Problems

1. At very low temperatures the heat capacity of a solid is proportional to T3, and we can
write Cp,m=aT3. What is the change in enthalpy of such a substance when it is heated from
0 to a temperature T?
2. A sample consisting of 1.00mol of perfect gas atoms, for which Cv,m=(3/2)R, initially at
p1=1.00atm and T1=300K, is heated reversibly to 400K at constant volume. Calculate the
final pressure at ∆U, q, and w.
3. When 229J of energy is supplied as heat to 3.0 mole Ar(g), the temperature of the sample
increases by 2.55K. calculate the molar heat capacities at constant volume and constant
pressure of the gas.
4. Given that the standard enthalpy of formation of HCl (aq) is -167kJ mol-1, what is the value
of ∆fH° (Cl-, aq)?
5. When 225mg of anthracene, C14H10(s), was burned in a bomb calorimeter the temperature
rose by 1.75K. Calculate the calorimeter constant. By how much will the temperature rise
when 150mg of phenol, C6H5OH(s), is burned in the calorimeter under the same
conditions? (∆cH° (C14H10 s)=-7061kJ mol-1 )
6. Use the equipartition principle to estimate the values of ϒ=Cp/Cv for gaseous ammonia and
methane. Do this calculation with and without the vibrational contribution to the energy.
Which is closer to the expected experimental value at 25°C?
7. At -5°C, the vapor pressure of ice is 3.012mm, whereas the vapor pressure of supercooled
liquid water is 3.163mm. Calculate the ∆G per mole for transition waterice at -5°C.
8. Calculate the ∆S per liter of solution when pure N2, H2, and NH3 gases are mixed to form
solution having the final composition 15% N2, 55% H2, and 30% of NH3 (at STP)
9. Assuming that the density of mercury remains constant at 13.5 g ml-1 at 25°C. Calculate
the ∆G of one mole of mercury when pressure is increased from 1 to 101atm.
10. Derive the expression (∂H/ ∂P) T= (∂S/∂P) T +V
11. Prove that it is impossible for two reversible adiabatic on a P-V diagram to intersect.
12. Derive an expression for the Joule-Thomson coefficient of a gas obeying the equation of
state P(V-b) =RT
13. The reversible work expended to produce in a sample of ferromagnetic material a
moment M by application of a magnetic field H is, -H dM. show that:
𝜕𝑀 𝜕𝐻
𝐶𝐻 − 𝐶𝑀 = −𝑇 ( ) ( )
∂T 𝐻 ∂T 𝑀
where 𝐶𝐻 , 𝐶𝑀 are the heat capacities at constant field and constant moment.

14. 10g of CO at 0°C are adiabatically and reversibly compressed from 1atm to 20 atm.
Calculate ∆E, ∆H, and ∆S for the change in the gas. Assume Cv=4.95cal/°C mole and ideal
gas behavior. Would it be possible to calculate ∆G from the data provided?