HYDROGEN

A. Position in Periodic Table

Hydrogen can be considered to belong to

the following group :
a) Group I A or the alkali metal group
b) Group VII A or the halogen family
c) Group IV A or the carbon family
 A. Position in Periodic Table
Similarity with alkali metals :
Loss of valence shell electron gives +1 ion (H+) like Li+, Na+, K+, etc
Differences with alkali metals :
1) Alkali metals are highly electropositive and extremely reactive
elements even at room temperature. Hydrogen is inert in room
temperature in the absence of catalyst
2) Alkali metals have very low ionization energies (520 to 375 kJ mol-1)
and electronegativities (0,7) in comparison with hydrogen (IE = 1310
kJ mol-1 and electronegativity = 1,6)
3) Alkali metals form ionic compounds containing M+ ions. Hydrogen
compounds are covalent or contain solvated ions, e.g. H3O+, NH4+,
ions
 A. Position in Periodic Table
Similarities with halogens :
1) By accepting one electron, hydrogen atom forms hydride ion H-, having
noble gas configuration 1s2. The electron affinity of hydrogen is +73 kJ
mol-1. Halogens have positive electron affinity and form stable halide
anions having noble gas configuration
2) Electrolysis molten NaX (X = H, Cl, Br, I) liberates the nonmetal at the
anode
3) Metal hydrides and halides are similar : SiH4 and SiCl4, CH4 and CCl4,
etc. In fact, halogens substitute hydrogen atoms in hydrocarbons, and
the covalent halides can be converted into covalent hydrides on reaction
with LiAlH4.
4) In the elemental state, both form diatomic molecules : H2, Cl2, Br2, etc
5) Hydrogen halides are similar to the interhalogen compounds in
properties, e.g HCl has almost average properties of H2 and Cl2
6) Ionization energy of hydrogen tom is comparable with that for halogens
(Cl = 1250 kJ mol-1)
 A. Position in Periodic Table
Differences with halogens :
1) Dissociation energy of H2 (436 kJ mol-1) is very high (Cl2 = 240, F2 =
155 kJ mol-1). Its electron affinity is very low (H = 73, F = 322, Cl =
348 kJ mol-1).
2) Ionic radius of hydride ion is very large (210 pm) for Z = 1 (Br- = 196
pm, I- = 216 pm)
3) Halides can act as bridging ligands for polynuclear complexes,
hydrides cant.
4) Halogens show oxidation states of +I, III, V, and VII. Hydrogen
shows only +I or I.
5) The maximum coordination number for hydrogen is two in hydrogen
bonding, that for halogens can be up to seven as in IF7.
6) Hydride ion is a strong Bronsted-Lowry base but halides ae very
weak Bronsted-Lowry base.
 A. Position in Periodic Table

Similarities with Carbon :

1) Metal hydrides and metal alkyls are similar in nature
and bonding, e.g ionic LiH and LiMe
2) When hydrogen and carbon form maximum number of
covalent bonds (one in HX and four in CX4) they attain
the nobel gas configuration and they have neither lone
pair of electrons (they are not Lewis bases) nor any low
energy orbitals to accept lone pair of electrons (not
Lewis acids)
 B. Isotopes of Hydrogen
Hydrogen has three isotopes : 1H, 2H or
deuterium, and 3H or tritium
These isotopes differ in the number of
neutron present, and hence the mass
number are also different.
The hydrogen isotopes have been given
different names and symbol because their
physical properties are quite different
 B. Isotopes of Hydrogen
1. Deuterium
Deuterium is prepared from the oxide D2O or
heavy water, which is prepared either by :
a. Electrolysis of water
b. Exchange reaction
The deutero compounds, in which the hydrogen
atom is replaced by the deuterium atom, can be
readily prepares from D2O by chemical
reactions.
 B. Isotopes of Hydrogen
1. Deuterium (continued)
Heavy water is the starting materials for other deutero compounds.
Its reaction are similar to those of water. Some typical reactions are :
a. With acidic and basic oxides to form deuteroacids DNO3, D2SO4,
D3PO4, etc
b. Deuterolysis of magnesium-nonmetal binary compounds to form
deutoride of nonmetals : ND3, PD3, B2D6, SiD4, etc
c. With anhydrous salts to form adduct containing D2O of
crystallization
d. Electrolysis to deuterium gas which forms DX with halogens X2
Deuterium is also used as a source of deutrons, projectiles for
nuclear reactions
Deuterium oxides is used as a moderator for the production of
thermal neutron
Though beneficial to health in small amount, pure D2O is poisonous
 B. Isotopes of Hydrogen
1. Deuterium ( continued)
a. N2O5 + D2O 2 DNO3
SO3 + D2O D2SO4
P4O10 + D2O 4 D3PO4
CaO + D2O Ca(OD)2
b. Mg3A2 + 6 D2O 3 Mg(OD)2 + 2 AD3 (A = B, N, P, As)
Mg2G + 4 D2O 2 Mg(OD)2 + GD4 (G= C, Si, Sn)
c. CuSO4 + 5 D2O CuSO4.5D2O
d. 2 D2O 2 D2 + O2
D2 + X2 2 DX (X = F, Cl, Br)
 B. Isotopes of Hydrogen
2. Tritium
In air, tritium is formed by the neutron bombardment of
14N :

