CHM 424: Non-Aqueous Solvents

After studying this chapter, the student will be able to

Understand classification of solvents
Know the characteristics of non-aqueous solvents
Understand various concepts of acids and bases
Distinguish between levelling and differentiating solvents
Learn about relative strength of acids and bases
Realise the hard acid-base concept

1.1  INTRODUCTION

Most of the inorganic reactions are studied in aqueous solution, water being
the best-known solvent due to its high value of dielectric constant. However,
many non-aqueous solvents have also been studied extensively in the last few
years. A large number of non-aqueous polar solvents such as liquid ammonia,
glacial acetic acid, sulphuric acid, sulphur dioxide and hydrogen halides have
been introduced. The behaviour of a solvent is determined on the basis of
several physical properties as discussed below:

1. Dielectric Constant
For an ionic crystal, coulombic force of attraction F between the cation and
anion is given by the expression :

where q1 and q2 are the charges on the cations and anions respectively, r is
the distance between the cation and the anion and D is a constant, known as
dielectric constant. D depends on the nature of the solvent used to dissolve
the ionic crystal. The expression shows that if a solvent has higher value of
D, it will reduce the F, i.e. it will weaken the attractive forces in the crystal
and will dissolve it quickly. Thus, solvents with a high value of dielectric
constant such as anhydrous hydrogen fluoride and water can easily dissolve
an ionic compound as compared to a solvent with low value of dielectric
constant (suitable for dissolving nonpolar compounds).

2. Dipole Moment
Greater is the polarity of a solvent or higher the dipole moment of the
solvent, greater is the solvation energy released and hence greater is the
solubility of a solute. In general, an ionising solvent has high values of both
dipole moment and dielectric constant, as evident from Table 1.1.
Table 1.1 Dipole moment and dielectric constants of some ionising solvents

Solvent Dipole moment (Debye units) Dielectric constant

HCN 2.93 106.8 (25°C)
HF 1.91 83.6 (0°C)
H2O 1.84 78.5 (25°C)
C2H5OH 1.69 24.2 (25°C)
SO2 1.63 17.4 (–19°C)
NH3 1.46 22.0 (–34°C)

3. Melting Point and Boiling Point

The range of temperature in which a solvent can exist as a liquid is indicated
by its melting point and boiling point. A good solvent must have a wide range
of existence as a liquid. It is evident from Table 1.2 that water and sulphuric
acid hold a wide range of temperature and exist as liquid while the other
listed solvents can be used only at low temperatures.
Table 1.2 Melting points, boiling points and critical constants of some solvents

4. Heat of Fusion and Vaporisation

The nature and strength of the intermolecular forces in the solid and the
liquid state are indicated by their molar heats of fusion and vaporisation
respectively. The high values of these parameters indicate the high
intermolecular forces. The values of these parameters have been given in
Table 1.3 for some solvents. It can be concluded from the table that the
intermolecular forces are weakest in HF and greatest in SO2.
Table 1.3 Molar heats of fusion and vaporisation of various solvents

Solvent Molar heat of fusion (kJ mol−1) Molar heat of vaporisation (kJ mol−1)
SO2 7.40 24.93
H2O 6.02 40.65
NH3 5.65 23.34
HF 4.58 30.28

The Trouton constant is normally used to account for the intermolecular

forces in normal liquids. It is the ratio of the heat of vaporisation (J) to the
boiling point (K) of a solvent. Its value comes out to be 90 JK–1 mol–1 for
normal liquids, i. e. the liquids without any association. The polar liquids
undergo association and have a high value of the Trouton constant. Such
solvents include H2O, HF, NH3 and alcohols.
1.2  CLASSIFICATION OF SOLVENTS

The solvents can be classified in a number of ways as follows:

1.2.1 Depending upon the Proton–Donor and

Proton–Acceptor Ability
1. Protonic or Protic Solvents
The solvents which can either donate and or accept protons depending upon
the nature of the other species are known as protonic or protic solvents. All
these solvents have hydrogen atoms in their formula. These are further of
three types:
(a) Protogenic or Acidic Solvents These solvents can donate protons
readily. For example, HF, H2SO4, CH3COOH, etc.
(b) Protophilic or Basic Solvents These solvents can accept protons
readily. For example, NH3, C5H5, NH2NH2, etc.
(c) Amphi-protic or Amphoteric Solvents These solvents can show dual
character, i.e. can donate or accept protons depending upon the nature of
the other species. For example, H2O, CH3COOH, NH3, etc.

2. Aprotic or Non-protonic Solvent

These solvents can neither donate nor accept protons irrespective of
presence/absence of hydrogen in their formula. For example, C6H6, SO2,
CCl4, CHCl3, etc.

1.2.2 Depending upon the Polarity of the Solvent

1. Polar, Ionising or Ionic Solvent
The solvents which have high polarity and can undergo auto-ionisation, are
called polar, ionising or ionic solvents. These solvents also have high
dielectric constants and dissolve ionic compounds. These solvents have high
tendency to undergo association which leads to increase in boiling point and
hence the liquid-state range of the solvent. For example, H2O, NH3, HF, SO2,
etc. The auto ionisation of these solvents can be shown as

2. Nonpolar or Non-ionising Solvents

The solvents which are nonpolar and hence do not ionise at all, are called
nonpolar or non-ionising solvents. These solvents have dielectric constants
and very little associating tendency. These solvents cannot undergo auto-
ionisation and cannot dissolve ionic solutes but dissolve nonpolar solutes. For
example, C6H6, CCl4, etc.

1.2.3 Third Classification

1. Aqueous Solvent Water is known as aqueous solvent.
2. Non-aqueous Solvent All other solvents are known as non-aqueous
solvents. For example, NH3, SO2, HF, CHCl3, C6H6, etc. Some
important non-aqueous solvents will be discussed in this chapter.

1.3  LIQUID AMMONIA

Liquid ammonia is one of the most extensively used non-aqueous solvents in

various inorganic and organic reactions. It exhibits many characteristics
similar to those of water except that its dielectric constant is lower than that
of water. Thus, it is a poor solvent for ionic substances but at the same time, a
better solvent for nonpolar molecules. Some substances show a higher
solubility in liquid ammonia due to formation of stable ammine complexes.

1.3.1 Comparative Account of H2O and Liquid

NH3 as Solvents
1. Dielectric constant of liquid NH3 (22) is lower than that of water
(78.5).
 2. Its freezing point (–77.7°C) and boiling point (–33.5°C) are much
lower than the freezing point (0°C) and boiling point of H2O (100°C).
Thus, the liquid range of NH3 is very less.
3. Dipole moment of NH3 (1.47) is lower as compared to that of water
(1.85).
4. Viscosity of liquid NH3 (2.65 millipoise) is much less than that of
water (10.08 millipoise). However, this effect promotes the ionic
mobilities and compensates the effect of low dielectric constant to
some extent.
The auto-ionisation of H2O and liquid ammonia can be compared as

Thus, auto-ionisation of NH3 is analogous to that of H2O; however the extent

of ionisation is very less.
Any substance which increases the concentration of NH+4 ion in liquid
NH3 is known as an ammono acid, while the substance which increases the
concentration of NH2–, NH2– or N3– ions in liquid NH3 is known as an
ammono base. The ammono acid and ammono base combine together to form
un-ionised NH3. This is known as the process of neutralisation.

1. Ammono Acids
The examples include ammonium salts, organic amide, acetic acid, sulphamic
acid etc.
2. Ammono Bases
The examples include amides, imides and nitrides

In aqueous medium, a compound is said to be amphoteric if it dissolves both

in acids and bases. Similar is the case in liquid ammonia too.
For example, zinc hydroxide is amphoteric in aqueous medium.

Similarly, zinc amide is amphoteric in liquid NH3

Thus, amphoterism in liquid NH3 is analogus to that in H2O.

1.3.2 Chemical Reactions in Liquid Ammonia

The chemical reactions that take place in liquid NH3 are as follows:

1. Metathetical or Precipitation Reaction

The precipitate formation depends upon the solubility of a substance in the
solvent. As already discussed, due to difference in physical properties of
liquid NH3 and H2O, various substances differ in their solubilities in these
solvents. Thus, many precipitation reactions that are normally not possible in
water, may take place in liquid NH3. Some particular examples are the
following:
(a) In aqueous medium,
 This is due to the reason that most of the Chlorides (except NaCl, BeCl2
and NH4Cl) are insoluble in liquid. NH3.
(b) Metal iodides and bromides can be precipitated by treatment of
solutions of various nitrates in liquid NH3 with ammonium halides.

(c) (NH4)2S in liquid NH3 is used to precipitate the sulphides of many

metals such as Mg, Ba, Pb, Bi, Mn, Cu, Zn, Cd, Hg from their nitrate
solutions.

2. Reactions of Ammono Acids

(a) Neutralisation KNH2 + NH4Cl → KCl↓ + 2NH3
(b) Reaction with Active Metals The solutions of ammonium salts in liquid
NH3 can react with active metals to give hydrogen analogous to that in
aqueous medium.
Co + H2SO4 → CoSO4 + H2
In liquid NH3,
Blue solutions of alkali metals in liquid NH3 get decolourised on
treatment with ammonium salts.

