Department of

Chemistry

19 September 2022 18:30 – 20:30

CHE 211: TEST 1 - Thermodynamics

INSTRUCTIONS

The question paper contains two (2) questions and five (5) printed pages, including this cover page. Please
check.

In calculations, you are advised to show all the steps in your working, giving your answer at each stage.

The relative allocation of marks to each part-question is indicated in the right hand margin.

Start an answer to a question on a fresh sheet of paper.

Attempt ALL questions.

The following data may be used in any question

Universal gas constant, R = 0.0821 L atm/mol/K = 8.314 J/molK
1 atm = 760 mmHg = 760 torr = 1.013 ×105 Pa

The following supporting material (s) should accompany this question paper:
Periodic table of elements

You may not start to read the questions printed on the subsequent pages
of this question paper until instructed to do so by the invigilator

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 Question One

Answer all parts

a) Define the following terms

[5 marks]
i. Thermodynamic system
ii. The surrounding and universe
iii. Thermodynamic state of a system
iv. Thermodynamic equilibrium
v. Thermodynamic process
b) Figure below shows the initial state of an apparatus consisting of an ideal gas in a bulb, a
stopcock, a porous plug, and a cylinder containing a frictionless piston. The walls are
diathermal (walls that permit heating as a mode of transfer of heat), and the surroundings
are at a constant temperature of 300.0 K and a constant pressure of 1.0 atm. When the
stopcock is opened, the gas diffuses slowly through the porous plug, and piston moves
slowly to the right. The process ends when the pressures are equalized and the piston stops
moving. The system is the gas. Assume that during the process the temperature throughout
the system differs only infinitesimally from 300.0 K and the pressure on both sides of the
piston differs only infinitesimally from 1.0 atm.

i. Which of these terms correctly describe the process: isothermal, isobaric, isochoric,
reversible, irreversible? Justify.
[4 marks]
ii. Calculate q and w.
[5 marks]

2
c) The frictionless piston-and-cylinder shown here contains one mole of a gas at a
temperature of 25 °C and a pressure of 1 atm. The piston has negligible mass. Heat can be
added to the gas by a heating coil.

The heating coil is connected to a 12 V source and a current of 1.23 A flows through the
coil for 11.85 minutes. The piston is fixed in position by the clamps and the temperature
of the gas raised to 651 K. Calculate the molar constant-pressure heat capacity of the gas.
Assume that the piston and cylinder cannot conduct heat.
[4 marks]
d) A sample of the sugar D-ribose (C5H10O5) of mass 0.727 g was weighed into a calorimeter
and then ignited in the presence of excess oxygen. The temperature rose by 0.910 K. In a
separate experiment in the same calorimeter, the combustion of 0.825 g of benzoic acid
(C6H5CO2H), for which the internal energy of combustion is -3251 kJ/mol, gave a
temperature rise of 1.940 K. Calculate the internal energy of combustion of D-ribose.
[6 marks]
e) From the following equations and heats of reaction, calculate the standard molar heat of
formation of AgCl at 25 °C.
[8 marks]

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 Question Two

Answer all parts

a) Show, using thermodynamic reasoning, that the heat capacities CV and Cp of a fixed amount
of an ideal gas are functions only of temperature.
[3 marks]
b) Enthalpy is defined as

H = U + PV (i)

Show by using (i) and the 1st law of thermodynamics, that for a closed system that can
only do expansion work reversibly at constant pressure, the heat supplied to the system
equals the change in its enthalpy i.e.
dH = dq

[4 marks]
c) Define entropy and state the second law of thermodynamics.
[2 marks]
d) Suppose you have two blocks of copper, each of heat capacity Cv = 200 JK-1. Initially one
block has a uniform temperature of 300 K and the other 310 K. Calculate the entropy
change that occurs when you place the two blocks in thermal contact with one another and

surround them with perfect thermal insulation. Is the sign of ∆S consistent with the second

law of thermodynamics? (Assume the process occurs at constant volume).

[5 marks]
e) The standard enthalpies of formation, ∆fH°, entropies, S°, and heat capacities, Cp° for H2,
N2, and NH3 are given below (all data are for 298 K)

∆fH° (kJmol-1) S° (JK-1mol-1) Cp° (JK-1mol-1)

H2 0 130.68 28.82

N2 0 191.61 29.13

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 NH3 -46.11 192.45 35.06

i. Using these values, calculate ∆rH°, ∆rS°, and ∆rG°, for the decomposition of NH3
at 298 K.
[6 marks]

ii. Use your answer to part (i) to deduce if the reaction is non-spontaneous,
spontaneous or at equilibrium.
[2 marks]
iii. State the relationships between ∆rH° (298 K) given above, and ∆rH°(T), the
standard enthalpy change for the reaction at a temperature other than 298 K.
Assume that in each case ∆rCp° is constant. Calculate ∆rH° at 500 K.
[6 marks]

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END OF QUESTION PAPER