HYDROGEN

&
ITS COMPOUNDS
 Hydrogen
❖ Atomic number =1

❖ Electronic configuration= 1s1

❖ First element in the periodic table.

❖ Most abundant element in the universe(70% by mass).

❖ Ionization Energy = 1312 KJ/mole

❖ Non-metal

❖ Electronegativity is 2.1

❖ Naturally occurring Hydrogen has 3 isotopes.

1 2 3
1H 1D 1T

NOTE: Tritium is radioactive and decays by 𝛽 emission (t1/2=12.33 years)

The 𝛽 emission is stopped by 0.6cm of air, so no shielding is required.
3 3 0
1T 2He + -1e
Q. [NEET 2021]
Comparison between H, D and T
 Position of Hydrogen in the Periodic table

Resemblance with

Alkali Metals Halogens

❖ Hydrogen has only one electron in its valence ❖ Hydrogen easily accepts one electron to
shell so that it can loose one electron easily and achieve noble gas configuration of He.
shows +1 oxidation state similar to alkali metals. ❖ Its IE is also very high 1312KJ/mole hence it
resembles more to halogens and does not
❖ However size of H+(proton) is extremely small, it posses metallic character.
has therefore very high polarizing power and (IE of Li = 520KJ/mole; IE of F=1680KJ/mole)
distorts the electron cloud on the other atoms.
Thus protons are always associated with other ❖ However it is less reactive than Halogens
atoms or molecules. For example in aqueous
solution HCl or H2SO4 exist as H3O+, and free
protons do not exist under normal conditions.

Conclusion : it is unique in behaviour and is, therefore, best placed separately in the periodic table.
 Molecular Hydrogen/ Dihydrogen (H2)

ORTHO HYDROGEN PARA HYDROGEN

❖ Both nuclei has same spin ❖ Both nuclei has opposite spin

❖ Total nuclear spin = ½ + ½ = 1 ❖ Total nuclear spin = ½ - ½ = 0

❖ More internal energy ❖ Less internal energy

At absolute zero, the gas contains 100% para form. But when the temperature is raised, some para form
changes to ortho form. At room temperature the gas contains about 75% ortho form and 25% para form.
 Preparation of Dihydrogen
[A] Laboratory Methods

1. By reaction of metals with dilute acids

METAL + dil. H+ H2(g)

For example, by the reaction of granulated Zinc with dilute HCl, H2 gas is liberated

Zn + 2HCl ZnCl2 + H2

NOTE : Metal should be above Hydrogen in the electrochemical series. Also

acid should be dilute, because at higher concentrations acids may behave as
oxidizing acids. For example,
Zn + dil.H2SO4 ZnSO4 + H2
Zn + conc.H2SO4 ZnSO4 + SO2 + H2O
2. By reaction of metals with aqueous alkali
Be

Al
NaOH/KOH

Ga

Sn

Pb

Zn
Q) Which of the following will give H2 gas with both
acids as well as base?

1. Zn

2. Al

3. Sn

4. Fe

5. Cu

6. Na

7. Mg
3. By reaction of Salt-Like Hydrides with water

H- + H2O OH- + H2
2. By Electrolysis of water

1
Anode: OH- H2O + O2 + 2e-
2

Cathode: 2H2O + 2e- 2OH- + H2

1
Overall: H2O H2 + O2
2

❖ Water does not conduct electricity very well, so it is usual to electrolyse aqueous solutions of NaOH
or KOH in a cell with Nickel anodes and iron cathodes.

❖ High purity (>99.95%) dihydrogen is obtained by electrolysing warm aqueous barium hydroxide
solution between nickel electrodes.

