CH 353 Fall 2016 Professor Campion

HW 6 Key

1. D 4.1 Describe how the concept of chemical potential unifies the discussion of
phase equilibria.

Chemical potential is the single function that governs phase stability. The phase
whose chemical potential is least under a set of given conditions is the most
stable.   Conditions   under   which   two   or   more   phases   have   equal   chemical
potentials are conditions under which those phases are at equilibrium. 

2. E 4.4(a) What is the maximum number of phases that can be in mutual

equilibrium in a two-component system?

Using the Gibbs phase rule with C = 2 gives

F  4P

The minimum physically meaningful value for F is 0, so the maximum number of
phases that can be in equilibrium is 4. 

3. E 4.5(a) Water is heated from 25°C to 100°C. By how much does its chemical
potential change?

Start with the fundamental equation of chemical thermodynamics: 

dG  Vdp  SdT

From this (and your memory), it should be clear that 

 G 
   S
 T p

For a system containing a single component (like water in this problem)

 G 
    Gm
 n T,p

Therefore

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  
   Sm
 T  p

We are looking for  μ(T2) ­  μ(T1), so we need to integrate the equation directly

above. If we assume that entropy is independent of the given temperature range
(do you think this is a reasonable assumption?), we get 

  Sm,H2O T

We can look up the standard molar entropy of water at 298 K (in the back of
Atkins 9e, for instance) and substitute the appropriate value for  T to get  μ  =
5.2 kJ mol­1. 
  

4. E 4.8(a) The molar volume of a certain solid is 161.0 cm3 mol−1 at 1.00 atm and
350.75 K, its melting temperature. The molar volume of the liquid at this
temperature and pressure is 163.3 cm3 mol−1. At 100 atm the melting temperature
changes to 351.26 K. Calculate the enthalpy and entropy of fusion of the solid.

Solve this problem using the Clapeyron equation: 

dp  trsS p
 
dT  trs V T

By straightforward substitution of the given values, you can find that fusS = 45.2
J K­1 mol­1. At the melting temperature, the solid and liquid are in equilibrium, so
fusG = 0, and 

 fus H  Tf  fusS  16 kJ mol1

5. E 4.13(a) In July in Los Angeles, the incident sunlight at ground level has a
power density of 1.2 kW m−2 at noon. A swimming pool of area 50 m2 is
directly exposed to the sun. What is the maximum rate of loss of water?
Assume that all the radiant energy is absorbed. You will need the enthalpy of
vaporization of water.

I thought this was a fun, practical problem. The rate of loss of mass of water
may be expressed as

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dm d q
  nM  , where n 
dt dt  vap H
dn dq / dt 1.2 x103 W m 2 (50 m 2 )
Thus    1.4 mol s 1
dt  vap H 44.0 x103 J mol 1
dm
and  1.4 mols 1 (18.02g mol 1 )  25g s 1
dt

6. P 4.8 The vapour pressure, p, of nitric acid varies with temperature as

follows:

What are (a) the normal boiling point and (b) the enthalpy of vaporization of nitric
acid?

This problem is mostly an exercise in plotting experimental data and linear fitting.
Integrate the Clausus­Clapeyron equation to get the following expression:

 vap H
ln p  cons tan t 
RT

Therefore, plot ln p versus 1/T, and identify ­vapH/R as the slope of the plot. So,
vapH   =   38   kJ   mol­1.   The   normal   boiling   point   occurs   at  p  =   1   atm.   You   can
interpolate on the plot to get Tb = 357 K. 

7. P 4.10 Construct the phase diagram for benzene near its triple point at 36
Torr and 5.50°C using the following data: ∆fus H = 10.6 kJ mol−1, ∆vap H = 30.8 kJ
mol−1, ρ(s) = 0.891 g cm−3, ρ(l) = 0.879 g cm−3.

Working   through  this problem completely would  be  tedious.  It  would   be  good

practice if you did, but the take home point is that you can determine the slopes
of   the   solid­liquid,   liquid­vapor,   and   solid­vapor   phase   boundaries   using
equations such as the Clapeyron and Clausius­Clapeyron equations. Recall that
these equations can be derived by setting chemical potentials (and the change in
the chemical potentials) of different phases equal to one another and by using
the fundamental equation of chemical thermodynamics.   

