Lecture 5

Heavy water (D₂O):

Method of preparation:
Repeated electrolysis of H₂O: On electrolysis of water (impure) H₂O dissociates into H⁺ and OH⁻
while a fractional part of D₂O will dissociate into D⁺ and OD⁻

H₂O ⇌ H⁺ + OH⁻

H₂O ⇌ D⁺ + OD⁻

D⁺ and OD⁻ due to more mass have less mobility i.e. why H⁺ and OH⁻ will move towards the
cathode and anode respectively while D⁺ and OD⁻ will be in solution.

Properties of Heavy water:

Physical properties:
(a) Heavy water is a colourless, odourless and tasteless mobile liquid.
(b) Nearly all the physical constants are higher than the corresponding values of ordinary water.
Dielectric constant of H2O is slightly more than D2O.

Chemical properties:
Heavy water is chemically similar to ordinary water. However, D₂O reacts more slowly than
H₂O in chemical reactions.

(a) Reaction of metals: D₂O reacts with alkali and alkaline earth metals liberates heavy
hydrogen.
2D₂O + 2Na → 2NaOD + D₂ (Sodium deuteroxide)
2D₂O + 2Ca → Ca(OD)₂ + D₂ (Calcium deuteroxide)

(b) Reaction with metallic oxides: D₂O reacts slowly with basic oxides to form heavy alkalies.
Na₂O + D₂O → 2NaOD
CaO + D₂O → Ca(OD)₂
(c) Reaction with nonmetallic oxides: D₂O reacts slowly with acidic oxides to form deutero acids.
N₂O₅ + D₂O → 2DNO₃ (Deutero nitric acid)
P₂O₅ + 3D₂O → 2D₃PO₄ (Deutero phosphoric acid)
SO₃ + D₂O → D₂SO₄ (Deutero sulphuric acid)

(d) Reaction with metallic carbides, phosphides, nitrides, arsenides, etc.: Like H₂O, heavy water
reacts with carbides, phosphides, nitrides, arsenides, etc., to form corresponding deutero
compounds.

CaC₂ + 2D₂O → Ca(OD)₂ + C₂D₂ (Deutero acetylene)

Al₄C₃ + 12D₂O → 4Al(OD)₃ + 3CD₄ (Deutero methane)

Mg₃N₂ + 6D₂O → 3Mg(OD)₂ + 2ND₃ (Deutero ammonia)

AlN + 3D₂O → Al(OD)₃ + ND₃ (Deutero ammonia)

Ca₃P₂ + 6D₂O → 3Ca(OD)₂ + 2PD₃ (Deutero phosphine)

Na₃As + 3D₂O → 3NaOD + AsD₃ (Deutero arsine)

(e) Electrolysis: A solution of heavy water containing Na₂CO₃ when electrolysed evolves heavy
hydrogen at the cathode.

Uses: As a neutron moderator: Fission in uranium-235 is brought by slow-speed neutrons. The

substances which are used for slowing down the speed of neutrons are called moderators. Heavy
water is used for this purpose in nuclear reactors.

Hydrogen peroxide (H₂O₂):

Hydrogen peroxide is an important chemical used in pollution control treatment of domestic
and industrial effluents.

The preparation of hydrogen peroxide (H₂O₂):

Laboratory method:

Using Sodium Peroxide and Sulphuric Acid:

Na₂O₂ + H₂SO₄ → Na₂SO₄ + H₂O₂

Using Hydrated Barium Peroxide and Sulphuric or Phosphoric Acid:

Acidifying barium peroxide and removing excess water by evaporation under reduced pressure
gives hydrogen peroxide.

With Sulphuric Acid:

BaO₂ · 8H₂O + H₂SO₄ → BaSO₄ + H₂O₂ + 8H₂O

Nowadays H3PO4 used instead of H2SO4 because H2SO4 increase catalytic decomposition of
H 2O 2.

With Phosphoric Acid:

3BaO₂ + 2H₃PO₄ → Ba₃(PO₄)₂ + 3H₂O₂

The preparation of hydrogen peroxide (H₂O₂) and deuterium peroxide (D₂O₂) using
peroxodisulphate:

Peroxodisulphate is obtained by electrolytic oxidation of acidified sulphate solutions at high

current density. It yields hydrogen peroxide upon hydrolysis. This method is now used for the
laboratory preparation of D₂O₂.

1. 2 HSO₄⁻ (aq) → HO₃SOOSO₃H (aq) (Electrolysis)

2. HO₃SOOSO₃H (aq) → 2 HSO₄⁻ (aq) + 2 H⁺ (aq) + H₂O₂ (aq) (Hydrolysis)

3. K₂S₂O₈ (s) + 2 D₂O (l) → 2 KDSO₄ (aq) + D₂O₂ (l)

Industrial Method:

Auto Oxidation of 2 Butyl Anthraquinol:

In this case 1% H2O2 is formed. It is extracted with water and concentrated to ~30% (by mass)
by distillation under reduced pressure. It can be further concentrated to ~85% by careful
distillation under low pressure. The remaining water can be frozen out to obtain pure H2O2 .

