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Intermolecular forces

Intermolecular Force
Basic Concept of intermolecular forc
e
• Broadly speaking, there are two types of intermolec
ular forces, Van der Waals’ forces and hydrogen
bonding.
Van der Waals’ force
Van der Waals’ force is electrostatic attraction
between dipole, i.e. the attraction between th
e positive end of one molecule and the negati
ve end of another molecule.
There are the types of dipoles: permanent dip
ole, instantaneous dipole and induced dipole.
Permanent Dipole
• A permanent dipole exists in all polar molec
ules.
Permanent Dipole

δ+ δ-
Instantaneous dipole
• An instantaneous dipole is a temporary dip
ole that exists as a result of fluctuation in t
he electron cloud. The temporary dipole in
duces a dipole in a neighbouring molecule.
This results in a weak and temporary force
of attraction between the two atoms.
Induced Dipole
• An induced dipole is a temporary dipole th
at is created due to the influence of a neigh
bouring dipole (which may be a permanent
or an instantaneous dipole)

Induced Dipole
• Van der Waals’ forces consists of three type
s of intermolecular attractions. They includ
e the permanent dipole - permanent di
pole interaction, permanent dipole -in
duced dipole interaction and instantan
eous dipole - induced dipole interactio
n.
Permanent dipole - permanent dipole intera
ction

• Polar molecules such as HCl have permanent mo


ments. They tends to orient one another, as a res
ult there are attractive forces between molecules
. The attraction between the δ+ and δ- of the pe
rmanent dipoles of neighbouring molecules is pe
rmanent dipole - permanent dipole interaction.
• Dipole-dipole attraction requires the presence o
f polar bonds and a unsymmetric molecule.
• Dipole—dipole interactions are the attractive forces between the permanent
dipoles of two polar molecules.
• Consider acetone (below). The dipoles in adjacent molecules align so that
the partial positive and partial negative charges are in close proximity.
These attractive forces caused by permanent dipoles are much stronger than
weak van der Waals forces.

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Permanent dipole -induced dipole interactio
n

• When a non-polar molecule approaches a polar


molecule (with a permanent dipole), a dipole wil
l be induced in the non-polar molecule. The dipo
le induced will be in opposite orientation to that
of the polar molecule.
• The dipole – induced dipole interactions are gen
erally weaker than dipole – dipole interactions
Instantaneous dipole - induced dipole interaction

• Take argon as an example. The electron cloud distribu


tion is generally symmetrical around the argon nucle
us. However, due to the instant mobility of the electro
n cloud ,its position fluctuates all the time.
• At any particular instant, it is likely to be concentrated
on one side of the atom than the other. Thus, the ato
m possesses an electric dipole moment at that partic
ular instant. It is known as the Instantaneous dipole
moment.
• The instantaneous dipole will induce a dipole moment (k
nown as the induced dipole moment) in the neighbouring
atom by attracting opposite charges. If the positive end of
the dipole is pointing towards a neighbouring atom, the
induced dipole will then have its negative end pointing to
wards the positive pole of that dipole. That makes the ins
tantaneous dipole attract the induced dipole. It is the typ
e of weak attraction that exists between atoms of noble g
ases and between non – polar molecules.
• Instantaneous dipole-induced dipole attraction also calle
d dispersion force or London force.
• They are much weaker than dipole – dipole interaction,
• van der Waals forces are also known as London forces.
• They are weak interactions caused by momentary changes in electron
density in a molecule.
• They are the only attractive forces present in nonpolar compounds.

Even though CH4 has no net


dipole, at any one instant its
electron density may not be
completely symmetrical,
resulting in a temporary dipole.
This can induce a temporary
dipole in another molecule. The
weak interactions of this type
constitutes van der Waals forces.

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• All compounds exhibit van der Waals forces.
• The surface area of a molecule determines the strength of the van der
Waals interactions between molecules. The larger the surface area, the
larger the attractive force between two molecules, and the stronger the
intermolecular forces.

Surface area and van der Waals forces

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• van der Waals forces are also affected by polarizability.
• Polarizability is a measure of how the electron cloud around an atom responds
to changes in its electronic environment.

Larger atoms, like iodine,


which have more loosely held
valence electrons, are more
polarizable than smaller atoms
like fluorine, which have more
tightly held electrons. Thus,
two F2 molecules have little
attractive force between them
since the electrons are tightly
held and temporary dipoles are
difficult to induce.

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Summary of intermolecular forces
Type of Interaction Magnitude (KJ mol-1)

Dipole - dipole 5 – 25

Dipole – induced dipole 2 - 10

Instantaneous dipole – 0.05 - 50


induced dipole
Physical Properties: Boiling Point
• The boiling point of a compound is the temperature at which
liquid molecules are converted into gas.
• In boiling, energy is needed to overcome the attractive forces in
the more ordered liquid state.
• The stronger the intermolecular forces, the higher the boiling
point. For compounds with approximately the same molecular
weight:

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Hydrogen bonding
The evidence for hydrogen bonding

• Many elements form compounds with hydroge


n - referred to as "hydrides". If you plot the boil
ing points of the hydrides of the Group 4 eleme
nts, you find that the boiling points increase as
you go down the group.
• The increase in boiling point happens becau
se the molecules are getting larger with mor
e electrons, and so van der Waals dispersion
forces become greater.
• If you repeat this exercise with the hydrides of
elements in Groups 5, 6 and 7, something odd
happens.
• Although for the most part the trend is exactly the
same as in group 4 (for exactly the same reasons),
the boiling point of the hydride of the first elemen
t in each group is abnormally high.
• In the cases of NH3, H2O and HF there must be so
me additional intermolecular forces of attraction,
requiring significantly more heat energy to break.
These relatively powerful intermolecular forces ar
e described as hydrogen bonds.
The origin of hydrogen bonding

• The molecules which have this extra bonding are:


Notice that in each of these molecules:
• The hydrogen is attached directly to one of the most
electronegative elements, causing the hydrogen to ac
quire a significant amount of positive charge.

