What is Hydrogen Bonding?

Hydrogen bonding refers to the formation of Hydrogen bonds, which are a special class of
attractive intermolecular forces that arise due to the dipole-dipole interaction between a
hydrogen atom that is bonded to a highly electronegative atom and another highly
electronegative atom which lies in the vicinity of the hydrogen atom. For example, in water
molecules (H2O), hydrogen is covalently bonded to the more electronegative oxygen atom.
Therefore, hydrogen bonding arises in water molecules due to the dipole-dipole interactions
between the hydrogen atom of one water molecule and the oxygen atom of another H2O
molecule.
Here, the location of the bond pair of electrons in the O-H bond is very close to the oxygen
nucleus (due to the large difference in the electronegativities of oxygen and hydrogen).
Therefore, the oxygen atom develops a partial negative charge (-δ) and the hydrogen atom
develops a partial positive charge (+δ). Now, hydrogen bonding can occur due to the
electrostatic attraction between the hydrogen atom of one water molecule (with +δ charge) and
the oxygen atom of another water molecule (with -δ charge). Thus, hydrogen bonds are a very
special class of intermolecular attractive forces that arise only in compounds featuring hydrogen
atoms bonded to a highly electronegative atom. Hydrogen bonds are mostly strong in
comparison to normal dipole-dipole and dispersion forces. However, they are weak compared to
true covalent or ionic bonds.

Table of Content

 Conditions
 Effects
 Examples
 Strength of Hydrogen Bond
 Properties
 Types of H-Bond
 Electron Sea Model

What are the Conditions for Hydrogen Bonding?

In a molecule, when a hydrogen atom is linked to a highly electronegative atom, it attracts the
shared pair of electrons more and so this end of the molecules becomes slightly negative while
the other end becomes slightly positive.  The negative end of one molecule attracts the positive
end of the other and as a result, a weak bond is formed between them. This bond is
called the hydrogen bond.
As a result of hydrogen bonding, a hydrogen atom links the two electronegative
atoms simultaneously, one by a covalent bond and the other by a hydrogen bond. The
conditions for hydrogen bonding are:
 1. The molecule must contain a highly electronegative atom linked to the hydrogen atom.
The higher the electronegativity more is the polarization of the molecule.
2. The size of the electronegative atom should be small. The smaller the size, the greater is
the electrostatic attraction.

Also Read:

 Chemical Bonding
 Covalent Bond

Effects of Hydrogen Bonding on Elements

Association
The molecules of carboxylic acids exist as dimer because of the hydrogen bonding.
The molecular masses of such compounds are found to be double than those calculated from
their simple formula.

Dissociation
In aqueous solution, HF dissociates and gives the difluoride ion instead of fluoride ion. This is
due to hydrogen bonding in HF. The molecules of HCl, HBr, HI do not form a hydrogen bond.
This explains the non-existence of compounds like KHCl2, KHBr2, KHI2.

Why do compounds having hydrogen bonding have high melting and boiling points?
The compounds having hydrogen bonding show abnormally high melting and boiling points.
The high melting and boiling point of the compound containing hydrogen bonds is due to the
fact that some extra energy is needed to break these bonds.

 The unusually high boiling point of hydrogen fluoride among the halogen acid is due to
the existence of hydrogen bonding.
 H2O is a liquid whereas H2S, H2Se and H2Te are all gases at ordinary temperature. In
water, hydrogen bonding causes linkages in the water molecules which result in the
boiling point of water is more than that of the other compounds.
 Ammonia has a higher boiling point than PH3 because there is hydrogen bonding in
NH3 but not in PH3.
 Ethanol has a higher boiling point than diethyl ether because there is hydrogen bonding in
the ethanol.

Examples of Hydrogen Bonding

Hydrogen Bonding in Hydrogen fluoride

Fluorine having the highest value of electronegativity forms the strongest hydrogen bond.
Hydrogen Bonding in Water
A water molecule contains a highly electronegative oxygen atom linked to the hydrogen atom.
Oxygen atom attracts the shared pair of electrons more and this end of the molecule becomes
negative whereas the hydrogen atoms become positive.

Hydrogen Bonding in Ammonia

It contains highly electronegative atom nitrogen linked to hydrogen atoms.
Hydrogen Bonding in Alcohols and Carboxylic acid
Alcohol is a type of an organic molecule which contains an -OH group. Normally, if any
molecule which contains the hydrogen atom is connected to either oxygen or nitrogen directly,
then hydrogen bonding is easily formed.

Hydrogen Bonding in Alcohols

 Hydrogen Bonding in Carboxylic acid

Hydrogen Bonding in Polymers

Hydrogen bonding is an important factor in determining the 3D structures and properties that
are acquired by synthetic and natural proteins.  Hydrogen bonds also play an important role in
defining the structure of cellulose as well as derived polymers such as cotton or flax.

Strength of the Hydrogen bond

The hydrogen bond is a weak bond. The strength of hydrogen bond is in-between the weak van
der Waals forces and the strong covalent bonds.
The dissociation energy of the hydrogen bond depends upon the attraction of the shared pair of
electrons and hence on the electronegativity of the atom.

Properties of Hydrogen Bonding

 Solubility: Lower alcohols are soluble in water because of the hydrogen bonding which
can take place between water and alcohol molecule.
 Volatility: As the compounds involving hydrogen bonding between different molecules
have a higher boiling point, so they are less volatile.
 Viscosity and surface tension: The substances which contain hydrogen bonding exists
as an associated molecule. So their flow becomes comparatively difficult. They have
higher viscosity and high surface tension.
 The lower density of ice than water: In the case of solid ice, the hydrogen bonding
gives rise to a cage-like structure of water molecules. As a matter of fact, each water
molecule is linked tetrahedral to four water molecules. The molecules are not as closely
packed as they are in a liquid state. When ice melts, this case like structure collapses and
 the molecules come closer to each other. Thus for the same mass of water, the volume
decreases and density increases. Therefore, ice has a lower density than water at 273 K.
That is why ice floats.
Related Articles

 Fajan’s rule
 Hybridization
 Molecular Orbital Theory

Types of Hydrogen Bonding

There are two types of H bonds, and it is classified as the following:

 Intermolecular Hydrogen Bonding

 Intramolecular Hydrogen Bonding

Intermolecular Hydrogen Bonding

When hydrogen bonding takes place between different molecules of the same or different
compounds, it is called intermolecular hydrogen bonding.
For example – hydrogen bonding in water, alcohol, ammonia etc.

Intramolecular Hydrogen Bonding

The hydrogen bonding which takes place within a molecule itself is called intramolecular
hydrogen bonding.
It takes place in compounds containing two groups such that one group contains hydrogen atom
linked to an electronegative atom and the other group contains a highly electronegative atom
linked to a lesser electronegative atom of the other group.
The bond is formed between the hydrogen atoms of one group with the more electronegative
atom of the other group

Symmetric Hydrogen Bond

This is a special type of hydrogen bond where the proton is usually placed in the middle
between two identical atoms. The strength of the bond between each atom is equal. The
symmetric hydrogen bond is a type of a three-centre four-electron bond. This bond is also much
stronger compared to the “normal” hydrogen bond and its strength is almost similar to a
covalent bond.