Hydrogen

Hydrogen is the most abundant element in the universe and

forms more compounds than any other element in the
periodic table. It is also the third most abundant element in
the Earth's crust, behind silicon and oxygen. Lavoisier in
1783 named the element hydrogen (from the Greek hydro
meaning water and genes meaning creator) because the gas
produces water when burned.
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Position in the periodic Table:

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Physical properties of Hydrogen

Pure hydrogen is a colorless, odorless and tasteless gas. Its
molecule is diatomic and is sparingly soluble in water.
Hydrogen possesses the smallest viscosity, the greatest power
of diffusion and effusion, and the highest specific heat.
Hydrogen is the best conductor of heat of all gases.
H
Chemical symbol

Boiling point

Atomic number

Electron
configuration

1s

Atomic weight
Melting point

1.00794 Ionic radius (H-)

-259 C

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-253 C

Ionization potential 13.598 eV

1

Pauling
electronegativity

2.1
1.54
3

Preparation of Hydrogen
1-By the action of metals with water, acids or alkalis
Hydrogen is evolved by the action of alkalis and some alkaline
earth metals with water. 2 Na 2 H O 2 NaOH
2

H2

It can also be produced the action of metals such as magnesium or

zinc with dilute acids such as sulphuric acid and hydrochloric acid
(laboratory method). Zn 2 HCl ZnCl H
2

Hydrogen is sometimes evolved by the action of alkalis on metals.

Thus a warm solution of sodium or potassium hydroxide dissolves
zinc, silicon or aluminum with the evolution of hydrogen and the
formation of aluminate, or zincate.

2 Al 2 NaOH 2 H 2O 2 NaAlO2 3H 2
Zn 2 KOH K 2 ZnO2 H 2

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2-Industrial method of preparation (Bosch process)

Hydrogen is prepared by passing steam over red hot coke at 1270 K.
First a mixture of CO and hydrogen known as water gas is formed.

Water gas is mixed with more of the steam and the gaseous mixture is
passed over heated catalytic mixture of ferric oxide (Fe2O3) and
chromium oxide (Cr2O3) at 773 K.

The resulting mixture is compressed to about 19000 mm of Hg pressure

and is passed into water. Carbon dioxide dissolves in water under
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pressure while
Hydrogen is released and collected. The carbon dioxide

2-The hydrolysis of metal hydrides.

CaH2 + 2H20 Ca(OH)2 + 2H2
3-By Electrolysis of Water
Pure hydrogen can be prepared by electrolysis of water in
presence of an electrolyte, either an acid or an alkali.
Generally, NaOH, KOH, or Ba(OH)2 is added, using nickel or
platinum electrodes. Very pure hydrogen is set free at the
cathode, while an equivalent quantity of oxygen is evolved at
the anode
2H2O O2 + 2H2
Anode Cathode
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Chemical properties of Hydrogen

Molecular hydrogen is chemically rather inert at ordinary temperature.

1-Reaction with non-metals

Hydrogen reacts with non-metals under specific conditions.

The reactivity of halogen towards hydrogen decreases as:

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F2 > Cl2 > Br2 > I2

2-Reaction with metal oxides

Being strong reducing agent hydrogen reduces metal oxides to
metals. For example,

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3-Reaction with unsaturated hydrocarbons

Unsaturated hydrocarbons such as ethylene and acetylene
react with hydrogen to give saturated hydrocarbons.

This reaction is used in the hydrogenation or hardening of oils.

The vegetable oils such as groundnut oil or cotton-seed oil are
unsaturated because they contain at least one double bond in
their molecules. Dihydrogen is passed through the oils at
about 473K in the presence of catalyst to form solid fats.

