Homework 3

David Sirajuddin
Physics 715 - Statistical Mechanics
Professor Michael Ramsey-Musolf
March 19, 2010
1. Show that
C
V
= T
_
_
S
T
_

[(N/T)

]
2
(N/)
T
_
(1)
The proof is furnished by dening the chemical potential such that the internal energy
U changes by an increment dN, for a dierential particle number dN, at constant
entropy S and volume V ,
dU = TdS PdV + dN
That is,
_
U
V
_
N,S
= P
_
U
S
_
N,V
= T
_
U
V
_
S,V
=
With this denition, the two TdS equations (Huang (1.13), (1.14)) may be recasted as
TdS = C
V
dT + T
_
N
T
_

d
TdS = C
P
dT T
_

T
_
N
dN
Equating the right-hand sides of these equations
C
V
dT + T
_
N
T
_

d = C
P
dT T
_

T
_
N
dN
Choosing and N to be independent variables:
1
dT =
_
T

_
N
d +
_
T
N
_

dN
Inserting this into the previous equation and rearranging admits
_
(C
P
C
V
)
_
T

_
N
T
_

T
_
N
_
d +
_
(C
P
C
V
)
_
T
N
_

T
_

T
_
N
_
dN
Given the choices of d and dN being independent, this equation implies the bracketed
coecients must independently vanish. The right-hand terms imply
(C
P
C
V
)
_
T
N
_

T
_

T
_
N
= 0
C
P
C
V
= T
(/T)
N
(T/N)

The lemmas provided by Huang are used to recast this equation into the desired form
given in the problem statement [1, pg. 20]. Lemma (b) implies,
C
P
C
V
= T
(/T)
N
(T/N)

= T
_

T
_
N
1
(T/N)

. .
=(N/T)
C
P
C
V
= T
_

T
_
N
_
N
T
_

(2)
The term (/T)
N
is replaced by use of the cyclic permutation lemma (c),
_

T
_
N
_
T
N
_

_
N

_
T
= 1 (3)
An expression for (/T)
N
is obtained from this equation by aid of lemma (b), which
allows the following identies,
_
T
N
_

=
1
(N/T)

_
T
N
_

_
N
T
_

= 1
_
N

_
T
=
1
(/N)
T

_
N

_
T
_

N
_
T
= 1
2
Thus, multiplying Eqn. (3) by the indicated derivatives above such that these prod-
ucts are equal to unity isolates an equation for (/T)
N
(which may be substituted
back into the original equation [Eqn. (2)] to recover the result). Performing this
multiplication on Eqn. (3) admits
_

T
_
N
$
$
$
$
$
$
$
$
$
$
$
_
_
T
N
_

_
N
T
_

_
=1
$
$
$
$
$
$
$
$
$
$
$
__
N

_
T
_

N
_
T
_
=1
=
_
N
T
_

_

N
_
T
giving
_

T
_
N
=
_
N
T
_

_

N
_
T
Using this result in Eqn. (2),
C
P
C
V
= T
_

_
N
T
_

_

N
_
T
_
_
N
T
_

= T
_
N
T
_
2

_

N
_
T
An application of lemma (b) once more implies (/N)
T
= 1/(/N)
T
so that the
above equation can be written
C
P
C
V
= T
[(N/T)

]
2
(N/)
T
C
V
= C
P
T
[(N/T)

]
2
(N/)
T
Finally, using the TdS equation involving C
P
above implies that C
P
= T(S/T)

,
which upon substitution veries the proposition
C
V
= T
_
_
S
T
_

[(N/T)

