NON-AQUEOUS SOLVENTS

Introduction:
Most of the chemical reactions familiar to us take place in aqueous solution since
water, due to the high value of its dielectric constant, has an increased ability to
dissolve the ionic compounds and many other substances. However there are many
chemical reactions which cannot be carried out in aqueous solution but can be
studied in a non-aqueous medium. A large number of non-aqueous solvents have
been discovered in the last few years. These solvents have a sizable value of their
dielectric constant and hence can dissolve many substances. Examples of such
solvents are anhydrous liq. NH3, liq.SO2, anhydrous HF, liq. N204, etc.

Classification of Solvents :
Solvents have been classified in a number of ways, depending on the properties
of the solvents. The most convenient classification of solvents is based on the
electrolytic characteristics of the solvents. This classification has been shown below:
1. Non-ionising solvents or Nonpolar liquids or Aprotic solvents: e.g.
benzene, carbon tetrachloride.
2. Ionising solvent or Polar liquids:
a. Protonic:
i. Protogenic (acidic solvents) Strong tendency to donate
protons. e.g.H2SO4,H2F2,CH3COOH
ii. Protophilic (basic solvents) Strong affinity to accept protons.
e.g. Liq. NH3, Pyridine, Ethylene diamine
iii. Amphiprotic (amphoteric solvents) Can act both as acids or bases.
e.g. H2O, CH3OH
b. Non-protonic: e.g. liq. SO2, BrF3, HgBr2
1. Non-ionising solvents (Non-polar solvents):
These solvents are also called aprotic solvents or non-protic or non-
protic solvents. These solvent have no hydrogen in their structure.
e.g. C6H6, CCI4, etc.These solvents have very little dielectric constant. They
dissolve non substances.
2. Ionising solvents (Polar solvents):
Examples of such solvents are H2SO4, H2F2, CH3COOH, H2O, liq. NH3, liq.
SO2, pyridine, BrF3, HgBr2, CH3OH etc. Polar solvents have associated
structures. Non-polar substances do not dissolve in these solvents because of
Dr. Shashi Bala, Dept of Chemistry, 1
University of Lucknow
 the squeezing effect produced by their associated structure. However ionic and
covalent polar substances dissolve in them. The dissolution of ionic substances
is due to their greater solvation energy than the lattice energy of the salts.
Several covalent substances dissolve forming H-bonds.

Classification of Ionising Solvents:

I. Protonic Solvents:
These solvents have hydrogen in their structure. These may be of the following
types:
A. Proto-genic solvents (Acidic solvents):
These solvents have a tendency to donate protons. e.g. H 2SO4,
H2F2,CH3COOH.
B. Protophilic solvents (Basic solvents):
These solvents have a tendency to accept protons. E.g. liq. NH 3,
pyridine, ethylenediamine etc.
C. Amphi-protic or amphoteric solvents:
These show dual character i.e. they can lose as well as accept protons, depending on
the nature of the reacting species, e.g. H 2O, alcohols, liq.NH3, CH3COOH, etc.
Amphoteric solvents undergo auto-ionisation (self-ionisation) in which a proton
transfer between two similar neutral molecules takes place and a cation-anion pair
of the solvent is obtained e.g.

Acid Base Acid Base

H2O + H2O = H30+ + OH-
+ -
NH3(l) + NH3(l) = NH4 + NH2

Dr. Shashi Bala, Dept of Chemistry, 2

University of Lucknow
 CH3COOH + CH3COOH = CH3COOH + + CH3COO-

II. Non-Protonic Solvents:

These solvents have nothing to do with protons.e.g. liq. SO 2, BrF3, HgBr2. Due
to self-ionisation they also furnish cations and anions, similar to protonic
solvents.

In this chapter we shall restrict our study on ionizing solvents only. i.e. in which
inorganic substances ionize and give ionic reactions as in H2O. Non-ionizing
solvents are of great interest in organic chemistry.

Physical Properties of Solvents and their Role in Chemical Reactions:

Every liquid cannot be used as a solvent in a chemical reaction.Here we compare the

properties of some non-aqueous solvents with the properties of H20.

1. Melting point and boiling point:

Most of the chemical reactions are carried out in the liquid phase. Hence the
melting point and boiling point of a solvent indicates the range of temperature
within which the solvent can be used. Melting points and boiling points( 0C) of
some solvents are given below:

Solvent Melting Boiling Characteristics

point point
H2O 0.0 100 Very convenient liquid
CH3COOH 16.16 118.1 Can act at ordinary temperature
NH3 -77.7 -33.4 Can act at low temperature
SO2 -75.5 -10.2 Can act at low temperature
HF -89.3 19.5 ----

Dr. Shashi Bala, Dept of Chemistry, 3

University of Lucknow
2. Dielectric constant (ɛ):
Dielectric constant (ɛ) of a solvent determine ability of the solvent to dissolve
polar and non-polar substances in it.The coulombic force (F) between a cation
and an anion of an ionic compound is given by the expression:

F = q1q2 / ɛ(r1+r2)2

In this expression q1 and q2 are the charges on cation and anion respectively, r1
and r2 are the radii of the two ions and ɛ is the dielectric constant of the solvent.
The value of ɛ depends on the nature of the solvent in which the ionic
compound is dissolved. The value of dielectric constant of some solvents are
given below.

