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C-09:- HYDROGEN

HYDROGEN ii. Electrolysis of water

1. Hydrogen is the most abundant element in the universe and electrolysis
2H2 O(𝑙) → 2H2 (g) + O2 (g)
the third most abundant on the surface of globe. It mainly Hydrogen is evolved at cathode having high purity. But
occurs in combined state. It is the 1st element in the periodic
method is expansive.
table. It was discovered by Henry Cavendish in 1766 and
iii. Lane’s process : (used for large scale production)
prepared the gas by treating iron with dil. H2 SO4 . Its name
3Fe + 4H2 O (steam) → Fe3 O4 + 4H2
was given by Lavoisier because it produces water.
iv. Industrial preparation of hydrogen: Bosch process:
2. Both H + and H − are stable in gaseous state. In this method water gas is mixes with steam and passed over
3. Electronic configuration of H + is 1𝑠 0 while that of H − is 1𝑠 2 . heated catalytic mixture of Fe2 O3 and Cr2 O3 at 773 K when
4. Hydride ion (H − ) cannot exist in aqueous medium, while H + CO2 and H2 are obtained. The mixture is compressed to 25
can exist in aqueous solution as H3 O+ . atmosphere pressure and passed into water, CO2 dissolve
5. Hydrogen is called a rogue element as it can be placed in 1𝑠𝑡 while H2 is set free.
group with alkali metal and in 17th group with halogens. 1270K
Red Alert C + H2 O →
6. DIHYDROGEN (𝐇𝟐 ) Water gas(Syn gas)
773 K
A. Preparation H2 + CO + H2 O CO2 + 2H2 .
Fe2 O3/ Cr2 O3
i. Laboratory method for preparation of hydrogen: In the The process of producing syn gas from coal or coke is called
laboratory hydrogen is prepared by the action of dil. H2 SO4 coal gasification and production of hydrogen gas from water
on granulated zinc. gas is called water gas shift reaction.
Pure zinc metal is not used because it reacts very slowly with B. Properties of dihydrogen
dil. H2 SO4 . The presence of impurities, however, increases i. 1L of H2 at N.T.P. weights 0.0899 g and its density is equal
the rate of reaction due to the formation of to 1/14 in that of air.
Electrochemical couples. ii. a) I.E. of hydrogen = 13.54 eV
Zn + H2 SO4 (dil. ) → ZnSO4 + 2 H2 b) E.A of hydrogen = 173 kcal/mol
Also, conc. H2 SO4 is not used for the preparation of c) Electronegativity of hydrogen = 2.1
dihydrogen because Zn form SO2 gas instead of H2 gas.
Zn + H2 SO4 (Conc. ) → ZnSO4 + SO2 + 2H2 O

Sr.No. Isotopes of hydrogen Protium (H) Deuterium (D) Tritium (T)

1 2 3
1. Symbol 1H or H 1H or D 1H or T
2. Atomic number 1 1 1
3. Mass number 1 2 3
4. Relative atomic mass 1.007825 2.014102 3.016049
5. Relative abundance 99.985% 0.0156% 10−15
6. Nuclear spin quantum number ½ 1 1/2
7. Radioactive nature Stable Stable Radioactive
3 3 0 (β-particle)
1H →2He +-1e
8. Half life --- --- 12.33 years
9. No. of neutrons 0 1 2
vii. Moist hydrogen gas is not dried by passing through conc.
iii. Hydrogen is the least denser gas known and least denser H2 SO4 as it may catch fire. So, P2 O5 may be used as a drying
liquid. agent for hydrogen gas.
iv. Metals which are more electropositive than hydrogen 7. NASCENT AND ATOMIC HYDROGEN
produce hydrogen gas on reaction with alkali or acid. A. Nascent hydrogen is the hydrogen at the moment of its
v. Isotopic effect. The difference in properties arising from the generation in a chemical reaction. It consists of atoms of
difference in mass is called isotopic effect. It is maximum for hydrogen and hence has more energy and so it is more
hydrogen because the percentage change in mass is maximum reactive and is a stronger reducing agent than ordinary
for isotopes of hydrogen. hydrogen.
vi. Hydrogen is inflammable, a mixture of 85% He and 15% H2
is used in the filling of aeroships and balloons.
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B. At high temperature (about 30000C) and low pressure
molecules of hydrogen dissociate to form atoms of hydrogen
known as atomic hydrogen.
C. Nascent hydrogen can be produced even at room
temperature but atomic hydrogen is produced at elevated
temperature.
