HYDROGEN BONDING

DEFINITION
The electrostatic attraction between partially positively
charged hydrogen atom bonded to a relatively
electronegative atom and another electronegative atom is
referred to as hydrogen bond.
It is represented by a dotted line as shown below.
CHARACTERISTIC

1) The hydrogen atom participating in H-bond must be covalently

bonded to a highly electronegative atom in order to acquire significant
positive charge. 
For example, H atom covalently bonded to electronegative atoms like
F, O and N can participate in hydrogen bonding. 
2) The acceptor electronegative atom should also possess at least one
lone pair and high charge density so as to attract positively charged
H atom effectively. Thus H-bonding is normally observed with smaller
and highly electronegative atoms such as F, O and N with lone pairs.
3) The H-bond is mostly electrostatic in nature. However, directional
nature of hydrogen bonding, shorter inter atomic distances
between molecules participating in H-bonding and limited number
of H-bond interactions suggest some covalent nature also. 
E.g. In HF, the number of H-bonds per each molecule is limited
to only two, since there is only one hydrogen per molecule and
only one lone pair on Fluorine can participate in H-bonding. The
directional nature is also evident from the following diagram.
4) The hydrogen bond is stronger than van der Waal's forces of
attraction. But it is weaker than the covalent bond and ionic bond
. 
The strength of Hydrogen bonds can range from very weak (1–2
kJ mol-1) to extremely strong (161.5 kJ mol-1).
TYPES OF HYDROGEN BONDING

Intermolecular Hydrogen Bonding

Intra-molecular Hydrogen Bonding
Intermolecular Hydrogen Bonding
The H-bond formed between two different molecules (of same or
different compounds) is referred to as intermolecular H-bond. In this
case, hydrogen of one molecule makes H-bond with electronegative
atom of another molecule. These molecules may belong to same
compound or different compounds.
Consequences of Intermolecular
Hydrogen Bonding
1) The boiling point, melting point, sublimation point as well
as enthalpy of vaporization of compounds increase due
to intermolecular H-bonding. 
E.g. The boiling point of H2O is high (373 K) due to
intermolecular hydrogen bonding and hence it exist as
liquid at room temperature, whereas H-bonds are
absent in H2S and hence it has low boiling point and
exists as a gas at room temperature
2) The solubility of compounds, showing intermolecular H-bonding, in
water increases due to formation of intermolecular H-bonds with
water. 
E.g. Ethyl alcohol, methyl alcohol, ammonia, HF, acetic acid etc.,
are fairly soluble in water due to their ability to form intermolecular
hydrogen bonds with water molecules. 
Intermolecular H-bonding between water and ammonia molecules is
shown below
3) Due to intermolecular H-bonding, para isomers have higher
boiling points and are fairly soluble in water. Therefore they
cannot be separated by steam distillation. 
E.g. Para hydroxy benzaldehyde has high boiling point and is
more soluble in water, than its ortho isomer, due to
intermolecular H-bonding and hence cannot be separated by
steam distillation.
4) Some molecules exist as dimers or trimers or polymers
in non-aqueous medium or in vapor state due to strong
intermolecular H-bonding. 
E.g. Acetic acid exists as dimer in benzene
Intra-molecular Hydrogen Bonding
The H-bond formed between a hydrogen and the electronegative
atom of same molecule is called as intra-molecular H-bond. This is
also termed as intra-molecular chelation, since a ring is formed
within the molecule.
E.g. Ortho hydroxy benzaldehyde and ortho nitro phenol show intra-
molecular hydrogen bonding.
Consequences of Intra-molecular
Hydrogen Bonding
The boiling point, melting point and solubilities of isomers containing
intra-molecular hydrogen bonds are lower than their isomers showing
intermolecular H- bonds. 
E.g. The boiling point and solubility of ortho hydroxy benzaldehyde
(salicylaldehyde) are lower than those of para hydroxy benzaldehyde. 
In ortho hydroxy benzaldehyde, there are intra-molecular hydrogen
bonds, whereas para hydroxy benzaldehyde forms inter molecular H-
bonds. Hence ortho hydroxy benzaldehyde is steam volatile and can be
separated easily from other isomers by steam distillation. 
In general, boiling point, melting point and solubility in water are lower
for ortho isomers due to intra-molecular hydrogen bonding when
compared to their para isomers.
Illustration of Hydrogen Bonding
Hydrogen bonding in water and ice
Boiling points of hydrides of 15, 16 & 17 groups
Boiling points and solubility of alcohols and
ethers
Comparison of boiling points of HF and H2O
Hydrogen bonding in DNA
H-bonding in Proteins and carbohydrates
 
