CHEMISTRY Theory Notes on Chemical Bonding-VI

H- Bonding
The idea of H-bonding was introduced to explain the nature of association in liquid state of Substances
like water, HF, NH3, etc.
In a hydrogen compound, when hydrogen is bonded to highly
electronegative atom (such as F, O, N) by a covalent bond, the electron
pair is attrached towards electronegative atom (such as F, O, N) by a
covalent bond, the electron pair is attracted towards electronegative
atom so strongly that a dipole results.If a member of such molecules are
brought nearer to each other, the positive end of one molecule and
negative end of other molecule will attract each other and weak electro-
static force will develop. Thus, these molecules will associate together to
form a cluster of molecules.
         
X – H ------- X – H ------ X – H ------- X – H ------- X – H
Here the attractive force that binds hydrogen atom of one molecule with electronegative atom of the
other molecule of the same or different substance is known as hydrogen bond.
H-bonding is of two types-
(a) Intermolecular H-bonding:
This type of bonding results between positive ends negative ends of different atom of the same or
different molecules.
This type of H-bonding increases the boiling point of the compound and also its solubility in water due to
association of several molecules of compound.
Inter-molecular H-bonding is also responsible for increase in the viscocity.
CH3 - CH2 - OH CH2 - OH CH2 - OH
| |
η = 1.2 CH2 - OH CH - OH
|
η = 17 CH2 - OH

η = 107
This type of H-bonding takes place between H and electronegative element present in the different
molecules of the same substance (as in between H2O and H2O) or different substances (as in between
H2O and NH3)
(A) In water molecules:
Due to polar nature of H2O, there is association of water molecules giveing a liquid state of abnormally
high b.p.:
 2  2  2  2
H – O .... H – O .... H – O .... H – O
| | | |
δ δ δ
H H H H δ
If we actually observe, one water molecules is joined to four water molecules- two with H-atoms and
other two with O-atom. Thus coordination number of water molecule in water is four.
(B) In HF there is again linear chain association by H-bonding
However in the gaseous state, several polymeric forms of the HF molecules exist in which the monomers
are held together through H-bonding. It exist as (HF)6 (cyclic), (HF)5 (cyclic), (HF)2 (diner) upto and
extent (HF, monomer)
(C) Carboxylic acid dimerises is gaseous state due to H-bonding

(D) Alcohol is said to be highly soluble in water due to crossed intermolecular H-bonding (between H2O
and R-OH molecules).
R H R
| | |

.... O – H .... O – H .... O – H

δ δ δ δ δ δ
However isomeric ether is less soluble in water due to its (ether) non-polar nature.
  
CH3–CH2– O – H CH3– O –CH3
polar less polar

Intra-Molecular H-bonding-
This type of bonding results between hydrogen & an electronegative element both present in the same
molecule.
This type of bonding decreases the boiling point of the compd.

(A) (B)

(C)
Nature and importance of H-Bond-
(1) H-bond is merely an alectrostatic force rather than a chemical bond.

(2) H-bond never involves more than two atoms.

(3) Bond energy of H-bond is in the range of 3 to 10 k cal/mole. Which is about (1/10)th the energy of
a covalent bond (50 to 100 k cal/mole)

(4) With the increase of electronegativity and decrease in size of the atom to which hydrogen is covalanthy
linked. The strength of the H-bond increases as

HF----H > H–O ----H > H–N ---- H

10 kcal/mol 7 kcal/mol 3 kcal/mol

Some properties explained by H-bonding-

(1) High B.P. & M.P. of NH3, H2O and HF in comparison to hydrides of other elements of V, VI and VII
grps. to which N, O and F belong respectively.
(2) H2O exists as liquid under normal conditions whereas H2S exists as a gas.
(3) A substance is said to be insoluble in water if it does not form H-bonding with H2O. Therefore,
Alkanes, Alkenes & Alkynes are in soluble whereas alcohols & acids are soluble in water.
* Ether is also insoluble.
* Chlorine has the same electronegativity as Nitrogen but does not form strong H-bonding. This is
because of the larger size than that of nitrogen with the result that its electrostatic attractions are weak.
(4) Dissociation- In liquid solutions, HF dissociates & gives the difluoride ion (HF2-) instead of fluoride
ion (F-). This is due to H-bonding in HF. This explains the existance of KHF2.
Association- Due to H-bonding carboxylic acid exict as dimers due to intermolecular H-bonding as
shown below.

(5) Solubility in water: Compounds which form hydrogen bonding with water will dissolvein water. For
example lower alcohol are soluble in water because their molecules can form H-bonds with water
  
.... H - O .... H - O .... H - O
\ \ \
C2H 5 H C2H 5
Similarly ammonia and amines are soluble in water due to H-bonding with water.
(6) The substances which can give more extensive hydrogen bonding will have higher viscosity and high
surface tension
Ethanol  Glycol  Glycerol
e.g. Higher viscosity and surface tension