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hydrogen bond

CHCH, CH,CH

HO
lone pair

Hydrogen bond1ng between ethanol molecules

(1 JOyD
0/d Con/ no9 m / V
C n terrn6/e(nly
 honolicg (n Nlh
hydrogen bond
HO*

H
Ne- IIH Ne11

H
H
lone pair

Hydrogen bonding between ammonia molecules.

Hydrogen bonds are often quoted as being the

intermolecularinteractions. This is true for somestrongest of all
ás water, but it is not true Tor the molecules such
majority of molecules containing
hydrogen bonds.
For example,
although the hydrogen bond is
of the short chain alcohols, significant in the case
e.g. methano! (CH,OH) and ethanol
(CH,CH,OH), becomes less significant for longer chain
it
suchas pentan-1-ol (CH,CH,CH,CH,CH,OH) alcohois
(see Topic 7B). The
same trend is exhibited
by the amines

HYDROGEN BONDING THROUGH FLUORINE

Theonly fluorine compound with intermolecular
bonding is hydrogern fluoride. hydrogen

hydrogen bond

Hd+
H Ho+
H
F

Hydrogen bonding between hydrogen fluoride molecules

 Strong and weak hydrogen bonds
It was once believed that hydrogen bonds were formed only when
hydrogen was bonded to oxygen,
nitrogen or fluorine. Richard
Nelmes of Edinburgh
University surprised the world of
sulfide had an chemistry
when he discovered that solid
hydrogen extended
system of hydrogen bonding, which was similar to that in ice.
Because sulfur has a low
between HSmotecutes iselectronegativity, the hydrogen
constdered to be weak. In fact,bond
magnitude of 7k moF compared with 27kjmotn ice. ithas a
Some strengths of
hydrogen bonds are shown in table C below. For
comparison, the strengths of the 'full' bonds in some of these
are also shown. species

H
H
SII H /338 17 449
H
NIi H-NNH
H
H
H H
22
498 29 373
H-F H=
H

55 373 H
ClI -O 98
F I UlH

151
169 169
-0 HIl F-

table C
Strengths of some hydrogen bonds.
You will notice that, in
most
much weaker than the full bonds. cases,
the hydrogen bornds are
very
You can also see that
of the the strengths
hydrogen bonds increase with the electronegativity
elementto which the hydrogen is attached. Hydrogen of the
strength increases as follows: bonding
HS<NH, <H,0<HF
Also note that the
hydrogen
that to a neutral molecule.
bond to an ion is much stronger than
The strongest
hydrogen bond shown in the table is that between HF
and F. In this species the two bond
identical. The resulting ion, lengths and bond sttengths are
as the solid sodium
[F-H-FJ, is so stable that it is obtainable
salt, sodium hydrogen difluoride, NaHF2
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 BRANCHED ALKANES
than their unbranched isomers (table A).
Branched chain alkanes have lower boiling temperatures

NAME OF ALKANE STRUCTURAL FORMULA BOILING TEMPERATURE K

H H H
H
pentane H H 309

H H H

H CH, H H

H 301
2-methylbutane
H

CH,

CH -CH 283
2,2-dimethylpropane
CH
table A
The more branching in the molecule, the fewer points of contact between adjacent molecules; 1.e.they
do not pack together as well. This leads to a decrease in the overall intermolecular force of attraction
between molecules and a decrease in boiling temperature.

AlcoKTr Sin a Koy Cgntan 0-4

/a n n Lerm&telsy 4 bonds n
Com
dd o fo Lendon lot Kay Kan knghu

alkzn Case CH 04 Ga
Ce h d
Ch, Bk md/écu/o kaue Smla CAann

hondhns e t s h betie
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9
Kks7eCule
eall mmbens / allahet semes, H
ondin ?sis pdemanan Grd Lerdon
Ondin e
ad (Karin
Theenthalpy change of vaporisation is á measure of the amount
enerzy that is reguired to completely separate the molecules of
a liquid and convert it into a gas at the same temperature.
therefore, a direct measure of the Lt 1S,
strength of the intermolecular
interactions. The greater the enthalpy change of vaporisation,
the
greater the forces of attraction between the inolecules.

3 oplingpanf y gen Ka hde

R d
73 p y Chrogen Kakoa (S
o
HEH Cl BKHI. TKe kgh Bp 4 E
is L
C'a igh eecio Kg Ausy 7 Flcih
AF

HI is e a k e y in
HBr
HCI
HE de fo
4
(ess ns
A
fig C
Number of period
Boiling temperatures of the
elecfr0n3
hydrogen halides.

The-steady inrease inboiling temperature from HCi to HI is the

Tesult of the
increasing number of electrons per molecule, which
n turn results in an increase in London forces
 There are three intermolecular interactions within each
compound. They are:
1 London forces
2 permanent dipole-dipole interactions
3 hydrogen bonding.

