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Hydrogen & It's Compounds

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HYDROGEN AND ITS COMPOUNDS

4.0 INTRODUCTION :
Hydrogen is the lightest element and also the lightest gas in the periodic table.
Order of Abundance of H :
Hydrogen is the most abundant element in the universe (70% of the total mass of the universe.)
Order of abundance of H : Universe > Sun > Earth
The planets Jupiter and Saturn consist mainly of H2. Similarly about half the mass of the sun and some other
stars is made up of hydrogen.
In Sun's atmosphere and in universe, it is found in atomic form. While in earth it is generally found in
molecular form. At Sun, the stratosphere is made up of H (atomic hydrogen) and they undergoes fusion and
converted into He nuclei and this reaction is exothermic.

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It is the ninth element on earth in order of abundance.
Earth does not posses enough gravitational force to retain live hydrogen molecule i.e. why it is not found in
earth atmosphere in atomic form.
Hydrogen is the most reactive element in atomic form but it is less reactive in molecular form because of
very high bond dissociation energy due to 1s -1s overlapping.

4.1 ISOTOPIC EFFECT :

The effect which can change the physical and chemical properties of isotopes is called isotopic effect.
It is because of difference in mass.
In isotopic effect maximum changes occurs in physical properties like melting point, boiling point, bond
energy, while minimum changes occurs in chemical properties like state of chemical reaction etc.
Imp. Isotopic effect is found only in hydrogen isotopes. Because there is a large difference in mass.

Ex. Which of the following reaction is fast and why ?

(i) CH4 + Cl2 → CH3Cl + HCl

(ii) CD4 + Cl2 → CD3Cl + DCl
Ans. (i) because C–H bond energy is less in comparison to C–D bond energy.

4.2 METHOD OF PREPARATION :

(a) From acids :
The metal which are placed above H in electrochemical series react with dil acids to liberate H2.
Fe + H2SO4 → FeSO4 + H2
e.g.
(dil.)
Cu + H2SO4 → No reaction
(dil.)
Lab preparation : When impure Zn reacts with dil. H2SO4 it forms H2
Zn + H2SO4 → ZnSO4 + H2
(impure) (dil)

Ex. Why we use impure Zn.

Ans. Because the rate of reaction with pure Zn is very slow.
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(b) By alkalies : Only (Be, Zn, Al, Sn, Pb, Si) (Amphoteric metal) react with boiling NaOH or KOH to evolve H2.
Zn + 2NaOH → Na2ZnO2 + H2↑
(sodium zincate)
2Al + 2NaOH + 2H2O → 2NaAlO2 + 3H2↑
(sodium meta aluminate)
Sn + 2NaOH + H2O → Na2SnO3 + 2H2↑
(sodium stannate)
Pb + 2NaOH + H2O → Na2PbO3 + 2H2↑
(sodium plumbate)
Si + 2NaOH + H2O → Na2SiO3 + 2H2↑
(sodium silicate)
Be + 2NaOH → Na2BeO2 + H2
(sodium beryllate)
(c) With water :

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(i) With cold water (7°C-25°C) : Li, K, Ba, Ca, Na, Sr
(ii) With hot water (25°C–90°C) : Mg, Al, Cr, Mn, Zn
(iii) With steam (greater then 100°C) : Fe, Cd, Ni, Sn, Pb
(d) Commercial or industrial method to prepare H2 :
The commonly used processes are outlined below:
(i) Electrolysis of acidified water using platinum electrodes gives hydrogen.
Electrolysis
2H2O(l) →
Traces of acid/base
2H2(g) + O2(g)
(ii) High purity (>99.95%) dihydrogen is obtained by electrolysing warm aqueous barium hydroxide
solution between nickel electrodes.
(iii) It is obtained as a by product in the manufacture of sodium hydroxide and chlorine by the electrolysis
of brine solution. During electrolysis, the reactions that take place are:
at anode: 2Cl–(aq) → Cl2(g) + 2e–
at cathode: 2H2O(l) + 2e– → H2 (g) + 2OH– (aq)
overall reaction : 2Na+ (aq) + 2Cl– (aq) + 2H2O(l) → Cl2(g) + H2(g) + 2Na+ (aq) + 2OH– (aq)
(iv) From hydrocarbons : Reaction of steam on hydrocarbons or coke at high temperatures in the
presence of catalyst yields hydrogen.
1270K
CnH2n+2 + nH2O 
Ni
→ nCO + (3n +1) H2
1270K
e.g., CH4(g) + H2O(g) 
Ni → CO(g) + 3H2(g)
The mixture of CO and H2 is called water gas. As this mixture of CO and H2 is used for the synthesis of
methanol and a number of hydrocarbons, it is also called synthesis gas or ‘syngas’. Now days ‘syngas’ is
produced from sewage, saw-dust, scrap wood, newspapers etc. The process of producing ‘syngas’ from coal
is called ‘coal gasification’.
(v) Bosch process :
1270K
C(s) + H2O(g)  → CO(g) + H2(g)
The production of dihydrogen can be increased by reacting carbon monoxide of syngas mixtures with steam
in the presence of iron chromate as catalyst.
673K
CO(g) + H2O(g) 
catalyst
→ CO2(g) + H2(g)
This is called water-gas shift reaction.
(vi) Lane's process :
Fe + H2 O → Fe3 O4 + H2 ↑
steam

