The Chemical Bond: OGN - Chapter 3

The Chemical Bond
OGN - Chapter 3
OGN Chapter 3: Bonding 1

Periodic Table

Link to Periodic Table
• http://www.mcs.net/~ars/spectro/elements.htm
If you use a search engine such as Altavista,

Yahoo, Hotbot, etc and look for “periodic
table” you will find many more.

Bond Properties
“Open shell atoms” may bond chemically via :
• sharing of electrons, (covalent).
• exchange of electrons, (ionic).
Key properties of the chemical bond
• bond length
• bond energy
• bond order (related to the other two)

Bond Lengths in Molecules
• are measured by spectroscopy or by

electron or X-ray diffraction
•The nuclei in a diatomic molecule

vibrate about average positions. The
bond length is the average internuclear
distance.

Water Hydrogen
nucleus
molecule, H2O 1 protons
liquid at 25OC
Angle = 109O
H
Single bond
Length = 109nm
Oxygen nucleus
8 protons+8
neutrons
Formaldehyde
molecule,
CH2O or H2CO Angle = ???O
solid at 25OC
Carbon nucleus
6 protons +
6 neutrons
Double bond
Length = ???nm
Bond Lengths in Molecules
• Within a periodic group, bond lengths of
diatomic molecules increase with increasing
atomic number
eg: N--H P--H As--H Sb--H Bi--H
•Bond lengths for atom pairs are almost the
same from molecule to molecule
eg: A carbon - carbon single bond has almost
the same length in every organic molecule

Bond Enthalpies
• Chemical bonds are formed when,
reaction, the overall energy of
the system can be lowered.
• Molecules adopt a geometry

which minimizes their energy.

0
Bond Enthalpies
•The energy required to break a bond is
called the bond dissociation energy, Ed
Ed is a measure of bond strength

1
• The heat absorbed at constant pressure is
called the bond enthalpy, H  E  RT
d d
Why constant pressure?
• Bonds generally get weaker with increasing

atomic number (some anomalies!! eg. F2).
HF HCl HBr HI
Hd 568 432 366 298
(kJ mol-1)
2
• Bond enthalpy also increases with
increasing multiplicity of bonds.
NNOOFF
945 kJ mol-1 498 kJ mol-1 158 kJ mol-1
Hd  Ed  RT

3
Compound Length Enthalpy
(nm) (kJ mol-1)
ethane, H3CCH3 153.6 348
ethene, H2CCH2 133.7 615
ethyne, HCCH 120.4 812
There are three different classes of C-C bonds.
We distinguish them in terms of bond order,
defined as the number of electron pairs shared
in a chemical bond.

4
Bond Orders
Hence a measured bond length of 120nm and
an enthalpy of 810 kJ mol-1 would indicate a
carbon-carbon triple bond.
C-C longest/weakest 1
C=C 2
C=C shortest/strongest 3

5
Special Cases
In some cases, the measured C-C distance and
bond enthalpy values do not match those
previously tabulated.
e.g. benzene, C6H6 has C-C distance = 1.397A,
and an enthalpy = 505 kJ mol-1
i.e intermediate between C-C
and C=C, with a bond order
of 1.5.
6
Ionic and Covalent Bonds
Chemical bonds arise from the sharing
or transfer of electrons between two or
more atoms.
A X A X
e-
transfer of e-
e-density shared
COVALENT IONIC
e.g. H-H e.g. Cs+I-

7
Polar Covalent Bonds
Most bonds lie somewhere in between
ie. partial transfer of e-
e.g. H + Cl -

8
Ionisation Energy (IE)
The energy necessary to pull an electron
off an atom (or molecule).
+ -

9
Electron Affinity (IE)
The energy gained by an atom (or
molecule) in receiving an electron.
+ -

0
Electronegativity (Mulliken)
Mulliken proposed that the electronegativity of
an atom be defined as
1
Electronegativity  ( IE1  Ea )
2

1
Electronegativity
• useful for predicting the likely extent
of charge transfer between 2 atoms.
e.g. Cs and F
IE1 EA
Cs low small
F high large

2
Electronegativity
IE1 EA
Cs low small
F high large
Electronegativity measures the ability

of an atom to attract electrons, and is
directly related to EA and IE. Let’s
look at several definitions.

