CH 3320

Physical Chemistry II

Solutions 1
Due 12:20 p.m. Mon. 9 Feb. 2015

Solution to Problem 1
Each of the stereocenters has 2 possibilities (right- or left-handed). There are 11 stereocenters,
so there are W = 211 total stereoisomers. Each occurs with equal likelihood, so the probability
of synthesizing the correct form by chance is
P =

1
( 0.049%)
211

Solution to Problem 2
Each of the 200 bonds can take on any one of the 3 conformations, for a total of
W = 3200 2.7 1095
total different conformations.
Solution to Problem 3
The number of ways that 10 indistinguishable objects can be arranged in 60 locations is


60!
60
= 75 394 027 566 7.5 1010
W =
=
10
10! 50!

Solution to Problem 4
The probability of obtaining n cis links after N reactions is given by the binomial distribution,


N
n N n
P (n) = pcis ptrans
,
n
if all of the reactions are independent. For the case of n = 40 and N = 100, we have


100
40
60
P (40) = 0.500 0.500
40
100!
= 0.500100
40! 60!
= 0.0108.
. There is only a 1.08% chance of having 40 cis bonds.

HW 1Solutions

CH 3320 | PChem II | Spring 2014 | Prof. S. J. Stuart

Page 1 of 9

Solution to Problem 5

a) The relative error in ln N ! is calculated using

=

(N ln N N ) ln N !
.
ln N !

Note that the order of the terms in the numerator is important if you want to get the
sign of the error correct. So, for various values of N we have:
(i)
5 ln 5 5 ln 5!
ln 5!
3.05 4.79
=
4.79
= 0.36
= 36%

|N =5 =

(ii)
|N =20 = 0.057 = 5.7%
(iii)
|N =100 = 0.0089 = 0.89%
b) The relative error in the more accurate approximation can be calculated using

(N ln N N + ln 2N ) ln N !
,
=
ln N !
so that, for various values of N ,
(i)
|N =5

5 ln 5 5 ln 5! + ln 25
=
ln 5!
4.771 4.79
=
4.785
= 0.0035
= 0.35%

(ii)
|N =20 = 9.8 105

HW 1Solutions

CH 3320 | PChem II | Spring 2014 | Prof. S. J. Stuart

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(iii)
|N =100 = 2.3 106
What you should observe from these isolated examples is that (1) the Stirling approximation
gets larger as N increases, decreasing to relative errors of less than 1% by the time your
calculator can not evaluate N !, and (2) including one extra term in the Stirling approximation
makes it considerably more accurate, by several orders of magnitude.
Solution to Problem 6
Using Stirlings Approximation,
ln 2015! 2015 ln 2015 2015
= 13316
(where the answer has been rounded to the appropriate number of significant digits, given the
typical accuracy of Stirlings Approximation). That means that
N ! = eln N !
= 10ln(N !)/ ln(10)
= 1013316/ ln(10)
= 105783 .
(Optionally, using the more accurate version of Stirlings Approximation,

ln N ! = N ln N N + ln 2N
would result in the more accurate answer 2015! 105785.06 = 1.06 105785 .)
Solution to Problem 7

a) When flipping 4N fair and independent coins, the probability of getting 2N heads is
 2N  2N 

1
1
1
4N !
4N
= 4N
.
P (2N ) =
2N
2
2
2 2N ! 2N !
Likewise, the probability of getting N heads is
 N  3N 

1
1
1 4N !
4N
P (N ) =
= 4N
.
N
2
2
2 N ! 3N !

HW 1Solutions

CH 3320 | PChem II | Spring 2014 | Prof. S. J. Stuart

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b) Solving for the ratio of these two quantities,

f=

P (N )
=
P (2N )

1
4N !
24N N ! 3N !
4N !
1
24N 2N ! 2N !

2N ! 2N !
.
N ! 3N !

Using Stirlings Approximation, we can write

ln f = 2N ln 2N 2N + 2N ln 2N 2N N ln N + N 3N ln 3N + 3N
= 4N ln 2N N ln N 3N ln 3N,
from which we can write
(2N )4N
N N (3N )3N
24N N 4N
=
N N 33N N 3N
24N
= 3N
3
= 24N 33N .

f =

c) We can show that f is a decreasing function of N by examining the derivative (for which
we will need to recall that d(ax )/dx = ax ln a),
df
dN

= 24N (ln 2)33N + 24N 33N ( ln 3)

= 24N 33N (ln 2 ln 3)
< 0

Because this derivative is always negative, the function f always decreases as N increases.
Thus the probability of getting N heads in 4N flips of a fair coin gets smaller, relative to
the probability of getting 2N heads, as N increases.