❖ Electrolysis of acidified water using platinum electrodes also gives hydrogen.

electrolysis 1
H2O H2 + O2
Trace acid 2
[A] Commercial Methods

1. By Bosch process
❖ In this process superheated steam is passed over red-hot coke
/hydrocarbons/wood/newspaper/sewage in presence of catalyst to obtain ‘synthetic gas’.
1000oC
C(s) + H2O(g) CO(g) + H2(g) (Coal gasification reaction)
1000oC
CnH(2n+2)(s) + nH2O(g) nCO(g) + (2n+1)H2(g)
Ni

❖ The mixture of CO and H2 is known as water gas/synthetic gas/syn gas because this gas is used to
prepare methanol and a number of hydrocarbons. This gas is also used as fuel in industries.
❖ CO and H2 can be removed by two methods: Carl Bosch

1. By liquefication and then fractional distillation

2. By water-gas shift reaction: In this process syn gas is mixed with steam, cooled to 400oC and then
passed over iron chromate catalyst. CO gets oxidized to CO2 which is removed by dissolving in water
under pressure, or reacting with K2CO3 solution giving KHCO3
3. As a byproduct in the manufacture of NaOH

Sodium Hydroxide and Chlorine gas are manufactured from the chlor-alkali
industry in which aq. NaCl is electrolysed to produce NaOH, Cl2 and H2.

Anode: 2Cl-(aq) Cl2(g) + 2e-

Cathode: 2H2O + 2e- 2OH-(aq) + H2(g)

Overall: 2Na+(aq) + 2Cl-(aq) + 2H2O Cl2(g) + H2(g) + 2Na+(aq) + 2OH-(aq)

This cell will be discussed later in detail in manufacturing of caustic soda (s-block)
NOTE:
In oil refineries, natural hydrocarbon mixtures of high molecular mass such as naphtha and fuel oil are ‘cracked’ to
produce lower molecular weight hydrocarbons which can be used as petrol. Hydrogen is a valuable by-product.

Presently ~77% of the industrial dihydrogen is produced from Petro-chemicals, 18% from coal, 4% from electrolysis
of aqueous solutions and 1% from other sources.
 Physical Properties of dihydrogen

Dihydrogen is a :

1. Colourless gas
2. Odourless gas
3. tasteless gas
4. combustible gas
5. It is lighter than air and
6. insoluble in water.
 Chemical Properties of dihydrogen

Due to 1s-1s overlapping bond energy of H2 is high Bond energy.

It is because of this factor that the dissociation of dihydrogen into its atoms is only ~0.081% around
2000K which increases to 95.5% at 5000K. Also, it is relatively inert at room temperature due to the
high H–H bond enthalpy.
Electric arc
H2 2H

This property is used for welding.

1. Reaction with Halogens

H2(g) + X2(g) 2HX(g)

It reacts with halogens, X2 to give hydrogen halides

The reaction with fluorine occurs even in the dark, with iodine it requires a catalyst
2. Reaction with Dioxygen

It reacts with dioxygen to form water. The reaction is highly exothermic.

2H2(g) + O2(g) 2H2O(l) + ∆H=-285.9KJ/mole

3. Reaction with dinitrogen (Haber’s process)

673K,200atm
3H2(g) + N2(g) 2NH3(g) + ∆H=-92.6KJ/mole
catalyst

This method is used for commercial preparation of NH3.

The process is reversible, and required conditions are low temperature(since process is exothermic)
and high pressure(since volume decreasing) .
But at very low temperature rate of reaction becomes slow.
Catalyst: 1. Fe powder with Mo as promoter (old)
2. Fe2O3 + Al2O3/K2O (recent)
4. Reaction with Metals
With many metals it combines at a high temperature to yield the corresponding hydrides

∆
H2 + 2M 2MH
 5. As a reducing agent
It reduces some metal ions in aqueous solution and oxides of metals (less active than iron) into
corresponding metals.

H2 + Pd2+(aq)

H2 + Cu2+(aq)

It reduces alkenes and alkynes into corresponding alkanes

Pt
H2C CH2 + 2H2 H3C CH3

Pt
HC CH + 3H2 H3C CH3

Hydrogenation of vegetable oils using

nickel as catalyst gives edible fats
(margarine and vanaspati ghee)
6. Hydroformylation reaction

R CH CH2 + H2 + CO R-CH2CH2CHO

R-CH2CH2CHO + H2 R-CH2CH2CH2OH
 Uses of Dihydrogen
1. The largest single use of dihydrogen is in the synthesis of ammonia which is used in
the manufacture of nitric acid and nitrogenous fertilizers.

