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247

3 Chemical bonding

This topic introduces the different ways by which chemical bonding occurs and the
effect this can have on physical properties.

3.3 Intermolecular forces, electronegativity and bond properties

INTERMOLECULAR FORCES

BILAL HAMEED INTERMOLECULAR FORCES

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 and co-ordinate Cambridge
(i) covalent International
bonding, AS andsuch
in molecules A Level Chemistry 9701
as hydrogen, syllabus
oxygen, Syllabus content
chlorine,
(dative covalent) hydrogen chloride, carbon dioxide, methane, ethene
bonding including Online Classes : Megalecture@gmail.com
(ii) co-ordinate (dative covalent) bonding, such as in the formation of the
shapes of simple
ammonium ion 248
and in the Al 2Cl 6 molecule
molecules
b) describe covalent bonding in terms of orbital overlap, giving σ and π
3 Chemical bonding bonds, including the concept of hybridisation to form sp, sp2 and sp3
orbitals (see also Section 14.3)
This topic introduces the different ways by which chemical bonding occurs and the effect this can have
c) explain the shapes of, and bond angles in, molecules by using the
on physical properties.
qualitative model of electron-pair repulsion (including lone pairs), using
as simple examples: BF3 (trigonal), CO2 (linear), CH4 (tetrahedral), NH3
Learning outcomes
(pyramidal), H2O (non-linear), SF6 (octahedral), PF5 (trigonal bipyramidal)
Candidates should be able
d) predict the shapes to: bond angles in, molecules and ions analogous
of, and
to those specified in 3.2(b) (see also Section 14.3)
3.1 Ionic bonding a) describe ionic bonding, as in sodium chloride, magnesium oxide and
3.3 Intermolecular a) calcium
describefluoride,
hydrogen including theusing
bonding, use of ‘dot-and-cross’
ammonia and waterdiagrams
as simple
forces, examples of molecules containing N–H and O–H groups
electronegativity
3.2 Covalent bonding a)
b) describe,
understand, including the terms,
in simple use of the
‘dot-and-cross’ diagrams:
concept of electronegativity and apply
andco-ordinate
and bond properties
(i) covalent bonding, in molecules such as hydrogen, oxygen, (see
it to explain the properties of molecules such as bond polarity chlorine,
(dative covalent) alsohydrogen
Section 3.3(c)), thecarbon
chloride, dipoledioxide,
moments of molecules
methane, ethene(3.3(d)) and the
bonding including behaviour of oxides with water (9.2(c))
(ii) co-ordinate (dative covalent) bonding, such as in the formation of the
shapes of simple c) explain the terms
ammonium ionbond energy,
and in the Al bond length and bond polarity and use
2Cl 6 molecule
molecules them to compare the reactivities of covalent bonds (see also Section
b) describe covalent bonding in terms of orbital overlap, giving σ and π
5.1(b)(ii))
bonds, including the concept of hybridisation to form sp, sp2 and sp3
d) orbitals
describe intermolecular
(see also Sectionforces
14.3) (van der Waals’ forces), based on
permanent and induced dipoles, as in, for example, CHCl 3(l); Br2(l) and
c) explain the shapes of, and bond angles in, molecules by using the
the liquid Group 18 elements
qualitative model of electron-pair repulsion (including lone pairs), using
as simple examples: BF3 (trigonal), CO2 (linear), CH4 (tetrahedral), NH3
3.4 Metallic bonding a) (pyramidal), H2O (non-linear),
describe metallic SF6 (octahedral),
bonding in terms of a lattice PF (trigonalions
of 5positive bipyramidal)
surrounded by delocalised electrons
d) predict the shapes of, and bond angles in, molecules and ions analogous
to those specified in 3.2(b) (see also Section 14.3)
3.5 Bonding and a) describe, interpret and predict the effect of different types of bonding
physical properties
3.3 Intermolecular (ionic bonding,
a) describe covalent
hydrogen bonding,
bonding, usinghydrogen
ammonia bonding,
and water other intermolecular
as simple
forces, interactions, metallic bonding) on the physical properties
examples of molecules containing N–H and O–H groups of substances
electronegativity b) understand,
b) deduce the type of bonding
in simple terms,present from of
the concept given information and apply
electronegativity
and bond properties c) itshow understanding
to explain of chemical
the properties reactions
of molecules in terms
such as bondofpolarity
energy (see
transfers
associated
also Sectionwith the the
3.3(c)), breaking
dipoleand makingof
moments ofmolecules
chemical bonds
(3.3(d)) and the
behaviour of oxides with water (9.2(c))
c) explain the terms bond energy, bond length and bond polarity and use
them to compare the reactivities of covalent bonds (see also Section
Back to contents page 5.1(b)(ii)) www.cie.org.uk/alevel 19
d) describe intermolecular forces (van der Waals’ forces), based on
permanent and induced dipoles, as in, for example, CHCl 3(l); Br2(l) and
the liquid Group 18 elements

3.4 Metallic bonding a) describe metallic bonding in terms of a lattice of positive ions
surrounded by delocalised electrons

3.5 Bonding and a) describe, interpret and predict the effect of different types of bonding
physical properties (ionic bonding, covalent bonding, hydrogen bonding, other intermolecular
interactions, metallic bonding) on the physical properties of substances
b) deduce the type of bonding present from given information
c) show understanding of chemical reactions in terms of energy transfers
associated with the breaking and making of chemical bonds

Back to contents page www.cie.org.uk/alevel 19

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249

BOND POLARITIES
In a covalent bond between two different atoms, the atoms do not
The example attract thetwo
in which electron pairatoms
hydrogen in thebond
bond equally.
is simple How strongly
because both atomstheareelectrons
the same. are attracted depends on the size of the individual atoms and their
nuclear
Also, each one charge.
has a single proton and a single electron, so the attractions are easy
to identify. In the F 2 molecule, the two F atoms attract the electrons in the bond
equally and thus the electrons lie symmetrically (Figure 3.87). This
However, many covalent bonds form between two different atoms.
molecule is non-polar.
These atoms often have different attractions for shared electrons.

