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�is manual provides detailed solutions to the (b) Exercises and the even-numbered Discus-
sion questions and Problems from the ��th edition of Atkins’ Physical Chemistry.

We have included page-speci�c references to equations, sections, �gures and other features
of the main text. Equation references are denoted [��B.�b–���], meaning eqn ��B.�b located
on page ��� (the page number is given in italics). Other features are referred to by name,
with a page number also given.
Generally speaking, the values of physical constants (from the �rst page of the main text)
are used to � signi�cant �gures except in a few cases where higher precision is required.
In line with the practice in the main text, intermediate results are simply truncated (not
rounded) to three �gures, with such truncation indicated by an ellipsis, as in 0.123...; the
value is used in subsequent calculations to its full precision.
�e �nal results of calculations, generally to be found in a box , are given to the precision
warranted by the data provided. We have been rigorous in including units for all quantities
so that the units of the �nal result can be tracked carefully. �e relationships given on
the back of the front cover are useful in resolving the units of more complex expressions,
especially where electrical quantities are involved.
Some of the problems either require the use of mathematical so�ware or are much easier
with the aid of such a tool. In such cases we have used Mathematica (Wolfram Research,
Inc.) in preparing these solutions, but there are no doubt other options available. Some of
the Discussion questions relate directly to speci�c section of the main text in which case we
have simply given a reference rather than repeating the material from the text.

In preparing this manual we have drawn on the equivalent volume prepared for the ��th edi-
tion of Atkins’ Physical Chemistry by Charles Trapp, Marshall Cady, and Carmen Giunta. In
particular, the solutions which use quantum chemical calculations or molecular modelling
so�ware, and some of the solutions to the Discussion questions, have been quoted directly
from the solutions manual for the ��th edition, without signi�cant modi�cation. More
generally, we have bene�ted from the ability to refer to the earlier volume and acknowledge,
with thanks, the in�uence that its authors have had on the present work.
�is manual has been prepared by the authors using the LATEX typesetting system, in
the implementation provided by MiKTEX ( ); the vast majority of the �gures
and graphs have been generated using PGFPlots. We are grateful to the community who
maintain and develop these outstanding resources.
Finally, we are grateful to the editorial team at OUP, Jonathan Crowe and Roseanna
Levermore, for their invaluable support in bringing this project to a conclusion.
In such a complex undertaking some errors will no doubt have crept in, despite the authors’
best e�orts. Readers who identify any errors or omissions are invited to pass them on to us
by email to .
D�A.� �e partial pressure of gas J, p J , in a mixture of gases is given by [�A.�–�], p J =
x J p, where p is the total pressure and x J is the mole fraction of J.
If the gases are perfect, the partial pressure is also the pressure the gas would
exert if it occupied on its own the same container as the mixture at the same
temperature. �is leads to Dalton’s law, which is that the pressure of a mixture
of gases is the sum of the pressures that each one would exert if it occupied the
container alone.
Dalton’s law is a limiting law because it holds exactly only in the limit that there
are no interactions between the molecules, which for real gases will be in the
limit of zero pressure.

E�A.�(b) From inside the front cover the conversion between pressure units is: � atm ≡
101.325 kPa ≡ ��� Torr.
(i) A pressure of ��.� kPa is converted to atm as follows
1 atm
22.5 kPa × = �.��� atm
101.325 kPa
(ii) A pressure of ��� Torr is converted to Pa as follows
1 atm 101.325 kPa
770 Torr × × = 103 kPa = 1.03 × 105 Pa
760 Torr 1 atm

E�A.�(b) �e perfect gas law [�A.�–�], pV = nRT, is rearranged to give the pressure,
p = nRT�V . �e amount n is found by dividing the mass by the molar mass of
Ar, ��.�� g mol−1 .

��� � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � �
n

(25 g) �8.3145 × 10−2 dm3 bar K−1 mol−1 � × (303.15 K)

p=
(39.95 g mol−1 ) 1.5 dm3
= 10.4 bar

So no , the sample would not exert a pressure of �.� bar, but ��.� bar if it were
a perfect gas.
E�A.�(b) Because the temperature is constant (isothermal) Boyle’s law applies, pV =
const. �erefore the product pV is the same for the initial and �nal states

p f Vf = p i Vi hence p i = p f Vf �Vi

�e initial volume is �.�� dm3 greater than the �nal volume so Vi = 2.14+1.80 =
3.94 dm3 .

Vf 2.14 dm3
pi = × pf = × (1.97 bar) = 1.07 bar
Vi 3.94 dm3

(i) �e in initial pressure is �.�� bar

(ii) Because � atm is equivalent to �.����� bar and also to ��� Torr, the initial
pressure expressed in Torr is
1 atm 760 Torr
× × 1.07 bar = ��� Torr
1.01325 bar 1 atm

E�A.�(b) If the gas is assumed to be perfect, the equation of state is [�A.�–�], pV = nRT.
In this case the volume and amount (in moles) of the gas are constant, so it
follows that the pressure is proportional to the temperature: p ∝ T. �e ratio of
the �nal and initial pressures is therefore equal to the ratio of the temperatures:
p f �p i = Tf �Ti . Solving for the �nal pressure p f (remember to use absolute
temperatures) gives

Tf
pf = × pi
Ti
(11 + 273.15) K
= × (125 kPa) = ��� kPa
(23 + 273.15) K

E�A.�(b) �e perfect gas law pV = nRT is rearranged to give n = pV �RT.

pV
n=
RT
(1.00 × 1.01325 × 105 Pa) × (4.00 × 103 m3 )
= = 1.66... × 105 mol
(8.3145 J K−1 mol−1 ) × ([20 + 273.15] K)

where 1 J = 1 kg m2 s−2 and 1 Pa = 1 kg m−1 s−2 have been used.

�e molar mass of CH4 is 12.01 + 4 × 1.0079 = 16.0416 g mol−1 , so the mass of
CH4 is (1.66... × 105 mol) × (16.0416 g mol−1 ) = 2.67 × 106 g or 2.67 × 103 kg.

E�A.�(b) �e vapour is assumed to be a perfect gas, so the gas law pV = nRT applies. �e
task is to use this expression to relate the measured mass density to the molar
mass.
First, the amount n is expressed as the mass m divided by the molar mass M to
give pV = (m�M)RT; division of both sides by V gives p = (m�V )(RT�M).
 �e quantity (m�V ) is the mass density ρ, so p = ρRT�M, which rearranges
to M = ρRT�p; this is the required relationship between M and the density.
ρRT (0.6388 kg m−3 ) × (8.3145 J K−1 mol−1 ) × ([100 + 273.15] K)
M= =
p 16.0 × 103 Pa
= 0.123... kg mol−1

where 1 J = 1 kg m2 s−2 and 1 Pa = 1 kg m−1 s−2 have been used. �e molar mass
of P is 30.97 g mol−1 , so the number of P atoms in the molecules comprising
the vapour is (0.123... × 103 g mol−1 )�(30.97 g mol−1 ) = 4.00. �e result is
expected to be an integer, so the formula is likely to be P4 .

E�A.�(b) �e vapour is assumed to be a perfect gas, so the gas law pV = nRT applies; the
task is to use this expression to relate the measured data to the mass m. �is
is done by expressing the amount n as m�M, where M is the the molar mass.
With this substitution it follows that m = MPV �RT.
�e partial pressure of water vapour is 0.53 times the saturated vapour pressure
M pV
m=
RT
(18.0158 g mol−1 ) × (0.53 × 0.0281 × 105 Pa) × (250 m3 )
=
(8.3145 J K−1 mol−1 ) × ([23 + 273.15] K)
= 2.7 × 103 g = �.� kg

E�A.�(b) Once the total amount and the total pressure p tot are known, the volume is
found using the perfect gas law. �e total amount in moles of the mixture of
gases is
m CH4 m Ar m Ne
n tot = n CH4 + n Ar + n Ne = + +
M CH4 M Ar M Ne
0.320 g 0.175 g 0.225 g
= −1 + −1 +
(12.01 + 4 × 1.0079) g mol 39.95 g mol 20.18 g mol−1
= 3.54... × 10−2 mol
�e mole fraction of neon is
n Ne 0.225 g 1
x Ne = = × = 0.314...
n tot 20.18 g mol−1 3.54... × 10−2 mol
Because p Ne = x Ne × p tot it follow that
p Ne 8.87 kPa
p tot = = = ��.� kPa
x Ne 0.314...
�e volume is calculated using the perfect gas equation with the known total
pressure and total amount
nRT (3.54... × 10−2 mol) × (8.3145 J K−1 mol−1 ) × (300 K)
V= =
p 28.2 × 103 Pa
= 3.14 × 10−3 m3 = �.�� dm3
E�A.�(b) �e vapour is assumed to be a perfect gas, so the gas law pV = nRT applies.
�e task is to use this expression to relate the measured pressure and volume
of a known mass of gas to the molar mass.
�e amount n is expressed as the mass m divided by the molar mass M to
give pV = (m�M)RT; this rearranges to M = mRT�pV which is the required
relationship. �e pressure in Torr is converted to Pa by noting that ��� Torr is
equivalent to � atm.
mRT
M=
pV
(33.5 × 10−6 kg) × (8.3145 J K−1 mol−1 ) × (298 K)
=
(152 Torr�760 Torr) × (1.01325 × 105 Pa) × (250 × 10−6 m3 )
= �.���� kg mol−1

�e relationships 1 J = 1 kg m2 s−2 and 1 Pa = 1 kg m−1 s−2 have been used;

note the conversion of the volume to m3 .

E�A.��(b) �e idea here is that the volume will go to zero at absolute zero. �e data given
are the slope of the volume/temperature plot, together with one �xed point, so
the equation of the straight line can be found, and then the required intercept.
�e equation of the line is
(V �dm3 ) = (0.0741) × (θ�○ C) + (c�dm3 )
�e �xed point given is that the volume at θ = 0 ○ C is ��.�� dm3 , so the constant
c is equal to this volume
(V �dm3 ) = (0.0741) × (θ�○ C) + 20.00
�is is solved for V = 0 to give (θ�○ C) = (−20.00)�(0.0741) = −270, hence
θ = −270 ○ C . �is is the estimate of absolute zero.

E�A.��(b) (i) �e mole fractions are

n H2 1.5 mol
x H2 = = = 3
x N2 = 1 − x H2 = 5
n H2 + n N2 1.5 mol + 2.5 mol 8 8

(ii) �e partial pressures are given by p i = x i p tot . �e total pressure is given

by the perfect gas law: p tot = n tot RT�V

3 (4.0 mol) × (8.3145 J K−1 mol−1 ) × (273.15 K)

p H2 = x H2 p tot = ×
8 22.4 × 10−3 m3
= 1.5 × 10 Pa
5

5 (4.0 mol) × (8.3145 J K−1 mol−1 ) × (273.15 K)

p N2 = x N2 p tot = ×
8 22.4 × 10−3 m3
= 2.5 × 10 Pa
5

Expressed in atmospheres these are �.� atm and �.� atm, respectively.
 (iii) �e total pressure is

(3.0 mol) × (8.3145 J K−1 mol−1 ) × (273.15 K)

= 4.0 × 105 Pa
22.4 × 10−3 m3
or �.� atm.
Alternatively, note that � mol at STP occupies a volume of ��.� dm3 which is
the stated volume. As there are a total of �.� mol present the (total) pressure
must therefore be �.� atm.

P�A.� Perfect gas behaviour indicates that pV ∝ T, where T is the absolute tempera-
ture. In terms of the temperature θ in ○ N, T is written T = θ + θ 0 , where θ 0 is
the absolute temperature of zero on the ○ N scale. �e proportionality is made
an equality by inserting a constant

pV = α(θ + θ 0 )

�e two data points given are expressed as the following two equations:

28 = α(0 + θ 0 ) 40 = α(100 + θ 0 )

�ese are solved simultaneously to give θ 0 = 233 K. �is means that 0 ○ N

corresponds to an absolute temperature of ��� K. It follows that, on the ○ N
scale, absolute zero is −233 ○ N.

P�A.� At absolute zero the volume will go to zero so the temperature corresponding
to absolute zero θ 0 is found by solving

0 = V0 (1 + αθ 0 ) hence θ 0 = −1�α

�e quantity α varies with pressure, and what is required is its value in the
limit that the pressure goes to zero, because in this limit perfect gas behaviour
is achieved. A plot of α against pressure, Fig. �.�, reveals a gentle curve which
�ts well to a polynomial of order �.
�e equation of the �tted line is
−1
(103 α)�○ C = 4.5000 × 10−9 × (p�Torr)2 + 7.5870 × 10−6 × (p�Torr) + 3.6635

�e intercept at p = 0 gives the low pressure limit of α as 3.6635 × 10−3 ○ C−1 ,

and hence
−1
θ 0 = −1�α = −1�(3.6635 × 10−3 ○ C ) = −273.96 ○ C

P�A.� For a given setting of the pivot, the balance point is reached for a given density
of gas, because it is the density which a�ects the buoyancy of the bulb. �e
density of the gas depends on its pressure and its molar mass: the greater the
molar mass, the higher the density for a given pressure.
 3.67

3.67

(103 α)�○ C−1

3.67

3.67

3.66

0 200 400 600

p�Torr

�e exact relationship is derived for a perfect gas by starting with pV = nRT.

�e amount in moles is n = m�M, where M is the molar mass and m is the
mass of the gas. It follows that pV = (m�M)(RT) which rearranges to pM =
(m�V )(RT). �e quantity m�V is the mass density ρ, and hence pM = ρRT.
If the �rst gas has molar mass M 1 and balances the pivot at pressure p 1 , and
likewise M 2 and p 2 for the second gas, then because the densities must be the
same it follows that (at �xed temperature)
p2 M2
p1 M1 = p2 M2 hence M1 =
p1

For the �rst experiment

p 2 M 2 (423.22 Torr) × (70.014 g mol−1 )

M1 = = = 90.588 g mol−1
p1 (327.10 Torr)

For the second experiment

p 2 M 2 (427.22 Torr) × (70.014 g mol−1 )

M1 = = = 102.01 g mol−1
p1 (293.22 Torr)

If the gases are behaving ideally, the two experiments should give the same
molar mass – which evidently they do not. Because the lower pressure is closer
to ideality, the second experiment is perhaps to be preferred, but high precision
is not justi�ed in quoting the result for the molar mass as ��� g mol−1 .
�e compounds CH� FCF� and CHF� CHF� have molar masses close to this
value.

P�A.� �e stoichiometric equation for the production of NH� is � H� + N� ��→

� NH� . Conversion of all of the H� (� moles) to ammonia results in the forma-
tion of 43 mol of NH� and consumes 23 mol of N� . A�er the reaction is complete
 the amounts are therefore
2 1 4
n H2 = 0 n N2 = 1 − = mol n NH3 = mol
3 3 3
�e total amount is 13 + 43 = 5
3
mol, from which the total pressure is calculated
using the perfect gas law
−1
nRT ( 3 mol) × (8.3145 J K mol ) × (273.15 K)
5 −1
p= = = 1.69 × 105 Pa
V 22.4 × 10−3 m3
�e partial pressures are calculated from the mole fractions and the total pres-
sure
n N2 1�3 mol
p N2 = x N2 p = p= × (1.69... × 105 Pa) = 0.338 × 105 Pa
n tot 5�3 mol
n NH3 4�3 mol
p NH3 = x NH3 p = p= × (1.69... × 105 Pa) = 1.35 × 105 Pa
n tot 5�3 mol

P�A.�� It is useful to recall that at STP � mol occupies a volume of ��.��� dm3 .
A concentration of ��� DU means that when all of the ozone in a column of
cross-sectional area �.�� dm2 is compressed into a disc with the same cross-
sectional area and at STP the thickness of the disc is ���/���� cm. Expressed
in dm, the thickness is therefore 2.50 × 10−2 dm, and so the volume of the disc
is (thickness × area) = (2.50 × 10−2 dm) × (1.00 dm2 ) = 2.50 × 10−2 dm3 . �e
amount in moles of ozone is therefore
2.50 × 10−2 dm3
n O3 = = 1.11... × 10−3 mol = 1.12 × 10−3 mol
22.414 dm3 mol−1
�e amount in moles corresponding to ��� DU is found by using a ratio
100 100
n O3 ,100 DU = × n O3 ,250 DU = × (1.11... × 10−3 mol) = 4.46 × 10−3 mol
250 250

�e volume of a column of cross-sectional area �.�� dm2 and height (50−10) =

40 km is (1.00 × 10−2 m2 ) × (40 × 103 m) = 400 m3 . If the amount in moles in
this column is 1.11... × 10−3 mol (corresponding to ��� DU) the concentration
is
1.11... × 10−3 mol
c O3 = = 2.79 × 10−6 mol m−3
400 m3
or 2.79 × 10−9 mol dm−3 . Using a ratio as before, the concentration corre-
sponding to ��� DU is (100�250)×2.79×10−9 mol dm−3 = 1.12 × 10−9 mol dm−3 .

P�A.�� (a) From the perfect gas law pV = nRT, the amount in moles is calculated
using n = pV �RT; the volume of the balloon is (4�3)πr 3 .

pV (1.01325 × 105 Pa) × ( 43 π[3.0 m]3 )

n= =
RT (8.3145 J K−1 mol−1 ) × ([25 + 273.15] K)
= 4.62... × 103 mol = 4.6 × 103 mol
 (b) �e mass of the volume of air displaced by the balloon is
4
mass = volume×density = ( π[3.0 m]3 )×(1.22 kg m−3 ) = 1.37...×102 kg
3
�e mass of the hydrogen in the balloon is

mass = amount in moles × molar mass

= (4.62 . . . × 103 mol) × (2 × 1.0079 × 10−3 kg mol−1 ) = 9.31... kg

�e mass that can be li�ed (the payload) is the di�erence between the
displaced mass and the mass of the gas in the balloon (ignoring the mass
of the material making up the balloon itself)

payload = (1.37... × 102 kg) − (9.31... kg) = 1.3 × 102 kg

(c) If the gas is helium, the mass of the gas in the balloon is

(4.62 . . . × 103 mol) × (4.00 × 10−3 kg mol−1 ) = 1.84... × 101 kg

and the payload is

payload = (1.37... × 102 kg) − (1.84... × 101 kg) = 1.2 × 102 kg

P�A.�� To solve this problem it is necessary to assume that the partial pressure of each
gas obeys a barometric formula in which the constant H depends on the iden-
tity of the gas

RT
p N2 = p 0,N2 exp(−h�H N2 ) H N2 =
M N2 g

and likewise for O� . �e mole fractions of the two gases at sea level, and hence
their partial pressures, are found from the mass composition at this level. Like-
wise, the mole fractions and partial pressures are found at the higher altitude
from the stated mass composition.
Imagine ���� g of atmosphere: at sea level this contains ��� g of N� and ��� g
of O� . �e mole fractions are

(800 g)�(2 × 14.01 g mol−1 )

x N2 = = 0.820
(800 g)�(2 × 14.01 g mol−1 ) + (200 g)�(2 × 16.00 g mol−1 )
Hence x O2 = 1 − x N2 = 0.180.
At the higher altitude the same mass of atmosphere contains ��� g of N� and
��� g of O� . �e mole fractions are

(900 g)�(2 × 14.01 g mol−1 )

x N′ 2 = = 0.911
(900 g)�(2 × 14.01 g mol−1 ) + (100 g)�(2 × 16.00 g mol−1 )

Hence x O′ 2 = 1 − x N′ 2 = 0.089.
At altitude h the partial pressures of the two gases are
p N2 = p 0,N2 exp(−h�H N2 ) p O2 = p 0,O2 exp(−h�H O2 )
Taking the ratio of these two equations gives
p N2 p 0,N2
= exp(−h�H N2 + h�H O2 )
p O2 p 0,O2
�e ratio of the partial pressures is the same as the ratio of the mole fractions
x N′ 2 x N2
= exp(−h�H N2 + h�H O2 )
x O′ 2 x O2
where x N2 is the mole fraction at h = 0. �is equation is rearranged to �nd h
x N′ 2 x O2
= exp(−h�H N2 + h�H O2 )
x O′ 2 x N2
x N′ 2 x O2 h h
ln � ′
�=− +
x O2 x N2 H N2 H O2
x N′ 2 x O2 hM N2 g hM O2 g
ln � �=− +
x O′ 2 x N2 RT RT
RT x N′ x O
ln � ′ 2 2 � = h
g(M O2 − M N2 ) x O2 x N2

Inserting the data gives

RT x N′ x O
h= ln � ′ 2 2 �
g(M O2 − M N2 ) x O2 x N2
(8.3145 J K−1 mol−1 )([25 + 273.15] K)
=
(9.807 m s−2 ) × [(2 × 16.00 × 10−3 kg mol−1 ) − (2 × 14.01 × 10−3 kg mol−1 )]
0.911 0.180
× ln � �
0.0890 0.820
= 51.4... km = 51 km
At this height the total pressure is found by summing the partial pressures at
this height. �e partial pressure at sea level is given by p 0,N2 = x N2 p 0 , so it
follows that
p N2 = x N2 p 0 exp(−h�H N2 ) p O2 = x O2 p 0 exp(−h�H O2 )
It is convenient to compute the scale heights H separately
RT (8.3145 J K−1 mol−1 )([25 + 273.15] K)
H N2 = =
M N2 g (2 × 14.01 × 10−3 kg mol−1 ) × (9.807 m s−2 )
= 9.02... × 103 m
RT (8.3145 J K−1 mol−1 )([25 + 273.15] K)
H O2 = =
M O2 g (2 × 16.00 × 10−3 kg mol−1 ) × (9.807 m s−2 )
= 7.90... × 103 m
 �e total pressure at height h is therefore
p = x N2 p 0 exp(−h�H N2 ) + x O2 p 0 exp(−h�H O2 )
51.4... × 103 m
= (0.820 × 1 atm) exp �− �
9.02... × 103 m
51.4... × 103 m
+ (0.180 × 1 atm) exp �− �
7.90... × 103 m
= 0.0030 atm
�e calculation is incomplete as it assumes that composition is a�ected only
by the mass and ignores the entropically driven mixing of gases. In fact, the
composition of the atmosphere remains pretty much constant up to ��� km.

D�B.� �e mean free path is given by [�B.��–��], λ = kT�σ p. In a container of con-

stant volume, the mean free path is directly proportional to temperature and
inversely proportional to pressure. �e former dependence can be rationalized
by noting that the faster the molecules travel, the farther on average they go
between collisions. �e latter also makes sense in that the lower the pressure,
the less frequent are collisions, and therefore the further the average distance
between collisions.
Perhaps more fundamental than either of these considerations is the depen-
dence on the size of the container and on the size of the molecules. �e ratio
T�p is directly proportional to volume for a perfect gas, so the average distance
between collisions is directly proportional to the size of the container holding a
given number of gas molecules. Finally, the mean free path is inversely propor-
tional to the size of the molecules as given by the collision cross section (and
therefore inversely proportional to the square of the radius of the molecule).

� mean speed is given by [�B.�–��], υ mean = (8RT�πM) , so υ mean ∝

1�2
E�B.�(b) (i) �e
1�M. �e ratio of the mean speeds therefore depends on the ratio of
the molar masses

200.59 g mol−1
1�2
υ mean,He M Hg 1�2
=� � =� � = �.��
υ mean,Hg M He 4.00 g mol−1

(ii) �e mean translational kinetic energy �E k � is given by 12 m�υ 2 �, where

�υ 2 � is the mean square speed, which is given by [�B.�–��], �υ 2 � = 3RT�M.
�e mean translational kinetic energy is therefore
1 1 3RT
�E k � = m�v 2 � = m � �
2 2 M
 �e molar mass M is related to the mass m of one molecule by M = mN A ,
where N A is Avogadro’s constant, and the gas constant can be written R =
kN A , hence
1 3RT 1 3kN A T 3
�E k � = m � � = m� � = kT
2 M 2 mN A 2
�e mean translational kinetic energy is therefore independent of the
identity of the gas, and only depends on the temperature: it is the same
for He and Hg.
�is result is related to the principle of equipartition of energy: a molecule
has three translational degrees of freedom (x, y, and z) each of which
contributes 12 kT to the average energy.

E�B.�(b) �e rms speed is given by [�B.�–��], υ rms = (3RT�M)1�2 ; M CO2 = 44.01 g mol−1 .

3 × (8.3145 J K−1 mol−1 ) × (293.15 K)

1�2 1�2
3RT
υ rms,CO2 = � � =� �
M CO2 44.01 × 10−3 kg mol−1
= 408 m s−1

where 1 J = 1 kg m2 s−2 has been used. Note that the molar mass is in kg mol−1 .

3 × (8.3145 J K−1 mol−1 ) × (293.15 K)

1�2
υ rms,He =� � = 1.35 km s−1
4.00 × 10−3 kg mol−1

E�B.�(b) �e Maxwell–Boltzmann distribution of speeds, f (υ), is given by [�B.�–��].

�e fraction of molecules with speeds between υ 1 and υ 2 is given by the integral
υ2
� f (υ) dυ
υ1

If the range υ 2 − υ 1 = δυ is small, the integral is well-approximated by

f (υ mid ) δυ
where υ mid is the mid-point of the velocity range: υ mid = 12 (υ 2 + υ 1 ). In this
exercise υ mid = 402.5 m s−1 and δυ = 5 m s−1 . M CO2 = 12.01 + 2 × 16.00 =
44.01 g mol−1 .

M 3�2 2 −Mυ 2mid

fraction = f (υ mid ) δυ = 4π × � � υ mid exp � � δυ
2πRT 2RT
44.01 × 10−3 kg mol−1
3�2
= 4π × � � × (402.5 m s−1 )2
2π × (8.3145 J K−1 mol−1 ) × (400 K)
−(44.01 × 10−3 kg mol−1 ) × (402.5 m s−1 )2
× exp � � × (5 m s−1 )
2 × (8.3145 J K−1 mol−1 ) × (400 K)
= �.����

where 1 J = 1 kg m2 s−2 has been used. �us, �.��% of molecules have velocities
in this range.
E�B.�(b) �e mean relative speed is given by [�B.��b–��], υ rel = (8kT�πµ)1�2 , where
µ = m A m B �(m A + m A ) is the e�ective mass. Multiplying top and bottom of
the expression for υ rel by N A and using N A k = R gives υ rel = (8RT�πN A µ)1�2
in which N A µ is the molar e�ective mass. For the relative motion of N� and O�
this e�ective mass is

M N2 M O2 (2 × 14.01 g mol−1 ) × (2 × 16.00 g mol−1 )

NA µ = = = 14.9... g mol−1
M N2 + M O2 (2 × 14.01 g mol−1 ) + (2 × 16.00 g mol−1 )

8 × (8.3145 J K−1 mol−1 ) × (298.15 K)

1�2 1�2
8RT
υ rel = � � =� � = 650 m s−1
πN A µ π × (14.9... × 10−3 kg mol−1 )

E�B.�(b) �e most probable speed is given by [�B.��–��], υ mp = (2RT�M)1�2 , the mean

speed is given by [�B.�–��], υ mean = (8RT�πM)1�2 , and the mean relative
√
speed between two molecules of the same mass is given by [�B.��a–��], υ rel =
2υ mean . M H2 = 2 × 1.0079 = 2.0158 g mol−1 .

2 × (8.3145 J K−1 mol−1 ) × (293.15 K)

1�2
2RT 1�2
υ mp =� � =� �
M 2.0158 × 10−3 kg mol−1
= 1.56 × 103 m s−1
8 × (8.3145 J K−1 mol−1 ) × (293.15 K)
1�2
8RT 1�2
υ mean =� � =� �
πM π × (2.0158 × 10−3 kg mol−1 )
= 1.75 × 103 m s−1
√ √
υ rel = 2υ mean = 2 × (1.75 × 103 m s−1 ) = 2.48 × 103 m s−1

E�B.�(b) �e collision frequency is given by [�B.��b–��], z = σ υ rel p�kT, with the

√ relative
speed for two molecules of the same type given by [�B.��a–��], υ rel = 2υ mean .
�e mean speed is given by [�B.�–��], υ mean = (8RT�πM)1�2 . From the Re-
source section the collision cross-section σ is �.�� nm2 .

σ υ rel p σ p √ 8RT 1�2

z= = × 2×� �
kT kT πM
(0.40 × 10−18 m2 ) × (1.01325 × 105 Pa) √
= × 2
(1.3806 × 10−23 J K−1 ) × (298.15 K)
8 × (8.3145 J K−1 mol−1 ) × (298.15 K)
1�2
� �
π × (2 × 16.00 × 10−3 kg mol−1 )
= 6.2 × 109 s−1

where 1 J = 1 kg m2 s−2 and 1 Pa = 1 kg m−1 s−2 have been used. Note the
conversion of the collision cross-section σ to m2 : � nm2 = (1 × 10−9 )2 m2 =
1 × 10−18 m2 .
E�B.�(b) From inside the front cover ��� Torr is equilvant to � atm, which is 1.01325 ×
105 Pa. �erefore a pressure of � nTorr is expressed in Pa as

1 atm 1.01325 × 105 Pa

1 nTorr = (1 × 10−9 Torr) × × = 1.33... × 10−7 Pa
760 Torr 1 atm

�e mean speed is given by [�B.�–��], υ mean = (8RT�πM)1�2 . �e collision

frequency is given by [�B.��b–��], z = σ υ rel p�kT, with the
√ relative speed for
two molecules of the same type given by [�B.��a–��], υ rel = 2υ mean . �e mean
free path is given by [�B.��–��], λ = kT�σ p

(i) �e mean speed is calculated as

8 × (8.3145 J K−1 mol−1 ) × (298.15 K)

1�2
8RT 1�2
υ mean = � � =� � = 475 m s−1
πM π × (2 × 14.01 × 10−3 kg mol−1 )

(ii) �e collision cross-section σ is calculated from the collision diameter d

as σ = πd 2 = π × (395 × 10−9 m)2 = 4.90... × 10−19 m2 . With this value
the mean free path is calculated as

kT (1.3806 × 10−23 J K−1 ) × (298.15 K)

λ= = = 6.30 × 104 m
σ p (4.90... × 10−19 m2 ) × (1.33... × 10−7 Pa)

where 1 J = 1 kg m2 s−2 and 1 Pa = 1 kg m−1 s−2 have been used. �e mean

free path is �� km, a distance very much greater than the dimensions of
the apparatus.
(iii) �e collision rate is calculated as

σ υ rel p σ p √ 8RT 1�2

z= = × 2×� �
kT kT πM
(4.90 × 10−19 m2 ) × (1.33... × 10−7 Pa) √
= × 2
(1.3806 × 10−23 J K−1 ) × (298.15 K)
8 × (8.3145 J K−1 mol−1 ) × (298.15 K)
1�2
� �
π × (2 × 14.01 × 10−3 kg mol−1 )
= 1.07 × 10−2 s−1

An alternative for the calculation of z is to use [�B.��–��], λ = υ rel �z,

rearranged to z = υ rel �λ
√ √
υ rel 2υ mean 2 × (475 m s−1 )
z= = = = 1.07 × 10−2 s−1
λ λ 6.30 × 104 m
As expected for such a low pressure, collisions are very infrequent, occur-
ing about once every ��� s.
E�B.�(b) collision cross section σ is written in terms of a diameter as σ = πd 2 , hence
�e �
d = σ�π
� �
d = σ�π = (0.36 × 10−18 m2 )�π = 3.38... × 10−10 m

�e mean free path is given by [�B.��–��], λ = kT�σ p. �is is rearranged to

give the pressure p with λ equal to �� times the estimate for the diameter of the
atoms
kT (1.3806 × 10−23 J K−1 ) × (298.15 K)
p= = = 3.4 × 106 Pa
σ(10d) (0.36 × 10−18 m2 ) × 10 × (3.38... × 10−10 m)

E�B.�(b) �e mean free path is given by [�B.��–��], λ = kT�σ p.

kT (1.3806 × 10−23 J K−1 ) × (217 K)

λ= = = 5.8 × 10−7 m = �.�� µm
σ p (0.43 × 10−18 m2 ) × (12.1 × 103 Pa)

P�B.� �e Maxwell–Boltzmann distribution of speeds in one dimension (here x) is

given by [�B.�–��]
m 1�2 −mυ 2x �2k T
f (υ x ) = � � e
2πkT
An analogous expression gives the distribution in the y direction, f (υ y ). �e
probability of �nding a particle with velocity between υ x and υ x + dυ x is given
by f (υ x ) dυ x , and similarly in the y direction. �e overall probability of �nding
a particle with velocity between υ x and υ x + dυ x , and between υ y and υ y + dυ y ,
is therefore
m 1�2 −mυ 2x �2k T m 1�2 −mυ 2y �2k T
�� � e � �� � e � dυ x dυ y
2πkT 2πkT
m
=� � e−m(υ x +υ y )�2k T dυ x dυ y
2 2

2πkT
m
=� � e−mυ �2k T dυ x dυ y
2

2πkT
��� � � � � � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � � � � � � ��
A

On the last line the speed υ, given by υ 2 = υ 2x + υ 2y , is introduced.

As discussed in Section �B.�(b) on page ��, the ‘area element’ dυ x dυ y can be
interpreted by imagining a velocity space with axes labelled (υ x , υ y ). In this
space, particles with speed υ lie on a circle of radius υ, so particles with speeds
between υ and υ + dυ lie in a ring of radius υ and thickness dυ. Because the
ring is very thin, its area is given by the circumference of the circle times the
width: 2πυ dυ.
�e total probability of a particle having speed υ and υ+dυ, f (υ)dυ, is therefore
found by multiplying the term A in the above expression, not by the area ele-
ment dυ x dυ y but by the area of the ring because this gives the total probability
 of having this range of speeds, regardless of direction
m
f (υ) dυ = � � e−mυ �2k T 2πυ dυ
2

2πkT
�e distribution of speeds in two dimension is therefore
m
f (υ) dυ = � � υe−mυ �2k T
2

kT
∞
�e average speed is found using [�B.�–��], �υ n � = ∫0 υ n f (υ) dυ. In this case
∞ m ∞ m
�υ� = � υ� � υe−mυ �2k T dυ = � υ 2 � � e−mυ �2k T dυ
2 2

0 kT 0 kT
�e required integral is of the form of G.� from the Resource section
∞ 1 π 1�2
� x 2 e−ax dx = � �
2

0 4 a3
With a = m�2kT the mean speed is
1�2
1 m π πkT 1�2
�υ� = � � � � = � �
4 kT (m�2kT)3 2m

P�B.� �e Maxwell–Boltzmann distribution of speeds in three dimensions is given

by [�B.�–��]
M 3�2 2 −M υ 2 �2RT
f (υ) = 4π � � υ e
2πRT
with M the molar mass. �e root mean square speed is given by [�B.�–��],
υrms = (3RT�M)1�2 , and mean speed is given by [�B.�–��], υmean = (8RT�πM)1�2 .
�e required proportions are found by integrating f (υ) between the relevant
limits for υ.
(a) �e fraction having speed greater than υrms is given by
∞
� f (υ) dυ
υ rms
�
Mathematical so�ware is used to evaluate the integral to give 6�π e3�2 +
�
erfc( 3�2), where erfc(x) is the complementary error function, erfc(x) =
1 − erf(x). �e result is evaluated numerically to give �.���, that is ��%
of molecules have speeds greater than the root mean square speed.
(b) �e remaining fraction, 1 − 0.391 = 0.608, have speeds smaller than υrms .
�us ��% of molecules have speeds smaller than the root mean square
speed.
√ limit υmean . Mathematical so�ware
(c) �e integral is as in (a), but with lower
gives the result 4�πe−4�π +erfc(2� π). �e result is evaluated numerically
to give �.���, that is ��% of molecules have speeds greater than the mean
speed, and so ��% of molecules have speeds smaller than the mean speed.
P�B.� �e Maxwell–Boltzmann distribution of speeds in three dimensions is given
by [�B.�–��]
M 3�2 2 −M υ 2 �2RT
f (υ) = 4π � � υ e
2πRT

with M the molar mass. �e mean of υ n is found using [�B.�–��], �υ n � =

∞ n
∫0 υ f (υ) dυ. �e required integral is therefore

∞ M 3�2 ∞ n+2 −M υ 2 �2RT

�υ n � = � υ n f (υ) dυ = 4π � � � υ e dυ
0 2πRT 0

For the case where n + 2 is odd, integral G.� from the Resource section is used

∞ m!
� x 2m+1 e−ax dx = m = 1, 2, 3, . . .
2

0 2a m+1

�e relationship between m and n is found by noting that for n = 1, 3, 5, . . .,

m will be 1, 2, 3, . . . (note that these generate only the odd values of n + 2). It
therefore follows that m = 12 (n + 1) and m + 1 = 12 (n + 3). �ese substitutions,
along with a = M�2RT allow the integral to be evaluated.

M 3�2 ∞ n+2 −M υ 2 �2RT

�υ n � = 4π � � � υ e dυ
2πRT 0

M 3�2 1 [ 2 (n + 1)]!
1
= 4π � �
2πRT 2 (M�2RT) 12 (n+3)
1 3�2 M 3�2 M − 2 (n+3) 1
1

= 2π � � � � � � [ 2 (n + 1)]!
π 2RT 2RT
1
1 1�2 2RT 2 n 1
= 2� � � � [ 2 (n + 1)]! odd n
π M

Hence
1
21�n 2RT 2 1
�υ n �1�n = � � �[ 2 (n + 1)]!�
1�n
odd n
π 1�2n M

For the case where n + 2 is even, integral G.� from the Resource section is used

∞ (2m − 1)!! π 1�2

� x 2m e−ax dx = � � m = 1, 2, 3, . . .
2

0 2m+1 a m a

where (2m − 1)!! = (2m − 1) × (2m − 3) × (2m − 5) × . . . 1 or 2.

�e relationship between m and n is found by noting that for n = 2, 4, 6, . . .,
m will be 2, 3, 4, . . . (note that these generate only the even values of n + 2). It
therefore follows that m = 12 (n + 2), m + 1 = 12 (n + 4) and (2m − 1) = (n + 1).
�ese substitutions, along with a = M�2RT allow the integral to be evaluated.
M 3�2 ∞ n+2 −M υ 2 �2RT
�υ n � = 4π � � � υ e dυ
2πRT 0

M 3�2 (2m − 1)!! π 1�2

= 4π � � � �
2πRT 2m+1 a m a
(n + 1)!!
1�2
M 3�2 π
= 4π � � � �
2πRT 1
22 (n+4)
(M�2RT) 2
1
(n+2) (M�2RT)
1 n�2 M 3�2 M − 2 (n+2) M −1�2
1

=� � � � � � � � (n + 1)!!
2 2RT 2RT 2RT
1 n�2 2RT n�2
=� � � � (n + 1)!!
2 M
RT n�2
=� � (n + 1)!! even n
M
Hence
RT 1�2
�υ n �1�n = � � [(n + 1)!!]
1�n
even n
M
Mathematical so�ware gives a solution for both even and odd n
∞ M 3�2 ∞ n+2 −M υ 2 �2RT
�υ n � = � υ n f (υ) dυ = 4π � � � υ e dυ
0 2πRT 0

1 RT n�2 1
= √ 2(n+2)�2 � � Γ( 2 [n + 3])
π M
where Γ(x) is the Euler gamma function.
If the argument x is an integer then Γ(x) = (x − 1)!. �is will be the case for
odd n, in which case
1 RT n�2 1
�υ n � = √ 2(n+2)�2 � � ( 2 [n + 1])! odd n
π M
which is the same result as found above.
1
If the argument of the Gamma function is an odd multiple of (that is 12 m,
with m = 1, 3, 5, . . .) then
2

√
(m − 2)!! π
Γ( 2 m) =
1
2(m−1)�2
�is will be the case for even n, in which case
√
1 (n+2)�2 RT n�2 (n + 3 − 2)!! π
�υ � = √ 2
n
� �
π M 2(n+3−1)�2
√
1 RT n�2
(n + 1)!! π
= √ 2(n+2)�2 � �
π M 2(n+2)�2
RT n�2
=�
� (n + 1)!! even n
M
which again is the same result as above.
P�B.� �e Maxwell–Boltzmann distribution of speeds in three dimensions is given
by [�B.�–��]
M 3�2 2 −M υ 2 �2RT
f (υ) = 4π � � υ e
2πRT
with M the molar mass, here taken to be �.� kg mol−1 . Plots of f (υ) are shown
in Fig. �.�.

0.005
T = 200 K
T = 400 K
0.004 T = 800 K
T = 1200 K
T = 1600 K
0.003 T = 2000 K
f (υ)

0.002

0.001

0.000
0 200 400 600 800 1 000
−1
υ�m s

P�B.�� �e Maxwell–Boltzmann distribution of speeds in three dimensions is given

by [�B.�–��]
M 3�2 2 −Mυ 2 �2RT
f (υ) = 4π � � υ e
2πRT
�e speed at which this function is a maximum is found by setting the deriva-
tive d f (υ)�dυ equal to zero. �e derivative is found using the product rule and
the chain rule

d f (υ) M 3�2 −2Mυ −M υ 2 �2RT

= 4π � � �2υe−Mυ �2RT + υ 2 � �e �
2

dυ 2πRT 2RT

�e derivative is set to zero and factors of e−M υ �2RT

2
and υ are identi�ed to give

M 3�2 −Mυ 2 �2RT M

4π � � ×e × υ × �2 − υ 2 � �� = 0
2πRT RT

�e solution when υ = 0 is not a maximum, and the solution e−M υ �2RT = 0

2

corresponds to the asymptotic behave at large speeds. �is leaves the maximum
 to be given by

M 2RT 1�2
2 − υ 2max � �=0 hence υ max = � �
RT M
�at this is a maximum can be veri�ed by inspecting a plot of f (υ).

D�C.� �e critical constants represent the state of a system at which the distinction
between the liquid and vapour phases disappears. �is situation is usually
described by saying that above the critical temperature the liquid phase cannot
be produced by the application of pressure alone. �e liquid and vapour phases
can no longer coexist, though supercritical �uids have both liquid and vapour
characteristics.

D�C.� �e van der Waals equation is a cubic equation in the volume V . Every cubic
equation has some values of the coe�cients for which the number of real roots
passes from three to one. In fact, any equation of state of odd degree n > 1 can
in principle account for critical behavior because for equations of odd degree
in V there are necessarily some values of temperature and pressure for which
the number of real roots of V passes from n to �. �at is, the multiple values of
V converge from n to � as the temperature approaches the critical temperature.
�is mathematical result is consistent with passing from a two phase region
(more than one volume for a given T and p) to a one phase region (only one V
for a given T and p), and this corresponds to the observed experimental result
as the critical point is reached.

E�C.�(b) �e van der Waals equation of state in terms of the volume is given by [�C.�a–
��], p = nRT�(V −b)−an 2 �V 2 . �e parameters a and b for H� S are given in the
Resource section as a = 4.484 atm dm6 mol−2 and b = 4.34 × 10−2 dm3 mol−1 .
With these units it is convenient to use R = 8.2057 × 10−2 dm3 atm K−1 mol−1 .
�e pressure is computed by substituting in the relevant data.
(i) T = 273.15 K, V = 22.414 dm3 , n = 1.0 mol
nRT an 2
p= − 2
V − nb V
(1.0 mol) × (8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (273.15 K)
=
(22.414 dm3 ) − (1.0 mol) × (4.34 × 10−2 dm3 mol−1 )
(4.484 atm dm6 mol−2 ) × (1.0 mol)2
− = 0.99 atm
(22.414 dm3 )2
 (ii) T = 500 K, V = 150 cm3 = 0.150 dm3 , n = 1.0 mol

nRT an 2
p= − 2
V − nb V
(1.0 mol) × (8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (500 K)
=
(0.150 dm3 ) − (1.0 mol) × (4.34 × 10−2 dm3 mol−1 )
(4.484 atm dm6 mol−2 ) × (1.0 mol)2
− = 1.9 × 102 atm
(0.150 dm3 )2

E�C.�(b) Recall that 1 atm = 1.01325 × 105 Pa, 1 dm6 = 10−6 m6 , and 1 Pa = 1 kg m−1 s−2

1.01325 × 105 Pa 10−6 m6

a = (1.32 atm dm6 mol−2 ) × × = 0.134 Pa m6 mol−2
1 atm 1 dm6
= 0.134 kg m−1 s−2 m6 mol−2 = 0.134 kg m5 s−2 mol−2

10−3 m3
b = (0.0436 dm3 mol−1 ) × = 4.36 × 10−5 m3 mol−1
1 dm3

E�C.�(b) �e compression factor Z is de�ned in [�C.�–��] as Z = Vm �Vm○ , where Vm○ is

the molar volume of a perfect gas under the same conditions. �is volume is
computed from the equation of state for a perfect gas, [�A.�–�], as Vm○ = RT�p,
hence Z = pVm �RT [�C.�–��].
(i) If Vm is ��% larger than the molar volume of a perfect gas, it follows that
Vm = Vm○ (1 + 0.12) = 1.12Vm○ . �e compression factor is then computed
directly as
Vm 1.12 × Vm○
Z= ○ = = �.��
Vm Vm○
(ii) From [�C.�–��] it follows that Vm = ZRT�p

ZRT 1.12 × (8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (350 K)

Vm = =
p 12 atm
= �.� dm3 mol−1

Because Z > 1, implying that Vm > Vm○ , repulsive forces are dominant.

E�C.�(b) (i) �e molar volume is computed from the equation of state for a perfect
gas, [�A.�–�], as Vm = RT�p

RT (8.3145 J K−1 mol−1 ) × ([25 + 273.15] K)

Vm = = = 1.24×10−4 m3 mol−1
p 200 × 105 Pa

hence Vm = 0.124 dm3 mol−1 .

 (ii) �e van der Waals equation of state in terms of the molar volume is given
by [�C.�b–��], p = RT�(Vm − b) − a�Vm2 . �is equation is a cubic in Vm ,
as is seem by multiplying both sides by (Vm − b)Vm2 and then gathering
the terms together

pVm3 − Vm2 (pb + RT) + aVm − ab = 0

�e values of the constants are given, as is the pressure and tempera-

ture. Given the units of the quoted values of a and b it is convenient
to convert the pressure of ��� bar (200 × 105 Pa) to atm, p = (200 ×
105 Pa) × (1 atm)�(1.01325 × 105 Pa) = 197.4 atm, and to use R =
8.2057 × 10−2 dm3 atm K−1 mol−1 . Inserting all of these values gives the
polynomial

197.4Vm3 − 30.762Vm2 + 1.364Vm − 0.04351 = 0

�e roots of this polynomial are found numerically using Mathematical

so�ware and of these roots only Vm = 0.112 dm3 mol−1 is a physically
plausible value for the molar volume (the other roots are complex). �is
molar volume is smaller than the molar volume of the corresponding
perfect gas by about ��%.
An alternative approach is to approximate the term a�Vm2 as a�(Vm○ )2 and
then rearrange the van der Waals equation to give a simpler expression for
Vm
RT a RT
p= − hence Vm = +b
(Vm − b) (Vm○ )2 p + [a�(Vm○ )2 ]

RT
Vm = +b
p + [a�(Vm○ )2 ]
(8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (298.15 K)
=
(197.4 atm) + [(1.364 atm dm6 mol−2 )�(0.124 dm3 mol−1 )2 ]
+ 3.19 × 10−2 dm3 mol−1 = 0.117 dm3 mol−1

�is approximate value for Vm is then used in place of Vm○ and the whole
process repeated. A�er a few iterations the value of Vm settles as �.��� dm3 mol−1 ,
which is the same as the value found by solving the cubic.

E�C.�(b) (i) �e compression factor Z is given in terms of the molar volume and pres-
sure by [�C.�–��], Z = pVm �RT, hence Vm = ZRT�p. �e volume occu-
pied by n mol is therefore V = nVm = nZRT�p
nZRT
V=
p
(8.2 × 10−3 mol) × (0.86) × (8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (300 K)
=
20 atm
= 8.7 × 10−3 dm3 = �.� cm3
 (ii) �e virial expansion in terms of Vm is given by [�C.�b–��], pVm = RT(1 +
B�Vm + . . .). �e relationship in [�C.�–��], Z = pVm �RT, is used to
rewrite the term pVm as ZRT. If only the �rst two terms of the expansion
are retained it follows that
B B
ZRT = RT �1 + � hence Z = �1 + �
Vm Vm
and therefore B = Vm (Z − 1). �e relationship Vm = ZRT�p is used to
give

ZRT
B = Vm (Z − 1) = (Z − 1)
p
(0.86) × (8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (300 K)
= × (0.86 − 1)
20 atm
= −0.15 dm3 mol−1

E�C.�(b) �e relation between the critical constants and the van der Waals parameters
is given by [�C.�–��]
a 8a
Vc = 3b pc = Tc =
27b 2 27Rb
All three critical constants are given, so the problem is over-determined: any
pair of the these expressions is su�cient to �nd values of a and b. It is con-
venient to use R = 8.2057 × 10−2 dm3 atm K−1 mol−1 and volumes in units of
dm3 .
If the expressions for Vc and p c are used, a and b are found in the following
way

Vc = 3b hence b = Vc �3 = (0.148 dm3 mol−1 )�3 = 0.0493 dm3 mol−1

a a
pc = = hence a = 27(Vc �3)2 p c
27b 2 27(Vc �3)2
a = 27(Vc �3)2 p c = 27([0.148 dm3 mol−1 ]�3)2 × (48.2 atm)
= 3.17 atm dm6 mol−2

�ere are three possible ways of choosing two of the expressions with which to
�nd a and b, and each choice gives a di�erent value. For a the values are �.��,
�.��, and �.��, giving an average of �.�� atm dm6 mol−2 . For b the values are
�.����, �.����, and �.����, giving an average of �.���� dm3 mol−1 .
In Section �C.�(a) on page �� it is argued that b = 4Vmolec N A , where Vmolec is
the volume occupied by one molecule. �is volume is written in terms of the
radius r as 4πr 3 �3 so it follows that r = (3b�16πN A )1�3 .

3 × (0.0546 dm3 mol−1 )

1�3 1�3
3b
r=� � =� � = 1.76×10−9 dm = ��� pm
16πN A 16π × (6.0221 × 1023 mol−1 )
E�C.�(b) (i) In Section �C.�(b) on page �� it is explained that at the Boyle temperature
Z = 1 and dZ�dp = 0; this latter condition corresponds to the second
virial coe�cient, B or B′ , being zero. �e task is to �nd the relationship
between the van der Waals parameters and the virial coe�cients, and the
starting point for this are the expressions for the product pVm is each case
([�C.�b–��] and [�C.�b–��])

RT a RT Vm a
van der Waals: p = − hence pVm = −
(Vm − b) Vm2 (Vm − b) Vm

B
virial: m = RT �1 + �
Vm
�e van der Waals expression for pVm is rewritten by dividing the denom-
inator and numerator of the �rst fraction by Vm

RT a
pVm = −
(1 − b�Vm ) Vm

�e dimensionless parameter b�Vm is likely to be � 1, so the approxima-

tion (1 − x)−1 ≈ 1 + x is used to give

a 1 a
pVm = RT(1 + b�Vm ) − = RT �1 + �b − ��
Vm Vm RT

Comparison of this expression with the virial expansion shows that

a
B=b−
RT
It therefore follows that the Boyle temperature, when B = 0, is Tb = a�Rb.
For the van der Waals parameters from the Resource section

a 4.484 atm dm6 mol−2

Tb = =
Rb (8.2057 × 10−2 dm atm K−1 mol−1 ) × (4.34 × 10−2 dm3 mol−1 )
3

= 1.26 × 103 K

(ii) In Section �C.�(a) on page �� it is argued that b = 4Vmolec N A , where

Vmolec is the volume occupied by one molecule. �is volume is written
in terms of the radius r as 4πr 3 �3 so it follows that r = (3b�16πN A )1�3 .

3 × (4.34 × 10−2 dm3 mol−1 )

1�3 1�3
3b
r=� � =� �
16πN A 16π × (6.0221 × 1023 mol−1 )
= 1.63 × 10−9 dm = ��� pm

E�C.�(b) �e reduced variables are de�ned in terms of the critical constants in [�C.�–��]

Vr = Vm �Vc p r = p�p c Tr = T�Tc

 If the reduced pressure is the same for two gases (�) and (�) it follows that

p(1) p(2) p(1)

(1)
= (2)
hence p(2) = (1)
× p(2)
c
pc pc pc
and similarly
T (1)
T (2) =
(1)
× Tc(2)
Tc
�ese relationships are used to �nd the pressure and temperature of gas (�)
corresponding to a particular state of gas (�); it is necessary to know the critical
constants of both gases.
(i) From the tables in the Resource section, for N� p c = 33.54 atm, Tc =
126.3 K, and for H� O p c = 218.3 atm, Tc = 647.4 K. Taking gas (�) as N�
and gas (�) as H� O, the pressure and temperature of H� O corresponding
to p(N2 ) = 1.0 atm and T (N2 ) = 298.15 K is calculated as

p(N2 ) 1.0 atm

p(H2 O) = (N )
× p(H
c
2 O)
= × (218.3 atm) = �.� atm
pc 2 33.54 atm

T (N2 ) 298.15 K
T (H2 O) = (N )
× Tc(H2 O) = × (647.4 K) = 1.5 × 103 K
Tc 2 126.3 K
(ii) For CO� p c = 72.9 atm, Tc = 304.2 K.

p(N2 ) 1.0 atm

p(CO2 ) = (N )
× p(CO
c
2)
= × (72.9 atm) = �.� atm
pc 2 33.54 atm

T (N2 ) 298.15 K
T (CO2 ) = (N )
× Tc(CO2 ) = × (304.2 K) = 7.2 × 102 K
Tc 2 126.3 K
(iii) For Ar p c = 48.0 atm, Tc = 150.7 K.

p(N2 ) 1.0 atm

p(Ar) = (N )
× p(Ar)
c = × (48.0 atm) = �.� atm
pc 2 33.54 atm

T (N2 ) 298.15 K
T (Ar) = (N )
× Tc(Ar) = × (150.7 K) = 3.6 × 102 K
Tc 2 126.3 K

E�C.�(b) �e van der Waals equation of state in terms of the molar volume is given by
[�C.�b–��], p = RT�(Vm − b) − a�Vm2 . �is relationship is rearranged to �nd b
RT a a RT
p= − hence p + 2 =
Vm − b Vm2 Vm Vm − b
pVm2 + a RT Vm2 Vm − b
hence = hence =
Vm2 Vm − b pVm2 + a RT
2
RT Vm
hence b = Vm −
pVm2 + a
 With the data given

RT Vm2
b = Vm − = (4.00 × 10−4 m3 mol−1 )
pVm2 + a
(8.3145 J K−1 mol−1 ) × (288 K) × (4.00 × 10−4 m3 mol−1 )2
−
(4.0 × 106 Pa) × (4.00 × 10−4 m3 mol−1 )2 + (0.76 m6 Pa mol−2 )
= 1.3 × 10−4 m3 mol−1

where 1 Pa = 1 kg m−1 s−2 and 1 J = 1 kg m2 s−2 have been used.

�e compression factor Z is de�ned in [�C.�–��] as Z = Vm �Vm○ , where Vm○ is
the molar volume of a perfect gas under the same conditions. �is volume is
computed from the equation of state for a perfect gas, [�A.�–�], as Vm○ = RT�p,
hence Z = pVm �RT, [�C.�–��]. With the data given

pVm (4.0 × 106 Pa) × (4.00 × 10−4 m3 mol−1 )

Z= = = �.��
RT (8.3145 J K−1 mol−1 ) × (288 K)

P�C.� (a) Using the perfect gas law, pV = nRT, the molar volume is calculate as

RT (8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (350 K)

Vm = = = ��.� dm3 mol−1
p 2.30 atm

(b) �e van der Waals equation of state in terms of the molar volume is given
by [�C.�b–��], p = RT�(Vm −b)−a�Vm2 ; the term a�Vm2 is due to attractive
interactions.
�is equation is a cubic in Vm which can be solved numerically. A simpler
approach is to approximate a�Vm2 as a�(Vm○ )2 , where Vm○ is the molar
volume of a perfect gas under the prevailing conditions. �e van der
Waals equation is then rearranged to give a simpler expression for Vm

RT a RT
p= − hence Vm = +b
(Vm − b) (Vm○ )2 p + [a�(Vm○ )2 ]

�e van der Waals constants for Cl� are a = 6.260 atm dm6 mol−2 and
b = 5.42 × 10−2 dm3 mol−1 . With these values, the �rst approximation to
the molar volume is calculated as
(8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (350 K)
Vm =
(2.30 atm) + [(6.260 atm dm6 mol−2 )�(12.5 dm3 mol−1 )2 ]
+ 5.42 × 10−2 dm3 mol−1 = 12.3 dm3 mol−1

�is approximate value for Vm is then used in place of Vm○ and the process
repeated, to give Vm = 12.3 dm3 mol−1 – the same value. �e process has
converged (to this level of precision).
P�C.� �e van der Waals equation in terms of the molar volume is given by [�C.�b–
��], p = RT�(Vm − b) − a�Vm2 . Multiplication of both sides by Vm gives

RT Vm a
pVm = −
(Vm − b) Vm

Division of the numerator and denominator of the �rst fraction by Vm , and

then taking a factor of RT on the right gives the required expression

1 a
pVm = RT � − � (�.�)
(1 − b�Vm ) RT Vm

�e approximation (1 − x)−1 ≈ 1 + x is the used to write 1�(1 − b�Vm ) as

(1 + b�Vm ) to give

b a 1 a
pVm = RT �1 + �− hence pVm = RT �1 + �b − ��
Vm Vm Vm RT
�e virial equation in terms of the molar volume is given by [�C.�b–��]

B
pVm = RT �1 + + . . .�
Vm

Comparison of this equation with eqn �.� shows that B = b − a�RT, as required.
�e value of the second virial coe�cient at the critical temperature of ���.� K
is found from the given van der Waals parameters as
a
B=b−
RT
1.390 atm dm6 mol−2
= (0.0391 dm3 mol−1 ) −
(8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (126.3 K)
= −0.0950... dm3 mol−1

With this value for B, the molar volume is computed using the virial equation
and with the approximation that the molar volume or the right-hand side of
the expression can be replaced by the molar volume of a perfect gas, Vm○ , under
the same conditions
RT B RT B RT B
Vm = �1 + �≈ �1 + ○ � = �1 + �
p Vm p Vm p RT�p
RT
hence Vm = +B
p
(8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (126.3 K)
= − 0.0950... dm3 mol−1
10 atm
= 0.941... = �.�� dm3 mol−1

Repeating the calculation at the Boyle temperature, ���.� K, gives B = −0.0126... dm3 mol−1
and Vm = 2.67... dm3 mol−1 hence Vm = 2.7 dm3 mol−1 .
 How close a gas under particular conditions is to perfect behaviour is assessed
by computing the compression factor Z, given by [�C.�–��], Z = pVm �RT. At
���.� K
pVm (10 atm) × (0.941... dm3 mol−1 )
Z= = = 0.91
RT (8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (126.3 K)
and at ���.� K
pVm (10 atm) × (2.67... dm3 mol−1 )
Z= = = 1.00
RT (8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (327.2 K)
�e latter conditions give Z = 1, as expected at the Boyle temperature, whereas
in the former case Z di�ers signi�cantly from �. �e gas is closer to perfect
behaviour at the Boyle temperature that at the critical temperature.

P�C.� �e molar volume for a perfect gas is computed from Vm = RT�p

RT (8.2057 × 10−2 dm3 atm K−1 mol−1 ) × (400 K)

Vm = = = 10.941 dm3 mol−1
p 3 atm
�e van der Waals equation of state in terms of the molar volume is given by
[�C.�b–��], p = RT�(Vm − b) − a�Vm2 . �is equation is a cubic in Vm , as is seen
by multiplying both sides by (Vm −b)Vm2 and then gathering the terms together

pVm3 − Vm2 (pb + RT) + aVm − ab = 0

Inserting the values of the van der Waals constants, a = 1.337 atm dm6 mol−2
and b = 3.20 × 10−2 dm3 mol−1 , and the stated temperature and pressure gives
the polynomial

3V 3 − 32.919Vm2 + 1.337Vm − 0.042784 = 0

�e roots of this polynomial are found numerically using mathematical so�-

ware and of these roots only Vm = 10.932 dm3 mol−1 is a physically plausible
value for the molar volume.
�e di�erence between the molar volume and that of a perfect gas is expressed
in terms of the fraction
Vm − Vm○ (10.932 dm3 mol−1 ) − (10.941 dm3 mol−1 )
= = −8.2 × 10−4
Vm○ 10.941 dm3 mol−1
�e di�erence between the molar volumes is therefore −0.082% of the molar
volume of the perfect gas.

P�C.� According to Table �C.� on page ��, for the Berthelot equation of state the
critical constants are given by

1 2aR 1�2 2 2a 1�2

pc = � � Vc = 3b Tc = � �
12 3b 3 3 3bR
 �e �rst step is to rewrite the bracket in the expression for Tc so that it matches
the bracket in the expression for p c
1�2 1�2 1�2
2 2a 1�2 R2 b2 2 2aR 1�2 b2
Tc = � � × � 2 � ×� 2� = � 3 � ×� 2�
3 3bR b R 3 3b R
��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � �� � � � � � � � � �
combine A

Term A is recognised as being 12p c . �e next step is to rewrite b in terms of

Vc , b = Vc �3, and then substitute this into the previous expression.

(Vc �3)2
1�2 1�2
2 b2 2 2 1 p c Vc
Tc = (12p c ) × � 2 � = (12p c ) × � � = × 12 × ×
3 R 3 R2 3 3 R

Tidying up the fractions gives Tc = (8�3)p c Vc �R .

�e critical temperature for this gas is therefore
8 p c Vc 8 (40 atm) × (160 × 10−3 dm3 mol−1 )
Tc = × = × = ��� K
3 R 3 8.2057 × 10−2 dm3 atm K−1 mol−1
In the Berthelot equation of state the parameter b is still interpreted as an
excluded volume in the same way as in the van der Waals equation. In Sec-
tion �C.�(a) on page �� it is argued that b = 4Vmolec N A , where Vmolec is the
volume occupied by one molecule. �is volume is written in terms of the radius
r as 4πr 3 �3 so it follows that r = (3b�16πN A )1�3 . Because Vc = 3b this can be
rewritten r = (Vc �16πN A )1�3

160 × 10−3 dm3 mol−1

1�3 1�3
Vc
r=� � =� �
16πN A 16π × (6.0221 × 1023 mol−1 )
= 1.74 × 10−9 dm = ��� pm

P�C.�� �e virial equation (up to the second term) in terms of the molar volume is
given by [�C.�b–��]
B
pVm = RT �1 + �
Vm
Division of each side by p gives
RT B
Vm = �1 + �
p Vm
�e quantity RT�p is recognised as the molar volume of a perfect gas, Vm○ , so
it follows that
B Vm B
Vm = Vm○ �1 + � hence ○ = Z = �1 + �
Vm Vm Vm

In Problem P�C.� it is shown that B is related to the van der Waals constants by
B = b − a�RT; using this, the compression factor is given by
b − a�RT
Z = �1 + �
Vm
 It follows that
a a
Z > 1 when b > and Z < 1 when b <
RT RT

P�C.�� �e starting point are the two equations

RT 2a 2RT 6a
− + =0 − =0
(Vm − b)2 Vm3 (Vm − b)3 Vm4

To eliminate a between these equations the �rst is multiplied by 3�Vm and then
they are added together to give
3RT 2RT
− + =0
Vm (Vm − b) 2 (Vm − b)3
�e term RT cancels, and the fractions are eliminated by multiplying through
by Vm (Vm − b)3 to give

−3(Vm − b) + 2Vm = 0

from which it follows that Vm = 3b at the critical point.

�is expression for Vm is then used in the �rst equation
RT 2a RT 2a
− + 3 =0 becomes − + =0
(Vm − b) 2 Vm (2b) 2 (3b)3

Multiplication through by 4 × 27 × b 3 eliminates the fractions to give

−27RTb + 8a = 0

from which it follows that T = 8a�27Rb at the critical point.

To �nd the pressure at the critical point these values of Vm and T are substituted
into the van der Waals equation in terms of the molar volume, [�C.�b–��]
RT a
p= − 2
(Vm − b) Vm
8a R a 8a a a
= − = − =
27Rb 2b (3b)2 54b 2 9b 2 27b 2

�e pressure at the critical point is therefore given by p = a�27b 2 .

P�C.�� �e virial equation in terms of the molar volume, [�C.�b–��], is

B C
pVm = RT �1 + + 2 + . . .� (�.�)
Vm Vm

�e virial equation in terms of the pressure, [�C.�a–��], is

pVm = RT �1 + B′ p + C ′ p2 + . . .� (�.�)
 Equation �.� is rewritten to give an expresion for the pressure

RT B C
p= �1 + + 2 + . . .�
Vm Vm Vm
�is expression for p is substituted into the right-hand side of eqn �.� to give

pVm = RT �1 + B′ p + C ′ p2 + . . .�
� B′ RT C′ R2 T 2 �
2
B C B C
= RT 1 + �1 + + 2 + . . .� + �1 + + 2 + . . .� + . . .
� Vm Vm Vm Vm2 Vm Vm �
(�.�)

On the right there is only one term in 1�Vm

B′ R 2 T 2
Vm
�is is identi�ed with the term in 1�Vm on the right-hand side of eqn �.�

B′ R 2 T 2 BRT
= hence B = B′ RT
Vm Vm

�ere are two terms in 1�Vm2 on the right-hand side of eqn �.�

B′ BR 2 T 2 C ′ R 3 T 3
+
Vm2 Vm2

�ese are identi�ed with the term in 1�Vm2 on the right-hand side of eqn �.�

B′ BR 2 T 2 C ′ R 3 T 3 CRT
+ = hence B′ BRT + C ′ R 2 T 2 = C
Vm2 Vm2 Vm2

With the substitution B = B′ RT, the relationship is C = R 2 T 2 [(B′ )2 + C ′ ] .

P�C.�� �e given equation of state is multiplied through by Vm2 to give

pVm2 = RT Vm + (a + bT)

�e partial di�erential with respect to T of both sides of the equation is then

computed, being careful to remember that Vm is a function of T so, for example,
the term RT Vm must be di�erentiated using the product rule. Calculating the
derivative is essentially an application of the chain rule.
∂Vm ∂Vm
2pVm � � = RT � � + RVm + b
∂T p ∂T p

�is equation is then rearranged by collecting the terms in ∂Vm �∂T together

∂Vm ∂Vm RVm + b

� � (2pVm − RT) = RVm + b hence � � =
∂T p ∂T p 2pVm − RT
P�C.�� In Section �C.�(b) on page �� it is explained that critical behaviour is associated
with oscillations in the isotherms predicted by a particular equation of state. In
particular, at the critical point a minimum and a maximum in the isotherm
coincide at the same pressure and volume, thus creating a point of in�exion.
�is is the critical isotherm, and is at the critical temperature.
A gas which shows critical behaviour can be lique�ed by the application of
pressure alone, provided the temperature is below the critical temperature.
An equation of state should predict that, as the volume decreases eventually
the pressure increases without limit. For gas A, in the limit b�Vm � 1 the
equation of state becomes pVm2 = bRT, which has the correct behaviour. As the
volume increases, the expectation is that the perfect gas law will be regained,
and for gas A the limit b�Vm � 1 gives pVm = RT, as expected. For gas B in
the limit Vm � b the perfect gas law results, but in the opposite limit, Vm � b,
the equation of state becomes −pb = RT, implying that the pressure reaches a
constant value of −RT�b which is problematic for positive b.
For there to be (at least) two extrema in the plots of Vm against p, the derivative
dVm �dT must have two roots – that is, values at which it is = 0. �is implies
that the expression for the derivative must be a quadratic in Vm , and therefore
that the expression for Vm must be a cubic in Vm . It is evident that neither of
the proposed equations of state are cubic in Vm , and so neither is expected to
show critical behaviour.

P�C.�� In Brief Illustration �C.� the reduced pressure is �.�� and the reduced temper-
ature is �.��; the critical constants for NH� are given in the Resource section as
p c = 111.3 atm and Tc = 405.5 K. �e pressure and temperature for the same
state as argon are therefore

p = 0.48 × (111.3 atm) = ��.�� atm T = 1.22 × (405.5 K) = ���.� K

P�C.�� �e equation of state for a perfect gas, [�A.�–�], is pV = nRT, and the van
der Waals equation of state in terms of the volume is given by [�C.�a–��], p =
nRT�(V −b)−an 2 �V 2 . From the Resource section the van der Waals parameters
for CO� are a = 3.610 atm dm6 mol−2 and b = 4.29 × 10−2 dm3 mol−1 .
Plots of p against V , Fig. �.�, show only minor deviations between a van der
Waals gas and a perfect gas under these conditions. Plotting p against 1�V
gives a straight line for the perfect gas, and as in seen in Fig. �.� the deviations
for the van der Waals gas are minor.

P�C.�� �e van der Waals equation in terms of the molar volume is given by [�C.�b–
��], p = RT�(Vm − b) − a�Vm2 , and the compression factor Z is given by [�C.�–
��], Z = pVm �RT, hence

Vm RT a Vm a
Z= � − 2�= − (�.�)
RT Vm − b Vm Vm − b RT Vm
 3.0
van der Waals
perfect
2.5

p�atm 2.0
��� K

1.5
��� K

1.0
15 20 25 30
V �dm 3

3.0
van der Waals
2.5 perfect
��� K
p�atm

2.0
��� K
1.5

1.0
0.03 0.04 0.05 0.06 0.07
(1�V )�(dm ) −3

To �nd the turning points in Z as a function of Vm the derivative dZ�dVm is

set to zero. In computing the derivative, write the �rst term as Vm (Vm − b)−1
and recognise the the need to use the product rule
dZ −Vm 1 a
= + + =0
dVm (Vm − b)2 Vm − b RT Vm2
hence Vm2 (a − bRT) − 2abVm + ab 2 = 0
To go to the second line the equation is multiplied through by RT Vm2 (Vm −b)2 .
�e resulting quadratic in Vm is solved in the usual way
1
Vm = �2ab ± �4a 2 b 2 − 4ab 2 (a − bRT)� �
1�2
2(a − bRT)
� bRT 1�2 �
b � �
hence Vm = �1 ± � � �
1 − bRT�a �
� a �
�
 �e positions of the turning points depend on the van der Waals parameters as
well as the temperature. �e predictions of these equation are best explored by
inserting some typical values.
For N� , a = 1.352 atm dm6 mol−2 and b = 0.0387 dm3 mol−1 . At ��� K the two
extrema occur at Vm = 0.237 dm3 mol−1 and Vm = 0.0211 dm3 mol−1 ; using
these values in eqn �.� gives compression factors of 0.962 and −3.82. �e latter
value is physically unreasonable, but the former is acceptable and for this value
the pressure is calculated as 99.3 atm.
For Ne a = 0.205 atm dm6 mol−2 and b = 0.0167 dm3 mol−1 . At ��� K one
of the extrema occurs at a negative value of Vm and the other occurs at 6.92 ×
10−3 dm3 mol−1 . However, this latter value gives a negative value of Z, which
is not acceptable. �erefore, there are no physically plausible conditions under
which Z is a minimum for Ne at ��� K.

I�.� According to the equipartition theorem (�e chemist’s toolkit � in Topic �A),
each quadratic contribution to the energy of a molecule contributes 12 kT to
the average energy per molecule. Translational kinetic energy is a quadratic
term, and because translation is possible in three dimensions, the quoted en-
ergy density of 0.15 J cm−3 is the result of three such contributions.
�e rotation of a molecule about an axis is also a quadratic contribution to the
energy, and in general three such contributions are expected corresponding to
rotation about three mutually perpendicular axes. However, linear molecules,
such as diatomics, do not show rotation about their long axes, so there are
only two contributions. �e contribution of rotation to the energy density will
therefore be 23 of that due to translation

��� � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
trans. rot.

total energy denisty = (0.15 J cm−3 ) + 23 × (0.15 J cm−3 ) = 0.25 J cm−3

D�A.� Work is done when a body is moves against an opposing force. For an in�nites-
imal displacement in the x-direction, dx, against a force F along that direction
the work done by the body is F dx.
When the energy of a system changes as a result of a temperature di�erence
between the system and its surroundings, the resulting energy transfer from the
hotter to the cooler body is described as heat. In thermodynamic terms, both
heat and work cause the internal energy of an object to change: if heat ‘�ows in’
the internal energy of the body rises, if the body ‘does work’, its internal energy
decreases.
If the internal energy of an object increases, this is interpreted in molecular
terms as the molecules moving up to higher energy levels. If the molecules
drop down to lower levels the resulting energy is available as heat or work.

D�A.� A reversible gas expansion is one in which the direction of the process can be re-
versed by an in�nitesimal change in the external pressure. �is is achieved if the
external pressure is altered so that it is only ever in�nitesimally di�erent from
the pressure of the gas which is expanding or contracting. In other words, the
external pressure must always match the pressure of the expanding/contracting
gas.

E�A.�(b) �e chemist’s toolkit � in Topic �A gives an explanation of the equipartition

theorem. �e molar internal energy is given by

Um = 1
2
× (νt + νr + 2νv ) × RT

where νt is the number of translational degrees of freedom, νr is the number

of rotational degrees of freedom and νv is the number of vibrational degrees
of freedom. As each gas molecule can move independently along the x, y
and z axis, the number of translational degrees of freedom is three. All the
listed molecules have three degrees of rotational freedom and none of them is
expected to have any vibrational modes which are signi�cantly excited at room
 temperature. �erefore, at room temperature, ozone, ethane and sulfur dioxide
are all expected to have an approximate molar internal energy of

Um = 12 ×(3+2+0)×RT = 3×(8.3145 J K−1 mol−1 )×(298.15 K) = 7.4 kJ mol−1

E�A.�(b) A state function is a property with a value that depends only on the current state
of the system and is independent of how the state has been prepared. Volume,
internal energy and density are all state functions.

E�A.�(b) �e system is expanding against a constant external pressure, hence the expan-
sion work is given by [�A.�–��], w = −pex ∆V . �e change in volume is the
cross-sectional area times the linear displacement

∆V = (75 cm2 ) × (25 cm) = 1875 cm3 = 1.87... × 10−3 m3

�e external pressure is 150 kPa = 1.50 × 105 Pa, therefore the expansion work
is
w = −(1.50 × 105 Pa) × (1.87... × 10−3 m3 ) = −281 J

Note that the volume is expressed in m3 . �e relationships 1 Pa = 1 kg m−1 s−2

and 1 J = 1 kg m2 s−2 are used to verify the units of the result.

E�A.�(b) For all cases ∆U = 0, because the internal energy of a perfect gas depends on
the temperature alone. E

(i) �e work of reversible isothermal expansion of a perfect gas is given by

[�A.�–��]
Vf
w = −nRT ln � �
Vi
20.0 dm3
= −(2.00 mol) × (8.3145 J K−1 mol−1 ) × (273.15 K) × ln � �
5.0 dm3
= −6.3 × 103 J = −�.� kJ

Note that the temperature is expressed in K in the above equation. Using

the First Law of thermodynamics, [�A.�–��], gives

q = ∆U − w = 0 − (−2.68 kJ) = +�.�� kJ

(ii) �e �nal pressure of the expanding gas is found using the perfect gas law,
[�A.�–�]

nRT (2.00 mol) × (8.3145 J K−1 mol−1 ) × (273.15 K)

pf = =
Vf (20.0 × 10−3 m3 )
= 2.27... × 105 Pa
 �is pressure equals the constant external pressure against which the gas
is expanding, therefore the work of expansion is

w = −pex × ∆V = (2.27... × 105 Pa) × (20.0 × 10−3 m3 − 5.0 × 10−3 m3 )

= −3.41 × 103 J = −3.41 kJ

and hence q = +3.41 kJ

(iii) Free expansion is expansion against zero force, so w = 0 and therefore
q = 0 as well.

E�A.�(b) For a perfect gas at constant volume pi �Ti = pf �Tf therefore,

Tf 356 K
pf = pi × = (111 kPa) × � � = 143 kPa
Ti 277 K
�e change in internal energy at constant volume is given by [�A.��b–��]

5
∆U = nC V ,m ∆T = (2.00 mol) × � × 8.3145 J K−1 mol−1 � × (356 K − 277 K)
2
= +3.28 × 103 J = +3.28 kJ

�e volume of the gas is constant, so the work of expansion is zero, w = 0 . �e

First Law of thermodynamics gives q = ∆U − w = +3.28 kJ − 0 = +3.28 kJ .

E�A.�(b) (i) �e work of expansion against constant external pressure is given by [�A.�–
��], w = −pex ∆V = −(7.7 kPa) × (2.5 dm3 ) = −19 J .
(ii) �e work done in a reversible, isothermal expansion is given by [�A.�–��]
w = −nRT ln(Vf �Vi ). �e amount in moles of argon is

m (6.56 g)
n= = = 0.164... mol
M (39.95 g mol−1 )
w = −(0.164... mol) × (8.3145 J K−1 mol−1 ) × (305 K)
[18.5 + 2.5] dm3
× ln � � = −53 J
18.5 dm3

Note that the modulus of the work done in a reversible expansion is greater
than the work for expansion against constant external pressure because
the latter is an irreversible process.

P�A.� �e First Law of thermodynamics states that ∆U = q + w. Work is done on

the electric heater, so w = +1 kJ. Heat is transferred to the surroundings, so
q = −1 kJ. �erefore overall

∆U = q + w = (−1 kJ) + (1 kJ) = 0

P�A.� (a) n = x�l = (90 nm)�(45 nm) = 2.0 therefore ν = n�N = 2.0�200 = 0.01
kT 1+ν
F= ln � �
2l 1−ν
(1.3806 × 10−23 J K−1 ) × (298.15 K) 1 + 0.01
= × ln � � = 9.1 × 10−16 N
(2 × 45 × 10 m)
−9 1 − 0.01

(b) �e equation to be plotted is F�N = 4.57 × 10−14 ln [(1 + ν)�(1 − ν)]; this
is shown in Fig. �.�.

2
1013 F� N

−2

−1.0 −0.5 0.0 0.5 1.0

ν

�e natural logarithm can be expanded using the Taylor series as ln(1 +

ν) ≈ ν + ν 2 �2! + ν 3 �3! + ..., which, for ν << 1, can be approximated as
ln(1 + ν) ≈ ν, and similarly, ln(1 − ν) ≈ −ν. �erefore,
kT kT νkT
F= [ln(1 + ν) − ln(1 − ν)] ≈ [ν − (−ν)] =
2l 2l l
Because ν = n�N, it follows that
νkT nkT
F= =
l Nl
Hooke’s law predicts F = const × x, that is the restoring force is directly
proportional to the displacement. Using n = x�l, the expression for the
force obtained in part (a) is rewritten as
nkT kTx
= ≡ const × x
Nl Nl2
�erefore Hooke’s law applies and kT�N l 2 is the force constant.
(c)
kT 1+ν kT 1+ν
dw = F dx = ln � � dx = ln � � (N l dν)
2l 1−ν 2l 1−ν
N kT 1+ν
= ln � � dν
2 1−ν
 Integrating both sides and using ∫ ln(1 ± x) dx = (x ± 1) ln (1 ± x) − x
gives
N kT Vf 1+ν
� dw = � ln � � dν
2 0 1−ν
N kT
w= [(ν + 1) ln(1 + ν) + ν − (ν − 1) ln(1 − ν) − ν]0νf
2
N kT 1 + ν νf
= �ln(1 + ν)(1 − ν) + ν ln � ��
2 1−ν 0
N kT 1 + νf
= �ln(1 + νf )(1 − νf ) + νf ln � ��
2 1 − νf

P�A.� �e expansion work is given by [�A.�–��], dw = −pex dV . For a reversible

expansion pex is always equal to the pressure of the gas so

nRT n 2 a
dw = −pgas dV = − � − 2 � dV
V V
Integrating both sides gives
Vf nRT n 2 a
w=� −� − 2 � dV
Vi V V
Vf
n2 a Vf 1 1
= �−nRT ln V − � = −nRT ln � � − n 2 a � − �
V Vi Vi Vf Vi

�e work done on the surroundings is the opposite of the work done on the
gas.
Vf 1 1
wsurr = nRT ln � � + n 2 a � − �
Vi Vf Vi
�e �rst term is identical to the work done on the surroundings by a per-
fect gas expanding under reversible isothermal conditions. Vf > Vi , therefore
n 2 a(1�Vf − 1�Vi ) is negative, so the overall work done on the surroundings by
the gas is smaller than it would be for a perfect gas. �e attraction between the
gas molecules has to be overcome when expanding, meaning that less energy
is available as work.

P�A.� Decomposition of �.� mol of calcium carbonate liberates �.� mol of carbon
dioxide. In either case the expansion is against constant external atmospheric
pressure, pex = 1.0 atm = 1.01325 × 105 Pa. �e �nal volume of the expanding
gas is found using the perfect gas equation, V = nRT�pex . �e change in
volume of the solid is negligible compared to the change in volume due to the
formation of the gas, therefore the overall change in volume of the system is
∆V = V . �e work against constant external pressure is
nRT
w = −pex ∆V = −pex × = −nRT = −(1.0 mol) × (8.3145 J K−1 mol−1 )
pex
× ([800 + 273.15] K) = −8.9 × 103 J = −8.9 kJ
P�A.�� �e reduced pressure of a van der Waals gas is given by [�C.�–��]
8Tr n 3n
pr = −
3Vr − 1 Vr2
�e reduced volume, pressure and temperature are given in terms of the van
der Waals parameters in [�C.�–��] and [�C.�–��], Vm,r = Vm �Vc = Vm �(3b)
, pr = p�pc = 27b 2 p�a and Tr = T�Tc = 27RbT�8a. In Problem P�A.� the
work done during the isothermal reversible expansion of a van der Waals gas
is found as
Vf − nb 1 1
w = −nRT ln � � − n2 a � − �
Vi − nb Vf Vi
�is expression is �rst rewritten in term of the molar volume and then in terms
of the reduced volume, temperature and pressure.

nVm,f − nb 1 1
w = −nRT ln � � − n2 a � − �
nVm,i − nb nVm,f nVm,i
Vm,f − b 1 1
= −nRT ln � � − na � − �
Vm,i − b Vm,f Vm,i
8a 3bVr,f − b 1 1
= −nR � � Tr ln � � − na � − �
27Rb 3bVr,i − b 3bVr,f 3bVr,i
8a 3Vr,f − 1 na 1 1
= −n � � Tr ln � �− � − �
27b 3Vr,i − 1 3b Vr,f Vr,i
�e reduced work is de�ned as wr = (3b�a)w, with this it follows that

8 3Vr,f − 1 1 1
wr = −n � � Tr ln � �−n� − �
9 3Vr,i − 1 Vr,f Vr,i
For expansion along the critical isotherm from Vm,i = Vc to Vm,f = xVc . It
follows that Vr,i = Vm,i �Vc = Vc �Vc = 1 and Vr,f = Vm,f �Vc = xVc �Vc = x.
Along the critical isotherm Tc = 1, therefore wr is
8 3x − 1 1
wr = −n � � ln � � − n � − 1�
9 2 x

D�B.� If a substance is heated at constant volume all of the energy as heat is trans-
formed into internal energy of the substance. If the same process is carried out
under conditions of constant pressure some of the energy as heat will be used
to expand the substance against the external pressure and so less of the energy
as heat is transformed into internal energy. �is e�ect is largest for gases whose
volumes change much more rapidly with temperature than do solids or liquids.
�e temperature of a substance is related to its internal energy, and therefore
as energy as heat is supplied the temperature increases. For a given amount
 of energy as heat this increase in internal energy is smaller for the constant-
pressure case than for the constant-volume case. �erefore the rise in temper-
ate is smaller for the constant-pressure process, and this implies that the heat
capacity is greater.

E�B.�(b) �e heat transferred under constant pressure equals the change in enthalpy
of the system, [�B.�b–��], qp = ∆H. �e relationship between the change in
enthalpy, change in temperature and the heat capacity is given by [�B.�b–��]

∆H (178 J)
C p,m = = = 52.6... J K mol−1 = 53 J K−1 mol−1
n∆T (1.9 mol) × (1.78 K)
For a perfect gas C p,m − C V ,m = R, [�B.�–��], therefore

C V ,m = C p,m −R = (52.6... J K−1 mol−1 )−(8.3145 J K−1 mol−1 ) = 44 J K−1 mol−1

E�B.�(b) �ere is no change in the number of gaseous species on going from reactants
to products, therefore ∆ng = 0 and ∆Hm = ∆Um .

E�B.�(b) (i) �e heat capacity can be expressed as C p = a + bT where a = 20.17 J K−1

and b = 0.3665 J K−2 . Integrating the relationship dH = C p dT on both
sides gives
T2 T2 T2
dH = � C p dT = � (a + bT)dT = �aT + 12 bT 2 �T
T2
�
T1 T1 T1 1

1
H(T2 ) − H(T1 ) = na(T2 − T1 ) + nb(T22 − T12 )
2
= (20.17 J K−1 ) × (373.15 K − 298.15 K)
+ 12 × (0.4001 J K−2 ) × [(373.15 K)2 − (298.15 K)2 ]
= +11.5... kJ = +11.6 kJ

Under constant pressure conditions ∆H = qp = +11.6 kJ .

�e work of expansion against constant pressure pex is given by [�A.�–
��], w = −pex ∆V = −pex (Vf − Vi ). Assume that the gas is in mechanical
equilibrium with its surroundings, therefore pex is the same as the pres-
sure of the gas, p. �e initial and �nal volumes are calculated from Tf and
Ti by Vf = nRTf �p and Vi = nRTi �p, therefore Vf − Vi = (Tf − Ti )nR�p.
Hence
nR
w = −p × (Tf − Ti ) = −nR∆T
p
= −(1.00 mol) × (8.3145 J K−1 mol−1 ) × (373.15 K − 298.15 K)
= −6.23... × 102 J = −624 J
∆U = q + w = (+11.6... kJ) + (−0.623... kJ) = +11.0 kJ
 (ii) �e energy and enthalpy of a perfect gas depends on the temperature
alone, hence ∆H and ∆U is the same as above, ∆H = ∆U = +11.6 kJ .
Under constant volume conditions there is no expansion work, w = 0 ,
therefore the heat is equal to the change in internal energy, qV = ∆U =
+11.0 kJ .

E�B.�(b) Under constant pressure qp = ∆H, therefore

qp = ∆H = nC p,m ∆T = (2.0 mol) × (37.11 J K mol−1 ) × (277 K − 250 K)

= 2.00... kJ = +2.0 kJ

�e de�nition of enthalpy is given by [�B.�–��], H = U + pV . For a change

at constant pressure, it follows that ∆H = ∆U + p∆V , where ∆V = Vf − Vi .
If the gas is assumed to be perfect, then Vf = nRTf �p and Vi = nRTi �p, so
∆V = (Tf − Ti )nR�p. Hence p∆V = nR(Tf − Ti ) = nR∆T.

∆U = ∆H − nR∆T
= (2.0... kJ) − (2.0 mol) × (8.3145 J K−1 mol−1 ) × (277 K − 250 K)
= +1.6 kJ

P�B.� �e volume of the room is V = (5.5 m)×(6.5 m)×(3.0 m) = 107.25 m3 . Using

1 atm = 1.01325 × 105 Pa, the amount in moles of gas in the room initially is

pV (1.01325 × 105 Pa) × (107.25 m3 )

n= = = 4.38... × 103 mol
RT (8.3145 J K−1 mol−1 ) × (298 K)

Assuming that the heat is transferred under constant pressure

qp = nC p,m ∆T = (4.38... × 103 mol) × (21 J K−1 mol−1 ) × (10 K) = 9.21 × 105 J

�e time needed to transfer this heat is ∆t = (9.21... × 105 J)�(1500 J s−1 ) =

6.1 × 102 s .

P�B.� Fitting the data set using a computer program to an expression in the form of
C −p,m
○
(T) = a+bT+cT −2 yields a = 28.8 J K−1 mol−1 , b = 2.79×10−2 J K−2 mol−1
and c = −1.51×105 J K mol−1 . Fitting the data set to an expression in the form of
C −p,m
○
(T) = α+βT+γT 2 yields α = 24.6 J K−1 mol−1 , β = 3.83×10−2 J K−2 mol−1
and γ = −6.58 × 10−6 J K−3 mol−1 . �is second expression gives a slightly better
�t to the data set than the �rst expression.
D�C.� When a system is subjected to constant pressure conditions, and only expan-
sion work can occur, the energy supplied as heat is the change in enthalpy of the
system. �us enthalpy changes in the system can be determined by measuring
the amount of heat supplied under constant-pressure conditions.
A very simple example o�en encountered in elementary laboratory classes is a
thermally insulated vessel (for example, a foam plastic co�ee cup) le� open to
the atmosphere: the heat released in the reaction is determined by measuring
the change in temperature of the contents.
For a combustion reaction a constant-pressure �ame calorimeter (Section �B.�(b)
on page ��) may be used. In this apparatus a certain amount of substance
burns in a supply of oxygen and the rise in temperature is monitored. More
sophisticated methods include isothermal titration calorimetry and di�erential
scanning calorimetry, both described in Section �C.� on page ��.

D�C.� �e main objection to the use of the term ‘heat’ to describe the energy change
associated with a physical or chemical process is that heat is not a state function.
�e value of the heat therefore depends on the path chosen.
If, in fact, the processes being described takes place at constant pressure, the
heat is equal to the enthalpy change. Because enthalpy is a state function, the
heat measured under these circumstance is a property of the physical or chem-
ical change itself, and not a�ected by the path taken, and so is a meaningful and
useful quantity to discuss.
It is more appropriate to talk about the enthalpy change, the change in a state
function, rather to talk about the heat which, because of an unstated restriction,
just so happens to have the same value.

E�C.�(b) Ethanol is vaporized at constant pressure, therefore q = ∆H.

q = ∆H = n∆ vap H −○ = (1.75 mol) × (43.5 kJ mol−1 ) = +76.1... kJ = +76.1 kJ
�e work of expansion under constant pressure is given by [�A.�–��], w =
−pex ∆V . Note that ∆V = Vf because the �nal state (gas) has a much larger
volume than the initial state (liquid). �e perfect gas law is used to calculate
Vf .
nRT
w = −pex ∆V = −pex (Vf − Vi ) ≈ −pex Vf = −pex × = −nRT
pex
= −(1.75 mol) × (8.3145 J K−1 mol−1 ) × (260 K) = −3.78... kJ = −3.78 kJ

�e First Law of thermodynamics [�A.�–��] gives

∆U = q + w = (+76.1 kJ) + (−3.78... kJ) = +72.3 kJ
E�C.�(b) �e chemical equation for combustion of phenol is C� H� O(s) + � O� (g) ��→
� CO� (g) + � H� O(l). �e standard enthalpy of combustion is calculated us-
ing [�C.�a–��] and using values for the standard enthalpies of formation from
Table �C.�.

∆ c H −○ = � ν∆ f H −
−
○
� ν∆ f H −○
products reactants

= 6∆ f H (CO2 , g) + 3∆ f H −○ (H2 O, l) − 7∆ f H −○ (O2 , g) − ∆ f H −○ (C6 H6 O, s)

−
○

= 6 × (−393.51 kJ mol−1 ) + 3 × (−285.83 kJ mol−1 )

− 0 − (−165.0 kJ mol−1 ) = −3054 kJ mol−1

E�C.�(b) �e standard enthalpy of formation of HI(aq) is ∆ r H −○ for the reaction

1
H (g) + 12 I2 (g)
2 2
��→ HI(aq)

Because HI is a strong acid, the reaction is e�ectively

1
H (g) + 12 I2 (g)
2 2
��→ H+ (aq) + I− (aq)

By de�nition, ∆ f H −○ (H+ , aq) = 0, so ∆ r H −○ for this reaction is ∆ f H −○ (I− , aq).

∆ r H −○ = ∆ f H −○ (I− , aq) = −55 kJ mol−1

E�C.�(b) �e equation for combustion of anthracene is C14 H10 (s) + 33 O2 (g) ��→
14 CO2 (g) + 5 H2 O(l). In a bomb calorimeter the heat is at constant volume
2

and is given by qv = n∆ c U −○ . ∆ c U −○ is related to ∆ c H −○ by [�B.�–��], ∆ r H −○ =

∆ r U −○ + ∆ng RT, where ∆ng is the change in the amount of gas molecules in the
reaction. In this case ∆ng = 16.5 mol − 14 mol = −2.5 mol, hence

∆ c U −○ = ∆ c H −○ − ∆ng RT
= (−7.06... × 106 J) − (−2.5 mol) × (8.3145 J K−1 mol−1 ) × (298 K)
= −7.05... × 103 kJ mol−1

�e heat released in the bomb calorimeter on combustion of 2.25 mg of an-

thracene (M = 178.219 g mol−1 ) is

2.25 × 10−3 g
qv = n∆ c U −○ = � �×(−7.05...×103 kJ mol−1 ) = −8.90 ...×10−2 kJ
178.219 g mol−1

�erefore the calorimeter constant is

�qv � (8.90 ... × 10−2 kJ)
C= = = 5.08... × 10−2 kJ K−1 = 5.09 × 10−2 kJ K−1
∆T (1.75 K)

�e chemical equation for combustion of phenol is C� H� O(s) + � O� (g) ��→

� CO� (g)+� H� O(l). Following the same logic as above, ∆ c H −○ = −3054 kJ mol−1 ,
 ∆ng = −1 mol and ∆ c U −○ = −3.05... × 103 kJ mol−1 . �e heat released on
combustion of 125 mg of phenol (M = 94.10 g mol−1 ) is

0.125 g −1
qv = n∆ c U −○ = � −1 � × (−3.05... × 10 kJ mol ) = −4.05... kJ
3
94.1074 g mol

�erefore ∆T = �qv ��C = (4.05... kJ)�(5.08... × 10−2 kJ K−1 ) = +79.6 K

E�C.�(b) (i) Reaction(�) is reaction(�) − � × reaction(�), therefore

∆ r H −○ (3) = ∆ r H −○ (2) − 2∆ r H −○ (1)

= (−483.64 kJ mol−1 ) − 2 × (+52.96 kJ mol−1 )
= −589.56 kJ mol−1

�e relationship between ∆ r H and ∆ r U is given by [�B.�–��], ∆ r H =

∆ r U + ∆ng RT where ∆ng is the change in the amount of gas molecules
in the reaction. For this reaction ∆ng = 2 mol + 2 mol − 4 mol − 1 mol =
−1 mol

∆ r U −○ = ∆ r H −○ − ∆ng RT
= (−589.56 × 103 J mol−1 )
− (−3.0 mol) × (8.3145 J K−1 mol−1 ) × (298 K) = −582 kJ mol−1

(ii) Reaction(�) represents the formation of � moles of HI(g) from its elements
in their reference states, therefore the standard enthalpy of formation of
HI(g) is

∆ f H −○ (HI, g) = 12 ∆ r H −○ (1) = 1
2
× (+52.96 kJ mol−1 ) = +26.48 kJ mol−1

Reaction(�) represents the formation of � moles of H� O(g) from its ele-

ments in their reference states, therefore

∆ f H −○ (H2 O, g) = 12 ∆ r H −○ (2) = 12 ×(−483.64 kJ mol−1 ) = −241.82 kJ mol−1

E�C.�(b) �e relationship between ∆ r H and ∆ r U is given by [�B.�–��], ∆ r H = ∆ r U +

∆ng RT where ∆ng is the change in the amount of gas molecules in the reaction.
For this reaction ∆ng = 14 mol + 6 mol − 15 mol = +5 mol

∆ r H −○ = ∆ r U −○ + ∆ng RT
= (−772.7 × 103 J mol−1 ) + (+5.0 mol) × (8.3145 J K−1 mol−1 ) × (298 K)
= −760.3 kJ mol−1

E�C.�(b) �e following reactions are used to construct a thermodynamic cycle which

gives the standard enthalpy of hydrogenation of ethyne to ethene.
 reaction ∆ r H −○ �kJ mol−1
(�) C� H� (g) + 52 O� (g) ��→ � CO� (g) + H� O(l) −1300
(�) C� H� (g) + � O� (g) ��→ � CO� (g) + � H� O(l) −1411
(�) H� (g) + 12 O� (g) ��→ H� O(l) −285.83
(�) C� H� (g) + H� (g) ��→ C� H� (g) ∆ r H −○ (4)

∆ r H −○ (4) = ∆ r H −○ (1) + ∆ r H −○ (3) − ∆ r H −○ (2)

= (−1300 kJ mol−1 ) + (−285.83 kJ mol−1 ) − (−1411 kJ mol−1 )
= −174.83 kJ mol−1

�e relationship between ∆ r H and ∆ r U is given by [�B.�–��], ∆ r H = ∆ r U +

∆ng RT where ∆ng is the change in the amount of gas molecules in the reaction.
For this reaction ∆ng = 1 mol − 1 mol − 1 mol = −1 mol

∆ r U −○ (298 K) = ∆ r H −○ (298 K) − ∆ng RT

= (−174.83 × 103 J mol−1 ) − (−1.0 mol) × (8.3145 J K−1 mol−1 )
× (298 K) = −172 kJ mol−1

�e di�erence of the molar heat capacities of products and reactants is cal-

culated using [�C.�b–��] and the corresponding heat capacity data from the
Resource section

∆ r C −p○ = � νC p,m −
−
○
� νC −p,m
○

products reactants

= C −p,m
○
(C2 H4 , g) − C −p,m
○
(C2 H2 , g) − C −p,m
○
(H2 , g)
−1
= (43.56 J K −1
mol ) − (43.93 J K −1
mol ) − (28.824 J K−1 mol−1 )
−1

= −29.1... J K−1 mol−1

It is assumed that all heat capacities are constant over the temperature range of
interest, therefore the integrated form of Kirchho� ’s Law is applicable, [�C.�d–
��]

∆ r H −○ (427 K) = ∆ r H −○ (298 K) + ∆T∆ r C −p○

= (−174.83 × 103 J mol−1 )
+ (427 K − 298 K) × (−29.1... J K−1 mol−1 ) = −179 kJ mol−1

E�C.�(b) �e reaction equation 12 N2 (g) + 32 H2 (g) ��→ NH3 (g) represents the forma-
tion of NH� (g) from its elements in their reference states, therefore ∆ r H −○ (298 K) =
∆ f H −○ (NH3 , g) = −46.11 kJ mol−1 . �e variation of standard reaction enthalpy
with temperature is given by Kirchho� ’s Law, [�C.�a–��]
T2
∆ r H −○ (T2 ) = ∆ r H −○ (T1 ) + � ∆ r C −p○ dT
T1
 �e di�erence of the molar heat capacities of products and reactants is given
by [�C.�b–��]

∆ r C −p○ = � νC p,m −
−
○
� νC −p,m
○

products reactants

= C −p,m
○
(NH3 , g) − 32 C −p,m
○
(H2 , g) − 21 C −p,m
○
(N2 , g)

�e heat capacities in Table �B.� are expressed in the form of C −p,m

○
= a + bT +
c�T therefore ∆ r C p = ∆a+∆bT +∆c�T where ∆a = a(NH3 , g)− 32 a(H2 , g)−
2 −
○ 2
1
2
a(N2 , g) and likewise for ∆b and ∆c.

∆a = (29.75 J K−1 mol−1 ) − 32 × (27.28 J K−1 mol−1 ) − 12 × (28.58 J K−1 mol−1 )

= −25.46 J K−1 mol−1
∆b = (25.1 × 10−3 J K−2 mol−1 ) − 32 × (3.26 × 10−3 J K−2 mol−1 )
− 12 × (3.77 × 10−3 J K−2 mol−1 ) = +18.325 × 10−3 J K−2 mol−1
∆c = (−1.55 × 105 J K mol−1 ) − 32 × (0.50 × 105 J K mol−1 )
− 12 × (−0.50 × 105 J K mol−1 ) = −2.05 × 105 J K mol−1

Integrating Kirchho� ’s Law gives

T2 ∆c
∆ r H −○ (T2 ) = ∆ r H −○ (T1 ) + � �∆a + ∆bT + � dT
T1 T2
1 1
= ∆ r H −○ (T1 ) + ∆a(T2 − T1 ) + 12 ∆b(T22 − T12 ) − ∆c �
− �
T2 T1
= (−46.11 × 103 J mol−1 ) + (−25.46 J K−1 mol−1 ) × (750 K − 298 K)
+ 12 × (+18.325 × 10−3 J K−2 mol−1 ) × [(750 K)2 − (298 K)2 ]
1 1
− (−2.05 × 105 J K mol−1 ) × � − �
750 K 298 K
= −53.7 kJ mol−1

P�C.� �e combustion equation for octane is C� H�� (l) + ��.� O� (g) ��→ � CO� (g) +
� H� O(l). �e standard enthalpy of combustion of octane is given in Table �C.�
as −5471 kJ mol−1 . �e amount in moles in 1.0 dm3 octane is

m ρV (0.703 g cm−3 ) × (1.0 × 103 cm3 )

n= = = = 6.15... mol
M M (114.2222 g mol−1 )
�e heat is

qp = n∆ c H −○ = (6.15... mol) × (−5471 kJ mol−1 ) = 3.4 × 104 kJ

P�C.� ∆ f H −○ (B� H� , g) is the standard enthalpy change of � B(s)+� H� (g) ��→ B� H� (g).
�is reaction is � × reaction(�) + reaction(�) − reaction(�) = reaction(�), and
 so

∆ f H −○ (B2 H6 , g) = 3∆ r H −○ (3) + ∆ r H −○ (2) − ∆ r H −○ (1)

∆ f H −○ (B2 H6 , g) = 3 × (−241.8 kJ mol−1 ) + (−2368 kJ mol−1 ) − (−1941 kJ mol−1 )
= −1152.4 kJ mol−1

P�C.� �e relationship between ∆ r H and ∆ r U is given by [�B.�–��], ∆ r H = ∆ r U +

∆ng RT where ∆ng is the change in the amount of gas molecules in the reaction.
For this reaction ∆ng = 2 mol − 0 mol = +2 mol

∆ r H −○ = ∆ r U −○ + ∆ng RT
= (+8.0 × 103 J mol−1 ) + (2.0 mol) × (8.3145 J K−1 mol−1 ) × (583 K)
= 17.6... kJ mol−1 = +18 kJ mol−1

Applying [�C.�a–��] to this reaction gives

∆ r H −○ = 2∆ f H −○ (C6 H6 , g) + ∆ f H −○ (Cr, s) − ∆ f H −○ (Cr(C6 H6 )2 , s)

�e standard enthalpies of formation of elements in their reference states are

zero at all temperatures, therefore ∆ f H −○ (Cr, s, 583 K) = ∆ f H −○ (Cr, s, 298 K) =
0. ∆ f H −○ (C� H� , g, ��� K) is equal to ∆ r H −○ of the reaction � C(s) + � H� (g) ��→
C� H� (g) at ��� K. �e di�erence of the molar heat capacities of products and
reactants of this reaction is calculated using [�C.�b–��] and data from Table
�C.�

∆ r C −p○ = � νC p,m −
−
○
� νC −p,m
○

products reactants

= C −p,m
○
(C6 H6 , g) − 3C −p,m
○
(H2 , g) − 6C −p,m
○
(graphite, s)
= (81.67 J K−1 mol−1 ) − 3 × (28.824 J K−1 mol−1 ) − 6 × (8.527 J K−1 mol−1 )
= −55.9... J K−1 mol−1

Assuming that ∆ r C −p○ is independent of temperature in the given range, using

data from Table �C.� and applying Kirchho� ’s Law [�C.�d–��] gives

∆ f H −○ (C6 H6 , g, 583 K) = ∆ r H −○ (583 K) + ∆ r H −○ (298 K) + ∆T∆ r C −p○

= (+82.93 × 103 J mol−1 ) + (583 K − 298 K)
× (−55.9... J K−1 mol−1 ) = +66.9... kJ mol−1

�erefore the standard enthalpy of formation of the chromium complex at 583 K

is

∆ f H −○ (Cr(C6 H6 )2 , s, 583 K) = 2∆ f H −○ (C6 H6 , g, 583 K) + ∆ f H −○ (Cr, s) − ∆ r H −○

= 2 × (+66.9... kJ mol−1 ) + 0 − (+17.6... kJ mol−1 )
= +116 kJ mol−1
P�C.� (a) Using [�C.�a–��] and the values for the standard enthalpies of formation
given in the problem

∆ r H −○ = � ν∆ f H −
−
○
� ν∆ f H −○
products reactants

= ∆ f H −○ (SiH2 , g) + ∆ f H −○ (H2 , g) − ∆ f H −○ (SiH4 , g)

= (+274 kJ mol−1 ) + 0 − (+34.3 kJ mol−1 ) = +239.7 kJ mol−1

(b) Similarly to part (a)

∆ r H −○ = ∆ f H −○ (SiH2 , g) + ∆ f H −○ (SiH4 , g) − ∆ f H −○ (Si2 H6 , g)

= (+274 kJ mol−1 ) + (+34.3 kJ mol−1 ) − (+80.3 kJ mol−1 )
= +228.0 kJ mol−1

�e enthalpy change is found using [�C.�–��], ∆H = ∫T12 C p,ex dT, where C p,ex
T
P�C.��
is the excess heat capacity reported by the instrument. �e integral is the area
under the trace, which is estimated to be ��� mJ: this is the estimate for ∆H.
From the data given the amount in moles in the sample volume of �.�� cm3 is
(0.80 cm3 ) × (2.17 × 10−3 g cm−3 )�(14.3 × 103 g mol−1 ) = 1.21... × 10−7 mol.
�e molar enthalpy of unfolding is therefore

∆H m = (230 × 10−3 J)�(1.21... × 10−7 mol) = 1.9 × 103 kJ mol−1

D�D.� An inversion temperature is the temperature at which the Joule–�omson co-

e�cient µ changes sign from negative to positive or vice-versa. For a perfect
gas µ is always zero, thus it cannot have an inversion temperature. As explained
in detail in Section �D.� on page ��, the existence of the Joule–�omson e�ect
depends upon intermolecular attractions and repulsions. A perfect gas has by
de�nition no intermolecular attractions and repulsions, so it cannot exhibit the
Joule–�omson e�ect.

E�D.�(b) �e molar volume of a perfect gas at 298 K is calculated as

RT (8.3145 J K−1 mol−1 ) × (298 K)

Vm = = = 2.47... × 10−2 m3 mol−1
p (1.00 bar) × [(105 Pa)�(1.00 bar)]
 �e van der Waals parameter a of sulfur dioxide is found in Table �C.�, and
needs to be converted to SI units
−2 10−6 m6 1.01325 × 105 Pa
a = (6.775 dm6 atm mol ) × � � × � �
1 dm6 1 atm
−2
= 0.686... m6 Pa mol
�erefore the internal pressure is
−2
a (0.686... m6 Pa mol )
πT = = = 1.12 × 103 Pa
Vm (2.47... × 10−2 m3 mol−1 )2
2

E�D.�(b) �e internal energy of a closed system of constant composition is a function of

temperature and volume. For a change in V and T, dU is given by [�D.�–��],
dU = π T dV + C V dT. At constant temperature, this reduces to dU = π T dV .
Substituting in the given expression for π T for a van der Waals gas and using
molar quantities
a
dUm = 2 dVm
Vm
�is expression is integrated between Vm,i and Vm,f to give
Vm,f Vm,f a
� dU m = � dVm
Vm,i Vm,i Vm2
hence
Vm,f
a 1 1
∆U m = − � = −a � − �
Vm Vm,i
2 Vm,f Vm,i
�e van der Waals parameter a for argon is found in Table �C.�, and needs to
be converted to SI units
−2 10−6 m6 1.01325 × 105 Pa
a = (1.337 dm6 atm mol ) × � � × � �
1 dm6 1 atm
−2
= 0.135... m6 Pa mol
−2 1 1
∆Um = −(0.135... m6 Pa mol ) � − �
30.00 × 10−3 m3 mol−1 1.00 × 10−3 m3 mol−1
= +1.30... × 102 J mol−1 = +131 J mol−1
�e work done by an expanding gas is given by [�A.�a–��], dw = −pex dV . For
a reversible expansion pex is the pressure of the gas, hence

w = − � pdVm

Substituting in the expression for the pressure of a van der Waals gas, [�C.�b–
��]
RT a RT a
w = −� − 2 dVm = − � dVm + � dVm
Vm − b Vm Vm − b Vm2
RT
= −� dVm + ∆Um
Vm − b
 �e second term is identi�ed as ∆U m from the above. According to the First
Law, ∆U = q + w, the �rst term in the expression above must be −q, therefore
Vm,f RT Vm,f − b
q=� dVm = RT ln(Vm − b)�Vm,f = RT ln � �
V
Vm,i Vm − b m,i
Vm,i − b
30.00 dm3 − 3.20 × 10−2 dm3
= (8.3145 J K−1 mol−1 ) × (298 K) × ln � �
1.00 dm3 − 3.20 × 10−2 dm3
= +8.50... × 103 J mol−1 = +8.51 kJ mol−1

where the value for b is taken from the Resource section. From the First Law
the work done is w = −q + ∆Um , hence

w = −q + ∆Um = −8.50... ×103 J mol−1 +1.30... ×102 J mol−1 = −8.37 kJ mol−1

E�D.�(b) �e volume of the liquid can be written as

V = V ′ (a + bT + cT 2 )

where a = 0.77, b = 3.7 × 10−4 K−1 and c = 1.52 × 10−6 K−2 . �e expansion
coe�cient is de�ned in [�D.�–��] as α = (1�V )(∂V �∂T) p . �e derivative with
respect to T is
∂V
� � = V ′ (b + 2cT)
∂T p
�erefore
1 b + 2cT
α= × [V ′ (b + 2cT)] =
V ′ (a + bT + cT )
2 a + bT + cT 2

Evaluating this expression at 310 K gives

(3.7 × 10−4 K−1 ) + 2 × (1.52 × 10−6 K−2 ) × (310 K)

α 310 =
(0.77) + (3.7 × 10−4 K−1 ) × (310 K) + (1.52 × 10−6 K−2 ) × (310 K)2
= +1.3 × 10−3 K−1

E�D.�(b) �e isothermal compressibility is de�ned in [�D.�–��], κ T = −(1�V )(∂V �∂p)T ,

therefore at constant temperature dV �V = −κ T dp. �is question is concerned
with changes in density, so the next step is to rewrite the volume in terms of
the density, ρ. If the mass is m, V = m�ρ, and therefore dV = (−m�ρ 2 )dρ.
�erefore
dV 1 m ρ m 1
= �− 2 dρ� = − � � � 2 � dρ = − dρ
V V ρ m ρ ρ
It therefore follows that
dρ 1
= κ T dp and hence dp = dρ
ρ κT ρ
 �is expression gives the relationship between the change in pressure and the
change in density. Approximating dρ by δρ and dp by δ p for su�ciently small
changes gives

1 δρ 1
δp = × =� � × (1.0 × 10−3 ) = +4.5 × 102 atm
κT ρ 2.21 × 10−6 atm−1

E�D.�(b) �e di�erence C p,m − C V ,m is given by [�D.��–��], C p,m − C V ,m = α 2 T Vm �κ T .

In this expression the molar volume is found from the mass density ρ and the
molar mass M by Vm = M�ρ. �e values of α and κ are available in the Resource
section, as is the mass density.

α 2 T Vm α 2 TM
C p,m − C V ,m = =
κT κT ρ
(11.2 × 10−4 K−1 )2 × (298 K) × (46.0674 g mol−1 )
=
[(76.8 × 10−6 bar) × (1 bar�105 Pa)] × (0.789 × 106 g m−3 )
= +28.4 J K−1 mol−1

�e units are K−1 Pa m3 mol−1 = K−1 (N m−2 ) m3 mol−1 = K−1 N m mol−1

= J K−1 mol−1

P�D.� �e pressure p is a function of T and V , therefore according to the Euler chain

relation and the reciprocal identity

∂p ∂p ∂V
� � = −� � � �
∂T V ∂V T ∂T p

Substituting this into the expression given for C p − C V gives

∂p ∂V ∂p ∂V ∂V
C p − CV = T � � � � = −T � � � � � �
∂T V ∂T p ∂V T ∂T p ∂T p
T(∂V �∂T)2p
=−
(∂V �∂p)T

For a perfect gas pV = nRT, therefore

∂V nR ∂V nRT
� � = and � � =− 2
∂T p p ∂p T p

It follows that
T(nR�p)2
C p − CV = − = nR
(−nRT�p2 )
which is the expected result quoted in [�B.�–��].
P�D.� Rearranging the van der Waals equation of state to give T as a function of p
and V gives

p(V − nb) na(V − nb)

T= +
nR V 2R

�e partial di�erentials are

∂T V − nb ∂p nR
� � = and � � =
∂p V nR ∂T V V − nb

As expected, these two partial di�erentials are the reciprocals of each other.

∂T 1
� � =
∂p V (∂p�∂T)V

P�D.� From the perfect gas law, [�A.�–�], pV = nRT. Writing n = m�M, where m is
the mass, it follows that

m RT pV
pV = RT and hence =
M M m

�e mass density, ρ is ρ = m�V , therefore (RT�M) = ρ�p.

1�2
γRT 1�2 γp
cs = � � =� �
M ρ

For argon, a monoatomic gas, C V ,m = 32 R and C p,m = 52 R therefore γ = C p,m �C V ,m

= 5�3.

−1
� 53 × (8.3145 J K−1 mol ) × (298.15 K) �
1�2

cs = = 322 m s−1
� (39.95 × 10−3 kg mol−1 ) �

P�D.� In How is that done? �D.� on page �� is is shown that

1 ∂H
µ=− � �
C p ∂p T
An expression for (∂H�∂p)T is developed as follows

∂H ∂H ∂V
� � =� � � � [change of variable]
∂p T ∂V T ∂p T
∂(U+pV ) ∂V
=� � � � [de�nition of H]
∂V T
∂p T
∂U ∂V ∂(pV ) ∂V
=� � � � +� � � �
∂V T ∂p T ∂V T ∂p T
∂p ∂V ∂(pV ) ∂U
= �T� � −p� � � +� � � equation for � � �
∂T V ∂p T ∂p T
∂V T
∂p ∂V ∂V ∂V
= T� � � � −p� � +V +p� �
∂T V ∂p T ∂p T ∂p T
∂p ∂V −T
= T� � � � +V = +V [chain relation]
∂T V ∂p T (∂T�∂V ) p
∂V
= −T� � +V [reciprocal identity]
∂T p
With this result
1 ∂H 1 ∂V
µ=− � � = �T � � − V�
C p ∂p T C p ∂T p

In order to compute the partial derivative (∂V �∂T) p it is convenient to take

the van der Waals equation and re-express it in the form of a virial expansion

RT a RT 1 a
p= − 2 = � − �
Vm − b Vm Vm 1 − b�Vm RT Vm

Assuming b�Vm � 1, the �rst fraction can be approximated using (1 − x)−1 ≈

1+x
RT b a
p= �1 + − �
Vm Vm RT Vm
RT b a 1 b a
hence Vm = �1 + − � = RT � + − �
p Vm RT Vm p pVm RT pVm

Within the parentheses the perfect gas equation is used to approximate pVm =
RT

1 b a RT a
Vm = RT � + − 2 2� = +b−
p RT R T p RT

It is now straightforward to compute the required partial derivative

∂Vm R a
� � = +
∂T p p RT 2
 Using this in the expression above for µ and switching to molar quantities

1 ∂Vm 1 R a
µ= �T � � − Vm � = �T � + � − Vm �
C p,m ∂T p C p,m p RT 2

�e above expression for Vm is used once more

1 R a RT a
µ= �T � + �−� +b− ��
C p,m p RT 2 p RT
1 RT a RT a
= � + − −b+ �
C p,m p RT p RT
1 2a
= � − b�
C p,m RT

which is the required result.

D�E.� In an adiabatic expansion the system does work but as no energy as heat is
permitted to enter the system, the internal energy of the system falls and so
consequently does the temperature. From the First Law, ∆U = w because q =
0. However, the change in internal energy is also related to the temperature
change and the heat capacity: ∆U = C V ∆T. Equating these two expressions
for ∆U gives w = C V ∆T, or dw = C V dT for an in�nitesimal change.
For a reversible expansion, the work is dw = −pdV . Equating these two ex-
pressions for the work gives −pdV = C V dT. �is equation is the point from
which the relationships between pressure, volume and temperature for a re-
versible adiabatic expansion are found: the heat capacity comes into the �nal
expressions via this route.
In words, the key thing here is that in an adiabatic process there is a change
in temperature, so it is not surprising that the properties of such a process are
related to the heat capacity because this quantity relates the energy and the
temperature rise.

E�E.�(b) Carbon dioxide is a linear polyatomic molecule which has three degrees of
translational and two degrees of rotational freedom. From the equipartition
theorem
C V ,m = 12 × (νt + νr + 2νv ) × R
where νt is the number of translational degrees of freedom, νr is the number
of rotational degrees of freedom and νv is the number of vibrational degrees of
freedom.
 (i) Without any vibrational contribution: C V ,m = 12 × (3 + 2 + 0) × R = 52 R.
For a perfect gas, [�B.�–��], C p,m = C V ,m + R, therefore

C V ,m + R 2 R + R 7
5
γ= = 5 = ≈ 1.40
C V ,m 2
R 5

(ii) With the vibrational contribution: �e number of vibrational modes is

νv = 3N − 5 for a linear molecule, where N is the number of atoms in the
molecule. �erefore νv = 3N − 5 = 4. �is gives C V ,m = 12 × (3 + 2 + 2 ×
4) × R = 13
2
R and thus C p,m = 15
2
R and so γ = 15�13 ≈ 1.15.
�e experimental value of γ for carbon dioxide is

C p,m C p,m (37.11 J K−1 mol−1 )

γ= = = = 1.29
C V ,m C p,m − R (37.11 J K−1 mol−1 ) − (8.3145 J K−1 mol−1 )
which is somewhat closer to the value expected if vibration is neglected, but
does not match that value closely. �is indicates that vibrations may be con-
tributing somewhat - for example the lower frequency bending modes.

E�E.�(b) For a reversible adiabatic expansion the initial and �nal states are related by
[�E.�a–��], (Tf �Ti ) = (Vi �Vf )1�c , where c = C V ,m �R. For a perfect gas C p,m −
C V ,m = R, [�B.�–��], so c = (C p,m − R)�R. Using the value of C p,m from the
Resource section gives

(37.11 J K−1 mol−1 ) − (8.3145 J K−1 mol−1 )

c= = 3.463
(8.3145 J K−1 mol−1 )
�erefore
1 1
Vi c 500 cm3
Tf = Ti � � = (298.15 K) × � �
3.463

= 200 K
Vf 2.00 × 10 cm
3 3

E�E.�(b) For a reversible adiabatic expansion the initial and �nal states are related by
[�E.�–��], p i Vi = p f Vf , where γ is the ratio of heat capacities, γ = C p,m �C V ,m .
γ γ

�e initial volume of the sample is

nRT (2.5 mol) × (8.3145 J K−1 mol−1 ) × (325 K)

Vi = = = 2.81... × 10−2 m3
p (2.40 × 105 Pa)
= 28.1... dm3

For a perfect gas C p,m − C V ,m = R, hence

C p,m C p,m (20.8 J K−1 mol−1 )

γ= = = = 1.66...
C V ,m C p,m − R (20.8 J K−1 mol−1 ) − (8.3145 J K−1 mol−1 )
�e �nal volume is given by

Vf = (28.1... dm3 )×(2.40×105 Pa�1.50×105 Pa)1�1.66... = 37.3... dm3 = 37 dm3

 �e initial and �nal states are also related by (Tf �Ti ) = (Vi �Vf )1�c where c =
C V ,m �R. For this gas

(20.8 J K−1 mol−1 ) − (8.3145 J K−1 mol−1 )

c= = 1.50...
(8.3145 J K−1 mol−1 )
and hence
1�1.50...
Vi 1�c 28.1... dm3
Tf = Ti � � = (325 K) × � � = 2.69... × 102 K = 269 K
Vf 37.3 dm3
�e work done by a perfect gas during adiabatic expansion is given by [�E.�–��]
w ad = C V ∆T = nC V ,m (Tf − Ti ) = n(C p,m − R)(Tf − Ti )
= (2.5 mol) × [(20.8 J K−1 mol−1 ) − (8.3145 J K−1 mol−1 )]
× (2.69... × 102 K − 325 K) = −1.7 kJ

E�E.�(b) �e work done in a reversible adiabatic expansion is given by [�E.�–��], w ad =

C V ∆T. �e task is to �nd ∆T. �e initial and �nal states in a reversible adia-
batic expansion are related by [�E.�b–��], Vi Tic = Vf Tfc , where c = C V ,m �R. If
the gas is assumed to be perfect, C p,m − C V ,m = R [�B.�–��], and so

C V ,m C p,m − R (29.125 J K−1 mol−1 ) − (8.3145 J K−1 mol−1 )

c= = = = 2.50...
R R (8.3145 J K−1 mol−1 )
�e temperature change is given by

Vi 1�c Vi 1�c
∆T = Tf − Ti = Ti � � − Ti = Ti �� � − 1�
Vf Vf
�erefore the work done is
Vi 1�c
w ad = C V ∆T = nC V ,m ∆T = nC V ,m Ti �� � − 1�
Vf
Vi 1�c
= n(C p,m − R)Ti �� � − 1�
Vf
3.12 g
=� � × [(29.125 J K−1 mol−1 )
28.02 g mol−1
� 1�2.50... �
� �
− (8.3145 J K−1 mol−1 )] × (296.15 K) × � − 1�
400 cm3
�
� 2.00 × 103 cm3 � �
� �
� �
= −325 J

E�E.�(b) �e initial and �nal states in a reversible adiabatic expansion are related by
[�E.�–��], p i Vi = p f Vf , therefore
γ γ

1.3
Vi γ 400 cm3
pf = pi � � = (97.3 Torr) × � � = 3.6 Torr
Vf 5.0 × 103 cm3
P�E.� In a reversible adiabatic expansion the initial and �nal states are related by
[�E.�a–��], (Tf �Ti ) = (Vi �Vf )1�c where c = C V ,m �R. Taking the logarithm
of both sides and using the relationship ln x a = a ln x gives
Tf 1 Vi
ln � � = ln � �
Ti c Vf
It follows that
ln (Vi �Vf ) ln (1�2)
c= = = 3.80...
ln (Ti �Tf ) ln (248.44 K�298.15 K)
C V ,m is calculated from c as follows

C V ,m = cR = (3.80...) × (8.3145 J K−1 mol−1 ) = 31.5... J K−1 mol−1

Likewise, the initial and �nal states are related by [�E.�–��], p i Vi = p f Vf ,

γ γ

where γ = C p,m �C V ,m . It follows that ln(p i �p f ) = γ ln(Vf �Vi ), hence

ln (p f �p i ) ln (81.840 kPa�202.94 kPa)

γ= = = 1.31...
ln (Vi �Vf ) ln (1�2)
Hence

C p,m = C V ,m γ = (31.5... J K−1 mol−1 ) × (1.31...) = 41.397 J K−1 mol−1

I�.� (a) �e table below displays computed enthalpies of formation (semi-empirical,

PM� level, PC Spartan ProTM ), enthalpies of combustion based on them
(and on experimental enthalpies of formation of H� O(l), −285.83 kJ mol−1 ,
and CO� (g), −393.51 kJ mol−1 ), experimental enthalpies of combustion
(from the Resource section), and the relative error in the enthalpy of com-
bustion.

compound ∆ f H −○ �kJ mol−1 ∆ c H −○ �kJ mol−1 ∆ c H −○ �kJ mol−1 % error

(calc.) (expt.)
CH� (g) −54.45 −910.7 −890 �.��
C� H� (g) −75.88 −1568.6 −1560 �.��
C� H� (g) −98.84 −2225.0 −2220 �.��
C� H�� (g) −121.6 −2881.6 −2878 �.��
C� H�� (g) −142.1 −3540.4 −3537 �.��

�e combustion reactions can be expressed as

Cn H2n+2 (g) + 12 (3n + 1)O2 (g) ��→ n CO2 (g)+(n+1)H2 O(l)

 �e enthalpy of combustion, in terms of enthalpies of formation, is
∆ c H −○ = n∆ f H −○ (CO2 ) + (n + 1)∆ f H −○ (H2 O) − ∆ f H −○ (Cn H2n+2 )
�e % error is de�ned as
∆ c H −○ (calc.) − ∆ c H −○ (expt.)
% error = × 100%
∆ c H −○ (expt.)
(b) �e errors are shown in the table above. It is evident that the agreement
is quite good.
(c) If the enthalpy of combustion is related to the molar mass by
∆ c H −○ = k[M�(g mol−1 )]n
it follows by taking logarithms that
ln �∆ c H −○ � = ln k + n ln[M�(g mol−1 )]
A plot of ln �∆ c H −○ � against ln[M�(g mol−1 )] is expected to be a straight
line with slope n and y-intercept ln �k�; see Fig. �.�.

compound M� ∆ c H −○ / ln[M�(g mol−1 )] ln �∆ c H −○ �(kJ mol−1 )�

g mol−1 kJ mol−1
CH� (g) ��.�� −910.72 �.��� �.���
C� H� (g) ��.�� −1568.6 �.��� �.���
C� H� (g) ��.�� −2225.0 �.��� �.���
C� H�� (g) ��.�� −2881.6 �.��� �.���
C� H�� (g) ��.�� −3540.4 �.��� �.���

8.5
ln �∆ c H −○ �(kJ mol−1 )�

8.0

7.5

7.0

6.5
2.5 3.0 3.5 4.0 4.5
−1
ln[M�(g mol )]

�e data are a good �t to the line

ln �∆ c H −○ �(kJ mol−1 )� = 0.90 × (ln[M�(g mol−1 )]) + 4.30
 �e data from these compounds support the proposed relationship, with
the parameters n = 0.90 and k = −e4.30 kJ mol−1 (g mol−1 )−0.9 , which is
k = −73.7 kJ mol−1 (g mol−1 )−0.9 .

I�.� �e change in reaction enthalpy with respect to temperature is described by

Kirchho� ’s Law, [�C.�a–��]. Assuming that the heat capacities are indepen-
dent of temperature, the integrated form of Kircho� ’s Law is applicable and is
given by [�C.�d–��]

∆ r H −○ (T2 ) = ∆ r H −○ (T1 ) + (T2 − T1 )∆ r C −p○

If ∆ r C −p○ is negative, then the reaction enthalpy will decrease with increasing
temperature, whereas if ∆ r C −p○ is positive, then the reaction enthalpy will in-
crease with increasing temperature.

(a)

∆ r C −p○ = � νC p,m −
−
○
� νC −p,m
○

products reactants

= 2C −p,m
○
(H2 O, l) − C −p,m
○
(O2 , g) − 2C −p,m
○
(H2 , g)
= 2 × (9R) − � 72 R� − 2 × � 72 R� = +7 12 R

∆ r C −p○ is positive, therefore the standard reaction enthalpy of reaction will

increase with increasing temperature.
(b)

∆ r C −p○ = C −p,m
○
(CO2 , g) + 2C −p,m
○
(H2 O, l) − 2C −p,m
○
(O2 , g) − C −p,m
○
(CH4 , g)
= � 72 R� + 2 × (9R) − 2 × � 72 R� − (4R) = +10 12 R

∆ r C −p○ is positive, therefore the standard reaction enthalpy of reaction will

increase with increasing temperature.

I�.� (a) From the equipartition principle (�e chemist’s toolkit � in Topic �A),
and assuming that only translational and rotational levels contribute, the
constant volume heat capacity of a gas of diatomic molecules is C V ,m =
5
2
R. For a perfect gas C p,m − C V ,m = R, [�B.�–��], therefore C p,m =
C V ,m + R = 72 R and so γ = C p,m �C V ,m = 75 . It follows that

γRT 1�2 7RT 1�2

cs = � � =� �
M 5M

(b) A linear triatomic has the same number of translational and rotational
modes of motion (three translational, two rotational) as a diatomic, so
the calculation is the same as in (a).
(c) A gas of non-linear triatomic molecules has one extra mode of rotational
motion when compared to a linear triatomic, so the constant volume heat
 capacity is C V ,m = 3R. Because C p,m − C V ,m = R it follows that C p,m =
C V ,m + R = 4R and so γ = C p,m �C V ,m = 43 .

γRT 1�2 4RT 1�2

cs = � � =� �
M 3M

�e air is mostly composed of diatomic and linear triatomic molecules, N� , O�

and CO� , hence γ ≈ 75 . �e average molecular weight of air is approximately
29.0 g mol−1 , therefore

7 × (8.3145 J K−1 mol−1 ) × (298.15 K)

1�2
7RT 1�2
cs = � � =� � = 346 m s−1
5M 5 × (29.0 × 10−3 kg mol−1 )
D�A.� Everyday experience indicates that the direction of spontaneous change in an
isolated system is accompanied by the dispersal of the total energy of the sys-
tem. For example, for a gas expanding freely and spontaneously into a vacuum,
the process is accompanied by a dispersal of energy and matter. For a perfect
gas this entropy change of such an expansion is derived in Section �A.�(a) on
page �� as ∆S = nR ln(Vf �Vi ). �e entropy change is clearly positive if Vf is
greater than Vi .
�e molecular interpretation of this thermodynamic result is based on the iden-
ti�cation of entropy with molecular disorder. An increase in disorder results
from the chaotic dispersal of matter and energy and the only changes that can
take place within an isolated system (the universe) are those in which this kind
of dispersal occurs. �is interpretation of entropy in terms of dispersal and
disorder allows for a direct connection of the thermodynamic entropy to the
statistical entropy through the Boltzmann formula S = k ln W, where W is
the number of microstates, the number of ways in which the molecules of the
system can be arranged while keeping the total energy constant.
�e concept of the number of microstates makes quantitative the more ill-
de�ned qualitative concepts of ‘disorder’ and ‘the dispersal of matter and en-
ergy’ used above to give a physical feel for the concept of entropy. A more
‘disorderly’ distribution of energy and matter corresponds to a greater number
of microstates associated with the same total energy.

E�A.�(b) For the process to be spontaneous it must be irreversible and obey the Clausius
inequality [�A.��–��] implying that ∆S tot = ∆S + ∆S sur > 0. In this case,
∆S tot = 105 J K−1 + (−95 J K−1 ) = +10 J K−1 , the total entropy increases and
thus the process is spontaneous .

E�A.�(b) �e thermodynamic de�nition of entropy is [�A.�a–��], dS = dq rev �T or for

a �nite change at constant temperature ∆S = q rev �T. �e transfer of heat is
speci�ed as being reversible, which can o�en be assumed for a large enough
metal block, therefore q rev = 250 kJ.
 (i)
q rev 250 kJ
∆S = = = 0.853 kJ = +853 J
T (273.15 K + 20 K)
(ii)
q rev 250 kJ
∆S = = = 0.670 kJ = +670 J
T (273.15 K + 100 K)

E�A.�(b) As explained in Section �A.�(a) on page �� the change in entropy for an isother-
mal expansion of a gas is calculated using
Vf m Vf
∆S = nR ln � � = R ln � �
Vi M Vi
4.00 g −1 750 cm3
=� −1 � × (8.3145 J K mol ) × ln �
−1
�
28.02 g mol 500 cm3
= +0.481 J K−1 .

E�A.�(b) �e change in entropy for an isothermal expansion of a gas is ∆S = nR ln (Vf �Vi )

as explained in Section �A.�(a) on page ��.

(i) Isothermal reversible expansion

14 g −1 4.60 dm3
∆S = � � × (8.3145 J K −1
mol ) × ln � �
28.02 g mol−1 1.20 dm3
= +0.81 J K−1 .

Because the process is reversible ∆S tot = � .

Because ∆S tot = ∆S + ∆S sur

∆S sur = ∆S tot − ∆S = −0.81 J K−1 .

(ii) Isothermal irreversible expansion against p ex = 0 Because entropy is a

state function and the initial and �nal states of the system are the same as
in (a), ∆S is the same.

∆S = +0.81 J K−1 .

Expansion against an external pressure of � does no work, and for an

isothermal process of an ideal gas ∆U = 0. From the First Law if follows
that q = 0 and therefore ∆S sur = � .

∆S tot = ∆S + ∆S sur = +0.81 J K−1 .

(iii) Adiabatic reversible expansion For an adiabatic expansion there is no heat
�owing to or from the surroundings, thus ∆S sur = � . For a reversible
process ∆S tot = � , therefore it follows that ∆S = � as well.
E�A.�(b) �e e�ciency is de�ned in [�A.�–��], η = �w���q h �, and for a Carnot cycle
e�ciency is given by [�A.�–��], η = 1 − (Tc �Th ). �ese two are combined
and rearranged into an expression for the temperature of the hot source

�w���q h � = 1 − (Tc �Th )

Tc
hence Th =
1 − �w���q h �
(273.15 K + 0 K)
= = 390 K .
1 − �3.00 kJ��� − 10.00 kJ�

E�A.�(b) �e e�ciency of a Carnot cycle is given by [�A.�–��], η = 1 − (Tc �Th ). �is is

rearranged to give an expression for the temperature of the cold sink

Tc = (1 − η) × Th = (1 − 0.10) × (273.15 K + 40 K) = 282 K .

Note that the temperature must be in kelvins.

P�A.� (a) �e �nal volume of the gas at 1.00 bar and 300 K temperature is found
using the perfect gas law [�A.�–�]:

nRT
Vf =
p
(0.10 mol) × (8.3145 × 10−2 dm3 bar K−1 mol−1 ) × (300 K)
=
1.00 bar
= 2.49... dm3 = 2.5 dm3 .

(b) �e expansion work against a constant external pressure is given by [�A.�–

��], w = −p ex (Vf − Vi ).

w = −p ex (Vf − Vi )
= −(1.00 × 105 Pa) × �2.49... × 10−3 m3 − 1.25 × 10−3 m3 �
= −1.24... × 102 J = −1.2 × 102 J .

�e work will be in joules if the pressure is expressed in pascals and the

volume in m3 .
(c) For an isothermal process of a perfect gas ∆U = 0. �e First Law [�A.�–
��], ∆U = q + w, is then used to �nd the heat

q = ∆U − w = 0 − (−1.24... × 102 J) = +1.24... × 102 J = +1.2 × 102 J .

As explained in Section �A.�(a) on page �� the change in entropy of an isother-

mal expansion of an ideal gas can be calculated from ∆S = nR ln (Vf �Vi ).
 �e entropy of the surroundings is given by [�A.�b–��], ∆S sur = −q rev �T, and
q sur = −q. �erefore

∆S tot = ∆S + ∆S sur
Vf −q
= nR ln � � +
Vi T
2.49... dm3
= (0.10 mol) × (8.3145 J K−1 mol−1 ) × ln � �
1.25 dm3
−(+1.24... × 102 J)
+
300 K
= +0.159... J K−1 = +0.16 J K−1 .

P�A.� �e isotherms correspond to constant temperature, and the adiabats corre-

spond to constant entropy. �is implies that Stages � and � of the Carnot cycle
are horizontal straight lines, whereas Stages � and � are vertical straight lines
on the temperature–entropy diagram, as shown in Fig. �.�.

Stage �
A B
Temperature, T

Stage � Stage �

D C
Stage �

Entropy, S

(a) �e entropy change for a reversible isothermal expansion is given in Sec-

tion �A.�(a) on page �� as ∆S = nR ln (Vf �Vi ). �us the entropy change
for Stage � is ∆S 1 = nR ln (VB �VA ) and for Stage � ∆S 3 = nR ln (VD �VC ) =
−nR ln (VB �VA ). �e area enclosed by the Carnot cycle is is just that of a
rectangle with sides nR ln (VB �VA ) and (Th − Tc ), thus

� TdS = Area = nR(Th − Tc ) ln (VB �VA ) .

(b) �e amount of heat extracted from the hot source is q h = nRTh ln (VB �VA )
as explained in Section �A.�(a) on page ��. �e e�ciency is de�ned in
[�A.�–��], η = �w���q h �, and for a Carnot cycle e�ciency is given by
 [�A.�–��], η = 1 − (Tc �Th ). Equating them an expression for the net
work is obtained

�w���q h � = 1 − (Tc �Th )

Tc
hence �w� = q h × �1 − �
Th
VB Tc
= nRTh ln � � × �1 − �
VA Th
= nR(Th − Tc ) ln (VB �VA ) .

(c) �e area of the temperature–entropy diagram of a Carnot cycle is equal

to the net work done in the cycle.

P�A.� As shown in Problem P�A.� for the process in which a heat pump extracts heat
q c = −�q� from the cold source and deposits heat q h = �q� + �w� into the hot sink
the overall change in entropy is

−�q� �q� + �w�

∆S = +
Tc Th

For the process to be permissible by the Second Law the Clausius inequality
[�A.��–��] must be satis�ed

−�q� �q� + �w�

+ ≥0
Tc Th

�e minimum work corresponds to the equlity. �is work is

Th
�w� = �q� × � − 1�
Tc

If energy as work or heat is expended for a period of time ∆t, the power is
(energy)�∆t. �us dividing both sides of the above equation by ∆t gives

�w� �q� Th
= × � − 1�
∆t ∆t Tc

�w��∆t is the power expended as work on the engine and �q��∆t is the power
expended due to the heat transferred, therefore

Th
Pwork = Pheat × � − 1�
Tc
(273.15 K + 18 K)
= 5 kW × � − 1�
(273.15 K + 13 K)
= 0.0874... kW = 0.09 kW .
E�B.�(b) �e entropy change of a phase transition is given by [�B.�–��], ∆ trs S = ∆ trs H�Ttrs .
As discussed in Section �B.� on page �� because there is no hydrogen bond-
ing in liquid cyclohexane it is safe to apply Trouton’s rule. �at is ∆ vap S −○ =
+85 J K−1 mol−1 . It follows that

∆ vap H −○ = Tb × ∆ vap S −○
= (273.15 K + 80.7 K) × (+85 J K−1 mol−1 )
= 3.00... × 104 J mol−1 = +30 kJ mol−1 .

E�B.�(b) (i) �e entropy change of a phase transition is given by [�B.�–��], ∆ trs S =

∆ trs H�Ttrs . For vaporisation this becomes

∆ vap H −○ + 35.27 × 103 J mol−1

∆ vap S −○ = =
Tb (273.15 K + 64.1 K)
= +104.6 J K−1 mol−1 .

(ii) Because the system at the transition temperature is at equilibrium, ∆S tot =

0, thus
∆S sur = −∆ vap S −○ = −104.6 J K−1 mol−1 .

E�B.�(b) �e change in entropy with temperature is given by [�B.�–��],

Tf dT
∆S = S(Tf ) − S(Ti ) = � Cp
Ti T

Assuming that C p is constant in the temperature range Ti to Tf , this becomes

∆S = C p ln (Tf �Ti ) as detailed in Section �B.� on page ��. �us, the increase
in the molar entropy of nitrogen gas is

273 K
∆S m = S m (273 K) − S m (298 K) = (29.125 J K−1 mol−1 ) × ln � �
298 K
= −2.55 J K−1 mol−1 .

E�B.�(b) As explained in Section �B.� on page �� the temperature variation of the en-
tropy at constant volume is given by
Tf dT
∆S = S(Tf ) − S(Ti ) = � CV
Ti T
 Assuming that C V = 32 R, the ideal gas limit, for the temperature range of
interest, the molar entropy at 250 K is given by

3 dT
250 K
S m (250 K) = S m (298 K) + � 2
R
298 KT
250 K
= S m (298 K) + × ln �
3
2
R �
298 K
= (154.84 J K−1 mol−1 )
250 K
+ ( 32 × 8.3145 J K−1 mol−1 ) × ln � �
298 K
= 153 J K−1 mol−1 .

E�B.�(b) Two identical blocks must come to their average temperature. �erefore the
�nal temperature is

Tf = 12 (T1 + T2 ) = 1
2
× (100 ○ C + 25 ○ C)
= 62.5... ○ C = 3.35... × 102 K = 336 K .

Although the above result may seem self-evident, the more detailed explaina-
tion is as follows. �e heat capacity at constant volume is de�ned in [�A.��–
��], C V = (∂U�∂T)V . As shown in Section �A.�(b) on page ��, if the heat
capacity is constant, the internal energy changes linearly with the change in
temperature. �at is ∆U = C V ∆T = C V (Tf − Ti ). For the two blocks at
the initial temperatures of T1 and T2 , the change in internal energy to reach
the �nal temperature Tf is ∆U 1 = C V ,1 (Tf − T1 ) and ∆U 2 = C V ,2 (Tf − T2 ),
respectively. �e blocks of metal are made of the same substance and are of
the same size, therefore C V ,1 = C V ,2 = C V . Because the system is isolated
the total change in internal energy is ∆U = ∆U 1 + ∆U 2 = 0. �is means that
∆U = C V ((Tf − T1 ) − (Tf − T2 )) = C V × (2Tf − (T1 + T2 )) = 0, which implies
that the �nal temperature is Tf = 12 (T1 + T2 ), as stated above.

�e temperature variation of the entropy at constant volume is given by [�B.�–

��], ∆S = C V ln (Tf �Ti ), with C p replaced by C V . Expressed with the speci�c
heat C V ,s = C V �m it becomes

Tf
∆S = mC V ,s ln � �
Ti

Note that for a solid the internal energy does not change signi�cantly with the
volume or pressure, thus it can be assumed that C V = C p = C. �e entropy
 change for each block is found using this expression
Tf
∆S 1 = mC V ,s ln � �
T1
3.35... × 102 K
= (1.00 × 104 g) × (0.449 J K−1 g−1 ) × ln � �
100 K + 273.15 K
= −4.75... × 102 J K−1 = −476 J K−1 .
Tf
∆S 2 = mC V ,s ln � �
T2
3.35... × 102 K
= (1.00 × 104 g) × (0.449 J K−1 g−1 ) × ln � �
25 K + 273.15 K
= 5.31... × 102 J K−1 = +532 J K−1 .
�e total change in entropy is
∆S tot = ∆S 1 + ∆S 2 = (−4.75... × 102 J K−1 ) + (5.31... × 102 J K−1 )
= 0.563... × 102 J K−1 = +56 J K−1 .
Because ∆S tot > 0 the process is spontaneous, in accord with experience.

E�B.�(b) Because entropy is a state function, ∆S between the initial and �nal states is
the same irrespective of the path taken. �us the overall process can be broken
down into steps that are easier to evaluate. First consider heating the initial
system at constant pressure to the �nal temperature. �e variation of entropy
with temperature at constant pressure is given by [�B.�–��], S(Tf ) = S(Ti ) +
C p ln (Tf �Ti ). �us the change in entropy, ∆S = S(Tf ) − S(Ti ), of this step is
Tf Tf
∆S 1 = C p ln � � = nC p,m ln � �
Ti Ti

Next consider an isothermal change in pressure. As explained in Section �A.�(a)

on page �� the change in entropy of an isothermal expansion of an ideal gas
is given by ∆S = nR ln (Vf �Vi ). Because for a �xed amount of gas at �xed
temperature p ∝ (1�V ) an equivalent expression for this entropy change is

pi
∆S 2 = nR ln � �
pf

�erefore the overall entropy change for the system is

Tf pi
∆S = ∆S 1 + ∆S 2 = nC p,m ln � � + nR ln � �
Ti pf
7 273.15 K + 135 K
= (2.00 mol) × � × 8.3145 J K−1 mol−1 � × ln � �
2 273.15 K + 25 K
1.50 atm
+ (2.00 mol) × (8.3145 J K−1 mol−1 ) × ln � �
7.00 atm
= (+18.2... J K−1 ) + (−25.6... J K−1 ) = −7.3 J K−1 .
E�B.�(b) Because entropy is a state function, ∆S between the initial and �nal states is
the same irrespective of the path taken. �us the overall process can be broken
down into steps that are easier to evaluate. First consider heating the ice at
constant pressure from the initial temperature to the melting point, Tm . �e
variation of entropy with temperature at constant pressure is given by [�B.�–
��], S(Tf ) = S(Ti ) + C p ln (Tf �Ti ). �us the change in entropy, ∆S = S(Tf ) −
S(Ti ), for this step is

Tm Tm
∆S 1 = C p ln � � = nC p,m (H2 O(s)) ln � �
Ti Ti

Next consider the phase transition from solid to liquid at the melting temper-
ature. �e entropy change of a phase transition is given by [�B.�–��], ∆ trs S =
∆ trs H�Ttrs , thus

−
○
∆ fus H m
∆S 2 = n
Tm

�en the liquid is heated to the boiling temperature, Tb . In analogy to the �rst
step

Tb
∆S 3 = nC p,m (H2 O(l)) ln � �
Tm

�e next phase transition is from liquid to gas

−
○
∆ vap H m
∆S 4 = n
Tb

Finally, the vapour is heated from Tb to Tf

Tf
∆S 5 = nC p,m (H2 O(g)) ln � �
Tb
 �erefore the overall entropy change for the system is

∆S = ∆S 1 + ∆S 2 + ∆S 3 + ∆S 4 + ∆S 5
−
○
Tm ∆ fus H m Tb
= nC p,m (H2 O(s)) ln � �+n + nC p,m (H2 O(l)) ln � �
Ti Tm Tm
−
○
∆ vap H m Tf
+n + nC p,m (H2 O(g)) ln � �
Tb Tb
15.0 g −1 273.15 K
= × (37.6 J K mol ) × ln �
−1
�
18.02 g mol−1 273.15 K − 12.0 K
15.0 g 6.01 × 103 J mol−1
+ ×
18.02 g mol−1 273.15 K
15.0 g −1 273.15 K + 100.0 K
+ −1 × (75.3 J K mol ) × ln �
−1
�
18.02 g mol 273.15 K
15.0 g 40.7 × 103 J mol−1
+ −1 ×
18.02 g mol 273.15 K + 100.0 K
15.0 g −1 273.15 K + 105.0 K
+ −1 × (33.6 J K mol ) × ln �
−1
�
18.02 g mol 273.15 K + 100.0 K
= (+1.40... J K−1 ) + (+18.3... J K−1 ) + (+19.5... J K−1 )
+ (+90.7... J K−1 ) + (0.372... J K−1 )
= +130.4 J K−1 .

P�B.� Because entropy is a state function, ∆S between the initial and �nal states is
the same irrespective of the path taken. �us the overall process can be broken
down into steps that are easier to evaluate.
First consider cooling the water at constant pressure to from the initial temper-
ature T to that of freezing, Tf . Entropy variation with temperature at constant
pressure is given by [�B.�–��], S(Tfinal ) = S(Tinitial ) + C p ln (Tfinal �Tinitial ).
�us the change in entropy, ∆S = S(Tfinal ) − S(Tinitial ), of this step is

Tf Tf
∆S 1 = C p ln � � = nC p,m (H2 O(l)) ln � �
T T

Next consider the phase transition from liquid to solid at the freezing temper-
ature; note that freezing is just the opposite of fusion, thus ∆H 2 = n(−∆ fus H m
−
○
).
�e entropy change of a phase transition is given by [�B.�–��], ∆ trs S = ∆ trs H�Ttrs ,
thus
∆H 2 −∆ fus H m
−
○
∆S 2 = =n
Tf Tf

�e ice is then heated to the �nal temperature, T. In analogy to the �rst step

T
∆S 3 = nC p,m (H2 O(s)) ln � �
Tf
�erefore the overall entropy change for the system is

∆S = ∆S 1 + ∆S 2 + ∆S 3
Tf −∆ fus H m
−
○
T
= nC p,m (H2 O(l)) ln � �+n + nC p,m (H2 O(s)) ln � �
T Tf Tf
−1 273.15 K
= (1.00 mol) × (75.3 J K mol ) × ln �
−1
�
273.15 K + 5.00 K
−6.01 × 103 J mol−1
+ (1.00 mol) ×
273.15 K
273.15 K + 5.00 K
+ (1.00 mol) × (37.6 J K−1 mol−1 ) × ln � �
273.15 K
= (−1.36... J K−1 ) + (−22.0... J K−1 ) + (+0.682... J K−1 )
= −22.6... J K−1 .

Consider the enthalphy change for the same path. �e variation of the enthalpy
with temperature at constant pressure is given by [�B.�b–��], ∆H = C p ∆T.
�us for the �rst and third steps, respectively

∆H 1 = nC p,m (H2 O(l))(Tf − T) and ∆H 3 = nC p,m (H2 O(s))(T − Tf )

�erefore the overall enthalpy change for the system is

∆H = ∆H 1 + ∆H 2 + ∆H 3
= nC p,m (H2 O(l))(Tf − T) + n(−∆ fus H m
−
○
) + nC p,m (H2 O(s))(T − Tf )
= (1.00 mol) × (75.3 J K−1 mol−1 ) × (−5.00 K)
+ (1.00 mol) × (−6.01 × 103 J mol−1 )
+ (1.00 mol) × (37.6 J K−1 mol−1 ) × (+5.00 K)
= (−3.76... × 102 J) + (−6.01... × 103 J) + (+1.88... × 102 J)
= −6.19... × 103 J

At constant pressure the heat released by the system is the enthalpy change of
the system, q = ∆H. Because q sur = −q, the entropy change of the surroundings
is
−q −(−6.19... × 103 J)
∆S sur = =
T 273.15 K + 5.00 K
= +22.2... J K−1

�erefore the total entropy change is

∆S tot = ∆S + ∆S sur = (−22.6... J K−1 ) + (+22.2... J K−1 )

= −0.401... J K−1 = −0.4 J K−1 .

Because the change in the total entropy is negative, the Second Law implies that
the process is not spontaneous .
P�B.� Consider heating nitrogen at constant pressure to from the initial to �nal tem-
peratures. �e variation of the entropy with temperature is given by [�B.�–��],
S(Tf ) = S(Ti ) + ∫Ti f (C p �T)dT. �e constant-pressure molar heat capacity
T

is given as a function of temperature of a form C p,m = a + bT, with a =

+28.58 J K−1 mol−1 and b = +3.77 × 10−3 J K−2 mol−1 . �us the molar entropy
at Tf = 373 K is
373 K
−
○
Sm (373 K) = S m
−
○
(298 K) + � (C p,m �T) dT
298 K
a + bT
373 K
= Sm
−
○
(298 K) + � dT
298 K T
373 K 1 373 K
= Sm
−
○
(298 K) + a × � dT + b × � dT
298 K T 298 K
373 K
= Sm
−
○
(298 K) + a × ln � � + b × (373 K − 298 K)
298 K
373 K
= (191.6 J K−1 mol−1 ) + (+28.58 J K−1 mol−1 ) × ln � �
298 K
+ (+3.77 × 10−3 J K−2 mol−1 ) × (373 K − 298 K)
= (191.6 J K−1 mol−1 )
+ (6.41... J K−1 mol−1 ) + (0.282... J K−1 mol−1 )
= +198.3 J K−1 mol−1 .

When the heat capacity is instead assumed to be temperature independent,

C p,m = 29.13 J K−1 mol−1 , the result is
373 K
−
○
Sm (373 K) = S m
−
○
(298 K) + � (C p,m �T) dT
298 K
373 K
= Sm
−
○
(298 K) + C p,m × ln � �
298 K
373 K
= (191.6 J K−1 mol−1 ) + (+29.13 J K−1 mol−1 ) × ln � �
298 K
= (191.6 J K−1 mol−1 ) + (6.53... J K−1 mol−1 )
= +198.1 J K−1 mol−1 .

�e di�erence between the results is relatively small (≈ 0.1 %). �is is because
the temperature variation of the heat capacity over this range is relatively small.

P�B.� (a) Rearranging Newton’s law gives

dT
= −αdt
T − Tsur
Integrating both sides give

ln (T − Tsur ) = −αt + D
 where D is an integration constant that is determinded applying the bound-
ary conditions T = Ti at t = 0. Hence, D = ln(Ti − Tsur ), and therefore

T − Tsur
ln � � = −αt .
Ti − Tsur

(b) �e above equation is rearranged to give an expression for T

T = Tsur + (Ti − Tsur ) × e−α t

Given that S(T) − S(Ti ) = C ln(T�Ti ), it follows that

T(t)
S(t) = S(T(t)) = S(Ti ) + C ln � �
Ti
Tsur + (Ti − Tsur ) × e−α t
= S(Ti ) + C ln � �.
Ti

P�B.� (a) Because enthalpy is a state function, ∆H between the initial and �nal
states is the same irrespective of the path taken. �us the overall process
can be broken down into steps that are easier to evaluate. First consider
condensation of vapour. Given that all the vapour turns to liquid water,
the heat released is the opposite of that of vaporization

∆H 1 = n(−∆ vap H −○ ).

�e newly formed liquid water is initially at the boiling point. �e next

step is the water cooling from the boiling to �nal temperatures. �e en-
thalpy change associated with a temperature change is given by [�B.�b–
��], ∆H = C p ∆T. �us

∆H 2 = C p ∆T = nC p,m (H2 O(l))(Tf − Tb )

�e �nal step is for the metal block to come to thermal equilibrium with
the water
m
∆H 3 = C p ∆T = C p,m (Cu(s))(Tf − Ti )
M
where Ti is the initial temperature of the block.
Because the system is insulated there is no overall change in the enthalpy
of the system as a whole, ∆H sys = ∆H 1 +∆H 2 +∆H 3 = 0. Putting together
the expresssions of enthalpy change at each step gives
m
n(−∆ vap H −○ ) + nC p,m (H2 O(l))(Tf − Tb ) + C p,m (Cu(s))(Tf − Ti ) = 0
M
Hence
m
Tf × �nC p,m (H2 O(l)) + C p,m (Cu(s))� =
M
m
= n∆ vap H −○ + nC p,m (H2 O(l)) × Tb + C p,m (Cu(s)) × Ti
M
 �us the �nal temperature is given by
n∆ vap H −○ + nC p,m (H2 O(l)) × Tb + (m�M)C p,m (Cu(s)) × Ti
Tf =
nC p,m (H2 O(l)) + (m�M)C p,m (Cu(s))
For convenience the numerator and denominator is estimated separately
numerator = (1.00 mol) × (4.07 × 104 J mol−1 )
+ (1.00 mol) × (75.3 J K−1 mol−1 ) × (373.15 K)
2.00 × 103 g
+� � × (24.44 J K−1 mol−1 ) × (273.15 K)
63.55 g mol−1
= +2.78... × 105 J mol−1

denominator = (1.00 mol) × (75.3 J K−1 mol−1 )

2.00 × 103 g
+� � × (24.44 J K−1 mol−1 )
63.55 g mol−1
= +8.44... × 102 J K−1 mol−1
Hence
+2.78... × 105 J mol−1
Tf = = 3.30... × 102 K = 330 K .
+8.44... × 102 J K−1 mol−1
(b) �e net heat transferred to the metal block is
m
∆H 3 = C p,m (Cu(s))(Tf − Ti )
M
2.00 × 103 g −1
= −1 × (24.44 J K mol ) × (3.30... × 10 K − 273.15 K)
−1 2
63.55 g mol
= +4.39... × 104 J = +43.9 kJ .
(c) �e entropy change of a phase transition is given by [�B.�–��], ∆ trs S =
∆ trs H�Ttrs . �us the entropy of the condensation step is
∆H 1 n(−∆ vap H −○ )
∆S 1 = =
Tb Tb
(1.00 mol) × (−4.07 × 104 J mol−1 )
=
373.15 K
= −1.09... × 102 J K−1
�e temperature dependence of the entropy at constant pressure is given
by [�B.�–��], ∆S = nC p,m ln (Tf �Ti ). �us, the changes in entropy for
the second and third steps are, respectively
Tf
∆S 2 = nC p,m (H2 O(l)) ln � �
Tb
3.30... × 102 K
= (1.00 mol) × (75.3 J K−1 mol−1 ) × ln � �
373.15 K
= −9.19... J K−1
 m Tf
∆S 3 = C p,m (Cu(s)) ln � �
M Ti
2.00 × 103 g −1 3.30... × 102 K
= × (24.44 J K −1
mol ) × ln � �
63.55 g mol−1 273.15 K
= +1.46... × 102 J K−1

�e overall entropy change for water is

∆S 1 + ∆S 2 = (−1.09... × 102 J K−1 ) + (−9.19... J K−1 ) = −118 J K−1 .

�e entropy change change for copper block is ∆S 3 = +146 J K−1 .

�e total entropy change is therefore

∆S tot = ∆S 1 + ∆S 2 + ∆S 3
= (−1.09... × 102 J K−1 ) + (−9.19... J K−1 ) + (+1.46... × 102 J K−1 )
= +27.8... J K−1 = +28 J K−1 .

P�B.�� (a) Because the working substance is assumed to be a perfect gas, its internal
energy depends on temperature only. DU as a function of temperature
is given by [�A.��b–��], ∆U = C V ∆T. Because the steps � and � are
adiabatic, q 1 = � and q 3 = � . �us, from the First Law, ∆U = q + w, the
work done in these steps is equal to the change in internal energy

w 1 = ∆U 1 = C V (TB − TA ) = nC V ,m (TB − TA ) .
w 3 = ∆U 3 = C V (TD − TC ) = nC V ,m (TD − TC ) .

Because the steps � and � are at constant volume, no work is done: w 2 = �

and w 4 = � . �us, from the First Law, ∆U = q +w, the heat in these steps
is equal to the change in internal energy

q 2 = ∆U 2 = C V (TC − TB ) = nC V ,m (TC − TB ) .
q 4 = ∆U 4 = C V (TA − TD ) = nC V ,m (TA − TD ) .

(b) �e e�ciency is de�ned as η = �w cycle ���q 2 �, thus

�w cycle � �w 1 + w 3 �
η= =
�q 2 � �q 2 �
nC V ,m × �(TB − TA ) + (TD − TC )�
=
nC V ,m × �TC − TB �
�(TD − TA ) − (TC − TB )�
=
�TC − TB �
TD − TA TD − TA
=� − 1� = �1 − �.
TC − TB TC − TB
(c) For a reversible adiabatic expansion in step �: VA TA c = VB TB c . �is is
rearranged to give a ratio of temperatures

TA VB 1�c
=� �
TB VA

Similarly, in step �: VC TC c = VD TD c , and noting that VA = VD and VB =

VC , the temperature ratio is

TD VC 1�c VB 1�c TA
=� � =� � =
TC VD VA TB

Using this to write TD = (TC TA )�TB and then substituting this into the
above expression for the e�ciency gives

(TC TA �TB ) − TA (TA �TB )(TC − TB )

η = �1 − � = �1 − �
TC − TB TC − TB
TA VB 1�c VB 1�c
= �1 − � = �1 − � � � = 1 − � � .
TB VA VA

In the last step it becomes apparent that the modulo is redundant because
VB < VA and c = C V ,m �R is positive.
(d) Because the steps � and � are adiabatic, no heat is exchanged between the
system and the surroundings, therefore ∆S 1 = ∆S sur,1 = � and ∆S 3 =
∆S sur,3 = � . As explained in Section �B.� on page �� the variation of the
entropy with temperature at constant volume is given by ∆S = C V ln (Tf �Ti ).
�us, the entropy changes for the steps � and � are, respectively

TC TC
∆S 2 = C V ln � � = nC V ,m ln � � .
TB TB
TA TA
∆S 4 = C V ln � � = nC V ,m ln � � .
TD TD

Because the processes during these steps are reversible, the total change
in entropy is zero, ∆S tot = ∆S + ∆S sur = 0. �erefore, the entropy change
of the surroundings for each process is, respectively, ∆S sur,2 = −∆S 2 =
−nC V ,m ln (TC �TB ) and ∆S sur,4 = −∆S 4 = −nC V ,m ln (TA �TD ) .
(e) Given C V ,m = 52 R and VA = 10VB , the e�ciency of the cycle is

VB R�C V ,m 1 2�5
η =1−� � = 1 − � � = 0.601... = 60.2% .
10VB 10

It is given that p C �p B = 5 and VB = VC . In this constant volume process

the perfect gas law, pV = nRT, implies that p ∝ T, therefore TC �TB =
p C �p B . It is shown above that TD �TC = TA �TB , so it also follows that
TA �TD = TB �TC = 1�5. �erefore the entropy changes in steps � and �
 are, respectively

∆S 2 = n � 52 R� ln(5)
= (1.00 mol) × ( 52 × �8.3145 J K−1 mol−1 � × ln(5)
= +33.5 J K−1 .
∆S 4 = n � 52 R� ln (1�5)
= (1.00 mol) × ( 52 × �8.3145 J K−1 mol−1 � × ln (1�5)
= −33.5 J K−1 .

�e entropy of the surroundings during these steps are thus, respectively,

∆S sur 2 = −33.5 J K−1 and ∆S sur 4 = +33.5 J K−1 . Finally, for the steps �
and � the entropy changes are always zero: ∆S 1 = ∆S sur,1 = � and ∆S 3 =
∆S sur,3 = � .

P�B.�� �e entropy dependence on temperature is given by [�B.�–��], S(Tf ) = S(Ti )+

∫Ti (C p �T)dT. �e empirical expression for the constant-pressure molar heat
Tf

capacity is given by [�B.�–��], C p,m = a + bT + c�T 2 . Using this, the expression

for the molar entropy variation becomes

Tf a + bT + c�T 2
S m (Tf ) = S m (Ti ) + � dT
Ti T
Tf dT Tf Tf dT
= S m (Ti ) + a � +b� dT + c �
Ti T Ti Ti T3
Tf c 1 1
= S m (Ti ) + a ln � � + b(Tf − Ti ) − � 2 − 2 �
Ti 2 Tf Ti

−
○
�erefore, using the data given in the Resource section, and given S m (298 K) =
−1 −1
192.45 J K mol , it follows that

(a) Tf = 100 ○ C

S m (373 K) = (192.45 J K−1 mol−1 )

373.15 K
+ (29.75 J K−1 mol−1 ) × ln � �
298 K
+ (25.1 × 10−3 J K−2 mol−1 ) × (373.15 K − 298 K)
−1.55 × 105 J K mol−1 1 1
− ×� − �
2 (373.15 K)2 (298 K)2
= (192.45 J K−1 mol−1 ) + (+6.69... J K−1 mol−1 )
+ (+1.88... J K−1 mol−1 ) − (+0.316... J K−1 mol−1 )
= +200.71 J K−1 mol−1 .
 (b) Tf = 500 ○ C

S m (773 K) = (192.45 J K−1 mol−1 )

773.15 K
+ (29.75 J K−1 mol−1 ) × ln � �
298 K
+ (25.1 × 10−3 J K−2 mol−1 ) × (773.15 K − 298 K)
−1.55 × 105 J K mol−1 1 1
− ×� − �
2 (773.15 K) 2 (298 K)2
= (192.45 J K−1 mol−1 ) + (+28.3... J K−1 mol−1 )
+ (+11.9... J K−1 mol−1 ) − (+0.743... J K−1 mol−1 )
= +232.00 J K−1 mol−1 .

E�C.�(b) Assuming that the Debye extrapolation is valid, the constant-pressure molar
heat capacity is C p,m (T) = aT 3 . �e temperature dependence of the entropy
is given by [�C.�a–��], S(T2 ) = S(T1 ) = ∫T12 (C p,m �T)dT. For a given temper-
T

ature T the change in molar entropy from zero temperature is therefore

T C p,m T aT ′ 3
S m (T) − S m (0) = � dT ′
= � dT ′
0 T′ 0 T′
T a
= a � T ′ dT ′ = T 3
2
0 3
Hence

1.956 × 10−4 J K−4 mol−1

S m (10 K) − S m (0) = × (10 K)3
3
= 6.5 × 10−2 J K−1 mol−1 .

E�C.�(b) �e standard reaction entropy is given by [�C.�b–��], ∆ r S −○ = ∑J ν J S m

−
○
(J),
where ν J are the signed stoichiometric numbers.

(i)

∆ r S −○ = S m
−
○
(Zn2+ , (aq)) + S m
−
○
(Cu, (s)) − S m
−
○
(Zn, (s)) − S m
−
○
(Cu2+ , (aq))
= (−112.1 J K−1 mol−1 ) + (33.150 J K−1 mol−1 )
− (41.63 J K−1 mol−1 ) − (−99.6 J K−1 mol−1 )
= −21.0 J K−1 mol−1 .
 (ii)

∆ r S −○ = 12S m
−
○
(CO2 , (g)) + 11S m
−
○
(H2 O, (l)) − S m
−
○
(sucrose, (s)) − 12S m
−
○
(O2 , (g))
= 12 × (213.74 J K−1 mol−1 ) + 11 × (69.91 J K−1 mol−1 )
− (360.2 J K−1 mol−1 ) − 12 × (205.138 J K−1 mol−1 )
= +512.0 J K−1 mol−1 .

E�C.�(b) Consider chemical equation

N2 (g) + 12 O2 (g) �→ N2 O(g)

Standard reaction entropy is given by [�C.�b–��], ∆ r S −○ = ∑J ν J S m

−
○
(J), where ν J
are singed stoichiometric coe�cients for a given reaction equation. �erefore,
using data from the Resource section

∆ r S −○ = nS m
−
○
(N2 O, (g)) − 12 nS m
−
○
(O2 , (g)) − nS m
−
○
(N2 , (g))
= (1.00 mol) × (219.85 J K−1 mol−1 )
− � 12 × 1.00 mol� × (205.138 J K−1 mol−1 )
− (1.00 mol) × (191.61 J K−1 mol−1 )
= −74.33 J K−1 .

P�C.� Consider the process of determining the calorimetric entropy from zero to
the temperature of interest. Assuming that the Debye extrapolation is valid,
the constant-pressure molar heat capacity at the lowest temperatures is of a
form C p,m (T) = aT 3 . �e temperature dependence of the entropy is given
by [�C.�a–��], S(T2 ) = S(T1 ) = ∫T12 (C p,m �T)dT. �us for a given (low)
T

temperature T the change in molar entropy from zero is

T C p,m T aT ′ 3
S m (T) − S m (0) = � dT ′
= � dT ′
0 T′ 0 T′
T a
= a � T ′ dT ′ = T 3 = 13 C p,m (T)
2
0 3
Hence
−
○
Sm (10 K) − S m
−
○
(0) = 1
3
× (4.64 J K−1 mol−1 ) = 1.54... J K−1 mol−1
−
○
�e increase in entropy on raising the temperature to the melting point is S m (234.4 K)−
−1
S m (10 K) = 57.74 J K mol . �e entropy change of a phase transition is
−
○ −1

given by [�C.�b–��], ∆ trs S(Ttrs ) = ∆ trs H(Ttrs )�Ttrs . �us

2322 J mol−1
−
○
∆ fus S m (234.4 K) = = 9.90... J K−1 mol−1
234.4 K
 Further raising the temperature to 298 K gives an increase in the entropy of
−
○
Sm (298 K) − S m
−
○
(234.4 K) = 6.85 J K−1 mol−1 .

Further raising the temperature to the boiling point, the entropy increases by
−
Sm○
(343.9 K) − S m
−
○
(234.4 K) = 10.83 J K−1 mol−1 . Finally, the contribution of
the second phase transition is

−
○
∆ vap H m 6.050 × 104 J mol−1
−
○
∆ vap S m (343.9 K) = =
Tb 343.9 K
= 1.75... × 10 J K mol−1
2 −1

�e �ird-Law standard molar entropy at 298 K is the sum of the above con-
tributions.

−
○
Sm (298 K) − S m
−
○
(0) = (1.54... J K−1 mol−1 ) + (57.74 J K−1 mol−1 )
+ (9.90... J K−1 mol−1 ) + (10.83 J K−1 mol−1 )
+ (1.75... × 102 J K−1 mol−1 )
= 256.0 J K−1 mol−1 .

P�C.� Assuming that the Debye extrapolation is valid, the constant-pressure molar
heat capacity is of a form C p,m (T) = aT 3 . �e temperature dependence of the
entropy is given by [�C.�a–��], S(T2 ) = S(T1 ) = ∫T12 (C p,m �T)dT. �us for a
T

given (low) temperature T the change in the molar entropy from zero is

T C p,m T aT ′ 3
S m (T) − S m (0) = � dT ′
= � dT ′
0 T′ 0 T′
T a
= a � T ′ dT ′ = T 3 = 13 C p,m (T)
2
0 3

Hence

−
○
Sm (10 K) − S m
−
○
(0) = 1
3
× (2.09 J K−1 mol−1 ) = 0.696... J K−1 mol−1

�e change in entropy is determined calorimetrically by measuring the area

under a plot of (C p,m �T) against T, as shown in Fig. �.�.
 T�K C p,m �(J K−1 mol−1 ) (C p,m �T)�(J K−2 mol−1 )
10 2.09 0.209 0
20 14.43 0.721 5
30 36.44 1.214 7
40 62.55 1.563 8
50 87.03 1.740 6
60 111.0 1.850 0
70 131.4 1.877 1
80 149.4 1.867 5
90 165.3 1.836 7
100 179.6 1.796 0
110 192.8 1.752 7
150 237.6 1.584 0
160 247.3 1.545 6
170 256.5 1.508 8
180 265.1 1.472 8
190 273.0 1.436 8
200 280.3 1.401 5

2.0
(C p,m �T)�(J K−2 mol−1 )

1.5

1.0

0.5

0.0
0 50 100 150 200
T�K

�e plot �ts well to a polynomial of order �. De�ne y = (C p,m �T)�(J K−2 mol−1 )
and x = T�K, so that the �tted function is expressed

y = c4 x 4 + c3 x 3 + c2 x 2 + c1 x + c0

where the best �tted coe�cients c i are

 ci 10 K to 200 K
c4 −1.0380 × 10−8
c3 +5.7041 × 10−6
c2 −1.1263 × 10−3
c1 +9.0159 × 10−2
c0 −6.1544 × 10−1

�e integral of the �tted functions over the range x i to x f is

xf
I=� c 4 x 4 + c 3 x 3 + c 2 x 2 + c 1 x + c 0 dx
xi
c4 c3 c2
= �x f 5 − x i 5 � + �x f 4 − x i 4 � + �x f 3 − x i 3 �
5 4 3
c1
+ �x f − x i � + c 0 (x f − x i )
2 2
2
Using the appropriate coe�cients and limits the integral gives
−
○
Sm (30 K) − S m
−
○
(10 K) = 2.96... × 102 J K−1 mol−1

�e standard �ird-Law molar entropy at 200 K is the sum of the both contri-
butions.
−
○
Sm (200 K) − S m
−
○
(0) = (S m
−
○
(200 K) − S m
−
○
(10 K))
+ (S m
−
○
(10 K) − S m
−
○
(0))
= (2.96... × 102 J K−1 mol−1 )
+ (0.696... J K−1 )
= ��� J K−1 mol−1 .

For entropy at 100 K, the above integral in needs to be calculated to the required
limit. �erefore
−
○
Sm (100 K) − S m
−
○
(10 K) = 1.37... × 102 J K−1 mol−1
�e other contribution is the same as before. Hence the molar entropy at 100 K
is
−
○
Sm (100 K) − S m
−
○
(0) = (0.696... J K−1 mol−1 ) + (1.37... × 102 J K−1 mol−1 )
= ��� J K−1 mol−1 .

P�C.� �e standard reaction entropy is given by [�C.�b–��], ∆ r S −○ = ∑J ν J S m

−
○
(J),
where ν J are the signed stoichiometric numbers.
∆ r S −○ (298 K) = S m
−
○
(NH3 , (g)) − 21 S m
−
○
(N2 , (g)) − 32 S m
−
○
(H2 , (g))
= (192.45 J K−1 mol−1 ) − 12 × (191.61 J K−1 mol−1 )
− 32 × (130.684 J K−1 mol−1 )
= −99.38... J K−1 mol−1 = −99.38 J K−1 mol−1 .
 �e standard reaction enthalpy is given by [�C.�b–��], ∆ r H −○ = ∑J ν J ∆ f H −○ (J).
�us

−
○ −
○ −
○
∆ r H −○ (298 K) = ∆ f H −○ (NH3 , (g)) − 12 ∆ f H −○ (H2 O, (g)) − 32 ∆ f H −○ (H2 , (g))
= (−46.11 kJ mol−1 ) − 12 × 0 − 32 × 0 = −46.11 kJ mol−1 .

