2
kPa 1.00 345 689 1033
k/10
6
s
1
7.18 9.58 12.2 15.8

Make an appropriate plot and estimate
V.
Solution:
Given: se above
Required: plot and estimate
V
P/10
2
kPa k/10
6
s
1
lnk
1.00
7.18 -11.844
3.45 9.58 -11.556
6.89 1.22 -11.314
10.3 1.58 -11.056

9-157

m 7.58108E-06 -11.83434645 b
Sm 1.89127E-07 0.012186716 Sb
R
2
0.998756818 0.014547781 Sy
F 1606.774843 2 DF
0
ln ln
V
k k P
RT

= . This means that a plot of lnk against P will yield a slope that is equal to
V
RT

. This information will allow us to determine the value of
V .
9-158
6 1 9 1
9 1 1
m 7.58108 10 kPa 7.58108 10 Pa
7.58108 10 Pa 8.3145 J K
V
RT
V

= = =
=
1
mol 298.15 K
( )
5 1 1
1 3
5 3 1
1.879 10 J Pa mol
1 J Pa 1 m therefore,
1.88 10 m mol
V
V

=
=
=

9-159
9.54. The fading of bromphenol blue in alkaline solution is a second-order reaction between hydroxide ions and the quinoid formof the
dye:
quinoid form(blue) +OH

carbinol form(colorless)
The following results show the variation of the second-order rate constant k with the hydrostatic pressure P at 25 C:
P/10
4
kPa 101.3 2.76 5.51 8.27 11.02
k/10
4
M
1
s
1
9.30 11.13 13.1 15.3 17.9

Estimate
V.
Solution:
Given: second order: P/10
4
kPa and k/10
4
M
1
s
1
above
Required:
V
We will use the same method as we did in the previous problem. We should first begin by adjusting the units to simplify our results.
1
3 3 3
1
1M 1mol L
1 L 1 m, 1 m 1000 dm
1M 1mol L
=
= =
=
1 L
3
1 m
3
1 m
( )
( ) ( )
3
3 3
1
3 1
1 1
4 3 1 4 1 4 3 1 1
1000 dm
1M 1.0 10 mol dm
1M 1000 dm mol
10 M 10000 dm mol and 10 M s 10 dm mol s

=
=
= =

The rate constant can now be expressed in the following form,
4 1 1 4 3 1 1
/10 M s /10 dm mol s k k

=
P/ kPa k/10
-4
M
1
s
1
k/dm
3
mol
-1
s
1
lnk
1013000.00 9.30E-04 9.30 2.2300
9-160
27600.00 1.11E-03 11.13 2.4096
55100.00 1.31E-03 13.10 2.5726
82700.00 1.53E-03 15.30 2.7279
110200.00 1.79E-03 17.90 2.8848


5.9127E-06 2.238955304
1.0317E-07 0.006964007
0.99908744 0.008981709
3284.45091 3
0
ln ln
V
k k P
RT

= . This means that a plot of lnk against P will yield a slope that is equal to
V
RT

. This information will allow us to determine the value of
V .
9-161
9 1
9 1 1
m 5.9127 10 Pa
5.9127 10 Pa 8.3145 J K
V
RT
V

= =
=
1
mol 298.15 K
( )
5 1 1
1 3
5 3 1
1.466 10 J Pa mol
1 J Pa 1 m therefore,
1.47 10 m mol
V
V

=
=
=

9-162
9.55. Use Figure 9.23 to make approximate estimates of the volumes of activation for the alkaline hydrolyses of methyl acetate, ethyl
acetate, and propionamide, at 25 C.
Solution:
Given: Figure 9.23, 25 C T =
Required: estimate
V in each case
FromFigure 9.23, at 10 000 lb per square inch, the values of
10
0
log
k
k
are:
Ethyl acetate: 0.105
Methyl acetate: 0.11
Propionamide: 0.20
The value of
10
0
log
k
k
when the pressure is 10 000 pounds per square inch is approximately 0.105. The slope of a plot in which natural
logarithms were used would therefore be,
0
3
0
2.303 0.105
ln
10000psi
1 psi 6.89 10 Pa therefore,
2.303 0.105
ln
10000 psi
k
k
k
k
=
=
=
3
6.89 10 Pa
1 psi
3
0
9 1
10
0
2.303 0.105
ln
10000 6.89 10 Pa
log 3.509 651 10 Pa
k
k
k
k

=

=

According to Eq. 9.129 (for ethyl acetate),
9-163
0

0
0
9 1 1
ln ln
ln ln ln since m
3.509 651 10 Pa 8.3145 J K
V
k k P
RT
V k V V
k k P P P
RT k RT RT
V

=

= = =
=
( )
1
mol 298.15 K
( )
6 1 1 1 3
6 3 1
8.69 979 10 J Pa mol since1 J Pa 1 m therefore,
8.70 10 m mol
V
V

= =
=

Similarly, for methyl acetate;
0

0
0
ln ln
ln ln ln
V
k k P
RT
V k V
k k P P
RT k RT

=

= =
9 1 1
since m
3.68 10 Pa 8.3145 J K
V
RT
V

=
=
( )
1
mol 298.15 K
( )
6 1 1 1 3
6 3 1
9.122 602 884 10 J Pa mol since1 J Pa 1 m therefore,
9.12 10 m mol
V
V

= =
=

For proprionamide the slope is;
0

0
0
ln ln
ln ln ln
V
k k P
RT
V k V
k k P P
RT k RT

=

= =
9 1 1
since m
6.685 10 Pa 8.3145 J K
V
RT
V

=
=
( )
1
mol 298.15 K
( )
5 1 1 1 3
5 3 1
1.657 190 225 10 J Pa mol since1 J Pa 1 m therefore,
1.66 10 m mol
V
V

= =
=

9-164


CHAPTER
1
1
0
0
Chemical Kinetics II.
Composite Mechanisms

Physical Chemistry
Electronic Edition


Chapter 10: Chemical Kinetics II. Composite Mechanisms Composite Mechanisms and Rate Equations
10-2
Chapter 10
Composite Mechanisms and Rate Equations
10.1. Suppose that a reaction of stoichiometry A +2B =Y +Z is believed to occur by the mechanism:

Where X is an intermediate. Write the expression for the rate of formation of Y.

Solution

10.2. Suppose that a reaction A +2B =2Y +2Z is believed to occur according to the mechanism:

Obtain an expression for the rate of formation of the product Y.

Solution

10.3. Suppose that a reaction of stoichiometry A +B =Y +Z is believed to occur according to the mechanism:

Apply the steady-state treatment and obtain an expression for the rate. To what expressions does the general rate equation reduce if;
a. The second reaction is slow, the initial equilibriumbeing established very rapidly?
b. The second reaction is very rapid compared with the first reaction in either direction?

Solution

10.4. A reaction of stoichiometry:
A +B =Y +Z
is found to be second order in A and zero order in B. Suggest a mechanismthat is consistent with this behavior.

Solution

Field Code Changed
10-3
10.5. The rate of formation of the product of a reaction is found to give a nonlinear Arrhenius plot, the line being convex to the 1/T axis
(i.e., the activation energy is higher at higher temperatures). Suggest a reason for this type of behavior.
(Hint: For this and the following problem, consider the possibility of two parallel reactions and of two consecutive reactions having
different activation energies.)

Solution

10.6. An Arrhenius plot is concave to the 1/T axis (i.e., it exhibits a lower activation energy at higher temperatures). Suggest a reason for
this type of behavior.

Solution

10.7. Nitrogen pentoxide reacts with nitric oxide in the gas phase according to the stoichiometric equation:
N2O5 +NO =3NO2
The following mechanismhas been proposed:

Assume that the steady-state treatment can be applied to NO3, and derive an equation for the rate of consumption of N2O5.

Solution

10.8. The reaction 2NO +O2 2NO2 is believed to occur by the mechanism:

Assume N2O2 to be in a steady state and derive the rate equation. Under what conditions does the rate equation reduce to second-
order kinetics in NO and first-order kinetics in O2?

Solution

*10.9. The gas-phase reaction:
Cl2 +CH4 CH3Cl +HCl
proceeds by a free-radical chain reaction in which the chain propagators are Cl and CH3 (but not H), and the chain-ending step is
2Cl Cl2. Write the mechanism, identify the initiation reaction and the chain-propagating steps, and obtain an expression for the
rate of the overall reaction.
Solution
10-4
10.10. The following mechanismhas been proposed for the thermal decomposition of pure ozone in the gas phase:

Derive the rate equation.

Solution

*10.11. A reaction occurs by the mechanism:

and the concentration of X is sufficiently small compared with the concentrations of A and B that the steady-state treatment applies.
Prove that the activation energy Ea at anytemperature is given by:
1 1 2 1 2 1
1 2
( )
a
k E E E k E
E
k k
+ +
=
+

that is, is the weighted mean of the values E1 +E2 E1, and E1, which apply, respectively, to the limiting cases of k1 k2 and k2
k1.

Solution

10.12. F. A. Lindemann [Trans. Faraday Soc., 17, 598(1922)] proposed the following mechanismfor a unimolecular gas reaction:

The species A* is an energized molecule that is present in low concentrations. Apply the steady-state treatment to A* and obtain an
expression for the rate in terms of [A], k1, k1, and k2. Show that the mechanismpredicts first-order kinetics at higher A
concentrations and second-order kinetics at lower ones.

Solution
10-5
*10.13. Certain polymerizations involve esterification reactions between COOH groups on one molecule and OH groups on another.
Suppose that the concentration of such functional groups is c and that the rate of their removal by esterification obeys the equation:
2
dc
kc
dt
=
Obtain an equation relating the time t to the fraction f of functional groups remaining and to the initial concentration c0 of functional
groups.

Solution

*10.14. Show that the mechanism:

leads to the result that the rate equation for the overall reaction is =k[H2][I2].

Solution

10.15. Apply the steady-state treatment to the following mechanism, in which Y and Z are final products and X is a labile intermediate:

Obtain an expression for the rate of formation of the product Z. What rate equations are obtained if (a) A and (b) B are present in
great excess?

Solution

Chapter 10: Chemical Kinetics II. Composite Mechanisms Photochemistry and Radiation Chemistry
10-6
Photochemistry and Radiation Chemistry
10.16. Calculate the maximumwavelength of the radiation that will bring about dissociation of a diatomic molecule having a dissociation
energy of 390.4 kJ mol
1
.

Solution

10.17. Hydrogen iodide undergoes decomposition into H2 +I 2 when irradiated with radiation having a wavelength of 207 nm. It is found
that when 1 J of energy is absorbed, 440 g of HI is decomposed. How many molecules of HI are decomposed by 1 photon of
radiation of this wavelength? Suggest a mechanismthat is consistent with this result.

Solution

10.18. A 100-watt mercury-vapor lamp emits radiation of 253.7 nmwavelength and may be assumed to operate with 100% efficiency. If all
the light emitted is absorbed by a substance that is decomposed with a quantumyield of unity, how long will it take for 0.01 mol to
be decomposed?

Solution

10.19. Suppose that the radiation emitted by the lamp in Problem10.18 is all absorbed by ethylene, which decomposes into C2H2 +H2
with a quantumyield of unity. How much ethyne will be produced per hour?

Solution

10.20. A 1000-watt mercury vapor flash lamp emits radiation of 253.7 nmwavelength, and the duration of the flash is 1 s. Suppose that
all of the radiation of a single flash is absorbed
by mercury vapor; how many atoms of excited mercury are formed?

Solution

10-7
*10.21. The photochemical reaction between chlorine and chloroformin the gas phase follows the stoichiometric equation:
CHCl3 +Cl2 =CCl4 +HCl
It is believed to occur by the mechanism:

Assume the rate of formation of Cl atoms in the initiation reaction to be 2Ia, where Ia is the intensity of light absorbed, and obtain an
expression for the overall rate in terms of Ia and [CHCl3].

Solution

*10.22. When water vapor is irradiated with a beamof high-energy electrons, various ions such as H
+
and O

appear. Calculate the
minimumenergies required for the formation of these ions, given the following thermochemical data:

Are the results you obtain consistent with the experimental appearance potentials of
19.5 eV for H
+
and 7.5 eV for O
?

Solution

10-8
10.23. The mercury-photosensitized hydrogenation of ethylene in the presence of mercury vapor is first-order with respect to ethylene and
half-order with respect to H2. Its rate is proportional to the square root of the intensity of the light absorbed. The following
mechanismhas been suggested to account for these observations:

Applying the steady-state approximation to [H] and [C2H5], verify that the mechanismindeed supports the observations. What is the
observed rate constant in terms of the rate constants of the elementary reactions?

Solution

Catalysis
10.24. The hydrolysis of a substance is specifically catalyzed by hydrogen ions, and the rate constant is given by:
k/dm
3
mol
1
s
1
=4.7 10
2
([H
+
]/mol dm
3
)
When the substance was dissolved in a 10
3
M solution of an acid HA, the rate constant was 3.2 10
5
dm
3
mol
1
s
1
. Calculate the
dissociation constant of HA.

Solution

*10.25. The following is a slightly simplified version of the mechanismproposed in 1937 by G. K. Rollefson and R. F. Faull [J. Amer.
Chem. Soc., 59, 625(1937)] to explain the iodine-catalyzed decomposition of acetaldehyde:
I 2 2I
I +CH3CHO HI +CH3CO
CH3CO CH3 +CO
CH3 +HI CH4 +I
2I I 2
Apply the steady-state treatment to I, CH3CO, and CH3 and obtain an expression for the rate.

Solution

10-9
*10.26. Suppose that a reaction is catalyzed by a series of homologous acids and that the Hammett equation (9.130) applies:
log10 ka =log10 k0 +
where is the substituent constant and is the reaction constant. Suppose that the corresponding equation for the dissociation of the
acid is:
log10 Ka =log10 K0 +'
where ' is the reaction constant for the dissociation; the substituent constants are the same in both equations. Prove that the
Brnsted equation:
a a a
k G K
=
applies. How does relate to the reaction constants and '?

Solution

10.27. The hydrolysis of ethyl acetate catalyzed by hydrochloric acid obeys the rate equation:
=k[ester][HCl]
and the reaction essentially goes to completion. At 25 C the rate constant is 2.80 10
5
dm
3
mol
1
s
1
. What is the half-life of the
reaction if [ester] =0.1 M and [HCl] =0.01 M?

Solution

10.28. The following mechanismhas been proposed for the alkaline hydrolysis of Co(NH3)5Cl
2+
:
Co(NH3)5Cl
2+
+OH
Co(NH3)4(NH2)Cl
+
+H2O
Co(NH3)4(NH2)Cl
+
Co(NH2)4(NH2)
2+
+Cl

Co(NH3)4(NH2)
2+
+H2O Co(NH3)5(OH)
2+

Assume Co(NH3)4(NH2)Cl
+
and Co(NH3)4(NH2)
2+
to be in the steady state and derive an expression for the rate of reaction.
Experimentally, the rate is proportional to [Co(NH)5Cl
2+
] [OH
]; does this fact tell us anything about the relative magnitudes of the rate
constants?

Solution

10-10
10.29. Confirmthat Eq. 10.68,
1
2
min
OH H
[H ] ( / )
w
k K k
+
+
=
follows fromEq. 10.66,
OH
0
H
[H ]
[H ]
w
k K
k k k
+
+
+
= + +

Solution

10.30. The following results have been obtained by D. B. Dahlberg and F. A. Long [J. Amer. Chem. Soc., 95, 3825(1973)] for the base-
catalyzed enolization of 3-methyl acetone.
Catalyst ClCH2COO
CH3COO

2
4
HPO
Ka/mol dm
3
1.39 10
3
1.80 10
5
6.25 10
8

k/dm
3
mol
1
s
1
1.41 10
3
1.34 10
2
0.26

Estimate the Brnsted coefficient .

Solution

10.31. Suggest a plausible mechanismfor the bromination of acetone catalyzed by hydroxide ions. As with the acid-catalyzed reaction
discussed in Section 10.9, the rate is independent of the bromine concentration.

Solution

10.32. It was found by J . Halpern and coworkers [J. Phys. Chem., 60, 1455(1956)] that the rate equation for the oxidation of molecular
hydrogen by dichromate ions
2
2 7
(Cr O ) catalyzed by Cu
2+
ions is of the form:
2 2
2
2
2
[H ][Cu ]
[H ] [Cu ]
k
k
+
+
=
+

(**Note that the rate is independent of the concentration of dichromate ions.)
Suggest a mechanismconsistent with this behavior, and apply the steady-state treatment to obtain the rate expression. Comment on
rate-controlling steps corresponding to special cases of the mechanism.
Solution

10-11
10.33. For the oxidation of molecular hydrogen by dichromate ions catalyzed by Ag
+
ions, A. H. Webster and J . Halpern [J. Phys. Chem.,
60, 280(1956)] obtained the rate equation:
2
2 2
2
2
[H ][Ag ]
[H ][Ag ]
[H ] [Ag ]
k
k
k
+
+
+
= +
+

The existence of two terms suggests that two mechanisms are occurring in parallel. Suggest the two mechanisms, applying the
steady-state treatment to obtain the second termin the rate equation.

Solution

10.34. The reaction:
Tl
+
+2Ce
4+
Tl
3+
+2Ce
3+
is catalyzed by Ag
+
ions. Under certain conditions the rate is proportional to
[Ce
4+
][Tl
+
][Ag
+
]/[Ce
3+
]
Suggest a mechanismconsistent with this behavior.

Solution

Chapter 10: Chemical Kinetics II. Composite Mechanisms Enzyme-Catalyzed Reactions
10-12
Enzyme-Catalyzed Reactions
10.35. The following rates have been obtained for an enzyme-catalyzed reaction at various substrate concentrations:
10
3
[S]/mol dm
3
Rate, /(arbitrary units)
0.4 2.41
0.6 3.33
1.0 4.78
1.5 6.17
2.0 7.41
3.0 8.70
4.0 9.52
5.0 10.5
10.0 12.5

Plot against [S], 1/ against 1/[S], and /[S] against , and fromeach plot estimate the Michaelis constant. Which plot appears to give the
most reliable value?

Solution
10.36. The following data have been obtained for the myosin-catalyzed hydrolysis of ATP, at 25 C and pH 7.0.

10
5
[ATP]/mol dm
3
10
6
/mol dm
3
s
1

7.5 0.067
12.5 0.095
20.0 0.119
32.5 0.149
62.5 0.185
155.0 0.191
320.0 0.195
10-13

Plot against [S], 1/ against 1/[S], and /[S] against , and fromeach plot calculate the Michaelis constant Km and the limiting rate V.

Solution

*10.37. The following values of V (limiting rate at high substrate concentrations) and Km have been obtained at various temperatures for the
hydrolysis of acetylcholine bromide, catalyzed by acetylcholinesterase.
T/C 10
6
V/mol dm
3
s
1
Km 10
4
/mol dm
3

20.0 1.84 4.03
25.0 1.93 3.75
30.0 2.04 3.35
35.0 2.17 3.05

a. Assuming the enzyme concentration to be 1.00 10
11
mol dm
3
, calculate the energy of activation, the enthalpy of activation, the
Gibbs energy of activation, and the entropy of activation for the breakdown of the enzyme-substrate complex at 25 C.
b. Assuming Km to be the dissociation constant k1/k1 for the enzyme-substrate complex
1
1
(ES E S),
k
k
+ determine the following
thermodynamic quantities for the formation of the enzyme-substrate complex at 25 C: G, H, S.
c. Fromthe results obtained in parts (a) and (b), sketch a Gibbs energy diagramand an enthalpy diagramfor the reaction.

Solution

10-14
*10.38. The following data relate to an enzyme reaction:
10
3
[s]/mol dm
3
10
5
V/mol dm
3
s
1

2.0 13
4.0 20
8.0 29
12.0 33
16.0 36
20.0 38

The concentration of the enzyme is 2.0 g dm
3
, and its molecular weight is 50 000. Calculate Km, the maximumrate V, and kc.

Solution

10.39. The following data have been obtained for the myosin-catalyzed hydrolysis of ATP.
Temperature/C kc 10
6
/s
1

39.9 4.67
43.8 7.22
47.1 10.0
50.2 13.9

Calculate, at 40 C, the energy of activation, the enthalpy of activation, the Gibbs energy of activation, and the entropy of activation.

Solution

10-15
*10.40. The following is a simplified version of the mechanismthat has been proposed by H. Theorell and Britton Chance for certain
enzyme reactions involving two substrates A and B.

Assume that the substrates A and B are in excess of E so that the steady-state treatment can be applied to EA and EZ, and obtain an
expression for the rate.

Solution

*10.41.When an inhibitor I is added to a single-substrate enzyme system, the mechanismis sometimes:

This is known as a competitive mechanism, since S and I compete for sites on the enzyme.
a. Assume that the substrate and inhibitor are present in great excess of the enzyme, apply the steady-state treatment, and obtain the
rate equation.
b. Obtain an expression for the degree of inhibition defined as:
0
0

where is the rate in the presence of inhibitor and 0 is the rate in its absence.

Solution

10-16
*10.42. Obtain the rate equation corresponding to the mechanism:

Assume ES and ES to be in the steady state and the substrate concentration to be much higher than the enzyme concentration.
Express the catalytic constant kc and the Michaelis constant Km in terms of k1, k1, k2, and k3.

Solution

*10.43. Enzyme-catalyzed reactions frequently follow an equation of the formof Eq. 10.85. Suppose that kc and Km show the following
temperature dependence:
kc =Ac exp(Ec/RT ) and Km =B exp(Hm /RT )
where Ac, B, Ec, and Hm are temperature-independent parameters. Explain under what conditions, with [S] held constant, the rate
may pass through a maximumas the temperature is raised.

Solution

10.44. Some enzyme reactions involving two substrates A and B occur by the following mechanism:
1
1
3 2
E A EA
EA+B EAB E Y Z
k
k
k k
+
+ +

(This is known as the ordered ternary-complex mechanism; A must add first to E, and the resulting complex EA reacts with B; the
complex EB is not formed.)
The concentrations of A and B are much greater than the concentration of E. Apply the steady-state treatment and obtain an
expression for the rate.

Solution

Chapter 10: Chemical Kinetics II. Composite Mechanisms Polymerization
10-17
10.45. The following ping-pong mechanismappears sometimes to apply to an enzyme-catalyzed reaction between two substrates A and
B to give the final products Y and Z:
1 2
1
3 4
E A EA EA +Y
EA +B EA B E Z
k k
k
k k
+
+

It can be assumed that the substrates are present in great excess of the enzyme and that steady-state conditions apply. Obtain an
expression for the rate of reaction.
Solution
Polymerization
10.46. The polymerization of styrene [M] catalyzed by benzoyl peroxide [C] obeys a kinetic equation of the form:
3/2 1/2
[M]
[M] [C]
d
k
dt
=
Obtain an expression for the kinetic chain length, in terms of [M], [C], and the rate constants for initiation, propagation, and
termination.
Solution

10.47. The polymerization of ethylene [M] photosensitized by acetone occurs by the mechanism:

CH3COCH3
hv
CO +2CH3

CH3 +C2H4
p
k
CH3CH2CH2

CH3CH2CH2 +C2H4
p
k
CH3CH2CH2CH2CH2

Rn +Rm
r
k
Mn +m

where one quantumgives 2CH3.
Show that the rate equation is:
1/2
[M] 2
[M]
p
t
d I
k
dt k
| |
=
|
\ .

where I is the intensity of light absorbed and kp and kt arethe rate constants for the propagation and termination steps, respectively.

Solution
Chapter 10: Chemical Kinetics II. Composite Mechanisms Essay Questions
10-18
Essay Questions
10.48. Explain the essential features of a chain reaction.

10.49. Give an account of catalysis by acids and bases, distinguishing between specific and general catalysts.

10.50. Will the rate of an enzyme-catalyzed reaction usually be more sensitive to temperature than that of the same reaction when it is
uncatalyzed? Discuss.

10.51. Explain how you would determine the parameters Km and kc for an enzyme reaction involving a single substrate.

10.52. Explain clearly the difference between collisions and encounters. What significance does this distinction have in chemical kinetics?

10.53. Explain clearly the kind of reasoning involved in deciding what might be the rate-controlling step in a chemical reaction.

10.54. Give a qualitative description of the electronic double-layer theories of Helmholtz, Gouy and Chapman, and Stern.
Chapter 10: Chemical Kinetics II. Composite Mechanisms Solutions
10-19
Solutions
10.1. Suppose that a reaction of stoichiometry A +2B =Y +Z is believed to occur by the mechanism:

Where X is an intermediate. Write the expression for the rate of formation of Y.
Solution:
( )
( )
1
2
A B X very slow
X B Y Z very fast
k
k
+
+ +

Because the second reaction is very fast, X is consumed once produced. So steady state approximation may be applied.
| |
| || | | || |
| |
| | | |
X 1 2
1
X
A B X B 0
A B
X
d
k k
dt
k
= = =
=
| |
2
B k
| |
| |
| |
| || |
| |
1
2
Y 2
1 2
A
X
Similarly
Y
X B
Y
k
k
d
k
dt
k k d
dt
=
= =
=
| || |
2
A B
k
| |
| || |
1
Y
A B
d
k
dt
=

10-20
10.2. Suppose that a reaction A +2B =2Y +2Z is believed to occur according to the mechanism:

Obtain an expression for the rate of formation of the product Y.
Solution:
( )
( )
1
1
2
A 2X very rapid equilibrium
X B Y Z slow
k
k
k
+ +

Adjust for the stoichiometric coefficients, we can write the reactions as follows:

( )
( )
1
1
2
1
A X very rapid equilibrium
2
X B Y Z slow
k
k
k
+ +

Theoverall reaction becomes:
1
1
1
A B Y Z
2
k
k
+ +

Let us write out the rate of formation for substance X and Y.
| |
| | | | | || |
1
2
1 1 2
X
A X X B
d
k k k
dt

=
| |
| || |
2
Y
X B
d
k
dt
=
Since X is an intermediate, steady state approximation can be applied.
10-21
| |
| | | | | || |
| | | | | || |
| | | | | | ( )
| |
| |
| |
1
2
1 1 2
1
2
1 1 2
1
2
1 1 2
1
2
1
1 2
X
A X X B 0
A X X B
A X B
A
X
B
d
k k k
dt
k k k
k k k
k
k k
= =
=
=
=
+

Plug the above expression into the expression for the rate of formation of Y
| |
| || |
| | | | | |
| |
2
1
2
2 1
1 2
Y
X B
Y A B
B
d
k
dt
d k k
dt k k
=
=
+

In this particular reaction, since the first step reaches equilibriumvery rapidly, it is safe to assume that
1 2
k k >> .
| | | | | |
| |
1
2
2 1
1 2
Y A B
B
d k k
dt k k
=
+

| |
| | | |
1/2
1
Y 2
1
Y
A B
d k
k
dt k
| |
= =
|
\ .

10-22
10.3. Suppose that a reaction of stoichiometry A +B =Y +Z is believed to occur according to the mechanism:

Apply the steady-state treatment and obtain an expression for the rate. To what expressions does the general rate equation reduce if;
a. The second reaction is slow, the initial equilibriumbeing established very rapidly?
b. The second reaction is very rapid compared with the first reaction in either direction?
Solution:

( )
( )
1
1
2
A X fast equilibrium
X B Y Z slow
k
k
k
+ +

We will begin by writing out the rate of formation and consumption for each species involved.
| |
| | | |
| |
| | | | | || |
| |
| || |
| |
| || |
| |
| || |
1 1
1 1 2
2
2
2
A
A X
X
A X X B
B
X B
Y
X B
Z
X B
d
k k
dt
d
k k k
dt
d
k
dt
d
k
dt
d
k
dt
=
=
=
=
=

According to the steady-state treatment, we can assume that
| | X
0
d
dt
= to a good approximation. This will enable us to find an expression for | | X .
10-23
| | | | | || |
| | | | | | ( )
| |
| |
| | ( )
1 1 2
1 1 2
1
1 2
A X X B
A X B
A
X
B
k k k
k k k
k
k k
= +
= +
=
+

a) Theinformation above leads us to believe that
1 2
k k
>> which means that,

| |
| |
| | ( )
| |
| | ( )
| |
| || |
| |
1
1 2
1
Y 2
1 2
1 2
Y
1 2
A
X
B
A
B
B
A B
B
k
k k
k
k
k k
k k
k k
=
+
(
= (
+
(

=
+
| || |
1 2
Y
1
this termcan be dropped
A B k k
k
=

b) Theinformation above leads us to believe that
2 1
k k
>> which means that,

10-24
| |
| |
| | ( )
| |
| | ( )
| |
| || |
1
1 2
1
Y 2
1 2
1 2
Y
1
A
X
B
A
B
B
A B
k
k k
k
k
k k
k k
k
=
+
(
= (
+
(

=
| |
2
1 2
Y
this termcan be dropped
B k
k k
+
=
| | | | A B
| |
2
B k
| |
Y 1
A k =

10-25
10.4. A reaction of stoichiometry:
A +B =Y +Z
is found to be second order in A and zero order in B. Suggest a mechanismthat is consistent with this behavior.
Solution:
Given that,
| | | | | |
| |
1
1
2 0 0
2
A B Y Z
A B since B 1 then,
A
k
k
K
K
+ +
= =
=

This means that substance B should not appear in the rate determining step.
( ) 1 2A X ( )
( )
very slow
2 X ( )
( )
( )
2B 2Y 2Z very fast
3 2A 2B 2Y 2Z
2
4 A B Y Z
+ +
+ +
+ +

10-26
lnk
1/T
10.5. Therate of formation of the product of a reaction is found to give a nonlinear Arrhenius plot, the line being convex to the 1/T axis (i.e., the
activation energy is higher at higher temperatures). Suggest a reason for this type of behavior.
(Hint: For this and the following problem, consider the possibility of two parallel reactions and of two consecutive reactions having different
activation energies.)

Solution:
We are told that a plot of lnk against 1/T produces a non-linear curve that is convex to the x-axis. The following diagramis a sketch of what this would
look like.
Based on the information given above, we can assume that two reactions are occurring simultaneously and that there is competition for a particular
reactant.

10-27
10.6. An Arrhenius plot is concave to the 1/T axis (i.e., it exhibits a lower activation energy at higher temperatures). Suggest a reason for this type of
behavior.

Solution:
Two consecutive reactions may be taking place here.


10-28
10.7. Nitrogen pentoxide reacts with nitric oxide in the gas phase according to the stoichiometric equation:

N
2O5 +NO =3NO2
Thefollowing mechanismhas been proposed:

Assume that the steady-state treatment can be applied to NO3, and derive an equation for the rate of consumption of N2O5.
Solution:
Let us begin by writing out the rate of formation and consumption for each species involved in the reaction.
( )
( )
( )
1
1
1
2
3
2 5 2
2 5 2 3
2 3 2 5
3 2
N O NO 3NO
1 N O NO NO
2 NO NO N O
3 NO NO 2NO
k
k
k
k
k
+
+
+
+

Since the first two equations can be combined to a single equilibrium, we can write,
( )
( )
| |
| | | || |
| |
| | | || | | || |
| |
| || |
1
1
2
2 5
3
2 5 2 3
3 2
2 5
N O 1 2 5 1 2 3
3
NO 1 2 5 1 2 3 2 3
NO 2 3
1 N O NO NO
2 NO NO 2NO
N O
N O NO NO
NO
N O NO NO NO NO
NO
NO NO
k
k
k
d
k k
dt
d
k k k
dt
d
k
dt
+
= =
= =
= =

According to the steady-state approximation,
10-29
| |
| | | || | | || |
| | | || | | || |
3
3
NO 1 2 5 1 2 3 2 3
1 2 5 1 2 3 2 3
NO
N O NO NO NO NO 0
N O NO NO NO NO
d
k k k
dt
k k k
= = =
= +

| | | | | | | | ( )
| |
| |
| | | | ( )
1 2 5 3 1 2 2
1 2 5
3
1 2 2
N O NO NO NO
N O
NO
NO NO
k k k
k
k k
= +
=
+

This can besubstituted into the rate of consumption for | |
2 5
N O and simplified.
| | | || |
| | | |
| |
| | | | ( )
| |
| || |
| | | | ( )
| | | | | | ( ) | || |
| | | | ( )
| || |
2 5
2 5
2 5
2 5
2 5
N O 1 2 5 1 2 3
1 2 5
N O 1 2 5 1 2
1 2 2
1 1 2 2 5
N O 1 2 5
1 2 2
1 2 5 1 2 2 1 1 2 2 5
N O
1 2 2
1 1 2 2 5
N O
N O NO NO
N O
N O NO
NO NO
NO N O
N O
NO NO
N O NO NO NO N O
NO NO
NO N O
k k
k
k k
k k
k k
k
k k
k k k k k
k k
k k
=
| |
= |
|
+
\ .
=
+
+
=
+
=
| || | | || |
1 2 2 5 1 1 2 2 5
N O NO NO N O k k k k
+
| | | | ( )
| || |
| | | |
2 5
1 2 2
1 2 2 5
N O
1 2 2
NO NO
N O NO
NO NO
k k
k k
k k
+
=
+

10-30
10.8. Thereaction 2NO +O2 2NO2 is believed to occur by the mechanism:

Assume N2O2 to be in a steady state and derive the rate equation. Under what conditions does the rate equation reduce to second-order kinetics
in NO and first-order kinetics in O2?
Solution:
Given: see above
Required: Under what conditions does the rate equation reduce to second-order kinetics in NO and first-order kinetics in O2?
( )
( )
( )
1
1
2
2 2
2 2
2 2
2 2 2 2
2NO O 2NO
1 2NO N O
2 N O 2NO
3 N O O 2NO
k
k
k
+

| |
| || |
| |
| | | | | || |
2
2 2
2
NO 2 2 2 2
2
2 2
N O 1 1 2 2 2 2 2 2
NO
O N O
N O
NO N O O N O
d
k
dt
d
k k k
dt

= =
= =

According to the steady state approximation,
| |
| | | | | || |
| | | | | || |
| | | | | | ( )
| |
| |
| | ( )
2 2
2
2 2
N O 1 1 2 2 2 2 2 2
2
1 1 2 2 2 2 2 2
2
1 2 2 1 2 2
2
1
2 2
1 2 2
N O
NO N O O N O 0
NO N O O N O
NO N O O
NO
N O
O
d
k k k
dt
k k k
k k k
k
k k
= = =
= +
= +
=
+

10-31
Substituting into the expression defining the rate of formation of | |
2
NO ,
| || |
| |
| |
| | ( )
2
2
NO 2 2 2 2
2
1
NO 2 2
1 2 2
O N O
NO
O
O
k
k
k
k k
=
| |
| =
|
+
\ .

| || |
| | ( )
2
2
1 2 2
NO
1 2 2
O NO
O
k k
k k
=
+

In order for the rate equation reduce to second-order kinetics in NO and first-order kinetics in O2,
1 2
k k
>> so that we may eliminate a terms in the

denominator. This yields the following:
| || |
| |
2
2
1 2 2
NO
1 2 2
O NO
O
k k
k k
=
+
( )
| || |
2
2
1 2
NO 2
1
O NO
k k
k
=

Thus, the rate equation will be second-order kinetics in NO and first-order kinetics in O2 when,
1 2
k k
>>

10-32
*10.9. Thegas-phase reaction:
Cl
2 +CH4 CH3Cl +HCl
proceeds by a free-radical chain reaction in which the chain propagators are Cl and CH3 (but not H), and the chain-ending step is 2Cl Cl2.
Write the mechanism, identify the initiation reaction and the chain-propagating steps, and obtain an expression for the rate of the overall
reaction.
Solution:
Following the method outlined in Section 10.5 Free Radical Reactions,
2 4 3
Cl CH CH Cl HCl + +
Initiation:
1
2
Cl Cl Cl
k
+
Propagation:
2
4 3
Cl CH HCl CH
k
+ +

3
3 2 3
CH Cl CH Cl Cl
k
+ +
Termination:
1
2
2Cl Cl
k

It is important to remember that the termination reaction always involves the regeneration of the initial species (the one that forms the free radicals in the
first place).
We can apply the steady-state approximation for the chlorine and CH3 radicals in order to obtain an expression for the overall rate of reaction.
| | | | | || |
| | | || |
| |
| |
3
2
1 2 2 4 3 2 3 1
Cl
3
2 4 3 2 3
CH
HCl 2 4
Cl
Cl Cl CH Cl CH Cl Cl
CH
Cl CH Cl CH Cl
HCl
Cl CH
d
k k k k
dt
d
k k
dt
d
k
dt
(

( ( = = +

(

( = =

( = =

10-33
| | | | | || |
| | | || |
3
2
1 2 2 4 3 2 3 1
Cl
3
2 4 3 2 3
CH
Cl
Cl Cl CH Cl CH Cl Cl 0 (1)
CH
Cl CH Cl CH Cl 0 (2)
d
k k k k
dt
d
k k
dt
(

( ( = = + =

(

( = = =

We recognize that the equations (1) and (2) have some common terms, such as | |
2 4
Cl CH k

(

and | || |
3 2 3
Cl CH Cl k . Since both equations equal to 0,
we can add themtogether in order those terms, and their sumstill adds up to 0.
| | | |
1 2 2 4
(1) (2):
Cl Cl CH k k

+
(

| || |
3 2 3
Cl CH Cl k + | |
2
1 2 4
Cl Cl CH k k

( ( +

| || |
3 2 3
Cl CH Cl k
| |
| |
2
1 2 1
1/2
1/2
1
2
1
0
Cl Cl =0
Cl Cl
k k
k
k
=
(

| |
( =
|

\ .

Substituting into the rata equation for the formation of HCl,
| |
| | | |
| || |
HCl 2 4
1/2
1/2
1
HCl 2 2 4
1
1/2
1/2
1
HCl 2 4 2
1
Cl CH
Cl CH
CH Cl
k
k
k
k
k
k
k
( =

| |
| |
| =
|
|
\ .
\ .
| |
=
|
\ .

10-34
10.10. Thefollowing mechanismhas been proposed for the thermal decomposition of pure ozone in the gas phase:

Derive the rate equation.
Solution:
Following the same method as we have done for the previous problems;

| |
| | | || |
| |
| | | || |
2
2
2
O 1 3 2 3
2
O 1 3 2 3
O
O O O
O
O O O
d
k k
dt
d
k k
dt
= = +
= =

Applying the steady state approximation to O,
| |
| | | || |
| | | || |
| |
| |
2
O 1 3 2 3
2
1 3 2 3
2
1 3
O
O O O 0
O O O
O
O
d
k k
dt
k k
k
= = =
=
=
| |
2 3
O k
| | | |
1
3
2
O O
k
k
=

Substitution into the expression for the rate of formation of oxygen yields,
( )
( )
1
2
3 3 2
3 2
1 2O O O O
2 O O 2O
k
k
+ +
+
10-35
| | | || |
| |
2
2
2
O 1 3 2 3
2
O 1 3 2
O O O
O
k k
k k
= +
= +
1
2
k
k
| | | |
| | | |
| |
2
2
3 3
2 2
O 1 3 1 3
2
O 1 3
O O
O O
2 O
k k
k
| |
|
|
\ .
= +
=

10-36
*10.11. A reaction occurs by the mechanism:

and the concentration of X is sufficiently small compared with the concentrations of A and B that the steady-state treatment applies. Prove that
the activation energy E
a at anytemperature is given by:
1 1 2 1 2 1
1 2
( )
a
k E E E k E
E
k k
+ +
=
+

that is, is the weighted mean of the values E1 +E2 E1, and E1, which apply, respectively, to the limiting cases of k1 k2 and k2 k1.
Solution:
1 2
1
A B X Z
k k
k

| |
| || | | | | |
| |
| |
X 1 1 2
Z 2
X
A B X X
Z
X
d
k k k
dt
d
k
dt
= =
= =

Applying the steady state approximation to substance X,
| |
| || | | | | |
| || | | | | |
| || | | |( )
| |
| || |
( )
X 1 1 2
1 1 2
1 1 2
1
1 2
X
A B X X 0
A B X X
A B X
A B
X
d
k k k
dt
k k k
k k k
k
k k
= = =
= +
= +
=
+

Substitution into the expression for the rate of formation of substance Z yields,
10-37
| |
| || |
( )
| || |
( )
Z 2
1
Z 2
1 2
1 2
Z
1 2
X
A B
A B
k
k
k
k k
k k
k k
=
| |
=
|
|
+
\ .
=
+

Let the rate constant
( )
1 2
1 2
k k
K
k k
=
+
and taking the natural log we obtain,
( )
1 2
1 2
1 2 1 2
ln ln
ln ln ln ln
k k
K
k k
K k k k k
| |
=
|
+
\ .
= + +

Differentiating both sides with respect to temperature leads to,
( )
( )
1 2 1 2
2 1 2
1 2 1 2
2 1 2 1 2
1 2 1 1
2 1 2 1 1 2
1 2
1 2
ln ln 1 1
ln ln 1 1 1
ln ln 1 1
ln ln
d k k d K k dk
dT dT k dT k k dT
d K k dk dk dk
dT dT k dT k k dT k k dT
d K k dk k dk
dT dT dT k k k k k k dT
k k
d K k dk
dT dT dT
+
= +
+
= +
+ +
| |
= +
|
+ +
\ .
+
= +
2
k
( )
1 1
2 1 2 1 2
1 1 2 1 1
1 2 1 2
ln
ln ln ln ln
k k
k k k k k dT
d K k k d k k k
dT dT k k dT k k dT

+ +
= +
+ +

Recall that Eq. 9.63 states,
1 1
2
lnk E
C
dT RT
= +
10-38
Rearranging to isolate the activation energy,
2 2 2 1 1 2
1 1 2
ln ln ln
similarly, and
k k k
E RT E RT E RT
dT dT dT

Substituting these expressions into the differentiated expression above yields,
2
1 1
1 2 1
1 2 1 2
ln
and therefore,
d K
E RT
dT
k k
E E E E
k k k k

=
= +
+ +

We can combine the terms by putting themover a common denominator.
( )
1 1 2 2 1 1 1
1 2 1 2 1 2
1 1 1 2 2 1 1 1
1 2
E k k E k E k
E
k k k k k k
E k E k E k E k
E
k k

+
= +
+ + +
+ +
=
+

Further simplification leads to the desired equation,
( )
1 2 1 1 2 1
1 2
E k k E E E
E
k k

+ +
=
+

10-39
10.12. F. A. Lindemann [Trans. Faraday Soc., 17, 598(1922)] proposed the following mechanismfor a unimolecular gas reaction:

Thespecies A* is an energized molecule that is present in low concentrations. Apply the steady-state treatment to A* and obtain an expression
for the rate in terms of [A], k
1, k1, and k2. Show that the mechanismpredicts first-order kinetics at higher A concentrations and second-order
kinetics at lower ones.
Solution:
Given: see above
Required: expression for rate, k1, k1, k2
| |
| | | |
| | | |
2
A 1 1
2
1 1 2
A
A
A A A
A
A A A A
d
k k
dt
d
k k k
dt
( = =

(

( ( = =

Applying the Steady-State treatment to A
we obtain the following expression:

| | | |
2
1 1 2
A
A
0
A A A A 0
d
dt
k k k

(

=
( ( = =

Rearranging and simplifying we obtain,
| | | |
| | | | ( )
| |
| | ( )
2
1 1 2
2
1 1 2
2
1
1 2
A A A A
A A A
A
A
A
k k k
k k k
k
k k

( ( = +

( = +

( =

+

10-40
Therate is given by,
2
A k

( =

We may substitute the above expression for A
which yields,
| |
| | ( )
2
1 2
1 2
A
A
k k
k k
=
+

At high pressures, we can work under the assumption that | |
1 2
A k k
>> therefore enabling us to remove the

2
k termin the denominator and further
simplify the expression.
| |
| |
2
1 2
1 2
A
A
k k
k k
=
+
( )
| |
2
1 2
A k k
| |
1
A k
| |
1 2
1
A
k k
k
=
(a first order rate equation)
At low pressure, we can work under the assumption that | |
2 1
A k k
>> and thus,

| |
| |
2
1 2
1
A
A
k k
k
=
( )
1 2
2
k k
k
+
| |
2
2
A
k
| |
2
1
A k =
(a second order rate equation)


10-41
*10.13. Certain polymerizations involve esterification reactions between COOH groups on one molecule and OH groups on another. Suppose that the
concentration of such functional groups is c and that the rate of their removal by esterification obeys the equation:

2
dc
kc
dt
=
Obtain an equation relating the time t to the fraction f of functional groups remaining and to the initial concentration c0 of functional groups.
Solution:
Given the differential equation
2
dc
kc
dt
= , we can start by choosing the boundary condition that at t =0, c =c0. Rearranging the above expression and
taking the integral of both sides, we obtain,
2
2
1
dc
kdt
c
dc
kdt
c
kt I
c
=
=
= +

Applying the boundary conditions to solve for I,
1
kt
c
=
0
1
I
I
c
+
=

Substituting this back into the integrated expression,
0
1 1
kt
c c
=
This can berewritten as,
10-42
0
0
c c
kt
cc
=
Theexpression for the fraction of functional groups remaining is therefore,
0
0
c c
f
c
=
Let us derive an expression relation the fraction of functional groups remaining to the initial concentration only,
0 0
0 0 0
0
0 0
0 0 0
0
0
0
0 0
0
0
1
Inverting the above expression:
1 1
1 1
1
1 1 1
1
1
c c c c
f c c c c
c kt
c c c c
f c
c c c
f
f c kt
f c kt
c kt
f c kt c kt
c kt
f
c kt

= = = =
=
=
+
= + =
=
+


10-43
*10.14. Show that the mechanism:

leads to the result that the rate equation for the overall reaction is =k[H2][I2].
Solution:
Recall that when reactions occur as fast equilibriums, we may write,
( )
| |
| |
( )
| |
| || |
2
1
1 2
2 2
2 2
I
1
I
H I
2
I H
k
K
k
k
K
k
= =
= =

Let us now rearrange these expressions in order to isolate I and H2I as they are important reagents in the rate determining step. Finding expressions for
these will allow us to determine the rate equation.
| |
| |
| | | |
| | | |
2
1
1 2
2
1
2
1
1
1 2
1
2
2
1
I
I
I I
I I
k
k
k
k
k
k
=
=
| |
=
|
\ .

| |
| || |
| | | || |
2 2
2 2
2
2 2
2
H I
I H
H I I H
k
k
k
k
=
=

10-44
Now substitute the expression for I into the above to obtain,
| | | | | |
1
1 2
2 1
2
2 2 2
2 1
H I I H
k k
k k

| |
=
|
\ .

Theoverall rate is given by the rate determining step which is the slow reaction in this case.
| || |
3 2
H I I k =
Substitution yields,
| | | | | |
1 1
1 1 2 2
2 1 1
2 2
3 2 2 2
2 1 1
I H I
k k k
k
k k k

| | | |
=
| |
\ . \ .

Simplification yields,
1
2
2 1
3
2 1
k k
k
k k

| |
=
|
\ .
| |
1
2
2
I | |
1
2
1
2
1
H
k
k
| |
|
\ .
| |
1
2
2
I
| || |
| || |
3 2 1
2 2
2 1
3 2 1
2 1
2 2
I H
letting , we obtain the final expression for the rate equation
I H
k k k
k k
k k k
k
k k
k

=
=
=

10-45
10.15. Apply the steady-state treatment to the following mechanism, in which Y and Z are final products and X is a labile intermediate:

Obtain an expression for the rate of formation of the product Z. What rate equations are obtained if (a) A and (b) B are present in great excess?
Solution:
Given: see above
Required: expression for rate of formation of Z, a), b)
We will begin by writing out the rates of consumption or production for each of the reacting species involved. We do know, however, that X is the
species for which we will be applying the steady-state treatment.
| |
| || | | | | || |
| |
| || | | | | || |
| |
| || | | | | || | | || |
A 1 1 2
B 1 1 3
X 1 1 2 3
A
A B X A X
B
A B X B X
X
A B X A X B X
d
k k k
dt
d
k k k
dt
d
k k k k
dt
= = +
= = +
= =

Applying the steady-state treatment for X, we obtain,
| |
| || | | | | || | | || |
| || | | | | || | | || |
1 1 2 3
1 1 2 3
X
0
A B X A X B X 0
A B X A X B X
d
dt
k k k k
k k k k
=
=
= + +

This can besimplified by factoring out X fromthe right hand side.
10-46
| || | | | | | | | ( )
| |
| || |
| | | | ( )
1 1 2 3
1
1 2 3
A B X A B
A B
X
A B
k k k k
k
k k k
= + +
=
+ +

Now we may write out the rates of formation for the product Z.
| |
| || |
Z 3
Z
B X
d
k
dt
= =
Substituting what we have found (while applying the steady-state treatment to X) above into the expression for the rate of formation of Z we obtain,
| || |
| |
| || |
| | | | ( )
| || |
| | | | ( )
Z 3
1
Z 3
1 2 3
2
1 3
Z
1 2 3
B X
A B
B
A B
A B
A B
k
k
k
k k k
k k
k k k
=
=
+ +
=
+ +

a) If reagent A is present in great excess, then we can work under the assumption that | | | |
2 1 3
A B k k k
>> + which allows us to simplify the rate

equation given above.
| || |
2
1 3
Z
1
A B k k
k
=
| | | |
2 3
A B k k + +
( )
| |
1 3
Z
A k k
=
| |
| |
2
2
B
A k
| |
2
1 3
Z
2
B
k k
k
=
10-47
b) If the reagent B is present in great excess then we can work under the assumption | | | |
3 1 2
B A k k k
>> + thus,
| || |
| |
2
1 3
Z
1 2
A B
A
k k
k k
=
+ | | ( ) 3
1 3
Z
B k
k k
+
=
| || |
2
A B
| |
3
B k
| || |
Z 1
A B k =
Since this simplified rate equation has the same formas that originally derived, the first reaction is rate determining.

10-48
10.16. Calculate themaximumwavelength of the radiation that will bring about dissociation of a diatomic molecule having a dissociation energy of
390.4 kJ mol
1
.
Solution:
Given:
1
diss
390.4 kJ mol E =
Required:
max

We know that the dissociation energy given above is the total dissociation energy per mole. It is important to determine the dissociation energy in
J oules. In order to do this, we will divide the dissociation energy by Avogadros number.
1
diss
390.4 kJ mol
E
=
23 1
6.022 10 mol
22
diss
19
diss
6.482 896 10 kJ
6.482 896 10 J
E
E
=
=

With this energy, we can determine the corresponding frequency by using the following expression,
E hv
E
v
h
=
=

Where h is Plancks constant and is measured in J s.
19
6.482 896 10 J
v
=
34
6.626 10 J
14 1
s
9.784 027 10 s v

=

Thesimple wave equation that relates the speed of light to wavelength and frequency can be used in order to determine the wavelength.
c v
c
v
=
=

Where c is the speed of light measured in ms
-1
.
10-49
8 1
2.998 10 ms
=
14 1
9.784 027 10 s
7
3.06 10 m

=

Since wavelengths are typically expressed in terms on nanometers, we can write,
7
3.06 10 m

=
9
1 nm
1 10 m
306 nm
| |
|
\ .
=

This wavelength corresponds to the maximumwavelength that will cause dissociation of this diatomic molecule.


10-50
10.17. Hydrogen iodide undergoes decomposition into H2 +I 2 when irradiated with radiation having a wavelength of 207 nm. It is found that when 1 J
of energy is absorbed, 440 g of HI is decomposed. How many molecules of HI are decomposed by 1 photon of radiation of this wavelength?
Suggest a mechanismthat is consistent with this result.

Solution:
Given: 207 nm, 1 J , 440 g E m = = =
Required: number of molecules of HI decomposed
It is first important to determine the number of moles of HI in 440 g. We can do this by using the molar mass of HI.
6
6
440 g 440 10 g
440 10 g
m
n
M
n
=
=
=
127.9 g
1
6
mol
3.440 188 10 mol n
=

With this, we are able to determine the number of molecules of HI by using Avogadros number.
6
#molecules 3.440 188 10 mol
=
23 1
6.022 10 mol
( )
18
#molecules 2.071 681 10 =

Given the wavelength, we can determine the corresponding frequency as was done in the previous problem.
8
2.998 10 m
c v
c
v
= =
1
9
s
207 10 m
15 1
1.448 309 10 s v

=

Using E hv = , we can determine the energy associated with this frequency and wavelength.
10-51
34
6.626 10 J s
E hv
E

=
=
( )
15 1
1.448 309 10 s
( )
19
9.596 497 10 J E

=

1 J oule of radiation will correspond to the following number of photons,
1 J
#photons=
19
9.596 497 10 J

18
#photons 1.04 10 =
A single photon will then be able to decompose
18
18
#molecules 2.071 681 10
1.99
#photons 1.04 10
= =
. Which is approximately 2 molecules of HI.

TheGerman photochemist Emil Gabriel Warburg found for this reaction, a quantumyield of 2 (as we have just done). In order to explain this, he
proposed the following mechanism:
2
2
HI H I
H HI H I
I I I
hv + +
+ +
+

When all three steps are added together, we obtain the following:
2 2
2HI H I hv + +


10-52
10.18. A 100-watt mercury-vapor lamp emits radiation of 253.7 nmwavelength and may be assumed to operate with 100% efficiency. If all the light
emitted is absorbed by a substance that is decomposed with a quantumyield of unity, how long will it take for 0.01 mol to bedecomposed?

Solution:
Given: 100 W, 253.7 nm, 0.01 mol P n = = =
Required: required to decompose t
Let us first determine the frequency associated with the radiation of 253.7 nm.
8
2.998 10 m
c v
c
v
= =
1
9
s
253.7 10 m
15 1
1.181 711 10 s v

=

Theenergy can be found using the following expression:
34
6.626 10 J s
E hv
E

=
=
( )
15 1
1.181 711 10 s
( )
19
7.830 10 J E

=

We know that a 100-W lamp emits 100 J oules per second (definition of a watt). Using this information, we can determine the number of photons
emitted per second.
100 J
#photons per second
P
E
= =
1
19
s
7.830 10 J
20
#photons per second 1.277 137 10 =

Since we are working in moles, let us change the above into molar units.
20 1
4
23 1
1.277 137 10 s
2.120 785 10 moles of photons per second
6.022 10 mol

In order for 0.01 moles of this substance to be decomposed, it will require
10-53
0.01 mol
t =
4
2.120785 10 mol
1
47.15 s 47 s
s
= =

10-54
10.19. Suppose that the radiation emitted by the lamp in Problem10.18 is all absorbed by ethylene, which decomposes into C2H2 +H2 with a quantum
yield of unity. How much ethyne will be produced per hour?

Solution:
Given: Problem10.18: 100 W, 253.7 nm, 0.01 mol P n = = =
Required: amount of ethylene produced per hour
Thelamp in the previous problemwas found to produce,
20 1
4
23 1
1.277 137 10 s
2.120 785 10 moles of photons per second
6.022 10 mol

Knowing this, we can determine how many moles of photons would be produced in 1 hour.
4 1
60 s 60 min
1 hour 3600 s
min hour
2.120 785 10 mol s n

= =
=
s
3600
hour
mol
0.76
hour
n
| |
|
\ .
=

Since ethylene is also a substance with a quantumyield of unity, then 0.76 moles of ethylene will be produced per hour.

10-55
10.20. A 1000-watt mercury vapor flash lamp emits radiation of 253.7 nmwavelength, and the duration of the flash is 1 s. Suppose that all of the
radiation of a single flash is absorbed by mercury vapor; how many atoms of excited mercury are formed?

Solution:
Given: flash lamp: 1000 W, 253.7 nm, 1 s P t = = =
Required:
Hg
produced N
We will begin by determining the frequency and energy associated with this wavelength.
8
2.998 10 m
c v
c
v
= =
1
9
s
253.7 10 m
15 1
34
1.181 711 10 s
6.626 10 J s
v
E hv
E
=
=
=
( )
15 1
1.181 711 10 s
( )
19
7.830 10 J E

=

Again, we know that a 1000-W lamp will emit 1000 J oules per second. With this, we can determine the number of photons emitted per second.
1000 J
#photons per second
P
E
= =
1
19
s
7.830 10 J
21
#photons per second 1.277 137 10 =

In a single microsecond, which is equal to,
6
1 s 1 10 s

= we will see that,
21 1
#photons 1.277 137 10 photons s
=
( )
6
1 10 s
( )
15
#photons 1.277 10 emitted =

Supposing that all of the radiation of a single flash (1 microsecond) is absorbed by mercury vapor, the number of photons emitted in this time will be
equal to the number of excited mercury atoms formed.
15
Hg
1.28 10 atoms N =

10-56

10-57
*10.21. The photochemical reaction between chlorine and chloroformin the gas phase follows the stoichiometric equation:

CHCl
3 +Cl2 =CCl4 +HCl
It is believed to occur by the mechanism:

Assume the rate of formation of Cl atoms in the initiation reaction to be2Ia, where Ia is the intensity of light absorbed, and obtain an expression
for the overall rate in terms of Ia and [CHCl3].

Solution:
We will begin by writing down the steady-state expressions for Cl and CCl3.
| |
| || | | || | | |
| |
| || | | || | | |
| || | | || | | |
2
2 3 3 3 2 4
2
2 3 3 3 2 4
2
3 3 2 2 3 4
Cl
2 Cl CHCl CCl Cl Cl
Cl
0
2 Cl CHCl CCl Cl Cl 0
2 CCl Cl Cl CHCl Cl
a
a
a
d
I k k k
dt
d
dt
I k k k
I k k k
= +
=
+ =
+ = +

| |
| || | | || |
| |
| || | | || |
| || | | || |
3
2 3 3 3 2
3
2 3 3 3 2
2 3 3 3 2
CCl
Cl CHCl CCl Cl
CCl
0
Cl CHCl CCl Cl 0
Cl CHCl CCl Cl
d
k k
dt
d
dt
k k
k k
=
=
=
=

10-58
Adding the two steady-state expressions, we obtain the following:
| || |
2 3
2 Cl CHCl
a
I k | || |
3 3 2
CCl Cl k + | |
| || |
2
4
2 3
Cl 0
Cl CHCl
k
k
=
| || |
3 3 2
CCl Cl k
| |
2
4
0
2 Cl 0
a
I k
=
=

Solving for Cl,
| |
| |
| |
2
4
2
4
1
2
4
2 Cl
2
Cl
2
Cl
a
a
a
I k
I
k
I
k
=
=
| |
=
|
\ .

Theoverall rate equation is given by,
| || |
HCl 2 3
Cl CHCl k = =
Substituting the expression for Cl into the above yields,
| |
1
2
2 3
4
2
CHCl
a
I
k
k
| |
=
|
\ .

10-59
*10.22. When water vapor is irradiated with a beamof high-energy electrons, various ions such as H
+
and O

appear. Calculate the minimumenergies
required for the formation of these ions, given the following thermochemical data:

Are the results you obtain consistent with the experimental appearancepotentials of
19.5 eV for H
+
and 7.5 eV for O
?

Solution:
Hydrogen ions are quite easily formed according to the following process:
2
H O H OH 2 e e
+
+ + +
This reaction can be generated through the addition of the following two equations:
( )
( )
2
1 H O H OH
2 H H 2 e e

+
+ +

Thestandard enthalpy of formation for the original reaction is therefore given by,
( ) ( )
( )
o o o
o 1
o 1
1
o 1
1
o
rxn 1 rxn 2
498.7 1312.2 kJ mol
1810.9 kJ mol
1 eV 96.47 kJ mol
1 eV
1810.9 kJ mol
96.47 kJ mol
18.77 163 885 eV 18.8 eV
H H H
H
H
H
H
= +
= +
=
=
=
=

10-60
Theabove value is lower than the observed value of 19.5 eV, indicating that the systempasses through a state of higher energy. The OH radical
probably dissipates energy in the formof translational, vibrational, and rotational energy.
O
-
ions are most easily formed by
2
H O 2H O e

+ +

This reaction can be generated through the addition of the following three equations:
( )
( )
( )
2
4 H O H OH
5 OH H O
6 O + O e

+
+

Thestandard enthalpy of formation for the original reaction is therefore given by,
( ) ( ) ( )
( )
o o o o
o 1
o 1
1
o 1
1
o
rxn 4 rxn 5 rxn 6
498.7 428.2 213.4 kJ mol
713.5 kJ mol
1 eV 96.47 kJ mol
1 eV
713.5 kJ mol
96.47 kJ mol
7.396 081 683 eV 7.4 eV
H H H H
H
H
H
H
= + +
= +
=
=
=
=

Theabove value is close to the observed appearance potential of 7.5 eV.

10-61
10.23. The mercury-photosensitized hydrogenation of ethylene in the presence of mercury vapor is first-order with respect to ethylene and half-order
with respect to H
2. Itsrate is proportional to the square root of the intensity of the light absorbed. The following mechanismhas been suggested
to account for these observations:

Applying the steady-state approximation to [H] and [C2H5], verify that the mechanismindeed supports the observations. What is the observed
rate constant in terms of the rate constants of the elementary reactions?

Solution:
Applying the steady-state approximation for H, we obtain,
| |
| | | || | | || | | |
2
H 1 2 2 2 4 3 2 5 2 4
H
2 Hg H H C H C H H H
d
k k k k
dt

( = = +

Applying the steady-state approximation to C2H5, we obtain,
| |
| || | | || |
2 5
2 5
C H 2 2 4 3 2 5 2
C H
H C H C H H
d
k k
dt
= =
Let us simplify both equations.
10-62
| |
| | | || | | || | | |
| | | || | | || | | |
| |
| || | | || |
| || | | || |
2
1 2 2 2 4 3 2 5 2 4
2
1 2 3 2 5 2 2 2 4 4
2 5
2 2 4 3 2 5 2
2 2 4 3 2 5 2
H
0
2 Hg H H C H C H H H 0
2 Hg H C H H H C H H
C H
0
H C H C H H 0
H C H C H H
d
dt
k k k k
k k k k
d
dt
k k
k k
=
( + =

( + = +

=
=
=

Adding both equations we obtain,
| | | || |
1 2 3 2 5 2
2 Hg H C H H k k
( +

| || |
2 2 4
H C H k = | |
| || |
2
4
2 2 4
H
H C H
k
k
+
| || |
3 2 5 2
C H H k =

| | | |
2
1 2 4
2 Hg H H k k
( =

Isolating for H will yield,
| | | |
| |
| |
| |
| |
2
1 2 4
2 1 2
4
1
2
1 2
4
2 Hg H H
2 Hg H
H
2 Hg H
H
k k
k
k
k
k
( =

(

=
| | (

| =
|
\ .

Substituting this expression into the steady-state approximation for C2H5,
10-63
| |
| || | | || |
| || | | || |
| |
| || |
| |
| |
| |
| |
| |
2 5
2 5
C H 2 2 4 3 2 5 2
2 2 4 3 2 5 2
2 2 4
2 5
3 2
1
2
1 2
2 2 4
2 5
3 2 4
C H
H C H C H H 0
H C H C H H
H C H
C H
H
2 Hg H
C H
C H
H
d
k k
dt
k k
k
k
k
k
k k
= = =
=
=
| | (

= |
|
\ .

Therate of formation of ethane is given by,
| |
| || |
2 6
2 6
C H 3 2 5 2
C H
C H H
d
k
dt
= =
This can also be written as,
| |
2 6
2 6
C H 3
C H d
k
dt
= =
| |
2 2
H k | |
2 4
3
C H
k | |
2
H
| |
| |
| |
| |
2 6
1
2
1 2
4
1
2
1 2 2 6
C H 2 2 4
4
2 Hg H
2 Hg H C H
C H
k
k
k d
k
dt k
| | (

|
|
\ .
| | (

| = =
|
\ .

Therate is indeed first order with respect to ethylene and half-order with respect to Hg* and H2. Since thenumber of moles of Hg
*
produced is directly
proportional to the intensity of the light absorbed, the rate is also proportional to the square root of the intensity of thelight. The observed rate constant
is therefore given by,
1
2
1
obs 2
4
2k
k k
k
| |
=
|
\ .

10-64
10.24. Thehydrolysis of a substance is specifically catalyzed by hydrogen ions, and the rate constant is given by:

k/dm
3
mol
1
s
1
=4.7 10
2
([H
+
]/mol dm
3
)
When the substance was dissolved in a 10
3
M solution of an acid HA, therate constant was 3.2 10
5
dm
3
mol
1
s
1
. Calculate the dissociation
constant of HA.

Solution:
Given:
2 3 1 1 3 5 3 1 1
0 HA
4.7 10 dmmol s , 10 M, 3.2 10 dm mol s k C k = = =
Required:
Theconcentration of H
+
ions in the solution is:
5
4 3
2
3.2 10
6.81 10 mol dm
4.7 10

Thedissociation constant is therefore
( )
2
4
4 3
3
6.81 10
4.64 10 mol dm
10
a
K
= =

10-65
*10.25. The following is a slightly simplified version of the mechanismproposed in 1937 by G. K. Rollefson and R. F. Faull [J. Amer. Chem. Soc., 59,
625(1937)] to explain the iodine-catalyzed decomposition of acetaldehyde:

I
2 2I
I +CH3CHO HI +CH3CO
CH3CO CH3 +CO
CH3 +HI CH4 +I
2I I2
Apply the steady-state treatment to I, CH3CO, and CH3 and obtain an expression for the rate.

Solution:
We can first associate reaction constants to the above reactions as k1, k2, k3, k4, and k5. Then we can write out the rate of formation or consumption for
the intermediate species I, CH3CO, and CH3. By the steady-state approximation, the rate of formation or consumption of these species equal to 0.
| |
| | | || | | || | | |
| |
| | | || | | || | | |
2
I 1 2 2 3 4 3 1
I
2
1 2 2 3 4 3 1
I
2 I I CH CHO CH HI I
I
0
2 I I CH CHO CH HI I 0
d
k k k k
dt
d
dt
k k k k
= = +
= =
+ =

| |
| || | | |
| |
| || | | |
3
3
3
CH CO 2 3 3 3
3
CH CO
2 3 3 3
CH CO
I CH CHO CH CO
CH CO
0
I CH CHO CH CO 0
d
k k
dt
d
dt
k k
= =
= =
=

| |
| | | || |
| |
| | | || |
3
3
3
CH 3 3 4 3
3
CH
3 3 4 3
CH
CH CO CH HI
CH
0
CH CO CH HI 0
d
k k
dt
d
dt
k k
= =
= =
=

10-66
All three of these steady-state approximations can be added together in order to eliminate terms. This process yields the following result:
| | | || |
1 2 2 3
2 I I CH CHO k k | || |
4 3
CH HI k + | |
| || |
2
1
2 3
I 0
I CH CHO
k
k
=
| |
3 3
CH CO k
| |
3 3
0
CH CO k
=
| || |
4 3
CH HI k
| | | |
2
1 2 1
0
2 I I 0 k k
=
=

Rearrange and simplify to isolate I.
| | | |
| | | |
| | | |
2
1 1 2
2
1
2
1
1
1 2
1
2
2
1
2 I I
I I
2
I I
2
k k
k
k
k
k
=
=
| |
=
|
\ .

Theoverall rate is given by,
| | | || |
CO 3 3 2 3
CH CO I CH CHO k k = =
Making the substitution for I, we will get,
| | | |
1
1 2
1
2
CO 2 2 3
1
I CH CHO
2
k
k
k
| |
=
|
\ .

10-67
*10.26. Suppose that a reaction is catalyzed by a series of homologous acids and that the Hammett equation (9.130) applies:

log
10 ka =log10 k0 +
where is the substituent constant and is the reaction constant. Suppose that the corresponding equation for the dissociation of the acid is:
log10 Ka =log10 K0 +'
where ' is the reaction constant for the dissociation; the substituent constants are the same in both equations. Prove that the Brnsted equation:
a a a
k G K
=
applies. How does relate to the reaction constants and '?

Solution:
Thefirst two equations above may be written in the following manner:
10 10 0
10 10 0
1 1
log log
1 1
log log
" "
a
a
k k
K K

= +
= +

Subtracting the second equation fromthe first yields,
10 10
1 1
log log constant
"
a a
k K

= =
Combine the terms to obtain,
10 10
1 1
"
10 10
1
10 1
"
1 1
log log constant
"
log log constant
log constant
a a
a
a
a a
k K
k K
k
K

=
=
=

This can also be written as,
10-68
10
"
log constant
a
a
k
K
=

Rearranging this expression to isolate k
a,
constant
"
"
10
a
a
a
a
k
G
K
k GK
= =
=

Note that
"
= thus,
a
a
k GK
=
represents the ratio of the two reaction constants.


10-69
10.27. Thehydrolysis of ethyl acetate catalyzed by hydrochloric acid obeys the rate equation:
=k[ester][HCl]
and the reaction essentially goes to completion. At 25 C the rate constant is
2.80 10
5
dm
3
mol
1
s
1
. What is the half-life of the reaction if [ester] =0.1 M and
[HCl] =0.01 M?

Solution:
Given: | || | | |
5 3 1 1
ester HCl , 25 C, 2.80 10 dm mol s , ester 0.1 M, k T k = = = =
| | HCl 0.01 M =
Required:
1/2
t
Since the reaction essentially goes to completion, we can assume that the concentration of hydrochloric acid remains unchanged throughout. We have
also been given the rate equation which is first order with respect to HCl but is overall second order. We can use the concentration of HCl in order to
determine the pseudo-first order rate constant.
Remembering that first order reactions have a rate constant with the units s
-1
(Table 9.1),
( )
| |
| |
( )| |
nd 5 3 1 1
1 3
3
nd
5 3 1
HCl 0.01 M
1 M mol L , 1 L 1 dm therefore,
HCl 0.01 M 0.01 mol dm
' 2 order HCl
' 2.80 10 dm mol
k
k k
k
=
=
= =
= =
=
=
( )
1 3
s 0.01 mol dm
( )
7 1
' 2.80 10 s k

=

Thehalf life for a first order reaction is given by Eq. 9.40:
1/2
ln2
t
k
=
10-70
This expression is also found in Table 9.1. Now, making the substitution of the pseudo-first order rate constant into Eq. 9.40 we obtain,
1/2 7 1
6
1/2
6.931 472
2.80 10 s
2.48 10 s
t
t

=
=


10-71

10.28. Thefollowing mechanismhas been proposed for the alkaline hydrolysis of Co(NH3)5Cl
2+
:
Co(NH3)5Cl
2+
+OH
Co(NH3)4(NH2)Cl
+
+H2O
Co(NH3)4(NH2)Cl
+
Co(NH2)4(NH2)
2+
+Cl

Co(NH3)4(NH2)
2+
+H2O Co(NH3)5(OH)
2+

Assume Co(NH3)4(NH2)Cl
+
and Co(NH3)4(NH2)
2+
to be in the steady state and derive an expression for the rate of reaction.
Experimentally, the rate is proportional to [Co(NH)5Cl
2+
] [OH
]; does this fact tell us anything about the relative magnitudes of the rate
constants?

Solution:
Lets make a couple of substitutions in order to simplify the list of reactions.
( )
( ) ( )
( ) ( )
( ) ( )
2
3 5
3 2 4
2
2 2 4
2
3 5
A Co NH Cl
X Co NH NH Cl
Y Co NH NH
Z Co NH OH
+
+
+
+
=
=
=
=

Rewriting the above reaction sequence we obtain,
( )
( )
( )
1
2
3
2
2
1 A OH X H O
2 X Y Cl
3 Y H O Z
k
k
k
+ +
+
+

Applying the steady state approximation to substance X,
10-72
| |
| | | |
| |
| | | |
| | | |
X 1 2
X
1 2
1
2
X
A OH X
X
0
A OH X
X A OH
d
k k
dt
d
dt
k k
k
k
( = =

= =
( =

( =

Applying the steady state approximation to substance Y,
| |
| | | || |
Y 2 3 2
Y
X Y H O
d
k k
dt
= =
| |
| | | || |
| |
| |
| |
| |
Y
2 3 2
2
3 2
2
Y
0
X Y H O
X
Y
H O
Y
d
dt
k k
k
k
k
= =
=
=
=
1
3 2
k
k k
| |
| |
| |
| |
| |
1
3 2
A OH
H O
A OH
Y
H O
k
k
| | (

|
|
\ .
(

=

Theoverall rate of reaction is therefore,
10-73
| || |
Z 3 2
Z 3
Y H O k
k
=
=
1
3
k
k
| |
| |
2
A OH
H O
(

| |
2
H O
| |
( )
Z 1
2
Z 1 3 5
A OH
Co NH Cl OH
k
k
+
( =

( ( =

10-74
10.29. Confirmthat Eq. 10.68,
1
2
min
OH H
[H ] ( / )
w
k K k
+
+
=
follows fromEq. 10.66,
OH
0
H
[H ]
[H ]
w
k K
k k k
+
+
+
= + +
Solution:
We have been told that,
OH
0
H
[H ]
[H ]
w
k K
k k k
+
+
+
= + +
This expression may be differentiated with respect to [H ]
+
. This process yields,
OH
0
H
OH
2 H
[H ]
[H ] [H ] [H ]
[H ] [H ]
w
w
k K
dk d
k k
d d
k K
dk
k
d
+
+
+
+ + +
+ +

= + +
`
)
=

Setting this expression equal to zero will allow us to further simplify and isolate for [H ]
+
min.
OH
2 H
OH
2 H
2 OH
H
1
2
OH
H
0
[H ]
[H ]
[H ]
[H ]
w
w
w
w
k K
k
k K
k
k K
k
k K
k
+
+
+
+
+
+
+
+
=
=
=
| |
= |
|
\ .

10-75
10.30. Thefollowing results have been obtained by D. B. Dahlberg and F. A. Long [J. Amer. Chem. Soc., 95, 3825(1973)] for the base-catalyzed
enolization of 3-methyl acetone.

Catalyst ClCH2COO
CH3COO

2
4
HPO
Ka/mol dm
3
1.39 10
3
1.80 10
5
6.25 10
8

k/dm
3
mol
1
s
1
1.41 10
3
1.34 10
2
0.26

Estimate the Brnsted coefficient .

Solution:
Given: see above
Required: Brnsted coefficient
Recall that
14
[H ][OH ] 10
w
K
+
= = . Since we have been given the acid dissociation constants and we require the base dissociation constants given
by,
| |
[HB ][OH ]
B
b
K
+
= and
| |
A H
HA
a
K
+
( (

=
We can convert the acid dissociation constants into base dissociation constants by dividing 10
-14
by each value.
| |
[H ][OH ]
[H ]
A H
HA
+
+
+

( (

| | HA
[OH ]
A H
( (

| |
| | HA [OH ] [H ][OH ]
A H A
HA
+
+
( ( (

10-76
which can be expressed as:
| |
| |
HA [OH ] [HB ][OH ]
B A
b
K
+
=
(

We should also take the natural log of
b
K and k in order to plot themagainst each other. By doing this, we will produce a straight-line graph whose
slope is equal to the Brnsted coefficient.

Catalyst ClCH2COO
CH3COO

2
4
HPO
Kb 7.19 10
12
5.56 10
10
1.60 10
7

k
lnKb
lnk
1.41 10
3
-25.66
-6.56
1.34 10
2
-21.31
-4.31
0.26
-15.65
-1.35

10-77
Fromthe equation of the line generated by Microsoft Excels trendline option, we can see that the slope of the curve is equal to,
m 0.5206
m 0.52
=
= =

10-78
10.31. Suggest a plausible mechanismfor the bromination of acetone catalyzed by hydroxide ions. As with the acid-catalyzed reaction discussed in
Section 10.9, the rate is independent of the bromine concentration.

Solution:
Thehydroxide ion is assumed to abstract a proton fromthe acetone molecule, giving the ion CH3COCH2
-
, which exists in a resonant state. If its
resonance structure reacts rapidly with a bromine molecule, the rate is independent of the bromine concentration.


10-79
10.32. It was found by J . Halpern and coworkers [J. Phys. Chem., 60, 1455(1956)] that the rate equation for the oxidation of molecular hydrogen by
dichromate ions
2
2 7
(Cr O ) catalyzed by Cu
2+
ions is of the form:

2 2
2
2
2
[H ][Cu ]
[H ] [Cu ]
k
k
+
+
=
+

(**Note that the rate is independent of the concentration of dichromate ions.)
Suggest a mechanismconsistent with this behavior, and apply the steady-state treatment to obtain the rate expression. Comment on rate-
controlling steps corresponding to special cases of the mechanism.

