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C-09:- HYDROGEN

HYDROGEN
Also, conc.
H 2 SO 4 is not used for the preparation of
1. Hydrogen is the most abundant element in the universe and
the third most abundant on the surface of globe. It mainly
dihydrogen because Zn form
SO 2 gas instead of H2
occurs in combined state. It is the 1st element in the periodic
table. It was discovered by Henry Cavendish in 1766 and gas.
prepared the gas by treating iron with dil.
H 2 SO 4 . Its Zn+ H 2 SO 4 ( Conc . ) ZnSO 4 + SO 2+ 2 H 2 O

name was given by Lavoisier because it produces water.


+ ii. Electrolysis of water
2. Both H and H are stable in gaseous state. 2 H 2 O(l)electrolysis 2 H 2 ( g )+O 2 (g)

+ 0
3. Electronic configuration of H is 1 s while that of Hydrogen is evolved at cathode having high purity. But
method is expansive.
iii. Lanes process : (used for large scale production)
2
H is 1 s . 3 Fe +4 H 2 O (steam) Fe3 O4 + 4 H 2

H iv. Industrial preparation of hydrogen: Bosch process:


In this method water gas is mixes with steam and passed over
4. Hydride ion cannot exist in aqueous medium, while Fe2 O3 and Cr 2 O3 at
heated catalytic mixture of

773 K when
CO2 and H 2 are obtained. The mixture
+ +

H can exist in aqueous solution as H 3 O . is compressed to 25 atmosphere pressure and passed into

water,
CO2 dissolve while H 2 is set free.
5. Hydrogen is called a rogue element as it can be placed in
st
1 group with alkali metal and in 17th group with C+ H 2 O1270 K

halogens.
Water gas(Syn gas)
Red Alert
Fe2 O3 / Cr O CO 2+2 H 2 .
H 2 3

( 2) 773 K
6. DIHYDROGEN H 2 +CO+ H 2 O

A. Preparation The process of producing syn gas from coal or coke is called
i. Laboratory method for preparation of hydrogen: In the coal gasification and production of hydrogen gas from water
laboratory hydrogen is prepared by the action of dil. gas is called water gas shift reaction.
B. Properties of dihydrogen
H 2 SO 4 on granulated zinc.
i. 1L of
H 2 at N.T.P. weights 0.0899 g and its density is
Pure zinc metal is not used because it reacts very slowly with
equal to 1/14 in that of air.
dil.
H 2 SO 4 . The presence of impurities, however, ii. a) I.E. of hydrogen = 13.54 eV
b) E.A of hydrogen = 173 kcal/mol
increases the rate of reaction due to the formation of c) Electronegativity of hydrogen = 2.1
Electrochemical couples.
Zn+ H 2 SO 4 ( dil . ) ZnSO 4 + 2 H 2
2

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% 1015
6. Nuclear spin quantum number 1 1/2
7. Radioactive nature Stable Stable Radioactive
1 H3 2He3+-1e0 (-particle)
8.
iii. Hydrogen Half lifeleast denser gas known and least
is the --- denser --- 12.33 years
9.
liquid. No. of neutrons 0 1 2
iv. Metals which are more electropositive than hydrogen
produce hydrogen gas on reaction with alkali or acid.
v. Isotopic effect. The difference in properties arising from the
difference in mass is called isotopic effect. It is maximum for
hydrogen because the percentage change in mass is maximum
for isotopes of hydrogen.
vi. Hydrogen is inflammable, a mixture of 85% He and 15%
H 2 is used in the filling of aeroships and balloons.
vii. Moist hydrogen gas is not dried by passing through conc.
H 2 SO 4 as it may catch fire. So, P2 O5 may be used
These two isomers have 1 and 0 nuclear spin respectively. The
as a drying agent for hydrogen gas. conversion of one isomer into another isomer is a slow
7. NASCENT AND ATOMIC HYDROGEN process. Ordinary dihydrogen is an equilibrium mixture of
A. Nascent hydrogen is the hydrogen at the moment of its ortho and para hydrogen.
generation in a chemical reaction. It consists of atoms of Ortho hydrogen para hydrogen
hydrogen and hence has more energy and so it is more
The amount of ortho and para hydrogen varies with
reactive and is a stronger reducing agent than ordinary
temperature as:
hydrogen.
i. At 20 K hydrogen contains mainly para hydrogen which is
B. At high temperature (about 30000C) and low pressure
more stable.
molecules of hydrogen dissociate to form atoms of hydrogen
ii. At the temperature of liquefaction of air, the ration of ortho
known as atomic hydrogen.
and para hydrogen is 1:1.
C. Nascent hydrogen can be produced even at room
iii. At the room temperature, the ratio of ortho to para
temperature but atomic hydrogen is produced at elevated
hydrogen is 3:1.
temperature. iv. Even at very high temperature, the ratio of ortho to para
D. Nascent hydrogen can never be isolated but atomic
hydrogen can never be more than 3:1.
hydrogen can be isolate. Note
E. Reducing power of atomic hydrogen is much greater than Thus, it has been possible to get pure para hydrogen by
that of nascent hydrogen. cooling ordinary hydrogen gas to a very low temperature
Red Alert
(close to 20 K) but it is never possible to get a sample of
8. ORTHO AND PARA HYDROGEN:
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


