Chapter 04 Chemical Equilibrium

CHAPTER
Chemical Equilibrium
LAIDLER . MEISER . SANCTUARY
Physical Chemistry
Electronic Edition
Publisher: MCH Multimedia Inc.
Problems and Solutions
Chapter 4: Chemical Equilibrium
Equilibrium Constants
Chapter 4
*problems with an asterisk are slightly more demanding
4.1.
A reaction occurs according to the equation:

2A Y + 2Z
If in a volume of 5 dm3 we start with 4 mol of pure A and find that 1 mol of A remains at equilibrium, what is the equilibrium
constant Kc?
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 dm6 mol2
A + 2B Z
In a volume of 5 dm3, 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 Kc for the reaction:

2SO3(g) 2SO2(g) + O2(g)
is 0.0271 mol dm3 at 1100 K. Calculate KP at that temperature.
Solution
4-2
4.5.
When gaseous iodine is heated, dissociation occurs:

I2 2I
It was found that when 0.0061 mol of iodine was placed in a volume of 0.5 dm3 at 900 K, the degree of dissociation (the fraction of
the iodine that is dissociated) was 0.0274. Calculate Kc and KP at that temperature.
Solution
4.6.
It has been observed with the ammonia equilibrium:

N2 + 3H2 2NH3
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, NO2, exists in equilibrium with dinitrogen tetroxide, N2O4:

N2O4(g) 2NO2(g)
At 25.0 C and a pressure of 0.597 bar the density of the gas is 1.477 g dm3. Calculate the degree of dissociation under those
conditions, and the equilibrium constants Kc, KP, and Kx. What shift in equilibrium would occur if the pressure were increased by the
addition of helium gas?
Solution
4-3
4.8.
At 25.0 C the equilibrium:

2NOBr(g) 2NO(g) + Br2(g)
is rapidly established. When 1.10 g of NOBr is present in a 1.0-dm3 vessel at 25.0 C the pressure is 0.355 bar. Calculate the
equilibrium constants KP, Kc, and Kx.
Solution
4.9.
At 100 C and 2 bar pressure the degree of dissociation of phosgene is 6.30 105. Calculate KP, Kc, and Kx for the dissociation:
COCl2(g) CO(g) + Cl2(g)
Solution
4.10.
In a study of the equilibrium

H2 + I2 2HI
1 mol of H2 and 3 mol of I2 gave rise at equilibrium to x mol of HI. Addition of a further 2 mol of H2 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:
H2(g) + I2(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-dm3 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
4-4
4.12. The degree of dissociation of N2O4(g) is 0.483 at 0.597 bar and 0.174 at 6.18 bar. The temperature is 298 K for both
measurements. Calculate KP, Kc, and Kx 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) + O2(g) 2Cl2(g) + 2H2O(g).
If y mol of HCl is formed, derive an expression for KP in terms of y and the partial pressure of oxygen.
(Hint: First develop expressions for the ratios xCl2 /xHCl and xH 2O /xCl2 in terms of y and PO2 )
Solution
4.14.
Using the result of Problem 4.13, evaluate KP for an experiment in which 49% HCl and 51% O2 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 H2, I2, and
HI present at equilibrium. KP = Kc = Kx = 65.0 for the reaction H2(g) + I2(g) 2HI(g).
(Hint: see Example 4.2)
Solution
4-5
Equilibrium Constants and Gibbs Energy Changes

4.16.
The equilibrium constant for the reaction

(C6H5COOH)2 2C6H5COOH
in benzene solution at 10 C is 2.19 103 mol dm3.
a. Calculate G for the dissociation of the dimer.
b. If 0.1 mol of benzoic acid is present in 1 dm3 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 CO2,

CO, and O2 are 0.6, 0.4, and 0.2 atm, respectively. Calculate G at 3000 K for the reaction:
2CO2(g) 2CO(g) + O2(g)
Solution
4.18.
The conversion of malate into fumarate:

1. malate(aq) fumarate(aq) + H2O(l)
is endergonic at body temperature, 37 C; G is 2.93 kJ mol1. In metabolism the reaction is coupled with
2. fumarate(aq) aspartate(aq)
for which G is 15.5 kJ mol1 at 37 C.
a. Calculate Kc for reaction 1.
b. Calculate Kc for reaction 2.
c. Calculate Kc and G for the coupled reaction 1 + 2.
Solution
4-6
4.19.
From the data in Appendix D, deduce the G and KP values for the following reactions at 25.0 C:
a.
b.
c.
d.
4.20.
N2(g) + 3H2(g) 2NH3(g)

2H2(g) + C2H2(g) C2H6(g)
H2(g) + C2H4(g) C2H6(g)
2CH4(g) C2H6(g) + H2(g)
Solution
Calculate Kc and Kx 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) + H2O(g) CO2(g) + H2(g)
is 1.00 105, and S is 41.8 J K1 mol1.
a. Calculate G and H at 25.0 C.
b. Suppose that 2 mol of CO and 2 mol of H2O are introduced into a 10-dm3 vessel at 25.0 C. What are the amounts of CO, H2O,
CO2, and H2 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 mol1. (Standard state = 1 mol dm3.) Suppose that an enzyme couples this reaction
with
2. ATP ADP + phosphate
for which G = 31.0 kJ mol1. 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
4-7
4.23.
Temperature Dependence of Equilibrium Constants
The equilibrium between citrate and isocitrate involves cis-aconitate as an intermediate:

citrate cis-aconitate + H2O 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 1029 mol4 dm12 at 25 C. What is the solubility of Cr(OH)3 in water at this temperature?
Solution

4.25.
A gas reaction:
A B+C
is endothermic and its equilibrium constant KP is 1 bar at 25 C.
a.
b.
c.
d.
e.
What is G at 25 C (standard state: 1 bar)?

Is S, with the same standard state, positive or negative?
For the standard state of 1 M, what are Kc and G?
Will KP at 40 C be greater than or less than 1 bar?
Will G at 40 C (standard state: 1 bar) be positive or negative?
Solution
4-8
4.26. A solution reaction:

A+B X+Y
is endothermic, and Kc 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:

C2H4(g) + H2(g) C2H6(g)
Calculate the following:
a.
b.
c.
d.
e.
f.
4.28.
G, H, and S at 25 C; what is the standard state?

KP at 25 C.
Kc at 25 C (standard state: 1 M).
G at 25 C (standard state: 1 M).
S at 25 C (standard state: 1 M).
KP at 100 C, on the assumption that H and S are temperature independent.
Solution
From the data in Appendix D, for the reaction:

2H2(g) + O2(g) 2H2O(g)
a. G, H, and S at 25 C (standard state: 1 bar).
b. KP at 25 C.
c. G and KP at 2000 C, on the assumption that H and S are temperature independent.
Solution
4-9
4.29.
Calculate the equilibrium constant at 400 K for the reaction:

3O2(g) 2O3(g).
where fG(O3, g) = 163.2 kJ mol1.
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):
G 31.0 kJ mol 1
H 20.1kJ mol 1
a. Calculate S.
b. Calculate Kc at 37 C.
c. On the assumption that H and S are temperature independent, calculate G and Kc 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,
H f kJ mol1
Entropy, S J K1
mol1
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
4-10
4.32.
a. An equilibrium constant Kc 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 Kc 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;
H2O H+ + OH
is 1.00 1014 mol2 dm6 at 25.0 C and 1.45 1014 mol2 dm6 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
4.34. The equilibrium constant KP for the reaction I2(g) + cyclopentane(g) 2 HI(g) + cyclopentadiene(g) varies with temperatures
according to the equation:
log10(KP/bar) = 7.55 4844/(T/K)

a. Calculate KP, G, H, S (standard state: 1 bar) at 400 C.
b. Calculate Kc and G (standard state: 1 M) at 400 C.
c. If I2 and cyclopentane are initially at 400 C and at concentrations of 0.1 M, calculate the final equilibrium concentrations of I2,
cyclopentane, HI, and cyclopentadiene.
Solution
4.35.
From the data in Appendix D, for the synthesis of methanol,

CO(g) + 2H2(g) CH3OH(l)
Calculate H, G, and S and the equilibrium constant at 25 C.
Solution
4-11
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
1
NO 2 (aq) O2 (g) NO3 (aq)
2
Calculate H, G, and S for this reaction from the following data, at 25 C:

f H
Ion
kJ mol
f G
kJ mol 1
NO 2
104.6
37.2
NO 3
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 102 M glucose-1-phosphate and 104 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

CO2(g) + H2(g) CO(g) + H2O(g)
a.
b.
c.
d.
e.
H, G, and S (standard state: 1 bar and 25 C).

The equilibrium constant at 25 C.
From the heat capacity data in Table 2.1, obtain an expression for H as a function of temperature.
Obtain an expression for ln KP as a function of temperature.
Calculate KP at 1000 K.
Solution
4-12
4.39.
Irving Langmuir [J. Amer. Chem. Soc., 28, 1357 (1906)] studied the dissociation of CO2 into CO and O2 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 KP for 2CO2(g) = 2CO(g) + O2(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:
volume of bulb = 249.8 cm3
amount of iodine = 1.958 mmol
Temperature/C
a.
b.
c.
d.
e.
Pressure/Torr
800
558.0
1000
748.0
1200
Calculate the degree of dissociation at each temperature.
Calculate Kc at each temperature, for the process I2 2I.
Calculate KP at each temperature.
Obtain values for H and U at 1000 C.
Calculate G and S at 1000 C.
1019.2
Solution
4-13
4.41. The following diagram shows the variation with temperature of the equilibrium constant Kc for a reaction. Calculate G, H, and
S at 300 K.
Solution
4.42.
The following values apply to a chemical reaction A Z:

H 85.2 kJ mol 1
S 170.2 J K 1 mol 1
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
4.43. The equilibrium constant Kc for the hydrolysis of adenosine triphosphate (ATP) to adenosine diphosphate (ADP) and phosphate is
1.66 105 mol dm3 at 37 C, and H is 20.1 kJ mol1. Calculate S for the hydrolysis at 37 C. On the assumption that H and
S are temperature independent, calculate Kc at 25 C.
Solution
4-14
4.44. A dissociation A2 2A has an equilibrium constant of 7.2 105 mol dm3 at 300 K, and a H value of 40.0 kJ mol1. 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 4.5 104 dm3 mol1 at 300 K, and a H value of 40.2 kJ mol1. 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, G f , is 162.3 kJ mol1, for a standard state of 1 bar. Calculate
the equilibrium constants KP, Kc, and Kx for the process:

3O2(g) 2O3(g)
What is the mole fraction of O3 present at 25 C at 2 bar pressure?
Solution
4.48.
For the equilibrium:

H2(g) + I2(g) 2HI(g)
The following data apply:
H (300 K) = 9.6 kJ mol 1
S (300 K) = 22.18 J K 1 mol 1
C p (500 K) = 7.11 J K 1 mol 1
The latter value can be taken to be the average value between 300 K and 500 K.
4-15
Binding to Protein Molecules
Calculate the equilibrium constants KP, Kc, and Kx 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
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 mol1 and S = 891 J K1 mol1. Assume these values to be temperature independent over
this narrow range, and calculate G and Kc 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
*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 = MA2, etc., all have the same equilibrium
constant Ks. Show that the average number of occupied sites per molecule is:
v
nK s [A]
1 K s [ 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:
M A MA K1
[MA]
[M][A]
MA A MA 2 K 2
[MA 2 ]
[MA][A]
4-16
MA n 1 A MA n K n
[MA n ]
[MA n 1 ][A]
Show that the average number of molecules of A bound per molecule M is:
v
K1[A] 2 K1 K 2 [A]2 n( K1 K 2 K 3 K n )[A]n

1 K1 [A] K1 K 2 [A]2 ( K1 K 2 K3 K n )[ A]n
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 K1 = K2 = K3 = Kn; certain statistical factors must be introduced. Thus,
if Ks is the equilibrium constant for the binding at a given site, K1 = nKs, since there are n ways for A to become attached to a given
molecule and one way for it to come off. Similarly K2 = (n 1)Ks/2; n 1 ways on and 2 ways off. Continue this argument and
develop an expression for v that will factorize into nKs[A]/(1 + Ks[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 Kn is much greater than K1, K2, etc. Show that now:
nK [A]n
1 K [A]n
Where K is the product of K1, K2, Kn. The British physiologist A. V. Hill suggested that binding problems can be treated by plotting:
ln
against ln[A]
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
4-17
Essay Questions
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.
4-18
Solutions
Solutions
4.1.
A reaction occurs according to the equation