(c) Protololysis Some compounds are incapable of donating protons to

water but can readily donate protons in liquid NH3 (protolysis).
Examples include urea, acetamide, acetamidine and sulphamide. These
are weakly basic in aqueous solution but behave as acid in liquid NH3
 The basicity of sulphamic acid is increased in liquid NH3.
In aqueous medium, H2NSO2OH + H2O → H2NSO2O– + H3O+
In liquid NH3,
CH3COOH, a weak acid in aqueous solution, behaves as a strong acid in
liquid NH3.

AgNH2, a weak base in aqueous solution, exhibits acidic property in

liquid NH3.

3. Reactions of Ammono Bases

Ammono bases are used to precipitate amides, imides and nitrides of many
metals. The general reaction can be represented as

It is evident that due to release of in all these reactions, the amide,

imide and nitride are all treated as ammono bases.
KNH2 + AgNO3 KNO3 + AgNH2.
KNH2 + PbI2 KI + HI + PbNH.
KNH2 + BiI3 KI + 2HI + BiN .

4. Solvolysis Reactions in Liquid NH3

In a solvolysis reaction, the solvent splits into its characteristic ions and
concentration of either of these ions increases due to interaction with cations
or anion of a salt. Solvolysis in H2O, alcohol and liq.NH3 are known as
hydrolysis, alcoholysis and ammonolysis respectively. For example, in
hydrolysis, concentration of either H3O+ or OH– is increased by auto-
ionisation of H2O.
Consider the
hydrolysis of CuSO4
Auto-ionisation of 2H2O + 2H2O 2H3O+ + 2OH−
H2O:
Ionisation of CuSO4:
Interaction of cation
with
characteristic ion of
solvent:

Similarly, in ammonolysis, concentration of either in or ion is

increased.
Auto-ionisation of H2O:
Ionization of SiCl4:
Interaction of cation with
characteristic ion of
solvent:

Some another examples of ammonolysis are given here:

(a) Ammonolysis of Inorganic Halides Ionic halides do not undergo
ammonolysis in liq.NH3, but many covalent halides tend to
ammonolyse.
 (b) Ammonolysis of Organic Halides Alkyl halides undergo slow
ammonolysis with liquid NH3 at its boiling point to give a mixture of
primary, secondary and tertiary amines.

Similarly,

(c) Ammonolysis of Cl2 and POCl3

(d) Ammonolysis of Alkali Metal Hydrides and Oxides

NaH + NH3 – NaNH2 + H2 Analogous NaH + H2O → NaOH +
to H2
Na2O + 2NH3 → 2NaNH2 + Na2O + H2O → 2NaOH
H2O

5. Solvation Reactions in Liquid NH3

In a solvation reaction, the solute and solvent species get attached to each
other by a coordinate or H-band to form an addition compound or adduct
known as solvate (Lewis acid-base reaction). Solvation in H2O and NH3 are
known as hydration and ammoniation respectively. Likewise, their adducts
are known as hydrate (for H2O) and ammoniate (for NH3). For example,
 BF3 + NH3 → BF3·NH3 (1 : 1 adduct)
SO3 + 2NH3 → SO3·2NH3 (1 : 2 adduct)
SiF4 + 2NH3 → SiF4·2NH3
Some other examples of ammoniation reaction are:
Cu2+ + 4NH3 → [Cu(NH3)4]2+
Co2+ + 4NH3 → [Co(NH3)6]2+
Ag+ + 2NH3 → [Ag(NH3)2]+ + 2H2O

6. Complex Formation in Liquid NH3

In aqueous system, many compounds react with the excess of alkalies to form
soluble complexes. For example,
Zn(NO3)2 + 4NaOH Na2[Zn(OH)4] + 2Na NO3
Zn(OH)2 + 2NAOH Na2[Zn(OH)4]
AlCl3 + 4NaOH Na[Al(OH)4] + 3NaCl
Similarly, in liquid NH3, many compounds react with the excess of an
ammino base to from soluble complexes—amido and/or imido.
For example :
(a) Zn(NO3)2 + 4KNH2 K2[Zn(NH2)4] + 2KNO3
Zn(NO3)2 + 4KNH2 K2[Zn(NH2)] + 2KNO3 + 2NH3
(b) Zn(OH)2 + 2NaNH2 Na2[Zn(NH2)4]
Zn(OH)2 + 2NaNH2 Na2[Zn(NH2)] + 2NH3
(c) AgNH2 + KNH2 K[Ag(NH2)2]
AgNH2 + KNH2 K[Ag(NH)] + NH3
(d) Zn(NH2)2 + 2NaNH2 Na2[Zn(NH2)4]
Zn(NH2)2 + 2NaNH2 Na2[Zn(NH2)2] + 2NH3
(e) AlCl3 + 4 NaNH2 Na[Al(NH)2]4 + 3NaCl

7. Redox Reaction in Liquid NH3

Many oxidising agents act as weaker oxidising agents in liquid ammonia than
in aqueous solutions e.g. KMnO4 is reduced to K2MnO4 in presence of KNH2
as
6KMnO4 + 6KNH2 6K2MnO4 + 4NH3 + N2
However, if instead of KNH2, potassium in liquid ammonia is used, KMnO4
is reduced to MnO.
6KMnO4 + 30K + 20NH3 → 6MnO + 18KNH2 + 18KOH + 3H2 + N2
Excess of K in liquid NH3 can reduce K2[Ni(CN)4] and [Pt(NH3)4]Br2 as
K2[Ni(CN)4] + 2K K4[Ni(CN)4]
[Pt(NH4)]Br2 + 2K [Pt(NH3)4] + 2KBr
K in liquid NH3 also reduces nitrous oxide to N2 as
2K + NH3 + N2O KNH2 + KOH + N2
Reaction with oxygen takes place as K + O2 KO2 ; 2K + O2
K2O2
Oxidising action of iodine is also weaker in liquid NH3
I2 + K4[Sn(NH2)6] _ K2[Sn(NH2)6] + 2KI
Sodium in liquid NH3 is able to reduce various substances as
2Na + S Na2S
Na + Cul Cu + Nal
2Na + O2 Na2O2
Liquid NH3 itself acts as a reducing agent for many subsances
2NH3 + 3Mg → Mg3N2 + 3H2
2NH3 + 3CuO → N2 + 3Cu + 3H2O

1.3.3 Solubility of Various Substances in Liquid

NH3
Liquid NH3 is a poor solvent for ionic substances due to its low dielectric
constant. However, most ammonium salts are soluble in water. Such
examples include CH3COONH4, NH4NO3 etc.
Similarly, most of the perchlorates, cyanides, thiocynates, nitrites and
nitrates are soluble in liquid ammonia. Amongst the halides, the fluorides are
least soluble and solubility increases from fluorides to iodides. Thus,
chlorides (except BeCl2 and NaCl) are insoluble, whereas the iodides are
freely soluble. Most of the bromides are slightly soluble in liquid NH3.
Sulphides, phosphates, oxides, hydroxides and carbonates are insoluble in
liquid NH3. Most of the metal amides are insoluble, except those of alkali
metals. Many metal salts dissolve in liquid NH3 due to the formation of
ammoniates. Some particular examples are
[Cu(NH3)4]2+, [Ni(NH3)6]2+, [Fe(NH3)6]2+, [CrNH3)6]3+, [Hg(NH3)2]2+ and
[Pt(NH3)4]2+, etc
Many organic compounds such as halogen compounds, alcohols, ketones,
esters, phenols, simple ether, amines are soluble in liquid NH3. However,
alkanes are insoluble, whereas alkenes, alkynes and aromatic hydrocarbons
are sparingly soluble. The nonmetals dissolve in liquid NH3 by reacing with
it.

The metals with low ionisation energies, high energies of solvation and
low energies of sublimation, alkali and alkaline earth metals (except Be)
readily dissolve in liquid ammonia. In case of alkali metals, the solubility
increases lower the group as Li < Na < K < Cs (Table 1.4).
Table 1.4 Solubility of alkali metals in liquid ammonia
 The solutions of alkali metals in liquid NH3 have very extraordinary
properties. This dissolution of alkali metals in liquid NH3 probably does not
involve a chemical change in the metal, as the metal is regenerated when the
solution is evaporated. (The alkaline earth metals are recovered as hexa-
amoniates). All the solutions are blue in dilute form, but bronze coloured
when the concentration exceeds 1 M. On further increase of concentration,
the colour disappears. The dissolution can be represented in terms of the
production of solvated metal ions and electrons produced by ionisation of the
metal atoms.

It is believed that the solvated electrons reside in the cavities surrounded by

the ammonia molecules (with their protons oriented towards the electrons
(Fig. 1.1). This representation attributes to the low density of these solutions
as compared to that of the solvent. The blue colour of the solution is due to
the presence of these solvated cations and electrons.

Fig. 1.1 Representation of solvated electrons

The dilute solution has very high electrical conductivity in the range of
fully ionised salts. As the concentration is increased, the conductivity
decreases and is characteristic of the metal. The dilute solutions are
paramagnetic due to presence of solvated electrons, but as the concentration
of the solution is increased, the magnetic succeptibility decreases and finally
the solution becomes diamagnetic. It is believed that with an increase in
concentration, the solvated cations tend to form aggregates such as M2, M3,
etc. The very dilute solutions are metastable and undergo decomposition in
the presence of a catalyst.
M + nNH3 → H2 + M(NH2)n
The decomposition reaction also takes place slowly upon long standing of
the solutions. Due to presence of ammoniated electrons, the blue solution of
alkali metals in liquid NH3 are strongly reducing.
1.3.4 Advantages of Liquid Ammonia as a Solvent
1. It is quite clear with the above discussion that use of liquid NH3 as a
solvent for dissolution of alkali metals is highly useful as the dissolved
alkali metals can be recovered easily from the solution by simple
evaporation.
2. The dilute blue solutions of alkali metals are very strong reducing
agents and can be used for reducing the substances soluble in liquid
NH3.
3. Many metallic salts that cannot be precipitated in aqueous medium are
easily obtained.
4. Liquid ammonia has very less tendency for solvolysis of dissolved
solutes.

