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Hydrogen
 Atomic Structure of Hydrogen

Electron
Electron = 1

Proton = 1

Nucleus
Neutron = 0

Hydrogen
 Isotopes of Hydrogen

Atomic Mass Relative

Name Symbol
number number abundance

Protium or 1
H 1 1 99.985 %
Hydrogen 1

2
Deuterium H1 1 2 0.0156 %

3
Tritium H1 1 3 10-15 %
 Isotopic Effect

Same causes
electronic similar For example, the reaction
configuration chemical between
of isotopes properties H2 and Cl2 is almost 13 times
faster than that between D2
and Cl2
Results in under similar conditions.
Difference in
difference in
bond
the rate of
enthalpies
reactions
Position of Hydrogen in
the Periodic Table
 Position of Hydrogen in the Periodic Table

Resemblance
Hydrogen is the first element of the
with alkali
periodic table as its atomic number is 1. 1 metals

a One electron in its valence

shell - 1s1

Electronic configuration 1s1 b Forms an unipositive ion

H+ (like Li+, Na+)

Hydrogen resembles alkali metals as

well as halogens in many properties.
 Position of Hydrogen in the Periodic Table

Forms oxides, halides, and

c d Good reducing agent
sulphides like alkali metals

Oxide Halide Sulphide Δ

CuO + H2 Cu + H2O

Na2O NaCl Na2S

Δ
H2O HCl H2S B2O3 + 6K 3K2O + 2B
 Position of Hydrogen in the Periodic Table

Has high ionisation

c
Resemblance with enthalpy like halogens
2 halogens
H 1312 kJ/mol

F 1680 kJ/mol
One electron less than that of its
a preceding inert gas configuration Cl 1255 kJ/mol

Forms a diatomic molecule H2

b
(like Cl2, Br2, I2)
Position of Hydrogen in the Periodic Table

Forms an uninegative ion

d
like halogens

e Forms compounds like halogens

CCl4 SiCl4 NaCl

CH4 SiH4 NaH

 Position of Hydrogen in the Periodic Table

Metallic character
Dissimilarities between (under normal conditions)
3 hydrogen and alkali metals

I.E. of hydrogen (1312 kJ/mol) is Alkali metals Hydrogen

very high compared to that
of alkali metals.

Li 520 kJ/mol

Na 495 kJ/mol
Position of Hydrogen in the Periodic Table

Dissimilarities between
4 hydrogen and halogens

The reactivity of hydrogen is very

low compared to that of halogens.

Oxides of halogens are acidic, while

the oxide of hydrogen is neutral.
 Occurrence

Most abundant element of

1
the universe (70% of the total mass)

It is much less abundant

2 (0.15 % by mass) in the earth’s
atmosphere due to its light nature

In combined form, it constitutes 15.4% of

3
the earth’s crust and the oceans
Elemental Form of Hydrogen

Shared pair
of electrons
 Preparation of Dihydrogen

1 By the action of water with metals

Action of water with Na, K, & Action of water with Mg, Al, & Zn
1 2
Ca at room temperature at the boiling temperature of water

Δ
2M + 2H2O Δ 2MOH + H2 2Al + 3H2O Al2O3 + 3H2

Δ
M = Na, K Mg + H2O MgO + H2
 Preparation of Dihydrogen

By the reaction of metals like Laboratory method: By the

3 Zn & Al with alkali 4 action of granulated zinc
with dilute HCl

Δ
Zn + 2NaOH Na2ZnO2 + H2 Zn (granulated) + 2HCl ZnCl2 + H2

Sodium zincate

Δ
2Al + 2H2O + 2NaOH 2NaAlO2 + 3H2

Sodium meta
aluminate
 Preparation of Dihydrogen

By the electrolysis of acidified

5 Preparation of pure dihydrogen 6 water using platinum electrodes

By the electrolysis of warm aq.