�e temperature dependence of the reaction entropy is given by [�C.�a–��],

∆ r S −○ (T2 ) = ∆ r S −○ (T1 ) + ∫T12 (∆ r C −p○ �T)dT. Similarly, the enthalpy depen-
T

dence on temperature is given by Kirchho� ’s law [�C.�a–��], ∆ r H −○ (T2 ) =

∆ r H −○ (T1 ) + ∫T12 ∆ r C −p○ dT. �e quantity ∆ r C −p○ is de�ned in [�C.�b–��], ∆ r C −p○ =
T

∑J ν J C p,m (J). For the reaction at 298 K

−
○

∆ r C −p○ = C −p,m
○
(NH3 , (g)) − 12 C −p,m
○
(N2 , (g)) − 32 C −p,m
○
(H2 , (g))
= (35.06 J K−1 mol−1 ) − 12 × (29.125 J K−1 mol−1 )
− 32 × (28.824 J K−1 mol−1 )
= −22.7... J K−1 mol−1

Assuming that ∆ r C −p○ is constant over the temperature range, the standard en-
tropy and enthalpy changes of the reaction are given, respectively, by [�C.�b–
��], ∆ r S −○ (T2 ) = ∆ r S −○ (T1 ) + ∆ r C −p○ ln(T2 �T1 ), and [�C.�d–��], ∆ r H −○ (T2 ) =
∆ r H −○ (T1 ) + ∆ r C −p○ (T2 − T1 ).

500 K
∆ r S −○ (500 K) = ∆ r S −○ (298 K) + ∆ r C −p○ × ln � �
298 K
= (−99.38... J K−1 mol−1 )
500
+ (−22.7... J K−1 mol−1 ) × ln � �
298
= +111.15 J K−1 mol−1 .

∆ r H −○ (500 K) = ∆ r H −○ (298 K) + ∆ r C −p○ × (500 K − 298 K)

= (−46.11 × 103 J mol−1 )
+ (−22.7... J K−1 mol−1 ) × (202 K)
= −50.70 kJ mol−1 .

P�C.� �e change in entropy is determined calorimetrically by measuring the area

under a plot of (C p,m �T) against T, as shown in Fig. �.�.
 T�K C p,m �(J K−1 mol−1 ) (C p,m �T)�(J K−2 mol−1 )
100 23.00 0.230 0
120 23.74 0.197 8
140 24.25 0.173 2
150 24.44 0.162 9
160 24.61 0.153 8
180 24.89 0.138 3
200 25.11 0.125 6

0.3
(C p,m �T)�(J K−2 mol−1 )

0.2

0.2

0.1
100 120 140 160 180 200
T�K

�e plot is found to be well �tted by a polynomial of order �. De�ne y =

(C p,m �T)�(J K−2 mol−1 ) and x = T�K, so that the �tted function is expressed

y = (5.9463 × 10−6 )x 2 − (2.8129 × 10−3 )x + 0.45100

�e integral of the �tted functions over the range x i to x f is

y(x f ) 5.9463 × 10−6
I=� y dy = �x f 3 − x i 3 �
y(x i ) 3
2.8129 × 10−3
− �x f 2 − x i 2 � + (0.45100) (x f − x i )
2
Evaluating this integral over the range of x of 100 to 200 gives
−
○
Sm (200 K) − S m
−
○
(100 K) = 16.7... J K−1 mol−1
−
○
Given S m (100 K) the entropy at 200 K is
−
○
Sm (200 K) = S m
−
○
(100 K) + (S m
−
○
(200 K) − S m
−
○
(100 K))
= (29.79 J K−1 mol−1 ) + (16.7... J K−1 mol−1 )
= 46.57 J K−1 mol−1 .
 Assuming the heat capacity to be constant over the temperature range of inter-
est, the change in entropy as a function of temperature is given by [�B.�–��],
S(Tf ) = S(Ti ) + C p ln (Tf �Ti ). �erefore
200 K
−
○
Sm (200 K) = (29.79 J K−1 mol−1 ) + (24.44 J K−1 mol−1 ) × ln � �
100 K
= 46.73 J K−1 mol−1 .

�e di�erence is slight as expected because C p,m does not vary signi�cantly in

the given temperature range.

P�C.�� �e temperature dependence of the entropy is given by [�C.�a–��], S(T2 ) =

S(T1 ) = ∫T12 (C p,m �T)dT. Given that the heat capacity at the lowest tempera-
T

tures is the sum of the Debye, aT 3 , and electronic, bT, contributions, the molar
heat capacity is C p,m (T) = aT 3 + bT. �erefore, the molar entropy from zero
as a function of temperature is given by
T C p,m T aT ′ 3 + bT ′
S m (T) − S m (0) = � dT ′
= � dT ′
0 T′ 0 T′
a
= T 3 + bT
3
Setting the contributions to the entropy corresponding to each term to be equal
gives
a 3
T = bT
3
�
3b
hence T=
a
�erefore this temperature is
�
� 3 × 1.38 × 10−3 J K−2 mol−1
T =� = 2.86 K .
0.507 × 10−3 JK−4 mol−1
Because the Debye term in the entropy expression has a cubic dependence on
T, as the temperature increases it will dominate over the linear electronic term.
�us, the Debye contribution .

D�D.� As is discussed in detail in Topic �D the criteria for spontaneity at constant

volume and temperature is expressed in terms of the Helmholtz energy, dA ≤ 0,
and at constant pressure and temperature in terms of the Gibbs energy, dG ≤ 0.
Both the Helmholtz and Gibbs energies refer to properties of the system alone.
However, because of the way they are de�ned these quantities e�ectively allow
 the entropy change of the system plus surroundings to be evaluated. For exam-
ple, at constant volume and temperature the change in the Helmholtz energy
is expressed in terms of the internal energy change and the entropy change
of the system: dA = dU − TdS. If this expression is divided by −T to give
−dA�T = −dU�T + dS the two terms on the right can bothe be identi�ed as
entropy changes.
�e �rst term, −dU�T, is equal to the entropy change of the surroundings
because dq sur = −dq, and at constant volume dq = dU. �e second term is
the entropy change of the system. �us the sum of the two is the total en-
tropy change, which the Second Law shows must be positive in a spontaneous
process. �erefore, the change in the Helmholtz energy is an indicator of the
total entropy change, even though the former refers only to the system. Similar
considerations can be applied to the Gibbs energy.
It is also possible to express the criterion for spontaneity in terms of the change
in H, U or S for the system. For example, as shown in Topic �D, dS U ,V ≥ 0.
However, the variables which are being held constant (here U and V ) do not
correspond to such easily realizable conditions such as constant temperature
and volume (or pressure) so such criteria are less applicable to chemical sys-
tems.

E�D.�(b) �e standard reaction Gibbs energy is given by [�D.�–���], ∆ r G −○ = ∆ r H −○ −

T∆ r S −○ . �e standard reaction enthalpy is given in terms of the enthalpies
of formation by [�C.�b–��], ∆ r H −○ = ∑J ν J ∆ f H −○ (J), where ν J are the signed
stoichiometric numbers.

(i)
∆ r H −○ = ∆ f H −○ (Zn2+ ,(aq)) + ∆ f H −○ (Cu ,(s))
− ∆ f H −○ (Zn ,(s)) − ∆ f H −○ (Cu2+ ,(aq))
= (−153.89 kJ mol−1 ) + 0 − 0 − (+64.77 kJ mol−1 )
= −218.66 kJ mol−1 .

Given the result for the previous execise, ∆ r S −○ = −21.0 J K−1 mol−1 .
∆ r G −○ = (−218.66 kJ mol−1 ) − (298.15 K) × (−0.0210 kJ K−1 mol−1 )
= −212.40 kJ mol−1 .

(ii)
∆ r H −○ = 12∆ f H −○ (CO2 ,(g)) + 11∆ f H −○ (H2 O ,(l))
− ∆ f H −○ (sucrose ,(s)) − 12∆ f H −○ (O2 ,(g))
= 12 × (−393.51 kJ mol−1 ) + 11 × (−285.83 kJ mol−1 )
− (−2222 kJ mol−1 ) − 12 × 0
= −5644.25 kJ mol−1 = −5644 kJ mol−1 .
 Given the result for the previous execise, ∆ r S −○ = +512.0 J K−1 mol−1 .

∆ r G −○ = (−5644.25 kJ mol−1 ) − (298.15 K) × (+0.5120 kJ K−1 mol−1 )

= −5797 kJ mol−1 .

E�D.�(b) �e standard reaction entropy is given by [�C.�b–��], ∆ r S −○ = ∑J ν J S m

−
○
(J),
where ν J are the signed stoichiometric numbers.

∆ r S −○ = S m
−
○
(CH3 CH2 COOH ,(l)) − S m
−
○
(CO ,(g)) − S m
−
○
(CH3 CH2 OH ,(l))
= (191 J K−1 mol−1 ) − (197.67 J K−1 mol−1 ) − (160.7 J K−1 mol−1 )
= −167... J K−1 mol−1

�e standard reaction enthalpy is given by [�C.�b–��], ∆ r H −○ = ∑J ν J ∆ f H −○ (J).

∆ r H −○ = ∆ f H −○ (CH3 CH2 COOH ,(l)) − ∆ f H −○ (CO ,(g))

− ∆ f H −○ (CH3 CH2 OH ,(l))
= (−510 kJ mol−1 ) − (−110.53 kJ mol−1 ) − (−277.69 kJ mol−1 )
= −121... kJ mol−1

�e standard reaction Gibbs energy is given by [�D.�–���], ∆ r G −○ = ∆ r H −○ −

T∆ r S −○ .

∆ r G −○ = (−121... J K−1 mol−1 ) − (298.15 K) × (−0.167... kJ K−1 mol−1 )

= −72 kJ mol−1 .

E�D.�(b) �e maximum non-expansion work is equal to the Gibbs free energy as ex-
plained in Section �D.�(e) on page ���. �e standard reaction Gibbs energy is
given by [�D.��b–���], ∆ r G −○ = ∑J ν J ∆ f G −○ (J), where ν J are the signed stoichio-
metric numbers. For the reaction C3 H8 (g) + 5O2 (g) �→ 3CO2 (g) + 4H2 O(l)

∆ r G −○ = 3∆ f G −○ (CO2 ,(g)) + 4∆ f G −○ (H2 O ,(l)) − ∆ f H −○ (C3 H8 ,(g))

− 5∆ f H −○ (O2 ,(g))
= 3 × (−394.36 kJ mol−1 ) + 4 × (−237.13 kJ mol−1 )
− (−23.49 kJ mol−1 ) − 5 × 0
= −2108.11 kJ mol−1 .

�erefore, the �w add,max � = �∆ r G −○ � = 2108.11 kJ mol−1 .

E�D.�(b) �e standard reaction Gibbs energy is given by [�D.��b–���], ∆ r G −○ = ∑J ν J ∆ f G −○ (J),

where ν J are the signed stoichiometric numbers.
 (i)

∆ r G −○ = ∆ f G −○ (Zn2+ ,(aq)) + ∆ f G −○ (Cu ,(s))

− ∆ f G −○ (Zn ,(s)) − ∆ f G −○ (Cu2+ ,(aq))
= (−147.06 kJ mol−1 ) + 0 − 0 − (+65.49 kJ mol−1 )
= −212.55 kJ mol−1 .

(ii)

∆ r G −○ = 12∆ f G −○ (CO2 ,(g)) + 11∆ f G −○ (H2 O ,(l))

− ∆ f G −○ (sucrose ,(s)) − 12∆ f G −○ (O2 ,(g))
= 12 × (−394.36 kJ mol−1 ) + 11 × (−237.13 kJ mol−1 )
− (−1543 kJ mol−1 ) − 12 × 0
= −5798 kJ mol−1 .

E�D.�(b) Consider the reaction

NH2 CH2 COOH(s) + 92 O2 (g) �→ 2CO2 (g) + 52 H2 O(l) + 12 N2 (g)

�e standard reaction enthalpy is given by [�C.�b–��], ∆ r H −○ = ∑J ν J ∆ f H −○ (J),

where ν J are the signed stoichiometric numbers.

∆ r H −○ = 2∆ f H −○ (CO2 ,(g)) + 52 ∆ f H −○ (H2 O ,(l)) + 12 ∆ f H −○ (N2 ,(g))

− ∆ f H −○ (NH2 CH2 COOH ,(s)) − 92 ∆ f H −○ (O2 ,(g))

when rearranged this gives

∆ f H −○ (NH2 CH2 COOH ,(s)) = 2∆ f H −○ (CO2 ,(g)) + 52 ∆ f H −○ (H2 O ,(l))

+ 12 ∆ f H −○ (N2 ,(g)) − 92 ∆ f H −○ (O2 ,(g)) − ∆ r H −○
= 2 × (−393.51 kJ) + 52 × (−285.83 kJ) + 12 × 0
− 92 × 0 − (−969 kJ mol−1 )
= −5.32... × 102 kJ mol−1

�e standard reaction entropy is given by [�C.�b–��], ∆ r S −○ = ∑J ν J S m

−
○
(J).
�erefore, for the formation of the compound

∆ f S −○ (NH2 CH2 COOH,(s)) = S m

−
○
(NH2 CH2 COOH ,(s)) − 2S m
−
○
(C ,(s))
− 52 S m
−
○
(H2 ,(g)) − S m
−
○
(O2 ,(g)) − 12 S m
−
○
(N2 ,(g))
= (103.5 J K−1 mol−1 ) − 2(5.740 J K−1 mol−1 )
− 52 (130.684 J K−1 mol−1 ) − (205.138 J K−1 mol−1 )
− 12 (191.61 J K−1 mol−1 )
= −5.35... × 102 J K−1 mol−1
 �e standard reaction Gibbs energy is de�ned in [�D.�–���], ∆ r G −○ = ∆ r H −○ −
T∆ r S −○ , thus
∆ f G −○ (CH3 COOC2 H5 ,(l)) = (−5.32... × 102 kJ mol−1 )
− (298.15 K)(−0.535... kJ K−1 mol−1 )
= −373 kJ mol−1 .

P�D.� (a) �e standard reaction Gibbs energy is de�ned in [�D.�–���], ∆ r G −○ =

∆ r H −○ − T∆ r S −○ . �is is rearranged to give the reaction entropy change
∆ r H −○ − ∆ r G −○
∆ r S −○ =
T
(−20 × 103 J mol−1 ) − (−31 × 103 J mol−1 )
= = +35 J K−1 mol−1 .
310 K
(b) �e number of moles that are hydrolysed each second is n = N�N A . �us
the amount of non-expansion work that is done �w non−exp � = (N�N A )�∆ r G −○ �.
Assuming that the cell is spherical, its volume is given by 43 πr 3 . �e
power density is the work that is done in a time interval for a unit volume.
�erefore
(N�N A )�∆ r G −○ �
Power density = 4
3
πr 3
(1.0 × 106 )�(6.0221 × 1023 mol−1 ) × � − 31 × 103 J mol−1 �
= 4
3
π(10 × 10−6 )3
= 12 W m−3 .
For a computer battery it is
15 W
Power density (battery) = = 1.5 × 105 W m−3
100 × 10−6 m3
�us the power density of the cell is much smaller.
(c) �e non-expansion work needed to produce 1 mol of glutamine is given
14.2 kJ. �us
�w non−exp � 14.2 kJ
n= = = 0.46 mol .
�∆ r G �
−
○
31 kJ mol−1

P�D.� �e standard reaction Gibbs energy is given by [�D.�–���], ∆ r G −○ = ∆ r H −○ −

T∆ r S −○ . �e standard reaction entropy is [�C.�b–��], ∆ r S −○ = ∑J ν J S m
−
○
(J), where
ν J are the signed stoichiometric numbers. �erefore
∆ r S 1−○ = S m
−
○
(Na+ ,(g)) + S m
−
○
(Cl− ,(g)) − S m
−
○
(NaCl ,(s))
= (148 J K−1 mol−1 ) + (154 J K−1 mol−1 ) − (72.1 J K−1 mol−1 )
= 229.9 J K−1 mol−1
 And so

∆ r G 1−○ = (787 kJ mol−1 ) − (298 K) × (0.2299 kJ K−1 mol−1 )

= +7.18... × 102 kJ mol−1 = +718 kJ mol−1 .

For the second step ∆ r G 2−○ = ∆ solv G −○ (Na+ ) + ∆ solv G −○ (Cl− ). �e Gibbs en-
ergy of solvation in water is given by Born equation [�D.��b–���], ∆ solv G −○ =
−(z i 2 �[r i �pm]) × 6.86 × 104 kJ mol−1 , thus

(+1)2 (−1)2
∆ r G 2−○ = − � + � × 6.86 × 104 kJ mol−1
[r(Na )�pm] [r(Cl− )�pm]
+

1 1
= −� + � × 6.86 × 104 kJ mol−1 = −7.28... × 102 kJ mol−1
170 211
= −729 kJ mol−1

�erefore the total Gibbs energy change of the process

∆ r G −○ = ∆ r G 1−○ + ∆ r G 2−○ = (+7.18... × 102 kJ mol−1 ) + (−7.28... × 102 kJ mol−1 )

= −10 kJ mol−1 .

�e change in negative implying that the process is spontaneous.

P�D.� As hinted, the entropy is related to Gibbs energy as S = − (∂G�∂T) p . Be-

cause the Born equation [�D.��a–���], ∆ solv G −○ = −[(z i 2 e2 N A )�(8πε 0 r i )] ×
[1 − (1�ε r )], does not have an explicit dependence on temperature. �us the
entropy contribution is neglected by this model, ∆ solv S −○ = � . �e standard re-
action Gibbs energy is given by [�D.�–���], ∆ r G −○ = ∆ r H −○ − T∆ r S −○ . �erefore

z i 2 e2 N A 1
∆ solv H −○ = ∆ solv G −○ = − × �1 − � .
8πε 0 r i εr

�e model is derived considering only the net work needed to transfer a charged
ion from vacuum to a given medium. �is implicitly assumes no heat exchange
during the process hence resulting in zero entropy contribution.

D�E.� �e relation (∂G�∂p)T = V , combined with the fact that the volume is always
positive, shows that the Gibbs function of a system increases as the pressure
increases (at constant temperature).
E�E.�(b) �e Gibbs energy dependence on temperature for a perfect gas is given by
[�E.��–���], G m (p f ) = G m (p i ) + RT ln(p f �p i ). From the perfect gas law p ∝
(1�V ). �is allows rewriting the previous equation for the change in Gibbs
energy due to isothermal gas expansion

Vi
∆G = nRT ln � �
Vf
52 cm3
= (6.0 × 10−3 mol) × (8.3145 J K−1 mol−1 ) × (298 K) × ln � �
122 cm3
= −13 J .

E�E.�(b) �e variation of the Gibbs energy with pressure is given by [�E.�–���], (∂G�∂T) p =
−S. �e change in entropy is thus

∂G f ∂G i ∂(G f − G i )
∆S = S f − S i = − � � +� � = −� �
∂T p ∂T p ∂T p

∂∆G ∂[(−73.1 J) + T × (42.8 J K−1 )]

= −� � = −� �
∂T p ∂T p

= −(42.8 J K−1 ) = −42.8 J K−1 .

E�E.�(b) �e Gibbs-Helmholtz relation for the change in Gibbs energy is given by [�E.��–
���], (∂[∆G�T]�∂T) p = −∆H�T 2 . Expressing for the change in enthalpy gives

∂[∆G�T] ∂[(−73.1 J)�T + (42.8 J K−1 )]

∆H = −T 2 � � = −T 2 � �
∂T p
∂T p
−73.1 J
= T2 � � = −73.1 J .
T2

E�E.�(b) �e molar Gibbs energy dependence on pressure for an incompressible sub-

stance is given by [�E.��–���], G m (p f ) = G m (p i ) +(p f − p i )Vm . Assuming that
the volume of liquid water changes little over the range of pressures considered

∆G = n[G m (p f ) − G m (p i )] = (p f − p i )nVm = (p f − p i )V
= [(500 × 103 kPa) − (100 × 103 Pa)] × (100 × 10−6 m3 ) = +40.0 J .

For the molar Gibbs energy

∆G ∆G M∆G
∆G m = = =
n m�M ρV
(18.02 g mol−1 ) × (+40.0 J)
= = +7.23 J mol−1 .
(0.997 g cm−3 ) × (100 cm3 )
E�E.�(b) As explained in Section �E.�(c) on page ���, the change in Gibbs energy of a
phase transition varies with pressure as ∆ trs G m (p f ) = ∆ trs G m (p i ) ∫ p i f ∆ trs Vm dp.
p

Assuming that ∆ trs Vm changes little over the range of pressures considered
∆G m = ∆ trs G m (p f ) − ∆ trs G m (p i ) = (p f − p i )∆ trs Vm
= [(5000 × 105 Pa) − (1 × 105 Pa)] × (0.5 × 10−6 m3 mol−1 )
= +2.5 × 102 J mol−1 .

E�E.�(b) �e Gibbs energy dependence on pressure for a perfect gas is given by [�E.��–
���], G m (p f ) = G m (p i ) + RT ln(p f �p i ), thus
pf
∆G m = RT ln � �
pi
100.0 kPa
= (8.3145 J K−1 mol−1 ) × (500 K) × ln � �
50.0 kPa
= +2.88... × 103 J mol−1 = +2.88 kJ mol−1 .

P�E.� �e standard reaction entropy is given by [�C.�b–��], ∆ r G −○ = ∑J ν J ∆ f G −○ (J),

where ν J are the signed stoichiometric numbers.
∆ r G −○ (298 K) = 2∆ f G −○ (NH3 (g)) − ∆ f G −○ (N2 (g)) − 3∆ f G −○ (H2 (g))
= 2 × (−16.45 kJ mol−1 ) − 0 − 3 × 0
= −32.90 kJ mol−1 .
Similarly, the standard reaction enthalpy is [�C.�b–��], ∆ r H −○ = ∑J ν J ∆ f H −○ (J).
∆ r H −○ (298 K) = 2∆ f H −○ (NH3 (g)) − ∆ f H −○ (N2 (g)) − 3∆ f H −○ (H2 (g))
= 2 × (−46.11 kJ mol−1 ) − 0 − 3 × 0
= −92.22 kJ mol−1 .

�e given expression for the reaction Gibbs energy dependence on temperature

is rearranged for ∆G(T2 ) and becomes
T2 T2
∆G(T2 ) = ∆G(T1 ) + ∆H �1 − �
T1 T1
Hence at temperatures 500 K and 1000 K, respectively
500 K 500 K
∆G(500 K) = (−32.90 kJ mol−1 ) + (−92.22 kJ mol−1 ) �1 − �
298 K 298 K
= +7.31 kJ mol−1 .

1000 K 1000 K
∆G(1000 K) = (−32.90 kJ mol−1 ) + (−92.22 kJ mol−1 ) �1 − �
298 K 298 K
= +107 kJ mol−1 .
P�E.� (a) p = (RT)�Vm

∂S ∂p ∂ RT R ∂ R
� � =� � =� � = � T� = .
∂V T ∂T V ∂T Vm V Vm ∂T V Vm

(b) p = (RT)�(Vm − b) − a�Vm2

∂S ∂p ∂ RT a
� � =� � =� � − ��
∂V T ∂T V ∂T Vm − b Vm2 V
R ∂ R
= � T� − 0 = .
Vm − b ∂T V Vm − b

(c) p = (RTe−a�(RT Vm ) )�(Vm − b)

∂S ∂p ∂ RTe−a�(RT Vm )
� � =� � =� �
∂V T ∂T V ∂T Vm − b V
a R
= �1 + � e−a�(RT Vm ) .
RT 2 Vm Vm − b

�e change in entropy for an isothermal expansion is

S(Vf ) Vf ∂S
∆S = � dS = � � � dV
S(Vi ) Vi ∂V T

Comparing the (∂S�∂V )T for the perfect and van der Waals gases implies that
the change in entropy due to expansion (i.e. positive change in V ) is always
larger for the van der Waals gases: (∂S�∂V )T ,vdW > (∂S�∂V )T ,perfect . �is is
because R�(Vm − b) > R�Vm for the excluded volume constant b is positive.
�e result is expected as the relative volume expansion for the van der Waals
gases is always slightly greater than that of the perfect gas due to the �xed �nite
excluded volume. �erefore, the entropy is expected to be more sensitive to the
changes in volume, especially at the very small volume.

P�E.� Using Maxwell’s relation (∂S�∂p)T = − (∂V �∂T) p and (∂S�∂T) p = C p �T the
given equation becomes

∂S ∂S ∂V Cp
dS = � � dp + � � dT = − � � dp + dT
∂p T ∂T p ∂T p T
1 1 ∂V
= �C p dT − � � � � T V dp�
T V ∂T p

�e expansion coe�cient is de�nded as α = (1�V )(∂V �∂T) p , therefore

TdS = C p dT − αT V dp

�e entropy change is de�ned in [�A.�a–��], dS = dq rev �T, hence q rev = ∫i TdS.

f

For an isothermal reversible process q = q rev and dT = 0. �erefore, assuming

 that V and α are constant for the range of pressures considered, the amount of
heat transferred is
S(p f ) pf
q=� dS = � −αT V dp = −αT V (p i − p f ) = −αT V ∆p
S(p i ) pi

= −(1.82 × 104 K ) × (273.15 K) × (100 × 10−6 m3 ) × (1.0 × 108 Pa)

−1

= −497 J .

P�E.� �e Gibbs-Helmholtz relation for the change in Gibbs energy is given by [�E.��–
���], (∂[∆G�T]�∂T) p = −∆H�T 2 . Integrating the equation between the tem-
peratures T1 and T2 and assuming that ∆H is temperature independent gives
T2 ∂ ∆G(T) T2 1
� � � dT = ∆H � − 2 dT
T1 ∂T T p
T1 T
∆G(T2 ) ∆G(T1 ) 1 1
− = ∆H � − �
T2 T1 T2 T1
�is is rearranged for ∆G(T2 )
T2 T2
∆ r G −○ (T2 ) = ∆ r G −○ (T1 ) + ∆ r H −○ �1 − �
T1 T1

Hence for n = 1, n = 2 and n = 3, respectively

190 K
∆ r G 1−○ (190 K) = (46.2 kJ mol−1 ) ×
220 K
190 K
+ (127 kJ mol−1 ) × �1 − �
220 K
= +57.2 kJ mol−1 .

190 K
∆ r G 2−○ (190 K) = (69.4 kJ mol−1 ) ×
220 K
190 K
+ (188 kJ mol−1 ) × �1 − �
220 K
= +85.6 kJ mol−1 .

190 K
∆ r G 3−○ (190 K) = (93.2 kJ mol−1 ) ×
220 K
190 K
+ (273 kJ mol−1 ) × �1 − �
220 K
= +112.8 kJ mol−1 .

I�.� �e statistical de�nition of entropy is given by [�A.�–��], S = k ln W, where W

is the number of microstates, the number of ways in which the molecules of a
system can be distributed over the energy states for a speci�ed total energy. As
explained in Section �A.�(a) on page �� the molecular interpretation of helps
to explain why, in the thermodynamic de�nition given by [�A.�a–��],dS =
q rev �T, the entropy change depends inversely on the temperature. In a system
at high temperature the molecules are spread out over a large number of energy
states. Increasing the energy of the system by the transfer of heat makes more
states accessible, but given that very many states are already occupied the pro-
portionate change in W is small. In contrast, for a system at a low temperature
fewer states are occupied, and so the transfer of the same energy results in a
proportionately larger increase in the number of accessible states, and hence
a larger increase in W. �is argument suggests that the change in entropy for
a given transfer of energy as heat should be greater at low temperatures than
at high, as in the thermodynamic de�nition. As discussed in Section �C.�(a)
on page ��, the statistical de�nition of entropy also justi�es the �ird Law
of thermodynamics. �e law states that the entropy of all perfect crystalline
substances is zero at T = 0. At a molecular level the absence of thermal motion
in a perfectly localized crystalline solid is interpreted as there is only one way
to arrange the molecules like that. �us, W = 1 and from S = k ln W it follows
that S = 0 as stated by the law.
D�A.� Mathematically the change in chemical potential when the pressure is changed
can be traced to the pV term within the Gibbs energy (part of the de�nition
of enthalpy); the product changes when the pressure changes. Physically, an
incompressible system does not store energy like a spring, which is the analogy
for a compressible gas; however, it can transmit energy in the same way that a
hydraulic �uid does. Furthermore, an incompressible system under pressure is
under stress at a molecular level. Its bonds or intermolecular repulsive forces
resist external forces without contraction.

D�A.� Consider the phase diagram shown in Fig. �A.� on page ��� and imagine start-
ing at a pressure and temperature somewhat above the critical point; only a
single phase is present, which would be described as a supercritical �uid. �en
proceed on an clockwise path centred on the critical point. Eventually the path
will reach the liquid–vapour phase boundary, and if the traverse is stopped at
this point the sample will be found to consist of liquid at the bottom of the tube
with vapour above, and a visible meniscus. As the path is continued the system
moves into the liquid phase (in principle the meniscus would rise up the tube
and then disappear) and once more only one phase is present. Eventually the
path takes the system above the critical point and back to the starting point.
�e somewhat curious thing about this path is that it takes us from vapour to
liquid via the usual process of condensation, but then returns the liquid to the
vapour phase without crossing a phase boundary, and so with no visible boiling.

E�A.�(b) In a phase diagram, a single phase is represented by an area, while a line rep-
resents a phase boundary where two phases coexist in equilibrium. Point a
lies within an area and therefore only one phase is present. Point d lies on
the boundary between two areas, and therefore two phases are present. Points
b and c each lie at the intersection of three phase boundaries, so in each case
three phases are present.
E�A.�(b) �e change in Gibbs energy when an in�nitesimal amount dn of substance is
moved from location � to location � is given by (Section �A.�(c) on page ���)
dG = (µ 2 − µ 1 )dn
Assuming that �.�� mmol is a su�ciently small amount to be regarded as in-
�nitesimal, the Gibbs energy change in this case is
∆G = (µ 2 − µ 1 )∆n = (−8.3 × 103 J mol−1 ) × (0.15 × 10−3 mol) = −1.2 J

E�A.�(b) Use the phase rule [�A.�–���], F = C − P + 2, with C = 4 (for four components).
Rearranging for the number of phases gives
P = C−F +2=4−F +2=6−F
�e number of variables that can be changed arbitrarily, F, cannot be smaller
than zero so the maximum number of phases in this case is � .

E�A.�(b) Use the phase rule [�A.�–���], F = C − P + 2, with C = 1 (one component).

Inserting P = 2 gives F = 1 − 2 + 2 = 1. �e condition P = 2 therefore represents
a line . A line has F = 1 because a variation in pressure determines the required
variation in the temperature needed to stay on the line. P = 2 indicates that two
phases are present, so this result con�rms that a situation in which two phases
are in equilibrium is represented by a line in a phase diagram.

E�A.�(b) (i) ��� K and � atm lies in the Ice I region of the phase diagram, so only
one phase (Ice I) will be present.
(ii) ��� K and �� atm lies in the liquid region, so only one phase (liquid) will
be present.
(iii) ���.�� K and ��� Pa corresponds to the triple point of water. So three phases
(Ice I, liquid water, and gas) will be present.

P�A.� (a) At ��� K and �.� atm, the phase diagram indicates that CO2 is a gas. On
increasing the pressure, a point will be reached at which gas and solid are
in equilibrium. Above this pressure only the solid form will exist.
(b) ��� K is above the critical temperature so distinct liquid and gas phases
do not exist. A single phase (a supercritical �uid) therefore exists at all
pressures (except perhaps at extremely high pressures when a solid might
be formed).
(c) ���.� K corresponds to the triple point of CO2 . Below �.�� atm (the pres-
sure corresponding to the triple point) CO2 will exist as a gas. At �.�� atm
solid, liquid and gas phases will all be present in equilibrium. Above
this pressure, the phase diagram shows that only the solid phase will be
present.

P�A.� A schematic phase diagram is shown in Fig �.�. Note that in reality the phase
boundaries may be curved rather than straight. �ere is one triple point which
is marked with a dot.
 s Triple point
⇧
⇧
p ⇧
⇧ γ
α ⇧
s (((
⇧ (
(((
⇧(
β

D�B.� Formally, the pressure derivative of the chemical potential is (∂µ�∂p)T = Vm .

Because the molar volume is always positive, the slope of the change in chemical
potential with respect to change in pressure is positive: that is, the chemical
potential increases with increasing pressure.

E�B.�(b) �e variation of chemical potential with temperature is given by [�B.�a–���],

(∂µ�∂T) p = −S m . For a �nite change this gives ∆µ = −S m ∆T.

∆µ(liquid) = −(65 J K−1 mol−1 ) × (−1.5 K) = +�� J mol−1

∆µ(solid) = −(43 J K−1 mol−1 ) × (−1.5 K) = +�� J mol−1

�e chemical potential of the liquid rises by more than that of the solid. So if
they were initially in equilibrium, the solid will be the more stable phase at the
lower temperature.

E�B.�(b) �e variation of chemical potential with temperature is given by [�B.�a–���],

(∂µ�∂T) p = −S m . For a �nite change this gives ∆µ = −S m ∆T, assuming that
S m is constant over the temperature range.

∆µ = −(53 J K−1 mol−1 ) × ([150 − 100] K) = −2.7 × 103 J mol−1

E�B.�(b) �e variation of chemical potential with pressure at constant temperature is

given by [�B.�b–���], (∂µ�∂p)T = Vm . For a �nite change, and assuming that
Vm is constant over the pressure range, this gives ∆µ = Vm ∆p. �e molar
 volume Vm is given by M�ρ where M is the molar mass of benzene and ρ is
the mass density.
∆µ = Vm ∆p = (M�ρ)∆p
78.1074 × 10−3 kg mol−1
= −3 × ([10 × 106 − 100 × 103 ] Pa)
876.5 kg m
= +8.8 × 102 J mol−1
Note that 1 Pa m3 = 1 J.

E�B.�(b) �e variation of vapour pressure with applied pressure is given by [�B.�–���],

p = p∗ eVm (l)∆ p�RT . Vm is given by Vm = M�ρ where M is the molar mass of
naphthalene (C10 H8 , M = 128.1632 g mol−1 ) and ρ is the mass density.
M 128.1632 g mol−1
Vm = = = 1.10... × 10−4 m3 mol−1
ρ 1.16 × 106 g m−3
(1.10... × 10−4 m3 mol−1 )×([15 × 106 − 1 × 105 ] Pa)
p = (2.0 × 103 Pa)×exp � �
(8.3145 J K−1 mol−1 ) × ([95 + 273.15] K)
= 3420 Pa = �.�� kPa

E�B.�(b) �e relationship between pressure and temperature along the solid–liquid bound-
ary is given by [�B.�–���], p = p∗ + (∆ fus H�T ∗ ∆ fus V )(T − T ∗ ), which is
rearranged to give ∆ fus H. In this case p∗ = 1.00 atm, T ∗ = 427.15 K, p =
1.2 MPa and T = 429.26 K.
p − p∗ ∗
∆ fus H = T ∆ fus V
T − T∗
(1.2 × 106 Pa) − [(1 atm) × (1.01325 × 105 Pa�1 atm)]
= × (427.15 K)
([429.26 − 427.15] K)
× ([152.6 − 142.0] × 10−6 m3 mol−1 )
= 2.36... × 103 J mol−1 = �.� kJ mol−1
�e entropy of transition is given by [�B.�–��], ∆ fus S = ∆ fus H�T, where T is
the transition temperature. At the melting temperature the entropy of fusion is
2.36... × 103 J mol−1
∆ fus S = = �.� J K−1 mol−1
427.15 K

E�B.�(b) �e integrated version of the Clausius–Clapeyron equation [�B.��–���] is given

by ln(p�p∗ ) = −(∆ vap H�R)(1�T − 1�T ∗ ). Rearranging for T gives
−1
1 R p
T =� − ln �
T ∗ ∆ vap H p∗
−1
1 8.3145 J K−1 mol−1 66.0 kPa
=� − × ln �
[20.0 + 273.15] K 32.7 × 103 J mol−1 58.0 kPa
= ��� K or ��.� ○ C
E�B.�(b) �e Clausius–Clapeyron equation [�B.�–���] is d ln p�dT = ∆ vap H�RT 2 . �is
equation is rearranged for ∆ vap H, and the expression for ln p is di�erentiated.
It does not matter that the pressure is given in units of Torr because only the
slope of ln p is required.
d ln p d 3036.8 K 3036.8 K
∆ vap H = RT 2 = RT 2 �18.361 − � = RT 2 � �
dT dT T T2
= (3036.8 K)R = (3036.8 K) × (8.3145 J K−1 mol−1 ) = ��.��� kJ mol−1

E�B.�(b) (i) �e Clausius–Clapeyron equation [�B.�–���] is d ln p�dT = ∆ vap H�RT 2 .

�is equation is rearranged for ∆ vap H, and the expression for ln p is dif-
ferentiated, noting from inside the front cover that ln x = (ln 10) log x. It
does not matter that the pressure is given in units of Torr because only
the slope of ln p is required.
d ln p d log p d 1625 K
∆ vap H = RT 2 = RT 2 ln 10 = RT 2 ln 10 �8.750 − �
dT dT dT T
1625 K
= RT 2 ln 10 � � = (1625 K)R ln 10
T2
= (1625 K) × (8.3145 J K−1 mol−1 ) × ln 10 = ��.�� kJ mol−1
(ii) �e normal boiling point refers to the temperature at which the vapour
pressure is � atm which is ��� Torr. �e given expression, log(p�Torr) =
8.750 − (1625K)�T is rearranged for T and a pressure of ��� Torr is
substituted into it to give
1625 K 1625 K
T= = = ���.� K or �.��� ○ C
8.750 − log(p�Torr) 8.750 − log 760
Note that this temperature lies outside the range 15 ○ C to 35 ○ C for which
the expression for log(p�Torr) is known to be valid, and is therefore an
estimate.

E�B.�(b) �e relationship between pressure and temperature along the solid–liquid bound-
ary is given by [�B.�–���], p = p∗ + (∆ fus H�T ∗ ∆ fus V )(T − T ∗ ). �e value of
∆ fus V is found using Vm = M�ρ where M is the molar mass and ρ is the mass
density:
M M
∆ fus V = Vm (l) − Vm (s) = −
ρ(l) ρ(s)
46.1 g mol−1 46.1 g mol−1
= − = 8.75... × 10−7 m3 mol−1
0.789 × 106 g m−3 0.801 × 106 g m−3
[�B.�–���] is then rearranged for T and the values substituted in to give
T ∗ ∆ fus V
T = T ∗ + (p − p∗ )
∆ fus H
= ([−3.65 + 273.15] K) + �[100 × 106 − 1 × 105 ] Pa�
([−3.65 + 273.15] K) × (8.75... × 10−7 m3 )
× = ��� K or −0.935 ○ C
8.68 × 103 J mol−1
E�B.��(b) �e integrated version of the Clausius–Clapeyron equation [�B.��–���] is given
by ln(p�p∗ ) = −(∆ vap H�R)(1�T −1�T ∗ ). In this case p∗ = 1 atm (correspond-
ing to the normal boiling point, T ∗ = 100 ○ C) and p = 1 bar (corresponding to
the standard boiling point). Rearranging for T and putting in the numbers
gives
−1
1 R p
T =� ∗ − ln �
T ∆ vap H p∗
−1
1 8.3145 J K−1 mol−1 1 × 105 Pa
=� − × ln �
[100 + 273.15] K 40.7 × 103 J mol−1 1.01325 × 105 Pa
= ���.�... K or ��.�... ○ C

�e standard boiling point is therefore lower than the normal boiling point by
373.15 K − 372.7... K = 0.37 K .

E�B.��(b) Using 1 W = 1 J s−1 and 1 ha = 1 × 104 m2 , the rate at which energy is absorbed
is
(0.87 kW m−2 ) × (1 × 104 m2 ) = 8.7 × 103 kJ s−1 . �e rate of vaporization is
then
rate of energy absorption 8.7 × 103 kJ s−1
= = 1.97... × 102 mol s−1
∆ vap H 44 kJ mol−1
Multiplication by the molar mass of water gives the rate of loss of water as
(1.97... × 102 mol s−1 ) × (18.0158 g mol−1 ) = �.� kg s−1 .

E�B.��(b) Vapour pressure as a function of temperature is given by [�B.��–���], except

that ∆ vap H is replaced by ∆ sub H. Using the triple point values for p∗ and T ∗
the partial pressure expected for ice at −5○ C is
∆ sub H 1 1
p = p∗ exp �− � − ∗ ��
R T T
51 × 103 J mol−1 1 1
= (611 Pa) × exp �− −1 � − ��
−1
8.3145 J K mol [−5 + 273.15] K 273.16 K
= �.�� kPa

�is is less than the partial pressure of water in the atmosphere, so yes , the
frost will sublime. A partial pressure of �.�� kPa or more would be needed to
ensure that the frost remains.

E�B.��(b) (i) Trouton’s rule (Section �B.� on page ��) states that ∆ vap H�T ≈ 85 J K−1 mol−1
where T is the normal boiling point. Rearranging for ∆ vap H gives

∆ vap H = (85 J K−1 mol−1 )T = (85 J K−1 mol−1 ) × ([69.0 + 273.15] K)

= 2.90... × 104 J mol−1 = �� kJ mol−1
 (ii) �e variation of vapour pressure with temperature is given by [�B.��–���]:
∆ vap H 1 1
p = p∗ exp �− � − ∗ ��
R T T
�e values T ∗ = 69.0 ○ C and p∗ = 1 atm or 1.01325 × 105 Pa, are used,
hence at ��○ C
p = (1.01325 × 105 Pa)
2.90... × 104 J mol−1 1 1
× exp �− � − ��
8.3145 J K−1 mol−1 (25 + 273.15) K (69.0 + 273.15) K
= �� kPa
and at ��○ C
p = (1.01325 × 105 Pa)
2.90... × 104 J mol−1 1 1
× exp �− −1 � − ��
−1
8.3145 J K mol (60 + 273.15) K (69.0 + 273.15) K
= �� kPa

E�B.��(b) �e relationship between pressure and temperature along the solid–liquid bound-
ary is given by [�B.�–���], p = p∗ + (∆ fus H�T ∗ ∆ fus V )(T − T ∗ ). �e molar
volume is Vm = M�ρ where M is the molar mass and ρ is the mass density
∆ fus V = Vm (l) − Vm (s) = M�ρ(l) − M�ρ(s)
�is expression is inserted into [�B.�–���], which is then rearranged for T. T ∗ ,
p∗ , and ∆ vap H are taken as the values corresponding to the normal melting
point of ice, that is, � ○ C (273.15 K) and � atm (101.325 kPa). It is assumed that
∆ vap H is constant over the temperature range of interest.

T∗ M M
T = T ∗ + (p − p∗ ) � − �
∆ fus H ρ(l) ρ(s)
273.15 K
= (273.15 K) + ([10 × 106 − 1.01325 × 105 ] Pa) ×
6.008 × 103 J mol−1
18.0158 g mol−1 18.0158 g mol−1
×� − � = ��� K or −0.74 ○ C
0.998 × 106 g m−3 0.915 × 106 g m−3

P�B.� At the triple point the vapour pressures of the solid and liquid are equal, so the
two expressions for the vapour pressure are set equal
10.5916 − (1871.2 K)�T = 8.3186 − (1425.7 K)�T
�is expression is rearranged to �nd T as
(1871.2 − 1425.7) K
T= = 1.95... × 102 K = ���.�� K
(10.5916 − 8.3186)
 �is temperature is then substituted back into one of the expressions for the
pressure
1871.2 K
log(p�Torr) = 10.5916 − = 1.04...
1.95... × 102 K
and so p = 101.04 ... Torr = ��.��� Torr .

P�B.� (a) �e temperature dependence of the vapour pressure is given by [�B.�a–

���], dp�dT = ∆ vap S�∆ vap V . �e entropy change is written as ∆ vap H�T
and ∆ vap V is Vm (g) − Vm (s).

dp ∆ vap H
=
dT T(Vm (g) − Vm (l))
14.4 × 103 J mol−1
=
(180 K) × ([14.5 × 10−3 − 115 × 10−6 ] m3 mol−1 )
= 5.56... × 103 Pa K−1 = �.�� kPa K−1

1 Pa m3 = 1 J has been used.

(b) �e Clausius–Clapeyron equation, [�B.�–���], is d ln p�dT = ∆ vap H�RT 2 .
�is is rewritten as dp�dT = p∆ vap H�RT 2 using dx�x = d ln x.

dp p∆ vap H (1.01325 × 105 Pa) × (14.4 × 103 J mol−1 )

= =
dT RT 2 (8.3145 J K−1 mol−1 ) × (180 K)2
= 5.41... × 103 Pa K−1 = �.�� kPa K−1

�e percentage error from the value in part (a) is

(5.56... − 5.41...) × 103 Pa K−1

× 100 % = �.�� %
5.56... × 103 Pa K−1

P�B.� (a) From the variation of chemical potential with temperature (at constant
pressure) [�B.�b–���], (∂µ�∂T) p = Vm , the slope of the chemical poten-
tial against pressure is equal to the molar volume. �e di�erence in slope
on either side of the normal freezing point of water is therefore

∂µ(l) ∂µ(s)
� � −� � = Vm (l) − Vm (s) = ∆ fus V .
∂p T ∂p T

Vm is given by M�ρ, so the di�erence in slope is

M M
∆ fus V = Vm (l) − Vm (s) = −
ρ(l) ρ(s)
18.0158 g mol−1 18.0158 g mol−1
= −
1.000 × 106 g m−3 0.917 × 106 g m−3
= −1.63... × 10−6 m3 mol−1 = −1.63 × 10−6 J Pa−1 mol−1

where 1 J = 1 Pa m3 has been used.

 (b) Similarly,

∂µ(g) ∂µ(l)
� � −� � = Vm (g) − Vm (s) = ∆ vap V
∂p T ∂p T
M M
= −
ρ(g) ρ(l)
18.0158 g mol−1 18.0158 g mol−1
= −
0.598 × 103 g m−3 0.958 × 106 g m−3
= 3.01... × 10−2 m3 mol−1 = 0.0301 J Pa−1 mol−1

(c) From part (b)

∂µ(g) ∂µ(l) ∂[µ(g) − µ(l)]

� � −� � = ∆ vap V hence � � = ∆ vap V
∂p T ∂p T ∂p p

Rewriting this for a �nite change gives ∆[µ(g) − µ(l)] = ∆ vap V × ∆p. So
if the pressure is increased by ∆p = 0.2 atm from 1.0 atm to 1.2 atm, the
change in µ(g) − µ(l) is

1.01325 × 105 Pa
∆[µ(g) − µ(l)] = (0.0301... J Pa−1 mol−1 ) × (0.2 atm) ×
1 atm
= 610 J mol−1

�erefore, since liquid water and vapour are in equilibrium at 100 ○ C

and 1.0 atm, if the pressure is raised to 1.2 atm the chemical potential of
water vapour will exceed that of liquid water by ��� J mol−1 . �e fact
that µ(g) > µ(l) indicates that the water vapour will have a tendency to
condense under these conditions.

P�B.� Using the perfect gas equation ([�A.�–�]) the amount in moles of water vapour,
n g , in the 50 dm3 of air a�er it has bubbled through the water is

p H2 O V
ng =
RT

where p H2 O is the vapour pressure of the water. �e heat required to vaporize

this amount of water is n g ∆ vap H:

p H2 O V
q=− × ∆ vap H
RT

where q is the heat which enters the liquid water; the minus sign is needed
because the heat has le� the water. �is heat is equal to q = n l C m ∆T (Sec-
tion �A.�(b) on page ��) where C m is the molar heat capacity and n l is the
amount in moles of water. n l is given by m�M where m is the mass of water
 and M is the molar mass. It follows that ∆T = q�n l C m

��� � � � � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � � � � ��
q

q q pH O V M
∆T = = =− 2 × ∆ vap H ×
n l C m (m�M)C m RT mC m
(3.17 × 103 Pa) × (50 × 10−3 m3 )
=− × (44.0 × 103 J mol−1 )
(8.3145 J K−1 mol−1 ) × ([25 + 273.15] K)
18.0158 g mol−1
× = −2.68... K
(250 g) × (75.5 J K−1 mol−1 )

So the �nal temperature will be (25 − 2.68...) ○ C = ��.� ○ C

P�B.�� (a) �e normal boiling point is the temperature at which the vapour pressure
is equal to 1 atm, or 760 Torr. From the data, this is at ���.� ○ C .
(b) �e integrated form of the Clausius–Clapeyron equation, given by [�B.��–
���], ln(p�p∗ ) = −(∆ vap H�R)(1�T − 1�T ∗ ), is rewritten as

p ∆ vap H 1 ∆ vap H
ln =− +
p∗ R T RT ∗

�is implies that a plot of ln(p�p∗ ) against 1�T should be a straight line
of slope −∆ vap H�R and intercept ∆ vap H�RT ∗ ; p∗ may be taken to be
760 Torr (1 atm). �e plot is shown in Fig. �.�.

θ�○ C p�Torr T −1 �K−1 ln(p�p∗ )

57.4 1 0.003 025 −6.633
100.4 10 0.002 677 −4.331
133.0 40 0.002 462 −2.944
157.3 100 0.002 323 −2.028
203.5 400 0.002 098 −0.642
227.5 760 0.001 997 0.000

�e data fall on a good straight line, the equation of which is

ln(p�p∗ ) = (−6.446 × 103 ) × (T −1 �K−1 ) + 12.91

�e slope is equal to −∆ vap H�R, so:

∆ vap H = −slope × R = −(−6.446 × 103 K) × (8.3145 J K−1 mol−1 )

= ��.� kJ mol−1

P�B.�� (a) �e expression dH = C p dT + V dp implies that for a phase change

d∆ trs H = ∆ trs C p dT + ∆ trs V dp

 1
0
−1
−2

ln(p�p∗ )
−3
−4
−5
−6
−7
0.0018 0.0022 0.0026 0.0030
T �K
−1 −1

�e Clayperon equation [�B.�a–���], dp�dT = ∆ trs S�∆ trs V , is rearranged

to give ∆ trs V dp = ∆ trs SdT and this is used to replace ∆ trs V dp in the
previous equation: d∆ trs H = ∆ trs C p dT + ∆ trs SdT. Replacing ∆ trs S by
∆ trs H�T gives the required expression:
∆ trs H
d∆ trs H = ∆ trs C p dT + dT
T

(b) Starting with the second expression, application of the quotient rule d(u�v) =
(vdu − udv)�v 2 to the le� hand side and d ln x = dx�x to the right hand
side gives

∆ trs H Td∆ trs H − ∆ trs HdT ∆ trs C p dT

d� � = ∆ trs C p d ln T hence =
T T2 T
�is expression is rearranged for d∆ trs H to obtain the �rst expression:
∆ trs H
d∆ trs H = ∆ trs C p dT + dT
T

P�B.�� �e variation of vapour pressure with applied pressure is given by [�B.�–���],

p = p∗ eVm ∆P�RT . In this case the change in pressure (due to the depth) is ∆P =
ρgd. Since ρ = M�Vm , equation [�B.�–���] becomes

p = p∗ eVm (M�Vm )gd�RT = p∗ e M gd�RT

At a depth of 10 m the e�ect on the vapour pressure is

(18.0158 × 10−3 kg mol−1 ) × (9.81 m s−1 ) × (10 m)

p�p∗ = exp � � = 1.00071
(8.3145 J K−1 mol−1 ) × ([25 + 273.15] K)

�e fractional increase in vapour pressure is therefore �.����� or �.��� % .

P�B.�� �e �rst derivative of chemical potential with respect to temperature is given
by equation [�B.�a–���], (∂µ�∂T) p = −S m . �e second derivative is therefore

∂2 µ ∂S m
� � = −� �
∂T p
2 ∂T p

Entropy is de�ned by dS = dq rev �T ([�A.�a–��]) and, from section Section �B.�

on page ��, at constant pressure dq rev = dH = C p dT. �erefore
C p,m dT ∂S m C p,m
dS m = and hence � � =
T ∂T p T
Consequently the curvature of the chemical potential with temperature is

(∂ 2 µ�∂T 2 ) p = −C p,m �T

Heat capacity is invariably positive, so this expression implies a negative cur-

vature (since T cannot be negative).
For water, the curvatures of the liquid and gas lines at the normal boiling point
(���.�� K) are:
∂ 2 µ(l) −C p,m (l) −75.3 J K−1 mol−1
liquid line: � � = = = −0.202 J K−2 mol−1
∂T 2 p T 373.15 K
∂ 2 µ(g) −C p,m (g) −33.6 J K−1 mol−1
gas line: � � = = = −0.0900 J K−2 mol−1
∂T 2 p T 373.15 K

�e magnitude of the curvature is therefore greater for the liquid.

I�.� (a) �e expressions are plotted on the graph shown in Fig. �.�. Note that the
liquid-vapour line is only plotted for T3 ≤ T ≤ Tc because the liquid phase
does not exist below the triple point and there is no distinction between
liquid and vapour above the critical point. �e solid-liquid line is plotted
for T ≥ T3 .
(b) �e standard melting point is the temperature corresponding to a pres-
sure of 1 bar on the solid-liquid boundary. Setting p = 1 bar in the equa-
tion for the solid-liquid boundary and substituting in the value of p 3
gives:
1 = 0.4362 × 10−6 + 1000(5.60 + 11.727x)x
�is equation is rearranged to the standard quadratic form
11727x 2 + 5600x − 0.9999995638 = 0
which on solving for x gives x = 1.78... × 10−4 or x = −0.477.... �en,
since x = T�T3 − 1 where T3 = 178.15 K, it follows that
T = 178.15(1.78... × 10−4 + 1) = 178.18 K
or T = 178.15(−0.477... + 1) = 93.11 K
 50

40

30

p�bar
Solid Liquid
20

10
Vapour
0
0 100 200 300 400 500 600 700
T�K

�e 93.11 K solution is rejected since it lies below T3 where the liquid, and
therefore the solid-liquid boundary, does not exist. �e standard melting
point is therefore estimated to be 178.18 K .

(c) �e standard boiling point is the temperature at the point on the liquid-
vapour phase boundary corresponding to p = 1 bar. Substituting this
value of p into the equation for the liquid-vapour boundary and noting
that ln 1 = 0 gives

0 = −10.418�y+21.157−15.996y+14.015y 2 −5.0120y 3 +4.7334(1− y)1.70

Solving numerically gives

y = 0.645... and so T = y × Tc = 0.645... × 593.95 = 383.54 K

(d) Use the Clapeyron equation for the liquid-vapour boundary [�B.�–���]:

dp ∆ vap H dp
= which rearranges to ∆ vap H = T∆ vap V ×
dT T∆ vap V dT

To �nd dp�dT, use d ln x = dx�x so that dp�dT = p × d ln p�dT. �e

expression for ln p is inserted and di�erentiated, and then evaluated at
the standard boiling point found above. For the evaluation of d ln p�dT it
does not matter that the expression has p in bar not Pa because the slope
 of ln p is independent of the units of p due to the logarithm.
dp d ln p d ln p dy
=p = p× ×
dT dT dy dT
d 10.418
= p× �− + 21.157 − 15.996y + 14.015y 2 − 5.0120y 3
dy y
d T
+ 4.7334(1 − y)1.70 � × � �
dT Tc
p 10.418
= ×� − 15.996 + 28.030y − 15.0360y 2
Tc y2

− 8.04678(1 − y)0.70 �

105 Pa 10.418
= �
593.95 K (0.645...)2
− 15.996 + 28.030(0.645...) − 15.0360(0.645...)2

− 8.04678(1 − 0.645...)0.70 � = 2.84... × 103 Pa K−1

�en
dp
∆ vap H = T∆ vap V ×
dT
= (383.54 K) × ([30.3 − 0.12] × 10−3 m3 mol−1 ) × (2.84... × 103 Pa K−1 )
= 33.0 kJ mol−1

I�.� (a) �e data are plotted in Fig. �.�.

4.0
p�MPa

2.0

0.0
100 120 140 160 180 200
T�K

�ese data �t well to the cubic

p�MPa = (4.989×10−6 K−3 )T 3 −(1.452×10−3 K−2 )T 2 +(0.1461 K−1 )T−5.058
�is equation is used to plot the line on the graph.
(b) �e standard boiling point corresponds to the temperature at which p =
1 bar or 0.1 MPa. �is value is substituted into the �tted function to give

0.1 = (4.989×10−6 K−3 )T 3 −(1.452×10−3 K−2 )T 2 +(0.1461 K−1 )T−5.058

which, on solving numerically using mathematical so�ware, yields

T = 1.11... × 10−2 K = ��� K

(c) �e Clapeyron equation for the liquid-vapour boundary is [�B.�–���]:

dp ∆ vap H dp
= hence ∆ vap H = T∆ vap V ×
dT T∆ vap V dT

�e value of dp�dT is obtained by di�erentiating the �tted function and

substituting in the value of T found above.

d(p�MPa)
= (14.967 × 10−3 K−3 )T 2 − (2.904 × 10−3 K−2 )T + (0.1461 K−1 )
dT
= (14.967 × 10−3 K−3 ) × (1.11... × 102 K)2
− (2.904 × 10−3 K−2 ) × (1.11... × 102 K) + (0.1461 K−1 )
= 8.57... × 10−3 K−1

so that
dp
= 8.57... × 10−3 MPa K−1 = 8.57... × 103 Pa K−1
dT
�erefore
dp
∆ vap H = T∆ vap V ×
dT
10−3 m3
= (1.11... × 102 K) × ([8.89 − 3.80 × 10−2 ] dm3 mol−1 ) ×
1 dm3
× (8.57 × 103 Pa K−1 ) = 8.49 kJ mol−1
D�A.� �e change in Gibbs energy at constant temperature is equal to the maximum
additional (non-expansion) work that the system can do dG = dw add,max , [�D.�–
���]. Changing the composition of a mixture gives rise to a change in Gibbs
energy, given by [�A.�–���], dG = µ A dn A + µ B dn B . . .. It therefore follows that

dw add,max = µ A dn A + µ B dn B . . .

and so non-expansion work can arise from the changing composition of a sys-
tem.

D�A.� �is is discussed in Section �A.� on page ���. �e chemical potential of a

perfect gas depends on its partial pressure p A via µ A = µ −A○ +RT ln p A . Consider
�rst the pure liquid, which has chemical potential µ ∗A (l) and vapour pressure
p∗A . When the liquid and gas are in equilibrium, their chemical potentials are
equal
µ ∗A (l) = µ −A○ (g) + RT ln p∗A
If A is now one component of a mixture, the chemical potentials of A in the
liquid and in the gas are still equal

µ A (l) = µ −A○ (g) + RT ln p A

Note that the ∗ is not present as A is not pure. �e �rst equation is taken away
from the second to give an expression for the chemical potential of A in the
liquid in terms of its partial pressure in the vapour
pA
µ A (l) = µ∗A (l) + RT ln (�.�)
p∗A

Raoult’s law gives the partial pressure of A is terms of the mole fraction in the
liquid: p A = x A p∗A , so it follows that p A �p∗A = x A and hence

µ A (l) = µ ∗A (l) + RT ln x A

�is equation relates the chemical potential of a component in a mixture to its

mole fraction.
 If Henry’s law applies, p A = K A x A , eqn �.� becomes

KA xA KA
µ A (l) = µ ∗A (l) + RT ln ∗
= µ ∗A (l) + RT ln ∗ +RT ln x A
pA pA
��� � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � �
�e term indicated by the brace is de�ned as a new standard chemcial potential
µ −A○ to give
µ A (l) = µ −A○ + RT ln x A
�is expression also relates the chemical potential of a component in a mixture
to its mole fraction.

E�A.�(b) �e partial molar volume of B is de�ned from [�A.�–���] as

∂V
VB = � �
∂n B p,T ,n ′

�e polynomial given relates υ to x, and so from this it is possible to compute

the derivative dυ�dx. �is required derivative is dV �dn B (where the partials
are dropped for simplicity), which is related to dυ�dx in the following way

dV dV dυ dx
� �=� �� �� �
dn B dυ dx dn B

Because x = n B �mol, dx�dn B = mol−1 , and because υ = V �cm3 , dυ�dV =

cm−3 and so dV �dυ = cm3 . Hence

dV dV dυ dx dυ
� �=� �� �� � = � � cm3 mol−1
dn B dυ dx dn B dx

�e required derivative is

dυ
� � = −22.574 9 + 1.137 84x + 0.030 69 x 2 + 0.009 36 x 3
dx
hence

VB = �−22.574 9 + 1.137 84 x + 0.030 69 x 2 + 0.009 36 x 3 � cm3 mol−1

E�A.�(b) �e partial molar volume of solute B (here MgSO� ) is de�ned from [�A.�–���]
as
∂V
VB = � �
∂n B p,T ,n ′
�e total volume is given as a function of the molality, but this volume is de-
scribed as that arising from adding the solute to � kg of solvent. �e molality of
a solute is de�ned as (amount in moles of solute)/(mass of solvent in kg), there-
fore because in this case the mass of solvent is � kg, the molality is numerically
equal to the amount in moles, n B .
�e polynomial given relates υ to x, and so from this it is possible to compute
the derivative dυ�dx. �is required derivative is dV �dn B (where the partials
are dropped for simplicity), which is related to dυ�dx in the following way

dV dV dυ dx
� �=� �� �� �
dn B dυ dx dn B

�e quantity x is de�ned as b�b −○ , but it has already been argued that the molal-
ity can be expressed as n B �(1 kg), hence x = n B �(mol) and therefore dx�dn B =
mol−1 . Because υ = V �cm3 , dυ�dV = cm−3 and so dV �dυ = cm3 . Hence

dV dV dυ dx dυ
� �=� �� �� � = � � cm3 mol−1
dn B dυ dx dn B dx
�e required derivative is

dυ
� � = 69.38(x − 0.070)
dx
Hence the expression for the partial molar volume of B (NaCl) is

VB = [69.38(x − 0.070)] cm3 mol−1

�e partial molar volume when b�b −○ = 0.050 is given by

VB = 69.38(x − 0.070) cm3 mol−1 = 69.38(0.050 − 0.070) cm3 mol−1

= −1.38... cm3 mol−1 = −1.39 cm3 mol−1

�e total volume is calculated from the partial molar volumes of the two com-
ponents, [�A.�–���], V = n A VA + n B VB . In this case V and VB are known,
so VA , the partial molar volume of the solvent water can be found from VA =
(V − n B VB )�n A .
�e total volume when b�b−○ = 0.050 is given by

V = 1001.21 + 34.69 × (0.050 − 0.070)2 = 1001.2... cm3

�e amount in moles of � kg of water is (1000 g)�[(16.00+2×1.0079) g mol−1 ] =

55.5... mol, hence

V − n B VB (1001.2... cm3 ) − (0.05 mol) × (−1.38... cm3 mol−1 )

VA = =
nA 55.5... mol
= 18.0 cm3 mol−1

where, as before, for this solution a molality of �.�� mol kg−1 corresponds to
n B = 0.05 mol.
E�A.�(b) For a binary mixture the Gibbs–Duhem equation, [�A.��b–���], relates changes
in the chemical potentials of A and B

n A dµ A + n B dµ B = 0

If it is assumed that the di�erential can be replaced by the small change

(0.22 n B ) × (−15 J mol−1 ) + n B δµ B = 0

(0.22 n B )
hence δµ B = − (−15 J mol−1 ) = +3.3 J mol−1
nB

E�A.�(b) Because the gases are assumed to be perfect and are at the same temperature
and pressure when they are separated, the pressure and temperature will not
change upon mixing. �erefore [�A.��–���], ∆ mix S = −nR(x A ln x A +x B ln x B ),
applies. �e amount in moles is computed from the total volume, pressure
and temperature using the perfect gas equation: n = pV �RT. Because the
separate volumes are equal, and at the same pressure and temperature, each
compartment contains the same amount of gas, so the mole fractions of each
gas in the mixture are equal at 0.5.

∆ mix S = −nR(x A ln x A + x B ln x B ) = −(pV �T)(x A ln x A + x B ln x B )

(100 × 103 Pa) × (250 × 10−6 m3 )
=− (0.5 ln 0.5 + 0.5 ln 0.5)
273.15 K
= +0.0634 J K−1

Note that the pressure in expressed in Pa and the volume in m3 ; the units of the
result are therefore (N m−2 ) × (m3 ) × (K−1 ) = N m K−1 = J K−1 .
Under these conditions the Gibbs energy of mixing is given by [�A.��–���],
∆ mix G = nRT(x A ln x A + x B ln x B ); as before n = pV �RT.

∆ mix G = nRT(x A ln x A + x B ln x B ) = (pV )(x A ln x A + x B ln x B )

= [(100 × 103 Pa) × (250 × 10−6 m3 )](0.5 ln 0.5 + 0.5 ln 0.5)
= −17.3 J

�e units of the result are (N m−2 )×(m3 ) = N m = J. As expected, the entropy

of mixing is positive and the Gibbs energy of mixing is negative.

E�A.�(b) �e partial pressure of gas A, p A above a liquid mixture is given by Raoult’s

Law, [�A.��–���], p A = x A p∗A , where x A is the mole fraction of A in the liquid
and p∗A is the vapour pressure over pure A. �e total pressure over a mixture
of A and B is p A + p B .
In this case the mixture is equimolar, so x A = x B = 12 . If A is �,�-dimethylbenzene
and B is �,�-dimethylbenzene the total pressure is

p = x A p∗A + x B p∗B = 12 (20 kPa) + 21 (18 kPa) = �� kPa

 �e composition of the vapour – that is the mole fractions of A and B in the
vapour – is calculated from their partial pressures according to [�A.�–�], p A =
y A p, where y A is the mole fraction of A in the vapour and p is the total pressure.
�e partial pressure of A is also given by p A = x A p∗A . �ese two expressions for
p A is equated to give

x A p∗A
y A p = x A p∗A hence yA =
p
�e composition of the vapour is therefore

x A p∗A
1
× (20 kPa)
yA = = 2
= �.��
p 19 kPa
x B p∗B
1
× (18 kPa)
yB = = 2
= �.��
p 19 kPa

E�A.�(b) �e total volume is calculated from the partial molar volumes of the two com-
ponents using [�A.�–���], V = n A VA + n B VB . �e task is therefore to �nd the
amount in moles, n A and n B , of A and B in a given mass m of solution. If the
molar masses of A and B are M A and M B then it follows that

m = nA MA + nB MB

�e mole fraction of A is de�ned as x A = n A �(n A + n B ), hence n A = x A (n A +

n B ) and likewise for B. With these substitutions for n A and n B the previous
equation becomes
m
m = x A M A (n A + n B ) + x B M B (n A + n B ) hence (n A + n B ) =
xA MA + xB MB
�is latter expression for the total amount in moles, (n A + n B ), is used with
n A = x A (n A + n B ) to give
mx A
n A = x A (n A + n B ) =
xA MA + xB MB
and likewise
mx B
nB =
xA MA + xB MB
With these expressions for n A and n B the total volume is computed from the
partial molar volumes
mx A VA mx B VB
V = n A VA + n B VB = +
xA MA + xB MB xA MA + xB MB
m
= [x A VA + x B VB ]
xA MA + xB MB
m
= [x A VA + (1 − x A )VB ]
x A M A + (1 − x A )M B

where on the last line x B = (1 − x A ) is used.

 �is expression for the volume of �.��� kg evaluates as

1000 g
V=
0.3713 × (241.1 g mol ) + (1 − 0.3713) × (198.2 g mol−1 )
−1

−1 −1
× �0.3713 × (188.2 cm3 mol ) + (1 − 0.3713) × (176.14 cm3 mol )�
= ���.� cm3

E�A.�(b) Consider a solution of A and B in which the fraction (by mass) of A is α.

�e total volume of a solution of A and B is calculated from the partial molar
volumes of the two components using [�A.�–���], V = n A VA + n B VB . In this
exercise V and VA are known, so the task is therefore to �nd the amount in
moles, n A and n B , of A and B in the solution of known mass density ρ.
�e mass of a volume V of the solution is ρV , so the mass of A is αρV . If
the molar mass of A is M A , then the amount in moles of A is n A = αρV �M A .
Similarly, n B = (1 − α)ρV �M B . �e volume is expressed using these quantities
as
αρV VA (1 − α)ρV VB
V = n A VA + n B VB = +
MA MB
�e term V cancels between the �rst and third terms to give

αρVA (1 − α)ρVB
1= +
MA MB

�is equation is rearranged to give an expression for VA

MA (1 − α)VB ρ
VA = �1 − �
αρ MB

In this exercise let A be H� O and B be ethanol, and as the mixture is ��% ethanol
and ��% H� O by mass, α = 0.8. �e molar mass of A (H� O) is M A = 16.00 +
2 × 1.0079 = 18.0158 g mol−1 and the molar mass of B (ethanol) is M B = 2 ×
12.01 + 16.00 + 6 × 1.0079 = 46.0674 g mol−1 . �e above expression for VA
evaluates as

MA (1 − α)VB ρ (18.0158 g mol−1 )

VA = �1 − �=
αρ MB 0.8 × (0.9687 g cm−3 )
−1
� (1 − 0.8) × (52.2 cm3 mol ) × (0.9687 g cm−3 ) �
× 1−
� 46.0674 g mol−1 �
−1
= ��.� cm3 mol

In evaluating this expression the density has been converted to units of g cm−3 :
968.7 kg m−3 = 968.7 × 103 × 10−6 g cm−3 = 0.9687 g cm−3 .
 150

100

p B �(kPa)
50

0
0.000 0.005 0.010 0.015 0.020
xB

E�A.�(b) Henry’s law gives the partial vapour pressure of a solute B as p B = K B x B ,

[�A.��–���]. A test of this law is to make a plot of p B against x B which is
expected to be a straight line with slope K B ; such a plot is shown in Fig. �.�
�e data fall on quite a good straight line, the equation of which is

p HCl �(kPa) = 8.41 × 103 × (x B ) − 2.784

If Henry’s law is obeyed the pressure should go to zero as x B goes to zero, and
the graph shows that this is not quite achieved. Overall the conclusion is that
these data obey Henry’s law reasonably well. �e Henry’s law constant K B is
computed from the slope as 8.4 × 103 kPa .

E�A.�(b) In Section �A.�(b) on page ��� it is explained that for practical applications
Henry’s law is o�en expressed as p B = K B b B , where b B is the molality of the
solute, usually expressed in mol kg−1 . �e molality is therefore calculated from
the partial pressure as b B = p B �K B .
Molality is the amount of solute per kg of solvent. �e mass m of a volume V
of solvent is given by m = ρV , where ρ is the mass density of the solvent. If the
amount of solute in volume V is n B , the molar concentration c B is related to
the molality by
�
bB

nB nB nB
cB = = =ρ = ρb B
V m�ρ m
Using Henry’s law the concentration is therefore given by

�
bB

pB ρx B p
c B = ρb B = ρ =
KB KB
where the partial pressure p B is expressed in terms of the mole fraction and the
total pressure p, p B = x B p.
 �e Henry’s law constant for CH� in benzene is 44.4 × 103 kPa kg mol−1 and
the density of benzene is �.��� g cm−3 .

ρp N2 (0.879 × 103 kg m−3 ) × (100 kPa)

c N2 = = −1 = 1.97... mol m−3
K N2 44.4 × 10 kPa kg mol
3

�e molar concentration is therefore 2.0 × 10−3 mol dm−3 .

E�A.��(b) In Section �A.�(b) on page ��� it is explained that for practical applications
Henry’s law is o�en expressed as p B = K B b B , where b B is the molality of the
solute, usually expressed in mol kg−1 . �e molality is therefore calculated from
the partial pressure as b B = p B �K B , and the partial pressure is expressed as
p B = x B p, where p is the total pressure �e Henry’s law constant for N� in water
is 1.56 × 105 kPa kg mol−1 , and for O� the constant is 7.92 × 104 kPa kg mol−1
�e total pressure is assumed to be � atm (101.325 kPa)

x N2 p 0.78 × (101.325 kPa)

b N2 = = = 5.1 × 10−4 mol kg−1
K N2 1.56 × 105 kPa kg mol−1

x O2 p 0.21 × (101.325 kPa)

b O2 = = −1 = 2.7 × 10
−4
mol kg−1
K O2 7.92 × 10 kPa kg mol
4

E�A.��(b) As explained in Exercise E�A.�(b) the concentration of a solute is estimated

as c B = ρp B �K B where ρ is the mass density of the solvent. �e Henry’s law
constant for CO� in water is 3.01 × 103 kPa kg mol−1 and the density of water
is �.��� g cm−3 or ��� kg m−3 .

ρp CO2 (997 kg m−3 ) × (2.0 atm) × (101.325 kPa�1 atm)

c CO2 = =
K CO2 3.01 × 103 kPa kg mol−1
= 67.1... mol m−3

�e molar concentration is therefore �.��� mol dm−3 .

P�A.� �e Gibbs–Duhem equation [�A.��b–���], expressed in terms of partial molar

volumes is n A dVA + n B dVB = 0. �is rearranges to
nA
dVB = − dVA
nB

Division of both the top of bottom of the fraction on the right by (n A + n B )

allows this equation to be rewritten in terms of the mole fractions

n A �(n A + n B ) xA xA
dVB = − dVA = − dVA = − dVA
n B �(n A + n B ) xB (1 − x A )
�e partial molar volumes are functions of the composition of the mixture
which is speci�ed by x A and x B . Both sides are integrated between the limits
(x A = 0, x B = 1), that is pure B, and an arbitrary composition (x A , x B ) to give
(x A ,x B ) (x A ,x B ) xA
� dVB = − � dVA
(x A =0,x B =1) (x A =0,x B =1) (1 − x A )
�e le�-hand side evaluates to VB − VB∗ , where VB∗ is the molar volume of pure
B, and VB is the partial molar volume at the speci�ed composition. It follows
that
(x A ,x B ) xA
VB = VB∗ − � dVA (�.�)
(x A =0,x B =1) (1 − x A )

If the variation of VA with x A is known, then the integral on the right can be
evaluated and hence a value found for VB .
Let component A be trichloromethane and component B be propanone. �e
task is �rst to use the given data of Vm as a function of x A to �nd VA as a function
of x A . �e de�nition of VA is
∂V
VA = � �
∂n A n B

which is interpreted as the slope of a plot of V against n A , at constant n B . �e

data provided is of the molar volume, de�ned as Vm = V �(n A + n B ), as a
function of x A , so the next step is to use these data to �nd V as a function
of n A at �xed n B . Arbitrarily, set n B = 1 mol so that

V = [n A + (1 mol)] Vm

�e mole fraction x A is given by x A = n A � [n A + (1 mol)] which rearranges to

(1 mol) × x A
nA = (�.�)
1 − xA
It follows that
(1 mol) × x A (1 mol)
V = [n A + (1 mol)] Vm = � + (1 mol)� Vm = Vm
1 − xA 1 − xA

�ese expressions are used to draw up the following table and plot the graph in
Fig. �.�.

−1
xA Vm �(cm3 mol ) V �(cm3 ) n A �(mol)
0 73.99 73.99 0
0.194 75.29 93.41 0.241
0.385 76.50 124.39 0.626
0.559 77.55 175.85 1.268
0.788 79.08 373.02 3.717
0.889 79.82 719.10 8.009
 600

V �(cm3 )
400

200

0
0 2 4 6 8
n A �(mol)

�e data fall on a good straight line which implies that the partial molar vol-
ume (the slope) is nearly constant with composition. However, for there to be
anything to do in the rest of the problem it is necessary to have some variation
in VA , so the data are �tted to a quadratic to give
V �(cm3 ) = 0.02524 (n A �mol)2 + 80.34 (n A �mol) + 74.03
From this an expression for VA is found by di�erentiation (recall that n B has
been held constant)
−1 ∂V
VA �(cm3 mol ) = � � = 0.05048 (n A �mol) + 80.34
∂n A n B
Now that an expression for VA is available the integral in eqn �.� can be evalu-
ated. �e upper limit of the integral is (x A = 0.5, x B = 0.5) because the partial
molar volume at x A = 0.5 is required. �e integral will be the area under a plot
of x A �(1 − x A ) against VA over this range from x A = 0 to x A = 0.5.
Equation �.� gives n A as a function of x A , so the partial molar volume can be
expressed as
−1 xA
VA �(cm3 mol ) = 0.05048 � � + 80.34
1 − xA
�is expression is used to draw up a table of values of VA in the required range
and then to make the plot of x A �(1 − x A ) against VA , shown in Fig. �.�.
−1
VA �(cm3 mol ) xA x A �(1 − x A )
80.3406 0.000 0.000
80.3462 0.100 0.111
80.3533 0.200 0.250
80.3623 0.300 0.429
80.3743 0.400 0.667
80.3911 0.500 1.000
 1.0

x A �(1 − x A )
0.5

0.0
80.34 80.35 80.36 80.37 80.38 80.39 80.40
−1
VA �(cm3 mol )

�e data fall on a good straight line and therefore the required integral is simply
the area of the triangle (shown shaded) bounded by x A �(1−x A ) = 0 and x A �(1−
−1
x A ) = 1; the corresponding values of VA �(cm3 mol ) are 80.3406 and 80.3911.
�e area is 2 × base × height
1

−1
area = 12 (80.3911 − 80.3406) × (1 − 0) = 0.02525 cm3 mol

�e partial molar volume of B is therefore

−1
VB = VB∗ − area = 73.99 − 0.02525 = ��.�� cm3 mol

P�A.� �e partial pressure of component A in the vapour is given by p A = y A p,

where p is the total pressure and y A the mole fraction in the vapour. �e mole
fractions of the two components are related by x B = 1 − x A . Using these rela-
tionships the following table is drawn up, and the data are plotted in Fig. �.�.

xA yA p�(kPa) p A �(kPa) xB yB p B �(kPa)

0 0 36.066 0 1 1 36.066
0.089 8 0.041 0 34.121 1.399 0.910 2 0.959 0 32.722
0.247 6 0.115 4 30.900 3.566 0.752 4 0.884 6 27.334
0.357 7 0.176 2 28.626 5.044 0.642 3 0.823 8 23.582
0.519 4 0.277 2 25.239 6.996 0.480 6 0.722 8 18.243
0.603 6 0.339 3 23.402 7.940 0.396 4 0.660 7 15.462
0.718 8 0.445 0 20.698 9.211 0.281 2 0.555 0 11.488
0.801 9 0.543 5 18.592 10.105 0.198 1 0.456 5 8.487
0.910 5 0.728 4 15.496 11.287 0.089 5 0.271 6 4.209
1 1 12.295 12.295 0 0 0
 A
30 B

p J �(kPa)
20

10

0
0.0 0.2 0.4 0.6 0.8 1.0
xA

Henry’s law [�A.��–���], applies to the solute at low concentrations p J = K J x J .

�e constant is estimated from the partial pressure at the smallest mole frac-
tion; these data are selected from the table.
p A 1.399 kPa p B 4.209 kPa
KA = = = ��.� kPa KB = = = ��.� kPa
xA 0.0898 xB 0.0895

P�A.� �e mass of haemoglobin in ��� cm3 of blood is [(100 cm3 )�(1000 cm3 )] ×
(150 g cm−3 ) = 15 g. In the lungs the haemoglobin is ��% saturated and so this
mass binds a volume 0.97 × (15 g) × (1.34 cm3 g−1 ) of O� . In the capillaries
the saturation drops to ��%, so the volume of O� released is

(0.97 − 0.75) × (15 g) × (1.34 cm3 g−1 ) = �.� cm3

D�B.� �e excess volume is de�ned as V E = ∆ mix V − ∆ mix V ideal . �e volume of

mixing of an ideal solution is zero, which can be understood at a molecular level
as a result of the A and B molecules �tting together in just the same way that A
or B molecules �t with one another. A thermodynamic explanation is that for
an ideal system the partial molar volume is not a function of composition. It
follows that the excess volume is equal to the volume of mixing V E = ∆ mix V ;
it is also useful to recall that ∆ mix V = Vmixed − Vseparated .
Melons are large relative to oranges. When melons pack together it is conceiv-
able that oranges could �t into the interstices between the melons. If this were
the case there would initially be no increase in volume as oranges are added to
melons – meaning that the volume of the mixed oranges and melons is smaller
 than when the two are separate. As a result, ∆ mix V will be negative and so will
the excess volume.
As the number of oranges is increased, the interstices would eventually all be
�lled, presumably when the ratio of oranges to melons is around �:�. A�er
this point, adding oranges will result in an increase in the volume and it is
conceivable that poor packing of objects of di�erent sizes could result in the
volume of the mixture being greater than that of the separated species. In this
case the excess volume will be positive.
When a melons are added to oranges the volume will always increase because
there are no spaces for the melons to occupy. If just a few melons are added
then these will not disrupt the packing of most of the oranges, so the excess
volume will be zero. However, as more are added the ine�ciency of packing
will result in a positive excess volume.

D�B.� �e boiling-point constant is given by [�B.�b–���], K = RT ∗2 �∆ vap H, where

T ∗ is the boiling point of the pure liquid and ∆ vap H is its enthalpy of vapori-
sation. However, by Trouton’s rule (Section �B.� on page ��), ∆ vap H�T ∗ is ap-
proximately constant, so the boiling-point constant is simply ∝ T ∗ . Di�erences
in boiling-point constants are therefore identi�ed as being due to di�erences in
the boiling points of the pure liquids. Water and benzene have di�erent boiling
points and so have di�erent boiling-point constants.

D�B.� �e typical experimental arrangement for observing osmosis involves a pure

solvent being separated from a solution by a semipermeable membrane through
which only the solvent can pass. �e chemical potential of the solvent in the
solution is lower than that of the pure solvent, therefore there is a tendency for
the solvent to pass through the membrane from the side on which it is pure
into the solution because this results in a reduction in Gibbs energy.
At a molecular level the process involves an increase in ‘randomness’ as in-
creasing the amount of solvent in the solution increases the number of possible
arrangements of solvent and solute molecules.

E�B.�(b) In Exercise E�A.�(b) it is found that the vapour pressure obeys

p B �(kPa) = 8.41 × 103 × (x B ) − 2.784 (�.�)

�e task is to work out the mole fraction that corresponds to the given molality.
�e molality of B is de�ned as b B = n B �m A , where n B is the amount in moles
of B and m A is the mass of solvent A. �e mole fraction of B is n B �(n A + n B ),
where n A is the amount in moles of A. �is amount is n A = m A �M A , where
M A is the molar mass of A. �ese relationships allow the mole fraction to be
rewritten as follows
nB nB
xB = =
n A + n B m A �M A + n B
 �e amount in moles of B is written is n B = b B m A ; using this the above expres-
sion for the mole fraction becomes
nB bB mA bB
xB = = =
m A �M A + n B m A �M A + b B m A 1�M A + b B

�e molar mass of A is ��.� g mol−1 , therefore the mole fraction corresponding

to b B = 0.25 mol kg−1 is

bB (0.25 mol kg−1 )

xA = = = 0.0181...
1�M A + b B 1�(74.1 × 10−3 kg mol−1 ) + (0.25 mol kg−1 )

�e pressure is found by inserting this value into eqn �.�

p A �(kPa) = 8.41 × 103 × (0.0181...) − 2.784 = 1.50... × 102

�e vapour pressure of B is therefore 1.5 × 102 kPa .

E�B.�(b) Raoult’s law, [�A.��–���], p A = x A p∗A relates the vapour pressure to the mole
fraction of A, therefore from the given data is it possible to compute x A . �e
task is to relate the mole fraction of A to the masses of A (the solvent) and B
(the solute), and to do this the molar masses M A and M B are introduced. With
these n A = m A �M A , where m A is the mass of A, and similarly for n B . It follows
that
nA m A �M A MB mA
xA = = =
n A + n B m A �M A + m B �M B M B m A + M A m B
�e �nal form of this expression for x A is rearranged to given an expression for
M B , which is the desired quantity; then x A is replaced by p A �p∗A
xA MA mB (p A �p∗A )M A m B
MB = =
m A (1 − x A ) m A [1 − (p A �p∗A )]

�e molar mass of the solvent �-propanol C� H� O, A, is 60.0932 g mol−1 , hence

(p A �p∗A )M A m B
MB =
m A [1 − (p A �p∗A )]
[(49.62 kPa)�(50.00 kPa)] × (60.0932 g mol−1 ) × (8.69 g)
=
(250 g) × [1 − (49.62 kPa)�(50.00 kPa)]
= ��� g mol−1

E�B.�(b) �e freezing point depression ∆Tf is related to the molality of the solute B, b B ,
by [�B.��–���], ∆Tf = K f b B , where K f is the freezing-point constant. From the
data and the known value of K f it is possible to calculate b B . �e task is then to
relate this to the given masses and the desired molar mass of the solute, M B .
�e molality of B is de�ned as b B = n B �m A , where m A is the mass of the solvent
A in kg. It follows that
nB m B �M B
bB = =
mA mA
 where m B is the mass of solute B. From the freezing point data b B = ∆Tf �K f ,
therefore
∆Tf m B �M B mB Kf
= hence M B =
Kf mA m A ∆Tf
With the data given and the value of the freezing-point constant from the Re-
source section
(5.00 g) × (6.94 K kg mol−1 )
MB = = ��� g mol−1
(0.250 kg) × (0.780 K)
Note that because molality is de�ned as (amount in moles)/(mass of solvent in
kg), the mass of solvent m A is used as �.��� kg.

E�B.�(b) �e freezing point depression ∆Tf is related to the molality of the solute B,
b B , by [�B.��–���], ∆Tf = K f b B , where K f is the freezing-point constant. �e
molality of the solute B is de�ned as b B = n B �m A , where n B is the amount in
moles of B and m A is the mass in kg of solvent A. �e amount is related to the
mass of B, m B , using the molar mass M B : n B = m B �M B . It therefore follows
that
Kf mB
∆Tf = K f b B =
MB mA
�e molar mass of NaCl is ��.�� g mol−1 . A volume ��� cm3 of water has mass
��� g to a good approximation. Using these values with the data given and the
value of the freezing-point constant from the Resource section gives the freezing
point depression as

Kf mB (1.86 K kg mol−1 ) × (2.5 g)

∆Tf = = = 0.397... K
M B m A (58.44 g mol−1 ) × (0.200 kg)
Note that because molality is de�ned as (amount in moles)/(mass of solvent
in kg), the mass of solvent m A is used as �.��� kg. �e new freezing point is
therefore 273.15 K − 0.397... K = ���.�� K

E�B.�(b) �e osmotic pressure Π is related to the molar concentration of solute B, [B],

by [�B.��–���], Π = [B]RT. �e freezing point depression ∆Tf is related to the
molality of B, b B , by [�B.��–���], ∆Tf = K f b B , where K f is the freezing-point
constant. �e task is to relate [B] to b B so that these two relationships can be
used together.
�e molar concentration [B] is given by [B] = n B �V , where n B is the amount
in moles of B and V is the volume of the solvent A. �is volume is related to
the mass of A, m A , using the mass density ρ: V = m A �ρ. It therefore follows
that
�
bB

nB nB nB
[B] = = = ρ = bB ρ
V m A �ρ m A
With this the osmotic pressure is related to the molality
Π Π Π
[B] = hence bB ρ = and so bB =
RT RT ρRT
 �e freezing point depression for a solution exerting this osmotic pressure is
therefore
Kf Π
∆Tf = K f b B =
ρRT
Note that because molality is de�ned as (amount in moles)/(mass of solvent in
kg), the mass of solvent m A must be in kg and therefore the mass density must
be used in kg volume−1 .
With the data given, the value of the freezing-point constant from the Resource
section, and taking the mass density of water as 1 g cm−3 = 1000 kg m−3 gives
the freezing point depression as

Kf Π (1.86 K kg mol−1 ) × (99.0 × 103 Pa)

∆Tf = =
ρRT (1000 kg m−3 ) × (8.3145 J K−1 mol−1 ) × (288 K)
= 0.0768... K

In this expression all of the quantities are in SI units therefore the temperature
is expected to be in K, which is veri�ed as follows

(K kg mol−1 ) × (Pa) Pa
=
(kg m ) × (J K mol ) × (K) J × m × K−1
−3 −1 −1 −3

kg m−1 s−2
= =K
(kg m2 s−2 ) × m−3 × K−1

�e freezing point is therefore 273.15 K − 0.0768... K = ���.�� K

E�B.�(b) �e Gibbs energy of mixing is given by [�B.�–���], ∆ mix G = nRT(x A ln x A +

x B ln x B ), the entropy of mixing by [�B.�–���], ∆ mix S = −nR(x A ln x A +x B ln x B ).
∆ mix H for an ideal solution is zero .
�e total amount in moles is 1.00 mol+1.00 mol = 2.00 mol. As equal amounts
in moles of the two components are mixed, the mole fractions of each are 12 .

∆ mix G = nRT(x A ln x A + x B ln x B )
= (2.00 mol) × (8.3145 J K−1 mol−1 ) × (298 K) × 2 × � 12 ln 12 � = −3.44 × 103 J
∆ mix S = −nR(x A ln x A + x B ln x B )
= −(2.50 mol) × (8.3145 J K−1 mol−1 ) × 2 × � 12 ln 12 � = +11.5 J K−1

E�B.�(b) �e entropy of mixing is given by [�B.�–���], ∆ mix S = −nR(x A ln x A +x B ln x B ),

and is a maximum when x A = x B = 12 . �is is evident from Fig. �B.� on page
���.
�e task is to relate the mole fraction of A (ethylbenzene) to the masses of A
and B (benzene), and to do this the molar masses M J are introduced. With
these n J = m J �M J , where m J is the mass of J. It follows that
nA m A �M A MB mA
xA = = =
n A + n B m A �M A + m B �M B M B m A + M A m B
 �is is rearranged to give an expression for m B �m A
MB mA MB mB MB 1
xA = = hence = � − 1�
M B m A + M A m B M B + M A (m B �m A ) mA MA xA
�e molar mass of A (ethylbenzene, C� H�� ) is ���.��� g mol−1 , and that of B
(benzene) is ��.���� g mol−1 . With these values and x A = 12

mB MB 1 78.1074 g mol−1 1
= � − 1� = � − 1� = �.����
mA MA xA 106.159 g mol−1 1�2
More simply, if equal amounts in moles of A and B are required, the ratio of
the corresponding masses of A and B must be equal to the ratio of their molar
masses: m B �m A = M B �M A .

E�B.�(b) �e ideal solubility of solute B at temperature T is given by [�B.��–���], ln x B =

(∆ fus H�R)(1�Tf − 1�T), where ∆ fus H is the enthalpy of fusion of the solute,
and Tf is the freezing point of the pure solute.
∆ fus H 1 1
ln x B = � − �
R Tf T
5.2 × 103 J mol−1 1 1
= � − � = −0.0885...
8.3145 J K−1 mol−1 (327 + 273.15) K (280 + 273.15) K
hence x B = 0.915....
�e mole fraction is expressed in terms of the molality, b B = n B �m A , where m A
is the mass of the solvent in kg, in the following way
nB nB n B �m A bB
xB = = = =
n A + n B m A �M A + n B 1�M A + n B �m A 1�M A + b B
xB
hence bB =
(1 − x B )M A
where M A is the molar mass of A, expressed in kg mol−1 . �e molar mass of
solvent bismuth is ���.�� g mol−1 or 208.98 × 10−3 kg mol−1 , therefore
xB 0.915...
bB = = = 51.6... mol kg−1
(1 − x B )M A (1 − 0.915...) × (208.98 × 10−3 kg mol−1 )

�e molality of the solution is therefore 52 mol kg−1 . �e molar mass of solute

Pb is ���.� g mol−1 , so the mass of Pb which is dissolved per kg is (51.6... mol kg−1 )
×(1 kg)×(207.2 g mol−1 ) = 11 kg . With so much more solute Pb than solvent
Bi, the solution cannot really be described as Pb dissolved in Bi.

E�B.�(b) �e vapour pressure of the solute in an ideal dilute solution obeys Henry’s law,
[�A.��–���], p B = K B x B , and the vapour pressure of the solvent obeys Raoult’s
law, [�A.��–���], p A = p∗A x A .
p B = K B x B = (73 kPa) × 0.066 = 4.81... kPa
p A = p∗A x A = (23 kPa) × (1 − 0.066) = 21.4... kPa
p tot = p A + p A = (4.81... kPa) + (21.4... kPa) = 26.3... kPa
 �erefore the pressure are p B = 4.8 kPa , p A = 21 kPa , and p tot = 26 kPa .
�e partial pressure of the gas is given by p A = y A p tot , where y A is the mole
fraction in the vapour

pA 21.4... kPa
yA = = = �.��
p tot 26.3... kPa
pB 4.81... kPa
yB = = = �.��
p tot 26.3... kPa

E�B.��(b) Let �,�-dimethylbenzene be A and �,�-dimethylbenzene be B. If the solution

is ideal the vapour pressure obeys Raoult’s law, [�A.��–���], p J = p∗J x J . �e
mixture will boil when the sum of the partial vapour pressures of A and B equal
the external pressure, here �� kPa.

p ext = p A + p B = x A p∗A + x B p∗B = x A p∗A + (1 − x A )p∗B

p ext − p∗B p ext − p∗A
hence x A = ∗ and by analogy x B = ∗
pA − pB ∗ p B − p∗A

(19 kPa) − (18 kPa) (19 kPa) − (20 kPa)

xA = = �.� xB = = �.�
(20 kPa) − (18 kPa) (18 kPa) − (20 kPa)
�e partial pressure of the gas is given by p J = y J p ext , where y J is the mole
fraction in the gas, and p J is given by p J = p∗J x J , hence y J = x J p∗J �p ext

x A p∗A (0.50) × (20 kPa)

yA = = = �.��
p ext (19 kPa)
x B p∗B (0.50...) × (18 kPa)
yB = = = �.��
p ext (19 kPa)

E�B.��(b) �e vapour pressure of component J in the solution obeys Raoult’s law, [�A.��–
���], p J = p∗J x J , where x J is the mole fraction in the solution. Is the gas the
partial pressure is p J = y J p tot , where y J is the mole fraction in the vapour.
�ese relationships give rise to four equations

p A = p∗A x A p B = p∗B (1 − x A ) p A = p tot y A p B = p tot (1 − y A )

where x A + x B = 1 is used and likewise for the gas. In these equations x A and
p tot are the unknowns to be found. �e expressions for p A are set equal, as are
those for p B , to give

p∗A x A
p∗A x A = p tot y A hence p tot =
yA
p∗B (1 − x A )
p∗B (1 − x A ) = p tot (1 − y A ) hence p tot =
1 − yA
 �ese two expressions for p tot are set equal and the resulting equation rear-
ranged to �nd x A
p∗A x A p∗B (1 − x A ) p∗B y A
= hence xA =
yA 1 − yA p∗A (1 − y A ) + p∗B y A
With the data given
p∗B y A (82.1 kPa) × (0.612)
xA = =
p A (1 − y A ) + p B y A (68.8 kPa) (1 − 0.612) + (82.1 kPa) × (0.612)
∗ ∗ ∗

= 0.653... and x B = 1 − 0.653... = 0.346...

�e composition of the liquid is therefore x A = 0.653 and x B = 0.347 .
�e total pressure is computed from p A = p tot y A and p A = p∗A x A to give p tot =
x A p∗A �y A
x A p∗A (0.653...) × (68.8 kPa)
p tot = = = ��.� kPa
yA 0.612

E�B.��(b) If the solution is ideal, the vapour pressure of component J in the solution
obeys Raoult’s law, [�A.��–���], p J = p∗J x J , where x J is the mole fraction in
the solution. In the gas the partial pressure is p J = y J p tot , where y J is the mole
fraction in the vapour.
Assuming ideality, the total pressure is computed as
p tot = p A + p B = p∗A x A + p∗B (1 − x A )
= (110.1 kPa) × (0.4217) + (76.5 kPa) × (1 − 0.4217) = 90.7 kPa
�e normal boiling point is when the total pressure is � atm, but the pressure
predicted by Raoult’s law is signi�cantly di�erent from this. Raoult’s law there-
fore does not apply and the solution is not ideal .
It is not possible to �nd y A , the composition of the vapour, from p A = p tot y A
because p A cannot be computed from the data given.

P�B.� �e freezing point depression ∆Tf is related to the molality of the solute B,
b B , by [�B.��–���], ∆Tf = K f b B , where K f is the freezing-point constant. �e
molality corresponding to the given freezing-point depression is therefore
∆Tf 0.0703 K
b B,app = = = 0.0377... mol kg−1
Kf 1.86 K kg mol−1
�e stated molality of the solution is 0.0096 mol kg−1 , so it is evident that there
are more species in the solution than the number of molecules of �(NO� )�
added. �e ratio of b B,app to b B gives an indication of the number of species
present per molecule dissolved
b B,app 0.0377... mol kg−1
= = 3.93...
bB 0.0096 mol kg−1
 �erefore, each molecule of �(NO� )� appears to dissociate into about � species
in solution.

P�B.� �e ideal solubility of solute B at temperature T is given by [�B.��–���], ln x B =

(∆ fus H�R)(1�Tf − 1�T), where ∆ fus H is the enthalpy of fusion of the solute,
and Tf is the freezing point of the pure solute.
�e �rst task is to relate the quoted solubility to the mole fraction of the solute.
�e data gives the solubility in g of solute per ��� g of solvent: let this quantity
be S and, for convenience, let the mass of solvent be m A . �e amount in moles
of solute is n B = S�M B , where M B is the molar mass of the solute in g mol−1 .
Likewise, the amount in moles of solvent is n A = m A �M A , where M A is the
molar mass of the solvent in g mol−1 . For the data given it is invariably the case
that n A � n B , so the mole fraction of B is well-approximated as x B = n B �n A =
SM A �m A M B .
With this the relationship for the ideal solubility is developed as

SM A ∆ fus H 1 1
ln � �=� �� − �
mA MB R Tf T
MA ∆ fus H ∆ fus H 1
ln S = − ln � �+ −
mA MB RTf R T
�e proposed relationship for the solubility, S = S 0 eτ�T , becomes, on taking
logarithms, ln S = ln S 0 + τ�T. �is is compared with the last line to identify
the terms as
MA ∆ fus H ∆ fus H
ln S 0 = − ln � �+ τ=−
mA MB RTf R

To test how the data �t to the proposed relationship a plot of ln S against 1�T
is made; such a plots is shown in Fig. �.�.

θ�○ C S�(g (100 g solv)−1 ) T�K (103 �T)�(K−1 ) ln S

0 36.4 273 3.66 3.59
20 34.9 293 3.41 3.55
40 33.7 313 3.19 3.52
60 32.7 333 3.00 3.49
80 31.7 353 2.83 3.46

�e data �t to quite a good straight line, the equation of which is

ln S�(g (100 g solv)−1 ) = 0.165 × (103 �T)�(K−1 ) + 2.99

�e immediate problem is that the parameter τ is expected to be negative (be-

cause τ = −∆ fus H�R, and ∆ fus H is positive), but the graph has a positive slope.
�e data do not, even at the simplest level, conform to the predictions of the
ideal solubility equation.
 3.60

ln S�(g (100 g solv)−1 )

3.55

3.50

3.45
2.8 3.0 3.2 3.4 3.6
(10 �T)�(K )
3 −1

P�B.� �e de�nition of the chemical potential of component A, µ A , is

∂G
µA = � �
∂n A n B , p,T

To use this de�nition an expression for G as a function of the n J is required.

�e excess Gibbs energy G E is de�ned in [�B.�–���], G E = ∆ mix G − ∆ mix G ideal ,

therefore ∆ mix G = G E + ∆ mix G ideal . �e Gibbs energy of mixing is also ex-
pressed as ∆ mix G = G − G unmixed , where G is the Gibbs energy of the mixture
and G unmixed is the Gibbs energy of the unmixed components. It follows that
G = ∆ mix G + G unmixed , and because ∆ mix G = G E + ∆ mix G ideal

��� � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � �
∆ mix G

G = G E + ∆ mix G ideal +G unmixed

�ese quantities are all molar, so the Gibbs energy of a mixture of n A moles of
A and n B moles of B is

G = (n A + n B )G E + (n A + n B )∆ mix G ideal + n A G m,A

∗
+ n B G m,B
∗

∗
where G m,A is the molar Gibbs energy of pure A.

�e ideal Gibbs energy of mixing (per mole) is given by [�B.�–���], ∆ mix G ideal =
RT(x A ln x A + x B ln x B ), and the expression for G E is given in the problem; this
latter is rewritten gRTx A x B using x B = (1 − x A ). �e �nal expression for G is

G = (n A +n B )gRTx A x B +(n A +n B )RT(x A ln x A +x B ln x B )+n A G m,A

∗
+n B G m,B
∗
 �e mole fractions are rewritten in terms of n A and n B to give

nA nB
G = (n A + n B )gRT � �� �
nA + nB nA + nB
nA nA nB nB
+ (n A + n B )RT �� � ln � �+� � ln � ��
nA + nB nA + nB nA + nB nA + nB
+ n A G m,A
∗
+ n B G m,B
∗

gRTn A n B nA nB
= + RT �n A ln � � + n B ln � �� + n A G m,A
∗
+ n B G m,B
∗
nA + nB nA + nB nA + nB
gRTn A n B
= + RT [n A ln n A − n A ln(n A + n B ) + n B ln n B − n B ln(n A + n B )]
nA + nB
+ n A G m,A
∗
+ n B G m,B
∗

�e algebra used in going to the last line is used to make it easier to compute the
derivative. In �nding the derivative recall that terms such as n A ln n A require
the application of the product rule.

∂G gRTn B gRTn A n B
� � = −
∂n A n B n A + n B (n A + n B )2
nA nB
+ RT �ln n A + 1 − ln(n A + n B ) − − � + G m,A
∗
(n A + n B ) (n A + n B )
=gRT(x B − x A x B ) + RT(1 + ln x A − x A − x B ) + G m,A
∗

=gRTx B (1 − x A ) + RT ln x A + G m,A
∗

=gRTx B2 + RT ln x A + G m,A
∗

On the second line the mole fractions are re-introduced, and in the subsequent
manipulations the relationship x A + x B = 1 is used. G m,A
∗
is identi�ed as the
∗
chemical potential of pure A, µ A , giving the result

µ A = µ ∗A + gRTx B2 + RT ln x A

�is function is plotted in Fig. �.�.

As g increases the deviation from ideal behaviour (the solid line) increases,
with the e�ect being larger at small x A , corresponding to larger x B .

P�B.� (a) �e van ’t Ho� equation is [�B.��–���], Π = [B]RT. If the ‘pressure’ P

is expressed as (mass/area), then to transform it to (force/area) requires
multiplication by the acceleration of free fall, g, because force = mass ×
acceleration: Π = gP.
If the ‘concentration’ c is expressed as (mass/volume), then to transform
it to (moles/volume) requires the use of the molar mass, M: [B] = c�M.
With these substitutions the van ’t Ho� equation becomes

cRT c R c
gP = hence P=� �� �T hence P=� � R′ T
M M g M
 2

(µ A − µ ∗A )�RT
0

−2 g =0
g = 0.5
g = 2.0
−4 g = 6.0

0.0 0.2 0.4 0.6 0.8 1.0

xA

where R′ = R�g. �e �nal equation is of the form of the van ’t Ho� equa-
tion, but with a modi�ed measure of concentration, c�M, and a modi�ed
gas constant, R ′ .
�is equation is rearranged to give an expression for R ′ , and the units
of this quantity are then found by inserting the units of the quantities
involved

PM (g cm−2 ) × (g mol−1 )
R′ = = = g cm K−1 mol−1
cT (g cm−3 ) × (K)

�e numerical value of R ′ is found from its de�nition

R 8.3145 J K−1 mol−1

R′ = = = 0.84784 kg m K−1 mol−1
g 9.8067 m s−2

�e units of R ′ are found by using 1 J = 1 kg m2 s−2 . �e �nal step is to

convert the numerical value of R′ from (kg m K−1 mol−1 ) to the required
(g cm K−1 mol−1 )

1000 g 100 cm
(0.84784 kg m K−1 mol−1 ) × × = 84784 g cm K−1 mol−1
1 kg 1m

(b) From now on the van ’t Ho� equation is written Π = (c�M)RT where the
units of Π and c are as described in (a), and R is 84784 g cm K−1 mol−1 . As
described in Section �B.�(e) on page ���, if it is assumed that the osmotic
pressure is given by a virial-type equation [�B.��–���] where just the �rst
two terms are retained, a plot of Π�c against c should give a straight line
with intercept RT�M. �e data are plotted in Fig. �.�.
 (10−2 Π�c) (10−2 Π�c)
c�(g cm−3 ) c�(g cm−3 )
�(g cm−2 �g cm−3 ) �(g cm−2 �g cm−3 )
2.6 0.005 0 19.0 0.145
2.9 0.010 31.0 0.195
3.6 0.020 38.0 0.245
4.3 0.033 52 0.27
6.0 0.057 63 0.29
12.0 0.100

60
(10−2 Π�c)�(g cm−2 �g cm−3 )

40

20

0
0.00 0.05 0.10 0.15 0.20 0.25 0.30
c�(g cm ) −3

It is evident from the graph that the data do not conform to this expecta-
tion. One approach is to select only the data at the lowest concentrations
because in this limit the expectation is that the two-term virial equation
will be su�cient to describe the data. Such a plot is shown in Fig. �.�.
(10−2 Π�c)�(g cm−2 �g cm−3 )

4.0

3.0

2.0
0.00 0.01 0.01 0.02 0.02 0.03 0.03 0.04
c�(g cm−3 )

�e data �t reasonably well to a straight line with intercept 2.307. From

 this the molar mass is calculated

(84784 g cm K−1 mol−1 ) × (298.15 K)

intercept = RT�M hence M=
102 × 2.307 g cm−2 �g cm−3

which gives M = 1.1 × 105 g mol−1 .

(c) Over the full range of concentrations the plot of Π�c against c is non-
linear, so the solvent is characterised a ‘good’. �is may be attributed to
both solvent and polymer being non-polar.
(d) �e virial-style equation with three coe�cients is

c c c 2 Π RT c c 2
Π= RT �1 + B + C � � � hence = �1 + B + C � � �
M M M c M M M

It is convenient to take the factor of M into the virial coe�cients to give

Π RT
= �1 + B′ c + C ′ c 2 �
c M
where B′ = B�M and likewise for C ′ . Using this, the data Π�c are �tted
to a quadratic in c.
If the �tted function is required to have the same intercept at c = 0 as in
part (a), the �tted function to the �rst � data points (chosen as these gave
the best �t) is

(Π�c)�( g cm−2 �g cm−3 ) = 55563(c�(g cm−3 ))2 +3784.2(c�(g cm−3 ))+230.7

It follows that
RT ′
B = 3784.2 g−1 cm4
M
From part (a) RT�M = 230.7 g cm−2 �g cm−3 , therefore

B′ = (3784.2 g−1 cm4 )�(230.7 g cm−2 �g cm−3 ) = 16.4 g−1 cm3

By a similar line of argument, C ′ = 241 g−2 cm6 .

(e) �e proposed virial equation with g = 1
4
is developed into a straight-line
plot as follows

Π RT
= �1 + B′ c + 14 B′2 c 2 �
c M
RT
= �1 + 12 B′ c�
2
M
Π 1�2 RT 1�2
hence � � = � � �1 + 21 B′ c� (�.�)
c M

A plot of (Π�c)1�2 against c should be a straight line; such a plot is shown

in Fig. �.�.
 80

(Π�c)1�2 �((g cm−2 �g cm−3 )1�2 )

60

40

20

0.00 0.05 0.10 0.15 0.20 0.25 0.30

c�(g cm ) −3

�e data �t to a modest straight line with equation

(Π�c)1�2 �((g cm−2 �g cm−3 )1�2 ) = 212.75(c�(g cm−3 )) + 13.902

From eqn �.� it follows that (slope)/(intercept)= 12 B′

212.75
B′ = 2 × = 30.6 g−1 cm3
13.902

�e third virial coe�cient is 14 B′2 which gives C ′ = 234 g−2 cm6 . �e

agreement with the results from part (d) is modest.

P�B.�� �e ideal Gibbs energy of mixing (per mole) is given by [�B.�–���], ∆ mix G ideal =
RT(x A ln x A + x B ln x B ). �e relationship is plotted for several temperatures in
Fig. �.��.

0
298 K
350 K
−100 400 K
(∆ mix G�R)�K

500 K

−200

−300

0.0 0.2 0.4 0.6 0.8 1.0

xA
 �e dependence of ∆ mix G on temperature is evidently greatest at x A = 12 .
�is is rationalised by noting that (∂∆ mix G�∂T) p = −∆ mix S and that ∆ mix S
is a maximum at x A = 12 . �e composition with the greatest temperature
dependence thus coincides with composition at which the entropy change is
greatest, which is x A = 12 .

P�B.�� �e ideal solubility is given by [�B.��–���]

∆ fus H 1 1 ∆ fus H −∆ fus H
ln x B = � − � hence x B = exp � � exp � �
R Tf T RTf RT
�e �rst exponential is independent of T and the derivative of the second term
is computed using the chain rule.
dx B ∆ fus H ∆ fus H −∆ fus H
= exp � � exp � �
dT RTf RT 2 RT
Changing Tf simple scales the derivative but does not otherwise a�ect the tem-
perature dependence. For the plots shown in Fig. �.�� a typical fusion temper-
ature of 300 K is used, and typical ∆ fus H values of +10 kJ mol−1 , +20 kJ mol−1 ,
and +30 kJ mol−1 are considered.

0.20
∆ fus H = 10 kJ mol−1
0.15 ∆ fus H = 20 kJ mol−1
(dx B �dT)�(K−1 )

∆ fus H = 30 kJ mol−1
0.10

0.05

0.00
200 250 300 350 400
T�K

�e temperature dependence of the solubility is stronger the greater ∆H fus , and

for these sets of parameters the solubility increases with T. �e plot shows a
maximum at much higher (and rather unrealistic) temperatures.

D�C.� A low-boiling azeotrope has a boiling temperature lower than that of either
component, so it is easier for the molecules to move into the vapour phase
 than in a ‘normal’ (non-azeotropic) mixture. �erefore, the liquid phase has
less favorable intermolecular interactions than in a ‘normal’ mixture, a sign
that the components are less attracted to each other in the liquid phase than to
molecules of their own kind. �ese intermolecular interactions are determined
by factors such as dipole moment (polarity) and hydrogen bonding.
Conversely, a high-boiling azeotrope has a boiling temperature higher than that
of either component, so it is more di�cult for the molecules to move into the
vapour phase. �is re�ects the relatively unusual situation of components that
have more favorable intermolecular interactions with each other in the liquid
phase than with molecules of their own kind.

E�C.�(b) �e temperature–composition phase diagram is a plot of the boiling point against

(�) composition of the liquid, x A and (�) composition of the vapour, y A . �e
horizontal axis is labelled z A , which is interpreted as x A or y A according to
which set of data are being plotted. In addition to the data in the table, the
boiling points of the pure liquids are added. �e plot is shown in Fig.�.��; the
lines are best-�t polynomials of order �.

θ�○ C xA yA θ�○ C xA yA
124 1 1 140 0.30 0.61
125 0.91 0.99 145 0.18 0.45
130 0.65 0.91 150 0.098 0.25
135 0.45 0.77 155 0 0

liquid
150 vapour
θ�○ C

140
y A = 0.81
x A = 0.50

130

0.0 0.2 0.4 0.6 0.8 1.0

zA

(i) �e vapour composition corresponding to a liquid composition of x A =

0.50 is found by taking the vertical line at this composition up to the
intersection with the liquid curve, and then moving across horizontally to
 the intersection with the vapour curve; this occurs at y A = 0.81 , which
gives the composition of the vapour. �e exact points of intersection can
be found either from the graph or by using the �tted functions.
(ii) A composition x B = 0.33 corresponds to x A = 0.67; from the graph this
corresponds to a vapour composition y A = 0.90 .

E�C.�(b) At the lowest temperature shown in the diagram the mixture is in the two-phase
region, and the two phases have composition of approximately x B = 0.88 and
x B = 0.05. �e level rule shows that there is about �.� times more of the B-poor
than of the B-rich phase. As the temperature is raised the B-rich phase becomes
slightly less rich in B, and the other phase becomes richer in B. �e lever rule
implies that the proportion of the B-poor phase increases as the temperature
rises.
At temperature T2 the vertical line intersects the phase boundary. At this point
the B-rich phase disappears and only one phase, with x B = 0.3, is present.

E�C.�(b) �e molar masses of aniline and hexane are ��.���� g mol−1 and ��.���� g mol−1 ,
respectively. �e mole fraction of aniline (A) is

(42.8 g)�(93.1253 g mol−1 )

xA = = 0.344...
(42.8 g)�(93.1253 g mol−1 ) + (75.2 g)�(86.1706 g mol−1 )

Hence x A = �.��� . Let the two phases be α (x A = 0.308) and β (x A = 0.618).

�e proportions of these two phases, n β �n α is given by the level rule, [�C.�–���]
n β l α 0.344... − 0.308
= = = �.���
n α l β 0.618 − 0.344...

�e aniline-poor phase is more abundant by a factor of about �.

E�C.�(b) An approximate phase diagram is shown in Fig. �.��; the given data points are
shown with dots and these are simply joined with straight lines as a guide to
the eye. �e shape conforms to the expected phase diagram for such a system.

(i) At �� ○ C the possibility of phase separation exists; as the amount of B

added to A increases, the mole fraction of A decreases and the phase
diagram is traversed along the dashed line from right to le�. When the
mole fraction of A is high a single phase forms, but as the mole fraction
goes below about �.� phase separation occurs. Initially, according to the
lever rule, the proportion of the B-rich phase is very small, but as more
and more B is added the proportion of this phase increases. When the
x A is just over �.��, there is very little of the A-rich phase present and as
the mole fraction decreases further a one-phase zone is reached in which
there is complete miscibility.
(ii) A temperature of ��.� ○ C is equal to the upper critical temperature, and
therefore the expectation is that A and B will mix in all proportions to
give a single phase.
 50

θ�○ C 45

40
0.0 0.2 0.4 0.6 0.8 1.0
xA

P�C.� If it is assumed that Raoult’s law applies, [�A.��–���], the partial vapour pres-
sures of DE and DP are
p DE = x DE p∗DE p DP = x DP p∗DP
where x J are the mole fractions and p∗J are the vapour pressures over the pure
liquids. �e total pressure is taken to be p tot = p DE + p DP .

(a) �e total pressure is given by

p tot = p DE + p DP = x DE p∗DE + x DP p∗DP
= 0.60 × (22.9 kPa) + 0.40 × (17.1 kPa) = ��.� kPa

(b) �e mole fraction in the vapour, y J , is related to the total pressure by p J =

y J p tot , so it follows that
pJ x J p∗J
yJ = =
p tot p tot
�erefore
x DE p∗DE 0.60 × (22.9 kPa)
y DE = = = �.��
p tot 0.60 × (22.9 kPa) + 0.40 × (17.1 kPa)
x DP p∗DP 0.40 × (17.1 kPa)
y DP = = = �.��
p tot 0.60 × (22.9 kPa) + 0.40 × (17.1 kPa)

P�C.� (a) �e temperature–composition phase diagram is a plot of the boiling point

against (�) composition of the liquid, x B , the mole fraction of butan-�-ol
and (�) composition of the vapour, y B . �e horizontal axis is labelled
z B , which is interpreted as x B or y B according to which set of data are
being plotted. In addition to the data in the table, the boiling point of
pure chlorobenzene is added. �e resulting phase diagram is shown in
Fig. �.��; the data points are just connected by best-�t polynomials.
 T�K xB yB T�K xB yB
404.86 0 0 390.15 0.368 7 0.513 8
396.57 0.106 5 0.285 9 389.03 0.501 7 0.584 0
393.94 0.170 0 0.369 1 388.66 0.609 1 0.640 9
391.60 0.264 6 0.450 5 388.57 0.717 1 0.707 0

405
liquid
vapour
400
T�K

395 l ×v

390

0.0 0.2 0.4 0.6 0.8

zB

(b) At a composition x B = 0.3, indicated by the dotted line, the boiling point
is when this line intersects the liquid line, which is at a temperature of
��� K .
(c) At ���.�� K the compositions are given by the points at which the hori-
zontal dashed line cuts the liquid and vapour curves (which in this case
also coincide with the given data points). �e compositions are therefore
x B = 0.17 and y B = 0.37 .
�e relative proportions of the two phases are given by the lever rule, the
mid point of the lever being x = 0.3; the distances l and v are marked on
the diagram
n l v 0.37 − 0.30
= = = 0.54
n v l 0.30 − 0.17
�erefore the vapour is about twice as abundant as the liquid phase.

P�C.� Let phase α have x A = 0.2 and phase β have x A = 0.6. By the lever rule, [�C.�–
���], the ratio of abundances of the two phases is
nα lβ
=
nβ lα
where l α is the ‘distance’ between the overall composition (here �.�) and the
composition of phase α (here �.�),and likewise for β
n α l β 0.4 − 0.2
= = =1
n β l α 0.6 − 0.4
 �e abundance of the two phases is therefore equal.

P�C.� �e relationship between the total pressure p and y A is given in [�C.�–���]

p∗A p∗B
p=
p∗A + (p∗B − p∗A )y A

Division by p∗A , and then division of the numerator and denominator of the
fraction on the right by p∗B gives the required form

p p∗B 1
= = ∗ ∗
p A p A + (p B − p A )y A (p A �p B ) + (1 − p∗A �p∗B )y A
∗ ∗ ∗ ∗

�e plot is shown in Fig. �.��.

1.0
(p∗A �p∗B ) = 2
0.8 (p∗A �p∗B ) = 4
(p∗A �p∗B ) = 30
0.6
p�p∗A

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
yA

P�C.�� �e values of x A at which ∆ mix G is a minimum are found by solving [�C.�–���]

xA
ln + ξ(1 − 2x A ) = 0 (�.�)
1 − xA

�is equation is rearranged to give an expression for ξ, which is plotted in

Fig. �.��
ln(x A �[1 − x A ])
ξ=
2x A − 1

�e way to interpret this graph is to choose a value for ξ and then read across to
locate the minima. If ξ < 2 there are no values of x A which solve the equation,
and hence no minima. For ξ > 2 there are two values of x A at which the plotted
function intersects a horizontal line at a given value of ξ. �e larger ξ becomes
the close one intersection (position of a minimum) moves towards x A = 0 and
the other towards x A = 1.
 5

ξ
2

1
0.0 0.2 0.4 0.6 0.8 1.0
xA

4 ln x A �(1 − x A )
ξ(2x A − 1) ξ = 1
2 ξ(2x A − 1) ξ = 2.5
ξ(2x A − 1) ξ = 4
0

−2

−4
0.0 0.2 0.4 0.6 0.8 1.0
xA

An alternative way to explore the solutions to eqn �.� is to plot ln x A �(1 − x A )

against x A , and on the same graph to plot ξ(2x A −1) also against x A . �e values
of x A at which the two curves intersect gives the position of the minima. Such
a plot is shown in Fig. �.��

�e plot illustrates that there are no intersections when ξ < 2, and that, as
before, the intersections that occur when ξ > 2 (highlighted as ○) move to the
edges of the plot as ξ increases. �ere is always an intersection at x A = 0, and as
is seen from Fig. �B.� this corresponds to a minimum for ξ < 2, and a maximum
for ξ > 2.

Mathematical so�ware can also be used to solve eqn �.� numerically for given
values of ξ. For example, for ξ = 2.5 the solutions are x A = 0.855 and x A =
0.145.
D�D.� �e schematic phase diagram is shown in Fig. �.��. Incongruent melting means
that the compound AB� does not occur in the liquid phase.

liquid

A(s) + B(l)
+ A(l) AB2(s),B(l)
B(l) + A(l)
A(l)
Temperature

+ B(s)
AB2(s),B(l)
A(l)
A(s) + AB2(s)
AB2(s) + B(s)

0 0.2 0.4 0.6 0.8 1

Mole fraction of B, xB AB2

E�D.�(b) �e schematic phase diagram is shown in Fig �.��. �e solid points are the
data given in the Exercise, and lines are simply plausible connections between
these points. �e small area to the le� of x N2 H4 = 0.07, enclosed by the phase
boundary and the line at −80 ○ C, corresponds to N� H� (l)+NH� (l)+NH� (s).

−20 liquid

−40
θ�○ C

N� H� (s)+N� H� (l)+NH� (l)

−60

−80 N� H� (s)+NH� (s)

0.0 0.2 0.4 0.6 0.8 1.0
x N2 H4

E�D.�(b) �e schematic phase diagram is shown in Fig �.��. �e solid points are the data
given in the Exercise, and lines are simply plausible connections between these
points. (�e dash-dotted lines are referred in to Exercise E�D.�(b).)
 �e stated mixture has x B2 H6 = 4�(1 + 4) = 0.8 and is indicated by the vertical
dashed line. �e mixture cools until about ��� K at which point solid �rst
forms. �e solid which forms is the �:� compound and as this happens the
liquid becomes richer in B� H� . Cooling continues with more and more of the
�:� compound being formed until ��� K, the second eutectic, at which point
the system completely solidi�es to a two-phase material consisting of the �:�
compound and solid B� H� .

(i) (ii) (iii) (iv) (v)

130

120
T�K

110

0.0 0.2 0.4 0.6 0.8 1.0

x B2 H6

E�D.�(b) �e compositions at which the cooling curves are plotted are indicated by the
vertical dash-dotted lines on the phase diagram for Exercise E�D.�(b), Fig. �.��.
�e cooling curves are shown in Fig �.��. �e break points, where solid phases
start to form are shown by the short horizontal lines, and the dotted lines in-
dicate the temperatures of the two eutectics (��� K and ��� K). �e horizontal
segments correspond to solidi�cation of a eutectic. Cooling curve (c) corre-
sponds to direct solidi�cation of the �:� complex.

E�D.�(b) �e feature that indicates incongruent melting is the intersection of the two
liquid curves at around x B ≈ 0.37. �e incongruent melting point is marked T1 .
�e composition of the eutectic is x B ≈ 0.58 and its melting point is labelled
T2 .

E�D.�(b) �e cooling curves are shown in Fig �.��; the break points are shown by the
short horizontal lines, and the temperatures T1 and T2 are indicated. For iso-
pleth a the �rst break point is where the isopleth crosses the liquid curve be-
tween temperatures T1 and T2 ; this is followed by a eutectic halt at T2 . For
isopleth b the �rst break point is somewhat above T1 where the isopleth crosses
the liquid curve, there is a second break point where the isopleth crosses the
boundary at T1 , and then a eutectic halt at T2 .
 135
130 (iii)
(i) (ii) (iv) (v)
125
120
T�K
115
110
105
time
temperature

T1

T2 a b

time

E�D.�(b) Figure �.�� shows the phase diagram to which dotted horizontal lines have
added at the relevant temperatures.

(i) At ��� ○ C the phase diagram shows a single liquid phase at all composi-
tions, so B is soluble in A in all proportions .
(ii) At ��� ○ C solid B exists in equilibrium with a liquid whose composition is
circled and labelled x 1 in the �gure. �at composition is x B = x 1 = �.�� .
(iii) At ��� ○ C the solubility of AB� in B is indicated by the point x 2 . At this
point two phases coexist: solid AB� and a liquid mixture of A and B with
mole fraction x B = x 2 = 0.41. Although the liquid does not contain any
AB� units, the liquid can be thought of as a mixture of dissociated AB�
in A. Let the amount in moles of the compound be n c and that of free
A be n a . �us, the amount of A (regardless of whether free or in the
compound) is n A = n a + n c and the amount of B is n B = 2n c . �e mole
fraction of B is
nB 2n c 2n c
xB = x2 = = =
n A + n B (n a + n c ) + 2n c n a + 3n c
 500

x1

Temperature, θ/°C
400
T1
x2
300

200
T2

100
0
0 0.2 0.4 0.6 0.8 1
Mole fraction of B, xB

�is relationship is rearranged and terms in n c are collected on one side

and those in n a on the other to give n a x 2 = n c (2 − 3x 2 ). �e mole ratio
of compound to free A is given by
nc x2 0.41
= = = �.��
n a 2 − 3x 2 2 − 3 × 0.41

P�D.� �e mole fraction of sulfur, x S , corresponding to compound Pn Sm is computed

from the molar masses of sulfur and phosphorus, M S and M P , as

mM S m × (32.06 g mol−1 )
xS = =
mM S + nM P m × (32.06 g mol−1 ) + n × (30.97 g mol−1 )

Using this expression, mole fractions corresponding to the three compounds

are: (�) P� S� , �.��; (�) P� S� , �.��; (�) P� S�� , �.��.
�e phase diagram is a variation of that shown in Fig. �D.� on page ��� except
that instead of one compound being formed there are three. �e diagram there-
fore separates into four sections, as shown schematically in Fig. �.��. Note that
no information is given on the temperature or composition of the eutectics, so
these have simply been selected arbitrarily.
�e diagram has four eutectics labelled e 1 , e 2 , e 3 , and e 4 ; eight two-phase
liquid-solid regions, t 1 through t 8 ; and four two-phase solid regions, S1 , S2 ,
S3 , and S4 . �e composition and physical state of the regions are as follows:

l: liquid S and P
S1 : solid P and solid P� S� S2 : solid P� S� and solid P� S�
S3 : solid P� S� and solid P� S�� S4 : solid P� S�� and solid S
t 1 : liquid P and S and solid P t 2 : liquid P and S and solid P� S�
t 3 : liquid P and S and solid P� S� t 4 : liquid P and S and solid P� S�
t 5 : liquid P and S and solid P� S� t 6 : liquid P and S and solid P� S��
t 7 : liquid P and S and solid P� S�� t 8 : liquid P and S and solid S
 �e cooling curve is shown to the right of the phase diagram in Fig. �.��. A
break in the curve occurs at point b 1 ≈ 125 ○ C as a result of solid P� S� forming;
a eutectic halt occurs at point e 1 ≈ 20 ○ C.

350

300
l

250
temperature / ºC

t5 t6

200 t4
e3
t7
150 t3

100 e2 b1
t2 S3 t8
S2
50 e4
t1 S4
0.44

0.64

0.72
e1 S1 e1
0
0 0.2 0.4 0.6 0.8 1.0 time
P4S10
P4S3

P4S7

xS

P�D.� �e information is used to construct the phase diagram shown in Fig �.��; the
solid dots correspond to the data and the lines are simply plausible connections
between these points.

1 000

800
a1
θ�○ C

e1
600 a2
e2

400
e3
0 20 40 60 80 100 time
MgCu� Mg� Cu % mass Mg

In Mgn Cum the mass percentage of Mg is computed from the molar masses of
Mg and Cu, M Mg and M Cu , as

nM Mg
100 ×
nM Mg + mM Cu
 For MgCu� the percentage is

1 × (24.31 g mol−1 )
100 × = 16
1 × (24.31 g mol−1 ) + 2 × (63.55 g mol−1 )

For Mg� Cu the percentage by mass of Mg is ��.

For the isopleth at ��% Mg at high temperatures the initially system corre-
sponds to a single-phase liquid system. At a 1 (at about ��� ○ C) MgCu� begins
to come out of solution and the liquid becomes richer in Mg, moving toward
e 2 . At a 2 there is solid MgCu� + liquid of composition e 2 (�� per cent by mass of
Mg). �is solution freezes without further change. �e cooling curve is shown
next to the phase diagram.

P�D.� �e schematic phase diagram is shown in Fig �.��. �e solid points are the
data given in the Exercise, and the lines are simply plausible connections be-
tween these points; the open circle is the incongruent melting of K� FeCl� . An
expanded section of the phase diagram is shown as this includes the part of
interest.

500

450
θ�○ C

400

350

300
0.3 0.4 0.5 0.6 0.7
K� FeCl� KFeCl� x FeCl2

�e compounds KFeCl� and K� FeCl� correspond to x FeCl2 = 1

2
and x FeCl2 = 13 ,
respectively; these compositions are shown on the diagram.
When a melt of composition x FeCl2 = 0.36 is cooled (the dotted line), solid is
�rst deposited when the temperature falls to around ��� ○ C. �e solid consists
of K� FeCl� , and as the temperature falls further the liquid grows progressively
richer in FeCl� . �is process continues until the temperature falls to ��� ○ C, at
which point the liquid has the same composition as the eutectic and the whole
sample solidi�es to a mixture of K� FeCl� and KFeCl� .
D�E.� �e lever rule, [�C.�–���], applies in a ternary system, but with an important
caveat. For binary systems the tie lines to which the rule appplies are always
horizontal and so can be added to the phase diagram at will. In contrast, for
a ternary system the tie lines have no such simple orientation and have to be
determined experimentally. �us the lever rule applies, but in order to use
it additional information is needed about the tie lines at the composition of
interest.

D�E.� �e composition represented by point c is approximately x Ni = 0.73, x Fe = 0.20,

x Cr = 0.07. �is is a three-phase region, with Fe, Ni and γFeNi present.

E�E.�(b) �e ternary phase diagram is shown in Fig �.��.

A
0.0
1.0
0.2
(ii) 0.8
xC 0.4 xA
(i) 0.6
0.6
0.4
0.8 (iii)
0.2
1.0
C 0.0 B
0.0 0.2 0.4 0.6 0.8 1.0
xB

E�E.�(b) �e composition by mass needs to be converted to mole fractions, which re-

quires the molar masses: M NaCl = 58.44 g mol−1 , M H2 O = 18.016 g mol−1 , and
M Na2 SO4 ⋅ 10 H2 O = 322.20 g mol−1 . Imagine that the solution contains �� g NaCl,
�� g Na� SO� ⋅ �� H� O and hence (100 − 33 − 33) = 34 g H2 O. �e mole fraction
of NaCl is
m NaCl �M NaCl
x NaCl =
m NaCl �M NaCl + m Na2 SO4 ⋅ 10 H2 O �M Na2 SO4 ⋅ 10 H2 O + m H2 O �M H2 O
(33 g)�(58.44 g mol−1 )
=
(33 g)�(58.44 g mol−1 ) + (33 g)�(322.20 g mol−1 ) + (34 g)�(18.016 g mol−1 )
= 0.22
 Likewise, x Na2 SO4 ⋅ 10 H2 O = 0.040 and x H2 O = 0.74; this point is plotted in the
ternary phase diagram shown in Fig �.��.
�e line with varying amounts of water but the same relative amounts of the
two salts (in this case, equal by mass), passes through this point and the vertex
corresponding to x H2 O = 1. �is line intersects the NaCl axis at a mole fraction
corresponding to a ��:�� mixture (by mass) of the two salts

(50 g)�(58.44 g mol−1 )

x NaCl = = 0.85
(50 g)�(58.44 g mol−1 ) + (50 g)�(322.20 g mol−1 )

�e line is shown on the diagram.

NaCl
0.0
1.0
0.2
0.8
x H2 O 0.4 x NaCl
0.6
0.6
0.4
0.8
0.2
1.0
H� O 0.0 Na� SO�
0.0 0.2 0.4 0.6 0.8 1.0
x Na2 SO4 ⋅ 10 H2 O

E�E.�(b) �e composition by mass needs to be converted to mole fractions, which re-

quires the molar masses: M CHCl3 = 119.37 g mol−1 , M H2 O = 18.016 g mol−1 ,
and M CH3 COOH = 60.052 g mol−1 . �e mole fraction of CHCl� is

m CHCl3 �M CHCl3
x CHCl3 =
m CHCl3 �M CHCl3 + m CH3 COOH �M CH3 COOH + m H2 O �M H2 O
(8.8 g)�(119.37 g mol−1 )
=
(8.8 g)�(119.37 g mol ) + (3.7 g)�(60.052 g mol−1 ) + (55.0 g)�(18.016 g mol−1 )
−1

= 0.023

Likewise, x CH3 COOH = 0.019 and x H2 O = 0.958. �is point in marked with
the open circle on the phase diagram shown in Fig. �.��; it falls clearly in the
one-phase region.

(i) When water is added to the mixture the composition moves the distance
to the lower-le� corner. �e system remains in the one-phase region
throughout.
 (ii) When ethanoic acid is added to the mixture the composition moves along
the dashed line to the vertex. �e system remains in the one-phase region
throughout.

CH� COOH
0.0
1.0
0.2
0.8
xW 0.4 xE
0.6
0.6
0.4
0.8
0.2
1.0
H� O 0.0 CHCl�
0.0 0.2 0.4 0.6 0.8 1.0
xT

E�E.�(b) �e points corresponding to the given compositions are marked with letters on
the phase diagram shown in Fig. �.��. Composition (i) is in a two-phase region,
(ii) is in a three-phase region, (iii) is in a two-phase region, and (iv) appears to
lie on the line separating di�erent phases.

0 1 H2O
S1
0.2 P = 1 0.8
S2
S5
0.4 0.6
i P=2
P=2 0.4
0.6
S3 iv
iii
0.8 P=3 0.2
ii
NH4Cl 1 0 (NH4)2SO4
0 0.2 0.4 S4 0.6 0.8 1

E�E.�(b) (i) Saturated solutions of NH� Cl in H� O in the presence of solid NH� Cl

appear as points on the le�-hand edge of the phase diagram. �ree rep-
resentative compositions are shown in Fig. �.��: S 1 corresponds to the
point at which the solution becomes a single phase, and is therefore the
highest concentration that can be achieved; S 2 has a higher mole fraction
 of NH� Cl than S 1 so it corresponds to a saturated solution in the presence
of solid NH� Cl; S 3 corresponds to yet more solid being present.
Adding (NH� )� SO� to each of these solutions corresponds to travers-
ing the dashed lines from S i to the lower right-hand vertex which cor-
responds to pure (NH� )� SO� . Starting from S 1 the system �rst traverses
a one-phase region, meaning that both salts are entirely dissolved, before
moving into a two phase region which implies that one of the salts will
precipitate out. �e tie lines are not given, but presumably as the amount
of (NH� )� SO� increases the composition of the aqueous solution moves
along the curve to the point where the four lines meet. At this point the
last drop of solution vanishes.
Starting from S 2 the system �rst traverses a two-phase region, meaning
that the (NH� )� SO� is going into solution. Eventually the system moves
into a one-phase region, which implies that addition of (NH� )� SO� has
caused the excess solid NH� Cl to dissolve. As with the path starting from
S 1 , this path eventually crosses into a two-phase region where the be-
haviour is as has already been described.
Starting from S 3 the system �rst traverses a two-phase region but in con-
trast to S 1 and S 2 it never enters a one-phase region.
(ii) It is �rst necessary to convert the given masses to mole fractions, using
M NH4 Cl = 53.49 g mol−1 and M(NH4 )2 SO4 = 132.14 g mol−1 . �e mole
fraction of NH� Cl is

(25 g)�(53.49 g mol−1 )

x NH4 Cl = = 0.45
(25 g)�(53.49 g mol−1 ) + (75 g)�(132.14 g mol−1 )

and hence x(NH4 )2 SO4 = 1 − x NH4 Cl = 0.55; this point is shown in Fig. �.��
as S 4 . Adding water to such a mixture involves traversing the dotted line
from S 4 to the apex of the diagram, which corresponds to pure H� O.
To start with the system is entirely solid, but when the line between the
three-phase to two-phase region is crossed the two phases in question
are some kind of solid and an aqueous solution, which appears for the
�rst time. As the two-phase region is traversed the composition of this
aqueous solution traverses the gray line until point S 5 where it meets the
dotted line. A�er this, the system moves into a one-phase region: all the
solids are dissolved.

P�E.� (a) �e given points are shown by �lled dots in the phase diagram shown
in Fig. �.��. �e fact that CO� and nitroethane have a two-phase region
between x nitroethane = 0.08 and �.��, and that there is a plait point at
x CO2 = 0.18, x nitroethane = 0.53 establishes some limits on the two-phase
region, the outline of which is indicated by a plausible line. Similarly, the
CO� /DEC two-phase region is established by the given data.
(b) Mixtures with nitroethane and CO� in a �xed ratio, but with increasing
amounts of DEC, fall on a straight line from some point on the right-hand
 edge to the lower-le� apex (pure DEC). �e two dashed lines shown just
touch the two-phase regions, so all compositions between these lines lie
in the one-phase region; this is the region where addition of DEC never
causes phase separation.

0 1 CO2

0.2 0.8

0.4 0.6
P=2
P=1
0.6 P 0.4

0.8 P 0.2

P=2
DEC 1 0 nitroethane
0 0.2 0.4 0.6 0.8 1

D�F.� Raoult’s law, p J = x J p∗J , [�A.��–���], expresses the partial pressure of J in the
gas phase in terms of its mole fraction in the liquid phase, x J , and the vapour
pressure over the pure liquid, p∗J . �is law only applies to ideal solutions, and
indeed is taken as a de�ning property of such solutions.
For non-ideal solutions Raoult’s law is modi�ed to p J = a J p∗J , where a J is
the activity. However, this relationship is best viewed as the de�nition of the
activity in terms of two measurable quantities, the pressures: a J = p J �p∗J . In
the limit x J → 1 the activity becomes equal to the mole fraction, so the general
equation involving the activity moves smoothly over to the relationship which
applies to ideal solutions. It is convenient to retain such similar relationships
for the ideal and non-ideal cases.

D�F.� �e coulombic (electrostatic) interactions of the ions in solution with each

other are responsible for the deviation of their activity coe�cients from the
ideal value of �. As a result of these interactions there is a build up of charge of
opposite sign around any given ion, called the ionic atmosphere, in the overall
electrically neutral solution. �e energy, and hence the chemical potential, of
any given ion is lowered as a result of the existence of this ionic atmosphere.
�e lowering of the chemical potential below its ideal value is identi�ed with a
negative value of RT ln γ± and hence a value of γ± less than unity.
D�F.� �e term B in the extended Debye–Hückel law, [�F.��a–���], and the Davies
equation, [�F.��b–���], can be interpreted as an indicator of the distance of
closest approach of the ions. However, both B and the parameter C in the latter
equation are best thought of as empirical parameters to be obtained by �tting
experimental data.

E�F.�(b) �e activity in terms of the vapour pressure p is given by [�F.�–���], a = p�p∗ ,

where p∗ is the vapour pressure of the pure solvent. �e vapour pressure of
pure water at ��� ○ C, the normal boiling point, is � atm. �erefore a = p�p∗ =
(90.00 kPa)�[(1 atm) × (101.325 kPa)�(1 atm)] = �.���� .

E�F.�(b) On the basis of Raoult’s law, the activity in terms of the vapour pressure p A is
given by [�F.�–���], a A = p A �p∗A , where p∗A is the vapour pressure of the pure
solvent. With the data given a A = p A �p∗A = (0.02239 atm)�(0.02308 atm) =
0.9701... = �.���� .
�e activity coe�cient is de�ned through [�F.�–���], a A = γ A x A . �e mole
fraction of solvent water (A) is computed as
nA
xA =
nA + nA
(0.920 × 103 g)�(18.0158 g mol−1 )
=
(0.920 × 103 g)�(18.0158 g mol−1 ) + (0.122 × 103 g)�(241 g mol−1 )
= 0.990...

Hence γ A = a A �x A = (0.9701...)�(0.990...) = �.��� .

E�F.�(b) On the basis of Raoult’s law, the activity in terms of the vapour pressure p J is
given by [�F.�–���], a J = p J �p∗J , where p∗J is the vapour pressure of the pure
solvent. �e partial vapour pressure of component J in the gas is given by p J =
y J p tot . In this case

p A y A p tot 0.314 × (1.00 atm) × [(101.325 kPa)�(1 atm)]

aA = = = = 0.435...
p∗A p∗A 73.0 kPa

�e activity of A is therefore a A = �.��� . �e activity coe�cient is de�ned

through [�F.�–���], a J = γ J x J , therefore γ A = a A �x A = 0.435...�0.220 = �.�� .
For the other component the mole fractions are y B = 1 − y A = 0.686 and x B =
1 − x A = 0.780. �e rest of the calculation follows as before
p B y B p tot 0.686 × (1.00 atm) × [(101.325 kPa)�(1 atm)]
aB = = = = 0.754...
p∗B p∗B 92.1 kPa

�e activity of B is therefore a B = �.��� and its activity coe�cient is given by

γ B = a B �x B = 0.754...�0.780 = �.��� .
 15
pA
pB
p tot
p�kPa 10

0
0.0 0.2 0.4 0.6 0.8 1.0
xA

E�F.�(b) For this model of non-ideal solutions the vapour pressures are given by [�F.��–
���], p A = p∗A x A exp(ξ[1− x A ]2 ) and likewise for p B ; the total pressure is given
by p tot = p A + p B . �e vapour pressures are plotted in Fig. �.��.

E�F.�(b) Ionic strength is de�ned in [�F.��–���]

I = 12 � z 2i (b i �b −○ )
i

where the sum runs over all the ions in the solution, z i is the charge number on
ion i, and b i is its molality. It is convenient to draw up a table of the contribu-
tion to the ionic strength from each ion, where the contribution is de�ned as
z 2i (b i �b −○ ). For K� [Fe(CN)� ] note that the molality of the K+ produced when it
dissolves is three times the molality of the solute.

solute (molality/mol kg−1 ) ion b i �b −○ zi contribution

K3 [Fe(CN)6 ] (0.040) K +
0.120 +1 0.120
[Fe(CN)6 ] 3–
0.040 −3 0.360
KCl (0.030) K +
0.030 +1 0.030
Cl –
0.030 −1 0.030
NaBr (0.050) Na +
0.050 +1 0.050
Cl –
0.050 −1 0.050

�e total of the contributions in the right-most column is �.���, therefore the

ionic strength is I = 12 × 0.640 = �.��� .

E�F.�(b) Ionic strength is de�ned in [�F.��–���]

I = 12 � z 2i (b i �b −○ )
i
 where the sum runs over all the ions in the solution, z i is the charge number
on ion i, and b i is its molality.

(a) �e aim here is to increase the ionic strength by 1.00 − 0.110 = 0.890; the
task is therefore to compute the mass m of KNO� which, when added to
a mass m w of water, gives this increase in the ionic strength.
A solution of KNO� of molality b contributes K+ at molality b and NO� –
at molality b. �e contribution to the ionic strength is therefore 12 [(+1)2 ×
b + (−1)2 × b]�b−○ = b�b −○ .
�e molality arising from dissolving mass m of KNO� in a mass m w of
solvent is (m�M)�m w , where M is the molar mass. It therefore follows
that to achieve the desired increase in ionic strength

m 1
× −○ = 0.890 hence m = 0.890 × Mm w b −○
Mm w b

�e molar mass of KNO� is ���.�� g mol−1 ; using this, and recalling that
the molality is expressed in mol kg−1 , gives

m = 0.890 × (101.11 × 10−3 kg mol−1 ) × (0.500 kg) × (1 mol kg−1 )

= 44.9... × 10−3 kg

Hence the ��.� g of KNO� needs to be added to achieve the desired ionic
strength.
(i) �e argument is as in (a) except that the added solute Ba(NO� )� makes
a di�erent contribution to the ionic strength. A solution of Ba(NO� )�
of molality b contributes Ba�+ at molality b and NO� – at molality 2b.
�e contribution to the ionic strength is therefore 12 [(+2)2 × b + (−1)2 ×
2b]�b −○ = 3b�b −○ . It therefore follows that to achieve the desired increase
in ionic strength

m 1
3× × −○ = 0.890 hence m= 1
3
× 0.890 × Mm w b −○
Mm w b

�e molar mass of Ba(NO� )� is ���.�� g mol−1 ; using this, and recalling

that the molality is expressed in mol kg−1 , gives

m= 1
3
× 0.890 × (261.35 × 10−3 kg mol−1 ) × (0.500 kg) × (1 mol kg−1 )
= 38.7... × 10−3 kg

Hence the ��.� g of Ba(NO� )� needs to be added to achieve the desired

ionic strength.

E�F.�(b) �e Debye–Hückel limiting law, [�F.��–���], is used to estimate the mean ac-
tivity coe�cient, γ± , at �� ○ C in water

log γ± = −0.509 �z+ z− � I 1�2 I = 12 � z 2i (b i �b −○ )

i
 where z± are the charge numbers on the ions from the salt of interest and I is
the ionic strength, de�ned in [�F.��–���]. In the de�nition of I the sum runs
over all the ions in the solution, z i is the charge number on ion i, and b i is its
molality.
A solution of Ca(NO� )� of molality b contributes Ca�+ at molality b and NO−3
at molality 2b. �e contribution to the ionic strength is therefore 12 [(+2)2 ×
b + (−1)2 × 2b]�b−○ = 3b�b −○ . A solution of NaCl of molality b ′ contributes Na+
at molality b′ and Cl – at molality b ′ . �e contribution to the ionic strength
is therefore 12 [(+1)2 × b ′ + (−1)2 × b ′ ]�b−○ = b ′ �b−○ . �e ionic strength of the
solution is therefore
(3b+b ′ )�b −○ = [3×(0.035 mol kg−1 )+1×(0.020 mol kg−1 )]�(1 mol kg−1 ) = 0.125

For solute Ca(NO� )� z+ = +2 and z− = −1 so the limiting law evaluates as

log γ± = −0.509 �z+ z− � I 1�2 = −0.509 �(+2) × (−1)� (0.125)1�2 = −0.359...

�e mean activity coe�cient is therefore γ± = 10−0.359 ... = 0.436... = 0.44 .

E�F.�(b) �e Davies equation is given in [�F.��b–���]

−A �z+ z− � I 1�2
log γ± = + CI
1 + BI 1�2
Because the electrolyte is �:� with univalent ions, the ionic strength is simply
I = b KCl �b −○ . �ere is no obvious straight-line plot using which the data can
be tested against the Davies equation, therefore a non-linear �t is made using
mathematical so�ware and assuming that A = 0.509; recall that the molali-
ties must be expressed in mol kg−1 . �e best-�t values are B = 1.53 and C =
−0.0686. With these values the predicted activity coe�cients are �.���, �.���
and �.���, which is very good agreement.

P�F.� �e Margules equations predict a vapour pressure given by [�F.��–���], p A =

p∗A x A exp(ξ[1− x A ]2 ); for small x A the vapour pressure is given by [�F.��–���],
p A = p∗A x A exp(ξ). Plots showing how the vapour pressures varies with x A for
the two cases are shown in Fig. �.��; an expansion for small x A is also shown.
A deviation of ��% between the two expressions occurs by about x A = 0.02.

P�F.� �e Debye–Hückel limiting law, [�F.��–���], and the Davies equation, [�F.��b–
���], are, respectively,

−0.509 �z+ z− � I 1�2

log γ± = −0.509 �z+ z− � I 1�2 log γ± = + CI
1 + BI 1�2
Figure �.�� shows a graphical comparison of the predictions of these two equa-
tions for the case of a �:� univalent electrolyte in aqueous solution at �� ○ C, with
B = 1.50 and C = 0; for such an electrolyte I = b�b −○ . �e two predictions for
㱠di�er by about ��% when I = 0.18 (I 1�2 = 0.42).
 2.0 0.4
full equation
1.5 approximate form 0.3
p A �p∗A
1.0 0.2

0.5 0.1

0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.00 0.01 0.02 0.03 0.04
xA xA

0.00
Debye–Hückel
Davies
−0.10
log γ±

−0.20

−0.30
0.0 0.1 0.2 0.3 0.4 0.5
1�2
I

I�.� On the basis of Raoult’s law, the activity in terms of the vapour pressure p J
is given by [�F.�–���], a J = p J �p∗J , where p∗J is the vapour pressure of the
pure solvent. �e activity coe�cient is de�ned through [�F.�–���], a J = γ J x J ,
therefore γ J = p J �p∗J x J .

�e data as given do not include values for the vapour pressure over the pure
liquids, so the �rst task is to plot p J against x J and extrapolate to x J = 1 to
�nd p∗J . �e vapour pressures are plotted in this way Fig. �.��, and the lin-
ear extrapolations to �nd the vapour pressures of the pure substances are also
shown. �ese give the values p∗E = 7.45 kPa and p∗B = 35.41 kPa; using these
values the activity coe�cients are computed as shown in the table.
 pE
pB
30

p J �kPa
20

10

0
0.0 0.2 0.4 0.6 0.8 1.0
xJ

xE p E �kPa xB p B �kPa γE γB γ E (Henry) G E �kJ mol−1

0.016 0 0.484 0.984 0 35.05 4.06 1.01 1.70 0.08
0.043 9 0.967 0.956 1 34.29 2.96 1.01 1.24 0.16
0.083 5 1.535 0.916 5 33.28 2.47 1.03 1.03 0.26
0.113 8 1.89 0.886 2 32.64 2.23 1.04 0.93 0.34
0.171 4 2.45 0.828 6 30.90 1.92 1.05 0.80 0.42
0.297 3 3.31 0.702 7 28.16 1.49 1.13 0.63 0.55
0.369 6 3.83 0.630 4 26.08 1.39 1.17 0.58 0.59
0.583 4 4.84 0.416 6 20.42 1.11 1.38 0.47 0.53
0.660 4 5.36 0.339 6 18.01 1.09 1.50 0.46 0.52
0.843 7 6.76 0.156 3 10.00 1.07 1.81 0.45 0.41
0.993 1 7.29 0.006 9 0.47 0.98 1.92 0.41 −0.03

On the basis of Henry’s law, the activity in terms of the vapour pressure p J is
given by [�F.��–���], a J = p J �K J , where K J is the Henry’s law constant for J as
a solute. �e activity coe�cient is de�ned as before, a J = γ J x J , and therefore
γ J = p J �K J x J .
To �nd the Henry’s law constant for E, the limiting slope of a plot of p E against
x E is taken. �e three data points given at the lowest values of x E do not ex-
trapolate back to the origin, which is not in accord with Henry’s law. Arguably
there are several equally valid ways of proceeding here, but one is to force the
best-�t line to pass through the origin and then use the �rst three data points;
this leads to the slope is shown by the dashed line in Fig. �.��. �e limiting
slope, taken in this way is 17.77 and so K E = 17.77 kPa. �is value is used to
compute the activity coe�cients for E based on Henry’s law, and the results are
shown in column headed γ E (Henry) in the table above. �e outcome is not
satisfactory because the expecting limiting behaviour γ E → 1 as x E → 0 is not
evidenced.
 �e excess Gibbs energy is de�ne in [�B.�–���] as G E = ∆ mix G − ∆ mix G ideal .
As explained in Section �F.� on page ���, the Gibbs energy of mixing is given
in terms of the activities as ∆ mix G = nRT (x A ln a A + x B ln a B ), whereas the
ideal Gibbs energy of mixing is ∆ mix G ideal = nRT (x A ln x A + x B ln x B ). �e
activities are written as a A = γ A x A and hence

G E = ∆ mix G − ∆ mix G ideal

= nRT (x A ln a A + x B ln a B ) − nRT (x A ln x A + x B ln x B )
= nRT (x A ln γ A x A + x B ln γ B x B ) − nRT (x A ln x A + x B ln x B )
= nRT (x A ln γ A + x B ln γ B )

Using the �nal expression G E �n is computed from the given data and using
the activity coe�cients (based on Raoult’s law) already derived. �e computed
values are given in the table.

I�.� On the basis of Raoult’s law, the activity in terms of the vapour pressure p J is
given by [�F.�–���], a J = p J �p∗J , where p∗J is the vapour pressure of the pure
substance. �e activity coe�cient is de�ned through [�F.�–���], a J = γ J x J ,
therefore γ J = p J �p∗J x J . �e partial pressure in the gas phase is determined
from the mole fraction in the gas phase, y J , p J = y J p tot , so the �nal calculation
is γ J = y J p tot �p∗J x J .
�e total pressure is given in kPa, whereas the vapour pressure over pure oxy-
gen is given in Torr. �e conversion is

(101.325 kPa)�(1 atm)

(p kPa) = (p′ Torr) ×
(760 Torr)�(1 atm)

�e temperature-composition phase diagram is shown in Fig. �.�� and the

computed values of the activity coe�cient are given in the table below. �e
fact that the activity coe�cient is close to � indicates near-ideal behaviour.

95
vapour
liquid
90
T�K

85

80

75
0.0 0.2 0.4 0.6 0.8 1.0
x O2 or y O2
 T�K x O2 y O2 p∗O2 �Torr γ O2
77.3 0 0 154
78 0.10 0.02 171 0.88
80 0.34 0.11 225 1.08
82 0.54 0.22 294 1.04
84 0.70 0.35 377 0.99
86 0.82 0.52 479 0.99
88 0.92 0.73 601 0.99
90.2 1.00 1.00 760 0.99

I�.� (a) To develop the expression for K into the form requested it is useful to
rewrite [MA] and [M]free in terms of the total concentration of macro-
molecule, [M]. �e total amount of A in the dialysis bag is [A]in = [A]free +
[A]bound , but the amount of A bound is equal to the amount of the macro-
molecule ligand complex, MA: [A]bound = [MA], therefore

[A]in = [A]free + [MA] hence [MA] = [A]in − [A]free

Recall that [A]free = [A]out and that, by de�nition ν = ([A]in −[A]out )�[M],
it therefore follows that

[MA] = [A]in − [A]out = ν[M]

Now consider the macromolecule, the total concentration of which is

[M]. It follows that [M] = [MA] + [M]free . �e expression just derived
for [MA], [MA] = ν[M] is substituted in to give [M] = ν[M] + [M]free ,
from which it follows that [M]free = [M](1 − ν)
With these expressions for [M]free and [MA], the expression for K is
developed into the requested form

[MA]c −○ ν[M]c −○ νc −○
K= = =
[M]free [A]free [M](1 − ν)[A]out (1 − ν)[A]out

where [A]free = [A]out is also used.

(b) �e equilibrium constant K ′ describes the equilibrium between a maco-
molecule with a single binding site, S, and the bound complex, SA

[SA]c −○
K′ =
[S]free [A]free
In part (a) ν is de�ned as the average number of bound ligands per macro-
molecule, and is therefore given by ν = [A]bound �[M]. Whereas M has N
binding sites, S only has one site, so the average number of ligands bound
per S is ν�N. �is number is also expressed (by analogy with the earlier
discussion) as [A]bound �[S], so it follows that ν�N = [A]bound �[S]. �e
�nal step is to realise that the concentration of bound ligand is equal to
 the concentration of the S–A complex, so [A]bound = [SA]. It therefore
follows that ν�N = [SA]�[S]. �is is rearranged to [SA] = [S]ν�N, which
is one of the terms needed in the expression for K ′ .
�e other term is [S]free which is related to [S] as follows. �e total con-
centration of S is given by [S] = [S]free + [SA], hence [S]free = [S] − [SA].
Substituting [SA] = [S]ν�N gives [S]free = [S] − [S]ν�N = (1 − ν�N)[S].
�e expression for the equilibrium constant is now developed as
[SA]c −○ ([S]ν�N)c −○ νc −○
K′ = = =
[S]free [A]free (1 − ν�N)[S][A]free [A]free (N − ν)
where to go to the �nal expression the numerator and demoninator are
multiplied by N and [S] is cancelled. �e Scatchard equation follows by
taking the factor (N − ν) to the le�
νc −○
K′ N − K′ν =
[A]free

(c) �e straight line plot is ν�[A]free against ν. �e task is therefore to deter-

mine ν from the data. Note that the data given are the total concentrations
of EB in and outside the bag. It therefore follows that

[EB]total,in = [EB]bound + [EB]free = [EB]bound + [EB]out

It follows that [EB]bound = [EB]total,in − [EB]out . Recall that ν is de�ned

as ν = [EB]bound �[M], therefore
[EB]total,in − [EB]out
ν=
[M]

�e given data and the derived values of ν are shown in the following table
(1 µM = 1 µmol dm−3 ), and plotted in Fig. �.��.

[EB]out �µM [EB]in �µM ν (ν�[EB]out )�(µM−1 )

0.042 0.292 0.250 5.95
0.092 0.590 0.50 5.41
0.204 1.204 1.00 4.90
0.526 2.531 2.01 3.81
1.150 4.150 3.00 2.61
�e data �t to quite a good straight line, the equation of which is

(ν�[EB]out )�(µM−1 ) = −1.17 × ν + 6.12

�e slope is −K ′ �c −○ where c −○ is the standard concentration, 1 mol dm−3 ,

but because [EB]out is used in µM, c −○ = 106 µM. It follows that the
(dimensionless) equilibrium constant is K ′ = 1.17 × 106 . �e intercept
gives K ′ N�c −○ , hence N = 5.23 : this is the average number of binding
sites per DNA molecule. �e graph is a good straight line, indicating that
the data �t the model quite well.
 6.0

(ν�[EB]out )�(µM−1 )
4.0

2.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
ν

I�.� �e dissolution of the protein according to the given equilibrium is described

by a solubility constant K s
PXv (s) ��⇀
� P (aq) + v X (aq)
v+ −
K s = a P a Xv
where the solubility constant is written in terms of the activities. Introducing
the activity coe�cients and molalities, b, gives
K s = γ±v+1 b P b Xv
At low to moderate ionic strengths the Debye–Hückel limiting law, [�F.��–���],
log γ± = −A�z− z+ �I 1�2 , is a reasonable approximation for the activity coe�-
cients.
Addition of a salt, such as (NH� )� SO� , causes I to increase, log γ± to become
more negative, and hence γ± to decrease. However, K s is an equilibrium con-
stant and remains unchanged. �erefore, the molality of Pv+ increases and the
protein solubility increases proportionately.
�is e�ect is also explicable in terms of Le Chatelier’s principle. As the ionic
strength increases by the addition of an inert electrolyte such as (NH� )� SO� ,
the ions of the protein that are in solution attract one another less strongly, so
that the equilibrium is shi�ed in the direction of increased solubility.
�e explanation of the salting out e�ect is somewhat more complicated and
can be related to the failure the Debye–Hückel limiting law at higher ionic
strengths. At high ionic strengths the Davies equation, [�F.��b–���], is a better
approximation
−A �z+ z− � I 1�2
log γ± = + CI
1 + BI 1�2
At low concentrations of inert salt, I 1�2 > I, the �rst term dominates, γ± de-
creases with increasing I, and salting in occurs; however, at high concentra-
tions, I > I 1�2 , the second term dominates, γ± increases with increasing I, and
salting out occurs. �e Le Chatelier’s principle explanation is that the water
molecules are tied up by ion-dipole interactions and become unavailable for
solvating the protein, thereby leading to decreased solubility.
I�.�� In Section �B.�(e) on page ��� the derivation of the expression for the osmostic
pressure starts by equating the chemical potential of A as a pure liquid subject
to pressure p with that of A in a solution of mole fraction x A containing solute B
and subject to pressure p+Π: µ ∗A (p) = µ A (x A , p+Π). �e chemical potential of
A in the solution is then expressed as µ A (x A , p + Π) = µ ∗A (p + Π) + RT ln x A ,
which assumes ideality. If the solution is not ideal, then the mole fraction is
replaced by the activity a A to give

µ ∗A (p) = µ∗A (p + Π) + RT ln a A

�e derivation then proceeds as before yielding the intermediate result −RT ln a A =

Vm Π for the non-ideal solution.
�e osmotic coe�cient � is de�ned as � = −(x A �x B ) ln a A , hence ln a A =
−�x B �x A . �is expression for ln a A is substituted into −RT ln a A = Vm Π to
give RT�x B �x A = Vm Π. �e �nal steps assume that the solution is dilute so
that x A ≈ 1 and x B = n B �(n A + n B ) ≈ n B �n A
xB
RT� = Vm Π
xA
nB
hence RT� = Vm Π
nA
nB
RT� =Π
n A Vm
RT�[B] = Π

To go to the last line V = n A Vm and [B] = n B �V are used.

D�A.� �e terms appearing in the equilibrium constant are the activities of the species
involved in the equilibrium, and these terms arise because the chemical po-
tential of each species depends on its activity. If a pure liquid or pure solid
is part of the equilibrium, its chemical potential contributes to the value of
∆ r G −○ . However, as the substance is in its pure form there is no composition
dependence of its chemical potential and hence no term in the equilibrium
constant. Put another way, such species have unit activity.

E�A.�(b) In general if the extent of a reaction changes by an amount ∆ξ then the amount
of a component J changes by ν J ∆ξ where ν J is the stoichiometric number for
species J (positive for products, negative for reactants). In this case ν A = −2
and ν B = +1.
n A = n A,0 + ∆n A = n A,0 + ν A ∆ξ = (1.75 mol) + (−2) × (0.30 mol) = �.�� mol
n B = n B,0 + ∆n B = n B,0 + ν B ∆ξ = (0.12 mol) + 1 × (0.30 mol) = �.�� mol

E�A.�(b) �e reaction Gibbs energy ∆ r G is de�ned by [�A.�–���], ∆ r G = (∂G�∂ξ) p,T .

Approximating the derivative by �nite changes gives
∂G ∆G −2.41 kJ
∆r G = � � ≈ = = −47 kJ mol−1
∂ξ p,T ∆ξ +0.051 mol

E�A.�(b) A reaction is exergonic if ∆ r G < 0 and endergonic if ∆ r G > 0. From the

Resource section the standard Gibbs energy change for the formation of liq-
uid benzene from its elements in their reference states at 298 K is ∆ f G −○ =
+124.3 kJ mol−1 . �is is positive so the reaction is endergonic .

�e reaction quotient is de�ned by [�A.��–���], Q = ∏J a J J . For the reaction

ν
E�A.�(b)
2A + B → 2C + D, ν A = −2, ν B = −1, ν C = +2, and ν D = +1. �e reaction
quotient is then
a C2 a D
Q = a −2
A aB aC aD = 2
−1 2
aA aB
 �e equilibrium constant is de�ned by [�A.��–���], K = �∏J a J J �equilibrium .
ν
E�A.�(b)
�e ‘equilibrium’ subscript indicates that the activities are those at equilibrium
rather than at an arbitrary stage in the reaction; however this subscript is not
usually written explicitly. In this case
3
a CHCl3 (l) a HCl(g)
K = a −1
CH 4 (g) a Cl 2 (g) a CHCl 3 (l) a HCl(g) =
−3 3
3
a CH4 (g) a Cl 2 (g)

�e activity of CHCl3 (l) is 1 because it is a pure liquid. Furthermore if the

gases are treated as perfect then their activities are replaced by a J = p J �p−○ . �e
equilibrium constant becomes

(p HCl �p−○ )3 p3 p−○

K= = HCl 3
(p CH4 �p )(p Cl2 �p )
−
○ −
○ 3 p CH4 p Cl2

E�A.�(b) �e standard reaction Gibbs energy is given by [�A.��a–���]

∆ r G −○ = � ν∆ f G −
−
○
� ν∆ f G −○
Products Reactants

�e relationship between ∆ r G −○ and K, [�A.��–���], ∆ r G −○ = −RT ln K, is then

used to calculate the equilibrium constant.

(i) For the reaction of mercury with chlorine

∆ r G −○ = ∆ f G −○ (HgCl2 , s) − {∆ f G −○ (Hg, l) + ∆ f G −○ (Cl2 , g)}

= ∆ f G −○ (HgCl2 , s) = −178.6 kJ mol−1

�en

−178.6 × 103 J mol−1

K = e−∆ r G = exp �− � = 2.02 × 1031
−
○
�RT
(8.3145 J K−1 mol−1 ) × (298 K)

(ii) For the reduction of copper ions by zinc

∆ r G −○ = ∆ f G −○ (Zn2+ , aq) + ∆ f G −○ (Cu, s)

− {∆ f G −○ (Zn, s) + ∆ f G −○ (Cu2+ , aq)}
= ∆ f G −○ (Zn2+ , aq) − ∆ f G −○ (Cu2+ , aq)
= (−147.06 kJ mol−1 ) − (+65.49 kJ mol−1 ) = −2.12... × 105 J mol−1

�en

−2.12... × 105 J mol−1

K = e−∆ r G = exp �− � = 1.80 × 1037
−
○
�RT
(8.3145 J K−1 mol−1 ) × (298 K)

Neither reaction has K < 1 at 298 K.

E�A.�(b) �e relationship between ∆ r G −○ and the equilibrium constant is given by [�A.��–
���], ∆ r G −○ = −RT ln K. �e ratio of the equilibrium constants for the two
reactions is
∆ r G 1−○ − ∆ r G 2−○
−
○
K 1 e−∆ r G 1 �RT
= −∆ G −○ �RT = exp �− �
K2 e r 2 RT
(−200 × 103 J mol−1 ) − (+30 × 103 J mol−1 )
= exp �− � = 1.1 × 1040
(8.3145 J K−1 mol−1 ) × (300 K)

E�A.�(b) �e reaction Gibbs energy at an arbitrary stage is given by [�A.��–���], ∆ r G =

∆ r G −○ + RT ln Q. In this case ∆ r G −○ = −4.73 kJ mol−1 . �e values of ∆ r G for
each value of Q are:
(i) At Q = 0.10
∆ r G = (−4.73 × 103 J mol−1 ) + (8.3145 J K−1 mol−1 )×(298 K)×ln(0.10)
= −1.04... × 104 J mol−1 = −10 kJ mol−1
(ii) At Q = 1.0
∆ r G = (−4.73 × 103 J mol−1 ) + (8.3145 J K−1 mol−1 )×(298 K)×ln(1.0)
= −4.73... × 103 J mol−1 = −4.7 kJ mol−1 (= ∆ r G −○ )
(iii) At Q = 10
∆ r G = (−4.73 × 103 J mol−1 ) + (8.3145 J K−1 mol−1 )×(298 K)×ln(10)
= +9.75... × 102 J mol−1 = +0.98 kJ mol−1
(iv) At Q = 100
∆ r G = (−4.73 × 103 J mol−1 ) + (8.3145 J K−1 mol−1 )×(298 K)×ln(100)
= +6.68... × 103 J mol−1 = +6.7 kJ mol−1
�e equilibrium constant K is the value of Q for which ∆ r G = 0. From the
above values, K will therefore be somewhere between 1.0 and 10. To �nd
exactly where by linear interpolation, note that according to ∆ r G = ∆ r G −○ +
RT ln Q, a plot of ∆ r G against ln Q should be a straight line. Consider the two
points on either side of zero, that is, (ii) and (iii). �e point ∆ r G = 0 occurs a
fraction (4.73...)�(0.975... + 4.73...) = 0.829... of the way between points (ii)
and (iii), so is at
ln K = ln 1 + (0.822...)×(ln 10 − ln 1) = 1.90...
Hence K = e1.90 ... = �.��
�e value is calculated directly by setting ∆ r G = 0 and Q = K in ∆ r G = ∆ r G −○ +
RT ln Q and rearranging for K
−4.73 × 103 J mol−1
K = e−∆ r G = exp �− � = 6.75
−
○
�RT
(8.3145 J K−1 mol−1 )×(298 K)
which is the same result as obtained from the linear interpolation.
E�A.�(b) For the reaction N2 O4 (g) � 2NO2 (g) the following table is drawn up by
supposing that there are n moles of N2 O4 initially and that at equilibrium a
fraction α has dissociated.

N2 O4 � �NO2
Initial amount n �
Change to reach equilibrium −αn +2αn
Amount at equilibrium (1 − α)n 2αn
1−α 2α
Mole fraction, x J
1+α 1+α
(1 − α)p 2α p
Partial pressure, p J
1+α 1+α

�e total amount in moles is n tot = (1−α)n+2αn = (1+α)n. �is value is used

to �nd the mole fractions. In the last line, p J = x J p has been used. Treating all
species as perfect gases so that a J = (p J �p−○ ), the equilibrium constant is

(p NO2 �p−○ )2 � 1+α �

2α p 2
2
a NO p2NO2 4α 2 p
K= 2
= = = =
a N2 O4 (p N2 O4 �p−○ ) p N2 O4 p−○ � (1−α)p � p−○ (1 − α)(1 + α) p−○
1+α

In this case α = 0.201 and p = 1.00 bar; recall that p−○ = 1 bar.

4 × 0.2012 1.00 bar

K= × = �.���
(1 − 0.201) × (1 + 0.201) 1 bar

E�A.��(b) �e relationship between K and K c is [�A.��b–���], K = K c × (c −○ RT�p−○ ) .

∆ν

For the reaction 3N2 (g) + H2 (g) � 2HN3 (g)

−2
∆ν = ν HN3 − ν N2 − ν H2 = 2 − 3 − 1 = −2 hence K = K c × (c −○ RT�p−○ )

p−○ �c −○ R evaluates to 12.03 K so the relationship can alternatively be written as

K = K c × [(12.03)�(T�K)]2 .

E�A.��(b) �e following table is drawn up:

A + B � C + 2D
Initial amount, n J,0 �mol �.�� �.�� � �.��
Change, ∆n J �mol −0.79 −0.79 +0.79 +1.58
Equilibrium amount,
�.�� �.�� �.�� �.��
n J �mol
Mole fraction, x J 0.178... 0.0309... 0.116... 0.674...
Partial pressure, p J (0.178...)p (0.0309...)p (0.116...)p (0.674...)p
 To go to the second line, the fact that 0.79 mol of C has been produced is
used to deduce the changes in the other species given the stoichiometry of the
reaction. For example, � mol of A is consumed for every � mol of C formed, so
∆ν A = −∆ν C = −0.79 mol. �e total amount in moles is n tot = (1.21 mol) +
(0.21 mol) + (0.79 mol) + (4.58 mol) = 6.79 mol. �is value is used to �nd the
mole fractions. In the last line, p J = x J p has been used.

(i) �e mole fractions are given in the above table.

(ii) Treating all species as perfect gases so that a J = p J �p−○ the equilibrium
constant is
2
aC aD (p C �p−○ )(p D �p−○ )2 p p2 x C x D2 p
K= = = C D −○ =
aA aB (p A �p )(p B �p )
−
○ −
○ pA pB p x A x B p−○
� 679 � � 458 �
79 2
1.00 bar
= 679
× = 9.60... = �.�
� 121
679
� � 97
3
� 1 bar

(iii) �e relationship between ∆ r G −○ and K [�A.��–���], ∆ r G −○ = −RT ln K, is

used to calculate ∆ r G −○ :

∆ r G −○ = −(8.3145 J K−1 mol−1 ) × ([25 + 273.15] K) × ln 9.60...

= −5.6 kJ mol−1

E�A.��(b) �e reaction for which ∆ r G −○ corresponds to the standard Gibbs energy of

formation of UH3 (s) is

U(s) + 32 H2 (g) � UH3 (s)

that is, the formation of one mole of UH3 from the elements in their reference
states. �e equilibrium partial pressure of hydrogen is used to calculate the
equilibrium constant K, which is then used with ∆ r G −○ = −RT ln K [�A.��–���]
to �nd ∆ r G −○ .
Treating hydrogen as a perfect gas, so that a H2 = p H2 �p−○ , and recalling that
a J = 1 for a pure solid gives

p−○
3�2 3�2
a UH3 (s) 1 105 Pa
K= = =� � =� �
a U(s) × a H2 (g)
3�2 1 × (p H2 �p )
−
○ 3�2 p H2 139 Pa

= 1.92... × 104

Hence

∆ r G −○ = −RT ln K
= −(8.3145 J K−1 mol−1 ) × (500 K) × ln(1.92... × 104 ) = −41.0 kJ mol−1
E�A.��(b) �e reaction corresponding to the standard Gibbs energy change of formation
of PH3 is
1
P (s) + 32 H2 (g) � PH3 (g)
4 4
�is is the reaction in question. �e reaction Gibbs energy for an arbitrary
reaction quotient is given by [�A.��–���], ∆ r G = ∆ r G −○ + RT ln Q. White
phosphorus (P4 , the reference state of phosphorus) is a solid and so has a = 1;
the other species are treated as perfect gases so that a J = p J �p−○ . �erefore the
reaction quotient Q is

(p PH3 �p−○ ) p PH3 × p−○ (0.6 bar) × (1 bar)1�2

1�2
a PH3
Q= = = = = 0.60
1�4 3�2
a P4 a H2 (p H2 �p−○ )3�2 p
3�2 (1.0 bar)3�2
H2

Hence
∆ r G = ∆ r G −○ + RT ln Q
= (+13.4 × 103 J mol−1 ) + (8.3145 J K−1 mol−1 ) × (298 K) × ln(0.60)
= +12 kJ mol−1
Because ∆ r G > 0 the spontaneous direction of the reaction under these condi-
tions is from right to le�.