However, with HCI, HBr and Hl, the electronegativity of the

halogen is low enough for the permanent dipole-dipole
interactions and the hydrogen bonding to be relatively
weak. The
predominant interaction in each compound is the London force.
The boiling temperature of HF is significantly higher than that
of the
other three hydrogen halides, despite having fewer
electrons per molecule. The Londonforce isweakerin HE, but
the bydrogen bonding is significantly greater because of the high
electronegativity of fluorine

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 ANOMALOUS PROPERTIES OF WATER
Water has some anomalous properties. The following two are
particularly important
1 It has a relativelyhigh meltingand boiling temperature for a
molecule with so few electrons.
2 The density of ice at 0°Cis less than that of water at 0 °C.

MELTING AND BOLING TEMPERATURES

Thehydrogenbondshetween water moleculesarerelatively
strong (see Topic 3E.2). As a result.the averallintermolecular

forçes of attraction in water are greater than

in the molecule. would be expected from the number of electrons (10)
Water, therefore, has an
(100°C. 373 K) at abnormally high melting temperature (0°C, 273
100kPa pressure. K) and boiling temperature
It is interesting to
compare the
boiling temperatures of water, ammonia and
hydrogen fHuonde

Boiling point of HF< H20. In HF molecule, there is

only one H F bond, though -

there are 3 unshared pairs of electrons on

fluorine atom. This means that there
can be an average of one
hydrogen bond per molecule.

However, in water there are20-H bonds and 2

unshared pair of electrons per
molecules, this means that each water molecule can form 2
hydrogen bonds,
hence the boiling point of water is higher than HF.

In NH, molecule, there are 3N-H bonds but only one unshared pair of electron
on nitrogen atom. This means that there can be an average
of only one
hydrogen bond permolecule (like HF), however the electronegativity of fluorine
is more than that of nitrogen. Therefore, the strength
of hydrogen bond is more
in HF than in NH, hence the boiling
point of HF is more than NH

lce is less dense than water and it floatswater. Water molecules are joined
on
together in an extensive 3-dimensional network, in which each oxygen atom is
bonded to 4 hydrogen atoms, 2 by hydrogen bonds and 2
by normal covalent
bonds in a nearly tetrahedral configuration.
Ice has highly ordered 3-dimensional hydrogen bonded structure which has
a

got open spaces, this is responsible for the low

density of ice.
When ice melts, the regular lattice breaks up, then the water molecules can pack
up more closely so the liquid has high density.

H-0-H-O

H-t-9-
4

COHPOUNDS THAT CAN FORM HYDROGEN BONDs WITH WATER

Aicohols contain an -O-H group and can therefore form hydrogen bonds with water
Fig F shows a molecule of ethanol forming a hydrogen bond to
water
hydrogen bond

CH,CH H

lone pair
figF Hydrogen bonding between ethanol and water.

Ethanol and water mix in all proportionshe-hyerogen honding between the ethanol and water
molecules is similar in strength to the hydrogen bonding in pure ethanol and in pure water

The solubility of alcohols in water decreases with increasing hydrocarbon chain length as London
forces predominate between the alcohol molecules.

COMPOUNDS THAT GANNOT FORM HYDROGEN BONDS WITH WATER

Non-polarL moleeules-Such as the alkanes do not dissolve in water The attraction between the alkane
molecules and water nolecules is not sufficiently strong to disrupt the hydrogen bonded system
betweenthe water molecules.
Many polar molecules also have limited solubility in water. This is because they either
hydrogen bonds with water, or the hydrogen bonds they do form are weak compared with the
do not form
hydrogen bonds in water
Ethoxyethane, CiH.CH,OCH,CH,is polar (dipole moment = 1.15 D) and yet is almost totally
immiscible with water The forces of attraction between ethoxyethane and water molecules are not
large enough to replace the relatively strong hydrogen bonding between the water molecules.

Halogenoalkanes (see Topic 10) are also not very soluble in water loI Similar reasons. They are
much more solublt in ethanoi, and thiS IS why some reactions of halogenaalkanes.are carried out in a
Iedium ol aqueous ethanol.
 CHOOSING SUITABLE SOLVENTS
For
asubstance to dissolve, the following two conditions must be met.
The solute particles must be separated from each other and then become surrounded by solvent
parhcdes
I h e forces of attraction between the solute and
solvent particles must be strong enough to
overcome the solvent-solvent forces arnd the solute-solute torces.

DISSOLVING iONIC SOLIDS

Many 1onic solids dissolve in water The energy
completely, or partially, supplied by the hydrationrequired-to.separate
of the ions
the ions in the solid is ene
Fig E shows the process of
dissolving for sodium chloride

0 H 5
H
dissolved chloride
on surrounded by
water molecules

H
Na H
C C Na
Nat
Na Na
a a
C C
Na Na C NaC
Na crNa C
H C NaNa
H

5+ HO

crystal of sodium chloridde H 5+

+ la
+ H O.

