Physical Chemistry 2nd Edition Ball

Solutions Manual
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Chapter 6
Equilibria for Single Component Systems
6.2. When freeze-drying a complex mixture like coffee, not just water but other volatile
components can be removed from the mixture. The net result is that when water is added
back to the dried coffee (but none of the other volatile components), the coffee probably
will not taste the same.

6.4. Solid and liquid phases of a substance can exist in the same closed, adiabatic system if
the conditions of the system (in particular, the temperature and the pressure) are such that
those conditions correspond to the melting or freezing point of the substance. At the
melting point (or freezing point), both the solid and liquid phases of the substance can co-
exist in an equilibrium state.

6.6. (a) The equilibrium shifts to the liquid phase.

(b) The equilibrium shifts to the gas phase.
(c) The equilibrium shifts to the solid phase.
(d) The system remains in the solid phase (unless there is a stable allotrope or crystal
form of the substance that is more stable at lower temperature. Metallic tin is an
example where this occurs.)

6.8. The algebraically equivalent way is to simply move the negative sign to the other side of
the equation: -dnliquid = dnsolid. The point is that either side of the equation can have the
negative sign.

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6.10. Assume we have a chemical compound, A. Sublimation of A can be represented by the

equation: A(s) → A(g) with an enthalpy of sublimation subH. We can also represent the
fusion and vaporization of A by the following equations:
A(s) → A(l)  fus H We will add these two equations together using Hess’s
A(l) → A(g)  vap H Law.

A(s) → A(g)  fus H +  vap H

Therefore subH= fusH+ vapH

6.12. The heat of fusion given up by the freezing water can be transferred (at least in part) to
the citrus fruit, keeping them warmer and (hopefully) keeping the fruit itself from
freezing.

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6.14. We will assume that 1g of the vapor is removed. The heat lost by the liquid is:
 kJ   1mole 
q = H vap  n =  43.99 (1g )  = 2.44kJ
 mol   18.01g 
Assuming that the temperature of the flask stays constant the only source of this energy is
from the conversion of water to ice (an exothermic process):
 1mole 
2.44kJ = H fus (x g )  . x=7.32 g of ice formed.
 18.01g 
qrev +30, 700 J/mol
6.16. DS = = = +86.9 J/mol·K , fairly close to what would be
T (80.1+ 273.15) K
predicted by Trouton’s rule.

q rev  fus H
6.18. Using the definition of entropy for this isothermal change: S = = and
T T
510,400 J/mol
substituting: 124.7 J/mol  K = T = 4093 K or 3820C.
T

6.20. Imagine taking water from ice at −5°C to liquid water at 5°C. We would need to work
this in 3 steps: ice changing temp from −5°C to 0°C, the phase transition, and the liquid
changing temperature from 0°C to 5°C. For both the first and third step we would use the
equation q=mcT, but the c used in step one is different from the c used in step 3! We
 H 
know that C p =   . If we plotted the molar enthalpy of a substance vs. temperature,
 T  P
the slope of that graph would be Cp. At phase transitions, the plot would be a vertical line,
the slope of which is equal to infinity. Therefore the heat capacity is infinite for a phase
transition.

6.22. The expression “dphase 1 = dphase 2” in the derivation of the Clapeyron equation does not
necessarily imply a closed system because we’re considering chemical potential, which is
an intensive variable.

6.24. We should recognize that thermodynamic values measured at standard conditions, like S
and H and V, may not be very applicable to extreme conditions of temperature and
pressure, since most common thermodynamic values are measured at normal pressure (1
atm) and normal temperatures (like 298 K). However, increasing the pressure by about 6
atm is scarcely a very extreme change in conditions, especially for a solid substance.
Therefore, our answer should be fairly accurate.

6.26. (a) Yes, because a gas phase is involved.

(b) Yes, because a gas phase is involved.
(c) No, because no gas phase is involved.

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(d) No, because no gas phase is involved.

(e) No, because the process isn’t an equilibrium phase change.
(f) No, because no gas phase is involved.
(g) No, because no gas phase is involved.
(h) Yes, because a gas phase is involved.