Solvent Value of ɛ Solvent Value of ɛ

H2O 78.5 (25°C) CH3COOH 9.7 (18°C)

NH3 22.0 (- 33. 5°C) HF 83.6 (0°C)

SO2 17.3(-16°C) N2O4 2.42 (0°C)

It may be clear from the above expression that if ɛ of a solvent is large, F

would be small i.e. if ɛ is large, small amount of energy would be required to
separate the ions and hence it would be easy for a solvent having a high value
of ε to dissolve an ionic compound in it. For example, since anhydrous HF and
H2O have high values of ɛ, these are the best solvents for ionic compounds.

On the other hand, since liq.NH3 and liq.SO2 has low values of ɛ , these
solvents show smaller ability to dissolve ionic compounds especially those
containing multi-charged ions. Thus carbonates, sulphates and phosphates
which contain multi-charged ions are insoluble in liq.NH3 and liq.SO2.

3. Dipole moment:
Greater is the polarity of the bond in a solvent molecule.greater is the charge
separation and higher will be the value for dipole moment. Substances having
high dipole moment values are good solvent for polar solutes. This is because
of the fact that greater is the polarity of a solvent molecule, greater is the
solvation energy released on dissolution of a solute. Dipole moment value of a
solvent also gives an idea about the extent of association of the molecules of a
liquid and hence its liquid range. Dipole moment values (in D) of H 2O, NH3
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University of Lucknow
 and SO2 are given below.

Solvent H2O NH3 SO2

Dipole moment 1.85 1.47 1.61

4. Viscosity:
Viscosity gives a measure of the fluidity of the solvent. Solvents like water,
carbon tetrachloride have low viscosity and flow rapidly under ordinary
temperature. In solvent of low viscosity, the operations such as precipitation,
crystallization, filtration, etc. can be easily carried out without any difficulty.
With increasing viscosity of a liquid, the difficulty of such operations increases.
Solvents like anhydrous sulphuric acid have higher viscosities and this reduces
their usefulness as solvent, Viscosity of H2O, NH3 and SO2 is 1.00, 0.241 and
0.009 respectively.

5. Proton affinity:
It is applicable for protonic solvents only. It greatly affects the behaviour of a
solute in a given solvent. NH 3 has greater proton affinity than H 2O. Hence
acetamide (CH3 CO NH2) which behaves as a very weak base in aqueous

↶
solution shows acidic properties in liq.NH3.

+ H2O ⇄ CH3 CO NH3+

↷
CH3 CO NH2 + OH-

CH3 CO NH2 + NH3 ⇄ CH3 CO NH- + NH4+

Dr. Shashi Bala, Dept of Chemistry, 5

University of Lucknow
Proton affinity (in kJ mol-) for H2O and NH3 are 760 and 865 respectively. The
properties of H2O, NH3 and SO2 other than those mentioned above are given below:
Property H2O NH3 SO2

Equivalent 6 x 10-8 5 x 10-8 1 x 10-7

conductance (ohm-1) (25°C) (133.4°C)

Critical temperature 374 132.4 157.5

(°C)

Critical pressure 217.7 112.0 77.8

Density (g/cc) 0.96 0.68 1.46

Types of Chemical Reactions Taking Place in Non-aqueous

Solvents:

1. Metathetical (Precipitation) Reactions

The reactions in which precipitate is formed by mixing two solutions of two
compounds are called metathetical or precipitation reactions. Thus precipitation
reactions are normally double decomposition. The formation of a precipitate in
different solvents depends on the solubilities of the products in those solvents.
For example the precipitate of AgCl is obtained by mixing BaCl2 and AGNO3
in aqueous medium.
water
BaCl2 + 2AgNO3 ---------> AgCl↓ + Ba(NO3)2

In liq.NH3 the above reaction is reversed, i.e., in liq.NH 3 ppt. of BaCl2 is

obtained by combining AgCl with Ba (NO3)2.

liq.NH3
2 AgCl + Ba(NO3)2 -----------> BaCl2 + 2AgNO3

Thus we see that reaction (i) is reversed on changing the solvent.

Dr. Shashi Bala, Dept of Chemistry, 6

University of Lucknow
 2. Acid-Base Reactions
We have already said that the ionic solvents are polar compounds and undergo
self-ionisation, Self-ionisation of some important solvents is given below:

Solvent Solvent cation Solvent anion

Dr. Trupti
(Acid ion) (Base ion)

OH- 2H2O ⇄ H3O+ +

+
2NH3 ⇄ NH4 + NH2-

Darji
+
2BrF3 ⇄ BrF2 + BrF 4-

2HgBr2 ⇄ HgBr+ + HgBr 3-

2SO2 ⇄ SO2+ + 3 2-
SO
+
2H2SO4 ⇄ H3SO4 + 4-
HSO
+
CH3COOH ⇄ CH3COOH2 +
CH3COO-
2HClO4 ⇄ H2ClO4 +
ClO 4-
3HF ⇄ H2F+ +
HF 2-
N2O4 ⇄ NO+ +
NO 3-

An acid-base reaction in a non-aqueous solvent can be explained on the basis

of the solvent system concept of acids and bases. According to this concept an
acid is a substance which contains the solvent cation and a base is a
substance which contains the solvent anion. For example since self-
ionisation of liq.NH3.