Solution:
Since we know that the rate is independent of the concentration of dichromate ions, we will begin with the reaction that occurs between the hydrogen
molecule and Cu
2+
. This reaction can likely be said to reach equilibriumrapidly. Thebalanced reactions are as follows:
1
1
2
2
2
2
Cu H CuH H
CuH Cu 2Cu H
k
k
k
+ + +
+ + + +
+ +
+ +

We can assume that the second step is the rate controlling step. Also, it should be noted that a third reaction (rapid) takes place with the dichromate ion.
We will apply the steady state approximation for the CuH
+
ion.
| |
| |
| |
| |
2 2
1 2 1 2
CuH
2 2
1 2 1 2
2 2
1 2 1 2
2
1 2
CuH
Cu H CuH H CuH Cu
CuH
0
Cu H CuH H CuH Cu 0
Cu H CuH H CuH Cu
Cu H CuH
d
k k k
dt
d
dt
k k k
k k k
k
+
+
+ + + + +
+
+ + + + +
+ + + + +
+ +
(

( ( ( ( ( = =

(

=
( ( ( ( ( =

( ( ( ( ( = +

( ( =

( )
| |
( )
2
1 2
2
1 2
2
1 2
H Cu
Cu H
CuH
H Cu
k k
k
k k
+ +
+
+
+ +
( ( +

(

( =

( ( +

10-80
Theoverall rate can then bewritten as:
2
2
2Cu
CuH Cu k
+
+ +
( ( =

Making the appropriate substitutions into the above, we obtain,
| |
( )
2
1 2
2
2
2Cu 2
1 2
Cu H
Cu
H Cu
k
k
k k
+
+
+
+ +
(

( =

( ( +

This expression simplifies to the following:
| |
( )
2
2
1 2 2
2
1 2
H Cu
H Cu
k k
k k
+
+ +
(

=
( ( +


10-81
10.33. For the oxidation of molecular hydrogen by dichromate ions catalyzed by Ag
+
ions, A. H. Webster and J . Halpern [J. Phys. Chem., 60,
280(1956)] obtained the rate equation:

2
2 2
2
2
[H ][Ag ]
[H ][Ag ]
[H ] [Ag ]
k
k
k
+
+
+
= +
+

The existence of two terms suggests that two mechanisms are occurring in parallel. Suggest the two mechanisms, applying the steady-state
treatment to obtain the second termin the rate equation.

Solution:
In the previous problem, this particular reaction was catalyzed by copper ions (please refer back to it in order to review the reactions). However, here,
we can see fromthe overall rate equation that there is an additional term(which means that two mechanisms are occurring in parallel).
It is safe to assume that the first termin the rate equation derives froma single step reaction involving a single hydrogen molecule and two Ag
+
ions.
Normally, we would not suggest that the order of each species is directly related to the stoichiometric values, but we will make this assumption in this
particular case. We can write the reaction as follows:
| |
1
2
2
1 2
AgH
2Ag H 2AgH
' Ag H
k
k
+
+ +
+
+
( = =

This reaction can then be followed by the rapid reduction of the dichromate ion by the former product. Conversely, we can say that the AgH
+
is rapidly
oxidized by the dichromate ion. The next terms can be explained in the same way that the previous probleminvolving copper was.
2
2
3
2
Ag H AgH H
AgH Ag AgH Ag
k
k
k
+ +
+ +
+ +
+ +

Applying the steady-state approximation to reactions two and three we obtain,
10-82
| |
| | | | | |
| |
| | | | | |
| | | | | |
| | | |( )
AgH 2 2 2 3
2 2 2 3
2 2 2 3
2 2 2 3
AgH
Ag H AgH H AgH Ag
AgH
0
Ag H AgH H AgH Ag 0
Ag H AgH H AgH Ag
Ag H AgH H Ag
d
k k k
dt
d
dt
k k k
k k k
k k k
+ + +
+ + +
+ + +
+ + +
( ( ( = =

=
( ( ( =

( ( ( = +

( ( ( = +

| |
| |
( )
2 2
2 3
Ag H
AgH
H Ag
k
k k
+
+ +
(

=
( ( +

Theoverall rate equation can then be written as:
| |
3
AgH
AgH Ag k
+
+
( =

Making the substitution for the AgH molecule into the expression above, we obtain,
| |
( )
2 2
3
AgH
2 3
Ag H
Ag
H Ag
k
k
k k
+
+
+
+ +
(

( =

( ( +

This can bere-written as:
| |
( )
2
2 3 2
2 3
Ag H
''
H Ag
k k
k k
+
+ +
(

=
( ( +

Putting both rate equations together, we will obtain the true rate equation.
10-83
| |
| |
( )
2
2
2 3 2
1 2
2 3
' ''
H Ag
2 H Ag
H Ag
k k
k
k k

+
+
+ +
= +
(

( = +

( ( +


10-84
10.34. Thereaction:
Tl
+
+2Ce
4+
Tl
3+
+2Ce
3+
is catalyzed by Ag
+
ions. Under certain conditions the rate is proportional to
[Ce
4+
][Tl
+
][Ag
+
]/[Ce
3+
]
Suggest a mechanismconsistent with this behavior.

Solution:
We are given that,
4
3
Ce Tl Ag
Ce
+ + +
+
( ( (

(

and
4 3 3
Tl 2Ce Tl 2Ce
+ + + +
+ +
Since the overall rate equation consists of a ratio, we know that there must be more than a single reaction taking place. We can also guess that the first
reaction is a rapid equilibriumand the second reaction is the rate controlling step (slow). We are also told that there is a catalyst involved so this will
take part in the initial fast equilibriumreaction.
1
1
4 3 2
Ag Ce Ce Ag
k
k
+ + + +
+ +

Thenewly oxidized silver ion will then react with Tl
+
through an oxidation/reduction.
2
2 2
Ag Tl Tl Ag
k + + + +
+ +
Since we know that the silver can only stably return to the +1 oxidation state via oxidation/reduction, we know that there must be a third step that
involves
2
Tl
+
in order to bring it to the fully oxidized formof +3. This next reaction will occur fairly quickly. Fromthe first step, we can use the
remaining Ce
4+
as an oxidizing agent (which will in turn be reduced to Ce
3+
).
3
2 4 3 3
Tl Ce Tl Ce
k + + + +
+ +
Let us verify our assumptions by adding up all of the reactions and checking to see whether all of the reactants and products are satisfied.
10-85
Ag
+ 1
1
4 3 2
Ce Ce Ag
k
k
+ + +
+ +
2
Ag
+
2
2
Tl Tl
k + +
+ Ag
+
+
2
Tl
+ 3 4 3 3
4 3 3
Ce Tl Ce
2Ce Tl 2Ce Tl
k + + +
+ + + +
+ +
+ +

Recall that:
2 3
1
4
1
Ag Ce
Ag Ce
k
K
k
+ +
+ +
( (

= =
( (

Theoverall rate of the reaction will be defined by the limiting step and is therefore;
2
2
Ag Tl k
+ +
( ( =

Making the appropriate rearrangements and simplifications to eliminate Ag
2+
(by substitution fromthe equilibriumconstant expression) we obtain,

4
2
3
Ag Ce
Tl
Ce
K
k
+ +
+
+
( (

( =

(

This can bere-written in as,
4
1 2
3
1
Ag Ce Tl
Ce
k k
k
+ + +
+
( ( (

=
(

Thus proving that,
4
3
Ce Tl Ag
Ce
+ + +
+
( ( (

(

10-86
10.35. Thefollowing rates have been obtained for an enzyme-catalyzed reaction at various substrate concentrations:

10
3
[S]/mol dm
-3
Rate, /(arbitrary units)
0.4 2.41
0.6 3.33
1.0 4.78
1.5 6.17
2.0 7.41
3.0 8.70
4.0 9.52
5.0 10.5
10.0 12.5

Plot against [S], 1/ against 1/[S], and /[S] against , and fromeach plot estimate the Michaelis constant. Which plot appears to give the most
reliable value?

Solution:
In order to create all of these plots, let us first write out a table that includes all of the values that we will be required to use.

10
3
[S] (mol dm
-3
) 1/ 1/[S] (10
-3
mol dm
-3
) /[S] (10
-3
mol dm
-3
)
0.4 2.41 0.4149 2.500 6.025
0.6 3.33 0.3003 1.667 5.550
1.0 4.78 0.2092 1.000 4.780
1.5 6.17 0.1621 0.667 4.113
2.0 7.41 0.1350 0.500 3.705
3.0 8.7 0.1149 0.333 2.900
10-87
4.0 9.52 0.1050 0.250 2.380
5.0 10.5 0.0952 0.200 2.100
10.0 12.5 0.0800 0.100 1.250

Plot 1: against [S]

TheMichaelis-Menten equation (Eq. 10.82) states that,
v max
Km
10-88
| |
| |
max
S
S
m
K
=
+

In this expression, Km =MichaelisMenten rate constant, [S] =substrate concentration, v =initial rate of production of the product, and v max =
maximuminitial rate of production of the product.
Notice that this plot produces a curved line which is not easy to work with. It essentially produces a saturation curve which is mostly only useful to
examine the relationship between the concentration of substrate and the rate of reaction. Here, we would need to look at the steepest part of the slope
which we can call a straight line. The highest point of this straight line would be equal to v
max. Fromthis point (v max), we could then draw a
straight line down to the x-axis. This gives us the value of the Michaelis-Menten rate constant, Km.
As you can guess, this particular method is not going to provide the most accurate or precise results due to the fact that there is a lot of guesswork and
estimation involved. Fromthe plot above, we have determined that
3 3
2 10 mol dm
m
K

.

Plot 2: 1/ against 1/[S]

10-89

| |
| |
max
S
S
m
K
=
+

Thetype of plot that you see here is called a double reciprocal plot. It is quite often used in enzyme kinetics and therefore the student should become
acquainted with this type of curve. Double reciprocal plots give us two pieces of critical information, v
max and 1/Km. They give us this information in
terms of y and x-intercept respectively. They can therefore be determined quite reliably (especially when using graphing programs). It is also interesting
to examine plots for enzyme inhibition at a variety of concentrations in order to see the effects on v max and 1/Km (usually as the concentration increases).
Double reciprocal plots also by their shape- allow us to determine the type of enzyme inhibition/catalysis occurring in our experiment.
v max
1/Km
10-90
This plot has told us that, 1/ 0.5
m
K = therefore,
1
3 3
0.5 2 10 mol dm
m m
K K

= =
Plot 3: /[S] against

| |
| |
max
S
S
m
K
=
+

10-91
Thefinal plot above produces a beautiful straight line graph which will allow us to performa linear regression and obtain the exact value for the
Michaelis-Menten rate constant. Since we have plotted /[S] against , we can use the Michaelis-Menten equation to help us determine what we need to
be looking for on the plot to give us our K
m value. It turns out that the slope of this plot allows us to determine Km.

Upon performing a linear regression (using Microsoft Excels linest function) we obtain the following regression statistics:
m -0.479 7.123 b
Sm 0.011 0.087 Sb
R
2
0.996 0.104 Sy
F 1924.562 7 DF

Thenumerical value in the first row and column provides the exact value of the slope (for the third curve). Therefore,
1
3 3
1/ 0.479
0.479
2.09 10 mol dm
m
m
m
K
K
K

=
=
=

So what is the difference between the second and third curves? As can be seen, the second plot is highly sensitive to increasingly large values of [S]
because there is bunching and crowding of the data points in that range. Looking at the far right of the plot, we can see that the double reciprocal
method is less sensitive to small values of [S] and therefore does not produce an evenly populated curve.
Thethird curve is actually the best since it is both evenly populated and allows for proper statistical analysis such as a linear regression. Using the linear
regression method, it is possible to determine (more precisely and accurately) the value for the Michaelis-Menten rate constant. It is the preferred
method when working quantitatively in enzyme catalysis.


10-92
10.36. Thefollowing data have been obtained for the myosin-catalyzed hydrolysis of ATP, at
25 C and pH 7.0.
10
5
[ATP]/mol dm
3
10
6
/mol dm
3
s
1

7.5 0.067
12.5 0.095
20.0 0.119
32.5 0.149
62.5 0.185
155.0 0.191
320.0 0.195

Plot against [S], 1/ against 1/[S], and /[S] against , and fromeach plot calculate the Michaelis constant Km and the limiting rate V.

Solution:
We will use the same method in this problemas we did in the previous.

10
5
[ATP]/mol dm
3
10
6
/mol dm
3
s
1
1/ 1/[S] /[S]
7.5 0.067 14.925 0.133 8.933E-03
12.5 0.095 10.526 0.080 7.600E-03
20.0 0.119 8.403 0.050 5.950E-03
32.5 0.149 6.711 0.031 4.585E-03
62.5 0.185 5.405 0.016 2.960E-03
155.0 0.191 5.236 0.006 1.232E-03
10-93
320.0 0.195 5.128 0.003 6.094E-04

Note that the limiting rate here is actually v max in plots two and three and is better described as twice the value at which saturation occurs in the first
plot.

Plot 1: against [ATP]

5 3
16.7 10 mol dm
m
K

and
6 3 1
max
0.22 10 mol dm s v

Plot 2: 1/ against 1/[ATP]
v max

Km

10-94

1
5 3
6 3 1
max max max
1/ 0.06 0.06 16.67 10 mol dm
1/ 4.7 1/ 4.7 0.21 10 mol dm s
m m m
K K K
v v v
= = =
= =

Plot 3: /[ATP] against
v max
1/Km
10-95

Linear regression statistics:
m -0.061 0.013 b
Sm 0.005 0.001 Sb
R
2
0.968 0.001 Sy
F 149.196 5 DF

Thenumerical value located in the first row and column provides us with the value for the slope. As we have previously seen, the slope is equal to
1/
m
K therefore,
1
5 3
1/ 0.061
0.061
16.39 10 mol dm
m
m
m
K
K
K

=
=
=

v max/Km

v max
10-96
Fromthe plot above, we can see that,
6 3 1
max
0.22 10 mol dm s v

=

10-97
*10.37. The following values of V (limiting rate at high substrate concentrations) and Km have been obtained at various temperatures for the hydrolysis
of acetylcholine bromide, catalyzed by acetylcholinesterase.
.
T/C 10
6
V/mol dm
3
s
1
Km 10
4
/mol dm
3

20.0
1.84 4.03
25.0 1.93 3.75
30.0 2.04 3.35
35.0 2.17 3.05

a. Assuming the enzyme concentration to be 1.00 10
11
mol dm
3
, calculate the energy of activation, the enthalpy of activation, the Gibbs
energy of activation, and the entropy of activation for the breakdown of the enzyme-substrate complex at 25 C.
b. Assuming Km to be the dissociation constant k1/k1 for the enzyme-substrate complex
1
1
(ES E S),
k
k
+ determine the following
thermodynamic quantities for the formation of the enzyme-substrate complex at 25 C: G, H, S.
c. Fromthe results obtained in parts (a) and (b), sketch a Gibbs energy diagramand an enthalpy diagramfor the reaction.

Solution:
Remember that we should change the temperature units to Kelvin! We will now construct a table that includes all of the values that we will need to
generate the desired plots.
T (K) V (mol dm
-3
s
-1
) Km (mol dm
-3
) 1/T (K) Log10(V) (mol
dm
-1
s
-1
)
Log10(Km) (mol
dm
-3
)
293 1.84E-06 4.03E-04 3.413E-03 -5.735 -3.395
298 1.93E-06 3.75E-04 3.356E-03 -5.714 -3.426
303 2.04E-06 3.35E-04 3.300E-03 -5.690 -3.475
308 2.17E-06 3.05E-04 3.247E-03 -5.664 -3.516

10-98
a) Slope of plot of log10V against 1/T=-430.9K

1
1
o 1 1
1
ln10 slope
19.14 430.9 8247.426 J mol
8.25 kJ mol
at 25C =8.314 298 =2478 J mol 2.48 kJ mol
8.25 2.48
5.77 kJ mol
E R
E
E
RT
H E RT
H
H
=
= =
=
=
=
=
=

10-99
1
1
1 1
19.14 7.51 298.15
42 864.76 623 J mol
42.9 kJ mol
5700 42 856
298.15
124 J K mol
G
G
G
S
S

=
=
=
=
=

| |
| |
( )
o 6 3 1 1
11 3
0
5 1
0
23 2
o B B
At 25.0C, 1.93 10 dm mol s
E 1.0 10 mol dm
/ E 1.93 10 s
1.3806503 10 m kg
exp / ; at 25.0C
c
c
V
k V
k T k T
k G RT
h h

=
=
= =
= =
2
s
1
K
298 K
34 2
6.626 10 m kg / s
( )
12 1
5 1
B
6.21 10 s
1.93 10 s
exp /
c
h
G RT k
k T
= =
12 1
6.21 10 s
( ) ( )
( )
( ) ( )
8 7.51

7.51
3.108 10 10
ln exp /
ln 10 8.314 298.15
ln 10 7.51 8.314 298.15
G G RT RT
G
G

= =
=
=
=

b) Slope of log10Km against 1/T plot=742.91

10-100

( )
o
o
o 1
o 1
o
10
o
(for dissociation) ln10 slope
(for dissociation) 19.14 742.91
(for dissociation) 14 219.2974 J mol
(for dissociation) 14.2 kJ mol
At 25.0C, log 3.426
(for dissociation) l
m
H R
H
H
H
K
G
=
=
=
=
=
= ( )
o
o 1
n
(for dissociation) 19.14 298.15 3.426
(for dissociation) 19 550.78 077 J mol
m
K RT
G
G

=
=
10-101
o 1
o 1
For association,
19.6 kJ mol
14.2 kJ mol
G
H
=
=

o o
o 1 1
o 1 1
14 219 19 551
113.265 135 J K mol
298.15
113.3 J K mol
G H
S
T
S

+ +
= = =
=

c)

10-102
*10.38. The following data relate to an enzyme reaction:
10
3
[s]/mol dm
3
10
5
V/mol dm
3
s
1

2.0 13
4.0 20
8.0 29
12.0 33
16.0 36
20.0 38

Theconcentration of the enzyme is 2.0 g dm
3
, and its molecular weight is 50 000 g/mol. Calculate Km, the maximumrate V, and kc.

Solution:
Given:
3 1
2.0 g dm , M 50 000 g mol C

= =
Required: determine Km, the maximumrate V, and kc.

10
3
[s] (mol dm
-3
) 10
5
V (mol dm
-3
s
1
) 1/[s] (1/mol dm
-3
) 1/V (1/ mol dm
-3
s
1
)
2 13 500 7692
4 20 250 5000
8 29 125 3448
12 33 083 3030
16 36 62.5 2778
20 38 50.0 2630

10-103

Theequation of the line generated is:
11.291 2081.8 y x = +
This means that 1/v max is equal to the y-intercept, thus,
1 3
max
1 3
max
4 3 1
max
1/ 2081.8 mol dm s
1/ 2081.8 mol dm s
4.804 10 mol dm s
v
v
v

=
=
=

Conversely, the value for 1/K
m is equal to the x-intercept which can be determined by looking at the plot above (or by setting y =0 and solving for x).
1/Km
1/v max
10-104
1
3 3
11.291 2081.8
11.291 2081.8 0
11.291 2081.8
2081.8
11.291
1/ 184.3769374
184.3769374
5.42 10 mol dm
m
m
m
y x
x
x
x
x K
K
K

= +
+ =
=
=
= =
=
=

It should be remembered that the Eq. 10.82 is not always the best way to represent the rate for a particular reaction. When we know that the Michaelis-
Menten equation can be applied but we are unsure of the mechanism, we should use Eq. 10.85 which state that:
| | | |
| |
o
E S
S
c
m
k
K
=
+

It is possible to then say that,
| |
| |
max
o
max
o
E
E
c
c
k
k
=
=

Let us now determine the value of the enzyme concentration.
| |
o
2 g
E =
3
dm
50 000 g
| |
1
5 3
o
mol
E 4.0 10 mol dm

=

10-105
4 3
4.804 10 mol dm
c
k

=
1
5 3
s
4.0 10 mol dm

1
12.01 s
c
k =


10-106
10.39. Thefollowing data have been obtained for the myosin-catalyzed hydrolysis of ATP.
Temperature/C kc 10
6
/s
1

39.9 4.67
43.8 7.22
47.1 10.0
50.2 13.9

Calculate, at 40 C, the energy of activation, the enthalpy of activation, the Gibbs energy of activation, and the entropy of activation.

Solution:
Given: see table above
Required:
H,
S, and
G at 40 C
Recall that,
/
e
ln ln
a
E RT
a
k A
E
k A
RT
=
=

So we can plot
1
ln vs. k
T
in order to determine the activation energy (which appears in the slope portion of the equation for the line). The k that
will be used is actually kc.
10-107

T /C T / K 1/T K
-1
kc /s
1
lnkc
39.90 313.05 3.19E-03 4.67E-06 -12.274
43.80 316.95 3.16E-03 7.22E-06 -11.839
47.10 320.25 3.12E-03 1.00E-05 -11.513
50.20 323.35 3.09E-03 1.39E-05 -11.184

Fromthe equation of the line, we see that the slope is m=-10 657. Fromthis, we can determine the activation energy.
m 10 567
10 567 K
a
a
E
R
E
= =
=
( )
1
8.3145 J K
( )
1
1
1
mol
87859 J mol
87.9 kJ mol
a
a
E
E
=
=

10-108
Fromthe previous chapter we know that,
a
H E RT = therefore,
1 1
87859 J mol 8.3145 J K H

=
( )
1
mol 313.15 K
( )
1
1
85 255 J mol
85.26 kJ mol
H
H
=
=

Also, we know that,
B
e
G
RT
c
k T
k
h

=
Which can be rearranged to solve for
G.
B
1
ln ln
ln ln
8.3145 J K
c
c
k T G
k
h RT
k T G
k
RT h
G

=

=
=
( )
1
mol 313.15 K
( )
23
1.381 10 J
ln

1
K
( )
313.15 K
( )
34
6.626 10 J
( )
( )
6 1
ln 4.72 10 s
s

| |
|

|
|
\ .

( )( )
1
2603.686 J mol 41.771 G

=
1
1
108 758 J mol
108.8 kJ mol
G
G
=
=

Using the equation

G H T S = we can determine the value for the entropy of activation.
10-109
( )

1 1
85 255 108 758 J mol
313.15 K
75.05 kJ K mol
T S H G
H G
S
T
S
S

=

=
=
=

10-110
*10.40. The following is a simplified version of the mechanismthat has been proposed by H. Theorell and Britton Chance for certain enzyme reactions
involving two substrates A and B.

Assume that the substrates A and B are in excess of E so that the steady-state treatment can be applied to EA and EZ, and obtain an expression
for the rate.

Solution:
Given: see above
Required: overall rate equation
Applying the steady-state approximation for EA, we obtain,
| |
| || | | | | || |
| |
| || | | | | || |
EA 1 1 2
1 1 2
EA
E A EA EA B
EA
0
E A EA EA B 0
d
k k k
dt
d
dt
k k k
= =
=
=

Applying the steady-state approximation for EZ, we obtain,
| |
| || | | |
| |
| || | | |
EZ 2 3
2 3
EZ
EA B EZ
EZ
0
EA B EZ 0
d
k k
dt
d
dt
k k
= =
=
=

We can now formulate an equation representing the initial concentration of the enzyme.
10-111
| | | | | | | |
o
E E EA EZ = + +
With this, it is obvious that the steady-state approximation for EA should be solved for E so that it can be expressed in terms of EA and substituted into
the equation for the initial concentration of the enzyme.
| || | | | | || |
| |
| | | || |
| |
1 1 2
1 2
1
E A EA EA B
EA EA B
E
A
k k k
k k
k
= +
+
=

| |
| | | || |
| |
| | | |
1 2
o
1
EA EA B
E EA EZ
A
k k
k
+
= + +
Thesteady-state approximation for EZ should be solved for EZ in order to express it in terms of EA which can also be substituted into the equation
representing the initial concentration of the enzyme.
| || | | |
| |
| || |
| |
| | | || |
| |
| |
| || |
2 3
2
3
1 2 2
o
1 3
EA B EZ
EA B
EZ
EA EA B EA B
E EA
A
k k
k
k
k k k
k k
=
=
+
= + +

Thefinal expression above can be factored which yields,
| | | |
| |
| |
| |
1 2 2
o
1 3
B B
E EA 1
A
k k k
k k
+

= + +
`

)

Theoverall rate is given by,
| || |
2
EA B k =
Therefore,
10-112
| |
| |
| |
| |
| |
| |
| |
| |
| |
| |
| | | |
| |
| |
| |
o
1 2 2
1 3
o
2
1 2 2
1 3
2
o
1 2 2
1 3
E
EA
B B
1
A
E
B
B B
1
A
E B
B B
1
A
k k k
k k
k
k k k
k k
k
k k k
k k
=
+
+ +
`

)
=
+
+ +
`

)
=
+
+ +
`

)

This can besimplified to the following expression:
| || | | |
| | | | | || |
1 2 3
o
1 3 1 3 2 3 1 2
A E B
A B A B
k k k
k k k k k k k k
=
+ + +

10-113
*10.41. When an inhibitor I is added to a single-substrate enzyme system, the mechanismis sometimes:

This is known as a competitive mechanism, since S and I compete for sites on the enzyme.
a. Assume that the substrate and inhibitor are present in great excess of the enzyme, apply the steady-state treatment, and obtain the rate
equation.
b. Obtain an expression for the degree of inhibition defined as:
0
0

where is the rate in the presence of inhibitor and 0 is the rate in its absence.

Solution:
a) We will apply the steady-state approximation to both ES and EI.
| |
| || | | | | |
| |
| || | | | | |
| |
| || | | |
| |
| || | | |
ES 1 1 2
1 1 2
EI
ES
S E ES ES
ES
0
S E ES ES 0
EI
I E EI
EI
0
I E EI 0
i i
i i
d
k k k
dt
d
dt
k k k
d
k k
dt
d
dt
k k
= =
=
=
= =
=
=

Solving the first equation for ES we obtain,
10-114
| |
| || |
1
1 2
S E
ES
k
k k
=
+

Solving the second equation for EI we obtain,
| || | | |
| |
| || |
I E EI
I E
EI
i i
i
i
k k
k
k
=
=

Solving the first equation again but this time in order to isolate E;
| || | | | | |
| || | | |( )
| |
| |( )
| |
1 1 2
1 1 2
1 2
1
S E ES ES
S E ES
ES
E
S
k k k
k k k
k k
k
= +
= +
+
=

Theinitial enzyme concentration is given by,
| | | | | | | |
o
E E ES EI = + +
Substituting the expressions found for E, ES and EI we obtain to following:
| |
| |( )
| |
| |
| || |
1 2
o
1
ES I E
E ES
S
i
i
k k k
k k
+
= + +
However, we can see here that we cannot further simplify this expression due to the presence of E. In order to eliminate this term, we can performthe
following operations:
10-115
| |
| |
| |( )
| |
| |
| || |( )
| |
| |
| |( )
| |
| |
| || |( )
| |
1 2
1
1 2
1
1 2 1 2
o
1 1
ES
I
S
EI
I ES
EI
S
ES I ES
E ES
S S
i
i
i
i
i
i
k k
k
k
k
k k k
k k
k k k k k
k k k
+
=
+
=
+ +
= + +

We will now factor out the ES termto obtain,
| | | |
( )
| |
| |( )
| |
1 2 1 2
o
1 1
I
E ES 1
S S
i
i
k k k k k
k k k

+ +

= + +
`

)

| |
2
ES k =

Written in terms of the initial concentration of enzyme the rate equation becomes,
| |
( )
| |
| |( )
| |
2
o
1 2 1 2
1 1
E
I
1
S S
i
i
k
k k k k k
k k k
=
+ +
+ +

It is possible to further simplify the denominator by multiplying all terms by the concentration S.
| | | |
( )
| |
| | ( )
2
o
1 2 1 2
1 1
E S
I
S
i
i
k
k k k k k
k k k
=
+ +
+ +

Let us combine the terms in the denominator,
10-116
( ) ( )
| | | |
( )
| |
| |
| | | |
| |
| |
1 2 1 2
1 1
1 2
1
2
o
I S
Recall that, and therefore,
I
1 S
E S
I
1 S
i
i
i
m i
i
m
i
m
i
k k k k k
k k k
k k k
K K
k k
K
K
k
K
K

+ +
+ +
+
= =
| |
+ +
|
\ .
=
| |
+ +
|
\ .

b) Given that
0
0

= ,
| | | |
| |
| |
| | | |
| |
| |
| | | |
0
0 0 0
2 o
2 o 2 o
1
E S
I
1 S
S
1
E S
E S
S
m
i m
m
k
K
K K
k
k
K

=
| |
+ +
|
+
\ .
=
+
| | | |
2 o
E S k
| |
| |
I
1 S
m
i
K
K
| |
+ +
|
\ .

10-117
| |
| |
| |
| |
| |
| |
S
1
I
1 S
I
I
1 S
m
m
i
m
i
m
i
K
K
K
K
K
K
K
+
=
| |
+ +
|
\ .
=
| |
+ +
|
\ .

10-118
*10.42. Obtain the rate equation corresponding to the mechanism:

Assume ES and ES to be in the steady state and the substrate concentration to be much higher than the enzyme concentration. Express the
catalytic constant kc and the Michaelis constant Km in terms of k1, k1, k2, and k3.

Solution:
Given: see mechanismabove
Required: overall rate equation
We will solve this problemin a similar manner as we did for the previous one. Let us begin by applying the steady-state treatment for ES and ES.
10-119
| |
| || | | | | |
| |
| || | | | | |
| || | | |( )
| |
| || |
| |
| |( )
| |
| |
| | | |
| |
| | | |
| |
| |
| | | | | | | |
| |
| |( )
| |
| |
| |
| | | |
( )
| |
ES 1 1 2
1 1 2
1 1 2
1
1 2
1 2
1
ES' 2 3
2 3
2
3
o
1 2 2
o
1 3
1 2 2
o
1 3
ES
S E ES ES
ES
0
S E ES ES
S E ES
S E
ES
ES
E
S
ES'
ES ES'
ES'
0
ES ES'
ES
ES'
E E ES ES'
ES ES
E ES
S
E ES 1
S
d
k k k
dt
d
dt
k k k
k k k
k
k k
k k
k
d
k k
dt
d
dt
k k
k
k
k k k
k k
k k k
k k
= =
=
= +
= +
=
+
+
=
= =
=
=
=
= + +
+
= + +
+

= + +
`

)

10-120
| |
| |
( )
| |
| | | |
| |
| |
| |
2
2 o
1 2 2
1 3
2 3
o
2 3
1 2 3
1 2 3
1 2
o
1 2
1 2
1 2
ES
E
1
S
E S
S
When S is large
E
and the catalytic constant is therefore
is the first termin the denominator of the rate equation
c
m
k
k
k k k
k k
k k
k k
k k k
k k k
k k
k k
k k
k
k k
K
=
=
+
+ +
+
=
+
+
+
=
+
=
+
1 2 3
1 2 3
:
m
k k k
K
k k k
+
=
+

10-121
*10.43. Enzyme-catalyzed reactions frequently follow an equation of the formof Eq. 10.85. Suppose that kc and Km show the following temperature
dependence:

k
c =Ac exp(Ec/RT ) and Km =B exp(Hm /RT )
where Ac, B, Ec, and Hm are temperature-independent parameters. Explain under what conditions, with [S] held constant, the rate may pass
through a maximumas the temperature is raised.

Solution:
Given: Eq. 10.85, kc =Ac exp(Ec/RT ) and Km =B exp(Hm /RT )
Required: when is [S] held constant?
Suppose that H
m is positive:
Km will then increase accordingly with an increase in temperature (linearly) and at sufficiently low temperature it will be much smaller that the
concentration of the substrate. Theeffective activation energy is therefore given by Ec and its rate will increase as thetemperature increases.
At sufficiently high temperatures, Km will be much larger than the concentration of the substrate and the effective activation energy will be given by Ec -
Hm.
If Hm is larger than Ec, effective activation energy will be negative. This would mean that the rate has gone through a maximumas the temperature
was increased.
If H
m is smaller than Ec, effective activation energy will be positive. This does not indicate that the rate has gone through a maximum! However, the
observed activation energy will be lower at higher temperatures. An Arrhenius plot will therefore show curvature (ie. bending away fromthe axes).

10-122
10.44. Some enzyme reactions involving two substrates A and B occur by the following mechanism:

(This is known as the ordered ternary-complex mechanism; A must add first to E, and the resulting complex EA reacts with B; the complex EB
is not formed.)
Theconcentrations of A and B are much greater than the concentration of E. Apply the steady-state treatment and obtain an expression for the
rate.

Solution:
Since we are told that the concentrations of A and B are much greater than the concentration E, we can apply the steady-state treatment to complexes EA
and EAB.
| |
| || | | | | || |
| |
| || | | | | || |
| || | | | | | ( )
| |
| || |
| | ( )
| |
| | | | ( )
| |
EA 1 1 2
1 1 2
1 1 2
1
1 2
1 2
1
EA
E A EA EA B
EA
0
E A EA EA B
E A EA B
E A
EA
B
EA B
E
A
d
k k k
dt
d
dt
k k k
k k k
k
k k
k k
k
= =
=
= +
= +
=
+
+
=

1
1
3 2
E A EA
EA+B EAB E Y Z
k
k
k k
+
+ +

10-123
| |
| || | | |
| |
| || | | |
| |
| || |
| |
| |
| |
EAB 2 3
2 3
2
3
3
2
EAB
EA B EAB
EAB
0
EA B EAB
EA B
EAB
EAB
EA
B
d
k k
dt
d
dt
k k
k
k
k
k
= =
=
=
=
=

Since | | | | | | | |
o
E E EA EAB = + + then we can write:
| |
| | | | ( )
| |
| |
| |
| |
| |
| |
| |
| | ( )
| |
| |
| |
| |
| |
| | | | ( )
| | | |
| |
| |
| |
| | | |
| | ( )
| | | | | |
1 2 3
o
1 2
3
1 2
2 3
o
1 2
3 1 2 3
o
2 1 2
3 1 2
3
o
2 1 2
EA B EAB
E EAB
A B
EAB
B
B EAB
E EAB
A B
EAB B EAB
E EAB
B A B
B
E EAB 1
B A B
k k k
k k
k
k k
k k
k k
k k k k
k k k
k k k
k
k k k
+
= + +
+
= + +
+
= + +
+

= + +
`

)

| |
3
EAB k =
Which can be written in the following manner:
10-124
| |
| |
| | ( )
| | | | | |
| |
| | ( )
| | | | | |
| | | || |
| | ( ) | | | || |
o
3 1 2
3
2 1 2
3 o
3 1 2
3
2 1 2
1 2 3 o
3 1 2 3 1 1 2
E
EAB
B
1
B A B
E
B
1
B A B
E A B
B A B A
k k k
k
k k k
k
k k k
k
k k k
k k k
k k k k k k k
=
+
+ +
=
+
+ +
=
+ + +


10-125
10.45. The following ping-pong mechanismappears sometimes to apply to an enzyme-catalyzed reaction between two substrates A and B to give the
final products Y and Z:

1 2
1
3 4
E A EA EA +Y
EA +B EA B E Z
k k
k
k k
+
+

It can be assumed that the substrates are present in great excess of the enzyme and that steady-state conditions apply. Obtain an expression for
the rate of reaction.

Solution:
Let us apply the steady-state approximation to EA, EA and EAB. This procedure yields;
10-126
| |
| || | | | | |
| |
| || | | | | |
| || | | | | |
| || | | |( )
| |
| | | || |
| |
| | | || |
| | | || |
| |
| || | | |
| |
| || | | |
| || | | |
EA 1 1 2
1 1 2
1 1 2
1 1 2
EA' 2 3
2 3
2 3
EA'B 3 4
3 4
3 4
EA
E A EA EA
EA
0
E A EA EA 0
E A EA EA
E A EA
EA'
EA EA' B
EA'
0
EA EA' B 0
EA EA' B
EA'B
EA' B EA'B
EA'B
0
EA' B EA'B 0
EA' B EA'B
d
k k k
dt
d
dt
k k k
k k k
k k k
d
k k
dt
d
dt
k k
k k
d
k k
dt
d
dt
k k
k k
= =
=
=
= +
= +
= =
=
=
=
= =
=
=
=

Since the overall rate equation is given by,
| || |
3
EA' B k =
We should define the initial enzyme concentration in terms as of EA but making the appropriate substitutions and rearrangements.
10-127
| | | | | | | | | |
| || | | |( )
| |
| |( )
| |
| | | || |
| |
| || |
| || | | |
| |
| || |
| |
| |( )
| |
| || |
| |
| || |
o
1 1 2
1 2
1
2 3
3
2
3 4
3
4
1 2 3 3
o
1 2 4
E E EA EA' EA'B
E A EA
EA
E
A
EA EA' B
EA' B
EA
EA' B EA'B
EA' B
EA'B
EA EA' B EA' B
E EA'
A
k k k
k k
k
k k
k
k
k k
k
k
k k k k
k k k
= + + +
= +
+
=
=
=
=
=
+
= + + +

Since the first termdoes not involve EA, we will need to make a second substitution.
| |( )
| |
| || |
( )
| |
( )| || |
| |
| |
( )
| |
| |
| | | |
( )
| |
| | | || |
| |
| || |
| | | |
( )
| |
| | | | | |
3
1 2
1 2 3 1 2 1 2 3 2
1 1 2 1 1 2
1 2 3 3 3
o
1 2 2 4
1 2 3 3 3
o
1 2 2 4
EA' B
EA EA' B B
or EA'
A A A A
B EA' B EA' B
thus, E EA' EA'
A
B B B
E EA' 1
A
k
k k
k k k k k k k k k
k k k k k k
k k k k k
k k k k
k k k k k
k k k k
+
+ + +
=
+
= + + +
+
= + + +
`

)

| || |
3
EA' B k =
10-128
| | | |
( )
| |
| | | | | |
3
o
3 3 3 1 2
1 2 2 4
E B
B B B
1
A
k
k k k k k
k k k k
=
+
+ + +

Simplification yields,
| | | || |
| | ( )| | ( )| || |
1 2 3 4 o
1 2 4 3 4 1 2 1 3 2 4
E A B
A B A B
k k k k
k k k k k k k k k k k
=
+ + + +

10-129
10.46. Thepolymerization of styrene [M] catalyzed by benzoyl peroxide [C] obeys a kinetic equation of the form:

Obtain an expression for the kinetic chain length, in terms of [M], [C], and the rateconstants for initiation, propagation, and termination.

Solution:
Given:
3/2 1/2
[M]
[M] [C]
d
k
dt
=
Required: expression for the kinetic chain length
Eq. 10.97,
| |
| | | |
1
3 1 2
2 2
M
M C
i
p
t
d k
k
dt k
| |
=
|
\ .

defines the polymerization rate for the rate of initiation, | || | M C
i i
k = (Eq. 10.96). The chain length is therefore equal to,
| |
| |
1
2
1
2
M
C
p
i
t
k
k
k
| |
|
\ .

10-130
10.47. Thepolymerization of ethylene [M] photosensitized by acetone occurs by the mechanism:

CH3COCH3
hv
CO +2CH3

CH
3 +C2H4
p
k
CH3CH2CH2

CH3CH2CH2 +C2H4
p
k
CH3CH2CH2CH2CH2

R
n +Rm
r
k
Mn +m

where one quantumgives 2CH3.
Show that the rate equation is:
1/2
[M] 2
[M]
p
t
d I
k
dt k
| |
=
|
\ .

where I is the intensity of light absorbed and kp and kt arethe rate constants for the propagation and termination steps, respectively.

Solution:
Given: rate of formation of CH3 is 2I
Required: see above
Thesteady-state equations are
| || | | | | |
| || | | || | | | | |
3 3
3 3 2 2 3 2 2
2 CH M CH R 0
FromEq. 20.2,
CH M CH CH CH M CH CH CH R 0
p t n
p p t n
I k k
k k k
=
=

and so on.
Thesumof all the equations is
10-131
| | ( )
| |
2
1
2
2 R 0
so that
2
R
t n
n
t
I k
I
k
=
| |
=
|
\ .

| | | |
| |
1
2
the rate of removal of monomer is
[M]
M R
[M] 2
M
p n
p
t
d
v k
dt
d I
k
dt k
= =
| |
=
|
\ .


CHAPTER
1
1
1
1
Quantum Mechanics
and Atomic Structure

Physical Chemistry
Electronic Edition


Chapter 11: Quantum Mechanics and Atomic Structure Electromagnetic Radiation and Wave Motion
11-2
Chapter 11
Electromagnetic Radiation and Wave Motion
11.1. Calculate, for light of 325 nmwavelength,
a. the frequency;
b. the wavenumber;
c. the photon energy in J , eV, and kJ mol
1
; and
d. the momentumof the photon.
Solution
11.2. A pulsar in the Crab Nebula, NP 0532, emits both radio pulses and optical pulses. A radio pulse is observed at 196.5 Mhz. Calculate
a. the corresponding wavelength;
b. the energy of the photon in J , eV and J mol
1
; and
c. the momentumof the photon.
Solution
11.3. The potassiumspectrumhas an intense doublet with lines at 766.494 nmand 769.901 nm. Calculate the frequency difference
between these two lines.
Solution
11.4. Suppose that the position y of a particle that travels along the Y axis of a coordinate systemis given by
( )
0
3 rad
sin
5
t
y t y C
s
( | |
= +
| (
\ .

What is the frequency of the wave motion?
Solution
11.5. A mass of 0.2 kg attached to a spring has a period of vibration of 3.0 s.
a. What is the force constant of the spring?
b. If the amplitude of vibration is 0.010 m, what is the maximumvelocity?
Solution
Chapter 11: Quantum Mechanics and Atomic Structure Particles and Waves
11-3
*11.6. If the average energy associated with a standing wave of frequency in a cavity is
( )
B
exp / 1
h
h k T

deduce the expression for the low-frequency limit of the average energy associated with the standing wave.
Solution
Particles and Waves
11.7. A sodiumlamp of 50-watt power emits yellow light at 550 nm. How many photons does it emit each second? What is the
momentumof each photon?
Solution
11.8. The threshold frequency 0 for emission of photoelectrons frommetallic sodiumwas found by Millikan, Phys. Rev., 7, 1916, p. 362,
to be 43.9 10
13
s
1
. Calculate the work function for sodium. A more recent value, for a carefully outgassed sample of sodium, is 5.5
10
13
s
1
. What work function corresponds to that value?
Solution
11.9. Calculate the value of the de Broglie wavelength associated with
a. an electron moving with a speed of 6.0 10
7
ms
1
(this is the approximate velocity produced by a potential difference of 10 kV).
b. an oxygen molecule moving with a speed of 425 ms
1
at 0 C.
c. an -particle emitted by the disintegration of radium, moving at a speed of 1.5 10
7
ms
1
.
d. an electron having a speed of 2.818 10
8
ms
1
.
Solution
11.10. Consider a colloidal particle with a mass of 6 10
16
kg. Suppose that its position is measured to within 1.0 nm, which is about the
resolving power of an electron microscope. Calculate the uncertainty in the velocity and comment on the significance of the result.
Solution
Chapter 11: Quantum Mechanics and Atomic Structure Particles and Waves
11-4
11.11. Calculate the velocity and the de Broglie wavelength of an electron accelerated by a potential of
a. 10 V,
b. 1 kV, and
c. 1 MV.
Solution
*11.12. The group velocity of a wave is given by the equation
( ) 1/
g
d
v
d
=
Prove that the group velocity of a de Broglie particle wave is equal to the ordinary velocity of the particle.
Solution
11.13. Photoelectric experiments show that about 5 eV of energy are required to remove an electron fromplatinum.
a. What is the maximumwavelength of light that will remove an electron?
b. If light of 150 nmwavelength were used, what is the velocity of the emitted electron?
Solution
11.14. Calculate the kinetic energy of an electron that has a wavelength of (a) 10 nm, (b) 100 nm.
Solution
11.15. Calculate the de Broglie wavelength of (a) an -particle (a heliumnucleus) accelerated by a field of 100 V, and (b) a tennis ball
served at 220 kmh
1
. (An -particle has a mass of 6.64 10
27
kg and a diameter of about 10
15
m. A standard tennis ball has a mass
of 55.4 g and a diameter of 6.51 cm.)
Solution
Chapter 11: Quantum Mechanics and Atomic Structure Quantum-Mechanical Principles
11-5
Quantum-Mechanical Principles
11.16. Assume that the three real functions 1,

2, and 3 are normalized and orthogonal. Normalize the following functions:
a. 1+2
b. 1

2
c. 1+2+3
d.
1 2 3
1 3
2 2
+
Solution
11.17. Is the function Ae
ax
an eigenfunction of the operator d
2
/dx
2
? If so, what is the eigenvalue?
Solution
11.18. Prove that m1 must be integral in order for the function
1
sinm =
to be an acceptable wave function.
Solution
11.19. The energy operator for a time-dependent system(Table 11.1) is
i
t

A possible eigenfunction for the systemis
(x, y, z, t) =(x, y, z) exp(2iEt/h)
Show that *, the probability density, is independent of time.
Solution
11-6
*11.20. Prove that the momentumoperator corresponding to px is a Hermitian operator.
Solution
11.21. Which of the following functions is an eigenfunction of the operator d/dx?
a. k d. exp(kx)
b. kx
2
e. exp(kx
2
)
c. sin kx f. exp(ikx)

(k is a constant, and i is the square root of minus one.) Give the eigenvalue where appropriate.
Solution
11.22. Figure 11.20 shows the angular momentumvectors for 1 =2 and for m=2, 1, 0, 1, 2. In each case, calculate the angles the
vectors make with the Z axis.
Solution
11.23. Show that the one-electron wave functions nlm are also eigenfunctions of the operator
2 2

( ).
x y
L L + What physical property
(observable) is associated with this operator?
Solution
11.24. Explain why the Heisenberg uncertainty principle would be violated if the harmonic oscillator ground-state energy were zero.
Solution
Particle in a Box
11.25. Calculate the lowest possible energy for an electron confined in a cube of sides equal to
a. 10 pmand
b. 1 fm(1 femtometre =10
15
m).
The latter cube is the order of magnitude of an atomic nucleus; what do you conclude fromthe energy you calculate about the
probability of a free electron being present in a nucleus?
Solution
11-7
11.26. A particle is moving in one dimension between x =a and x =b. The potential energy is such that the particle cannot be outside these
limits and that the wave function in between is
=A/x
a. Determine the normalization constant A.
b. Calculate the average value of x.
Solution
11.27. An electron is confined in a one-dimensional box 1 nmlong. How many energy levels are there with energy less than 10 eV? How
many levels are there with energy between 10 and 100 eV?
Solution
11.28. Determine whether the eigenfunctions obtained in Section 11.6 for a particle in a one-dimensional box are eigenfunctions for the
momentumoperator. If they are, obtain the eigenvalues; if they are not, explain why.
Solution
*11.29.Treat the three-dimensional particle in a box of sides a, b, and c by analogy with the treatment in Section 11.6. Assume the potential
to be zero inside the box and infinite outside, and proceed by the following steps:
a. Write the basic differential equation that must be solved for the three-dimensional problem.
b. Separate the equation from(a) into terms involving X(x), Y( y), and Z(z).
c. Determine the expressions for X, Y, and Z.
d. Obtain the expression (Eq. 11.150) for the total energy.
Solution
11.30. What is the quantum-mechanical probability of finding the particle in a one-dimensional box in the middle third of the box?
Derive an expression that shows how this quantity depends on the quantumnumber n.
Solution
11-8
.31. The classical probability for finding a particle in the region x to x +dx in a one-dimensional box of length a is dx/a.
a. Derive the classical probability for finding the particle in the middle third of the box.
b. Show that as n , the quantum probability obtained in the previous problem becomes identical to the classical result.
Solution
*11.32. Problem11.25 is concerned with the calculation of the minimumenergy for an electron confined in a cube. Another approach to the
problemis to consider, on the basis of the uncertainty principle (Eq. 11.60), the uncertainty in the energy if the uncertainty in the
position is equal to the length of the side of the cube. Calculate E for a cube of sides equal to
a. 10 pmand
b. 1 fm(10
15
m),
and compare the results with the minimumenergies found for Problem11.25.
Solution
*11.33. Prove that any two wave functions for a particle in a one-dimensional box of length a are orthogonal to each other; that is, they
obey the relationship
0
0,
a
m n
dx m n =

Solution
11.34. Use the trial function = x(a x) and Eq. 11.247 to calculate an energy for a particle in a one-dimensional box of length a.
Solution
11.35. a. At a node, a wave function passes through zero. For the problemof the particle in a box, how many nodes are there for n =2 and
n =3?
b. Fromthe expression for the radial function for the 3s electron (Table 11.4), obtain expressions for the position of the radial nodes
(i.e., the nodes in the solution of the radial equation) in terms of Z and a0.

Solution

Chapter 11: Quantum Mechanics and Atomic Structure Vibration and Rotation
11-9
Vibration and Rotation
11.36. The vibration frequency of the N2 molecule corresponds to a wave number of 2360 cm
1
. Calculate the zero-point energy and the
energy corresponding to v =1.
Solution
*11.37. If a rigid body rotates in the XY plane, about the Z axis, the angular momentumoperator is
L i

(see Figure 11.15). If the moment of inertia is I, what is the energy operator?
(For additional problems dealing with molecular vibrations and rotations, see Chapter 13.)
Solution
The Atom
11.38. Calculate the ionization energy of the hydrogen atomon the basis of the Bohr theory.
Solution
11.39. Calculate, on the basis of the Bohr theory, the linear velocity of an electron (mass =9.11 10
31
kg) in the ground state of the
hydrogen atom. To what de Broglie wavelength does this velocity correspond? Deduce an equation for the de Broglie wavelength, in
a Bohr orbit of quantumnumber n, with Z =1, in terms of a0 and n. What is the ratio of the circumference of a Bohr orbit of
quantumnumber n to the de Broglie wavelength?
Solution
11.40. For a hydrogenlike atom(a one-electron systemwith a charge number of Z), find the radius of the sphere on which the probability of
finding the 1s electron is a maximum. Compare the result to the expression of Eq. 11.44.
Solution
Chapter 11: Quantum Mechanics and Atomic Structure The Atom
11-10
*11.41. Calculate the reduced masses of the hydrogen and deuteriumatoms, using the following masses for the particles:
Electron: 9.1095 10
31
kg
Proton: 1.6727 10
27
kg
Deuteriumnucleus: 3.3434 10
27
kg

a. Explain qualitatively what effect the different reduced masses will have on the Bohr radii and therefore on the positions of the
lines in the atomic spectra.
b. The Balmer spectrumof hydrogen has a line of wavelength 656.47 nm. Deduce the wavelength of the corresponding line in the
spectrumof deuterium.
Solution
11.42. Calculate the wavelength and energy corresponding to the n =4 to n =5 transition in the hydrogen atom.
Solution
11.43. Calculate, in joules and in atomic units, the potential energy of an electron in the n =2 orbit of the hydrogen atom.
Solution
11.44. The first ionization energy of the Li atomis 5.39 eV. Estimate an effective nuclear charge Zeff for the valence electron in the Li
atom.
Solution
11.45. The first ionization energy of the Na atomis 5.14 eV. Estimate the effective nuclear charge Zeff for the valence electron in the Na
atom.
Solution
*11.46. Use Slaters method (Section 11.13) to determine the effective nuclear charge for
a. a 3s electron in the chlorine atom,
b. a 3p electron in the phosphorus atom, and
c. the 4s electron in the potassiumatom.
Solution
Chapter 11: Quantum Mechanics and Atomic Structure The Atom
11-11
*11.47. A normalized Slater orbital for the 1s orbital in the heliumatomis
3/2
eff
1s eff 0
0
1
exp( / )
Z
Z r a
a
| |
=
|
\ .

where Zeff is the effective charge number. It leads to the following expression for the energy
2
2
eff eff
0
27
.
8
e
E Z Z
a
| |
=
|
\ .

Treat Zeff as a variation parameter, and calculate a minimumenergy in terms of e and a0. Why is the optimumvalue of Zeff different
fromthe actual charge number?
Solution
*11.48. Use the wave function for the 1s orbital of the hydrogen atom, given in Table 11.5, to obtain an expression for the probability that
the electron lies between the distance r and r +dr fromthe nucleus. (Use spherical polar coordinates, for which the volume element
is r
2
dr sin d d .)
Solution
*11.49. Unslds theorem(Section 11.8) states that, for a given value of l, the sumof the values of
2
,
,
[ ( ) ( )]
l m m
l m

is independent of and , i.e., is a constant. Write all these functions for the 2p orbitals (see Tables 11.2 and 11.3), and show that
their sumshows no angular dependence.
Solution
Chapter 11: Quantum Mechanics and Atomic Structure Essay Questions
11-12
Essay Questions
11.50. With emphasis on the physical significance, explain precisely what is meant by a normalized wave function.
11.51. Explain clearly the relationship between the Heisenberg uncertainty principle and the question of whether two operators commute.
11.52. Give an account of the main principles underlying the variation method in quantummechanics.
11.53. Discuss the reasons for abandoning the Bohr theory of the atom.
Chapter 11: Quantum Mechanics and Atomic Structure Solutions
11-13
Solutions
11.1. Calculate, for light of 325 nmwavelength,
a. the frequency;
b. the wavenumber;
c. the photon energy in J , eV, and kJ mol
1
; and
d. the momentumof the photon.
Solution:
Given: 325 nm =
Required: , , , p
a. The frequency is calculated fromEq. 11.1
8 1
9
14 1
14 1
2.998 10 ms
325 10 m
9.224615385 10 s
9.22 10 s
c
c
=
=
=
=

b. The wavenumber is given by the inverse of the wavelength.
7
1
4 1
1
1
325 10 cm
30769.23077cm
30.8 10 cm
=
=
=
=

c. The photon energy is given by in the Key Equations section as
11-14
34
6.626 10 J s
E h

=
=
( )
14 1
9.224615385 10 s
( )
19
19
6.11223015 10 J
6.11 10 J
=
=

In electron volts we get,
19
6.11223015 10 J
=
19
1.602 10 J
1
eV
3.815374628eV
3.82eV
=
=

In kJ per mole we get,
( )( )
19 23 1
1
1
6.11223015 10 J 6.022 10 mol
368078.4999J mol
368kJ mol
=
=
=

d. The momentumis given by Eq. 11. 55
34
9
27 1
27 1
6.626 10 J s
325 10 m
2.03876923 10 kgms
2.04 10 kgms
h
p
p
p
p
=
=

11-15
11.2. A pulsar in the Crab Nebula, NP 0532, emits both radio pulses and optical pulses. A radio pulse is observed at 196.5 Mhz. Calculate
a. the corresponding wavelength;
b. the energy of the photon in J , eV and J mol
1
; and
c. the momentumof the photon.
Solution:
Given: 196.5 Mhz =
Required: , , p
e. The wavelenth is calculated fromEq. 11.1
8 1
2.998 10 ms
c
c

=
=
=
6 1
196.5 10 s
1.525699746 m
1.526 m
=
=

f. The photon energy is given by in the Key Equations section as
34
6.626 10 J s
E h

=
=
( )
6 1
196.5 10 s
( )
25
25
1.302009 10 J
1.302 10 J
=
=

In electron volts we get,
11-16
25
1.302009 10 J
=
19
1.602 10 J
1
7
7
eV
8.127397004 10 eV
8.127 10 eV
=
=

In kJ per mole we get,
( )( )
25 23 1
1
2 1
1.302009 10 J 6.022 10 mol
0.078406982J mol
7.841 10 kJ mol

=
=
=

g. The momentumis given by Eq. 11. 55
34
34 1
34 1
6.626 10 J s
1.525699746 m
4.34292528 10 kgms
4.343 10 kgms
h
p
p
p
p
=
=
=


11-17
11.3. The potassiumspectrumhas an intense doublet with lines at 766.494 nmand 769.901 nm. Calculate the frequency difference
between these two lines.
Solution:
Given:
1 2
, 766.494 nm 769.901 nm = =
Required:
The frequency difference is calculated by converting the wavelengths to their respective frequencies. Using Eq. 11.1,
8 1
1 9
14 1
1
8 1
2 9
14 1
2
1 2
14 1 14 1
12 1
12 1
2.998 10 ms
766.494 10 m
3.911315679 10 s
2.998 10 ms
769.901 10 m
3.894007152 10 s
3.911315679 10 s 3.894007152 10 s
1.730852735 10 s
1.731 10 s
c
c
=
=
=
=
=
=
=


11-18
11.4. Suppose that the position y of a particle that travels along the Y axis of a coordinate systemis given by
( )
0
3 rad
sin
5
t
y t y C
s
( | |
= +
| (
\ .

What is the frequency of the wave motion?
Solution:
Given: equation above
Required:
To find the frequency, we compare this equation to that given by Eq. 11.6,
( ) sin y A t = +
Angular frequency is defined in Eq. 11.4 as
( ) 2 rad =
Therefore frequency is obtained as,
2 rad
3
=
=
5 rad
1
s
2

rad
1
1
3
s
10
0.3s
=
=

11-19
11.5. A mass of 0.2 kg attached to a spring has a period of vibration of 3.0 s.
a. What is the force constant of the spring?
b. If the amplitude of vibration is 0.010 m, what is the maximumvelocity?
Solution:
Given: 0.2kg, 3.0 s, 0.010m m A = = =
Required:
max
,
h
k v
a. The force constant of the spring can be determined using Eq. 11.15
( )
2
1
2
2
h
h
k
m
k m
=
=

The period is the inverse of the frequency, thus,
2
2
1
1
1
1
0.2kg 2
3.0 s
0.877298169kgs
0.88Nm
h
h
h
k
k
k
=
=
| |
=
|
\ .
=
=

b. The maximumvelocity is determined by taking the first derivative of Eq. 11.6.
( )
( )
max
sin
cos
y A
dy
v A
d

= +
= = +

Since cos 1 for all angles, it follows that the maximumvelocity is,
11-20
max
v A =
Substituting for Eq. 11.14 we can finally solve.
max
max

0.877298169 kg
h
k
v A
m
v
=
=
2
s
0.2 kg
( )
1
max
2 1
max
0.010m
0.020943951ms
2.1 10 ms
v
v

=
=


11-21
*11.6. If the average energy associated with a standing wave of frequency in a cavity is
( )
B
exp / 1
h
h k T

deduce the expression for the low-frequency limit of the average energy associated with the standing wave.
Solution:
Given: expression above
Required: expression for the standing wave
The low-frequency limit can be obtained by use of the series expansion
2
e 1 ...
2!
x
x
x = + + +
When x is small, we can make the approximation e 1
x
x = + , where
B
h
x
k T
= .
Thus, when
B
h k T << ,
B
B
1 1
h
k T
h
k T

= =
+

Electromagnetic waves are transverse waves having two degrees of freedom. The value
B
k T is divided between the two degrees of freedom.


11-22
11.7. A sodiumlamp of 50-watt power emits yellow light at 550 nm. How many photons does it emit each second? What is the
momentumof each photon?
Solution:
Given: 50 W, 550nm P = =
Required: / s, E p
We first determine the energy emitted in each photon using E h = . The frequency is calculated fromEq. 11.1
34
6.626 10 J s
c
c
hc
E
E
=
=
=
=
( )
8
2.998 10 m
1
s
( )
9
550 10 m
19
3.61177236 10 J E

=

Recall that
1
1W 1 J s
= , therefore we can determine the number of photons emitted each second by dividing power by energy of a photon.
/ s
50 J
/ s
P
E
E
E
=
=
1
19
s
3.61177236 10 J
20 1
20 1
/ s 1.384361886 10 s
/ s 1.4 10 s
E
E
=
=

The momentumis given by Eq. 11. 55
11-23
34
9
27 1
27 1
6.626 10 J s
550 10 m
1.20472727 10 kgms
1.20 10 kgms
h
p
p
p
p
=
=

11-24
11.8. The threshold frequency 0 for emission of photoelectrons frommetallic sodiumwas found by Millikan, Phys. Rev., 7, 1916, p. 362,
to be 43.9 10
13
s
1
. Calculate the work function for sodium. A more recent value, for a carefully outgassed sample of sodium, is 5.5
10
13
s
1
. What work function corresponds to that value?
Solution:
Given:
13 1 13 1
recent
43.9 10 s , 5.5 10 s = =
Required: w
The work function, w, is given in Eq. 11.37,
2
1
2
h mu w = +
When the kinetic energy,
2
1
2
mu is zero, we get the expression
0
h w = , with
0
as the threshold frequency. Solving for w we get,
0
34
6.626 10 J s
w h
w
=
=
( )
13 1
43.9 10 s
( )
19
19
2.908814 10 J
2.91 10 J
w
w
=
=

In eV, work is given as,
19
2.908814 10 J
w
=
19
1.602 10 J
1
eV
1.815739076 eV
1.82 eV
w
w
=
=

For the more recently determined value the work is,
11-25
34
6.626 10 J s w

=
( )
13 1
5.5 10 s
( )
20
20
20
3.6443 10 J
3.6 10 J
3.6443 10 J
w
w
w
=
=
=
19
1.602 10 J
1
eV
0.2274843945 eV
0.23 eV
w
w
=
=

11-26
11.9. Calculate the value of the de Broglie wavelength associated with
a. an electron moving with a speed of 6.0 10
7
ms
1
(this is the approximate velocity produced by a potential difference of 10 kV).
b. an oxygen molecule moving with a speed of 425 ms
1
at 0 C.
c. an -particle emitted by the disintegration of radium, moving at a speed of 1.5 10
7
ms
1
.
d. an electron having a speed of 2.818 10
8
ms
1
.
Solution:
Given: see above
Required:
deBroglie

The de Broglie wavelength is given by Eq. 11. 56,
h h
p mu
= =
a. The mass of an electron is
31
9.11 10 kg m

= , therefore
( )
( )( )
34
31 7 1
11
11
6.626 10 J s
9.11 10 kg 6.0 10 ms
1.212221 10 m
1.2 10 m 12 pm
=

=
= =

b. The mass of O2 is obtained fromits molar mass divided by the number of molecules per mole (Avogadros constant).
11-27
( )
2
2
2
1
O
1
O
1
O 23 1
34
1
1
23 1
11
11
2 15.9994 gmol
31.9988 gmol
31.9988 gmol 1 kg
6.022 10 mol 1000g
6.626 10 J s
31.9988 gmol 1 kg
425ms
6.022 10 mol 1000g
2.93406385 10 m
2.93 10 m 29.3 pm
M
M
m
=
=
=
=
| |
\ .
=
= =

c. An alpha particle consist of two protons and two neutrons and can be written as He
2+
. Hence, its molar mass is 4 g mol
-1
. We can then
solve in a similar manner as part b.
( )
1
23 1
34
1
7 1
23 1
15
15
4 gmol 1 kg
6.022 10 mol 1000g
6.626 10 J s
4 gmol 1 kg
1.5 10 ms
6.022 10 mol 1000g
6.65029533 10 m
6.7 10 m 6.7 fm
m
=
| |

|
\ .
=
= =

d. The mass of an electron is
31
9.11 10 kg m

= , therefore
( )
( )( )
34
31 8 1
12
12
6.626 10 J s
9.11 10 kg 2.818 10 ms
2.58102414 10 m
2.58 10 m 2.58 pm
=

=
= =

11-28
11.10. Consider a colloidal particle with a mass of 6 10
16
kg. Suppose that its position is measured to within 1.0 nm, which is about the
resolving power of an electron microscope. Calculate the uncertainty in the velocity and comment on the significance of the result.
Solution:
Given:
16
6 10 kg, 1.0 nm m q = =
Required: u , comment on the result
The uncertainty of the velocity is given in Eq. 11.61
2
q u
m

Since
2
h
= , we can substitute and solve for u .

( )
( )( )
34 2 1
16 9
11 1
11 1
4
4
6.626 10 J s kgm s
4 6 10 kg 10 m
8.78800544 10 ms
9 10 ms
h
q u
m
h
u
m q
u
u
u
=
=
=
=

With this uncertainty in velocity, the position of the particle one second later would be uncertain to
11 1
2 9 10 ms
or 0.18 nm. This is

only 0.18% of the diameter of the particle, and the uncertainty principle therefore does not present a serious problemfor particles of this
magnitude. For particles of molecular sizes, the uncertainty is much greater.

11-29
11.11. Calculate the velocity and the de Broglie wavelength of an electron accelerated by a potential of
a. 10 V,
b. 1 kV, and
c. 1 MV.
Solution:
Given: potentials above
Required:
deBroglie
, u
To solve this problem, we use the procedure given in Example 11.2.
When a charge, q, is placed in an electric potential field, V, it experiences a force depending upon its position and starts to accelerate and
pick up kinetic energy. This is given by Ek =qV.
a. For a potential of 10 V,
( )( )
19
18
1.602 10 C 10 V
1.602 10 J
k
k
k
E eV
E
E
=
=
=

The kinetic energy is
2
1
2
mu and therefore
18
31
1
6 1
2 1.602 10 J
9.11 10 kg
1875370.435ms
1.9 10 ms
u
u
u
=
=

FromEq. 11.56, the de Broglie wavelength is,
11-30
( )
( )( )
34
31 1
10
10 2
6.626 10 J s
9.11 10 kg 1875370.435ms
3.87834098 10 m
3.9 10 m 3.9 10 pm
h h
p mu
= =
=
= =

b. Using the same procedure above, we obtain,
( )( )
19
16
16
31
1
7 1
1.602 10 C 1000 V
1.602 10 J
2 1.602 10 J
9.11 10 kg
18753704.35ms
1.9 10 ms
k
k
E
E
u
u
u
=
=

=
=
=

The de Broglie wavelength is therefore,
( )
( )( )
34
31 1
11
11
6.626 10 J s
9.11 10 kg 18753704.35ms
3.87834098 10 m
3.9 10 m 3.9 10 pm
h
mu
=
= =

c. Using the same procedure above, we obtain,
11-31
( )( )
19 6
13
13
31
1
8 1
1.602 10 C 10 V
1.602 10 J
2 1.602 10 J
9.11 10 kg
593044203.2ms
5.9 10 ms
k
k
E
E
u
u
u
=
=

=
=
=

( )
( )( )
34
31 1
12
12
6.626 10 J s
9.11 10 kg 593044203.2ms
1.2264391 10 m
1.2 10 m 1.2 pm
h
mu
=
= =

11-32
*11.12. The group velocity of a wave is given by the equation
( ) 1/
g
d
v
d
=
Prove that the group velocity of a de Broglie particle wave is equal to the ordinary velocity of the particle.
Solution:
Given: group velocity
Required: proof
Fromthe expression E h = and the definition of kinetic energy
2
1
2
mu , a particle of mass m has a frequency of,
2
2
E
h
mu
h
=
=

Substituting the de Broglie wavelength, Eq. 11.56, into the newly acquired expression for frequency, we can eliminate the velocity term.
2
2
2
2
h
mu
h
u
m
m h
h m
h
m
=
=
| |
=
|
\ .
=

The group velocity is therefore,
11-33
( )
( )
2
1/
2
1/
g
g
d
v
d
h
d
m
v
d
=
| |
|
\ .
=

1
2
2
g
g
h
v
m
h
v
m
| || |
=
| |
\ .\ .
=

And fromabove,
g
v u =


11-34
11.13. Photoelectric experiments show that about 5 eV of energy are required to remove an electron fromplatinum.
a. What is the maximumwavelength of light that will remove an electron?
b. If light of 150 nmwavelength were used, what is the velocity of the emitted electron?
Solution:
Given: 5 eV, Pt E =
Required:
max
, u
a. The minimumfrequency such that an electron can be removed fromplatinumis given by,
min
min
E h
E
h
=
=

And the corresponding maximumwavelength is therefore given by Eq. 11.1. Solving for
max
we get,
8 1
2.998 10 ms
c
c
ch
E

=
=
=
=
( )
34
6.626 10 J
s
( )
19
5 1.602 10 J

( )
7
7
2.479993508 10 m
2.480 10 m 248 nm
=
= =

b. The wavelength 150 nmcorresponds to a frequency of
11-35
( )
( )
8 1
9
15 1
2.998 10 ms
150 10 m
1.998666667 10 s
c
c
=
=
=

And to an energy of
34
6.626 10 J s E

=
( )
15 1
1.998666667 10 s
( )
18
1.32431653 10 J E

=

The excess energy is therefore the difference between this value and the energy required to remove an electron fromplatinum.
( )
18 19
excess
19
excess
1.32431653 10 J 5 1.602 10 J
5.23316533 10
E
E

=
=

2
1
2
mu and therefore
19
31
1
6 1
2 5.23316533 10 J
9.11 10 kg
1071859.934ms
1.072 10 ms
u
u
u
=
=


11-36
11.14. Calculate the kinetic energy of an electron that has a wavelength of (a) 10 nm, (b) 100 nm.
Solution:
Given: 10 nm, 100 nm = =
Required:
k
E
Fromthe de Broglie equation, Eq. 11.56,
h
p
= and therefore
h
p
= .
The kinetic energy
k
E is given by
2
2
k
p
E
m
=
Therefore,
2
2
2
k
h
E
m
=
a. Solving for the kinetic energy where 10 nm = gives,
( )
( )( )
2
34
2
31 9
21
21
6.626 10 J s
2 9.11 10 kg 10 10 m
2.40965291 10 J
2.4 10 J
k
k
k
E
E
E
=

=
=

b. Solving for the kinetic energy where 100 nm = gives,
11-37
( )
( )( )
2
34
2
31 9
23
23
6.626 10 J s
2 9.11 10 kg 100 10 m
2.40965291 10 J
2.4 10 J
k
k
k
E
E
E
=

=
=


11-38
11.15. Calculate the de Broglie wavelength of (a) an -particle (a heliumnucleus) accelerated by a field of 100 V, and (b) a tennis ball
served at 220 kmh
1
. (An -particle has a mass of 6.64 10
27
kg and a diameter of about 10
15
m. A standard tennis ball has a mass
of 55.4 g and a diameter of 6.51 cm.)
Solution:
Given: a.
27 15
100 V, 6.64 10 kg, 10 m V m d

= = =
b.
1
tennisball tennisball
220 kmh , 55.4 g, 6.51 cm u m d = = =
Required:
deBroglie

d. For a potential of 100 V, the energy of an alpha particle is,
( )( )
19
17
2 1.602 10 C 100 V
3.204 10 J
k
k
k
E eV
E
E
=
=
=

2
1
2
mu and therefore
17
27
1
2 3.204 10 J
6.64 10 kg
98237.479m66s
u
u
=

( )
( )( )
34
27 1
12
12
6.626 10 J s
6.64 10 kg 98237.479m66s
1.01579516 10 m
1.02 10 m
h
mu
=
=

11-39
Thus the wavelength is about 1000 times larger than the diameter of the particle.
e. We convert the velocity of the tennis ball to ms
-1
and then determine the wavelength.
3
1
1
10 m h
220kmh
km 3600s
61.11111111 ms
u
u
=
=

( )
( )( )
34
3 1
34
34
6.626 10 J s
55.4 10 kg 61.11111111 ms
1.95713817 10 m
1.96 10 m
=
=

This is about
32
3 10 times smaller than the diameter of the tennis ball.


11-40
11.16. Assume that the three real functions 1,

2, and 3 are normalized and orthogonal. Normalize the following functions:
a. 1+2
b. 1

2
c. 1+2+3
d.
1 2 3
1 3
2 2
+
Solution:
Given: three real functions 1,

2, and 3 ; all normalized and orthogonal
Required: Normalize a d
a. The normalization condition for any function is given by Eq. 11. 89 as,
* 1 d =

In other words, to normalize the function
1 2
+ , we multiply by its conjugate and set its integral equal to 1. Since we are told that all three
functions are real, the conjugate of
1 2
+ is simply
1 2
+ . When solving we introduce a factor N.
Reading sections titled Normalization andNormalization Condition will help further understand normalization.
( ) ( )
( )
1 2 1 2
2
2
1 2
2 2 2
1 1 2 2
1
1
2 1
N N d
N d
N d d d

+ + =
+ =
(
+ + =

The first and last integrals are equal to unity since 1

and2 are normalized, as given in the problem. The second integral is equal to zero
( ) 1 2
2 0 d =
since the wave function is orthogonal. Eq. 11.111 defines orthogonality as,
*
1 2
0 d =

This leads to the result,
11-41
| |
2
2
1 0 1 1
2 1
1
2
N
N
N
+ + =
=
=

The normalized wave function is therefore,
( )
1 2
1
2
+
b. We apply the same rationale as above to solve for the normalized wave functions in the following cases.
( )
| |
( )
2
2
1 2
2 2 2
1 1 2 2
2
2
1 2
1
2 1
1 0 1 1
2 1
1
2
1
2
N d
N d d d
N
N
N

=
(
+ =

+ =
=
=

c.
11-42
( )
| |
( )
2
2
1 2 3
2 2 2 2
1 2 3 1 2 1 3 2 3
2
2
1 2 3
1
2 2 2 1
1 1 1 0 0 0 1
3 1
1
3
1
3
N d
N d d d d d d
N
N
N

+ + =
(
+ + + + + =

+ + + + + =
=
=
+ +

d.
| |
2
2
1 2 3
2 2 2 2
1 2 3 1 2 1 3 2 3
2
2
1 2 3
1 2 3
1 3
1
2 2
1 3 2 2 3 2 3
1
2 2 2 2 2
1 1 1 0 0 0 1
3 1
1
3
1 1 3
3 2 2
1 1 1
3 6 2
N d
N d d d d d d
N
N
N

| |
+ =
|
|
\ .
(
+ + =
(

+ + + + + =
=
=
| |
+
|
|
\ .
| |
+
|
\ .

11-43
11.17. Is the function Ae
ax
an eigenfunction of the operator d
2
/dx
2
? If so, what is the eigenvalue?
Solution:
Given: Ae
ax

Required: answer the question, find eigenvalue if applicable
If Ae
ax
is an eigenfunction of d
2
/dx
2
, an operation on Ae
ax
twice by d/dx will give the orginal function multiplied by a constant.
( )
( )

2
e e
e e
ax ax
ax ax
d
A Aa
dx
d
Aa Aa
dx
=
=

Since the operation returns the original function multiplied by a constant, a
2
, then Ae
ax
is an eigenfunction of the operator d
2
/dx
2
with
eigenvaluea
2
.
2
eigenvalue a =

11-44
11.18. Prove that m1 must be integral in order for the function
sin
l
m =
to be an acceptable wave function.
Solution:
Given: function above
Required: proof
For the wave function to be single valued,
sin
l
m = must equal ( ) ( ) sin 2
l
m = +
Using the double angle formulas, we obtain the expression for ( ) ( ) sin 2
l
m = + as,
( )
( )
sin 2
sin sin cos sin cos
sin cos2 sin2 cos
l l
l l l l
m m
A B A B B A
m m m m

= +
+ = +
= +

For this to equal sin
l
m , cos2
l
m must be 1 and therefore2 0
l
m = . This is only true if
l
m is an integer value.

11-45
11.19. The energy operator for a time-dependent system(Table 11.1) is
i
t

A possible eigenfunction for the systemis
(x, y, z, t) =(x, y, z) exp(2iEt/h)
Show that *, the probability density, is independent of time.
Solution:
Given: energy operator, (x, y, z, t)
Required: Show that *, the probability density, is independent of time.
First of all, we do not consider the energy operator to solve this problem.
We are given eigenfunction,
( ) ( )
2 /
, , , , , e
iEt h
x y z t x y z

=
Its conjugate is given by,
( ) ( )
2 /
* , , , * , , e
iEt h
x y z t x y z

=
The probability density is therefore,
2 / 2 /
0
* *e e
* * e
* *
iEt h iEt h

=
=
=

The exponential term, containing the time dependence is cancelled out, leaving only the functions which is simply a function of x, y and z.
Therefore the probability density is independent of time.
Formatted: French (France)
11-46
*11.20. Prove that the momentumoperator corresponding to px is a Hermitian operator.
Solution:
Given: px
Required: proof
The momentumoperator px is given in Table 11.1 as,
i
x

The definition for a Hermitian operator is given by Eq. 11.106,
*
2 1 1 2

( )* F d F d =

Where
F is an operator and
1 2
and are any two functions.
Using the momentumoperator and the functions ( ) ( ) and x x for clarity we must prove that,
* * i dx i dx
x x

| | | |
=
| |
\ . \ .