E�A.��(b) �e standard Gibbs energy change for the reaction is given in terms of the
standard Gibbs energies of formation by [�A.��a–���]:
∆ r G −○ = ∆ f G −○ (PbI2 , aq) − ∆ f G −○ (PbI2 , s)
�is is rearranged for ∆ f G −○ (PbI2 , aq) and ∆ r G −○ is replaced by −RT ln K [�A.��–
���] to give
∆ f G −○ (PbI2 , aq) = ∆ r G −○ + ∆ f G −○ (PbI2 , s) = −RT ln K + ∆ f G −○ (PbI2 , s)
= −(8.3145 J K−1 mol−1 ) × (298.15 K) × ln(1.4 × 10−8 )
+ (−173.64 × 103 J mol−1 ) = −1.3 × 102 kJ mol−1

P�A.� �e required reaction can be generated from the following sum:

CO(g) + H2 (g) � H2 CO(l) ∆ r G −○ (1) = +28.95 kJ mol−1

H2 CO(l) � H2 CO(g) ∆ r G −○ (2)
CO(g) + H2 (g) � H2 CO(g) ∆ r G −○ (3) = ∆ r G −○ (1) + ∆ r G −○ (2)

If H2 CO(g) is treated as a perfect gas, so that a H2 CO(g) = p H2 CO �p−○ , then

noting that a J = 1 for a pure liquid, the equilibrium constant for the second
reaction is
a H CO(g) (p H2 CO �p−○ ) p H2 CO 1500 Torr 1 atm 1.01325 bar
K2 = 2 = = = × ×
a H2 CO(l) 1 p−○ 1 bar 760 Torr 1 atm
= 1.99...
 Using [�A.��–���], ∆ r G −○ = −RT ln K, the equilibrium constant for the re-
quired reaction is

K 3 = e−∆ r G
−
○
(3)�RT

∆ r G −○ (1) + ∆ r G −○ (2) ∆ r G −○ (1) − RT ln K 2

= exp �− � = exp �− �
RT RT
∆ r G −○ (1) 28.95 × 103 J mol−1
= K 2 exp �− � = (1.99...)×exp �− �
RT (8.3145 J K−1 mol−1 )×(298 K)
= 1.69 × 10−5

P�A.� �e reaction Gibbs energy for an arbitrary reaction quotient is given by [�A.��–
���], ∆ r G = ∆ r G −○ + RT ln Q. Q is given by [�A.��–���], Q = ∏J a J J . In each
ν

case a J = 1 for pure solids and a J = p J �p−○ for gases, assuming perfect behaviour.
Reaction (i): H2 O(g) � H2 O(s)
a H2 O(s) 1 p−○
Q= = =
a H2 O(g) (p H2 O �p−○ ) p H2 O
p−○
∆ r G = ∆ r G −○ + RT ln � �
p H2 O
= (−23.6 × 103 J mol−1 ) + (8.3145 J K−1 mol−1 ) × (190 K)
1 bar
× ln � � = +1.5 kJ mol−1
0.13 × 10−6 bar

Reaction (ii): H2 O(g) + HNO3 (g) � HNO3 .H2 O(s)

p−○
2
a HNO3 .H2 O(s) 1
Q= = =
a H2 O(g) a HNO3 (g) (p H2 O �p−○ )(p HNO3 �p−○ ) p H2 O p HNO3
p−○
2
∆ r G = ∆ r G −○ + RT ln � �
p H2 O p HNO3
= (−57.2 × 103 J mol−1 ) + (8.3145 J K−1 mol−1 ) × (190 K)
(1 bar)2
× ln � � = +2.0 kJ mol−1
(0.13 × 10−6 bar) × (0.41 × 10−9 bar)

Reaction (iii): 2H2 O(g) + HNO3 (g) � HNO3 .2H2 O(s)

p−○
3
a HNO3 .2H2 O(s) 1
Q= = =
2
aH 2 O(g)
a HNO3 (g) (p H2 O �p−○ )2 (p HNO3 �p−○ ) p H2 O p HNO3
2

p−○
3
∆ r G = ∆ r G −○ + RT ln � �
p2H2 O p HNO3
= (−85.6 × 103 J mol−1 ) + (8.3145 J K−1 mol−1 ) × (190 K)
(1 bar)3
× ln � � = −1.4 kJ mol−1
(0.13 × 10−6 bar)2 × (0.41 × 10−9 bar)
 Reaction (iv): 3H2 O(g) + HNO3 (g) � HNO3 .3H2 O(s)

p−○
4
a HNO3 .3H2 O(s) 1
Q= = =
3
aH 2 O(g)
a HNO3 (g) (p H2 O �p−○ )3 (p HNO3 �p−○ ) p3H2 O p HNO3
p−○
4
∆ r G = ∆ r G −○ + RT ln � 3
�
p H2 O p HNO3
= (−112.8 × 103 J mol−1 ) + (8.3145 J K−1 mol−1 ) × (190 K)
(1 bar)4
× ln � � = −3.5 kJ mol−1
(0.13 × 10−6 bar)3 × (0.41 × 10−9 bar)

�e results show that ∆ r G < 0 for reactions (iii) and (iv), so HNO3 .2H2 O
and HNO3 .3H2 O can form spontaneously under the prevailing conditions.
To identify which of these solids is most stable, consider the conversion of
HNO3 .2H2 O into HNO3 .3H2 O. �e required reaction is constructed by adding
reaction (iv) to the reverse of reaction (iii):

∆ r G�(kJ mol−1 )
HNO3 .2H2 O(s) � 2H2 O(g) + HNO3 (g) +1.35...
3H2 O(g) + HNO3 (g) � HNO3 .3H2 O(s) −3.50...
HNO3 .2H2 O(s) + H2 O(g) � HNO3 .3H2 O(s) −2.2

Since ∆ r G < 0 for this conversion, it follows that HNO3 .3H2 O is the thermo-
dynamically most stable solid (at least out of the four considered) under the
prevailing conditions.

P�A.� �e standard reaction enthalpy and entropy are calculated using standard en-
thalpies of formation and standard molar entropies respectively ([�C.�a–��]
and [�C.�a–��])
∆ r H −○ = 2∆ f H −○ (NO2 , g) − ∆ f H −○ (N2 O4 , g)
= 2 × (+33.18 kJ mol−1 ) − (+9.16 kJ mol−1 ) = +57.20 kJ mol−1
∆ r S −○ = 2S m
−
○
(NO2 , g) − S m
−
○
(N2 O4 , g)
= 2 × (+240.06 J K−1 mol−1 ) − (+304.29 J K−1 mol−1 ) = +175.83 J K−1 mol−1
�e relationship between the equilibrium constant and ∆ r G −○ is [�A.��–���],
∆ r G −○ = −RT ln K, and ∆ r G −○ is related to ∆ r H −○ and ∆ r S −○ according to [�D.�–
���], ∆ r G −○ = ∆ r H −○ − T∆ r S −○ . �erefore
K = e−∆ r G = e−(∆ r H = e−∆ r H
−
○ −
○
�RT −T ∆ r S −○ )�RT −
○
�RT ∆ r S −○ �R
e
−1
+57.20 × 10 J mol 3
+175.83 J K−1 mol−1
= exp �− � × exp � �
(8.3145 J K−1 mol−1 ) × (298 K) 8.3145 J K−1 mol−1
��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
enthalpy contribution to K entropy contribution to K

=e −23.0 ...
×e 21.1 ...
= (9.41... × 10 −11
) × (1.52... × 109 ) = 0.144
 �e calculation shows that ∆ r H −○ and ∆ r S −○ make contributions to K in opposite
directions: ∆ r H −○ acts to make K very small while ∆ r S −○ acts to make K very
large and the overall result is that K is close to 1. �e negative value of ∆ r H −○
can be interpreted in terms of the forward reaction involving the breaking of
the N–N bond in N� O� , while the positive value of ∆ r S −○ can be attributed to
the reaction forming two moles of gas from one mole. At 298 K the calculation
shows that the ∆ r H −○ contribution is slightly larger than the ∆ r S −○ contribution
which is re�ected in K being less than 1.

D�B.� �is is discussed in Section �B.� on page ��� and in Section �B.� on page ���.

E�B.�(b) For the reaction Br2 (g) � 2Br(g) the following table is drawn up by supposing
that there are n moles of Br2 initially and that at equilibrium a fraction α has
dissociated.

Br2 � �Br
Initial amount n �
Change to reach equilibrium −αn +2αn
Amount at equilibrium (1 − α)n 2αn
1−α 2α
Mole fraction, x J
1+α 1+α
(1 − α)p 2α p
Partial pressure, p J
1+α 1+α

�e total amount in moles is (1−α)n+2αn = (1+α)n. �is value is used to �nd

the mole fractions. In the last line, p J = x J p [�A.�–�] has been used. Treating
all species as perfect gases, so that a J = (p J �p−○ ), the equilibrium constant is

(p Br �p−○ )2 � 1+α �
2α p 2
2
a Br p2Br 4α 2 p
K= = = = =
a Br2 (p Br2 �p−○ ) p Br2 p−○ � (1−α)p � p−○ (1 − α)(1 + α) p−○
1+α

In this case α = 0.24 and p = 1.00 bar; recall that p−○ = 1 bar.
4 × 0.242 1.00 bar
K= × = 0.244... = �.��
(1 − 0.24) × (1 + 0.24) 1 bar

�e temperature dependence of K is given by [�B.�–���],

∆ r H −○ 1 1
ln K 2 − ln K 1 = − � − �
R T2 T1
 assuming that ∆ r H −○ is constant over the temperature range of interest.

112 × 103 J mol−1 1 1

ln K 2 = ln(0.244...) − −1 −1 � − � = 0.275...
8.3145 J K mol 2000 K 1600 K

�at is, K 2 = �.� , a larger value than at 1600 K, as expected for this endothermic
reaction.

E�B.�(b) �e data in the Resource section is used to calculate ∆ r G −○ and ∆ r H −○ at ��� K

∆ r G −○ = ∆ f G −○ (CHCl3 , l) + 3∆ f G −○ (HCl, g) − ∆ f G −○ (CH4 , g)

= (−73.7 kJ mol−1 ) + 3 × (−95.30 kJ mol−1 ) − (−50.72 kJ mol−1 )
= −3.08... × 102 kJ mol−1
∆ r H = ∆ f H −○ (CHCl3 , l) + 3∆ f H −○ (HCl, g) − ∆ f H −○ (CH4 , g)
−
○

= (−134.1 kJ mol−1 ) + 3(−92.31 kJ mol−1 ) − (−74.81 kJ mol−1 )

= −3.36... × 102 kJ mol−1

�e equilibrium constant at 25 ○ C (= 298.15 K) is calculated from ∆ r G −○ using

[�A.��–���], ∆ r G −○ = −RT ln K

∆ r G −○ −3.08... × 105 J mol−1

ln K = − =− = 1.24... × 102
RT (8.3145 J K−1 mol−1 ) × (298.15 K)
hence K = 1.29... × 1054 = 1.3 × 1054

Assuming that ∆ r H −○ is constant over the temperature range of interest, the

temperature dependence of K is given by [�B.�–���],

∆ r H −○ 1 1
ln K 2 − ln K 1 = − � − �
R T2 T1

�is is used to calculate the equilibrium constant at 50 ○ C (= 323.15 K)

−3.36... × 105 J mol−1 1 1

ln K 2 = ln(1.29... × 1054 ) − � − �
8.3145 J K−1 mol−1 323.15 K 298.15 K
= 1.14... × 102

�at is, K 2 = 3.6 × 1049 , a smaller value than at 25 ○ C, as expected for this
exothermic reaction.

E�B.�(b) Assuming that ∆ r H −○ is constant over the temperature range of interest, the
temperature dependence of K is given by [�B.�–���],

∆ r H −○ 1 1
ln K 2 − ln K 1 = − � − �
R T2 T1
 Using ∆ r G −○ = −RT ln K to substitute for K 1 and setting ln K 2 = ln 1 = 0 (the
crossover point) gives
∆ r G −○ (T1 ) ∆ r H −○ 1 1
=− � − �
RT1 R T2 T1
Rearranging for T2 gives
T1 ∆ r H −○ (1120 K) × (+125 kJ mol−1 )
T2 = = = 1.4 × 103 K
∆r H −○− ∆ r G (T1 ) (+125 kJ mol−1 ) − (+22 kJ mol−1 )
−○

E�B.�(b) �e van ’t Ho� equation [�B.�–���], d ln K�dT = ∆ r H −○ �RT 2 , is rearranged to

obtain an expression for ∆ r H −○
d ln K
∆ r H −○ = RT 2
dT
d B C B 3C 3C
= RT 2 �A + + 3 � = RT 2 �− 2 − 4 � = −R �B + 2 �
dT T T T T T
3 × (2.1 × 10 K )
7 3
= −(8.3145 J K−1 mol−1 ) × �(−1176 K) + �
(450 K)2
= 7.19... × 103 J mol−1 = 7.2 kJ mol−1
�e standard reaction entropy is obtained by �rst �nding an expression for
∆ r G −○ using [�A.��–���]
B C C
∆ r G −○ = −RT ln K = −RT �A + + � = −R �AT + B + 2 �
T T3 T
�e equation ∆ r G −○ = ∆ r H −○ − T∆ r S −○ [�D.�–���] is then rearranged to �nd
∆ r S −○
� �
∆ r H −○ − ∆ r G −○ 1 � �
∆r S =
−
○
= �−R �B + 3C
� + R �AT + B + 2 ��
C
� T �
T T � T 2
�
���� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � ���
∆r H −
○ −∆ r G − ○

2C 2 × (2.1 × 107 K2 )
= R �A − 3 � = (8.3145 J K−1 mol−1 ) × �−2.04 − �
T (450 K)3
= −21 J K−1 mol−1

An alternative approach to �nding ∆ r S −○ is to use the variation of G with T

which is given by [�E.�–���], (∂G�∂T) p = −S. �is implies that d∆ r G −○ �dT =
−∆ r S −○ where the derivative is complete (not partial) because ∆ r G −○ is indepen-
dent of pressure. Using the expression for ∆ r G −○ from above it follows that

� �
d∆ r G −○ � �
∆r S = − −
○
=−
d �−R �AT + B + C
��
2C
= R �A − 3 �
� T �
dT dT � 2
� T
���� � � � � � � � � � � � � � � � � � � � � � � � � �−○� � � � � � � � � � � � � � � � � � � � � � � � � ��
∆r G

which is the same expression obtained above.

E�B.�(b) Treating all species as perfect gases so that a J = p J �p−○ , the equilibrium constant
for the reaction CH3 OH(g) + NOCl(g) � HCl(g) + CH3 NO2 (g) is

a CH3 NO2 a HCl (p CH3 NO2 �p−○ )(p HCl �p−○ ) p CH3 NO2 p HCl
K= = =
a CH3 OH a NOCl (p CH3 OH �p−○ )(p NOCl �p−○ ) p CH3 OH p NOCl
(x CH3 NO2 p)(x HCl p) x CH3 NO2 x HCl
= = = Kx
(x CH3 OH p)(x NOCl p) x CH3 OH x NOCl

where K x is the part of the equilibrium constant expression that contains the
equilibrium mole fractions of reactants and products. Because K is indepen-
dent of pressure, and K = K x in this case, it follows that K x does not change
when the pressure is changed. Hence the percentage change in K x is zero .

E�B.�(b) �e following table is drawn up for the N2 (g) + O2 (g) � 2NO(g) reaction,
supposing that in order to reach equilibrium the reaction proceeds to the right
by an amount z moles.

N2 + O2 � 2NO
Initial amount n N2 ,0 n O2 ,0 �
Change to reach equilibrium −z −z +2z
Amount at equilibrium n N2 ,0 − z n O2 ,0 − z 2z
n N2 ,0 − z n O2 ,0 − z 2z
Mole fraction, x J
n tot n tot n tot
(n N2 ,0 − z)p (n O2 ,0 − z)p 2z p
Partial pressure, p J
n tot n tot n tot

�e total amount in moles is n tot = n N2 ,0 +n O2 ,0 at all times. Treating all species

as perfect gases so that a J = p J �p−○ the equilibrium constant is
2
a NO (p NO �p−○ )2 p2NO
K= = =
a N2 a O2 (p N2 �p )(p O2 �p ) p N2 p O2
−
○ −
○

(2z p�n)2 4z 2
= =
[(n N2 ,0 − z)p�n tot ] [(n O2 ,0 − z)p�n tot ] (n N2 ,0 − z)(n O2 ,0 − z)

Rearranging gives

K(n N2 ,0 − z)(n O2 ,0 − z) = 4z 2
Hence (4 − K)z 2 + K(n N2 ,0 + n O2 ,0 )z − n N2 ,0 n O2 ,0 K = 0

�e initial amounts are calculated as

5.0 g 2.0 g
n N2 ,0 = = 0.178... mol n O2 ,0 = = 0.0625... mol
28.02 g mol−1 32.00 g mol−1
 Substituting the values for n J and K into the above equation, dividing through
by mol2 and writing x = z�mol yields the quadratic
(3.99...)x 2 + (4.07... × 10−4 )x − 1.88... × 10−5 = 0
which has solutions x = 2.12... × 10−3 and x = −2.22... × 10−3 implying z =
(2.12... × 10−3 mol) or z = (−2.22... × 10−3 mol). �e negative value of z is
rejected because that would imply a negative amount of NO. �e mole fraction
of NO present at equilibrium is therefore
2z 2 × (2.12... × 10−3 mol)
x NO = = = �.���
n N2 ,0 + n O2 ,0 (0.178... mol) + (0.0625... mol)

E�B.�(b) �e temperature dependence of K is given by [�B.�–���]

∆ r H −○ 1 1 R ln(K 2 �K 1 )
ln K 2 − ln K 1 = − � − � hence ∆ r H −○ = −
R T2 T1 (1�T2 ) − (1�T1 )
(i) If the equilibrium constant is doubled then K 2 �K 1 = 2
(8.3145 J K−1 mol−1 ) × ln 2
∆ r H −○ = − = +38.7 kJ mol−1
[1�(325 K)] − (1�[310 K])
(ii) If the equilibrium constant is halved then K 2 �K 1 = 1�2
(8.3145 J K−1 mol−1 ) × ln(1�2)
∆ r H −○ = − = −38.7 kJ mol−1
[1�(325 K)] − (1�[310 K])

E�B.�(b) �e relationship between ∆ r G −○ and K is given by [�A.��–���], ∆ r G −○ = −RT ln K.

Hence if K = 1, ∆ r G −○ = −RT ln 1 = 0. Furthermore ∆ r G −○ is related to ∆ r H −○
and ∆ r S −○ by [�D.�–���], ∆ r G −○ = ∆ r H −○ − T∆ r S −○ , so if K = 1
∆ r H −○
∆ r H −○ − T∆ r S −○ = 0 hence T=
∆ r S −○
Values of ∆ r H −○ and ∆ r S −○ at ��� K are calculated using data from the Resource
section.
∆ r H −○ = ∆ f H −○ (CuSO4 , s) + 5∆ f H −○ (H2 O, g) − ∆ f H −○ (CuSO4 .5H2 O, s)
= (−771.36 kJ mol−1 ) + 5 × (−241.82 kJ mol−1 ) − (−2279.7 kJ mol−1 )
= +299.24 kJ mol−1
∆ r S −○ = S m
−
○
(CuSO4 , s) + 5S m
−
○
(H2 O, g) − S m
−
○
(CuSO4 .5H2 O, s)
= (109 J K−1 mol−1 ) + 5 × (188.83 J K−1 mol−1 ) − (300.4 J K−1 mol−1 )
= 752.75 J K−1 mol−1
Substituting these values into the equation found above, assuming that ∆ r H −○
and ∆ r S −○ do not vary signi�cantly with temperature over the range of interest,
gives:
∆ r H −○ 299.24 × 103 J mol−1
T= = = 398 K
∆ r S −○ 752.75 J K−1 mol−1
E�B.�(b) (i) Treating the vapour as a perfect gas so that a J = p J �p−○ , and noting that
pure solids have a J = 1, the equilibrium constant for the dissociation
NH4 Cl(s) � NH3 (g) + HCl(g) is

a NH3 ,g a HCl,g (p NH3 �p−○ )(p HCl �p−○ ) p NH3 p HCl

K= = =
a NH4 Cl,s 1 p−○ 2

Furthermore, because NH3 and HCl are formed in a 1 ∶ 1 ratio, they each
have a mole fraction of 1�2 and the partial pressure of each is half the total
pressure: p A2 = p B = 12 p. �e equilibrium constant at 427 ○ C is therefore

( 12 p)( 12 p) p2 (608 kPa)2

K= = = = 9.24... = �.��
p −
○2 4p−○ 2
4 × (100 kPa)2

(ii) �e standard reaction Gibbs energy at ��� ○ C is obtained using ∆ r G −○ =

−RT ln K [�A.��–���]

∆ r G −○ = −(8.3145 J K−1 mol−1 ) × ([427 + 273.15] K) × ln(9.24...)

= −1.29... × 104 J mol−1 = −12.9 kJ mol−1

(iii) �e variation of K with temperature, assuming that ∆ r H −○ does not vary

with T over the temperature range of interest, is given by [�B.�–���]

∆ r H −○ 1 1 R ln(K 2 �K 1 )
ln K 2 −ln K 1 = − � − � hence ∆ r H −○ = −
R T2 T1 (1�T2 ) − (1�T1 )

Noting that the above equilibrium constant expression K = p2 �4p−○ im-

2

plies that ln(K 2 �K 1 ) = ln(p22 �p21 ), ∆ r H −○ is calculated as

(8.3145 J K−1 mol−1 ) × ln �(1115 kPa)2 �(608 kPa)2 �

∆ r H −○ = −
[1�(459 + 273.15) K] − [1�(427 + 273.15) K]
= +1.61... × 105 J mol−1 = +162 kJ mol−1

(iv) �e standard reaction entropy is obtained from ∆ r G −○ and ∆ r H −○ by rear-

ranging ∆ r G −○ = ∆ r H −○ − T∆ r S −○ [�D.�–���]:

∆ r H −○ − ∆ r G −○ (1.61... × 105 J mol−1 ) − (−1.29... × 104 J mol−1 )

∆ r S −○ = =
T 700.15 K
= +249 J K−1 mol−1

P�B.� (a) �e reaction CH4 (g) � C(s, graphite) + 2H2 is the reverse of the forma-
tion reaction of methane, so

∆ r H −○ = −∆ f H −○ (CH4 , g) = −(−74.85 kJ mol−1 ) = +74.85 kJ mol−1

∆ r S −○ = −∆ f S −○ (CH4 , g) = −(−80.67 J K−1 mol−1 ) = +80.67 J K−1 mol−1
 �e equilibrium constant K is calculated using ∆ r G −○ = −RT ln K [�A.��–
���], with ∆ r G −○ being obtained from ∆ r G −○ = ∆ r H −○ − T∆ r S −○ [�D.�–���]

∆ r H −○ − T∆ r S −○
K = e−∆ r G = exp �− �
−
○
�RT
RT
(74.85 × 103 J mol−1 ) − (298 K) × (80.67 J K−1 mol−1 )
= exp �− �
(8.3145 J K−1 mol−1 ) × (298 K)
= 1.24 × 10−9

(b) �e temperature dependence of K is given by [�B.�–���]

∆ r H −○ 1 1
ln K 2 = ln K 1 − � − �
R T2 T1
assuming that ∆ r H −○ is constant over the temperature range of interest.
�e value of K at 50 ○ C is therefore

ln K 2 = ln(1.24... × 10−9 )
74.85 × 103 J mol−1 1 1
− −1 � − �
−1
8.3145 J K mol (50 + 273.15) K 298 K
= −18.1... hence K 2 = 1.30 × 10−8

(c) �e following table is drawn up, assuming that the initial amount of methane
is n and that at equilibrium a fraction α has dissociated. Graphite is a solid
so is not included in the calculations.

CH4 (g) � 2H2 (g) + C(s)

Initial amount n � —
Change to reach equilibrium −αn +2αn —
Amount at equilibrium (1 − α)n 2αn —
1−α 2α
Mole fraction, x J —
1+α 1+α
(1 − α)p 2α p
Partial pressure, p J —
1+α 1+α

�e total amount in moles is n tot = (1 − α)n + 2αn = (1 + α)n. �is

value is used to �nd the mole fractions. Treating CH4 and H2 as perfect
gases, so that a J = p J �p−○ , and recalling that pure solids have a J = 1, the
equilibrium constant is

a C (p H2 �p−○ )2 × 1 � 1+α �
2α p 2
2
aH p2H2
K= 2 = = =
a CH4 (p CH4 �p ) −
○ p CH4 p −
○ (1−α)p
� 1+α � p−○
4α 2 p 4α 2 p
= =
(1 − α)(1 + α) p−○ 1 − α 2 p−○
 Rearranging for α gives
1 1
K 2 1.24... × 10−9 2
α=� � =� �
4(p�p ) + K
−
○ 4 × (0.010 bar)�(1 bar) + 1.24... × 10−9

= 1.76 × 10−4

(d) If the pressure is increased, K will not change, because the equilibrium
constant is independent of pressure. However, the above expression for
the degree of dissociation, α = [K�(4p�p−○ + K)]1�2 , indicates that α will
decrease as p increases due to the denominator becoming larger. �is is
in accord with Le Chatelier’s principle, which predicts that an increase in
pressure will cause the reaction to adjust so as to minimise the pressure
increase. �is it can do by reducing the number of particles in the gas
phase, which implies a shi� CH4 (g) ← 2H2 (g) + C(s), corresponding to
a lower degree of dissociation.
If the temperature is increased, then the van ’t Ho� equation [�B.�–���],
d ln K�dT = ∆ r H −○ �RT 2 predicts that K will increase because ∆ r H −○ is
positive for this reaction, so that d ln K�dT and therefore also dK�dT is
positive. �e expression for the degree of dissociation, α = [K�(4p�p−○ +
K)]1�2 , shows that this increase in K will result in an increase in α. �is
is most clearly seen by noting that because α � (p�p−○ ) the expression
for α may be approximated as [K�(4p�p−○ )]1�2 which will increase as K
increases. �e result that α increases with T is again in accord with Le
Chatelier’s principle, which predicts that for this endothermic reaction
the equilibrium will shi� towards the products if the temperature rises.

P�B.� �e van ’t Ho� equation [�B.�–���] is

d ln K ∆ r H −○ d ln K ∆ r H −○
= which can also be written − =
dT RT 2 d(1�T) R
�e second form implies that a graph of − ln K against 1�T should be a straight
line of slope ∆ r H −○ �R; such a plot is shown in Fig. �.�.

T�K K 1�(T�K) − ln K
300 4.0 × 1031 0.003 33 −72.8
500 4.0 × 1018 0.002 00 −42.8
1 000 5.1 × 108 0.001 00 −20.0

�e data fall on a good straight line, the equation of which is

ln K = (−2.259 × 104 ) × 1�(T�K) + 2.463

∆ r H −○ �R is determined from the slope

∆ r H −○ = R × (slope × K) = (8.3145 J K−1 mol−1 ) × (−2.259 × 104 K)

= −1.9 × 102 kJ mol−1
 0

−20

−40

− ln K
−60

−80

0.000 0.001 0.002 0.003 0.004

1�(T�K)

P�B.� Treating NH3 as an ideal gas (so that a J = p J �p−○ ) and noting that pure solids
have a J = 1, the equilibrium constant for the decomposition CaCl2 .NH3 (s) �
CaCl2 (s) + NH3 (g) is
a CaCl2 ,s a NH3 ,g 1 × (p NH3 �p−○ ) p NH3
K= = = −○
a CaCl2 .NH3 ,s 1 p
At 400 K, the value of K is therefore (1.71 kPa)�(100 kPa) = 0.0171.
�e starting point for �nding the temperature dependence of ∆ r G −○ is the tem-
perature dependence of K, which is given by [�B.�–���]
∆ r H −○ 1 1
ln K 2 = ln K 1 − � − �
R T2 T1
Using ∆ r G −○ = −RT ln K [�A.��–���] to replace ln K 2 by −∆ r G −○ �RT2 , and
setting T2 = T where T is any temperature between 350 K and 470 K, gives
∆ r G −○ ∆ r H −○ 1 1
− = ln K 1 − � − �
RT R T T1
�is expression is rearranged for ∆ r G −○
1 1 ∆ r H −○
∆ r G −○ = −RT ln K 1 + T∆ r H −○ � − � = ∆ r H −○ − �R ln K 1 + �T
T T1 T1
Setting T1 = 400 K and K 1 = 0.0171 as calculated above gives

∆ r G −○ = +78 × 103 J mol−1 − �(8.3145 J K−1 mol−1 ) × ln(0.0171)

78 × 103 J mol−1
+ �T
400 K
= (+78 × 103 J mol−1 ) − (1.6 × 102 J K−1 mol−1 )T

or, dividing through by kJ mol−1 : ∆ r G −○ �kJ mol−1 = 78 − 0.16(T�K)

P�B.� �e following table is drawn up for the I2 (g) � 2I(g) equilibrium:

I2 � 2I
Initial amount n I2 0
Change to reach equilibrium −αn I2 +2αn I2
Amount at equilibrium (1 − α)n I2 2αn I2
1−α 2α
Mole fraction, x J
1+α 1+α
(1 − α)p 2α p
Partial pressure, p J
1+α 1+α

�e total amount in moles is n tot = (1 − α)n I2 + 2αn I2 = (1 + α)n I2 . �is value

is used to �nd the mole fractions. Treating all species as perfect gases, so that
a J = p J �p−○ , the equilibrium constant is:

a 2 (p I �p−○ )2 � 1+α �
2α p 2
p2I 4α 2 p
K= I = = = =
a I2 (p I2 �p ) p I2 p
−
○ −
○ (1−α)p
� 1+α � p −
○ (1 − α)(1 + α) p −
○

�e total amount in moles is found from the pressure using the perfect gas law
[�A.�–�], pV = n tot RT. With this, α can then be determined.
pV
pV = n tot RT = (1 + α)n I2 RT hence α= −1
n I2 RT
�ese expressions are used to calculate α and hence K from the given data; the
results are shown in the table below. �e standard enthalpy of dissociation is
then found using the van ’t Ho� equation [�B.�–���]:
d ln K ∆ r H −○ d ln K ∆ r H −○
= which can also be written − =
dT RT 2 d(1�T) R
�e second form implies that a graph of − ln K against 1�T should be a straight
line of slope ∆ r H −○ �R; the plot is shown in Fig. �.�.

T�K 100p�atm 104 n I2 �mol α K 104 �(T�K) − ln K

973 6.244 2.4709 0.0846 1.824 × 10−3 10.277 6.307
1 073 7.500 2.4555 0.1888 1.123 × 10−2 9.320 4.489
1 173 9.181 2.4366 0.3415 4.911 × 10−2 8.525 3.014

�e data fall on a good straight line, the equation of which is

ln K = 1.880 × 104 �(T�K) − 13.02
∆ r H −○ �R is determined from the slope
∆ r H −○ = R × (slope × K) = (8.3145 J K−1 mol−1 ) × (1.880 × 104 K)
= +156 kJ mol−1
 8.0

6.0

− ln K
4.0

2.0

0.0
8.0 8.5 9.0 9.5 10.0 10.5
10 �(T�K)
4

P�B.�� �e equilibrium for which ∆ r H −○ is the enthalpy change of solution is A(g) �

A(solv) where A is H2 or CO. Replacing activities of solutes by molar concen-
trations and activities of gases by partial pressures, the equilibrium constant for
this reaction is:

a A,solv ([A]�c −○ ) sA sA
K= = = −○ −○ = = s A �mol dm−3 bar−1
a A,g p A �p −
○ c �p (1 mol dm−3 )�(1 bar)

where s A = [A]�p A is the solubility. �e standard enthalpy of solution is ob-

tained using the van ’t Ho� equation [�B.�–���], d ln K�dT = ∆ r H −○ �RT 2 .
Replacing ∆ r H −○ by ∆ sol H −○ and noting from inside the front cover that ln x =
ln 10 × log x gives

d ln K d log K
∆ sol H −○ = RT 2 = RT 2 ln 10 ×
dT dT
d
= RT 2 ln 10 × log(s�mol cm−3 bar−1 )
dT

where the expression for K from above has been used. It does not matter
whether s is in mol dm−3 bar−1 or mol cm−3 bar−1 because the only di�erence
is a constant factor which vanishes on di�erentiating the logarithm. �e en-
thalpies of solvation for H2 and CO are therefore

d 768 768 K
H2 : ∆ sol H −○ = RT 2 ln 10 × �−5.39 − � = RT 2 ln 10 ×
dT T�K T2
= R ln 10 × (768 K) = (8.3145 J K−1 mol−1 ) × ln 10 × (768 K)
= +14.7 kJ mol−1
 d 980 980 K
CO: ∆ sol H −○ = RT 2 ln 10 × �−5.98 − � = RT 2 ln 10 ×
dT T�K T2
= R ln 10 × (980 K) = (8.3145 J K−1 mol−1 ) × ln 10 × (980 K)
= +18.8 kJ mol−1

P�B.�� �e relationship between K and K c is given by [�A.��b–���]

c −○ RT
∆ν
K = Kc × � � where ∆ν = ν(products) − ν(reactants)
p−○
�is expression for K is substituted into the van ’t Ho� equation [�B.�–���],
d ln K�dT = ∆ r H −○ �RT 2
� ∆ν �
� c −○ RT � ∆ r H −○
ln �K c × � −○ � �
�
d
dT � � = RT 2
p �
� �
�e le� hand side of this expression is evaluated to give
� ∆ν �
� c −○ RT � c −○ R
ln �K c × � −○ � �
�
d d
� = �ln K c + ∆ν ln � −○ � + ∆ν ln T�
dT � p � dT p
� �
d ln K c ∆ν
= +
dT T
so that
d ln K c ∆ν ∆ r H −○ d ln K c ∆ r H −○ ∆ν
+ = hence = −
dT T RT 2 dT RT 2 T
If ∆ r H −○ is assumed not to vary with temperature between T1 and T2 , this ex-
pression may be integrated between T1 and T2 :
T2 T2 ∆ r H −○ ∆ν
� d ln K c = � � − � dT
T1 T1 RT 2 T
to give

∆ r H −○ 1 1 T2
ln K c (T2 ) − ln K c (T1 ) = − � − � − ∆ν ln � �
R T2 T1 T1

D�C.� A galvanic cell is an electrochemical cell that produces electricity as a result

of the spontaneous reaction occuring inside it. An electrolytic cell is an elec-
trochemical cell in which a non-spontaneous reaction is driven by an external
source of current.
D�C.� �e relationship between the cell potential and the Gibbs energy change of the
cell reaction, ∆ r G = −νFE cell only applies under reversible conditions. �is is
achieved by balancing the cell with an equal and opposite externally applied
potential. Under these circumstances, no current �ows.

E�C.�(b) (i) �e reduction half-reactions, together with their standard electrode po-
tentials from the Resource section, are
R: Ag2 CrO4 (s) + 2e− → 2Ag(s) + CrO2−
4 (aq) E −○ (R) = +0.45 V
L: Cl2 (g) + 2e− → 2Cl− (aq) E −○ (L) = +1.36 V
�e cell reaction is obtained by subtracting the le�-hand reduction half-
reaction from the right-hand reduction half reaction

Ag2 CrO4 (s) + 2Cl− (aq) → 2Ag(s) + Cl2 (g) + CrO2−

4 (aq)

�e standard cell potential is calculated as the di�erence of the two stan-

−
○
dard electrode potentials [�D.�–���], E cell = E −○ (R) − E −○ (L)
−
○
E cell = (+0.45 V) − (+1.36 V) = −0.91 V

(ii) �e reduction half-reactions and their standard electrode potentials are

R: Sn4+ (aq) + 2e− → Sn2+ (aq) E −○ (R) = +0.15 V
L: Fe3+ (aq) + e− → Fe2+ (aq) E −○ (L) = +0.77 V
�e cell reaction is obtained by subtracting the le�-hand reduction half-
reaction from the right-hand reduction half-reaction, a�er �rst multiply-
ing the le�- hand half-reaction by two so that the numbers of electrons in
both half-reactions are the same.

Sn4+ (aq) + 2Fe2+ (aq) → Sn2+ (aq) + 2Fe3+ (aq)

�e standard cell potential is

−
○
E cell = (+0.15 V) − (+0.77 V) = −0.26 V

(iii) �e reduction half-reactions and their standard electrode potentials are

R: MnO2 (s) + 4H+ (aq) + 2e− → Mn2+ (aq) + 2H2 O(l)
L: Cu2+ (aq) + 2e− → Cu(s)
with E −○ (R) = +1.23 V and E −○ (L) = +0.34 V. �e cell reaction (R − L) is
therefore

MnO2 (s) + 4H+ (aq) + Cu(s) → Mn2+ (aq) + 2H2 O(l) + Cu2+ (aq)

and the standard cell potential is

−
○
E cell = (+1.23 V) − (+0.34 V) = +0.89 V
E�C.�(b) (i) �e required reduction half-reactions are
R: 2H2 O(l) + 2e− → H2 (g) + 2OH− (aq) E −○ (R) = −0.83 V
L: 2Na+ (aq) + 2e− → 2Na(s) E −○ (L) = −2.71 V
�e cell reaction (R − L) generated from these reduction half-reactions is
2H2 O(l)+2Na(s) → H2 (g)+2OH− (aq)+2Na+ (aq) which is equivalent
to the required reaction. �e cell required is

Na(s)�NaOH(aq)�H2 (g)�Pt(s)

�e platinum electrode is an ‘inert metal’ that acts as a source or sink

of electrons. Note that there is no interface between the half cells because
they have a common electrolyte (NaOH(aq)). �e standard cell potential
is
−
○
E cell = E −○ (R) − E −○ (L) = (−0.83 V) − (−2.71 V) = +1.88 V

(ii) �e required reduction half-reactions are

R: I2 (g) + 2e− → 2I− (aq) E −○ (R) = +0.54 V
L: 2H+ (aq) + 2e− → H2 (g) E −○ (L) = 0 (by de�nition)
�e cell reaction (R − L) generated from these reduction half-reactions is
I2 (g) + H2 (g) → 2I− (aq) + 2H+ (aq) which is equivalent to the required
reaction. �e cell required is

Pt(s)�H2 (g)�HI(aq)�I2 (g)�Pt(s)

and the standard cell potential is

−
○
E cell = E −○ (R) − E −○ (L) = +0.54 V

(iii) One possible pair of reduction half-equations is

R: 2H+ (aq) + 2e− → H2 (g) E −○ (R) = 0 (by de�nition)

L: 2H2 O(l) + 2e− → H2 (g) + 2OH− (aq) E −○ (L) = −0.83 V
�e cell reaction (R − L) generated from these reduction half-reactions
is 2H+ (aq) + 2OH− (aq) → 2H2 O(l) which is equivalent to (twice) the
required reaction. �e required cell is

Pt(s)�H2 (g)�NaOH(aq)��HCl(aq)�H2 (g)�Pt(s)

and the standard cell potential is

−
○
E cell = E −○ (R) − E −○ (L) = −(−0.83 V) = +0.83 V

An alternative pair of reduction half-equations is

R: O2 (g) + 4H+ (aq) + 4e− → 2H2 O(l) E −○ (R) = +1.23 V
L: O2 (g) + 2H2 O(l) + 4e− → 4OH− (aq) E −○ (L) = +0.40 V
 for which the required cell is

Pt(s)�O2 (g)�NaOH(aq)��HCl(aq)�O2 (g)�Pt(s)

�e cell reaction is the same as before and the standard cell potential is
−
○
therefore also the same: E cell = (+1.23 V) − (+0.40 V) = +0.83 V.

E�C.�(b) (i) �e reduction half-reactions for the cell in question are:

R: 2AgCl(s) + 2e− → 2Ag(s) + 2Cl− (aq)
L: 2H+ (aq) + 2e− → H2 (g)
which reveal that ν = 2 for the given cell reaction. �e Nernst equation
[�C.�–���] is E cell = E cell
−
○
− (RT�νF) ln Q. Noting that a J = 1 for pure
solids the Nernst equation in this case is

RT a2 + a2 −
E cell = E cell
−
○
− ln � H Cl �
2F a H2
Note that HCl(aq) must be treated as separate H+ and Cl− ions since it is
a strong acid and therefore fully dissociated in water. If the H2 is treated as
a perfect gas then a H2 = p H2 �p−○ , which gives a H2 = 1 in this case because
the hydrogen is at the standard pressure. �is gives
RT
E cell = E cell
−
○
− ln (a H+ a Cl− )
F
As discussed in Section �F.� on page ��� the activities of the H+ and Cl−
are given by a = γ± (b�b −○ ) where γ± is the mean activity coe�cient of the
electrolyte which in this case is common to both electrodes. Making this
substitution and denoting the molality of the common HCl solution by b
gives
RT γ2 b2
E cell = E cell
−
○
− ln � ± 2 �
F b −○
(ii) �e relationship between the cell potential and ∆ r G is given by [�C.�–
���], ∆ r G = −νFE cell :

∆ r G = −2 × (96485 C mol−1 ) × (0.4658 V) = −89.9 kJ mol−1

where 1 C V = 1 J has been used.

(iii) �e Debye–Hückel limiting law [�F.��–���] is log γ± = −A�z+ z− �I 1�2 . In
this equation A = 0.509 for an aqueous solution at �� ○ C, z+ and z− are the
charges on the ions, and I is the ionic strength which for a solution con-
taining two types of ion is given by [�F.��–���], I = 12 (b+ z+2 + b− z−2 )�b−○ .
For an HCl solution of molality b, z+ = 1 (for H+ ), z− = −1 (for Cl− ) and
b+ = b− = b. �erefore
1�2
log γ± = −A�z+ z− �� 12 (b+ z+2 + b− z−2 )�b −○ �
1�2 b 1�2
= −A × �(+1) × (−1)� × � 21 (b × 12 + b × (−1)2 )�b−○ � = −A � �
b −○
 −
○
�e Nernst equation from part (i) is rearranged for E cell and the expres-
sion for γ± is substituted in, noting from inside the front cover that ln x =
ln 10 × log x.

RT γ2 b2 2RT b
−
○
E cell = E cell + ln � ± 2 � = E cell + �ln � −○ � + ln 10 × log γ± �
F b −○ F b
2RT � � b b 1�2 �
�
= E cell + �ln � −○ � − ln 10 × A � −○ � �
F � � b b �
�
2 × (8.3145 J K−1 mol−1 ) × (298.15 K)
= (+0.4658 V) +
96485 C mol−1
� 1�2 �
� 0.01 mol kg−1 0.01 mol kg−1 �
×� �ln � � − ln 10 × (0.509) × � � �
�
� −1 −1
�
� 1 mol kg 1 mol kg �
= +0.223 V

−
○
Finally, note that E cell = E −○ (R)−E −○ (L) = E −○ (AgCl�Ag, Cl− )−E −○ (H+ �H2 ).
Because E (H �H2 ) = 0 (by de�nition), it follows that E −○ (AgCl�Ag, Cl) =
−
○ +
−
○
E cell = +0.223 V

E�C.�(b) �e reduction half-reactions for the cell in question are

R: 2NO−3 (aq) + 4H+ (aq) + 2e− → 2NO2 (g) + 2H2 O(l)

L: Zn2+ (aq) + 2e− → Zn(s)

which reveal that ν = 2 for the given cell reaction. As explained in Section �C.�(a)
on page ��� the maximum non-expansion (electrical) work that a reaction when
it advances by an in�nitesimal amount dξ at some composition is given by
dw e = ∆ r G dξ. �e reaction Gibbs energy ∆ r G therefore represents the work
done per mole of reaction, that is, when the reaction advances by ∆ξ = 1 mol at
constant composition. �e reaction Gibbs energy is related to the cell potential
according to [�C.�–���], ∆ r G = −νFE cell , so assuming that the cell is operating
under standard conditions the electrical work that can be done (per mole of
reaction) is

dw e �dξ = ∆ r G −○ = −2FE cell

−
○
= −2 × (96485 C mol−1 ) × (−0.040 V)
= +7.7 kJ mol−1

�e positive value indicates that work has been done on the system by the
surroundings.

E�C.�(b) �e Nernst equation [�C.�–���] is E cell = E cell

−
○
− (RT�νF) ln Q. If Q changes
from Q 1 to Q 2 then the change in cell potential is given by

RT RT RT Q2
E cell,1 − E cell,2 = �E cell
−
○
− ln Q 2 � − �E cell
−
○
− ln Q 1 � = − ln � �
νF νF νF Q1
 For ν = 3 and Q 2 �Q 1 = 5 the change in cell potential is

(8.3145 J K−1 mol−1 ) × (298 K)

E cell,1 − E cell,2 = − × ln 5 = −0.014 V
3 × (96485 C mol−1 )

where 1 J C−1 = 1 V is used.

P�C.� �e reduction half-reactions for the speci�ed cell are

R: 1
O (g) + 2H+ (aq) + 2e−
2 2
→ H2 O(l)
L: 2H+ (aq) + 2e− → H2 (g)

for which ν = 2. �e cell reaction (R − L) is 12 O2 (g) + H2 (g) → H2 O(l),

which corresponds to the formation reaction for H2 O(l) from its elements.
�e standard Gibbs energy of formation of H2 O(l) is therefore equal to ∆ r G −○
for this reaction; in turn this is given by [�C.�–���], ∆ r G −○ = −νFE cell
−
○
.

∆ f G −○ (H2 O, l) = −νFE cell

−
○
= −2×(96485 C mol−1 )×(+1.23 V) = −237 kJ mol−1

P�C.� (a) �e reduction half-reactions for the cell are:

R: Ag+ (aq,m R ) + e− → Ag(s)
L: Ag+ (aq,m L ) + e− → Ag(s)
for which ν = 1. �e overall cell reaction is

Ag+ (aq,m R ) → Ag+ (aq,m L )

If m L is increased, then there is an increased tendency for the cell reaction

to shi� in the direction Ag+ (aq,m R ) ← Ag+ (aq,m L ). �erefore ∆ r G for
the cell reaction will increase, and so E cell will decrease because ∆ r G =
−νFE cell . �is is con�rmed by the Nerst equation for this cell

RT a Ag+ (aq,m L )
E cell = E cell
−
○
− ln � �
F a Ag+ (aq,m R )

If m L is increased then a Ag+ (aq,m L ) will increase and consequently E cell

will decrease.
(b) �e reduction half-reactions for the cell are
R: 2H+ (aq) + 2e− → H2 (g,p R )
L: 2H+ (aq) + 2e− → H2 (g,p L )
for which ν = 2. �e overall cell reaction is

H2 (g,p L ) → H2 (g,p R )

If p L is increased then there is an increased tendency for the cell reaction

as written to move in the forwards direction. �erefore ∆ r G for the cell
 will decrease and so E cell will increase . �is is con�rmed by the Nernst
equation. Treating the hydrogen as a perfect gas so that a H2 = p H2 �p−○ ,
the Nernst equation for this cell is

RT pR
E cell = E cell
−
○
− ln � �
2F pL

If p L is increased then E cell will increase.

(c) �e reduction half-reactions for the cell are
R: MnO2 (s) + 4H+ (aq) + 2e− → Mn2+ (aq) + 2H2 O(l)
L: [Fe(CN)6 ]3− (aq) + e− → [Fe(CN)6 ]4− (aq)
�e overall cell reaction, a�er multiplying the le�-hand reduction half-
reaction by � so that both half-reactions have ν = 2, is

MnO2 (s) + 4H+ (aq) + 2[Fe(CN)6 ]4− (aq)

→ Mn2+ (aq) + 2H2 O(l) + 2[Fe(CN)6 ]3− (aq)

If the pH in the right-hand compartment is decreased, corresponding

to an increase in the H+ concentration, then there will be an increased
tendency for the cell reaction as written to move in the forward direction.
�erefore ∆ r G for the cell will decrease and so E cell will increase . �is
is con�rmed by the Nernst equation. Noting that pure solids and liquids
have a J = 1, the Nernst equation for this cell is

RT � a Mn2+ a[Fe(CN)6 ]3− �

2
E cell = E cell
−
○
− ln
2F � a H4 a2
+
[Fe(CN)6 ]4− �

If the pH is decreased then a H+ will increase and therefore E cell will in-
crease.
(d) �e reduction half-reactions for the cell are
R: Br2 (l) + 2e− → 2Br−
L: Cl2 (g) + 2e− → 2Cl−
�e overall cell reaction is

Br2 (l) + 2Cl− (aq) → 2Br− (aq) + Cl2 (g)

If the concentration of HCl in the le�-hand compartment is increased,

then there will be an increased tendency for the overall cell reaction as
written to shi� in the forward direction. �erefore ∆ r G for the cell will
decrease and so E cell will increase . �is is con�rmed by the Nernst equa-
tion. Noting that pure liquids have a J = 1 the Nernst equation for this cell
is
2
RT a Br − a Cl
E cell = E cell
−
○
− ln � 2 2 �
2F a Cl−
If HCl is added then a Cl− will increase so E cell will increase.
(e) TO DO/CHECK
 (f) �e reduction half-reactions for the cell are
R: MnO2 (s) + 4H+ (aq) + 2e− → Mn2+ (aq) + 2H2 O(l)
L: Fe2+ (aq) + 2e− → Fe(s)
�e overall cell reaction is
MnO2 (s) + 4H+ (aq, L) + Fe(s) → Mn2+ (aq) + 2H2 O(l) + Fe2+ (aq)
where H+ (aq, L) has been written to emphasise that it is H+ in the le�-
hand compartment that is involved in the reaction. If acid is added to
both compartments then the acid added to the right-hand compartment
will have no e�ect, because H+ (aq, R) does not appear in the overall cell
reaction. However, the acid added to the le�-hand compartment will
increase the tendency of the cell reaction as written to move in the for-
ward direction. �erefore ∆ r G for the cell will decrease and so E cell will
increase .
�is is con�rmed by the Nernst equation. Noting that pure solids and
liquids have a J = 1, the Nernst equation for this cell is

RT � a Mn2+ a Fe2+ �
E cell = E cell
−
○
− ln
2F � a H4
+ (aq,L) �

�e addition of acid to the le�-hand compartment will increase a H+ (aq,L)

which will result in E cell increasing. �e fact that acid has also been added
to the right-hand compartment has no e�ect on E cell because a H+ (aq,R)
does not appear in the Nernst equation.

D�D.� �is is discussed in Impact ��.

E�D.�(b) (i) �e following electrodes are combined

R: Cu2+ (aq) + 2e− → Cu(s) E −○ (R) = +0.34 V
L: Sn2+ (aq) + 2e− → Sn(s) E −○ (L) = −0.14 V
�e cell reaction (R−L) is Cu2+ (aq)+Sn(s) → 2Cu(s)+Sn2+ (aq), which
is equivalent to the required reaction, and has ν = 2. �e standard cell
−
○
potential is given by [�D.�–���], E cell = E −○ (R) − E −○ (L)
−
○
E cell = (+0.34 V) − (−0.14 V) = +0.48V
�e relationship between the equilibrium constant and the standard cell
−
○
potential is given by [�C.�–���], E cell = (RT�νF) ln K. Rearranging gives

νF −○ 2 × (96485 C mol−1 )
ln K = E cell = × (+0.48 V) = 37.3...
RT (8.3145 J K−1 mol−1 ) × (298 K)
 where 1 V = 1 J C−1 is used. Hence K = 1.7 × 1016 .
(ii) �e following electrodes are combined
R: Cu2+ (aq) + 2e− → Cu(s) E −○ (R) = +0.34 V
L: 2Cu+ (aq) + 2e− → 2Cu(s) E −○ (L) = +0.52 V
�e cell reaction is Cu2+ (aq) + Cu(s) → 2Cu+ (aq) which is the required
reaction, and has ν = 2. �erefore, using the same equations as in part (i)
−
○
E cell = E −○ (R) − E −○ (L) = (+0.34 V) − (+0.52 V) = −0.18 V
νF −○ 2 × (96485 C mol−1 )
ln K = E cell = × (−0.18 V) = −14.0...
RT (8.3145 J K−1 mol−1 ) × (298 K)

Hence K = 8.2 × 10−7

E�D.�(b) �e reduction half-reactions for the given cell are

R: 2Bi3+ (aq) + 6e− → 2Bi(s)

L: Bi2 S3 (s) + 6e− → 2Bi(s) + 3S2− (aq)

�e cell reaction (R − L) is 2Bi3+ (aq) + 3S2− (aq) → Bi2 S3 (s). �e equilibrium

−
○
constant for this reaction is calculated using [�C.�–���], E cell = (RT�νF) ln K.
Rearranging for ln K and noting that ν = 6 gives

νF −○ 6 × (96485 C mol−1 )
ln K = E cell = ×(+0.96 V) = 2.24...×102
RT (8.3145 J K−1 mol−1 ) × (298.15 K)

where 1 V = 1 J C−1 is used. Hence K = 2.30... × 1097 .

�e dissolution reaction, Bi2 S3 (s) → 2Bi3+ (aq) + 3S2− (aq), corresponds to the
reverse of the cell reaction as written above. �e required equilibrium constant
is therefore the reciprocal of the one just calculated
1
K diss = = 4.3 × 10−98
2.30... × 1097

E�D.�(b) (i) �e reduction half-reactions for the speci�ed cell, and their electrode
potentials, are
R: O2 (g) + 4H+ (aq) + 4e− → 2H2 O(l) E −○ (R) = +1.23 V
L: 2RSSR(aq) + 4H+ (aq) + 4e− → 4RSH(aq) E −○ (L) = −0.34 V
where RSH represents cysteine, HSCH2 CH(NH2 )CO2 H, and RSSR rep-
resents cystine, the oxidised dimer [SCH2 CH(NH2 )CO2 H]2 .
�e overall cell reaction is

O2 (g) + 4RSH(aq) → 2H2 O(l) + 2RSSR(aq) ν=4

and the standard cell potential is

−
○
E cell = E −○ (R) − E −○ (L) = (+1.23 V) − (−0.34 V) = +1.57 V
 �e standard reaction Gibbs energy is related to the standard cell poten-
tial according to [�C.�–���], ∆ r G −○ = −νFE cell
−
○
. �erefore

∆ r G −○ = −νFE cell
−
○
= −4 × (96485 C mol−1 ) × (+1.57 V)
= −6.1 × 102 kJ mol−1

E�D.�(b) Under basic conditions, the required reduction half-equations and their stan-
dard electrode potentials are

R: 2Cl2 (g) + 4e− → 4Cl− (aq) E −○ (R) = +1.36 V

L: O2 (g) + 2H2 O(l) + 4e− → 4OH− (aq) E −○ (L) = +0.40 V

�e cell reaction (R−L) is 2Cl2 (g) + 4OH− (aq) → 4Cl− (aq) + O2 (g) + 2H2 O(l).
�e standard cell potential is
−
○
E cell = E −○ (R) − E −○ (L) = (+1.36 V) − (+0.40 V) = +0.96 V
−
○
�e positive value of E cell indicates that yes , chlorine has a thermodynamic
tendency to oxidize water to oxygen gas under standard conditions in basic
solution.

P�D.� (a) �e reduction half-reactions for the reduction of CO2 and CO to methane
are
R: CO(g) + 6H+ (aq) + 6e− → CH4 (g) + H2 O(l)
L: CO2 (g) + 8H+ (aq) + 8e− → CH4 (g) + 2H2 O(l)
�e right-hand reduction half-reaction is multiplied by four and the le�-
half reduction half-reaction by three so that both involve the same num-
ber of electrons, ν = 24. Subtraction of the le�-hand half-reaction from
the right-hand half-reaction gives the overall cell reaction as

4CO(g) + 2H2 O(l) → CH4 (g) + 3CO2 (g) ν = 24

�e standard reaction Gibbs energy of this reaction is calculated using

standard formation Gibbs energies from the Resource section.

∆ r G −○ = 3∆ f G −○ (CO2 , g) + ∆ f G −○ (CH4 , g)
− 4∆ f G −○ (CO, g) − 2∆ f G −○ (H2 O, l)
= 3 × (−394.36 kJ mol−1 ) + (−50.72 kJ mol−1 )
− 4 × (−137.17 kJ mol−1 ) − 2 × (−237.13 kJ mol−1 )
= −210.86 kJ mol−1

�e negative value of ∆ r G −○ indicates that the cell reaction as written is

spontaneous under standard conditions. �is means that, in the sponta-
neous cell reaction, reduction is taking place at the right-hand electrode.
�erefore the right-hand electrode is the cathode.
 (b) �e cell potential under standard conditions, corresponding to all gases
being at � bar pressure assuming perfect gas behaviour, is calculated from
∆ r G −○ using [�C.�–���]. Note from above that ν = 24.

∆ r G −○ −210.86 × 103 J mol−1

−
○
E cell =− =− = +0.09106 V
νF 24 × (96485 C mol−1 )

P�D.� �e reduction half-equations for the cell are

R: Hg2 Cl2 (s) + 2e− → 2Hg(l) + 2Cl− (aq)

L: 2H+ (aq) + 2e− → H2 (g)

�e overall cell reaction is

Hg2 Cl2 (s) + H2 (g) → 2Hg(l) + 2H+ (aq) + 2Cl− (aq) ν=2

Noting that pure solids and liquids have a J = 1, the Nernst equation is

RT a2 + a2 −
E cell = E cell
−
○
− ln � H Cl �
2F a H2

Because the hydrogen gas is at standard pressure, a H2 = 1. Hence

RT RT
E cell = E cell
−
○
− ln �a H
2
+ a Cl− � = E cell −
2 −
○
ln (a H+ a Cl− )
2F F
�e activities in this expression are written in terms of the molality of HCl(aq),
b, through a H+ = γ± b�b −○ and a Cl− = γ± b�b−○ as explained in Section �D.�(a)
on page ���. �is gives

RT γ2 b2 2RT b 2RT
E cell = E cell
−
○
− ln � ± 2 � = E cell
−
○
− ln � −○ � − ln γ±
F b −○ F b F

From the Debye–Hückel law the mean activity coe�cient is given by [�F.��–
���], log γ± = −A�z+ z− �I 1�2 where A is a dimensionless constant, z+ and z−
are the charges on the H+ and Cl− ions and I is the ionic strength. For an
electrolyte containing only two ions, the ionic strength is given by [�F.��–���],
I = 12 (b+ z+2 + b− z−2 )�b −○ . In the case of HCl, z+ = +1, z− = −1, and b+ = b− = b.
�erefore
I = 12 [b × (+1)2 + b × (−1)2 ]�b−○ = b�b −○
and hence

log γ± = −A�z+ z− �I 1�2 = −A × �(1) × (−1)� × (b�b −○ )1�2 = −A(b�b −○ )1�2

Noting from inside the front cover that ln x = ln 10 × log x, the expression for
E cell then becomes

2RT b 2RT b 1�2

E cell = E cell
−
○
− ln � −○ � − × ln 10 × −A � −○ �
F b F b
Rearranging gives

��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � intercept ��� � � � � � � � � � � � �� � � � � � � � � � � � � ��� � � � � � ���1�2

� � � � ��
y slope x

2RT b � 2ART ln 10 b
E cell + ln � −○ � = E cell −
○
+ × � −○ �
F b F b
�is expression implies that a plot of y against (b�b −○ )1�2 , where y is given by
the expression E cell + (2RT�F) ln(b�b−○ ), should be a straight line of intercept
−
○
E cell and slope 2ART ln 10�F. Recall that b −○ = 1 mol kg−1 , so in calculating
b�b , b must be converted to mol kg−1 . �e plot is shown in Fig. �.�.
−
○

b�mmol kg−1 E�V (b�b −○ )1�2 y�V

1.607 7 0.600 80 0.040 10 0.270 24
3.076 9 0.568 25 0.055 47 0.271 04
5.040 3 0.543 66 0.071 00 0.271 82
7.693 8 0.522 67 0.087 71 0.272 56
10.947 0.505 32 0.104 63 0.273 33

0.274

0.272
y�V

0.270

0.02 0.04 0.06 0.08 0.10 0.12

(b�b ) −
○ 1�2

�e data fall on a reasonable straight line, the equation of which is

y�V = 0.047678 × (b�b−○ )1�2 + 0.26838

−
○
E cell is determined from the intercept as 0.26838 V
�e mean activity coe�cients are calculated using the equation
2RT b 2RT
E cell = E cell
−
○
− ln � −○ � − ln γ±
F b F
which was found above. Rearranging for ln γ± gives
F b
ln γ± = �E −○ − E cell � − ln � −○ �
2RT cell b
 −
○
Using the value of E cell obtained above with the values of E cell and b from the
data in the question yields the following values for ln γ± and γ± :

b�mmol kg−1 E�V ln γ± γ±

1.607 7 0.600 80 −0.036 294 0.964 4
3.076 9 0.568 25 −0.051 965 0.949 4
5.040 3 0.543 66 −0.066 969 0.935 2
7.693 8 0.522 67 −0.081 438 0.921 8
10.947 0.505 32 −0.096 482 0.908 0

P�D.� �e standard potential of the AgCl/Ag,Cl− couple corresponds to the stan-

dard potential of a cell in which the right-hand electrode is the AgCl/Ag,Cl−
electrode and the le�-hand electrode is the standard hydrogen electrode. �e
reduction half-reactions for this cell are

R: AgCl(s) + e− → Ag(s) + Cl− (aq)

L: H+ (aq) + e− → 12 H2 (g)

�e overall cell reaction is

AgCl(s) + 12 H2 (g) → Ag(s) + Cl− (aq) + H+ (aq) ν=1

Because E −○ (L) = 0 by de�nition, E cell

−
○
= E −○ (R) = E −○ (AgCl�Ag, Cl− ) for this
−
○
cell. �e given expression for the electrode potential is therefore equal to E cell .
�e �rst step in the calculation is to obtain values of ∆ r G −○ , ∆ r S −○ , and ∆ r H −○ for
−
○
the cell using the given expression for E cell . �ese are then used together with
values taken from the Resource section of ∆ f G −○ , ∆ f H −○ , and S m −○
for the other
species in the cell reaction to obtain the corresponding values for Cl− .
�e standard reaction Gibbs energy is related to the standard cell potential
according to [�C.�–���], ∆ r G −○ = −νFE cell
−
○
. �e given expression is for the
dimensionless quantity E cell �V, so to obtain E cell
−○ −
○
from this it is necessary to
multiply the expression by V

∆ r G −○ = −νF × [E cell
−
○
�V] × V
= −νF × �0.23659 − 4.8564 × 10−4 (θ�○ C) − 3.4205 × 10−6 (θ�○ C)2

+ 5.869 × 10−9 (θ�○ C)3 � × V

�e values are required at 298 K, which corresponds to θ = (298 − 273.15) =

24.85 ○ C. �e value of ∆ r G −○ is therefore:

∆ r G −○ = −1 × (96485 C mol−1 ) × �0.23659 − 4.8564 × 10−4 × (24.85)

− 3.4205 × 10−6 × (24.85)2 + 5.869 × 10−9 × (24.85)3 � × V

= −21.4... kJ mol−1
�e relationship between ∆ r S −○ and E cell
−
○ −
○
is given by [�C.�–���], dE cell �dT =
∆ r S �νF. �e expression for E cell �V is di�erentiated to give
−
○ −
○

−
○
d(E cell �V)
= −4.8564 × 10−4 − 6.841 × 10−6 (θ�○ C) + 1.7607 × 10−8 (θ�○ C)2
d(θ�○ C)
−
○
To relate this to dE cell �dT, note that because θ�○ C = T�K − 273.15, d(θ�○ C) =
d(T�K). Noting further that d(T�K) = dT�K and that d(E cell −○
�V) = dE cell
−
○
�V
gives
−
○
d(E cell �V) dE cell
−
○
�V K dE cell
−
○ −
○
dE cell −
○
d(E cell �V) V
= = hence = ×
d(θ�○ C) dT�K V dT dT ○
d(θ� C) K
−
○
Substituting this into [�C.�–���], dE cell �dT = ∆ r S −○ �νF, and rearranging for
−
○
∆ r S gives
−
○
d(E cell �V) V
∆ r S −○ = νF × ○
×
d(θ� C) K
V
= νF ×� − 4.8564 × 10−4 − 6.841 × 10−6 (θ�○ C) + 1.7607 × 10−8 (θ�○ C)2 �×
K
= 1 × (96485 C mol−1 ) × � − 4.8564 × 10−4 − 6.841 × 10−6 × (24.85)

+ 1.7607 × 10−8 × (24.85)2 � × (V�K) = −62.2... J K−1 mol−1

Finally ∆ r H −○ is calculated from [�D.�–���], ∆ r G −○ = ∆ r H −○ − T∆ r S −○

∆ r H −○ = ∆ r G −○ + T∆ r S −○
= (−21.4... × 103 J mol−1 ) + (298 K) × (−62.2... J K−1 mol−1 )
= −40.0... kJ mol−1

�e overall cell reaction is

AgCl(s) + 12 H2 (g) → Ag(s) + Cl− (aq) + H+ (aq)

�ese values of ∆ r G −○ , ∆ r S −○ , and ∆ r H −○ are used with data from the Resource
section to calculate ∆ f G −○ (Cl− ), ∆ f H −○ (Cl− ), and S m
−
○
(Cl− )
Noting from Section �D.�(a) on page ��� that ∆ f G −○ (H+ , aq) = 0, and also that
elements in their reference states have ∆ f G −○ = 0, the standard reaction Gibbs
energy for the reaction is given by

∆ r G −○ = ∆ f G −○ (Cl− , aq) − ∆ f G −○ (AgCl, s)

Hence ∆ f G −○ (Cl− , aq) = ∆ r G −○ + ∆ f G −○ (AgCl, s)

= (−21.4... kJ mol−1 ) + (−109.79 kJ mol−1 ) = −131.3 kJ mol−1

Similarly, noting from Section �C.� on page �� that ∆ f H −○ (H+ , aq) = 0, and
that elements in their reference states have ∆ f H −○ = 0, the standard reaction
enthalpy is
∆ r H −○ = ∆ f H −○ (Cl− , aq) − ∆ f H −○ (AgCl, s)
 Hence ∆ f H −○ (Cl− , aq) = ∆ r H −○ + ∆ f H −○ (AgCl, s)
= (−40.0... kJ mol−1 ) + (−127.07 kJ mol−1 ) = −167.1 kJ mol−1
−
○
Finally, noting from Section �C.�(b) on page �� that S m (H+ , aq) = 0, the
standard reaction entropy is
∆ r S −○ = S m
−
○
(Ag, s) + S m
−
○
(Cl− , aq) − S m
−
○
(AgCl, s) − 12 S m
−
○
(H2 , g)
Hence
−
○
Sm (Cl− , aq) = ∆ r S −○ + S m
−
○
(AgCl, s) + 12 S m
−
○
(H2 , g) − S m
−
○
(Ag, s)
= (−62.2... J K−1 mol−1 ) + (96.2 J K−1 mol−1 )
+ 12 × (130.684 J K−1 mol−1 ) − (42.55 J K−1 mol−1 )
= 56.8 J K−1 mol−1

I�.� (a) �e ionic strength is given by [�F.��–���], I = 12 �b+ z+2 + b− z−2 � �b−○ , where
z+ and z− are the charges on the ions. For the CuSO4 compartment,
z+ = 2, z− = −2, and b+ = b− = b CuSO4 :
I = 12 �b+ z+2 + b− z−2 � �b−○ = 12 �b CuSO4 × (+2)2 + b CuSO4 × (−2)2 � �b −○
1.00 × 10−3 mol kg−1
= 4(b CuSO4 �b−○ ) = 4 × = 4.00 × 10−3
1 mol kg−1
Because the charges are the same for ZnSO� it follows that I = 4(b ZnSO4 �b−○ )
= 1.20 × 10−2 .
(b) According to the Debye–Hückel limiting law (Section �F.�(b) on page
���), the mean activity coe�cient is given by [�F.��–���], log γ± = −A�z+ z− �I 1�2 ,
where A = 0.509 for aqueous solutions at �� ○ C. For the CuSO4 solution
log γ±,CuSO4 = −(0.509) × �(2) × (−2)� × (4.00 × 10−3 )1�2 = −0.128...
Hence γ±,CuSO4 = 10−0.128 ... = 0.743... = 0.743 . For the ZnSO4 solution

log γ±,ZnSO4 = −(0.509) × �(2) × (−2)� × (1.20 × 10−2 )1�2 = −0.223...

Hence γ±,ZnSO4 = 10−0.223 ... = 0.598... = 0.598 .
(c) Noting that pure solids have a J = 1 and writing the activities of ions in
solution as a = γ± (b�b−○ ), the reaction quotient for the reaction
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
is given by
a Zn2+ γ±,ZnSO4 (b Zn2+ �b −○ ) γ±,ZnSO4 b Zn2+
Q= = = ×
a Cu2+ γ±,CuSO4 (b Cu2+ �b −○ ) γ±,CuSO4 b Cu2+
0.598... 3.00 × 10−3 mol kg−1
= × = 2.41... = �.��
0.743... 1.00 × 10−3 mol kg−1
 (d) �e reaction is thought of as being composed of the reduction half-reactions
R: Cu2+ (aq) + 2e− → Cu(s)
L: Zn2+ (aq) + 2e− → Zn(s)
which show that ν = 2 for this reaction. �e standard cell potential is
calculated from ∆ r G −○ using [�C.�–���], E cell
−
○
= −∆ r G −○ �νF:

∆ r G −○ −212.7 × 103 J mol−1

−
○
E cell =− =− = +1.102 V
νF 2 × (96485 C mol−1 )

Note that 1 J C−1 = 1 V.

(e) �e cell potential is given by the Nernst equation [�C.�–���]:
RT
E cell = E cell
−
○
− ln Q
νF
(8.3145 J K−1 mol−1 ) × ([25 + 273.15] K)
= (+1.102 V) − × ln(2.41...)
2 × (96485 C mol−1 )
= +1.09 V

I�.� �e reaction for the autoprotolysis of liquid water is

H2 O(l) → H+ (aq) + OH− (aq)

�is reaction is split into the reduction half-reactions

R: H2 O(l) + e− → 12 H2 (g) + OH− (aq)

L: H+ (aq) + e− → 12 H2 (g)

Because the standard electrode potential for the le�-hand half-reaction is zero
by de�nition, the standard cell potential for this cell is equal to the standard
electrode potential of the H2 O/H2 ,OH− electrode. �e equilibrium constant
−
○
K w for the cell reaction is then given by [�C.�–���], E cell = (RT�νF) ln K.
Rearranging for ln K and using ν = 1, K = K w , and E cell = E −○ (H2 O�H2 , OH− )
−
○

gives
F
ln K w = × E −○ (H2 O�H2 , OH− )
RT
Noting from inside the front cover that ln x = ln 10 × log x, and also that pK w =
− log K w allows the above equation to be rewritten as
ln K w F
pK w = − log K w = − =− × E −○ (H2 O�H2 , OH− )
ln 10 RT ln 10
�e task is therefore to �nd E −○ (H2 O�H2 , OH− ) from the given data. To do
this, the speci�ed cell is written in terms of its reduction half-reactions

R: AgCl(s) + e− → Ag(s) + Cl− (aq)

L: H2 O(l) + e− → 12 H2 (g) + OH− (aq)
�e cell reaction, which has ν = 1, is

AgCl(s) + 12 H2 (g) + OH− (aq) → Ag(s) + Cl− (aq)

Noting that a J = 1 for pure solids, and that in this cell a H2 = 1 because the
hydrogen is at standard pressure, the Nernst equation for the cell is

RT RT a Cl−
E cell = E cell
−
○
− ln Q = E cell
−
○
− ln � �
νF F a OH−

Writing the activities as a = γ± (b�b −○ ), the Nernst equation becomes

RT γ± (b Cl− �b −○ ) RT b Cl−
E cell = E cell
−
○
− ln � � = E cell
−
○
− ln � �
F γ± (b OH− �b )−○ F b OH−

�e standard cell potential is split into contributions from the two electrodes
−
○
using [�D.�–���], E cell = E −○ (R) − E −○ (L)

RT b Cl−
E cell = E −○ (AgCl�Ag, Cl− ) − E −○ (H2 O�H2 , OH− ) − ln � �
F b OH−
Hence
RT b Cl−
E −○ (H2 O�H2 , OH− ) = E −○ (AgCl�Ag, Cl− ) − E cell − ln � �
F b OH−

�is equation is used with b Cl− = 0.01125 mol kg−1 , b OH− = 0.0100 mol kg−1 ,
and the values of E cell and E −○ (AgCl�Ag, Cl− ) to calculate E −○ (H2 O�H2 , OH− )
at each temperature. �e relation derived earlier

pK w = −(F�RT ln 10)E −○ (H2 O�H2 , OH− )

is then used to calculate pK w . �e results are given in the following table.

θ�○ C T�K E cell �V E −○ (AgCl�Ag, Cl− )�V E −○ (H2 O�H2 , OH− )�V pK w
20.0 293.15 1.047 74 0.225 02 −0.825 70 14.20
25.0 298.15 1.048 64 0.222 30 −0.829 37 14.02
30.0 303.15 1.049 42 0.219 59 −0.832 91 13.85

To �nd ∆ r S −○ for the autoprotolysis, the relationship between E cell

−○
and temper-
ature [�C.�–���], dE cell �dT = ∆ r S �νF is used. If ∆ r S is constant over the
−
○ −○ −
○
−
○
temperature range this equation implies that a plot of E cell against T should
be a straight line of slope ∆ r S −○ �νF. In this case E cell
−○
for the autoprotolysis
reaction is equal to E −○ (H2 O�H2 , OH− ) as explained earlier. �e plot is shown
in Fig. �.�.
�e data fall on a good straight line, the equation of which is

E −○ (H2 O�H2 , OH− )�V = −7.229 × 10−4 × (T�K) − 0.6137

 −0.825

E −○ (H2 O�H2 , OH− )�V

−0.830

−0.835
292 294 296 298 300 302 304
T�K

∆ r S −○ �νF is determined from the slope

∆ r S −○ = νF × slope × V K−1
= 1 × (96485 C mol−1 ) × (−7.229 × 10−4 V K−1 )
= −68.5... J K−1 mol−1 = −68.6 J K−1 mol−1
�e standard enthalpy change for the autoprotolysis is calculated from [�D.�–
���], ∆ r G −○ = ∆ r H −○ − T∆ r S −○ , with ∆ r G −○ being given by [�C.�–���], ∆ r G −○ =
−νFE cell
−
○ −
○
. In this case E cell = E −○ (H2 O�H2 , OH− ) and ν = 1. Using the value
○
for 25.0 C gives
∆ r H −○ = ∆ r G −○ + T∆ r S −○ = −νFE −○ (H2 O�H2 , OH− ) + T∆ r S −○
= −1 × (96485 C mol−1 ) × (−0.829...V) + (298.15 K) × (−68.5... J K−1 mol−1 )
= +59.6 kJ mol−1

I�.� �e reduction half-reactions, and the overall cell reaction, for the speci�ed cell
(R − L) are:

R: AgCl(s) + e− → Ag(s) + Cl− (aq)

L: H+ (aq) + e− → 12 H2 (g)
R − L: AgCl(s) + 12 H2 (g) → Ag(s) + Cl− (aq) + H+ (aq) ν=1

Noting that a J = 1 for pure solids and that in this cell a H2 = 1 because the
hydrogen is at standard pressure, the Nernst equation is
RT
E cell = E cell −
ln (a Cl− a H+ )
−
○
F
In addition, the base B and its conjugate acid are in equilibrium:
a B a H+
BH+ (aq) � B(aq) + H+ (aq) Ka =
a BH+
�e expression for K a is rearranged to give a H+ = K a a BH+ �a B and this is sub-
stituted into the Nernst equation to give
RT RT a Cl− a BH+ K a
E cell = E cell
−
○
− ln (a Cl− a H+ ) = E cell
−
○
− ln � �
F F aB
Replacing activities by a J = γ J (b J �b −○ ) [�F.��–���] gives

RT (γ Cl− b Cl− �b −○ )(γ BH+ b BH+ �b −○ )K a

E cell = E cell
−
○
− ln � �
F (γ B b B �b −○ )

In this case b Cl− = b BH+ = b B so the Nernst equation simpli�es to

RT γ Cl− γ BH+ bK a RT γ 2 bK a
E cell = E cell
−
○
− ln � × −○ � = E cell
−
○
− ln � ± −○ �
F γB b F b

where the mean activity coe�cient of the BH+ and Cl – ions is given by [�F.��–
���], γ± = (γ Cl− γ BH+ )1�2 and the neutral base B is assumed to be an ideal solute
so that γ B = 1. Noting from inside the front cover that ln x = ln 10 log x, the
Nernst equation becomes

RT ln 10 γ 2 bK a
E cell = E cell
−
○
− log � ± −○ �
F b
RT ln 10 b
= E cell
−
○
− �2 log γ± + log � −○ � − pK a �
F b
where pK a = − log K a has been used. Next the Davies equation [�F.��b–���],
log γ± = −A�z+ z− �I 1�2 �(1+BI 1�2 )+CI, is used to substitute for log γ± . �e ionic
strength I is given by [�F.��–���], I = 12 ∑ i z 2i (b i �b −○ ), where z i is the charge
on ion species i and the sum extends over all the ions present in the solution.
In this case, b BH+ = b Cl− = b, and b H+ is neglected because it will be much
smaller on account of the equilibrium involving the base B. �erefore the ionic
strength is

I = 12 �z BH
2
+ b + z Cl− b� �b
2 −
○
= 12 �12 × b + (−1)2 × b� �b −○ = b�b−○

and therefore
A�z BH+ × z Cl− �I 1�2 A(b�b−○ )1�2 b
log γ± = − + CI = − + C � −○ �
1 + BI 1�2 1 + B(b�b −○ )1�2 b
Substitution of this expression into the Nernst equation derived above gives

RT ln 10 A(b�b −○ )1�2 b b
E cell = E cell
−
○
− �2 �− + C � −○ �� + log � −○ � − pK a �
F 1 + B(b�b −○ )1�2 b b

which rearranges to

F(E cell − E cell −○

) 2A(b�b −○ )1�2 b b
= − 2C � −○ � − log � −○ � + pK a
RT ln 10 1 + B(b�b −○ )1�2 b b
��� � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � �
y
 De�ning (b�b −○ )1�2 as x and the le�-hand side as y, and introducing A = 0.5091
gives
1.0182x
y= − 2Cx 2 − 2 log x + pK a
1 + Bx
which is �tted to the data using mathematical so�ware to give the following val-
ues for the parameters: B = 2.54 , C = −0.204 , and pK a = 6.74 . �ese values
have been used to draw the line on the graph shown in Fig. �.�.

b�mmol kg−1 E cell �V (b�b−○ )1�2 y

0.01 0.744 52 0.100 8.823 73
0.02 0.728 53 0.141 8.553 44
0.03 0.719 28 0.173 8.397 08
0.04 0.713 14 0.200 8.293 30
0.05 0.708 09 0.224 8.207 94
0.06 0.703 80 0.245 8.135 42
0.07 0.700 59 0.265 8.081 16
0.08 0.697 90 0.283 8.035 69
0.09 0.695 71 0.300 7.998 67
0.10 0.693 38 0.316 7.959 29

8.8
)�RT ln 10

8.6

8.4
F(E cell − E cell
−
○

8.2

8.0
0.05 0.10 0.15 0.20 0.25 0.30 0.35
(b�b )
−
○ 1�2

I�.� From Impact � the reaction for the hydrolysis of ATP to ADP and inorganic
phosphate P−i is

ATP(aq) + H2 O(l) → ADP(aq) + P−i (aq) + H3 O+ (aq)

Under biological standard conditions, that is, pH = 7, the standard reaction

Gibbs energy at �� ○ C is given in Impact � as ∆ r G ⊕ = −31 kJ mol−1 .
In an environment in which pH = 7.0 and the ATP, ADP and P−i concentrations
are all �.� mmol dm−3 , the reaction Gibbs energy is given by [�A.��–���],

∆ r G = ∆ r G ⊕ + RT ln Q ⊕

where Q ⊕ is the reaction quotient calculated relative to the biological standard

state. Because pH is de�ned by pH = − log a H3 O+ , pH � corresponds to a H3 O+ =
10−7 so that when computing Q ⊕ the activity of H� O+ is measured relative to
an activity of 10−7 rather than an activity of � as is usually the case. In practice
this means that a H3 O+ is replaced by (a H3 O+ �10−7 ) in the expression for Q ⊕ .
For the ATP hydrolysis reaction this gives

a ADP × a P−i × (a H3 O+ �10−7 )

∆ r G = ∆ r G ⊕ + RT ln � �
a ATP × a H2 O

Water is a pure liquid so a H2 O = 1, and for the environment speci�ed in the

question, pH = 7 so a H3 O+ = 10−7 . For the other species activities are approxi-
mated by concentrations according to a J = [J]�c −○ where c −○ = 1 mol dm−3 .

([ADP]�c −○ )([P−i ]�c −○ )(10−7 �10−7 )

∆ r G = ∆ r G ⊕ + RT ln � �
([ATP]�c −○ )
[ADP][P−i ]
= ∆ r G ⊕ + RT ln � �
[ATP]c −○
= (−31 × 103 J mol−1 ) + (8.3145 J K−1 mol−1 ) × ([37 + 273.15] K)
(1.0 × 10−3 mol dm−3 ) × (1.0 × 10−3 mol dm−3 )
× ln � �
(1.0 × 10−3 mol dm−3 ) × (1 mol dm−3 )
= −49 kJ mol−1

�is is to be compared with the value under standard biological conditions,

which is −31 kJ mol−1 , and also with the value under the usual standard con-
ditions. �e di�erence between ∆ r G −○ and ∆ r G ⊕ is that the former has a H+ = 1
and the latter has a H+ = 10−7 . Given that

a ADP a Pi a H3 O+
∆ r G = ∆ r G −○ + RT ln � �
a ATP a H2 O

setting all the activities to � except for that for H� O+ which is set to 10−7 gives
∆r G ⊕
∆ r G ⊕ = ∆ r G −○ + RT ln 10−7
hence

∆ r G −○ = ∆ r G ⊕ − RT ln 10−7
= (−31 × 103 J mol−1 )−(8.3145 J K−1 mol−1 )×([37 + 273.15] K)×ln 10−7
= +11 kJ mol−1
I�.�� A bacterium could potentially oxidise ethanol to ethanal, ethanoic acid, or
CO2 (g), while nitrate, NO−3 (aq), could potentially be reduced to a number
of possible species including NO2 (g), NO−2 (aq), NO(g), N2 (g), or NH+4 (aq).
Assuming complete oxidation of ethanol to CO2 and complete reduction of
NO−3 to NH+4 the reduction half-reactions are

R: NO−3 (aq) + 10H+ + 8e− → NH+4 (aq) + 3H2 O(l)

L: 2CO2 (g) + 12H+ + 12e− → CH3 CH2 OH(aq) + 3H2 O(l)

�e right-hand half reaction is multiplied by three and the le�-hand half re-
action by two in order that both involve the same number of electrons. �e
overall reaction is

2CH3 CH2 OH(aq) + 3NO−3 (aq) + 6H+ (aq) → 4CO2 (g) + 3NH+4 (aq) + 3H2 O(l)

�e data in the Resource section is used to calculate ∆ r G −○ for this reaction:

∆ r G −○ = 4∆ f G −○ (CO2 , g) + 3∆ f G −○ (NH+4 , aq) + 3∆ f G −○ (H2 O, l)

− 2∆ f G −○ (CH3 CH2 OH, aq) − 3∆ f G −○ (NO−3 , aq) − 6∆ f G −○ (H+ , aq)
= 4 × (−394.36 J mol−1 ) + 3 × (−79.31 J mol−1 ) + 3 × (−237.13 J mol−1 )
− 2 × (−174.78 J mol−1 ) − 3 × (−108.74 J mol−1 ) = −1851 kJ mol−1

�e negative value of ∆ r G −○ indicates that the reaction is exergonic, so yes , a

bacterium could evolve to use this reaction to drive endergonic processes such
as the formation of ATP for use in cellular processes.
�e calculation is valid under standard conditions, which includes a H+ = 1
(pH = 0). As explained in Impact � on the website of this text, pH = 0 is
not normally appropriate for biological conditions so it is common to adopt
the biological standard state in which pH = 7.0. �e reaction Gibbs energy
for the oxidation of ethanol by nitrate under standard biological conditions is
calculated by using the appropriate value of a H+ in [�A.��–���], ∆ r G = ∆ r G −○ +
RT ln Q, leaving all other species with a J = 1. �e reaction consumes six
moles of H+ so under standard biological conditions Q = 1�a H 6
+ . Noting from

inside the front cover that ln x = ln 10 log x, and also that pH = − log a H+ , and
assuming T = 298 K, gives

1
∆ r G = ∆ r G −○ + RT ln Q = ∆ r G −○ + RT ln � 6
�
aH +

= ∆ r G −○ − 6RT ln 10 log(a H+ ) = ∆ r G −○ + 6RT ln 10×pH

= (−1.85... × 106 J mol−1 ) + 6×(8.3145 J K−1 mol−1 )×(298 K)×ln 10×7
= −1611 kJ mol−1

�us the reaction remains exergonic under standard biological conditions.

I�.�� (a) �e standard reaction enthalpy is found using the van ’t Ho� equation
[�B.�–���]:
d ln K ∆ r H −○ d ln K ∆ r H −○
= which can also be written − =
dT RT 2 d(1�T) R
�e second form implies that a graph of − ln K against 1�T should be a
straight line of slope ∆ r H −○ �R, from which ∆ r H −○ can be determined. �e
value of ∆ r S −○ is found by combining ∆ r G −○ = ∆ r H −○ − T∆ r S −○ [�D.�–���]
and ∆ r G −○ = −RT ln K [�A.��–���]. Equating these expressions for ∆ r G −○
gives
∆ r H −○ 1 ∆ r S −○
−RT ln K = ∆ r H −○ − T∆ r S −○ hence − ln K = −
R T R
Assuming that ∆ r H −○ and ∆ r S −○ do not very signi�cantly over the temper-
ature range of interest this equation implies that a plot of − ln K against
1�T should be a straight line of intercept −∆ r S −○ �R, from which ∆ r S −○ can
be determined; such a plot is shown in Fig. �.�. �e plot will have a slope
of ∆ r H −○ �R, as already deduced above.

T�K K 1�(T�K) − ln K
233 4.13 × 108 0.004 29 −19.8
248 5.00 × 107 0.004 03 −17.7
258 1.45 × 107 0.003 88 −16.5
268 5.37 × 106 0.003 73 −15.5
273 3.20 × 106 0.003 66 −15.0
280 9.62 × 105 0.003 57 −13.8
288 4.28 × 105 0.003 47 −13.0
295 1.67 × 105 0.003 39 −12.0
303 6.02 × 104 0.003 30 −11.0
�e data fall on a reasonable straight line, the equation of which is
− ln K = −8 787 × 1�(T�K) + 17.62
∆ r H −○ �R is determined from the slope
∆ r H −○ = R × (slope × K) = (8.3145 J K−1 mol−1 ) × (−8787 K)
= −73.0... kJ mol−1 = −73.1 kJ mol−1
−∆ r S −○ �R is determined from the intercept
∆ r S −○ = −R × intercept = −(8.3145 J K−1 mol−1 ) × (+17.62)
= −1.46... × 102 J K−1 mol−1 = −147 J K−1 mol−1

(b) �e standard reaction enthalpy for the reaction 2ClO(g) → (ClO)2 (g) is
expressed in terms of standard enthalpies of formation
∆ r H −○ = ∆ f H −○ [(ClO)2 , g] − 2∆ f H −○ (ClO, g)
 −10

−15

− ln K

−20
0.0032 0.0036 0.0040 0.0044
1�(T�K)

Hence

∆ f H −○ [(ClO)2 , g] = ∆ r H −○ + 2∆ f H −○ (ClO, g)
= (−73.0... kJ mol−1 ) + 2 × (+101.8 kJ mol−1 )
= +131 kJ mol−1

Similarly
∆ r S −○ = S m
−
○
[(ClO)2 , g] − 2S m
−
○
(ClO, g)
Hence
−
○
Sm [(ClO)2 , g] = ∆ r S −○ + 2S m
−
○
(ClO, g)
= (−1.46... × 102 J K−1 mol−1 ) + 2 × (226.6 J K−1 mol−1 )
= 307 J K−1 mol−1
D�A.� �e ultimately unsuccessful classical approach to the description of black-body
radiation involved assuming that the radiation resulted from oscillating electric
charges in the walls of the body, and that each oscillator has the same average
energy as predicted by the equipartition principle. �is view results in the
ultra-violet catastrophe, in which the radiation increases without limit as the
wavelength becomes shorter.
Planck assumed two things: �rst, that the oscillators could only have energies
given by E = nhν, where ν is the frequency and n is 0, 1, 2, . . .; second, that the
probability of an individual oscillator having a particular energy is described
by the Boltzmann distribution. As the frequency of the oscillator or the value
of n increases, so does its energy and the Boltzmann distribution predicts that
such a state is less likely. In addition, the highest frequency oscillations may
not be excited at all, that is have n = 0, on the grounds that the resulting state
has too high an energy to be populated. Planck’s theory therefore avoids the
ultraviolet catastrophe by having no excitation of highest frequency oscillators.

D�A.� By wave-particle duality it is meant that in some experiments an entity be-

haves as a wave while in other experiments the same entity behaves as a par-
ticle. Electromagnetic radiation behaves as a wave in di�raction experiments
but it behaves as particulate photons in absorption and emission spectroscopy.
Electrons behave as waves in di�raction experiments, but as particles in the
photoelectric e�ect.
�e development of quantum theory is much concerned with the need to em-
brace this wave-particle duality and, as is explained in the following Topics,
this is exempli�ed by the introduction of the wavefunction to describe the
properties of a particles and the notion of ‘complementary variables’ such as
position and momentum.

E�A.�(b) Wien’s law [�A.�–���], λ max T = 2.9 × 10−3 m K, is rearranged to give the
wavelength at which intensity is maximised

λ max = (2.9 × 10−3 m K)�T = (2.9 × 10−3 m K)�(2.7 K) = 1.1 × 10−3 m

E�A.�(b) Assuming that the object is a black body is equivalent to assuming that Wien’s
law [�A.�–���], λ max T = 2.9 × 10−3 m K, holds. Using λν = c (where c is the
speed of light in a vacuum), Wien’s law is expressed in terms of the frequency
of maximum intensity (ν max )

Tc�ν̃ max = 2.9 × 10−3 m K

�is is rearranged to give the temperature

T =(2.9 × 10−3 m K) × ν max �c

(282 × 109 Hz)
= (2.9 × 10−3 m K) × = �.� K
(2.9979 × 108 m s−1 )

E�A.�(b) Molar heat capacities of monatomic non-metallic solids obey the Einstein re-
lation [�A.�a–���]

θ E 2 eθ E �2T
2
C V ,m (T) = 3R f E (T), f E (T) = � � � θ �T �
T e E −1

where the solid is at temperature T and is characterized by an Einstein temper-

ature θ E . �us, for a solid at 500 K with an Einstein temperature of 300 K

300 K 2 e(300 K)�2(500 K)

2
f E (500 K) = � � � (300 K)�(500 K) � = 0.970...
500 K e −1

Hence, C V ,m (500 K) = (0.97) × 3R

E�A.�(b) �e energy of the quantum is given by the Bohr frequency condition [�A.�–
���], ∆E = hν, and the frequency is ν = 1�T. �e energy per mole is ∆E m =
N A ∆E.
(i) For T = 2.50 fs

∆E = (6.6261 × 10−34 J s)�(2.50 × 10−15 s) = 2.65 × 10−19 J

∆E m = (2.65... × 10−19 J) × (6.0221 × 1023 mol−1 ) = ��� kJ mol−1

(ii) For T = 2.21 fs

∆E = (6.6261 × 10−34 J s)�(2.21 × 10−15 s) = 3.00 × 10−19 J

∆E m = (3.00... × 10−19 J) × (6.0221 × 1023 mol−1 ) = ��� kJ mol−1

(iii) For T = 1.0 ms

∆E = (6.6261 × 10−34 J s)�(1.0 × 10−3 s) = 6.6 × 10−31 J

∆E m = (6.6... × 10−31 J) × (6.0221 × 1023 mol−1 )
= 3.99 × 10−10 kJ mol−1
E�A.�(b) �e energy of a photon with wavelength λ is given by

E = hν = hc�λ = (6.6261 × 10−34 J s) × (2.9979 × 108 m s−1 )�λ

= (1.9825 × 10−25 J)�(λ�m)

�e energy per mole is given by

E m = N A E = (0.11939 J mol−1 )�(λ�m)

Hence, the following table is drawn up

λ E E m �kJ mol−1
(a) 200 nm 991 zJ 597
(b) 150 pm 1.32 pJ 7.96 × 105
(c) 1.00 cm 19.8 yJ 1.19 × 10−2

E�A.�(b) When a photon is absorbed by a free hydrogen atom, the law of conservation of
energy requires the kinetic energy acquired by the atom is E k , the energy of the
absorbed photon. Assuming relativistic corrections are negligible the kinetic
energy is E k = E photon = 12 m H υ 2 . �e atom is accelerated to the speed,

2E photon 1�2 2N A E photon 1�2

υ=� � =� �
mH MH
2 × (6.0221 × 1023 mol−1 ) × E photon
1�2

=� �
(1.0079 × 10−3 kg mol−1 )
= (3.45... × 1013 m s−1 ) × �E photon �J�
1�2

�e photon energies have been calculated in Exercise E�A.�(b), and thus the
following table can be drawn up

λ E υ�km s−1
(a) 200 nm 991 zJ 17.3
(b) 150 pm 1.32 pJ 631
(c) 1.00 cm 19.8 yJ 0.0773

E�A.�(b) �e total energy emitted from a laser at (constant) power P in a time interval ∆t
is P∆t. �e energy of a single photon of wavelength λ is E = hc�λ. Hence, the
total number of photons emitted in this time interval is the total energy emitted
divided by the energy per photon (assuming the light is monochromatic)
P∆t P∆tλ
N= =
E photon hc
�us, for a time interval of 1 s and a wavelength of 700 nm
 (i) P = 0.10 W

(0.10 W) × (1 s)(700 × 10−9 m)

N= = 3.52 × 1017
(6.6261 × 10−34 J s) × (2.9979 × 108 m s−1 )

(ii) P = 1.0 W

(1.0 W) × (1 s)(700 × 10−9 m)

N= = 3.52 × 1018
(6.6261 × 10−34 J s) × (2.9979 × 108 m s−1 )

E�A.�(b) As described in Section �A.� on page ���, photoejection can only occur if the
energy of the incident photon is greater than or equal to the work function of
the metal �. If this condition is ful�lled, the energy of the emitted photon is
given by [�A.��–���], E k = hν − Φ = hc�λ − Φ. To convert the work function to
Joules, multiply through by the elementary charge, as described in Section �A.�
on page ���,

Φ = 2.09 eV × e = 2.09 eV × 1.602 × 10−19 J eV−1 = 3.35... × 10−19 J

�
and since E k = 1�2m e υ 2 , υ = 2E k �m e

(i) For λ = 650 nm

hc (6.6261 × 10−34 J s) × (2.9979 × 108 m s−1 )

E photon = =
λ 650 × 10−9 m
= 3.06... × 10 J
−19

�is is less than the threshold energy, hence no electron ejection occurs.
(ii) For λ = 195 nm

(6.6261 × 10−34 J s) × (2.9979 × 108 m s−1 )

E photon = = 1.02... × 10−18 J
195 × 10−9 m
�is is greater than the the threshold frequency, and so photoejection can
occur, leading to a kinetic energy of

E k = hc�λ − Φ = 1.02... × 10−18 J − 3.35... × 10−19 J = 6.84 × 10−19 J

�
υ= 2 × (6.84 × 10−19 J)�(9.109 × 10−31 kg) = �.�� Mm s−1

E�A.�(b) If the power, P, is constant, the total energy emitted in time ∆t is P∆t. �e
energy of each emitted photon is E photon = hν = hc�λ. �e total number of
photons emitted in this time period is therefore the total energy emitted divided
by the energy per photon

N = P∆t�E photon = P∆tλ�hc

 �e conservation of linear momentum requires that the loss of a photon must
impart an equivalent momentum in the opposite direction to the spacecra�,
hence the total momentum p imparted to the spacecra� in time ∆t is

p = N p photon = N h�c = P∆tλ�hc × h�λ = P∆t�c

Because p = (mυ)spacecraft , the �nal speed of the spacecra� is

υ = P∆t�cm spacecraft
(1.5 × 103 W) × (10 y) × (3.1536 × 107 s y−1 )
= = ��� m s−1
(2.9979 × 108 m s−1 ) × (10 kg)
Noting that the number of seconds in one year is

365 × 24 × 60 × 60 = 3.1536 × 107

E�A.��(b) �e de Broglie relation is [�A.��–���], λ = h�p = h�(mυ). �erefore,

h 6.6261 × 10−34 J s
υ= = = 7.27 × 106 m s−1
m e λ (9.1094 × 10−31 kg) × (100 × 10−12 m)
�e kinetic energy acquired by an electron accelerated through a potential E is
eE: E k = 12 m e υ 2 = eE. Solving for the potential di�erence gives

m p υ 2 (1.6726 × 10−27 kg) × (3.93 × 103 m s−1 )2

E= = = 8.19 × 10−2 V
2e 2 × (1.6022 × 10−19 C)

E�A.��(b) �e de Broglie relation is [�A.��–���] λ = h�p = h�(mυ). Hence,

h 6.6261 × 10−34 J s
υ= = = 1.3 × 10−5 m s−1
m e λ (1.6726 × 10−27 kg) × (3 × 10−2 m)

E�A.��(b) According to the de Broglie relation, [�A.��–���] the momentum of a photon

is
h 6.6261 × 10−34 J s
p= = = 1.89 × 10−27 kg m s−1
λ 350 × 10−9 m
�e momentum of a particle is p = mυ, so the speed of a hydrogen molecule
that has the above momentum is
p p 1.89 × 10−27 kg m s−1
υ= = =
m H2 M H2 �N A (2.058 × 10−3 kg mol−1 )�(6.0221 × 1023 mol−1 )
= 0.566 m s−1

E�A.��(b) �e de Broglie wavelength is [�A.��–���], λ = h�p. �e kinetic energy of an

electron accelerated through a potential E is eE. �us, since E k = p2 �2m e ,
�
p = (2m e E k ) = (2m e eE) . Hence λ = h� (2m e eE.
1�2 1�2
 (i)
6.6261 × 10−34 J s
λ=
[2 × (9.1094 × 10−31 kg) × (1.6022 × 10−19 C) × (100 V)]
1�2

= ��� pm

(ii)
6.6261 × 10−34 J s
λ=
[2 × (9.1094 × 10−31 kg) × (1.6022 × 10−19 C) × (1.0 × 103 V)]
1�2

= �� pm

(iii)
6.6261 × 10−34 J s
λ=
[2 × (9.1094 × 10−31 kg) × (1.6022 × 10−19 C) × (100 × 105 V)]
1�2

= �.�� pm

P�A.� Converting the wavenumbers given to wavelengths, the boundary wavelengths

are

λ 1 = (1000 × 102 m−1 )−1 = 1.00 × 10−5 m

λ 2 = (1010 × 102 m−1 )−1 = 9.90... × 10−6 m

A cavity approximates an ideal black body, hence the Planck distribution [�A.�a–
���], applies
8πhc
ρ(λ, T) =
λ �e
5 hc�λk T − 1�

Because the wavelength range is small (99 nm), the energy density is approxi-
mated by
∆E(T) = ρ(λ, T)∆λ
Taking λ = 9.95... µm gives

hc (6.6261 × 10−34 J s) × (2.9979 × 108 m s−1 )

= = 1.44... × 103 K
λk (9.95... × 10−6 m) × (1.3806 × 10−23 J K−1 )
and
8πhc 8π × (6.6261 × 10−34 J s) × (2.9979 × 108 m s−1 )
= = 51.1... J m−4
λ5 (9.95... × 10−6 m)5

1
∆E(T) = (51.1... J m−4 ) × × (99... × 10−9 m)
e(1.44 ...×103 K)�T −1
5.06... × 10−6 J m−3
=
e(1.44 ...×103 K)�T − 1
 (a)
5.06... × 10−6 J m−3
∆E(298 K) = = 3.96 × 10−8 J m−3
e(1.44 ...×103 K)�(298 K) − 1
(b)
5.06... × 10−6 J m−3
∆E(4 K) = = 5.12 × 10−163 J m−3
−1
e(1.44 ...×103 K)�(4 K)

P�A.� �e Planck distribution is [�A.�a–���],

8πhc
ρ(λ, T) =
λ5 �e hc�λk T − 1�

�e value of λ at which ρ is at a maximum is found by solving dρ�dλ = 0.

dρ d
= 8πhc �λ−5 (e hc�λk T − 1)−1 �
dλ dλ
dλ−5 d(e hc�λk T − 1)−1
= 8πhc �(e hc�λk T − 1)−1 + λ−5 �
dλ dλ
hc
= 8πhc �−5λ−6 (e hc�λk T − 1)−1 + λ−5 (e hc�λk T − 1)−2 2 e hc�λk T �
λ kT
8πhc hce hc�λk T
= 7 hc�λk T �5λ + �
λ (e − 1) kT(e hc�λk T − 1)
�us, at λ = λ max ,
x max ex max − 5(ex max − 1) = 0
where x max = hc�λ max kT. �is equation is solved numerically by x max = 4.965,
giving
hc (6.6261 × 10−34 J s) × (2.9979 × 108 m s−1 )
λ max T = = = 2.9 × 10−3 K m
4.965k 4.965 × (1.3806 × 10−23 J K−1 )
as in the text.

P�A.� �e total energy absorbed by the atmosphere is 70% of the total energy incident
on the top of the atmosphere
343 W m2 × 0.7 = 240.1 W m2
At equilibrium, the total energy absorbed is equal to the total energy emitted,
which is determined by the Stefan–Boltzmann law
E abs = E em = 5.672 × 10−8 (T�K)4 W m2
�is is rearranged to

T = �240.1 K4 W m2 �5.672 × 10−8 W m2 � = ��� K

1�4

Wien’s law [�A.�–���], λ max T = 2.9 × 10−3 m K, is rearranged to give

λ max = (2.9 × 10−3 m K)�(255... K) = 1.14 × 10−5 m

P�A.� (a) As λ decreases, hc�λkT increases, and so e hc�λk T increases. �erefore, for
very short wavelengths, e hc�λk T is very large and 1 is negligible compared
to this. Hence,
8πhc 8πhc
lim ρ(λ, T) = = 5 e−hc�λk T
λ→0 λ 5 e hc�λk T λ

(b) Comparison with the empirical expression gives the constants as a = 8πhc ,
and b = −hc�λ .
(c) �e total energy density at temperature T is given by [�A.�–���],
∞ ∞ 8πhc −hc�λk T
E(T) = � ρ(λ, T) dλ = � e dλ
0 0 λ5
Let x = hc�λkT, or λ = hc�xkT. �en, dλ = −hc�x 2 kT dx
∞ 1 dx kT 4 ∞ 3 −x
E(T) = 8πhc � e−x 2 = 8πhc � � � x e dx
0 hc�xkT x hc 0

8π(KT)4 48πk 4 4
= × 3! = T
(hc) 3 (hc)3
�e integral is of the form of Integral E.� with n = 3 and k = 1. �is is
consistent with the Stefan–Boltzmann law, as the energy density is pro-
portional to T 4 .
(d) �e energy spectral density is maximized at λ = λ max , where dρ�dλ = 0.
�is gives
dρ d
= 8πhc �λ−5 e−hc�λk T �
dλ dλ
dλ−5 −hc�λk T de−hc�λk T
= 8πhc � e + λ−5 �
dλ dλ
hc
= 8πhc �−5λ−6 e hc�λk T + λ−5 × 5 e hc�λk T �
λ kT
8πhce hc�λk T hc
= �−5λ + �
λ7 kT
�is expression equals 0 at λ = λ max , and is solved when
hc
−5λ max + =0
kT
hc
λ max T =
5k
�at is λ max T is a constant, which is consistent with Wien’s law

P�A.�� �e Einstein temperature is given by θ E = hν E �k; this has units of K (temper-

ature), as expected
(J s) × (s−1 )
= K
J K−1
 In terms of temperature, the Einstein equation for molar heat capacity is [�A.�a–
���],
θ E 2 eθ E �2T
2
C V ,m (T) = 3R f E (T), f E (T) = � � � θ �T �
T e E −1
At high temperatures, this tends towards the classical value,
2
θE 2 1
lim C V ,m (T) = 3R � � � � = 3R
T→∞ T 1 + θ E �T − 1

�is limit is valid when θ E �T � 1 , which is equivalent to hν E �kT � 1 . �e

conversion between frequency and temperature is
h 6.6261 × 10−34 J s
θE = νE = (ν E �Hz) = (4.79... × 10−11 K) × (ν E �Hz)
k 1.3806 × 10−23 J K−1
(a) For diamond, ν E = 46.5 THz and hence θ E = 2.23... × 103 K

2.23... × 103 K � e2.23 ...×10 K�(2×298 K) �

2 3 2

f E (298 K) = � � = 0.0314
298 K � e2.23 ...×10 K�(298 K) − 1 �
3

C V ,m (298 K) = 3R × (0.0314)
(b) For copper, ν E = 7.15 THz and hence θ E = 343... K

343... K 2 e343 ... K�(2×298 K)

2
f E (298 K) = � � � 343 ... K�(298 K) � = 0.896
298 K e −1

C V ,m (298 K) = 3R × (0.896)

D�B.� �ese terms are best illustrated by referring to a one-dimensional system. �e

probability density P(x) is de�ned so that P(x) dx is the probability of �nding
the system between x and x + dx. �e value of the wavefunction itself, ψ(x),
is the probability amplitude. �e probability density is given in terms of this
amplitude as P(x) = ψ ∗ (x)ψ(x).

E�B.�(b) �e task is to �nd N such that ψ = N sin(3πx�L) satis�es the normalization

condition [�B.�c–���], ∫ ψ ∗ ψ dτ = 1. In this case the integration is over x and
the range is 0 to L; the function is real, so ψ = ψ ∗ .
=sin 6π=0
L ��� � � � � � � � � � � �� � � � � � � � � � � � ��
N �
2
sin (3πx�L)dx = N [L�2 − (L�12π) sin(6πL�L)] = N 2 (L�2)
2 2
0
 �e integral is of the form of Integral T.� with a = L and k = 3π�L. For
the wavefunction to be normalized, the integral must be 1 and therefore the
normalizing factor is N = (2�L)1�2 .

E�B.�(b) �e task is to �nd N such that ψ = N exp(−ax) satis�es the normalization

condition [�B.�c–���], ∫ ψ ∗ ψ dτ = 1. In this case the integration is over x and
the range is 0 to ∞. �e function is real, so ψ = ψ ∗ and the integral is therefore
∞
N 2 ∫0 exp(−2ax)dx.
∞ ∞
N2 � e−2ax dx = −(N 2 �2a) e−2ax �0 = −(N 2 �2a)(e−∞ − e0 ) = (N 2 �2a)
0

where exp(−∞) = 0 and exp(0) = 1 are used. Setting the integral equal to 1
gives N = (2a)1�2 .

E�B.�(b) (i) �e function ψ = sin(ax) cannot be normalized as the area under ψ ∗ ψ =

sin2 (ax) is in�nite when the limits of x are ±∞. However, over a �nite
region, the wavefunction can be normalized.
(ii) cos(ax) exp(−x 2 ) can be normalized as it goes to � as x goes to ±∞ so
the integral of ψ ∗ ψ over all space is �nite.
A function is an acceptable wavefunction if it: (�) is not in�nite over a �nite re-
gion; (�) is single-valued; (�) is continuous; (�) has a continuous �rst derivative.
Both functions satisfy all of these conditions and so are acceptable wavefunc-
tions.

E�B.�(b) �e probability of �nding an electron in an in�nitesimal region dx around x

is P(x)dx = ψ ∗ (x)ψ(x)dx, provided that ψ(x) is a normalized wavefunction.
�e wavefunction is real so that ψ ∗ = ψ, hence the probability is given by

P(x)dx = �(2�L)1�2 sin(3πx�L)� dx = (2�L) sin2 (3πx�L)dx

2

Hence, at x = L�6, P(L�6)dx = (2�L) sin(π�2)dx = (2�L)dx .

E�B.�(b) �e normalized wavefunction is ψ(x) = (2�L)1�2 sin(2πx�L). �e probability

of �nding the electron between x = 0 and x = L�3 is, using Integral T.�
L�3
� (2�L) sin2 (3πx�L) dx = (2�L) � x�2 − (L�12π) sin(6πx�L)�0 �
L�3
0
= (2�L)([L�6 − (L�12π) sin(2π)] − [0 − (L�12π) sin(0)])
= (2�L)[L�6 − 0] = �/�

E�B.�(b) Both x and L have dimensions of length, so 2πx�L is dimensionless, as required

for the argument of a sine function. �e dimensions of the wavefunction come
from the normalizing factor (2�L)1�2 which has dimensions (length)−1�2 . �e
probability is �ψ(x)�2 dx: �ψ(x)�2 has dimensions of (length)−1 , and dx has
dimensions of length. Hence, �ψ(x)�2 dx is dimensionless, as required.
E�B.�(b) A function is an acceptable wavefunction if it: (�) is not in�nite over a �nite
region; (�) is single-valued; (�) is continuous; (�) has a continuous �rst deriva-
tive. Note that for a particle on a ring, the condition to be single valued implies
the function must be periodic over 2π, meaning that the function ‘joins up’
with itself as it goes through 2π. Expressed mathematically this condition is
ψ(�) = ψ(� + 2π), where � is the angle.

(i) cos � is periodic over 2π and satis�es all the other conditions so it is an
acceptable wavefunction.
(ii) sin � is periodic over 2π and satis�es all the other conditions so it is an
acceptable wavefunction.
(iii) cos(0.9�) is not periodic over 2π (in fact it is periodic over (2π)�0.9). �e
function does not ‘join up’ a�er the angle goes through 2π and therefore
it is not an acceptable wavefunction.

E�B.�(b) �e normalized wavefunction is ψ(x) = (2�L)1�2 sin(3πx�L), and so the prob-

ability density is P(x) = �ψ(x)�2 = (2�L) sin2 (3πx�L). �is is maximized when
sin2 (3πx�L) = 1, and so when sin(3πx�L) = ±1. �ese values occur when
3πx�L = π�2, 3π�2, 5π�2 and hence x = L�6, L�2, 5L�6 .
Nodes occur when the wavefunction goes through zero: sin(3πx�L) = 0. �e
sine function is zero when 3πx�L = π, 2π, hence x = L�3, 2L�3 . �e wave-
function goes to zero at x = 0 and x = L, but these do not count as nodes as the
wavefunction does not pass through zero.

P�B.� (a) �e task is to �nd N such that ψ = N cos(�) satis�es the normalization
condition [�B.�c–���], ∫ ψ ∗ ψ dτ = 1. In this case the integration is over �
and the range is 0 to 2π; the function is real so ψ ∗ = ψ. Using the identity
sin2 x + cos2 x = 1 the integrand is expressed as cos2 � = 1 − sin2 �, and
then the integral is evaluated using Integral T.�
2π
N2 � (1 − sin2 �) d� = N 2 � ��0 − (2π�2) + (1�4) sin(4π)� = πN 2
2π
0

Setting this equal to 1 gives N = (π)−1�2 .

(b) �e task is to �nd N such that ψ = N sin(m l �) satis�es the normalization
condition [�B.�c–���], ∫ ψ ∗ ψ dτ = 1. In this case the integration is over
� and the range is 0 to 2π; the function is real so ψ ∗ = ψ. �e integral is
evaluated using Integral T.�
=0
2π ��� � � � � � � � � � �� � � � � � � � � � �
N �
2
sin (m l �) d� = N [(2π�2) − (1�4m l ) sin(4m l π)] = πN 2
2 2
0

where sin nπ = 0 for integer n is used. Setting the result equal to 1 gives
N = (π)−1�2 .
P�B.� �e task is to �nd N such that ψ = N exp(−ax 2 ) exp(−by 2 ) satis�es the nor-
malization condition [�B.�c–���], ∫ ψ ∗ ψ dτ = 1. �e integration is over x
and y, with both ranging from −∞ to ∞. �e wavefunction is real, and so the
integral to evaluate is
∞ ∞
N2 � � e−2ax e−2b y dxdy
2 2

−∞ −∞

�is integral separates into a product of two integrals

∞ ∞
N2 � e−2ax dx � e−2b y dy
2 2

−∞ −∞

For both the integrand is even, such that it is the same at x and −x, or y and
−y. Hence the integral between −∞ and ∞ is simply twice that between 0 and
∞. Using this gives
∞ ∞
4N 2 � e−2ax dx � e−2b y dy
2 2

0 0

�e integrals are evaluated using Integral G.� to give

4N 2 × 12 (π�2a)1�2 × 12 (π�2b)1�2 = N 2 (π 2 �4ab)1�2

Setting this equal to 1 gives N = (4ab�π 2 )1�2 .

�e task is to �nd N such that ψ(x) = Ne−ax , satis�es the normalization

2
P�B.�
condition [�B.�c–���], ∫ ψ ∗ ψ dτ = 1. �e integration is over x ranging from
−∞ to ∞. �e required integral is
∞
N2 � e−2ax dx
2

−∞

�e integrand is even, and so the integral from −∞ to ∞ is twice the integral

from 0 to ∞. �e integral is evaluated using Integral G.�
∞
2N 2 � e−2ax dx = 2N 2 × 12 (π�2a)1�2
2

Setting this equal to one gives N = (2a�π)1�4 .

�e total probability of �nding the particle at a distance x ≥ x 0 is therefore
∞
(2a�π)1�2 � e−2ax dx
2

x0

With a = 0.2 m−2 and x 0 = 1 m this integral becomes

∞
(0.4�π)1�2 � e−0.4×x dx
2

which evaluates numerically to 0.186 .

P�B.� �e probability of �nding the particle within the range x = a to x = b, and
y = c to y = d is
b d
P(a → b, c → d) = � � �ψ(x, y)�2 dxdy
a c
b d
=� � (2�L)2 sin2 (πx�L) sin2 (πy�L) dxdy
a c

�e integral separates into integrals over x and y

b d
=� (2�L) sin2 (πx�L) dx × � (2�L) sin2 (πx�L) dx
a c

Both integrals are evaluated using Integral T.� to give the probability as
b−a 1 2πb 2πa d−c 1 2πd 2πc
� − �sin � � − sin � ��� � − �sin � � − sin � ���
L 2π L L L 2π L L
Hence
(a) a = 0, b = L�2, c = 0, d = L�2; P = �/�
(b) a = L�4, b = 3L�4, c = L�4, d = 3L�4; P = 14 (1 + 2�π)2 = �.���

∞
P�B.�� (a) Normalization requires �nding N such that N 2 ∫−∞ exp(−x 2 �a 2 )dx = 1.
Because the integrand is symmetric, the integral from −∞ to +∞ is twice
that from 0 to +∞. With this, the integral is evaluated using Integral G.�
∞
2N 2 � e−x �a 2
dx = 2N 2 × 12 (πa 2 )1�2
2

Setting this equal to � gives N = (πa 2 )−1�4 . �e required probability is

given by
a a
�(πa 2 )−1�4 exp(−x 2 �a 2 )� dx = 2(πa 2 )−1�2 � exp(−x 2 �a 2 )dx
2
�
−a 0
= erf(1) = �.���
�is integral has no analytical solution, but is easily evaluated using math-
ematical so�ware.

D�C.� In quantum mechanics an observable quantity (such as energy, position or

momentum) is represented by a particular operator Ω̂. If the wavefunction
is ψ the average value of the quantity represented by the operator Ω̂ is given by
�Ω� = ∫ ψ ∗ Ω̂ψ dτ, called the expectation value. For the special case that ψ is
an eigenfunction of Ω̂, the expectation value is the eigenvalue corresponding
to this eigenfunction.
E�C.�(b) To construct the potential energy operator, replace the position x in the clas-
sical expression by the position operator x̂. �is operator is just multiplication
by x, x̂ = x×, therefore the potential energy operator is V̂ = D e (1 − e−ax )2 .

E�C.�(b) A function ψ is an eigenfunction of an operator Ω̂ if Ω̂ψ = ωψ where ω is a

constant called the eigenvalue.

(i) (d2 �dx 2 ) cos(kx) = −k 2 cos(kx). Hence cos kx is an eigenfunction of

the operator d2 �dx 2 , with eigenvalue −k 2 .
(ii) (d2 �dx 2 )eik x = (d�dx)ikeik x = −k 2 eik x . Hence eik x is an eigenfunction
of the operator d2 �dx 2 , with eigenvalue −k 2 .
(iii) (d2 �dx 2 )kx = (d�dx)k = 0 = 0 × kx. Hence kx is an eigenfunction of
the operator d2 �dx 2 with eigenvalue 0 .
(iv) (d2 �dx 2 )e−ax = (d�dx)(−2axe−ax ) = 2ae−ax (2ax 2 − 1). Hence this
2 2 2

function is not an eigenfunction of the operator d2 �dx 2 .

E�C.�(b) Wavefunctions ψ 1 and ψ 2 are orthogonal if ∫ ψ ∗1 ψ 2 dτ = 0, [�C.�–���]. Here

ψ 1 (x) = sin(4πx�L), ψ 2 (x) = sin(2πx�L), and the region is 0 ≤ x ≤ L. �e
integral is evaluated using Integral T.�
L
� ψ 1 ψ 2 dτ = �
∗
sin(4πx�L) sin(2πx�L) dx
0
= [(L�4π) sin(2π) − (L�12π) sin(6π)] = 0

where sin(nπ) = 0 for integer n is used. �us, the two wavefunctions are
orthogonal.

E�C.�(b) Wavefunctions ψ 1 and ψ 2 are orthogonal if ∫ ψ ∗1 ψ 2 dτ = 0, [�C.�–���]. Here

ψ 1 (x) = cos(3πx�L), ψ 2 (x) = cos(5πx�L), and the region is −L�2 ≤ x ≤ L�2.
�e integral is evaluated using Integral T.�

L�2
� ψ 1 ψ 2 dτ = �
∗
cos(3πx�L) cos(5πx�L) dx
−L�2

= (−L�4π) sin(−2πx�L) + (L�16π) sin(8πx�L)�−L�2

L�2

= [(−L�4π) sin(−π) + (L�16π) sin(4π)]

− [(−L�4π) sin(π) + (L�16π) sin(−4π)] = 0

where sin(nπ) = 0 for integer n is used. �us, the two wavefunctions are
orthogonal.
E�C.�(b) Two wavefunctions ψ i and ψ j are orthogonal if ∫ ψ ∗i ψ j dτ = 0, [�C.�–���].
In this case the integration is from � = 0 to � = 2π. Let ψ i = exp(i�), the
wavefunction with m l = +1, and ψ j = exp(−2i�), the wavefunction with m l =
−2. Note that the functions are complex, so ψ ∗i = exp(−i�). �e integrand is
therefore
ψ ∗i ψ j = exp(−i�) exp(−2i�) = exp(−3i�)
and the integral evaluates as
2π
� exp(−3i�) d� = (−1�3i) exp(−3i�)�0
2π
0
=1 =1
��� � � � � � � � � �� � � � � � � � � � �� ��� � � � �� � � � ��
= (−1�3i)[exp(−6πi) − exp(i0)] = 0

�e identity exp(ix) = cos x + i sin x (�e chemist’s toolkit �� in Topic �C on

page ���) is used to evaluate exp(−6πi) = cos(−6π) + i sin(−6π) = 1 + 0 = 1.
�e integral is zero, so the functions are indeed orthogonal.

E�C.�(b) �e normalized wavefunction is ψ(x) = (2�L)1�2 sin(πx�L). �e operator for

position is x̂ = x, therefore the expectation value of the position of the electron
is [�C.��–���]
L
�x� = � ψ ∗ x̂ψ dτ = (2�L) � x sin2 (πx�L) dx
0

�is integral is of the form of Integral T.�� with k = π�L and a = L

=sin 2π=0 =cos 2π=1

� 2 ��� � � � � � � � � �� � � � � � � � � � �� � ��� � � � � � � � � � � � � � � � � � � � � � ��
2� �
� �
��
�
= � −
L L
sin �
2πL
�−
1
� cos �
2πL
� −1��
L � 4 4 × π�L 8 × (π�L) �� ��
� ��
�
L 2 L
� �
2 L2
= × = L�2
L 4
Because the probability density �ψ(x)�2 is symmetric about x = L�2, the ex-
pected result is �x� = L�2.

E�C.�(b) �e normalized wavefunction is ψ(x) = (2�L)1�2 sin(πx�L). �e expectation

value of the momentum is ∫ ψ ∗ p̂ x ψ dx, and the momentum operator is p̂ x =
(ħ�i)d�dx, therefore
L
�p x � = (2�L) � sin(πx�L) p̂ x sin(πx�L) dx
0
L
= (2ħ�iL) � sin(πx�L)(d�dx) sin(πx�L) dx
0

Using (d�dx) sin(πx�L) = (π�L) cos(πx�L) gives

L
�p x � = (2πħ�iL 2 ) � sin(πx�L) cos(πx�L) dx
0
 �e integral is of the form of Integral T.� with a = L, k = π�L
2πħ 1 πL
�p x � = × sin2 � � = 0
iL 2 2 × π�L L
�is result is interpreted as meaning that there are equal probabilities of having
momentum in the positive and negative x directions.

E�C.�(b) For the case when m l = +1 the normalized wavefunction is ψ+1 (�) = (2π)−1�2 ei� .
∗
�is is complex, and so ψ+1 = (2π)−1�2 e−i� . �e angular momentum operator
is (ħ�i)(d�d�), therefore its expectation value is given by
2π 2π
�
∗
ψ+1 (ħ�i)(d�d�)ψ+1 d� = (1�2π)(ħ�i) � e−i� (d�d�)ei� d�
0 0
2π
= (1�2π)(ħ�i)(i) � e−i� ei� d�
0
2π
= (1�2π)(ħ�i)(i) � 1 d�
0
= (1�2π)(ħ�i)(i)(2π) = ħ

For the general case the normalized wavefunction is ψ m l (�) = (2π)−1�2 eim l �
and ψ ∗m l (�) = (2π)−1�2 eim l � .
2π 2π
� ψ ∗m l (ħ�i)(d�d�)ψ m l d� = (1�2π)(ħ�i) � e−im l � (d�d�)eim l � d�
0 0
2π
= (1�2π)(ħ�i)(im l ) � e−m l i� eim l � d�
0
= (1�2π)(ħ�i)(im l )(2π) = m l ħ

E�C.�(b) �e uncertainty in the momentum is given by ∆p = m∆υ where m is the mass

and ∆υ is the uncertainty in the velocity. �e minimum uncertainty in the
position of the electron is given as 100 pm .
�e uncertainties in position and momentum are must obey the Heisenberg
uncertainty principle [�C.��a–���], ∆p∆q ≥ (ħ�2), which in this case is ex-
pressed as m∆υ∆q ≥ (ħ�2). �is is rearranged to give the uncertainty in the ve-
locity, ∆υ ≥ ħ�(2m∆q), giving a minimum uncertainty of ∆υ min = ħ�(2m∆q),
which is evaluated as
1.0546 × 10−34 J s
= 5.79 × 105 m s−1
2 × (9.1094 × 10−31 kg) × (100 × 10−12 m)

E�C.��(b) �e desired uncertainty in the momentum is

∆p = 0.0010 × 10−2 p = 1.00 × 10−5 m e υ

= 1.00 × 10−5 × (9.1094 × 10−31 kg) × (995 × 103 m s−1 )
= 9.06... × 10−30 kg m s−1
 �e Heisenberg uncertainty principle, [�C.��a–���] is rearranged to give the
uncertainty in the position as ∆q ≥ ħ�(2∆p), which gives a minimum uncer-
tainty of ∆q min = ħ�(2∆p). �is is evaluated as

1.0546 × 10−34 J s
= 5.82 × 10−6 m
2 × (9.06... × 10−30 kg m s−1 )

(a) Consider the integral I = ∫0 sin(nπx�L) sin(mπx�L) dx. Using the iden-
L
P�C.�
tity, sin A sin B = 12 cos(A − B) − 12 cos(A + B) with A = nπx�L and
B = mπx�L, this can be rewritten as
L L
I = 12 � cos[(n − m)πx�L] dx − 12 � cos[(n + m)πx�L] dx (�.�)
0 0

(b) In the case of n = 2, m = 1 the two integrands are cos(πx�L) and cos(3πx�L)
which are plotted in Fig. �.�

1.0 cos(πx�L)
cos(3πx�L)
0.5

x�L
0.2 0.4 0.6 0.8 1.0
−0.5

−1.0

(c) It is seen that each of these functions are antisymmetric about x = L�2,
such that the value of the function as L�2 + δ is minus that at L�2 − δ. As
a result, the integral of these functions over a symmetrical region about
x = L�2 is zero.
An alternative way of coming to the same conclusion is to note that the
integral of the �rst half of a cosine wave is zero on account of the enclosed
area above and below the x-axis being the same (the solid curve). Sim-
ilarly, the integral of three complete half cosine waves is also zero (the
dashed curve).
(d) For the general case n and m and both integers, and so n ± m are also
integers. �e two integrands in eqn �.�, when considered over the range
x = 0 → L, will each comprise a complete number of half cosine waves.
By the same argument as in (c), these functions will integrate to zero and
hence the wavefunctions are orthogonal for n ≠ m.
 ∗
P�C.� An operator Ω̂ is hermitian if ∫ ψ ∗i Ω̂ψ j dτ = �∫ ψ ∗j Ω̂ψ i dτ� , [�C.�–���]. Pro-
ceed by integrating by parts (�e chemist’s toolkit �� in Topic �C on page ���)
to give

2π ħ d ħ � ∗ 2π 2π dψ ∗ �
� ψ ∗i � � ψ j d� = ψ i ψ j �0 − � ψ j i d�
0 i d� i � ��� � � � � � � � � � � � 0 d� �
A

�e term A is zero because the wavefunction must be single valued, requiring

ψ i (�) = ψ i (� + 2π), and so ψ i (0) = ψ i (2π). It follows that
2π ħ d ħ 2π dψ ∗
� ψ ∗i � � ψ j d� = − � ψ j i d�
0 i d� i 0 d�
�e term of the right is written as a complex conjugate to give
∗ ∗
2π ħ d ħ 2π dψ i 2π ħ d
� ψ ∗i � � ψ j d� = � � ψ ∗j d�� = �� ψ ∗j � � ψ i d��
0 i d� i 0 d� 0 i d�
Note that because the complex conjugate of the whole term is taken, to com-
pensate for this the complex conjugate of the terms inside the bracket need to
be taken too ψ = [ψ ∗ ]∗ ; i∗ = −i is also used. �is �nal equation is consistent
with [�C.�–���] and so demonstrates that the angular momentum operator is
hermitian.

P�C.� �e expectation value is given by [�C.��–���], �Ω� = ∫ ψ ∗ Ω̂ψ dτ, where ψ is

normalized. However, if ψ is an eigenfunction of Ω̂ each measurement gives
the corresponding eigenvalue, and this is therefore also the expectation value.

(a) �e function N exp(ikx) is an eigenfunction of the linear momentum

operator p̂ x = (ħ�i)(d�dx)
ħ d ħ
Neik x = × Nikeik x = ħk × Neik x
i dx i
and the eigenvalue is ħk . Hence, the expectation value is equal to this.
(b) �e wavefunction N cos kx is not an eigenfunction of the linear momen-
tum operator, so the expectation value has to be computed by evaluating
the integral. First consider the e�ect of applying this operator to the wave-
function

p̂ x ψ = (ħ�i)(d�dx)N cos(kx) = −(ħk�i)N sin kx

It follows that the expectation value is given by

∞
�p x � = −(ħk�i)N 2 � cos(kx) sin(kx) dx = 0
−∞

�e integrand is an odd function, meaning that its value at −x is the

negative of that at x, which means that its integral over a symmetric range
is zero.
 (c) �e wavefunction Ne−ax is not an eigenfunction of the linear momen-
2

tum operator. Consider the e�ect of applying this operator to the wave-
function

p̂ x ψ = (ħ�i)(d�dx)Ne−ax = (ħ�i) × −2axNe−ax

2 2

�e expectation value of the momentum is then

∞
�p x � = (−2aN 2 ħ�i) � xe−2ax dx = �
2

−∞

As before, the integrand is an odd function so its integral over a symmet-

ric range is zero.

P�C.� (a) �e wavefunction ψ(x) = cos(χ)eik x + sin(χ)e−ik x is a superposition of

the functions ψ+ = eik x and ψ− = e−ik x . �ese are eigenfunctions of the
linear momentum operator with eigenvalues +ħk and −ħk respectively,
as
ħ d eik x ħ ħ d e−ik x ħ
= × ikeik x = ħkeik x = × −ike−ik x = −ħke−ik x
i dx i i dx i
As the wavefunction is a superposition of eigenfunctions of the linear mo-
mentum operator, the probability of measuring a particular momentum
eigenvalue is the square modulus of the corresponding coe�cent, �c k �2 in
the expression for ψ. Hence the probability of �nding the electron with
linear momentum +kħ is �c+ �2 = �cos χ�2 = cos2 χ
(b) �e probability of �nding the electron with linear momentum −kħ is
�c− �2 = �sin χ�2 = sin2 χ
(c) If the probability of �nding the electron with momentum +kħ √ is 0.9, then
�c+ �2 = 0.9, and assuming that c+ is real and positive , c+ = 0.9 = 0.95 .
�e probabilities must sum to 1 and so the probability of �nding √ the
electron with momentum −kħ is 0.1, then �c+ �2 = 0.1 and so c− = 0.1 =
0.32
(d) �e kinetic energy operator is Eˆk = p̂2x �2m = −(ħ 2 �2m)d2 �dx 2 , where m
is the mass of the electron. Consider applying this operator to ψ±

ħ 2 d2 ik x ħ 2 k 2 ik x
Eˆk ψ+ = − e = e
2m dx 2 2m
ħ 2 d2 −ik x ħ 2 k 2 −ik x
Eˆk ψ− = − e = e
2m dx 2 2m
Hence, both components are eigenfunctions of the kinetic energy oper-
ator with the same eigenvalue, (ħk)2 �2m, and so the overall wavefunc-
tion is also an eigenfunction of the kinetic energy operator, eigenvalue
(ħk)2 �2m. �e kinetic energy of the electron is thus (ħk)2 �2m

P�C.�� (a) Figure �.� shows that as N increases the symmetrical peak around x = 0
narrows and sharpens.
 1.0 N =2
N =5
0.5

0.0

−0.5

−1.0 −0.5 0.0 0.5 1.0

x

1.0 N =2
N =5

0.5

0.0
−1.0 −0.5 0.0 0.5 1.0
x

(b) Figure �.� shows that, as before, the probability density narrows and sharp-
ens as the superposition is extended.

(c) In order to compute �x 2 �, the expectation value of x 2 , it is necessary to

normalize the wavefunction. If attention is focused on the �nite range
−1 ≤ x ≤ +1 the normalizing factor N is found by evaluating

�
� �
�
−1
� 1 �
2
+1 N
N =� 2 �
2
� � cos(kπx)� dx �
�
� N −1 k=1 �
�
� �

Because the square of a sum involving (possibly) many terms is involved,

this appears to be a formidable task. However, some experimentation
with some modest values of N using mathematical so�ware implies that
the term in the braces is simply (1�N), so the normalizing factor is N =
 (N)1�2 . With this, the expectation value is computed using
2
+1 N
�x 2 � = (N) × (1�N 2 ) � � � cos(kπx)� x 2 dx
−1 k=1

Mathematical so�ware gives the values 0.0628 for N = 5, 0.0305 for N =

10, and 0.0254 for N = 12. �e corresponding values of �x 2 �1�2 are 0.251,
0.175 and 0.159. �ere is a decreasing trend in the value of �x 2 �1�2 which
makes sense as the superposition becomes narrower as N increases.
(d) �is wavefunction is the superposition of N terms each of which has
the form N −1 cos(kπx). Momentum is more easily discussed by using
the identity cos(kπx) = 12 (eikπx + e−ikπx ). �e wavefunction is then a
superposition of N terms of the form (1�2N)eikπx and N of the form
(1�2N)e−ikπx . �e �rst of these terms corresponds to a momentum +kħ,
and the second to a momentum −kħ.
�e normalizing factor is N 1�2 , so the coe�cient of each of the terms in
the expansion (of the form e±ikπx ) is N 1�2 �2N = 1�2N 1�2 . �e probability
of observing the momentum corresponding to any one term is given by
the square is this coe�cient, which is 1�4N.

P�C.�� To evaluate the commutator of the position and momentum operators consider
the e�ect of the commutator on an arbitrary function ψ

ħ d(xψ) ħ dψ
[ p̂ x , x̂]ψ = ( p̂ x x̂ − x̂ p̂ x )ψ = � −x �
i dx i dx

to evaluate the �rst derivative the product rule is used

ħ dψ dx dψ ħ
= �x +ψ −x �= ψ
i dx dx dx i

Because [ p̂ x , x̂]ψ = (ħ�i)ψ it follows that the commutator is the constant term
ħ�i. Hence the expectation value is given by

ψ ∗ (ħ�i)ψ dτ
�[ p̂ x , x̂]� = ∫ = ħ�i
∫ ψ ∗ ψ dτ

P�C.�� To evaluate the commutator consider its e�ect on an arbitrary wavefunction ψ

[â, ↠]ψ = (â â † − ↠â)ψ

1 1 1 1
= � √ (x̂ + i p̂ x ) √ (x̂ − i p̂ x ) − √ (x̂ − i p̂ x ) √ (x̂ + i p̂ x )� ψ
2 2 2 2
= 2 �(x̂ − ix̂ p̂ x + i p̂ x x̂ + p̂ x ) − (x̂ + ix̂ p̂ x − i p̂ x x̂ + p̂2x )� ψ
1 2 2 2

= i( p̂ x x̂ − x̂ p̂ x )ψ
 �e quantity in the parentheses is the commutator [ p̂ x , x̂]. �e commutator of
the position and momentum operators is given by [�C.��–���], [x̂, p̂ x ] = iħ,
therefore [ p̂ x , x̂] = −iħ

[â, â † ]ψ = i[ p̂ x , x̂]ψ = i(−iħ)ψ = ħψ

Hence [â, â † ] = ħ .

D�D.� �e hamiltonian for a particle in a two- or three-dimensional box is separa-

ble into a sum of terms each of which depends on just one of the variables
x, y or z. �erefore the solutions to the Schrödinger equation are products
of separate functions of each of these variables, Ψ(x, y, z) = ψ(x)ψ(y)ψ(z).
In the hamiltonian the terms in the three variables are all of the same form,
so the wavefunctions are likewise of the same form. Similarly, the boundary
conditions along each direction are the same, so the quantization which this
imposes is the same. As a result the wavefunctions are simply a product of the
wavefunctions that would be found by solving the Schrödinger equation along
each direction separately.
�e energy levels of two- and three-dimensional boxes can be degenerate, that
is there are di�erent wavefunctions which have the same energy. �is is usually
a consequence of the box having a certain kind of symmetry, for example in a
two-dimensional box in which the two sides are the same length the levels with
quantum numbers n 1 = l, n 2 = m and n 1 = m, n 2 = l are degenerate.

E�D.�(b) �e linear momentum of a free electron is given by

p = ħk = (1.0546 × 10−34 J s) × (5 × 109 m−1 ) = 5 × 10−25 kg m s−1

where 1 J = 1 kg m2 s−2 is used; note that 1 nm−1 = 1 × 109 m−1 . �e kinetic

energy is given by [�D.�–���]

(ħk)2 ((1.0546 × 10−34 J s) × (5 × 109 m−1 ))2

Ek = = = 2 × 10−19 J
2m 2 × (9.1094 × 10−31 kg)

E�D.�(b) �e electron is travelling in the positive x direction hence the momentum and
the velocity υ are both positive. �e momentum of this particle is given by

p = mυ = (1.0 × 10−3 kg) × (+10 m s−1 ) = +0.01 kg m s−1

 �e values of k is therefore

p +0.01 kg m s−1
k= = = +9.5 × 1031 m−1
ħ 1.0546 × 10−34 J s

where 1 J = 1 kg m2 s−2 is used. �e wavefunction is then, with x is measured

in metres,
ψ(x) = eik x = e+i(9.5×10 m−1 )x
31

E�D.�(b) �e energy levels of a particle in a box are given by [�D.�–���], E n = n 2 h 2 �8mL 2 ,

where n is the quantum number. With the mass equal to that of the electron
and the length as �.� nm, the energies are

n2 h2 (6.6261 × 10−34 J s)2

En = = n 2
×
8mL 2 8 × (9.1094 × 10−31 kg) × (1.5 × 10−9 m)2
= n 2 × (2.67... × 10−20 J)

To convert to kJ mol−1 , multiply through by Avogadro’s constant and divide by

1000.

6.0221 × 1023 mol−1

= n 2 × (2.67... × 10−20 J) × = n 2 × (16.1... kJ mol−1 )
1000

To convert to electronvolts divide through by the elementary charge

1
= n 2 × (2.67... × 10−20 J) × = n 2 × (0.167... eV)
1.6022 × 10−19 C

To convert to reciprocal centimetres, divide by hc, with c in cm s−1

(2.67... × 10−20 J)
= n2 ×
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
= n 2 × (1.34... × 103 cm−1 )

�e energy separation between two levels with quantum numbers n 1 and n 2 is

∆E(n 1 , n 2 ) = E n 2 − E n 1 = (n 22 − n 12 ) × (2.67... × 10−20 J)

�e values in the other units are found by using the appropriate value of the
constant, computed above.

(i) ∆E(2, 3) = 1.3 × 10−19 J , �� kJ mol−1 , �.�� eV , or 6.7 × 103 cm−1

(ii) ∆E(6, 7) = 3.5 × 10−19 J , 2.1 × 102 kJ mol−1 , �.� eV ,

or 1.8 × 104 cm−1
E�D.�(b) �e wavefunctions are ψ 1 (x) = (2�L)1�2 sin(πx�L) and ψ 3 (x) = (2�L)1�2 ×
sin(3πx�L). �ey are orthogonal if ∫ ψ ∗1 ψ 2 dτ = 0. In this case the integral is
taken from x = 0 to x = L as outside this range the wavefunctions are zero. �e
required integral is of the form of Integral T.�, with A = π�L, B = 3π�L, and
a=L
2 L πx 3πx 2 sin(−2πL�L) sin(4πL�L)
� sin � � sin � � dx = � − �
L 0 L L L −4π�L 8π�L
2 sin(−2π) sin(4π)
= � − �=0
L −4π�L 8π�L
where sin nπ = 0 for integer n is used. �e two wavefunctions are orthogonal.

E�D.�(b) �e particle in a box wavefunction with quantum number n is given by ψ n (x) =

(2�L)1�2 sin(nπx�L) �e probability of �nding the electron in a small region of
space δx centred on position x is approximated as ψ 2 (x)δx. For this Exercise
x = 0.66L, δx = 0.02L.
For the case where n = 1
�
ψ 1 (0.66L)2 × 0.02L = � 2�L sin (π(0.66L)�L)� × 0.02L
2

= (2�L) sin2 (0.66π) × 0.02L = �.���

For the case where n = 2

�
ψ 2 (0.66L)2 × 0.02L = � 2�L sin (2 × π(0.66L)L)� × 0.02L
2

= (2�L) sin2 (1.32π) × 0.02L = �.���

�
E�D.�(b) �e wavefunction with n = 2 and is ψ 2 (x) = 2�L sin(2πx�L), which leads to
a probability density P2 (x) = �ψ 2 (x)�2 = (2�L) sin2 (2πx�L). Graphs of these
functions are shown in Fig �.�.

ψ2
ψ 22

x�L
0.2 0.4 0.6 0.8 1.0

�e probability density is symmetric about x = L�2. �erefore, there is an equal

probability of observing the particle at an arbitrary position x ′ and at L − x ′ , so
it follows that the average position of the particle must be at L�2.
 �
E�D.�(b) �e wavefunction with n = 1 is ψ 1 (x) = 2�L sin(πx�L), which leads to a
probability density P1 (x) = �ψ 1 (x)�2 = (2�L) sin2 (πx�L). Graphs of these
functions are shown in Fig �.�.

ψ1
ψ 12

x�L
0.2 0.4 0.6 0.8 1.0

�e probability density is symmetric about x = L�2. �erefore, there is equal

probability density at positions (L�2) + δ and (L�2) − δ, so it follows that the
average position of the particle must be at L�2.
�e expectation value of x 2 is found from the integral ∫0 P1 (x)x 2 dx. Al-
L

though the probability density will be the same at positions (L�2) − δ and
(L�2) + δ, the function x 2 will increase by more between (L�2) and (L�2) + δ,
than between (L�2) − δ and (L�2), so in the integral the point at (L�2) + δ has
greater weight. It is therefore expected that �x 2 � > (L�2)2 .

E�D.�(b) For an electron in a cubic well, of side length L the energy of the state character-
ized by quantum numbers n 1 , n 2 and n 3 is given by [�D.��b–���], E n x ,n y ,n z =
h 2 (n 2x +n 2y +n 2z )�8m e L 2 where n x , n y , n z are integers ≥ 1. Hence, the minimum
or zero-point energy has n x = n y = n z = 1,

E 1,1,1 = h 2 (12 + 12 + 12 )�8m e L 2 = 3h 2 �8m e L 2

Setting this equal to the rest energy, m e c 2 gives

3h 2 �8m e L 2 = m e c 2
� �
L = 3�8 × (h�m e c) = 3�8 λ C

where λ C = h�(m e c) is the Compton wavelength.

E�D.�(b) �e wavefunction for a particle�in a one-dimensional box with length L and in

the state with n = 5 is ψ(x) = 2�L sin(5πx�L) giving a probability density of
P(x) = �ψ(x)�2 = (2�L) sin2 (5πx�L).
As this is a trigonometric function, the function is maximized when sin2 (5πx�L)
= 1, which is when sin(5πx�L) = ±1; these values occur when the argument of
the sine function is an odd multiple of π�2

5πx�L = π�2, 3π�2, 5π�2, 7π�2, ... hence x = L�10, 3L�10, L�2, 7L�10, 9L�10
 �e probability density is zero when the wavefunction is zero, which is when
the argument of the sine function is a multiple of π

5πx�L = 0, π, 2π, ... hence x = 0, L�5, 2L�5, 3L�5, 4L�5, L

E�D.��(b) �e energy levels of a particle in a cubical box with side L are given by [�D.��b–
���], E n = h 2 n 2 �8mL 2 , with n 2 = n 2x + n 2y + n 2z . When the side is decreased to
0.9 × L the energies become E n′ = h 2 n 2 �8m(0.9 × L)2 = h 2 n 2 �8m(0.81 × L 2 )
giving a fractional change of
E n′ − E n [h 2 n 2 �8m(0.81 × L 2 )] − [h 2 n 2 �8mL 2 ] 1
= = − 1 = �.���
En h 2 n 2 �8mL 2 0.81

E�D.��(b) �e energy levels of a particle in a box of length L are given by [�D.�–���],

E n = h 2 n 2 �8mL 2 . �is energy is equal to the average thermal energy when
kT�2 = h 2 n 2 �8mL 2 , leading to n = (2L�h)(mkT)1�2 .
For an argon atom, mass 39.95 m u in a box for length 0.1 cm this evaluates as
2(0.1 × 10−2 m)
n=
6.6261 × 10−34 J s
× �(39.95 × 1.6605 × 10−27 kg) × (1.3806 × 10−23 J K−1 ) × (298 K)�
1�2

= 5.0 × 107

E�D.��(b) �e wavefunction of a particle in a square box of side length L with quantum

numbers n 1 = 1, n 2 = 3 is ψ 1,3 (x, y) = (2�L) sin (πx�L) sin (3πy�L). �e cor-
responding probability density is P1,3 (x, y) = (2�L) sin2 (πx�L) sin2 (3πy�L).
2

�e probability density is maximized when sin (πx�L) × sin2 (3πy�L) = 1

2

which occurs only when each sin term is equal to ±1. �e term in x is equal to
� when πx�L = π�2 and hence x = L�2. For the term in y
sin (3πy�L) = ±1
3πy�L = π�2, 3π�2, 5π�2 hence y = L�6, L�2, 5L�6.

Hence the maxima occur at (x, y) = (L�2, L�6), (L�2, L�2), (L�2, 5L�6)
Nodes occur when the wavefunction passes through zero, which is when either
of the sin terms are zero, excluding the boundaries at x = 0, L y = 0, L because at
these points the wavefunction does not pass through zero. �ere are therefore
no nodes associated with the function sin (πx�L). In the y-direction there are
nodes when
sin (3πy�L) = 0
3πy�L = π, 2π hence y = L�3, 2L�3
�ere is thus a node when y = L�3 and for any value of x, that is a nodal line at
y = L�3 and parallel to the x-axis . Likewise the node at y = 2L�3 corresponds
to a nodal line at y = 2L�3 and parallel to the x-axis .
E�D.��(b) �e energy levels for a �D rectangular box, side lengths L 1 , L 2 are

h 2 n 12 n 22
E n 1 ,n 2 = � + �
8m L 21 L 22

where n 1 and n 2 are integers greater than or equal to 1.

For the speci�c case where L 1 = L, L 2 = 2L,

h 2 n 12 n 22 h2 n2
E n 1 ,n 2 = � 2+ �= �n 12 + 2 �
8m L (2L) 2 8mL 2 4

�e energy of the state with n 1 = 2, n 2 = 8 is then

h2 82 h2
E 2,2 = �22 + � = (20)
8mL 2 4 8mL 2

By inspection, the �rst term in the sum is equal to 4 and the second is equal to
16, it can be arranged for these to be swapped. �is requires n 12 = 16 and so n 1 =
4 and n 22 �4 = 4, and so n 2 = 4. Hence, the state (4, 4) is degenerate with (2, 8) .
�e question notes that degeneracy frequently accompanies symmetry, and
suggests that one might be surprised to �nd degeneracy in a box with unequal
lengths. Symmetry is a matter of degree. �is box is less symmetric than a
square box, but it is more symmetric than boxes whose sides have a non-integer
or irrational ratio. Every state of a square box except those with n 1 = n 2 is
degenerate (with the state that has n 1 and n 2 reversed). Only a few states in this
rectangular box are degenerate. In this system, a state (n 1 , n 2 ) is degenerate
with a state (n 2 �2, 2n 1 ) as long as the latter state (a) exists (that is n 2 �2 must
be an integer) and √ (b) is distinct from (n 1 , n 2 ). A box with incommensurable
sides, say, L and 2L, would have no degenerate levels .

E�D.��(b) �e energy levels of a cubic box are given by [�D.��b–���]

h2
E n 1 ,n 2 ,n 3 = (n 2 + n 22 + n 32 )
8mL 2 1
where n 1 , n 2 , n 3 are integers greater than or equal to 1. Hence the lowest energy
state is that with n 1 = n 2 = n 3 = 1, with energy

h2 h2
E(1,1,1) = (1 2
+ 1 2
+ 1 2
) = (3)
8mL 2 8mL 2
and so the energy of the level with energy 14�3 times that of the lowest is
14h 2 �8mL 2 , which will be produced by states for which n 12 +n 22 +n 32 = 14. �ere
are six states with this energy, (n 1 , n 2 , n 3 ) = (1, 2, 3), (1, 3, 2), (2, 1, 3), (2, 3, 1),
(3, 1, 2), (3, 2, 1), and so the degeneracy is � .

E�D.��(b) �e transmission probability [�D.��a–���] depends on the energy of the tun-

nelling particle relative to the barrier height (ε = E�V0 = (1.5 eV)�(2.0 eV)
 = 0.75), the width of the barrier, (L = 100 pm), and the decay parameter of the
wavefunction inside the barrier (κ)
(2m(E − V0 ))1�2
κ=
ħ
(2 × (1.6726 × 10−27 kg) × [(2.0 − 1.5) eV × 1.6022 × 10−19 J eV−1 ])1�2
=
1.0546 × 10−34 J s
= 1.58... × 10 m
11 −1

Such that κL = (1.58... × 1011 m−1 ) × (100 × 10−12 m) = 15.8..., and so the
transmission probability is given by
−1 −1
(eκ L − e−κL )2 (e15.8 ... − e−15.8 ... )2
T = �1 + � = �1 + � = 5.7 × 10−14
16ε(1 − ε) 16 × 0.75 × (1 − 0.75)

P�D.� (i) �e energy levels of a particle in a cubic box are given by [�D.��b–���]
E(n x , n y , n z ) = h 2 n 2 �8mL 2 where n 2 = n 2x + n 2y + n 2z , and L is the side
length of the box, such that its volume is V = L 3 . For a cubic box, volume
1.00 m3 , L = (1.00 m3 )1�3 = 1.00 m. �e mass of a N� molecule is
28.00 m u = 4.6494 × 10−26 kg. To �nd the value of n that makes the
energy equal to the average thermal energy, set E n = 32 kT and solve for n
√
L 12mkT
n=
h
(1.00 m)×�12×(4.6494 × 10−26 kg)×(300 K)×(1.3806 × 10−23 J K−1 )�
1�2

=
6.6261 × 10−34 J s
= 7.25 × 10 10

(ii) �e separation between neighbouring levels is

h2 h 2 (2n + 1)
∆E = E n+1 − E n = �(n + 1) 2
− n 2
� =
8mL 2 8mL 2
and so for this case
(6.6261 × 10−34 J s)2 × (2 × 7.25 × 1010 + 1)
∆E = = 1.71 × 10−31 J
8 × (4.6494 × 10−26 kg) × (1.00 m)2
(iii) �e de Broglie wavelength is given by [�A.��–���], λ = h�p, and the
kinetic energy is E k = p2 �2m. In this case E k = 32 kT, hence p2 �2m = 32 kT
√
which is rearranged for the momentum to give p = 3mkT. Hence, the
de Broglie wavelength is
h
λ= √
3mkT
6.6261 × 10−34 J s
=
�3×(4.6494 × 10−26 kg)×(1.3806 × 10−23 J K−1 )×(300 K)�
1�2

= 27.6 pm
P�D.� �e wavefunction with n = 2 is ψ 2 (x) = (2�L)1�2 sin(2πx�L), and this is used
in [�C.��–���], �Ω� = ∫ ψ ∗ Ω̂ψ dτ, to compute the expectation value for the
cases Ω̂ = p̂ x = (ħ�i)d�dx and Ω̂ = p̂2x . �e e�ect of p̂ x on the wavefunction is

p̂ x ψ 2 = (ħ�i)d�dx �(2�L)1�2 sin(2πx�L)� = (ħ�i)(2�L)1�2 (2π�L) cos(2πx�L)

and the e�ect of p̂2x is found by applying p̂ x to this result

p̂2x ψ 2 = (ħ�i)d�dx �(ħ�i)(2�L)1�2 (2π�L) cos(2πx�L)�

= ħ 2 (2�L)1�2 (2π�L)2 sin(2πx�L)

Hence
L L
�p x � = � ψ ∗2 p̂ x ψ 2 dx = (ħ�i)(2�L)(2π�L) � sin(2πx�L) cos(2πx�L)d x
0 0

�is integral is of the form of Integral T.� with k = 2π�L, a = L

�p x � = (ħ�i)(2�L)(2π�L) × (L�4π) sin2 (2πL�L) = 0

L L
�p2x � = � ψ ∗2 p̂2x ψ 2 dx = ħ 2 (2�L)(2π�L)2 � sin2 (2πx�L) dx
0 0

�is integral is of the form of Integral T.� with k = 2π�L, a = L

�p2x � = ħ 2 (2�L)(2π�L)2 × [L�2 − (L�8π) sin(4πL�L)] = 4π 2 ħ 2 �L 2

P�D.� �e wavefunction of the state with quantum number n, in the range 0 ≤ x ≤ L,

is ψ n (x) = (2�L)1�2 sin(nπx�L).
(a) �e probability density is Pn (x) = �ψ n (x)�2 = (2�L) sin2 (nπx�L) which
is symmetric about x = L�2, meaning that Pn (L�2 + x) = Pn (L�2 − x) for
all x. Hence, the particle is equally likely to be at position x as at L−x, and
so the average position must be in the middle of this range, i.e. �x� = L�2 .
(b) �e particle has kinetic energy (only) when it is in the box, but as it
is constrained to be within the box it must move back and forth at a
constant speed between the two in�nite walls. �erefore the probability
of the particle travelling with momentum +p (to the right) is equal to the
probability of it travelling with momentum −p (to the le�), and so the
average value of the momentum must be 0 .
(c)
L L
�x 2 � = � ψ ∗n x̂ 2 ψ n dx = (2�L) � x 2 sin2 (nπx�L) dx
0 0

�e integral is of the form of Integral T.�� with a = L and k = nπ�L

�x 2 � = (2�L)[L 3 �6 − �L 3 �4πn − L 3 �8n 3 π 3 � sin(2nπL�L)

− �L 3 �4n 2 π 2 � cos(2nπL�L)] = L 2 (1�3 − 1�2n 2 π 2 )
 (d) �e wavefunction is an eigenfunction of the hamiltonian which, because
the potential is zero inside the box, is just the operator for kinetic en-
ergy. �is operator can be written p̂2x �2m, so the wavefunction is also an
eigenfunction of p̂2x with eigenvalue 2m times the energy eigenvalue. In
this case, the eigenvalue of p̂2x is 2m × n 2 h 2 �8mL 2 = n 2 h 2 �4L 2 . Because
the wavefunction is an eigenfunction of p̂2x , the expectation value is equal
to the eigenvalue: �p2x � = n 2 h 2 �4L 2 .

P�D.� (a) Because the particle is moving back and forth with constant speed its
probability density within the box must be uniform at P0 . �e total prob-
ability must be �, so it follows that ∫0 P0 dx = 1. Evaluating the integral
L

give P0 L = 1, hence P0 = 1�L, as required.

(b) �e average value of any quantity is the value of that quantity in an in-
�nitesimal interval at an arbitrary position, multiplied by the probability
of being in that interval and then summed (integrated) over all possible
positions. If the probability density is P(x), the required average is �x n � =
∫0 x P(x)dx. �e integral is only over the range 0 to L because outside
L n

this region the probability density is zero.

(c)
L L
�x� = � xP(x) dx = (1�L) � x dx
0 0

= (1�L) (x 2 �2)�0 = (1�L)(L 2 �2 − 0) = L�2

L

L L
�x 2 � = � x 2 P(x) dx = (1�L) � x 2 dx
0 0

= (1�L) (x 3 �3)�0 = (1�L)(L 3 �3 − 0) = L 2 �3

L

(d) �x� is identical with the quantum result for all values of n. �e quan-
tum result for �x 2 � is L 2 (1�3 − 1�2n 2 π 2 ). For large n the second term
in parentheses becomes negligible compared to the �rst, in which case
�x 2 � = L 2 �3, which is the classical result. �e correspondence principle
is satis�ed.

P�D.�� (a) Outside the box, L�2 < x < −L�2, the potential is in�nite and so the wave-
function is zero. Inside the box the potential is zero and the Schrödinger
equation is (−ħ 2 �2m)d2 ψ�dx 2 = Eψ. �e wavefunction must be contin-
uous at the walls of the box so the boundary conditions are ψ(±L�2) = 0
(b) Substituting ψ(x) = cos(kx) into the Schrödinger equation gives

−(ħ 2 �2m)(d2 �dx 2 ) cos kx = −(ħ 2 �2m)(−k 2 cos kx)

= E cos kx

which is true if E = ħ 2 k 2 �2m. �e boundary conditions are satis�ed if

cos(±kL�2) = cos(kL�2) = 0, which occurs if kL�2 = (2n + 1)π�2 for
 integer n; it follows that k = (2n + 1)π�L. Negative values of n do not
generate distinct solutions: for example if n = −2, k = −3π�L and the
wavefunction is cos(−3πx�L). However, because cos(−θ) = cos(θ) this
wavefunction is cos(3πx�L), which is that for n = 1. All negative values
of n therefore simply duplicate solutions given by positive values of n. In
summary
ψ n (x) = cos([2n+1]πx�L) E n = h 2 (2n+1)2 �8mL 2 n = 0, 1 . . .
It follows that the three lowest energy wavefunctions are ψ 0 = cos(πx�L),
ψ 1 = cos(3πx�L), and ψ 3 = (cos 5πx�L); these are depicted in Fig. �.�

ψn
1.0 ψ0
ψ1
ψ2
0.5

x�L
−0.4 −0.2 0.2 0.4
−0.5

−1.0

(c) Substituting ψ(x) = sin k ′ x into the Schrödinger equation gives

−(ħ 2 �2m)(d2 �dx 2 )(sin k ′ x) = −(ħ 2 �2m)(−k ′2 sin k ′ x) = E sin k ′ x
�e energy is therefore E = ħ 2 k ′2 �2m. �e boundary conditions are
sin(±k ′ L�2) = 0, which is satis�ed by k ′ L�2 = n′ π for integer n′ . Negative
values of n′ do not generate distinct wavefunctions and n′ = 0 is not
permitted as the wavefunction is zero everywhere. In summary
ψ ′n ′ (x) = sin(2n′ πx�L) E n ′ = h 2 (2n′ )2 �8mL 2 n′ = 1, 2 . . .
�e wavefunctions with the three lowest energies are thus ψ ′1 = sin(2πx�L),
ψ ′2 = sin(4πx�L), and ψ ′3 = sin(6πx�L); these are depicted in Fig. �.�.
(d) Expressed as multiples of h 2 �8mL 2 the cosine solutions have energies �,
�, ��, . . . , and the sine solutions have energies �, ��, ��, . . . . �ese are the
same set of energies as for the box between � and L, n 2 h 2 �8mL 2 .
(e) �e normalized cos wavefunctions are ψ = N cos[(2n + 1)πx�L], and
are normalized when ∫−L�2 ψ ∗ ψ dx = 1. �e integral is evaluated by �rst
L�2

using the identity cos2 x + sin2 x = 1 and then Integral T.�

L�2 L�2
N2 � cos2 [(2n + 1)πx�2L] dx = N 2 � 1 − sin2 [(2n + 1)πx�2L] dx
−L�2 L�2
−L�2
= N 2 x − N 2 {x�2 − (L�2(2n + 1)π) sin[(2n + 1)πx�L]}�L�2 = N 2 (L�2)
 ψ ′n ′
1.0 ψ ′1
ψ ′2
0.5 ψ ′3

x�L
−0.4 −0.2 0.2 0.4
−0.5

−1.0

setting this equal to � gives N = (2�L)1�2 . Similarly for the sin functions,
again using Integral T.�
L
N2 � sin2 [2n′ πx�L]dx = N 2 [x�2 − (L�8n′ π) sin(4n′ πx�L)�L�2
L�2
0
= N 2 (L�2)

setting this equal to � gives N = (2�L)1�2 .

(f) �e probability density for all wavefunctions is symmetric about the cen-
ter of the box, which at this case is at x = 0. Hence, the average value of x
must be at the center, and so �x� = 0.

P�D.�� �e text de�nes the transmission probability as the ratio �A′ �2 ��A�2 , where the
coe�cients A and A′ are de�ned in [�D.��–���] and [�D.��–���] respectively.
Four equations are given in [�D.��a–���] and [�D.��b–���] for the �ve un-
known coe�cients of the full wavefunction.
(a) A + B = C + D
(b) CeκW + De−κW = A′ eikW
(c) ikA − ikB = κC − κD
(d) κCeκW − κDe−κW = ikA′ eikW
�e coe�cient A′ is needed in terms of A alone, and hence B, C and D need to
be eliminated. B occurs only in (a) and (c). Solving these equations and setting
the results equal to each other yields

B = C + D − A = A − (κ�ik)C + (κ�ik)D

Solving this for C,

2A + D(κ�ik − 1) 2Aik + D(κ − ik)
C= =
κ�ik + 1 κ + ik
�e desired A′ appears only in (b) and (d). Solve these for A′ and set them
equal to each other.

A′ = e−ikW (CeκW − De−κW ) = (κe−ikW �ik)(CeκW − De−κW )

Solve the resulting equation for C, and set it equal to the previously obtained
expression for C

(κ�ik + 1)De−2κW (κ + ik)De−2κW 2Aik + D(κ − ik)

C= = =
κ�ik − 1 κ − ik κ + ik
Solve this resulting equation for D in terms of A

(κ + ik)2 e−2κW − (κ − ik)2 2Aik

D=
(κ − ik)(κ + ik) κ + ik
and so
2Aik(κ − ik)
D=
(κ + ik)2 e−2κ L − (κ − ik)2
Substituting this expression back into the expression for C yields

2Aik(κ + ik)e−2κW
C=
(κ + ik)2 e−2κW − (κ − ik)2
Substituting this into expression (b) for A′

2Aike−ikW
A′ = [(κ + ik)e−κW + (κ − ik)e−κ L ]
(κ + ik)2 e−2κL − (κ − ik)2

A′ 4ikκe−ikW e−κW 4ikκe−ikW

= =
A (κ + ik)2 e−2κL − (κ − ik)2 (κ + ik)2 e−κ L − (κ − ik)2 eκW
�is leads to a transition probability of

A′ 4ikκe−ikW −4ikκeikW
2
T =� � =� � � �
A (κ + ik)2 e−κL − (κ − ik)2 eκW (κ − ik)2 e−κ L − (κ + ik)2 eκW
�e denominator, expanded separately is

(κ + ik)2 (κ − ik)2 e−2κW − (k − ik)4 − (k + ik)4 + (κ − ik)2 (κ + ik)2 e2κW

= (κ 2 + k 2 )2 (e2κW + e−2κW ) − (κ 2 − 2iκk − k 2 )2 − (κ 2 + 2iκk − k 2 )2
= (κ 4 + 2κ 2 k 2 + k 4 )(e2κW + e−2κW ) − (2κ 4 − 12κ 2 k 2 + 2k 4 )

�e term 12κ 2 k 2 can be written as −4κ 2 k 2 + 16k 2 κ 2 , which allows terms to be

collected

(κ 4 +2κ 2 k 2 +k 4 )(e2κW −2+e−2κW )+16κ 2 k 2 = (κ 2 +k 2 )2 (eκW −e−κW )2 +16κ 2 k 2

Hence, the probability is

16k 2 κ 2
T=
(κ 2 + k 2 )2 (eκW − e−κW )2 + 16κ 2 k 2
 to proceed to eqn �D.��a, invert this expression
−1
(κ 2 + k 2 )2 (eκW − e−κW )2 + 16κ 2 k 2
T =� �
16k 2 κ 2
−1
(κ 2 + k 2 )2 (eκW − e−κW )2
=� + 1�
16κ 2 k 2

Now express (k 2 + κ 2 )�k 2 κ 2 in terms of a ratio of energies, ε = E�V0 . k and κ

are de�ned by [�D.��–���] and [�D.��–���], respectively. �e factors in ħ and
m cancel out, leaving κ ∝ (V0 − E) and k ∝ E, which gives

(κ 2 + k 2 )2 (E + V0 − E)2 V02 1
= = =
k κ
2 2 E(V0 − E) E(V0 − E) ε(1 − ε)

making the transmission probability

−1
(eκW − e−κW )2
T =� + 1�
16ε(1 − ε)

When κW � 1 the negative term inside the parentheses is negligible compared

to the positive term, and the 1 is negligible compared to the exponential term,
such that
−1
e2κW
T ≈� � = 16ε(1 − ε)e−2κW
16ε(1 − ε)

P�D.�� �e probability of the particle being inside the barrier is the integral of the
probability density, �ψ�2 , within the barrier which extends from x = 0 to x = ∞
∞ ∞
P=� (Ne−κ x )2 dx = N 2 � e−2κ x dx = N 2 �2κ
0 0

�e average penetration depth is interpreted as the expectation values of x,

computed inside the barrier. �e required integral is of the form of Integral
G.� with k = 2κ.
∞ ∞
�x� = � x(Ne−κ x )2 dx = N 2 � xe−2κ x dx = N 2 �(2κ)2
0 0

D�E.� For the harmonic oscillator the spacing of the energy levels is constant. �ere-
fore, relative to the energy of the oscillator, the spacing becomes progressively
smaller as the quantum number increases. In the limit of very high quantum
numbers this spacing becomes negligible compared to the total energy, and
e�ectively the energy can take any value, as in the classical case.
 As is shown in Fig. �E.� on page ���, as the quantum number becomes large the
probability density clusters more and more around the classical turning points
of the classical harmonic oscillator (that is, the points at which the kinetic
energy is zero). Because the classical oscillator is moving most slowly near
these points, they are the displacements at which it is most probable that the
oscillator will be found. Again, the quantum and classical results converge at
high quantum numbers

E�E.�(b) �e zero-point energy of a harmonic oscillator is given by [�E.�–���], E 0 =

1
2
ħω, where the frequency ω is given by [�E.�–���], ω = (k f �m)1�2 . For this
system,

E0 = × (1.0546 × 10−34 J s) × �(285 N m−1 )�(5.16 × 10−26 kg)�

1 1�2
2

= 3.92 × 10−21 J

E�E.�(b) �e separation between adjacent energy levels of a harmonic oscillator is [�E.�–

���], ∆E = ħω, where the frequency, ω is given by [�E.�–���], ω = (k f �m)1�2 .
�is is rearranged for the force constant as k f = m(∆E�ħ)2 . Evaluating this
gives

k f = (2.88 × 10−25 kg) × �(3.17 × 10−21 J)�(1.0546 × 10−34 J s)� = 260 N m−1
2

E�E.�(b) �e separation between adjacent energy levels of a harmonic oscillator is [�E.�–

���], ∆E = ħω, where the frequency, ω is given by [�E.�–���], ω = (k f �m)1�2 .
�e Bohr frequency condition [�A.�–���], ∆E = hν, can be rewritten in terms
of the wavelength as ∆E = hc�λ. �e wavelength of the photon corresponding
to a transition between adjacent energy levels is therefore given by ħω = hc�λ,
or ħ(k f �m)1�2 = hc�λ. Solving for λ gives λ = 2πc�(k f �m)1�2 ; with the data
given

2π × (2.9979 × 108 m s−1 )

λ=
�(544 N m−1 )�(15.9949 × 1.6605 × 10−27 kg)�
1�2

= 1.32 × 10−5 m

E�E.�(b) �e wavefunctions are depicted in Fig. �E.� on page ���; they are real. Two
wavefunctions are orthogonal if ∫ ψ ∗i ψ j dτ = 0. In this case the wavefunctions
are ψ 1 (y) = N 1 ye−y �2 and ψ 2 (y) = N 2 (y 2 − 1)e−y �2 , and the integration is
2 2

from y = −∞ to +∞. �e integrand is ψ 2 ψ 1 = N 2 N 1 (y 3 − y)e−y , which is

2

an odd function, meaning that its value at −y is the negative of its value at +y.
�e integral of an odd function over a symmetric range is zero, hence these
wavefunctions are orthogonal.
E�E.�(b) �e zero-point energy of a harmonic oscillator is given by [�E.�–���], E 0 =
1
ħω, where the frequency ω is given by [�E.�–���], ω = (k f �µ)1�2 . �e e�ec-
tive mass µ of a diatomic AB is given by [�E.�–���], µ = (m A m B )�(m A + m B ).
2

In the case of a homonuclear diatomic A� this reduces to µ = m A �2. For this

system,

E0 = 1
2
× (1.0546 × 10−34 J s)
× �(2293.8 N m−1 )�( 12 × 14.0031 × 1.6605 × 10−27 kg)�
1�2

= 2.3422 × 10−20 J

E�E.�(b) �e energy levels of a harmonic oscillator are [�E.�–���], E υ = (υ + 12 )ħω, with

ω = (k f �m)1�2 and υ = 0, 1, 2.... �e energy of the state with υ = 1 is E 1 = 32 ħω.

(i) For the system with k f = 1000 N m−1 the energy of the state with υ = 1 is

E1 = 3
2
× (1.0546 × 10−34 J s) × [(1000 N m−1 )�(1 × 1.6605 × 10−27 kg)]1�2
= 1.22... × 10−19 J = 1.23 × 10−19 J

�e classical turning points of this state occur when E 1 = 12 k f x tp

2
. Solving
�
this for x tp leads to x tp = ± 2E 1 �k f , giving a separation of
� �
2 2E 1 �k f = 2 2 × (1.22... × 10−19 J)�(1000 N m−1 ) = 31.3... pm

As a percentage of the typical bond length, 110 pm, this is

(31.3... pm)�(110 pm) × 100% = 28.5%

(ii) For the system with k f = 100 N m−1 the energy of the state with υ = 1 is

E1 = 3
2
× (1.0546 × 10−34 J s) × [(100 N m−1 �(1 × 1.6605 × 10−27 kg)]1�2
= 3.88... × 10−20 J = 3.88 × 10−20 J

�e classical turning points of this state occur when E 1 = 12 k f x tp

2
. Solving
�
this for x tp leads to x tp = ± 2E 1 �k f , giving a separation of
� �
2 2E 1 �k f = 2 2 × (3.88... × 10−20 J)�(100 N m−1 ) = 55.7... pm

As a percentage of the typical bond length, 110 pm, this is

(55.7... pm)�(110 pm) × 100% = 50.7%

E�E.�(b) �e wavefunctions are depicted in Fig. �E.� on page ���. �e general form of
the harmonic oscillator wavefunctions is ψ υ = N υ H υ (y)e−y �2 , where N υ is
2

a normalization constant and H υ (y) is the Hermite polynomial of order υ in

the reduced position variable y. Nodes occur when the wavefunction passes
 through zero. �e wavefunction asymptotically approaches zero at y = ±∞,
but as the function does not pass through zero these limits do not count as
nodes. �e nodes in the wavefunction therefore correspond to the solutions of
H υ (y) = 0. H υ (y) is a polynomial of order υ, meaning that the highest power
of y that occurs is y υ ; such polynomials in general have υ solutions and hence
there are υ nodes. �erefore (a) the wavefunction with υ = 5 has 5 nodes; (b)
the wavefunction with υ = 35 has 35 nodes.

�e wavefunction with υ = 3 is ψ 3 (y) = N 3 (y 3 − 3y)e−y �2 . Nodes occur when

2
E�E.�(b)
the wavefunction passes through zero; the wavefunction approaches zero at
y = ±∞, but these do not count as nodes as the wavefunction does not pass
through zero. It is evident that the nodes occur when y 3 − 3y = y(y 2 − 3) = 0
√
which solves to give nodes at y = 0, ± 3 .

�e wavefunction with υ = 3 is ψ 3 (y) = N 3 (8y 3 − 12y)e−y �2 , which gives a

2
E�E.�(b)
probability density of P(y) = �ψ 3 (y)�2 = N 32 (8y 3 − 12y)2 e−y . �e extrema are
2

located by di�erentiating the wavefunction, setting the result to 0 and solving

for y. �e di�erential is evaluated using the product rule

dψ 3 (y) � d(8y 3 − 12y)2 −y 2 de−y �

2

= N 32 e + (8y 3 − 12y)2
dy � dy dy �
= N 32 [2(8y 3 − 12y)(24y 2 − 12)e−y + (8y 3 − 12y)2 × (−2ye−y )]
2 2

It is necessary to use mathematical so�ware to �nd the solutions of dψ 3 (y)�dy =

0; these solutions are

0.000 ± 0.6021 ± 1.225 ± 2.0341 ±∞

It is evident from inspection of the wavefunction that y = 0 is a mimimum in

the probability density, and that there is also a minimum when (8y 2 − 12) = 0,
which corresponds to y = ±1.225. It follows that maxima occur at y = ±0.6021
and y = ±2.034 .

P�E.� (a) In the case that m B � m A , m A + m B ≈ m B , and so µ AB ≈ m A m B �m B =

m A . �e ratio of the vibrational frequencies is then

ω A′ B = ω AB (µ AB �µ A′ B )1�2 ≈ ω AB (m A �m A′ )1�2

If the frequencies are expressed in Hz the analogous result is

ν A′ B ≈ ν AB (m A �m A′ )1�2

(b) Using the previous result gives ν 2H35 Cl ≈ ν 1H35 Cl (m 1H �m 2H )1�2 = (5.63 ×
1014 Hz) × (1 m u �2 m u )1�2 = 3.98 × 1014 Hz .
 (c) Comparing it to the result from Problem P�E.�, there is a 1.5% di�erence,
which is relatively small. �e assumption of replacing the e�ective mass
by the mass of the lighter nucleus is quite a good approximation.
(d) A C–H vibration in an organic molecule can be thought of as the H atom
moving against the rest of the molecule, which has a much greater mass.
�erefore, to some rough approximation such vibrations can be modelled
by a diatomic X–1 H in which m X � m H . In such a situation the analysis
in part (a) applies and the vibrational frequency of X–2 H is well approxi-
mated as (1 m u �2 m u )1�2 = 0.7 times that of X–1 H.