]
2
(N/)
T
_
(4)
which veries the relation.
3
Figure 1: Proposed perpetual motion machine. The diagram on the right emphasizes the
meniscus of the vapor-water interface, shown with a radius of curvature r [2]
2. Consider the following proposal for a perpetual motion machine, shown in the dia-
gram below. The very narrow left-hand tube is connected top and bottom to a broad
tube. The water wets the tube walls so surface tension pulls the water in the capillary
tube up to an elevation h above the level in the thick tube. The system is at uniform
temperature T. The pressure in the vapor at (a) is lower than the pressure at (b) be-
cause (a) is higher than (b). Since the temperatures at (a) and (b) are equal, and since
the equilibrium vapor pressure is a function of T alone, given by the Clausius Clapeyron
relation, the vapor cannot be in equililbrium at (a) and (b) both. It appears that water
must be evaporating at (a) and condensing at (b). The ow of vapor drives the paddle
wheel, perpetually converting heat fully to mechanical work.
Start with the fact that this proposal is physically incorrect and compute the fraction
dierence p/p between the equilibrium vapor pressures of a at surfact and one with
curvature r in terms of r, T, the surface tension (the force/unit length), and the
specic volume v
f
= m/ of the uid. You may assume that the boundary of the vapor
and the water in the capillary tube is very nearly a section of a sphere with radius
r h, that the vapor is close to an ideal gas with specic volume v
vap
v
f
, and that
[p/p[ 1. Show that this perpetual motion machine cannot physically be realized.
The perpetual motion machine is shown to violate the Second Law by way of Kelvins
statement. Beginning with the suggestion, the dierence p/p between the equilibrium
vapor pressures and one with curvature r is calculated in terms of known parametes r,
T, and surface tension , and the specic volume v
f
= m/ of the uid.
Using the parameters labeled in the gure, the column of water is analyzed. The weight
of this column is R
2
h(
v
)g, where
v
is the mass density of water vapor, and
is the density of water. That is to say, the total weight is the dierence between the
water weight and the vapor it displaces. Given that
v
, the weight of the column
is approximately R
2
hg. The static scenario implies this weight is balanced by the
4
upward capillary force 2R,
&
R

2
hg = 2
&

R
Rhg = 2
h =
2
Rg
Which governs the height h to which the column may rise to. A second relation for
this height may be obtained by examining the dierence in vapor pressure at a height
h and at the elevation b,
P =
v
hg
h =
P

v
g
Equating these two expressions for h, and treating the vapor as an ideal gas, such
that
v
= P/R
w
T where R
w
is the gas constant for water vapor, gives the pressure
dierence
P

v
g
=
2
Rg
P =
2
v
R
=
2P
RR
w
T

P
P
=
2
RR
w
T
Putting rho = 1/v
f
(possibly a mistype in the problem statement?), and rewriting the
column radius R = r sin gives the nal equation for the fractional pressure dierence
P
P
=
2
r sin
v
f
R
w
T
(5)
For reasonable values of the quantities for water ( 72.8 dynes/cm, v
f
= 1 cm
3
/g,
R
w
= 461.5 J/(kg K), T = 273.15 K) the right-hand side is less than unity. This
implies the alleged evaporation does not occur, instead the water vapor condenses
so that the paddle wheel cannot be driven. Thus, no further violation of thermody-
namic laws need to be investigated given the machine does not operate as suggested.
the perpetual motion machine cannot physically be realized.
5
3. Two species of gas molecules, A and B,react chemically according to the formula
A + A B (6)
Let C
(0)
A
and C
(0)
B
= 1 C
(0)
A
be the concentrations of the two species of gas, treated as
ideal, when they are mixed and allowed to come into chemical equilibrium at temperature
T and pressure P
(0)
. Suppose that C
(0)
A
1. If the pressure is doubled to P =
2P
(0)
at constant T, what is the new equilibrium concentration, C
A
? Recall that the
concentration of particles of type k in a mixture is
C
k
=
N
k

N
j
, (7)
where N
j
is the number of particles of type j.
At chemical equilibrium, a minimum state of the change in Gibbs potential G is
reached. The Gibbs potential may be expressed, in general, as a sum over species of
type i
G =

i
N
i

i
dG =

i
N
i
d
i
+

i
dN
i
where N and are the number of particles and chemical potential (Gibbs potential
per mole), respectively. An additional relation for dG may be obtained using relation
(xxx) from problem (4). In this case, since the particle number is allowed to change, a
term

i
N
i

i
must be appended,
dG = SdT + V dP +

i
dN
i
Equating the right-hand sides of these two equations for dG admits

i
N
i
d
i
+

i
dN
i
= SdT + V dP +

i
dN
i

i
N
i
d
i
= SdT + V dP
Recalling that the process under consideration is isothermal implies dT 0, and
noting that

i
N
i
d
i
= N
A
d
A
+ N
A
d
A
N
B
d
B
= 2N
A
d
A
N
B

B
gives
2N
A
d
A
N
B

B
= V dP (8)
6
Expressions for
A
and
B
may be developed successively from the above equation by
invoking the ideal gas law (V/N = RT/P), where R is the universal gas constant, and
T is the temperature. Holding
B
constant implies d
B
0, such that
2N
A
d
A
= V dP
A
d
A
=
1
2
V
N
A
dP
A
=
1
2
RT
P
A
dP
A
_

