1

ELECTRONEGATIVITY : UNIT-2

The ability of an atom to attract the bond e– pair towards it, in a covalent bond.

 The “Most electro–negative” Group of elements is Group 7.

 The “Most electro–negative” element is Fluorine.
 The “Least electro–negative” Group of elements is Group 1.

Electro–negativity

H El.
3 2 1
N
E
Li Be B C N O F G.

Na Cl
4

 Hydrogen is supposed to be classified under Group 1, as H too has just 1 electron in the outer shell.

There is „enormously high‟ electronegativity difference between H–F bond, O–H bond & N–H bond.

(iii) (ii) (i)

H N O F
Highest el-negativity Diff.

δ+ δ–
H F

H F

δ– δ+
O H
δ+δ+δ+
Note : The bond electron pair is placed more towards
O H the atom which is partially negative (δ–)

δ– δ+
N H

N H
 INTER–MOLECULAR FORCES (I.M.F.) 2

I.M.F. that exist b/w I.M.F. that exist b/w

POLAR MOLECULES NON–POLAR MOLECULES
“London” forces
“HYDROGEN” bonds “Dipole–Dipole” bonds “Vander Waal’s” forces
(permanent Dipole-PDP) (dispersion forces
/ instantaneous forces
/ induced dipoles / temporary dipoles)
strongest type Moderately strong weakest type

 exist in molecules with ;  exist in other polar  exist in ANY molecules

molecules
Highest elect.

* H–F
eg : Fδ+– Fδ– Fδ+– Fδ–
Negativity
difference

* O–H (eg : H2O)

Hδ+ Clδ– H δ+ Clδ–
* N–H (eg : NH3) London forces /
Vanderwaal’s forces

Oδ– DP-DP * How London / VWFs arise :

δ+ δ+
H H * For a moment, a non–polar
molecule gets polarised
δ– temporarily as the whole e–
eg : O
Oδ– cloud moves to one side.

Hδ+ Hδ+ C δ+ F–F F–F

Hydrogen bond
H3 C CH3 * This will result in a very weak charge
separation, (Hence the name
DP-DP “temporary dipoles”.)
Nδ– δ+ δ–
F–F
δ– F –F
Hδ+ O
+
Hδ+ Hδ
δ+ * The adjacent non–polar molecule then
Hδ+ C gets induced by this, thus becomes a
polar molecule too. (Hence the term
– H3C CH3
Nδ “induced dipoles”
δ+
H
δ+ δ– δ+ δ–
Hδ+ F –F F –F
+
Hδ
London / VWF
* However, these I.M.Forces
+ – + – are very weak.
Hδ Fδ Hδ Fδ

 Types of I.M.F. available :  Types of I.M.F. available :  Types of I.M.F. available :

* Hydrogen bonds * DP–DP bonds * London Forces / VWF

* London Forces / VWF * London Forces / VWF * ………………………………….…..

(iii) (ii) (i)

H N O F (i) H– F bond
Highest el-negativity Diff.
(ii) O–H bond
(iii) N–H bond
 HOW TO DECLARE WHICH SUBSTANCE (OUT OF GIVEN TWO) HAS THE HIGHER
3 MELTING TEMPERATURE (Tm) OR BOILING TEMPERATURE (Tb)

Rule 1 : THE GENERAL RULE :

In the event of melting/ boiling, the type of attraction that has to be broken & its STRENGTH,
must be considered.

inside the lattice or between the molecules/atoms

[Inter–Molecular Forces]
Always STRONGER TYPE than Inter–Molecular Forces
Eg : Eg :
* Mg (Giant metallic lattice) * STRONG * O2 (simple cov. molecule) * weak
* Graphite (Giant cov. lattice) * HF (simple cov. Molecule) Int. Mol. F.
BONDS
* NaCl (Giant ionic lattice) * CH4 (simple cov. Molecule)

HIGHER Tm / Tb LOWER Tm / Tb

Rule 2 : Checking which given simple covalent molecular substance has higher Tm or Tb

Check if the substance concerned has the :

(i) Strongest I.M.F. type which is Hydrogen Bonds ; so that they have the HIGHEST Tm or Tb.

Those which have O–H, N–H & H–F bonds form H–Bonds. * Exception : Those which have bulky
alkyl /aromatic group attached to it, do
NOT (or less likely) form H–Bonds (as
eg : CH3OH CH3NH2 HF
there are a few sites for H–Bonding)
Q : Which one has higher Tb, CH3CH2OH or CH3CHO ?
eg : –CH2CH2CH2CH2OH
A : CH3CH2OH, forms stronger H–bonds (CH3CHO weaker DP–DP)

(ii) Permanent Dipole–Permanent Dipole (DP–DP); so that they have HIGHER Tm or Tb. than those with
LONDON (V.W.F).
Rule 4 : This is generally applicable to structural isomers.
Eg : CH3
(DP–DP) (LONDON) * Lesser gap btw CH3CH2CH2CH3 CH3CHCH3 * More
Molecules gap
eg : O CH3 CH area CH3CH2CH2CH3
* More surface CH3
* Stronger London
CH3CCH3 CH3CHCH3 forces CH3CHCH3

(Mr=58)

Rule 3 : This rule is GENERALLY applicable to „NON–POLAR” molecules.