NH4Cl(acid) + KNH2 (base) ⇄ KCl(salt) + 2NH3(solvent)

Dr. Shashi Bala, Dept of Chemistry, 7

University of Lucknow
 Acidic character of CH3COOH in H2O and liq. NH3:

When CH3COOH reacts with H2O and liq.NH3 (solvents), H2O and liq, NH3
both accept a proton from CH3COOH to produce H2O+ and NH + ions. Due to
4

the production of these ions, CH3COOH behaves as an acid in both the

solvents.

CH3COOH + H2O ⇄ H3O+ + CH3CO0-

Acid (weak acid) Base Acid Base

CH3COOH + NH3 ⇄ NH4+ + CH3CO0-

Acid (weak acid) Base Acid Base

Now since the proton accepting ability of H 2O is less than that of

liq.NH3, CH3COOH behaves as weak acid in aqueous solution and acts as a
strong acid in liq.NH3 hence sometimes liquid ammonia also termed as
levelling solvent.
3. Solvation Reactions: Formation of Solvates

Solvation reaction is a general reaction in which a solute (a cation, an anion or

a neutral molecule) reacts with one or more molecules of a solvent (e.g.H 2O,
liq.NH3, liq.SO2 etc.) to form a product in which the solute and solvent species
are attached to each other by a H-bond or by a coordinate bond. The product
formed is called solvate. Solvate is an addition compound and hence is also
called an adduct. The addition compound contains solvent of crystallisation.
In the formation of a solvate, the solvent acts as a Lewis base while the solute
species behaves as a Lewis acid. When the solvent used is water, the
solvation reaction is called hydration and the addition compound formed is
called hydrate. Hydrate contains one or more molecules of water as water of
crystallisation. Similarly when the solvent is liq. NH, the reaction is called
ammoniation and the addition compound formed is called
ammoniate.Ammoniate contains one or more molecules of ammonia as
ammonia of crystallisation.

4. Solvolytic Reactions: Solvolysis

Solvolytic reactions are the reactions in which the solvent molecules react with
Dr. Shashi Bala, Dept of Chemistry, 8
University of Lucknow
 the solute molecule (salt) or ion in the way which consists of the following
steps:
(a) The solvent molecule undergoes auto-ionisation (self-ionisation) to give
solvent cations and solvent anions.
(b) The solute (salt) splits into solute cations and solute anions. The solute
cations or solute anions interact with the solvent cations or solvent anions. Due
to this interaction the concentration of the solvent cations or solvent anions is
increased.When H2O and NH3 are used as solvents in the solvolytic reactions,
the reactions are called hydrolysis and ammonolysis (or ammonolysis
reactions) respectively.
Liquid Ammonia (Liq. NH3) Solubility

of Various Substances in Liq.NH3 :

A. Solubility of ionic compounds (inorganic salts):

We know that ammonia has a low value of its dielectric constant (= 22 at

-34°C). This low value suggests that liq.NH 3 has a poor ability to dissolve ionic
compounds. Ammonium salts (e.g. NH4NO, NH4SCN, CH3COONH4 etc.) and
most of the nitrites, nitrates, cyanide, thiocyanate, perchlorates, are soluble in
liq.NH3. Salts containing highly charged ions (e.g., oxides, sulphides,
sulphates, phosphates and carbonates) are insoluble. Fluorides and chlorides
(except Be2+ and Na+ chlorides) are practically insoluble, bromides are less
soluble while iodides are freely soluble. Thus the solubility of the halides of a
given metal increases in going from fluoride to iodide (MF <MCL < MBr
<MI).
Most of the metal amides (except those of alkali metals) are insoluble. The salts
of some metals (e.g. Ni2+, Cu2+, Zn2+ etc.) react with liq.NH 3 and form ammine
complexes.
B. Solubility of non-ionic compounds (organic compounds):

Halogen compounds, alcohols, ketones, esters, simple ethers, amines, phenol

and its derivatives etc. are soluble. Alkanes are insoluble and alkenes and
alkynes are slightly soluble. In this sense, liq.NH3 is a better solvent for non
ionic and nonpolar compounds (organic compounds).
C. Solubility of non-metals:

The non-metals like S, P, I2, Se etc. are soluble and they react with the solvent.

Dr. Shashi Bala, Dept of Chemistry, 9

University of Lucknow
 D. Solubility of alkali metals and alkaline earth metals:
All the alkali metals and alkaline earth metals (excepting Be) are soluble in
liq.NH3.100g of liq.NH3 dissolves 10.9g of Li, 24.8g of Na, 46.8g of K (all at-
33°C) and 334g of Cs (at -50°C). Thus we see that the solubility of alkali
metals in liq. NH3 increases as we pass from Li to Cs (Li < Na < K< Cs).

