Physical Chemistry Homework #2 Oct /14/2021

(Due: 3:10pm, Oct/28/2021)

Problem 1
a. The following figure shows a Carnot cycle in the form of a pressure-volume
diagram. Sketch the corresponding entropy-temperature diagram, labeling the
individual steps A → B(𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚 𝑎𝑡 𝑇 ) , B → C (𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐), C →
D(𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚 𝑎𝑡 𝑇 ), and D → A (𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 ).
b. Suppose that a reversible Carnot engine operates between 300K and a higher
temperature 𝑇 . If the engine produces 10kJ of work per cycle and the entropy
change in the isothermal expansion at 𝑇 is 100JK-1, what are 𝑞 , 𝑞 , and 𝑇 ?

Problem 2
Calculate the entropy of mixing per mole of air, taking the composition by volume to
be 79% N2, 20% O2, and 1% Ar.

Problem 3
At 100℃ 200g of mercury are added to 80g of water at 20℃ in a vessel that has a
water equivalent of 20g. The specific heat capacities of water and mercury may be
taken as constant at 4.18 and 0.140 JK-1 g-1, respectively. Calculate the entropy
change of (a) the mercury; (b) the water and vessel; (c) the mercury, water, and vessel
together.

Problem 4
One mole of an ideal gas is initially at 10 bar and 298K. It is allowed to expand
against a constant external pressure of 2 bar to a final pressure of 2bar. During this
process, the temperature of the gas falls to 253.2 K. Find ∆U, ∆H, ∆S, ∆S , and
∆S for the process. Assume that the thermal surroundings remain at 298K
throughout. Devise at least three different paths to accomplish this change and show
that no matter which path is used, the desired values are the same.

Problem 5
The heat of vaporization of water at 25℃ is 44.01kJ mol-1, and the equilibrium vapor
pressure at that temperature is 0.0313 atm. Calculate ∆S, ∆H, and ∆G when 25℃ and a
pressure of 10-5 atm, assuming the vapor to behave ideally.
Physical Chemistry Homework #2 Oct /14/2021
(Due: 3:10pm, Oct/28/2021)

Problem 6
Calculate the absolute entropy of SO2 (g) at 300.0K and 1 bar given the following
information : 𝑆 ° (15.0𝐾 ) = 1.26𝐽𝐾 𝑚𝑜𝑙 ,𝐶 , (𝑠) = 32.65𝐽𝐾 𝑚𝑜𝑙 , 𝑇 =
197.64𝐾,∆ 𝐻° = 7402𝐽𝑚𝑜𝑙 , 𝐶 , (𝑙) = 87.20𝐽𝐾 𝑚𝑜𝑙 , 𝑇 =
263.28𝐾, ∆ 𝐻° = 24937𝐽𝑚𝑜𝑙 , 𝐶 , (𝑔) = 39.88𝐽𝐾 𝑚𝑜𝑙 .

Problem 7
Obtain an expression for the Joule-Thomson coefficient for a gas obeying the
equation of state
P(𝑉 − 𝑏) = 𝑅𝑇
in terms of R, T, P, 𝑉 , and 𝐶 , .

Problem 8
Derive the following equation:
a. 𝐶 = −𝑇
b. = −𝑇