Using integration by parts on the left side gives,
| |
*
* * i dx i i dx
x x

| | | |
=
| |
\ . \ .

11-47
The first termis zero since all wave functions must asymptotically go to zero at . The second termis
*
0
*
i dx
x
i dx
x
| |
=
|
\ .
| |
=
|
\ .

Which is the same as the right hand side as the equation given above. Therefore operator is Hermitian.

11-48
11.21. Which of the following functions is an eigenfunction of the operator d/dx?
a. k d. exp(kx)
b. kx
2
e. exp(kx
2
)
c. sin kx f. exp(ikx)

(k is a constant, and i is the square root of minus one.) Give the eigenvalue where appropriate.
Solution:
Given: a d
Required: eigenfunction of d/dx, eigenvalues
As stated in problem11.17, if the operation returns the original function multiplied by a constant, the function is an eigenfunction.
a. ( ) 0 0
dk
k
dx
= =
Therefore k is an eigenfunction of the operator d/dx with eigenvalue 0 =
b.
2
2
dkx
kx
dx
=
kx
2
is not an eigenfunction of the operator d/dx.
c.
sin
cos
d kx
k kx
dx
=
sinkx is not an eigenfunction of the operator d/dx.
d.
e
e
kx
kx
d
k
dx
=
e
kx
is an eigenfunction of the operator d/dx with eigenvalue k =
e.
2
2 e
2 e
kx
kx
d
kx
dx
=
2
e
kx
is not an eigenfunction of the operator d/dx.
11-49
f.
e
e
ikx
ikx
d
ik
dx
=
e
ikx
is an eigenfunction of the operator d/dx with eigenvalue ik =

11-50
11.22. Figure 11.20 shows the angular momentumvectors for 1 =2 and for m=2, 1, 0, 1, 2. In each case, calculate the angles the
vectors make with the Z axis.
Solution:
Given: Figure 11.20
Required:
Fromthe figure, we see that the length L of each vector is given by
( ) 2 2 1
6
L
L
= +
=

The Z component in each case is given by
l
m
Using trigonometry, we see that the cosine of each angle is therefore cos
6
l
m
= .
Solving for the case where 2
l
m = ,
1
2
cos
6
35.26438968
35.3
| |
=
|
\ .
=
=

Using the procedure as above, we obtain the following results.
2 1 0 1 2
/ deg 35.3 65.9 90.0 114.1 144.7
l
m

11-51
11.23. Show that the one-electron wave functions nlm are also eigenfunctions of the operator
2 2

( ).
x y
L L + What physical property
(observable) is associated with this operator?
Solution:
Given: nlm and
2 2

( ).
x y
L L +
Required: proof
FromEq. 11. 203 we are given that
2 2 2 2

x y z
L L L L = + +
Therefore, by rearranging we get
2 2 2 2

x y z
L L L L + =
To show that the one-electron wave functions nlm are also eigenfunctions of this operator, we performthe following,
( ) ( )
2 2 2 2

x y nlm z nlm
L L L L + =
Then fromEq. 11. 208 and Eq. 11.211, we substitute the eigenvalues below
( ) ( )
( ) ( )
2 2 2
2 2
1
1
l nlm
l nlm
l l m
l l m
= +
= +

Therefore nlm are eigenfuntions of the operator
2 2

x y
L L + with eigenvalues ( ) ( )
2 2
1
l
l l m + .
The operator
2 2

x y
L L + corresponds to
2 2
x y + and the equation,
2 2 2
x y a + = ,
Which is the equation for a circle with radius a. The physical property corresponding to the operator is thus the square of the radius of the
base of the angular momentumvector as it rotates about the Z axis. (see Figure 11.20)
11-52
11.24. Explain why the Heisenberg uncertainty principle would be violated if the harmonic oscillator ground-state energy were zero.
Solution:
Given: situation above
Required: explain
If the harmonic oscillator ground state energy were zero, the implications is that the kinetic and potential energies are both zero (since
neither can take on negative values). Therefore the momentumis exactly zero. Also, fromthe nature of the potential-energy function, the
total energy can only be zero at x =0. Therefore, this leads to a situation where we know the values of the momentumand position
simultaneously and exactly. This is a violation of the Uncertainty Principle.

11-53
11.25. Calculate the lowest possible energy for an electron confined in a cube of sides equal to
a. 10 pmand
b. 1 fm(1 femtometre =10
15
m).
The latter cube is the order of magnitude of an atomic nucleus; what do you conclude fromthe energy you calculate about the
probability of a free electron being present in a nucleus?
Solution:
Given: electron in a box, a = 10 pm, a =1 fm
Required: E
FromEq. 11.151 the expression for the energy of a particle in a box is given by
2
2 2 2
1 2 3 2
( )
8
h
E n n n
ma
= + +
For the lowest energy possible we set
1 2 3
1 n n n = = = . Using m as the mass of an electron, we solve for E in each case.
( )
( )
2
34
31 2
3 6.626 10 J s
8 9.11 10 kg
E
a

a.
( )
( )( )
12
11
2
34
2
31 11
15
15
10 10 m
1.0 10 m
3 6.626 10 J s
8 9.11 10 kg 1.0 10 m
1.80723968 10 J
1.8 10 J
a
a
E
E
E
=
=
=

=
=

In eV,
11-54
15
1.80723968 10 J
E
=
19
1.602 10 J
1
4
eV
11281.14658eV
1.1 10 eV
E
E
=
=

b.
( )
( )( )
15
2
34
2
31 15
7
7
7
1 10 m
3 6.626 10 J s
8 9.11 10 kg 1 10 m
1.807239682 10 J
1.81 10 J
1.807239682 10 J
a
E
E
E
E
=

=
=
=
19
1.602 10 J
1
12
12
eV
1.128114658 10 eV
1.13 10 eV
E
E
=
=

The latter energy is so large that one electron would not remain in the nucleus, but would be emitted as a particle.

11-55
11.26. A particle is moving in one dimension between x =a and x =b. The potential energy is such that the particle cannot be outside these
limits and that the wave function in between is
=A/x
a. Determine the normalization constant A.
b. Calculate the average value of x.
Solution:
Given: , , / x a x b A x = = =
Required: A, x
a. The normalization condition is given by Eq. 11.89
* 1 d =

For this wave function, the normalization condition becomes,
* 1
b
a
dx =

Solving for A we obtain,
11-56
( )( )
2
2
2
2
2
2
/ / 1
1
1
1
1 1
1
1
b
a
b
a
b
a
A x A x dx
A
dx
x
A
x
A
a b
b a
A
ab
ab
A
b a
ab
A
b a
=
=
(
=
(

(
+ =
(

(
=
(

=

b. To find the average value of x we use Eq.11.104
*( )
*
F d
F F
d

Since we have normalized the function,
1 ab
b a x
| |
=
|
\ .
, the denominator becomes 1 and we can solve as,
11-57
*( )
1
x x dx
ab
x
b a x

=
=
x
| |
|
\ .
| |
1
1
ln
ln
b
a
b
a
b
a
ab
dx
b a x
ab
x dx
b a x
ab
x x
b a
ab b
x
b a a
| |
|
\ .
=

11-58
11.27. An electron is confined in a one-dimensional box 1 nmlong. How many energy levels are there with energy less than 10 eV? How
many levels are there with energy between 10 and 100 eV?
Solution:
Given: 1 nm, 10 eV, 100 eV a E E = = =
Required: n
To calculate the nth energy level, we use Eq. 11.149
( )
( )( )
2
2 34
2
31 9
20 2
20 2
19 1
2
6.626 10 J s
8 9.11 10 kg 1 10 m
6.02413227 10 J
6.02413227 10 J
1.602 10 J eV
0.3760382192 eV
0.3760382192eV
n
n
n
n
n
n
E
E n
n
E
E n
E
n
=

=
=
=

At 10 eV,
10eV
0.3760382192eV
5.15684415
5
n
n
n
=
=

Thus, levels 1 through 5 have energies less than 10 eV.
At 100 eV,
11-59
100eV
0.3760382192eV
16.30737305
16
n
n
n
=
=

Thus, levels 6 through 16 have energies between 10 eV and 100 eV.

11-60
11.28. Determine whether the eigenfunctions obtained in Section 11.6 for a particle in a one-dimensional box are eigenfunctions for the
momentumoperator. If they are, obtain the eigenvalues; if they are not, explain why.
Solution:
Given: Section 11.6
Required: determined if eigenfunctions, eigenvalues
The solution for a particle in a one-dimensional box is given by Eq.11.148 as
2
sin
n
n x
a a
| |
=
|
\ .

The momentumoperator px is given in Table 11.1 as,
i
x

As stated in problem11.17, if the operation returns the original function multiplied by a constant, the function is an eigenfunction.
2
sin
2
sin
2
cos
n
i
x
n x
i
x a a
n x
i
a x a
n n x
i
a a a
| |
| |
=
| |
|
\ .
\ .
| | | |
=
| |
\ . \ .
| | | |
=
| |
\ . \ .

Since the result is not a constant multiplied by
n
,
n
is not an eigenfunction of the momentumoperator. This conclusion is related to the
Heisenberg uncertainty principle; the position and momentumoperators do no commute, there are no common eigenfunctions, and the two
properties cannot be measured simultaneously and precisely. However, the eigenfunction
n
, like any other function, can be expressed as
a linear combination of the set of momentumeigenfunctions (compare Eq. 11.117 to Eq. 11.120). The physical significance of this is that
11-61
the function
n
corresponds to the wave train of particular momentumbeing reflected at the walls of the box and giving rise to a wave train
in the opposite direction.

11-62
*11.29. Treat the three-dimensional particle in a box of sides a, b, and c by analogy with the treatment in Section 11.6. Assume the potential
to be zero inside the box and infinite outside, and proceed by the following steps:
a. Write the basic differential equation that must be solved for the three-dimensional problem.
b. Separate the equation from(a) into terms involving X(x), Y( y), and Z(z).
c. Determine the expressions for X, Y, and Z.
d. Obtain the expression (Eq. 11.150) for the total energy.
Solution:
Given: three-dimensional particle in a box
Required: see above
a. The basic differential equation that must be solved is a three-dimensional formof the Schrodinger, Eq. 11.86.
H E =
FromTable 11.1 we get,
( )
2
2
, ,
2
p
E x y z E
m
+ =

Notice that this is analogous to Eq. 11.85
b. The potential energy,
p
E can be set to zero inside the box, and using the definition for the Del-squared or Laplacian operator, Eq. 11.81,
we get,
2 2 2
2
2 2 2
2 2 2 2
2 2 2
2 2 2
2 2 2 2
2
2
x y z
E
m x y z
mE
x y z

= + +

| |
+ + =
|

\ .

+ + =

The energy, E, is separated into its component parts,
x y z
E E E E = + +
11-63
And the wave function is factored as,
( ) ( ) ( ) X x Y y Z z =

Substitution of the factored wave function gives,
2 2 2
2 2 2 2 2 2
2 2 2
y x z
mE mE mE XYZ XYZ XYZ
XYZ
x y z
| |
+ + =
|

\ .

Dividing by XYZ to eliminate the wave function fromthe right hand side of the equation gives,
2 2 2
2 2 2 2 2 2
2 2 2 1 1 1 y x z
mE mE mE XYZ XYZ XYZ
XYZ x XYZ y XYZ z

+ + =

c. Solving the first termwe get
2
2
2
2
2 2
2 2
2 2
2 2
1 1
1 1
1 1
1 1
XYZ XYZ
XYZ x XYZ x x
XYZ X
YZ
XYZ x XYZ x x
XYZ X
YZ
XYZ x XYZ x
XYZ X
XYZ x X x
| |
=
|
\ .
| |
=
|
\ .

=

=

Therefore,
2
2 2
2 1
x
mE X
X x
=

Similarly, we get
11-64
2
2 2
2
2 2
2 1
2 1
y
z
mE Y
Y x
mE Z
Z x

d. The total energy is given by Eq. 11.150 as
2 2 2 2
3 1 2
2 2 2
8
n n n h
E
m a b c
| |
= + +
|
\ .

This becomes
2 2 2 2 2 2
2 2 2
8 8 8
y x z
x y z
n h n h n h
E E E E
ma mb mc
= + + = + +
If a b c = = , then
( )
2
2 2 2
2
8
x y z
h
E n n n
ma
= + +

11-65
11.30. What is the quantum-mechanical probability of finding the particle in a one-dimensional box in the middle third of the box?
Derive an expression that shows how this quantity depends on the quantumnumber n.
Solution:
Given: one-dimensional box
Required: probability
The quantummechanical probability is given by
* P d =

Since we are trying to find the particle in the middle third of the box, we consider the region between the first third and the second third of
the box. If the box is of length a, then we have the boundaries / 3 and 2 / 3 a a .
We use the wave function in the formof Eq. 11.148 to solve.
2
2 /3
/3
2 /3
2
/3
2
sin
2
sin
a
a
a
a
n x
P dx
a a
n x
P dx
a a
| |
| |
=
| |
|
\ .
\ .
| |
=
|
\ .

Using the fact that ( )
2
1
sin 1 cos2
2
bx bx = , we continue to solve.
11-66
2 /3
/3
2 /3
/3
2 /3
/3
2 1 2
1 cos
2
1 2
1 cos
1 2
sin
2
1 2 4 2
sin sin
3 3 2 3 2 3
1 4 2
sin sin
3 2 3 2 3
a
a
a
a
a
a
n x
P dx
a a
n x
P dx
a a
a n x
P x
a n a
a a a an a an
P
a n a n a
a a n a n
P
a n n

| | | |
=
| |
\ . \ .
| |
=
|
\ .
( | |
=
| (
\ .
( | | | |
= +
| | (
\ . \ .
| | |
= +
|
\ . \
1 1 4 2
sin sin
3 2 3 3
n n
P
n

( |
| (
.
( | | | |
=
| | (
\ . \ .

11-67
11.31. The classical probability for finding a particle in the region x to x +dx in a one-dimensional box of length a is dx/a.
a. Derive the classical probability for finding the particle in the middle third of the box.
b. Show that as n , the quantum probability obtained in the previous problem becomes identical to the classical result.
Solution:
Given: box of length a, Ponedimension =dx/a
Required: P, proof
a. We use a similar approach as problem11.30 to obtain the classical probability for finding the particle in the middle third of the box.
Since the classical probability of finding a particle in the region x to x +dx in a one-dimensional box of length a is dx/a, then the probability
for finding the particle in the middle third of the box is calculated fromthe integral between / 3 and 2 / 3 a a .
2 /3
classical
/3
2 /3
classical
/3
classical
classical
classical
1 2
3 3
1
3
1
3
a
a
a
a
dx
P
a
x
P
a
a a
P
a
a
P
a
P
=
=
| |
=
|
\ .
| |
=
|
\ .
=

b. The result obtained in the previous problemis
1 1 4 2
sin sin
3 2 3 3
n n
P
n

( | | | |
=
| | (
\ . \ .

Since n can only be an integer, the quantity in the square brackets in the solution can only have three values.
11-68
4 2
sin sin 0 if 3,6,9
3 3
3 if 1,4,7
3 if 2,5,8
n n
n
n
n
( | | | |
= =
| | (
\ . \ .
= =
= =

Therefore, we determine that as n , the second term will vanish, since we multiply the square bracket by
1
2n
. This yields a result
identical to the classical probability above.
quantum
1 1
3 2
P
n
=
quantum classical
4 2
sin sin
3 3
1
3
n n
P P
( | | | |
| | (
\ . \ .
= =

11-69
*11.32. Problem11.25 is concerned with the calculation of the minimumenergy for an electron confined in a cube. Another approach to the
problemis to consider, on the basis of the uncertainty principle (Eq. 11.60), the uncertainty in the energy if the uncertainty in the
position is equal to the length of the side of the cube. Calculate E for a cube of sides equal to
a. 10 pmand
b. 1 fm(10
15
m),
and compare the results with the minimumenergies found for Problem11.25.
Solution:
Given: electron in a box, a = 10 pm, a =1 fm, Eq. 11.60
Required: E , compare the results with the Problem11.25
The uncertainty principle is given as Eq. 11.60,
1
2
q p
Since
2
and
2 2
p h
E
m
= = , we use rearrange Eq. 11.60 to obtain an expression for E .
( )
2
2
2
2
1
2 2
4
1
4 2
32
h
p
q
h
p
q
h
E
q m
h
E
m q
| |
=
|
\ .
=
| |
=
|
\ .
=

c.
11-70
( )
( )( )
12
11
2
34
2
2 31 11
17
17
10 10 m
1.0 10 m
6.626 10 J s
32 9.11 10 kg 1.0 10 m
1.52593053 10 J
1.5 10 J
a
a
E
E
E
=
=
=

=
=

In eV,
17
1.52593053 10 J
E
=
19
1.602 10 J
1
eV
95.25159367eV
95eV
E
E
=
=

d.
( )
( )( )
15
2
34
2
2 31 15
9
9
9
1 10 m
6.626 10 J s
32 9.11 10 kg 1 10 m
1.525930531 10 J
1.5 10 J
1.525930531 10 J
a
E
E
E
E
=

=
=
=
19
1.602 10 J
1
9
eV
9525159367eV
9.5 10 eV
E
E
=
=

These uncertainties are considerably smaller than the energies calculated for the particle in a box. If we compare the expression for E used
in problem11.25 to the one used for E , we find that they are smaller by a factor of,
11-71
( )
2 2
2 2
2
2
3
8
32
3
E h h
E ma
m q
E h
E
| |
| |
= |
|
|
\ .
\ .
=
8m
2
a
2
32 m | |
|
|
\ .
( )
2
q
2
h
2
12 118.4352528
E
E

| |
|
|
|
\ .
= =


11-72
*11.33. Prove that any two wave functions for a particle in a one-dimensional box of length a are orthogonal to each other; that is, they
obey the relationship
0
0,
a
m n
dx m n =

Solution:
Given: one-dimensional box of length a, two wave functions
Required: proof
To solve this problem, we take the wave functions for levels m and n in the formof Eq. 11. 148,
2
sin
m
m x
a a
| |
=
|
\ .
and
2
sin
n
n x
a a
| |
=
|
\ .

Substituting
x
y
a
= simplifies the problem. Therefore

dy
dx a
a
dx dy
=
=

And the boundaries become,
( ) 0
0; 0
;
x y
a
a
x a y
= = =
= =
( )
a
=

Solving the integral, we get
11-73
0
0
0
2 2
sin sin
2
sin sin
m n
dy
my ny dy
my ny dy

The integral sin sin my ny dy
is a standard integral with the solution

( ) ( ) sin sin 1
sin sin
2
m n y m n y
my ny dy
m n m n
+ (
=
(
+

Therefore we get,
0
2
sin sin my ny dy
1
2
( ) ( )
( )
0
0
sin sin
sin 1
sin sin
m n y m n y
m n m n
m n
my ny dy
m n
+ (
(
+

( ) sin m n
m n
+
+
( ) sin 0 m n
m n
( ) sin 0 m n
m n
+
+
+
| |
0
0
1
sin sin 0
sin sin 0
my ny dy
my ny dy

(
(
(

=
=

As we can see, at the lower limit, both terms are zero since sin0 0 = . At the upper limit, both terms are also zero since m and n are integers,
and any sine of any integer of will return 0.
Therefore the integral is zero and the wave functions and
m n
are orthogonal.


11-74
11.34. Use the trial function = x(a x) and Eq. 11.247 to calculate an energy for a particle in a one-dimensional box of length a.
Solution:
Given: , Eq. 11.247, one-dimensional box of length a
Required: E
Energy is given by Eq. 11.247 as,
*
*
H d
E
d

=

The
H operator is given in Table 11.1 as,

2
2
2
p
E
m
+

The potential energy,
p
E can be set to zero inside the box, and the Del-squared or Laplacian operator, is given by Eq. 11.81
2 2 2
2
2 2 2
x y z

= + +

For a one-dimensional box,
2
2
2
d
dx
=
Using
2
h
= , and the boundaries of the box as 0 and a, we rewrite Eq. 11.247 as

11-75
( )
( ) ( )
( )
2 2
2
0
2
0
2
2
2 2
0
2
2
0
2
8
a
a
a
a
d
dx
m dx
E
dx
d x a x
h
x a x dx
m dx
E
x a x dx
| |

|
\ .
=
| |
|
|
\ .
=

Solving the denominator and numerator separately provides a much easier way to obtain the result.
The numerator is,
11-76
( )
( ) ( )
( )
( )
( )
( )
( )( )
( )
( ) ( )
2
2
2 2
0
2 2
2
2 2
0
2
2
0
2
2
0
2
2
2
0
2 2 3
2
0
2 3
2
2
2 3 3
2
8
8
2
8
2
8
4
4 2 3
0
4 2 3
4 2 3
a
a
a
a
a
a
d x a x
h
x a x dx
m dx
d ax x
h
x a x dx
m dx
d a x h
x a x dx
m dx
h
x a x dx
m
h
ax x dx
m
h ax x
m
a a a h
m
h a a
m
| |
|
|
\ .
| |
| =
|
\ .
| |
=
|
\ .
=
=
(
=
(

(
= (
(

(
=
3 2
2
24
a h
m
(
=

The denominator is,
11-77
( )
( )
( )
2
2
0
2 2 2
0
2 2 3 4
0
3 4 5
2
0
3 4 5
2
5 5 5
2
2
3 2 5
0
3 2 5
3 2 5
a
a
a
a
x a x dx
x a ax x dx
a x ax x dx
x x x
a a
a a a
a a
a a a
= +
= +
(
= +
(

( | | | | | |
= +
( | | |
\ . \ . \ .
= +

5
5
1 1 1
3 2 5
30
a
a
| |
= +
|
\ .
=
Therefore E is,
3 2 5
2
3 2
2 5
2
2 3
2
2 3
2
2 2
24 30
30
24
30
3 8
10
8
5
4
a h a
E
m
a h
E
m a
h
E
ma
h
E
ma
h
E
ma
=
=
=
| |
=
|
\ .
=

11-78
Notice that for n =1, the exact energy is
2
3
8
h
ma

And that in this case we have
2
10
times the exact energy.


11-79
11.35. a. At a node, a wave function passes through zero. For the problemof the particle in a box, how many nodes are there for n =2 and
n =3?
b. Fromthe expression for the radial function for the 3s electron (Table 11.4), obtain expressions for the position of the radial nodes
(i.e., the nodes in the solution of the radial equation) in terms of Z and a0.
Solution:

Given: particle in a box, n =2 and n =3, 3s electron, Table 11.4
Required: number of nodes, position of nodes in terms of Z and a0 (r)
a. For n =2, there is one node. For n =3, there are two nodes. We do not count the points x = 0 and x =a, where the wave function
becomes zero but does not pass through it.
b. FromTable 11.4, we have the radial function for the 3s electron is,
0
3/2
2 2
/3
30 2
0 0 0
1 4 4
6 e
9 9 3
Zr a
Z Zr Z r
R
a a a
| | | |
= +
| |
\ . \ .

Since we know the nodes are at a position where the wave function passes through zero, we set the expression equal to zero to solve for r.
0
3/2
2 2
/3
30 2
0 0 0
1 4 4
6 e 0
9 9 3
1
9 3
Zr a
Z Zr Z r
R
a a a
| | | |
= + =
| |
\ . \ .
3/2
0
Z
a
| |
|
\ .
0
2 2
/3
2
0 0
4 4
6 e
9
Zr a
Zr Z r
a a
| |
+
|
\ .
2 2
2
0 0
2
2 2
0 0
0
4 4
6 0
9
4
6 4 0
9
Zr Z r
a a
Z
a Za r r
=
+ =
+ =

We can solve for r using the quadratic equation.
11-80
( ) ( )
2
2
2
2
0 0 0
2
2 2
2 2 0
0 0
2
4
2
1 4
4 4 4 6
9 4
2
9
32 1
4 16
3 8
9
b b ac
r
a
Z
r Za Za a
Z
Z a
r Za Z a
Z

=
| |
| |
| =
|
| | |
\ .
\ .
|
\ .
| |
= |
|
| |
\ .
|
\ .

( )
0 0 2
0 0 2
0 0 2
0
0
9 32
4 16
8 3
9 16
4
8 3
9 4
4
8 3
9 1
1
2 3
3
3 3
2
r Za Za
Z
r Za Za
Z
r Za Za
Z
a
r
Z
a
r
Z
| |
=
|
|
\ .
| |
=
|
|
\ .
| |
= |
|
\ .
| |
= |
|
\ .
=

Therefore the two radial nodes are located at distances of
( )
0
3
3 3
2
a
r
Z
= + and
( )
0
3
3 3
2
a
r
Z
= fromthe nucleus.


11-81
11.36. The vibration frequency of the N2 molecule corresponds to a wave number of 2360 cm
1
. Calculate the zero-point energy and the
energy corresponding to v =1.
Solution:
Given: N2,
1
2360 cm , 1 = =
Required: Zero-point energy
The zero-point energy at 1 = can be calculated using,
0
3
2
E h =
Frequency,
0
, is calculated from, Eq. 11.1,
34
1
3
2
3
6.626 10 J s
2
c
c
c
E hc
E
=
=
= =
=
=
( )
10
2.998 10 cm
1
s
( )
1
2360 cm
( )
20
20
7.03212079 10 J
7.032 10 J
E
E
=
=


11-82
*11.37. If a rigid body rotates in the XY plane, about the Z axis, the angular momentumoperator is
L i

(see Figure 11.15). If the moment of inertia is I, what is the energy operator?
(For additional problems dealing with molecular vibrations and rotations, see Chapter 13.)
Solution:
Given: the angular momentumoperator, I
Required: energy operator
The energy is related to the angular momentumby Eq. 11.215,
2
2
k
L
E E
I
= =
The energy, or Hamiltonian operator is therefore,
( )
2
2
2
2 2
2
2 2
2
2 2
2 2
1
2
1
1
2
2
2
8
E i
I
E i
I
E
I
h
h
E
I

| |
=
|
\ .
| |
=
|
\ .

=
=

=

11-83
11.38. Calculate the ionization energy of the hydrogen atomon the basis of the Bohr theory.
Solution:
Given: hydrogen atom
Required: ionization energy
The energy required to remove the electron fromthe lowest energy level in hydrogen ( )
1
1 n = to infinity, ( )
2
n = is the ionization energy.
We use Eq. 11.50, Eq. 11.1 and the expression for energy, E h = , to solve.
2 2
1 2
2 2
1 2
34
1 1 1
1 1
6.626 10 J s
R
n n
c
c
c
E hcR
n n
E
| |
= =
|
\ .
=
= =
| |
=
|
\ .
=
( )
8
2.998 10 m
1
s
( )
7 1
1.0968 10 m
( ) 2 2
1 1
1

18
18
2.17876556 10 J
2.179 10 J
E
E
| |
|
\ .
=
=

In eV,
18
2.17876556 10 J
E
=
19
1.602 10 J
1
eV
13.6002844eV
13.60eV
E
E
=
=

11-84
11.39. Calculate, on the basis of the Bohr theory, the linear velocity of an electron (mass =9.11 10
31
kg) in the ground state of the
hydrogen atom. To what de Broglie wavelength does this velocity correspond? Deduce an equation for the de Broglie wavelength, in
a Bohr orbit of quantumnumber n, with Z =1, in terms of a0 and n. What is the ratio of the circumference of a Bohr orbit of
quantumnumber n to the de Broglie wavelength?
Solution:
Given:
31
9.11 10 kg, , 1 m n Z = =
Required: ( ) ( )
deBroglie deBroglie deBroglie
, , expression , : expression u C
Velocity is given in Eq. 11.39 as,
( 0,1,2, )
2
h
L mur n n n
= = = =
Since we are told the electron is in the ground state of the hydrogen atom, n =1 and velocity is therefore,
2
h
u
mr
=
FromEq. 11. 44, we take
0
r a = . This is because a0 is a length and is the radius of the orbit for n =1 for the hydrogen atomitself (Z =1).
The length a0 is known as the Bohr radius and has a value of 52.92 pm(1 picometre =10
12
m).
( )
( )( )
34
31 12
1
6 1
6.626 10 J s
2 9.11 10 kg 52.92 10 m
2187425.903 ms
2.19 10 ms
u
u
u
=

=
=

The de Broglie wavelength is given by Eq. 11.56,
h h
p mu
= =
11-85
Solving, using the velocity determined above we get,
( )
( )( )
34
31 1
10
10
6.626 10 J s
9.11 10 kg 2187425.903 ms
3.32506166 10 m
3.33 10 m 333 pm
=
= =

To find the de Broglie expression for wavelength in terms of a0 and n we use Eq. 11.56 and Eq. 11.39.
2
2
2
nh
u
mr
r h
n mu
h r
mu n
=
=
= =

FromEq. 11. 43 with Z =1,
( )
2
0
2
0
2
0
0
2
2
n
r a
Z
r a n
a n
n
a n

=
=
=
=

The expression for circumference is 2 C r = , hence
2
0
2 C n a = and the ratio : C is
11-86
0
2
:
a
C

=
2
n
0
2 a n
: C n =


11-87
11.40. For a hydrogen-like atom(a one-electron systemwith a charge number of Z), find the radius of the sphere on which the probability of
finding the 1s electron is a maximum. Compare the result to the expression of Eq. 11.44.
Solution:
Given: a one-electron system, charge of Z
Required: r
The radius of the sphere of maximumprobability corresponds to the maximumin the radial probability function, given in Section 11.8 by
2 2
1
4
s
r
We find the maximumr by differentiating the radial probability function with respect to r and setting it equal to zero.
Using Eq. 11.193, and Z, we solve to obtain r.
11-88
0
2 /
2
1 3
0
e
4
r a
s
a
P
=
=
2
1
r
0
0
0 0
0
3
2 /
0
3
2 / 2
0
3 3
2Z / 2Z / 2
0 0 0
3
2Z /
0
e
4 e 0
2
8 e 4 e 0
8 e
Zr a
Zr a
r a r a
r a
Z
a
dP d Z
r
dr dr a
Z Z Z
r r
a a a
Z
a
| | | |
| |
\ .\ .
| |
| |
| = =
|
|
\ .
\ .
| | | | | |
+ =
| | |
\ . \ . \ .
| |
|
\ . 0
0
0
0
1 0
1 0
0,1 0
Z
r r
a
Z
r r
a
Z
r r
a
a
r
Z
| | | |
=
| |
|
\ . \ .
| |
=
|
\ .
= =
=

We ignore the r =0 value since it does not make sense for the radius to be zero. The expression for r obtained here is identical to Eq. 11.43
for the case of a 1s electron.

11-89
*11.41. Calculate the reduced masses of the hydrogen and deuteriumatoms, using the following masses for the particles:
Electron: 9.1095 10
31
kg
Proton: 1.6727 10
27
kg
Deuteriumnucleus: 3.3434 10
27
kg

a. Explain qualitatively what effect the different reduced masses will have on the Bohr radii and therefore on the positions of the
lines in the atomic spectra.
b. The Balmer spectrumof hydrogen has a line of wavelength 656.47 nm. Deduce the wavelength of the corresponding line in the
spectrumof deuterium.
Solution:
Given: particle masses above, 656.47 nm =
Required: , a, b,
The reduced mass is calculated fromEq. 11.152,
1 2
1 2
m m
m m
=
+

For hydrogen we get,
11-90
( )
( )( )
( )
( )( )
H
H
H
31 27
H 31 27
31
H
31
H
D
D
D
31 27
D 31 27
31
D
D
9.1095 10 kg 1.6727 10 kg
9.1095 10 kg 1.6727 10 kg
9.10454 10 kg
9.1045 10 kg
9.1095 10 kg 3.3434 10 kg
9.1095 10 kg 3.3434 10 kg
9.10702 10 kg
e
e
e
e
m m
m m
m m
m m
=
+

=
+
=
=
=
+

=
+
=
=
31
9.1070 10 kg

a. The reduced mass and the Bohr radius are related by Eq. 11.44,
2
0
0 2
h
a
e
=
The Bohr radius is inversely proportional to the reduced mass, therefore it is slightly smaller for deuteriumthan it is for hydrogen.
Additionally, the Bohr radius is inversely proportional to the energies. Therefore, the energies are slightly greater for deuteriumthan it is for
hydrogen. The frequencies of the transitions are therefore slightly greater for deuterium, and the wavelengths are slightly shorter.
b. The wavelengths are in the inverse ratio of the reduced masses, and therefore we have the ratio,
H
D
9.1045
9.1070
=
The wavelength of the line in the spectrumof deuteriumis therefore,
11-91
9.1045
656.47 nm
9.1070
656.2897897 nm
656.29 nm
=
=
=

11-92
11.42. Calculate the wavelength and energy corresponding to the n =4 to n =5 transition in the hydrogen atom.
Solution:
Given: n =4, n =5, hydrogen atom
Required: , E
FromEq. 11.50, we can calculate the wavelength,
2 2
1 2
1
2 2
1 2
1
7 1
2 2
6
6
1 1 1
1 1
1 1
1.0968 10 m
4 5
4.05219 10 m
4.0522 10 m
v R
n n
R
n n
| |
= =
|
\ .
| | | |
=
| |
|
\ . \ .
| | | |
=
| |
\ . \ .
=
=

Energy is determined fromEq. 11.1 and E h = ,
34
6.626 10 J s
E h
c
hc
E
E
=
=
=
=
( )
8
2.998 10 m
1
s
( )
6
4.05219 10 m
20
20
4.90222 10 J
4.902 10 J
E
E
=
=

11-93
11.43. Calculate, in joules and in atomic units, the potential energy of an electron in the n =2 orbit of the hydrogen atom.
Solution:
Given: n =2, hydrogen atom
Required: Ep
We use Eq. 11.48, with Z =1 for a hydrogen atomto solve for Ep,
( )
( ) ( )
2 2
2
0 0
2
19
12 2 1 2 2 12
18
18
4
1.602 10 C
4 8.854 10 C N m 2 52.92 10 m
1.08967 10 J
1.090 10 J
p
p
p
p
Z e
E
n a
E
E
E

=

=
=

In atomic units of
2
0 0
4
e
a
,
2
2
1
2
0.25au
p
p
E
E
=
=

11-94
11.44. The first ionization energy of the Li atomis 5.39 eV. Estimate an effective nuclear charge Zeff for the valence electron in the Li
atom.
Solution:
Given:
ionization
5.39 eV E =
Required: Zeff
Problems 11.44 and 11.45 are conveniently worked out with reference to Problem11.38, where we deter. emied the ionization energy for
hydrogen as 13.60 eV. FromEq. 11.49,
2 2
2
0 0
8
k p
Z e
E E E
n a
= + =
the first ionization energy is proportional to
2
eff
2
Z
n
.
For H, Zeff =1 and n =1, hence,
2
eff
2
2
2
13.60 eV
1
13.60 eV
1
13.60 eV
Z
I
n
I
I
| |
=
|
\ .
| |
=
|
\ .
=

For Li, n =2, hence,
11-95
2
eff
2
2
eff
2
eff
13.60 eV
13.60 eV
2 5.39 eV
Z
I
n
n I
Z
Z
| |
=
|
\ .
=
=
( )
13.60 eV
eff
eff
1.259084635
1.26
Z
Z
=
=

11-96
11.45. The first ionization energy of the Na atomis 5.14 eV. Estimate the effective nuclear charge Zeff for the valence electron in the Na
atom.
Solution:
Given:
ionization
5.14 eV E =
Required: Zeff
For Na, n =3, hence,
2
eff
2
2
eff
2
eff
13.60 eV
3
13.60 eV
3 5.14 eV
Z
I
n
I
Z
Z
| |
=
|
\ .
=
=
( )
13.60 eV
eff
eff
1.844307618
1.84
Z
Z
=
=

11-97
*11.46. Use Slaters method (Section 11.13) to determine the effective nuclear charge for
a. a 3s electron in the chlorine atom,
b. a 3p electron in the phosphorus atom, and
c. the 4s electron in the potassiumatom.
Solution:
Given: a c,
Required: Zeff
Using the Slater method, we find Zeff fromEq. 254,
eff
Z Z =
We use the four rules to help solve for Zeff.
a. The nuclear charge of Cl is, Z =17. We then subtract:
0.30 for the other 3s electron
5 0.35 for the five 3p electrons
8 0.85 for the eight 2s and 2p electrons,
2 1.00 for the two 1s electrons
eff
eff
17 0.30 5 0.35 8 0.85 2 1.00
6.15
Z
Z
=
=

b. The nuclear charge of P is, Z =15. We then subtract:
2 0.30 for the 3s electron
2 0.35 for the other 3p electrons
2 1.00 for the two 1s electrons
eff
eff
15 2 0.30 2 0.35 8 0.85 2 1.00
4.9
Z
Z
=
=

c. The nuclear charge of K is, Z =19. We then subtract:
11-98
10 1.00 for the 1s, 2s and 2p electrons
eff
eff
19 8 0.85 10 1.00
2.2
Z
Z
=
=

11-99
*11.47. A normalized Slater orbital for the 1s orbital in the heliumatomis
3/2
eff
1s eff 0
0
1
exp( / )
Z
Z r a
a
| |
=
|
\ .

where Zeff is the effective charge number. It leads to the following expression for the energy
2
2
eff eff
0
27
.
8
e
E Z Z
a
| |
=
|
\ .

Treat Zeff as a variation parameter, and calculate a minimumenergy in terms of e and a0. Why is the optimumvalue of Zeff different
fromthe actual charge number?
Solution:
Given: E
Required: Emin in terms of e and a0, optimumZeff
To solve we minimize E with respect to Zeff,
2
eff
eff 0
2
0
27
2 0
8
dE e
Z
dZ a
e
a
| |
= =
|
\ .
eff
eff
eff
27
2 0
8
27
2 0
8
27
16
Z
Z
Z
| |
=
|
\ .
=
=

Solving for Emin in terms of e and a0, we get,
11-100
eff
2
2
min
0
2
min
0
27
16
27 27 27
16 8 16
729
256
Z
e
E
a
e
E
a
=
| |
| | | |
= |
| |
|
\ . \ .
\ .
| |
=
|
\ .

11-101
*11.48. Use the wave function for the 1s orbital of the hydrogen atom, given in Table 11.5, to obtain an expression for the probability that
the electron lies between the distance r and r +dr fromthe nucleus. (Use spherical polar coordinates, for which the volume element
is r
2
dr sin d d .)
Solution:
Given: Table 11.5
Required: P in spherical polar coordinates
The expression for the wave function for the 1s orbital of the hydrogen atomis given in Table 11.5 as,
0
3/2
/
1 100
0
1 1
e
r a
s
a

| |
= =
|
\ .

To find P, we must solve for,
0
2 /
3
0
1
* e
r dr
r a
r
dr
a

+
=

Multiplying by the volume element, integrating from0 to and from0to2 , we convert to spherical polar coordinates.
( )
0
2
2 / 2
3
0 0
0
0
0
0
0
2
2
0
0
2
0
1
* e sin
separatingthe integrals,
sin cos
sin 1 1
sin 2
2
r a
r dr d d
a
d
d
d
d
d

=
=
=
=
=
=

11-102
Therefore we get,
4 P =
1
0
0
2 / 2
3
0
2 / 2
3
0
e
4
e
r a
r a
r dr
a
P r dr
a
=

11-103
*11.49. Unslds theorem(Section 11.8) states that, for a given value of l, the sumof the values of
2
,
,
[ ( ) ( )]
l m m
l m

is independent of and , i.e., is a constant. Write all these functions for the 2p orbitals (see Tables 11.2 and 11.3), and show that
their sumshows no angular dependence.
Solution:
Given: Unslds theorem, Tables 11.2 and 11.3
Required: functions for the 2p orbitals, show there is no angular dependence in their sum
FromTables 11.2 and 11.3, we have the following for l =1 and ml =-1, 0, 1.
1 10
0 1 1
1
cos 6
cos
2
1 3
sin
2 2
sin
= =
= =
=

The functions for the 2p orbitals are therefore,
10 0
11 1
1 1 1
6 1
cos
2 2
3 1
sin cos
2
3 1
sin sin
2

=
=
=

The sumof their squares is,
11-104
( ) ( )
2 2 2
2 2 2 2 2
2 2 2 2
2 2
6 1 3 1 3 1
cos sin cos sin sin
2 2 2 2
6 1 3 1 3 1
cos sin cos sin sin
4 2 4 4
3
cos sin cos sin
4
cos sin 1

| | | | | |
= + +
| | |
| | |
\ . \ . \ .
= + +
= + +
+ =

( )
2 2
3
cos sin
4
3
4

= +
=

This solution is independent of and .


CHAPTER
1
1
3
3
Foundations of
Chemical Spectroscopy

Physical Chemistry
Electronic Edition

Chapter 13: Foundations of Chemical Spectroscopy Absorption of Radiation
13-2
Chapter 13
Absorption of Radiation
13.1. The molar absorption coefficient of human hemoglobin (molecular weight 64 000) is 532 dm
3
cm
1
mol
1
at 430 nm. A solution of
hemoglobin in a cuvette having a light path of 1 cm was found at that wavelength to have a transmittance of 76.7%. Calculate the
concentration in mol dm
3
and in g dm
3
.
Solution
13.2. A spectrophotometer has a meter that gives a reading directly proportional to the amount of light reaching the detector. When the
light source is off, the reading is zero. With pure solvent in the light path, the meter reading is 78; with a 0.1 M solution of a solute
in the same solvent, the meter reading is 55. The light path is 0.5 cm. Calculate the absorbance, the transmittance, and the molar
absorption coefficient.
Solution
13.3. The transmission of a potassium chromate solution was measured at a wavelength of 365 nm using a cell with a 1.0-cm path length.
The data are as follows:
Transmission 0.357 0.303 0.194 0.124
Conc. 10
4
/mol dm
3
0.90 1.10 1.50 1.90

Calculate the molar Naperian absorbance and the molar decadic absorbance.
Solution
13.4. An aqueous solution containing 0.95 g of oxygenated myoglobin (M
r
=18 800) in 100 cm
3
gave a transmittance of 0.87 at 580 nm,
with a path length of 10.0 cm. Calculate the molar absorption coefficient.
Solution
13.5. A substance in aqueous solution at a concentration of 0.01 M shows an optical transmittance of 28% with a path length of 2 mm.
Calculate the molar absorption coefficient of the solute. What would be the transmittance in a cell 1-cm thick?
Solution
13.6. The molar absorption coefficient of hemoglobin at 430 nm is 532 dm
3
mol
1
cm
1
. A solution of hemoglobin was found to have an
absorbance of 0.155 at 430 nm, with a light path of 1.00 cm. Calculate the concentration.
Solution
Chapter 13: Foundations of Chemical Spectroscopy Atomic Spectra
13-3
13.7. A 10 M solution of a substance gave an absorbance of 0.1028 with a light path of 1 cm. Calculate the molar absorption coefficient.
What would be the percentage light transmittance of a 1-m solution with the same light path?
Solution
13.8. Two substances of biological importance, NAD
+
and NADH, have equal absorption coefficients, 1.8 10
4
dm
3
mol
1
cm
1
, at 260
nm (a wavelength at which absorption coefficients are equal is known as the isosbestic point
6
). At 340 nm, NAD
+
does not absorb at
all, but NADH has an absorption coefficient of 6.22 10
3
dm
3
mol
1
cm
1
. A solution containing both substances had an absorbance
of 0.215 at 340 nm and of 0.850 at 260 nm. Calculate the concentration of each substance.
Solution
13.9. The transmittance of a 0.01 M solution of bromine in carbon tetrachloride, with a path length of 2 mm, is 28%. Calculate the molar
absorption coefficient of bromine at that wavelength. What would the percentage transmittance be in a cell 1-cm thick?
Solution
13.10. An acid HA ionizes in aqueous solution into H
+
and A
ions. At a wavelength of 430 nm HA does not absorb light, but A
does so
with an absorption coefficient of 458 dm
3
cm
1
mol
1
. A solution of the acid at a concentration of 0.1 M was found to have a
transmittance of 1.47% at 430 nm with a path length of 1 cm and at 25 C. Calculate the dissociation constant of HA at 25 C, and
G for the dissociation process.
Solution
Atomic Spectra
13.11. In the Balmer series of the hydrogen atom, the first emission line is observed at 656.3 nm. Calculate the value of the Rydberg
constant. What is the energy of the light quanta emitted during the transition?
Solution
13.12. The ground state of the Li atom has the electronic configuration 1s
2
2s
1
. What is its spectroscopic term? If the 2s electron is excited
to the 2p state, what terms are then possible?
Solution
13.13. Suppose that an excited state of the carbon atom has the electronic configuration 1s
2
2s
2
2p
1
3p
1
. What are the possible spectroscopic
terms?
Solution

6
Fromthe Greek prefix iso-, the same, and sbestos, quench. This word is sometimes incorrectly written as isobestic.
Chapter 13: Foundations of Chemical Spectroscopy Atomic Spectra
13-4
13.14. What are the terms for the following electronic configurations?
a. Na (1s
2
2s
2
2p
6
3p
1
)
b. Sc (1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
1
)
Solution
13.15. What values of J may arise in the following terms?
1
P,
3
P,
4
P,
1
D,
2
D,
3
D,
4
D
Solution
*13.16. Calculate the Land-g-factor for a
2
P
1/2
level. What would be the anomalous Zeeman splitting for this level in a magnetic field of
4.0 T?
Solution
*13.17. Calculate the spacing between the lines for a
3
D
1

3
P
0
transition, in an anomalous Zeeman experiment with a magnetic field of 4.0
T.
Solution
Rotational and Microwave Spectra
13.18. The separation between neighboring lines in the pure rotational spectrum of
35
Cl
19
F is found to be 1.023 cm
1
. Calculate the
interatomic distance.
Solution
13.19. The lines in the pure rotational spectrum of HF are 41.9 cm
1
apart. Calculate the interatomic distance. Predict the separation
between the lines for DF and TF.
Solution
13.20. In the microwave spectrum of
12
C
16
O the separation between lines has been measured to be 115270 MHz. Calculate the interatomic
distance.
Solution
*13.21. The J = 0 J =1 line in the microwave absorption spectrum of
12
C
16
O and of
13
C
16
O was measured by Gillam et al., [Phys. Rev.
78, 140(1950)]. In its ground vibrational state, the former has the value 3.842 35 cm
1
and the latter, the value 3.673 37 cm
1
.
Calculate
a. the bond length of the
12
C
16
O molecule,
b. the relative atomic mass of
13
C,
c. the bond length of the
13
C
16
O molecule.
Solution
Chapter 13: Foundations of Chemical Spectroscopy Vibrational-Rotational and Raman Spectra
13-5
13.22. The microwave spectrum of
16
O
12
C
32
S shows absorption lines separated by 12.163 GHz. That of
16
O
12
C
34
S shows lines separated by
11.865 GHz. The determination of the bond distances involves solving two simultaneous quadratic equations, which is best done by
successive approximations. To avoid all that labor, simply confirm that the results are consistent with r(OC) =116 pm and r(C
S) =156 pm.
Solution
Vibrational-Rotational and Raman Spectra
13.23. The maximum potential energy that a diatomic molecule can store is
2
1
,
2
kx where x is the amplitude of vibration. If the force
constant k is 1.86 10
3
N m
1
, calculate the maximum amplitude of vibration for the CO molecule in the v =0 vibrational state.
Compare this to the bond length obtained in Problem 13.21. Use the value of u
r
in that problem.
Solution
13.24. Consider the following molecules: H
2
, HCl, CO
2
, CH
4
, H
2
O, CH
3
Cl, CH
2
Cl
2
, H
2
O
2
, NH
3
, and SF
6
. Which of them will give
a. a pure rotational spectrum,
b. a vibrational-rotational spectrum,
c. a pure rotational Raman spectrum,
d. a vibrational Raman spectrum?
Solution
13.25. Analysis of the vibrational-rotational spectrum of the H
35
Cl molecule shows that its fundamental vibrational frequency
0
is 2988.9
cm
1
. Calculate the force constant of the HCl bond.
Solution
13.26. A few transitions in the P and R branches of the infrared spectrum of H
35
Cl spectrum are identified below.
J 0 1 2 3 4 5 6
P (cm
1
) 2865.10 2843.62 2821.56 2798.94 2775.76 2752.04
R (cm
1
) 2906.24 2925.90 2944.90 2963.29 2981.00 2998.04

Using Eqs. 13.134 or 13.135 as appropriate, calculate
0
and the rotational constant . B

Solution
13-6
13.27. Comparison of the results of Problem 13.26 to experimental values for H
35
Cl (
0
=2990 cm
1
, and B
=10.59 cm
1
) shows that Eqs.
13.134 and 13.135 do not accurately relate the observed transitions to the rotational quantum numbers. Much of the error results
from not taking the anharmonicity of the potential energy curve into account. Using the definition (see Eq. 13.138) T
v,J
= ( +
1
2
)
0

(v +
1
2
)
2

0
x
e
+ J(J +1) , B
derive a more accurate expression for T

v,J
for the v = 0 v = 1 transitions of a diatomic molecule.
[Even this is an approximate treatment because we are ignoring the coupling of rotations with vibrations.]
Solution
13.28. From the results of Problems 13.26 and 13.27 and the experimental value of
0
for H
35
Cl given in Problem 13.27, estimate the value
of the anharmonicity constant x
e
. Use the average of the P and R branch values for
0
from Problem 13.26.
Solution
13.29. The vibrational Raman spectrum of
35
Cl
2
shows series of Stokes and anti-Stokes lines; the separation between the lines in each of
the two series is 0.9752 cm
1
. Estimate the bond length in Cl
2
.
Solution
13.30. The dissociation energy of H
2
is 432.0 kJ mol
1
and the fundamental vibrational frequency of the molecule is 1.257 10
14
s
1
.
Calculate the classical dissociation energy. Estimate the zero-point energies of HD and D
2
and their dissociation energies.
Solution
13.31. A molecule AB
2
is known to be linear but it is not known whether it is BAB or ABB. Its infrared spectrum is found to
show bands corresponding to three normal modes of vibration. Which is the structure?
Solution
13.32. The frequency of the OH stretching vibration in CH
3
OH is 3300 cm
1
. Estimate the frequency of the OD stretching vibration in
CH
3
OD.
Solution
13.33. The spectroscopic constants for the OH radical are
0
=3737.76 cm
1
,
0
x
e
=84.8813 cm
1
, B
= 18.9108 cm
1
. Predict the
frequencies at which (a) the P branch transitions ending in, and (b) the R branch beginning in, J =0, 1, 2 will be observed.
Solution
13.34. Irradiation of acetylene with mercury radiation at 435.83 nm gives rise to a Raman line at 476.85 nm. Calculate the vibrational
frequency that corresponds to this shift.
Solution
13-7
13.35. The fundamental vibrational frequency of H
127
I is 2309.5 cm
1
. Calculate the force constant of the bond.
Solution
*13.36. The following are some normal modes of vibration for several molecules:
[[Image]]
In each case, determine the point group and refer to Appendix E on p. 1028 to determine whether the vibration is active in the
infrared and in the Raman spectrum. Then check your conclusions by reference to the appendix to this chapter (p. 707).
Solution
*13.37. Prove that the force constant k corresponding to the Morse potential function (Eq. 13.146) at small bond extensions is
k =2D
e
a
2

Calculate the vibration frequency v
0
on the basis of the following Morse parameters for H
35
Cl:
D
e
=4.67 eV
a =1.85 10
8
cm
1

Solution
*13.38. The Morse function is only one of several models used to describe the behavior of the potential energy of diatomic molecules. A
popular and very accurate model introduced by Murrell and Sorbie [J. Chem. Soc., Faraday Trans. 2, 70, 1552(1974)] is the so-
called Extended Rydberg function, which is written as
1
2 3
1 2 3
( ) (1 )e ,
a x
p e
E x D a x a x a x

= + + +
where x =r r
e
, as in the case of the Morse potential of Eq. 13.146, and the a
i
are constants for a given molecule.
a. Derive an expression for the force constant in terms of the parameters D
e
and a
i
.
b. Show that in order for a function of this form to have a minimum at r =r
e
, a
1
must be both the coefficient of x and the
exponential parameter.
Solution
*13.39. Yet another model for a diatomic potential is the Bond Order function used by Garcia and Lagan [Mol. Phys. 56, 621(1985)],
which is given as
( ) ( )
1
exp .
N
p e n
n
E x D c n x
=
=

Show that for N =2, with appropriate choices for the coefficients c
1
and c
2
, this is identical to the Morse potential of Eq. 13.146
expressed as E
p
=De(1 e
x
)
2
D
e
.
Solution
Chapter 13: Foundations of Chemical Spectroscopy Electronic Spectra
13-8
*13.40. The parameters for the bond order (see Problem 13.39) potential of the
35
Cl
16
O radical with N =4 are (in atomic units) c
1
=2.691
042, c
2
=2.545 521, c
3
=1.017 916, c
4
=0.163437, De =0.10302, and =1.763 768. What is the vibrational frequency (in cm
1
)
predicted by this model? [Note that the force constant can be expressed in units of energy area
1
.]
Solution
*13.41. A model for the
14
N
14
N
16
O
+
ion assigns the following force constants for the two stretching frequencies: k
12
=1092.8 N m
1
, and
k
23
=890.68 N m
1
. Use Eqs. 13.17113.174 to calculate the two stretch frequencies obtained from the model.
Solution
*13.42. The fundamental and a few successive overtones of the
2
H
+
molecule lie at 2191, 2064, 1941, 1821, 1705, 1591, 1479 and 1368 cm
1
, respectively.
a. Starting from Eq. 13.139, derive an expression that can be used to obtain both
0
and x
e
by a suitable analysis of the data.
b. Perform the analysis and calculate both
0
and x
e
.
Solution
Electronic Spectra
13.43. Sketch potential energy curves for a diatomic molecule in its ground electronic state and n an excited state, consistent with the
following observations:
a. There is a strong 0 0 absorption band, and strong 0 0, 1 1, and 2 2 emission bands.
b. The strongest absorption band is 4 0, and the strongest emission band is 0 2.
c. There is no sharp rotational fine structure in absorption, but there is a sharp emission spectrum.
d. The absorption spectrum shows a well-defined fine structure for the 0 0, 1 0, 2 0, 3 0, and 4 0 transitions and for
the 6 0 and 7 0, but not in between.
Solution
*13.44. Using the data in Example 13.12 on p. 702, determine the area under the curve in a plot of v against v. Extrapolate to zero v to
obtain v
max
, since the Birge-Sponer extrapolation shows that at that point v = v
max
. A better value may be obtained by a nonlinear
extrapolation. What are the values of v not given in the table?
Solution
13.45. Calculate the dissociation energy of the hydrogen molecule ion from the vibrational energy level separations of
2
H .
+
The values for
the transitions 1 0, 2 1, , are, respectively, 2191, 2064, 1941, 1821, 1705, 1591, 1479, 1368, 1257, 1145, 1033, 918, 800,
677, 548, 411, with all values given in cm
1
. Use both a linear plot and a curve to obtain answers.
Solution
Chapter 13: Foundations of Chemical Spectroscopy Electronic Spectra
13-9
13.46. The electronic spectra of diatomic molecules in the gas phase typically show extensive vibrational structure superimposed on the
broader electronic transition. Taking the equilibrium geometry of the ground electronic state to be the zero energy, the G
() of Eq.
13.138 can be used to express the energies of the vibrational states v (in cm
1
) of this electronic state. Denoting the minimum
energy of the excited electronic state as
e
T
(in cm
1
), the vibrational energy levels v of the excited state can be expressed as
( ).
e
T G +

Derive an expression for the frequencies of the transitions between the vibrational levels of the ground and
excited electronic states. (Note that the vibrational frequencies and anharmonicity constants are not the same for the ground and
excited electronic states.)
Solution
13.47. An easy and reliable way to analyze the electronic spectrum of a diatomic molecule is to use the equation derived in Problem 13.46
as the model for a multiple regression analysis (several plotting packages and mathematics packages such as Mathcad can perform
this task) to simultaneously identify the five unknowns,
0 0 0
, , , ,
e e
T x
and
0 e
x [McNaught, J. Chem. Ed. 57, 101(1980)]. The
following data are from the electronic spectrum of iodine.
0 (nm) 1 (nm) 2 (nm)
17 567.2 15 581.0 10 607.3
18 564.2 16 577.8 11 603.1
19 561.5 17 574.2 12 599.1
20 558.5 18 571.3 13 595.5
21 555.8 19 568.3 14 591.8
22 553.0 20 565.2 15 588.1
23 550.1 21 559.6 16 584.8
24 547.8 22 556.9 17 581.2
25 542.7 23 554.2 18 578.1
26 540.7 24 551.8 19 575.1
27 538.5 25 549.0 20 572.4

Perform a multiple regression analysis and identify the spectroscopic parameters of the ground and excited electronic states.
Literature values are (in cm
1
)
e
T
=15730,
0
=132.1,
0 e
x =1.051,
0
=214.5, and
0 e
x =0.614.
Solution
Chapter 13: Foundations of Chemical Spectroscopy Essay Questions
13-10
13.48. The dissociation energy (from the zero-point level) of the ground state
3
2 g
( ) O

molecule is 5.09 eV. There exists an electronically
excited
3
u
state of O
2
, whose zero-point level lies 6.21 eV above the zero-point level of the ground state. The ground-state
molecule dissociates into two ground-state O(
3
P) atoms, while the
3
u
species dissociates into one ground-state O(

3
P) atom and an
O*(
1
D) atom that lies 1.97 eV above the ground state. Sketch the potential-energy curves and calculate the dissociation energy of
3
2 u
( ) O

into O +O*(
1
D).
Solution
13.49. The spectroscopic dissociation energy D
0
is the energy required to dissociate the molecule in its ground vibrational state. This is
always slightly smaller than the actual depth of the electronic potential energy because of the zero-point energy of the molecule (see
Figure 13.22). Given that for HCl, De =4.6173 eV,
0
=2989 cm
1
, and
0 e
x =52.82 cm
1
, calculate the value of D
0
for HCl.
Solution
13.50. The dissociation energy (from the zero-point level) of the ground state NO(X
2
) molecule is 6.6 eV. There exists an electronically
excited B
2
state of NO whose zero-point level lies at 5.7 eV above the zero-point level of the ground state. The ground-state
molecule dissociates into ground state N(
4
S) +O(
3
(P)), while the B
2
species dissociates into two ground-state atoms N(
2
D) +O(
3
P)
that lie 3.3 eV above its ground state. Sketch the potential energy curves and calculate the dissociation energy of NO into N(
2
D) +
O(
3
P).
Solution
13.51. Sodium vapor, which consists mainly of Na
2
molecules, has a system of absorption bands in the green, the origin of the 0, 0 band
being at 20 302.6 cm
1
. From the spacing of the vibrational levels it can be deduced that the dissociation energy of the upper state is
0.35 eV. The dissociation of the excited Na
2
gives a normal atom and an atom that emits the yellow sodium D line at 589.3 nm.
Calculate the energy of dissociation of Na
2
in its ground state.
Solution
For additional problems, see the books listed at the end of the problems in Chapter 12 (pp. 634-635).

Essay Questions
13.52. State the laws of Lambert and Beer, and write an equation comprising the two laws.
13.53. Explain clearly what is meant by absorbance and transmittance, and derive a relationship between them.
13.54. Give an account of the fundamental origins of ultraviolet and infrared spectra.
13.55. Explain the selection rules for infrared spectra, with examples.
Chapter 13: Foundations of Chemical Spectroscopy Solutions
13-11
Solutions
13.1. The molar absorption coefficient of human hemoglobin (molecular weight 64 000) is 532 cm
1
mol
1
at 430 nm. A solution of
hemoglobin in a cuvette having a light path of 1 cm was found at that wavelength to have a transmittance of 76.7%. Calculate the
concentration in mol dm
3
and in g dm
3
.

Solution:

Given:
1 1
64000, 532 cm mol 430 nm, 1cm, 76.7% MW l T = = = = =
Required: c in mol dm
3
and in g dm
3

To determine the concentration of the hemoglobin solution, we use the Beer-Lambert Law, given by Eq. 13.45. This is one of the most
important laws in understanding the foundation of chemical spectroscopy.

0
10
log
I
A cl
I
= =

Since cl is dimensionless, the molar absorption coefficient then has the units dm
3
mol
1
cm
1

Eq. 13.39 defines the transmittance as,

0
I
T
I

Using the above and rearranging Eq. 13.45, we can obtain an expression that can be used to solve the problem.
13-12
( )
0
1
0
0
10
0
10
10
3 1
0.767
0.767 1.303780965
log
log
log 1.303780965
532dm cm
I
I
I
I
I
cl
I
I
I
c
l
c
=
= =
=
=
=
( )
1
mol 1 cm
( )
3
4 3
0.000215739 mol dm
2.16 10 mol dm
c
c

=
=

Converting to g dm
-3
we use the molecular weight given in the problem
0.000215739 mol c =
3 1
dm 64000g mol

3
3
13.807297 2 gdm
13.8 gdm
c
c
=
=

13-13
13.2. A spectrophotometer has a meter that gives a reading directly proportional to the amount of light reaching the detector. When the
light source is off, the reading is zero. With pure solvent in the light path, the meter reading is 78; with a 0.1 M solution of a solute
in the same solvent, the meter reading is 55. The light path is 0.5 cm. Calculate the absorbance, the transmittance, and the molar
absorption coefficient.

Solution:

Given:
0
78
, 0.1 , 0.5 cm
55
I
c M l
I
= = =

Required: , , A T
To find the absorbance, we use the value given for
0
I
I
and substitute it into Eq. 13.45,
0
10
10
log
78
log 0.151731913
55
0.152
I
A cl
I
A
A
= =
= =
=

The transmittance is defined in Eq. 13.39 as,

0
55
78
0.705128205
0.705
I
T
I
T
T
T
| |
=
|
\ .
=
=

To find the molar absorption coefficient, we simply use Eq. 13.45 once more.

13-14
3
3 1 1
3 1 1
0.151731913
0.1mol dm 0.5cm
3.034638264dm cm mol
3.03dm cm mol
A cl
A
cl

=
=
=
=
=

13-15
13.3. The transmission of a potassium chromate solution was measured at a wavelength of 365 nm using a cell with a 1.0-cm path length.
The data are as follows:
Transmission 0.357 0.303 0.194 0.124
Conc. 10
4
/mol dm
3
0.90 1.10 1.50 1.90

Calculate the molar Naperian absorbance and the molar decadic absorbance.

Solution:

Given: 365 nm, 1.0 cm, l c = =
Required: Naperian and decadic absorbance

To solve this problem, we use Eq. 13.45 and form a plot of logT against concentration.
10
0
log
2.303
I cl
I

=
This should give a straight line with a slope of
2.303
l
. See the plot below.

13-16
The values used the create the plot are:
Transmission 0.357 0.303 0.194 0.124
Conc. 10
4
/mol
dm
3

0.9 1.1 1.5 1.9
logT -0.44733 -0.51856 -0.7122 -0.90658
The slope of the plot obtained is
3 3 1
0.4653 10 dm mol m

= .
Since
3 3 1
0.4653 10 dm mol
2.303
l

= we can then solve for the molar absorption coefficient.

3 3 1
3 3 1
3 3 1
2 1
2 1
0.4653 10 dm mol
2.303
0.4653 10 dm mol 2.303
1.0 cm 0.1 dm
0.4653 10 dm mol 2.303
0.1 dm
10715.859dm mol
1071.5859m mol
l
l
l
=

=
= =

=
=
=

The decadic absorbance coefficient for a 10 M solution is then,
3
10715.859 dm
A cl
A
=
=
1
mol
1
cm
6
10 10 mol

3
dm
1cm
0.10715859
0.107
A
A
=
=


13-17
13.4. An aqueous solution containing 0.95 g of oxygenated myoglobin (M
r
=18 800) in 100 cm
3
gave a transmittance of 0.87 at 580 nm,
with a path length of 10.0 cm. Calculate the molar absorption coefficient.

Solution:

Given:
3
0.95g, 18 800, 100 cm, 0.87, 580nm, 10.0cm
r
m M V T l = = = = = =
Required:

To calculate we use the Beer-Lambert Law in Eq. 13.45.
0
10
log
I
A cl
I
= =
The absorbance is first calculated by taking the inverse log of the transmittance.
( )
1
10
1
10
log
log 0.87
0.060480747
A T
A
A
=
=
=

We then calculate the concentration of the hemoglobin.
3 3
3 3
1dm 1000cm
100cm 0.1dm
1
0.95 g
n m
c
V M V
c
=
=
| |
= =
|
\ .
=
18800 g
3 1
3
4 3
1
0.1dm mol
0.000505319mol dm
5.05319 10 mol dm
c
c

| |
|
\ .
=
=

Solving for we obtain,
13-18
4 3
3 1 1
3 1 1
0.060480747
5.05319 10 mol dm 10.0 cm
11.96882159dm cm mol
12.0dm cm mol
A
cl

=
=

=
=

13-19
13.5. A substance in aqueous solution at a concentration of 0.01 M shows an optical transmittance of 28% with a path length of 2 mm.
Calculate the molar absorption coefficient of the solute. What would be the transmittance in a cell 1-cm thick?

Solution:

Given: 0.01 , 0.28, 2mm c M T l = = =
Required:
1cm
,
l
T
=

To calculate we use the Beer-Lambert Law in Eq. 13.45. We can solve in a similar manner to problem 13.4.
( )
0
10
1
10
1
10
log
log
log 0.28
0.552841969
I
A cl
I
A T
A
A
= =
=
=
=

3
3 1 1
3 1 1
0.552841969
0.01mol dm 0.2 cm
276.4209843dm cm mol
276dm cm mol
A
cl

=
=
=
=

To determine the transmittance when the path length is 1.0 cm, we use the molar absorption coefficient obtained above and solve for the
absorbance.
3
276.4209843 dm
A cl
A
=
=
1
cm
1
mol
0.01mol
3
dm
1.0 cm
2.764209843 A =

13-20
From Eq. 13.43 we can find the transmittance,
10
10
10
0.764209843
log % 2
log % 2 2.764209843
log % 0.764209843
% 10
0.17210368%
0.17%
T A
T
T
T
T
T
=
=
=
=
=
=


13-21
13.6. The molar absorption coefficient of hemoglobin at 430 nm is 532 dm
3
mol
1
cm
1
. A solution of hemoglobin was found to have an
absorbance of 0.155 at 430 nm, with a light path of 1.00 cm. Calculate the concentration.

Solution:

Given:
1 1
532 cm mol 430 nm, 1.00cm, 0.155 l A = = = =
Required: c

This problem is similar to problem 13.1, however is much simpler to solve. By rearranging Eq. 13.45, we can obtain the concentration

3 1 1
0.155
532 dm mol cm
A cl
A
c
l
c
=
=
=
1.00 cm
3
4 3
0.000291353 mol dm
2.91 10 mol dm
c
c

=
=

13-22
13.7. A 10 M solution of a substance gave an absorbance of 0.1028 with a light path of 1 cm. Calculate the molar absorption coefficient.
What would be the percentage light transmittance of a 1-m solution with the same light path?

Solution:

Given: 10 , 0.1028, 1cm c M A l = = =
Required:
1
,
c M
T

=

To calculate we rearrange the Beer-Lambert Law, Eq. 13.45.

6 3
3 1 1
4 3 1 1
0.1028
10 10 mol dm 1 cm
10280dm cm mol
1.028 10 dm cm mol
A cl
A
cl

=
=
=

=
=

To determine the transmittance when the concentration is 1 M, we use the molar absorption coefficient obtained above and solve for the
absorbance.
4 3
1.028 10 dm
A cl
A
=
=
1
cm
1
mol
6
10 mol
3
dm
1.0 cm
2
1.028 10 A

=

13-23
10
2
10
10
1.98972
log % 2
log % 2 1.028 10
log % 1.98972
% 10
97.6607376%
97.66%
T A
T
T
T
T
T
=
=
=
=
=
=

13-24
13.8. Two substances of biological importance, NAD
+
and NADH, have equal absorption coefficients, 1.8 10
4
dm
3
mol
1
cm
1
, at 260
nm (a wavelength at which absorption coefficients are equal is known as the isosbestic point
6
). At 340 nm, NAD
+
does not absorb at
all, but NADH has an absorption coefficient of 6.22 10
3
dm
3
mol
1
cm
1
. A solution containing both substances had an absorbance
of 0.215 at 340 nm and of 0.850 at 260 nm. Calculate the concentration of each substance.

Solution:

Given:
4 3 1 1
both
260 nm; 1.8 10 dm mol cm , 0.850 A = = =
3 3 1 1
NADH
340 nm; 6.22 10 dm mol cm , 0.215 A = = =
Required:
NAD NADH
, c c
+

Since we are told that at 340 nm, NAD
+
does not absorb at all, we can find the concentration for NADH by applying the Beer-Lambert law
at 340 nm. We can assume the path length, l =1.00 cm which is the standard value.

NADH
3 3 1 1
0.215
6.22 10 dm mol cm
A cl
A
c
l
c
=
=
=
1.00 cm
5 3
NADH
5 3
NADH
3.45659 10 mol dm
3.46 10 mol dm
c
c

=
=

To find the concentration of NAD+, we first calculate the absorbance of NADH at 260 nm.
4 3
1.8 10 dm
A cl
A
=
=
1
cm
1
mol
5
3.45659 10 mol

3
dm
1.00 cm
0.622186495 A =

The remaining absorbance at 260 nm will be purely the absorbance of NAD+,

6
Fromthe Greek prefix iso-, the same, and sbestos, quench. This word is sometimes incorrectly written as isobestic.
13-25
NAD+
NAD+
0.850 0.622186495
0.227813505
A
A
=
=

Now we can solve for concentration in a similar manner as above.
NAD+
4 3 1 1
0.227813505
1.80 10 dm mol cm
A
c
l
c
=
=
1.00 cm
5 3
NAD+
5 3
NAD+
1.26563 10 mol dm
1.27 10 mol dm
c
c

=
=

13-26
13.9. The transmittance of a 0.01 M solution of bromine in carbon tetrachloride, with a path length of 2 mm, is 28%. Calculate the molar
absorption coefficient of bromine at that wavelength. What would the percentage transmittance be in a cell 1-cm thick?

Solution:

Given: 0.01 , 0.28, 2mm c M T l = = =
Required:
1cm
,
l
T
=

This problem is parallel to problem 13.5. To calculate we use the Beer-Lambert Law in Eq. 13.45.

( )
0
10
1
10
1
10
log
log
log 0.28
0.552841969
I
A cl
I
A T
A
A
= =
=
=
=

3
3 1 1
3 1 1
0.552841969
0.01mol dm 0.2 cm
276.4209843dm cm mol
276dm cm mol
A
cl

=
=
=
=

To determine the transmittance when the path length is 1.0 cm, we use the molar absorption coefficient obtained above and solve for the
absorbance.
3
276.4209843 dm
A cl
A
=
=
1
cm
1
mol
0.01mol
3
dm
1.0 cm
2.764209843 A =

13-27
10
10
10
0.764209843
log % 2
log % 2 2.764209843
log % 0.764209843
% 10
0.17210368%
0.17%
T A
T
T
T
T
T
=
=
=
=
=
=

13-28
13.10. An acid HA ionizes in aqueous solution into H
+
and A
ions. At a wavelength of 430 nm HA does not absorb light, but A
does so
with an absorption coefficient of 458 dm
3
cm
1
mol
1
. A solution of the acid at a concentration of 0.1 M was found to have a
transmittance of 1.47% at 430 nm with a path length of 1 cm and at 25 C. Calculate the dissociation constant of HA at 25 C, and
G for the dissociation process.

Solution:

Given:
3 1 1
430 nm, 458 dm cm mol , 0.01 , 1.47% 0.0147, 1cm, 25 C c M T l T = = = = = = =
Required: ,
c
K G

To calculate the dissociation constant and Gibbs free energy, we need to recall the principles we learned in chapter 4.

The dissociation of the acid is given by,

HA H A
+
+

| |
H A
HA
c
K
+
( (

=
And therefore K
c
is calculated by determining the concentration of the anion A
-
which is equal to c. This value is also the same
concentration of H
+
.

( )
0
10
1
10
1
10
log
log
log 0.0147
1.832682665
I
A cl
I
A T
A
A
= =
=
=
=

To find c, we rearrange Eq. 13.45,
13-29
3 1 1
1.832682665
458dm mol cm
A cl
A
c
l
c
=
=
=
1.00 cm
3 3
4.001491 10 mol dm c

=

At equilibrium we have the following situation,

3 3 3
HA H A
0.1 0 0
0.1 4.001491 10 4.001491 10 4.001491 10
initial
equilibrium
c M
c M M M
+

+

Solvingfor K
c
we obtain,

3
4.001491 10 mol
c
K
=
3
dm
3 3
3
4.001491 10 mol dm
1 4.001491 10 mol

(
(

3
dm
5 3
5 3
1.60763 10 mol dm
1.607 10 mol dm
c
c
K
K

(

=
=

To find the Gibbs free energy we use Eq. 4. 27
1
ln
8.3145J K
c
G RT K
G
=
=
1
mol 298.15 K
( )
5 3
1
1
ln 1.60763 10 mol dm
27363.26517 J mol
27.4 kJ mol
G
G

=
=

13-30
13.11. In the Balmer series of the hydrogen atom, the first emission line is observed at 656.3 nm. Calculate the value of the Rydberg
constant. What is the energy of the light quanta emitted during the transition?

Solution:

Given: 656.3nm = , Balmer series,
Required: , R

To find Rydbergs constant, we use the principles we learned in Chapter 11. We can find R using Eq. 11.50 and the fact that for the Balmer
series, n =3. n
1
=2.

2 2
1 2
9 2 2
9
1
7 1
1 1 1
1 1 1
656.3 10 m 2 3
35 1
4 656.3 10 m
10970592.63m
1.097 10 m
R
n n
R
R
R
R
| |
= =
|
\ .
| |
=
|
\ .
| |
=
|
\ .
=
=

To find the energy we use,
34
6.626 10 J s
hc
E
E
=
8
2.998 10 m
1
s
9
656.3 10 m
19
19
3.02678 10 J
3.027 10 J
E
E
=
=

13-31
13.12. The ground state of the Li atom has the electronic configuration 1s
2
2s
1
. What is its spectroscopic term? If the 2s electron is excited
to the 2p state, what terms are then possible?

Solution:

Given: Li, 1s
2
2s
1

Required: spectroscopic terms for 2s
1
and 2p
1
states

The 1s
2
electrons form a closed shell and need not be considered.

13-32
13.13. Suppose that an excited state of the carbon atom has the electronic configuration 1s
2
2s
2
2p
1
3p
1
. What are the possible spectroscopic
terms?

Solution:


13-33
13.14. What are the terms for the following electronic configurations?
a. Na (1s
2
2s
2
2p
6
3p
1
)
b. Sc (1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
1
)

Solution:


13-34
13.15. What values of J may arise in the following terms?
1
P,
3
P,
4
P,
1
D,
2
D,
3
D,
4
D

Solution:


13-35
*13.16. Calculate the Land-g-factor for a
2
P
1/2
level. What would be the anomalous Zeeman splitting for this level in a magnetic field of
4.0 T?

Solution:


13-36
*13.17. Calculate the spacing between the lines for a
3
D
1

3
P
0
transition, in an anomalous Zeeman experiment with a magnetic field of 4.0
T.

Solution:

Given:
3
D
1

3
P
0
, B =4.0 T
Required: E

This problem is very similar to example 13.8 given in the text, and can be solved in a similar manner.

For the
3
P
0
level, g
J
=0. The splitting of the line is therefore entirely due to the splitting of
3
D
1
level. For this level, g
J
is,
( ) ( ) ( )
( )
1 2 1 2 2 3
1
2 2
1
2
J
J
g
g
+
= +
=

It will be split into three levels with M
J
=1, 0, -1, and the separation between the levels is given by Eq. 13.88,
24 1
1
9.273 10 J T
2
J B
E g B
E

=
= 4.0 T
23
1.8546 10 J E

=

Converting this energy level difference to the spacing in cm we get,
23
1.8546 10 J
E
=
34
6.626 10 J
s
10 1
2.998 10 cms

0.933613656cm
0.93cm
E
E
=
=

13-37
13.18. The separation between neighboring lines in the pure rotational spectrum of
35
Cl
19
F is found to be 1.023 cm
1
. Calculate the
interatomic distance.

