1

Heavy Water, Hydrogen Peroxide

1. Heavy water [D2O]
- Oxide of heavy hydrogen (deuterium oxide)
- Urey (1932) discovered D2O
- 1 part of D2O is present in 6000 parts of
ordinary water
- Represented as 2H2O or D2O
- Molecular weight is 20
- Obtained by multistage electrolysis of about
0.5 N NaOH Solution
2. Preparation:
Heavy water is prepared by the following
methods
(a) By fractional distillation of ordinary water
(b) By fractional freezing
(c) Prolonged electrolysis of water
(a) By fractional distillation of ordinary water:
Boiling point of H2O=100C Boiling point of
D2O= 101.42 C The fractional distillation of
ordinary water is done in a long fractionating
column (about 40 feet height) and the process is
repeated several times. The lighter fraction
(H2O) is distilled first and the heavier fraction
(D2O) is left in the vessel it self.
(b) By fractional freezing:
Freezing point of H2O = 0C Freezing point of
D2O = 3.82C From the data it is obvious that
two compounds can be separated by fractional
freezing.
(c) Prolonged electrolysis of water:
In this process, continuous and prolonged
electrolysis of ordinary water (containing NaOH)
is carried out. The electrolytic cell was designed
by Brown, Dagget and Urey. The electrolysis is
completed in five or seven stages :
First stage:
- Thirty electrolytic cells are used each cell is
filled with 3% solution of NaOH [77 litres]
in ordiary water
- Electrotysis is carried out for 72 hours. An
electric current of 110 volts is used for
electrolysis.
- After 72 hours, the total charge gets reduced
to 1/6 of its volume and contains about 2.5%
of heavy water
Second stage:
-. The. residue from the first stage is
elctrolysed-using 6 cells.
- The electrolysis is continued till the content
of heavy water is increased to 12%
- The gases evolved are burnt in oxygen and
water so formed is returned to the first stage
cell.
Third stage:

The residue from the second stage is further

electrolysed till the heavy water
concentration is increased to 60%
- the gases evolved are burnt in oxygen and
the water formed is returned to second stage
cell.
Fourth stage:
- The residual water obtained from third stage
is further electrolysed.
- The electrolysis is continued till the content
of heavy water is raised to 99.5%
- The gases are burnt and the water formed is
sent to third stage cell.
Fifth stage: .
- 99.5% heavy water obtained from the fourth
stage
is distilled.
- This distillate is then further electrolysed.
The gas evolved is pure D2. This D2 when
burnt in oxygen yields 100% D2O
O2
[D2
D2O]
burnt
3. Properties of heavy water
Physical : Heavy water [D2O16] is a colourless,
odourless and tasteless liquid.
Its physical constants in general are higher than
the corresponding values for ordinary water.
The data are given in the table.
Physical property
H2O
D2O
Maximum density
1.00 at 277 1.073 at 284.6K
(g/ml.) point
K
Melting
0Cor273K
3.82C or 276.82
Boling point
100Cor373 101.42 or 374 or
Specific heat
l.00 cal/gK
1.01'caVgKLatent heat of fusion
79.7cal/g
75.5cal/g
Latent heat of
539cal/g
557cal/g
Viscosity at 20C
10.09
12.6 millipoise
Surface tension at
72.8
67.8 dynes/cm
Dielectric constant
82.0
80.5
Solubility of NaCl
359g
305g
Molecular mass
18.016
20.03
Dissociation constant 1.0 x 1014
0.3 x 1014
Chemical reactions:
H2O and D2O have similar chemical properties.
However the rate of heavy water reactions is slow.
This is attributed to the fact that deuterium bond is
stronger than protium bond
(i)

Properties

Chemical equations

Action of metals

2D2O+2Na
2D2O + Ca
with hot metals
4D2O + 3Fe
D2O + Zn

2NaOD + D2
Ca(OD)2 + D2
Fe3O4 + D2
ZnO + D2

2
(ii)

Action of metallic
oxide (sodium
deuteroxide)

Na2O + D2O

(iii)

Action of nonmetallic oxide

SO3 + D2O
D2SO4
deutero sulphuric acid
N2O5 + D2O
2DNO3
P2Os + 3D2O
2D3PO4

(iv)

Action of Carbides

Action of nitride

(vi)

Action of phosphide

(vii) Exchange reaction

(viii) Deuterolysis

(ix)