1
However, in HF, F is more electronegative than H and attracts the
electrons in the H–F bond more strongly than the H atom does. The
electrons in the bond thus lie closer to the F than to the H (Figure 3.8
H–F is a polar molecule. The unsymmetrical distribution of electron
density results in small charges on the atoms. F is − because the electro
However,
in the bond lie closer to F, whereas electron in HF,has
density F isbeen
morepulled
electron
aw
from H, so it is +. electrons in the H–F bond more stron
BOND POLARITIESelectrons in the bond thus lie closer to
H–F is a polar molecule. The unsymm
Now consider a diatomic molecule composed density results in small charges on the
of two different elements; HF is a common in the bond lie closer to F, whereas el
example. from H, so it is +.
It has been experimentally shown that the
tes a small negativeelectrons in the H—F bond are not equally However, in
shared; the electrons spend more time in the electrons in th
vicinity of the fluorine atom. electrons in th
There are various scales of electronegativity and it is important
H–F istoa realise
polar
This is because fluorine is a more
that, although they are derived from physical quantities (such as bond
density results
electronegative element
energies),
− indicates than hydrogen.
the numbers themselves are not physical quantities;
a small negative they
in the havelie
bond
charge. units and must only be used in a comparative way. The most fromcommonly
H, so it i
used scale of electronegativity is that developed by Linus Pauling. The
2

There areare
electronegativity values for some elements various
shownscales of electronega
in Table 3.11.
that, although they are derived from p
energies), the numbers
Noble gases do not have electronegativity values asthemselves
they do notare
als have higher units and must only be used in a com
gativities thanBILAL
metals.
HAMEED form compounds. INTERMOLECULAR FORCES
used scale of electronegativity is that d
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electronegativity values for some elem
 bond enthalpy reflects the strength of the covalent bond. As we 151
I–I
ve from single to double to triple bonds theClasses
Online number: of electrons in
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250
bond increases resulting in an increase in electrostatic forces and a Table 1 Average bond enthalpies
tening of the bond length. This trend can be seen in the carbon– at 298 K
on bond of the homologous series of alkanes, alkenes, and alkynes.

nd polarity POLAR BONDS

polarity of a bond can be described by the difference in
Polar covalent bond is the preferred term for a bond made up of
tronegativity of the bonded atoms (tables 3 and 4).
unequally shared electron pairs.
m Electronegativity Bond 4(Electronegativity) Bond enthalpy/
One end of the bond (in this case, the F atom)
kJ molis
–1 more electron rich
2.2
(higher electron density), hence,
1.8 more negative.
567
4.0 H–F

3.2
The other end
H–Clof the bond1.0
(in this case, the431
H atom) is less electron rich
(lower electron density), hence, δ-
r 3.0 H–Br 0.8 more positive. 366
δ+
These two ends,
le 3 Electronegativity values
one somewhat positive and the other
Table 4 Bond polarity and bond enthalpy at 298 K
somewhat negative may be described as electronic H F
orine has the highest electronegativity value of any element.
polarity of the poles, hence
H–F bond the term
results in a polar
partialcovalent
charge on bonds.
each
m. The bond is said to have ionic character. The partial charges
3
act one another, increasing the strength of the bond (figure 1). Figure 1 The polar H–F bond

153

POLAR BONDS
In a polar covalent bond, the shared electrons, which are in a molecular orbital,
are more likely to be found nearer to the atom whose electronegativity is higher.

This unequal distribution of charge makes the bond polar covalent.

To emphasize the dipole nature of the HF molecule, the formula can be written
as Hδ+ Fδ−. The symbol δ means partial.
With polar molecules, such as HF, the symbol δ+ is used to show a partial
positive charge on one end of the molecule.
Likewise, the symbol δ− is used to show a partial negative charge on the other
end.

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251

ELECTRONEGATIVITY
Electronegativity is a measure of the ability of an atom to attract electrons
in a chemical bond. Elements with high electronegativity have a greater
ability to attract electrons than do elements with low electronegativity.
The four most electronegative elements are F, O, N, Cl.
electronegativity increases

increases
Electronegativity increases across a period and decreases down a group
5

BOND POLARITIES
Non-polar bond Polar bond
• Similar atoms have the same • Different atoms have different
electronegativity electronegativities
• They will both pull on the • One will pull the electron pair closer to its end
electrons to the same extent • It will be slightly more negative than average, δ-
• The electrons will be equally • The other will be slightly less negative, or more
shared positive, δ+
• A dipole is formed and the bond is said to be
polar
• Greater electronegativity difference = greater
polarity