A

(0)
A
d
A
=
_
P
A
P
(0)
1
2
RT
P
A
dP
A

(0)
A
=
RT
2
ln
_
P
A
P
(0)
_

A
=
(0)
A
+
RT
2
ln
_
P
A
P
(0)
_
And, similarly, letting
A
be xed (d
A
0) gives a relation for
B
N
B
d
B
= V dP
B
d
B
=
V
N
B
dP
B
=
RT
P
B
dP
B
_

B

(0)
B
d
B
=
_
P
B
P
(0)
RT
P
B
dP
B

(0)
B
= RT ln
_
P
B
P
(0)
_

B
=
(0)
B
+ RT ln
_
P
B
P
(0)
_
where the notation P
A
= C
A
P and P
B
= C
B
P denotes partial pressures attributed
to each respective molecule, with concentrations C
A
, C
B
as dened in the problem
statement. Using these two expressions, the Gibbs potential may be written down
G = 2
A
N
A

B
N
B
= 2N
A
_

(0)
A
+
RT
2
ln
_
P
A
P
(0)
__
N
B
_

(0)
B
+ RT ln
_
P
B
P
(0)
__
The number of molecules N
A
And N
B
may be replaced in terms of concentrations.
Recalling that C
A
= N
A
/N, C
B
= N
B
/N, for N = N
A
+ N
B
, yields
7
G = 2NC
A
_

(0)
A
+
RT
2
ln
_
P
A
P
(0)
__
NC
B
_

(0)
B
+ RT ln
_
P
B
P
(0)
__
G
N
= 2C
A
_

(0)
A
+
RT
2
ln
_
P
A
P
(0)
__
C
B
_

(0)
B
+ RT ln
_
P
B
P
(0)
__
(9)
Equation (xxx) may be used to nd the equilibrium chemical potential = (P
(0)
) at
P = P
(0)
, where C
A
= C
(0)
A
, C
B
= C
(0)
B
= 1 C
(0)
A
, and C
(0)
A
1,
(P
(0)
) = 2C
(0)
A
_

(0)
A
+
RT
2
ln
_
P
(0)
A
P
(0)
__
C
(0)
B
..
=1C
(0)
A
_

(0)
B
+ RT ln
_
P
(0)
B
P
(0)
__
= 2C
(0)
A
_

(0)
A
+
RT
2
ln
_
P
(0)
A
P
(0)
__
(1 C
(0)
A
)
_

(0)
B
+ RT ln
_
P
(0)
B
P
(0)
__
Inserting expressions for the partial pressures P
(0)
A
= C
A
P
(0)
and P
B
= C
B
P
(0)
,
(P
(0)
) = 2C
(0)
A
_

(0)
A
+
RT
2
ln
_
C
A
P
(0)
P
(0)
__
(1 C
(0)
A
)
_

(0)
B
+ RT ln
_
C
B
P
(0)
P
(0)
__
(10)
= 2C
(0)
A
_

(0)
A
+
RT
2
ln
_
C
A

P
(0)

P
(0)
__
(1 C
(0)
A
)
_

(0)
B
+ RT ln
_
(1 C
A
)

P
(0)

P
(0)
__
(P
(0)
) = 2C
(0)
A
_

(0)
A
+
RT
2
ln C
A
_
(1 C
(0)
A
)
_

(0)
B
+ RT ln(1 C
A
)
_
Given that the concentration C
A
1, the logarithm functions may be expanded.
Recalling the well-known expansion
1
1 x
=

n=0
x
n
Integration of the series term by term gives
ln(1 x) =

n=1
x
n
n
= x
x
2
2
. . . x
To rst order for the right-hand logarithm term. The left-hand logarithm is of the
form ln x, this series may be obtained from above with the replacement x x + 1.
ln(x) =

n=1
(1)
n+1
(x 1)
n
n
= (x 1)
(x 1)
2
2
. . . (x 1)
8
Inputting these approximations above, where x = C
A
, 1 C
A
admits
(P
(0)
) = 2C
(0)
A
_

