Kech 202
Kech 202
Kech 202
CHEMISTRY
UNIT 9
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HYDROGEN
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HYDROGEN
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9.2 DIHYDROGEN, H2
9.2.1 Occurrence
Dihydrogen is the most abundant element in
the universe (70% of the total mass of the
universe) and is the principal element in the
Property
Hydrogen
Deuterium
Tritium
0.0156
1.008
2.014
3.016
Melting point / K
13.96
18.73
20.62
Boiling point/ K
20.39
23.67
25.0
0.09
0.18
0.27
0.117
0.197
0.904
1.226
435.88
443.35
74.14
74.14
1312
73
37
Density / gL
10
15
99.985
Enthalpy of bond
dissociation/kJ mol
at 298.2K
Internuclear distance/pm
277
208
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nH2O
1270K
Ni
Sodium zincate
278
1270K
CH4 ( g ) + H2 O ( g )
CO ( g ) + 3H2 ( g )
Ni
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C n H2n
e.g.,
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HYDROGEN
279
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2H2O(l);
H V = 285.9 kJ mol
H V = 92.6 kJ mol 1
H2 ( g ) + Pd2 + ( aq ) Pd ( s ) + 2H + ( aq )
yH2 ( g ) + M x O y ( s ) xM ( s ) + yH 2O ( l )
279
cobalt
CO ( g ) + 2H2 ( g )
CH3OH ( l )
catalyst
280
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9.5 HYDRIDES
Dihydrogen, under certain reaction conditions,
combines with almost all elements, except
noble gases, to form binary compounds, called
hydrides. If E is the symbol of an element then
hydride can be expressed as EHx (e.g., MgH2)
or EmHn (e.g., B2H6).
The hydrides are classified into three
categories :
(i) Ionic or saline or saltlike hydrides
(ii) Covalent or molecular hydrides
(iii) Metallic or non-stoichiometric hydrides
9.5.1 Ionic or Saline Hydrides
These are stoichiometric compounds of
dihydrogen formed with most of the s-block
elements which are highly electropositive in
character. However, significant covalent
character is found in the lighter metal hydrides
such as LiH, BeH2 and MgH2. In fact BeH2 and
MgH2 are polymeric in structure. The ionic
hydrides are crystalline, non-volatile and nonconducting in solid state. However, their melts
conduct electricity and on electrolysis liberate
dihydrogen gas at anode, which confirms the
existence of H ion.
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CHEMISTRY
anode
2H ( melt )
H2 ( g ) + 2e
Saline hydrides react violently with water
producing dihydrogen gas.
NaH ( s ) + H2 O ( aq ) NaOH ( aq ) + H2 ( g )
280
Problem 9.2
Would you expect the hydrides of N, O
and F to have lower boiling points than
the hydrides of their subsequent group
members ? Give reasons.
HYDROGEN
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9.6 WATER
A major part of all living organisms is made
up of water. Human body has about 65% and
some plants have as much as 95% water. It is
a crucial compound for the survival of all life
forms. It is a solvent of great importance. The
distribution of water over the earths surface
is not uniform. The estimated world water
supply is given in Table 9.2
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Solution
Although phosphorus exhibits +3 and +5
oxidation states, it cannot form PH5.
Besides some other considerations, high
aH value of dihydrogen and egH value
of hydrogen do not favour to exhibit the
highest oxidation state of P, and
consequently the formation of PH5.
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Solution
On the basis of molecular masses of NH3,
H2O and HF, their boiling points are
expected to be lower than those of the
subsequent group member hydrides.
However, due to higher electronegativity
of N, O and F, the magnitude of hydrogen
bonding in their hydrides will be quite
appreciable. Hence, the boiling points
NH3, H2O and HF will be higher than the
hydrides of their subsequent group
members.