• Each of the elements to which the hydrogen is attach


ed is not only significantly negative, but also has at le
ast one "active" lone pair.
Lone pairs at the 2-level have the electrons contained
in a relatively small volume of space which therefore
has a high density of negative charge. Lone pairs at hi
gher levels are more diffuse and not so attractive to p
ositive things.
Consider two water molecules coming close togethe
r.
• The δ + hydrogen is so strongly attracted to the lone p
air that it is almost as if you were beginning to form a
co-ordinate (dative covalent) bond. It doesn't go that f
ar, but the attraction is significantly stronger than an o
rdinary dipole-dipole interaction.
• Hydrogen bonds have about a tenth of the strength of
an average covalent bond, and are being constantly br
oken and reformed in liquid water. If you liken the cov
alent bond between the oxygen and hydrogen to a sta
ble marriage, the hydrogen bond has "just good friend
s" status. On the same scale, van der Waals attractions
represent mere passing acquaintances!
Hydrogen Bonding in Water and Ice
 Hydrogen bonding exists in both water and ice.
 In water, the molecules are in constant motion. Hydr
ogen bonds are formed and broken continually. The a
rrangement of a minimum and molecules are in rand
om.
 In ice, molecular motion is of a minimum and molecu
les are oriented in such a way that the maximum nu
mber of hydrogen bonds are formed.
Why ice float on water???
Why ice can float on water???
 Each water molecule is made of 2 hydrogen ato
ms and 1 oxygen atom. These are connected to
one another by very strong chemical bonds calle
d covalent bonds. Water molecules are connecte
d to each other by much weaker chemical bonds
called hydrogen bonds between the positively ch
arged hydrogen atoms, and one negatively char
ged oxygen atom in a neighboring water molecul
e.
 Ice floats because it is less dense than liquid wat
er. Ice is about 9% less dense.
 Ice has an open-cage structure with very ineff
icient packing of molecules.The hydrogen bo
nds not only help to held the water molecules
rigidly as solid , but also hold the molecules a
part & ice is less dense than water. As there a
re many space in open-cage structure, when
the bond broke, some molecules can occupy
the space,the volume of ice decrease.
 At 0℃(ice melt),much of hydrogen bond structure i
s broken(the regular lattice breaks up), water mole
cules pack more closely together & density rise.
 When the temperature is above 0℃, kinetic energ
y increase, and causing an increasing % of hydro
gen bonds.
 When the temperature is above 4℃, vibration incr
ease, the volume increase, and cause the decrea
sing of density.
 When the temperature is 100 ℃, all hydrogen bon
d will break.
Importance of Hydrogen Bond
s Water and Ice
 In water, the strong hydrogen bonding result in s
ome ordered packing of water molecules over a
short range. The fact that ice is less dense than
water at 0 ℃ makes ponds and lakes freeze fro
m the surface downwards. The layer of ice insul
ates the water below and prevents complete soli
dification. That allows fish, aquatic plants and ot
her aquatic organisms to survive.
Hydrogen Bonding in Protein
s
 Hydrogen bonding pla
ys a crucial role in the
structures of many su
bstances such as prot
eins and deoxyribonu
cleic acids (DNA). Th
e primary structure of
a protein is a polypept
ide which is a polymer
of amino acids.
 Polypeptide chins form a helical structure o
wing to the hydrogen bonds formed betwee
n the N-H and C=O groups. This creates th
e secondary structure of proteins.

 In many proteins, including those in hair, wo


ol and nails, hydrogen bonding causes the
polypeptide chains to become twisted into ti
ghtly coiled helices.
Hydrogen Bonding in DNA
 DNA is present in the nuclei of living cells
and carries genetic information. It consists
of two macromolecular strands spiralling a
round each other in the form of a double h
elix.
 The DNA molecule consists of two helical
nucleic acid chains. Each nucleic acids is
made up of three components:
1. a sugar;
2. a phosphoric acid unit; and
3. a nitrogen-containing heterocyclic bas
e: adenine, cytosine, guanine or thymi
ne.
 The two nucleic acid chains are held t
ogether by hydrogen bonds. These hy
drogen bonds are formed between sp
ecific pairs of bases on the chains. Fo
r example, two hydrogen bonds are fo
rmed between an adenine unit in one
chain and a thymine unit in the other
while three hydrogen bonds are form
ed between a guanine unit in one cha
in and a cytosine unit in the other.
 When a cell divides, the double helix of the
DNA molecule uncoils by breaking down th
e hydrogen bonds. A complementary chain
is formed adjacent to each of the newly for
med double helices is received by each of
the two cells. This gives an explanation for
the same DNA in every normal cell of an o
rganism.
Group Member
 CHEUNG YI TONG (6)
 TSUI MAN KI (27)
THE END

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