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Formation of Hydrides
Hydrogen behaves like a negative ion when it combines with some
metals forming hydrides H-. The type of hydride which an element
forms depend on it's electropositivity,

a.Ionic or salt-like hydrides

Only elements with very high electropositivity can transfer
electrons to the hydrogen atom and form salt-like hydrides. These
include the alkali metals (group 1) and the alkaline earth metals
(group 2 with the exception of Be and Mg), and lanthanum. These
are solids with ionic lattices, and have high melting points. They
conduct electricity when fused, liberate hydrogen at the anode and
thereby confirm that they contain the hydride ion H-.
They react with water and liberate hydrogen.

LiH

H
O

LiOH

H
2
2
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10

They are powerful reducing agents especially at high temp. for

example:

2CO NaH HCOONa C

b.Covalent Hydrides
Molecular hydrides are formed by the combination of elements of
comparatively higher electronegativity as of p block elements.
These bonds are mostly covalent in character with partly ionic
character too (for example, in HF). These hydrides have molecular
lattices held together by weak van der Waals forces. In some cases,
hydrogen bonds are also formed. This accounts for their softness,
low melting and boiling points volatility, and lack of conductivity.
The electronegativity difference between hydrogen and the atom
bonded to it, determines the properties of covalent hydrides. When
moving from left to right along a given row in the periodic table
. hydrides 11/24/16
become increasingly acidic in character
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. NH3 is a weak base, H2O is neutral and HF is acidic

. PH3 is a weak base, H2S is a weak acid and HCl is highly acidic
The hydrides of Group 13 (e.g., BH3 and AlH3) are electron deficient
compounds and exist in polymerised forms [e.g., B2H6 and (AlH3)n].
Carbon forms polynuclear hydrides wherein numerous hydrocarbons are
generated.
All these hydride compounds are covalently bonded. Although LiAlH4 is
H- donors it also contains covalent Al-H bonds. LiAlH4 can be formed
from the reaction of LiH with Al2Cl6.
8 LiH + Al2Cl6 2 LiAlH4 + 6 LiCl

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c.Metallic or Interstitial Hydrides:

Metallic hydrides are formed by most of the d block
elements (i.e., transition elements), on reacting with hydrogen.
Hydrogen exists in the atomic rather than ionic form. Due to
small size of hydrogen atoms when compared to the metal
atoms, hydrogen atoms occupy interstitial positions in the
metal lattices; hence interstitial hydride and can be considered
as solid solutions. Beryllium and magnesium of 's' block
elements also form metallic hydrides. Metallic or interstitial
hydrides compounds are non-stoichiometric and their
composition varies with temperature and pressure. They give
out hydrogen easily and are strong reducing agents, suggesting
.that the presence of hydrogen in its atomic state
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13

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The Hydrogen Ion

The energy required to remove the electron from the hydrogen atom (i.e.
the ionization energy of hydrogen) is 1311 kJ mole-1. This is a very large
amount of energy, and consequently the bonds formed by hydrogen are
mainly covalent. Hydrogen fluoride is the compound most likely to
contain H+, since it has the greatest difference in elctronegativity, but
even here the bond is only 45% ionic. Thus hydrogen can only form the
hydrogen ion if its compounds are dissolved in media which solvate
protons and where the solvation energy provides sufficient energy to
offset the very high ionization energy of hydrogen. Thus in water,
solvated hydrogen ions H3O+ occur, the heat of solvation being 1091
kJmol-1 compounds which form solvated hydrogen ions in a suitable
solvent are acids.

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The Hydrogen Bond

The hydrogen bond is the strongest form of intermolecular
attraction. It comes about due to the polarity of X-H bonds in
molecules, where X is some electronegative element such as F, O,
N or Cl. The electrons in the X-H bond are pulled mostly over to
the atom X leaving the hydrogen atoms with a partial positive
charge (+). Because hydrogen has no inner electron shells to
shield the charge of its positively charged nucleus, it can then
interact with a negatively charged, electron rich, atom Y on another
molecule forming the hydrogen bond.
X-HY
The HY interaction is considered to be essentially electrostatic
and the distance between the two atoms is generally longer than a
normal H-Y bond, while the X-H bond is usually slightly
lengthened. In the strongest hydrogen bonds, the X-H and H-Y
distances can become almost equal. Here, the H-Y interaction is
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closer to a covalent interaction.