3
Electronegativity
Electron donors such as alkali metals with low
IE’s and low EA’s have low electronegativities
and are thus termed “electropositive”.
• electron acceptors like the halogens are highly
electronegative.
Problem - this definition doesn’t take into

account the chemical environment of the atom
in question.
4
Electronegativity (Pauling)
There are other ways of defining
electronegativity
eg. Pauling - developed a scale of average

electronegativities.
0.7 (Cs) - 3.98 (F) (see O+N, Fig. 14.1).

5
Trends: electronegativity increases across
period, as size decreases, and nuclear charge
increases.
K (0.82) Br(2.96)
electronegativity decreases down period, as
atomic size increases rapidly with atomic
number. C(2.55)
Pb(2.10)
6
NOTE
late transition elements
go against the trend (very slow
increase in size with increasing
nuclear charge).

7
Electronegativity and Bond Type
The difference between electronegativities

of two bonded atoms is a measure of the
bond polarity, with the more
electronegative atom having more of the
electron density.

8
Examples
Na (0.93) Cl (3.16) (EN)=2.23,
ionic, Na+Cl-
H (2.2) Cl (3.16) (EN)=0.96,

polar covalent, H+Cl-
Cl (3.16) Cl (3.16) (EN)=0,

covalent, Cl-Cl
9
Bonding Summary
Electronegativity Bond
Difference Type
small covalent
intermediate polar covalent
large ionic

0
Ionic Bonding
We can use a simple approach to
calculate the lowering of energy as
two atoms are brought together to
form an ionic molecule.

1
Ionic Bonding (Step 1)
Calculate the energy required to form the two
separated ions from two separated atoms.
K(g) K+(g) + e- E = IE1 = +419 kJ mol-1
F(g) + e- F-(g) E = -EA = -328 kJ mol-1
Adding the two equations
K(g) + F(g) K+(g) + F-(g) E = 419 + (-328)
= +91 kJ mol-1

2
Ionic Bonding (Step 2)
Treating the ions as point charges, we next calculate
the energy lowering as the ions are brought together.
In this process there is a large energy release
(denoted by Ecoul
K+ F- Ecoul = -640 kJ mol-1
At a distance Re = 217nm, the energy reaches a
minimum value. Adding (step1 + step2) :
E = (+91) + (-640) = -549 kJ mol-1

3
Ionic Bonding (Result)
Therefore KF is more stable than the component
atoms by Ed = 549 kJ mol-1.
Although it costs energy to transfer an electron

from a K atom to a F atom, this energy is more
than recovered as the ions approach each other
to form an ionic solid.

4
Ionic Bonding (Experiment)
Experimentally determined Ed value is 498 kJ
mol-1.The discrepancy is not unreasonable since-
• we ignored repulsive interactions.

• we assumed a purely ionic KF bond.
• we assumed point charges on the nuclei.

5
Coulomb Interaction Energy
As two ions approach each other, there is an
attractive (Coulomb) force between them
which leads to an interaction energy of the
form
Z1 Z 2 e 2
E coul 
4  0 R
OGN•Chapter 3: Bonding 3
6
Coulomb Interaction Energy
Z Z e 2
Ecoul  1 2
4  R
0
R is distance between the two ion centres.
• Z1e and Z2e are the charges on the two ions.
• 0 is a constant (the dielectric constant).
If Z1 and Z2 have opposite signs, the total
energy is lowered as the ions approach each
other from infinity.