Oxidation of Isopropyl Alcohol:

CH₃CH(OH)CH₃ + O₂ → CH₃COCH₃ + H₂O₂

Chemical Properties:
It acts as an oxidizing as well as a reducing agent in both acidic and alkaline media. Simple
reactions are described below.

(i) Oxidizing action in acidic medium

2Fe²⁺(aq) + 2H⁺(aq) + H₂O₂(aq) → 2Fe³⁺(aq) + 2H₂O(l)

PbS(s) + 4H₂O₂(aq) → PbSO₄(s) + 4H₂O(l)

(ii) Reducing action in acidic medium

2MnO₄⁻ + 6H⁺ + 5H₂O₂ → 2Mn²⁺ + 8H₂O + 5O₂

HOCl + H₂O₂ → H₃O⁺ + Cl⁻ + O₂

(iii) Oxidizing action in basic medium

2Fe²⁺ + H₂O₂ → 2Fe³⁺ + 2OH⁻

Mn²⁺ + H₂O₂ → Mn⁴⁺ + 2OH⁻

(iv) Reducing action in basic medium
I₂ + H₂O₂ + 2OH⁻ → 2I⁻ + 2H₂O + O₂

2MnO₄⁻ + 3H₂O₂ → 2MnO₂ + 3O₂ + 2H₂O + 2OH⁻

Physical Properties: In the pure state H2O2 is an almost colourless (very pale blue) liquid. H2O2 is
miscible with water in all proportions and forms a hydrate H2O2.H2O (mp 221K).

- Melting point/K: 272.4

- Boiling point (extrapolated)/K: 423
- Vapour pressure (298K)/mmHg: 1.9
- Density (solid at 268.5K)/g cm⁻³: 1.64
- Density (liquid at 298K)/g cm⁻³: 1.44
- Viscosity (290K)/centipoise: 1.25
- Dielectric constant (298K)/C²/N m²: 70.7
- Electrical conductivity (298K)/Ω⁻¹ cm⁻¹: 5.1 × 10⁻⁸

Structure:
Hydrogen peroxide has a non-planar structure. The molecular dimensions in the gas phase and
solid phase are shown below
Storage:
H₂O₂ decomposes slowly on exposure to light.

2H₂O₂ (l) → 2H₂O (l) + O₂ (g)

H₂O₂ cannot be stored in simple glass bottles since the rough surface of glass [alkali oxides
present in it] is excited by light and decomposes H₂O₂. So the H₂O₂ is usually stored in colored,
paraffin wax-coated, plastic bottles.
- Always add a small quantity of inhibitor or negative catalyst to H₂O₂ to prevent
decomposition, such as H₃PO₄, acetanilides, etc.

Uses:
Its wide scale use has led to tremendous increase in the industrial production of H₂O₂. Some of
the uses are listed below:

(i) In daily life it is used as a hair bleach and as a mild disinfectant. As an antiseptic it is sold in
the market as perhydrol.

(ii) It is used to manufacture chemicals like sodium perborate and per-carbonate, which are
used in high quality detergents.

(iii) It is used in the synthesis of hydroquinone, tartaric acid and certain food products and
pharmaceuticals (cephalosporin) etc.

(iv) It is employed in the industries as a bleaching agent for textiles, paper pulp, leather, oils,
fats, etc.

(v) Nowadays it is also used in Environmental (Green) Chemistry. For example, in pollution
control treatment of domestic and industrial effluents, oxidation of cyanides, restoration of
aerobic conditions to sewage wastes, etc.

Hard Water and Soft Water:

Rain water is almost pure (may contain some dissolved gases from the atmosphere). Being a
good solvent, when it flows on the surface of the earth, it dissolves many salts. Presence of
calcium and magnesium salts in the form of hydrogen carbonate, chloride and sulphate in water
makes water ‘hard’. Hard water does not give lather with soap. Water free from soluble salts of
calcium and magnesium is called Soft water. It gives lather with soap easily.

Hard water forms scum/precipitate with soap. Soap containing sodium stearate (C₁₇H₃₅COONa)
reacts with hard water to precipitate out Ca/Mg stearate.

2C₁₇H₃₅COONa(aq) + M²⁺(aq) → (C₁₇H₃₅COO)₂M ↓ + 2Na⁺(aq); M is Ca/Mg

It is, therefore, unsuitable for laundry. It is harmful for boilers as well, because of deposition of
salts in the form of scale. This reduces the efficiency of the boiler.

The hardness of water is of two types: (i) temporary hardness, and (ii) permanent hardness.

Temporary Hardness:

Temporary hardness is due to the presence of magnesium and calcium hydrogen-carbonates. It

can be removed by:

(i) Boiling: During boiling, the soluble Mg(HCO₃)₂ is converted into insoluble Mg(OH)₂ and
Ca(HCO₃)₂ is changed to insoluble CaCO₃. It is because of high solubility product of Mg(OH)₂ as
compared to that of MgCO₃, that Mg(OH)₂ is precipitated. These precipitates can be removed by
filtration. Filtrate thus obtained will be soft water.

