UNICAMP Chem Handout

Instituto de Qumica
Chemical structure and reactivity:

an orbital based approach
James Keeler
University of Cambridge
Department of Chemistry
0: Introduction 1
0: Introduction
0: Introduction 2
How the lectures work1.1.1 Section title
we will follow the book pretty closely: what you will see on
the screen is in the text
the title of each frame will (usually) match the section
headings in the book
if a frame is just a gure, then the title will give the Figure
number for example:
0: Introduction 3
Fig 2.9 Shaded plot of 1s orbital
0: Introduction 4
Philosophy
we can understand, or at least rationalize, a great deal of
chemistry by thinking about orbitals and their interactions
not only structure and shape, but also reactivity
a qualitative understanding of atomic and molecular orbitals is
sufcient we do not need to do any calculations
I hope to show you how this unifying concept can be used to
make sense of a lot of chemistry
0: Introduction 5
Rough outline
thorough revision of atomic orbitals (especially shapes and
energies)
simple molecular orbitals (diatomics)
extending these ideas to larger molecules and in brief
solids
how orbitals can be used to understand reactions
if time permits, some other topics (e.g. thermodynamics)
0: Introduction 6
Lets begin
0: Introduction 7
Instituto de Qumica
James Keeler
2: Electrons in atoms 1
2: Electrons in atoms
Fig 2.1
e
n
e
r
g
y
classical quantum
for small objects energy is quantized and can only take specic
values: contrast the classical world where energy varies smoothly
Fig 2.2
classical quantum
in quantum mechanics we can only specify the probability of an
object being at a particular place
2.1.2 Probability interpretation
[(x, y, z)]
2
is the probability density
formally:
prob. of being in volume V at position (x, y, z)
= [(x, y, z)]
2
.,,.
prob. density
V
.,,.
volume
loosely: the probability of nding the electron at a particular
position is proportional to the square of the wavefunction
2.1.3 Energy
kinetic energy: due to motion
potential energy: e.g. due to interaction between charges
hydrogen atom: negative electron interacting with positive
nucleus (Coulomb potential)
r
r
V
(
r
)
0
2.2 Introducing orbitals
solve the Schr odinger equation for the hydrogen atom
the resulting wavefunctions are called the (hydrogen) atomic
orbitals (AOs)
the mathematical forms and energies can be found exactly
these are the familiar 1s, 2s, 2p etc.
understanding their shapes and energies is crucial
2.2.1 Representing orbitals on paper
mathematical form of the 1s orbital
1s
(r) = N
1s
exp (r/a
0
)
r: electronnucleus distance; a
0
: Bohr radius (52.9 pm);
N
1s
is a normalizing factor
plot
1s
(r) as a function of r
r / pm
a
0
0
0 40 80 120
2a
0
3a
0
1
s
(
r
)
need to understand that this is a three-dimensional function
there are many ways of representing it
Fig 2.7: cubes
(a) (b) (c)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
0
0
0
0
1
1
1
0
0
0
0
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
0
0
0
1
3
5
3
1
0
1
3
10
15
10
3
1
1
5
15
26
15
5
1
1
3
10
15
10
3
1
0
1
3
5
3
1
0
0
0
1
1
1
0
0
0
0
1
1
1
0
0
0
2
5
7
5
2
0
1
5
15
26
15
5
1
1
7
26
100
26
7
1
1
5
15
26
15
5
1
0
2
5
7
5
2
0
0
0
1
1
1
0
0
shading and numbers indicate relative value of the orbital
wavefunction
Fig 2.8: Contour plot
x
y
(a) (b) (c)
1
1
1
3
3
10
10
30
lines connect positions at which the wavefunction has a constant
value (like contours on a map)
Fig 2.9: Shaded plot
density of colour indicates value of wavefunction (ring at maximum
density)
Fig 2.10: Iso-surface
(a) (b) (c)
surface connects positions at which the wavefunction has a
constant value (a three-dimensional contour)
the apparent size depends on value at which the iso-surface
is drawn
2.2.2 Radial distribution function
probability of nding the electron in a thin shell of radius r and
thickness r i.e. summed over all angles
a thin shell
x y
z
dene radial distribution function, P
1s
(r)
P
1s
(r) = 4r
2
[
1s
(r)]
2
P
1s
(r) r is the probability of nding the electron in a shell of
radius r and thickness r
Fig 2.12
r
a
0 0 2a
0
3a
0
a
0 0 2a
0
3a
0
a
0 0 2a
0
3a
0
1s
(r) P
1s
(r) [
1s
(r)]
2
r
2
(a) (b) (c)
4r
2
r is volume of shell
as r increases volume of shell increases, but value of
wavefunction decreases
result in a maximum in the RDF
2.3 Hydrogen atomic orbitals
three quantum numbers characterise each orbital
principal quantum number, n: takes values 1, 2, 3 . . .
orbital angular momentum quantum number, l: takes values
from (n 1) down to 0, in integer steps
magnetic quantum number, m
l
: takes values from +l to l in
integer steps
there are (2l + 1) different values of m
l
K shell
n = 1
l = 0 only
m
l
= 0 only
letters represent different values of l
l letter
0 s
1 p
2 d
3 f
only orbital is 1s
L shell
n = 2
l takes values (n 1) down to 0 i.e. l = 1 and l = 0
m
l
takes values from +l to l in integer steps
for l = 1, m
l
= 1, 0, 1 the three 2p AOs
for l = 0, m
l
= 0 the 2s AO
L shell: three 2p, 2s
M shell
n = 3, hence l = 2, 1, 0
for l = 2, m
l
= 2, 1, 0, 1, 2 the ve 3d AOs
for l = 1, m
l
= 1, 0, 1 the three 3p AOs
for l = 0, m
l
= 0 the 3s AO
M shell: ve 3d, three 3p, 2s
Orbital energies
the energy only depends on n
E
n
=
Z
2
R
H
n
2
Z: nuclear charge (here = 1); R
H
: Rydberg constant
R
H
= 2.180 10
18
J 1312 kJ mol
1
13.6 eV
energies measured downwards from ionization
e
n
e
r
g
y

/

e
V
0
-5
-10
-15
n = 1
n = 2
n = 3
ionization
Orbital energies
the energy only depends on n
E
n
=
Z
2
R
H
n
2
orbitals with the same n have the same energy: they are said
to be degenerate
e.g. the ve 3d, the three 3p and the 3s all have the same
energy
2.3.2 Shapes of the 2s and 2p orbitals; Fig 2.14 cubes
(a) (b) (c)
positive at the centre, crossing to negative at large distances
Fig 2.15 Iso-surface
x y
z
x y
z
(a) (b)
positive at the centre, crossing to negative at large distances
spherical
Fig 2.16 Contour plot/density plot
(a) (b) (c)
-4 0 4 8 -8
-4
0
4
8
-8
red: positive; blue: negative; green: zero
radial node: value of r at which the wavefunction crosses zero
(note that at a node the wavefunction must cross zero, not just
be zero)
2p: Fig 2.17 Iso-surface
x y
z
x y
z
x y
z
(a) (b) (c)
2p
z
2p
x
2p
y
red: positive; blue: negative
three degenerate orbitals, pointing along x, y and z
each has a nodal plane (also called an angular node i.e.
angles at which the wavefunction crosses zero)
Fig 2.18 2p
z
cubes
(a) (b) (c)
z
x
y
the xy plane is a nodal plane for the 2p
z
AO
Fig 2.19 2p
y
cubes
(a) (b) (c)
z
x
y
the xz plane is a nodal plane for the 2p
y
AO
Fig 2.20 Contour plot/density plot
(a) (b)
-4 0 4 8 -8
-4
0
4
8
-8
x
z
nodal plane (xy) appears as a line
Fig 2.21 How not to draw a p orbital
the positive and negative lobes do not touch
the shape of the lobes is incorrect
2.2.3 Mathematical form of the 1s, 2s and 2p orbitals
x
y
r
z
use spherical polar coordinates
wavefunction is a product of a radial part and an angular part
n,l,ml
(r, , ) = R
n,l
(r)
.,,.
radial part
Y
l,ml
(, )
.,,.
angular part
note that the wavefunctions are labelled with quantum
numbers
Recall radial distribution function
probability of nding the electron in a thin shell of radius r and
thickness r i.e. summed over all angles
P
n,l
(r) is related simply to the radial part of the wavefunction
P
n,l
(r) = r
2
[R
n,l
(r)]
2
the angular part Y
l,ml
(, ) does not affect the RDF
Fig 2.23 Radial parts and RDFs for 1s, 2s and 2p
r / a
0
r / a
0
P(r) R(r)
(a) (b)
2 4 6 8 10
2 4 6 8 10
1s
1s
2p 2p
2s
2s
radial node for 2s but not for 1s and 2p; 2p goes to zero at
nucleus (but this is not a node, as wavefunction does not
cross zero)
2s and 2p larger than 1s: principal maximum at larger r
2s and 2p have subtly different distributions of electron
density; note especially the subsidiary maximum, close to the
nucleus, for the 2s
Fig 2.28 Radial parts and RDFs for 3s, 3p and 3d
r / a
0
r / a
0
(r) P(r)
(a) (b)
2s
3p
3p
3s
3s
3d
3d
5 10 15 20 25 30
5 10 15 20 25 30
two radial nodes for 3s, one for 3p, none for 3d
3p and 3d go to zero at nucleus
larger than 2s (and 1s)
Fig 2.29 Contour plot/density plot for 3s
(a)
(b) (c)
-10
0
10
20
-20
-10 0 10 20 -20
spherical; two radial nodes
Fig 2.30 Iso-surface plots of three 3p
x x x y y y
z z z (a) (b) (c)
3p
z
3p
x
3p
y
basically like 2p with a nodal plane (angular node)
radial node cuts the lobes
Fig 2.31 Contour plot/density plot for 3p
z
(a)
(b)
y

o
r

z
x
-10
0
10
20
-20
-10 0 10 20 -20
radial node appears as a (green) circle
angular node appears as a (green) line
Fig 2.32 Iso-surface plots of three of the 3d
x
x
x
y y y
z z z (a) (b) (c)
3d
xz
3d
yz
3d
xy
two angular nodes
e.g. for 3d
xz
, yz and xy are nodal planes
Fig 2.33 Contour plot/density plot for 3d
xz
(a)
(b)
z
x
-10
0
10
20
-20
-10 0 10 20 -20
angular nodes (two) appear as a (green) line
Fig 2.34 Iso-surface plots of the other two 3d
x x y y
z z
(b) (a)
3d
x2-y2 3d
z2
still have two angular nodes, but these no longer correspond
to simple planes such as the xy plane
Fig 2.35 Contour plot/density plot for 3d
x
2
y
2 and 3d
z
2
(a) (b) (c) (d)
yz
x or y x
3d
x2-y2 3d
z2
the two angular nodes appear as a green lines
for 3d
x
2
y
2 these two angular nodes are planes bisecting the
xz and yz planes
Fig 2.36 Angular nodes in 3d
z
2
x y
z
angular nodes are two cones with (latitude) angles of 54.7
and 125.3
2.4 Spin
electrons have intrinsic source of angular momentum, called
spin angular momentum
need to add another quantum number s, the spin angular
momentum quantum number; always takes value of
1
2
associated quantum number m
s
takes values +
1
2
and
1
2
(like
relation between l and m
l
)
m
s
= +
1
2
, spin up or
m
s
=
1
2
, spin down or
2.5 Hydrogen-like atoms
these have just one electron, but nuclear charge is larger
e.g. He
+
(Z = 2), Li
2+
(Z = 3)
energy scales as Z
2
E
n
=
Z
2
R
H
n
2
orbitals shrink
1 2 3 4 5
r / a
0
P
(
r
)
Z=1
Z=2
Z=3
2.6 Multi-electron atoms
hydrogen is particularly simple as there is only one electron
from He onwards we need to take account of
electronelectron repulsion: this makes things much more
complicated
1
2
+2
we use the orbital approximation: electrons are assumed to
be moving in the mean eld of all the other electrons
as a result, each electron can be assigned to a hydrogen-like
orbital
2.6 Multi-electron atoms: electronic congurations
electrons assigned hydrogen-like orbitals; up to two (spin
paired) electrons per orbital
leads to the familiar electronic congurations:
He: 1s
2
; Li 1s
2
2s
1
; B: 1s
2
2s
2
2p
1
; Ne 1s
2
2s
2
2p
6
the orbitals are similar to, but not the same as, the hydrogen
orbitals; exact form can only be found from computer
calculations
in particular the energies are no longer simply related to the
value of n
Fig 2.43 Orbital energies: rst two periods
1 2 3 4 5 6 7 8 9 10
-60
-50
-40
-30
-20
-10
0
1s
1
s
2
1
s
2
2
s
1
1
s
2
2
s
2
.
.
.
2
p
1
.
.
.
2
p
2
.
.
.
2
p
3
.
.
.
2
p
4
.
.
.
2
p
5
.
.
.
2
p
6
1
s
1
2s
2p
H He Li Be B C N O F Ne
e
n
e
r
g
y

/

e
V
1s quickly falls in energy after it is lled
2s lower in energy than 2p: this is why 2s is lled rst
2s and 2p fall steadily in energy across the period
gap between 2s and 2p widens
Screening
in Li, the 1s
2
are closer to the nucleus than the 2s
the 1s
2
can be thought of a screening the 2s from the nucleus
if the screening is perfect, the 2s sees a nuclear charge of +1
Z=+3
2s
1s
2
(a)
Z
eff
=+1
2s
(b)
the charge experienced by an electron is called the effective
nuclear charge, Z
e
Effective nuclear charge
assume orbital energy follow same form as for hydrogen but
replace Z with Z
e
E
n
=
Z
2
e
R
H
n
2
rearrange to give Z
e
in terms of the orbital energy E
n
Z
e
=
_
n
2
E
n
R
H
for Li, 2s has energy 5.34 eV, giving Z
e
=1.25
Z
e
is much less than the actual nuclear charge (3), so
screening is signicant (but not perfect)
Penetration
another way of looking at this is say that the 2s penetrates to a
small extent inside the region occupied by the 1s
2
useful way of explaining why 2s and 2p have different energies
approximate RDFs for Li (Z
e
for 1s is 3, but for 2s and 2p is 1)
2s
1s
2p
2 4 6 8 10
r / a
0
the 2s penetrates more into the region occupied by the 1s than
does the 2p
2s experiences a higher Z
e
and so is lower in energy than 2p
Fig 2.43 Orbital energies: rst two periods
1 2 3 4 5 6 7 8 9 10
-60
-50
-40
-30
-20
-10
0
1s
1
s
2
1
s
2
2
s
1
1
s
2
2
s
2
...2
p
1
...2
p
2
...2
p
3
...2
p
4
...2
p
5
...2
p
6
1
s
1
2s
2p
H He Li Be B C N O F Ne
e
n
e
r
g
y
/ e
V
1s quickly falls in energy after it is lled: the 2s and 2p
electrons are not effective at shielding the 1s from the
increased nuclear charge
2s and 2p fall steadily in energy across the period: the 2s and
2p electrons are only partially effective at screening one
another from the increased nuclear charge
gap between 2s and 2p widens: 2s penetrates more to the
nucleus and so experiences more of the increased nuclear
charge 2: Electrons in atoms 49
Fig 2.42 Orbital energies: rst three periods
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
-120
-140
-80
-100
-60
-40
-20
0
1s
1
s
2
1
s
2
2
s
1
1
s
2
2
s
2
.
.
.
2
p
1
.
.
.
3
p
1
.
.
.
3
p
2
.
.
.
3
p
3
.
.
.
3
p
4
.
.
.
3
p
5
.
.
.
3
p
6
.
.
.
3
s
1
.
.
.
3
s
2
.
.
.
2
p
2
.
.
.
2
p
3
.
.
.
2
p
4
.
.
.
2
p
5
.
.
.
2
p
6
1
s
1
2s
2p
3s
3p
H He Li Na Be B C N O F Ne Mg Al Si P S Cl Ar
e
n
e
r
g
y

/

e
V
3s/3p higher in energy than 2s/2p: attributed to increase in n
2s/2p quickly fall in energy after after they are lled
3s and 3p fall steadily in energy; 3s is below 3p
gap between 3s and 3p widens
2.6.5 Excited states and empty orbitals
recall: orbital energy depends on average repulsion with all
other electrons
thus orbital energy depends on precisely which other orbitals
are occupied
orbital energies are therefore not a xed ladder of levels
for example:
-25
-20
-15
-10
-5
2s
2
2p
2
2p
2s
2s
1
2p
3
2p
4
e
n
e
r
g
y

/

e
V
energy of an empty orbital is the energy that an electron
would have, were it to occupy that orbital
2.7 Ionization energy
ionization energy (IE) is energy required to remove a
particular electron to innity
i.e. for the process
A(g) A
+
(g) + e
energy change is
IE = energy of A
+
energy of A
one electron atom: energy of A
+
is zero and energy of A is
simply the energy of the electron in its orbital, hence
one-electron atom : IE = orbital energy
Ionization of multi-electron atoms
ionization energy (IE) is energy required to remove a
particular electron to innity
IE = energy of A
+
energy of A
recall energy of an electron in an orbital depends on which
other orbital are occupied
i.e. orbital energies change when an electron is removed
it can therefore only be an approximation that
IE orbital energy
Fig 2.51 Ionization energies
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
0
5
10
15
20
25
1
s
2
1
s
2
2
s
1
1
s
2
2
s
2
.
.
.
2
p
1
.
.
.
3
p
1
.
.
.
3
p
2
.
.
.
3
p
3
.
.
.
3
p
4
.
.
.
3
p
5
.
.
.
3
p
6
.
.
.
3
s
1
.
.
.
3
s
2
.
.
.
2
p
2
.
.
.
2
p
3
.
.
.
2
p
4
.
.
.
2
p
5
.
.
.
2
p
6
1
s
1
H He Li Na Be B C N O F Ne Mg Al Si P S Cl Ar
e
n
e
r
g
y