Ba(OH)2 between Ni
electrodes
2H2O(l) 2H2(g) + O2(g)

Dihydrogen of high purity At At

(> 99.95%) is obtained. cathode anode
 Preparation of Dihydrogen

7 Preparation from hydrocarbons

1270 K
CH4 (g) + H2O (g) CO (g) + 3H2 (g)
Ni

8 Coal gasification

1270 K
C (s) + H2O (g) CO (g) + H2 (g)

Water gas
(Syngas)
 Preparation of Dihydrogen

The yield of dihydrogen can be Methods to separate CO2 from H2

increased by reacting CO of the syngas
mixture with steam in the presence of 1. CO2 is dissolved in water
iron chromate as the catalyst. under high pressure (20-25
atm) and the H2 left
undissolved is collected.

Water-gas shift reaction 2. Carbon dioxide is removed

by scrubbing with sodium
arsenite solution.
673 K
CO (g) + H2O (g) CO2 (g) + H2 (g)
catalyst
 Preparation of Dihydrogen

At anode:
2Cl– (aq) Cl2 (g) + 2e–
Commercial production
8 of dihydrogen At cathode:
2H2O (l) + 2e– H2 (g) + 2OH– (aq)

As a byproduct in the Overall reaction:

manufacture of NaOH and Cl2 by
2Na+ (aq) + 2Cl– (aq) + 2H2O (l)
the electrolysis of brine solution

Cl2 (g) + H2 (g) + 2Na+ (aq) + 2OH– (aq)

 Physical Properties

Covalent radius (pm) = 37

It is a colourless, tasteless, and

Ionic radius (H–) (pm) = 208 odourless gas. It is insoluble in
water. It is highly combustible.

I.E. (kJ/mol) = 1312

Electron gain enthalpy

(kJ/mol) = - 73
Chemical Properties of Dihydrogen

Dihydrogen is quite stable and

dissociates into hydrogen atoms
at high temperature in an electric arc.

Δ
H2 H + H

ΔH ≈ 440 kJ mol-1
 Chemical Properties of Dihydrogen

Reaction with metals to Reaction with halogens to

1 form corresponding hydrides 2 form hydrogen halides

2M (g) + H2 (g) 2MH (s) H2 (g) + X2 (g) 2HX (g)

M = Alkali metal X = F, Cl, Br, I

Order of
reactivities

F2 > Cl2 > Br2 > I2

Chemical Properties of Dihydrogen

3 Reaction with dioxygen

catalyst or
2H2 (g) + O2 (g) 2H2O (l)
heating

ΔH° ≈ - 285 kJmol-1

 Chemical Properties of Dihydrogen

673 K, 200 atm

4 Reaction with dinitrogen 3H2 (g) + N2 (g) 2NH3 (g)
Fe/Mo

ΔH° = - 92.6 kJmol-1

Hydrogenation of
5 unsaturated alkenes Ni or Pd
CH2 CH2 + H2 CH3 CH3
473 K

Ni or Pd
HC CH + 2H2 CH3 CH3
473 K
 Chemical Properties of Dihydrogen

6 Hydroformylation of olefins

It yields aldehydes, which further

undergo reduction to give alcohols.

Catalyst
RCH CH2 + H2 + CO RCH2CH2CHO

Catalyst
RCH2CH2CHO + H2 RCH2CH2CH2OH
 Chemical Properties of Dihydrogen

473 K
Hydrogenation of Vegetable oil + H2 Edible fats
7 Ni
vegetable oils
(Margarine and
vanaspati ghee)

Reaction with metal ions

8 and metal oxides

H2 (g) + Pd2+ (aq) Pd (s) + 2H+ (aq)

yH2 (g) + MxOy (s) xM (s) + yH2O (l)

 Reducing
agent

Hydrogenation Used as a
of vegetable rocket fuel
oils
Uses of
Dihydrogen
Used in Preparation
fuel cells for of many
generating compounds
electrical Oxy/atomic like NH3
energy hydrogen
torch for
welding
 Hydrides

Dihydrogen combines with a

large number of non-metals Ionic or Saline or
and metals, except noble Salt like hydrides
gases, under certain suitable
reaction conditions to form
compounds called hydrides. Covalent or
Hydrides
Molecular hydrides

Metallic or Non-
Example: MgH2, B2H6
stoichiometric
hydrides
 Ionic or Saline Hydrides

Lighter metal hydrides such

as LiH, BeH2 and MgH2 have
e a r e sto ic hiometric significant covalent character.
Thes drogen
u n d s o f d ih y
compo
h m o s t o f th e s-block
wit
n ts w h ic h a re highly
eleme n ature.
p o s it iv e in
electro
BeH2 and MgH2 are
polymeric in nature.
 Ionic or Saline Hydrides

Crystalline

In solid
state

Non-volatile Non-conducting
 Ionic or Saline Hydrides

On electrolysis, molten saline

hydrides liberates H2 gas at anode. Ionic hydrides are powerful
reducing agents.
2H- (molten) H2 (g) + 2e- (at anode)

Saline hydrides react violently PbSO4 + 2CaH2 PbS + 2Ca(OH)2

with water liberating H2.