Hydrogen Bonding in Water and Ice
Each water molecule can form four H-bonds in tetrahedral
geometry due to presence of two lone pairs on oxygen
and two hydrogen atoms as illustrated below
Why density of ice is less than water?
Solid water (ice) has less density than water due to stable hydrogen
bonding which forces the crystalline structure to be very open
(hexagonal type of) creating some extra interstitial space. Hence ice
occupies more volume and hence less density than water. 
Note: Water contracts until the temperature is decreased to 4 oC like
any other liquid. Then it starts expanding with further decrease in
temperature. It expands about 9% at its freezing point.
Remember that the hydrogen bonds in water are not stable. They
constantly breakup and reform. But in ice they are stable and cannot be
shaken out of position due to insufficient thermal energy available at
low temperatures.
Boiling Points of Hydrides of 15, 16 & 17
Groups
The boiling points of compounds increase with increase in
the molecular weight since the van der Waal's forces of
attraction also increases with increase in the size of
molecule. 
Hence we expect smooth increase in the boiling points of
hydrides down the group. However, contrary to the
expectation, the BP's of hydrides of group 15, 16 and 17 of
the periodic table, are decreased from the first member to
the next and then show regular increment while going
down in each group.
The trend in BP's of hydrides of group 15 is:
NH3 > PH3 < AsH3 < SbH3 < BiH3
The order of BP's of hydrides of group 16 is: 
H2O > H2S <  H2Se < H2Te < H2Po
And the trend in BP's of hydrides of group 17 is:
HF > HCl < HBr < HI
The unexpected higher boiling points of NH3, H2O and
HF are due to intermolecular hydrogen bonding
Boiling Points and Solubility of Alcohols
and Ethers

Alcohols, R-OH can form intermolecular

hydrogen bonds due to presence of -OH group
that acts as donor group for H-bonding, whereas
ethers, R-O-R lack such groups and cannot
exhibit H-bonding. Hence alcohols posses high
boiling points and are fairly soluble in water.
However, ethers show lower boiling points than
their isomeric alcohols and are sparingly soluble
in water.
Comparison of Boiling Points of HF and H2O 

H2O has more boiling point than HF even though the H-bonds in
HF are more stronger and molar mass of HF (20.01 g mol-1) is
greater than that of H2O (18 g mol-1).
Reasons: 
1) In H2O,  there are twice the number of hydrogen bonds per
molecule than in HF. 
2) HF exists as (HF)6 cluster of molecules even in vapor state.
Hence it require less energy for transition from liquid state to
vapor state. Less number of bonds have to be broken while liquid
HF is converted to gaseous HF.
Hence the boiling point of H2O is higher than HF.
Hydrogen Bonding in DNA
H-bonds plays major role in the formation of double helical
structure of DNA. The hydrogen bonding between base
pairs are responsible for the double stranded structure and
those between phosphates cause the DNA strand to twist.
In DNA, it is observed that Adenine (A) always pairs with
Thymine (T) and Guanine (G) always pairs with Cytosine
(C) and hence the number of Adenine molecules is always
equal to the number of Thymine molecules and the number
of Guanine molecules is same as that of  Cytosine
molecules in DNA.
It is because, A forms two H-bonds with T,
whereas G forms three hydrogen bonds with C.
Other combinations will result in less number of
H-bonds.
H-bonding in Proteins and Carbohydrates
The hydrogen bonds also play major role in the secondary and tertiary
structures of proteins. The carboxylic group oxygens and amide group
hydrogens participate in the H-bonding and confer stable and specific
structural conformations to the proteins.
Many carbohydrates like mono and disaccharides are soluble in water due
to formation of intermolecular H-bonds with water. For example, glucose,
fructose, sucrose, maltose, lactose etc. are fairly soluble in water.
Some polysaccharides also show strong affinity with water and form
lyophilic colloids. E.g. Starch
The fibrous nature of cellulose can attributed to the formation of H-bonds.
Synthetic polymers like nylon are also strengthened by the hydrogen
bonds.