The relatively bigger molecule (with greater no of electrons) has relatively

STRONGER LONDON (V.W.F.) FORCES; hence HIGHER Tm or Tb

(LONDON)
BIGGER molecule (with greater no of electrons)
eg : CH3Cl CH3I
Rule 4 :
** Note : They form DP–DP bonds too (which depend on electro–neg. difference‟).
But in this case it is the size of molecules (with greater no of electrons) matters
most, rather than electro–negativity difference‟.
 4
Q 1 : State & explain which one has greater boiling point (Tb) I2 or F2.

A 1: Both form London Forces, as both are non–polar (polar/non–polar) molecules.

……. ……..
I I I I F -F F-F
London Forces London Forces

* I2 molecule is bigger (bigger/smaller) * F2 molecule is smaller (bigger/smaller)

with higher (higher/lesser) number of electrons. with lesser (higher/lesser) no. of electrons.

* (relatively) stronger (stronger/weaker) * (relatively) weaker (stronger/weaker)

London Forces London Forces

* higher (higher/lower) Tb. * . lower (higher/lower) Tb.

Q 2 : (a) Lower members of alcohols

such as methanol, are miscible
with water.

Give appropriate diagrams &

explain why they are miscible.

As shown in the diagram, methanol

forms intermolecular Hydrogen bonds
with water; hence, miscible.

(b) Given below are the boiling points of hydrides of group 6 elements.

0
Tb / C
H2O

H2Te

H2Se

H2S

(i) Explain why the boiling point of water is greater than those of hydrides of group 6 elements.

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(ii) Explain why the boiling points from H2S to H2Te, increases.

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 5 SOLUBILITY OF MOLECULAR SUBSTANCES

 The intermolecular forces between the following are involved.

The intermolecular forces The intermolecular forces The intermolecular forces
between between between
SOLUTE molecules SOLVENT molecules SOLUTE & SOLVENT molecules

I.M.F. I.M.F. I.M.F.

 When ALL 3 types of forces are about the same strength, the solute dissolves freely in solvent.

 Non-polar molecules (eg : H/C) mix with non-polar solvents (eg: cyclohexane, , C6H12) as the
intermolecular forces involved are LONDON FORCES.

London F. London F. London F.

 Non-polar solutes do not dissolve in polar solvents.

Eg: Non–polar molecules can separate easily as they have weak London forces, but Hydrogen bonds
between water molecules will not break. Therefore, no H-bonds will form between the non–polar
molecules of solute & polar water molecules.

London F. Hydrogen Bonds

 But organic compounds (that are polar) that can bond with H2O by means of H-bonds, will dissolve as
bonds are all of the same type.

Eg ; ethanol is miscible with water as the two types of molecules will bond by means of hydrogen bonds.

However, alcohols with long C-chains will be less soluble with water, as the no of sites for H-bonding will be
less with the long C-chain.

This phenomenon matters in the solubility of medicines.

Medicines which require high solubility in water
Pain killers need the speed action. High solubility of the
drug increases the necessary concentration in the blood for
it to be effective.
„Hydrophilic‟ (water–loving) groups can be introduced to
the drug. Eg ; introducing ionic groups (–COO-), –OH, –
NH2 groups that form hydrogen bonds with water.
Medicines which require high solubility in fats.
Oinments such as „oil of wintergreen‟ need to be
soluble in skin & fatty tissue. So they have long
C–chains („Lipophilic groups) in their molecules.
They form London forces.
1. An experiment to determine the effect of
6
an electrostatic force on a jet of liquid is
carried out using the apparatus as shown.

Which of the following liquids would not be

significantly deflected by the electrostatic
force applied ?

A CH3OH charged rod

B CCl4
C CHCl3
D H2O

2. Given below are the Tbs of hydrides of G–7 elements.

(i) Explain why the Tb of HF is greater than
0
those of hydrides of group 7 elements.
Tb / C
HF .............................................................................................

..............................................................................................
HI
.............................................................................................
HCl HBr
..............................................................................................

hydrides of group 6 ..............................................................................................

(ii) Explain why the boiling points from HCl to HI increases. ....................................................................................................

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3. (a) Arrange the following bonds in the descending order of their electronegativity difference.
Bond O–H H–Cl N–H H–F

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(b) (i) Indicate the state symbols of the following PURE compounds (at r.t.p.), in brackets.

H2O (….) HCl (….) NH3 (….) HF (….)

(ii) Indicate the „strongest‟ type of I.M.F.s present in the following pure compounds (at r.t.p.).

Compound H2O HCl NH3 HF

Type of the I.M.F.

(iii) Predict, which of the above the compounds, has the highest Tb. Justification is not required.

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(iv) Predict with reasoning, which of the above the compounds, has the lowest Tb.

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(v) Explain why HF has lower Tb than water, although the electronegativity difference is higher in H–F.

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