Tutorial 2 Spring 2018-19

CY11001 (Physical Chemistry) Tutorial 2
Assume ideal behaviour unless stated otherwise
1. A sample consisting of 3.00 mol of a diatomic perfect gas at 200 K is compressed

reversibly and adiabatically until its temperature reaches 250 K. Given that 𝐶𝐶𝑉𝑉,𝑚𝑚 =
27.5 J K-1 mol-1, calculate 𝑞𝑞, 𝑤𝑤, ∆𝑈𝑈, ∆𝐻𝐻 and ∆𝑆𝑆.
2. Calculate ∆𝑆𝑆 (for the system) when the state of 3.00 mol of a perfect gas, for which
𝐶𝐶𝑝𝑝,𝑚𝑚 = 5/2 R, is changed from 25 °C and 1.00 atm to 125 °C and 5.00 atm. How do you
rationalize the sign of ΔS?
3. Consider a system consisting of 2.0 mol CO 2 (g), initially at 25 °C and 10 atm and
confined to a cylinder of cross-section 10.0 cm2. It is allowed to expand adiabatically
against an external pressure of 1.0 atm until the piston has moved outwards through
20 cm. Assume that carbon dioxide may be considered a perfect gas with 𝐶𝐶𝑉𝑉,𝑚𝑚 = 28.8 J
K-1 mol-1 and calculate 𝑞𝑞, 𝑤𝑤, ∆𝑈𝑈, ∆𝑇𝑇 and ∆𝑆𝑆
4. Calculate the change in the entropies of the system and the surroundings, and the
total change in entropy, when a sample of nitrogen gas of mass 14 g at 298 K and
1.00 bar doubles its volume in (a) an isothermal reversible expansion, (b) an
isothermal irreversible expansion against 𝑝𝑝𝑒𝑒𝑒𝑒𝑒𝑒 = 0, and (c) an adiabatic reversible
expansion.
5. The m o l a r heat capacity, 𝐶𝐶𝑝𝑝,𝑚𝑚 ( i n J o u l e K - 1 m o l - 1 ) of chloroform (CHCl 3 ) in the

range 240 K to 330 K is given by 𝐶𝐶𝑝𝑝,𝑚𝑚 = 91.47 + 7.5 × 10−2 𝑇𝑇 where, 𝑇𝑇 is the
absolute temperature. In a particular experiment, 1.00 mol CHCl 3 is heated from 273
K to 300 K. Calculate ∆𝑆𝑆.
6. 20 lit of nitrogen gas at 100 atm and 200 °C expands adiabatically against a
constant external pressure of 1 atm until the equilibrium is attained. Calculate ΔS
for (a) the change and (b) if the process is carried out reversibly to the same
final pressure. Given: 𝐶𝐶𝑝𝑝,𝑚𝑚 =7 cal/mol/K
7. If α (isobaric expansion coefficient) = 1.82 × 10-4 K-1 and κ (isothermal
𝜕𝜕𝜕𝜕
compressibility) = 3.87 × 10-5 atm-1 at 20 °C for mercury, then determine � � for
𝜕𝜕𝜕𝜕 𝑉𝑉
mercury.
8. The enthalpy of vaporization of ethanol is 43.5 kJ/mol at its normal boiling point of
352 K. Calculate (a) the entropy of vaporization of ethanol at this temperature, and
(b) the entropy change of its surroundings.
9. Calculate the difference in the molar entropy between liquid water and ice at – 5 °C
and 1 atm. The difference in the heat capacities on melting is 37.3 J/K. Calculate the
change in entropy for the system, surrounding, and the universe, and concludes if the
ice would melt spontaneously at – 5 °C at 1 atm.
10. A sample consisting of 1 mol Ar is expanded isothermally at 0 °C from 22.4 dm3 to

44.8 dm3 (a) reversibly, (b) against a constant external pressure equal to the final
pressure of the gas, and (c) freely (against zero external pressure). For the three
processes calculate q, w, ΔU, and ΔH.
11. When 229 J of energy is supplied as heat to 3.0 mol Ar(g) at 1 atm, the temperature of
the sample increases by 2.55 K. Calculate the molar heat capacities at constant volume
and constant pressure of the gas.
12. A sample of 4.0 mol O 2 is originally confined in 20 dm3 at 270 K and then undergoes
adiabatic expansion against a constant pressure of 600 Torr until the volume has
increased by a factor of 3.0. Calculate q, w, ΔT, ΔU, and ΔH. Cp,m=29.355 J K-1 mol-1 for
O 2 . (The final pressure of the gas is not necessarily 600 Torr.)
13. For each of the following processes, deduce whether the quantities q, w, ΔU, and ΔH
are positive, negative or zero – (a) Reversible melting of ice at 1 atm and 0 °C (b)
Reversible adiabatic expansion of a perfect gas (c) Adiabatic expansion of a perfect gas
into a vacuum (Joule experiment) (d) Reversible heating of a perfect gas at a constant
pressure.
14. The isothermal compressibility of copper at 293 K is 7.35×10-7 atm-1. Calculate the
change in pressure that must be applied in order to increase its density by 0.08 %.
15. Given that μ = 0.25 K atm-1 for nitrogen, calculate the value of its isothermal Joule–
Thomson coefficient. Calculate the energy that must be supplied as heat to maintain
constant temperature when 15.0 mol N 2 flows through a throttle in an isothermal
Joule–Thomson experiment and the pressure drop is 75 atm. [ Given:C p,m = 29.125 J K-1
mol-1]
16. Suppose that 3.0 mol N 2 (g) occupies 36 cm3 at 300 K and expands to 60 cm3.
Calculate ΔG for the process.
17. 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.

Tutorial 2 Spring 2018-19

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CY11001 (Physical Chemistry) Tutorial 2

Assume ideal behaviour unless stated otherwise

1. A sample consisting of 3.00 mol of a diatomic perfect gas at 200 K is compressed

5. The m o l a r heat capacity, 𝐶𝐶𝑝𝑝,𝑚𝑚 ( i n J o u l e K - 1 m o l - 1 ) of chloroform (CHCl 3 ) in the

10. A sample consisting of 1 mol Ar is expanded isothermally at 0 °C from 22.4 dm3 to

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