(0)
A
+
RT
2
(C
A
1)
_
(1 C
(0)
A
)
_

(0)
B
+ RT(C
A
)
_
= 2C
(0)
A

(0)
A
+ RTC
A
(C
A
1)
. .
RT(C
(0)
A
)
2
RTC
(0)
A

(0)
B
+ RTC
(0)
A
+ C
(0)
A

(0)
B
RT(C
(0)
A
)
2
= 2C
(0)
A

(0)
A
+
$
$
$
$
$
$
RT(C
(0)
A
)
2

RTC
(0)
A

(0)
B
+

RTC
(0)
A
+ C
(0)
A

(0)
B

$
$
$
$
$
$
RT(C
(0)
A
)
2
= 2C
(0)
A

(0)
A

(0)
B
+ C
(0)
A

(0)
B

1
(P
(0)
) = 2C
(0)
A

(0)
A

(0)
B
(1 C
(0)
A
)

(0)
B
=
2C
(0)
A

(0)
A

1
1 C
(0)
A

(0)
B
2C
(0)
A

(0)
A

1
; C
(0)
A
1
where the notation
1
(P
(0)
) denotes state 1. In the nal step, the approximation
was invoked that C
(0)
A
1. While the chemical potential
1
is still unknown, some
manipulation is performed to facilitate as nal of a result as possible. When the
pressure is increased to state 2 at P = 2P
(0)
, the concentrations are C
A
and C
B
=
1C
A
. A second equation can be constructed from Eqn. (xxx) at a chemical potential
of
2
=
2
(2P
(0)
), where the partial pressures P
(0)
A
= 2C
A
P
(0)
and P
B
= 2C
B
P
(0)
=
2(1 C
A
)P
(0)
are inserted

2
= 2C
A
_

(0)
A
+
RT
2
ln
_
2C
A
P
(0)
P
(0)
__
(1 C
A
)
_

(0)
B
+ RT ln
_
2C
B
P
(0)
P
(0)
__
= 2C
A
_

(0)
A
+
RT
2
ln
_
2C
A

P
(0)

P
(0)
__
(1 C
A
)
_

(0)
B
+ RT ln
_
2(1 C
A
)

P
(0)

P
(0)
__

2
= 2C
A
_

(0)
A
+
RT
2
ln(2C
A
)
_
(1 C
A
)
_

(0)
B
+ RT ln[2(1 C
A
)]
_
In this scenario, no knowledge of smallness of either concentration is known, so the
terms must strictly be left in the logarithm arguments. However, motivated by the
smallness of C
(0)
A
, an enforcement of C
A
1 is made in order to furnish an analytical
result. As before, the logarithm terms may be represented as
ln(2C
A
) (2C
A
1) and ln[2(1 C
A
)] 2C
A
Putting these into the above equation yields
9

