Exam 2

Problem 1:

For a pure, simple fluid the molecular form of the corresponding states principle can be
written

P* = f1 (T *,V*) (1)

where P* = Pσ 3 / ε , T * = kT / ε , V* = V / σ 3 , f1 is a universal function for all the

fluids in the corresponding states group, and s and e are distance and energy
parameters in the intermolecular potential energy function.

(a) What assumptions are implicit in this equation? Explain why argon,
krypton and methane obey this law, but water, methanol, neopentane and helium do
not.

(b) Show that if eqn. (1) is valid, an equally valid form is

Pr = f2 (Tr ,Vr ) (2)

where Pr = P / Pc , Tr = T / Tc , Vr = V / Vc .

(c) For more complex fluids a three-parameter corresponding states

principle is often used,

Pr = f3 (Tr ,Vr , X) (3)

where X is some appropriate third parameter. Discuss appropriate criteria for choosing
a suitable third parameter X, and give an example of a widely used third parameter of
this kind.

(d) The surface tension of saturated liquid argon at 69.4K (T* = 0.570) is
0.01726 J/m2. Using the data presented in Table 1:
(i) estimate the surface tension of saturated liquid nitrogen and saturated liquid
water at the same reduced temperature. The reduced surface tension can be written as:

γσ 2
γ*=
ε

Table 1: Experimental surface tension data at T* = 0.570 for various substances.

σ(Å) ε/k  (K)     MW (g/mol) γ    (J/m2)  

Argon 3.429 121.85 39.948 0.01626
Nitrogen 3.663 96.92 14.006 0.01347
Water 2.641 809.1 18.015 0.04048

(ii) Compare your estimates to the experimental values given in Table 1.

Comment on the accuracy of each estimate using the CST approximations as support.

Given:

æ ¶P ö æ ¶ 2 P ö
Critical point conditions: ç ÷ = 0, ç 2 ÷ = 0
è ¶V øTC è ¶V øTC
Boltzmann’s constant: k = 1.38066 x 10-23 J.K-1

Problem 2.

For a mixture of spherical molecules the second virial coefficient is given by

B = ∑ ∑ xα xβ Bαβ (4)
α β
where
∞

Bαβ = 2π ∫ dr r 2 1− e ( −uαβ (r )/kT

) (5)
0

where uαβ (r) is the pair potential for a molecule of component a interacting with a
molecule of component b, and is of the form

⎛ r ⎞
uαβ (r) = ε αβ f ⎜ ⎟ (6)
⎝ σ αβ ⎠

where f is assumed to be the same function for all pairs in the mixture. The unlike pair
parameters ε αβ and σ αβ are often approximated by the Lorentz-Berthelot combining
rules, which relate them to the like pair parameters:

( )
1/2
ε αβ = ε αα ε ββ (7)

(
σ αβ = σ αα + σ ββ / 2 ) (8)

(a) Derive an equation for B for a mixture of square well molecules, having the pair
potential

uαβ (r) = ∞ r < σ αβ

= −ε αβ σ αβ < r < Rσ αβ (9)
=0 r ≥ Rσ αβ

What is the limit for Bab when T approaches infinity? Do you expect the square well
model to work well at high temperatures?

(b) For pair potentials of the form of eqn. (6), show that Bab obeys a corresponding
states relation of the form

*
Bαβ = f (Tαβ* ) (10)

where Bαβ *
= Bαβ / (2 / 3)πσ αβ
3
, Tαβ* = kT / ε αβ . Also, show that an equivalent
corresponding states relation for the second virial coefficient is

Bab / Vcab = f (T / Tcab )

where Vcab and Tcab are a “pseudocritical volume” and “pseudocritical temperature” for
a fluid with potential parameters eab and sab. Show that if these unlike parameters
obey the Lorentz-Berthelot rules given above, the pseudocritical temperature Tcαβ is
defined by

Tcαβ = (Tcα Tcβ )

1/2
(11)

where Tcα and Tcβ are the critical temperatures for pure a and pure b, respectively.
Derive the corresponding equation for the pseudocritical volume Vcab in terms of the
pure component critical volumes, Vca and Vcb .

Given: In simple corresponding states theory the reduced (i.e. dimensionless) critical
temperature, Tc* = kTc / e , pressure, Pc* = Pcs 3 / e , and volume, Vc* = Vc / s 3 , are
universal

constants.

