The document discusses hydrogen bonding, describing its nature, types, and significance in various substances, such as water, alcohols, and biological macromolecules. It explains both intermolecular and intramolecular hydrogen bonds, their roles in determining physical properties like boiling points and structure in proteins and DNA. Additionally, the document covers advanced concepts such as symmetric hydrogen bonds and their implications in chemistry.

1. 1
By
KAUSHAL KUMAR SAHU
Assistant Professor (Ad Hoc)
Department of Biotechnology
Govt. Digvijay Autonomous P. G. College
Raj-Nandgaon ( C. G. )

2.  INTRODUCTION
 BONDING
 HISTORY
 TYPES OF HYDROGEN BOND
 HYDROGEN BONDS IN WATER
 HYDROGEN BONDING IN ALCOHOL
 HYDROGEN BONDS IN DNAAND PROTEINS
 HYDROGEN BONDS IN POLYMERS
 SYMMETRIC HYDROGEN BOND
 DIHYDROGEN BOND
 ADVANCE THEORY OF THE HYDROGEN BOND
 HYDROGEN BONDING PHENOMENA
 CONCLSION
 REFERENCES
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3.  hydrogen bond is the attractive interaction
of a hydrogen atom with an electronegative
atom, such as nitrogen, oxygen or fluorine,
that comes from another molecule or
chemical group.
 The hydrogen must be covalently bonded to
another electronegative atom to create the
bond. These bonds can occur between
molecules (intermolecularly), or within
different parts of a single molecule
(intramolecularly).
 The hydrogen bond is stronger than a van der
Waals interaction, but weaker than covalent
or ionic bonds.
 This type of bond occurs in both inorganic
molecules such as water and organic
molecules such as DNA. 3

4.  In the book The Nature of the Chemical Bond,
Linus Pauling credits T. S. Moore and T. F.
Winmill with the first mention of the hydrogen
bond, in 1912.
 Moore and Winmill used the hydrogen bond to
account for the fact that trimethylammonium
hydroxide is a weaker base than
tetramethylammonium hydroxide.
 The description of hydrogen bonding in its
more well-known setting, water, came some
years later, in 1920, from Latimer and
Rodebush. 4

5.  A hydrogen atom attached to a relatively electronegative atom is a hydrogen bond donor.
 This electronegative atom is usually fluorine, oxygen, or nitrogen.
 An electronegative atom such as fluorine, oxygen, or nitrogen is a hydrogen bond acceptor,
regardless of whether it is bonded to a hydrogen atom or not.
 An example of a hydrogen bond donor is ethanol, which has hydrogen bonded to oxygen;
an example of a hydrogen bond acceptor which does not have a hydrogen atom bonded to
it is the oxygen atom on diethyl ether.
 Hydrogen attached to carbon can also participate in hydrogen bonding when the carbon
atom is bound to electronegative atoms, as is the case in chloroform, CHCl3.
 The electronegative atom attracts the electron cloud from around the hydrogen nucleus
and, by decentralizing the cloud, leaves the atom with a positive partial charge. Because of
the small size of hydrogen relative to other atoms and molecules, the resulting charge,
though only partial, represents a large charge density.
 A hydrogen bond results when this strong positive charge density attracts a lone pair of
electrons on another heteroatom, which becomes the hydrogen-bond Acceptor.
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6. Intermolecular hydrogen bond
 This occurs when the hydrogen
bonding is between H-atom of one
molecule and an atom of the
electronegative element of another
molecule. For example-
 Hydrogen bond between the
molecules of hydrogen fluoride.
 Hydrogen bond in alcohol or water
molecules.
 Intermolecular hydrogen bond results
into association of molecules. Hence,
it usually increases the melting point,
boiling point, viscosity, surface
tension, solubility, etc.
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An example of intermolecular
hydrogen bonding in a self-
assembled dimer complex
reported by Meijer and
coworkers.

