59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov.

1, 2018

Assigned questions for Lecture 13 are listed below. The questions occur in the following
editions of “Physical Chemistry” by P.W. Atkins:

10th edition 9th edition 8th edition

Note: The letter “P” in front of a number indicates that the question is in the “Problem” category
as opposed to the “Exercise” category in Atkins’ books. Updates are highlighted in yellow.
There are a lot of questions that are now missing, which is unfortunate. Note: There are two
separate problem sets associated with Lecture 13.

Set 1

Question 13.01*
n/a n/a n/a n/a
Missing after 7th Ed. (not sure why). 

(Ex. 5.4a, 7th edition). Express (∂S/∂V)T in terms of α and κT.
(Ex. 5.4b, 7th edition). Express (∂S/∂p)T in terms of α.

Question 13.02
3E.1 3D.1 3.16 3.16
Same question format, variation in numbers between 10th and 11th Eds. vs. 8th and 9th Eds.

3.16(a) Suppose that 3.0 mmol N2(g) occupies 36 cm3 at 300 K and expands to 60 cm3. Calculate
ΔG for the process.

3.16(b) Suppose that 2.5 mmol Ar(g) occupies 72 dm3 at 298 K and expands to 100 dm3.
Calculate ΔG for the process.

3E.1(a) Suppose that 2.5 mmol N2(g) occupies 42 cm3 at 300 K and expands isothermally to 600
cm3. Calculate ΔG for the process.

3E.1(b) Suppose that 6.0 mmol Ar(g) occupies 52 cm3 at 298 K and expands isothermally to 122
cm3. Calculate ΔG for the process.

Question 13.03

3E.2 3D.2 3.17 3.17
Same questions.

3D.2(a) The change in the Gibbs energy of a certain constant–pressure process was found to fit
the expression ΔG/J = −85.40 + 36.5(T/K). Calculate the value of ΔS for the process.
3D.2(b) The change in the Gibbs energy of a certain constant–pressure process was found to fit
the expression ΔG/J = −73.1 + 42.8(T/K). Calculate the value of ΔS for the process.

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Question 13.04*

n/a n/a 3.18 3.18
Missing from 10th and 11th Eds. No idea why.
3.18(a) Calculate the change in Gibbs energy of 35 g of ethanol (mass density 0.789 g cm-3)
when the pressure is increased isothermally from 1 atm to 3000 atm.

3.18(b) Calculate the change in Gibbs energy of 25 g of methanol (mass density 0.791 g cm-3)
when the pressure is increased isothermally from 100 kPa to 100 MPa. Take κT = 1.26 × 10-9 Pa-1.

Question 13.05*
n/a n/a n/a n/a
Missing in all editions after 7th Ed. 

(Ex. 5.8a, 7th edition). When 2.00 mol of has at 330 K and 3.50 atm is subject to isothermal
compression, its entropy decreases by 25.0 J K-1. Calculate (a) the final pressure of the gas and
(b) the ΔG for the compression.

(Ex. 5.8b, 7th edition). When 3.00 mol of has at 230 K and 150 kPa is subject to isothermal
compression, its entropy decreases by 15.0 J K-1. Calculate (a) the final pressure of the gas and
(b) the ΔG for the compression.

Question 13.06*
n/a n/a 3.19 3.19
Missing from the 10th and 11th Eds. Not sure why. But: See E3E.6 in 11th Ed. for something
similar (see Q13.09 below).
3.19(a) Calculate the change in chemical potential of a perfect gas when its pressure is increased
isothermally from 1.8 atm to 29.5 atm at 40°C.

3.19(b) Calculate the change in chemical potential of a perfect gas that its pressure is increased
isothermally from 92.0 kPa to 252.0 kPa at 50°C.

Question 13.07*
n/a n/a 3.2 3.2
Missing from the 10th Ed. Not sure why.
3.20(a) The fugacity coefficient of a certain gas at 200 K and 50 bar is 0.72. Calculate the
difference of its molar Gibbs energy from that of a perfect gas in the same state.

3.20(b) The fugacity coefficient of a certain gas at 290 K and 2.1 MPa is 0.68. Calculate the
difference of its molar Gibbs energy from that of a perfect gas in the same state.