2. Dihydrogen is used in the manufacture of vanaspati fat by the hydrogenation of

polyunsaturated vegetable oils like soyabean, cotton seeds etc.

3. It is used in the manufacture of bulk organic chemicals, particularly methanol.

Co catalyst
CO(g) + H2(g) CH3OH(l)

4. It is widely used for the manufacture of metal hydrides

5. It is used for the preparation of hydrogen chloride, a highly useful chemical.

6. In metallurgical processes, it is used to reduce heavy metal oxides to metals.

7. Atomic hydrogen and oxy-hydrogen torches find use for cutting and welding
purposes. Atomic hydrogen atoms (produced by dissociation of dihydrogen with
the help of an electric arc) are allowed to recombine on the surface to be
welded to generate the temperature of 4000 K.
8. It is used as a rocket fuel in space research.
9. Dihydrogen is used in fuel cells for generating electrical energy. It has many
advantages over the conventional fossil fuels and electric power. It does not
produce any pollution and releases greater energy per unit mass of fuel in
comparison to gasoline and other fuels.
 Hydrides
Binary compounds of Hydrogen are known as hydrides. These are of three types.
1. Ionic hydrides/salt-like hydrides
2. Covalent hydrides/Molecular hydrides
3. Metallic/interstitial hydrides

1. Ionic or salt-like hydrides

These type of hydrides are formed by the metal of s-block and electropositive metals.
These compounds have high melting and boiling points. When these metals are heated with H2
ionic hydrides are formed.
∆
M + H2 MH

These are ionic in nature which can be proved by following evidence.

1. Their melts conducts electricity which confirm the presence of ions.
2. H2 is liberated at the anode, thus confirming the presence of H- ion.
3. On hydrolysis these salts produces H2 gas
Due to high polarization BeH2, MgH2 and AlH3 are covalent in nature

LiH has also significant covalent character but it is largely ionic in nature. So the
other alkali metal hydrides must be ionic in nature

LiH + H2O
LiH + AlCl3
LiH + BH3
2. Covalent or Molecular hydrides

❖ Hydrides of p-block elements are covalent in nature since there is small difference in
electronegativity between the atom and hydrogen. Examples are CH4, NH3, H2O, HF, H2S, PH3 , BH3
etc.
❖ These are of three types:
1. Electron-deficient Hydrides : those hydrides in which central atom has incomplete octet in its
valence shell. These behave as Lewis acids. Examples : BH3 , AlH3 , BeH2 etc.

2. Electron-precise Hydrides : Electron-precise compounds have the required number of electrons to

write their conventional Lewis structures. In other words, these hydrides have complete octet and no
lone pairs on central atom. Examples : CH4, SiH4 , GeH4 etc.

3. Electron-rich Hydrides : Electron-rich hydrides have excess electrons which are present as lone pairs.
In other words, these hydrides have complete octet and lone pairs on central atom. Examples : NH3,
H2O , HF etc. These hydrides can behave as lewis
2. Metallic or interstitial hydrides.

❖ These hydrides are mainly formed by d and f block elements.

❖ However elements of group 6 to 9 (except Cr) do not form
these hydrides, and this part of the periodic table is known as
hydrogen gap.
❖ they are almost always nonstoichiometric for example, LaH2.87,
YbH2.55, TiH1.5–1.8, ZrH1.3–1.75, VH0.56, NiH0.6–0.7, PdH0.6–0.8 etc.
❖ Earlier it was thought that in these hydrides, hydrogen fill the
interstitial spaces of the lattice and therefore called as
interstitial hydrides.
❖ These hydrides may be regarded as solid solutions of metal and
hydrogen.
❖ Metals which can dissolve varying amount of hydrogen in this
way can act as catalyst for hydrogenation reaction, like Pt and
Pd. So these have strong reducing properties.