1.3.5 Disadvantages of Using Liquid Ammonia as a

Solvent
1. Liquid range for ammonia lies in between –33.5°C to –77.7°C. Hence,
low temperature or high pressure has to be maintained while working
with it.
2. Liquid ammonia is hygroscopic in nature, hence the reactions are
carried out in sealed tubes so as to avoid contact with moisture.
3. Due to offensive odour of liquid NH3, special techniques are required
to use it as a solvent and reaction medium.

1.4  LIQUID SULPHUR DIOXIDE

Liquid SO2 is a nonprotonic solvent as it contains no hydrogen atoms and

hence does not give a proton (H+) on ionisation. The concept of acids and
bases based upon the solvent system was first given for sulphur dioxide. The
auto-ionisation of SO2 was suggested as

The thionyl ion is analogous to the hydronium ion, while the sulphite ion is
analogous to the hydroxyl ion and the amide ion.
Although SO2 is a gas under normal temperature and pressure, yet it is
extensively used in industries as it can be readily liquified. Its liquid range is
sufficiently high (–10°C to –75.5°C) and hence it can be used as a solvent for
many covalent substances. Due to its low dielectric constant (17.4 at –20°C),
it is a poor solvent for ionic compounds, however, the highly charged ionic
species are soluble in this solvent. This is due to the presence of the π
electrons in the SO2 molecules which leads to formation of ven der Waals
interactions between the solute and solvent molecules.The physical properties
of liquid SO2 are given in Table 1.5.
Table 1.5 Physical properties of liquid sulphur dioxide

Property Value
Trouton’s constant 22.7
Dipole moment 1.61 Debye
Dielectric constant 17.4 (−20°C)
Freezing point −75.5°C
Boiling point −10°C
Specific condutance 3.4 × 10−8 ohm−1 cm−1 (−10°C)
Density 1.46 g ml−1 (−10°C)
Viscocity 0.428 centipoise (−10°C)
Enthalpy of fusion 1.97 kcal mol−1
Enthalpy of vaporisation 5.96 kcal mol−1

1.4.1 Solubility of Substances in Liquid SO2

Iodides and thiocyanates of alkali metals are the most soluble. The
solubilities of other halides decreases in the order MI > MBr > MCl > MF.
Most of the ammonium, thallium and mercuric salts are insoluble. Most of
the sulphites, cyanides and acetates are moderately soluble. Many covalent
halides such as PBr3, BCl3, AlCl3, AsCl3, CCl4, SiCl4, GeCl4, SnCl4, IBr are
soluble in liquid SO2.PCl3, POCl3, and SOCl2 are highly soluble in
accordance with the hard soft interaction principles.
Aliphatic hydrocarbons are insoluble but the aromatic hydrocarbons and
alkenes are highly soluble. In fact, liquid SO2 is used as a reaction medium in
a number of organic reactions and for solvent extraction method to separate
the aromatic and aliphatic hydrocarbons.

1.4.2 Conductivity of Salt Solutions in Liquid SO2

The dissociation and conductivity of electrolytes in liquid SO2 is roughly
related to the size of cation as
Na+ < NH4+ < K+ < Rb+ < (CH3)3S+ < (CH3)4N+ and
for various anions as
Solutions of many highly soluble covalent compounds are highly
conducting in nature.

1.4.3 Chemical Reactions in Liquid SO2

1. Acid–Base Reactions
In accordance with the auto-ionisation of liquid SO2, the compounds which
contain or increase the concentration of ions act as bases, while the
compounds which contain or increase the concentration of SO2+ act as acids
in liquid SO2.

Thus, SOCl2, SOBr2, SO(SCN)2 etc. behaves as acid in liquid SO2 while the
substances such as K2SO3, Cs2SO3, [N(CH3)4]2 SO3 act as a base.
The acid base reaction in liquid SO2 can be represented as
SOCl2 + Cs2SO3 2CsCl + 2SO2
SOBr2 + [N(CH3)4]2SO3 2[N(CH3)4]Br + 2SO2

2. Precipitation Reactions
In accordance with the specific solubility relationships, several insoluble
materials can be precipitated in liquid SO2 as mentioned below:
(a) Metal chlorides are precipated from the solutions of soluble metallic
salts and SOCl2 in liquid SO2.
 2KI + SOCl2 2KCl ↓ + SOI2
2Ag(CH3COO) + SOCl2 2AgCl ↓ + SO(CH3COO)2
From these reactions, many new thionyl derivatives are obtained.
(b) Precipitates of other compounds have also been obtained.
AlCl3 + 3NaI 3NaCl ↑ +AlI3
SbCl3 + 3LiI SbI3 ↓ + 3LiCl
PbF2 + Li2SO4 PbSO4 ↓ + 2LiF
BaI2 + Zn(CNS)2 Ba(CNS)2 ↓ + ZnI2

3. Solvolysis Reactions in Liquid SO2

The solvolysis reactions are quite typical and differ from the true solvolysis
reactions.
(a) Many covalent halides form oxyhalides during solvolysis and increase
the concentration of SO2+ ions.
PCl5 + SO2 (liq.) → POCl3 + SOCl2
AsCl5 + SO2 (liq.) → AsOCl3 + SOCl2
UCl6 + 2SO2 (liq.) → UO2Cl2 + 2SOCl2
WCl6 + SO2 (liq.) → WOCl4 + SOCl2
(b) CH3COONH4 increases the concentration of ion during solvolysis
in liquid SO2.
2CH3COONH4 + 2SO2 (liq.) → (NH4)2SO3 + (CH3CO)2O + SO2
(c) Zinc diethyl reacts in a typical way.
Zn(C2H5)2 + SO2 (liq.) → ZnO + (C2H5)2SO

4. Solvation Reactions in Liquid SO2

Liquid SO2 can act as a lewis base and forms a variety of solvates containing
one or more molecules of sulphur dioxide. Some typical examples are
LiI·2SO2, KBr·4SO2, NaI·4SO2, KI·4SO2, RbI·4SO2, SrI·4SO2, AlCl3·2SO2,
K(SCN)·2SO2, Cs(SCN)·SO2, [(CH3)4N]·3SO2, Dioxane·2SO2.

5. Complex Formation in Liquid SO2

Due to presence of lone pair of electrons on both the S and O atoms, it can
form many complexes,
(a) Many compounds react with a compound containing ions to form
precipitates, which dissolve in excess of due to formation of
soluble complexes.
Reaction with AlCl3
2 AlCl3 + 3K2SO3 Al2(SO3)3 ↓ + 6KCl
Al2(SO3)3 + 3K2SO3 2K3[Al(SO3)3]
Similarly, soluble sulphito complex, [N(CH3)4]3[Al(SO3)3], is obtained
by treating AlCl3 with excess of [N(CH3)4]2SO3.
Reaction with ZnCl2
ZnCl2 + K2SO3 ZnSO3 + 2KCl
ZnSO3 + K2SO3 2KCl + K2[Zn(SO3)2]
Similarly,
SbCl3 + KCl K3[SbCl6]
SbCl5 + KCl K[SbCl6]
SbCl5 + NOCl [N(CH3)4][SbCl6]
(b) Solubility of many compounds in SO2 is increased greatly on addition
of KI or PbI due to formation of soluble comlexes.
KI + I2 KI3
RbI + I2 RbI3
2KI + HgI2 K2[HgI4]
6. Amphoteric Behaviour in Liquid SO2
Many compounds whose hydroxides are amphoteric in aqueous medium
behave in an analogous way in liquid SO2.
AlCl3 reacts with NaOH to give gelatinous precipitate of Al(OH)3.

The precipitates dissolve in excess of NaOH to form the soluble complex.

Al(OH)3 can be reprecipitated from the soluble complex by the addition of

HCl.
Na(Al(OH)4) + HCl Al(OH)3 ↓ + NaCl + H2O
Similarly, in liquid SO2, the reaction takes place as
2AlCl3 + 3K2(SO3) Al2(SO3)3 + 6KCl
Al2(SO3)3 + 3K2 SO3 2K[Al(SO3)3]
Al2(SO3)3 can be reprecipitated as
2K3[Al(SO3)3] + 3SOCl2 6KCl + Al2(SO3)3 + 6SO2

7. Redox Reactions in Liquid SO2

Liquid SO2 does not have redox properties like gaseous SO2 and is used only
as a medium for redox reactions. Interestingly, I2 is reduced by a sulphite in
liquid SO3.
I2 + K2SO3 2KI + K2SO4 + SO2
I2 + 2R2SO3 2RI + R2SO4 + SO2
While, a soluble iodide is oxidised by SbCl5 or FeCl3 in liquid SO2.
6KI + 3SbCl5 3I2 + SbCl3 + 2K3[SbCl6]
 2KI + 2FeCl3 I2 + 2FeCl2 + 2KCl
Table 1.6 Comparison of H2O, liquid NH3 and liquid SO2 as solvents.