For many3applications that we deal with in statistical mechanics it is possible to write

Problem
the canonical partition function in the form

3N /2
1 ⎛ 2π mkT ⎞
Z ( qelec qrot qvib )
N
Q=
N ! ⎜⎝ h2 ⎟⎠

provided that intramolecular rotations can be negelected. Here Z is the configuration

integral,

( )
Z = ∫ ...∫ d r1 d r2 ... d rN d ω 1 d ω 2 ... d ω N exp ⎡⎣ −U r N ,ω N / ( kT ) ⎤⎦

and integrations over the dri are over the volume of the system, and integrations over
the wi are over all possible values of the molecular orientation angles.

(a) What assumptions are implicit in writing Q in this form?

(b) Which parts of the partition function can usually be treated classically at room
temperature, and which cannot? What is the criterion that determines whether we can
use classical mechanics or not?

(c) Which parts of the partition function depend on the volume of the system? Which
parts of the partition function depend on the temperature?

(d) Which part(s) of the partition function must be known to determine the pressure, P
(i.e. the equation of state)? Why is this difficult to evaluate for a liquid?
(e) Which part(s) of the partition function must be known to determine the internal
energy, U?

Given:

Q = ∑ne
− En /kT

⎛ ∂lnQ ⎞
P = kT ⎜
⎝ ∂V ⎟⎠ T ,N
⎛ ∂lnQ ⎞
U = kT 2 ⎜
⎝ ∂T ⎟⎠ N ,V
Problem 1

(a) The two assumptions made are:

(i) No quantum effects for translation
(ii) The total intermolecular potential energy of interaction depends on only 2
potential parameters, ε and σ.

The simple corresponding states principle works well for argon, krypton and
methane because these are relatively heavy molecules for which quantum effects for
translation are negligible at normal temperatures, and because their intermolecular
potential energy is well described by a function with only two parameters. For water,
methanol and neopentane a two-parameter potential is insufficient so the second
approximation is not valid. For helium, since this is a very light molecule quantum
effects for translation will be significant and cause departures from simple
corresponding states.

(b) At the critical point

⎛ ∂P * ⎞
⎜⎝ ∂V * ⎟⎠ = 0
C

⎛ ∂2 P* ⎞
⎜⎝ ∂V *2 ⎟⎠ = 0
C
Applying the two equations to equation (1):

( )
f1' TC*,VC* = 0 (1)
f (T ,V ) = 0
1
'' *
C
*
C
(2)
Solving equations (1) and (2) for the two unknowns TC* and VC*
 kTC
TC* = = c1 = constant
ε
V
VC* = C3 = c2 N A = constant
σ
ε T
∴ = C
k c1
VC
σ3 =
c2 N A
PCσ 3
∴ PC* = = f1 (TC* ,VC* ) = f1 ( c1 ,c2 N A ) = c3 = constant
ε
ε P
= C
σ 3
c3
∴Eqn.(3-c) becomes
P ⎛ T V⎞
c3 = f1 ⎜ c1 ,c2 N A ⎟
PC ⎝ TC VC ⎠
or
Pr = f2 (Tr ,Vr )

(c)
The appropriate criteria for choosing a third parameter, X, are:
(a) it should be sensitive to the acentricity of the intermolecular forces, i.e. to
departures from assumption (ii) above, namely that the intermolecular forces
can be described by a two-parameter potential function.
(b) It should be easy to measure, so that its’ value is likely to have been measured
for many different substances.
An example is the Pitzer acentric factor, ω, which is a measure of the slope of the plot
of log10Prsat vs. 1/T. This is sensitive to departures from approximation (ii), so that the
slopes of such a plot are very different for water, benzene and the inert gases. Also,
vapor pressure is very easy to measure.

(d)

γ*=(γ  σ2)/(  (ε/k)*k)  

T*=69.4/121.85=0.5696  
γ =(0.01726*(3.429E-­‐‑10)2)/(  (121.85)*k)=1.136  
*

γN,H2O  =  (  (ε/k)*k*  γ*)/  σ2  

For  nitrogen:  
T=T*(ε/k)=0.5696*96.92=55.21  K  
γN  =(96.92*1.38066E-­‐‑23*1.136)/ (3.663E-10)^2 = 0.009973 J.m-2

For water:
 T=  T*(ε/k)=0.5696*809.1=460.86  K
γH20=(809.1*1.38066E-­‐‑23*1.136)/ (2.641E-10)^2 = 0.1819 J.m-2  

The result for nitrogen is lower than the experimental value but not by a great deal.
This difference is due to the fact that the simple corresponding states theory is not
highly accurate for nitrogen, also the CST calculation does not properly account for
three-body forces which are known to have a large effect on surface tension.

