Hydrogen Bonding

When hydrogen atom is bonded to a highly electronegative atom by a covalent

bond then the bond pair of electrons is displaced towards the electronegative
atom. When solitary electron of hydrogen atom lies away from it, its nucleus gets
exposed and this behaves as a bare proton. Such a bare hydrogen nucleus
exerts a strong electrostatic attraction on the electronegative atom of the
adjacent molecule and forms a bond.

For example, bond between hydrogen atom and fluorine atom of the neighboring
molecule.

In this hydrogen atom acts as abridge between two atoms holding one atom by
covalent bond and other atom by hydrogen bond. The hydrogen bond is
represented by dotted lines (----) and covalent bond is represented by solid line
(─). Thus hydrogen bond is defined as the electrostatic force of attraction, which
exists between covalently bonded hydrogen atom of one molecule and the
electronegative atom of the other molecule.

Strength of Hydrogen Bond:

Hydrogen bond is much weaker than covalent bond and its strength ranges from
10 to 40 kJ mol-1 while covalent bond is ten times stronger than hydrogen bond.
Bond length of hydrogen bomb is larger than that of covalent bond.
Cause of Formation of Hydrogen Bond:

When hydrogen atom is bonded to highly electronegative atom A (F, O or N) then

the electron pair shared between the two atoms lie far away from the hydrogen
atom. As a result, hydrogen atom becomes highly electropositive with respect to
the other atom. Since the electrons are displaced towards A and it acquires
partial negative charge while hydrogen atom gets partial positive charge.

In other words the bond H ─ A becomes polar and may be represented as H + ─

A -. Electrostatic force of attraction between positively charged hydrogen atom of
one molecule and negatively charged atom of neighbouring molecule results in
the formation of hydrogen bomb.

Conditions for Hydrogen Bonding:

Conditions that are required for hydrogen bonding are:

1) The atom which is bonded to the hydrogen atom should be highly

electronegative e.g. F, O or N.

2) The electronegative atom should be of small size – smaller the size of the
electronegative atom greater will be the attraction for bonded pair and
greater will be the polarity between H and electronegative atom. This
results in the formation of stronger hydrogen bond. Example – NH3 shows
hydrogen bonding while HCl doesn’t show. It is because Cl (chlorine) is
bigger in size than N (nitrogen).
 Difference between Hydrogen bond and Covalent bond:

Examples of Hydrogen Bonded Compounds:

1) Hydrogen Fluoride: It consists of long zigzag chains of molecules joined

together by hydrogen bond (HF)n. These chains become linear in liquid
and gaseous state.
2) Water: In water molecule, there are two covalent bonds (O-H) and two
hydrogen bonds between Oxygen and hydrogen atoms. As a result of this,
four hydrogen atoms, two by covalent bonds and two by hydrogen bond
tetrahedrally surround each oxygen atom.
 3) Ammonia: In ammonia, each hydrogen atom acquires a positive charge
due to the difference in electronegativity between nitrogen and hydrogen
atoms. Thus, in the molecule, there is one negative site and three positive
sites so that ammonia molecules associate through hydrogen bonding to
form long chains.

Types of Hydrogen Bonding:

Hydrogen bond can be classified into two types:

a) Inter molecular hydrogen bond b) Intra molecular hydrogen bond

a) Intermolecular hydrogen bond:

This type of bond is formed between two different molecules of the same or
different substances.

Examples:

1) Hydrogen bond between the molecules of Hydrogen Fluoride.

2) Hydrogen bond in alcohol or water molecule.
3) Hydrogen bond in ammonia molecule.
4) Hydrogen bond in hydrogen peroxide.
5) Hydrogen bond between carboxylic acids.

Effects of Intermolecular Hydrogen Bonding:

1. It results into the association of molecules.

2. Intermolecular bond increases the melting point, boiling point, viscosity,

surface tension, solubility, etc.
 b) Intra molecular Hydrogen Bond:

This type of bond is formed between the hydrogen atom and the highly
electronegative atom (F, O or N) present in the same molecule.

Examples of Intramolecular Hydrogen bonding are

1) 3,4-dihydroxy-3-cyclobutene-1,2-dione

2) 4-hydroxy-5-methyl-4-cyclopentene-1,3-dione
3) 2-hydroxy-1,4-naphthoquinone

4) 3-hydroxy-2-methyl-4-pyrone
5) 2,5-dihydroxy-1,4-benzoquinone

6) 3-hydroxy-1,2-dimethyl-4(1H)-pyridone
7) Tropolone

Consequences of Hydrogen Bonding:

Hydrogen bond influences the properties of the substances, particularly their
physical properties like melting point, boiling point, solubility. The effect of
intramoleular hydrogen bond is negligible as compared to the inter molecular
hydrogen bond because it involves only the individual molecules.
Otherwise its effects on some of the physical properties are:

1) Physical state:

Intermolecular hydrogen bonding influences the physical state of the

substances.

