Prof.

Anchordoqui
Problems set # 2

September 9, 2014

Physics 303

1. Van der Waals equation of state for a non-ideal gas describing its transition to liquid has the
form


a
P + 2 (v b) = RT,
v
where a describes attraction of the gas molecules and b describes the volume occupied by the
molecules and thus excluded from their motion. (i) Plot isotherms of this gas for diferent T ,
setting a = b = R = 1. Verify that at high T isotherms are close to those for an ideal gas, but
for lower T they become distorted. Show that below a critical temperature T < TC there is a
local maximum and minimum of P . The transition between the two types of curves (that is where
T = TC ) is a curve having an inflection point called the critical point (CP). This transition curve is
known as the critical curve. (ii) Calculate the isothermal compressibility of the van der Waals gas
in terms of (v, T ). Obtain its high-temperature limit. What happens with it at the critical point?
(iii) Find the critical point parameters using the analysis in (i) as a hint.
Solution: (i) See Fig. 1. Straightforward calculus analysis would determine the exact location of
maxima and minima. (ii) Rewrite the compressibility as T = v1

the equation of state for P as P =

RT
vb

v
P

= v1

P
v

1
T

and solve

va2 . You can see that the b-term increases pressure whereas

the a-term decreases pressure, as expected. Differentiating P you first find

2

P
v

RT
= (vb)
2 +

2a
v3

(vb) /v
1
that yields T = v1 2a/v3 RT
= RT 2a(vb)/v
3 . At high temperatures v becomes large, so
/(vb)2
you can neglect the terms with a and b to obtain T = v/(RT ) = P 1 , which is the result for an
ideal gas. With lowering T , the volume decreases and the negative term
denominator
causes
 in
 the 

2P
=
=
0,
that
is
T to diverge at the critical point. (iii) To find the critcal point use P
v
v 2

P
v

RT
= (vb)
2 +

2a
v3

= 0 and

2P
v 2

2RT
= (vb)
3

6a
v4

= 0. Getting rid of the denominators, you

obtain the following system of equations RT v 3 = 2a(v b)2 and RT v 4 = 3a(v b)3 . Divide the
second equation by the first one to get v = 23 (v b). Solving this equation you obtain the critical
8a
.
volume: vC = 3b. After that you can obtain the critical temperature RTC = v2a3 (vC b)2 = 27b
Finally, the critical pressure follows from the equation of state: PC =

RTC
vC b

a
2
vC

a
.
27b2

2. Using the Berthelot equation of state,

P =
q

RT
a

,
v b T v2

8a
1
show that vC = 3b, TC = 27bR
, and PC = 12b
with the experimental values given in Table 1.

hand,

P
V

RT
2a
= (vb)
2 + T v 3 and

P
= 0
 2V CP
P
2RT
= (vb)
3
V 2

Solution: At the critical point



2aR
3b .

1
Compare the numerical value of RTC PC1 vC

and

2P
V 2 CP

= 0. For the equation of state at

T6a
. The condition at the critical point leads to
v4

Figure 1: Isotherms of the van der Waals gas.

RTC
(vC b)2

2a
3
TC vC

and

2RTC
(vC b)3

6a
4 .
TC vC

Solve the system of equations to obtain vC = 3b, TC =

aR
C
TCav2 = 216b
which yield PC = vRT
3 . The theoreticall value,
c b
c
than the experimental value for all the given gases.

RTC
PC vC

8a
27Rb ,

= 2.67, is always smaller

Q
= CV + R (1 b) .
dT
3. Using the Dieterici equation of state,


b=0
C=C
RTP = CV a+ R
P =
exp
,
RT C
v ! 1
b ! 1 vb
C=

a
a
show that vC = 2b, TC = 4Rb
, and find
, PC =
the numerical value of RTC PC1 vC1 . How does
4e2 b2
CP
this compare with the tabulatedCexperimental
values?
1
R
V
CV
R
CP CV R
 
 2 =
C = CV
=
= 0,
P
P
Solution: At the critical
= 01 and V
= 0. For the 1equation of state at
1 point V
2

2P
V 2

CP
h
i
P
a
a/(RT v) RT +
=
e
and
2
(vb)v 2
h V
io (vb)
1
2
a v2 (vb)
. The condition at the
2 + v 3 (vb)
a
system of equations. Solve the system to obtain vC = 2b, TC = 4Rb
.
RTC a/(RTC vC )
a
of state to obtain PC = vC b e
= 4b2 e2 . The theoretical value

CP
RT a/(RT v)
e
,
the
partial
derivatives
vb
n
h
i
1 a
1
a
2RT
a/(RT
v)
e

2
2
vb + (vb)3
v vb RT v

hand P =

read

=
critical point determine a
Substitute in the equation
C
of PRT
= 3.69, which is greater than the experimental values of He, H2 , O2 , CO2 , but is less than
C vc
that of H2 O.

4. (i) Making use of the

triple productfind the expansivity of a substance obeying the Dieterici equation of state. (ii) At high a
high specific volumens (low densities) all
P + temperature
(V and
b) =
RT,
2 for large values of T and v, the expression for obtained
gases approximate an ideal gas. Show V
that
in (i) goes over to the corresponding equation for an ideal gas.

b=

1
Table 1: Measurements of RTC PC1 vC
1
RTC PC1 vC
3.06
3.27
3.42
3.61
4.29

Substance
He
H2
O2
CO2
H2 O

Solution: (i) From the triple product you know that

v
T

eterici equation of state, these partial derivatives are given by:



1

P
RT
a
v
a/(RT v)
P T = v T = vb e
RT v 2
R+a/(vT )
RvT /(vb)a/v . (ii) For large v and T , v 

expected in ideal gas.

1
vb

i1

 P
P
T

. Finally, =

 

P
v
T v P T .
R a/(RT v)
1
vb e

1
v

v
T

=


= v1

P
T

For the Di+

a
RT v

 
v

b and RvT  a, the expression for reduces to

and

v
P T =
T 1 as

5. Show that and T are infinite at the critical point.

and hence . On


P
V

 
T

V
T

 
P

T
P

1/V
V
P
= 0
P T = (P/V )T . At the critical point V
 
the other hand, = V1 V
T P can be rewritten using the tripe product,
 
1
1
P
1, as = V1 (P/V
.
At
the
critical
point
= 0 and so
V
)T (T /P )V

Solution: On the one hand, T = V1