Solution:

Given:
35
Cl
19
F,
1
2 1.023cm B

=
Required: r

Eq. 13.93 gives the relationship between interatomic distance, inertia and reduced mass.
2 2 1 2
0 0
1 2
mm
I r r
m m
= =
+

To solve for interatomic distance, we first calculate the moment of inertia from Eq. 13.100 since we already have the value of the rotational
constant, B.
2
2
34
8
8
6.626 10 J s
h
B
Ic
h
I
cB
I
=
=
2 10
8 2.998 10 cm
1
s
1
0.5115 cm
46
5.47248 10 J I

=

The reduced mass is calculated using Eq.13.94,
( )
1 2
1 2
1 1
1 23 1
23
26
35gmol 19gmol
35 19 gmol 6.022 10 mol
2.04497 10 g
2.04497 10 kg
mm
m m
=
+
=
+
=
=

Rearranging Eq. 13.93 and solving for r we obtain,
13-38
2
0
46
26
10
5.47248 10 J
2.04497 10 kg
1.63587 10 m
164pm
I r
I
r
r
r
r
=
=
=
=

13-39
13.19. The lines in the pure rotational spectrum of HF are 41.9 cm
1
apart. Calculate the interatomic distance. Predict the separation
between the lines for DF and TF.

Solution:

Given:

HF,
1
2 41.9cm B

=
Required: r, 2B
DF
, 2B
TF

This problem can be solved in a similar manner as problem 13.18.

2 2 1 2
0 0
1 2
mm
I r r
m m
= =
+

constant, B.
2
2
34
8
8
6.626 10 J s
h
B
Ic
h
I
cB
I
=
=
2 10
8 2.998 10 cm
1
s
1
20.95 cm
47
1.33612 10 J I

=

( )
1 2
1 2
1 1
1 23 1
24
27
1gmol 19gmol
1 19 gmol 6.022 10 mol
1.57755 10 g
1.57755 10 kg
mm
m m
=
+
=
+
=
=

13-40

2
0
47
27
11
1.33612 10 J
1.57755 10 kg
9.20305 10 m
92pm
I r
I
r
r
r
r
=
=
=
=

To find the separation, we take a look at Eq. 13.93 and 13.100 and notice that the separation B is inversely proportional to I and therefore, to
the reduced mass . The interatomic separations are assumed to be the same. The reduced mass for HF, DF and TF are in the ratio:

HF DF TF
1 19 2 19 3 19
: :
20 21 22
1 : 1.90 : 2.72

=

Using the ratios, the predicted separations are,
1
DF
1
DF
1
DF
1
TF
1
TF
1
TF
2 41.9 cm 1.90
2 21.9975 cm
2 22.0 cm
2 41.9 cm 2.72
2 15.36333 cm
2 15.4 cm
B
B
B
B
B
B
=
=
=
=
=
=

13-41
13.20. In the microwave spectrum of
12
C
16
O the separation between lines has been measured to be 115270 MHz. Calculate the interatomic
distance.

Solution:

Given:
12
C
16
O, 2 115270MHz B =
Required: r


2 2 1 2
0 0
1 2
mm
I r r
m m
= =
+

constant, B.
2
2
34
8
8
6.626 10 J s
h
B
Ic
h
I
cB
I
=
=
2 6 1
1
8 115270 10 s
2

46
1.45605 10 J I

=

( )
1 2
1 2
1 1
1 23 1
23
26
12.000gmol 15.995gmol
12.000 15.995 gmol 6.022 10 mol
1.13853 10 g
1.13853 10 kg
mm
m m
=
+
=
+
=
=

13-42

2
0
46
26
10
1.45605 10 J
1.13853 10 kg
1.13088 10 m
113pm
I r
I
r
r
r
r
=
=
=
=

13-43
*13.21. The J = 0 J =1 line in the microwave absorption spectrum of
12
C
16
O and of
13
C
16
O was measured by Gillam et al., [Phys. Rev.
78, 140(1950)]. In its ground vibrational state, the former has the value 3.842 35 cm
1
and the latter, the value 3.673 37 cm
1
.
Calculate
a. the bond length of the
12
C
16
O molecule,
b. the relative atomic mass of
13
C,
c. the bond length of the
13
C
16
O molecule.

Solution:

Given:

12 16 1 13 16 1
C O; 3.842 35 cm , C O; 3.673 37 cm
j j
= =

Required:
( ) ( )
12 16 13 16
C O , , C O
r
r M r

a. This problem can be solved in a similar manner as problem 13.18 since interatomic distance is the same as bond length.

2 2 1 2
0 0
1 2
mm
I r r
m m
= =
+

First, we calculate the moment of inertia from Eq. 13.99 and Eq. 13.100. For the transition J = 0 J =1, 2B = and therefore
( )
( )
2
2
34
2 1
2 1
8
2
8
2 6.626 10 J s
j
j
j
J B
h
J
Ic
h
I
c
I
= +
= +
=

=
2 10
8 2.998 10 cm
1 1
s 3.842 35 cm
1
s
46
46 2
1.45701 10 J s
1.45701 10 kgm
I
I
=
=

13-44
( )
1 2
1 2
1 1
3 1
1 23 1
26
12.000gmol 15.994914gmol
10 kgg
12.000 15.994914 gmol 6.022 10 mol
1.13853 10 kg
mm
m m
=
+
=
+
=

2
0
46
1.45701 10 kg
I r
I
r
r
=
=
=
2
26
m
1.13853 10 kg
10
1.13125 10 m
113.1pm 0.1131 nm
r
r
=
= =

b. To find the reduced mass, we take a look at Eq. 13.93 and 13.100 and notice that the separation B is inversely proportional to the
reduced mass .
If M
r
is the relative mass of
13
C, and subscript 1 refers to
12
C
16
O and, subscript 2 refers to
13
C
16
O, we have,
13-45
1 1
2 2
1
3.842 35 cm
B
B
=
1
3.673 37 cm
( )
15.994914 12.000 15.994914
12.000 15.994914 15.994914
15.994914
1.046001356 0.145853207
15.994914
15.994914
7.171603411
15.994914
7.171603411 15.994914 15.994914
114.7091798 8.823
r
r
r
r
r
r
r r
M
M
M
M
M
M
M M

=
+ +
| |
=
|
+
\ .
=
+
+ =
= 310589
13.00069613
r
r
M
M =

c. This problem can be solved in a similar manner as part a.

2 2 1 2
0 0
1 2
mm
I r r
m m
= =
+

First, we calculate the moment of inertia from Eq. 13.99 and Eq. 13.100. For the transition J = 0 J =1, 2B = and therefore
( )
( )
2
2
34
2 1
2 1
8
2
8
2 6.626 10 J s
j
j
j
J B
h
J
Ic
h
I
c
I
= +
= +
=

=
2 10
8 2.998 10 cm
1 1
s 3.673 37 cm
1
s
46
46 2
1.52404 10 J s
1.52404 10 kgm
I
I
=
=

13-46

( )
1 2
1 2
1 1
3 1
1 23 1
26
13.00335gmol 15.994914gmol
10 kgg
13.00335 15.994914 gmol 6.022 10 mol
1.19103 10 kg
mm
m m
=
+
=
+
=

2
0
46 2
1.52404 10 kgm kg
I r
I
r
r
=
=
=
2
26
m
1.19103 10 kg
10
1.13119 10 m
113.1pm 0.1131 nm
r
r
=
= =

Therefore, there is essentially no difference in the bond length with the
13
C isotope.

13-47
13.22. The microwave spectrum of
16
O
12
C
32
S shows absorption lines separated by 12.163 GHz. That of
16
O
12
C
34
S shows lines separated by
11.865 GHz. The determination of the bond distances involves solving two simultaneous quadratic equations, which is best done by
successive approximations. To avoid all that labor, simply confirm that the results are consistent with r(OC) =116 pm and r(C
S) =156 pm.

Solution:

Given:
16 12 32 16 12 34
O C S; 2 12.163 GHz, O C S, 2 11.865 GHz B B = =
Required: confirm that the results are consistent with ( ) ( ) O C 116 pm, C S 156 pm r r = =

To confirm that the bond distances are consistent with ( ) ( ) O C 116 pm, C S 156 pm r r = = , we can calculate and compare the moments
of inertia based on the absorption line separations and the bond distances.

The B values are half the separations,
16 12 32 9 1
16 12 34 9 1
O C S; 6.0815 10 s
O C S, 5.9325 10 s
B
B
=
=

We can then calculate the moment of inertia from Eq. 13.100 since we already have the value of the rotational constant, B.
( )
2
2
34
16 12 32
8
8
6.626 10 J s
O C S
h
B
Ic
h
I
cB
I
=
=
2 9 1
8 6.0815 10 s

( )
( )
16 12 32 45
34
16 12 34
O C S 1.37991 10 J
6.626 10 J s
O C S
I
I
=
2 9 1
8 5.9325 10 s

( )
16 12 34 45
O C S 1.41457 10 J I

=

The moment of inertial of a linear triatomic molecule is given by Eq. 13.103
13-48
( )
2
1 12 3 23 2 2
1 12 3 23
mr m r
I mr m r
m
= +
We can write x for r
12
and y for r
23
, and M
1
, M
2
and M
3
for the molar masses. We then obtain the following quadratic equations,
( )
( )
( )
( )
2
1 3 16 12 32 2 2
1 3
45 42 2
2
1 3
16 12 34 2 2
1 3
45 42 2
1
O C S
1.37991 10 J 1.37991 10 gm
1
O C S
1.41457 10 J 1.41457 10 gm
M x M y
I M x M y
L M
M x M y
I M x M y
L M

| |
= + |
|
\ .
= =
| |
= +
|
|
\ .
= =

Insertion of
23 1 1 1 1
1 3 3
6.022 10 mol , 16gmol , 32gmol , 34 gmol , L M M M

= = = =
1
60gmol , 116pm, and 156 pm M x y
= = = into
the left hand side (LHS) and right hand side (RHS) of these equations gives,

( )
( ) ( )
( )
16 12 32
42 2
2
1 1
2 2
1 1
1
23 1
2 1
O C S ;
LHS:
1.37991 10 gm
RHS:
16gmol 116 pm 32gmol 156 pm
60 gmol
6.022 10 mol
830139.7333gpm mol
I

=
| |

|
= +
|
\ .
=
23 1
6.022 10 mol
2
12
42 2
42 2
10 m
pm
1.37851 10 gm
LHS RHS 1.38 10 gm
| |
|
\ .
=
=

13-49
( )
( ) ( )
( )
16 12 34
42 2
2
1 1
2 2
1 1
1
23 1
2 1
O C S ;
LHS:
1.41457 10 gm
RHS:
60 gmol
6.022 10 mol
844574.9333gpm mol
I

=
| |

|
+
|
\ .
=
=
23 1
6.022 10 mol
2
12
42 2
42 2
10 m
pm
1.40248 10 gm
LHS RHS 1.4 10 gm
| |
|
\ .
=
=

13-50
13.23. The maximum potential energy that a diatomic molecule can store is
2
1
,
2
kx where x is the amplitude of vibration. If the force
constant k is 1.86 10
3
N m
1
, calculate the maximum amplitude of vibration for the CO molecule in the v =0 vibrational state.
Compare this to the bond length obtained in Problem 13.21. Use the value of u
r
in that problem.

Solution:

Given:
3 1
CO
1.86 10 N m , 0 k v = = , Problem 13.21
Required: x, compare with r in Problem 13.21

To solve for amplitude of vibration, x, we substitute using Eq. 13.123 and rearrange the equation given above to get,

2
2
1
2
1
2 4
1
2
1
2
h k
kx
h
x
k
h
x
k

=
=
| |
=
|
|
\ .

We use
26
1.19103 10 kg

= from Problem 13.21, substitute and solve to obtain,
( )
( )
1
34 2
3 1 26
1
23 2
2
1
23 2
2
12 3
6.626 10 J s 1
2 1.86 10 N m 1.19103 10 kg
2.24054 10 m
2.24054 10 m
4.73344 10 m 4.73344 10 nm 0.0473344
x
x
x
x

| |
=
|
|

\ .
=
=
= = =

13-51
In Problem 13.21, the bond length for the CO molecule was found as 0.1131 nm r = .
Compared to x,

3
4.73344 10 nm
% change

= 100%
0.1131 nm
% change 4.1844748%
% change 4.2%
=
=

The extension therefore represents about a 4% change.

13-52
13.24. Consider the following molecules: H
2
, HCl, CO
2
, CH
4
, H
2
O, CH
3
Cl, CH
2
Cl
2
, H
2
O
2
, NH
3
, and SF
6
. Which of them will give
a. a pure rotational spectrum,
b. a vibrational-rotational spectrum,
c. a pure rotational Raman spectrum,
d. a vibrational Raman spectrum?

Solution:

Given: H
2
, HCl, CO
2
, CH
4
, H
2
O, CH
3
Cl, CH
2
Cl
2
, H
2
O
2
, NH
3
, and SF
6

Required: see above

a. pure rotational
spectrum
b. vibrational-
rotational spectrum
c. pure rotational
Raman spectrum
d. vibrational
Raman spectrum
H
2

HCl
CO
2

CH
4

H
2
O
CH
3
Cl
CH
2
Cl
2

H
2
O
2

NH
3

SF
6

13-53
13.25. Analysis of the vibrational-rotational spectrum of the H
35
Cl molecule shows that its fundamental vibrational frequency
0
is 2988.9
cm
1
. Calculate the force constant of the HCl bond.

Solution:

Given: H
35
Cl,
0
=2988.9 cm
1

Required: k

The force constant is defined in terms of the fundamental frequency in Eq. 13.122,
2 2
0
4 k =

The frequency, in terms of inverse seconds is given by,
0
10
2.998 10 cm
v v c
v
=
=
1 1
s 2988.9 cm
13 1
8.9907 10 s v =


( )
1 2
1 2
1 1
3 1
1 23 1
27
34.96885gmol 1.007825gmol
10 kgg
34.96885 1.007825 gmol 6.022 10 mol
1.62669 10 kg
mm
m m
=
+
=
+
=

Solving for k we get,
( )
2 2
0
2
2 13 1 27
2
2
4
4 8.9907 10 s 1.62669 10 kg
519.1007608kgs
519.10kgs
k
k
k
k

=
=
=
=

13-54
13.26. A few transitions in the P and R branches of the infrared spectrum of H
35
Cl spectrum are identified below.
J 0 1 2 3 4 5 6
P (cm
1
) 2865.10 2843.62 2821.56 2798.94 2775.76 2752.04
R (cm
1
) 2906.24 2925.90 2944.90 2963.29 2981.00 2998.04

Using Eqs. 13.134 or 13.135 as appropriate, calculate
0
and the rotational constant . B

Solution:

Given: table above
Required:
0
, . B

Equations 13.135 and 13.136,
( )
0 0
2 1 2 J B J B = + + = +

and ( )
0 0
2 1 2 J B J B = + =

,
Both show that a plot of the observed frequencies as a function of J will be a straight line with slope 2B =

and intercept
0
.
A linear regression of the values in the P branch gives the following plot.

13-55
This gives,
2888.70 22.614J =

From which we obtain the fundamental vibrational frequency as,
1
0
2888.70 cm

=

And the value B
as,
1
22.614
2
11.307cm
B
B

Similarly, we can perform a linear regression of the values in the B branch to give the following results.

2907.3 18.363J =

13-56
From which we obtain the fundamental vibrational frequency as,
1
0
2907.3 cm

=

And the value B
as,
1
18.363
2
9.1815cm
B
B

13-57
13.27. Comparison of the results of Problem 13.26 to experimental values for H
35
Cl (
0
=2990 cm
1
, and B
=10.59 cm
1
) shows that Eqs.
13.134 and 13.135 do not accurately relate the observed transitions to the rotational quantum numbers. Much of the error results
from not taking the anharmonicity of the potential energy curve into account. Using the definition (see Eq. 13.138) T
v,J
= ( +
1
2
)
0

(v +
1
2
)
2

0
x
e
+ J(J +1) , B
derive a more accurate expression for T

v,J
for the v = 0 v = 1 transitions of a diatomic molecule.
[Even this is an approximate treatment because we are ignoring the coupling of rotations with vibrations.]

Solution:

Given T
v,J
= ( +
1
2
)
0
(v +
1
2
)
2

0
x
e
+ J(J +1) , B

Required: expression for T
v,J
for the v = 0 v = 1 transitions of a diatomic molecule

To derive a more accurate expression for T
v,J
, we first write the following expressions for
v = 0 and v =1,
( )
( )
0, 0 0
1, 0 0
1 1
1
2 4
3 9
1
2 4
J e
J e
T x J J B
T x J J B

= + +
= + +

This gives,
( ) ( ) ( )
0, 1, 1, 0,
0, 1, 0 0
2 1 1
J J J J
J J e
T T T
T x B J J J J

=
= + + +

For 1 J J J = = (the P branch), this reduces to,
0 0
2 2
e
x BJ =

For 1 J J J = = + (the R branch), this reduces to,
0 0
2 2
e
x BJ = +

13-58
13.28. From the results of Problems 13.26 and 13.27 and the experimental value of
0
for H
35
Cl given in Problem 13.27, estimate the value
of the anharmonicity constant x
e
. Use the average of the P and R branch values for
0
from Problem 13.26.

Solution:

Given: Problem 13.26, Problem 13.27
Required: x
e

First we take the average of the P and R branch values for
0
from Problem 13.26 to get,
( )
1 1
0
1
0
1
2888.70 cm 2907.3 cm
2
2898cm
= +
=

The more accurate treatment of Problem 13.27 shows that this is actually the value of
0 0
2
e
x .
Therefore we can equate the two and solve for x
e

0 0
1 1 1
1
2 1
2
2990cm 2898cm 2 2898cm
0.015873016cm
1.587 10 cm
e
e
e
e
x
x
x
x

=
=
=
=

13-59
13.29. The vibrational Raman spectrum of
35
Cl
2
shows series of Stokes and anti-Stokes lines; the separation between the lines in each of
the two series is 0.9752 cm
1
. Estimate the bond length in Cl
2
.

Solution:

Given:
1
4 0.9752 cm B =
Required: r

From Figure 13.27, we know that the separation is 4B. Therefore the value of B is,
1
1
1
0.9752 cm
4
0.2438cm
B
B
=
=


2 2 1 2
0 0
1 2
mm
I r r
m m
= =
+

We calculate the moment of inertia from Eq. 13.100
2
2
34
8
8
6.626 10 J s
h
B
Ic
h
I
cB
I
=
=
2 1
8 0.2438 cm

10
2.998 10 cm
1
s
45
1.14814 10 J I

=

13-60
( )
1 2
1 2
1 1
1 23 1
26
35gmol 35gmol
35 35 gmol 6.022 10 mol
2.90601 10 kg
mm
m m
=
+
=
+
=

2
0
45
26
10
1.14814 10 J
2.90601 10 kg
1.98769 10 m
199pm
I r
I
r
r
r
r
=
=
=
=

13-61
13.30. The dissociation energy of H
2
is 432.0 kJ mol
1
and the fundamental vibrational frequency of the molecule is 1.257 10
14
s
1
.
Calculate the classical dissociation energy. Estimate the zero-point energies of HD and D
2
and their dissociation energies.

Solution:

Given:
1 14 1
0
432.0 kJ mol , 1.257 10 s
p
E = =
Required: classical dissociation , estimatedzero point , dissociation E E E ,

The zero point energy of H
2
is given by
0
34
1
2
1
6.626 10 J s
2
E h
E
=
=
14 1
1.257 10 s
20
4.16444 10 J E

=
3
kJ
10
J
23 1
1
1
6.022 10 mol
25.0782637kJ mol
25.08kJ mol
E
E

=
=

To find the classical dissociation energy, we add the zero point energy to the dissociation energy given above.
1 1
1
25.08kJ mol 432.0 kJ mol
457.08kJ mol
E
E
= +
=

The reduced masses of H
2
, HD and D
2
are in the ratio,

13-62
2 2
H HD D
1 1 1 2 2 2
: :
1 1 1 2 2 2
1 2
: : 1
2 3
4
1 : : 2
3

+ + +
=

From Eq. 13.123,
0
1
2
k

=
we know that frequency is inversely related to , therefore the estimated
0
for HD and D
2
are,
( )
( )
( )
( )
14 1
0
14 1
0
14 1
0 2
13 1
0 2
4
HD 1.257 10 s
3
HD 1.08859 10 s
D 1.257 10 s 2
D 8.88833 10 s
=
=
=
=

13-63
Therefore,

( )
34
1
HD 6.626 10 J s
2
E

=
14 1
1.08859 10 s
( )
20
HD 3.60651 10 J E

=
3
kJ
10
J
( )
( )
23 1
1
34
2
6.022 10 mol
HD 21.71841345kJ mol
and
1
D 6.626 10 J s
2
E
E

=
=
13 1
8.88833 10 s
( )
20
2
D 2.9447 10 J E

=
3
kJ
10
J
( )
23 1
1
2
6.022 10 mol
D 17.73301032kJ mol E

=

The estimated dissociation energies are therefore the difference between the dissociation energies above and the classical dissociation
energy,

1 1
1
1
2
1 1
1
1
HD;
457.08kJ mol 21.71841345kJ mol
435.3615866kJ mol
435.36kJ mol
D ;
457.08kJ mol 17.73301032kJ mol
439.3469897kJ mol
439.35kJ mol
E
E
E
E
E
E

=
=
=
=
=
=

13-64
13.31. A molecule AB
2
is known to be linear but it is not known whether it is BAB or ABB. Its infrared spectrum is found to
show bands corresponding to three normal modes of vibration. Which is the structure?

Solution:

Given: AB
2
, three normal modes of vibration in IR spectrum
Required: structure

The symmetric molecule, BAB, only has two modes that are active in the infrared region:

B AB

and
BAB

(two degenerate modes)
The symmetric stretch is inactive.

The unsymmetrical molecule, ABB have three modes that are active in the infrared region:

ABB

and

A BB

and

ABB

(two degenerate modes)

Therefore the structure of the molecule is ABB.
13-65
13.32. The frequency of the OH stretching vibration in CH
3
OH is 3300 cm
1
. Estimate the frequency of the OD stretching vibration in
CH
3
OD.

Solution:

Given:
1
O H
3 300 cm

=
Required:
O D

To calculate the frequency of the OD stretching vibration, we rely on Eq. 13.123 which
0
1
2
k

=
which shows that the frequency is inversely related to .

The reduced masses are calculated using Eq.13.94, and are in the following ratio

( )
( )
1 2
1 2
1 1
OH 1 23 1
1 1
OD 1 23 1
OD
OH
1gmol 16gmol 1 16
1 16 gmol 6.022 10 mol 17
2gmol 16gmol 2 16
2 16 gmol 6.022 10 mol 18
2 16
mm
m m
L
L

=
+

= =
+

= =
+
=
18L
17L
1 16
17
9
=

The force constants are the same, and therefore the frequency of the OD stretching vibration is given by,
13-66

OD OH
1
OD
1
OD
1
OD
17
9
17
3300 cm
9
2401.102688 cm
2401 cm

=
=
=
=

13-67
13.33. The spectroscopic constants for the OH radical are
0
=3737.76 cm
1
,
0
x
e
=84.8813 cm
1
, B
= 18.9108 cm
1
. Predict the
frequencies at which (a) the P branch transitions ending in, and (b) the R branch beginning in, J =0, 1, 2 will be observed.

Solution:

Given:
1 1 1
0 0
3737.76 cm , 84.8813 cm , 18.9108 cm
e
x B = = =

Required: for the branch and branch; for 0,1, 2 P R J =

a. In problem 13.27, we derived an equation for the P branch transitions, given by,
0 0
2 2
e
x BJ =

For this situation the equation becomes,
1 1 1
3737.76 cm 2 84.8813 cm 2 18.9108 cm J =

The frequencies are then calculated by substituting the values of J into the equation.

J 0 1 2
( )
1
cm

3 567.997 3 530.176 3 492.354

b. For the R branch transitions, we use the second equation derived in problem 13.27,
0 0
1 1 1
2 2
3737.76 cm 2 84.8813 cm 2 18.9108 cm
e
x BJ
J

= +
= +

J 0 1 2
( )
1
cm

3 567.997 3 605.819 3 643.641

13-68
13.34. Irradiation of acetylene with mercury radiation at 435.83 nm gives rise to a Raman line at 476.85 nm. Calculate the vibrational
frequency that corresponds to this shift.

Solution:

Given:
0 1
435.83 nm, 476.85 nm = =
Required:

To calculate the vibrational frequency that corresponds to the shift, we first calculate the wavenumbers that correspond to each wavelength.

9
1 1
9
1 1
435.83 nm;
1
435.83 10 m
2294472.615m 22944.72615cm
476.85 nm;
1
476.85 10 m
2097095.523m 20970.95523cm
= =
=
= =

The frequency that corresponds to the vibration in the C
2
H
2
molecule, (ie the C-C stretch) is the difference of the two,

1 1
1
1
22944.72615cm 20970.95523cm
1973.770928cm
1973.8cm
=
=
=


13-69
13.35. The fundamental vibrational frequency of H
127
I is 2309.5 cm
1
. Calculate the force constant of the bond.

Solution:

Given: H
127
I,
0
=2 309.5 cm
1

Required: k


The force constant is defined in terms of the fundamental frequency in Eq. 13.122,
2 2
0
4 k =

The frequency, in terms of inverse seconds is given by,
0
10
2.998 10 cm
v v c
v
=
=
1 1
s 2309.5 cm
13 1
6.92388 10 s v =


( )
1 2
1 2
1 1
3 1
1 23 1
27
126.9gmol 1.007825gmol
10 kgg
126.9 1.007825 gmol 6.022 10 mol
1.66039 10 kg
mm
m m
=
+
=
+
=

Solving for k we get,
( )
2 2
0
2
2 13 1 27
2
2
4
4 6.92388 10 s 1.66039 10 kg
314.244591kgs
314.24kgs
k
k
k
k

=
=
=
=

13-70
*13.36. The following are some normal modes of vibration for several molecules:

In each case, determine the point group and refer to Appendix E on p. 1028 to determine whether the vibration is active in the
infrared and in the Raman spectrum. Then check your conclusions by reference to the appendix to this chapter (p. 707).

Solution:

Given: image above
Required: determine point group, activity of vibration

13-71
cis-C
2
H
2
Cl
2
: C
2v
point group
Infrared Raman
a.
1
a active active
b.
1
b inactive active
c.
2
a active active
d.
1
a active active

trans-C
2
H
2
Cl
2
: C
2h
point group
Infrared Raman
e.
g
a inactive active
f.
u
a active inactive
g.
u
b active inactive
h.
g
a inactive active

Benzene: D
6h
point group
Infrared Raman
i.
1g
a
inactive active
j.
2u
a active inactive
k.
1u
b inactive inactive

13-72
*13.37. Prove that the force constant k corresponding to the Morse potential function (Eq. 13.146) at small bond extensions is
k =2D
e
a
2

Calculate the vibration frequency v
0
on the basis of the following Morse parameters for H
35
Cl:
D
e
=4.67 eV
a =1.85 10
8
cm
1

Solution:

Given: Morse potential,
35 8 1
H Cl, 4.67 eV, 1.85 10 cm
e
D a = =
Required: proof, v
0

The Morse potential function is given by Eq. 13.146
( )
2
1 e
ax
p e
E D =

At small x values the exponential may be expanded to 1 ax , and the potential energy will therefore be given by,

13-73
*13.38. The Morse function is only one of several models used to describe the behavior of the potential energy of diatomic molecules. A
popular and very accurate model introduced by Murrell and Sorbie [J. Chem. Soc., Faraday Trans. 2, 70, 1552(1974)] is the so-
called Extended Rydberg function, which is written as
1
2 3
1 2 3
( ) (1 )e ,
a x
p e
E x D a x a x a x

= + + +
where x =r r
e
, as in the case of the Morse potential of Eq. 13.146, and the a
i
are constants for a given molecule.
a. Derive an expression for the force constant in terms of the parameters D
e
and a
i
.
b. Show that in order for a function of this form to have a minimum at r =r
e
, a
1
must be both the coefficient of x and the
exponential parameter.
Solution:

Given: Extended Rydberg function
Required: expression for k, proof


13-74
*13.39. Yet another model for a diatomic potential is the Bond Order function used by Garcia and Lagan [Mol. Phys. 56, 621(1985)],
which is given as
( ) ( )
1
exp .
N
p e n
n
E x D c n x
=
=

Show that for N =2, with appropriate choices for the coefficients c
1
and c
2
, this is identical to the Morse potential of Eq. 13.146
expressed as E
p
=De(1 e
x
)
2
D
e
.


13-75
*13.40. The parameters for the bond order (see Problem 13.39) potential of the
35
Cl
16
O radical with N =4 are (in atomic units) c
1
=2.691
042, c
2
=2.545 521, c
3
=1.017 916, c
4
=0.163437, De =0.10302, and =1.763 768. What is the vibrational frequency (in cm
1
)
predicted by this model? [Note that the force constant can be expressed in units of energy area
1
.]

Solution:

Given:
Required:


13-76
*13.41. A model for the
14
N
14
N
16
O
+
ion assigns the following force constants for the two stretching frequencies: k
12
=1092.8 N m
1
, and
k
23
=890.68 N m
1
. Use Eqs. 13.17113.174 to calculate the two stretch frequencies obtained from the model.

Solution:

Given:
1 1
12 23
1 092.8 N m , and 890.68 N m k k = =
Required:
1 2
,

To solve for the stretching frequencies, we need to solve the quadratic equation given by Eq. 13.171. For the molar masses, we use
3 1 3 1
1 2 3 23 1 23 1
14.00 10 kgmol 16.00 10 kgmol
and
6.022 10 mol 6.022 10 mol
m m m

= = =

( )
( ) ( )
12 23 1 2 3 2 2 3 1 2
12 23
1 2 2 3 1 2 3
2 29 57
0
1.65847 10 4.95245 10 0
k k m m m m m m m
k k
mm m m mm m

+ + | | + +
+ + =
|
\ .
+ =

This resembles Eq. 131.172,
2
b +c =0, and therefore the solutions are obtained by solving Eq. 13.173 and 13.174.

13-77
( ) ( )
( )
( )
2 29 57
2
1
2
29 29 57
28 2
1
2
2
2
29 29 57
29 2
2
1.65847 10 4.95245 10 0
4
2
1.65847 10 1.65847 10 4 4.95245 10
2
3.90618 10 s
4
2
1.65847 10 1.65847 10 4 4.95245 10
2
1.26785 10 s
b b c
b b c

+ =

=

=
=
+
=
+
=
=

We then calculate the stretching frequencies from,
28 2
1 10 1
1
1
1
1
29 2
2 10 1
1
2
1
2
2
3.90618 10 s
2 2.998 10 cms
1049.215077cm
1049.2cm
1.26785 10 s
2 2.998 10 cms
1890.265202cm
1890.3cm
c
=

=
=
=

=
=

13-78
*13.42. The fundamental and a few successive overtones of the
2
H
+
molecule lie at 2191, 2064, 1941, 1821, 1705, 1591, 1479 and 1368 cm
1
, respectively.
a. Starting from Eq. 13.139, derive an expression that can be used to obtain both
0
and x
e
by a suitable analysis of the data.
b. Perform the analysis and calculate both
0
and x
e
.

Solution:

Given:
Required: expression for
0
and x, calculate
0
and x
e

a. Eq. 13.139 is given by
( )
0
1 1
1
2 2
e
G x
( | | | |
= + +
| | (
\ . \ .

Therefore, for a transition, , we can write,
13-79
0 0
2 2
0
0
1 1 1 1
1 1
2 2 2 2
1 1 1 1
2 2 2 2
1
2
e e
e e
G x x
G x x
G
( ( | | | | | | | |
= + + + +
| | | | ( (
\ . \ . \ . \ .
(
| | | | | | | |
= + + + + +
(
| | | |
\ . \ . \ . \ . (

= +

2
1 1
2 2
e
x
| |
+
|
\ .
2
2 2
0
2 2
0
2
0
1
2
1 1
2 2
1 1
4 4
1
4
e
e e
e e
e
x
G x x
G x x
G x
(
| |
+ +
(
|
\ . (

(
| | | |
= + + +
(
| |
\ . \ . (

( | | | |
= + + + + +
| | (
\ . \ .
= + + +

2
1
4

( )
( ) ( ) ( )
( )
| | ( ) ( )
2 2
0
2 2
0 0
0 0 0 0 0
or we can simplify as,
1
e
e
e e e
G x
G x
G
x x x
( | |
( |
( \ .
( = + +

( = +

= + + = +

Therefore a plot of the left-hand side as a function of ( ) + will yield a straight line, from which
0
and
e
x can be calculated. If we
consider the case where 1 = , the left hand side is simply the observed fundamental and overtone signals, and the analysis is
particularly simple.
b. From the data given above, we obtain the following plot.


13-80
13.43. Sketch potential energy curves for a diatomic molecule in its ground electronic state and n an excited state, consistent with the
following observations:
a. There is a strong 0 0 absorption band, and strong 0 0, 1 1, and 2 2 emission bands.
b. The strongest absorption band is 4 0, and the strongest emission band is 0 2.
c. There is no sharp rotational fine structure in absorption, but there is a sharp emission spectrum.
d. The absorption spectrum shows a well-defined fine structure for the 0 0, 1 0, 2 0, 3 0, and 4 0 transitions and for
the 6 0 and 7 0, but not in between.

Solution:

a.

b.

13-81
c.

d.


13-82
*13.44. Using the data in Example 13.12 on p. 702, determine the area under the curve in a plot of v against v. Extrapolate to zero v to
obtain v
max
, since the Birge-Sponer extrapolation shows that at that point v = v
max
. A better value may be obtained by a nonlinear
extrapolation. What are the values of v not given in the table?

Solution:

Given: Example 13.12
Required: area under the curve, values of v not given in the table


13-83

13.45. Calculate the dissociation energy of the hydrogen molecule ion from the vibrational energy level separations of
2
H .
+
The values for
the transitions 1 0, 2 1, , are, respectively, 2191, 2064, 1941, 1821, 1705, 1591, 1479, 1368, 1257, 1145, 1033, 918, 800,
677, 548, 411, with all values given in cm
1
. Use both a linear plot and a curve to obtain answers.


13-84

13.46. The electronic spectra of diatomic molecules in the gas phase typically show extensive vibrational structure superimposed on the
broader electronic transition. Taking the equilibrium geometry of the ground electronic state to be the zero energy, the G
() of Eq.
13.138 can be used to express the energies of the vibrational states v (in cm
1
) of this electronic state. Denoting the minimum
energy of the excited electronic state as
e
T
(in cm
1
), the vibrational energy levels v of the excited state can be expressed as
( ).
e
T G +

Derive an expression for the frequencies of the transitions between the vibrational levels of the ground and
excited electronic states. (Note that the vibrational frequencies and anharmonicity constants are not the same for the ground and
excited electronic states.)

Solution:

Given: Eq. 13.138
Required: expression for

Eq. 13.138 is given by
( )
2
0
1 1
2 2
e
G x
(
| | | |
= + +
(
| |
\ . \ . (

The ground state vibrational energies are given by,
2
0 0
1 1
2 2
e
G x
| | | |

= + +
| |
\ . \ .

And the excited state energies are expressed as,
2
0 0
1 1
2 2
e e
G T x
| | | |

= + + +
| |
\ . \ .

Therefore, the energy difference for the transitions are given by,
2 2
0 0 0 0
1 1 1 1
2 2 2 2
e e e
G G T x x

( (
| | | | | | | |

= = + + + + +
( (
| | | |
\ . \ . \ . \ . ( (

13-85
This cannot be simplified any further.

13-86
13.47. An easy and reliable way to analyze the electronic spectrum of a diatomic molecule is to use the equation derived in Problem 13.46
as the model for a multiple regression analysis (several plotting packages and mathematics packages such as Mathcad can perform
this task) to simultaneously identify the five unknowns,
0 0 0
, , , ,
e e
T x
and
0 e
x [McNaught, J. Chem. Ed. 57, 101(1980)]. The
following data are from the electronic spectrum of iodine.
0 (nm) 1 (nm) 2 (nm)
17 567.2 15 581.0 10 607.3
18 564.2 16 577.8 11 603.1
19 561.5 17 574.2 12 599.1
20 558.5 18 571.3 13 595.5
21 555.8 19 568.3 14 591.8
22 553.0 20 565.2 15 588.1
23 550.1 21 559.6 16 584.8
24 547.8 22 556.9 17 581.2
25 542.7 23 554.2 18 578.1
26 540.7 24 551.8 19 575.1
27 538.5 25 549.0 20 572.4

Perform a multiple regression analysis and identify the spectroscopic parameters of the ground and excited electronic states. Literature
values are (in cm
1
)
e
T
=15730,
0
=132.1,
0 e
x =1.051,
0
=214.5, and
0 e
x =0.614.

13-87
13.48. The dissociation energy (from the zero-point level) of the ground state
3
2 g
( ) O

molecule is 5.09 eV. There exists an electronically
excited
3
u
state of O
2
, whose zero-point level lies 6.21 eV above the zero-point level of the ground state. The ground-state
molecule dissociates into two ground-state O(
3
P) atoms, while the
3
u
species dissociates into one ground-state O(

3
P) atom and an
O*(
1
D) atom that lies 1.97 eV above the ground state. Sketch the potential-energy curves and calculate the dissociation energy of
3
2 u
( ) O

into O +O*(
1
D).


13-88
13.49. The spectroscopic dissociation energy D
0
is the energy required to dissociate the molecule in its ground vibrational state. This is
always slightly smaller than the actual depth of the electronic potential energy because of the zero-point energy of the molecule (see
Figure 13.22). Given that for HCl, De =4.6173 eV,
0
=2989 cm
1
, and
0 e
x =52.82 cm
1
, calculate the value of D
0
for HCl.

Solution:

Given:
1 1
0 0
HCl; 4.6173 eV, 2989 cm , 52.82 cm
e e
D x = = =
Required: D
0

To find the spectroscopic dissociation energy, we first calculate
0
G
from Eq. 13.138

( )
2
0
2
0 0
0 0 0
1 1
0
1
0
1
0
1 1
2 2
1 1
0 0
2 2
1 1
2 4
1 1
2989 cm 52.82 cm
2 4
1481.295 cm
1481.295 cm
e
e
e
G x
G x
G x
G
G
G

(
| | | |
= + +
(
| |
\ . \ . (

(
| | | |
= + +
(
| |
\ . \ . (

=
=
=
=
10
2.998 10 cm
1
s
34
6.626 10 J
s
19
1.602 10 J
( )
1
0
eV
0.1836801eV G

To solve for D
0
, we solve as follows,
13-89
0 0 0
0 0 0
0
0
0
1 1
2 4
1 1
0.1836801eV
2 4
4.6173 eV 0.1836801eV
4.4336199 eV
4.4336 eV
e e
e
D D x
G x
D
D
D

| |
=
|
\ .
= =
=
=
=

13-90
13.50. The dissociation energy (from the zero-point level) of the ground state NO(X
2
) molecule is 6.6 eV. There exists an electronically
excited B
2
state of NO whose zero-point level lies at 5.7 eV above the zero-point level of the ground state. The ground-state
molecule dissociates into ground state N(
4
S) +O(
3
(P)), while the B
2
species dissociates into two ground-state atoms N(
2
D) +O(
3
P)
that lie 3.3 eV above its ground state. Sketch the potential energy curves and calculate the dissociation energy of NO into N(
2
D) +
O(
3
P).


13-91
13.51. Sodium vapor, which consists mainly of Na
2
molecules, has a system of absorption bands in the green, the origin of the 0, 0 band
being at 20 302.6 cm
1
. From the spacing of the vibrational levels it can be deduced that the dissociation energy of the upper state is
0.35 eV. The dissociation of the excited Na
2
gives a normal atom and an atom that emits the yellow sodium D line at 589.3 nm.
Calculate the energy of dissociation of Na
2
in its ground state.

Solution:

Given:
1
2 0
Na ; 20302.6 cm , 0.35 eV, 589.3nm
e
D = = =
Required: D
0

The wavenumber
1
20302.6 cm corresponds to a frequency of,
1
20302.6 cm =
10
2.998 10 cm
1
14 1
s
6.08672 10 s =

And therefore an energy of,
34
6.626 10 J s
E h
E
=
=
14 1
6.08672 10 s
19
19
4.03306 10 J
4.03306 10 J
E
E
=
19
1.602 10 J
( )
1
eV
2.51751581eV E
=

The wavelength at 589.3nm corresponds to a frequency of,
8
2.998 10 m

=
1
9
s
589.3m 10 m
14 1
5.08739 10 s =

13-92
34
6.626 10 J s
E h
E
=
=
14 1
5.08739 10 s
19
19
3.37091 10 J
3.37091 10 J
E
E
=
19
1.602 10 J
( )
1
eV
2.104185905eV E
=

The dissociation energy therefore becomes,


0
0
0
2.51751581eV 0.35 eV 2.104185905eV
0.763329904eV
0.763329904 eV
D
D
D
= +
=
= ( )
1
19
1.602 10 J eV

23 1
1
0
1
0
6.022 10 mol
73640.29841J mol
73.6kJ mol
D
D

=
=

CHAPTER
1
1
4
4
Some Modern Applications
of Spectroscopy

Physical Chemistry
Electronic Edition


Chapter 14: Some Modern Applications of Spectroscopy Spectral Line Widths
14-2
Chapter 14
Spectral Line Widths
14.1. The sun emits a spectral line at 677.4 nm and it has been identified as due to an ionized
57
Fe atom, which has a molar mass of 56.94
g mol
1
. The spectral line has a width of 0.053 nm. Estimate the temperature of the surface of the sun.
Solution
14.2. Estimate the lifetime of a state that, because of lifetime broadening, gives rise to a line of width
a. 0.01 cm
1
,
b. 0.1 cm
1
,
c. 1.0 cm
1
,
d. 200 MHz.
Solution
14.3. Lasers are commonly used in physical chemistry research laboratories to generate the reactive intermediates required in the study of
elementary reactions. For example, highly reactive oxygen atoms in the ground electronic state [O(
3
P)] can be generated from NO
2

by laser-induced dissociation:
3
2
NO NO( , ) O( P).
hv
v J + The velocity distribution of the oxygen atoms thus generated (using a
laser with =355 nm) shows two broad peaks centered at 900.00 and 1400.00 m s
1
, respectively, and leads to the formation of the
NO(v =0) and the NO(v = 1) states [Hradil et al., J. Chem. Phys. 99, 4455(1993)].
a. Identify the NO vibrational state that corresponds to each O atom velocity peak, and justify your choice.
b. If a total of 7400 cm
1
of energy is available to the fragments, what are the velocities of the NO fragment corresponding to each of
the peaks in the oxygen velocity distribution? (These velocities are measured with respect to a fixed laboratory coordinate system
and, therefore, are the absolute velocities of the fragments. Assume that the NO molecules are the J =0 rotational state.) For the
NO molecule,
1
0
1904cm . v =
Solution
Resonance Spectroscopy
14.4. Calculate the magnetic flux density that is required to bring a free electron (g =2.0023) into resonance in an EPR spectrometer
operating at a wavelength of 8.00 mm.
Solution
Chapter 14: Some Modern Applications of Spectroscopy Resonance Spectroscopy
14-3
14.5. An EPR spectrometer is operated at a frequency of 10.42 GHz and a study is made of methyl radicals. Resonance is observed at a
magnetic flux density of 0.37175 T.
a. Calculate the g value of the methyl radical.
b. Calculate the field required for resonance when the spectrometer is operating at 9.488 GHz.
Solution
14.6. How many hyperfine lines would you expect to find in the ESR spectrum of
2
H,
19
F,
35
Cl,
37
Cl? Calculate the nuclear magnetic
moment is each case. (Refer to Table 14.1, p. 735.)
Solution
14.7. Determine the number of hyperfine lines expected in the ESR spectrum of
63
Cu, which has a spin I of 1.
Solution
14.8. In a nuclear magnetic resonance instrument operating at a frequency of 60 MHz, at what magnetic fields would you expect to
observe resonance with
1
H
35
Cl?
Solution
14.9. The chemical shift of methyl protons in acetaldehyde is 2.20 ppm, and that of the aldehydic proton is 9.80 ppm. What is the
difference in the effective magnetic field for the two types of proton when the applied field is 1.5 T? If resonance is observed at 60
MHz, what is the splitting between the methyl and aldehyde proton resonances?
Solution
14.10 The nuclear spin quantum number I of the
39
K nucleus is
3
,
2
and the nuclear g factor is 0.2606. How many orientations does the
nucleus have in a magnetic field? At what frequency would there be resonance in a field of 1.0 T?
Solution
14.11. The
11
B nucleus has a spin I of
3
2
and a nuclear g factor of 1.7920. At what field would resonance be observed at 60 MHz?
Solution
Chapter 14: Some Modern Applications of Spectroscopy Essay Questions
14-4
14.12. The Fourier transform is the mathematical foundation for much of modern spectroscopy. The idea behind Fourier transform
spectroscopy is to use a pulse of energy, which contains many frequencies, to probe the sample many times each second. The
cumulative signal recorded from the pulses, which is a time-dependent oscillatory function F(t), has the general form shown in
Figure 14.25a. The Fourier transform of such a function results in a function of frequencies, which we may denote I(), obtained as
i t
0
( ) Re ( )e I A F t dt

(
=
(

where Re represents the real part of the function. Perform the Fourier transform of F(t) =[cos(
1
t) +cos(
2
t)] exp(t/T), where T is
a relaxation time, and obtain an expression for I(). Analyze the behavior of this function by assigning arbitrary values to the
constants and plotting it as a function of q. Use the fact that e
it
=cos t +i sin t, and
2 2 2
t/T
2 2 2 2
0
[1 ( ) ]
cos( )cos( )e
[1 ( ) ][1 ( ) ]
a b T
at bt dt T
a b T a b T
+ +
=
+ + +

Solution
14.13. The lifetime of
57
Fe* is 2 10
7
s. Calculate the uncertainty in the frequency of the radiation emitted and in the wavenumber.
Solution
14.14. The free radical CH
3
is found experimentally to be planar. Give an interpretation of this result in terms of orbital hybridization.
What microwave spectrum would the radical show? What vibrations would be active in the infrared?
Solution
14.15. A complete photoelectron spectrum of the nitrogen molecule (see Figure 14.45) is given by Bock and Mollre [J. Chem. Educ. 51,
506(1974)]. The spectrum extends from about 411 eV (the peak corresponding to the 1s
g
is at approximately 410 eV) to about 15.0
eV, with the peak corresponding to the 2p
g
electron occurring at 15.88 eV. If we were to use a radiation source of wavelength 58.4
nm, which of the peaks in the spectrum can be studied? What will be the wavelength required to extend the range to 410 eV?
Solution

For additional problems, see the books listed at the end of the problem section in Chapter 12 (p. 634).

Essay Questions
14.16. Explain the selection rules for Raman spectra, with examples.
14.17. Describe the physical interaction that leads to nuclear magnetic resonance.
14.18. Give an account of the fundamental principles underlying Mssbauer spectroscopy.

Chapter 14: Some Modern Applications of Spectroscopy Solutions
14-5
Solutions
14.1. The sun emits a spectral line at 677.4 nm and it has been identified as due to an ionized
57
Fe atom, which has a molar mass of 56.94
g mol
1
. The spectral line has a width of 0.053 nm. Estimate the temperature of the surface of the sun.

Solution:

Given:
57 1
Fe, 677.4 nm, 56.94 g mol , 0.053 nm M = = =
Required: T

To solve this problem we need to use Eq. 14.4.
1/2
B
2 (2 / )
v
v k T m
c
| |
=
|
\ .

Through substitution and rearrangement, Eq. 14.4, gives an expression for temperature in terms of wavelength.
1/2
B
2
B
9
2 (2 / )
2 2
0.053 10 m
k T m
c
c m
T
k
M
m
L
T
| |
=
|
\ .
| |
=
|
\ .
=
=
8 1
9
2.998 10 ms
2 677.4 10 m

2
56.94 g | |
|
\ .
1
mol
3 1
10 kg g

23 1
6.022 10 mol
23 1
2 2
1
2 1.381 10 J K
470888.0375 m s kg T
| |
| |
|
|
|
\ .
\ .
=
1
J
5
K
4.71 10 K T =

Therefore the temperature of the sun is approximately
5
4.71 10 K .

14-6
14.2. Estimate the lifetime of a state that, because of lifetime broadening, gives rise to a line of width
a. 0.01 cm
1
,
b. 0.1 cm
1
,
c. 1.0 cm
1
,
d. 200 MHz.

Solution:

Given: , v v
Required:

The lifetime of a state is given by and can be determined by rearranging Eq. 14.3
12
1
12
1
2.7 10
/cm
/s
2.7 10
s
/cm
v
v

12
10
12
11
12
12
2.7 10
a. s
0.01
2.7 10 s
2.7 10
b. s
0.1
2.7 10 s
2.7 10
c. s
1.0
2.7 10 s
=
=
=
=
=
=

d. In this case, we first need to convert as follows,
14-7
12 10 1
6 1
10
10
2.7 10 2.998 10 cms
s
200 10 s
4.0473 10 s
4.05 10 s
=
=

14-8
14.3. Lasers are commonly used in physical chemistry research laboratories to generate the reactive intermediates required in the study of
elementary reactions. For example, highly reactive oxygen atoms in the ground electronic state [O(
3
P)] can be generated from NO
2

by laser-induced dissociation:
3
2
NO NO( , ) O( P).
hv
v J + The velocity distribution of the oxygen atoms thus generated (using a
laser with =355 nm) shows two broad peaks centered at 900.00 and 1400.00 m s
1
, respectively, and leads to the formation of the
NO(v = 0) and the NO(v = 1) states [Hradil et al., J. Chem. Phys. 99, 4455(1993)].
a. Identify the NO vibrational state that corresponds to each O atom velocity peak, and justify your choice.
b. If a total of 7400 cm
1
of energy is available to the fragments, what are the velocities of the NO fragment corresponding to each of
the peaks in the oxygen velocity distribution? (These velocities are measured with respect to a fixed laboratory coordinate system
and, therefore, are the absolute velocities of the fragments. Assume that the NO molecules are the J =0 rotational state.) For the
NO molecule,
1
0
1904cm . v =

Solution:

Given:
1 1 1
1 2 tot 0
355 nm, 900.00, 1400.00 m s , 7400 cm , 1904cm u u = = = = =
Required: NO vibrational state, , v v

a. In this experiment, the energy absorbed by the NO
2
molecule is used for bond dissociation to produce ( ) ( )
3
NO 0,1 O P v = + , and the
remaining energy is given to the translational motion of the two fragments. Since it takes less energy to form the NO ( ) 0 v = than the
NO ( ) 1 v = state, the formation of NO( ) 0 v = will correspond to higher O atom velocity. (Actually, higher velocities of both
fragments)

b. To find the velocities of the NO fragments corresponding to each of the peaks in the oxygen velocity distribution, we first calculate the
energy of the O atom fragment corresponding to each peak.
1
1
2
O O O
1
O
at 900.00 m s :
1
2
1 0.016kg mol
2
u
E m u
E
=
=
=
23 1
6.022 10 mol
( )
2
1
20 2 2
O
20
O
900.00 m s
1.07605 10 kgm s
1.07605 10 J
E
E
=
=

14-9
1
2
1
O
at 1400.00 m s :
1 0.016kg mol
2
u
E
=
=
23 1
6.022 10 mol
( )
2
1
20
O
1400.00 m s
2.60379 10 J E

=

The energy of the NO molecule in the

0 0
34
0
0state:
1
2
1
6.626 10 J s
2
v
E hc
E
=
=
=
10
2.998 10 cm
1
s
1
1904cm
20
0
1 0
34
1
1.89112 10 J
1state:
3
2
3
6.626 10 J s
2
E
v
E hc
E
=
=
=
=
10
2.998 10 cm
1
s
1
1904cm
20
1
5.67337 10 J E

=

Since the total energy available to the fragments is
tot tot
34
tot
6.626 10 J s
E hc
E
=
=
10
2.998 10 cm
1
s
1
7400 cm
19
tot
1.46999 10 J E

=

The translational energy available to the NO fragment (since rotational energy is zero) will be,
14-10
( )
( )
2
tr tot O O
tr
NO
NO
1
NO
2
NO
and therefore
v
E E E m u
E
u
m
| |
= +
|
\ .
=

( ) ( )
( )
( )
1
O
19 20 20
tr
20
tr
tr
NO
NO
20 23 1
NO
at 1, 900.00 m s :
NO 1.46999 10 J 5.67337 10 J 1.07605 10 J
NO 7.95049 10 J
NO
7.95049 10 J 6.022 10 mol
v u
E
E
E
u
m
u

= =
= +
=
=

=
1
0.03 kg mol
( ) ( )
( )
1
NO
1
NO
1
O
19 20 20
tr
19
tr
19 23 1
NO
1263.300345m s
1263m s
at 0, 1400.00 m s :
NO 1.46999 10 J 1.89112 10 J 2.60379 10 J
NO 1.0205 10 J
1.0205 10 J 6.022 10 mol
u
u
v u
E
E
u

=
=
= =
= +
=

=
1
0.03 kg mol
1
NO
1
NO
1431.25272m s
1431m s
u
u
=
=

14-11
14.4. Calculate the magnetic flux density that is required to bring a free electron (g =2.0023) into resonance in an EPR spectrometer
operating at a wavelength of 8.00 mm.

Solution:

Given: 2.0023, 8.00 mm g = =
Required: B

To calculate the magnetic flux density, we can use Eq. 14.43,
B o
E hv g B = =

Rearranging, we obtain
B
hv
B
g
=

Converting the wavelength to frequency, and then solving, we obtain B as,
B
34
6.626 10 J
c
v
h c
B
g
B
=
=
=
s
24
2.023 9.274 10 J

8
1
2.998 10 m
T

1
s
3
8.00 10 m
1.323518752T
1.32T
B
B
=
=

14-12
14.5. An EPR spectrometer is operated at a frequency of 10.42 GHz and a study is made of methyl radicals. Resonance is observed at a
magnetic flux density of 0.37175 T.
a. Calculate the g value of the methyl radical.
b. Calculate the field required for resonance when the spectrometer is operating at 9.488 GHz.

Solution:

Given: 10.42 GHz, 0.37175 T B = =
Required: g, B at 9.488 GHz =

a. To solve for the g value of the methyl radical, we use Eq. 14.43,
B o
E hv g B = =

Rearranging, we obtain
B
34
6.626 10 J
hv
g
B
g
=
s
9 1
10.42 10 s

0.37175 T
24
9.274 10 J

1
T
2.002631679
2.003
g
g
=
=

b. To calculate the magnetic field at 9.488 GHz = , we can use Eq. 14.43 in the form of,
B
34
6.626 10 J
hv
B
g
B
=
s
9 1
9.488 10 s

2.002631679 T
24
9.274 10 J

1
T
0.338499424T
0.3385T
B
B
=
=

14-13
14.6. How many hyperfine lines would you expect to find in the ESR spectrum of
2
H,
19
F,
35
Cl,
37
Cl? Calculate the nuclear magnetic
moment is each case. (Refer to Table 14.1, p. 735.)

Solution:

Given:
2 19 35 37
H, F, Cl, Cl
Required: hyperfine lines,
N
for each

2
H
19
F
35
Cl
37
Cl
Spin, I
1

1
2

3
2

3
2

M
I
values 1, 0, 1
1 1
,
2 2
+
3 1 1 3
, , ,
2 2 2 2
+ +
3 1 1 3
, , ,
2 2 2 2
+ +

Number of lines 3 2 4 4
g
N

(from Table 14.1)
0.857387 5.257 0.54727 0.4555
27 1
/10 J T
N


14-14
14.7. Determine the number of hyperfine lines expected in the ESR spectrum of
63
Cu, which has a spin I of 1.

Solution:

Given:
63
Cu, I =1.
Required: number of hyperfine lines

The number of hyperfine lines corresponds to the total number of M
I
values. For I =1, 1, 0, 1
I
M = and therefore three lines are
expected.

14-15
14.8. In a nuclear magnetic resonance instrument operating at a frequency of 60 MHz, at what magnetic fields would you expect to
observe resonance with
1
H
35
Cl?

Solution:

Given: 60 MHz =
Required:
1 35
at which the instrument resonates with H Cl B

To calculate B, we use Eq. 14.43 to first determine the energy which corresponds to 60 MHz = .
B o
34
6.626 10 J s
E hv g B
E
= =
=
6 1
60 10 s

26
3.9756 10 J E

=

Resonance could be observed with the proton and with
35
Cl.

For the proton we use the g
N
value for
1
H in Table 14.1,
26
3.9756 10 J
N N
N N
E g B
E
B
g
B
=
27
5.5856 5.0508 10 J
1
T
1.409200143T
1.41T
B
B
=
=

For
35
Cl, we use the g
N
value found in Table 14.1,
14-16
26
3.9756 10 J
N N
N N
E g B
E
B
g
B
=
27
0.54727 5.0508 10 J
1
T
14.38271478T
14.4T
B
B
=
=

(This is outside the normal instrumental range).

14-17
14.9. The chemical shift of methyl protons in acetaldehyde is 2.20 ppm, and that of the aldehydic proton is 9.80 ppm. What is the
difference in the effective magnetic field for the two types of proton when the applied field is 1.5 T? If resonance is observed at 60
MHz, what is the splitting between the methyl and aldehyde proton resonances?

Solution:

Given:
Methyl Aldehydic
2.20ppm, 9.80ppm, 1.5T, 60MHz B = = = =
Required:
eff
, B

The effective magnetic field is given by,
( )
eff
6
eff
5
eff
eff
9.80 2.20 10 1.5T
1.14 10
11.4T
B B
B
B
B
=
=
=
=

The frequency splitting can be calculated by multiplying the difference in shifts by 60 MHz,
( )
6 1
6 6 1
60 10 s
9.80 2.20 10 60 10 s
456Hz

=
=
=

14-18
14.10 The nuclear spin quantum number I of the
39
K nucleus is
3
,
2
and the nuclear g factor is 0.2606. How many orientations does the
nucleus have in a magnetic field? At what frequency would there be resonance in a field of 1.0 T?

Solution:

Given:
39
3
K, , 0.2606, 1.0 T
2
N
I g B = = =
Required: number of orientations,

The number of orientations of the nucleus in a magnetic field is the total number of M
I
values,
3 1 1 3
, , ,
2 2 2 2
I
M = + +

Therefore there are four orientations in the magnetic field.

To calculate , we rearrange Eq. 14.43 in the following manner,

27
0.2606 5.0508 10 J
N N
N N
E h g B
g B
h

= =
=

=
1
T 1.0 T
34
6.626 10 J
s
1986475.219Hz
1.986MHz
=
=

14-19
14.11. The
11
B nucleus has a spin I of
3
2
and a nuclear g factor of 1.7920. At what field would resonance be observed at 60 MHz?

Solution:

Given:
11
3
B, , 1.7920, 60 MHz
2
N
I g = = =
Required: B

To calculate B, we rearrange Eq. 14.43 in the following manner,
34
6.626 10 J
N N
N N
E hv g B
hv
B
g
B
= =
=
=
s
6 1
60 10 s

27
1.7920 5.0508 10 J
1
T
4.392426518T
4.3924T
B
B
=
=

14-20
14.12. The Fourier transform is the mathematical foundation for much of modern spectroscopy. The idea behind Fourier transform
spectroscopy is to use a pulse of energy, which contains many frequencies, to probe the sample many times each second. The
cumulative signal recorded from the pulses, which is a time-dependent oscillatory function F(t), has the general form shown in
Figure 14.25a. The Fourier transform of such a function results in a function of frequencies, which we may denote I(), obtained as
i t
0
( ) Re ( )e I A F t dt

(
=
(

where Re represents the real part of the function. Perform the Fourier transform of F(t) =[cos(
1
t) +cos(
2
t)] exp(t/T), where T is
a relaxation time, and obtain an expression for I(). Analyze the behavior of this function by assigning arbitrary values to the
constants and plotting it as a function of q. Use the fact that e
it
=cos t +i sin t, and
2 2 2
t/T
2 2 2 2
0
[1 ( ) ]
cos( )cos( )e
[1 ( ) ][1 ( ) ]
a b T
at bt dt T
a b T a b T
+ +
=
+ + +

Solution:

14-21
14.13. The lifetime of
57
Fe* is 2 10
7
s. Calculate the uncertainty in the frequency of the radiation emitted and in the wavenumber.

Solution:

Given:
57 7
Fe*, 2 10 s =
Required: uncertainty in ,

From the uncertainty principle we have Eq. 14.2,
/2 E

34
4
6.626 10 J s
h
E
E

=

7
4 2 10 s
28
2.6364 10 J E

=

We can solve for the uncertainty in the frequency is therefore
28
2.6364 10 J
E h
E
h
=

34
6.626 10 J
1
5 1
s
397887.3577s
3.98 10 s
=
=

In terms of wavenumbers, this becomes,
14-22
1
10 1
1
397887.3577s
2.998 10 cms
397887.3577 s
c
=
=

10 1
2.998 10 cms
5 1
5 1
1.32718 10 cm
1.33 10 cm

=
=

14-23
14.14. The free radical CH
3
is found experimentally to be planar. Give an interpretation of this result in terms of orbital hybridization.
What microwave spectrum would the radical show? What vibrations would be active in the infrared?

Solution:

The planar form of CH
3
must arise from sp
2
hybridization. This leads to the D
3h
point group. Since planar CH
3
has no dipole moment, it
shows no microwave spectrum.

The vibrations that would be active in the infrared are show in Figure 13.25 for BF
3
. As discussed in the text, all normal modes except the
completely symmetric one (
1
a
), give an infrared spectrum. In other words, an infrared spectrum is given by

1
a
and e
vibrations.

14-24
14.15. A complete photoelectron spectrum of the nitrogen molecule (see Figure 14.45) is given by Bock and Mollre [J. Chem. Educ. 51,
506(1974)]. The spectrum extends from about 411 eV (the peak corresponding to the 1s
g
is at approximately 410 eV) to about 15.0
eV, with the peak corresponding to the 2p
g
electron occurring at 15.88 eV. If we were to use a radiation source of wavelength 58.4
nm, which of the peaks in the spectrum can be studied? What will be the wavelength required to extend the range to 410 eV?

Solution:

Given: 58.4nm =
Required: which peaks would be studied, to extend range to 410 eV

To determine the peak which would be studied, we first calculate the energy of the radiation with 58.4nm, =

34
6.626 10 J s
hc
E hv
E
= =
=
8
2.998 10 m
1
s
9
58.4 10 m
18
3.4015 10 J E

=
18
1eV
1.602 10 J
21.23282113eV E
=

Therefore, this source can be used to study peaks with energy below 21.2 eV, which corresponds to all peaks shows in Figure 14.45.

In order to study peaks up to an energy of 410 eV, the wavelength of radiation required would be,

34
6.626 10 J
hc
E
=
s
8 1
2.998 10 ms

410 eV
1eV
18
1.602 10 J
9
3.02438 10 m
3.02nm
=
=


CHAPTER
1
1
5
5
Statistical Mechanics

Physical Chemistry
Electronic Edition


Chapter 15: Statistical Mechanics Permutations and Combinations:
15-2
Chapter 15
Permutations and Combinations:
15.1. Use Stirlings formula to calculate and approximate value for ln(N!) and compare with the exact value for N=5, 10, 50, 100, 1,000
and 10,000!
Solution
Work out the following examples:

15.2. The number of possible arrangements of 4 objects (A B C D) among 4 positions (do not list them).
Solution
15.3. The number of possible arrangements of 3 objects (A B C) among 4 positions. List them all.
Solution
15.4. Use the binomial distribution to work out the binomial coefficients for ( )
n
1 2
x x + for n=5. Arrange the numbers in Pascals
triangle. Work out the quantities
4
3
| |
|
\ .

5
3
| |
|
\ .
and
5
2
| |
|
\ .
to check your entries.
Solution
15.5. Consider two sets of indistinguishable objects, {A A} and {B B B}. Work out and list the possible arrangements of these in 5
boxes, one object per box. Check your number against the formula.
!
!
!
n
r
c
c
n
P
n
=

Solution
15.6. Work out the number of ways that the three objects (A B C) can be placed in 5 boxes, no more than one object per box. List all the
possibilities to confirm your number.
Solution
Chapter 15: Statistical Mechanics Quantum statistics
15-3
15.7. Work out the number of ways that the three objects (A A A) can be placed in 5 boxes, no more than one object per box. List all the
!
( ) ! !
n
r
n
C
n r r
=

Solution
15.8. Work out the number of ways that the two objects (A B) can be placed in 3 boxes with no restriction on the number of objects per
box. List all the possibilities to confirm your number.
Solution
15.9. Work out the number of ways that the two objects (A A) can be placed in 4 boxes without restriction on the number of objects per
Solution
15.10. When we remove the condition of distinguishability from the n objects of Eq.(A.5), we divide by n! to obtain Eq.(A.6). By
considering the simple case of 2 objects and 3 boxes, (same as problem 2g) show that it is improper similarly to divide Eq.(A.7) by
n! to obtain the desired result for Eq.(A.8).
Solution
15.11. A partially deuterated methane sample is analyzed and found to contain equal molar quantities of hydrogen and deuterium. On a
random basis, calculate the percentage of species CH
4
, CH
3
D, CH
2
D
2
, CHD
3
,CD
4
.
Solution
Quantum statistics
15.12. Show that
!
ln
!( ) !
m
n m n
(
(

and
( ) 1 !
ln
!( 1) !
m n
n m
+ (
(

both approach ln
!
n
m
n
(
(

as n becomes large, provided that m>>n. (Use
Stirlings formula and use the fact that m>>n, and m>>1).)
Solution
15-4
15.13. Show that the maximum entropy, S, is obtained when all the probabilities,
i
p are equal, where
1
ln
n
i i
i
S p p
=
=
and
1
1
n
i
i
p
=
=

(This shows us that complete lack of knowledge of which state the system is in results in the highest entropy. When all states are
equally likely, we have no preferential state, and this means the most random or highest entropy.)
Solution
15.14. Prove that for an N particle quantum state, the wave function must be either odd or even under the permutation of any two of the N
particles.
(This symmetry, of course, distinguishes bosons from fermions.)
Solution
15.15. A more accurate form of Stirlings approximation is
ln ! ln ln 2 N N N N N = +
In the stopcock opening and closing example, recalculate the effect of
II III
S

using the above approximation and show that the
entropy change is negligible compared to
I II
S

. Assume that the two volumes are equal, and consider what happens to this new
entropy change 0
II III
S

< as the number of particles goes to infinity
(Although we observe no noticeable change when we physically close the stopcock in going from state II to III, there is a change
due to our definition. This problem asks you to look into. The reason the change is negligible from our theory is because we are
dealing with an enormous number of particles, and can use Stirlings approximation. However, if we had only a few particles, then
the effect of closing the stopcock would lead to a difference between the two states, II and III, i.e. the entropy would show a
decrease. This underscores the fact that we can not define entropy for a small number of particles because entropy is a statistical
quantity.)
Solution
15-5
15.16. Using:
1 2
1 2
N N
V V
= prove the relationship:
( ) ( ) ( )
( ) ( )
( )
( ) ( )
( ) ( )
( ) ( ) ( )
1 2 1
2
1 2 1 2
1 2 1 2 1 2 1 2
1 2 1 2
1 2 1 2
/ / ! !
ln ln
! !
/ / ! !
N N N
N
c c
N N N N
c c
V V V V N N N N N N
N N N N
V V V V N N
(
(
+ +
(
( =
(
+ ( +

(

Solution
15.17. Without considering energy, calculate the statistical weights for 30 quanta distributed amongst 30 oscillators for the following
distributions of the quanta:
0 1 2 29
0, 30, 0 N N N

= = =
0 1 2 3 29
1, 28, 1, 0 N N N N

= = = =
0 1 2 3 29
10, 10, 10, 0 N N N N

= = = =
(This is a problem of combinatorials, how many ways can 30 indistinguishable objects be distributed between 30 levels. For
oscillators, we usually label the lowest state by a 0, so we go up to the 29
th
level. In general, there is usually degeneracy (more
than one state with the same energy) Here we are calculating the degeneracy for various possible energies. In case a) the energy is
1
30 , for b) the energy is
0 1 2
28 2 + + and for c)
0 1 2
10 10 10 + + . The problem calculates the number of ways (the
statistical weight) that indistinguishable quantum can be arranged to give that particular energy.)
Solution
15.18. Show that Eq.(15.148) satisfies FD and BE conditions of respectively no more that 1 particle, on the average, in a state, and any
number of particles in a state. Let ( ) exp /
B
x k T
= (

Solution
Chapter 15: Statistical Mechanics Transformations of statistical and thermodynamic functions
15-6
Transformations of statistical and thermodynamic functions
15.19. Starting from
ln ( , , )
B
S k E V N =
obtain the equation:
ln ( , , )
B
PV k T T V =
where ( , , ) T V is the grand partition function. Do NOT derive the ideal gas law (i.e. do not assume the particles do not interact).
(The grand partition function is one that is commonly used in chemical reactions.)
Solution
15.20. Derive expressions for the energy U=E, the entropy S the pressure P and the Helmholtz energy A, and the Gibbs energy G in terms
of the Canonical ensemble, Q.
Solution
15.21. Find the natural function for the isothermal-isobaric ensemble, ( , , ) T P N , i.e. for variables T, P and N.
Solution
15.22. Obtain an expression for C
P
in terms of the partition function Q for the system.
Solution
15.23. Obtain an expression for the pressure P in terms of the molecular partition function q, for (a) distinguishable molecules and (b)
indistinguishable molecules. Express the result in terms of the number of molecules N and also the amount of substance n.
Solution
15.24. The partition function for each degree of vibrational freedom is
B
1/ 1 exp
hv
k T
( | |
( |
\ .
(Eq.(15.173)). Obtain from this expression
the limiting value of the vibrational contribution to C
V
as T approaches infinity.
Solution
Chapter 15: Statistical Mechanics Partition functions
15-7
15.25. Chemical reactions often lead to the formation of products whose energy distributions show significant deviations from the
statistical distribution of Eq. 15.40. In a study of an elementary reaction with
16
O
1
H radical as one of the products [Zhang, van
der Zande, Bronikowski, and Zare, J. Chem. Phys. 94, 2704(1994)], the following rotational distribution was observed for the OH(v
= 0) state (normalized such that n
J
/N =1). Compare this to the statistical distribution expected from Eq.(15.84) at 298 K. The
equilibrium bond distance of OH is 0.96966 .
J 7 8 9 10 11 12 13
n
J
/N 0.0181 0.0232 0.0356 0.0475 0.0377 0.0762 0.1045
J 14 15 16 17 18 19 20
n
J
/N 0.1266 0.1459 0.1466 0.1306 0.0907 0.0167 0.0000
Solution
Partition functions
15.26. Suppose that an array of harmonic oscillators has common frequency of
11
10 = s
-1
. Calculate the ratio of the number of
oscillators in the 10
th
quantum state (n=9) to those in the ground state at 0 K, 300 K and 1000 K. The energy levels are given by
1
( )
2
n
n h = + .
(This is a straight application of the Boltzmann distribution. Each energy level is non-degenerate.)
Solution
15.27. Calculate the average value of the energy per mole at the various temperatures for the oscillators in problem 17.

(This is best done by evaluating the partition function for harmonic oscillators and applying the general formula for .
Solution

15-8
15.28. The energy levels for a harmonic oscillator are given by
1
2
n
n h
| |
= +
|
\ .
.
a. Derive an expression for the mean-square fluctuation,
2
2
E
E E = in energy for these oscillators.
b. Use
11 -1
10 s = and the partition function from problem set 2 to evaluate the mean-square fluctuation.
c. Compare
E
toU E = .
d. What happens as the temperature is raised?
e. What happens as the number of particles increases?
(Fluctuations are generally negligible relative to macroscopic quantities but are important for many processes under certain
conditions, such as phase transitions.)
Solution
15.29. If the molecular partition function can be written as a product of factors,
int tr
q q q = , then energy, entropy and the other
thermodynamic properties can be written as a sum of terms. Show that this is true for E, S and A.
Solution
15.30. Calculate
2
2
8
h
ma
for helium in a one-dimensional box of a=10 cm and determine the energy level spacing for the first four levels.
Compare this with k
B
T. At what temperature are the energy levels spacing comparable in magnitude?
Solution
15.31. Calculate
v
for H
2
(frequency =4162 cm
-1
) and I
2
(frequency =213.1 cm
-1
). Calculate q
v
for these gases at 300 K.
Solution
15.32. Starting with the molecular partition function, prove for diatomic molecules in the high temperature limit that the translational,
rotational and vibrational contributions to the heat capacity agree with the expression from equipartition.
Solution
15-9
15.33. Work out the heat capacity, C
v
, at 300 K for the diatomic molecules listed below. Keep only the translational, rotational and
vibrational motion. Use table below for the rotational and vibrational temperatures. Only use the high temperature approximation if
it is valid. HCl, N
2
, O
2
, I
2
q
tr
q
r
q
v

HCl High temp. 19.73 1.0000016
N
2
High temp. 104.89 1.0000146
O
2
High temp. 144.92 1.00059
I
2
High temp. 555.5 1.552

Solution
15.34. The high temperature limit of the rotational partition function for diatomics is
r
r
T
q

Give a brief explanation of the quantum mechanical origin of the symmetry number . Use equations where appropriate.
Solution
Chapter 15: Statistical Mechanics Partition Functions for Some Special Cases
15-10
15.35. Prove that the Einstein function for the vibrational contribution to the heat capacity, Eq.(15.183) can be written as,
( )
2
cos
2 2
V
Einstein
u u
C R
| |
=
|
\ .

where

v
B
h
u
k T T

= = .
Show that the limiting value of Einstein function, Eq.(15.183),is the gas constant, R. (Recall that the Einstein vibration is restricted
to one frequency only so this is consistent with equipartition that states at high temperatures the contribution to the heat capacity is
equal to R for each degree or freedom. In this case, there is only one degree of freedom.)
Solution

Partition Functions for Some Special Cases
15.36. Starting with Eq. (15.156) obtain an expression for the molar internal energy U
m
of an ideal monatomic gas.
Solution
15.37. Calculate the molecular translational partition functions q
t
for (a) N
2
, (b) H
2
O, (c) C
6
H
6
in a volume of 1 m
3
at 300 K. In each case,
calculate also ln Q
t,m
, where Q
t,m
is the molar translational partition function.
Solution
15.38. The internuclear distance for N
2
is 0.1095 nm. Determine the molecular rotational partition function q
r
and ln Q for N
2
at 300 K.
Solution
15.39. Use the data in Table 15.3 (p. 807) to calculate, with reference to v =0, the molecular vibrational partition function for CO
2
at (a)
300 K and (b) 3000 K.
Solution
Chapter 15: Statistical Mechanics Partition Functions for Some Special Cases
15-11
15.40. Expressions such as the Sackur-Tetrode equation for the entropy contain a term ln (constant T). At temperatures close to the
absolute zero this term has large negative values, and the expression therefore leads to a negative value of the entropy. Comment on
this.
Solution
15.41. Calculate the entropy of argon gas at 25 C and 1 bar pressure.
Solution
15.42. From the data in Table 15.3, calculate, with reference to v =0, the molecular vibrational partition function for Br
2
at (a) 300 K and
(b) 3000 K.
Solution
15.43. Give the symmetry numbers of the following molecules: C
3
O
2
(carbon suboxide), CH
4
, C
2
H
4
, C
2
H
6
in the staggered conformation,
C
2
H
6
in the eclipsed conformation, CHCl
3
, C
3
H
6
(cyclopropane), C
6
H
6
(benzene), NH
2
D, CH
2
Cl
2
.
Solution
15.44. Show that the rotational partition function for a linear molecule can be expressed as
q
r
=k
B
T/Bh
where B is the rotational constant defined by Eq.(13.63).
Solution
*15.45. Calculate the molar translational entropy of chlorine gas at 25 C and 0.1 bar pressure.
Solution
*15.46. The carbon monoxide molecule has a moment of inertia of 1.45 10
46
kg m
2
and its vibrational frequency is 6.50 10
13
s
1
.
Calculate the translational, rotational, and vibrational contributions to the molar entropy of carbon monoxide at 25 C and 1 bar
pressure.
Solution
Chapter 15: Statistical Mechanics Equilibrium constants
15-12
15.47. Suppose that a system has equally spaced energy levels, the separation between neighboring levels being . Prove that the fraction
of the molecules in state i, having energy
i
greater than the energy of the lowest level, is
B B

1 exp exp
i
k T k T
| | | |
| |
\ . \ .

