Hydrogen and its compounds

Position of hydrogen in periodic table:

Hydrogen didn’t belong to any group in the periodic table. The properties of Hydrogen resembles
with both 1st and 17th group elements. It also shows some differences with both group 1 and 17
elements.

Similarities with group 1 and group 17 elements:

1. Electronic configuration:
General electronic configuration of group 1 elements is ns 1 and hydrogen also has 1s 1. Like
alkali metals, H has one electron in the valence shell.

Electronic configuration of 17th group elements is ns 2 np5. These elements should get one
electron to reach the noble gas configuration and H also get noble gas configuration by taking
one electron.

2. Electro positive/electron negative character:

Like first group elements H loses one electron and forms mono positive cation

H  H   e

Na  Na   e 

When hydrogen reacts with metals, it forms compounds similar to halogens as H is more
electro negative compared to alkali and alkaline earth metals. Examples: NaH, CaH2 and LiH

3. Oxidation state:
Like alkali metals, hydrogen exhibit +1 oxidation state in many of its compounds.

Like halogens, hydrogen exhibit -1 oxidation state in metal hydrides.

4. Reducing agent:
Like alkali metals, hydrogen also acts as a good reducing agent by losing its valence electron.

Fe3O4  4 H 2   3Fe  4 H 2O


CuO  H 2   Cu  H 2O
5. Combination with electron negative elements/ electro positive elements:
Alkali metals combine with more electron negative metals and forms compounds like NaCl,
Na2O and Na2S
Hydrogen also forms similar compounds HCl, H2O, H2S

Just like halogens, hydrogen also combines with alkali metals to form salt with similar
formula

NaH , LiH , CaH 2

NaCl , LiCl , CaCl2

Just like halogens, hydrogen also combines with non metals to form covalent compounds

CCl4, SiCl4 , GeCl4

CH 4 , SiH 4 , GeH 4

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 Hydrogen and its compounds

6. Atomicity of hydrogen is 2 just like halogens. Ionization energy of hydrogen is comparable to

IE values of halogens.

Differences between H and group 1 elements:

1. Ionization energy – IE value of H is very high in comparison with group 1 elements.

2. Existence of H+ - H+ doesn’t exist in aqueous solution. it exists as H9O4+ and is represented as

H3O+.

3. Difference in halides – H forms covalent hydrides but group 1 elements form ionic halides.

Differences between H and group 17 elements:

1. Least tendency of hydride formation – hydride will be formed only with group 1 and 2
elements.

2. Absence of lone pair of electrons – halogens possesses unpaired electrons in free state but
hydrogen doesn’t.

3. Nature of oxides – oxides of halogens are acidic but oxides of hydrogen are neutral

Isotopes of hydrogen:
Property Protium or hydrogen Deuterium or heavy hydrogen Tritium
1 2 3
Symbol 1H or H 1H or D 1H or T
No of protons 1 1 1
No of electrons 1 1 1
No of neutrons 0 1 2
% Abundance 99.985 0.015 10-15
Radio active nature Non radio active Non radio active Radio active

Isotopes show different physical properties but show same chemical properties. They differ only in
the rate of reactions. Heavier isotope undergoes reaction slowly and lighter one undergoes fast.

Ortho and para hydrogens:

Hydrogen molecule exists in two forms depending upon the direction of spin of two nuclei. When the
spins of two nuclei are in the same direction (parallel spins), dihydrogen is called ortho hydrogen
and when the spins of the nuclei are in the opposite direction (anti parallel spins), dihydroge is called
para hydrogen.

Spin isomerism is also found in other symmetrical molecules whose nuclei has spin momenta, e.g. D2,
N2, F2, Cl2. These isomers differ in physical properties like boiling points, specific heats, and thermal
conductivities because of the difference in the internal energy.

The para form has the lowest energy, and at absolute zero the gas contains 100% of para form. As the
temperature raised, some of the para form changes to ortho form. At higher temperatures the gas
contains 75% of ortho form.

Para hydrogen usually prepared by passing a mixture of two forms of hydrogen through a tube packed
with charcoal cooled to liquid air temperature. Para hydrogen prepared in this way can be kept for
weeks at room temperature in a glass vessel, because of ortho para conversion is slow in the absence
of catalysts. Suitable catalysts are charcoal, atomic hydrogen, metals such as Fe, Ni, Pt and Wand para
magnetic substances or ions such as O 2, NO, NO2, Co+2 and Cr2O3.