NaH (s) + H2O (l) NaOH (aq) + H2 (g)

 Ionic or Saline Hydrides

LiH is used in the synthesis

of other useful hydrides.

8LiH + Al2Cl6 2LiAlH4 + 6LiCl

2LiH + B2H6 2LiBH4

 Covalent or Molecular Hydrides

Covalent hydrides involve the formation of

covalent bonds between H atoms
s e a r e th e c ompounds
The most of and other atoms by sharing of electrons.
d ro g e n w it h
of h y
lements
the p-block e
h ic h h a v e r e latively
w
e le c tr o n e g ativity.
high
HCl, H2O, CH4,
Examples
PH3, NH3 etc.
 Covalent or Molecular Hydrides

1 Electron-deficient hydrides
Volatile

Molecular
hydrides 2 Electron-precise hydrides
Soluble in organic
solvents
3 Electron-rich hydrides
 Covalent or Molecular Hydrides

Electron deficient Electron precise Electron rich

hydrides hydrides hydrides

Have lesser number Have excess of

Have the required
of electrons than electrons which
number of electrons
that required for are present as
to write their
writing the lone pairs around
conventional Lewis
conventional Lewis the central highly
structures.
structure. E.N. atom.

B2H6 and hydrides of CH4 and hydrides of

H2O, NH3, HF
group 13 elements group 14 elements
 Metallic/Interstitial Hydrides

Hydrides formed by many d & f block

elements except the metals of group 7, 8, The inability of metals of groups
& 9. 7, 8, & 9 of the periodic table to
form hydrides is referred to as
hydride gap of d-block.
They are almost always
non-stoichiometric, being deficient in
hydrogen.
Chromium - the only 6th group
metal which form metallic
LaH2.87 , YbH2.55 , TiH1.5-1.8 , ZrH1.3-1.75 , hydrides, (CrH).
VH0.56 , NiH0.6-0.7 , PdH0.6-0.8 etc.
 Metallic/Interstitial Hydrides

Earlier, it was thought that hydrogen occupies

interstices in the metal lattice, producing
distortion without any change in its type.

Recent studies have shown that except

for hydrides of Ni, Pd, Ce, and Ac, others have
different lattice from that of the parent metals.
 Applications

Property of absorption of hydrogen

on transition metals is largely used in
catalytic reduction/hydrogenation reactions.
 Ortho and Para Hydrogen

H2 has
two forms

Ortho hydrogen Para hydrogen

Parallel nuclear
Paired nuclear spins
spins
 Did You Know?

Dihydrogen is used as fuel, as it liberates

large amount of heat on combustion.
 Water

Hydrogen Bond

Shape Bent shape

 Physical Properties of Water

Comparison to
H2S and H2Se.

In comparison to H2S and H2Se, H2O

has high freezing point, high b.p.,
high heat of vapourisation, and high
heat of fusion due to H bonding.
 Ice

t a tm o s p h e ri c p ressure, ice
A
ll is e s in th e h e xagonal
crys ta
low
form, and at very
m p e ra tu re , it c ondenses
te
to cubic form.