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4.3 PHYSICAL PROPERTIES OF HYDROGEN :
(i) Hydrogen is the lightest, colorless, odourless and tasteless gas. It is sparingly soluble in water. It is
inflammable and less reactive gas.
(ii) Its m.p. (– 259.20C) and b.p. (–2520C) are very low indicating less intermolecular attraction. Due to
low m.p. liquid hydrogen is used as a cryogenic fluid (to produce low temperature).
(iii) H—H bond energy is 104 Kcal mol–1 or 436 KJ/mol
(iv) H – H bond length is 74 pm so H2 is less reactive and require high temp for reaction.
4.4 USES OF HYDROGEN :
1. Hydrogenation of vegetable oil to form solid fats i.e. vanaspati ghee.
2. In liquid form as a rocket fuel. (Liquid H2 + Liquid O2)
3. In a air ship of balloons as a mixture of Hydrogen & Helium [15% H2 + 85% He]
4. Formation of different compounds.
Like → NH3, (Haber process) alkane, alcohol and other hydrocarbons

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BEGINNER'S BOX-1
1. Which of the following produces hydrolith with dihydrogen ?
(1) Mg (2) Al (3) Cu (4) Ca
2. Hydrogen combines with other elements by :-
(1) Losing an electron (2) Gaining an electron
(3) Sharing an electron (4) Losing, gaining or sharing electron
3. Hydrogen readily combines with non-metals and thus it shows its :-
(1) Electronegativity character (2) Electropositive character
(3) Both (1) and (2) (4) None of these
4. The oxidation states shown by hydrogen are :-
(1) –1 only (2) Zero only (3) +1, –1, 0 (4) +1 only
5. Hydrogen readily combines with metals and thus shows its :-
(1) Electropositive character (2) Electronegative character
(3) Both (1) and (2) (4) None of these
6. In which of the compounds does hydrogen have an oxidation state of –1 :-
(1) CH4 (2) NH3 (3) HCl (4) CaH2
7. Match List I (Fuels) with List II (composition) and select the correct answer using the codes given below the
lists :-
List I (Fuels) List II (Composition)
A. Water gas i. A mixture of CO and N2
B. Producer gas ii. Methane
C. Coal gas iii. A mixture of CO and H2
D. Natural gas iv. A mixture of CO, H2, CH4 and CO2
A B C D
(1) iii i iv ii
(2) iii i ii iv
(3) i iii iv ii
(4) iii ii iv i
8. H2 react with halogen in presence of catalyst to form hydrogen halide HX. X (Halogen) is :-
(1) Cl2 (2) Br2 (3) F2 (4) I2
9. Which of the following is a method of preparation of H2 ?
(1) reaction of granulated Zn with dil. HCl (2) reaction of Zn with aqueous Alkali.
(3) by electroysis of Brine solution (4) All of the above

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4.5 HYDRIDES
The binary compounds of hydrogen with different elements are called hydrides.
These are of three types :
(a) Ionic/Salt like/Saline hydrides :
 Compounds of hydrogen with s-block elements except beryllium & magnesium are called ionic
hydrides.
LiH, NaH, KH, RbH, CsH, CaH2, SrH2, BaH2
BeH2, MgH2 are covalent polymeric hydride.
 Structure of these hydrides are similar to rock salt, so they are also called salt like/saline hydrides.
 Down the group, atomic size↑ Lattice energy↓ stability↓ Melting point↓ Boiling point↓
 On electrolysis of these hydrides, hydrogen is liberated at anode.
 On reaction with water these hydrides will form hydrogen
NaH + H2O → NaOH + H2

