6 Problem, €4 Solutions on Thermodynum'ca €4 Statistical Mechanics
Solution:
This is a process of adiabatic free expansion of an ideal gas. The
internal energy does not change; thus the temperature does not change,
that is, the final temperature is still T .
1005
An insulated chamber is divided into two halves of volumes. The left
half contains an ideal gas at temperature TOand the right half is evacuated.
A small hole is opened between the two halves, allowing the gas t o flow
through, and the system comes to equilibrium. No heat is exchanged with
the walls. Find the final temperature of the system.
(Columbia)
Solution:
After a hole has been opened, the gas flows continuously t o the right
side and reaches equilibrium finally. During the process, internal energy of
the system E is unchanged. Since E depends on the temperature T only
for an ideal gas, the equilibrium temperature is still To.
Fig. 1.3.
1006
Define heat capacity C, and calculate from the first principle the nu-
merical value (in caloriesj'C) for a copper penny in your pocket, using your
best physical knowledge or estimate of the needed parameters.
(UC,Berkeley)
Solution:
C,,= ( d Q / d T ) , . The atomic number of copper is 64 and a copper
penny is about 32 g, i.e., 0.5 mol. Thus C, = 0.5 x 3R = 13 J/K.
Thermodynamics 7
1007
Specific heat of granite may be: 0.02,0.2,20,2000 cal/g.K.
(Columbia)
Solution:
The main component of granite is CaC03; its molecular weight is 100.
The specific heat is C = 3R/100 = 0.25 cal/g. K. Thus the best answer is
0.2 cal/g.K.
1008
The figure below shows an apparatus for the determination of C,/C,
for a gas, according t o the method of Clement and Desormes. A bottle
G, of reasonable capacity (say a few litres), is fitted with a t a p H, and a
manometer M. The difference in pressure between the inside and the out-
side can thus be determined by observation of the difference h in heights of
the two columns in the manometer. The bottle is filled with the gas t o be
investigated, at a very slight excess pressure over the outside atmospheric
pressure. The bottle is left in peace (with the t a p closed) until the tem-
perature of the gas in the bottle is the same as the outside temperature
in the room. Let the reading of the manometer be hi. The t a p H is then
opened for a very short time, just sufficient for the internal pressure to
become equal to the atmospheric pressure (in which case the manometer
reads h = 0). With the t a p closed the bottle is left in peace for a while,
until the inside temperature has become equal t o the outside temperature.
Let the final reading of the manometer be h. From the values of h; and h,
it is possible to find Cp/Cv. (a) Derive an expression for C,/Cv in terms of
h; and h, in the above experiment. (b) Suppose that the gas in question
is oxygen. What is your theoretical prediction for C,/Cv at 2OoC, within
the framework of statistical mechanics?
(UC,Berkeley)
Fig. 1.4.
0 Problems 8 Sdutioru on Thermodyurmica 8 Statiaticd Mechanics
Solution:
(a) The equation of state of ideal gas is pV = nkT. Since the initial
and final T , V of the gas in the bottle are the same, we have p f / p ; = n f / n ; .
Meanwhile, nf/n; = V / V ' , where V' is the volume when the initial
gas in the bottle expands adiabatically to pressure P O . Therefore
-=(E)7
V'
V
1
1 "=(a)+,
Pi
Since h;/ho << 1 and h f / h o << 1, we have 7 = h;/(h;- h f ) .
(b) Oxygen consists of diatomic molecules. When t = 2OoC, only
the translational and rotational motions of the molecules contribute t o the
specific heat. Therefore
1009
(a) Starting with the first law of thermodynamics and the definitions
of cp and c,, show that
cp-c,= [ P + ( a au
v)T1 (%)
P
where cp and c, are the specific heat capacities per mole at constant pres-
sure and volume, respectively, and U and V are energy and volume of one
mole.
(b) Use the above results plus the expression
p+(%),=T(%) V
to find cp - c, for a Van der Waals gas
Use that result to show that as V --+ 00 at constant p , you obtain the ideal
gas result for cp - c,.
(SUNY, Buflulo)
Thermodynamics 9
Solution:
(a) From H = U + pV, we obtain
(%)p= (%),+p(%) P *
Let U = U [ T V
, ( T ,p ) ] . The above expression becomes
Hence
P
(b) For the Van der Waals gas, we have
R
RT 2a(V - b)
v3
Hence ,
R
c p - C" =
1 - 2a( 1 - b / V ) 2 / V R T '
When V -+ 00, c p - c , + R, which is just the result for an ideal gas.
1010
One mole of gas obeys Van der Waals equation of state. If its molar
internal energy is given by u = cT - a/V (in which V is the molar volume,
a is one of the constants in the equation of state, and c is a constant),
calculate the molar heat capacities C , and C,.
( was co nsin)
Solution:
c,=(%) = c ,
V
%= (g)p+p(%)p= (%)v+ [ ( 3 , + P l
x(%) = c + ( & + p ) ( E ) .
P P