1.5  ANHYDROUS HYDROGEN FLUORIDE

Anhydrous hydrogen fluoride is an excellent ionising solvent. Because to its

special characteristics, HF persists as (HF)6 in the vapour phase and forms
chains and rings of various sizes due to H-bonding. Its boiling point is 19.4°C
and freezing point is –89.4°C. Thus, it has a wide liquid range compared to
other non-aqueous solvents. It has high dielectric constant (83.6 at 0°C) and a
dipole moment (1.90 D) quite close to that of water. However, due to its low
specific conductance, poisonous character and ability to dissolve only a few
substances without any chemical reaction limits its use as a non-aqueous
solvent. Table 1.7 lists the characteristic physical properties of HF.
Table 1.7 Physical properties of Anhyd. HF.

Property Value
Freezing point −89.4°C
Boiling point +19.4°C
Dipole moment 1.90D
Dielectric constant 83.6 (0°C)
Density 0.99 g ml−1
Viscocity 0.256 centipoise (15°C)
Specific conductance 1.4 × 10−5 ohm−1 cm−1 (15°C)

Auto-ionisation of HF
Liquid HF is highly ionised as
 Due to H-bonding in HF, the reaction can be represented as

Thus, any substance which increases the concentration of H2F+ will act as
an acid and the substance which increase the concentration of F– will act as a
base in HF. However, even acids which appear strong in aqueous solution,
behave as bases in HF.

Electron-aceptor fluorides such as BF3, AsF3, SnF4, PF5 and SbF5 act as an
acid in HF.

These solutions can dissolve electropositive metals such as Mg.

Ionic fluorides such as the fluorides of alkali metals, alkaline earth metals,
silver and thallium (I) act as bases in HF as the concentration of F– ions is
increased and that of H2F+ ions is decreased.

KH2F3 has also been formed with HF.

The acids which are weak in aqueous solutions behave as bases in HF.
For example :

1.5.1 Chemical Reactions in Liquid HF

1. Precipitation Reactions
Sulphates, periodates and perchlorates of non-alkali metals are easily
precipitated in liquid HF.
2AgF + Na2SO4 Ag2SO4 ↓ + 2NaF
TlF + KClO4 TlClO4 ↓ + KF
AgF + KIO4 AgIO4 ↓ + NaF
AgNO3 + BF3 + 2HF → AgBF4 + H2NO3F

2. Protonation of Organic Compounds

Organic compounds such as alkanes, benzene, ethers, ethanol, aldehydes,
ketones, carboxylic acids, etc. give conducting solutions in HF due to
protonation on dissolution. The solubility is increased further by addition of
fluoride acceptors (BF3, SbF5).

3. Formation of Addition Compounds

Metallic fluorides form a number of addition compounds in the HF. For
example, KF.2HF, KF.3HF and NH4F.HF.

4. Redox Reaction
Metals and hydrofluoro acids undergo redox reactions in HF.
3HAsF6 + 2Ag 2AgAsF6 + AsF3 + 3HF
These reactions are analogous to those taking place between metal and HNO3
in aqueous solutions.

5. Solvolysis Reactions
Simple salts undergo solvolysis as
 KCN + HF → HCN ↑ + K+ + F–
KCl + HF → HCl ↑ + K+ + F–
Some salts undergo solvolysis which is followed by further reaction as
follows:
(a) KNO3 + HF → HNO3 + K+ + F–
HNO3 + 2HF → H2NO3+ + F–
H2NO3+ + HF → NO2+ + H3O+ + F–
(b) H2SO4 + 2HF → H2SO4 + 2K+ + 2F–
H2SO4 + HF → HSO3F + H2O
H2O + HF → H3O+ + F–

1.5.2 Solubility of Some Compounds in Liquid HF

AlF3 is slightly soluble in liquid HF. However, the solubility increases on
addition of NaF.
AlF3 + NaF Na[AlF4]
AlF3 is precipitated back on the addition of BF3.
Na[AlF4] + BF3 → AlF3 ↓ + NaBF4
Similarly, solubility of CrF3 in HF is enhanced in presence of NaF.
CrF3 + 3NaF → Na[CrF6]
CrF3 is precipitated back on the addition of RF3.
Na3[CrF6] + 3BF3 → CrF3 ↓ + 3NaBF4

1.6  ANHYDROUS SULPHURIC ACID

Anhydrous sulphuric acid is a highly associated solvent due to presence of H-

bonding. As a result, it has a high boiling point and high viscosity, even 25
times more than that of water. Thus, the solutes dissolve very slowly in this
solvent and are not easily crystallised. Hence, it is not preferred as a solvent
for usual reactions. It is rather used as a dehydrating agent to extract water
from chemical compounds.

1. Auto-protolysis of H2SO4
H2SO4 undergoes auto-protolysis as

Thus, any substance which increases the concentration of acts as an

acid and the substance which increases the concentration of acts as a
base in H2SO4. However, there are other species formed in the following
dissolution equilibria:

2. Substances as Base in H2SO4

The substances which behave as a base in water are also basic in H2SO4.

The substances which dissociate to produce HSO–4 ions act as a base in

H2SO4.

The substances with lone pairs of electrons such as amides behave as

bases in H2SO4, as they accept protons from it.

The substances which act as an acid in aqueous solutions (including weak

acids and strong acids) act as bases in H2SO4.

HNO3 reacts with H2SO4 as

Acetic acid readily accepts a proton from H2SO4.

However, a number of carboxylic acids decompose in H2SO4 to give acyl

ion.

For example,

Mesitoic acid is recovered back if water is added, while addition of

methanol gives methylester (impossible to obtain via direct reaction). Some
carboxylic acids decompose to give carbon monoxide in H2SO4.

Except alkanes, most organic compounds dissolve in H2SO4 and are easily
protonated. Water easily accepts protons from H2SO4.

3. Substances as Acids in H2SO4

Perchloric acid, chlorosulphuric acid and fluorosulphuric acid behave as
weak acids in sulphuric acid.

Sulphur dioxide and borontris(hydrogensulphate) are moderately strong acids

in H2SO4.

Similar is the case of fuming sulphuric acid (oleum) and hydrogen

tetrakis(hydrogensulphato)borate.

HB(HSO4)4 can be obtained in solution form by dissolving boric acid in

sulphuric acid followed by addition of excess of fuming sulphuric acid.

The extremely strong acids which are even more acidic than H2SO4, are
known as super acids. Mixtures of very strong Lewis acids such as SbF5 and
very acidic protonic solvents such as HSO3F, HF, CF3SO3H and H2S2O7 are
the particular examples of such super acids.
A mixutre of SbF5 in HSO3F is termed magic acid and it can protonate
even an extremely weak base.

1.6.1 Chemical Reactions in Anhydrous H2SO4

1. Redox Reactions in H2SO4

Anhydrous sulphuric acid acts as a mild oxidising agent. Chalcogens give
colored solutions with H2SO4 containing cations such as (blue), (red)
and (green). Similarly, I3+ is obtained as

2. Solvolysis in H2SO4
SeO2 undergoes slow solvolysis in H2SO4 as

Some organic compounds such as nitriles, nitro compounds, sulphones and

sulphoxides also undergo slow solvolysis in H2SO4 as
1.7  ACETIC ACID

Acetic acid is a commonly used laboratory solvent. It is non-ionic, nontoxic

and stable in ordinary conditions. It has a wide liquid range between 16.6 and
118°C. Acetic acid exists as a dimer due to formation of H-bond and is an
associated solvent. This association results in its high boiling point and
unique properties. It has zero dipole moment and very low dielectric constant
(7.1), yet a large number of ionic compounds are soluble in this solvent.
Many compounds solubilise in acetic acid due to H-bond formation.Thus, it
is a good solvent for many organic and inorganic compounds.
Auto-ionisation of acetic acid can be represented as

Thus, substances giving or increasing the concentration of are

regarded as acids and those giving or increasing the concentration of
CH3COO– are considered bases.
All strong acids in aqueous medium act as acids in acetic acid; HClO4
being the strongest.

Weak organic bases such as acetamide, amines, acetanilide and

heterocyclic bases behave as strong bases in acetic acid.

Acetic acid is commonly used as a solvent medium for titration of weak

organic bases, which is not possible in aqueous medium.
A typical acid base reaction in acetic acid can be represented as
CH3COONa + HCl → NaCl + CH3COOH
Salts of alkali and alkaline earth metals with organic acid act as bases in
acetic acid.
CH3COONa → CH3COO– + Na+
Zinc acetate shows amphoteric behaviour in acetic acid.
1.7.1 Chemical Reactions in Acetic Acid
1. The precipitates of Many compounds can be obtained in acetic acid as
BaI2 + 2NaNO3 Ba(NO3)2↓ + 2NaI
CaCl2 + 2AgNO3 Ca(NO3)2 + 2AgCl.
2CH3COONa + Cu(NO3)2 Cu(CH3COO)2 + 2NaNO3
Pb(CH3COO)2 + 2KCl PbCl2↓ + 2 CH3COOH
Cd(CH3COO)2 + H2S CdS↓ + 2 CH3COOH
2. Complex formation reactions in acetic acid take place as

3. Solvolysis reactions in acetic acid can be exemplified as :

Acetic acid forms solvates such as CH3COOK·2CH3COOH.