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252

Linus Pauling
Linus Pauling
related
Linus the MOLECULAR
related
Paulingelectronegativity
the
related the POLARITY
electronegativity
electronegativity
difference diffbetween
erencediffbetween
erence between
two atomstwo
Thetoatoms
thetwo ionic
toatoms
the
electronegativity character
ionic
to the
character
of
ionic
difference a between
bond.
character
of aHe
bond.
twosuggested
of He
a bond.
atoms suggested
that
Heansuggested
covalently that an that an
bonded Exam
electronegativity
electronegativity
togetherelectronegativity
difference
results in diff
theof erence
1.7diff
electronscorresponded
oference
1.7 more
lying corresponded
of 1.7 tocorresponded
towards50%one to
ionic
50%
atom character
ionic
to 50%
than character
the in in If aske
ionic character in
a bond and
aother.
bondreasoned
Weand
a call
bond
reasoned
that
such and aa bond
greater
reasoned
thatpolar.
a electronegativity
greater
that aelectronegativity
greater electronegativity
difference diffthan
erencethis
diffthan
erence that th
thisthan this
corresponded
corresponded
tocorresponded
a structure
to a structure
that
to was
a structure
that
more wasionic
that
more than
was
ionic
more
covalent,
than
ionic
covalent,
whereas
than covalent,
whereas whereas two e
However, whether an overall molecule is polar also depends on the
if the diff
ifshape
erence
the diff differe
ofifis
erence
thethe
less diff
than
iserence
molecule. less
thatthan
the
is less
that
bonding
than
the that
bonding
is more
the bonding
iscovalent
more covalent
isthan
moreionic.
covalent
than ionic.
than ionic.
This is aThis
useful
is aidea,
This
usefulbut
is idea,
a ituseful
must
butidea,
be
it must
used
butbe with
it must
used
great
with
be used
caution.
great
with
caution.
For
great
instance,
caution.
For instance, and c
For instance,
The polarity of molecules is distinct from the polarity of individual bonds; less th
KI (electronegativity
KI (electronegativity
KI (electronegativity
difference diff1.7)
erencewould
diff1.7)
erence
come
would1.7)
outcome
would
of this
outcome
discussion
of this
outdiscussion
of this discussion
a non-polar molecule may have polar bonds.
as havingas 50%
having
ionic
as50%
having
and
ionic
50%
50%and
covalent
ionic
50%andcovalent
character,
50% covalent
character,
and NaIcharacter,
and
(diffNaI
erence
and
(diffNaI
erence
(difference
of 1.6) would
of 1.6)appear
would
of 1.6)to
appear
would
be mostly
toappear
be covalent,
mostly
to becovalent,
mostly
whereas covalent,
whereas
both behave
whereas
both asbehave
bothasbehave as
predominantly
predominantly
ionic
predominantly
compounds.
ionic compounds.
ionic
Pauling,
compounds.
Pauling,
in his original
Pauling,
in his original
discussion
in his original
discussion
of discussion
of of
this, wasthis,
actually
was this,
actually
referring
was referring
actually
to diatomic
referring
to diatomic
molecules
to diatomic
molecules
and not
7 molecules
and
to macroscopic
not and
to macroscopic
not to macroscopic
compounds.
compounds.compounds.

The electronegativity
The electronegativity
The electronegativity
differencediffbetween
erence diffbetween
erence
two atoms between
twocovalently
atomstwocovalently
atoms
bonded covalently
bonded bonded
togethertogether
results in
together
results
the electrons
inresults
the electrons
in
lying
themore
electrons
lyingtowards
morelying
towards
onemoreatomtowards
onethan
atom the
one
than
atomthethan the
other. We
other.
call We
such
other.
call
a bond
such
We calla bond
suchHowever,
polar. a bondHowever,
polar. whether
polar. However,
whether
an overallwhether
an molecule
overallanmolecule
overall
is molecule
is is
polar also
polar
depends
alsopolar
depends
on also POLAR
the shape
depends
on theMOLECULES
theofshape
on the
molecule.
of shape
the molecule.
of the molecule.
For a For
molecule
For a molecule
to
Forbe
a molecule a polar
to molecule
topolar
be be
it polar
must
to be
it musthave
ithave
must
polar
aapositive
have
it must
a positive
positive have
endto ato
end thepositive
end
the to the
molecule end to the
moleculemolecule
andand molecule
a negative
andend.
a negative a negative
and
end.
For a For instance,
negative
end.
instance, HCl,For
NH instance,
3 HCl,
end.andFor
HNH
2O 3 and
instance,
HCl,
are allNHH 32O
and
HCl,
polar. are
NHHall
23OandareHall
2O are all
polar (Figure
polar (Figure
polar
3.89). These
(Figure
3.89). molecules
These
3.89). molecules
These
all havemolecules
all
an have
overall
an
all dipole
These molecules all have an overall dipole moment, and the arrow
overall
have andipole
overall moment,
moment, dipole moment,
and the and
arrow
theindicates
indicates arrow
and theindicates
the
arrow
the direction direction
of indicates
thedipole
the direction
of the direction
dipole
moment.of themoment.
dipole
of themoment.
dipole moment.

8
Saying
momen
AlthoughAlthough
individual
Although
individual
bondsindividual
may
bondsbemay polar,
bonds
bethe
may
polar,
overall
bethe
polar,
overall
molecule
the molecule
overall molecule
saying t
may bemaynon-polar
be may
non-polar
if,beowing
non-polar
if, to
owing
theif,symmetry
to
owing
the symmetry
to of
thethe
symmetry
molecule,
of the molecule,
ofthe
the molecule,
the the
dipole moments
dipole moments
BILAL HAMEED dipole
of themoments
individual
of the individual
of bonds
the individual
cancel
bonds out.
cancel
bonds out.
cancel out.
INTERMOLECULAR FORCES
www.youtube.com/megalecture
a bond and reasoned that a greater electronegativity difference
a bond than this
and reasoned that the
that a greater bonding between
electronegativity diffe
corresponded to a structure that wasOnlinemoreClasses
ionic than covalent, whereas
corresponded two elements is ionic
to a structure that was more ionic than cov if the
: Megalecture@gmail.com
f the difference is less than that the bonding is more covalent
if253 than
the diff diffthe
ionic.is less than that
erence erence is more
bonding than cov
is more 1.7
This is a useful idea, but it must be used with great caution.
ThisForis a instance,
useful idea, but it mustandbecovalent
used withif the diffcautio
great eren
KI (electronegativity difference 1.7) would come out ofKI this(electronegativity
discussion less1.7)
difference than 1.7. come out of
would
as having 50% ionic and 50% covalent character, and NaIas (diff erence
having 50% ionic and 50% covalent character, and NaI
of 1.6) would appear to be mostly covalent,POLAR
whereas bothof behave
1.6) would
MOLECULES as appear to be mostly covalent, whereas both
predominantly ionic compounds. Pauling, in his originalpredominantly
discussion of ionic compounds. Pauling, in his original
his, was actually referring to diatomic molecules and not this,
to was actually referring to diatomic molecules and not
macroscopic
compounds. compounds. δ+
CHCl3 δ+ NH3 Cl
δ+ δ-
H δ- δ- O C
N