/

e
V
ionization energy
- (orbital energy )
IE orbital energy works pretty well
but drop in IE from N to O is a particularly noticeable deviation
explanation for this is due to the effects of quantum
mechanical exchange energy
2.7.3 Exchange energy
how do we ll up the 2p AOs as we go across the Second
Period?
experimentally, the lowest-energy arrangements are
p
6
p
1
p
2
p
3
p
4
p
5
B
C
N
O
F
Ne
rationalization is that we are maximizing the number of
parallel spins
Fig 2.53
possible arrangements for p
3
(a)
(b)
(c)
(d)
(a) has three pairs of parallel spins: 12, 13 & 23
(b) has one pair of parallel spins: 12; (c) has the same, but
this time it is 23
(d) has one pair of parallel spins: 12
each pair of parallel spins lowers the energy due to a purely
quantum mechanical effect (the exchange energy); (a) is
therefore the lowest energy arrangement
Fig 2.53
possible arrangements for p
3
(a)
(b)
(c)
(d)
(a) is the lowest energy arrangement
this is not because:
electrons repel one another, so placing them in separate

orbitals minimizes the repulsion
electrons with parallel spins avoid one another, so having

parallel spins further lowers the energy
common, but entirely wrong, explanations
Exchange energy
ionization energy is difference
IE = energy of A
+
energy of A
need to work out the exchange contribution to the total energy
of A and A
+
simple model: each pair of parallel spin electrons lowers the
energy by K
e.g. 2p
2
has an exchange energy of K, but 2p
3
has an
exchange energy of 3K
Tabulate exchange energy
atom ion
element cong. Eexch(atom) cong. Eexch(ion) Eexch(ion) Eexch(atom)
B 2p
1
0 2p
0
0 0
C 2p
2
K 2p
1
0 K
N 2p
3
3K 2p
2
K 2K
O 2p
4
3K 2p
3
3K 0
F 2p
5
4K 2p
4
3K K
Ne 2p
6
6K 2p
5
4K 2K
right-hand column gives the exchange contribution to the
ionization energy
exchange contribution increases the ionization energy of N
relative to C, and C relative to B
Fig 2.54 Exchange contributions
p1 p2 p3 p4 p5 p6
p0 p1 p2 p3 p4 p5
e
x
c
h
a
n
g
e

e
n
e
r
g
y

E
e
x
c
h
(
io
n
)

-

E
e
x
c
h
(
a
t
o
m
)
atom
ion
(a) (b)
(c)
-6K
-4K
-2K
0
2K
-6K
-4K
-2K
0
2K
5
10
15
20
B C N O F Ne
p1 p2 p3 p4 p5 p6
p0 p1 p2 p3 p4 p5
atom
ion
B C N O F Ne
p1 p2 p3 p4 p5 p6
p0 p1 p2 p3 p4 p5
atom
ion
B C N O F Ne
io
n
iz
a
t
io
n

e
n
e
r
g
y

/

e
V
(a) gives exchange contribution to each conguration, (b)
gives difference in these contributions, (c) shows effect of
superimposing the exchange effects on a general rise in the IE
Fig 2.54 Exchange contributions
p1 p2 p3 p4 p5 p6
p0 p1 p2 p3 p4 p5
e
x
c
h
a
n
g
e

e
n
e
r
g
y

E
e
x
c
h
(
io
n
)

-

E
e
x
c
h
(
a
t
o
m
)
atom
ion
(a) (b)
(c)
-6K
-4K
-2K
0
2K
-6K
-4K
-2K
0
2K
5
10
15
20
B C N O F Ne
p1 p2 p3 p4 p5 p6
p0 p1 p2 p3 p4 p5
atom
ion
B C N O F Ne
p1 p2 p3 p4 p5 p6
p0 p1 p2 p3 p4 p5
atom
ion
B C N O F Ne
io
n
iz
a
t
io
n

e
n
e
r
g
y

/

e
V
the high IE of N relative to O is often said to be due to some
special stability of a half-lled shell: the proper explanation is
more complex, and is due to the change in the exchange
contribution on going from A to A
+
2: Electrons in atoms
the end
Instituto de Qumica
James Keeler
3: Electrons in molecules: diatomics 63
3: Electrons in molecules:
diatomics
Molecular orbitals
assign electrons to molecular orbitals (MOs) in analogy to
atomic orbitals
a powerful framework for understanding structure and bonding
can explain, for example:
H
2
exists as a stable molecule, He
2
is unknown, but He
+
2
has
been detected
the bond dissociation energy of Be

2
is less than one tenth of
that of either Li
2
or B
2
N
2
has a stronger bond than does O
2
the bond in N
+
2
is weaker than that in N
2
, but the bond in O
+
2
is
stronger than that in O
2
in LiH, the hydrogen has a partial negative charge, whereas

in FH, the hydrogen has a partial positive charge
O
2
is paramagnetic, meaning that it is drawn into a magnetic
eld, but N
2
is not
3.1 Introducing molecular orbitals
+1 +1
-1
in H
+
2
there are several interactions which contribute to the
energy
electronnuclear attraction (blue)
nuclearnuclear repulsion (red)
there is also a contribution to the energy from the kinetic
energy of the electron
the equilibrium bond length (that with the lowest energy) is
determined by the balance between all of these
Fig 3.2 Contributions to the energy
R Re
0
e
n
e
r
g
y
e-n
n-n
ke
tot
H+H
+
H2
+
en: electronnuclear attraction (blue)
nn: nuclearnuclear repulsion (red)
ke: kinetic energy of the electron (green)
total energy (black) is the sum of all
these, and is a minimum at R
e
3.1.1 Linear combination of atomic orbitals
a convenient and intuitive way of constructing MOs
combine 1s AOs from the two atoms (A and B)
MO = c
A
(1s AO on atom A) + c
B
(1s AO on atom B)
c
A
and c
B
are the orbital coefcients; they are just numbers,
whose values determine how much of each AO is present in
the MO
in H
+
2
the situation is very simple: there are two MOs
+
= [(1s AO on atom A) + (1s AO on atom B)]
= [(1s AO on atom A) (1s AO on atom B)]

Fig 3.3 Bonding and antibonding MOs
quantum mechanics allows us to compute the energies of
+
and
as a function of the bond length

R / a
0
E
+
E
-
e
n
e
r
g
y
2 4 6 8
energy of
+
(E
+
) falls as atoms approach, reaching a
minimum: called the bonding MO
energy of
(E
) rises as atoms approach: called the

antibonding MO
x
y
z
x
y
z
x
y
z
x
y
z
x
y
z
x
y
z
R = 6 a0 R = 4 a0 R = 2.5 a0
(a)
(b)
equilibrium bond length is 2.5 a
0
(a), bonding MO: results from constructive or in-phase overlap
(b), antibonding MO: results from destructive or out-of-phase
overlap
R = 6 a0 R = 4a0 R = 2.5a0
(a)
(b)
(a), bonding MO: builds up electron density between the
nuclei this is why the energy falls
(b), antibonding MO: electron density pushed away from the
internuclear region
3.1.3 Symmetry labels for MOs
assign , or based on what happens to the wavefunction
as you traverse the indicated path
no sign change
cross one nodal plane
cross two nodal planes
3.1.3 Symmetry labels for MOs
(a) (b) (c)
start at any point, move to centre, carry on in same direction
for same distance
if end up at an equivalent point, object possesses a centre of
inversion
(a) and (c) each have a centre of inversion, (b) does not
a homonuclear diatomic has a centre of inversion
Fig 3.9 Symmetry labels for MOs
(a) (b)
(a) in bonding, (b) is antibonding MO
both have no sign change as you go round the internuclear
axis
on inversion, bonding MO does not change sign g
on inversion, antibonding MO changes sign u
bonding MO is
g
; antibonding MO is
u
3.1.4 MO diagrams
(a) (b) (c)
R = 6 a
0
R = 4 a
0
R = 2.5 a
0
1
g
1
u
1s(A)
A B A B A B
1s(B)
e
n
e
r
g
y
vertical scale is energy
energies of AOs shown to left and right; energies of MOs
shown in middle
as bond length decreases, interaction increases and energy
shift to MOs increases
antibonding MO goes up in energy more than bonding MO
goes down
3.1.6 Overlap
R / a
0
1s(A)
1s(A) 1s(B)
1s(B)
o
v
e
r
la
p
,

S
(
R
)
1 2 3 4 5 6
0.2
0.0
0.4
0.6
0.8
1.0
the overlap integral is the area under a plot of the product of
the two wavefunctions
S(R) falls off as the internuclear separation increases
S(R) is a guide to how much the bonding MO will be lowered
in energy compared to the AOs
note that at short distances internuclear repulsion increases
and the bonding MO will then rise in energy
3.1.7 Summary
MOs are formed from the linear combination of AOs on
different atoms
in H
+
2
combining two 1s AOs gives two MOs: one bonding and
one antibonding
bonding MO shows a minimum in its energy at a certain
separation; the energy of the antibonding MO simply
increases as the internuclear separation decreases
bonding MO arises from an in-phase or constructive
combination of the AOs; this leads to a concentration of
electron density in the internuclear region
antibonding MO arises from an out-of-phase or destructive
combination of the AOs; this leads to electron density being
excluded from the internuclear region and being concentrated
on the periphery
3.2 H
2
, He
2
and their ions
1g
1u
H
2
+
1g
1u
H
2
1g
1u
He
2
+
/ H
2
-
1s 1s
molecule conguration diss. energy / kJ mol
1
bond length / pm
H
+
2
1
1
g
256 106
H2 1
2
g
432 74
He
+
2
1
2
g
1
1
u
241 108
He2 1
2
g
1
2
u
not observed
3.3 Homonuclear diatomics of the Second Period
moving from H
2
to Second Period diatomics brings extra
complications
more AOs to overlap (2s and 2p)
different types of overlap ( and )
we are guided by ve rules for forming MOs; these arise from
the underlying quantum mechanics
3.3.1 Rules for forming MOs
1. the combination of a certain number of AOs produces the
same number of MOs
2. only AOs of the correct symmetry will interact to give MOs
3. the closer in energy the AOs, the larger the interaction when
MOs are formed
4. each MO is formed from a different combination of AOs; AOs
which are close in energy to the MO contribute more than
those which are further away in energy
5. the size of the AOs must be compatible for there to be a
strong interaction when MOs are formed
Rule 2: symmetry
consider the overlap of a 2s with a 2p
x
AO (internuclear axis is
along z)
positive
overlap
negative
overlap
1s
2p
x
z
positive overlap of the upper lobe is equal and opposite to the
negative overlap of the lower lobe
net overlap is zero: no MOs are formed
2s is symmetric with respect to the yz plane, whereas 2p
x
is
anti-symmetric i.e. they do not have the same symmetry
Rule 2: symmetry
correct symmetry to overlap
no overlap
1s
1s
1s 1s
2p
z
2p
z
2p
z
2p
z
2p
x
2p
x
2p
x
2p
x
overlap which leads to bonding is shown; there is also an
antibonding MO formed
Rules 3 and 4: energy match
increasing energy gap between AOs
A B A
B
A
B
A
B
*
*
*
*
as energy separation of AOs increases, change in energy on
forming the MO decreases
antibonding MO (indicated by

) lies above the highest energy
AO, bonding MO lies below the lowest energy AO
if the energy mismatch between the AOs is large, then there is
hardly any change in the energy
(a) (b) (c)
*
*
* A B A
B
A
B
unless AOs have the same energy they make an uneven
contribution to the MOs
greatest contribution is from the AO closest in energy to the
MO
if the energy mismatch between the AOs is large, then there is
hardly any contribution from one of the AOs
As the energy separation between the AOs increases:
the bonding MO lies closer and closer in energy to that of the
lower energy AO
the antibonding MO lies closer and closer in energy to that of
the higher energy AO
the contribution to the bonding MO from the lower energy AO
increases, while that from the higher energy AO decreases
the contribution to the antibonding MO from the higher energy
AO increases, while that from the lower energy AO decreases
Rule 5: size
(a) (b)
(a) overlap of 2s, (b) overlap of 1s (the 1s are contracted due
to experiencing a relatively high effective nuclear charge)
although energy match is good, the two 1s are too contracted
to overlap signicantly
for the Second Period diatomics, we can simply ignore the 1s
AOs
Types of MOs from 2s and 2p AOs; Fig 3.19
(a) (b)
-4 -2 0 2 4 6 -6
-4
-6
-2
0
2
4
6
g

u
assume only 2s2s and 2p2p overlap (energy match)
2s2s gives bonding
g
and antibonding
u

u
has nodal plane between the two atoms
only outer part of 2s involved in overlap
Fig 3.20 MOs from 2s overlap
(a) (b) x
y
z
x
y
z
g

u
2s2s gives bonding
g
and antibonding
u

u
Fig 3.21 Cartoon representation of MOs from 2s
overlap
+
+
u
grey indicates positive; white indicates negative
in-phase and out-of-phase overlap
Fig 3.22 MOs from 2p overlap
(a) (b)
g

u
x
y
z
x
y
z
head on overlap of 2p
z
gives bonding
g
and antibonding
u

u
(a) (b)
g

u
-4 -2 0 2 4 6 -6
-4
-6
-2
0
2
4
6
head on overlap of 2p
z
gives bonding
g
and antibonding
u

u
Fig 3.24 Cartoons representation of 2p -type overlap
+

g
+

u
(a) (b)
(c) (d)
g u
x
y
z
x
y
z
x
y
z
x
y
z
side ways overlap of 2p
x
(or 2p
y
) gives bonding
u
and
antibonding
g
both have a nodal plane containing the internuclear axis
form a degenerate pair
(a) (b)
u g
-4 -2 0 2 4 6 -6
-4
-6
-2
0
2
4
6
z
x
both have a nodal plane containing the internuclear axis
antibonding MO has nodal plane between the two nuclei
second pair of MOs in perpendicular plane
Fig 3.27 Cartoons representation of 2p -type overlap
+

u
+

g
3.3.3 Idealized MO diagram for homonuclear diatomic
only allow 2s2s and 2p2p overlap
ignore 1s AOs (too contracted)
sequentially number MOs with same symmetry label e.g. 1
g
,
2
g
etc.
Fig 3.28 Idealized MO diagram for homonuclear diatomic
2
g
2
u
3
g
1
u
2p
2s 2s
2p
1
g
3
u
AOs on A AOs on B MOs
Fig 3.29 MO diagram for O
2
16 electrons giving conguration
1
2
g
1
2
u
2
2
g
2
2
u
3
2
g
1
4
u
1
2
g
1
g
and 1
u
neither bonding nor
antibonding: ignore
8 bonding electrons, 4 antibonding hence net
bonding i.e. stable with respect to
dissociation into atoms
bond order (BO)
BO =
1
2
(no. of bonding electrons
no. of antibonding electrons)
= 2
2
g
2
u
3
g
1
u
1
g
3
u
Fig 3.30 O
2
is paramagnetic
paramagnetism: drawn into a magnetic eld
associated with unpaired electrons
conguration of O
2
has two unpaired electrons in
g
1
2
g
1
2
u
2
2
g
2
2
u
3
2
g
1
4
u
1
2
g
triumph of MO theory to explain paramagnetism
MO diagram for F
2
18 electrons giving conguration
1
2
g
1
2
u
2
2
g
2
2
u
3
2
g
1
4
u
1
4
g
8 bonding electrons, 6 antibonding hence net
bonding i.e. stable with respect to
dissociation into atoms
BO = 1
dissociation energy of O
2
494 kJ mol
1
, but
for F
2
it is 154 kJ mol
1
2
g
2
u
3
g
1
u
1
g
3
u
Ions of O
2
3
g
1
u
1
g
3
u
species bond length / pm diss. energy / kJ mol
1
BO paramag?
O
+
2
112 643 2.5 yes
O2 121 494 2 yes
O
2
135 395 1.5 yes
O
2
2
149 204 1 no
Fig 3.31 Allowing for sp mixing
2g
2u
3g
2g
3g
3u
2u
3u
(a)
MO1
MO2
MO3
MO4
MO5
MO6
2p
2s
(b)
1u
1u
1g 1g
orbitals (including MOs) with same symmetry and which are
reasonably close in energy can mix
result is the higher energy MO goes up in energy, and the
lower energy MO goes down
2
g
and 3
g
mix: 3
g
becomes less bonding and may lie
above 1
u
sp mixing decreases across the period
Fig 3.34 Energies of occupied MOs
2
u
1
u
1
g
2
g
3
g
Li
2
Be
2
B
2
C
2
N
2
O
2
F
2
-5
0
-10
-15
-20
-25
-30
-35
o
r
b
it
a
l
e
n
e
r
g
y