2A Y + 2Z
If in a volume of 5 dm3 we start with 4 mol of pure A and find that 1 mol of A remains at equilibrium, what is the equilibrium
constant Kc?
Solution:
Given: V 5 dm3 , ninitial 4 mol, nequilibrium 1 mol

Required: Kc
This equilibrium problem can be solved using a table:
ninitial
nequilibrium
Cequilibrium
2A
4
1
1
5
Y
0
1.5
1.5
5
Y Z
For this reaction, Kc is given by the equation K c
2
A
2Z
0
3.0
3.0
5
mol
mol
mol dm-3
1.5
3.0
mol dm 3
mol dm 3
5
5
Kc
2
1.0
mol dm 3
. Solving using the concentrations at equilibrium gives the following,
K c 2.7 mol dm 3
Back to Problem 4.1
Back to Top
4-19
4.2.
Solutions
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: Kc = 0.1, nBinitial 3 mol , nYequilibrium 2 mol

Required: nAinitial
ninitial
A
nAinitial
nequilibrium
nAinitial 2
B
3

Rearranging for, nA gives, nA
nAinitial 2 mol
nAinitial
Z
0
mol
mol
Y Z . Assuming the total volume is constant for the reaction,

A B
Kc
nY nZ
.
nA nB
nY nZ
and therefore nAinitial can be determined.
K c nB
2 mol 2 mol
0.1 1 mol
2 mol 2
Y
0
mol
0.1 1 mol
2 mol
nAinitial 42 mol
Back to Problem 4.2
Back to Top
4-20
Solutions
4.3.
A + 2B Z
is 0.25 dm6 mol2. In a volume of 5 dm3, what amount of A must be mixed with 4 mol of B to yield 1 mol of Z at equilibrium?
Solution:
Given: Kc = 0.25 dm6 mol2, V= 5 dm3, nBinitial 4 mol , nZequilibrium 1 mol

Required: nAinitial
+
Z
0
mol
ninitial
A
nAinitial
nequilibrium
nAinitial 1
mol
Cequilibrium
nAinitial 1
2
5
1
5
mol dm-3
2B
4
Z . Rearranging for A , gives, A = Z

2
2
K c B
A B
and nAinitial can be determined from
this expression.
Ainitial
1 mol
5 dm3
Ainitial
1 mol
3
5 dm
nAinitial 26 mol
1
3
mol dm
5
2
2
0.25 dm 6 mol 2 mol dm 3

5
5 mol dm 3
Back to Problem 4.3
Back to Top
4-21
Solutions
The equilibrium constant Kc for the reaction
4.4.
2SO3(g) 2SO2(g) + O2(g)

is 0.0271 mol dm3 at 1100 K. Calculate KP at that temperature.
Solution:
Given: Kc = 0.0271 mol dm3, T = 1100 K

Required: KP
The relationship between Kc and KP is given by Eq. 4.26,
KP = Kc(RT)v where v 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 SO3,
v = +1 mol.
Solving for KP gives,
K P 0.0271 mol dm 3 0.083 145 bar dm3 K -1 mol1 1100 K
K P 2.478 55 bar
K P 2.48 bar
Back to Problem 4.4
Back to Top
4-22
4.5.
Solutions
When gaseous iodine is heated, dissociation occurs:

I2 2I
It was found that when 0.0061 mol of iodine was placed in a volume of 0.5 dm3 at 900 K, the degree of dissociation (the fraction of
the iodine that is dissociated) was 0.0274. Calculate Kc and KP at that temperature.
Solution:
Given: nI2 initial 0.0061 mol , V = 0.5 dm3, T = 900 K, , degree of dissociation = 0.0274
Required: Kc and KP
ninitial
nequilibrium
I2
0.0061
0.00611 0.0274
2I
0
0.0061 0.0274 2
mol
5.9329 103
3.3428 104
mol
I . Solving using the concentrations at equilibrium gives the following,

I2
2
3.3428 104
mol dm 3
0.5
Kc
5.9329 103
mol dm 3
0.5
K c 3.7669 105 mol dm 3

K c 3.77 105 mol dm 3

KP = Kc(RT)v, where v 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,
4-23
Solutions
v = +1 mol.
K P 3.77 105 mol dm 3
0.083 145 bar dm3 K -1 mol1 900 K
K P 0.002 821 bar

K P 2.82 103 bar
Back to Problem 4.5
Back to Top
4-24
4.6.
Solutions
It has been observed with the ammonia equilibrium:

N2 + 3H2 2NH3
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,

nNH 2
NH 3
Kc
3
3
N 2 H 2 nN nH
2
If nN2 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 N2 requires that V is increased. If the proportional increase in V2 is greater than the
increase in nN2 , the equilibrium will shift to the left when N2 is added.
The volume is proportional to nNH3 nN2 nH2 and V2 is proportional to nNH3 nN2 nH 2
. If nN2 is much larger than nNH3 nH 2 , V2 will
increase approximately with n 2 N2 and therefore increases more strongly than nN2 . If nN2 is not much larger than nNH3 nH2 , an increase
in nN2 will have a relatively small effect on V2. The increase in ammonia dissociation when N2 is added is therefore expected when N2 is in
excess, but not otherwise.
On the other hand, n3H2 appears in the equilibrium expression; this varies more strongly than V2, and added H2 therefore cannot lead to the
dissociation of ammonia.
Back to Problem 4.6
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4-25
4.7.
Solutions
Nitrogen dioxide, NO2, exists in equilibrium with dinitrogen tetroxide, N2O4:

N2O4(g) 2NO2(g)
At 25.0 C and a pressure of 0.597 bar the density of the gas is 1.477 g dm3. Calculate the degree of dissociation under those
conditions, and the equilibrium constants Kc, KP, and Kx. What shift in equilibrium would occur if the pressure were increased by the
addition of helium gas?
Solution:
Given: T 25C 298.15K, P 0.597 bar, = 1.477 g dm 3

Required: , degree of dissociation, Kc, KP, and Kx. 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 dm3 there
are nN2O4 moles of N2O4 and nNO2 moles of NO2. Therefore the total number of moles is given by n nN2O4 nNO2 .
Using the ideal gas law, PV = nRT , and solving for n, nN 2O4 and nNO2 can be obtained.
n=
n=
PV
RT
(0.597
(0.083 145 bar
bar ) 1 dm3
dm3 K -1 mol-1
)
)(298.15 K )
n = 0.024 083 mol

nN2O4 + nNO2 = 0.024 083 mol
The mole fractions can also be determined using the density of the gas given in the problem.
4-26
m M N2O4 nN2O4 M NO2 nNO2
, where m Mn
V
V
2 14.006 74 g mol
-1
92.011 08 g mol n
N 2O4
2n
2n
1 dm
1 dm
46.005 54 g mol 2n
N 2O4
1 dm
46.005 54 g mol-1 nNO2
-1
4 15.9994 g mol-1 nN2O4 14.006 74 g mol-1 2 15.9994 g mol-1 nNO2
-1
Solutions
nNO2
1.477 g
dm 3
N2 O4
nNO2
N2 O4
nNO2 0.032 105 mol
1 dm
3
46.005 54 g mol
-1
Now we have two equations and two unknowns, and therefore we can solve for the mole fractions.
nN2O4 nNO2 0.024 083 mol
(1)
2nN2O4 nNO2 0.032 105 mol
(2)
Subtracting (1) from (2) gives,

nN2O4 0.008 022 mol
nN2O4 8.02 103 mol
nNO2 0.024 083 mol 0.008 022 mol
nNO2 0.016 061 mol
nNO2 1.61102 mol
If the degree of dissociation is , the amounts of N2O4 and NO2 present are:
4-27
Solutions
N 2 O 4 : P 1
NO 2 : 2 P
Since partial pressures are proportional to the number of moles of each species present,
nN2O4 P 1
nNO2 2 P
therefore,
nNO2
nN 2O4
2 P
P 1
Solving for gives,
1 2 P nN O
P nNO

2
2nN 2O4
nNO2
2 nN 2 O 4
nNO2
2nN2O4 nNO2
nNO2
nNO2
2nN2O4 nNO2
0.016 061 mol
2 0.008 022 mol 0.016 061 mol
0.500 265
0.500
4-28
Solutions
NO2 . From our assumption that in 1 dm3 there are n

The equilibrium constant for this reaction is given by K c
N O
N 2O4
2
moles of N2O4 and
nNO2 moles of NO2, we can solve for Kc.

2
0.016 061 mol
1 dm3
Kc
0.008
022
mol
3
1 dm
K c 0.032 156 mol dm 3

K c 0.0322 mol dm 3
Since there are two moles of nitrogen dioxide produced from one mole of dinitrogen tetroxide,
v = +1 mol.
K P 0.032 156 mol dm 3
0.083145 bar dm3 K -1 mol1 298.15 K
K P 0.797 137 bar

K P 0.797 bar
The relationship between Kx and KP is given by Eq. 4.32,

KP = KxPv , where v is the difference between the moles of products to the moles of products.
Rearranging for Kx gives,
K x K P P v
4-29
Solutions
v = +1 mol.
Kx can therefore be solved, giving,
K x 0.797 137 bar 0.597 bar
K x 1.335 238
K x 1.34
The addition of helium gas would have no effect on the equilibrium since the concentrations, partial pressures, and mole fractions would
remain unchanged.
Back to Problem 4.7
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4-30
4.8.
Solutions
At 25.0 C the equilibrium:

2NOBr(g) 2NO(g) + Br2(g)
is rapidly established. When 1.10 g of NOBr is present in a 1.0-dm3 vessel at 25.0 C the pressure is 0.355 bar. Calculate the
equilibrium constants KP, Kc, and Kx.
Solution:
Given: m 1.10 g, V 1 dm3 T 25C 298.15K, P 0.355 bar

Required: KP, Kc, and Kx
NO Br2 .To calculate K , we must first determine n , the number of moles

The equilibrium constant for this reaction is given by K c
c
NOBr
2
NOBr
2
initially present of NOBr,

nNOBr
mNOBr
M NOBr
nNOBr
1.10 g
14.006 74 g mol 15.9994 g mol-1 79.904 g mol-1
-1
nNOBr 0.010 008 mol

nNOBr 0.01 mol
If is the degree of dissociation, then the number of moles of each gas at equilibrium is given in the following table:
ninitial
nequilibrium
2NOBr
0.01
0.011
2NO
0
0.01
Br2
0

0.01
2
mol
mol
The total number of moles is given by n nNOBr nNO nBr2
4-31
Solutions

n 0.011 0.01 0.01
2

n 0.01 0.01
2
n 0.01 0.005
Using the ideal gas law, PV = nRT , and solving for n, can be obtained
n=
n=
PV
RT
(0.355
(0.083 145 bar
bar ) 1 dm3
dm3 K -1 mol-1
)
)(298.15 K )
n = 0.014 32 mol
where n = 0.01 + 0.005a
n - 0.01
a=
0.005
0.014 32 mol - 0.01
a=
0.005
a = 0.864
From , nNOBr , nNO , and nBr2 can be obtained.
nNOBr 0.01 mol 1
nNO 0.01 mol
nBr2 0.005 mol
nNOBr 0.01 mol 1 0.864
nNO 0.01 mol 0.864
nBr2 0.005 mol 0.864
nNOBr 1.36 103 mol
nNO 8.64 103 mol
nBr2 4.32 103 mol
Solving for Kc gives,
4-32
Solutions
8.64 103 mol 4.32 103 mol
1 dm3
1 dm3
Kc
2
3
1.36 10 mol
1 dm3
-3
K c 0.174 35 mol dm
K c 0.174 mol dm -3
Since there are three moles of total gas produced from two moles of NOBr,
v = +1 mol.
K P 0.174 35 mol dm 3
0.083145 bar dm
K -1 mol1 298.15 K
K P 4.322 08 bar
K P 4.32 bar
K x K P P v
Since there are three moles of total gas produced from two moles of NOBr,
v = +1 mol.