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 Hydrogen and its compounds

Hydrogen:
Preparation of dihydrogen (H2):
1. H2 can be produced in the laboratory by treating granulated Zn with either HCl or NaOH

Zn + 2HCl ® ZnCl2 + H 2

Zn + 2NaOH ® Na2 ZnO2 + H 2

2. Electrolysis of acidified water using Pt electrodes gives hydrogen. Pure hydrogen can be
produced by the electrolysis of warm aqueous Ba(OH)2 solution between Ni electrodes.

2H 2O(l) ¾Traces
¾¾¾¾¾
Electrolysis
of acid/base
® 2H 2 (g) + O2 (g)

3. It is obtained as a bi-product in the manufacture of NaOH and chlorine by the electrolysis of

brine (concentrated NaCl solution) solution.

At anode : 2Cl - ® Cl2 + 2e-

At cathode : 2H 2O + 2e- ® H 2 + 2OH -

Overall reaction : 2Cl - + 2H 2O ® Cl2 + H 2 + 2OH -

Na+ will not be participating in this reaction as Na is highly reactive. It acts as a spectator ion in this
reaction.

4. Reaction of steam on hydrocarbons or coke at high temperatures in the presence of catalyst yield
hydrogen

Cn H 2n+2 + nH 2O ¾1270
¾¾
Ni
K
® nCO + (2n + 1)H 2

CH 4 + H 2O ¾1270
¾¾
Ni
K
® CO + 3H 2

C(s) + H 2O(g) ¾1270

¾¾ K
® CO(g) + H 2 (g)

CO(g) + H 2O(g) ¾FeCrO

¾¾
673K
4
® CO2 (g) + H 2 (g)

The mixture of CO and H2 is called water gas. As the mixture of CO and H2 is used for the synthesis
of methanol and many hydrocarbons, it is also called as synthesis gas or syngas. The process of
producing syngas from coal (reaction 3) is

called coal gasification. The last reaction is called water gas shift reaction. Majority of the H2 can
be produced from petro chemicals.

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 Hydrogen and its compounds

Properties of hydrogen:
It is colourless, odourless, tasteless and combustible gas (inflammable gas). The bond dissociation
energy of H-H is very high. Because of this, H2 is inert at room temperature. At higher temperature it
does combine with almost all the elements.

It reacts with halogens to produce halogen halides (HF, HCl, HBr, HI). Reactivity with H2 reduces
from fluorine to iodine. With fluorine, reaction happens even in the dark but with iodine catalyst is
required.

H 2 (g) + X2 (g) ® 2HX(g); (X = F,Cl, Br, I )

It reacts with O2 to form water and the reaction is highly exothermic. With N 2 it gives ammonia
(Haber’s process).

2H 2 (g) + O2 (g) ¾catalyst

¾¾¾¾ or heating
® 2H 2O(l); DH = -285.9kJ mol -1

3H 2 (g) + N 2 (g) ¾673K

¾¾¾¾¾¾¾
, 200 atm, Fe(catalyst )
® 2NH 3 (l); DH = -92.6kJ mol -1

It combines with many metals at high temperature to produce metal hydrides. In metal hydrides
hydrogen shows -1 oxidation state. When metal hydride is added to water, hydrogen gas will be
produced.
H 2 (g) + 2M (g) ® 2MH (s); where M is alkali metal

MH (s) + H 2O(l) ® MOH (aq) + H 2 (g)

It reduces some metal ions in aqueous solution and oxide of the metals (less reactive than iron) into
corresponding metals.
H 2 (g) + Pd +2 (aq) ® Pd(s) + 2H + (aq)

yH 2 (g) + M xOy (s) ® xM (s) + yH 2O(l)

It can be used as reducing agent in presence of finely divided transition metals (Pd, Ni, Pt etc) in
several organic reactions. Metal acts as catalyst in these reactions.

i) Hydrogenation of vegetable oils using Ni as catalyst gives edible fats (margarine and
vanaspati ghee).
ii) Hydro formylation of olefins yield aldehydes, which further undergoes reduction to
give alcohols.
CH 2  CH 2  H 2 
Ni
 CH 3  CH 3

H 2  CO  RCH  CH 2  RCH 2CH 2CHO

H 2  RCH 2CH 2CHO  RCH 2CH 2CH 2OH

Uses of hydrogen:
1. It is used in the synthesis of NH3 which is used in the manufacture of HNO3 and nitrogen
fertilizers

