CHY121 - Basic Physical Chemistry

Tutorial session – 8

1. Why is the heat capacity at constant pressure of a substance normally greater than its
heat capacity at constant volume?

2. The value of ∆rH0 at 25 0C and 1 bar is 290.8 kJ for the reaction:

2 ZnO(s) + 2 S(s) ⇾ 2 ZnS(s) + O2 (g).

Assuming ideal behaviour, calculate the value of ∆rU0 for this reaction.

3. Can a gas be liquefied through an isoenthalpic expansion if µJ−T = 0 ? Justify.

𝜕𝐶𝑉
4. Show that ( ) = 0 for an ideal gas.
𝜕𝑉 𝑇

𝛼 𝑅
5. Show that for a van der Waals gas, = 𝑉−𝑏.
𝜅

6. 10 moles of an ideal gas expands isothermally and reversibly from a pressure of 10 atm
to 2 atm at 300 K . What is the largest mass which can be lifted through a height of 1 m
in this expansion?

7. Establish the relation between 𝑞𝑃 and 𝑞𝑉 in Haber synthesis of ammonia, assuming that
the gaseous reactants and products are ideal.

8. Liquid water decreases in volume with increasing temperature between 0 0C and 4 0C

at 1 atm. What will be the sign of coefficient of thermal expansion?

9. 𝐶𝑃,𝑚 of a certain substance in the temperature range 250 K to 500 K at 1 bar pressure
is given by 𝐶𝑃,𝑚 = 𝑏 + 𝑘𝑇, where 𝑏 and 𝑘 are certain known constants. If 𝑛 moles of
this substance is heated from 𝑇1 to 𝑇2 at 1 bar (where 𝑇1 and 𝑇2 are in the range 250
K to 500 K), find the expression for ∆𝐻.

10. When a gas at 22 atm and 5 0C was allowed to expand adiabatically to a final pressure
of 1 atm, the temperature fell by 10 K. Calculate the Joule-Thomson coefficient, 𝜇𝐽−𝑇 ,
at 5 0C, assuming it remains constant over this temperature range.
11. Starting with the van der Waals equation of state, find an expression for the total
differential dP in terms of dV and dT. By calculating the mixed partial derivatives
𝜕 𝜕𝑃 𝜕 𝜕𝑃
(𝜕𝑇 (𝜕𝑉) ) and (𝜕𝑉 (𝜕𝑇) ) , determine if dP is an exact differential.
𝑇 𝑉 𝑉 𝑇

𝑇
12. The heat capacity of solid lead oxide is given by 𝐶𝑝,𝑚 = 44.35 + 1.47 × 10-3 in
𝐾
-1 -1
units of J K mol . Calculate the change in enthalpy of 1 mol of PbO(s) if it is cooled
from 500 K to 300 K at constant pressure.

𝜕𝑈 3𝑎
13. Derive the following relation, (𝜕𝑉 ) = 2 , for the internal pressure of a gas
𝑚 𝑇 √𝑇𝑉𝑚 (𝑉𝑚 +𝑏)
𝑅𝑇 𝑎 1
that obeys the equation of state, 𝑃 = 𝑉 −𝑏 − 𝑇 𝑉 (𝑉 +𝑏).
𝑚 √ 𝑚 𝑚