8. D 5.3 Explain the origin of colligative properties.

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Recall   that   the   chemical   potential,   μ,   is   the   molar   Gibbs   energy.   For   a
particular component, i, the chemical potential is defined as 

 G 
i   
 n i T,p,n other

The  chemical  potential  is therefore  an  indicator of spontaneous change  in

processes where the number of moles of a substance changes (as occurs in
chemical reactions and phase changes). Now, all of the colligative properties
are a result of the lowering of the chemical potential of the solvent due to the
presence of the solute. A solution contains a solvent and a solute. Clearly, a
solution  has greater  entropy than  a  pure  substance.  At this  point, we  can
make two assumptions: 1) the solute is excluded from the solvent on freezing
and 2) the solute in nonvolatile. If these criteria are fulfilled, then the boiling
point   of   the   solution   will   be   elevated   relative   to   the   pure   solvent,   and   the
freezing point will be depressed. These colligative properties are illustrated
graphically in Figure 5.20 from Atkins 9e below: 

9. E 5.8(b) Consider a container of volume 250 cm 3 that is divided into two

compartments of equal size. In the left compartment there is argon at 100
kPa and 0°C; in the right compartment there is neon at the same temperature
and pressure. Calculate the entropy and Gibbs energy of mixing when the
partition is removed. Assume that the gases are perfect.

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The gases are assumed to be perfect, so mentioning that their identities differ
is a red herring. The Gibbs energy of mixing perfect gases is 

 mix G  nRT  x A ln x A  x B ln x B   pV  x A ln x A  x B ln x B 
1 1 1 1
 
 100 kPa 250 cm3  ln  ln 
2 2 2 2
 17.3J

 mix,ideal gas H  0 and

G  H  TS so

 mix G
 mix S   0.635 J K 1
T

10. E 5.10(b) What proportions of benzene and ethylbenzene should be mixed (a)
by mole fraction, (b) by mass in order to achieve the greatest entropy of
mixing? You will need to differentiate a certain equation to get the answer.
What assumption is made in deriving this equation and why is it valid for this
system of benzene and ethylbenzene? Refer to ideal solutions, gases, and the
relative strengths of intermolecular interactions in your explanation.

In order to form an ideal solution, the components of the solution (let’s call them
A and B) must satisfy the following criterion: the strengths of the A­A, A­B, and B­
B interactions must be of similar magnitude. Since the structures of benzene and
ethylbenzene are similar, it follows that they form an approximately ideal solution
when mixed. From the solution to problem to number 10, the entropy of mixing 

 mix S   nR  x benzene ln x benzene  x ethylbenzene ln x ethylbenzene 

This equation must be differentiated (with respect to either mole fraction), set
equal   to   0,   and   solved   to   find   the   composition   of   the   mixture   that   gives   the
maximum entropy of mixing. (At this point, it may be intuitively clear to you that
entropy is maximized when equal amounts of benzene and ethylbenzene and
benzene  are  present, but let’s continue  with  the  algebra  and  calculus.)  For  a
binary mixture

x benzene  x ethylbenzene  1

Solving for xethylbenzene and substituting gives 

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 mix S   nR  x benzene ln x benzene  (1  x benzene ) ln(1  x ethylbenzene ) 

Use the product rule to get 
d( mix S)
 nR  ln x benzene  1  ln(1  x benzene )  1
dx benzene
 x 
 nR  ln benzene 
 1  x benzene 

Substitute xbenzene =1/2 to get 0. The mass ratio should be 0.74.  

11. P 5.9 Plot the vapour pressure data for a mixture of benzene (B) and acetic
acid (A) given below and plot the vapour pressure/composition curve for the
mixture at 50°C. Confirm that Raoult’s and Henry’s laws are obeyed in the
appropriate regions.

Plotting the data is straightforward. Both Raoult’s and Henry’s law say that the
vapor pressure of a component of a mixture is linearly proportional to its mole
ratio. However, in the case of Raoult’s law, the proportionality constant is the
vapor   pressure   of   the   pure   component   of   interest.   For   Henry’s   law,   the
proportionality constant is creatively called the Henry’s law constant. You can
look up the values of these constants for benzene and acetic acid using various
sources. Raoult’s law is obeyed well when the component of interest is present at
high concentration or when the solution is nearly ideal. Henry’s law is obeyed
well when the component of interest is present at low concentration.   