2NaOD

CaC2 + 2D2O
Ca(OD)2 + C2D2
deutero acetylene
A14C3+12D2O
4A1(OD)3 + 3CD4
deutero methand
Mg3N2 + 6D2O
3Mg(OD)2 + ND3
A1N + 3D2O
A1(OD)3 +ND3
deutero phosphine
Ca3P2 + 6D2O

3Ca(OD)2+2PD3

NaOH + D2O
HC1(aq) + D2O
A1C13 + 3D2

NaOD + HDO
DCl + HDO
A1(OD)3 + 3DCl
aluminium deuterium
deutero
chloride
hydroxide

Electrolysis

Electrolysis

2D2O

2D2 + O2

(at cathode) (at anode)

(x)

Action of metal
hydride

CaH2+D2O

4Ca (OD)2+DH

Uses
(i) Heavy water is used in nuclear reactors in
slowing down neutrons (as a moderator)
(ii) Heavy water is used in the production of
deuterium (electrolysis or by decomposition with
metals)
(iii) Heavy water is used as a tracer compound to
study the mechanism of the reaction.
Example (1): Oxidation of Ph2 CHOH by
alkaline KMnO4
OH-Mn 4M nO4Ph 2CDhH OH O H- Ph 2CO

Ph2CHOH
Ph2CDOH

MnO-4
OH

MnO-4
OH -

Ph2CO
Ph2CO

Reaction (1) Takes place 6.7 times as fast as

reaction (2). This indicates that the C-H bond is
broken in the reaction.
Example(2): H3PO2 is a monobasic acid
+D2O
H3PO2
DH2PO2 + HDO
Only one hydrogen of the acid is found to exchange
for deuterium. Since deuterium is known to
exchange only with ionic hydrogen. This suggests
that H3PO2 is monobasisc acid.
(iv) Number of compounds (e.g ND3, CD4, C2D2,
D2S04) can be prepared using heavy water.
Note: In india heavy water manufacturing is carried
out at Nangal, Rawatbhata, Rourkela.
Disadvantage : Heavy water of high concentration
retard the
growth of plants and living organism, germination
of seeds is also stopped.

Hydrogen peroxide [H2O2]

- Discovered by L.J. Thenard (1818)
- It is called oxygenated water
- Found in small quantity in atmosphere and
plants Laboratory preparation:
(i) From sodium peroxide:
Na2O2 + H2SO4 (20%)
Na2SO4 + H2O2
The solution of H2O2 always contains some Na2SO4.
On Alteration a 30% solution of H2O2 is obtained.
(ii) From barium peroxide:
BaO2.8H2O + H2SO4 BaSO4 + H2O2 + 8H2O
It should be noted thatH2SO4 should be replaced by H3PO4 as it
catalyses the decomposition of H2O2 formed.
Anhydrous barium peroxide does not react
readily with H2SO4 because a layer of BaSO4 is
coated over the surface and the reaction ceases.
3BaO
Ba3 (PO4)2 + 3H2O2
2 + 2H3PO4
Barium phosphate is filtered and the solution
contains only H2O2. Barium phosphate is
decomposed by H2SO4
Ba3(PO4)2 + 2H2SO4
3BaSO4 + H3PO4
(iii) H2O2 can be obtained by passing CO2 gas
through Ba02 solution (Merck's process)
BaO2 + CO2 + H2O
BaCO3 + H2O2
BaCo3 is filtered off.
Manufacture of H2O2
Primarily two methods are used to manufacture
H2O2
(i) Electrolytic method (ii) Auto-oxidation of 2-butyl
anthraquinol
(i) Electrolytic method (a) Electrolysis of 50%
H2SO4
In the electrolysis of 50% H2SO4 using platinum
electrodes, first we obtain peroxydisulphuric acid
(H2S2O8) which on distillation produces 30% H2O2
2H2SO4
At cathode :
2H+ + 2e
At anode:
2HSO4
2HSO4

2H+ + 2HSO4
H2 (reduction)

2HSO4 + 2e (oxidation)
H2S2O8

Distillation:H2S2O8 + 2H2O

2H2SO4 +H2O2

(1) Electrolysis of ammonium hydrogen sulphate

In the electrolysis of ammonium hydrogen sulphate,
ammonium per sulphate is formed. It is separated
and distilled with dil.H2SO4 to give 30-40% H2O2
(aqueous solution)
NH4HSO4
NH4SO4 + H+
+

At cathode: 2H + 2e
H2 (reduction)
At anode: 2NH4SO4
(NH4)2 S2O8 + 2e
(oxidation)