�e vibrational frequency in Hz, ν is given by ν = (1�2π) (k f �µ)

1�2
P�E.� ; using this
the following table is drawn up

12
C 16O 13
C 16O 12
C 18O 13
C 18O
µ�m u 6.85... 7.17... 7.2 7.54...
ν�THz 64.3 62.8 62.7 61.3

P�E.� As in Problem P�E.�, the force constant can be found from the wavenumber of
the υ = 0 → 1 transition, k f = µ(2πν̃c)2 . �is allows the following table to be
drawn up

1
H 35Cl 1
H 81Br 1
H 127I 12
C 16O 14
N 16O
ν̃� cm−1 2990 2650 2310 2170 1904
µ� m u 0.972... 0.987... 0.992... 6.85... 7.46...
kf � N m −1
512 409 312 1902 1595

Hence, the order of increasing sti�ness is HI<HBr<HCl<NO<CO

P�E.� Assuming that one can identify the CO peak in the infrared spectrum of the
complex, taking infrared spectra of each of the isotopic variants of the com-
plexes can show which atom binds to the haem group and determine the C – O
force constant. Compare isotopic variants to ��C ��O as the standard; when an
isotope changes but the vibrational frequency does not, then the atom whose
isotope was varied is the atom that binds to the haem. (As usual, the better the
experimental results agree with the whole set of predictions, the more con�-
dence one would have with the conclusion.)
As it is expected that the force constant for the bond will remain constant,
and that the atom that bonds to the haem group will be immobilized, meaning
that appropriate mass for this system is the mass of the unbound atom, allows
predictions to be made for the �wavenumbers of each isotope in the case of C
and O binding, using ν̃ 2 = ν̃ 1 µ 1 �µ 2 , where 1 refers to the free case and 2 to
the bound case.
 isotopomer ν̃�cm−1 ν̃�cm−1
if C binds if O binds
12 16
C O 1421 1640
13 16
C O 1421 1576
12 18
C O 1339 1640
13
C 18O 1339 1576

�e force constant is found using ν̃ = (1�2πc) (k f �µ) , rearranged to k f =

1�2

µ(2πν̃c)2 .

�e ground-state wavefunction is found from [�E.�–���] as ψ 0 (y) = N 0 e−y �2

2
P�E.�� .
�e normalization constant is found by evaluating
+∞ +∞
N 02 � e−y dy = 2N 02 � e−y dy = 2N 02 × ( 12 π 1�2 ) = 1
2 2

−∞ 0

where required integral is of the form of Integral G.� with k = 1. �e normalized

wavefunction is therefore ψ 0 (y) = π−1�4 e−y �2 .
2

(a) For the expectation value of y, the integral to evaluate is

∞ ∞
�y� = � ψ ∗0 y ψ 0 dy = π−1�2 � y e−y dy
2

−∞ −∞

�e integrand is an odd function, meaning that its value at −y ′ is the

negative of its value at y ′ , and so when integrated over a symmetrical
range about y = 0 the result is necessarily zero. Hence �y� = 0 .
(b) To calculate �y 2 � the required integral is of the form of Integral G.� with
k=1
∞ ∞
�y 2 � = � ψ ∗0 y 2 ψ 0 dy = π−1�2 � y 2 e−y dy
2

−∞ −∞
∞
= 2π−1�2 � y 2 e−y dy = 2π−1�2 × 14 π 1�2 =
2
1
2
0

(c) �e �rst excited state is ψ 1 (y) = N 1 ye−y �2

2
. �e normalization constant
is found by evaluating
+∞ +∞
N 12 � y 2 e−y dy = 2N 12 � y 2 e−y dy = 2N 12 × ( 14 π 1�2 ) = 1
2 2

−∞ 0

where required integral is of the form of Integral G.� with k = 1. �e

normalized wavefunction is therefore ψ 1 (y) = (4�π)1�4 y e−y �2 .
2

�e expectation value of y is zero for the same reason as in (a). To calcu-

late �y 2 � the required integral is of the form of Integral G.� with k = 1
∞ ∞
�y 2 � = � ψ ∗1 y 2 ψ 1 dy = (4�π)1�2 � y 4 e−y dy
2

−∞ −∞
∞
= 2(4�π)1�2 � y 4 e−y dy = 2(4�π)1�2 × 38 π 1�2 =
2
3
2
0
P�E.�� In general
∞ ∞
�x n �υ = α n �y n �υ = α n � ψ ∗υ y n ψ υ dx = α n+1 � ψ 2υ y n dy
−∞ −∞

as x = α y. �en
∞
�x 3 �υ = α 4 � ψ 2υ y 3 dy = 0
−∞

as the square of the wavefunction always an even function, the integrand is odd.
∞
�x 4 �υ = α 5 � ψ υ y 4 ψ υ dy
−∞

Consider the term y 4 ψ υ = y 4 N υ H υ e−y �2 . �e y 4 H υ term can be rewritten by

2

using the property yH υ = υH υ−1 + 12 H υ four times, as

y 4 H υ = y 3 [yH υ ] = υy 3 H υ−1 + 12 y 3 H υ
= y 2 [υ(υ − 1)H υ−2 + (υ + 12 )H υ + 14 H υ+2 ]
= y[ 14 ( 12 H υ+3 + (υ + 2)H υ+1 ) + (υ + 12 )( 12 H υ+1 + υH υ−1 )
+ υ(υ − 1)( 12 H υ−1 + (υ − 2)H υ−3 ]
= y � 18 H υ+3 + 34 (υ + 1)H υ+1 + 32 υ 2 H υ−1 + υ(υ − 1)(υ − 2)H υ−3 �

�e only terms from the above that will contribute to the expectation value will
be those that produce H υ , due to orthogonality of the hermite polynomials.
�ese are yH υ−1 and yH υ+1 . Hence,

= 34 y[(υ + 1)H υ+1 + 2υ 2 H υ−1 ] + ...

= 34 �(υ + 1)( 12 H υ+2 + (υ + 1)H υ ) + 2υ 2 ( 12 H υ + (υ − 1)H υ−2 )� + ...
= 34 [(υ + 1)2 + υ 2 ]H υ + ... = 34 [2υ 2 + 2υ + 1]H υ ...

Hence,
∞
�x 4 �υ = α 4 34 [2υ 2 + 2υ + 1] � (N υ H υ e−y ) d(α y) = α 4 34 [2υ 2 + 2υ + 1]
�2 2
2

−∞

∞
For the last step the normalization condition ∫−∞ (N υ H υ e−y ) d(α y) = 1 is
�2 2
2

used.

P�E.�� As is shown in Example �E.� on page ���, in terms of the dimensionless variable
y the classical turning points are at y tp = ±(2υ + 1)1�2 , where υ is the quantum
number of the state. �e wavefunction of the state with quantum number υ
is ψ υ = N υ H υ e−y �2 , where H υ is the Hermite polynomial of order υ. �e
2

normalization constant N υ is found from

∞
N υ2 � H υ2 e−y dy = 1
2

−∞
 ∞
From Table �E.� on page ��� these polynomials have the property ∫−∞ H υ2 e−y dy =
2

π 1�2 2υ υ! so it follows that N υ2 = 1�(π 1�2 2υ υ!). �e probability of �nding the

particle outside the range of the turning points is then
∞ 2 ∞
Pυ = 2 �√ �ψ υ �2 dy = � H υ2 e−y dy
2
√
2υ+1 π 1�2 2υ υ! 2υ+1
1 ∞
= � H υ2 e−y dy
2
√
π 2 υ!
1�2 υ−1 2υ+1

�e integral is evaluated using mathematical so�ware to give the results in the

following which are plotted in Fig. �.�. �e probability of a classical oscillator
being found in a non-classical region is, of course, zero and the correspondence
principle indicates that the quantum result must converge to this value as the
quantum number becomes large. �e results show that P is indeed a decreasing
function of υ, albeit rather slowly. �e probability reduces to about �.�� for
υ = 200.

υ 0 1 2 3 4 5 6 7
Pυ 0.157 0.112 0.0951 0.0855 0.0789 0.0740 0.0702 0.0670

0.15

0.10
Pυ

0.05

0.00
0 1 2 3 4 5 6 7
υ

P�E.�� Oscillations are expected about a minimum in the potential energy, because
this corresponds to the equilibrium arrangement. For a potential of the form
V = V0 cos 3�, the (�rst) minimum is when 3� = π, that is � = π�3 or 60○ . �e
form of the potential close to the minimum is found by expanding the function
in a Taylor series about the point � = π�3

dV (�) d2 V (�)
V �V0 = V (π�3) + � � (� − π�3) + 12 � � (� − π�3)2
d� �=π�3
d� 2 �=π�3

= cos(π) + (−3 sin 3�)�=π�3 (� − π�3) + 12 (−9 cos 3�)�=π�3 (� − π�3)2

= −1 + 12 × 9(� − π�3)2
 Apart from the constant, the leading term is quadratic in the displacement from
the minimum at � = π�3. By analogy with the harmonic potential V = 12 k f x 2 ,
the force constant is 9V0 .

�e energy levels are therefore

E υ = (υ + 12 )ħω ω = (9V0 �m eff )1�2

where m eff is the appropriate e�ective mass for the motion.

As the energy increases the amplitude of the motion increases and it begins to
sample parts of the potential which are no longer well-represented by a quadratic
function. Additional terms are needed to describe the potential, and from the
form of the cosine function it is evident that these terms will �atten out the po-
tential meaning that it rises less steeply than the quadratic function developed
above. As a result the energy levels will get closer together.

�e general form of the harmonic wavefunctions are ψ υ = N υ H υ (y)e−y �2 ,

2
P�E.��
where N υ is the normalization constant and H υ (y) is a Hermite polynomial of
order υ, expressed in terms of the reduced position variable y. Nodes in the
wavefunction occur when the wavefunction passes through zero. �e wave-
functions go asymptotically to zero at y = ±∞ on account of the term e−y �2 ,
2

but these do not count as nodes as the wavefunction does not pass through
zero. �erefore, nodes in the wavefunction correspond to those values at which
Hv (y) = 0.

�e �rst six Hermite polynomials are plotted in Figs �.� and �.��; note that the
normalizing factors have been included.

2
υ=0
υ=1
1 υ=2
H υ (y)

−1

−2
−1.5 −1.0 −0.5 0.0 0.5 1.0 1.5
y
 υ=3
2 υ=4
υ=5

H υ (y) 0

−2

−2 −1 0 1 2
y

D�F.� Rotational motion on a ring and on a sphere share the following features: (a)
quantization arising as a result of the need to satisfy a cyclic boundary con-
dition; (b) energy levels which go inversely with the moment of inertia; (c)
the lack of zero-point energy; (d) degeneracy; (e) quantization of the angular
momentum about one axis.

E�F.�(b) �e magnitude of the angular momentum associated with a wavefunction with

angular momentum quantum number l is given by [�F.��–���], magnitude =
ħ[l(l + 1)]1�2 . Hence for l = 2 the magnitude is ħ[2(2 + 1)]1�2 = 61�2 ħ .
�e projection of the angular momentum onto the z-axis is given by [�F.�–���],
ħm l , where m l is a quantum number that takes values between −l and +l in
integer steps, m l = −l , −l + 1, . . . + l. Hence the possible projections onto the
z-axis are −2ħ, −ħ, 0, ħ, 2ħ .

E�F.�(b) �e wavefunction of a particle on a ring, with quantum number m l is ψ m l =

eim l � = cos(m l �) + i sin(m l �) in the range 0 ≤ � ≤ 2π. �e real and imaginary
parts of the wavefunction are therefore cos(m l �) and sin(m l �) respectively.
Nodes occur when the function passes through zero, which for trigonometric
functions are the same points at which the function is zero. Hence in the real
part, nodes occur when cos(m l �) = 0, and so when m l � = (2n + 1)π�2 for
integer n, which gives � = (2n + 1)π�2m l . In the imaginary part, nodes occur
when sin(m l �) = 0 and so when m l � = nπ for an integer n, which gives � =
nπ�m l .
 (i) With m l = 1, nodes in the real part occur at π�2, 3π�2 , and in the imag-
inary part at 0, π . �ere are � nodes in each of the parts.
(ii) With m l = 2, nodes in the real part occur at π�4, 3π�4, 5π�4, 7π�4 , and
in the imaginary part at 0, π�2, π, 3π�2 . �ere are � nodes in each of the
parts.

E�F.�(b) �e normalization condition is ∫ ψ ∗m l ψ m l dτ = 1. In this case the integral is

over � in the range 0 ≤ � ≤ 2π, and the wavefunction is ψ m l = N cos m l �,
hence
2π
N 2 � ψ ∗m l ψ m l dτ = N 2 � cos2 (m l �) d�
0
�e integral is evaluated by using the identity cos2 θ +sin2 θ = 1, hence cos2 θ =
1 − sin2 θ, and then using Intergral T.� with a = 2π and k = m l
2π 2π 2π
N2 � [1 − sin2 (m l �)] d� = N 2 � d� − N 2 � sin2 (m l �) d�
0 0 0
= 2πN − N 2 � 12 × 2π − (1�4m l ) sin(2πm l )�
2

Because sin(2πm l ) = 0 for integer m l it follows that the integral evaluates to

πN 2 and hence the normalization factor is N = π−1�2 .

�e integral to evaluate is ∫0 cos(m l �) cos(m′l �)d�. Using the identity given

2π
E�F.�(b)
in the question, the integral can be rewritten as
1 2π
� cos[(m l + m′l )�] + cos[(m l − m′l )�]d�
2 0
1 sin[(m l + m′l )�] sin[(m l − m′l )�]
2π
= + �
2 m l + m′l m l − m′l 0
1 sin[2π(m l + m′l )] − sin 0 sin[2π(m l − m′l )] − sin 0
= � + �
2 m l + m′l m l − m′l
= 0
Hence these two wavefunctions are orthogonal.

E�F.�(b) �e energy levels on a particle on a ring are [�F.�–���], E m l = m 2l ħ 2 �2I where

I is the momentum of inertia of the system, I = mr 2 , see �e chemist’s toolkit
�� in Topic �F on page ���. �is is equal to the classical average energy when
1
kT = m 2l ħ 2 �2I. Here kT = (1.3806×10−23 J K−1 )×(298 K) = 4.11... ×10−21 J.
Solving this for �m l � gives
2

1�2
kTmr 2
�m l � = � �
ħ2
[(1.6726 × 10−27 kg) × (100 × 10−12 m)2 (4.11... × 10−21 J)]1�2
=
1.0546 × 10−34 J s
= 2.49
As m l must be integral the closest level is �m l � = 2.
E�F.�(b) �e energy levels are [�F.��–���], E l = ħ 2 l(l + 1)�2I, where I is the moment
of inertia. �e minimum energy to start it rotating is the minimum excitation
energy, the energy to take it from the motionless l = 0 to the rotating l = 1
state, ∆E = E 1 − E 0 = (ħ 2 �2I)(1(1 + 1) − 0(0 + 1)] = ħ 2 �I. Evaluating this gives

∆E = (1.0546 × 10−34 J s)2 �(3.07 × 10−47 kg m2 ) = 3.62 × 10−22 J

E�F.�(b) �e energy levels are [�F.��–���], E l = ħ 2 l(l + 1)�2I, where I is the moment
of inertia. So that the excitation energy is ∆E = E 2 − E 1 = (ħ 2 �2I)[2(2 + 1) −
1(1 + 1)] = 2ħ 2 �I. Evaluating this gives

∆E = 2(1.0546 × 10−34 J s)2 �(3.07 × 10−47 kg m2 ) = 7.25 × 10−22 J

E�F.�(b) �e energy levels are [�F.��–���], E l = ħ 2 l(l + 1)�2I, where I is the

�moment
of inertia. �e corresponding angular momentum is �l 2 �1�2 = ħ l(l + 1).
Hence, the minimum energy allowed is 0, through this corresponds to zero
angular momentum, and so rest and not motion. So the minimum energy of
rotation occurs for the state that has l = 1. �e angular momentum of that state
� √ √
is �l 2 �1 = ħ 1(1 + 1 = 2ħ = 2 × (1.0546 × 10−34 J s) = 1.49 × 10−34 J s .
1�2

E�F.�(b) �e diagrams shown in Fig. �.�� are drawn by forming a vector of length [l(l +
√
1)] 1�2
and with a projection m l on the z-axis. For l = 6 the vector is of length
42 and has possible projections from −6 to +6 in integer steps on the z-axis;
the vectors are labelled with the value of m l . Each vector may lie anywhere on
a cone described by rotating the vector about the z-axis.

E�F.��(b) Following the pattern shown in Fig. �F.� on page ���, the spherical harmonic
Y4,0 is expected to show four angular nodes. �e angle θ = 0 speci�es a point
on the z-axis; this does not describe an angular node or plane.
�
E�F.��(b) �e real part of the spherical harmonic Y2,+2 is − 12 3�π sin2 θ cos 2�. Angular
nodes occur when cos 2� = 0, i.e. at � = π�4, 3π�4, 5π�4, 7π�4 .
�
�e imaginary part of the same spherical harmonic is − 12 3�π sin θ sin 2�.
�is has angular nodes when sin 2� = 0, i.e. at � = 0, π�2, π, 3π�2

E�F.��(b) �e rotational energy depends only on the quantum number l [�F.��–���], but
there are distinct states for every allowed value of m l , which can range from −l
to +l in integer steps. �ere are 2l + 1 such states, as there are l of these with
m l > 0, l of these with m l < 0 and m l = 0. Hence l = 4 has a degeneracy of � .

E�F.��(b) �e diagram shown in Fig. �.�� is drawn by forming a vector of length [l(l +
√
1)] 1�2
and with a projection m l on the z-axis. For l = 3 the vector is of length
12 and has projection −3, . . . + 3 in integer steps on the z-axis. Each vector
may lie anywhere on a cone described by rotating the vector about the z-axis.
For l = 0 the angular momentum is zero, and no vector can be drawn.
 z
+6
+6
+5
+5
+4
+4
+3
+3
+2
+2
+1
+1

0 0

−1
−1
−2
−2
−3
−3
−4
−4
−5
−5
−6
−6

E�F.��(b) �e angle in question is that between the z-axis and the vector representing the
�
angular momentum. �e projection of the vector onto the z-axis is m l ħ, and
the length of the vector is ħ l(l + 1). �erefore the angle θ that the vector
�
makes to the z-axis is given by cos θ = m l � l(l + 1).
When l is very large, the number of projections onto the z axis, (2l + 1), is also
very large implying that the angular momentum vector can take any direction.
In addition, for l >> 1, the vector representing
� the state with m l = l makes an
angle with the z-axis given by cos θ = l� l(l + 1) ≈ l�l = 1. �us, in this limit,
θ = 0 and the vector may point along the z-axis. Both of these results �t in with
the correspondence principle.

P�F.� (a) A function ψ is an eigenfunction of an operator Ω̂ if Ω̂ψ = ωψ where ω is

a constant called the eigenvalue.
(i) lˆz (ei� ) = (ħ�i)d�d�(ei� ) = (ħ�i) × iei� = ħei� . Hence ei� is an
eigenfunction of the operator (ħ�i)d�d�, eigenvalue ħ .
(ii) lˆz (e−2i� ) = (ħ�i)d�d�(e−2i� ) = (ħ�i) × −2ie−2i� = −2ħe−2i� . Hence
e−2i� is an eigenfunction of the operator (ħ�i)d�d�, eigenvalue −2ħ .
 z
+3 +3

+2 +2

+1 +1

0 0

−1 −1

−2 −2

−3 −3

(iii) lˆz (cos �) = (ħ�i)d�d�(cos �) = (ħ�i) × (− sin �) = −(ħ�i) sin �.

Hence cos � is not an eigenfunction of the operator (ħ�i)d�d�.
(iv) lˆz (cos χei� +sin χe−i� ) = (ħ�i)(d�d�)(cos χei� +sin χe−i� ) = (ħ�i)×
(i cos χei� − i sin χe−i� ) = ħ(cos χei� − sin χe−i� ). Hence cos χei� −
sin χe−i� is not an eigenfunction of the operator (ħ�i)d�d�.
(b) For ψ = cos �,

∫0 ψ lˆz ψ d� −(ħ�i) ∫0 cos � sin � d� −(ħ�2i) sin 4π

2π ∗ 2π
�l z � = = = 2π = 0
∫0 ψ ∗ ψ d� ∫0 cos2 � d� ∫0 cos2 � d�
2π 2π

where Integral T.� is used to evaluate the numerator.

For ψ = cos χei� + sin χe−i� ,

∫0 ψ lˆz ψ d� ∫0 (cos χe + sin χe )ħ(cos χe − sin χe ) d�

2π ∗ −i�
2π i� i� −i�
�l z � = =
∫0 ψ ∗ ψ d� ∫0 (cos χe−i� + sin χei� )(cos χei� + sin χe−i� ) d�
2π 2π

ħ ∫0 cos2 χ − sin2 χ − cos χ sin χe−2i� + cos χ sin χe2i� d�

2π
=
∫0 cos2 χ + sin χ + cos χ sin χe−2i� + cos χ sin χe2i� d�
2π 2

Note that as ein� is periodic over 2π for integer n, ∫0 ein� d� = 0. Hence

2π

ħ2π(cos2 χ − sin2 χ)
�l z � = = ħ cos 2χ
2π(cos2 χ + sin2 χ)

(c) (i) For ψ = ei�

T̂ψ = −(ħ 2 �2I)d2 (ei� )�d� 2 = −(ħ 2 �2I)(i)2 ei� = (ħ 2 �2I)ei�

Hence ψ is an eigenfunction with eigenvalue ħ 2 �2I .

 (ii) For ψ = e−2i�

T̂ψ = −(ħ 2 �2I)d2 (e−2i� )�d� 2 = −(ħ 2 �2I)(−2i)2 e−2i� = (4ħ 2 �2I)e−2i�

Hence ψ is an eigenfunction with eigenvalue 4ħ 2 �2I .

(iii) For ψ = cos �

T̂ψ = −(ħ 2 �2I)d2 (cos �)�d� 2 = (ħ 2 �2I) cos �

Hence ψ is an eigenfunction with eigenvalue ħ 2 �2I .

(iv) For ψ = cos χei� + sin χe−i�

T̂ψ = −(ħ 2 �2I)d2 (cos χei� + sin χe−i� )�d� 2

= (ħ 2 �2I)(cos χei� + sin χe−i� )

Hence ψ is an eigenfunction with eigenvalue ħ 2 �2I .

(d) A function is a de�nite state of a particular variable if it is an eigenfunc-
tion of the corresponding operator. Hence, all four wavefunctions are
de�nite kinetic energy states, but only ei� and e−2i� are de�nite angular
momentum states.

P�F.� �e rotational energy levels of a free molecule are given by [�F.��–���], E l =

ħ 2 l(l + 1)�2I, where l = 0, 1, 2... and I is the moment of inertia, which for a
diatomic molecule is I = µR 2 , where µ is the reduced mass of the molecule and
R is the bond length.
For �H ���I, the reduced mass is

µ = (1 m u )(127 m u )�[(1 + 127) m u ] = 0.992... m u

= (0.992... m u ) × (1.6605 × 10−27 kg) = 1.64... × 10−27 kg

�is gives the moment of inertia as I = (1.64...×10−27 kg)×(160×10−12 m)2 =

4.21...×10−47 kg m2 , and so the energy levels become E l = (1.0546×10−34 J s)2 �[2×
4.21... × 10−47 kg m2 ] × l(l + 1) = l(l + 1) × (1.31... × 10−22 J).
Using this the energies of the �rst four levels are computed as

E 0 = 0, E 1 = 2.64 × 10−22 J, E 2 = 7.91 × 10−22 J, E 3 = 1.58 × 10−21 J

�
P�F.� �e function Y1,+1 = − 12 3�2π sin θei� . �e integral to evaluate is
π 2π
∗
� � Y1,+1 Y1,+1 sin θ dθ d�
θ=0 �=0
�
∗
Y1,+1 is complex , and so Y1,+1 = − 12 3�2π sin θe−i� . Hence, the integrand is
� �
− 12 3�2π sin θe−i� × − 12 3�2π sin θei� × sin θ
= (3�8π) sin3 θei(�−�) = (3�8π) sin3 θ
 Hence,
π 2π 3 π 2π
I=� �
∗
Y1,+1 Y1,+1 sin θ dθ d� = � � sin3 θ dθ d�
θ=0 �=0 8π θ=0 �=0
Because the integrand is a function of θ only, the two integrals can be separated
3 2π π 3 1
I= � d� � sin3 θ dθ = �� × (2 − (sin2 π + 2) cos π)
2π
8π 0 0 8π 0 3
3 2 − (0 + 2)(−1)
= (2π − 0) × =1
8π 3
where Integral T.� is used to evaluate the integral in θ. It is con�rmed that the
function is normalized.

P�F.� (a) �e function Yl ,m l is an eigenfunction of the operator Λ̂ 2 with eigen-

value −l(l + 1) for any allowed m l . Hence for ψ = c 1 Yl ,m l + c 2 Yl ,m ′l ,
Λ̂ 2 ψ = Λ̂ 2 (c 1 Yl ,m l + c 2 Yl ,m ′l ) = c 1 Λ̂ 2 Y1,m l + c 2 Λ̂ 2 Y1,m ′l as Λ̂ 2 is a linear
operator. �is is equal to c 1 [−l(l + 1)]Yl ,m l + c 2 [−l(l + 1)]Yl ,m ′l = −l(l +
1)[c 1 Yl ,m l + c 2 Yl ,m ′l ] = −l(l + 1)ψ. Hence, this is an eigenfunction,
eigenvalue −l(l + 1) .
� �
(b) �e relevant functions are Y1,+1 = − 12 3�2π sin θei� , Y1,−1 = − 12 3�2π×
sin θe−i� . �is gives the following combinations,
� �
ψ a = −Y1,+1 + Y1,−1 = 12 3�2π sin θei� + 12 3�2π sin θe−i�
� �
= N 3�2π sin θ(ei� + e−i� )�2 = 3�2π sin θ 12 (ei� + e−i� )
�
= 3�2π sin θ cos �

using cos x = 12 (eix + e−ix )

� �
ψ b = i(Y1,+1 + Y1,−1 ) = −(i�2) 3�2π sin θei� − (i�2) 3�2π sin θe−i�
� �
= −i 3�2π sin θ(ei� − e−i� )�2 = −i 3�2π sin θ(i sin �)

using sin x = (eix + e−ix )�2i

�
= 3�2π sin θ sin �

Both of which are real functions .

(c) Writing ψ a = N a sin θ cos � and ψ b = N b sin θ sin �, these are orthogonal
if ∫�=0 ∫θ=0 ψ ∗a ψ b sin θ dθ d� = 0. As ψ a is real this integral becomes
2π π

2π π
� � (N a sin θ cos �) × (N b sin θ sin �) × sin θ dθ d�
�=0 θ=0
2π π
= N a Nb � � sin3 θ sin � cos �dθd�
�=0 θ=0
 as the integrand can be written as the product of a function of θ with a
function of �, the integral can be separated
2π π
= N a Nb � sin � cos � d� � sin3 θ dθ
0 0
π
= (N a N b �2) × sin2 ��0 × �
2π
sin3 θ dθ
0
π
= (N a N b �2) × [sin2 (2π) − sin2 (0)] × � sin3 θ dθ
0
= 0
Hence, ψ a and ψ b are orthogonal.
(d) �e wavefunctions are normalized if
2π π 2π π
� � ψ ∗a ψ a sin θ dθ d� = 1 and � � ψ ∗b ψ b sin θ dθ d� = 1
�=0 θ=0 �=0 θ=0

Note that both ψ a and ψ b are real. For ψ a this integral is

2π π 2π π
I =� � (N a sin θ cos �)2 sin θ dθ d� = N a2 � � sin3 θ cos2 � dθ d�
�=0 θ=0 �=0 θ=0

�is integral can be separated

2π π 2π π
I = N a2 � cos2 � d� � sin3 θ dθ = N a2 � 1 − sin2 � d� � sin3 θ dθ
0 0 0 0

�e integral in � can be evaluated using Integral T.� and the integral in θ

using Integral T.�

I = N a2 [2π − 2π�2 + (1�4) sin 2(2π)](1�3)[2 − (sin2 π + 2) cos π]

= N a2 (π)(4�3)
�
�e normalizing factor is therefore N a = 3�4π .
For ψ b ,
2π π 2π π
I =� � (N b sin θ sin �)2 sin θ dθ d� = N b2 � � sin3 θ sin2 � dθ d�
�=0 θ=0 �=0 θ=0

�is integral can be separated

2π π
I = N b2 � sin2 � d� � sin3 θ dθ
0 0

�e integral in � is evaluated using Integral T.� and the integral in θ using

Integral T.�

I = N b2 [2π + 2π�2 − (1�4) sin 2(2π)](1�3)[2 − (sin2 π + 2) cos π]

= N b2 (π)(4�3)
�
�e normalizing factor is therefore N b = 3�4π .
 (e) Angular nodes occur when these wavefunctions pass through zero, and
so for ψ a occur when cos � = 0, that is when � = π�2, 3π�2 : this corre-
sponds to the yz plane . For ψ b they occur when sin � = 0, that is when
� = 0, π , which is the xz plane .

P�F.�� �e Hamiltonian for a hydrogen atom is

ħ2 ∂2 ħ 2 lˆ2 e2
Ĥ = − r + −
2mr ∂r 2 2mr 2 4πε 0 r

�e operators lˆz and lˆ2 only operate on the angles θ and �, and so commute
with the operators that a�ect r only, such that

ħ 2 ˆ ˆ2 2
ˆ2 , Ĥ] = ħ [ lˆ2 , lˆ2 ]
[ lˆz , Ĥ] = [ l z , l ] [ l
2mr 2 2mr 2

For the latter, for an arbitrary function f , [ lˆ2 , lˆ2 ] f = lˆ2 lˆ2 f − lˆ2 lˆ2 f = 0. Hence,
[ lˆ2 , lˆ2 ] = 0, and so [ lˆ2 , Ĥ] = 0, meaning that the total angular momentum
operator commutes with the Hamiltonian.
For the former, [ lˆz , lˆ2 ] f = [ lˆz , lˆx2 + lˆy2 + lˆz2 ] f = [ lˆz , lˆx2 ] f + [ lˆz , lˆy2 ] f + [ lˆz , lˆz2 ] f .
Using the relation given in the question, [ lˆz , lˆx2 ] = [ lˆz , lˆx ] lˆx + lˆx [ lˆz , lˆx ] = iħ lˆy lˆx +
iħ lˆx lˆy , and [ lˆz , lˆy2 ] = [ lˆz , lˆy ] lˆy + lˆy [ lˆz , lˆy ] = −[ lˆy , lˆz ] lˆy − lˆy [ lˆy , lˆz ] = −iħ lˆy lˆx −
iħ lˆx lˆy . Finally, [ lˆz , lˆz2 ] = lˆz lˆz2 − lˆz2 lˆz = lˆz3 − lˆz3 = 0. Hence, [ lˆz , lˆ2 ] = iħ lˆy lˆx +
iħ lˆx lˆy − iħ lˆy lˆx − iħ lˆx lˆy + 0 = 0, meaning that the z component of the angular
momentum operator commutes with the Hamiltonian.
�is is important as it implies that all functions that are eigenfunctions of the
Hamiltonian of a H atom are also eigenfunctions of lˆz and lˆ2 .

P�F.�� (a) Write the solutions ψ(r, θ, �) = R(r)Y(θ, �), and then the Schrödinger
equation, Ĥψ = Eψ becomes

ħ 2 ∂ 2 (rRY) ħ2 2
− − Λ̂ (RY) = ERY
2mr ∂r 2 2mr 2

Note that the derivatives in r only a�ects R, and Λ̂ 2 only operates on Y,

such that

ħ 2 Y ∂ 2 (rR) ħ2 R 2
− − Λ̂ Y = ERY
2mr ∂r 2 2mr 2

Dividing this equation by the function RY then gives

ħ 2 ∂ 2 (rR) ħ2
− − Λ̂ 2 Y = E
2mrR ∂r 2 2mr 2 Y
 �e �rst term on the le� hand side depends only on r, but the second term
depends on r and the angles. Hence, to make this equation separable,
multiply through by r 2 , and rearrange to give

ħ 2 r ∂ 2 (rR) ħ 2 Λ̂ 2 Y
− − Er 2 =
2mR ∂r 2 2mY
�e le� side is dependent only on r and the right side depends only on
the angles. Hence, this equation is only true for all r and all angles if both
sides are equal to the same constant, arbitrarily called λ. �is gives two
equations
ħ 2 r ∂ 2 (rR) ħ 2 Λ̂ 2 Y
− − Er 2
= λ =λ
2mR ∂r 2 2mY
�e solutions to the second equation are the spherical harmonics, which
are eigenfunctions of the operator Λ̂ 2 , with eigenvalue −l(l + 1), which
gives −ħ 2 l(l + 1)Y�2mY = λ and so λ = −ħ 2 l(l + 1)�2m. �is makes the
equation in r
ħ 2 r ∂ 2 (rR) ħ 2 l(l + 1)
− − Er 2
= −
2mR ∂r 2 2m
which is rearranged to

ħ 2 ∂ 2 (rR) ħ 2 l(l + 1)
− + R = ER
2mr 2 ∂r 2mr 2
(b) For the case when l = 0, this becomes

ħ 2 ∂ 2 (rR)
− = ER
2mr ∂r 2

For the trial solution R(r) = N sin(nπr�a)�r, and so rR = N sin(nπr�a)

ħ 2 ∂ 2 (N sin(nπr�a)) N sin(nπr�a)
− =E
2mr ∂r 2 r

Note that d2 sin ax�dx 2 = da cos ax�dx = −a 2 sin ax

ħ2 nπ 2
− × − � � N sin(nπr�a) = EN sin(nπr�a)�r
2mr a
Which is solved if
ħ 2 (nπ)2 (h�2)2 n 2 h2 n2
E= = =
2ma 2 2ma 2 8ma 2
where ħ = h�2π has been used
(c) As the wavefunction must be zero outside the cavity, and be continuous,
the wavefunction must equal zero at r = a, for all angles, and so the
boundary condition is that R(a) = 0. Hence sin(nπa�a)�a = 0, which
is true if sin(nπ) = 0, which implies that n must be integral. Hence, the
allowed energies are E n = n 2 h 2 �8ma 2 , n = 1, 2, 3...
I�.� Macroscopic synthesis and material development always contains elements of
randomness at the molecular level. Crystal structures are never perfect. A
product of organic synthesis is never absolutely free of impurities, although
impurities may be at a level that is lower than measurement techniques make
possible. Alloys are grainy and slightly non-homogeneous within any particu-
lar grain. Furthermore, the random distribution of atomic/molecular positions
and orientations within, and between, macroscopic objects causes the conver-
sion of energy to non-useful heat during manufacturing processes. Production
e�ciencies are di�cult to improve. Nanometre technology on the 1 nm to
100 nm scale may resolve many of these problems. Self-organization and pro-
duction processes by nanoparticles and nanomachines may be able to exclude
impurities and greatly improve homogeneity by e�ective examination and se-
lection of each atom/molecule during nanosynthesis and nanoproduction pro-
cesses. Higher e�ciencies of energy usage may be achievable as nanomachines
produce idealized materials at the smaller sizes and pass their products to larger
nanomachines for production of larger scale materials.
�e directed, non-random, use of atoms and molecules by nanotechniques
holds the promise for the production of smaller transistors and wires for the
electronics and computer industries. Unusual material strengths, optical prop-
erties, magnetic properties, and catalytic properties may be achievable. Higher
e�ciencies of photo-electronic conversion would have a great impact.

I�.� (a) �e �rst step is to compute the total energy of the system of N A particles,
which is identi�ed as the internal energy U. �e energy levels for a parti-
cle in a cubic box of side L are given by [�D.��b–���], E n = h 2 n 2 �8mL 2 ,
where n 2 = n 12 + n 22 + n 32 . If there are N A particles, all occupying the
level corresponding to a particular value of n, the internal energy of the
system is U = N A E n = N A h 2 n 2 �8mL 2 . Using V = L 3 the length is
written in terms of the volume as L = V 1�3 , hence L 2 = V 2�3 and therefore
U = N A h 2 n 2 �8mV 2�3 .
If the expansion is adiabatic (that is, not heat �ows into or out of the
system) then from the First Law, dU = dq + dw, it follows that dU = dw.
�e work done on expansion is therefore computed by �nding how U
changes with volume, speci�cally by �nding ∂U�∂V .
∂U ∂ NA h2 n2 −2 N A h 2 n 2 NA h2 n2
= � � = × = −
∂V ∂V 8mV 2�3 adia 3 8mV 5�3 12mV 5�3
�e change in internal energy on expansion through dV will therefore be

��� � � � � � � ��� � � � � � � � �
A

∂U NA h2 n2
dU = � � dV = − dV (�.�)
∂V adia 12mV 5�3
�e work is equal to this change in internal energy. For a �nite change
the expression is integrated with respect to V between limits V1 and V2 ,
with ∆V = V2 − V1 .
 (b) It is evident from eqn �.� that dU, and hence the work, goes as n 2 .
(c) �e work of expansion against an external pressure p ex is given by [�A.�a–
��], dw = −p ex dV . In eqn �.� the term A which multiplies dV refers to
the sample itself, and so must presumably in some way re�ect the pressure
of the sample, not the external pressure. However, if the expansion is
reversible, the external pressure is equal to the internal pressure and the
term A can then be identi�ed as the pressure. �erefore, if it is assumed
that the expansion is both adiabatic and reversible

NA h2 n2
p=
12mV 5�3
�e expression can be rewritten in terms of the average energy of each
particle which, because they all occupy the same level, is simply E av =
n 2 h 2 �8mL 2 = n 2 h 2 �8mV 2�3 , hence

��� � � � � �� � � � � � ��
E av

2 2
NA h n 8N A n 2 h 2 2N A E av
p= = =
12mV 5�3 12V 8mV 2�3 3V
�is expression is reminiscent of the form of the pressure derived using
the kinetic theory of gases (Topic �B): pV = 13 nMυ 2rms , where n is the
amount in moles, M is the molar mass, and υ rms is the root-mean-square
speed. Because M = mN A , where m is the mass of a molecule, the ex-
pression can be rewritten

��� � � � � �� � � � � �
Ek

pV = 13 nmN A υ 2rms = n 23 N A 12 mυ 2rms

�e term 12 mυ 2rms is identi�ed as the average kinetic energy of one molecule

and, because in the kinetic theory the only energy a molecule possesses is
kinetic, E k can further be identi�ed as the average energy, E av . �us, for
one mole (n = 1)
2N A E av
pV = 23 N A E av hence p=
3V
�e two expressions for the pressure are therefore directly comparable
within the restrictions imposed.
(d) For an isothermal expansion heat would have to enter the system in order
to maintain its temperature, and this would involve promoting particles
to higher energy levels. As the volume increases the energy levels move
closer together, so the promotion of particles to higher levels needs to
o�set this e�ect as well.

I�.� (a) In Problem P�D.� and Problem P�D.� it is shown that for a particle in a
box in a state with quantum number n

∆x = L(1�12 − 1�2n 2 π 2 )1�2 and ∆p x = nh�2L

 hence

∆x∆p x = L(1�12 − 1�2n 2 π 2 )1�2 × nh�2L = (nh�2)(1�12 − 1�2n 2 π 2 )1�2

For n = 1

∆x∆p x = L(1�12 − 1�2π 2 )1�2 × h�2L = (h�2)(1�12 − 1�2π 2 )1�2 ≈ 0.57ħ

and for n = 2 ∆x∆p x ≈ 1.7ħ. �e Heisenberg uncertainty principle

is satis�ed in both cases, and it is evident that ∆x∆p x is an increasing
function of n. �e principle is therefore satis�ed for all n > 1.
(b) In Problem P�E.�� it is shown that for a harmonic oscillator in a state with
quantum number υ
∆x υ ∆p υ = (υ + 12 )ħ
�erefore, for the ground state with υ = 0, ∆x∆p = 12 ħ: the Heisenberg
uncertainty principle is satis�ed with the smallest possible uncertainty. It
follow that for υ > 0 the principle is also satis�ed because ∆x υ ∆p υ is an
increasing function of υ.
D�A.� (i) �e principal quantum number n determines the energy of a hydrogenic
atomic orbital through [�A.�–���].
(ii) �e azimuthal quantum number l determines the magnitude of the or-
bital angular momentum, given by [l(l + 1)]1�2 ħ.
(iii) �e magnetic quantum number m l determines the z-component of the
orbital angular momentum, given by m l ħ.
(iv) �e spin quantum number s determines the magnitude of the spin angu-
lar momentum, given by [s(s + 1)]1�2 ħ; for hydrogenic atomic orbitals s
can only be 12 .
(v) �e quantum number m s determines the z-component of the spin angu-
lar momentum, given by m s ħ; for hydrogenic atomic orbitals m s can only
be ± 12 .

E�A.�(b) �e energy of the level of a hydrogenic atom with quantum number n is given
by [�A.��–���], E n = −hc R̃ H Z 2 �n 2 , where Z is the atomic number of the atom.
As described in Section �A.�(d) on page ���, the degeneracy of a state with
quantum number n is n 2 .

• With Z = 2, E n = −4hc R̃ H �n 2 ; the state with E = −4hcR H has n = 1, and

hence degeneracy (1)2 = � .
• With Z = 4, E n = −16hc R̃ H �n 2 ; the state with energy E = −hcR H �4 =
−16hc R̃ H �(8)2 has n = 8, and hence degeneracy (8)2 = �� .
• With Z = 5, E n = −25hc R̃ H �n 2 ; the state with energy E = −hcR H =
−25hc R̃ H �(5)2 has n = 5, and hence degeneracy (5)2 = �� .

E�A.�(b) �e task is to �nd the value of N such that the integral ∫ ψ ∗ ψ dτ = 1, where
ψ = N(2− r�a 0 )e−r�2a 0 . �e integration is over the range r = 0 to ∞, θ = 0 to π,
 and � = 0 to 2π; the volume element is r 2 sin θ dr dθ d�. �e required integral
is therefore
∞ π 2π
N2 � � � (2 − r�a 0 )2 r 2 e−r�a 0 sin θ dr dθ d�
0 0 0

�e integrand is a product of functions of each of the variables, and so the

integral separates into three
∞ π 2π
N2 � (2 − r�a 0 )2 r 2 e−r�a 0 dr � sin θ dθ � d�
0 0 0

�e integral over r is found by �rst expanding the bracket to give

∞ ∞
� (2 − r�a 0 )2 r 2 e−r�a 0 dr = � (4r 2 − 4r 3 �a 0 + r 4 �a 02 )e−r�a 0 dr
0 0
2! 4 3! 1 4!
=4 − + 2 = 8a 03 − 24a 03 + 24a 03 = 8a 03
(1�a 0 ) 3 a 0 (1�a 0 ) 4 a 0 (1�a 0 )5
�ese integrals are evaluated using Integral E.� with the appropriate value of n
and k = 1�a 0 . �e integrals over the angles are straightforward
π 2π
� sin θ dθ � d� = (− cos θ)�0 × ��0 = 4π
π 2π
0 0

�e complete integral evaluates to N 2 × 4π × 8a 03 ; setting this equal to � gives

N = (32πa 3 )−1�2 .

E�A.�(b) �e wavefunction is given by [�A.��–���], ψ n,l ,m l = Yl ,m l (θ, �)R n,l (r); for the
state with n = 3, l = 0, m l = 0 this is

ψ 3,0,0 = Y0,0 (θ, �)R 3,0 (r) = (4π)−1�2 (243)−1�2 (Z�a 0 )3�2 (6 − 6ρ + ρ 2 )e−ρ�2

where the radial wavefunction is taken from Table �A.� on page ���, the angular
wavefunction (the spherical harmonic) is taken from Table �F.� on page ���,
and ρ = 2Zr�na 0 . �e probability density is therefore

P3,0,0 = �ψ 3,0,0 �2 = (4π)−1 (243)−1 (Z�a 0 )3 (6 − 6ρ + ρ 2 )2 e−ρ

�e probability density at the nucleus, ρ = 0, is then (4π)−1 (243)−1 (Z�a 0 )3 (6)2 =

Z 3 �(27πa 3 ) .

E�A.�(b) �e radial wavefunction of a �s orbital is taken from Table �A.� on page ���,
R 3,0 (r) = N(6 − 6ρ + ρ 2 )e−ρ�2 , where ρ = 2Zr�na 0 ; for n = 3, ρ = 2Zr�3a 0 .
�e extrema are located by �nding the values of ρ for which dR 3,0 �dρ = 0; the
product rule is required

dR 3,0 d(6 − 6ρ + ρ 2 ) −ρ de−ρ�2

=N e + N(6 − 6ρ + ρ 2 )
dρ dρ dρ
= (2ρ − 6)e−ρ�2 − 12 �6 − 6ρ + ρ 2 � e−ρ�2
= −(ρ 2 − 10ρ + 18)e−ρ�2
 Setting the term in the parentheses to zero and solving the resulting quadratic
√ √
gives ρ = 5 ± 7, so extrema occur at r = (3a 0 �2Z)(5 ± 7) .
�e simplest way to identify the nature of the extrema is √ to make a plot of
R 3,0 (ρ), from
√ which it is immediately evident that ρ = 5 − 7 is a minimum
and ρ = 5 + 7 is a maximum.

E�A.�(b) Assuming that the electron is in the ground state, the wavefunction is ψ =
Ne−r�a 0 , and so the radial distribution function, given by [�A.��a–���], is R(r) =
4πr 2 ψ 2 = 4πN 2 r 2 e−2r�a 0 . �e �rst step is to �nd the value of r at which this is
a maximum, and this is done by solving dR(r)�dr = 0; for such a calculation
the constants 4πN 2 can be discarded.
dR(r)
= 2r e−2r�a 0 − (2r 2 �a 0 ) e−2r�a 0
dr
�e derivative is zero at r = 0 and r = a 0 , with the latter being the maximum.
�e radial distribution function falls to a fraction f of its maximum at radius
r ′ given by R(r ′ )�R(a 0 ) = f , hence

R(r ′ ) 4πN 2 r ′2 e−2r �a 0 r ′2 e−2r �a 0

′ ′

f = = =
R(a 0 ) 4πN 2 a 02 e−2a 0 �a 0 a 02 e−2

�e solutions to this equation need to be found numerically using mathemat-

ical so�ware. For f = 0.5 the solutions are r ′ = 0.381a 0 and 2.08a 0 . For
f = 0.75 the solutions are r ′ = 0.555a 0 and 1.64a 0 .

E�A.�(b) �e radial wavefunction is R 4,1 = N(20 − 10ρ + ρ 2 )e−ρ�2 where ρ = Zr�2a 0 .

Radial nodes occur when the wavefunction passes through 0, which is √ when
20 − 10ρ + ρ 2 = 0. �e roots of this quadratic equation are at ρ = 5 ± 5 and
√
hence the nodes are at r = (2a 0 �Z)(5 ± 5) . �e wavefunction goes to zero
as ρ → ∞, but this does not count as a node as the wavefunction does not pass
through zero.

E�A.�(b) Angular nodes occur when sin2 θ sin 2� = 0, which occurs when either of sin2 θ
or sin 2� is equal to zero; recall that the range of θ is 0 → π and of � is 0 → 2π.
Although the function is zero for θ = 0 this does not describe a plane, and so
is discounted. �e function is zero for � = 0 with any value of θ: this is the xz
plane (the solution � = π corresponds to the same plane). �e function is also
zero for � = π�2 with any value of θ: this is the yz plane. �ere are two nodal
planes, as expected for a d orbital.

E�A.�(b) �e radial distribution function is de�ned in [�A.��b–���], P(r) = r 2 R(r)2 .

For the �s orbital R(r) is given in Table �A.� on page ��� as R 2,0 = N(6 −
6ρ + ρ 2 )e−ρ�2 where ρ = 2Zr�na 0 , which for n = 3 is ρ = 2Zr�3a 0 . With
the substitution r 2 = ρ 2 (3a 0 �2Z)2 , the radial distribution function is therefore
P(ρ) = N 2 (3a 0 �2Z)2 ρ 2 (6 − 6ρ + ρ 2 )2 e−ρ .
 Mathematical so�ware is used to �nd the values of ρ for which dP(ρ)�dρ = 0,
giving the results ρ = 0, 0.493, 1.27, 2.79, 4.73, 8.72. �e simplest way to
identify which of these is a maximum is to plot P(ρ) against ρ, from which it is
evident that ρ = 0.493, 2.79, 8.72 are all maxima, with the principal maximum
being at ρ = 8.72. �e maximum in the radial distribution function is therefore
at r = 8.72 × (3a 0 �2Z) .

E�A.�(b) �e radius at which the electron is most likely to be found is that at which the
radial distribution function is a maximum. �e radial distribution function is
de�ned in [�A.��b–���], P(r) = r 2 R(r)2 . For the �p orbital R(r) is given in
Table �A.� on page ��� as R 3,0 = N(4 − ρ)ρe−ρ�2 where ρ = 2Zr�na 0 , which
for n = 3 is ρ = 2Zr�3a 0 . With the substitution r 2 = ρ 2 (3a 0 �2Z)2 , �e radial
distribution function is therefore P(ρ) = N 2 (3a 0 �2Z)2 (4 − ρ)2 ρ 4 e−ρ .
To �nd the maximum in this function the derivative is set to zero and the re-
sulting equation solved for ρ. Mathematical so�ware gives the following values
of ρ: 0, 2, 4, 8. It is evident that P(ρ) is zero at ρ = 0 and ρ = 4, and that
P(ρ) tends to zero as ρ → ∞. �erefore ρ = 2 and ρ = 8 must correspond
to maxima; a plot of P(ρ) shows that the latter is the principal maximum; this
occurs at r = 8(3a 0 �2Z) .

E�A.��(b) �e N shell has n = 4. �e possible values of l (subshells) are �, corresponding

to the s orbital, l = 1 corresponding to the p orbitals, l = 2 corresponding to
the d orbitals, and l = 3 corresponding to the f orbitals; there are therefore
� subshells . As there is one s orbital, � p orbitals, � d orbitals and � p orbitals,
there are �� orbitals in total.

� of the orbital angular momentum of an orbital with quantum

E�A.��(b) �e magnitude
number l is l(l + 1)ħ. �e total number of nodes for an orbital with quantum
number n is n − 1, l of these are angular and so the number of radial nodes is
n − l − 1.

orbital n l ang. mom. angular nodes radial nodes

√
�d � � 6ħ � �
√
�p � � 2ħ � �
√
�p � � 2ħ � �

E�A.��(b) All the �d orbitals have the same value of n and l, and hence have the same
radial function, which is given in Table �A.� on page ��� as R 3,2 = N ρ 2 e−ρ�2
where ρ = 2Zr�na 0 , which for n = 3 is ρ = 2Zr�3a 0 . Radial nodes occur when
the wavefunction passes through zero. �e function goes to zero at ρ = 0 and as
ρ → ∞, but it does not pass through zero at these points so they are not nodes.
�e number of radial nodes is therefore �.
P�A.� Two wavefunctions, ψ 1 and ψ 2 are orthogonal if the integral ∫ ψ ∗1 ψ 2 dτ is equal
to zero. In spherical polar coordinates the range of integration is r = 0 to ∞,
θ = 0 to π and � = 0 to 2π; with a volume element is r 2 sin θ dr dθ d�.
(i) Hydrogenic �s and �s orbitals take the form ψ 1s = R 1,0 (r)Y0,0 (θ, �) and
ψ 2s = R 2,0 (r)Y0,0 (θ, �). Because the angular function is the same for
the two orbitals, the orthogonality must arise from the radial parts, so
only these need be considered further. �e radial functions are R 1,0 (ρ) =
N 1,0 e−ρ�2 , where ρ = 2Zr�a 0 and R 2,0 (ρ′ ) = N 2,0 (2 − ρ′ )e−ρ �2 where
′

ρ′ = Zr�a 0 . �e latter is rewritten in terms of ρ by noting that ρ′ = ρ�2:

R 2,0 (ρ) = N 2,0 (2 − ρ�2)e−ρ�4 . �e relevant integral is conveniently taken
over ρ rather than r. Noting that r 2 = ρ 2 (a 0 �2Z)2

��� � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � �
C
∞
� ρ (a 0 �2Z) R 1,0 R 2,0 dρ = (a 0 �2Z)2 N 1,0 N 2,0
2 2
0
∞
×� e−ρ�2 (2 − ρ�2)e−ρ�4 ρ 2 dρ
0
∞
=C� (2ρ 2 − ρ 3 �2)e−3ρ�4 dρ
0
2! 3!
= 2C � � − 12 C � �
(3�4)3 (3�4)4
128 1 1536
= 2C × − C× =0
27 2 81
�e integrals are evaluated using Integral E.� with k = 3�4 and the rele-
vant value of n. �e integral is zero and therefore the �s and �s orbitals
are orthogonal .
(ii) It is explained in Section �A.�(g) on page ��� that the px and p y orbitals
are proportional to x and y respectively. �erefore, in Cartesian coordi-
nates, the integral of the product of these two functions is proportional
∞ ∞ ∞
to ∫−∞ ∫−∞ ∫−∞ x y dx dy dz. �e integrand is an odd function of both
x and y, so when evaluated over a symmetrical range the result is zero.
�ese orbitals are therefore orthogonal .
Alternatively, consider the angular parts of the orbitals given in [�A.��–
���]: px ∝ sin θ cos � and p y ∝ sin θ sin �. �e product of these two
contains the term (cos � sin �) which is equal to 12 sin 2�. �e integral
of this function over the range � = 0 to 2π is zero (the integral over two
complete sine waves). �erefore the functions are orthogonal.

P�A.� Ionization of He+ and Li�+ both occur from the ground state, with n = 1. �e
ionization energy is the energy needed to take the electron from its original
state to the state with n = ∞, which has energy zero by de�nition. �erefore
the ionization energy is simply minus the energy of the ground state. Using
[�A.��–���] follows that I = hcZ 2 R̃ N . �e ratio of the ionization energies of
Li+ , Z = 3, and He+ , Z = 2, is therefore I Li �I He = (3�2)2 (R̃ Li �R̃ He ).
 �e Rydberg constants for Li and He are in principle di�erent because the
reduced masses of the atoms are di�erent. However, this di�erence is too small
to have a signi�cant e�ect on the result of the present calculation, given the
precision of the data. �erefore, it is assumed that R̃ Li �R̃ He = 1 and hence

I Li = I He (3�2)2 = (54.36 eV) × (3�2)2 = 122.3 eV

P�A.� From [�A.��–���], the wavefunctions for the px and p y orbitals can be written
as ψ p x = r f (r) sin θ cos � and ψ p y = r f (r) sin θ sin �. �en, using the identities
cos x = (eix + e−ix )�2 and sin x = (eix − e−ix )�2i, these wavefunctions can be
rewritten

ψ p x = (2)−1 r f (r) sin θ(ei� + e−i� ) ψ p y = (2i)−1 r f (r) sin θ(ei� − e−i� )

�e form of the operator lˆz is given in [�F.�b–���], lˆz = (ħ�i)∂�∂�. To deter-

mine whether or not ψ p x is an eigenfunction of lˆz , the operator is allowed to
act on the function
ħ ∂ 1 ħ1
r f (r) sin θ(ei� + e−i� ) = r f (r) sin θ(iei� − ie−i� )
i ∂� 2 i2

It is evident that the e�ect of the operator is not to regenerate the original
function times a constant, so ψ p x is not an eigenfunction of the operator. A
similar calculation shows that the same is true for ψ p y .
However, the functions e±i� are eigenfunctions of lˆz , (ħ�i)∂�∂� e±i� = ±ħe±i� .
Using the identities e±ix = cos x ± i sin x, suitable combinations of ψ p x and ψ p y
are found which are proportional to e±i� , and hence which are eigenfunctions
of lˆz . �ere are two such combinations

ψ p x ± i × ψ p y = r f (r) sin θ cos � + i × r f (r) sin θ sin � = r f (r) sin θ e±i�

P�A.� �e expectation value of 1�r is given by �1�r� = ∫ ψ ∗ r −1 ψ dτ. �e wavefunction

can be written as a product of a radial part and an angular part ψ = R(r)Y(θ, �).
As 1�r is a function of r only, the integral over the angles can be evaluated
separately, and because the Y(θ, �) are normalized with respect to integra-
∞
tion over the angles the integral simpli�es to �1�r� = ∫0 R(r)2 (1�r)r 2 dr =
∞
∫0 R(r) r dr.
2

(a) For a �s orbital the radial function is R 1,0 (r) = 2(Z�a 0 )3�2 e−Zr�a 0 (Ta-
ble �A.�) and so
∞
�r −1 � = 4(Z�a 0 )3 � re−2Zr�a 0 dr = 4(Z�a)3 [1!�(2Z�a 0 )2 ] = Z�a 0
0

where the integral is evaluated using Integral E.� with n = 1 and k =

2Z�a 0 .
 (b) For �s the radial function is R 2,0 (r) = 8−1�2 (Z�a 0 )3�2 [2 − Zr�a 0 ]e−Zr�2a 0
and so
∞
�r −1 � = 8−1 (Z�a 0 )3 � r(2 − Zr�a 0 )2 e−Zr�a 0 dr
0
∞
= 8−1 (Z�a 0 )3 � (4r − 4Zr 2 �a 0 + Z 2 r 3 �a 02 )e−Zr�a 0 dr
0
= 8−1 (Z�a 0 )3 (a 0 �Z)2 (4 − 8 + 6) = Z�4a 0

(c) For a �p orbital, R 2,1 (r) = 24−1�2 (Z�a 0 )3�2 (Zr�a 0 )e−Zr�2a 0 and so
∞
�r −1 � = � r �24−1�2 (Z�a 0 )3�2 (Zr�a 0 )e−Zr�2a 0 � dr
2

0
∞
= (Z 5 �24a 05 ) � r 3 e−Zr�a 0 dr = (Z 5 �24a 05 ) × 3!�(Z�a 0 )4 = Z�4a 0
0

�e expectation value of 1�r is the same for �s and �p.

(d) �ere is no reason to assume that �1�r� = 1��r�. To take a speci�c exam-
ple, in the case of a �s orbital �r� = 3a 0 �2Z and �1�r� = Z�a 0 .

P�A.�� (a) �e main di�erence between the Bohr and quantum models is that in the
Bohr model the trajectory (that is the position) of the electron is precisely
de�ned, whereas in quantum mechanics only the probability distribution
of the position can be predicted.
(b) In quantum mechanics the magnitude of the orbital angular� momentum
of an electron with quantum number l is given by ħ l(l + 1). In con-
trast, in the Bohr model the magnitude depends on n and is nħ. In the
Bohr model the ground state, with n = 1, has angular momentum ħ,
whereas in quantum mechanics the ground state (�s) has zero angular
momentum. As has already been commented on, the predicted distribu-
tion of the electron is quite di�erent in the two cases.
(c) �e angular momentum of the ground state and the spatial distribution
of the electron can be probed experimentally by various kinds of spec-
troscopy.

D�B.� �is is covered in any introductory or general chemistry text.

D�B.� See Section �B.� on page ���.

E�B.�(b) Hydrogenic orbitals are written in the form [�A.��–���], R n,l (r)Yl ,m l (θ, �),
where the appropriate radial function R n,l is selected from Table �A.� on page
��� and the appropriate angular function Yl ,m l is selected from Table �F.� on
page ���. Using Z = 2 for the �s and Z = 1 for the �s gives

ψ 1s (r) = R 1,0 Y0,0 = 2(2�a 0 )3�2 e−2r�a 0 × (4π)−1�2

ψ 3s (r) = R 3,0 Y0,0
= (243)−1�2 (2�3a 0 )3�2 [6 − 6(2r�3a 0 ) + (2r�3a 0 )2 ]e−r�3a 0 × (4π)−1�2

�e overall wavefunction is simply the product of the orbital wavefunctions

Ψ(r 1 , r 2 ) = ψ 1s (r 1 )ψ 3s (r 2 )

E�B.�(b) For a subshell with angular momentum quantum number l there are 2l + 1
values of m l , each of which corresponds to a separate orbital. Each orbital
can accommodate two electrons, therefore the total number of electrons is 2 ×
(2l + 1). �e subshell with l = 5 can therefore accommodate 2(10 + 1) = ��
electrons.

E�B.�(b) All con�gurations have the [Kr] core. �e table shows the ‘accepted’ con�gu-
rations for the ground states.

Y Zr Nb Mo Tc
2 1 2 2 1 4 1 5
5s 4d 5s 4d 5s 4d 5s 4d 5s 4d5
2

Ru Rh Pd Ag Cd
1 7 1 8 10 1 10
5s 4d 5s 4d 4d 5s 4d 5s 4d10
2

E�B.�(b) �s2 �s2 �p6 = [Ar]

E�B.�(b) Across the period the energy of the orbitals generally decreases as a result of
the increasing nuclear charge. �e second ionization energy corresponds to an
electron being removed from the ion M+ . For Li+ this would involve removing
an electron from the �s orbital, which is much lower in energy (and therefore
harder to ionize) than the �s. For Be+ it is a �s electron which is ionized,
and as this element has the lowest nuclear charge of the remaining elements in
Period � it is expected to have the highest orbital energy and hence the lowest
ionization energy.

P�B.� �e electronic con�guration of the Y atom is [Kr] �d1 �s2 as opposed to �d2 �s1 .
�is is due to the �s orbital being much larger and di�use than the �d orbitals,
 and so the average distance between electrons is larger and so the average re-
pulsion between electrons is much smaller. [Kr] �d1 �s2 is therefore the lower
energy, more stable con�guration.
�e Ag atom has the con�guration [Kr] �d10 �s 1 , as opposed to [Kr] �d9 �s2 . �e
number of both spin up and spin down electrons is the same in both of these
con�gurations, but the number of parallel spin pairs within the �d subshell
is larger for the con�guration [Kr] �d10 �s1 , which means this con�guration
is lower in energy, as a parallel spin pair is lowest in energy when between
two electrons within the same subshell. Also this has fewer electrons in higher
energy subshells.

P�B.� �e electronic con�guration of Fe is [Ar] �d6 �s2 , of Fe�+ it is [Ar] �d6 , and of
Fe�+ it is [Ar] �d5 . Hence, the outermost electron in both ions is in a �d orbital,
with the only di�erence between these con�gurations that Fe�+ has one of the
�ve �d orbitals doubly occupied.
�ere is more repulsion between the � �d electrons in Fe�+ than the � �d elec-
trons in Fe�+ , and there is no compensating increase in the atomic number to
draw the electrons towards the nucleus, and so the Fe�+ ion is expected to be
the larger of the two ions.

D�C.� �e selection rules are given in [�C.�–���]. In part these can be rationalised
by noting that a photon has one unit of (spin) angular momentum and that
in the spectroscopic transition this angular momentum must be conserved.
�e selection rule for l, ∆l = ±1, can be understood as a single electron in
the atom changing angular momentum by one unit in order to accommodate
the angular momentum from the photon. �is selection is derived in How
is that done? �C.� on page ��� by considering the relevant transition dipole
moment. �e selection rule for the total spin, ∆S = 0, stems from the fact that
the electromagnetic radiation does not a�ect the spin directly.
�e selection rules for multi-electron atoms are harder to rationalise not least
because the change in the overall angular momentum (L and J) is a�ected both
by changes in the angular momenta of individual electrons and by the way in
which these couple together.

D�C.� �is is discussed in Section �C.�(b) on page ���.

E�C.�(b) �e spectral lines of a hydrogen atom are given by [�A.�–���], ν̃ = R̃ H (n−2

1 −
n−2
2 ), where R̃ H is the Rydberg constant and ν̃ is the wavenumber of the tran-
sition.
 �e Pfund series corresponds to n 1 = 5. �e lowest energy transition, which
would involve a photon with the longest wavelength, is to the next highest
energy level which has n 2 = 6 . Transitions to higher energy levels involve more
an more energy, and the limit of this is the transition to n 2 = ∞ which involves
the greatest possible energy change and hence the shortest wavelength.

E�C.�(b) he energy levels of a hydrogenic atom are E n = −hcZ 2 R̃ N n−2 , where Z is the
atomic number; for all but the most precise work it is su�cient to approximate
R̃ N by R̃∞ . �e wavenumber of the transition between states with quantum
numbers n 1 and n 2 in the Li2+ ion is given by a modi�ed version of [�A.�–���],
ν̃ = Z 2 R̃∞ (n−2
1 − n 2 ). For the 5 → 4 transition and with Z = 3
−2

ν̃ = 32 × (1.0974 × 105 cm−1 ) × (4−2 − 5−2 ) = 2.22 × 105 cm−1

λ = ν̃−1 = 1�[32 × (1.0974 × 105 cm−1 ) × (4−2 − 5−2 )]
= 4.49... × 10−5 cm = ��� nm
ν = c�λ = (2.9979 × 108 m s−1 )�(4.49... × 10−7 m) = ��� THz

E�C.�(b) �e selection rules for a many-electron atom are given in [�C.�–���]. For a
single electron these reduce to ∆l = ±1; there is no restriction on changes in n.
(i) �d (n = 5, l = 2) → �s (n = 2, l = 0) has ∆l = −2, and so is forbidden .
(ii) �p (n = 5, l = 1) → �s (n = 1, l = 0) has ∆l = −1, and so is allowed .
(iii) �p (n = 3, l = 1) → �f (n = 2, l = 3) has ∆l = +2, and so is forbidden .

E�C.�(b) �e single electron in a f orbital has l = 3 and hence L = 3, and s = 12 hence

S = 12 . �e spin multiplicity is 2S + 1 = 2. Using the Clebsh–Gordon series,
[�C.�–���], the possible values of J are J = L + S, L + S − 1, . . . �L − S� = 72 , 52 .
Hence, the term symbols for the levels are 2 F7�2 , 2 F5�2 .

E�C.�(b) For a p electron l = 1 and s = 12 . Using the Clebsh–Gordon series, [�C.�–���],

the possible values of j are l + s, l + s − 1, . . . �l − s�, which in this case are
j = 32 , 12 .

For an h electron l = 5 and s = 1

2
hence j = 11 9
,
2 2
.

E�C.�(b) �e Clebsch–Gordan series [�C.�–���] gives the possible values of J as J =

j 1 + j 2 , j 1 + j 2 − 1, . . . � j 1 − j 2 �. With j 1 = 5, j 2 = 3, the possible values of J are
J = 8, 7, 6, 5, 4, 3, 2 .

E�C.�(b) �e symbol F implies that the total orbital angular momentum L = 3 , the su-
perscript � implies that the multiplicity 2S + 1 = 3, so that the total spin angular
momentum S = 1 . �e subscript � implies that the total angular momentum
J =4.
E�C.�(b) �e Clebsch–Gordan series, [�C.�–���], is used to combine two spin angular
momenta s 1 and s 2 to give S = s 1 + s 2 , s 1 + s 2 − 1 ..., �s 1 − s 2 �.
(i) Four electrons are treated by �rst combing the angular momenta of two
electrons, then combining the result with the spin of the third electron,
and then with the spin of the fourth. For two electrons, each with s = 12 ,
S ′ = 1, 0. Combining S ′ = 1 with s 3 = 12 for the third spin gives S ′′ =
1 + 12 , �1 − 12 � = 32 , 12 . Combining S ′ = 0 with s 3 = 12 just gives S ′′ = 12 . �e
process is continued with the fourth electron: S ′′ = 32 with s 4 = 12 gives
S = 2, 1; S ′′ = 12 with s 4 = 12 gives S = 1, 0. In summary the possible
values for the total spin are S = 2, 1, 0 , with multiplicities �, �, � .
(ii) For �ve electrons the values of S from (i) are combined with a further
spin s 5 = 12 . For S = 2 the result is 52 , 32 ; S = 1 gives 32 , 12 ; and S = 0
gives just 12 . �e possible values for the total spin for �ve electrons are are
S = 52 , 3 1
,
2 2
, with multiplicities �, �, � .

E�C.�(b) �e valence electron con�guration of the V�+ is [Ar] �d3 . With � electrons
occupying the � d orbitals the Pauli principle places no restrictions on the num-
ber of parallel spins because the � electrons can occupy separate orbitals. �e
procedure used in Exercise E�C.�(b) part (i) can therefore be followed, giving
the possible values of S for � electrons as S = 32 , 12 . �e quantum number M S ,
which speci�es the z-component of the spin angular momentum, takes values
S, (S −1) . . . −S. �erefore for S = 32 , M S = ± 32 , ± 12 and for S = 12 , M S = ± 12 .

E�C.��(b) �ese electrons are not equivalent, as they are in di�erent subshells, hence all
the terms that arise from the vector model and the Clebsch–Gordan series are
allowed. �e orbital angular momentum of the p and d electrons are l 1 = 1 and
l 2 = 2 respectively, and these are combined using L = l 1 +l 2 , l 1 +l 2 −1, ... �l 1 −l 2 �
which in this case gives L = 3, 2, 1. �e spin angular momenta of each electron
is s 1 = s 2 = 12 , and these combine in the same way to give S = 1, 0; these values
of S have spin multiplicities of 2S +1 = 3, 1. �e terms which arise are therefore
3 1 3
F, F, D, 1 D, 3 P, and 1 P.
�e possible values of J are given by J = L + S, L + S − 1, ..., �L − S�, and
hence for S = 1, L = 3 the values of J are �, �, and �. For S = 1, L = 2 the
values of J are �, �, and �. For S = 1, L = 1 the values of J are �, �, and �. For
S = 0 and any value of L only J = L is possible. �e term symbols are therefore
3
F4 , 3 F3 , 3 F2 , 3 D3 , 3 D2 , 3 D1 , 3 P2 , 3 P1 and 3 P0 , and 1 F3 , 1 D2 , and 1 P1 .
From Hund’s rules, described in Section �C.�(d) on page ���, the lowest energy
state is the one with the greatest spin, then the greatest orbital angular momen-
tum and then, because the shell is less than half full, the smallest J. �is is 3 F2 .

E�C.��(b) (i) 3 D has L = 2, S = 1 and so J = 3, 2, 1 only. �ere are 2J + 1 values of M J ,

which for these three values of J gives 7, 5, 3 states, respectively. (ii) 4 D has
L = 2, S = 32 , and so J = 72 , 52 , 32 , 12 with 8, 6, 4, 2 states, respectively. (ii) 2 G
has L = 4, S = 12 , and so J = 92 , 7
2
with 10, 8 states, respectively.
E�C.��(b) Closed shells have total spin and orbital angular momenta of zero, and so do
not contribute to the overall values of S and L. (i) �d10 �s2 is a closed shell
con�guration with L = 0, S = 0, and J = 0. �e term symbol is 1 S0 .
(ii) For the con�guration �d10 �s2 �p5 only the p electrons need be considered as
the others are in a closed shell. Because of the spin pairing required by the Pauli
principle the con�guration p5 has the same terms as p1 : this is o�en expressed
by saying that p5 is the ‘absence’ of one electron or a ‘hole’. Holes behave just
like electrons when it comes to formulating term symbols. �erefore, one ‘hole’
in a p sub-shell has l = 1 and s = 12 , so L = 1, S = 12 , and J = 32 , 12 . �e term
symbols are therefore 2 P3�2 and 2 P1�2 .

E�C.��(b) �e two terms arising from an f 1 con�guration are 2 F7�2 , 2 F5�2 , which have
S = 12 , L = 3 and J = 72 , 52 . �e energy shi� due to spin-orbit coupling is given
by [�C.�–���], E L,S , J = 12 hc Ã[J(J + 1) − L(L + 1) − S(S + 1)], where à is the
spin-orbit coupling constant. Hence, E 3,1�2,7�2 = +(3�2)hc à , and E 3,1�2,5�2 =
−2hc à .

E�C.��(b) �e selection rules for a many-electron atom are given in [�C.�–���].

(i) 2 P3�2 (S = 12 , L = 1, J = 32 ) → 2 S1�2 (S = 1

2
,L = 0, J = 12 ) has ∆S = 0,
∆L = −1, ∆J = −1 and so is allowed .
(ii) 3 P0 (S = 1, L = 1, J = 0) → 3 S1 (S = 1, L = 0, J = 1) has ∆S = 0, ∆L = −1,
∆J = +1 and so is allowed .
(iii) 3 D3 (S = 1, L = 2, J = 3) → 1 P1 (S = 0, L = 1, J = 1) has ∆S = −1, ∆L = −1,
∆J = −2 and so is forbidden by the S and J selection rules.

P�C.� �e wavenumbers of the spectral lines of the H atom for the n 2 → n 1 transition
is given by [�A.�–���], ν̃ = R̃ H (n−2
1 − n 2 ), where R̃ H is the Rydberg constant
−2

for Hydrogen, R̃ H = 109677 cm . Hence, the wavelength of this transition is

−1

λ = ν̃−1 = R̃−1
H (n 1 − n 2 ) .
−2 −2 −1

�e lowest energy, and therefore the longest wavelength transition (the one
at λ max = 656.46 nm = 6.5646 × 10−5 cm) is assumed to correspond to the
transition from n 1 + 1 → n 1

1 1 1 (n 1 + 1)2 − n 12 2n 1 + 1
= − = 2 = 2
λ max R̃ H n 1 (n 1 + 1)
2 2 n 1 (n 1 + 1)2 n 1 (n 1 + 1)2

From the given data (λ max R̃ H )−1 = [(6.5646 × 10−5 cm) × (109677 cm−1 )]−1 =
(7.19...)−1 . �e value of n 1 is found by seeking an integer value of n 1 for which
n 12 (n 1 + 1)2 �(2n 1 + 1) = 7.19.... For n 1 = 2 the fraction on the le� is 42 × 92 �5 =
7.2. �erefore, the series is that with n 1 = 2 .
 �erefore the wavelengths of the transitions are given by λ−1 = (109677 cm−1 )×
(2−2 − n−2
2 ), and n 2 = 3, 4, 5, 6; the next line has n 2 = 7, and so has a
wavelength of
−1
λ = �(109677 cm−1 ) × (2−2 − 7−2 )� = 3.97... × 10−5 cm = 397.13 nm

�e ionization energy of the atom when it is in the lower state of quoted transi-
tions is the energy to remove electron from the n = 2 state, which is the energy
for the transition ∞ → 2

I = hc R̃ H (2−2 − ∞−2 ) = 14 hc R̃ H
= 1
4
× (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (109677 cm−1 )
= 5.4466 × 10−19 J or 3.3995 eV

P�C.� �e wavenumbers of transitions between energy levels in hydrogenic atoms are

given by a modi�ed version of [�A.�–���], ν̃ = Z 2 R̃ Li �n−2
1 − n 2 � where Z is
−2

the nuclear charge, for Li2= Z = 3, and R̃ N is the Rydberg constant for Li. �e
Lyman series all have n 1 = 1 so the wavenumber of the transitions are given by

ν̃ n 2 = 9R̃ Li �1 − n−2
2 �

If the three lines given correspond to n 2 = 2, 3, 4, then using this value for
n 2 the fraction ν̃ n 2 �9(1 − n−2
2 ) should be constant, and equal to R̃ Li . �is is
explored in the following table

n2 2 3 4
ν̃ n 2 � cm−1 740 747 877 924 925 933
ν̃ n 2 �[9(1 − n−2 2 )]� cm
−1
109 740 109 741 109 740

�e ratio is indeed constant, con�rming that the correct value of n 2 has been
chosen; the average value of R̃ Li is ��� ��� cm−1 .
�e Balmer series all have n 1 = 2 so the wavenumber of the transitions are
given by
ν̃ n 2 = 9R̃ Li � 14 − n−2
2 �

�e longest wavelength transition has n 2 = 3

ν̃ 3 = 9(109 740 cm−1 ) � 14 − 3−2 � = ��� ��� cm−1

�e next longest has n 2 = 4 and a similar calculation gives ν̃ 4 = 185 186 cm−1 .
�e energy needed to ionize an electron from the ground state, with n = 1, is
simply minus the energy of this state, which is 9(109 740 cm−1 ) = 987 660 cm−1
or ���.�� eV .
P�C.� �e �p con�guration has just one electron outside a closed subshell. �at elec-
tron has l = 1, s = 1�2, and j = 1�2 or 3�2, so the atom has L = 1, S = 1�2,
and J = 3�2 or 1�2. �e term symbols are 2 �P1�2 and 2 P3�2 of which the former
has the lower energy. �e �d con�guration also has just one electron outside a
closed subshell; that electron has l = 2, s = 1�2, and j = 3�2 or 5�2, so the atom
has L = 2, S = 1�2, and J = 5�2 or 3�2. �e term symbols are 2 D5�2 and 2 D3�2
of which the former has the lower energy.
�e spin-orbit coupling energy can be estimated using [�C.�–���], but this
gives the energy of 2 P1�2 relative to 2 P3�2 , or 2 D5�2 relative to 2 D3�2 . �e ex-
pression cannot be used to compare the energy of 2 D and 2 P.

P�C.� �e energy levels of a hydrogenic atom are given by [�A.��–���], E n = −hc R̃ N �n 2 ,

where R̃ N is the Rydberg constant for the nucleus in question which in turn is
proportional to the reduced mass of the nucleus–electron system [�A.��–���],
µ N = m N m e �(m N + m e ). �e ratio of the wavenumbers of the same transition
in two hydrogenic atoms with the same nuclear charge is proportional to the
ratio of the Rydberg constants, and hence to the ratio of the reduced masses
ν̃ D R̃ D µ D m D m e �(m D + m e ) m D (m H + m e )
= = = =
ν̃ H R̃ H µ H m H m e �(m H + m e ) m H (m D + m e )
�is expression is rearranged to give
(ν̃ D �ν̃ H )m H m e
mD =
m e + m H [1 − (ν̃ D �ν̃ H )]
Given the high precision of the data, it is necessary to use an equivalent high
precision for the fundamental constants (taken from the inside of the front
cover of the text) and to use the mass of the H nucleus as 1.007 825 m u . Using
such data it is found that m D = 3.345 19 × 10−27 kg or 2.014 52 m u .
�e ionization energy is simply hc R̃ N and because the wavenumbers of the
transitions are proportional to the relevant value of R̃ N it follows that
I H R̃ H ν̃ H 82 259.098 cm−1
= = = = �.��� ���
I D R̃ D ν̃ D 82 281.476 cm−1

P�C.�� (a) �e separation of the lines observed in the spectrum when a magnetic
�eld is applied is a direct re�ection of the energy splitting of the energy
levels. �erefore, the separation of the lines δ ν̃, expressed as a wavenum-
ber, is hcδν̃ = µ B B.
µB B (9.274 × 10−24 J T−1 ) × (2 T)
δν̃ = = = 0.94 cm−1
hc (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
(b) �e �rst line in the Balmer series (n = 2 → 3) has wavenumber
ν̃ 2,3 = R̃ H (1�22 − 1�32 ) = 15 233 cm−1
�erefore the normal Zeeman splitting is very small compared to the
di�erence in the energy of the states involved in typical transitions.
P�C.�� For a ‘red star’, with a surface temperature in the range � ��� K to � ��� K, the
thermal energy is insu�cient to cause the excitation of the electron in hydrogen
from its ground state: no emission spectra from hydrogen is therefore seen. In
contrast, for a ‘blue star’, with a surface temperature in the range �� ��� K to
�� ��� K, the thermal energy is su�cient to cause ionization of the electron.
�erefore, neither absorption not emission from hydrogen is seen simply be-
cause there are no hydrogen atoms present – they have all been ionized. If
the with a surface temperature is in the range � ��� K to �� ��� K the thermal
energy is su�cient to cause excitation of hydrogen atoms, but not su�cient to
cause extensive ionization. Intense hydrogen emission lines are seen from such
stars.
�is explanation can be explored in a more quantitative way be examining how
the frequency spectrum of black body radiation changes with temperature,
and examining what part of the radiation is at high enough frequencies to
cause excitation or ionization. �e Planck distribution is given by [��A.�–���],
ρ(ν) = 8πhν 3 c −3 (e hν�k T − 1)−1 , and in Fig. �.� this is plotted against hν�I,
where I is the ionization energy of hydrogen, for three di�erent temperatures.
At 25000 K a signi�cant fraction of the radiation is at frequencies above that
needed to ionize hydrogen (hν�I > 1).

0.006 25 000 K
20 000 K
15 000 K
ρ(ν)h 2 c 3 �8πI 3

0.004

0.002

0.000
0.0 0.5 1.0 1.5 2.0
hν�I

I�.� (a) �e energy levels of a Hydrogen atom (with Z = 1) are given by [�A.��–
���], E n = −hc R̃ H n−2 , where R̃ H = 109 677 cm−1 is the Rydberg constant
for the Hydrogen atom. Hence, the separation between between the en-
ergy levels n and n + 1 is

1 1 (n + 1)2 − n 2
∆E = E n+1 − E n = hc R̃ H � − � = hc R̃ H 2
n 2 (n + 1) 2 n (n + 1)2
= hc R̃ H (2n + 1)�[n 2 (n + 1)2 ] ≈ 2hc R̃ H �n 3
 where the approximation is for n � 1 so that (2n +1) ≈ 2n and (n +1)2 ≈
n2
(b) For n = 100, this becomes

∆E = 2hc R̃ H �1003
= 2 × (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (109 677 cm−1 )�1003
= 4.357 × 10−24 J

�e average radius of a H ���s orbital (Z = 1, n = 100, l = 0) is given by

the expression in Integrated activity I�.�

(100)2 a 0 0(0 + 1)
�r�100,0,0 = �1 + 12 �1 − �� = 15 000 a 0
1 1002

�e ionization energy for an electron in the state with n = 100 is simply

minus the orbital energy

I = hc R̃ H �1002
= (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (109677 cm−1 )�1002
= 2.179 × 10−22 J

(c) �e energy available in a collision is of the order of 12 kT (from the equipar-

tition principle), which at ��� K is 12 × (1.3806 × 10−23 J K−1 ) × (298 K) =
2.06 × 10−21 J. �is is well in excess of the ionization energy, so a collision
could easily result in ionization.
(d) �e minimum velocity required for ionization will be when the kinetic
energy of the H atom, E k = 12 mυ 2 is equal to the ionization energy I;
hence υ = (2I�m)1�2

υ = (2I�m)1�2 = [2 × (2.179 × 10−22 J)�(1.0078 × 1.6605 × 10−27 kg)]1�2

= 510 m s−1

where the mass of H is taken as 1.0078 m u .

(e) �e radial wavefunction for a ���s orbital will have a �nite value at the
nucleus and �� radial nodes. �e exponentially decaying part of the wave-
function, which dominates for su�ciently large distances, is of the form
e−r�100a 0 .
D�A.� Promotion and hybridization are two modi�cations to the simplest version of
valence-bond (VB) theory, adopted to overcome obvious mismatches between
predictions of that theory and observations. In its simplest form VB theory
assumes that the functions ψ A and ψ B that appear in a VB wavefunction, [�A.�–
���], are orbitals in free atoms occupied by unpaired electrons. For exam-
ple, such a theory would predict that carbon, with the electronic con�guration
2s2 2p2 , would form two bonds on account if it having two unpaired electrons.
�is prediction is at odds with the characteristic valency of four shown by
carbon.
To account for the tetravalence of carbon it is supposed that one of the �s
electrons is excited (‘promoted’) to the empty �p orbital, giving a con�guration
of 2s1 2p3 . �ere are now four unpaired electrons (in the �s and �p orbitals)
available for forming four valence bonds.
Hybrid orbitals are invoked to account for the fact that valence bonds formed
from atomic orbitals would have di�erent orientations in space than are com-
monly observed. For instance, the four bonds in CH� are observed to be equiv-
alent and directed toward the corners of a regular tetrahedron. By contrast,
bonds made from the three distinct �p orbitals in carbon would be expected to
be oriented at ��○ angles from each other, and those three bonds would not be
equivalent to the bond made from a �s orbital. Hybrid atomic orbitals, in this
case sp3 hybrids, are formed by combining the atomic orbitals in such a way
that the hybrid orbitals have the required directional properties.

D�A.� �e part of the VB wavefunction that depends on spatial coordinates is given

in [�A.�–���], Ψ(1, 2)space = ψ A (1)ψ B (2) + ψ A (2)ψ B (1). �e complete wave-
function includes a spin part, σ(1, 2)

Ψ(1, 2) = {ψ A (1)ψ B (2) + ψ A (2)ψ B (1)} σ(1, 2)

�e Pauli principle requires that the wavefunction must be antisymmetric, that

is it must change sign, upon interchange of particle labels: Ψ(2, 1) = −Ψ(1, 2).
�e spatial part is symmetric under this interchange of labels Ψ(2, 1)space =
+Ψ(1, 2)space , therefore the spin part must be antisymmetric σ(2, 1) = −σ(1, 2).
�e antisymmetric spin wavefunction for two spins is the one in which the spins
 are paired
σ(2, 1) = (1�2)1�2 {α(1)β(2) − β(1)α(2)}
In summary, the form of the VB wavefunction which results in a the lower-
ing of the energy, and hence bond formation, is symmetric with respect to
interchange of the electron labels, and in order to satisfy the Pauli principle
the associated spin wavefunction must be anti-symmetric with respect to this
exchange. �is wavefunction corresponds to one in which the spins are paired.

E�A.�(b) �e nitrogen atoms in N2 are sp hybridized. �e σ bond is formed by the over-

lap of two sp hybrid atomic orbitals oriented towards each other along the inter-
nuclear axis. Using [�A.�–���], the spatial part of the valence-bond wavefunc-
tion of the σ orbital is written Ψ(1, 2) = ψNspA (1)ψNspB (2)+ψNspA (2)ψNspB (1).
�is wavefunction is symmetric, therefore it has to be combined with the anti-
symmetric two-electron spin wavefunction given by [�B.�–���], σ− (1, 2). �e
resulting complete, asymmetric two-electron wavefunction satis�es the Pauli
principle and has the form of

Ψσ (1, 2) = [ψNspA (1)ψNspB (2) + ψNspA (2)ψNspB (1)] × [α(1)β(2) − β(1)α(2)]

�e two π orbitals are formed by the side-by-side overlap of two px and two p y
orbitals. Following the same logic as above, the valence-bond wavefunction for
the 2p y π orbital is written as

Ψπ (1, 2) = [ψNp y A (1)ψNp y B (2) + ψNp y A (2)ψNp y B (1)] × [α(1)β(2) − β(1)α(2)]

and similarly for the 2px π orbital.

E�A.�(b) �e resonance hybrid wavefunction constructed from one two-electron wave-

function corresponding to the purely covalent form of the bond and one two-
electron wavefunction corresponding to the ionic form of the bond is given in
[�A.�–���] as Ψ = Ψcovalent + λΨionic . �erefore the (unnormalized) resonance
hybrid wavefunction of N2 with two ionic structures is written as ΨN2 = ΨN–N +
λΨN+ N− + κΨN2− N2+ .
�e valence bond description of the triple bond in N� is give in Example E�A.�(b).
Omitting the spin functions for simplicity, the spatial wavefunction is a product
of that for the σ bond, and that for each of the π bonds

[ψNspA (1)ψNspB (2) + ψNspA (2)ψNspB (1)]

× [ψNp y A (3)ψNp y B (4) + ψNp y A (4)ψNp y B (3)]
× [ψNp x A (5)ψNp x B (6) + ψNp x A (6)ψNp x B (5)]

Somewhat arbitrarily electrons � and � have been assigned to the �rst valence-
bond wavefunction, � and � to the next and so on.
�e ionic structure N+ N – can be thought of as arising when electrons � and
� are both located in Npx B . In this case, the part of the wavefunction in the
 third bracket becomes [ψNp x B (5)ψNp x B (6)]. �is is just one possibility: ionic
structures also arise when electrons � and � are on the same atom (leading to a
modi�cation of the second bracket), or � and � are on the same atom (leading
to a modi�cation of the �rst bracket).
�e ionic structure N� – N�+ can be thought of as arising when electrons � and
� are both located in Npx A , and electrons � and � are both located in Np y A .
In this case, the third bracket becomes [ψNp x A (5)ψNp x A (6)] and the second
bracket becomes [ψNp y A (3)ψNp y A (4)]. Similar wavefunctions for N� – N�+ can
be written by rearranging any two of the valence electrons.

E�A.�(b) A good starting point is to construct Lewis structures in which bonded pairs
of electrons are identi�ed by a line and lone pairs by the usual double dot; the
charges are formal.

S 2
S
O O O O

A VB wavefunction is written for each bonded pair. It is convenient to assume

that sulfur and oxygen atoms are sp2 hybridized. Each of the S–O σ bonds is
formed by the overlap of one sp2 hybrid on sulfur and one sp2 hybrid on an
oxygen atom projecting towards each other. �ere is also a π bond formed
between the unhybridized �p atomic orbital on sulfur and an unhybridized �p
atomic orbitals on the oxygen. �is π bond is involved in resonance, as it can be
between the sulfur and any of the oxygen atoms. �e lone pairs on the oxygen
atoms are either accommodated in sp2 orbitals or in an out-of-plane �p orbitals
if the latter is not involved in a π bond. �e lone pair on the sulfur atom in SO2
resides in an sp2 hybrid atomic orbital.

E�A.�(b) �e ground state electronic con�guration of phosphorus is [Ne]3s2 3p1x 3p1y 3p1z .
In the ground state it has three unpaired electrons on the three di�erent �p
orbitals, therefore it is able to form three covalent bonds. Promotion of an elec-
tron from �s orbital to �d results in the con�guration [Ne]3s1 3p1x 3p1y 3p1z 3d1 .
�ese orbitals can then be used to form �ve hybrids, each of which can form a
bond.

E�A.�(b) Carbon atoms C�–C� in �,�-pentadiene are sp2 hybridized, whereas carbon
atom C� is sp3 hybridized. �e σ framework of the molecule consists of C–H
and C–C σ bonds. �e C–H σ bonds are formed by the overlap of sp2 or sp3
hybrid atomic orbitals on the carbon atoms with the �s atomic orbitals on the
corresponding hydrogen atoms. Similarly, the C–C σ bonds are formed by the
overlap of sp2 or sp3 hybrid atomic orbitals on neighbouring carbon atoms. �e
two π bonds are formed by the side-by-side overlap of unhybridized �p orbitals
on carbon atoms C� and C�, and likewise between C� and C�.
E�A.�(b) �e carbon and nitrogen atoms in pyridine are sp2 hybridized. �e C–N and
C–C σ bonds are formed by the overlap of sp2 hybrid atomic orbitals on neigh-
bouring carbon or nitrogen atoms with each other. �e C–H σ bonds are
formed by the overlap of a carbon sp2 hybrid atomic orbital with a hydrogen
�s atomic orbitals. Formally there are three π bonds in pyridine. Each of them
is a result of the overlap of a pair of unhybridized �p atomic orbitals on the
nitrogen or the carbon atoms. �ere is a lone pair on nitrogen residing in an
sp2 hybrid atomic orbital.

E�A.�(b) �e condition of orthogonality is given by [�C.�–���], ∫ Ψi∗ Ψ j dτ = 0 for i ≠ j.

�e atomic orbitals are all real, therefore Ψi∗ = Ψi . �e orthogonality condition
becomes

� h 1 h 2 dτ = � [(sin ζ)s + (cos ζ)p] × [(cos ζ)s − (sin ζ)p] dτ

∗

��� � � � � ��� � � � � � ��� � � � � � ��� � � � � � � ��� � � � � � ��� � � � � � �

1 0 0

= sin ζ cos ζ � s2 dτ − sin2 ζ � sp dτ + cos2 ζ � ps dτ

��� � � � � � � � � � � � � �
1

− cos ζ sin ζ � p2 dτ = sin ζ cos ζ − cos ζ sin ζ = 0

All the integrals of the form ∫ sp dτ are zero because the s and p orbitals are
orthogonal, and all the integrals of the form ∫ s2 dτ and ∫ p2 dτ are � because
the orbitals are normalized. �e condition for the orthogonality of h 1 and h 2
is satis�ed.

E�A.�(b) A normalized wavefunction satis�es [�B.�c–���], ∫ ψ ∗ ψ dτ = 1. �e wave-

function is normalized by �nding the values of N 1 and N 2 for which h 1 =
N 1 [(sin ζ)s + (cos ζ)p] and h 2 = N 2 [(cos ζ)s − (sin ζ)p] satisfy this condition.
�e orbital wavefunctions s and p are real, as are N 1 and N 2 , therefore, for h 1

� h 1 h 1 dτ = N 1 � [(sin ζ)s + (cos ζ)p] dτ

∗ 2 2

� �
� ��� � � � � ��� � � � � � ��� � � � � � � � � � � � � � ��� � � � � � ��� � � � � � ��
1 1 0
� �
� �
= N 12 �sin2 ζ � s2 dτ + cos2 ζ � p2 dτ +2 sin ζ cos ζ � sp dτ �
� �
� �
� �
� �
= N 12 [sin2 ζ + cos2 ζ] = N 12

�e integral ∫ sp dτ is zero because the s and p orbitals are orthogonal. �e

integrals ∫ s2 dτ and ∫ p2 dτ are � because the s and p orbitals are normalized.
�e identity sin2 θ + cos2 θ = 1 is used in the last step. �e normalization
condition is N 12 = 1, therefore N 1 = 1. A similar calculation shows that N 2 = 1
also.
P�A.� For the purposes of this problem, the px orbital has the same properties as a unit
vector along the x-axis and the p y orbital is likewise a unit vector along the y-
axis. �e hybrid orbital ψ is represented by a vector resulting from the addition
of the vectors representing the px and p y orbitals. �e s orbital is spherically
symmetric about the origin, therefore it has no e�ect on the direction of the
hybrid.

ψ �
3
p
2 y

α β
� x
− 12 px

�e angle α is calculated as
� � √
α = tan−1 � 3�2� 1�2� = tan−1 3 = 60○

�erefore the vector representing ψ makes and angle β = 180○ −α = 180○ −60○ =
120○ to the x-axis.

P�A.� Following the same logic as in Problem P�A.� and Problem P�A.�, the vector
representation of the two hybrid atomic orbitals is as shown below.

h1

θ�2
x

h2

It follows from the diagram that for h 1 the contribution from px is proportional
to cos θ�2, and the contribution from p y is proportional to sin θ�2; for h 2 all
that is di�erent is that the sign of the contribution from p y is reversed. Both
hybrids will have a contribution from the s orbital, and so can be written

h 1 = s+λ �cos(θ�2) px + sin(θ�2) p y � h 2 = s+λ �cos(θ�2) px − sin(θ�2) p y �

 �e parameter λ is to be determined, but it is the same for both hybrids as
they are equivalent. �e value of λ is found by using the requirement that the
hybrids are orthogonal, ∫ h 1 h 2 dτ = 0

� [s+λ �cos(θ�2)px + sin(θ�2)p y �][s+λ �cos(θ�2)px − sin(θ�2)p y �] dτ = 0

Because the atomic orbitals are orthonormal the integral is evaluates to

1 + λ 2 �cos2 (θ�2) − sin2 (θ�2)� = 1 + λ 2 cos θ

where the identity cos 2x = cos2 x − sin2 x is used. Setting this to zero gives
λ = ±(−1� cos θ)1�2 .
�e ratio of p to s in a hybrid is given by the ratio of the squares of the coe�-
cients of the contributing atomic orbitals. For these hybrids

p character [λ cos(θ�2)]2 + [±λ sin(θ�2)]2

= = λ2
s character 12
where the identity cos2 x +√sin2 x = 1 is used. �erefore what is usually known
as an√sp2 hybrid has λ = 2, an sp hybrid has λ = 1, and an sp3 hybrid has
λ = 3. �e plotshown in Fig. �.� shows the relationship between λ 2 and the
angle between the hybrids.

3.0

2.5

2.0
λ2

1.5

1.0
100 120 140 160 180
sp3 sp2 θ�○ sp

D�B.� As described in Section �B.�(b) on page ���, the reason why the bonding molec-
ular orbital is lower in energy than the atomic orbitals is not entirely clear.
However, it is clear that bonding character correlates strongly with molecular
 orbitals that have an accumulation of electron density between nuclei due to
overlap and constructive interference of their component atomic orbitals. A
simple and plausible explanation of this correlation is that enhanced electron
probability between nuclei lowers the potential energy by putting electrons in
a position where they can be attracted to two nuclei at the same time; however,
the source of the reduced energy may be more complicated.

E�B.�(b) �e normalization condition is given by [�B.�c–���], ∫ ψ ∗ ψ dτ = 1. �e wave-

function is normalized by �nding N such that ψ = N(ψA + λψB + λ′ ψB′ ) satis�es
this condition. �e wavefunctions ψA , ψB and ψB′ are all real as is N, therefore

� Ψ Ψ dτ = N � (ψA + λψB + λ ψB ) dτ
∗ 2 ′ ′ 2

��� � � � � � � � � � � � � � � � ��� � � � � � � �� � � � � � � � ��� � � � � � � � �� � � � � � � � � � � ��� � � � � � � � � � � � ��� � � � � � � � � � � � �

1 1 1 S

= N � � ψA dτ +λ � ψB dτ +λ � ψB dτ +2λ� ψA ψB dτ
2 2 2 2 ′2 ′2

S′
��� � � � � � � � � � � � ��� � � � � � � � � � � � � ��� � � � � � � � � � � �� � � � � � � � � � � � � �
0

+ 2λ � ψA ψB dτ +2λλ � ψB ψB′ dτ �
′ ′ ′

= N 2 (1 + λ 2 + λ′2 + 2λS + 2λ′ S)

�e integrals ∫ ψA2 dτ, ∫ ψB2 dτ and ∫ ψB′ dτ are � because the wavefunctions
2

ψA , ψB and ψB′ are normalized; ∫ ψB ψB′ dτ = 0 because the exercise speci�es

that these are orthogonal. �e value of this integral must equal �, therefore the
normalization constant is N = 1�(1 + λ 2 + λ′2 + 2λS + 2λ′ S)1�2 .

E�B.�(b) �e condition of orthogonality is given by [�C.�–���], ∫ ψ ∗i ψ j dτ = 0 for i ≠ j.

�e given molecular orbital, ψ i = 0.727A + 0.144B is real, therefore ψ ∗i = ψ i .
�e new linear combination of A and B, which is orthogonal to ψ i must have
the form of ψ j = A + βB, where the coe�cient of wavefunction A is chosen
to be � for simplicity. Substitution of these wavefunctions in the condition of
orthogonality gives

� ψ i ψ j dτ = � (0.727A + 0.144B) × (A + βB)dτ

∗

��� � � � � � � � � � � � � � ��� � � � � � ��� � � � � � � ��� � � � � � � � � � � � � � � �

1 1 S

= 0.727� A2 dτ +0.144β � B 2 dτ +(0.727β + 0.144)� AB dτ

= 0.727 + 0.144β + (0.727β + 0.144)S

Using S = 0.117 the value of the integral becomes 0.744 + 0.229β. �is value
must be zero for the two wavefunctions to be orthogonal, therefore β = −3.25
and so ψ j = A − 3.25B.
 Normalization of ψ i follows the same logic as in Exercise E�B.�(a). First the
wavefunction is written as ψ i = N(0.727A + 0.144B) and then the normaliza-
tion constant N is found such that ∫ ψ ∗ ψ dτ = 1.

� ψ i ψ i dτ = � [N(0.727A + 0.144B)] dτ
∗ 2

� ��� � � � � � � � � � � � � � ��� � � � � � ��� � � � � � � ��� � � � � � � � � � � � � � � ��

1 1 S

2� �
= N �0.727 � A dτ +0.144 β � B dτ +(2 × 0.727 × 0.144)� AB dτ �
2 2 2 2
� �
� �
= N 2 (0.549 + 0.209S)
√
Using S = 0.117 gives a value of 0.573N 2 for the integral, therefore N = 1� 0.573
= 1.32. �erefore the normalized wavefunction is

ψ i = 1.32 × (0.727A + 0.144B) = 0.960A + 0.190B

Normalization of ψ j follows a similar procedure as for ψ i , giving N = 0.304

and therefore ψ j = 0.304A − 0.989B .

E�B.�(b) �e energy of the σ∗ antibonding orbital in H� + is given by [�B.�–���], E σ∗ =

EH�s + j 0 �R − ( j − k)�(1 − S). Molecular potential energy curves are usually
plotted with respect to the energy of the separated atoms, therefore the energies
to be plotted are E σ∗ − EH�s = j 0 �R − ( j − k)�(1 − S). Using [�B.�d–���],
j 0 �a 0 = 27.21 eV = 1 Eh , the energy for R�a 0 = 1 is computed as

(1 E h ) (0.729 E h ) − (0.736 E h )
E σ∗ − EH�s = − = +1.05 E h
1 (1 − 0.858)

Similar calculations give the following energies

R�a 0 � � � �
(E σ∗ − EH�s )�Eh +1.05 +0.340 +0.132 +5.52 × 10−2

�ese data are plotted in Fig. �.�. �e data are �tted well by the following cubic

(E σ − EH�s )�E h = −0.0616(R�a 0 )3 + 0.6203(R�a 0 )2 − 2.1385(R�a 0 ) + 2.6288

Note that this cubic equation has no physical meaning, it is only used to draw
the line on the plot above.

E�B.�(b) �e sketch below shows the bonding and the antibonding face-to-face overlap
of two d orbitals, resulting in δ molecular orbitals. �e bonding molecular or-
bital is symmetric with respect to inversion, therefore it is labelled δg , whereas
the antibonding molecular orbital is antisymmetric with respect to inversion,
and is labelled δu .
 1.0

(E σ∗ − EH�s )�E h
0.5

0.0
1 2 2 3 3 4 4
R�a 0

y y

x x

δ g bonding δ u antibonding

P�B.� �e bonding and antibonding molecular orbitals resulting from the linear com-
bination of hydrogenic atomic orbitals are given by

ψ± = N± (ψH�sA ± ψH�sB )
1 1
= N± � e−rA �a 0 ± e−rB �a 0 �
(πa 0 )
3 1�2
(πa 03 )1�2

where rA and rB are the distances of the electron from nucleus A and B, respec-
tively. Given that the internuclear separation along the z-axis is R, in Cartesian
coordinates rA and rB become

rA = (x 2 + y 2 + z 2 )1�2 and rB = (x 2 + y 2 + (z − R)2 )1�2

�erefore the wavefunction is

N±
ψ± = �e−(x +y +z ) �a 0 ± e−(x +y +(z−R) ) �a 0 �
2 2 2 1�2 2 2 2 1�2

(πa 0 )
3 1�2

�e normalisation constants at the experimental internuclear separation (R =

106 pm = 2.00 a 0 ) are calculated in Example �B.� on page ���, giving N+ =
 0.56 and N− = 1.10. Both of the bonding and antibonding wavefunctions are
real, therefore ψ± = ψ±∗ . �e square of the wavefunction gives the probability
density of �nding the electron at a particular position. �e volume element δV
given in this problem (1.00 pm3 ) is small enough that it is assumed that the
wavefunction has a constant value over the entire volume element. �erefore
the probability is simply ψ 2 δV .
(a) At nucleus A x = y = z = 0 the probability is computed as

N+2
ψ+2 δV = �e0 + e−2.00 a 0 �a 0 � δV
2

(πa 0 )
3

0.562
= �1 + e−2.00 � × (1.00 pm3 ) = 8.7 × 10−7
2
[π × (52.91 pm)3 ]

(b) �e probability of �nding the electron at nucleus B must be the same as

the probability of �nding the electron at nucleus A due to the inherent
symmetry of the problem. �erefore P = 8.7 × 10−7 .
(c) �e Cartesian coordinates of the position halfway between A and B are
x = y = 0 and z = 1.00 a 0 . At this position the probability is computed as

N+2 2
ψ+2 δV = �e−1.00 a 0 �a 0 + e−[((1.00 a 0 )−(2.00 a 0 )) ] �a 0 � δV
2 1�2

(πa 0 )
3

0.562
= �e−1.00 + e−1.00 � × (1.00 pm3 ) = 3.6 × 10−7
2
[π × (52.91 pm)3 ]

(d) At 20 pm along the bond from nucleus A and 10 pm perpendicularly

the coordinates are z = 20 pm = 0.378... a 0 and x 2 + y 2 = (10 pm)2 =
(0.189... a 0 )2 . At this position the probability is computed as

N+2
ψ+2 δV = �e−[(0.189... a 0 ) +(0.378... a 0 ) ] �a 0
2 2 1�2

(πa 03 )
2
+e−[(0.189... a 0 ) +((0.378... a 0 )−(2.00 a 0 ))2 ]1�2 �a 0
� δV
2

0.562
= �e−0.422... + e−1.63... � × (1.00 pm3 )
2
[π × (52.91 pm)3 ]
= 4.9 × 10−7

�e calculation of the probabilities when the electron occupies the antibonding

orbital follows exactly the same procedure as above, and gives the following re-
sults: (a) P = 1.9 × 10−6 ; (b) P = 1.9 × 10−6 ; (c) P = 0 , which is the expected
result, as the antibonding orbital has a node going through the point halfway
between the two nuclei; (d) P = 5.5 × 10−7

P�B.� �e bonding and antibonding MO wavefunctions are ψ± = N± (ψ A ±ψ B ), where

N± is the normalizing factor. �is factor depends on the distance between
the nuclei (Example �B.� on page ���), but this just scales the orbital without
changing any of its key features. �erefore, this normalizing factor, as well as
those for ψ A and ψ B given in Brief illustration �B.� on page ��� are simply
ignored. Without loss of generality, it is assumed that atom A is located at
z A1 = 0 and atom B at z B1 = R, the internuclear separation. �e requirement
is to plot the wavefunction along the z-axis, so x A1 = y A1 = 0, and likewise for
atom B. With all of these conditions imposed the function to be plotted is
ψ± = e−�z��a 0 ± e−�(z−R)��a 0
�e modulus sign is needed because the argument of the exponential is the
distance from the nucleus, which is always positive.
(a) �e wavefunction corresponding to the bonding molecular orbital is plot-
ted in Fig. �.� for three di�erent internuclear separations. �e positions
of the nuclei for each wavefunction are indicated by dotted lines. None of
the plotted wavefunctions have any nodes. �e value of the wavefunctions
and hence the electron densities in the internuclear region are larger than
the sum of the values of the corresponding wavefunctions describing the
hydrogenic atomic orbitals. �is feature is responsible for the bonding.
However, with increasing internuclear separation this surplus electron
density at the internuclear region diminishes, the overall energy of the
wavefunction increases and hence the wavefunction becomes less and less
bonding.
(b) �e wavefunction corresponding to the antibonding molecular orbital at
three di�erent internuclear separations is plotted in Fig. �.�. �e wave-
functions have a node halfway between the two nuclei, which results in
less electron density in the internuclear region compared to if the wave-
functions were not overlapping. �is feature is responsible for the an-
tibonding e�ect. With increasing internuclear separation this de�ciency
in electron density at the internuclear region decreases, the overall energy
of the wavefunction decreases and hence the wavefunction becomes less
and less antibonding.

R = 5a 0

R = 3a 0

R = 2a 0

−4 −2 0 2 4 6 8 10
z�a 0
 R = 5a 0

R = 3a 0

R = 2a 0
z�a 0
−4 −2 0 2 4 6 8 10

D�C.� �e building-up principle for homonuclear diatomic molecules is essentially

the same as for atoms, but the diatomic molecular orbitals used in the former
are di�erent in name and in nature than the atomic orbitals used in the latter.
A diagram of energy levels (orbitals) and degeneracies is needed. For diatomic
molecules, these energy levels are either nondegenerate (for σ bonds) or doubly
degenerate (for all others). �e orbitals are populated with electrons, placing
each successive electron in the lowest-energy orbital available, no more than
two electrons per orbital. Hund’s rule indicates that di�erent degenerate or-
bitals should be populated �rst, with electrons that have parallel spins, before
pairing two electrons in the same degenerate orbital.

D�C.� �e bond strength is related to the extent to which the occupied bonding molec-
ular orbitals are lowered in energy compared to the constituent atomic orbitals.
As described in Topic �B for the case of H� + , this lowering in energy depends
on the size of the term k, [�B.�c–���], which is a measure of the interaction
between a nucleus and the excess electron density in the internuclear region
arising from overlap.
�e overlap integral, S, is a di�erent quantity than k, but its behaviour with
(for example) internuclear distance is quite similar. �us the overlap integral
is o�en taken as a proxy for k, not least as it much easier to imagine how
the overlap varies when the orbital or the internuclear distance is varied. It is
therefore common to speak of a bond being strong when ‘there is good overlap’.
�e fact that there is a correlation between overlap and bond strength may,
however, simply be fortuitous as the theory does not indicate such a connection.

E�C.�(b) �e molecular orbital diagram for O2 2− and F2 − is shown in Fig. �C.�� on page
���, and that of N2 is shown in Fig. �C.�� on page ���. According to the Pauli
principle, up to two valence electrons can be placed in each of the molecular
 orbitals. First the lowest energy orbital is �lled up, then the next lowest and so
on, until all the valence electrons are used up.
(i) F2 − has 7+7+1 = 15 valence electrons (VE) overall, therefore the ground-
state electron con�guration is 1σ 2g 1σ∗2 2 4 ∗4 ∗1
u 2σ g 1π u 1π g 2σ u . �e bond or-
der is de�ned in [�C.�–���] as b = 2 (N − N ), therefore b = 12 (8−7) = 12 .
1 ∗

(ii) N2 : 5 + 5 = 10 VE; 1σ 2g 1σ∗2

u 2σ g 1π u ; b = 2 (8 − 2) = 3.
2 4 1

(iii) O2 2− : 6 + 6 + 2 = 14 VE; 1σ 2g 1σ∗2

u 2σ g 1π u 1π g ; b = 2 (8 − 6) = 1.
2 4 ∗4 1

E�C.�(b) �e molecule with the greater bond order is expected to have the larger dis-
sociation energy. Qualitatively Li2 and Be2 share the same molecular orbital
energy level diagram, shown in Fig. �C.�� on page ���. Li2 has 1 + 1 = 2
valence electrons overall, therefore its ground-state electron con�guration is
1σ 2g . �e bond order is de�ned in [�C.�–���] as b = 12 (N − N ∗ ), therefore
b = 12 (2 − 0) = 1.
Be2 has 2 + 2 = 4 valence electrons, its con�guration is 1σ 2g 1σ∗2
u , and the bond
order is b = 12 (2 − 2) = 0. Li2 has greater bond order than Be2 , therefore Li2 is
expected to have the larger bond dissociation energy.

E�C.�(b) �e species with the smaller bond order is expected to have larger bond length.
�e molecular orbital diagram of O2 and its ions is shown in Fig. �C.�� on page
���. �e ground state electron con�guration and the bond order of the species
in the order of increasing number of valence electrons, VE, is given below.

O2 + 6 + 6 − 1 = 11 VE 1σ 2g 1σ∗2 2 4 ∗1
u 2σ g 1π u 1π g b = 12 (8 − 3) = 5
2
O2 6 + 6 = 12 VE ... 1π∗2
g b= 1
2
(8 − 4) =2
O2 −
6 + 6 + 1 = 13 VE ... 1π∗3
g b= 1
2
(8 − 5) = 3
2
O2 2− 6 + 6 + 2 = 14 VE ... 1π∗4
g b= 1
2
(8 − 6) =1

�e bond order increases in the order O2 2− , O2 − , O2 , O2 + , therefore the bond

length is expected to increase in the same order.

E�C.�(b) �e molecular orbital energy level diagram for Li2 , Be2 , B2 , C2 , N2 and related
ions is shown in Fig. �C.�� on page ���, and for O2 , F2 , Ne2 and related ions
in Fig. �C.�� on page ���. Following the same logic as in Exercise E�C.�(b) and
Exercise E�C.�(b) gives

Li2 + 1 + 1 − 1 = 1 VE 1σ 1g b = 12 (1 − 0) = 1
2
Be2 + 2 + 2 − 1 = 3 VE 1σ 2g 1σ∗1
u b = 12 (2 − 1) = 1
2
B2 + 3 + 3 − 1 = 5 VE 1σ 2g 1σ∗2 1
u 1π u b = 12 (3 − 2) = 1
2
C2 + 4 + 4 − 1 = 7 VE 1σ 2g 1σ∗2 3
u 1π u b = 12 (5 − 2) = 3
2
N2 +
5 + 5 − 1 = 9 VE 1σ 2g 1σ∗2
u 1π 4u 2σ 1g b = 12 (7 − 2) = 5
2
O2 + 6 + 6 − 1 = 11 VE 1σ 2g 1σ∗2
u 2σ 2g 1π 4u 1π∗1
g b = 12 (8 − 3) = 5
2
F2 + 7 + 7 − 1 = 13 VE 1σ 2g 1σ∗2
u 2σ 2g 1π 4u 1π∗3
g b = 12 (8 − 5) = 3
2
Ne2 + 8 + 8 − 1 = 15 VE 1σ 2g 1σ∗2
u 2σ 2g 1π 4u 1π∗4 ∗1
g 2σ u b = 12 (8 − 7) = 1
2
 Li2 − 1 + 1 + 1 = 3 VE 1σ 2g 1σ∗1
u b = 12 (2 − 1) = 1
2
Be2 − 2 + 2 + 1 = 5 VE 1σ 2g 1σ∗2 1
u 1π u b = 12 (3 − 2) = 1
2
B2 − 3 + 3 + 1 = 7 VE 1σ 2g 1σ∗2 3
u 1π u b = 12 (5 − 2) = 3
2
C2 − 4 + 4 + 1 = 9 VE 1σ 2g 1σ∗2 4 1
u 1π u 2σ g b = 12 (7 − 2) = 5
2
N2 − 5 + 5 + 1 = 11 VE 1σ 2g 1σ∗2 4 2 ∗1
u 1π u 2σ g 1π g b = 12 (8 − 3) = 5
2
O2 −
6 + 6 + 1 = 13 VE 1σ 2g 1σ∗2
u 2σ 2g 1π 4u 1π∗3
g b = 12 (8 − 5) = 3
2
F2 − 7 + 7 + 1 = 15 VE 1σ 2g 1σ∗2
u 2σ 2g 1π 4u 1π∗4
g 2σ∗1
u b = 12 (8 − 7) = 1
2
Ne2 − 8 + 8 + 1 = 17 VE 1σ 2g 1σ∗2
u 2σ 2g 1π 4u 1π∗4
g 2σ∗2 1
u 3σ g b = 12 (9 − 8) = 1
2

Note that the extra electron in Ne� is accommodated on a bonding molecular

orbital resulting from the overlap of the �s atomic orbitals.

E�C.�(b) �e molecular orbital energy level diagram for Li2 , Be2 , B2 , C2 , N2 and their
ions is shown in Fig. �C.�� on page ���, and for O2 , F2 , Ne2 and their ions in
Fig. �C.�� on page ���. �e lowest unoccupied molecular orbital (LUMO) is
the molecular orbital which is the lowest in energy and is not occupied by any
electrons. �e LUMO of each of the listed ions is indicated by a box around it.

Li2 + 1 + 1 − 1 = 1 VE 1σ 1g 1σ∗0
u

Be2 + 2 + 2 − 1 = 3 VE 1σ 2g 1σ∗1 0
u 1π u

B2 + 3 + 3 − 1 = 5 VE 1σ 2g 1σ∗2 1 0
u 1π u 2σ g

C2 + 4 + 4 − 1 = 7 VE 1σ 2g 1σ∗2 3 0
u 1π u 2σ g

N2 + 5 + 5 − 1 = 9 VE 1σ 2g 1σ∗2 4 1 ∗0
u 1π u 2σ g 1π g

O2 + 6 + 6 − 1 = 11 VE 1σ 2g 1σ∗2 2 4 ∗1 ∗0
u 2σ g 1π u 1π g 2σ u

F2 + 7 + 7 − 1 = 13 VE 1σ 2g 1σ∗2 2 4 ∗3 ∗0
u 2σ g 1π u 1π g 2σ u

Ne2 + 8 + 8 − 1 = 15 VE 1σ 2g 1σ∗2 2 4 ∗4 ∗1 0
u 2σ g 1π u 1π g 2σ u 3σ g

Li2 − 1 + 1 + 1 = 3 VE 1σ 2g 1σ∗1 0
u 1π u

Be2 − 2 + 2 + 1 = 5 VE 1σ 2g 1σ∗2 1 0
u 1π u 2σ g

B2 − 3 + 3 + 1 = 7 VE 1σ 2g 1σ∗2 3 0
u 1π u 2σ g

C2 − 4 + 4 + 1 = 9 VE 1σ 2g 1σ∗2 4 1 ∗0
u 1π u 2σ g 1π g

N2 − 5 + 5 + 1 = 11 VE 1σ 2g 1σ∗2 4 2 ∗1 ∗0
u 1π u 2σ g 1π g 2σ u

O2 − 6 + 6 + 1 = 13 VE 1σ 2g 1σ∗2 2 4 ∗3 ∗0
u 2σ g 1π u 1π g 2σ u

F2 − 7 + 7 + 1 = 15 VE 1σ 2g 1σ∗2 2 4 ∗4 ∗1 0
u 2σ g 1π u 1π g 2σ u 3σ g

Ne2 − 8 + 8 + 1 = 17 VE 1σ 2g 1σ∗2 2 4 ∗4 ∗2 1 ∗0
u 2σ g 1π u 1π g 2σ u 3σ g 3σ u
 Note that the extra electron in Ne� is accommodated on a bonding molecular
orbital resulting from the overlap of the �s atomic orbitals.

E�C.�(b) �e energy of the incident photon must equal the sum of the ionization energy
of the orbital and the kinetic energy of the ejected photoelectron, [�C.�–���],
hν = I + 12 me υ 2 . �erefore the kinetic energy of the photoelectron is Ek =
21 eV − 12 eV = 9 eV, which corresponds to a speed of

2 × (9 eV) × (1.6022 × 10−19 J eV−1 )

1�2
2Ek 1�2
υ=� � =� � = 1.78 × 106 m s−1
me (9.1094 × 10−31 kg)

P�C.� When the internuclear separation is zero the areas of constructive interference
get exactly cancelled by the areas of destructive interference, therefore the over-
lap integral is zero. As the nuclei are moving further away from each other,
the area of constructive interference increases at the expense of the area with
destructive interference, leading to a maximum value in the overlap integral. At
large internuclear separations the overlap of the orbitals becomes insigni�cant,
resulting in zero overlap. Figure �.� shows a plot of the overlap integral
R R 1 R 2
S=� � �1 + � � + � � � e−R�a 0
a0 a0 3 a0

1.0
S

0.5

0.0
0 2 4 6 8 10 12
R�a 0

�e position of the maximum overlap is found by di�erentiating the overlap

integral with respect to x = R�a 0 (the product rule is used), and then setting
the derivative to zero.
dS
= �1 + 2x + x 2 � e−x − �x + x 2 + 13 x 3 � e−x
dx
To �nd the turning points set dS�dx = 0; the factor e−x is cancelled to give
1 + 2x + x 2 − �x + x 2 + 13 x 3 � = 1 + x − 13 x 3 = 0
 It is the easiest to use mathematical so�ware to solve this equation. �e only
real solution is R�a 0 = 2.10, hence the overlap is maximum at R = 2.10 a 0 .

P�C.� �e energy of the incident photon must equal the sum of the ionization energy
of the orbital and the kinetic energy of the ejected photoelectron, [�C.�–���],
hν = 12 me υ 2 + I. Rearranging the equation to give the ionisation energy of the
orbital gives I = hν − 12 me υ 2 , therefore the ionisation energy of the orbitals
from which the electrons were ejected are

I 1 = (21.21 eV) − (11.01 eV) = 10.20 eV

I 2 = (21.21 eV) − (8.23 eV) = 12.98 eV
I 3 = (21.21 eV) − (15.22 eV) = 5.99 eV

�e orbital energies are the negative of the ionisation energies. �e molecular

orbital energy level diagram is shown in Fig �.�, the dashed arrows represent
the ionisation.

0 eV

−5.99 eV
energy

−10.20 eV

−12.98 eV

D�D.� In forming a bond an atom must, to some extent, give up electron density to
be shared with other atoms in the molecule. �e energy needed to do this is
connected with the value of the ionization energy of the orbital. Equally, the
atom will to some extent acquire additional electron density to interact with,
and the energy gained from acquiring this density is connected in some way to
the electron a�nity. �us both electron gain and electron loss, in the loosest
sense, are involved in the process of bonding. It is for this reason that ionization
energy and electron a�nity are involved in the estimation of atomic orbital
energies for participation in bonding. See Section �D.�(a) on page ���.
D�D.� �e Coulomb integral is essentially the energy of an electron when it occupies
an atomic orbital in the molecule.
�e resonance integral is a contribution to the energy of a molecule that can be
associated with an electron interacting with more than one nucleus at once.

E�D.�(b) �e molecular orbital energy level diagram for a heteronuclear diatomic AB

is similar to that for a homonuclear diatomic A2 (Fig. �C.�� on page ��� or
Fig. �C.�� on page ���) except that the atomic orbitals on A and B are no longer
at the same energies. As a result the molecular orbitals no longer have equal
contributions from the orbitals on A and B; furthermore, it is more likely that
the s and p orbitals will mix. From simple considerations it it not possible to
predict the exact ordering of the resulting molecular orbitals, so the diagram
shown Fig. �.� is simply one possibility. Note that because the heteronuclear
diatomic no longer has a centre of symmetry the g/u labels are not applicable.
�e electronic con�gurations are:
(i) XeF (�� valence electrons) 1σ 2 2σ 2 3σ 2 1π 4 2π 4 4σ 1 ; (ii) PN (�� valence elec-
trons) 1σ 2 2σ 2 3σ 2 1π 4 ; (iii) SO – (�� valence electrons) 1σ 2 2σ 2 3σ 2 1π 4 2π 3 .

A Molecule B
4σ
2π
3p of 5p

2p

1π
3σ
2σ
3s or 5s

2s
1σ

E�D.�(b) �e molecular orbital diagram of IF is similar to the one shown in the solu-
tion to Exercise E�D.�(b) where the orbitals on atom A are �s and �p. It is
not possible to predict the precise energy ordering of the orbitals from simple
considerations, so this diagram is simply a plausible suggestion.
IF has 7 + 7 = 14 valence electrons, therefore the ground state electron con�gu-
ration is 1σ 2 2σ 2 3σ 2 1π 4 2π 4 . IF+ has one fewer electron than IF, therefore it has
one fewer electron on the antibonding 2π orbital. IF – has one more electron
than IF, therefore it has one more electron accommodated on the antibonding
4σ orbital. Hence the order of decreasing bond order is IF+ , IF, IF – , which is
expected to be the same as the order of increasing bond length.
E�D.�(b) A suitable MO diagram in shown in the solution to Exercise E�D.�(b). �e ion
with the greater bond order is expected to have the shorter bond length. SO+
has 6 + 6 − 1 = 11 valence electrons, therefore the ground state electron con-
�guration is 1σ 2 2σ 2 3σ 2 1π 4 2π 1 . SO – has two more electrons, both accom-
modated in the antibonding 2π orbital. It follows that SO+ has a greater bond
order than SO – , therefore SO+ is expected to have the shorter bond length.

E�D.�(b) �e relationship between the Pauling and Mulliken electronegativities is given

by [�D.�–���], χPauling = 1.35χMulliken − 1.37. A plot of the Pauling electroneg-
1�2

ativities of Period � atoms against the square root of their Mulliken electroneg-
ativities is shown in Fig. �.�.

3.0
χPauling

2.0

1.0
1.0 1.2 1.4 1.6 1.8 2.0
1�2
χMulliken

�e equation of the best �t line is χPauling = 2.68χMulliken − 1.88, which is very

1�2

far from the expected relationship.

E�D.�(b) �e orbital energy of an atomic orbital in a given atom is estimated using the
procedure outlined in Brief illustration �D.� on page ���, and using data from
the Resource section. �e orbital energy of hydrogen is

αH = − 12 [I + Eea ]
(1 eV)
= − 12 ×[(1312.0 kJ mol−1 )+(72.8 kJ mol−1 )]× = −7.18 eV
(96.485 kJ mol−1 )

�e conversion factor between kJ mol−1 and eV is taken from the front cover
of the book. Similarly for bromine

αBr = − 12 [I + Eea ]
(1 eV)
= − 12 ×[(1139.9 kJ mol−1 )+(324.5 kJ mol−1 )]× = −7.59 eV
(96.485 kJ mol−1 )
E�D.�(b) �e orbital energies of hydrogen (αH = −7.18 eV) and bromine (αBr = −7.59 eV)
are calculated in Exercise E�D.�(b). Taking β = −1.0 eV as a typical value and
setting S = 0 for simplicity, substitution into [�D.�c–���] gives
2 1�2
2β
E± = 12 (αH + αBr ) ± 12 (αH − αBr ) �1 + � � �
αH − αBr
= 12 [(−7.18 eV) + (−7.59 eV)]
� 2 �1�2
� (−2.0 eV) �
± [(−7.18 �
eV) − (−7.59 eV)] �1 + � � �
(−7.18 eV) − (−7.59 eV) �
1
2
� �
� �
= (−7.38... eV) ± (1.02... eV)
�erefore the energy of the bonding molecular orbital is E− = (−7.38... eV) −
(1.02... eV) = −8.40 eV , and the antibonding orbital is at an energy level of
E+ = (−7.38... eV) + (1.02... eV) = −6.36 eV .

E�D.�(b) �e orbital energies of hydrogen (αH = −7.18 eV) and bromine (αBr = −7.59 eV)
are calculated in Exercise E�D.�(b). Taking β = −1.0 eV as a typical value, and
setting S = 0.2, substitution into [�D.�a–���] gives
αH + αBr − 2βS ± [(2βS − (αH + αBr ))2 − 4(1 − S 2 )(αH αBr − β 2 )]1�2
E± =
2(1 − S 2 )
(−14.3... eV) ± (1.03... eV)
= = (−7.48... eV) ± (0.539... eV)
(1.92)
�erefore the energy of the bonding molecular orbital is E− = (−7.48... eV) −
(0.539... eV) = −8.02 eV , and the antibonding orbital is at an energy level of
E+ = (−7.48... eV) + (0.539... eV) = −6.95 eV .

P�D.� (a) �e secular equations for a heteronuclear diatomic molecule with one
basis orbital per atom are given by [�D.�a–���] and [�D.�b–���]. In this
problem there are two atoms but three basis orbitals, so there are three
secular equations which can be generalized from those for the case of two
basis orbitals
(αA − E)cA + (βAB − SAB E)cB + (βAC − SAC E)cC = 0
(βBA − SBA E)cA + (αB − E)cB + (βBC − SBC E)cC = 0
(βCA − SCA E)cA + (βCB − SCB E)cB + (αC − E)cC = 0
In this case, orbitals B and C are on the same atom. It follows that the
resonance integral βBC and the overlap integral SBC are zero, as the atomic
orbitals on one atom are orthogonal to each other. �erefore the secular
equations simplify to
(αA − E)cA + (βAB − SAB E)cB + (βAC − SAC E)cC = 0
(βBA − SBA E)cA + (αB − E)cB = 0
(βCA − SCA E)cA + (αC − E)cC = 0
 and hence the secular determinant is
��� αA − E βAB − SAB E βAC − SAC E ���
��� ���
��� βBA − SBA E αB − E 0 ���
��� β − S E αC − E ���
� CA CA 0 �

(b) Substituting in the given values of the Coulomb integrals and the reso-
nance integrals gives
��� (−7.2 eV) − E (−1.0 eV) − SAB E (−0.8 eV) − SAC E ���
��� ���
��� (−1.0 eV) − SBA E (−10.4 eV) − E 0 ���
��� (−0.8 eV) − S E (−8.4 eV) − E ���
� CA 0 �
(i) If the overlap integrals are set to zero the secular determinant ex-
pands to give

−E 3 − (26 eV)E 2 − (221.08 eV2 )E − (613.936 eV3 )

Setting this to zero and �nding the roots of the cubic (using mathe-
matical so�ware) gives the energies E 1 = −10.7 eV , E 2 = −8.71 eV
and E 3 = −6.58 eV .
For the case where the overlap is zero the hamiltonian matrix is (ex-
pressed in units of eV)

� −7.2 −1.0 −0.8 �

� −1.0 −10.4 0 �
� −0.8 0 −8.4 �

�e matrix of eigenvectors which diagonalizes this matrix is found

using mathematical so�ware as

� 0.294 0.349 0.890 �

� 0.950 −0.206 −0.233 �
� 0.102 0.914 −0.392 �

�e entries in each column of this matrix above give the coe�cients

of the atomic orbitals for the corresponding molecular orbital; the
columns correspond to the molecular orbitals in the same order as
the energies are quoted above. For example the molecular orbital
with E 1 = −10.7 eV is Ψ1 = 0.294 ψ A + 0.950 ψ B + 0.102 ψ C .
(ii) If the overlap integrals SAB and SAC are set to �.�, the secular deter-
minant becomes
��� (−7.2 eV) − E (−1.0 eV) − 0.2E (−0.8 eV) − 0.2E ����
��� ���
��� (−1.0 eV) − 0.2E (−10.4 eV) − E 0 ��
��� (−0.8 eV) − 0.2E (−8.4 eV) − E ����
� 0
= (−0.92)E 3 − (24.528 eV)E 2 − (214.392 eV2 )E − (613.936 eV3 )

�e energies are found by setting the polynomial to zero and then

�nding the roots using mathematical so�ware. �e three roots give
 the energies E 1 = −10.9 eV , E 2 = −8.86 eV and E 3 = −6.93 eV . It
is seen that the energies are not greatly a�ected by the including the
e�ect of non-zero overlap.
When the overlap is non-zero, it is not quite so straightforward to
�nd the coe�cients of the molecular orbitals. It is necessary to return
to the secular equations and, for each energy, to solve them to �nd
the coe�cients.

D�E.� �ese are all terms originally associated with the Hückel approximation used
in the treatment of conjugated π electron molecules, in which the π electrons
are considered independent of the σ electrons. �e π electron binding energy is
the sum of the energies of each π electron in the molecule. �e delocalization
energy is the di�erence in energy of the π electrons between the conjugated
molecule with n π bonds and the energy of n ethene molecules, each of which
has one π bond. �e π bond formation energy is the energy released when a
π bond is formed. It is obtained from the total π electron binding energy by
subtracting the contribution from the Coulomb integrals, α.

D�E.� Gaussian type orbitals centred on atomic nuclei have the advantage over hydro-
genic orbitals that the product of two Gaussian functions on di�erent centres is
equivalent to a single Gaussian function located at a point between the centres.
�erefore, two-electron integrals on three and four di�erent atomic centres can
be reduced to integrals over two di�erent centres, which are much easier to
evaluate numerically; see Section �E.�(a) on page ���.

E�E.�(b) (i) Without taking the Hückel approximations, the secular determinant of
the H4 molecule is written as
��� α 1 − E β 12 − S 12 E β 13 − S 13 E β 14 − S 14 E ���
��� ���
��� β 21 − S 21 E α2 − E β 23 − S 23 E β 24 − S 24 E ���
��� β − S E β 32 − S 32 E α3 − E β 34 − S 34 E ���
��� 31 31 ���
��� β 41 − S 41 E β 42 − S 42 E β 43 − S 43 E α4 − E ���

where α n is the Coulomb integral of the orbital on atom n, β nm is the

resonance integral accounting for the interaction between the orbitals on
atoms n and m, E is the energy of the molecular orbital and S nm is the
overlap integral between the orbtials on atoms n and m.
Within the Hückel approximations the energy of the basis atomic orbitals
is taken to be independent of the position of the corresponding atoms in
the molecule, therefore all Coulomb integrals are set equal to α (given
 that there is only one type of basis atomic orbital and only one type of
atom is involved in the problem). Interaction between orbitals on non-
neighbouring atoms is neglected, that is β nm = 0 if atoms n and m are
not neighbouring. All other resonance integrals are set equal to β. �e
overlap between atomic orbitals is also neglected, therefore all overlap
integrals S nm with n ≠ m are set to zero. Hence the secular determinant
for linear H� is
��� α − E ���
��� β 0 0 ���
��� β α−E β 0 ���
��� 0 α−E ���
��� β β ���
��� 0 0 β α−E ���

(ii) In this case hydrogen atoms � and � are neighbours, therefore β 14 = β,

and the secular determinant is
��� α − E ���
��� β 0 β ���
��� β α−E β 0 ���
��� 0 α−E ���
��� β β ���
��� β 0 β α−E ���

E�E.�(b) (i) �e energies of the π molecular orbitals of the allyl system are calculated
in Example �E.� on page ��� as E = α + 1.41β, α, α − 1.41β. Note that
α and β are negative quantities, therefore the molecular orbital lowest in
energy is the one with energy of α + 1.41β. �e allyl radical has three
π electrons and therefore the ground state ic con�guration is ψ 12 ψ 21 . �e
π-electron binding energy is E π = 2(α + 1.41β) + α = 3α + 2.82β .
(ii) �e energies of the π molecular orbitals of cyclobutadiene are calculated
in Example �E.� on page ��� as E = α + 2β, α, α, α − 2β. In the cyclobu-
tadiene cation there are three π electrons and the ground state electronic
con�guration is ψ 12 ψ 21 . �e π-electron binding energy is E π = 2(α +2β)+
α = 3α + 4β .

E�E.�(b) �e delocalization energy is the energy di�erence between the π-electron bind-
ing energy E π and the hypothetical π-electron binding energy if the given species
had isolated π bonds; Edeloc = E π − N π (α + β), where N π is the number of
π electrons. �e π-bond formation energy is de�ned in [�E.��–���] as Ebf =
E π − N π α.

(i) �e allyl radical has � π electrons and its π-electron binding energy is
calculated in Exercise E�E.�(b) as E π = 3α + 2.82β. �erefore Edeloc =
(3α + 2.82β) − 3(α + β) = −0.18β and Ebf = (3α + 2.82β) − 3α = 2.82β .
�e calculation of Edeloc does not quite work in this case because the third
electron in the allyl radical would not be placed in a localized π bonding
orbital but in a out-of-plane p orbital, with energy α. �e localized energy
is therefore 2(α + β) + α = 3α + 2β and hence Edeloc = 0.82β.
 (ii) �e cyclobutadiene cation has � π electrons and its π-electron binding
energy is calculated in Exercise E�E.�(b) as E π = 3α + 4β. �erefore
Edeloc = (3α + 4β) − 3(α + β) = β and Ebf = (3α + 4β) − 3α = 4β .

E�E.�(b) (i) Following the same logic as in Exercise E�E.�(b) and applying the Hückel
approximations as explained there the secular determinant for azulene
is written as (the numbers in bold refer to the numbering of the carbon
atoms in the molecule)
� � � � � � � � � ��
� α−E β 0 0 0 0 0 0 0 β
� β α−E β 0 0 0 0 0 0 0
� 0 β α−E β 0 0 0 0 0 0
� 0 0 β α−E β 0 0 0 0 β
� 0 0 0 β α−E β 0 0 0 0
� 0 0 0 0 β α−E β 0 0 0
� 0 0 0 0 0 β α−E β 0 0
� 0 0 0 0 0 0 β α−E β 0
� 0 0 0 0 0 0 0 β α−E β
�� β 0 0 β 0 0 0 0 β α−E

(ii) Similarly for acenaphthylene

� � � � � � � � � �� �� ��
� α−E β 0 0 0 0 0 0 0 0 β 0
� β α−E β 0 0 0 0 0 0 0 0 0
� 0 β α−E β 0 0 0 0 0 0 0 0
� 0 0 β α−E β 0 0 0 0 0 0 β
� 0 0 0 β α−E β 0 0 0 0 0 0
� 0 0 0 0 β α−E β 0 0 0 0 0
� 0 0 0 0 0 β α−E β 0 0 0 0
� 0 0 0 0 0 0 β α−E β 0 0 β
� 0 0 0 0 0 0 0 β α−E β 0 0
�� 0 0 0 0 0 0 0 0 β α−E β 0
�� β 0 0 0 0 0 0 0 0 β α−E β
�� 0 0 0 β 0 0 0 β 0 0 β α−E

E�E.�(b) To calculate the π-electron binding energy of the given systems, it is necessary
to calculate the energies of the occupied molecular orbitals. �is is done by di-
agonalising the hamiltonian matrix: the diagonal elements of the resulting ma-
trix are the energies of the molecular orbitals. �e hamiltonian matrix has the
same form as the secular matrix except that the diagonal elements are α instead
of α − E. Alternatively, the energies can be found my �nding the eigenvalues of
the hamiltonian matrix, or by multiplying out the secular determinant, setting
the resulting polynomial in E to zero and then �nding the roots. Mathematical
so�ware is needed for all of these approaches.
�e secular determinants are derived in Exercise E�E.�(b), and from these the
form of the hamiltonain matrix is easily found.
 (i) �e entries of the diagonalized hamiltonian matrix for azulene are E = α+
2.31β, α +1.65β, α +1.36β, α +0.887β, α +0.477β, α −0.400β, α −0.738β,
α − 1.58β, α − 1.87β, α − 2.10β. �e π system of azulene accommodates
�� electrons, therefore the � lowest energy π molecular orbitals are �lled.
�e π-electron binding energy is therefore E π = 2(α + 2.31β) + 2(α +
1.65β) + 2(α + 1.36β) + 2(α + 0.887β) + 2(α + 0.477β) = 10α + 13.4β .
(ii) �e entries of the diagonalized hamiltonian matrix for acenaphthylene
are E = α + 2.47β, α + 1.69β, α + 1.68β, α + β, α + 0.831β, α + 0.638β,
α−0.285β, α−β, α−1.31β, α−1.43β, α−1.92β, α−2.36β. �e π system of
acenaphthylene accommodates �� electrons, therefore the � lowest energy
π molecular orbitals are �lled. �e π-electron binding energy is therefore
E π = 2(α + 2.47β) + 2(α + 1.69β) + 2(α + 1.68β) + 2(α + β) + 2(α +
0.831β) + 2(α + 0.638β) = 12α + 16.6β .

E�E.�(b) �e hamiltonian for a single electron in H2 + is given by [�B.�–���]. It has a

kinetic energy term, T̂ = −(ħ 2 �2me )∇21 , and a potential energy term, V̂ . �e
species LiH2+ has two electrons, therefore the kinetic energy term is written as

ħ2 2 ħ2 2
T̂ = − ∇1 − ∇
2me 2me 2
�e energy of interaction between an electron and a nucleus with charge num-
ber Z at distance r is given by −Ze 2 �4πε 0 r. �e potential energy operator
consists of terms for each electron interacting with the H nuclues (Z = 1) and
the Li nucleus (Z = 3)

e2 1 1 3 3 1
V̂ = − � + + + − �
4πε 0 r 1H r 2H r 1Li r 2Li r 12
�e �rst term represent the interaction between electron � and the H nucleus,
and the second is for electron � with the same nucleus. �e third and fourth
terms represent the interactions of the two electrons with the Li nucleus. �e
last term accounts for the repulsion between the two electrons. �e complete
electronic hamiltonian is Ĥ elec = T̂ + V̂ . Because only the electronic hamilto-
nian is required, the repulsion between the two nuclei is not included.

P�E.� (a) Benzene has six carbon atoms in the ring, N = 6, therefore the values k
can take are k = 0, ±1, ±2, +3 and hence the corresponding energies are
E 0 = α + 2β, E±1 = α + β, E±2 = α − β, and E+3 = α − 2β.
Cyclooctatetraene has eight carbon atoms in the ring, N = 8, therefore the
values k can take are k = 0, ±1, ±2, ±3, +4 and hence the corresponding
energies are E 0 = α + 2β, E±1 = α + 1.41β, E±2 = α, E±3 = α − 1.41β, and
E+4 = α − 2β.
In both cases the molecular orbitals come in degenerate pairs, except for
the lowest energy, most bonding molecular orbital, and for the highest
energy, most antibonding molecular orbital.
 (b) �e delocalisation energy is given by Edeloc = E π − N π (α + β), where
N π is the number of π electrons. In the ground state of benzene, two
electrons occupy the orbital with energy E 0 and four electrons occupy the
degenerate pair of orbitals with energy E±1 . Hence the π-electron binding
energy of benzene is E π = 2E 0 + 4E±1 = 2(α + 2β) + 4(α + β) = 6α + 8β.
�erefore the delocalization energy is Edeloc = 6α + 8β − 6(α + β) = 2β .
To calculate the delocalization energy of hexatriene, the energies of the
occupied molecular orbitals are required. �e six electrons in the π sys-
tem of hexatriene occupy the three lowest energy orbitals, therefore the
π-electron binding energy is

E π = 2E 1 + 2E 2 + 2E 3
= 2[α + 2β cos(π�7)] + 2[α + 2β cos(2π�7)] + 2[α + 2β cos(3π�7)]
= 6α + (6.98...)β

Hence the delocalization energy of hexatriene is Edeloc = 6α +(6.98...)β −

6(α + β) = 0.99β . �e lowering in energy as a result of delocalization
in benzene in greater than in hexatriene, consistent with the ‘aromatic’
system in benzene.
(c) �e π-electron binding energy in cyclooctatetraene is

E π = 2E 0 + 4E±1 + 2E±2 = 2(α + 2β) + 4(α + 1.41β) + 2α = 8α + 9.64β

�e delocalization energy is therefore Edeloc = 8α + 9.64β − 8(α + β) =

1.64β .
�e π-electron binding energy in octatetraene is

E π = 2E 1 + 2E 2 + 2E 3 + 2E 4
= 2[α + 2β cos(π�9)] + 2[α + 2β cos(2π�9)]
+ 2[α + 2β cos(3π�9)] + 2[α + 2β cos(4π�9)]
= 8α + (9.51...)β

�erefore the delocalization energy is Edeloc = 8α +(9.51...)β −8(α + β) =

1.52β . �e di�erence in delocalization energies between cyclooctate-
traene and octatetraene is much smaller than the di�erence in the values
for benzene and hexatriene. �is is taken as an result of benzene being
‘aromatic’ in contrast to cyclooctatetraene which is sometimes described
as ‘antiaromatic’.

P�E.� Within the Hückel approximations, the secular determinant of ethene is

α−E β
� �
β α−E

�e hamiltonian matrix is of the same form, but with diagonal elements α

α β 0 1
H=� � = α� + β � �
β α 1 0
As explained in the text, in order to �nd the energies it is su�cient to diagonal-
ize the matrix on the right, and this is convenient because most mathematical
so�ware packages are only able to diagonalize numerical matrices. �e matrix
which achieves the diagonalization is

0.707 0.707
� �
0.707 −0.707

and the diagonal elements are ±1.00, implying that the energies are α ± 1.00 β.

�e secular determinant and hamiltonian matrix for butadiene are

��� α − E ���
��� β 0 0 ��� �0 1 0 0 �
��� β α − E β 0 ��� �1 0 1 0 �
��� 0 ��� H = α� + β � �
��� β α−E β ��� �0 1 0 1 �
��� 0 0 β α−E ��� �0 0 1 0 �

�e matrix which achieves the diagonalization is

� 0.372 0.602 0.602 0.372 �

� 0.602 0.372 −0.372 −0.602 �
� �
� 0.602 −0.372 −0.372 0.602 �
� 0.372 −0.602 0.602 −0.372 �

�e diagonal elements are ±1.62, and ±0.618, implying that the energies are
α ± 1.62 β and α ± 0.618 β.

�e secular determinant and hamiltonian matrix for hexatriene are

��� α − E β 0 ��� �0 0�
��� ���
0 0 0 1 0 0 0
���� − ��� �1 0�
β α E β 0 0 0 � 0 1 0 0 �
��� 0 β α−E β 0 ���� �0 0�
H = α� + β � �
0 1 0 1 0
��� �
��� 0 0 β α−E β 0 ���� �0
� 0 1 0 1 0�
�
� �0
��� 0
��� 0 0 β α − E β ���� � 0 0 1 0 1�
�
�� 0 0 0 0 β α − E ���� �0 0 0 0 1 0�

�is is diagonalized by the matrix

� 0.232 0.418 0.521 0.521 0.418 0.232 �

� −0.232 −0.521 −0.418 �
� 0.418 0.521 0.232 �
� −0.418 −0.418 0.232 �
� 0.521 0.232 0.521 �
� −0.232 −0.418 −0.521 �
� 0.521 0.418 0.232 �
� −0.521 0.232 −0.521 �
� 0.418 0.232 0.418 �
� 0.232 −0.418 0.521 −0.521 0.418 −0.232 �

�e diagonal elements are ±1.80, ±1.25, and ±0.445, implying that the energies
are α ± 1.80 β, α ± 1.25 β, and α ± 0.445 β
 �e secular determinant and hamiltonian matrix for octatetraene are
��� α − E β 0 ����
��� 0 0 0 0 0 �0 1 0 0 0 0 0 0�
���� β α − E β 0 ���� �1 0 1 0 0 0 0 0�
�
0 0 0 0
� �
��� 0 β α−E β 0 0 0 0 ���� �0 1 0 1 0 0 0 0�
� �
��� �
��� 0 β α−E β 0 ���� �0 0 1 0 1 0 0 0�
H = α�+β � �
0 0 0
��� 0 �
��� 0 0 β α−E β 0 0 ���� �0 0 0 1 0 1 0 0�
� �
� �0 0 0 0 1 0 1 0�
��� 0 0 0 0 β α−E β 0 ���� � �
��� 0 � �
��� β α − E β ���� �0 0 0 0 0 1 0 1�
�
0 0 0 0
��� 0 0 0 0 0 0 β α − E ���� �0 0 0 0 0 0 1 0�

�is is diagonalized by the matrix

� 0.161 0.303 0.408 0.464 0.464 0.408 0.303 0.161 �

� 0.303 0.464 0.408 0.161 −0.161 −0.408 −0.464 −0.303 �
� �
� −0.408 −0.408 0.408 0.408 �
� 0.408 0.408 0 0 �
� −0.161 −0.408 −0.303 0.303 0.408 −0.161 −0.464 �
� 0.464 �
� −0.161 −0.408 0.303 0.303 −0.408 −0.161 0.464 �
� 0.464 �
� −0.408 −0.408 0.408 −0.408 �
� 0.408 0 0.408 0 �
� �
� 0.303 −0.464 0.408 −0.161 −0.161 0.408 −0.464 0.303 �
� 0.161 −0.303 0.408 −0.464 0.464 −0.408 0.303 −0.161 �

�e diagonal elements are ±1.88, ±1.53, ±1.00, and ±0.347, implying that the
energies are α ± 1.88 β, α ± 1.53 β, α ± 1.00 β, and α ± 0.347 β.
Each column of the diagonalization matrices gives the coe�cients of the atomic
orbitals for the corresponding molecular orbitals. For each molecule, the �rst
column gives the coe�cients for the lowest energy π molecular orbital. All of
these coe�cients have positive signs, therefore the lowest energy π molecular
orbital has no nodes and the lowest energy π molecular orbital is delocalized
over all carbon atoms in the chain. On going to successive columns to the right
the energy of the molecular orbital increases and the number of sign changes
within a column increases. �ese sign changes correspond to nodes in the
molecular molecular orbitals.

P�E.� �e bonding and antibonding e�ects of the HOMO and LUMO have to be con-
sidered to predict the changes in bond strength that accompany the transition.
�e ground state electron con�guration of butadiene is 1π 2 2π 2 , therefore the
HOMO of butadiene is the 2π molecular orbital. Looking at Fig. �E.� on page
���, this molecular orbital is bonding between carbon atoms C� and C� and
likewise between C� and C�, but antibonding between C� and C�. �e LUMO
of butadiene is the 3π molecular orbital, which is antibonding between carbon
atoms C� and C� and likewise between C� and C�, but bonding between C�
and C�. �erefore promotion of an electron from the HOMO to the LUMO
weakens the bonding between C� and C� and likewise between C� and C�, but
strengthens the bonding between C� and C�.
�e HOMO of benzene is the e1g orbital and the LUMO is the e2u orbital. One
of the e1g orbitals, the one on the right in Fig. �E.� on page ���, is bonding
between two pairs of neighbouring carbon atoms, and nonbonding between all
 other pairs of neighbours. One of the e2u orbitals, the one on the le� in Fig. �E.�
on page ���, is antibonding between the same two pairs of neighbouring carbon
atoms as above, and nonbonding between all other pairs of neighbours. �ere-
fore promotion of an electron between these two orbitals decreases the bond
strength between these two pairs of neighbours, and leaves the bond strength
unchanged between all other pairs.
However, the situation is more complicated due to the degeneracy of the HOMO
and LUMO. Promotion of an electron between all possible pairs of HOMO and
LUMO have to be considered together. Due to the six-fold rotational symme-
try of benzene, the bond strength between each pair of atoms is expected to
change the same way. �e HOMO of benzene is overall bonding, whereas the
LUMO is antibonding, therefore promotion of an electron from the HOMO
to the LUMO will, in fact, decrease the bond strength between all pairs of
neighbouring carbon atoms in the molecule.

P�E.� To estimate if the given species are stable with respect to dissociation into smaller
entities, the standard internal energy change for each dissociation reaction is
calculated and its sign examined. �is change in internal energy is given by the
change in the total electron binding energies (Etot ).
�e energies of the molecular orbitals are calculated using the expression given
in Problem P�E.�. �e occupied orbitals are identi�ed and with this infor-
mation it is then possible to calculate the total electron binding energy of the
hydrogen ring compounds, as in the table below (VE is the number of valence
electrons)

species VE energies of occupied MOs E tot

H� � α + 2β, α (degenerate) 4α + 4β
H� +
� α + 2β, α + 0.618β (degenerate) 4α + 5.24β
H� –
� α + 2β, α + 0.618β (degenerate) 6α + 6.47β
H� � α + 2β, α + β (degenerate) 6α + 8β
H� +
� α + 2β, α + 1.25β (degenerate) 6α + 9β
H� � α+β 2α + 2β
H� +
� α + 2β 2α + 4β
–
H � α 2α

�e table includes some other species of interest in these calculations. Note that
in Problem P�E.� it is shown that H3 + is lower in energy than H+ +H2 , therefore
the positively charged hydrogen ring compounds are more likely to dissociate
into H2 and H3 + , than to H2 and H+ . �e negatively charged hydrogen ring
compounds are likely to give H2 and H− as dissociation products.
�e stability of each species is examined in turn.

(i) �e dissociation of H4 is likely to give two H2 molecules, H4 ��→ 2 H2 .

�erefore ∆ r U −○ = Etot (products) − Etot (reactants) = 2(2α + 2β) − (4α +
 4β) = 0. �is means that there is no change in energy on dissociation,
but the process is likely to occur because of the increase in entropy that
will result.

(ii) �e most likely dissociation process for H5 + is H5 + ��→ H2 + H3 + .

�erefore ∆ r U −○ = (2α + 2β) + (2α + 4β) − (4α + 5.24β) = 0.76β. �is
value is negative, hence H5 + is likely to be unstable with respect to H2 and
H3 + .

(iii) �e most likely dissociation process for H5 − is H5 − ��→ 2 H2 + H− .

�erefore ∆ r U −○ = 2(2α + 2β) + (2α) − (6α + 6.47β) = −0.47β. �is
value is positive, hence H5 − is likely to be stable with respect to H2 and
H− .

(iv) �e most likely dissociation process for H6 is H6 ��→ 3 H2 . �erefore

∆ r U −○ = 3(2α + 2β) − (6α + 8β) = −2β. �is value is positive, hence H6
is likely to be stable with respect to H2 .

(v) �e most likely dissociation process for H7 + is H7 + ��→ 2 H2 + H3 + .

�erefore ∆ r U −○ = 2(2α + 2β) + (2α + 4β) − (7α + 9β) = −β. �is value
is positive, hence H7 + is likely to be stable with respect to H2 and H3 + .

P�E.�� Data for ethanol (C� is the oxygen-bearing carbon):

ethanol AM�* PM�* experimental

C�–C�/pm ���.� ���.� ���.�
C�–O/pm ���.� ���.� ���.�
C�–H/pm ���.� ���.� ���
C�–H/pm ���.� ���.� ���
O–H/pm ��.� ��.� ��.�
C�–C�–O/○ ���.�� ���.�� ���.�
C�–O–H/○ ���.�� ���.��
H-C�–H/○ ���.�� ���.��
H–C�–H/○ ���.�� ���.��
∆ f H −○ (g) / kJ mol−1 −262.18 −237.87 −235.10
dipole/D �.�� �.�� �.��

Both methods give fair agreement with experiment but PM� gives a better
estimate of formation enthalpy.

Data for �,�-dichlorobenzene (C� is a chlorine-bearing carbon):

 �,�-dichlorobenzene AM�* PM�* experimental
C�–C�/pm ���.� ���.� ���.�
C�–C�/pm ���.� ���.� ���.�
C�–Cl/pm ���.� ���.� ���.�
C�–H/pm ���.� ���.�
Cl–C�–C�/○ ���.�� ���.��
C�–C�–H/○ ���.�� ���.��
Cl–C�–C�–H/○ �.�� �.��
∆ f H −○ (g) / kJ mol−1 ��.�� ��.�� ��.�
dipole/D �.�� �.�� �.�

Both methods give poor agreement with the experimental formation enthalpy
but both methods are in broad agreement with experimental structural values.

I�.� (a) All the coe�cients of the atomic orbitals for the molecular orbital ψ 1 are
positive, therefore it is a fully bonding molecular orbital. �e molecular
orbital ψ 3 has alternating positive, negative and then positive coe�cients,
therefore it is a fully antibonding molecular orbital. �e molecular orbital
ψ 2 is non-bonding, with no interaction between atomic orbitals on adja-
cent atoms.

(b) �e oxygen, carbon and nitrogen atoms all contribute one p orbital (the
�pz atomic orbital) to the π system, therefore they must be sp2 hybridized.
All the σ bonds to an sp2 hybridized atom must lie in the same plane,
therefore all the atoms connected to the oxygen, carbon and nitrogen
atoms must lie in the same plane together with the oxygen, carbon and
the nitrogen atoms.
(c) �e molecular orbital energy level diagram is shown in part (a). �ere
are four electrons in the π system of the peptide link. Two electrons come
from the formal π bond between the oxygen and the carbon atoms, and
 two from the formal lone pair on the nitrogen atom. Hence the two low-
est energy molecular orbitals, that is the bonding and the non-bonding
molecular orbitals, are �lled.
(d) �is picture of bonding in the peptide group does not invoke delocal-
ization. �e lowest energy, bonding molecular orbital, ψ 4 , represents a
localized π bond between the oxygen and the carbon atoms. According
to this representation, the next highest energy molecular orbital, ψ 5 , is
the lone pair on nitrogen, a non-bonding molecular orbital. �e high-
est energy molecular orbital, ψ 6 is the antibonding π∗ molecular orbital
between the oxygen and the carbon atoms. �e four electrons in the π
system occupy the two lowest energy molecular orbitals.

E O
C N ψ6

O ψ5
C N

O ψ4
C N

(e) Assume that the oxygen, carbon and nitrogen atoms are sp2 hybridized.
�e p orbital on nitrogen is in the plane in which the oxygen, carbon and
their neighbouring atoms are, therefore the two other atoms connected
to nitrogen must lie in a plane perpendicular to this one. �erefore the
oxygen, carbon, nitrogen and the neighbouring atoms cannot all lie in the
same plane.
(f) �e bonding molecular orbital ψ 1 must be lower in energy than ψ 4 , be-
cause ψ 1 extends over three atoms and is bonding between two pairs of
atoms, whereas ψ 4 extends over two atoms only and is bonding between
one pair of atoms only. Following the same logic, ψ 3 must be higher in
energy than ψ 6 . Disregarding the small di�erence in the Coulomb inte-
gral of nitrogen and oxygen, the nonbonding orbitals have approximately
the same energies.
(g) Only the two lowest energy molecular orbitals are occupied in either case.
Occupation of the non-bonding orbital does not result in any di�erence
in the π-electron binding energies. �e bonding molecular orbital in the
case of the planar peptide link is lower in energy, hence occupation of
this orbital results in greater π-electron binding energy when compared
with the occupation of the bonding molecular orbital in the non-planar
peptide link. �erefore planar geometry is the lower energy conformation
of the peptide link.
I�.� �e lower the energy of the vacant orbital, the lower the energy cost of transfer-
ring an electron into that orbital. Hence the tendency of the species to accept
electrons is greater, and so the standard reduction potential of the given species
is also greater. �erefore lower LUMO energy leads to greater standard reduc-
tion potential.

I�.� (a) �e table below lists the energy of the HOMO and the LUMO of the
relevant molecules calculated using the PM� method. �e energy gap
∆E between the HOMO and LUMO is given in eV, as well as the corre-
sponding wavenumber of the transition.
molecule ELUMO EHOMO ∆E (∆E�hc) ν̃obs
/eV /eV /eV �(104 cm−1 ) �cm−1
C� H� �.�� −10.6 ��.� �.�� �����
C� H� �.��� −9.47 �.�� �.�� �����
C� H� −0.249 −8.90 �.�� �.�� �����
C� H�� −0.557 −8.58 �.�� �.�� �����
C�� H�� −0.756 −8.38 �.�� �.��

10
(∆E�hc)�(104 cm−1 )

6
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
ν̃obs �(10 cm )
4 −1

(b) A plot of the predicted frequency of the transitions against the observed
frequencies is shown in Fig. �.�. �e data points are of a good �t to a
straight line. �e equation of the best �t line is
(∆E�hc)�(104 cm−1 ) = 1.09 ν̃obs �(104 cm−1 ) + 2.78

(c) �e HOMO–LUMO energy gap for decapentaene calculated using the

PM� method corresponds (∆E�hc)�(104 cm−1 ) = 6.15, therefore the
predicted wavenumber of the transition is given by
6.15 − 2.78
ν̃obs �(104 cm−1 ) = = 3.09
1.09
hence the transition is predicted to be at 3.09 × 104 cm−1 .
(d) �e computational method used in this problem adequately predicts the
trend in the transition wavenumber but performs poorly in predicting its
absolute value; an error of about 30000 cm−1 is typical. �e calibration
procedure is used to correct the predicted transition wavenumber so that
it agrees as closely as possible with the observed values as possible.
D��A.�

symmetry operation symmetry element

identity, E the entire object
n-fold rotation n-fold axis of symmetry, C n
re�ection mirror plane, σ
inversion centre of symmetry, i
n-fold improper rotation n-fold improper rotation axis, S n

D��A.� A molecule may be chiral (optically active) only if it does not possess an axis of
improper rotation, S n .

E��A.�(b) From the table in Section ��A.�(c) on page ��� a molecule belonging to the
point group D 3h , such as BF� (Fig. ��.�), possesses
• the identity E
• a C 3 axis perpendicular to the plane of the molecule and passing through
the boron atom
• three C 2 axes , each passing through the boron and one of the �uorine
atoms
• a horizontal mirror mirror plane σh in the plane of the molecule
In addition
• the elements C 3 and σh jointly imply the presence of an S 3 axis coincident
with the C 3 axis
• the presence of the C 3 axis and three C 2 axes jointly imply the presence of
three vertical mirror planes σv , each containing the C 3 axis and passing
through the boron and one of the �uorines
 C2,σv
σh
F

C3,S3

F F
C2,σv C2,σv

E��A.�(b) �e point group of the trans-di�uoroethene molecule is identi�ed by following

the �ow diagram in Fig. ��A.� on page ���. Firstly, the molecule is not linear,
which leads to the question “Two or more C n , n > 2?” �ere is one C 2 axis
perpendicular to the plane of the molecule, but no higher order axes, so the
answer to this question is ‘No’. However the fact that it does have a C 2 axis
means that the answer to the next question “C n ?” is ‘Yes’.
�is leads to the question “Select C n with the highest n; then, are there nC 2
perpendicular to C n ?” �e answer to this is ‘No’ because the C 2 axis identi�ed
so far is the only C n axis possessed by the molecule; there are therefore no C 2
axes perpendicular to it.
�is leads to the question “σh ?” to which the answer is ‘Yes’ because there is a
horizontal mirror plane in the plane of the molecule, perpendicular to the C 2
axis. �is leads to the result C nh , and because the C n axis with highest n in this
molecule is C 2 , it follows that the point group is C 2h .
Alternatively, the point group may be identi�ed from the table in Fig. ��A.� on
page ��� by drawing an analogy between the shape of the trans-di�uoroethene
molecule and the shape that appears in the in the box corresponding to C 2h .
From the table in Section ��A.�(c) on page ��� a molecule belonging to the
point group C 2h such as trans-di�uoroethene posseses
• the identity E
• a C 2 axis , perpendicular to the plane of the molecule and passing through
the midpoint of the C=C double bond.
• a horizontal mirror plane σh in the plane of the molecule
In addition
• �e C 2 and σh elements jointly imply a centre of inversion i , which lies
at the midpoint of the C=C double bond.
�ese symmetry elements are shown in Fig. ��.�.

σh
F

F C2,i
E��A.�(b) �e objects to be assigned are shown in Fig. ��.�. For clarity not all symmetry
elements are shown.

C2 σ

C2
C∞ C2

C2,σv C2

σh

C3,S3 C3

C2,σv C2 C2
C2,σv

(i) A sharpened cylindrical pencil is assigned a point group using the �ow
diagram in Fig. ��A.� on page ���, assuming that the main part of the
pencil is a perfect cylinder with no lettering or other pattern and that the
sharpened tip is a perfect cone. It is linear, in the sense that rotation by any
angle around the long axis of the pencil is a symmetry operation so that
the pencil possesses a C∞ axis. However, unless it has been sharpened
at both ends, it does not possess a centre of inversion i. From the �ow
diagram this establishes its point group as C∞v .
Alternatively the point group may be identi�ed from the summary table
in Fig. ��A.� on page ��� by drawing an analogy between the shape of the
pencil and the cone in the cell of the table corresponding to C∞v .
(ii) Modelling the box as a cuboid with length, width and height all di�erent
and ignoring any lettering, pattern, and any means of opening the box, its
point group is established using the �ow diagram in Fig. ��A.� on page
���. It has three C 2 axes, each passing through the centre of a pair of
opposite faces. It also has three mirror planes, one perpendicular to each
of the three C 2 axes. Using the �ow diagram this establishes its point
group as D 2h .
Alternatively the point group may be identi�ed from the summary table
in Fig. ��A.� on page ��� by noting that the symmetry of the box is the
same as that of the rectangle in the cell corresponding to D 2h .
(iii) An unpatterned co�ee mug with a handle has a plane of symmetry that
contains the handle, but no other symmetry elements apart from the iden-
tity. Using the �ow diagram in Fig. ��A.� on page ��� this identi�es its
point group as C s .
(iv) �e described propeller has a C 3 axis along the axis of the propeller and a
σh mirror plane perpendicular to this which contains the three blades. It
 also has three C 2 axes perpendicular to the C 3 axis, each passing through
one of the blades, as well as three σv mirror planes and an S 3 axis. Us-
ing the �ow diagram in Fig. ��A.� on page ��� these symmetry elements
establish the point group as D 3h .
(v) If the blades on the propeller are twisted then the C 3 axis and the three C 2
axes are retained but the there are no longer any mirror planes. Using the
�ow diagram in Fig. ��A.� on page ��� the point group is therefore D 3 .

E��A.�(b) �e molecules to be assigned are shown in Fig. ��.�. For clarity not all symme-
try elements are shown.

C2,σv C2,σv
σv σv σ
Cl

O Cl Cl
O

Furan C 2v γ-pyran C 2v �,�,�-trichlorobenzene C s

In each case the point group is identi�ed using the �ow diagram in Fig. ��A.�
on page ��� having identi�ed the symmetry elements, or by drawing an analogy
with one of the shapes in the summary table in Fig. ��A.� on page ���.

(i) Furan possesses the symmetry elements

• the identity, E
• a C 2 axis that lies in the plane of the molecule and passes through
the oxygen atom.
• two di�erent vertical mirror planes σv , both containing the C 2 axis
but with one lying in the plane of the molecule and the other per-
pendicular to it.
�e point group is C 2v .
(ii) Assuming the six-membered ring to be planar, γ-pyran possesses the sym-
metry elements
• the identity, E
• a C 2 axis that lies in the plane of the molecule and passes through
the oxygen atom and the opposite carbon
• two di�erent vertical mirror planes σv , both containing the C 2 axis
but with one lying in the plane of the molecule and the other perpen-
dicular to it and containing just the oxygen and the opposite carbon.
�e point group is C 2v .
(iii) �,�,�-trichlorobenzene has a mirror plane σ in the plane of the molecule
but no other symmetry elements apart from the identity. Its point group
is therefore C s .
E��A.�(b) �e molecules to be assigned are shown in Fig. ��.� along with some of their
symmetry elements. For clarity not all symmetry elements are shown in all
cases.

C3,S3
σv
OC
C5,S5 OC CO
Fe
σv
F
F C2 C2 OC CO CO
H F σh
C2 F
F F F Cl F Fe
F σh
F OC CO
σv F OC
C∞

HF C∞v IF� D 5h ClF� C 2v Fe� (CO)� D 3h

C3
C2,S4
C4,S4 F
C3,S6
F
C2
i
F

cubane O h tetra�uorocubane Td

(i) HF is a linear molecule and does not possess a centre of inversion. Using
the �owchart in Fig. ��A.� on page ��� this is su�cient to establish the
point group as C∞v .
(ii) IF� possesses a C 5 axis that passes through the iodine and the two axial
�uorine atoms, and �ve C 2 axes perpendicular to the C 5 axis, each of
which passes through the iodine and one of the �ve equatorial �uorine
atoms. It also has a σh mirror plane containing the iodine and all �ve
equatorial �uorines. �ese symmetry elements establish the point group
as C 5h . �e molecule also has �ve σv mirror planes each containing the
iodine, the two axial �uorines and one of the equatorial �uorines, and an
S 5 axis coincident with the C 5 axis.
(iii) �e T-shaped molecule ClF� has a C 2 axis that passes through the chlorine
and the �uorine at the base of the T. It also has two σv mirror planes
containing this axis; one of these corresponds to the plane of the molecule
and contains all four atoms while the other is perpendicular to it and
just contains the chlorine and the �uorine at the base of the T. �ese
symmetry elements establish the point group as C 2v .
 (iv) Fe� (CO)� possesses a C 3 axis that passes through the two iron atoms, and
a σh mirror plane perpendicular to this axis that passes through the three
bridging CO groups. �ere are also three C 2 axes perpendicular to the C 3
axis, each passing through one of the three bridging CO groups. �ese
symmetry elements establish the point group as D 3h . �e molecule also
has an S 3 axis coincident with the C 3 axis, and three σv planes, each
passing through the two iron atoms, one of the bridging CO groups, and
one of the terminal CO groups on each iron.
(v) Cubane has the same symmetry as a cube. It has three C 4 axes, each
passing through the centre of a pair of opposite faces, and three σh mirror
planes, one perpendicular to each C 4 axis. It also has four C 3 axes, each
passing through a pair of diagonally opposite corners, six C 2 axes which
pass through the centres of diagonally opposite edges, and six σd mirror
planes perpendicular to these six C 2 axes. Finally there are three S 4 axes
coincident with the C 4 axes, four S 6 axes coincident with the C 3 axes, and
a centre of inversion i. �is set of symmetry elements matches that given
for the O h group in the table in Section ��A.�(e) on page ���, and O h is
also the conclusion reached from the �ow diagram in Fig. ��A.� on page
���.
(vi) In tetra�uorocubane, the four C 3 axes which pass through opposite cor-
ners of the cube are retained, as are the six σd planes. However, the C 4
axes through opposite sides of the cube are replaced by C 2 axes due to the
reduced symmetry, and the C 2 axes that were present passing through
opposite edges are no longer present. �e σh mirror planes are also lost,
as is the centre of inversion and the S 6 axes, but the three S 4 axes are still
present. �e set of symmetry elements present matches that given for the
Td group in the table in Section ��A.�(e) on page ���, and Td is also the
conclusion reached from the �ow diagram in Fig. ��A.� on page ���.

E��A.�(b) �e molecules are shown in Fig. ��.� along with their point groups. For clarity
not all symmetry elements are shown.

C3 C3,S3

σv σv
H Cl
σh σh
Cl F σ
C2 Cl P NO2
F Cl
F F Cl C2,i
F O2N NO2

CHF� , C 3v PCl� , D 3h trans-C� H� F� �,�,�-trinitrobenzene

C 2h Cs

As explained in Section ��A.�(a) on page ���, only molecules belonging to the

groups C n , C nv , and C s may be polar.
 (i) CHF� , �uoroform, belongs to point group C 3v so it may be polar . �e
dipole must lie along the C 3 axis, which passes through the hydrogen and
the carbon.
(ii) PCl� has a trigonal bipyramidal shape and belongs to point group D 3h .
�erefore it may not be polar.
(iii) trans-di�uoroethene belongs to point group C 2h so it may not be polar.
(iv) �,�,�-trinitrobenzene belongs to point group C s so it may be polar .

E��A.�(b) �ere are �� distinct isomers of dichloroanthracene, which are shown in Fig. ��.�
together with their point groups. All isomers have a mirror plane in the plane
of the paper; additional symmetry elements are marked.

Cl Cl Cl
1 9 8 Cl
Cl 2 7
C2
C2,σv
3 6
4 10 5 Cl Cl Cl

�,� isomer C s �,� isomer C s �,� isomer C 2v �,� isomer C 2h

Cl Cl
Cl Cl Cl Cl
Cl

Cl C2,σv

�,� isomer C s �,� isomer C s �,� isomer C 2v �,� isomer C s

Cl
Cl Cl
Cl Cl
C2
C2,σv C2,σv
Cl Cl Cl

�,�� isomer C s �,� isomer C 2v �,� isomer C 2h �,� isomer C 2v

Cl

Cl C2
Cl C2,σv
Cl
Cl
Cl C2,σv

�,� isomer C s �,�� isomer C s �,�� isomer D 2h

E��A.�(b) As explained in Section ��A.�(b) on page ���, to be chiral a molecule must not
possess an axis of improper rotation, S n . �is includes mirror planes, which
 are the same as S 1 , and centres of inversion, which are the same as S 2 . �e table
in Section ��A.�(e) on page ��� shows that a molecule belonging to Th pos-
sesses S 6 , i, and σh symmetry elements, so such a molecule may not be chiral .
Similarly the table in Section ��A.�(e) on page ��� shows that a molecule be-
longing to Td possesses S 4 and σd symmetry elements, so such a molecule
may not be chiral .

P��A.� �e molecules are shown in Fig. ��.� along with some of their key symmetry el-
ements. For clarity the sulfur atoms have been omitted and not all symmetry el-
ements are shown. �e point group of each species is determined using the �ow
diagram in Fig. ��A.� on page ���. �en, as explained in Section ��A.�(a) on
page ���, molecules belonging to C n , C nv , or C s may be polar while molecules
belonging to all other point groups are not.

C4 C4 C4

F Cl Cl
F i F F F F i F

F F F F F F
C4 F C4 F Cl

SF� SF� Cl trans-SF� Cl�

O h , not polar C 4v , polar D 4h , not polar

F Cl C3 F
F Cl F Cl F Cl
C2
F Cl F Cl Cl Cl C2
F F F

cis-SF� Cl� fac-SF� Cl� mer-SF� Cl�

C 2v , polar C 3v , polar C 2v , polar

P��A.� �ere are �ve distinct geometric isomers which are shown in Fig. ��.� together
with their point groups and some of their symmetry elements. For clarity not
all symmetry elements are shown.
As explained in Section ��A.�(b) on page ��� a molecule is only chiral only if it
does not possess an S n axis; this includes mirror planes σ, which are equivalent
to S 1 , and centres of inversion i, which are equivalent to S 2 . Of the �ve isomers
only the all-cis isomer, which possesses no symmetry elements apart from the
identity and therefore belongs to the point group C 1 , is chiral.
 C2
A σv σv σv
A B C A
B i C
C B A C B A C A
C B C2
A C B C2 A C C2 B A C2 C B
C2 A B C B

all trans A trans B trans C trans all cis

D 2h C 2v C 2v C 2v C1

σd NH2

σd C2'
HON
H2N
NOH
Ni N
C2
σd
NOH C2,S4
H2N HON

C2'
NH2

P��A.� �e [Ni(C7 H9 N5 O2 )2 ]2+ ion is shown in Fig. ��.��.