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 These hydrides form complex hydrides which are very good reducing agents.
4LiH + AlCl3 → LiAlH4 + 3LiCl
LiAlH4 → Lithium aluminium hydride
NaBH4 → Sodium borohydride
(b) Metallic / Interstitial hydrides :
 They are the compounds of d & f-block elements. In these hydrides hydrogen occupies interstitial sites
present in metallic lattice, so they are called interstitial hydrides.
 Properties of these hydrides are similar to parent metals, so they are also known as metallic hydrides.
 These hydrides are non stoichiometric in nature (i.e. having variable composition)
ZrHx (x = 1.3 – 1.75)
TiHx (x = 1.8 – 2)
 Metals of group 7,8,9 don't form any hydrides so this particular part of periodic table is known as
hydride gap.
 In group-6 only one hydride CrH is formed.
(c) Covalent/Molecular hydrides
 They are the compounds of hydrogen with p-block elements CH4, NH3, H2O, HF, etc.
 These hydrides exist as molecules, so they are also known as molecular hydrides. There hydrides are
non-conductor of electricity.
These hydrides are again divides into 3 categories.
(a) Electron deficient hydrides :
They are the hydrides of group 13 elements.
e.g. BH3, AlH3, GaH3 – In these hydrides central element does not have complete octet. i.e.
why they are called electron deficient compounds.
(b) Electron precise hydrides :
They are the hydrides of group 14 element.
e.g. CH4, SiH4, GeH4 – In these type of hydrides central element has 8e– in its outer most shell.
(c) Electron rich hydrides :
These are the hydrides of group 15, 16 and 17
.. .. ..
e.g. NH3, H2O , HF.. – In these hydrides lone pair are present on central element which can be
..
..

given to others. So they are called electron rich hydrides.

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4.6 HARD AND SOFT WATER
Water which produces lather with soap is soft water while water which does not produces lather with soap
is hard water. The hardness of water is caused by presence of bicarbonates, chlorides and sulphates of
calcium and magnesium.
Ca (aq) + 2C17H35COO (aq) → (C17H35COO)2Ca ↓
2+ –

Mg2 + (aq) + 2C17 H35 COO − (aq) → (C17 H35 COO)2 Mg ↓

Anion of soap Inso lub le precipitates

Hardness of water are of two types :

(a) Temporary hardness (b) Permanent hardness
(a) Temporary hardness : This is due to the presence of bicarbonates of calcium and magnesium.
Temporary hardness in water is easily removed by boiling, as the bicarbonates decompose readily and
the insoluble compounds are precipitated.

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Boiling
Ca(HCO3 )2  → CaCO3 + H2 O + CO2
(Inso lub le)

Boiling
Mg(HCO3 )2  → Mg(OH)2 + 2CO2
(inso lub le)

Temporary hardness can also be removed by Clark's process which involves the addition of slaked lime
[Ca(OH)2].
Ca(HCO3)2 + Ca(OH)2→ 2CaCO3 + 2H2O
(Inso lub le)

It is essential to add only the calculated amount of Ca(OH)2 because excess will cause artificial hardness.
(b) Permanent hardness : This is due to the presence of sulphates or chlorides of both of calcium and
magnesium. This type of hardness cannot be removed by boiling or by the addition of slaked lime.
The various water softeners are :
(i) Washing soda : It removes both the temporary and permanent hardness by converting
soluble calcium and magnesium compounds into insoluble compounds.
CaCl2 + Na2CO3 → CaCO3 + 2NaCl
(Insoluble)

CaSO4 + Na2CO3→ CaCO3 + Na2 SO4

(Inso lub le)

Ca(HCO3)2 + Na2CO3 → CaCO3 + 2NaHCO3

(Insoluble) (Soluble)

In place of sodium carbonate, caustic soda or sodium phosphate can also be used.
MgCl2 + 2NaOH → Mg(OH)2 + 2NaCl
(Inso lub le)

3MgSO4 + 2Na3PO4 → Mg3 (PO4 )2 + 3Na2SO4

(Inso lub le)

(ii) Calgon : The complex salt of metaphosphoric acid, sodium hexametaphosphate (NaPO3)6, is
known as calgon. It is represented as Na2[Na4(PO3)6]. Calcium and magnesium salts present in
hard water react with calgon to give complex salts.
2CaSO4 + Na2[Na4(PO3)6] → Na2[Ca2(PO3)6] + 2Na2SO4
2MgSO4 + Na2[Na4(PO3)6] → Na2[Mg2(PO3)6] + 2Na2SO4