2
= 2C
A
_

(0)
A
+
RT
2
(2C
A
1)
_
(1 C
A
)
_

(0)
B
+ RT(2C
A
)
_
= 2C
A

(0)
A
+ RTC
A
(2C
A
1)
. .
RT(2C
2
A
RTC
A

(0)
B
+ 2RTC
A
+ C
A

(0)
B
2RTC
2
A
= 2C
A

(0)
A
+
$
$
$
$
$
2RT(C
2
A

$
$
$
$
RTC
A

(0)
B
+ 2
$
$
$
$
RTC
A
+ C
A

(0)
B

$
$
$
$$
2RTC
2
A
= 2C
A
(
(0)
A
+
(0)
B
) + C
A
RT

2
= C
A
[2(
(0)
A
+
(0)
B
) + RT]
C
A
=

2
2(
(0)
A
+
(0)
B
) + RT
Recalling, from above,
(0)
B
2C
(0)
A

(0)
A

1
, provides the nal form
C
A
=

2
2(
(0)
A
+ 2C
(0)
A

(0)
A

1
) + RT
(11)
4. (Huang 2.2)
A substance whose state is specied by P, V, T can exist in two distinct phases. At a
given temperature T the two phases can coexist if the pressure is P(T). The following
information is known about the two phases (1 and 2). At the temperatures and pressures
where they can coexist in equilibrium,
(i) there is no dierence in the specic volume of the two phases (v
1
= v
2
);
(ii) there is no dierence in the specic entropy of the two phases (s
1
= s
2
);
(iii) the specic heat c
P
and the volume expansion coecient are dierent for the
two phases (c
P
1 ,= c
P
2, and
1
,=
2
).
(a) Find dP(T)/dT as a function of T
The solution is motivated by result (2.12) of Huang, which gives the slope dP(T)/dT
in P-T space of the coexistence line between the two phases
dP(T)
dT
=
s
v
(12)
for the changes in states 1 and 2 in the specic entropy (s s
2
s
1
) and specic
volume (v v
2
v
1
). Given the information in the problem statement, criterion
(i) implies v = 0, while (ii) shows that s = 0. Thus Eqn. (xxx) admits an
indeterminate form
dP(T)
dT
=
0
0
10
In correspondence with the discussion in Huang on pages 34-35, the right hand
side of Eqn. (xxx) may be expressed in terms of chemical potentials g (Gibbs
energy per unit mass). This form may be developed from the denition of the
Gibbs energy G to obtain the dierential dG. The dierential may then be
modied by the division of the mass of the substance to give the dierential of
the chemical potential dg. Beginning with the Gibbs free energy G dened in
terms of the Helmholtz free energy F:
G = F + PV and F = E TS
where
P = Pressure
V = Volume
E = Internal energy
T = Temperature
S = Entropy
Using the denition of F in the Gibbs potential provides G = E TS + PV .
Dierentiating this expression
dG = dE TdS SdT + PdV + V dP
= (
$
$
$
TdS $
$
$
PdV )
$
$
$
TdS SdT +$
$
$
PdV + V dP
dG = SdT + V dP
dg = sdT + vdP (13)
where in the second step, the rst law (dE = TdS PdV ) was employed. The
nal step follows from division of the third line by the mass of the substance to
recast the dierential in terms of intensive quantities g, s, and v. For specicity,
this dierential may be rendered in terms of a dierence in intensive quanties
between states 1 and 2 by taking a dierence between the two states, giving
dg = sdT + vdP
This dierential furnishes the following two denitions,
_
g
T
_
P
= s and
_
g
P
_
T
= v
Given these relationships, Eqn. (xxx, dP/dT equation) may be translated in
terms of partial derivatives of the chemical potential
11
dP(T)
dT
=
s
v
=
0
0
=
(g/T)
P
(g/P)
T
x
y
=
_

2
g
T
2
_
P
_

T
_
P
_
g
P
_
T
(14)
The indeterminate form allowed an application of LHopitals rule in the nal
step with a partial dierentiation with respect to T at constant pressure P was
performed. The partial derivatives in terms x and y may be put in terms of
the specic heat c
P
and thermal expansion coecient , respectively, given in
the problem statement. Working on term x, a relation for the specic heat is
obtained from the TdS Eqn. (1.14)
TdS = C
p
dT T
_
V
T
_
P
dP
which, at constant pressure P, implies
TdS = C
p
dT T
_
V
T
_
P
dP
. .
dP=0

_
S
T
_
P
=
C
P
T
C
P
= T
_
S
T
_
P
c
P
= T
_
s
T
_
P
In the nal step, the equation was divided by the mass of the substance. Recalling
denition (xxx) (s = (g/T)
P
), the specic heat per mass is found to be given
in terms of the chemical potential g
c
P
= T
_
s
T
_
P
= T
_

T
_
P
_
g
T
_
P
c
P
= T
_

2
g
T
2
_
P

c
P
T
=
_

2
g
T
2
_
P
12
Considering two states 1 and 2, a dierence of the above equation provides

c
P
T
=
_

2
g
T
2
_
P
= x (15)
Which is identied as term x, the numerator in Eqn. (xxx). Term y (denomina-
tor) in Eqn. (xxx) may be recasted in terms of the thermal expansion coecient
using a similar procedure. Recalling that the thermal expansion coecient is de-
ned by = V
1
(V/T)
P
, and invoking the denition (xxx) for specic volume
v = (g/T)
P
, gives the desired form
=
1
V
_
V
T
_
P
=
1
v
_
v
T
_
P
=
1
v
_

T
_
P
_
g
P
_
T
v =
_

T
_
P
_
g
P
_
T
= y (16)
Such that an expression for the partial derivative y is obtained. Combining
results (xxx) and (yyy) gives into Eqn. (zzz) for the slope of the transition line
dP(T)/dT admits the nal result
dP(T)
dT
=
_