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Question 13.08
3E.3 3D.3 3.21 3.21
Sort of the same style question. Use of mass density in 10th Ed. is similar to Question 13.04.

3.21(a) Estimate the change in the Gibbs energy of 1.0 dm3 of benzene when the pressure acting
on it is increased from 1.0 atm to 100 atm.

3.21(b) Estimate the change in the Gibbs energy of 1.0 dm3 of water when the pressure acting on
it is increased from 100 kPa to 300 kPa.
3E.3(a) Estimate the change in the Gibbs energy and molar Gibbs energy of 1.0 dm3 of octane
when the pressure acting on it is increased from 1.0 atm to 100 atm. The mass density of octane
is 0.703 g cm−3.

3E.3(b) Estimate the change in the Gibbs energy and molar Gibbs energy of 100 cm3 of water
when the pressure acting on it is increased from 100 kPa to 500 kPa. The mass density of water
is 0.997 g cm−3.

Question 13.09
3E.6 3D.4 3.22 3.22
Same question in 10th and earlier editions.
3D.4(a) Calculate the change in the molar Gibbs energy of hydrogen gas when its pressure is
increased isothermally from 1.0 atm to 100.0 atm at 298 K.

3D.4(b) Calculate the change in the molar Gibbs energy of oxygen when its pressure is increased
isothermally from 50.0 kPa to 100.0 kPa at 500 K.



Changed in 11th Ed.

3E.6(a) Calculate the change in the molar Gibbs energy of a perfect gas when its pressure is
increased isothermally from 1.0 atm to 100.0 atm at 298 K.

3E.6(b) Calculate the change in the molar Gibbs energy of a perfect gas when its pressure is
increased isothermally from 50.0 kPa to 100.0 kPa at 500 K.

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Set 2

Question 13.10*
n/a n/a P3.22 P3.22
Part (a) is missing in all editions after the 7th Ed, in 9th-11th Eds.


(Ex. 5.14a, 7th edition). The molar Helmholz energy of a certain gas is given by
a
Am = − − RT (ln Vm − b) + f (T )
Vm

where a and b are constants and f(T) is a function of temperature only. Obtain the equation of
state of the gas.

(Ex. 5.14b, 7th edition). The molar Gibbs energy of a certain gas is given by

1 1
Gm = RT ln p + A + Bp+ 2 Cp 2+ 3 Dp 3

where A, B, C and D are constants. Obtain the equation of state of the gas.

Question 13.11
P3E.4 P3D.4 P3.23ab P3.23ab
9th Ed. and earlier:
P3.23 Evaluate (∂S/∂V)T for (a) a van der Waals gas, (b) a Dieterici gas (see Lecture 4, real
gases). For an isothermal expansion, for which kind of gas (and a perfect gas) will ΔS be
greatest?Explain your conclusion.


Changed in the 10th:


3D.4 Two empirical equations of state of a real gas are as follows:

Evaluate (∂S/∂V)T for each gas. For an isothermal expansion, for which kind of gas (also consider
a perfect gas) will ΔS be greatest? Explain your conclusion.


And yet again in the 11th (see next page):

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Question 13.12*
P3E.1 3D.1 n/a n/a
Missing in 8th and 9th Eds. 

(P5.1, 7th edition). Calculate ΔrGo (375 K) for the reaction 2CO(g) + O2(g) → 2CO2(g) from the
Gibbs-Helmholz equation, and the values of ΔrGo (298 K) and ΔrHo (298 K).
11th Ed.:



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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Question 13.13*
n/a n/a P3.24 P3.24
Missing from the 10th ed. Not sure why.
P3.24 Show that, for a perfect gas, (∂U/∂S)V = T and (∂U/∂V)S = -p.

Question 13.14*
n/a P3D.5 P3.25 P3.25
Same questions in 10th and earlier. Missing in 11th. However, this is just what is asked of you in
classes for L13, and part of this is covered in tutorial.
3D.5 Two of the four Maxwell relations were derived in the text, but two were not. Complete
their derivation by showing that (∂S/∂V)T = (∂p/∂T)V and (∂T/∂p)S = (∂V/∂S)p.

Question 13.15*
n/a 3D.6a,b P3.26, P3.30 P3.26, P3.30
In the 10th Ed, the problems are joined together into one (a and b). Missing from the 11th Ed.