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1. The nuclei of tritium (1H3) atom would contain neutrons deficient compounds. They act as Lewis acids i.e., electron
A. 1 B. 2 acceptors.
C. 3 D. 4 ii. Electron-precise: Electron-precise hydrides have the require
2. The lightest element among the following is number of electrons to write their conventional Lewis
A. He B. Cs
structures. All elements of group 14 form such compounds
C. H D. 1
(e.g.,
CH 4 .
Red Alert
9. HYDRIDES iii. Electron-rich hydrides : Electron-rich hydrides have excess
Dihydrogen, under certain reaction conditions, combines with electrons which are present as Ione pairs. Elements of group
almost all elements, except noble gases, to form binary
compounds, called hydrides. NH
The hydrides are of three types:
15-17 form such compounds. has 1-Ione pair,
A. Ionic or Saline hydrides
These are stoichiometric compounds of dihydrogen formed

with most of the s -block elements which are highly H 2 O -2 and HF -3 Ione pairs). They will behave as
electropositive in character. The ionic hydrides are crystalline, Lewis bases i.e., electron donors. The presence of Ione pairs
non-volatile and non-conducting in solid state. However, they on highly electronegative atoms like N, O and F in hydrides
conduct electricity and on electrolysis liberate dihydrogen gas results in hydrogen bond formation between the molecules.
This leads to the association of molecules.
at anode, which confirms the existence of H ion. C. Metallic or Non-stoichiometric (or interstitial) Hydrides
These are formed by many d-block and f-block elements. The
2 H ( melt ) anode H 2 ( g ) +2 e metals of group 7,8 and 9 do not form hydride. This is known

as hydride gap. Even from group 6, only chromium forms
Saline hydrides react violently with water, producing CrH. These hydrides conduct heat and electricity though not
dihydrogen gas. as efficiently as their parent metals do. They are always non
NaH ( s ) + H 2 O ( aq ) NaOH ( aq ) + H 2 (g) stoichiometric, being deficient in hydrogen. For example,
LaH 2.87, YbH 2.55 , TiH 1.5 1.8 , ZrH 1.31.75
Lithium hydride is rather unreactive at moderate temperature

with
O2 or C l 2 . It is, therefore used in the synthesis hydrides. The law of constant composition does not hold
good.
of other useful hydrides e.g. The property of absorption of hydrogen on transition metals is
8 LiH + A l 2 C l 6 2 LiA l H 4 + 6 LiC l widely used in catalytic reduction/ hydrogenation reactions
for the preparation of large number of compounds. Some of
2 LiH +B 2 H 6 2 LiBH 4 the metals (e.g. Pd, Pt) can accommodate a very large volume
of hydrogen and therefore, can be used as its storage media.
Note This property has high potential for hydrogen storage and as a
Ca H 2 is called hydrolith. source of energy.
Note
B. Covalent or molecular hydride PH 5 although have +5
Dihydrogen forms molecular compounds with most of the Phosphorus does not form