Chemical Reactions Taking Place in Liq. NH3

1. Metathetical (Precipitation) Reactions

Examples of some precipitation reactions taking place in liq. NH 3 are given

below.

a. Chlorides are precipitated:

2NH4CI(Ammono acid) + Sr(NO3)2 → SrCl2 ↓ + 2NH4N03
Ba(NO3)2 + 2AgCl → BaCl2 ↓ + 2AgNO3

b. Bromides and iodides are precipitated:

Sr(NO)2 + 2NH4Br (Ammono acid) → SrBr2 ↓ + 2NH4N03

Zn(NO)2 + 2NH4I (Ammono acid) → ZnI2 ↓ + 2NH4N03

c. Amides (NH2-), imides (NH2-) and nitrides (N3-)can be

precipitated:

KNH2(Ammono base) + AgNO3 → KNO3 + AgNH2↓ (Amide)

KNH2 + 3HgI2 → 2KI + 4HI +Hg3N2↓(Nitride)

d. Sulphides are precipitated:

(NH4)2S(ammono acid) + 2AgNO3 → Ag2S↓ + 2NH4NO3

(NH4)2S(ammono acid) + M(NO3)2(M=Ba,Cu,Cd) → MS↓ + 2NH4NO3

e. Barium alcoholate can be precipitated:

K(OC2H5) + Ba(NO3)2 → Ba(OC2H5)2↓ + 2KNO3

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University of Lucknow
 2. Acid-base Neutralisation reaction(salt formation) reactions

A compound containing or making available NH + or4 NH2- or N3-

ion(ammono base)to form the salt and the solvent NH3.

NH4Cl → NH +4 + Cl-
KNH2 → K+ + NH -
On adding: NH4Cl + 2KNH2 → K+ + Cl- + NH + 4+ NH -

or NH4Cl(ammono acid) + KNH2(ammono base) → KCl(salt) + 2NH3(solvent) or

NH +(solvent cation) + NH -(solvent anion) → 2NH (solvent)
Above
4 equation indicates 2that neutralisation reaction in liq.NH3can also be
defined as the combination3 of solvent cation(NH +) and solvent anion(NH -) to
4
form the un-ionised solvent(liq.NH ). Other examples in liq.NH3 are:
2
Ammono acid Ammono base Ammono salt Solvent
NH4X (Cl,NO3) + NaNH2 → NaX + 2NH3
2NH4X (Cl,I) + PbNH → PbX2 + 2NH3
3NH4X (Cl,I) + BiN → BiX3 + 4NH3
2CH3COONH4 + Zn(NH2)2 → Zn(CH3COO)2 + 4NH3

3. Amphoteric Behaviour of Zn(NH2)2 in Liq.NH3:

Zn (NH2)2 dissolves in ammono acid as well as in ammono base in liq. NH 3 and

hence is said to show amphoteric character in liq. NH3.

Zn(NH2)2 + 2NH4CI ( Ammono acid)

→ ZnCl2(Salt) + 4NH3(Solvent)
Zn(NH2)2 + 2NaNH2 ( Ammono base) → Na2[Zn(NH2)] + 2NH3

Above reactions can be compared with the following reactions in aqueous

solution. In these reactions Zn(OH)2 shows amphoteric character since it
dissolves in HCL (acid) as well as in NaOH (base).

Zn(OH)2 + 2HCI → ZnCl2 + 2H2O Zn(OH)2

+ 2NaOH → Na2[ZnO2] + 2H2O

Dr. Shashi Bala, Dept of Chemistry, 11

University of Lucknow
 4. Ammonation Reaction : Formation of Ammoniates (Solvation
Reactions - Formation of Solvates):

Solvation reaction in which liq, NH 3 is used as solvent is called ammonation

reaction and the solvate formed is called ammoniate. In the formation of
ammoniate liq. NH3 (solvent) acts as a Lewis base and the solute behaves as a
Lewis acid. The formation of some ammoniates in liq. NH3 has been shown
below. These ammoniates may be 1 : 2 or 1: 1 adducts.

Solute (Lewis acid) Solvent (Lewis base) Ammoniates

SO3 + 2NH3 → SO3.2NH3 (1:2 adduct)

SiF4 + 2NH3 → SiF4.2NH3 (1:2 adduct)

BF3 + NH3 → BF3.NH3 (1:1 adduct)

The formation of NH 4+by action of liq.NH3 on H O is also an example of

2
ammoniation.More examples of ammoniates formed by liq. NH 3 with inorganic
salts are MgI2. 6NH3, Nil2. 6NH3, Nal. 4NH3 etc. In the formation of these
ammoniates, NH3 molecules (solvent molecules) are coordinated to the metal
ions of the inorganic salt (solute).