�e complex possesses a C 2 axis which passes through the nickel and the two
pyridine nitrogens, and an S 4 axis coincident with this. Viewing the complex
down this C 2 axis reveals two C 2′ axes and two mirror planes, which are dihedral
planes σd because they bisect the angle between the C 2′ axes. Using the �ow
diagram in Fig. ��A.� on page ��� these symmetry elements establish the point
group as D 2d .

D��B.� A representative is a mathematical operator, usually taking the form of a matrix,

that represents the e�ect of a particular symmetry operation. It is constructed
by considering the e�ect of the operation on a particular set of basis functions.
�e set of all these mathematical operators corresponding to all the operations
of the group is called a representation.

D��B.� �e process by which a representation is reduced in described in Section ��C.�(b)

on page ���.
E��B.�(b) BF� belongs to the point group D 3h . �e C 3 operation corresponds to rota-
tion by 120○ around the C 3 axis which passes through the boron atom and is
perpendicular to the plane of the molecule.

C3
p1
p3 p2

p4

Using the orbital numbering shown in Fig. ��.��, a 120○ rotation in the direction
indicated leaves the boron p orbital p1 unchanged but permutes the �uorine
orbitals: p2 is converted to p3 , p3 to p4 , and p4 to p2 . �is e�ect is written as
( p1 p3 p4 p2 ) ← ( p1 p2 p3 p4 ) which is expressed using matrix multiplica-
tion as
D(C 3 )
��� � � � � � � � � � � �� � � � � � � � � � � � � �
�1 0 0 0�
�0 0 0 1�
( p1 p3 p4 p2 ) = ( p1 p2 p3 p4 ) � � = ( p1 p2 p3 p4 )D(C 3 )
�0 1 0 0�
�0 0 1 0�

�e representative of this operation is therefore

�1 0 0 0�
�0 0 0 1�
D(C 3 ) = � �
�0 1 0 0�
�0 0 1 0�

E��B.�(b) BF� belongs to the point group D 3h . �e σh operation corresponds to a re-

�ection in the plane of the molecule, while the C 3 operation corresponds to
rotation by 120○ around the C 3 axis which passes through the boron atom and
is perpendicular to the plane of the molecule (Fig. ��.��).

C3
p1
p3 p2
σh
p4

Using the orbital numbering shown in Fig. ��.��, the matrix representatives
for the σh and C 3 operations were found in Exercise E��B.�(a) and Exercise
 E��B.�(b) to be

� −1 0 0 0 � �1 0 0 0�
� 0 −1 0 0 � �0 0 0 1�
D(σh ) = � � D(C 3 ) = � �
� 0 0 � �0 0�
and
0 −1 1 0
� 0 0 0 −1 � �0 0 1 0�

�e matrix representative of the operation C 3 σh is found by multiplying the

matrix representatives of C 3 and σh . Basic information about how to handle
matrices is given in �e chemist’s toolkit �� in Topic �E on page ���.

�1 0 0 0 � � −1 0 0 0 � � −1 0 0 0 �
�0 0 0 1 �� 0 −1 0 0 � � 0 0 0 −1 �
D(C 3 )D(σh ) = � �� �= � �
�0 1 0 0 �� 0 0 −1 0 � � 0 −1 0 0 �
�0 0 1 0 �� 0 0 0 −1 � � 0 0 −1 0 �

�e operation corresponding to this representative is found by considering its

e�ect on the starting basis

� −1 0 0 0 �
� 0 0 0 −1 �
( p1 p2 p3 p4 ) � � = ( −p1 −p3 −p4 −p2 )
� 0 −1 0 0 �
� 0 0 −1 0 �

�e operation C 3 σh therefore changes the sign of p1 , and converts p2 , p3 and

p4 into −p3 , −p4 , and −p2 respectively. �is is precisely the same outcome
as achieved by the S 3 operation , that is, a ���○ rotation around the C 3 axis
followed by a re�ection in the σh plane. �us, D(C 3 )D(σh ) = D(S 3 ).

E��B.�(b) Fig. ��.�� shows BF� , an example of a molecule with D 3h symmetry. �e three
C 2 axes are labelled C 2 , C 2′ and C 2′′ , and likewise for the σv mirror planes.

C2',σv'
C2',σv' C2',σv'
4 F 1 F F
2 3
2
1 3 4

F F F F F F

C2'',σv'' 3 C2,σv C2'',σv'' 4 C2,σv C2'',σv'' C2,σv

2 1

C 2′′−1 σv C 2′′ = σv′ C 2−1 σv′ C 2 = σv′′ C 2′−1 σv′′ C 2′ = σv

�e criteria for two operations R and R ′ to be in the same class is given by

[��B.�–���], R′ = S −1 RS where S is another operation in the group. �e task is
therefore to �nd an operation S in D 3h such that this equation is satis�ed when
R and R′ are two of the σv planes.
 Referring to the �rst diagram in Fig. ��.��, to show that σv and σv′ are in the
same class consider the operation C 2′′−1 σv C 2′′ . Start at the arbitrary point �, and
recall that the operations are applied starting from the right. �e operation C 2′′
moves the point to �, and then σv moves the point to �. �e inverse of a C 2
rotation is itself, C 2′′−1 = C 2′′ , so the e�ect of C 2′′−1 is to move the point to �.
From the diagram it can be seen that � can be reached by applying σv′ to point
�, thus demonstrating that C 2′′−1 σv C 2′′ = σv′ and hence that σv and σv′ belong to
the same class.
In a similar way the second diagram in Fig. ��.�� shows that C 2−1 σv′ C 2 = σv′′ and
hence that σv′ and σv′′ belong to the same class, while the third diagram shows
that σv′′ and σv belong to the same class.

E��B.�(b) �e orthonormality of irreducible representations is de�ned by [��B.�–���],

1 0 for i ≠ j
� N(C)χ (C)χ (C) = �
Γ (i) Γ ( j)
(��.�)
h C 1 for i = j

where the sum is over all classes of the group, N(C) is the number of operations
in class C, and h is the number of operations in the group (its order). χ Γ (C)
(i)

is the character of class C in irreducible representation Γ(i) , and similarly for

χ Γ (C).
( j)

�e character table for the point group D 3h is given in the Resource section. �e
operations of the group are {E, σh , 2C 3 , 2S 3 , 3C 2′ , 3σv }, and h = 12. �ere are
� classes and the values of N(C) are the numbers multiplying the operations
listed.
�e irreducible representation E′ has characters {�, �, −1, −1, �, �}. With Γ(i) =
E′ and Γ( j) = A′1 , which has characters {�, �, �, �, �, �}, eqn ��.� evaluates as
1
12
{1×2×1 + 1×2×1 + 2×(−1)×1 + 2×(−1)×1 + 3×0×1 + 3×0×1} = 0

With Γ(i) = E′ and Γ( j) = A′2 , which has characters {�, �, �, �, −1, −1}, the sum
is
1
12
{1×2×1 + 1×2×1 + 2×(−1)×1 + 2×(−1)×1 + 3×0×(−1) + 3×0×(−1)} = 0

With Γ(i) = E′ and Γ( j) = E′′ , which has characters {�, −2, −1, �, �, �}, the sum
is
1
12
{1×2×2 + 1×2×(−2) + 2×(−1)×(−1) + 2×(−1)×1 + 3×0×0 + 3×0×0} = 0

�ese results con�rm that the E′ irreducible representation is orthogonal to A′1 ,

A′2 , and E′′ .

E��B.�(b) �e D 4h character table is given in the Resource section. As explained in Sec-

tion ��B.�(a) on page ���, an s orbital on a central atom always spans the totally
symmetric representation of a group, which in D 4h is A1g , as it is unchanged
under all symmetry operations. �e symmetry species of the p and d orbitals
 are found using the information on the right hand side of the character table.
�e position of z in the table shows that pz , which is proportional to z f (r), has
symmetry species A2u in D 4h . Similarly the positions of x and y in the char-
acter table shows that px and p y , which are proportional to x f (r) and y f (r)
respectively, jointly span the irreducible representation of symmetry species
Eu .
In the same way the positions of z 2 , x 2 − y 2 , and x y in the character table
show that dz 2 , dx 2 −y 2 , and dx y have symmetry species A1g , B1g , and B2g
respectively, while the positions of yz and zx show that d yz and dzx jointly
span Eg .

E��B.�(b) As explained in Section ��B.�(c) on page ���, the highest dimensionality of

irreducible representations in a group is equal to the maximum degree of de-
generacy in the group. �e highest dimensionality is found by noting the max-
imum value of χ(E) in the character table. An icosahedral nanoparticle has I h
symmetry, the character table for which is given in the Online resource centre.
�e maximum value of χ(E) is �, corresponding to the H irreducible represen-
tations. �erefore the maximum degeneracy of a particle inside an icosahedral
nanoparticle is �ve .

E��B.�(b) As explained in Section ��B.�(c) on page ���, the highest dimensionality of any
irreducible representation in a group is equal to the maximum degree of de-
generacy in the group. �e highest dimensionality is found by noting the max-
imum value of χ(E) in the character table. �,�-dichlorobenzene has D 2h sym-
metry, and from the D 2h character table in the Resource section the maximum
value of χ(E) is �, that is, all irreducible representations are one-dimensional.
�erefore the maximum degeneracy of the orbitals in �,�-dichlorobenzene is
�.

P��B.� Fig. ��.�� shows that a C 2 rotation followed by a re�ection in a mirror plane
perpendicular to the C 2 axis is equivalent to an inversion i. Hence σh C 2 = i.

C2
1
2

i
σh
3

Because criterion � of the de�nition of a group given in Section ��B.� on page

��� speci�es that RR ′ is equivalent to a single member of the group, it follows
 that if a group has both a C 2 operation and a σh operation it must also have the
operation σh C 2 , which as shown above is i.

P��B.� �e methane molecule and H�s orbitals are shown in Fig. ��.��, along with one
operation of each class. Note that di�erent operations in the same class may
give di�erent representatives, but these representatives will necessarily all have
the same trace.

C3
C2,S4 σd
sA
H

sB
sD
H H
H
sC

�e C 3 operation shown in Fig. ��.�� leaves sA unchanged but converts sB into

sC , sC into sD , and sD into sB : ( sA sC sD sB ) ← ( sA sB sC sD ). �is is written
using matrix multiplication as
D(C 3 )
��� � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � �
� 1 0 0 0 �
� 0 0 0 1 �
( sA sC sD sB ) = ( sA sB sC sD )� �
� 0 1 0 0 �
� 0 0 1 0 �

�e matrix D(C 3 ) is the representative of the C 3 operation in this basis. Sim-

ilarly, the C 2 operation shown in Fig. ��.�� exchanges sA and sB , and also ex-
changes sC and sD . �is is written using matrix multiplication as
D(C 2 )
��� � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � �
� 0 1 0 0 �
� 1 0 0 0 �
( sB sA sD sC ) = ( sA sB sC sD )� �
� 0 0 0 1 �
� 0 0 1 0 �

�e σd operation shown in Fig. ��.�� leaves sA and sB unchanged and exchanges

sC and sD ; this gives
D(σ d )
��� � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � �
� 1 0 0 0 �
� 0 1 0 0 �
( sA sB sD sc ) = ( sA sB sC sD )� �
� 0 0 0 1 �
� 0 0 1 0 �
 �e S 4 operation shown in Fig. ��.�� converts sA to sD , sB to sC , sC to sA , and
sD to sB , giving
D(S 4 )
��� � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � �
� 0 0 1 0 �
� 0 0 0 1 �
( sD sC sA sB ) = ( sA sB sC sD )� �
� 0 1 0 0 �
� 1 0 0 0 �

Finally, the E operation leaves all orbitals unchanged, meaning that its repre-
sentative is simply the identity matrix
D(E)
��� � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � �
� 1 0 0 0 �
� 0 1 0 0 �
( sA sB sC sD ) = ( sA sB sC sD )� �
� 0 0 1 0 �
� 0 0 0 1 �

P��B.� In the previous exercise, the representatives were found to be

�1 0 0 0� �0 0 0 1� �0 1 0 0� �0 0 1 0�
�0 1 0 0� �0 0 1 0� �1 0 0 0� �0 0 0 1�
D(E)= � � D(C 2x )= � � D(C 2 )= � � D(C 2z )= � �
y
�0 0 1 0� �0 1 0 0� �0 0 0 1� �1 0 0 0�
�0 0 0 1� �1 0 0 0� �0 0 1 0� �0 1 0 0�

�0 0 1 0� �1 0 0 0� �0 1 0 0� �0 0 0 1�
�0 0 0 1� �0 1 0 0� �1 0 0 0� �0 0 1 0�
D(i) = � � D(σ )= �
xy
� D(σ )= �
yz
� D(σ )= �
xz
�
�1 0 0 0� �0 0 1 0� �0 0 0 1� �0 1 0 0�
�0 1 0 0� �0 0 0 1� �0 0 1 0� �1 0 0 0�

�e group multiplications are veri�ed by multiplying the corresponding matrix

representatives
D(C 2z ) D(C 2 ) D(C 2x )
y

��� � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � �� ��� � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � �� ��� � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � ��

� 0 0 1 0 �� 0 1 0 0 � � 0 0 0 1 �
� 0 0 0 1 �� 1 0 0 0 � � 0 0 1 0 �
D(C 2z )D(C 2 ) = � �� �=� � = D(C 2x )
y
� 1 0 0 0 �� 0 0 0 1 � � 0 1 0 0 �
� 0 1 0 0 �� 0 0 1 0 � � 1 0 0 0 �

D(σ x z ) D(C 2z ) D(C 2 )

y

��� � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � �� ��� � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � �� ��� � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � ��

� 0 0 0 1 �� 0 0 1 0 � � 0 1 0 0 �
� 0 0 1 0 �� 0 0 0 1 � � 1 0 0 0 �
D(σ )D(C 2 ) = � �� �=� � = D(C 2 )
xz z y
� 0 1 0 0 �� 1 0 0 0 � � 0 0 0 1 �
� 1 0 0 0 �� 0 1 0 0 � � 0 0 1 0 �
D(C 2 ) D(σ x z )
y
D(i)
��� � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � �� ��� � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � �� ��� � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � ��
� 0 0 1 0 �� 0 1 0 0 � � 0 0 0 1 �
� 0 0 0 1 �� 1 0 0 0 � � 0 0 1 0 �
D(i)D(C 2 ) = � �� �=� � = D(σ x z )
y
� 1 0 0 0 �� 0 0 0 1 � � 0 1 0 0 �
� 0 1 0 0 �� 0 0 1 0 � � 1 0 0 0 �
P��B.� Performing the matrix multiplications gives

01 01 10 01 0 −i i 0
σx σx = � � � � = � � = σ0 σx σ y = � �� �=� � = iσz
10 10 01 10 i 0 0 −i
01 1 0 0 −1 01 10 01
σ x σz = � �� �=� � = −iσ y σx σ0 = � � � � = � � = σx
10 0 −1 1 0 10 01 10

0 −i 01 −i 0 0 −i 0 −i 10
σ y σx = � �� � = � � = −iσz σ y σ y = � �� � = � � = σ0
i 0 10 0 i i 0 i 0 01
0 −i 1 0 0i 0 −i 10 0 −i
σ y σz = � �� � = � � = iσx σ y σ0 = � �� � = � � = σy
i 0 0 −1 i0 i 0 01 i 0

1 0 01 0 1 1 0 0 −i 0 −i
σz σ x = � �� � = � � = iσ y σz σ y = � �� �=� � = −iσx
0 −1 10 −1 0 0 −1 i 0 −i 0
1 0 1 0 10 1 0 10 1 0
σz σz = � �� � = � � = σ0 σ z σ0 = � �� � = � � = σz
0 −1 0 −1 01 0 −1 01 0 −1

10 01 01 10 0 −i 0 −i
σ0 σ x = � � � � = � � = σx σ0 σ y = � �� �=� � = σy
01 10 10 01 i 0 i 0
10 1 0 1 0 10 10 10
σ0 σ z = � �� �=� � = σ z σ0 σ0 = � � � � = � � = σ0
01 0 −1 0 −1 01 01 01

�e RR′ multiplication table is therefore

R ↓ R′ → σx σy σz σ0
σx σ0 iσz −iσ y σx
σy −iσz σ0 iσx σy
σz iσ y −iσx σ0 σz
σ0 σx σy σz σ0

�e four matrices do not form a group under multiplication. �is is because

they do not satisfy criterion � in Section ��B.� on page ���, that the combination
RR ′ must be equivalent to a single member of the collection. For example,
σx σ y = iσz , but iσz is not one of the four matrices.

P��B.�� �e two wavefunctions are shown schematically in Fig. ��.��, where the shading
indicates the sign of the wavefunction.
It is clear from Fig. ��.�� that a C 4+ rotation, taken to be 90○ anticlockwise,
converts ψ 2,3 into ψ 3,2 and ψ 3,2 into −ψ 2,3 : ( ψ 3,2 −ψ 2,3 ) ← ( ψ 2,3 ψ 3,2 ). Sim-
ilarly C 4− transforms ( −ψ 3,2 ψ 2,3 ) ← ( ψ 2,3 ψ 3,2 ), C 2 changes the sign of both
wavefunctions, while E leaves both unchanged. Writing these using matrix
multiplication gives
 y y
L L

L x L x

ψ 2,3 = � L2 � sin � 2πx

L
� sin � 3πL y � ψ 3,2 = � L2 � sin � 3πx
L
� sin � 2π y
L
�

D(E)
��� � � � � � � � � �� � � � � � � � � �
1 0
For E: ( ψ 2,3 ψ 3,2 ) = ( ψ 2,3 ψ 3,2 )� �
0 1
D(C 4+ )
��� � � � � � � � � � � �� � � � � � � � � � � � ��
0 −1
For C 4+ : ( ψ 3,2 −ψ 2,3 ) = ( ψ 2,3 ψ 3,2 )� �
1 0
D(C 4− )
��� � � � � � � � � � � �� � � � � � � � � � � � ��
0 1
For C 4− : ( −ψ 3,2 ψ 2,3 ) = ( ψ 2,3 ψ 3,2 )� �
−1 0
D(C 2 )
��� � � � � � � � � � � � � � �� � � � � � � � � � � � � � ��
−1 0
For C 2 : ( −ψ 2,3 −ψ 3,2 ) = ( ψ 2,3 ψ 3,2 )� �
0 −1

�e characters are

χ(E) = 2 χ(C 4+ ) = 0 χ(C 4− ) = 0 χ(C 2 ) = −2

Noting that C 4+ and C 4− are in the same class and appear in the column labelled
2C 4 , the C 4 character table in Table ��B.� on page ��� shows that the basis
of ψ 2,3 and ψ 3,2 spans the doubly degenerate irreducible representation E. It
follows that these two wavefunctions are degenerate.

D��C.� �e key point is that only orbitals (or combinations of orbitals) which transform
as the same symmetry species (irreducible representation) can overlap to form
molecular orbitals. �e �rst step is therefore to classify the valence orbitals
according to symmetry. Usually, it is possible to identify sets of such orbitals
which are interconverted by the operations of the group and so can be consid-
ered separately from other sets. Having classi�ed a set of orbitals according to
 symmetry the projection operator is then used to construct symmetry-adapted
linear combinations (SALCs) each of which transforms as a single symmetry
species (irreducible representation). �e molecular orbitals are formed from
the overlap of these SALCs.

E��C.�(b) As explained in Section ��C.� on page ��� an integral can only be non-zero if
the integrand spans the totally symmetric irreducible representation, which in
D 3h is A′1 . From Section ��C.�(a) on page ��� the symmetry species spanned by
the integrand px zpz is found by the forming the direct product of the symmetry
species spanned by px , z, and pz separately. �ese are read o� the D 3h character
table by looking for the appropriate Cartesian functions listed on the right of
the table: x and hence px spans E′ , while z and hence pz both span A′′2 . �e
direct product required is therefore E′ × A′′2 × A′′2 .
�e order does not matter, so this is equal to A′′2 × A′′2 × E′ . �is is equal to
A′1 × E′ because, from the second simplifying feature listed in Section ��C.�(a)
on page ���, the direct product of an irreducible representation such as A′′2
with itself is the totally symmetric irreducible representation A′1 . In turn, A′1 ×
E′ is simply equal to E′ because, from the �rst simplifying feature listed in
Section ��C.�(a) on page ���, the direct product of the totally symmetric irre-
ducible representation with any other representation is the latter representation
itself: A′1 × Γ(i) = Γ(i) . �e integrand therefore spans E′ . �is is not the totally
symmetric irreducible representation, therefore the integral is zero .

E��C.�(b) As explained in Section ��C.� on page ���, an electric dipole transition is forbid-
den if the electric transition dipole moment µ q,fi is zero. �e transition dipole
moment is given by [��C.�–���], µ q,fi = −e ∫ ψ ∗f qψ i dτ where q is x, y, or z.
�e integral is only non-zero if the integrand contains the totally symmetric
irreducible representation, which from the D 6h character table is A1g .
For a transition A1g → E2u , the symmetry species of the integrand is given by
the direct product A1g × Γ(q) × E2u . �e order does not matter so this is equal
to A1g × E2u × Γ(q) , which is simply equal to E2u × Γ(q) because, from the �rst
simplifying feature listed in Section ��C.�(a) on page ���, the direct product of
the totally symmetric irreducible representation with any other representation
is the latter representation itself. �erefore A1g × E2u = E2u .
�e direct product E2u × Γ(q) contains the totally symmetric irreducible repre-
sentation only if Γ(q) spans E2u because, according to the second simplifying
feature listed in Section ��C.�(a) on page ���, the direct product of two irre-
ducible representations contains the totally symmetric irreducible representa-
tion only if the two irreducible representations are identical. �e D 6h character
table shows that none of x, y or z span E2u , so it follows that the integrand does
not contain A1g and hence the transition is forbidden .

E��C.�(b) As explained in Section ��C.�(a) on page ��� the symmetry species of x yz is

determined by forming the direct product between the irreducible representa-
tions spanned by x, y and z individually. Inspection of the D 2h character table
 shows that x spans B3u in D 3h while y and z span B2u and B1u respectively. �e
direct product is

y
E C 2x C 2 C 2z i σ x y σ yz σ zx
B3u � −1 −1 � −1 � −1 �
B2u � −1 � −1 −1 � � −1
B1u � � −1 −1 −1 −1 � �
product � � � � −1 −1 −1 −1

�e characters in the product row are those of symmetry species Au , thus con-
�rming that the function x yz has symmetry species Au in D 2h .

E��C.�(b) �e OF� molecule and the two combinations of p y orbitals are shown in Fig. ��.��.

z z

C2,σv C2,σv

σv' O σv' O
y y
py(B) py(A)

p y (A) + p y (B) p y (A) − p y (B)

�e �rst combination, p y (A) + p y (B), is le� unchanged by E and σv′ , but has
its sign changed by the C 2 and σv operations. Its characters are therefore

χ(E) = 1 χ(C 2 ) = −1 χ(σv ) = −1 χ(σv′ ) = 1

Inspection of the C 2v character table shows that these are the characters of the
B2 irreducible representation, so p y (A) + p y (B) spans B2 .
�e second combination, p y (A) − p y (B), is unchanged by all of the operations
of the group and therefore spans the totally symmetric irreducible representa-
tion A1 .
As explained in Section ��C.�(a) on page ���, only orbitals of the same sym-
metry species may have a nonzero overlap. Inspection of the C 2v character
table shows that the oxygen �s and �pz orbitals both have A1 symmetry, so
they can interact with the p y (A) − p y (B) combination of �uorine orbitals. �e
oxygen �p y orbital has B2 symmetry, so it can interact with the p y (A) + p y (B)
combination of �uorine orbitals. �e oxygen �px orbital has B1 symmetry, so
cannot interact with either combination of �uorine orbitals.

E��C.�(b) As explained in Section ��C.�(a) on page ���, only orbitals of the same symme-
try species may have a nonzero overlap. Inspection of the D 3h character table
 shows that the boron �s and pz orbitals span A′1 and A′′2 respectively, while the
px and p y orbitals jointly span E′ . �erefore pz can interact with the A′′2 SALC,
while none of the boron valence orbitals have the correct symmetry to interact
with the E′′ SALC.
�e character table also shows that dz 2 spans A′1 , dx 2 −y 2 and dx y jointly span E′ ,
and d yz and dzx jointly span E′′ . �erefore the none of the d orbitals have the
correct symmetry to interact with the A′′2 SALC, but d yz and dzx can interact
with the E′′ SALC.

E��C.�(b) As explained in Section ��C.� on page ���, a transition from a state with sym-
metry Γ(i) to one with symmetry Γ(f) is only allowed if the direct product
Γ(f) × Γ(q) × Γ(i) contains the totally symmetric irreducible representation,
which in C 2v is A1 . In this case Γ(i) = B1 and Γ(q) = Γ(y) = B2 because, from
the C 2v character table, y spans B2 . �e required direct product is therefore
Γ(f) × B2 × B1 . �e product B2 × B1 is evaluated by multiplying the characters
of the two representations.

E C 2 σv σv′
B2 � −1 −1 �
B1 � −1 � −1
product � � −1 −1

�e characters of the product row correspond to those of A2 , therefore B2 ×B1 =

A2 and hence Γ(f) × B2 × B1 = Γ(f) × A2 . If this product is to span A1 then
the symmetry of the upper state Γ(f) must be A2 because, according to the
second simplifying feature of direct products listed in Section ��C.�(a) on page
���, the direct product of two irreducible representations only spans the totally
symmetric irreducible representation if the two irreducible representations are
identical.

E��C.�(b) �e number of times n(Γ) that a given irreducible representation Γ occurs in a

representation is given by [��C.�a–���], n(Γ) = (1�h) ∑C N(C)χ(Γ) (C)χ(C),
where h is the order of the group, N(C) is the number of operations in class C,
χ(Γ) is the character of class C in the irreducible representation Γ, and χ(C) is
the character of class C in the representation being reduced. In the case of D 2 ,
h = 4.

n(A1 ) = 14 �N(E)× χ(A1 ) (E)× χ(E) + N(C 2z )× χ(A1 ) (C 2z )× χ(C 2z )

+ N(C 2 )× χ(A1 ) (C 2 )× χ(C 2 ) + N(C 2x )× χ(A1 ) (C 2x )× χ(C 2x )�
y y y

= 14 (1×1×6 + 1×1×(−2) + 1×1×0 + 1×1×0) = 1

 Similarly

n(B1 ) = 14 (1×1×6 + 1×1×(−2) + 1×(−1)×0 + 1×(−1)×0) = 1

n(B2 ) = 14 (1×1×6 + 1×(−1)×(−2) + 1×1×0 + 1×(−1)×0) = 2
n(B3 ) = 14 (1×1×6 + 1×(−1)×(−2) + 1×(−1)×0 + 1×1×0) = 2

�e representation therefore spans A1 + B1 + 2B2 + 2B3 .

E��C.�(b) �e number of times n(Γ) that a given irreducible representation Γ occurs in a

representation is given by [��C.�a–���], n(Γ) = (1�h) ∑C N(C)χ(Γ) (C)χ(C),
where h is the order of the group, N(C) is the number of operations in class C,
χ(Γ) is the character of class C in the irreducible representation Γ, and χ(C) is
the character of class C in the representation being reduced. In the case of O h ,
h = 48.
Because the representation being reduced has characters of zero for all classes
except E, C 4 , C 42 , σh and σd , only these latter �ve classes make a non-zero
contribution to the sum and therefore only these classes need be considered.
�e number of times that the irreducible representation A1g occurs is therefore

n(A1g ) = 1
48
�N(E)× χ(A1g ) (E)× χ(E) + N(C 4 )× χ(A1g ) (C 4 )× χ(C 4 )
+ N(C 42 )× χ(A1g ) (C 42 )× χ(C 42 ) + N(σh )× χ(A1g ) (σh )× χ(σh )
+ N(σd )× χ(A1g ) (σd )× χ(σd )�
= 1
48
(1×1×6 + 6×1×2 + 3×1×2 + 3×1×4 + 6×1×2) = 1

Similarly

n(A2g ) = 1
48
(1×1×6 + 6×(−1)×2 + 3×1×2 + 3×1×4 + 6×(−1)1×2) = 0
n(Eg ) = 48 (1×2×6 + 6×0×2 + 3×2×2 + 3×2×4 + 6×0×2) = 1
1

n(T1g ) = 481
(1×3×6 + 6×1×2 + 3×(−1)×2 + 3×(−1)×4 + 6×(−1)×2) = 0
n(T2g ) = 48 (1×3×6 + 6×(−1)×2 + 3×(−1)×2 + 3×1×4 + 6×1×2) = 0
1

n(A1u ) = 481
(1×1×6 + 6×1×2 + 3×1×2 + 3×(−1)×4 + 6×(−1)×2) = 0
n(A2u ) = 48 (1×1×6 + 6×(−1)×2 + 3×1×2 + 3×(−1)×4 + 6×1×2) = 0
1

n(Eu ) = 48
1
(1×2×6 + 6×0×2 + 3×2×2 + 3×(−2)×4 + 6×0×2) = 0
n(T1u ) = 48 (1×3×6 + 6×1×2 + 3×(−1)×2 + 3×1×4 + 6×1×2) = 1
1

n(T2u ) = 481
(1×3×6 + 6×(−1)×2 + 3×(−1)×2 + 3×1×4 + 6×(−1)×2) = 0

�e representation therefore spans A1g + Eg + T1u .

E��C.�(b) As explained in Section ��C.� on page ���, a transition from a state with sym-
metry Γ(i) to one with symmetry Γ(f) is only allowed if the direct product Γ(f) ×
 Γ(q) × Γ(i) contains the totally symmetric irreducible representation, which
for both molecules is A1g . �e ground state is totally symmetric, implying
that it transforms as A1g . �erefore the direct product becomes Γ(f) × Γ(q) ×
A1g . �is is simply Γ(f) × Γ(q) because, from the �rst simplifying feature of
direct products listed in Section ��C.�(a) on page ���, the direct product of the
totally symmetric representation A1g with any other representation is the latter
representation itself.
If Γ(f) × Γ(q) is to be A1g , then Γ(f) must equal Γ(q) because, from the second
simplifying feature of direct products listed in Section ��C.�(a) on page ���,
the direct product of two irreducible representations only contains the totally
symmetric irreducible representation if the two irreducible representations are
identical.

(i) Anthracene belongs to point group D 2h . �e D 2h character table in the

Resource section shows that x transforms as B3u , y transforms as B2u , and z
transforms as B1u . �erefore anthracene can be excited to B3u , B2u , or B1u
states by x, y, and z polarised light respectively.
(ii) Coronene belongs to point group D 6h . �e D 6h character table in the
Online resource centre shows that shows that z transforms as A2u , and x
and y together transform as E1u . �erefore light polarized along z can
excite coronene to a A2u state, and x or y polarised light can excite it to
an E1u state.

P��C.� �e distorted molecules are shown in Fig. ��.�� together with some of the sym-
metry operations.

C3
σv C2
sA sD
H
σv H
H
sC
sB H H
sD
H H sA sB
H σv'
sC

C 3v C 2v

(a) In the C 3v distorted case sA is una�ected by any of the operations of the

group and is not mixed with the other H�s orbitals. It therefore transforms
as the totally symmetric irreducible representation A1 .
�e irreducible representations spanned by sB , sC , and sD are identi�ed
by forming the representatives of the operations with this basis. Only one
operation in each class needs to be considered. �e C 3 operation converts
sB into sC , sC into sD , and sD into sB : ( sC sD sB ) ← ( sB sC sD ). �is is
written using matrix multiplication as
D(C 3 )
��� � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � �
� 0 0 1 �
( sC sD sB ) = ( sB sC sD )� 1 0 0 �
� 0 1 0 �

Similarly
D(σ v )
��� � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � �
� 1 0 0 �
For σv : ( sB sD sC ) = ( sB sC sD )� 0 0 1 �
� 0 1 0 �

D(E)
��� � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � �
� 1 0 0 �
For E: ( sB sC sD ) = ( sB sC sD )� 0 1 0 �
� 0 0 1 �
�e characters of the representatives are

χ(E) = 3 χ(C 3 ) = 0 χ(σv ) = 1

�is result can be arrived at much more quickly by noting that: (�) only
the diagonal elements of the representative matrix contribute to the trace;
(�) orbitals which are unmoved by an operation will result in a � on the
diagonal; (�) orbitals which are moved to other positions by an operation
will result in a � on the diagonal. �e character is found simply by count-
ing the number of orbitals which do not move. In the present case � are
unmoved by E, none are unmoved by C 3 , and � is unmoved by σv . �e
characters are therefore {3, 0, 1}.
�is representation is decomposed using the method described in Sec-
tion ��C.�(b) on page ���. �e number of times n(Γ) that a given irre-
ducible representation Γ occurs in a representation is given by [��C.�a–
���],
1
n(Γ) = � N(C)χ(Γ) (C)χ(C)
h C
where h is the order of the group, N(C) is the number of operations in
class C, χ(Γ) is the character of class C in the irreducible representation Γ,
and χ(C) is the character of class C in the representation being reduced.
In the case of C 3v , h = 6. �e number of times that the irreducible
representation A1 occurs is

n(A1 ) = 16 �N(E)× χ(A1 ) (E)× χ(E) + N(C 3 )× χ(A1 ) (C 3 )× χ(C 3 )

+ N(σv )× χ(A1 ) (σv )× χ(σv )�
= 16 (1×1×3 + 2×1×0 + 3×1×1) = 1
 Similarly

n(A2 ) = 16 (1×1×3 + 2×1×0 + 3×(−1)×1) = 0

n(E) = 16 (1×2×3 + 2×(−1)×0 + 3×1×1) = 1

�e three H�s orbitals sB , sC , and sD therefore span A1 + E; adding this to

the result from above that sA spans A1 gives 2A1 + E.
As explained in Section ��C.�(a) on page ���, only orbitals of the same
symmetry species may have a nonzero overlap. �e C 3v character table
also shows that the dz 2 orbital spans A1 in C 3v , dx y and dx 2 −y 2 jointly
span E, and dx z and d yz also jointly span E. It follows that dz 2 can form
molecular orbitals with the A1 combinations of hydrogen orbitals while
the other d orbitals can all form molecular orbitals with the E combi-
nations of hydrogen orbitals. So yes , more d orbitals can be involved in
forming molecular orbitals than in the case of tetrahedral methane where,
as shown in the previous exercise, only dx y , d yz and dx z are able to form
molecular orbitals.
(b) �e irreducible representations spanned by the H�s orbitals in the C 2v
distorted molecule, shown in the right-hand side of Fig. ��.��, are found
in the same way as above. It is convenient to consider sA and sB separately
from sC and sD . �is is because sA and sB are mixed with each other but
not with sC or sD by the operations of the group. Similarly sC and sD are
mixed with each other but not with sA or sB . For sA and sB the matrix
representatives are

1 0 0 1
D(E) = � � D(C 2 ) = � �
0 1 1 0

1 0 0 1
D(σv ) = � � D(σv′ ) = � �
0 1 1 0

for which the characters are

χ(E) = 2 χ(C 2 ) = 0 χ(σv ) = 2 χ(σv′ ) = 0

As before, this result is obtained with much less e�ort by simply counting
the number of orbitals which are not moved by each operation. Using
the decomposition formula, or simply by inspection of the C 2v character
table, this representation decomposes to A1 + B1 . Analysing sC and sD in
the same way gives the representatives as

1 0 0 1
D(E) = � � D(C 2 ) = � �
0 1 1 0

0 1 1 0
D(σv ) = � � D(σv′ ) = � �
1 0 0 1

�e characters are

χ(E) = 2 χ(C 2 ) = 0 χ(σv ) = 0 χ(σv′ ) = 2

 which decomposes to A1 + B2 .
Combining these results, the four H�s orbitals therefore span 2A1 + B1 +
B2 . Inspection of the C 2v character table indicates that z 2 , and hence
dz 2 , spans A1 , so this orbital can form molecular orbitals with the A1
combinations of hydrogen orbitals. Because both x 2 and y 2 span A1 , x 2 −
y 2 and hence dx 2 −y 2 also spans A1 and can therefore also form molecular
orbitals with the A1 combination of hydrogen orbitals. �e orbitals dzx
and d yz span B1 and B2 respectively, so can form molecular orbitals with
the B1 and B2 combinations of hydrogen orbitals. However, dx y spans A2
and therefore remains non-bonding because the hydrogen orbitals do not
span A2 .
�erefore yes , more d orbitals can form molecular orbitals than for tetra-
hedral methane, but not as many for the C 3v distorted molecule where all
�ve d orbitals could be involved in forming molecular orbitals.

P��C.� �e character table for the I h point group is available in the Online resource
centre.

(a) As explained in Section ��C.� on page ���, a photon-induced transition

from a state with symmetry Γ(i) to one with symmetry Γ(f) is only allowed
if the direct product Γ(f) × Γ(q) × Γ(i) contains the totally symmetric
irreducible representation, A1g . Because the ground state is A1g the direct
product becomes Γ(f) × Γ(q) × A1g . �is is simply Γ(f) × Γ(q) because the
direct product of the totally symmetric irreducible representation with
any other representation is the latter representation itself.
If the product Γ(f) ×Γ(q) is to be A1g , then Γ(f) must equal Γ(q) because the
direct product of two irreducible representations only contains the totally
symmetric irreducible representation if the two irreducible representa-
tions are identical. However, inspection of the I h character table shows
that Γ(q) = T1u , because x, y and z together span the T1u irreducible rep-
resentation. Because neither of the lowest-lying excited states are of T1u
symmetry, photon-induced transitions to these states are not allowed .
(b) If the centre of inversion is removed then the distorted molecule has I
symmetry. For this point group the character table in the Resource section
shows that Γ(q) spans T1 . By the same reasoning as above it follows that
transitions to an excited state with symmetry T1 are allowed but transi-
tions to a state with symmetry G are not .

P��C.� As explained in Section ��C.� on page ���, a photon-induced transition from

a state with symmetry Γ(i) to one with symmetry Γ(f) is only allowed if the
direct product Γ(f) × Γ(q) × Γ(i) contains the totally symmetric irreducible
representation, A1g . For a transition from an A1g ground state to an Eu excited
state the direct product becomes Eu ×Γ(q) ×A1g . �is is simply Eu ×Γ(q) because
the direct product of the totally symmetric irreducible representation A1g with
any other representation is the latter representation itself.
 �is product only contains A1g if Γ(q) = Eu because the direct product of
two irreducible representations only contains the totally symmetric irreducible
representation if the two irreducible representations are identical. Inspection
of the D 4h character table shows that x and y jointly span Eu , and therefore
the transition is allowed provided q = (x, y), that is with x and y polarised
radiation.

P��C.� �e tetra�uoroethene molecule is shown in Fig. ��.��.

y y
y y
C2,σyz C2,σyz
σxy σxy
pB pA pB pA
C2z
x x
x x
C2,σzx C2,σzx
pC pD pC pD

pz orbitals px orbitals

(a) �e representation for the four pz orbitals could be determined by �nding

the representatives using the method in Section ��B.�(a) on page ���, and
then �nding the traces of each of the representatives. �e same result can
be arrived at much more quickly by noting that: (�) only the diagonal
elements of the representative matrix contribute to the trace; (�) orbitals
which are unmoved by an operation will result in a +1 on the diagonal;
(�) orbitals which are unmoved by an operation by are changed in sign
will result in a −1 on the diagonal; (�) orbitals which are moved to other
positions by an operation will result in a � on the diagonal. �e character
is found simply by counting +1 for orbitals which do not move and −1 for
orbitals which do not move but which do change sign.
Referring to Fig. ��.�� it is seen that � orbitals are una�ected by E, all of the
orbitals are moved by each of the C 2 operations and i. �e re�ections σ yz
and σ zx move all of the orbitals, but σ x y leaves all four orbitals unmoved,
but with a sign change. �e characters are therefore
y
E C 2z C2 C 2x i σxy σ yz σ zx
� � � � � −4 � �

�is representation is decomposed using the method described in Sec-

tion ��C.�(b) on page ���. �e number of times n(Γ) that a given irre-
ducible representation Γ occurs in a representation is given by [��C.�a–
���],
n(Γ) = (1�h) � N(C)χ(Γ) (C)χ(C)
C
 where h is the order of the group, N(C) is the number of operations in
class C, χ(Γ) is the character of class C in the irreducible representation Γ,
and χ(C) is the character of class C in the representation being reduced.
For the point group D 2h , h = 8. Because the representation to be reduced
has characters of zero for all classes except E and σ x y , only these latter
two classes will make a non-zero contribution to the sum. �e number of
times that the irreducible representation Ag occurs is

n(Ag ) = 18 �N(E)× χ(Ag ) (E)× χ(E) + N(σ x y )× χ(Ag ) (σ x y )× χ(σ x y )�

= 18 (1×1×4 + 1×1×(−4)) = 0

Similarly

n(B 1g ) = 18 (1×1×4 + 1×1×(−4)) = 0

n(B 2g ) = 18 (1×1×4 + 1×(−1)×(−4)) = 1
n(B 3g ) = 18 (1×1×4 + 1×(−1)×(−4)) = 1
n(A u ) = 18 (1×1×4 + 1×(−1)×(−4)) = 1
n(B 1u ) = 18 (1×1×4 + 1×(−1)×(−4)) = 1
n(B 2u ) = 18 (1×1×4 + 1×1×(−4)) = 0
n(B 3u ) = 18 (1×1×4 + 1×1×(−4)) = 0

�e four pz orbitals therefore span B2g + B3g + Au + B1u .

(b) �e SALCs of B2g , B3g , Au and B1u symmetries are generated by applying
the projection operator to the p A orbital using the method described in
Section ��C.�(b) on page ���.

y
Row E C 2z C 2 C 2x i σ x y σ yz σ zx
� e�ect on pA pA pC −pB −pD −pC −pA pB pD
� characters for B2g � −1 � −1 � −1 � −1
� row � × row � pA −pC −pB pD −pC pA −pB pD
� characters for B3g � −1 −1 � � −1 � −1
� row � × row � pA −pC pB −pD −pC pA pB −pD
� characters for Au � � � � −1 −1 −1 −1
� row � × row � pA pC −pB −pD pC pA −pB −pD
� characters for B1u � � −1 −1 −1 −1 � �
� row � × row � pA pC pB pD pC pA pB pD

�e SALCs are formed by summing rows �, �, �, and � and dividing each

 by the order of the group (h = 8).

Row �: ψ (B2g ) = 18 (pA − pC − pB + pD − pC + pA − pB + pD )

= 1
4
(pA − pB − pC + pD )
Row �: ψ (B3g ) = 18 (pA − pC + pB − pD − pC + pA + pB − pD )
= 1
4
(pA + pB − pC − pD )
Row �: ψ (A u )
= 1
8
(pA + pC − pB − pD + pC + pA − pB − pD )
= 1
4
(pA − pB + pC − pD )
Row �: ψ (B1u ) = 18 (pA + pC + pB + pD + pC + pA + pB + pD )
= 1
4
(pA − pB + pC − pD )

(c) �e �px orbitals, shown in the right-hand half of Fig. ��.��, are analysed
in the same way. �e characters are found by noting that under the E
operation the four px orbitals are not moved so χ(E) = 4. Similarly under
the C 2z operation the orbitals are all moved so χ(C 2z ) = 0. Using this
approach the characters are written down as
y
E C 2z C2 C 2x i σxy σ yz σ zx
� � � � � � � �
Using the decomposition formula, or simply by inspection of the charac-
ter table, this is decomposed to Ag + B1g + B2u + B3u . Use of the projec-
tion operator then gives
y
Row E C 2z C 2 C 2x i σ x y σ yz σ zx
� e�ect on pA pA −pC −pB pD −pC pA −pB pD
� characters for Ag � � � � � � � �
� row � × row � pA −pC −pB pD −pC pA −pB pD
� characters for B1g � � −1 −1 � � −1 −1
� row � × row � pA −pC pB −pD −pC pA pB −pD
� characters for B2u � −1 � −1 −1 � � −1
� row � × row � pA pC −pB −pD pC pA −pB −pD
� characters for B1u � −1 −1 � −1 � −1 �
� row � × row � pA pC pB pD pC pA pB pD
Hence the SALCs are

ψ (Ag ) = 14 (pA − pB − pC + pD ) ψ (B1g ) = 14 (pA + pB − pC − pD )

ψ (B2u ) = 14 (pA − pB + pC − pD ) ψ (B3u ) = 14 (pA + pB + pC + pD )

D��A.� Doppler broadening. �is contribution to the linewidth is due to the Doppler
e�ect which shi�s the frequency of the radiation emitted or absorbed when the
molecules involved are moving towards or away from the detecting device. In
a gas, molecules have a wide range of speeds in all directions and the detected
spectral line is the absorption or emission pro�le arising from the resulting
Doppler shi�s. �e shape of a Doppler-broadened spectral line re�ects the
Maxwell distribution of speeds in the sample.
Lifetime broadening. �is kind of broadening is a quantum mechanical e�ect
which predicts that for a state with a lifetime τ there is an energy uncertainty
δE given by δE ≈ ħ�τ. �is uncertainty in the energy translates to absorption
(or emission) over a range of frequencies and hence a linewidth. �e lifetime
of a state may be limited by the rate of spontaneous emission from the state, in
which case the resulting broadening is called natural line broadening.
Collisions between molecules are e�cient at changing their rotational and vi-
brational energies, and therefore the lifetimes of such states are limited by the
the collision rate. �e resulting line broadening is called collisional or pressure
line broadening.
�e rate of spontaneous emission cannot be changed; hence its contribution is
the same regardless of phase. Doppler broadening is expected to contribute in a
similar way for both gases and liquids. �e higher density of liquids compared
to gases implies that collisions will be more frequent and hence the collisional
line broadening will be greater for a liquid.

E��A.�(b) �e ratio A�B is given by [��A.�a–���], A�B = 8πhν 3 �c 3 ; the frequency ν is

related to the wavelength though ν = c�λ.

(i) For radiofrequency radiation with ν = 500 MHz

A 8πhν 3 8π × (6.6261 × 10−34 J s) × (500 × 106 s−1 )3

= =
B c3 (2.9979 × 108 m s−1 )3
= 7.73 × 10−32 J s m−3
 (ii) For microwave radiation with λ = 3.0 cm

A 8πh(c�λ)3 8πh 8π × (6.6261 × 10−34 J s)

= = 3 = = 6.2 × 10−28 J s m−3
B c3 λ (3.0 × 10−2 m)3

E��A.�(b) �e Beer–Lambert law [��A.�–���], I = I 0 10−ε[J]L relates the intensity of the

transmitted light I to that of the incident light I 0 .

I�I 0 = 10−ε[J]L = 10−(227 dm mol−1 cm−1 )×(2.52×10−3 mol dm−3 )×(0.200 cm)
3

= 0.768...

Using this, the percentage reduction in intensity is calculated as 100(I 0 −I)�I 0 =

100(1 − I�I 0 ) = 100(1 − 0.768...) = ��.�% . Note the conversion of L to cm and
[J] to mol dm−3 in order to match the units of ε.

E��A.�(b) �e Beer–Lambert law [��A.�–���], I = I 0 10−ε[J]L relates the intensity of the

transmitted light I to that of the incident light I 0 . If a fraction T of the incident
light is transmitted through the sample, I = TI 0 and hence I�I 0 = T; T is the
transmittance. It follows that log T = −ε[J]L hence ε = −(log T)�[J]L. If ��.�%
of the light is transmitted, T = 0.615

ε = −(log T)�[J]L = −[log(0.615)]�(0.717 × 10−3 mol dm−3 ) × (0.250 cm)

= 1.17... × 103 dm3 mol−1 cm−1

Note the conversion of L to cm and [J] to mol dm−3 in order to give the usual
units of ε. To convert the molar absorption coe�cient to cm2 mol−1 simply
multiply the above value by 103 to convert dm3 to cm3 . �e units are then
cm3 mol−1 cm−1 = cm2 mol−1 . Hence ε = 1.18 × 106 cm2 mol−1 .

E��A.�(b) �e Beer–Lambert law [��A.�–���], I = I 0 10−ε[J]L relates the intensity of the

transmitted light I to that of the incident light I 0 . If a fraction α is absorbed,
then a fraction T = 1−α of the incident light passes through the sample, I = TI 0
and hence I�I 0 = T; T is the transmittance. It follows that log T = −ε[J]L
hence [J] = −(log T)�εL. If ��.�% of the light is absorbed, α = 0.483 and
T = 1 − 0.483 = 0.517

[J] = −(log T)�εL = −[log(0.517)]�(423 dm3 mol−1 cm−1 ) × (0.650 cm)

= 1.04... × 10−3 mol dm−3 = 1.04 mM

Note the use of L in cm.

E��A.�(b) �e transmittance T is the ratio I�I 0 , hence the Beer–Lambert law [��A.�–���]
can be written T = I�I 0 = 10−ε[J]L . It follows that log T = −ε[J]L and hence ε =
−(log T)�[J]L. With this, the following table is drawn up, with L = 0.250 cm.
 [dye]/(mol dm−3 ) 0.0010 0.0050 0.0100 0.0500
T�% 68 18 3.7 1.03 × 10−5
T 0.68 0.18 0.037 1.03 × 10−7
ε�(dm3 mol−1 cm−1 ) 670 596 573 559

�e molar absorption coe�cient is clearly not independent of the concentra-

tion; this may indicate that the dye molecules are interacting with one another
at higher concentrations.

E��A.�(b) �e transmittance T is the ratio I�I 0 , hence the Beer–Lambert law [��A.�–���]
can be written T = I�I 0 = 10−ε[J]L . It follows that log T = −ε[J]L and hence
ε = −(log T)�[J]L. With the given data, T = 0.29 and L = 0.500 cm, the molar
absorption coe�cient is calculated as

ε = −(log 0.29)�[(18.5×10−3 mol dm−3 )×(0.500 cm)] = 58.1... dm3 mol−1 cm−1

�e molar absorption coe�cient is therefore ε = 58 dm3 mol−1 cm−1 . For a

path length of �.��� cm the transmittance is

T = 10−(58.1 ... dm mol−1 cm−1 )×(0.250 cm)×(18.5×10−3 mol dm−3 )

= 0.538...
3

Hence T = 54% . Note the conversion of the concentration to mol dm−3 .

E��A.�(b) �e ratio of the incident to the transmitted intensities of light a�er passing
through a sample of length L, molar concentration [J], and molar absorption
coe�cient ε is given by [��A.�–���], T = I�I 0 = 10−ε[J]L . It follows that log T =
−ε[J]L, which rearranges to give L = −(log T)�ε[J].
�e missing piece of information (in fact misplaced to Exercise E��A.�(a)) is
that the concentration of the absorber is �� mmol dm−3 . �e light intensity is
reduced to half when T = 0.5, hence the thickness of the sample is calculated
as

L = −(log 0.5)�[(30 dm3 mol−1 cm−1 ) × (0.010 mol dm−3 )] = �.� cm

�e light intensity is reduced to one tenth when T = 0.1

L = −(log 0.1)�[(30 dm3 mol−1 cm−1 ) × (0.010 mol dm−3 )] = �.� cm

E��A.�(b) �e integrated absorption coe�cient is given by [��A.��–���], A = ∫band ε(ν̃) dν̃,

where the integration is over the band, and ν̃ = λ−1 is the wavenumber. �e
band extends from ��� nm, corresponding to ν̃ = (167 × 10−7 cm)−1 = 5.98... ×
104 cm−1 , peaking at ��� nm, ν̃ = (200 × 10−7 cm)−1 = 5.00 × 104 cm−1 , and
ending at ��� nm, ν̃ = (250 × 10−7 cm)−1 = 4.00 × 104 cm−1 .
 �e given equation of the parabolic lineshape, ε(ν̃) = ε max [1 − k(ν̃ − ν̃ max )2 ] is
conveniently rewritten as ε(x) = ε max [1 − kx 2 ], where x = ν̃ − ν̃ max . �e edges
of the lineshape are at the wavenumber at which ε(x) = 0

0 = ε max [1 − kx 2 ] hence x = ±k −1�2

�e area under the lineshape is therefore

+k −1�2 +k −1�2
A=� ε max (1 − kx 2 ) dx = ε max (x − kx 3 �3)�−k −1�2
−k −1�2
= ε max (2k −1�2 − (2�3)k × k −3�2 ) = (4�3)ε max k −1�2

For the speci�ed lineshape, ε(ν̃) goes to zero at 5.98... × 104 cm−1 and at 4.00 ×
104 cm−1 . It follows that 2k −1�2 = (5.98... − 4.00) × 104 cm−1 and hence

A = (4�3) × (3.35 × 104 dm3 mol−1 )

× 12 × [(5.98... − 4.00) × 104 cm−1 ]
= 4.44 × 108 dm3 mol−1 cm−1

E��A.�(b) �e Doppler linewidth is given by [��A.��a–���], δν obs = (2ν 0 �c)(2kT ln 2�m)1�2 ;

division of both sides by the speed of light converts δν obs and ν 0 to wavenum-
bers, allowing the expression to be written δν̃ obs = (2ν̃ 0 �c)(2kT ln 2�m)1�2 .
�e mass of �H ���I is taken as 128 m u . With these data the linewidth is calcu-
lated as

2 × 2308 cm−1 2 × (1.3806 × 10−23 J K−1 ) × (400 K) × ln 2

1�2
δν̃ obs = × � �
2.9979 × 108 m s−1 128 × 1.6605 × 10−27 kg
= 2.92 × 10−3 cm−1

where 1 J = 1 kg m2 s−2 is used.

E��A.��(b) If a light source of frequency ν 0 is approached at a speed s, the Doppler shi�ed

frequency ν a is [��A.��a–���],

1 + s�c
1�2
νa = ν0 � �
1 − s�c

Writing the frequencies in terms of the wavelength as ν = c�λ and then invert-
ing before sides gives
1 − s�c
1�2
λa = λ0 � �
1 + s�c
Solving this for the speed s leads to

1 − (λ a �λ 0 )2
s = c� �
1 + (λ a �λ 0 )2
 Hence, to achieve a doppler shi�ed wavelength of ��� nm, the speed needs to
be
1 − (530 nm�680 nm)2
s=c× = (0.244...) × c
1 + (530 nm�680 nm)2
Hence, for this large Doppler shi�, the speed of approach needs to be at ��.�%
of the speed of light, which is 7.31 × 107 m s−1 .

E��A.��(b) �e uncertainty in the energy of a state with lifetime τ is δE ≈ ħ�τ. �erefore a

spectroscopic transition involving this state has an uncertainty in its frequency,
and hence a linewidth, of the order of δν = δE�h ≈ (2πτ)−1 . �is expression
is rearranged to give the lifetime as τ = (2πδν)−1 ; expressing the linewidth as
a wavenumber gives τ = (2πδ ν̃c)−1 .
(i) For δν = 200 MHz
τ = [2π × (200 × 106 Hz)]−1 = 7.95... × 10−10 s = ��� ps

(ii) For δν̃ = 2.45 cm−1

τ = [2π × (2.45 cm−1 ) × (2.9979 × 1010 cm s−1 )]−1 = 2.16... × 10−12 s
= �.�� ps

E��A.��(b) �e uncertainty in the energy of a state with lifetime τ is δE ≈ ħ�τ. �erefore a

spectroscopic transition involving this state has an uncertainty in its frequency,
and hence a linewidth, of the order of δν = δE�h ≈ (2πτ)−1 . If each collision
deactivates the molecule, the lifetime is �/(collision frequency), but if only �
in N of the collisions deactivates the molecule, the lifetime is N/(collision fre-
quency). �us τ = N�z, where z is the collision frequency. �e linewidth is
therefore δν = (2πN�z)−1 .
(i) If each collision is e�ective at deactivation, N = 1 and with the data given
δν = [2π × 1�(1.0 × 109 s−1 )]−1 = 1.59 × 108 Hz = �.�� GHz

(ii) If only � in �� collisions are e�ective at deactivation, N = 10

δν = [2π × 10�(1.0 × 109 s−1 )]−1 = 1.59 × 107 Hz = �� MHz

P��A.� �e argument takes the same steps as in How is that done? ��A.� on page ���
up to the derivation of dI�I = −κ[J] dx. �is expression is integrated as before,
but instead of [J] being constant, it is given by [J] = [J]0 e−x�x 0
I L
� (1�I) dI = � −κ[J]0 e−x�x 0 dx
I0 0

ln(I�I 0 ) = −κ[J]0 (−x 0 e−x�x 0 )�0 = −κ[J]0 x 0 (1 − e−L�x 0 )

L

hence lg(I�I 0 ) = −(κ� ln 10)[J]0 x 0 (1 − e−L�x 0 )

 For this case the Beer–Lambert law is lg(I�I 0 ) = −ε[J]0 x 0 (1 − e−L�x 0 ) , where
ε = κ� ln 10.
In the limit L � x 0 , e−L�x 0 → 0 and hence lg(I�I 0 ) = −ε[J]0 x 0 . In this limit
the absorption is independent of the length of the sample. If x 0 � L then
the exponential may be expanded up to the linear term to give (1 − e−L�x 0 ) ≈
(1 − 1 + L�x 0 ) ≈ L�x 0 . �en lg(I�I 0 ) = −ε[J]0 L , which is the form of the
Beer–Lambert law for a constant concentration.

P��A.� Suppose that species A and B associate to give a complex AB according to the
equilibrium: A + B ��⇀ � AB. Suppose that species A absorbs at a particular
wavelength with absorption coe�cient ε A , and that species AB absorbs at the
same wavelength but with absorption coe�cient ε AB ; B does not absorb at this
wavelength. �e absorbance at this wavelength is

A λ = ε A [A]L + ε AB [AB]L

If the initial amount of A is [A]0 and at equilibrium the amount of AB is [AB]e ,

mass balance requires [A] = [A]0 − [AB]e . It follows that

A λ = ε A ([A]0 − [AB]e ) L + ε AB [AB]e L = ε A [A]0 L + (ε AB − ε A )[AB]e L

��� � � � � � ��� � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � � � � ��
term � term �

As the amount of added B is changed, term � remains the same, but in gen-
eral term � will change because of the resulting change in [AB]e . However, if
the wavelength is chosen such that ε AB = ε A , term � will go to zero and the
absorbance will be invariant to the amount of B added. �is is the isosbestic
point.

P��A.� Because only the area under the absorption band is of interest it can be as-
sumed, without loss of generality, that the band is centred on ν̃ = 0. �e band-
shape is then given by ε(ν̃) = ε max e−a ν̃ , where the parameter a determines the
2

width. �is parameter is found by �nding the wavenumbers ν̃ 1�2 at which ε has
fallen to half its maximum value

= ε max e−a(ν̃ 1�2 )

2
1
ε
2 max
hence ln 12 = −a(ν̃ 1�2 )2
hence (ν̃ 1�2 )2 = ln 2�a

where to go to the last line ln 12 = − ln 2 is used. �e wavenumbers of the points

at which ε has fallen to half its maximum value are therefore ±(ln 2�a)1�2 , and
hence the separation between these is 2(ln 2�a)1�2 . �is separation is the width
at half-height ∆ν̃ 1�2

4 ln 2
∆ν̃ 1�2 = 2(ln 2�a)1�2 hence a=
(∆ν̃ 1�2 )2
 Having established the relationship between the parameter a and the width at
half-height, the integral over the band is computed
+∞ +∞
A=� ε(ν̃) dν̃ = � ε max e−a ν̃ dν̃ = ε max (π�a)1�2
2

−∞ −∞

�e integral needed is of the form of Integral G.� with k = a. Now the expres-
sion for a derived above is used to give

π(∆ν̃ 1�2 )2
1�2
π 1�2
A = ε max � � = ε max � � ∆ν̃ 1�2
4 ln 2 4 ln 2
= ε max (1.0645)∆ν̃ 1�2

Making measurements from the plot in the text gives ε max = 9.8 dm3 mol−1 cm−1
and ∆ν̃ 1�2 = 4500 cm−1 , hence A = 4.7×104 dm3 mol−1 cm−2 . If several points
are measured from the plot these can be used as the input data to a non-linear
least-squares �tting procedure, most conveniently done using mathematical
so�ware. With such an approach the best-�t gaussian line is (omitting units
for clarity)
ε(ν̃) = 9.704 e−(1.405×10
−7
)×(ν̃−2.814×10 4 )2

Integrating this function gives A = 4.5 × 104 dm3 mol−1 cm−2 . A better �t is
obtained by using the sum of two gaussians, each with separate parameters:

ε(ν̃) = 5.757 e−(1.310×10 + 5.807 e−(3.180×10

−7 −7
)×(ν̃−2.916×10 4 )2 )×(ν̃−2.725×10 4 )2

Integrating this function gives A = 4.6 × 104 dm3 mol−1 cm−2 .

P��A.� (a) �e lines from the star are all at longer wavelength, and hence lower fre-
quency, than for the Earth-bound observations, therefore the object is
receding . �e ratio f is computed as f = ν r �ν = λ�λ r because the
frequency is inversely proportional to the wavelength. Writing x = s�c
gives

1 − x 1�2 1− f2
f =� � hence f 2 (1 + x) = (1 − x) hence x=
1+x 1+ f2

It follows that s = c[1 − (λ�λ r )2 ]�[1 + (λ�λ r )2 ]. With this expression s is

computed for each of the lines

λ r �nm 438.882 441.000 442.020

λ�nm 438.392 440.51 441.510
s�(105 m s−1 ) 3.34894 3.33285 3.46095

�e average of these measurements is 3.38 × 105 m s−1 . �e spread of

values is much larger than the apparent precision of the data.
 (b) �e radial velocity of the star with respect to the Sun could be computed
if the Earth’s speed with respect to the Sun along the Sun-star vector at
the time of the spectral observation is known. �is could be estimated
from quantities available through astronomical observation: the Earth’s
orbital velocity times the cosine of the angle between that velocity vector
and the Earth-star vector at the time of the spectral observation. (�e
Earth-star direction, which is observable by Earth-based astronomers,
is practically identical to the Sun-star direction, which is technically the
direction needed.) Alternatively, repeat the experiment half a year later.
At that time, the Earth’s motion with respect to the Sun is approximately
equal in magnitude and opposite in direction compared to the original
experiment. Averaging f values over the two experiments would yield f
values in which the Earth’s motion is e�ectively averaged out.

P��A.�� �e Doppler lineshape is given in How is that done? ��A.� on page ���: I =
Ae−mc (ν−ν 0 ) �2ν 0 k T , where A is a constant of proportionality. It is convenient
2 2 2

to rewrite this in terms of the dimensionless parameter x = (ν − ν 0 )�ν 0 , to give

I = Ae−mc x �2k T . �e derivative lineshape, D(x) is
2 2

dI −2xmc 2 −mc 2 x 2 �2k T mc 2 −mc 2 x 2 �2k T

D(x) = =A e = −A xe
dx 2kT kT
It is convenient to de�ne α = mc 2 �kT, giving

D(x) = −Aα x e−α x �2

2

�is lineshape is plotted in Fig ��.� for di�erent values of α. �e lineshape goes
to zero as x → ±∞ on account of the exponential term, is zero at x = 0, and
has a negative-going minimum at positive x and a positive-going maximum,
symmetrically placed, at negative x. As T increases (α decreases) the maximum
and minimum decrease in size and the line becomes broader.
�e positions of the maximum and minimum are found by di�erentiating once
more with respect to x and setting the result equal to zero.

dD(x)
= −Aα e−α x �2 + Aα 2 x 2 e−α x �2
2 2

dx

�is derivative is zero when x = ±α −1�2 : these values correspond to the posi-
tions of maximum and minimum. �e separation between these two is 2α −1�2 :
this goes as T 1�2 .

P��A.�� Figure ��.� shows plots the interferogram which would arise from a monochro-
matic beam sampled at di�erent distance increments δ (expressed as a multiple
of ν̃p). �e solid line shows the underlying continuous function which, for the
values chosen, goes through three complete cycles.
�e points indicated with open and closed triangles indicate the values which
would be recorded for the two smallest increments. �ese points on their own
 α=1
α = 0.5
α = 0.25

arb. units
�

−4 −2 0 2 4
x

provide a pretty good approximation to the curve: the minima and maxima
are su�ciently well de�ned that it is clear that there are three cycles, and so the
wavenumber is correctly represented.
�e points indicated by the open circles just capture the minima and maxima,
and no other detail; they are just su�cient to imply that there are three cycles.
In fact these measurements correspond to the Nyquist condition which states
that at least two data points are required per cycle in order to measure the
wavenumber correctly. �e �lled circles have the largest value of the increment,
and it is clear from the digram that they are spaced too widely to represent the
waveform correctly – in fact they are consistent with a curve at one third of the
wavenumber shown by the complete curve.
�is diagram illustrates that in order to infer the wavenumber correctly it is
necessary to sample the interferogram such that there are at least two data
points per cycle. �erefore, the upper limit on the wavenumber which can be
correctly measured using an interferometer is set by the amount by which the
mirror is moved in each step.

D��B.� Centrifugal distortion increases the moment of inertia and hence decreases the
rotational constant. �erefore, the separation between levels is decreased.

D��B.� �is is discussed in Section ��B.�(a) on page ���.

D��B.� BeF� is linear; 19 F has spin 12 and is therefore a fermion. �e argument is

therefore exactly the same as for 1 H2 , and so the molecule does indeed exist
in ortho and para forms. �e Be atom has no e�ect on the argument as it is at
the centre of symmetry.
 2.0
δ = 0.11
δ = 0.23
1.5
1 + cos(2πν̃p) δ = 0.50
δ = 0.73
1.0

0.5

0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
ν̃p

1
D��B.� H2 molecules can exist in two forms: the para form has antisymmetric nuclear
spin wavefunctions and the ortho form has symmetric nuclear spin wavefunc-
tions. As discussed in Section ��B.� on page ���, it follows that because of
these arrangements of the nuclear spins the ortho form must have rotational
wavefunctions restricted to odd J values. Ortho hydrogen therefore cannot
exist in the J = 0 state and hence it always has some rotational energy: that
is, it has rotational zero-point energy.

E��B.�(b) Expressions for the moments of inertia are given in Table ��B.� on page ���;
PH� is a symmetric rotor and the second entry under symmetric rotors is the
required one. �e moment or inertia about the threefold axis is I��

I�� = 2m H (1 − cos θ)R 2

= 2[(1.0078) × (1.6605 × 10−27 kg)] × (1 − cos 93.5○ ) × (142 × 10−12 m)2
= 7.16... × 10−47 kg m2 = 7.16 × 10−47 kg m2

�e corresponding rotational constant is given by [��B.��b–���]

ħ 1.0546 × 10−34 J s
à = =
4πcI�� 4π × (2.9979 × 1010 cm s−1 ) × (7.16... × 10−47 kg m2 )
= 3.91 cm−1

E��B.�(b) �ere is an error in the Exercise: the molecule is AB� , not AB� . �e required
expressions are the �rst listed under symmetric rotors in Table ��B.� on page
���
m A (m B + m A )
I� = m A f 1 (θ)R 2 + f 2 (θ)R 2
m
mC
+ �(3m A + m B )R ′ + 6m A R[ 13 f 2 (θ)]1�2 � R′
m
I�� = 2m A f 1 (θ)R 2

Note that the molecule described by these relationships is BA� C, which be-
comes BA� by letting C=A; the question refers to a molecule AB� , but for con-
sistency with the main text the exercise will be continued with BA� . Let m C =
m A and R ′ = ρR to give

m A (m B + m A )
I� = m A f 1 (θ)R 2 + f 2 (θ)R 2
m
mA
+ �(3m A + m B )ρR + 6m A R[ 13 f 2 (θ)]1�2 � ρR
m
with m = m B + 4m A . At the tetrahedral angle cos θ tet = − 13 ; hence f 1 (θ tet ) = 4
3
and f 2 (θ tet ) = 13 ; this gives

m A (m B + m A ) 1 2
I� = m A 43 R 2 + 3
R
m
mA
+ �(3m A + m B )ρR + 6m A R[ 13 × 13 ]1�2 � ρR
m
m A (m B + m A ) 1 2 m A
= m A 43 R 2 + 3
R + {(3m A + m B )ρR + 2m A R} ρR
m m
I�� = 2m A 43 R 2

To simplify the expression somewhat let m B = αm A . �is gives m = αm A +

4m A = (4 + α)m A

m A2 (α + 1) 1 2
I� = m A 43 R 2 + R
(4 + α)m A 3
mA
+ {(3 + α)ρm A R + 2m A R} ρR
(4 + α)m A
(α + 1) 1 1
I� �(m A R 2 ) = 43 + + {(3 + α)ρ + 2} ρ
(4 + α) 3
(4 + α)
4(4 + α) + (1 + α) + 3[(3 + α)ρ + 2ρ] 17 + 5α + 15ρ + 3ρα
= =
3(4 + α) 3(4 + α)
I�� �(m A R 2 ) = 8
3

A useful check at this point is to set ρ = 1 which gives I� �(m A R 2 ) = 8

3
, the
expected values for a tetrahedral BA� molecule.
�e variation of the moments of inertia with ρ are shown in Fig. ��.�; I� is shown
for three representative values of α. As expected, I� and I�� converge onto the
same value when ρ = 1. I�� is independent of ρ as this axis passes along the bond
with length R′ , and so the moment of inertia is una�ected by variations in R ′ .
 4.0
I��
I� α = 1
I� α = .2
3.5 I� α = 5
I�m A R 2

3.0

2.5
1.0 1.2 1.4 1.6 1.8 2.0
ρ

E��B.�(b) To be a symmetric rotor a molecule most possess an n-fold axis with n > 2. (i)
Ethene has three two-fold axes, but no axes with n > 2 and so is an asymmetric
rotor. (ii) SO� is trigonal planar; it has a three-fold axis and so is a symmetric
rotor. (iii) ClF� is ‘T-shaped’ and has a two-fold axis; it is an asymmetric rotor.
(iv) N� O is a linear rotor.

E��B.�(b) In order to determine two unknowns, data from two independent experiments
are needed. In this exercise two values of B for two isotopologues of OCS are
given; these are used to �nd two moments of inertia. �e moment of inertia of
a linear triatomic is given in Table ��B.� on page ���, and if it is assumed that
the bond lengths are una�ected by isotopic substitution, the expressions for
the moment of inertia of the two isotopologues can be solved simultaneously
to obtain the two bond lengths.

�e rotational constant in wavenumber is given by [��B.�–���], B̃ = ħ�4πcI;

multiplication by the speed of light gives the rotational constant in frequency
units B = ħ�4πI, which rearranges to I = ħ�4πB

I OCS = (1.0546 × 10−34 J s)�[4π × (6081.5 × 106 Hz)] = 1.37... × 10−45 kg m2

I OCS′ = (1.0546 × 10−34 J s)�[4π × (5932.8 × 106 Hz)] = 1.41... × 10−45 kg m2

In these expressions the isotopologue with ��S is denoted S and that with ��S is
denoted S′ . It is somewhat more convenient for the subsequent manipulations
to express the moments of inertia in units of the atomic mass constant m u and
 nm.
2
109 nm 1 mu
I OCS = (1.37... × 10−45 kg m2 ) × � � ×
1m 1.6605 × 10−27 kg
= 0.831... m u nm2
2
109 nm 1 mu
I OCS′ = (1.41... × 10−45 kg m2 ) × � � ×
1m 1.6605 × 10−27 kg
= 0.851... m u nm2

Using the expressions from Table ��B.� on page ���, the moments of inertia
are expressed in terms of the masses and bond lengths, where the former are
expressed as multiples on m u . In this case A = ��O, B = ��C and C = ��S or ��S

(m O R − m S R′ )2
I OCS = m O R 2 + m S R′2 −
mO + mC + mS
(15.9949R − 31.9721R′ )2
= 15.9949R 2 + 31.9721R ′2 −
15.9949 + 12.0000 + 31.9721
(15.9949R − 31.9721R′ )2
= 15.9949R + 31.9721R −
2 ′2
59.967
(m R − m R )
′ 2
= m O R 2 + m S′ R ′2 −
O S ′
I OCS′
m O + m C + m S′
(15.9949R − 33.9679R′ )2
= 15.9949R 2 + 33.9679R ′2 −
15.9949 + 12.0000 + 33.9679
(15.9949R − 33.9679R′ )2
= 15.9949R + 33.9679R −
2 ′2
61.9628
�ese two equations need to be solved simultaneously for R and R′ , but be-
cause they are quadratics this is a very laborious process by hand: it is best
achieved using mathematical so�ware. �is gives the resulting bondlengths as
R = R OC = 0.1161 nm and R′ = R CS = 0.1561 nm .

E��B.�(b) �e centrifugal distortion constant is given by [��B.��–���], D̃ J = 4B̃ 3 �ν̃ 2 . With

the given data D̃ J = 4(0.0809 cm−1 )3 �(323.2 cm−1 )2 = 2.028 × 10−8 cm−1 .
�e rotational constant is inversely proportional to the moment of inertia of
the molecule, I = m eff R 2 where R is the bond length and m eff is the e�ective
mass. Assuming that isotopic substitution does not a�ect the bond length, it
follows that B̃ ∝ m−1 eff . Assuming that isotopic substitution does not a�ect
−1�2
the force constant, the vibrational frequency is proportional to m eff . �us
−1�2 2
D̃ ∝ (m−1eff ) �(m eff ) = m eff . For this estimation it is su�cient to use integer
3 −2

masses, and because a ratio is involved these can be expressed as multiples of

mu .

79 × 81 81 + 81 2
D̃ 81Br2 �D̃ 81Br 79Br = (m eff 81Br 79Br �m eff 81Br2 ) = � × � = �.��
2
79 + 81 81 × 81
E��B.�(b) For a molecule to show a pure rotational (microwave) absorption spectrum is
must have a permanent dipole moment. All of the molecules given satisfy this
requirement.

E��B.�(b) �e wavenumbers of the lines in the rotational spectrum are given by [��B.��a–
���], ν̃(J) = 2B̃(J + 1); the J = 2 ← 1 transition is therefore at ν̃(1) = 2B̃(1 +
1) = 4B̃. �e rotational constant is given by [��B.�–���], B̃ = ħ�4πcI, and the
moment of inertia is given by m eff R 2 , where m eff = m 1 m 2 �(m 1 + m 2 ).

(12.0000 × 15.9949)m u2 1.6605 × 10−27 kg

I= × × (112.81 × 10−12 m)2
(12.0000 + 15.9949)m u 1 mu
= 1.44... × 10−46 kg m2
ħ 1.0546 × 10−34 J s
B̃ = =
4πcI 4π × (2.9979 × 1010 cm s−1 ) × (1.44... × 10−46 kg m2 )
= 1.93... cm−1

�e transition occurs at 4B̃ = 4 × (1.93... cm−1 ) = �.��� cm−1 . Expressed in

frequency units this is 4c B̃ = 4 × (2.9979 × 1010 cm s−1 ) × (1.93... cm−1 ) =
2.31... × 1011 Hz = ���.� GHz .
Centrifugal distortion will lower the frequency.

E��B.�(b) �e wavenumbers of the lines in the rotational spectrum are given by [��B.��a–
���], ν̃(J) = 2B̃(J + 1). �e J = 1 ← 0 transition is therefore at ν̃(0) = 2B̃(0 +
1) = 2B̃, hence B̃ = (16.93�2) cm−1 . �e rotational constant is given by [��B.�–
���], B̃ = ħ�4πcI, and the moment of inertia is given by m eff R 2 , where m eff =
m 1 m 2 �(m 1 + m 2 ). It follows that R = (ħ�4πcm eff B̃)1�2 .

(1.0078 × 80.9163)m u2 1.6605 × 10−27 kg

m eff = × = 1.65 . . . × 10−27 kg
(1.0078 + 80.9163)m u 1 mu

1.0546 × 10−34 J s
1�2
R=� �
4π×(2.9979 × 10 cm s )×(1.65... × 10−27 kg)×[(16.93�2)cm−1 ]
10 −1

= 141.4 pm

E��B.�(b) �e wavenumbers of the lines in the rotational spectrum are given by [��B.��a–
���], ν̃(J) = 2B̃(J + 1); the lines are therefore spaced by 2B̃, it therefore follows
that B̃ = (1.033�2) cm−1 . �e rotational constant is given by [��B.�–���],
B̃ = ħ�4πcI, and the moment of inertia is given by m eff R 2 , where m eff =
m 1 m 2 �(m 1 + m 2 ). It follows that I = ħ�4πc B̃ and R = (I�m eff )1�2 .

I = ħ�4πc B̃
1.0546 × 10−34 J s
= = 5.420 × 10−46 kg m2
4π × (2.9979 × 1010 cm s−1 ) × [(1.033�2) cm−1 ])
 (34.9688 × 18.9984)m u2 1.6605 × 10−27 kg
m eff = × = 2.04... × 10−26 kg
(34.9688 + 18.9984)m u 1 mu

R = (I�m eff )1�2 = [(5.420... × 10−46 kg m2 )�(2.04... × 10−26 kg)]1�2

= 162.8 pm

E��B.��(b) �e most occupied J state is given by [��B.��–���], J max = (kT�2hc B̃)1�2 − 12 .

(i) At 25 ○ C, ��� K, this gives

J max =
(1.3806 × 10−23 J K−1 )×(298 K)
1�2
� � − 1
2×(6.6261 × 10−34 J s)×(2.9979 × 1010 cm s−1 )×(0.0809 cm−1 ) 2

= ��

(ii) At 100 ○ C, ��� K, this gives

J max =
(1.3806 × 10−23 J K−1 )×(373 K)
1�2
� � − 1
2×(6.6261 × 10−34 J s)×(2.9979 × 1010 cm s−1 )×(0.0809 cm−1 ) 2

= ��

E��B.��(b) For a molecule to show a pure rotational Raman spectrum it must have an
anisotropic polarizability. With the exception of spherical rotors, all molecules
satisfy this requirement. �erefore CH� Cl� , CH� CH� and N� O all give rota-
tional Raman spectra.

E��B.��(b) �e Stokes lines appear at wavenumbers given by [��B.��a–���], ν̃(J +2 ← J) =

ν̃ i − 2B̃(2J + 3), where the wavenumber of the incident radiation is ν̃ i , and J is
the quantum number of the initial state. With the given data

ν̃(4 ← 2) = 20 623 cm−1 − 2 × (1.4457 cm−1 )(2 × 2 + 3) = 20 603 cm−1

E��B.��(b) �e Stokes lines appear at wavenumbers given by [��B.��a–���], ν̃(J +2 ← J) =

ν̃ i − 2B̃(2J + 3), where the wavenumber of the incident radiation is ν̃ i , and J is
the quantum number of the initial state. It therefore follows that the separation
between adjacent lines is 4B̃, hence B̃ = (3.5312�4) cm−1 .
�e rotational constant is given by [��B.�–���], B̃ = ħ�4πcI, and the moment
of inertia is given by m eff R 2 , where m eff = m 1 m 2 �(m 1 + m 2 ). It follows that
I = ħ�4πc B̃ and R = (I�m eff )1�2 .

I = ħ�4πc B̃
1.0546 × 10−34 J s
= = 3.17... × 10−46 kg m2
4π × (2.9979 × 1010 cm s−1 ) × [(3.5312�4) cm−1 ]
 For a homonuclear diatomic the e�ective mass is simply m eff = 12 m

3.17... × 10−46 kg m2
1�2
R = (I�m eff )1�2 = � 1 �
2
× 18.9984 × (1.6605 × 10−27 kg)
= 141.79 pm

��
E��B.��(b) C ��S� is a linear molecule; the carbon atom has no e�ect on the nuclear statis-
tics as it is at the centre. ��S has spin zero, so the behaviour is analogous to that
of ��C ��O� : only even J levels are permissible.
Changing the carbon to ��C has not e�ect as this atom is at the centre.

P��B.� Suppose that the centre of mass is at a distance x from B, and therefore (R − x)
from A and (R′ + x) from C. Balancing moments gives

mA R − mC R′
m A (R − x) = m B x + m C (R ′ + x) hence x =
m
where the total mass is m = m A + m B + m C , the moment of inertia is therefore

I = m A (R − x)2 + m B x 2 + m C (R ′ + x)2

�rst gather terms in powers of x

= m A R 2 + m C R ′2 − 2x(m A R − m C R ′ ) + x 2 (m A + m B + m C )
= m A R 2 + m C R ′2 − 2x(m A R − m C R ′ ) + x 2 m

the substitute for x

I = m A R 2 + m C R ′2 − 2(m A R − m C R ′ )(m A R − m C R ′ )�m

+ (m A R − m C R ′ )2 m�m 2
= m A R 2 + m C R ′2 − 2(m A R − m C R ′ )2 �m + (m A R − m C R′ )2 �m
= m A R 2 + m C R ′2 − (m A R − m C R′ )2 �m

P��B.� �e wavenumbers of the lines expected for a diatomic are given by [��B.��a–
���], ν̃(J) = 2B̃(J + 1); the separation of the lines is 2B̃. �e spacing between
adjacent lines in the given data is not constant, but varies between ��.� cm−1
and ��.� cm−1 , with an average of ��.� cm−1 ; a reasonable �rst guess at the
value of B̃ is therefore 12 × (20.5 cm−1 ) = 10.25 cm−1 . With this estimate it
is then possible to assign the lines, that is determine the value of J associated
with each. From ν̃ = 2B̃(J + 1) it follows that J = ν̃�2B̃ − 1. For the �rst line
J = (83.32 cm−1 )�(20.5 cm−1 ) − 1 = 3.1 which indicates that this is likely to
be the line ν̃(3); similar calculations for the other lines indicates that they are
ν̃(4) . . . ν̃(10).
�e variation in the spacing is attributed to the e�ects of centrifugal distortion.
In this case the wavenumbers of the lines are given by [��B.��b–���], ν̃(J) =
2B̃(J + 1) − 4 D̃ J (J + 1)3 . Division of both side of this expression by (J + 1)
indicates that a plot of ν̃(J)�(J + 1) against (J + 1)2 should be a straight line
with slope −4 D̃ J and intercept 2B̃

� �
intercept slope
ν̃(J)
= 2B̃ −4 D̃ J (J + 1)2
J+1
�e data are tabulated below; δ̃ is the di�erence between successive lines. �e
plot is shown in Fig. ��.�.

ν̃(J)�cm−1 δ̃�cm−1 J [ν̃(J)�(J + 1)]�cm−1 (J + 1)2

83.32 3 20.83 16
104.13 20.81 4 20.83 25
124.73 20.60 5 20.79 36
145.37 20.64 6 20.77 49
165.89 20.52 7 20.74 64
186.23 20.34 8 20.69 81
206.60 20.37 9 20.66 100
226.86 20.26 10 20.62 121

20.9
[ν̃(J)�(J + 1)]�cm−1

20.8

20.7

20.6
0 20 40 60 80 100 120
(J + 1) 2

�e data are quite a good �t to the line

[ν̃(J)�(J + 1)]�cm−1 = −2.0534 × 10−3 × (J + 1)2 + 20.866
�e value of the rotational constant is found from the intercept: (B̃�cm−1 ) =
1
2
× intercept. Some elementary statistics on the best-�t line indicates an error
of about 0.005 cm−1 in the intercept, so the best estimate for the rotational
constant is B̃ = 10.433 ± 0.002 cm−1 . �e slope is (−4 D̃ J �cm−1 ), hence D̃ J =
5.13 × 10−4 cm−1 .
�e rotational constant is given by [��B.�–���], B̃ = ħ�4πcI; it follows that
I = ħ�4πc B̃

1.0546 × 10−34 J s
I= = 2.6832 × 10−47 kg m2
4π × (2.9979 × 1010 cm s−1 ) × (10.433 cm−1 )

�e moment of inertia is I = m eff R 2 , where m eff is the e�ective mass, m eff =

m H m Cl �(m H + m Cl ). It therefore follows that

I(m H + m Cl )
1�2
R = (I�m eff )1�2 = � �
m H m Cl
(2.6832 × 10−47 kg m2 ) × (1.0078 + 34.9688)
1�2
=� � = ���.� pm
(1.0078 × 34.9688) × (1.6605 × 10−27 kg)

Note the factor 1 m u = 1.6605 × 10−27 kg used to convert the masses to kg. If
the average spacing is used as an estimate for B̃ the resulting bond length is
���.� pm, which is signi�cantly di�erent.
To predict the corresponding lines in the spectrum of �H ��Cl it is necessary
to know the values of the rotational constant and the centrifugal distortion
constant. �e rotational constant is inversely proportional to the e�ective mass.
�erefore, assuming that the bond length is the same in the isotopologues, B̃
for �H ��Cl is computed from ratio of e�ective masses

B̃ 2H 35Cl �B̃ 1H 35Cl = m eff , 1H 35Cl �m eff , 2H 35Cl

B̃ 2H 35Cl = B̃ 1H 35Cl × m eff , 1H 35Cl �m eff , 2H 35Cl
m 1H m 35Cl m 2 + m 35Cl
= B̃ 1H 35Cl × × H
m 1H + m 35Cl m 2H m 35Cl
1.0078 × 34.9688 2.0140 + 34.9688
= (10.433 cm−1 ) × ×
1.0078 + 34.9688 2.0140 × 34.9688
= 5.367 cm−1

As explained in Exercise E��B.�(b), the D̃ J ∝ m−2

eff . Because this term only has
a small e�ect it is su�cient to assume that the values of the e�ective masses of
�
HCl and �HCl are dominated by the much lighter �H or �H to give m eff , 1H 35Cl ≈
1 m u and m eff , 2H 35Cl ≈ 2 m u , thus

D̃ J, 2H 35Cl = D̃ J, 1H 35Cl × (1�2)2 = (5.13 × 10−4 cm−1 ) × 1

4
= 1.28 × 10−4 cm−1

With these values of B̃ and D̃ J the wavenumbers of the lines in the spectrum of
H Cl are computed using ν̃(J) = 2B̃(J +1)−4 D̃ J (J +1)3 to give the following
� ��

J 3 4 5 6 7 8 9 10
ν̃(J)�cm−1 42.90 53.61 64.29 74.96 85.61 96.23 106.83 117.39
P��B.� �e wavenumbers of the lines expected for a diatomic are given by [��B.��a–
���], ν̃(J) = 2B̃(J + 1); the separation of the lines is 2B̃. From the data given
the average spacing is ����.�� MHz, and hence B = 3013.8 MHz . �e preci-
sion of this value is likely to be lower than the apparent precision of data: for
example, the two separations measurable from the spectrum di�er by �.� MHz,
indicating that there must be some scatter on the data at this level.
�e rotational constant is given by [��B.�–���], B̃ = ħ�4πcI. Expressed in
frequency units this is B = ħ�4πI. It follows that I = ħ�4πB

1.0546 × 10−34 J s
I = ħ�4πB = = 2.78... × 10−45 kg m2
4π × (3013.8... × 106 Hz)

�e e�ective mass is
m 63Cu m 79Br 62.9296 × 78.9183
m eff = = = 35.0114 m u
m 63Cu + m 79Br 62.9296 + 78.9183

Because I = m eff R 2 it follows that

R = (I�m eff )1�2

= �(2.78... × 10−45 kg m2 )�(35.0114 × [1.6605 × 10−27 kg])� = ��� pm
1�2

P��B.� �e data are tabulated below and the plot is shown in Fig. ��.�.

ν̃(J)�cm−1 J [ν̃(J)�2(J + 1)]�cm−1 (J + 1)2

3.845 033 0 1.922 517 1
7.689 919 1 1.922 480 4
11.534 510 2 1.922 418 9
15.378 662 3 1.922 333 16
19.222 223 4 1.922 222 25

�e data are a good �t to the line

[ν̃(J)�(J + 1)]�cm−1 = −1.225 660 × 10−5 × (J + 1)2 + 1.922 529

�e value of the rotational constant is found from the intercept: (B̃�cm−1 ) =

intercept. Some elementary statistics on the best-�t line indicates an error of
about 10−7 cm−1 in the intercept (which seems improbably small); using this,
the rotational constant is quoted as B̃ = 1.922 529 cm−1 . �e slope is related
to the centrifugal distortion constant as (−2 D̃ J �cm−1 ), and the error is about
10−8 cm−1 hence D̃ J = 6.128 × 10−6 cm−1 .
 1.922 60

[ν̃(J)�2(J + 1)]�cm−1
1.922 50

1.922 40

1.922 30

1.922 20
0 5 10 15 20 25
(J + 1) 2

P��B.�� (a) �e selection rules are ∆J = ±1, ∆K = 0. An allowed absorption transi-

tion from (J, K) to (J + 1, K) has wavenumber

ν̃ = F̃(J + 1, K) − F̃(J, K)
= B̃(J + 1)(J + 2) + (Ã − B̃)K 2 − D̃ J (J + 1)2 (J + 2)2
− D̃ JK (J + 1)(J + 2)K 2 − D̃ K K 4
− �B̃J(J + 1) + (Ã − B̃)K 2 − D̃ J J 2 (J + 1)2

− D̃ JK J(J + 1)K 2 − D̃ K K 4 �
= 2B̃(J + 1) − D̃ J [(J + 1)2 (J + 2)2 − J 2 (J + 1)2 ]
− D̃ JK K 2 [(J + 1)(J + 2) − J(J + 1)]
= 2B̃(J + 1) − D̃ J [(J 2 + 2J + 1)(J 2 + 4J + 4) − J 2 (J 2 + 2J + 1)]
− D̃ JK K 2 [J 2 + 3J + 2 − J 2 − J]
= 2B̃(J + 1) − D̃ J [4 + 12J + 12J 2 + 4J 3 ] − D̃ JK K 2 [2J + 2]
= 2B̃(J + 1) − D̃ J 4(J + 1)3 − D̃ JK 2K 2 (J + 1)

�e wavenumber of the lines in the absorption spectrum are given by

ν̃(J, K) = 2B̃(J + 1) − 4 D̃ J (J + 1)3 − 2 D̃ JK (J + 1)K 2 (��.�)

(b) It is �rst helpful to compute the separation between the lines

51.0718 102.1408 102.1426 153.2076 153.2103

� � � �
51.069 0.0018 51.065 0.0027

Recall that B � D. �e separation of about �� GHz is likely to correspond

to 2B; if this is so then, ignoring centrifugal distortion, the expectation is
ν(0) = 2B = 51 GHz, ν(1) = 4B = 102 GHz, and ν(2) = 6B = 153 GHz.
From eqn ��.� it is seen that for each transition (J + 1 ← J) there are
separate lines for each value of K 2 . �e K quantum number takes values
from −J to +J in integer steps, and so has (2J + 1) values. However, the
energy goes as K 2 , of which there are only (J + 1) distinct values. �e
transition 1 ← 0 has J = 0 and hence K = 0 only: there is one line. �e
transition 2 ← 1 has J = 1 and hence K = 0, 1 : there are two lines, and
because the term in K 2 is negative, the line for K = 1 is at lower frequency
that that for K = 0. �e transition 3 ← 2 has J = 2 and hence K = 0, 1, 2
: there are three lines, running to lower frequency as K increases.
�e following table indicates the quantum numbers for each line and their
frequencies expressed in terms of the various constants.
line observed freq./GHz J K ν(J, K)
1 51.0718 0 0 2B − 4D J
2 102.1408 1 1 4B − 32D J − 4D JK
3 102.1426 1 0 4B − 32D J
not given 2 2 6B − 108D J − 24D JK
4 153.2076 2 1 6B − 108D J − 6D JK
5 153.2103 2 0 6B − 108D J
�e assignment of lines � and � needs some comment. With the assign-
ment given the separation of lines � and � is 6D JK , and the separation of
lines � and � is 4D JK ; these separations are therefore expected to be in the
ratio 6�4 = 1.5. From the data the ratio is (153.2103−153.2076)�(102.1426−
102.1408) = 1.5, which is consistent with the assignment. Such consis-
tency is not achieved with any other values of K for lines � and �.
With this assignment it is possible to �nd the constants but taking dif-
ferences between multiples of the frequencies of di�erent lines from the
table:
line � − line � = 4D JK = 102.1426 − 102.1408 = 0.0018 GHz

hence D JK = 1
4
× 0.0018 GHz = 0.45 MHz .

line � − 2 × line � = −24D J = 102.1426 − 2 × 51.0718 = −0.0010 GHz

hence D J = 24
1
× 0.0010 GHz = 0.042 MHz . A di�erent choice gives a
di�erent value, indicating that the accuracy of the data is perhaps lower
than it appears

2 × line � − 3 × line � = −120D J = 2 × 153.2103 − 3 × 102.1426

= −0.0072 GHz

hence D J = 1
120
× 0.0072 GHz = 0.060 MHz .

line � − 8 × line � = −12B = 102.1426 − 8 × 51.0718 = −306.43 GHz

1
hence B = × 306.4 GHz = 25.536 GHz
12
 It is not possible to �nd A, nor is it possible to �nd D K , as these constants
do not a�ect the frequencies of the lines.

P��B.�� �e issue here is whether or not the rotational transitions of the molecule have
wavenumbers which overlap the range for which the black-body radiation is
signi�cant. �e cosmic microwave background corresponds to about �.� K, and
the wavelength of the maximum radiation density can be found using Wien’s
law, [�A.�–���], λ max T = 2.9 × 10−3 m T. Expressing this as a wavenumber
gives

1�λ max = T�(2.9 × 10−3 m T) = (2.7 K)�(2.9 × 10−3 m T) = 931 m−1

�e peak in the energy density of the black body is therefore at around �.�� cm−1 .
�e rotational constant of CN is �.��� cm−1 , so the �rst line occurs at 2B̃ =
3.782 cm−1 , and subsequent lines at �.��� cm−1 , ��.��� cm−1 and so on. �e
�rst few of these fall conveniently close to the maximum of the black-body
radiation. In contrast, for CH the �rst line is at ��.�� cm−1 , which is already at
a much higher wavenumber than the maximum of the black-body radiation.
�us, in order to study the energy distribution by looking at the lines from a
molecule, CN is much more useful than CH as the CN spectrum overlaps the
region of interest.

P��B.�� �e �rst step is to �nd an expression for the moment of inertia of benzene about
any axis in the plane; as long as the axis lies in the plane and passes through the
centre its location can be chosen freely. Consider the arrangement shown below
in which the axis (shown by the horizontal line) is chosen to pass through two
carbon atoms on opposite sides of the ring. Recall that the distance from the
centre to the vertices is equal to the length of the sides; let this length√be R. �e
perpendicular distance d from one atom to the axis is R sin 60○ = R 3�2. �e
four carbon atoms which are away from the axis are all at the same distance
and so their contribution to the moment of inertia is therefore 4m C (3�4)R 2 =
3m C R 2 ; the other two atoms lie on the axis and so make no contribution.

R d R
��○

Now consider the six hydrogen atoms. �ese also form a hexagon, but with
a larger side, which is denoted R′ . Starting from the centre, the distance to a
carbon atom is R, and the distance to a hydrogen atom in the same direction is
R ′ . It follows that R CH = R′ − R, and as has already been established R CC = R.
 �e contribution that the hydrogen atoms make to the moment of inertia is, by
analogy with the discussion above, 3m H R′2 . �erefore I H = 3m C R 2 + 3m H R ′2
and I D = 3m C R 2 + 3m D R′2 .
To �nd R multiply I H by m D , and I D by m H to give

m D I H = 3m D m C R 2 + 3m D m H R′2 m H I D = 3m H m C R 2 + 3m H m D R ′2

�en, subtract the two expressions and rearrange

mD IH − mH ID
m D I H − m H I D = 3m D m C R 2 − 3m H m C R 2 hence R2 =
3m C (m D − m H )
With the data given

(2.0140) × (1.4759 × 10−45 kg m2 ) − (1.0078) × (1.7845 × 10−45 kg m2 )

R2 =
3 × (12.0000) × (2.0140 − 1.0079) × (1.6605 × 10−27 kg)
= 1.95... × 10−20 m2

�erefore the CC bond length is ���.� pm .

�e value of R′ is obtained by subtracting I H from I D so as to eliminate the
term in R 2
ID − IH
I D − I H = 3R′2 (m D − m H ) hence R ′2 =
3(m D − m H )
With the data given

(1.7845 × 10−45 kg m2 ) − (1.4759 × 10−45 kg m2 )

R ′2 =
3 × (2.0140 − 1.0079) × (1.6605 × 10−27 kg)
= 6.15... × 10−20 m2

�erefore R′ = 248.1 pm and hence R CH = R′ − R = 248.1 − 139.7 = ���.� pm

D��C.� �e rotational constant depends inversely on the moment of inertia, which in

turn depends on the square of the bond length. However, because the molecule
is vibrating, the bond length is constantly changing. Vibration is much faster
than rotation, so for the purposes of calculating the moment of inertia it is
generally a good approximation to take an average over the vibrational motion
and use �R 2 � in place of R 2 . It follows that B ∝ 1��R 2 �.
If the vibration is assumed to be harmonic �R 2 � increases with increasing vi-
brational energy. However, for a typical anharmonic vibration there is a much
greater e�ect on �R 2 � arising from the asymmetry of the potential. Put simply,
instead of the molecule oscillating symmetrically about the equilibrium posi-
tion, the bond stretches more than it is compressed, resulting in the average
 bond length increasing. As the vibrational energy increases the potential curve
becomes shallower for bond extension and the average bond length increases
further.
�e value of 1��R 2 � therefore decreases as the vibrational quantum number υ
increases, and as a result the rotational constant B is a decreasing function of
the υ. For typical molecules, this e�ect of the anharmonicity is dominant, and
it is not unusual for the rotational constant to decrease by �–� per cent when
going from the υ = 0 to the υ = 1 vibrational level.

D��C.� Because bonding is principally a matter resulting from electrostatic interac-

tions, the addition of a neutral particle to the nucleus is not expected to alter the
geometry of a molecule (bond lengths, bond angles), nor is it expected to alter
the force constants which describe the stretching of bonds. However, rotational
spectra, and the rotational �ne structure which is associated with vibrational
spectra, depend on the rotational constants, and in turn these depend on the
e�ective mass. Likewise, vibrational frequencies also depend on the e�ective
mass, and so they too will be a�ected.
Di�erent isotopes may have di�erent nuclear spins and this can a�ect the pat-
tern of intensities of lines arising from di�erent rotational states.

E��C.�(b) �e vibrational frequency of a harmonic oscillator is given by [�E.�–���], ω =

(k f �m)1�2 ; ω is an angular frequency, so to convert to frequency in Hz, ν, use
ω = 2πν. �erefore 2πν = (k f �m)1�2 . Rearranging this gives the force constant
as k f = m(2πν)2

k f = (0.0010 kg) × (2π × 10.0 Hz)2 = 3.95 N m−1

where 1 N = 1 kg m s−2 and 1 Hz = 1 s−1 are used.

E��C.�(b) �e vibrational frequency, expressed as a wavenumber, of a harmonic oscillator

is given by [��C.�b–���], ν̃ = (1�2πc)(k f �m eff )1�2 , where m eff is the e�ective
mass, given by m eff = m 1 m 2 �(m 1 + m 2 ). Assuming that the force constants of
the two isotopologues are the same, ν̃ simply scales as (m eff )−1�2 . �e fractional
change is therefore

ν̃ 1H 35Cl − ν̃ 2H 37Cl
1�2
ν̃ 2 37 m 1 35
= 1 − H Cl = 1 − � eff , H Cl �
ν̃ 1H 35Cl ν̃ 1H 35Cl m eff , 2H 37Cl
1.0078 × 34.9688 2.0140 + 36.9651 1�2
=1−� × � = 0.283...
1.0078 + 34.9688 2.0140 × 36.9651

�e fractional change, expressed as a percentage, is therefore ��.��% .

E��C.�(b) �e wavenumber of the fundamental vibrational transition is simply equal to
the vibrational frequency expressed as a wavenumber. �is is given by [��C.�b–
���], ν̃ = (1�2πc)(k f �m eff )1�2 , where m eff is the e�ective mass, given by m eff =
m 1 m 2 �(m 1 + m 2 ). It follows that k f = m eff (2πc ν̃)2 . With the data given
78.9183 × 80.9163
kf = × (1.6605 × 10−27 kg)
78.9183 + 80.9163
× [2π × (2.9979 × 1010 cm s−1 ) × (323.2 cm−1 )]2
= 245.9 N m−1

Note the conversion of the mass to kg.

E��C.�(b) �e wavenumber of the fundamental vibrational transition is simply equal to

the vibrational frequency expressed as a wavenumber. �is is given by [��C.�b–
���], ν̃ = (1�2πc)(k f �m eff )1�2 , where m eff is the e�ective mass, given by m eff =
m 1 m 2 �(m 1 + m 2 ). Assuming that the force constants of the two isotopologues
are the same, ν̃ simply scales as (m eff )−1�2 . �erefore
1�2 1�2
ν̃ 2HX m 1 m eff , 1HX
= � eff , HX � hence ν̃ 2HX = ν̃ 1HX × � �
ν̃ 1HX m eff , 2HX m eff , 2HX

Using these relationships, the following table is drawn up

n n n n
H ��F H ��Cl H ��Br H ���I
ν̃ 1HX �cm−1 4141.3 2988.9 2649.7 2309.5
m eff , 1HX �m u 0.9570 0.9796 0.9954 0.9999
m eff , 2HX �m u 1.8210 1.9043 1.9651 1.9825
ν̃ 2HX �cm−1 3002.3 2143.7 1885.8 1640.1

E��C.�(b) �e terms (energies expressed as wavenumbers) of the harmonic oscillator are

given by [��C.�b–���], G̃(υ) = (υ + 12 )ν̃; these are wavenumbers and so can
be converted to energy by multiplying by hc to give E(υ) = (υ + 12 )hc ν̃. �e
�rst excited state has υ = 1, and the second has υ = 2. �e relative popula-
tion of these levels is therefore given by the Boltzmann distribution, n 2 �n 1 =
e−(E 2 −E 1 )�k T . �e energy di�erence E 2 − E 1 = hc ν̃, and hence n 2 �n 1 = e−hc ν̃�k T .
It is convenient to compute the quantity hc ν̃�k �rst to give

(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (321 cm−1 )

hc ν̃�k =
1.3806 × 10−23 J K−1
= 461.8... K

It follows that n 2 �n 1 = e−(461.8 ... K)�T

(i) At ��� K, n 2 �n 1 = e−(461.8 ... K)�(298 K) = �.���
(ii) At ��� K, n 2 �n 1 = e−(461.8 ... K)�(800 K) = �.���
 As expected, the relative population of the upper level increases with tempera-
ture.

E��C.�(b) Note: the data in the Exercise are in error, the transitions should be at ����.�� cm−1 ,
����.�� cm−1 , and ����.�� cm−1 .
Taking y e = 0 is equivalent to using the terms for the Morse oscillator, which
are given in [��C.�–���], G̃(υ) = (υ + 12 )ν̃ − (υ + 12 )2 ν̃x e . �e transition υ ← 0
has wavenumber

∆G̃(υ) = G̃(υ) − G̃(0)

= [(υ + 12 )ν̃ − (υ + 12 )2 ν̃x e ] − [(0 + 12 )ν̃ − (0 + 12 )2 ν̃x e ]
= υ ν̃ − υ(υ + 1)ν̃x e

Data on three transitions are provided, but only two are needed to obtain values
for ν̃ and x e . �e ∆G̃(υ) values for the �rst two transitions are

1←0 ν̃ − 2ν̃x e = 2329.91 cm−1

2←0 2ν̃ − 6ν̃x e = 4631.20 cm−1

Multiplying the �rst expression by � and subtracting the second gives

3(ν̃ − 2ν̃x e ) − (2ν̃ − 6ν̃x e ) = ν̃

hence ν̃ = 3 × (2329.91 cm−1 ) − (4631.20 cm−1 ) = 2358.5 cm−1

�is value for ν̃ is used in the �rst equation, which is then solved for x e to give
x e = 12 − (2329.91 cm−1 )�[2 × (2358.53 cm−1 )] = 6.07 × 10−3 .

E��C.�(b) �e strategy here is to see if the data can be modelled by the energy levels of the
Morse oscillator. �is is tested by using the result from [��C.�b–���], ∆G̃ υ+1�2 =
ν̃ − 2(υ + 1)x e ν̃, where ∆G̃ υ+1�2 = G̃(υ + 1) − G̃(υ). �is implies that a plot
of ∆G̃ υ+1�2 against (υ + 1) will have slope −2x e ν̃ and intercept ν̃. �e data are
shown in the table and the plot in Fig. ��.�.

υ G̃ υ �cm−1 ∆G̃ υ+1�2 �cm−1 υ+1

0 1 144.83 2 230.07 1
1 3 374.90 2 150.61 2
2 5 525.51 2 071.15 3
3 7 596.66 1 991.69 4
4 9 588.35

�e data are a good �t to the line

∆G̃ υ+1�2 �cm−1 = −79.46 × (υ + 1) + 2 309.5

 2 200

∆G̃ υ+1�2 �cm−1

2 100

2 000

1 2 3 4
υ+1

�is con�rms that the data are well-described by the Morse levels. From the
slope

x e ν̃�cm−1 = − 12 × slope = − 12 (−79.46) hence x e ν̃ = 39.73 cm−1

and from the intercept

ν̃�cm−1 = intercept = 2 309.5 hence ν̃ = 2 309.5 cm−1

�e depth of the well, D̃ e is then found using [��C.�–���], x e = ν̃�4 D̃ e rear-

ranged to D̃ e = ν̃�4x e = ν̃ 2 �4ν̃x e . �e dissociation energy is D̃ 0 = D̃ e − G̃(0)
(Fig. ��C.� on page ���), hence

ν̃ 2
D̃ 0 = D̃ e − G̃(0) = − G̃(0)
4ν̃x e
(2309.5 cm−1 )2
= − (1144.83 cm−1 ) = 3.24 × 104 cm−1
4 × (39.73 cm−1 )

To convert to eV, the conversion 1 eV = 8065.5 cm−1 from inside the front cover
is used to give D 0 = 4.02 eV .
�e result is only quoted to modest precision because in e�ect the dissociation
limit is extrapolated from just a few levels near to the bottom of the potential
energy well.

E��C.�(b) �e wavenumber of the transition arising from the rotational state J in the P
branch (∆J = −1) of the fundamental transition (υ = 1 ← υ = 0) is given
by [��C.��a–���], ν̃ P (J) = ν̃ − 2B̃J. In this case ν̃ = 2648.98 cm−1 and B̃ =
8.465 cm−1 hence

ν̃ R (2) = (2648.98 cm−1 ) − 2 × (8.465 cm−1 ) × 2 = ����.� cm−1

P��C.� �e potential energy function for a Morse oscillator is given by [��C.�–���],
V (x) = hc D̃ e (1 − e−ax )2 , and the force constant is de�ned in [��C.�b–���] as
k f = (d2 V �dx 2 )0 .

d
hc D̃ e (1 − e−ax )2 = 2hc D̃ e (1 − e−ax )(ae−ax ) = 2hc D̃ e a(e−ax − e−2ax )
dx
d2 d
V (x) = 2hc D̃ e a(e−ax − e−2ax ) = 2hc D̃ e a(−ae−ax + 2ae−2ax )
dx 2 dx
Evaluation the second derivative at x = 0 gives

k f = (d2 V �dx 2 )0 = 2hc D̃ e a(−a + 2a) = 2hc D̃ e a 2

P��C.� �e quoted vibrational terms, G̃(υ) = (υ + 12 )ν̃ − (υ + 12 )2 x e ν̃, are those of a

Morse oscillator. �erefore [��C.�b–���] applies, ∆G̃ υ+1�2 = ν̃ − 2(υ + 1)x e ν̃,
where ∆G̃ υ+1�2 = G̃(υ + 1) − G̃(υ), applies. It is therefore expected that a plot
of ∆G̃ υ+1�2 against (υ + 1) will have slope −2x e ν̃ and intercept ν̃. �e data are
shown in the table and the plot in Fig. ��.�.

υ G̃ υ �cm−1 ∆G̃ υ+1�2 �cm−1 υ+1

0 142.81 284.50 1
1 427.31 283.00 2
2 710.31 281.50 3
3 991.81

285

284
∆G̃ υ+1�2 �cm−1

283

282

281
0.5 1.0 1.5 2.0 2.5 3.0 3.5
υ+1

�e data are a good �t to the line

∆G̃ υ+1�2 �cm−1 = −1.500 × (υ + 1) + 286.00

 �is con�rms that the data are well-described by the Morse levels. From the
slope
x e ν̃�cm−1 = − 12 × slope = − 12 (−1.500) hence x e ν̃ = 0.750 cm−1
and from the intercept
ν̃�cm−1 = intercept = 286.00 hence ν̃ = 286.00 cm−1
�e zero-point energy is G̃(0), which is, from the data given, 142.81 cm−1 .
�e depth of the well, D̃ e is then found using [��C.�–���], x e = ν̃�4 D̃ e rear-
ranged to D̃ e = ν̃�4x e = ν̃ 2 �4ν̃x e . �e dissociation energy is D̃ 0 = D̃ e − G̃(0)
(Fig. ��C.� on page ���), hence
ν̃ 2
D̃ 0 = D̃ e − G̃(0) = − G̃(0)
4ν̃x e
(286.00 cm−1 )2
= − (142.81 cm−1 ) = 2.71 × 104 cm−1
4 × (0.750 cm−1 )
To convert to eV, the conversion 1 eV = 8065.5 cm−1 from inside the front cover
is used to give D 0 = 3.36 eV . �e result is only quoted to modest precision
because in e�ect the dissociation limit is extrapolated from just a few levels
near to the bottom of the potential energy well.
In the harmonic limit the vibrational frequency is given by [��C.�b–���], ν̃ =
(1�2πc)(k f �m eff )1�2 , with the e�ective mass given by m eff = m 1 m 2 �(m 1 +m 2 ).
It follows that k f = m eff (2πc ν̃)2 .
22.9898 × 126.9045
kf = × (1.6605 × 10−27 kg)
22.9898 + 126.9045
× [2π × (2.9979 × 1010 cm s−1 ) × (286.00 cm−1 )]2
= 93.8 N m−1

P��C.� �e Morse potential is given by [��C.�–���], V (x) = hc D̃ e (1 − e−ax )2 , where

a = (m eff ω 2 �2hc D̃ e )1�2 . �e task is to relate the constant a to the given values
of ν̃ and ν̃x e . �is is done by starting with [��C.�–���], x e = ν̃�4 D̃ e , hence
D̃ e = ν̃�4x e ; using ν̃ = ω�(2πc) this becomes D̃ e = ω�8πcx e . �is is then used
in the expression for a to give
1�2 1�2
m eff ω 2 m eff ω 2 8πcx e
a=� � =� × �
2hc D̃ e 2hc ω
m eff 4πx e (2πc ν̃)
1�2 1�2
m eff 4πx e ω 1�2 8π 2 cm eff x e ν̃
=� � =� � =� �
h h h
where ω = 2πc ν̃ is used once more. With the data given
84.9118 × 1.0078
m eff = × (1.6605 × 10−27 kg) = 1.65... × 10−27 kg
84.9118 + 1.0078
8π 2 (2.9979 × 1010 cm s−1 ) × (1.65... × 10−27 kg) × (14.15 cm−1 )
1�2
a=� �
6.6261 × 10−34 J s
= 9.14... × 109 m−1 = 9.14... nm−1
 �e well depth D̃ e is computed using D̃ e = ν̃�4x e = ν̃ 2 �4x e ν̃; with the given data
D̃ e = (936.8 cm−1 )2 �(4 × [14.15 cm−1 ]) = 15 505 cm−1 . With these values of
a and D e , and using x = R − R e , the potential is plotted in Fig. ��.�.

30 000
J =0
J = 40
J = 80
[V (R)�hc]�cm−1

20 000 J = 100

10 000

0
200 400 600 800
R�pm

If rotation is included the potential is modi�ed to V ∗ = V + hc B̃J(J + 1), which

is conveniently rewritten as V ∗ �hc = V �hc + B̃J(J + 1) so that the value of
V ∗ �hc is plotted as a wavenumber. Because B̃ ∝ R−2 , the value of B̃ at any R is
related to its value at the equilibrium bond length as

B̃(R) R e2 R e2
= hence B̃(R) = B̃(R e )
B̃(R e ) R 2 R2

�e e�ective potential function to plot is therefore

R e2
V ∗ �hc = D̃ e (1 − e−a(R−R e ) )2 + B̃(R e ) J(J + 1)
R2

�is is plotted in Fig. ��.� for the indicated values of J. It is seen that as J
increases the depth of the potential well decreases, and that for J = 100 there is
no minimum in the potential, implying that the molecule is not bound.

P��C.� �e vibrational terms of the Morse oscillator are [��C.�–���], G̃(υ) = (υ +

1
2
)ν̃ −(υ+ 12 )2 x e ν̃. Because of the term in x e , which goes as υ 2 , the energy levels
get closer together and eventually the spacing goes to zero at the dissociation
limit. �is spacing is given by [��C.�b–���], ∆G̃ υ+1�2 = ν̃ − 2(υ + 1)x e ν̃, where
∆G̃ υ+1�2 = G̃(υ + 1) − G̃(υ). �e quantum number of the state at which the
spacing goes to zero is therefore found by solving ∆G̃ υ max +1�2 = 0

ν̃ − 2(υ max + 1)x e ν̃ = 0 hence υ max = 1�2x e − 1

 An alternative approach is say that G̃(υ) reaches a maximum value at the dis-
sociation limit, and therefore to �nd this limit by solving dG̃(υ)�dυ = 0

d
�(υ + 12 )ν̃ − (υ + 12 )2 x e ν̃� = ν̃ − 2(υ + 12 )x e ν̃
dυ
solving 0 = ν̃ − 2(υ max + 12 )x e ν̃ gives υ max = 1�2x e − 1
2

�e di�erence between this result and that previously obtained is not signi�cant
because υ max is an integer, whereas both of the expressions derived treat υ as
a continuous variable; it will therefore be necessary to round to the nearest
integer.
Yet another approach is to seek the value of υ at which the energy of the term
reaches D̃ e
(υ max + 12 )ν̃ − (υ max + 12 )2 x e ν̃ = D̃ e
�is is most easily solved by letting y = (υ max + 12 ) to give the quadratic

0 = y 2 x e ν̃ − y ν̃ + D̃ e
hence y = (1�2x e ν̃) �ν̃ ± (ν̃ 2 − 4x e ν̃ D̃ e )1�2 �

Using x e = ν̃�4 D̃ e from [��C.�–���] gives

y = (1�2x e ν̃) �ν̃ ± (ν̃ 2 − ν̃ 2 )1�2 � = 1�2x e

hence υ max = 1�2x e − 12 .

P��C.�� �e rotational constant is given by [��B.�–���], B̃ = ħ�4πcI, and the moment

of inertia is given by m eff R 2 , with m eff = m 1 m 2 �(m 1 + m 2 ). It follows that
R = (ħ�4πcm eff B̃)1�2 .

12.0000 × 15.9949
m eff = × (1.6605 × 10−27 kg) = 1.13... × 10−26 kg
12.0000 + 15.9949

For the υ = 0 state B̃ = 1.9314 cm−1 and hence

R = (ħ�4πcm eff B̃)1�2

1.0546 × 10−34 J s
1�2
=� �
4π × (2.9979 × 1010 cm s−1 ) × (1.13... × 10−26 kg) × (1.9314 cm−1 )
= 112.8 pm

Repeating the calculation for the υ = 1 state B̃ = 1.6116 cm−1 gives 123.5 pm .
In fact the data are in error: the rotational constant for υ = 0 is 1.9225 cm−1
giving R = 113.1 pm, and for υ = 1 it is 1.9050 cm−1 giving R = 113.6 pm. �is
variation by a fraction of a percent is more typical.
P��C.�� �e expectation is that the separation between the lines in the P and R branches
will be approximately constant at 2B̃; however the separation of the �rst line of
the R branch, ν̃ R (0), from the �rst line of the P branch, ν̃ P (1), is approximately
4B̃. Examination of the data shows that the separation between the lines at
����.�� cm−1 and at ����.�� cm−1 is approximately twice that between the
other lines. �erefore ����.�� cm−1 is assigned as the �rst line of the R branch,
the transition J = 1 ← 0, and ����.�� cm−1 is assigned as the �rst line of the P
branch, the transition J = 0 ← 1. �e assignment of the other lines follows by
working out from these.
In the method of combination di�erences, lines sharing a common upper (or
lower) J level are identi�ed and a plot is made of the di�erence between the
wavenumbers of these pairs of lines against J. According to [��C.��b–���] a
plot of ν̃ R (J) − ν̃ P (J) against (J + 12 ) will have slope 4B̃ 1 , and according to
[��C.��a–���] a plot of ν̃ R (J − 1) − ν̃ P (J + 1) against (J + 12 ) will have slope
4B̃ 0 . �e data are shown in the tables and the corresponding lines are plotted
in Fig. ��.�.

J ν̃ R (J)�cm−1 ν̃ P (J)�cm−1 [ν̃ R (J) − ν̃ P (J)]�cm−1 J + 12

0 2 906.25 0.5
1 2 925.92 2 865.14 60.78 1.5
2 2 944.99 2 843.63 101.36 2.5
3 2 963.35 2 821.59 141.76 3.5
4 2 981.05 2 799.00 182.05 4.5
5 2 998.05

J ν̃ R (J)�cm−1 ν̃ P (J)�cm−1 [ν̃ R (J −1) − ν̃ P (J +1)]�cm−1 J + 12

0 2 906.25 0.5
1 2 925.92 2 865.14 62.62 1.5
2 2 944.99 2 843.63 104.33 2.5
3 2 963.35 2 821.59 145.99 3.5
4 2 981.05 2 799.00 4.5
5 2 998.05

Both plots show good straight lines. For the plot of ν̃ R (J) − ν̃ P (J) the slope
is 40.42 and hence B̃ 1 = (slope�4) cm−1 = ��.�� cm−1 . For the second plot
of ν̃ R (J − 1) − ν̃ P (J + 1) the slope is 41.68 and hence B̃ 0 = (slope�4) cm−1 =
��.�� cm−1 .

P��C.�� For a harmonic potential the virial theorem ([�E.��–���]) states that �V � =
�E k �. �e total energy is the sum of the kinetic and potential energies, therefore
E tot = �V � + �E k �. It therefore follows that E tot = 2�V �.
 ν̃ R (J) − ν̃ P (J)
ν̃ R (J −1) − ν̃ P (J +1)
150
�cm−1

100

1 2 3 4 5
J+ 1
2

For a harmonic oscillator E tot = (υ + 12 )ħ(k f �m)1�2 and V = 12 k f x 2 hence

2 × � 12 k f x 2 � = (υ + 12 )ħ(k f �m)1�2
hence �x 2 � = k f−1 ħ(υ + 12 )(k f �m)1�2
= (υ + 12 )ħ(1�k f m)1�2
�e average of x 2 therefore increases with the vibrational energy (is indicated
by the quantum number υ).
�e rotational constant is given by B̃ = ħ�4πcI = ħ�4πcm eff R 2 . Because the
bond is vibrating much faster than the molecule is rotating, the term R 2 is
replaced by the average �R 2 � over a vibration. It is shown in Problem P��C.��
that �R 2 � = R e2 + �x 2 �. �erefore, because �x 2 � increases with υ, so does �R 2 �
and therefore the rotational constant B̃ decreases with υ.
If the potential is anharmonic the vibration is no longer symmetric about the
equilibrium separation: the average of R is greater than R e because the bond
stretches more than it compresses. �e greater the vibrational energy, the more
asymmetric the vibration becomes and hence the greater �R� becomes. As a
result the rotational constant decreases with increasing vibrational quantum
number. Usually this e�ect is much greater than that expected for a harmonic
potential.

P��C.�� If the centrifugal force balances exactly the force due to extending the bond
from R e to R c , the following applies
k f (R c − R e ) = m eff ω 2 R c hence (R c − R e ) = m eff ω 2 R c �k f (��.�)
It is helpful to recall the steps for converting a classical expression for the rota-
tional energy into the corresponding quantum expression. �e (kinetic) energy
of a body with moment of inertia I rotating at (angular) velocity ω is E = 12 Iω 2 .
�e rotational angular momentum J is given by J = Iω. It therefore follows
that E = 12 (Iω)2 �I = J 2 �2I.
�e classical angular momentum J is then replaced by the quantum expression
[J(J + 1)]1�2 ħ to give E = J(J + 1)ħ 2 �2I, where J is the rotational quantum
number. �is expression is written E = J(J + 1)hB where B = ħ�4πI = h�8π 2 I,
the rotational constant in frequency units.
�e aim of the derivation is to generate an expression which can be compared
with E(J) = hBJ(J + 1) − hD J J 2 (J + 1)2 ; the �rst term is recognised as orig-
inating from a classical term J 2 (as in the above discussion), and the second
term is recognised as originating from a classical term J 4 .
�e �rst step is to write the rotational energy as a sum of two terms

�
E1

J 2 ��1 � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � ��2
E2

E= + k f (R c − R e ) (��.�)
2I 2
�e �rst term is the rotational energy of a rigid rotor, the second term is the
energy that arises from stretching the bond from R e to R c : it is simply the
harmonic potential energy. From now on attention is focused on this second
term. �e expression for (R c − R e ) from eqn ��.� is inserted to give
2
m eff ω 4 R c2 m eff
2
ω 4 R c2
E 2 = 12 k f (R c − R e )2 = 12 k f =
k f2 2k f

Because the aim is to generate a term of the form J 4 = (Iω)4 , rewrite ω 4 as

(Iω)4 �I 4 . �en recognise that I = m eff R c2 and cancel one factor of I

2
m eff (Iω)4 R c2 m eff (Iω)4 (m eff R c2 ) m eff (Iω)4
E2 = = =
2k f I 4 2k f I 4 2k f I 3

For a harmonic oscillator the vibrational frequency is given by ω HO = (k f �m eff )1�2 ,

hence (m eff �k f ) = 1�ω 2HO ; using this gives

(Iω)4 J4
E2 = 2
=
2ω HO I 3 2ω 2HO I 3

To create the quantum expression replace J with [J(J + 1)]1�2 ħ to give

J 2 (J + 1)2 ħ 4 2 3 3
2 ħ 8 2 4(hB)
E2 = = J 2
(J + 1) � � = J 2
(J + 1)
2ω 2HO I 3 2I 2ħ 2 ω 2HO ħ 2 ω 2HO
��� � � �� � � �
(hB)3

To write the expression in wavenumbers, divide both sides by hc to give

4(hB)3 4(hB)3
Ẽ 2 = E 2 �hc = J 2 (J + 1)2 = J 2
(J + 1) 2
ħ 2 ω HO × hc
2 ch 3 ω 2HO �4π 2
 Finally, note that the harmonic frequency can be expressed as a wavenumber:
ν̃ = ω HO �2πc, hence ω 2HO = 4π 2 c 2 ν̃ 2 , and that the rotational constant can also
be expressed as a wavenumber B = c B̃

4(hc B̃)3 2 4B̃

3
Ẽ 2 = J 2 (J + 1)2 = J 2
(J + 1)
ch 3 (4π 2 c 2 ν̃ 2 )�4π 2 ν̃ 2

If follows that D̃ J = 4B̃ 3 �ν̃ 2 , as required.

For completeness it is necessary to consider the term E 1 in eqn ��.� in some
more detail. �is term contains the moment of inertia which, as a result of the
stretching of the bond, is given by I = m eff R c2 .

J2 J2
E1 = =
2I 2m eff R c2

From eqn ��.� R c = R e �(1 − m eff ω 2 �k f ). It therefore follows that

J 2 (1 − m eff ω 2 �k f )2
=
2m eff R e2

If it is assumed that m eff ω 2 �k f � 1 (which is the case for typical molecules),

then this term may be ignored and hence

J2 J2
E1 = =
2m eff R e 2I eq
2

where I eq is the moment of inertia corresponding to the equilibrium separation

– that is, in the absence of any centrifugal distortion.

P��C.�� According to [��C.��b–���] ν̃ R (J) − ν̃ P (J) = 4B̃ 1 (J + 12 ), and according to

[��C.��a–���] ν̃ R (J − 1) − ν̃ P (J + 1) = 4B̃ 0 (J + 12 ). Hence

ν̃ R (1) − ν̃ P (1) = 6B̃ 1 and ν̃ R (0) − ν̃ P (2) = 6B̃ 0

�erefore

B̃ 1 = [(2150.858 cm−1 ) − (2139.427 cm−1 )]�6 = �.��� cm−1

B̃ 0 = [(2147.084 cm−1 ) − (2135.548 cm−1 )]�6 = �.��� cm−1

Because only data from a few lines have been used, high precision is not war-
ranted.
D��D.� �e gross selection rule for vibrational Raman scattering is that for a particular
normal mode to be active the vibration must result in a change in the polar-
izability as the molecule vibrates about the equilibrium position. �e origin
of this rule is that such an change in the polarizability will result in the dipole
induced in the molecule by the electric �eld of the incident radiation being
altered as the molecule vibrates. It is this modulation of the dipole that results
in Raman scattering.

E��D.�(b) With the exception of homonuclear diatomics, all molecules have at least one
infrared active normal mode. Of the molecules listed, CH� CH� , CH� , and
CH� Cl have infrared active modes.

E��D.�(b) According to [��D.�–���], a non-linear molecule has 3N − 6 vibrational normal

modes, where N is the number of atoms in the molecule; a linear molecule has
3N − 5 normal modes.
(i) C� H� is non-linear, has N = 12 and hence �� normal modes.
(ii) C� H� CH� is non-linear, has N = 15 and hence �� normal modes.
(iii) HC ≡ C – C ≡ CH is linear, has N = 6 and hence �� normal modes.

E��D.�(b) According to [��D.�–���], a linear molecule has 3N − 5 normal modes, where

N is the number of atoms in the molecule. �ere are �� atoms in this linear
molecule, and so there are 3(36) − 5 = ��� normal modes.

E��D.�(b) According to [��D.�–���], a non-linear molecule has 3N − 6 vibrational normal

modes, where N is the number of atoms in the molecule; therefore SO� has
� normal modes. �e terms (energies expressed as wavenumbers) for normal
mode q are given by [��D.�–���], G̃ q (υ) = (υ q + 12 )ν̃ q , where υ q is the quantum
number for that mode and ν̃ q is the wavenumber of the vibration of that mode.
�ese terms are additive, so the ground state term corresponds to each mode
having υ q = 0

G̃ 1 (0) + G̃ 2 (0) + G̃ 3 (0) = 1

2
(ν̃ 1 + ν̃ 2 + ν̃ 3 )

E��D.�(b) A planar AB� molecule has no permanent dipole moment, but in the normal
mode in which the central atom is displaced vertically out of the plane of the
molecule, a dipole will be induced in this direction. During the vibration, the
A atom passes back and forth through the plane of the molecule, resulting in
an oscillating dipole: the normal mode will therefore be infrared active .
 �is mode is in fact not Raman active , something which is best deduced using
the symmetry arguments discussed in Topic ��E. �e rule of mutual exclusion
does not apply.

E��D.�(b) �e benzene molecule has a centre of symmetry, so the rule of mutual exclusion
applies. �e molecule has no permanent dipole moment but if it is distorted
into a boat-like shape the expectation is that there will be an induced dipole
and that therefore the mode will be infrared active .
According to the rule of mutual exclusion, such a mode is not Raman active .

E��D.�(b) �e exclusion rule applies only to molecules with a centre of symmetry. C� H�

does possess such symmetry, and so the exclusion rule does apply .

P��D.� NO� + is isoelectronic with CO� , so the molecule is linear. Around the central
N there are four electron pairs, arranged as two double bonds.
�e normal modes of NO� + are analogous to those of CO� shown in Fig. ��D.�
on page ���. �e one Raman active normal mode at ���� cm−1 is the symmetric
stretch (ν 1 ). �e lowest frequency mode at ��� cm−1 is the (doubly degenerate)
bend (ν 3 ): typically, bends are a lower frequencies than stretches. �e infrared
active mode at ���� cm−1 is the asymmetric stretch (ν 2 ).
�e weak absorption at ���� cm−1 is likely to be either an overtone or a com-
bination band. �e most likely candidate is for one quantum to be excited
into each of the modes ν 1 and ν 2 ; such a transition would have wavenumber
1400 cm−1 + 2360 cm−1 = 3760 cm−1 . �e numbers do not agree exactly due
to the e�ects of anharmonicity.

E��E.�(b) Note that there is an error in the Exercise: the displacements span A1g + 2A1u +
2E1u + E1g .
�e displacements include translations and rotations. For the point group D∞h ,
(x, y) and z transform as E1u and A1u , respectively. �e rotations (R x , R y )
transform as E1g ; for a linear molecule there is no rotation about the inter-
nuclear axis and so the symmetry species for R z is not taken away. Taking
these symmetry species away leaves just the symmetry species of the normal
modes as A1g + A1u + E1u . �eses correspond to � normal modes, which is
the number expected for a linear triatomic (the E1u is doubly degenerate).
E��E.�(b) A mode is infrared active if it has the same symmetry species as one of the
functions x, y, and z; in this point group these span E1u + A1u . A mode is
Raman active if it has the same symmetry as a quadratic form; in this group
such forms span A1g + E1g + E2g .
�erefore the A1u and E1u normal modes are infrared active , and the A1g
mode is Raman active . �e rule of mutual exclusion applies.

E��E.�(b) (i) H� O belongs to the point group C 2v . Rather than considering all � dis-
placement vectors together it is convenient to consider them in sub-sets
of displacement vectors which are mapped onto one another by the op-
erations of the group. �e x, y, and z vectors on the oxygen are not
mapped onto the displacements of the H atoms and so can be considered
separately. In fact, because these displacement vectors are attached to the
principal axis, they transform as the cartesian functions x, y, and z as
listed in the character table: that is as B1 + B2 + A1 .
Assuming the same axis system as in Fig. ��E.� on page ���, the two x
displacements on the H atoms map onto one another, as do the two y
displacements, as do the two z displacements: however, the x, y, and z
displacements are not mixed with one another. For the two z displace-
ments the operation E leaves both una�ected so the character is �; the C 2
operation swaps the two displacements so the character is �; the σv (xz)
operation swaps the two displacements so the character is �; the σv′ (yz)
operation leaves the two displacements una�ected so the character is �.
�e representation is therefore (2, 0, 0, 2), which is easily reduced by in-
spection to A1 + B2 . For the two y displacements the argument is essen-
tially the same, resulting in the representation (2, 0, 0, 2), which reduces
to A1 + B2 .
For the two x displacements the operation E leaves both una�ected so
the character is �; the C 2 operation swaps the two displacements so the
character is �; the σv (xz) operation swaps the two displacements so the
character is �; the σv′ (yz) operation leaves the two displacements in the
same position by changes their direction, so the character is −2. �e rep-
resentation is therefore (2, 0, 0, −2), which is easily reduced by inspection
to A2 + B1 .
�e � displacements therefore transform as 3A1 + A2 + 2B1 + 3B2 .
�e displacements include translations and rotations. For the point group
C 2v , x, y, and z transform as B1 , B2 , and A1 , respectively. �e rotations
R x , R y , and R z transform as B2 , B1 , and A2 , respectively. Taking these
symmetry species away leaves just the normal modes as 2A1 + B2 .
A mode is Raman active if it has the same symmetry as a quadratic form;
in this group such forms span A1 + A2 + B1 + B2 . �erefore all of the
normal modes are Raman active.
(ii) H� CO is a straightforward extension of the case of H� O as both molecules
belong to the point group C 2v . �e H� C portion lies in the same position
as H� O, with the carbonyl O atom lying on the z axis (the principal axis).
�e analysis therefore includes three more displacement vectors for the
 O, and as they are connected to the principal axis they transform as the
cartesian functions x, y, and z, that is as B1 + B2 + A1 . �e tally of
normal modes is therefore those for H� O plus these three in addition:
3A1 + B1 + 2B2 . All these modes are Raman active.

P��E.� It is helpful to tabulate the given data

band in infrared/cm−1 870 1370 2869 3417

−1
band in Raman/cm 877 1408 1435 3407

Bands which are are described as deriving from the same normal mode are
listed in the same column. It is evident that the rule of mutual exclusion does
not apply, therefore the molecule cannot have a centre of symmetry.

(i) If the molecule were linear it would have 3 × 4 − 5 = � normal modes.

(ii) Assuming � is planar the molecule possesses a centre of symmetry, a mir-
ror plane in which the molecule lies, and a C 2 axis perpendicular to the
plane of the molecule and passing through the mid-point of the O–O
bond. �e point group is therefore C 2h .
Assuming � is planar the molecule possesses: a C 2 axis lying in the plane
of the molecule, passing through the mid-point of the O–O bond and
perpendicular to this bond; and two mirror planes, one in the plane of
the molecule and one perpendicular to this and containing the C 2 axis.
�e point group is therefore C 2v .
� has a C 2 axis passing through the mid-point of the O–O bond and
bisecting the dihedral angle formed between the two O–H bonds. �e
point group is therefore C 2 .
(iii) �is part of the question can be answered without determining the sym-
metry species of the normal modes in each case. As has already been
noted, the data indicate that the rule of mutual exclusion is not obeyed,
so this immediately rules out structure �.
In the point group C 2 , (x, y, z) span the symmetry species A and B, and
the quadratic forms span the same species. �erefore all normal modes
(which have to transform as either A or B, the only two symmetry species
in the group) are in principle both Raman and infrared active. �is is
inconsistent with the data, which shows modes which are only seen in
either the Raman or the infrared.
In the point group C 2v , (x, y, z) span the symmetry species A1 + B1 + B2 ,
but the quadratic forms span A1 + A2 + B1 + B2 . �is means that any
mode active in the infrared is also active in the Raman, which is again
inconsistent with the data.
�e data do not appear to be consistent with any of the three structures.
However, it must be kept in mind that the prediction of whether or not a
normal mode is active in the infrared or Raman is simply a prediction in
 principle. It may be that for other reasons a particular normal mode gives
a band with such low intensity that it cannot be detected. �e consensus
view for H� O� is that it has structure �.

For reference the symmetry species of the normal modes are: � 3Ag + Au + 2Bu ;
� 3A1 + A2 + 2B2 ; � 4A + 2B.

D��F.� �is is explained in Section ��F.�(c) on page ���. A progression is set of transi-
tions arising from a common vibrational level in one electronic state to succes-
sive vibrational levels in another electronic state. If the potential energy curve
of the upper electronic state is displaced to a shorter or longer equilibrium bond
length than that of the ground state, then the Franck–Condon factors are likely
to make it possible to see a vibrational progression arising from the υ = 0 level
in the ground electronic state (for small molecules only this level is likely to be
populated).

D��F.� Colour can arise by the emission, absorption, or scattering of electromagnetic

radiation by an object. Many molecules have electronic transitions that have
wavelengths in the visible portion of the electromagnetic spectrum. When
a substance emits radiation, the perceived colour of the object will be that
of the emitted radiation, and it may be an additive colour resulting from the
emission of more than one wavelength of radiation. When a substance absorbs
radiation its colour is determined by the subtraction of those wavelengths from
white light. For example, absorption of red light results in the object being
perceived as green. Scattering, including the di�raction that occurs when light
falls on a material with a grid of variation in texture or refractive index having
dimensions comparable to the wavelength of light (for example, the plumage
of a bird), may also form colour.

D��F.� �e electronic con�guration of Zn�+ is ... 3s2 3p6 3d10 . �e �d sub-shell is full,
so no transitions involving the rearrangement of these electrons is possible.

E��F.�(b) �e term symbol indicates �� = 1, which means that one electron must have
λ = 0 and one have λ = ±1, implying that one electron is in a σ and one in a π
orbital. �e total spin, S, is �, meaning that the two electrons must have parallel
spins. �e overall symmetry with respect to inversion is u, which implies one
electron has g and one has u symmetry. �e con�guration is therefore σ 1g π 1u .
E��F.�(b) Filled orbitals make no contribution to Λ and S, and so can be ignored. �e
electronic con�guration of O� is ... 1π 2g , so that of O� – is ... 1π 3g . With three
electrons in a pair of degenerate orbitals two of the spins must be paired, so
the overall spin S is 12 , and hence (2S + 1) = 2. �e degenerate π orbitals have
λ = ±1. �erefore two electrons are in the orbital with λ = +1 and one in the
orbital with λ = −1 to give Λ = +1 + 1 − 1 = +1, or two have λ = −1 and one has
λ = +1 to give Λ = −1 − 1 + 1 = −1. Overall, Λ = ±1, which is represented by
Π. �e symmetry with respect to inversion is g × g × g = g. �e term symbol is
therefore 2 Π g .

E��F.�(b) �e electronic con�guration given is 1σ 2g 1σ 2u 1π 2u 1π 2g . �e �lled orbitals, 1σ 2g

and 1σ 2u , make no contribution to Λ and S, and so can be ignored. With two
electrons in a pair of degenerate π u orbitals, the spins may either be paired or
parallel. Likewise, the two electrons in the degenerate π g orbitals may either be
paired or parallel. �e overall result is that the maximum number of parallel
spins is 4 × 12 = 2, corresponding to S = 2; it is also possible for all the spins to
be paired up giving S = 0. �e intermediate value S = 1 is also possible. �e
spin multiplicities are therefore � , � and � .
�e two electrons in the π u have overall symmetry with respect to inversion
(parity) u × u = g. �e two electrons in the π g have overall symmetry with
respect to inversion (parity) g × g = g. �us the overall symmetry with respect
to inversion is g .

E��F.�(b) (i) Allowed

(ii) Allowed
(iii) Symmetry forbidden

E��F.�(b) Note: there is an error in the Exercise. �e second function should be ψ ′1 =

N 1 (x − x 0 )e−a(x−x 0 ) �2 .
2

To evaluate the normalizing factor for the function e−ax �2

2
requires the integral
+∞
� e−ax dx
2

−∞

which is of the form of Integral G.� with k = a and evaluates to (π�a)1�2 . �e

normalizing factor is therefore N 0 = (a�π)1�4 .
To evaluate the normalizing factor for the function (x−x 0 )e−a(x−x 0 ) �2
2
requires
the integral
+∞
� (x − x 0 )2 e−a(x−x 0 ) dx
2

−∞

�e substitution y = x −x 0 makes this of the form of Integral G.� with k = a and

evaluates to 12 (π�a 3 )1�2 . �e normalizing factor is therefore N 1 = (4a 3 �π)1�4 .
 �e Franck–Condon factor is given by [��F.�–���] and involves the square of
integral of the product of the two wavefunctions
+∞
I = N1 N0 � e−ax �2
(x − x 0 )e−a(x−x 0 ) �2
2 2
dx
−∞
+∞
= (a�π)1�4 (4a 3 �π)1�4 � (x − x 0 )e−a[x �2+(x−x 0 )2 �2]
2
dx
−∞
+∞
= (2a 2 �π)1�2 � (x − x 0 )e−a[x �2+x 2 �2−x x 0 +x 02 �2]
2
dx
−∞
+∞
= (2a 2 �π)1�2 � (x − x 0 )e−a[x −x x 0 +x 02 �2]
2
dx
−∞
+∞
= (2a 2 �π)1�2 � (x − x 0 )e−a(x−x 0 �2) e−ax 0 �4 dx
2 2

−∞

the �nal equality above is veri�ed by expanding out the square and recombining
the terms. �e next step is to take out the constant factors and split the integral
into two using (x − x 0 ) = (x − x 0 �2) − x 0 �2
+∞
I = (2a 2 �π)1�2 e−ax 0 �4 � (x − x 0 )e−a(x−x 0 �2) dx
2 2

−∞

= (2a 2 �π)1�2 e−ax 0 �4

2

+∞ +∞
× �� (x − x 0 �2)e−a(x−x 0 �2) dx − (x 0 �2) � e−a(x−x 0 �2) dx�
2 2

−∞ −∞

�e �rst integral is of an odd function over a symmetric interval and so is zero.

�e second integral is of the form of Integral G.� with k = a and evaluates to
(π�a)1�2 (it does not matter that it is centred at x 0 rather than �). Hence

I = −(2a 2 �π)1�2 e−ax 0 �4 (x 0 �2)(π�a)1�2 = −(2a)1�2 (x 0 �2)e−ax 0 �4

2 2

�e Franck–Condon factor is I 2 = (ax 02 �2)e−ax 0 �2 . As expected, this factor is

2

zero when x 0 = 0 as then the two wavefunctions align and have zero overlap on
account of one being even and one being odd. By taking the derivative of I 2 with
respect to x 0 it is easily shown that the Franck–Condon factor is a maximum
at x 0 = ±(2�a)1�2 .

E��F.�(b) �e Franck–Condon factor is given by [��F.�–���] and involves the square of

integral of the product of the two wavefunctions. �e region over which both
wavefunctions are non-zero is from L�2 to L: this is the domain of integration
L
I = (2�L) � sin(πx�L) sin(π[x − L�2]�L) dx
L�2

Note that sin(π[x − L�2]�L) = sin(πx�L − π�2) = − cos(πx�L), this gives a

useful simpli�cation
L
I = −(2�L) � sin(πx�L) cos(πx�L) dx
L�2
 Next de�ne θ = πx�L so that the limits are θ = π�2 to θ = π, and dx = (L�π)dθ
π
= −(2�L)(L�π) � sin θ cos θ dθ
π�2

�e integral is evaluated by noting that d�dθ(sin2 θ) = 2 sin θ cos θ

= −(2�L)(L�π) 12 �sin2 θ�π�2 = −(2�L)(L�π) 12 (0 − 1) = 1�π

π

�e Franck–Condon factor is I 2 = 1�π 2 ; numerically this is �.���.

E��F.�(b) �e wavenumbers of the lines in the R branch are given in [��F.�–���], ν̃ R (J) =
ν̃ + (B̃′ + B̃)(J + 1) + (B̃′ − B̃)(J + 1)2 . �e band head is located by �nding
the value of J which gives the largest wavenumber, which can be inferred by
solving dν̃ R (J)�dJ = 0.
d
�ν̃ + (B̃′ + B̃)(J + 1) + (B̃′ − B̃)(J + 1)2 � = (B̃′ + B̃) + 2(J + 1)(B̃′ − B̃)
dJ

Setting the derivative to zero and solving for J gives

−(B̃′ + B̃) B̃ − 3B̃′

J head = − 1 =
2(B̃′ − B̃) 2(B̃′ − B̃)

A band head only occurs in the R branch if B̃′ < B̃.

E��F.�(b) Because B̃′ > B̃ a band head will occur in the P branch.
�e wavenumbers of the lines in the P branch are given in [��F.�–���], ν̃ P (J) =
ν̃ − (B̃′ + B̃)J + (B̃′ − B̃)J 2 . �e band head is located by �nding the value
of J which gives the smallest wavenumber, which can be inferred by solving
dν̃ P (J)�dJ = 0.
d
�ν̃ − (B̃′ + B̃)J + (B̃′ − B̃)J 2 � = −(B̃′ + B̃) + 2J(B̃′ − B̃)
dJ

Setting the derivative to zero and solving for J gives

B̃′ + B̃
J head =
2(B̃′ − B̃)

With the data given

10.470 + 10.308
J head = = 64.1
2(10.470 − 10.308)
Assuming that it is satisfactory simply to round this to the nearest integer the
band head occurs at J = 64 .
E��F.�(b) �e fact that a band head is seen in the P branch implies that B̃′ > B̃. It is shown
in Exercise E��F.�(a) that the band head in the P branch occurs at

B̃′ + B̃
J head = (��.�)
2(B̃′ − B̃)

�is rearranges to
2J + 1
B̃′ = B̃ × (��.�)
2J − 1
A band head at J = 25 might arise from a value of J determined from eqn ��.�
anywhere in the range 24.5 to 25.5, followed by subsequent rounding. Using
these non-integer values of J in eqn ��.� gives B̃′ in the range �.�� cm−1 to
�.�� cm−1 .
�e bond length in the upper state is shorter than that in the lower state (a
shorter bond means a smaller moment of inertia and hence a larger rotational
constant).

E��F.��(b) Assuming that the transition corresponds to that between the two sets of d
orbitals which are split as a result on the interaction with the ligands (Sec-
tion ��F.�(a) on page ���), the energy of the transition is the value of ∆ o . Hence
˜ o = 1�(305 × 10−7 cm) = 3.28 × 104 cm−1 or �.�� eV . �is value is very
∆
approximate as it does not take into account the energy involved in rearranging
the electron spins.

E��F.��(b) A rectangular wavefunction with value h between x = 0 and x = a is normal-

ized if the area under the square of the wavefunction is equal to �: in this case
1 = ah 2 , hence h = a−1�2 . For the wavefunction which is non-zero between
x = ca and x = a the height is likewise h′ = [a(1 − c)]−1�2 . �e region where
the wavefunctions are both non-zero is x = ca to x = a (because c < 1); this is
the domain of integration. �e transition moment is

1�2
a 1 a
� ψ i xψ f dx = � � � x dx
ca a × a(1 − c) ca
1�2 1�2
1 1
=� � � 12 x 2 �c a = � � (a 2 − c2 a2 )
a 1
a (1 − c)
2 a (1 − c)
2 2

1 − c2 a
=
(1 − c)1�2 2

For c � 1 it is possible to approximate 1 − c 2 ≈ 1 and (1 − c)−1�2 ≈ 1 + c�2. �e

transition moment is then given by (1 + c�2)(a�2). �e moment is a�2 when
c = 0, that is when the two wavefunctions are the same; for small c the moment
increases linearly with c.
 As c approaches � the evaluation of the transition moment is made easier by the
following manipulations

1 − c2 (1 − c 2 )(1 + c)1�2 (1 − c 2 )(1 + c)1�2 (1 − c 2 )(1 + c)1�2

= = =
(1 − c)1�2 (1 − c)1�2 (1 + c)1�2 [(1 − c)(1 + c)]1�2 (1 − c 2 )1�2
= (1 − c 2 )1�2 (1 + c)1�2 = (1 − c)1�2 (1 + c)1�2 (1 + c)1�2 = (1 − c)1�2 (1 + c)

In the limit that c = 1 this term, and hence the transition moment, goes to zero.
�e value of c for which the moment is a maximum is found by di�erentiation
d
(1 − c)1�2 (1 + c) = − 12 (1 − c)−1�2 (1 + c) + (1 − c)1�2
dc

setting the derivative to zero and multiplying by (1 − c)1�2 gives

0 = − 12 (1 + c) + (1 − c) hence c= 1
3

�e maximum transition moment occurs at c = 13 , and has the value (8�27)1�2 a

≈ 0.54 a.

E��F.��(b) �e Gaussian functions are written e−α x �2 , where the parameter α determines
2

the width. To evaluate the normalizing factor for the function e−α x �2 requires
2

the integral
+∞
� e−α x dx
2

−∞

which is of the form of Integral G.� with k = α and evaluates to (π�α)1�2 . �e

normalizing factor is therefore N = (α�π)1�4 . �e other Gaussian has half
the width of the �rst, so is of the form e−4α x �2 , and the normalizing factor is
2

N ′ = (4α�π)1�4 .
�e transition moment is given by the integral
+∞
I = (2α�π)1�2 � xe−α x �2 −4α x 2 �2
2
e dx
−∞
+∞
= (2α�π)1�2 � xe−5α x �2
2
dx
−∞

�e integrand is odd and the integral is over a symmetric interval, therefore the
integral, and hence the transition moment is zero .

E��F.��(b) �e absorption at ��� nm is likely to be due to an π∗ ← n transition. �e

wavelength is typical for such transitions, and they are weak because they are
symmetry forbidden.
�e absorption at ��� nm is likely to be due to a π∗ ← π transition. Of the two
transitions it is the stronger and it is at a somewhat longer wavelength than for
an isolated π bond as a result of the conjugation with the carbonyl π bond.
P��F.� �e relevant selection rules are ∆S = 0, ∆Λ = 0, ±1, + ↔ +, − ↔ −, u ↔ g.

�e ground state has S = 12 , Λ = 0, + symmetry, and has parity u (that is, it

is odd with respect to inversion). Transitions to other doublet states with Λ =
0 or 1, with + symmetry (where relevant), and parity g are allowed, therefore.
�us the allowed transitions are to 2 Σ+g and to 2 Π g .

P��F.� �e dissociation energy of the upper state is found using a Birge–Sponer extrap-
olation (Section ��C.�(b) on page ���). Figure ��.�� shows that the di�erence
between two successive lines of the progression from υ = 0 corresponds to the
quantity ∆G̃ υ′ +1�2 identi�ed in Fig. ��C.� on page ���:

∆G̃ υ′ +1�2 = ν̃ 0,υ′ +1 − ν̃ 0,υ′

Having found these values of ∆G̃ υ′ +1�2 they are plotted against υ′ + 12 and the
line extrapolated until it intersects the horizontal axis, as in Fig. ��C.� on page
���. �e enclosed area is D̃ ′0 , the dissociation energy of the upper state. �e
data are given in the following table and the Birge–Sponer plot is shown in
Fig. ��.��.

D̃′0
(υ′ +1) ∆ Ẽ at
υ′
υ =0
′

ν̃ 0,υ′
ν̃ 0,υ′ +1
ν̃ 0,0 D̃ 0

υ=0
 υ′ ν̃ 0,υ′ �cm−1 ∆G̃ υ′ +1�2 �cm−1 υ′ + 1�2
0 50 062.6 662.8 0.5
1 50 725.4 643.6 1.5
2 51 369.0 619.6 2.5
3 51 988.6 590.4 3.5
4 52 579.0 564.4 4.5
5 53 143.4 536.2 5.5
6 53 679.6 497.4 6.5
7 54 177.0 464.8 7.5
8 54 641.8 436.4 8.5
9 55 078.2 381.8 9.5
10 55 460.0 343.1 10.5
11 55 803.1 304.2 11.5
12 56 107.3 253.0 12.5
13 56 360.3 209.7 13.5
14 56 570.0

600
∆G̃ υ′ +1�2 �cm−1

400

200

0
0 5 10 15
υ + 1�2
′

�e data are a good �t to the quadratic

∆G̃ υ′ +1�2 �cm−1 = −1.1247 × (υ + 1�2)2 − 19.423 × (υ + 1�2) + 674.16

�e extrapolation is shown by the dotted curve, and by setting the above quadratic
to zero it is found that the intersection with the horizontal axis is at (υ′ +1�2) =
17.33. �e area under the curve, D̃ ′0 , is found from the integral
17.33
D̃ ′0 = � [−1.1247 × (υ + 1�2)2 − 19.423 × (υ + 1�2) + 674.16] d(υ + 1�2)
0

which evaluates to D̃ ′0 = 6815 cm−1 = 0.8450 eV .

 Figure ��.�� also shows the relationship between the dissociation energy of the
ground electronic state, that of the excited electronic state, the energy di�erence
∆ Ẽ at between the atomic states into which the two electronic states dissociate,
and the energy of the ν̃ 0,0 transition. It follows from the diagram that

D̃ 0 + ∆ Ẽ at = ν̃ 0,0 + D̃′0
hence D̃ 0 = ν̃ 0,0 + D̃′0 − ∆ Ẽ at
= (50 062.6 cm−1 ) + (6815 cm−1 )
1 cm−1
− (190 × 103 J mol−1 )×
(1.9864 × 10−23 J)×(6.0221 × 1023 mol−1 )
= 4.10 × 104 cm−1 = 5.08 eV

where the conversion factor between cm−1 and J from inside the front cover is
used.

P��F.� (a) �e photoelectron spectrum involves a transition from the ground state
of the molecule to an electronic state of the molecular ion. �e energy
needed for the transition is measured indirectly by measuring the energy
of the ejected electron, but in all other respects the spectrum is interpreted
in the same way as electronic absorption spectra.
A spacing of �.�� eV corresponds to (0.41 eV) × (8065.5 cm−1 )�(1 eV) =
3307 cm−1 . �is is comparable to the vibrational frequency of the sym-
metric stretch in neutral H� O, so the observed spacing in the band can be
associated with a vibrational progression involving transitions to excited
states of this normal mode. �at such transitions are observed implies
that they have favourable Franck–Condon factors, and this means that
the equilibrium geometry of the ion must be di�erent from that of the
molecule. In particular it implies that the change in geometry is at least
in part similar to the change in geometry associated with the symmetric
stretch. From this it is possible to infer that the electron which has been
ionized is responsible for bonding along the direction of the symmetric
stretch – presumably O–H σ-type bonding. (In fact only a modest vibra-
tional progression is seen for this band, indicating that the electron which
is ionized has only a small e�ect on the bonding).
(b) A spacing of �.��� eV corresponds to (0.125 eV)×(8065.5 cm−1 )�(1 eV) =
1008 cm−1 . �is is roughly comparable to the vibrational frequency of the
bending mode in neutral H� O, so the observed spacing in the band can be
associated with a vibrational progression involving transitions to excited
states of this normal mode. In contrast to (a), for this band there is a long
vibrational progression which implies that the geometry of the ion must
be signi�cantly di�erent to that of the neutral molecule. Furthermore,
this change must involve a change in the equilibrium bond angle as this is
the change in geometry associated with the bending mode. �e implica-
tion is that the electron which is ionized is a bonding electron, and from
an orbital which has a strong in�uence on the bond angle.
 �e fact that the vibrational frequency is lower in the ion than in the
neutral molecule is a result of the removal of a bonding electron: the ion
is less tightly held, and so has lower vibrational frequencies.

P��F.� �e energy levels of a particle in a one-dimensional box are E n = n 2 ħ 2 π 2 �2mL 2 .

�e linear triene has � π electrons which will occupy levels �, � and � (pairwise),
so the HOMO–LUMO transition is from n = 3 to n = 4. If the average C–C
bond length is taken as d, then the triene is modelled as a box of length L = 5d.
�e transition energy is therefore

(42 − 32 )ħ 2 π 2 7ħ 2 π 2
∆E lin = E 4 − E 3 = =
2m e (5d) 2 50m e d 2

�e energy levels of a particle on a ring of radius R are given by [�F.�–���],

E m = m 2 ħ 2 �2mR 2 , where m = 0, ±1, ±2 . . .. �e cyclic triene has � π electrons
which will occupy levels �, ±1 (pairwise), so the HOMO–LUMO transition is
from m = 1 to m = 2. If the average C–C bond length is taken as d, then the
radius of the circle into which a hexagon with this side can be inscribed is also
d. �e transition energy is therefore

(22 − 12 )ħ 2 3ħ 2
∆E cyc = E 2 − E 1 = =
2m e d 2 2m e d 2

�e ratio between the transition energies is

∆E cyc 3ħ 2 50m e d 2 75
= × = 2 ≈ 1.09
∆E lin 2m e d 2 7ħ π
2 2 7π
On going from the linear to the cyclic polyene the energy gap therefore increases .

P��F.�� Tryptophan (Trp) and tyrosine (Tyr) show the characteristic absorption of a
phenyl group at about ��� nm. Cysteine (Cys) and glycine (Gly) lack the phenyl
group, as is evident from their spectra.

P��F.�� (a) �e ground state of O� is a spin triplet, with S mol = 1. An oxygen atom
has the con�guration ... 2p4 , which means that two of the electrons must
be paired up in a single p orbital, but that the other two can be arranged
to have parallel spins, S = 1, or paired spins S = 0.
According to the Clebsch–Gordon series, [�C.�–���], combining S atom,1 =
1 with S atom,2 = 1 gives an overall spin of 2, 1, 0. �us, the two oxy-
gen atoms could both have S = 1 and combine to give S mol = 1 for the
molecule.
Similarly, combining S atom,1 = 1 with S atom,2 = 0 gives an overall spin of 1
only. �us, one of the oxygen atoms could have S = 1 and one could have
S = 0, and give S mol = 1 for the molecule.
�e molecule could dissociate into atoms which are a singlet and a triplet
or into two triplets .
 (b) �e ground state of N� is a spin singlet, with S mol = 0. A nitrogen atom
has the con�guration ... 2p3 ; these electrons can be con�gured to give a
total spin of S = 32 or S = 12 .
According to the Clebsch–Gordon series, [�C.�–���], combining S atom,1 =
3
2
with S atom,2 = 32 gives an overall spin of 3, 2, 1, 0. �us, the two
nitrogen atoms could both have S = 32 and combine to give S mol = 0
for the molecule.
Similarly, combining S atom,1 = 12 with S atom,2 = 12 gives an overall spin
of 1, 0 . �us, the two nitrogen atoms could both have S = 12 . However,
combining S atom,1 = 12 with S atom,2 = 32 gives an overall spin of 2, 1, but
not zero.
�e molecule could dissociate into atoms which are two quartets or into
a two doublets .

D��G.� �e characteristics of �uorescence which are consistent with the accepted mech-
anism are: (�) it ceases as soon as the source of illumination is removed; (�)
the time scale of �uorescence, 10−9 s, is typical of a process in which the rate
determining step is a spontaneous radiative transition between states of the
same multiplicity; (�) it occurs at longer wavelength (lower frequency) than
the exciting radiation; (�) its vibrational structure is characteristic of that of a
transition from the ground vibrational level of the excited electronic state to the
vibrational levels of the ground electronic state; and (�) the observed shi�ing,
and in some instances quenching, of the �uorescence spectrum by interactions
with the solvent.

D��G.� Referring to Fig. ��G.� on page ��� it is seen that the point at which predisso-
ciation starts (and the spectrum becomes blurred) is at the energy at which the
dissociative electronic state crosses the bound electronic state. �e observation
of the wavenumber of this point gives the energy separation between the lower
electronic state and this crossing point.

E��G.�(b) Naphthalene does not absorb at ��� nm, but benzophenone does (as stated in
Exercise E��G.�(a)). Presumably in the solid solution there are interactions be-
tween the benzophenone and naphthalene molecules which allow the transfer
of energy from electronically excited benzophenone to naphthalene. �e latter
then emits photons as it returns to its ground state: this is the phosphorescent
transition.
E��G.�(b) �is observed increase in the linewidth is a result of predissociation, as il-
lustrated in Fig. ��G.� on page ���. Where the dissociative 1 Σ+u state crosses
the bound upper electronic state the possibility exists that molecules in the
upper electronic state will undergo radiationless transitions to the dissociative
state leading to subsequent dissociation. �is process reduces the lifetime of
the excited states and so increases the linewidth of the associated transitions
(lifetime broadening, see Section ��A.�(b) on page ���).

P��G.� (a) �e Beer–Lambert law is [��A.�–���], I = I 0 10−ε[J]L . It follows that

I abs (ν̃) = I 0 (ν̃) − I(ν̃)

= I 0 (ν̃) − I 0 (ν̃)10−ε(ν̃)[J]L = I 0 (ν̃)[1 − 10−ε(ν̃)[J]L ]

(b) �e problem states that the intensity of �uorescence I(ν̃ f ) is proportional

to � f and I abs (ν̃), hence

I(ν̃ f ) ∝ � f I 0 (ν̃) �1 − 10−ε(ν̃)[J]L �

For weak absorbance, ε(ν̃)[J]L � 1, the expansion 10−x ≈ 1 − x ln(10) is

used to give

I(ν̃ f ) ∝ � f I 0 (ν̃) {1 − 1 + ln(10)ε(ν̃)[J]L}

∝ � f I 0 (ν̃)ε(ν̃)[J]L

which is the required result

P��G.� (a) �e coherence length is given by l C = λ 2 �2∆λ. With the data given

(633 × 10−9 m)2

lC = = �.�� m
2 × 2.0 × 10−12 m
�is is very much larger than the coherence length for a light bulb.
(b) In the limit that ∆λ → 0 the coherence length becomes in�nite.

P��G.� Each photon with wavelength λ has energy hc�λ, therefore N such photons
have energy N hc�λ. If the laser delivers a power P for time t, the energy is
Pt. Equating these two expressions gives Pt = N hc�λ and hence t = N hc�λP.
With the data given

106 × (6.6261 × 10−34 J s) × (2.9979 × 108 m s−1 )

t= = �.�� ns
(488 × 10−9 m) × (1.0 × 10−3 W)
 R�2
d
R

R�2

I��.� (a) �e geometry of the molecule is illustrated in Fig. ��.��.

�e moment of inertia about the axis parallel to the symmetry axis, that
is the axis passing through the middle of the molecule and perpendicular
to the plane of the molecule, is given by

I�� = � m i r 2i = 3m H d 2
i

where r i is the perpendicular distance from the√axis to mass m i . From

√
the diagram is follows that (R�2)�d = cos 30○ = 3�2, hence d = R� 3
√
I�� = 3m H (R� 3)2 = m H R 2

�e moment of inertia perpendicular to the symmetry axis is indepen-

dent of where this axis is located provided it passes through the centre of
the molecule and lies in the plane of the molecule: one such convenient
choice is the dashed line shown in the �gure.

I� = 2m H (R�2)2 = 1
m R2
2 H

As expected, I�� = 2I� .

(b) �e moment of inertia is related to the rotational constant through [��B.�–
���], B̃ = ħ�4πcI� ; note that the rotational constant B̃ is always associated
with the moment of inertia perpendicular to the symmetry axis. It follows
that I� = ħ�4πc B̃ and hence, using the result above, 12 m H R 2 = ħ�4πc B̃.
�is rearranges to give the following expression for R
1�2
ħ
R=� �
2πm H c B̃
1.0546 × 10−34 J s
1�2
=� �
2π(1.67... × 10 kg) × (2.9979 × 1010 cm s−1 ) × (43.55 cm−1 )
−27

= ��.�� pm
 where the mass in kg is given by (1.0079 m u )×(1.6605×10−27 kg)�(1 m u )
= 1.67... × 10−27 kg. An alternative value for R is found from the other
rotational constant. Here C̃ = ħ�4πcI�� and hence m H R 2 = ħ�4πc C̃.
1�2
ħ
R=� �
4πm H c C̃
1.0546 × 10−34 J s
1�2
=� �
4π(1.67... × 10 kg) × (2.9979 × 1010 cm s−1 ) × (20.71 cm−1 )
−27

= ��.�� pm

(c) With the given value of R, the rotational constant is computed from B̃ =
ħ�4πcI� = ħ�2πm H cR 2
1.0546 × 10−34 J s
B̃ =
2π(1.67... × 10−27 kg) × (2.9979 × 1010 cm s−1 ) × (87.32 × 10−12 m)2
= ��.�� cm−1

�e other rotational constant is just half of this, C̃ = 21.94 cm−1

−1�2
(d) For a harmonic oscillator the vibrational frequency goes as m eff , where
m eff is the e�ective mass. �e value of the e�ective mass depends on the
vibration in question, but in this case as all the atoms are the same it is
reasonable to assume that the e�ective mass of H� + will be proportional
to m H , and that of D� + will be proportional to m D . It therefore follows
that
m H 1�2
ν̃ D = ν̃ H � �
mD
1.0079 1�2
= (2521.6 cm−1 ) × � � = ����.� cm−1
2.0140
�e rotational constants are inversely proportional to the moment of in-
ertia, and for this molecule all the atoms are the same so the rotational
constant goes as m−1 .
mH
B̃ D = B̃ H
mD
1.0079
= (43.55 cm−1 ) × = ��.�� cm−1
2.0140
A similar calculation gives C̃ D = 10.36 cm−1 .

−1�2
I��.� (a) For a harmonic oscillator the vibrational frequency goes as m eff , where
m eff is the e�ective mass; for a diatomic the e�ective mass is simply 12 m.
It therefore follows that
m16 O 1�2
ν̃ 18O2 = ν̃ 16O2 � �
m18 O
15.9949 1�2
= (844 cm−1 ) × � � = ��� cm−1
17.9992
 (b) �e bond order of O� is �, and to form the anions electrons are added
to the anti-bonding π g molecular orbital, thereby decreasing the bond
order to �.� for O� – and � for O� � – . �e steady decrease in the bond order
is matched by the steady decrease in the vibrational frequency. �ere is
thus a correlation between bond strength and vibrational frequency, as
expected.
(c) �e observed vibrational frequency of O� bound to haemerythrin most
closely matches that for O� � – , so of the alternatives o�ered Fe�+
� O�
�–

seems the most likely.

(d) �e observation of two bands attributable to O–O stretching implies that
the O� is bound is such a way that the two oxygen atoms are no longer
equivalent. If this is the case, when the isotopologue ��O ��O is used,
two di�erent frequencies will result because the two ends of the oxygen
molecule are now distinguished. �is eliminates structures � and �.

I��.� Expressed in terms of the absorbance A the Beer–Lambert law is given by [��A.�c–
���], A = ε[J]L. To convert the given absorbance into a molar absorption
coe�cient requires [J] in mol dm−3 , which is computed using the perfect gas
law, pV = nRT, rearranged to n�V = p�RT. Assuming that the quoted com-
position of CO� , ‘�.� per cent’, refers to a mole per cent, x CO2 = 0.021, so
p CO2 = 0.021×(1.00 bar) = 0.021 bar. In the calculation of n�V it is convenient
to use R = 8.3145 × 10−2 dm3 bar K−1 mol−1
n p 0.021 bar
= =
V RT (8.3145 × 10−2 dm3 bar K−1 mol−1 ) × (298 K)
= 8.47... × 10−4 mol dm−3

�e given expression for A(ν̃) is therefore converted to an expression for the

molar absorption coe�cient using

ε(ν̃) = A(ν̃)�[J]L = A(ν̃)�[(8.47... × 10−4 mol dm−3 ) × (10 cm)]

= (1.17... × 102 mol−1 dm3 cm−1 ) × A(ν̃)

(a) Graphs of A(ν̃) and ε(ν̃) are shown in Fig. ��.��. �is band is likely to be
due to the fundamental transition of the antisymmetric stretching normal
mode of CO� , which has ν̃ 2 = 2349 cm−1 . �e broad features are the
unresolved P and R branches; no Q branch is expected for this mode. �e
principal contribution to the linewidth of an infrared transition is likely
to be pressure broadening.
(b) Expressions for the wavenumbers of the lines in the P and R branches are
given in [��C.��a–���] and [��C.��c–���]

ν̃ P (J) = ν̃ − 2B̃J ν̃ R (J) = ν̃ + 2B̃(J + 1)

Here ν̃ = 2349 cm−1 . As described in Section ��B.� on page ���, because

��
O is a boson, only even rotational states are occupied (and, in fact, odd
rotational states in the �rst excited vibrational state of the anti-symmetric
 ε(ν̃)�mol−1 dm3 cm−1
2.0
1.5 200

A(ν̃)
1.0
100
0.5
0.0 0
2 300 2 350 2 400 2 300 2 350 2 400
−1 −1
ν̃�cm ν̃�cm

stretch), so in the above expression J takes the values 0, 2, 4 . . .. �e

rotational constant is computed from [��B.�–���], B̃ = ħ�4πcI, where
I = 2m O R 2 . With the data given

I = 2 × (15.9949 m u )×(1.6605 × 10−27 kg)×(116.2 × 10−12 m)2 �(1 m u )

= 7.17... × 10−46 kg m2
1.0546 × 10−34 J s
B̃ = = 0.3903 cm−1
4π×(2.9979 × 1010 cm s−1 ) × (7.17... × 10−46 kg m2 )
�e intensity of the transition from level J is proportional to the popula-
tion of that level, taking into account the degeneracy

intensity ∝ (2J + 1)e−hc B̃�k T

Using these expressions the positions and intensities of the lines in the P
and R branches are computed and a synthetic spectrum constructed by
assuming a linewidth and lineshape (here arbitrarily taken as a Gaussian).
Two such spectra are shown in Fig. ��.��: in (a) the linewidth has been
chosen so that the lines are well resolved; in (b) a much wider line is used
so that the lines in the P and R branches merge into a broad contour. �e
spectrum in (b) is roughly similar to that in Fig. ��.��, but the asymmetry
between the two branches is not reproduced by the calculation.

(a) (b)

2300 2320 2340 2360 2380 2400 2300 2320 2340 2360 2380 2400
~ ~
v / cm−1 v / cm−1

(c) �e transmittance T is de�ned as I�I 0 and hence from the Beer–Lambert

law [��A.�–���], T = e−ε[J]L ; it follows that log T = −A. �e concentration
 of CO� is computed as in (a) using [CO2 ] = x CO2 p atm �RT; both the
atmospheric pressure and temperature vary with the height, and therefore
so will the concentration. �e pressure varies with height according to
p(h) = p 0 e−h�H , where the scale height H is about ���� m. �e total
absorbance up to height h 0 is therefore given by integral
h0 h0 x CO2 p
A=� ε[CO2 ] dh = ε � dh
0 0 RT
h0 x CO2 p 0 e−h�H
= ε� dh
0 R(288 − 0.0065h)
h0 e−h�H
= εx CO2 p 0 � dh
0 R(288 − 0.0065h)

where h is in m.

�is integral cannot be solved by hand, but some work with mathematical
so�ware and a typical value of ε shows that the absorbance exceeds � by
the time h 0 = 30 m. Over such a small height it is safe to assume that the
pressure and temperature are constant, in which case the calculation of
the absorbance is much simpler
x CO2 p
A = ε[CO2 ]h 0 = ε h0
RT
= [ε�(mol−1 dm3 cm−1 )]
(3.3 × 10−4 ) × (1 bar)
× × (h 0 �cm)
(8.3145 × 10−2 dm3 bar K−1 mol−1 ) × (288 K)
= (1.378 × 10−5 ) × [ε�(mol−1 dm3 cm−1 )] × (h 0 �cm)

�e transmittance is T = 10−A .
Figure ��.�� shows plots of the transmittance as a function of height for
some representative values of the molar absorption coe�cient. For the
maximum value of ε seen in this absorption band (refer to Fig. ��.��) the
transmittance drops to �.� a�er less than � m. For a value of ε more typical
of the average (say ε = 100 mol−1 dm3 cm−1 ), the transmission drops to
�.� a�er about �.� m. Even for values of ε typical of the extremities of
the band, the transmission has fallen to �.� within �� m or so. A surface
plot of the transmission as a function of both wavenumber and height is
shown in Fig. ��.��.

I��.� �e electronic ground state of a closed-shell molecule transforms as the totally

symmetric irreducible representation. �is is because all of the orbitals are
doubly occupied by spin paired electrons. �e overall symmetry of a �lled
orbital is found from the direct product Γ(i) × Γ(i) , where Γ(i) is the irreducible
representation as which the orbital transforms. When multiplied out, such a
 1.0
ε = 200 mol−1 dm3 cm−1
0.8 ε = 100
ε = 50
0.6 ε = 25

T
0.4

0.2

0.0
0 5 10 15 20 25 30
h 0 �m

~
v /cm−1

h0 /m

product always includes the totally symmetric irreducible representation and it

is this symmetry species which needs to be combined with the anti-symmetric
spin function for two spin-paired electrons.

(a) Ethene belongs to the point group D 2h : assume that the molecule lies
in the x y-plane, with the C–C bond along x. �e π bonding molecular
orbital transforms in the same way as the cartesian function z, that is as
B1u . �e π∗ anti-bonding molecular orbital transforms in the same way
as the cartesian function xz, that is as B2g . �e excited state (π)1 (π∗ )1
therefore has symmetry B1u × B2g = B3u (the direct product is found by
multiplying together the characters of the two irreducible representations,
as described in Section ��C.�(a) on page ���).
 �e transition moment is given by ∫ ψ f ∗ µ̂ψ i dτ, and the symmetry species
of the integrand is found using the direct product; µ̂ transforms as x, y, or
z, which in this case is B3u , B2u , or B1u . �e integral is only non-zero if the
integrand transforms as the totally symmetric irreducible representation,
which is the case here when the component of the dipole is along x

� � �
ψf µ̂ x ψi

B3u × B3u × Ag = Ag

�us the π → π∗ transition is symmetry allowed , with the transition

dipole along x .
(b) A carbonyl group (as exempli�ed by that in methanal) is assumed to be-
long to the point group C 2v : assume that the H� CO fragment lies in the
xz-plane, with the C–O bond along z. �e π∗ anti-bonding molecular
orbital transforms in the same way as the cartesian function y, that is as
B2 .
A non-bonding electron on oxygen is usually considered to be in a �px
orbital which transforms as B1 . When an electron is promoted from n to
π∗ , the excited state has symmetry B2 × B1 = A2 . �e symmetry of the
integrand for the transition moment is

� � �
ψf µ̂ ψi

A2 × Γx , y,z × A1 = A2 × Γx , y,z

Because Γx , y,z ≠ A2 this product is never A1 , so the integral is zero and

the transition is forbidden .