H2
TiCl4 + Mg/Na Ti(s) TiHn(s)
High pressure

❖ These hydrides are brittle, less dense than parent metals and
theses hydrides are heated they decompose, giving hydrogen
and metal.
WATER (H2O)

Structure and Bonding

Why ice floats on water?
CHEMICAL PROPERTIES OF WATER

1. Amphoteric nature
NEET 2019

Q) Conjugate base for Bronsted acids H2O and HF are :

(1) H3O+ and F–, respectively

(2) OH– and F–, respectively
(3) H3O+ and H2F+, respectively
(4) OH– and H2F+, respectively
2. Redox reactions

H2O can behave as both oxidizing as well as reducing agent.

3. Hydrolysis reaction

Those nucleophilic substitution reactions in which water behaves as nucleophile are

known as hydrolysis reactions.

PCl5 + H2O CO2 + H2O

PCl3 + H2O B2O3 + H2O

SF4 + H2O Cl2O7 + H2O

SF6 + H2O Cl2O5 + H2O

Cl2O3 + H2O
SiCl4 + H2O
Cl2O + H2O
BCl3 + H2O N2O3 + H2O
P4O10 + H2O N2O5 + H2O
P4O6 + H2O N2O4 + H2O
SO2 + H2O N3- + H2O
SO3 + H2O P3- + H2O
4. Hydrate formation

From aqueous solutions many salts can be crystallised as hydrated salts. Such an association of water is of
different types viz.

(i) coordinated water

Cr3+ + 6H2O [Cr(H2O)6]3+

Fe3+ + 6H2O [Fe(H2O)6]3+

(ii) interstitial water

here water is present in the interstitial spaces of ionic solids like BaCl2.2H2O

(iii) hydrogen-bonded water

Here water is present with H-bond
Examples: Blue vitriol (CuSO4.5H2O) , green
vitriol (FeSO4.7H2O
TYPES OF WATER

There are two types of water

1. Soft water: this type of water produces foam/lather with soap.
2. Hard water: this type of water does not give any foam/lather with soap.

Soap contains fatty acids like sodium stearate (C17H35COONa), which reacts
with water to form foam. Hard water contains impurities of Ca2+ and Mg2+
salts which reacts with fatty acids to form precipitate/scum of
(C17H35COO)2Ca and (C17H35COO)2Mg
The hardness of water is of two types:
1. Temporary hardness
Temporary hardness is due to the presence of magnesium and calcium hydrogencarbonates. It
can be removed by :
(i) Boiling
∆
Ca(HCO3)2 CaCO3 + CO2
White ppt.
∆
Mg(HCO3)2 Mg(OH)2 + CO2
White ppt.
(ii) Clarke’s Method
In this method calculated amount of lime is added to hard water. It precipitates out calcium carbonate
and magnesium hydroxide which can be filtered off.

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

White ppt.

Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O

White ppt. White ppt.

2. Permanent Hardness
It is due to the presence of soluble salts of magnesium and calcium in the form of chlorides and
sulphates in water. It is removed by:
(i) Treatment with washing soda (sodium carbonate):
Washing soda reacts with soluble calcium and magnesium chlorides and sulphates in hard water
to form insoluble carbonates.

Mg2+/Ca2+(aq) + Na2CO3 MgCO3/CaCO3 + 2Na+(aq)

White ppt.
(ii) Calgon’s method:
Sodium hexametaphosphate (Na6P6O18), commercially called ‘calgon’, when added to hard water,
the following reactions take place

Na6P6O18 2Na+ + Na4P6O182-

Ca2+/Mg2+ + Na4P6O182- [Na2CaP6O18]2-/ [Na2MgP6O18]2- + 2Na+

The complex ion of Mg2+ and Ca2+ remains in the solution.

Sodium hexametaphosphate (Na6P6O18)

(iii) Ion-exchange method: This method is also called zeolite/permutit process. Hydrated sodium
aluminium silicate is zeolite/permutit. For the sake of simplicity, sodium aluminium silicate
(NaAlSiO4) can be written as NaZ. When this is added in hard water, exchange reactions takes
place.