5. Ammonolysis or Ammonolytic Reaction :(Solvolysis or Solvolytic

Reactions)

The solvolytic reactions taking place in aqueous medium (H 2O) and liq. NH3
are called hydrolysis and ammonolysis (or ammonolytic reactions)
respectively. In hydrolysis H2O is used as a solvent while in ammonolysis liq.
NH3 is used as a solvent.

Examples of ammonolysis:

a. Ammonolysis of SnCl4, SiCl4 and SO2CI2 :

In the ammonolysis of SnCl4 and SO2CI2 (solute) the concentration of NH

+
(solvent
4 cations) is increased as shown below:

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University of Lucknow
 8NH3 (Solvent) ⇌ 4NH +(Solvent cations) + 4NH -(Solvent anions)
4

SnCl4(Solute) → Sn4+ (Solute cations) + 4Cl-

Sn4+ (Solute cations) + 4NH 2-(Solvent anions) → Sn(NH2) 4

On adding: SnCl4(Solute) + 8 NH3 (Solvent) → Sn(NH2)4 + 4Cl- + 4NH4+

b. Ammonolysis of alkali metal hydrides and oxides:

The ammonolysis of alkali metal hydrides and oxides gives alkali metal
amides (MNH2). In these reactions the concentration of NH - ions
2
(solvent anions) is increased..

NaH (Solute) + NH3(Solvent) → NaNH2 + H2

or H- + NH3 → NH2- + H 2 ( In water: H- + H O 2 → OH- + H
2
Na2O (Solute) + 2NH3 (Solvent) → 2NaNH2 + H2O

c. Ammonolysis of TiCl4:

Ammonolysis of TiCl4 (salt) in presence of excess of liq. NH 3 produces

Ti(NH2)4. In each step Cl-atom of the salt undergoing ammonolysis is
replaced by -NH2 group.

TiCl4 + NH3 → TiCl3(NH2) + HCI

TiCl3 (NH2) + NH3 → TiCl2(NH2)2 + HCl TiCl2
(NH2)2 + NH3 → TiCl(NH2)3 + HCl TiCl(NH2)3
+ NH3 → Ti(NH2)4 + HCl
On adding: TiCl4 + 4NH3 → Ti(NH2)4 + 4HCI

d. Ammonolysis of alkyl and aryl halides:

The ammonolysis of alkyl halides RX(R = alkyl group. X = Cl, Br, I)

takes place slowly at the boiling point of lig.NH 3. In this reaction mixture
of primary (RNH2) secondary (R2NH) and tertiary (R3N) amines is
obtained.

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University of Lucknow
 RX + 2NH3 → R(NH2) + NH +4 + X-

2RX + 3NH3 → R2(NH) + 2NH +4+ 2X-

3RX + 4NH3 → R3N + 3NH +4 + 3X-

C6H5Cl + 2NH3 → C6H5NH2 + NH +4+ Cl-

e. Ammonolysis reactions:

In all these reactions the concentration of NH + is increased.

4

Hg2Cl2 + 2NH3 → Hg(NH2)Cl + Hg + NH +4 + Cl-

BX3 + 6NH3 → B(NH2)3 + 3NH 4+ + 3X-

AlCl3 + 2NH3 → AlCl2(NH2) + NH4+ + Cl- (In water : AlCl3 + 2H2O

→ AlCl2(OH) + H3O+ + Cl-)

Cl2 + 2NH3 → Ci(NH2) + NH4+ + 3Cl- (In water :Cl2 + 2H2O →

Cl(OH) + H3O+ + Cl-)

POCl3 + 6NH3 → PO(NH2)3 + 3NH4++3Cl-(In water:POCl3 + 6H2O

→ PO(OH)3 + 3H3O++ 3Cl-)

PCl3 + 6NH3 → P(NH2)3 + 3NH ++3Cl

4
-

HCl + NH3 → NH 4+ + Cl-

6. Complex Formation Reactions:

a. Many metal salts (e.g. Zn(NO3)2, AICi3, etc.) react with excess of KNH2
solution in liq NH3 to form soluble amido complexes. For example:
i. Zn2+ + 4NH2-(excess) → [Zn(NH2)4]2-

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University of Lucknow
 Zn(NO3)2 + 2KNH2 → K2[Zn(NH2)2] (insoluble) + 2KNO3

Zn(NH2)2 + 2KNH2(excess) → K2[Zn(NH2)4]

On adding: Zn(NO3)2 + 4KNH2 → K2[Zn(NH2)4] (soluble) + 2KNO3

Above reaction that occurs in aqueous(H2O) medium.

Zn(NO3)2 + NaOH → Zn(OH)2 (insoluble) + 2NaNO3

Zn(OH)2 + 2NaoH(excess) → Na2[Zn(OH)4]

On adding: Zn(NO3)2 + 4NaOH → Na2[Zn(OH)4] (soluble amido

complex) + 2NaNO3

ii. Al3+ + 4NH 2-(excess) → [Al(NH )2]-

4

AICI3 + 3KNH2 → Al(NH2)3 (insoluble) + 3KCI

Al(NH2)3 + KNH2(excess) → K[Al(NH2)4]

On adding: AICI3 + 4KNH2 → K[Al(NH2)4] (soluble amido complex)

+ 3KCI

This reaction can be compared with the reaction of AICl3 with excess of NaOH
taking place in aqueous solution.