+
H
6+

dissolved sodium ion surrounded

by water molecules
fig E Dissolving of sodium chloride

The - ends of the water molecules attract

the sodium ions
The sodium ions then become
lattice
sufficiently to remove them from the
surrounded by water molecules, as
between the sodium ions and the water molecules is
called an ion-dipole interaction.
shówn."The interaction
he dt end of the water molecules attracts the chlonide ions. Once they are in solution, the
chloride ions becone sur rounded by water nolecules, as shgWn. The chloride: ions are hydrogen
bonded to the water molecules

ne aboVe proceSses are kriowii as

hydrauOn and the energy released is
known as the hydratiot
energy
 (15

Dissolving and ionic solid in water:

In an ionic solid, the positive and negative ions are held together by strong
electrostatic forces, therefore energy is required to break the lattice (lattice

energy)
atoms have and oxygen
Water molecules are polarized so that the hydrogen
atoms have d'charges.

Attractive forces between the water molecules and

the ions break the lattice and

the individual ions the water. Water molecules arrange

spread throughout
themselves around the dispersed ions. With a positive ion, the negatively charged
oxygen of water molecule is
closer and with a negative ion, the positively charged
This process of water molecules
hydrogen of the water molecule is closer.
is known as hydration and the energy
arranging themselves around an ion
produced is known as hydration energy.

cnergy. f the
There is a balance between the lattice energy and hydration
need to break up the lattice,
hydration energy is enough to balance the energy

that compound is soluble in water.

less than the hydration energy.

in the case of NaOH, lattice energy is much
is
with water, the e x c e s s energy from hydration
Therefore, when NaOH is mixed
That is, dissolving NaOH in water is an
released and the solution gets warmer.
exothermic change.

is higher than the hydration energy,

LiF is insolubie in water, since lattice energy
it is insoiuble in water.
which is not enOugh to break down the lattice and hence,
NaCl is soluble in water because the
hydration energy is enough to balance the
energy needed to break off the lattice.

Solubility of alcohols in water

Alcohols are soluble in water because they have polar OH
group and can form
hydrogen bonds with water.
Eg
------ O - H - - - - O - H ------

R H

The solubility
of alcohois in water decreases with increase in chain
length of
alcohol. This is because a smaller proportion of the molecule is
polar and the
other part is non-polar.

Carboxylic acids are soluble in water due to their ability to form hydrogen bonds
with water due to the presence of polar OH group.

Eg

R-C-0 ----- H-0

O H H

Non-polar substances are insoluble in water:

Forces between the non-polar molecular (eg: hexane) are much weaker than the
hydrogen bonds between water molecules, therefore, the non-polar molecules
are unable to disrupt the hydrogen bonded structure of water molecule and
hence remain as separate layer.
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 (

Q) Compare the boiling points of hydrides of group4.

Ans) The order is CH< SiH< GeH4 < SnHa

This is because the atomic size (size of electron cloud) and hence the
vander Waal's force increases as we move down from C to Sn. Atoms with
large electron cloud tend not to hold their outer electrons so tightly. So
large electron cloud tend to be deformed easily, this favors the existence of
instantaneous dipole and creation of induced dipole, therefore Vander
Waal's force increases.

Trends in boiling and melting temperature of alkanes:

The melting and boiling temperatures

of alkanes increases as the chain length
increases. The intermolecular forces in alkanes is the weak instantaneous
dipole-
induced dipole forces though they are weak, they hold the
particles in organic
liquids and solids. These forces become larger as the length of the molecular
increases because there are more places where these forces can operate.

VolatilityY:

It is a measure of how easily the molecules escape from a liquid. A volatile liquid
loses molecules from the surface very easily so it will have a low boiling point.

Effect of branching in the carbon chains on the boiing and melting temperature
of alkanes-
Branching of the molecules lower the boiling temperature because the side
chain interfere with the packing together of molecules and reduces the
formation ofintermolecular forces between the induced dipoles. 7e mere tKA
Ch * e e y tKa- p0int3 Confech hewem h aag ap
mtaculis Thns /eaads o am Gveyail Ae CALEALe 1n 1nfeymatè Cnlan bY
Branching of molecules increases the meiting temperature of alkanes (or other

hydrocarbons)

Explanation: melting point depend on packing of molecules in the crystal

lattice, branched hydrocarbons have a more compact packing and hence possess
a higher melting point.

Solubility:
solvents other than water are known as non-aqueous solvents)

Ex: Hexane, ether, paraffin, etc.)

Soiubility is the amount of substance dissolved in 100g of a solvent at a particular

temperature

Highly polar substances such as NaCl, KCI, etc. (ionic solids) dissolves in polar
solvents Iike water but not in non-polar solvents like hexane.

Polar organic substances such as sucrose, glucose, etc. are soluble in water due
to their ability to form H bonds with water, but not in hexane

Non-polar solids such as candle was doesn't dissolve in water but dissolves in
hexane.

A polar liquid and a non-poiar iiquid such as water and petro! are immiscible and
form separate layers with one floating over another. All these points prove that
Like dissolves like'

BAMBOIR8AO RiGN
instantaneous dipole induced dipole
ondon 1orces
interaction

permanent dipole-perimnanent dipole

Permanent dipole,
InteractION