What is the limiting value of this fraction as T ? Explain your answer.
Solution
*15.48. Deduce the following from the Sackur-Tetrode equation (Eq.(15.159)), which applies to an ideal monatomic gas:
a. The dependence of entropy on relative molecular mass M
r
; also, obtain an expression for dS
m
/dM
r
.
b. The dependence of heat capacity C
P
on relative molecular mass.
c. The dependence of entropy on temperature; also obtain an expression for dS
m
/dT.
Solution
*15.49. Molecules absorbed on a surface sometimes behave like a two-dimensional gas. Derive an equation, analogous to the Sackur-
Tetrode Eq. (15.159), for the molar entropy of such an adsorbed layer of atoms, in terms of the molecular mass m and the surface
area A. What would be the molar entropy if 10
10
argon atoms were adsorbed on an area of 1 cm
2
at 25 C?
Solution
Equilibrium constants
15.50. Calculate the dissociation constant K
c
for the reaction
( ) ( )
3 3
2
O 2O P

at 1 000 K expressing the answer in mole l
-1
. Ignore nuclear degeneracy. Use the data from the table of Problem 51, along with the
value
9
1.25 10 cm
o
= .
Solution
15-13
15.51. From the data in Table 15.5, calculate K
P
at 1000 K for the water-gas reaction
CO
2
(g) +H
2
(g) = CO(g) +H
2
O(g)
Solution
15.52. Without making detailed calculations but by using symmetry numbers, estimate the equilibrium constants for the following
reactions:
a.
35
Cl
35
Cl +
37
Cl =
35
Cl
37
Cl +
35
Cl
b.
35
Cl
35
Cl +
37
Cl
37
Cl = 2
35
Cl
37
Cl
c. C
35
Cl
4
+
37
Cl = C
37
Cl
35
Cl
3
+
35
Cl
d. N
35
Cl
3
+
37
Cl = N
37
Cl
35
Cl
2
+
35
Cl
e.
35
Cl
2
O +
37
Cl =
37
Cl
35
ClO +
35
Cl
(Because of the similarity of the masses, these estimates will be quite accurate.)
D. M. Bishop and K. J . Laidler, J. Chem. Phys., 42, 1688(1965), have defined a statistical factor for a reaction as the number of
equivalent ways in which a reaction can occur. Thus for reaction (a) from left to right the statistical factor is 2, since the
37
Cl atom
can abstract either of the two
37
Cl atoms. For the reverse reaction the statistical factor r is 1, since the
35
Cl atom can only abstract the
35
Cl atom in order to give the desired products. If two identical molecules are involved, the statistical factor must be taken as the
number of equivalent products divided by 2; thus for reaction (b) from right to left the statistical factor is
1
2
.
Bishop and Laidler proved that the ratio l/r of statistical factors is always equal to the ratio
A
B
/
Y
Z
of symmetry numbers. Verify
that this is true for the given reactions.
This statistical factor procedure is useful in providing a simple insight into the factors that appear in equilibrium constants.
Solution
15-14
*15.53. Calculate the equilibrium constant at 1000 C for the dissociation
I
2
= 2I
given the following information: moment of inertia of I
2
=7.426 10
45
kg m
2
, wavenumber for I
2
vibration =213.67 cm
1
, U
0
=
148.45 kJ mol
1
. The I atom is in a
2
P
3/2
state; neglect higher states.
Solution
*15.54. Calculate the equilibrium constant K
P
for the dissociation
Na
2
= 2Na
at 1000 K, using the following data: internuclear separation in Na
2
=0.3716 nm, vibrational wavenumber =159.2 cm
1
, U
0
=
70.4 kJ mol
1
. The Na atom is in a
2
S
1/2
state; neglect hiher states.
Solution
P
at 1200 K for Cl
2
= 2Cl, from the following data: internuclear separation in Cl
2
=199 pm,
wavenumber for vibration =565.0 cm
1
, U
0
=240.0 kJ mol
1
. The ground state of Cl is a doublet,
2
3 1
,
2 2
P , the
separation between the states being 881 cm
1
.
Solution
15.56. Calculate the isotopic ratio K
H
/K
D
at 300 K for the reactions
H
2
= 2H and D
2
= 2D
Take the zero-point energies of H
2
and D
2
to be 26.1 kJ mol
1
and 18.5 kJ mol
1
, respectively.
Solution
Chapter 15: Statistical Mechanics Transition state theory
15-15
Transition state theory
15.57. On the basis of transition-state theory, make rough estimates of the preexponential factors at 300 K for the following types of gas
reactions:
a. A bimolecular reaction between an atom and a diatomic molecule, with the formation of a linear activated complex.
b. A bimolecular reaction between two diatomic molecules, the activated complex being nonlinear with one degree of restricted
rotation.
c. A bimolecular reaction between two nonlinear molecules, the activated complex being nonlinear with no restricted rotation.
d. A trimolecular reaction between three diatomic molecules, the activated complex being nonlinear with one degree of restricted
rotation.
Take the translational partition functions (for three degrees of freedom) to be 10
33
m
3
, the rotational functions for each degree of
freedom to be 10, the function for a restricted rotation to be 10, and the vibrational functions to be unity. Express the calculated
preexponential factors in molecular units (m
3
s
1
) and in molar units (dm
3
mol
1
s
1
).
Solution
15.58. The rate constant for the reaction
2NO +O
2
2NO
2

has been found to be proportional to T
3
. Suggest an explanation for this behavior.
Solution
15.59. Deduce the temperature dependency of the preexponential factor of the following types of reactions, where A represents an atom, L
a linear molecule, and N a nonlinear molecule:
A +L; A +N; L +L; L +N; N +N
Solution
15-16
15.60. The rate of the reaction
O
+
+N
2
NO
+
+N
has been found over a certain temperature range to be proportional to T
0.5
(M. McFarland et al., J. Chem. Phys., 59, 6620(1973).
How can this be explained in terms of simple transition-state theory?
Solution
15.61. For the case of two atoms giving a product, A +B = [AB]

Product, show that transition-state theory yields essentially the
same expression for the rate constant as the collision theory expression of Eq. (9.76).
Solution
15.62. In mass-spectrometric experiments, P. Kebarle and coworkers (J. Chem. Phys., 52, 212(1970) have found that under certain
conditions the rate constant for the reaction
+ +
2 2 3 2
N +N +N N +N
is proportional to T
2.5
Solution

15.63. On the basis of transition-state theory, and assuming the vibrational partitions to be temperature-independent, deduce the
temperature dependence of the preexponential factor for each of the following reactions:
a. 2ClO Cl
2
+O
2

b. NO +O
3
NO
2
+O
2

c. NO
2
+F
2
NO
2
F +F
d. 2NOCl 2NO + Cl
2

e. 2NO +Br
2
2NOBr
Solution
15-17
15.64. Benzaldehyde is oxidized by permanganate in aqueous solution. Suppose that the aldehydic hydrogen atom is replaced by a
deuterium atom; what can be said on the basis of transition-state theory about the kinetic isotope ratio k
H
/k
D
at 25 C? The
wavenumber of the aldehydic CH vibration is 2900 cm
1
.
Solution
15.65. A transition-state theory study of the reaction O(
3
P) +HCl generated the following information at T =600 K:
Reactants
O q
t
1.767 10
32
m
3
(for 3 degrees of freedom)
HCl q
t
6.084 10
32
m
3
q
r
39.40 (for 2 degrees of freedom)

0
2991.0 cm
1

Transition state (bent)
q
t
1.050 10
33
m
3
q
r
1730 (for 3 degrees of freedom)

1
1407.9 cm
1

2
266.8 cm
1

The maximum of the reaction path is at 45.97 kJ mol
1
. Calculate the rate constant at this temperature.
(Note: Some interesting problems on transition-state theory involving the use of a computer are to be found in S. J . Moss and C. J .
Coady, J. Chem. Ed., 60, 455(1983).)
Solution
Chapter 15: Statistical Mechanics Essay questions
15-18
Essay questions
15.66. The molar entropy of a gas increases with the temperature and with the molecular weight. Give a physical explanation of these two
effects.
15.67. Explain the factors that influence the magnitudes of partition functions, and comment on the magnitudes of the molecular partition
functions for translational, rotational, and vibrational energy. What characteristics of a molecule will lead to a high value of (a) q
t
,
(b) q
r
, and (c) q
v
?

15.68. Discuss the assumptions and limitations of conventional transition-state theory. Mention briefly procedures that have been used to
overcome some of the limitations.
15.69. On the basis of the treatment of equilibrium constants in terms of partition functions, explain the factors that account for the effects
of isotopic substitution.
Chapter 15: Statistical Mechanics Solutions
15-19
Solutions
15.1. Use Stirlings formula to calculate and approximate value for ln(N!) and compare with the exact value for N=5, 10, 50, 100, 1,000
and 10,000!
Solution:
Given: Stirlings formula, several values of N.
Required: calculate and approximate value for ln(N!)
We can use the stirlings formula from Eq. 15.25 to solve for the approximate value of ln(N!) :
ln ! ln or !
e
n
n
n
n n n n n = =
Note that the above formula works best if n is greater than 10.

N exact ln(N!) stirling's formula Error (%)

5 4.787492 3.047 36.35
10 15.10716 13.026 13.78
50 148.478 145.601 1.94
100 363.739 360.517 0.89
1000 5912.123 5907.755 0.07
10000 81959.46 82103.4 0.0018

15-20
( ) ln( !) ( ln )
ln( !)
ABS N N N N
Error
N

=
(Note: 10,000! is considerably less than (6.023 x 10
23
)! whence Stirlings formula is essentially exact.)

15-21
15.2. The number of possible arrangements of 4 objects (A B C D) among 4 positions (do not list them).
Solution:
Given: 4 objects (A B C D)
Required: the number of possible arrangements
The four objects are distinguishable, so there are
4
4
4! 24 P = = arrangements.


15-22
15.3. The number of possible arrangements of 3 objects (A B C) among 4 positions. List them all.
Solution:
Given: 3 objects (A B C)
Required: the number of possible arrangements among 4 positions
4
3
4!
24
(4 3)!
P = =

ABC_ AB_C A_BC _ABC
ACB_ AC_B A_CB _ACB
BAC_ BA_C BAC_ _BAC
BCA_ BC_A B_AC _BAC
CAB_ CA_B C_AB _CAB
CBA_ CB_A C_BA _CBA

15-23
15.4. Use the binomial distribution to work out the binomial coefficients for ( )
n
1 2
x x + for n=5. Arrange the numbers in Pascals
triangle. Work out the quantities
4
3
| |
|
\ .

5
3
| |
|
\ .
and
5
2
| |
|
\ .
to check your entries.
Solution:
Given: see above
Required: binomial coefficients
5 5 4 3 2 2 3 4 5
1 2 1 1 2 1 2 1 2 1 2 2
( ) 5 10 10 5 x x x x x x x x x x x x + = + + + + +

Work out Pascals triangle:
1
1 2 1
1 3 3 1
1 4 6 4 1
1 5 10 10 5 1
Use
!
( )! !
n
n r
r r
r
n P n
C
r P n r r
| |
= = =
|
\ .
to check the entries and spot check Pascals Triangle:
4
4
3
| |
=
|
\ .

5
10
3
| |
=
|
\ .
and
5
10
2
| |
=
|
\ .
etc.

15-24
15.5. Consider two sets of indistinguishable objects, {A A} and {B B B}. Work out and list the possible arrangements of these in 5
boxes, one object per box. Check your number against the formula.
!
!
!
n
r
c
c
n
P
n
=

Solution:
Given: {A A}, {B B B}, one object per box
Required: list all possible arrangements that can be placed in 5 boxes
! 5!
5
! 5!
10
! 3!2!
n
r
c
c
n
P P
n
= = =

BBBAA ABBAB
AABBB BABBA
BAABB ABABB
BBAAB BBABA
ABBBA BABAB

15-25
15.6. Work out the number of ways that the three objects (A B C) can be placed in 5 boxes, no more than one object per box. List all the
Solution
Given: (A B C), one object per box
5
3
! 5!
60
( )! (2)!
m
n
m
P P
m n
= = =

ABC_ _ A_BC_ _ABC_ A_ _BC AB_ _C AB_C_ A_B_C _ _ABC _A_B_C _AB_C
Now permute each of these ten columns 6 times keeping the empty boxes straight, AS ABOVE:
ABC_ _ etc.
ACB_ _
BAC_ _
BCA_ _
CAB_ _
CBA_ _

15-26
15.7. Work out the number of ways that the three objects (A A A) can be placed in 5 boxes, no more than one object per box. List all the
!
( ) ! !
n
r
n
C
n r r
=

Solution:
Given: (A A A), one object per box
5
3
! 5!
10
( )! ! (5 3)!3!
n
r
n
C C
n r r
= = =

AAA_ _ A_ _ AA
_ AAA _ A _A _ A
_ _ AAA A _AA_
_A_AA AA _ _ A
_AA_ A AA _ A _

15-27
15.8. Work out the number of ways that the two objects (A B) can be placed in 3 boxes with no restriction on the number of objects per
Solution:
Given: (A B), no restriction on the number of objects per box
2
3 9
n
N m = =

AB _ _ _ AB
_ AB _ B _ A
_ _ AB B A _
A _ B _ B A
A B _

15-28
15.9. Work out the number of ways that the two objects (A A) can be placed in 4 boxes without restriction on the number of objects per
Solution:
Given: (A A), no restriction on the number of objects per box
( ) ( ) 1 ! 4 2 1 !
10
!( 1)! 2!3!
m n
N
n m
+ +
= =

AA _ _ _ _ A A _
_ AA _ _ _ _ A A
_ _ AA _ A _ A _
_ _ _ AA A _ _ A
A A _ _ _ A _ A

15-29
15.10. When we remove the condition of distinguishability from the n objects of Eq.(A.5), we divide by n! to obtain Eq.(A.6). By
considering the simple case of 2 objects and 3 boxes, (same as Problem 15.8) show that it is improper similarly to divide Eq.(A.7)
by n! to obtain the desired result for Eq.(A.8).
Solution:
Given: 2 objects, 3 boxes
Required: see above
!
( )!
m
n
m
N P
m n
= =
Eq.(A.5) for distinguishable

!
( )! !
m
m n n
Eq.(A.6) for indistinguishable

Can we do the same for:
Eq.(A.7)
n
N m = for distinguishable
!
n
m
N
n
= for indistinguishable?
The answer is no. We must use:
( ) 1 !
!( 1)!
m n
N
n m
+
=

Show this for the case of 2 objects and 3 boxes:

Wrong:
2
3
4.5
! 2!
n
m
N
n
= =
Correct:
( ) ( ) 1 ! 3 2 1 !
6
!( 1)! 2!(3 1)!
m n
N
n m
+ +
= =

AA _ _ A _ A
_ AA _ _ A A
_ _ AA A A _

It will be seen from this problem that m
n
/n! is a number lying between m!/(n!(m-n)!) (Eq.(A.6) and (m+n-1)!/n!(m-1)!, Eq.(A.8). When
arrangements that differ between the two ways of counting, (due to distinguishability), represent a negligible part of the total number of
arrangements, the difference between the ways of counting becomes unimportant.

15-30
15.11. A partially deuterated methane sample is analyzed and found to contain equal molar quantities of hydrogen and deuterium. On a
random basis, calculate the percentage of species CH
4
, CH
3
D, CH
2
D
2
, CHD
3
,CD
4
.
Solution:
Given: see above
Required: calculate % of species CH
4
, CH
3
D, CH
2
D
2
, CHD
3
,CD
4
on a random basis.

Let the probability of an H appearing by P
H
and a D appearing as P
D
. These probabilities are take as equal and P
H
=P
D
=0.5.

There can be up to 4 bonds, so we have:

4 4 3 1 2 2 1 3 4
( ) 4 6 4
H D H H D H D H D D
P P P P P P P P P P + = + + + +

The chance of 4 H is
4
H
P =1/16
The chance of 3 H and 1 D is
3 1
4
H D
P P =1/4
2 2
6
H D
P P =6/16=3/8
1 3
4
H D
P P =1/4
The chance of 4 D is
4
D
P =1/16

15-31
15.12. Show that
!
ln
!( ) !
m
n m n
(
(

and
( ) 1 !
ln
!( 1) !
m n
n m
+ (
(

both approach ln
!
n
m
n
(
(

as n becomes large, provided that m>>n. (Use
Stirlings formula and use the fact that m>>n, and m>>1).)
Solution:
Given: see above
Required: see above

times
! ( 1)( 2)...( 1)
ln ln
!( )! !
( 1)( 2)...( 1) ( 1)( 2)...( )
lim ln ln
! !
...
ln ln
! !
n
n
n
m m m m m n
n m n n
m m m m n m m m m n
n n
m m m m m
n n
( + (
=
( (

+ ( ( (
=
( ( (

(
( (
= =
( (

(

and

( )
( 1)( 2)...( 2) ( 1)! 1 !
ln ln
!( 1)!
m n m n m m m n
n m
+ + + (
=
(

!( 1)! n m
2 terms
2
( 1)( 2)...( 2)
lim ln ln
! !
ln
!
n
n
n
m n
n
n
m n
m n m n m m
n n
m
n
>>
>>
(
(
(

( (
( ( ( + +
= =
( ( (

( (

(

15-32
Alternately we can start with Eqs.(15.56) and (15.59) to obtain Eq.(15.60):

BE
ln ln 1 ln 1
j j
j j
j j j
N g
g N
g N
( | | | |
= + + + + ( | |
| |
(
\ . \ .

ln ln 1 ln 1
j j
D j j
j j j
N g
g N
g N
( | | | |
= + ( | |
| |
(
\ . \ .

( ) ( )
ln
ln ln
j j
g N j j
j j
j j
j j j j j
j
g N
N N
N
N N g N N N
>>
( | |
+ ( |
|
(
\ .
(
= +

We have used: ln 1
j
j j
j
N
g N
g
| |
|
|
\ .
by expanding the natural logarithm, ( ) ln 1 x x for small x. Once again, neglect g
j
relative to
N
j
which gives Eq2.(15.60) and (15.61),
( ) ( )
ln ln ln
D j j j j j
j
N g N N N
(
= +

This result is of tremendous importance in permitting us to ignore the restrictions of Bose-Einstein and Fermi-Dirac quantum statistics when
the number of accessible quantum states (the m boxes) far exceed the number of molecules (the n objects).

15-33
15.13. Show that the maximum entropy, S, is obtained when all the probabilities,
i
p are equal, where
1
ln
n
i i
i
S p p
=
=
and
1
1
n
i
i
p
=
=

(This shows us that complete lack of knowledge of which state the system is in results in the highest entropy. When all states are
equally likely, we have no preferential state, and this means the most random or highest entropy.)

Solution:
Given: see above
Required: prove the above expression for equal probabilities
To solve for this problem, we can use the Lagrange multipliers. Take the derivative with respect to each probability subject to the
condition,
1
1
n
i
i
p
=
=
. For maximum entropy, we set the results equal to zero:

,
ln 1 0
j
i
i
p j i
S
p
p

| |
= + =
|
\ .

so,
1
2
3
ln 1
ln 1
ln 1
p
p
p
+ =
+ =
+ =
hence all the p
i
s must be equal and ( ) exp 1
i
p =

Since
1
1
n
i
i
p
=
=
then

( ) ( ) ( )
1 1 1
1 exp 1 exp 1 1 exp 1
n n n
i
i i i
p n
= = =
= = = =

so

15-34
1
ln 1
n

| |
=
|
\ .
so
1
i
p
n
=


15-35
15.14. Prove that for an N particle quantum state, the wave function must be either odd or even under the permutation of any two of the N
particles.
(This symmetry, of course, distinguishes bosons from fermions.)
Solution:
Given: N particle quantum state
Required: prove the above
Let (1,2,3,.... ) N be an N particle state. Now permute two particles:
(1,2,3,. ... ... ) (1,2,3,. ... ... )
ij
P i j N a j i N =
but two permutations must get us back to the same state that we started from,
2
(1,2,3,. ... ... ) (1,2,3,. ... ... )
ij ij
P P j i N a i j N =
The only way this can happen is if
2
1 a = or 1 a = .

15-36
15.15. A more accurate form of Stirlings approximation is
In the stopcock opening and closing example, recalculate the effect of
II III
S

using the above approximation and show that the
entropy change is negligible compared to
I II
S

. Assume that the two volumes are equal, and consider what happens to this new
entropy change 0
II III
S

< as the number of particles goes to infinity
(Although we observe no noticeable change when we physically close the stopcock in going from state II to III, there is a change
due to our definition. This problem asks you to look into. The reason the change is negligible from our theory is because we are
dealing with an enormous number of particles, and can use Stirlings approximation. However, if we had only a few particles, then
the effect of closing the stopcock would lead to a difference between the two states, II and III, i.e. the entropy would show a
decrease. This underscores the fact that we can not define entropy for a small number of particles because entropy is a statistical
quantity.)
Solution:
Given: altered version of Stirlings approximation
Required: the effect of
II III
S

The expression from the notes using the usual form of Stirlings approximation is:
( ) ( ) ( )
( )
( ) ( )
( ) ( )
1 2
1 2
1 2 1 2
1 2 1 2
1 1 2 2 1 2 1 2 1 2
1 2 1 2 1 1 1 2 2 2
!
ln
! !
ln ln ln
0
ln ln ln
N N
II III N N
N N N N
S A
N N N N
N N N N N N N N N N
A
N N N N N N N N N N
+

+

=
`
+

)
+ + + +

= =
`
+ + + +

)

15-37
We note that all the terms cancel. If we use the better approximation for Strirlings approximation,
we get:
( ) ( ) ( )
( )
1 2
1 2
1 2 1 2
1 2 1 2
!
ln
! !
N N
II III N N
N N N N
S A
N N N N
+

+

=
`
+

)

( ) ( ) ( )
( ) ( )
( )
1 1 2 2 1 2 1 2 1 2 1 2
1 2 1 2 1 1 1 1 2 2 2 2
1 2
1 2
ln ln ln ln 2
ln ln ln 2 ln ln 2
ln
2
N N N N N N N N N N N N
A
N N
A
N N

+ + + + + +

=
`
+ + + +
)
+
=

Let us assume that V
1
=V
2
.so N
1
=N
2
=N/2 giving
( ) ( )
( )
1 2
1 2
2 2
1 2
2 / 2 2 2
ln ln ln ln
2 2 2
2 / 2
N N
N N N A N A
A A
N N N N
N

=
+
= =
=

write this as:
2 2
ln ln ln
2 2
A A
N
N
| |
=
|
\ .

15-38
This shows that there is a decrease in entropy for large N, but this is negligible. The correction from this shows a decrease in entropy of
ln A N when the stopcock is closed. If we plug in A=k, then we get
( ) ( ) ( )
23 23 23 22
ln ln 1.38 10 ln 6.23 10 1.38 10 55 7.6 10 A N k N

= = = =
which is negligible. Suppose we had 10
10
moles, the calculation would change to:
( ) ( ) ( )
23 33 23 22
ln ln 1.38 10 ln 6.23 10 1.38 10 78 10.7 10 A N k N

= = = =
which is still negligible.
15-39
15.16. Using:
1 2
1 2
N N
V V
= prove the relationship:
( ) ( ) ( )
( ) ( )
( )
( ) ( )
( ) ( )
( ) ( ) ( )
1 2 1
2
1 2 1 2
1 2 1 2 1 2 1 2
1 2 1 2
1 2 1 2
/ / ! !
ln ln
! !
/ / ! !
N N N
N
c c
N N N N
c c
V V V V N N N N N N
N N N N
V V V V N N
(
(
+ +
(
( =
(
+ ( +

(

Solution:
Given:
1 2
1 2
N N
V V
=
Required: prove the above relationship
Cancel the V
c
s:
( ) ( ) ( )
( )
( ) ( ) ( )
( )
( ) ( ) ( )
( )
1 2 1 2
1 2
1 2 1 2 1 2
1 2
1 2
1 2 1 2 1 2 1 2
1 2 1 2 1 2 1 2
1 2 1 2
1 2 1 2
/ / ! !
ln ln
/ / ! ! ! !
!
ln
! !
N N N N
N N
c c c
N N N N N N
c c
c c
N N
N N
V V V V N N V V N N V
V V
V V V V N N V V N N
V V N N
V V N N
+
+ +
+
( (
+ + | |
= ( (
|
+ + ( ( \ .

(
+
= (
+ (

Now consider only the powers (since the factorials remain):
( ) ( )
( )
( ) ( )
1 2
1 2
1 2
1 1 2 2 1 2 1 2
1 2
ln ln ln ln
N N
N N
V V
N V N V N N V V
V V
+
(
= + + + (
+ (

Use
1 2 2 1
NV N V = to get
15-40
( )
2 2
1 2 2 1
1 1 2 2 1 2
1 2
ln ln ln
N V N V
N V N V N N
N N
| | +
= + +
|
\ .

Now write out all the terms as a sum of lns:
( ) ( )
2 2
1 1 2 2 1 2 1 2 2 1 1 1 1 2
2 1 2 2
ln ln ln ln ln
ln ln
N V N V N N N V N V N N N N
N N N N
= + + + + +
+ +

Now we can use the fact that
1 2 2 1
NV N V = to get
( ) { } ( )
1 1 2 2 1 2 1 2 1 2 1 1 1 2
2 1 2 2
ln ln ln ln ln
ln ln
N V N V N N NV N N N N N N
N N N N
= + + + + +
+ +

and expand the terms:
( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) ( ) ( )
( ) ( )
1 1 2 2 1 2 1 2 1 2 1 2
1 1 1 2 2 1 2 2
1 1 2 2 1 2 1 1 2 2 1 2 1 2
1 1 1 2 2 1 2 2
1 1 2 2 1 1 2 1 1 2 2 2 1 2 1 2
1
ln ln ln ln
ln ln ln ln
ln ln ln ln ln
ln ln ln ln
ln ln ln ln ln ln ln
N V N V N N NV N N N N
N N N N N N N N
N V N V N N N N N V N N N N
N N N N N N N N
N V N V N N N N N V N V N N N N
N
= + + + +
+ + + +
= + + + + +
+ + + +
= + + +
+
1 1 2 2 1 2 2
ln ln ln ln N N N N N N N + + +

collect and cancel terms:
15-41
1 1 2 2
ln ln N V N V = +
1 1
ln N N
2 1
ln N N
1 2 2 2
ln ln N V N V ( ) ( )
1 2 1 2
1 1
ln
ln
N N N N
N N
+ +
+
1 2 2 1
ln ln N N N N + +
( ) ( )
( ) ( )
2 2
1 1 1 2 1 2 2 2 1 2 1 2
1
1 1 2 2 2 1 2 1 2
2
ln
ln ln ln ln ln
ln ln ln ln
N N
N V N V N N N N N N N N
V
N N N N N N N N N
V
+
= + + + +
| |
= + + + +
|
\ .

Using
1 1
2 2
V N
V N
=
( ) ( )
( ) ( )
1
1 1 2 2 2 1 2 1 2
2
1 1 1 2 1 2 2 2 1 2 1 2
ln ln ln ln
ln ln ln ln ln
N
N N N N N N N N N
N
| |
= + + + +
|
\ .
= + + + +

1 1 1 2
ln ln N N N N =
1 2
ln N N + ( ) ( )
( ) ( )
( )
1 2
1 2
2 2 1 2 1 2
1 1 2 2 1 2 1 2
1 2
1 2
ln ln
ln ln ln
ln
N N
N N
N N N N N N
N N N N N N N N
N N
N N
+
+ + +
= + + +
(
= (
+ (

which is in the form we want.
15-42
15.17. Without considering energy, calculate the statistical weights for 30 quanta distributed amongst 30 oscillators for the following
distributions of the quanta:
0 1 2 29
0, 30, 0 N N N

= = =
0 1 2 3 29
1, 28, 1, 0 N N N N

= = = =
0 1 2 3 29
10, 10, 10, 0 N N N N

= = = =
(This is a problem of combinatorials, how many ways can 30 indistinguishable objects be distributed between 30 levels. For
oscillators, we usually label the lowest state by a 0, so we go up to the 29
th
level. In general, there is usually degeneracy (more
than one state with the same energy) Here we are calculating the degeneracy for various possible energies. In case a) the energy is
1
30 , for b) the energy is
0 1 2
28 2 + + and for c)
0 1 2
10 10 10 + + . The problem calculates the number of ways (the
statistical weight) that indistinguishable quantum can be arranged to give that particular energy.)
Solution:
Given: see above
Required: statistical weights
The number of ways of producing the energies of these distributions is simply:

30
1
!
i
i
N
N
=

a.
0 1 2 29
0, 30, 0 N N N

= = =
30
1
! 30!
1
0! 30! 0!....0!
i
i
N
N
=
=

15-43
b.
0 1 2 3 29
1, 28, 1, 0 N N N N

= = = =
30
1
! 30!
30 29 870
1! 28!1!....0!
i
i
N
N
=
= =

c.
0 1 2 3 29
10, 10, 10, 0 N N N N

= = = =
12
30
1
! 30!
29 26 23 22 2119 17 13 11 5 1.8503323 10
10!10!10!....0!
i
i
N
N
=
= =

15-44
15.18. Show that Eq.(15.148) satisfies FD and BE conditions of respectively no more that 1 particle, on the average, in a state, and any
number of particles in a state. Let ( ) exp /
B
x k T
= (

Solution:
Given: ( ) exp /
B
x k T
= (

Required: show above statement
The expression for BE (-) statistics and FD (+) statistic is
( )
BE
FD
1 1
( )
e 1 exp / 1
x
B
Z x
k T

=
(

) )

Since the range of is x , we have for FD statistics, (+) sign:
FD FD FD
( ) 1; (0) 1/ 2; ( ) 0; Z Z Z = = =
For BE statistics, (-) sign:
BE BE BE
( ) 1; (0) ; ( ) 0; Z Z Z = = =
Hence the average population of an eigenstate for fermions cannot exceed 1 while there is no restriction on the average population of an
eigenstate for bosons.
15-45
15.19. Starting from
ln ( , , )
B
S k E V N =
obtain the equation:
ln ( , , )
B
PV k T T V =
where ( , , ) T V is the grand partition function. Do NOT derive the ideal gas law (i.e. do not assume the particles do not interact).
(The grand partition function is one that is commonly used in chemical reactions.)
Solution:
Given: ln ( , , )
B
S k E V N =
Required: derive ln ( , , )
B
PV k T T V =
Grand Canonical ensemble: change variable N to , and E to T :

We have already changed the variables from ln ( , , ) S k E V N = , see Eq.(15.107), E to T, giving A/T, so now, using the Legendre
transformation,

( )
, ,
, ,
ln ( , , )
1 1
( , , )
B
T V
T V
A
k Q T V N
T
A
A A A A
T
T V N N N
T N T T N T T

=
(
| |
(
| | (
|
= = + = +
( |
(
|

\ . (

(
\ .

Following the same procedure, we get,

1
ln ( , , ) ( , , )
A E
k T V T V N S N
T T T T
= = + = + +

15-46
To identify the function that is natural for the grand canonical ensemble, note that the Gibbs energy for a one-component system is,

G N H TS E PV TS = = = + (a)

divide by T and rearrange,

E PV
N S
T T T
= + (b)

Comparing Eq.(a) with Eq.(b) shows that,

ln ( , , )
B
PV
k T V
T
=
15-47
15.20. Derive expressions for the energy U=E, the entropy S the pressure P and the Helmholtz energy A, and the Gibbs energy G in terms
of the Canonical ensemble, Q.
Solution:
Given: U =E, S, P, A, G, Q
Required: derivation
We have:
ln ( , , )
B
A k T Q T V N =
and
dA Sdt PdV =
using

T V
A A
P S
V T
| | | |
= =
| |

\ . \ .

gives
ln
ln
B
V V
A Q
S kT k Q
T T
| | | |
= = +
| |

\ . \ .

ln
B
T T
A Q
P k T
V V
| | | |
= =
| |

\ . \ .

and from A=E-TS
2
ln

B
V
Q
E k T
T
| |
=
|
\ .

15-48
finally the Gibbs energy is
ln
ln +
B B
T
Q
G A PV k T Q k TV
V
| |
= + =
|
\ .

15-49
15.21. Find the natural function for the isothermal-isobaric ensemble, ( , , ) T P N , i.e. for variables T, P and N.
Solution:
Given: isothermal-isobaric
Required: natural function
We have:
ln ( , , ) ( , , ) microcanonical ensemble
( , , ) ln ( , , ) ln ( , , ) canonical ensemble
( , , ) ln ( , , ) ln ( , , )
B
B
B
S k U V N U V N
T V N k T V N k Q T V N
T V k T V k T V
= =
=
= grand canonical ensemble
( , , ) ln ( , , ) ln ( , , ) isothermal-isobaric ensemble
B
T P N k T P N k T P N =

We know that the natural function of the variables , , T V N is A/T, so all we have to do is apply the Legendre transformation for V to T,
( )
,
, ,
/ 1
( , , )
1
T V
T V N
A T A A A
T P N P P
T P T T P
A A PV G
VP
T T T T
| | | |
= = +
| |

\ .
\ .
+ | |
= = =
|
\ .

so, as no surprise the isothermal-isobaric ensemble is
( , , ) ln ( , , ) ln ( , , )
B B
G
T P N k T P N k T P N
T
= =
or
ln ( , , )
B
G k T T P N =

15-50
15.22. Obtain an expression for C
P
in terms of the partition function Q for the system.
Solution:
Given: C
p
, Q
Required: see above
We know that
p
P
H
C
T
| |
=
|
\ .
,
and that
2
0 B B
ln
V
Q
H U k T Nk T
T
| |
= +
|
\ .

if
0
0 U = , substitution of the above expression into the expression for
p
C will yield:

2
B B
2
B B
ln
ln
p
P
V
p
P
p
V
P
H
C
T
Q
k T Nk T
T
C
T
Q
C k T Nk
T T
| |
=
|
\ .
| | ( | |
+
| | (
\ .

|
=
|
|
|
\ .
( | |
= +
` | (

\ . )


15-51
15.23. Obtain an expression for the pressure P in terms of the molecular partition function q, for (a) distinguishable molecules and (b)
indistinguishable molecules. Express the result in terms of the number of molecules N and also the amount of substance n.
Solution:
Given: P, q, N, n
Required: see above
From Eq. 3.118,

B
ln
T T
A Q
P k T
V V
| | | |
= =
| |

\ . \ .

a. From Eq. 15.45 for distinguishable molecules
N
Q q =
Take the natural logarithm on both sides yield:
ln ln Q N q =
Therefore,

( )
B
B
B
B
ln
ln
ln ln
ln
ln
T
T
T
T
T
Q
P k T
V
N q
P k T
V
q N N q
P k T
V
q
P Nk T
V
q
P nRT
V
| |
=
|
\ .
| |
=
|
\ .
+ | |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .

15-52
b. From Eq. 15.47 for indistinguishable molecules,
!
N
q
Q
N
=
Take the natural logarithm on both sides yield:
ln ln ln !
N
Q q N =
ln ln ln Q N q N N N = +
Similarly to a., we will substitute the above expression into
B
ln
T
Q
P k T
V
| |
=
|
\ .
, and will yield the same answer as a.:

B
ln
T
Q
P k T
V
| |
=
|
\ .


15-53
15.24. The partition function for each degree of vibrational freedom is
B
1/ 1 exp
hv
k T
( | |
( |
\ .
(Eq.(15.173)). Obtain from this expression
the limiting value of the vibrational contribution to C
V
as T approaches infinity.
Solution:
Given:
B
1/ 1 exp
hv
k T
( | |
( |
\ .
,T
Required: limiting value of the vibrational contribution to C
V

In the limit as T the vibrational partition function becomes

B
B
1
1 1
k T
h h
k T

=
| |

|
\ .

Then

0, m m
U U RT =
and

1 1
,
8.3145 J K mol
V m
C R

= =
15-54
15.25. Chemical reactions often lead to the formation of products whose energy distributions show significant deviations from the
statistical distribution of Eq. 15.40. In a study of an elementary reaction with
16
O
1
H radical as one of the products [Zhang, van
der Zande, Bronikowski, and Zare, J. Chem. Phys. 94, 2704(1994)], the following rotational distribution was observed for the OH(v
= 0) state (normalized such that n
J
/N =1). Compare this to the statistical distribution expected from Eq.(15.84) at 298 K. The
equilibrium bond distance of OH is 0.96966 .
J 7 8 9 10 11 12 13
n
J
/N 0.0181 0.0232 0.0356 0.0475 0.0377 0.0762 0.1045
J 14 15 16 17 18 19 20
n
J
/N 0.1266 0.1459 0.1466 0.1306 0.0907 0.0167 0.0000
Solution:
Given: v = 0, n
J
/N =1, T =298 K,
OH
0.96966 d =
Required: comparison to statistical distribution
The reduced mass of
16
O
1
H is

1
1.0078 g mol

=
15.9949 g
1
mol
( )
1
1.0078 15.9949 g mol
+
23 1
1
6.022 10 mol
kg
1000 g
27
1.574 335 324 10 kg
=

The moment of inertia is

( )( )
2
27 10 47 2
1.574 335 324 10 kg 0.96966 10 m 1.480 253 857 10 kg m I

= =
The rotational partition function is

47
B
2
2 1.480 253 857 10 kg
2
r
Ik T
q
= =
h
2
m
( )
23 2
1.381 10 m
kg
2
s
1
K
( )
298 K
( )
( )
2
34 4
6.626 10 m
2
kg
2
s
0.277 506 523 at 298 K

r
q T = =

15-55
Now, using Eq. 15.40 with 2 1
J
g J = + , and
( )
2
1
2
J
J J
I
+
=
h

, we write

( )
2
B
1)
2 1
exp
2
J
r
J J
n J
N q Ik T
(
+
+
( =
(

h
.
A plot of this fraction as a function of J along with the experimental distribution is shown in the accompanying figure.

15-56
15.26. Suppose that an array of harmonic oscillators has common frequency of
11
10 = s
-1
. Calculate the ratio of the number of
oscillators in the 10
th
quantum state (n=9) to those in the ground state at 0 K, 300 K and 1000 K. The energy levels are given by
1
( )
2
n
n h = + .
(This is a straight application of the Boltzmann distribution. Each energy level is non-degenerate.)
Solution:
Given:
11
10 = s
-1,
n =9, T =0 K, 300 K, 1000 K,
1
( )
2
n
n h = +
Required: ratio of the number of oscillators
( )
( )( )
( )
( )( )
( )
10 9
0 0
34 11 -1
23 -1
34 11 -1
23 -1
1
exp 9
2 exp( )
exp 9
exp( ) 1
exp
2
9 6.623 10 J s 10 s
9
exp exp
1.38 10 J K
9 6.623 10 J s 10 s
exp ex
1.38 10 J K
B
h
N
h
N
h
h
k T T
T

| | | |
+
| |
\ . \ .
= = =
| | | |
| |
\ . \ .
| |
| |
| = =
|
|
\ .
\ .
| |
| = =
|
\ .
2 -1
3.8874 10 K
p
T
| |
|
\ .

15-57
( )
( )
2 -1
10
0
2 -1
10
0
10
0
2 -1
10
0
10
0
2 -1
10
0
( ) 3.8874 10 K
exp
(0) 3.8874 10 K
exp
0
(0)
0
(300) 3.8874 10 K
exp exp 1.129
300
(300)
0.274
(1000) 3.8874 10 K
exp exp 0.38874
1000
N T
N T
N
N
N
N
N
N
N
N
N
N
| |
=
|
\ .
| |
=
|
\ .
=
| |
= =
|
\ .
=
| |
= =
|
\ .

10
0
(1000)
0.678
N
N
=
15-58
15.27. Calculate the average value of the energy per mole at the various temperatures for the oscillators in problem 17.

(This is best done by evaluating the partition function for harmonic oscillators and applying the general formula for .
Solution:
Given: problem 17
Required: average value of the energy per mole
You need to know the following sum:
( )
( ) 0
1
exp
1 exp( )
n
xn
x
=
=

Now calculate the partition function for the case that the energy is:
1
( )
2
n
n h = +
( ) ( ) | |
0
exp / exp
i B
i n
q k T nh = = (

so
( )
1
1 exp( )
q
h
=

Now use:
1 ln
o
dq d q
q d d

= =
15-59
( )
( )
( )
2
exp 1 1 1 1
1 exp( )
1 exp( )
1
h dq d
h
q d q d h q
h
q

| |
| |
= = |
|
|
|

\ .
\ .
( )
1
1 exp( ) h
| |
|
|

\ .
( )
( ) ( )
exp
1 exp( ) 1 exp( )
h h
h
h h

| |
=
|
|

\ .

so
( )
1
exp( ) 1
o
dq h
q d h

= =

or
( ) ( )
2 exp( ) 1
h h
h

= +

15-60
( )
23
23 -1
( ) (0)
2 exp( ) 1 2
6.623 10
3.31 10 J molecule (zero point energy)
2
h h h h
T

= + = +

= =
( ) ( )
( ) ( )
( )
( )
23 -1
23 23 -1
23 -1 23 -1
21 21 21
6.623 10 J molecule
(300)
2 2 exp( ) 1
exp(6.623 10 J / 1.38 10 J K 300 K ) 1
6.623 10 J molecule 6.623 10 J molecule
2 1.0161 1 2 0.0161
0.0331 10 4.173 10 =4.206 10
h h h
h
h h

= + = +

= + = +
= +
-1
J molecule
( ) ( )
( ) ( )
( )
( )
23 -1
23 23 -1
23 -1 23 -1
20 20
6.623 10 J molecule
(1000)
2 2 exp( ) 1
exp(6.623 10 J / 1.38 10 J K 1000 K ) 1
6.623 10 J molecule 6.623 10 J molecule
2 1.0048 1 2 0.0048
0.00331 10 1.3798 10 =1.383 10
h h h
h
h h

= + = +

= + = +
= +
20 -1
J molecule
-1
-1
-1
(0) 19.5 J mol
(300) 2.533 kJ mol
(1000) 8.329 kJ mol
E N
E
E
E
=
=
=
=


15-61
15.28. The energy levels for a harmonic oscillator are given by
1
2
n
n h
| |
= +
|
\ .
.
a. Derive an expression for the mean-square fluctuation,
2
2
E
E E = in energy for these oscillators.
b. Use
11 -1
10 s = and the partition function from problem set 2 to evaluate the mean-square fluctuation.
c. Compare
E
toU E = .
d. What happens as the temperature is raised?
e. What happens as the number of particles increases?
(Fluctuations are generally negligible relative to macroscopic quantities but are important for many processes under certain
conditions, such as phase transitions.)
Solution:
Given:
1
2
n
n h
| |
= +
|
\ .

Required: see above
a.
exp
j
j
j B
E
E
k T
E
q
| |
|
\ .
=

or
exp exp
j j
j
j j B B
E E
E E
k T k T
| | | |
=
| |
\ . \ .

Differentiate with respect to T,
15-62

2
2
,
exp exp
j j
j j
j j V N B B B
E E E E
E E
T Qk T k T k T
| | | | | |
+ =
| | |
\ .
\ . \ .

or

2 2
2 2 2
E B V
E E E E k T C = = =

2
E B V
k T C =
so the ratio of energy fluctuation to the average energy is

2 1/2
( )
B V E
k T C
E E
=
b. From Eq.(15.128)

( )
2
2 2
ln
1
B
V
V
V
Nk E q
C
T T
T
| |
| | |
= =
|
|
\ .
|
\ .

therefore
( ) ( )
2 2 2 2
2
2 2 2
ln ln
1 1
B
E B V B
V V
Nk T q q
k T C k N
T
T T
| | | |

| |
= = =
| |
| |
\ . \ .

From Eq.(15.155), we have
( )
1
1 exp( )
q
h
=

Differentiating twice wrt 1/T,
15-63
( )
2
2
2 3
exp
ln
1
1 exp
B
B
V
B
h
k T q h
k
h
T
k T
| |
| |
|
| |
| \ .
=
|
|
| | \ . | | |
\ .
| |
\ . \ .

this gives
( )
2
2
2 3/2
exp
2 ln
1
1 exp
B
E B V B
V
B
h
k T q
k T C k N h N
h
T
k T
| |
| |
|
| \ .
= = =
|
| | | | |
\ .
| |
\ . \ .

or in numbers:

( )
( )
23
3/2
exp
exp 2.4/ 2
6.623 10 J
1 exp( 4.799/ ) 3
1 exp
2
B
E
B
h
T k T
h N N
T h
k T

| |
|

\ .
= =
| | | |

| |
\ . \ .

c. We can calculate the average energy,
( ) ( ) ( ) ( )
2 2 exp( ) 1 exp( ) 1
h h Nh Nh
E N
h h

= + = = +

giving

( )( )
( ) ( )
23 23 -1
23 23 -1
6.023 10 molecule 6.623 10 J molecule
2
exp(6.623 10 J / 1.38 10 J K K ) 1
39.9 J
19.9 J
exp(4.799/ ) 1
Nh
E
T
E n
T

= +

| |
= +
|
\ .

15-64
where n is the number of moles. Therefore the the ratio is

( )
( )
23
3/2
exp 2.4/
6.623 10 J
1 exp( 4.799/ )
39.9 J
19.9 J
exp(4.799/ ) 1
E
T
T N
E n
T
(

(
=
(
| |
+ (
|
\ . (

which shows that the fluctuations are very small.
d. Clearly at T=0 K the exponentials in the numerator vanish, while the denominator shows the second term vanishes. As T increases,
these terms become important. If you want to expand the exponentials in 1/T, then you will see what happens at high temperature,
but that is not necessary for the problem.
e. From the above equation,
2
3/2
exp
2
1 exp
B
E B V E
B
h
k T
k T C h N
h
k T
| |
|
\ .
= = =
| | | |

| |
\ . \ .

It is clear that the fluctuations increase as the square root of N. Parts d. and show us that fluctuations increase with temperature and
density.

15-65
15.29. If the molecular partition function can be written as a product of factors,
int tr
q q q = , then energy, entropy and the other
thermodynamic properties can be written as a sum of terms. Show that this is true for E, S and A.
Solution:
Given:
int tr
q q q =
Required: show that E, S, and A can be written as a sum of terms
( )
1 2 2 2
2 1 2
1 2 1 2
ln ln
ln ln
o
V
V
o o o
V V
q q q
E E RT RT
T T
q q
E E RT E E E E
T T
| | | |
= =
| |

\ .
\ .
( | | | |
= + = +
| | (

\ . \ .

For the entropy and the Hemlholtz energy you have to decide where the factorial goes. Therefore we write
int tr
q q q =
int
int
int
int
ln
ln ln 1
ln
ln ln
ln 1
ln ln
tr
B tr
V
tr tr
B
V V
q q
S Nk q q N
T
q q q
Nk q
N T T
( | |
= +
( |
\ .

( | | | |
= +
( | |

\ . \ .

int
int
ln ln
ln 1 ln
ln ln
tr tr
B B
V V
q q q
Nk Nk q
N T T
( ( | | | |
= +
( ( | |

\ . \ .

int
int
int
ln ln
ln ln 1 ln
ln ln
tr tr
B B
V V
tr
q q q
Nk N Nk q
N T T
S S
( ( | | | |
= +
( ( | |

\ . \ .

= +

int
int
ln 1 ln 1 ln
tr
B B B
tr
q q
A Nk T Nk T Nk T q
N N
A A
( (
= + = +
( (

= +

15-66
From here on, you can put in the
int
q as a product and the energies, entropy and free energies become a sum.

15-67
15.30. Calculate
2
2
8
h
ma
for helium in a one-dimensional box of a=10 cm and determine the energy level spacing for the first four levels.
Compare this with k
B
T. At what temperature are the energy levels spacing comparable in magnitude?
Solution:
Given: a=10 cm
Required: value of
2
2
8
h
ma
, energy level spacing, compare energy level spacing with k
B
T, temperature at which the energy levels spacing are
comparable
( )
( )
2
34
2
2 2
27 2
2
40
2
6.626 10 J -s
8
8 4 1.673 10 kg 0.1 m
8.2 10 J
8
h
ma
h
ma
=

=

Energy levels:
2 2
2
8
n h
ma

n energy (J ) difference(J ) degrees K
1
40
8.2 10

40
24.6 10

16
1.8 10

2
40
32.8 10

40
41 10

16
3 10

3
40
73.8 10

40
57 10

16
4 10

4
40
131. 10

15-68
The thermal energy is k
B
T, and the energy splitting for the translational energy is of the order of
16
10
K. That is, only at temperatures below

about 10
-16
K are these states not in the high temperature approximation. Therefore at any reasonable temperature, the translation energy
levels are all occupied and are in the classical limit (high T).
15-69
15.31. Calculate
v
for H
2
(frequency =4162 cm
-1
) and I
2
(frequency =213.1 cm
-1
). Calculate q
v
for these gases at 300 K.
Solution:
Given: for H
2
: frequency =4162 cm
-1
, for I
2
: frequency =213.1 cm
-1
, T =300 K
Required:
v
, q
v
1
1 exp
v
v
q
T
=
| |

|
\ .

For H
2
,
( )( )( )
( )
34 -1 10 -1
23 -1
6.626 10 J -s 4162 cm 3 10 cm s
1.381 10 J K
5990 K
v
B
v
h
k

= =
=

1 1
5859
5990 1 0.9998293
1 exp
300
v
q = = =
| |

|
\ .

For I
2
,
( )( )( )
( )
34 -1 10 -1
23 -1
6.626 10 J -s 213.1 cm 3 10 cm s
306.7 K
1.381 10 J K
v
B
h
k

= = =

1
1.562
306.7
1 exp
300
v
q = =
| |

|
\ .

15-70
15.32. Starting with the molecular partition function, prove for diatomic molecules in the high temperature limit that the translational,
rotational and vibrational contributions to the heat capacity agree with the expression from equipartition.
Solution:
Given: see above
Required: see above
This is for diatomics.
2
2
ln
tr tr B
tr o B
V V
q q Lk T
E E Lk T
T q T
| | | |
= =
| |

\ . \ .

3/2
2 2
1/2
2
2 3
2
2
B B B
tr o
B
Lk T mk Lk T
E E T
q h
mk
| |
= =
|
\ .
2
T
h
3/2
2
B
mk
| |
|
\ .
2
h
3/2
1/2
2 2
1/2
3/2
3
2
3 3 3 3
2 2 2 2
B B
tr o B
T
Lk T Lk T
E E T Lk T RT
T T
| |
|
\ .
= = = =

Rotation:
r
r
T
q

2 2
B r B
r o
V r
r
Lk T q Lk T
E E
q T
T
| |
= =
|
\ .
1
r
| |
|
|
\ .
2
V
B
r o B
T
T
Lk T
E E Lk T RT
T
| |
|
\ .
= = =

Vibration:
v
v
T
q =

15-71

2 2
v B B
v o
V r
v
q Lk T Lk T
E E
q T
T
| |
= =
|
\ .
1
v
| |
|
|
\ .
2
V
B
v o B
T
T
Lk T
E E Lk T RT
T
| |
|
\ .
= = =


15-72
15.33. Work out the heat capacity, C
v
, at 300 K for the diatomic molecules listed below. Keep only the translational, rotational and
vibrational motion. Use table below for the rotational and vibrational temperatures. Only use the high temperature approximation if
it is valid. HCl, N
2
, O
2
, I
2
q
tr
q
r
q
v

HCl High temp. 19.73 1.0000016
N
2
High temp. 104.89 1.0000146
O
2
High temp. 144.92 1.00059
I
2
High temp. 555.5 1.552

Solution:
Given: T =300 K, above table
Required: C
v

v
K

r
K r
e
D
o
eV
HCl 4140 15.2 1.275 4.43
N
2
3340 2.86 1.095 9.76
O
2
2230 2.07 1.204 5.08
I
2
310 0.054 2.667 1.54

Translantional:
15-73
3/2
2 3
2
B
t
mk T V
q V
h
| |
= =
|

\ .
From question 1, these are all high temperature so we can take the contribution to the heat capacity as
3
2
R
Rotational:
0
( 1)
(2 1)exp(
r
r
j
j j
q j
T
=
+
= +
where
2
2
8
r
B
h
k I
=

or at high temperatures:
r
r
T
q

If we look at the table, we can see that the largest rotational temperature is 15.2 K. Hence only for HCl might we have a deviation from the
high temperature approximation. So for HCl we have:
0
1 2 3 4 5 6 7 8
( 1) 15.2 2 15.2 6 15.2
(2 1)exp 1 3exp 5exp ...
300 300 300
1 2.7109 3.6893 3.8110 3.2671 2.4058 1.5480 0.8787 0.4427 0.1987
r
j
j j j j j j j j j
j j
q j
=
= = = = = = = = =
+ | | | | | |
= + = + +
| | |
\ . \ . \ .
= + + + + + + + + +

9 10
0.079..
20.03
j =
+
=

If we compare this with the high temperature limit, we get:
300
19.73
15.2
r
r
T
q = = =
Therefore for the rotational motion, HCl is in the high temperature limit at 300 K. Hence all the others are in the
high temperature limit too.
Vibrational:
15-74
1
1 exp
v
v
q
T
| | | |
=
| |
\ . \ .
We can just plug in the values and calculate the result (see next table):
1
4140
1 exp 1.0000016
300
v
q
| | | |
= =
| |
\ . \ .
etc. (see table) Clearly all but I
2
are close to 1 meaning that the vibrational contributions are not in
the high temperature approximation.
To calculate the heat capacity for each, the contribution from translational and rotational is the same, being the high temperature
approximation:
3 5
2 2
tranlational
Rotational
V
C R R R = + = which is good for HCl, N
2
and O
2
. For I
2
, we have to do a bit more work:
From Eq.(9.38):
( )
2 2
2 2 2 2
ln ln
1
B B
V
V
V
V
Lk Lk E q q
C
T T T x
T
| |
| | | | |
= = =
| |
|

\ .
\ .
|
\ .
where x=T
-1
.
This is the calculation for the contribution from vibration to the heat capacity of I
2
.
15-75
2
2 2 2 2
2 2
ln ln 1
1 1 1
1
v
v v v B B B
V
V V v
V
B B
x
v v
q q q Lk Lk Lk
C
T x T x x T x q x
Lk Lk
T x q x e T x q
| | | | | |
= = =
| | |

\ . \ .
\ .
| | (
= =
|
(

\ .
( )
2
1
v
v
x
v
x
e
e
( ) ( )
( )
( )
( )
( )
( )
2 2 2 2
2
2 310/300
2 2 2 2
310/300
1
1 1
1
310
0.8524
300
1 1
v v
v v
v
v
v
x x
v B v B v v B
x x
x
x
B B v
x
e Lk Lk e Lk
T x T x T e e
e
Lk Lk e e
R
T
e e

| |
|
|
|
\ .
| |
| | | |

|
| | = = =
| | |

\ . \ .
\ .
| | | |
| |
= = =
| |

\ . \ .

Hence the heat capacity of I
2
is
5
0.8524
2
V
C R R = + =3.3524R=27.87 J K
-1
Mol
-1
Experimentally, the heat capacities of HCl, N
2
, and O
2
are very close to 2.5R. This shows that the at 300 K the calculations are correct if
the vibrational contributions are ignored. In contrast for Iodine, has contributions from the vibrational parts. Unfortunately it is a solid at
300 K and does not boil until over 400 K, so we do not have data at 300 K. On the other hand, above the boiling point you can see that the
heat capacity of iodine will be 3.5 R, since the vibrational contributions will then be in high temperature limit.

15-76
15.34. The high temperature limit of the rotational partition function for diatomics is
r
r
T
q

Give a brief explanation of the quantum mechanical origin of the symmetry number . Use equations where appropriate.
Solution:
Given:
r
r
T
q

Required: explanation
Symmetry restrictions due to permutation symmetry lead to the sum over rotational states omitting certain values. For homonuclear
diatomics, one half of the states are missing. For example,
16
2
O (Hill page 469) has a rotational partition function of,
hightemperature
all values
1
... ...
2
rn
j even j
q
=
=

This explains the quantum mechanical origin of the symmetry number =2.

15-77
15.35. Prove that the Einstein function for the vibrational contribution to the heat capacity, Eq.(15.183) can be written as,
( )
2
cos
2 2
V
Einstein
u u
C R
| |
=
|
\ .

where

v
B
h
u
k T T

= = .
Show that the limiting value of Einstein function, Eq.(15.183),is the gas constant, R. (Recall that the Einstein vibration is restricted
to one frequency only so this is consistent with equipartition that states at high temperatures the contribution to the heat capacity is
equal to R for each degree or freedom. In this case, there is only one degree of freedom.)
Solution:
Given: see above
Required: see above
The vibrational contribution to the heat capacity, Eq.(15.166)

2
/
2
/
1
E
E
T
E
V
T
e
C R
T
e
| |
=
|
( \ .

2 2
2 2
/2 /2
1
u
V
u u u
u e u
C R R
e e e
= =
( (

where /
E
u T = . Using
1 2
cosech
sinh
u u
u
u e e
= =
gives,
2
2
2
/2 /2
4
cosech
4 2 2
V
u u
u u u
C R R
e e
| |
= =
|
\ . (

15-78
15.36. Starting with Eq. (15.156) obtain an expression for the molar internal energy U
m
of an ideal monatomic gas.
Solution:
Given: Eq. 15.156
Required: obtain expression for U
m
Einsteins expression is:
( )
( )
( ) ( )
2
2
exp
exp 1
V
Einstein
u u
C R
u
=

where
E E
B
h
u
k T T

= = so as T , 0 u , and ( ) exp 1 u except for the denominator,
( )
( )
( ) ( ) ( )
2 2
0
2 2
exp
1 1 exp 1
T
V
Einstein
u u u
C R R R
u u
= =
+


15-79
15.37. Calculate the molecular translational partition functions q
t
for (a) N
2
, (b) H
2
O, (c) C
6
H
6
in a volume of 1 m
3
at 300 K. In each case,
calculate also ln Q
t,m
, where Q
t,m
is the molar translational partition function.
Solution:
Given: V =1 m
3
, T =300 K
Required: molar translational partition functions, ln Q
t,m
From Eq. 15.86, we know that

( )
( )
( )
( )
( )
3 2
B
3
3 2
23
3 2
3
34
3 2
70
2
2 1.381 10 300
m/kg
6.626 10
1.444 10 m/kg
t
t
t
mk T V
q
h
q
q
=

=
=

15-80

a. For N
2
:
2 14.0067 g
m

=
1
mol
3 1
10 kg g

23 1
6.022 10 mol
( )
( )
( )
26
3 2
23 26
3
34
32
23
23 32
,
4.651 843 241 10 kg
2 1.381 10 300 4.651 843 241 10
6.626 10
1.449 10
For indistinguishable molecules,
ln ln ln
Here 6.022 10
ln 6.022 10 ln 1.449 10 6.02
t
t
t m
m
q
q
N
Q N q N N N
N
Q
=

=
=
= +
=
=
( )
23 23
23
25
,
25
,
2 10 ln 6.022 10
6.022 10
ln 1.222 388 923 10
ln 1.223 10
t m
t m
Q
Q

+
=
=

b. For H
2
O:
18.015 g
m =
1
mol
3 1
10 kg g

23 1
6.022 10 mol

15-81
( )
( )
( ) ( )
26
3 2
23 26
3
34
31
23 31 23 23
,
23
25
,
,
2.991 531 053 10 kg
2 1.381 10 300 2.991 531 053 10
6.626 10
7.47 10
ln 6.022 10 ln 7.47 10 6.022 10 ln 6.022 10
6.022 10
ln 1.182 489 333 10
ln
t
t
t m
t m
t m
m
q
q
Q
Q
Q
=

=
=
=
+
=
25
1.182 10 =

c. For C
6
H
6
:
78.114 g
m =
1
mol
3 1
10 kg g

23 1
6.022 10 mol
( )
( )
( ) ( )
25
3 2
23 26
3
34
32
23 32 23 23
,
23
25
,
1.297 143 806 10 kg
2 1.381 10 300 1.297 143 806 10
6.626 10
6.746 10
ln 6.022 10 ln 6.746 10 6.022 10 ln 6.022 10
6.022 10
ln 1.315 011 864 10
ln
t
t
t m
t m
t
m
q
q
Q
Q
Q
=

=
=
=
+
=
25
,
1.315 10
m
=

15-82
15.38. The internuclear distance for N
2
is 0.1095 nm. Determine the molecular rotational partition function q
r
and ln Q for N
2
at 300 K.
Solution:
Given: d =0.1095 nm, T =300 K
Required: q
r
, lnQ
14.0067 g
Mass of N atom=
1
mol
3 1
10 kg g

23 1
6.022 10 mol
26
Mass of N atom 2.325 921 621 10 kg
=

Moment of inertia of N
2

( )
2
26 9
46 2
1
2.325 921 621 10 0.1095 10
2
1.394 419 086 10 kg m
I
I

=
=

The symmetry number is 2.

( )( )( )
( )
( ) ( )
2 46 23
2
34
23
24
24
8 1.394 419 086 10 1.381 10 300
2 6.626 10
51.947 556 65
51.9
ln ln
ln 6.022 10 ln 51.947 556 65
ln 2.378 831 327 10
ln 2.38 10
r
r
r
r r
r
r
r
q
q
q
Q L q
Q
Q
Q
=
=
=
=
=
=

15-83
15.39. Use the data in Table 15.3 (p. 807) to calculate, with reference to v =0, the molecular vibrational partition function for CO
2
at (a)
300 K and (b) 3000 K.
Solution:
Given: Table 15.3, v =0
Required: molecular vibrational partition function for CO
2
The molecular vibrational partition function is

2
1 1 1
1890 3360 954
1 exp 1 exp 1 exp
v
q
T T T
| |
|
| =
| | | | | | |

| | | |
\ . \ . \ . \ .

a.
2
1 1 1
1890 3360 954
1 exp 1 exp 1 exp
300 300 300
v
q
| |
|
| =
| | | | | | |

| | | |
\ . \ . \ . \ .

1.001 839 683 1.000 013 674 1.088 662 816
1.090 680 524
1.09
v
v
v
q
q
q
=
=
=

b.
2
1 1 1
1890 3360 954
1 exp 1 exp 1 exp
3000 3000 3000
v
q
| |
|
| =
| | | | | | |

| | | |
\ . \ . \ . \ .

2.139 457 549 1.484 295 694 13.477 045 2
42.797 537 98
42.8
v
v
v
q
q
q
=
=
=

15-84
15.40. Expressions such as the Sackur-Tetrode equation for the entropy contain a term ln (constant T). At temperatures close to the
absolute zero this term has large negative values, and the expression therefore leads to a negative value of the entropy. Comment on
this.
Solution:
Given: see above
Required: comment on the observed phenomenon
The Sackur-Tetrode equation is based on Eq. 15.86 for the translational partition function. This expression was obtained by replacing a
summation (Eq. 15.83) by an integration (Eq. 15.84), a procedure that is valid only if the spacing between the translation levels is much
smaller than
B
k T . This approximation is not valid at extremely low temperatures, and the Sackur-Tetrode equation then is inapplicable.

15-85
15.41. Calculate the entropy of argon gas at 25 C and 1 bar pressure.
Solution:
Given: 25 C, 1 bar T P = =
Required: entropy
From the Sackur-Tetrode equation (Eq. 15.88),

1 1
/ J K mol 108.74 12.47ln
r
S M

= +
For argon, 39.948
r
M = and therefore,

1 1
1 1
/ J K mol 108.74 45.98 154.7
154.7 J K mol
S
S

= + =
=

15-86
15.42. From the data in Table 15.3, calculate, with reference to v =0, the molecular vibrational partition function for Br
2
at (a) 300 K and
(b) 3000 K.
Solution:
Given: Table 15.3, v =0
Required: molecular vibrational partition function
The value of
v
is 470 K and thus,

1
470 K
1 exp
v
q
T
=
| |
|
\ .

a. At T =300 K,
1
470 K
1 exp
300 K
1.263 806 81
1.26
v
v
v
q
q
q
=
| |
|
\ .
=
=

b. At T =3000 K,
1
470 K
1 exp
3000 K
6.896 028 941
6.90
v
v
v
q
q
q
=
| |
|
\ .
=
=

15-87
15.43. Give the symmetry numbers of the following molecules: C
3
O
2
(carbon suboxide), CH
4
, C
2
H
4
, C
2
H
6
in the staggered conformation,
C
2
H
6
in the eclipsed conformation, CHCl
3
, C
3
H
6
(cyclopropane), C
6
H
6
(benzene), NH
2
D, CH
2
Cl
2
.
Solution:
Given: see above
Required: symmetry numbers
15-88

15-89
15.44. Show that the rotational partition function for a linear molecule can be expressed as
q
r
=k
B
T/Bh
where B is the rotational constant defined by Eq.(13.63).
Solution:
Given: see above
Required: see above
The rotational constant is

2
8
h
B
I
=
We know that

2
B
2
8
r
Ik T
q
h
=
Therefore, we can substitute the expression for B into the above equation and yield:

B
r
k T
q
Bh
=
15-90
*15.45. Calculate the molar translational entropy of chlorine gas at 25 C and 0.1 bar pressure.
Solution:
Given: 25 C, 1 bar T P = =
Required: molar translational entropy
We use Eq. 15.88 with
B
:
m
Lk T
V
P
=

3 2
B B
2
2 5
ln
2
m
mk T k T
S R R
h P
(
| |
= +
(
|
\ . (

For Cl
2
,
2 35.45 g
m

=
1
mol
3 1
10 kg g

23 1
6.022 10 mol
25
1.177 349 718 10 kg

4
0.1 bar 1.00 10 Pa P = =
Plug the values into the expression for S
m
, we get:
( )
( )
1 1 1 1
3 2
23
25
2 4
34
1 1 1 1
5
8.3145 J K mol 8.3145 J K mol
2
1.381 10 298.15
2 1.177 349 718 10
ln
1.00 10
6.626 10
20.786 25 J K mol 8.3145 J K mol
ln 2.187 125 651
m
m
S
S

= +
(
| |

(
|
(
|
( \ .

= +

( )
63 25
1 1 1 1
1 1
1 1
10 4.117 451 5 10
20.786 25 J K mol 745.777 858 7 J K mol
766.564 108 7 J K mol
766.6 J K mol
m
m
m
S
S
S

= +
=
=

15-91
*15.46. The carbon monoxide molecule has a moment of inertia of 1.45 10
46
kg m
2
and its vibrational frequency is 6.50 10
13
s
1
.
Calculate the translational, rotational, and vibrational contributions to the molar entropy of carbon monoxide at 25 C and 1 bar
pressure.
Solution:
Given:
46 2 13 1
1.45 10 kg m , 6.50 10 s , 25 C, 1 bar I T P
= = = =
Required: translational, rotational, and vibrational contributions to the molar entropy
The translational entropy is given by the Sackur-Tetrode equation (Eq. 15.90)
( )
1 1
,
/ J K mol 108.74 12.47ln
t m r
S M

= +
Here, Mr is the relative molecular mass of the compound
For carbon monoxide, the relative molecular mass is

1
12.00 16.01 28.01 g mol
r
M

= + =
Therefore,

( )
1 1
,
1 1
,
1 1
,
/ J K mol 108.74 12.47ln 28.01
150.297 043 J K mol
150.3 J K mol
t m
t m
t m
S
S
S

= +
=
=

The rotational partition function is

2
B
2
2 46
8
8 1.45 10 kg
r
r
Ik T
q
h
q

=

=
2
m
23 2
1.381 10 m
kg
2
s
1
K
298.15 K
( )
2
34 4
6.626 10 m
2
kg
2
s
107.370 101 5
r
q =

15-92
The rotational entropy is

B B
,
,
ln
ln
ln
ln since
ln
r
r
V
N r
r m r r r
V
r m r
Q
S k T k Q
T
q
S RT R q Q q
T
S R R q
| |
= +
|
\ .
| |
= + =
|
\ .
= +

1 1
,
1 1
,
1 1
,
/ J K mol 8.3145 8.3145ln107.370 101 5
47.195 444 68 J K mol
47.2 J K mol
r m
r m
r m
S
S
S

= +
=
=

Since
13 1
6.50 10 s = , the spacing between vibrational energy levels is

34 13 20
20
B
6.626 10 6.50 10 4.3069 10 J
4.3069 10 J
h
h
k T
= =
=
23 2 2
1.381 10 m kg s

1
K
298.15 K
( )
B
10.460 111 07
1
1.000 028 658
1 exp 10.460 111 07
1
v
v
h
k T
q
q
=
= =

The vibrational energy is therefore negligible.

15-93
15.47. Suppose that a system has equally spaced energy levels, the separation between neighboring levels being . Prove that the fraction
of the molecules in state i, having energy
i
greater than the energy of the lowest level, is
B B

1 exp exp
i
k T k T
| | | |
| |
\ . \ .

What is the limiting value of this fraction as T ? Explain your answer.
Solution:
Given: see above
Required: limiting value as T , explanation
The fraction of molecules in the i-th level is

B
3 1 2
B B B
B
B B B
B B
exp
1 exp exp exp ...
exp
2 3
1 exp exp exp ...
1 exp exp
i
i
i
k T
k T k T k T
k T
k T k T k T
k T k T
| |
|
\ .
| | | | | |
+ + + +
| | |
\ . \ . \ .
| |
|
\ .
=
| | | | | |
+ + + +
| | |
\ . \ . \ .
( | | | |
=
( | |
\ . \ .

The limiting value of this fraction when T is zero; this is because the molecules are now distributed evenly among an infinite number
of levels.
15-94
*15.48. Deduce the following from the Sackur-Tetrode equation (Eq.(15.159)), which applies to an ideal monatomic gas:
a. The dependence of entropy on relative molecular mass M
r
; also, obtain an expression for dS
m
/dM
r
.
b. The dependence of heat capacity C
P
on relative molecular mass.
c. The dependence of entropy on temperature; also obtain an expression for dS
m
/dT.
Solution:
Given: ideal monatomic gas
Required: deduction from the Sackur-Tetrode equation
a. ( )
3
constant ln 1
2
m r
S R M = +
( )
3
2
2
m
r r
dS R
dM M
=
b. The heat capacity of
P
C is ( ) ( ) ln
P P
H T S T = and therefore does not depend on
r
M . The Sackur-Tetrode equation can be
written as
( )
5
constant ln 3
2
m
S R T = +
and therefore
( )
,
5
4
2
P m
C R =
There is no dependence on
r
M .

15-95
c. From Eq. (3),
( )
5
5
2
m
dS R
dT T
=
15-96
*15.49. Molecules absorbed on a surface sometimes behave like a two-dimensional gas. Derive an equation, analogous to the Sackur-
Tetrode Eq. (15.159), for the molar entropy of such an adsorbed layer of atoms, in terms of the molecular mass m and the surface
area A. What would be the molar entropy if 10
10
argon atoms were adsorbed on an area of 1 cm
2
at 25 C?
Solution:
Given: see above, 10
10
argon atoms,
2
1 cm, 25 C A T = =
Required: derivation for the molar entropy, molar entropy
For two-dimensional translational motion,

B
2
B 2
B B
B 2
B
2
2
ln ln ln 2
ln
ln
1
ln 2
2
2 ln
t
A
m
m
mk TA
q
h
q A
Q N N N mk T N
N Nh
Q
S k T k Q
T
A
S RT R R mk T
T Nh
mk TA
S R R
Nh
=
| | | |
= + = +
| |
\ . \ .
| |
+ +
|
\ .
| |
= + +
|
\ .
| |
= +
|
\ .

For Ar,
39.948 g
m =
1
mol
3 1
10 kg g

23 1
6.022 10 mol
26
6.633 676 519 10 kg
=
If
10
10 molecules are absorbed on an area of 1 cm
2
at 25 C ,
15-97

1 1 1 1 26
2 8.3145 J K mol 8.3145 J K mol ln 2 6.633 676 519 10 kg
m
S

= +
23 2
1.381 10 m

kg
2
s
1
K
4 2
10 m
298.15 K
( )
2
10 34 4
10 6.626 10 m

2
kg
2
s
( )
1 1 1 1 7
1 1
1 1
16.629 J K mol 8.3145 J K mol ln 3.908 947 05 10
161.977 798 4 J K mol
162.0 J K mol
m
m
m
S
S
S

(
(
(
= +
=
=

15-98
15.50. Calculate the dissociation constant K
c
for the reaction
( ) ( )
3 3
2
O 2O P
at 1 000 K expressing the answer in mole l
-1
. Ignore nuclear degeneracy. Use the data from the table of Problem 51, along with the
value
9
1.25 10 cm
o
= .
Solution:
Given: 1 000 K T = , table of Problem 51,
9
1.25 10 cm
o
=
Required: K
c
The calculation here is
For our case:
O
2
z 2O

2
o
O 0
5.08 eV E D = =
2
2
1 O
O
exp
o
p
q D
K
q N kT
| |
=
|
\ .

2
O t r v e
q q q q q = and
O t e
q q q =

2
2
triplet statedegeneracy 3/2
O
O / 2
4
1
3
2 1
v
B
t r v e T
r
m k T
T
q q q q q
h e
| | | |
| |
= =
| | |

\ .
\ . \ .

15-99
( )
2
3/2
27 23
O 2
34
triplet statedegeneracy
2230/1000
4 32 1.673 10 1.381 10 1000
6.626 10
1000 1
3
2 2.07 1
q
e
| |

|
=
|
\ .
| || |

| |

\ .\ .