Solution to Problem 8
In a room with V = 100 m3 , T = 298 K and P = 1 atm, the number of molecules of an ideal
gas is
n =

PV
(1 atm) (100 m3 )
1000 L 6.022 1023

RT
m3
mol
0.08206 L atm mol1 K1 (298 K)

= 2 1027 .
a) The probability that only 0.3n of the molecules will be found in one half of the room is,
using the binomial distribution,


n
0.3n
0.7n
P (0.3n) = 0.5 0.5
0.3n
n!
= 0.5n
.
(0.3n)! (0.7n)!
HW 1Solutions

CH 3320 | PChem II | Spring 2014 | Prof. S. J. Stuart

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Using Stirlings Approximation gives

ln P (0.3n) = n ln 0.5 + n ln n n 0.3n ln 0.3n + 0.3n 0.7n ln 0.7n + 0.7n
= n ln 0.5 + n ln n 0.3n ln 0.3n 0.7n ln 0.7n.
Substituting n = 2 1027 gives
ln P (0.3n) = 2 1026 ,
so that
26

25

P (0.3n) = e210 = 10910 .

b) Similarly, the probability that exactly half of the molecules are in half of the room is
P (0.5n) = 0.5n

n!
(0.5n)! (0.5n)!

so that
0.5n (0.3n)!n!(0.7n)!
P (0.3n)
=
P (0.5n)
0.5n (0.5n)!n!(0.5n)!
=

(0.5n)! (0.5n)!
,
(0.3n)! (0.7n)!

the natural log of which can be written using Stirlings Approximation as



P (0.3n)
ln
= 0.5n ln 0.5n + 0.5n ln 0.5n 0.3n ln 0.3n 0.7n ln 0.7n
P (0.5n)
= n ln 0.5n 0.3n ln 0.3n 0.7n ln 0.7n.
Substituting n = 2 1027 gives

ln
so that

P (0.3n)
P (0.5n)

= 2 1026

P (0.3n)
26
25
= e210 = 10910
P (0.5n)

and, thankfully, the probability that 70% of the air will suddenly rush to the other side
of the room is vanishingly small.
c) If we repeat this problem with unequally divided portions of the room, so that a molecule
has a p = 0.0001 chance of being in the smaller volume, then the probability that a
fraction f of the n molecules is in this volume instead of the expected pn molecules is
P (f n) = pf n (1 p)(1f )n

HW 1Solutions

n!
.
(f n)! [(1 f )n]!

CH 3320 | PChem II | Spring 2014 | Prof. S. J. Stuart

Page 5 of 9

The ratio of this probability to the probability of the expected pn molecules in the smaller
volume is
n!
pf n (1 p)(1f )n (f n)! [(1f
P (f n)
)n]!
= pn
n!
P (pn)
p (1 p)(1p)n (pn)! [(1p)n]!
Using Stirlings Approximation we can write the natural log of this as
ln

P (f n)
=f n ln p + (1 f )n ln(1 p) + n ln n n f n ln f n + f n
P (pn)
(1 f )n ln(1 f )n + (1 f )n pn ln p (1 p)n ln(1 p) n ln n
+ n + pn ln pn pn + (1 p)n ln(1 p)n (1 p)n
=(f p)n ln p + (p f )n ln(1 p) f n ln f n (1 f )n ln(1 f )n
+ pn ln pn + (1 p)n ln(1 p)n

Substituting f = 0.0006, p = 0.001, and n = 2 1027 gives

ln
and

P (f n)
= 2 1023
P (pn)

P (f n)
23
23
= e210 = 10110
P (pn)

This is quite a bit larger than the probability that 70% of the air will leave a full half of
the room, but still ridiculously small.

Solution to Problem 9
There are few enough macrostates with Etot = 14 that we can enumerate them directly, and
calculate the multiplicity of each one:
n0
12
11
10
9
8
7
6
5

n1
0
2
4
6
8
10
12
14

n2
7
6
5
4
3
2
1
0

Etot
14
14
14
14
14
14
14
14

W =

21!
n0 !n1 !n2 !