p -block elements. Most familiar examples are CH 4 , oxidation state because enthalpy of atomization of hydrogen
is very high. Also electron gain enthalpy value of hydrogen do
NH 3 , H 2 O and HF. Hydrogen compounds of non- not favour the higher oxidation state of phosphorous.
i. Metals like Pd. Pt, Au, Ni etc. have the property of absorbing
metals have been considered as hydrides. Being covalent, they large quantity of hydrogen at normal or higher temperature.
are volatile compounds. This phenomenon is known as occlusion of hydrogen. The
Molecular hydrides are further classified into three types occlusion property of these metals is in order. Colloidal
according to the relative numbers of electrons and bonds in palladium > Palladium> Platinum> Gold> Nickel.
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
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ii. Hydrogen acts both as oxidising and reducing agent since it B. Hardness of water is due to the presence of bicarbonates,
+ chlorides and sulphates of Ca and Mg in it.
can form both cations H (by loss of electron) and anion 2+ 2+
C. The Ca and Mg ions react with the anions of

H (by gain of electron). fatty acids (stearic, palmitic, oleic acids etc.) present in soaps to
form curdy white precipitates. As a result hard water does not
Check Your Grasp produce lather with soap immediately.
3. The absorption of hydrogen by metals is called C
A. dehydrogenation B. hydrogenation
C. occlusion D. absorption COO
4. Which of the following produces hydrolith with
17 H 35
dihydrogen?
2
C17 H 35
A. Mg B. Al
C. Cu D. Ca ++CaCl2
( H 2 O) Na
WATER
COO
1. In nature water exists in all the three phases i.e. solid (ice),
liquid (water) and gas (steam or water vapours). Sod. Stearate Cal.stearate
3 (Soap) (Curdy white ppt.)
2. In water molecule, oxygen is sp - hybridised and TRICK
i. Temporary hardness is due to the presence of bicarbonates of
contains two Ione pair of electrons due to which water has
calcium and magnesium.
0
bent structure with HOH bond angel of 104.5 . ii Permanent hardness is due to the present of soluble chlorides
and sulphates of calcium and magnesium.
3. The dipole moment of water is 1.84 D. Red Alert
4 D. Removal of hardness of water
4. Water has maximum density at 277 K ( 0 C). i. Ions exchange method: This is the most modern method for
2+ 2+

5. Rain water is purest form of water. softening of hard water. Here Ca and Mg ions
6. Pure water is not a good conductor so it is made conductor by
adding small amount of acid or alkali. present in hard water are exchanged by those ions present in ion
7. Water is known as universal solvent due to its high dielectric exchangers which are mainly of two types: Zeolite (naturally
constant i.e.82. occurring) and permutit (synthetic).
8. Ice floats on water. Due to its cage like structure in which
represented by the general formula
Na2 Z where Z=
there are empty spaces and hence greater volume. So the
density of ice is lower than water. Also, water has maximum A l 2 Si2 O8 . x H 2 O is called inorganic ion exchanger.
0
density at 4 C because when ice melts fill the empty
ii. Cation exchange resins : These consists of giant
spaces first and volume decreases. hydrocarbon frame work (R) attached to acidic groups such as
9. Amphoteric nature: COOH SO 2 OH
(carboxylic) or (sulphonic acid)
++ OH groups and are represented by the general formula
H 2 O H 3 O
RCOOH or
14 2 2
K w =1.0 10 mol /L at 298 K RSO 2 OH . Since the + ions of the acidic groups
H
Red Alert
10. HARD AND SOFT WATER
A. Water that produces lather with soap readily is called soft 2+ 2+

water. For example, rain water, distilled water and are exchanged with Ca and Mg ions present in hard
demineralised water.
Water which does not produce lather with soap readily is called water, water becomes free from cations by treatment with cation
hard water. For example: sea water, river water, spring water, exchangers.
lake water and well water.
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ii. Anion exchange resins: These resins contain basic group


9. The HOH angle in water in water molecule is

such as OH (hydroxide) ions usually in the form of about
A. 900 B. 1800
substituted ammonium hydroxides attached to giant
hydrocarbon frame work (R). These may be represented by the C. 1020 D. 1050
D
general formula R +
NH 3 OH . Since these resins
HEAVY WATER ( 2 O)


can exchange OH ions with anions such as C l and Red Alert
1. Heavy water was discovered by Urey, an American chemist in
2 1932.
SO 4 ions present in hard water, water becomes free from 2. A. Boiling point of heavy water is 101.40 C .