12. E 5.6(b) The addition of 5.00 g of a compound to 250 g of naphthalene

lowered the freezing point of the solvent by 0.780 K. Calculate the molar
mass of the compound.

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You   can   look   up   the   cryoscopic   constant,   K f,   in   various   references.   For

naphthalene,   you   should   get   something   like   K f  =   6.94   K   kg   mol­1.   The
temperature   change   increases   linearly   with   solute   molality,   b napthalene,
according to 

T  K b b napthalene

Recall   that   the   molality   is   defined   as   the   number   of   moles   of   solute   per
kilogram   of   solvent.   Now,   this   problem   is   solvable   by   straightforward
substitution. The molar mass of the unknown compound is 178 g mol ­1. 

13. D6.5 Explain the molecular basis of the van’t Hoff equation for the
temperature dependence of K.

The   molecular  basis  of  the   van’t  Hoff   equation   stems  from  the   Boltzmann
distribution   of   molecules   over   the   available   energy   levels.   Recall   that   the
number of molecules in a state A relative to the number of molecules in state
B is given by   

nA
 e  (EB  EA )/k BT
nB

So, when the temperature is changed the Boltzmann distribution adjusts. For
an   endothermic   reaction   a   temperature   increase   causes   an   increased
population   of   the   higher   energy   states   of   products   at   the   expense   of   the
population of the lower energy states of reactants and the reaction shifts to
the right. The converse applies to a temperature increase for an exothermic
reaction and the reaction shifts to the left.  

14. D6.8 Devise a method for the determination of the pH of an aqueous solution.
(Any chemists in this class will see this in analytical chemistry, but I wanted
to make sure that engineers see it).

Consider an experimental setup containing two electrochemical half cells. In
one cell, you have some solution with hydrogen ions whose concentration you
want   to   measure.   In   the   other   half   cell,   you   have   some   substance   at   a
reference electric potential. If the half cells are at a different electric potential,
a current will flow when the two are connected by a conductive wire. The
magnitude of the current (or voltage) will vary with the concentration of H +. 

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15. E 6.1(a) Consider the reaction A -> 2B. Initially 1.50 mol of A is present and
no B. What are the amounts of A and B when the extent of reaction is 0.60
mol?

The number of moles of some substance J is a function of the variable that
we call the extent of reaction. Specifically,  . Recall that νJ < 0
n J  n J (0)  J 
for reactants while νJ > 0 for products. Now substituting values gives 

n A  1.5 mol  1(0.60 mol)  0.9 mol

n B  0  2 (0.60 mol)  1.2 mol

16. E 6.2(b) When the reaction 2 A → B advances by 0.051 mol (that is, Δξ =
+0.051 mol) the Gibbs energy of the system changes by −2.41 kJ. What is the
reaction Gibbs energy at this stage of the reaction? At this point, in which
direction will the reaction proceed and why?
The   reaction   Gibbs   energy   is   defined   as   .
 G   G 
rG     
  p,T   p,T
Substituting values gives ΔrG = ­47 kJ mol­1. The reaction will proceed to the
right (more B will be made) because the reaction Gibbs energy is negative.  

17. E 6.3(b) The standard Gibbs energy of the reaction 2 NO 2(g) → N2O4(g) is
−4.73 kJ mol− at 298 K. What is the value of ΔrG when Q = (a) 0.10, (b) 1.0, (c)
10, (d) 100? Estimate (by interpolation) the value of K from the values you
calculate. What is the actual value of K?

Recall   that   .   From   above, .

 r G   r G 0  RT ln Q  r G 0  4.73kJ mol 1
Substituting the given values of the reaction quotient allows us to make the
following table: 

Par Q ΔrG (kJ mol­1)
t 

(a) 0.1 ­10.44

0

(b) 1.0 ­4.73

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(c) 10 0.98

(d) 100 6.69

When   ,   the   reaction   is   at   equilibrium,   and   the   reaction   quotient   is

rG  0
equal to the equilibrium constant. From the table, the reaction Gibbs energy is
equal to 0 between Q = 1.0 and 10. You can plot these data to better estimate
the   equilibrium    constant,   but   I   would   just   say   it   is   around   5.   Since
(p N2O4 / p0 )
K eq 
(p NO2 / p0 ) 2
this implies that the amount of N 2O4 is about 5 times greater than the amount
of   NO2  at   equilibrium.   (Note   that   the   division   by   p 0  is   done   to   make   the
equilibrium   constant   dimensionless).   To   get   a   more   exact   value   for   the
equilibrium constant, solve the following equation for K:   
0
K  e  rG /RT