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(iii) Permutit process : Permutit is hydrated sodium
alumino silicate Hard water
[Na2Al2Si2O8. xH2O] or [Na2O.Al2O3.2SiO2.xH2O]
NaCl solution
Permutit is also known as sodium zeolite (Na2Z)
means Zeolite is Al2Si2O8.xH2O.
In this process when hard water is poured into Na2Z Soft water
chamber, it may contain organic impurities like Graves
plant. These impurities can be removed by gravel.
On moving upwards hard water will react with Na2Z
Impurities
during this reaction Na+ ions of Na2Z will replace
Mg+2 & Ca+2 of impurities.
Na2Z + CaCl2 → 2NaCl + CaZ
NaCl is dissolved in water & water becomes soft.
After some time when Na2Z is completely converted into CaZ. Process is stopped and for
regeneration of Na2Z. We use NaCl solution.

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2NaCl + CaZ → CaCl2 + Na2Z
(iv) Ion exchange resin : This process removes both temporary and permanent hardness. Also,
by this process we can remove both cation & anion of hardness.
This process contain two chambers.
(a) Cation exchange resin : This resin contains granular insoluble organic acid having giant
molecules with RCOO–H+ group.
(b) Anion exchange resin : This resin contain giant organic molecules with basic groups
derived from amines with RNH 3+ OH −
Process : When hard water is poured into first chamber the cation of hardness (Mg ,Ca )
+2 +2

removed by H+ ions of organic acid.

2RCOO H + CaCl2 → (RCOO)2Ca + 2H + 2Cl
– + + –

2RCOO–H+ + MgSO4 → (RCOO)2Mg + 2H+ + SO4–2

+ – 2– –
Hard water H , Cl , SO4 , HCO3

Ca2+, Mg2+, SO42–,Cl–

Dilute acid for

regeneration
regeneration

Alkali for

Cation Anion
exchanger exchanger

Soft water
Waste Waste
Pure water
This water becomes soften but not used for drinking purpose because this water contain the
impurity of acid. To remove anion of hardness this acidic water then passed through another
– –2 –
bed containing anion exchanger. This exchanger removes anion like Cl , SO4 & HCO3 .
RNH+3 OH – + H+ + Cl → RNH3+ Cl – + H + OH
–

This water is free from impurities & can be used for drinking purpose.
After sometime when both resin gets exhausted process is stopped.
Regeneration of resin :
(i) Cation exchange resin : We use dil acid.
2H+Cl– + (RCOO)2Ca → 2RCOO–H+ + CaCl2
(ii) Anion exchange resin : We use dil NaOH solution
RNH 3+ Cl− + Na+OH– → Na+Cl– + RNH3+OH–

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4.7 HEAVY WATER (D2O)
Method of preparation :
Repeated electrolysis of H2O : On electrolysis of water (impure) H2O dissociate into H+ & OH– while a
fractional part of D2O will dissociate into D+ & OD–
+ –
H2O  H + OH
D2O  D+ + OD–
D+ & OD– due to more mass have less mobility i.e. why H+ & OH– will move towards cathode & anode
+ –
respectively while D & OD will be in solution.
This process is repeated six times.
Properties of Heavy water :
Physical properties :
(a) Heavy water is a colourless, odourless and tasteless mobile liquid.

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(b) Nearly all the physical constants are higher than the corresponding values of ordinary water.
(dielectric constant order H2O > D2O).
Chemical properties :
(a) Heavy water is chemically similar to ordinary water. However, D2O reacts more slowly than H2O in
chemical reactions.
(b) All chemical properties are same, but reactions are slow.
Uses : As a neutron moderator : Fission in uranium-235 is brought by slow speed neutrons. The
substances which are used for slowing down the speed of neutrons are called moderators. Heavy water is
used for this purpose in nuclear reactors.
4.8 H2O2 (HYDROGEN PEROXIDE)
Method of preparation (According to NCERT)
(i) Acidifying barium peroxide and removing excess water by evaporation under reduced pressure gives
hydrogen peroxide.