anions by treatment with anion exchangers. B. Melting point of heavy water is 3.820 C .
NaPO C. It is used in the nuclear reactors as
Na 4
iv. The formula of calgon is Na or it is i. a coolant and
2 ii. a moderator

D. All the reactions of heavy water are similar to water but the
commonly called sodium hexa metaphosphate. rate is slower than that of water. So, heavy water is not used
E. Degree of hardness in biological system.
The amount of hardness causing substance present in a certain T
volume of water measures the extent of hardness in terms of 3. Super heavy water is oxide of tritium ( 2 O) .
calcium carbonate although this is never responsible for
causing hardness of water because of its insoluble character.
This is due to the ease in calculation, as its molecular weight 4. A. Melting point of T 2 O=9 0 C .
is exactly 100.
0
Check Your Grasp B. Boiling point of T 2 O=104 C
5. Temporary hardness of water is due to the presence of
A. magnesium bicarbonate B. calcium chloride T 2 O=1.33 g/cc .
C. magnesium sulphate D. calcium carbonate C. Density of
6. Permutit is technical name given to H
A. aluminates of calcium and sodium
B. silicates of calcium and sodium HYDROGEN PEROXIDE ( 2 O 2)
C. hydrated silicates of aluminum and sodium
D. silicates of calcium and magnesium
H 2 O has structure 1.
H 2 O2 was discovered by the French chemist J. Thenard
7.
A. linear B. tetrahedral in 1818.
C. pyramidal D. bent 2.
H 2 O2 is thick syrupy liquid with pale blue colour and
8. Calgon used as water softener is
Na4 Na 2 bitter taste.
A. B. A. Preparation
Na2 Na 4
i. By J.L Thenard method
BaO 2 .8 H 2 O+ H 2 SO 4 BaSO 4 + H 2 O2 +8 H 2 O
Na
Na Barium peroxide (PPt)
PO
C. D. Here, white ppt of
BaSO 4 are removed leaving 5%
Na 4
Na 2 H 2 O2 .
solution of
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This method is not used widely as


H 2 O2 perpared i. Dipole moment of
H 2 O2 is 2.1 D.

2+ ii. Melting point of


H 2 O2 is 272.4 K.
contains some heavy Ba ions. These catalysed the
iii. Density of
H 2 O2 is 1.44 g/cm 3 .

decomposition of
H 2 O2 . To prevent this H 2 SO 4 is Red Alert
3. STRUCTURE OF
H 2 O2
PO
It has a non-planar open book structure. The OH bond
replaced by
H 3 PO 4 and Ba3
gets
length is 95 pm and O -O bond length is 147.5 pm. The
completely precipitated. H-
PO 94.80 and the dihedral angle is
O-O bond angle is

3 BaO 3 .8 H 2 O+ 3 H 3 PO 4 Ba3 111.50 .
(ppt)

ii. Mercks process


Na2 O2 + H 2 SO 4 Na 2 SO 4 + H 2 O2
Sod. Peroxide
Here ice cold dilute
H 2 SO 4 is used. Upon cooling

crystals of
Na 2 SO 4 . 10 H 2 O Separate out and 30%

H 2 O2 is obtained.

iii. By electrolysis of 50%


H 2 SO 4 solution

2 H 2 SO 4 electrolysis H 2 S2 O 8 + H 2
1.

Peroxodisulphuric acid.
4.
H 2 O2 is diamagnetic and more highly associated via
H 2 S2 O8 obtained at anode and H 2 at cathode.
hydrogen bonding than water.
2.
H 2 S2 O8 +2 H 2 O 2 H 2 SO 4 + H 2 O2 H 2 O2 is slightly stronger acid than water.
5.
Peroxodisulphuric acid
iv. From 2- ethyl anthraquinol : K
293 K .
at

Pure
H 2 O2 turns blue litmus red but its dilute solution is

neutral to litmus.
6.
H 2 O2 is a powerful oxidising agent but a weak reducing
The 2-Ethyl anthraquinone formed can be used again and
hence this process is very cheap. agent. In the presence of strong oxidising agents,
H 2 O2

