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Synopsis :
Hydrogen is the most abundant element in the universe.
It is the 9th most abundant element in the earth's crust.
It occurs only in the combined state except in volcanic gases where it occurs in free state.
It is the first element in the periodic table.
It is the lightest of all the elements.
It is the only element without neutrons i.e. Protium.
It is the element with ambiguious position in the periodic table, as it resembles both I-A and
VII-A group elements.
Hydrogen should belong to the s-block as its electron configuration is 1s1.
The properties in which hydrogen resembles alkali metals are
a) Like alkali metals it has one electron in s-orbital of valence shell.
b) Like Alkali metals, it forms H+ ion.
c) Like Alkali metals it forms monoxides and peroxides.
d) Like Alkali metals, it acts as reductant.
The properties in which Hydrogen resembles Halogens are
a) Like Halogens it exists as diatomic molecule (H2)
b) Like Halogens it gains one electron to attain inert gas configuration
c) The I.P value of "H" is similar to that of Halogens.
d) Like halogens it forms univalent anion i.e H.
Hydrogen has 3 isotopes. They are
Protium
1
1H
Deuterium
1H
Tritium
1H
Theoritically the number of possible Hydrogen molecules is six. They are H2, D2, T2, HD, HT
and DT.
Ordinary Hydrogen contains only 0.02% Deuterium.
Hydrogen and Deuterium can be separated by gas diffusion principle.
Hydrogen is more reactive than Deuterium.
All the isotopes of Hydrogen have
a) same chemical properties
b) same atomic radii
c) same bond lengths
The isotopes of Hydrogen differ widely due to large difference in mass numbers.
a) Number of neutrons b) Chemical reactivity
1
c) Physical properties
d) Nuclear radii
e) Bond energy
The properties or physical constants which are lower for hydrogen than that of deuterium are
i) Molecular weight
ii) Boiling point
iii) Melting point
iv) Latent heat of fusion
v) Latent heat of vaporization
vi) Bond energy
vii) Activation energy
Chemical reactivity is higher for hydrogen than that of Deuterium.
On electrolysis of water, H2 is released six times faster than that of D2.
Ordinary Hydrogen contains Tritium and protium in the ratio 1 : 1017.
Tritium can be obtained in the nuclear transformations such as
14
1
12
3
7N + on 6C + 1T (occurs in nature)
6
1
4
3
3Li + on 2He + 1T (takes place in nuclear reactors)
The radioactive isotope of Hydrogen is Tritium. It is a beta emitter and its half life is 12.26
years
3
3
0
1T 2 He + - 1e ( - particle)
Tritium is harmless, as it emits only low energetic -radiation and will not emit harmful -rays.
In the study of mechanism of various chemical reactions, Deuterium and Tritium are used as
tracers.
As the mass number increases the chemical reactivity decreases. So chemically least reactive
isotope of Hydrogen is Tritium.
Uses of Hydrogen
Hydrogen is used
i) in the manufacture of chemicals
ii) in metallurgy
iii) as a source of atomic energy
iv) as a fuel.
a) Synthesis of Ammonia by Haber's process.
ZZZ
X
N2(g) + 3H2(g) YZZ
Z 2 NH3(g)
b) Preparation of HCl
water
ZnO.CrO
water gas
(catalyst )
e
At cathode : O2 + 2H2O 4
4OH
Cell reaction : 2H2 + O2 2H2O
The efficiency of fuel cells is very high because the heat energy is directly converted into
electrical energy. Theoretically the efficiency of fuel cell should be 100 % but practically an
efficiency
of
60 - 70% has been achieved so far.
Hydrogen is used as a reducing agent in the extraction of heavier metals like Molybdenum and
Tungsten.
WO3 + 3H2 W + 3H2O
The energy emitting from sun and stars is due to nuclear fusion reactions involving Hydrogen
nuclei.
Fusion reaction
2
2
4
1H + 1H 2He
Energy released
23 108 KJ / mole of
3
"He"
+ 1H 2He
1
+ 0n
17.2 108 KJ / mole of
"He"
41H1 2He4 + 2
0
1e
26 108 KJ / mole of
"He"
1H
673K
2K + H2
2KH
1073 K
CaH2
Ca + H2
1123 K
SrH2
Sr + H2
These are white colourless solids (crystalline) having high melting point and boiling point
easily decomposed by water, alcohol, CO2 (or) SO2
decompose
at
2H(molten)
H2(g) + 2e
This reaction provides chemical evidence for the presence of H in these hydrides
This type of hydrides are formed only by elements with electronegativity value that is less than
2.1.