H2SO4
Distillation: (NH4)2S2O8 + 2H2O
NH4HSO4+H2O2
(ii) Auto-oxidation of 2-butyl anthraquinol:
This is the most modern method and needs H2,
atmospheric oxygen and water as the major raw
material.
H2(Pd)

1-Butyl anthraquinone

2-Butyl anthraquinol

O2 (air)
2-Butyl anthraquinone
+ H2O2

First and foremost 2- butyl anthraquinone is

catalytically reduced to 2- butyl anthraquinol in
organic solvent by H2 and Pd (caytalyst).
Secondly, 2- butyl anthraquinol is oxidised by air to
2- butyl
anthraquinone. H2O2 obtained in the process is
extracted with
water to give 20% H2O2 solution.
2- butyl anthraqunone is thus reused. The process is
repeated,
thus it is a cyclic process.
8. Concentration of H2O2
It is difficult to concentrate the dilute solution
obtained in the above processes. Because of the
explosive decomposition of H2O2 into H2O and
O2. This is catalysed by organic matter and
metal ions.
Few methods of concentration are:
(i) Water is carefully evaporated from the
aqueous solution of H2O2 to get its 30%
solution.
(ii) At 35-40C, distillation of the above solution
is carried out under reduced pressure to get 90%
concentration,
(iii) With the help of dry ice and ether, the 90%
solution is cooled to get the crystal of H2O2.
Crystals are separated melted and refrozen to get
99% H2O2
9. Physical properties
(i) Pure anhydrous H2O2 is syrupy liquid (bluish
tinge)
(ii) It boils at 152C and freezes at -0.89C
(iii) Its specific gravity is 1.46 at 0C
(iv) It is diamagenetic
(v) It decomposes at its boiling point.
(vi) It can be distilled under reduced pressure. Its
dipole moment is 2.1D
(vii) It is associated liquid due to hydrogen
bonding.
10.Chemical properties:
(a) Decomposition
It is unstable and decomposes on.standing or
on heating

H2O2 + H2O2
2H2O + O2
It is an example of auto oxidation reduction
reaction.
H2O2[O.N. of O = 1]
H2O2[O.N. of O = l ]

O2 [O.N. of 'O' = O]
O[O.N. of O= 2]

Note: Pt, Au, Ag, MnO2, carbon accelerates the

decomposition of H2O2. Alcohol, glycerol,
acetanilide rertard the decomposition of H2O2
(b) Acidic nature:
Hydrogen peroxide (pure) is acidic. It is neutral
towards litmus. In aqueous solution it ionises in
two steps
H2O2
H+ + HO2.(hydroperoxide ion)

HO2
H+ + O22 (peroxide ion)
Mostly it forms peroxides :
2NaOH + H2O2
Na2CO3 + H2O2

Na2O2 + 2H2O
Na2O2 + CO2 + H2O

(c)
Bleaching action: It exhibit mild
bleaching action. H2O2 H2O + O, coloured
material + O Colourless
(d)
Addition reaction:
CH, + H2O2
CH2OH
||
|
CH2
CH2OH
ethylene
ethylene glycol
(e) Oxidising properties:
In acidic medium: H2O2 + 2H+ + 2e
2H2O
In basic medium: H2O2 + 2OH- + 2e
2H2O +
2O2 Potential equation: H2O2
H2O + O
Examples:
(i)PbS to PbSO4 (black to white)
PbS + 4H2O2
PbSO4 + 4H2O
(ii) Na2SO3 to Na2SO4
Na2SO3 + H2O2
Na2SO4 + H2O
(iii) KI to I2
2KI + H2O2
2KOH + I2
(iv) H2S to S
H2S + H2O2
2H2O+S
(v) Na2AsO3 to Na3AsO4
Na3AsO3 + H2O2
Na3AsO4 +
H2O
(vi) NaNO2 to NaNO3
NaNO2 + H2O2
NaNO3 + H2O
(vii) K4Fe(CN)6 to K3Fe(CN)6
2K4Fe(CN)6+H2SO4 + H2O2
2K3Fe(CN)6+K2SO4+2H2O
(viii) FeSO4 to Fe2(SO4)3
2FeSO4 + H2SO4 + H2O2
Fe2(SO4)3 + 2H2O
(ix) K2Cr2O7 to CrO5 [Blue perchromate]
K2Cr2O7 + H2SO4 + 4H2O2
2CrO5 + K2SO4 + 5H2O