1.8  LIQUID DINITROGEN TETROXIDE, N2O4

Liquid dinitrogen tetroxide, N2O4, has been used extensively as a protic non-
aqueous solvent, because of its convenient liquid range (–11.2°C to 21.1°C)
and the ease of its preparation. It has a very low dielectric constant (2.42) and
hence is a poor solvent for polar substances but good solvent for nonpolar
substances. The low specific conductance of the solvent (1.3 × 10–13 ohm–1
cm–1 at 10°C) indicates that the self-ionisation of N2O4 is extremely small.
However, the specific conductance increases on addition of a polar solvent
such as nitromethane or by the addition of a donor, thereby increasing its
self-ionisation. The chemistry of N2O4 can be rationalised in terms of the
equation corresponding to its self-ionisation as

Thus, any substance furnishing the NO+ ion would behave as an acid and
those furnishing NO3– would behave as a base in liquid N2O4. Hence, NOCl,
NOBr, etc., behave as an acid in N2O4, while AgNO3, [Et2NH2]NO3, etc.,
behave as a base in N2O4.
The acid-base neutralisation reaction in liquid N2O4 can be represented as
NOCl + AgNO3 → AgCl + N2O4
(Analogous to the neutralisation reactions in NH3 and H2O)
KNH2 + NH4Cl KCl + 2NH3
HCl + NaOH NaCl + 2H2O

Chemical Reactions in Liquid N2O4

1. Reaction with Metals

The behaviour of liquid N2O4 with metals is analogous to that of water. Very
active metals (liquid Na, K) react with liquid N2O4 readily.
M + N2O4 (l) → MNO3 + NO
M + H2O → MOH + ½ H2
Less active metals (Zn, Sn, Fe) are less reactive with liquid N2O4 and the
reactivity increases with the addition of NOCl.
Likewise the reactivity of these metals with H2O increases with the
addition of HCl.
M + 2NOCl MCl2 + 2NO
M + 2HCl MCl2 + H2 (M = Zn, Sn, Fe)
The behaviour of the amphoteric metals such as Zn and Al towards liquid
N2O4 is analogous to that in aqueous solutions and ammonia

Similarly, Zn(NO3)2 reacts with diethylammonium nitrate to form

nitratozincates.
Zn(NO3)2 + x[Et2NH2]NO3 [Et2NH2]x [Zn(NO3)x+2]
Zn + 2NOCl ZnCl2 + 2NO
In aqueous solutions,
Zn + 2NaOH + 2H2O → Na2[Zn(OH)4] + H2
Zn(OH)2 + 2NaOH Na2[Zn(OH)4]
In liquid ammonia,
Zn + 2KNH2 + 2NH3 → K2[Zn(NH2)4] + H2
Zn(NH2)2 + 2KNH2 K2[Zn(NH2)4]

2. Solvolytic Reactions
Some solvolytic reactions in liquid N2O4 are
[Et2NH2]Cl + N2O4(l)→[Et2NH2]NO3 + NOCl
[Mg(H2O)6]Cl2 + N2O4(l) → [Mg(H2O)6](NO2)2 + 2NOCl
Li2CO3 and KCl are solvolysed in presence of traces of water.
KCl + N2O4(l) NOCl + KNO3↓
Li2CO3 + 2N2O4(l) 2LiNO3 + N2O3 + CO2↑
Thus, liquid N2O4 is used to prepare anhydrous nitrates of metals which
are otherwise difficult to obtain in aqueous systems.
Metal carbonyls are also solvolysed with liquid N2O4
Mn2(CO)10 + N2O4(l) → Mn(CO)5NO3 + Mn(CO)4NO + CO
Some solvolysis reaction results in the formation of complexes.
Ca + 3N2O4 → [Ca(NO3)2.N2O4] + 2NO
AlCl3 + 4N2O4 → NO[Al(NO3)4] + 3NOCl
Decomposition of these complexes yields the otherwise inaccessible
anhydrous nitrates.

3. Solvate Formation
Many metals and nitrates of Zn, Fe and U are known to form solvates in
N2O4. These solvates are formulated as complex salts.

N2O4 is a powerful oxiding agent and reacts explosively with organic

substances. Hence, these reactions are carried out with extreme care.

1.9  MOLTEN SALTS AND IONIC LIQUIDS

Molten salts have been used extensively as non-aqueous solvents since

1960s. The term molten salt was initially used for a salt which is solid at
standard temperature and pressure but exists in liquid phase at elevated
temperature. But some molten salts exist as liquid at standard temperature
and pressure and were called ambient molten salts while those earlier
known were called high temperature molten salts. Later on, the definition
was changed to include all the salts which melt without any decomposition or
vapourisation.
Depending upon the melting point and working range of temperature,
molten salts have been classified into two broad categories : high-temperature
molten salts and ionic-liquids.

1. High-temperature Molten Salts

This category includes those salts and eutectics which melt above 100°C to
give liquids, without any salt decomposition or vaporisation. These salts and
eutectics may be ionic or covalent compounds and can be divided into two
broad categories:
(a) Ionic High-temperature Molten Solids The category includes those
salts and eutectics whose melts are ionic. Examples of such salts are
fused alkali metal salts and the ionic metal halides of Group IIA, Al and
the nitrates of transition metals with comparatively much lower m.pt.
than the corresponding individual alkali metal salt. For example,
eutectic of LiF (830°C), NaF (880°C) and KF (912°C) melts at 454°C.
Solution of alkali metal salts in liquid AlCl3 also gives an ionic high-
temperature molten salt, such as NaAlCl4 (152°C).
 The ionic melt behaves as a good electrolyte and behaves normally to
cryoscopy. Thus, the number of ions of BaF2 and CaBr2 is 3 in molten
NaCl.
BaF2 Ba2+ + 2F–
CaBr2 Ca2+ + 2Br–
However, the salt, with common ion as that of the ionic salt behaves
anomalously. For example, the number of ions given by NaF in NaCl
is 1, while CaBr2 in CaCl2 is 2.
NaF Na+ + F–
CaBr2 Ca2+ + 2Br–
Ionic melts dissolve the solutes appreciably and this feature can be
accounted either on the basis of inclusion of solutes in the ‘hole’ of the
ionic structures as exemplified by the noble gases in molten nitrates or
due to chemical interaction as exemplified by HF in NaF/ZnF4 (60: 40
mole %). It has also been found that metals dissolve appreciably in the
ionic melts and tend to form otherwise unstable species.
(b) Covalent High-temperature Molten Salts These molten salts are
covalently bonded compounds and ionize as the aprotic solvents. The
particular examples are covalent halides of Group IIIA, IVA, transition
and inner transition metals.
The solubility of metals in these melts is accounted either on the basis of
coordination bond formation or on the basis of formation of subhalides.
For example,
Cd + CdCl2 → Cd2Cl2
(c) Reactions in High-temperature Molten Salts
(i) Auto-ionization and Acid-base Reactions Some molten salts
undergo auto-ionisation up to some extent.
The auto-ionisation in covalent high-temperature molten salts can be
represented as
2HgX2 HgX+ + HgX3–
 As per the solvent concept, any species which increases the
concentration of HgX3– ion will give an acidic solution while the
species which increases the concentration of HgX3– ion will give a
basic solution. For example, solution of Hg(ClO4)2 in HgX2 is
acidic while that of KX is basic and these two neutralise in presence
of HgX2 melts.

The ionic melt of sodium tetrachloroaluminate is considered to auto-

ionise as

The concentration of basic chloride ion is considered to increase by

the addition of the weakly basic fluoride ion, strongly basic oxide
ion and water, while the concentration of the acidic polymeric ion
is increased with the addition of protons or AlCl3.
(ii) Reactions Involving Participation of the Metals a Reactant Bi
forms Bi+, and in molten NACL/ALCL3. Similarly
, have
been formed. Many unstable compounds have also been obtained.

The most important use of these reactions is in the slag formation

which takes place only in molten form.

Due to excellent solvent property of molten salts, many reactions

have been carried out which are otherwise not possible in aqueous
medium.
2. Ionic Liquids
Ionic liquids are defined as those molten salts whose melting points lie below
100°C. Ionic liquids are based on cationic moities such as substituted
imidazolium, pyridinium, pyrrolidinium, piperidinium, ammonium,
phosphonium, pyrazolium, thiazolium and sulfonium, etc. The anions vary
from halides to coordinates such as and
organics such as ,(CF3SO2)2N, etc. Ethanolammonium
nitrate (m.pt. 50–56°C) was the first ionic liquid reported by Gabriel and
Weines in 1888, and Walden was the pioneer in the synthesis of first ionic
liquid, ethylammonium nitrate (m.pt. 12°C).
Two important categories of ionic liquids are the Room Temperature
Ionic Liquids (RTILs) which exist as liquid even at room temperature due to
their very low melting point, and the ionic liquids which have melting points
above the room temperature (but below 100°C). Ionic liquids act as a green
solvent as well as catalysts for organic synthesis of many compounds. A
recent analogues of ionic liquids have been released in 2003 in the form of
Deep Eutectic Solvent (DES), an ionic solvent which is simply a mixture of
metal or organic salt (or its hydrate) and hydrogen donors. The first DES was
prepared by mixing choline chloride and urea in a 1:2 molar ratio. DES has
much lower melting point than either of its components. For example,
eutectic mixture of choline chloride (302°C) and urea (133°C) melts at 12°C.
Some other examples of DES are ZnCl2/choline chloride,
COCl2.6H2O/chlorine chloride and ZnCl2/urea. DES resemble ionic liquids
in its proporties and are also able to dissolve many metals and their oxides.
Thus, DES provide a better solvent medium due to cheaper synthesis, less
toxicity and biodegradability.