2. It is used in the manufacture of vanaspati fats (from soya been, cotton seeds etc), metal
hydrides, hydrogen halides, in metallurgical process to reduce metal oxides to metals

3. Atomic hydrogen and oxy-hydrogen torches find use for cutting and welding purpose

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 Hydrogen and its compounds

4. Used as rocket fuel. Also used in the making of fuel cells

5. It is used in the manufacture of bulk organic chemicals particularly methanol

CO(g) + 2H 2 (g) ¾catalyst

¾¾
cobalt
® CH 3OH(l)

Hydrides:
Hydrogen forms hydrides with almost all elements except noble gases. Hydrides can be classified into
three types
(i) Ionic or Salt like hydrides:
These are formed when hydrogen combined with alkali or alkaline earth metals
(except Be). They are ionic in nature and they are used as reducing agents. Examples:
LiH, NaH, CaH2 etc.

BeH2 and MgH2 are polymeric in nature. LiH is unreactive and is used in the
synthesis of LiAlH4 (a complex hydride)
8LiH + Al2Cl6 ® 2LiAlH 4 + 6LiCl

2LiH + B2 H 6 ® 2LiBH 4

(ii) Covalent or Molecular hydrides:

When hydrogen reacts with more electron negative elements such as p block
elements, these hydrides will be formed. In these hydrides, hydrogen is linked with
other elements by covalent bonds. Examples: HCl, H2O, PH3 , NH3 etc. Covalent
hydrides further classified into three types. They are
B2 H6 – electron rich covalent hydride
CH4 – electron precise covalent hydride
NH3 – electron rich covalent hydride

(iii) Metallic or Non stoichiometric hydrides:

These hydrides are generally formed by hydrogen when combined with transition
metals (group 3,4,5), only Cr in group 6 and f block elements.

Group 7, 8, 9 of d block elements do not form hydrides at all. This is known as

hydride gap of d block.

In these compounds H atoms occupy interstitial positions in the metal lattice. The
composition of these hydrides may not correspond to simple whole number ratio and
therefore they are also called as non stoichiometric hydrides. The composition also
varies with conditions of temperature and pressure. These hydrides are also known as
interstitial hydrides. Examples: LaH2.87, YbH2.55, TiH1.5-1.8, ZrH1.3-1.75, VH0.56, NiH0.6-
0.7, PdH0.6-0.8, etc.

Hydrogen peroxide:
Preparation of H2O2:
From sodium peroxide or barium peroxide:

Na2O2 + H 2SO4 ® Na2 SO4 + H 2O2

This reaction is known as Merck’s method.

BaO2 .8H 2O(s) + H 2 SO4 (aq) ® BaSO4 (s) + H 2O2 + 8H 2O(l)

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 Hydrogen and its compounds

In this method, anhydrous BaO2 can’t be used since the precipitate BaSO4 forms a protective layer
around un reacted barium peroxide there by preventing the further reaction.

Hydrogen peroxide prepared in this method contains contains Ba +2 which act as catalyst for the
decomposition of H2O2. Even H2SO4 acts as a catalyst for decomposition of H2O2 therefore, the use of
weaker acids such as CO2 or H2CO3 and H3PO4 are preferred to H2SO4

BaO2 + H 2O + CO2 ® BaCO3 + H 2O

3BaO2 + 2H 3PO4 ® Ba3 (PO4 )2 + 3H 2O

All most all the metal impurities present in BaO 2 and which catalyse the decomposition of hydrogen
peroxide are removed as insoluble phospahates. So this H2O2 can be stored for longer duration.

Manufacture of H2O2:
Electrolysis of 50% H2SO4 using Pt as anode and graphite as cathode gives H2O2. The reactions
involved are

2H 2 SO4 ® 2H + + 2HSO4 -

At cathode :2H + + 2e- ® H 2

At anode :2HSO4 - ® H 2 S2O8 + 2e-

Peroxy disulphuric acid

Peroxy di sulphuric acid formed around anode is with drawn and then distilled with water under
reduced pressure. The low boiling H2O2 distils over along with water leaving behind high boiling
H2SO4 which is recovered and recycled.