/

e
V
Fig 3.38 Heteronuclear diatomic: LiH
1s
2s
Li H
2
3
only consider 2s on Li and 1s on H
AO energies do not match resulting in unsymmetrical MOs
2 bonding MO mostly on H: H is
note: no g or u labels on MOs
Fig 3.39 Heteronuclear diatomic: HF
1s
F H
3 3
1 1
4
2px / 2py
2pz
H - F
H - F
only consider 2p on F since 2s too low in energy; 1s on H
2p
x
and 2p
y
have no AOs on H with correct symmetry to
overlap nonbonding MOs (1)
3 bonding MO mostly on F: F is
Fig 3.41 NO, NN and CO
2
u
3
u
1
u
1
g
1
2
2
2
g
3
4
6
5
1
3
4
5
3
g
2s
2s
2p
2p
C - O N - N N - O
(c) (b) (a)
6
more electronegative atom has lower energy AOs
1 / 1
u
are bonding
5 / 3
g
weakly bonding
NN and CO are isoelectronic and lled up to 5 / 3
g
; NO
has one extra electron in 2
Fig 3.42 NO, NN and CO
3
4
1
5
2
3
4
1
5
2u
3g
2
g
1u
C - O N - N N - O
symmetrical in NN, but bonding MOs polarized towards more
electronegative atom in NO and CO
Fig 3.44 Heteronuclear diatomic: LiF
F Li
3
3
4
4
5
1
1
2s
2s
2p
Li - F
Li - F
AOs on F much lower in energy than those on Li
2p
x
and 2p
y
have no AOs on Li with correct symmetry to
overlap nonbonding MOs (1)
energy separation of Li and F AOs so large that there is little
mixing
as if an electron transferred from Li to F (ionic)
3.5.3 The HOMO and the LUMO
highest occupied molecular orbital (HOMO)
lowest unoccupied molecular orbital (LUMO)
in CO HOMO is 5 and LUMO is 2
diatomics
the end
Instituto de Qumica
James Keeler
4: Electrons in molecules: polyatomics 111
polyatomics
MOs for larger molecules
as the number of atoms and AOs increases, so does the
number and complexity of the MOs
computer programs available to compute MOs
but a pencil and paper approach is still a useful guide
symmetry can provide helpful simplication
likewise hybrid atomic orbitals
4.1 Linear H
+
3
2
1
1
3
3
2
mirror plane swaps atoms 1 and 3 i.e. they are equivalent
mirror plane does not swap atom 2 with any of the others
recall only orbitals with the same symmetry overlap
we will classify AOs according to their symmetry with respect
to this mirror plane
Fig 4.2 Effect of mirror plane
2
1
3
symmetric
swapped by
mirror plane
consider 1s AO on each H, and consider effect of reection in
mirror plane
AO on atom 2 reected into itself: symmetric
AO on atom 1 swapped with 3, likewise 3 swapped with 1
AOs on 1 and 3 are neither symmetric nor antisymmetric
Fig 4.3 Symmetry orbitals
1 3
1 3
symmetric: 1s(1) + 1s(3)
antisymmetric: 1s(1) - 1s(3)
the combination 1s(1) + 1s(3) is reected onto itself with no
sign change: symmetric
the combination 1s(1) 1s(3) is reected onto minus itself:
antisymmetric
combinations of AOs which are either symmetric or symmetric
under a particular symmetry operation are called symmetry
orbitals (SOs)
symmetric: orange; antisymmetric: green
Fig 4.4 MO diagram for H
+
3
SO1
SO2
SO3
MO1
MO3
MO2
atom 2 on left, atoms 1 and 3 on right
note colour coding: symmetric: orange; antisymmetric: green
only orbitals with the same symmetry interact
as usual, form bonding MO from in-phase overlap and
antibonding MO from out-of-phase overlap
Fig 4.4 MO diagram for H
+
3
SO1
SO2
SO3
MO1
MO3
MO2
MO1 is symmetric and bonding
MO3 is symmetric and antibonding
SO3 is the only antisymmetric orbital: it has nothing to overlap
with
SO3 becomes the nonbonding MO2
SO2 and SO3 have similar energies as little overlap between
non-adjacent atoms
Fig 4.5 Calculated MOs for H
+
3
MO1 MO2 MO3
these t closely with our simple MO picture
however, it turns out that H
+
3
is not linear but an equilateral
triangle
. . . use the same procedure
Fig 4.6 Triangular H
+
3
: effect of mirror plane
2
1
3
symmetric
swapped by
mirror plane
choose one mirror plane (dashed line)
AO on atom 1 reected into itself: symmetric
AO on atom 2 swapped with 3, likewise 3 swapped with 2
Fig 4.7 Symmetry orbitals
symmetric
antisymmetric
SO1 SO2
SO3
combine the AOs on atoms 2 and 3 to form SOs
symmetric (orange): SO2; antisymmetric (green): SO3
orbital on atom 1 forms the symmetric SO1
Fig 4.8 MO diagram for triangular H
+
3
SO2
SO1
MO1
MO3
MO2 SO3
SO2 has adjacent AOs with positive overlap; SO3 has
adjacent AOs with negative overlap
SO2 is lower in energy than SO3
SO3 is only antisymmetric SO; becomes nonbonding MO2
symmetric SOs, SO1 and SO2 overlap to give bonding MO1
and antibonding MO3
Fig 4.9 Calculated MOs for triangular H
+
3
MO1 MO3 MO2
1
3 2
these t closely with our simple MO picture
4.1.3 Optimum geometry for H
+
3
SO1
SO2
SO3
MO1
MO3
MO2
SO2
SO1
MO1
MO3
MO2 SO3
there are just two electrons, located in MO1
MO1 is lower in energy/more strongly bonding for the
triangular case than for the linear case . . .
. . . because there are three favourable interactions (one along
each edge) as opposed to only two in the linear case
Fig 4.10 Geometry optimization
60 100 140 180
e
n
e
r
g
y
/
lowest total energy with a bond angle of 60
computer programs which calculate MOs will also optimise

the geometry by seeking lowest energy
MOs of H
2
O: Fig 4.14 symmetry orbitals
SO1 SO2 SO4 SO5 SO3
symmetric symmetric symmetric antisymmetric
2s 2p
z 1s(A) 1s(B) 2p
y
swapped by mirror plane
antisymmetric
classify according to mirror plane
oxygen 2s and 2p
z
are symmetric; 2p
y
is antisymmetric
oxygen 2p
x
has node in plane of molecule: cannot overlap
with hydrogen 1s
as before, form two SOs from hydrogen 1s
Fig 4.15 MOs of H
2
O
MO1
MO2
2px
MO3
MO4
MO5
MO6
SO1
SO2
SO4
SO5
SO3
orange: symmetric; green: antisymmetric
SO1, SO2 and SO4 all overlap to give the symmetric MOs
MO1 lies below all the symmetric SOs; MO6 lies above
MO3 somewhere in the middle
Fig 4.15 MOs of H
2
O
MO1
MO2
2px
MO3
MO4
MO5
MO6
SO1
SO2
SO4
SO5
SO3
SO3 and SO5 all overlap to give the antisymmetric MOs (MO2
& MO5)
the oxygen 2p
x
is nonbonding (MO4)
8 electrons ll up to MO4; only one strictly nonbonding pair of
electrons (in MO4)
Fig 4.16 Computer-calculated MOs of H
2
O
MO1
MO2
MO3
MO4
Fig 4.17 Computer-calculated MOs of CH
4
MO1 MO2
MO3 MO4
going much further pretty hard . . .
. . . hybrid atomic orbitals provide a way forward
4.4 Hybrid atomic orbitals
problem with MOs is that the AOs do not necessarily point in
the right directions e.g. tetrahedral CH
4
several AOs overlap to form an MO, which is likely to be
spread over several atoms
a different approach: combine the AOs on one atom to form
new orbitals designed to point in the desired directions
these are called hybrid atomic orbitals, HAOs
an HAO can then overlap with just one other orbital to give a
bonding and an antibonding MO
4.4.1 sp
3
hybrids; Fig 4.18
(a) (b) (c) (d)
four sp
3
hybrids
x y
z
a b
c
d
HAOs formed from 2s and the three 2p
designed to point to the corners of a tetrahedron
Fig 4.19 contour plot of one of the sp
3
hybrids
-4 -6 -2 0 2 4 6
-4
-6
-2
0
2
4
6
note the directional properties
Fig 4.19 Describing bonding in CH
4
using sp
3
hybrids
*
sp
3 1s
C-H
one HAO overlaps with one hydrogen 1s to give a bonding
MO and a
antibonding MO
bonding MO concentrates electron density along the CH
direction
repeat for all four HAOs, giving four bonding MOs
2 electrons is each gives four two-centre two-electron bonds
Fig 4.21 CH
4
MO diagram using sp
3
hybrids
4()
4(*)
4(sp
3
)
2p
2s
4(1s)
note four HAOs giving four distinct and directional bonding
MOs
Describing the bonding in ethane using sp
3
hybrids
in each CH
3
fragment, three MOs formed by overlap of an
sp
3
HAO with a hydrogen 1s
remaining sp
3
HAO on each carbon overlaps with the same
orbital on the other carbon to give CC and
MOs
contour plots
*
C-C
4.4.2 sp
2
hybrids
these lie on a plane and point at 120
to one another: ideal for

describing doubly-bonded carbon compounds
ethene
C C
H
H H
H
4.4.2 sp
2
hybrids; Fig 4.24
(a)
a b
c
(b) (c) (d)
x y
z
three sp
2
hybrids 2p
z
three HAOs formed from 2s and two 2p AOs
lie in a plane, and pointing at 120
to one another
the remaining 2p AO (here 2p
z
) is not involved in forming the
HAOs and points out of the plane of the HAOs
Fig 4.25 Contour plots of sp
2
hybrids
(a) (b) (c)
y
x
-4 -6 -2 0 2 4 6
-4
-6
-2
0
2
4
6
note directional properties
Fig 4.26 bonding framework in ethene

*
sp
2
1s

*
sp
2
sp
2
sp
2
overlaps with hydrogen 1s to give CH and
sp
2
HAOs on different carbons overlap to give CC and
occupation of all the MOs accounts for 10 electrons

Fig 4.26 bonding in ethene

2p
z
2p
z
*
2p
z
AOs on each carbon overlap to give and
MOs
these have a nodal plane in the plane of the molecule (no
overlap between the and orbitals, therefore)
occupation of the MO accounts for the nal two electrons
Fig 4.27 Rotation about the bond in ethene
(a) (b) (c)
rotation about the CC bond reduces overlap between the 2p
z
AOs
if rotate through 90
then no overlap i.e. the bond is broken

origin of high barrier to rotation about a C=C bond
4.4.3 sp hybrids; Fig 4.28
(a)
a
b
(b) (c) (d)
two sp hybrids
2p
x
2p
y
z x
y
two HAOs formed from 2s and one 2p AO
HAOs point at 180
to one another
the remaining two 2p AOs (here 2p
x
and 2p
y
) are not involved
in forming the HAOs; these 2p AOs point perpendicular to the
line of HAOs
Fig 4.29 Contour plots of sp hybrids and unhybridized 2p
(a) (b) (c)
z
x
-4 -6 -2 0 2 4 6
-4
-6
-2
0
2
4
6
2p
x
note directional properties
Fig 4.30 Bonding in ethyne
*
sp
1s
*
sp sp
2p
x
2p
x
*
2p
y
2p
y
*
sp overlaps with hydrogen 1s to give CH and
sp HAOs on different carbons overlap to give CC and

Fig 4.30 Bonding in ethyne
*
sp
1s
*
sp sp
2p
x
2p
x
*
2p
y
2p
y
*
2p
x
MOs
2p
y
MOs
occupation of all the bonding MOs accounts for all 10
electrons
4.5 Comparing the hybrid and full MO approaches
we have already looked at the MO description of N
2
: involves
2s and 2p AOs, with signicant mixing between 2s and 2p
HAO approach: use sp hybrids on the nitrogen
overlap of two sp HAOs gives bonding and antibonding MO
other sp HAOs point away from bond and when lled become
lone pairs
overlap of 2p
x
and 2p
y
gives two bonding MOs and two
antibonding MOs
Fig 4.31 Comparing the hybrid and full MO approaches
*
*
2
g
3
g
2
u
3
u
(a) (b)
2p
2p
x,y
sp
d
sp
a
sp
b
sp
c
2s
2p
2s
1
u
1
g
AO AO HAO HAO
HAO: ()
2
()
4
(sp
c
)
2
(sp
d
)
2
i.e. bond, two bonds and two lone pairs
MO: (2
g
)
2
(2
u
)
2
(1
u
)
4
(3
g
)
2
i.e. two bonds and . . .
4.5.1 More about lone pairs
two electrons in out-of-plane 2p
x
AO in H
2
O are clearly
non-bonding and hence a lone pair
if both the bonding and the corresponding antibonding MOs
are lled, the result is no net bonding arising from the four
electrons
could describe this a two lone pairs
e.g. in N
2
(2
g
)
2
(2
u
)
2
is equivalent to two lone pairs, just as
in the HAO approach
e.g. in F
2
(2
g
)
2
(2
u
)
2
(1
u
)
4
(3
g
)
2
(1
g
)
4
is equivalent to two
lone pairs from lled MOs and four lone pairs from lled
MOs i.e. six lone pairs in total
4.6 Extending the hybrid concept
recall HAOs designed to point towards the other atoms
by varying the ratio of s to p in the hybrids can adjust the
angle between the hybrids
sp
sp
2
sp
3
%

s

c
h
a
r
a
c
t
e
r
/ degree
100 120 140 160 180
10
20
30
40
50
e.g. in H
2
O to obtain the required bond angle of 104.5
we
need 21% 2s in two of the hybrids (the other two have
proportionately more s character)
4.33 HAOs for H
2
O
HAO1 HAO2 HAO3 HAO4
x
y
z
x x
y
z
x
y
z
y
z
HAO1 and HAO2 point toward H, and form two-centre
two-electron bonds
HAO3 and HAO4 point away from the H atoms; occupied to
give two lone pairs
could describe the hybridization as approximately sp
3
4.7 Bonding in organic molecules: saturated systems
CH
3
F
CH
3
OH
CH
3
NH
2
can describe carbon as sp
3
hybridized
can assume the same for the F, O and N
HAOs not involved in bonding become lone pairs if lled
HOMO is lone pair (higher in energy than bonding pairs);
LUMO?
Fig 4.35 Identifying the LUMO
*
sp
3
sp
3
C-C
*
sp
3 1s
C-H
*
sp
3
1s
X-H
*
sp
3
sp
3
C-X
(a) (b) (c) (d)
X is an electronegative atom (lower energy AOs than carbon)
compared to CC, poorer energy match in CX so
not
raised in energy so much
hence CX
lower than CC
; former is the LUMO

same when comparing CH and XH; latter
is the LUMO
4.7.2 Aldehydes, ketones and imines
methanal
imine
can describe carbon as sp
2
hybridized; same for oxygen and
nitrogen
CO interaction involves overlap of two sp
2
HAOs to give a
bond
and two out-of-plane 2p AOs to give a bond
other HAOs on N and O lled to give lone pairs
HOMO is lone pair; LUMO is
(lower in energy than
)
4.7.4 Energy ordering of orbitals
as a general rule
highest energy
antibonding
antibonding
nonbonding orbitals (including lone pairs)
bonding
lowest energy bonding
in CH
3
X have already seen we need to choose between
different
MOs to identify LUMO

4.8 Delocalized bonding
C
C
C
C
C
C
H
H
H
H
H
H
benzene
R C
OH
O
R C
O
O
R C
O
O
(a)
(b) (c)
H
C
C
C
C
H
H
H
H
H
butadiene
examples of molecules with evidence for delocalized bonding
benzene is a regular hexagon: all CC bonds same length
CO bond length in carboxylate intermediate between COH
and C=O
in butadiene barrier to rotation about central CC bond is
signicantly greater than that for rotation about CC single
bond, but less than that for rotation about C=C double bond
4.8.1 Orbitals in a row
for a row of orbitals there is a simple way of nding the MOs
(a) number the atoms (here 14)
1 2 3 4
1 0 2 3 4 5
1 0 2 3 4 5
1 0 2 3 4 5
(a)
(b)
(c)
(d)
(b) add an extra atom at position 0 and position 5
(c) inscribe half sine-wave between 0 and 5
(d) orbital coefcients are proportional to the heights
4.8.1 Orbitals in a row
1 2 3 4
1 0 2 3 4 5
1 0 2 3 4 5
1 0 2 3 4 5
(a)
(b)
(c)
(d)
inscribed half sine wave gives the lowest energy MO
now inscribe two half sine waves between 0 and 5 to give next
highest energy MO
and then three half sine waves and so on
Fig 4.38 MOs for four orbitals in a row ( overlap)
1
2
3
4
one, two, three and four half sine wave to give four MOs
recall number of MOs = number of AOs
note increasing number of nodes as energy increases
Butadiene
H
C
C
C
C
H
H
H
H
H
butadiene
carbon sp
2
- carbon sp
2
carbon sp
2
- hydrogen 1s
carbon sp
2
hybridized: overlap to give framework
2p AOs out of plane of molecule: overlap to give four
delocalized MOs
four electrons in system: occupy 1 and 2 MOs
Fig 4.38 MOs of butadiene
1
2
conguration (1)
2
(2)
2
1 bonding between all adjacent atoms
2 bonding between 12 and between 34; antibonding
between 23
result is signicant bonding between 12 and 34, and
partial bonding between 23
Fig 4.38 Computed MOs of butadiene
HOMO
LUMO LUMO + 1
HOMO - 1
very similar to simple prediction
HOMO is 2; LUMO is 3
Allyl cation and allyl anion
H
C
C
C
H
H
H
H
allyl cation
H
C
C
C
H
H
H
H
allyl anion
ions thought to be planar and symmetrical
sp
2
hybridize carbons: overlap to form framework
three out of plane 2p AOs overlap to give system: three
orbitals in a row
Fig 4.1 MOs for allyl cation and allyl anion
1
2
3
anion cation
inscribe sine waves as before
1 bonding across adjacent atoms; 2 nonbonding
anion has 4 electrons: (1)
2
(2)
2
bonding entirely due to 1, but occupation of 2 increases
electron density on end atoms
Fig 4.1 MOs for allyl cation and allyl anion
1
2
3
anion cation
cation has 2 electrons: (1)
2
bonding entirely due to 1
highest electron density in middle
4.8.2 Resonance structures
H
C
C
C
H
H
H
H
allyl cation
H
C
C
C
H
H
H
H
allyl anion
H
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
H
benzene H
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
H
(a)
(d)
(g)
(a), (d) & (g) show different (localized) representations of the
structures: called resonance structures; connected by
on its own, each structure is inadequate; taken together they
are a more accurate representation
allyl cation
allyl anion
C
C
C
H
H
H
H
H
C
C
C
H
H
H
H
H
C
C
C
H
H
H
H
H
C
C
C
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
H
(b) (c)
(e) (f)
(h) (i)
C
C
C
C
C
C
H
H
H
H
H
H
(b)/(c) (e)/(f) (h)/(i) are alternative representations
note use of dashed bonds; partial charges indicated () or (+)
Fig 4.43 Resonance structures for butadiene
H
C
C
C
C
H
H
H
H
H
H
C
C
C
C
H
H
H
H
H
H
C
C
C
C
H
H
H
H
H
A B C
in order to place double bond between atoms 2 and 3, need to
draw resonance structures with charge separation (A and C)
these structures are higher in energy and so contribute less
contrast allyl ions where both resonance structures contribute
identically
each resonance structure is a possible localized
representation
not all resonance structures contribute equally
the molecule does not icker between resonance structures
delocalized MOs provide a more natural description of
delocalized bonding
4.9 Delocalized structures including heteroatoms
e.g. the carboxylate anion
carboxylate anion
R C
O
O
R C
O
O
resonance structures rationalize that fact that CO bond
length is intermediate between typical CO and C=O
alternatively, choose sp
2
hybrids for C and O . . .
. . . and form MOs from three out-of-plane 2p AOs
4.9.1 Carboxylate anion
approximate system by three 2p AOs in a row (not in fact
identical)
1 2 3
four electrons, occupy 1 and 2: partial bond across all
atoms and highest electron density on end atoms
computed MOs compare well
HOMO HOMO - 3 LUMO
4.9.2 Enolates
formed by removing a proton from a carbon adjacent to
carbonyl (the carbon)
H
3
C
C
H
O
C
C
H
O
H
H
base
C
C
H
O
H
H
C
C
H
O
H
H
A B
enolate
both resonance structures A and B contribute signicantly
model bonding in CCO as three atoms in a row
4.9.2 Enolates
approximate system by three 2p AOs in a row (not in fact
identical)
1 2 3
four electrons, occupy 1 and 2
computed MOs compare well
HOMO HOMO - 2 LUMO
computed charges 0.81 on oxygen, +0.34 on carbonyl
carbon, 0.62 on carbon
4.9.3 Amides
e.g. methanamide
H
C
NH
2
O
methanamide
X-ray diffraction data indicates a planar structure
taken to imply delocalized bonding over OCN fragment
4.9.3 Amides
computed MOs
HOMO HOMO - 2 LUMO
again reminiscent of three orbitals in a row
resonance structures: B must contribute signicantly
H
C
N
O
A B
H
H
H
C
N
O
H
H
Summary
can always nd the MOs using a computer program, but we
can make some useful predictions about the MOs using
pencil and paper
symmetry can help in forming MOs
hybrid atomic orbitals can be used to give a simple description
of the bonding
the MOs in simple delocalized systems can be constructed
using a geometric argument
for delocalized systems these MOs give a useful alternative
to the use of resonance structures
polyatomics
the end
Instituto de Qumica
James Keeler
5: Bonding in solids 178
5: Bonding in solids
Bonding in solids
types of bonding in solids:
molecular solids, which contain discrete molecules, held
together by weak interactions, such as hydrogen bonds
giant covalent solids, in which there is a network of covalent
bonds extending throughout the entire structure
metallic solids, in which there is extensive delocalization of the
electrons
ionic solids, in which it is the interactions between discrete
ions which hold the structure together
5.1 Metallic bonding: introducing bands
in a metal, electrons occupy orbitals which are delocalized
through the entire structure
formed in exactly the same way as MOs, but on a much larger
scale
the resulting sets of MOs are know as bands
to start with, think about this in one dimension only
Fig 5.1 Chain of s orbitals
number of atoms in chain
e
n
e
r
g
y
MOs arising from longer and longer chains of s orbitals
N AOs give N MOs
ranging from fully bonding between all adjacent orbitals to
fully antibonding
Fig 5.2 Density of states
e
n
e
r
g
y
density of
states
in the limit of large N, so many orbitals that the energy is quasi
continuous
density of states number of levels per unit energy greatest
at lowest and highest energies
these MOs called crystal orbitals (COs) form a band
Fig 5.3 Formation of a band
e
n
e
r
g
y
decreasing
spacing
increasing
interaction
b
o
n
d
i
n
g
C
O
s
a
n
t
i
b
o
n
d
i
n
g
C
O
s
range of energies as a function of separation
at large separation, no interaction energy same as AO
as separation decreases, interaction increases so separation
between most bonding and most antibonding CO increases:
bandwidth increases
note half bonding and half antibonding COs
5.1.2 Conduction of electricity
partially filled band
e
n
e
r
g
y