2
g
T
2
_
P
_

T
_
P
_
g
P
_
T
=
(c
p
/T)
v
dP(T)
dT
=
1
Tv
_
c
P

_
(17)
Which gives the mapping dP(T)/dT of the coexistence line in P T space of a
second order transition
(b) What is the qualitative shape of the transition region in the P V diagram? In
what way is it dierent from that of an ordinary gas-liquid transition?
Given that the specic volumes are the same for the substance in both phases, the
P V diagram diers from an ordinary rst-order transition from gas-liquid in that
there is no horizontal region at the transition volume. Instead, the P V trace exhibits
a discontinuity at this volume.
13
5 (Huang 2.4)
Show that the heat capacity at constant volume C
V
of a Van der Waals gas is a function
of the temperature alone.
The specic heat at constant volume C
V
is given by
C
V
=
_
U
T
_
V
(18)
where U, T, and V are the internal energy, temperature, and volume respectively. To
show that C
V
is a function of temperature alone, the internal energy must be shown
to be a function of only temperature and volume (U = U(T, V )) such that its partial
derivative with respect to T at constant V gives C
V
= C
V
(T) (as prescribed above).
A relation for U is obtained from the dQ equations, in which an intermediate result
quoted by Huang proves useful (Eqn. (1.12)):
_
U
V
_
T
= T
_
P
T
_
V
P
Recalling the equation of state for a Van der Waals gas
P(T, V ) =
RT
V b

a
V
2

_
P
T
_
V
=
R
V b
for the universal gas constant R, and Van der Waals constants a and b. The above
relation for the internal energy U may be partially integrated
_
U
V
_
T
= T
_
P
T
_
V
P
=

T
_
R
V b
_

RT
V b

a
V
2
_
_
U
V
_
T
= +
a
V
2
U =
a
V
2
+ U
0
(T) (19)
Where in the nal steps the integration has been performed, and an integration con-
stant U
0
(T) has been appended in accordance with the restriction on the internal
energys partial derivative (U/V )
T
. Inserting this result for U in Eqn. (xxx)
14
C
V
=
_
U
T
_
V
=

T
__

a
V
2
=0
+ U
0
(T)
__
V
C
V
=
_
U
0
(T)
T
_
V
implying,
C
V
=
_
U
0
(T)
T
_
V
= C
V
(T) (20)
which shows for a Van der Waals gas, the specic heat at constant volume is a function
of temperature alone.
6 (Huang 3.4)
Consider a mixture of two gases whose molecules have masses m and M, respectively,
and which are subjected to external forces

F and

Q, respectively. Denote the respec-
tive distribution functions by f and g. Assuming that only binary collisions between
molecules are important, derive the Boltzmann transport equation for this system.
The Boltzmann transport equation is found by considering a balance statement among
a system of two transport equations f(r, p, t) and g(r, p, t) at times t and t +t in the
presence of binary collisions, subject to respective forces

F and

Q,
f(r +vt, p +

Ft, t + t) = f(r, p, t) +
_
f
t
_
coll
t (21)
g(r +vt, p +

Qt, t + t) = g(r, p, t) +
_
g
t
_
coll
t (22)
where v represents velocity, and the collision operators are denoted by (f/t)
coll
and
(g/t)
coll
, which are physically representative of the net rate of particle transitions
belonging to the distribution functions f and g respectively in six-dimensional position
and momentum, (r, p), space. Expanding the left-hand sides of these equations to rst
order in t, and letting t 0 admits
_

t
+
p
m

r
+

F
p
_
f(r, p, t) =
_
f
t
_
coll
(23)
_

t
+
p
M

r
+

Q
p
_
g(r, p, t) =
_
g
t
_
coll
(24)
15
The notation
r
and
p
indicates the gradient operator with respect to r and p,
respectively. In order to derive explicit forms of the collision opeators, the binary
collisions between like-particles of mass m belonging to distribution f are examined as
per Huang (pgs. 60-62). Once a tractable form of the collision operator is obtained, the
remaining terms may be pieced together heuristically by analog. Before proceeding,
the collisional operators are split into two terms representing the dierent types of
binary collisions possible:
_
f
t
_
coll
= J
mm
(f) + J
mM
(f, g)
_
g
t
_
coll
= J
MM
(g) + J
Mm
(f, g)
The subscripts denote the types of collisions involved in each term, labeled by mass,
while the arguments indicate the distribution functions dependence. Combining these
two expressions for the collisional operators in Eqns. (xxx) and (yyy),
_

t
+
p
m

r
+

F
p
_
f(r, p, t) = J
mm
(f) + J
mM
(f, g) (25)
_

t
+
p
M

r
+

Q
p
_
g(r, p, t) = J
MM
(g) + J
Mm
(f, g) (26)
Further, in the notation of Huang, the collisional term J
mm
may be represented as a
net rate of generation,
J
mm
(f) = R