Al3+ + 4OH- → [Al(OH)4]-(soluble hydroxo complex) or [AlO - + 2H

2 O]

AICI3 + 3NaOH → [Al(OH)3](ppt) + 3NaCl

[Al(OH)3](ppt) + 4NaOH(excess) → Na[Al(OH)4] (soluble hydroxo

complex)

On adding: AICI3 + 4NaOH(excess) → 3NaCl + Na[Al(OH)4]

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University of Lucknow
 b. Many metal amides,imides and nitrides dissolve in the excess of KNH2
in liq. NH3 to form soluble amido complexes. For example
i. Zn(NH2)2 + 2KNH2 (excess) → K2[Zn(NH2)4] (soluble amido
complex)
ii. AgNH2 + KNH2 (excess) → K[Ag(NH2)2]
iii. Al(NH2)3 + KNH2 (excess) → K[Al(NH2)4]

7. Redox Reactions:
a. Redox reactions in which liq. NH3 serves as a medium only.
i. KMnO4 acts as a weak oxidising agent in liq. NH 3. It oxidises
KNH2 to N2 in liq. NH3 and is itself reduced to K2MnO4.

6KMnO4(Mn=+7) + 6KNH2(N=-3) → 6K2MnO4(Mn=+6) + 6NH3 + N2(N=0)

ii. Iodine also acts as a weak oxidising agent in liq.NH 3.It oxidises
potassium ammonostannite, K4[Sn(NH2)6] to potassium
ammonostannate, K2[Sn(NH2)6] and is itself reduced to KI.

I2 (I=0) + K4[Sn(NH2)6] (Sn=+2) → K2[Sn(NH2)6] (Sn=+4) + 2KI (I=-1)

b. Redox reactions in which liq. NH3 (N= -3, H = +1) itself acts as a
reducing agent:
i. 4NH3(N=-3) + 5O (O=0) → 4NO (N=+2) +6H2O (O=-2)
ii. 2NH3(N=-3) + 3CuO (Cu=+2) → N2 (N=0) + 3Cu (Cu=0)+ 3H2O
c. Redox reactions in which alkali metals in liq. NH3 acts as
reducing agents:

Liq.NH3 can dissolve the alkali metals in it. The solution thus obtained
contains ammoniated electrons. These electrons reduce various
substances. Thus alkali metals in liq. NH 3 are able to reduce a variety of
substances and are themselves oxidised to some alkali metal salt.

i. Sodium in liq.NH3 reduces ammonium salt to H2

2Na (Na=0) + 2NH4Br (H=1) → 2NaBr (Na=+1) + H2 (H=0)

Dr. Shashi Bala, Dept of Chemistry, 16

University of Lucknow
 ii. Potassium in liq. NH3 reduces nitrous oxide (N2O) to N2 2K

(K=0) + NH3 + N2O → KNH2 (K=+1) + KOH + N2 (N=0)

iii. Sodium in liq. NH3 reduces elemental sulphur to sodium sulphide

(Na2S)

S (S=0) + 2Na (Na=0) → Na2S (Na=+1,S=-2)

iv. Li and Na in liq.NH3 reduce elemental oxygen to their peroxide,

while other alkali metals give their peroxide (M2O2) as well as
superoxide (MO2).

2K (K=0) + O2 (O=0) → K2O2 (K=+1,O=+1) (peroxide - white)

K (K=0) + O2 (O=0) → KO2 (K=+1,O=-1/2) (superoxide-yellow)

v. Na in liq. NH3 reduces CuI to Cu

Cul (Cu=+1) + Na (Na=0) → Cu (Cu=0)+ Nal (Na+1)

vi. K in liq. NH3 reduces KMnO4 to MnO and is itself oxidised to

KNH2.

30K(K=0)+20NH3+6KMnO4(Mn =+7) →
6MnO(Mn=+2)+18KNH2(K=+1)+18KOH +3H2+N2

vii. Na in liq. NH3 reduces Znl2 to NaZn4 and is itself oxidised to Nal.

4ZnI2 (Zn=+2)+ 9Na (Na=0) → NaZn4 (Zn=-1/4) + 8NaI (Na+1)

viii. Excess of K in liq. NH3 reduces K2[Ni(CN)4] and

[Pt(NH3)4]Br2 to K4[Ni(CN)4] and [Pt(NH3)4]0respectively.

K2[Ni(CN)4] (Ni=+2)(excess of K in liq. NH3 (-330C) → K4[Ni(CN)4] (Ni=0)

[Pt(NH3)4]Br2 (Pt=+2)((excess of K in liq. NH3 (-330C) → [Pt(NH3)4]0 (Pt=0)

Dr. Shashi Bala, Dept of Chemistry, 17
University of Lucknow
8. Dissociation of Weak Acids by Liq. NH3:

Since liq. NH3 has strong proton accepting ability, it accepts a proton from
weak acids like CH3COOH.