D. Nascent hydrogen can never be isolated but atomic
hydrogen can be isolate.
E. Reducing power of atomic hydrogen is much greater than
that of nascent hydrogen.
Red Alert
8. ORTHO AND PARA HYDROGEN:
These two isomers have 1 and 0 nuclear spin respectively.
The conversion of one isomer into another isomer is a slow
process. Ordinary dihydrogen is an equilibrium mixture of
ortho and para hydrogen.
Ortho hydrogen ⇌ para hydrogen
The amount of ortho and para hydrogen varies with
temperature as:
i. At 20 K hydrogen contains mainly para hydrogen which is
more stable.
ii. At the temperature of liquefaction of air, the ration of ortho
and para hydrogen is 1:1.
iii. At the room temperature, the ratio of ortho to para
hydrogen is 3:1.
iv. Even at very high temperature, the ratio of ortho to para
hydrogen can never be more than 3:1.
Note
Thus, it has been possible to get pure para hydrogen by
cooling ordinary hydrogen gas to a very low temperature
(close to 20 K) but it is never possible to get a sample of
hydrogen containing more than 75% of ortho hydrogen. The
physical properties of dihydrogen are not affected
significantly by nuclear spin. However, some notable
differences:
i. The thermal conductivity of para – hydrogen is about 50%
greater than that of ortho – hydrigeb.
ii. The melting point of para hydrogen is 0.15 K below that of
hydrogen containing 75% ortho hydrogen.
Check Your Grasp
1. The nuclei of tritium (1H3) atom would contain neutrons
A. 1 B. 2
C. 3 D. 4
2. The lightest element among the following is
A. He B. Cs
C. H D. 1
Red Alert
9. HYDRIDES
Dihydrogen, under certain reaction conditions, combines with
almost all elements, except noble gases, to form binary
compounds, called hydrides.
The hydrides are of three types:
A. Ionic or Saline hydrides
These are stoichiometric compounds of dihydrogen formed
with most of the 𝑠-block elements which are highly
electropositive in character. The ionic hydrides are crystalline,
non-volatile and non-conducting in solid state. However, they
conduct electricity and on electrolysis liberate dihydrogen gas
at anode, which confirms the existence of H − ion.
anode
2H(melt) → H2 (g) + 2e
Saline hydrides react violently with water, producing
dihydrogen gas.
NaH (𝑠) + H2 O (𝑎𝑞) → NaOH (aq) + H2 (g)
Lithium hydride is rather unreactive at moderate temperature
with O2 or C𝑙2 . It is, therefore used in the synthesis of other
useful hydrides e.g.
8 LiH + A𝑙2 C𝑙6 → 2LiA 𝑙H4 + 6LiC𝑙
2LiH + B2 H6 → 2LiBH4
Note
CaH2 is called hydrolith.
B. Covalent or molecular hydride
Dihydrogen forms molecular compounds with most of the 𝑝-
block elements. Most familiar examples are CH4 , NH3 , H2 O
and HF. Hydrogen compounds of non-metals have been
considered as hydrides. Being covalent, they are volatile
compounds.
Molecular hydrides are further classified into three types
according to the relative numbers of electrons and bonds in
their Lewis structure.
i. Electron – deficient: An electron-deficient hydride have
deficient for few electrons for writing its conventional Lewis
structure. All elements of group 13 will form electron –
deficient compounds. They act as Lewis acids i.e., electron
acceptors.
ii. Electron-precise: Electron-precise hydrides have the require
number of electrons to write their conventional Lewis
structures. All elements of group 14 form such compounds
(e.g., CH4 ).
iii. Electron-rich hydrides : Electron-rich hydrides have excess
electrons which are present as Ione pairs. Elements of group
15-17 form such compounds. (NH3 has 1-Ione pair, H2 O -2
and HF -3 Ione pairs). They will behave as Lewis bases i.e.,
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electron donors. The presence of Ione pairs on highly
electronegative atoms like N, O and F in hydrides results in
hydrogen bond formation between the molecules. This leads
to the association of molecules.
C. Metallic or Non-stoichiometric (or interstitial) Hydrides
These are formed by many d-block and f-block elements. The
metals of group 7,8 and 9 do not form hydride. This is known
as hydride gap. Even from group 6, only chromium forms
CrH. These hydrides conduct heat and electricity though not
as efficiently as their parent metals do. They are always non
stoichiometric, being deficient in hydrogen. For example,
LaH2.87, YbH2.55 , TiH1.5−1.8 , ZrH1.3−1.75 hydrides. The law of
constant composition does not hold good.