6.28. First we need to calculate the molar volumes of Ga(s) and Ga(l):
æ 69.723g öæ 1cm3 öæ 1mL öæ 1L ö
1mole Ga(s) : ç ÷ç ÷ç 3 ÷ç ÷ = 0.0118L / mol
è 1mole Ga øè 5.91g øè 1cm øè 1000mL ø
æ 69.723g öæ 1cm3 öæ 1mL öæ 1L ö
1mole Ga(l) : ç ÷ç ÷ç 3 ÷ç ÷ = 0.0114L / mol
è 1mole Ga øè 6.09g øè 1cm øè 1000mL ø
So, DV = (0.0114 - 0.0118)L / mol = -3.51´10-4 L / mol and DT = 298.1- 302.9K = -4.8K.
J
18.45 æ 1L × atm ö
DS K·mol
Using Eqn.6.10, Dp = DT = (-4.8K ) çè ÷ = 2490atm
DV -4
-3.51´10 L / mol 101.32J ø
Approximately 2490 atm of pressure is required to only slightly change the melting point
of the solid.

6.30. Using the fact that V was –0.0070 L/mol for the phase change in exercise 6.23, and the
fact that the monoclinic-to-rhombic phase change must have a H of –0.368 kJ/mol:
æ DH ö Tf æ -368 J/mol öæ (100 + 273.15) K öæ 1 L × atm ö
Dp = ç ÷ ln = ç ÷ç ln ÷ç ÷ p = 6.3 atm, so
è DV ø Ti è -0.0070 L/mol øè (95.5 + 273.15) K øè 101.32 J ø
that increasing the pressure by 6.3 atm to 7.3 atm should make the rhombic phase more
stable.

6.32. No, the behavior of chemical hot packs cannot be described using the Clapeyron equation
or the Clausius-Clapeyron equation because supersaturated solutions are not equilibrium
systems, nor does the process involve a phase change (it involves a solubility change).

6.34. We want to calculate the boiling point of benzene at 1 atm. For this we need to use Eqn.
6.14:
p2 H  1 1
ln =−  − 
p1 R  T2 T1 
J
33.9  10 3
ln
1atm
=− mol  1 − 1 
; T2 = 351.6K = 78.4  C

0.241atm
8.314
J  T2 40 + 273.15 
Kmol
The measured normal boiling point of benzene is around 80°C.

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dp H  p
6.36. If we use = as the form of the Clausius-Clapeyron equation, we can
dT RT 2
substitute directly the values given in the problem:
dp (71,400 J/mol)  (7.9  10 -5 bar)
= = 7.8  10 −6 bar/K.
dT (8.314 J/mol  K)(22.0 + 273.15 K) 2

æ 46.07g öæ 1mL öæ 1L ö
6.38. The molar volume of ethanol can be found: ç ÷ç ÷ç ÷ = 0.058L / mol
è 1mole øè 0.789g øè 1000mL ø

( ) 9.869 110Pa

−6
L atm 
0.058 8.5310 6 Pa
mol 
 
 Latm 
 9.869  10 −6 atm 
 ( 293 .15 K )
( )
 0.0821
p = pe
* V ( l ) p / RT
= 5.95  10 Pa e 3
= 7298Pa 
 Kmol 
 = 0.072atm
 1Pa 
6.40. Since applied pressure is not a vapor pressure, we will use eqn. 6.17.
p*  Latm   2.00 
RT ln  0.0821 (298.15K ) ln  
p * V (l)P p  Kmol   1.47 
ln = ; P = = = 63.9atm
p RT V ( l) L
0.118
mol
Where the molar volume has been calculated using:
æ 147.0g öæ 1mL öæ 1L ö
1, 4 - dichlorobenzene : ç ÷ç ÷ç ÷ = 0.118L / mol
è 1mole øè 1.25g øè 1000mL ø

p1 40,660 J/mol  1 1 
6.42. ln =−  −  p1 = 96.9 atm .
1 atm 8.314 J/mol  K  (300 + 273.15 K 373.15 K 
A pressure of 96.9 atm (which is an increase of 95.9 from normal atmospheric pressure)
corresponds to a depth of (95.9)(10 m) = 959 meters of depth, or over 3100 feet. The
deepest ocean point is found in the Mariana Trench (36,000 ft). Underwater volcanoes
this deep can still boil water because haven’t exceeded the critical pressure of water.