7
Ionic Bonding

8
Ionic Solids
Note that molecules like KF(g) would exist only
at very high temperatures.
At ordinary temperatures, the process
n KF(g) ionic solid
is highly exothermic.
Ionic solids are very stable 3D lattices, with
very high melting points

9
Covalent Bonding
Involves e- sharing between the two bonded atoms.
e.g. Consider forming H2+ from 2 H nuclei and 1e- .
[H-H]+
distance Re = 106nm
Ed = 255.5 kJ mol-1

0
Covalent Bonding
(a) e- between nuclei, strengthens bond

HA+ e- H B+
(b) e- outside internuclear region, weaker bond
e- HA+ H B+

1
Covalent Bonding
Covalent bonding arises when e- spends most of
its time between the nuclei.
This simple picture is readily extended to other
molecules :
H H H O H
OGN Chapter 3:HBonding H2 O 4

2
2
Covalent Bonding
Covalent bonding arises when e- spends most of
its time between the nuclei.
This simple picture is readily extended to other
molecules :
H H H O H
H2 H2 O
or 10100 others
3
Dipole Moments and Ionic
Character
It is useful to have some measure of ionic character
when considering a series of molecules such as
H2 (covalent) HF (polar covalent) K+F- (ionic)
The dipole moment of a molecule () can be
determined by spectroscopic measurements. For a
diatomic molecule AX
+Q -Q

A X
 = QR
R

4
Dipole Moments and Ionic
Character
+Q -Q
 A X  = QR
R
•the SI unit for  is the Coulomb meter (Cm).
• the Debye is commonly used

1 D = 3.336 x 10-30 Cm.
5
Dipole Moments Example
Consider the polar covalent molecule HF
If HF were totally ionic (H+F-), we would expect
 = ( 1 electronic charge ) ( 1 HF distance )

= (1.60 x 10-19 C) (9.17 x 10-11 m)
= 1.47 x 10-29 Cm = 4.40 D

6
Dipole Moments Example
 (Calc)= 1.47 x 10-29 Cm = 4.40 D

However the measured  for HF is only 1.83 D !!
We can use this result to express the percentage
ionic character in HF as
+ - 1.83
H-F   0. 42 (42%)
4. 40

7
Table of Dipole moments
for diatomics
Molecule (D) % ionic character
H2 0 0
CO 0.112 2
HCl 1.109 18
NaCl 9.001 79
NaF 8.156 88
We now have two measures of ionic character, the
electronegativity and the dipole moment.
8
The Shapes of Molecules
Molecular structure plays a key role
in determining chemical properties.
Valence shell electron pair repulsion

theory (VSEPR) allows molecular
structures to be predicted.

9
The Shapes of Molecules
HOW ?
• the structure around a given atom is
determined principally by minimizing electron
pair repulsions.
• bonding and non-bonding electron pairs
around a given atom are positioned as far apart
as possible.

0
Applying VSEPR to real
molecules
To apply VSEPR to real molecules, we
write the Lewis structure
• determine the steric number (SN) of the
central atom.
 number atoms  number lone pairs 

SN  bonded to central atom    on central atom 

1
Applying VSEPR to real molecules

SN  
number atoms   
number lone pairs
bonded to central atom  on central atom 
• double or triply bonded atoms count the
same as single bonded atoms in determining
the SN (SN in CO2 is 2).
• use steric number to predict the molecular
geometry.
• name the molecular structure, based on the
positions of the atoms.
2
Boron trifluoride, BF3 and ammonia, NH3
F B F H N H
F H
SN(B) = 3 SN(N)=4
BF3 has 3 electron pairs = trigonal planar.
NH3 has 4 electron pairs around the central N, but
the molecular structure is trigonal pyramidal. (The
lone pair helps to determine shape, but it is not an atom !).

3
Methane, CH4
109
SN=4, so VSEPR predicts a tetrahedral

arrangement of 4 electron pairs
• “normal” tetrahedral angle is 109.5 O
• Experimental angle CH4 109.5 O (0 lps)

4
Ammonia, NH3
lone pairs require
N more space than
H H bonding pairs
107
H
• Experimental angle NH3 107 O (1 lps)

5
Water, H2O
lone pairs require
O more space than
H bonding pairs
104
H
• Experimental angle H2O 104.5 (2 lps)

6
VSEPR rules
c b
The order of electron pair repulsions is A
bp-bp (a) < bp-lp (b) < lp-lp (c) Y
a
X
Molecule SN # lone pairs
PF5 5 0
SF4 5 1
ClF3 5 2
XeF2 5 3

7
VSEPR notes
PF5 - there are 2 axial and 3 equatorial sites.
SF4 - seesaw, or distorted pyramid structure ?

The seesaw structure minimizes lone pair-bond
pair repulsions :
2 at 90, and 2 at 120 is preferable to
3 at 90 and 1 at 180.

