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Chem S 360: Advanced Physical Chemistry I

Exercise 1 (September 19, 2022)

Problem 1
Oxidation of glucose is the principle source of energy for animal cells. Assume glucose
(C6H12O6(s)) reacts with oxygen (O2(g)) to produce carbon dioxide (CO2(g)) and liquid water (H2O(l)).

C6H12O6(s) CO2(g) H2O(l)

Δ H f ° [kJ /mol] ‒1274.4 ‒393.509 ‒285.830

(a) Write a balanced chemical reaction and determine the standard heat of reaction.
(b) Assuming a person needs 150 kJ of energy per kg of body mass per day, and this energy
comes solely from glucose, how much glucose is needed to sustain a 60 kg person?
(c) There are about 7 billion people in the world. How much CO2 do they produce a day only
through respiration?

Problem 2

From the following data, determine Δ H f ° for diborane, B2 H 6 (g) , at 298 K:

(1) B2 H 6 ( g ) +3 O2 ( g ) → B 2 O3 ( s ) +3 H 2 O(g) Δ H r °=−1941 kJ mo l

−1

()
−1
3 Δ H r °=−2368 kJ mo l
(2) 2 B ( s ) + O ( g ) → B2 O 3 (s )
2 2

(3) H ( g )+ ( ) O ( g ) → H O(g)
−1
1 Δ H r °=−241.8 kJ mo l
2 2 2
2

Problem 3
A gas at 250 K and 15 atm has a molar volume 12% smaller than that calculated from the
perfect gas law.
(a) Calculate the compression factor under these conditions.
(b) Calculate the molar volume of the gas.
(c) Which are dominating in the sample: the attractive or the repulsive forces?
Problem 4
Two kmol of nitrogen gas are compressed isothermally (T=298 K) and reversibly from an initial
pressure Pi of 1 MPa to a final pressure Pf of 5 MPa. Derive an expression for and calculate the
work done on the gas during the compression if it follows:
(a) The ideal gas law.
(b) The van der Waals (vdW) equation of state.

vdW coefficients a [atm dm6 mol-2] b [dm3 mol-1]

N2 1.352 0.0387

Problem 5
A process stream is being cooled from 25 ℃ to 0 ℃ using chilled brine. The rate of heat
removal is 50 kW .
(a) What is the theoretical coefficient of performance (CoP)?
(b) What is the theoretical power requirement for the refrigeration system?
(c) If the actual CoP is 2.5, what is the power requirement to run the refrigeration system?

Problem 6
A sample consisting of 2.00 mol of diatomic perfect gas molecules at 250 K is compressed
reversibly and adiabatically until its temperature reaches 300 K.

Given that C v =27.5 J K−1 mol−1, calculate:

(a) q
(b) w
(c) ΔU
(d) ΔH
(e) ΔS

Problem 7
Calculate Δ H tot and Δ S tot when two iron blocks, each of mass 1.00 kg, one at 200 ℃ and the
other at 25 ℃ , are placed in contact in an isolated container. The specific heat capacity of iron
is 0.449 J K−1 g−1 and may be assumed constant over the temperature range involved.

Problem 8
Nitric acid hydrates have received much attention as possible catalysts for heterogeneous
reactions that bring about the Antarctic ozone hole. Worsnop et al. investigated the
thermodynamic stability of these hydrates under conditions typical of the polar winter
stratosphere. They report thermodynamic data for the sublimation of mono-, di-, and
trihydrates to nitric acid and water vapors:
HN O3 ∙ n H 2 O ( s ) → HN O3 ( g ) +n H 2 O( g)

for n = 1, 2, and 3. Given Δ G r ° and Δ H r ° for these reactions at 220 K, use the Gibbs-Helmholtz
equation to compute Δ G r ° at 190 K.

n 1 2 3
Δ G r ° [kJ/mol] 46.2 69.4 93.2
Δ H r ° [kJ/mol] 127 188 237

Problem 9
A gaseous sample consisting of 1.00 mol molecules is described by the equation of state:
P V m=RT (1+BP)

Initially at 373 K, it undergoes Joule-Thomson expansion from 100 atm to 1.00 atm. Given that
5
C p= R , μ=0.21 K at m−1, B=−0.525
2 ( )
K
T
at m−1, and that these are constant over the

temperature range involved, calculate Δ T and Δ S for the gas.

Problem 10
Pure substances are described by a “fundamental equation” that relates their energy and
entropy to extensive variables. The fundamental equation for a particular substance is given as:
3
aUV b n
S= −
n UV
where S is the entropy, U is the internal energy, V is the total volume and n is the number of
moles. The variables a and b are constants. An equation of state can be derived for this
substance using the equation:
1 P μ
dS= dU + dV − dn
T T T
from which we find the following:

P
T
=( )
∂S
∂V U,n

=(
∂U )
1 ∂S
T V ,n

P 1
(a) Derive expressions for and as functions of n, V, and U.
T T
(b) Eliminate U from the above expressions to find an expression for P in terms of V and T.

Problem 11
The ideal gas is defined as:
(a) P-V-T behavior is described by the equation of state PV=RT.
(b) Internal energy is only a function of temperature.
Denbigh suggests an alternative definition: a single-component ideal gas is a substance whose
chemical potential is given by:
G=RT ln ( P )+ λ(T )

Prove that properties (a) and (b) follow from Denbigh’s definition.