Hydrogen compounds of high electropositive metals may be regarded as the metal hydride.
The density of these hydrides is greater than that of the metal from which they are formed.
These ionic hydrides are stoichiometric and have high heats of formation.
4
HCOONa + C
2CO + NaH
SiCl4 + 4NaH
SiH4 + 4NaCl
4) Reduces organic acids to alcohols
3H2 + N2 2NH3
5
3) By reduction of certain compounds by nascent hydrogen (or) by using reducing agent like
LiAlH4 (ether solution)
AsCl3 + 6(H) AsH3 + 3HCl
ether
SnCl4 + LiAlH4
LiCl + AlCl3 + SnH4
s tan nane
Element
Group No. in
the P.T.
Formula of the
hydride
III (13)
B2H6
Diborane (6)
Diborane
IV (14)
CH4
Methane
Methane
V (15)
NH3
Azane
Ammonia
V (15)
PH3
Phosphane
Phosphine
As
V (15)
AsH3
Arsane
Arsine
Sb
V (15)
SbH3
Stibane
Stibine
Vi (16)
H2O
Oxidane
Water
VI (16)
H 2S
Sulphane
Hydrogen sulphide
VII (17)
HF
Hydrogen Fluoride
Hydrogen fluoride
Cl
VII (17)
HCl
Hydrogen chloride
Hydrogen chloride
IUPAC
Common
Molecular hydrides are soft, have low melting point and low boiling point.
Molecular hydrides are volatile in nature have low electrical conductivity.
METALLIC HYDRIDES:
Most of the d-block elements and f block elements from metallic hydrides on reacting with
hydrogen.
Ex. CrH, CrH2, ZnH2, ThH2
Metallic hydrides are normally prepared by heating the metal with hydrogen under high
pressure.
Most of the metallic hydrides are metallic conductors and have variable composition.
These hydrides have properties similar to those of parent metals.
Metallic hydrides are hard, have metallic lustre and have magnetic properties.
The density of these hydrides is less than that of the parent elements.
6
Semiwater gas:
Preparation : A mixture of steam and air passed over red hot layers of coal.
Composition : H2 10 12%
CO 25 28%
CO2 4 5%
50 55%
N2
CH4 1 2%
Calorific value : 75.24 KJ mol1
Carburetted water gas:
Preparation : Hydrocarbons from the cracking of petroleum oils are mixed with water gas.
Composition : water gas + hydrocarbons
Calorific value : 15,048 KJ mol1
FUEL CELLS:
In the combination of fuel gases like H2, CO and methane energy produced is converted into
electrical energy in the fuel cells.
A fuel cell consist of porous carbon electrodes suspended in NaOH solution. H2 and O2 gases
are bubbled at the surface of electrodes.
Electrodes are embedded with suitable catalyst.
The electrode reaction in hydrogen fuel cell
+4e
At cathode : O2(g) + 2H2O(l)
4OH (aq)
At anode
2e
2H2O(aq)
: 2[H2(g) + 2 OH(aq)
In fuel cells the heats of combustion of fuel materials are directly converted into electrical
energy.
In the traditional methods of generating electricity by H2 (or) C by nuclear reactor there is a
loss of energy in such process.
The fuel cell have more efficiency and prevents the atmospheric pollution.
In spite of the fuel value of hydrogen (heat combustion of H2 = 242 KJ mol1). It is not used
frequently due to the following reasons.
1) Hydrogen elements is not present in the free state in nature.
2) The storing and Transportation of hydrogen gas is dangerous and involves risks.
WATER :
Water is called as universal solvent because it is an excellent solvent for ionic compounds and
polar covalent compounds.
3/4th of earth's surface is covered by water.
Purest form of natural water is rain water.
Potable water means which is for drinking.
Hardness of water:
Chemically soap is sodium stearate.
Water which gives good lather readily with soap is known as soft water.
8
Mg(HCO3)2
MgCO3 + H2O + CO2
In Clark's method temporary hardness can be removed by adding a calculated quantity of milk
of lime. Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
If excess of lime is added it will cause permanent hardness.
Using Na2CO3 both temporary and permanent hardness can be removed.
The methods used for removing permanent hardness are
a) Permutit method
b) Ion exchange method
c) Calgon method
a) Permutit is an artificial zeolite. Chemically permutit is hydrated sodium aluminum ortho
silicate. Its formula is Na2 Al2 Si2 O8. x H2O.
b) Gan's permutit process is also known as Base exchange process.
