Gibbs Free Energy and Equilibrium

in Chemical Systems 1

Minimalist Coverage Basic Chemical Thermodynamics, E. B. Smith,

Sections 4.1 − 4.4, 4.9 − 4.15

Longer Coverage Physical Chemistry, R. A. Alberty, 3rd ed, Sections 4.1−

4.6, 4.8, 5.1.

Homework: 1 atm = 105 Nm−2 = 760mm Hg

1. Is the Gibbs Free Energy a State Function?

2. Alberty, 4.9. In Section 3.4 we calculated that the enthalpy of freezing

water at −10C is −5619Jmol−1 , and we calculated that the entropy
of freezing water is −20.54JK −1 mol−1 at −10C. What is the Gibbs
energy of freezing water at −10C?

3. Alberty, 4.10a, theory problem. Integrate the Gibbs-Helmholtz

equation to obtain an expression for ∆G2 at temperature T2 in terms
of ∆G1 at T1, assuming that ∆H is independent of temperature.

4. Alberty, 4.11 When a liquid is compressed its Gibbs energy is in-

creased. To a first approximation

the increase in Gibbs energy can be
calculated using ∂G
∂P T
= V , assuming constant volume. What is the
change in Gibbs energy for one mole of liquid water when it is com-
pressed to 1000atm (the density of water is approximately 1 g cm−3 )?

5. Alberty, 4.13 The standard entropy of O2 (g) at 298K and 1atm is

listed in Appendix C.2 as 205.138JK −1 mol−1 , and the standard Gibbs
energy of formation is listed as 0kJmol−1 . Assuming that O2 is an
ideal gas, what will be the entropy and Gibbs energy of formation for
one mole of gas at 100atm and 298K?
1
Paul Maslen, Rm 428 B&S, ext 6282, [email protected]
http://crab.rutgers.edu/ maslen/Courses/PChemI

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6. Alberty, 4.14 One mole of helium is compressed isothermally and
reversibly at 100C from a pressure of 2 to 10atm. Calculate (a) ∆q,
(b)∆w, (c)∆G, (d) ∆A, (e) ∆H, (f) ∆U and (g) ∆S, assuming that
helium is an ideal gas.

7. Alberty, 4.15 One mole of toluene is vaporized at its boiling point,

111C. The heat of vaporization at this temperature is 361.9Jg −1 .
For the vaporization of one mole of toluene calculate (a) ∆w, (b)∆q,
(c)∆H, (d) ∆U, (e) ∆G, (f) ∆S.

8. Alberty, 4.16, theory question If the Gibbs energy varies with tem-
perature according to

G/T = a + b/T + c/T 2

how will the enthalpy and entropy vary with temperature? Check that
these three equations are consistent.
(hint: review the derivation of the Gibbs-Helmholtz equation for the
variation of G with temperature.)

9. Alberty, 4.17 Calculate the change in Gibbs energy when one mole of
suppercooled water at −3C freezes at constant T and P . The density
of ice is 917 kg m−3 , and its vapor pressure is 475P a. The density of
supercooled water at −3C is 999.6 kg m−3, and its vapor pressure is
489P a.
hint:

(a) Calculate the volume of the solid and the liquid

(b) Calculate ∆G along the following reversible path between the ini-
tial and final states:
i. Initial state is one mole of liquid at 1 atm.

ii. Next state is one mole of liquid at 489P a. ∆G = VliquiddP
iii. Next state is one mole of gas at 489P a. This is at equilibrium
with the liquid, so what is ∆G?
iv. Next state is one mole of gas at 475P a. ∆G = RT ln(Pfinal /Pinitial).
v. Next state is one mole of solid at 475P a. This is at equilibrium
with the gas, so what is ∆G?