I��.�� �e energy of the HOMO, E HOMO , is reported in the table below, based on
calculations performed with Spartan �� using the DFT/B�LYP/�-��G* method.
�e experimentally determined energy of the I� –aromatic hydrocarbon charge
transfer bands is also given.
Figure ��.�� shows a plot of E HOMO against hν max ; the best-�t straight line is
also shown. �ere is a modest correlation between the two quantities.

hydrocarbon hν max /eV E HOMO �eV

benzene �.��� −6.70
biphenyl �.��� −5.91
naphthalene �.��� −5.78
phenanthrene �.��� −5.73
pyrene �.��� −5.33
anthracene �.��� −5.23
 −5.5
E HOMO �eV

−6.0

−6.5

2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2

hν max �eV
D��A.� �e energy levels associated with the interaction between magnetic nuclei and
an applied magnetic �eld scale directly with the �eld, with the constant of
proportion depending on the identity of the nucleus. �e interaction between
an electron and an applied magnetic �eld behaves in the same way, but the
interaction is much greater, by a factor of the order of ����.

E��A.�(b) �e nuclear g-factor g I is given by [��A.�c–���], g I = γ N ħ�µ N , where µ N is the

nuclear magneton (5.051 × 10−27 J T−1 ) and γ N is the nuclear magnetogyric
ratio, the value of which depends on the identity of the nucleus. �e units of ħ
are J s and g I is a dimensionless number, so the nuclear magnetogyric ratio γ N
has units (J T−1 )�(J s) = T−1 s−1 .
In SI units, � T = � kg s−2 A−1 hence γ N has units (kg s−2 A−1 )−1 × (s−1 ) =
A s kg−1 .

E��A.�(b) �e magnitude of the angular momentum is given by [I(I + 1)]1�2 ħ where

I is the nuclear spin quantum number. For a 14 N nucleus, I = 1, hence the
√
magnitude of the angular momentum is [1(1 + 1)]1�2 ħ = 2ħ .
�e component of the angular momentum along the z-axis is m I ħ where m I =
I, I−1, ..., −I. For a 14 N nucleus, the components along the z-axis are 0, ±ħ and
the angle between angular momentum vector and the z-axis takes the values

±ħ
θ = 0, ± cos−1 � √ � = 0, ±0.7854 rad (or 0○ , ±45.00○ )
2ħ

E��A.�(b) �e NMR frequency is equal to the Larmor precession frequency, ν L , which

is given by [��A.�–���], ν L = γ N B0 �2π, where B0 is the magnitude of the
magnetic �eld and γ N is the nuclear magnetogyric ratio. Use Table ��A.� on
page ��� in the Resource section for the value of γ N . Hence,

γ N B0 (25.177 × 107 T−1 s−1 ) × (17.1 T)

νL = = = 6.85 × 108 Hz = 685 MHz
2π 2π
E��A.�(b) �e energies of the nuclear spin states in a magnetic �eld are given by [��A.�d–
���], E m I = −g I µ N B0 m I where g I is the nuclear g-factor, µ N is the nuclear
magneton, B0 is the magnitude of the magnetic �eld, and the component of
the angular momentum on a speci�ed axis is m I ħ where m I = I, I − 1, ..., −I.
�erefore, since the possible values of m I are 0, ±1, the energies of nuclear spin
states are

E m I = −g I µ N B0 m I
= −(0.404) × (5.0508 × 10−27 J T−1 ) × (10.50 T) × m I
= (−2.14... × 10−26 J) × m I

Hence E 0 = 0 and E±1 = ∓2.14 × 10−26 J .

E��A.�(b) �e energy level separation is ∆E = hν where ν = γ N B0 �2π, [��A.�–���].

Hence, in megahertz, the frequency separation is

γ N B0 (1.93 × 107 T−1 s−1 ) × (14.4 T)

ν = 10−6 × = 10−6 × = 44.2 MHz
2π 2π

E��A.�(b) For nuclei the energy level separation is ∆E = hν where ν = γ N B0 �2π, [��A.�–
���]. For the same magnetic �eld the Larmor frequencies, and hence the energy
separations, of the two nuclei are in the ratio of their magnetogyric ratios

ν14 N ∆E(14 N) γ N (14 N)

= =
ν1 H ∆E(1 H) γ N (1 H)
hence
γ N (14 N) γ N (14 N)
∆E(14 N) = ∆E(1 H) × = hν 1H ×
γ N (1 H) γ N (1 H)
With the values given

(1.93 × 107 T−1 s−1 )

∆E(14 N) = (6.6261 × 10−34 J s) × (600 × 106 Hz) ×
(26.75 × 107 T−1 s−1 )
= 2.87 × 10−26 J

�e energies of the electron spin states in a magnetic �eld are given by [��A.��c–
���], E m s = g e µ B B0 m s where g e = 2.0023 is the g-value of the free electron, B0
is the magnitude of the magnetic �eld, m s = ± 12 , and µ B is the Bohr magneton.
�e energy separation is therefore

∆E = E+1�2 − E−1�2 = ( 12 g e µ B B0 ) − (− 12 g e µ B B0 ) = g e µ B B0
= (2.0023) × (9.2740 × 10−24 J T−1 ) × (0.300 T)
= 5.57 × 10−24 J

Hence the energy level separation of the electron is much greater than that of
the ��N nucleus under the conditions given.
E��A.�(b) �e ground state has m I = + 12 (α spin) and population N α , and the upper
state has m I = − 12 (β spin) and population N β . �e total population N is N =
N α + N β , and the population di�erence is N α − N β . �e Boltzmann distribution
gives N β �N α = e−∆E�k T , where ∆E is the energy di�erence between the two
states: ∆E = γ N ħB0 . It follows that N β = N α e−∆E�k T . With these results

N α − N β N α − N β N α (1 − e−∆E�k T ) 1 − e−∆E�k T
= = =
N N α + N β N α (1 + e−∆E�k T ) 1 + e−∆E�k T

Because ∆E � kT the exponential e−∆E�k T is approximated as 1 − ∆E�kT to

give

N α − N β 1 − (1 − ∆E�kT) ∆E�kT ∆E γ N ħB0

≈ = = =
N 1 + (1 − ∆E�kT) 2 + ∆E�kT 2kT 2kT

For a 13 C nucleus and at ��� K

N α − N β γ N ħB0 (6.73 × 107 T−1 s−1 ) × (1.0546 × 10−34 J s) × B0
= =
N 2kT 2 × (1.3806 × 10−23 J K−1 ) × (298 K)
= 3.42... × 10−6 × (B0 �T)

For B0 = 0.50 T, (N α − N β )�N = 4.3 × 10−7 ; for B0 = 2.5 T, the ratio is

2.2 × 10−6 ; for B0 = 15.5 T, the ratio is 1.34 × 10−5 .

E��A.�(b) �e population di�erence for a collection of N spin- 12 nuclei is given by [��A.�b–

���], (N α − N β ) ≈ Nγ N ħB0 �2kT, where N α is the number of spins in the
lower energy state and N β is the number of spins in the higher energy state.
At constant magnetic �eld, (N α − N β )�N ∝ T −1 . Hence, for the relative
population di�erence to be increased by a factor of �, the temperature must
decreased by this same factor – that is the temperature must by multiplied by
factor of �.� .
For many samples this is simply not a feasible way of increasing the sensitivity
as the solvent would freeze long before the temperature had been lowered by
this amount. High-resolution spectra require the sample to remain in a liquid
solution.

E��A.�(b) �e resonance frequency ν NMR in an NMR spectrometer is given by [��A.�–

���], hν NMR = γ N ħB0 , where γ N is the nuclear magnetogyric ratio and B0 is
the magnetic �eld strength. �e EPR resonance frequency ν EPR is given by
[��A.��b–���], hν EPR = g e µ B B0 , where g e is the magnetogyric ratio of the
electron.
�e EPR resonance frequency in a magnetic �eld for which the NMR frequency
for 1 H nuclei is ν NMR is calculated by taking the ratio of the two resonance
conditions, assuming B0 is equal for both systems. Hence,
hν EPR g e µ B B0 ν EPR ge µB
= hence =
hν NMR γ N ħB0 ν NMR γ N ħ
 With the data given
ge µB
ν EPR = ν NMR ×
γN ħ
2.0023 × (9.2740 × 10−24 J T−1 )
= (500 × 106 Hz) ×
(26.75 × 107 T−1 s−1 ) × (1.0546 × 10−34 J s)
= 3.3 × 1011 Hz = 0.33 GHz

P��A.� �e relative sensitivity of NMR spectroscopy R is proportional to I(I + 1)γ N

3
.
1
Relative to that of H, the sensitivity is
I(I + 1)γ N3 3
R(nuclide) γN
S= = = 43 I(I + 1) � �
( 2 )( 2 )γ N ( H) N ( H)
1 3
R(1 H) 3 1 γ 1

Taking account of the natural abundance A of each isotope, the sensitivity ratio
becomes
3
A(nuclide) 4 γN A(nuclide)
S =S×
′
= 3 I(I + 1) � � ×
A(1 H) γ N (1 H) A(1 H)
For ��N, γ N = −2.712 × 107 T−1 s−1 , and the natural abundance is �.���%.

nuclide A�% I S S′
1 1
H ��.���� 2
� �
2
H �.���� � 9.65 × 10 −3
1.51 × 10−6
13
C �.��� 1
2
1.59 × 10−2 1.76 × 10−4
14
N ��.��� � 1.01 × 10−3 1.00 × 10−3
15
N �.��� 1
2
1.04 × 10−3 3.80 × 10−6
11 3
B ��.� 2
�.��� �.���

P��A.� �e NMR signal intensity, I, is proportional to the number of protons in a slice

of width δ z at horizontal distance z from the centre of the disk, as shown in
Fig ��.�. �e number of protons in the slice is proportional to the volume of
the slice, which is proportional to the cross-sectional area of the slice. �is
area is 2r sin θ × δ z , which implies that the intensity is proportional to the
length of the slice and thus ∝ 2r sin θ. Noting that cos θ = z�r it follows
that I ∝ 2 sin [cos−1 (z�r)] . Figure ��.� shows the expected line shape from
the disc; the horizontal axis corresponds to the distance from the centre, but
because of the �eld gradient it is also a frequency axis.

D��B.� �ese are discussed in Section ��B.� on page ���.

 δz

θ
(0, 0) z z

2.0

1.5
Intensity

1.0

0.5

0.0
−1.5 −1.0 −0.5 0.0 0.5 1.0 1.5
z�r

D��B.� �is is discussed in detail in Section ��B.�(d) on page ���. In summary, two
nuclei are chemically equivalent if they are related by a symmetry operation of
the molecule. Such nuclei will have the same resonance frequency, that is, the
same chemical shi�. Examples are the protons in benzene, and H-� and H-� in
�-nitrophenol. In benzene the protons are related by a C 6 operation (as well as
others) and in �-nitrophenol the protons are related by re�ection in a mirror
plane perpendicular to the plane of the ring and passing through C-� and C-�.
Two chemically equivalent nuclei A and A′ are magnetically equivalent if the
coupling between A and any other magnetic nucleus in the molecule, say Z,
is the same as the coupling between A′ and Z. If Z itself is to be magnetically
equivalent to Z′ , then the couplings A–Z, A–Z′ , A′ –Z, and A′ –Z′ must all be
equal: that is, the couplings between any member of a group of equivalent spins
with any member of another group of equivalent spins must be the same in
order for the groups each to be magnetically equivalent.
For example, in PF� , which has a trigonal bi-pyramidal structure, the three
equatorial �uorines are magnetically equivalent, as are the two axial �uorines.
 A second example is �,�,�-trichlorobenzene: H–� and H–� are magnetically
equivalent as they both have the same coupling to H-�. Chemical equivalence
does not imply magnetic equivalence. In the case of �-nitrophenol, protons
H-� and H-�, though chemically equivalent, are not magnetically equivalent
because the coupling of H-� to H-� is di�erent from the coupling of H-� to
H-�.

E��B.�(b) �e δ scale is de�ned by [��B.�a–���], δ = (ν − ν○ ) × 106 �ν○ , where δ is the

chemical shi� of the peak, ν is the resonance frequency of the peak, and ν○ is
the resonance frequency of the standard. Hence

ν − ν○ (125.148750 MHz) − (125.130000 MHz)

δ= × 106 = × 106 = ���
ν ○ (125.130000 MHz)

E��B.�(b) �e δ scale is de�ned by [��B.�a–���], δ = (ν − ν○ ) × 106 �ν○ , where δ is the

chemical shi� of the peak, ν is the resonance frequency of the peak, and ν○ is
the resonance frequency of the standard. Hence

ν − ν○ −1875 Hz
δ= × 106 = × 106 = −14.98
ν○ (125.130000 × 106 Hz)

E��B.�(b) �e resonance frequency ν is given by [��B.�–���], ν = ν○ + (ν spect �106 )δ,

where ν○ is the resonance frequency of the standard. �e frequency separation
of the two peaks, ∆ν, is
ν spect ν spect ν spect
∆ν = ν 2 − ν 1 = [ν○ + � � δ 2 ] − [ν○ + � 6 � δ 1 ] = � 6 � (δ 2 − δ 1 )
10 6 10 10
100.130000 × 106 Hz
=� � (50.0 − 25.5) = 2450 Hz
106

E��B.�(b) �e resonance frequency ν is given by [��B.�–���], ν = ν○ + (ν spect �106 )δ,

where ν○ is the resonance frequency of the standard. �e frequency separation
of the two peaks, ∆ν is
ν spect ν spect ν spect
∆ν = ν 2 − ν 1 = �ν○ + � � δ 2 � − �ν○ + � 6 � δ 1 � = � 6 � (δ 2 − δ 1 )
10 6 10 10

Rearrange to make ∆δ the subject.

106 106
∆δ = δ 2 − δ 1 = ∆ν × � � = (25000 Hz) × = ���
ν spec 200.130000 × 106 Hz
E��B.�(b) �e combination of [��B.�–���], Bloc = B0 + δB, and [��B.�–���], δB = −σB0 ,
gives the relationship Bloc = (1 − σ)B0 . For �σ ○ � << 1, [��B.�–���] gives δ =
(σ ○ − σ) × 106 . Hence,

∆δ = δ 2 −δ 1 = (σ ○ −σ2 )×106 −(σ ○ −σ1 )×106 = −(σ2 −σ1 )×106 = −(∆σ)×106

∆Bloc = (1 − σ2 )B0 − (1 − σ1 )B0 = −(σ2 − σ1 )B0 = −(∆σ)B0

Substituting for ∆σ gives ∆Bloc = (∆δ�106 )B0 .
(i) For B0 = 1.5 T, ∆Bloc = [(3.36 − 1.16)�106 ] × (1.9 T) = 4.2 × 10−6 T =
4.2 µT .
(ii) For B0 = 15 T, ∆Bloc = [(3.36 − 1.16)�106 ] × (16.5 T) = 3.63 × 10−5 T =
36.3 µT .

E��B.�(b) �e resonance frequency ν is given by [��B.�–���], ν = ν○ + (ν spect �106 )δ,

where ν○ is the resonance frequency of the standard. �e resonance from TMS
is taken as the origin so ν○ = 0.
For 1 H nuclei, I = 12 and so the signal due to nucleus A is split into 2nI + 1 =
2×2× 12 +1 = 3 peaks, with a splitting equal to the coupling constant J AX = 5 Hz,
and with intensity ratio �:�:�. Similarly, the signal due to nucleus X is split into
2nI + 1 = 2 × 1 × 12 + 1 = 2 peaks with a splitting equal to the coupling constant
J AX = 5 Hz.
For a spectrometer operating at 500 MHz,

ν spect 500 × 106 Hz

νA = ν○ + � �δ = 0+ × 1.50 = 750 Hz
10 6 106

ν spect 500 × 106 Hz

νX = ν○ + � � δ = 0 + × 4.50 = 2250 Hz
106 106
For the A spin there will be three lines at ��� Hz, ��� Hz, and ��� Hz; for X spin
there will be two lines at ����.� Hz, and ����.� Hz. �e integrated intensity of
the X spin multiplet will be twice that of the A spin multiplet.

νX νA

J AX = 5 Hz
1500 Hz J AX = 5 Hz

ν increasing

��
E��B.�(b) F NMR: the four 19 F nuclei are equivalent and so all have the same shi�. �is
resonance is split by coupling to the single 11 B nucleus into 2nI + 1 lines; here
n = 1 and I = 3�2 so there are � lines of equal intensity. �e splitting between
 each is the B–F coupling constant, and the multiplet is centred at the shi� of
the �uorine.
��
B NMR: the 11 B nucleus is coupled to four equivalent 19 F nuclei, giving a
multiplet with 2nI + 1 lines; here n = 4 and I = 12 so there are � lines. �ese
lines have intensities in the ratio �:�:�:�:�, each line is separated from the next
by the B–F coupling constant, and the whole multiplet is centred at the shi� of
the boron.

E��B.�(b) In ��NH+4 the four �H nuclei are equivalent, and are coupled to a single ��N
nucleus with I = 1. �is splits the resonance into 2nI + 1 = 2 × 1 × 1 + 1 = 3
lines with intensity ratio �:�:�.
In ��NH+4 coupling to a single ��N nucleus with I = 12 splits the resonance into
2nI + 1 = 2 × 1 × 1 + 1 = 2 lines with intensity ratio �:�.

E��B.�(b) Coupling to a nucleus with I = 1 splits the original resonance into 2I + 1 = 3

lines of equal intensity: the lines appear at ν and ν ± J, where J is the coupling
constant. Coupling to a second spin-� nucleus splits each of these three lines
into three in the same way. Because the two spins to which the coupling occurs
are equivalent, the coupling is the same and some of the lines fall on top of one
another, giving enhanced intensity. �e result is a �:�:�:�:� multiplet , as shown
in Fig ��.�.

J AX

ν increasing

E��B.��(b) �e multiplet resulting from coupling to two inequivalent I = 1 nuclei origi-

nates from the resonance of nucleus A being split into (2I + 1) = 3 lines by
coupling with the X1 nucleus, and then each of these lines being split into three
by coupling to the X2 nucleus.
Since the coupling between A and X1 is not the same as that between A and
X2 , no lines are necessarily coincident and so nine lines of equal intensity are
observed, as shown in Fig. ��.�.
 J AX1

J AX2

E��B.��(b) Coupling to one I = 52 nucleus results in the original line being split into (2I +
1) = 6 lines. Each of these lines is then split into six in the same way by coupling
to the second I = 52 nucleus, and then split again by coupling to the third
nucleus.
As a result of each nucleus being equivalent, the splittings are the same and thus
some lines are coincident and give rise to absorption lines of increased inten-
sity. �e overall result is a �:�:�:��:��:��:��:��:��:��:��:��:��:�:�:� multiplet , as
is shown in Fig. ��.�.

J AX

E��B.��(b) A group of nuclei are chemically equivalent if they are related by a symmetry
operation of the molecule and therefore have the same chemical shi�. Two
chemically equivalent nuclei A and A′ are magnetically equivalent if the cou-
pling between A and any other magnetic nucleus in the molecule, say Z, is
the same as the coupling between A′ and Z. If Z itself is to be magnetically
equivalent to Z′ , then the couplings A–Z, A–Z′ , A′ –Z, and A′ –Z′ must all be
equal: that is, the couplings between any member of a group of equivalent spins
with any member of another group of equivalent spins must be the same in
order for the groups each to be magnetically equivalent.
In �,�,�-trichlorobenzene, H4 and H6 are chemically equivalent because they
are related by a 180○ degree rotation about the C2 –C5 axis; H5 is unique. �e
 coupling between H4 and H5 is the same as that between H6 and H5 , there-
fore the test for magnetic equivalence is satis�ed: H4 and H6 are magnetically
equivalent.

Cl

Cl Cl

H6 H4

H5

E��B.��(b) �e molecule SF−5 is square pyramidal. �e four equatorial �uorine atoms, Fe ,

are related by a ��○ rotation about the Fa –S bond: these four atoms are therefore
chemically equivalent. �e axial �uorine atom, Fa , is unique.
Each Fe has the same coupling to Fa , thus satisfying the test for magnetic equiv-
alence: the four equatorial �uorine atoms are magnetically equivalent.

-
Fa

Fe S Fe
Fe Fe

E��B.��(b) Coalescence of two NMR lines due to rapid nuclei exchange occurs when the
condition given in [��B.��–���], τ = 21�2 �πδν, is satis�ed; in this expression τ
is the lifetime of an environment, and δν is the di�erence between the Larmor
frequencies of the two environments. Using [��B.�–���],
νspec νspec νspec
δν = ν 2 − ν 1 = �ν○ + � � δ 2 � − �ν○ + � 6 � δ 1 � = � 6 � (δ 2 − δ 1 )
10 6 10 10
For a proton jumping between two sites with �rst-order rate constant k, k = 1�τ

νspec 350 × 106

δν = � � (δ 2 − δ 1 ) = � � (5.5 − 4.2) = 455 Hz
106 106

1 πδν π × (455 Hz)

k= = = = 1.0 × 103 s−1
τ 21�2 21�2

P��B.� �e 19 F NMR spectrum has two multiplets: a doublet and a quintet. �e former
indicates coupling to one spin- 12 nucleus, the latter indicates coupling to four
equivalent spin- 12 nuclei.
 VSEPR suggest that IF� is square pyramidal. �e four equatorial �uorine atoms
Fe are chemically equivalent as they are related by a ��○ rotation about the I–Fa
axis; the axial �uorine atom Fa is unique. Each Fe has the same coupling to Fa ,
therefore the four equatorial F atoms are magnetically equivalent.
�e Fa atom will therefore appear as a �:�:�:�:� quintet, and the Fe atoms as a
doublet. �e splitting between the lines of the multiplets is the same in both
cases.

Fa

Fe I Fe
Fe Fe

P��B.� �e Karplus equation is given in [��B.��–���], 3 J HH = A + B cos � + C cos 2�.

Figure ��.� illustrates that increasing parameter C reduces the value of 3 J HH in
the range 45○ < � < 135○ . In the ranges � < 45○ and � > 135○ , increasing
parameter C increases the value of 3 J HH , with the greatest in�uence when the
X–H bonds are aligned parallel or anti-parallel (� = 0 or � = 180○ ).

15
C = 3 Hz
C = 5 Hz
C = 6 Hz
10
J HH �Hz

5
3

0
0 30 60 90 120 150 180
��○

Figure ��.� illustrates that making parameter B more positive increases the
value of 3 J HH in the range 0○ < � < 90○ , with the greatest in�uence when the
X–H bonds are aligned parallel (� = 0) and minimal in�uence near � = 90○ .
Changing the value of B has no a�ect on the size of the coupling at � = 90○ .
Increasing the value of B reduces the value of 3 J HH in the range 90○ < � <
180○ , with greatest in�uence when � = 180○ . Increasing parameter A simply
increases the value of 3 J HH for all angles.

P��B.� Note that there is an error in the problem as printed. �e relationship between
the Sn–Sn and H–H couplings should be expressed as
(3 J SnSn �Hz) = 78.86 × (3 J HH �Hz) + 27.84
 15
B = −2 Hz
B = −1 Hz
B = −0.1 Hz
10
J HH �Hz

5
3

0
0 30 60 90 120 150 180
��○

(a) �e Karplus equation for 3 J HH is a linear equation in cos � and cos 2�,
and the experimentally determined equation for 3 J SnSn is linear in 3 J HH .
If F( f ) is linear in f , and f (x) is linear in x, it follows that F(x) is also
linear in x. �erefore 3 J SnSn is a linear equation in cos � and cos 2�.
(b) Substitution of the Karplus equation for 3 J HH into the expression for 3 J SnSn
gives a Karplus-type expression for the latter.

(3 J SnSn � Hz) = 78.86 × (3 J HH � Hz) + 27.84

= 78.86 × (A + B cos � + C cos 2�) + 27.84
= (78.86A + 27.84) + 78.86B cos � + 78.86C cos 2�
= A′ + B′ cos � + C ′ cos 2�

Taking the values A = 7 Hz, B = −1 Hz, and C = 5 Hz from the text

gives the parameters in this new Karplus-type equation as (A′ �Hz) =
78.86×(7)+27.84 = 580, (B′ �Hz) = 78.86×(−1) = −78.9, and (C ′ �Hz) =
78.86 × (5) = 394. �us, the Karplus-type equation for the Sn–Sn cou-
plings is
(3 J SnSn � Hz) = 580 − 78.9 cos � + 394 cos 2�
A plot of 3 J SnSn as a function of � is shown in Fig. ��.�.
(c) A staggered conformation with the SnMe� groups trans to each other
(� = 180○ ) is the preferred arrangement as this minimised the steric
repulsion between the bulky SnMe� groups.

SnMe�
H H

H H
SnMe�
 1 000

J SnSn �Hz
500
3

0
0 30 60 90 120 150 180
��○

P��B.� �e average of Bnuc over all orientations is found by integrating the expression
for Bnuc over the polar angles θ and �, with θ in the range � to π, and � in the
range 0 to 2π; the volume element is sin θ dθ d�. �e constants which appear
in the expression for Bnuc , (γN ħµ 0 m I )�(4πR 3 ), are written as A.
π 2π
�Bnuc � = A � � (1 − 3 cos2 θ) sin θ dθ d�
θ=0 �=0
π 2π
= A� (sin θ − 3 cos2 θ sin θ) dθ � d�
θ=0 �=0

�e integral of the second term is found by recognising that (d�dθ) cos3 θ =

−3 cos2 θ sin θ

�Bnuc � = A �− cos θ + cos3 θ�θ=0 × ����=0

π 2π

= A[(− cos π + cos3 π) − (− cos 0 + cos3 0)] [2π − 0]

= A[(−(−1) + (−1)3 ) − (−(1) + (1)3 )] [2π] = 0
��� � � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � � �� ��� � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � �
=0 =0

Hence �Bnuc � = 0 .

D��C.� Relaxation results from the interaction between individual spins and local mag-
netic �elds which arise in various ways. As is described in Topic ��A, the inter-
action between a spin and a magnetic �eld depends on the magnetogyric ratio
of the spin: the greater the magnetogyric ratio, the stronger the interaction.
�us, a given local �eld has a greater interaction with a nucleus with a greater
 magnetogyric ratio and, all other things being equal, the relaxation caused by
these �elds will therefore be faster the greater the magnetogyric ratio.
�e magnetogyric ratio for �H is about four times that of ��C, hence the inter-
actions between �H and local �elds is stronger leading to faster relaxation and
shorter relaxation times. A somewhat separate issue is that in typical molecules
H atoms tend to be more accessible than C atoms, and so if the local �eld is from
outside the molecule it may be felt more strongly by the more exposed H atoms.

D��C.� �is is discussed in Section ��C.� on page ���.

E��C.�(b) From the discussion in Section ��C.�(a) on page ���, the �ip angle � of a pulse
of duration ∆τ is given by � = γN B1 ∆τ, where B1 is the strength of the applied
�eld. It follows that B1 = ��γN ∆τ. With the data given

� π�2
B1 = = = 1.2 mT
γN ∆τ (26.752 × 107 T−1 s−1 ) × (5 × 10−6 s)

�e corresponding 180○ pulse has twice the �ip angle so, for the same B1 , ∆τ
is doubled: ∆τ = 2 × (5 µs) = 10 µs .

E��C.�(b) �e e�ective transverse relaxation time, T2∗ , is given by [��C.�–���], T2∗ =

1�π∆ν 1�2 , where ∆ν 1�2 is the width of the (assumed) Lorentzian signal mea-
sured at half the peak height. Hence

1 1
T2∗ = = = 0.027 s
π∆ν 1�2 π × (12 Hz)

E��C.�(b) �e amplitude of the free induction decay, S(t), is proportional to e−t�T2 , where
t is time and T2 is the transverse relaxation time. If S(t 2 ) = 12 S(t 1 ) then

S(t 2 ) 1 e−t 2 �T2

= = = e−(t 2 −t 1 )�T2 = e−∆t�T2
S(t 1 ) 2 e−t 1 �T2

taking logarithms gives

ln 12 = −∆t�T2 therefore ∆t = −T2 ln 12 = T2 ln 2

With the data given

∆t = (0.050 s) × ln 2 = 0.035 s
E��C.�(b) Mono�uoroethanoic acid has two carbon environments: an sp3 hybridised car-
bon and a carboxylic acid carbon. �e ��C NMR spectrum shows a signal at
δ = 79 which is due to the sp3 carbon. �is C atom is adjacent to two protons
and one F atom. Coupling with the two protons splits the carbon signal into
a triplet, which is further split by the coupling to the F atom into a doublet of
triplets.
When the ��C NMR spectrum is observed with proton decoupling, splittings
due to C–H coupling are collapsed, leaving just the doublet due to coupling to
F. �e splitting is the one-bond C–F coupling, 1 J = 160 Hz.
�e signal at δ = 179 is due to the carboxylic acid carbon. �is is also split into a
doublet of triplets by coupling to two protons and one F, but as these couplings
are over two bonds they are much smaller than those seen for other carbon.
When proton decoupling is used, this multiplet collapses to a doublet for the
same reasons as above.

E��C.�(b) �e maximal NOE enhancement is given by [��C.�–���], η = γ X �2γ A , where

γ X and γ A are the magnetogyric ratios of nuclei X and A, respectively.
γ1 H (26.752 × 107 T−1 s−1 )
η= = = �.����
2γ19 F 2 × (25.177 × 107 T−1 s−1 )

P��C.� �e free-induction decay consists of signals of the form given by [��C.�–���]

S(t) = S 0 cos (2πν L t)e−t�T2

If there are several lines, the overall signal is the sum of several such signals,
each in principle with a di�erent intensity, frequency, and transverse relaxation
time. As described in the problem, the frequencies measured by the spectrom-
eter are the o�set frequencies, given by δν L �106 , where δ is the chemical shi�.
In this case the peak at δ = 3.2 in an ��� MHz spectrometer gives signal at
3.2 × (800 × 106 Hz)�(106 ) = 2560 Hz; similarly, the other peaks give signals
at ���� Hz and ���� Hz. �e intensities are all assumed to be the same, S 0 .
Because the oscillations in the free-induction decay are rapid it is only possible
to see them clearly by plotting a small section of signal, which is what is shown
in Fig. ��.�.
If the signal at δ = 5.0 is reduced in intensity to S 0 �10, the free-induction
decay, Fig. ��.��, shows a clear reduction in the highest-frequency component.
�e overall decay of the function is seen by plotting it out to longer times,
as in Fig. ��.�� (note that, for practical reasons, in this plot the data points
in insu�ciently closely spaced to reproduce the waveform precisely, but the
overall decay is correctly represented).

P��C.� (a) �e NMR lineshape is approximated using a Lorentzian function of the

form
S 0 T2
IL (ω) =
1 + T2 (ω − ω 0 )2
2
 1.0

0.5

S(t)�S(0) 0.0

−0.5

−1.0
0.000 0.001 0.002 0.003 0.004 0.005
t� s

1.0

0.5
S(t)�S(0)

0.0

−0.5

−1.0
0.000 0.001 0.002 0.003 0.004 0.005
t� s

where ω = 2πν is the angular frequency, ω 0 is the resonance frequency,

S 0 is a constant, and T2 is the transverse relaxation time. Inspection of the
function shows that it must be a maximum at ω = ω 0 as this minimises
the denominator. At this point the function has the value IL (ω 0 ) = S 0 T2 .
�e peak reaches its half-height of S 0 T2 �2 when
S 0 T2
S 0 T2 �2 = hence (ω 1�2 − ω 0 )2 = 1�T22
1+ T2 (ω 1�2
2 − ω 0 )2

It follows that ω 1�2 = ω 0 ± 1�T2 . Converting from angular frequency

using ω = 2πν gives ν 1�2 = ν 0 ± 1�2πT2 . Hence the width at half-height
is 2 × (1�2πT2 ) = 1�πT2 in Hz, or 2�T2 when expressed as an angular
frequency.
(b) �e NMR lineshape can also be approximated using a Gaussian function
of the form
IG (ω) = S 0 T2 e−T2 (ω−ω 0 )
2 2
 1.0

0.5

S(t)�S(0)
0.0

−0.5

−1.0
0.0 0.2 0.4 0.6
t� s

�e exponential term is a maximum when ω = ω 0 , so the maximum of

the function is IG (ω 0 ) = S 0 T2 . �e peak reaches its half-height of S 0 T2 �2
when

S 0 T2 �2 = S 0 T2 e−T2 (ω 1�2 −ω 0 ) (ω 1�2 − ω 0 )2 = (ln 2)�T22

2 2
hence

It follows that ω 1�2 = ω 0 ± (ln 2)1�2 �T2 . Converting from angular fre-
quency using ω = 2πν gives ν 1�2 = ν 0 ± (ln 2)1�2 �2πT2 . �e width at
half-height is 2 × ν 1�2 = (ln 2)1�2 �πT2 in Hz, or 2(ln 2)1�2 �T2 when
expressed as an angular frequency.
(c) Choosing x = T2 (ω − ω 0 ) then both functions can be re-written.
1
IL (ω)�S 0 T2 = IG (ω)�S 0 T2 = e−x
2

1 + x2
Figure ��.�� shows plots of both functions. �e most noticeable feature
is that the Gaussian is more compact and decays more quickly than does
the Lorentzian. �e functions as plotted are not normalised: if they were,
such that the area under the curves is equal, the Lorentzian would have a
lower peak height than the Gaussian.

P��C.� �e shape of a spectral line, I(ω), is given by the Fourier transform of the free-
induction decay G(t)
∞
I(ω) = Re �� G(t)eiωt dt�
0

�e form of this integral means that the Fourier transform is linear, in the sense
that the Fourier transform of G 1 (t) + G 2 (t) is equal to the Fourier transform
of G 1 (t) + the Fourier transform of G 2 (t).
It is shown in the previous Problem that the Fourier transform of a cos ω 0 t e−t�τ
consists of two Lorentzians at ω = ±ω 0 , with width 2�τ, and height scaled by a.
 1.0
IL
0.8 IG

I(x)�S 0 T2
0.6

0.4

0.2

0.0
−4 −2 0 2 4
x

�erefore the Fourier transform of a cos ω 1 t e−t�τ + b cos ω 2 t e−t�τ will consist
of two Lorentzians at ω = ±ω 1 , with height scaled by a, and two Lorentzians at
ω = ±ω 2 , with height scaled by b; all the peaks will have width 2�τ.

P��C.� �e di�erential equation which describes the time-dependence of the z-magnetization

is given in Problem P��C.�

dM z (t) M z (t) − M 0
=−
dt T1
Separate the di�erential equation and integrate between t = 0 and t = τ, and
the corresponding limits M z (0) = −M 0 and M z (τ).
M z (τ) 1 τ 1
� dM z (t) = − � dt
−M 0 M z (t) − M 0 0 T1

M (τ) t τ
�ln (M z (t) − M 0 )�−Mz 0 = �− �
T1 0
M z (τ) − M 0 τ
ln � �=−
−2M 0 T1
hence M z (τ) = M 0 (1 − 2e−τ�T1 )

�e time τ null at which M z (τ null ) = 0 is found by solving

M 0 (1 − 2e−τ null �T1 ) = 0 hence τ null = T1 ln 2

With the given data, T1 ln 2 = 0.50 s, hence T1 = (0.50 s)� ln (2) = 0.72 s .

P��C.�� Figure ��.�� shows the motion of magnetization vectors from typical ‘fast’ and
‘slow’ spin packets (relative to the rotating frame frequency) during the spin
echo sequence. �e ��○ pulse rotates the magnetization onto −y, and then
during the delay τ the vectors from the spin packets fan out. �e ���○ pulse
 applied about x rotates the vectors to mirror-image positions with respect to
the xz-plane. In the subsequent period the vectors continue as before, but at
the end of the delay τ they converge onto the +y axis. Refocusing occurs, as it
did in Fig. ��C.�� on page ���, but along the opposite axis.

z z

90○ pulse

x y x y

τ
z z
slow spins

180○ pulse

x y x fast spins y

τ
z

x y

P��C.�� �e magnitude of the local magnetic �eld is given by [��B.��a–���]

γ N ħµ 0 m I
Bloc = − (1 − 3 cos2 θ)
4πR 3

where Bloc is the local magnetic �eld, γ N is the nuclear magnetogyric ratio,
µ 0 is the vacuum permeability, m I ħ is the z-component of the spin angular
momentum, R is the internuclear separation, and θ is the angle between the
direction of local �eld vector and the direction of the applied magnetic �eld.
�e average over angles θ = 0 → θ ′ is found by integrating Bloc over this range,
with the appropriate volume element, which is sin θ dθ. �e integral is divided
 θ′
by ∫0 sin θ dθ to ensure normalization

θ′
∫ Bloc sin θ dθ
�Bloc � = 0 θ ′
∫0 sin θ dθ
θ′
γ N ħµ 0 m I ∫0 (1 − 3 cos2 θ) sin θ dθ
= × θ′
4πR 3 ∫0 sin θ dθ

�e integral in the denominator evaluates to 1 − cos θ ′ . �e integral in the

θ′
numerator separates into two: the �rst is ∫0 sin θ dθ which similarly evaluates
to 1 − cos θ ′ . �e second is evaluated as follows
θ′
I = −3 � cos2 θ sin θ dθ
0

Recognise that (d�dθ) cos3 θ = −3 cos2 θ sin θ

θ′
I = −3 �− 13 cos3 θ�0 = cos3 θ ′ − 1

Putting this all together gives

γ N ħµ 0 m I (1 − cos θ ′ ) + (cos3 θ ′ − 1)
�Bloc � = ×
4πR 3 1 − cos θ ′
γ N ħµ 0 m I cos θ (cos2 θ ′ − 1)
′
= ×
4πR 3 1 − cos θ ′
γ N ħµ 0 m I cos θ ′ (cos θ ′ + 1)′ (cos θ ′ − 1)
= ×
4πR 3 1 − cos θ ′
γ N ħµ 0 m I
=− × cos θ ′ (cos θ ′ + 1)
4πR 3

When θ ′ = π, (cos θ ′ + 1) = (cos π + 1) = 0 and, as expected, the �eld averages

to zero.
�e separation R was found in Problem P��C.�� to be 158 pm. With θ ′ = 30○ in
the above expression, and taking m I = + 12 , the average �eld is computed as

γ N ħµ 0 m I
�Bloc � = − × cos θ ′ (cos θ ′ + 1)
4πR 3
(26.752 × 107 T−1 s−1 ) × (1.0546 × 10−34 J s) × (1.257 × 10−6 T2 J−1 m3 )
=−
2 × 4π × (158 × 10−12 m)3
× cos 30○ × (cos 30○ + 1)
= −(3.57... × 10−4 T) × (31�2 �2) × (31�2 �2 + 1)
= −0.578 mT
D��D.� �e hyper�ne parameter a for the coupling between a nucleus and the elec-
tron in a radical is easily measured from the splittings of the lines in the EPR
spectrum caused by the nucleus in question. If the quantitative relationship
between a and ρ is know (for example, as it is for aromatic systems, the Mc-
Connell equation) it is possible to map out the spin density in the molecule, thus
revealing the spatial distribution of the molecular orbital which is occupied by
the unpaired electron.

E��D.�(b) �e EPR resonance condition is given by [��D.�–���], hν = g µ B B0 , where ν is

the spectrometer operating frequency, g is the g-value of the radical, µ B is the
Bohr magneton, and B0 is the magnetic �eld. Rearranging the expression gives

hν (6.6261 × 10−34 J s) × (9.2482 × 109 Hz)

g= = = �.����
µ B B0 (9.2740 × 10−24 J T−1 ) × (330.02 × 10−3 T)

E��D.�(b) As described in Section ��D.� on page ���, the splitting between the lines in
the multiplet is the hyper�ne coupling constant. In this case the splitting is
(338.0 − 335.8) mT = 2.2 mT, (335.8 − 333.6) mT = 2.2 mT, and (333.6 −
331.4) mT = 2.2 mT. �erefore a = 2.2 mT .
�e g-value is computed from the centre of the multiplet, which is at (333.6 +
1
2
× 2.2) mT = 334.7 mT. �en, using [��D.�–���], hν = g µB B0

hν (6.6261 × 10−34 J s) × (9.332 × 109 Hz)

g= = = �.����
µB B0 (9.2740 × 10−24 J T−1 ) × (334.7 × 10−3 T)

E��D.�(b) �e total local magnetic �eld is given by [��D.�–���], Bloc = B0 + am I 1 , where

m I 1 = ± 12 and a is the hyper�ne coupling constant. Further interactions with a
second and a third proton give the overall �eld as

Bloc = B0 + am I 1 + am I 2 + am I 3

where each m I i = ± 12 . �ere are � possible combinations of the m I i and hence

� lines. �e centre of the spectrum is at 332.8 mT.
For example, the line with all m I i = + 12 is at

B�mT = 332.8 + 12 × 2.11 + 12 × 2.87 + 12 × 2.89 = 336.735

and that with m I 1 = − 12 , m I 2 = + 12 , and m I 3 = + 12 is at

B�mT = 332.8 − 12 × 2.11 + 12 × 2.87 + 12 × 2.89 = 334.625

Repeating this process gives the � lines as (in order)

 ���.���, ���.���, ���.���, ���.���, ���.���, ���.���, ���.��� and ���.��� mT
All � lines have equal intensity . However, the third and fourth peak, and the
��h and sixth peak, are closely spaced and so, if the instrument does not have
high enough resolution, may overlap with one another to give a peak of double
height.

E��D.�(b) (i) �e expectation is that the CH� protons will have a larger hyper�ne con-
stant than the CH� protons. �erefore the main splitting will be into
a triplet (�:�:�), and each of the lines of the triplet may be further split
by a smaller amount into a quartet (�:�:�:�). If all the lines are resolved
the spectrum will be a triplet of quartets, a total of �� lines with relative
intensities �:�:�:�; �:�:�:�; �:�:�:�.
(ii) �e splittings due to couplings to equivalent spin � nuclei are illustrated in
Fig. ��D.� on page ���. Coupling to the CD� deuterons will give �ve lines
with intensities (�:�:�:�:�). �e smaller coupling to the CD� deuterons will
split each of these lines into seven, with intensities (�:�:�:�:�:�:�), giving
�� lines in total.

E��D.�(b) �e resonance frequency is related to the g-value by [��D.�–���], hν = g µB B0 .

Rearranging this gives B0 = h�B .
(i) For a spectrometer operating at 9.501 GHz,
hν (6.6261 × 10−34 J s) × (9.501 × 109 Hz)
B0 = = = 339.0 mT
g µB 2.0024 × (9.2740 × 10−24 J T−1 )
(ii) For a spectrometer operating at 34.77 GHz,
hν (6.6261 × 10−34 J s) × (34.77 × 109 Hz)
B0 = = = 1.241 T
g µB 2.0024 × (9.2740 × 10−24 J T−1 )

E��D.�(b) If a radical contains N equivalent nuclei with spin quantum number I, then
there are 2N I+1 hyper�ne lines. �e radical contains two magnetic nuclei, N =
2, and there are a total of �ve hyper�ne lines. �erefore 2N I+1 = 2×2×I+1 = 5
hence I = 1 . �e splitting pattern arising from coupling to equivalent nuclei
with I = 1 is shown in Fig. ��D.�: coupling to two such nuclei gives �ve lines in
the intensity ratio �:�:�:�:�.

P��D.� �e EPR resonance condition is given by [��D.�–���], hν = g µ B B0 , where ν is

the spectrometer operating frequency, g is the g-value of the radical, µ B is the
Bohr magneton and B0 is the magnetic �eld. �e expression is rearranged to
make g the subject.
When the applied magnetic �eld is parallel to the OO direction,
hν (6.6261 × 10−34 J s) × (9.302 × 109 Hz)
g= = = �.���
µ B B0 (9.2740 × 10−24 J T−1 ) × (333.64 × 10−3 T)
 When the applied magnetic �eld lies along the bisector of the ONO angle,

hν (6.6261 × 10−34 J s) × (9.302 × 109 Hz)

g= = = �.���
µ B B0 (9.2740 × 10−24 J T−1 ) × (331.94 × 10−3 T)

P��D.� �e splitting due to the two N atoms results in 2N I + 1 = 2 × 2 × 1 + 1 = 5 lines

with relative intensity ratio �:�:�:�:�, a quintet . Adjacent lines are separated by
a(N) = 0.148 mT. Each of these lines is further split into a �:�:�:�:�, a quintet
by coupling to four H atoms results (2N I + 1 = 2 × 4 × 12 + 1 = 5). Adjacent
lines in the quintet are separated by a(H) = 0.112 mT. Because the two hyper-
�ne constant are similar the multiplets overlap extensively, giving a complex
multiplet.
Figure ��.�� shows how the complete multiplet is formed from �ve overlapping
�:�:�:�:� quintets, a–e, centred at the positions of the lines of the �:�:�:�:� quintet,
and with intensities in proportion. For example, quintet a is centred at the �eld
of the le�-most line of the �:�:�:�:� a quintet, and has relative intensity �. Quintet
b is centred at the �eld of the next le�-most line of the �:�:�:�:� a quintet, and
has relative intensity �. �e dotted lines show the relationship of the multiplets
a–e to the lines in the �:�:�:�:� a quintet.

b d
a e

complete multiplet

�:�:�:�:� quintet

P��D.� �e McConnell equation is given in [��D.�–���], a = Qρ, where a is the hy-

per�ne coupling constant observed for a H atom in a given molecule, Q is
a constant, and ρ is the spin density on the adjacent carbon atom. For the
benzene radical anion, Q = 2.25 mT; the same value is used for each of the
anions considered here. For example, at position � in �

a 0.011 mT
ρ= = = 4.89 × 10−3
Q 2.25 mT
�e spin densities for each carbon, computed in the same way, are shown in
Fig. ��.��.
 NO� NO�

4.89 × 10−3 NO� �.��� �.���

− −

7.64 × 10−3 4.89 × 10−3 �.��� NO�

7.64 × 10 −3 �.���
NO�

�.���� �.����
−

�.���� �.����
NO�

P��D.� Simple considerations indicate that the EPR spectrum of � will be a �:�:� triplet
on account of the coupling of the electron to a single ��N, which has I = 1. Elec-
tron exchange, resulting from the physical interaction of two radicals, results
in a scrambling of the spin state of the electron because the electron which
is exchanged has an equal change of being in the α or β spin states. Such
scrambling at �rst causes a broadening of the lines in the hyper�ne multiplet,
and if it is at a high enough rate the lines merge. For even faster rates, the
merged line narrows. �is is analogous to the e�ect that chemical exchange
has on the coupling patterns seen in NMR, Section ��B.� on page ���.

I��.� (a) �e spin densities, computed by molecular modelling so�ware (ab initio,
density functional theory, Gaussian ��), are shown below

O 0.409

− 0.082
0.299 0.271

− 0.135 − 0.129
0.369

CH3
− 0.024

�e computed spin densities for the the two protons ortho to the oxygen,
and to the two protons meta to the oxygen are di�erent. �is is undoubt-
edly a computational artefact, a result of the minimum-energy structure
having one methyl proton in the plane of the ring, which makes the right
and le� side of the ring slightly non-equivalent. Fast internal rotation
 is expected to make the two meta protons, and the two ortho protons,
equivalent. �e spin density at the ortho carbons is therefore taken as
�.���, and that at the meta carbons as −0.132.
(b) �e hyper�ne coupling constants resulting from coupling to the ring pro-
tons are computed using the McConnell equation, [��D.�–���]: a = Qρ,
with Q = 2.25 mT. Hence a ortho = 0.285 × (2.25 mT) = 0.641 mT,
and a meta = 0.132 × (2.25 mT) = 0.297 mT. �e hyper�ne coupling for
interaction with the methyl protons cannot be calcuated in the same way
but is given by the so�ware as �.��� mT. �e EPR spectrum will show
a rather complex multiplet arising from splitting into a �:�:� triplet as a
result of the coupling to the ortho protons, each line is then split into a
�:�:� triplet as a result of the coupling to the meta protons, and each line
is split once more into a �:�:�:� quartet as a result of the coupling to the
methyl protons.

I��.� Terms such as [I], [EI], [E], νI , νEI and ν need to be eliminated from the ex-
pressions. First, note that total I (free I plus bound I) is the same as initial I;
similarly, total E (free E plus bound E) is the same as initial E.
[I]tot = [I]0 = [I] + [EI] and [E]tot = [E]0 = [E] + [EI]
Using this, the expression for KI is rewritten
[E][I] ([E]0 − [EI])([I]0 − [EI])
KI = =
[EI] [EI]

Because [I]0 >> [E]0 it follows that [I]0 must also be much greater than [EI],
even if all of the E binds I. Hence [I]0 − [EI] ≈ [I]0 . �is is substituted into the
above expression which is then solved for [EI].
([E]0 − [EI])[I]0 [E]0 [I]0
KI = hence [EI] = (��.�)
[EI] KI + [I]0

�e expression for ν is written using [I] = [I]0 − [EI] to give

[I]νI + [EI]νEI νI ([I]0 − [EI]) + νEI [EI]
ν = fI νI + fEI νEI = =
[I] + [EI] [I]0
�is is rearranged to given an expression for [EI], and then [EI] is substituted
using eqn ��.�
(ν − νI )[I]0 δν[I]0 [E]0 [I]0 δν[I]0
[EI] = = hence =
νEI − νI ∆ν KI + [I]0 ∆ν
where δν and ∆ν as as de�ned in the text. Finally, [I]0 is made the subject to
give
∆ν
[I]0 = [E]0 − KI
δν
It follows from this that a plot of [I]0 against 1�(δν) is a straight line with slope
[E]0 ∆ν and y-intercept −KI .
D��A.� �e principle of equal a priori probabilities is the assumption that the popula-
tion of any physical state depends only on its energy and not how that energy
is distributed. For example, a state in which a certain amount of the energy of a
molecule is in translational motion is just as likely as a state where this energy is
in rotational motion, or in vibrational motion, or split between these di�erent
modes.

D��A.� Because the Boltzmann distribution gives the ratio of populations of states of
di�erent energy as a function of temperature, it accounts for the temperature
dependence of many physical and chemical phenomena. �ese include: the
intensities of spectral transitions (Topic ��A); chemical equilibrium (Topic ��F),
in which the distribution of reactant and product species is determined by
a single Boltzmann distribution over the states of the system; the Maxwell–
Boltzmann distribution of molecular speeds in the kinetic model of gases (Topic
�B); collision theory, in which the temperature dependence of the rate of reac-
tion is understood through the Boltzmann distribution (Topic ��A).

E��A.�(b) �e weight of a con�guration is given by [��A.�–���], W = N!�(N 0 !N 1 !N 2 !...),

thus
21!
W= = 2.05 × 1012
6! × 0! × 5! × 0! × 4! × 0! × 3! × 0! × 2! × 0! × 0! × 1!

E��A.�(b) (i) 10! = 10 × 9 × 8 × 7 × 6 × 5 × 4 × 3 × 2 × 1 = 3 628 800 .

(ii) Stirling’s approximation for x � 1 is given by [��A.�–���], ln (x!) ≈
x ln x − x. �is is rearranged for to x! ≈ e(x ln x−x) , thus

10! ≈ e(10×ln 10−10) = 4.54 × 105 .

 (iii) Using the more accurate version of Stirling’s approximation

10! ≈ (2π)(1�2) × 10(10+1�2) × e−10 = 3.60 × 106

E��A.�(b) �e Boltzmann population ratio is given by [��A.��a–���], N i �N j = e−β(ε i −ε j ) ,

where β = 1�(kT). As temperature approaches zero, β approaches in�nity. �e
relative populations of two levels, assuming ε 0 < ε 1 , is therefore

N 1 �N 0 = lim e−β(ε 1 −ε 0 ) = �
β→+∞

In this limit, only the lower state is occupied.

E��A.�(b) �e Boltzmann population ratio is given by [��A.��a–���], N i �N j = e−β(ε i −ε j ) .

�is is rearranged to β = − ln(N i �N j )�∆ε , where ∆ε = (ε i − ε j ). Substituting
β = 1�(kT) and rearranging for T gives
∆ε hc ν̃
T =− =−
k ln (N 1 �N 0 ) k ln (N 1 �N 0 )
(6.6261 × 10 J s) × (2.9979 × 1010 cm s−1 ) × (300 cm−1 )
−34
=−
(1.3806 × 10−23 J K−1 ) × ln(1�2)
= 623 K

E��A.�(b) �e Boltzmann population ratio for degenerate energy levels is given by [��A.��b–
���], N i �N j = (g i �g j )e−β(ε i −ε j ) . �e rotational term of a spherical rotor is
given by [��B.�–���], F̃(J) = B̃J(J + 1) and, as explained in Section ��B.�(c) on
page ���, its degeneracy is given as g J = (2J + 1)2 . �e rotational energy is
related to the rotational term as ε J = hc F̃(J). �erefore
N 5 (2 × 5 + 1)2
= × e−hc B̃[5×(5+1)−0×(0+1)]�k T = 121 × e−30 B̃hc�k T
N 0 (2 × 0 + 1)2
using kT�hc = 207.224 cm−1 at 298.15 K (from inside the front cover)
N5
= 121 × e−30×(2.71 cm )�(207.224 cm ) = ��.�
−1 −1

N0

E��A.�(b) �e Boltzmann population ratio for degenerate energy levels is given by [��A.��b–
���], N i �N j = (g i �g j )e−β(ε i −ε j ) . �is is rearranged to
β = − ln[(N i �N j )(g j �g i )]�∆ε where ∆ε = (ε i − ε j )
Substituting β = 1�(kT) and rearranging for T gives
∆ε hc ν̃
T =− =−
k ln[(N 1 �N 0 )(g 0 �g 1 )] k ln [(N 1 �N 0 )(g 0 �g 1 )]
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (360 cm−1 )
=−
(1.3806 × 10−23 J K−1 ) × ln [(15%�85%) × (1�2)]
= 213 K
P��A.� �e energy of a con�guration is E�ε = N 1 + 2N 2 + 3N 3 . . ., and the weight of a
con�guration is given by [��A.�–���], W = N!�(N 0 !N 1 !N 2 !...). �e con�gura-
tions satisfying the total energy constraint E = 9ε are

N0 N1 N2 N3 N4 N5 N6 N7 N8 N9 W
� � � � � � � � � � �
� � � � � � � � � � ��
� � � � � � � � � � ��
� � � � � � � � � � ���
� � � � � � � � � � ��
� � � � � � � � � � ���
� � � � � � � � � � ���
� � � � � � � � � � ��
� � � � � � � � � � ���
� � � � � � � � � � ���
� � � � � � � � � � ����
� � � � � � � � � � ���
� � � � � � � � � � ���
� � � � � � � � � � ���
� � � � � � � � � � ����
� � � � � � � � � � ����
� � � � � � � � � � ���
� � � � � � � � � � ��
� � � � � � � � � � ����
� � � � � � � � � � ����
� � � � � � � � � � ���
� � � � � � � � � � ����
� � � � � � � � � � ����
� � � � � � � � � � ���
� � � � � � � � � � ���
� � � � � � � � � � ����
� � � � � � � � � � ���
� � � � � � � � � � ��
� � � � � � � � � � �

Hence the most probable con�guration is {4, 2, 2, 1, 0, 0, 0, 0, 0, 0} , which is

the most reminiscent of an exponential distribution.

P��A.� �e Boltzmann distribution is given by [��A.��b–���], N i �N = e−βε i �q, where q

is the partition function de�ned in [��A.��–���], q = ∑ i e−βε i , and β = 1�(kT).
 Without loss of generality let the energy of A be �, which implies that ε B =
5.0 kJ mol−1 and ε C = ε B + 0.5 kJ mol−1 = 5.5 kJ mol−1 . �e partition function
is

q = e−βε A + e−βε B + e−βε C = 1 + e−βε B + e−βε C

�e proportion of molecules in conformation B is

N B e−βε B e−βε B
= =
N q 1 + e−βε B + e−βε C

Because ε i = E i �N A and k = R�N A , βε i = E i �RT, it follows that

NB e−E B �RT
=
N 1 + e B �RT + e−E C �RT
−E
−1
− (8.31455.0×10 J mol 3

e J K−1 mol−1 )×(273

=
K)

3 J mol−1 −1
− (8.31455.0×10 − (8.31455.5×10
1+e +e
J mol 3
J K−1 mol−1 )×(273 K) J K−1 mol−1 )×(273 K)

= 0.092

P��A.� In Section ��A.�(a) on page ��� it is shown that ln W = ln N! − ∑ i ln N i !. �e

full version of Stirling’s approximation is used for the factorials to give

ln W = ln[(2π)1�2 N N+1�2 e−N ] − � ln[(2π)1�2 N j N j +1�2 e−N j ]

j

= ln(2π) + (N +
1
2
1
2
) ln N − N − � � 12 ln(2π) + (N j + 12 ) ln N j − N j �
j

Because ∑ j N j = N it follows that

ln W = 12 ln(2π) + (N + 12 ) ln N − � �(N j + 12 ) ln N j + 12 ln(2π)�

��� � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � j
A ��� � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � �
B

�e next step is to compute ∂ ln W�∂N i : only the non-constant terms A and B

contribute to the derivative. First, consider the di�erential of term A

∂[(N + 12 ) ln N] ∂(N + 12 ) ∂ ln N
=� � ln N + (N + 12 ) � �
∂N i ∂N i ∂N i
∂N 1 ∂N
=� � ln N + (N + 12 ) � �
∂N i N ∂N i

As explained in the text, (∂N�∂N i ) = 1. It therefore follows that

∂[(N + 12 ) ln N] 1 N+ 1
= ln N + (N + 12 ) = ln N + 2
∂N i N N
 Next, consider the di�erential of term B

∂ ∑ j �(N j + 12 ) ln N j � ∂(N j + 12 ) ∂ ln N j
= � �� � ln N j + (N j + 12 ) � ��
∂N i j ∂N i ∂N i
∂(N j + 12 ) 1 ∂N j
= � �� � ln N j + (N j + 12 ) � ��
j ∂N i N j ∂N i

Only the derivatives with j = i are non-zero to give

Ni + 1
= ln N i + 2
Ni

Bringing the terms together gives the expression for the derivative

∂ ln W N+ 1
Ni + 1
= ln N + 2
− ln N i − 2
∂N i N Ni

For a macroscopic sample N � 1 and N i � 1, so N + 1

2
≈ N and N i + 1
2
≈ Ni ;
with these approximations

∂ ln W
= ln N + 1 − (ln N i + 1)
∂N i

�is is identical to the expression found in How is that done? ��A.� on page ���,
and so it is concluded that for macroscopic samples the use of the full version
of Stirling’s approximation has no e�ect (with the possible exception of states
with very low populations).

D��B.� It is possible for there to be di�erent wavefunctions which have the same en-
ergy: such wavefunctions are said to be degenerate. If this is the case, for a
given ‘energy level’, that is a given value of the energy, there are several ‘states’
each of which is distinct but has the same energy.
�e partition function is computed as a sum over the states. However, because
degenerate states have the same energy, the sum may be computed as a sum over
energy levels, as long as the degeneracy g i of each level is taken into account.

q = � e−βε i = � g i e−βε i
states i levels i
E��B.�(b) (i) �e thermal wavelength is de�ned in [��B.�–���], Λ = h�(2πmkT)1�2 .
Because the mass of a molecule m is m = M�N A and k = R�N A it follows
that
h hN A
Λ= =
[2π(M�N A )(R�N A )T]1�2 (2πMRT)1�2

(6.6261 × 10−34 J s) × (6.0221 × 1023 mol−1 )

Λ(300 K) =
[2π×(0.02018 kg mol−1 )×(8.3145 J K−1 mol−1 ) × (300 K)]1�2
= 2.24... × 10−11 m = 2.244 × 10−11 m

Similarly, Λ(3000 K) = 7.095 × 10−12 m

(ii) �e translational partition function in three dimensions is given by [��B.��b–
���], q T = V �Λ 3 .

q T (300 K) = (1.00 × 10−6 m3 )�(2.24... × 10−11 m)3 = 8.85 × 1025

q T (3000 K) = 2.80 × 1027

E��B.�(b) �e translational partition function in three dimensions is given by [��B.��b–

���], q T = V �Λ 3 , where Λ is the thermal wavelength de�ned in [��B.�–���],
Λ = h�(2πmkT)1�2 .

V �Λ 3Ar
3
T
qAr Λ Ne 3 h�(2πm Ne kT)1�2 m Ar 3�2
= = � � = � � = � �
T
qNe V �Λ 3Ne Λ Ar h�(2πm Ar kT)1�2 m Ne
Because the mass of a molecule m is m = M�N A it follows that

39.95 g mol−1
3�2
T
qAr M Ar 3�2
= � � = � � = �.���
T
qNe M Ne 20.18 g mol−1

E��B.�(b) �e rotational partition function of a symmetric linear rotor is given by [��B.��a–

���], q R = kT�(2hc B̃), where the rotational constant is de�ned in [��B.�–���],
B̃ = ħ�(4πcI). �e moment of inertia of a diatomic is I = µR 2 , where R is the
bond length and µ = m A m B �(m A +m B ). For a homonuclear diatomic m A = m B
so it follows that µ = m B �2. Using m = M�N A , this becomes µ = M B �2N A .
M B R 2 (0.01401 kg mol−1 ) × (109.75 × 10−12 m)2
I = µR 2 = =
2N A 2 × (6.0221 × 1023 mol−1 )
= 1.40... × 10−46 kg m2

kT kT 4πcI kT 4πcI kT
qR = =� �� �=� �� �= 2 I
2hc B̃ 2hc ħ 4πcħ ħ ħ
(1.3806 × 10−23 J K−1 ) × (300 K)
= × (1.40... × 10−46 kg m2 ) = ��.�
(1.0546 × 10−34 J s)2
E��B.�(b) �e rotational partition function of a non-linear rotor is given by [��B.��–���],
q R = (1�σ)(kT�hc)3�2 (π�ÃB̃C̃)1�2 , where σ is the symmetry number. H� O
has a twofold axis so σ = 2.

(i) At 25 ○ C, which is 298.15 K

1 kT 3�2 π 1�2
qR = � � � �
2 hc ÃB̃C̃
(1.3806 × 10−23 J K−1 ) × (298.15 K)
3�2
1
= � �
2 (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
1�2
π
� �
(27.877 cm ) × (14.512 cm−1 ) × (9.285 cm−1 )
−1

= ��.�

(ii) At 100 ○ C, which is 373.15 K

(1.3806 × 10−23 J K−1 ) × (373.15 K)

3�2
1
qR = � �
2 (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
1�2
π
� �
(27.877 cm−1 ) × (14.512 cm−1 ) × (9.285 cm−1 )
= ��.�

E��B.�(b) �e rotational partition function of a heteronuclear diatomic is given by [��B.��–

���], q R = ∑ J (2J + 1)e−β hc B̃ J(J+1) . �is is evaluated explicitly by summing
successive terms until they become too small to a�ect the result to a given level
of precision. �e partition function in the high-temperature limit is given by
[��B.��a–���], q R = kT�hc B̃. For the data given it follows that

k×T (1.3806 × 10−23 J K−1 ) × T

qR = =
hc B̃ (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (6.511 cm−1 )
= (0.106... K−1 ) × T

�e values of q R computed in these two di�erent ways are compared in Fig. ��.�.
�e high temperature limit becomes accurate to within � % of the exact solution
at around 61 K .

E��B.�(b) �e partition function is given by [��B.�b–���], q R = ∑ J g J e−βε J , where the de-

generacy is given as g J = (2J +1)2 , as explained in Section ��B.�(c) on page ���,
and ε J is given by [��B.�b–���], ε J = hc B̃J(J + 1). �is is evaluated explicitly by
summing successive terms until they become too small to a�ect the result to a
given level of precision.
�e partition function in the high-temperature limit is given by [��B.��b–���],
q R = (kT�hc)3�2 (π�ÃB̃C̃)1�2 = π 1�2 (kT�hc B̃)3�2 , because for a spherical rotor
 10

6
qR
4

2 exact
high T limit
0
0 20 40 60 80
T�K

B̃ = Ã = C̃. Ignoring the role of the nuclear spin means that all J states are
accessible and have equal weight. For the data given it follows that

k × T 3�2
q R = π 1�2 � �
hc B̃
(1.3806 × 10−23 J K−1 )
3�2
= π 1�2 � � × T 3�2
(6.6261 × 10−34 J s)×(2.9979 × 1010 cm s−1 )×(0.0572 cm−1 )
= (75.0... K−3�2 ) × T 3�2

�e values of q R computed in these two di�erent ways are compared in Fig. ��.�.
�e high temperature limit becomes accurate to within � % of the exact solution
at around 0.4 K .

40
qR

20

exact
high T limit
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
T�K

E��B.�(b) (i) CO� is a centrosymmetric linear molecule and so has σ = 2 .

 (ii) O� has a twofold rotational axis bisecting the O–O–O angle; rotation
about this axis interchanges two identical oxygen atoms, therefore σ = 2 .
(iii) SO� is trigonal planar. It has a threefold rotational axis perpendicular
to the plane of the molecule and passing through the S atom, and three
twofold axes, each located along an S–O bond. �e symmetry number is
therefore given by σ = 3 × 2 = 6 .
(iv) For a molecule with high symmetry, such as octahedral SF� , the simplest
was to determine the symmetry number is to count the total number of
rotational symmetry operations, C n , listed in the character table of the
relevant point group, which in this case is O h . �e identity operation E
is equivalent to a C 1 rotation axis, so is included in the count. For O h
the relevant operations are (E, 8C 3 , 6C 2 , 6C 4 , 3C 2 ), giving a total of ��.
Hence σ = 24 .
(v) �e same procedure is used as in (iv). Al� Cl� belongs to the point group
D 2h , which has rotational operations (E, C 2x , C 2 , C 2z ). �erefore σ = 4 .
y

E��B.�(b) �e rotational partition function of an asymmetric rotor is given by [��B.��–

���], q R = (1�σ)(kT�hc)3�2 (π�ÃB̃C̃)1�2 , where σ is the symmetry number.
Pyridine has a twofold rotational axis along the C4 –N bond; rotation about
this axis interchanges pairs of identical atoms, therefore σ = 2. An alternative
way of deriving the value of the symmetry number is to note that both pyridine
and H� O belong to the point group C 2v , and so they have the same symmetry
number, which in the text is shown to be � for H� O.

1 kT 3�2 π 1�2
qR = � � � �
2 hc ÃB̃C̃
(1.3806 × 10−23 J K−1 ) × (298.15 K)
3�2
1
= � �
2 (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
1�2
π
� �
(0.2014 cm ) × (0.1936 cm−1 ) × (0.0987 cm−1 )
−1

= 4.26 × 104

E��B.�(b) �e vibrational partition function is given by [��B.��–���], q V = 1�(1−e−β hc ν̃ ),

where β = 1�kT. �e high-temperature approximation is given by [��B.��–
���], q V ≈ kT�hc ν̃.

k×T (1.3806 × 10−23 J K−1 ) × T

=
hc ν̃ (6.6261 × 10 J s) × (2.9979 × 1010 cm s−1 ) × (214.5 cm−1 )
−34

= (3.24... × 10−3 K−1 ) × T

�e values of q V computed using these two di�erent expressions are compared

in Fig. ��.�. �e high temperature limit becomes accurate to within � % of the
exact solution at 3000 K .
 10

qV 5

exact
high T limit
0
0 500 1 000 1 500 2 000 2 500 3 000
T�K

E��B.��(b) �e vibrational partition function for each mode is given by [��B.��–���], q V =

1�(1−e−β hc ν̃ ), where β = 1�kT. �e overall vibrational partition function is the
product of the partition functions of the individual modes; the bend is included
twice as it is doubly degenerate.

(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )

hcβ =
(1.3806 × 10−23 J K−1 ) × (900 K)
= 1.59... × 10−3 cm

−1
q V1 = �1 − e−hc β ν̃ 1 �
−1
= �1 − e−(1.59 ...×10 � = 1.00...
−3
cm)×(3311 cm−1 )

Similarly
−1
q V2 = �1 − e−(1.59 ...×10 � = 1.47...
−3
cm)×(712 cm−1 )

−1
q V3 = �1 − e−(1.59 ...×10 � = 1.03...
−3
cm)×(2097 cm−1 )

q V = q V1 × (q V2 )2 × q V3 = (1.00...) × (1.47...)2 × (1.03...) = 2.25

E��B.��(b) �e vibrational partition function for each mode is given by [��B.��–���], q V =

1�(1−e−β hc ν̃ ), where β = 1�kT. �e overall vibrational partition function is the
product of the partition functions of the individual modes, taking into account
the stated degeneracies.

(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )

hcβ =
(1.3806 × 10−23 J K−1 ) × (500 K)
= 2.87... × 10−3 cm
 −1
q V1 = �1 − e−hc β ν̃ 1 �
−1
= �1 − e−(2.87 ...×10 � = 2.49...
−3
cm)×(178 cm−1 )

Similarly

−1
q V2 = �1 − e−(2.87 ...×10 � = 4.38...
−3
cm)×(90 cm−1 )

−1
q V3 = �1 − e−(2.87 ...×10 � = 1.25...
−3 −1
cm)×(555 cm )

−1
q V4 = �1 − e−(2.87 ...×10 � = 3.30...
−3
cm)×(125 cm−1 )

q V = q V1 × (q V2 )2 × (q V3 )3 × (q V4 )3
= (2.49...) × (4.38...)2 × (1.25...)3 × (3.30...)3 = 3.43 × 103

E��B.��(b) �e partition function is given by [��B.�b–���], q = ∑ i g i e−βε i , where g i is

degeneracy and the corresponding energy is given as ε i = hc ν̃ i . At T = 2000 K

(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )

βhc = = 7.19... × 10−4 cm
(1.3806 × 10−23 J K−1 ) × (1900 K)

�erefore the electronic partition function is

q E = g 0 + g 1 × e−βε 1 + g 2 × e−βε 2
= 3 + 1 × e−(7.19 ...×10 cm)×(850 cm )
−4 −1

+ 5 × e−(7.19 ...×10
−4
cm)×(1100 cm−1 )

= 3 + 0.542... + 2.26... = 5.809 (��.�)

�e population of level i with degeneracy g i is N i = (N g i �q)e−βε i , therefore

the relative populations of the levels are proportional to g i e−βε i , which are the
terms in eqn ��.�. �us the populations, relative the ground state are

N 0 �N 0 ∶ N 1 �N 0 ∶ N 2 �N 0 = 3�3 ∶ (0.542...�3) ∶ (2.26...�3)

= 1 ∶ 0.181 ∶ 0.755

P��B.� �e vibrational partition function is given by [��B.��–���], q V = 1�(1−e−β hc ν̃ ),

where β = 1�kT and ν̃ is the wavenumber of the vibration. �e high-temperature
approximation is given by [��B.��–���], qHT V
= kT�hc ν̃. If the characteristic
vibrational temperature θ is de�ned as θ V = hc ν̃�k, the two forms of the
V

partition function become

1 T
qV = q VHT =
1 − e−θ V �T θV
 Plotting these as a function of T�θ V gives a universal curve which applies to all
vibrational wavenumbers; such a plot is shown in Fig ��.�. �e high-temperature
value is within ��% of the exact value when

(q V − q VHT )�q V = 0.1

�ere is no analytical solution for the value of T�θ V which solves this equation.
However, by plotting the fraction on the le� against T�θ V , it is easy to see that
this ��% deviation is reached when T�θ V ≈ 4.7

10 exact
high temperature
qV

0
0 2 4 6 8 10
V
T�θ

P��B.� �e translational partition function for a particle in a one-dimensional box of

width X is given by [��B.�–���], q XT = X�Λ where Λ = h�(2πmkT)1�2 . �is
expression is rearranged to give the temperature in terms of Λ, and then in
terms of q XT
h2 h 2 (q XT )2
T= =
2πmkΛ 2 2πmkX 2
�e expression is further developed using m = M�N A and k = R�N A , and then
evaluated for the given data and q XT = 10

N A2 h 2 (q XT )2
T=
2πMRX 2
(6.0221 × 1023 mol−1 )2 × (6.6261 × 10−34 J s)2 × (10)2
=
2π × (1.008 × 10−3 kg mol−1 ) × (8.3145 J K−1 mol−1 )
1
×
(100 × 10−9 m)2
= 0.0302... K = �.��� K .

As explained in Section ��B.�(a) on page ���, the exact partition function is

given as q XT = ∑∞
n=1 e
−(n 2 −1)βε
, where ε = h 2 �8mX 2 and β = 1�kT. For the
 given data βε is evaluated at the above temperature as

h2 h 2 N A2
βε = =
8mkT X 2 8MRT X 2
(6.0221 × 1023 mol−1 )2 × (6.6261 × 10−34 J s)2
=
8 × (1.008 × 10−3 kg mol−1 ) × (8.3145 J K−1 mol−1 )
1
× = 0.00785...
(0.0302... K) × (100 × 10−9 m)2

With this value the partition function is then evaluated term by term to give
∞
q XT = � e−(n −1)βε
= 1 + e−3βε + e−8βε + e−15βε + ...
2

n=1
= 1 + 0.977... + 0.939... + 0.889... + ... = �.��

Even under these conditions, the integral approximation deviates by less than
�% from the explicit sum.

P��B.� �e partition function is given by [��B.�b–���], q = ∑ i g i e−βε i , where g i is

degeneracy and the corresponding energy is given as ε i = hc ν̃ i , and β = 1�kT.
Here g i = 2J + 1, where J is the right subscript in the term symbol. At 3287 ○ C,
which is 3556 K
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
hcβ = = 4.04... × 10−4 cm
(1.3806 × 10−23 J K−1 ) × (3556 K)

�erefore the electronic partition function is

q E = 5 + 7 × e−(4.04 ...×10 cm)×(170 cm )

−4 −1

+ 9 × e−(4.04 ...×10 cm)×(387 cm ) + 3 × e−(4.04 ...×10

−4 −1 −4
cm)×(6557 cm−1 )

= 5 + 6.53... + 7.69... + 0.211... = 19.4....

�e population of level i is N i �N = (g i × e−hc β ν̃ i )�q E . �us

N(3 F2 ) 5 N(3 F3 ) 6.53...

= = �.��� = = �.���
N 19.4... N 19.4...
N(3 F4 ) 7.69... N(5 F1 ) 0.211...
= = �.��� = = �.����
N 19.4... N 19.4...

P��B.� �e wavenumbers of the lines in the pure rotational spectrum of a diatomic

are given by [��B.��a–���], ν̃(J + 1 ← J) = 2B̃(J + 1). �erefore a plot of
ν̃(J + 1 ← J) against 2(J + 1) is expected to be a straight line with slope B̃. �e
separation of successive lines is 2B̃, and from the �rst few lines a consistent
value of B̃ ≈ 10.6 cm−1 is found. Using this, the assignment of the lines is
con�rmed as 1 ← 0 for that at ��.�� cm−1 , and 2 ← 1 for that at ��.�� cm−1 .
�e given lines are therefore successive members of ν̃(J + 1 ← J) starting from
 J = 0. With the lines assigned the plot can be made and indeed it is a very good
straight line whose slope gives B̃ = 10.593 cm−1 .
�e rotational partition function of a heteronuclear diatomic is given by [��B.��–
���], q R = ∑ J (2J + 1)e−β hc B̃ J(J+1) . At 25 ○ C, kT�hc = 207.225 cm−1 .

βhc B̃ = (10.593 cm−1 )�(207.225 cm−1 ) = 5.11... × 10−2

Evaluating the sum term by term gives q R =��.�� ; the terms with J > 14 do not
contribute signi�cantly.

P��B.�� �e partition function is given by [��B.�a–���], q = ∑ i e−βε i , where the energy

of state i is given as ε i = hc ν̃ i , and β = 1�kT.
q V = 1 + e−hc β ν̃ 1 + e−hc β ν̃ 2 + e−hc β ν̃ 3 + e−hc β ν̃ 4

�e population of state i is N i �N = e−hc ν̃ i �(k T) �q V

(a) At T = 100 K
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
hcβ = = 1.43... × 10−2 cm
(1.3806 × 10−23 J K−1 ) × (100 K)

q V = 1 + e−(1.43 ...×10 cm)×(215.30 cm ) + e−(1.43 ...×10 cm)×(425.39 cm )

−2 −1 −2 −1

+ e−(1.43 ...×10 cm)×(636.27 cm ) + e−(1.43 ...×10 cm)×(845.93 cm )

−2 −1 −2 −1

= 1 + 0.0451... + 2.19... × 10−3 + 1.05... × 10−4 + 5.17... × 10−6

= 1.04... = �.��

N 0 �N = 1�1.04... = �.���
N 1 �N = 0.0451...�1.04... = 4.31 × 10−2
N 2 �N = (2.19... × 10−3 )�1.04... = 2.10 × 10−3

(b) At T = 298 K
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
hcβ = = 4.82... × 10−3 cm
(1.3806 × 10−23 J K−1 ) × (298 K)

q V = 1 + e−(4.82 ...×10 cm)×(215.30 cm ) + e−(4.82 ...×10 cm)×(425.39 cm )

−3 −1 −3 −1

+ e−(4.82 ...×10 cm)×(636.27 cm ) + e−(4.82 ...×10 cm)×(845.93 cm )

−3 −1 −3 −1

= 1 + 0.353... + 0.128... + 4.63... × 10−2 + 1.68... × 10−2

= 1.54... = �.��

N 0 �N = 1�1.54... = �.���
N 1 �N = 0.353...�1.54... = �.���
N 2 �N = 0.128...�1.54... = 8.30 × 10−2
D��C.� �is is described in Brief illustration ��C.� on page ���.

E��C.�(b) �e mean energy of a molecule is given by [��C.�–���], �ε� = (1�q) ∑ i ε i e−βε i ,

where ε i = hc ν̃ i , β = 1�kT, and q is the partition function given by [��A.��–
���], q = ∑ i e−βε i . �erefore for the two-level system

0 + εe−βε ε hc ν̃
�ε� = = βε =
1 + e−βε e + 1 e hc ν̃�k T + 1
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (600 cm−1 )
=
e (6.6261×10 (1.3806×10
J s)×(2.9979×10 cm s )×(600 cm −1 )
+1
−34 10 −1
−23 J K−1 )×(400 K)

= 1.23 × 10 −21
J

E��C.�(b) �e mean molecular energy is given by [��C.�a–���], �ε� = −(1�q)(∂q�∂β)V ,

where β = 1�kT and q is the partition function. �e rotational partition func-
tion of a heteronuclear diatomic is given in terms of the rotational constant B̃
by [��B.��–���], q R = ∑ J (2J + 1)e−β hc B̃ J(J+1) .

1 ∂q R 1
�ε R � = − � � = � hc B̃J(J + 1)(2J + 1)e
−β hc B̃ J(J+1)
q R ∂β V q R J

�e terms of the sum above and also of the sum needed to compute q R are
evaluated and summed until the result has converged to the required precision.
�e equipartition value is �ε R � = kT. �ese two expressions for the energy are
plotted as a function of T in Fig. ��.�. �e value from the equipartition theorem
comes within � % of the exact value at 66.2 K .

E��C.�(b) �e mean molecular energy is given by [��C.�a–���], �ε� = −(1�q)(∂q�∂β)V ,

where β = 1�kT, and q is the partition function given by [��B.�b–���], q R =
∑ J g J e−βε J . �e energy levels of a spherical rotor are given in [��B.�–���], ε J =
hc B̃J(J + 1) and, as is explained in Section ��B.�(c) on page ���, each has a
degeneracy g J = (2J + 1)2 . It follows that

q R = �(2J + 1)2 e−β hc B̃ J(J+1)

J

1 ∂q R 1
�ε R � = − � � = � hc B̃J(J + 1)(2J + 1) e
2 −β hc B̃ J(J+1)
q R ∂β V q R J

�e terms in the sum needed to compute q R and �ε R � are evaluated and summed
until the result has converged to the required precision. �e equipartition value
 8

�ε R � × 1022 �J
6

2 exact
equipartition
0
0 10 20 30 40 50 60 70
T�K

6
�ε R � × 1024 �J

2
exact
equipartition
0
0.0 0.1 0.2 0.3 0.4
T�K

is �ε R � = 32 kT, because for this non-linear molecule there are three rotational
degrees of freedom. �ese two expressions for the energy are plotted as a func-
tion of T in Fig. ��.�. �e value from the equipartition theorem comes within
� % of the exact value at 0.29 K .

E��C.�(b) �e mean vibrational energy is given by [��C.�–���], �ε V � = hc ν̃�(e β hc ν̃ − 1);

this result is exact. �e equipartition value is �ε V � = kT, because there are two
quadratic terms for a harmonic oscillator. �ese two expressions for the energy
are plotted as a function of T in Fig. ��.�. �e value from the equipartition
theorem comes within � % of the exact value at 3.19 × 103 K .

E��C.�(b) �e mean vibrational energy per vibrational mode is given by [��C.�–���], �ε Vi � =

hc ν̃ i �(e β hc ν̃ i −1); this result is exact. �e overall vibrational energy is the sum of
the contributions from each normal mode, taking into account the degeneracy
 4

�ε V � × 1020 �J
2

exact
equipartition
0
0 500 1 000 1 500 2 000 2 500 3 000 3 500
T�K

of each

�ε V � = �ε V1 � + 2 × �ε V2 � + �ε V3 �

�e equipartition value is �ε V � = 4kT, because there are two quadratic terms

for a harmonic oscillator, and four modes in total. �ese two expressions for the
energy are plotted as a function of T in Fig. ��.�. �e value from the equiparti-
tion theorem comes within �% of the exact value at 2.52 × 104 K .

150
�ε V � × 1020 �J

100

50
exact
equipartition
0
0 5 000 10 000 15 000 20 000 25 000 30 000
T�K

E��C.�(b) �e mean vibrational energy per vibrational mode is given by [��C.�–���], �ε Vi � =

hc ν̃ i �(e β hc ν̃ i −1); this result is exact. �e overall vibrational energy is the sum of
the contributions from each normal mode, taking into account the degeneracy
of each

�ε V � = �ε V1 � + 2 × �ε V2 � + 3 × �ε V3 � + 3 × �ε V4 �
 �e equipartition value is �ε V � = 9kT, because there are two quadratic terms
for a harmonic oscillator, and nine modes in total. �ese two expressions for
the energy are plotted as a function of T in Fig. ��.�. �e value from the equipar-
tition theorem comes within �% of the exact value at 3.92 × 103 K .

40.0
�ε V � × 1020 �J

20.0

exact
equipartition
0.0
0 1 000 2 000 3 000 4 000
T�K

E��C.�(b) �e mean molecular energy is given by [��C.�a–���], �ε� = −(1�q)(∂q�∂β)V ,

where β = 1�kT and q is the partition function given by [��B.�b–���], q =
∑ i g i e−βε i , where g i is degeneracy and the corresponding energy is given as
ε i = hc ν̃ i . At T = 2000 K
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
βhc = = 7.19... × 10−4 cm
(1.3806 × 10−23 J K−1 ) × (1900 K)
�erefore the electronic partition function is
q E = g 0 + g 1 e−β hc ν̃ 1 + g 2 e−β hc ν̃ 2 = 5.80...
�erefore the mean energy is
1 ∂q E hc
�ε E � = − � � = �g 1 ν̃ 1 e−β hc ν̃ 1 + g 2 ν̃ 2 e−β hc ν̃ 2 �
q E ∂β V q E
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
=
5.80...
× �1 × (850 cm−1 ) × e−(7.19 ...×10 cm)×(850 cm )
−4 −1

+5 × (1100 cm−1 ) × e−(7.19 ...×10 �

−4
cm)×(1100 cm−1 )

= 1.01 × 10−20 J

P��C.� �e mean molecular energy is given by [��C.�–���], �ε� = (1�q) ∑ i ε i e−βε i ,

where β = 1�kT, and q is the partition function given by [��A.��–���], q =
 ∑ i e−βε i . �erefore

q = e−β0 + e−βε + e−β2ε = 1 + e−βε + e−β2ε

1 εe−βε + 2εe−2βε
�ε� = �0 + εe−βε + 2εe−β2ε � =
q 1 + e−βε + e−2βε
e βε + 2
= ε� �
e2βε + e βε + 1

To go to the last line the denominator and numerator of the fraction have both
been multiplied by e2βε .

P��C.� �e equipartition limit for the vibrational energy is kT. Consider

kT − �ε V �
= 0.02
�ε V �
hc ν̃
kT = 1.02 × �ε V � = 1.02 ×
e β hc ν̃ − 1
Because β = 1�kT it follows that

e β hc ν̃ − 1 = 1.02 × βhc ν̃

Using the Taylor expansion ex = 1 + x + 12 x 2 + 16 x 3 + ... and x = βhc ν̃

�1 + x + 12 x 2 + 16 x 3 + ...� − 1 = 1.02 × x
x + 12 x 2 + 16 x 3 + ... = 1.02 × x

For high temperature limit x � 1 is assumed, thus expansion terms a�er x 3

are ignored
x 3 + 3x 2 − 0.12x = 0
�is equation has three solutions
√
−3 +
9 + 4 × 0.12
x1 = = 0.0394...
√ 2
−3 − 9 + 4 × 0.12
x2 = = −3.03... x3 = 0
2
Only the postive root is physically meaningful, thus

hc ν̃ (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )

T= = × ν̃
kx (1.3806 × 10−23 J K−1 ) × (0.0394...)
= (36.4 K cm) × ν̃
P��C.� �e partition function given by [��B.�b–���], q = ∑ i g i e−βε i , where g i is de-
generacy. �e energy is given as E nl = kθ X nl 2
, where θ is the characteristic
temperature, θ = ħ �2m e R k. Taking E 1,0 as the ground state
2 2

q = � g l e−βε nl = � (2l + 1)e−β(E nl −E 1,0 )

levels levels

= � (2l + 1)e −(θ�T)×(X nl −X 1,0 )

2 2

levels

Relevant values are tabulated below and using these the sum is computed nu-
merically to give the plot shown in Fig. ��.��.

n � � � � � �
l � � � � � �
X nl �.��� �.��� �.��� �.��� �.��� �.���
gl � � � � � �
X nl 2 �.�� ��.�� ��.�� ��.�� ��.�� ��.��
X nl 2 − X 1,0 2 �.�� ��.�� ��.�� ��.�� ��.�� ��.��

8.0

6.0

4.0
q

2.0

0.0
0 5 10 15 20 25
T�θ

�e mean energy is given by [��C.�a–���], �ε� = ε gs − (1�q) �∂q�∂β�V . �ere-

fore
1
�ε� − E 1,0 = � (2l + 1)e
−β(E nl −E 1,0 )
× (E nl − E 1,0 )
q levels
kθ
= � (2l + 1)e
−(θ�T)×(X nl −X 1,0 )
× (X nl − X 12 0 )
2 2
2
q levels

�is quantity is plotted in Fig. ��.��.

 20

(�ε� − E 1,0 ) �kθ

15

10

0
0 5 10 15 20 25
T�θ

P��C.� (a) �e mean molecular energy is given by [��C.�a–���]

�ε� = −(1�q)(∂q�∂β)V
where β = 1�kT and q is the partition function given by [��A.��–���],
q = ∑ i e−βε i . For the uniformly spaced set of energy levels, ε j = jε, the
partition function is given by [��B.�a–���], q = ∑ j e−β jε = 1�(1 − e−βε ).
With these results the mean energy is calculated as
1 dq −εe−βε
�ε� = − = −(1 − e−βε )
q dβ (1 − e−βε )2
εe−βε ε
= = βε
(1 − e ) (e − 1)
−βε

Setting �ε� = aε
aε = ε�(e βε − 1)
e βε = 1 + 1�a
1 1
thus β = ln �1 + �
ε a
Given �ε� = ε, it follows that a = 1. Because T = 1�kβ and ε = hc ν̃
ε hc ν̃
T= =
k ln(2) k ln(2)
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (50 cm−1 )
=
(1.3806 × 10−23 J K−1 ) × ln(2)
= 1.0 × 102 K
(b) If �ε� = aε it follows from the above discussion that βε = ln(1 + 1�a),
therefore
1 1 1
q= = = = a+1
1 − e−βε 1 − e− ln(1+1�a) 1 − a�(a + 1)
D��D.� An ensemble is a set of a large number of imaginary replications of the actual
system. �ese replications are identical in some, but not all, respects. For
example, in the canonical ensemble, all replications have the same number of
particles, the same volume, and the same temperature, but they need not have
the same energy.
Ensembles are useful in statistical thermodynamics because it is mathemati-
cally more tractable to perform an ensemble average to determine the (time
averaged) thermodynamic properties than it is to perform an average over time
to determine these properties. Recall that macroscopic thermodynamic prop-
erties are averages over the time dependent properties of the particles that com-
pose the macroscopic system. In fact, it is taken as a fundamental principle
of statistical thermodynamics that the (su�ciently long) time average of every
physical observable is equal to its ensemble average. �is principle is connected
to a famous assumption of Boltzmann’s called the ergodic hypothesis.

D��D.� In the context of ensembles, the thermodynamic limit is achieved as the num-
ber of replications Ñ approaches in�nity. In this limit, the dominating con�g-
uration is overwhelmingly the most probable con�guration, and its properties
are essentially the same as those of the system.

E��D.�(b) It is essential to include the factor 1�N! when considering indistinguishable

particles which are free to move. �us, such a factor is always needed for gases.
In the solid state, particles are distinguished by their positions in the lattice and
therefore the particles are regarded as distinguishable on the basis that their
locations are distinguishable. For the cases mentioned, the factor 1�N! is only
needed for CO� gas: all the others materials are solids, for which the factor is
not needed.

P��D.� �e mean energy of a system is given by [��D.�–���], �E� = − (∂ ln Q�∂β)V .

Using this expression for �E� the required derivative is found by changing the
order of the mixed partial derivatives

∂�E� ∂ ∂ ln Q ∂ ∂ ln Q
� � = −� � � � = −� � � �
∂V T ∂V ∂β V T ∂β ∂V T V

A perfect gas is a collection of indistinguishable independent molecules, thus

its canonical partition function is given by [��D.�b–���], Q = q N �N!, where q
is the molecular partition function. For a perfect gas q is just the translational
partition function given by [��B.��b–���], q T = V �Λ 3 , where Λ is the thermal
 wavelength, which is independent of volume. With these results the derivative
of Q is developed as follows

∂ ln Q ∂ ln(q N �N!) ∂(N ln q − ln N!)

� � =� � =� �
∂V T ∂V T
∂V T
∂ ln q ∂ ln(V �Λ 3 ) ∂ ln V N
=N� � =N� � =N� � =
∂V T ∂V T
∂V T V

At constant V , N�V does not depend on β thus

∂�E� ∂ ∂ ln Q ∂N�V
� � = −� � � � = −� � =0
∂V T ∂β ∂V T V ∂β V

D��E.� �e expressions for q, U, and S that have been derived are applicable to T < 0
as well as T > �. However, if a plot of q or U against T is made (for example, for
a two-level system), sharp discontinuities on passing through zero are found. It
is seen that T = +0 (corresponding to only the lower state being populated) is
quite distinct from T = −0, when only the upper state is populated. �e entropy
S is continuous at T = 0, but all these functions are continuous if β = 1�kT is
used as the independent variable. �is indicates that β ∝ 1�T may be a more
natural variable than T.

D��E.� �is is discussed in Section ��D.� on page ��� and the consequences for the
calculation of the entropy are further explored in Section ��E.�(a) on page ���.

D��E.� �is is discussed in Section ��E.�(e) on page ���.

E��E.�(b) �e equipartition value for C V ,m is expressed in [��E.�–���]: each transla-

tional or rotational mode contributes 12 R, and each active vibrational mode
contributes R.
(i) O� : three translational modes, three rotational modes (non-linear), and
no active vibrational modes: C V ,m �R = 3 × 12 + 3 × 12 = 3 .
(ii) C� H� : three translational modes, three rotational modes (non-linear),
and no active vibrational modes: C V ,m �R = 3× 12 +3× 12 = 3 . �ere is one
low-frequency normal mode which, if active, will contribute a further R.
(iii) CO� : three translational modes, two rotational modes (linear), and no
active vibrational modes: C V ,m �R = 3 × 12 + 2 × 12 = 52 .
E��E.�(b) �e equipartition value for C V ,m is expressed in [��E.�–���]: each transla-
tional or rotational mode contributes 12 R, and each active vibrational mode
contributes R. �e number of vibrational modes for a linear molecule is (3N −
5), which is � for CO� �is molecule has three translational modes, and two
rotational modes (linear) giving C V ,m = 52 R; if the � vibrations are included,
C V ,m = 13
2
R.
γ = C p,m �C V ,m = (C V ,m + R)�C V ,m = 1 + R�C V ,m
γ = 1 + R�(5R�2) = 1.40 no vibrational contribution
γ = 1 + R�(13R�2) = 1.15 with vibrational contribution
�e experimental value for γ is �.��; evidently the vibrational modes contribute
to some small extent.

E��E.�(b) �e partition function of this two-level system is

q = g 0 + g 1 e−β hc ν̃
where g 0 and g 1 are the degeneracies of the ground and �rst excited state,
respectively. �e mean energy is given by [��C.�a–���], �ε� = −(1�q)(∂q�∂β)V
g 1 hc ν̃ e−β hc ν̃ g 1 hc ν̃
�ε� = =
g 0 + g 1 e−β hc ν̃ g 0 e β hc ν̃ + g 1
N A g 1 hc ν̃
hence U m = N A �ε� =
g 0 e β hc ν̃ + g 1
By de�nition C V ,m = (∂U m �∂T)V , therefore
∂U m ∂U m dβ ∂U m −1
C V ,m = � � =� � =� � ×
∂T V ∂β V dT ∂β V kT 2
1 g 0 hc ν̃e β hc ν̃
= × N A g 1 hc ν̃
kT 2 (g 0 e β hc ν̃ + g 1 )2
N A (hc ν̃)2 g 0 g 1 e β hc ν̃
=
kT 2 (g 0 e β hc ν̃ + g 1 )2

In this case g 0 = 3 and g 1 = 2. With the data given

hc ν̃ = (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (7918.1 cm−1 )
= 1.57... × 10−19 J
at ��� K βhc ν̃ = hc ν̃�kT
= (1.57... × 10−19 J)�[(1.3806 × 10−23 J K−1 ) × (400 K)] = 28.4...

N A (hc ν̃)2 6 e β hc ν̃
C V ,m =
kT 2 (3 e β hc ν̃ + 2)2
(6.0221 × 1023 mol−1 )×(1.57... × 10−19 J)2 6 e28.4 ...
=
(1.3806 × 10−23 J K−1 ) × (400 K)2 (3 e28.4 ... + 2)2
= 1.92 × 10−9 J K−1 mol−1
 Because hc ν̃ � kT only the ground state is occupied and there is essentially no
electronic contribution to the heat capacity.

E��E.�(b) �e contribution of a collection of harmonic oscillators to the standard molar

entropy is given by [��E.��b–���] (note that there is an error in the expression
in the text: the argument of the exponential term in the ln should be negative)

θ V �T
= R� − ln(1 − e−θ �T )� θ V = hc ν̃�k
V
V
Sm
eθ V �T−1

�is function is plotted in Fig ��.��.

�e following table shows the vibrational temperatures and the contribution to
the molar entropy for each of the normal modes

��� K ��� K
ν̃�cm−1 θ V �K T�θ V V
Sm �R T�θ V SmV
�R
��� ��� �.��� �.��� �.��� �.���
��� ���� �.��� �.��� �.��� �.���
���� ���� �.���� 7.642 × 10−4 �.���� �.�����
���� ���� �.����� 2.161 × 10−6 �.���� 8.158 × 10−4
���� ���� �.����� 1.455 × 10−6 �.���� 6.503 × 10−4

�e molar entropy is obtained by summing the contributions from each normal

mode, taking into account the double degeneracy of the modes at ��� cm−1 and
��� cm−1 by counting each twice. �us at ��� K S mV
= 5.88 J K−1 mol−1 and at
V
��� K S m = 16.5 J K−1 mol−1 .

2
Sm
V
�R

0
0 1 2 3 4 5
V
T�θ
E��E.�(b) �e translational contribution to the standard molar entropy is given by the
Sackur–Tetrode equation [��E.�b–���]

kTe5�2
−
○
Sm = R ln � � Λ = h�(2πmkT)1�2
p−○ Λ 3

(i) Taking the mass of H� O as 18.016 m u

6.6261 × 10−34 J s
Λ=
�2π(18.016×1.6605 × 10−27 kg)×(1.3806 × 10−23 J K−1 )×(298 K)�
1�2

= 5.05 . . . × 10−11 m
(1.3806 × 10−23 J K−1 ) × (298 K) × e5�2
−
○
Sm = (8.3145 J K−1 mol−1 ) × ln � �
(105 N m−2 ) × (5.05 . . . × 10−11 m)3
= ���.� J K−1 mol−1

(ii) Taking the mass of CO� as 44.01 m u

6.6261 × 10−34 J s
Λ=
�2π(44.01×1.6605 × 10−27 kg)×(1.3806 × 10−23 J K−1 )×(298 K)�
1�2

= 1.52 . . . × 10−12 m
(1.3806 × 10−23 J K−1 ) × (298 K) × e5�2
−
○
Sm = (8.3145 J K−1 mol−1 ) × ln � �
(105 N m−2 ) × (1.52 . . . × 10−12 m)3
= ���.� J K−1 mol−1

E��E.�(b) �e translational contribution to the standard molar entropy is given by the

Sackur–Tetrode equation [��E.�b–���]

kTe5�2
−
○
Sm = R ln � � Λ = h�(2πmkT)1�2
p−○ Λ 3

−
○
It follows that S m = A ln(T 5�2 m 3�2 ), where A is a constant. �erefore

−
○
(CO2 , T1 ) − S m
−
○
(H2 O, T2 ) = A ln(T1 m CO2 ) − A ln(T2 m H2 O )
5�2 3�2 5�2 3�2
Sm

−
○
If S m (CO2 , T1 ) = S m
−
○
(H2 O, 298)

0 = A ln[T1 m CO2 ] − A ln[(298 K)5�2 m H2 O ]

5�2 3�2 3�2

hence T1 m CO2 = (298 K)5�2 m H2 O

5�2 3�2 3�2

(298 K)5�2 × (18.016)3�2

2�5
T1 = � � = ��� K
(44.01)3�2
E��E.�(b) �e rotational partition function for a non-linear molecule is given by [��B.��–
���]
1 kT 3�2 π 1�2
qR = � � � �
σ hc ÃB̃C̃
For SO� the symmetry factor σ = 2, the same value as for H� O. At ��� K
(1.3806 × 10−23 J K−1 ) × (298 K)
kT�hc =
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
= 207.1... cm−1
q R = 12 (207.1... cm−1 )3�2 ×
1�2
π
� �
(2.02736 cm ) × (0.34417 cm−1 ) × (0.293535 cm−1 )
−1

= ����
�e entropy is given in terms of the partition function by [��E.�a–���]
S m = [U m (T) − U m (0)]�T + R ln q
�is is the appropriate form for the rotational contribution; for the translational
contribution the ln term is ln qe�N. At ��� K kT�hc = 207 cm−1 which is signif-
icantly greater than any of the rotational constants, therefore the equipartition
theorem can be used to �nd U m (T): there are three rotational modes, therefore
U m (T) − U m (0) = 32 RT.
R
Sm = ( 32 RT)�T + R ln q R = R( 23 + ln q R )
= (8.3145 J K−1 mol−1 ) × [ 32 + ln(5837)]
= ��.�� J K−1 mol−1

E��E.�(b) Only the ground electronic state contributes to the electronic partition func-
tion, which is therefore simply the degeneracy of the ground state q E = g 0 . �e
spin degeneracy is given by the value of S: g 0 = (2S + 1) = (2 × 52 + 1) = 6. �e
entropy is given in terms of the partition function by [��E.�a–���]
S m = [U m (T) − U m (0)]�T + R ln q
�is is the appropriate form for the electronic contribution; for the translational
contribution the ln term is ln qe�N. In this case U m (T) − U m (0) = 0 as only
the ground state is considered

S m = R ln q = R ln 6 = ��.�� J K−1 mol−1

E��E.�(b) �e contribution of a collection of harmonic oscillators to the standard molar

entropy is given by [��E.��b–���] (note that there is an error in the expression
in the text: the argument of the exponential term in the ln should be negative)
θ V �T
= R� − ln(1 − e−θ �T )� θ V = hc ν̃�k
V
V
Sm
e θ V �T
−1
 �e following table shows the vibrational temperatures and the contribution to
the molar entropy for each of the normal modes

��� K ��� K
ν̃�cm −1
θ �K
V
θ �T
V
SmV
�R θ �T
V
SmV
�R
��� ��� �.�� �.��� �.�� �.���
��� ���� �.�� �.��� �.�� �.���
���� ���� �.��� 7.643 × 10−4 �.��� �.�����
���� ���� ��.�� 2.161 × 10−6 �.��� 8.158 × 10−4
���� ���� ��.�� 1.455 × 10−6 �.��� 6.503 × 10−4

�e molar entropy is obtained by summing the contributions from each normal

mode, taking into account the double degeneracy of the modes at ��� cm−1 and
��� cm−1 by counting each twice. �us at ��� K S mV
= 5.88 J K−1 mol−1 and at
V
��� K S m = 16.5 J K−1 mol−1 .

P��E.� �e unpaired electron in NO� will interact with the magnetic �eld and give
rise to two energy levels, corresponding to the spin-up and spin-down states.
�erefore, these electron spin levels form a two-level system, an expression for
the heat capacity of which is derived in the solution to Exercise E��E.�(b).

N A (hc ν̃)2 g 0 g 1 e β hc ν̃
C V ,m =
kT 2 (g 0 e β hc ν̃ + g 1 )2

where g 0 and g 1 are the degeneracies of the ground and �rst excited levels,
respectively, and (hc ν̃) is the energy separation of the two levels.
For a spin both levels are non-degenerate: g 0 = 1 and g 1 = 1. �e energy
levels of a electron spin in a magnetic �eld are given by [��A.��c–���], E m =
g e µ B B0 m, where g e is the g-value of the electron (taken as �), µ B is the Bohr
magneton, B0 is the applied magnetic �eld, and m = ± 21 for the two states. �e
energy separation of the states is therefore E+1�2 − E−1�2 = g e µ B B0 ; this it the
equivalent of the term (hc ν̃) in the above expression, hence

N A (g e µ B B0 )2 e β g e µ B B0 e β g e µ B B0
C V ,m = = N k(βg µ B ) 2
(e β g e µ B B0 + 1)2 (e β g e µ B B0 + 1)2
A e B 0
kT 2

With the data given, and at �� K

βg e µ B B0 = g e µ B B0 �kT
2 × (9.2740 × 10−24 J T−1 ) × (5.0 T)
= = 0.134...
(1.3806 × 10−23 J K−1 ) × (50 K)
e0.134 ...
C V ,m �R = (0.134...)2 0.134 ... = 4.49 × 10−3
(e + 1)2
 A similar calculation at ��� K gives (βg e µ B B0 ) = 0.0225... and a resulting heat
capacity C V ,m �R = 1.27 × 10−4 .
Assuming that vibrations do not contribute, the equipartition value for the heat
capacity of NO� arises from three translational and three rotational modes,
hence C V ,m �R = 3. At �� K the electron spin contribution expressed as a
fraction of the overall heat capacity is 4.49 × 10−3 �3 = 1.50 × 10−3 or �.�� % .
At ��� K the electron spin contribution is 4.2 × 10−3 % of the overall heat
capacity.

P��E.� An expression for the heat capacity of a two-level system is derived in the so-
lution to Exercise E��E.�(b).

N A (hc ν̃)2 g 0 g 1 e β hc ν̃
C V ,m =
kT 2 (g 0 e β hc ν̃ + g 1 )2

where g 0 and g 1 are the degeneracies of the ground and �rst excited levels,
respectively, and (hc ν̃) is the energy separation of the two levels.
For a linear rotor the terms are given by [��B.��–���], F̃(J) = B̃J(J + 1), so the
separation of the J = 0 and J = 2 terms is 6B̃: this is the equivalent of the term
ν̃. �e degeneracy of each level is (2J + 1), so g 0 = 1 and g 2 = 5.
�e heat capacity is therefore

N A (6hc B̃)2 5 e6β hc B̃ 5 e6β hc B̃

C V ,m = = N k(6βhc B̃) 2
(e6β hc B̃ + 5)2 (e6β hc B̃ + 5)2
A
kT 2

With the data given

6βhc B̃ = 6hc B̃�k × T −1

6×(6.6261 × 10−34 J s)×(2.9979 × 1010 cm s−1 )×(60.684 cm−1 )
= ×T −1
1.3806 × 10−23 J K−1
= (525.4... K) × T −1

A plot of C V ,m as a function of T is shown in Fig. ��.��.

P��E.� �e partition function of this two-level system is

q = 1 + e−βδ

where δ is the energy spacing between the two levels and where it is assumed
that both are non-degenerate. �e mean energy is given by [��C.�a–���], �ε� =
−(1�q)(∂q�∂β)V

δ e−βδ δ
�ε� = = βδ
1+e −βδ e +1
NA δ
hence U m = N A �ε� = βδ
e +1
 1.5

1.0
C V ,m �R

0.5

0.0
0 100 200 300 400 500
T�K

�e entropy is given in terms of the partition function by [��E.�a–���]

NA δ
S m = [U m (T) − U m (0)]�T + R ln q = + R ln(1 + e−βδ )
T(e βδ + 1)
δβ
= R� + ln(1 + e−βδ )�
(e βδ + 1)

where N A �T = N A βk = Rβ is used. �e required temperature coe�cient is

found from
dS m dS m dβ dS m −1
= = ×
dT dβ dT dβ kT 2
−R d δβ
= � βδ + ln(1 + e−βδ )�
kT dβ (e + 1)
2

−R −δ 2 βe βδ δ δe−βδ
= � + − �
kT 2 (e βδ + 1)2 (e βδ + 1) 1 + e−βδ
R (δβ)2 e βδ δβ δβe−βδ
= � βδ − + �
T (e + 1)2 (e βδ + 1) 1 + e−βδ
Rk (δβ)2 e βδ δβ δβe−βδ
= (δβ) � βδ − βδ + �
δ (e + 1) 2 (e + 1) 1 + e−βδ

�e �nal line shows that the size of the derivative is scaled by 1�δ, but that the
temperature dependence is a function of the dimensionless parameter βδ. It
is not possible to �nd the maximum value of the derivative analytically, but
by plotting a graph this maximum is easily located at βδ ≈ 3.243, which is
alternatively expressed as kT ≈ δ�3.243.
When kT � δ all of the particles are in the lower level, which can only be
achieved in one way so the contribution to the entropy is zero. When kT � δ
the entropy reaches a limiting value because the populations of the two levels
are equal and no longer changing. In between these two extremes the entropy
 rises, and it makes sense that the rate of change of the entropy is greatest when
kT ≈ δ because this is the temperature at which the population of the upper
level starts to become signi�cant.

P��E.� It will be useful �rst to consider ∂q�∂β

∂
� e j = − � ε je j
−βε −βε
∂β j j

= −(1�β) � βε j e−βε j = −q̇�β

j

Likewise ∂q̇�∂β
∂
� βε j e j = � ε j e j − � βε j e j
−βε −βε 2 −βε
∂β j j j

= q̇�β − (1�β) �(βε j )2 e−βε j = q̇�β − q̈�β

j

In summary
∂q q̇ ∂q̇ q̇ q̈
=− = − (��.�)
∂β β ∂β β β
�e mean energy is given by [��C.�a–���], �ε� = −(1�q)(∂q�∂β)V
1 ∂q 1 q̇
�ε� = − =
q ∂β q β
where the �rst relationship from eqn ��.� is used. �e molar internal energy is
therefore
1 q̇ q̇
U m = N A �ε� = N A = RT
qβ q
where N A �β = N A kT = RT is used.
By de�nition C V ,m = (∂U m �∂T)V . It is convenient to compute the derivative
with respect to β and to use U m = N A q̇�q β.
∂U m ∂U m ∂β ∂U m −1 −N A ∂ q̇
C V ,m = � � =� � =� � × =
∂T V ∂β V ∂T ∂β V kT 2 kT 2 ∂β q β
−N A −q̇ ∂q ∂q̇ 1
= � �q + β � + �
kT 2 (q β)2 ∂β ∂β q β
−N A −q̇ q̇ q̇ q̈ 1
= � �q − β � + � − � �
kT (q β)
2 2 β β β qβ
−N A −q̇ q̇ 2 q̇ q̈
= � 2+ + − �
kT q β
2 (q β)2 q β 2 q β 2
q̇ 2 q̈
= −Rβ 2 � − �
(q β)2 q β 2
� 2�
� q̈ q̇ �
= R�
�q −� � �
� q � �
� �
 On the penultimate line N A �kT 2 = N A kβ 2 = Rβ 2 is used.
�e molar entropy is given by [��E.�a–���]

S m = [U m (T) − U m (0)]�T + R ln q
q̇
= R � + ln q�
q

To use the data given, account needs to be taken of the degeneracies and it is
convenient to write the energies in terms of wavenumbers to give

q = � g j e−hc β ν̃ j q̇ = βhc � g j ν̃ j e−hc β ν̃ j q̈ = β 2 h 2 c 2 � g j ν̃ 2j e−hc β ν̃ j

j j j

At ���� K

(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )

hc�kT = = 2.87... × 10−4 cm
(1.3806 × 10−23 J K−1 ) × (5000 K)

term g ν̃�cm−1 hcβ ν̃ ge−hc β ν̃ hcβ ν̃ge−hc β ν̃ (hcβ ν̃)2 ge−hc β ν̃

1
S0 � � � � � �
3
P0 � ����� �.���� 1.8591 × 10 −3
�.����� �.�����
3
P1 � ����� �.���� 5.5453 × 10−3 �.����� �.�����
3
P2 � ����� �.���� 9.1337 × 10 −3
�.����� �.�����
1
P1 � ����� ��.��� 1.2492 × 10 −4
1.260 × 10 −3
�.�����
3
S1 � ����� ��.��� 2.1308 × 10 −5
2.526 × 10 −4
2.9946 × 10−3

�e sum of the terms in the ��h column is q, the sixth is q̇, and the seventh is
q̈
q = 1.016 684 q̇ = 0.105 691 q̈ = 0.671 954

� 2�
� q̈ q̇ �
= R� −� � �
�
q �
C V ,m
�q �
� �
0.671954 0.105690 2
= (8.3145 J K−1 mol−1 ) × � −� � �
1.016684 1.016684
= �.�� J K−1 mol−1

P��E.�� Contributions to the entropy from translation and rotation are expected, along
with a smaller contribution from vibration. N� has a 1 Σ ground electronic state
which is non-degenerate and so makes no contribution to the entropy.
 �e translational contribution to the standard molar entropy is given by the
Sackur–Tetrode equation [��E.�b–���]

kTe5�2
T
Sm = R ln � � Λ = h�(2πmkT)1�2
p−○ Λ 3

Taking the mass of N� as 28.02 m u

6.6261 × 10−34 J s
Λ=
�2π(28.02×1.6605 × 10−27 kg)×(1.3806 × 10−23 J K−1 )×(298 K)�
1�2

= 1.91... × 10−11 m
(1.3806 × 10−23 J K−1 ) × (298 K) × e5�2
T
Sm = (8.3145 J K−1 mol−1 ) × ln � �
(105 N m−2 ) × (1.91... × 10−11 m)3
= 1.50... × 102 J K−1 mol−1

�e rotational contribution to the entropy is given by [��E.��a–���]; this high-

temperature form is applicable at ��� K because this temperature is much higher
than the characteristic rotational temperature, θ R = hc B̃�k = 2.88 K.

kT
R
Sm = R �1 + ln �
σ hc B̃
= (8.3145 J K−1 mol−1 ) × �1+
(1.3806 × 10−23 J K−1 ) × (298 K)
ln �
2(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (1.9987 cm−1 )
= 41.1... J K−1 mol−1

�e characteristic vibrational temperature is θ V = hc ν̃�k = 3392 K. �is is

so much greater than ��� K that it may safely be assumed that the vibrational
contribution is negligible at this temperature (a calculation using [��E.��b–���]
V
gives S m ≈ 0.001 J K−1 mol−1 , con�rming that validity of this assumption). �e
molar entropy is therefore

−
○
Sm = Sm
T
+ Sm
R
= 1.50... × 102 + 41.1... = ���.� J K−1 mol−1

�e calculated and experimental values agree to within �.�%, so it can be con-

cluded that there is no residual entropy in the solid at � K.

P��E.�� (a) �e probability distribution over the rotational states is given by

nJ 1
P(J) = = (2J + 1)e−hc B̃ J(J+1)�k T q R = kT�hc B̃
N qR

�e high-temperature form of q R is appropriate because θ R = 2.78 K,

which is much less than the lowest temperature to be explored. Figure ��.��
shows plots of P(J) for ��� K and ���� K. In both cases it is seen that the
 0.15
���� K
��� K
0.10

P(J)

0.05

0.00
0 10 20 30 40
J

distribution peaks before tailing o�: at the lower temperature the peak
comes at a lower value of J and the distribution is narrower. Even at
the lowest temperature, many states have signi�cant probabilities of being
occupied.
�e probability distribution over the vibrational states is given by

nυ 1 −hc ν̃υ�k T
P(υ) = = e q V = (1 − e−hc ν̃�k T )−1
N qV

Figure ��.�� shows plots of P(υ) for ��� K and ���� K. Because the vi-
brational temperature is so high (θ V = 3122 K) at ��� K only the ground
state is occupied, and even at ���� K there is only a small probability of
the �rst excited state being occupied.

1.0
���� K
0.8 ��� K

0.6
P(υ)

0.4

0.2

0.0
0 1 2
υ

(b) �e rotational partition function of a heteronuclear diatomic is given by

[��B.��–���], q R = ∑ J (2J + 1)e−β hc B̃ J(J+1) . �is expression can be written
 in terms of the vibrational temperature θ R = hc B̃�k as

q R = �(2J + 1)e−J(J+1)θ �T
R

In the high-temperature limit this sum is well-approximated by [��B.��a–

���], q R = kT�(hc B̃) = T�θ R . For the data given

(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (1.931 cm−1 )

θR =
1.3806 × 10−23 J K−1
= 2.77... K

�is is much less than even the lowest temperature (��� K) to be consid-
ered, so the high-temperature form of the partition function will give a
precise result. For example, explicit summation at ��� K gives q R = 36.3,
whereas using the high-temperature approximation gives 36.0, an error
of just �.�%. �e error will reduce as the temperature increases.
(c) �e translational contribution to U m will be given by the equipartition
theorem as U mT
= 32 RT, and likewise the rotational contribution (two
rotational modes) is U m R
= RT. �e vibrational contribution must be
calculated explicitly using [��C.�–���]

N A hc ν̃ Rθ V
V
Um = =
e hc ν̃�k T − 1 eθ V �T − 1
�ese three contributions are compared in Fig. ��.��.

translation
[U m (T) − U m (100)]�kJ mol−1

rotation
10 vibration

0
200 400 600 800 1 000
T�K

�e translational and rotational contributions to the heat capacity are

temperature independent because the internal energy is linear in the tem-
perature: C VT ,m = 32 R and C VR ,m = R. �e vibrational contribution to the
heat capacity is given by [��E.�–���]

θ V � e−θ �2T �
2 V 2

C VV ,m = R� �
T � 1 − e−θ �T �
V
 2.0
translation
rotation
1.5
C V ,m �R vibration

1.0

0.5

0.0
200 400 600 800 1 000
T�K

�ese three contributions are compared in Fig. ��.��.

�e translational contribution to the standard molar entropy is given by
the Sackur–Tetrode equation [��E.�b–���]

kTe5�2
T
Sm = R ln � � Λ = h�(2πmkT)1�2
p−○ Λ 3

Taking the mass of CO as 28.01 m u and inserting the values of the other
constants gives
T
Sm �R = ln[(46.8... K−5�2 )T 5�2 ]
�e rotational contribution to the entropy is given by [��E.��a–���] with
σ =1
kT T
R
Sm �R = 1 + ln = 1 + ln R
hc B̃ θ
�e vibrational contribution to the standard molar entropy is given by
[��E.��b–���] (note that there is an error in the expression in the text:
the argument of the exponential term in the ln should be negative)

θ V �T
�R = − ln(1 − e−θ �T )
V
V
Sm
e θ V �T
−1
�ese three contributions are compared in Fig. ��.��.

P��E.�� �e partition function for a two-level system with energy spacing ε is

q = 1 + e−βε

An expression for the internal energy is given in Brief illustration ��C.� on page
���
NA ε
U m = βε
e +1
 translation
rotation

[S m (T) − S m (100)]�R
40
vibration

20

0
200 400 600 800 1 000
T�K

and hence the molar entropy is give by [��E.�a–���]

S m = U m �T + R ln q
NA ε
= + R ln(1 + e−βε )
T(e βε + 1)
βε
= R � βε + ln(1 + e−βε )�
e +1
where to go to the last line N A �T = N A kβ = Rβ is used.
Figure ��.�� shows a plot of the molar entropy as a function of βε. In the limit
�βε� → 0, which corresponds to large positive temperatures or large negative
temperatures, the entropy reaches a maximum, corresponding to equal pop-
ulations of the two levels. As βε becomes more positive, corresponding to a
decreasing (but always positive) temperature, the entropy decreases as the pop-
ulations of the levels become more unequal. In the limit βε � 0, corresponding
to a very low positive temperature, only the ground state is populated: this can
only be achieved in one way, therefore the entropy is zero.
As βε becomes more negative, corresponding to a negative temperature which
is increasing towards zero, the entropy decreases as the populations of the lev-
els become more unequal. In the limit βε � 0, corresponding to a negative
temperature with very small magnitude, only the upper state is populated: this
can only be achieved in one way, therefore the entropy is zero.

P��E.�� �e equipartition value for the C V ,m is expressed in [��E.�–���]: each trans-

lational or rotational mode contributes 12 R, and each active vibrational mode
contributes R. Because C p,m − C V ,m = R it follows that

γ = C p,m �C V ,m = (C V ,m + R)�C V ,m = 1 + R�C V ,m

(a) A diatomic has three translational modes, and two rotational modes giv-
ing C V ,m = 52 R. Hence γ = 1+R�(5R�2) = 1.40 and c s = (1.40RT�M)1�2 .
 0.8

0.6

S m �R 0.4

0.2

0.0
−10 −5 0 5 10
βε

(b) �e same calculation applies to a linear triatomic.

(c) For a non-linear triatomic there is one additional rotational mode giving
C V ,m = 3R. Hence γ = 1 + R�(3R) = 4�3 and c s = (3RT�4M)1�2 .

Taking the molar mass of air as ��.� g mol−1 and using the value of γ for a
diatomic gives at ��� K
1.40RT 1�2
cs = � �
M
1.40 × (8.3145 J K−1 mol−1 ) × (298 K)
1�2
=� � = 346 m s−1
29.0 × 10−3 kg mol−1

P��E.�� It is convenient to rewrite the given expression for the energy by multiplying
the numerator and denominator by eε�k T to give
Nε
E=
eε�k T + 1
(a) By de�nition C V ,m = (∂U m �∂T)V . Here U m is E with N = N A therefore
∂ NA ε ε eε�k T NA ε
C V ,m = � � ε�k T =
∂T V e +1 kT 2 (eε�k T + 1)2
ε 2 eε�k T ε 2 eε�k T
= NA k � � = R � �
kT (eε�k T + 1)2 kT (eε�k T + 1)2
Multiplying the numerator and denominator of this expression by e−2ε�k T
gives the required expression.
(b) Figure ��.�� shows a plot of C V ,m as a function of the dimensionless pa-
rameter kT�ε.
(c) �ere is a maximum in the plot but it is not possible to �nd an analytic
expression for its position. Graphical work indicates that the maximum
is at kT�ε = 0.417 .
 0.4

C V ,m �R
0.2

0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
kT�ε

D��F.� �is is discussed in Section ��F.�(c) on page ���.

E��F.�(b) �e Gibbs energy is computed from the partition function using [��F.�–���],
G(T) = G(0) − nRT ln q�N. As usual, the partition function is factored into
separate contributions from translation, rotation and so on. �e factor of 1�N
is usually taken with the translational contribution, so that, for example, the
rotational contribution to the Gibbs energy is −nRT ln q R , or −RT ln q R for the
molar quantity.
�e rotational partition function of a non-linear rotor is given by [��B.��–���],
q R = (1�σ)(kT�hc)3�2 (π�ÃB̃ C̃)1�2 , where σ is the symmetry number. O� has
a twofold axis so σ = 2.

1 kT 3�2 π 1�2
qR = � � � �
2 hc ÃB̃C̃
(1.3806 × 10−23 J K−1 ) × (298. K)
3�2
1
= � �
2 (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
1�2
π
� �
(3.553 cm ) × (0.4452 cm−1 ) × (0.3938 cm−1 )
−1

= 3.34... × 103
R
Gm = −RT ln q R
= −(8.3145 J K−1 mol−1 ) × (298 K) × ln(3.34... × 103 ) = −20.11 kJ mol−1

�e vibrational partition function for each mode is given by [��B.��–���], q V =

 1�(1 − e−β hc ν̃ ), where β = 1�kT.

(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )

hcβ =
(1.3806 × 10−23 J K−1 ) × (298 K)
= 4.82... × 10−3 cm

−1
q V1 = �1 − e−hc β ν̃ 1 �
−1
= �1 − e−(4.82 ...×10 � = 1.00...
−3
cm)×(1110 cm−1 )

−1
q V2 = �1 − e−(4.82 ...×10 � = 1.03...
−3
cm)×(705 cm−1 )

−1
q V3 = �1 − e−(4.82 ...×10 � = 1.00...
−3
cm)×(1042 cm−1 )

q =
V
q V1 × q V2 × q V3 = (1.00...) × (1.03...) × (1.00...) = 1.04...

Hence

V
Gm = −RT ln q V
= −(8.3145 J K−1 mol−1 ) × (298 K) × ln(1.04...) = −0.112 kJ mol−1

E��F.�(b) �e Gibbs energy is computed from the partition function using [��F.�–���],
G(T) = G(0) − nRT ln q�N. As usual, the partition function is factored into
separate contributions from translation, rotation and so on. �e factor of 1�N
is usually taken with the translational contribution, therefore the electronic
contribution to the Gibbs energy is −nRT ln q E , or −RT ln q E for the molar
quantity.
�e electronic partition function of this two-level system is

q E = g 0 + g 1 e−β hc ν̃

where g 0 and g 1 are the degeneracies of the ground and �rst excited state,
respectively. In this case g 0 = 3 and g 1 = 2. With the data given

βhc ν̃ = hc ν̃�kT
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (7918.1 cm−1 )
=
(1.3806 × 10−23 J K−1 ) × (400 K)
= 28.4...
q = 3 + 2e−28.4 ... = 3.00...
E

E
Gm = −(8.3145 J K−1 mol−1 ) × (400 K) × ln(3.00...) = −3.65 kJ mol−1

Because hc ν̃ � kT only the ground state is occupied and essentially only this
state contributes to the Gibbs energy.
E��F.�(b) ⇀ A� + B� is given by [��F.��b–���]
�e equilibrium constant for � AB ���

qA−○2 ,m qB−○2 ,m −∆ r E 0 �RT

K= e
(qAB,m
−
○ )2

where A is ��Br and B is ��Br. It is convenient to consider the contribution of

each mode to the fraction in the above expression separately.

�e standard molar translational partition function is qm−○ = Vm−○ �Λ 3 , with Λ =

h�(2πmkT)1�2 , therefore qm−○ goes as m 3�2 . In the fraction all of the other con-
stants cancel to leave

qA−○ ,m qB−○ ,m
3�2
mA mB
� 2 −○ 2 2 � = � 22 2 �
(qAB,m ) trans m AB

(2 × 78.92) × (2 × 80.92)
3�2
=� � = 0.999...
(78.92 + 80.92)2

For a diatomic the rotational partition function in the high-temperature limit is

given by [��B.��b–���] q R = kT�σ hc B̃ where σ = 1 for heteronuclear and σ = 2
for homonuclear diatomics. �e rotational constant is given by [��B.�–���], B̃ =
ħ�4πcI, with I = µR 2 and µ = m A m B �(m A + m B ). To a good approximation it
can be assumed that the bond length does not vary with isotopic substitution,
so it follows that q R goes as 1�σ B̃ which is as µ�σ. For a homonuclear diatomic,
µ = m�2. In the fraction all of the other constants cancel to leave

qA 2 qB 2 (µ A2 �2)(µ B2 �2) µ A2 µ B2
� � = =
(qAB ) rot
2 [(µ AB �1)]2 2
4µ AB
× 78.92 × 12 × 80.92
1
= 2
= 0.250...
4[(78.92 × 80.92)�(78.92 + 80.92)]2

�e vibrational partition function is given by [��B.��–���] q V = (1−e−hc ν̃�k T )−1 .

�e vibrational frequency goes as (k f �m eff )1�2 where k f is the force constant
and m eff = m A m B �(m A +m B ). To a good approximation it can be assumed that
the force constant does not vary with isotopic substitution, so it follows that for
isotopic species ν̃ A2 �ν̃ AB = (m eff ,AB �m eff ,A2 )1�2 . Applying this expression gives

(78.92 × 80.92)�(78.92 + 80.92)

1�2
ν̃ A2 = (323.22 cm−1 ) � �
1
2
× 78.92
= 325.3... cm−1
(78.92 × 80.92)�(78.92 + 80.92)
1�2
ν̃ B2 = (323.22 cm−1 ) � �
1
2
× 80.92
= 321.3... cm−1
Using these frequencies the vibrational partition functions are evaluated as

(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (323.22 cm−1 )

hc ν̃�kT =
(1.3806 × 10−23 J K−1 ) × (298 K)
= 1.56...
V
qAB = (1 − e−1.56 ... )−1 = 1.26...

and likewise

qAV2 = 1.26... qBV2 = 1.26...

�e fraction for vibration is therefore

qA 2 qB 2 (1.26...) × (1.26...)
� � = = 0.999...
(qAB )2 vib (1.26...)2

�e term ∆ r E 0 is computed as

∆ r E 0 = N A hc(−D̃ 0,A2 − D̃ 0,B2 + 2 D̃ 0,AB )

�e dissociation energy is related to the well depth D̃ e by D̃ 0 = D̃ e − 12 ν̃, where

1
2
ν̃ is the energy of the vibrational ground state. To a good approximation it
can be assumed that D̃ e is una�ected by isotopic substitution, hence

∆ r E 0 = 12 N A hc(ν̃ 0,A2 + ν̃ 0,B2 − 2ν̃ 0,AB )

= 12 (6.0221 × 1023 mol−1 ) × (6.6261 × 10−34 J s)
× (2.9979 × 1010 cm s−1 ) × ([325.3... + 321.3... − 2 × 323.33] cm−1 )
= +1.24... J mol−1

Hence

e−∆ r E 0 �RT = e−(+1.24 ... J mol = 0.999...

−1
)�[(8.3145 J K−1 mol−1 )×(298 K)]

Putting together all of the parts gives the equilibrium constant as

K = (0.999...) × (0.250...) × (0.999...) × (0.999...) = �.���

��� � � � � � � ��� � � � � � � � � ��� � � � � � � ��� � � � � � � � � ��� � � � � � � ��� � � � � � � � � ��� � � � � � � ��� � � � � � � � �
trans rot vib ∆ r E 0 term

What is evident from this calculation is that di�erence in mass between the
two isotopes is a small fraction of their actual mass, and therefore to an ex-
cellent approximation it can be assumed that the partition functions for the
isotopologues are all the same with the exception of the symmetry factor which
is di�erent for the homo- and heteronuclear diatomics. In essence the value of
the equilibrium constant is simply determined by the factor of σ 2 = 4 appearing
in the denominator, hence K = 14 .
P��F.� �e equilibrium constant for this reaction is given by [��F.��b–���]
−
○ −
○
qHDO,m qHCl,m
K= e−∆ r E 0 �RT
qH−○2 O,m qDCl,m
−
○

It is convenient to consider the contribution of each mode to the fraction in the

above expression separately.
�e standard molar translational partition function is qm−○ = Vm−○ �Λ 3 , with Λ =
h�(2πmkT)1�2 , therefore qm−○ goes as m 3�2 . In the fraction all of the other con-
stants cancel to leave
−
○ −
○ 3�2
qHDO,m qHCl,m m HDO m HCl
� −○ −
○
� =� �
qH2 O,m qDCl,m trans m H2 O m DCl
19.02 × 36.46 3�2
=� � = 1.04...
18.02 × 37.46

Assuming the high-temperature limit, the rotational partition function for a

heteronuclear diatomic is given by [��B.��b–���], q R = kT�hc B̃, and for a
nonlinear molecule by [��B.��–���], q R = (1�σ)(kT�hc)3�2 (π�ÃB̃C̃)1�2 ; the
symmetry number is � for H� O and � for HDO. In the fraction the terms in
kT�hc cancel to leave

1�2
qHDO qHCl 2 Ã H2 O B̃ H2 O C̃ H2 O B̃ DCl
� � = � �
qH2 O qDCl rot 1 Ã HDO B̃ HDO C̃ HDO B̃ HCl
2 (27.88) × (14.51) × (9.29)
1�2
5.449
= � � = 1.70...
1 (23.38) × (9.102) × (6.417) 10.59

�e vibrational partition function is given by [��B.��–���] q V = (1−e−hc ν̃�k T )−1 ,

which is conveniently expressed as q V = (1 − e−(1.4388 cm K)ν̃�T )−1 . �is term is
temperature dependent and so needs to be re-evaluated at each temperature.
�e vibrational partition function for HDO and H� O is the product of the
partition function for each normal mode, for example

qHV2 O = q(3656.7
V
cm−1 ) × q(1594.8 cm−1 ) × q(3755.8 cm−1 )
V V

�e term ∆ r E 0 is computed as

∆ r E 0 = E 0 (HDO) + E 0 (HCl) − E 0 (H2 O) − E 0 (DCl)

To a good approximation it can be assumed that the pure electronic energy

of a species is una�ected by isotopic substitution, however the vibrational zero
point energy will be a�ected. For a harmonic oscillator the energy of the ground
state is 12 hc ν̃, therefore to compute the total vibrational zero point energy of
HDO and H� O the contribution from each normal mode has to be taken into
 account.

E 0 (H2 O)vib = 12 N A hc(3656.7 + 1594.8 + 3755.8) = N A hc(4503.65 cm−1 )

E 0 (HDO)vib = 12 N A hc(2726.7 + 1402.2 + 3707.5) = N A hc(3918.2 cm−1 )
E 0 (HCl)vib = N A hc(1495.5 cm−1 ) E 0 (DCl)vib = N A hc(1072.5 cm−1 )
∆ r E 0 = N A hc(3918.2 + 1495.5 − 4503.65 − 1072.5)
= N A hc(−162.5 cm−1 )

�us the term −∆ r E 0 �RT evaluates as

−∆ r E 0 −N A hc(−162.5 cm−1 )
=
RT RT
= −(6.0221 × 1023 mol−1 ) × (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
(−162.5 cm−1 )
× = (233.7 K)�T
(8.3145 J K−1 mol−1 ) × T

With these expressions the equilibrium constant is evaluated using mathemat-

ical so�ware to give K = 3.90 at ��� K and K = 2.42 at ��� K. �e value of the
equilibrium constant is dominated by the symmetry factors and the e−∆ r E 0 �RT
term.

P��F.� �e standard molar Gibbs energy is computed from the partition function us-
ing [��F.�b–���], G m−
○
(T) = G m−
○
(0) − RT ln qm−○ �N A . As usual, the partition
function is factored into separate contributions from translation, rotation and
so on. �e factor of 1�N A is usually taken with the translational contribution.
�e standard molar translational partition function is given by qm−○ = Vm−○ �Λ 3 =
RT�p−○ Λ 3 . Taking the mass of BSi as 10.81 + 28.09 = 38.90 m u , Λ is given by
[��B.�–���]

Λ = h�(2πmkT)1�2
6.6261 × 10−34 J s
=
[2π(38.90×1.6605 × 10−27 kg)×(1.3806 × 10−23 J K−1 )×(2000 K)]1�2
= 6.25... × 10−12 m
RT
qm−○ �N A = −○ 3
p Λ NA
(8.3145 J K−1 mol−1 ) × (2000 K)
=
(105 N m−2 ) × (6.25... × 10−12 m)3 × (6.0221 × 1023 mol−1 )
= 1.12... × 109

For a heteronuclear diatomic the rotational partition function in the high tem-
perature limit is given by [��B.��b–���] q R = kT�hc B̃. �e rotational constant
 is given by [��B.�–���], B̃ = ħ�4πcI, with I = µR 2 and µ = m A m B �(m A + m B ).

ħ (m A + m B )
B̃ =
4πcR 2 m A m B
1.0546 × 10−34 J s
=
4π × (2.9979 × 1010 cm s−1 ) × (190.5 × 10−12 m)2
(10.81 + 28.09) 1
× × = 0.595... cm−1
10.81 × 28.09 1.6605 × 10−27 kg
kT
qR =
hc B̃
(1.3806 × 10−23 J K−1 ) × (2000 K)
=
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (0.595... cm−1 )
= 2.33... × 103

�e vibrational partition function is given by [��B.��–���], q V = 1�(1−e−β hc ν̃ ),

where β = 1�kT.

(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )

hcβ =
(1.3806 × 10−23 J K−1 ) × (2000 K)
= 7.19... × 10−4 cm
−1
q V = �1 − e−(7.19 ...×10 � = 2.34...
−4
cm)×(772 cm−1 )

�e electronic ground state has a degeneracy of � (the spin multiplicity); the

excited state has spin degeneracy of � and an orbital degeneracy of �, giving a
total degeneracy of �.

q E = g 0 + g 1 e−hc β ν̃
= 4 + 4e−(7.19 ...×10 = 4.01...
−4
cm)×(8000 cm−1 )

�e overall partition function is the product of these individual contributions,

therefore
−
○
Gm (2000)−G m
−
○
(0) = −RT ln qm−○ �N A
= −(8.3145 J K−1 mol−1 ) × (2000 K)
×ln �(1.12... × 109 )×(2.33... × 103 )×(2.34...)×(4.01...)�
= −512 kJ mol−1

P��F.� �e standard molar Gibbs energy is computed from the partition function us-
ing [��F.�b–���], G m −
○
(T) = G m−
○
(0) − RT ln qm−○ �N A . As usual, the partition
function is factored into separate contributions from translation, rotation and
so on; the factor of 1�N A is usually taken with the translational contribution.
�e standard molar translational partition function is given by qm−○ = Vm−○ �Λ 3 =
RT�p−○ Λ 3 . Taking the mass of C� as 3(12.01) = 36.03 m u , Λ is given by [��B.�–
���]. At ��.�� K

Λ = h�(2πmkT)1�2
6.6261 × 10−34 J s
=
[2π(102.9×1.6605 × 10−27 kg)×(1.3806 × 10−23 J K−1 )×(10.00 K)]1�2
= 9.19... × 10−11 m
RT
qm−○ �N A = −○ 3
p Λ NA
(8.3145 J K−1 mol−1 ) × (10.00 K)
=
(105 N m−2 ) × (9.19... × 10−11 m)3 × (6.0221 × 1023 mol−1 )
= 1.77... × 103

A similar calculation at ���.� K gives qm−○ �N A = 5.61... × 105

For a nonlinear molecule the rotational partition function is given by [��B.��–

���], q R = (1�σ)(kT�hc)3�2 (π�ÃB̃C̃)1�2 ; assuming that the molecule is ‘bent’
(angular), σ = 2. �e rotational constant, in the high-temperature limit, is
given by [��B.�–���], B̃ = ħ�4πcI. �e �rst step is to compute the rotational
constants.

ħ
B̃ =
4πcI
6.6261 × 10−34 J s
=
4π(2.9979 × 1010 cm s−1 ) × (1.6605 × 10−27 kg) × (39.340 × 10−20 m2 )
=0.428... cm−1

Similar calculations gives the other two rotational constants as 0.431... cm−1
and 54.7... cm−1 . Expressed as characteristic rotational temperatures these give
θ R = hc B̃�k = 0.616 K, 0.621 K, and 78.7 K. At �� K, and possibly even at ��� K,
the condition T > θ R is not satis�ed for all the rotational constants, therefore
the high-temperature expression for the partition function cannot be used.

As described, the C� molecule is an asymmetric rotor, for which there is no ex-

plicit expression for the energy levels. However, given that two of the rotational
constants are quite similar, it is reasonable to approximate the molecule as a
symmetric rotor with à = 54.7... cm−1 and B̃ = 0.430... cm−1 (the latter being
the average of the two similar rotational constants). �e partition function is
then evaluated term by term using the approach described in How is that done?
��B.� on page ���; this is best done using mathematical so�ware. At �� K the
result is q R = 16.5... and at ��� K q R = 323.4...
 At ��� K the high temperature form of the partition function gives
q R = (1�σ)(kT�hc)3�2 (π�ÃB̃C̃)1�2
(1.3806 × 10−23 J K−1 ) × (100.0 K)
3�2
= 12 � �
6.6261 × 10−34 J s
1�2
π
� �
(0.428... cm−1 ) × (0.431... cm−1 ) × (54.7... cm−1 )
= 161.3...
Taking into account the symmetry factor, this is very close to the value obtained
by explicit summation. At ��.�� K the high-temperature form gives (excluding
the symmetry factor) q R = 10.2... which, as expected, does not agree with
the result obtained by explicit summation. �e nuclear spin e�ects are more
complex to account for in the term-by-term summation, and in the absence
of a detailed analysis of this it is simply assumed that a symmetry factor of � is
appropriate, giving the �nal value of the rotational partition function at ��.�� K
of q R = 12 × 16.5... = 8.25....
�e vibrational partition function for each mode is given by [��B.��–���], q V =
1�(1 − e−β hc ν̃ ), where β = 1�kT. At ��.�� K
(6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 )
hcβ =
(1.3806 × 10−23 J K−1 ) × (10.00 K)
= 0.143... cm
−1
q V1 = �1 − e−hc β ν̃ 1 �
−1
= �1 − e−(0.143 ... cm)×(63.4 cm � = 1.00...
−1
)

�e partition functions for the other normal modes also evaluate to 1.00...;
given the low temperature, it is is to be expected that q V will be essentially � as
only the ground state contributes. �e overall vibrational partition function is
the product of these individual contributions: q V = 1.00.... A similar calcula-
tion at ���.� K gives q V = 1.67....
�e overall partition function is the product of these contributions from the
di�erent modes, therefore
−
○
Gm (10.00)−G m
−
○
(0) = − RT ln qm−○ �N A
= −(8.3145 J K−1 mol−1 ) × (10.00 K)
×ln �(1.77... × 103 )×(8.25...)×(1.00...)�
= −798 J mol−1
−
○
A similar calculation at ���.� K gives G m (100.0) − G m
−
○
(0) = −15.7 kJ mol−1 .

I��.� Note that there is an error in the question: the expression for ξ(β) should
include an additional factor of g(J). To make the notation more compact the
energy levels will be written ε J and the degeneracies g J ; derivatives with respect
to β will be assumed to be at constant V .
First, an expression for C V is developed.

1 dq 1 d
U = −N = −N −βε
� gJ e J
q dβ q dβ J
1
= N � g J ε J e−βε J
q J

Noting that d�dT = −kβ 2 (d�dβ)

dU dU
CV = = −kβ 2
dT dβ
�
d �1 �
�
= −N kβ 2 � � g J ε J e−βε J �
�
dβ � q J �
�
� −1 dq �
� 1 �
= −N kβ 2 � 2 � g J ε J e−βε J − � g J ε 2J e−βε J �
� q dβ J �
� q J �
� �
�1 � −βε J ′ � � −βε J �
�
= −N kβ 2 � 2 −βε J �
1
�q2 � � g ′ ε J′ e � g ε e − � g ε e �
� �� J � q J �
J J J J J
� J′ �

�e numerator and denominator of the �nal term in the bracket are both mul-
tiplied by q, and then a factor of 1�q 2 is taken outside the bracket to give

� �
�� �
CV = � � g J ′ ε J ′ e−βε J′ � �� g J ε J e−βε J � − q � g J ε 2 e−βε J �
−N kβ 2
�� �� J � �
� J′ �
J
q2
� J �
2�
−N kβ �� �� g J ′ ε J ′ e−βε J′ � �� g J ε J e−βε J �
= ��
2
� J′ �� J �
�
q
�
� −βε J ′ � �
�
2 −βε J � �
− � g J′ e � gJ εJ e
� J′ �� J ���
�

�e product of the sums are next rewritten as double sums

−N kβ 2 � �
� �
CV = �� g J g J ′ ε J ε J ′ e−β(ε J +ε J′ ) − � g J g J ′ ε 2J e−β(ε J +ε J′ ) �
� J, J ′ �
q2 � J, J ′ �

Taking a hint from the �nal result, consider the double sum

�(ε J − ε J ′ ) g J g J ′ e
2 −β(ε J +ε J ′ )

J, J ′

= � ε 2J g J g J ′ e−β(ε J +ε J′ ) + � ε 2J ′ g J g J ′ e−β(ε J +ε J′ ) − 2 � ε J ε J ′ g J g J ′ e−β(ε J +ε J′ )

J, J ′ J, J ′ J, J ′
�e �rst two sums only di�er by swapping the indices J and J ′ , so they are in
fact identical. Hence the last line may be written

= 2 � ε 2J g J g J ′ e−β(ε J +ε J′ ) − 2 � ε J ε J ′ g J g J ′ e−β(ε J +ε J′ )
J, J ′ J, J ′

Apart from an overall sign and a factor of 12 , these two terms are the same as
those in the bracket in the expression for C V above, hence

−N kβ 2 � �
� �
CV = �� g J g J ′ ε J ε J ′ e−β(ε J +ε J′ ) − � g J g J ′ ε 2J e−β(ε J +ε J′ ) �
� J, J ′ �
q2 � J, J ′
�
N kβ 2
= �(ε J − ε J ′ ) g J g J ′ e
2 −β(ε J +ε J ′ )
2q 2 J, J ′

which is the required expression.

For a diatomic βε J = βhc B̃J(J + 1) = hc B̃J(J + 1)�kT = θ R J(J + 1)�T, where
θ R = hc B̃�k; the degeneracy is g J = (2J + 1). For the molar quantity N A kβ 2 =
N A k�k 2 T 2 = R�k 2 T 2 . �e molar hear capacity is therefore given by
1 1
C V ,m �R = (hc B̃)2
k 2 T 2 2q 2
× �[J(J + 1) − J ′ (J ′ + 1)]2 (2J + 1)(2J ′ + 1) e−θ [J(J+1)+J ′ (J ′ +1)]�T
R

J, J ′
2
θR 1
=� �
T 2q 2
× �[J(J + 1) − J ′ (J ′ + 1)]2 (2J + 1)(2J ′ + 1) e−θ [J(J+1)+J ′ (J ′ +1)]�T
R

J, J ′

�is expression is used to generate the curves in Fig. ��.�� for particular pairs of
values of J and J ′ , that is just one term from the double sum. However, the term
for J = 0, J ′ = 1 is identical to that for J = 1, J ′ = 0, so the curves plotted in the
�gure are twice the value for the particular combination of J and J ′ indicated.
�is double sum is not a particularly e�cient method for computing the heat
capacity, but it can be evaluated using mathematical so�ware to give the curve
also shown in Fig. ��.��. For a plot up to T�θ R = 5 if is su�cient to consider
contributions from levels with J ≤ 10; this makes the calculation more tractable.
 J = 0, J ′ = 1
1.0 J = 0, J ′ = 2
J = 1, J ′ = 2
J = 1, J ′ = 3
C V ,m �R

J = 0, J ′ = 3
0.5 total

0.0
0 1 2 3 4 5
R
T�θ
D��A.� When the applied �eld changes direction slowly, the permanent dipole moment
has time to reorientate and so follows the �eld: the whole molecule rotates
into a new direction in response to a change in the �eld. However, when the
frequency of the �eld is high, a molecule cannot change direction fast enough to
follow the change in direction of the applied �eld and the dipole moment then
makes no contribution to the polarization of the sample. Because a molecule
takes about � ps to turn through about � radian in a �uid, the loss of this contri-
bution to the polarization occurs when measurements are made at frequencies
greater than about 1011 Hz (in the microwave region). It is said that orientation
polarization, the polarization arising from the permanent dipole moments, is
lost at such high frequencies
�e next contribution to the polarization to be lost as the frequency is raised
is the distortion polarization, the polarization that arises from the distortion of
the positions of the nuclei by the applied �eld. �e molecule is distorted by
the applied �eld, and the molecular dipole moment changes accordingly. �e
time taken for a molecule to bend is approximately the inverse of the molec-
ular vibrational frequency, so the distortion polarization disappears when the
frequency of the radiation is increased through the infrared.
At even higher frequencies, in the visible region, only the electrons are mobile
enough to respond to the rapidly changing direction of the applied �eld. �e
polarization that remains is now due entirely to the distortion of the electron
distribution, and the surviving contribution to the molecular polarizability is
called the electronic polarizability.

E��A.�(b) �e molecules are shown in Fig. ��.�: SO� is trigonal planar, XeF� is square
planar, and SF� is based on a trigonal bipyramid with one equatorial position
not occupied by a ligand.
SO� and XeF� are nonpolar because, although there are partial charges on each
of the atoms, the dipole moments associated with each bond cancel to give no
resultant dipole. However, SF� is polar because the dipole moments do not
cancel.
 δ- F F δ-
O δ-
δ-
δ+ δ+ δ- F δ+ δ+
F Xe F S
δ+ δ+ δ- δ+ δ+ F δ+ δ+
S δ-
δ- δ+
O O
δ- F δ- Fδ-

An alternative approach is use a symmetry argument. As explained in Sec-

tion ��A.�(a) on page ���, only molecules belonging to point groups C n , C nv
or C s may have a permanent electric dipole moment. SO� and XeF� belong to
point groups D 3h and D 4h respectively, so they are not polar, while SF� belongs
to point group C 2v so is polar.

E��A.�(b) �e magnitude of the resultant dipole moment, µres , is given by [��A.�a–���],

µres = (µ 12 + µ 22 + 2µ 1 µ 2 cos θ)1�2 .

µres = �(2.5 D)2 + (0.5 D)2 + 2 × (2.5 D) × (0.5 D) × cos 120○ � = 2.3 D
1�2

E��A.�(b) �e arrangement of charges is shown on the le� of Fig. ��.�

u
−2e
6
y�nm

" µx
4
1" 3 " ⇠
" µ⇠⇠⇠⇠θ µ y
"○ 9
⇠⇠ ?
4e u −2e
u
"
" 30 -
��� x�nm

�e x component of the dipole are given by [��A.�a–���], µ x = ∑J Q J x J , and

similarly for the y and z components; note that in this case µ z = 0 because
all of the point charges have a z coordinate of zero. �e components are then
combined using [��A.�b–���], µ = (µ 2x + µ 2y + µ z2 )1�2 , which is represented
graphically on the right of Fig. ��.�.

µ x = � Q J x J = � − 2 × (1.6022 × 10−19 C) × (162 × 10−12 m)

J

− 2 × (1.6022 × 10−19 C) × (143 × 10−12 m) × cos 30○ �

1D
× = −27.4... D
3.3356 × 10−30 C m
 where 1 D = 3.3356 × 10−30 C m is used from inside the front cover.

µ y = � QJ yJ
J

= −2 × (1.6022 × 10−19 C) × (143 × 10−12 m) × sin 30○

1D
× = −6.86... D
3.3356 × 10−30 C m

�e magnitude of the resultant is

µ = �µ 2x + µ 2y � = �(−27.4... D)2 + (−6.86... D)2 � = 28 D

1�2

and, from the diagram on the right of Fig. ��.�, the direction is given by

6.86... D
θ = tan−1 � � = 14○
27.4... D

E��A.�(b) �e relationship between the induced dipole moment µ ∗ and the electric �eld
strength E is given by [��A.�a–���], µ∗ = αE, where α is the polarizability.
�e polarizability volume α ′ is related to the polarizability α by [��A.�–���],
α ′ = α�4πε 0 . Combining these equations, rearranging for E, and using 1 V =
1 J C−1 gives

µ∗ (2.5 × 10−6 D) × [(3.3356 × 10−30 C m)�(1 D)]

E= =
4πε 0 α ′ 4π × (8.8542 × 10−12 J−1 C2 m−1 ) × (1.05 × 10−29 m3 )
= 7.1 × 103 V m−1

E��A.�(b) �e molar polarization Pm is de�ned by [��A.��–���], Pm = (N A �3ε 0 )(α +

µ 2 �3kT), where α is the polarizability of the molecule and µ is its dipole mo-
ment. �is equation is written as

NA α NA µ2 1
Pm = +
3ε 0 9ε 0 k T

which implies that a graph of Pm against 1�T should be a straight line with
slope N A µ 2 �9ε 0 k and intercept N A α�3ε 0 . However, as there are only two data
points it is convenient to calculate the required quantities directly from the
data. Writing the molar polarization at the two temperatures as Pm (T1 ) and
Pm (T2 ) and considering Pm (T2 ) − Pm (T1 ) gives

NA µ2 1 1
Pm (T2 ) − Pm (T1 ) = � − �
9ε 0 k T2 T1
 which is rearranged to give

9ε 0 k Pm (T2 ) − Pm (T1 )
1�2
µ=� × �
NA 1�T2 − 1�T1
9 × (8.8542 × 10−12 J−1 C2 m−1 ) × (1.3806 × 10−23 J K−1 )
=�
6.0221 × 1023 mol−1
(71.43 × 10−6 m3 mol−1 ) − (75.74 × 10−6 m3 mol−1 )
1�2
× �
1�(421.7 K) − 1�(320.0 K)
= 3.23... × 10−30 C m = 0.9690 D

�e value of α is found using this value of µ together with one of the data points;
both give the same answer. Rearranging [��A.��–���], Pm = (N A �3ε 0 )(α +
µ 2 �3kT), for α and using the data for 320.0 K gives

3ε 0 Pm µ2
α= −
NA 3kT
3 × (8.8542 × 10−12 J−1 C2 m−1 ) × (75.74 × 10−6 m3 mol−1 )
=
6.0221 × 1023 mol−1
(3.23... × 10−30 C m)2
− = 2.552 × 10−39 C2 m2 J−1
3 × (1.3806 × 10−23 J K−1 ) × (320.0 K)

E��A.�(b) �e relationship between relative permittivity and molar polarization is given

by the Debye equation, [��A.��–���], (ε r − 1)�(ε r + 2) = ρPm �M. Rearranging
gives
ρPm ρPm 2ρPm
εr − 1 = (ε r + 2) hence ε r − 1 = ε r � �+
M M M
ρPm 2ρPm 1 + 2ρPm �M
hence ε r �1 − �=1+ hence ε r =
M M 1 − ρPm �M

Taking the molar mass as M = 85.0 g mol−1 gives

1 + 2ρPm �M
εr =
1 − ρPm �M
1 + 2 × (1.92 g cm−3 ) × (32.16 cm3 mol−1 )�(85.0 g mol−1 )
= = 8.97
1 − (1.92 g cm−3 ) × (32.16 cm3 mol−1 )�(85.0 g mol−1 )

E��A.�(b) �e relationship between the refractive index n r at a speci�ed wavelength and

the relative permittivity ε r at the same wavelength is given by [��A.��–���],
n r = ε r , hence ε r = n r2 . In addition the relationship between relative per-
1�2

mittivity and the polarizability α is given by the Clausius–Mossotti equation,

[��A.��–���], (ε r − 1)�(ε r + 2) = ρN A α�3Mε 0 . In using this equation it is
assumed that there are no contributions from permanent electric dipole mo-
ments to the polarization, either because the molecules are nonpolar or because
 the frequency of the applied �eld is so high that the molecules cannot orientate
quickly enough to follow the change in direction of the �eld. Replacing ε r by
n r2 in the Clausius–Mossotti equation gives

n r2 − 1 ρN A α 3Mε 0 n r2 − 1
= hence α= × 2
n r2 + 2 3Mε 0 ρN A nr + 2

Taking M = 65.5 g mol−1 gives

3 × (65.5 g mol−1 ) × (8.8542 × 10−12 J−1 C2 m−1 ) 1.6222 − 1

α= ×
(2.99 × 106 g m−3 ) × (6.0221 × 1023 mol−1 ) 1.6222 + 2
= 3.40 × 10−40 C2 m2 J−1

E��A.�(b) �e relationship between the refractive index n r at a speci�ed wavelength and

the relative permittivity ε r at the same wavelength is given by [��A.��–���],
n r = ε r . In order to �nd ε r the Clausius–Mossotti equation, [��A.��–���],
1�2

(ε r − 1)�(ε r + 2) = ρN A α�3Mε 0 , is used, with the value of the polarizability

α being determined from the polarizability volume α ′ using [��A.�–���], α ′ =
α�4πε 0 .
In using the Clausius–Mossotti equation it is assumed that there are no con-
tributions from permanent electric dipole moments to the polarization, either
because the molecules are nonpolar or because the frequency of the applied
�eld is so high that the molecules cannot orientate quickly enough to follow
the change in direction of the �eld.
�e �rst step is to rearrange the Clausius–Mossotti equation for ε r
ε r − 1 ρN A α ρN A α
= hence εr − 1 = (ε r + 2)
ε r + 2 3Mε 0 3Mε 0
ρN A α 2ρN A α 1 + 2ρN A α�3Mε 0
hence ε r �1 − �=1+ hence ε r =
3Mε 0 3Mε 0 1 − ρN A α�3Mε 0

Replacing α by 4πε 0 α ′ and ε r by n r2 gives

1 + 2ρN A (4πε 0 α ′ )�3Mε 0 1 + 8πρN A α ′ �3M 1 + 2C

n r2 = = =
1 − ρN A (4πε 0 α ′ )�3Mε 0 1 − 4πρN A α ′ �3M 1−C

where C = 4πρN A α ′ �3M. Using M = 72.3 g mol−1 = 0.0723 kg mol−1 gives

C = 4πρN A α ′ �3M
4π × (865 kg m−3 ) × (6.0221 × 1023 mol−1 ) × (2.2 × 10−30 m3 )
=
3 × (0.0723 kg mol−1 )
= 0.0663...
1 + 2C 1�2 1 + 2 × 0.0663... 1�2
nr = � � =� � = �.�
1−C 1 − 0.0663...
E��A.�(b) �e Debye equation, [��A.��–���], is (ε r −1)�(ε r +2) = ρPm �M, where Pm is the
molar polarizability. �e latter is de�ned by [��A.��–���], Pm = (N A �3ε 0 )(α +
µ 2 �3kT), where µ is the dipole moment and α is the polarizability, which is
related to the polarizability volume α ′ according to [��A.�–���], α ′ = α�4πε 0 .
Replacing α in the expression for Pm by 4πε 0 α ′ gives

NA µ2
Pm = �4πε 0 α ′ + �
3ε 0 3kT
6.0221 × 1023 mol−1 �
= × 4π × (8.8542 × 10−12 J−1 C2 m−1 )
3 × (8.8542 × 10 J C m ) �
−12 −1 2 −1

(5.17 × 10−30 C m)2

× (1.5 × 10−29 m3 ) + �
3 × (1.3806 × 10−23 J K−1 ) × ([25 + 273.15] K)
= 8.69... × 10−5 m3 mol−1

�e Debye equation is then rearranged for ε r

ε r − 1 ρPm 1 + 2ρPm �M
= hence εr =
εr + 2 M 1 − ρPm �M

�e molar mass of bromobenzene, C� H� Br is 156.9995 g mol−1 or 0.156995 kg mol−1 .

Hence the relative permittivity is

1 + 2ρPm �M
εr =
1 − ρPm �M
1 + 2 × (1491 kg m−3 ) × (8.69... × 10−5 m3 mol−1 )�(0.156995 kg mol−1 )
=
1 − (1491 kg m−3 ) × (8.69... × 10−5 m3 mol−1 )�(0.156995 kg mol−1 )
= ��

P��A.� �e hydrogen peroxide molecule is shown in Fig. ��.�. For convenience the
bond lengths are denoted r OH and r OO .

y y

HA HA
φ
rOH HD
rOO z
OB OC O
x

HD

Because the molecule is neutral overall, the choice of origin is arbitrary, and
is chosen for convenience to be the OB oxygen, with the z axis along the O–O
 bond and the y axis along the OB –HA bond. With this coordinate system, the
coordinates of the atoms are

HA (0, r OH , 0) OB (0, 0, 0) OC (0, 0, r OO ) HD (r OH sin �, r OH cos �, r OO )

�e x component of the dipole µ x is given by [��A.�a–���], µ x = ∑J Q J x J , and

similarly for the y and z components. �e magnitude of the dipole is given by
[��A.�b–���], µ = (µ 2x + µ 2y + µ z2 )1�2 .

µ x = � Q J x J = +qr OH sin � µ y = � Q J y J = +qr OH + qr OH cos � µz = 0

J J

µ 2 = µ 2x + µ 2y + µ z2 = (qr OH sin �)2 + (qr OH + qr OH sin �)2

= q 2 r OH
2
(sin2 � + 1 + 2 cos � + cos2 �) = q 2 r OH
2
(2 cos � + 2)
�
where cos2 � + sin2 � = 1 is used. Hence µ = qr OH 2 cos � + 2. �e quantity
µ�qr OH is plotted as a function of � in Fig. ��.�.

2.0
µ�qr OH

1.0

0.0
0 60 120 180 240 300 360
��deg

P��A.� �e complex is shown in Fig. ��.�, in which the charges on the nitrogen and
carbon are denoted −q and +q and the C–N distance by r CN .

O
-q rCN
H3N +q
C

�e dipole is directed along the N–C bond, taken to be the x-axis, and its
magnitude is given by [��A.�a–���], µ x = ∑J Q J x J . Note that µ = µ x in this
 case as µ y and µ z are both zero. �e complex overall is neutral so the origin
of the coordinate system is arbitrary and is chosen for convenience to be at
the nitrogen atom; the carbon atom then has x-coordinate r CN . �e dipole is
therefore µ = qr CN and hence
µ
µ = � Q J x J = qr CN hence q=
J r CN

Dividing through by e gives the charge as a multiple of e as

µ 1.77 D × [(3.3356 × 10−30 C m)�(1 D)]

q�e = = = �.���
r CN e (299 × 10−12 m) × (1.6022 × 10−19 C)

�e nitrogen atom therefore has a charge of −0.123e and the carbon atom a
charge of +0.123e.

P��A.� �e relationship between induced dipole moment µ ∗ and electric �eld strength
E is given by [��A.�a–���], µ ∗ = αE where α is the polarizability. �e polar-
izability volume α ′ is related to α by [��A.�–���], α ′ = α�4πε 0 , so the induced
dipole is µ ∗ = αE = 4πε 0 α ′ E. Replacing E by the given expression Q�4πε 0 r 2
gives
α′ Q α′ Q
1�2
Q
µ∗ = 4πε 0 α ′ × = hence r=� �
4πε 0 r 2 r2 µ∗
�e charge on a proton is equal to e, so

α′ e (1.48 × 10−30 m3 ) × (1.6022 × 10−19 C)

1�2 1�2
r=� ∗� =� �
µ (1.85 D) × [(3.3356 × 10−30 C m)�(1 D)]
= 1.96... × 10−10 m = 196 pm

P��A.� �e temperature-dependence of molar polarization is given by [��A.��–���],

NA α NA µ2 1 NA µ2
Pm = + × or Pm = 43 πN A α ′ +
3ε 0 9ε 0 k T 9ε 0 k

where in the second form the de�nition of polarizability volume, which is given
by [��A.�–���], α ′ = α�4πε 0 , is used to replace α by 4πε 0 α ′ . �is equation im-
plies that a graph of Pm against 1�T should be a straight line of slope N A µ 2 �9ε 0 k
and intercept 43 πN A α ′ .
�e molar polarization is calculated from the data using the Debye equation
[��A.��–���], (ε r −1)�(ε r +2) = ρPm �M, which is rearranged to Pm = (M�ρ)(ε r −
1)�(ε r + 2). Taking the molar mass of methanol as M = 32.0416 g mol−1 and
the density as ρ = 0.791 g cm−3 at all temperatures, values of Pm are as shown
in the table below and are plotted in Fig. ��.�. �e plot shows that Pm is neither
linear in 1�T for the liquid state, nor constant for the solid.
 θ�○ C εr 1�(T�K) Pm �cm3 mol−1
−185 3.2 0.011 34 17.14
−170 3.6 0.009 69 18.81
−150 4.0 0.008 12 20.25
−140 5.1 0.007 51 23.39
−110 67.0 0.006 13 38.75
−80 57.0 0.005 18 38.45
−50 49.0 0.004 48 38.12
−20 43.0 0.003 95 37.81
0 38.0 0.003 66 37.47
20 34.0 0.003 41 37.13

40
Pm �cm3 mol−1

liquid solid
30

20

←� increasing T
10
0.003 0.004 0.005 0.006 0.007 0.008 0.009 0.010 0.011 0.012
1�(T�K)

To interpret these data, note that the temperature-dependent term N A µ 2 �9ε 0 kT

in the expression for Pm stems from the orientation contribution to the polar-
ization, that is, the tendency of polar molecules to align themselves in response
to the electric �eld. If the molecules are not able to rotate then there is no
contribution from this term and therefore Pm is expected to be lower and also
independent of temperature.
�e plot shows that as liquid methanol is cooled, Pm begins to increase less
rapidly than expected, that is, the points begin to level o�. �is indicates that
hydrogen-bonding between methanol molecules is hindering molecular rota-
tion and reducing the orientation polarization. �e e�ect extends below the
melting point with the −110 ○ C data point exhibiting liquid-like, hindered ro-
tation. �e large decline of Pm below −110 ○ C is interpreted as corresponding to
a stronger hindrance of the dipole moment rotation but the non-constancy of
Pm seems to indicate that rotational excitation is never completely eliminated.
 Because the points do not give a straight line, it is not possible to determine
reliable values of µ or α ′ from these data.

P��A.�� �e temperature-dependence of molar polarization is given by [��A.��–���],

NA α NA µ2 1 NA µ2 1
Pm = + × or Pm = 43 πN A α ′ + ×
3ε 0 9ε 0 k T 9ε 0 k T

where in the second form the de�nition of polarizability volume, which is given
by [��A.�–���], α ′ = α�4πε 0 , is used to replace α by 4πε 0 α ′ . �is equation im-
plies that a graph of Pm against 1�T should be a straight line of slope N A µ 2 �9ε 0 k
and intercept 43 πN A α ′ . �e data are plotted in Fig. ��.�.

T�K 1�(T�K) Pm �cm3 mol−1

384.3 0.002 60 57.40
420.1 0.002 38 53.50
444.7 0.002 25 50.10
484.1 0.002 07 46.80
521.0 0.001 92 43.10

60

55
Pm �cm3 mol−1

50

45

40
0.0018 0.0020 0.0022 0.0024 0.0026
1�(T�K)

�e data fall on a good straight line, the equation for which is

(Pm �cm3 mol−1 ) = (2.091 × 104 ) × 1�(T�K) + 3.27

Identifying the slope with N A µ 2 �9ε 0 k gives

N A µ 2 �9ε 0 k = (2.091 × 104 cm3 mol−1 K) = (2.091 × 10−2 m3 mol−1 K)

 and hence
1�2
9ε 0 k
µ=� × (2.091 × 10−2 m3 mol−1 K)�
NA
9 × (8.8542 × 10−12 J−1 C2 m−1 ) × (1.3806 × 10−23 J K−1 )
=�
6.0221 × 1023 mol−1
1�2
×(2.09 × 10−2 m3 mol−1 K)� = 6.17... × 10−30 C m = �.�� D

Similarly, identifying 43 πN A α ′ with the intercept gives

3
α′ = × (3.27 cm3 mol−1 )
4πN A
3 −1
= −1 × (3.27 cm mol ) = 1.30 × 10
3 −24
cm3
4π × (6.0221 × 10 mol )
23

P��A.�� �e relationship between refractive index and relative permittivity is given by

[��A.��–���], n r = ε r . In addition the relationship between relative permit-
1�2

tivity and the molar polarization is given by the Debye equation [��A.��–���],
(ε r − 1)�(ε r + 2) = ρPm �M where ρ is the mass density and M is the molar
mass.
�e mass density ρ is given by M�Vm , where Vm is the molar volume. Assuming
perfect gas behaviour, Vm = RT�p, so ρ = pM�RT and hence the Debye
equation becomes
ε r − 1 pPm pPm
= hence εr − 1 = (ε r + 2)
εr + 2 RT RT
If ε r ≈ 1 then (ε r + 2) ≈ 3 so the equation becomes
pPm 3pPm
εr − 1 = ×3 hence εr = 1 +
RT RT

Introducing n r = ε r and using the series expansion (1 + x)1�2 ≈ 1 + 12 x for

1�2

small x gives

3pPm 1�2 3pPm 3pPm

n r = �1 + � ≈ 1 + 12 × =1+
RT RT 2RT
�is expression implies that a plot of n r against p should be a straight line of
slope 3Pm �2RT. Hence, by measuring n r as a function of pressure, the molar
polarization Pm can be determined.
�e molar polarization is given by [��A.��–���], Pm = (N A �3ε 0 )(α + µ 2 �3kT).
However, assuming that the frequency of oscillation of the electric �eld is high,
as it will be for visible light, there will be no contribution from orientation po-
larization because the molecules cannot reorientate themselves quickly enough
to follow the �eld. �erefore the term µ 2 �3kT in the expression for Pm does
 not contribute, and the equation reduces to Pm = N A α�3ε 0 . �is expression is
used in that for the slope

3Pm 3 NA α α
slope = = =
2RT 2RT 3ε 0 2kTε 0
It is therefore possible to determine α from the slope of the graph, and hence
α′.

D��B.� �e arrangement of charges corresponding to the various multipoles are shown

in Fig. ��A.� on page ���. According to [��B.�–���], the potential energy of
interaction between an n-pole and an m-pole goes as 1�r n+m+1 . Two examples
of this relationship are derived in the text for the interaction between: (i) a point
charge (n = 0) and a dipole (m = 1), giving a 1�r 0+1+1 = 1�r 2 dependence; and
(ii) a dipole (n = 1) and a dipole (m = 1) giving a 1�r 1+1+1 = 1�r 3 dependence.
In both cases this form of the interaction arises by assuming that the distance
r is much greater than the separation between charges which form the dipole.
Consider the interaction between a point charge and a dipole, with the point
charge along the line of the dipole. �e point charge interacts with the two
charges which form the dipole: these interactions are opposite in sign but dif-
ferent in magnitude because the distances between the point charge and the
two charges which form the dipole are not the same. As the point charge moves
further away, these interactions both decrease in magnitude. However, because
the distance between these charges is becoming less signi�cant compared to
the distance of the point charge, the magnitude of the interaction with each
becomes more similar. As a result, the terms with opposite sign come closer
to cancelling one another out and the overall interaction therefore goes to zero
faster than does the simple interaction between point charges.
E�ectively, as r increases the two charges which form the dipole merge and
begin to cancel one another. �is is why the potential energy of interaction
falls o� more quickly than it does for the interaction between two point charges.
For quadrupoles and high n-poles the e�ect is greater, leading to an even faster
fall o� of the interaction, presumably because the e�ective cancellation of the
charges happens more quickly when there are more charges forming the n-pole.

D��B.� �is is discussed in Section ��B.� on page ���.

E��B.�(b) �e interaction between a point charge and a point dipole orientated directly
away the charge is given by [��B.�–���], V = −µ 1 Q 2 �4πε 0 r 2 . In this case the
 magnesium ion has a charge of +2e = +2 × (1.6022 × 10−19 C).

µ1 Q2
V =−
4πε 0 r 2
(1.08 D) × �(3.3356 × 10−30 C m)�(1 D)� × 2 × (1.6022 × 10−19 C)
=−
4π × (8.8542 × 10−12 J−1 C2 m−1 ) × (300 × 10−12 m)2
= −1.15... × 10−19 J

�e potential energy if the dipole has the reverse orientation is +1.15...×10−19 J

so the energy required to reverse the direction is

∆V = (1.15... × 10−19 J) × 2 = 2.30... × 10−19 J = 2.31 × 10−19 J

�e energy per mole is found by multiplying by N A

∆Vm = (2.30... × 10−22 kJ) × (6.0221 × 1023 mol−1 ) = 139 kJ mol−1

E��B.�(b) �e potential energy interaction between two parallel point dipoles separated
by distance r at angle Θ is given by [��B.�b–���], V = µ 1 µ 2 (1−3 cos2 Θ)�4πε 0 r 3 .
However, because in this case the interaction is not in a vacuum, it is necessary
to replace ε 0 by ε 0 ε r where ε r is the relative permittivity of the medium.

µ 1 µ 2 (1 − 3 cos2 Θ)
V=
4πε 0 ε r r 3
(2.7 D) × (1.85 D) × �(3.3356 × 10−30 C m)�(1 D)� × (1 − 3 cos2 45○ )
2

=
4π × (8.8542 × 10−12 J−1 C2 m−1 ) × 3.5 × (3.0 × 10−9 m)3
= −2.6 × 10−24 J which corresponds to −1.6 J mol−1

E��B.�(b) �e shape of a linear quadrupole is given in Fig. ��A.� on page ���; an example
of such an arrangement is a CO� molecule which has negative charges on the
oxygen atoms and a balancing positive charge on the central carbon. Two
such quadrupoles are shown in Fig. ��.�, arranged so that they are parallel and
separated by a distance r �e distances between atoms that are not directly
√ Pythagoras’ theorem, so that the distances
opposite each other are found using
A–E, � √
B–D, B–F and C–E are all r 2 + l 2 , while the distances A–F and C–D are
both r 2 + (2l)2 = r 2 + 4l 2 .
�e interaction energy is derived in a similar way to that used in Section ��B.�(b)
on page ��� for dipole–dipole interactions. �e total interaction energy is the
sum of nine pairwise terms, one for each combination of a point charge in one
quadrupole with a point charge in the other quadrupole. Each term has the
form Q 1 Q 2 �4πε 0 r 12 where Q 1 and Q 2 are the charges being considered in that
 r
A D
-Q -Q
l B r 2+4l 2 E l
+2Q r 2+l 2 +2Q
l l
C r F
-Q -Q

term and r 12 is the distance between them.

��� � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � �� � � � � � � � � � � � �� ��� � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � �� � � � � � � � � � � � ��

A–D A–E A–F B–D

1 (−Q)(−Q) (−Q)(2Q) (−Q)(−Q) (2Q)(−Q)

V =− � + √ + √ + √
4πε 0 r r2 + l 2 r 2 + 4l 2 r2 + l 2
(2Q)(2Q) (2Q)(−Q) (−Q)(−Q) (−Q)(2Q) (−Q)(−Q)
+ + √ + √ + √ + �
r r2 + l 2 r 2 + 4l 2 r2 + l 2 r
��� � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � �� � � � � � � � � � � � �� ��� � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � �� � � � � � � � � � � � �� ��� � � � � � � � � � � � � � � � � � � � � � � � � �
B–E B–F C–D C–E C–F
2 2 2
1 6Q 8Q 2Q
= � −√ +√ �
4πε 0 r r2 + l 2 r 2 + 4l 2
Q2 8 2
= �6 − � +� �
4πε 0 r 1 + (l�r) 2 1 + 4(l�r)2
Q2
= �6 − 8(1 + x 2 )−1�2 + 2(1 + 4x 2 )−1�2 �
4πε 0 r

where x = l�r. Assuming that r � l, so that x � 1, the series expansion

(1 + y)n = 1 + ny + 12 n(n − 1)y 2 + ... can be used: it is su�cient to retain
the �rst three terms, (1 + y)−1�2 ≈ 1 − 12 y + 38 y 2 . �e required expansions are
therefore (1 + x 2 )−1�2 ≈ 1 − 12 x 2 + 38 x 4 and (1 + 4x 2 )−1�2 ≈ 1 − 2x 2 + 6x 4

Q2
V= �6 − 8�1 − 12 x 2 + 38 x 4 + ...� + 2�1 − 2x 2 + 6x 4 + ...��
4πε 0 r
Q2 Q2
= �6 − 8 + 4x 2 − 3x 4 + 2 − 4x 2 + 12x 4 � = × 9x 4
4πε 0 r 4πε 0 r
Q2 l 4 9Q 2 l 4
= × 9� � =
4πε 0 r r 4πε 0 r 5

E��B.�(b) �e average energy of interaction between rotating polar molecules is given by

the Keesom interaction [��B.�–���].