Water is denser than ice

Structure of Ice

Hydrogen Bond

Oxygen
Hydrogen
 Chemical Properties of Water

1
H2O (l) + NH3 (aq) ⇌ OH- (aq) + NH4+ (aq)
Amphoteric nature

H2O (l) + H2S (aq) ⇌ H3O+ (aq) + HS - (aq)

H2O (l) + H2O (l) ⇌ H3O+ (aq) + OH- (aq)

 Chemical Properties of Water

2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) Redox reaction

Oxidising
agent

2F2 (g) + 2H2O (l) 4H+ (aq) + 4F– (aq) + O2 (g)

Reducing
agent
 Chemical Properties of Water

3
P4O10 (s) + 6H2O (l) 4H3PO4 (aq)
Hydrolysis reaction

N3– (s) + 3H2O (l) NH3 (g) + 3OH– (aq)

SiCl4 (l) + 2H2O (l) Δ SiO2 (s) + 4HCl (aq)

 Chemical Properties of Water

4
Coordinated Hydrates
a E.g.: [Cr(H2O)6]3+ 3Cl–
water formation

Hydrogen E.g.: [Cu(H2O)4]2+SO42–.H2O

b bonded water in CuSO4.5H2O

Interstitial
c water
E.g.: BaCl2.2H2O
 Hard and Soft Water

Soft water Hard water

Gives lather with Does not give lather

soap easily with soap

Water containing calcium

Water free from soluble
& magnesium in the form
salts of calcium and
magnesium of hydrogen carbonates,
chlorides, and sulphates.

E.g., Distilled water, E.g., Sea water, river water,

rain water tap water
 Causes of Hardness of Water

Presence of bicarbonates, chlorides, and

sulphates of calcium and magnesium.

M2+ (aq) + 2C17H35COONa (aq) (C17H35COO)2M + 2Na+ (aq)

From hard Sodium Metal stearate

water stearate (ppt)
(soap)

Where, M = Ca or Mg
 Softening of Water

Temporary
hardness
Softening
of water
Permanent
hardness
 Hardness of water

Temporary Permanent
hardness hardness

Due to the presence

Due to the presence
of soluble salts of Ca
of soluble bicarbonates
& Mg in the form of
of Ca & Mg.
chlorides and sulphates.
 Removing Temporary Hardness

Softening of Water by Boiling

Boil
Ca(HCO3)2 CaCO3 + CO2 + H2O
Soluble Insoluble

Boil
Mg(HCO3)2 MgCO3 + CO2 + H2O
Soluble Insoluble
 Softening of Water by Clark’s method

Ca(HCO3)2 + Ca(OH)2 (calculated amount) 2CaCO3 + 2H2O

Soluble Lime water Insoluble

Mg(HCO3)2 + 2Ca(OH)2 (calculated amount) 2CaCO3 + MgCO3 + 2H2O

Soluble Lime water Insoluble Insoluble
 Removal of Permanent Hardness

a Addition of washing soda

MCl2 + Na2CO3 MCO3 + 2NaCl

ppt

MSO4 + Na2CO3 MCO3 + Na2SO4

ppt

M = Ca, Mg
 Removal of Permanent Hardness

Hydrated sodium
aluminium silicate,
NaAlSiO4 (NaZ)
Also called zeolite/
b Ion-exchange method permutit method.

2NaZ (s) + M2+ (aq) MZ2 (s) + 2Na+ (aq) M2+ = Ca2+/Mg2+

Exhausted zeolite is regenerated

by treating with NaCl (aq)

MZ2 (s) + 2NaCl (aq) 2NaZ (s) + MCl2 (aq)

 Removal of Permanent Hardness

c Calgon’s method

Calgon ( Na6P6O18 or Na2[Na4(PO3)6] ) forms

soluble complexes with Mg2+ and Ca2+ ions.

Na6P6O18 2Na+ + Na4P6O182-

M2+ + Na4P6O182- [Na2MP6O18]2- + 2Na+

M = Mg, Ca
 Removal of Permanent Hardness

Reactions with cation exchange resin,

d Synthetic resin method
RSO3H + NaCl RSO3Na + HCl

Involves the use of

cation/anion
2RNa (s) + M2+ (aq) R2M (s) + 2Na+ (aq)
exchange resin for the
softening of water.
M2+ = Ca2+/Mg2+
 Removal of Permanent Hardness

Pure de-mineralised water A cation exchange (in

(free from all soluble mineral salts) the H+ form) and an anion
is obtained by passing water exchange (in the OH- form)
successively through

2RH (s) + M2+ (aq) MR2 (s) + 2H+ (aq)

 Removal of Permanent Hardness

In anion exchange process, OH– exchanges

anions like Cl–, HCO3–, SO42–, etc.