+
+
+
+
+
+
+
+
+
+
-
-
-
-
-
-
-
-
-
-
(a) (b) (c)
key feature of metals is that they conduct electricity
this is due to bands being partially lled
an applied electric eld shifts the energies of the COs (up at
negative end, down at positive)
electrons can cascade down in energy from lled to empty
COs: hence conduction
5.1.2 Conduction of electricity
filled band
e
n
e
r
g
y

+
+
+
+
+
+
+
+
+
+
-
-
-
-
-
-
-
-
-
-
(d) (e) (f)
now consider case of a full band
COs still shift in energy . . .
. . . but no empty lower energy COs for electrons to cascade
down into
hence insulator
5.1.3 Bands in three dimensions / overlapping bands
same basic idea applies in three dimensions, but resulting
bands more complex
overlap between AOs in different directions will be different
bands may overlap: for example bands arising from 2s and
from 2p
s

b
a
n
d
p

b
a
n
d
(a) (b)
rather than lling the top of s band, electrons ll the bottom of
p band as this lowers overall energy: complex pattern of band
occupancy
5.1.3 Overlapping bands
N orbitals overlap to give N COs that form a band
it takes 2N electrons to ll this band
in Li, band from 2s is half full, but in Be band is completely full
insulator?
Be is a metal, so presumably another band overlaps (e.g. 2p)
s

b
a
n
d
p

b
a
n
d
(a) (b)
5.1.5 Band gaps and semiconductors
e
n
e
r
g
yband gap
c
o
n
d
u
c
t
i
o
n
b
a
n
d
v
a
l
e
n
c
e
b
a
n
d
separation between full and empty band is called the band
gap
lled band is called the valence band; empty band is called
the conduction band
if band gap is large, the material is an insulator (full band)
5.1.5 Band gaps and semiconductors
if band gap is small enough, electrons can be thermally
excited to the conduction band
now have a partially lled (conduction) band, so material will
conduct . . .
. . . but not very well a semiconductor
conductivity increases with increasing temperature as more
electrons are promoted to conduction band
opposite to a metal, where conductivity decreases with
increasing temperature
Band gaps from Group 14 elements
measured band gaps
band gap
element / eV / kJ mol
1
C (diamond) 6.0 580
Si 1.1 107
Ge 0.67 64.2
Sn 0.08 7.7
Sn 0 0
Pb 0 0
C insulator; Si & Ge semiconductors; Sn and Pb metals
Band gaps from Group 14 elements
in solid with tetrahedral coordination can assume sp
3
hybridization at each atom
overlap of sp
3
on adjacent atoms gives and
MO
these then overlap to give a band (full; the valence band)
and a
band (empty; conduction band)

band structure varies down group
*
C Si Ge Sn
band gap depends on energy separation of and
MOs,
and interaction between these orbitals as the band is formed
from these MOs: opposing factors
5.2 Ionic solids
ionic solids are held together by electrostatic interaction
between (charged) ions
lattice enthalpy: energy released on forming lattice from
gaseous ions
M
+
(g) + X
(g) MX(s)
values can be determined experimentally using BornHaber
cycle
values can be estimated using the simple ionic model
5.2.1 The ionic model for lattice enthalpies
assume the ions are hard spheres with an electrostatic
interaction and a short-range repulsive term
resulting expression
H
lattice
= N
A
A
z
+
z
e
2
4
0
r
e
_
1
1
n
_
N
A
Avogadros constant
A Madelung constant (depends on crystal structure)
z
numerical charges on the ions

n parameter describing repulsion term (n = 9 . . . 12)
r
e
separation of ions in lattice
can assign (and tabulate) radii of individual ions and hence
compute r
e
= (r
+
+ r
)
5.2.3 The Kapustinskii equation
a more approximate, but still useful, expression for the lattice
enthalpy
H
lattice
/ kJ mol
1
1.07 10
5
n
ions
z
+
z
(r
+
+ r
)/pm
n
ions
is the number of ions in the formula unit e.g. 2 for NaCl,
3 for CaF
2
table of ionic radii (subject to considerable variation)
ion r+ / pm ion r+ / pm ion r / pm ion r / pm
Li
+
68 O
2
142 F
133
Na
+
100 Mg
2+
68 S
2
184 Cl
182
K
+
133 Ca
2+
99 Se
2
197 Br
198
Rb
+
147 Sr
2+
116 Te
2
217 I
220
Cs
+
168 Ba
2+
134
5.2.4 Validity of the ionic model
0.0020 0.0025 0.0030 0.0035 0.0040 0.0045 0.0050 0.0055
500
600
700
800
900
1000
1100
Group I halides
Cu(I) halides
Tl(I) halides
Ag(I) halides
1/(r+ + r-) / pm-1
-
la
t
t
ic
e

e
n
e
r
g
y

/

k
J

m
o
l -
1
lattice energy plotted against 1/(sum of ionic radii); dashed
line is prediction of Kapustinskii equation
good agreement for Group 1 halides
much poorer agreement for Tl(I), Ag(I) and Cu(I) halides;
lattice energies greater than predicted by ionic model
attributed to a covalent contribution to the lattice energy
5: Bonding in solids
the end
Instituto de Qumica
James Keeler
6: Thermodynamics and the Second Law 198
6: Thermodynamics and
the Second Law
Important questions
what determines whether or not a reaction will go?
what determines the position of equilibrium?
it is the Second Law of Thermodynamics that controls these
things
key relationships
r
G
= RT ln K
r
G
=
r
H
T
r
S
r
G
: standard Gibbs energy change;

r
H
: standard
enthalpy change;
r
S
: standard entropy change for the

reaction
6.1 Spontaneous processes
a spontaneous process is something that goes without
intervention from us e.g.
NH
3
(g) + HCl(g) NH
4
Cl(s)
the reverse does not happen (but we can intervene to make it
happen)
more subtly, reactions come to a position of equilibrium
dened by a particular value of K e.g.
CH
3
COOH + H
2
O CH
3
COO
+ H
3
O
+
K =
[CH
3
COO
][H
3
O
+
]
[CH
3
COOH][H
2
O]
the approach to equilibrium is spontaneous; when we reach
equilibrium, there is no further change
Is energy minimization the criterion
for a spontaneous process?
reaction goes because the products are more stable than the
reactants
more stable means lower energy . . .
. . . so heat is given out?
e
n
e
r
g
y
reactants
products
+ heat
thus spontaneous reactions must be exothermic
WRONG!
Spontaneous endothermic processes
dissolving NH
4
NO
3
(s) in water
the equilibrium 2 NO
2
(g) N
2
O
4
(g)
2 NO
2
N
2
O
4
exothermic
low pressure
100% NO
2
high pressure
100% N
2
O
4

atmos. pressure
70% NO
2

N
2
O
4
2 NO
2
endothermic
exothermic
2 NO
2
(g) N
2
O
4
(g)
endothermic
N
2
O
4
(g) 2 NO
2
(g)
6.2 Properties of matter: state functions
the density of a material is independent of how that material is
prepared: it is a property of matter a state function
state dened by temperature, pressure etc.
enthalpy, H, is a state function
the enthalpy change,
r
H, for
H
2
(g) +
1
2
O
2
(g) H
2
O(g)
has a xed value (at given temperature)
we will identify two other important state functions: entropy
and Gibbs energy
6.3 Entropy and the Second Law
the Second Law controls whether or not a process will be
spontaneous
Second Law: In a spontaneous process, the entropy of
the Universe increases
but what is entropy? how can we measure it? how can we
measure its change for the Universe?
to start with we will take a microscopic view of entropy
it is often said that entropy is randomness but what does
this actually mean and how can we use this concept?
6.3.1 A microscopic view of entropy
molecules have a large number of energy levels available to
them
e.g. energy levels due to translation, rotation and vibration
in a macroscopic sample there are an extremely large number
of ways that the molecules could be arranged amongst the
energy levels
it is quite impossible to know the details, but we can fall back
on a statistical approach
this leads to a (microscopic) denition of entropy
A simple example
14 molecules
energy levels 0, 1, 2, . . . in arbitrary units
total energy is 10 units
think about how we can arrange the 14 particles in the energy
levels such that the total energy is 10
A simple example
one possible distribution is
energy,
i
0 1 2 3 4 5
population, n
i
8 3 2 1 0 0
check number 8 + 3 + 2 + 1 + 0 + 0 = 14
check energy
E = n
0
0
+ n
1
1
+ n
2
2
+ n
3
3
. . .
= 8 0 + 3 1 + 2 2 + 1 3
= 10
how many ways can we arrange the molecules in the energy
levels and achieve this distribution?
A simple example
how many ways can we arrange the molecules in the energy
levels and achieve this distribution?
energy,
i
0 1 2 3 4 5
population, n
i
8 3 2 1 0 0
a simple combinatorial problem
W =
N!
n
1
! n
2
! n
3
! . . .
where e.g. 5! = 5 4 3 2 1 and 0! = 1
in this case N = 14, n
0
= 8, n
1
= 3, n
2
= 2 and n
3
= 1, so
W = 1.8 10
5
even for just 14 molecules there are very many possible ways
of achieving this distribution
Other distributions
another possible distribution with 14 molecules and 10 units of
energy
energy,
i
0 1 2 3 4 5
population, n
i
12 0 0 0 0 2
for which W = 91
another possibility
energy,
i
0 1 2 3 4 5
population, n
i
10 1 1 1 1 0
for which W = 2.4 10
4
and on and on . . .
Fig 6.2 Possible distributions
the three we have considered so far
0
1
2
3
4
5
6
7
(a) (b) (c)
(a) W = 1.8 10
5
, (b) W = 91, (c) W = 2.4 10
4
The most probable distribution
can be shown that one distribution has the largest value of W
this is the one for which the populations n
i
obey the
Boltzmann distribution
n
i
= n
0
exp
_
i
k
B
T
_
i
is the energy, T is the temperature, and k
B
is the Boltzmann
constant
populations fall off exponentially with the energy, and more
slowly at higher temperatures
e
n
e
r
g
y
population
low T high T
Entropy and the most probable distribution
for large numbers of molecules it turns out that the most
probable distribution is effectively the only distribution which
occurs
recall that this is the Boltzmann distribution
Boltzmann hypothesized that
S = k
B
ln W
max
where W
max
is the number of ways that the most probable
distribution can be achieved and S is the entropy
units of S are J K
1
or J K
1
mol
1
Fig 6.2 Possible distributions
the three we have considered so far
0
1
2
3
4
5
6
7
(a) (b) (c)
(a) has the largest W and is the one which obeys the
Boltzmann distribution
Using Boltzmanns denition of entropy
recall S = k
B
ln W
max
this puts in a quantitative and precise form the idea that
entropy is randomness: in fact, entropy is related to the
number of ways that molecules can be arranged amongst
energy levels
can use this to understand how entropy responds to various
changes
e.g. heating, expansion, molecular mass, change of state
Fig 6.4 Heating the sample
heating means putting in energy, so molecules promoted to
higher energy levels
for example
0
1
2
3
4
5
(a) (b)
increase
energy
W = 1.8 X 10
5
W = 2.5 X 10
6
Boltzmann distribution in each case
heating increases W and hence the entropy increases
Fig 6.5 Effect of temperature
effect of adding a xed amount of energy (here 5 units)
0
1
2
3
4
5
(a) cool (b) warm (c) hot
4.0 X 10
3
1.8 X 10
5
2.5 X 10
6
(a) is cool, (b) is warm and (c) is hot i.e. temperature
reects the amount of energy
W increases by more in going cool warm, than warm hot
when certain amount of energy is absorbed, the increase in
entropy is greater the lower the temperature
Fig 6.6 Expanding a gaseous sample
quantum mechanics tells us that when a gas is expanded the
(translational) energy levels get closer together
e.g.
0
1
2
3
4
5
(a) (b)
decrease
spacing
W = 1.8 X 10
5
W = 1.5 X 10
7
decreasing the spacing increases W
expanding a gas increases the entropy
Increasing the molecular mass
quantum mechanics tells us that when the mass of a molecule
increases the (translational) energy levels get closer together
hence, as with expanding a gas, W increases
heavier molecules have greater entropy than lighter ones (all
other things being equal)
Changes of state
in a gas molecules are free to move, and hence have many
translational energy levels
in a solid, the molecules are not free to move, and so have
signicantly fewer energy levels available
for liquids, the situation is intermediate
hence entropy of gas > liquid > solid
Summary
the entropy increases with temperature i.e. as energy is
supplied to the system, its entropy will increase
absorption of a given amount of energy gives rise to a larger
increase in entropy the lower the initial temperature
the entropy increases as a gas is expanded, and decreases
as a gas is compressed
the entropy of a gas increases as the mass of the
atoms/molecules increases
the entropy of the gaseous state of a substance is greater
than that of the liquid state, which in turn is greater that the
entropy of the solid state
The way forward
you may have come across the idea that entropy is
randomness; but what is randomness?
we have seen that entropy is related to the number of ways
that molecules can be arranged amongst energy levels
the is quantiable (unlike randomness)
to proceed further we need to use a different, but entirely
equivalent, denition of entropy in terms of heat
What is heat?
a form of energy involved in bringing a hot object in contact
with a cool object to a common temperature
hot
warm
cold
heat
we talk about a ow of heat, but it is not a substance or uid
heat is not a property of matter: it is something that happens
Reversible heat
a reversible process is one whose direction can be changed
by a very small change in some variable
for example
T + T
T
T - T
T
A
B
A
B
a small temperature difference T leads to a ow of heat
changing the difference from +T to T alters the direction of
ow: process is therefore reversible
if a nite temperature difference, then process is not reversible
Internal energy and enthalpy
internal energy (U) and enthalpy (H) are both state functions
they are properties of matter
the change in internal energy U is equal to the heat q under
conditions of constant volume
the change in enthalpy H is equal to the heat q under
conditions of constant pressure
for chemists, constant pressure is most common, so we tend
to use enthalpy
Entropy in terms of heat
can dene entropy in terms of heat instead of in terms of W:
entirely equivalent approaches
for a process at temperature T
sys
involving transfer of heat
q
rev
change in entropy =
q
rev
T
sys
note qualication that the heat has to be reversible (we will
come back to this)
two immediate consequences
1. supplying heat (energy) increases the entropy (q positive)
2. the lower the temperature, the greater the increase in entropy
these are exactly what we found before
6.5.1 Measuring entropy
entropy is a property of matter, so we can tabulate its value for
substances
method of determining the entropy involves measuring heat
capacities
extensive tabulations available (values depend on
temperature)
absolute entropies: entropy goes to zero at absolute zero
Recap: 6.3 Entropy and the Second Law
the Second Law controls whether or not a process will be
spontaneous
Second Law: In a spontaneous process, the entropy of
the Universe increases
how can we measure the entropy change for the Universe?
6.6 Calculating the entropy change of the Universe
factorize the Universe into the thing we are interested in the
system and everything else the surroundings
Universe
system
surroundings
we think of as
compute entropy change of each part separately
S
univ
= S
surr
+ S
sys
S
sys
from tabulated data
Entropy change of the surroundings
entropy change of surroundings only due to heat ow between
system and surroundings
heat ows in the opposite sense from point of view of system
and surroundings
system
surroundings
q
sys
positive
q
surr
negative
q
surr
= q
sys
as surroundings are very large, heat is reversible from the
point of view of the surroundings
Entropy change of the surroundings
use the denition of entropy (nite change)
S
surr
=
q
rev,surr
T
surr
heat of the surroundings is reversible
S
surr
=
q
surr
T
surr
constant pressure q
sys
= H
sys
; also q
surr
= H
sys
hence
S
surr
=
q
surr
T
surr
=
H
sys
T
surr
Entropy change of the Universe
separation
S
univ
= S
surr
+ S
sys
S
surr
in terms of H
sys
to give
S
univ
=
H
sys
T
surr
.,,.
surroundings
+ S
sys
.,,.
system
this is an important and practical relationship
by inspecting the sign of S
univ
can work out if a process is
spontaneous
6.6.1 Putting the Second Law to work: how to make ice
we know that liquid water freezes to give ice provided the
temperature is below 0

C
in other words, the process is spontaneous below this
temperature
liquid water ice is exothermic and involves a reduction in
entropy of the system
compute the entropy change of the Universe in the usual way
S
univ
=
H
sys
T
surr
.,,.
positive for water ice
+ S
sys
.,,.
negative for water ice
entropy change of the Universe
S
univ
=
H
sys
T
surr
.,,.
positive for water ice
+ S
sys
.,,.
negative for water ice
S
univ
will be positive, and the process spontaneous, if the
rst term is more positive than the latter term is negative
in other words, the entropy increase of the surroundings must
compensate for the entropy decrease of the system
this is just a question of making the temperature low enough,
as lowering the temperature results in a larger increase in
entropy of the surroundings
Fig 6.12 Making ice
liquid water ice
reduction in entropy of system, S
sys
< 0
increase in entropy of surroundings, S
surr
> 0
exothermic, H
sys
< 0
for the process to be spontaneous the temperature must be
low enough for the increase in entropy of the surroundings to
compensate for the decrease in entropy of the system
can put in some numbers to make the point: enthalpy of
freezing of liquid water is 6.01 10
3
J mol
1
, and entropy
change is 22.0 J K
1
mol
1
calculate S
univ
at 10