8
VSEPR notes
ClF3 - the 2 lone pairs occupy equatorial positions

to minimize the lone pair - lone pair interaction.
XeF2 - similarly, 3 lone pairs in equatorial sites.

9
VSEPR notes
Since we can predict the shapes of molecules, we
can also predict their dipole moments.
- +
If we represent the dipole of an individual bond
as a vector then the dipole moment of a
polyatomic molecule is the vector sum of each of
the vectors for the individual bonds.

0
What is the shape of the ozone
molecule, O3
It has 18 valence electrons, with 24 electrons needed to
form three completed octets, 6 shared electrons gives 3
bonds.
SN of central O atom is 2+1=3.
arrangement of electron pairs is trigonal ( 2 bp + 1 lp ).
molecule is V-shaped therefore dipole moment is non-
zero.

1

The Chemical Bond: OGN - Chapter 3

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The Chemical Bond: OGN - Chapter 3

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The Chemical Bond

OGN Chapter 3: Bonding 1

OGN Chapter 3: Bonding 2

If you use a search engine such as Altavista,

OGN Chapter 3: Bonding 4

OGN Chapter 3: Bonding 5

• are measured by spectroscopy or by

•The nuclei in a diatomic molecule

OGN Chapter 3: Bonding 6

OGN Chapter 3: Bonding 9

• Molecules adopt a geometry

OGN Chapter 3: Bonding 1

Ed is a measure of bond strength

OGN Chapter 3: Bonding 1

Why constant pressure?

• Bonds generally get weaker with increasing

OGN Chapter 3: Bonding 1

OGN Chapter 3: Bonding 1

OGN Chapter 3: Bonding 1

OGN Chapter 3: Bonding 1

ie. partial transfer of e-

OGN Chapter 3: Bonding 1

OGN Chapter 3: Bonding 1

OGN Chapter 3: Bonding 2

OGN Chapter 3: Bonding 2

OGN Chapter 3: Bonding 2

Electronegativity measures the ability

OGN Chapter 3: Bonding 2

Problem - this definition doesn’t take into

eg. Pauling - developed a scale of average

0.7 (Cs) - 3.98 (F) (see O+N, Fig. 14.1).

OGN Chapter 3: Bonding 2

OGN Chapter 3: Bonding 2

The difference between electronegativities

OGN Chapter 3: Bonding 2

H (2.2) Cl (3.16) (EN)=0.96,

Cl (3.16) Cl (3.16) (EN)=0,

intermediate polar covalent

OGN Chapter 3: Bonding 3

OGN Chapter 3: Bonding 3

OGN Chapter 3: Bonding 3

OGN Chapter 3: Bonding 3

Although it costs energy to transfer an electron

OGN Chapter 3: Bonding 3

• we ignored repulsive interactions.

OGN Chapter 3: Bonding 3

OGN Chapter 3: Bonding 3

OGN Chapter 3: Bonding 3

OGN Chapter 3: Bonding 3

OGN Chapter 3: Bonding 4

(a) e- between nuclei, strengthens bond

OGN Chapter 3: Bonding 4

OGN Chapter 3:HBonding H2 O 4

OGN Chapter 3: Bonding 4

•the SI unit for  is the Coulomb meter (Cm).

• the Debye is commonly used

 = ( 1 electronic charge ) ( 1 HF distance )

OGN Chapter 3: Bonding 4

 (Calc)= 1.47 x 10-29 Cm = 4.40 D

OGN Chapter 3: Bonding 4

Valence shell electron pair repulsion

OGN Chapter 3: Bonding 4