Homework 6

Duygu Can & Nese Aral 10 Dec 2010

homework 6 solutions

1.1 Problem 5.1

Question
A circular cylinder of radius R rotates about the long axis with angular velocity
. The cylinder contains an ideal gas of atoms of mass M at temperature .
Find an expression for the dependence of the concentration n(r) on the radial
distance r from the axis, in terms of n(0) on the axis. Take as for an ideal
gas.

Solution

The relation between the concentration of the particles and total chemical
energy of the system can be found by combining Eq. (5.12a) and Eq. (5.15) in
the book as follows:
= ext + int ,

where ext is the potential energy per particle in the external potential and
int is given by
 
n
int = ln , with nQ = (M /2h2 )3/2 .
nQ

The particles are under the centrifugal force F (r) = M 2 r, so their potential
energy can be calculated as
r r
M 2 r2
Z Z
V (r) = F (r0 )dr0 = M 2 r0 dr0 = .
0 0 2

Then the total chemical potential of the system becomes

M 2 r2
 
n(r)
= ln .
nQ 2

Solving this equation for n(r) we get

2 2
n(r) = nQ e/ eM r /2
.

Since the chemical potential is constant at a given temperature, the term

nQ e/ is also constant. So we can write
2 2
n(r) = n(0)eM r /2
.

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 Problem 5.6

1.2 Problem 5.6

Question
(a) Consider a system that may be unoccupied with energy zero or occupied
by one particle in either of two states, one of energy zero and one of energy .
Show that the Gibbs sum for this system is
= 1 + + exp(/ ) (1.1)
Our assumption excludes the possibility of one particle in each state at the
same time . Notice that we include in the sum a term for N = 0 as a particular
state of a system of a variable number of particles.
(b) Show that the thermal average occupancy of the system is
+ exp(/ )
<N > (1.2)

(c) Show that the thermal average occupancy of the state at energy is
< N () >= exp(/ )/ (1.3)

(d) Find an expression for the thermal average energy of the system
(e) Allow the possibility that the orbital at 0 and may be occupied by one
particle at the same time; show that
= 1 + + exp(/ ) + 2 exp(/ ) = (1 + )[1 + exp(/ )] (1.4)
Because can be factored as shown, we have in effect two independent systems.

Solution

(a) The Gibbs sum is given by Eq. (5.61) in the book as

X
= N es / .
ASN

In our system we have three different states for which occupancy and the cor-
responding energy values are (0,0), (1,0) and (1,). Inserting these values into
the Gibbs sum we get
= 1 + + e/ .

(b) Recalling Eq. (5.62) in the book, for the average number of particles we
can write

hN i = ln =

/
+ e
= .

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1. Homework 6 Solutions

(c) Total number of the particles in the system is

hN i = hN (n = 0)i + hN (n = )i.
Comparing this equation with the one found in part (b) we see that
/
hN ()i = e .

(d) Using Eq. (5.63) in the book, the internal energy can be calculated as
1 X
U = hi = s N es /

ASN
1 e/
= (0 + 0 + e/ ) =
Z
= hN ()i.

(e) We have to add a new state to the system having occupancy N=2 and
energy s =  + 0 = . The contribution to the Gibbs sum of this new state is
2 e/ , hence we get
new = + 2 e/ = 1 + + e/ + 2 e/
= (1 + )[1 + e/ ].

1.3 Problem 5.8

Question
In carbon monoxide poisoning the CO replaces the O2 adsorbed on
hemoglobin(Hb) molecules in the blood. To show the effect, consider a model
for which each adsorption site on a heme may be vacant or may be occupied
either with energy A by one molecule O2 or with energy B by one molecule
CO. Let N fixed heme sites be in equilibrium with O2 and CO in the gas
phases at concentrations such that the activities are (O2 ) = 1 105 and
(CO) = 1 107 , all at body temperature 37o C. Neglect any spin multiplic-
ity factors. (a)First consider the system in the absence of CO. Evaluate A
suc that 90 percent of Hb sites are occupied by O2 . Express the answer in eV
per O2 . (b) Now admit the CO under specified conditions. Find B such that
only 10 percent of Hb sites are occupied by O2 .

Solution

(a) In our model we have three different states with occupancy numbers and
corresponding anergy values as (1, A ), (1, B ) and (0,0), where (0,0) corre-
sponds to the vacant state. So the Gibbs sum for the system can be given

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 Problem 5.10

by X
= N e/ = 1 + A eA / + B eB / .
ASN

The fraction of sites occupied by O2 is fA = (A eA / )/. In the absence of

CO2 , B = 0 and the Gibbs sum reduces to

= 1 + A eA /

and we get
A eA /
fA = .
1 + A eA /
where A = 105 . Setting fA = 0.9 we can solve this equation for A . Here
= 0.0267eV , calculated for body temperature of 310 K. Hence we get

A = 0.366eV.

(b) In the presence of CO2 the fraction of sites occupied with O2 becomes

A eA /
fA = .
1 + A eA / + B eB /

We want that only 10% of the sites are occupied with O2 , so setting 0.1 for fA
and using the result of part (a), A = 0.366eV we can solve the last equation
for B , which gives
B = 0.55eV.

1.4 Problem 5.10

Question
The number of particles is not constant in a system in diffusive contact with a
reservoir. We have seen that
 

< N >= (1.5)
,V

from (59). (a) Show that

2 2
< N 2 >= (1.6)
2
The mean square deviation < (N )2 > of N from < N > is defined by

< (N )2 > = < (N < N >)2 >=< N 2 > < N >2 (1.7)
"  2 #
2
1 1
< (N )2 > = 2 2 (1.8)
2

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1. Homework 6 Solutions

(b) Show that this may be written as

< (N )2 >= < N > / (1.9)

In Chapter 6 we apply this result to the ideal gas to find that

< (N )2 > 1
2
= (1.10)
<N > N
is the mean square fractional fluctuation in the population of an ideal gas in
diffusive contact with a reservoir. If < N > is order of 1020 atoms, then the
fractional fluctuation is exceedingly small. In such a system the number of
particles is well defined even though it cannot be rigorously constant because
diffusive contact is allowed with the reservoir. When < N > is low, this
relation can be used in experimental determination of the molecular weight of
large molecules such as DNA of MW 108 101 0.

Solution

(a) Using Eq.(5.52) and (5.53) we can write

X 1 X 2 (N / ) 2 2 X (N )/ 2 2
hN 2 ii = N 2 P (N ) = N e = 2
e =
2
ASN ASN

(b) Using Eq. (5.80) we can write

2
2
   
hN i 1
= 2 = h(N )2 i,
2

where the last equality follows by comparison with Eq. (5.82).