The property of absorption of hydrogen on transition metals is
widely used in catalytic reduction/ hydrogenation reactions
for the preparation of large number of compounds. Some of
the metals (e.g. Pd, Pt) can accommodate a very large volume
of hydrogen and therefore, can be used as its storage media.
This property has high potential for hydrogen storage and as a
source of energy.
Note
Phosphorus does not form PH5 although have +5 oxidation
state because enthalpy of atomization of hydrogen is very
high. Also electron gain enthalpy value of hydrogen do not
favour the higher oxidation state of phosphorous.
i. Metals like Pd. Pt, Au, Ni etc. have the property of absorbing
large quantity of hydrogen at normal or higher temperature.
This phenomenon is known as occlusion of hydrogen. The
occlusion property of these metals is in order. Colloidal
palladium > Palladium> Platinum> Gold> Nickel.
ii. Hydrogen acts both as oxidising and reducing agent since it
can form both cations H + (by loss of electron) and anion H −
(by gain of electron).
Check Your Grasp
3. The absorption of hydrogen by metals is called
A. dehydrogenation B. hydrogenation
C. occlusion D. absorption
4. Which of the following produces hydrolith with
dihydrogen?
A. Mg B. Al
C. Cu D. Ca
WATER (𝐇𝟐 𝐎)
1. In nature water exists in all the three phases i.e. solid (ice),
liquid (water) and gas (steam or water vapours).
2. In water molecule, oxygen is 𝑠𝑝3 - hybridised and contains
two Ione pair of electrons due to which water has bent
structure with HOH bond angel of 104.50 .
3. The dipole moment of water is 1.84 D.
4. Water has maximum density at 277 K (40 C).
5. Rain water is purest form of water.
6. Pure water is not a good conductor so it is made conductor by
adding small amount of acid or alkali.
7. Water is known as universal solvent due to its high dielectric
constant i.e.82.
8. Ice floats on water. Due to its cage like structure in which
there are empty spaces and hence greater volume. So the
density of ice is lower than water. Also, water has maximum
density at 40 C because when ice melts fill the empty spaces
first and volume decreases.
9. Amphoteric nature:
H2 O ⇌ H3 O+ + OH −
K w = 1.0 × 10−14 mol2 /L2 at 298 K
Red Alert
10. HARD AND SOFT WATER
A. Water that produces lather with soap readily is called soft
water. For example, rain water, distilled water and
demineralised water.
Water which does not produce lather with soap readily is called
hard water. For example: sea water, river water, spring water,
lake water and well water.
B. Hardness of water is due to the presence of bicarbonates,
chlorides and sulphates of Ca and Mg in it.
C. The Ca2+ and Mg 2+ ions react with the anions of fatty acids
(stearic, palmitic, oleic acids etc.) present in soaps to form curdy
white precipitates. As a result hard water does not produce
lather with soap immediately.
2C17 H35 COO− Na+ + CaCl2 → (C17 H35 COO)2 Ca ↓ +2NaC𝑙
Sod. Stearate Cal.stearate
(Soap) (Curdy white ppt.)
TRICK
i. Temporary hardness is due to the presence of bicarbonates of
calcium and magnesium.
ii Permanent hardness is due to the present of soluble chlorides
and sulphates of calcium and magnesium.
Red Alert
D. Removal of hardness of water
i. Ions exchange method: This is the most modern method for
softening of hard water. Here Ca2+ and Mg 2+ ions present in
hard water are exchanged by those ions present in ion
exchangers which are mainly of two types: Zeolite (naturally
occurring) and permutit (synthetic).
represented by the general formula Na 2 Z where Z=
A𝑙2 Si2 O8 . 𝑥H2 O is called inorganic ion exchanger.
ii. Cation exchange resins : These consists of giant
hydrocarbon frame work (R) attached to acidic groups such as
– COOH (carboxylic) or −SO2 OH (sulphonic acid) groups and
are represented by the general formula R − COOH or
R − SO2 OH. Since the H + ions of the acidic groups are
exchanged with Ca2+ and Mg 2+ ions present in hard water,
water becomes free from cations by treatment with cation
exchangers.
ii. Anion exchange resins: These resins contain basic group
such as OH − (hydroxide) ions usually in the form of substituted
ammonium hydroxides attached to giant hydrocarbon frame
work (R). These may be represented by the general formula
R −+NH3 OH − . Since these resins can exchange OH − ions with
anions such as C𝑙 − and SO2− 4 ions present in hard water, water
becomes free from anions by treatment with anion exchangers.