The electronegativity difference

C
between
Cl
δ-
The electronegativity
two atoms Hcovalently bonded
H difference between
Cl two atoms cova
Cl δ+ δ+

ogether results in the electrons

δ- Cl
lying more
δ-
towards one
δ+
together
atomδ+than
H results
the in theδ-electrons
COCl
lying
δ+
more towards one a
δ- δ+ 2

other. We call such a bond polar. However, whether an other. overallWe call suchis a bond polar. However, whether an o
molecule
polar also depends on the shape of the molecule. polar also depends on the shape of the molecule.
For a molecule to be polar it must have a positive end For a molecule to be polar it must have a positive en
to the
molecule and a negative end. For instance, HCl, NHmolecule and a negative end. For instance, HCl, NH3
3 and H2O are all
polar (Figure 3.89). These molecules all have an overall d
polar (Figure 3.89). These molecules all have an overall dipole moment,
and the arrow indicates the direction of the dipole mome
and the arrow indicates the direction of the dipole moment.
9

Saying that a molecule has a

NON-POLAR Although MOLECULES individual bonds may be
moment polar,
is just the overa
another way
Although individual bonds may be polar, the overallmay molecule
be non-polar if, owing tothat
the itsymmetry
Although individual
saying is polar. of the
may be non-polar if, owing to thebonds may beofpolar,
symmetry the
the dipoleoverall molecule
molecule, the
moments of the individual bonds cancel ou
dipole momentsmay
of be
thenon-polar if, owing
individual bondstocancel
the symmetry
out. of the molecule,
the dipole moments of the individual bonds cancel out.
CO2 is a non-polar molecule. Each C–O bond is pola
CO2 is a non-polar molecule. Each C–O bond is
CO2 is a non-polar molecule. Each C–Opolar, because
is bond
more oxygen
iselectronegative
polar, than carbon, but overall the dipol
s more electronegative thanoxygen
because carbon,isbut overall
more the dipoles
electronegativetherecancel
is no
than so thatbutdipole moment and the molecule is no
overall
carbon,
here is no overall overall
dipole moment andcancel
the dipoles the molecule is non-polar.
so that there isBF is also non-polar.
no3 overall dipole Again, each individual bond is p
BF3 is also non-polar. Again, each individual bond is polar but the
moment and the molecule is non-polar.dipoles cancel.
dipoles cancel.
BF3 is also non-polar. Again, each individual bond is polar but
the dipoles cancel.

10

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 means that the b
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254 That we simp
intermolecular fo
can be seen if we
NON-POLAR MOLECULES
In contrast, a molecule containing polar bonds may be either polar or non-
polar depending on the relative arrangement of the bonds and any lone pairs
ofCCl 4 is non-polar,
electrons,CCl
e.g. but CHCl
4 isCCl
non-polar, is polar
3but CHCl (Figure
4 is non-polar, but
3.90).
3 isCHCl
polar (Figure 3.90).
3 is polar.
p
why as to why
nswer
gh
olar: ‘although
olar
l bond is polar
erence in
oms,
ty of the atoms,
of the
symmetry of the
el’.
ipoles cancel’. Explain why BrF has a higher boiling
point than ClBr, despite ClBr having Br2 is the only
the greater relative molecular mass.
11
boiling point as
Some polarSome
and non-polar
polar and molecules
non-polar are shown in
molecules areTable
shown3.12.
in Table 3.12.
therefore, stronge
uct
s the of product
the of the
ween
stancethe between the
eis (D).
the debye (D).

Cis-1,2-dichloro
This will also be discussed on pages isomers – they d
487–491. DIPOLE MOMENTS C=C (Figure 3.9

g atoms
he in order
following of in order of 15 Sort the
atoms 15following
Sort themolecules
following into polar and
molecules into polar and
allest first):
gativity (smallest first): non-polar molecules. For the polar molecule
non-polar molecules. For the polar molecule
Br H NaBr Na draw diagrams
drawshowing
diagramstheshowing
dipoles.the dipoles.
ecules
polar from from the following XeF6
the following
molecules XeF
XeF46 SF
XeF4 4 PCl
SF45 SF
PCl2 5 SF2
lecules,
he draw diagrams
e polar molecules, draw diagrams SF 6 ClF
SF65 BrF
ClF35 SOCl
BrF3 2 SOCl2
he dipoles.
HCNPH3 SCl
PH23 CF
SCl4 2 CF4
O
OCl32 BCl
O3 3 C
BClCl
2 32 C2Cl2 Both molecul
CH2Cl2
except that one
the boiling poin
12
interactions in th
lecular
ow
w intermolecular

oww physical Br2 is a liquid

Br2atis room
a liquidtemperature. It consists of
at room temperature. It discrete
consists molecules
of discrete in
molecules in
which
lecular molecular
ovalent the two Br atoms are joined by a covalent bond (an intramolecular
which the two Br atoms are joined by a covalent bond (an intramolecular
end on theBILALforce).
HAMEED But if Br2 isBut
force). to if
beBra 2liquid, there
is to be must there
a liquid, be some forces
must be some Hydrogen bondi
INTERMOLECULAR
between
forces between FORCES
molecules holding them in thethemliquid
in state (otherwise it would beitawould
gas). be a gas).
forces
ints These forces
of points of
molecules holding
are intermolecular
These
the liquid
forces (Figure
forces are intermolecular
state (otherwise
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3.91).
forces (Figure 3.91).
responsible for ic
boiling
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255

SKILL CHECK 1
Decide whether the following bonds are polar or non-polar. if the
bond is polar, state which is the δ+ atom, and explain whether or not
the molecule is polar:
A C-O as in CO2
B C-I as in CH3I

13

SKILL CHECK 2
Predict which of the following bonds are polar, and, if polar, in which
direction the electrons are pulled:
a. O—S b. Cl—Cl c. C—N d. I—Cl

Predict whether each of the following molecules is polar:

a. BCl3 b. HCl c. NH3 d. SiCl4

14

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256

SKILL CHECK 3
Predict whether each of the following molecules is polar:
a. CO2 b. BrCl c. SCl2 d. CS2

Using the shapes drawn on slide 48 to 51, predict whether each of the
following molecules is polar:
a. CF4 b. Cl2O c. PF3 d. NCl3 e. SiCl4 f. SO3

15

INTERMOLECULAR FORCES
Intermolecular forces are weak attractive forces between molecules.
These forces determine such properties as the solubility of one substance in
another and the freezing and boiling points of liquids.
Without intermolecular forces there could be no molecular liquids or solids.