4-33
K x 4.322 08 bar 0.355 bar
Solutions
K x 12.174 87
K x 12.2
Back to Problem 4.8
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4-34
Solutions
At 100 C and 2 bar pressure the degree of dissociation of phosgene is 6.30 105. Calculate KP, Kc, and Kx for the dissociation:
4.9.
COCl2(g) CO(g) + Cl2(g)

Solution:
Given: T 100 C 373.15 K, P 2 bar, 6.30 105

The equilibrium constant in terms of partial pressures is given by K P
PCO PCl2
PCOCl2
To calculate KP, 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:
COCl2
P 1
CO
P
Cl2
P
bar
The total number pressure is given by Ptotal PCOCl2 PCO PCl2

Ptotal P 1 P P
Ptotal P P
P 1 2 bar
P
P
2 bar
1
2 bar
1 6.30 10 5
P 1.999 87 bar
P 2 bar
Solving for KP, we obtain,
4-35
KP
KP
KP
Solutions
P P
P 1
P 2
1
2 bar 6.30 105
1 6.30 10
5
K P 7.9385 109 bar

K P 7.94 109 bar
KP = Kc(RT)v, where v is the difference between the moles of products to the moles of products. Rearranging for Kc gives,
Kc = KP(RT)-v
Since there are two moles of gas produced from one moles of COCl2,
v = +1 mol
K c 7.9385 109 bar
0.083 145 bar dm
K 1 mol1 373.15 K
K c 2.558 697 1010 mol dm 3

K c 2.56 1010 mol dm 3
4-36
Solutions
K x K P P v
Since there are two moles of gas produced from one moles of COCl2,
v = +1 mol
K x 7.9385 109 bar
bar
K x 3.969 25 109
K x 3.97 109
Back to Problem 4.9
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4-37
4.10.
Solutions
In a study of the equilibrium

H2 + I2 2HI
1 mol of H2 and 3 mol of I2 gave rise at equilibrium to x mol of HI. Addition of a further 2 mol of H2 gave an additional x mol of HI.
What is x? What is K at the temperature of the experiment?
Solution:
Given: nH2 1 mol, nI2 3 mol, nH2 added 2 mol
Required: x, K
ninitial
nequilibrium
nafter H2 added
H2
1
x
2
3 x
I2
3
x
2
3 x
2HI
0
x
mol
mol
2x
mol
HI . Assuming the volume is constant, the expression for K becomes,

For this reaction, K is given by the equation K
H 2 I2
2
nHI 2
K
nH 2 nI2
K is always constant, therefore the two expressions obtained at equilibrium and after H2 is added can be used to solve for x.
4-38
Solutions
4 x2
3 x 3 x
x
x
1 3
2
2
x
x
2
3 x 4 1 3
2
2
9 6 x x 2 12 8x x 2
2x 3
x
3
2
Substituting for x, K can be solved.

2
3
4
2
K 2
3
3
2
9
K
2
3

2
9
K
9

4
K 4
Back to Problem 4.10
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4-39
4.11.
Solutions
The equilibrium constant for the reaction below is 20.0 at 40.0 C:

H2(g) + I2(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-dm3 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: K 20.0, T 40.0 C 313.15 K, P 0.10 bar, m 12.7 g, V 10 dm3

Required: nH2
First, the number of moles of I2 is given by,
nI2
nI2
m
M
12.7 g
2 126.904 47
g mol-1
nI2 0.050 037 6 mol

nI2 0.050 mol
By examining the reaction, the consumption of 0.050 mol of I2 leads to the formation of 0.10 mol of HI.
The equilibrium constant for this reaction in terms of partial pressures is given by,
KP
PHI 2
, where PHI is obtained from the ideal gas law.
PH2 PI2
4-40
PHI
PHI
Solutions
nRT
V
0.10 mol 0.083 145 bar dm
K -1 mol-1
313.15 K
10 dm3
PHI 0.26037 bar
Rearranging and solving for PH 2 gives,

PH2
0.260 37 bar
20 0.1 bar
PH2 0.033 896 bar

Then, if PH 2 is the partial pressure of H2 after equilibrium is established, nH 2 equilibrium can be obtained using the ideal gas law.
nH2 equilibrium
nH2 equilibrium
PH 2V
RT
0.033 896
0.083 145 bar
bar 10 dm3
dm3 K -1 mol-1 313.15 K
nH2 equilibrium 0.013 018 mol

This means 0.013 018 mol of H2 is produced in the equilibrium mixture, and 0.05 mol of H2 is required to remove the 0.05 mol of I2. nH 2 is
therefore equal to 0.013018 mol +0.05 mol.
nH2 0.013 018 mol 0.05 mol
nH2 0.063 018 mol
nH2 0.063 mol
Back to Top
4-41
Solutions
4.12. The degree of dissociation of N2O4(g) is 0.483 at 0.597 bar and 0.174 at 6.18 bar. The temperature is 298 K for both
measurements. Calculate KP, Kc, and Kx in each case.
(Hint: See Example 4.1.)

Solution:
Given: P 0.597 bar 0.483, P 6.18 bar 0.174, T 25 C 298.15 K

Required: KP, Kc, and Kx in each case
Suppose that we start with 1 mol of N2O4 and that mol have become converted into NO2; the amounts at equilibrium are
N 2 O 4 2NO 2
1
The total amount is given by, 1 2 1 . If P is the total pressure, the partial pressures are
N 2O4 :
1
2
P and NO 2 :
P
1
1
The equilibrium constant in terms of partial pressures is given by K P
PNO 2 2
PN2O 4
Solving for KP, we obtain,
4-42
Solutions
2 2
P
1
KP
1
P
1
KP P
4 2
KP P
4 2
1 1
KP P
4 2
1 2
At P 0.597 bar ,
K P 0.597 bar
4 0.483
1 0.483
K P 0.726 60 bar
K P 0.727 bar
At P 6.18 bar ,
K P 6.18 bar
4 0.174
1 0.174
K P 0.771 79 bar
K P 0.772 bar
Kc = KP(RT)-v
4-43
Solutions
v = +1 mol.
Solving for Kc at P 0.597 bar gives,
K c 0.726 60 bar 0.083 145 bar dm3 K 1 mol1 298.15 K
K c 0.029 31 mol dm 3
K c 2.93 102 mol dm 3
Solving for Kc at P 6.18 bar gives,
K c 0.771 79 bar 0.083 145 bar dm3 K 1 mol1 298.15 K
K c 0.031 13 mol dm 3
K c 3.11102 mol dm 3
K x K P P v
v = +1 mol.
Solving for Kx at P 0.597 bar gives,
4-44
K x 0.726 60 bar
0.597
bar
Solutions
K x 1.217 09
K x 1.22
Solving for Kx at P 6.18 bar gives,
K x 0.771 79 bar
6.18 bar
K x 0.124 89
K x 0.125
Back to Top
4-45
4.13.
Solutions
One mole of HCl mixed with oxygen is brought into contact with a catalyst until the following equilibrium has been established:
4HCl(g) + O2(g) 2Cl2(g) + 2H2O(g).
If y mol of HCl is formed, derive an expression for KP in terms of y and the partial pressure of oxygen.
(Hint: First develop expressions for the ratios xCl2 /xHCl and xH 2O /xCl2 in terms of y and PO2 )
Solution:
Given: nHCl 1 mol

Required: KP in terms of y and PO2
Rewriting the reaction in terms of one mole of HCl gives,
HCl
1-y
O2
PO2
Cl2
H2O
y/2
y/2
From examining the equation above, it is possible to establish the following relationships:
xCl2
xHCl
xH O
y
, and 2 1
2 1 y
xCl2
These ratios also hold for partial pressures and solving for KP ,
4-46
KP
1
2
P P
P P
Cl2
HCl
KP
O2
1
2
1
4
PCl2
PHCl PO2
KP
H2O
Solutions
1
4
2 1 y
P
O2
1
4
Back to Top
4-47
4.14.
Solutions
Using the result of Problem 4.13, evaluate KP for an experiment in which 49% HCl and 51% O2 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% O2, P = 1 bar, T = 480 C = 753.15 K, y = 0.76

Required: KP
The result from problem 4.13 gives KP as.
KP
2 1 y
P
O2
1
4
Solving using PO2 0.511 bar

KP
0.76
2 1 0.76
K P 1.873 61 bar
K P 1.9 bar
1
1
0.51 bar 4
1
4
1
4
Back to Top
4-48
Solutions
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 H2, I2, and
HI present at equilibrium. KP = Kc = Kx = 65.0 for the reaction
H2(g) + I2(g) 2HI(g).

(Hint: see Example 4.2)
Solution:
Given: mHI 10.0 g, T = 731 K, KP = Kc = Kx = 65.0

Required: xH2 , xI2 , xHI
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 KP, Kc, and Kx are all the same and that
they are dimensionless.
Since there are no reactants present initially, we can write,
H2(g)
x
+ I2(g)
x
2HI(g)
n-2x
Where n is the initial amount of HI present,

nHI
nHI
m
M
1.007 94 g mol
10.0 g
1
126.904 47 g mol1
nHI 0.078 178 mol

nHI 7.8179 102 mol
The equilibrium constant for this reaction in terms of partial pressures is given by,
PHI 2
KP
, which can be written in terms of moles as,
PH2 PI2
4-49
Solutions
nHI 2
KP
nH2 nI2
Solving for the x, the mole fractions xH2 , xI2 , xHI can be obtained.
n 2x
KP
x x
n 2x
65.0
65.0
65.0
x2
n 2x
x
n
2
x
7.8179 102 mol

x
2
7.8179 10 mol
x
10.062 26
x 7.7695 103 mol
8.062 26 2
The mole fractions are given by the expressions,
xH2 xI2
x
n 2x
, and xHI
n
n
Solving for xH2 , xI2 , and xHI gives,
4-50
xH2
Solutions
7.7695 103 mol

xI2
7.8179 102 mol
xH2 xI2 0.099 381

xH2 xI2 9.94 102
xHI
7.8179 102 mol 2 7.7695 103 mol

7.8179 102 mol
xHI 0.080 124

xHI 8.01102
Back to Top
4-51
4.16.
Solutions

(C6H5COOH)2 2C6H5COOH
in benzene solution at 10 C is 2.19 103 mol dm3.
a. Calculate G for the dissociation of the dimer.
b. If 0.1 mol of benzoic acid is present in 1 dm3 of benzene at 10 C, what are the concentrations of the monomer and of the dimer?
Solution:
Given: T 10.0 C 283.15 K, K 2.19 10 3 mol dm 3 , n 0.1 mol, V 1 dm 3

Required: G, Cmonomer, Cdimer
a. Solving for G , given by Eq. 4.27, G RT ln K c
G 8.3145 J K mol1 283.15 K ln 2.19 10 3 mol dm 3

G 14 417 J mol1
G 14.4 kJ mol1
b. This equilibrium problem can be solved using a table:

Cinitial
Cequilibrium
(C6H5COOH)2
0
x
2C6H5COOH
0.1
0.1-2x
mol dm-3
mol dm-3
The equilibrium constant for this reaction is given by,
C6 H5COOH
C6 H 5COOH 2
2
Kc
Using the concentrations at equilibrium given in the table, x can be obtained.
4-52
2.19 10
0.1 2x
Solutions
x
0.01 0.40219 x 4 x 2 0
Using the quadratic formula, the expression can be further simplified.
b b 2 4ac
x
2a
0.40219
0.40219
2 4
4 4 0.01
0.40219 0.041914
8
x 0.055513 mol dm 3 or x 0.0450345 mol dm 3
x
From the equilibrium concentrations, we know that there are (0.1-2x) mol dm-3 of C6H5COOH, therefore, we take x 0.0450345 since 2x
cannot be greater than 0.1.
Therefore,
Cmonomer 0.045 034 5 mol dm 3
Cmonomer 5 102 mol dm 3
Cdimer 0.1 mol dm 3 2 0.045 034 5 mol dm 3
Cdimer 0.009 931 mol dm 3

Cdimer 1102 mol dm 3
Back to Top
4-53
4.17.
Solutions
At 3000 K the equilibrium partial pressures of CO2,

CO, and O2 are 0.6, 0.4, and 0.2 atm, respectively. Calculate G at 3000 K for the reaction:
2CO2(g) 2CO(g) + O2(g)
Solution:
Given: T 3000 K, PCO2 0.6 atm, PCO 0.4 atm, PO2 0.2 atm
Required: G
G is given by Eq. 4.20 as G RT ln K P
The equilibrium constant for this reaction is given by
KP
PCO 2 PO2
PCO2 2
Solving for G gives,

PCO 2 PO2
G RT ln
PCO 2
2
G 8.3145 J K mol
0.4 atm 2 0.2 atm

3000 K ln
0.6
atm
G 60 372.45 J mol1
G 6 10 kJ mol1
Back to Top
4-54
4.18.
Solutions
The conversion of malate into fumarate:

1. malate(aq) fumarate(aq) + H2O(l)
is endergonic at body temperature, 37 C; G is 2.93 kJ mol1. In metabolism the reaction is coupled with
2. fumarate(aq) aspartate(aq)
for which G is 15.5 kJ mol1 at 37 C.
a. Calculate Kc for reaction 1.
b. Calculate Kc for reaction 2.
c. Calculate Kc and G for the coupled reaction 1 + 2.
Solution:
Given: T1 37C = 310.15 K, G1 2.93 kJ mol 1

T2 37C = 310.15 K, G2 15.5 kJ mol 1
Required Kc1, Kc2, Kc1+2, G1+2
a. The relationship between G and Kc is given by Eq. 4.27,
G RT ln K c
Rearranging and solving for Kc gives,
ln K c
K c e
G
RT
G
RT
K c1 e
2.93103 J mol 1
8.3145 J K 1 mol 1 310.15 K
K c1 0.321 03
K c1 0.321
4-55
Solutions
b. Using the procedure in part a, Kc2 can be obtained.
8.3145 J
15.5103 J mol 1
Kc 2
K 1 mol 1 310.15 K
K c 2 407.761
K c 2 408
c. The coupled reaction of 1 + 2 is given by,

malate(aq) aspartate(aq) + H2O(l)
Kc1+2 is given by Eq. 4.65,
K1 K 2 K 3
Therefore solving for Kc1+2 gives,
K c1+2 K c1 K c 2
K c1+2 0.321 408
K c1+2 130.968
K c1+2 131
G1+2 is given by Eq. 4.67, the sum of the free energies of each reaction
G3 G1 G2
Solving for G1+2 gives,
G1 2 2.93 kJ mol 1 15.5 kJ mol 1

G1 2 12.57 kJ mol 1
G1 2 12.6 kJ mol 1
Back to Top
4-56
4.19.
Solutions
From the data in Appendix D, deduce the G and KP values for the following reactions at 25.0 C:
a. N2(g) + 3H2(g) 2NH3(g)
b. 2H2(g) + C2H2(g) C2H6(g)
c. H2(g) + C2H4(g) C2H6(g)
d. 2CH4(g) C2H6(g) + H2(g)
Solution:
Given: T 25C = 298.15 K , Appendix D

Required: G and KP for a-d
a. From Eq. 3.91 the Gibbs energies of formation can be used to obtain G for each reaction.
G f G products f G reactants
G 2 16.4 kJ mol1 0 3 0
G 32.8 kJ mol1
The relationship between G and KP is given by Eq. 4.20,

G RT ln K P
Rearranging and solving for KP gives,
ln K P
KP e
G
RT
G
RT
32.8103 J mol 1
KP e
8.3145 J
mol
298.15 K
K P 557 552 bar 2

K P 5.58 105 bar 2
4-57
Solutions
b. Using the same procedure as part a,
G 32.0kJ mol1 2 0 209.9 kJ mol 1
G 241.9 kJ mol1
G 242 kJ mol1
241.9103 J mol 1
KP e
8.3145 J K 1 mol 1
298.15 K
K P 2.392 522 1042 bar 2

K P 2.39 1042 bar 2
c. Using the same procedure as part a,
G 32.0kJ mol1 0 68.4 kJ mol1
G 100.4 kJ mol1
G 100 kJ mol1
100103 J mol 1
KP e
8.3145 J
mol
298.15 K
K P 3.304 94 1017 bar 1

K P 3.30 1017 bar 1
d. Using the same procedure as part a,
G 32.0kJ mol1 0 2 50.5 kJ mol1
G 69 kJ mol1
4-58
69103 J mol 1
KP e
8.3145 J
mol
Solutions
298.15 K
K P 8.161 64 1013
K P 8.2 1013
Back to Top
4-59
Solutions
Calculate Kc and Kx for each of the reactions in Problem 4.19 assuming total pressures of 1 bar in each case.
4.20.
Solution:
Given: P =1 bar, Problem 4.19

Required: Kc, and Kx in each case
The relationship between Kc and KP is given by Eq. 4.26, KP = Kc(RT)v, where v is the difference between the moles of products to the
moles of products. Rearranging for Kc gives,
Kc = KP(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 Kc,
K c 5.58 105 bar 2
0.083 145 bar dm3 K 1 mol1 298.15 K
K c 908.013 mol2 dm 6
K c 9.08 102 mol2 dm 6

K x K P P 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 Kx
4-60
K x 5.58 105 bar 2

K x 5.58 10
1 bar
Solutions
Repeating this procedure for each reaction gives the following results:
KP
Kc = KP(RT)-v
K x K P P v
a.
5.58 105 bar 2
9.08 102 mol2 dm 6
5.58 105
b.
2.39 1042 bar 2
3.89 1039 mol2 dm 6
2.39 1042
c.
3.30 1017 bar 1
1.33 1016 mol dm 3
3.30 1017
d.
8.2 1013
8.2 1013
8.2 1013
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4-61
Solutions
4.21. At 25.0 C the equilibrium constant for the reaction:
CO(g) + H2O(g) CO2(g) + H2(g)

is 1.00 105, and S is 41.8 J K1 mol1.
a. Calculate G and H at 25.0 C.
b. Suppose that 2 mol of CO and 2 mol of H2O are introduced into a 10-dm3 vessel at 25.0 C. What are the amounts of CO, H2O,
CO2, and H2 at equilibrium?
Solution:
Given: T 25C = 298.15 K, K 1.00 10 5 , S 41.8 J K 1 mol 1

nCO 2 mol, nH 2O 2 mol, V 10 dm 3
Required: G, H at 25.0 C and, nCO equilibrium , nH 2O equilibrium , nCO2 equilibrium , nH 2 equilibrium

a. The relationship between G and K is given by
G RT ln K
G 8.3145 J K 1 mol1 298.15 K ln 1.00 10 5

G 28 540 J mol1
G 2.85 kJ mol1
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,
4-62
H G T S
H 28 540 J mol1
Solutions
298.15 K 41.8 J K
mol 1
H 41 002 J mol1
H 41.0 kJ mol1
b. This equilibrium problem can be solved using a table:
CO(g)
2
2 x
ninitial
nequilibrium
H2O(g)
2
2 x
CO2(g)
0
x
H2(g)
0
x
For this reaction, the equilibrium constant is given by the equation K c K P
mol
mol
CO2 H 2 .
CO H 2O
The total volume is constant for the reaction, and cancels out, therefore we can write,
Kc K P
nCO2 nH 2
nCO nH 2O
Solving for x, we can then obtain nCO equilibrium , nH 2 O equilibrium , nCO2 equilibrium , and nH 2 equilibrium
4-63
Kc K P
x x
2 x 2 x
x2
1.00 10 5
2 x
10 5 2 x x
2 10 5 x 10 5 x
2 10 5 x 1 10 5
x
2 10 5
Solutions
10 5
x 0.006 304 6
Therefore,
nCO 2 equilibrium nH 2 equilibrium x
nCO 2 equilibrium nH 2 equilibrium 0.006 304 6
nCO2 equilibrium nH 2 equilibrium 6.30 103
nCO equilibrium nH 2O equilibrium 2 x
nCO equilibrium nH 2O equilibrium 2 0.006 304 6
nCO equilibrium nH 2O equilibrium 1.993 695 4
nCO equilibrium nH 2O equilibrium 1.99
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4-64
Solutions
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 mol1. (Standard state = 1 mol dm3.) Suppose that an enzyme couples this reaction
with
2. ATP ADP + phosphate
for which G = 31.0 kJ mol1. 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: G1 23.8 kJ mol 1 , G2 31.0 kJ mol 1 ,

T 37.0C = 310.15 K, n 1 mol, V 1 dm 3
Required: K1 , K 2 , K 3
Z . Therefore the units of K will be in mol1 dm3 . The relationship between G

c
A B
and Kc is given by Eq. 4.27,

G RT ln K c
Rearranging and solving for Kc gives,
4-65
ln K c
Kc e
Solutions
G
RT
G
RT
23.8103 J mol 1
K1 e
8.3145 J
K 1 mol 1
310.15 K
K1 9.812 13 105 mol dm 3

K1 9.81105 mol dm 3
K2 can be obtained by following the same procedure. Kc is given by K c
31.0103 J mol 1
K2 e
8.3145 J
mol
ADP phosphate . Therefore the units of K will be in mol dm 3

c
ATP
310.15 K
K 2 166 269 mol dm 3

K 2 1.66 105 mol dm 3
For the coupled reaction, K3 is given by Eq. 4.65,

K1 K 2 K 3
Solving for K3 gives,
K 3 9.81 105 mol1 dm3
1.66 10
mol dm 3
K 3 16.2846
K 3 16.3
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4-66
Solutions
4.23. The equilibrium between citrate and isocitrate involves cis-aconitate as an intermediate:
citrate cis-aconitate + H2O 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: T 25C = 298.15 K, pH = 7.4, xcitrate 0.909, xcis aconitate 0.029, xisocitrate 0.062
Required: K1 , K 2 , K 3 , G
The individual reactions are given by,
1. citrate cis-aconitate + H2O
2. cis-aconitate + H2O isocitrate
3. citrate cis-aconitate + H2O isocitrate
xcis aconitate xH 2O
K1 is given by the equation K1
.
xcitrate
4-67
K1
Solutions
xcitrate
where xH 2O 1
K1
0.029
0.031 903 2
0.909
K1 3.19 102
K2 is given by the equation K 2
xisocitrate

K1
xcis aconitate xH2O

xcitrate
where xH2O 1
0.062
2.137 93
0.029
K 2 2.14
K2
K3 is the overall rate constant and is given by Eq. 4.65,

K1 K 2 K 3

K 3 3.190 32 102 2.137 92
K 3 0.068 207
K 3 6.82 102
The relationship between G and K is given by,

4-68
Solutions
G RT ln K
G 8.3145 J K 1 mol 1 298.15 K ln 0.068 207

G 6656.545 J mol 1
G 6.66 kJ mol 1
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4-69
Solutions
4.24. The solubility product of Cr(OH)3 is 3.0 1029 mol4 dm12 at 25 C. What is the solubility of Cr(OH)3 in water at this temperature?
Solution:
Given: K sp = 3.0 10 29 mol 4 dm 12 T 25C = 298.15 K

Required: solubility of Cr(OH)3
When Cr(OH)3 dissolves, the reaction becomes
Cr OH 3 s
3
Cr 3
A
3OH
3a
Where a is the solubility in mol dm
Ksp is given by the K sp a 3a 27 a 4 .

3
Solving for a,
a
K sp
3.0 10
27
29
mol4 dm 12
27
a 3.246 68 10 8 mol dm 3
a 3.2 10 8 mol dm 3
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4-70
Solutions
4.25. A gas reaction:
A B+C
is endothermic and its equilibrium constant KP is 1 bar at 25 C.
a.
b.
c.
d.
e.
What is G at 25 C (standard state: 1 bar)?