BaO2 .8H2 O(s) + H2 SO4 → BaSO4 (s) + H2 O2 (aq) + 8H2 O( )

(ii) Industrial Method : Auto oxidation of 2 ethyl anthraquinol ( cyclic process) :

OH O
C2H5
O2 C2H5

 
 H2O2+
H 2

OH O

(iii) Electrolytic Process : (Used 50%) H2SO4 in electrolytic cell using Pt as anode and graphite as cathode.
2H2SO4 → 2H+ + 2HSOΘ4

At Cathode 2H
+
+ 2e– → H2 ↑
+ 2e –
→ H2 S2 O8     
At Anode 2HSO4 –
:
( Peroxo disulphuric acid )
H2S2O8 + H2O → H2SO4 + H2SO5 [Peroxo monosulphuric acid (Caro's acid)]
H2SO5 + H2O → H2SO4 + H2O2

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Physical properties :
(i) Pure H2O2 is colourless, odourless liquid and impure with bluish layer.
(ii) It has more Hydrogen bonding then H2O. So, order of boiling point is H2O2 > D2O > H2O

 
Order of melting point = H2 O° 2 < H2° O 
 −0.35 C 0 C

(iii) It is soluble in H2O, alcohol and ether.
(iv) It has bitter taste and harmful for skin.
(v) It is a dibasic weak acid.
(vi) It has oxidising as well as reducing property.
(vii) H2O2 easily decompose in presence of light and temperature, so H2O2 always kept in dark bottles and
kept at cool places and small amount of inhibitor is added like R–OH, glycerol and Acetone.
(viii) 30% solution of H2O2 is called Perhydrol.

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(ix) H2O2 decomposes at its boiling point hence its distillation is carried out under reduced pressure.
Chemical properties :

(A) Oxidising and Reducing behaviour of H2O2

Oxidising behaviour Reducing behaviour

–1 –1
H2O2 H2O2
RA Fe
+2
Fe
+3 O3 O2
O2
(I) H2O2 OA
H2O (II) NO – NO3
– Ag2O Ag
2
∆
disproportionate H2O +½ O2 –2 I2 I–
S SO4 +
H +2
–2 Mn
–
H2O MnO 4 +4
— Mn
OH
0
O2

Structure of hydrogen peroxide

H H
95.0pm 98.8pm
147.5pm 111.5° 145.8pm 90.2°
94.8° 101.9°
H H

(a) Gas phase (a) Solid phase

Uses
(i) Bleaching agent (ii) Hair dying
(iii) H2O2 + N2H4 as Rocket propellent (iv) H2O2 as oxidant and reductant
(v) Antiseptic

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BEGINNER'S BOX-2
1. The structure of H2O2 is
H H
H H
(1) O O (2) O O (3) H–O–O–H (4) O O
H OH
2. Temporary hardness may be removed from water by adding
(1) CaCO3 (2)Ca(OH)2 (3)CaSO4 (4) HCl

3. Temporary hardness of water can be removed by

(1) Addition of potassium permanganate (2) Boiling
(3) Filtration (4) Addition of chlorine

4. When zeolite (Hydrated sodium aluminium silicate) is treated with hard water the sodium ions are exchanged
with
–
(1)OH ions (2) SO42–ions (3) Ca2+ ions (4) H+ions

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5. When temporary hard water containing Mg(HCO3)2 is boiled the ppt. formed is of
(1) MgCO3 (2) MgO (3)Mg(OH)2 (4) None of these

6. Which of the following can effectively remove all types of hardness of water
(1) Soap (2) Washing soda (3) Slaked lime (4) None of these

7. Impurity of Mg(HCO3)2 is removed from water on boiling. It removes in the form of

(1) MgCO3 (2) Mg(OH)2 (3) Mg(HCO3)2 (4) None of these

8. In cation exchange process for permanent hardness, H+ exchange for Na+, Mg+2, Ca+2 and other cation
present in water. This process result in proton release and thus makes the nature of water :-
(1) Acidic (2) Basic (3) Neutral (4) Amphoteric

9. Which of the following option is correct ?

[Statement T for true & F for false]
(a) H2O2 is almost colourless (very pale blue) liquid
(b) H2O2 is miscible with water in all proportion and forms hydrated H2O2.H2O
(c) 1% H2O2 is concentrated to 30% by distillation under reduced pressure
(d) 1 ml of 30 % H2O2 solution will give 100 ml of oxygen at STP
(1) TTTT (2) FTTT (3) FTFT (4) FFTT

10. In a following chemical reaction

MnO4– + H+ + H2O2 →
The incorrect option is
(1) O2 is release (2) Mn+7 reduced into Mn+2
(3) H2O2 acts as an oxidising agent (4) All of these

ANSWER'S KEY
Que. 1 2 3 4 5 6 7 8 9
BEGINNER'S BOX-1
Ans. 4 4 2 3 2 4 1 4 4
Que. 1 2 3 4 5 6 7 8 9 10
BEGINNER'S BOX-2
Ans. 2 2 2 3 3 2 2 1 1 3
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