Chem 120B Problem Set 1 Due: September 10, 2014

1. (i) Show that the mean square uctuation in any quantity A can be written in terms of its mean and
mean square values, (A)
2
= A
2
A
2
. (Here, as usual, the uctuation in A is dened as
A = AA.)
(ii) Generalize this result to the case of two different uctuation quantities, i.e., show that AB =
AB AB.
2. Consider a system of N molecules contained in a xed volume V . Imagine dividing this total volume
into a large number M of microscopic subvolumes v (so that M = V/v), and let n
i
be the number
of molecules within subvolume i. (This notional division does not prevent molecules from moving
among subvolumes; it is just a way to keep track of their spatial distribution.) As molecules move
within the container, the values of n
1
, n
2
, . . . , n
M
uctuate, while the total number
N =
M

i=1
n
i
remains constant.
What is the average number of molecules within a single subvolume, n
i
? Make your argument
carefully, using the fact that all subvolumes are statistically equivalent, i.e., they undergo the same set
of uctuations. Write your answer for n
i
in terms of v and the total density
0
= N/V .
3. The notation

3
i=1
x
i
is shorthand for a sum over the quantities x
1
, x
2
, and x
3
,
3

i=1
x
i
= x
1
+x
2
+x
3
.
(i) Write out the double summation
3

i=1
3

j=1
A
ij
explicitly in terms of the quantities A
11
, A
12
, etc.
(ii) Let S =

3
i=1
x
i
. Write the quantity S
2
in terms of x
1
, x
2
, and x
3
.
(iii) Now consider the case A
ij
= x
i
x
j
. Using your results from parts (i) and (ii), show that
3

i=1
3

j=1
A
ij
= S
2
,
and therefore that

i
x
i

2
=

j
x
i
x
j
.
(iv) Write out all terms in the sum

3
i=1
x
2
i
, and show that it is in general different from (

3
i=1
x
i
)
2
.
4. Consider a dilute solution with a total number N
tot
of solute molecules contained in a total volume
V
tot
. The total number density of solutes is thus
0
= N
tot
/V
tot
.
We will focus on a limited region of the solution, marked by a dashed line in the sketch below.
Chem 120B, Fall 2014 1
h
i
= 1
h
j
= 0
cell i,
cell j,
(Lattice cells and solute molecules not drawn to scale)
This observation region has a volume V . As solutes move across its boundary, the number N of solute
molecules inside the observation region uctuates about an average value N.
In order to examine uctuations in N, it is useful to imagine dividing the observation region into
microscopic cells of a cubic lattice, each with volume v. Let n
i
be the number of solute molecules in
cell number i in a given measurement. We will take the solution to be sufciently dilute that nding
two solutes in the same cell is negligibly unlikely. In other words, either n
i
= 0 or n
i
= 1. Assume
as well that uctuations in different cells are uncorrelated.
(i) Estimate the size of typical uctuations in N by calculating the root mean square deviation =

(N)
2
, where N = N N is the deviation of N from its average value. The correct answer
can be written solely in terms of N,
0
, and v. (Hint: Note that n
2
i
= n
i
.)
(ii) Show that (N)
2
= N in the limit of very low concentration,
0
v 1.
(iii) Calculate /N and comment on the size of uctuations in N relative to its mean when the
observation region is macroscopically large.
5. Consider the dilute solution of question 4 from a slightly different perspective: Any of the M cells
in the observation region should be occupied (n
i
= 1) with probability p
1
=
0
v. The probability
P(n
1
, n
2
, . . . , n
M
) of nding the system in a particular conguration of the observation volume (in
which the values of n
1
, n
2
, . . . , n
M
are all specied) is thus p
N
1
(1 p
1
)
MN
.
(i) Show and/or explain these two facts, p
1
=
0
v and P(n
1
, n
2
, . . . , n
M
) = p
N
1
(1 p
1
)
MN
.
(ii) Let W(N) be the number of congurations of the observation volume when N solutes are present.
Calculate the probability P(N) of observing a given value of N, in terms of p
1
, W(N), M, and N.
(iii) Later in the course, we will show that, when N and M are large,
ln W(N) M [ln + (1 ) ln(1 )] ,
where = N/M is the fraction of occupied cells. Using this fact, write ln P(N)/M solely in terms
of and p
1
.
(iv) Using a computer, plot your result for P(N) as a function of the fraction of occupied lattice cells,
. On a single graph, show results for p
1
= 0.1 and the cases M = 10, M = 100, M = 1, 000, and
M = 10, 000.
(v) Comment on the trends evident from your graph and your expectations for a macroscopic obser-
vation volume (with M 10
24
).
Chem 120B, Fall 2014 2