CrO5 changes to Cr2 (SO4)3

4CrO5 + 6H2SO4
+ 7O2

2Cr(SO4)3 + 6H2O

(x) HCHO to HCOOH (Alkaline medium)

Pyrogallol
2HCHO + H2O2
2HCOOH + H2
[The reaction proceeds with emission of light]
(xi) Benzene to Phenol [FeSO4]
C6H6 + H2O2
C6H5OH + H2O
Reducing properties
In acidic medium: H2O2
2H++ O2 + 2e
In alkaline medium (Powerful action):
H2O2 + 2OH
2H2O + O2 + 2e
Potential equation: H2O2 + O
H2O + O2

Examples
(i) KMnO4 to MnSO4 [Decolonization]
2KMnO4 + 3H2SO4 + 5H2O2
K2SO4 +
2MnSO4+ 8H2O + SO2
(ii) K2Cr2O7 to Cr2(SO4)3
K2Cr2O7+4H2SO4+3H2O2
K2SO4+Cr2(SO4)3+7
H2O+3O2 (iii) Ag2O to Ag
Ag2O + H2O2
2Ag + H2O + O2
(iv) O3 to O2
O3 + H2O2
H2O + 2O2
(v) PbO2 to PbO
PbO2 + H2O2
PbO + H2O + O2
(vi) Cl2 to HCl
Cl2 + H2O2
2HCl + O2
(vii) K3Fe(CN)6 to K4Fe(CN)6 [Alkaline medium]
K3Fe(CN)6+2KOH+H2O2
K4Fe(CN)6 +2H2O
+O2
(viii) Fe2(SO4)3 to FeSO4 (Alkaline medium)
Fe2(SO4)3+2KOH+H2O2
2FeSO4 +K2SO4
+2H2O+O2
(ix) NaOCltoNaCl
NaOCl + H2O2
NaCl + H2O + O2
13. Strength of H2O2 solution:
The concentration of H2O2 is expressed in terms
of volume strength e.g. '10 volume' '20 volume'
or '30 volume'.
It indicates the volume of oxygen obtained at
NTP by 1 ml of that H2O2 solution.
Few important formulae:
Volume strength = 5.6 x normality
Volume strength = 11.2 x molarity
Concentration from volume strength to (w/V)
percent
Volume strength
17
Cone, in percent = x
5.6
10
Concentration from (w/V) percent to volume
strength
112
Volume strength = x (w/V) percent
34
14. Uses:
(i) Bleaching action: Mild bleaching agent for
delicate articles such as hair, silk, wool, ivory

feather etc.
H2O2,NH3
[Hair
Hair (golden yellow)].
(ii) Converting black lead paintings to white:
H2O2 converts black PbS to white lead sulphate
(reaction associated with painting).
(iii) Qxidant in laboratory
(iv) In detection of Ti, V and Cr ions.
(v) Igniting liquid fuel in rocket engines: It is
used as a concentrated source of oxygen required
to ignite the liquid fuel in jet and rocket.
(vi) Hydrazine hydrate is used in the rockets
NH2:NH2 + 2H2O2
N2 + 4H20
The reaction is exothermic and accompanied by
large increase in volume so that rocket is
propelled.
(vii) As an anitseptic and germicide: For
washing wound, teeth and ears used as antiseptic
in surgical treatment,
(viii) As an antichlor to remove traces of chlorine.
15.Test of H2O2:
(i) Black stain of PbS on filter paper becomes white
with H2O2 due to formation of PbSO4.
(ii) With titanium sulphate H2O2 gives orange red
colour due to the formation of pertitanic acid.
Ti(SO4)2 + H2O2 + 2H2O
H2TiO4 + 2H2SO4
(iii) Gives blue colour with acidified K2Cr2O7 due
to the formation of CrO5 (blue perchromate).
(iv) Liberates iodine with KI in the presence of
FeSO4, which gives blue colour with starch
solution.
16. Structure of H2O2:
H2O2 is a tautomeric mixture of two forms in
equilibrium.
H H
OO
H

H
A [Bayer formula] B [Kingzett formula]

Evidence in favour of structure A

H2O2 behaves as a weak dibasic acid. It forms
two kinds of salt.
NaOOH and NaOONa
Evidence in favour of structure B
The oxidising property of H2O2 is easily
explained (co-ordinate bond is broken).
H

H
O

O + O
H

For the structure (A) the data are as under:

OO bond distance = 1.48

OH bond distance = 0.97

HOO bond angle = 97

angle between the plane
containing hydrogen atom = 94