B. Physical aspect of
H 2 O2
behaves as a reducing agent both in acidic as well as alkaline
medium.
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Since,
H 2 O2 can reduce chlorine hence, acts as an Concentration of
H 2 O2 is expressed in terms of volume

anticholor in bleaching by destroying the unreacted chlorine. strength e.g., 10 volume, 15 volume, 20 volume etc. for
H 2 O2 shows bleaching action due to nascent oxygen. example, 10 volume of
H 2 O2 solution means that 1 mL
7.
O 3 and H 2 O2 is permanent and of this solution on evolves 10 mL of
O2 at N.T.P.
8. Bleaching action of

is due to oxidation . Sometimes the concentration of


H 2 O2 in a solution is
9.
H 2 O2 is used as an antiseptic under the name perhydrol.
expressed as percentage of
H 2 O2 in solution (w/v). For

It is (27.531 ) H 2 O2 solution or 100 volume example, the strength and normality of 10 volumes of
According to the stoichiometry
H 2 O2 solution. 2 H 2 O2 2 H 2 O+O2

10. 93%
H 2 O2 solution is used as an oxidising agent fo 2 (2+32 ) 22400 mL

rocket fuel and as a propellant for torpedos and submarines. =68g at N.T.P.
H 2 O2 22400 mL of
O2 at N.T.P. are obtained from 68 g of
11. CONCENTRATION OF
H 2 O2 is concentrated to about 30% by slow H 2 O2
Dilute

evaporation on a water bath. It is further concentrated to 10 mL of O2 at N.T.P. are obtained from


H 2 SO 4 as
90% in a vacuum desiccator using conc. 68 10

dehydration agent. Further concentration to 99% is obtained 22400
by distillation under reduced pressure. Last traces of
g=0.303 g of H 2 O2
moisture in 99% of
H 2 O2 are removed or anhydrous
Also 10 mL of
O2 at N.T.P is obtained from 1 mL of
H 2 O2 is obtained by cooing it to 263 K in a cold bath of
solution of 10 volumes of
H 2 O2
ether and dry ice followed by seeding with a few crystals of
H 2 O2 when needle-shaped crystals of 100% Thus, 1 mL of the 10 volumes
H 2 O2 solution contains
solid

H 2 O2 separate out. These crystals are removed, dried and 0.303 g of


H 2 O2

1000 mL of the given H 2 O2 solution contains


melted to get 100%
H 2 O2 .
0.0303
Red Alert 1000=30.3 g/litre of H 2 O2
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12. STORAGE OF
H 2 O2
Hence, the strength of 10 vol.
H 2 O solution 30.3
H 2 O2 is not stored in glass bottles since the alkali metals
g/litre
oxides present in glass catalyse its decomposition. It is, H 2 O2 (in percentage)
therefore, stored in paraffin wax coated glass, plastic or or Strength of 10 volume of
Teflon bottles. Small amounts of acid, glycerol, alcohol,

acetanilide and
H 3 PO 4 are often used as stabilizers to 0.0303
100=0.303 ( w/ v)
check its decomposition.
10
Red Alert
Red Alert
13. STRENGTH OF HYDROGEN PEROXIE SOLUTION
Since Eq. wt. of
H 2 O2 =17, Mol. wt. of H 2 O2 =34
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Normality of the given H 2 O2 solution B.


H 2 O2 can act as a reducing agent

30.3 C.
H 2 O2 has acidic properties
=1.79 N
17 H 2 O2 has basic properties
D.
Molarity of given
H 2 O2 solution 14. Which of the following acts as both reducing and
oxidising agent?
30.3 A.
H 2 SO 4 B.
H 2 O2
=0.89 N
34
C. KOH D.
KMnO 4
EXAMPLE
EXAMPLE:1 The percentage by weight of hydrogen in
H 2 O2 is
A. 5.88 B. 6.25
C. 25 D. 50
SOLUTION: Mol mass of
H 2 O2=21+16 2

=34
2
Percentage of hydrogen = 100 =
34

100
=5.88
17
Check Your Grasp
10. The boiling point of heavy water is
A. 1000 C B. 103.40 C

C. 101.40 D. 1040 C

11. Decomposition of
H 2 O2 is prevented by

A. NaOH B.
MnO2
C. acetanilide D. oxalic acid
12. The structure of
H 2 O2 is
A. open book like B. linear
C. closed book D. pyramidal
13. Which of the following statement is incorrect?
A.
H 2 O2 can act as an oxidising agent

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