Is S, with the same standard state, positive or negative?
For the standard state of 1 M, what are Kc and G?
Will KP at 40 C be greater than or less than 1 bar?
Will G at 40 C (standard state: 1 bar) be positive or negative?
Solution:
Given: K P = 1 bar, T 25C = 298.15 K

Required:
a. G is given by Eq. 4.20, G RT ln K P
G 8.3145 J K 1 mol 1 298.15 K ln 1 bar

G 0 J mol 1
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,
H G
T
G 0
H
S
T
S
4-71
Solutions
Since the reaction is endothermic,

H 0
S 0
c. The relationship between Kc and KP is given by Eq. 4.26,
Kc = KP(RT)-v
Since there are two moles of gas produced from one mole of A,
v = +1 mol.
Solving for Kc at P 1 bar gives,
K c 1 bar
0.083 145 bar dm
K 1 mol1 298.15 K
K c 0.040 339 4 mol dm 3

K c 4.03 102 mol dm 3
G is given by Eq. 4.27, G RT ln K c

G RT ln K c
G 8.3145 J K -1 mol1 298.15 K ln 4.033 94 102 mol dm 3

G 7958.545 J mol1
G 7.96 kJ mol1
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, KP, will increase.
K P 1 bar
4-72
Solutions
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.
G 0
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4-73
Solutions
4.26. A solution reaction:
A+B X+Y
is endothermic, and Kc 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: K c = 10, T 25C = 298.15 K

Required:
a. An exergonic reaction is one that releases energy, i.e., G 0
G is given by Eq. 4.27,
G RT ln K c
G 8.3145 J K -1 mol1 298.15 K ln 10

G 5708.035 J mol1
G 5.7 kJ mol1
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,
4-74
Solutions
H G
T
where G 0 and H 0 for an endothermic process,
S 0
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4-75
Solutions
From the data given in Appendix D, for the reaction:
4.27.
C2H4(g) + H2(g) C2H6(g)

a. G, H, and S at 25 C; what is the standard state?
b. KP at 25 C.
c. Kc 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. KP at 100 C, on the assumption that H and S are temperature independent.
Solution:
Given: Appendix D, T 25C 298.15 K

Required:
a. From Eq. 3.91 the Gibbs energies of formation can be used to obtain G for each reaction.
G 32.0 kJ mol1 68.4 kJ mol1 0
G 100.4 kJ mol1
G 100 kJ mol1
From Eq. 2.53 the enthalpies of formation can be used to obtain H for each reaction.
H f H products f H reactants
H 84.0 kJ mol1 52.4 kJ mol 1 0
H 136.4 kJ mol 1
H 136 kJ mol 1
The relationship between G, H and S is given by Eq. 3.90,

4-76
Solutions
S
H G
T
136.4 103 J mol1 100.4 103 J mol1
298.15 K
S 120.744 59 J mol1 K
S 121 J mol1 K
b. The relationship between KP and G is given by Eq. 4.20, G RT ln K P . Rearranging and solving for KP gives,
ln K P
KP e
G
RT
G
RT
100.4103 J mol 1
KP e
8.3145 J
mol
298.15 K
K P 3.883 65 1017 bar 1

K P 3.88 1017 bar 1
Kc = KP(RT)-v
Since there is one mole of gas produced from two moles of gas reactants,
v = -1 mol.
4-77
Solutions
K c 3.883 65 1017 bar 1 0.083 145 bar dm3 K -1 mol1 298.15 K
K c 9.627 44 1018 dm3 mol1

K c 9.63 1018 dm3 mol1
d. The relationship between Kc and G is given by Eq. 4.27, G RT ln K c

G 8.3145 J K 1 mol 1 298.15 K ln 9.627 44 1018 dm 3 mol1

G 108 358 J mol 1
G 108 kJ mol 1
e. Solving for S using the expression obtained in part a. gives,

S
136.4 103 J mol1 108 358 J mol 1
298.15 K
S 94.051 49 J mol1 K 1
S 94.1 J mol1 K 1
f. Assuming that H and S are temperature independent, we solve for KP,
4-78
Solutions
G H T S
G 100C 136.4 103 J mol1 373.15 K
120.744 59 J mol
K 1
G 91 462.268 J mol 1
KP e
G
RT
91 462.268 J mol 1
K P 100C e
8.3145 J
mol
373.15 K
K P 6.351 13 1012 bar 1

K P 6.35 1012 bar 1
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4-79
4.28.
Solutions
From the data in Appendix D, for the reaction:

2H2(g) + O2(g) 2H2O(g)

a. G, H, and S at 25 C (standard state: 1 bar).
b. KP at 25 C.
c. G and KP at 2000 C, on the assumption that H and S are temperature independent.
Solution:

Required:
a. From Eq. 3.91 the Gibbs energies of formation can be used to obtain G for the reaction.
G 2 228.6 kJ mol1 2 0 0
G 457.2 kJ mol1
H 2 241.826 kJ mol1 2 0 0
H 483.652 kJ mol1
The relationship between G and H is given by Eq. 3.90,

4-80
H G
T
483.652 103 J mol1 457.2 103 J mol1
Solutions
S
S =
298.15 K
S = 88.720 44 J mol K 1
1
S = 88.72 J mol1 K 1
b. The relationship between KP and G is given by Eq. 4.20, G RT ln K P . Rearranging and solving for KP gives,
ln K P
KP e
G
RT
G
RT
457.2103 J mol 1
KP e
8.3145 J K 1 mol 1
298.15 K
K P 1.252 03 1080 bar 1

K P 1.252 1080 bar 1
c. Assuming that H and S are temperature independent, we solve for G and KP at 2000 C.
4-81
Solutions
G H T S
G 2000C 483.652 103 J mol1 2273.15 K
88.720 44 J mol
K 1
G 281 977.1318 J mol 1

G 282.0 kJ mol 1
KP e
G
RT
281 977.1318 J mol 1
K P 2000C e
8.3145 J K 1 mol 1
2273.15 K
K P 3 015 697.02 bar 1

K P 3.016 106 bar 1
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4-82
Solutions
Calculate the equilibrium constant at 400 K for the reaction:
4.29.
3O2(g) 2O3(g).
where fG(O3, g) = 163.2 kJ mol1.
Solution:
Given: T 400 K , fG(O3, g) = 163.2 kJ mol1

Required: K
From Eq. 3.91 the Gibbs energies of formation can be used to obtain G for the reaction.
G 2 163.2 kJ mol1 3 0
G 326.4 kJ mol1
The relationship between K and G is given by G RT ln K P . Rearranging and solving for K gives,
ln K
K e
G
RT
G
RT
326.4103 J mol 1
K e
8.3145 J K 1 mol 1
400 K
K 2.385 38 1043
K 2.39 1043
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4-83
4.30.
Solutions
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):
G 31.0 kJ mol 1
H 20.1kJ mol 1
a. Calculate S.
b. Calculate Kc at 37 C.
c. On the assumption that H and S are temperature independent, calculate G and Kc at 25 C.
Solution:
Given: T 37 C 313.15 K, G 31.0 kJ mol 1 , H 20.1 kJ mol 1

Required:
a. The relationship between G and H is given by Eq. 3.90,
S
S
H G
T
20.1 103 J mol1 31.0 103 J mol1
310.15 K
S 35.144 29 J mol K 1
1
S 35.1 J mol1 K 1
b. The relationship between Kc and G is given by Eq. 4.27, G RT ln K c . Rearranging and solving for Kc gives,
4-84
ln K c
Kc e
G
RT
G
RT
8.3145 J
31.0 103 J mol 1
Kc
Solutions
K 1 mol 1 310.15 K
K c 166269.3995 mol dm 3
K c 1.66 105 mol dm 3
c. Assuming that H and S are temperature independent, we solve for G and Kc at 25 C.

G H T S
G 25C 20.1103 J mol1 298.15 K
35.14429 J mol
K 1
G 30 578.270 06 J mol 1
G 30.6 kJ mol 1
Kc e
G
RT
30 578.270 06 J mol 1
K c 25C e
8.3145 J K 1 mol 1
298.15 K
K c 227 539.635 mol dm 3

K c 2.28 105 mol dm 3
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4-85
Solutions
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,
H f kJ mol1
Entropy, S J K1
mol1
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.
H 165.98 kJ mol1 146.44 kJ mol1
H 19.54 kJ mol1
From Eq. 3.69 the absolute entropies can be used to obtain H for each reaction.
S S products S reactants
S 306.4 J K 1 mol 1 349.0 J K 1 mol 1
S 42.6 J K 1 mol 1
Solving for G,
4-86
Solutions
G H T S
G 100C 19.54 103 J mol1 298.15 K
42.6 J mol
K 1
G 6838.81 J mol 1
G 6.84 kJ mol 1
b. To calculate the partial pressures, we need to obtain the equilibrium constant KP. The relationship between KP and G is given by Eq.
4.20, G RT ln K P . Rearranging and solving for KP gives,
KP e
G
RT
6838.81 J mol 1
K P 100C e
8.3145 J K 1 mol 1
298.15 K
K P 15.779 83 bar 1
The expression for K P is given by, K P
Pneopentane
Pn pentane
At equilibrium, we have
n-pentane
1-x
Therefore K P becomes, K P
neopentane
x
x
. Solving for x, we can obtain the partial pressures.
1 x
4-87
Solutions
K P 1 x x
KP KP x x 0
K P x K P 1 0
x K P 1 K P
x
KP
K P 1
15.779 83
15.779 83 1
x 0.940 405 bar

Pneopentane x 0.940 bar
Pn pentane 1 x 1bar 0.940 405 bar
Pn pentane 0.059 595 bar
Pn pentane 0.060 bar
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4-88
4.32.
Solutions
a. An equilibrium constant Kc 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 Kc is decreased by a factor of 3 under the same conditions?
Solution:
Given: T1 25.0C 298.15 K, T2 40.0C 313.15 K

Required: H
a. The problem states that K c 2 3K c1 . To obtain H , the standard enthalpy change, we use Eq.4.83.
d ln K c
U
d (1/T )
R
d ln K c
H
This can be written as,

since U and H are very close in solution.
d (1/T )
R

d ln K c
H R
d (1/T )
K 1 1
H R ln c 2
K c1 T2 T1
3 K c1
H 8.3145 J K 1 mol 1 ln
K c1

1
1

313.15 K 298.15 K
H 8.3145 J mol 1 ln 3 1.606 586 19 104
H 56 856.033 83 J mol 1
H 56.9 kJ mol 1
4-89
Solutions
b. The problem states that K c 2 K c1 . Using the same procedure as part a., H can be obtained.
3
K 1 1
H R ln c 2
K c1 T2 T1
K c1
H 8.3145 J K 1 mol 1 ln
3K c1

1
1

313.15 K 298.15 K
H 8.3145 J mol 1 ln 1.606 586 19 104

3
H 56 856.033 83 J mol 1
H 56.9 kJ mol 1
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4-90
4.33.
Solutions
a. The ionic product [H+] [OH], which is the equilibrium constant for the dissociation of water;
H2O H+ + OH
is 1.00 1014 mol2 dm6 at 25.0 C and 1.45 1014 mol2 dm6 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: K1 1.00 10 14 mol2 dm 6 , T1 25.0C 298.15 K K 2 1.45 10 14 mol2 dm 6 , T2 30.0C 303.15 K

Required:
a. To obtain H , the standard enthalpy change, we use Eq.4.83.
d ln K c
U
d (1/T )
R
d ln K c
H
d (1/T )
R

d ln K c
H R
d (1/T )
K 1 1
H R ln 2
K1 T2 T1
1.45 10 14 mol2 dm 6
H 8.3145 J K 1 mol 1 ln
1.00 10 14 mol2 dm 6

H 8.3145 J mol 1 ln 1.45 5.531 942 105

1
1

303.15 K 298.15 K
H 55 845.943 25 J mol 1
H 55.8 kJ mol 1
To obtain S we use the relationship between G, H and S given by Eq. 3.90,
4-91
Solutions
To continue to solve, we must determine G. The relationship between K and G is given by G RT ln K .
G 8.3145 J K 1 mol 1 298.15 K ln 1.00 1014 mol2 dm 6

G 79 912.492 32 J mol 1
Solving for S gives,
S
S
H G
T
55 845.943 25 J mol 1 79 912.492 32 J mol 1
298.15 K
S 80.719 60 J mol K 1
1
S 80.7 J mol1 K 1
b. To obtain K at 37C we use Eq.4.83.
d ln K c
U
d (1/T )
R
d ln K c
H
d (1/T )
R
Rearranging and solving for K2, the solubility product at37C, gives,
4-92
Solutions
K 1 1
H
ln 2
R
K1 T2 T1
K
H 1 1
ln 2

R T2 T1
K1
ln K 2 ln K1
ln K 2
K2 e
H 1 1

R T2 T1
H 1 1
ln K1
R T2 T1
H 1 1

ln K1
R
T
T
2 1
Solving for K2,
K2 e
K2 e
K2 e
55 845.943 25 J mol 1
1
1
8.3145 J K 1 mol 1 310.15 K 298.15 K
14
mol2 dm 6
ln 1.0010
6716.692 916 1.29770110 32.236 19

-4
31.364 564 09
K 2 2.390 798 10 14 mol2 dm 6

K 2 2.39 10 14 mol2 dm 6
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4-93
4.34.
Solutions
The equilibrium constant KP for the reaction I2(g) + cyclopentane(g) 2 HI(g) + cyclopentadiene(g) varies with temperatures
according to the equation:
log10(KP/bar) = 7.55 4844/(T/K)
a. Calculate KP, G, H, S (standard state: 1 bar) at 400 C.
b. Calculate Kc and G (standard state: 1 M) at 400 C.
c. If I2 and cyclopentane are initially at 400 C and at concentrations of 0.1 M, calculate the final equilibrium concentrations of I2,
cyclopentane, HI, and cyclopentadiene.
Solution:
Given: T 400C 673.15 K