The influence of hydrogen bonding is most evident in the behaviour

of the XH3 compounds of the group 15 elements; the XH2 compounds
of group 16; and the XH acids of group 17. The boiling points of NH3,
H20 and HF are much higher than those of PH3, H2S and HCl
respectively. This is because the electronegativities of N (3.07), O
(3.50) and F (4.10) are much greater than that of H (2.20), whereas the
eletronegativities of P (2.06), S (2.44) and Cl (2.83) are much more
comparable to that of H.
The X-H bonds in these three first row compounds are much more
polar than those of the second row compounds leading to stronger
intermolecular associations through hydrogen bonding and higher
boiling point. Conversely, the electronegativity of C (2.50) is much
less than for N, O and F and comparable to H leading to very little
polarity in the C-H bonds of methane, CH4. Because of this CH4 has a
much lower boiling point than SiH4.
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Hydrogen bonds are vital for life, which needed liquid water in which
to start. Without hydrogen bonding interactions, water would be
expected to boil at around -100 C rather than +100 C, and so there
would be no liquid water on the Earth.
Hydrogen bonds are mostly electrostatic attractions, and as such they
are weaker than covalent bonds, but stronger than Van der Waals
interactions.

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H
N

H
H

H
F

F
H
F

Associated NH3 Molecules

Associated HF Molecules
H

Isotopes of Hydrogen:
If atoms of the same element have different mass numbers they are
called isotopes. The difference in mass number arises because the
nucleus contains a different number of neutrons.
These isotopes have the same electronic configuration and have
essentially the same chemical properties. The only difference in
chemical properties is equilibrium constants and the rates of reactions.
H is more11/24/16
rapidly adsorbed on to surfaces than D for example. 19

Isotope

Protium

Symbol

Atomic number

Number of neutrons

Mass number

Natural abundance

99.9844%

0.0156%

very small

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Deuterium
H or D

Tritium
3

H or T

20

Special Forms of Hydrogen

1-Ortho and Para Hydrogen
The hydrogen molecule H2 exists in two different forms known as
ortho and para hydrogen. The nuclear spins of the two atoms in the
molecule are either in the same direction or in opposite direction
and give rise to spin isomerism. This is also found in other
symmetrical molecules whose nuclei have spin momenta, e.g. O2,
N2, F2, Cl2.

Ordinary hydrogen is an equilibrium mixture of ortho and para

hydrogen.
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The amount of ortho and para hydrogen varies with temperature as:
At 0K, hydrogen contains mainly para hydrogen which is more
stable.
At the room temperature, the ratio of ortho to para hydrogen is 3 : 1.
Even at very high temperatures, the ratio of ortho to para hydrogen
can never be more than 3 : 1.

2-Nascent Hydrogen
The hydrogen gas, which is just liberated as a result of a chemical is
called nascent hydrogen or newly born hydrogen and is more
chemically active than ordinary hydrogen. Thus it reduces ferric
chloride to ferrous chloride, if metallic zinc and HCl are placed in a
ferric chloride solution 2 FeCl H ( nacent ) 2 FeCl 2 HCl
3

The great reactivity of nascent hydrogen is explained by the fact that

is consists of hydrogen molecules to which some of the energy
liberated by
the reaction is imparted, thus increasing its chemical22
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Uses of Hydrogen
It is used as a reducing agent in industry and laboratories.
It is used to prepare hydrogenated vegetable oils.
It is used for welding purposes in both the oxy-hydrogen
torch and the atomic-hydrogen torch, when temperatures of
the order of 2500C and 4000C are required respectively.
It is used as a rocket fuel in the form of liquid hydrogen and
liquid oxygen.
It is used in the manufacture of synthetic petrol.
It is used in the preparation of many compounds such as
methane, ammonia, water gas, and fertilizers such as urea,
ammonium
sulphate, etc.
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