Using this equation gives K = 6.74. 
18. McQuarrie Example 26-3
a) You can relate an equilibrium constant defined in terms of partial pressures, K p,
to an equilibrium constant defined in terms of concentrations, Kc, by using the
following equation:
co RT  y  z  a  b
K p  Kc ( o )
p
This equation applies to the generic reaction , and the values
aA  bB ƒ yY  zZ
of co and po are 1 mol L-1 and 1 bar. Explain how the conversion factor was
obtained.

The conversion factor in going from Kp to Kc was obtained by assuming the ideal
gas law applies. Specifically, N/V = c = RT/p.

b) Consider the following reaction:

3 1
NH3 (g) € H 2 (g)  N 2 (g)
2 2
Given that Kp = 1.36 x 10-3 at 298 K, determine the corresponding value of Kc.

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In this case, νA= 1, νY= 3/2, and νZ= 1/2. Substituting the given values into the
above equation gives  .   
Kp
Kc   5.49 x10 5
24.79

19. E 6.6(b) Using standard Gibbs free energies and enthalpies of formation from
a source of your choosing, calculate the standard Gibbs energy and the
equilibrium constant at (a) 25°C and (b) 50°C for the reaction
. Assume that the reaction enthalpy
is independent of temperature. Can you think of an instrument that could
measure the partial pressures of CH 4 and Cl2 when this reaction is at
equilibrium?

(a) Using data tables at T1 = 25°C, we find 
 r G 0  f G 0 (CHCl3 ,l)  3 f G 0 (HCl, l)  f G 0 (CH 4 , g)
 73.66 kJ mol1  3(95.30 kJ mol 1 )  (50.72 kJ mol 1 )
 308.84 kJ mol 1
0
K  e r G /RT1

 1.30 1054
(b) To find the standard Gibbs energy of reaction and the equilibrium constant
at T2 = 50°C by the approach used in part (a) (this approach required no
assumptions) we would need tabulated Gibbs energies of formations of
these chemicals at 50°C. But these might not have been measured. As an
alternative, we can use the van’t Hoff equation
r H0  1 1 
ln K(T2 )  lnK(T1 )    
R  T2 T1 

Now the standard heat of reaction can be found using the standard heats of
formation
 
 r H 0   f H 0 (CHCl3 , l)  3 f H 0 (HCl, l)   f H 0 (CH 4 , g)
 134.47 kJ mol1  3( 92.31kJ mol1 )  (74.81kJ mol1 )
 336.59 kJ mol1

Substituting values gives   .  1054  and 1049  are damn

K(50C)  e  3.57 10
114.1 49

large numbers indeed. I think the number of atoms making up the Earth is
around  this  size.   The   products  are   overwhelmingly   present  in   the   majority
here, so it would be very challenging to detect the partial pressures of the
reactants.

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20. E 6.23(b) Calculate the equilibrium constant of the following redox reaction at
25°C from standard potential data (see the CRC, Atkins 9e appendix, or most
analytical chemistry textbooks for standard reduction potentials).

The half cell reactions are 
Cu 2  (aq)  2e   Cu(s)
Sn(s)  2e   Sn 2 (aq)
And the corresponding reduction reactions and standard potentials are
Cu 2   2e   Cu(s) E 0red  0.34 V
Sn 2  2e   Sn(s) E 0red  0.14V
As the reaction is written, the cathode (where reduction takes place) is copper
and the anode is tin. The overall cell potential that would be measured is 
E 0cell  E 0cathode  E anode
0
 (0.34  ( 0.14))V  0.48 V
Now recall from Campion’s PowerPoint presentation that 
 r G 0   FE 0cell
F is the Faraday constant and  ν  is the number of electrons involved in the
redox reaction. By using an approach similar to that used in problems 5 and
7, you can find that the equilibrium constant  .  
K  e37.4  1.7 1016

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