1.10  CONCEPT OF ACID–BASE

Concept of acid–base chemistry has developed since the time of alchemists.

During ancient times, acids were characterised as sour substances which
turned blue litmus paper red, while bases were characterised as bitter
substances which turned red litmus paper blue and reacted with acids to form
salts. First attempt for acid–base theory was made by Lavoisier in 1776. He
defined acid as an oxide of N, P, S and base as a substance that reacted with
acids to form salts.
However, the first satisfactorily explanation for acid-base chemistry was
produced by Ostwald and Arrhenius in 1884 which won Nobel Prize for
Arrhenius. Some important theories are the following:

1.10.1 Arrhenius Theory (Water Ion System)

Arrhenius concept was based on the existence of ions in aqueous solution. He
proposed the self – ionization of water as
H2O H+ + OH–
Acid was defined as the substance that produced H+ and base was defined as
the substance that produced OH– in aqueous solution. Thus, HCl was
characterised as an acid and NaOH as a base according to the following
reactions.

The neutralization process was represented as a reaction that involves the

combination of H+ and OH- to produce H2O.

1. Applications of Arrhenius Concept

(a) This concept helped to explain the acidic nature of aqueous solution
of non-metallic oxides such as CO2, SO2, SO3, N2O3, N2O5, P4O6,
P4O10, etc.

Thus, due to release of H+ ions these solutions are acidic.

(b) This concept helped to explain the basic nature of aqueous solution of
metallic oxides such as CaO, Na2O and the compounds derived from
 NH3.

(c) This concept explains the neutralisation of acid-base in aqueous

solutions.
(d) This concept helps to understand the acid-base equilibria of weak
acids and bases.
Strong acids and strong bases ionise completely in the aqueous solutions,
while weak acids and weak bases do not dissociate completely in the aqueous
solutions. Thus, the dissociation of weak acid and bases can be represented as
an equilibrium process, for aqueous solutions:

Where HA is a weak acid and BOH is a weak base, Ka and Kb stand for
ionization constant of weak acid and base respectively.
According to Arrhenius, greater the values of Ka, stronger is the acid and
greater the value of Kb, stronger is the base. Generally, strong acids have Ka
greater than 10–2 and strong bases have Kb greater than 10–2. This concept
was widely accepted due to its simplicity and extensive use of water as a
solvent for reactions. However, due to some limitations the need of new
concept was soon realized.

2. Limitations of Arrhenius Concept

(a) The main limitation of this concept was its application for aqueous
solutions only. For example, NH3 + HCl → NH4Cl is an acid–base
reaction to produce NH4Cl, a salt but there is no involvement of H2O as
a solvent.
(b) This concept is not applicable for non-aqueous solvents. For example,
NH4NO3 acts as an acid in liquid NH3 but does not produces H+ ion.
 (c) This concept cannot explain the acidic characters of many salts such as
AlCl3 in aqueous solutions.

1.10.2 Bronsted-Lowry Concept (Proton-Donor-

Acceptor System)
Bronsted and Lowry in 1923 independently defined acid as proton donors and
bases as proton acceptors.

In this reaction, HCl donates a proton to H2O and thus acts as an acid, water
accepts a proton from HCl and thus acts as a base. In the reverse reaction,
H3O+ donates a proton to Cl– ion and therefore acts as an acid, Cl– ion
accepts a proton from H3O+ and, therefore, acts as a base, i.e.

Such pairs of substances which can be formed from each other by the gain or
loss of a proton are called Conjugate acid–base pairs. Thus, HCl is the
congujate acid of Cl– ion and Cl– ion is the conjugate base of HCl. Similarly,
water is the conjugate base of H3O+ ion and H3O+ ion is the conjugate acid of
water. This reaction can be written more accurately as

1. Monoprotonic, Polyprotonic and Amphiprotonic

Substances
The substance which can lose one proton is called monoprotonic acid, while
the substance which can lose two or more protons is called polyprotonic acid.
For example, HF and H2O are monoprotonic acids, and H2S and H2SO4 are
polyprotonic acids.
Similarly, the substance which can accept one proton is called
monoprotonic base, while the substance which can accept two or more
protons is called polyprotonic base. For example, Cl– and H2O are
monoprotonic bases, while and S2– are polyprotonic bases.
The substance which can lose as well as accept proton(s) is called
amphiprotonic substance. For example, H2O can accept H+ to behave as a
base and can lose H+ to behave as an acid as evident from the following
reaction:

2. Uses of Bronsted Concept

1. This concept confirmed the existence of H+ as H3O+ and the
amphiprotic nature of H2O as

In the first reaction, H2O is proton acceptor, but in the second reaction
H2O is proton donor. Hence, H2O is amphiprotic, i.e. it can donate as
well as accept protons.
2. According to this concept, even ion can act as acids or bases.
3. According to this concept strength of an acid depends upon its
tendency to lose protons and the strength of a base depends upon its
tendency to gain protons. It means as the reaction I & II are favoured
in forward direction, HCl is a stronger acid and H3O+ is a weaker acid.
Similarly H2O is a stronger base and Cl- is a weaker base. It means that
every strong acid has a weak conjugate base and vice versa.
4. This concept is extended to the use of non-aqueous solvents such as
liquid ammonia, glacial acetic acid, anhydrous sulphuric acid and all
hydrogen containing solvents.
NH3 + HCl → NH4+ + Cl–
NH3 is acting as a base, as it accepts H+ from HCl. The presence of
OH– group is not essential for a substance to act as a base.
 5. According to this concept, tendency of an acid to lose protons depends
upon the tendency of a base to gain protons. For example, acetic acid
acts as an acid in water since it loses proton to water. However in
benzene, acetic acid does not act as an acid, since benzene does not
accept the proton.
When two acids are mixed, the weaker acid acts as a base for the
stronger acid.

In all these reactions, HClO4 is acting as an acid, while the so – called

stronger acids HF, H2SO4 and HNO3 being less acidic than HClO4 are
acting as a base.

3. Limitations of Bronsted-Lowry Concept

1. This concept cannot explain the acidic character of non-protonic acids
(which cannot give a proton). For example BF3, AlCl3, etc.
2. This concept cannot explain a number of acid – base reaction which
take place in the absence of the solvent or without proton transfer.
For example  CaO + SO3 → CaSO4

4. Levelling Effect of Solvents

It has been seen that all strong acids appear almost equally strong in aqueous
solutions. The ionisation of a strong acid is almost complete in water. Thus,
the relative strengths of strong acids cannot be compared in aqueous
solutions. Therefore, HClO4, HBr, H2SO4, HCl and HNO3 all appear equally
strong in water.

The solvent in which strong acids ionise to same extent and behave
equally strong is known as levelling solvent and the phenomenon is called
levelling effect of solvent. Thus water acts as a levelling solvent for strong
acid. However, if CH3COOH is used as a solvent, the ionization can be
represented as

Acetic acid has a little tendency to accept protons. Thus, the equilibrium is
not much towards right, even the strong acids are only weakly ionised. The
solvent in which strong acids ionise to different extents and donot behave
equally strong is known as a differentiating solvent. Thus acetic acid acts as a
differentiating solvent for strong acids such as HClO4, HBr, H2SO4, HCl and
HNO3. These acids have been found in the order of their decreasing strength
as HClO4 > HBr > H2SO4 > HCl > HNO3. On the other hand, weak acids do
not ionise completely in presence of water and hence can be compared for
their relative order of strengths in their aqueous solutions.
This concept is applicable for bases as well. However, same solvent may
not act as levelling solvent for both acids and bases. For example, acetic acid
acts as a levelling solvent for all bases, so that sodium hydroxide, a very
strong base and aniline, a very weak base behave equally strong in
comparatively stronger acid, acetic acid. On the other hand, these bases ionise
to different extents in presence of a weak acid, water. Thus water acts as a
differentiating solvent for bases.
Liquid ammonia is a better proton acceptor than proton donor. Hence,
even a weak acid behaves like a strong acid due to considerable ionisation in
liquid ammonia.

It has been observed that all strong acids and weak acids appear to be
almost equally strong when liquid ammonia is used as the solvent.
Quite interestingly, all acids ionise as bases in hydrogen fluoride and
acetic acid appears to be stronger base than nitric acid in presence of
hydrogen fluoride. This is due to the reason that hydrogen fluoride is too
strong to show any proton accepting properties. Hence, the normal acids
ionise as bases when present in solutions of hydrogen fluoride as
 However, a weaker acid acetic acid which is comparatively better proton
accepter, readily ionises as a base in solution of hydrogen fluoride as

Levelling Effect in Terms of Solvent-System Concept The levelling

effect can be better justified in terms of solvent – system concept. According
to this concept, the acids and bases which ionise completely in the solvent to
give its characteristic cation and anion behave as a strong acid and base. On
the other hand, the acid and base which do not ionise completely in the
solvent to give its characteristic cation and anion behave as a weak acid and
base.
If H2O is used as a solvent, its autoionization can be represented as
H2O + H2O H3O+ + OH–
Any substance which ionizes completely in water to give H3O+ , would be
strong acid and any substance which ionizes completely in water to give OH–
would be a strong base. Since all strong acids ionise completely in water to
give H3O+ ions, hence they appear equally strong in aqueous solutions.
However all bases do not ionise completely in water to give OH- ions and
thus can be differentiated according to their relative strength.
If CH3COOH is used as a solvent, its auto-ionisation can be represented
as

The normally strong acids HCl, H2SO4 and HNO3 do not dissociate
completely in acetic acid and the concentration of CH3COOH2+ varies
accordingly.