Required:
a. KP can be obtained from the equation log10(KP/bar) = 7.55 4844/(T/K).
log10 K P / bar 7.55

K P 10
4844
T / K
4844
7.55
4844
7.55
673.15
K P 10
K P 2.259 34 bar 1
K P 2.26 bar 1
The relationship between KP and G is given by Eq. 4.20, G RT ln K P
G 8.3145 J K 1 mol 1 673.15 K ln 2.259 34 bar 1

G 4561.885 J mol 1
G 4.56 kJ mol 1
4-94
Solutions
The temperature dependence of the equilibrium constant is given by the equation

log10(KP/bar) = 7.55 4844/(T/K). From this equation, H, by converting it into Eq. 4.75, ln K P
H
I .
RT
To convert log10KP to ln KP , we use the law of logarithm that states log a blogb x log a x
ln 10log10 K P ln K P
ln K P 2.303log10 K P
4844
2.303log10 K P
2.303+7.55
T
To solve for H, we drop the 7.55 term and multiply by R

H 2.303R log10 K P
H 2.303 8.3145 J K 1 mol 1 4844 K
H 927 54.334 J mol 1

H 92.75 kJ mol 1

S
H G
T
927 54.334 J mol1 4561.885 J mol1
673.15 K
S 144.568 J mol1 K
S 145 J mol1 K
4-95
Solutions
b. The relationship between Kc and KP is given by Eq. 4.26,

Kc = KP(RT)-v
Since there are three moles produced from two moles of gas reactants,
v = +1 mol.
K c 2.259 34 bar 1 0.083 145 bar dm3 K -1 mol1 673.15 K
K c 0.040 368 dm3 mol1

K c 4.04 102 dm3 mol 1
The relationship between Kc and G is given by Eq. 4.27, G RT ln K c

G 8.3145 J K 1 mol 1 673.15 K ln 0.040 368 dm3 mol1

G 17 964.488 26 J mol 1
G 18.0 kJ mol 1
c. To calculate the equilibrium concentrations, we need to obtain the expression for the equilibrium constant Kc.
HI cyclopentadiene
Kc
I2 cyclopentane
2
At equilibrium, we have
I2(g)
0.1 x
cyclopentane(g)
0.1 x
2 HI(g)
2x
cyclopentadiene(g)
x
4-96
Solutions
Therefore K c becomes,
2x x
Kc
0.1 x 0.1 x
2
Kc
4 x3
0.1 x
Solving for x, we can obtain the equilibrium concentrations.

0.040 368 dm3 mol1
4 x3
0.1 x
2
0.040 368 dm3 mol1 0.1 x 4 x3
2
0.040 368 dm3 mol1 0.01 0.2 x x 2 4 x3

4.0368 104 dm3 mol1 8.0736 102 dm3 mol1 x 4.0368 102 dm3 mol1 x 2 4 x3 0
To obtain x we can graph the equation and find the solution.
x 0.005 006 32 mol dm 3
4-97
Solutions
cyclopentadiene x 0.005 006 32 mol dm3

cyclopentadiene 5.01103 mol dm 3
HI 2 x 2 0.005 006 32 mol dm 3
HI 0.010 012 64 mol dm 3
HI 1.00 102 mol dm 3
I2 cyclopentane 0.1 x
I2 cyclopentane 0.09499368 mol dm 3
I2 cyclopentane 9.50 102 mol dm 3
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4-98
4.35.
Solutions
From the data in Appendix D, for the synthesis of methanol,

CO(g) + 2H2(g) CH3OH(l)
Calculate H, G, and S and the equilibrium constant at 25 C.

Solution:

Required: H, G, S, K
H 239.2 kJ mol1
110.53 kJ mol
2 0
H 128.67 kJ mol1
H 128.7 kJ mol1
From Eq. 3.91 the Gibbs energies of formation can be used to obtain G for each reaction.
G 166.6 kJ mol1
kJ mol
2 0
G kJ mol1
G kJ mol1
4-99
H G
T
1
J mol J mol1
Solutions
S
S =
298.15 K
S = J mol1 K
S = J mol1 K
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4-100
4.36.
Solutions
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
1
NO 2 (aq) O 2 (g) NO3 (aq)
2
Calculate H, G, and S for this reaction from the following data, at 25 C:

Ion
f H
kJ mol
f G
kJ mol 1
NO 2
104.6
37.2
NO 3
207.4
111.3
Solution:
Given: T 25C 298.15 K

Required: H, G, S
1
H 207.4 kJ mol1 104.6 kJ mol1 0

2
H 102.8 kJ mol1
1
G 111.3 kJ mol1 37.2 kJ mol1 0

2
G 74.1 kJ mol1
4-101
Solutions

H G
T
102.8 103 J mol1 74.1 103 J mol1
S
S =
298.15 K
S 96.260 27 J mol1 K 1
S 96.26 J K 1 mol1
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4-102
4.37.
Solutions
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 102 M glucose-1-phosphate and 104 M glucose-6-phosphate. In which direction
does reaction occur under these conditions?
Solution:
Given: T 25C 298.15 K , xglucose 6 phosphate 0.95

Required:
a. To calculate G, we first find the equilibrium constant for the reaction.
K
K
glucose 6 phosphate
glucose 1 phosphate
xglucose 6 phosphate
1 xglucose 6 phosphate
solving for K gives,

0.95
K
1 0.95
K 19
The relationship between K and G is given by, G RT ln K
4-103
Solutions
G 8.3145 J K 1 mol 1 298.15 K ln 19

G 7299.170 52 J mol 1
G 7.3 kJ mol 1
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.
K
glucose 6 phosphate 104

glucose 1 phosphate 102
102
GK 102 8.3145 J K 1 mol 1 298.15 K ln 102

GK 102 11 416.070 33 J mol 1
G G GK 102
G 7299.170 52 J mol 1 11 416.070 33 J mol 1
G 18 715.245 35 J mol 1
G 19 kJ mol 1
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4-104
Solutions
From the data in Appendix D, for the reaction
4.38.
CO2(g) + H2(g) CO(g) + H2O(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 KP as a function of temperature.
e. Calculate KP at 1000 K.
Solution:

Required:
a. From Eq. 2.53 the enthalpies of formation can be used to obtain H for each reaction.
H 110.53 kJ mol1 241.826 kJ mol1 393.51 kJ mol1 0
H 41.154 kJ mol1
G 111.3 kJ mol1 kJ mol1 228.6 kJ mol1
G kJ mol1
4-105
Solutions
S
S =
H G
T
102.8 103 J mol1 74.1 103 J mol1
298.15 K
S 96.26027 J mol1K 1
S 96.26 J K 1 mol1
b. The relationship between K and
c. Heat capacity is given by equation 2.52 as,

1
H m (T2 ) H m (T1 ) d (T2 ) e(T22 T12 ) f
2
1 1

T2 T1
From the values in Table 2.1 we can obtain d, e and f.

d d (products) d (reactants)
d 28.41 30.54 44.22 27.28
d 12.55 J K 1 mol 1
e e(products) e(reactants)
e 4.10 10.29 10 3 8.79 3.26 10 3
e 2.34 10 3 J K 2 mol 1
4-106
Solutions
f f (products) f (reactants)
f 4.6 0 104 86.2 5.0 104
f 76.6 104 J K mol 1
Solving for an expression for H as a function of temperature gives,
H T2 41 154 J mol1 12.55 J K 1 mol 1 T2
1
2
2.34 10 3 J K 2 mol 1 T22 298.15 K
1
76.6 104 J K mol 1
T2 298.15 K
Simplifying we obtain,
1
1
2
H T2 41 154 12.55T2 1.17 10 3 T22 298.15 76.6 104
T2 298.15
76.6 104 76.6 104
2
3 2
3
H T2 41 154 12.55T2 1.17 10 T2 1.17 10 298.15
T2
298.15
H T2 41 154 12.55T2 1.17 10 3 T22 104.005
H T2 43 619.172 12.55T2 1.17 10 3 T22
76.6 104
2569.177
T2
76.6 104
T2
H T 43 619 J mol1 1.17 10 3 J K 2 mol 1T 2 12.55 J K 1 mol 1T
76.6 104 J K mol 1

T
d. To obtain an expression for lnKP, we use Eq. 4.72,

d ln K P H
dT
RT 2
Rearranging for lnKP gives,
4-107
Solutions
H
dT
RT 2
H
dT
ln K P
RT 2
d ln K P
Substituting the expression obtained in part c., we obtain,

H T 43 619 1.17 10 3 T 2 12.55T
To obtain I, we use the result from part b.
76.6 104
T
ln K P
H
dT
RT 2
ln K P
43 619 1.17 10 3 T 2 12.55 T 76.6 104 1
dT
RT 2
T
RT 2
RT 2
RT2
1.17 10 3 J K 1 mo
1
1
ln K P
8.3145 J K 1 mol1 43 619 J mol
43 619 1.17 10 3 12.55 76.6 104
dT
RT 2
R
RT
RT 3
1
12.55 43 619 76.6 104
ln K P 1.17 10 3
dT
R
T
T2
T3
1
43 619 76.6 104
e. To calculate KP at 1000 K, we use the
ln K P 1.17 10 3 T 12.55ln T
I , where I is an integration factor
2
expression obtained in part d.
2T
R
T
ln K P
1
43 619 38.3 104 K
3
1
ln K P
1.17 10 K 1000 K 12.55ln 1000 K
8.3145 J K 1 mol1
1000 K 1000 K 2
1
43 619 38.3 104 K
3
1
ln K P
1.17 10 K 1000 K 12.55ln 1000 K
8.3145 J K 1 mol1
1000 K 1000 K 2
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4-108
4.39.
Solutions
Irving Langmuir [J. Amer. Chem. Soc., 28, 1357 (1906)] studied the dissociation of CO2 into CO and O2 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 KP for 2CO2(g) = 2CO(g) + O2(g) at each temperature, and estimate H, G, and S at 1395 K.
Solution:
Given: P = 1atm, percent dissociation

Required: K P at T =1395 , K P at T =1443 , K P at T =1498 , H T =1395, GT =1395, S T =1395
To determine KP we find an expression in terms of the amounts of CO2, CO and O2.
2CO2
1-x
KP
xCO
2CO
x
02
x/2
xO2
CO 2
x

2
KP
2
1 x
KP
1 x3
2 1 x 2
Solving for KP at each temperature gives,
4-109
K P at T =1395
1 0.0140 10
2 1 0.0140 102
Solutions
K P at T =1395 1.372 38 1012 atm

where 1 atm 1.01325 bar
K P at T =1395 1.390 57 1012 bar
K P at T =1395 1.39 1012 bar
K P at T =1443
1 0.0250 10
2 1 0.0250 102
K P at T =1443 7.816 41 1012 atm

K P at T =1443 7.919 98 1012 bar
K P at T =1443 1.39 1012 bar
K P at T =1498
1 0.0471 10
2 1 0.0471 102
K P at T =1498 5.229 28 1011 atm

K P at T =1498 5.298 57 1011 bar
K P at T =1498 5.30 1011 bar
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4-110
Solutions
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:
volume of bulb = 249.8 cm3
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 Kc at each temperature, for the process I2 2I.
c. Calculate KP at each temperature.
d. Obtain values for H and U at 1000 C.
e. Calculate G and S at 1000 C.
Solution:
Given: n 1.958 103 mol, V 249.8 103 dm3

Required:
a. The reaction in this problem is given by
2I
I2
y/2
mol
x
The degree of dissociation, , can be obtained by first determining the number of moles of I2 and I present.
The total number of moles present at equilibrium is given by,
4-111
Solutions
y
1.958 103 mol
2
(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
x y
x y
PV
RT
1 atm
3
3
558.0 torr
249.8 10 dm
760.0
torr
3
0.082 06 atm dm K 1 mol 1 1073.15 K
x y 2.082 67 103 mol
(2)
Now we have two equations and two unknowns, and subtracting (1) from (2), we can obtain y.
y
1.2467 104 mol
2
y 2.4934 104 mol
x 2.082 67 103 mol 2.4934 104 mol
x 1.8333 103 mol
Solving for the degree of dissociation,
4-112
T 1073.15 K 1
T 1073.15 K
T 1073.15 K
Solutions
x
2
1.8333 103 mol