Mg(HCO₃)₂ —Heating→ Mg(OH)₂ ↓ + 2CO₂ ↑

Ca(HCO₃)₂ —Heating→ CaCO₃ ↓ + H₂O + CO₂ ↑

(ii) Clark’s method: In this method calculated amount of lime is added to hard water. It
precipitates out calcium carbonate and magnesium hydroxide which can be filtered off.

Ca(HCO₃)₂ + Ca(OH)₂ → 2CaCO₃ ↓ + 2H₂O

Mg(HCO₃)₂ + 2Ca(OH)₂ → 2CaCO₃ ↓ + Mg(OH)₂ ↓ + 2H₂O

Permanent Hardness:
Permanent hardness is due to the presence of soluble salts of magnesium and calcium in the
form of chlorides and sulphates in water. It cannot be removed by boiling. It can be removed by
the following methods:

1. Treatment with washing soda (sodium carbonate):

Washing soda reacts with soluble calcium and magnesium chlorides and sulphates in hard water
to form insoluble carbonates.

MCl₂ + Na₂CO₃ → MCO₃ ↓ + 2NaCl

(M = Mg, Ca)

MSO₄ + Na₂CO₃ → MCO₃ ↓ + Na₂SO₄

2. Calgon's method:
Sodium hexametaphosphate (Na₆P₆O₁₈), commercially called 'calgon', when added to hard
water, the following reactions take place:
Na₂P₆O₁₈ → 2Na⁺ + Na₄P₆O₁₈²⁻Ê
(M = Mg, Ca)

M²⁺ + Na₄P₆O₁₈²⁻ → [Na₂MP₆O₁₈]²⁻ + 2Na⁺

The complex anion keeps the Mg²⁺ and Ca²⁺ ions in solution.

(iii) Ion-exchange method: This method is also called zeolite/permutt process. Hydrated sodium
aluminium silicate is zeolite/permutt. For the sake of simplicity, sodium aluminium silicate
(NaAlSiO₄) can be written as NaZ. When this is added in hard water, exchange reactions take
place.

2NaZ(s) + M²⁺(aq) → MZ₂(s) + 2Na⁺(aq)

(M = Mg, Ca)

Permutt/zeolite is said to be exhausted when all the sodium in it is used up. It is regenerated for
further use by treating with an aqueous sodium chloride solution.

MZ₂(s) + 2NaCl(aq) → 2NaZ(s) + MCl₂(aq)

(iv) Synthetic resins method: Nowadays hard water is softened by using synthetic cation
exchangers. This method is more efficient than zeolite process. Cation exchange resins contain
large organic molecule with -SO₃H group and are water insoluble. Ion exchange resin (RSO₃H) is
changed to RNa by treating it with NaCl. The resin exchanges Na⁺ ions with Ca²⁺ and Mg²⁺ ions
present in hard water to make the water soft. Here R is resin anion.

2RNa(s) + M²⁺(aq) → R₂M(s) + 2Na⁺(aq)

The resin can be regenerated by adding aqueous NaCl solution.

Pure de-mineralised (de-ionized) water free from all soluble mineral salts is obtained by passing
water successively through a cation exchange (in the H⁺ form) and an anion-exchange (in the
OH⁻ form) resins.

2RH(s) + M²⁺(aq) → MR₂(s) + 2H⁺(aq)

In this cation exchange process, H⁺ exchanges for Na⁺, Ca²⁺, Mg²⁺ and other cations present in
water. This process results in proton release and thus makes the water acidic. In the anion
exchange process:
RNH₂ (s) + H₂O (l) ⇌ RNH₃⁺.OH⁻ (s)

RNH₃⁺.OH⁻ (s) + X⁻ (aq) ⇌ RNH₃⁺.X⁻ (s) + OH⁻ (aq)

OH⁻ exchanges for anions like Cl⁻, HCO₃⁻, SO₄²⁻ etc. present in water. OH⁻ ions, thus, liberated
neutralise the H⁺ ions set free in the cation exchange.
H⁺ (aq) + OH⁻ (aq) → H₂O (l)

The exhausted cation and anion exchange resin beds are regenerated by treatment with dilute
acid and alkali solutions respectively.

Dihydrogen as Fuel:

The Hydrogen Economy emphasizes using dihydrogen (H₂) as a fuel due to its high energy
content per mass (143 kJ/g) and cleaner combustion, which mainly produces water, reducing
pollutants. However, challenges include efficient storage and safe transportation.

In October 2005, India initiated a pilot project on using H₂ as a fuel. Several measures were
adopted to improve storage technologies, such as pressurized and liquid hydrogen tanks and
metal hydrides. The project also focused on developing infrastructure for H₂ production and
distribution to support broader adoption.

Despite these efforts, the widespread use of H₂ as a fuel still faces technical and economic
hurdles, including high production costs and the need for substantial investments in
infrastructure. Nonetheless, H₂ holds significant promise for a sustainable and eco-friendly
energy future.