16

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257

INTERMOLECULAR FORCES
Weak intermolecular forces arise from electrostatic attractions between
dipoles, including attractions between:

• Molecules with permanent dipoles such as hydrogen chloride

• A permanent dipole in one molecule and a dipole induced in a
neighbouring molecule, such as the attraction between iodine and
water

• Temporary dipoles are created fleetingly in non-polar atoms or

molecules

17

VAN DER WAALS’ FORCES DUE TO PERMANENT DIPOLES

Van der Waal’s forces due to permanent dipoles are interactions between
polar molecules - the positive end of one molecule attracts the negative
end of a neighbouring molecule.

H Cl H Cl H Cl H Cl
δ+ δ- δ+ δ- δ+ δ- δ+ δ-

δ- δ- δ-
Cl Cl Cl van der Waal’s forces
C C C
Cl δ- Cl δ- Cl δ-
H H H
δ+ Cl δ+ Cl δ+ Cl
δ- δ- δ-

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VAN DER WAALS’ FORCES DUE TO PERMANENT DIPOLES

he H–Cl

l(l) but,
molecular
– 19

ttractions.
ar
der Waals’
n der All other things being equal:
this basically means that we should
ole VAN DER WAALS’compare compounds
FORCES with relative
IN NON-POLAR MOLECULES
molecular
ling pointsIntermolecular forces also existmasses as molecules.
in non-polar similar Van
as der Waal’s forces
possible.
due to induced dipoles are the intermolecular attraction resulting from the
uneven distribution of electrons and the creation of temporary dipoles.
ecular massBecause electrons move quickly in

be similar.orbitals, their position is constantly

changing; at Ifanymolecules with similar relative
given instant they
ractions ascould be anywhere in an atom.
molecular masses are compared,
moleculesThe possibility will exist that one side
polar molecules have higher
es and will have more electrons than the other.
melting and boiling points than
ust be This will give rise to a dipole.
non-polar molecules. 20

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259

VAN DER WAALS’ FORCES DUE TO INDUCED DIPOLES

Consider liquid argon. The electrons in an atom are in constant motion, and at any one
time the electrons will not be symmetrically distributed about the nucleus.

This results in a temporary (instantaneous) dipole in the atom, which will induce an
opposite dipole in a neighbouring atom.
These dipoles will attract each other so that there is an attractive force between atoms.

Although the dipoles are constantly disappearing and

reappearing, the overall force between the argon
atoms is always attractive, because a dipole always
induces an opposite one.

21

molecular mass also increases, and we normally talk about ‘an increase in the
er Waals’ forces VAN DER WAALS’ FORCES DUE TO INDUCED DIPOLES
strength of van der Waals’ forces as the relative molecular mass increases’.
he relative
A clear correlation between boiling point and relative molecular/
ncreases. In general, van der Waals’ forces get stronger as the number of electrons in a
atomic mass can be seen down group 7 (blue line) and down group 0 (red
molecule increases.
line) in Figure 3.94. As the number of electrons increases, the relative molecular
mass also increases, resulting in an increase in the strength of van der Waals’ forces.

22

Consider group 7: fluorine (Mr 38.00) is a gas at room temperature,

but iodine (Mr 253.80) is a solid. This is because there are more electrons
in an iodine molecule, and the atoms making up the molecule are larger.
More electrons means that the temporary dipoles will be larger with INTERMOLECULAR
BILAL HAMEED
more FORCES
electrons moving around. The larger atoms in the molecule means that
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the outer electrons will be less strongly held, and therefore the induced
 In addition to the relatively weak forces described above, ionic and covalent bonds
(discussed in detail in Chapter 5) are strong forces that greatly affect the melting point
of a compound:
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260 a major source of
! In ionic solids, ionic bonds (electrostatic interactions) provide
attraction between particles. These types of solids tend to be hard but brittle (the
ionic lattice can crack) and have very high melting points. Lattice energy is a measure
of the strength of the interactions between ions in the lattice of an ionic solid. The
larger the lattice energy, the stronger the ion-ion interactions.
! In covalent solids, particles are bound to each other within strong networks of covalent
VAN DER WAALS’ FORCES DUE TO INDUCED DIPOLES
bonds. These solids are often exceptionally hard and have very high melting points.

e 11-2: a) b) Attraction c) Electrons b.p. / oC

− δ−
Inter-
+ δ+ − δ+ δ+
ecular eδ- e− δ+ δ+ NOBLE GASES
ctions − 2+ 2+
δ-
hydrogen bond
+ δ- δ−
δ+ He 2 -269
nclude − + e −
e −
δ+
dipole- van der Waal’s forces Ne 10 -246
inter- − + due to induced dipoles dipoles
ctions, induced Ar 18 -186
ondon + −
ersion Kr 36 -152
+ −
s, and ALKANES
drogen Attraction δ− δ+ δ− δ+
bonds. Repulsion CH4 10 -161
C2H6 18 -88
C3H8 26 -42

oving Through States with Phase Diagrams

23
The previous sections described how microscopic interactions between particles can lead to
large-scale differences in the properties of a sample, especially by causing the sample to be
in different states (solid, liquid, or gas). This section describes some tools you can use to
track the state of a sample as it moves through different regions of temperature, pressure, or
added heat energy.

