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24, 2015
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
3.16
3.16
Same question format, variation in numbers between 10th 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
G 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 G for the process.
3D.1(a) Suppose that 2.5 mmol N2(g) occupies 42 cm3 at 300 K and expands isothermally to 600
cm3. Calculate G for the process.
3D.1(b) Suppose that 6.0 mmol Ar(g) occupies 52 cm3 at 298 K and expands isothermally to 122
cm3. Calculate G for the process.
Question 13.03
3D.2
3.17
3.17
Same questions.
3D.2(a) The change in the Gibbs energy of a certain constantpressure process was found to fit
the expression G/J = 85.40 + 36.5(T/K). Calculate the value of S for the process.
3D.2(b) The change in the Gibbs energy of a certain constantpressure process was found to fit
the expression G/J = 73.1 + 42.8(T/K). Calculate the value of S for the process.
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Question 13.04*
n/a
3.18
3.18
n/a
n/a
3.19
3.19
3.20
3.20
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Question 13.08
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.
3D.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 cm3.
3D.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 cm3.
Question 13.09
3D.4
3.22
3.22
Same question.
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.
Set 2
Question 13.10*
n/a
P3.22
P3.22
Part (a) is missing in all edition after the 7th Ed in 9th and 10 Eds.
(Ex. 5.14a, 7th edition). The molar Helmholz energy of a certain gas is given by
Am =
a
RT (lnVm 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 + Cp 2 + Dp 3
2
3
University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko!
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
where A, B, C and D are constants. Obtain the equation of state of the gas.
Question 13.11
P3D.4
P3.23ab
P3.23ab
Evaluate (S/V)T for each gas. For an isothermal expansion, for which kind of gas (also consider
a perfect gas) will S be greatest? Explain your conclusion.
Question 13.12*
3D.1
n/a
n/a
P3.24
P3.24
P3.25
P3.25
Same questions.
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.
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Question 13.15
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).
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 , and the
isothermal compressibility, T.
P3.30 The Joule coefficient, J, is defined as J = (T/V)U. Show that JCV = p aT/T.
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 = (1/V)(V/T)p, and the
isothermal compressibility, T = (1/V) (V/p)T.
(b) The Joule coefficient, j, is defined as = (T/V)U. Show that JCV = p T/T.
Question 13.16*
n/a
P3.27
P3.27
P3.28
P3.28
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
P3D.7
P3.33
P3.33
Same questions, except for addition of highlighted term in 10th Ed, which seems to be a misprint.
3D.7 Suppose that S is regarded as a function of p and T. Show that TdS = CpdT TVdp. Hence,
show that the energy transferred as heat when the pressure on an incompressible liquid or solid is
increased by p is equal to TVp, 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. ( = 1.82 10-4 K-1.)
10th Ed. misprint (online Ed). Likely, this is suppose to be: = (1/V)(V/T)p
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Answer 13.01*
n/a
n/a
n/a
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Answer 13.04*
n/a
3.18
3.18
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.
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Answer 13.05*
n/a
n/a
n/a
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Answer 13.06*
n/a
3.19
3.19
Answer 13.07*
n/a
3.20
3.20
10
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Answer 13.10a*
n/a
P3.22
3.19
Part (a) is missing in all edition after the 7th Ed in 9th and 10 Eds.
11
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Answer 13.12*
n/a
n/a
n/a
12
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Answer 13.13*
n/a
P3.24
P3.24
13
59-240 Physical Chemistry - Question Set #13 - Lecture 13 - v. 1.2 - updated Nov. 24, 2015
Answer 13.16*
n/a
P3.27
P3.27
Answer 13.17*
n/a
P3.28
P3.28
14