1
1.958 103 mol
0.063 874
ntotal
T 1073.15 K 6.39 102

Repeating this procedure, we can determine at 1273.15 K,
x y
x y
PV
RT
1 atm
3
3
748.0 torr
249.8 10 dm
760.0
torr
3
0.082 06 atm dm K 1 mol 1 1273.15 K
x y 2.353 25 103 mol
(3)
y
3.9525 104 mol
2
y 7.905 104 mol
x 2.353 25 103 mol 7.905 104 mol
x 1.562 75 103 mol
4-113
T 1273.15 K 1
T 1273.15 K
T 1273.15 K
Solutions
x
2
3
1.562 75 10 mol
1
1.958 103 mol
0.201 86
ntotal
T 1273.15 K 0.202
Repeating this procedure, we can determine at 1473.15,
PV
RT
1 atm
3
3
1019.2 torr
249.8 10 dm
760.0
torr
x y
3
0.082 06 atm dm K 1 mol 1 1473.15 K
x y
x y 2.771 15 103 mol
(4)
y
8.1315 104 mol
2
y 1.6263 103 mol
x 2.771 15 103 mol 7.905 104 mol
x 1.144 85 103 mol
4-114
T 1473.15 K 1
T 1473.15 K
T 1473.15 K
Solutions
x
2
3
1.144 85 10 mol
1
1.958 103 mol
0.415 30
ntotal
T 1473.15 K 0.415
b. To determine the value of Kc at each temperature, we use the number of moles of I2 and I, i.e. the values of x and y obtained in part a. The
expression for the equilibrium constant is given by,
I , where C n
Kc
V
I2
2
y

V
Kc
x

V
y2 1
Kc
x V
At T = 1073.15 K,
2.4934 10
1.8333 10
Kc
K c 1.357 56 10
1
mol 249.8 10
mol
mol dm
dm3
K c 1.358 104 mol dm 3

At T = 1273.15 K,
4-115
Kc
7.905 10
mol
1.562 75 10
mol
Solutions
1
249.8 103 dm3
K c 1.600 74 103 mol dm 3

K c 1.601 103 mol dm 3
At T = 1473.15 K,
1.6263 10 mol
1
1.144 85 10 mol 249.8 10

2
Kc
dm3
K c 9.248 27 103 mol dm 3

K c 9.248 103 mol dm 3
Since there are two moles of I produced from one mole of I2,
v = +1 mol.
Solving for KP at T = 1073.15 K gives,
K P 1.357 56 104 mol dm 3
0.083 145 bar dm
K -1 mol1 1073.15 K
K P 0.012 113 bar

K P 0.0121 bar
At T = 1273.15 K,
4-116
K P 1.60 074 103 mol dm 3
Solutions
0.083 145 bar dm3 K -1 mol1 1273.15 K
K P 0.169 448 bar

K P 0.1694 bar
At T = 1473.15 K,
K P 9.248 27 103 mol dm 3
0.083 145 bar dm
K -1 mol1 1473.15 K
K P 1.132 77 bar
K P 1.133 bar
d.
e. The relationship between KP and G is given by Eq. 4.20, G RT ln K P
G 8.3145 J K 1 mol 1 1273.15 K ln 0.169 448 bar

G 18 791.664 J mol 1
G 18.79 kJ mol 1

S
S =
H G
T
J mol1 18 791.664 J mol1
1273.15 K
4-117
Solutions
S = J mol1 K
S = J mol1 K
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4-118
Solutions
4.41. The following diagram shows the variation with temperature of the equilibrium constant Kc for a reaction. Calculate G, H, and
S at 300 K.
Solution:
Given: Graph
Required: G, H, and S at 300 K
The relationship between Kc and G is given by Eq. 4.27, G RT ln K c
G 8.3145 J K 1 mol 1 300 K ln 5.7 103

G 12 889.028 J mol 1
G 12.9 kJ mol 1
The temperature dependence of equilibrium constants is given by Eq. 4.83 as
4-119
Solutions
d ln K c
U
.
d (1/T )
R
d ln K c
H
d (1/T )
R

d ln K c
H R
d (1/T )
K 1 1
H R ln c 2
K c1 T2 T1
5.7 103 1
1
H 8.3145 J K 1 mol 1 ln
4
7.8 10 300 K 340 K
5.7 103
H 8.3145 J mol 1 ln
3.921 57 104
4
7.8 10
H 42 169.192 J mol 1
H 42.2 kJ mol 1

S
H G
T
42 169.192 J mol1 12 889.028 J mol1
300 K
4-120
Solutions
S 183.5274 J mol1 K
S 184 J mol1 K
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4-121
Solutions
The following values apply to a chemical reaction A Z:
4.42.
H 85.2 kJ mol 1
S 170.2 J K 1 mol 1
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: H 85.2 kJ mol 1 , S 170.2 J K 1 mol 1 , T 300 K
Required: Kc, T where K = 1

G 85.2 103 J mol 1 300 K
170.2 J K
mol 1
G 341 40 J mol 1
The relationship between Kc and G is given by Eq. 4.27, G RT ln K c . Rearranging and solving for Kc gives,
ln K c
Kc e
G
RT
G
RT
34 140 J mol 1
Kc e
8.3145 J
mol
300 K
K c 879 344.891 2
K c 8.79 105
4-122
Solutions
The equilibrium constant is equal to unity when G is equal to zero.

G RT ln 1
G RT 0
G 0
Rearranging Eq. 3.90 we can obtain the temperature at which this occurs.
G H T S
H G
, where G 0
S
H
T
S
T
85.2 103 J mol 1
170.2 J K 1 mol 1
T 500.587 54 K
T 501 K
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4-123
Solutions
4.43. The equilibrium constant Kc for the hydrolysis of adenosine triphosphate (ATP) to adenosine diphosphate (ADP) and phosphate is
1.66 105 mol dm3 at 37 C, and H is 20.1 kJ mol1. Calculate S for the hydrolysis at 37 C. On the assumption that H and
S are temperature independent, calculate Kc at 25 C.
Solution:
Given: Kc = 1.66 105 mol dm3, H = 20.1 kJ mol1 T 37C 303.15 K

Required: S where T 37C 303.15 K , Kc where T 25C 298.15 K
The equilibrium in this problem is given by
ATP ADP + phosphate
Rearranging gives,
S
H G
T
To obtain G, we use the relationship between Kc and G, given by Eq. 4.27, G RT ln K c

G 8.3145 J K 1 mol 1 310.15 K ln 1.66 105 mol1 dm3

G 30 995.818 38 J mol 1
S
20.1103 J mol 1 30 995.818 38 J mol 1
S 35.130 802 J K
303.15 K
mol 1
S 35.1 J K 1 mol 1
4-124
Solutions
Assuming H and S are temperature independent, we can calculate Kc from Eq. 4.27 by first obtaining G from Eq. 3.90 at 25 C
G H T S
G 20.1103 J mol 1 298.15 K
35.130 802 J K
mol 1
G 30 574.248 62 J mol 1
G RT ln K c
Kc e
G
RT
30 574.248 62 J mol 1
Kc e
8.3145 J K 1 mol 1
298.15 K
K c 227 170.8135 mol dm 3

K c 2.27 105 mol dm 3
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4-125
Solutions
4.44. A dissociation A2 2A has an equilibrium constant of 7.2 105 mol dm3 at 300 K, and a H value of 40.0 kJ mol1. 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: K c 7.2 10 5 mol dm 3 T 300 K, H 40.0 kJ mol 1

Required: S , T where K 1
Rearranging gives,
S
H G
T

G 8.3145 J K 1 mol 1 300 K ln 7.2 10 5 mol dm 3

G 23 793.216 63 J mol 1
S
40.0 103 J mol 1 23 793.216 63 J mol 1
S 54.022 611 J K
300 K
mol 1
S 54 J K 1 mol 1
4-126
Solutions
G RT ln 1
G RT 0
G 0
G H T S
H G
, where G 0
S
H
T
S
T
40.0 103 J mol 1
54.022 611 J K 1 mol 1

T 740.430 706 K
T 740 K
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4-127
Solutions
4.45. A reaction A + B Z has an equilibrium constant of 4.5 104 dm3 mol1 at 300 K, and a H value of 40.2 kJ mol1. 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: K c 4.5 104 dm3mol 1 T 300 K, H 40.2 kJ mol 1

Required: S , T where K 1
Rearranging gives,
S
H G
T

G 8.3145 J K 1 mol 1 300 K ln 4.5 104 dm3 mol 1

G 26 725.507 96 J mol 1
S
40.2 103 J mol 1 26 725.507 96 J mol 1
S 44.914 973 J K
300 K
mol 1
S 44.9 J K 1 mol 1
4-128
Solutions
G RT ln 1
G RT 0
G 0
G H T S
H G
, where G 0
S
H
T
S
T
40.2 103 J mol 1
44.914 973 J K 1 mol 1

T 895.024 472 K
T 895 K
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4-129
Solutions
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: Tb 58.2 C, PT 9.3 C 0.1334 bar, T 25 C

Required: H , S , G
First of all, the equilibrium represented in this problem is given by
Br2 (l) Br2 (g)
To solve for G we can use Eq. 4.20

G RT ln K P
We use the vapour pressure as a measure of the equilibrium constant and under the equilibrium conditions, Tb 58.2 C 331.35 K we
obtain,
G T 331.35 K 8.3145 J K 1 mol1 331.35 K ln 1 bar

G 331.35 K 0 J mol 1
Where T 9.3 C 282.45 K , we obtain
G 282.45 K 8.3145 J K 1 mol1 282.45 K ln 0.1334 bar

G 282.45 K 4 730.685 837 J mol1
G 282.45 K 4 731 J mol1
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.
4-130
Solutions
G H T S
4 731 J mol1 H 282.45 K S
(1)
0 J mol1 H 331.35 K S
(2)
Subtracting (2) from (1) and then solving gives,

4 730.685 837 J mol 1 48.9 K S
S
4 730.685 837 J mol 1

48.9 K
S 96.742 042 J K 1 mol1

S 96.74 J K 1 mol1
G H T S 0
H T S
H 331.35 K
96.742 042 J K
mol1
H 32 055.475 5 J mol 1
H 32 055 J mol 1
To solve for the vapour pressure at T 25 C 298.15 K , first we find the value for G, and solve for vapour pressure using Eq. 4.20.
4-131
G H T S
G 32 055 J mol 1 298.15 K
Solutions
96.74 J K
mol1
G 3 211.969 J mol1
G RT ln P
G
RT
P e
3 211.969 J mol1
8.3145 J K 1 mol1 298.15 K
Pe
P 0.273 709 522 bar
P 0.273 7 bar
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4-132
4.47.
Solutions
The standard Gibbs energy of formation of gaseous ozone at 25 C, G f , is 162.3 kJ mol1, for a standard state of 1 bar. Calculate
the equilibrium constants KP, Kc, and Kx for the process:
3O2(g) 2O3(g)
What is the mole fraction of O3 present at 25 C at 2 bar pressure?
Solution:
Given: T 25 C 298.15 K, G f 162.3 kJ mol1 , P 2 bar

First of all, the G for the reaction can be calculated from the standard Gibbs energy of formation for gaseous ozone as,
G 2 G f 2 162.3 kJ mol1
G 324.6 kJ mol 1
Rearranging Eq. 4.20, as shown in Problem 4.46, gives an expression for the KP
G RT ln K P
KP e
KP e
RT
324 600 J mol1
8.3145 J K 1 mol1 298.15 K
K P 1.357 68 1057 bar 1

K P 1.36 1057 bar 1
The unit of bar-1 appears because the standard state is 1 bar.