Tritium can also be prepared by :

a. Deutron bombardment of D3PO4 or (ND4)2SO4
b. Bombardment by beryllium by deutrons from a
cyclotron
c. Slow neutron bombardment of lithium or lithium salts
 B. Isotopes of Hydrogen
2. Tritium (continued)
a.

b.

c.
 C. Molecular Hydrogen
Hydrogen gas can be prepared by :
a. The action of active metals (more electropositive than
tin) on dilute mineral acids
b. The action of alkali and alkaline earth metals on water
c. Passing steam over hot Fe, Ni, Co, Mn, Zn, or Mg
(boiling water)
d. Boiling metalloids and amphoteric metals with alkalis
e. The electrolysis of ionic hydrides LiH or CaH2
f. Electrolysis of water with Pt/C electrode and Na2SO4
salt as catalysator
g. etc
Find the reactions !
 C. Molecular Hydrogen
Hydrogen gas is manufactured by :
a. Electrolysis of electrolysis of NaOH solution with Ni or Fe
electrodes
b. Catalytic reduction of steam by coke, or by CO using Fe2O3
catalyst (Bosch process)
c. Catalytic oxidation of hydrocarbons with steam at 1200 K in the
presence of Ni catalyst, followed by the oxidation of CO to CO2 by
steam at 670 K
d. Cracking of petroleum, in which higher alkanes and cycloalkanes
give lower hydrocarbons and aromatic compounds with release of
hydrogen
e. As a byproduct in other industrial operations like manufacture of
NaOH
Find the reactions !
 C. Molecular Hydrogen

Pure hydrogen is prepared by :

a. Dissolving pure magnesium metal in
pure dilute HNO3
b. Electrolysis of warm Ba(OH)2 solution
with nickel electrodes in U-tube
Commercial hydrogen has H2S, CO, CO2,
and O2 as the main impurities.
Find the purification methods !
 C. Molecular Hydrogen
Properties of hydrogen :
a. Hydrogen is colorless, odorless, and tasteless
gas
b. It is slightly soluble in water
c. It is the lightest of all the known elements
d. It is unreactive at room temperature, in the
absent of any catalyst. At elevated
temperatures, it reacts with many substances
 D. Uses of Hydrogen
Being the essential element for all living matter
It is used for hydrogenation of oils
It is used in reductions of metals like Mo, W, etc
It is used in desulphurization of petrol
It is used as raw material in the manufacture of
ammonia, methanol, HCl, plastics, and fuel gases
It is used as a coolant for steam driven turbines
It is used as a filling material for research balloons.
In conjuction with hydrogen peroxide, it can be used as
rocket fuel
 E. Classification of Hydrides
Saline or ionic hydrides
Hydrogen form ionic hydrides with very
electropositive metals
Covalent hydrides
Hydrogen form covalent hydrides with all
nonmetal elements
Metallic hydrides
Hydrogen form metallic hydrides with
some transition metals
 F. Hydrates
Hydrates : solid formed by certain compound
molecules and certain numbers of water
molecules
The water molecules bonded to cation through
oxygen molecules (a) or to anion/rich-electron
species through hydrogen atoms
Generally, the hydrate compound will release its
crystal water when heated and formed
anhydrous compound which has different
properties
 G. Hard and Soft Water
Water containing soluble salts of Ca2+ and Mg2+ is called hard water
as it does not form lather easily with soap solution. Soap is chiefly a
mixture of sodium salts of long chain fatty acids, mainly stearic and
oleic acids, which form lather with water by decreasing its surface
tension. Ca2+ and Mg2+ precipitate the stearate and oleate ions so
that lather is not formed.
If water contains the hydrogen carbonates HCO3- of these ions, the
hardness can e removed by boiling when the carbonates get
precipitated. Such hardness is called temporary hardness.
M(HCO3)2 MCO3 + CO2 + H2O ( M = Mg or Ca)
If the hardness is due to the presence of sulphates or chlorides of
these ions , it is called permanent hardness and can not removed by
boiling.
Water from natural sources may contain salts beneficial to health. It
is then called spa or mineral water and is used for making beers,
drinks, and tonics.
 G. Hard and Soft Water
The process of removing the hardness from water is called water
softening. The chief methods used are :
a. Precipitation methods : addition of calculated amount of lime for
temporary hardness or sodium carbonate to permanent hardness
precipitates the metal carbonates.
Mg(HCO3)2 + Ca(OH)2 MgCO3 + CaCO3 + 2 H2O
MgSO4 + Na2CO3 MgCO3 + Na2SO4
b. Exchange method : The Ca2+ and Mg2+ ions can be exchanged by
H+ ion passing through cation exchanger. He exchanger used may
be naturally occurring zeolites or synthetic permutits (
aluminosilicates). The exhausted exchangers can be regenerated by
passing strong solution of NaCl.
Na2(zeo) + Ca2+ Ca(zeo) + 2 Na+
 G. Hard and Soft Water
c. Phosphate methods or the Calgon process : condensed
polyphosphates can be used for he complexation of metal
cationas. Generally called the hexametaphosphate
implying P6O18-6 ion. The removal of hardness can be
expressed as :
Na6P6O18 2 Na+ + P6O18Na42- (ionization)
P6O18Na42- + M2+ P6O18Na2M2- + 2 Na+ (complexation
of M2+ as
the anions)
P6O18Na2M2- + M2+ P6O18M22- + 2 Na+
 H. Anomaly of Water

Density of liquid H2O is higher than ice

Maximum density of water at temperature
of 4 oC