7. Intramolecular hydrogen bond
 This bond is formed between the
hydrogen atom and an atom of the
electronegative element (F, O, N),
of the same molecule.
 Intramolecular hydrogen bond
results in the cyclization of the
molecules and prevents their
association.
 Consequently, the effect of this
bond on the physical properties is
negligible. For example,
intramolecular hydrogen bonds
are present in molecules such as
o-nitrophenol, o-nitrobenzoic
acid, etc.
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Intramolecular hydrogen bonding in
acetyl-acetone helps stabilize the enol
tautomer

8.  The most ubiquitous, and perhaps simplest, example of a hydrogen bond is found
between water molecules.
 In a discrete water molecule, there are two hydrogen atoms and one oxygen atom. Two
molecules of water can form a hydrogen bond between them; the simplest case, when
only two molecules are present, is called the water dimer and is often used as a model
system.
 When more molecules are present, as is the case of liquid water, more bonds are
possible because the oxygen of one water molecule has two lone pairs of electrons, each
of which can form a hydrogen bond with a hydrogen on another water molecule.
 This can repeat such that every water molecule is H-bonded with up to four other
molecules, as shown in the figure (two through its two lone pairs, and two through its
two hydrogen atoms).
 Hydrogen bonding strongly affects the crystal structure of ice, helping to create an
open hexagonal lattice.
 The density of ice is less than water at the same temperature; thus, the solid phase of
water floats on the liquid, unlike most other substances.
 Liquid water's high boiling point is due to the high number of hydrogen bonds each
molecule can form relative to its low molecular mass.
 Owing to the difficulty of breaking these bonds, water has a very high boiling point,
melting point, and viscosity compared to otherwise similar liquids not conjoined by
hydrogen bonds.
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9. 9
Model of hydrogen bonds (1)
between molecules of water

10.  An alcohol is an organic molecule
containing an -OH group.
 Any molecule which has a hydrogen
atom attached directly to an oxygen
or a nitrogen is capable of hydrogen
bonding. Such molecules will
always have higher boiling points
than similarly sized molecules
which don't have an -OH or an -NH
group. The hydrogen bonding
makes the molecules "stickier", and
more heat is necessary to separate
them.
 Ethanol, CH3CH2-OH, and
methoxymethane, CH3-O-CH3, both
have the same molecular formula,
C2H6O.
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11.  Hydrogen bonding also plays an important role in determining
the three-dimensional structures adopted by proteins and nucleic
bases.
 In these macromolecules, bonding between parts of the same
macromolecule cause it to fold into a specific shape, which helps
determine the molecule's physiological or biochemical role.
 The double helical structure of DNA, for example, is due largely
to hydrogen bonding between the base pairs, which link one
complementary strand to the other and enable replication.
 In the secondary structure of proteins, hydrogen bonds form
between the backbone oxygens and amide hydrogens.
 When two strands are joined by hydrogen bonds involving
alternating residues on each participating strand, a beta sheet is
formed.
 Hydrogen bonds also play a part in forming the tertiary structure
of protein through interaction of R-groups.
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The structure
of part of a
DNA double
helix

12. 12
Hydrogen bonding between guanine and
cytosine, one of two types of base pairs in DNA

13.  Many polymers are strengthened by hydrogen bonds in their main chains.
 Among the synthetic polymers, the best known example is nylon, where hydrogen
bonds occur in the repeat unit and play a major role in crystallization of the material.
The bonds occur between carbonyl and amine groups in the amide repeat unit.
 They effectively link adjacent chains to create crystals, which help reinforce the
material.
 The effect is greatest in aramid fibre, where hydrogen bonds stabilize the linear
chains laterally.
 The chain axes are aligned along the fibre axis, making the fibres extremely stiff and
strong.
 Hydrogen bonds are also important in the structure of cellulose and derived polymers
in its many different forms in nature, such as wood and natural fibres such as cotton
and flax.
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Para-aramid structure