Similarly, CH3COOH ionises almost completely in ammonia and leads to

the formation of ion, characteristic cation of the solvent, ammonia. Thus,
acetic acid behaves as a strong acid in ammonia.

1.10.3 Lux-Flood Concept

This concept was originally proposed by Lux and was extended by Flood.
According to this concept, acids were defined as oxide ion acceptor and base
as oxide-ion donor. For example:

This concept is applicable for anhydrous reaction and high temperature

reaction involving molten oxides.

1.10.4 Lewis Concept (Electron Donor Acceptor

System)
In 1923, Lewis developed a broader concept of acid–base reactions in terms
of the electronic structure of the compounds. According to this concept, acid
was defined as electron acceptor and base as electron donor. The acid–base
reaction was defined as the process of neutralisation involving the formation
of a coordinate bond. For example,

H+ accepts electron pair from NH3 molecule and thus acts as an acid, while
NH3 donates an electron pair to H+ and thus acts as a base. This concept can
be elaborated as given ahead:

1. Lewis Acids
(a) Simple Cations All cations are regarded as lewis acids. The strength of
these cations in general, increase with decrease in ionic radius and
increase in the positive charge carried by the cation. For eg. Na+, K+ are
weak lewis acids and H+, Fe2+ are strong Lewis bases.
 (b) Electron Deficient Compounds All molecules which have a central
atom with an incomplete octet act as lewis acids For example – BF3,
AlCl3 etc.
(c) Molecules with Central Atom Containing Vacant d-orbitals All
molecules which have central atom with vacant d-orbitals, can extend
their valence. For e.g. SiF4, SnCl4, SF4, TeCl4, PX3, PF5 etc.
(d) Elements with Sextent of Electrons Two elements in the periodic
table, S and O with sextent of electrons are regarded as lewis acids.

(e) Molecules Containing Multiple Bond between Atoms of Dissimilar

Electro-negativity In such compounds, the electron – density of π-
electrons is displaced towards more electronegative atom and the less
electronegative atom becomes electron deficient. Hence, it can accept an
electron pair from a lewis base.

2. Lewis Bases
(a) Neutral molecules with lone pair of electrons on atleast one of the
atoms. For example, :NH3, etc.
(b) All anions likeF−, OH−, CN−, etc.

3. Limitations of Lewis Concept

This concept includes the reactions in which no protons are involved and the
reactions which take place in absence of solvent. But there are some
limitations of this concept –
 (a) This concept is based on the formation of coordinate bond. But many
acid – base reactions donot involve any coordinate bond formation and
are too rapid.
(b) This concept does not help in determination of relative strength of acids
and bases.

1.10.5 Solvent System Concept

In 1928, Cady and Elsey proposed a general concept applicable to protonic
and non-protonic solvents for acid – base reactions. According to this
concept, acid was defined as a substance which, either by direct dissociation
or by reaction with the solvent gives the anion characteristic of that solvent
and base was defined as a substance, which either by direct dissociation or by
reaction with the solvent gives the cation characteristic of that solvent.
For example, the characteristic cation and anion of H2O are H3O+ and
OH– respectively:

Thus, all the compounds which produce H3O+ ions in H2O will act as
acids and all the compounds which produce OH– ions in H2O will act as
bases.

Neutralisation reaction has been defined as the combination of solvent

characteristic cations and anions.
This concept can explain many acid–base reactions in protonic and non-
protonic solvents. However, it is not applicable to acid–base reactions which
take place in absence of solvents. It can also not explain the acid–base
reactions which take place in those solvents which donot autoionize.
For example, liquid SO2 cannot autoionize because of very low dielectric
constant. Reaction between Cs2SO3 and SOCl2 in liq. SO2 takes place as
Cs2SO3 + SOCl2 2CsCl + 2SO2
There is no explanation of such cases in this concept.
1.10.6 Usanovich Concept (Positive Negative
System)
This concept defines acid as any species which can neutralise a base to form
salt, either by giving cations or combining with anions or electrons.
Conversely, a base is a species which reacts with acids & is capable of giving
anions or electrons or combining with cations. In short, this concept includes
all the earlier concepts of acids and bases as well as redox reactions
Examples
1. 2Na + Cl2 → 2NaCl

2. Fe(CN)2 + 4CN → K4[Fe(CN)6]

This concept however considers all the reactions as acid–base reactions,

which can be better considered from some other point of view.

1.10.7 Pearson Concept (HSAB Concept of Hard

and Soft Acids and Bases)
In coordination chemistry, metal ions and ligands have been seen to have
preferential affinity for particular ligands and metal ions respectively.
Depending upon this tendency, Pearson classified metal ions and ligands into
hard and soft acids and bases:
(a) Hard Acids These are the metal ions which are small in size, have a
high positive charge and a noble gas electronic configuration and are not
very polarisable. These metal ions include cations from groups 1, 2 and
light transition and inner transition metals.
(b) Hard Bases These are the anions or neutral molecules which are having
 high electronegativity and are not easily polarisable. These
preferentially react with hard acids.
(c) Soft Acids These are the metal ions which are large in size, have low
positive or zero charge and do not possess noble gas electronic
configuration. These are easily polarised and include heavy metal ions.
(d) Soft Bases These are the anions or neutral molecules with low
electronegativity and easily polarisable anions. These react with soft
acids.
However, there are some cations of transition and inner transition metals
which behave as soft and hard acids in different cases, depending upon
their oxidation state. Similarly, some bases also lie in intermediate
category. The table below shows complete classifications:
Table 1.8 Classifications of hard/soft acids and bases

1. HSAB Principle—Principle of Hard and Soft

Acids and Bases
According to this principle, hard acids prefer to combine with hard bases and
soft acids prefer to combine with soft bases to form stable products. Hard –
soft acid base or soft – hard acid base combinations yield comparatively less
stable product.

2. Nature of Bonding
Bonding between hard acids and hard bases is predominantly ionic due to
transfer of electrons from hard bases to the vacant d-orbitals of hard acids. In
case of soft acids and soft bases, covalent bond is formed by π-interaction
between the easily polarisable cations and anions.

3. Applications of HSAB Principle

(a) This principle is mainly used to explain the relative stability of
complexes. For example , is stable, but does not exist. It can be
explained as

As already discussed, soft acid-soft base interaction yields stable

complex.
(b) This principle is used to predict the feasibility of reaction between two
compounds. For example, Hg(OH)2 dissolves readily in acidic aqueous
solution, but HgS does not. Hg(OH)2 is a product of soft acid-hard base
combination, so it is unstable and dissociates readily. Whereas HgS is a
product of soft acid-soft base combination. Hence it is stable & does not
dissociate easily. Similarly, Lil and CsF react easily as

(c) This principle is used to predict the existence of certain metal ores. For
example, hard acids like Mg2+, Ca2+ and Al3+ exist as oxides or
carbonates, because oxides and carbonates are hard bases. Where as soft
acids like Ag+, Cu+ and Hg2+ exist as sulphides, because sulphide is a
soft base.
(d) It has been observed that a strong and or base can displace a weaker one
, irrespective of the HSAB principle.
For example,

In this case, very strong but soft base, sulphite ion is displacing the
weak but hard base from the hard acid, H+.
Similar is the case for displacement of weaker soft base, by the very
–
strong hard base, OH ion from the soft acid, methyl mercury cation:
 (e) The hardness or softness of a site can be changed with the addition of
substituent. Addition of hard (electronegative) atoms can harden an
otherwise soft site and vice -versa.

Similarly,

This tendency of a centre which is attached with soft ligands to favour

further coordination by a soft ligand and vice – versa is termed as
‘symbiosis’.