NH3 (l) + CH3COOH → NH4+ +CH3COO-

CH3COOH is completely ionised in liq. NH3 and hence acts as a strong acid in
liq, NH3.

9. Reactions in Which NH3 accepts a Proton : Pyrolysis :

NH3 is a powerful proton acceptor to form NH + ion.
4 For example:

a. NH3 picks up a proton from H2O to form NH + and

4 OH- ions

NH3 + HOH → NH +4+ OH-

The high solubility of NH3 in H2O is due to the above reaction

b. CH3COOH is a weak acid in H 2O but shows strong acidic character in

+
liq.NH3 because NH3 picks up a proton from CH3COOH to form NH
ion. 4

NH3 (l) + CH3COOH → NH +4 +CH3COO-

c. Urea (NH2CONH2) and acetamide (CH3CONH2) are weakly basic in

aqueous solution but show acidic properties in liq. NH 3
+
since these compounds can donate a proton to NH 3 to produce NH
ion.4

H2N-CO-NH2 + NH3 → H2N-CO-NH- + NH + 4

H3C-CO-NH2 + NH3 → H3C-CO-NH- + NH + 4

d. Sulphonic acid (NH2SO2OH) behaves as a dibasic acid in liq. NH3 H2N-

SO2-OH + 2NH3 → HN--SO2-O- + 2NH + 4

Dr. Shashi Bala, Dept of Chemistry, 18
University of Lucknow
 Here it may be noted that NH2SO2OH acts as a monobasic acid in
aqueous solution, since only the OH group present in this compound
donates a proton to H2O.

H2N-SO2-OH + H2O → H2N--SO2-O- + H3O+

e. AgNH2 behaves as a weak base in aqueous solution but in liq.NH3 it

behaves as an acid.

AgNH2 + 2NH3 → [Ag(NH2)2]- + NH +4

In all the above examples concentration of NH 4 increased.

Hence,according to Cady and Esley concept of acids and bases, all these
substances behave as acids in liq.NH3.

Advantages of Using Liquid Ammonia as a Solvent:

1. All the alkali metals,without reacting with liq. NH 3, is soluble in this solvent.
The dissolved alkali metals can be recovered by evaporating the alkali metal-
liq.NH3 solution.
2. The alkali metal-liq NH3 solution contains ammoniated electrons and hence
these solutions act as strong reducing agents.
3. The study of precipitation reactions taking place in liq.NH 3 these reactions can
be used to precipitate metallic halides, sulphides, alcoholates, amide, imide and
nitrides.

Disadvantages of Using Liquid Ammonia as a Solvent :

1. Low temperature or high pressure is necessary while working with

liq.NH3.This is because of the fact that the liquid range for liq.NH 3 is from -
34.0°C to -77.70C.
2. Liq. NH3 is hygroscopic in nature and hence all the reaction must be carried out
in a sealed tube.

Dr. Shashi Bala, Dept of Chemistry, 19

University of Lucknow
 3. Liq, NH3 has an offensive odours and hence the use of liq.NH 3 as a solvent and
as a reaction medium requires special technique.

Liquid Sulphur Dioxide (Liq.SO2)

Introduction: Liq.SO2 is a non-protonic solvent,because it cannot give a proton on

self ionisation. Under normal tempereture and pressure, sulphur dioxide is a gas but
can be readily liquefied.It has a wide liquid range from
-10.00C(b.p.) to -75.50C(m.p.) and hence can be used as a solvent.It’s dielectric
constant is low (=17.4 at -200C) and hence it is poor solvent for ionic compounds but
acts as a good solvent for covalent compound.

Solubility of various substances in liq.SO2:

A. Solubility of ionic compounds (inorganic salts):

Iodide and thiocyanates : Most soluble Sulphates,sulphides,oxides and
hydroxides : Partially insoluble Ammonium,thallium and mercuric
salts : Soluble
B. Solubility of non-ionic compounds (covalent compound) :
Covalent halide like IBr,BCl3,AlCl3,AsCl3,PBr3,CCl4,SiCl4 and SnCl4 :
Soluble
Organic compound like amines, ether, alcohols, benzene, alkenes,
pyridine,quinoline, Halogen derivatives and acid chlorides : Soluble Alkanes :
Insoluble
C. Solubility of metals:
Metals are insoluble in liq.SO2
D. Conductivity of salt solution:
Conductivity of electrolyte solution of salt containing
Na+,NH 4+,K+,(CH )3 S3 + and (CH ) N3
+
increase with the increase in the size of
4
these cations. Increasing order of conductivity :
Na+ < NH 4+ < K+ < (CH )3 S3+ < (CH ) 3N+
4
SIze of anions in increasing order of conductivity:
SCN- < ClO -4< Cl- < I-

Dr. Shashi Bala, Dept of Chemistry, 20

University of Lucknow
Auto-Ionisation of liq.SO2:

SO2 + SO2 ⇄ SO2+(thionyl ion) + SO 32-(sulphite ion)

(solvent) (solvent) (solvent cation:acid) (solvent anion:base)

Compare the self ionisation of liq. SO2 with water and liq.NH3: SO2+ ion analogous to
H3O+ and NH + ions while SO4 2- ion is analogous3 to OH- and NH - ions produced by
2
the self-ionisation of H2O and liq. NH3 respectively.