2NaZ + M2+ 2Na+ + MZ2 M = Mg2+ , Ca2+

Permutit/zeolite is said to be exhausted when all the sodium in it is used up. It is

regenerated for further use by treating with an aqueous sodium chloride solution.
(iv) Synthetic resins method:

Cation exchangers Anion exchangers

NEET 2019
The method used to remove temporary hardness of water is :

(1) Clark's method

(2) Ion-exchange method
(3) Synthetic resins method
(4) Calgon's method
HYDROGEN PEROXIDE (H2O2)

❖ Hybridization: ❖ Polar and non-planer compound

❖ Structure: ❖ It can form Hydrogen bonds
❖ Restricted rotation between O-O bonds
❖ Oxidation state = -1 (on oxygen)
METHOD OF PREPARATION OF HYDROGEN PEROXIDE

1. By acidification of peroxides
Acidifying barium peroxide and removing excess water by evaporation under reduced pressure gives
hydrogen peroxide.

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

2. By electrolysis of H2SO4
3. By auto-oxidation of 2-alkylanthraquinols

OH O

CH3 O2 (air) CH3

+ H2O2
H2 / Pd
OH O

2-ethylanthraquinol 2-ethylanthraquinone

Industrially H2O2 is prepared by the auto-oxidation of 2-alklylanthraquinols.

In this case 1% H2O2 is formed. It is extracted with water and concentrated to ~30% (by mass) by distillation
under reduced pressure. It can be further concentrated to ~85% by careful distillation under low pressure.
The remaining water can be frozen out to obtain pure H2O2.
CHEMICAL PROPERTIES OF HYDROGEN PEROXIDE
It acts as an oxidising as well as reducing agent in both acidic and alkaline media.

2H2O2 2H2O + O2

1. Oxidising action in acidic medium 2. Oxidising action in basic medium

H+
H2O2 + Fe2+ H2O + Fe3+ H2O2 + Fe2+ Fe3+ + OH-

H+
H2O2 + PbS H2O + PbSO4 H2O2 + Mn2+ Mn4+ + OH-
3. Reducing action in acidic medium 4. Reducing action in basic medium

H+ OH-
H2O2 + MnO4- H2O + Mn2+ + O2 H2O2 + MnO4- H2O + MnO2 + O2

OH-
H2O2 + HOCl HCl + H2O + O2 H2O2 + I2 I- + H2O + O2

Storage
H2O2 decomposes slowly on exposure to light

2H2O2 2H2O + O2

In the presence of metal surfaces or traces of alkali (present in glass containers), the above reaction is catalysed. It is,
therefore, stored in wax-lined glass or plastic vessels in dark. Urea can be added as a stabiliser. It is kept away from dust
because dust can induce explosive decomposition of the compound.
HEAVY WATER (D2O)

It is prepared by exhaustive electrolysis of water.

❖ H2O dissociates to about 3 times the extent of D2O. Hence D2O has more bond energy.
❖ O-H bonds are broken more easily (about 18 times) thus when it is electrolysed H2 is
liberated much faster than D2.
❖ About 29000 liters of water must be electrolysed to give 1L of D2O
CHEMICAL PROPERTIES OF HYDROGEN PEROXIDE

Its chemical properties are similar to that of H2O

SO3 + D2O

N2O5 + D2O

CaC2 + D2O

Al4C3 + D2O
Match the following and identify the correct option. NEET 2020

(a) CO(g) + H2(g) (i) Mg(HCO3)2 + Ca(HCO3)2

(b) Temporary hardness of water (ii) An electron deficient hydride

(c) B2H6 (iii)Synthesis gas

(d) H2O2 (iv) Non-planar structure

(a) (b) (c) (d)

(1) (iii) (iv) (ii) (i)
(2) (i) (iii) (ii) (iv)
(3) (iii) (i) (ii) (iv)
(4) (iii) (ii) (i) (iv)