Na2Al2Si2O8.xH2O + Ca2+ CaAl2Si2O8.xH2O + 2Na+
The exhausted permutit is regenerated by treating 10% NaCl solution [Brine solution]
Calgon is sodium hexameta phosphate. Its formula is Na2 [Na4(PO3)6)] or (NaPO3)6
Calgon removes hardness by forming complex compounds with the Ca2+ and Mg2+ ions of hard
water or by adsorption.
Ion exchange method:
Deionised water is obtained in ion exchange method. It is free from all ions. It can be used in
place of distilled water.
Cation exchange resin is RCOOH or RSO3H and anion exchange resin is RNH3OH.
weight of CaCO3
106
weight of H2O
th
D 2 + O 2
Na
D 2 +
Na O
CaO
NaOD Sodium-deuteroxide
NaOD
Ca(OD)2 Calcium deuteroxide
SO3
Deutero Ammonia
Ca3P2
Ca(OD) 2 + PD 3
Deutero phosphine
CaC2
Ca(OD)2 + C2D2
Deutero acetylene
Al C
3
4
Al(OD) 3 + CD 4
Deutero methane
Be(OD)2 + CD 4
Be2C
Deutero methane
Uses of D2O:
i) D2O is used as a moderator in nuclear reactors to slow down the neutrons.
ii) As tracer in studying reaction mechanisms.
Ex.: Mechanism of electrophilic substitutions of Aromatic compounds, Metabolic processes.
11
At cathode
2H + + 2e
Re duction
H2
At anode
2HSO4
Oxidation
H2S2O8 + 2e-
Sample of H2O2
Normality, N
1.7% w/v
0.5 M
1N
3.4% w/v
1M
2N
6.8% w/v
2M
4N
10 vol. H2O2
3% w/v
0.89 M
1.78 N
30% w/v
8.9 M
17.8 N
Perhydol is 30% (w/v). Its Morality is 8.9M Normality is 17.8 N and it contains 300g/lit (or)
0.3g/ml.
On long standing or on heating H2O2 undergoes decomposition. The equation for the
decomposition of H2O2 is
2H2O2 2H2O + O2
13
14
H2O2
Oxidant
The standard reduction potential values indicate that H2O2 is a strong oxidising agent in acidic
medium and weak oxidising agent in basic medium.
Oxidising properties of H2O2:
black PbS
H 2 O + PbSO 4 white
Fe 2 (SO 4 )3 + H 2 O
Ferrous salts
FeSO 4 +H2SO 4
KI+H O
2 l 2 + KOH
Na SO
2
3
H2O + Na2SO 4
Sod.sulphi te
KNO
H2O2
H 2 O + KNO 3
Pot.Nitrite
Na AsO
3
3
H 2 O + Na 3 AsO 4
sod. Arsenite
K [Fe(CN)
6
4
H2O + K 3 [Fe(CN)6 ]
pot.Ferrocyanide
potassium ferri-cyanide
acidified K Cr O
7
2 2
(or )chromicacid
in ether
HCHO
HCOOH + H 2
alkaline pyrogallol
C H / FeSO
4
66
C 6H5 OH + H 2 O
The bleaching action of H2O2 is due to its oxidising nature. H2O2 H2O + (O)
H2O2 is used to bleach silk, wool, ivory and hair.
H2O2 is used to bleach black hair to golden yellow colour under the common name Auricome.
The fundamental equation for reducing property of H2O2 is
H2O2 + (O) H2O + O2
In both acidic and basic media, H2O2 shows reducing properties as
(oxidation)
H2O2 O2 + 2H+ + 2e (E = 0.67 V )
(acidic )
2OH
(oxidation) O + 2H O + 2e
+
H 2 O 2
2
2
(basic )
(E = +0.08V )
15
acidified KMnO
Cl
HCl + O 2
Br
HBr + O 2
moist Ag O
2
Ag + O 2
alkalineK [Fe(CN)
3
6
K 4 [Fe(CN)6 ] + O 2
pot Ferrocyanide
NaOCl
H2O
NaCl + O 2
NaOBr
NaBr + O 2
PbO
PbO + O 2
2 Mn2 + + O2
alkaline Fe3 + (Ferricsalts )
Fe 2+ (Ferrous ) + O
O 3 (disproportionation )
O2 + H2O
O
1
94 .48
1.48A
H
Open book
structure of H-
1110.301
16
17