C, 263 K
S
univ
=
H
sys
T
surr
+ S
sys
=
6.01 10
3
263
22.0
= 22.9 22.0
= +0.9 J K
1
mol
1
S
univ
is positive entropy of Universe increases process
is spontaneous according to Second Law
repeat calculation at +10

C, 283 K
S
univ
=
H
sys
T
surr
+ S
sys
=
6.01 10
3
283
22.0
= 21.2 22.0
= 0.8 J K
1
mol
1
S
univ
is negative entropy of Universe decreases
process is not allowed according to Second Law
repeating calculation at 0

C, 273.15 K, gives S
univ
= 0; this
is the condition for equilibrium
Spontaneous endothermic processes
endothermic processes have positive H
sys
recall that
S
univ
=
H
sys
T
surr
.,,.
surroundings
+ S
sys
.,,.
system
for an endothermic process entropy of surroundings will
decrease . . .
. . . so entropy of Universe can only increase if the entropy of
the system increases sufciently
in order to be spontaneous, endothermic processes must
be accompanied by an increase in entropy of the system
6.6.2 Summary
S
univ
=
H
sys
T
surr
+ S
sys
S
univ
> 0 for a spontaneous process
S
univ
= 0 at equilibrium
a process in which the entropy of the system decreases can
be spontaneous provided that H
sys
is sufciently negative
and T
surr
is low enough
an endothermic process can be spontaneous provided that
S
sys
is sufciently positive and T
surr
is high enough
6.7 Gibbs energy
a more convenient way of working out the consequences of
the Second Law
denition of the Gibbs energy, G
G = H TS
for a change at constant temperature
G
sys
= H
sys
T
sys
S
sys
now divide by T
sys
G
sys
T
sys
=
H
sys
T
sys
+ S
sys
assume system and surroundings at same temperature
6.7 Gibbs energy
compare
G
sys
T
sys
=
H
sys
T
sys
+ S
sys
with
S
univ
=
H
sys
T
sys
+ S
sys
it follows that
G
sys
T
sys
= S
univ
in other words G
sys
/T
sys
is the same as S
univ
6.7 Gibbs energy
we have shown
G
sys
T
sys
= S
univ
in a spontaneous process, entropy of Universe increases,
therefore Gibbs energy of system must decrease
convenient as Gibbs energy just refers to the system
the Second Law can be restated as in a spontaneous process
the Gibbs energy of the system decreases i.e. G
sys
< 0
at equilibrium, G
sys
= 0
6.7.1 Making ice again
recall for liquid water ice, H is 6.01 kJ mol
1
, and S is
22.0 J K
1
mol
1
at 263 K
G = H T S
= 6.01 10
3
263 (22.0)
= 224 J mol
1
G < 0 process is spontaneous
at 283 K
G = 6.01 10
3
283 (22.0)
= +216 J mol
1
G > 0 process is not spontaneous
6.7.2 Summary
G = H T S
for a process taking place at constant temperature
G = H T S, where all of the quantities refer to the
system
G/T is the entropy change of the Universe
for a process to be spontaneous, the Gibbs energy must
decrease i.e. G must be negative
at equilibrium, there is no further change in Gibbs energy i.e.
G = 0
6.8 Chemical equilibrium
key relationships
r
G
= RT ln K
r
G
=
r
H
T
r
S
K: equilibrium constant;
r
G
: standard Gibbs energy

change;
r
H
: standard enthalpy change;

r
S
: standard
entropy change for the reaction
derivation of these is too involved for the present course
but we can appreciate why they arise and their consequences
Fig 6.13 The approach to equilibrium
decreasing Gibbs energy of pure products
G

p
u
r
e

r
e
a
c
t
a
n
t
s

p
u
r
e

p
r
o
d
u
c
t
s

(a)
Gibbs energy is a function of composition meaning the
amount (or ratio) of reactants and products
G falls in a spontaneous process
starting from any composition we end up at the point with
lowest G: this is the position of equilibrium
decreasing Gibbs energy of pure products
G

p
u
r
e

r
e
a
c
t
a
n
t
s

p
u
r
e

p
r
o
d
u
c
t
s

(a)
note that as the Gibbs energy of the pure products falls, the
position of equilibrium moves towards the products
this means that the equilibrium constant, K, increases
it turns out that K depends on the difference in Gibbs energy
between pure products and pure reactants
decreasing Gibbs energy of pure reactants
G

p
u
r
e

r
e
a
c
t
a
n
t
s

p
u
r
e

p
r
o
d
u
c
t
s

(b)
note that as the Gibbs energy of the pure reactants
decreases, the position of equilibrium moves towards the
reactants
this means that the equilibrium constant, K, decreases
K depends on the difference in Gibbs energy between pure
products and pure reactants
6.8.2 Writing the equilibrium constant
for the equilibrium
aA + bB cC + dD
we usually write the equilibrium constant K as
K =
[C]
c
[D]
d
[A]
a
[B]
b
however, strictly speaking all concentrations should be divided
by the standard concentration, c
, to give
K =
([C]/c
)
c
([D]/c
)
d
([A]/c
)
a
([B]/c
)
b
this makes K dimensionless
6.8.3 The standard Gibbs energy change
for the equilibrium
aA + bB cC + dD
the standard Gibbs energy change is dened as the change in
Gibbs energy when a moles of A react with b moles of B to
give c moles of C and d moles of D, with all of the substances
being in their standard states
standard states (all at stated temperature)
phase denition of standard state
gas the pure gas at a pressure of 1 bar
liquid the pure liquid
solid the pure solid
solution an (ideal) solution with the solute at the standard
concentration of 1 mol dm
3
6.8.3 The standard Gibbs energy change
for the equilibrium
2H
2
(g) + O
2
(g) 2H
2
O(g)

r
G
is the change in Gibbs energy change when two moles

of pure H
2
and one mole of pure O
2
, unmixed, go to two
moles of pure H
2
O, all species at 1 bar pressure and at the
stated temperature

r
G
, and hence K, only depends on the Gibbs energies of

the pure species
this is why this relationship is so useful, since the Gibbs
energies of pure substances can be tabulated
6.9 Finding the standard Gibbs energy change
to use
r
G
= RT ln K
r
G
=
r
H
T
r
S
we need to be able to nd
r
G
do this by nding
r
H
using tabulated standard enthalpies of

formation
and by nding
r
S
using tabulated standard absolute

entropies
6.9.1 Finding the standard enthalpy change,
r
H
the standard enthalpy of formation of a compound,

f
H
, is
dened as the enthalpy change when one mole of that
compound is formed from its constituent elements in their
reference states, all species being present in their standard
states
from which it follows that
r
H
=
_
sum of
f
H
of products
_
_
sum of
f
H
of reactants
_
diagramatically
-
a

f
H
(
A
)
-
b

f
H
(
B
)
c

f
H
(
C
)
d

f
H
(
D
)
r
H
aA + bB cC + dD
elements in their
reference states
6.9.2 Finding the standard entropy change,
r
S
tabulated data of standard absolute entropies S
m
are available
from which it follows that
r
S
=
_
sum of S
m
of products
_
_
sum of S
m
of reactants
_
and then
r
G
=
r
H
T
r
S
and then
r
G
= RT ln K
6.9.5 Temperature dependence
recall that
r
G
=
r
H
T
r
S
generally
r
H
and
r
S
have only a weak temperature

dependence, but as
r
G
includes the term T

r
S
,
r
G
can
be strongly temperature dependent
also recall
r
G
= RT ln K, hence
r
H
T
r
S
= RT ln K
so expect K to be temperature dependent
rearrange:
ln K =
r
H
RT
+
r
S
R
hence temperature dependence of K depends on
r
H

6.10 Interpreting the value of
r
G
recall
r
G
= RT ln K, divide by RT to give
r
G
RT
= ln K
take logarithms
K = exp
_
r
G
RT
_
sign of
r
G
determines whether reactants or products are

favoured at equilibrium
r
G / RT
-2 -1 1 0 2
1
2
3
4
K
products
favoured
reactants
favoured
r
G
negative
r
G
means products favoured, positive

r
G
means
reactants favoured
positive
r
G
does not mean that the reaction will not go, but
just that products are favoured (K < 1)
equilibrium composition for A B
r
G / RT
r
G / kJ mol
-1
%B %B
-4 -2 0 2 4 -10 -15 -5 0 5 10 15
20
40
60
80
100
20
40
60
80
100
(a) (b)
r
G
-60 -40 -20

10
2
10
-2
10
-4
10
-6
10
-8
10
-10
10
-12
10
4
10
6
10
8
10
10
10
12
20 40 60
r
G
o
/ kJ mol
-1
K

(
lo
g

s
c
a
le
) 100 K
298 K
800 K
products
favoured
reactants
favoured
note the logarithmic scale
at 298 K, if
r
G
> 30 kJ mol
1
K is so small that essentially
no products formed
if
r
G
< 30 kJ mol
1
K is so large that essentially reaction
goes to completion
at higher temperature, K changes more slowly with
r
G

6.12
r
H
and
r
S
for reactions involving ions in solution

we want to think about the dissolution equilibrium
NaCl(s) Na
+
(aq) + Cl
(aq)
equilibrium constant, and hence solubility, depends on a
subtle balance between enthalpy and entropy effects
we will rst look at how the standard entropy and enthalpy of
hydration of an ion varies
these values refer to the following process
M
z+ or z
(g) M
z+ or z
(aq, 1 mol dm
3
)
described as
hyd
H
and
hyd
S

Table 6.2 Standard enthalpies of hydration of ions
ion hydH
/ kJ mol
1
hydS
/ J K
1
mol
1
ionic radius / pm
Li
+
538 76
Na
+
424 102
K
+
340 138
Rb
+
315 152
Cs
+
291 167
Be
2+
2524 45
Mg
2+
1963 72
Ca
2+
1616 100
Sr
2+
1483 118
F
504 133
Cl
359 181
Br
328 196
I
287 220

hyd
H
is negative (as expected)

hyd
H
becomes more negative as size of ion decreases and

as charge increases
Table 6.2 Standard entropies of hydration of ions
ion hydH
/ kJ mol
1
hydS
/ J K
1
mol
1
ionic radius / pm
Li
+
141 76
Na
+
110 102
K
+
72.5 138
Rb
+
63.8 152
Cs
+
57.9 167
Be
2+
308 45
Mg
2+
329 72
Ca
2+
250 100
Sr
2+
203 118
F
139 133
Cl
76.3 181
Br
60.0 196
I
41.9 220

hyd
S
is negative; reduction in entropy due to restriction of

solvent around ion

hyd
S
becomes more negative as size of ion decreases and

as charge increases
6.13.1 Solubility of ionic solids
solubility determined by the equilibrium constant for the the
dissolution equilibrium
MX(s) M
+
(aq) + X
(aq)
analyse using Hess cycle
MX(s)
M
+
(g)
X
-
(g)
M
+
(aq)
X
-
(aq)
4
1
2
3
+ +
need to look at how each term varies with M and X
equilibrium constant depends on a subtle balance between
enthalpy and entropy effects
6.13.1 Solubility of ionic solids NaCl
r
G
o
r
H
o
-
T

r
S
o
r
G
o
r
H
o
-
T

r
S
o
(a) (b)
-1200
-900
-600
-300
300
600
900
1200
-100
-75
-50
-25
25
50
75
100 MX(s)
M
+
(g)
X
-
(g)
M
+
(aq)
X
-
(aq)
4
1
2
3
+ +
(b) is ten-fold vertical scale expansion; plot T
r
S
as this is
added to
r
H
look at
r
H
for each step

1 strongly endothermic (breaking lattice)
2 and 3 strongly exothermic (solvation)
4 overall, just slightly endothermic
6.13.1 Solubility of ionic solids NaCl
r
G
o
r
H
o
-
T

r
S
o
r
G
o
r
H
o
-
T

r
S
o
(a) (b)
-1200
-900
-600
-300
300
600
900
1200
-100
-75
-50
-25
25
50
75
100 MX(s)
M
+
(g)
X
-
(g)
M
+
(aq)
X
-
(aq)
4
1
2
3
+ +
look at T
r
S
for each step

1 large increase in entropy (solid gas): T
r
S
negative
2 and 3 reduction in entropy (restriction of solvent): T
r
S
positive
4 overall, T
r
S
slightly negative
overall result T
r
S
more negative than

r
H
is positive:
r
G
is negative and NaCl has signicant solubility

6.13.1 Solubility of ionic solids LiF
r
G
o

r
H
o

-
T

r
S
o

r
G
o

r
H
o

-
T

r
S
o

(c) (d)
-1200
-900
-600
-300
300
600
900
1200
-100
-75
-50
-25
25
50
75
100
MX(s)
M
+
(g)
X
-
(g)
M
+
(aq)
X
-
(aq)
4
1
2
3
+ +
for LiF
r
H
of step 4 is just negative (i.e. solvation terms win)

but T
r
S
is positive due to unfavourable entropy of

solvation of two small ions
T
r
S
more positive than

r
H
is negative:
r
G
is positive
and LiF has very limited solubility
Fig 6.21 Comparing NaCl and LiF
r
G
o
r
H
o
-
T

r
S
o
r
G
o
r
H
o
-
T

r
S
o
r
G
o
r
H
o
-
T

r
S
o
r
G
o
r
H
o
-
T

r
S
o
NaCl LiF
(a) (b) (c) (d)
-1200
-900
-600
-300
300
600
900
1200
-1200
-900
-600
-300
300
600
900
1200
-100
-75
-50
-25
25
50
75
100
-100
-75
-50
-25
25
50
75
100
very subtle differences in the balance between terms account
for the high solubility and NaCl and the low solubility of LiF
Fig 6.22 Solubility of CaCO
3
r G
o

r H
o

-
T

r S
o

-2000
-1000
1000
0
2000
3000
MX(s)
M
+
(g)
X
-
(g)
M
+
(aq)
X
-
(aq)
4
1
2
3
+ +
much higher lattice energy and enthalpy of solvation due to
higher charge on ions; overall
r
H
very slightly exothermic

T
r
S
larger than for NaCl (again, effect of higher charges)

overall T
r
S
>
r
H
so
r
G
is positive: CaCO
3
is rather
insoluble an entropy effect
6.13.2 Acid strengths of HF and HCl
acid strength determined by the equilibrium
HX(aq) H
+
(aq) + X
(aq).
HF rather a weak acid, whereas HCl is strong
analyse using the Hess cycle
HX(aq)
HX(g) H(g) + X(g) H
+
(g) + X
-
(g)
H
+
(aq) + X
-
(aq)
1
4
5
2 3
(a) (b) (c)
-1500
-1000
-500
0
500
1000
1500
-80
-60
-40
-20
0
20
40
60
80
-60
-40
-20
0
20
40
60
HX(aq)
HX(g) H(g) +X(g) H
+
(g) +X
-
(g)
H
+
(aq) + X
-
(aq)
1
4
5
2 3
1
4 5
2 3
1
4 5
5
2
3
r
H
o

/

k
J

m
o
l -
1
-
T

r
S
o

/

k
J

m
o
l -
1
-
T

r
S
o
r
H
o
-
T

r
S
o
r
H
o
k
J

m
o
l -
1
data for HF
data for HCl
data for HF
data for HCl
HF
HCl
steps 1, 2 and 3 all endothermic, but 4 strongly exothermic as
involves solvation of ions
overall, slightly exothermic more so for HCl
(a) (b) (c)
-1500
-1000
-500
0
500
1000
1500
-80
-60
-40
-20
0
20
40
60
80
-60
-40
-20
0
20
40
60
HX(aq)
HX(g) H(g) +X(g) H
+
(g) +X
-
(g)
H
+
(aq) + X
-
(aq)
1
4
5
2 3
1
4 5
2 3
1
4 5
5
2
3
r
H
o

/

k
J

m
o
l -
1
-
T

r
S
o

/

k
J

m
o
l -
1
-
T

r
S
o
r
H
o
-
T

r
S
o
r
H
o
k
J

m
o
l -
1
data for HF
data for HCl
data for HF
data for HCl
HF
HCl
T
r
S
negative for steps 1 and 2 (dissociation), but

signicantly positive for step 4 (solvation)
overall, T
r
S
slightly positive more so for HF

(a) (b) (c)
-1500
-1000
-500
0
500
1000
1500
-80
-60
-40
-20
0
20
40
60
80
-60
-40
-20
0
20
40
60
HX(aq)
HX(g) H(g) +X(g) H
+
(g) +X
-
(g)
H
+
(aq) + X
-
(aq)
1
4
5
2 3
1
4 5
2 3
1
4 5
5
2
3
r H
o

/

k
J

m
o
l -
1
-
T

r S
o

/

k
J

m
o
l -
1
-
T

r S
o
r H
o
-
T

r S
o
r H
o
k
J

m
o
l -
1
data for HF
data for HCl
data for HF
data for HCl
HF
HCl
now look at (c), which compares HF and HCl
for HF the positive T
r
S
dominates, whereas for HCl the

negative
r
H
dominates
this outcome would have been hard to predict, as it involves a
very subtle balance between opposing factors
6.15 How much product is there at equilibrium?
this, of course, depends on the equilibrium constant, but the
connection is not so simple
consider the gas-phase equilibrium
A
2
(g) 2 A(g)
dene as the fraction of the initial dimer which has
dissociated
= 1 means complete dissociation; = 0 means no
dissociation
for the equilibrium A
2
(g) 2 A(g)
K =
(p
A
/p
)
2
p
A2
/p
=
p
2
A
p
A2
p
where p
is the standard pressure, and p