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iv. The formula of calgon is Na 2 [Na 4(PO3 )6 ] or (NaPO3 )x it is This method is not used widely as H2 O2 perpared contains
commonly called sodium hexa metaphosphate. some heavy Ba2+ ions. These catalysed the decomposition of
E. Degree of hardness H2 O2 . To prevent this H2 SO4 is replaced by H3 PO4 and Ba 3
The amount of hardness causing substance present in a certain (PO4 )2 gets completely precipitated.
volume of water measures the extent of hardness in terms of 3 BaO3 . 8H2 O + 3H3 PO4 → Ba 3 (PO4 )2 + 24H2 O + 3H2 O2
calcium carbonate although this is never responsible for (ppt)
causing hardness of water because of its insoluble character.
This is due to the ease in calculation, as its molecular weight ii. Merck’s process
is exactly 100. Na 2 O2 + H2 SO4 → Na 2 SO4 + H2 O2
Check Your Grasp Sod. Peroxide
5. Temporary hardness of water is due to the presence of Here ice cold dilute H2 SO4 is used. Upon cooling crystals of
A. magnesium bicarbonate B. calcium chloride Na 2 SO4 . 10H2 O Separate out and 30% H2 O2 is obtained.
C. magnesium sulphate D. calcium carbonate iii. By electrolysis of 50% 𝐇𝟐 𝐒𝐎𝟒 solution
6. Permutit is technical name given to electrolysis
1. 2H2 SO4 → H2 S2 O8 + H2
A. aluminates of calcium and sodium
Peroxodisulphuric acid.
B. silicates of calcium and sodium
H2 S2 O8 obtained at anode and H2 at cathode.
C. hydrated silicates of aluminum and sodium
2. H2 S2 O8 + 2H2 O → 2H2 SO4 + H2 O2
D. silicates of calcium and magnesium
Peroxodisulphuric acid
7. 𝐇𝟐 𝐎 has structure
iv. From 2- ethyl anthraquinol :
A. linear B. tetrahedral
C. pyramidal D. bent
8. Calgon used as water softener is
A. Na 2 [Na4 (PO3 )6 ] B. Na 4 [Na 2(PO3 )6 ]
C. Na 2 [Na 4(PO4 )5 ] D. Na 4 [Na2 (PO4 )6 ]
9. The 𝐇 − 𝐎 − 𝐇 angle in water in water molecule is about
A. 900 B. 1800
0
C. 102 D. 1050
HEAVY WATER (𝐃𝟐 𝐎) The 2-Ethyl anthraquinone formed can be used again and
Red Alert hence this process is very cheap.
1. Heavy water was discovered by Urey, an American chemist B. Physical aspect of 𝐇𝟐 𝐎𝟐
in 1932. i. Dipole moment of H2 O2 is 2.1 D.
2. A. Boiling point of heavy water is 101.40 C. ii. Melting point of H2 O2 is 272.4 K.
B. Melting point of heavy water is 3.820 C. iii. Density of H2 O2 is 1.44 g/cm3.
C. It is used in the nuclear reactors as Red Alert
i. a coolant and 3. STRUCTURE OF 𝐇𝟐 𝐎𝟐
ii. a moderator It has a non-planar open book structure. The O − H bond
D. All the reactions of heavy water are similar to water but the length is 95 pm and O-O bond length is 147.5 pm. The H-
rate is slower than that of water. So, heavy water is not used O-O bond angle is 94.80 and the dihedral angle is 111.50 .
in biological system.
3. Super heavy water is oxide of tritium(T2 O).
4. A. Melting point of T2 O = 90 C.
B. Boiling point of T2 O = 1040 C
C. Density of T2 O = 1.33 g/cc.
HYDROGEN PEROXIDE (𝐇𝟐 𝐎𝟐 )
1. H2 O2 was discovered by the French chemist J. Thenard in
1818.
2. H2 O2 is thick syrupy liquid with pale blue colour and bitter
taste.
A. Preparation
i. By J.L Thenard method
BaO2 . 8H2 O + H2 SO4 → BaSO4 + H2 O2 + 8H2 O
Barium peroxide (PPt)
Here, white ppt of BaSO4 are removed leaving 5% solution of
H2 O2 .