For Example both H2O and H2S are the hydrides of the elements present in
the same group (16). So they should have the same physical properties. But it
is not like this H2O is liquid at room temperature. Where as H2S is a gas. This
is all due the difference in the electronegativity of atoms O-H bond (3.5-2.1)
1.4 While in S-H bond (2.5-1.4) 0.4 only. Thus O-H bond is more polar than
S-H bond (negligible polarity).

Due to polarity, there is inter molecular hydrogen bonding present in H2O

molecules and they get associated, grow into molecular size and exist in
liquid state at room temperature. But H2S molecule does not get associated
due to the absence of intermolecular hydrogen bond and exist as a gas at
room temp.

2) Melting and Boiling point:

Presence of hydrogen bonding in the compounds also effects the melting

point and boiling point. There is increase in the melting and boiling points
because the electrostatic force of attraction in the molecules becomes large.
Consequently, larger energy is required to separate these molecules before
they can melt or boil.

Comparison of melting and boiling points (K)

From the above table it is clear that the melting and boiling points increase as
the molecular mass increases in group14. This is because as the size of
elements of group14 increases, the number of electrons also increases. With
this van der Waal’s forces also increase.
But there is abnormality in the melting point and boiling point in the first
member of group 15(NH3) group16 (H2O), and group17 (HF).

These molecules have relatively high melting and boiling points due to inter
molecular hydrogen binding. Larger the hydrogen bond higher the boiling
point.

Graph between boiling point and molecular mass

3) Solubility:

Hydrogen bonding also influences the solubility of a solute in a solvent.

For example, alcohols are organic in nature and are expected to insoluble
in water, which has inorganic nature. But alcohols readily dissolve in water
even at room temperature due to the presence of hydrogen bonding in
their molecules. Energy is released as a result of attraction. Since the
energy of the system involving alcohol and water decreases, this favors
the solubility.
a) Solubility of alcohol in water

b) Solubility of glucose in water

4) Association:

Due to the presence of intermolecular hydrogen bonding two or more

molecules exist as associated molecules e.g. Carboxylic acid exist as
dimmer.

5) Surface tension and viscosity:

There is increase in surface tension and viscosity of liquids due to the

presence of hydrogen bond e.g. Glycerol and Sulphuric acid are highly
viscous due to the presence of intermolecular hydrogen bonding.
 Hydrogen Bonding in Ice and Water:

Hydrogen bonding in ice Hexagonal structure of ice (Ice Ih)

The unique behavior of water is due to the presence of hydrogen bonding

between its molecules. It is a common observation that density of ice is less than
that of water because it always floats over water. It is a well-known fact that
density of water is maximum at 4oc.
• Ice is lighter than water – From X ray studies it has been found that each
oxygen atom in ice is tetrahedrally surrounded by four hydrogen atoms.
Two hydrogen atoms are linked to oxygen atom by covalent bonds at a
distance of 1.00oA.The other two hydrogen atoms are linked to the central
oxygen atom by hydrogen bonds at a distance of 1.76oA.

• The oxygen atoms of water molecules are located at the corners of

tetrahedron. As a result of tetrahedral arrangement of water molecule in
the solid state the ice structure extends in 3 dimensions. The water
molecule present in the centre of the tetrahedron is attached to four H2O
molecules present at its 4 corners with hydrogen bonds.
 Open structure of ice

Each oxygen atom is linked to two hydrogen atoms by covalent bonds and other
two by hydrogen bonds. In this arrangement of H2O molecules certain vacant
spaces are left which gives rise to an open cage like structure for ice having a
larger volume for the given mass of water. As a result density of ice is less than
water.

• Water has maximum density and minimum volume at 4oc. Ice melts at 0oc
and water also freezes at the same temperature. This means that both ice
and water are present at 0oc.When temperature rises, energy is absorbed
and the open cage structure starts collapsing due to the breakdown of
hydrogen bonds. This makes the water molecule come closer and also the
water molecule separated from ice structure fill the vacant spaces in the
open cage structure.
This will lead to the increase in density of water on heating above the melting
point of ice and becomes maximum at 4oc.Beyond this temperature the effect of
increase in kinetic energy is more than the effect of decrease in hydrogen
bonding. This means that beyond 4oc, the volume of water is expected to
increase and density to decrease. In other words the density of water increases
from 0 to 4oc and then decreases. Thus water has maximum density and
minimum volume at 4oc.

• This behaviour of water is immensely helpful for aquatic life. In severe cold
surface of sea water freezes but water present below the surface is at
4oc.Therefore Sea animals can safely live at this temperature even when
the upper surface is frozen.

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