The result for water is more than four times the experimental value. This is because
water cannot be described by a two-parameter potential function, and surface tension is
very sensitive to this breakdown of assumption (ii).

Problem 2

(a)
( )
∞
Bαβ = 2π ∫ drr 2 1− e
−uαβ (r )/kT
0

drr 2 (1− e−∞ ) + 2π ∫ ( )+ 0

σ αβ Rσ αβ
= 2π ∫
ε /kT
drr 2 1− e αβ
0 σ αβ

2π 3 2π 3
=
3
σ αβ + σ αβ ( R 3 − 1) 1− e αβ
3
ε /kT
( )
B = ∑ α ∑ β xα xβ Bαβ

When T approaches infinity the second term on the right vanishes and Bαβ approaches
( 2π / 3)σ αβ3 . This is physically incorrect, it should approach zero. Thus the square
well model does not work well at high temperature, but is a useful model at lower
temperatures.

(b) Defining reduced distance and temperature as r ∗ = r / σ αβ , T ∗ = kT / ε αβ , eqn.

(5) and (6) give:

∞
Bαβ = 2π ∫ dr ∗r ∗2 1− e
0 ( ( )
− f r ∗ /Tαβ
∗

)
or
∗
Bαβ = Bαβ / ( 2 / 3) πσ αβ
3
∞
= 3∫ dr ∗r ∗2 1− e
0 ( ( )
− f r ∗ /Tαβ
∗

) = f (T ∗
αβ )

Also, by applying the critical point conditions, ( ∂P / ∂V )T = 0, ( ∂ 2 P / ∂V 2 )T = 0 , to the

c c

reduced equation of state, P* = f(T*,V*), we find that

Tc*=c1, Vc*=c2NA and Pc*=c3, where c1, c2 and c3 are universal constants, then σ αβ
3
can
be replaced by Vc and ε αβ / k by Tcαβ in the above equation, so that an equivalent form
of the corresponding states principle is

Bαβ / Vcαβ = f (T / Tcαβ )

Moreover, the pseudocritical temperature and volume are related to the potential
parameters by:

⎛ε ⎞ ⎛ε ε ⎞
1/2

= c1 (Tcα Tcβ )
1/2
T αβ
= c1 ⎜ αβ ⎟ = c1 ⎜ αα 2 ββ ⎟
c
⎝ k ⎠ ⎝ k ⎠
1
( 1
) ( )
3
Vcαβ = c2 N Aσ αβ
3
= c2 N A σ αα + σ ββ = c1/3
2 N A σ αα + c2 N A σ ββ
1/3 1/3 1/3

8 8

(
1 1/3
)
3
= Vc,α + Vc,1/3β
8

where the Lorentz-Berthelot combining rules of eqns. (7) and (8) have been used for the
unlike pair parameters.

Problem 3

(a) The underlying assumption is that individual contributions to Q are

independent. For instance, this means that the electronic states of the system are
not appreciably affected by the rotational or vibrational modes, and vice versa.
(b)  The translational part, ( 2π mkT / h 2 )
3N /2
, configurational part, Z, and rotational
part, qrot, can usually be treated classically because many energy levels are
occupied and these are closely spaced compared to the thermal energy, kT. The
latter is the condition for being able to use classical statistical mechanics.
(c) The pressure is given by

⎛ ∂lnQ ⎞
P = kT ⎜
⎝ ∂V ⎟⎠ N ,T
so the only parts of the partition function that contribute to the pressure are
those that depend on the volume. In the semi-classical approximation the only
part of Q that depends on V is the configurational part, Z.

All of the parts of the partition function – translational, configurational,

electronic, rotational and vibrational – depend on the temperature through the
exponential term, exp(-E/kT).
(d)   The configurational part, the configuration integral, Z, must be known in order
to calculate the pressure. The pressure consists of a contribution from the ideal
gas term, ρ kT , and a part from the intermolecular forces (configurational part).
These are usually of similar magnitude but of opposite sign, thus reducing the
accuracy with which the pressure can be calculated.
(e)   The internal energy is given by

⎛ ∂lnQ ⎞
U = kT 2 ⎜
⎝ ∂T ⎟⎠ N ,V

Since all parts of the partition function depend on T, they all contribute to U.