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4. H2 O2 is diamagnetic and more highly associated via Also 10 mL of O2 at N.T.P is obtained from 1 mL of solution
hydrogen bonding than water. of 10 volumes of H2 O2
5. H2 O2 is slightly stronger acid than water. Thus, 1 mL of the 10 volumes H2 O2 solution contains
(𝐾𝑎 = 1.55 × 10−12 at 293 𝐾). 0.303 g of H2 O2
Pure H2 O2 turns blue litmus red but its dilute solution is ∴ 1000 mL of the given H2 O2 solution contains
neutral to litmus. 0.0303
= × 1000 = 30.3 g/litre of H2 O2
1
6. H2 O2 is a powerful oxidising agent but a weak reducing
Hence, the strength of 10 vol. H2 O solution = 30.3 g/litre
agent. In the presence of strong oxidising agents, H2 O2
or Strength of 10 volume of H2 O2 (in percentage)
behaves as a reducing agent both in acidic as well as alkaline 0.0303
= × 100 = 0.303% (w/v)
medium. 10
Since, H2 O2 can reduce chlorine hence, acts as an anticholor Red Alert
in bleaching by destroying the unreacted chlorine. Since Eq. wt. of H2 O2 =17, Mol. wt. of H2 O2 =34
30.3
7. H2 O2 shows bleaching action due to nascent oxygen. ∴ Normality of the given H2 O2 solution = = 1.79 N
17
8. Bleaching action of O3 and H2 O2 is permanent and is due to 30.3
Molarity of given H2 O2 solution = = 0.89 N
oxidation . 34
EXAMPLE
9. H2 O2 is used as an antiseptic under the name perhydrol. It is
EXAMPLE:1 The percentage by weight of hydrogen in
(27.5 − 31%) H2 O2 solution or 100 volume H2 O2 solution.
𝐇𝟐 𝐎𝟐 is
10. 93% H2 O2 solution is used as an oxidising agent fo rocket
A. 5.88 B. 6.25
fuel and as a propellant for torpedos and submarines.
C. 25 D. 50
11. CONCENTRATION OF 𝐇𝟐 𝐎𝟐
SOLUTION: Mol mass of H2 O2 = 2 × 1 + 16 × 2 =34
Dilute H2 O2 is concentrated to about 30% by slow 2 100
evaporation on a water bath. It is further concentrated to ∴ Percentage of hydrogen = × 100 = = 5.88%
34 17
90% in a vacuum desiccator using conc. 𝑯𝟐 𝑺𝑶𝟒 as Check Your Grasp
dehydration agent. Further concentration to 99% is obtained 10. The boiling point of heavy water is
by distillation under reduced pressure. Last traces of A. 1000 C B. 103.40 C
0
moisture in 99% of H2 O2 are removed or anhydrous H2 O2 is C. 101.4 D. 1040 C
obtained by cooing it to 263 K in a cold bath of ether and dry 11. Decomposition of 𝐇𝟐 𝐎𝟐 is prevented by
ice followed by seeding with a few crystals of solid H2 O2 A. NaOH B. MnO2
when needle-shaped crystals of 100% H2 O2 separate out. C. acetanilide D. oxalic acid
These crystals are removed, dried and melted to get 100% 12. The structure of 𝐇𝟐 𝐎𝟐 is
H2 O2 . A. open book like B. linear
Red Alert C. closed book D. pyramidal
12. STORAGE OF 𝐇𝟐 𝐎𝟐 13. Which of the following statement is incorrect?
H2 O2 is not stored in glass bottles since the alkali metals A. H2 O2 can act as an oxidising agent
oxides present in glass catalyse its decomposition. It is, B. H2 O2 can act as a reducing agent
therefore, stored in paraffin wax coated glass, plastic or C. H2 O2 has acidic properties
Teflon bottles. Small amounts of acid, glycerol, alcohol, D. H2 O2 has basic properties
acetanilide and H3 PO4 are often used as stabilizers to check 14. Which of the following acts as both reducing and
its decomposition. oxidising agent?
Red Alert A. H2 SO4 B. H2 O2
13. STRENGTH OF HYDROGEN PEROXIE SOLUTION C. KOH D. KMnO4
Concentration of H2 O2 is expressed in terms of volume
strength e.g., 10 volume, 15 volume, 20 volume etc. for
example, 10 volume of H2 O2 solution means that 1 mL of this
solution on evolves 10 mL of O2 at N.T.P.
Sometimes the concentration of H2 O2 in a solution is
expressed as percentage of H2 O2 in solution (w/v). For
example, the strength and normality of 10 volumes of
According to the stoichiometry
2H2 O2 → 2H2 O + O2
2(2 + 32) 22400 mL
=68g at N.T.P.
22400 mL of O2 at N.T.P. are obtained from 68 g of H2 O2
68×10
∴ 10 mL of O2 at N.T.P. are obtained from =
22400
g = 0.303 g of H2 O2
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