Kc = KP(RT)-v
4-133
Solutions
Since there are two moles of ozone produced from three moles of oxygen, v = -1 mol.
K c K P RT
K c 1.357 68 1057 bar 1 8.3145 J K 1 mol1 298.15 K
K c 3.365 63 1054 J mol 1 bar 1

where 1 bar 105 Pa
3.365 63 1054 J mol1 bar 1
Kc
105 Pa bar 1
K c 3.365 63 1059 J mol1 Pa 1

where 1 J Pa 1 1 m3 and therefore 103 J Pa 1 1 dm3
K c 3.37 1056 dm3 mol1

K x K P P v
Since there are two moles of ozone produced from three moles of oxygen, v = -1 mol.
Solving for Kx at P = 2 bar gives,
K x K P P v
K x 1.357 68 1057 bar 1
2 bar
1
K x 2.715 35 1057
K x 2.72 1057
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4-134
4.48.
Solutions
For the equilibrium:

H2(g) + I2(g) 2HI(g)
The following data apply:
H (300 K) = 9.6 kJ mol 1

S (300 K) = 22.18 J K 1 mol 1
C p (500 K) = 7.11 J K 1 mol 1
The latter value can be taken to be the average value between 300 K and 500 K.
Calculate the equilibrium constants KP, Kc, and Kx 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: H (300 K) 9.6 kJ mol1 , S (300 K) 22.18 J K 1 mol1 ,

CP (500 K) 7.11 J K 1 mol1 , P 10 atm
Required: KP, Kc, and Kx at 500 K, x
The relationship between enthalpy and heat capacity for changes in temperature is given by Eq. 2.46.
H H 2 H1 CP T2 T1
Therefore at T = 500 K, the enthalpy for the equilibrium becomes,
H 2 H1 CP T2 T1
H 500 K 9 600 J mol1 7.11 J K 1 mol1 500 K 300 K
H 500 K 9 600 J mol1 7.11 J K 1 mol1 200 K
H 500 K 11 022 J mol1
4-135
Solutions
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, H T S 0
H T S
Using Eq. 2.46 and integrating we then obtain,
H 2 H1 CP T2 T1
H T S
CP dT
T
T
S (T2 ) S (T1 ) CP ln 2
T1
S (T2 ) S (T1 )
T2
T1
500 K
S (T500 K ) 22.18 J K 1 mol 1 7.11 J K 1 mol 1 ln
300 K
S (T500 K ) 18.548 029 82 J K 1 mol1
The Gibbs free energy at T = 500 K is,

G (500 K) H T S
G (500 K) 11 022 J mol1 500 K 18.548 029 82 J K 1 mol1
G (500 K) 20 296.014 91 J mol1
The relationship between Gibbs free energy and KP is given by Eq. 4.20. Rearranging as shown in Problem 4.46, gives an expression for the
KP
4-136
Solutions
G RT ln K P
KP e
KP e
RT
20296.014 91 J mol1
8.3145 J K 1 mol1 500 K
K P 131.904 354 4
K P 132

KP = Kc(RT)v,
KP = KxPv , where v 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, Kc and Kx have the same value as KP and therefore,
K P K c K x 132
To find the mole fraction, we determine the expression for Kx based on the equilibrium.
4-137
Solutions
H 2 (g)
I 2 (g)
ninitial
nequilibrium
2 x
nfinal
1 x
1 x
2x
Kx
2x
1 x
2HI (g)
4 x2
1 x
solving for x, we obtain

4 x2
1 x
132
2x
132
1 x
2 x 11.489 125 29 1 x
x
11.489 125 29
13.489 125 29
x 0.851 732 417

x 0.852
Pressure has no effect on the mole fraction.
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4-138
Solutions
*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 mol1 and S = 891 J K1 mol1. Assume these values to be temperature independent over
this narrow range, and calculate G and Kc 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 mol1 and S = 891 J K1 mol1, T = 40.0 C, 42.0 C, 44.0 C, 46.0 C, 48.0 C, and 50.0 C
Required: G and Kc at T given, Tequilibrium
To solve for G we use Eq. 3.90, G H T S
For T = 40.0 C,
G 283 000 J mol 1 313.15 K
891 J K
mol 1
G 3 983.35 J mol 1
G 398 kJ mol 1
The relationship between Gibbs free energy and Kc is given by Eq. 4.27. Rearranging gives an expression for the Kc
G RT ln K c
Kc e
RT
For T = 40.0 C,
4-139
Kc e
3 983.35 J mol1
8.3145 J K 1 mol1 313.5 K
Solutions
K c 0.216 56
K c 0.217
Applying the same method to each temperature, we then obtain,

Temperature
G kJ mol-1
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 Tequilibrium occurs when
4-140
Solutions
G H T S 0
H
Tequilibrium
S
Tequilibrium
Tequilibrium
283 000 J mol 1
891 J K 1 mol 1
317.620 651 K
Tequilibrium 317.6 K 44.47 C
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4-141
Solutions
*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 = MA2, etc., all have the same equilibrium
constant Ks. Show that the average number of occupied sites per molecule is:
nK s [A]
v
1 K s [ 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.
Ks
SA
The equilibrium constant becomes
Ks
[SA]
, where [S] is the concentration of unoccupied sites and [SA] in the concentration of occupied sites.
[S][A]
Rearranging the equilibrium constant in terms of [S] gives,
SA
Ks A
The total concentration of sites, n[M], upon rearrangement, becomes,

n M S SA
n M
SA SA

Ks A
n M SA
1
K s A
4-142
Solutions
The average number of sites occupied per molecule is the total concentration of occupied sites divided by the total concentration of M.
v
v
SA
M
n
1
Ks A
v
nK s A
1 K s A
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4-143
Solutions
*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:
M A MA K1
[MA]
[M][A]
MA A MA 2 K 2
MA n 1 A MA n K n
[MA 2 ]
[MA][A]
[MA n ]
[MA n 1 ][A]
Show that the average number of molecules of A bound per molecule M is:
K1[A] 2 K1 K 2 [A]2 n( K1 K 2 K3 K n )[A]n
v
1 K1 [A] K1 K 2 [A]2 ( K1 K 2 K3 K n )[ A]n
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
M 0 M MA MA 2 ... MA n
The total concentration of the occupied sites is the total concentration of the bound A molecules,
A b MA 2 MA 2 ... n MA n
The first few equilibrium constants are given above as,
4-144
K1
Solutions
MA , K MA 2 , K MA3
M A 2 MA A 3 MA 2 A
Rearranging the equilibrium constants in terms of [A] gives,
MA K1 M A
2
MA 2 K 2 MA A K1K 2 M A
3
MA3 K3 MA 2 A K1K 2 K3 M A
Expressing every term in terms of [A] gives,
A b MA 2 MA 2 ... n MA n
n
2
A b M K1 A 2 K1K 2 A ... n K1K 2 ...K n A
similarly,
M 0 M MA MA 2 ... MA n
2
n
M 0 M 1 K1 A K1K 2 A ... K1K 2 ...K n A
The average number of molecules of A bound per molecule M is then given by
A b
M 0
M K1 A 2 K1K 2 A ... n K1K 2 ...K n A

2
n
M 1 K1 A K1K 2 A ... K1K 2 ...K n A
2
K1 A 2 K1 K 2 A ... n K1 K 2 ...K n A
2
1 K1 A K1 K 2 A ... K1 K 2 ...K n A
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4-145
Solutions
*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 K1 = K2 = K3 = Kn; certain statistical factors must be introduced. Thus,
if Ks is the equilibrium constant for the binding at a given site, K1 = nKs, since there are n ways for A to become attached to a given
molecule and one way for it to come off. Similarly K2 = (n 1)Ks/2; n 1 ways on and 2 ways off. Continue this argument and
develop an expression for v that will factorize into nKs[A]/(1 + Ks[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,
K1 nK s
Ks
2
K
K3 n 2 s
3
K 2 n 1
and therefore, K n
Ks
n
Substituting this into the Adair equation we get,

K1 A 2 K1 K 2 A ... n K1 K 2 ...K n A
2
1 K1 A K1 K 2 A ... K1 K 2 ...K n A
2
nK s A n n 1 K s 2 A ... nK s n A
2
1 nK s A n n 1 K s 2 A ... K s n A
2
The coefficients are the binomial coefficients and therefore the expression reduces to,
4-146
Solutions
nK s A 1 n 1 K s A ... K s n 1 A
n 1
1 nK s A n n 1 K s 2 A ... K s n A
2
nK s A 1 K s A
n 1
1 K A
nK A 1 K A
v
1 K A 1 K A
n
nK s A
1 K s A
which is the expression obtained in Problem 4.50.
A method to test the equilibrium would be to plot
1
1
against
Rearranging the above equation gives,
v
A
nK s A
1 Ks A
1 1 Ks A
v
nK s A
Ks A
1
1
v nK s A n K s A
1 1
1

v n nK s A
One of the intercepts will be
1
.
n
4-147
Alternatively, v can be plotted against
Solutions
v
A
nK s A
1 Ks A
v vK s A nK s A
v nK s A vK s A
v
Ks A
v n
nv
v
Ks A
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4-148
Solutions
*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 Kn is much greater than K1, K2, etc. Show that now:
nK [A]n
1 K [A]n
Where K is the product of K1, K2, Kn. The British physiologist A. V. Hill suggested that binding problems can be treated by
plotting:
ln
against ln[A]
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 Kn is much greater than K1, K2, and so on, then the equation obtained in Problem 4.51 reduces to the following
K1 A 2 K1 K 2 A ... n K1 K 2 ...K n A
2
1 K1 A K1 K 2 A ... K1 K 2 ...K n A
2
n K1 K 2 ...K n A
1 K1 K 2 ...K n A
nK A
1 K A
Where K K1 K 2 ...K n is the overall equilibrium constant for the binding of n molecules, we then obtain
4-149
nA
Solutions
MA n
The fraction of sites occupied,

K A
1 K A
or,
K A
against A is therefore n. If the sites are identical and independent (Problem 4.50), then the slope is 1.
1
Intermediate behaviour can give nonlinear plots; the maximum slope of a Hill plot cannot be greater than n.
The slope of the plot of ln
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4-150

Chapter 04 Chemical Equilibrium

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Chapter 04 Chemical Equilibrium

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CHAPTER

LAIDLER . MEISER . SANCTUARY

Problems and Solutions

Chapter 4: Chemical Equilibrium

A reaction occurs according to the equation:

The equilibrium constant for a reaction below is 0.1:

The equilibrium constant Kc for the reaction:

Chapter 4: Chemical Equilibrium

When gaseous iodine is heated, dissociation occurs:

It has been observed with the ammonia equilibrium:

Nitrogen dioxide, NO2, exists in equilibrium with dinitrogen tetroxide, N2O4:

Chapter 4: Chemical Equilibrium

At 25.0 C the equilibrium:

In a study of the equilibrium

Chapter 4: Chemical Equilibrium

Chapter 4: Chemical Equilibrium

Equilibrium Constants and Gibbs Energy Changes

Equilibrium Constants and Gibbs Energy Changes

The equilibrium constant for the reaction

At 3000 K the equilibrium partial pressures of CO2,

The conversion of malate into fumarate:

Chapter 4: Chemical Equilibrium

Equilibrium Constants and Gibbs Energy Changes

N2(g) + 3H2(g) 2NH3(g)

At 25.0 C the equilibrium constant for the reaction:

Suppose that there is a biological reaction:

Chapter 4: Chemical Equilibrium

Temperature Dependence of Equilibrium Constants

The equilibrium between citrate and isocitrate involves cis-aconitate as an intermediate:

Temperature Dependence of Equilibrium Constants

What is G at 25 C (standard state: 1 bar)?

Chapter 4: Chemical Equilibrium

Temperature Dependence of Equilibrium Constants

4.26. A solution reaction:

From the data given in Appendix D, for the reaction:

G, H, and S at 25 C; what is the standard state?

From the data in Appendix D, for the reaction:

Chapter 4: Chemical Equilibrium

Temperature Dependence of Equilibrium Constants

Calculate the equilibrium constant at 400 K for the reaction:

a. Calculate G for n-pentane neopentane.

Chapter 4: Chemical Equilibrium

Temperature Dependence of Equilibrium Constants

log10(KP/bar) = 7.55 4844/(T/K)

From the data in Appendix D, for the synthesis of methanol,

Chapter 4: Chemical Equilibrium

Temperature Dependence of Equilibrium Constants

Calculate H, G, and S for this reaction from the following data, at 25 C:

When the reaction:

From the data in Appendix D, for the reaction

H, G, and S (standard state: 1 bar and 25 C).

Chapter 4: Chemical Equilibrium

Temperature Dependence of Equilibrium Constants

Chapter 4: Chemical Equilibrium

Temperature Dependence of Equilibrium Constants

The following values apply to a chemical reaction A Z:

Chapter 4: Chemical Equilibrium

Temperature Dependence of Equilibrium Constants

the equilibrium constants KP, Kc, and Kx for the process:

For the equilibrium:

Chapter 4: Chemical Equilibrium

Binding to Protein Molecules

Chapter 4: Chemical Equilibrium