vi. Next state is one mole of solid at 1 atm. ∆G = Vsolid dP

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10. Alberty, 4.18 Calculate the Gibbs energy of fusion when one mole of
supercooled water at −3C freezes at constant T and P . The enthalpy
of fusion of ice is 6000Jmol−1 at 0C. The heat capacities of water and
ice in the vicinity of the freezing point are 75.3 and 38 JK −1 mol−1
respectively.
11. Alberty, 4.24 Calculate ∆mixG and ∆mixS for the formation of a
quantity of air containing 1 mol of gas by mixing nitrogen and oxygen
at 298K. Air may be taken to be 80% nitrogen and 20% oxygen.
12. Alberty, 4.25 A mole of gas A is mixed with a mole of gas B at 1
atm pressure and 298K. How much work is required to separate these
gases to produce a container of each at 1 atm and 298K?
13. Alberty, 4.29 Show that
   
∂U ∂H ∂H ∂G
= =
∂S V
∂S P
∂P S
∂P T

14. Alberty, 4.32 What is the effect of pressure on the entropy, enthalpy,
and internal energy of an incompressible fluid?
15. Alberty, 4.39 The heat of vaporization of liquid oxygen at its boiling
point (−183C) at 1 atm is 6820Jmol−1 . For the reversible vaporization
of one mole of liquid oxygen calculate (a) ∆q (b) ∆U (c) ∆S (d) ∆G.
16. The equilibrium constant for the reaction
H2 + I2  2HI
is 45.6 at 764K and is 60.8 at 667K. Estimate the enthalpy change
which accompanys one mole of the forward reaction.
17. Formic acid is partially associated into dimers in the gas vapour phase.
The mole fraction present as monomer is 0.228 at 283K and 10mm Hg
pressure, and 0.715 at 333K and 16mm Hg. Calculate the enthalpy
change on dimerization.
18. In a mixture at 1 atmosphere the partial pressure of CO in equilibrium
with CO2 and C was as follows:
T/K 1083 1173 1253
Partial Pressure of CO/atm 0.931 0.978 0.991

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 Calculate the enthalpy change accompanying the reaction

CO2 + C− > 2CO

19. For the gas phase reaction

cyclopentene + I2 = cyclopentadiene + 2HI

log Kp = 7.55 − 4817T −1

in the temperature range 450 − 690K.
Calculate the standard enthalpy, entropy and Gibbs Free Energy changes
accompanying the reaction at 573K.


∂U
20. theory problem: Show that for an ideal gas ∂V = 0.
T
There are many ways to do this. One possible route is outlined here.
Alternatively, figure out your own way, or follow Alberty. Show your
working.

(a) Rearrange the combined first and second law:

dU = T dS − P dV

to express dS as a function of U and V .

(b) Take the U ↔ T transform of dS to obtain a new state function,
dX.
(c) Equate the two mixed second derivatives

of X to obtain a Maxwell’s
∂U
relation, and rearrange to express ∂V in terms of P , T , and their
T
derivatives.


∂U
(d) Show that ∂V T
= 0 by making use of P V = nRT .

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21. theory problem: Deduce a relation between CV and CP , valid for all
materials (solids, liquids and gases).



∂S ∂S
(a) Using /dq = T dS, show that CV = T ∂T V
and CP = T ∂T P
.
(b) Starting from the ‘taylor series’:
 
∂S ∂S
dS(T, V ) = dT + dV
∂T V
∂V T


∂S
divide through by dT at constant P , and hence express in



∂T P
∂S ∂S ∂V
terms of ∂T V
, ∂V
and ∂T
,
T P


∂S
(c) Obtain a Maxwell relation for ∂V
, by equating the mixed second
T
derivatives of A, where

dA = −SdT + P dV


∂S
Substitute this expression for back into the expression for

∂V T
∂S
∂T P
.


∂S
(d) Finally, substitute this expression for ∂T into the expression for
P
CP , and hence obtain a relation between CP and CT .
(e) For an ideal gas, simplify the relation between CP and CV by using
P V = nRT .