A
is the partial
pressure of A
can show that
K =
4
2
1
n
0
RT
p
V
where n
0
is the initial number of moles of A
2
, and V is the
volume of the vessel
recall
K =
4
2
1
n
0
RT
p
V
for small degrees of dissociation, << 1
K =
4
2
n
0
RT
p
V
hence =
_
Kp
V
4n
0
RT
_
1
2
as little dissociation number of moles is n
0
hence
pV = n
0
RT and so (n
0
RT)/V = p
substituting this for p
=
_
Kp
4p
_
1
2
hence as p increases, decreases: exactly what you would
expect on the basis of Le Chateliers principle
6: Thermodynamics and
the Second Law
the end
Instituto de Qumica
James Keeler
7: Trends in bonding 276
7: Trends in bonding
Trends in bonding
the periodic table
variation in orbital energy, size, ionization energy and electron
afnity
use these to discuss variation in bonding across the periodic
table
a very broad brush
7.1 Electronic conguration and the periodic table
lanthanides
actinides
17 18 16 15 14 13 2 1
3 4 5 6 7 8 9 10 11 12
s-block
d-block
f-block
p-block
period 1
period 2
period 3
period 4
period 5
period 6
period 7
[He]
[Ne]
[Ar]
[Kr]
[Xe]
[Rn]
Pr
59
-6s2
5d0
4f3
Ce
58
-6s2
5d1
4f1
Pm
61
-6s2
5d0
4f5
Nd
60
-6s2
5d0
4f4
Eu
63
-6s2
5d0
4f7
Sm
62
-6s2
5d0
4f6
Tb
65
-6s2
5d0
4f9
Gd
64
-6s2
5d1
4f7
Ho
67
-6s2
5d0
4f11
Dy
66
-6s2
5d0
4f10
Tm
69
-6s2
5d0
4f13
Er
68
-6s2
5d0
4f12
Lu
71
-6s2
5d1
Yb
70
-6s2
5d0
4f14
Pa
91
-7s2
6d1
5f2
Th
90
-7s2
6d2
5f0
Np
93
-7s2
6d1
5f4
U
92
-7s2
6d1
5f3
Am
95
-7s2
6d0
5f7
Pu
94
-7s2
6d0
5f6
Bk
97
-7s2
6d0
5f9
Cm
96
-7s2
6d1
5f7
Es
99
-7s2
6d0
5f11
Cf
98
-7s2
6d0
5f10
Md
101
-7s2
6d0
5f13
Fm
100
-7s2
6d0
5f12
No
102
-7s2
6d0
5f14
H
1
1s1
Be
4
-2s2
Li
3
-2s1
C
6
-2s2
2p2
B
5
-2s2
2p1
O
8
-2s2
2p4
N
7
-2s2
2p3
Ne
10
-2s2
2p6
He
2
1s2
F
9
-2s2
2p5
Mg
12
-3s2

Na
11
-3s1
Si
14
-3s2
3p2
Al
13
-3s2
3p1
S
16
-3s2
3p4
P
15
-3s2
3p3
Ar
18
-3s2
3p6
Cl
17
-3s2
3p5
Ca
20
-4s2
K
19
-4s1
Ti
22
-4s2
3d2
Sc
21
-4s2
3d1
Cr
24
-4s1
3d5
V
23
-4s2
3d3
Fe
26
-4s2
3d6
Mn
25
-4s2
3d5
Ni
28
-4s2
3d8
Co
27
-4s2
3d7
Zn
30
-4s2
3d10
Cu
29
-4s1
3d10
Ge
32
-4s2
4p2
Ga
31
-4s2
4p1
Se
34
-4s2
4p4
As
33
-4s2
4p3
Kr
36
-4s2
4p6
Br
35
-4s2
4p5
Sr
38
-5s2

Rb
37
-5s1
Zr
40
-5s2
4d2
Y
39
-5s2
4d1
Mo
42
-5s1
4d5
Nb
41
-5s1
4d4
Ru
44
-5s1
4d7
Tc
43
-5s2
4d5
Pd
46
-5s0
4d10
Rh
45
-5s1
4d8
Cd
48
-5s2
4d10
Ag
47
-5s1
4d10
Sn
50
-5s2
5p2
In
49
-5s2
5p1
Te
52
-5s2
5p4
Sb
51
-5s2
5p3
Xe
54
-5s2
5p6
I
53
-5s2
5p5
Ba
56
-6s2
Cs
55
-6s1
Hf
72
-6s2
5d2
La
57
-6s2
5d1
4f0
Ra
88
-7s2
Fr
87
-7s1
Ac
89
-7s2
6d1
5f0
W
74
-6s2
5d4
Ta
73
-6s2
5d3
Os
76
-6s2
5d6
Re
75
-6s2
5d5
Pt
78
-6s1
5d9
Ir
77
-6s2
5d7
Hg
80
-6s2
5d10
Au
79
-6s1
5d10
Pb
82
-6s2
6p2
Tl
81
-6s2
6p1
Po
84
-6s2
6p4
Bi
83
-6s2
6p3
Rn
86
-6s2
6p6
At
85
-6s2
6p5
periods; groups; blocks; electronic congurations
Fig 7.2 Orbital energies
O
r
b
ita
l e
n
e
r
g
y
/ e
V
Atomic Number
1s
2s
2p
3s
3p
3d
4s
4p
H
He
Li Na
K
Be B
C
N
O
F
Ne
Mg
Al
Si
P
S
Cl
Ar
Ca Sc Ti V
Cr
Mn Fe Co Ni
Cu
Zn
Ga
Ge
As
Se
Br
Kr
0 5 10 15 20 25 30 35
-45
-40
-35
-30
-25
-20
-15
-10
-5
0
explain trends using the concepts of penetration and
screening
for each successive element nuclear charge increased by one
and one electron added
Fig 7.2 Orbital energies
O
rb
ita
l e
n
e
rg
y
/ e
V
Atomic Number
1s 2s
2p
3s
3p
3d
4s
4p
H
He
Li Na
K
Be B
C
N
O
F
Ne
Mg
Al
Si
P
S
Cl
Ar
Ca Sc Ti V
Cr
Mn Fe Co Ni
Cu
Zn
Ga
Ge
As
Se
Br
Kr
0 5 10 15 20 25 30 35
-45
-40
-35
-30
-25
-20
-15
-10
-5
0
K Zn; 4s energy falls slowly as increased nuclear charge is
well screened from the 4s by the electron added to the 3d
from Ga onwards energy of 4s drops rapidly as this is not well
screened by electrons being added to 4p
as discussed before, s drops more quickly than p
7.2.1 The effective nuclear charge
recall from orbital energy E
n
can dene effective nuclear
charge Z
e
by assuming hydrogen-like energies
E
n
=
Z
2
e
R
H
n
2
n in the principal quantum number
hence
Z
e
=
_
n
2
E
n
R
H
if the other electrons perfectly screen the nucleus from the
electron of interest, Z
e
= 1
less than perfect screening results in a larger Z
e
Fig 7.4 Z
eff
for highest energy occupied orbital
0
2
4
6
8
10
12
14
16
0
2
4
6
8
10
12
14
16
1 3 5 7 9 11 13 15 17 2 4 10 8 6 12 14 16 18
Group Number
Cu Zn
B
C
Al
Ga
Si
P
S
Cl
Ge
As
Se
Br
Tl
Kr
In
Sn
Pb
Sb
Bi
Te
Po
I
At
Xe
Rn
Au
Hg
H
Na
K
Rb
Li
Cs
Be
Mg
Ca
Sr
Ba
Sc Ti V Cr Mn
Fe Co
Ir
Os
Re
W
Ta
Hf Lu
Cd
Ag
Ni
Pd
Pt
Rh Ru
Mo
Nb
Tc
Zr
Y
E
f f e
c
t i v
e
N
u
c
l e
a
r
C
h
a
r
g
e
, Z
e
f f
(
C
l e
m
e
n
t i )
N
O
F
Ar
Ne
He
Z
e
increases across a given period (same colour)
Z
e
increases down a given group
7.2.1 The effective nuclear charge
orbital energy increases as go down group, so how can Z
e
be
increasing?
recall
Z
e
=
_
n
2
E
n
R
H
as go down group E
n
decreases (E
n
become less negative),
but n
2
increases
the effect of increasing n dominates, so Z
e
increases down
the group
Fig 7.5 The Second Period anomaly
O
r
b
it
a
l
e
n
e
r
g
y

/

e
V
-40
-30
-20
-10
0
Group 1 Group 2 Group 13 Group 14 Group 15 Group 16 Group 17
s orbitals
p orbitals
Li Na
K Rb Cs
Be
Mg
Ca Sr
Ba
B
Al Ga In Tl
C
N
P As
Sb Bi
O
S
Se
Te Po
F
Cl
Br
I At
Si Ge Sn Pb
energies of s and p orbitals of the Second Period seem to be
lower than expected
for example: steady increase along the series SSeTePo,
but sharper increase on going from O to S
The Second Period anomaly
attributed to particularly small value of n, the principal
quantum number, for the Second Period (n = 2)
plot of 1/n
2
against n
principal quantum number, n
2 3 4 5 6
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
-
1
/
n
2
note large jump in 1/n
2
when n goes from 2 to 3
7.2.3 The effects of the d-block
O
r
b
it
a
l
e
n
e
r
g
y

/

e
V
-40
-30
-20
-10
0
Group 1 Group 2 Group 13 Group 14 Group 15 Group 16 Group 17
s orbitals
p orbitals
Li Na
K Rb Cs
Be
Mg
Ca Sr
Ba
B
Al Ga In Tl
C
N
P As
Sb Bi
O
S
Se
Te Po
F
Cl
Br
I At
Si Ge Sn Pb
note 4s (red circle) lower in energy than 3s (green circle) for
groups 13, 14 and 15 normally we would expect the 4s to
be higher
in these groups, in going from the Period 2 to the Period 3
elements Z has increased by 8
but from Period 3 to Period 4, Z has increased by 18 due to
lling the 3d
Fig 7.7 The effects of the d-block
2 3 4 5
0
5
10
Li
Be
Ca
Sr
Mg
Na B
N
P
Ga
As
I n
Br
Sb
I
Cl
F
Al
K
Rb 1
2
13
15
17
e
f
f
e
c
t
iv
e

n
u
c
le
a
r

c
h
a
r
g
e

period
g
r
o
u
p

look at from the point of view of Z
eff
Z
eff
increases steadily along BeMgCa
but for BAlGa extra jump on going AlGa due to lling
of 3d
7.2.5 Electronegativity and orbital energies
electronegativity is a beloved concept in chemistry
Pauling dened it as the power of an atom when in a
molecule to attract electrons to itself
he noticed that an AB bond was always stronger than the
average strength of AA and BB bonds
Paulings scale based on bond energies E
AA
, E
BB
and E
AB
E
AB

_
E
AA
E
BB
= C
_
A

B
_
2
A
and
B
are the electronegativities of A and B; C is a
constant
Fig 7.10 Correlation of electronegativity
with orbital energy
0 5 10 15 20 25 30
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
P
a
u
lin
g

e
le
c
t
r
o
n
e
g
a
t
iv
it
y
minus the weighted average orbital energy of s and p valence electrons / eV
F
O Cl
Br
I
Xe
Mg
Cs
K
Al
Zn Sn
Si
H
P
S
C
N
Kr
surprisingly good correlation between Paulings values and
(minus) the weighted orbital energies of the s and p
7.3 Atomic sizes across the periodic table
somewhat hard to dene what we mean by the size of an
atom
simple model relates atomic radius to Z
eff
and n (a
0
is Bohr
radius)
r =
a
0
n
2
Z
e
surprisingly good correlation
0 5 10 15 20 25 30 35
0
50
100
150
200
250
A
t
o
m
ic

r
a
d
iu
s

/

p
m
Atomic number
experimentally determined
Li
B
Al Sc
Ga
Na
K
Kr
Ar
Ne
He
modelled using r =
a0 n
2
Z
eff
Fig 7.12 Atomic radii
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
0 0
50 50
100 100
150 150
200 200
250 250
Group Number
A
t o
m
i c
R
a
d
i u
s
/ p
m
Tl
Ge
As Se
Br Kr
Pb Bi
Po
At? In
Sn Sb Te
I Xe
Rn
H
Na
K
Rb
Li
Cs
Be
Mg
Ca
Sr
Ba
Sc
Ti
V
Cr
W
Lu
Mo
Nb
Ta
Cu
Zn
Au
Hg
Mn Fe Co
Ir Os Re Cd
Ag
Ni
Pd
Pt
Rh Ru Tc
Zr
Hf
Y
Si
Al
P
S Cl Ar
B
C
N O F Ne
He
Ga
size maximum for Group 1 element and then decreases
across period
size increases down a group: increase in n dominates over
increase in Z
e
Fig 7.13 Atomic radii
2 3 4 5 6
50
100
150
200
Period
B
Al
Si
Tl
Pb
In
Sn
Ga
Ge
C
He
Ne
Ar
Kr
Xe
a
t
o
m
i
c

r
a
d
i
u
s

/

p
m
large increase in going from Period 2 to Period 3 element in
same group (effect of small value of n)
Ga smaller than Al (effect of lling the 3d)
7.3.1 Size, overlap and bond strengths
smaller valence orbitals generally overlap more effectively
than larger ones, hence giving stronger bonds
bond energies of the Group 1 diatomics (gas phase)
molecule H
2
Li
2
Na
2
K
2
Rb
2
Cs
2
bond strength / kJ mol
1
436 100 71 50 47 43
clear trend, with H
2
especially strong
Fig 7.14 Overlap integral of valence s orbitals
0 100 200 300 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
H2
H2
o
v
e
r
la
p

in
t
e
g
r
a
l
Internuclear separation / pm
K2
K2
Li2
Li2
for H (1s), Li (2s) and K (3s)
dashed lines show experimentally determine bond lengths
note larger overlap for smaller orbitals
7.4 Ionization energies and electron afnities;
Fig 7.15 ionization energies
1 3 5 7 9 11 13 15 17
S5
0
0
5
5
10
10
15
15
20
20
25
2 4 10 8 6 12 14 16 18
H
Na
K
Rb
Li
Cs
Be
Mg
Ca
Sr
Ba
Sc
Y
Ti V Cr
Mn Fe Co Cu
Zn
B
C
N
O
F
Ne
He
Al
Si
P S
Cl
Ar
As Se
Br
Tl
Kr
In
Sn
Pb
Sb
Bi
Te
Po
I
At
Xe
Rn
Au
Hg
Pt Ir
Os
Re W Ta
Hf
Lu
Group Number
F
i r
s
t I o
n
i z
a
t i o
n
E
n
e
r
g
y
/ e
V
Ge
Ga
recall IE is approximately minus the orbital energy
IE increases across period: due to increase in Z
eff
IE generally decreases down a group: due to increase in n
Fig 7.16 Second period anomaly again
Group 13
Group 14
Group 15
A
v
e
r
a
g
e

i
o
n
i
z
a
t
i
o
n

e
n
e
r
g
y

o
f

v
a
l
e
n
c
e

e
l
e
c
t
r
o
n
s

/

e
V
Period Period Period
B
Al Ga
In
Tl
C
Si Ge
Sn
Pb
N
P
As
Sb Bi
2 3 4 5 6 2 3 4 5 6 2 3 4 5 6
10
20
30
40
50
60
plotted quantity is average IE for removal of the valence
electrons e.g. for Group 13 average of rst three IEs
sharp drop in average IE when going from Period 2 to
Period 3 as we have seen before (small value of n)
small rise when going AlGa and SiGe as we have seen
before (lling of d block)
Fig 7.17 Electron afnities
17 18 16 15 14 13 2 1
3 4 5 6 7 8 9 10 11 12
s block
d block
p block
period 1
period 2
period 3
period 4
period 5
period 6
Lu
??
H
73
Be
0
Li
60
C
122
B
27
O
141
N
0
Ne
0
He
0
F
328
Mg
0

Na
53
Si
134
Al
43
S
200
P
72
Ar
0
Cl
349
Ca
2
K
48
Ti
8
Sc
18
Cr
64
V
51
Fe
16
Mn
0
Ni
112
Co
64
Zn
0
Cu
118
Ge
130
Ga
29
Se
195
As
78
Kr
0
Br
325
Sr
5

Rb
47
Zr
41
Y
30
Mo
72
Nb
86
Ru
101
Tc
53
Pd
54
Rh
110
Cd
0
Ag
126
Sn
116
In
29
Te
190
Sb
103
Xe
0
I
295
Ba
14
Cs
46
Hf
0
W
79
Ta
31
Os
106
Re
14
Pt
205
Ir
151
Hg
0
Au
223
Pb
35
Tl
19
Po
183
Bi
91
Rn
0
At
270
electron afnity, EA, is minus the energy for process
X(g) + e
(g)
the more positive the EA, the more favourable it is for an
electron to be attached to the atom
note high values for oxygen and halogens
17 18 16 15 14 13 2 1
3 4 5 6 7 8 9 10 11 12
s block
d block
p block
period 1
period 2
period 3
period 4
period 5
period 6
Lu
??
H
73
Be
0
Li
60
C
122
B
27
O
141
N
0
Ne
0
He
0
F
328
Mg
0

Na
53
Si
134
Al
43
S
200
P
72
Ar
0
Cl
349
Ca
2
K
48
Ti
8
Sc
18
Cr
64
V
51
Fe
16
Mn
0
Ni
112
Co
64
Zn
0
Cu
118
Ge
130
Ga
29
Se
195
As
78
Kr
0
Br
325
Sr
5

Rb
47
Zr
41
Y
30
Mo
72
Nb
86
Ru
101
Tc
53
Pd
54
Rh
110
Cd
0
Ag
126
Sn
116
In
29
Te
190
Sb
103
Xe
0
I
295
Ba
14
Cs
46
Hf
0
W
79
Ta
31
Os
106
Re
14
Pt
205
Ir
151
Hg
0
Au
223
Pb
35
Tl
19
Po
183
Bi
91
Rn
0
At
270
adding electron to an atom with a lled shell is unfavourable,
as electron has to go into orbital with larger n: e.g. Group 18
which have negative EAs
same is true for atoms with lled subshells: e.g. Group 2
where ns is full and electrons has to go into np, and Group 12
where nd is full
in Group 15 electron is added to half-lled shell: no increase
in exchange energy, lower EA than otherwise expected
17 18 16 15 14 13 2 1
3 4 5 6 7 8 9 10 11 12
s block
d block
p block
period 1
period 2
period 3
period 4
period 5
period 6
Lu
??
H
73
Be
0
Li
60
C
122
B
27
O
141
N
0
Ne
0
He
0
F
328
Mg
0

Na
53
Si
134
Al
43
S
200
P
72
Ar
0
Cl
349
Ca
2
K
48
Ti
8
Sc
18
Cr
64
V
51
Fe
16
Mn
0
Ni
112
Co
64
Zn
0
Cu
118
Ge
130
Ga
29
Se
195
As
78
Kr
0
Br
325
Sr
5