50,388
2,116,296
11,639,628
19,399,380
12,471,030
3,325,608
352,716
11,628

The state with the highest multiplicity is the one with n0 = 9, n1 = 6, and n2 = 4.
Solution to Problem 10

HW 1Solutions

CH 3320 | PChem II | Spring 2014 | Prof. S. J. Stuart

Page 6 of 9

The entropy can be calculated from the probability distribution using

X
S = k
pi ln pi
i

= k (0.4161 ln 0.4161 + 0.0007 ln 0.0007 + 0.5832 ln 0.5832)

= 0.365k


= 0.365 1.38 1023 J/K
= 9.45 1024 J/K.

Solution to Problem 11

a)
P1
= e(E1 E0 )/kT
P0

J
kJ
1000 kJ
100.0 mol
= exp
8.3145 molJ K 298 K

!
= 2.96 1018

b)
J
kJ
1000 kJ
20.0 mol
P1
= e(E1 E0 )/kT = exp
P0
8.3145 molJ K 298 K

!
= 0.000312

c)
kJ
J
1.00 mol
1000 kJ
P1
= e(E1 E0 )/kT = exp
P0
8.3145 molJ K 298 K

!
= 0.668

Solution to Problem 12

a)
eEt /kT
eEt /kT + 2eEg /kT
1
=
(E
1 + 2e g Et )/kT
1

=
0.87 kcal
1000
mol
1 + 2 exp 8.3145
J

pt =

cal 4.184 J
kcal
cal

mol K

350 K

= 0.64

HW 1Solutions

CH 3320 | PChem II | Spring 2014 | Prof. S. J. Stuart

Page 7 of 9

b)
pt =
(Eg Et )/kT

pt + 2pt e

e(Eg Et )/kT =

Eg Et
=
kT
Eg Et =
=
=

1
2e(Eg Et )/kT

1+
1
1 pt
2pt
1 pt
ln
2pt
1 pt
kT ln
2pt
J
1 cal 1 kJ
1 0.559
8.3145
298 K ln
mol K 4.184 J 1000 J
2 0.559
kcal
0.551
mol

Solution to Problem 13

HW 1Solutions

CH 3320 | PChem II | Spring 2014 | Prof. S. J. Stuart

Page 8 of 9

The left hand side is

3 X
3 X
3
X

(xi xj xk ) = x1 x1 x1 + x1 x1 x2 + x1 x1 x3

i=1 j=1 k=1

+x1 x2 x1 + x1 x2 x2 + x1 x2 x3
+x1 x3 x1 + x1 x3 x2 + x1 x3 x3
+x2 x1 x1 + x2 x1 x2 + x2 x1 x3
+x2 x2 x1 + x2 x2 x2 + x2 x2 x3
+x2 x3 x1 + x2 x3 x2 + x2 x3 x3
+x3 x1 x1 + x3 x1 x2 + x3 x1 x3
+x3 x2 x1 + x3 x2 x2 + x3 x2 x3
+x3 x3 x1 + x3 x3 x2 + x3 x3 x3
= 111+112+113
+1 2 1 + 1 2 2 + 1 2 3
+1 3 1 + 1 3 2 + 1 3 3
+2 1 1 + 2 1 2 + 2 1 3
+2 2 1 + 2 2 2 + 2 2 3
+2 3 1 + 2 3 2 + 2 3 3
+3 1 1 + 3 1 2 + 3 1 3
+3 2 1 + 3 2 2 + 3 2 3
+3 3 1 + 3 3 2 + 3 3 3
= 1+2+3+2+4+6+3+6+9
+2 + 4 + 6 + 4 + 8 + 12 + 6 + 12 + 18
+3 + 6 + 9 + 6 + 12 + 18 + 9 + 18 + 27
= 216.
The right hand side is
3
X

!3
xi

= (x1 + x2 + x3 )3

i=1

= (1 + 2 + 3)3
= 63
= 216,
which is the same as the left side. This problem also illustrates nicely why we factored the
multiple sums into a product of single sums: it requires much less work to obtain the answer
that way.

HW 1Solutions

CH 3320 | PChem II | Spring 2014 | Prof. S. J. Stuart

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