R
where R and

R are the number of collisions in a collision duration t in which one of
the initial and nal particles, respectively, is in d
3
rd
3
p about (r, p). An explicit form
for J
mm
(f) is obtained in order to inform how to piece together the remaining J terms.
The term J
mm
(f) is developed in Huang by considering transitions between two par-
ticles 1 and 2 to states 1

and 2

. Following this discussion, the rate of transitions

12 1

in a volume element d
3
r centered at r in a collision interval t is given by
dN
12
dP
121

2
t
for an initial number dN
12
of particle pairs colliding with momenta ( p
1
, p
2
). The proba-
bility of transition dP
121

2
is furnished by the transition matrix, T
fi
= 1

, 2

[T(E)[1, 2),
where T(E) is an operator that projects the scattering transition from initial (i) to nal
(f) states. The dierential rate is thus given by
16
dP
121

2
= d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2

4
(P
f
P
i
)
3
(

P

P

)(E E

)
The normalization factors (e.g. (2)
3
) multiplying each delta function and volume
element in d
3
p space is taken to be absorbed within the transition matrix T,

P and
E represent the total momenta and energies respectively, and the primed notation
denotes the nal states.
An explicit form for dN
12
is facilitated by introduction of the two-particle correlation
function F, dened by
dN
12
= F(r, p
1
, p
2
, t)d
3
rd
3
p
1
d
3
p
2
Owing to these denitions, it follows that the rates R and

R for particle 1 are given
by integrating the transition rate dN
12
dP
121

2
over all relative nal momenta p

1
, p

2
and initial momentum p
2
,
R =
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2
F(r, p
1
, p
2
, t)

R =
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
i
P
f
)[T
if
[
2
F(r, p
1
, p
2
, t)
Noting that for binary electromagnetic interactions, T
fi
= T
if
and the delta functions
are identical, the net generation rate J
mm
= R

R is obtained
J
mm
=
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2
(F
1

2
F
12
) (27)
with the shorthand F
1

2
= F(r, p
1
, p
2
, t). To obtain J
mm
in terms of the distribution
function f, an assumption of molecular chaos is employed, such that the probability
of nding any given particle is independent. The correlation function may then be
represented as
F(r, p
1
, p
2
, t) = f(r, p
1
, t)f(r, p
2
, t)
With this approximation, Eqn. (xxx) takes on its nal form
J
mm
(f) =
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2
(f
1
f
2
f
1
f
2
)
For the dened notation f
1
= f(r, p
1
, t), and similarly for the other terms. By analog,
the remaining collisional operators may now be assembled:
17
Sirajuddin, David Homework 3 Physics 715, Spring 2010
J
mM
(f) =
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2
(f
1
g
2
f
1
g
2
)
J
MM
(f) =
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2
(g
1
g
2
g
1
g
2
)
J
Mm
(f) =
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2
(g
1
f
2
g
1
f
2
)
Inputting these terms into Eqns. (xxx) and (yyy) provide a system of coupled Boltz-
mann equations
_

t
+
p
1
m

r
+

F
p
1
_
f(r, p
1
, t) =
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2
(f
1
f
2
f
1
f
2
)
+
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2
(f
1
g
2
f
1
g
2
)
and
_

t
+
p
1
M

r
+

Q
p
1
_
g(r, p
1
, t) =
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2
(g
1
g
2
g
1
g
2
)
+
_
d
3
p
2
d
3
p

1
d
3
p

4
(P
f
P
i
)[T
fi
[
2
(g
1
f
2
g
1
f
2
)
Where the collisionality between both species renders the equations simulataneous.
It is lastly noted that since J
mM
= J
Mm
, the collisional operators on the right-hand
sides of the above equations admit only three distinct terms. These operators may be
interpreted, or shown to be proportional to by direct integration over p

1
, as dierential
scattering cross sections between like-particles (m m, M M) and unlike-particles
(mM).
References
[1] Huang, Kerson Statistical Mechanics 1987. John Wiley & Sons, Inc. Canada.
[2] Ramsey-Musolf, Michael Physics 715 - Statistical Mechanics Class Notes, University of
Wisconsin - Madison. Spring 2010.
18