Rb
47
Zr
41
Y
30
Mo
72
Nb
86
Ru
101
Tc
53
Pd
54
Rh
110
Cd
0
Ag
126
Sn
116
In
29
Te
190
Sb
103
Xe
0
I
295
Ba
14
Cs
46
Hf
0
W
79
Ta
31
Os
106
Re
14
Pt
205
Ir
151
Hg
0
Au
223
Pb
35
Tl
19
Po
183
Bi
91
Rn
0
At
270
ignoring lled and half-lled shells, there is a general increase
in EA across a period: attribute to increase in Z
eff
of the orbital
into which the electron is going
not surprising, therefore, that halogens (Group 17) have the
greatest EAs
values of EAs for Period 2 elements are lower than would be
expected on basis of the rest of the members of the group . . .
Fig 7.18 Electron afnities second period anomaly
At
I
Br
Cl
F
Po
Te
Se S
O
(minus) valence orbital energy / eV
e
le
c
tr
o
n
a
ffin
ity
/ k
J
m
o
l -
1
8 10 12 14 16 18 20
100
200
300
400
500
?
?
Group 17
Group 16
132 kJ mol
-1

less than
expected
85 kJ mol
-1

less than
expected
might expect a correlation between (minus) the energy of the
orbital into which the electron is placed and the EA
in Groups 16 & 17 this works well for Periods 36, but the EAs
for Group 2 elements are less than would be predicted on this
basis
this may be due to the small size of F and O resulting in
greater electronelectron repulsion
7.5 Summary of the trends in orbital energies and sizes
orbitals energies follow a fairly regular pattern, decreasing
across a period, and increasing down a group
Z
eff
values (determined from orbital energies) generally
increase across a period and down a group
the trend in orbital energies (or effective nuclear charges)
provides an explanation for the trends in orbital sizes,
ionization energies and electron afnities
atomic sizes generally decrease across a period and increase
down a group
Period 2 elements often have anomalous properties when
compared to their other group members: e.g. lower orbital
energies; smaller sizes
7.6 Bonding in the elements non-metals
when an element bonds to itself there is automatically a good
energy match between the orbitals
recall in diatomics the strength of bonding depends on the
number of bonding and antibonding electrons
plot bond strength against number of electrons
1 2 3 4 5 6 7 8
0
200
400
600
800
1000
Li2
Be2
B2
C2
N2
O2
F2
Ne2
number of valence electrons per atom
b
o
n
d

s
t
r
e
n
g
t
h

/

k
J

m
o
l -
1
N
2
has all bonding MOs and only one antibonding MO lled;
others have fewer bonding or more antibonding electrons
Fig 7.20 Enthalpy of atomization of elements
Li
Be
B
C
Si
Ge
P
Al
Ga Ca
Mg
Na
K
As
Se
O
Cl
Br
N
S
F
s
ta
n
d
a
r
d
e
n
th
a
lp
y
o
f a
to
m
iz
a
tio
n
/ k
J
m
o
l -
1
1 2 3 4 5 6 7
0
100
200
300
400
500
600
700
800
number of valence electrons per atom
plot enthalpy of atomization; in most cases of a solid
in contrast to diatomics, reaches a maximum for carbon;
similarly for later periods, maximum always for Group 14
values generally decrease down a given group: overlap
poorer for larger orbitals
data for a given period roughly symmetrical about Group 14
element
Why maximum for Group 14?
in diatomic there is a low energy antibonding MO (2
u
) which
is always occupied
in 3D solid, each atom has four valence atomic orbitals (s and
three p): for N atoms therefore have 2N bonding MOs and 2N
antibonding MOs, to make a total of 4N MOs
Group 14 elements of four valence electrons each, so these
ll the 2N bonding MOs exactly, and all the antibonding MOs
are empty
Group 15 elements have to put electrons into antibonding
MOs, and Group 13 elements do not have enough electrons
to ll bonding MOs weaker bonding
Group 14 elements
diamond structure (carbon)
tetrahedral coordination: each atoms has four sp
3
HAOs
N atoms therefore give 2N bonding MOs and 2N antibonding
MOs
for carbon, 4 electrons per atom exactly ll the bonding MOs
other Group 14 elements, except Pb, have allotropes with the
diamond structure
Group 15 elements
atoms now each contribute ve valence electrons; N atoms,
hence 5N electrons
the 5N electrons ll the 2N bonding MOs, and leave N
electrons to go into antibonding MOs; the result is reduced
bonding
as we saw before, each antibonding electron can be thought
of as cancelling out the effect of a bonding electron
result is 3 electrons per atom contributing to bonding plus 2
electrons having no net contribution
these two electrons are a lone pair
Group 15 elements
with exception of nitrogen all elements show several
allotropes; their structures can be considered as having three
bonds per atom and one lone pair
hexagonal-rhombohedral -As
-As, -Sb, and -Bi
A
B
C
A
B
both resemble diamond, but with three bonds and a lone pair
instead of fourth bond
Group 16 elements
six valence electrons per atom: 4N electrons ll the bonding
MOs and 2N go into antibonding MOs
2N in antibonding MOs cancel 2N in bonding MOs two
bonds and two lone pairs per atom
at room temperature stable form of sulfur is rhombic or
-sulfur; above 96

C stable form is monoclinic or -sulfur
both forms consist of puckered eight-membered rings, packed
together
Fig 7.25 Rhombic sulfur
(a) (b) (c)
S
8
rings in different environments shown in different colours
Fig 7.26 & 7.27 Tellurium
sprial chains (two bonds per atom and two lone pairs);
repeats every four atoms
packing of chains
(a) (b)
Group 17 elements
seven valence electrons per atom: 4N electrons ll the
bonding MOs and 3N go into antibonding MOs
3N in antibonding MOs cancel 3N in bonding MOs one
bond and three lone pairs per atom
exist as diatomic molecules
solid I
2
: layers of diatomic molecules
(a) (b)
7.6.6 Second Period anomaly
Period 2 elements nitrogen and oxygen exist as gas-phase
molecules, whereas other members of the group exist as
solids
bond strength of F
2
(159 kJ mol
1
) is weaker than that of Cl
2
(243 kJ mol
1
) or Br
2
(193 kJ mol
1
)
explanation comes from considering the MO diagram
7.6.6 Second period anomaly
2g
2u
3g
1u
1g
3u
antibonding 1
g
is raised more than bonding 1
u
is lowered
in F
2
antibonding effect of 1
g
more than cancels bonding
effect of 1
u
bond is weakened
called the antibonding effect
Antibonding effect
2p 2p 3p 3p
u
(a) (b)
E
E'
F F Cl Cl Cl
2
F
2
in F
2
antibonding
g
raised by E more than bonding
u
is
lowered
same effect in Cl
2
, but E
is smaller than E due to poorer

overlap of larger 3p AOs
antibonding effect is greater in F
2
; this accounts for the
relative weakening of the bond
Lone-pair lone-pair repulsion
alternative explanation for the weaker bond in F
2
is the larger
repulsion between lone pairs in F
2
when compared to Cl
2
in MO picture, lone pairs can be thought of as arising from
lled bonding/antibonding pairs of MOs
two lone pairs from (2
g
)
2
/(2
u
)
2
; four lone pairs from
(1
u
)
4
/(1
g
)
4
hence three lone pairs per atom
Bond strengths in p-block diatomics
second period diatomic B
2
C
2
N
2
O
2
F
2
1
297 607 945 498 159
third period diatomic Al
2
Si
2
P
2
S
2
Cl
2
1
133 327 490 425 243
for Groups 13, 14 & 15 diatomic from Period 2 has stronger
bond than that from Period 2
explanation is better overlap of smaller orbitals from Period 2
element
for Groups 1315 the
g
antibonding MOs are not occupied,
but for Groups 16 and 17 elements these start to be occupied
for these elements the antibonding effect starts to kick in,
making O
2
only a little stronger than S
2
, but F
2
signicantly
weaker than Cl
2
7.7 Metallic structures
metals adopt structures which have many close contacts
(nearest neighbours) per atom
bonding is best described as delocalized and involving the
formation of bands
common structures are based around the idea of close
packing of spheres i.e. the way in which the maximum number
of spheres can be packed into a give space
such structures naturally maximize the number of nearest
neighbours
7.7.1 Close-packed structures: Fig 7.33
(a)
(b)
(a) shows closest packing possible in a layer; 6 contacts per
sphere
(b) next layer arranged so that spheres lie over the interstices:
results in three more contacts
two ways of achieving this: shown in yellow and in blue
(a) (b)
A
A
B
Hexagonal close-packed
if third layer lies over atoms of rst layer, result is hexagonal
close packing
layer structure described as ABAB; 12 contacts per atom
(c) (d)
A
A
B
C
Cubic close-packed
if third layer arranged to lie in the other set of interstices it
does not lie over the rst layer
the fourth layer lies over the rst, result is cubic close packing
structure described as ABC; 12 contacts per atom
7.7.2 Non close-packed structures: Fig 7.37 & 7.38
in body-centred cubic, only eight atoms arranged at corners
of a cube in contact with central atom
building up the structure
(a) (b)
within a layer, spheres arranged on a square grid
atoms in successive layers do not touch (not close packed)
7.7.3 Bonding in metals; Fig 7.39
Cs
Rb
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Sr
Y
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
Ba
Lu
Hf
Ta
W
Re Os
Ir
Pt
Au
Hg
s
t
a
n
d
a
r
d

e
n
t
h
a
lp
y

o
f

a
t
o
m
iz
a
t
io
n

/

k
J

m
o
l -
1
Group number
1 2 3 4 5 6 7 8 9 10 11 12
0
100
200
300
400
500
600
700
800
900
enthalpy of atomization of metals
similar trend to that seen for p-block elements
however, now need also to consider d electrons and the
bands that are formed
Fig 7.40 Band structure for Period 6 elements
in
c
re
a
s
in
g
e
n
e
rg
y
5d-band
6s-band
6p-band
proposed band structure for Period 6 elements; bonding COs
are shaded
one 6s per atom, so corresponding band can accommodate
2N electrons
5d band can accommodate 10N electrons
Fig 7.40 Band structure for Period 6 elements
in
c
re
a
s
in
g
e
n
e
rg
y
5d-band
6s-band
6p-band
as cross Period 6 initially electrons ll bonding COs in 5d and
6s bands
these bonding COs will be exactly lled by 6N electrons,
which is tungsten (W): this element has maximum bonding
further electrons go into antibonding COs, weakening the
bonding
Fig 7.39 Enthalpy of atomization of metals
Cs
Rb
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Sr
Y
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
Ba
Lu
Hf
Ta
W
Re Os
Ir
Pt
Au
Hg
s
t
a
n
d
a
r
d

e
n
t
h
a
lp
y

o
f

a
t
o
m
iz
a
t
io
n

/

k
J

m
o
l -
1
Group number
1 2 3 4 5 6 7 8 9 10 11 12
0
100
200
300
400
500
600
700
800
900
for Period 6, reaches a maximum at tungsten (W)
for other periods, behaviour is more erratic: due to other
overlapping bands being occupied (e.g. p band)
7.8 The transition from metals to non-metals
metals delocalized bonding; eight to twelve nearest
neighbours; conduct electricity because of partially
lled bands
semimetals fewer nearest neighbours than metals; poorer
conductors of electricity than metals; electrical
conductivity of both metals and semimetals
decreases as the temperature is increased
semiconductors conduct electricity poorly; conductivity increases
with temperature as electrons promoted across band
gap
non-metals electrical insulators; lled bands with large band gap;
structures consist of more localized bonding with four
or fewer bonds per atom
Fig 7.41 The transition from metals to non-metals
metal semimetal semiconductor non-metal
Lu
H
Be Li
C
C
B O N Ne
He
F
Mg

Na Si Al S
P
P
Ar Cl
Ca K Ti Sc Cr V Fe Mn Ni Co Zn Cu Ge Ga
Se
Se
As
As
Kr Br
Sr

Rb Zr Y Mo Nb Ru Tc Pd Rh Cd Ag
Sn
Sn
In Te Sb Xe I
Ba Cs Hf W Ta Os Re Pt Ir Hg Au Pb Tl Po Bi Rn
At
?
period 2
period 3
period 4
period 5
period 6
17 18 16 15 14 13 2 1
3 4 5 6 7 8 9 10 11 12
s block
d block
p block period 1
bcc hcp
hcp hexagonal close-packed
hcp
ccp
ccp cubic close-packed
hcp hcp hcp hcp
hcp
ccp
ccp
ccp
ccp ccp
ccp
ccp
ccp
ccp
ccp ccp ccp
hcp hcp
hcp hcp
hcp hcp
hcp hcp hcp
ccp
bcc
bcc body centred cubic
bcc bcc
bcc
bcc bcc
bcc bcc bcc
bcc bcc
bcc bcc
Orbital sizes and overlap
metal semimetal semiconductor non-metal
Lu
H
Be Li
C
C
B O N Ne
He
F
Mg

Na Si Al S
P
P
Ar Cl
Ca K Ti Sc Cr V Fe Mn Ni Co Zn Cu Ge Ga
Se
Se
As
As
Kr Br
Sr

Rb Zr Y Mo Nb Ru Tc Pd Rh Cd Ag
Sn
Sn
In Te Sb Xe I
Ba Cs Hf W Ta Os Re Pt Ir Hg Au Pb Tl Po Bi Rn
At
?
period 2
period 3
period 4
period 5
period 6
17 18 16 15 14 13 2 1
3 4 5 6 7 8 9 10 11 12
s block
d block
p block period 1
bcc hcp
hcp hexagonal close-packed
hcp
ccp
ccp cubic close-packed
hcp hcp hcp hcp
hcp
ccp
ccp
ccp
ccp ccp
ccp
ccp
ccp
ccp
ccp ccp ccp
hcp hcp
hcp hcp
hcp hcp
hcp hcp hcp
ccp
bcc
bcc body centred cubic
bcc bcc
bcc
bcc bcc
bcc bcc bcc
bcc bcc
bcc bcc
across period orbitals decrease in size: elements move
towards non-metallic structures with localized bonding and
fewer nearest neighbours
down group orbitals increase in size: elements move towards
metallic structures with delocalized bonding and many nearest
neighbours
for example, bond strength in Li
2
is 51 kJ mol
1
, but enthalpy
of atomization of Li(s) is 159 kJ mol
1
: delocalized bonding
clearly favoured
Intermediate structures: semimetals
Group 15 element As Sb Bi
distance to nearest three atoms within layer (r1) / pm 252 288 306
distance to nearest three atoms from adjacent layer (r2) / pm 312 335 351
ratio r2/r1 1.24 1.16 1.15
r
1
is distance to atoms in same layer
r
2
is distance to atoms in adjacent layer
as go down group, ratio r
2
/r
1
decreases
i.e. trend towards a (more close packed) metallic structure
7.9 Bonding between the elements
H Li Na K Rb Cs
H 436 238 186 175 167 175
Li 100 83 72
Na 71 62 62 59
K 50
Rb 47 46
Cs 43
bond strengths of hydrides and mixed diatomics of Group 1
need to consider not only the size of the orbitals but also the
energy match
Group 1 homonuclear diatomics all similar bond strengths, but
much less than H
2
for mixed diatomics, bond is stronger if it involves a smaller
orbital
bonding
2p2p overlap barrier 2p3p overlap barrier 3p3p overlap barrier
H2C=CH2 274 H2C=SiH2 149 H2Si=SiH2 105
H2C=NH 265 H2C=PH 180 H2Si=PH 120
HN=NH 251 HN=PH 185 HP=PH 142
energy (kJ mol
1
) needed to rotate about various bonds
rotating about the bond breaks the bond, so this is a
measure of the bond strength
size of orbital has a strong inuence, with 2p2p overlap by
far the strongest
accounts for bonds being common in Period 2, but much
less common thereafter
7.9.2 Covalent vs ionic bonding: Fig 7.42
LiF BeF
BF
CF
NF
B2
C2
N2
O2
F2
CO
NO
FO
BO
BeO
LiO b
o
n
d

s
t
r
e
n
g
t
h

/

k
J

m
o
l -
1
6 7 8 9 10 11 12 13 14
0
200
400
600
800
1000
1200
total number of valence electrons
bond strengths (gas phase) of various Period 2 diatomics
as for homonuclear diatomics, reaches a maximum with 10
valence electrons
but nature of bonding is not always the same . . .
Fig 7.43 Form of bonding MOs for XF
F-F O-F N-F
C-F B-F Be-F Li-F
bonding MO is symmetrical in F
2
. . .
. . . but as X becomes less electronegative (higher orbital
energy), MO is more and more dominated by the contribution
from the F
contribution of bonding is signicant for F
2
, partial for BF
and negligible for LiF
Fig 7.44 MO perspective
F Li
N
N2
N
LiF
3
4
5
1
2s
2s 2s
2s
2p
2p 2p
2u
3u
1u
1g
2
g
3g
(b) (a)
in N
2
orbital energies match; 10 valence electrons give triple
bond
in LiF, mismatch in orbital energies essentially no overlap
Fig 7.44 MO perspective
F Li
N
N2
N
LiF
3
4
5
1
2s
2s 2s
2s
2p
2p 2p
2u
3u
1u
1g
2
g
3g
(b) (a)
effectively in LiF an electron from Li 2s ends up in 4, which is
essentially F 2p: large reduction in energy, hence strong bond
might characterise as Li
+
F
: ionic contribution
ionic contribution is part of MO approach not something
extra 7: Trends in bonding 336
7.9.3 The classication of compounds as ionic or covalent
Ionic
high melting points and boiling points
the ability to conduct electricity when molten, but not when
solid
generally high solubility in polar solvents such as water
7.9.3 The classication of compounds as ionic or covalent
Covalent
often low melting points and boiling points
are unable to conduct electricity when solid or molten
generally more soluble in non-polar solvents such as toluene
or hexane
often have structures with discrete molecular units
Fig 7.45 Boiling points of halides
SiF4
(15)
NaF
(21)
NaCl
(13)
AlF3
(17)
AlBr3
(8)
AlI3
(6)
AlCl3
(9)
NaBr
(12) NaI
(10)
SiCl4
(7)
SiI4
(4)
SiBr4
(6)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
b
o
ilin
g

p
o
in
t

/

o
C
boiling point of halides; (difference in orbital energies)
high b. pt of NaX indicates ionic
low b. pt of SiX
4
indicates covalent
high b. pt of AlF
3
indicates ionic, but low b. pt of AlI
3
indicates
covalent
Fig 7.46 Van Arkel diagram
0 5 10 15 20 25 30
0
5
10
15
20
25
Cs K Na
Li/Ca
Mg Be
Ga
Sn
Si
Sb As
P
H I
C
S Br Cl N O F
CsF
LiF
MgO
AlN
NP
CsCl
NaCl
MgCl2
AlCl3
SiCl4
CCl4
MgBr2 LiH
AlAs
GaAs
GaSb
AlLi
Al3Mg2
TiB2
NO
BeO
MgF2
BeF2
SiO2
CO2
B2O3
P2O3
Mg3N2
BF3
CF4
NF3
OF2
Li2O
B
Al
Ti
(minus) average orbital energy of X and Y / eV
d
iffe
r
e
n
c
e
b
e
tw
e
e
n
o
r
b
ita
l e
n
e
r
g
ie
s
o
f X
a
n
d
Y
/ e
V
`IONIC
`
C
O
V
A
L
E
N
T
`
M
E
T
A
L
L
IC
for binary compounds, plot of difference in orbital energy