H 2 S2O8 + H 2O ® H 2 SO4 + H 2 SO5

Peroxy mono sulphuric acid
H 2 SO5 + H 2O ® H 2 SO4 + H 2O2

H 2 S2O8 + 2H 2O ® H 2O2 + 2H 2 SO4

Modification:
Recently instead of 50% of H2SO4, equimolar mixture of H2 SO4 and ammonium sulphate is taken for
the electrolysis. The reactions involved are

(NH 4 )2 SO4 + H 2 SO4 ® 2NH 4 HSO4

2NH 4 HSO4 ® 2H + + 2NH 4 SO4 -

At cathode :2H + + 2e- ® H 2

At anode :2NH 4 SO4 - ® (NH 4 )2 S2O8 + 2e-

Peroxy disulphuric acid

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 Hydrogen and its compounds

Ammonium persulphate formed around anode is with drawn and distilled with water to give H2O2.

(NH 4 )2 S2O8 + 2H 2O ® 2NH 4 HSO4 + H 2O2

This process is now used only to prepare D2O2 in the laboratory.

K2 S2O8 + 2D2O ® 2KDSO4 + D2O2

By auto oxidation of 2-ethyl anthraquinol:
2-ethyl anthraquinol is oxidized to 2-ethyl anthra quinone and H2O2. O2 is used as oxidizing agent. 2-
ethyl anthra quinone can be reduced back to starting material by using H2/Pd. In overall reaction
oxygen and hydrogen only will be consumed.
OH O

CH3 O2 CH3
H2O 2
+
H2/Pd

OH O
Properties of H2O2:
(a) Decomposition:
It disproportionates to water and oxygen on heating or on exposure to light or on long standing.
This reaction can be catalyzed in presence of metals and alkali (present in glass containers). It is
stored in wax lined glass or plastic vessels.
Urea can be added as a stabilizer.

H 2O2 ® H 2O + O2 (b) acidic behavior:

it ionizes in water as

It’s acidic character can be confirmed with reactions with NaOH and Na 2CO3

2NaOH + H 2O2 ® Na2O2 + 2H 2O

2Na2CO3 + H 2O2 ® Na2O2 + H 2O + CO2

Oxidizing and reducing nature:

It acts as an oxidizing as well as reducing agent n both acidic and alkaline medium.
Oxidizing nature:
(i) In acidic medium:

2Fe+2 (aq) + 2H + (aq) + H 2O2 (aq) ® 2Fe+3 (aq) + 2H 2O(l)

PbS(s) + 4H 2O2 (aq) ® PbSO4 (s) + 4H 2O(l)

H 2 S + H 2O2 ® S + 2H 2O

K 2Cr2O7 + H 2 SO4 + 4H 2O2 ® 2CrO5 + K 2 SO4 + 5H 2O

2K 4 [Fe(CN )6 ] + H 2 SO4 + H 2O2 ® 2K 3[Fe(CN )6 ] + K 2 SO4 + 2H 2O

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 Hydrogen and its compounds

(ii) In basic medium:

2Fe+2 + H 2O2 ® 2Fe+3 + 2OH -

Mn +2 + H 2O2 ® Mn +4 + 2OH -
Reducing nature:
(i) In acidic medium:

K 2Cr2O7 + 4H 2 SO4 + 3H 2O2 ® Cr2 (SO4 )3 + K 2 SO4 + 7H 2O + 3O2

2MnO4 - + 6H + + 5H 2O2 ® 2Mn +2 + 8H 2O + 5O2

HOCl + H 2O2 ® H 3O + + Cl - + O2

(ii) In basic medium:

2MnO4 - + 3H 2O2 ® 2MnO2 + 2H 2O + 3O2 + 2OH -

I 2 + H 2O2 + 2OH - ® 2I - + 2H 2O + O2
Bleaching action:
It can produce nascent oxygen upon decomposition, which acts as bleaching agent. The nascent
oxygen reacts with coloured material and and converts to clourless material by oxidation.

Addition reactions:
Hydrogen peroxide reacts with alkenes to form glycols

CH 2 = CH 2 + H 2O2 ® CH 2 (OH ) - CH 2 (OH )

Structure:
Hydrogen peroxide has open book structure (non planar).

The O-O linkage is called peroxy bond and it is unstable

because of lp-lp repulsions.

Heavy water is D2O and is used moderator in nuclear reactors and in exchange reactions in study
of mechanisms. It will be prepared from electrolytic enrichment of normal water.

H2 releases large quantities of heat on combustion. For the same mass, H2 releases 3 times more
energy than petrol. Pollutants in combustion of H2 will be less than petrol. So H2 can be used as fuel.
Now a days, it is also used in fuel cells for the generation of electric power.

Note: Please study hardness of water from stoichiometry notes (concept: degree of hardness)

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