Chemical reaction taking place in Liq.SO2 :

1) Metathetical (Precipitation) Reaction:

a) Thionyl chloride (SO2Cl2) in liq.SO2 has helped to prepare many

compounds.
2KBr + SOCl2 → 2KCl↓ + SOBr2
2KI + SOCl2 → 2KCl↓ + SOI2
NH4(SCN) + SOCl2 → NH4Cl↓ + SO(SCN)2
2Ag(CH3COO) + SOCl2 → 2AgCl↓ + SO(CH3COO)2

b) Some other reaction precipitation reaction that carried out in

liq.SO2:
SbCl3 + 3LiI → SbI3↓ + 3LiCl
PbF2 + Li2SO4 → PbSO4↓ + 2LiF
AlCl3 + 3NaI → AlI3↓ + 3NaCl
BaI2 + Zn(CNS)2 → Ba(CNS)2↓ + ZnI2

2) Acid-Base neutralisation (salt formation) reaction:

In these reactions compounds contain SO 2+ ion(acid) combined with
compounds containing SO3 ion(base) to form the salt and the solvent
(liq.SO2).E.g.
a) SOCl2(acid) + Cs2SO3(base) → 2CsCI(salt) + 2SO2(solvent)
Or SO 2+ + 2Cl- + 2Cs+ + SO 2- 3 .→ 2Cs+Cl- + SO2+ + SO 2-
3

b) SO(SCN)2 + K2CO3 → 2K(SCN) + 2SO2

c) SOBr2 + [N(CH3)4]2SO3 → 2[N(CH3)4]Br + 2SO2

3) Amphoteric behavior of salts in liq.SO2 :
Dr. Shashi Bala, Dept of Chemistry, 21
University of Lucknow
 a) Acidic and basic character with salts of Zn(II) and Al(III)

ZnCl2(acid) + K2SO3 → ZnSO3 + 2KCl

ZnSO3(base) + K2SO3 → K2[Zn(SO3)2]
2AlCl3(acid) + 3K2SO3 → Al2(SO3)3 + 6KCl
Al2(SO3)3(base) + 3K2SO3 → 3K3[Al(SO3)3]

b) Acidic and basic behavior with AlCl3 and GaCl3

AlCl3(acid) + 3OH- → Al(OH)3(ppt) + 3Cl-

2AlCl3(base) + 3SO 2-3 → Al(SO ) 3 + 6Cl-
3

4) Solvation Reactions : Formation of Solvates:

Like water and liq. NH3,liq.SO2 also form addition compounds(solvates) with
solutes.
E.g.LiI.2SO2, KBr.4SO2, MI.4SO2 (M=Na,K,Rb), MI2.4SO2 (M=Ca,Ba,Sr),
AlCl32SO2

5) Solvolytic or solvolysis reaction:

PCl5 +→ POCl3 + SOCl2

SO2
(l)
NbCl5 +→ NbOCl3 + SOCl2 (at 700 C)
SO2(
l)
WCl6 + SO2(l) → WOCl4 + SOCl2 (at 700 C)
UCl6 2SO2(l) → UO2Cl2 + 2SOCl2

6) Complex formation reaction:

A large number of complex compounds is formed by SbCl3 and SbCl5 in liq.SO2.
SbCl3 + 3KCl → K3[SbCl6] (in liq. SO2)
SbCl5 + KCl → K[SbCl6] (in liq. SO2)
SbCl5 + CH3COCl → [CH3CO][SbCl6] (in liq. SO2)
2SbCl3 + 3SOCl2 → [SO]3[SbCl6]2 (in liq. SO2)
SbCl5 + NOCl → [NO][SbCl6] (in liq. SO2)

7) Redox reaction:
Dr. Shashi Bala, Dept of Chemistry, 22
University of Lucknow
 Liq.SO2 does not have any strong oxidising or reducing properties, although it
may serve as a medium for redox reaction. It reduced iodine but not bromine.
I2 + 2RSO3 → RSO4 + RI2 + SO2

3SbCl5 ⇄ 3I2
Conversely soluble iodide oxidised to free iodine by SbCl5. 6KI +
+ SbCl3 + 2K3[SbCl6] (in liq.SO2)

8) Reactions with Organic compounds:

a) Hydrocarbons undergo sulfonation in liq.SO2 :
C6H6 + ClSO3H → C6H5SO3H + HCl

b) Friedel-Craft’s reaction :
AlCl3 which is used as a catalyst and reaction carried out in liq.SO2 medium.

c) Bromination: Liq. SO2 is also used as a solvent in various

Bromination reactions.

Dr. Shashi Bala, Dept of Chemistry, 23

University of Lucknow
Dr. Shashi Bala, Dept of Chemistry, 24
University of Lucknow