RNH2 (s) + H2O (l) ⇌ RNH3+.OH– (s)

RNH3+ .OH– (s) + X– (aq) ⇌ RNH3+ X– (s) + OH– (aq)

H+ (aq) + OH– (aq) H2O (l)

 Measurement of Hardness

Hardness is measured in terms of ppm (parts

per million) of CaCO3 or equivalent to it.

Hardness Mass of CaCO3

(in ppm) = Total mass of solution
✕ 106
Properties of D2O

Colourless, tasteless,
& odourless liquid
Values of all physical
constants are higher
than that of H2O
Chemically, it is similar
to H2O
It’s chemical
reactions are slower
than those of H2O
Uses of Heavy Water

Moderator in nuclear reactors

Used in exchange reactions for the

study of the reaction mechanism

For the preparation of other

deuterium compounds
Preparation of Deuterium Compounds

CaC2 + 2D2O C2D2 + Ca(OD)2

SO3 + D2O D2SO4

Al4C3 + 12D2O 3CD4 + 4Al(OD)3

 Hydrogen Peroxide (H2O2)

Non-linear, Open book -O-O- linkage is called

non-planar structure peroxy linkage

98.8 pm 145.8 pm 95.0 pm 147.5 pm

90.2° 111.5°

101.9° 94.8°

Solid phase Gas phase

 Preparation of H2O2
2 2

Acidifying barium peroxide and removing excess of water

by evaporation under reduced pressure gives H2O2.

BaO2.8H2O + H2SO4 BaSO4 + H2O2 + 8H2O

Cold ppt.

Air
O2
+ H2O2
H2
Reduction
2-Ethyl anthraquinol (Ni) 2-Ethyl anthraquinone
 Preparation of H2O2

Prepared by the electrolysis of 50% H2SO4

solution at 0°C using inert electrodes.

Cathode Platinum

Anode Graphite

-
H2SO4 ⇌ H+ + HSO4
 Preparation of H2O2

At anode: 2HSO4
- S2O82- + 2H+ + 2e-

1
At cathode: H+ + e- H2
2

80-90°C
H2S2O8 + H2O 2H2SO4 + H2O2
distillation

BaCl2

BaSO4 + H2O2 (aq)

 Physical Properties of H2O2

Colourless viscous liquid which

01 appears blue in larger quantities.

02 Miscible with water in all proportions.

b.p. (144°C) & density are more than that of

03 water and F.P. (–4°C) is less than that of water.
Volume Strength of H2O2

Strength of H2O2 is represented

as 10 V, 20 V, 30 V, etc.

20 V H2O2 means one litre of this

sample of H2O2 on decomposition
gives 20 L of O2 gas at STP.
 Chemical Properties

1 Oxidising action
in acidic medium

2Fe2+ (aq) + 2H+ (aq) + H2O2 (aq) 2Fe3+ (aq) + 2H2O (l)

PbS (s) + 4H2O2 (aq) PbSO4 (s) + 4H20 (l)

2Fe2+ + H2O2 2Fe3+ + 2OH–

2 Oxidising action
in basic medium
Mn2+ + H2O2 Mn4+ + 2OH–
 Chemical Properties

Reducing action
3 in acidic medium

2MnO4- + 6H+ + 5H2O2 2Mn2+ + 8H2O + 5O2

HOCl + H2O2 H3O+ + Cl– + O2

 Chemical Properties

Reducing action
4 in basic medium

I2 + H2O2 + 2OH– 2I– + 2H2O + O2

–
2MnO4 + 3H2O2 2MnO2 + 3O2 + 2H2O + 2OH–
 Storage of H2O2

H2O2 decomposes slowly on exposure to light

2H2O2 (l) 2H2O (l) + O2 (g)

Decomposition of H2O2 is catalysed in the presence

of metal surfaces or traces of metal ions.

Stored in wax-lined glass or plastic vessels in dark.

Urea can be added as a stabiliser.
 Antiseptic

Pollution Hair bleach &

control mild disinfectant

Uses of
Hydrogen
Peroxide
Manufacture Synthesis of
chemicals like hydroquinone,
sodium tartaric acid
perborate
Bleaching agent