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281
Source
% of Total
Oceans
97.33
0.008
2.04
Ground water
0.61
Lakes
0.009
Soil moisture
0.005
0.001
0.0001
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CHEMISTRY
18.0151
20.0276
Melting point/K
273.0
276.8
Boiling point/K
373.0
374.4
285.9
294.6
40.66
41.61
6.01
276.98
1.0000
Viscosity/centipoise
0.8903
2
1
cm )
1.107
78.06
5.7 10
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1.1059
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78.39
284.2
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H2 O
1
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Property
282
HYDROGEN
283
3+
Cu ( H2O )4
2+
SO2
4 .H2 O in CuSO 4 .5H 2 O,
Problem 9.4
How many hydrogen-bonded water
molecule(s)
are
associated
in
CuSO4.5H2O?
( aq ) + NH 4 ( aq )
+
Solution
Only one water molecule, which is outside
the brackets (coordination sphere), is
hydrogen-bonded. The other four
molecules of water are coordinated.
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H2 O ( l ) + H2 S ( aq ) H3O + ( aq ) + HS ( aq )
The auto-protolysis (self-ionization) of water
takes place as follows :
H2O ( l ) + H2O ( l ) H3O + ( aq ) + OH ( aq )
acid-1
base-2
acid-2
base-1
(acid)
(base)
(conjugate (conjugate
acid)
base)
(2) Redox Reactions Involving Water: Water
can be easily reduced to dihydrogen by highly
electropositive metals.
2H2O ( l ) + 2Na ( s ) 2NaOH ( aq ) + H2 ( g )
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Cr ( H2O )6 3Cl
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H2 O ( l ) + NH3 ( aq ) OH
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CHEMISTRY
2
Na 6 P6 O18 2Na + + Na 4 P6 O18
(M = Mg, Ca)
2
M2 + + Na 4 P6 O18
[ Na 2 MP6 O18 ]
+ Mg ( OH )2 +2H2O
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2+
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2NaZ ( s ) + M2 + ( aq ) MZ 2 ( s ) + 2Na + ( aq )
(M = Mg, Ca)
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2+
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Heating
Ca ( HCO3 )2
CaCO3 +H2O + CO2
+ 2Na +
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Heating
Mg ( HCO3 )2
Mg ( OH )2 + 2CO2
2RH ( s ) + M2+ ( aq ) MR 2 ( s ) + 2H + ( aq )
+
In this cation exchange process, H exchanges
+
2+
2+
for Na , Ca , Mg and other cations present
in water. This process results in proton release
and thus makes the water acidic. In the anion
exchange process:
HYDROGEN
285
H2 / Pd
( oxidised product )
(s)
+ OH ( aq )
+
3
RNH .X
H + ( aq ) + OH ( aq ) H2O ( l )
The exhausted cation and anion exchange
resin beds are regenerated by treatment with
dilute acid and alkali solutions respectively.
9.7 HYDROGEN PEROXIDE (H2O2)
Hydrogen peroxide is an important chemical
used in pollution control treatment of domestic
and industrial effluents.
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9.7.1 Preparation
It can be prepared by the following methods.
(i) Acidifying barium peroxide and removing
excess water by evaporation under reduced
pressure gives hydrogen peroxide.
( s ) + X ( aq )
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RNH .OH
O2 ( air )
H2 O 2 +
2 ethylanthraquinol
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+
3
RNH 3+ .OH ( s )
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RNH 2 ( s ) + H 2 O ( l )
Hydrolysis
Problem 9.5
Calculate the strength of 10 volume
solution of hydrogen peroxide.
Solution
10 volume solution of H2O2 means that
1L of this H2O2 solution will give 10 L of
oxygen at STP
2H2O2 ( l ) O2 ( g ) + H2O ( l )
234 g
22.7 L at STP
68 g
On the basis of above equation 22.7 L of
O2 is produced from 68 g H2O2 at STP
10 L of O 2 at STP is produced from
68 10
g = 29.9 g
22.7
30 g H2O2
Melting point/K
272.4
Boiling point(exrapolated)/K
423
Viscosity (290K)/centipoise
Vapour pressure(298K)/mmHg
Density (solid at 268.5K)/g cm
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1.44
1.25
1.9
1.64
cm
70.7
1
5.1 10
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9.7.3 Structure
Hydrogen peroxide has a non-planar
structure. The molecular dimensions in the gas
phase and solid phase are shown in Fig 9.3
2Fe3+ ( aq ) + 2H2O ( l )
CaC2 + 2D2O C2 D2 + Ca ( OD )2
SO3 + D2O D2 SO4
2H2O + 2OH
9.7.5 Storage
H2O2 decomposes slowly on exposure to light.