against average orbital energy
elements appear along the bottom: Cs on left (highest energy
orbitals) to F on right (lowest energy orbitals)
ionic compounds at top: largest difference in orbital energies
metallic to covalent as go across (orbital size)
7: Trends in bonding
the end
Instituto de Qumica
James Keeler
8: Describing reactions using orbitals 342
8: Describing reactions
using orbitals
Describing reactions using orbitals
reactions can be understood/rationalized by thinking about the
way in which the electrons are redistributed during the
reaction
this means thinking about how the orbitals are interacting and
changing during a reaction
will focus on reactions in organic chemistry
close relation to, and possibly the basis for, arrow pushing
8.1 The redistribution of electrons in a reaction
(a)
H
+
H
-
H-H
(b)
simplest reaction (gas phase) between H
and H
+
to give H
2
clearly a redistribution of electrons between the atoms: from
the H
to the covalent bond

can represent using curly arrows
H
+
H
-
H-H
arrow indicates motion of a pair of electrons
8.1.2 Protonation of water; Fig 8.3
large separation new O-H bond at 1.5 x re
MO3
MO2
MO1
H3O+
H+
MO4
H2O
MOs plotted for three different arrangements
in H
2
O MO1 and MO2 are strongly bonding; MO3 is weakly
bonding; MO4 is lone pair
8.1.2 Protonation of water; Fig 8.3
large separation new O-H bond at 1.5 x re
MO3
MO2
MO1
H3O+
H+
MO4
H2O
MO1 & MO2 simply extend to cover the H
+
MO3 more signicant change: becomes strongly bonding
MO4 becomes weakly bonding. All MOs change.
8.1.2 Protonation of water
curly arrow mechanism (note curly arrow starts from lone pair)
O
H
H
H
O
H
H
H
+
+
the positive charge on the oxygen is a formal charge
the actual charge distribution, shown in (b), is quite different
O
H
H
H
O
H
H
H
+
O
H
H
H
+
+0.48
+0.48
-0.44
+0.48
(a) (b) (c)
(c) is a better representation as it does not imply that the
charge resides on one atom
8.1.3 Formal charges
formal charges arise from a particular way of assigning
electrons to atoms
assumes that each pair of electrons in a bond is shared
equally between the atoms
in H
3
O
+
oxygen has half share in the three pairs of electrons
in the bonds, plus one lone pair: total is 5 electrons
isolated oxygen needs 6 valence electrons to be neutral,
hence in H
3
O
+
oxygen formal change on the oxygen is +1
these charges do not necessarily bear any relation to actual
distribution of electron density
8.2 HOMOLUMO interactions
although all MOs change during a reaction, often the most
signicant interaction is between highest occupied MO
(HOMO) and the lowest unoccupied MO (LUMO)
types of orbital interaction (blue: reactants; green: change on
interaction)
(a) (b) (c)
(a) lled/empty lowering of energy
(b) lled/lled no change in energy
(c) empty/empty no change in energy (orbitals not
occupied)
HOMO/LUMO of type (a)
8.2 HOMOLUMO interactions
HOMOLUMO likely to be reasonably closely matched in
energy hence signicant interaction
there are two possible HOMO/LUMO pairs
LUMO
HOMO
MOs for
reactant A
MOs for
reactant B
LUMO
HOMO
HOMO A LUMO B OR HOMO B LUMO A
closest energy match gives strongest interaction: focus on this
choice (here HOMO A LUMO B)
8.2.1 Identifying the HOMO and LUMO
identifying the HOMO and LUMO is a useful rst step
rough energy ordering
highest energy
antibonding
antibonding
nonbonding orbitals (including lone pairs)
bonding
lowest energy bonding
HOMO often a lone pair on heteroatom
LUMO often a non-bonding orbital, or a
or
MO
often several candidates for HOMO/LUMO
8.2.2 How orbitals change during a reaction
using computer calculations can follow how MOs change
during reaction
the change is always steady, but sometimes MOs change in
unexpected ways
due to mixing between MOs (of same symmetry)
A B
B A
orbitals in
reactants
orbitals in
products
A A
B B
orbitals in
reactants
orbitals in
products
(a) (b)
e
n
e
r
g
y
(a) no mixing (different symmetry)
(b) mixing (same symmetry) results in avoided crossing;
A acquires contribution from B
8.3 Interactions involving nonbonding LUMOs
interaction of two species to form a single adduct; LUMO is a
nonbonding MO
Lewis acid: a species which can accept electrons to form a
bond e.g. H
+
, BH
3
, BF
3
, AlCl
3
in BH
3
and BF
3
LUMO is effectively a p orbital
(a)
(b)
BH3
BF3
LUMO can interact with high-energy pair of electrons to form
a new bond
8.3.1 The reaction of BH
3
with H
HOMO is 1s on H
; LUMO is 2p on BH
3
how the HOMO changes over the reaction
large separation new B-H bond at 2 x re new B-H bond at 1.5 x re
BH4
-
H
- BH3
orbital becomes a bonding MO as reaction proceeds;
hybridization on B changes from sp
2
to sp
3
8.3.1 The reaction of BH
3
with H
cartoon of the initial HOMOLUMO interaction

H
H B
H H
+
hydride
HOMO
borane
LUMO
curly arrow mechanism
H
H B
H H
- -
H
B
H
H
H
different representations of BH
4
-
H
B
H
H
H
-
H
B
H
H
H
(a) (b)
Angle of attack: Fig 8.12
from which direction does the H
approach (called the angle

of attack)?
want to maximize the HOMO/LUMO overlap in the early
stages
two different approaches
positive
overlap
negative
overlap
B
H
positive
overlap
B H
(b) (a)
(a) has greater overlap than (b): therefore preferred
8.3.2 Nucleophiles, bases, acids and electrophiles
BH
3
is Lewis acid; can describe H
as Lewis base
H
more usually described as nucleophile: nucleus loving

donates electrons
BH
3
can be described as electrophile: electron loving
accepts electrons
H
+
is an electrophile or Lewis acid
in inorganic chemistry, electron donors bonded to metal atoms
are called ligands
8.3.3 The protonation of ethene
HOMO is bonding MO; interaction with LUMO causes a bond
to break
overall reaction
C C
H H
H H
H
C C
H
H
H
H
H
+
+
HOMO is bonding MO of ethene; LUMO is 1s on H
+
how the orbitals change (Fig 8.13)
(a) H
+
(b) (c)
intermediate
separation
equilibrium
geometry
large separation
ethene
note bond is broken
Fig 8.14 curly arrow mechanism
C C
H H
H H
H
C C
H
H
H
H
H
+
+
C C
H H
H H
H
C C
H
H
H
H
H
+
+
(a)
(b)
(a) shows electrons from bond forming new bond to H
+
alternative (b) emphasizes that proton becomes attached to
right-hand carbon
note formal positive charge on left-hand carbon
Fig 8.15 How LUMO of the product is formed
H
+ (a)
ethene
large separation
intermediate
separation
equilibrium
geometry
(b) (c)
LUMO of ethene + H
+
; to start with it is the 1s on H
+
, but in
the product it is essentially a 2p on the left-hand carbon
cartoon of the LUMO of the product
C C
H
H
H
H
H
+
8.4 Interactions involving antibonding LUMOs
in previous examples, electrons donated into vacant
nonbonding MO formation of new bond
if LUMO is an antibonding MO the result will be that a bond in
the electrophile is broken
rst consider case where LUMO is

8.4.1 Nucleophilic attack on a carbonyl
R1 R2
O
R1 R2
Nu O
Nu
-
-
+
a new bond is formed between the nucleophile and the carbon
of the carbonyl
the C=O double bond becomes a single bond
the geometry about the central carbon changes from trigonal
planar to tetrahedral
the nucleophile loses a negative charge (either going from
negative to neutral, or from neutral to positive)
the oxygen becomes negatively charged
Methanal and H
H H
O
H H
H O
H
-
-
+
tetrahedral ion
carbonyl bond is polarized: partial positive charge on carbon
has initial favourable interaction with H
HOMO is H 1s; LUMO is
of C=O
larger contribution on carbon
Methanal and H
large separation new C-H bond at 2 x re new C-H bond at 1.2 x re

CH3O
-
methanal
H
-
(a)
(b)
(a) shows evolution of HOMO
1s on H
ends up as lone pair on oxygen (mainly a 2p AO)

(b) shows what happens to bonding MO: bond is broken
and electron density ends up forming new CH bond
behaviour of the MOs is unexpected and due to extensive
mixing
Curly arrow mechanism
H H
O
H
-
H H
H O
-
arrow suggests that electrons from H
end up forming CH
bond, and electrons from bond end up on the oxygen
not consistent with the detailed picture arising from the
MOs . . .
. . . but the overall result is the same
probably not meaningful to take about where a particular pair
of electrons goes
Angle of attack
positive
overlap
positive
overlap
negative
overlap
negative
overlap
H
H
H
C O
H
(b) (c) (a)
H
C O
H
H
C O
H
hydride
1s
carbonyl *
H
(a) if H
approaches in the plane, no net overlap

(b) approaching the face of the molecule has same problem
(c) side-on approach gives best overlap
Optimum angle of attack: Fig 8.20
Nu
R2
C O
R
1
109
o
calculations indicate most favourable line of attack at an angle
of approximately 109
to plane of molecule
8.5 Interactions involving antibonding LUMOs
donation of electrons into
MO leads to bond breaking and

the departure of a group
called nucleophilic substitution
example
- -
+ + X
R
X
H
H
Nu
R
Nu
H
H
features
a new bond is formed between the nucleophile and the central

carbon
as the CX bond is broken, the leaving group X
is released
the geometry around the carbon undergoes an inversion; in

some sense it is turned inside-out (like an umbrella)
H
+ CH
3
Cl
HOMO is 1s on H
LUMO is CCl
(lower in energy than CC
)
different representations of the LUMO
H
H
H
Cl C
(a)
(b)
(c)
Fig 8.22 Key MOs in H
+ CH
3
Cl reaction
Cl
-
PRODUCTS
REACTANTS
H
-
CH4
CH3Cl
decreasing carbon-hydrogen distance
increasing carbon-chlorine distance
(a) The HOMO
evolution of the HOMO
starts to include a contribution from LUMO (CCl
)
ends up as p orbital on Cl
Fig 8.22 Key MOs in H
+ CH
3
Cl reaction
Cl
-
PRODUCTS
REACTANTS
H
-
CH
4
decreasing carbon-hydrogen distance
increasing carbon-chlorine distance
(b) The -bonding MO
CH
3
Cl
evolution of the CCl bonding MO
starts to include a contribution from HOMO (1s on H
)
electron density along CCl decreased: bond breaking
ends up as CH bonding MO
Curly arrow mechanism / angle of attack
as before, the arrows do not quite match what how the orbitals
change
-
-
+ Cl
H
Cl
H
H
H
H
H
H
H
1 2
angle of attack: optimum from the rear, as this gives best
overlap
H
H
H
Cl C
positive
overlap
positive
overlap
negative
overlap
(b) (a)
H
H
H
H
Cl C
H
8.6 Summary of the effects of
different HOMOLUMO interactions
a useful starting point is to identify the electrons which have
the highest overall energy in either reactant; lowering the
energy of these can provide a strong driving force for the
reaction to occur
a particularly important interaction is between the HOMO of
one reactant with the LUMO of the other
new bonds may be formed when electrons are donated into
vacant nonbonding or antibonding orbitals; putting electrons
into an antibonding orbital breaks an existing bond, whereas
putting electrons into a nonbonding orbital does not
a curly arrow mechanism provides a convenient way of
summarizing the net redistribution of electrons between the
reactants and products; each arrow does not represent the
behaviour of the electrons in a particular MO
8.7 The role of protonation in reactions
many reactions only go at a reasonable rate after the starting
material has been protonated or combined with a Lewis acid
for example, hydrolysis of ethyl ethanoate occurs several
thousand times faster as the acidity of the solution is
increased from pH 7 to pH 1
initial step is attack from oxygen lone pair of H
2
O into the
of the C=O
Me OEt
O
Me OEt
O H
2
O H
2
O
-
+
products
other steps
this step is considerably faster if the C=O is rst protonated on
oxygen
Me OEt
O
H
H
2
O
+
products
faster
Me OEt
OH H
2
O
+
other steps
Lowering the energy of the CO
MO
why does protonation speed up the reaction?
rst: makes carbonyl carbon more +, hence stronger
interaction with nucleophile
second: protonation lowers energy of oxygen AOs, and hence
lowers energy of
MO
*
C 2p
O 2p
O
+
2p
+
C=O-M
+
C=O-M
* C=O
C=O
Fig 8.25 Effect of protonation on MOs
(a) (b) (c)
Li
+
Li
+
(a) is unprotonated: note oxygen is main contributor to , and
carbon to
(b) is protonated: oxygen orbital lowered, poorer energy
match with carbon
result is an increase in the asymmetry of the contributions
coordination by Li
+
has similar effect
Fig 8.26 Representations of the protonated carbonyl
H
H
O
H
H
O
H
H
O
H
H
O
H H
-
+
+ +
filled bonding MO
with equal contributions
from O and C AOs
filled O 2p AO
filled bonding MO
from O and C AOs
filled O 2p AO
vacant C 2p AO
vacant * antibonding MO
from O and C AOs
vacant C 2p AO
vacant * antibonding MO
from O and C AOs
(a) (b) (c) (d)
(a) and (b) are resonance forms for the unprotonated
carbonyl; (c) and (d) are for the protonated carbonyl
8.8 Intramolecular orbital interactions
so far have considered interaction of HOMO and LUMO on
different molecules
for example between CH
3
NH
2
and CH
3
CH
2
Cl; HOMO is lone
pair on N, LUMO is CCl
N
H
H
H
H
H
C
H
H
H
H
C l
H
(a) (b)
what happens if the NH
2
and Cl groups are in the same
molecule?
8.8 Intramolecular orbital interactions
if the NH
2
and Cl groups in same molecule the HOMO can
be thought of as a combination of the MOs shown in (a) and
(b)
N
H
H
H
H
H
C
H
H
H
H
C l
N
H
H
H
H
C l
H
(a) (b) (c)
interaction of nitrogen lone pair strengthens CN bond and
weakens CCl bond; note character of CN bond
in fact, no compound has been isolated with NH
2
and Cl
groups on adjacent carbons
what presumably happens is that the C=N bond develops
fully, and the Cl is ejected
N
H
H
H
H
Cl
N
H
H
H
H
Cl
-
+
relation between MOs
N
H
H
H
H
Cl
(c) (d)
N
H
H
H
H
Cl
-
Cl
-
+
Fig 8.28 Crystal structure of CH
3
OCH
2
Cl
136 pm
182 pm
O
H
Cl
H
H H
H
similar situation, but this compound exists
however, CO bond is shorter and CCl bond is longer than
typical values; taken to indicate signicant interaction between
oxygen lone pair and CCl

8.9 Rearrangement reactions
class of reactions in which the bonding is rearranged: no
encounter between two reactants
for example, pericyclic reactions
heat or UV light
cis-1,3,5-hexatriene 1,3-cyclohexadiene
new CC bond formed and bonds rearranged
Fig 8.29 Different outcomes
Me
H
H
Me
Me
H
Me
H
Me
H
H
Me
H
Me
Me
H
heat
UV light
remarkable observation of different product depending on
whether heat or UV light used to promote the reaction
product can be interpreted in terms of the end groups rotating
in same or opposite senses
explanation can be formed in terms of what is happening to
the MOs
Fig 8.30 The MOs of 1,3,5-hexatriene
1
2
3
MOs of these orbitals in a row can be formed by inscribing
whole numbers of half sine waves
Fig 8.31 How the MOs change during
the cyclisation of 1,3,5-hexatriene
MO C
MO B
MO A
MO C
MO B
MO A
i ii iii iv v vi vii
starting position on left; product on right
energy ordering (lowest) A
, C
, B
(highest)
Fig 8.31 How the MOs change during
the cyclisation of 1,3,5-hexatriene
MO C
MO B
MO A
MO C
MO B
MO A
i ii iii iv v vi vii
twisting end groups towards one another gives in-phase
overlap for A and C, but out-of-phase for B
resulting strong mixing gives rise to an unexpected outcome
e.g. C in fact becomes a bonding MO in product, whereas A
gives bond
can draw the electrons moving either way
neither represents at all what is happening with the MOs
8: Describing reactions
using orbitals
the end

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Instituto de Qumica

Chemical structure and reactivity:

electrons repel one another, so placing them in separate

electrons with parallel spins avoid one another, so having

the bond dissociation energy of Be

in LiH, the hydrogen has a partial negative charge, whereas

= [(1s AO on atom A) (1s AO on atom B)]

as a function of the bond length

) rises as atoms approach: called the

lowest total energy with a bond angle of 60

computer programs which calculate MOs will also optimise

to one another: ideal for

occupation of all the MOs accounts for 10 electrons

then no overlap i.e. the bond is broken

sp HAOs on different carbons overlap to give CC and

4: Electrons in molecules: polyatomics 145

; former is the LUMO

(lower in energy than

MOs to identify LUMO

band (empty; conduction band)

numerical charges on the ions

: standard Gibbs energy change;

: standard entropy change for the

: standard Gibbs energy

: standard enthalpy change;

is the change in Gibbs energy change when two moles

, and hence K, only depends on the Gibbs energies of

using tabulated standard enthalpies of

using tabulated standard absolute

the standard enthalpy of formation of a compound,

tabulated data of standard absolute entropies S

have only a weak temperature

includes the term T

6: Thermodynamics and the Second Law 255

determines whether reactants or products are

means products favoured, positive

-60 -40 -20

6: Thermodynamics and the Second Law 258

for reactions involving ions in solution

6: Thermodynamics and the Second Law 259

is negative (as expected)

becomes more negative as size of ion decreases and

is negative; reduction in entropy due to restriction of

becomes more negative as size of ion decreases and

for each step

for each step

more negative than

is negative and NaCl has signicant solubility

of step 4 is just negative (i.e. solvation terms win)

is positive due to unfavourable entropy of

more positive than

very slightly exothermic

larger than for NaCl (again, effect of higher charges)

negative for steps 1 and 2 (dissociation), but

slightly positive more so for HF

dominates, whereas for HCl the

is the standard pressure, and p

is smaller than E due to poorer

for binary compounds, plot of difference in orbital energy

to the covalent bond

cartoon of the initial HOMOLUMO interaction

approach (called the angle

more usually described as nucleophile: nucleus loving