Phases and phase diagrams

Each state (solid, liquid, gas) is called a phase. When matter moves from one phase to another
due to changes in temperature and/or pressure, that matter is said to undergo a phase transi-
tion. The way a particular substance moves through states as temperature and pressure vary is
EXAMPLES OF VAN DER WAAL’S
summarized by a phase diagram. Phase diagrams usually display pressure on the vertical axis
and temperature on the horizontal axis. Lines drawn within the temperature-pressure field of
the diagram represent the equilibrium boundaries between phases. A representative phase dia-
BOILING
gram is shown in FigurePOINTS
11-3. ReferOF HYDRIDES
back OF
to this figure as GROUP 14
you read through the section.

to gas is called boiling, and the temperature at which boiling occurs is

Moving from liquid 100
called the boiling point. The normal boiling point is when this transition occurs at 1 atmos-
phere of pressure. Moving from solid topoints
The boiling liquid is
ofcalled melting,increase
the hydrides and the temperature at which
with increasing number of
melting occurs is called the melting point. The melting point temperature is the same as the
electrons. CH4 has the lowest boiling point as it is the smallest molecule.
freezing point temperature, but freezing implies matter moving from liquid to solid phase.
The melting point a substance has at 1atm pressure is called the normal melting point. Just
BOILING POINT / C°

as freezing and melting points are the same, condensation points and boiling points are the
0
same temperature. For this reason published 50 tables are of100
freezing points
140 and boiling points.
Mr

PbH4

SiH4 GeH4 Larger molecules have more electrons and

therefore have greater intermolecular forces and
therefore higher boiling points.
-160 CH4

24

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261

Let us compare the boiling points of the hydrides of group 6 elements:

HYDRIDES OF GROUP 16

25

The boiling point increases from H2S to H2Te, as would be expected

from the increase in the strength of van der Waals’ forces as the relative
molecular mass increases.
H2O has, however, a much higher boiling point than would be
expected from its relative molecular mass. This suggests that there must
be intermolecular forces other than van der Waals’ forces between H2O There is mo
than just an
molecules and that these intermolecular forces are stronger than van der
HYDROGEN between dip
Waals’ forces. These extra intermolecularBONDING
forces between H2O molecules
to a very ele
are called hydrogen bonds. A hydrogen bond between two water molecules
the electron
is shown in Figure 3.98. HO 100
2
strongly from
an interactio
The higher than
It is important to realise that, although hydrogen bonding is the density of th
expected boiling in one mole
BOILING POINT / C°

strongest of the intermolecularHF forces, it is much weaker than

0
points of NHbonding.
covalent 3, H2O GROUP VI
50 100 140
Mr
in a differen
and HF are due to GROUP V
HI
a directiona
NH3 HS
intermolecular
2
GROUP VII bonds. If the
Hydrogen bonding occurs between molecules HCl when a very PbH4 dipole–dipo
HYDROGEN HBr
electronegative atom (N, O, F) is joined to a hydrogen atomGROUP in the
IV electronegat
BONDING PH 3
expected to
molecule. The electronegative atom withdraws electron GeH
density from the 4

SiH
H, polarising the bond such that there is a strong interaction between the
-160
4 bonding, bu
+ H and the − atom (N, O,CHF) on the other molecule. be explained
26 4
more diffuse
The hydrogen bonding between ammonia molecules and hydrogen
interacting e
fluoride molecules is shown in Figure 3.99.

BILAL HAMEED INTERMOLECULAR FORCES

The requ
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 expected from its relative molecular mass. This suggests that there must
be intermolecular forces other than van der Waals’ forces between H2O There is mo
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molecules :and
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that these intermolecular forces are stronger than van der
between dip
262
Waals’ forces. These extra intermolecular forces between H2O molecules
to a very ele
are called hydrogen bonds. A hydrogen bond between two water molecules
the electron
is shown in Figure 3.98. strongly fro
an interactio
It is important to realise that, although hydrogen bonding is the density of th
HYDROGEN BONDING
strongest of the intermolecular forces, it is much weaker than in one mole
covalent bonding. in a differen
Strong hydrogen bonds can form with a hydrogen atom that is covalently bonded to a directiona
bonds. If th
very electronegative atoms in the upper-right part of the periodic table: nitrogen, dipole–dipo
Hydrogen bonding occurs between molecules when a very
oxygen, and fluorine. electronegative atom (N, O, F) is joined to a hydrogen atom in the electronega
molecule. The electronegative atom withdraws electron density from the expected to
elements: When a hydrogen atom bonds to an atom of N, O, or F, the hydrogen atom has a bonding, bu
H, polarising the bond such that there is a strong interaction between the
large, partially positive charge. + H and the − atom (N, O, F) on the other molecule. be explaine
more diffus
The hydrogen bonding between ammonia molecules and hydrogen
The partially positive hydrogen atom interacting
fluorideofmolecules
polar molecules
is shown incan be 3.99.
Figure attracted to the
unshared pairs of electrons of neighbouring molecules.

The requ
are that
a very el
O, F – w
one lone
27

expected
he relative

ld be
here must
ween H2O There is more to hydrogen bonding
than just an electrostatic interaction
han van der
between dipoles. When H is attached
O molecules HYDROGEN BONDING
to a very electronegative atom,
ater molecules
the electron density is pulled away
One reason
strongly from thethat hydrogen
H. There is then bonds are such strong forces is because the
an interaction between the electron
is the hydrogen
density of theatom ison
lone pair small
N, O andor F has only one electron.
han in one molecule and the H nucleus
When thatmolecule.
in a different electron is pulled
There is thus away by a highly electronegative atom, there
a directional component to hydrogen
are no more electrons under it. Thus, the single proton of the hydrogen
bonds. If the interaction were purely
y dipole–dipole,
nucleus Cl, with theexposed.
is partially same
in the electronegativity as N, would also be
ity from the expected
As to participate
a result, in hydrogen
hydrogen’s proton is strongly attracted to the lone pair of
between the bonding, but it does not. This could
electrons
be explained of other
by the highermolecules.
energy and The combination of the large
more diffuse lone pair on the Cl not
hydrogen electronegative difference (high polarity) and hydrogen’s small size
interacting effectively with the H.
accounts for the strength of the hydrogen bond.