2H2 O2 ( l ) 2H2 O ( l ) + O2 ( g )
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HYDROGEN
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Table 9.5 The Energy Released by Combustion of Various Fuels in Moles, Mass and Volume
Energy released on
combustion in kJ
state)
Dihydrogen
(in gaseous
state)
Dihydrogen
(in liquid)
LPG
CH4 gas
Octane
(in liquid
state)
per mole
286
285
2220
880
5511
per gram
143
142
50
53
47
12
9968
25590
35
34005
per litre
SUMMARY
Hydrogen is the lightest atom with only one electron. Loss of this electron results in an
elementary particle, the proton. Thus, it is unique in character. It has three isotopes,
1
2
3
namely : protium (1H), deuterium (D or 1H) and tritium (T or 1H). Amongst these three,
only tritium is radioactive. Inspite of its resemblance both with alkali metals and halogens,
it occupies a separate position in the periodic table because of its unique properties.
Hydrogen is the most abundant element in the universe. In the free state it is almost
not found in the earths atmosphere. However, in the combined state, it is the third most
abundant element on the earths surface.
Dihydrogen on the industrial scale is prepared by the water-gas shift reaction from
petrochemicals. It is obtained as a byproduct by the electrolysis of brine.
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288
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EXERCISES
288
9.1
Justify the position of hydrogen in the periodic table on the basis of its electronic
configuration.
9.2
Write the names of isotopes of hydrogen. What is the mass ratio of these isotopes?
9.3
Why does hydrogen occur in a diatomic form rather than in a monoatomic form
under normal conditions?
9.4
9.5
9.6
(i)
H 2 ( g ) + M m O o ( s )
(ii)
CO ( g ) + H 2 ( g )
catalyst
HYDROGEN
289
(iii)
C3H8 ( g ) + 3H2O ( g )
catalyst
(iv)
heat
Zn ( s ) + NaOH ( aq )
9.8
9.9
9.10
Do you expect the carbon hydrides of the type (CnH2n + 2) to act as Lewis acid or
base? Justify your answer.
9.11
9.12
How do you expect the metallic hydrides to be useful for hydrogen storage?
Explain.
9.13
How does the atomic hydrogen or oxy-hydrogen torch function for cutting and
welding purposes ? Explain.
9.14
Among NH3, H2O and HF, which would you expect to have highest magnitude of
hydrogen bonding and why?
9.15
Saline hydrides are known to react with water violently producing fire. Can CO2,
a well known fire extinguisher, be used in this case? Explain.
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9.7
9.16
9.17
9.18
9.19
Consider the reaction of water with F2 and suggest, in terms of oxidation and
reduction, which species are oxidised/reduced.
9.20
(vi) Ca 3 N 2 ( s ) + H2O ( l )
Classify the above into (a) hydrolysis, (b) redox and (c) hydration reactions.
9.21
289
9.22
9.23
Discuss the principle and method of softening of hard water by synthetic ionexchange resins.
9.24
9.25
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CHEMISTRY
9.27
Is demineralised or distilled water useful for drinking purposes? If not, how can
it be made useful?
9.28
9.29
9.30
Knowing the properties of H2O and D2O, do you think that D2O can be used for
drinking purposes?
9.31
9.32
How can saline hydrides remove traces of water from organic compounds?
9.33
What do you expect the nature of hydrides is, if formed by elements of atomic
numbers 15, 19, 23 and 44 with dihydrogen? Compare their behaviour towards
water.
9.34
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9.35
9.36
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9.26
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(i) hydrogen economy (ii) hydrogenation (iii) syngas (iv) water-gas shift reaction
(v) fuel-cell ?
290