P3.26 Use the Maxwell relations to express the derivatives (a) (∂S/∂V)T and (∂V/∂S)p and

(b) (∂p/∂S)V and (∂V/∂S)p in terms of the heat capacities, the expansion coefficient α, and the
isothermal compressibility, κT.
P3.30 The Joule coefficient, µJ, is defined as µJ = (∂T/∂V)U. Show that µJCV = p – aT/ΚT.

3D.6 (a) Use the Maxwell relations to express the derivatives (∂S/∂V)T, (∂V/∂S)p, (∂p/∂S)V, and
(∂V/∂S)p in terms of the heat capacities, the expansion coefficient α = (1/V)(∂V/∂T)p, and the
isothermal compressibility, κT = −(1/V) (∂V/∂p)T. 

(b) The Joule coefficient, µj, is defined as = (∂T/∂V)U. Show that µJCV = p − αT/κT.

Question 13.16*
n/a n/a P3.27 P3.27
Missing from the 10th ed. Not sure why.
3.27 Use the Maxwell relations to show that the entropy of a perfect gas depends on the volume
as S ∝ R ln V.

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Question 13.17*
n/a n/a P3.28 P3.28
Missing from the 10th ed. Not sure why.
P3.28 Derive the thermodynamic equation of state


( ∂T ) ( ∂T )
∂H ∂V
=V−T
p p

Derive an expression for (∂H/∂p)T for (a) a perfect gas and (b) a van der Waals gas. In the latter
case, estimate its value for 1.0 mol Ar(g) at 298 K and 10 atm. By how much does the enthalpy
of the argon change when the pressure is increased isothermally to 11 atm?

Question 13.18*
n/a P3D.7 P3.33 P3.33
Same questions, except for addition of highlighted term in 10th Ed, which seems to be a misprint.
And of course…missing from the illustrious 11th Ed.
3D.7 Suppose that S is regarded as a function of p and T. Show that TdS = CpdT −αTVdp. Hence,
show that the energy transferred as heat when the pressure on an incompressible liquid or solid is
increased by Δp is equal to αTVΔp, where O = (1/V)(9V/9T)p. Evaluate q when the pressure
acting on 100 cm3 of mercury at 0 °C is increased by 1.0 kbar. (α = 1.82 × 10-4 K-1.)

10th Ed. misprint (online Ed). Likely, this is suppose to be: α = (1/V)(∂V/∂T)p

Note for F2018:


It seems that the Atkins editing team has removed most question involving partial
derivatives and the second-law toolbox - contrary to most of major texts on
thermodynamics. Lots more unhelpful discussion questions though!


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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Answer 13.01*
n/a n/a n/a n/a
Missing after 7th Ed. (not sure why).

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Answer 13.04*

n/a n/a 3.18 3.18
Missing from 10th and 11th Eds. No idea why.

Note: You will not have to decide whether to integrate or assume that the volume is constant in
an exam situation. This will be made very clear.


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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Answer 13.05*
n/a n/a n/a n/a
Missing in all editions after 7th Ed.

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Answer 13.06*
n/a n/a 3.19 3.19
Missing from the 10th Ed. Not sure why.

Answer 13.07*
n/a n/a 3.2 3.2
Missing from the 10th Ed and later. Not sure why.

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Answer 13.10a*
n/a n/a P3.22 3.19
Part (a) is missing in all edition after the 7th Ed in 9th and 10 Eds.

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Answer 13.12*
n/a n/a n/a n/a
Missing in all editions after 7th Ed.

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Answer 13.13*
n/a n/a P3.24 P3.24
Missing from the 10th ed and later. Not sure why.

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Answer 13.15*
n/a 3D.6a,b P3.26, P3.30 P3.26, P3.30
In the 10th Ed, the problems are joined together into one (a and b). Missing from the 11th Ed.


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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Answer 13.16*
n/a P3.27 P3.27
Missing from the 10th ed. Not sure why.

Answer 13.17*
n/a P3.28 P3.28
Missing from the 10th ed. Not sure why.

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59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 2.0 - updated Nov. 1, 2018

Answer 13.18*
n/a P3D.7 P3.33 P3.33
Same questions, except for addition of highlighted term in 10th Ed, which seems to be a misprint.
And of course…missing from the illustrious 11th Ed.

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