28
The requirements for H bonding
are that the H atom is attached to
a very electronegative atom – N,
O, F – which possesses at least
one lone pair of electrons.

BILAL HAMEED INTERMOLECULAR FORCES

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 There is no hydrogen bonding between molecules of CH3CH2F, as the
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263

CH3OCH3 is an ether with the structure shown in Figure 3.100. It is a

polar molecule, but there is no hydrogen bonding between molecules.
EXAMPLES OF HYDROGEN BONDING
The hydrogen bonding between some molecules of ethanol is shown in
Figure 3.101.
The cis form has a lower melting point, because as well as intermolecular
hydrogen bonding it is also able to participate in intramolecular hydrogen
bonding (Figure 3.102). This means that there is less hydrogen bonding
between molecules andethanol
that the intermolecular forces are weaker than in
Substanceshydrogen
the trans form. The trans form participates only in intermolecular that are able to
n influence Ethanol (C2H5OH) is very soluble in water, because ethan
bonding, as the COOH groups are further away from each other; thehydrogen bonding
participate in
ances in hydrogen bond to the water (Figure 3.105). The hydrogen
intermolecular forces are therefore stronger in the transwill generally be soluble in water,
form.
cules that are as they are able to hydrogen bond between water and ethanol molecules in the solution rele
d are soluble to the water. pays back the energy to break theacid
hydrogen bonds in pure
but-2-ene-1,4-dioic
discussed ethanol.
Only intermolecular forces are broken when covalent molecular
Consider
substances arethe cis andortrans
melted forms
boiled – of butenedioic
covalent bondsacid:
are not broken.

ethanol inuence
water Octan-1-ol is insoluble in water. Although there is some h
We have looked at several factors that infl the strength of The stronger the intermolecular
bonding between the O–H group of the alcohol and the
intermolecular forces and hence the melting and boiling points of forces, the more energy must be chain prevents water molecules on
the long hydrocarbon
covalent substances. Now let us consider all the above points together supplied to hydrogen
break them and theto each other (Figure 3.106). Energy is
bonding
with some examples. higher the boiling point.
break the hydrogen bonds between the water molecules, b
paid back as only van der Waals’ forces form between the
Intermolecular forces increase in strength as: 29
and the hydrocarbon part of the molecule.
van der Waals’ forces < permanent dipole–dipole < hydrogen bonding
WEAKEST STRONGEST
Relative molecular mass –
If relative molecular masses are approximately equal, then the boiling generally substances with higher
points usually go in the order shown in Table 3.13. relative molecular masses have
higher melting points and boiling
points due to stronger van der
Waals’ forces.

SOLUBILITY
Generally a substance will dissolve in a solvent if the intermolecular forces in the solute
and solvent are similar. E.g. pentane is readily soluble in hexane but not in water.
Compare the
Theboiling points of
amount of sulfur,
energy chlorine and argon.
required to break the van der Waals’ forces in pure hexane and
pure pentane is paid back when van der Waals’ forces are formed between the
Sulfur, chlorine and argon are all non-polar substances, and therefore the strongest intermolecular forces are van
molecules
der Waals’ forces. of hexane
Any difference betweenand
thesepentane
substances is thus due to the strength of van der Waals’ forces,
which is affected by relative molecular mass (relative atomic mass for argon). Sulfur forms S8 molecules with a
relative molecular mass of 256.48; Cl2 has a relative molecular mass of 70.90; and Ar has a relative atomic
Consider themass of
dissolving of sodium chloride:
39.95. Therefore the boiling point of sulfur would be expected to be highest, as S8 has a greater relative molecular
‘+ water’
mass and therefore stronger van der Waals’ forces than Cl2 and Ar. More energy is thus required to break the
NaCl(s) NaCl(aq)
intermolecular forces in sulfur than to break the intermolecular forces in chlorine and the interatomic forces in Ar.
Chlorine would be expected to have a higher boiling point than Ar, again due to the greater The mass aqueous solution contains aqueous ions (Na+(aq) and
and the stronger
van der Waals’ forces. Ion–dipole interactions form between the water and the i
3.107). Energy is required to break the electrostatic forces
lattice but energy is released when hydrated ions are form
released when the hydrated ions are formed is comparable
required to break apart the lattice then the substance is ge
30

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SOLUBILITY
Pentane does not dissolve in water because there is hydrogen bonding
between water molecules.

If pentane were to dissolve in water there would be van der Waals’ forces
between water molecules and pentane. The energy released if van der Waals’
forces were to form between water molecules and pentane molecules would not
pay back the energy required to break the hydrogen bonds between water
molecules, as hydrogen bonds are stronger than van der Waals’ forces

31

SOLUBILITY
Ethanol (C2H5OH) is very soluble in water, because ethanol is able to form
hydrogen bonds with the water.
Substances that are able to
The hydrogen bonding between water andinethanol
participate moleculesEthanol
hydrogen bonding in the (C2H5OH) is very soluble in water, beca
will generally be soluble in water, hydrogen bond to the water (Figure 3.105). The
solution releases energy and pays back the energy to break
as they are able to hydrogen bond the hydrogen
between water and ethanol molecules in the solu
to the water. pays back the energy to break the hydrogen bond
bonds in pure water and pure ethanol. ethanol.

ethanol in water Octan-1-ol is insoluble in water. Although there

bonding between the O–H group of the alcohol
the long hydrocarbon chain prevents water molec
hydrogen bonding to each other (Figure 3.106).
break the hydrogen bonds between the water mo
paid back as only van der Waals’ forces form betw
32 and the hydrocarbon part of the molecule.