6.44. We want to boil methanol at a temperature of 298.15K. The equation we need is:
p2 H  1 1
ln =−  − 
p1 R  T2 T1 
J
38.56  10 3
p
ln 2 = − mol  1
−
1 
 ; p 2 = 0.096atm
1atm
8.314
J  298.15K 351K 
Kmol
The pressure has to be reduced to approximately 10% of normal atmospheric pressure for
methanol to boil at room temperature.

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6.46. (a) In order for the term dA to have units of energy, and dA has units of m2,  must have
units of J/m2.
(b) The derivative of A, in terms of r, is dA = 8r dr and the derivative of V in terms of r
is dV = 4r2 dr. Substituting into the right side of the equation:
2dV 2(4r 2 dr )
= = 8rdr = dA . (c) By simply rearranging the expression, we can
r r
dA  r 2dV
get dV = . (d) According to the expression dA = , droplets with smaller
2 r
radii will contribute to a larger dA, which will in turn contribute to a larger value of
dG. Since this expression relates the change in area to the change in volume – which
relates directly to how fast the droplet is evaporating, we use this expression for dA,
not the expression in part b. (e) According to our analysis in part d, smaller droplets
should evaporate faster than large droplets. (f) See part e.

6.48. Large bodies of ice can move because large amounts of pressure at the bottom of an ice
body can favor the liquid phase over the solid phase. While it’s doubtful that liquid water
exists at the bottom of a glacier, the ‘solid’ ice may not be as solid as we may think!

dp  S
6.50. For H2O, Vsolid  Vlqd so V = Vlqd − Vsolid is negative. Using eqn 6.9, = , we can
dT V
see that the derivative must be negative since entropy increases for the solid to liquid
phase transition. This derivative is just the slope of the solid/liquid equilibrium line in the
phase diagram of Figure 6.5.

6.52. In Figure 6.16 the regions: solid, liquid, and gas, have 2 degrees of freedom since there is
only one phase present. The lines have one degree of freedom since there are two phases
present, and the triple point has 0 degrees of freedom.

6.54. This situation is similar to that of a gas adsorbed onto a surface (a 2-D gas). The equation
of state for a 2-D gas is  A = nRT where  is the surface pressure and A is the surface
area. The Gibbs phase rule does still apply since there are three independent variables: ,
T, and A.

  
6.56. For equation 6.20,   = − S , the units of  are J/mol and the unit on T is K, so the
 T  p ,n
overall unit on the left side is J/molK, which are the units for molar entropy. For
  
equation 6.21,   = V , the units of  are J/mol and the unit on p is atm or bar,
 p  T ,n
while the unit on the molar volume is L/mol. However, if we remember that the unit J can
be written in terms of Latm, then the units of  can be written as Latm/mol, which when
divided by the unit atm equal units of L/mol, which are the units of molar volume.

6.58. Figure 6.6 shows 12 phase boundaries.

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6.60. If there were such a thing as a single-axis phase diagram, equation 6.17 would probably
be rewritten as ‘degrees of freedom = 2 – P’, because there would be one less variable
needed to determine the exact state of the system.

6.62. Higher pressures would be necessary to keep a vapor in a liquid state. This is evident
from equations 6.21 and 6.24, since vapor phases always have much higher molar
volumes than the liquid phases. This is not always the case for liquid-solid phase changes
(see exercise 6.58, and remember the phase diagram of water).

6.64. Yes. At these intersections three phases of the compound are in equilibrium with
each other. That is the definition of a triple point.

T
6.66. The answer will depend on the Figure and the line chosen. All of them are
p
derivatives, but the phases involved vary with the line.

6.68. As sulfur goes from rhombic to monoclinic, the entropy should be increasing, just like it
would if it were melting or vaporizing as the temperature is increased.

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