14.  A symmetric hydrogen bond is a special type of hydrogen bond in which the
proton is spaced exactly halfway between two identical atoms.
 The strength of the bond to each of those atoms is equal.
 It is an example of a 3-center 4-electron bond. This type of bond is much
stronger than "normal" hydrogen bonds. The effective bond order is 0.5, so its
strength is comparable to a covalent bond. It is seen in ice at high pressure,
and also in the solid phase of many anhydrous acids such as hydrofluoric acid
and formic acid at high pressure.
 It is also seen in the bifluoride ion [F−H−F]−.
 Symmetric hydrogen bonds have been observed recently spectroscopically in
formic acid at high pressure .
 Each hydrogen atom forms a partial covalent bond with two atoms rather
than one. Symmetric hydrogen bonds have been postulated in ice at high
pressure .
 Low-barrier hydrogen bonds form when the distance between two
heteroatoms is very small.
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15.  The hydrogen bond can be compared with the closely related
dihydrogen bond, which is also an intermolecular bonding
interaction involving hydrogen atom.
 These structures have been known for some time, and well
characterized by crystallography; however, an understanding of
their relationship to the conventional hydrogen bond, ionic bond,
and covalent bond remains unclear.
 Generally, the hydrogen bond is characterized by a proton
acceptor that is a lone pair of electrons in nonmetallic atoms.
 In some cases, these proton acceptors may be pi-bonds or metal
complexes. In the dihydrogen bond, however, a metal hydride
serves as a proton acceptor; thus forming a hydrogen-hydrogen
interaction.
 Neutron diffraction has shown that the molecular geometry of
these complexes is similar to hydrogen bonds, in that the bond
length is very adaptable to the metal complex/hydrogen donor
system.
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16.  The hydrogen bond remains a fairly mysterious object in the theoretical study of
quantum chemistry and physics.
 Most generally, the hydrogen bond can be viewed as a metric dependent
electrostatic scalar field between two or more intermolecular bonds.
 This is slightly different than the intramolecular bound states of, for example,
covalent or ionic bonds; however, hydrogen bonding is generally still a bound state
phenomenon, since the interaction energy has a net negative sum.
 The question of the relationship between the covalent bond and the hydrogen bond
remains largely unsettled, though the initial theory proposed by Linus Pauling
suggests that the hydrogen bond has a partial covalent nature.
 While alot of experimental data has been recovered for hydrogen bonds in water, for
example, that provide good resolution on the scale of intermolecular distances and
molecular thermodynamics, the kinetic and dynamical properties of the hydrogen
bond in dynamical systems remains largely mysterious.
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17.  Dramatically higher boiling points of NH3, H2O, and HF
compared to the heavier analogues PH3, H2S, and HCl.
 Increase in the melting point, boiling point, solubility, and
viscosity of many compounds can be explained by the concept
of hydrogen bonding.
 Viscosity of anhydrous phosphoric acid and of glycerol.
 Dimer formation in carboxylic acids and hexamer formation in
hydrogen fluoride, which occur even in the gas phase, resulting
in gross deviations from the ideal gas law.
 Pentamer formation of water and alcohols in apolar solvents.
 High water solubility of many compounds such as ammonia is
explained by hydrogen bonding with water molecules.
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18.  The fact that ice is less dense than liquid water is
due to a crystal structure stabilized by hydrogen
bonds.
 Smart rubber utilizes hydrogen bonding as its sole
means of bonding, so that it can "heal" when torn,
because hydrogen bonding can occur on the fly
between two surfaces of the same polymer.
 Strength of nylon and cellulose fibres.
 Wool, being a protein fibre is held together by
hydrogen bonds, causing wool to recoil when
stretched. However, washing at high temperatures
can permamently break the hydrogen bonds and a
garment may permanently lose its shape.
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19.  A hydrogen bond is a type of attractive (dipole-dipole)
interaction between an electronegative atom and
a hydrogen atom bonded to another
electronegative atom. This bond always involves
a hydrogen atom. Hydrogen bonds can occur
between molecules or within parts of a
single molecule. A hydrogen bond tends to be stronger
than van der Waals forces, but weaker than covalent
bonds or ionic bonds.
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20.  Nelson and Cox- principle of biochemistry
 Gerald Karp- cell and molecular biology
 Lodish- molecular cell biology
 www.wikipedia.com
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