( ) ( )( )( )
2
3/2
20 35 -3
O
6.6129 10 241.54 9.23 3 1.137 10 m q = =
and
( )
16 -3
O 3
9
1
3 6.788 10 m
m
1.25 10 cm 0.01
cm
t e
q q q
= = =
| |

|
\ .

so

( )
( )( )
( )
( ) ( )
2
26
2
1 O
O
2 2
16 -3
-3 35 23
-19 -1
23
2.555 10
25
exp
6.788 10 m
m 1.137 10 6.022 10
5.08 eV 1.602 10 J eV
exp
1.381 10 1000
1.34 10 exp 58.929
o
p
B
q D
K
q N k T
| |
= =
|
\ .
| || |
| |
=
| |

\ .\ .
| |

|

\ .
=
3
51 -1 6
3
51 -1 27 -1
m
3.43 10 molecule 10
m
3.43 10 molecule 2.063 10 mol
l
l

=
= =

This is
1
p
K , to get ( )
1
1 1
c p
K K RT

=
15-100
15.51. From the data in Table 15.5, calculate K
P
at 1000 K for the water-gas reaction
CO
2
(g) +H
2
(g) = CO(g) +H
2
O(g)
Solution:
Given: Table 15.5, 1000 K T =
Required: K
P
( )
( )
( )
o 1
298
o o 1
298 0
o 1
0
o 1
1000
110.53 241.82 393.51 41.16 kJ mol from Table 15.5
8.665 9.902 8.468 9.360 0.739 kJ mol
41.16 0.739 40.421 kJ mol
40 420 1000 204.18 196.83 226.54 137.07 3020 J mol
l
H
H H
H
G
= + =
= + =
= =
= + =
3020
n 0.363 220 879
8.3145 1000
0.695 432 809
0.695
P
P
P
K
K
K
= =
=
=

15-101
15.52. Without making detailed calculations but by using symmetry numbers, estimate the equilibrium constants for the following
reactions:
a.
35
Cl
35
Cl +
37
Cl =
35
Cl
37
Cl +
35
Cl
b.
35
Cl
35
Cl +
37
Cl
37
Cl = 2
35
Cl
37
Cl
c. C
35
Cl
4
+
37
Cl = C
37
Cl
35
Cl
3
+
35
Cl
d. N
35
Cl
3
+
37
Cl = N
37
Cl
35
Cl
2
+
35
Cl
e.
35
Cl
2
O +
37
Cl =
37
Cl
35
ClO +
35
Cl
(Because of the similarity of the masses, these estimates will be quite accurate.)
D. M. Bishop and K. J . Laidler, J. Chem. Phys., 42, 1688(1965), have defined a statistical factor for a reaction as the number of
equivalent ways in which a reaction can occur. Thus for reaction (a) from left to right the statistical factor is 2, since the
37
Cl atom
can abstract either of the two
37
Cl atoms. For the reverse reaction the statistical factor r is 1, since the
35
Cl atom can only abstract the
35
Cl atom in order to give the desired products. If two identical molecules are involved, the statistical factor must be taken as the
number of equivalent products divided by 2; thus for reaction (b) from right to left the statistical factor is
1
2
.
Bishop and Laidler proved that the ratio l/r of statistical factors is always equal to the ratio
A
B
/
Y
Z
of symmetry numbers. Verify
that this is true for the given reactions.
This statistical factor procedure is useful in providing a simple insight into the factors that appear in equilibrium constants.
Solution:
Given: above reactions
Required: equilibrium constants
The symmetry numbers are given below the molecules (They are 1 for atoms.) and the statistical factors are shown above and below the
arrows; for simplicity
35
Cl is written as Cl and
37
Cl as Cl*.
15-102
*15.53. Calculate the equilibrium constant at 1000 C for the dissociation
I
2
= 2I
given the following information: moment of inertia of I
2
=7.426 10
45
kg m
2
, wavenumber for I
2
1
, U
0
=
148.45 kJ mol
1
. The I atom is in a
2
P
3/2
state; neglect higher states.
Solution:
Given: above reaction, 1000 C T = , I
2
=7.426 10
45
kg m
2
, wavenumber for I
2
1
, U
0
=148.45 kJ mol
1
,
2
P
3/2

state
Required: equilibrium constant
Mass of I atom,

126.90 g
m =
1
mol
3 1
10 kg g

23 1
6.022 10 mol
25
2.107 273 331 10 kg
=
From Eq. 15.86, the translational partition function for the I atom, with
3
1 m V = , is

( )
( )
3 2
B
3
25
2
2 2.107 273 331 10 kg
I
t
t
mk T V
q
h
q

=

=
23 2
1.381 10 m
kg
2
s
1
K
( )
( )
3 2
3
34 6
6.626 10 m
3
kg
3
s
1273.15 K
( )
3 2
3
1 m
( )
34
I 1.221 10
t
q =

The degeneracy of the ground state is

3
2 1 4
2
| |
+ =
|
\ .

15-103
Thus
( )
34 34
I 4 1.221 10 4.884 10
t
q = =
For the iodione molecule,

( )
25
2
2 2 2.107 273 331 10 kg
I
t
q

=
23 2
1.381 10 m
kg
2
s
1
K
( )
( )
3 2
3
34 6
6.626 10 m
3
kg
3
s
1273.15 K
( )
3 2
3
1 m
( ) ( )
3 2 34
2
I 2 I 3.453 10
t t
q q = =

From Eq. 15.95,
( )
B
2
2 45
2
2
8 7.426 10 kg
I
r
r
Ik T
q
h
q

=

=
2
m
23 2
1.381 10 m
kg
2
s
1
K
1273.15 K
( )
2
34 4
2 6.626 10 m
2
kg
2
s
( )
4
2
I 1.174 10
r
q =

15-104
And from Eq. 15.102,

( )
( )
( )
B
2
34
8 23
2
2
1
1 exp
1
I
6.626 10 21 367.0 2.998
1 exp
10 1.381 10 1273.15
1
I
1 0.785 520 326
I 4.662 446 486
v
v
v
v
q
h
k T
q
q
q

=
| |
|
\ .
=
| |
|

\ .
=
=

The molecular partition function for
2
I is thus

2
2
34 4
I
39
I
3.453 10 1.174 10 4.662 446 486
1.890 072 814 10
q
q
=
=

From Eq. 15.140, the molecular equilibrium constant, K, is
( )
0 Y Z
A B
2
34
39
exp
4.884 10
148 450 1273.15
exp
1.890 072 814 10 8.3145
y z
v
a b
U q q
K N
q q RT
K
| |
=
|
\ .
| |
=
|
\ .

( )( )
30 7
24
1.262 038 998 10 8.120 10
1.025 362 665 10
K
K
=
=

Its value in molar units is

24
1.025 362 665 10 molecule
c
K =
3 1
23
1
m molecule
6.022 10

3 3 3
mol
1.702 694 562 mol m 1.702 694 562 10 mol dm
c
K

= =

15-105
At
3
1273.15 K, 1 mol dm 105.8 bar T

= =

3 3
1.702 694 562 10 mol dm
P
K

=
3
105.8 bar
1 mol dm
0.180 257 057 bar

0.180 bar
P
P
K
K
=
=

(The experimental value obtained by Starck and Bodenstein in 1910 was 0.165 atm =0.167 bar.)
15-106
P
for the dissociation
Na
2
= 2Na
at 1000 K, using the following data: internuclear separation in Na
2
1
, U
0
=
70.4 kJ mol
1
. The Na atom is in a
2
S
1/2
state; neglect hiher states.
Solution:
Given: 1000 K T = , internuclear separation in Na
2
1
, U
0
=70.4 kJ mol
1
,
2
S
1/2
state
Required: K
P
Mass of Na atom is:
22.99 g
m =
1
mol
3 1
10 kg g

23 1
6.022 10 mol
26
3.817 668 549 10 kg
=
The electronic partition function is
1
2 1 2
2
| |
+ =
|
\ .
.
The molecular partition function for Na is

( )
( )
( )
( )
3 2
26 23
3
34
33
2 2 3.817 668 549 10 1.381 10 1000
Na
6.626 10
Na 1.311 10
q
q
=

For Na
2
,

( )
( )
( )
( ) ( )
( )
3 2
26 23
2 3
34
33
2
2 2 3.818 10 1.381 10 1000
Na
6.626 10
Na 1.854 10 Na 2
t
t t
q
q q
= =

15-107
Moment of inertia of Na
2
is,

( )
2
26 9
45 2
3.817 668 549 10 0.3716 10
2
2.636 072 43 10 kg m
I
I

=
=

( )
( )
( )
( )
( )
2 45 23
2 2
34
2
2
10 34
23
2
8 2.636 10 1.381 10 1000
Na
2 6.626 10
Na 3273.466 428
1
Na
159.2 2.998 10 6.626 10
1 exp
1.381 10 1000
Na 4.885 909 311
r
r
v
v
q
q
q
q

=

=
=
| |
|

\ .
=

Thus, the partition function of Na
2
at 1000 K is

33
37
1.854 10 3273.466 428 4.885 909 311
2.965 261 662 10
=
=

The molecular equilibrium constant is

( )
2
33
37
25
1.311 10
70 400
exp
2.965 261 662 10 8.3145 1000
1.218 742 727 10
K
K
| |
=
|

\ .
=

25
1.218 742 727 10 molecule
c
K =
3 1
23
1
m molecule
6.022 10

3 3
mol
20.238 172 16 mol m 0.020 238 172 16 mol dm
c
K

= =

At
3
1000 K, 1 mol dm 83.1 bar T

= =
15-108

3
0.020 238 172 16 mol dm
P
K

=
3
83.1 bar
mol dm
1.681 792 106 bar

1.68 bar
P
P
K
K
=
=


15-109
P
at 1200 K for Cl
2
= 2Cl, from the following data: internuclear separation in Cl
2
=199 pm,
wavenumber for vibration =565.0 cm
1
, U
0
=240.0 kJ mol
1
. The ground state of Cl is a doublet,
2
3 1
,
2 2
P , the
separation between the states being 881 cm
1
.
Solution:
Given: 1200 K T = , internuclear separation in Cl
2
=199 pm, wavenumber for vibration =565.0 cm
1
, U
0
=240.0 kJ mol
1
,
2
3 1
,
2 2
P ,separation between states =881 cm
-1
.
Required: K
P
Mass of Cl atom is

35.45 g
m =
1
mol
3 1
10 kg g

23 1
6.022 10 mol
26
5.886 748 589 10 kg
=
Translational partition function for the Cl atom with
3
1 m V = , is

( )
( )
( )
( )
3 2
26 23
3
34
33
2 5.886 748 589 10 1.381 10 1200
Cl
6.626 10
Cl 1.651 10
t
t
Q
Q
=

The degeneracy of the
2
3 2
P state is 4; that of the
2
12
P is 2; the electronic partition function is thus,

( )
( )
( )
B
10 34
23
Cl 4 2exp
881 2.998 10 6.626 10
Cl 4 2exp
1.381 10 1200
Cl 4.695 654 774
e
e
e
Q
k T
Q
Q
| |
= +
|
\ .
| |
= +
|

\ .
=

15-110
The complete partition function for the Cl atom is thus

( )
( )
33
33
Cl 1.651 10 4.695 654 774
Cl 7.752 526 032 10
Q
Q
=
=

For the Cl
2
molecule,
( ) ( )
3 2 33
2
Cl 2 Cl 4.669 733 183 10
t t
q q = =
The moment of inertia of Cl
2
is

( )
2
2 2 26 10 2
Cl
45 2
1 1
5.886 748 589 10 1.99 10 kg m
2 2
1.165 605 654 10 kg m
I r m r
I

= = =
=

The rotational partition function of ( )
2
Cl 2 = is

( )
( )
( )
2 45 23
2 2
34
2
8 1.165 605 654 10 1.381 10 1200
Cl
2 6.626 10
Cl 1736.934 508
r
r
q
q
=

The vibrational partition function is

( )
( )
2
10 34
23
2
1
Cl
565 2.998 10 6.626 10
1 exp
1.381 10 1200
Cl 2.032 545 566
r
r
q
q
=
| |
|

\ .
=

The molecular partition function of Cl
2
is thus,
15-111

( )
( )
33
2
37
2
I 4.669 733 183 10 1736.934 508 2.032 545 566
I 1.648 601 918 10
q
q
=
=

The molecular equilibrium constant is thus

( )
2
33
37
20
7.752 526 032 10
240 000
exp
1.648 601 918 10 8.3145 1200
1.303 447 699 10
K
K
| |
=
|

\ .
=

Its value in molar units is

20
1.303 447 699 10 molecule
c
K =
3 1
23
1
m molecule
6.022 10

4 3 7 3
mol
2.164 476 419 10 mol m 2.164 476 419 10 mol dm
c
K

= =

At 1200 K,
3
1 mol dm 99.8 bar
=

7 3
3
5
5
99.8 bar
2.164 476 419 10 mol dm
mol dm
2.160 147 466 10 bar
2.16 10 bar
P
P
P
K
K
K

=
=
=

15-112
15.56. Calculate the isotopic ratio K
H
/K
D
at 300 K for the reactions
H
2
= 2H and D
2
= 2D
Take the zero-point energies of H
2
and D
2
to be 26.1 kJ mol
1
and 18.5 kJ mol
1
, respectively.
Solution:
Given:
2 2
1 1
0,H 0,D
300 K, 26.1 kJ mol , 18.5 kJ mol T E E

= = =
Required: K
H
/K
D
The equilibrium constant,
H
K , is

2
2
0 H
H
exp
E q
q RT
| |
|
\ .

H
q (translational only) involves
1.5
H
m
2
H
q (translational and two degrees of rotational freedom) involves
2.5
H
m . The preexponential factor in the expression for the equilibrium is
thus proportional to
0.5
m . The isotope ratio is thus
15-113

( )
0.5 1
H
D
0.5
H
D
26.1 18.5 kJ mol 1
exp
2
1 44 600 J
exp
2
K
K RT
K
K
( +
| |
=
( |
\ .

| |
=
|
\ .
1
mol
8.3145 J
1
K
1
mol
300 K
8 H
D
8 H
D
8 H
D
0.707 106 781 1.716 471 994 10
1.213 728 986 10
1.21 10
K
K
K
K
K
K
(
(
(

=
=
=

15-114
15.57. On the basis of transition-state theory, make rough estimates of the preexponential factors at 300 K for the following types of gas
reactions:
a. A bimolecular reaction between an atom and a diatomic molecule, with the formation of a linear activated complex.
b. A bimolecular reaction between two diatomic molecules, the activated complex being nonlinear with one degree of restricted
rotation.
c. A bimolecular reaction between two nonlinear molecules, the activated complex being nonlinear with no restricted rotation.
d. A trimolecular reaction between three diatomic molecules, the activated complex being nonlinear with one degree of restricted
rotation.
Take the translational partition functions (for three degrees of freedom) to be 10
33
m
3
, the rotational functions for each degree of
freedom to be 10, the function for a restricted rotation to be 10, and the vibrational functions to be unity. Express the calculated
preexponential factors in molecular units (m
3
s
1
) and in molar units (dm
3
mol
1
s
1
).
Solution:
Given: above gas reactions, 300 K T = , translational partition function =10
33
m
-3
, rotational functions =10, function for rectricted rotation
=10, vibrational functions =1
Required: estimates of the preexponential factors
At 300 K,
12 1 B
6.25 10 s
k T
h
= , which for present purposes is rounded to

12 1.
6 10 s

a. For the atom the partition function is
33 3
10 m
. The diatomic molecule has three degrees of translational freedom (which will be
written as
3
t ), two degrees of rotational freedom (
2
r ), and one of vibrational freedom (v ). Its partition function is thus
33 2 35 3
10 10 10 m
= .
The linear triatomic activated complex has
3
t ,
2
r , and
3
, and its partition function is

33 2 35 3
10 10 10 m
=
The estimated preexponential factor is
15-115

35 3
12 1 B
33 35 6
A B
10 m
6 10 s
10 10 m
k T q
h q q

21 3 1 B
A B
6 10 m s
k T q
h q q

=
Multiplication by
23 1
6 10 mol
and by
3 3
1000 dm m
gives

6 3 1 1
4 10 dm mol s A

=
b. Diatomic molecule A:
3 2
t r
33 35 3
A B
10 100 10 m q q

= = =
Activated complex: ( )
3 3 4
t r rr (One vibration has been replaced by a restricted rotation | | rr .)

33 4 37 3
10 10 10 m q

= =
Thus

( )
37 3
12 21 3 1
2
35
21 3 1 23 1
3 1 1
6 3 1 1
10 m
6 10 6 10 m s
10
6 10 m s 6 10 mol
3600 m mol s
4 10 dm mol s
A
A
A
A

= =
=
=
=

c. (The numbers of vibrational modes are now unspecified, but this makes no difference since they are unity.)
Reactants A and B:
3 3 33 3 36 3
10 10 10 m t r q

= =
Activated compex:
3 3 36 3
10 m t r q

=
15-116
( )
36
12 24 3 1
2
36
3 3 1 1
10
6 10 6 10 m s
10
4 10 dm mol s
A
A

= =
=

d. Reactants A, B, and C:
3 3 36 3
10 m t r q

=
Activated complex: ( )
3 3 37 3
10 m t r rr q

=
( )
37
12 59 6 1
3
36
29 3 1 1
10
6 10 6 10 m s
10
4 10 dm mol s
A
A

= =
=

15-117
15.58. The rate constant for the reaction
2NO +O
2
2NO
2

has been found to be proportional to T
3
Solution:
Given: above reaction,
3
rate constant T
~
The fact that there is no exponential dependence suggests that
0
0 E = . The temperature dependence arises entirely from the preexponential
terms. For each of the three linear reactants there are three degrees of translational freedom and two of rotation, and they vary with
temperature as (see Table 15.4)

1.5 2.5
T T T =
The activated complex is presumably nonlinear, and if there is no restricted rotation the temperature dependence is as

1.5 1.5 3
T T T =
The preexponential factor is thus proportional to

( )
3
3.5
3
2.5
T
T T
T
=
To explain the dependence on
3
T
we must allow the activated complex to have one degree of restricted rotation, so that its partition
function is proportional to

1.5 1.5 0.5 3.5
T T T T =
The preexponential factor is then proportional to
15-118

( )
3.5
3
3
2.5
T
T T
T
=
We can postulate an activated complex of the following structure

with restricted rotation about the OO bond.

15-119
15.59. Deduce the temperature dependency of the preexponential factor of the following types of reactions, where A represents an atom, L
a linear molecule, and N a nonlinear molecule:
A +L; A +N; L +L; L +N; N +N
Solution:
Given: above types of reactions
Required: temperature dependency of the preexponential factor
The temperature dependencies of the partition function are as follows:

3 1.5
3 2 1.5 2.5
3 3 1.5 1.5 3
A: :
L: :
N: :
t T
t r T T T
t r T T T
=
=

The nonlinear activated complexes have partition functions proportional to
1.5 1.5 3
T T T = . The temperature dependencies for the various
types of reactions are therefore as follows:

3
0
1.5 2.5
3
0.5
1.5 3
3
1
2.5 2.5
3
1.5
2.5 3
3
2
3 3
A L:
A N:
L L:
L N:
N N:
TT
T
T T
TT
T
T T
TT
T
T T
TT
T
T T
TT
T
T T
+ =
+ =
+ =
+ =
+ =

15-120
15.60. The rate of the reaction
O
+
+N
2
NO
+
+N
has been found over a certain temperature range to be proportional to T
0.5
(M. McFarland et al., J. Chem. Phys., 59, 6620(1973).
How can this be explained in terms of simple transition-state theory?
Solution:
0.5
reaction rate T
~
For the preceding problem it was shown that for an atom reacting with a linear molecule, the preexponential factor is proportional to
0
T if
the activated complex is nonlinear. If the activated complex is linear the temperature dependence is
2.5
0.5
1.5 2.5
TT
T
T T
= . It thus appears that the

activated complex is linear, and that the temperature dependence is due entirely to the preexponential factor.
15-121
15.61. For the case of two atoms giving a product, A +B = [AB]

Product, show that transition-state theory yields essentially the
same expression for the rate constant as the collision theory expression of Eq. (9.76).
Solution:
Given: above reaction
Required: prove the above statement
Starting with Eq. 15.152, we get

0 B
A B B
exp ,
E k T q
k
h q q k T
| | | |
=
| |
\ .
\ .

where

( )
( ) ( )
3 2
A B B B
3 2
3 2 3 2
A B B B
A B 3 3
2
2
2 2
;
m m k T
Ik T
q
h
m k T m k T
q q
h h

+ (
| |
=
|
\ .
= =
h

Substituting the partition functions in the first equation, where ( )
2
2 A B
A B
A B
AB
m m
I r r d
m m

| |
= + =
|
+
\ .
, and simplifying, we get

12
2 0 B
B
8
exp
AB
E k T
k d
k T
| | | |
=
| |
\ . \ .
,
Which, when multiplied by the Avogadro constant (and also multiplying the numerator and denominator of the argument of the exponential
term with the Avogadro constant), is essentially the same as Eq. (9.76).
15-122
15.62. In mass-spectrometric experiments, P. Kebarle and coworkers (J. Chem. Phys., 52, 212(1970) have found that under certain
conditions the rate constant for the reaction
+ +
2 2 3 2
N +N +N N +N
is proportional to T
2.5
Solution:
2.5
reaction rate T
~
The partition function for the ion N
+
is proportional to
1.5
T , while that for
2
N is proportional to
2.5
T . If the activated complex is nonlinear,
its partition function is proportional to
3
T . The temperature dependence of the preexponential factor is thus, according to transition-state
theory,

( )
3
2.5
2
1.5 2.5
TT
T
T T
= ,
The results can therefore be explained in terms of a nonlinear complex, with
0
0 E = .
15-123
15.63. On the basis of transition-state theory, and assuming the vibrational partitions to be temperature-independent, deduce the
temperature dependence of the preexponential factor for each of the following reactions:
a. 2ClO Cl
2
+O
2

b. NO +O
3
NO
2
+O
2

c. NO
2
+F
2
NO
2
F +F
d. 2NOCl 2NO + Cl
2

e. 2NO +Br
2
2NOBr
Solution:
Given: above reactions
Required: deduce temperature dependence of the preexponential factor
The activated complexes will be assumed in all cases to be linear and to have no restricted rotation. If an activated complex is linear, the
temperature dependence decreases by 0.5, while each degree of restricted rotation increases the dependence by 0.5.
a.
( )
3
1
2
2.5
TT
T
T
=
b.
3
1.5
2.5 3
TT
T
T T
=
c.
3
1.5
3 2.5
TT
T
T T
=
d.
( )
3
2
2
3
TT
T
T
=
15-124
e.
( )
3
0.5
3
1.5
TT
T
T
=
15-125
15.64. Benzaldehyde is oxidized by permanganate in aqueous solution. Suppose that the aldehydic hydrogen atom is replaced by a
deuterium atom; what can be said on the basis of transition-state theory about the kinetic isotope ratio k
H
/k
D
at 25 C? The
wavenumber of the aldehydic CH vibration is 2900 cm
1
.
Solution:
Given: above information,
1
25 C, 2900 cm . T

= =
Required: see above
The two molecules differ only by isotopic substitution and will have different vibrational frequencies for the bond where substitution
occurs. We make the reasonable assumption that the change in nuclear mass will not affect the electronic energy and therefore the force
constant, k, will remain the same. The only difference occurs when the reduced mass of the two forms enter the equations. The reduced
mass is given by Eq. 13.94 or 13.118, from which the reduced mass of the deuterated form is found to be smaller than that of the form with
the normal hydrogen.

Then from Eq. 13.123, the smaller value of
D
makes
0
v for the deuterated bond greater than
0
v for the hydrogen bond. Consequently, the
bond energy of the deuterated form is greater than that of the hydrogen form. This has the effect of putting the deuterated form at a lower
potential energy than the hydrogen form, and therefore causing a greater expenditure of energy to promote the deuterated form to the
activated state. Therefore the CH cleavage is greater than that of the CD bond for the same energy input and the reaction rate of the
CH form should be faster.
15-126
15.65. A transition-state theory study of the reaction O(
3
P) +HCl generated the following information at T =600 K:
Reactants
O q
t
1.767 10
32
m
3
HCl q
t
6.084 10
32
m
3
q
r
39.40 (for 2 degrees of freedom)

0
2991.0 cm
1

Transition state (bent)
q
t
1.050 10
33
m
3
q
r
1730 (for 3 degrees of freedom)

1
1407.9 cm
1

2
266.8 cm
1

The maximum of the reaction path is at 45.97 kJ mol
1
. Calculate the rate constant at this temperature.
(Note: Some interesting problems on transition-state theory involving the use of a computer are to be found in S. J . Moss and C. J .
Coady, J. Chem. Ed., 60, 455(1983).)
Solution:
Given: T =600 K, above information,
Required: rate constant
Since the vibrational partition functions are not given, we calculate them below:
15-127

1
2
1
HCl
B
1
B
1
B
2991.0
1 exp 1.000 784 342,
1407.9
1 exp 1.035 752 093,
266.8
1 exp 2.120 407 02.
v
v
v
hc
q
k T
hc
q
k T
hc
q
k T
( | |
= =
( |
\ .
( | |
= =
( |
\ .
( | |
= =
( |
\ .

Now, the quantity
0
E appearing in the exponent of Eq. 15.152 has to be evaluated. This is the energy difference between the zero point
energy of the reactants and that of the transition state,
( )
1
0
1
45 970 1407.9 266.8 2991.0 38 097 J mol .
2
E Lhc

= + + =
Therefore, we calculate

( )( )( )
( )( )( )( )
33
B
32 32
21 3 1
21 3 1
1.050 10 1730 1.035 752 093 2.120 407 02
38 097
exp
1.767 10 6.084 10 39.4 1.000 784 342
5.677 833 797 10 m s
5.678 10 m s
k T
k
h RT
k
k

| | | |
=
| |
\ . \ .
=
=

The translational partition functions are calculated for unit volume and hence, although strictly speaking, their units are simply
-3
m , we may
interpret this to mean state
-3
m or molecules
-3
m .

CHAPTER
1
1
6
6
The Solid State

Physical Chemistry
Electronic Edition


Chapter 16: The Solid State Crystal Lattices, Unit Cells, Density
16-2
Chapter 16
Crystal Lattices, Unit Cells, Density
16.1. How many basis groups are there in

a. An end-centered lattice;
b. A primitive lattice?

Solution

16.2. How many lattice points are there in a unit cell of

a. A face-centered lattice;
b. A body-centered lattice?

Solution

*16.3. a. Determined the efficiency of area utilization in packing circles onto the lattice points of a square lattice.
b. Compare that value with the efficiency of packing circles onto a triangular lattice.
c. Which packing uses area more efficiently and by how much?

Solution

16.4. a. Calculate the percentage of free space (volume of the cell minus the volume of the atoms in the unit cell) in each of the three
cubic lattices if all atoms in each are of equal size and touch their nearest neighbors.
b. Using the calculated values, determine which of the three structures represents the most efficient packing (least amount of used
space).

Solution

16.5. Derive an equation to relate the density D of a right-angled unit cell to its edge lengths a, b, and c and the number of formula units z
per unit cell.

Solution

Chapter 16: The Solid State Crystal Lattices, Unit Cells, Density
16-3
16.6. Silver crystallizes in a face-centered cubic unit cell with a silver atom on each lattice point.

a. If the edgelength of the unit cell is 4.0862 , what is the atomic radium of silver?
b. Calculate the density of silver.

Solution

16.7. Barium crystallizes with an edge length of 5.025 in a body-centered cubic unit cell.

a. Calculate the atomic radius of barium using this information.
b. Calculate the density of barium.

Solution

16.8. Aluminum crystallizes in a face-centered cubic lattice with an aluminum atom on each lattice point with the edge length of the unit
cell equal to 4.0491 .

a. Calculate the atomic radius of aluminum.
b. Determine the density of aluminum.

Solution

16.9. Crystals of p, p-dibromo-, -difluorostilbene [BrC
6
H
4
C(F)=]
2
are orthorhombic with edge lengths a =28.32 ; b =7.36 ; c =
6.08 . If there are four molecules in a unit cell, calculate the density of the crystal.

Solution

16.10. How many formula units exist in pure crystalline Si, which occurs in a face-centered cubic lattice, if its density is 2.328 99 g cm
-3

and its cell length is a =50431 066 ? The atomic mass of Si is 28.085 41 g mol
-1
.

Solution

Chapter 16: The Solid State Miller Indices and the Bragg Equation
16-4
16.11. Sodium chloride crystallizes in a face-centered cubic lattice with four NaCl units per unit cell. If the edge length of the unit cell is
5.629 , what is the density of the crystal? Compare your answer to the value given in the CRC Handbook.

Solution

16.12. LiH crystallizes with a face-centered cubic structure. The edge length of the unit cell of LiH is 4.08 . Assume anion-anion contact
to calculate the ionic radius of H
-
. Compare your answer to the value using the radium of Li
+
as 0.68 .

Solution

16.13. KCl is tetramolecular and crystallizes in a face-centered cubic lattice. If the edge length is 6.278 , what is the density of KCl?
Compare your answer to the value in the CRC Handbook.

Solution

16.14. Calcium Fluoride crystallizes in a face-centered cubic lattice where a =b =c, and it has a density of 3.18 g cm
-3
. Calculate the unit
cell length for CaF
2
.

Solution

Miller Indices and the Bragg Equation
16.15. Calculate the Miller indices of the parallel planes in a cubic lattice that intercepts the unit cell length at x =a,
1
2
y a = , and
2
3
z a = .

Solution

16.16. Determine the distance (i.e. d value) of the closest plane parallel to the 100, 110, and 111 faces of the cubic lattice.

Solution

Chapter 16: The Solid State Miller Indices and the Bragg Equation
16-5
16.17. What are the Miller indices of the plane that cuts through the crystal axes at

a. (2a, b, 3c);
b. (2a, -3b, 2c);
c. (a, b, -c);

Solution

16.18. Determine the value of d
hkl
in terms of the cell constants and angles for

a. The orthorhombic unit cell,
b. The tetragonal unit cell.

Solution

16.19. Calculate the separation between planes in a cubic lattice with unit cell length of 389 pm when the indices are

a. 100;
b. 111;
c. 121

Solution

16.20. Copper sulfate single crystals are orthorhombic with unit cells of dimensions a =488 pm, b =666 pm, c =832 pm. Calculate the
diffraction angle from Cu K
X rays
( = 154.18 pm) for first-order reflections from the (100), (010), and (111) planes.

Solution
16.21. Determine the angle of reflection when copper K
radiation (0.154 18 nm) is incident on a cubic crystal with a lattice constant d

hkl
of
0.400 nm.

Solution

Chapter 16: The Solid State Interpretation of X-Ray Data
16-6
16.22. Single crystals of FeSO
4
are orthorhombic with unit cell dimensions a =482 pm, b =684 pm, c =867 pm. Calculate the diffraction
angle from Te K
, X rays ( = 45.5 pm) from the (100), (010), and (111) planes

Solution

16.23. Single crystals of Hg(CN)
2
are tetragonal with unit cell dimensions a =967 pm and
c =892 pm. Calculate the first-order diffraction angles from the (100) and (111) planes when Cu K
X rays ( = 154 pm) are used.

Solution

16.24. A two-dimensional lattice is depicted in Figure 16.1 with planes superimposed on it parallel to the third direction. Determine the
Miller indices for each set of planes representing the external habit of the left-hand crystal.

Solution

16.25. The layers of atoms in a crystal are separated by 325 pm. At what angle in a diffractometer will diffraction occur using

a. molybdenum K
X rays ( = 70.8 pm);

b. copper K
X rays ( = 154 pm)?

Solution

16.26. Calculate the wavelength of an electron that is accelerated through a potential difference of approximately 40 kV.

Solution

Interpretation of X-Ray Data
16.27. Find the X-ray wavelength that would give a second-order reflection (n =2) with a angle of 10.40 from planes with a spacing of
4.00 .

Solution

Chapter 16: The Solid State Interpretation of X-Ray Data
16-7
16.28. A substance forms cubic crystals. A powder pattern shows reflections that have either all even or all odd indices. What type of unit
cell does it have?

Solution
16.29. A powder pattern of a cubic material has lines that index as (110), (200), (220), (310), (222), (400). What is its type of unit cell?

Solution

*16.30. The successive sin
2
values obtained from a powder pattern for -Fe are 1, 2, 3, 4, 5, 6, 7, 8, 9, etc.

a. If iron is in the cubic system, which type of unit cell is present?
b. If a copper X-ray tube is used ( = 154.18 pm), calculate the length of the side of the unit cell and the value of from (100)
planes. The density of -Fe is 7.90 g cm
-3
.
c. What is the radium of the iron atom if the central atom in the cubic cell is assumed to be in contact with the corner atoms?

Solution

16.31. Potassium metal has a density of 0.856 g cm
-3
and has a body-centered cubic lattice. Calculate the length of the unit cell a and the
distance between (200), (110), and (222) planes. Potassium has an atomic mass of 39.102 g mol
-1
.

Solution

16.32. Low-angle lines in the Cu K
powder pattern of KCl are found to be at =14.18, 20.25, and 25.10. Find the crystal type from
these data. (For Cu K
= 154.18 pm.) What other information is needed for a definitive determination?

Solution

16.33. The smallest observed diffraction angle of silver taken with Cu K
radiation
( = 154.18 pm) is 19.176. This angle is associated with the (111) plane in the cubic close-packed structure of silver.

a. Determine the value of the unit cell length a.
b. If D(Ag) =10.500 g cm
-3
and M =107.87 g mol
-1
, calculate the number of atoms in the unit cell.

Solution

Chapter 16: The Solid State Bonding in Crystals and Metals
16-8
16.34. Sodium fluoride is known to form a cubic closed-packed structure. The smallest angle obtained with Cu K
radiation ( = 1.5418 )
is 16.72 and is derived from the (111) planes. Find the value of a, the unit cell parameter.

Solution

16.35. The X-ray powder pattern of NaCl is taken with a chromium tube giving Cr K
=229.1 pm. The values of the lines are: 2036,

2358, 354, 4221, 4443, 5420, 6217, 6516. From these data determine the value of each d
hkl
and index the lines. From
the hkl values, show that this is a face-centered system.

Solution

Bonding in Crystals and Metals
16.36. Cadmium sulfide has been used as a yellow pigment by artists. The sulfide crystallizes with cadmium occupying
1
2
of the tetrahedral
holes in a closest-packed array of sulfide ions. What is the formula of cadmium sulfide?

Solution

16.37. Rutile is a mineral that contains titanium and oxygen. The structure of rutile may be described as a closest-packed array of oxygen
atoms with titanium in
1
2
of the octahedral holes. What is the formula of rutile? What is the oxidation number of titanium?

Solution

16.38. A tetrahedral hole is shown in Figure 16.33. Determine the largest sphere of radius r that can fit into a tetrahedral hole when the
surrounding four spherical atoms of the lattice are in contact. Let the lattice atom have radium R.

Solution

16.39. An octahedral hole is surrounded by six spheres of radium R in contact. If one-sixth of each of the six coordinating spheres
contributes to the volume of the octahedron surrounding the hole, calculate the maximum radius of the sphere that can be
accommodated.

Solution

Chapter 16: The Solid State Supplementary Problems
16-9
16.40. Calculate the value of E
c
of the RbBr from the following information:
1
414 kJ mol
f
H

= ; I (ionization energy, Rb) =397 kJ
mol
-1
;
sub
(Rb) H =

1
84 kJ mol
; D
0
(Br
2
) =192 kJ mol
-1
; A (electron affinity, Br) =318 kJ mol
-1
.

Solution

Supplementary Problems
16.41. Some of the d spacings for the mineral canfieldite (Ag
8
SnS
6
) are 3.23, 3.09, 3.04, 2.81, and 2.74 obtained with Cu K
X rays ( =
1.5418 ).

a. Find the corresponding angles of diffraction.

b. This is a cubic system with a =21.54 ; determine the hkl values for the first 3 d spacings.

Solution

16.42. A copper selenide mineral (Cu
5
Se
4
) called athabascaite is orthorhombic with a =8.277,
b =11.982, c =6.441. Strong intensity lines using Cu K
X rays ( = 154.18 pm) are observed at 12.95, 13.76, and 14.79.

Determine the d spacings and assign hkl values to these lines.

Solution

*16.43. Zinc blende is the face-centered cubic form of ZnS with Zn at
1 1 1
0,0,0; , ,0;0, ,0;
2 2 2

1 1
, ,0
2 2
and with S at
1 1 1 1 3 3 3 1 3 3 3 1
, , ; , , ; , , ; , , .
4 4 4 4 4 4 4 4 4 4 4 4

a. Determine the structure factor from the (111) planes that gives rise to the lowest angle reflection at =14.30 using Cu K
( =
154.18 pm).
b. Calculate the dimension a of the unit cell.

Solution

Chapter 16: The Solid State Essay Questions
16-10
16.44. Calculate the Debye temperature of tungsten that is isotropic (an assumption of the Debye model). The cutoff frequency is given by
1
1
3
3
3 3
9 1 2
4
D
l t
N
V c c
| |
| |
= +
| |
\ .
\ .

where
5 1
5.2496 10 cms
l
c

=
and
5 1
2.9092 10 cms
t
c

=
are the longitudinal and trasverse elastic wave velocities, respectively, in tungsten.

Solution

Essay Questions
16.45. List the 14 Bravais lattices and group them into P, I, F, C, and R cells.
16.46. Explain why the initial X-ray investigation of the two face-centered cubic structures, NaCl and KCl, showed that NaCl was face
centered whereas KCl was simple cubic.
16.47. If
c
H were required rather than
c
E , what modification of the Born-Haber cycle would be needed?
16.48. X-ray diffraction is often used to measure residual stress in metals. Suggest that change in the measured parameters allow this
determination.
16.49. Gold diffuses faster in lead at 300C than does sodium chloride in water at 15C. Point defects based on vacancies can account for
such high rates. For an ionic material, suggest ways in which such vacancies can occur without altering the stoichiometry of the
crystal.

Chapter 16: The Solid State Solutions
16-11
Solutions
16.1. How many basis groups are there in

a. An end-centered lattice;
b. A primitive lattice?

Solution:

Given: see above

Required: number of basis groups

a. The end-centered lattice has
( ) ( )
1 1
8 2 2
8 2
+ = lattice points. Since one basis is a
each lattice point, each unit cell has two basis groups.

b. The primitive lattice has one lattice point and there is therefore only one basis group.

16-12
16.2. How many lattice points are there in a unit cell of

a. A face-centered lattice;
b. A body-centered lattice?

Solution:

Given: see above

Required: number of lattice points
a. A unit cell has 8 lattice points at the corners of a cube; each corner is shared with seven other unit cells. Therefore, only 1/8 of
the 8 belong to a particular face-centered cubic (fcc) cell. Each face has an additional lattice point shared between two cells;
there are therefore
( )
1
6 3
2
= lattice points in the faces. For the unit cell: 1 (from corners) +3 (from faces) =4 lattice points.

b. A body-centered cubic (bcc) lattice has 1 lattice point belonging to the unit cell plus
( )
1
8
8
corner points. There are thus 1 +1
=2 lattice points.
16-13
16.3. a. Determined the efficiency of area utilization in packing circles onto the lattice points of a square lattice.
b. Compare that value with the efficiency of packing circles onto a triangular lattice.
c. Which packing uses area more efficiently and by how much?
Solution:

Given: see above

Required: see above

a. Consider the array of circles:

The area belonging to each circle is shown as a dotted box of area
2
4R . The area of the circle is
2
R .
2
efficiency of filling space

R
=
2
4R
0.785 398 163
efficiency of filling space 0.785 or 78.5%
=
=

b. Circles on triangular lattice are shown below:

16-14
The hexagonal area belonging to a single circle is shown by the dotted lines. The hexagonal area is made up of 12 right triangles,
each having an area of

2
1 1 1
2 3 2 3
R R R
| | | | | |
=
| | |
\ .\ . \ .

The total area is
( )
2 2
1
12 3 2 3
2
R R = , and the efficiency of filling space is given by
2
R
2
2 3R
0.906 899 682

2 3
efficiency of filling space 0.907 or 90.7%
= =
=

c. The triangular form is more efficient by a factor of
90.689 9682
1.154 700 538
78.539 8163
1.15
=
=

16-15
16.4. a. Calculate the percentage of free space (volume of the cell minus the volume of the atoms in the unit cell) in each of the three
cubic lattices if all atoms in each are of equal size and touch their nearest neighbors.
b. Using the calculated values, determine which of the three structures represents the most efficient packing (least amount of used
space).
Solution:

Given: see above

Required: see above

a. A simple cubic crystal lattice of side 2r contains one atom of radium r.
( )
3
3
3 3
3
3
3
Free space volume of cube volume of atom
4
Free space 2
3
Free space 8 4.188 790 205
Free space 3.811 209 795
3.811 209 795
Percent free space 100 47.640 1224%
8
Percent free space 47.64%
r r
r r
r
r
r
=
=
=
=
= =
=

A body-centered cube contains two atoms of radius r in the unit cell. The length of the edge of the cube is calculated using the
Pythagorean theorem:
16-16

The diagonal of the cube is 4r.
( )
2
2 2
4r d e = +
but
2 2 2
d e e = +
so
( )
2
2
3
3
4 3
4
(length of edge)
3
4 4
Free space 2
3 3
r e
r
e
r
r
=
=
| | | |
=
| |
\ . \ .

3 3
3
3
Free space 12.316 805 74 8.377 580 41
Free space 3.939 225 33
3.939 225 33
Percent free space
r r
r
r
=
=
=
3
12.316 805 74r
100
Percent free space 31.982 523 83%
=
=

16-17
A face-centered cube contains four atoms of radius r in the unit cell. The length of the edge of the cube is calculated using the
Pythagorean theorem:

( )
2
2 2 2
4 2
2 2
r e e e
e r
= + =
=

( )
3
3
3 3
3
3
4
Free space 2 2 4
3
Free space 22.627 417 16.755 160 82
Free space 5.872 256 18
5.872 256 18
Percent free space
r r
r r
r
r
| |
=
|
\ .
=
=
=
3
22.627 417r
100 25.951 951%
=
=

b. The face-centered cube has the least amount of unused space.

16-18
16.5. Derive an equation to relate the density D of a right-angled unit cell to its edge lengths a, b, and c and the number of formula units z
per unit cell.

Solution:

Given: see above

Required: derive an equation that relates D to a, b, and c and z

The volume of a unit cell with right angles is the product abc of its edges. Since one mole of the crystal contains z unit cells, the molar
volume is
m
abc
V
z
= . The molar mass M divided by the molar volume V
m
is the density D:
3
3
kg m atom
, where is the Avogadro's number in
mol atom mol
kg
m
av av
m
m
M
N N
V
M
D
V
| |
=
|
\ .
= =

Therefore,
av
m
av
M M
D
abcN
V
z
Mz
D
abcN
= =
=

16-19
16.6. Silver crystallizes in a face-centered cubic unit cell with a silver atom on each lattice point.

a. If the edgelength of the unit cell is 4.0862 , what is the atomic radius of silver?
b. Calculate the density of silver.

Solution:

Given: characteristic of silver atom, edge length

Required: atomic radius and density

a. In a face-centered cube containing identical atoms of radius r, the edge length is 2 2 r . For silver, the edge length is 4.0862 .
Edge length 4.0862 2 2
4.0862
2 2
1.444 689 865
1.4447
r
r
r
r
= =
=
=
=

b. The volume of a unit cell is
3
8
23 3
10 cm
4.0862
6.822 740 578 10 cm

V
V
| |
=
|
\ .
=

One unit cell contains four atoms, so 1 mol of Ag contains
23
23 1
6.022 10 atoms 1 unit cell
1.5055 10 unit cells mol
mol 4 atoms

=

16-20
The mass of 1 mol of Ag is 107.8682 g mol
-1
. The density is
1
107.8682 g mol
m
M
D
V
= =
23 1
1.5055 10 cells mol
( ) ( )
23 3
3
3
6.822 740 578 10 cm
10.501 559 89 g cm
10.512 g cm
D
D
=
=

16-21
16.7. Barium crystallizes with an edge length of 5.025 in a body-centered cubic unit cell.

a. Calculate the atomic radius of barium using this information.
b. Calculate the density of barium.

Solution:

Given: characteristics of barium, edge length

Required: atomic radius, density

a. In a body-centered cubic unit cell, the metal atoms are in contact along the diagonal of the cube. The diagonal of the cube forms
a right triangle with the unit cell edge and the diagonal of a face. Use the Pythagorean theorem to determine the length of the
diagonal, d, on the face of the cube in terms of e.

2 2 2 2
2
2
d e e e
d e
= + =
=

The diagonal of the cube is the length of four atomic radii and can be calculated by again using the Pythagorean theorem.
( ) ( ) ( )
( )
( )
2 2 2
2
2
2 2
Diagonal 4 2
Diagonal 16 3
Diagonal 4 3
3 3
5.025 2.175 888 827
4 4
2.176
r e e
r e
r e
e
r
r
= = +
= =
= =
= = =
=

b. Given a body-centered cubic structure, each unit cell contains two atoms. Use the unit cell edge length to calculate the unit cell
volume and the volume occupied by each atom. Multiply to obtain the molar volume and divide the gram atomic weight by this
value to obtain density (e =edge length).
16-22
( )
3
3 8 22 3
22 3 23 3
23 3
(cell) 5.025 10 cm 1.268 843 906 10 cm
1.268 843 906 10 cm 6.344 219 531 10 cm
(atom)
2 atoms atom
6.344 219 531 10 cm
(mole)
atom
V e
V
V

= = =

= =
=
23
6.022 10 atoms | |
|
\ .
3
mol
38.204 890 02 cm
(mole)
mol
V
| |
|
\ .
=

3
137.33 g 38.204 890 02 cm
(Ba)
mol mol
137.33 g
(Ba)
mol
D
D
| |
| |
=
| |
\ .
\ .
=
mol

| |
|
\ .
3
3
3
38.204 890 02 cm
(Ba) 3.594 566 034 g cm
(Ba) 3.595 g cm
D
D
| |
|
\ .
=
=

16-23
16.8. Aluminum crystallizes in a face-centered cubic lattice with an aluminum atom on each lattice point with the edge length of the unit
cell equal to 4.0491 .

a. Calculate the atomic radius of aluminum.
b. Determine the density of aluminum.

Solution:

Given: characteristics of aluminum, edge length

Required: atomic radius, density

a. In a body-centered cubic unit cell, the metal atoms are in contact along the diagonal of the cube. The diagonal of the cube forms a
right triangle with the unit cell edge and the diagonal of a face. Use the Pythagorean theorem to determine the length of the diagonal,
d, on the face of the cube in terms of e.

( ) 2 4.0491
(Al) 1.431 573 034
4
(Al) 1.432
r
r
= =
=

b. Follow the same procedure for density as used in Problem 16.7, but noting that a face-centered cubic cell contains four atoms per
cell instead of two.
16-24
( )
3
3 8 23 3
23 3
(cell) 4.0491 10 cm 6.638 584 809 10 cm
6.638 584 809 10 cm
(mol)
cell
V e
V

= = =
=
1 cell
4 atoms
23
6.022 10 atoms
3 1
mol
(mol) 9.994 389 43 cm mol
26.9815 g
(Al)
mol
V
D
=
=
1 mol
3
3
3
2.699 664 666 g cm
9.994 389 43 cm
(Al) 2.700 g cm D
=
=


16-25
16.9. Crystals of p, p-dibromo-, -difluorostilbene [BrC
6
H
4
C(F)=]
2
are orthorhombic with edge lengths a =28.32 ; b =7.36 ; c =
6.08 . If there are four molecules in a unit cell, calculate the density of the crystal.

Solution:

Given: see above

Required: density of the crystal

From Problem 16.5:

, where is the Avogadro's number and is the molar mass
av
av
Mz
D N M
abcN
=

Molar mass of [BrC
6
H
4
C(F)=]
2
=373.94 g mol
-1

1
4 373.94 g mol
D
=
( )
( ) ( ) ( )
3
28.32 7.36 6.08
8 1
10 cm

( )
3
23 1
6.022 10 mol

( )
3
3
1.959 9569 g cm
1.96 g cm
D
D
=
=

16-26
16.10. How many formula units exist in pure crystalline Si, which occurs in a face-centered cubic lattice, if its density is 2.328 99 g cm
-3

and its cell length is a =50431 066 ? The atomic mass of Si is 28.085 41 g mol
-1
.

Solution:

Given: characteristics of Si, its density, cell length, and atomic mass

Required: number of formula

From Problem 16.5:

av
av
Mz
D N M
abcN
=

For a face-centered cubic lattice, all edge lengths are equal, that is a =b =c.
2.328 99 g
av
DabcN
z
M
z
=
=
3
cm
5.431 066
( )
3
8
10 cm
1

( )
3
23 1
6.022 10 mol
( )
28.085 41 g
1
mol
7.999 868 501

8
z
z
=
=

16-27
16.11. Sodium chloride crystallizes in a face-centered cubic lattice with four NaCl units per unit cell. If the edge length of the unit cell is
5.629 , what is the density of the crystal? Compare your answer to the value given in the CRC Handbook.

Solution:

Given: characteristics of sodium chloride, edge length

Required: density

av
av
Mz
D N M
abcN
=

For sodium chloride, 4, 58.45 z M = = . As the crystal is a face-centered cubic lattice,

a =b =c =5.629
1
4 58.45 g mol
av
Mz
D
abcN
D
=
=
( )
5.629
( )
3
8 1
10 cm

( )
3
23 1
6.022 10 mol
( )
3
3
3 o
2.176 7573 g cm
2.176 g cm
CRC value 2.165 g cm at 25C
D
D
=
=
=

The lower density given in the handbook may be due to voids and other imperfections in the crystal.

16-28
16.12. LiH crystallizes with a face-centered cubic structure. The edge length of the unit cell of LiH is 4.08 . Assume anion-anion contact
to calculate the ionic radius of H
-
. Compare your answer to the value using the radium of Li
+
as 0.68 .

Solution:

Given: LiH characteristics, edge lenth

Required: ionic radius

The structure is face-centered cubic with the hydride ions in contact along the diagonal of the face as shown in the figure.

From the figure,

( ) ( )
2 2
H
H
H
4 2 4.08
1.442 497 834
1.44
d
d
d
=
=
=

Another way to look at this problem is to consider that lithium ions fill the space along the edge, giving an edge length of
Li H
2 2 r r
+
+ . The
radius of the hydride ion is computed from the edge length e and the reported radius of Li
+
(0.68 ).

16-29
( )
( )
Li H
H
H
H
H
4.08 2 2
2 0.68 2
2 0.68
2
4.08 1.36
2
1.36
e r r
e r
e
r
r
r
+
= = +
= +
=
=

A recent edition of the CRC Handbook gives two values for Li
+
: with coordination number 4, its radius is 0.56 ; with coordination number
6, its radius is 0.76 . The value of 0.68 just cited is found in an older edition and represents an average value. Any value of
H
r

will
depend upon the value of
Li
r
+
used in this method. It is common to consider that the anions are in contact with the cations occupying the
open space. There is no requirement that the anions and the cations contact. Therefore, the first method gives a better estimate of the
maximum size of H
-
.
16-30
16.13. KCl is tetramolecular and crystallizes in a face-centered cubic lattice. If the edge length is 6.278 , what is the density of KCl?
Compare your answer to the value in the CRC Handbook.

Solution:

Given: characteristics of KCl, edge length

Required: density

The molar mass of KCl is
1
74.55 g mol
.

1
4 74.55 g mol
av
Mz
D
abcN
D
=
=
( )
6.278
8 1
10 cm

( )
3
23 1
6.022 10 mol
( )
3
3
3
2.001 257 414 g cm
2.001 g cm
value 1.984 g cm
D
D
CRC
=
=
=

16-31
16.14. Calcium Fluoride crystallizes in a face-centered cubic lattice where a =b =c, and it has a density of 3.18 g cm
-3
. Calculate the unit
cell length for CaF
2
.

Solution:

Given: characteristics of calcium fluoride, density

Required: unit cell length

The molar mass of calcium fluoride is
1
78.08 g mol

There are four calcium ions per unit cell and eight associated fluoride ions. Consequently, z =4 and rearrangement of
3
with gives
4 78.08 g
av
av
Mz
D a b c
abcN
Mz
a
DN
= = =
= =
1
mol
( )
3.18 g
( )
3 23 1
cm 6.022 10 mol

( )
3 22 3
8
8
1.630 917 245 10 cm
5.463 580 021 10 cm
5.46 10 cm 5.46 546 pm
a
a
a
=
=
= = =


16-32
16.15. Calculate the Miller indices of the parallel planes in a cubic lattice that intercepts the unit cell length at x =a,
1
2
y a = , and
2
3
z a = .

Solution:

Given: cubic lattice, x =a,
1
2
y a = , and
2
3
z a = .

Required: Miller indices

The intercepts along the axes are spaces at a/h, b/k, c/l. For a cubic system

2 3
1 , 1; , 2; ,
2 3 2
a a a a a
a h k l
h k l
= = = = = =

Clearing fraction we have

( ) ( ) 243 hkl =

16-33
16.16. Determine the distance (i.e. d value) of the closest plane parallel to the 100, 110, and 111 faces of the cubic lattice.

Solution:

Given: see above

Required: see above

The faces are shown in the figures below:

The spacings are calculated from the formula

2 2 2
hkl
a
d
h k l
=
+ +

Or from trigonometry as demonstrated from the 110 planes:

16-34
2 2 2
110 110
2 2
110
110
2
2
d d a
d a
a
d
+ =
=
=

The results are

110 110 111

2 3
a a
d a d d = = =


16-35
16.17. What are the Miller indices of the plane that cuts through the crystal axes at

a. (2a, b, 3c);
b. (2a, -3b, 2c);
c. (a, b, -c);

Solution:

Given: see above


Originals Reciprocals Miller indices
a. (2a, b, 3c)
1 1
,1,
2 3

(362)
b. (2a, -3b, 2c)
1 1 1
, ,
2 3 3

(323)
c. (a, b, -c) 1,1, 1
(111)

16-36
16.18. Determine the value of d
hkl
in terms of the cell constants and angles for

a. The orthorhombic unit cell,
b. The tetragonal unit cell.

Solution:

Given: see above

Required: value of d
hkl

a. In the orthorhombic system, all three sides are different and all angles are 90. Therefore, all sine terms are equal to one and all
cosine terms are equal to zero. From Eq. 16.19,

2
2 2 2
2 2 2
1
hkl
d
h k l
a b c
=
+ +

or

12
2 2 2
2 2 2 hkl
h k l
d
a b c
| |
= + +
|
\ .

b. For the tetragonal system, a =b =c and all angles are 90. Therefore, all sine terms are equal to one and all cosine terms are equal to
zero. From Eq. 16.19.

2
2 2 2
2 2 2
1
hkl
d
h k l
a b c
=
+ +

Then with a =b,

16-37
2
2 2 2
2 2
1
hkl
d
h k l
a c
=
+
+

or

12
2 2 2
2 2 hkl
h k l
d
a c
| | +
= +
|
\ .

16-38
16.19. Calculate the separation between planes in a cubic lattice with unit cell length of 389 pm when the indices are

a. 100;
b. 111;
c. 121

Solution:

Given: see above

Required: separation between planes

( )
12
2 2 2
hkl
a
d
h k l
=
+ +

a.
100
389 pm
1
d =
100
389 pm d =

b.
( )
111 12
2 2 2
389 pm 389 pm
3
1 1 1
d = =
+ +

111
111
224.589 254 7 pm
225 pm
d
d
=
=

c.
( )
12 121
2
2 2
389 pm 389 pm
6
1 2 1
d = =
(
+ +

121
121
158.808 585 pm
159 pm
d
d
=
=

16-39
16.20. Copper sulfate single crystals are orthorhombic with unit cells of dimensions a =488 pm, b =666 pm, c =832 pm. Calculate the
diffraction angle from Cu K
X rays
( = 154.18 pm) for first-order reflections from the (100), (010), and (111) planes.

Solution:

Given: characteristics of copper sulfate, cell dimensions, = 154.18 pm, planes indices.

Required: diffraction angle.

2 sin =154 pm
hkl
d =

From Problem 16.18,

16-40
2 2 2
2 2 2 2
100 2 2
100
010 2 2
010
2 2 2 2 2 2 2
111
6 6 6
2
111
6
2
111
111
1
1 1
; 488 pm
1 1
; 666 pm
1 1 1 1 1 1 1
488 666 832
1
4.199 140 016 10 2.254 506 759 10 1.144 619 083 10
1
7.898 265 858 10
355
h k l
d a b c
d a
d a
d b
d b
d a b c
d
d
d

= + +
= = =
= = =
= + + = + +
= + +
=
=
100
.823 089 3 pm
154 pm
sin
2d
= =
2 488 pm
( )
100
100
010
0.157 786 885
9.078 462 401
9.08
154 pm
sin
2d
=
=
=
= =
2 666 pm
( )
010
010
0.115 615 615
6.639 134 078
6.64
=
=
=

111
154 pm
sin
2d
= =
2 356 pm
( )
111
111
0.216 292 134
12.491 345 05
12.49
=
=
=

16-41
16.21. Determine the angle of reflection when copper K
radiation (0.154 18 nm) is incident on a cubic crystal with a lattice constant d

hkl
of
0.400 nm.

Solution:

Given: = 0.154 18 nm, d
hkl
=0.400 nm

Required: angle of reflection

Assuming a first-order reflection,

2 sin
0.154 18 nm
d =
2 0.400 nm =
( )
sin
sin 0.192 725
11.111 854 97
11.1
=
=
=

16-42
16.22. Single crystals of FeSO
4
are orthorhombic with unit cell dimensions a =482 pm, b =684 pm, c =867 pm. Calculate the diffraction
angle from Te K
, X rays ( = 45.5 pm) from the (100), (010), and (111) planes

Solution:

Given: characteristics of FeSO
4
crystal, cell dimensions, = 45.5 pm, plane indices

Required: diffraction angle

2 sin =45.5 pm
hkl
d =

From Eq. 16.19 or Problem 16.18,

16-43
2 2 2
2 2 2 2
100 2 2
100
010 2 2
010
2 2 2 2 2 2 2
111
6 6 6
2
111
6
2
111
111
1
1 1
; 482 pm
1 1
; 684 pm
1 1 1 1 1 1 1
482 684 867
1
4.304 333 603 10 2.137 409 801 10 1.330 337 413 10
1
7.772 080 818 10
hkl
h k l
d a b c
d a
d a
d b
d b
d a b c
d
d
d

= + +
= = =
= = =
= + + = + +
= + +
=
=
100
358.699 974 7 pm
45.5 pm
sin
2d
= =
2 482 pm
( )
100
100
010
0.047 199 17
2.705 318 347
2.71
45.5 pm
sin
2d
=
=
=
= =
2 684 pm
( )
010
010
0.033 260 233
1.906 022 56
1.91
=
=
=

111
45.5 pm
sin
2d
= =
2 359 pm
( )
111
111
0.063 370 473
3.633 295 227
3.63
=
=
=

16-44
16.23. Single crystals of Hg(CN)
2
are tetragonal with unit cell dimensions a =967 pm and
c =892 pm. Calculate the first-order diffraction angles from the (100) and (111) planes when Cu K
X rays ( = 154 pm) are used.

Solution:

Given: characteristics of Hg(CN)
2
crystal, cell dimensions, = 154 pm, plane indices

Required: first-order diffraction angles

2 sin =154 pm
hkl
d =

From Eq. 16.19 or Problem 16.18,

16-45
2 2 2
2 2 2
100 2 2
100
2 2 2
2 2 2
111
6 6
2
111
111
100
1
1 1
; 967 pm
1 1 1 1
967 892
1
2.138 833 844 10 1.256 811 921 10
542.673 745 5 pm
154 pm
sin
2
hkl
h k l
d a c
d a
d a
d
d
d
d

+
= +
= = =
+
= +
= +
=
= =
2 967 pm
( )
100
100
111
0.079 627 714
4.567 167 086
4.57
154 pm
sin
2d
=
=
=
= =
2 543 pm
( )
111
111
0.141 804 788
8.152 295 044
8.15
=
=
=

16-46
16.24. A two-dimensional lattice is depicted in Figure 16.1 with planes superimposed on it parallel to the third direction. Determine the
Miller indices for each set of planes representing the external habit of the left-hand crystal.

Solution:

Given: figure 16.1


The Miller indices depend upon the way in which we draw the unit cell. Four different ways and their corresponding values are shown.
Notice that the right-hand cell has been used for convenience. The planes in the left-hand cell will have exactly the same indices.

Notice that the angle between dots is not exactly 90. This does not matter since the a vector that determines the reciprocal lattice will be
perpendicular to the actual planes

The indices are A, (0, 1, 0); B, (-1, 1, 0); C, (2, 1, 0), and D, (1, 1, 0).

16-47
16.25. The layers of atoms in a crystal are separated by 325 pm. At what angle in a diffractometer will diffraction occur using

a. molybdenum K
X rays ( = 70.8 pm);

b. copper K
X rays ( = 154 pm)?

Solution:

Given: see above

Required: angle of diffraction

a. Let n =1 in the Bragg equation 2 sin n d =
Then
1
sin
2d
| |
=
|
\ .

( )
1
1
70.8
sin
2 325
sin 0.108 923 076
6.253 239 405
6.25
| |
=
|
\ .
=
=
=

b.
1
sin
2d
| |
=
|
\ .

( )
1
1
154
sin
2 325
sin 0.236 923 076
13.705 008 73
13.71
| |
=
|
\ .
=
=
=

Notice that the shorter the wavelength, the smaller the diffraction angle.

16-48
16.26. Calculate the wavelength of an electron that is accelerated through a potential difference of approximately 40 kV.

Solution:

Given: see above

Required: wavelength

The kinetic energy of the electron is
2
1
2
mu and is also VQ; it thus follows that
( )( )
( )
12
12
3 19
31
12
16 1
2 2
8 1
2
2 40 10 V 1.60 10 C
9.11 10 kg
1 V C 1 J
1.405 049 396 10 J kg
Since J kg m s
1.185347795 10 ms
VQ
u
m
u
u
u
| |
=
|
\ .
| |
= |
|
\ .
=
=
=
=

Substituting into the de Broglie equation (Eq. 11.56) gives
( )( )
34
31 8 1
12
6.63 10 J s
9.11 10 kg 1.19 10 ms
6.115 728 399 10 m
6.12 pm
h
mu
=

=
=

16-49
16.27. Find the X-ray wavelength that would give a second-order reflection (n =2) with a angle of 10.40 from planes with a spacing of
4.00 .

Solution:

Given: n =2, =10.40, plane spacing =4.00

Required: X-ray wavelength

( ) ( )
2 sin
2 sin
2 4.00 sin 10.40
2
0.722 076 581
0.722
n d
d
n
=
=
(

=
=
=

16-50
16.28. A substance forms cubic crystals. A powder pattern shows reflections that have either all even or all odd indices. What type of unit
cell does it have?

Solution:

Given: see above

Required: type of cell

From Figure 16.28, it is determined that the face-centered cubic (fcc) system is the only one that conforms to the data. Note that the
symmetry of the crystal determines which indices will appear.

[image]

16-51
16.29. A powder pattern of a cubic material has lines that index as (110), (200), (220), (310), (222), (400). What is its type of unit cell?

Solution:

Given: see above, lines indexes

Required: type of unit cell

From Figure 16.28, it can only be bcc

[image]

16-52
*16.30. The successive sin
2
values obtained from a powder pattern for -Fe are 1, 2, 3, 4, 5, 6, 7, 8, 9, etc.

a. If iron is in the cubic system, which type of unit cell is present?
b. If a copper X-ray tube is used ( = 154.18 pm), calculate the length of the side of the unit cell and the value of from (100)
planes. The density of -Fe is 7.90 g cm
-3
.
c. What is the radium of the iron atom if the central atom in the cubic cell is assumed to be in contact with the corner atoms?

Solution:

Given: see above

Required: see above

a. From Figure 16.28, it is seen that the ratio 7 is not allowed for cubic systems. The ratio must be 2, 4, 6, and so on. Consequently, the
structure is bcc.

b. For a bcc system, a =b =c, z =2, and from Problem 16.5,
3
D zMa L = or
3
2 55.85 g
a =
1
mol
( )
7.90 g
( )
3 23 1
cm 6.022 10 mol

( )
3 23 3
8
2.347 931 004 10 cm
2.863 486 304 10 cm
286.348 630 4 pm
286 pm
a
a
a
a
=
=
=
=

For 100 type planes, d is a/2 since the planes are actually (200). Therefore, from2 sin d n = ,

154.18 pm
sin =
286 pm
0.539 090 909
32.621 774 51
32.6
=
=
=

16-53
c. The body diagonal is the smallest interatomic distance and has the value
3
2
a
. Therefore, the radius is the distance from the center
of one Fe atom to the center of the central atom divided by 2:
Fe
Fe
Fe
3 3 286.348 630 4 pm
2 2 4
123.992 594 1 pm
124.0 pm
a
r
r
r
= =
=
=

16-54
16.31. Potassium metal has a density of 0.856 g cm
-3
and has a body-centered cubic lattice. Calculate the length of the unit cell a and the
distance between (200), (110), and (222) planes. Potassium has an atomic mass of 39.102 g mol
-1
.

Solution:

Given: characteristics of potassium metal, density, plane indices, atomic mass

Required: length of the unit cell, distance between the given planes

There are two atoms in a body-centered lattice and we may write:

( ) ( )
( )
( )
3
1
3
23 1 3
3
number of atoms/cell atomic mass
Density , where is the Avogadro's number
2 39.102 g mol
0.856 g cm
6.022 10 mol
2 39.102 g
av
av
N
N a
a
a
=
=
=
1
mol
( )
23 1
6.022 10 mol
( )
0.856 g
( )
3
8
cm
5.333 408 111 10 cm
533.340 811 1 pm
533.3 pm
a
a
a
=
=
=

Then from the equation

16-55
( ) ( )
12 12
2 2 2 2 2 2
200
200
110
110
1 533.340 811 1 pm
533.340 811 1 pm
For (200) planes, 266.670 405 6 pm
4
266.7 pm
533.340 811 1 pm
For (110) planes, 377.128 904 2 pm
2
377.1 pm
For (222) planes,
hkl
d
h k l h k l
d
d
d
d
= =
+ + + +
= =
=
= =
=
222
222
533.340 811 1 pm
153.962 230 4 pm
12
154.0 pm
d
d
= =
=

16-56
16.32. Low-angle lines in the Cu K
powder pattern of KCl are found to be at =14.18, 20.25, and 25.10. Find the crystal type from
these data. (For Cu K
= 154.18 pm.) What other information is needed for a definitive determination?

Solution:

Given: pH 7,
5 1
/ 2.18 10 V K E T =

Required: see above

First, determine the d values for the three lines and take their ratios:

( ) ( ) ( )
( ) ( ) ( )
1 2 3
1 2 3
1 2 3
1 2 3

2 2 2
sin 14.18 sin 20.25 sin 25.10
1 1 1
: : : :
sin 14.18 sin 20.25 sin 25.10
: : 4.082 149 659 : 2.889 195 951 : 2.357 381 803
: : 1
d d d
d d d
d d d
d d d
= = =
=
=
= : 0.707 763 358 : 0.577485393

From Problem 16.16, for the cubic lattice,

100
110
111
2
0.707
2
3
0.5773
3
d a
a
d
a
d
=
= =
= =

The ratios thus correspond to the cubic structure. To confirm the structure, if K
+
and Cl- reflect equally d =a/2, the theoretical density could
be compared to the experimental value.

16-57
16.33. The smallest observed diffraction angle of silver taken with Cu K
radiation
( = 154.18 pm) is 19.176. This angle is associated with the (111) plane in the cubic close-packed structure of silver.

a. Determine the value of the unit cell length a.
b. If D(Ag) =10.500 g cm
-3
and M =107.87 g mol
-1
, calculate the number of atoms in the unit cell.

Solution:

Given: see above

Required: value of the unit cell length, number of atoms in the unit cell

a.
( )
111
154.18 pm
235.877 596 9 pm
2sin 2sin 19.076
d
= = =
( )
( )
12
2 2 2
12
2 2 2
235.877 596 9 pm
235.877 596 9 pm
1 1 1
408.551 982 2 pm
408.6 pm
a
h k l
a
a
a
=
+ +
=
+ +
=
=

b. The effective volume of each Ag atom is

Ag
107.87 g
V
av
M
DN
= =
1
mol
10.500 g
( )
3 23 1
m 6.022 10 mol

( )
( )
23 3
Ag
7 3
Ag
3
3 7 3
cell
V 1.705 967 01 10 cm
V 1.705 967 01 10 pm
V 408.6 pm 6.821 738 806 10 pm a
=
=
= = =

16-58
The number of atoms per unit cell is

7 3
cell
Ag
6.821 738 806 10 pm
V
V
N

= =
7 3
1.705 967 01 10 pm
3.998 751 89
4 This is an indication that Ag is fcc. N
=
=

16-59
16.34. Sodium fluoride is known to form a cubic closed-packed structure. The smallest angle obtained with Cu K
radiation ( = 1.5418 )
is 16.72 and is derived from the (111) planes. Find the value of a, the unit cell parameter.

Solution:

Given: see above

Required: the unit cell parameter

( )
( )
111
111
111 12
2 2 2
154.2 pm
2sin 2sin 16.72
267.992 288 4 pm
3
267.992 288 4 pm
3
464.176 259 6 pm
464.2 pm
d
d
a a
d
h k l
a
a
a
= =
=
= =
+ +
=
=
=

16-60
16.35. The X-ray powder pattern of NaCl is taken with a chromium tube giving Cr K
=229.1 pm. The values of the lines are: 2036,

2358, 354, 4221, 4443, 5420, 6217, 6516. From these data determine the value of each d
hkl
and index the lines. From
the hkl values, show that this is a face-centered system.

Solution:

Given: above data

Required: see above

First, calculate decimal equivalent of values and the sin . From each value of , calculate the value of
2sin
hkl
d
= .

sin
229.1 pm
2sin
hkl
d
= h k l a
20 36' 20.600 0.351 841 648 325.572 599 6 1 1 1 564.0
23 58' 23.967 0.406 210 411 281.996 711 3 2 0 0 564.0
35 4' 35.067 0.574 533 936 199.378 997 2 2 2 0 564.0
42 21' 42.350 0.673 657 707 170.041 845 9 3 1 1 563.8
44 43' 44.717 0.703 605 57 162.804 282 5 2 2 2 564.0
54 20' 54.333 0.812 419 487 140.998 587 3 4 0 0 564.0
62 17' 62.283 0.885 255 665 129.397 647 3 3 1 564.0
65 16' 65.267 0.908 267 352 126.119 253 4 2 0 563.9

Ignore the final two columns for the time being.
Assume that NaCl has a cubic crystal structure.
16-61
Then

2 2 2
hkl
a d h k l = = + +

If we index the first three angles obtained from NaCl according to the (100), (110), (111) planes of the simple cubic lattice, the value of a
should be the same in each case.

( )
( )
( )
2
2 2
2 2 2
1 0 0 325.572 599 6 pm 1 325.572 599 6 pm
1 1 0 281.996 711 3 pm 2 398.803 573 7 pm
1 1 1 199.378 997 2 pm 3 345.334 553 1 pm
hkl
hkl
hkl
a d
a d
a d
= + + = =
= + + = =
= + + = =

Since the unit cell dimension a is not the same, this does not allow indexing as a simple cubic system.

An attempt to index the first line with
110
d gives

( )
2 2
325.572 599 6 pm 1 1 0 460.429 185 9 pm a = + + =

And the next set of hkl values must give the value

2 2 2
460.429 185 9 pm
hkl
a
h k l
d
+ + = =
281.996 711 3 pm
1.632 746 651 =

No set of integers will give this value.

If the first line is indexed as 111, we have

( )
2 2 2
325.572 599 6 pm 1 1 1 563.908 284 1 pm a = + + =

And, as in the last case, the next line must be indexed such that

16-62
2 2 2
563.908 284 1 pm
hkl
a
h k l
d
+ + = =
281.996 711 3 pm
1.999 698 087 2 = =

This allows h, k, or l =2 corresponding to planes (200), (020), (002).

The rest of the planes can be indexes as listed in the final columns of the table with the corresponding values of a. These correspond to the
lines expected for an fcc structure as listed in Figure 16.20.

16-63
16.36. Cadmium sulfide has been used as a yellow pigment by artists. The sulfide crystallizes with cadmium occupying
1
2
of the tetrahedral
holes in a closest-packed array of sulfide ions. What is the formula of cadmium sulfide?

Solution:
Given: see above

Required: formula of cadmium sulfide

In a closest-packed array there are two tetrahedral holes for each anion. If only half the tetrahedral holes are occupied, the numbers of
anions and cations are equal. The formula for cadmium sulfide is CdS.

16-64
16.37. Rutile is a mineral that contains titanium and oxygen. The structure of rutile may be described as a closest-packed array of oxygen
atoms with titanium in
1
2
of the octahedral holes. What is the formula of rutile? What is the oxidation number of titanium?

Solution:

Given: see above

Required: formula of rutile, the oxidation number of titanium

In a closest-packed array, there is one octahedral hole for each anion. If only half of the octahedral holes are occupied by titanium atoms,
there are twice as many oxygen atoms as titanium ions, and the formula as TiO
2
. With each oxygen as -2, the titanium must be +4.

16-65
16.38. A tetrahedral hole is shown in Figure 16.33. Determine the largest sphere of radius r that can fit into a tetrahedral hole when the
surrounding four spherical atoms of the lattice are in contact. Let the lattice atom have radium R.

Solution:

Given: Figure 16.33, above information

Required: see above

The contributions of the four atoms in contact forming the tetrahedral void may be represented at the corners A, B, C, and D. A plane
through A and B and bisecting the line CD is represented as follows:

Here the atoms at A and B are shown by arcs. The right triangle AGV is similar to the right triangle ABF. Therefore

2
3
AG AB
AV AF
= =
16-66
Then the maximum radius of the circle representing the void can be no more thanAV R , that is,

2
3
3 2
0.224 744 871
2
0.225
AG R
AV R r
r R R
r R
= =
+
= =
=

16-67
16.39. An octahedral hole is surrounded by six spheres of radium R in contact. If one-sixth of each of the six coordinating spheres
contributes to the volume of the octahedron surrounding the hole, calculate the maximum radius of the sphere that can be
accommodated.

Solution:

Given: see above

Required: maximum radius

Take a section through an octahedron with sides of unit length:

The diagonal AC is 2.

From the isosceles right triangle,

2
1
AC
AB
=

16-68
If r is the radius of the void, then

2 2 2
2 1
2 0.414 213 562
0.414
R r
R
r R R R
r R
+
=
= =
=

16-69
16.40. Calculate the value of E
c
of the RbBr from the following information:
1
414 kJ mol
f
H

= ; I (ionization energy, Rb) =397 kJ
mol
-1
;
sub
(Rb) H =

1
84 kJ mol
; D
0
(Br
2
) =192 kJ mol
-1
; A (electron affinity, Br) =318 kJ mol
-1
.

Solution:

Given: above data

Required: value of E
c

From Eq. 16.58,

( )
sub 0
1
1
1
2
1
414 84 192 397 318 kJ mol
2
673 kJ mol
C f
C
C
E H H D I A
E
E
= + + +
(
= + + +
(

=


16-70
16.41. Some of the d spacings for the mineral canfieldite (Ag
8
SnS
6
) are 3.23, 3.09, 3.04, 2.81, and 2.74 obtained with Cu K
X rays ( =
1.5418 ).

a. Find the corresponding angles of diffraction.

b. This is a cubic system with a =21.54 ; determine the hkl values for the first 3 d spacings.

Solution:

Given: see above

Required: angles of diffraction, hkl values

a. 2 sin n d =

d/pm 323 309 304 284 274

13.81 14.45 14.69 15.75 16.33

b.
2 2 2
2 2
1 h k l
d a
+ +
=
16-71
( )
2 2 2
2 2
For 323 pm:
1 1
323 pm
21.54
d
h k l
d
=
+ +
= =
2 1
10 pm
( )
( )
2
2 2 2
2 2 2
2 2 2
2 2
44.471 968 48
6 2 2 36 4 4 44
For 309 pm:
1 1
309 pm
21.54
h k l
d
h k l
d
+ + =
+ + = + + =
=
+ +
= =
2 1
10 pm
( )
2
2 2 2
2 2 2
48.593 081 35
4 4 4 48
h k l + + =
+ + =

( )
2 2 2
2 2
For 304 pm
1 1
304 pm
21.54
d
h k l
d
=
+ +
= =
2 1
10 pm
( )
2
2 2 2
2 2 2
50.204 683 17
5 4 3 50
h k l + + =
+ + =

Note that other combinations of hkl values are possible, as well as different orders of the values given. As higher values of hkl are
used, more possibilities exist, making it more difficult to decide on the correct values. Help in this task is provided by knowledge of
the lines that are forbidden for the particular crystal type, and of the extinction caused by absorption by different atoms in the crystal
layers.

16-72
16.42. A copper selenide mineral (Cu
5
Se
4
) called athabascaite is orthorhombic with a =8.277,
b =11.982, c =6.441 . Strong intensity lines using Cu K
X rays ( = 154.18 pm) are observed at 12.95, 13.76, and 14.79.

Determine the d spacings and assign hkl values to these lines.

Solution:

Given: see above

Required: d spacings, assign hkl values

12.95 13.76 14.79
2 2 2
2 2 2 2
2 sin
344 pm; 324 pm; 302 pm
1
n d
d d d
h k l
d a b c

=
= = =
= + +

With the values given,

( )
2 2 2
2 2 2 2
2 2 2
2
1
822.7 1198.2 644.1
/pm
1
676 835.29 1435 683.24 414 864.81
h k l
d
h k l
d
= + +
= + +

With d =344 pm, agreement is obtained with 2, 0, and 1 h k l = = = :

6
2
2 2 2
2 2 2
6 6
6
1
LHS 8.450 513 791 10
344
2 0 1
RHS
822.7 1198.2 644.1
RHS 5.909 857 33 10 0 2.410 423 772 10
RHS 8.320 281 102 10
= =
= + +
= + +
=

16-73

6
2
2
2
6
1
LHS 9.525 986 892 10
324
2
RHS 0 0
644.1
RHS 9.641 695 086 10
= =
= + +
=


6
2
2
2
6
1
LHS 10.964 431 38 10
302
4
RHS 0 0
1198.2
RHS 11.144 519 59 10
= =
= + +
=

In the latter case, agreement is obtained with h =1, k =0, and l =2 (RHS =11.0 10
-6
), but in view of the crystal type (040) is more likely.

