Hydrogen gas is manufactured by

(1) Electrolysis of NaOH solution with Ni or Fe electrode:

2H2O  2H2 + O2
(2) Catalytic reduction of steam by coke, or by CO using Fe2O3 catalyst (Bosch
process):

750 K
C + H2O CO + H2 (water gas)

670-770 K
CO + H2O CO2 + H2
Fe2O3

(3) Catalytic oxidation of hydrocarbons with steam at 1200 K in the presence

of nickel catalyst, followed by oxidation of CO to CO2 by steam at 670 K:
Ni, 1200 K
CnH2n+2 + nH2O nCO + 2nH2

Natural gases are mainly mixtures of CH4, C2H6 and H2. The alkanes are
oxidized to CO with steam using alumina as catalyst. The product is called
syntetic fuel gas. CO is oxidized further to CO2 as in Bosch process.
Al2O3
CH4 + H2O CO + 3H2O
Al2O3
C2H6 + 2H2O 2CO + 5H2
(4) Cracking of petroleum, in which higher alkanes and cycloalkanes give
lower hydrocarbons abd aromatic compounds with the release of hydrogen
(reaction (6) above).
(5) As a hydroproduct in other industrial operations like manufacture of
NaOH, or of Cl2 from saturated NaCl.

Preparation of Pure Hydrogen

Pure hydrogen is prepared by (i) dissolving pure magnesium metal in pure
dilute HNO3, or (ii) electrolysis of warm Ba(OH)2 solution with nickel
electrodes in a U-tube.
Commercial hydrogen has H2S, CO, CO2, and O2 as the main impurities. It
is purified as follows:
(a) Caustic potash (KOH) solution absorbs H2S and other sulphur com-
pounds
H2S + 2KOH  K2S + 2H2O
(b) Ammoniacal copper formate absorbs CO completely:
[Cu(NH3)4]2+ + HCOO- + 2CO  [Cu(CO)2(OOCH)]+ + 4NH3
(c) CO2 is removed by absorption in water under pressure to obtain soda
water. Residual CO2 is absorbed in aqueous ethanolamine solutions:
2HOCH2CH2NH2 + CO2 + H2O  (HOCH2CH2NH3+)2CO32-