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Octan-1-ol is insoluble in water. Although there is some hydrogen
bonding265
between the O–H group of the alcohol and the water molecules,
the long hydrocarbon chain prevents water molecules on either side from
hydrogen bonding to each other (Figure 3.106). Energy is needed to
break the hydrogen bonds between the water molecules, but this is not
paid back as only van der Waals’ forces form between the water molecules
SOLUBILITY
and the hydrocarbon part of the molecule.

Octan-1-ol is insoluble in water. Although

there is some hydrogen bonding between
the O–H group of the alcohol and the
water molecules, the long hydrocarbon
chain prevents water molecules on either
side from hydrogen bonding to each
other.

Energy is needed to break the hydrogen

bonds between the water molecules, but
this is not paid back as only van der Waals’
forces form between the water molecules
and the hydrocarbon part of the molecule.
33

Consider the dissolving of sodium chloride:

‘+ water’
NaCl(s) NaCl(aq)

The aqueous solution contains aqueous ions (Na+(aq) and Cl−(aq)).

Ion–dipole interactions form between the water and the ions (Figure
3.107). Energy is required to break the electrostatic forces in the ionic
lattice but energy is released when hydrated ions are formed. If the energy
released when the hydrated ions are formed is comparable to the energy
SKILL CHECK 4
required to break apart the lattice then the substance is generally soluble.

Explain why, in comparison with the other group 6 hydrides, water has
an anomalous boiling temperature.

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SKILL CHECK 5
State all the forces operating between molecules of:
(a) ammonia, NH3
(b) methane, CH4

(c) oxygen fluoride, OF2

35

HYDROGEN BONDING IN ICE

• Each water molecule is hydrogen-bonded to 4
others in a tetrahedral formation

• Ice has a “diamond-like” structure

• Volume is larger than the liquid making it less
dense

• When ice melts, the structure collapses slightly

and the molecules come closer; they then move a
little further apart as they get more energy as they
warm up
Hydrogen bonding
This is why water has a maximum density at 4°C and Lone pair
ice floats.

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 –100 PH3
GeH4
H2O
Barking Dog Art
Group 14 SiH4 100
–150
Online Classes : Megalecture@gmail.com Group 16

CH4 267 50
HF
–200

boiling point/°C
2 3 4 5 Group 17
0
period NH3
H2S
gure 3.54 Thymine, adenine, cytosine –50
Group 15 HC
nd guanine are bases in DNA. The hydrogen 03_53 Cam/Chem AS&A2
PH3
onding between them allows the DNA
olecule to replicate (make new copies of
self) and also allows the genetic code to be
Barking Dog Art HYDROGEN BONDING IN DNA –100
Group 14 SiH4
xpressed in the synthesis of proteins. –150
CH4
–200
C O N N N O N 2 3
C C
C C C C C C C C

N NFigure 3.54 Thymine, adenine, cytosine

C N N C C N N C
and guanine are bases in DNA. The hydrogen 03_53 Cam/Chem AS&A2
to DNA bondingto DNA
between them allows the DNA
N C C N N C C N chainto replicate (make new copies of
chain molecule Barking Dog Art
itself) and also allows the genetic code to be
O to DNA O N
o DNA expressed in the synthesis of proteins.
hain chain
thymine adenine cytosine guanine

C O N N
66
C
C C C C C

N
C N N C C
Cam/Chem AS&A2 66
_Chem_BP_044-068.indd 30/09/14 5:52 PM
to DNA
N C C N N
g Dog Art chain

to DNA O to DNA
chain chain
thymine adenine cytos

37
66

Remember that proteins are

made up of a specific sequence 03_54 Cam/Chem AS&A2 66
181333_03_AS_Chem_BP_044-068.indd
of amino acids (called the
Barking Dog Art
primary structure). This sequence
gives the protein its shape and
therefore its function, and it is protein. It is these proteins produced by the cell that carry out the
the sequence of nucleotide thousands of biochemical processes that are responsible for life.
bases within each gene that For a cell to produce a protein, the gene must first undergo a process
dictates the primary structure called transcription. This occurs in the nucleus, and the first step in this
of the protein produced. In process is the unwinding and separation of the two strands of DNA on
other words, the information which the gene is situated. In a similar manner to DNA replication, this
for the structure of each protein exposes the nucleotide bases of the gene and allows the bases on one of
is carried in the sequence of
nucleotide bases within the
SKILL CHECK 6
the DNA strands to be used as a template.
Transcription differs to DNA replication, however, in that only one
particular gene. strand of DNA is used as a template and the complementary strand
What is involved when a hydrogen bond is formed between two
produced is a ribonucleic acid called messenger RNA (mRNA). The
complementary strand of mRNA is built up through complementary
RNA nucleotides (called ribonucleotides) forming base pairs with
molecules? the exposed bases of the DNA template. Guanine pairs with cytosine
and adenine pairs with uracil (not thymine, as in DNA). As each
Translation is the process of
ribonucleotide comes in and forms a base pair, it is joined covalently to
A a hydrogen atom bonded to an atom less electronegative than itself
protein synthesis in which the
the growing mRNA chain by a phosphodiester link. This results in the
code held in the sequence of
production of a strand of mRNA that has the complementary sequence
bases of the mRNA is translated
of bases to the gene of the DNA template strand. This mRNA then leaves
B a lone pair of electrons
into the sequence of amino acids
the nucleus and enters the cytoplasm, where it takes part in the second
(primary structure) of the protein.
process to produce a protein, known as translation.

C an electrostatic attraction between opposite charges

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SKILL CHECK 7
Which types of intermolecular forces can exist between adjacent urea
molecules?

A hydrogen bonding

B permanent dipole-dipole forces

C temporary induced dipole-dipole forces

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