16-74
*16.43. Zinc blende is the face-centered cubic form of ZnS with Zn at
1 1 1
0,0,0; , ,0;0, ,0;
2 2 2

1 1
, ,0
2 2
and with S at
1 1 1 1 3 3 3 1 3 3 3 1
, , ; , , ; , , ; , , .
4 4 4 4 4 4 4 4 4 4 4 4

a. Determine the structure factor from the (111) planes that gives rise to the lowest angle reflection at =14.30 using Cu K
( =
154.18 pm).
b. Calculate the dimension a of the unit cell.

Solution:

Given: see above

Required: structure factor, dimension a of the unit cell

a. From Eq. 16.38,

( ) ( )
( ) ( )
1
Zn
S
exp 2
1 1 1 1 1 1
exp2 0 exp2 exp2 exp2
2 2 2 2 2 2
1 1 1 1 3 3 3 1 3
exp2 exp2 exp2
4 4 4 4 4 4 4 4 4

N
j j j j
j
F hkl f i hx ky lz
F hkl f i i i i
f i i i
=
( = + +

( | | | | | |
= + + + + + +
| | | (
\ . \ . \ .
| | | | | |
+ + + + + + + + +
| | |
\ . \ . \ .
( )
( ) ( )
( )
Zn S
Zn S
3 3 1
exp2
4 4 4
3 7
1 3exp 2 exp 3exp
2 2
4 4

i F hkl
i i
F hkl f i f
F hkl f i f
( | |
+ + +
|(
\ .
( | | | |
= + + + (
| | (
\ . \ .
=

16-75
b.
( )
( )
12
2 2 2
2sin
154.18 pm 3
2 0.247
540.582 173 1 pm
540.6 pm
a h k l
a
a
a
= + +
=
=
=

16-76
16.44. Calculate the Debye temperature of tungsten that is isotropic (an assumption of the Debye model). The cutoff frequency is given by
1
1
3
3
3 3
9 1 2
4
D
l t
N
V c c
| |
| |
= +
| |
\ .
\ .

where
5 1
5.2496 10 cms
l
c

=
and
5 1
2.9092 10 cms
t
c

=
are the longitudinal and trasverse elastic wave velocities, respectively, in tungsten.

Solution:

Given: see above

Required: Debye temperature of tungsten

The number of atoms per unit volume must be calculated

av
N N D
V A
=

Where A is the atomic mass, D is the density, and N
av
is the Avogadros number.

13
13
3 3
9 1 2
4V
19.271 g
9
4
D
l t
D
N
c c
| |
| |
= +
| |
\ .
\ .
=
3
cm
( )
23 1
6.022 10 mol
( )
183.85 g
1
mol
( )
13
5
1

5.2496 10 cm
(
(
(

( )
3
1 5
2
s 2.9092 10 cm
( )
13
3
1
12 1
s
8.004 707 251 10 s
D
(
(
(

=

16-77
Then
34
6.6262 10 J
D
D
B
h
k
= =
s
( )
12 1
8.004 707 251 10 s
( )
23
1.3807 10 J
( )
1
K

384.1586962 K
384 K
D
D
=
=


CHAPTER
1
1
7
7
The Liquid State

Physical Chemistry
Electronic Edition


Chapter 17: The Liquid State Thermodynamic Properties of Liquids
17-2
Chapter 17
Thermodynamic Properties of Liquids
17.1. The density of liquid ethanol at 20 C is 0.790 g cm
3
, and the van der Waals constant a is 1.218 Pa m
6
mol
2
. Estimate the internal
pressure and the potential-energy contribution to the internal energy.
Solution
17.2. In Example 17.3 (page 905), we obtained the internal pressure of liquid water from the van der Waals constant a. A more reliable
value is obtained by use of Eq. 17.2, from the thermal pressure coefficient ( / ) ;
V
P T this quantity is the ratio / of the coefficient
of expansion [ (1/ )( / ) ]
P
V V T = to the compressibility [ (1/ )( / ) ].
T
V V P = For water at 1 bar pressure and 298 K the thermal
pressure coefficient is 6.60 10
6
Pa K
1
. Calculate the internal pressure.
Solution
17.3. The density of liquid benzene at 0 C is 0.899 g cm
3
, and the van der Waals constant a is 1.824 m
6
mol
2
Pa. Estimate the internal
Solution
17.4. Make a better estimate of the internal energy of liquid benzene from its thermal pressure coefficient ( / ) ,
V
P T

which at 298 K and 1
bar pressure is 1.24 10
6
Pa K
1
.
Solution
17.5. Calculate the internal pressures of the following liquids at 298 K and 1 bar pressure from their thermal pressure coefficients, which
are as follows:
Hg: 4.49 10
6
Pa K
1

n-Heptane: 8.53 10
5
Pa K
1

n-Octane: 1.01 10
6
Pa K
1

Diethyl ether: 8.06 10
5
Pa K
1

Solution
Chapter 17: The Liquid State Intermolecular Energies
17-3
17.6. The thermal pressure coefficient ( / ) ,
V
P T for CCl
4
vapor at 298 K and 10 Pa pressure, is 115 Pa K
1
. That for liquid CCl
4
at 298
K and 1 bar pressure is 1.24 10
6
Pa K
1
. Calculate the internal pressures of the vapor and the liquid under these conditions.
Solution
*17.7. The following data apply to liquid acetic acid at 1 atm pressure and 293 K: density, d =1.049 g cm
3
; coefficient of expansion,
=1.06 10
3
K
1
; compressibility, =9.08 10
10
Pa
1
; van der Waals constant, a =1.78 m
6
Pa mol
2
. Make two
estimates of the internal pressure P
i
, (a) using and and (b) using a.
Solution
*17.8. a. Derive the relationship
2
P V
VT
C C

=
where is the coefficient of expansion and is the compressibility.
b. The value of C
V,m
for liquid CCl
4
at 298 K and at 1 bar pressure is 89.5 J K
1
mol
1
. Obtain the value of C
P,m
using the following
data: V
m
=97 cm
3
mol
1
; =1.24 10
3
K
1
; =10.6 10
5
bar
1
.
c. Calculate C
P,m
C
V,m
for liquid acetic acid using the data given in Problem 17.7.
Solution
Intermolecular Energies
17.9. A liquid having a molar volume of 50 cm
3
is converted into a vapor having a molar volume of 50 dm
3
. By what factor does the
average intermolecular energy change?
Solution
17.10. Calculate the maximum energy of attraction, in J and in kJ mol
1
, when a Ca
2+
ion is separated from a molecule of dipole moment
6.18 10
30
C m (=1.85 D; this is the dipole moment of water) by a distance of 500 pm in a vacuum.
Solution
17-4
17.11. Calculate the energy of attraction, in J and in kJ mol
1
, when a Ca
2+
ion is separated in a vacuum from a Cl

ion by a distance of 500
pm.
Solution
1
, when a Ca
2+
ion is separated in a vacuum by a distance of 500 pm, from a
nonpolar molecule (having zero dipole moment) but a polarizability of 2.0 10
30
m
3
.
Solution
17.13. Calculate the average energy of attraction, in J and in kJ mol
1
, for two molecules of dipole moments 6.18 10
30
C m separated in a
vacuum at 25 C by a distance of 500 pm.
Solution
17.14. The following values for A and B in the Lennard-J ones 612 function (Eq. 17.21) have been given for N
2
:
A =1.34 10
5
J pm
6
B =3.42 10
10
J pm
12
Calculate the equilibrium separation r
0
and the classical dissociation energy E
0
, in J and in J mol
1
.
Solution
*17.15. The following data apply to HBr: dipole moment, =2.60 10
30
C m; polarizability, =3.58 10
30
m
3
; oscillation frequency,
v
0
=3.22 10
15
s
1
. Estimate the dipole-dipole, dipole-(induced dipole), and dispersion energies in J and in kJ mol
1
for two HBr
molecules separated by 500 pm, at 25 C.
Solution
17-5
*17.16. The following are the polarizabilities and oscillation frequencies for Ne, Ar, and Kr:
Ne Ar Kr
Polarizability, /10
30
m
3
0.396 1.63 2.48
Frequency, v
0
/10
15
s
1
5.21 3.39 2.94

Calculate the dispersion energies for Ne, Ar, and Kr corresponding to a separation of 500 pm. Related data for He and Xe are given
in Table 17.3; plot the five calculated values against the boiling points of the noble gases:
He Ne Ar Kr Xe
Boiling point, T
b
/K 4.22 27.3 87.3 119.9 165.1

Solution
*17.17. In Table 17.3 and Problem 17.16 the dispersion energies of noble gases were calculated for a constant interatomic distance of 500
pm. More realistic values are:
He Ne Ar Kr Xe
Interatomic distances/pm 240 320 380 400 420

Recalculate the dispersion energies for these distances, and again plot the five values against the boiling points, which were given in
Problem 17.16.
The experimental value for the enthalpy of vaporization of liquid argon is 6.7 kJ mol
1
. Make an estimate of the enthalpy of vaporization
from your calculated value of E
p
(at 380 pm), assuming the liquid to have a close-packed structure with each atom having 12 nearest
neighbors.
Solution
Chapter 17: The Liquid State Essay Questions
17-6
*17.18. Estimate the interaction energy between an argon atom and a water molecule at a separation of 600 pm, which is approximately the
distance of closest approach. The necessary data are: H
2
O: dipole moment, =6.18 10
30
C m; Ar: polarizability, =1.63 10
30
m
3
.
Argon forms a solid hydrate, Ar 5H
2
O, but the binding energy between Ar and H
2
O is about 40 kJ mol
1
, which is a good deal
larger than the energy calculated from the dipole moment and polarizability. Suggest a reason for this discrepancy.
Solution
*17.19. a. The Lennard-J ones potential
6
n
A B
E
r r
= +
can be formulated in a different way by expressing A and B in terms of the minimum energy E
min
and the value r
0
of r at the
minimum energy. Obtain the expression for E in terms of E
min
and r
0
.
b. If r* is the value of r when E =0, obtain the relationship between r* and r
0
.
c. The Lennard-J ones potential is often used with n =12, and the equations are then simpler. Obtain E in terms of E
min
and r
0
and in
terms of E
min
and r*, for this special case of n =12.
Solution
Essay Questions
17.20. Explain qualitatively how intermolecular forces of attraction are related to the following properties of a liquid:
a. vapor pressure;
b. enthalpy of vaporization;
c. normal boiling point;
d. entropy of vaporization.
17.21. Explain clearly the difference between dipole-dipole and London (dispersion) forces. With reference to a few examples, discuss the
magnitudes of attractive energies arising from these forces.
Chapter 17: The Liquid State Solutions
17-7
Solutions
17.1. The density of liquid ethanol at 20 C is 0.790 g cm
3
, and the van der Waals constant a is 1.218 Pa m
6
mol
2
. Estimate the internal
Solution:
Given:
3 6 2
20 C, 0.790 g cm , 1.218 Pa m mol T a = = =
Required: ,
i p
P E
The internal pressure where the van der Waals equation applies, is given by Eq. 17.4
2
T m
U a
V V
| |
=
|
\ .

Since we have the density of ethanol, we can calculate the molar volume using the molar mass of ethanol.
( )
1
ethanol
1
ethanol
ethanol
1
3
3
2 12.011 6 1.00794 15.9994 gmol
46.06904gmol
46.06904 g mol
0.790 g cm
58.31524051cm
m
m
m
M
M
M
V
V
V
= + +
=
=
=
=
3
1 6
3
m
mol 10
cm

5 3 1
5.831524051 10 m mol
m
V

=

17-8
Solving for P
i
gives,
( )
6 2
2
5 3 1
3
1.218 Pa m mol
5.831524051 10 m mol
358165001.6Pa
3.58 10 bar
i
i
i
P
P
P

=
=
=

From Eq. 17.9, we solve for E
p

6 2
5 3 1
3 1
1
1.218 Pa m mol
5.831524051 10 m mol
20886.47821Pam mol
20.9kJ mol
p
m
p
p
p
a
E
V
E
E
E

=
=
=
=


17-9
17.2. In Example 17.3 (page 905), we obtained the internal pressure of liquid water from the van der Waals constant a. A more reliable
value is obtained by use of Eq. 17.2, from the thermal pressure coefficient ( / ) ;
V
P T this quantity is the ratio / of the coefficient
of expansion [ (1/ )( / ) ]
P
V V T = to the compressibility [ (1/ )( / ) ].
T
V V P = For water at 1 bar pressure and 298 K the thermal
pressure coefficient is 6.60 10
6
Pa K
1
. Calculate the internal pressure.
Solution:
Given:
6 1
1 bar, 298K, 6.60 10 Pa K
V
P
P T
T
| |
= = =
|
\ .

Required:
i
P from Eq. 17.2
The internal pressure given by Eq. 17.2 is
100000 Pa 298 K
T V
i
U P
P T
V T
P
| | | |
= +
| |

\ . \ .
= +
6 1
6.60 10 Pa K
( )
3
1966700000 Pa
19667 bar
19.7 10 bar
i
i
i
P
P
P
=
=
=


17-10
17.3. The density of liquid benzene at 0 C is 0.899 g cm
3
, and the van der Waals constant a is 1.824 m
6
mol
2
Pa. Estimate the internal
Solution:
Given:
3 6 2
0 C, 0.899 g cm , 1.824 Pa m mol T a = = =
Required: ,
i p
P E
We solve this problem using the same procedure as in problem 17.1.
The molar volume is calculated from the molar mass of benzene
( )
1
benzene
1
benzene
benzene
1
3
3
6 12.011 6 1.00794 gmol
78.11364gmol
78.11364 g mol
0.899 g cm
86.8894772 cm
m
m
m
M
M
M
V
V
V
= +
=
=
=
=
3
1 6
3
m
mol 10
cm

5 3 1
8.68894772 10 m mol
m
V

=

Solving for P
i
gives,
( )
6 2
2
5 3 1
3
1.824 Pa m mol
8.68894772 10 m mol
241596403.9Pa
2.42 10 bar
i
i
i
P
P
P

=
=
=

From Eq. 17.9, we solve for E
p

17-11
6 2
5 3 1
3 1
1
1.824 Pa m mol
8.68894772 10 m mol
20992.18523Pam mol
21.0kJ mol
p
m
p
p
p
a
E
V
E
E
E

=
=
=
=

17-12
17.4. Make a better estimate of the internal energy of liquid benzene from its thermal pressure coefficient ( / ) ,
V
P T

which at 298 K and 1
bar pressure is 1.24 10
6
Pa K
1
.
Solution:
Given:
6 1
1 bar, 298K, 1.24 10 Pa K
V
P
P T
T
| |
= = =
|
\ .

Required:
i
P from Eq. 17.2
100000 Pa 298 K
T V
i
U P
P T
V T
P
| | | |
= +
| |

\ . \ .
= +
6 1
1.24 10 Pa K
( )
3
369420000 Pa
3694.2 bar
3.69 10 bar
i
i
i
P
P
P
=
=
=


17-13
17.5. Calculate the internal pressures of the following liquids at 298 K and 1 bar pressure from their thermal pressure coefficients, which
are as follows:
Hg: 4.49 10
6
Pa K
1

n-Heptane: 8.53 10
5
Pa K
1

n-Octane: 1.01 10
6
Pa K
1

Diethyl ether: 8.06 10
5
Pa K
1

Solution:
Given: 1 bar, 298K, given above
V
P
P T
T
| |
= =
|
\ .

Required:
i
P
100000 Pa 298 K
T V
i
U P
P T
V T
P
| | | |
= +
| |

\ . \ .
= +
6 1
4.49 10 Pa K
( )
1337920000 Pa
13379.2 bar
i
i
P
P
=
=

a.
4
1.34 10 bar
i
P =
Repeating the same procedure as above, we obtain the following results:
b.
3
2.54 10 bar
i
P =
c.
3
3.01 10 bar
i
P =
d.
3
2.40 10 bar
i
P =
17-14
17.6. The thermal pressure coefficient ( / ) ,
V
P T for CCl
4
vapor at 298 K and 10 Pa pressure, is 115 Pa K
1
. That for liquid CCl
4
at 298
K and 1 bar pressure is 1.24 10
6
Pa K
1
. Calculate the internal pressures of the vapor and the liquid under these conditions.
Solution:
Given:
1
vapor
, vapor
298K, 10 Pa, 115 Pa K ,
V
P
T P
T
| |
= = =
|
\ .

6 1
liquid
, liquid
1bar, 1.24 10 Pa K
V
P
P
T
| |
= =
|
\ .

Required:
i
P for vapor and liquid
, vapor
10 Pa 298 K
T V
i
U P
P T
V T
P
| | | |
= +
| |

\ . \ .
= +
1
115Pa K
( )
, vapor
, vapor
, vapor
34260 Pa
0.34260 bar
0.343bar
i
i
i
P
P
P
=
=
=

For the liquid,
, liquid
100000 Pa 298 K
i
P = +
6 1
1.24 10 Pa K
( )
, liquid
, liquid
3
, liquid
369420000 Pa
3694.2 bar
3.69 10 bar
i
i
i
P
P
P
=
=
=

17-15
*17.7. The following data apply to liquid acetic acid at 1 atm pressure and 293 K: density, d =1.049 g cm
3
; coefficient of expansion,
=1.06 10
3
K
1
; compressibility, =9.08 10
10
Pa
1
; van der Waals constant, a =1.78 m
6
Pa mol
2
. Make two estimates of the
internal pressure P
i
, (a) using and and (b) using a.
Solution:
Given:
3 3 1 10 1
1 atm, 293K, 1.049 g cm , 1.06 10 K , 9.08 10 Pa P T d = = = = =

6 2
vdw
1.78 m Pa mol a =
Required: a)
i
P from and and
b)
i
P from using a
a. From Eq. 17.2, and knowing that the thermal pressure coefficient ( / )
V
P T is the ratio /,
T V
U P
P T
V T
| | | |
= +
| |

\ . \ .
becomes
i
P P T

| |
= +
|
\ .

Solving for
i
P we obtain,
100 000 Pa 293 K
i
P = +
3 1
1.06 10 K

10 1
3
9.08 10 Pa
341 948 458.2 Pa
3419.484 582 bar
3.42 10 bar
i
i
i
P
P
P

| |
|
|
\ .
=
=
=

b. The internal pressure where the van der Waals equation applies, is given by Eq. 17.4
2
T m
U a
V V
| |
=
|
\ .

Using the density, we can calculate the molar volume using the molar mass of acetic acid.
17-16
( )
1
1
1
3
2 12.011 4 1.00794 2 15.9994 gmol
60.05256gmol
60.05256 g mol
1.049 g cm
m
m
M
M
M
V
d
V
= + +
=
=
=

3
57.24743565 cm
m
V =
3
1 6
3
m
mol 10
cm

5 3 1
5.724743565 10 m mol
m
V

=

Solving for P
i
gives,
( )
6 2
2
5 3 1
3
1.78 Pa m mol
5.724743565 10 m mol
543135171.5Pa
5.43 10 bar
i
i
i
P
P
P

=
=
=

17-17
*17.8. a. Derive the relationship
2
P V
VT
C C

=
where is the coefficient of expansion and is the compressibility.
b. The value of C
V,m
for liquid CCl
4
at 298 K and at 1 bar pressure is 89.5 J K
1
mol
1
. Obtain the value of C
P,m
using the following
data: V
m
=97 cm
3
mol
1
; =1.24 10
3
K
1
; =10.6 10
5
bar
1
.
c. Calculate C
P,m
C
V,m
for liquid acetic acid using the data given in Problem 17.7.
Solution:
Given:
1 1
,
298 K, 1bar, 89.5 J K mol ,
V m
T P C = = =

3 1 3 1 5 1
97 cm mol , 1.24 10 K , 10.6 10 bar
m
V = = = ,
data fromProblem 17.7
Required: see above
a. To derive the above relationship we start with Eq. 2.117 found in Chapter 2.
P V
T P
U V
C C P
V T
( | | | |
= +
| | (

\ . \ .

Using one of the thermodynamic equations of state, Eq. 3.128,
T V
U P
P T
V T
| | | |
= +
| |

\ . \ .

We make the following substitution:
17-18
P V
C C P = P
V P
P V
V P
P V
T
T T
P V
C C T
T T
( | | | |
+
| | (

\ . \ .

| | | |
=
| |

\ . \ .

Using the definitions of the cubic expansion coefficient and the isothermal compressibility as defined by Eq. 3.139 and Eq. 142 we further
solve,
1
P
V
V T
| |
\ .
and
1
T
V
V P
| |
\ .

The expression first becomes,
( )
P V
V
P
C C T V
T

| |
=
|
\ .

1
P T
P T
V
V P
V
V T V
V P
T V
P
T
| | | |
=
| |

\ . \ .
| | | |
=
| |

\ . \ .
| |
=
|
\ .

Thus,
( )
2
P V
P V
C C T V
VT
C C
=
=

b. Using the expression above we can solve for C
P,m
.
17-19
( ) ( )( )
2
, .
2
3 1 6 3 1
1 1
,
5 1
1.24 10 K 97 10 m mol 298 K
89.5 J K mol
10.6 10 bar
m
P m V m
P m
V T
C C
C
= +

= +
5
10 bar
1
1 1
,
1 1
,
Pa
131.4300619J K mol
131J K mol
P m
P m
C
C
=
=

c. From the data given in problem 17.7 we have,
5 3 1 3 1 10 1
5.724743565 10 m mol , 1 atm, 293K, 1.06 10 K , 9.08 10 Pa
m
V P T

= = = = =
Therefore
, , P m V m
C C is calculated as,
( ) ( )( )
2
3 1 5 3 1
, , 10 1
1 1
, ,
1 1
, ,
1.06 10 K 5.724743565 10 m mol 293 K
9.08 10 Pa
20.75628092J K mol
20.8J K mol
P m V m
P m V m
P m V m
C C
C C
C C

=
=

17-20
17.9. A liquid having a molar volume of 50 cm
3
is converted into a vapor having a molar volume of 50 dm
3
. By what factor does the
average intermolecular energy change?
Solution:
Given:
3 3
,1 , 2
50cm, 50dm
m m
V V = =
Required: factor of intermolecular energy change
Since the intermolecular energy is inversely proportional to the sixth power of the intermolecular distance, it is inversely proportional to the
square of the volume (Eq. 17.4,
2
T m
U a
V V
| |
=
|
\ .
). The volume has increased by a factor of 10
3
, and the energy therefore changes by a factor of
10
-6
.


17-21
17.10. Calculate the maximum energy of attraction, in J and in kJ mol
1
, when a Ca
2+
ion is separated from a molecule of dipole moment
6.18 10
30
C m (=1.85 D; this is the dipole moment of water) by a distance of 500 pm in a vacuum.
Solution:
Given:
30
6.18 10 C m, 500pm r = =
Required:
p
E
We can calculate the maximum energy using Eq. 17.13,
2
0
cos
4
A
p
z e
E
r

=
For a separated species, this simplifies to
2
0
4
A
p
z e
E
r
= since cos 1 =
Solving, we obtain,
( )( )( )
( )( )
19 30
2
12 2 1 2 10
20
20
2 1.602 10 C 6.18 10 C m
4 8.854 10 C N m 5.00 10 m
7.11855086 10 Nm
7.12 10 J
p
p
p
E
E
E

=

=
=

Converting to kJ per mole, we multiply by Avogadros number and 10
-3
.
( )( )
20 23 1
1
1
7.11855086 10 J 6.022 10 mol
42867.91327J mol
42.9kJ mol
p
p
p
E
E
E
=
=
=

17-22
1
, when a Ca
2+
ion is separated in a vacuum from a Cl

ion by a distance of 500
pm.
Solution:
Given: 500pm r =
Required:
p
E
We can calculate the maximum energy using Eq. 17.12,
( )( )( )
( )( )
( )( )
2
A B
0
2
19
12 2 1 2 10
19 1
19
19 23 1
1
1
4
2 1 1.602 10 C
4 8.854 10 C N m 5.00 10 m
9.22647126 10 N m
9.23 10 J
9.22647126 10 J 6.022 10 mol
555618.0991J mol
556kJ mol
p
p
p
p
p
p
p
z z e
E
r
E
E
E
E
E
E

=

=

=
=
=
=
=


17-23
1
, when a Ca
2+
ion is separated in a vacuum by a distance of 500 pm, from a
nonpolar molecule (having zero dipole moment) but a polarizability of 2.0 10
30
m
3
.
Given:
30 3
2.00 10 m, 500pm r = =
Required:
p
E
In this case, we calculate the energy of attraction using Eq. 17.14,
2
A
4
0
( )
8
p
z e
E
r

=
Solving, we obtain,
( )( )
( )( )
( )( )
2
A
4
0
2
30 3 19
4
12 2 1 2 10
20
20
20 23 1
1
1
( )
8
2.00 10 m 2 1.602 10 C
8 8.854 10 C N m 5.00 10 m
1.4762354 10 Nm
1.48 10 J
1.4762354 10 J 6.022 10 mol
8889.889586J mol
8.89kJ mol
p
p
p
p
p
p
p
z e
E
r
E
E
E
E
E
E
=

=

=
=
=
=
=


17-24
17.13. Calculate the average energy of attraction, in J and in kJ mol
1
, for two molecules of dipole moments 6.18 10
30
C m separated in a
vacuum at 25 C by a distance of 500 pm.
Solution:
Given:
30
6.18 10 C m, 25 C, 500pm T r = = =
Required:
p
E
We solve for the average energy of attraction using Eq. 17.17.
( )
( ) ( )( )( )
( )( )
2 2
A B
2 2 2 6
0 B
4
30
2 6
2 12 2 1 2 23 1 10
21
21
21 23 1
1
24
6.18 10 C m
24 8.854 10 C N m 1.381 10 J K 298 K 5.00 10 m
1.22161 10 J
1.22 10 J
1.22161 10 J 6.022 10 mol
735.653542J mol
0.736kJ
p
p
p
p
p
p
p
E
k Tr
E
E
E
E
E
E

=

=
=
=
=
=
1
mol


17-25
17.14. The following values for A and B in the Lennard-J ones 612 function (Eq. 17.21) have been given for N
2
:
A =1.34 10
5
J pm
6
B =3.42 10
10
J pm
12
Calculate the equilibrium separation r
0
and the classical dissociation energy E
0
, in J and in J mol
1
.
Solution:
Given: Eq. 17.21,
5 6 10 12
1.34 10 J pm, 3.42 10 J pm A B = =
Required: r
0,
E
0

To solve for the equilibrium separation, we take the derivative of Eq. 17.21 and set it equal to zero. The resulting value of r corresponds to
r
0
.
6 12
7 13
6
1/6
0
1/6
10 12
0 5 6
0
0
6 12
0
6 12
2
2 3.42 10 J pm
1.34 10 J pm
414.946288 pm
415 pm
p
p
A B
E
r r
dE
A B
dr r r
Ar B
B
r
A
r
r
r
= +
= =
=
| |
=
|
\ .
| |
=
|
\ .
=
=

17-26
To solve for the energy at separation we use Eq. 17.21, substitution for the radius solved above.
( ) ( )
0 6 12
0 0
5 6 10 12
0 6 12
21
0
21
0
1.34 10 J pm 3.42 10 J pm
414.946288 pm 414.946288 pm
1.3125731 10 J
1.31 10 J
A B
E
r r
E
E
E
= +

= +
=
=

Multiplying by Avogadros number and 10
-3
we convert to kJ per mole.
( )( )
21 23
0
1
0
1
0
1.3125731 10 J 6.022 10 mol
790.4315205J mol
0.790kJ mol
E
E
E
=
=
=


17-27
*17.15. The following data apply to HBr: dipole moment, =2.60 10
30
C m; polarizability, =3.58 10
30
m
3
; oscillation frequency,
v
0
=3.22 10
15
s
1
. Estimate the dipole-dipole, dipole-(induced dipole), and dispersion energies in J and in kJ mol
1
for two HBr
molecules separated by 500 pm, at 25 C.
Solution:
Given:
30 30 3 15 1
0
2.60 10 C m, 3.58 10 m, 3.22 10 s , 500pm, 25 C v r T = = = = =
Required: dipole-dipole energy, dipole-(induced dipole) energy, and dispersion energy
To determine the dipole-dipole energy for the two HBr molecules we use Eq. 17.17.
( )
( ) ( )( )
( )( )
2 2
A B
2 2 2 6
0 B
4
30
2 6
2 12 2 1 2 23 1 10
23
23
23 23 1
24
2.60 10
24 8.854 10 C N m 1.381 10 J K 298.15 K 5 10 m
3.825 206 2 10 J
3.83 10 J
3.825 206 2 10 J 6.022 10 mol
23.035 391 74 J
p
p
p
p
p
p
E
k Tr
E
E
E
E
E

=

=
=
=
=
1
2 1
mol
2.30 10 kJ mol
p
E

=

The dipole-(induced dipole) energy is given by Eq. 17.18.
17-28
( )( )
( )( )
( )( )
2
6
2
30 3 30
6
12 2 1 2 10
23
23
23 23 1
1
2 1
2
3.58 10 m 2.60 10 C m
2 8.854 10 C N m 5.00 10 m
2.78413513 10 J
2.78 10 J
2.78413513 10 J 6.022 10 mol
16.766606177J mol
1.68 10 kJ mol
p
p
p
p
p
p
p
E
r
E
E
E
E
E
E
0
=

=

=
=
=
=
=

The potential energy due to the dispersion forces is given by Eq. 17.19.
( )( )( )
( )
( )( )
2
0
6
2
34 15 1 30
6
10
21
21
21 23 1
1
1
3
4
3 6.626 10 J s 3.22 10 s 3.58 10
4 5.00 10 m
1.31254618 10 J
1.31 10 J
1.31254618 10 J 6.022 10 mol
790.4153124J mol
0.790kJ mol
p
p
p
p
p
p
p
hv
E
r
E
E
E
E
E
E
=

=
=
=
=
=
=

17-29
*17.16. The following are the polarizabilities and oscillation frequencies for Ne, Ar, and Kr:
Ne Ar Kr
Polarizability, /10
30
m
3
0.396 1.63 2.48
Frequency, v
0
/10
15
s
1
5.21 3.39 2.94

Calculate the dispersion energies for Ne, Ar, and Kr corresponding to a separation of 500 pm. Related data for He and Xe are given
in Table 17.3; plot the five calculated values against the boiling points of the noble gases:
He Ne Ar Kr Xe
Boiling point, T
b
/K 4.22 27.3 87.3 119.9 165.1

Solution:
Given:
0
, , , 500 pm, Table 17.3
b
v T r =
Required: E
p
, plot E
d
against T
b

Since we are given incomplete information for the frequency for He and Xe, we use Eq. 17.19 and the data found in Table 17.3 to solve for
v
0
.
17-30
( ) ( )
( )( )
6
0 2
6
12 1
0,He 2
34 30 3
39 1 1
0,He
39 1
0,He
4
3
For He
4 500 10 m 4.6 J mol
3 6.626 10 J s 0.20 10 m
3.615 806 419 10 mol s
3.615 806 419 10 mol
p
r E
h
=

=

=
=
1
23 1
s
6.022 10 mol
15 1
0,He

6.004 328 162 10 s

=

( ) ( )
( )( )
6
12 1
0,Xe 2
34 30 3
39 1 1
0,He
For Xe
4 500 10 m 850.0 J mol
3 6.626 10 J s 4.00 10 m
1.670 345 357 10 mol s

=

=

39 1
0,He
1.670 345 357 10 mol
=
1
23 1
s
6.022 10 mol
15 1
0,He

2.773 738 553 10 s

=

17-31
( )( )( )
( )
( )( )
( )( )
2
0
6
2
34 1 2 3
0
6
12
2
22 1 2 3
0
2
22 15 30
24 1
22
3
4
3 6.626 10 J s s m
4 500 10 m
3.180 48 10 s m
For He
3.180 48 10 6.004 328 162 10 0.20 10
7.638 658 253 10 J ; 4.6 J mol
For Xe
3.180 48 10 2.7
p
p
p
p
p
p
h
E
r
E
E
E
E
E

=
=
=
=
( )( )
( )( )
( )( )
2
15 30
21 1
2
22 15 30
22 1
22 15 30
73 738 553 10 4.00 10
1.411 491 199 10 J ; 850 J mol
For Ar
3.180 48 10 3.39 10 1.63 10
2.864 623 669 10 J ; 172.507 637 3 J mol
For Ne
3.180 48 10 5.21 10 0.396 10
p
p
p
p
E
E
E
E

=
=
=
=
( )( )
2
23 1
2
22 15 30
22 1
2.598 488 29 10 J ; 15.648 096 48 J mol
For Kr
3.180 48 10 2.94 10 2.48 10
5.750 999 912 10 J ; 346.325 214 7 J mol
p
p
p
E
E
E

=
=
=

17-32

Check Ep for He and Xe , directly taken from book or have to calculate it? Have the same values anyhow


17-33
*17.17. In Table 17.3 and Problem 17.16 the dispersion energies of noble gases were calculated for a constant interatomic distance of 500
pm. More realistic values are:
He Ne Ar Kr Xe
Interatomic distances/pm 240 320 380 400 420

Recalculate the dispersion energies for these distances, and again plot the five values against the boiling points, which were given in
Problem 17.16.
The experimental value for the enthalpy of vaporization of liquid argon is 6.7 kJ mol
1
. Make an estimate of the enthalpy of vaporization
from your calculated value of E
p
(at 380 pm), assuming the liquid to have a close-packed structure with each atom having 12 nearest
neighbors.
Solution:
Given: Table 17.3, Problem 17.16, r =500 pm,
Required: E
d
, plot E
d
against T
b
The values previously calculated (Problem 17.16) will be multiplied by the factor
6
500
pm r
| |
|
\ .
and then divided by the corresponding inteatomic distances to the power of 6 according to the following equation
2
0
6
3
4
p
h
E
r

=
Sample calculation for He:
( ) ( )
24
6
24 23 1
6
1
7.638 658 253 10 J
500
new 7.638 658 253 10 J 6.022 10 mol
240
new 376.106 126 2 J mol
p
p
p
E
E
E
=
| |
=
|
\ .
=

17-34
The values of
1
J mol
d
E

are then:
He Ne Ar Kr Xe
For 500 pm 4.6 15.6 173 346 850
For r 376 228 895 1321 2420

If each Ar atom has 12 nearest neighbors, the estimated enthalpy of vaporization is
( )
1 1
12
895 J mol 5370 J mol
2
| |
=
|
\ .

This is not bad agreement considering the simplicity of the model.


17-35
*17.18. Estimate the interaction energy between an argon atom and a water molecule at a separation of 600 pm, which is approximately the
distance of closest approach. The necessary data are: H
2
O: dipole moment, =6.18 10
30
C m; Ar: polarizability, =1.63 10
30
m
3
.
Argon forms a solid hydrate, Ar 5H
2
O, but the binding energy between Ar and H
2
O is about 40 kJ mol
1
, which is a good deal
larger than the energy calculated from the dipole moment and polarizability. Suggest a reason for this discrepancy.
Solution:
Given:
2
30 30 3 1
H O Ar binding
600 pm, 6.18 10 C m, 1.63 10 m, 40 kJ mol r E = = = =
Required: E
interaction
, explain the discrepancy
The interaction energy, with = 1, is given by Eq. 17.18
2
6
2
p
E
r
0
=
Since only H
2
O has a permanent dipole, the potential energy is halved, giving,
2
6
4
p
E
r
0
=
Solving for interaction energy of
2
Ar H O gives,
( )( )
( )( )
( )( )
2
30 3 30
6
12 2 1 2 10
23
23
23 23 1
1
3 1
1.63 10 m 6.18 10 C m
4 8.854 10 C N m 6.00 10 m
1.19924432 10 J
1.20 10 J
1.19924432 10 J 6.022 10 mol
7.221849302J mol
7.22 10 kJ mol
p
p
p
p
p
p
E
E
E
E
E
E

=

=
=
=
=
=

17-36
This value is far lower that the binding energy between
2
Ar 5H O of 40 kJ mol
-1
since there would be additional hydrogen bonding between
neighbouring water molecules.

17-37
*17.19. a. The Lennard-J ones potential
6
n
A B
E
r r
= +
can be formulated in a different way by expressing A and B in terms of the minimum energy E
min
and the value r
0
of r at the
minimum energy. Obtain the expression for E in terms of E
min
and r
0
.
b. If r* is the value of r when E =0, obtain the relationship between r* and r
0
.
c. The Lennard-J ones potential is often used with n =12, and the equations are then simpler. Obtain E in terms of E
min
and r
0
and in
terms of E
min
and r*, for this special case of n =12.
Solution:
Given: Lennard-J ones potential
Required: a. E in terms of E
min
and r
0

b. relationship between r* and r
0

c. E in terms of E
min
and r
0
, and in terms of E
min
and r* for n =12
a. We begin by taking the derivative of the Lennard-J ones potential and set it equal to zero. The resulting value of r corresponds to r
0
.
6
7 1
0 0
7 1
0 0
6
0
6
n
n
n
A B
E
r r
dE A nB
dr r r
A nB
r r
+
+
= +
= =
=

Rearranging to obtain expressions for A and B we get,
6 6
0 0
6
and
6
n n
nBr Ar
A B
n

= =
After substitution, the minimum energy becomes,
17-38
6
0
min 6
0 0
min 6 6
0 0
6 1
6
n
n
Ar A
E
r r n
A A
E
r nr
| |
= +
|
\ .
= +

Therefore A can be written as,
6
0 min
6
nr E
A
n
=

Similarly, we determine B as,
0 min
6
6
n
r E
B
n
=

Then, substituting back into the original equation, we haveE in terms of E
min
and r
0
.
6
0 min 0 min
6
6
0 0
min min 6
6
0 0
min
6 1 1
6 6
6
6 6
6
6 6
n
n
n
n
n
nr E r E
E
r n r n
r r n
E E E
n r n r
r r E n
E n r n r
| | | |
= +
| |

\ . \ .
| | | |
= +
| |

\ . \ .
| | | |
= +
| |

\ . \ .

b. If r* is the value of r when E =0, then from the Lennard-J ones potential we have,
( ) ( )
6
0
* *
n
A B
r r
= +
Rearranging this expression for r* we get,
17-39
( ) ( )
( )
( )
( )
6
6
6
* *
*
*
*
n
n
n
A B
r r
r B
A
r
B
r
A
=
=
=

Using the expressions for A and B derived above we obtain the relationship between r* and r
0
( )
( )
6
6
0 min 0 min
6 0 min
6
*
6 6
6
*
n
n
n
n
r E nr E
r
n n
r E
r
| | | |
=
| |

\ . \ .
=
6 n
6 n
| |

|
|
\ .
6
0 min
nr E
( )
6
0
6
0
6
*
n
n r
r
nr
| |
|
|
\ .
=

( ) ( )
6 6
0
6
0
6
*
* 6
n n
n
r r
n
r
r n

=
| |
=
|
\ .

c. For n =12 we use the result from part a. to get E in terms of E
min
and r
0
, and in terms of E
min
and r*.
6 12
0 0
min
6 12
0 0
min
12 6
6 12 6 12
2
r r E
E r r
r r
E E
r r
| | | |
= +
| |

\ . \ .
| |
| | | |
= |
| |
|
\ . \ .
\ .

For n =12, we get
0
r from the result of part b.
17-40
( )
6
1
1
0
6
0
12 6
0
6
0
6
6
0
* 6
* 6
12
* 6
2
*
2 *
n
n
r
r n
r n
r
r
r
r
r
r r
| |
| |
| |
| =
| |
|
\ .
\ .
\ .
| |
=
|
\ .
| |
=
|
\ .
| |
=
|
\ .
=

Therefore,
( )
( )
12
2
6
6
min
6 12
min
6 12
min
2 *
*
2 2
* *
4 4
* *
4
r
r
E E
r r
r r
E E
r r
r r
E E
r r
| |
| |
|
| | |
=
|
|
|
\ .
| |
|
\ .
\ .
| |
| | | |
= |
| |
|
\ . \ .
\ .
| |
| | | |
= |
| |
|
\ . \ .
\ .


CHAPTER
1
1
8
8
Surface Chemistry
and Colloids

Physical Chemistry
Electronic Edition


Chapter 18: Surface Chemistry and Colloids Adsorption Isotherms
18-2
Chapter 18
Adsorption Isotherms
18.1. A surface is half-covered by a gas when the pressure is 1 bar. If the simple Langmuir isotherm(Eq. 18.6) applies:
a. What is K/bar
-1
?
b. What pressures give 75%, 90%, 99%, 99.9% coverage?
c. What coverage is given by pressures of 0.1 bar, 0.5 bar, 1000 bar?

Solution

18.2. Show that, if V is the volume of gas adsorbed at pressure P, and the Langmuir isothermis obeyed, a plot of P/V against P is linear.
Explain how, fromsuch a plot, the volume V0 corresponding to complete coverage and the isothermconstant K can be determined.

Solution

18.3. The following results were reported by Langmuir for he adsorption of nitrogen on mica at 20 C:

Pressure/atm 2.8 4 6 9.4 17.1 33.5
Amount of gas
adsorbed/mm
3
at 20
C and 1 atm 12 15.1 19 23.9 28.2 33
a. Make a linear plot of these values in order to test the Langmuir isotherm, Eq. 18.6. If it applies, evaluate the constant K.
b. Suppose that 10
15
molecules cover 1 cm
2
of the surface. Make an estimate of the effective surface area in Langmuirs experiment.

Solution

18.4. a. Show that for small coverages a systemobeying the Langmuir isothermwill give a linear plot of ln (/P) against P, with a slope
of unity.
b. What is the slope if ln (Va/P) is plotted against Va at small coverages? (Va is the volume of gas adsorbed.)

Solution

Chapter 18: Surface Chemistry and Colloids Adsorption Isotherms
18-3
18.5. The following are the volumes of ammonia, reduced to STP, adsorbed by 1 g of charcoal at 0 C:

Pressure/kPa 6.8 13.5 26.7 53.1 79.4
Volume/cm
3
74 111 147 177 189
Make a plot to see if the data are consistent with the Langmuir isotherm. If so, evaluate the constants K and V0, the volume adsorbed
when the surface is saturated.

Solution

18.6. a. Suggest a method of making a linear plot to test the applicability of the Brunauer, Emmett, and Teller (BET) isotherm(Eq. 18.25)
when volumes adsorbed, V, are known at various pressures.
b. Show that the BET equation reduces to the Langmuir isothermwhen
0
. P P

Solution

18.7. The following data were obtained for the adsorption of krypton on a 1.21 g sample of a porous solid:

Pressure/Torr 1.11 3.08
Volume adsorbed/cm
3
(STP) 1.48 1.88
If the saturation vapor pressure is 19.0 Torr, estimate a surface area for the solid, assuming that a molecule of krypton occupies an
area of
21 2
2.1 10 m.

Solution

*18.8. Derive the equation
( )
3 2
12 0
3 4 12
B
exp
1 2
2
a
g
g
b E h
c
b RT
mk T

| |
=
|
\ .

For the case of adsorption with dissociation (i.e., ( )
2 0
A 2S 2 S A ; E + is the energy of adsorption per mole.

Solution
Chapter 18: Surface Chemistry and Colloids Kinetics of Surface Reactions
18-4
( )
0
12
B
exp
2
2
a
a g
g
b E h
c c
b RT
mk T
| |
=
|
\ .

For the case of adsorption where the adsorbed molecules are completely mobile on the surface (i.e., have two degrees of
translational freedom).

Solution

Kinetics of Surface Reactions
18.10. A first-order surface reaction is proceeding at a rate of
4 3 1
1.5 10 mol dm s

and has a rate constant
3 1
2.0 10 s

. What will be the
rate and the rate constant if

a. the surface area is increased by a factor of 10?
b. the amount of gas is increased tenfold at constant pressure and temperature?
If these values of and k apply to a reaction occurring on the surface of a spherical vessel of radius 10 cm:
c. What will be the rate and rate constant in a spherical vessel, of the same material, of radius 100 cm, at the same pressure and
temperature?
d. Define a new rate constant k that is independent of the gas volume V and the area S of the catalyst surface.
e. What would be its SI unit?

Solution

18.11. A zero-order reaction is proceeding at a rate of
3 3 1
2.5 10 mol dm s

and a rate constant
3 3 1
2.5 10 mol dm s

.

a. How will the changes a, b, and c in Problem18.10 affect the rate and the rate constant in this case?
b. Again, define a rate constant that is independent of S and V.
c. What would be its SI unit?

Solution

Chapter 18: Surface Chemistry and Colloids Kinetics of Surface Reactions
18-5
18.12. The decomposition of ammonia on platinum,
3 2 2
2NH N 3H = +
is first order in NH3 and the rate is inversely proportional to the hydrogen concentration (Eq. 18.39). Write the differential rate equation for
the rate of formation of hydrogen, dx/dt, in terms of the initial concentration of ammonia, a0, and the concentration x of hydrogen at time t.

Solution

*18.13. On the basis of the mechanismgiven on p. 943, derive an expression for the rate of formation of hydrogen atoms when hydrogen
gas is in contact with hot tungsten. Under what conditions is the order of reaction one-half?

Solution

18.14. A unimolecular surface reaction is inhibited by a poison I and obeys Eq. 18.36. If E is the activation energy corresponding to the
reaction of the adsorbed substrate molecule (i.e., corresponding to k) and
A
H and
I
H are the enthalpies of adsorption of A and I, what is
the activation energy

a. at very low concentration of A and I?
b. at a very high concentration of A and a very low concentration of I?
c. at a very low concentration of A and a very high concentration of I?

Solution

18.15. Suppose that a reaction
A Y Z +
Occurs initially as a homogeneous first-order reaction (rate constant k) but that the product Z is adsorbed on the surface and catalyzes the
reaction according to a law that is zero order in A and first order in Z (i.e., the termin the rate equation is | | Z
c
k ). Obtain a differential
equation for the rate of appearance of Z, and integrate it to give z as a function of time.

Solution

Chapter 18: Surface Chemistry and Colloids Surface Tension and Capillarity
18-6
18.16. Suggest explanations for the following observations, in each case writing an appropriate rate equation based on a Langmuir
isotherm:

a. The decomposition of phosphine (PH3) on tungsten is first order at low pressures and zero order at higher pressures, the activation
energy being higher at the higher pressures.
b. The decomposition of ammonia on molybdenumis retarded by the product nitrogen, but the rate does not approach zero as the
nitrogen pressure is increased.
c. On certain surfaces (e.g., Au) the hydrogen-oxygen reaction is first order in hydrogen and zero order in oxygen, with no decrease
in rate as the oxygen pressure is greatly increased.
d. The conversion of para-hydrogen into ortho-hydrogen is zero order on several transition metals.

Solution

Surface Tension and Capillarity
18.17. The surface tension of water at 20 C is 7.27 10
2
N m
1
and its density is 0.998 g cm
3
. Assuming a contact angle of zero,
calculate the rise of water at 20 C in a capillary tube of radius (a) 1 mmand (b) 10
3
cm. Take g =9.81 ms
2
. (Capillaries in a tree have
radii of about 10
3
cm, but sap can rise in a tree to much greater heights than obtained in this calculation. The reason is that the rise of sap
depends to a considerable extent on osmotic flow; because of evaporation the leaves contain solutes of higher concentration than the trunk
of the tree, and osmotic flow therefore occurs to the leaves.)

Solution

18.18. The density of liquid mercury at 273 K is 13.6 g cm
3
and the surface tension is 0.47 N m
1
. If the contact angle is 140, calculate the
capillary depression in a tube of 1-mmdiameter.

Solution

18.19. The density of water at 20 C is 0.998 g cm
3
and the surface tension is 7.27 10
2
N m
1
. Calculate the ratio between the
vapor pressure of a mist droplet having a mass of 10
12
g and the vapor pressure of water at a plane surface.

Solution

Chapter 18: Surface Chemistry and Colloids Surface Films
18-7
18.20. The two arms of a U-tube have radii of 0.05 cmand 0.10 cm. A liquid of density 0.80 g cm
3
is placed in the tube, and the height in
the narrower armis found to be 2.20 cmhigher than that in the wider arm. Calculate the surface tension of the liquid, assuming =0.

Solution

18.21. A tube is placed in a certain liquid and the capillary rise is 1.5 cm. What would be the rise if the same tube were placed in another
liquid that has half the surface tension and half the density of the first liquid? Assume that =0 in both cases.

Solution

18.22. When a certain capillary tube is placed in water, the capillary rise is 2.0 cm. Suppose that the tube is placed in the water in such a
way that only 1.0 cmis above the surface; will the water flow over the edge? Explain your answer.

Solution

*18.23. A layer of benzene, of density 0.8 g cm
3
, is floating on water of density 1.0 g cm
3
, and a vertical tube of internal
diameter 0.1 mmis inserted at the interface. It is observed that there is a capillary rise of 4.0 cmand that the contact angle is 40. Calculate
the interfacial tension between water and benzene.

Solution

18.24. A liter of water at 20 C is broken up into a spray in which the droplets have an average radius of 10
5
cm. If the surface tension of
water at 20 C is 7.27 10
2
N m
1
, calculate the Gibbs energy change when the droplets are formed.

Solution

Surface Films
18.25. Benjamin Franklin demonstrated on a number of occasions that a teaspoonful of oil put on water would produce a layer half an acre
in area (1 acre =4840 square yards; 1 yard =0.915 m). Assume a teaspoonful to be 1 cm
3
, and estimate the thickness of the film.

Solution

Chapter 18: Surface Chemistry and Colloids Surface Films
18-8
18.26. A fatty acid was spread on the surface of water in a Langmuir filmbalance at 15 C, and the following results obtained:

Area/cm
2
g
1
5.7 28.2 507 1070 2200 11100
Surface pressure/ 10
3
N
m
1

30 0.3 0.2 0.1 0.05 0.01

Estimate the molecular weight of the acid and the area per molecule when the filmwas fully compressed.

Solution

18.27. N. K. Adamcarried out surface filmstudies using a Langmuir filmbalance 14.0 cmin width having a floating barrier 13.8
cmlong. In one investigation he introduced 52.0 g of 1-hexadecanol (C16H33OH) onto the surface and measured the force on the float at
various lengths of the film, obtaining the following results:

Length/cm Force on float/10
5
N
20.9 4.14
20.3 8.56
20.1 26.2
19.6 69.0
19.1 108.0
18.6 234
18.3 323
18.1 394
17.8 531

Estimate the area per molecule when the filmwas fully compressed.

Solution
Chapter 18: Surface Chemistry and Colloids Essay Questions
18-9
Essay Questions
18.28. Describe some of the most important characteristics of a chemisorbed layer. In what ways does a physisorbed (van der Waals) layer
differ?

18.29. Derive the Langmuir adsorption isotherms for two substances competitively adsorbed on a surface. Show how these equations
interpret the kinetics of bimolecular surface reactions, distinguishing between Langmuir-Hinshelwood and Langmuir-Rideal mechanisms.

18.30. Explain clearly the distinction between inherent and induced heterogeneity of surfaces.

18.31. Explain the difference between lyophilic and lyophobic sols, with reference to some of the properties in which they differ.

18.32. What information can be obtained fromlight-scattering experiments on colloidal particles in aqueous solution?

Chapter 18: Surface Chemistry and Colloids Solutions
18-10
Solutions
18.1. A surface is half-covered by a gas when the pressure is 1 bar. If the simple Langmuir isotherm(Eq. 18.6) applies:
a. What is K/bar
-1
?
b. What pressures give 75%, 90%, 99%, 99.9% coverage?
c. What coverage is given by pressures of 0.1 bar, 0.5 bar, 1000 bar?

Solution:

Given: simple Langmuir isothermapplies, P =1 bar

Required: see above

a. For a surface that is half-covered, 0.5 = . Using Eq. 18.6 for the simple Langmuir isotherm, we replace the concentration [A] by
the pressure, to obtain the value of K in bar.
| |
| |
A
1 A
1 bar
0.5
1 1 bar
0.5 0.5
1 bar
K
K
K
K
K K
K
=
+
=
+
+ =
=

18-11
b. Here, we use a modified version of Eq. 18.6, with K replaced by P, in order to solve for the unknown pressure.We can derive a
standard equation to solve for this particular problemas the initial pressure is 1 bar.
( )
1 bar
1 1 bar
1
1
For 75% coverage:
0.75 0.75
1 0.75 0.25
3 bar
For 90% coverage:
0.90 0.90
1 0.90 0.10
P
P
P P
P P
P
P
P
P
P
=
+
+ =
=
=
=
= =
=
= =

9 bar
For 99% coverage:
0.99 0.99
1 0.99 0.01
99 bar
For 99.9% coverage:
0.999 0.999
1 0.999 0.001
999 bar
P
P
P
P
P
=
= =
=
= =
=

18-12
c. This problemis similar to b., but with pressure as the known variable and percent coverage as the unknown variable. We can
slightly modify the previous derived equation as follow:
( )
1 bar
1 1 bar
1
1
For 0.1 bar pressure:
0.1 0.1
1 0.1 1.1
0.090 909 09
0.091 or 9.1%
For 0.5 bar pressure:
0.5 0.5
1 0.5 1.5
0.333 333 333
0.33 or 33%
For 1000 bar pressure:
1000
1
P
P
P P
P P
P
P
=
+
+ =
+ =
=
+
= =
+
=
=
= =
+
=
=
=
+
1000
1000 1001
0.999 000 999
0.999 or 99.9%
=
=
=

18-13
18.2. Show that, if V is the volume of gas adsorbed at pressure P, and the Langmuir isothermis obeyed, a plot of P/V against P is linear.
Explain how, fromsuch a plot, the volume V0 corresponding to complete coverage and the isothermconstant K can be determined.

Solution:

Given: Langmuir isotherm

Required: show that plot of P/V against P is linear, explanation

The Langmuir isothermin terms of pressure P is, fromEq. 18.6,
0
1
KP
KP
V
V
=
+
=

and therefore
0
1
V KP
V KP
=
+

which rearranges to
0 0 0
1 1 P KP P
V V K V K V
+
= = +
A plot of P/V against P is therefore linear; the slope is 1/V0 and the intercept on the P/V0 axis is 1/V0K. The quantities V0 and K can thus be
obtained separately.


18-14
18.3. The following results were reported by Langmuir for he adsorption of nitrogen on mica at 20 C:

Pressure/atm 2.8 4 6 9.4 17.1 33.5
Amount of gas
adsorbed/mm
3
at 20
C and 1 atm 12 15.1 19 23.9 28.2 33
a. Make a linear plot of these values in order to test the Langmuir isotherm, Eq. 18.6. If it applies, evaluate the constant K.
b. Suppose that 10
15
molecules cover 1 cm
2
of the surface. Make an estimate of the effective surface area in Langmuirs experiment.

Solution:

Given: above table

Required: test for Langmuir isotherm, constant K, effective surface area

We know that the amount of gas adsorbed x is proportional to the percent coverage . Therefore,
| |
| |
A
1 A
aK
x
K
=
+

However, instead of the concentration, pressure is given. To convert pressure in atmospheres to concentrations, we use the ideal gas law:
atm P
n P
V RT
= =
( )
3
0.082 05 dm atm
1
K
( )
1
mol 293.15 K
( )

18-15
To convert the amount of gas adsorbed to moles:
1 atm
PV
n
RT
= =
( )( )
3
3
dm
0.082 05 dm atm
V
1
K
( )
1
mol 293.15 K
( )
3
mm V
n =
( )
3
0.082 05 dm
( )
( )
3
1
dm
mol 293.15

3 3
100 mm
3
1
mm
24 052 957.5 mol
V
n
=

Thus, the table given above becomes
-3
0.116 0.166 0.249 0.391 0.711 1.39
Amount of gas
adsorbed/10
-7
mol 4.99 6.28 7.90 9.94 11.7 13.7
a. A linear plot may be obtained by plotting 1/x against 1/[A]:
| |
1 1 1
A x aK a
= +
[A]
-1
/dm
3
mol
-1
8.62 6.02 4.02 2.56 1.41 0.719
x
-1
/10
6
mol
-1
2..00 1.59 1.27 1.01 0.85 0.73
Froma plot of x
-1
against [A]
-1
or fromlinear regression,
6
3 1
1.63 10 mol
3.82 dm mol
a
K
=
=

Here the solution manual doesnt have a plot or linear regression. Maybe add the plot and the linear regression for clearer explanation?
18-16
b. Complete coverage corresponds to
6
1.63 10 mol
( )
23 1
6.022 10 molecules mol

( )
17
9.815 86 10 molecules =
For 10
15
molecules that covers 1 cm
2
of the surface, the effective surface area in Langmuirs experiment will be:
17
9.815 86 10 molecules
( )
2
15
1 cm
10 molecules
2
2 2 2
981.586 cm
effective surface area: 9.8 10 cm or 0.098 m
| |
=
|
\ .

18-17
18.4. a. Show that for small coverages a systemobeying the Langmuir isothermwill give a linear plot of ln (/P) against P, with a slope
of unity.
b. What is the slope if ln (Va/P) is plotted against Va at small coverages? (Va is the volume of gas adsorbed.)

Solution:

Given: small coverages, see above

Required: see above

a. In order to derive the equation for the plot of ln (/P) against P, we first start with Eq.18.7,
( )
1
1 1
1 KP
=
+

Rearranging,

( )( ) 1 1 1
1
KP + =
1 KP KP + =
( ) ( )

1 2
KP KP
KP

=
=

Taking the natural logarithmon both sides yield:

( )
( ) ( )
1
ln ln ln 1 3
ln ln if 1
K
P
K
P
K
P

=
= +
( ) 4

A plot of ln (/P) against is thus linear with a slope of -1.
The problemas to prove that plot of ln (/P) against P is linear, instead of ln (/P) against . The solution manual is also wrong.
18-18
b. Since
0
, Eq. (4) can be written as V V =
0
0
ln ln ln
V V
V K
P V
| |

|
\ .

A plot of ln (V/P) against V thus has a slope of -1/V0.
18-19
18.5. The following are the volumes of ammonia, reduced to STP, adsorbed by 1 g of charcoal at 0 C:

Pressure/kPa 6.8 13.5 26.7 53.1 79.4
Volume/cm
3
74 111 147 177 189
Make a plot to see if the data are consistent with the Langmuir isotherm. If so, evaluate the constants K and V0, the volume adsorbed
when the surface is saturated.

Solution:

Given: above table

Required: constant K and V0

The Langmuir isothermcan be used in the form
0 0 0
1 1 1
or
1
V KP
V KP V V KP V
= = +
+

The data are plotted as 1/V against 1/P in the accompanying figure. The Langmuir isothermis obeyed, with
3 2 1
0
222 cm and 7.35 10 kPa V K

= =
[image]
18-20
18.6. a. Suggest a method of making a linear plot to test the applicability of the Brunauer, Emmett, and Teller (BET) isotherm(Eq. 18.25)
when volumes adsorbed, V, are known at various pressures.
b. Show that the BET equation reduces to the Langmuir isothermwhen
0
. P P

Solution

Given: volumes at various pressures

Required: see above

a. The BET isothermcan be tested in a number of ways, for example by plotting ( )
0
P V P P against P.

b. If
0
P P , the isothermbecomes
0 0
1 P P
V V K V
= +
The fraction covered
0
V
V
= and therefore,
1 P
P
K
= +
or

1
KP
KP
=
+

Which is the Langmuir isotherm.


18-21
18.7. The following data were obtained for the adsorption of krypton on a 1.21 g sample of a porous solid:

Pressure/Torr 1.11 3.08
Volume adsorbed/cm
3
(STP) 1.48 1.88
If the saturation vapor pressure is 19.0 Torr, estimate a surface area for the solid, assuming that a molecule of krypton occupies an
area of
21 2
2.1 10 m.

Solution:
Given: above table, vapor pressure =19.0 Torr, area/molecule of krypton =
21 2
2.1 10 m.

Required: surface area for the solid
Inserting of the data into the BET isotherm(Eq. 18.25) gives two simultaneous equations:

( )
( )
( )
( )
0
0 0 0
0 0
0 0
0
1
first set:
1.11 19.0 1 1.11
1.48 19.0 1.11
1 1.11
0.796 534 376 1
second set:
3.08 19.0 1
1.88 19.0 3.08
PP P
V P P V K V
V K V
V K V
V
= +
= +
= +
( )
0
0 0
3.08
1 3.08
1.955 254 998 2
K V
V K V
+
= +

Now we have two equations and two unknowns and we can therefore solve for the values of K and V0
18-22

( )
( )
0 0
0
0
0
using equation 1 to isolate an expression for
1 1.11
0.796 534 376
0.796 534 376 1 1.11
0.796 534 376 1.11 1
0.796 534 376 1.11 1
K
V K V
V K K
V K K
K V
= +
= +
=
=

18-23

( )
0
0 0
0
0
0
0
1
0.796 534 376 1.11
replace the above expression into equation 2
1 3.08
1.955 254 998
1 3.08
1.955 254 998
1
0.796 534 376 1.11
0.796 534 376 1.11 3.08
1.955 254 998
K
V
V K V
V
V
V
V
V
=
= +
= +
| |
|
\ .
+
=
( ) ( )
0
0 0
0
0
3
0
0 0
1.955 254 998 0.796 534 376 1.97
1.158 720 56 1.97
1.97
1.158 720 56
1.700 151 069 cm
substitute this value into equation 1 or 2 will solve for the value of
1 1.11
0.796 534 376
0.796 53
V V
V
V
V
K
V K V
= +
=
=
=
= +
( )( )
1
1 1.11
4 376
1.700 151 069 1.700 151 069
1
0.796 534 376 0.652 883 158
1.700 151 069
1
0.143 651 217
1.700 151 069
1
0.143 651 217 1.700 151 069
4.094 521 704 Torr
K
K
K
K
K

= +
= +
=
=
=

18-24
Now that we have the value of V0, it is possible to determine the number of molecules
At S.T.P., 22.7 L =22 700 cm3 is the volume occupied by 1 mol. A volume of 1.700 151 069 cm3 thus contains
3
1 mol
22 700 cm
3
1.700 151 069 cm
5
5
7.489 652 286 10 mol
7.489 652 286 10 mol
( )
23 1
6.022 10 molecules mol

( )
19
4.510 268 607 10 molecules =

The surface area is thus
21 2
2.1 10 m
molecule
19
4.510 268 607 10 molecules
2
2
0.094 715 64 m
surface area 947 cm
=
=

18-25
( )
3 2
12 0
3 4 12
B
exp
1 2
2
a
g
g
b E h
c
b RT
mk T

| |
=
|
\ .

For the case of adsorption with dissociation (i.e., ( )
2 0
A 2S 2 S A ; E + is the energy of adsorption per mole.
Solution:
Given: see above
Required: derivation for the case of adsorption with dissociation
The process is
( )
2
A 2S 2 S A +
and

( )
2 2
2 2
2
1
1
a a
c
g s g s
c
g
c N
K
c c N V N
K
c
= =
| |
=
|
\ .

In terms of partition functions,

( )
( )
2
0
2
3 2
0
3 2
B
exp
exp if 1
2
a
c
g s
a
c s
g
q E
K
q q RT
h b E
K q
RT
mk T b
| |
=
|
\ .
| |
= =
|
\ .

Therefore

( )
3 2
12 0
3 4
12
B
exp
1 2
2
a
g
g
h b E
c
RT
mk T b

| |
=
|
\ .

18-26
( )
0
12
B
exp
2
2
a
a g
g
b E h
c c
b RT
mk T
| |
=
|
\ .

For the case of adsorption where the adsorbed molecules are completely mobile on the surface (i.e., have two degrees of
translational freedom).
Solution:
Given: see above
Required: derivation for adsorption where the adsorbed molecules are mobile on the surface
The adsorption centers need no longer be regarded as reactants; the equilibriumis between gas molecules and molecules forming the two-
dimensional layer:

( )
( )
B 0
2
3 2
B
3
2
exp
2
a a
c
g g
a
c
g
c N S
K
c N V
mk T E
b
h RT
K
mk T
b
h
= =
| |
|
\ .
=

Therefore

( )
0
12
B
exp
2
a
a g
g
b E h
c c
b RT
mk T
| |
=
|
\ .

18-27
18.10. A first-order surface reaction is proceeding at a rate of
4 3 1
1.5 10 mol dm s

and has a rate constant
3 1
2.0 10 s

. What will be the
rate and the rate constant if

a. the surface area is increased by a factor of 10?
b. the amount of gas is increased tenfold at constant pressure and temperature?
If these values of and k apply to a reaction occurring on the surface of a spherical vessel of radius 10 cm:
c. What will be the rate and rate constant in a spherical vessel, of the same material, of radius 100 cm, at the same pressure and
temperature?
d. Define a new rate constant k that is independent of the gas volume V and the area S of the catalyst surface.
e. What would be its SI unit?
Solution:
Given: reaction rate =
4 3 1
1.5 10 mol dm s

, rate constant =
3 1
2.0 10 s

Required: see above
a. The rate and the rate constant are both increased by a factor of 10:
3 3 1 2 1
1.5 10 mol dm s ; 2.0 10 s k

= =
b. The rate of conversion (mol s
-1
) remains the same, but since the volume is increased by a factor of 10, the rate is reduced by a factor
of 10, as is the rate constant:
5 3 1 4 1
1.5 10 mol dm s ; 2.0 10 s k

= =
c. Increasing the radius by a factor of 10 increases the surface area by a factor of 100 and the volume by a factor of 1000. The rate and
the rate constant are thus reduced by a factor of 10:
5 3 1 4 1
1.5 10 mol dm s ; 2.0 10 s k

= =
d. Since k is proportional to S and inversely proportional to V, the constant '
kV
k
S
= is independent of V and S.
e. Its SI units is ms
-1
.
18-28
18.11. A zero-order reaction is proceeding at a rate of
3 3 1
2.5 10 mol dm s

and a rate constant
3 3 1
2.5 10 mol dm s

.

a. How will the changes a, b, and c in Problem18.10 affect the rate and the rate constant in this case?
b. Again, define a rate constant that is independent of S and V.
c. What would be its SI unit?
Solution:
Given: reaction rate =
3 3 1
2.5 10 mol dm s

, rate constant =
3 3 1
2.5 10 mol dm s

Required: see above
The arguments here are the same as in Problem18.10, and thus,
a. ( )
2 3 1
a' 2.5 10 mol dm s k

=

2 1
2.5 10 s

=

( )
4 3 1
4 1
b' 2.5 10 mol dm s
2.5 10 s
k

=
=

( )
4 3 1
4 1
c' 2.5 10 mol dm s
2.5 10 s
k

=
=

b. ' k kV S =
c.
2 1
mol m s

18-29
18.12. The decomposition of ammonia on platinum,
3 2 2
2NH N 3H = +
is first order in NH3 and the rate is inversely proportional to the hydrogen concentration (Eq. 18.39). Write the differential rate equation for
the rate of formation of hydrogen, dx/dt, in terms of the initial concentration of ammonia, a0, and the concentration x of hydrogen at time t.
Solution:
Given: see above
Required: see above
To solve this problem, we can use a table that shows the initial concentrations of the reactants and the products and the concentration after a
time t, assuming that x amount of 3H2 has been consumed.
3
2NH
= 2
N
+ 2
3H
Initial concetrations 0
a
0 0
Concentrations after time t:
0
2
3
x
a

3
x

x

0
0
0
2
3
3 2
3
2
3
x
k a
dx
dt x
ka kx dx
dt x
ka dx k
dt x
| |
|
\ .
=
=
=

18-30
*18.13. On the basis of the mechanismgiven on p. 943, derive an expression for the rate of formation of hydrogen atoms when hydrogen
gas is in contact with hot tungsten. Under what conditions is the order of reaction one-half?
Solution:
Given: see above
Required: derivation for the rate of formation of hydrogen atoms
FromEq. 18.14, the fraction of bare surface is
| |
12
12
2
H 1 K
| |
12
12
2
1
1
1 H K
=
+

Rate of H atomformation is thus,

( )| |
| |
| |
2
2
12
12
2
1 H
H
1 H
k
k
K

=
=
+

Kinetics are one-half order when | |
12
12
2
H 1 K ; i.e., at high pressure when the surface is fully covered:
| |
12
2 12
H
k
K
=

18-31
18.14. A unimolecular surface reaction is inhibited by a poison I and obeys Eq. 18.36. If E is the activation energy corresponding to the
reaction of the adsorbed substrate molecule (i.e., corresponding to k) and
A
H and
I
H are the enthalpies of adsorption of A and I, what is
the activation energy

a. at very low concentration of A and I?
b. at a very high concentration of A and a very low concentration of I?
c. at a very low concentration of A and a very high concentration of I?
Solution:
Given: see above
Required: see above
We know that exp
E
k
RT
| |
|
\ .
,
A
exp
H
K
RT
| |
|
\ .
and
I
exp
i
H
K
RT
| |
|
\ .

a. | |
( )
A
A exp
E H
kK
RT
+ (
=
(

b. exp
E
k
RT
| |
=
|
\ .

c.
| |
| |
( )
A I
A
exp
I
i
E H H kK
K RT
+ (
=
(


18-32
18.15. Suppose that a reaction
A Y Z +
Occurs initially as a homogeneous first-order reaction (rate constant k) but that the product Z is adsorbed on the surface and catalyzes the
reaction according to a law that is zero order in A and first order in Z (i.e., the termin the rate equation is | | Z
c
k ). Obtain a differential
equation for the rate of appearance of Z, and integrate it to give Z as a function of time.
Solution:
Given: see above
Required: obtain differential equation, integration to give Z as a function of time
We can start by constructing a table similar to Problem18.12
A Y + Z
Initially: 0
a
0 0
At time t: 0
a z z z

( )
( )
( )
0
0
0
0
s
s
s
s
dz
k a z k z
dt
dz
ka kz k z
dt
dz
ka k k z
dt
dz
dt
ka k k z
= +
= +
= +
=
+

Let ( )
0 s
ka k k z y + = ; ( )
( )
and
s
s
dy
dy k k dz dz
k k
= =

18-33

( )
( )
( )
( )
( )
0
1
1
ln I
substitute:
1
ln I
s
s
s
s
dy
dt
k k y
y t
k k
ka k k z t
k k
=
= +
+ = + (

In order to solve for the constant I, we apply the boundary condition, 0, 0 z t = =

( )
( )
( )
( )
0
0
1
ln 0 0 I
1
ln I
s
s
s
ka k k
k k
ka
k k
+ = + (

Now, we substitute the expression for the constant I back in to the integrated equation to obtain an expression for z.
18-34
( )
( )
( )
( )
( )
( )
( )
( ) ( ) { }
( )
( )
( )
( )
( )
( )
( ) ( )
( )
0
0 0
0 0
0
0
0
0
0
0
0 0
0
1
ln I
1 1
ln ln
1
ln ln
1
ln
ln
exp
exp
exp
s
s
s
s s
s
s
s
s
s
s
s
s
s s
s
ka k k z t
k k
ka k k z t ka
k k k k
ka k k z ka t
k k
ka k k z
t
k k ka
ka k k z
t k k
ka
ka k k z
t k k
ka
ka k k z ka t k k
k k z ka
+ = + (

+ = + (

+ = (

+ (
=
(

+ (
=
(

+
= (

+ = (

= ( )
( )
( )
( )
( ) { }
0
0 0
0
exp
exp 1
s
s
s
s
s
t k k ka
ka t k k ka
z
k k
ka
z t k k
k k
(

(

=
= (

18-35
18.16. Suggest explanations for the following observations, in each case writing an appropriate rate equation based on a Langmuir
isotherm:

a. The decomposition of phosphine (PH3) on tungsten is first order at low pressures and zero order at higher pressures, the activation
energy being higher at the higher pressures.
b. The decomposition of ammonia on molybdenumis retarded by the product nitrogen, but the rate does not approach zero as the
nitrogen pressure is increased.
c. On certain surfaces (e.g., Au) the hydrogen-oxygen reaction is first order in hydrogen and zero order in oxygen, with no decrease
in rate as the oxygen pressure is greatly increased.
d. The conversion of para-hydrogen into ortho-hydrogen is zero order on several transition metals.
Solution:
Given: Langmuir isotherm, information above
Required: suggest explanations
a. The general rate equation is Eq. 18.34. At low pressures the surface is sparsely covered and
| |
observed 0
A ;
a a ad
kK E E H = = +
At high pressure it is fully covered and

observed 0
; & 0
a a ad
k E E H = = <
b. Reaction occurs on certain surface sites on which N2 is not adsorbed. The rate equation is Eq. 18.36.
c. This is a Langmuir-Rideal mechanism. The general equation is Eq. 18.44; | |
2
H 2
H K is small and | |
2
O 2
O K is large, so that
| |
2
H k =
d. The mechanismis
[image]
with the surface fully covered. The rate is
| |( )
2
2
H 1 k =
18-36
where 1 is given by Eq. 18.15; thus

k
K
=
18-37
18.17. The surface tension of water at 20 C is 7.27 10
2
N m
1
and its density is 0.998 g cm
3
. Assuming a contact angle of zero,
calculate the rise of water at 20 C in a capillary tube of radius (a) 1 mmand (b) 10
3
cm. Take g =9.81 ms
2
. (Capillaries in a tree have
radii of about 10
3
cm, but sap can rise in a tree to much greater heights than obtained in this calculation. The reason is that the rise of sap
depends to a considerable extent on osmotic flow; because of evaporation the leaves contain solutes of higher concentration than the trunk
of the tree, and osmotic flow therefore occurs to the leaves.)
Solution:
Given:
2 1 3 2
20 C, 7.27 10 N m , 0.998 g cm , 0 , 9.81 ms T g

= = = = =

3
1 2
1 mm, 10 cm r r

= =
Required: rise of water
According to Eq. 18.54, the capillary rise is given by

2
h
gr
=
We first convert everything to SI units.

0.998 g =
3
cm
1 kg
1000 g
3 3
100 cm
3
3
m
998 kg m

=

a.
3
For 1 mm 10 m, r

= =
18-38
( )
( )( )( )
2 1
3 2 3
2
2
2 7.27 10 N m
998 kg m 9.81 ms 10 m
kg m
we know that 1N 1
s
kg
2 7.27 10
h
h

=
=
=
m
2
s
1
m
998 kg
| |
|
|
\ .
( )
3 2
m 9.81 ms

( )( )
3
2
10 m
0.148 513 13 m
1.49 10 mor 1.49 cm
h
h
=
=

b.
3 5
For 10 cm 10 m, r

= =
( )
( )( )( )
2 1
3 2 5
2 7.27 10 N m
998 kg m 9.81 ms 10 m
1.485 131 323 m
1.49 m
h
h
h

=
=
=

18-39
18.18. The density of liquid mercury at 273 K is 13.6 g cm
3
and the surface tension is 0.47 N m
1
. If the contact angle is 140, calculate the
capillary depression in a tube of 1-mmdiameter.
Solution:
Given:
3 1
273 K, 13.6 g cm , 0.47 N m , 140 , 1 mm T d

= = = = =
Required: capillary depression
FromEq. 18.55,

2 cos
13.6 g
h
gr

=
=
3
cm
1 kg
1000 g
3 3
100 cm
( ) ( )
( )( )( )
3
3
3
4
1
3 2 4
m
13 600 kg m
10 m
5 10 m
2 2
2 0.47 N m cos 140
13 600 kg m 9.81 ms 5 10 m
0.010 794 534 m
10.8 mm
d
r
h
h
h

=
= = =
=
=

18-40
18.19. The density of water at 20 C is 0.998 g cm
3
and the surface tension is 7.27 10
2
N m
1
. Calculate the ratio between the
vapor pressure of a mist droplet having a mass of 10
12
g and the vapor pressure of water at a plane surface.
Solution:
Given:
3 2 1 12
20 C, 0.998 g cm , 7.27 10 N m , 10 g T m

= = = =
Required: ratio between the vapor pressure of a mist droplet and of water
12
10 g
Volume of droplet
M

= =
0.998 g
( )
3
12 3
18 3
3
13
13
18 3
7
cm
1.002 004 008 10 cm
1.002 004 008 10 m
4
3
3
4
3 1.002 004 008 10 m
4
6.207 646 102 10 m
V
V
V r
V
r
r
r
=
=
=
| |
=
|
\ .
(
( =
(

=

18-41
( )
0
2 1 3
0
2
ln
2 7.27 10 N m 18.02 10 kg
ln
P M
P rRT
P
P

=

=
1
mol
( )
998 kg
( )( )
3 7 1
m 6.207 646 102 10 m 8.3145 J mol

1
K
( )
298.15 K
( )
2 2
2
2
0
kg m
we know that 1N 1 and 1 J 1 kg m s
s
kg
2 7.27 10
ln
P
P
= =
=
m
2
s
1
m
( )
3
3
18.02 10
998 m
| |
|
|
\ .
( )
7
6.207 646 102 10 m
( )
8.3145 kg
2
m
2
s
( )
( )
( )
3
0
3
0
298.15
ln 1.706 046 055 10
exp 1.706 046 055 10
P
P
P
P
=
=

0
0
1.001 707 502
1.0017
P
P
P
P
=
=

18-42
18.20. The two arms of a U-tube have radii of 0.05 cmand 0.10 cm. A liquid of density 0.80 g cm
3
is placed in the tube, and the height in
the narrower armis found to be 2.20 cmhigher than that in the wider arm. Calculate the surface tension of the liquid, assuming =0.
Solution:
Given:
3
1 2
0.05 cm, 0.10 cm, 0.80 g cm , 2.20 cm, 0 r r h
= = = = =
Required:
FromEq. 18.54, the height is
2
r g
and the difference in heights is

1 2
2 1 1
h
g r r
| |
=
|
\ .

