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Problem Set 2

10.

Atkins 2.6, 2.7, and 2.8. These are review exercises on

fundamental definitions associated with work.

11.

Atkins 2.10 and 2.11. What is the work if 2.10 is in fact

constant volume? Then work 2.10 assuming that the piston
plus atmosphere created an external force equivalent to
10 atm. To work 2.11, realize that reactions in open
vessels most effectively push back the atmosphere.

12.

Atkins 2.13.

13.

Atkins 2.18 and 2.19. Be sure to understand this pair

on partial derivatives.

14.

15.

Atkins 2.20. Assume that vibrational energy gives QQ

contribution to the polyatomic molecule. If you deduce
C , what is C for these fellows?
v
p
Atkins 2.22. A fundamental exercise on heat.

16.

Atkins 2.25.

A simple problem for real gases.

Obviously the finale for Chapter 2.

2.6. A chemical reaction occurs in a vessel of cross-section

100 cm 2 fitted with a loosely fitted seal. During the reaction
the seal is pushed out through 10 em against the external
pressure of 1.0 atm . How much work does the reaction do
on the outside world?
2.7. Using the same system as in the last Problem,
calculate the work done when the pressure of the atmosphere is replaced by a mass of 5.0 kg acting downwards on
the vertical piston. What is the work done when the same
mass stands on a piston of cross-section 200 cm 2 and moves
through the same distance.
2.8. In another reaction occurring within the same apparatus employed in the last Problem , a contraction of
10 em occurs. Discuss the work involved in the change .

2.10. 1.0 mol CaC0 3 was heated to 700 oc, when it decomposed. The operation was carried out in a container
closed by a piston which was initially resting on the sample
and was restrained throughout by the atmosphere. How
much work was done during complete decomposition?
2.11. The same experiment as in the last Problem was
repeated, the only difference being that the carbonate was
heated in an open vessel. How much work was done during
decomposition?

2.13. We have to be able to deal with the work involved

in the expansion of real gases. In the case of reversible
expansion or compression this involves knowing how the
pressure varies with the volume of the enclosed system.
Information of this kind is contained in the equation of
state, and the next few problems explore the consequences
of employing some of the approximate equations that are
available. In the first place, calculate the work done in an
isothermal, reversible expansion of a gas that satisfies the
virial equation of state, pVm = RT(1 + B ! Vm + ... ).

2.18. The technique of partial differentiation is straightforward once one realizes that only the variable stated
explicitly, e.g. the x in 3f/8x, is varied, all others being
regarded as constants. In order to get further practice , take
(a) the perfect gas equation, (b) the Dieterici equation,
Box 1.1 , and evaluate (3p / 8T)v and (3p / 3V)T. Go on to
confirm that 8 2p / 8V aT = 8 2p / 3T av.
2.19. Partial derivatives can (and, in thermodynamics , do)
have real physical meaning. For instance take the expressions for the two partial derivatives of p for a perfect gas
obtained in the last Problem and answer the following. In
an estimation of the pressure exerted by a gas, the
temperature was uncertain by 1 percent and the volume
was uncertain by 2 percent. What is the uncertainty in the
prediction of the pressure arising from (a) the temperature
uncertainty, (b) the volume uncertainty, (c) both.

2.20. The equipartition principle , Section 0.1(f) , Jets us

calcl!late the internal ~nergy of a perfect gas. In the case of
a monatomic gas it gives U =~nRT. This result (and
others like it for more complicated molecules) gives a very
quick way of predicting the heat capacity of these materials.
Deduce the value of the molar hefit capacity of (a) a
monatomic perfect gas, (b) a gas of rotating, translating,
nonlinear, polyatomic molecules.

2.22. The constant-pressure heat capacity of helium is

20.79 j K- 1 How much heat is required to raise the
temperature of a sample of 1.0 mol by 10 K at 25 oc (a)
when it is in a constant volume vessel at a pressure of
19 atm, (b) when it is in a vessel fitted with a piston
subjected tp a constant external.pressure of 10 atm? How
much wprk is done in each case? .

2.25. A kettle containing 1.0 kg of boiling water is

heat~d

until evaporation is complete. Calculate (a) w , (b) q, (c)

b.U, (d) b.H for the process. (b.Hvap,m = 40.6 kJ mol- 1 at
373 K; treat H 2 0(g) as a perfect gas.)