C 2µ 12 µ 22
�V � = − C=
r6 3(4πε 0 )2 kT
 In this case µ 1 = µ 2 , so

2µ 14
C=
3(4πε 0 )2 kT
2 × �(2.5 D) × (3.3356 × 10−30 C m)�(2.5 D)�
4

=
3×(4π × (8.8542 × 10−12 J−1 C2 m−1 ))2 ×(1.3806 × 10−23 J K−1 )×(273 K)
= 6.90... × 10−77 J m6

C 6.90... × 10−77 J m6
Hence �V � = − = − = −6.9 × 10−23 J . �is energy
r6 (1.0 × 10−9 m)6
corresponds, a�er multiplication by N A , to −41 J mol−1 . �is is very much
smaller than the average molar kinetic energy of the molecules which, as ex-
plained in Section �A.�(a) on page ��, is given by
3
2
RT = 3
2
× (8.3145 J K−1 mol−1 ) × (273 K) = 3.4 kJ mol−1

E��B.�(b) �e energy of the dipole–induced dipole interaction between a polar molecule

such as water and a polarizable molecule such as CCl� is given by [��B.�–���],
V = −µ 12 α 2′ �4πε 0 r 6 . From the data in the Resource section the dipole moment
of water is �.�� D and the polarizability volume of CCl� is 10.3 × 10−30 m3 .

µ 12 α 2′
V =−
4πε 0 r 6
�(1.85 D) × (3.3356 × 10−30 C m)�(1 D)� × (10.3 × 10−30 m3 )
2

=−
4π × (8.8542 × 10−12 J−1 C2 m−1 ) × (1.0 × 10−9 m)6
= −3.52... × 10−24 J

�is interaction energy corresponds, a�er multiplication by Avogadro’s con-

stant, to −2.1 J mol−1 .

E��B.�(b) �e London formula for the energy of the dispersion interaction is given by
[��B.�–���]
C I1 I2
V = − 6 C = 32 α 1′ α 2′
r I1 + I2
In the case that the two interacting species are the same, with polarizability
volume α ′ and ionisation energy I, this expression becomes

I 2 3 ′2 3α ′2 I
C = − 32 α ′2 = α I hence V =−
2I 4 4r 6
Table ��A.� on page ��� in the Resource section gives the polarizability volume
of argon as α ′ = 1.66 × 10−30 m3 and Table �B.� on page ��� gives the �rst
ionisation energy as I = 1520.4 kJ mol−1 , so

3α ′2 I 3×(1.66 × 10−30 m3 )2 ×(1520.4 × 103 J mol−1 )

V =− = − = �.� J mol−1
4r 6 4 × (1.0 × 10−9 m)6
P��B.� �e electrostatic interaction between two charges is given by Coulomb’s law,
given in �e chemist’s toolkit � in Topic �A on page �� as V = Q 1 Q 2 �4πεr.
According to the electrostatic model, the energy of interaction of a hydrogen
bond in a vacuum is
Q 1 Q 2 (+0.42 × 1.6022 × 10−19 C) × (−0.84 × 1.6022 × 10−19 C)
V= =
4πε 0 r 4π × (8.8542 × 10−12 J−1 C2 m−1 ) × (170 × 10−12 m)
= −4.78... × 10−19 J

�e energy required to break the hydrogen bond is therefore 4.8 × 10−19 J ,

which corresponds to 2.9 × 102 kJ mol−1 .
�e energy of interaction in water, where ε = ε 0 ε r ≈ ε 0 × 80, is

Q 1 Q 2 (+0.42 × 1.6022 × 10−19 C) × (−0.84 × 1.6022 × 10−19 C)

V= =
4πεr 4π × (8.8542 × 10−12 J−1 C2 m−1 ) × 80 × (170 × 10−12 m)
= −5.98... × 10−21 J

�e energy required to break the hydrogen bond is therefore 6.0 × 10−21 J ,

which corresponds a�er multiplying by Avogadro’s constant to �.� kJ mol−1 .
�is is much less than the energy required to break the bond in a vacuum.

P��B.� �e most favourable orientation is that in which the positive end of the dipole,
that is, the side of the molecule with the δ+ hydrogen atoms, lies closer to the
anion (Fig. ��.�).

H δ+
δ−
O µ
H δ+

�e interaction potential energy between a dipole µ and a charge Q is given

by [��B.�–���], V = −µQ�4πε 0 r 2 ; the �eld experienced by a charge Q is E =
−(1�Q)(dV �dr). �e �eld experienced by the anion is therefore

1 dV 1 d µQ µ d −2 µ
E =− =− �− �= �r � = −
Q dr Q dr 4πε 0 r 2 4πε 0 dr 2πε 0 r 3

Noting that 1 J C−1 = 1 V, the �eld experienced at each of the distances is

(a) At �.� nm

µ (1.85 D) × (3.3356 × 10−30 C m)�(1 D)

E =− = −
2πε 0 r 3 2π × (8.8542 × 10−12 J−1 C2 m−1 ) × (1.0 × 10−9 m)3
= −1.1 × 108 V m−1
 (b) At �.� nm

µ (1.85 D) × (3.3356 × 10−30 C m)�(1 D)

E =− = −
2πε 0 r 3 2π × (8.8542 × 10−12 J−1 C2 m−1 ) × (0.3 × 10−9 m)3
= −4.1 × 109 V m−1

(c) At �� nm

µ (1.85 D) × (3.3356 × 10−30 C m)�(1 D)

E =− = −
2πε 0 r 3 2π × (8.8542 × 10−12 J−1 C2 m−1 ) × (30 × 10−9 m)3
= −4.1 × 103 V m−1

P��B.� (a) �e London formula for the energy of the dispersion interaction is given
by [��B.�–���]
C I1 I2
V = − 6 C = 32 α 1′ α 2′
r I1 + I2
In the case that the two interacting species are the same, with polarizabil-
ity volume α ′ and ionisation energy I, this expression becomes

I 2 3 ′2 3α ′2 I
C = − 32 α ′2 = α I hence V =−
2I 4 4r 6
In this case, using the given data and the polarizability volume of benzene
from the previous problem, the energy of interaction is

3α ′2 I
V =−
4r 6
3×(1.04 × 10−29 m3 )2 ×(5.0 eV)×(1.6022 × 10−19 C)�(1 eV)
=−
4×(0.4 × 10−9 m)6
= −1.58... × 10−20 J

�is interaction energy corresponds to −9.6 kJ mol−1 .

(b) Because the force is the negative slope of the potential energy, an expres-
sion for the force is obtained by di�erentiating the expression for V

dV d 3α ′2 I 9α ′2 I
F=− = − �− 6 � = − 7
dr dr 4r 2r

�e negative sign indicates that the force is attractive; the force goes to
zero as the distance goes to in�nity.

P��B.� �e arrangement is shown in Fig. ��.��. For convenience the distances are
denoted by R and r. �e task is to calculate the potential energy of interaction
between the O–H group and the oxygen atom OB as a function of the angle θ,
assuming the distances r and R to be �xed. Because the electrostatic interaction
 OB
200 pm -0.83e
R
θ
-0.83e +0.45e
r H
OA 95.7 pm

of OB with the O–H group is of interest, the interaction between OA and the H
atom is not included in this calculation.
�e sum of the potential energies of OB interacting with OA and with H is given
by
QA QB QH QB
V= +
4πε 0 r AB 4πε 0 r HB
where Q A , Q B and Q H are the partial charges on the atoms. �e OA –OB dis-
tance is �xed as R, and from Fig. ��.�� the H–OB distance is found using the
2
cosine rule as r HB = R 2 + r 2 − 2Rr cos θ. Hence, using the partial charges and
distances given in the question, the interaction energy is

(−0.83e)(−0.83e) (+0.45e)(−0.83e)
V= + √
4πε 0 R 4πε 0 R 2 + r 2 − 2Rr cos θ
e2 � 0.45 × 0.83 �
= 0.832 − �
4πε 0 R � (1 + (r�R) − 2(r�R) cos θ �
2

(1.6022 × 10−19 C)2

= × �0.6889
4π × (8.8542 × 10−12 J−1 C2 m−1 ) × (200 × 10−12 m)
0.3755
−� �
1 + [(95.7 pm)�(200 pm)] − 2 × [(95.7 pm)�(200 pm)] × cos θ
2

0.3755
= (1.15... × 10−18 J) × �0.6889 − √ �
1.22... − 0.957 cos θ
�is energy corresponds, a�er multiplying by Avogadro’s constant, to

0.3755
V = (6.94 . . . × 102 kJ mol−1 ) × �0.6889 − √ �
1.22... − 0.957 cos θ
�is function is plotted in Fig. ��.��. As expected the minimum energy occurs
for θ = 0○ , when the δ+ hydrogen lies between the δ− oxygen atoms. Note that
the energy is only negative (that is, favourable) over a small range of angles
about this minimum.

P��B.�� Figure ��.�� shows a molecule A interacting with the molecules in a volume
dτ located at distance R. �e number of molecules in the volume dτ is N dτ
where N is the number density, the number of molecules per unit volume. If
the potential energy of interaction of A with a single molecule at distance R is
 300

200

V �kJ mol−1
100

−180 −120 −60 0 60 120 180

θ�deg

R
A dτ

V (R) then the energy of interaction of A with the volume dτ, which contains
N dτ molecules, is V (R)N dτ.

�e total interaction of A with all the N molecules in the sample, as opposed

to just those in the volume element dτ, is found by integrating over all relevant
space, giving ∫ V (R)N dτ. Multiplication by 12 N then gives the total interac-
tion for all the N molecules of the sample as U = 21 N ∫ V (R)N dτ. �e factor
of 12 is necessary to avoid double-counting, for example to avoid counting the
interaction of molecule B with A as a distinct and additional contribution to
that of A interacting with B.

�e cohesive energy density is then given by

1
U 2N 1 N
U= = � V (R)N dτ = 2 � � N� V (R) dτ =
1
2
N 2� V (R) dτ
V V V

where V is the total volume of the sample and N�V is equal to the number
density N .

To perform the integration, note from �e chemist’s toolkit �� in Topic �F on

page ��� that in spherical polar coordinates the volume element dτ is given by
R 2 sin θ dR dθ d�, and that the limits of the integrals are � = 0 to � = 2π, θ = 0
to θ = π, and, in this case, R = d to R = ∞. Replacing V (R) by a van der Waals
 attraction of the form −C 6 �R 6 and performing the integration gives
∞ π 2π C6 2
U = 12 N 2� � � − R sin θ dR dθ d�
R=d θ=0 �=0 R6
∞ C6 π 2π
= 12 N 2� − 4 dR × � sin θ dθ × � d�
d R 0 0
∞
C6 C6
= 12 N 2 × � 3 � × [− cos θ]0 × [�]0 = 12 N 2 × �− 3 � × 2 × 2π
π 2π
3R d 3d
C
= − 23 πN 2 3
6
d
�e number density N is related to the mass density ρ by noting that in volume
V there are N V molecules and hence N V �N A moles. �e mass of this amount
is M × N V �N A , where M is the molar mass. �erefore the mass density ρ is
ρ = M × N V �N A V = MN �N A ; rearranging this gives N = N A ρ�M. Using
this expression for N in the expression for U gives

NA ρ 2 C6 N2
U = − 23 π � � 3 = − 23 π 3 A 2 ρ 2 C 6
M d d M

D��C.� �is is discussed in Section ��C.� on page ���.

E��C.�(b) �e vapour pressure of a liquid when it is dispersed as spherical droplets of

radius r is given by the Kelvin equation [��C.��–���], p = p∗ e2γVm (l)�rRT , where
p∗ is the vapour pressure of bulk liquid to which no additional pressure has
been applied. Because the mass density of a substance with molar volume
Vm and molar mass M is given by ρ = M�Vm , it follows that Vm = M�ρ.
Substituting this into the Kelvin equation gives p = p∗ e2γ(M�ρ)�rRT .
�e surface tension γ of water at 35 ○ C is not given in Table ��C.� on page ���,
so the value at this temperature is estimated from the graph in Fig. ��C.� on
page ��� as being approximately 71 mN m−1 , which is equal to 71 × 10−3 J m−2 .
Hence, taking p∗ as �.��� kPa and M as ��.���� g mol−1 (18.0158×10−3 kg mol−1 ),

2γM�ρ
p = p∗ exp � � = (5.623 kPa)
rRT
2×(71 × 10−3 J m−2 )×(18.0158 × 10−3 kg mol−1 )�(994.0 kg m−3 )
× exp � �
(20 × 10−9 m)×(8.3145 J K−1 mol−1 )×([35 + 273.15] K)
= �.� kPa
E��C.�(b) �e height climbed by a liquid in a capillary tube of radius r is given by [��C.�–
���], h = 2γ�ρg acc r, assuming that the contact angle is zero. Rearranging for
γ, replacing r by 12 d where d is the diameter of the tube, and noting that 1 N =
1 kg m s−2 gives

γ = 12 ρg acc rh = 14 ρg acc dh
= 14 (0.9956 × 103 kg m−3 )×(9.807 m s−2 )×(0.320 × 10−3 m)
×(9.11 × 10−2 m) = 0.0711... kg s−2 = 71.2 mN m−1

E��C.�(b) �e pressure di�erence between the inside and outside of a spherical droplet is
given by the Laplace equation [��C.�–���], p in = p out + 2γ�r. Hence, noting
that 1 Pa = 1 N m−2 ,

2γ 2 × (22.39 × 10−3 N m−1 )

∆p = p in − p out = = = ��� kPa
r (220 × 10−9 m)

E��C.�(b) �e height climbed by a liquid in a capillary tube of radius r is given by [��C.�–

���], h = 2γ�ρg acc r, assuming that the contact angle is zero. Rearranging for γ
and noting that 1 N = 1 kg m s−2 gives

γ = 12 ρg acc rh
= 12 ×(0.9500×103 kg m−3 )×(9.807 m s−2 )×(0.300×10−3 m)
×(10.00×10−2 m) = 0.139... kg s−2 = 139.7 mN m−1

P��C.� �e dependence of the surface tension on surfactant concentration is given by

[��C.��–���], (∂γ�∂ ln[c�c −○ ])T = −RTΓS . �is equation implies that a plot of γ
against ln(c�c −○ ) has a slope equal to −RTΓS . �e data are plotted in Fig. ��.��.

[A]�mol dm−3 ln([A]�c −○ ) γ�N m−1

0.10 −2.303 0.070 2
0.20 −1.609 0.067 7
0.30 −1.204 0.065 1
0.40 −0.916 0.062 8
0.50 −0.693 0.059 8

�e points appear to lie on a curve rather than a straight line, indicating that ΓS
is not constant over this range of concentration. �e data are a good �t to the
quadratic

(γ�N m−1 ) = −0.003288 × [ln([A]�c −○ )] − 0.01614 × ln([A]�c −○ ) + 0.05042

2
 0.070

γ�N m−1
0.065

0.060

−2.5 −2.0 −1.5 −1.0 −0.5

ln([A]�c −○ )

�is equation has been used to draw the line on Fig. ��.��. Di�erentiation gives

∂γ
� � = [−0.006576 × ln([A]�c −○ ) − 0.01614] × (N m−1 )
∂ ln([A]�c −○ ) T

Equating this expression for the slope to −RTΓS and rearranging gives

[0.006576 × ln([A]�c −○ ) + 0.01614] × (N m−1 )

ΓS =
RT
�is result is used to calculate ΓS at any concentration of interest. For example,
at [A] = 0.1 mol dm−3 , using c −○ = 1 mol dm−3 and 1 J = 1 N m, the surface
excess concentration is
�0.006576 × ln �[0.1 mol dm−3 ]�[1 mol dm−3 ]� + 0.01614� × (N m−1 )
ΓS =
(8.3145 J K−1 mol−1 ) × ([20 + 273.15] K)
= 4.1 × 10−7 mol m−2

D��D.� �e primary structure of a macromolecule is the sequence of small molecular

residues making up the polymer, whereas the secondary structure is the (of-
ten local) spatial arrangement of a chain. �e tertiary structure is the overall
three-dimensional structure of a single macromolecule. Two or more macro-
molecules may form an aggregation that yields an overall quaternary structure.

D��D.� In these expressions N is the number of monomer units and l is the length of
each unit. �e conditions for the validity of these expressions are the same as
those used in the derivation of the probability distribution for a random coil,
 in particular the model does not take into account the impossibility of two or
more monomer units occupying the same space.

(a) Contour length: the length of the macromolecule measured along its back-
bone, that is the length of all its monomer units placed end to end. �is
is the stretched-out length of the macromolecule with bond angles main-
tained within the monomer units and ���○ angles at unit links.
(b) Root mean square separation: a measure of the average separation of the
ends of a random coil.
(c) Root mean square separation: a measure of the average separation of the
ends of a tetrahedrally (θ = 109.5○ ) constrained jointed chain.
(d) Root mean square separation: a measure of the average separation of the
ends of a constrained jointed chain in which each successive individual
bond is constrained to a single cone of angle θ relative to its neighbour.
�e factor F is given by F = [(1 − cos θ)�(1 + cos θ)]1�2 .
(e) Radius of gyration of a one-dimensional random coil.
(f) Radius of gyration of a three-dimensional random coil.
(g) Radius of gyration of a tetrahedrally (θ = 109.5○ ) constrained jointed
chain.

E��D.�(b) �e number-average molar mass is given by [��D.�a–���], M n = (1�N total )

∑ i N i M i . Denoting the polymers as � and � gives

∑i N i M i N1 M1 + N2 M2
Mn = =
N total N total

Because the two polymers are present in a 3 ∶ 2 ratio of amounts in moles, and
hence also a 3 ∶ 2 ratio of numbers of molecules, the numbers of each polymer
are N 1 = 35 N total and N 2 = 25 N total . Hence

N 1 M 1 + N 2 M 2 5 N total M 1 + 5 N total M 2 3
3 2
Mn = = = 5 M 1 + 25 M 2
N total N total
= 3
5
× (62 kg mol−1 ) + 25 × (78 kg mol−1 ) = �� kg mol−1

�e weight-average molar mass is given by [��D.�b–���], M W = (1�m total )

∑ i m i M i , where m i is the mass of polymer i present. Using m i = n i M i and
m total = ∑ i m i gives

∑ i m i M i ∑ i (n i M i )M i ∑ i n i M i2
MW = = =
∑i m i ∑i n i M i ∑i n i M i
 From above the amounts in moles of each polymer are 35 n total and 25 n total so

n 1 M 12 + n 2 M 22 5 n total M 12 + 5 n total M 22 3M 12 + 2M 22
3 2
MW = = 3 =
n1 M1 + n2 M2 n
5 total 1
M + 25 n total M 2 3M 1 + 2M 2
3 × (62 kg mol−1 )2 + 2 × (78 kg mol−1 )2
= −1 −1 = �� kg mol−1
3 × (62 kg mol ) + 2 × (78 kg mol )

E��D.�(b) �e root mean square separation of the ends of a freely jointed one-dimensional
chain is given by [��D.�–���], R rms = N 1�2 l, where N is the number of monomer
units and l is the length of each unit. In this case

R rms = N 1�2 l = 12001�2 × (1.125 nm) = ��.�� nm

E��D.�(b) �e contour length R c of a polymer is given by [��D.�–���], R c = N l, and the

root mean square separation of the ends of a freely jointed one-dimensional
chain is given by [��D.�–���], R rms = N 1�2 l. In both cases N is the number of
monomer units and l is the length of each unit.
�e monomer of polypropene –[CH� CH(CH� )]n – is taken to be CH� CH(CH� ).
�e number of monomers in the chain is given by

M polymer 174 × 103 g mol−1

N= = = 4.13... × 103
M CH2 CH(CH3 ) 42.0774 g mol−1

�e length of each CH� CH(CH� ) unit is estimated as the length of a two C–C
bonds: one C–C bond in the centre and half a bond length either side where the
unit connects to carbons in adjacent units. From Table �C.� on page ��� in the
Resource section a C–C bond length is approximately ��� pm, so the monomer
length l is taken as 2 × (154 pm) = 308 pm. �e contour length and root mean
square separation are then given by

R c = N l = (4.13... × 103 ) × (308 pm) = 1.27... × 106 pm = 1.27 µm

R rms = N 1�2 l = (4.13... × 103 )1�2 × (308 pm) = 1.98... × 104 pm = 19.8 nm

E��D.�(b) �e radius of gyration R g of a one-dimensional random coil is given by [��D.�a–

���], R g = N 1�2 l. Rearranging gives

18.9 × 10−9 m
2
Rg 2
N =� � =� � = 1.8 × 103
l 450 × 10−12 m

E��D.�(b) �e probability that the ends of a one-dimensional random coil are a distance
nl apart is given by [��D.�–���], P = (2�πN)1�2 e−n �2N where N is the total
2

number of monomers in the chain and l is the length of each monomer unit.
 �e monomer of polyethene –[CH� CH� ]n – is taken to be CH� CH� , so the
number of monomers in the chain is given by

M polymer 85 × 103 g mol−1

N= = = 3.03... × 103
M CH2 CH2 28.0516 g mol−1

�e length of each CH� CH� unit is estimated as the length of a two C–C bonds:
one C–C bond in the centre and half a bond length either side where the unit
connects to carbons in adjacent units. From Table �C.� on page ��� a C–C
bond length is approximately ��� pm, so the monomer length l is taken as 2 ×
(154 pm) = 308 pm.
If the end-to-end distance is d, then d = nl and hence n = d�l. In this case
d = 15 nm and l = 308 pm hence

d 15 × 10−9 m
n= = = 48.7...
l 308 × 10−12 m
�e probability of the ends being this distance apart is therefore

2 1�2 −n 2 �2N
P=� � e
πN
1�2
2
=� � × e−(48.7 ...) �2×(3.03 ...×10 3 )
= 9.8 × 10−3
2

π × (3.03... × 103 )

E��D.�(b) �e probability distribution function for a three-dimensional freely jointed chain

is given by [��D.�–���]

a 3
3 1�2
f (r) = 4π � � r 2 e−a a=� �
2 2
r
π 1�2 2N l 2
where N is the number of monomers in the chain, l is the length of each monomer,
and f (r) dr is the probability that the ends of the chain are a distance between
r and r + dr apart.
�e monomer of polyethene –[CH� CH� ]n – is taken to be CH� CH� , so the
number of monomers in the chain is given by

M polymer 75 × 103 g mol−1

N= = = 2.67... × 103
M CH2 CH2 28.0516 g mol−1

�e length of each CH� CH� unit is estimated as the length of a two C–C bonds:
one C–C bond in the centre and half a bond length either side where the unit
connects to carbons in adjacent units. From Table �C.� on page ��� a C–C
bond length is approximately ��� pm, so the monomer length l is taken as 2 ×
(154 pm) = 308 pm = 0.308 nm. �erefore
1�2
3 1�2 3
a=� � =� � = 0.0769... nm−1
2N l 2 2 × (2.67... × 10 ) × (0.308 nm)2
3
 3
a
f (14.0 nm) = 4π � � r 2 e−a
2 2
r
π 1�2
0.0769... nm−1
3
= 4π � � × (14.0 nm)2 × e−(0.0769 nm ) ×(14.0 nm)
−1 2 2

π 1�2
= 0.0631... nm−1

�e probability that the ends will be found in a narrow range of width δr =

0.1 nm at 14.0 nm is therefore

f (14.0 nm)δr = (0.0631... nm−1 ) × (0.1 nm) = 6.3 × 10−3

E��D.�(b) As explained in Section ��D.�(b) on page ���, the radius of gyration of a con-
strained chain is given by the value for a free chain multiplied by a factor F,
where F is given by [��D.�–���], F = [(1 − cos θ)�(1 + cos θ)] . For θ =
1�2

120○ ,
1 − cos θ 1�2 1 − cos 120○ 1�2
F=� � =� � = 1.73...
1 + cos θ 1 + cos 120○
�is corresponds to a percentage increase of [(1.73...) − 1] × 100% = +��.�% .
�e volume is proportional to the cube of the radius, so the volume of the
constrained chain is related to that of a free chain by a factor of F 3 = (1.73...)3 =
5.19.... �is corresponds to a percentage increase of [(5.19...) − 1] × 100% =
+���% .

E��D.�(b) As explained in Section ��D.�(c) on page ���, the root mean square separation
of the ends of a partially rigid chain with persistence length l p is given by the
value for a free chain multiplied by a factor F, where F is given by [��D.��–���],
F = (2l p �l − 1)1�2 . �e contour length is given by [��D.�–���], R c = N l, so a
persistence length of �.�% of the contour length corresponds to l p = 0.025R c =
0.025N l. Hence, for N = 1000,

2 × (0.025N l)
1�2 1�2
2l p
F=� − 1� =� − 1� = (0.050N − 1)
1�2
l l
= (0.050 × 1000 − 1) = 7.00 . . .
1�2

�is corresponds to a percentage increase of [(7.00...) − 1] × 100% = +600% .

�e volume is proportional to the cube of the radius, so the volume of the par-
tially rigid chain is related to that of a free chain by a factor of F 3 = (7.00...)3 =
3.43... × 102 . �is corresponds to a percentage increase of [(3.43... × 102 ) − 1] ×
100% = (3.42 × 104 )% .

E��D.�(b) By analogy with [��D.��–���], the radius of gyration R g of a partially rigid coil
is related to that of a freely jointed chain according to R g = F × R g,free where
 F = (2l p �l −1)1�2 . �e radius of gyration for a three-dimensional freely jointed
chain is given by [��D.�b–���], R g,free = (N�6)1�2 l, so
1�2
2l p N 1�2
R g = F × R g,free =� − 1� ×� � l
l 6

Rearranging gives

2l p N 6R g2 2l p 2
l 6R g
R g2 = � − 1� � � l 2 hence = −1 hence lp = � 2 + 1�
l 6 Nl2 l 2 Nl

�erefore for the polymer in question, taking l = 0.164 nm,

6 × (3.0 nm)2
2
l 6R g 0.164 nm
lp = � 2 + 1� = � + 1� = �.�� nm
2 Nl 2 1500 × (0.164 nm)2

E��D.��(b) Modelling the polyethene as a �D random coil perfect elastomer, the restoring
force is given by [��D.��a–���], F = (kT�2l) ln[(1 + λ)�(1 − λ)] where λ =
x�N l.
�e monomer of polyethene –[CH� CH� ]n – is taken to be CH� CH� , so the
number of monomers in the chain is given by

M polymer 85 × 103 g mol−1

N= = = 3.03... × 103
M CH2 CH2 28.0516 g mol−1

�e length of each CH� CH� unit is estimated as the length of a two C–C bonds:
one C–C bond in the centre and half a bond length either side where the unit
connects to carbons in adjacent units. From Table �C.� on page ��� a C–C
bond length is approximately ��� pm, so the monomer length l is taken as 2 ×
(154 pm) = 308 pm = 0.308 nm. �e value of λ corresponding to a �.� nm
extension is therefore
x 2.0 nm
λ= = = 2.14... × 10−3
N l (3.03... × 103 ) × (0.308 nm)

Because λ � 1 the simpli�ed equation for the restoring force, [��D.��b–���],

F = (kT�N l 2 )x is used. Noting that 1 J m−1 = 1 N gives

kT (1.3806 × 10−23 J K−1 ) × ([25 + 273.15] K)

F= x = × (2.0 × 10−9 nm)
Nl2 (3.03... × 103 ) × (0.308 × 10−9 m)2
= 2.9 × 10−14 N

E��D.��(b) �e entropy change when a �D random coil is stretched or compressed by a

distance x is given by [��D.��–���], ∆S = − 12 kN ln[(1 + λ)(1+λ) (1 − λ)(1−λ) ]
where λ = x�R c . �e contour length R c is given by [��D.�–���], R c = N l, so it
follows that λ = x�N l.
 �e monomer of polyethene –[CH� CH� ]n – is taken to be CH� CH� , so the
number of monomers in the chain is given by

M polymer 85 × 103 g mol−1

N= = = 3.03... × 103
M CH2 CH2 28.0516 g mol−1

�e length of each CH� CH� unit is estimated as the length of a two C–C bonds:
one C–C bond in the centre and half a bond length either side where the unit
connects to carbons in adjacent units. From Table �C.� on page ��� a C–C
bond length is approximately ��� pm, so the monomer length l is taken as 2 ×
(154 pm) = 308 pm = 0.308 nm. �e value of λ corresponding to a �.� nm
extension is therefore
x 2.0 nm
λ= = = 0.00214...
N l (3.03... × 103 ) × (0.308 nm)
�e entropy change is therefore

∆S = 12 kN ln �(1 + λ)(1+λ) (1 − λ)(1−λ) �

= 1
2
× (1.3806 × 10−23 J K−1 ) × (3.03... × 103 )
× ln �(1 + 0.00214...)(1+0.00214 ...) × (1 − 0.00214...)(1−0.00214 ...) �
= −9.60... × 10−26 J K−1

�e molar entropy change is obtained by multiplying by Avogadro’s constant

∆S m = (−9.60... × 10−26 J K−1 ) × (6.0221 × 1023 mol−1 ) = −0.058 J K−1 mol−1

P��D.� �e probability distribution for the separation of the ends in a �D random coil
is given by [��D.�–���]

a 3
3 1�2
f (r) = 4π � � r 2 e−a a=� �
2 2
r
where
π 1�2 2N l 2
(a) �e root-mean-square separation is given by R rms = �r 2 �1�2 where the
mean value of r 2 is calculated as
∞ a 3
�r 2 � = � r 2 f (r) dr = � r 2 × 4π � � r 2 e−a
2 2
r
dr
0 π 1�2

a 3 ∞ a 3 3 π 1�2
= 4π � � � r 4 e−a r dr = 4π � 1�2 � × � �
2 2

π 1�2 π 8(a 2 )2 a 2
��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
0

Integral G.� with k = a 2

3 3 2N l 2
= = � � = Nl2
2a 2 2 3

Hence R rms = �r 2 �1�2 = (N l 2 )1�2 = N 1�2 l , in agreement with [��D.�–

���].
 (b) �e mean separation is
∞ a 3
�r� = � r f (r) dr = � r × 4π � � r 2 e−a
2 2
r
0 π 1�2

a 3 ∞ a 3
1 2 1
= 4π � � � r 3 e−a r = 4π � � × = � �
2 2

π 1�2 π 1�2 2(a 2 )2 π 1�2 a

��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
0

Integral G.� with k = a 2

2
2 2N l 8N
= � �= � �l
π 1�2 3 3π

(c) �e most probable separation is the value of r for which f (r) is a maxi-
mum. Di�erentiating f (r) using the product rule gives

d f (r) a 3
= 4π � 1�2 � × �(2r)(e−a r ) + (r 2 )(−2a 2 re−a r )�
2 2 2 2

dr π
a 3
= π � 1�2 � × 2re−a r �1 − a 2 r 2 �
2 2

π
At the maximum d f (r)�dr = 0, which implies that

1 2N l 2 2N 1�2
r(1 − a 2 r 2 ) = 0 hence r mp = =� �= � � l
a 3 3

�e solution r = 0 is rejected because this does not correspond to a max-

imum, as implied by the fact that f (0) = 0.
For the case that N = 4000 and l = 154 pm these expressions give

R rms = N 1�2 l = 40001�2 × (154 pm) = 9.73... × 103 pm = �.�� nm

8N 1�2 8 × 4000 1�2
�r� = � � l =� � × (154 pm) = 8.97... × 103 pm = �.�� nm
3π 3π
2N 1�2 2 × 4000 1�2
r mp =� � l =� � × (154 pm) = 7.95... × 103 pm = �.�� nm
3 3

P��D.� �ere is some lack of clarity in the text over the de�nition of the radius of
gyration, R g . For a polymer consisting of N identical monomer units, R g is
de�ned as
N
R g2 = (1�N) � r 2i (��.�)
i=1

where r i is the distance of monomer unit i from the centre of mass. In other
words, the radius of gyration is the root-mean-square of the distance of the
monomer units from the centre of mass.
A related quantity is the moment of inertia I about an axis, which is de�ned in
the following way
N
I = � md i2 (��.�)
i=1
where m is the mass of the monomer unit and d i is the perpendicular distance
from the monomer to the axis. In general, the distance d i is not the same as r i :
the �rst is the perpendicular distance to the axis, the second is the distance to
the centre of mass.
A radius of gyration can be related to a moment of inertia by imagining a rigid
rotor consisting of a mass m tot equal to the total mass of the polymer held at a
distance R g from the origin; the moment of inertia of this rotor is I = m tot R g2 ,
and hence R g2 = I�m tot . However, note that this radius of gyration is associated
by the rotation about a particular axis.

(a) For the purposes of this discussion there is no distinction between a ‘thin
disc’ and a ‘long rod’: both are cylinders with circular cross sections of
radius a and length either h or l. �e case of a solid rod is considered in
(b).
(b) For a solid rod it is convenient to use eqn ��.� for rotation about (i) the
long axis of the rod, and (ii) an axis perpendicular to this and which passes
through the centre of mass. �e long axis of the rod de�nes the z-axis and
the centre of mass is at z = 0; the rod therefore extends from −l�2 to +l�2
along z. It is convenient to use cylindrical polar coordinates described
in �e chemist’s toolkit �� in Topic �F on page ���. In such a coordinate
system the volume element is r dr d� dz, and � ranges from 0 to 2π.
Equation ��.� is adapted for a solid object by replacing the mass by a
volume element dV which has mass ρ dV , where ρ is the mass density; the
summation becomes an integration over the relevant coordinates which
describe the rod: z = −l�2 to +l�2, � = 0 to 2π, and r = 0 to a. To compute
the moment of inertia about the long axis note that the perpendicular
distance to the axis is r so the integral is

z=+l �2 r=a �=2π

I�� = � � � r 2 × ρ dV
z=−l �2 r=0 �=0
z=+l �2 r=a �=2π
=ρ � � � r 2 × r dz dr d�
z=−l �2 r=0 �=0
z=+l �2 r=a �=2π
=ρ � dz � r 3 dr � d�
z=−l �2 r=0 �=0

a4
=ρ × l × × 2π = ρl a 4 π�2
4

�e total mass of the rod is m tot = ρV = ρπa 2 l, hence the moment of

inertia is I�� = 12 m tot a 2 . A rigid rotor with the same mass as the rod has
moment of inertia I = m tot R g,�� 2
. Equating the moments of inertia gives an
expression for the radius of gyration as R g,�� = (1�2)1�2 a .
To compute the moment of inertia perpendicular to the long axis, say
about the x-axis, it is necessary to know the perpendicular distance d
between an arbitrary point (x, y, z) and that axis. �is distance is that
between the points (x, y, z) and (x, 0, 0); by Pythagoras’ theorem d 2 =
 y 2 + z 2 = r 2 sin2 � + z 2 . �e moment is inertia is therefore found from the
integral

I=� (r 2 sin2 � + z 2 ) × ρ dV = ρ � r 2 sin2 � dV + ρ � z 2 dV

cyl. cyl. cyl.
��� � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � ��� � � � � � � � � � � � � �
A B

where the integration is over the complete cylinder. �e integrals A and

B are conveniently evaluated separately.
z=+l �2 r=a �=2π
A =ρ � � � r 2 sin2 � × r dz dr d�
z=−l �2 r=0 �=0
z=+l �2 r=a �=2π
=ρ � dz � r 3 dr � sin2 � d�
z=−l �2 r=0 �=0

a4
=ρ × l × × π = ρl a 4 π�4 = m tot a 2 �4
4
where the integral over � is found using Integral T.� with k = 1 and a =
2π.
z=+l �2 r=a �=2π
B =ρ � � � z 2 × r dz dr d�
z=−l �2 r=0 �=0
z=+l �2 r=a �=2π
=ρ � z 2 dz � r dr � d�
z=−l �2 r=0 �=0
3
l a2
=ρ × × × 2π = ρl 3 a 2 π�12 = m tot l 2 �12
12 2
�e moment of inertia about the perpendicular axis is therefore

I� = A + B = m tot a 2 �4 + m tot l 2 �12 = m tot (a 2 �4 + l 2 �12)

A rigid rotor with the same total mass has moment of inertia I = m tot R g,�
2
,
hence R g,� = (a 2 �4 + l 2 �12)1�2 .
(c) Consider the moment of inertia about the z-axis passing through the
centre of a solid sphere. �e square of the perpendicular distance of a
point to this axis is x 2 + y 2 , hence I = ∫sphere (x 2 + y 2 )ρ dV . In spherical
polar coordinates

x 2 + y 2 = r 2 sin2 θ cos2 � + r 2 sin2 θ sin2 � = r 2 sin2 θ

�e integral is therefore evaluated as

r=a θ=π �=2π
I =ρ � � � (r 2 sin2 θ) × r 2 sin θ dr dθ d�
r=0 θ=0 �=0
r=a θ=π �=2π
=ρ � r 4 dr � sin3 θ dθ � d�
r=0 θ=0 �=0
5
a 4
=ρ × × × 2π
5 3
 where the integral over θ is of the form of Integral T.� with k = 1 and
a = π. �e total mass of the sphere is m tot = ρV = (4�3)ρπa 3 , hence the
moment of inertia can be expressed as

3 a5 4
I = m tot × × ρ × × × 2π = 2
m a2
5 tot
4ρπa 3 5 3
A rigid rotor with the same mass as the sphere has moment of inertia
I = m tot R g2 , hence R g = (2�5)1�2 a . Note that this is the radius of gyration
associated with rotation about this axis.

P��D.� �e radius of gyration R g is found by equating m total R g2 to the moment of inertia

I, hence R g2 = I�m total . �e moment of inertia is given by I = ∑ Nj m j R 2j , where
m j is the mass of unit j and R j is its distance from the centre of mass. If all N
units have the same mass m then I = m ∑ j R 2j and m total = Nm. Hence

1 1 1
Rg = � mjRj =
2
× m � R 2j = � R 2j
m total j Nm j N j

P��D.� As explained in �e chemist’s toolkit �� in Topic �E on page ���, the frequency of

a harmonic oscillator with mass m and force constant k f is ν = (1�2π)(k f �m)1�2 .
�e force constant is given by [��D.��c–���], k f = kT�N l 2 . �e mass is taken
as the mass of one monomer, which is given by m = M�N N A where M is the
molar mass of the macromolecule and N is the number of monomers in the
chain. Combining these expressions gives
1�2
1 k f 1�2 1 kT�N l 2 1 RT 1�2
ν= � � = � � = � �
2π m 2π M�N N A 2πl M

where R = kN A is used.
�e monomer of polyethene –[CH� CH� ]n – is taken to be CH� CH� . �e length
of each CH� CH� unit is estimated as the length of a two C–C bonds: one C–C
bond in the centre and half a bond length either side where the unit connects
to carbons in adjacent units. From Table �C.� on page ��� a C–C bond length
is approximately ��� pm, so the monomer length l is taken as 2 × (154 pm) =
308 pm. Noting that 1 J = 1 kg m2 s−2 and 1 Hz = 1 s−1 , the vibration frequency
is therefore

1 RT 1�2
ν= � �
2πl M
(8.3145 J K−1 mol−1 ) × ([20 + 273.15] K)
1�2
1
= � �
2π × (308 × 10−12 m) 65 kg mol−1
= 3.16... × 109 Hz = �.� GHz

�e expression shows that the frequency increases with temperature and de-
creases with increasing molar mass. �e T 1�2 dependence re�ects the thermal
 energy needed to establish a displacement from equilibrium. �e M −1�2 de-
pendence indicates that a larger chain mass requires more thermal energy to
establish the same displacement.

P��D.�� As explained in Section ��D.� on page ��� the glass transition temperature cor-
responds to a transition from a state of high to low chain mobility as the temper-
ature decreases. �is corresponds to the freezing of the internal bond rotations.
In e�ect, the easier such rotations are, the lower Tg . Internal rotations are more
di�cult for polymers that have bulky side chains than for polymers without
such chains because the side chains of neighbouring molecules can impede
each other’s motion. Of the four polymers in this problem, polystyrene has the
largest side chain (phenyl) and the largest Tg . �e chlorine atoms in poly(vinyl
chloride) interfere with each other’s motion more than the smaller hydrogen
atoms that hang from the carbon backbone of polyethylene. Poly(oxymethylene),
like polyethylene, has only hydrogen atoms protruding from its backbone; how-
ever, poly(oxymethylene) has fewer hydrogen protrusions and a still lower Tg
than polyethylene.

D��E.� �is is discussed in Section ��E.�(a) on page ���.

D��E.� Sterols, like cholesterol, prevent the hydrophobic chains of lipids bilayers from
‘freezing’ into a gel and, by disrupting the packing of the chains, spread the
melting point of the membrane over a range of temperatures.

E��E.�(b) �e isoelectric point of a protein is the pH at which the protein has no net
charge and therefore is una�ected by an electric �eld. �is is the pH at which
the velocity is zero; solving for this gives

0 = 0.80 − (4.0 × 10−3 )(pH) − (5.0 × 10−2 )(pH)2

Solving this equation for pH gives

�
−(−4.0 × 10−3 ) ± (−4.0 × 10−3 )2 − 4 × (−5.0 × 10−2 ) × (0.8)
pH =
2 × (−5.0 × 10−2 )
= +3.96... or − 4.04...

�e negative solution is rejected as it is outside the pH range �.�–�.� over which

the expression is valid. �erefore the isoelectric point is �.� .
P��E.� �e equilibrium constant for the formation of micelles containing N monomers,
M N , is given by [��E.�b–���] (the factors of 1�c −○ are omitted for clarity)
[M N ]
K=
([M]total − N[M N ]) N
In the text the fraction of surfactant molecules present as micelles is de�ned
as f = [M N ]�[M]total ; it could be argued that a better de�nition would be f =
N × [M N ]�[M]total on the grounds that each micelle contains N monomers.
Using the �rst de�nition for f the equilibrium constant is rewritten
f
K=
[M]total
N−1 (1 − N f )N
�is equation is solved numerically to �nd f as a function of [M]total for given
values of K and N. �e results for three such situations are shown in Fig. ��.��.
For N = 30 there is a sudden increase in f once [M]total �c −○ exceeds a certain
value; this corresponds to the critical micelle concentration. �is concentration
depends on both N and K.

0.4
f (K = 1 N = 3)
10 f (K = 1 N = 30)
0.3 10 f (K = 10−6 N = 30)

0.2
f

0.1

0.0
0 2 4 6 8 10
[M]total �c −○

I��.� (a) �e Lennard-Jones potential is given by [��B.��–���], VLJ (r) = 4ε{(r 0 �r)12 −
(r 0 �r)6 }. As shown in Fig. ��B.� on page ���, the depth of the potential
well is given by ε and the position of the minimum is given by r e = 21�6 r 0 .
̃ e = 1.51 × 10−23 J and
�e results for He� give the depth of the well as hc D
the position of the minimum as R = 297 pm so it follows that
re 297 pm
ε = 1.51 × 10−23 J and r0 = = = ��� pm
21�6 21�6
A plot of the potential with these values is shown in Fig. ��.��.
 (b) �e Morse potential is given by [��C.�–���], VM (x) = hc D ̃ e (1 − e−ax )2 ,
̃
where x = r − r e and hc D e is the depth of the well. With this poten-
tial VM (0) = 0, in contrast to the Lennard-Jones potential for which
VLJ (∞) = 0. To compare the two, the Morse potential is replotted as
VM (x) = hc D̃ e �1 − e−a(r−r e ) �2 − hc D
̃ e ; this is shown plotted in Fig. ��.��
using the given values of hc D ̃ e = 1.51 × 10−23 J and a = 5.79 × 1010 m−1 .

4
Lennard-Jones
Morse
2
V �(10−23 J)

−2
250 300 350 400 450 500
r�pm

I��.� (a) �e charges on the atoms as calculated using a �-��G* basis are shown in
the table below, and the diagram shows the numbering of the atoms and
the charges on the heteroatoms.

–0.61
O5 H 1, 2, 3

H +0.75 6 –0.29
C –0.79 C
H 4 H
C8 N
–0.58 7 H
9, 10, 11
H H
4
 atom type number q�e x/Å y/Å z/Å
C 4 0.746 0.469 −0.168 −0.583
O 5 −0.611 1.228 −0.554 −1.430
C 6 −0.288 0.674 −2.216 0.767
N 7 −0.790 0.143 −0.896 0.509
C 8 −0.577 −0.186 1.194 −0.685
H 3 0.231 1.339 −2.475 −0.041
H 1 0.168 1.227 −2.235 1.700
H 2 0.168 −0.122 −2.951 0.819
H 9 0.161 −0.848 1.425 0.141
H 10 0.207 0.591 1.946 −0.738
H 11 0.207 −0.746 1.236 −1.611
H 12 0.380 −0.492 −0.509 1.167
�e dipole moment along x is computed as µ x = ∑ i q i x i , where i is
the index for the atom, q i is its charge, and x i its coordinate. Using the
data in the table the components of the dipole moment are easily com-
puted in units of the elementary charge times Å, and then these values
are converted to Debye in the usual way. �e total dipole moment is
µ = (µ 2x + µ 2y + µ z2 )1�2 .

µ x = −0.461 e Å
= (−0.461 × 10−10 m) × (1.6022 × 10−19 C)�(3.3356 × 10−30 C m)
= −2.212 D
Similarly µ y = 0.607 D and µ z = 2.897 D, giving µ = 3.695 D .
�e energy of interaction of two dipoles is given by [��B.�b–���]
µ1 µ2
V= × (1 − 3 cos2 Θ)
4πε 0 r 3
With the data given, and converting to molar units
[(3.695 D) × (3.3356 × 10−30 C m)�(1 D)]2 )
V=
4π × (8.8542 × 10−12 J−1 C2 m−1 ) × (3.0 × 10−9 nm)3
× (1 − 3 cos2 Θ) × (6.0221 × 1023 mol−1 )
= (30.4... J mol−1 ) × (1 − 3 cos2 Θ)
A plot of this function is shown in Fig. ��.��.
(b) �e maximum of the dipole–dipole interaction is −61 J mol−1 which is
only �.�% of the energy of the hydrogen bond.

I��.� Starting from G = U − T S − tl, the di�erential is formed and the basic equation
dU = TdS + tdl is introduced to give
dG = dU − d(T S) − d(tl) = dU − TdS − SdT − tdl − ldt
= TdS + tdl − TdS − SdT − tdl − ldt = −SdT − ldt
 20

V �(J mol−1 )
−20

−40

−60
0 50 100 150 200 250 300 350
Θ�○

�e Helmholtz energy A is given by [�D.�a–��], A = U − T S. Forming the

di�erential gives

dA = dU − d(T S) = dU − TdS − SdT = TdS + tdl − TdS − SdT = −SdT + tdl

�e Maxwell relations are derived using the method described in Section �E.�(a)
on page ���. Because G is a state function, dG = −SdT − ldt is an exact
di�erential. �erefore according to the criterion in [�E.�–���], (dg�dy)x =
(dh�dx) y if d f = gdx + hdy is an exact di�erential, it follows that

∂S ∂l ∂S ∂l
−� � = −� � hence � � =� �
∂t T ∂T t ∂t T ∂T t

Applying the same approach to dA = −SdT + tdl gives

∂S ∂t ∂S ∂t
−� � =� � hence � � = −� �
∂l T ∂T l ∂l T ∂T l

To deduce the equation of state, the basic equation dU = TdS + tdl is divided
by dl and the condition of constant T is imposed

∂U ∂S ∂t ∂t
� � = T � � + t = −T � � + t = t − T � �
∂l T ∂l T ∂T l ∂T l

In the second step the Maxwell relation (∂S�∂l)T = −(∂T�∂t) l , derived above,
is used.

I��.� �e osmotic pressure Рis expressed in terms of the concentration [J] by the

virial-like expression of [�B.��–���], Π = RT �[J] + B[J]2 �. In this equation
the units of B are the inverse of the units of [J].
�e osmotic virial coe�cient arises largely from the e�ect of excluded volume.
If a solution of a macromolecule is imagined as being built by the successive
addition of macromolecules of e�ective radius a to the solvent, each one being
excluded by the ones that preceded it, then B is the excluded volume per mole
of molecules. �e volume of a molecule is v mol = (4�3)πa 3 , but the excluded
volume is determined by the smallest distance possible between centres of two
molecules, which is 2a. �erefore the excluded volume is (4�3)π(2a)3 = 8v mol
for a pair of molecules. �e volume excluded per molecule is one-half this
volume or 4v mol . �us, for an e�ective radius of a = γR g = 0.85R g the osmotic
virial coe�cient is
16π 16π
B = 4N A v mol = NA a3 = N A γ 3 R g3
3 3

(a) For a freely jointed chain R g = (N�6)1�2 l hence

16π N 3�2
B= NA γ3 � �
3 6
16π 4000 3�2
= (6.0221 × 1023 mol−1 ) × [0.85×(154 × 10−12 m)]3 � �
3 6
= 0.39 m3 mol−1 .

(b) For a chain with tetrahedral bond angles R g = (N�3)1�2 l hence

16π N 3�2
B= NA γ3 � �
3 3
16π 4000 3�2
= (6.0221 × 1023 mol−1 ) × [0.85×(154 × 10−12 m)]3 � �
3 3
= 1.1 m3 mol−1 .
D��A.� Lattice planes are labelled by their Miller indices h, k, and l, where h, k, and
l refer respectively to the reciprocals of the smallest intersection distances (in
units of the lengths of the unit cell, a, b and c) of the plane along the a, b, and
c axes. �ese axes may be non-orthogonal.

E��A.�(b) �e volume of an orthorhombic unit cell is given by V = abc, and the mass
of the unit cell m is given by m = ρV , where ρ is the mass density. Using the
estimate of mass density ρ = 2.9 g cm−3

m = abcρ = [(589 × 822 × 798) × 10−36 m3 ] × (2.9 × 106 g m−3 )

= 1.12... × 10−21 g

�e mass of the unit cell is also related to the molar mass by m = nM =

N M�N A M where n is the amount in moles in the unit cell, M is the molar
mass, and N is the number molecules per unit cell.

mN A (1.12... × 10−21 g) × (6.0221 × 1023 mol−1 )

N= = = 4.99...
M 135.01 g mol−1

If it is assumed that there are no defects in the crystal lattice then N is expected
to be an integer and hence N = 5 . With this value a more precise value of the
mass density is calculated as
m NM
ρ= =
V NA V
5 × (135.01 g mol−1 )
= = �.�� g cm−3
(6.0221 × 1023 mol−1 ) × [(589 × 822 × 798) × 10−36 m3 ]

E��A.�(b) Miller indices are of the form (hkl) where h, k, and l are the reciprocals of
the intersection distances along the a, b and c axes, respectively. If the recipro-
cal intersection distances are fractions then the Miller indices are achieved by
multiplying through by the lowest common denominator.
 intersect axes at (−a, 2b, −c) (a, 4b, −4c)
remove cell dimensions (−1, 2, −1) (1, 4, −4)
take reciprocals (−1, 1
2
, −1) (−1, 14 , − 14 )
Miller indices (2̄12̄) (4̄11̄)

E��A.�(b) �e separation of (hkl) planes d hk l of a cubic lattice is given by [��A.�a–���],

d hk l = a�(h 2 + k 2 + l 2 )1�2 .

(712 pm) (712 pm)

d 123 = = ��� pm d 222 = = ��� pm
(12 + 22 + 32 )1�2 (22 + 22 + 22 )1�2

(712 pm)
d 246 = = ��.� pm
(22 + 42 + 62 )1�2

E��A.�(b) �e separation of (hkl) planes d hk l of an orthorhombic lattice is given by

l = h �a + k �b + l �c . �erefore, d hk l = (h �a +
2 2 2 2 2 2 2 2 2
[��A.�b–���], 1�d hk
k �b + l �c )
2 2 2 2 −1�2
.

−1�2
32 12 22
d 312 =� + + �
(769 pm)2 (891 pm)2 (690 pm)2
= (2.48... × 1019 )−1�2 m = ��� pm

P��A.� From Fig. ��A.� on page ��� it is seen that the unit cell can be envisaged as a
prism of height b whose base is a parallelogram with sides a and c and interior
angle β. �e volume V of the unit cell is b times the area of the parallelogram,
which is depicted below.

(180○ − β)
@ β @
a@ a@ x
@ @
c

�e area of the parallelogram is cx, and x = a sin(180○ − β). It follows that

V = bcx = bc × [a sin(180○ − β)]. �is is further developed using the identity
sin(A − B) = sin(A) cos(B) − cos(A) sin(B) to give

V = bca[sin(180○ ) cos(β) − cos(180○ ) sin(β)]

= −bca(−1) sin(β) = abc sin β
P��A.� Refer to Fig. ��A.� on page ��� to see how the angles are de�ned in relation
to a, b and c. �e volume of the unit cell, V , is V = a ⋅ b × c where a, b and
c are vectors de�ning the sides of the unit cell. Writing vector a in terms of
its components along the orthogonal set of unit vectors i, j and k gives a =
a i i + a j j + a k k. It is convenient to �rst �nd V 2 , given by

V 2 = (a ⋅ b × c)(a ⋅ b × c)
��� a i a j a k a i ���
� aj ak ���
= ����� b i b j b k b i bj bk ���
��� c c ���
� i j ck ci cj ck �
��� a i a j a k a i b i c i ����
�
= ����� b i b j b k a j b j c j ����
�
��� c c b k c k ����
� i j ck ak
Note that transposing a matrix does not alter the value of the determinant.
��� a i a i + a j a j + a k a k a i b i + a j b j + a k b k a i c i + a j c j + a k c k ���
� �
= ����� b i a i + b j a j + b k a k b i b i + b j b j + b k b k b i c i + b j c j + b k c k �����
��� c a + c a + c a c i b i + c j b j + c k b k c i c i + c j c j + c k c k ����
� i i j j k k
��� a ⋅ a a ⋅ b a ⋅ c ���
� �
= ����� a ⋅ b b ⋅ b b ⋅ c �����
��� a ⋅ c b ⋅ c c ⋅ c ���
� �
��� ac cos β ����
���
2
a ab cos γ
= ��� ab cos γ 2
bc cos α ����
���
b
��� ac cos β bc cos α ��
� c2
= a b c (1 − cos α − cos β − cos2 γ + 2 cos α cos β cos γ)
2 2 2 2 2

For the penultimate line the fact that γ is the angle between a and b is used
so that the dot product is a ⋅ b = ab cos γ, and likewise for the other pairs of
vectors; the �nal line simply involves evaluating the determinant. �us for a
triclinic unit cell

V = abc(1 − cos2 α − cos2 β − cos2 γ + 2 cos α cos β cos γ)1�2

For a monoclinic unit cell α = γ = 90○ so cos α = cos γ = 0 and

V = abc(1 − cos2 β)1�2 = abc sin β

where the identity cos2 θ + sin2 θ = 1 has been used. For a orthorhombic unit
cell α = β = γ = 90○ so cos α = cos β = cos γ = 0 and

V = abc

A tetragonal unit cell, as shown in Fig. ��A.� on page ���, has a = b ≠ c so

V = (651 pm)2 × (934 pm) = 3.96 × 10−28 m3

P��A.� For an orthorhombic unit cell, V = abc. Given that m = M�N A , where m is the
mass per repeating unit CH� CH� and M is its molar mass (M = 28.0... g mol−1 ),
it follows that for two repeating units per cell the mass density ρ is
2m 2M
ρ= =
V N A abc
2 × (28.0... g mol−1 )
=
(6.0221 × 1023 mol−1 ) × (740 pm) × (493 pm) × (253 pm)
= �.�� g cm−3

P��A.� For an orthorhombic unit cell, V = abc. Because there are 8 molecules per
unit cell, the mass density ρ is ρ = 8m�V = 8M�N A V where m is the mass per
molecule, V is the volume of the unit cell and M is the molar mass.
M = M([N(C4 H9 )4 ][Ru(N)(S2 C6 H4 )2 ]) + 2M(C6 H4 S2 2− )
= [(637.9...) + 2 × (140.2...)] g mol−1 = 918.3... g mol−1

8M
ρ=
N A abc
8 × (918.3... g mol−1 )
= −1
(6.0221 × 1023 mol ) × (3.6881 nm) × (0.9402 nm) × (1.7652 nm)
= �.�� g cm−3

For the osmium analogue, M = 1007.5... g mol−1 . �e osmium mass density is

estimated, assuming that the unit cell volume remains constant, using

M(Os)ρ Ru (1007.5... g mol−1 ) × (1.99 g cm−3 )

ρ Os = = = �.�� g cm−3
M(Ru) 918.3... g mol−1

D��B.� �e scattering factor determines how strongly an atom scatters the X-rays, and
hence how strong the contribution from a particular atom is to a re�ection. It is
de�ned and described in Section ��B.�(c) on page ���. For forward scattering,
the scattering factor is equal to the number of electrons in the atom.

E��B.�(b) Bragg’s law [��B.�b–���], λ = 2d sin θ, describes the relationship between wave-
length of the X-rays λ, the Bragg angle θ, and the plane separation d. �us
λ = 2d sin θ = 2 × (99.3 pm) × sin (19.76○ ) = ��.� pm
E��B.�(b) As shown in Fig. ��B.�� on page ���, for the cubic F lattice re�ections from
planes where h, k and l are all even or all odd are present in the di�raction
pattern. Hence the �rst three possible re�ections occur for planes (���), (���)
and (���). Using the Bragg law [��B.�b–���], λ = 2d hk l sin θ, and the expres-
sion for the spacing of the planes [��A.�a–���], d hk l = a�(h 2 + k 2 + l 2 )1�2 , the
following table is drawn up

Miller indices (111) (200) (220)

d hk l a�(1 + 1 + 1 )
2 2 2 1�2
a�(2 ) 2 1�2
a�(22 + 22 )1�2
d hk l �pm 234.9... 203.5 143.8...
sin θ 0.274... 0.316... 0.448...
θ�○ 15.9 18.5 26.6

E��B.�(b) �e separation of the (hkl) planes of an orthorhombic lattice is given by [��A.�b–

l = h �a + k �b + l �c . �is distance is used with [��B.�b–���]
2 2 2 2 2 2 2
���], 1�d hk
to compute the angle of re�ection as θ = sin−1 (λ�2d hk l ).

Miller indices (100) (010) (111)

(1�d hk
2
l )�pm
−2
1 �574.1
2 2
1 �796.8
2 2
12 �574.12 + 12 �796.82 + 12 �495.92
d hk l �pm 574.1 796.8 339.5...
θ�○ 4.166○ 3.001○ 7.057○

E��B.�(b) �e Bragg law [��B.�b–���], λ = 2d sin(θ), is rearranged to give the glancing

angle as 2θ = 2 sin−1 (λ�2d), where d is the plane separation and λ is the
wavelength of the X-rays. For the case where λ = 93.222 pm,

2θ = 2 × sin−1 [(93.222 pm)�2 × (82.3 pm)] = 68.9...○

For the case where λ = 95.123 pm,

2θ = 2 × sin−1 [(95.123 pm)�2 × (82.3 pm)] = 70.6...○

�e di�erence in the glancing angles is 70.6...○ − 68.9...○ = 1.61○ .

E��B.�(b) In Section ��B.�(c) on page ��� it is shown that the scattering factor in the
forward direction, f (0), is equal to the total number of electrons in the species,
N e . �us for Mg�+ f (0) = 10 .

E��B.�(b) �e structure factor is given by [��B.�–���]

Fhk l = � f j ei� hk l ( j)
j
 where f j is the scattering factor of species j and � hk l ( j) = 2π(hx j + ky j + lz j )
is the phase of the scattering from that species.
It is assumed that all the atoms are the same and have the same scattering factor
f . Species at the corners of the unit cell are shared between eight adjacent unit
cells so they have weight 18 and so the contribution from each is 18 f . �e atom
at position ( 12 , 12 , 12 ) has weight 1 with scattering factor f .
Fhk l = � f j ei� hk l ( j)
j

= f �1 + e2iπk +e2iπl +e2iπ(k+l ) +e2iπh +e2iπ(h+k) +e2iπ(h+l ) +e2iπ(h+k+l ) �

1
8

+ f e2iπ( 2 h+ 2 k+ 2 l )
1 1 1

�e indices h, k and l are all integers, and einπ = (−1)n for integer n. For the
terms in the bracket all the exponents are even multiples of iπ, so all the terms
are equal to +1 and together they contribute + f to the structure factor. �e
term due to the central atom evaluates to f (−1) h+k+l . For (h + k + l) even this
term is f so the structure factor is Fhk l = f + f = 2 f , for (h + k + l) odd this
term is − f so the structure factor is Fhk l = f − f = 0 .

E��B.�(b) �e cubic I unit cell is shown in Fig. ��A.� on page ���. �e structure factor is
given by [��B.�–���]
Fhk l = � f j ei� hk l ( j)
j

where f j is the scattering factor of species j and � hk l ( j) = 2π(hx j + ky j + lz j )

is the phase of the scattering from that species.
�e ions at the corners of the unit cell are shared between eight adjacent unit
cells so they have weight 18 and therefore, if they all have the same scattering
factor f , the contribution from each is 18 f . As is shown in Exercise E��B.�(b),
these ions together contribute + f to the structure factor.
�e body centre atom at position ( 12 , 12 , 12 ) has weight � with a scattering factor
given as twice that of the other ions, hence its contribution is 2 f . �e contri-
bution of this ion to the structure factor is
2 f e2iπ( 2 h+ 2 k+ 2 l ) = 2 f (−1)(h+k+l )
1 1 1

�e structure factor is therefore Fhk l = f + 2 f (−1)(h+k+l ) . For (h + k + l) odd,

Fhk l = f − 2 f = − f , and for (h + k + l) even, Fhk l = f + 2 f = 3 f .

E��B.�(b) �e electron density distribution ρ(r) in the unit cell is given by [��B.�–���],
ρ(r) = (1�V ) ∑ hk l Fhk l e−2πi(hx+k y+l z) , where V is the volume of the unit cell.
In this case the structure factors are only given for the x direction so the sum
is just over the index h. Furthermore, because Fh = F−h the summation can be
taken from h = 0 to h = +∞
∞ ∞
V ρ(x) = � Fh e−2πihx = F0 + � �Fh e−2πihx + F−h e2πihx �
h=−∞ h=1
∞ ∞
= F0 + � Fh �e−2πihx + e2πihx � = F0 + 2 � Fh cos(2πhx)
h=1 h=1
 In this case there are a total of ten terms to include, h = 0 to 9. Figure ��.� shows
a plot of V ρ(x) against x; the electron density is at a maximum of 142�V at
x = 0 or x = 1, the boundaries of the unit cell.

150

V ρ(x) 100

50

−50
0.0 0.2 0.4 0.6 0.8 1.0
x

E��B.�(b) �e Patterson synthesis is given by [��B.�–���],

1
P(r) = � �Fhk l � e
2 −2πi(hx+k y+l z)
V hk l

In this case the structure factors are only given for the x direction so the sum
is just over the index h. Furthermore, because Fh = F−h the summation can be
taken from from h = 0 to h = +∞. Using a similar line of argument to that in
Exercise E��B.�(b), the Patterson synthesis is
∞
V P(x) = F02 + 2 � Fh2 cos(2πhx)
h=1

In this case there are a total of ten terms to include, h = 0 to 9. Figure ��.� shows
a plot of V P(x) against x. As expected, there strong feature at the origin; this
arises from the separation between each atom and itself. �ere is also a strong
feature at x = 1 which indicate that atoms are separated by 1 × a unit along the
x-axis.

E��B.��(b) To constructor the Patterson map, choose the position of one atom to be the
origin. �en add peaks to the map corresponding to vectors joining each pair
of atoms (Fig. ��.�). �e vector between atom A and atom B has the same
magnitude as that between B and A, but points in the opposite direction; the
map therefore includes two symmetry related peaks on either side of the origin.
�e vectors between each atom and itself give a peak at the centre point of the
Patterson map, and the many contributions at this position create an intense
peak.
 1 000

500
V P(x)

−500
−1.0 −0.5 0.0 0.5 1.0
x

Carbon atoms in benzene Patterson map

R12 R14

R13
R14
R13 R12

E��B.��(b) Using the de Broglie relation [�A.��–���], λ = h�p = h�(m e υ), where p is the
momentum, m e is the mass of a electron and υ its speed, it follows that

h 6.6261 × 10−34 J s
υ= = = 6.93 × 103 km s−1
λm e (105 × 10−12 m) × (9.1094 × 10−31 kg)

E��B.��(b) From the equipartition principle the kinetic energy is E k = 12 kT. �is en-
ergy can be written in terms of the momentum as p2 �(2m) and hence p =
(mkT)1�2 . �e de Broglie relation [�A.��–���], λ = h�p, is then used to �nd
the wavelength

h 6.6261 × 10−34 J s
λ= =
(mkT) 1�2 [(9.1094 × 10−31 kg) × (1.3806 × 10−23 J K−1 ) × (380 K)]1�2
= 9.58 nm
P��B.� Combining Bragg’s law [��B.�b–���], λ = 2d sin θ, with the expression for the
the separation of planes for a cubic lattice [��A.�a–���], d hk l = a�(h 2 + k 2 +
l 2 )1�2 , gives sin θ = (λ�2a) (h 2 + k 2 + l 2 )1�2 .
�e di�raction patterns for cubic cells of di�erent types is illustrated in Fig. ��B.��
on page ���. Di�raction is possible for all (hkl) planes for a cubic P lattice, but
re�ections corresponding to (h + k + l) odd are absent for a cubic I lattice. For a
cubic F lattice, re�ections are absent where two out of h, k and l are odd. �ese
systematic absences in a di�raction pattern allow the lattice type to be assigned.
�e observation of a (100) re�ection, for which (h + k + l) is odd, rules out
cubic I. �e observation of a (110) re�ection, for which h and k are odd, but
l is even, rules out cubic F. �erefore polonium must be cubic P, for which all
re�ections are present.
�e sequence of re�ections expected for cubic P is shown in Fig. ��B.�� on
page ���: the ��h, sixth and seventh re�ections are (210), (211) and (220),
respectively. �e sine of the re�ection angle is proportional to (h 2 + k 2 + l 2 )1�2 ,
which for these three re�ections is 51�2 , 61�2 , and 81�2 : the separation between
the sixth and seventh is indeed larger than that between the ��h and sixth, as
described.
�e cell dimension is calculated from a = λ(h 2 + k 2 + l 2 )1�2 �(2 sin θ); each
re�ection allows a separate determination of a. For the (100) re�ection
λ(h 2 + k 2 + l 2 )1�2 λ(12 + 02 + 02 )1�2 λ(1)1�2
a= = =
2 sin θ 2 sin θ 2 sin θ
(154 pm) × (1)1�2
= = 3.42... × 102 pm
2 × 0.225
Similar calculations for the other re�ections given a = 3.44... × 102 pm and
a = 3.43... × 102 pm. �e average is a = 344 pm .

P��B.� Combining Bragg’s law [��B.�b–���], λ = 2d sin θ, with the expression for the
the separation of planes for a cubic lattice [��A.�a–���], d hk l = a�(h 2 + k 2 +
l 2 )1�2 , gives sin θ = (λ�2a) (h 2 + k 2 + l 2 )1�2 . For the same re�ection, a is
proportional to 1� sin θ, therefore
sin θ NaCl (564 pm) × (sin 6.00○ )
a KCl = a NaCl = = 628.7... pm = ��� pm
sin θ KCl sin 5.38○
�e mass density ρ is ρ = m�V , where m is the mass of the unit cell. If there
are N formula units per cell then ρ = N M�N A V , where M is the molar mass
of a formula unit. Based on the cell parameter a, the ratio of densities of KCl
and NaCl is therefore
ρ KCl 3
M KCl a NaCl (74.55 g mol−1 ) × (564 pm)3
= = = �.���
ρ NaCl M NaCl a KCl (58.44 g mol−1 ) × (628.7... pm)3
3

�e experimentally determined ratio of mass densities is �.�� g cm−3 /�.�� g cm−3 =

�.���, which is close to the value determined from the di�raction data. �e data
therefore support the X-ray analysis.
P��B.� �e intensity of a re�ection is proportional to the square modulus of the struc-
ture factor given by [��B.�–���], Fhk l = ∑ j f j ei� hk l ( j) , where the phase is � hk l ( j) =
2π(hx j + ky j + l z j ).
For atoms at positions (�,�,�), (�, 12 , 12 ), ( 12 , 12 , 12 ), and ( 12 , �, 34 ) with the same
scattering factor f
Fhk l = f �e0i + eiπ(k+l ) + eiπ(h+k+l ) + eiπ(h+3l �2) �
For the (114) re�ection, F114 = f �1 + e5πi + e6πi + e7πi �. Using the result eiπn =
(−1)n it follows that F114 = f (1−1+1−1) = � . �e I atoms therefore contribute
no net intensity to the (114) re�ection.

P��B.� �e scattering intensity is given by the Wierl equation [��B.�–���],

I(θ) = � f i f j sin (sR i j )�(sR i j )
i, j

where s = 4π sin (θ�2)�λ and the sum is over all pairs of atoms in the species.
(a) For the Br� molecule, f 1 = f 2 = f with R 12 = R. �us I(θ) = f 2 sin (sR)�(sR).
To �nd the positions of the �rst maximum and minimum, di�erentiate I
with respect to θ and set equal to zero.
dI dI ds 2π f 2
= = [sR cos(sR) − sin(sR)] cos (θ�2) = 0
dθ ds dθ s 2 Rλ
Rearranging sR cos(sR) − sin(sR) = 0 gives tan(sR) = sR which is solved
numerically to give solutions at sR = 0, 4.493, 7.725, .... Inspection of
the form of the function I(θ) shows that the solution sR = 0 corresponds
to the �rst maximum, therefore sR = 4.493 corresponds to the �rst min-
imum. �e angle θ is computed from sR using θ = 2 sin−1 (sλ�4π) =
2 sin−1 (sRλ�4πR). Taking the Br� bond length as ���.� pm gives for
neutron scattering
(4.493) × (78 pm)
θ max = � θ min = 2 × sin−1 = 14.0○
4π(228.3 pm)
and for electron scattering
(4.493) × (4.0 pm)
θ max = � θ min = 2 × sin−1 = 0.72○
4π(228.3 pm)
(b) For CCl� there are four carbon-chlorine pairs and six chlorine-chlorine
pairs
sin sR CCl 2 sin sR ClCl
I = 4 f C f Cl + 6 f Cl
sR CCl sR ClCl
sin �(8�3) sR CCl �
1�2
sin sR CCl
= 4 × 6 × 17 × f 2
+ 6 × (17)2 × f 2
sR CCl (8�3) sR CCl
1�2

sin �(8�3) sR CCl �

1�2
I sin sR CCl
= 408 + 1061.8... ×
f2 sR CCl sR CCl
 2 000 �.��� �.��� ��.��

1 500

1 000 �.��� �.��� ��.�� ��.��

I� f 2

500

0 2 4 6 8 10 12 14 16
sR CCl

A plot of I� f 2 against sR CCl is shown in Fig. ��.�. �e values of sR CCl

at which the maxima and minima occur are found using mathematical
so�ware or, alternatively, the values can be estimated from the graph.
�ese values are indicted on the plot.
From the experimental data on the angles at which extrema occur, θ ex , it is
possible to calculate an experimental value s ex using s ex = 4π sin (θ ex �2)�λ.
From the graph the values of (sR)theo at which extrema occur are known,
so from each item of data a value of R is found by computing R ex =
(sR)theo �s ex . �e data and computed values are shown in the table.
To complete these calculations it is necessary to know the de Broglie wave-
length associated with �� keV electrons. �e kinetic energy is E = p2 �(2m e )
= eV where p is momentum, m e is the electron mass, e is its charge and
V is the potential di�erence applied. Using the de Broglie relation,
h h
λ= =
p (2m e eV )1�2
6.6261 × 10−34 J s
=
[2×(9.1094 × 10−31 kg) × (1.6022 × 10−19 C) × (1.00 × 104 V)]1�2
= 12.2... pm

maxima minima
○ ○ ○ ○
θ ex 3.17 5.37 7.90 1.77 4.10○ 6.67○ 9.17○
s ex �pm−1 �.���� �.���� �.���� �.���� �.���� �.���� �.����
(sR)theo �.��� �.��� ��.�� �.��� �.��� ��.�� ��.��
R ex �pm ���.� ���.� ���.� ���.� ���.� ���.� ���.�

�e outlying values 168.3 pm and 183.8 pm are rejected, to give an average

 value of R CCl = 178 pm .

D��C.� In a face-centred cubic close-packed lattice, there is an octahedral hole in the

centre. �e rock-salt structure can be thought of as being derived from an fcc
structure of Cl – ions in which Na+ ions have �lled the octahedral holes.
�e caesium-chloride structure can be considered to be derived from the ccp
structure by having Cl – ions occupy all the primitive lattice points and octahe-
dral sites, with all tetrahedral sites occupied by Cs+ ions. �is is rather di�cult
to visualize and describe without carefully constructed �gures or models: refer
to S.-M. Ho and B.E. Douglas, J. Chem. Educ. ��, ���, (����), for the appropri-
ate diagrams.

E��C.�(b) �e distance x, indicated in Fig. ��.�, is half of the width of the triangular face
of a rod. �e area A of this face is 12 × base × height which is A = 12 × 2x ×
√
2x × sin 60○ = 3x 2 . �e small equilateral triangles which are formed √ by the
spaces between the rods have edges of length x and thus area A space = 3x 2 �4.
Each rod is adjacent to � of these small triangular spaces, but in turn each of
these spaces is in contact with � rods. Overall, therefore, there are two small
triangular spaces per rod. �e length of the rods is irrelent to the packing
fraction, and so
√ 2
A 3x 2
f = =√ √ =
A + 2A space 3x 2 + 2 × 3x 2 �4 3

E��C.�(b) �e packing fraction is f = NVa �Vc where N is the number of spheres per unit
cell, Va = 4πR 3 �3 is the volume of each sphere of radius R, and Vc is the volume
of the unit cell.
An orthorhombic C cell is shown in Fig. ��A.� on page ���. �e spheres touch
along a face diagonal which therefore has length 4R. If the edge of the cube
 length a it follows, by considering a face, that (4R)2 = a 2 + a 2 and hence
has √
a = 8R. For this cell N = 2 and hence

2 × 4πR 3 �3 π
f = √ = √ = �.����
( 8R) 3 6 2

E��C.�(b) �e coordination number N of an ionic lattice depends on the radius ratio of

the cation and anion of the lattice. �e radius-ratio rule, which considers the
maximum possible packing density of hard spheres of a given radius around a
hard sphere of a di�erent radius, provides a method to determine the structure
type. �e radius ratio is γ = r s �r l where r s is the radius of the smallest ion and
r l is the radius of the largest ion. If γ ≤ (21�2 − 1) then N < 6; for (21�2 − 1) <
γ < (31�2 − 1) then N = 6; for γ ≥ (31�2 − 1) then N = 8.
�e range for sixfold coordination is therefore 0.414 < γ < 0.732, and hence
r l × 0.414 < r s < r l × 0.732. For the case of the Rb+ anion (149 pm) × 0.414 =
61.7 pm and (149 pm) × 0.732 = 109 pm. �erefore for sixfold coordination
the smallest radius for the anion is ��.� pm , whilst for eightfold coordination
the smallest radius is ��� pm .

E��C.�(b) �e unit cell volume V is related to the packing density f and the atomic vol-
ume v by f V = v. Assuming the atoms can be approximated as spheres then
v = 4πR 3 �3 where R is the atomic radius. �e packing densities for bcc and hcp
are �.���� and �.����, respectively (Exercise E��C.�(a)). With the given data

Vbcc v bcc f hcp (R bcc )3 f hcp 1223 × 0.7405...

= × = = = 0.988...
Vhcp v hcp f bcc (R hcp )3 f bcc 1263 × 0.6802...

�us transformation from hcp to bcc causes cell volume to contract by 1.2%

E��C.�(b) �e lattice enthalpy ∆H L is the change in standard molar enthalpy for the pro-
cess MX(s) → M+ (g) + X− (g) and its equivalent. �e value of the lattice en-
thalpy is determined indirectly using a Born–Haber cycle, as shown in Fig. ��.�
(all quantities are given in kJ mol−1 ). From the cycle it follows that

−524 kJ mol−1 + ∆H L = (148 + 2187 + 31 + 193 − 2 × 331) kJ mol−1

�us ∆H L = ���� kJ mol−1

P��C.� Figure ��.� shows the packing of the ellipses; the area of an ellipse is πab where a
and b are the semi-major and -minor axes, respectively. �e unit cell, indicated
by the dashed lines, is a parallelogram and contains one rod cross-section. A
pair of stacked ellipses have relative coordinates (x, y) and (x, y + 2b). �e
adjacent column of ellipses is centred b higher and so the contact point has
y-coordinate b�2 higher. �e equation for an ellipse is (x�a)2 + (y�b)2 = 1,
 Mg2+ (g)+� Br(g)
��� Mg2+ (g)+ Br� (g)
2 × −331
�� Mg2+ (g)+ Br� (l) Mg2+ (g) + � Br – (g)

����
Mg(g)+ Br� (l) ∆H L
��� Mg(s)+ Br� (l)

−524 MgBr� (s)

√
and with this the x coordinate corresponding to y =√b�2 is found as x = 3a�2.
√
If follows that the distance h is given by h = 2x = a 3, and thus the area of the
unit cell is 2bh = 2 3ab. It follows that the packing density is

1 × πab π
f = √ = √ = �.���
2 3ab 2 3

�e eccentricity of an ellipse is de�ned as ε = [1 − (b 2 �a 2 )]1�2 . �e packing

fraction is independent of a and b and thus is independent of eccentricity.

2a

2b
h

P��C.� (a) �e general expression for the energy levels in a one-dimensional metallic
conductor is given by [��C.�–���], E(k) = α + 2β cos(kπ�[N + 1]) where
k = 1, 2, ..., N. It is convenient to �rst compute dE�dk

dE d kπ 2βπ kπ
= �α + 2β cos � �� = − sin � �
dk dk N +1 N +1 N +1

�e identity cos2 x +sin2 x = 1 is used to write sin x = �1 − cos2 x�

1�2
, and
in turn this is used to rewrite sin[kπ�(N+1)] as �1 − cos (kπ�[N + 1])� .
2 1�2

�e expression for the energy levels, E(k) = α + 2β cos[kπ�(N + 1)], is

 rearranged to give cos (kπ�[N + 1]) = (E − α)�(2β). �ese two substi-
tutions are used in the expression for the derivative
1�2
dE 2βπ kπ 2βπ kπ
=− sin � �=− �1 − cos2 � ��
dk N +1 N +1 N +1 N +1
� 2�
2βπ � �
1�2

=− �1 − � E − α � �
�
N +1 � �
2β �
� �
Density of states ρ(E) is de�ned as ρ(E) = dk�dE, thus

dk 1 (N + 1)�2βπ
ρ(E) = = =−
dE dE�dk 2 1�2
�1 − � E−α
2β
� �

(b) As E → α ± 2β, E − α → ±2β, and thus (E − α)�2β → ±1. It follows that

(N + 1)�2βπ
ρ(E) → − =∞
[1 − (±1)2 ]
1�2

�us the density of states increases towards the edges of the bands in a
one-dimensional metallic conductor.

P��C.� �e wavefunction for a ring of N atoms must be such that it has the same value
at the (hypothetical) atom with index (N +1) as it does for the atom with index
� because, in a ring these two atoms are the same. �is can only be achieved if
the wavefunction varies in such a way that it goes through a whole number of
cycles around the ring.
�e wavefunction for a line of atoms is not constrained in this way, so if a linear
chain were to have its ends ‘connected’ to form a ring, some wavefunctions of
the linear chain would not satisfy requirements necessary to be a wavefunction
for a ring of atoms.
�e energy levels of a line of atoms are non-degenerate, but for a ring all of the
levels, apart from the one with k = 0, are doubly degenerate. �is degeneracy
can be associated with the possibility that the electron can travel clockwise or
anti-clockwise around the ring. For a chain, no such net motion is possible.

P��C.� (a) Assuming that the ionic radius of Ca+ is close to that of K+ , the radius-
ratio rule can be used to predict the lattice structure of CaCl. �e radius
ratio is γ = 138 pm�181 pm = 0.762; this is > 0.732, therefore eightfold
coordination, as in CsCl, is predicted and the appropriate value of the
Madelung constant (Table ��C.� on page ���) is A = 1.763.
�e Born–Mayer equation, [��C.�–���], is used to estimate the lattice
enthalpy since when zero-point contributions to potential energy are ne-
glected then lattice enthalpy is equal to the negative of Ep,min . In this
expression, z i is the charge number of ion i, d is the distance between
 neighbouring centres, A is the Madelung constant, ε 0 is the vacuum per-
mittivity and d ∗ is taken to be ��.� pm.
Taking the ionic radii from Table ��C.� on page ��� as r Ca+ ≈ r K+ =
138 pm and r Cl− = 181 pm, d = (138 + 181) pm = 319 pm.

N A �z A z B �e 2 d∗
Ep,min = − �1 − � A
4πε 0 d d
(6.0221 × 1023 mol−1 ) × (1.6022 × 10−19 C)2
=
4π × (8.8542 × 10−12 J−1 C2 m−1 ) × (319 pm)
34.5 pm
× �1 − � × 1.763 = −685 kJ mol−1
319 pm

�us the lattice enthalpy of CaCl(s) is ∆H L = 685 kJ mol−1 .

�e relevant Born–Haber cycle is shown in Fig. ��.�; all of the enthalpy
changes quoted in the diagram are in kJ mol−1 . �e �rst ionisation energy
of Ca, +���.� kJ mol−1 , is taken from Table �B.� in the Resource section.
It follows from the cycle that ∆ f H −○ = 176 + 589.7 + 122 − 349 − 685 =
−146 kJ mol−1

Ca+ (g)+Cl(g)
��� Ca+ (g)+ 12 Cl� (g) −349
Ca+ (g) + Cl – (g)
���
Ca(g)+ 12 Cl� (g)

��� Ca(s)+ 12 Cl� (g) −∆H L = −685

∆ f H −○ CaCl(s)

(b) �e disproportionation reaction for CaCl(s) is � CaCl(s) → Ca(s)+CaCl� (s).

Using data from Table �C.� in the Resource section and using the enthalpy
of formation of CaCl(s) calculated in part (a),

∆ r H −○ = ∆ f H −○ (Ca(s)) + ∆ f H −○ (CaCl2 (s)) − 2∆ f H −○ (CaCl(s))

= [0 − 795.8 − 2(−146)] kJ mol−1 = −504 kJ mol−1

Hence the disproportionation reaction is strongly exothermic. �e en-

tropy change for this reaction is expected to be close to zero since there
is no change in the number of species or their physical state, so it can
reasonably by concluded that ∆ r G −○ will also be negative, thus favouring
the products of the reaction. �us, it is plausible that CaCl is thermody-
namically unstable with respect to disproportionation.
P��C.�� �e Madelung constant is found by considering the contributions to the po-
tential energy of an ion that arise from interactions with the surrounding ions,
taking into account their number and distance from the ion in question. Con-
sider the central cation, and assume that the successive circles of anions and
cations are at distances r, 2r . . .. �e �rst circle contains four anions, so the
interaction with these will result in a negative contribution to the potential
energy of −4×e 2 �(4πε 0 r). �e next closest are four cations, and these will make
a positive contribution to the potential energy of +4 × e 2 �(4πε 0 2r). Similar
considerations apply to further circles of ions giving a series

4e 2 4e 2 4e 2 4e 2
V =− + − + +...
4πε 0 r 4πε 0 (2r) 4πε 0 (3r) 4πε 0 (4r)
e2 1 1 1
=− × 4 × �1 − + − + . . .�
4πε 0 r 2 3 4
�e series in parenthesis is the series expansion of ln 2, so the potential energy
is
e2
V =− × 4 × ln 2
4πε 0 r
�e Madelung constant in therefore A = 4 ln 2 = 2.773 .
For the periodic lattices described in the text the same result is obtained regard-
less of which ion it chosen as the ‘central’ ion in the calculation. �is is certainly
not the case for the arrangement considered in this Problem simply because the
arrangement of ions is not periodic and no unit cell can be de�ned.

E��D.�(b) �e relationship between the applied pressure p, the bulk modulus K, and the
fractional change in volume ∆V �V is given by [��D.�b–���], K = p�(∆V �V ).
From Exercise E��D.�(a) the bulk modulus of polystyrene is �.�� GPa. �e
fractional change in the volume is therefore

∆V p 1000 × 105 Pa
= = = 0.029...
V K 3.43 × 109 Pa
�e change in volume is expressed in terms of the initial and �nal volumes, Vi
and Vf

∆V �V = (Vf − Vi )�Vi hence Vf = (∆V �V )Vi + Vi

where it is assumed that the change in volume is small enough that V is well-
approximated by Vi . �us Vf = −(0.029... × 1.0 cm3 ) + 1.0 cm3 = �.�� cm3 .
Note that ∆V must be negative because the sample is compressed by the addi-
tional pressure.
E��D.�(b) �e Young’s modulus E is related to the stress σ and the strain ε by [��D.�a–���],
E = σ�ε. Stress is given by σ = F�A where F is the force applied and A is the
cross-sectional area. Strain is given by ε = ∆L�L where L is the initial length
of the rod. It follows that E = FL�A∆L and hence F = EA∆L�L. �e Young’s
modulus of polystyrene is �.�� GPa.

EA∆L
F=
L
(4.42 × 109 Pa) × [π × (0.5 × 10−3 m)2 ] × (10.05 cm − 10.00 cm)
= = �� N
10.00 cm

E��D.�(b) Poisson’s ratio, ν P , is de�ned in [��D.�–���], ν P = εtrans �εnorm , where εtrans is

the transverse strain and εnorm is the normal (uniaxial) strain. If the normal
strain is �.�%, it follows that the change in length ∆Lnorm is

∆Lnorm = εnorm Lnorm = 0.02 × (0.1 m) = 2.0 × 10−3 m

�e transverse strain is εtrans = ν P εnorm , so the change in dimension in the

transverse direction ∆Ltrans is

∆Ltrans = εtrans Ltrans = ν P εnorm Ltrans = 0.41 × 0.02 × (0.1 m) = 8.2 × 10−4 m

It is expected that the result of applying the stress will be to decrease the size
of the cube in the transverse dimension (that is ∆Ltrans is negative), and that
the decrease will be the same in each transverse direction. �e volume a�er the
stress has been applied is therefore

(0.1 m + 2.0 × 10−3 m) × (0.1 m − 8.2 × 10−4 m)2 = 1.00334... × 10−3 m3

�e change in volume is 1.00334...×10−3 m3 −1.0×10−3 m3 = 3.3 × 10−3 dm3

P��D.� If neighbouring molecules interact by a Lennard-Jones potential energy then

the bulk modulus K is related to the Lennard-Jones parameter ε (the depth of
the potential well) by K = 8N A ε�Vm , where Vm is the molar volume. �e molar
volume is expressed in terms of the molar mass M and the mass density ρ as
Vm = M�ρ. From the Resource section the mass density for water at 298 K is
1.0 g cm−3 , and the molar mass is 18.01... g mol−1 .

KVm KM (3.4 × 109 Pa) × (18.01... g mol−1 )

ε= = =
8N A 8N A ρ 8 × (6.0221 × 1023 mol−1 ) × (1.0 × 106 g m−3 )
= 1.27... × 10−20 J

Hence ε = (1.27... × 10−20 J) × (6.0221 × 1023 mol−1 ) = 7.7 kJ mol−1

E��E.�(b) Assuming that the temperature, T, is not so high that many electrons are excited
to states above the Fermi energy, E F , the Fermi–Dirac distribution can be writ-
ten as [��E.�b–���], f (E) = 1�[e(E−E F )�k T + 1], where f (E) is the probability
of occupation of a state with energy E.
For E = E F − kT, f (E F − kT) = 1�[e(E F −k T−E F )�k T + 1] = 1�[e−1 + 1] = �.���
Compared to the state with energy E = E F + kT, for E = E F − kT the probability
of the state being occupied is much greater, and this is simply a re�ection of
the fact that the probability of a state being occupied decreases as the energy
increases.

E��E.�(b) �e Fermi–Dirac distribution is given by [��E.�b–���], f (E) = 1�[e(E−E F )�k T +

1], where f (E) is the probability of occupation of a state with energy E, and
E F is the Fermi energy. In this case E F = 2.00 eV = 3.20... × 10−19 J, using the
conversion factor from inside of the front cover. With some rearrangement of
the expression for f (E) it follows that
E = kT ln[1� f (E) − 1] + E F
= (1.3806 × 10−23 J K−1 ) × (298 K) × ln (1�0.10 − 1) + (3.20... × 10−19 J)
= 3.29... × 10−19 J = �.�� eV

E��E.�(b) Gallium is a Group �� element and germanium is a Group �� element. �us, an

electron can be transferred from a germanium atom to a neighbouring gallium
atom, thereby creating a hole in the valence band and increasing the conduc-
tivity of the material relative to pure germanium. �is type of doping results in
an p-type semi-conductor.

P��E.� �e Fermi–Dirac distribution is [��E.�a–���], f (E) = 1�[e(E−µ)�k T +1], where

f (E) is the probability of occupation of a state with energy E and µ is the
chemical potential.
(i) For E < µ then lim (E − µ)�kT = −∞ so lim f (E) = 1�(e−∞ + 1) = �
T→0 T→0
For E > µ then lim (E − µ)�kT = +∞ so lim f (E) = 1�(e∞ + 1) = 1�∞ = �
T→0 T→0
(ii) �e integral is evaluated at T = 0 by splitting it into two and using the
limits obtained in (i).
f (E)=1 f (E)=0
∞ µ � ∞ �
N =� ρ(E) f (E) dE = � ρ(E) f (E) dE + � ρ(E) f (E) dE
0 0 µ
µ µ
=� ρ(E) dE = � CE 1�2
dE = 2
3
C µ 3�2
0 0
 Substituting C = 4πV (2m e �h 2 )3�2 gives

8πV 2m e 3�2 3�2

N= � 2 � µ
3 h
(iii) Rearranging the previous equatio to make µ the subject gives
3N 2�3 h 2
µ=� �
8πV 2m e
With N = N�V gives

3N 2�3 h 2
µ=� �
8π 2m e
(iv) If each sodium atom contributes one electron to the solid, N is equal to the
number of sodium atoms in the solid. �e mass density ρ is expressed as
ρ = MN�N A V = MN �N A , where M is the molar mass of sodium. Hence
N = ρN A �M
3ρN A 2�3 h 2
µ=� �
8πM 2m e
3 × (9.7 × 105 g m−3 ) × (6.0221 × 1023 mol−1 )
2�3
=� �
8π × (22.99 g mol−1 )
(6.6261 × 10−34 J s)2
× = 5.049... × 10−19 J = �.� eV
2 × (9.1094 × 10−31 kg)

P��E.� �e conductance, G, of germanium is predicted to have an Arrhenius-like tem-

perature dependence. �e given equation is rearranged to give a straight-line
plot
Eg
G = G 0 e−E g �2k T hence ln G = ln G 0 −
2kT
Hence a plot of ln G against (1�T) should be a straight line with slope −E g �2k.�e
data are plotted in Fig. ��.�.

T�K G�S (1�T)�K−1 ln (G�S)

312 0.084 7 0.003 21 −2.469
354 0.429 0 0.002 82 −0.846
420 2.860 0 0.002 38 1.051

Linear regression analysis gives the equation for the best-�t line as
ln (G�S) = (−4.270 × 103 ) × (1�T)�K−1 + 11.22
�e band gap is computed from the slope
E g = −2k × (slope)
= −2×(1.3806 × 10−23 J K−1 ) × (−4.270 × 103 K) = 1.179 × 10−19 J
= �.��� eV
 1

ln (G�S)
−1

−2

0.0024 0.0026 0.0028 0.0030 0.0032

(1�T)�K−1

P��E.� It is assumed that the volume of the unit cell does not change on substitution
of Ca for Y. A tetragonal unit cell has volume V = a 2 c, where a and c are the
sides of the unit cell. �e mass density ρ is given by ρ = m�V , where m is the
total mass of the unit cell. �erefore ρ = N M�(N A V ) where N is the number
of formula units per unit cell and M is the molar mass of a formula unit. It
follows that M = ρN A V �N.
�ere are two formula units in each unit cell so N = 2 and
M = 2(200.59) + 2(137.33) + 88.91(1 − x) + 40.08x + 2(63.55)
+ 7.55(16.00)] g mol−1 = (1012.65 − 48.83x) g mol−1
From the data given
M = 12 ρN A a 2 c
= 12 (7.651 × 106 g m−3 ) × (6.0221 × 1023 mol−1 ) × (0.38606 × 10−9 m)2
× (2.8915 × 10−9 m)
= 992.82 g mol−1
Equating the expression for M with its numerical value gives 992.82 = (1012.65−
48.83x), hence x = (1012.65 − 992.82)�48.83 = �.��� .

E��F.�(b) �e magnetic moment m is given by [��F.�–���], m = g e [S(S +1)]1�2 µ B , where

g e = 2.0023 and µ B = eħ�(2m e ). For Mn2+ , 5.3µ B = g e [S(S + 1)]1�2 µ B , the
constant µ B cancels leaving a quadratic which is solved for S
√
S 2 +S−(5.3�2.0023) = 0 S = 12 (−1± 1 + 4 × 1 × 7.006...) = −0.500±2.693...
2
 Of the two solutions, S = −3.19 is non-physical, and the solution S = 2.19
is reasonably close to S = 2. A plausible conclusion is that Mn�+ has four
unpaired electrons. Most Mn�+ complexes in fact have �ve unpaired electrons.

E��F.�(b) �e molar susceptibility χ m of a substance is given by [��F.�–���], χ m = χVm ,

where χ is the volume magnetic susceptibility and Vm is the molar volume.
�e mass density ρ can be written ρ = M�Vm , hence Vm = M�ρ. With the data
given

χM (−7.9 × 10−7 ) × (6 × 12.01 + 12 × 1.0079) g mol−1

χ m = χVm = =
ρ 0.811 g cm−3
= −8.2 × 10−11 m3 mol−1

E��F.�(b) �e molar susceptibility χ m of a substance is given by [��F.�b–���], the Curie

law,
C N A g e2 µ 0 µ B2 S(S + 1)
χm = where C =
T 3k
�is is rearranged to give the spin quantum number as
3kT χ m
S(S + 1) =
N A g e2 µ 0 µ B2
3 × (1.3806 × 10−23 J K−1 ) × (298 K)
=
(6.0221 × 1023 mol−1 ) × (2.0023)2
6.00 × 10−8 m3 mol−1
×
(1.2566 × 10−6 J s2 C−2 m−1 ) × (9.2740 × 10−24 J T−1 )2
= 2.838...
To sort out the units the relations 1 T = 1 kg s−2 A−1 and 1 A = 1 C s−1 , hence
1 C = 1 A s, are useful. �e value of S is found by solving the quadratic
√
S 2 + S − 2.838... = 0 S = 12 (−1 ± 1 + 4 × 1 × 2.838...) = −0.500 ± 1.757...
�e root S = −2.26 is non-physical. �e other root, S = 1.26, implies an
e�ective number of electrons of 2 × 1.26 = �.� (higher precision is not justi�ed
because the expected result is an integer).
�e � electrons in a Ni�+ octahedral complex are arranged in the t2g and eg
orbitals such that there are � unpaired electrons. �e discrepancy between this
and the value of determined above arises because the analysis here considers
only the contribution from the electron spins and does not include any possible
orbital contribution; in addition, the e�ect of interactions between the spins is
not considered.

E��F.�(b) �e spin contribution to the molar magnetic susceptibility is given by equation

the Curie law, [��F.�b–���]
C N A g e2 µ 0 µ B2 S(S + 1)
χm = where C=
T 3k
 If octahedral coordination and a high-spin arrangement are assumed, the � d
electrons in Mn�+ are arranged as t32g e2g so theoretically there are � unpaired
electrons and S = 52

N A g e2 µ 0 µ B2 (6.0221 × 1023 mol−1 ) × (2.0023)2

=
3k 3 × (1.3806 × 10−23 J K−1 )
× (1.2566 × 10−6 J s2 C−2 m−1 ) × (9.2740 × 10−24 J T−1 )2
= 6.302... × 10−6 m3 K mol−1

To sort out the units the relations 1 T = 1 kg s−2 A−1 and 1 A = 1 C s−1 , hence
1 C = 1 A s, are useful. �e molar susceptibility follows as

(6.302... × 10−6 m3 K mol−1 ) × ( 52 )( 52 + 1)

χm = = 1.85 × 10−7 m3 mol−1
298 K

E��F.�(b) Superconductors classed as Type I show abrupt loss of superconductivity when

an applied magnetic �eld exceeds a critical value Hc characteristic of the mate-
rial. �e dependence of Hc on T is given by [��F.�–���], Hc (T) = Hc (0) �1 − T 2 �Tc2 �,
provided T ≤ Tc . �is relationship is rearranged to give T for a given applied
�eld

Hc (T) 150 kA m−1

1�2 1�2
T = Tc �1 − � = (9.5 K) �1 − � = �.� K
Hc (0) 158 kA m−1
�e material must be cooled to 2.1 K or lower to remain superconducting in a
magnetic �eld of 150 kA m−1 .

P��F.� No data is given in the degeneracy of the electronic levels, so any possible e�ect
of this is ignored in this answer (in fact both the ground and excited states are
doubly degenerate, which does not a�ect the result). Assuming that the ground
state has energy zero, and the excited state has energy ε, it follows that p 1 �p 0 =
e−ε�k T , where p 0 and p 1 are the probability of the ground and excited states
being occupied. By de�nition p 0 + p 1 = 1, so it follows that p 1 = e−ε�k T �(1 +
e−ε�k T ). Multiplying top and bottom of this expression by eε�k T gives p 1 =
1�(eε�k T + 1)
Since the ground state of NO exhibits no paramagnetism, only molecules in
the excited state contribute to the molar magnetic susceptibility. Consequently,
[��F.�b–���] must be modi�ed to include the probability of the state being
occupied

p 1 N A g e2 µ 0 µ B2 S(S + 1) N A g e2 µ 0 µ B2 S(S + 1)
χm = =
3kT 3kT(eε�k T + 1)

�e magnetic moment m is given by [��F.�–���], m = g e {S(S + 1)}1�2 µ B .

Rearranging this gives S(S + 1) = [m�(g e µ B )] , which is substituted into the
2
 previous equation to give
NA µ0 m2 N A µ 0 × (2µ B )2
χm = =
3kT(eε�k T + 1) 3kT(eε�k T + 1)
where m = 2µ B is used, as given in the question.
It is convenient to evaluate the term ε�k = hc ν̃�k
hc ν̃ (6.6261 × 10−34 J s) × (2.9979 × 1010 cm s−1 ) × (121.1 cm−1 )
= = 174.24... K
k 1.3806 × 10−23 J K−1
and also to evaluate
4N A µ 0 µ B2 4 × (6.0221 × 1023 mol−1 ) × (1.2566 × 10−6 J s2 C−2 m−1 )
=
3k 3 × (1.3806 × 10−23 J K−1 )
× (9.2740 × 10−24 J T−1 )2 = 6.286... × 10−6 m3 mol−1 K
�e �nal expression for the molar susceptibility is therefore
(6.286... × 10−6 m3 mol−1 K)
χm =
(T�K) × (1 + e(174.2 K)�(T�K) )
�is quantity is plotted as a function of temperature in Fig. ��.��. Initially χ m
increases due to the increasing population of the (paramagnetic) upper state.
Eventually, a temperature is reached at which the populations of the two states
are pretty much equal, and then χ m starts to fall o� in the way predicted by the
Curie law. �us, there is a maximum in the plot of χ m against T.

10
χ m �(10−9 m3 mol−1 )

0
0 50 100 150 200 250 300
T� K

D��G.� See Section ��G.� on page ���. Signi�cant non-linear e�ects are only seen when
strong (oscillating) electric �elds are applied. �e intense light available from
some lasers provides such a �eld.
E��G.�(b) �e maximum wavelength that allows promotion of electrons is
hc (6.6261 × 10−34 J s) × (2.9979 × 108 m s−1 )
λ= = = 1.10... × 10−6 m
∆ε (1.12 eV) × (1.6022 × 10−19 J eV−1 )
or �.�� µm

P��G.� (a) �e excited states of a dimer have energies ν̃± = ν̃mon ± β̃. With the given
parameters β̃ is evaluated as
2
µmon
β̃ = (1 − 3 cos2 θ)
4πε 0 hcr 3
[4.00 × (3.3356 × 10−30 C m)]2
=
4π(8.8542 × 10−12 J−1 C2 m−1 ) × (6.6261 × 10−34 J s)
(1 − 3 cos2 θ)
×
(2.9979 × 10 m s−1 ) × (0.50 × 10−9 m)3
8

= (6.44... × 104 m−1 )(1 − 3 cos2 θ) = (6.44... × 102 cm−1 )(1 − 3 cos2 θ)
�erefore the energies are
ν̃± �cm−1 = 25 000 ± (6.44... × 102 )(1 − 3 cos2 θ)
A plot of these as a function of θ is shown in Fig. ��.��.
(b) By analogy with [��C.�–���] the energies are given by
ν̃ chain = ν̃mon + 2Ṽ cos (kπ�[N + 1])
where k = 1, 2, 3, . . . , N. From part (i) when θ = 0, β̃ = −1.28... ×
103 cm−1 ; this is the value of Ṽ .
�e lowest-energy spectroscopic transition is from the ground state (de-
�ned to have energy zero) to the state with k = 1, and therefore occurs at
a wavenumber of
ν̃ min = ν̃mon + 2Ṽ cos (π�[N + 1])
ν̃ min �cm−1 = 25000 − (2.57... × 103 ) cos (π�[N + 1])
�is value of k makes cos(kπ�[N +1]) as close as possible to its maximum
value of �, and because Ṽ is negative, this gives the lowest energy.

N =5 ν̃ min �cm−1 = 25000 − (2.57... × 103 ) cos (π�6) = 2.277 × 104

N = 10 ν̃ min �cm−1 = 25000 − (2.57... × 103 ) cos (π�11) = 2.253 × 104
N = 15 ν̃ min �cm−1 = 25000 − (2.57... × 103 ) cos (π�16) = 2.247 × 104
N =∞ ν̃ min �cm−1 = 25000 − (2.57... × 103 ) cos (π�∞) = 2.242 × 104

For large N the cosine term tends to � and the transition is as ν̃mon + 2Ṽ .
 (c) Because the model considers only nearest neighbour interactions, the tran-
sition dipole moment of the lowest energy transition is independent of
the size of the chain.

27 000
ν̃+
ν̃−
26 000
ν̃± � cm−1

25 000

24 000

23 000
0 50 100 150
○
θ�

I��.� �e scattering factor f (θ) is given by [��B.�–���]

∞ sin kr 2 4π
f (θ) = 4π � ρ(r) r dr k= sin θ
0 kr λ
�e quantity 4πr 2 ρ(r) is identi�ed as the radial distribution function P(r),
which is given in terms of the radial wavefunction of the orbital, P(r) = R(r)2 r 2
∞ sin kr
f (θ) = � P(r) dr
0 kr
�e requested plot is of f (θ) as a function of ξ = sin θ�λ, hence k = 4πξ and
∞ sin(4πξr) 1 ∞
f (θ) = � P(r) dr = � R(r)2 sin(4πξr) r dr
0 4πξr 4πξ 0
From Table �A.� on page ��� the �s hydrogenic orbital the radial wavefunction
is R(r) = 2(Z�a 0 )3�2 e−Zr�a 0 , and so the radial distribution function is P(r) =
R(r)2 r 2 = 4(Z�a 0 )3 r 2 e−2Zr�a 0 . �e integral has to be evaluated numerically
using mathematical so�ware. �e parameter ξ is some fraction of 1�λ, where
λ is the wavelength of the X-rays used. Typically λ = 100 pm so ξ is less
than 1010 m−1 . �e upper limit of the integration can conveniently be set to
a modest multiple of the Bohr radius, say 100a 0 , because beyond this distance
the electron density will be negligible. �e computed scattering factor is shown
in Fig. ��.�� for Z = 1 and Z = 2. As expected, for forward scattering, ξ = 0,
the scattering factor is equal to the number of electrons, in this case �. As ξ
increases the scattering factor falls o�, but the decay is slower for the more
compact orbital with Z = 2.
For a �s hydrogenic orbital

R(r) = 8−1�2 (Z�a 0 )3�2 (2 − Zr�a 0 )e−Zr�2a 0

P(r) = 8−1 (Z�a 0 )3 (2 − Zr�a 0 )2 r 2 e−Zr�a 0

�e computed scattering factor is shown in Fig. ��.�� for Z = 1 and Z = 2.

As for the �s orbital the scattering factor is equal to � for forward scattering.
Compared to the �s the scattering from �s falls o� more quickly and also shows
some small negative excursions.

1.0
Z=1
0.8 Z=2

0.6
f

0.4

0.2

0.0
0.000 0.002 0.004 0.006 0.008 0.010
12
ξ�(10 m)

1.0
Z=1
Z=2

0.5
f

0.0
0.000 0.001 0.002 0.003 0.004 0.005
12
ξ�(10 m)
D��A.� �e di�usion constant is given by [��A.�–���], D = 13 λυ mean . �e mean free
path λ decreases as the pressure is increased ([��A.�a–���]), so D decreases
with increasing pressure and, as a result, the gas molecules di�use more slowly.
�e mean speed υ mean increases with the temperature ([��A.�b–���]), so D also
increases with temperature. As a result, molecules in a hot gas di�use more
quickly than those when the gas is cool (for a given concentration gradient).
Because the mean free path increases when the collision cross-section σ of
the molecules decreases, the di�usion coe�cient is greater for small molecules
than for large molecules.
�e viscosity is given by [��A.��c–���], η = 13 υ mean λmN . �e mean free path
is inversely proportional to the pressure and N is proportional to the pres-
sure, therefore the product λN , and hence the viscosity, is independent of
pressure. �e physical reason for this pressure-independence is that as the
pressure increases more molecules are available to transport the momentum,
but they carry it less far on account of the decrease in mean free path. �e
mean speed goes as T 1�2 (at constant volume) and so the viscosity increases
with temperature. �is is because at high temperatures the molecules travel
more quickly, so the �ux of momentum is greater.

E��A.�(b) For a perfect gas, the collision �ux Z w is [��A.�a–���], Z w = p�(2πmkT)1�2 .

�e number of helium molecule collisions within area A in time interval t is
therefore N = Z w At. �e mass m is written in terms of the molar mass M:
m = M�N A .

1�2
p pN A
N = Z w At = At = At
(2πmkT)1�2 (2πMkT)1�2
(111 Pa) × (6.0221 × 1023 mol−1 )1�2 × [(3.5 × 4.0) × 10−4 m2 ] × (10 s)
=
[2π × (0.004 kg mol−1 ) × (1.3806 × 10−23 J K−1 ) × (1500 K)]1�2
= 5.3 × 1022 collisions
E��A.�(b) �e di�usion constant is given by [��A.�–���], D = 13 λυmean , where λ is the
mean free path length λ = kT�σ p [��A.�a–���], and υmean is the mean speed
υmean = (8RT�πM)1�2 [��A.�b–���].

1 kT 8RT 1�2
D= � �
3 σ p πM
(1.3806 × 10−23 J K−1 )×(293.15 K) 8×(8.3145 J K−1 mol−1 )×(293.15 K)
1�2
= � �
3 × (4.3 × 10−19 m2 ) × (p�Pa) π × (0.02802 kg mol−1 )
1
= (1.476... m2 s−1 ) ×
p�Pa

�e �ux of nitrogen molecules atoms J z is related to the di�usion coe�cient D

and the concentration gradient dN �dz by [��A.�–���], J z = −DdN �dz. From
the perfect gas equation, pV = N kT, the number density is expressed in terms
of the pressure as N = N�V = p�kT. With this, the concentration gradient is
written in terms of the pressure gradient: dN �dz = (1�kT)dp�dz, and hence
the �ow is J z = −(D�kT)dp�dz

−D dp −1 (1.476... m2 s−1 ) × (1.2 × 105 Pa m−1 )

Jz = = ×
kT dz p�Pa (1.3806 × 10−23 J K−1 ) × (293.15 K)
−1
= (4.37... × 1025 m2 s−1 ) ×
p�Pa

p�Pa D�(m2 s−1 ) J z �(m−2 s−1 ) (J z �N A )�(mol m−2 s−1 )

���.� 1.48 × 10−5 −4.38 × 1023 −0.73
1.00 × 105 1.48 × 10−5 −4.38 × 1020 −7.3 × 10−4
2.00 × 107 7.38 × 10−8 −2.19 × 1018 −3.6 × 10−6

E��A.�(b) �e thermal conductivity is given by [��A.��c–���], κ = νpD�T, where the

di�usion coe�cient D is given by [��A.�–���], D = λυ mean �3. �e mean free
path λ is given by [��A.�a–���], λ = kT�σ p, and the mean speed υ mean is
given by [��A.�b–���], υmean = (8RT�πM)1�2 . �e quantity ν is the number
of quadratic contributions to the energy, and this is related to the heat capacity
by C V ,m = νkN A , hence ν = C V ,m �kN A . �e thermal conductivity is therefore
expressed as

νpD νpλυ mean C V ,m p kT 8RT 1�2 C V ,m 8RT 1�2

κ= = = � � = � �
T 3T kN A 3T σ p πM 3σ N A πM
20.8 J K−1 mol−1
hence κ =
3 × (4.3 × 10−19 m2 ) × (6.0221 × 1023 mol−1 )
8 × (8.3145 J K−1 mol−1 ) × (298 K)
1�2
� �
π × (2.802 × 10−2 kg mol−1 )
= 1.3 × 10−2 J K−1 m−1 s−1
E��A.�(b) �e thermal conductivity is given by [��A.��c–���], κ = νpD�T, where the
di�usion coe�cient D is given by [��A.�–���], D = λυ mean �3. �e mean free
path λ is given by [��A.�a–���], λ = kT�σ p, and the mean speed υ mean is
given by [��A.�b–���], υmean = (8RT�πM)1�2 . �e quantity ν is the number
of quadratic contributions to the energy, and this is related to the heat capacity
by C V ,m = νkN A , hence ν = C V ,m �kN A . �e thermal conductivity is therefore
expressed as

νpD νpλυ mean C V ,m p kT 8RT 1�2 C V ,m 8RT 1�2

κ= = = � � = � � (��.�)
T 3T kN A 3T σ p πM 3σ N A πM

Rearranging gives an expression for σ in terms of the thermal conductivity

C V ,m 8RT 1�2
σ= � �
3κN A πM
�e value of C p,m is given in the Resource section; C V ,m is found using C p,m −
C V ,m = R for a perfect gas. �e tabulated values of the thermal conductivity
are at ��� K. �ese can be converted to values at ��� K by using the fact
that κ ∝ T 1�2 , which follows from eqn ��.� provided that the hat capacity
can be assumed to be constant over the temperature range of interest. Hence
κ 298 K ≈ (298 K�273 K) κ 273 K ; with the value from the Resource section this
1�2

gives κ 298 K = 2.40 × 10 (298�273)1�2 = 2.50... × 10−2 J K−1 m−1 s−1

−2

(29.125 J K−1 mol−1 ) − (8.3145 J K−1 mol−1 )

σ=
3 × (2.50... × 10−2 J K−1 m−1 s−1 ) × (6.0221 × 1023 mol−1 )
8 × (8.3145 J K−1 mol−1 ) × (298 K)
1�2
� � = 0.218 nm2
π × (2.802 × 10−2 kg mol−1 )

�e value reported in Table �B.� on page �� is 0.43 nm2 .

E��A.�(b) �e �ux of energy is given by [��A.�–���], J z = −κ dT�dz. �e value of the

thermal conductivity κ for N� at ��� K is determined in Exercise E��A.�(b) as
1.3 × 10−2 J K−1 m−1 s−1 . As is seen in that Exercise, κ ∝ T 1�2 provided that
the heat capacity is constant over the temperature range of interest. It therefore
follows that κ 290 K = (290 K�298 K) κ 298 K = 1.28... × 10−2 J K−1 m−1 s−1 .
1�2

With these data the �ux is computed as

Jz = −κ dT�dz = −(1.28...×10−2 J K−1 m−1 s−1 )×(8.5 K m−1 ) = −0.11 J m−2 s−1

E��A.�(b) �e �ux of energy is given by [��A.�–���], J z = −κ dT�dz, where κ is the

thermal conductivity and the negative sign indicates �ow of heat is towards
the lower temperature. �e rate of energy transfer is r = J z A, where A is the
cross-sectional area. �e temperature gradient is approximated as dT�dz =
∆T�∆z. �e value of κ is approximated as the value given for N� in the Re-
source section, �� mW K−1 m−1 ; because � W = � J s−1 it follows that κ =
 2.4 × 10−2 J K−1 m−1 s−1 .
∆T
r = J z A = −κA
∆z
[(0) − (70)] K
= −(2.4 × 10−2 J K−1 m−1 s−1 ) × (2.00 m2 ) × = �� W
0.0500 m

E��A.�(b) �e viscosity η is given by [��A.��c–���], η = pMD�RT. In turn the di�usion

constant is given by [��A.�–���], D = 13 λυmean , where λ is the mean free
path length λ = kT�σ p [��A.�a–���], and υmean is the mean speed υmean =
(8RT�πM)1�2 [��A.�b–���]. �e �rst step is to �nd an expression for η as a
function of temperature

pMD pM kT 8RT 1�2 M 8RT 1�2 1 8RM 1�2 1�2

η= = � � = � � = � � T
RT RT 3σ p πM 3σ N A πM 3σ N A π
1
=
3 × (8.8 × 10 m ) × (6.0221 × 1023 mol−1 )
−19 2

8 × (8.3145 J K−1 mol−1 ) × (0.078... kg mol−1 )

1�2
� � T 1�2
π
= (8.08... × 10−7 kg K−1�2 m−1 s−1 ) × (T� K)1�2

where 1 J = 1 kg m2 s−2 has been used to arrive at the units on the �nal line. Us-
ing this expression the following table is drawn up (recall that 10−7 kg m−1 s−1 =
1 µP)

T�K η�(kg m−1 s−1 ) η�(µP)

��� 1.34 × 10−5 ���
��� 1.40 × 10−5 ���
���� 2.56 × 10−5 ���

E��A.�(b) In the solution to Exercise E��A.�(b) it is shown that

1 8RMT 1�2 1 8RMT 1�2

η= � � hence σ= � �
3σ N A π 3ηN A π

Recalling that 10−7 kg m−1 s−1 = 1 µP, the cross section is computed as
1
σ=
3 × (1.66 × 10−5 kg m−1 s−1 ) × (6.0221 × 1023 mol−1 )
8 × (8.3145 J K−1 mol−1 ) × (0.02802 kg mol−1 ) × (273 K)
1�2
� �
π
= �.��� nm2
E��A.�(b) �e rate of e�usion, r is given by [��A.��–���], r = pA 0 N A �(2πMRT)1�2 ; this
rate is the number of molecules escaping through the hole in a particular period
of time, divided by that time. �e mass loss ∆m in period ∆t is therefore ∆m =
∆t pA 0 N A �(2πMRT)1�2 × m, where m is the mass of a molecule. �is mass is
written m = M�N A and so it follows ∆m = ∆t pA 0 M 1�2 �(2πRT)1�2 . Evaluating
this with the values given

∆t pA 0 M 1�2
∆m =
(2πRT)1�2
(86 400 s) × (0.224 Pa) × π × ( 12 × 3.00 × 10−3 m)2 × (0.300 kg mol−1 )1�2
=
[2 × π × (8.3145 J K−1 mol−1 ) × (450 K)]1�2
= 4.89 × 10−4 kg = ��� mg

E��A.��(b) �e rate of e�usion, r is given by [��A.��–���], r = pA 0 N A �(2πMRT)1�2 ; this

rate is the number of molecules escaping through the hole in a particular period
of time, divided by that time. �e mass loss ∆m in period ∆t is therefore ∆m =
∆t pA 0 N A �(2πMRT)1�2 × m, where m is the mass of a molecule. �is mass is
written m = M�N A and so it follows ∆m = ∆t pA 0 M 1�2 �(2πRT)1�2 . �is is
rearranged to give an expression for p

∆m(2πRT)1�2 ∆m 2πRT 1�2

p= = � �
∆tA 0 M 1�2 ∆tA 0 M
2.77 × 10−4 kg 2π × (8.3145 J K−1 mol−1 ) × (573.15 K)
1�2
= � �
(500 s) × π × (2.5 × 10−4 m)2 0.200 kg mol−1
= 1.09 × 103 Pa

E��A.��(b) �e rate of e�usion, r is given by [��A.��–���], r = pA 0 N A �(2πMRT)1�2 ; this

rate is the number of molecules escaping through the hole in a particular period
of time, divided by that time. In this experiment the pressure changes so the rate
of e�usion changes throughout the experiment; nevertheless, the rate is always
proportional to M −1�2 . �e two experiments involve comparing the time for
the same drop in pressure, therefore the only factor that a�ects this time is the
molar mass of the e�using gas. Because the rate is proportional to M −1�2 the
time for a given fall in pressure will be proportional to the inverse of this, that
is M 1�2 . It follows that

rate for gas A time for gas B M B 1�2

= =� �
rate for gas B time for gas A MA

�erefore
1�2
82.3 s MB 82.3 2
=� � hence M B = (28.02 g mol−1 ) � � = ��� g mol−1
18.5 s M N2 18.5
E��A.��(b) �e rate of e�usion is given by [��A.��–���], dN�dt = pA 0 N A �(2πMRT)1�2 ;
this is the rate of change of the number of molecules. If it is assumed that the
gas is perfect, the equation of state pV = N kT allows the number to be written
as N = pV �kT, and therefore dN�dt = (V �kT)dp�dt. �e rate of change of
the pressure is therefore

dp kT pA 0 N A RTA 0 A 0 RT 1�2
=− = − × p = − � � ×p
dt V (2πMRT)1�2 V (2πMRT)1�2 V 2πM
��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
α

�e minus sign is needed because the pressure falls with time. �is di�eren-
tial equation is separable and can be integrated between p = p i and p = p f ,
corresponding to t = 0 and t = t.
pf t
� (1�p) dp = � −α dt hence ln(p f �p i ) = −αt
pi 0

�e time for the pressure to drop by the speci�ed amount is therefore

V 2πM 1�2
t = − ln(p f �p i )�α = ln(p i �p f ) � �
A 0 RT
1.22 × 105 Pa (22.0 m3 ) 2π × (2.802 × 10−2 kg mol−1 )
1�2
= ln � � � �
1.05 × 10 Pa [π(5.0 × 10 m) ] (8.3145 J K−1 mol−1 ) × (293 K)
5 −5 2

= 3.57 × 106 s = ��.� days

P��A.� �e thermal conductivity is given by [��A.��c–���], κ = νpD�T, where the

di�usion coe�cient D is given by [��A.�–���], D = λυ mean �3. �e mean free
path λ is given by [��A.�a–���], λ = kT�σ p, and the mean speed υ mean is
given by [��A.�b–���], υmean = (8RT�πM)1�2 . �e quantity ν is the number
of quadratic contributions to the energy

νpD νpλυ mean νp kT 8RT 1�2 νk 8RT 1�2

κ= = = � � = � �
T 3T 3T σ p πM 3σ πM

At ��� K the expectation is that three translational degrees of freedom and

two rotational degrees of freedom will contribute, giving ν = 5�2 (recall that
for a linear molecule there is no rotation about the long axis). At �� K the
temperature is far too low for the rotational degrees of freedom to contribute
and so ν = 3�2. �e ratio κ 300 K �κ 10 K is therefore

κ 300 K ν 300 K (300 K)1�2 (5�2) × (300 K)1�2

= = = �.��
κ 10 K ν 10 K (10 K)1�2 (3�2) × (10 K)1�2

P��A.� �e rate of e�usion, r is given by [��A.��–���], r = pA 0 N A �(2πMRT)1�2 ; this

rate is the number of molecules escaping through the hole in a particular period
 of time, divided by that time. �e mass loss ∆m in period ∆t is therefore ∆m =
∆t pA 0 N A �(2πMRT)1�2 × m, where m is the mass of a molecule. �is mass is
written m = M�N A and so it follows ∆m = ∆t pA 0 M 1�2 �(2πRT)1�2 . �is is
rearranged to give an expression for p

∆m(2πRT)1�2 ∆m 2πRT 1�2

p= = � �
∆tA 0 M 1�2 ∆tA 0 M
(4.3 × 10−8 kg) 2π × (8.3145 J K−1 mol−1 ) × (1273.15 K)
1�2
= � �
(7200 s) × [π(5.0 × 10−4 m)2 ] 0.07264 kg mol−1
= 7.28 × 10−3 Pa

P��A.� �e rate of e�usion is given by [��A.��–���], dN�dt = pA 0 N A �(2πMRT)1�2 ;

this is the rate of change of the number of molecules. If it is assumed that the
gas is perfect, the equation of state pV = N kT allows the number to be written
as N = pV �kT, and therefore dN�dt = (V �kT)dp�dt. �e rate of change of
the pressure is therefore

dp kT pA 0 N A RTA 0 A 0 RT 1�2
=− = − × p = − � � ×p
dt V (2πMRT)1�2 V (2πMRT)1�2 V 2πM
��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
α

�e minus sign is needed because the pressure falls with time. �is di�eren-
tial equation is separable and can be integrated between p = p 0 and p = p,
corresponding to t = 0 and t = t.

p t
� (1�p) dp = � −α dt hence ln(p�p 0 ) = −αt
p0 0

�e time dependence of the pressure is therefore given by

A 0 RT 1�2 V 2πM 1�2

p = p 0 e−α t α = � � or p = p 0 e−t�τ τ = � �
V 2πM A 0 RT

�e time t 1�2 for the pressure to fall from p 0 to p 0 �2 is given by

ln[(p 0 �2)�p 0 ] = −αt 1�2 hence t 1�2 = (ln 2)�α

�e half life of the pressure is therefore

V ln 2 2πM 1�2
t 1�2 = � �
A0 RT

�is half-life is independent of the pressure.

D��B.� �e Grotthuss mechanism for conduction by protons in water is described
in Section ��B.�(a) on page ��� and illustrated in Fig. ��B.� on page ���. It
seems plausible that such a mechanism could also occur in the relatively open
hydrogen bonded structure of ice.

E��B.�(b) �e temperature dependence of the viscosity η is given by [��B.�–���], η =

η 0 eE a �RT , where η 0 is viscosity in the limit of high temperature and E a is the
associated activation energy. Taking the natural logarithm gives ln η = ln η 0 +
E a �RT. Hence

Ea 1 1
ln η 1 − ln η 2 = (ln η 0 + E a �RT1 ) − (ln η 0 + E a �RT2 ) = � − �
R T1 T2

Rearranging gives an expression for the activation energy

ln (η 1 �η 2 )
Ea = R
(T1−1 − T2−1 )
ln [(1.554 cP)�(1.450 cP)]
= (8.3145 J K−1 mol−1 )
[(293.15 K)−1 − (313.15 K)−1 ]
= �.�� kJ mol−1

E��B.�(b) According to the law of independent migration of ions, the limiting molar
conductivity Λ○m of an electrolyte is given by the sum of the limiting molar
conductivities λ i of the ions present, [��B.�–���], Λ○m = ν+ λ+ + ν− λ− ; in this
expression ν+ and ν− are the numbers of cations and anions provided by each
formula unit of electrolyte. For each of the given electrolytes it follows that

Λ○KF = λ K+ + λ F− Λ○KCH3 CO2 = λ K+ + λ CH3 CO2 −

Λ○Mg(CH3 CO2 )2 = λ Mg2+ + 2λ CH3 CO2 −

�ese expressions are manipulated to give Λ○MgF2

Λ○MgF2 = λ Mg2+ + 2λ F−
= (Λ○Mg(CH3 CO2 )2 − 2λ CH3 CO2 − ) + 2(Λ○KF − λ K+ )
= Λ○Mg(CH3 CO2 )2 + 2Λ○KF − 2(λ CH3 CO2 − + λ K+ )
= Λ○Mg(CH3 CO2 )2 + 2Λ○KF − 2Λ○KCH3 CO2
= [18.78 + 2(12.89) − 2(11.44)] mS m2 mol−1 = ��.�� mS m2 mol−1
E��B.�(b) �e ion molar conductivity λ is given in terms of the mobility u by [��B.��–���],
λ = zuF, where z is the charge number of the ion (unsigned) and F is Faraday’s
constant; it follows that u = λ�zF. Note that 1 S = 1 C V−1 s−1 .

5.54 mS m2 mol−1
u F− = = 5.74×10−5 mS m2 C−1 = 5.74 × 10−8 m2 V−1 s−1
(1)(96485 C mol−1 )

7.635 mS m2 mol−1
u Cl− = −1 = 7.913×10 mS m C
−5 2 −1
= 7.91 × 10−8 m2 V−1 s−1
(1)(96485 C mol )
7.81 mS m2 mol−1
u Br− = = 8.09×10−5 mS m2 C−1 = 8.09 × 10−8 m2 V−1 s−1
(1)(96485 C mol−1 )

E��B.�(b) �e ion molar conductivity λ is given in terms of the mobility u by [��B.��–���],

λ = zuF, where z is the charge number of the ion (unsigned) and F is Faraday’s
constant. Note that 1 S = 1 C V−1 s−1 .

λ = zuF = (1)×(4.24×10−8 m2 V−1 s−1 )×(96485 C mol−1 ) = �.�� mS m2 C−1

E��B.�(b) �e dri� speed s of an ion is given by [��B.�b–���], s = uE, where E is the

electric �eld strength. �is �eld strength is given by E = ∆��l where ∆� is the
potential di�erence between two electrodes separated by distance l.
∆� 24.0 V
s = uE = u = (4.01 × 10−8 m2 V−1 s−1 ) ×
l 5.00 × 10−3 m
= 1.92 × 10 m s = ��� µm s
−4 −1 −1

E��B.�(b) �e Einstein relation, [��B.��–���], u = zDF�RT, gives the relationship be-

tween the mobility u, the charge number of the ion z, and the di�usion coe�-
cient D.
uRT (4.24 × 10−8 m2 V−1 s−1 ) × (8.3145 J K−1 mol−1 ) × (298 K)
D= =
zF (1) × (96485 C mol−1 )
= 1.09 × 10−9 m2 s−1

P��B.� To �t the data to the expression η = const.×eE a �Rθ , the natural logarithm is �rst
taken and then the base changed to common logarithms using ln x = log x ×
ln 10
Ea Ea
ln η = ln const. + hence log η = const. +
RT RT ln 10
�e log of the ratio η�η∗ , where η∗ is the viscosity at temperature T ∗ , is there-
fore
Ea 1 1
log η�η∗ = log η − log η∗ = � − � (��.�)
R ln 10 T T ∗
 �is expression is compared with that in the question by taking T ∗ = (20 +
273) = 293 K and rewriting the relationship as

1.3272[20 − (T�K − 273)] − 0.001053[20 − (T�K − 273)]2

log η�η 20 =
(T�K − 273) + 105
where θ�○ C = (T�K − 273) is used. One approach is to generate values of
log η�η 20 in the range �� ○ C to ��� ○ C and then plot these data against 1�T;
according to eqn ��.� the slope of such a graph is E a �R ln 10. Such a plot is
shown in Fig. ��.�.

0.0

−0.2
log(η�η 20 )

−0.4

−0.6
0.0026 0.0028 0.0030 0.0032 0.0034
(1�T�K)

�e data are a modest �t to a straight line with equation

log (η�η 20 ) = (7.4667 × 102 ) × 1�(T�K) − 2.5655

�e activation energy is computed from the slope as

E a = R ln 10 × (slope)
= (8.3145 J K−1 mol−1 ) × (ln 10) × (7.4667 × 102 K) = ��.� kJ mol−1

P��B.� �e conductance G is the reciprocal of the resistance R, G = 1�R. �e con-

ductivity of the solution in the cell depends on the measured conductance and
the physical dimensions of the cell. However, because in these measurements
the same cell is being used, it follows that the conductivity of the solution is
given by κ = A�R, where A is a constant. If the resistance of two solutions are
measured in the cell the ratio of the measured resistances is the inverse of the
ratio of their conductivities: R 1 �R 2 = κ 2 �κ 1 .
Both solutions are aqueous and hence their conductivities consist of contribu-
tions from the water component and acid component. �erefore
κ(acid solution) κ(acid) + κ(water) R(KCl solution)
= =
κ(KCl solution) κ(KCl) + κ(water) R(acid solution)
 Hence

R(KCl solution)
κ(acid) = × [κ(KCl) + κ(water)] − κ(water)
R(acid solution)
33.21 Ω
= × [(1.1639 + 0.076) S m−1 ] − (0.076 S m−1 )
300.0 Ω
= 61.2... mS m−1

�e molar conductivity, Λm is de�ned by equation [��B.�–���], Λm = κ�c,

where κ is conductivity and c is concentration. �us for 0.100 mol dm−3 ethanoic
acid,

κ(acid) 61.2... mS m−1 61.2... × 10−3 S m−1

Λm = = =
c 0.100 mol dm−3 0.100 × 103 mol m−3
= 0.613 mS m2 mol−1 = �.�� S cm2 mol−1

P��B.� (a) & (b) �e dri� speed s of an ion is given by [��B.�b–���], s = uE. �e electric
�eld strength E is given by E = ∆��l where ∆� is the potential di�erence
between two electrodes separated by distance l. Hence s = uE = u∆��l,
and the time taken to travel distance l is t = l�s.

100 V
For Li+ s = (4.01 × 10−8 m2 V−1 s−1 ) × = ��.� µm s−1
5.00 × 10−2 m
l 5.00 × 10−2 m
t= = = ��� s
s 80.2 × 10−6 m s−1
100 V
For Na+ s = (5.19 × 10−8 m2 V−1 s−1 ) × = ��� µm s−1
5.00 × 10−2 m
l 5.00 × 10−2 m
t= = = ��� s
s 104 × 10−6 m s−1
100 V
For K+ s = (7.62 × 10−8 m2 V−1 s−1 ) × = ��� µm s−1
5.00 × 10−2 m
l 5.00 × 10−2 m
t= = = ��� s
s 152 × 10−6 m s−1

(a) An alternating potential di�erence with frequency ν = 2.0 kHz requires

time t 1�2 = 1�2ν to complete a half-cycle. �e electric �eld strength is
given by E = E0 sin (2πνt) where E0 = (100 V)�(0.05 m) = 2.00 ×
103 V m−1
�e instantaneous displacement is given by s dt, so the net displacement
d is found by integrating this over a half cycle with s = uE0 sin(2πνt); the
 solvent diameter is taken at �.� nm.
1�2ν uE0
d=� uE0 sin(2πνt) dt =
0 πν
(4.01 × 10−8 m2 V−1 s−1 ) × (2.00 × 103 V m−1 )
d(Li ) =
+
= ��.� nm
π × (2 × 103 s−1 )
= �� solvent diameters
(5.19 × 10−8 m2 V−1 s−1 ) × (2.00 × 103 V m−1 )
d(Na+ ) = = ��.� nm
π × (2 × 103 s−1 )
= �� solvent diameters
(7.62 × 10−8 m2 V−1 s−1 ) × (2.00 × 103 V m−1 )
d(K+ ) = = ��.� nm
π × (2 × 103 s−1 )
= �� solvent diameters

P��B.� A spherical particle of radius a and charge ze travelling at a constant speed

through a solvent of viscosity η has mobility u given by [��B.�–���], u = ze� f ,
where f is the frictional coe�cient with Stokes’ law value f = 6πηa. It follows
that a = ze�6πηu. �e mobility is related to the di�usion coe�cient D by
the Einstein relation, [��B.��–���], u = zDF�RT, hence D = uRT�zF. �e
viscosity of water is 0.891 × 10−3 kg m−1 s−1 .
ze (1) × (1.6022 × 10−19 C) × 1012
a� pm = =
6πηu 6π × (0.891 × 10−3 kg m−1 s−1 ) × (u� m2 V−1 s−1 )
9.53... × 10−6
=
(u� m2 V−1 s−1 )
uRT (u� m2 V−1 s−1 ) × (8.3145 J K−1 mol−1 ) × (298 K)
D� m2 s−1 = =
zF (1) × (96485 C mol−1 )
= (2.56... × 10−2 ) × (u� m2 V−1 s−1 )

Li+ Na+ K+ Rb+

u�(10−8 m2 V−1 s−1 ) �.�� �.�� �.�� �.��
D�(10 −9
m s )
2 −1
�.�� �.�� �.�� �.��
a� pm ��� ��� ��� ���
ionic radius, r+ � pm �� ��� ��� ���

As commented on in the text, although a ‘free’ Li+ is much smaller than a free
Na+ ion the hydrodynamic radius of Li+ is greater than that of Na+ on account
of the more intense electric �eld generated by the smaller ion resulting in more
solvent molecules be attracted. �e number of water molecules being dragged
along with an ion is estimated as
volume of the solvated ion − volume of the free ion a 3 − r+3
Nw = =
volume of one water molecule r w3
 �e volumes are given by 43 πr 3 with the relevant radius: a is the hydrodynamic
radius, r+ is the radius of the ion, and r w is the radius of a water molecule, taken
to be ��� pm.
2383 − 593
N w (Li+ ) = = 3.9 = �
1503
1843 − 1023
N w (Na+ ) = = 1.5 = � to �
1503

D��C.� See the text following [��C.�–���].

E��C.�(b) �e root mean square displacement in three dimensions is given by [��C.��b–

���], �r 2 �1�2 = (6Dt)1�2 , where D is the di�usion coe�cient and t is the time
period.
�r 2 � (1.0 × 10−2 m)2
t= = = 7.4 × 103 s
6D 6 × (2.26 × 10−9 m2 s−1 )

E��C.�(b) �e di�usion in one dimension from a layer of solute is described by [��C.��–

���]
n0
c(x, t) = e−x �4D t
2

A(πDt)1�2
where c(x, t) is the concentration at time t and distance x from the layer, and
n 0 is the amount in moles in the layer of area A placed at x = 0. If the mass of
I� is m, then n 0 = m�M, where M is the molar mass (���.� g mol−1 ).
m
c(x, t) = e−x �4D t
2

MA(πDt) 1�2

(0.01 kg) × e−(5.0×10 m) �4×(4.05×10 m s )t

−2 2 −9 2 −1

c(5.0 cm, t)=

(253.8 g mol−1 )×(10.0 × 10−4 m2 )×[π(4.05 × 10−9 m2 s−1 )t]1�2
= [(3.49... × 102 mol dm−3 ) × (t� s)−1�2 ]e−1.54 ...×10 �(t� s)
5

c(5.0 cm, 10 s) = (3.49... × 102 mol dm−3 ) × (10)−1�2 × e−1.54 ...×10 �(10)
5

= 0.00 mol dm−3

c(5.0 cm, 24 h) = (3.49... × 102 mol dm−3 )[24(3600)]−1�2 × e−1.54 ...×10 �[24(3600)]
5

= 0.199 mol dm−3

Di�usion is a very slow process: a�er �� s the concentration at a height of �� cm
is zero to within the precision of the calculation.
E��C.�(b) �e thermodynamic force F is given by [��C.�b–���]
RT ∂c
F =− � �
c ∂x T , p

Substituting c(x) = c 0 − βc 0 x 2 into the above expression gives

RT 2βxRT
F =− (−2βc 0 x) =
c 0 − βc 0 x 2 1 − βx 2
�e constant α is found by noting that c = c 0 �2 at x = 20 cm = 0.20 m. Hence
c 0 �2 = c 0 − βc 0 × (0.20 m)2 and therefore β = 12.5 m−2 .
At T = 298 K and x = 8 cm the force is
2 × (12.5 m−2 ) × (8 × 10−2 m) × (8.3145 J K−1 mol−1 ) × (298 K)
F=
1 − (12.5 m−2 ) × (8 × 10−2 m)2
= �.� kN mol−1

A similar calculation at x = 16 cm gives F = �.� kN mol−1 .

E��C.�(b) �e thermodynamic force F is given by [��C.�b–���]

RT ∂c
F =− � �
c ∂x T , p

Substituting c(x) = c 0 e−α x into the above expression gives

2

RT
F =− −α 2 (−2αc 0 xe
−α x 2
) = 2αxRT
c0 e x

�e constant α is found by noting that c = c 0 �2 at x = 10 cm = 0.10 m. Hence

c 0 �2 = c 0 e−α(0.10 m) and therefore α = ln 2�(0.10 m)2 = 69.3 m−2
2

�e thermodynamic force at T = 291 K and x = 10.0 cm is

F = 2(69.3 m−2 )×(0.10 m)×(8.3145 J K−1 mol−1 )×(291 K) = ��.� kN mol−1

E��C.�(b) �e root mean square displacement in three dimensions is given by [��C.��b–

���], �r 2 �1�2 = (6Dt)1�2 , where D is the di�usion coe�cient and t is the time
period. Hence,
�r 2 � (1.0 × 10−2 m)2
t= = = 4.1 × 103 s
6D 6 × (4.05 × 10−9 m2 s−1 )

E��C.�(b) �e Stokes–Einstein equation [��C.�b–���], D = kT�6πηa, relates the di�u-

sion coe�cient D to the viscosity η and the radius a of the di�using particle,
which is modelled as a sphere. Recall that 1 cP = 10−3 kg m−1 s−1 .

kT (1.3806 × 10−23 J K−1 ) × (298 K)

a= = = �.��� nm
6πηD 6π × (1.00 × 10−3 kg m−1 s−1 ) × (1.055 × 10−9 m2 s−1 )
E��C.�(b) �e Einstein–Smoluchowski equation [��C.��–���], D = d 2 �2τ, relates the dif-
fusion coe�cient D to the jump distance d and time τ required for a jump.
Approximating the jump length as the molecular diameter, then d ≈ 2a where
a is the e�ective molecular radius. �is is estimated using the Stokes–Einstein
equation [��C.�b–���], D = kT�6πηa, to give 2a = 2kT�6πηD.
Combining these expressions and using the value η = 0.386 × 10−3 kg m−1 s−1
for the viscosity of heptane gives
2 2
d2 1 2kT 1 kT
τ= = � � = � �
2D 2D 6πηD 18D 3 πη
(1.3806 × 10−23 J K−1 ) × (298 K)
2
1
= � �
18 × (3.17 × 10−9 m2 s−1 )3 π × (0.386 × 10−3 kg m−1 s−1 )
= 2.01 × 10−11 s = 20.1 ps

E��C.�(b) �e root mean square displacement in three dimensions is given by equation

[��C.��b–���], �r 2 �1�2 = (6Dt)1�2 , where D is the di�usion coe�cient and t is
the time period. �erefore t = �r 2 ��6D.
For an iodine molecule in benzene, D = 2.13 × 10−9 m2 s−1

�r 2 � (1.0 × 10−3 m)2

t(1.0 mm) = = = �� s
6D 6 × (2.13 × 10−9 m2 s−1 )

�r 2 � (1.0 × 10−2 m)2

t(1.0 cm) = = = 7.8 × 103 s = 2.2 h
6D 6 × (2.13 × 10−9 m2 s−1 )

For a sucrose molecule in water, D = 0.5216 × 10−9 m2 s−1

�r 2 � (1.0 × 10−3 m)2

t(1.0 mm) = = = ��� s
6D 6 × (0.5216 × 10−9 m2 s−1 )

�r 2 � (1.0 × 10−2 m)2

t(1.0 cm) = = = 3.2 × 104 s = 8.9 h
6D 6 × (0.5216 × 10−9 m2 s−1 )

P��C.� �e thermodynamic force F is given by [��C.�b–���]

RT ∂c
F =− � �
c ∂x T , p

Substituting c(x) = c 0 e−ax into the above expression gives

2

RT
F =− −ax 2 (−2ac 0 xe
−ax 2
) = 2axRT
c0 e
 Hence for a = 0.10 cm−2 = 0.10 × 104 m−2 ,
F = 2 × (0.10 × 104 m−2 ) × (8.3145 J K−1 mol−1 ) × (298 K) × (x� m)
= (4.95... × 106 N mol−1 ) × (x� m)
= (5.0 MN mol−1 ) × (x� m)
= (8.2 × 10−18 N molecule−1 ) × (x� m)

200
F� kN mol−1

−200

−4.0 −2.0 0.0 2.0 4.0

x� cm

A plot of the thermodynamic force per mole against x is shown in Fig. ��.�. It
demonstrates that the force is directed such that mass is pushed by the thermo-
dynamic force toward the ends of the tube, down the concentration gradient. A
negative force pushes mass toward the le� (x < 0) and a positive force pushes
mass toward the right (x > 0).

P��C.� �e concentration c of di�used solute at radius r is give by [��C.��–���]. In that

equation n 0 is the total amount of solute present, and this can be expressed as
n 0 = m�M where m is the mass of solute and M is the molar mass, to give

n 0 e−r �4D t mer �4D t

2 2

c(r, t) = =
8(πDt)3�2 8M(πDt)3�2

(10.0 g) × (10−3 ) × e−(10×10 m) �[4t×(5.22×10 m s )]

−2 2 −10 2 −1

c(10 cm, t) =
8 × (342.30 g mol−1 ) × (π(5.22 × 10−10 m2 s−1 )t)3�2
= (5.49... × 107 mol dm−3 ) × (t�s)−3�2 × e−4.78 ...×10 �(t�s)
6

c(10 cm, 1.0 h) = (5.49... × 107 mol dm−3 ) × (3600)−3�2 × e−4.78 ...×10 �3600
6

= 0.00 mol dm−3

c(10 cm, 1.0 wk) = (5.49... × 107 )(6.048 × 105 s)−3�2 × e−4.78 ...×10 �(6.048×10 5 s)
6

= 4.25 × 10−5 mol dm−3

 �e process is very slow; even a�er � hour the concentration at a radius of ��
cm is zero to within the precision of the calculation.

P��C.� (a) �e generalised di�usion equation is given by [��C.�–���], where c is

concentration, t is time, D is the di�usion coe�cient, x is displacement
and υ is the velocity of convective �ow.

∂c ∂2 c ∂c
=D 2 −υ
∂t ∂x ∂x
An expression for c(x, t) is a solution of the di�usion equation if substi-
tution of the expression for c(x, t) into each side of the di�usion equation
gives the same result. �e proposed solution is
c0
c(x, t) = e−(x−x 0 −υt) �4D t
2

(4πDt) 1�2

LHS
∂c 1 (x − x 0 )2 υ 2
= c(x, t) �− + − �
∂t 2t 4Dt 2 4D
RHS
∂2 c ∂c ∂ −(x − x 0 − υt) −(x − x 0 − υt)
D −υ =D � c(x, t)� − υ � c(x, t)�
∂x 2 ∂x ∂x 2Dt 2Dt
(x − x 0 − υt)2 − 2Dt (x − x 0 − υt)
= D� c(x, t)� + υ � c(x, t)�
(2Dt)2 2Dt
(x − x 0 − υt)2 1 υ
= c(x, t) � − + (x − x 0 − υt)�
4Dt 2 2t 2Dt
1 (x − x 0 )2 υ 2
= c(x, t) �− + − �
2t 4Dt 2 4D

�e LHS is equal to the RHS, and so the proposed function is indeed a

solution to the generalised di�usion equation.
As t → 0 the exponential term e−x �4D t falls o� more and more rapidly,
2

implying that in the limit t = 0 all the material is at x = 0. �e exponential

function dominates the term t 1�2 in the denominator.
(b) Using the values D = 5 × 10−10 m2 s−1 and υ = 10−6 m s−1 , Fig. ��.� shows
the concentration pro�le against time at di�erent distances (x − x 0 ) =
0.5 mm, 1.0 mm, 5.0 mm. As expected, the initial concentration at a given
distance is zero. As time passes, the concentration begins to increase to
a maximum value when (x − x 0 = υt) and then, as di�usion continues
in the x-direction, the concentration begins to decrease toward zero at
longer times. �e value of c(x, t)�c 0 reaches its maximum value at longer
times as the value of (x−x 0 ) is increased since it takes longer for the solute
to reach distance (x − x 0 ).
 800
(x − x 0 ) = 0.5 mm
(x − x 0 ) = 1.0 mm
600
(x − x 0 ) = 5.0 mm

c(x, t)�c 0 400

200

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
t� hours

200 t = 1 hr
t = 5 hrs
150 t = 20 hrs
c(x, t)�c 0

100

50

0
0 2 4 6 8 10
x� cm

Setting x 0 = 0, Fig. ��.� shows the concentration pro�le against distance x

at di�erent � hour, � hours and �� hours. �e shorter the time, the closer
the maximum is to the origin; for longer times, the maximum moves
out to larger distances as a result of the convective �ow. In addition, as
time proceeds di�usion occurs and this causes the bell-shaped curves to
widen and spread. Because the amount of material is conserved, the area
under each curve must be the same: this is why their maximum amplitude
decreases as they spread out.

(c) De�ning x c = x 0 + υt and z = (x − x c )�(4D)1�2 allows a general set of

concentration pro�les at di�erent times to be plotted without specifying
either x 0 , υ or D.

c 0 e−(x−x 0 −υt) �4D t c 0 e−(x−x c ) �4D t c 0 e−z �t

2 2 2

c(x, t) = = =
(4πDt)1�2 (4πD)1�2 t 1�2 (4πD)1�2 t 1�2
 1.0
t = 1 hr
0.8 t = 5 hrs
t = 20 hrs
0.6

C�hrs−1�2
0.4

0.2

0.0
−4 −2 0 2 4
z

Hence
(4πD)1�2 c(x, t) 1
C(z, t) = = 1�2 e−z �t
2

c0 t
as required.
A plot of C as a function of z for times �, �, and �� hours is shown in
Fig. ��.�. �ese long times have been chosen unit because of the slow rate
of di�usion.

P��C.� �e probability of being n steps from the origin is P(nd) = N!�(N−N R )!N R !2 N
where N R is the number of steps taken to the right and N is the total number
of steps. Note that n = N R − N L and N = N R + N L , where N L is the number of
steps taken to the le�.
N−n
NR = N − NL = NL + n hence NL =
2
N+n
NL = N − NR = NR − n hence NR =
2
N! N!
therefore P(nd) = = N+n
[N − ( N−n
2
)]! � N−n
2
�! 2 N � 2
�! � N−n
2
�! 2 N

�e combination N = 4 and n = 6 is physically impossible, so P(6d) = � .

�e combination N = 6 and n = 6 has probability
6!
P(6d) = = �.����
� 6+6
2
�! � 6−6
2
�! 26

�e combination N = 12 and n = 6 has probability

12!
P(6d) = = �.����
� 12+6
2
�! � 12−6
2
�! 212
P��C.�� �e root-mean-square-displacement in three dimensions is given by [��C.��b–
���], �r 2 �1�2 = (6Dt)1�2 , where t is the time period and D is the di�usion
coe�cient. It follows that t = �r 2 ��6D
�r 2 � (1.0 × 10−6 m)2
t= = = 1.7 × 10−2 s
6D 6 × (1.0 × 10−11 m2 s−1 )

I��.� (a) �e di�usion equation is [��C.�–���].

∂c ∂2 c
=D 2
∂t ∂x
�e proposed solution is
c(x, t) = c 0 + (c s − c 0 )[1 − erf(ξ)]

where ξ(x, t) = x�(4Dt)1�2 and erf(ξ) = 2π−1�2 ∫0 e−y dy. Note that, by
ξ 2

de�nition, ∂[erf(ξ)]�∂ξ = 2π−1�2 e−ξ .

2

�e �rst step is to examine the initial and boundary conditions. At t = 0,

∞
ξ(x, 0) = ∞. Hence erf(ξ) = 2π−1�2 ∫0 e−y dy = (2π−1�2 )×( 12 π 1�2 ) = 1
2

and c(x, 0) = c 0 + (c s − c 0 )[1 − 1] = c 0 for 0 < x < ∞. At x = 0,

ξ(0, t) = 0. Hence erf(ξ) = 2π−1�2 ∫0 e−y dy = (2π−1�2 ) × 0 = 0 and
0 2

c(0, t) = c 0 +(c s −c 0 )[1−0] = c s for 0 ≤ t ≤ ∞. �erefore, this expression

for c(x, t) satis�es the initial and boundary conditions.
To determine whether or not the proposed solution solves the di�usion
equation it is substituted into the each side. For the LHS
∂c ∂(c 0 + (c s − c 0 )[1 − erf(ξ)]) ∂[erf(ξ)] ∂ξ
= = −(c s − c 0 )
∂t ∂t ∂ξ ∂t
2 ∂[x�(4Dt)
1�2
]
= −(c s − c 0 )(2π−1�2 e−ξ )
∂t
x x(c s − c 0 ) x 2 �4D t
= −(c s − c 0 )(2π−1�2 e−x �4D t ) � �=
2
e
(4D) t
1�2 3�2 (4πD)1�2 t 3�2
For the RHS
∂2 c ∂ ∂[erf(ξ)] ∂ξ
D =D �−(c s − c 0 ) �
∂x 2 ∂x ∂ξ ∂x
2D(c s − c 0 ) ∂[e−x �4D t ] 2D(c s − c 0 ) −x −x 2 �4D t
2

=− =− � e �
(4πDt)1�2 ∂x (4πDt)1�2 2Dt
x(c s − c 0 )
= ex �4D t
2

(4πD)1�2 (t)3�2
�erefore the LHS is equal to the RHS and the proposed form of c(x, t)
does indeed satisfy the di�usion equation, as well as the initial and bound-
ary conditions.
(b) Di�usion through aveoli sites (about � cell thick) of oxygen and carbon
dioxide between lungs and blood capillaries (also about � cell thick) oc-
curs through about 75 µm (the diameter of a red blood cell). �us, the
range 0 ≤ x ≤ 100 µm is reasonable for concentration pro�les for the
di�usion of oxygen into water. Given the maximum distance, the longest
time is estimated using [��C.��–���].
2
πxmax π(0.1 × 10−3 m)2
tmax ≈ = = 3.74 s
4D 4(2.10 × 10−9 m2 s−1 )

�e plots shown in Fig. ��.� are with c 0 = 0, c s = 2.9 × 10−4 mol dm−3 ,
and D = 2.10 × 10−9 m2 s−1 .

3.0
t = 0.05 s
t = 0.25 s
t = 0.75 s
104 c�(mol dm−3 )

2.0 t=2s

1.0

0.0
0.00 0.02 0.04 0.06 0.08 0.10
x�mm
D��A.� A reaction order for a particular species can only be ascribed when the rate
is simply proportional to a power of the concentration of that species. For
example, if the rate law is of the form υ = k r [A] a [B]b . . . an order is ascribable
to both A and B, but if the rate law is of the form υ = (k 1 [A])�(k 2 + k 3 [B]), an
order is ascribable to A, but not to B.

D��A.� �is is discussed in Section ��A.� on page ���.

E��A.�(b) Assuming perfect gas behaviour the total pressure is proportional to the amount
in moles of gas present, provided that the temperature is constant and the vol-
ume of the container is �xed. Imagine that a certain amount of N� is consumed
so that its partial pressure falls by ∆p. Due to the stoichiometry of the reaction
the partial pressure of H� will fall by 3∆p, and the partial pressure of NH� will
increase by 2∆p. �e overall change in the total pressure will by −∆p − 3∆p +
2∆p = −2∆p.
If the initial pressure is p 0 then, because the reactant gases are in their stoi-
chiometric ratios, the partial pressure of N� is 14 p 0 . If a fraction α of the N�
is consumed, its partial pressure falls to 14 p 0 (1 − α), thus ∆p = 41 p 0 α. It has
already been established that the total pressure changes by −2∆p, therefore the
�nal pressure is
p f = p 0 − 2∆p = p 0 − 2( 14 p 0 α) = p 0 (1 − 12 α)
When the reaction is complete, α = 1 and hence p f = 12 p 0 , which is in accord
with the overall stoichiometry of the reaction in which four moles of gas go to
two.

E��A.�(b) �e stoichiometry of the reaction shows that one mole of CH� CH� is formed
for every two moles of CH� consumed. �e rate of formation of CH� CH� is
therefore half the rate of consumption of CH� . As explained in Section ��A.�(a)
on page ��� the rate of consumption of a reactant R is given by −d[R]�dt.
�erefore the rate of formation of CH� CH� is
d[CH3 CH3 ] 1 d[CH3 ] 1
= 2 ×− = 2 ×−(−1.2 mol dm−3 s−1 ) = +0.6 mol dm−3 s−1
dt dt
E��A.�(b) For a homogeneous reaction in a constant volume system the rate of reaction
is given by [��A.�b–���], υ = (1�ν J )d[J]�dt, which is rearranged to d[J]�dt =
ν J υ. In these expressions ν J is the stoichiometric number of species J, which
is negative for reactants and positive for products. For this reaction ν A = −1,
ν B = −3, ν C = +1 and ν D = +2.
For A d[A]�dt = ν A υ = (−1) × (2.7 mol dm−3 s−1 ) = −2.7 mol dm−3 s−1
For B d[B]�dt = ν B υ = (−3) × (2.7 mol dm−3 s−1 ) = −8.1 mol dm−3 s−1
For C d[C]�dt = ν C υ = (+1) × (2.7 mol dm−3 s−1 ) = +2.7 mol dm−3 s−1
For D d[D]�dt = ν D υ = (+2) × (2.7 mol dm−3 s−1 ) = +5.4 mol dm−3 s−1

�e rate of consumption of A is 2.7 mol dm−3 s−1 , the rate of consumption of

B is 8.1 mol dm−3 s−1 , the rate of formation of C is 2.7 mol dm−3 s−1 , and the
rate of formation of D is 5.4 mol dm−3 s−1 .

E��A.�(b) For a homogeneous reaction in a constant volume system the rate of reaction
is given by [��A.�b–���], υ = (1�ν J )d[J]�dt, where ν J is the stoichiometric
number of species J which is negative for reactants and positive for products.
For species B, which has ν B = −3, this gives
1 d[B] 1
υ= = × (−2.7 mol dm−3 s−1 ) = �.�� mol dm−3 s−1
ν B dt −3
Because B is consumed in the reaction, the rate of change in the concentration
of B, d[B]�dt, is negative and equal to minus the rate of consumption of B.
Rearranging [��A.�b–���] then gives
For A d[A]�dt = ν A υ = (−1) × (0.90 mol dm−3 s−1 ) = −0.90 mol dm−3 s−1
For B d[C]�dt = ν C υ = (+1) × (0.90 mol dm−3 s−1 ) = +0.90 mol dm−3 s−1
For D d[D]�dt = ν D υ = (+2) × (0.90 mol dm−3 s−1 ) = +1.8 mol dm−3 s−1

�e rate of consumption of A is 0.90 mol dm−3 s−1 , the rate of formation of C

is 0.90 mol dm−3 s−1 , and the rate of formation of D is 1.8 mol dm−3 s−1 .

E��A.�(b) As explained in Section ��A.�(b) on page ��� the units of k r are always such as
to convert the product of concentrations, each raised to the appropriate power,
into a rate expressed as a change in concentration divided by time. In this
case the rate is given in mol dm−3 s−1 , so if the concentrations are expressed
in mol dm−3 the units of k r will be dm6 mol−2 s−1 because
[A] [B]2
��� � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � �� ��� � � � � � � � � � � � �� � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
kr

(dm6 mol−2 s−1 ) × (mol dm−3 ) × (mol dm−3 )2 = mol dm−3 s−1
�e rate of reaction is given by [��A.�b–���], υ = (1�ν J )(d[J]�dt), where ν J
is the stoichiometric number of species J. Rearranging gives d[J]�dt = ν J υ. In
this case ν C = +1, ν A = −1, and υ = k r [A][B]2 so
d[C] d[A]
= ν C υ = k r [A][B]2 = ν A υ = −k r [A][B]2
dt dt
 �e rate of formation of C is therefore d[C]�dt = k r [A][B]2 and the rate of
consumption of A is −d[A]�dt = k r [A][B]2 .

E��A.�(b) �e rate of reaction is given by [��A.�b–���], υ = (1�ν J )(d[J]�dt). In this case

ν C = +1 so
1 d[C] 1
υ= = k r [A][B][C]−1 = k r [A][B][C]−1
ν J dt +1
As explained in Section ��A.�(b) on page ��� the units of k r are always such as
to convert the product of concentrations, each raised to the appropriate power,
into a rate expressed as a change in concentration divided by time. In this
case the rate is given in mol dm−3 s−1 , so if the concentrations are expressed
in mol dm−3 the units of k r will be s−1 because
[A] [B] [C]−1
� ��� � � � � � � � � � � � �� � � � � � � � � � � � � ��� � � � � � � � � � � � �� � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
kr

(s−1 ) × (mol dm−3 ) × (mol dm−3 ) × (mol dm−3 )−1 = mol dm−3 s−1

E��A.�(b) As explained in Section ��A.�(b) on page ��� the units of k r are always such as
to convert the product of concentrations, each raised to the appropriate power,
into a rate expressed as a change in concentration divided by time.
(i) A second-order reaction expressed with concentrations in molecules per
cubic metre is one with a rate law such as υ = k r [A]2 . If the rate is given
in molecules m−3 s−1 then the units of k r will be m3 molecules−1 s−1 be-
cause
[A]2
��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � �
kr

(m3 molecules−1 s−1 ) × (molecules m−3 )2 = molecules m−3 s−1

A third-order reaction expressed with concentrations in molecules per
cubic metre is one with a rate law such as υ = k r [A]2 [B]. �e units of k r
will then be m6 molecules−2 s−1 because
[A]2 [B]
��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � � �
kr

(m6 molecules−2 s−1 ) × (molecules m−3 )2 × (molecules m−3 )

= molecules m−3 s−1
(ii) If the rate laws are expressed with pressures in pascals then a second-order
reaction is one with a rate law such as υ = k r p A p B and a third-order
reaction is one with a rate law such as υ = k r p A p B p C . If the rate is given
in Pa s−1 then the units of k r will be Pa−1 s−1 and Pa−2 s−1 respectively.

��� � � � � � � � � � � � � � � � � � � � � �
kr pA pB

For second-order (Pa−1 s−1 ) × (Pa) × (Pa) = Pa s−1

��� � � � � � � � � � � � � � � � � � � � � � �
kr pA pB pC

For third-order (Pa−2 s−1 ) × (Pa) × (Pa) × (Pa) = Pa s−1

E��A.�(b) If k a ′ [A] � k b , which might occur when the concentration of A is very high,
then the term k b in the denominator of the rate law is negligible compared to
the k a ′ [A] term and so the rate law becomes
υ = k a k b [A]2 �k a ′ [A] = k r,eff [A] where k r,eff = k a k b �k a ′
Under these conditions the concentration of A appears raised to the power +1
so the reaction is �rst order in A.
If instead k a ′ [A] � k b , which might occur when the concentration of A is
very low, the term k a ′ [A] is negligible in the denominator and so the rate law
becomes
υ = k a k b [A]2 �k b = k a [A]2
Under these conditions the order with respect to A is +2.
In between these two limits, when k a ′ [A] and k b are comparable, no order with
respect to A can be de�ned.

E��A.�(b) �e gaseous species is denoted A and the order with respect to A as a. �e rate
law expressed in terms of partial pressure is then υ = k r p Aa . Taking (common)
logarithms gives
log υ = log k r + log p Aa = log k r + a log p A
where the properties of logarithms log(x y) = log x + log y and log x a = a log x
are used.
�is expression implies that a graph of log υ against log p A will be a straight line
of slope a, from which the order can be determined. However, because there
are only two data points a graph is not necessary so an alternative approach is
used.
If the initial partial pressure of the compound is p A,0 then the partial pressure
when a fraction f has reacted, so that a fraction 1 − f remains, is (1 − f )p A,0 .
Data are given for two points, f 1 = 0.100 and f 2 = 0.200. Denoting the rates
at these points by υ 1 and υ 2 and using the expression log υ = log k r + a log p A
from above gives the equations
log υ 1 = log k r + a log [(1 − f 1 )p A,0 ] log υ 2 = log k r + a log [(1 − f 2 )p A,0 ]
Subtracting the second equation from the �rst gives
log υ 1 − log υ 2 = a log [(1 − f 1 )p A,0 ] − a log [(1 − f 2 )p A,0 ]
Hence
υ1 (1 − f 1 )p A,0 1 − f1
log � � = a log � � = a log � �
υ2 (1 − f 2 )p A,0 1 − f2
where the property of logarithms log x −log y = log(x�y) is used and the factor
of p A,0 is cancelled.
Rearranging for a gives

log(υ 1 �υ 2 ) log �(10.01 Pa s−1 )�(8.90 Pa s−1 )�

a= = = �.��
log [(1 − f 1 )�(1 − f 2 )] log [(1 − 0.100)�(1 − 0.200)]
P��A.� �e rate law is assumed to take the form υ 0 = k r [Y] a [complex]b where υ 0 is the
initial rate, and a and b are the orders with respect to Y and the complex. De-
noting k r [Y] a by k r,eff gives υ 0 = k r,eff [complex]b , which on taking logarithms
gives

log υ 0 = log k r,eff + log[complex]b = log k r,eff + b log[complex]

where the properties of logarithms log(x y) = log x + log y and log x a = a log x
are used.
�is expression implies that a graph of log υ 0 against log[complex] will be a
straight line of slope b and intercept log k r,eff . �e data are plotted in Fig. ��.�
for both initial concentrations of Y
Case (i): [Y] = 2.7 × 10−3 mol dm−3

[complex] υ0 log([complex] log(υ 0

�mol dm−3 �mol dm−3 s−1 /mol dm−3 ) �mol dm−3 s−1 )
0.008 01 125 −2.096 2.097
0.009 22 144 −2.035 2.158
0.012 11 190 −1.917 2.279

Case (ii): [Y] = 6.1 × 10−3 mol dm−3

[complex] υ0 log([complex] log(υ 0

�mol dm−3 �mol dm−3 s−1 /mol dm−3 ) �mol dm−3 s−1 )
0.008 01 640 −2.096 2.806
0.009 22 730 −2.035 2.863
0.012 11 960 −1.917 2.982

Both sets of data fall on good straight lines, the equations for which are

case (i): log(υ 0 �mol dm−3 s−1 ) = 1.014 × log([complex]�mol dm−3 ) + 4.222
case (ii): log(υ 0 �mol dm−3 s−1 ) = 0.984 × log([complex]�mol dm−3 ) + 4.868

Both lines have a slope of approximately �, so it is concluded that the order with
respect to the complex is � . Hence the rate law is υ 0 = k r,eff [complex].
�e intercepts are identi�ed with log k r,eff in each case. For case (i), the inter-
cept at log([complex]�mol dm−3 ) = 0 is log υ 0 �mol dm−3 s−1 = 4.222, which
on taking the antilogarithm corresponds to υ 0 = 1.66... × 104 mol dm−3 s−1
when [complex] = 1 mol dm−3 . Because the rate law has already been estab-
lished to be υ 0 = k r,eff [complex], it follows that

υ0 1.66... × 104 mol dm−3 s−1

k r,eff ,i = = = 1.66... × 104 s−1
[complex] 1 mol dm−3
 3.0

log(υ 0 �mol dm−3 s−1 )

case (ii)

2.5

case (i)
2.0

−2.2 −2.1 −2.0 −1.9 −1.8

−3
log([complex]�mol dm )

Similarly, for case (ii) the intercept is log υ 0 �mol dm−3 s−1 = 4.868 which cor-
responds to υ 0 = 7.37... × 104 mol dm−3 s−1 when [complex] = 1 mol dm−3 .
Hence
υ0 7.37... × 104 mol dm−3 s−1
k r,eff ,ii = = = 7.37... × 104 s−1
[complex] 1 mol dm−3

Because k r,eff = k r [Y]b , taking the logarithm gives

log k r,eff = log k r + log[Y]b = log k r + b log[Y]

where the properties of logarithms log(x y) = log x + log y and log x a = a log x
are used.
�is expression implies that a graph of log k r,eff against log[Y] will be a straight
line of slope b. However, because there are only two data points, one for [Y] =
2.7 mmol dm−3 and one for [Y] = 6.1 mmol dm−3 , a graph is not necessary and
an alternative approach is used. �e two data points give the equations

log k r,eff ,i = log k r + b log[Y]i and log k r,eff ,ii = log k r + b log[Y]ii

Subtracting the second equation from the �rst gives

log k r,eff ,i − log k r,eff ,ii = b log [Y]i − b log[Y]ii

Hence, using log x − log y = log(x�y),

k r,eff ,i [Y]i
log � � = b log � �
k r,eff ,ii [Y]ii

Rearranging for b gives

log (k r,eff ,i �k r,eff ,ii ) log �(1.66... × 10 s )�(7.37... × 10 s )�

4 −1 4 −1
b= = = 1.83 . . .
log ([Y]i �[Y]ii ) log �(2.7 mmol dm−3 )�(6.1 mmol dm−3 )�
 �is value is moderately close to �, implying that the reaction is second-order
with respect to Y.
�e value of k r is found using k r,eff = k r [Y]b with the value of b just found.
Taking b = 2 and rearranging gives k r = k r,eff �[Y]2 .

1.66... × 104 s−1

For case (i) kr = = 2.28... × 109 dm6 mol−2 s−1
�2.7 × 10−3 mol dm−3 �
2

7.37... × 104 s−1

For case (ii) kr = = 1.98... × 109 dm6 mol−2 s−1
�6.1 × 10−3 mol dm � −3 2

�e average value of k r from these two results is 2.1 × 109 dm6 mol−2 s−1 .

D��B.� In general the rate of a reaction depends on the concentration of the various
species involved. If all but one of the species is placed in large excess, such
that their concentrations do not vary with time, the rate law may reduce to the
simple form υ = k r′ [A] a , where A is the species not in excess. If this is the case,
the power a is the order with respect to A: if a = 1 the reaction is said to be
pseudo�rst order with respect to A, if a = 2 it is pseudosecond order. It is also
possible that under certain conditions a more complex rate law will simplify to
pseudo�rst or pseudosecond order. For example if the rate law is of the form
υ = (k 1 [A]2 )�(k 2 +k 3 [A]), when k 3 [A] � k 2 the rate law becomes pseudo�rst
order in A, but when k 3 [A] � k 2 , the rate law is pseudosecond order in A.

E��B.�(b) �e integrated rate law for a �rst-order reaction of ethanol CH� CH� OH is given
by [��B.�b–���], ln([CH3 CH2 OH]�[CH3 CH2 OH]0 ) = −k r t. Rearranging for
k r and taking [CH3 CH2 OH] = 56.0 mmol dm−3 when t = 1.22 × 104 s gives

1 [CH3 CH2 OH] 1 56.0 × 10−3 mol dm−3

k r = − ln � �=− ln � �
t [CH3 CH2 OH]0 1.22 × 104 s 220 × 10−3 mol dm−3
= 1.12 × 10−4 s−1

E��B.�(b) �e fact that the two half lives are not the same establishes that the reaction is
not �rst-order because, as explained in Section ��B.� on page ���, a �rst-order
reaction has a constant half-life. For orders n ≠ 1 the half-life is given by [��B.�–
���], t 1�2 = (2n−1 − 1)�[(n − 1)k r [A]0n−1 ]. Denoting the two measurements by
 t 1�2,i and t 1�2,ii and expressing concentration in terms of partial pressure gives
the two equations

2n−1 − 1 2n−1 − 1
t 1�2,i = t 1�2,ii =
(n − 1)k r p A,i
n−1
(n − 1)k r p A,ii
n−1

�e second equation is divided by the �rst to give

n−1
t 1�2,ii p A,i t 1�2,ii p A,i
=� � hence log � � = (n − 1) log � �
t 1�2,i p A,ii t 1�2,i p A,ii

where log x a = a log x is used. Rearranging for n gives

log �t 1�2,ii �t 1�2,i � log [(178 s)�(340 s)]

n= +1= + 1 = 8.24 × 10−3
log (p A,i �p A,ii ) log [(55.5 kPa)�(28.9 kPa)]

�is is very close to zero, so the reaction is zeroth-order .

E��B.�(b) For the reaction 2A(g) → products the rate, as given by [��A.�b–���], υ =
(1�ν J )(d[J]�dt), is
1 dp A
υ=
−2 dt
where concentrations are expressed in terms of partial pressures. It is given
that the reaction is �rst-order in A, so υ = k r p A . Combining this with the
above expression for υ gives
1 dp A dp A
= kr pA hence = −2k r p A
−2 dt dt
�is has the same form, except with 2k r instead of k r , as [��B.�a–���], (d[A]�dt) =
−k r [A], for which it is shown in Section ��B.� on page ��� that the half-life and
the integrated rate law are
ln 2
t 1�2 = [A] = [A]0 e−k r t
kr
�e expressions for the reaction in question are analogous, but with k r replaced
by 2k r .
ln 2
t 1�2 = p A = (p A,0 )e−2k r t
2k r
�e half-life is
ln 2 ln 2
t 1�2 = = = 9.74 × 105 s
2k r 2 × 3.56 × 10−7 s−1
�e partial pressures at the speci�ed times are calculated from the above inte-
grated form of the rate law. Hence

t = 50 s p A = (33.0 kPa) × e−2×(3.56×10 = ��.� kPa

−7
s−1 )×(50 s)

t = 20 min p A = (33.0 kPa) × e−2×(3.56×10 = ��.� kPa

−7 −1
s )×([20×60] s)
E��B.�(b) �e reaction is of the form A + 2B → P. From Table ��B.� on page ��� the
integrated rate law for this reaction, assuming that it has rate law υ = k r [A][B],
is
[A]0 [B]0 (1 − e([B]0 −2[A]0 )k r t )
[P] =
2[A]0 − [B]e([B]0 −2[A]0 )k r t
�e equation gives the concentration of a product P produced in 1 ∶ 1 sto-
ichiometry with the reactant A. It therefore applies to the species C in the
reaction A + 2B → C + D. Hence
[A]0 [B]0 (1 − e λ )
[C] = λ = ([B]0 − 2[A]0 )k r t
2[A]0 − [B]0 e λ

For t = 20 s

λ = �(0.130 mol dm−3 ) − 2 × (0.027 mol dm−3 )� × (0.34 dm3 mol−1 s−1 )
× (20 s) = 0.516...
(0.027 mol dm−3 ) × (0.130 mol dm−3 ) �1 − e0.516 ... �
[C] =
2 × (0.027 mol dm−3 ) − (0.130 mol dm−3 ) × e0.516 ...
= �.��� mol dm−3

For t = 15 min

λ = �(0.130 mol dm−3 ) − 2 × (0.027 mol dm−3 )� × (0.34 dm3 mol−1 s−1 )
× ([15 × 60] s) = 23.2...
(0.027 mol dm−3 ) × (0.130 mol dm−3 ) �1 − e23.2 ... �
[C] =
2 × (0.027 mol dm−3 ) − (0.130 mol dm−3 ) × e23.2 ...
= �.��� mol dm−3

E��B.�(b) Using [��A.�b–���], υ = (1�ν J )(d[J]dt), the rate of the reaction 2A → P is

υ = − 12 (d[A]�dt). Combining this with the rate law υ = k r [A]3 gives

1 d[A] d[A]
− = k r [A]3 hence = −2k r [A]3
2 dt dt
�is rate law is integrated following the method in Section ��B.� on page ���.
�e equation is �rst rearranged to

��� � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � �
Integral A.�

d[A] [A] t
− = 2k r hence −� [A]−3 d[A] = 2k r � dt
[A]3 [A]0 0

where the limits of the integration arise because the concentration is [A]0 at
t = 0 and at a later time t it is [A]. Performing the integration gives

[A] 1 1
[A]−2 �[A] = 2k r t�0 � − � = 2k r t
1 t 1
hence
2 0 2
[A] 2 [A]20
 Rearranging for t gives

1 1 1
t= � − �
4k r [A] 2 [A]20
1
=
4 × �6.50 × 10 dm6 mol−2 s−1 �
−4

� 1 1 �
×� − �
2 = 1.6 × 10 s or �� days
6
� �0.015 mol dm−3 � �0.067 mol dm−3 � �
2

E��B.�(b) From Table ��B.� on page ���, the integrated rate law for a second-order reac-
tion of the type A + 2B → P is

1 [A]0 ([B]0 − 2[P])

kr t = ln
[B]0 − 2[A]0 ([A]0 − [P]) [B]0
Because one mole of P is formed for every mole of A that reacts, it follows that
[P] = [A]0 − [A], because the quantity [A]0 − [A] is equal to the amount of A
that has reacted. �e term [A]0 −[P] in the above expression is therefore simply
equal to [A]. Similarly, [P] = 12 ([B]0 − [B]) because one mole of P is formed
for every two moles of B that react. Rearranging gives [B]0 − 2[P] = [B]. It
follows that the integrated rate equation can be written as

1 [A]0 [B] 1 [B]�[B]0

kr t = ln hence kr t = ln
[B]0 − 2[A]0 [A][B]0 [B]0 − 2[A]0 [A]�[A]0

(i) A�er � hour the amount of A has fallen by �.��� mol dm−3 from �.���
mol dm−3 to �.��� mol dm−3 . �e stoichiometry of the reaction means
that B must have fallen by twice this amount, that is by �.��� mol dm−3 ,
from its initial value of �.��� mol dm−3 to �.��� mol dm−3 . Rearranging
the above integrated rate equation for k r and using these values, together
with t = 1 h × (602 s h−1 ) = 3600 s, gives

1 [B]�[B]0
kr = ln
([B]0 − 2[A]0 ) t [A]�[A]0
1
=
��0.030 mol dm � − 2 × �0.050 mol dm−3 �� × (3600 s)
−3

� �0.010 mol dm � � �0.030 mol dm � �

−3 −3
× ln
� �0.040 mol dm−3 � � �0.050 mol dm−3 � �

= 3.47... × 10−3 dm3 mol−1 s−1 = �.� dm3 mol−1 s−1

(ii) �e half-life of a reactant is the time taken for the concentration of that
reactant to fall to half its initial value. �us the half-life of A is the time
taken for [A] to fall to 12 [A]0 = (0.050 mol dm−3 )�2 = 0.0250 mol dm−3 .
However, this is not possible from the given starting conditions, because
the stoichiometry of the reaction requires the concentration of B to fall
 by twice this amount, that is, by �.��� mol dm−3 , but the concentration
of B is only �.��� mol dm−3 to start with. �e half-life of A is therefore
in�nite , since the condition [A] = 0.0250 mol dm−3 can never be reached.
�e half-life of B is the time at which [B] = 12 [B]0 = (0.030 mol dm−3 )�2 =
0.015 mol dm−3 . To achieve this the concentration of B must fall by �.���
mol dm−3 , which from the stoichiometry of the reaction means that the
concentration of A must fall by 12 ×(0.015 mol dm−3 ) = 0.0075 mol dm−3 .
�e concentration of A will therefore be
[A]0
��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
[A] = (0.050 mol dm−3 ) −(0.0075 mol dm−3 ) = 0.0425 mol dm−3

Rearranging the integrated rate equation for t and using these concentra-
tions for A and B gives

1 1 [B]�[B]0
t= ln
k r [B]0 − 2[A]0 [A]�[A]0
1 1
= −1 −1 ×
−3 3
3.47...×10 dm mol s (0.030 mol dm )−2×(0.050 mol dm−3 )
−3

(0.015 mol dm−3 )�(0.030 mol dm−3 )

× ln � � = 2.2 × 103 s or �.�� h
(0.0425 mol dm−3 )�(0.050 mol dm−3 )

P��B.� �e concentration of B is given in the question as

nk r t[A]20 [B] nk r t[A]0

[B] = hence =
1 + k r t[A]0 [A]0 1 + k r t[A]0
�e concentration of A for a second-order reaction is given by [��B.�b–���],

[A]0 [A] 1
[A] = hence =
1 + k r t[A]0 [A]0 1 + k r t[A]0

�ese expressions are plotted in Fig. ��.� as [A]�[A]0 or [B]�[A]0 against k r t[A]0 .