Thus

( )( )
( )
( )( )
4 3 3 3 2
1
3 3 2
2 1 1
0.022 m
5 10 m 10 m 0.80 10 kg m 9.81 ms
2 2000 1000 m
0.022 m
0.80 10 kg m 9.81 ms
0.022 m

| |
=
|
\ .
1
0.254 841 998 kg m
=
( )
2
2
1
1
s
0.086 328 kg s
0.086 328 N m
0.086 N m
=
=
=

18-43
18.21. A tube is placed in a certain liquid and the capillary rise is 1.5 cm. What would be the rise if the same tube were placed in another
liquid that has half the surface tension and half the density of the first liquid? Assume that =0 in both cases.
Solution:
Given: capillary rise =1.5 cm, =0,
2 1
1
2
= ,
2 1
1
2
=
Required: capillary rise in new liquid
The rise is proportional to
and is therefore the same in the second liquid, i.e., 1.5 cm.

18-44
18.22. When a certain capillary tube is placed in water, the capillary rise is 2.0 cm. Suppose that the tube is placed in the water in such a
way that only 1.0 cmis above the surface; will the water flow over the edge? Explain your answer.
Solution:
Given: capillary rise =2.0 cm, 1,0 cmabove surface
Required: Explanation
No, the water does not flow over the edge. The meniscus will rise to the top of the tube and then the radius of curvature will decrease until
the capillary pressure just balances the pressure of the column of liquid; equilibriumis then established. This will occur when the radius of
curvature at the surface is half what it is in a longer tube.

18-45
*18.23. A layer of benzene, of density 0.8 g cm
3
, is floating on water of density 1.0 g cm
3
, and a vertical tube of internal
diameter 0.1 mmis inserted at the interface. It is observed that there is a capillary rise of 4.0 cmand that the contact angle is 40. Calculate
the interfacial tension between water and benzene.
Solution:
Given:
3 3
benzene water
0.8 g cm , 1.0 g cm , 0.1 mm, 4.0 cm, 40
i
d h

= = = = =
Required:
The equation that applies is an extension of Eq. 18.55:

( )
( )
3 3
2cos
where is the difference between the two densities. Then
1.00 0.80 10 kg m
rh g

=
9.81 m
(

( )
2
s 0.040 m
( )
4
0.5 10 m
( )
( )
( )
3 2
3 1 2
2cos 40
2.561 209 102 10 kg s
2.56 10 N m N kg ms
=
=


18-46
18.24. A liter of water at 20 C is broken up into a spray in which the droplets have an average radius of 10
5
cm. If the surface tension of
water at 20 C is 7.27 10
2
N m
1
, calculate the Gibbs energy change when the droplets are formed.
Solution:
Given:
5 2 1
water droplet
20 C, 1 L, 10 cm, 7.27 10 N m T V r

= = = =
Required: Gibbs energy change
The Gibbs energy change is the work done, which is the surface tension multiplied by the change in surface area (Eq. 18.50).
The surface are of the water in bulk can be estimated on the assumption that the liter of water was present as a sphere. The volume,
3
1 dm,
is
3 3
10 m
, and the radius r is

3
13
13
3 3
4
3
3
4
3 10 m
4
0.062 035 049 m
V r
V
r
r
r
=
| |
=
|
\ .
| |
=
|
\ .
=

The surface area,
2
4 r , is thus
( )
2
2
4 0.062 035 049 m =0.048 359 758 m
The surface are of each droplet is
( )
2
7 13 2
5
4 10 m 1.256 637 061 10 m
here is the average radius of each droplet, i.e., 10 cm r
=

And the volume of each droplet is
18-47
( )
3
7 21 3
4
10 m 4.188 790 205 10 m
3

=
The number of droplets is therefore the volume of water in bulk divided by the volume of each droplet

3 3
17
21 3
10 m
2.387 324 146 10 droplets
4.188 790 205 10 m

Now that we know the number of droplets and the surface area for a single droplets, we can calculate the total surface area of the droplets:

( )( )
17 13 2 2
2.387 324 146 10 1.256 637 061 10 m 299 99.999 99 m
=
This is effectively the increase in surface area, and the increase in Gibbs energy is

( )( )
2 1 2
Gibbs energy surfae area
Gibbs energy 7.27 10 N m 299 99.999 99 m
Gibbs energy 2 180.999 999 J
Gibbs energy 2.181 kJ

=
=
=
=

18-48
18.25. Benjamin Franklin demonstrated on a number of occasions that a teaspoonful of oil put on water would produce a layer half an acre
in area (1 acre =4840 square yards; 1 yard =0.915 m). Assume a teaspoonful to be 1 cm
3
, and estimate the thickness of the film.
Solution:
Given: see above
Required: estimation of the thickiness of the film
( )
2
2 2
An acre is 4840 square yards 4840 0.915 m 4052 m = = . Thus, half an acre is approximately
2
2000 m . The thickness of the filmis
thus

6 3
10
2
10 m
5 10 m 5
2000 m
= =
This is a reasonable estimate, considering the approximate nature of the area and volume. Lord Rayleigh later estimated the thickness of an
oil filmto be about 10 , and similar values were obtained in Langmuirs work.
18-49
18.26. A fatty acid was spread on the surface of water in a Langmuir filmbalance at 15 C, and the following results obtained:

Area/cm
2
g
1
5.7 28.2 507 1070 2200 11100
Surface pressure/ 10
3
N
m
1

30 0.3 0.2 0.1 0.05 0.01

Estimate the molecular weight of the acid and the area per molecule when the filmwas fully compressed.
Solution:
Given: 15 C T = , above table
Required: molecular weight of the acid, area per molecule when filmis fully compressed
At the three lower pressures, A is constant within the experimental error and has a value of

( )
4 1 1
1.11 10 N mkg J kg

=
A is equal to RT and therefore,

1
A 8.3145 288.15 2395.823 175 J mol

= =
The molar mass is thus

2395.823 175 J
1
4
mol
1.11 10 J
1 1
1
1
0.215 839 925 kg mol 215.839 925 7 g mol
kg
MW 216 g mol

= =
=

At the highest pressure, i.e., when the filmis fully compressed, the area is
2 1
5.7 cm g
. Since
23
216 g 6.022 10 molecules, =

23 6
15
6.022 10 10
1 g 2.787 962 963 10 molecules
216

= =
18-50
Thus, 1 molecule occupies

2 1
5.7 cm g
area per molecule

=
15 1
2.787 962 963 10 molecule g
15 2 1
area per molecule 2.044 503 487 10 cm molecule

=

2 1
2 1
area per molecule 0.204 450 348 nm molecule
area per molecule for fully compressed film 0.204 nm molecule
=
=

18-51
18.27. N. K. Adamcarried out surface filmstudies using a Langmuir filmbalance 14.0 cmin width having a floating barrier 13.8
cmlong. In one investigation he introduced 52.0 g of 1-hexadecanol (C16H33OH) onto the surface and measured the force on the float at
various lengths of the film, obtaining the following results:

Length/cm Force on float/10
5
N
20.9 4.14
20.3 8.56
20.1 26.2
19.6 69.0
19.1 108.0
18.6 234
18.3 323
18.1 394
17.8 531

Estimate the area per molecule when the filmwas fully compressed.
Solution:
Given: see above
Required: estimate the area per molecule for fully compressed film.
The molecular weight of 1-hexadecanol is 242.43 g mol
-1
, and 52.0 g therefore contains
52.0 g
242.43 g
1
1 g
mol

6
10 g
( )( )
7
7 23 1 17
2.144 949 057 10 mol

2.144 949 057 10 mol 6.022 10 molecules mol 1.291 688 322 10 molecules

=
=
We can start by constructing a table showing all
surface pressures and area per molecule
18-52
Length/cm Area/cm
2
Force/10
-5
N
Surface Pressure/
10
-4
N m
-1

Area per
molecule/nm
2

20.9 292.6 4.14 3.00 0.227
20.3 284.2 8.56 6.20 0.220
20.1 281.4 26.2 19.0 0.218
19.6 274.4 69.0 50.0 0.212
19.1 267.4 108 78.3 0.207
18.6 260.4 234 169.6 0.202
18.3 256.2 323 234.1 0.198
18.1 253.4 394 285.5 0.196
17.8 249.2 531 384.8 0.193
Here,
Area Length filmwidth =
Surface Pressure Force length of floating barrier =
( )
17
Area
Area per molecule
number of molecules i.e. 1.291 688 322 10 molecules
=

18-53
Since we do not know if fully compressed corresponds to the largest surface pressure in the above table, we can plot a graph of Surface
pressure vs. Area per molecule, and do extrapolation to find the value of area per molecule for fully compressed film.
[image]
Fromthe graph, area that corresponds to fully compressed layer =0.19 nm
2
.
Formatted: Normal

CHAPTER
1
1
9
9
Transport Properties

Physical Chemistry
Electronic Edition


Chapter 19: Transport Properties Viscosity
19-2
Chapter 19
Viscosity
19.1. In a normal adult at rest the average speed of flow of blood through the aorta is 0.33 m s
1
. The radius of the aorta is 9 mm and the
viscosity of blood at body temperature, 37 C, is about 4.0 10
3
kg m
1
s
1
. Calculate the pressure drop along a 0.5 m length of the
aorta.
Solution
19.2. A typical human capillary is about 1 mm long and has a radius of 2 m. If the pressure drop along the capillary is 20 Torr,
a. calculate the average linear speed of flow of blood of viscosity 4.0 10
3
kg m
1
s
1
;
b. calculate the volume of blood passing through each capillary per second; and
c. estimate the number of capillaries in the body if they are supplied by the aorta described in Problem 19.1.
Solution
*19.3. The viscosity of ethylene at 25.0 C and 101.325 kPa is 9.33 10
6
kg m
1
s
1
. Estimate
a. the molecular diameter,
b. the mean free path,
c. the frequency of collisions Z
A
experienced by a givenmolecule, and
d. the collision density Z
AA
.

Solution
19-3
*19.4. For nonassociated liquids the fluidity (i.e., the reciprocal of the viscosity) obeys to a good approximation an equation of the
Arrhenius form
/
e
a
E RT
A

=
where A and E
a
are constants.
a. For liquid CCl
4
the viscosity at 0.0 C is 1.33 10
3
kg m
1
s
1
and the activation energy E
a
is 10.9 kJ mol
1
. Estimate the
viscosity at 40.0 C.
b. The Arrhenius equation does not apply well to associated liquids such as water, but it can be used over a limited temperature
range. At 20.0 C the viscosity of water is 1.002 10
3
kg m
1
s
1
and the activation energy for fluidity 18.0 kJ mol
1
. Estimate the
Solution
19.5. At 20.0 C the viscosity of pure toluene is 5.90 10
4
kg m
1
s
1
. Calculate the intrinsic viscosities of solutions containing 0.1 g dm
3
of polymer in toluene and having the following viscosities:
a. 5.95 10
4
kg m
1
s
1
b. 6.05 10
4
kg m
1
s
1
c. 6.27 10
4
kg m
1
s
1
These solutions are sufficiently dilute that the reduced specific viscosity can be taken to be the intrinsic viscosity.
Solution
*19.6. Suppose that solutions (a) and (c) in Problem 19.5 correspond to polymers of molecular weights 20 000 and 40 000, respectively.
Assuming the Mark-Houwink equation 19.33 to apply, make an estimate of the molecular weight of the polymer in solution (b).
Solution
19-4
19.7. a. The activation energy for the fluidity of n-octane is 12.6 kJ mol
1
and the viscosity at 0 C is 7.06 10
4
kg m
1
s
1
. Estimate the
viscosity at 40.0 C, assuming the Arrhenius equation to apply.
b. A better temperature law for the viscosity of n-octane has been found to be
=A(T/K)
1.72
exp(543/(T/K)
where T is expressed in kelvins.
Make another estimate of the viscosity at 40 C. What is the effective activation energy at 20 C?
Solution
*19.8. Over its entire liquid range the viscosity of water is represented to within 1% by the following empirical formula:
3 2
(20 C) 3.1556( 20.0) 1.925 10 ( 20.0)
ln
( C) 109.0
t t
t t

| | +
=
|
+
\ .

where t is the value of the temperature in degrees Celsius. Make a better estimate of the viscosity of water than obtained by the use
of the Arrhenius equation (Problem 19.4b).
To what activation energies does this empirical expression correspond at
a. 20 C?
b. 100 C?
Give a qualitative explanation for the difference between the two values.
Solution
*19.9. Consider a hypothetical gas in which the molecules have mass but no size and do not interact with each other.
a. What would be the viscosity of such a gas?
b. Suppose instead that the molecules have zero size but attract one another. What can you then say about the viscosity?
c. If they repel one another, what would the viscosity be?
d. Give a clear explanation of your conclusions in all three cases.
Solution
Chapter 19: Transport Properties Diffusion
19-5
Diffusion
19.10. The molecular diameter of the helium atom is 0.225 nm. Estimate, at 0 C and 101.325 kPa,
a. the viscosity of the gas,
b. the self-diffusion coefficient,
c. the mean speed of the molecules,
d. the mean free path,
e. the collision frequency Z
A
, and
f. the collision density Z
AA
.

Solution
19.11. Calculate the mean square distance traveled by a molecule of H
2
at 20 C and 101.325 kPa in 10 s (D =1.005 10
4
m
2
s
1
).
Solution
19.12. Solutions of (a) glucose (D =6.8 10
10
m
2
s
1
) and (b) tobacco mosaic virus (D =5.3 10
12
m
2
s
1
) were maintained at a
constant temperature of 20 C and without agitation for 100 days. How far would a given molecule of each be expected to diffuse in
that time?
Solution
19.13. Estimate the diffusion coefficient of cupric sulfate in water at 25 C from the molar conductivities given in Table 7.3 (p. 291).
Solution
19.14. Estimate the diffusion coefficient of sodium acetate in water at 25 C from the following mobility values:
Na
+
: 5.19 10
4
cm
2
V
1
s
1

CH
3
COO
: 4.24 10
4
cm
2
V
1
s
1

Solution
Chapter 19: Transport Properties Sedimentation and Diffusion
19-6
19.15. The diffusion coefficient for horse hemoglobin in water is 6.3 10
11
m
2
s
1
at 20 C. The viscosity of water at 20 C is 1.002 10
3
kg m
1
s
1
and the specific volume of the protein is 0.75 cm
3
g
1
. Assume the hemoglobin molecule to be spherical and to obey
Stokess law, and estimate its radius and the molecular weight.
Solution
19.16. If the diffusion coefficient for insulin is 8.2 10
11
m
2
s
1
at 20 C, estimate the mean time required for an insulin molecule to
diffuse through a distance equal to the diameter of a typical living cell ( 10 m).
Solution
*19.17. A colloidal particle is spherical and has a diameter of 0.3 m and a density of 1.18 g cm
3
. Estimate how long it will take for the
particle to diffuse through a distance of 1 mm in water at 20 C ( =1.002 10
3
kg
3
m
1
s
1
; the density of water at 20 C =0.998
g cm
3
). (See also Problem 19.21.)
Solution
Sedimentation and Diffusion
19.18. Diphtheria toxin was found to have, at 20 C, a sedimentation coefficient of 4.60 Svedbergs and a diffusion coefficient of
5.96 10
7
cm
2
s
1
. The toxin has a specific volume of 0.736 cm
3
g
1
, and the density of water at 20 C is 0.998 g cm
3
. Estimate a
value for the molecular weight of the toxin.
Solution
19.19. A protein has a sedimentation coefficient of 1.13 10
12
s
1
at 25 C and a diffusion coefficient of 4.2 10
11
m
2
s
1
. The density of
the protein is 1.32 g cm
3
and that of water at 25 C is 0.997 g cm
3
. Calculate the molecular weight of the protein.
Solution
*19.20. A protein of molecular weight 60 000 has a density of 1.31 g cm
3
and in water at 25 C ( =0.997 g cm
3
; =8.937 10
4
kg m
1
s
1
) it has a sedimentation coefficient of 4.1 10
13
s
1
. Calculate the frictional coefficient f
a. from the sedimentation coefficient, and
b. by the use of Stokess law.
Suggest a reason why the two values are not quite the same.
Solution
19-7
*19.21. How long will it take the particle from Problem 19.17 to sediment a distance of 1 mm in the earths gravitational field (g =9.81 m s
2
)?
Solution
*19.22. An aqueous colloidal solution contains spherical particles of uniform size and of density 1.33 g cm
3
. The diffusion coefficient at 25
C is 1.20 10
11
m
2
s
1
; make an estimate of the sedimentation coefficient ((H
2
O) =0.997 g cm
3
; (H
2
O) =8.937 10
4
kg m
1
s
1
).
Solution
19.23. At 20 C, -globulin has a sedimentation constant of 7.75 10
13
s, a diffusion coefficient in water of 4.8 10
11
m
2
s
1
, and a
density of 1.353 g cm
3
. The density of water at 20 C is 0.998 g cm
3
.
a. Estimate the molecular weight of -globulin.
b. Assuming the Stokes-Einstein equation to apply, estimate the radius of the protein molecule. The viscosity of water at 20 C is
1.002 10
3
kg m
1
s
1
.
Solution
*19.24. A sample of human hemoglobin had a sedimentation constant of 4.48 Svedbergs in water at 20 C and a diffusion coefficient of 6.9
10
11
m
2
s
1
. The specific volume of human hemoglobin is 0.749 cm
3
g
1
3
.
a. Estimate the molecular weight of human hemoglobin.
b. How far would a molecule diffuse in 1 minute?
c. Neglect diffusion and estimate how far a molecule would sediment in 1 minute.
d. In a centrifuge rotating at 15 000 rpm, how far would a molecule sediment in 1 minute if it were 20 cm from the center of
rotation?
e. Assume the molecule to be spherical and estimate its radius by the use of the Stokes-Einstein equation.
f. Estimate the radius from the molecular weight and the density.
Solution
19-8
*19.25.In the first decade of the twentieth century J ean Perrin carried out important investigations on the sedimentation, in the gravitational
field, of particles of gamboge, mastic, and other paint pigments. Consider particles of density 1.2 g cm
3
and of the following radii:
a. 1 mm
b. 0.1 mm
c. 10 m
d. 1 m
e. 10 nm
In each case, assuming Stokess law to apply, estimate the distance the particle would sediment in 1 hour, in water at 20 C
(viscosity, =1.002 10
3
kg m
1
s
1
and density 0.998 g cm
3
).
f. In the case of the particle having a radius of 10 nm, what speed of rotation in an ultracentrifuge would be required to bring about a
sedimentation of 1 mm in 1 hour? Take the distance from the axis of rotation to be 10 cm.
Solution
*19.26. Perrin also carried out, using pigment particles, experiments on Brownian movement in which he determined distances traveled by
individual particles in various periods of time. For each of the particles of five different radii mentioned in the previous problem,
estimate the diffusion coefficient and the average distance traveled in 1 hour. Take the water temperature again as 20C and use the
data of Problem 19.25.
Solution
*19.27. A pure protein in water is centrifuged to equilibrium at 25 C and at 25 000 rpm. At distances of 8.34 cm and 9.12 cm from the axis
of rotation the concentrations of the protein are measured to be 3.52 g cm
3
and 22.49 g cm
3
, respectively. The specific volume V
1

of the protein is 0.78 cm
3
g
1
3
.Calculate the molecular weight of the protein.
Solution
*19.28. A protein has a molecular weight of 1 000 000 and a specific volume of 0.81 cm
3
g
1
. In an ultracentrifuge at 25 C, what speed of
revolution is required to produce at equilibrium a concentration ratio of 20/1 at distances 10.00 cm and 9.00 cm from the axis of
revolution? The density of water at 25 C is 0.997 g cm
3
.
Solution
Chapter 19: Transport Properties Essay Questions
19-9
Essay Questions
19.29. Explain how the rate of diffusion through a membrane depends on
a. the size of the diffusing substance, and
b. its solubility in the membrane.
19.30. Explain clearly the different mechanisms involved in the viscosity of gases and the viscosity of liquids.

Chapter 19: Transport Properties Solutions
19-10
Solutions
19.1. In a normal adult at rest the average speed of flow of blood through the aorta is 0.33 m s
1
. The radius of the aorta is 9 mm and the
viscosity of blood at body temperature, 37 C, is about 4.0 10
3
kg m
1
s
1
. Calculate the pressure drop along a 0.5 m length of the
aorta.
Solution:
Given:
1 3 1 1
blood aorta
0.33ms , 9 mm, 4.0 10 kgm s , 0.5 m v r l
= = = =
Required: P
To solve this problem we will use Eq. 19.10, the Poiseulle Equation.
4
1 2
( )
8
P P R dV
dt l
=
Rearranging for P we get,
4
8 l dV
P
R dt
=
To find the volume rate of flow, we find the area of the cross section of the aorta and multiply by the rate of blood flow through the aorta.
( ) ( )
blood
2
aorta
2
aorta blood
2
3 1
5 3 1
9 10 m 0.33ms
8.39748 10 m s
dV
A v
dt
A r
dV
r v
dt
dV
dt
dV
dt

=
=
=
=
=

19-11
Solving for P we get,
( )( )
( )
( )
3 1 1
5 3 1
4
3
1 2
1 2
8 4.0 10 kgm s 0.5 m
8.39748 10 m s
9 10 m
65.18518519kgm s
1kgm s 1 Pa
65Pa
P
P
P
=
=
=

19-12
19.2. A typical human capillary is about 1 mm long and has a radius of 2 m. If the pressure drop along the capillary is 20 Torr,
a. calculate the average linear speed of flow of blood of viscosity 4.0 10
3
kg m
1
s
1
;
b. calculate the volume of blood passing through each capillary per second; and
c. estimate the number of capillaries in the body if they are supplied by the aorta described in Problem 19.1.
Solution:
Given:
3 1 1
1 mm, 2 m, 20 Torr, 4.0 10 kgm s l r P = = = =
Required:
blood
, , number of capillaries
dV
v
dt

a. To calculate the average linear speed of blood flow, we use Eq. 19.10,
4
1 2
( )
8
P P R dV
dt l
=
The volume rate of flow is found from the area of the cross section of the aorta multiplied by the rate of blood flow through the aorta.
blood
2
aorta
2
aorta blood
dV
A v
dt
A r
dV
r v
dt
=
=
=

Rearranging to solve for
blood
v we obtain,
19-13
4
2
aorta blood
blood
8
P R
r v
l
P
v
=
4
8
R
l
2
aorta
aorta
2
blood
8
20 Torr
r
R r
PR
v
l
P
=
=
Pa
133.3
Torr
1 2
1kgm s 1 Pa =

( )( )
( )( )
2
1 2 6
blood
3 1 1 3
4 1
blood
4 1
blood
20 133.3kgm s 2 10 m
8 4.0 10 kgm s 1 10 m
3.3325 10 m s
3.3 10 m s
v
v
v

=

=
=

b. The volume of blood flow is defined above as,
( ) ( )
2
aorta blood
2
6 4 1
15 3 1
15 3 1
2 10 m 3.3325 10 m s
4.18774 10 m s
4.2 10 m s
dV
r v
dt
dV
dt
dV
dt
dV
dt

=
=
=
=

c. To calculate the number of capillaries, we divide the volume of flow through the aorta (from Problem 19.1) by the volume of flow
through the capillaries.
19-14
capillaries
aorta
5 3 1
Number of capillaries
8.39748 10 m s
Number of capillaries
dV
dV
dt dt

=
=
15 3 1
4.18774 10 m s

10
Number of capillaries 20052513128
Number of capillaries 2.0 10
=
=

19-15
*19.3. The viscosity of ethylene at 25.0 C and 101.325 kPa is 9.33 10
6
kg m
1
s
1
. Estimate
a. the molecular diameter,
b. the mean free path,
c. the frequency of collisions Z
A
experienced by a givenmolecule, and
d. the collision density Z
AA
.
Solution:
Given:
6 1 1
25.0 C, 101.325 kPa, 9.33 10 kgm s T P = = =
Required:
A AA
, , , d Z Z
a. The molecular diameter is given in Eq. 19.15 as,
2
2 2
mu
d
=
And therefore d is,
2 2
mu
d
=
We calculate u from Table 1.3 as,
19-16
( ) ( )
B
A
1 1
1
1
8
2 12.011 g mol 4 1.00794 g mol
28.05376 g mol
28.05376 g mol
k T
u
m
M
m
N
M
M
m
=
=
= +
=
=
23 1
6.022 10 mol
( )( )
( )
3
26
23 1
26
1
10
4.65855 10 kg
8 1.381 10 J K 298.15K
4.65855 10 kg
474.4157955ms
m
u
u
=

Solving for the diameter, we obtain
( )( )
( )
26 1
6 1 1
10
10
4.65855 10 kg 474.4157955ms
2 2 9.33 10 kgm s
5.16317 10 m
5.16 10 m
d
d
d
=
=

b. The mean free path is given in Chapter 1 by Eq. 1.68
2
A A
2
V
d N
=
From the ideal gas law,
19-17
( )( )
1 1
3
101325 Pa
8.3145 J K mol 298.15
40.87386075 mol m
40.87386075 mol
n P
V RT
n
V
n
V
N
V

=
=
=
=
2 3 1 3
6.022 1 m mol 0

2 3 5
2.46142 m 10
N
V
=

Therefore the mean free path is,
( ) ( )
25
2
10 3
8
8
1
2 5.16317 10 m 2.46142 m
3.43017 10 m
3.43 10 m
10
=

=
=

c. The expression for Z
A
is also found in Chapter 1 as Eq. 1.66,
2
A
1 A A
A
2
(SI unit:s )
d u N
Z
V

=
Which we recognize as,
A
A
u
Z
=
A
474.4157955 m
Z =
1
8
s
3.43017 10 m
1
A
10 1
A
13830675103s
1.38 10 s
Z
Z
=
=

19-18
d. From Eqs. 1.59 and 1.61,
( )( )
AA A
1 3
AA
35 3 1
AA
35 3
25
1
AA
1
2
1
13830675103s 2.46142 m
2
1.70216 10 m s
1.70 10 m
10
s
N
Z Z
V
Z
Z
Z

=
=
=
=

19-19
*19.4. For nonassociated liquids the fluidity (i.e., the reciprocal of the viscosity) obeys to a good approximation an equation of the
Arrhenius form
/
e
a
E RT
A

=
where A and E
a
are constants.
a. For liquid CCl
4
the viscosity at 0.0 C is 1.33 10
3
kg m
1
s
1
and the activation energy E
a
is 10.9 kJ mol
1
. Estimate the
b. The Arrhenius equation does not apply well to associated liquids such as water, but it can be used over a limited temperature
range. At 20.0 C the viscosity of water is 1.002 10
3
kg m
1
s
1
and the activation energy for fluidity 18.0 kJ mol
1
. Estimate the
Solution:
Given:
3 1 1 1
4 0.0 C
CCl : 1.33 10 kg m s , 10.9 kJ mol , 40.0 C
a
E T

= = =

3 1 1
20.0 C, 1.002 10 kg m s T

= =
Required:
40.0 C

, for CCl
4
and water
a. Since A is a constant, we first calculate
/
e
a
E RT
at each temperature,

3 1
1 1
3
3 1
1 1
0.0 C
10.9 10 J mol
exp exp
8.3145 J K mol 273.15 K
exp 8.234 485 424 10
40.0 C
10.9 10 J mol
exp exp
8.3145 J K mol 313.15 K
exp
a
a
a
a
T
E
RT
E
RT
T
E
RT
E
RT

=
| | | |
=
| |

\ .
\ .
| |
=
|
\ .
=
| | | |
=
| |

\ .
\ .
| |
\
2
1.520 131 7 10
=
|
.

19-20

Since we are told viscosity has the inverse relationship to the fluidity , we calculate the viscosity at 40.0 C as,
3
40.0 C 0.0 C 2
3
3 1 1
40.0 C 2
4 1 1
40.0 C
4 1 1
40.0 C
8.234485 10
1.5201317 10
8.234485 10
1.33 10 kg m s
1.5201317 10
7.20455 10 kg m s
7.20 10 kg m s

=
=

b. Repeating the same procedure above for water, we get,

19-21
3 1
1 1
4
3 1
1 1
20.0 C
18 10 J mol
exp exp
8.3145 J K mol 293.15 K
exp 6.205 331 937 10
40.0 C
18 10 J mol
exp exp
8.3145 J K mol 313.15 K
exp
a
a
a
a
T
E
RT
E
RT
T
E
RT
E
RT

=
| | | |
=
| |

\ .
\ .
| |
=
|
\ .
=
| | | |
=
| |

\ .
\ .
| |
=
|
\ .
o o
o
o
o
4
4
4 40.0 C 20.0 C
4
3 1 1
4 40.0 C
4 1 1
40.0 C
4 1
40.0 C
9.944 936 073 10
6.205 331 937 10
9.944 936 073 10
6.205 331 937 10
1.002 10 kg m s
9.944 936 073 10
6.252 169 501 10 kg m s
6.25 10 kg m s

=
=
1

19-22
19.5. At 20.0 C the viscosity of pure toluene is 5.90 10
4
kg m
1
s
1
. Calculate the intrinsic viscosities of solutions containing 0.1 g dm
3
of polymer in toluene and having the following viscosities:
a. 5.95 10
4
kg m
1
s
1
b. 6.05 10
4
kg m
1
s
1
c. 6.27 10
4
kg m
1
s
1
These solutions are sufficiently dilute that the reduced specific viscosity can be taken to be the intrinsic viscosity.
Solution:
Given:
4 1 1 3
pure
20.0 C, 5.90 10 kgm s , 0.1 g dm T = = =
Required: | |
Since we are told that the reduced specific viscosity can be taken to be the intrinsic viscosity, we solve using Eq. 19.31,
| |
0
0
1
reducedspecificviscosity

=
a.
| |
| |
| |
4 1 1 4 1 1
3 4 1 1
3 1
2 3 1
1 5.95 10 kgm s 5.90 10 kgm s
0.10gdm 5.90 10 kgm s
0.084745763dm g
8.5 10 m kg
=
=

b.
| |
| |
| |
4 1 1 4 1 1
3 4 1 1
3 1
3 1
1 6.05 10 kgm s 5.90 10 kgm s
0.10gdm 5.90 10 kgm s
0.254237288dm g
0.25m kg
=
=

19-23
c.
| |
| |
| |
4 1 1 4 1 1
3 4 1 1
3 1
3 1
1 6.27 10 kgm s 5.90 10 kgm s
0.10gdm 5.90 10 kgm s
0.627118644dm g
0.63m kg
=
=


19-24
*19.6. Suppose that solutions (a) and (c) in Problem 19.5 correspond to polymers of molecular weights 20 000 and 40 000, respectively.
Assuming the Mark-Houwink equation 19.33 to apply, make an estimate of the molecular weight of the polymer in solution (b).
Solution:
Given: Problem 19.5,
1 1
a c
20 000 g mol , 40 000g mol M M

= = , Eq.19.33
Required:
b
M
The Mark-Houwink equation, given by Eq.19.33 is
[ ]
r
kM
=
If it is obeyed, a plot of log [] against log M
r
will be a straight line.
Taking the logarithms of the solutions to Problem 19.5 gives,
| | ( )
| |
| | ( )
| |
| | ( )
| |
a
a
b
b
c
c
log log 0.084745763
log 1.071882007
log log 0.254237288
log 0.594760753
log log 0.627118644
log 0.202650288
=
=
=
=
=
=

The logarithms of the molar masses,
( )
( )
a
a
c
c
log log 20000
log 4.301029996
log log 40000
log 4.602059991
M
M
M
M
=
=
=
=

Since we assume a linear relationship the slope will be,
19-25
| | | |
| | | |
( )
c a
c a
log log
log log
0.202 650 228 1.071 882 007
4.602 059 991 4.301 029 996
2.887 525 474
m
M M
m
m

=
=

Using y mx b = + , we can use the coordinate of | |
a a
log and log M to determine the intercept b.
| |
a a
log log
1.071 882 007 4.301 029 996 2.887 525 474
13.491 212 568
m M b
b
b
= +
= +
=

the molar mass will then be,
| |
( )
b b
b
b
4.466 264254
b
1
b
4 1
b
log log
0.594 760 753 2.887 525 474 13.491 212 568
log 4.466 264 254
10
29 259.321 7 g mol
2.9 10 g mol
m M b
M
M
M
M
M
= +
= +
=
=
=
=

19-26
19.7. a. The activation energy for the fluidity of n-octane is 12.6 kJ mol
1
and the viscosity at 0 C is 7.06 10
4
kg m
1
s
1
. Estimate the
viscosity at 40.0 C, assuming the Arrhenius equation to apply.
b. A better temperature law for the viscosity of n-octane has been found to be
=A(T/K)
1.72
exp(543/(T/K)
where T is expressed in kelvins.
Make another estimate of the viscosity at 40 C. What is the effective activation energy at 20 C?
Solution:
Given:
1 4 1 1
0.0 C
12.6 kJ mol , 7.06 10 kg m s
a
E

= =
Required:
40.0 C

using the Arrhenius equation and the equation above, E
a

a. To solve this problem, we use the same procedure using in Problem 19.4.
19-27
( )
( )( )
( )
( )
( )( )
( )
3 1
a
1 1
3
a
3 1
a
1 1
3
a
40
0.0 C
12.6 10 J mol
exp / exp
8.3145 J K mol 273.15 K
exp / 3.895 402 10
40.0 C
12.6 10 J mol
exp / exp
8.3145 J K mol 313.15 K
exp / 7.912 639 816 10
T
E RT
E RT
T
E RT
E RT
=
| |

| =
|
\ .
=
=
| |

| =
|
\ .
=
( )
3
.0 C 0.0 C 3
3
4 1 1
40.0 C 3
4 1 1
40.0 C
4 1 1
40.0 C
3.895 402 10
7.912 639 816 10
3.895 402 10
7.06 10 kg m s
7.912 639 816 10
3.475 646 404 10 kg m s
3.48 10 kg m s
| |
=
|
\ .
=
=

b. Using the equation above, we get a better estimate.
( ) ( )
( ) ( )
1.72
1.72
1.72
/ K exp 543 / K
0.0 C
543
exp 543/ 273.15 exp
273.15
A T T
T
T T
= (

=
| |
=
|
\ .

19-28
( )
( ) ( )
( )
1.72 4
1.72
1.72
1.72 4
4
40.0 C 0.0 C 4
4 1
40.0 C
exp 543/ 4.706 868 453 10
40.0 C
543
exp 543/ 313.15 exp
313.15
exp 543/ 2.886 486 719 10
2.886 486 719 10
4.706 868 453 10
7.06 10 kg m s
T T
T
T T
T T

=
=
| |
=
|
\ .
=
=
( )
4
1
4
4 1 1
40.0 C
4 1 1
40.0 C
2.886 486 719 10
4.706 868 453 10
4.329 544 461 10 kg m s
4.33 10 kg m s
| |
\ .
=
=

To calculate the activation energy we use the fluidity. The fluidity can be expressed as,
( )
1
1.72
1
1 4515 J mol
/ K exp A T
RT
| |
= =
|
\ .

The activation energy at 20 C is, by definition,
19-29
( )
2
a
1
1
2
1
2
2
a
ln
4515 J mol
ln 1.72ln / K
ln 1.72 4515 J mol
ln 1.72 4515 J mol
d
E RT
dT
T
RT
d
dT T RT
d RT
dT RT
E RT
=
=
= +
+
=
=
1
2
1.72 4515 J mol RT
RT
+
1
a
1.72 8.3145 J K E

| |
|
\ .
=
( )
1
mol 293.15 K
( )
1
1
a
1
a
4515 J mol
8707.320 561 J mol
8.71 kJ mol
E
E
+
=
=

19-30
*19.8. Over its entire liquid range the viscosity of water is represented to within 1% by the following empirical formula:
3 2
(20 C) 3.1556( 20.0) 1.925 10 ( 20.0)
ln
( C) 109.0
t t
t t

| | +
=
|
+
\ .

where t is the value of the temperature in degrees Celsius. Make a better estimate of the viscosity of water than obtained by the use
of the Arrhenius equation (Problem 19.4b).
To what activation energies does this empirical expression correspond at
a. 20 C?
b. 100 C?
Give a qualitative explanation for the difference between the two values.
Solution:
Given: empirical formula, 20 C, 100 C T T = =
Required:
water
,
a
E
In problem 19.4b, we make an estimate at 40.0 C T = . We are also given,
3 1 1
20 C
1.002 10 kg m s

= Using the empirical formula, our
improved estimate is,
19-31
( ) ( )
( )
( ) ( )
( )
( ) ( )
2
3
3
3 1 1
40 C
3
3 1 1
40 C
40 C
3.1556 40 20.0 1.925 10 40 20.0 (20 C)
ln
(40 C) 109.0 40
3.1556 20.0 1.925 10 400
ln 1.002 10 kg m s ln
149.0
3.1556 20.0 1.925 10 400
ln ln 1.002 10 kg m s
149.0
ln 6.905757
+ | |
=
|
+
\ .
+
=
+
=
=
7.334495531
40 C
4 1 1
40 C
4 1 1
40 C
276 0.428738255
e
6.52633 10 kg m s
6.53 10 kg m s
=
=
=

To find the activation energies, we use the definition
2
2
ln
ln
a
a
d
E RT
dT
d
E RT
dT
=
=

From the empirical relationship, with
( ) ( )
( ) ( )( ) ( ) ( )
( )
( )( ) ( ) ( )
( )
2
20 C
3
2
2
2
2
273.15
293.15 293.15
ln ln
164.15
where 3.1556, 1.925 10
2 293.15 164.15 293.15 293.15
ln
164.15
2 586.3 164.15 293.15 293.15 ln
164.15
t
T t
a T b T
T
a b
a b T T a T b T
d
dT
T
a bT b T a T b T d
dT
T

= +
+
=
= =
+
=
+
=

19-32
a. At 20.0 C T = , the activation energy is,
( )( )
( ) ( )( ) ( )
2
1
8.3145 J K mol 293.15K
2 293.15K 586.3 293.15K 164.15 293.15K 293.15
a
E
a b b a
=
+
( )
2
293.15K 293.15 b
( )
( )( )
( )( ) ( ) ( )
( )
( )
2
2
1
3 3
2
1
1
293.15K 164.15
8.3145 J K mol 293.15K
3.1556 2 1.925 10 293.15K 586.3 1.925 10 293.15K 164.15
293.15K 164.15
17478.6615 J mol
17.5kJ mol
a
a
a
E
E
E
=
+
=
=

b. At 100.0 C T = , the activation energy is,
( )( )
( ) ( )( ) ( ) ( )
( )
2
1
2
2
1
1
8.3145 J K mol 373.15K
2 373.15 586.3 373.15 164.15 373.15 293.15 373.15 293.15
373.15 164.15
12168.60604 J mol
12.2kJ mol
a
a
a
E
a b b a b
E
E
=
+
=
=

19-33
*19.9. Consider a hypothetical gas in which the molecules have mass but no size and do not interact with each other.
a. What would be the viscosity of such a gas?
b. Suppose instead that the molecules have zero size but attract one another. What can you then say about the viscosity?
c. If they repel one another, what would the viscosity be?
d. Give a clear explanation of your conclusions in all three cases.
Solution:
Given: a d
Required: clear explanations
a. In a hypothetical gas in which the molecules have no size, there are no collisions and there no exchanges of momentum between
molecules. If there are no forces between the molecules, two layers can move past each other freely, and the viscosity is zero.

b. If the molecules have no size but attract one another, a force is required to move one layer past another. The gas will therefore have a
viscosity. Increasing the temperature will increase the molecular speeds and will decrease the viscosity, as in a liquid.

c. If the molecules have no size but repel one another, a force again will be required to move one layer past another. There will again be a
viscosity, which decreases with increasing temperature.

19-34
19.10. The molecular diameter of the helium atom is 0.225 nm. Estimate, at 0 C and 101.325 kPa,
a. the viscosity of the gas,
b. the self-diffusion coefficient,
c. the mean speed of the molecules,
d. the mean free path,
e. the collision frequency Z
A
, and
f. the collision density Z
AA
.

Solution:
Given: 0.225 nm, 0 C, 101.325 kPa d T P = = =
Required:
A AA
, , , , , D u Z Z
a. To find viscosity, we use Eq. 19.16,
1/2 1/2
B B
3/2 2 1/2
( ) ( ) mk T mk T
d

= =
For the helium atom, the mass is given by,
A
4.0026 g
M
m
N
m
=
=
1
mol
23 1
6.022 10 mol
3 1
10 kg g

27
6.64663 10 kg m

=

Solving for we get,
19-35
( )( )( )
( )
1/2
27 23 1
2
3/2 9
5 1 1
5 1 1
6.64663 10 kg 1.381 10 J K 273.15K
0.225 10 m
1.77627 10 kgm s
1.78 10 kgm s

(

=
=
=

b. We calculate the self-diffusion coefficient from Eq. 19.57,
( )( )( )
( )( )
B
B
5 1 1 23 1
27
5 2 1
5 2 1
1.77627 10 kgm s 1.381 10 J K 273.15K
6.64663 10 kg 101325Pa
9.94913 10 m s
9.95 10 m s
D
D
mN mP
V k T
k T
D
mP
D
D
D

=
=
= =
=

=
=
=

c. We calculate u from Table 1.3 as,
19-36
( )( )
( )
B
23 1
27
1
3 1
8
8 1.381 10 J K 273.15K
6.64663 10 kg
1202.172472ms
1.20 10 ms
k T
u
m
u
u
u
=
=

d. The mean free path is given in Chapter 1 by Eq. 1.68
2
A A
2
V
d N
=
From the ideal gas law,
1
8.3145 J K
n P
V RT
V
N
=
=
1
mol
( )
273.15 K
( )
( )
2 1 3
6.022 10 101325 Pa mol
( )
26 3
3.72203 10 m
V
N
=

Therefore the mean free path is,
26 3
3.722 03 10 m
=
9
2 0.225 10 m

( )
2
7
7
1.654817375 10 m
1.65 10 m
=
=

e. The expression for Z
A
is also found in Chapter 1 as Eq. 1.66,
19-37
2
A
1 A A
A
2
(SI unit:s )
d u N
Z
V

=
Which we recognize as,
A
A
u
Z
=
A
1202.172472 m
Z =
1
7
s
1.65482 10 m
1
A
9 1
A
7264683644s
7.26 10 s
Z
Z
=
=

f. From Eqs. 1.59 and 1.61,
( )( )
AA A
1
1 26 3
AA
34 3 1
AA
34 3 1
AA
1
2
1
7264683644s 3.72203 m
2
9.75903 10 m s
9.76 10 m
10
s
N
Z Z
V
Z
Z
Z

=
=
=
=

19-38
19.11. Calculate the mean square distance traveled by a molecule of H
2
at 20 C and 101.325 kPa in 10 s (D =1.005 10
4
m
2
s
1
).
Solution:
Given:
4 2 1
2
H : 101.325 kPa, 10 s, 1.005 10 m s P t D = = =
Required:
2
x
From Eq. 19.48, the mean square distance is given by,
2
2
2 4 2 1
2
2
2 1.005 10 m s
x Dt
x Dt
x
=
=
=
( )
10 s
( )
2
2
0.044833024m
4.5cm
x
x
=
=

19-39
19.12. Solutions of (a) glucose (D =6.8 10
10
m
2
s
1
) and (b) tobacco mosaic virus (D =5.3 10
12
m
2
s
1
) were maintained at a
constant temperature of 20 C and without agitation for 100 days. How far would a given molecule of each be expected to diffuse in
that time?
Solution:
Given:
10 2 1 12 2 1
glucose virus
6.8 10 m s , 5.3 10 m s , 20.0 C, 100 days D D T t = = = =
Required:
2
x
From Eq. 19.48, the mean square distance is given by,
2
2
2
2
x Dt
x Dt
=
=

Converting the time in days to time in seconds we can solve for the mean square distance,
2 10 2 1
glucose
100 24 60 60
8640000 s
2 6.8 10 m s
t
t
x
=
=
=
( )
8640000 s
( )
2
glucose
2
glucose
0.108399262 m
11cm
x
x
=
=

For the virus,
2 12 2 1
virus
2 5.3 10 m s x =
( )
8640000 s
( )
2
virus
2
virus
0.009569953 m
0.96cm
x
x
=
=

19-40
19.13. Estimate the diffusion coefficient of cupric sulfate in water at 25 C from the molar conductivities given in Table 7.3 (p. 291).
Solution:
Given: 25 C, T = Table 7.3
Required: D
To solve this problem, we follow the example set by Example 19.4
Using Eq. 19.73, at 25 C,
( )( )
( ) ( )
2
1 1
1 2 1
2
1
7 1 2 2
7 2 1
8.3145J K mol 298.15K
( cm mol )
96500Cmol 2
1.33103 10 J C cm
1.33103 10 cm s
i
RT
D
F z
D
D
D

=
=
=
=

From Table 7.3, we obtain the molar conductivities,
2
2
4
2 1
1
Cu
2
2 1
1
SO
2
56.6Scm mol
80.0Scm mol
=
=

For Cu
2+
,
( )( )
7
6 2 1
1.33103 10 56.6
7.5336 10 cm s
D
D
+
=
=

For SO
4
2
,
19-41
( )( )
7
5 2 1
1.33103 10 80.0
1.06482 10 cm s
D
D
=
=

Using Eq. 19.74,
( )( )
6 2 1 5 2 1
6 2 1 5 2 1
2
2 7.5336 10 cm s 1.06482 10 cm s
7.5336 10 cm s 1.06482 10 cm s
D D
D
D D
D
+
+

=
+

=
+

6 2 1
6 2 1
8.82413 10 cm s
8.82 10 cm s
D
D

=
=

19-42
19.14. Estimate the diffusion coefficient of sodium acetate in water at 25 C from the following mobility values:
Na
+
: 5.19 10
4
cm
2
V
1
s
1

CH
3
COO
: 4.24 10
4
cm
2
V
1
s
1

Solution:
Given: 25 C, T =
3
4 2 1 1 4 2 1 1
, Na , CH COO
5.19 10 cm V s , 4.24 10 cm V s
e e
u u
+
= = mobility
Required: D
To solve this problem we use Eq. 19.72,
B
i
k T
D u
Q
=
Since the charge on 1 mole of an equivalent ion QL, is 96 500 C mol
-1
, we can write Eq. 19.72 as,
1
8.3145J K
e
RT
D u
Q
D
=
=
1
mol
( )
298.15 K
( )
1
96500C mol
( )
( ) 0.025688789V
e
e
u
D u =

For Na
+
,
0.025688789 V D
+
=
( )
4 2 1
5.19 10 cm V
( )
1
5 2 1
s
1.33325 10 cm s D

+
=

For CH
3
COO
,
0.025688789 V D
=
( )
4 2 1
4.24 10 cm V
( )
1
5 2 1
s
1.0892 10 cm s D

=

19-43
Using Eq. 19.74,
( )( )
5 2 1 5 2 1
5 2 1 5 2 1
2
2 1.33325 10 cm s 1.0892 10 cm s
1.33325 10 cm s 1.0892 10 cm s
D D
D
D D
D
+
+

=
+

=
+

5 2 1
5 2 1
1.19893 10 cm s
1.20 10 cm s
D
D
=
=

19-44
19.15. The diffusion coefficient for horse hemoglobin in water is 6.3 10
11
m
2
s
1
at 20 C. The viscosity of water at 20 C is 1.002 10
3
kg m
1
s
1
and the specific volume of the protein is 0.75 cm
3
g
1
. Assume the hemoglobin molecule to be spherical and to obey
Stokess law, and estimate its radius and the molecular weight.
Solution:
Given:
11 2 1 3 1 1 3 1
specific
6.3 10 m s , 20 C, 1.002 10 kgm s , 0.75 cm g D T V = = = =
Required: , r M
Stokes law is given by Eq. 19.77 as,
B
6
k T
D
r
=
Solving for r, the radius of the hemoglobin molecule we get,
B
23 1
6
1.381 10 J K
k T
r
D
r
=
( )
293.15 K
( )
( )( )
3 1 1 11 2 1
9
9
6 1.002 10 kgm s 6.3 10 m s
3.40231 10 m
3.4 10 m 3.4 nm
r
r

=
= =

To get the molar mass, we first calculate the volume, assuming the molecule is perfectly spherical.
19-45
( )
( )
3
3
9
25 3
A
specific
25 3
23 1
6 3 1
1
5 1
4
3
4
3.40231 10 m
3
1.64972 10 m
1.64972 10 m
6.022 10 mol
0.75 10 m g
132461.7981g mol
1.3 10 g mol
V r
V
V
V
M N
V
M
M
M
=
=
=
=
=
=

19-46
19.16. If the diffusion coefficient for insulin is 8.2 10
11
m
2
s
1
at 20 C, estimate the mean time required for an insulin molecule to
diffuse through a distance equal to the diameter of a typical living cell ( 10 m).
Solution:
Given:
11 2 1
8.2 10 m s , 20 C, 10 m D T x = = =
Required: t
The mean time can be obtained from From Eq. 19.48,
( )
( )
2
2
2
6
11 2 1
2
2
10 10 m
2 8.2 10 m s
0.609756098s
0.61s
x Dt
x
t
D
t
t
t
=
=
=
=

19-47
*19.17. A colloidal particle is spherical and has a diameter of 0.3 m and a density of 1.18 g cm
3
. Estimate how long it will take for the
particle to diffuse through a distance of 1 mm in water at 20 C ( =1.002 10
3
kg
3
m
1
s
1
; the density of water at 20 C =0.998
g cm
3
). (See also Problem 19.21.)
Solution:
Given:
3
0.3 m, 1.18 g cm , 1mm, 20 C, d x T = = = =

3 1 1 3
water
1.002 10 kgm s , 1.18 g cm = =
Required: t
The mean time can be obtained from Eq. 19.48,
2
2
2
2
x Dt
x
t
D
=
=

Stokes law gives D in Eq. 19.77 as,
B
7
23 1
6
1.5 10 m
2
1.381 10 J K
k T
D
r
d
r
D

=
= =
=
( )
293.15 K
( )
( )( )
3 1 1 7
12 2 1
6 1.002 10 kgm s 1.5 10 m
1.42897 10 m s D

=

19-48
Solving for t, we get,
( )
( )
2
3
12 2 1
5
10 m
2 1.42897 10 m s
349902.0854 s
3.5 10 s
t
t
t
=
=

19-49
19.18. Diphtheria toxin was found to have, at 20 C, a sedimentation coefficient of 4.60 Svedbergs and a diffusion coefficient of 5.96 10
7
cm
2
s
1
. The toxin has a specific volume of 0.736 cm
3
g
1
3
. Estimate a value for the
molecular weight of the toxin.
Solution:
Given:
13 7 2 1 3 1
specific
20 C, 4.60 10 s, 5.96 10 cm s , 0.736 cm g , T s D V
= = = =
3
0.998 g cm =
Required: M
The molar mass is given by the Svedberg equation, Eq. 19.93,
2
(1 )
RTs
M
D V
=

Substitution into this equation gives the molar weight of the toxin.
1
8.3145J K
M
=
( )
1
mol 293.15 K
( )( )
( )
13
11 2 1 3 1
4.60 10 s
5.96 10 m s 1 0.736 cm g

( )
3
0.998 g cm
( ) ( )
1 2 2
2 2
1
3 1
70.86289428J mol m s
1J 1kg m s
70.9 kg mol
70.9 10 g mol
M
M
M

=
=
=
=

19-50
19.19. A protein has a sedimentation coefficient of 1.13 10
12
s
1
at 25 C and a diffusion coefficient of 4.2 10
11
m
2
s
1
. The density of
the protein is 1.32 g cm
3
and that of water at 25 C is 0.997 g cm
3
. Calculate the molecular weight of the protein.
Solution:
Given:
12 11 2 1 3
protein
25 C, 1.13 10 s, 4.2 10 m s , 1.32 gcm , T s D

= = = =
2
3
H O
0.997 g cm =
Required: M
We solve this problem in the same manner as Problem 19.18, making the substitution for V
2
as
protein
1
.
2
(1 )
RTs
M
D V
=

Substitution into this equation gives the molar weight of the protein .
1
8.3145J K
M
=
( )
1
mol 298.15 K
( )( )
( )
12
3
11 2 1
1.13 10 s
0.997 g cm
4.2 10 m s 1

( )
3
1.32 gcm
1
5 1
272.5658949kg mol
2.7 10 g mol
M
M
| |
|
|
|
\ .
=
=

19-51
*19.20. A protein of molecular weight 60 000 has a density of 1.31 g cm
3
and in water at 25 C ( =0.997 g cm
3
; =8.937 10
4
kg m
1
s
1
) it has a sedimentation coefficient of 4.1 10
13
s
1
. Calculate the frictional coefficient f
a. from the sedimentation coefficient, and
b. by the use of Stokess law.
Suggest a reason why the two values are not quite the same.
Solution:
Given:
1 3 11 1
protein
25 C, 60000 gmol , 1.31 gcm , 4.1 10 s , T M s

= = = =
2
3 4 1 1
H O
0.997 g cm , 8.937 10 kg m s = =
Required: f from a and b
a. To calculate the frictional coefficient from the sedimentation coefficient, we use Eq. 19.86,
2
2
(1 ) V m x
f

= , where
2
s
x
= from Eq. 19.87.

Therefore we get the frictional coefficient as,
2
2
(1 )
(1 )
V m
s
f
V m
f
s
=

To solve for f we first calculate the mass of the protein.
A
1
60.000 kg mol
M
m
N
m
=
=
23 1
6.022 10 mol
23
9.96347 10 kg m

=

19-52
Using the substitution for V
2
as
protein
1
.
3
0.997 g cm
1
f
=
( )
3
1.31 gcm
( )
23
13 1
9.96347 10 kg
4.1 10 s
| |
|

|
|
\ .

11 1
11 1
5.8063 10 kgs
5.8 10 kgs
f
f
=
=

b. To solve for the frictional coefficient from Stokes Law, we use Eq. 19.76,
6 f r =
We assume the protein is perfectly spherical and use the volume of the sphere to find r.
23
9.96347 10 kg
m
V
V
=
3
1.31 10 kg
3
26 3
3
1/3
1/3
26 3
9
m
7.6057 10 m
4
3
3
4
3 7.6057 10 m
4
2.62835 10 m
V
V r
V
r
r
r
=
=
| |
=
|
\ .
| |
=
|
\ .
=

Using r, we now solve for f.
19-53
9
6 2.62835 10 m f

=
( )
4 1
8.937 10 kg m
( )
1
11 1
11 1
s
4.42768 10 kg s
4.43 10 kg s
f
f
=
=

The two values are not quite the same since in the Stokes calculation, we assumed that the molecule is perfectly spherical.

19-54
*19.21. How long will it take the particle from Problem 19.17 to sediment a distance of 1 mm in the earths gravitational field (g =9.81 m s
2
)?
Solution:
Given: Problem 19.17,
2
1mm, 9.81 m s x g = =
Required: t
The limiting rate of sedimentation is given by Eq. 19.85 as,
2
(1 )
6
V mg
r
=
To solve for v we first calculate the mass of the particle using volume and density,
( ) ( )
3
3
7 3 3
17
4
3
4
1.5 10 m 1.18 10 kgm
3
1.66819 10 kg
m
V
m r
m
m
=
| |
=
|
\ .
=
=

The speed is therefore,
3
0.998 gcm
1
=
3
1.18 gcm
17
1.66819 10 kg
| |
|
|
\ .
( ) ( )
2
7
9.81 m s
6 1.5 10 m

( )
3
1.002 10 kg
1
m
( )
1
9 1
s
8.90928 10 ms

=

19-55
Since speed is the distance travelled over time, the particle sediments a distance of 1 mm in,
3
9 1
5
1 10 m
8.90928 10 ms
112242.4976s
1.12 10 s
d
t
d
t
t
t
t
=
=
=
=

19-56
*19.22. An aqueous colloidal solution contains spherical particles of uniform size and of density 1.33 g cm
3
. The diffusion coefficient at 25
C is 1.20 10
11
m
2
s
1
; make an estimate of the sedimentation coefficient ((H
2
O) =0.997 g cm
3
; (H
2
O) =8.937 10
4
kg m
1
s
1
).
Solution:
Given:
3 11 2 1
1.33g cm , 25 C, 1.20 10 m s , d T D = = =
2 2
3 4 1 1
H O H O
0.997 g cm , 8.937 10 kg m s = =
Required: s
To find the sedimentation coefficient, we will use Eq. 19.89,
2
(1 )
6
V m
s
r
=
We find the radius using Stokes Law, Eq. 19.77,
B
B
23 1
6
6
1.381 10 J K
k T
D
r
k T
r
D
r

=
=
=
( )
298.15 K
( )
( )( )
4 1 1 11 2 1
8
6 8.937 10 kg m s 1.20 10 m s
2.03683 10 m r

=

19-57
The mass of each particle is calculated using volume and density,
( ) ( )
3
3
8 3 3
20
4
3
4
2.03683 10 m 1.33 10 kgm
3
4.70764 10 kg
m
V
m r
m
m
=
| |
=
|
\ .
=
=

The sedimentation coefficient is,
3
0.997gcm
1
s
=
3
1.33gcm
20
4.70764 10 kg
| |
|
|
\ .
( )
4
6 8.937 10 kg
1
m
( )
1 8
s 2.03683 10 m
( )

11
11
3.43517 10 s
3.44 10 s
s
s
=
=

19-58
19.23. At 20 C, -globulin has a sedimentation constant of 7.75 10
13
s, a diffusion coefficient in water of 4.8 10
11
m
2
s
1
, and a
density of 1.353 g cm
3
. The density of water at 20 C is 0.998 g cm
3
.
a. Estimate the molecular weight of -globulin.
b. Assuming the Stokes-Einstein equation to apply, estimate the radius of the protein molecule. The viscosity of water at 20 C is
1.002 10
3
kg m
1
s
1
.
Solution:
Given:
13 11 2 1 3
20 C, 7.75 10 s, 4.8 10 m s , =1.353 g cm , T s D

= = =
2
3 3 1 1
H O
0.998 g cm , 1.002 10 kgm s = =
Required: M, r
a. We solve this problem in the same manner as Problem 19.18, making the substitution for V
2
as
1
.
2
(1 )
RTs
M
D V
=

Substitution into this equation gives the molar weight of the protein .
1
8.3145J K
M
=
( )
1
mol 293.15 K
( )( )
( )
13
3
11 2 1
7.75 10 s
0.998 g cm
4.8 10 m s 1

( )
3
1.353 gcm
1
5 1
149.9878034kg mol
1.5 10 g mol
M
M
| |
|
|
|
\ .
=
=

19-59
b. To estimate radius, we use the Stokes-Einstein equation, Eq.19.77
B
B
23 1
6
6
1.381 10 J K
k T
D
r
k T
r
D
r

=
=
=
( )
293.15 K
( )
( )( )
3 1 1 11 2 1
6 1.002 10 kg m s 4.8 10 m s

9
9
4.46553 10 m
4.5 10 m
r
r
=
=

19-60
*19.24. A sample of human hemoglobin had a sedimentation constant of 4.48 Svedbergs in water at 20 C and a diffusion coefficient of 6.9
10
11
m
2
s
1
. The specific volume of human hemoglobin is 0.749 cm
3
g
1
3
.
a. Estimate the molecular weight of human hemoglobin.
b. How far would a molecule diffuse in 1 minute?
c. Neglect diffusion and estimate how far a molecule would sediment in 1 minute.
d. In a centrifuge rotating at 15 000 rpm, how far would a molecule sediment in 1 minute if it were 20 cm from the center of
rotation?
e. Assume the molecule to be spherical and estimate its radius by the use of the Stokes-Einstein equation.
f. Estimate the radius from the molecular weight and the density.
Solution:
Given:
13 11 2 1 3 1
2
20 C, 4.48 10 s, 6.9 10 m s , 0.749 cm g , T s D V

= = = =
2
3
H O
0.998 g cm

=
Required: a f
To solve this problem, we can refer to Example 19.6 for extra help.
a. The molar mass is obtained from Eq. 19.93,
2
1
(1 )
8.3145J K
RTs
M
D V
M
=
( )
1
mol 293.15 K
( )( )
( )
13
11 2 1 3 1
4.48 10 s
6.9 10 m s 1 0.749 cm g

( )
3
0.998 g cm
( ) ( )
1 2 2
2 2
1
3 1
62.67538594J mol m s
1J 1kg m s
62.7 kg mol
62.7 10 g mol
M
M
M

=
=
=
=

19-61
b. Using Einsteins equation, Eq. 19.48, the molecule would diffuse,
2
2
2 11 2 1
2
2
2 6.9 10 m s
x Dt
x Dt
x
=
=
=
( )
60 s
( )

2 5
2 5
9.09945 10 m
9.1 10 m
x
x
=
=

c. The sedimentation coefficient is the rate of sedimentation for an acceleration of gravity of unity. In a gravitational field of g =9.8 m s
2
the rate of sedimentation is,
2 13
12 1
9.81 ms 4.48 10 s
4.39488 10 ms
v
v

=
=

Therefore the distance travelled is,
12 1
4.39488 10 ms
d vt
d

=
=
( )
60 s
( )
10
10
2.63693 10 m
2.64 10 m
d
d
=
=

d. The rate of sedimentation in an ultracentrifuge is given by Eq. 19.87
2
s x =
The speed of revolution is
1
1
15000 rpm
2
60 s min
1570.796327 rad s

| |
=
|
\ .
=

19-62
The rate of sedimentation, with x =20 cm is,
( )( ) ( )
2
13 1
7 1
4.48 10 s 1570.796327 rad s 0.2m
2.21079 10 ms
=
=

7 1
2.21079 10 ms
d vt
d

=
=
( )
60 s
( )
5
5
1.32647 10 m
1.33 10 m
d
d
=
=

e. To estimate radius, we use the Stokes-Einstein equation, Eq.19.77
B
B
23 1
6
6
1.381 10 J K
k T
D
r
k T
r
D
r

=
=
=
( )
293.15 K
( )
( )( )
3 1 1 11 2 1
9
9
6 1.002 10 kg m s 6.9 10 m s
3.10646 10 m
3.1 10 m
r
r

=
=

f. Using molecular weight and the density we can make another estimate for the radius.
The mass of the molecule is given by,
19-63
A
1
62.67538594 kg mol
M
m
N
m
=
=
23 1
6.022 10 mol
22
1.04077 10 kg m

=

Using density,
19
1.04077 10 g
m
V
V
=
=
( )
6 3 1
0.749 10 m g
( )
29 3
3
1/3
1/3
29 3
10
10
7.79539 10 m
4
3
3
4
3 7.79539 10 m
4
2.65002 10 m
2.65 10 m
V
V r
V
r
r
r
r
=
=
| |
=
|
\ .
| |
=
|
\ .
=
=

This is in reasonable agreement with the radius obtained in part e. The molecule is not in fact spherical, and the equation is more
satisfactory for larger particles.
19-64
*19.25.In the first decade of the twentieth century J ean Perrin carried out important investigations on the sedimentation, in the gravitational
field, of particles of gamboge, mastic, and other paint pigments. Consider particles of density 1.2 g cm
3
and of the following radii:
a. 1 mm
b. 0.1 mm
c. 10 m
d. 1 m
e. 10 nm
In each case, assuming Stokess law to apply, estimate the distance the particle would sediment in 1 hour, in water at 20 C
(viscosity, =1.002 10
3
kg m
1
s
1
and density 0.998 g cm
3
).
f. In the case of the particle having a radius of 10 nm, what speed of rotation in an ultracentrifuge would be required to bring about a
sedimentation of 1 mm in 1 hour? Take the distance from the axis of rotation to be 10 cm.
Solution:
Given:
3 3 1 1 3
water
, , 1.2 g cm 1 h, 20 C, 1.002 10 kg m s , 0.998 g cm r t T = = = =
Required: d , v
a. To solve for the distance travelled, we need to calculate the sedimentation coefficient, given by Eq. 19.89,
2
(1 )
6
V m
s
r
=
The mass of the particle is calculated as,
( ) ( )
3
3
3 3 3
6
4
3
4
1 10 m 1.2 g cm 1200kg m
3
5.02655 10 kg
m V
m r
m
m
=
=
= =
=

19-65
Making the substitution for V
2
as
1
, the sedimentation coefficient is,

3
0.998 g cm
1
s
=
3
1.2g cm
6
5.02655 10 kg
| |
|
|
\ .
( )
3
6 1.002 10 kg
1
m
( )
1 3
s 1 10 m
( )
0.04479929s s =

The rate of sedimentation in a gravitational field is therefore,
2
1
9.81 ms 0.04479929s
0.439481038ms
v
v
=
=

1
0.439481038ms
d vt
d

=
=
( )
3600 s
( )
3
1582.131737m
1.58 10 m
d
d
=
=

Repeating the same procedure for b e we can solve for the distance of sedimentation.

19-66
b.
( ) ( )
3
3 3
9
3
4
0.1 10 m 1200kg m
3
5.02655 10 kg
0.998 g cm
1
m
m
s
=
=
=
3
1.2g cm
9
5.02655 10 kg
| |
|
|
\ .
( )
3
6 1.002 10 kg
1
m
( )
1 3
s 0.1 10 m
( )
4
4.479929 10 s s =

2 4
3 1
9.81 ms 4.479929 10 s
4.39481038 10 ms
v
v
=
=

3 1
4.39481038 10 ms d

=
( )
3600 s
( )
15.82131737m
15.8m
d
d
=
=

c.
( ) ( )
3
6 3
12
3
4
10 10 m 1200 kg m
3
5.026 548 246 10 kg
0.998 g cm
1
s=
m
m
=
=
3
1.2 g cm
12
5.026 548 246 10 kg
| |
|
|
\ .
3
6 1.002 10 kg

1
m
( )
1 6
s 10 10 m

( )
6
4.479 929 031 10 s s

=

19-67
2 6
5 1
9.81 m s 4.479 929 031 10 s
9.394 810 379 10 m s

=
=

5 1
4.39481038 10 ms d

=
( )
3600 s
( )
1
0.1582132m
1.58 10 m
d
d
=
=

d.
( ) ( )
3
6 3
15
3
4
1 10 m 1200kg m
3
5.02655 10 kg
0.998 g cm
1
m
m
s
=
=
=
3
1.2g cm
15
5.02655 10 kg
| |
|
|
\ .
( )
3
6 1.002 10 kg
1
m
( )
1 6
s 1 10 m
( )
8
4.479929 10 s s =

2 8
7 1
9.81 ms 4.479929 10 s
4.39481038 10 ms
v
v
=
=

7 1
4.39481038 10 ms d

=
( )
3600 s
( )
3
0.001582132m
1.58 10 m
d
d
=
=

19-68
e.
( ) ( )
3
9 3
21
3
4
10 10 m 1200kg m
3
5.02655 10 kg
0.998 g cm
1
m
m
s
=
=
=
3
1.2g cm
21
5.02655 10 kg
| |
|
|
\ .
( )
3
6 1.002 10 kg
1
m
( )
1 9
s 10 10 m
( )
12
4.479929 10 s s =

2 12
11 1
9.81 ms 4.479929 10 s
4.39481038 10 ms
v
v
=
=

11 1
4.39481038 10 ms d

=
( )
3600 s
( )
7
7
1.58213 10 m
1.58 10 m
d
d
=
=

f. The rate of sedimentation in an ultracentrifuge is given by Eq. 19.87
2
s x =
The rate of sedimentation is,
3
7 1
1 10 m
3600 s
2.77778 10 ms
=
=

The sedimentation coefficient is calculated as,
19-69
( ) ( )
3
9 3
21
3
4
10 10 m 1200kg m
3
5.02655 10 kg
0.998 g cm
1
m
m
s
=
=
=
3
1.2g cm
21
5.02655 10 kg
| |
|
|
\ .
( )
3
6 1.002 10 kg
1
m
( )
1 9
s 10 10 m
( )
12
4.479929 10 s s =

This leads to,
7
2.77778 10 m
sx
=
( )
1
12 3
s
4.479929 10 s 10 10 m

( )
1
4
2490.079326rads
(revolutions per second)
2
396.3084334 rps
23778.506 rpm
2.38 10 rpm
=
=
=

19-70
*19.26. Perrin also carried out, using pigment particles, experiments on Brownian movement in which he determined distances traveled by
individual particles in various periods of time. For each of the particles of five different radii mentioned in the previous problem,
estimate the diffusion coefficient and the average distance traveled in 1 hour. Take the water temperature again as 20C and use the
data of Problem 19.25.
Solution:
Given: Problem 19.25
Required: D,
2
x
The diffusion coefficient is given by Eq. 19.77 as,
B
6
k T
D
r
=
Solving using the data from part a of the previous question we get,
B
23 1
6
1.381 10 J K
k T
D
r
D

=
=
( )
293.15 K
( )
3 1
6 1.002 10 kg m
( )
1 3
s 10 10 m
( )
16 2 1
16 2 1
2.14346 10 m s
2.143 10 m s
D
D
=
=

19-71
Using Einsteins equation, Eq. 19.48,
2
2
2 16 2 1
2
2
2 2.14346 10 m s
x Dt
x Dt
x

=
=
=
( )
3600 s
( )
2 6
2 6
1.24229 10 m
1.242 10 m
x
x
=
=

Repeating the above procedure for b e, we summarize with the following results,

/ m r
16 2 1
10 / m s D

2
/ m x
a.
3
10

2.143 1.242
b.
4
10

21.43 3.928
c.
5
10

214.3 12.42
d.
6
10

2143 39.28
e.
8
10

5
2.143 10
392.8

19-72
*19.27. A pure protein in water is centrifuged to equilibrium at 25 C and at 25 000 rpm. At distances of 8.34 cm and 9.12 cm from the axis
of rotation the concentrations of the protein are measured to be 3.52 g cm
3
and 22.49 g cm
3
, respectively. The specific volume V
1

of the protein is 0.78 cm
3
g
1
3
.Calculate the molecular weight of the protein.
Solution:
Given:
3 3
1 2 1 2
25 C, 25000rpm, 8.34 cm, 9.12 cm, 3.52 g cm , 22.49 g cm T x x = = = = =

3 1 3
1 water
0.78 cm g , 0.997gcm V = =
Required: M
We can calculate the molecular weight from Eq. 19.98,
2 1
2 2 2
2 2 1
2 ln( / )
(1 ) ( )
RT c c
M
V x x
=

Solving for we get,
1
1
25000rpm
2
60smin
2617.993878rads

=
=

Taking the density of the protein as a measure of the concentration, we solve.]
1
2 8.3145 J K
M
=
1
mol
( )
298.15 K
( )
3
22.49 g cm
ln

3
3.52 g cm
3 1
1 0.78 cm g
| |
|
|
\ .
( )
3
0.997 g cm
( ) ( )
( ) ( ) ( )
( )
2 2 2
1 2 2
1
1
3 1
2617.993 878 rad s 9.12 10 m 8.34 10 m
4.430 571 965 kg mol
4430.571 965 g mol
4.43 10 g mol
M
M
M

=
=
=

19-73
*19.28. A protein has a molecular weight of 1 000 000 and a specific volume of 0.81 cm
3
g
1
. In an ultracentrifuge at 25 C, what speed of
revolution is required to produce at equilibrium a concentration ratio of 20/1 at distances 10.00 cm and 9.00 cm from the axis of
revolution? The density of water at 25 C is 0.997 g cm
3
.
Solution:
Given:
6 1 3 1
2 2 1 1 2
, 10 gmol , 0.81 cm g 25 C, / 20/1, 10.00 cm, 9.00cm T M V c c x x
= = = = = =
3
water
0.997gcm =
Required:
We can solve for using Eq. 19.98,
( )
( ) ( )
( )
( ) ( )
2 1
2 2 2
2 2 1
2 1
2 2
2 2 1
1
2 ln
1
2 ln
1
2 8.3145 J K
RT c c
M
V x x
RT c c
V M x x

=

=

=
1
mol
( )
298.15 K
( ) ( )
3 1
ln 20
1 0.81 cm g
( )
3
0.997 g cm
( ) ( )
3 1
10 kg mol
( ) ( ) ( )
( )
( )
2 2
2 2
1
1
3
10.00 10 m 9.00 10 m
201.552 775 1 rad s
in rpm,
201.552 775 1 rad s 60 s
2
1924.687 227 rpm
1.9 10 rpm
=
=
=


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CHAPTER

= and now solve for M

= = = and solve for density

= and solve for P

from the appendix in Chapter 1, the denominator can be simplified.

from the appendix in Chapter 1, the expression can be simplified.

from the appendix to Chapter 1, the denominator can be simplified.

where a and b are constants not equal to zero

33.435 072 214 kJ absorbed q = =

( ) 120.264 582 1 298.15 K

( ) 120.264 582 1 298.15 K

( ) 120.264 582 1 298.15 K

], which is the equilibrium constant for the dissociation of water;

. The relationship between G

. Solving for x, we can obtain the partial pressures.

], which is the equilibrium constant for the dissociation of water;

Chapter 4: Chemical Equilibrium Solutions

to remove the negative sign, we obtain,

38.084 632 52 atm

are 174.0 and 65.6

=0.179 and the molar conductivity is 426.16

ions? Take the

against I for a uni-univalent electrolyte in water at 25 C, with B =0.51 mol

ions but not to palmitate ions. Calculate the concentrations of Na

ions on the two sides of the

ions but not to P

ions. The initial

and determine and K.

= . This leads to a table of values with the following:

are 174.0 and 65.6

from the molar conductivity of NH

ions. To determine the total amount deposited, we use Eq. 7.6.

=0.179 and the molar conductivity is 426.16

ions? Take the

for each ion

= , and since [Ag ] [Cl ]

against I for a uni-univalent electrolyte in water at 25 C, with B =0.51 mol

, explain the sign

ions but not to palmitate ions. Calculate the concentrations of Na

ions on the two sides of the

ions but not to P

ions. The initial

. The ratio of the speeds with which these ions

. Derive an expression for the emf of this cell.

of the electrolyte MCl? E for the M(s)|M

where z is the number of electrons.

Ag (aq) Cl (aq) AgCl(s)

Tl(s) Cl 0.02 TlCl(s) m e

. The ratio of the speeds with which these ions

. Derive an expression for the emf of this cell.

fumarate 2H 2 succinate 0.031V (1)

of the electrolyte MCl? E for the M(s)|M

The half reactions for each electrode are:

? What would be the effect on the rate constant k?

G at 400 C, and the preexponential factor.

H, the Gibbs energy of activation

G, and the entropy of activation

H, the Gibbs energy of activation

? What would be the effect on the rate constant k?

in order to obtain the following Eq. 9.47:

is the time that corresponds to,

49.8 3.7 kJ mol

will generate a straight line.