P��B.� �e order is determined by testing the �t of the data to integrated rate law
expressions. A zeroth-order reaction of the form A → P has an integrated rate
law given by [��B.�–���], [A] = [A]0 − k r t, so if the reaction is zeroth-order
then a plot of [A] against t will be a straight line of slope −k r . In this case, A
is (CH� )� CBr. On the other hand, a �rst-order reaction has an integrated rate
law given by [��B.�b–���], ln([A]�[A]0 ) = −k r t, so if the reaction is �rst-order
then a plot of ln [A]�[A]0 against t will be a straight line of slope −k r . Finally,
if the order is n ≥ 2 the integrated rate law is given in Table ��B.� on page ���
as
1 1 1 1 1
kr t = � − � hence = (n−1)k r t+
n − 1 ([A]0 − [P]) n−1 [A]0
n−1
[A] n−1 [A]0n−1
 2.0
B, n = 2

[A]�[A]0 or [B]�[A]0
1.5

1.0
B, n = 1

0.5 B, n = 1
2

A
0.0
0 1 2 3 4 5
kr t

where to obtain the second expression the relation [P] = [A]0 − [A] is substi-
tuted and the equation rearranged. �is expression implies that if the reaction
has order n ≥ 2 a plot of 1�[A]n−1 against t will be a straight line of slope
(n − 1)k r .
�e data are plotted assuming zeroth-, �rst-, second-, and third-order in Fig. ��.�.
�e �rst-order plot shows the best �t to a straight line, so it is concluded that
the reaction is �rst-order .

[A] [A] 1�[A] 1�[A]2

t�h ln
�mol dm−3 [A]0 �dm3 mol−1 �dm6 mol−2
0 0.103 9 0.000 9.62 9.263 × 101
3 0.089 6 −0.148 11.16 1.246 × 102
6 0.077 6 −0.292 12.89 1.661 × 102
10 0.063 9 −0.486 15.65 2.449 × 102
18 0.035 3 −1.080 28.33 8.025 × 102
31 0.020 7 −1.613 48.31 2.334 × 103

�e equation of the line in the �rst-order plot is

ln([A]�[A]0 ) = −5.42 × 10−2 × (t�h) + 1.54 × 10−2

Identifying the slope with −k r as discussed above gives the �rst-order rate con-
stant as k r = 5.42 × 10−2 h−1 .
�e concentration of (CH� )� CB� remaining a�er 43.8 h is calculated using the
integrated rate law for a �rst-order reaction, [��B.�b–���], [A] = [A]0 e−k r t

[A] = (10.39 × 10−2 mol dm−3 ) × e−(5.42×10

−2
h−1 )×(43.8 h)

= 0.97 × 10−2 mol dm−3

 zeroth-order 0.0 �rst-order
0.10

[A]�mol dm−3

ln([A]�[A]0 )
−0.5

0.05 −1.0

−1.5
0.00
0 10 20 30 0 10 20 30
t�h t�h
60
second-order 2 000 third-order
[A]−1 �dm3 mol−1

[A]−2 �dm6 mol−2

40
1 000
20
0
0
0 10 20 30 0 10 20 30
t�h t�h

P��B.� Noting from the de�nition pH = − log([H+ ]�mol dm−3 ) that the H+ concen-
tration is given by ([H+ ]�mol dm−3 ) = 10−pH , the initial rate is

υ = k r [HSO3 − ]2 [H+ ]2
= (3.6 × 106 dm9 mol−3 s−1 ) × (50 × 10−6 mol dm−3 )2 × (10−5.6 mol dm−3 )2
= 5.7 × 10−14 mol dm−3 s−1

From the de�nition of reaction rate [��A.�b–���], υ = (1�ν J )(d[J]�dt), the

rate is written in terms of the HSO� – concentration as υ = − 12 d[HSO3 − ]�dt.
Combining this with the rate law υ = k r [HSO3 − ]2 [H+ ]2 gives

d[HSO3 − ] d[HSO3 − ]
− 12 = k r [HSO3 − ]2 [H+ ]2 hence = −2k r [H+ ]2 [HSO3 − ]2
dt dt

Because the pH and hence [H+ ] is assumed constant, this is written as

d[H+ ]
= −k r,eff [HSO3 − ]2 where k r,eff = 2k r [H+ ]2
dt

�is expression corresponds to the rate law of an e�ective second-order reac-

tion, for which the half-life is given by [��B.�–���], t 1�2 = 1�(k r,eff [A]0 ). Hence
 the time taken for the HSO� – concentration to fall to half its initial value is
1 1
t 1�2 = =
k r,eff [HSO3 ]0 2k r [H ] [HSO3 − ]0
− + 2

1
=
2 × (3.6 × 106 dm9 mol−3 s−1 ) × (10−5.6 ) × (50 × 10−6 mol dm−3 )2
2

= 4.4 × 108 s or �� years

P��B.� Visual inspection of the data suggests that the half-life is constant at about
� minutes. �is indicates that the reaction is �rst-order because �rst order
reactions have a constant half-life.
Using [��A.�b–���], υ = (1�ν J )(d[J]�dt), the rate is written as υ = − 12 d[N2 O5 ]�dt.
Combining this with υ = k r [N2 O5 ], the rate law for a �rst-order reaction, gives
d[N2 O5 ] d[N2 O5 ]
− 12 = k r [N2 O5 ] hence = −k r,eff [N2 O5 ] where k r,eff = 2k r
dt dt
�e integrated form of this rate law is given by [��B.�b–���]
ln([N2 O5 ]�[N2 O5 ]0 ) = −k r,eff t or ln[N2 O5 ] = ln[N2 O5 ]0 − k r t
�is expression implies that a graph of ln[N2 O5 ] against t will be a straight line
of slope −k r,eff = −2k r . To estimate k r without drawing a graph, pairs of data
are considered and used to estimate the slope according to
∆ ln[N2 O5 ] ln[N2 O5 ] t+∆t − ln[N2 O5 ] t
slope = =
∆t ∆t
Taking ∆t = 1 min the results are

t�min [N2 O5 ]�mol dm−3 ln([N2 O5 ]�mol dm−3 ) slope�min−1

0 1.000 0.000 −0.350
1 0.705 −0.350 −0.350
2 0.497 −0.699 −0.354
3 0.349 −1.053 −0.350
4 0.246 −1.402 −0.352
5 0.173 −1.754

�e approximately constant value of the slope con�rms that the reaction is �rst-
order. �e average value of the slope is −0.350... min−1 ; identifying this with
−2k r as described above gives k r = 0.175 min−1 .
In an alternative approach, ln[N2 O5 ] is plotted against t, as shown in Fig. ��.�.
�e data lie on a good straight line, thus con�rming that the reaction is �rst-
order. �e equation of the line is
ln([N2 O5 ]�mol dm−3 ) = −0.351 × (t�min) + 1.077 × 10−3

Identifying the slope with −2k r gives k r = 0.175 min−1 .

 0.0

ln([N2 O5 ]�mol dm−3 )

−0.5

−1.0

−1.5

−2.0
0 1 2 3 4 5
t�min

P��B.�� �e reaction is con�rmed to be �rst-order by �tting the data to an integrated

rate law. �e integrated rate law for a �rst order reaction is given by [��B.�b–
���], ln([A]�[A]0 ) = −k r t; this expression implies that if the hydrolysis of
sucrose is �rst order then a graph of ln([sucrose]�[sucrose]0 ) against t should
be a straight line of slope −k r . �e data are plotted in Fig. ��.�

[sucrose] [sucrose]
t�103 s ln
�mol dm−3 [sucrose]0
0 0.316 0.000
14 0.300 −0.052
39 0.274 −0.143
60 0.256 −0.211
80 0.238 −0.283
110 0.211 −0.404
140 0.190 −0.509
170 0.170 −0.620
210 0.146 −0.772

�e data lie on a good straight line, thus con�rming that the reaction is �rst-
order. �e equation of the line is

ln([sucrose]�[sucrose]) = −3.670 × 10−3 × (t�min) + 3.052 × 10−3

Identifying the slope with −k r gives = k r = 3.670 × 10−3 min−1 . �e half-life

of a �rst-order reaction is given by [��B.�–���], t 1�2 = ln 2�k r .

ln 2 ln 2
t 1�2 = = = 189 min
kr 3.670 × 10−3 min−1
 ln([sucrose]�[sucrose])
0.0

−0.2

−0.4
0 50 100
t�min

P��B.�� �e order is determined by testing the �t of the data to integrated rate law ex-
pressions. If the rate law is υ = k r [ClO]n , where n is the order to be determined,
expressing υ in terms of the rate of change of concentration of [ClO] using
[��A.�b–���], υ = (1�ν J )(d[J]�dt) gives
1 d[ClO] d[ClO]
v= = k r [ClO]n hence = −2k r [ClO]n
−2 dt dt
Integrated rate laws are given in Table ��B.� on page ���, but care is needed
because these are for reactions of the form A → P but here the reaction is
2ClO → products.
For n = 0, Table ��B.� on page ��� shows that a reaction A → P with rate law
υ = d[P]�dt = k r has integrated rate law A = A0 − k r t. To adapt this expression
for the reaction in question, the rate law for the reaction in the table is �rst
written as d[A]�dt = −k r using d[P]�dt = −d[A]�dt for a reaction of the form
A → P. �is rate law matches that found above, d[ClO]�dt = −2k r [ClO]n ,
for n = 0 and A = ClO, except that k r is replaced by 2k r . �e integrated rate
law will therefore be the same except with k r replaced by 2k r , that is, [ClO] =
[ClO]0 −2k r t. �is expression implies that if the reaction is zeroth-order a plot
of [ClO] against t will give a straight line of slope −2k r .
Similarly Table ��B.� on page ��� gives the integrated rate law for a �rst-order
reaction A → P with rate law υ = d[P]�dt = k r [A] as ln([A]0 �[A]) = k r t,
equivalent to [��B.�b–���], ln([A]�[A]0 ) = −k r t. By the same reasoning as
above the integrated rate law for the reaction will be ln([ClO]�[ClO]0 ) = −2k r t,
implying that a plot of ln([ClO]�[ClO]0 ) against t will give a straight line of
slope −2k r .
Finally, if the order is n ≥ 2 the integrated rate law for a reaction A → P with
rate law υ = d[P]�dt = k r [A]n is given in Table ��B.� on page ��� as

1 1 1 1 1
kr t = � − � hence = (n−1)k r t+
n − 1 ([A]0 − [P])n−1 [A]0n−1 [A]n−1 [A]0n−1
where to obtain the second expression the relation [P] = [A]0 − [A] is substi-
tuted and the equation rearranged. Adapting this expression for the reaction
in question gives 1�[ClO]n−1 = 2(n − 1)k r t + 1�[ClO]0n−1 . �is expression
implies that if the reaction has order n ≥ 2 a plot of 1�[ClO]n−1 against t will
be a straight line of slope 2(n − 1)k r .
�e data are plotted assuming zeroth-, �rst-, second-, and third-order in Fig. ��.�.

[ClO] [ClO] 1�[ClO] 1�[ClO]2

t�ms ln
�µmol dm−3 [ClO]0 �dm3 µmol−1 �dm6 µmol−2
0.12 8.49 0.000 0.118 0.013 9
0.62 8.09 −0.048 0.124 0.015 3
0.96 7.10 −0.179 0.141 0.019 8
1.60 5.79 −0.383 0.173 0.029 8
3.20 5.20 −0.490 0.192 0.037 0
4.00 4.77 −0.577 0.210 0.044 0
5.75 3.95 −0.765 0.253 0.064 1

0.0
8 zeroth-order �rst-order
ln([ClO]�[ClO]0 )
[ClO]�µmol dm−3

−0.2

6 −0.4

−0.6
4
−0.8
0 2 4 6 0 2 4 6
t�ms t�ms
[ClO]−1 �dm3 µmol−1

[ClO]−2 �dm6 µmol−2

0.25 second-order 0.06 third-order

0.20
0.04
0.15
0.02
0.10
0 2 4 6 0 2 4 6
t�ms t�ms

None of the plots give a perfect straight line due to experimental scatter in the
data. �e values of the product moment correlation coe�cient for each of the
plots are −0.945, −0.971, 0.987 and 0.989 for zeroth-, �rst-, second-, and third-
order respectively, suggesting that the second-, third- or a higher order plot
gives the best �t.
 If the reaction is second-order, the rate constant is found from the equation of
the line in the second-order plot

[ClO]−1 �dm3 µmol−1 = 2.368 × 10−2 × (t�ms) + 0.118

Identifying the slope with −2(n − 1)k r as discussed above, noting that n = 2 for
a second-order plot, gives gives the second-order rate constant as

k r = − 12 × (−2.368 × 10−2 dm3 µmol−1 ms−1 )

= 1.18... × 10−2 dm3 µmol−1 ms−1
106 µmol 103 ms
= (1.18... × 10−2 dm3 µmol−1 ms−1 ) × ×
1 mol 1s
= 1.18 × 107 dm3 mol−1 s−1

�e half-life of a non-�rst-order reaction depends on the initial concentration,

and for a reaction with order n > 1 is given by [��B.�–���], t 1�2 = (2n−1 −
1)�([n−1]k r [A]0n−1 ). However, this is for a reaction of the form A → products.
In this case the reaction is 2A → products, so k r must be replaced by 2k r as
explained earlier. �e half-life is then given by

2n−1 − 1
t 1�2 =
2(n − 1)k r [ClO]0n−1

If the reaction is second-order, using [ClO]0 = 8.49 µmol dm−3 and the value
of k r from above gives

22−1 − 1 1
t 1�2 = =
2(2 − 1)k r [ClO]2−1
0 2 × 1 × (1.18... × 10 dm3 µmol−1 ) × (8.49 µmol)
−2

= �.�� ms

P��B.�� (a) If the reaction A + B → P is mth order in A and nth order in B the rate
law is
d[P]
υ= = k r [A]m [B]n
dt
For a short time period the derivative is approximated by �nite changes

δ[P]
= k r [A]m [B]n hence δ[P] = k r [A]m [B]n δt
δt
�e concentration of P at a time δt a�er the start of the reaction is there-
fore
[P] = [P]0 + δ[P] = 0 + δ[P] = k r [A]m [B]n δt
Dividing by [A], which is assumed to be approximately constant over the
short time range δt, then gives [P]�[A] = k r [A]m−1 [B]n δt as required.
(b) �e reaction propene+HCl → chloropropane has the form of the reaction
A + B → P analysed in part (a). Setting A as propene, B as HCl and
P as chloropropane, and expressing concentrations in terms of partial
pressures, the result derived in part (a) becomes
p chloropropane
= k r p propene
m−1 n
p HCl δt ∝ p propene
m−1
p propene
�e fact that p chloropropane �p propene is independent of p propene implies that
m − 1 = 0 and hence m = 1. �erefore the reaction is �rst-order in
propene.
If instead HCl is treated as A and propene as B, the result from part (a)
becomes
p chloropropane
= k r p HCl
m−1
p propene δt
p HCl
where the order with respect to propene has been set to � as deduced
above. Taking common logarithms gives
p chloropropane
log = log �k r p propene δt� + (n − 1) log p HCl
p HCl
where log(x y) = log x + log y and log x a = a log x are used. �is expres-
sion implies that a plot of log(p chloropropane �p HCl ) against log p HCl will be
a straight line of slope n − 1. Such a plot is shown in Fig. ��.�.
p chloropropane p chloropropane
p HCl �atm log(p HCl �atm) log � �
p HCl p HCl
10.0 0.05 1.00 −1.30
7.5 0.03 0.88 −1.52
5.0 0.01 0.70 −2.00

−1.0
log(p chloropropane �p HCl )

−1.5

−2.0

0.6 0.7 0.8 0.9 1.0 1.1

log(p HCl �atm)

�e data lie on a modest straight line, the equation of which is

log(p chloropropane �p HCl ) = 2.3 × log(p HCl �atm) − 3.6
 �e slope is moderately close to �, suggesting that n − 1 = 2 and hence
n = 3. �erefore the reaction may be third-order in HCl. However there
are only three data points, they do not lie very close to a straight line, and
slope of the line is not very close to �, so the conclusion should be treated
with caution in the absence of further data.

P��B.�� �e stoichiometry of the reaction 2A + 3B → P implies that when the con-

centration of P has increased from � to x, the concentration of A has fallen to
[A]0 − 2x and the concentration of B has fallen to [B]0 − 3x. �is is because
each P that forms entails the disappearance of two A and three B. �e rate law
υ = d[P]�dt = k r [A][B] then becomes

d[P] dx
= k r ([A]0 − 2x)([B]0 − 3x) hence = k r ([A]0 − 2x)([B] − 3x)
dt dt
where to go to the second expression [P] = x is used, which implies that d[P]dt =
dx�dt. �e expression is rearranged and the initial condition x = 0 when t = 0
is applied. �is gives the integrations required as
x 1 t
� dx = � k r dt
0 ([A]0 − 2x)([B]0 − 3x) 0

�e right-hand side evaluates to k r t. �e le�-hand side is evaluated using the

integrals from the Resource section
x 1 x 1
� dx = � dx
0 ([A]0 − 2x)([B]0 − 3x) 0 2( [A]0 − x) × 3( [B]0 − x)
1
2
1
3

��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � ��
Integral A.�

1 x 1
= � dx
6 0 ( 12 [A]0 − x)( 13 [B]0 − x)
1 1 ( 13 [B]0 − x)( 12 [A]0 )
= × 1 × ln
6 3 [B]0 − 12 [A]0 ( 12 [A]0 − x)( 13 [B]0 )
1 ([B]0 − 3x)[A]0
= ln
2[B]0 − 3[A]0 ([A]0 − 2x)[B]0

Combining this with the right-hand side the integrated rate law is

1 ([B]0 − 3x)[A]0
ln = kr t
2[B]0 − 3[A]0 ([A]0 − 2x)[B]0

P��B.�� A reaction of the form A → P that is nth order in A has rate law υ = k r [A]n .
Combining this with [��A.�b–���], υ = (1�ν J )(d[J]�dt) gives

1 d[A]
= k r [A]n hence − [A]−n d[A] = k r dt
−1 dt
 Initially, at t = 0, the concentration of A is [A]0 , and at a later time t it is [A].
�ese are used as the limits of the integration to give

��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
Integral A.�

[A] [A] t
t 1
� −[A]−n d[A] = � k r dt hence [A]−(n−1) � = k r t�
[A]0 0 n−1 [A]0 0
1 1 1
hence � − � = kr t (for n ≠ 1)
n − 1 [A] n−1 [A]0n−1

�is integrated rate law is equivalent to that given in Table ��B.� on page ���
and is valid for all values of n, including fractional values, except for n = 1.
Dividing through by k r gives

1 1 1
t= � − �
(n − 1)k r [A] n−1 [A]0n−1

Setting t = t 1�2 when [A] = 12 [A]0 gives

1 1 1 2n−1 − 1
t 1�2 = � 1 − � =
(n − 1)k r ( 2 [A])n−1 [A]0n−1 (n − 1)k r [A]0n−1

Similarly, setting t = t 3�4 when [A] = 34 [A]0 gives

1 1 1 ( 43 )n−1 − 1
t 3�4 = � 3 − � =
(n − 1)k r ( 4 [A])n−1 [A]0n−1 (n − 1)k r [A]0n−1

Hence
t 1�2 (2n−1 − 1)�(n − 1)k r [A]0n−1 2n−1 − 1
= 4 n−1 = 4 n−1
t 3�4 [( 3 ) − 1]�(n − 1)k r [A]0n−1
(3) −1

D��C.� If the equilibrium position shi�s with pressure, a pressure jump can be used
to alter the rate of the reaction. For such an e�ect on equilibrium, the volume
change of the reaction must be non-zero.

E��C.�(b) �e binding of the drug to protein is represented by the equilibrium

⇀ Complex
Protein + Drug ��′�
kr

kr

�e equilibrium constant in terms of rate constants is given by [��C.�–���], K =

k r c −○ �k r′ . Because the forward and backward reactions are of di�erent order, the
 c −○ is included so that the ratio of k r , with units dm3 mol−1 s−1 , to k r′ , with units
s−1 , is turned into a dimensionless quantity. Rearranging for k r′ gives

k r c −○ (1.5 × 108 dm3 mol−1 s−1 ) × (1 mol dm−3 )

k r′ = =
K 200
= 7.5 × 10 s5 −1

E��C.�(b) �e relaxation time in a jump experiment is given by [��C.�a–���], τ = 1�(k r +

k r′ ). Both forward and reverse reactions are �rst-order, so their rate constants
are related to their half-lives according to [��B.�–���], t 1�2 = ln 2�k r , which is
rearranged to k r = ln 2�t 1�2 . �is is used to replace k r and k r′ in the expression
for τ to give
−1
� ln 2 ln 2 � ln 2 ln 2 −1
τ = (k r + k r′ )−1 = + ′ =� + � = 21 ms
� t 1�2 t 1�2 � 24 ms 39 ms

P��C.� �e forward and backward reactions are

d[A] d[A]
A → 2B = −k r [A] 2B → A = k r′ [B]2
dt dt
�e concentration of A is reduced by the forward reaction at a rate k r [A] but
is increased by the backward reaction at a rate k r′ [B]2 . �e net rate of change is
therefore d[A]�dt = −k r [A] + k r′ [B]2 . If the initial concentration of A is [A]0 ,
the stoichiometry of the reaction implies that [B] = 2([A]0 − [A]). �erefore

d[A]
= −k r [A] + 4k r′ ([A]0 − [A])2
dt
To solve this di�erential equation, it is convenient to de�ne a new variable
x = [A]�[A]0 , so that [A] = [A]0 x and d[A]�dt = [A]0 dx�dt. Making these
substitutions gives

dx
[A]0 = −k r [A]0 x + 4k r′ ([A]0 − [A]0 x)2 = −k r [A]0 x + 4k r′ [A]20 (1 − x)2
dt
Dividing this expression through by [A]0 and then taking out a factor of 4k r′ [A]0
gives

dx kr
= −k r x + 4k r′ [A]0 (1 − x)2 = 4k r′ [A]0 �− ′ + (1 − x)2 �
dt 4k r [A]0
kr
= 4k r′ [A]0 �− + 1 − 2x + x 2 �
4k r [A]0
′

kr
= 4k r′ [A]0 �x 2 + �2 − � x + 1�
4k r′ [A]0
�e term in square brackets is a quadratic in x which may therefore be written
(a − x)(b − x), where a and b are the roots of x 2 − (2 + k r �4k r′ [A]0 )x + 1 = 0,
that is �
−(2 + k r �4k r′ [A]0 ) + (2 + k r �4k r′ [A]0 )2 − 4
a=
2
and b is the same but with the negative square root. �erefore
dx x 1 t
= 4k r′ [A]0 (a − x)(b − x) hence � dx = � 4k r′ [A]0 dt
dt 1 (a − x)(b − x) 0

where the initial condition that x = [A]�[A]0 = 1 when t = 0 is applied. �e

integral on the right is 4k r′ [A]0 t, while the integral on the le� is evaluated using
integral A.� in the Resource section to give
1 (b − x)(a − 1)
ln = 4k r′ [A]0 t
b − a (a − x)(b − 1)
Rearranging for x gives
(b − x)(a − 1)
= e4(b−a)k r [A]0 t
′

(a − x)(b − 1)
b − 1 4k r′ [A]0 t
hence (b − x) = (a − x) e
a−1
a(b − 1) 4(b−a)k r′ [A]0 t b − 1 4(b−a)k r′ [A]0 t
hence b − e = x �1 − e �
a−1 a−1
b − [a(b − 1)�(a − 1)]e4(b−a)k r [A]0 t
′

hence x =
1 − [(b − 1)�(a − 1)]e4(b−a)k r [A]0 t
′

�is expression gives x = [A]�[A]0 as a function of time; as de�ned above a

and b are constants that depend on the relative values of k r , k r′ , and [A]0 .
As an example, for the speci�c case k r = k r′ [A]0 evaluation of the expression
for a and b given above yields a = 1.64... and b = 0.609.... Putting these into
the expression for x and replacing k r′ [A]0 by k r in the exponents for clarity in
this speci�c case gives

��� � � � � � � ��� � � � � � � � � ��� � � � � �� � � � � � �� ��� � � � � � � � �� � � � � � � � ��

b a(b−1)�(a−1) 4(b−a)

(0.609...) + (1.00...) × exp[(−4.12...) k r t]

x=
1 + (0.609...) × exp[(−4.12...) k r t]
��� � � � � � � ��� � � � � � � � � ��� � � � � � � � �� � � � � � � � ��
(b−1)�(a−1) 4(b−a)

�e dimensionless quantity x = [A]�[A]0 is plotted against the likewise dimen-

sionless quantity k r t in Fig. ��.�. �e graph shows that initially the concentra-
tion of A decreases, because the backwards reaction is unimportant compared
to the forwards reaction due to little product B being present, but then levels o�
as the system comes to equilibrium. An expression for [B] is found by recalling
from above that [B] = 2([A]0 − [A]). �erefore
[B] (0.609...) + (1.00...)e(−4.12 ...)k r t
= 2(1 − x) = 2 �1 − �
[A]0 1 − (0.609...)e(−4.12 ...)k r t
�is expression for [B]�[A]0 is also plotted on Fig. ��.�.
 1.0
A
0.8

[A]�[A]0 or [B]�[A]0
0.6

0.4
B
0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
kr t

P��C.� A mechanism containing three steps is

⇀ B ���⇀ C ���⇀D
kb
A ��′�
ka kc
′ ′
ka kb kc

At equilibrium, the forward and backward reactions of each step are equal.

ka
Step � k a [A]eq = k a′ [B]eq hence [B]eq = [A]eq ×
k a′
Step � k b [B]eq = k b′ [C]eq
kb ka kb
hence [C]eq = [B]eq × ′
= [A]eq × ′ × ′
kb ka kb
Step � k c [C]eq = k c′ [D]eq
kc ka kb kc
hence [D]eq = [C]eq × ′
= [A]eq × ′ × ′ × ′
kc ka kb kc

Generalising this process it is clear that for a reaction

⇀ B ���⇀ C ���⇀ D ���

⇀ ... ���
⇀P
kb
A ��′�
ka kc
′ ′
ka kb kc

the equilibrium concentration of the �nal product P, and the equilibrium con-
stant for the overall reaction A � P, are

ka kb kc [P]eq ka kb kc
[P]eq = [A]eq × × × × ... hence K= = ′ × ′ × ′ × ...
k a′ k b′ k c′ [A]eq ka kb kc

P��C.� �e reaction A � B+C is analysed in How is that done? ��C.� on page ��� where
it is shown that the relaxation time τ is given by 1�τ = k r + k r′ ([B]eq + [C]eq ).
In addition, the equilibrium constant is given by [��C.�–���], K = (k a �k a′ ) ×
 (k b �k b′ ) × ..., but in this case in order for K to be dimensionless it is necessary
to include a factor of 1�c −○ because k r is a �rst-order rate constant with units
s−1 while k r′ is a second-order rate constant with units dm3 mol−1 s−1 .
kr
K= hence k r = k r′ c −○ K
k r′ c −○
�is is substituted into the expression for 1�τ to give
1�τ = k r′ c −○ K + k r′ ([B]eq + [C]eq )
which is then rearranged for k r′
1 1 1
k r′ = × −○ =
τ c K + [B]eq + [C]eq 3.0 × 10−6 s
1
×
(1 mol dm )×(2.0×10 )+(0.20×10−3 mol dm−3 )+(0.20×10−3 mol dm−3 )
−3 −16

= 8.33... × 108 dm3 mol−1 s−1 = 8.3 × 108 dm3 mol−1 s−1
�e rearranged expression for K above is then used to �nd k r
k r = k r′ c −○ K = (8.33... × 108 dm3 mol−1 s−1 ) × (1 mol dm−3 ) × (2.0 × 10−16 )
= 1.7 × 10−7 s−1

D��D.� �e temperature dependence of some reactions is not Arrhenius-like, in the

sense that a straight line is not obtained when ln k r is plotted against 1�T.
However, it is still possible to de�ne an activation energy using [��D.�–���],
E a = RT 2 (d ln k r �dT). �is de�nition reduces to the earlier one (as the slope
of a straight line) for a temperature-independent activation energy. However,
this latter de�nition is more general, because it allows E a to be obtained from
the slope (at the temperature of interest) of a plot of ln k r against 1�T even if
the Arrhenius plot is not a straight line. Non Arrhenius behaviour is sometimes
a sign that quantum mechanical tunnelling is playing a signi�cant role in the
reaction. A reaction with a very small or zero activation energy, so that k r = A,
such as for some radical recombination reactions in the gas phase, has a rate
that is largely temperature independent.

E��D.�(b) �e rate constant k r for the decomposition is calculated at each temperature

using the Arrhenius equation [��D.�–���], k r = Ae−E a �RT . �e half-life is given
by [��B.�–���], t 1�2 = ln 2�k r . Combining these expressions gives
ln 2 ln 2 E a �RT
t 1�2 = = e
Ae−E a �RT A
 (i) At 20 ○ C

ln 2 261 × 103 J mol−1

t 1�2 = × exp � �
4.00 × 1015 s−1 (8.3145 J K−1 mol−1 ) × ([20 + 273.15] K)
= 5.6 × 1030 s or 1.8 × 1023 years

(ii) At 500 ○ C

ln 2 261 × 103 J mol−1

t 1�2 = × exp � �
4.00 × 1015 s−1 (8.3145 J K−1 mol−1 ) × ([500 + 273.15] K)
= �� s

E��D.�(b) �e relationship between the values of a rate constant at two di�erent tempera-
tures is given by [��D.�–���], ln(k r,2 �k r,1 ) = (E a �R)(1�T1 − 1�T2 ). Rearrang-
ing for E a gives

R ln(k r,2 �k r,1 ) (8.3145 J K mol ) × ln �(4.01 × 10 )�(2.25 × 10 )�

−1 −1 −2 −2
Ea = =
1�T1 − 1�T2 1�([29 + 273.15] K) − 1�([37 + 273.15] K)
= 5.62... × 104 J mol−1 = ��.� kJ mol−1

�e frequency factor is found by rearranging the Arrhenius equation [��D.�–

���], k r = Ae−E a �RT , for A. �e data for both temperatures gives the same result.

At T1 A = k r eE a �RT1
5.62...×104 J mol−1
= (2.25×10−2 dm3 mol−1 s−1 )×exp
(8.3145 J K−1 mol−1 )×([29+273.15] K)
= 1.21 × 108 dm3 mol−1 s−1
At T2 A = k r eE a �RT2
5.62...×104 J mol−1
= (4.01×10−2 dm3 mol−1 s−1 )×exp
(8.3145 J K−1 mol−1 )×([37+273.15] K)
= 1.21 × 108 dm3 mol−1 s−1

E��D.�(b) �e relationship between the values of a rate constant at two di�erent tempera-
tures is given by [��D.�–���], ln(k r,2 �k r,1 ) = (E a �R)(1�T1 − 1�T2 ). Rearrang-
ing for E a , and using k r,2 �k r,1 = 2 because the rate constant doubles between
the two temperatures, gives

R ln(k r,2 �k r,1 ) (8.3145 J K−1 mol−1 ) × ln 2

Ea = = = �� kJ mol−1
1�T1 −1�T2 1�([25+273.15] K)−1�([35+273.15] K)
E��D.�(b) �e relationship between the values of a rate constant at two di�erent tempera-
tures is given by [��D.�–���], ln(k r,2 �k r,1 ) = (E a �R)(1�T1 − 1�T2 ). Rearrang-
ing gives
−1
R k r,2 1 1 1 R k r,2
ln = − hence T2 = � − ln �
E a k r,1 T1 T2 T1 E a k r,1

If k r is to increase by 10 % then k r,2 = k r,1 +0.10×k r,1 = 1.10×k r,1 , so k r,2 �k r,1 =
1.10. Hence, taking T1 = 25 ○ C,
−1
1 8.3145 J K−1 mol−1
T2 = � − ln 1.10� = ���.� K = ��.� ○ C
[25 + 273.15] K 99.1 × 103 J mol−1

E��D.�(b) As explained in Section ��D.�(a) on page ��� the fraction f of collisions that are
su�ciently energetic to be successful is given by the exponential factor e−E a �RT .

80 × 103 J mol−1
f = e−E a �RT = exp �− � = 4.4 × 10−9
(8.3145 J K−1 mol−1 ) × (500 K)

P��D.� �e Arrhenius equation [��D.�–���], ln k r = ln A− E a �RT, implies that a plot of

ln k r against 1�T should give a straight line of slope −E a �R and intercept ln A.
�e data are plotted in Fig. ��.�.

θ�○ C T�K k r �s−1 1�(T�K) ln(k r �s−1 )

0.0 273.2 2.46 × 10−3 0.003 66 −6.01
20.0 293.2 4.51 × 10−2 0.003 41 −3.10
40.0 313.2 5.76 × 10−1 0.003 19 −0.55

�e data fall on a good straight line, the equation for which is

ln(k r �s−1 ) = (−1.167 × 104 ) × 1�(T�K) + 36.71

Identifying the slope with −E a �R gives the activation energy as

E a = −slope × R = −(−1.167 × 104 K) × (8.3145 J K−1 mol−1 ) = ��.� kJ mol−1

P��D.� �e Arrhenius equation [��D.�–���], ln k r = ln A− E a �RT, implies that a plot of

ln k r against 1�T should give a straight line of slope −E a �R and intercept ln A.
�e data are plotted in Fig. ��.��.

T�K k r �dm3 mol−1 s−1 1�(T�K) ln(k r �dm3 mol−1 s−1 )

300.3 1.44 × 107 0.003 33 16.48
341.2 3.03 × 107 0.002 93 17.23
392.2 6.90 × 107 0.002 55 18.05
 0

−2

ln(k r �s−1 )
−4

−6

0.0031 0.0033 0.0035 0.0037

1�(T�K)

18.0
ln(k r �dm3 mol−1 s−1 )

17.5

17.0

16.5

0.0024 0.0026 0.0028 0.0030 0.0032 0.0034

1�(T�K)

�e data fall on a good straight line, the equation for which is

ln(k r �dm3 mol−1 s−1 ) = (−2.007 × 103 ) × 1�(T�K) + 23.15

Identifying the slope with −E a �R gives the activation energy as

E a = −slope × R = −(−2.007 × 103 K) × (8.3145 J K−1 mol−1 ) = ��.� kJ mol−1

Identifying the intercept with ln A gives the frequency factor as

A = e23.15 dm3 mol−1 s−1 = 1.13 × 1010 dm3 mol−1 s−1

�e units of A are the same as the units of k r .

P��D.� (a) �e rate constant is estimated using the Arrhenius equation [��D.�–���],
 k r = Ae−E a �RT .

−14.1 × 103 J mol−1

k r = (1.13 × 109 dm3 mol−1 s−1 )×exp � �
(8.3145 J K−1 mol−1 )×(263 K)
= 1.79... × 106 dm3 mol−1 s−1

�e rate equation for the bimolecular reaction CH4 +OH → CH3 +H2 O is
υ = −d[CH4 ]�dt = k r [CH4 ][OH], so the rate of consumption of methane
is
d[CH4 ]
− = k r [CH4 ][OH]
dt
= (1.79... × 106 dm3 mol−1 s−1 ) × (40 × 10−9 mol dm−3 )
× (3.5 × 10−15 mol dm−3 )
= 2.51... × 10−16 mol dm−3 s−1 = 2.5 × 10−16 mol dm−3 s−1

(b) Multiplication of the rate in mol dm−3 s−1 by the volume of the atmo-
sphere gives the rate in mol s−1 , and multiplication by the molar mass of
methane, 16.0416 g mol−1 , gives the rate in g s−1 . Finally, multiplication
by the length of a year in seconds, 365 × 24 × 602 = 31536000 s, gives the
mass consumed anually.

m = (2.51... × 10−16 mol dm−3 s−1 ) × (4 × 1021 dm3 ) × (16.0416 g mol−1 )

1 kg
× (31536000 s) × = 5.1 × 1011 kg
1000 g

D��E.� �e rate-determining step is what it says it is, the step whose rate determines
the overall rate of reaction. Any steps subsequent to the rate-determining step
cannot, by de�nition, go any faster than the rate-determining step, and in fact
they proceed at the same rate as the rate-determining step. A step prior to the
rate-determining step may proceed faster that the rate-determining step.

D��E.� If several steps are involved in a reaction mechanism it is possible that changes
in the concentrations of the species involved will result in a change in the rate-
determining step, and hence a change in the rate law. �is may result in a
change of order. A simple example is the Lindemann–Hinshelwood mecha-
nism considered in Section ��F.� on page ��� where there is a change for �rst-
to second-order kinetics depending on the pressure of the reactants.

D��E.� In a multi-step mechanism it is possible that the overall rate constant for the
reaction will be a composite of the rate constants for di�erent steps. If, in this
 expression for the overall rate constant, a rate constant for an individual step
appears to a negative power, k r−a , then this term will decrease with increasing
temperature and so make a negative contribution to the overall activation en-
ergy. If this e�ect is the dominant one, the overall activation energy may be
negative. A simple example of this behaviour is possible for reactions involving
pre-equilibrium, as discussed in Section ��E.� on page ���.

E��E.�(b) (i) �e pre-equilibrium A + B � U is described by the equilibrium constant

K given by

[U]�c −○ [U]c −○ K[A][B]

K= = hence [U] =
([A]�c −○ )([B]�c −○ ) [A][B] c −○

�e equilibrium constant K is written in terms of rate constants using

[��C.�–���], K = (k a �k a′ ) × (k b �k b′ ) × .... However, in order to make
K dimensionless it is necessary in this case to include a factor of 1�c −○
because k a is a second-order rate constant with units dm3 mol−1 s−1 while
k a′ is a �rst-order rate constant with units s−1 . �us K = k a c −○ �k a′ , which,
on substituting into the above expression for [U] yields

k a c −○ [A][B] k a
[U] = × = ′ [A][B]
k a′ c −○ ka

�is expression is alternatively obtained by noting that at equilibrium

the rates of the forward and reverse reactions are the same (provided the
formation of H can be ignored)

ka
k a [A][B] = k a′ [U] hence [U] = [A][B]
k a′

�e rate of formation of H is d[H]�dt = k b [U]; substituting the expres-

sion for [U] into this gives

d[H] ka kb
= k b [U] = [A][B]
dt k a′

(ii) �e net rate of change in the concentration of U is

d[U]
= k a [A][B] − k a′ [U] − k b [U]
dt
In the steady-state approximation this is assumed to be zero

k a [A][B] − k a′ [U] − k b [U] = 0 hence k a [A][B] = [U](k a′ + k b )

k a [A][B]
hence[U] =
k a′ + k b
 �e rate of formation of H is given by d[H]�dt = k b [U]; substituting the
above expression for [U] into this gives
d[H] k a k b [A][B]
= k b [U] =
dt k a′ + k b
If the rate of decay of U back to A+B is much faster than the decay of U to
H, that is if k a′ [U] � k b [U], the k b term in the denominator is neglected
in comparison to k a′ and the expression becomes
d[H] k a k b [A][B] k a k b
≈ = ′ [A][B]
dt k a′ ka
which is the same as the rate law derived in part (i) assuming a pre-
equilibrium. �is is because under these assumptions the removal of U to
form product is then too slow to a�ect the maintenance of the equilibrium
between A, B and U.
On the other hand, if the rate of conversion of U to H with rate k b [U]
is much faster than the decay back to starting materials with rate k a′ [U],
that is if k b � k a′ , the denominator of the rate law is approximated by k b
and the rate law becomes
d[H] k a k b [A][B]
≈ = k a [A][B]
dt kb
�is rate law corresponds to the �rst step A+B → U being rate-determining:
once U has formed from A and B in this step it immediately goes on to
form product.

E��E.�(b) If step (�) forms a pre-equilibrium, the equilibrium constant K is given by

([CH2 ClCH2 O− ]�c −○ ) [CH2 ClCH2 O− ]c −○
K= =
([CH2 ClCH2 OH]�c )([OH ]�c ) [CH2 ClCH2 OH][OH− ]
−
○ − −
○

K[CH2 ClCH2 OH][OH− ]

�is is rearranged to [CH2 ClCH2 O− ] =
c −○
�e rate of formation of (CH� CH� )� O is given by the rate of step (�),
d[(CH2 CH2 )2 O]
= k 2 [CH2 ClCH2 O− ]
dt
Substituting the above expression for [CH2 ClCH2 O− ] into this gives
d[(CH2 CH2 )2 O] k 2 K
υ= = −○ [CH2 ClCH2 OH][OH− ]
dt c
�is is the required expression. �e factor of 1�c −○ is necessary for the rate
equation to be dimensionally consistent.

E��E.�(b) �e overall activation energy for a reaction consisting of a pre-equilibrium

followed by a rate-limiting elementary step is given by [��E.��–���], E a = E a,a +
E a,b − E a,a′ , where E a,a and E a,a′ are the forward and reverse activation ener-
gies for the pre-equilibrium and E a,b is the activation energy for the following
elementary step. In this case
E a = (27 kJ mol−1 ) + (15 kJ mol−1 ) − (35 kJ mol−1 ) = +7 kJ mol−1
 �e concentrations of A, I, and P in the reaction mechanism A → I → P are
ka kb
P��E.�
given by [��E.�a–���], [��E.�b–���], and [��E.�c–���].
ka
[A] = [A]0 e−k a t [I] = �e−k a t − e−k b t � [A]0
kb − ka
k a e−k b t − k b e−k a t
[P] = �1 + � [A]0
kb − ka

�ese expressions are plotted for [A]0 = 1 mol dm−3 , k b = 1 s−1 , and four dif-
ferent values of k a in Fig. ��.��. Note that the �nal plot has a di�erent horizontal
scale to the others.

1.0 k a = 10 s−1 , k b = 1 s−1 1.0 k a = 0.5 s−1 , k b = 1 s−1

[J]�mol dm−3

[J]�mol dm−3
P A
P
0.5 A 0.5
I I

0.0 0.0
0 2 4 0 2 4
t�s t�s

1.0 k a = 0.1 s−1 , k b = 1 s−1 1.0 k a = 0.01 s−1 , k b = 1 s−1

[J]�mol dm−3

[J]�mol dm−3

A A

0.5 0.5
P P
I
0.0 0.0 I
0 2 4 0 20 40
t�s t�s

In the �rst plot, k a � k b , so A is quickly converted to I, and I is then converted

more slowly to P. �e rise in P mirrors the fall in I. On the other hand, in
the last plot k a � k b , so as soon as I is formed it immediately goes on to P.
Consequently the concentration of I remains low and approximately constant,
and the rise in P mirrors the fall in A. �is latter situation is the one to which
the steady-state approximation applies. �e maximum concentration reached
by I decreases, and moves to later times, as the ratio k a �k b decreases.

For the scheme A ⇄ B ⇄′ C the net rates of change of the concentrations of A,

ka kb
P��E.�
k a′ kb
 B, and C are
d[A] d[B]
= −k a [A] + k a′ [B] = k a [A] − k a′ [B] − k b [B] + k b′ [C]
dt dt
d[C]
= k b [B] − k b′ [C]
dt
If B is a reactive intermediate that reacts almost as soon as it is formed, the
steady-state approximation applies to B and d[B]�dt = 0. �erefore

k a [A] − k a′ [B] − k b [B] + k b′ [C] = 0 hence k a [A] − k a′ [B] = k b [B] − k b′ [C]

��� � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � �
term � term �

From the discussion above, it is evident that term � is equal to −d[A]�dt and
term � is equal to d[C]�dt. �erefore

d[A] d[C]
− =
dt dt

which is precisely what is expected for the scheme A ⇄ C.

kr

k r′

P��E.� Application of the steady-state approximation to the intermediate N� O� gives

d[N2 O2 ]
= k a [NO]2 − k a′ [N2 O2 ] − k b [N2 O2 ][O2 ] = 0
dt
�is is rearranged for [N2 O2 ].

k a [NO]2
[N2 O2 ] (k a′ + k b [O2 ]) = k a [NO]2 hence [N2 O2 ] =
k a′ + k b [O2 ]

�e rate of formation of NO2 is then

d[NO2 ] 2k a k b [NO]2 [O2 ]

= 2k b [N2 O2 ][O2 ] =
dt k a′ + k b [O2 ]

�e factor of � arises because two NO� molecules are formed in the �nal step.
To go to the �nal expression, the concentration of N� O� from above is substi-
tuted in.

(a) �e rate equations for the mechanism hhhh... ⇄ hchh... ⇄′ cccc... are
ka kb
P��E.�
k a′ kb

d[hhhh...]
= −k a [hhhh...] + k a′ [hchh...]
dt
d[hchh...]
= k a [hhhh...] − k a′ [hchh...] − k b [hchh...] + k b′ [cccc...]
dt
d[cccc...]
= k b [hchh...] − k b′ [cccc...]
dt
 (b) Applying the steady-state approximation to hchh... so that d[hchh...]�dt =
0 gives

k a [hhhh...] − k a′ [hchh...] − k b [hchh...] + k b′ [cccc...] = 0

k a [hhhh...] + k b′ [cccc...]
hence [hchh...] =
k a′ + k b
Substituting this into the expression for d[hhhh...]�dt gives

d[hhhh...] k a [hhhh...] + k b′ [cccc...]

= −k a [hhhh...] + k a′ � �
dt k a′ + k b
k a′ k a k ′ k ′ [cccc...]
= − �k a − � [hhhh...] + a b′
k a′ + kb ka + kb
′ ′
ka kb k k
=− ′ [hhhh...] + ′ a b [cccc...]
ka + kb ka + kb
��� � � � ��� � � � � ��� � � � ��� � � � �
kr k r′

Similarly for d[cccc...]�dt

d[cccc...] k a [hhhh...] + k b′ [cccc...]

= kb � � [hchh...] − k b′ [cccc...]
dt k a′ + k b
k a k b [hhhh...] k b k b′
= − �k ′
− � [cccc...]
k a′ + k b b
k a′ + k b
ka kb k′ k′
= ′ [hhhh...] − ′ a b [cccc...]
ka + kb ka + kb
��� � � � ��� � � � � ��� � � � ��� � � � �
kr k r′

�ese expressions have precisely the same form as those for the mecha-
nism hhhh... ⇄ cccc... for which the expressions are
kr

k r′

d[hhhh...] d[cccc...]
= −k r [hhhh...]+k r′ [cccc...] = k r [hhhh...]−k r′ [cccc...]
dt dt
�us the two mechanisms are equivalent provided hchh... can be regarded
as being a steady-state intermediate, that is, if the rate of its breakdown is
much faster than the rate of its formation.
An alternative, and rather simpler approach, is to use the same argument as
deployed in Problem P��E.�.

P��E.�� �e reaction is shown schematically in Fig. ��.��.

As explained in Section ��E.� on page ���, thermodynamic control arises when
the reaction is allowed to reach equilibrium. �e reactant R is therefore con-
sidered to be in equilibrium with both P1 and with P2

R ��′⇀
� P1 R ��′⇀
� P2
k1 k2

k1 k2
 E

R
P2
P1

At equilibrium, the rates of the forward and backward reactions of R to P1 are

equal, as are those to P2 . �erefore
k 1 [R] k 2 [R]
k 1 [R] = k 1′ [P1 ] hence [P1 ] = ; k 2 [R] = k 2′ [P2 ] hence [P2 ] =
k 1′ k 2′
�e ratio of the two products is therefore

[P2 ] k 2 [R]�k 2′ k 2 k 1′ K2
= = =
[P1 ] k 1 [R]�k 1′ ′
k2 k1 K1

⇀ P� and R ���
where K 1 and K 2 are the equilibrium constants for R ��� ⇀ P� ,
respectively.

D��F.� In the analysis of stepwise polymerization, the rate constant for the second-
order condensation is assumed to be independent of the chain length and to
remain constant throughout the reaction. It follows, then, that the degree of
polymerization is given by [��F.��b–���], �N� = 1 + k r t[A]0 . �erefore, the
average molar mass can be controlled by adjusting the initial concentration of
monomer and the length of time that the polymerization is allowed to proceed.
As discussed in Section ��F.�(b) on page ���, chain polymerization involves
initiation, propagation, and termination steps. �e derivation of the overall
rate equation utilizes the steady-state approximation and leads to the following
expression for the average number of monomer units in the polymer chain
([��F.��–���]) �N� = 2k r [M][In]−1�2 where k r = k p (4 f k i k t )−1�2 , and where
k p , k i , and k t are the rate constants for the propagation, initiation, and ter-
mination steps respectively, and f is the fraction of radicals that successfully
initiate a chain. It is seen that the average molar mass of the polymer is directly
proportional to the monomer concentration, and inversely proportional to the
square root of the initiator concentration, and to the rate constant for initiation.
�erefore, the slower the initiation of the chain, the higher the average molar
mass of the polymer.
D��F.� As temperature increases, the rate of an enzyme-catalyzed reaction is expected
to increase. However, at a su�ciently high temperature the enzyme denatures
and a decrease in the reaction rate is observed. Temperature related denatura-
tion is caused by the action of vigorous vibrational motion, which destroys sec-
ondary and tertiary protein structure. Electrostatic, internal hydrogen bond-
ing, and van der Waals interactions that hold the protein in its active, folded
shape are broken with the protein unfolding into a random coil. �e active site
and enzymatic activity is lost.
�e rate of a particular enzyme-catalyzed reaction may also appear to decrease
at high temperature in the special case in which an alternative substrate re-
action, which has a relatively slow rate at low temperature, has the faster rate
increase with increasing temperature. A temperature may be reached at which
the alternative reaction predominates.

E��F.�(b) �e e�ective rate constant for the Lindemann–Hinshelwood mechanism is given

by [��F.�–���], 1�k r = k a′ �k a k b + 1�k a [A]. �e di�erence between the e�ective
rate constant at two pressures is therefore

1 1 1 1 1 1�[A]2 − 1�[A]1
− = � − � hence ka =
k r,2 k r,1 k a [A]2 [A]1 1�k r,2 − 1�k r,1

�e rate constant for the activation step, k a , is therefore

1�(25 Pa) − 1�(1.09 × 103 Pa)

ka = = 9.9 × 10−6 Pa−1 s−1
1�(2.2 × 10−4 s−1 ) − 1�(1.7 × 10−3 s−1 )

or 9.9 MPa−1 s−1 .

E��F.�(b) �e fraction of condensed groups at time t of a stepwise polymerisation is given

by [��F.��–���], p = k r t[A]0 �(1 + k r t[A]0 ). Hence, a�er ��.�� h, or 10.00 h ×
(602 s)�(1 h) = 3.60 × 104 s,

k r t[A]0
p=
1 + k r t[A]0
(2.80 × 10−2 dm3 mol−1 s−1 ) × (3.60 × 104 s) × (50.0 × 10−3 mol dm−3 )
=
1 + (2.80 × 10−2 dm3 mol−1 s−1 ) × (3.60 × 104 s) × (50.0 × 10−3 mol dm−3 )
= 0.980... = �.���

�e degree of polymerisation in a stepwise polymerisation is given by [��F.��a–

���], �N� = 1�(1 − p).

1 1
�N� = = = ��
1 − p 1 − 0.980...
E��F.�(b) �e kinetic chain length in a chain polymerisation reaction is given by [��F.��c–
���], λ = k r [M][In]−1�2 . �e ratio of chain length under the two di�erent sets
of conditions is therefore
−1�2 −1�2
λ 2 k r [M]2 [In]2 [M]2 [In]2 1 −1�2
= =� �×� � = 5.0 × � � = ��.�
λ 1 k r [M]1 [In]−1�2 [M]1 [In]1 10.0
1

E��F.�(b) �e Michaelis–Menten equation for the rate of an enzyme-catalysed reaction

is given by [��F.��a–���], υ = υ max �(1 + K M �[S]0 ). Rearranging for υ max gives

KM 0.032 mol dm−3

υ max = υ �1 + � = (0.205 mmol dm−3 s−1 ) × �1 + �
[S]0 0.875 mol dm−3
= �.��� mmol dm−3 s−1

E��F.�(b) �e catalytic e�ciency is de�ned in the exercise as k b �K M , and υ max is related to

k b according to [��F.��b–���], υ max = k b [E]0 , hence k b = υ max �[E]0 . �erefore,
the catalytic e�ciency is

kb υ max 4.25 × 10−4 mol dm−3 s−1

= =
K M K M [E]0 (0.032 mol dm−3 ) × (3.60 × 10−9 mol dm−3 )
= 3.7 × 106 dm3 mol−1 s−1

P��F.� �e kinetic chain length in a chain polymerization is given by [��F.��c–���],

λ = k r [M][In]−1�2 . �is represents the average number of molecules in a chain
produced by one initiating radical, at the point at which the chain is terminated.
Disproportionation termination does not change the number of monomers in
the chain, so the average polymer length is equal to the kinetic chain length

�N� = λ = k r [M][In]−1�2

�is is in contrast to mutual termination, where as explained in Section ��F.�(b)

on page ��� the average number of monomers in a terminated polymer is the
sum of the numbers of monomers in the two combining polymer chains.

P��F.� �e Michaelis–Menten mechanism is

⇀ ES ��→ E + P
E + S ��′�
ka kb
ka

If E, S and ES form a pre-equilibrium, then the rate of the forward step in this
equilibrium, k a [A][S], must be equal to the rate of the reverse step, k a′ [ES].
Hence k a [E][S] = k a′ [ES]. �e total concentration of enzyme is [E]0 = [E] +
 [ES], so [E] = [E]0 − [ES]. Substituting this into the expression previously
found gives
k a [E]0 [S]
k a ([E]0 − [ES]) [S] = k a′ [ES] hence [ES] =
k a [S] + k a′
�e rate of product formation is given by the rate of the second step, υ = k b [ES],
hence
k b k a [E]0 [S] k b [E]0 k b [E]0
υ= = =
k a [S] + k a
′ 1 + k a �k a [S] 1 + k a′ �k a [S]0
′

To go to the �nal expression, the fact that the substrate is typically in large
excess compared to the enzyme, so that the free substrate concentration [S] is
approximately equal to the initial substrate concentration [S]0 , is used.
�e equation based on the steady-state approximation is given by [��F.��–���],
k b [E]0 k a′ + k b
υ= where KM =
1 + K M �[S]0 ka
�is is the same as the pre-equilibrium equation if k a′ � k b , that is, if the ES
complex is much more likely to revert to E+S than to react onward to products.
�is condition is assumed in applying the pre-equilibrium hypothesis, which
requires that the reaction of ES to products is too slow relative to the reversion
of ES to E + S to signi�cantly a�ect the setting up of the pre-equilibrium.

P��F.� �e rate of product formation is υ = k c [ES′ ], so the task is to �nd an expression

for [ES′ ]. �e steady-state approximation is applied to the two intermediates
ES and ES′
d[ES] d[ES′ ]
= k a [E][S]−k a′ [ES]−k b [ES] ≈ 0 and = k b [ES]−k c [ES′ ] ≈ 0
dt dt
�e concentration of free enzyme E is given by [E] = [E]0 − [ES] − [ES′ ].
Substituting this into the steady-state expression for [ES] gives
k a ([E]0 − [ES] − [ES′ ]) [S] − k a′ [ES] − k b [ES] = 0
hence k a [S][E]0 − k a [S][ES] − k a [S][ES′ ] − k a′ [ES] − k b [ES] = 0
�e steady-state expression for [ES′ ] implies that [ES] = k c [ES′ ]�k b . �is is
used to substitute for [ES] in the above expression to give
kc kc
k a [S][E]0 − k a [S] [ES′ ] − k a [S][ES′ ] − k a′ [ES′ ] − k c [ES′ ] = 0
kb kb
�is expression is multiplied through by k b and divided through by k a [S]
k a′ k c kb kc
k b [E]0 − k c [ES′ ] − k b [ES′ ] − [ES′ ] − [ES′ ] = 0
k a [S] k a [S]
k a′ k c kb kc
hence k b [E]0 = [ES′ ] �k c + k b + + �
k a [S] k a [S]
k c (k a′ + k b )
= [ES′ ] �(k b + k c ) + �
k a [S]
 k b [E]0 k c (k a′ + k b )
Dividing through by (k b + k c ) gives = [ES′ ] �1 + �
kb + kc k a (k b + k c )[S]

(k b �[k b + k c ]) [E]0
hence [ES′ ] =
1 + (k c [k a′ + k b ]�k a [k b + k c ]) �[S]

�is expression is substituted into υ = k c [ES′ ] to give

(k b k c �[k b + k c ]) [E]0
υ = k c [ES′ ] =
1 + (k c [k a′ + k b ]�k a [k b + k c ]) �[S]0

Note that [S] is replaced by [S]0 because the substrate is typically in large excess
relative to the enzyme so that [S] ≈ [S]0 . �e �nal rate equation has the same
form as the Michaelis–Menten equation [��F.��a–���], with

υ max k b k c [E]0 k c (k a′ + k b )
υ= , with υ max = and KM =
1 + K M �[S]0 kb + kc k a (k b + k c )

P��F.� (a) �e Michaelis–Menten equation [��F.��–���] is υ = k b [E]0 �(1+K M �[S]0 ),

or [��F.��a–���] υ = υ max �(1 + K M �[S]0 ). Rearranging gives

KM
υ �1 + � = υ max
[S]0
υK M
hence υ + = υ max
[S]0
υ 1 υ max
hence =− υ+
[S]0 KM KM

�is expression implies that a plot of υ�[S]0 against υ should be a straight

line of slope −1�K M and intercept υ max �K M .
(b) Note that the question should read a Hanes plot of [S]0 �υ against [S]0 , not
υ�[S]0 against [S]0 .
�e Michaelis–Menten equation [��F.��a–���] is inverted and then mul-
tiplied through by [S]0 to give

1 1 + K M �[S]0 [S]0 [S]0 KM

= hence = +
υ υ max υ υ max υ max

�is expression implies that a plot of [S]0 �υ against [S]0 should be a

straight line of slope 1�υ max and intercept K M �υ max .
(c) �e data are plotted as a Lineweaver–Burk plot in Fig. ��.��, as an Eadie–
Hofstee plot in Fig. ��.��, and as a Hanes plot in Fig. ��.��. In all cases the
data lie on a good straight line.
[H2 O2 ]� υ�mol 1�([H2 O2 ]� 1�(υ�mol υ�[H2 O2 ] [H2 O2 ]�υ
mol dm−3 dm−3 s−1 mol dm−3 ) dm−3 s−1 ) �s−1 �s
0.300 4.431 3.333 0.225 7 14.77 0.067 7
0.400 4.518 2.500 0.221 3 11.30 0.088 5
0.500 4.571 2.000 0.218 8 9.14 0.109 4
0.600 4.608 1.667 0.217 0 7.68 0.130 2
0.700 4.634 1.429 0.215 8 6.62 0.151 1

0.230
Lineweaver–Burk plot
1�(υ�mol dm−3 s−1 )

0.225

0.220

0.215
1.0 1.5 2.0 2.5 3.0 3.5
−3
1�([H2 O2 ]�mol dm )

15 Eadie–Hofstee plot
(υ�[H2 O2 ])�s−1

10

5
4.40 4.45 4.50 4.55 4.60 4.65 4.70
−3 −1
υ�(mol dm s )

For the Lineweaver–Burk plot, the equation of the line is

1�(υ�mol dm−3 s−1 ) = 5.190 × 10−3 × 1�([H2 O2 ]�mol dm−3 ) + 0.2084

�e intercept is identi�ed with 1�υ max so that

1
υ max = = 4.79... mol dm−3 s−1 = �.�� mol dm−3 s−1
0.2084 mol dm−3 s−1
 0.15 Hanes plot

([H2 O2 ]�υ)�s
0.10

0.05
0.2 0.3 0.4 0.5 0.6 0.7 0.8
−3
[H2 O2 ]�(mol dm )

�e slope is identi�ed with K M �υ max so that

��� � � � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � � � � � � � � ��
slope υ max

K M = (5.190 × 10−3 s) × (4.79... mol dm−3 s−1 ) = �.���� mol dm−3

For the Eadie–Hofstee plot, the equation of the line is

(υ�[H2 O2 ])�s−1 = −40.02 × (υ�mol dm−3 s−1 ) + 192.1

�e slope is identi�ed with −1�K M so that

−1
KM = = 0.0249... mol dm−3 = �.���� mol dm−3
−40.02 dm3 mol−1
�e intercept is identi�ed with υ max �K M so that

��� � � � � � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � � � � � � ��
KM
�
intercept

υ max = ( 192.1 s−1 ) × (0.0249... mol dm−3 ) = �.�� mol dm−3 s−1

For the Hanes plot, the equation of the line is

([H2 O2 ]�υ)�s = 0.2084 × ([H2 O2 ]�mol dm−3 ) + 5.189 × 10−3

�e slope is identi�ed with 1�υ max so that

1
υ max = = 4.79... mol dm−3 s−1 = �.�� mol dm−3 s−1
0.2084 dm3 mol−1 s
�e intercept is identi�ed with K M �υ max so that

��� � � � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � � � � � � � � � � ��
intercept υ max

K M = (5.189 × 10−3 s) × (4.79... mol dm−3 s−1 ) = �.���� mol dm−3

�e three plots thus give essentially the same values of K M and υ max for
these data.
E��G.�(b) �e primary quantum yield is de�ned by [��G.�a–���], � = N events �N abs . In
this equation N abs is the number of photons absorbed and N events is, in this
case, the number of molecules of A that decompose, N decomposed . Rearranging
gives
N decomposed n decomposed N A n formed N A
N abs = = =
� � �
In the �nal expression, n formed is the amount in moles of B that is formed, which
from the stoichiometry of the reaction A → B + C is equal to the amount of A
that decomposes. �e quantum yield is 120 mmol einstein−1 , or 0.120 mol mol−1
= 0.120, hence

n formed N A (1.77 × 10−3 mol) × (6.0221 × 1023 mol−1 )

N abs = = = 8.88 × 1021
� 0.120

E��G.�(b) �e �uorescence quantum yield is given by [��G.�–���], � F,0 = k F τ 0 . �e

observed lifetime τ 0 is given by [��G.�b–���], τ 0 = 1�(k F + k ISC + k IC ), which
is written as τ 0 = 1�k r where k r = k F + k ISC + k IC is the e�ective �rst-order
rate constant for the decay of the excited state of the �uorescing species. For a
�rst-order process k r is related to the half-life according to [��B.�–���], t 1�2 =
ln 2�k r , and combining this expression with τ 0 = 1�k r gives t 1�2 = ln 2�(1�τ 0 ) =
ln 2τ 0 . Hence τ 0 = t 1�2 � ln 2.
Rearranging [��G.�–���] then gives

� F,0 � F,0 � F,0 ln 2 0.16 × ln 2

kF = = = = = 7.4 × 107 s−1
τ0 t 1�2 � ln 2 t 1�2 1.5 × 10−9 s

E��G.�(b) �e Stern–Volmer equation [��G.�–���] is � F,0 �� F = 1 + τ 0 k Q [Q], where � F

and � F,0 are the �uorescence quantum yields with and without the quencher.
�e rate of �uorescence υ, and hence the �uorescence intensity, is directly pro-
portional to the �uorescence quantum yield according to [��G.�b–���], � =
υ�I abs . �erefore to reduce the �uorescence intensity to 75% of the unquenched
value requires � F = 34 � F,0 and hence � F,0 �� F = 43 . Rearranging the Stern–
Volmer equation then gives

� F,0 �� F − 1 4�3 − 1
[Q] = =
τ0 kQ (3.5×10 s)×(2.5×109 dm3 mol−1 s−1 )
−9

= �.��� mol dm−3

E��G.�(b) �e e�ciency of resonance energy transfer η T is de�ned by [��G.�–���], η T =
1 − � F �� F,0 , and the distance-dependence of the e�ciency is given by [��G.�–
���], η T = R 06 �(R 06 + R 6 ), where R is the donor–acceptor distance and R 0 is a
constant characteristic of the particular donor–acceptor pair.
In this case a decrease of the �uorescence quantum yield by ��% implies that
� F = (1 − 0.15)� F,0 = �.��� F,0 . Hence the e�ciency is η T = 1 − � F �� F,0 =
1 − 0.85 = 0.15. Rearranging [��G.�–���] for R, and taking R 0 = 2.2 nm from
Table ��G.� on page ���, gives

1 − ηT 1 − 0.15 1�6
1�6
R = R0 � � = (2.2 nm) × � � = �.� nm
ηT 0.15

P��G.� �e quantum yield in terms of the rates of processes is given by [��G.�b–���],

rate of process, υ
�= hence υ = � × (rate of photon absorption)
rate of photon absorption
�e rate of photon absorption is calculated by �rst �nding the fraction of pho-
tons that are absorbed by the layer of stratosphere. �is is done using the
Beer–Lambert law [��A.�–���], which states that the intensity of transmitted
radiation I is related to the intensity of incident radiation I 0 according to I =
I 0 10−ε[J]L , where [J] is the concentration of the absorbing substance, L is the
thickness of the sample through which the radiation is passed, and ε is the
the molar absorption coe�cient. �e fraction of photons that are transmitted
through the layer of stratosphere is therefore I�I 0 = 10−ε[O3 ]L , and the fraction
f that are absorbed is

f = 1 − I�I 0 = 1 − 10−ε[O3 ]L
= 1 − 10−(260 dm mol−1 cm−1 )×(8×10−9 mol dm−3 )×(1.0 km)×[(10 5 cm)�(1 km)]
= 0.380...
3

�e rate of photon absorption is then calculated by considering a column of the

stratosphere with a cross sectional area of 1 cm2 and a height of 1 km = 105 cm.
A �ux of 1 × 1014 photons cm−2 s−1 means that each second 1 × 1014 photons
arrive at the top of this column. Of these photons, a fraction f = 0.380... are
absorbed as they pass through the column, so the column absorbs 0.380...×1014
photons per second. �e rate of photon absorption per dm3 of stratosphere is
found by dividing by the volume of the column, which is (1 cm2 ) × (105 cm) =
105 cm3 , or 102 dm3 . Hence
0.380... × 1014 s−1
rate of photon absorption = 3 = 0.380... × 1012 dm−3 s−1
10 dm
2

Multiplication by the quantum yield � gives the rate of ozone consumption in

molecules dm−3 s−1 , and division by N A then gives the rate in mol dm−3 s−1 .

� 0.380... × 1012 dm−3 s−1

�

υ = 0.94 × = 5.9 × 10−13 mol dm−3 s−1

6.0221 × 1023 mol−1
P��G.� �e Stern–Volmer equation [��G.�–���] is � F,0 �� F = 1 + τ 0 k Q [Q]. By analogy
with this expression, the e�ect of a quencher on the phosphorescence quantum
yield � P is � P,0 �� P = 1+ τ 0 k Q [Q], where � P,0 is the phosphorescence quantum
yield in the absence of the quencher.
By analogy with [��G.�–���], � F,0 = k F τ 0 , the phosphorescence quantum yield
is � P,0 = k P τ 0 , where k P is the rate constant for phosphorescence. �is implies
that the rate constant for phosphorescence, and hence the rate of phospho-
rescence, which in turn determines the intensity of the phosphorescence, is
proportional to the quantum yield. �erefore I P,0 �I P = � P,0 �� P , which on
substitution into the equation � P,0 �� P = 1 + τ 0 k Q [Q] above gives

I P,0 1 1 τ0 kQ
= 1 + τ 0 k Q [Q] hence = + [Q]
IP I P I P,0 I P,0

�is expression implies that a plot of 1�I P against [Q] should be a straight line
of slope τ 0 k Q �I P,0 and intercept 1�I P,0 . �e data are plotted in Fig. ��.��.

[Q]�(mol dm−3 ) I P �(arbitrary units) I P−1 �(arbitrary units)−1

0.001 0 0.41 2.44
0.005 0 0.25 4.00
0.010 0 0.16 6.25

6
I P−1 �(arbitrary units)−1

0.000 0.002 0.004 0.006 0.008 0.010 0.012

[Q]�(mol dm−3 )

�e data lie on a good straight line, the equation of which is

I P−1 �(arbitrary units)−1 = (4.25 × 102 ) × ([Q]�mol dm−3 ) + 1.97

�e intercept is identi�ed with 1�I P,0 so that

1
I P,0 = = 0.507... arbitrary units
1.97 (arbitrary units)−1
 �e slope is identi�ed with τ 0 k Q �I P,0
τ0 kQ
= 4.25 × 102 dm3 mol−1 (arbitrary units)−1
I P,0
�e value of I P,0 is known from the intercept, but it is necessary to �nd τ 0
before this expression can be used to calculate k Q . �is is done using [��G.�a–
���], [S∗ ] = [S∗ ]0 e−t�τ 0 , for the decay of the excited species in the absence of
a quencher. �e half-life of the phosphorescent species S∗ , and therefore of
the phosphorescence, is the time taken for [S∗ ] to reach half its initial value.
�erefore
[S ]0
1 ∗
2
= [S∗ ]e−t 1�2 �τ 0 hence 2 = e t 1�2 �τ 0 hence τ 0 = t 1�2 � ln 2
Substituting this into the expression above involving the slope of the graph gives
t 1�2 k Q
= 4.25 × 102 dm3 mol−1 (arbitrary units)−1 , hence
I P,0 ln 2
(0.507... arbitrary units)× ln 2 ×(4.25 × 102 dm3 mol−1 (arbitrary units)−1 )
kQ =
29 × 10−6 s
= 5.1 × 106 dm3 mol−1 s−1

P��G.� �e e�ciency of energy transfer in terms of the donor–acceptor distance is

given by [��G.�–���], η T = R 06 �(R 06 + R 6 ). Taking the reciprocal of both sides
gives
1 R6 + R6 R6
= 0 6 =1+ 6
ηT R0 R0
�is expression implies that a plot of η T against R 6 should be a straight line of
intercept � and slope 1�R 06 . �e data are plotted in Fig. ��.��.

R�nm ηT R 6 �nm6 1�η T

1.2 0.99 3.0 1.01
1.5 0.94 11 1.06
1.8 0.97 34 1.03
2.8 0.82 4.8 × 102 1.22
3.1 0.74 8.9 × 102 1.35
3.4 0.65 1.5 × 103 1.54
3.7 0.40 2.6 × 103 2.50
4.0 0.28 4.1 × 103 3.57
4.3 0.24 6.3 × 103 4.17
4.6 0.16 9.5 × 103 6.25

�e data lie on a modest straight line with intercept close to �, so it is concluded

that these data are consistent with [��G.�–���]. �e equation of the line is
1�η T = (5.5 × 10−4 ) × R 6 �nm6 + 0.97
 6

4
1�η T

0
0 2 000 4 000 6 000 8 000 10 000
R �nm
6 6

�e slope is identi�ed with 1�R 06 , so R 0 for the naphthyl–dansyl pair is

1�6
1
R0 = � � = �.� nm
5.5 × 10 nm
−4 −6

I��.� �e step S → I is autocatalytic because the rate of this step, dS�dt = rSI,
is proportional to I which is a product of the step. �e step I → R is not
autocatalytic because its rate dR�dt = aI does not depend on the product R
of the step.
Whether the disease spreads or dies out depends on whether the number in-
fectives I increases or decreases with time. For the disease to spread,
dI
= rSI − aI > 0 hence a�r < S
dt
Similarly, for the disease to die out,
dI
= rSI − aI < 0 hence a�r > S
dt

�e total rate of change of all species present is

dN dS dI dR
= + + = (−rSI) + (rSI − aI) + (aI) = 0
dt dt dt dt
�e result dN�dt = 0 implies that the total population is constant.

I��.� It is supposed that each monomer has one end group A with which it can join
to another monomer. In a polymer, only the terminal monomer unit in the
chain has a free end group.
�e probability PN that a polymer consists of N monomers is equal to the
probability that it has N − 1 reacted end groups and one unreacted end group.
�e fraction of end groups that have reacted is p and the fraction of free end
groups remaining is 1 − p, so the probability that a polymer contains N − 1
reacted groups and one unreacted group is p N−1 × (1 − p). �e average value
of N is then given by
∞ ∞ ∞
�N� = � N PN = � N p N−1 (1 − p) = (1 − p) � N p N−1
N=1 N=1 N=1

To evaluate the sum, it is noted that N p N−1 corresponds to the derivative of p N .

Hence
∞ ∞
d N d ∞ N d
� Np
N−1
=� p = �� p � = �p + p2 + p3 + ...�
N=1 N=1 dp dp N=1 dp

�e expression in square brackets is a geometric series with �rst term p and

common ratio p; the sum to in�nity of this series is therefore p�(1 − p). Hence
∞
d p (1 − p) + p 1
� Np
N−1
= � �= =
N=1 dp 1 − p (1 − p)2 (1 − p)2

�e average value of N is therefore

∞
1 1
�N� = (1 − p) � N p N−1 = (1 − p) × =
N=1 (1 − p) 2 1− p

�is is the same result as [��F.��a–���] which is derived in Section ��F.�(a) on

page ��� by a di�erent method. However the approach used here is more easily
generalised to �nd an expression for �N 2 �.
∞ ∞ ∞
�N 2 � = � N 2 PN = � N 2 p N−1 (1 − p) = (1 − p) � N × N p N−1
N=1 N=1 N=1

�e quantity N p N−1 is recognised as the derivative of p N

∞
d N d ∞
�N 2 � = (1 − p) � N × p = (1 − p) � � N p N �
N=1 dp dp N=1
∞
d
= (1 − p) �p � N p N−1 �
dp N=1

�e sum ∑∞
N=1 N p
N−1
was already evaluated above; its value is 1�(1 − p)2 .
Hence
d 1 1+ p 1+ p
�N 2 � = (1 − p) �p × � = (1 − p) × =
dp (1 − p)2 (1 − p)3 (1 − p)2

�e average values of M and M 2 are found by noting that the molar mass of a
polymer with N monomers is given by M = N M 1 where M 1 is the mass of a
 single polymer unit. Hence
1 M1
�M� = �N M 1 � = M 1 �N� = M 1 × =
1− p 1− p
1+ p M 2 (1 + p)
�M 2 � = �(N M 1 )2 � = �M 12 N 2 � = M 12 �N 2 � = M 12 × = 1
(1 − p) 2 (1 − p)2
�erefore
M 12 (1 + p) M 12 p M 1 p1�2
��M 2 � − �M�2 � =� − � = �M 12 �=
1�2
(1 − p) 2 (1 − p) 2 (1 − p) 2 1− p

�e root mean square deviation of the polymer mass is then

(�M 2 � − �M�2 )1�2 = ��(M 1 N)2 � − �M 1 N�2 � = �M 12 �N 2 � − M 12 �N�2 �

1�2 1�2

1�2
p M 1 p1�2
= M 1 ��N 2 � − �N�2 � = M1 × � � =
1�2

��� � � � � � � � � � � � � � � � � �� � � � � � � � � � � � � � � � � � (1 − p)2 1− p
var(N)

as before.
�e time dependence of p is given by [��F.��–���], p = k r t[A]0 �(1 + k r t[A]0 ).
Substituting this into the expression for (�M 2 � − �M�2 )1�2 gives the root mean
square deviation as a function of time as
1�2 −1
M 1 p1�2 k r t[A]0 k r t[A]0
= M 1 p1�2 (1 − p)−1 = M 1 � � �1 − �
1− p 1 + k r t[A]0 1 + k r t[A]0
1�2 −1
k r t[A]0 1
= M1 � � � �
1 + k r t[A]0 1 + k r t[A]0
= M 1 {k r t[A]0 (1 + k r t[A]0 )}
1�2

I��.� �e rate of the forward and backward steps are

d[B] d[B]
A→B = IA B→A = −k r [B]2
dt dt
�e overall rate of change of [B] is therefore d[B]�dt = I A − k r [B]2 . In the
steady state, d[B]�dt = 0, hence

I a 1�2
k r [B]2 = I a hence [B] = � �
kr
�is concentration can di�er signi�cantly from an equilibrium distribution
because changing the illumination may change the rate of the forward reaction
without a�ecting the reverse reaction. �is is in contrast to corresponding
equilibrium expression, in which the ratio [B]�[A] depends on a ratio of rate
constants for the forward and reverse reactions as explained in Section ��C.�
on page ���.
D��A.� To the extent that real gases deviate from perfect gas behaviour, they do so
because of intermolecular interactions. Interactions tend to be more important
at high pressures, when the size of the molecules themselves is not negligible
compared to the average intermolecular distance (mean free path). Attractive
interactions might enhance a reaction rate compared to the predictions of col-
lision theory, particularly if the parts of the molecules that are attracted to each
other are the reactive sites. Similarly, repulsive interactions might reduce the
frequency of collisions compared to what would be predicted for perfect gases.

D��A.� Reactions between complex molecules might be expected to have strong steric
requirements (small steric factors) as a result of the reaction requiring a par-
ticular orientation and approach of the reacting parts of the molecule: the
more complex the molecules, the smaller the fraction of collisions which are
potentially reactive.
In the RRK theory of unimolecular reactions molecular complexity plays a dif-
ferent role in that it governs the distribution of energy in the excited molecule.
In this theory the rate constant for the unimolecular decay of an energized
molecule A* is given by [��A.��–���],

E ∗ s−1
k b (E) = �1 − � kb
E
Here E ∗ is the minimum energy that must be accumulated in a bond for it to
break, E is the total energy, and s is the number of modes of motion (modelled
as harmonic oscillators) that the molecule possesses. �e term in parentheses is
less than �, therefore the expression implies that the more complex the molecule
(the greater s), the smaller the rate constant becomes.

E��A.�(b) �e collision frequency is given by [�B.��b–��], z = σ υ rel p�kT, where σ is the

collision cross-section, given in terms of the collision diameter d as σ = πd 2 ,
and υ rel is the mean relative speed of the colliding molecules. �is speed is
given by [�B.��b–��], υ rel = (8kT�πµ)1�2 , with µ = m A m B �(m A + m B ). For
 collisions between like molecules µ = m�2 and υ rel = (16kT�πm)1�2 .

σ υ rel p πd 2 p 16kT 1�2 π 1�2

z= = � � = 4d 2 p � �
kT kT πm mkT
= 4 × (360 × 10−12 m)2 × (120 × 103 Pa)
1�2
π
� �
(28.01 × 1.6605 × 10−27 kg) × (1.3806 × 10−23 J K−1 ) × (303 K)
= 7.90 × 109 s−1

To con�rm the units of z it is useful to recall that 1 J = 1 kg m2 s−2 and 1 Pa =

1 kg m−1 s−2 .
�e collision density between identical molecules is given by [��A.�b–���]

4kT 1�2 2
Z AA = σ � � N A [A]2
πm
where [A] is the molar concentration of the gas. In turn, this is expressed in
terms of the pressure using the perfect gas equation to give [A] = n A �V =
p A �RT.

4kT 1�2 N A2 p2A 2 πkT

1�2
p2A π 1�2
Z AA = πd 2 � � = 2d � � = 2d 2 � 3 3 � p2A
πm R T
2 2 m k T
2 2 mk T
= 2 × (360 × 10−12 m)2 × (120 × 103 Pa)2
1�2
π
� �
(28.01 × 1.6605 × 10 kg) × (1.3806 × 10−23 J K−1 )3 × (303 K)3
−27

= 1.13 × 1035 m−3 s−1

�e above expression shows that z ∝ pT −1�2 , but at constant volume p ∝ T,

therefore the overall temperature dependence is z ∝ T 1�2 . �e percentage
increase in z on increasing T by �� K is therefore
3131�2 − 3031�2
= 0.0163... = �.�%
3031�2
Similarly the �nal expression for the collision density shows Z AA ∝ p2 T −3�2
which, with p ∝ T, gives Z AA ∝ T 2 T −3�2 ∝ T 1�2 . �is is the same dependence
as z, so the same percentage increase will result.

E��A.�(b) �e collision theory expression for the rate constant is given in [��A.�–���].
In this expression, the factor e−E a �RT is identi�ed as the fraction of collisions f
having at least kinetic energy E a along the �ight path. For example with E a =
15 kJ mol−1 and T = 300 K
Ea 15 × 103 J mol−1
= = 6.01... f = e−6.01 ... = 2.45 × 10−3
RT (8.3145 J K−1 mol−1 ) × (300 K)

A similar calculation gives f = 0.105 at T = 800 K. With E a = 150 kJ mol−1

the result is f = 7.64 × 10−27 at T = 300 K, and f = 1.61 × 10−10 at T = 800 K.
E��A.�(b) �e method for calculating the fractions is shown in the solution to Exercise
E��A.�(b). For E a = 15 kJ mol−1 and T = 300 K it is found that f = 2.44...×10−3
and increasing the temperature to ��� K gives f = 2.96...×10−3 . �e percentage
increase is
(2.96... × 10−3 ) − (2.44... × 10−3 )
100 × = ��%
2.44... × 10−3
A similar calculation gives an increase by �.�% at ��� K. With E a = 150 kJ mol−1
the result is ���% at T = 300 K, and ��% at T = 800 K.

E��A.�(b) �e collision theory expression for the rate constant is given in [��A.�–���].
1�2
8kT
kr = σ NA � � e−E a �RT
πµ
= (0.30 × 10−18 m2 ) × (6.0221 × 1023 mol−1 )
8 × (1.3806 × 10−23 J K−1 ) × (450 K)
1�2
� �
π(3.930 × 1.6605 × 10−27 kg)
× e−(200×10 J mol−1 )�[(8.3145 J K−1 mol−1 )×(450 K)]
3

= 1.7 × 10−15 mol−1 m3 s−1

�e units are best resolved by realising that (8kT�πµ)1�2 is a speed, with units
m s−1 . Note that �.�� nm2 is 0.30 × 10−18 m2 .

E��A.�(b) As described in Section ��A.�(b) on page ���, the reactive cross section may be
estimated from the (non-reactive) collision cross sections of A and B: σest =
(σA + σB )2 . �e steric factor is given by the ratio of the experimental
1 1�2 1�2
4
reactive cross section, σexp , to the estimated cross section

σexp 8.7 × 10−22 m2

P= =
σest [(0.88 × 10−18 m2 )1�2 + (0.40 × 10−18 m2 )1�2 ]2 �4
= 1.4 × 10−3

E��A.�(b) In the RRK theory the rate constant for the unimolecular decay of an energized
molecule A* is given by [��A.��–���],

E ∗ s−1
k b (E) = �1 − � k b = (1 − x)s−1 k b
E
where x = E ∗ �E. For a linear molecule with � atoms there are 3N −5 = 3×4−5 =
7 normal modes, so s = 7. �is expression is rearranged for x to give

x = 1 − [k b (E)�k b ]1�(s−1)
= 1 − [0.025]1�(7−1) = �.��
E��A.�(b) In the RRK theory the rate constant for the unimolecular decay of an energized
molecule A* is given by [��A.��–���],

k b (E) E ∗ s−1
= �1 − �
kb E

where E ∗ is the minimum energy needed to break the bond, and E is the energy
available from the collision. With the data given

k b (E) 300 kJ mol−1

12−1
= �1 − � = 4.19 × 10−5
kb 500 kJ mol−1

P��A.� �e �rst step is to analyse the given rate constant data in terms of the Arrhenius
equation, k r = Ae−E a �RT . A plot of ln k r against 1�T has slope −E a �R and
intercept ln A. �e data are tabulated below and the plot is shown in Fig. ��.�.

T�K (103 �T)�K−1 k r �(cm3 mol−1 s−1 ) ln[k r �(cm3 mol−1 s−1 )]
600 1.67 4.6 × 102 6.13
700 1.43 9.7 × 103 9.18
800 1.25 1.3 × 10 5
11.8
1 000 1.00 3.1 × 106 14.9

15
ln[k r �(cm3 mol−1 s−1 )]

10

5
1.0 1.2 1.4 1.6 1.8
(10 �T)�K
3 −1

�e data are a good �t to the line

ln[k r �(cm3 mol−1 s−1 )] = −1.331 × 104 �(T�K) + 28.30

From the intercept ln A = 28.30 and hence A = 1.944 × 1012 cm3 mol−1 s−1 ;
for the next part of the calculation this is conveniently expressed as 1.944 ×
106 m3 mol−1 s−1 .
 �e collision theory expression for the rate constant is given in [��A.�–���]
1�2
8kT
kr = σ ∗ NA � � e−E a �RT
πµ
Here σ ∗ is interpreted as the reactive cross-section, related to the collision
cross-section σ by σ ∗ = Pσ, where P is the steric factor. Comparison of the
above expression for k r with the Arrhenius equation, k r = Ae−E a �RT , gives
the frequency factor as A = σ � N A (8kT�πµ) ; this is rearranged to give an
1�2
∗
expression for σ . �e mass of the NO� radical is 46.01 m u , therefore the
reduced mass of the collision is µ = 12 × 46.01 m u = 3.81... × 10−26 kg. For
the calculation the temperature is taken to be in the middle of the data, which
is ��� K.
A πµ 1�2
σ∗ = � �
N A 8kT
1.944 × 106 m3 mol−1 s−1 π(3.81... × 10−26 kg)
1�2
= � �
6.0221 × 1023 mol−1 8 × (1.3806 × 10−23 J K−1 ) × (750 K)
= 3.88... × 10−21 m2 = 0.0039 nm2

�e units are best resolved by realising that (8kT�πµ)1�2 is a speed, with units
m s−1 . �e steric factor is P = σ ∗ �σ = (3.88... × 10−21 m2 )�(0.60 × 10−18 m2 ) =
�.���� .

P��A.� In Example ��A.� on page ��� it is shown that for the harpoon mechanism the
reactive cross-section σ ∗ can be estimated as
2
e2
σ = πR
∗ ∗2
= π� �
4πε 0 (I − E ea )
With the data for Na and Cl� , and using the conversion 1 eV = 1.6022 × 10−19 J
from inside the font cover
(1.6022 × 10−19 C)2
2
σ = π�
∗
�
4π(8.8542 × 10−12 J−1 C2 m−1 ) × (5.1 − 1.3) × (1.6022 × 10−19 J)
= 4.51... × 10−19 m2 = �.�� nm2
�e results of similar calculations for the other combinations of alkali metal
and halogen are given in the table. All the values of σ ∗ in the table are smaller
than the experimental values, but they do show the correct trends down the
columns. �e variation with E ea across the table is not so good.

σ ∗ �nm2 Cl� Br� I�

Na �.�� �.�� �.��
K �.�� �.�� �.��
Rb �.�� �.�� �.��
Cs �.�� �.�� �.��
D��B.� In the cage e�ect, a pair of molecules may be held in close proximity for an
extended period of time by the presence of other neighbouring molecules, typ-
ically solvent molecules. Such a pair is called an encounter pair, and their
time near each other is called an ‘encounter’ as opposed to a simple collision.
An encounter may include a series of collisions. Furthermore, as a result of
collisions with neighbouring molecules, an encounter pair may pick up enough
energy to react, even though the pair may not have had enough energy when
�rst formed.

E��B.�(b) �e second-order rate constant for a di�usion-controlled reaction is given by

[��B.�–���], k d = 4πR ∗ DN A , where R∗ is the critical distance and D is the
di�usion constant. As explained in the text, D is the sum of the di�usion
constants of the two species, therefore in this case D is twice the value given.
With the data given

k d = 4π × (0.4 × 10−9 m) × (2 × 5.2 × 10−9 m2 s−1 ) × (6.0221 × 1023 mol−1 )

= 3.1 × 107 m3 mol−1 s−1

E��B.�(b) For a di�usion-controlled reaction the rate constant is approximated by [��B.�–

���], k d = 8RT�3η, where η is the viscosity. Recall that 1 P = 10−1 kg m−1 s−1 ,
so that 1 cP = 10−3 kg m−1 s−1 .
(i) For decylbenzene

8 × (8.3145 J K−1 mol−1 ) × (298 K)

kd = = 1.97 × 106 m3 mol−1 s−1
3 × (3.36 × 10−3 kg m−1 s−1 )

In sorting out the units it is useful to recall 1 J = 1 kg m2 s−2 .

(ii) For sulfuric acid

8 × (8.3145 J K−1 mol−1 ) × (298 K)

kd = = 2.4 × 105 m3 mol−1 s−1
3 × (27 × 10−3 kg m−1 s−1 )

E��B.�(b) For a di�usion-controlled reaction the rate constant is approximated by [��B.�–

���], k d = 8RT�3η, where η is the viscosity. Recall that 1 P = 10−1 kg m−1 s−1 ,
so that 1 cP = 10−3 kg m−1 s−1 . �erefore the rate constant is

8 × (8.3145 J K−1 mol−1 ) × (320 K)

kd =
3 × (0.601 × 10−3 kg m−1 s−1 )
= 1.18... × 106 m3 mol−1 s−1 = 1.18 × 106 m3 mol−1 s−1
 �e half-life of a second-order reaction is given by [��B.�–���], t 1�2 = 1�k r [A]0 .
�e initial concentration is �.� mmol dm−3 which is �.� mol m−3 . With the data
given
1
t 1�2 = = �� ns
(1.18... × 106 m3 mol−1 s−1 ) × (2.0 mol m−3 )

E��B.�(b) �e second-order rate constant for a di�usion-controlled reaction is given by

[��B.�–���], k d = 4πR ∗ DN A , where R∗ is the critical distance and D is the
di�usion constant. As explained in the text D is the sum of the di�usion con-
stants of the two species. �e value of D is estimated using the Stokes–Einstein
equation, D = kT�6πηR, and with the data given separate values of D are
computed for the two species. �e critical distance is taken as R∗ = R A + R B .
Recall that 1 P = 10−1 kg m−1 s−1 , so that 1 cP = 10−3 kg m−1 s−1 .

k d = 4π(R A + R B )(D A + D B )N A
kT 1 1
= 4πN A (R A + R B ) � + �
6πη R A R B
= 4π × (6.0221 × 1023 mol−1 ) × (421 + 945)
(1.3806 × 10−23 J K−1 ) × (293 K) 1 1
× � + �
6π × (1.35 × 10−3 kg m−1 s−1 ) 421 945
= 5.64... × 106 m3 mol−1 s−1

�e initial concentrations are [A] = 0.155 mol dm−3 = 0.155 × 103 mol m−3
and [B] = 0.195 mol dm−3 = 0.195 × 103 mol m−3 . �e initial rate is therefore

d[P]
= k d [A][B]
dt
= (5.64... × 106 m3 mol−1 s−1 )
× (0.155 × 103 mol m−3 ) × (0.195 × 103 mol m−3 )
= 1.71 × 1011 mol m−3 s−1

Using [��B.�–���], k d = 8RT�3η, the rate constant is

8 × (8.3145 J K−1 mol−1 ) × (293 K)

kd = −1 −1 = 4.81 × 106 m3 mol−1 s−1
3 × (1.35 × 10 kg m s )
−3

�is value would result in a somewhat slower initial rate, casting some doubt
therefore on the validity of the approximations used.

P��B.� It is convenient to plot the function as

[J]∗ A e−x �4D t−k r t

2

=
n0 (πDt)1�2
 For the plots shown in Fig. ��.� the di�usion constant is chosen as D = 4.1 ×
10−9 m2 s−1 , the value suggested in Brief illustration ��B.� on page ���. �e
plot on the le� is for k r = 0. As expected, as time increases the material spreads
further from the origin and the pro�le �attens. �e plot on the right is for
k r = 2×10−3 s−1 . Now, because reaction also consumes the material, the curves
are all at lower values with the longer time curves being more a�ected because
more material has been consumed by the reaction.

kr = 0

800 t = 100 s
t = 200 s
t = 1000 s
([J]∗ A�n 0 )�m−1

600

400

200

0
0 2 4 6 8
x�mm
k r = 2 × 10−3 s−1

800 t = 100 s
t = 200 s
t = 1000 s
600

400

200

0
0 2 4 6 8
x�mm

P��B.� (a) For a di�usion-controlled reaction the rate constant is approximated by

[��B.�–���], k d = 8RT�3η, where η is the viscosity, given at ��� K as
1.06 × 10−3 kg m−1 s−1 in the Resource section

8 × (8.3145 J K−1 mol−1 ) × (298 K)

kd = = 6.23 × 106 m3 mol−1 s−1
3 × (1.06 × 10−3 kg m−1 s−1 )
 (b) �e second-order rate constant for a di�usion-controlled reaction is also
given by [��B.�–���], k d = 4πR∗ DN A , where R∗ is the critical distance
and D is the sum of the di�usion constants of the two species. It is conve-
nient to express the rate constant as 2.77×106 m3 mol−1 s−1 . Rearranging
the expression gives

kd 2.77 × 106 m3 mol−1 s−1

R∗ = =
4πDN A 4π × (1 × 10−9 m2 s−1 ) × (6.0221 × 1023 mol−1 )
= �.� nm

D��C.� �e Eyring equation, [��C.��–���], results from activated complex theory which
is an attempt to account for the rate constants of bimolecular reactions by con-
sidering the scheme A + B ��⇀ � C‡ ��→ P, where C‡ is an activated complex.
In the formulation of the theory, it is assumed that the activated complex and
the reactants are in equilibrium. �e concentration of the activated complex
is calculated in terms of an equilibrium constant, which in turn is calculated
from the partition functions of the reactants and a postulated form of the ac-
tivated complex. It is further supposed that one normal mode of the activated
complex, the one corresponding to displacement along the reaction coordinate,
has a very low force constant. Displacement along this mode leads to products,
provided that the complex enters a certain con�guration of its atoms, known
as the transition state.

D��C.� �e primary kinetic isotope e�ect is the change in rate constant of a reac-
tion in which the breaking of a bond involving the isotope occurs in the rate-
determining step. �e reaction coordinate in a C–H bond-breaking process
corresponds to the stretching of that bond. �e vibrational energy of the stretch-
ing depends upon the e�ective mass of the C and H atoms. Upon deuteration,
the zero-point energy of the bond is lowered due to the greater mass of the deu-
terium atom. However, the height of the energy barrier is not much changed
because the relevant vibration in the activated complex has a very low force
constant, so there is little zero-point energy associated with this vibration of
the complex, and hence little change in its zero-point energy upon deuteration.
�e net e�ect is an increase in the activation energy of the reaction. It is then
expected that the rate constant for the reaction will be lowered in the deuterated
molecule, and this is what is observed.
Sometimes the rate of reaction is lowered upon deuteration to an extent even
greater than can be accounted for by this analysis. In such cases, quantum-
mechanical tunneling may be part of the reaction mechanism. �e probability
of tunneling is highly sensitive to mass, so it is much less likely (and therefore
much slower) for deuterium than for 1 H. If the rate of a reaction is altered
by isotopic substitution it implies that the substituted site plays an important
 role in the mechanism of the reaction. For example, an observed e�ect on
the rate can identify bond breaking events in the rate determining step of the
mechanism. On the other hand, if no isotope e�ect is observed, the site of the
isotopic substitution may play no critical role in the mechanism of the reaction.

E��C.�(b) �e empirical expression is compared to the Arrhenius equation k r = Ae−E a �RT ,

allowing the activation energy to be determined from E a �R = 5925 K; hence
E a = (8.3145 J K−1 mol−1 ) × (5925 K) = 49.2... kJ mol−1 . �e frequency factor
is A = 6.92 × 1012 dm3 mol−1 s−1 = 6.92 × 109 m3 mol−1 s−1 .
�e relationship between E a and ∆‡ H for a bimolecular solution-phase reac-
tion is given by [��C.��–���], ∆‡ H = E a − RT = (49.2... × 103 J mol−1 ) −
(8.3145 J K−1 mol−1 ) × (298 K) = ��.� kJ mol−1 . �e relationship between
A and ∆‡ S for a bimolecular solution-phase reaction is given by [��C.��b–���]

kT RT ∆‡ S�R
A=e e
h p−○
Ap−○ h
hence ∆‡ S = R ln
ekRT 2
= (8.3145 J K−1 mol−1 )
(6.92 × 109 m3 mol−1 s−1 ) × (105 Pa) × (6.6261 × 10−34 J s)
× ln
e(1.3806 × 10−23 J K−1 ) × (8.3145 J K−1 mol−1 ) × (298 K)2
= −34.1 J K−1 mol−1

Note the conversion of the units of A to m3 mol−1 s−1 .

E��C.�(b) �e empirical expression is compared to the Arrhenius equation k r = Ae−E a �RT ,

allowing the activation energy to be determined from E a �R = 4972 K; hence
E a = (8.3145 J K−1 mol−1 ) × (4972 K) = 41.3... kJ mol−1 . �e frequency factor
is A = 4.98 × 1013 dm3 mol−1 s−1 = 4.98 × 1010 m3 mol−1 s−1 .
�e relationship between E a and ∆‡ H for a bimolecular solution-phase reac-
tion is given by [��C.��–���], ∆‡ H = E a − RT = (41.3... × 103 J mol−1 ) −
(8.3145 J K−1 mol−1 ) × (298 K) = +38.8... kJ mol−1 . �e relationship between
A and ∆‡ S for a bimolecular solution-phase reaction is given by [��C.��b–���]

kT RT ∆‡ S�R
A=e e
h p−○
Ap−○ h
hence ∆‡ S = R ln
ekRT 2
= (8.3145 J K−1 mol−1 )
(4.98 × 1010 m3 mol−1 s−1 ) × (105 Pa) × (6.6261 × 10−34 J s)
× ln
e(1.3806 × 10−23 J K−1 ) × (8.3145 J K−1 mol−1 ) × (298 K)2
= −17.6... J K−1 mol−1
 Note the conversion of the units of A to m3 mol−1 s−1 . ∆‡ G is found by com-
bining the values of ∆‡ H and ∆‡ S in the usual way

∆‡ G = ∆‡ H − T∆‡ S
= (+38.8... × 103 J mol−1 ) − (298 K) × (−17.6... J K−1 mol−1 )
= +��.� kJ mol−1

E��C.�(b) �e rate constant for a bimolecular gas phase reaction is given by [��C.��a–���]

kT RT ∆‡ S�R −E a �RT
k r = e2 e e
h p−○

�is rearranges to

hp−○ k r hp−○ Ea
∆‡ S = R ln �k r eE a �RT � = R ln � �+
e2 kRT 2 e kRT
2 2 T
= (8.3145 J K−1 mol−1 )
(0.35 m3 mol−1 s−1 ) × (6.6261 × 10−34 J s) × (105 Pa)
× ln � �
e2 (1.3806 × 10−23 J K−1 ) × (8.3145 J K−1 mol−1 ) × (338 K)2
39.7 × 103 J mol−1
+
338 K
= −124 J K−1 mol−1

E��C.�(b) In Example ��C.� on page ��� the following expression for the rate constant for
a reaction between structureless particles is derived
1�2
8kT
kr = NA � � σ ∗ e−∆E 0 �RT
πµ

�e activation energy is obtained from its usual de�nition, [��D.�–���]

d ln k r
E a = RT 2
dT
� �
�
2 d � �
� 8kT
1�2 �
� ∆E 0 �
∗�
�
�
= RT �ln �N A � � σ �− �
dT � �
� �
� � �
�
πµ RT
� �
1 ∆E 0
= RT �
2
+ � = 2 RT + ∆E 0
1
2T RT 2

�erefore ∆E 0 = E a − 12 RT and hence

1�2
8kT
kr = NA � � σ ∗ e1�2 e−∆E a �RT
πµ
 �e rate constant for a bimolecular gas phase reaction is given by [��C.��a–���]
kT RT ∆‡ S�R −E a �RT
k r = e2 e e
h p−○
Comparing these two expressions gives
1�2
8kT kT RT ∆‡ S�R
NA � � σ ∗ e1�2 = e2 e
πµ h p−○
�is is rearranged to give ∆‡ S, noting that for a collision between like molecules
µ = 12 m

� hp−○ �
1�2
8kT
∆ S = R ln N A �
‡
� σ∗
� πµ e3�2 kRT 2 �
= (8.3145 J K−1 mol−1 )
�
� 8 × (1.3806 × 10−23 J K−1 ) × (450 K)
1�2
× ln �
�(6.0221 × 10 23
mol −1
) × � �
� π × 12 × 92 × (1.6605 × 10−27 kg)
�
× (0.45 × 10−18 m2 )
�
(6.6261 × 10−34 J s) × (105 Pa) �
× �
�
e3�2 (1.3806 × 10−23 J K ) × (8.3145 J K mol ) × (450 K)2 �
−1 −1 −1
�
= −79 J K−1 mol−1

E��C.�(b) It is convenient to convert the units of the frequency factor and express it as
A = 2.3 × 1010 m3 mol−1 s−1 . �e relationship between E a and ∆‡ H for a
bimolecular gas-phase reaction is given by [��C.��–���], ∆‡ H = E a − 2RT =
(30.0 × 103 J mol−1 ) − 2 × (8.3145 J K−1 mol−1 ) × (298 K) = +25.0... kJ mol−1 =
+25 kJ mol−1 . �e relationship between A and ∆‡ S for a bimolecular gas-
phase reaction is given by [��C.��a–���]
kT RT ∆‡ S�R
A = e2 e
h p−○
Ap−○ h
hence ∆‡ S = R ln 2
e kRT 2
= (8.3145 J K−1 mol−1 )
(2.3 × 1010 m3 mol−1 s−1 ) × (105 Pa) × (6.6261 × 10−34 J s)
× ln
e2 (1.3806 × 10−23 J K−1 ) × (8.3145 J K−1 mol−1 ) × (298 K)2
= −32.4... J K−1 mol−1 = −32 J K−1 mol−1
∆‡ G is found by combining the values of ∆‡ H and ∆‡ S in the usual way
∆‡ G = ∆‡ H − T∆‡ S
= (+25.0... × 103 J mol−1 ) − (298 K) × (−32.4... J K−1 mol−1 )
= +�� kJ mol−1
E��C.�(b) �e variation of the rate constant with ionic strength is given by [��C.��–���],
lg k r = lg k r○ + 2Az A z B I 1�2 ; at ��� K and for aqueous solutions A = 0.509. In
the absence of further information assume z A = +1 and z A = +1. Rearranging
for lg k r○ gives

lg k r○ = lg k r − 2Az A z B I 1�2
= lg(1.55 dm6 mol−2 min−1 ) − 2 × (0.509) × (+1) × (+1) × (0.0241)1�2
= 0.0322...

�erefore k r○ = 1.08 dm6 mol−2 min−1 .

E��C.�(b) �e e�ect of deuteration on the rate constant is given by [��C.��–���]

� 1�2 �
k r (C–D) ħω(C–H) �
� µ CH �
�
= e−ζ ζ= �1 − � � �
k r (C–H) �
� �
�
� �
2kT µ CD

In this expression ω(C–H) = (k f �µ CH )1�2 . It can be adapted for other pairs of

isotopes by changing the e�ective masses and the force constant.
�e e�ective mass for 12 C–16 O is
mC mO 12 × 15.9949
µ CO = = m u = 6.85... m u = 1.13... × 10−26 kg
m C + m O 12 + 15.9949

Likewise for 12 C–18 O (denoted C–O′ ) the e�ective mass is

m C m O′ 12 × 17.9992
µ CO′ = = m u = 7.19... m u
mC + mO ′ 12 + 17.9992

With the given force constant

1750 N m−1
1�2
ω(C–O) = � � = 3.92... × 1014 s−1
1.13... × 10−26 kg

At ��� K

(1.0546 × 10−34 J s) × (3.92... × 1014 s−1 ) 6.85... 1�2

ζ= �1 − � � �
2 × (1.3806 × 10−23 J K−1 ) × (298 K) 7.19...
= 0.121...
k r (C–O′ )
= e−ζ = e−.121 ... = �.��
k r (C–O)

Raising the temperature will decrease ζ which will have the e�ect of increasing
the ratio k r (C–O′ )�k r (C–O) and so moving it closer to �. �at is, the isotope
e�ect will be reduced.
P��C.� �e �rst step is to analyse the given rate constant data in terms of the Arrhenius
equation, k r = Ae−E a �RT . A plot of ln k r against 1�T has slope −E a �R and
intercept ln A. �e data are tabulated below and the plot is shown in Fig. ��.�.

θ�○ C T�K (103 �T)�K−1 k r �s−1 ln(k r �s−1 )

−24.82 248.33 4.027 1.22 × 10−4 −9.011
−20.73 252.42 3.962 2.31 × 10−4 −8.373
−17.02 256.13 3.904 4.39 × 10−4 −7.731
−13.00 260.15 3.844 8.50 × 10−4 −7.070
−8.95 264.20 3.785 1.43 × 10−3 −6.550

−7.0
ln(k r �s−1 )

−8.0

−9.0
3.80 3.85 3.90 3.95 4.00
(10 �T)�K
3 −1

�e data are a good �t to the line

ln(k r �s−1 ) = −1.035 × 104 �(T�K) + 32.66

From the intercept ln A = 32.66 and hence A = 1.526×1014 s−1 . From the slope
−E a �R = 1.035 × 104 K, hence E a = 86.3... kJ mol−1 = ��.� kJ mol−1 .
�is reaction is �rst order, so the argument leading to the expression for the rate
constant in terms of partition functions needs to be modi�ed. Crucially, the
equilibrium constant for the formation of the activated complex, K ‡ = p C‡ �p A ,
no longer includes a p−○ term. Similarly, for this equilibrium the conversion
from partial pressures to concentrations does not involve an RT term because
in this case these terms cancel between products and reactants: in other words
the equilibrium constant has the same value regardless of whether partial pres-
sures or concentrations are used. Following this through, the argument in the
text leads to a modi�ed version of [��C.��–���]
kT ‡
k r,1st = κ K
h
 �e activation energy is obtained from its usual de�nition, [��D.�–���]
d ln k r,1st d kT ‡
E a = RT 2 = RT 2 ln �κ K �
dT dT h
� 1 d ln K �
‡
= RT 2
+
�T dT �
1 ∆‡ H
= RT 2 � + � = RT + ∆‡ H
T RT 2

where to go to the last line the equivalent of d ln K�dT = ∆ r H −○ �RT 2 is used.

�e expression for k r,1st is then written in terms of ∆‡ G, ∆‡ H, and ∆‡ S
kT ‡ kT −∆‡ G�RT
k r,1st = κ K =κ e
h h
kT ∆‡ S�R −∆‡ H�RT kT ∆‡ S�R
=κ e e = �κ e e� e−E a �RT
h h
where to go to the �nal expression ∆‡ H = E a − RT is used. �e quantity in the
bracket is identi�ed as the frequency factor A.
From the graph E a = 86.3... kJ mol−1 , therefore
∆‡ H = E a − RT = (86.3... × 103 kJ mol−1 ) − (8.3145 J K−1 mol−1 ) × (253 K)
= +84.2... kJ mol−1 = +84.2 kJ mol−1
Assuming κ = 1
kT ∆‡ S�R
A= e e
h
Ah
hence ∆‡ S = R ln
kTe
(1.526 × 1014 s−1 ) × (6.6261 × 10−34 J s)
= (8.3145 J K−1 mol−1 ) ln
(1.3806 × 10−23 J K−1 ) × (253 K) × e
= +19.6... J K−1 mol−1 = +19.7 J K−1 mol−1

∆‡ G is found by combining the values of ∆‡ H and ∆‡ S in the usual way

∆‡ G = ∆‡ H − T∆‡ S
= (+84.2... × 103 J mol−1 ) − (253 K) × (+19.6... J K−1 mol−1 )
= +��.� kJ mol−1

P��C.� �e suggested starting point, [��C.�–���], is an expression for the equilibrium

constant for the formation of the activated complex in terms of the partition
functions
N A q −○ ‡
K = −○ −C○ e−∆E 0 �RT
‡
qA qB
 For reactions with the same activation energy their relative rate constants will
depend only on the ratio of partition functions, so attention is focused on this
quantity. To simplify the notation, the overline, double dagger and standard
symbols will be omitted. �e translational contribution to the partition func-
tion is written q T , and the rotational contribution is written q R for each degree
of rotational freedom; similarly, the vibrational contribution is written q V for
each normal mode.
For the reaction between atoms, the reactants only have translational contribu-
tions, but the activated complex has both translational and rotational contribu-
tions (two rotational degrees of freedom as the species is linear). �ere is no
vibrational contribution because the only vibration corresponds to the reaction
coordinate.
qC q T × (q R )2 (q R )2
� � = =
qA qB atom qT × qT qT
If the reactant A is non-linear and has N atoms it has three rotational degrees of
freedom and 3N −6 normal modes; similar considerations apply to B which has
N ′ atoms. �e activated complex also has three rotational degrees of freedom
and N act = 3(N + N ′ )−5 normal modes, the one corresponding to the reaction
coordinate being omitted.
qC q T × (q R )3 × (q V ) N act
� � = T
qA qB mol q × (q R )3 × (q V )3N−6 × q T × (q R )3 × (q V )3N ′ −6
(q V )7
=
q T × (q R )3
where to go to the last line the calculation [3(N +N ′ )−5]−(3N −6)−(3N ′ −6) =
7 is used.
�e ratio of the rates for the molecular and atomic reactants is therefore
k r,mol (q V )7 qT (q V )7 (1)7
= T = R 5 = = 3 × 10−8
k r,atom q × (q ) (q )
R 3 R 2 (q ) (101.5 )5
�e reaction with molecules is indeed very much slower.

P��C.� �e variation of the rate constant with ionic strength is given by [��C.��–���],
lg k r = lg k r○ +2Az A z B I 1�2 ; at ��� K and for aqueous solutions A = 0.509. A plot
of lg k r against I 1�2 is used to explore whether or not this relationship applies;
for the solution given I = 3[Na2 SO4 ]�mol kg−1 .

[Na2 SO4 ]�mol kg−1 I 1�2 k r �(dm3�2 mol−1�2 s−1 ) lg[k r �(dm3�2 mol−1�2 s−1 )]
0.2 0.775 0.462 −0.335
0.15 0.671 0.430 −0.367
0.1 0.548 0.390 −0.409
0.05 0.387 0.321 −0.493
0.025 0.274 0.283 −0.548
0.012 5 0.194 0.252 −0.599
0.005 0.122 0.224 −0.650
 lg[k r �(dm3�2 mol−1�2 s−1 )]
−0.4

−0.5

−0.6

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

1�2
I

�e plot is shown in Fig ��.�: it is evident that the data do not fall on a straight
line. �is is perhaps not surprising as the ionic strengths used are considerably
in excess of those for which the Debye–Hückel limiting law is expected to apply.
�e three data points at lowest ionic strength do fall on a good line, as is shown
in the plot, and these have a slope of +0.67. Such a value implies

2 × (0.509) × (z A z B ) = +0.67 hence (z A z B ) = +0.658

�is result makes no sense in terms of the theory, so little can be deduced other
than the fact that the two species have charges with the same sign.

P��C.� �e variation of the rate constant with ionic strength is given by [��C.��–���],
lg k r = lg k r○ +2Az A z B I 1�2 ; at ��� K and for aqueous solutions A = 0.509. A plot
of lg k r against I 1�2 is used to explore whether or not this relationship applies.

I I 1�2 k r �(dm3 mol−1 s−1 ) lg[k r �(dm3 mol−1 s−1 )]

0.002 5 0.050 0 1.05 0.021
0.003 7 0.060 8 1.12 0.049
0.004 5 0.067 1 1.16 0.064
0.006 5 0.080 6 1.18 0.072
0.008 5 0.092 2 1.26 0.100

�e plot is shown in Fig ��.�; the data do not fall on a straight line. �e limiting
slope, taken from the �rst three points, is +2.54. Such a value implies

2 × (0.509) × (z A z B ) = +2.54 hence (z A z B ) = +2.5

�is result implies that both ions have charges with the same sign, and if one
has charge � the other may have a charge of � or �.
 0.10

lg[k r �(dm3 mol−1 s−1 )]

0.08

0.06

0.04

0.02
0.04 0.05 0.06 0.07 0.08 0.09 0.10
1�2
I

P��C.�� �e equilibrium constant for the dissociation of the weak acid HA according to
HA ��� ⇀ H+ + A – is written in terms of activities, and then in terms of activity
coe�cients and concentrations; it is assumed that the activity coe�cient for the
neutral species is unity.

a H+ a A− γ H+ [H+ ]γ A− [A− ] γ±2 [H+ ][A− ]

Ka = = =
a HA γ HA [HA]c −○ [HA]c −○

Taking logarithms gives

[A− ]
lg K a = lg[H+ ] + 2 lg γ± + lg
[HA]c −○

Inserting the Debye–Hückel limiting law, lg γ± = −A�z+ z− �I 1�2 , and taking z+ =

+1 and z− = −1, gives

[A− ]
lg K a = lg[H+ ] − 2AI 1�2 + lg
[HA]c −○
[A− ]
hence lg[H+ ] = lg K a − lg + 2AI 1�2
[HA]c −○

�e rate is written r = k r [H+ ][B], hence

lg r = lg(k r [B]) + lg[H+ ]

[A− ]
= lg(k r [B]) + lg K a − lg + 2AI 1�2
[HA]c −○
k r K a [B][HA]c −○
= lg + 2AI 1�2
[A− ]

�e prediction is that the log of the rate will go as I 1�2 .

D��D.� �e saddle point on the potential energy surface corresponds to the transition
state of a reaction. �e saddle-point energy is the minimum energy required
for reaction; it is the minimum energy for a path on the potential energy sur-
face that leads from reactants to products. Because many paths on the surface
between reactants and products do not pass through the saddle point, they
necessarily pass through points of greater energy, so the activation energy can
be greater than the saddle-point energy. �us, the saddle-point energy is a
lower limit to the activation energy.

D��D.� Molecular beams may be used to prepare molecules in speci�c rotational and
vibrational states, and then to examine the results of collisions between such
precisely prepared species. Section ��D.�(a) on page ��� describes how molec-
ular beams are prepared such that the molecules in them have a very nar-
row range of velocities and therefore relatively few collisions to redistribute
their energies. Molecules in such beams can be prepared in speci�c vibrational
states, for example, by using lasers to excite vibrations. Crossing two molecular
beams allows collisions to be staged between two sets of precisely characterized
molecules. Detectors can then be used to study the results of those collisions,
recording the number of molecules in which particular states that are scattered
in a given direction.

E��D.�(b) Refer to Fig. ��D.�� on page ���, which shows a repulsive potential energy sur-
face as well as trajectories of both a successful reaction and an unsuccessful one.

trajectory passes through the transition state (marked as ‡ ○). �e unsuccessful

�e trajectories begin in the lower right, representing reactants. �e successful

trajectory is fairly straight from the lower right through the transition state,
indicating little or no vibrational excitation in the reactant. �erefore most of
its energy is in translation. �is trajectory runs up a steep portion of the surface
and rolls back down the valley representing the reactant. Without vibrational
energy, it cannot go around the corner to the transition state.
In contrast, the successful trajectory is able to turn the corner only because
it has a substantial amount of energy in vibration, which is represented by
side to side motion in the valley representing reactants. �at is, the reactant
is relatively high in vibrational energy. Once this successful trajectory passes
through the transition state, it follows a straight course into the valley rep-
resenting products, so the product is high in translational energy and low in
vibrational energy.

E��D.�(b) �e numerator of [��D.�–���] is integrated with the assumption that P(E) = 1

for E < V , and zero otherwise. E�ectively this means computing the integral
 over the range E = 0 to E = V with P(E) = 1
∞ V
� P(E) e−E�k T dE = � e−E�k T dE
0 0

= −kT e−E�k T �0
V

= −kT(e−V �k T − 1) = kT(1 − e−V �k T )

When kT � V the exponential term goes to zero, leaving a linear dependence
on T. When kT � V the exponential is expanded as (1 − V �kT), which leads
to a result independent of T.

P��D.� �e change in intensity of the beam, dI, is proportional to the number of scat-
terers per unit volume, N , the intensity of the beam, I, and the path length dL.
�e constant of proportionality is the collision cross-section σ, the ‘target area’
of each scatterer.
1
dI = −σN I dL hence dI = −σN dL hence d ln I = −σN dL
I
If the incident intensity at L = 0 is I 0 , and the intensity a�er scattering through
length L is I, integration gives
I L
� d ln I = � −σN dL hence ln I�I 0 = −σN L
I0 0

For scattering by CH� F� I�I 0 = 0.60, whereas for scattering over the same
length by Ar I�I 0 = 0.90 at the same pressure. �e ratio of the logarithms
of these fractions is the ratio of the collision cross sections.
ln 0.60 σCH2 F2
= = �.�
ln 0.90 σAr
�e very polar species CsCl is scattered more strongly by the polar CH� F� than
by atomic Ar.

P��D.� For a collinear approach the potential energy surface is described in terms of
that for HOD, the H–O distance RH–O , and the D–O distance RD–O . When the
H–O distance is large the variation of the potential energy is essentially that
of an isolated OD molecule with RD–O . When the D–O distance is large the
variation of the potential energy is essentially that of an isolated OH molecule
with the distance RH–O .

D��E.� Electron tunnelling plays an important role in electron transfer. As is discussed

in Section �D.� on page ���, it is expected that tunnelling will be more impor-
tant for electrons than any other particles that participate in chemical reactions
 because electrons are so much lighter than atoms or ions. Tunnelling is respon-
sible for the exponential distance dependence of the factor H et (d)2 , given by
[��E.�–���], and the electron-transfer rate constant, given by [��E.�–���], is
directly proportional to H et (d)2 . A full discussion is found in Section ��E.� on
page ���.

E��E.�(b) �e distance dependence of H et (d)2 given by [��E.�–���], H et (d)2 = H et

○2 −βd
e .

H et (d 2 )2
= e−β(d 2 −d 1 )
H et (d 1 )2
= e−(30 nm = 9.35... × 10−14
−1
)[(2.0 nm)−(1.0 nm)]

Increasing the distance from �.� nm to �.� nm reduces H et (d)2 by �� orders

of magnitude.

E��E.�(b) �e rate constant for electron-transfer is given by [��E.�–���] together with

[��E.�–���]

(∆ r G −○ + ∆E R )2
1�2
1 π3
k et = � � H et (d)2 e−∆ G�RT ∆‡ G =
‡

h RT∆E R 4∆E R

For the two reactions given, ∆E R and H et (d)2 are assumed to be the same,
therefore

k et,2
= e−(∆ G 2 −∆ G 1 )�RT ln k et,2 �k et,1 = −(∆‡ G 2 − ∆‡ G 1 )�RT
‡ ‡
hence
k et,1

�e term (∆‡ G 2 − ∆‡ G 1 )�RT is then developed as

∆‡ G 2 − ∆‡ G 1 (∆ r G 2−○ + ∆E R )2 − (∆ r G 1−○ + ∆E R )2
=
RT 4∆E R RT
(∆ r G 2 ) − (∆ r G 1−○ )2 + 2∆E R (∆ r G 2−○ − ∆ r G 1−○ )
−○ 2
=
4∆E R RT
1 (∆ r G 2 ) − (∆ r G 1−○ )2
−
○ 2
= � + 2(∆ r G 2−○ − ∆ r G 1−○ )�
4RT ∆E R

Putting this with the expression for ln k r,2 �k r,1 gives

−1 (∆ r G 2−○ )2 − (∆ r G 1−○ )2
ln k et,2 �k et,1 = � + 2(∆ r G 2−○ − ∆ r G 1−○ )�
4RT ∆E R
�is expression is then rearranged for ∆E R

(∆ r G 2−○ )2 − (∆ r G 1−○ )2
−4RT ln k et,2 �k et,1 − 2(∆ r G 2−○ − ∆ r G 1−○ ) =
∆E R
(∆ r G 2−○ )2 − (∆ r G 1−○ )2
∆E R =
−4RT ln k et,2 �k et,1 − 2(∆ r G 2−○ − ∆ r G 1−○ )
(∆ r G 1−○ )2 − (∆ r G 2−○ )2
∆E R =
4RT ln k et,2 �k et,1 + 2(∆ r G 2−○ − ∆ r G 1−○ )

�e data are given in eV so it is convenient to express 4RT in eV with the help

of the conversion factors inside the front cover
1 eV
4RT = 4×(8.3145 J K−1 mol−1 )×(298 K)× = 0.102... eV
96.485 × 103 J mol−1
With the data given

(∆ r G 1−○ )2 − (∆ r G 2−○ )2
∆E R =
4RT ln k et,2 �k et,1 + 2(∆ r G 2−○ − ∆ r G 1−○ )
(−0.665 eV)2 − (−0.975 eV)2
=
(0.102... eV) × ln (3.33×10 s−1 )
+ 2[(−0.975 eV) − (−0.665 eV)]
6

(2.02×10 5 s−1 )

= 1.53... eV = �.�� eV

Using the data for the �rst value of the rate constant

(∆ r G −○ + ∆E R )2 [(−0.665 eV) + (1.53... eV)]2

∆‡ G = = = 0.122... eV
4∆E R 4 × (1.53... eV)

�e expression for k r given by [��E.�–���] is then rearranged to �nd H et (d)2

RT∆E R 1�2 ∆‡ G�RT

H et (d)2 = hk et � � e
π3

As the values of ∆E R and ∆‡ G have already been found in eV, it is convenient

to express the term RT also in eV; following the same process as above gives
RT = 0.0256... eV.

H et (d)2 = (6.6261 × 10−34 J s) × (2.02 × 105 s−1 )

(0.0256... eV) × (1.53... eV)
1�2
� � e(0.122 ... eV)�(0.0256 ... eV)
π3
= 5.59... × 10−28 J eV = 8.97... × 10−47 J2

On the �nal line the units are converted using 1 eV = 1.6021 × 10−19 J. Hence
H et (d) = 9.47 × 10−24 J .
E��E.�(b) �e rate constant for electron-transfer is given by [��E.�–���] together with
[��E.�–���]

(∆ r G −○ + ∆E R )2
1�2
1 π3
k et = � � H et (d)2 e−∆ G�RT ∆‡ G =
‡

h RT∆E R 4∆E R

For the two reactions given, ∆E R and ∆‡ G are assumed to be the same. �e
distance dependence of H et (d)2 is given by [��E.�–���], H et (d)2 = H et
○2 −βd
e ,
therefore
k et,2 (H et (d)2 )2
= = e−β(d 2 −d 1 )
k et,1 (H et (d)2 )1
hence ln(k et,2 �k et,1 ) = −β(d 2 − d 1 )
ln(k et,2 �k et,1 )
therefore β = −
(d 2 − d 1 )
ln[(4.51 × 104 s−1 )�(2.02 × 105 s−1 )]
β=− = 12.5... nm−1
(1.23 nm) − (1.11 nm)
�e rate constant for d 3 = 1.59 nm is then found using the result above

k et,3 = k et,1 e−β(d 3 −d 1 )

= (2.02 × 105 s−1 ) × e−(12.5 ... nm
−1
)×[(1.59 nm)−(1.11 nm)]

= ��� s−1

P��E.� Using the Marcus cross-relation, and assuming f = 1, the rate constant may be
expressed k r = (k AA k DD K)1�2 , where in this case A is the Ru�+ complex and
D is the Fe�+ complex. �e equilibrium constant K for the overall reaction is
found from the standard potentials. Subtracting the second half-cell reaction
from the �rst gives (omitting the ligands for brevity)

Ru�+ + Fe�+ ��→ Ru�+ + Fe�+ E −○ = +1.26 V − (+0.77 V) = +0.49 V

In this reaction one electron is involved, therefore the standard Gibbs energy
change is given by [�C.�–���], ∆ r G −○ = −FE −○ , and the equilibrium constant by
∆ r G −○ = −RT ln K, hence
K = e−∆ r G = eF E
−
○ −
○
�RT �RT

= e(96485 C mol
−1
)×(+0.49 V)�[(8.3145 J K−1 mol−1 )×(298 K)]

= 1.93 . . . × 108
�e rate constant for the overall process is therefore
k r = (k AA k DD K)1�2
= [(4.0 × 108 dm3 mol−1 s−1 ) × (4.2 dm3 mol−1 s−1 ) × (1.93 . . . × 108 )]1�2
= 5.7 × 108 dm3 mol−1 s−1
P��E.� �e variation of the electron-transfer rate constant with ∆ r G −○ is given by [��E.�–
���]
∆ r G −○ ∆ r G −○
2
RT
ln k et = − � � − 12 � � + const.
4∆E R RT RT
A plot of ln k et against −∆ r G −○ is expected to be an inverted parabola and, as
described in the text, the maximum occurs at −∆ r G −○ = ∆E R . �e plot is shown
in Fig ��.�.

−∆ r G −○ �eV k et �(106 s−1 ) lg[k et �(106 s−1 )]

0.665 0.657 −0.182
0.705 1.52 0.182
0.745 1.12 0.049
0.975 8.99 0.954
1.015 5.76 0.760
1.055 10.1 1.004

1.0
lg[k et �(106 s−1 )]

0.5

0.0

0.6 0.7 0.8 0.9 1.0 1.1 1.2

−∆ r G �eV
−
○

�e data are rather poor �t to the second-order polynomial

lg[k et �(106 s−1 )] = −3.682 × (−∆ r G −○ �eV)2 + 9.157 × (−∆ r G −○ �eV) − 4.5983
which is shown on the plot. �e maximum of this function occurs when the
derivative is zero, that is when 2×−3.682×(−∆ r G −○ �eV)+9.157 = 0; this occurs
at (−∆ r G −○ �eV) = 1.24.... �erefore ∆E R = 1.2 eV .

P��E.� �e theoretical treatment given in the text applies only at relatively high tem-
peratures. At temperatures above ��� K, the reaction in question is observed to
follow a temperature dependence consistent with [��E.�–���], namely increas-
ing rate with increasing temperature. Below ��� K, the temperature dependent
terms in the equation are replaced by Franck–Condon factors (Topic ��F); that
is, temperature-dependent terms are replaced by temperature-independent wave-
function overlap integrals.
I��.� Typical orders of magnitudes are qmT �N A ≈ 107 , q R ≈ 10 per rotational degree of
freedom, q V ≈ 1 per vibrational degree of freedom, and q E ≈ 1. Vibrational and
electronic contributions will therefore be ignored from now on. According to
transition-state theory the rate constant is given by ([��C.��–���] and [��C.�–
���])
kT RT N A qC−○‡ −∆E 0 �RT
kr = κ e
h p−○ qC−○ qB−○
At ��� K the factors in from the the ratio of partition functions evaluate to
1.5 × 1011 m3 mol−1 s−1 , assuming κ = 1.
For a reaction between structureless particles A, B, and C‡ all have contribu-
tions from translation; in addition, C‡ has two rotational degrees of freedom,
therefore
N A × qmT × (q R )2 −∆E 0 �RT
k r = (1.5 × 1011 m3 mol−1 s−1 ) × e
qmT × qmT
(q R )2 −∆E 0 �RT
= (1.5 × 1011 m3 mol−1 s−1 ) × e
qmT �N A
(10)2
= (1.5 × 1011 m3 mol−1 s−1 ) ×
107
= (1.5 × 106 m3 mol−1 s−1 ) × e−∆E 0 �RT

In collision theory the rate constant is given by [��A.�–���]

1�2
8kT
kr = σ NA � � e−E a �RT
πµ
For a typical value σ = 0.4 nm2 and a mass of 2 × 10−26 kg, at ��� K

k r = (1.7 × 108 m3 mol−1 s−1 ) × e−E a �RT

Assuming that E a ≈ ∆E 0 , collision theory gives a rate constant greater by about
a factor of ���, implying a steric factor of about �.��; this is a plausible result.
If A and B are non-linear triatomics, then A, B and C‡ all have three rotational
degrees of freedom
N A × qmT × (q R )3
k r = (1.5 × 1011 m3 mol−1 s−1 ) × e−∆E 0 �RT
qmT × (q R )3 × qmT × (q R )3
1
= (1.5 × 1011 m3 mol−1 s−1 ) × R 3 e−∆E 0 �RT
(q ) × qmT �N A
1
= (1.5 × 1011 m3 mol−1 s−1 ) ×
(10)3 × 107
= (15 m3 mol−1 s−1 ) × e−∆E 0 �RT
�e steric factor is now 9 × 10−8 – very much smaller than for the reaction
between structureless particles.
D��A.� �e Auger e�ect is described in Section ��A.�(b) on page ���. In Auger electron
spectroscopy the electron beam is only able to a�ect species on the surface
and perhaps a few layers into the bulk, and therefore the emitted electrons are
characteristic of the surface and the species adsorbed onto it. �e energies of
the emitted electrons are characteristic of the material present and so provide
a �ngerprint of the sample.
In scanning Auger microscopy (SAM) the electron beam is narrowly focused so
that electrons are excited only from a small region (of dimension about �� nm).
By scanning the beam across the sample it is possible to build up a map of the
composition.
In scanning tunnelling microscopy (STM) a topological map of the surface is
built up, and under favourable circumstances individual atoms may be identi-
�ed; the resolution is thus much greater than that achieved in SAM. However,
STM gives no clues as to the identity of the atoms on the surface, in contrast to
SAM.

E��A.�(b) �e collision �ux, Z w , is given by [��A.�–���], Z w = p�(2πMkT�N A )1�2 where

p is the pressure of gas, M is the molar mass of the molecule, k is Boltzmann’s
constant, T is the temperature and N A is Avogadro’s constant. From inside the
front cover, 760 Torr = 1 atm = 1.01325 × 105 Pa, therefore 1 Torr is 133.32 Pa.

(i) For a nitrogen molecule, the molar mass M = 2 × (14.01 g mol−1 ) =

28.02 g mol−1 , therefore for p = 10.0 Pa

p
Zw =
(2πMkT�N A )1�2
(10.0 Pa)×(6.0221 × 1023 mol−1 )1�2
=
�2π×(28.02 × 10−3 kg mol−1 )×(1.3806 × 10−23 J K−1 )×(298.15 K)�
1�2

= 2.88... × 1023 m−2 s−1 = 2.88 × 1019 cm−2 s−1

 For p = 0.150 µTorr
p
Zw =
(2πMkT�N A )1�2
(0.150 × 10−6 Torr)×(133.32 Pa Torr−1 )×(6.0221 × 1023 mol−1 )1�2
=
�2π×(28.02 × 10−3 kg mol−1 )×(1.3806 × 10−23 J K−1 )×(298.15 K)�
1�2

= 5.76... × 1017 m−2 s−1 = 5.76 × 1013 cm−2 s−1

(ii) For methane, the molar mass M = (12.011 g mol−1 )+4×(1.0079 g mol−1 ) =
16.043 g mol−1 , therefore for p = 10.0 Pa
p
Zw =
(2πMkT�N A )1�2
(10.0 Pa)×(6.0221 × 1023 mol−1 )1�2
=
�2π×(16.043 × 10−3 kg mol−1 )×(1.3806 × 10−23 J K−1 )×(298.15 K)�
1�2

= 3.80... × 1023 m−2 s−1 = 3.81 × 1019 cm−2 s−1

For p = 0.150 µTorr,

p
Zw =
(2πMkT�N A )1�2
(0.150 × 10−6 Torr)×(133.32 Pa Torr−1 )×(6.0221 × 1023 mol−1 )1�2
=
�2π×(16.043 × 10−3 kg mol−1 )×(1.3806 × 10−23 J K−1 )×(298.15 K)�
1�2

= 7.61... × 1017 m−2 s−1 = 7.62 × 1013 cm−2 s−1

E��A.�(b) �e collision �ux, Z w , is given by [��A.�–���], Z w = p�(2πMkT�N A )1�2 where

p is the pressure of gas, M is the molar mass of the molecule, k is Boltzmann’s
constant, T is the temperature and N A is Avogadro’s constant.
�e collision rate, z, is given by z = AZ w where A is the surface area. Hence,
Ap
z = AZ w =
(2πMkT�N A )1�2

For N� the molar mass M = 2 × (14.01 g mol−1 ) = 28.02 g mol−1 . �us, for
A = π(d�2)2 , where d is the diameter of the circular surface, rearranging the
above expression gives

r(2πMkT�N A )1�2
p=
A
5.00 × 1019 s−1
=
π×(0.5 × 2.0 × 10−3 m)2
2π×(28.02 × 10−3 kg mol−1 )×(1.3806 × 10−23 J K−1 )×(525 K)
1�2
� �
6.0221 × 1023 mol−1
= 7.3 × 102 Pa
E��A.�(b) For a perfect gas, and at constant temperature, p ∝ 1�V , where V is the volume
occupied by the gas at pressure p. �erefore

p 2 V1 V1 p 1
= hence V2 =
p 1 V2 p2

�e surface coverage θ is given by θ = V �V∞ where V is the volume of gas

adsorbed at a particular pressure p and V∞ is the volume of gas which gives
a complete monolayer, but where the volume has been corrected to the same
pressure p.
At 5.0 bar, the volume adsorbed is a complete monolayer and thus V∞ = 6.6 cm3
at 5.0 bar. At 0.30 bar, this same volume is

(6.6 cm3 ) × (5.0 bar)

V∞,0.3 bar = = 110 cm3
0.3 bar
Hence the surface coverage is

11 cm3
θ= = 0.1
110 cm3

E��A.�(b) For a process to be spontaneous it must be accompanied by a reduction in

the Gibbs energy, that is ∆G < 0, where ∆G = ∆H − T∆S. If adsorption is
endothermic, ∆H > 0, but nevertheless observed to be spontaneous, it must
be that ∆S > 0. �is is unusual for adsorption of a gas because such a process
involves the loss of translational degrees of freedom. However, if the adsorbed
molecule dissociates on binding it is possible for the entropy to increase, ∆S >
0.

P��A.� �e collision �ux, Z w , is given by [��A.�–���], Z w = p�(2πMkT�N A )1�2 where

p is the pressure of gas, M is the molar mass of the molecule, k is Boltzmann’s
constant, T is the temperature and N A is Avogadro’s constant.

(a) For an oxygen molecule, the molar mass M = 2 × (16.00 g mol−1 ) =

32.00 g mol−1 , therefore at T = 300 K and p = 100 kPa,
p
Zw =
(2πMkT�N A )1�2
(100 × 103 Pa)×(6.0221 × 1023 mol−1 )1�2
=
�2π×(32.00 × 10−3 kg mol−1 )×(1.3806 × 10−23 J K−1 )×(300 K)�
1�2

= 2.68... × 1027 m−2 s−1 = 2.69 × 1023 cm−2 s−1

(b) At p = 1.00 Pa the collision rate is reduced by a factor of 105 compared to

(a): Z w = 2.69 × 1018 cm−2 s−1
 Assume that on the surface the atoms are centred on a square grid of side a 0 ,
the lattice spacing, with the atoms in contact (a face of a simple cubic lattice). It
follows that the radius of each atom is half the lattice spacing r = a 0 �2. Hence,
the area, A, of a single surface atom is approximated by A = πr 2 = π( 12 a 0 )2 =
1
4
πa 02 .
For p = 100 kPa, the number of collisions made with a single surface atom in
each second by oxygen is

n col = AZ w ∆t = 14 πZ w a 02 ∆t
= 41 π × (2.68... × 1027 m−2 s−1 ) × (291 × 10−12 m)2 × (1 s) = 1.79 × 108

For p = 1.00 Pa, the number of collisions is reduced by a factor of 105 compared
to the calculation just made: AZ w = 1.79 × 103 .

P��A.� Using Bragg’s law, λ = 2d sin θ, it is observed that for a given wavelength,
the greater the separation d of atomic layers within a lattice, the smaller the
scattering angle θ.�erefore, in terms of the LEED pattern, the farther apart
the atoms responsible for the pattern, the closer the spots appear in the LEED
pattern.
�erefore, tripling the horizontal separation between the atoms corresponds
to the spot separation reducing to a third of the original separation between
the spots. �e vertical separation between atoms is unchanged, therefore the
vertical separation of LEED spots in that dimension remains unchanged. �e
result is shown in Fig. ��.�.

Original LEED pattern Reconstruction LEED pattern

D��B.� �e assumptions made in deriving the Langmuir isotherm are:

 (�) Adsorption cannot proceed beyond monolayer coverage.
(�) All sites are equivalent and the surface is uniform.
(�) �e ability of a molecule to adsorb at a given site is independent of the
occupation of neighbouring sites.
For the BET isotherm assumption (�) is removed so that multi-layer coverage
is possible. In the derivation of this isotherm a distinction is made between the
energetics involved in forming the �rst and subsequent layers.

E��B.�(b) �ere is an error in the Exercise: the volume at the lower pressure should be
1.52 cm3 .
�e Langmuir isotherm is [��B.�–���], θ = α p�(1 + α p), with α = k a �k d . �e
surface coverage may be written in terms of the volume of gas adsorbed V ,
θ = V �V∞ , where V∞ is the volume corresponding to complete coverage. For
two di�erent pressures
V1 α p1 V2 α p2
= =
V∞ 1 + α p 1 V∞ 1 + α p 2

Inverting both sides

V∞ 1 V∞ 1
= +1 = +1
V1 α p1 V2 α p2

To eliminate α �rst multiply the le�-hand equation by 1�p 2 and the right-hand
equation by 1�p 1

V∞ 1 1 V∞ 1 1
= + = +
p 2 V1 α p 1 p 2 p 2 p 1 V2 α p 1 p 2 p 1

Subtracting the two equations gives then eliminates α

V∞ V∞ 1 1
− = −
p 2 V1 p 1 V2 p 2 p 1
1�p 2 − 1�p 1 p1 − p2
hence V∞ = =
1�p 2 V1 − 1�p 1 V2 p 1 �V1 − p 2 �V2

where for the last step top and bottom are multiplied by p 1 p 2 .
With the data given
p1 − p2
V∞ =
p 1 �V1 − p 2 �V2
(56.4 kPa) − (108 kPa)
= = 27.4 cm3
(56.4 kPa)�(1.52 cm3 ) − (108 kPa)�(2.77 cm3 )
E��B.�(b) �e residence half-life is given by [��B.��–���], t 1�2 = τ 0 eE a,des �RT . �e acti-
vation energy for desorption, E a,des , is approximated as minus the enthalpy of
adsorption.

t 1�2 = (1.0 × 10−14 s) e(155×10 J mol−1 )�[(8.3145 J K−1 mol−1 )×(500 K)]
3

= 1.6 × 102 s

E��B.�(b) �e Langmuir isotherm is [��B.�–���], θ = α p�(1 + α p). �e surface coverage

may be written in terms of the volume of gas adsorbed V , θ = V �V∞ , where
V∞ is the volume corresponding to complete coverage. Equivalently, θ may be
expressed in terms of the mass adsorbed, θ = m�m∞ , where m∞ is the mass
corresponding to complete coverage. For two di�erent pressures
m1 α p1 m2 α p2
= =
m∞ 1 + α p 1 m∞ 1 + α p 2
�e aim is to �nd m∞ , and the algebra to do this is just the same as the method
for �nding V∞ in Exercise E��B.�(b) with volumes replaced by masses. �e
result is
p1 − p2
m∞ =
p 1 �m 1 − p 2 �m 2
(36.0 kPa) − (4.0 kPa)
= = 0.84 mg
(36.0 kPa)�(0.63 mg) − (4.0 kPa)�(0.21 mg)
�e surface coverage at the �rst pressure is therefore
m1 0.63 mg
θ1 = = = 0.75
m∞ 0.84 mg

At the second pressure θ 2 = (0.21 mg)�(0.84 mg) = 0.25 .

E��B.�(b) �e Langmuir isotherm is [��B.�–���], θ = α p�(1 + α p), inverting both sides

gives

1 1 1 1 1−θ
= +1 hence = −1=
θ αp αp θ θ

Inverting again gives

θ θ
αp = hence p=
1−θ α(1 − θ)
With the data given
0.20
p= −1 = 0.46 kPa
(0.548 kPa ) × (1 − 0.20)

A similar calculation for θ = 0.75 gives 5.5 kPa .

E��B.�(b) �e isosteric enthalpy of adsorption is de�ne as [��B.�b–���]

∂ ln(α p−○ ) ∆ ad H −○
� � =−
∂(1�T) θ R

From the Langmuir isotherm is follows that α = θ�p(1 − θ) but, because an

isosteric process is being considered (θ is constant), this reduces to α = C�p,
where C is a constant. With just two sets of data the derivative is approximated
as the �nite interval to give
ln(C p−○ �p 2 ) − ln(C p−○ �p 1 ) ∆ ad H −○
=−
(1�T2 ) − (1�T1 ) R
∆ ad H −○ 1 1
hence ln p 1 �p 2 = − � − �
R T2 T1
∆ ad H −○ 1 1
hence ln p 2 = ln p 1 + � − �
R T2 T1

�e data gives the enthalpy of desorption as +12.2 J for 1.00 mmol of gas,
therefore the molar enthalpy of adsorption is −12.2 kJ mol−1 .

−12.2 kJ mol−1 1 1
ln (p 2 �kPa) = ln(8.86 kPa) + −1 −1 � − � = 2.49...
8.3145 J K mol 318 K 298 K

�erefore (p 2 �kPa) = e2.49 ... , giving p 2 = 12.1 kPa .

E��B.�(b) �e isosteric enthalpy of adsorption is de�ne as [��B.�b–���]

∂ ln(α p−○ ) ∆ ad H −○
� � =−
∂(1�T) θ R

From the Langmuir isotherm is follows that α = θ�p(1 − θ) but, because an

isosteric process is being considered (θ is constant), this reduces to α = C�p,
where C is a constant. With just two sets of data the derivative is approximated
as the �nite interval to give
ln(C p−○ �p 2 ) − ln(C p−○ �p 1 ) ∆ ad H −○
=−
(1�T2 ) − (1�T1 ) R
∆ ad H −○ 1 1
hence ln(p 1 �p 2 ) = − � − �
R T2 T1
R ln(p 2 �p 1 )
hence ∆ ad H −○ =
1�T2 − 1�T1
With the data given

(8.3145 J K−1 mol−1 ) × ln[(1.02 × 106 Pa)�(350 × 103 Pa)]

∆ ad H −○ =
1�(240 K) − 1�(180 K)
= −6.40 kJ mol−1
E��B.�(b) �e rate constant for desorption is assumed to follow an Arrhenius law, k des =
Ae−E a,des �RT . Recall that for a �rst order process the half life is simply propor-
tional to the inverse of the rate constant, therefore the time needed for a certain
amount to desorb is also inversely proportional to the rate constant. �us

τ 1 �τ 2 = e−(E a,des �R)(1�T2 −1�T1 )

E a,des 1 1
hence ln(τ 1 �τ 2 ) = − � − �
R T2 T1
−R ln(τ 1 �τ 2 )
hence E a,des =
(1�T2 − 1�T1 )
With the data given

−(8.3145 J K−1 mol−1 ) ln[(1856 s)�(8.44 s)]

E a,des =
1�(1012 K) − 1�(873 K)
= 2.85... × 105 J mol−1 = 285 kJ mol−1

�e times for desorption at di�erent temperatures are computed using

τ 1 �τ 2 = e−(E a,des �R)(1�T2 −1�T1 ) hence τ 2 = τ 1 e(E a,des �R)(1�T2 −1�T1 )

�e time needed at ��� K is related to that at ��� K

τ 2 = (1856 s) e[(2.85 ...×10 J mol−1 )�(8.3145 J K−1 mol−1 )][1�(298 K)−1�(873 K)]
5

= 1.5 × 1036 s

E�ectively, the gas does not desorb at this temperature. Repeating the calcula-
tion at ���� K

τ 2 = (1856 s) e[(2.85 ...×10 J mol−1 )�(8.3145 J K−1 mol−1 )][1�(1500 K)−1�(873 K)]
5

= 0.14 ms

E��B.�(b) �e average time that a species remains adsorbed is proportional to its half-life,
given by [��B.��–���], t 1�2 = τ 0 eE a,des �RT . �erefore, if the two times are τ 1 and
τ 2 at temperatures T1 and T2

τ 2 �τ 1 = e(E a,des �R)(1�T2 −1�T1 )

E a,des 1 1
hence ln(τ 2 �τ 1 ) = � − �
R T2 T1
R ln(τ 2 �τ 1 )
hence E a,des =
1�T2 − 1�T1
�e data gives the lifetime at the higher temperature as τ 2 = τ 1 (1 − 0.35) =
0.65 τ 1

(8.3145 J K−1 mol−1 ) ln[(0.65τ 1 )�(τ 1 )]

E a,des =
1�(1000 K) − 1�(600 K)
= 5.4 kJ mol−1
E��B.�(b) �e half-life for a species on the surface is given by [��B.��–���], t 1�2 = τ 0 eE a,des �RT .

(i) With E a,des = 20 kJ mol−1

at ��� K t 1�2 = (0.12 ps) e(20×10 J mol−1 )�[(8.3145 J K−1 mol−1 )×(298 K)]
3

= 3.8 × 102 ps
at ��� K t 1�2 = (0.12 ps) e(20×10 J mol−1 )�[(8.3145 J K−1 mol−1 )×(800 K)]
3

= 2.4 ps

(ii) With E a,des = 200 kJ mol−1

at ��� K t 1�2 = (0.12 ps) e(200×10 J mol−1 )�[(8.3145 J K−1 mol−1 )×(298 K)]
3

= 1.36... × 1034 ps = 1.4 × 1022 s

at ��� K t 1�2 = (0.12 ps) e(200×10 J mol−1 )�[(8.3145 J K−1 mol−1 )×(800 K)]
3

= 1.37... × 1012 ps = 1.4 s

P��B.� As is shown in Example ��B.� on page ���, a suitable plot to test the Langmuir
isotherm is of p�V against p; such a plot has intercept 1�αV∞ and slope 1�V∞ .
�e table of data is given below and the plot is shown in Fig. ��.�.

p�Pa V �cm3 (p�V )�(Pa cm−3 )

25 0.042 595
129 0.163 791
253 0.221 1 145
540 0.321 1 682
1 000 0.411 2 433
1 593 0.471 3 382

Omitting the data points for the two highest pressures gives a reasonable straight
line with equation
(p�V )�(Pa cm−3 ) = 2.135 × (p�Pa) + 547.9

V∞ is found from the slope as V∞ = 1�slope = 1�(2.135) cm3 = 0.47 cm3 .

�e value of α is found from (slope)/(intercept), α = (2.135)�(547.9) Pa−1 =
3.9 × 10−3 Pa−1 .

P��B.� Note: the volume data given in the Problem is in error. �e values in the table
should be, reading le� to right, 1.22 1.33 1.31 1.36 1.40 in cm3 .
As is shown in Example ��B.� on page ���, a suitable plot to �t data to the
Langmuir isotherm is of p�V against p; such a plot has intercept 1�αV∞ and
slope 1�V∞ . �e table of data is given below and the plot is shown in Fig. ��.�.
 3 000

(p�V )�(Pa cm−3 )

2 000

1 000

0 500 1 000 1 500

p�Pa

p�atm V �cm3 (p�V )�(atm cm−3 )

0.050 1.22 0.0410
0.100 1.33 0.0752
0.150 1.31 0.115
0.200 1.36 0.147
0.250 1.40 0.179
(p�V )�(atm cm−3 )

0.15

0.10

0.05

0.05 0.10 0.15 0.20 0.25

p�atm

�e data fall on a reasonable straight line with equation

(p�V )�(atm cm−3 ) = 0.6941 × (p�atm) + 7.147 × 10−3

V∞ is found from the slope as V∞ = 1�slope = 1�(0.6941) cm3 = 1.44 cm3 .

 �e number of H� molecules in this volume is found using the perfect gas law
N A pV
N=
RT
(6.0221 × 1023 mol−1 ) × (1.01325 × 105 Pa) × (1.44 × 10−6 m3 )
=
(8.3145 J K−1 mol−1 ) × (273.15 K)
= 3.86... × 1019

�e area of a molecule is estimated from the mass density of the liquid in the
following way. Consider a volume V of the liquid which has mass density ρ;
the mass of the liquid is V ρ and this corresponds to V ρ�M moles, where M
is the molar mass. �e number of molecules in the volume is N = N A V ρ�M,
therefore the volume occupied by one molecule is V �N = M�N A ρ.
If the molecule is considered to be a sphere of radius R, then 43 πR 3 = M�N A ρ,
from which it follows that R = (3M�4N A ρπ)1�3 . �erefore the area of the
‘silhouette’ of the sphere is A = πR 2 = π(3M�4N A ρπ)2�3 . With the data given

3 × (2.0158 g mol−1 )
2�3
A= π� �
4 × (6.0221 × 1023 mol−1 ) × (0.708 g cm−3 ) × π
= 3.40... × 10−16 cm2 = 3.40... × 10−20 m2

�e surface area is therefore (3.86... × 1019 ) × (3.40... × 10−20 m2 ) = 1.3 m2 .

P��B.� (a) As is shown in Example ��B.� on page ���, a suitable plot to �t data to the
Langmuir isotherm is of p�V against p; such a plot has intercept 1�αV∞
and slope 1�V∞ . �e table of data is given below and the plot is shown in
Fig. ��.�; it is clear from this that the data do not conform to the Langmuir
isotherm.
p�kPa V �cm3 (p�V )�(kPa cm−3 ) z y�(10−3 cm−3 )
13.3 17.9 0.743 0.067 3.980
26.7 33.0 0.809 0.134 4.669
40.0 47.0 0.851 0.200 5.319
53.3 60.8 0.877 0.267 5.976
66.7 75.3 0.886 0.334 6.645
80.0 91.3 0.876 0.400 7.302

(b) In [��B.�–���] the BET isotherm is manipulated into a straight-line plot

z 1 (c − 1)
= + z z = p�p∗
(1 − z)V cVmon cVmon

�us a plot of z�(1 − z)V against z is expected to be a straight line with

slope (c − 1)�cVmon and intercept 1�cVmon ; note that (slope)/(intercept)
= c − 1. For brevity the term z�(1 − z)V is denoted y. �e manipulated
data is shown in the table above and the plot is shown in Fig. ��.�.
 0.90

(p�V )�(kPa cm−3 )

0.85

0.80

0.75

0.70
20 40 60 80
p�kPa

7
y�(10−3 cm−3 )

0.0 0.1 0.2 0.3 0.4

z

�e data are a good �t to a straight line with equation

y�(10−3 cm−3 ) = 9.939 × (z) + 3.329

�e parameter c is found using

slope 9.939
= c−1 hence c =1+ = 3.99
intercept 3.329

�e intercept is 1�cVmon , therefore

1 1
Vmon = = = 75.3 cm3
c × (intercept) 3.99 × 10−3 × (3.329 cm−3 )

P��B.� Note: there is missing data from this Problem, which is that the two tempera-
tures referred to are ��� ○ C and ��� ○ C.
 �e isosteric enthalpy of adsorption is de�ned as [��B.�b–���]

∂ ln(α p−○ ) ∆ ad H −○
� � =−
∂(1�T) θ R

With just two sets of data the derivative is approximated as the �nite interval
to give

ln(α 2 p−○ ) − ln(α 1 p−○ ) ∆ ad H −○

=−
(1�T2 ) − (1�T1 ) R
∆ ad H −○ 1 1
hence ln α 2 �α 1 = − � − �
R T2 T1

With the data given

(−160 × 103 J mol−1 ) 1 1

ln α 2 �α 1 = − −1 −1 � − �
8.3145 J K mol 773 K 673 K
= −3.69...

�erefore α 2 �α 1 = e−3.69 ... = 0.0247 .

�e Freundlich isotherm is written c ads = Kc sol ; taking logarithms gives ln c ads

1�n
P��B.��
= ln K + (1�n) ln c sol . �is implies that a plot of ln c ads against ln c sol should be
a straight line of slope 1�n and intercept ln K. �e data are given below and the
plot is shown in Fig. ��.�.

c sol �(mg g−1 ) c ads �(mg g−1 ) ln[c sol �(mg g−1 )] ln[c ads �(mg g−1 )]
8.26 4.41 2.111 1.48
15.65 9.20 2.750 2.22
25.43 35.20 3.236 3.56
31.74 52.00 3.458 3.95
40.00 67.20 3.689 4.21

�e data fall on a modest straight line, the equation of which is

ln[c ads �(mg g−1 )] = 1.849 × ln[c sol �(mg g−1 )] − 2.554

�e slope is 1�n, therefore n = 1�slope = 1�(1.849) = 0.54 . �e intercept gives

ln K and hence K = 0.078 mg g−1 .
To compute the fractional coverage θ it would be necessary to know the mass
needed for a monolayer. �is is of no particular signi�cance for this isotherm.

P��B.�� �e Langmuir isotherm would be di�erent in the three cases.

(a) For adsorption without dissociation [��B.�–���], θ = α p�(1 + α p)
 4

ln[c ads �(mg g−1 )]

3

1
2.0 2.5 3.0 3.5 4.0
ln[c sol �(mg g )]
−1

(b) For adsorption with dissociation into two species the isotherm is [��B.�–
���], θ = (α p)1�2 �[1 + (α p)1�2 ]

(c) By extension, for adsorption with dissociation into three species the isotherm
is θ = (α p)1�3 �[1 + (α p)1�3 ]

A plot of θ against p at low pressures (where the denominator is approximately

�) would show progressively weaker dependence on p for dissociation into two
or three species.

D��C.� �e two relevant equations derived in How is that done? ��C.� on page ��� are

(α A p A + 1)θ A + α A p A θ B = α A p A α B p B θ A + (α B p B + 1)θ B = α B p B

�e �rst is multiplied by α B p B and the second by (α A p A + 1) to give

α B p B (α A p A + 1)θ A + α B p B α A p A θ B = α B p B α A p A
(α A p A + 1)α B p B θ A + (α A p A + 1)(α B p B + 1)θ B = (α A p A + 1)α B p B

�e terms in θ A are now the same, and so will disappear when the two equations
are subtracted to give

α B p B α A p A θ B − (α A p A + 1)(α B p B + 1)θ B = α B p B α A p A − (α A p A + 1)α B p B

 �e expression for θ B then follows with some rearrangement and simpli�cation

α B p B α A p A − (α A p A + 1)α B p B
θB =
α B p B α A p A − (α A p A + 1)(α B p B + 1)
−α B p B
=
αB pB αA pA − αA pA αB pB − αA pA − αB pB − 1
αB pB
=
αA pA + αB pB + 1

which is the required expression. �at for θ B is simply found by swapping the
indices A and B: the equations all remain valid under such a change.

E��C.�(b) �e amount in moles of CO gas is found using the perfect gas law.

pV (1 bar)×(105 Pa) 3.75 × 10−6 m3

n= = ×
RT 1 bar (8.3145 J K−1 mol−1 ) × (273.15 K)
= 1.65... × 10−4 mol

which corresponds to N A n = (6.0221 × 1023 mol−1 ) × (1.65 × 10−4 mol) =

9.94... × 1019 molecules.
A rough calculation of the surface area notes that the collision cross section
is σ = πd 2 , where d is the diameter of the colliding spheres. �erefore d =
(σ�π)1�2 , and hence r = 12 (σ�π)1�2 . �e area of one molecule is πr 2 = π 14 σ�π =
1
4
σ. In the tables, no value for the collision cross section of CO is given, so the
value for N� is used. �e surface area is therefore (9.94... × 1019 ) × 14 × (0.43 ×
10−18 m2 ) = 11 m2 .
In fact circles do not cover a plane completely, and it can be shown that the
highest coverage which can be achieved is one in which the circles cover �.��
of the area of the plane. �e estimate of the area therefore needs to be scaled
up by a factor of 1�0.91 ≈ 1.1 to give 12 m2 .

P��C.� �e rate law for a unimolecular decomposition occurring on a surface is given

by [��C.�–���]
kr α p
υ=
1 + αp
HI is adsorbed strongly on gold, implying that α p � 1, and so the rate law
reduces to υ = k r : that is, zeroth order and thus independent of pressure. On
platinum, absorption is weaker implying that α p � 1. In this limit the rate law
becomes υ = k r α p: that is, �rst order in the pressure.
D��D.� �is is discussed in Section ��D.� on page ���.

E��D.�(b) If the anodic process is dominant, the current density is given by [��D.�a–���],
ln j = ln j 0 + (1 − α) f η, where f = F�RT. At ���.�� K

f = (96485 C mol−1 )�[(8.3145 J K−1 mol−1 ) × (298.15 K)] = 38.921 V−1

where the units are resolved by recalling 1 V = 1 J C−1 . Taking the di�erence of
two expressions for ln j for di�erent overpotentials gives

ln( j 2 � j 1 ) = (1 − α) f (η 2 − η 1 )
ln( j 2 � j 1 )
hence η 2 = + η1
(1 − α) f
ln(72�17.0)
= + 0.105 V = �.�� V
(1 − 0.42) × (38.921 V−1 )

E��D.�(b) If the anodic process is dominant, the current density is given by [��D.�a–���],
j = j 0 e(1−α) f η , where f = F�RT. At ���.�� K, f = 38.921 V−1 . Rearranging for
j 0 and then using the data given

j 0 = j e−(1−α) f η
= (17.0 mA cm−2 ) e−(1−0.42)×(38.921 V = �.� mA cm−2
−1
)×(0.105 V)

E��D.�(b) If the anodic process is dominant, the current density is given by [��D.�a–���],
j = j 0 e(1−α) f η , where f = F�RT. At ���.�� K, f = 38.921 V−1 . Taking the ratio
of two expressions for j for di�erent overpotentials gives

j 2 � j 1 = j 0 e(1−α) f η 2 � j 0 e(1−α) f η 1
hence j 2 = j 1 e(1−α) f (η 2 −η 1 )
= (1.22 mA cm−2 ) e(1−0.5)×(38.921 V = �.� mA cm−2
−1
)×[(0.60−0.50) V)]

E��D.�(b) (i) �e Butler–Volmer equation is [��D.�–���], j = j 0 (e(1−α) f η − e−α f η ).

For Fe�+ on Pt j 0 = 2.5 × 10−3 A cm−2 and α = 0.58; at ���.�� K, f =
38.921 V−1 . For an overpotential of +0.30 V the current density is

j = (2.5 × 10−3 A cm−2 )

× (e(1−0.58)×(38.921 V − e−0.58×(38.921 V )
−1 −1
)×(0.30 V) )×(0.30 V)

= 0.34 A cm −2
 (ii) If the current is entirely anodic, only the �rst term is needed

j = (2.5 × 10−3 A cm−2 ) × e(1−0.58)×(38.921 V

−1
)×(0.30 V)

= 0.34 A cm−2

�e result con�rms that the current is indeed dominated by the anodic

term, which is the term for which the power of the exponential is positive.

E��D.�(b) �e Butler–Volmer equation is [��D.�–���], j = j 0 (e(1−α) f η − e−α f η ). �e

overpotential is equal to the applied potential E minus the potential developed
by the electrode which, assuming standard conditions, is +0.77 V: η = E −
(0.77 V). With the given value for j 0 , and assuming α = 0.5

j = (2.5 mA cm−2 ) × (e(1−0.5)× f ×[E−(0.77 V)] − e−0.5× f ×[E−(0.77 V)] )

j = (2.5 mA cm−2 ) × (e0.5 f [E−(0.77 V)] − e−0.5 f [E−(0.77 V)] )

E��D.�(b) At equilibrium, only the exchange current �ows, therefore for an electrode with
area A the current is j 0 A, and thus the charge passing in time t is (current ×
time): q = j 0 At. If each species passing through the double layer carries one
fundamental change, the number of charges is N = q�e = j 0 At�e. �us the
number per second through an area of �.� cm2 is, for H+ /Cu,

N�t = j 0 A�e = (1.0 × 10−6 A cm−2 ) × (1 cm2 )�(1.6022 × 10−19 C)

= 6.24... × 1012 s−1 = 6.2 × 1012 s−1

A similar calculation for Ce�+ /Pt gives 2.5 × 1014 s−1 .

�e number of atoms covering � cm2 of electrode is (10−4 m2 )�(260×10−12 m)2
= 1.47... × 1015 . �erefore for H+ /Cu the number of times per second that each
atom is involved in a electron transfer event is (number of such events)/(number
of atoms) = (6.24... × 1015 s−1 )�(1.47... × 1015 ) = 4.2 × 10−3 s−1 . A similar
calculation for Ce�+ /Pt gives �.�� s−1 .

E��D.�(b) In the linear region the current density and overpotential are related by [��D.�–
���], η = RT j�F j 0 , therefore the current density is j = ηF j 0 �RT. For an
electrode of area A the current is I = jA, and therefore the resistance is
η η RT
r= = =
I ηF j 0 A�RT F j 0 A

For H+ /Pb
(8.3145 J K−1 mol−1 ) × (298 K)
r= = 5.1 × 109 Ω
(96485 C mol−1 ) × (5.0 × 10−12 A cm−2 ) × (1.0 cm2 )

�e units are resolved by using (from inside the front cover) 1 V = 1 J C−1 and
1 Ω = 1 V A−1 . A similar calculation for Fe�+ /Pt gives 10 Ω .
E��D.�(b) Because the standard potential of Zn2+ /Zn is −0.76 V, under standard condi-
tions Zn metal will only be deposited when the applied potential is more nega-
tive than −0.76 V. �e current density is given by [��D.�–���], j = j 0 (e(1−α) f η −
e−α f η ), but under these conditions only the second term (the cathodic current)
is signi�cant. Using the data given for H+ , assuming α = 0.5, and recalling that,
at ���.�� K, f = 38.921 V−1

j H+ = − j 0 e−α f η
= −(0.79 × 10−3 A cm−2 ) e−0.5×(38.921 V
−1
)×(−0.76 V)

= −2.1 × 103 A cm−2

It is usually considered that the metal can be deposited if the current density for
discharge of H+ is less than about 1 mA cm−2 . In this case, the current density
for discharge of H+ is vastly in excess of this criterion, which means that zinc
metal will not be deposited, and all that will happen is the evolution of H� .

P��D.� Simultaneous deposition is expected if the two potentials are the same, and this
is acheived by altering the ratio of the concentrations of Pb�+ and Sn�+ . Using
the Nernst equation [�C.�–���], the potentials of the two half cells are
RT
E(Pb2+ �Pb) = E(Pb2+ �Pb)−○ + ln a Pb2+
2F
RT
E(Sn2+ �Sn) = E(Sn2+ �Sn)−○ + ln a Sn2+
2F
�ese will be equal when
RT RT
E(Pb2+ �Pb)−○ + ln a Pb2+ = E(Sn2+ �Sn)−○ + ln a Sn2+
2F 2F
From which it follows that
2F
ln(a Sn2+ �a Pb2+ ) = �E(Pb2+ �Pb)−○ − E(Sn2+ �Sn)−○ �
RT
2 × (96485 C mol−1 )
= [(−0.126 V) − (−0.136 V)]
(8.3145 J K−1 mol−1 )×(298 K)
= 0.778...

�erefore a Sn2+ �a Pb2+ = e0.778 ... = �.�� . By making the concentration of Sn�+
a bit over twice that of Pb�+ , simultaneous deposition can be achieved.

P��D.� �e overpotential is η = E ′ − E, where E is the equilibrium potential; in this

case η = E ′ + (0.388 V). �e data given correspond to positive overpotentials,
so the anodic current will dominate and hence ln j = ln j 0 + (1 − α) f η. For
the In�+ /In electrode three electrons are transferred, therefore the relationship
needs to be modi�ed to ln j = ln j 0 + 3(1 − α) f η. A plot of ln j against η will
have slope 3(1 − α) f and intercept ln j 0 . Such a plot is shown in Fig. ��.�.
 E ′ �V η�V j�(A m−2 ) ln[ j�(A m−2 )]
−0.365 0.023 0.590 −0.528
−0.350 0.038 1.438 0.363
−0.335 0.053 3.507 1.255

1.0
ln[ j�(A m−2 )]

0.5

0.0

−0.5
0.02 0.03 0.03 0.04 0.04 0.05 0.05 0.06
η�V

�e data fall on a good straight line with equation

ln[ j�(A m−2 )] = 59.41 × (η�V) − 1.894

From the slope it follows that 3 × (1 − α) × (38.921 V−1 ) = 59.41 V−1 hence
α = 0.49 . �e exchange current density is computed from the intercept as
j 0 = 0.150 A m−2 .
Note that there is an error in the problem: the cathodic current should be
computed for E ′ = −0.365 V. �e cathodic current is j c = − j 0 e−3α f η , thus
with the data already determined

j c = −(0.150 A m−2 ) e−3(0.49)×(38.921 V = −0.0402 A m−2

−1
)×[(−0.365+0.388) V]

P��D.� (a) �e Butler–Volmer equation, [��D.�–���], j = j 0 (e(1−α) f η − e−α f η ) is

expanded to second order in f η

j = j 0 �1 + (1 − α) f η + 12 (1 − α)2 f 2 η 2 − 1 + α f η − 12 α 2 f 2 η 2 �
= j 0 � f η + 12 f 2 η 2 (1 − 2α)� = j 0 f η + j 0 β f 2 η 2
� ��� � � � � �� � � � � � ��
term � term �

where β = 12 (1 − 2α) is used.

�e current density is integrated over a complete period with η = η 0 cos ωt;
the period is 2π�ω and the result of the integration is the total charge
 passing over this time. Term � integrates to zero because the integral of a
cosine wave over a complete period is zero. �e integral of term � is
2π�ω 2π�ω 2π�ω
j 0 β f 2 η 20 � cos2 ωt dt = 12 j 0 β f 2 η 20 � dt + 12 j 0 β f 2 η 20 � cos 2ωt dt
��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � ��� � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � � �
0 0 0

term �

where the identity cos A = 2 1

2
(1+cos 2A) is used.
Term � is zero as it is the
integral of a cosine wave over two complete periods. �e other integral
evaluates to 2π�ω and therefore the charge passing over the complete
period is
2π
1
j β f 2 η 20
2 0
ω
�e mean current over the complete period is found by dividing the charge
passing by the time, which is the period 2π�ω. �erefore

j av = 12 j 0 β f 2 η 20 = j 0 f 2 η 20 12 ( 12 − α)

As required, the mean current goes to zero when α = 12 .

(b) For H+ /Pt j 0 = 7.9 × 10−4 A cm−2 ; with the data given
j av = (7.9 × 10−4 A cm−2 ) × (38.921 V−1 )2 × (0.010 V)2 × 12 (0.5 − 0.38)
= 7.2 µA cm−2

P��D.� (a) �is voltammogram is that expected for a reversible process, as described
in Section ��D.� on page ���, and characteristic of a process with a ‘large’
exchange current density. Only a small overpotential is required to achieve
a signi�cant current.
(b) �e �rst part of the voltammogram shows two successive reductions, at
di�erent potentials. Both of these reductions appear to be reversible as the
current changes direction on the reverse sweep, with two features which
complement those in the �rst part of the sweep.
(c) �is voltammogram is that expected for a irreversible process, as described
in Section ��D.� on page ���, and characteristic of a process with a ‘small’
exchange current density. In this case a larger overpotential is needed to
generate a signi�cant current and the cathodic process dominates.
(d) �e �rst part of the voltammogram shows two successive reductions, at
di�erent potentials. �e second of these appears to be reversible as the
current changes direction for the �rst part of the reverse sweep, but the
second reduction appears to be irreversible as there is no negative-going
current associated with it.

I��.� �e relativistic correction term is

e∆� (1.6022 × 10−19 C) × (50 × 103 V)
= = 0.0489...
2m e c 2 2 × (9.1094 × 10−31 kg) × (2.9979 × 108 m s−1 )2
 �e non-relativistic wavelength is

h
λnon-rel =
(2m e e∆�)1�2
6.6261 × 10−34 J s
=
[2×(9.1094 × 10−31 kg)×(1.6022 × 10−19 C)×(50 × 103 V)]1�2
= 5.48 pm

With the relativistic correction

6.6261 × 10−34 J s
λrel =
[2×(9.1094 × 10−31 kg)×(1.6022 × 10−19 C)×(50 × 103 V)]1�2
1
× = 5.36 pm
(1 + 0.0489...)1�2

�ere is a signi�cant di�erence of about �%. Whether or not this will a�ect
any particular measurement depends on whether it is necessary to know the
wavelength to high precision.

I��.� �e tunneling of a particle through a rectangular barrier is described in Sec-

tion �D.� on page ���. �e decay of the wavefunction in the barrier depends
on the parameter κ given by κ = [2m(V0 − E)]1�2 �ħ, where E is the energy and
V0 is the height of the barrier. In this case (V0 − E) = 2.0 eV and so

κ = [2×(9.1094 × 10−31 kg)×(2.0×1.6022 × 10−19 J)]1�2 �(1.0546 × 10−34 J s)

= 7.24... × 109 m−1

Assuming that κL � 1 for the distances L considered in this calculation, the

transmission probability T is approximated by [�D.��b–���], T = 16ε(1 −
ε) e−2κ L , where ε = E�V0 . When the distance increases from L 1 to L 2 the ratio
of the transmission probabilities is

T2 �T1 = e−2κ(L 2 −L 1 )
= e−2×(7.24 ...×10 m−1 )×[(0.60−0.50)×10−9 m]
= 0.235
9

Assuming that the current is proportional to the transmission probability, this

ratio would also be the ratio of the currents.