4. Theoretical Basis to HSAB Principle

Several explanations have been put forth to provide the theoretical basis for
hard-hard and soft-soft interactions. The most simple explanation is based on
the type of bonding involved between the groups. It is believed that the hard-
hard interactions involve the electrostatic interactions and thus bonding
between hard acid-hard base must be predominantly ionic. It is due to the
reason that most of the typical acids include the small sized and highly
charged positive metal ions. Such metal ions would preferably favour ionic
bonding with the non-polarisable hard bases and the resulting compound
would be highly stable. On the other hand, hard-soft interactions would be
unfavourable and the resulting species are comparatively less stable.
Electrostatic explanation cannot be accounted for soft-soft interactions, due to
inclusion of the large sized and easily polarisable species which prefer
covalent bonding instead of ionic bonding. On this basis, Misons and co-
workers (1967) have proposed an equation to correlate the hard-hard or soft-
soft interaction as:
pK = − log K = αX + βY + γ
where K is the dissociation constant of the acid – base complex, X and Y are
the parameters of the acids, and α and β are the parameters for the bases. γ is
the constant for adjustment of all the values on the same scale. It has been
found that for hard acids, γ < 2.8 and for soft acids, γ > 3.2. The value of γ
lies in between 2.8 and 3.2 for borderline acids. The value of b increases with
increase in the softness of the base. For hard bases, b < 3 and for soft bases, b
> 5. Table 1.9 lists the values of parameter for some of the hard-soft acids.
Table 1.9 Values of γ for some hard and soft acids

It can be simplified in terms of electronegativity. Most of the species with

high electronegativities are hard, while the species with low
electronegativities are soft. Thus, trifluoromethyl group is harder as
compared to methyl group. Similarly boron trifluoride is harder than borane.
The concept can be elaborated on the basis of HOMO – LUMO approach.
The polarizability of soft species can be accounted due to small HOMO –
LUMO gap as compared to non – polarizability of hard species due to large
HOMO – LUMO gap. Further, due to presence of large number of d-
electrons in metal and empty low lying un-occupied acceptor orbitals on the
ligands, π interactions take place. For example, the small size and presence of
low lying π* acceptor orbitals in CO makes it as the best soft ligand.

1.11  ACID STRENGTH BEHAVIOUR IN THE PERIODIC

TABLE

1. Hydrides of Group 17
When we consider the acid strength of hydrides of Group 17 elements, HX,
one would except the increase in acid strength with increase in the
electronegativity of X. Because higher the electronegativity of X, greater is
the electron pulling capacity and easier is the release of H+. Thus, the order of
acid strength should be
HF > HCl > HBr > HI
However, the actual order is
HF < HCl < HBr < HI
This is due to the reason that there are a number of other factors involved
in the process as discussed below with the help of a Born-Haber type cycle:
Acid strength can be represented as the tendency of hydrated HX
molecule to form hydrogen ions, H+. The energy cycle involves different
stages such as dissociation, ionisation and hydration.

Applying Hess’s Law, Acid strength = ΔHdehydration + DE + IE + EA +

ΔHhydration
Table 1.10 lists the values of all the energies associated with the cycle.

Table 1.10 Energy values (KJ mor–1)

It is evident from the table 6.9 that the acid strength value for HF is small
and increases with maximum for HI. This is due to the high dissociation
energy, high heat of dehydration of HF and low electron affinity of F−.

2. Oxoacids of Same Elements

The acid strength of oxoacids of halogens (for a particular halogen) increases
in the order
 +1  +3  +5  +7
 HXO < HXO2 < HXO3 < HXO4
This is due to the reason that higher the oxidation state of the central
atom, higher is its electronegativity, greater is the tendency to pull the
electrons and easier is the removal of H+. Now, the oxidation state of halogen
in these oxoacids is +1, +3, +5 and +7 respectively. Thus, the halogen with
highest oxidation state is most electronegative and hence most acidic.
Similarly, acid strength order of oxyacids of other elements varies as
H2SO3 < H2SO4 and HNO2 < HNO3
However, in case of oxyacids of phosphorus, the order of acidic strength is
+1  +3  +4
H3PO2 > H3PO3 > H3PO4
This is due to the reason that in case of oxyacids of phosphorus, acidic
strength depends on the number of dissociable protons (protons attached to
oxygen atom). The structure of these oxyacids reveal that the number of
dissociable protons (number of OH groups) increases from H3PO2 (one) to
H3PO4 (three). Thus acidity of these oxyacids increases in the order H3PO4 <
H3PO3 < H3PO2.

3. Hydrides of Non-metals of Second Period

The acid strength of hydrides of non-metals of 2nd period varies in the order
as
CH4 < NH3 < H2O < HF
This is due to increasing electronegativity of the non-metal in the order C < N
< O < F. As a result, the stability of their conjugate bases increases in the
order.
 Similarly, on moving down a group (except Group 17) the acid strength
increases (basic strength decreases) with decrease in electronegativity of the
elements in the same group.
Thus, the order for increasing acid strength is
NH3 < PH3 < AsH3 < SbH3 < BiH3
H2O < H2S < H2Se < H2Te

4. Oxoacids of Similar Structures

The acid strength of oxoacids of similar structures increases with increase in
the electronegativity of the central atom as
HIO3 < HBrO3 < HClO3
HNO3 > HPO3 > HAsO3
H3PO4 > H3AsO4 > H3SbO4
H2SO4 > H2SeO4 > H2TeO4

The solvent behaviour is determined by its dielectric constant, dipole

moment, melting point, boiling point, and heat of fusion and vaporisation. A
solvent which can donate or accept protons is known as protic solvent while
which cannot donate or accept protons is known as aprotic solvent. A solvent
which can donate as well accept protons is known as an amphiprotic solvent.
The solvent which can undergo auto ionisation is known as an ionising
solvent, and which cannot ionise at all is known as a non-ionising solvent. In
general terms, the solvents other than water are known as non aqueous
solvents while water is known as the aqueous solvent.
Due to low dielectric constant and low dipole moment, liquid ammonia
acts as a better solvent for nonpolar molecules. It auto-ionises to give
ammonium ion and amide ion (imide and nitride ions can also be formed).
Any substance which increases the concentration of ammonium ion in liquid
ammonia is known as ammono acid, while the substance which increases the
concentration of amide, imide or nitride ions in liquid ammonia is known as
ammono base. Most of the chlorides can be precipitated in liquid ammonia
while many active metals react with solutions of ammonium salts in liquid
ammonia to liberate hydrogen. Alkali metals dissolve in liquid ammonia to
give blue solutions which are very strong reducing agents.
Liquid SO2 is an aprotic solvent which dissociates to give thionyl ion and
sulphite ion. Thus, accordingly, producing substances act as acids while
producing substances acts as bases in liquid SO2. Anhydrous HF is an
excellent ionising solvent which ionises to give fluoronium ion and fluoride
ion. The strong acids in water behave as bases in HF while the electron
acceptor fluorides act as acids in HF. However, the weak acids in water
behave as bases in HF. Anhydrous sulphuric acid is a highly associated non-
aqueous solvent and is used as a dehydrating agent. Only some substances act
as acids in H2SO4; these are chlorosulphuric acid, fluorosulphuric acid,
perchloric acid, sulphuric dioxide, trisboron (hydrogen sulphate) and mixture
of strong lewis acids and highly acidic protonic solvents.
Acetic acid is a commonly used laboratory solvent. All strong acids in
aqueous media act as acids in acetic acid while weak organic bases and salts
of ‘s’ -block elements with organic acids act as a base. Liquid N2O4 is also an
excellent aprotic non-aqueous solvent. Nitrosyl ion producing substances act
as acids while nitrate ion producing substances act as a base in N2O4. It is
also a powerful oxidising agent and reacts vigorously with organic
substances.
Molten salts have proved to be excellent non-aqueous solvent and refer to
the salts which melt without any decomposition or vaporisation. These are
classified into high temperature molten salts with m.pt. above 100°C and
ionic liquids with m.pt. below 100°C. Molten salts are good conductors and
are highly stable thermally as well as w.r.t. oxidation.
EXAMPLE 1 Predict the behaviour of (NH4)2SO4 and urea in water,
liquid NH3 and anhydrous H2SO4.
(a) Behaviour of (NH4)2SO4 and urea in water
(NH4)2SO4 dissociates in water to give and .

ions further react with H2O to give H3O+ ions and NH4OH is
formed.
+ 2H2O NH4OH + H3O+

Urea behaves as a non-electrolyte in water.

(b) Behaviour of (NH4)2 SO4 and urea in liquid NH3
(NH4)2SO4 dissociates in liquid NH3 and concentration of ion is
increased, the characteristic cation of liquid NH3. Hence, the solution is
acidic.
(NH4)2SO4 2 +
Urea gives ion in liquid NH3 due to protolysis.
NH2CONH2 + NH3(l) → NH2CONH– +
(c) Behaviour of (NH4)2SO4 and urea in anhydrous H2SO4
(NH4)2SO4 dissociates in anhydrous H2SO4 and concentration of is
increased, the characteristic anion of H2SO4 and the solution is basic.

Urea accepts a proton from H2SO4 and concentration of HSO–4 is

increased.Thus, the solution is basic.

EXAMPLE 2 Complete the following equations:

1. CH3C = NHNH2 + NH3(l) →
2. Pbl2 + KNH2
 3. UCl6 + SO2(l) →
4. CrF3 + 3NaF
5. KCl + N2O4(l)

1. CH3C = NHNH2 + NH3 (l) CH3C = NHNH− +

Acetamidine undergoes protolysis in liquid NH3 and behaves as an
acid in liquid NH3
2. KNH2 is an ammono base and forms PbNH, lead imide.
PbI2 + KNH2 KI + HI + PbNH↓
3. UCl6 undergoes solvolysis in liquid SO2 and forms oxylchloride. It
also results in an increase in concentration of SO2+ ion.
4. CrF3 dissolves in NaF in presence of anhydrous HF due to the
formation of sodium hexafluoro- chromate (III)
CrF3 + 3NaF → Na3[CrF6]
5. KCl gets solvolysed by N2O4(l) in presence of traces of water.
KCl + N2O4 NOCl + KNO3↓.
EXAMPLE 3 What happens when
(a) Potassium is treated with nitrous oxide in presence of liquid NH3?
(b) Mercury (II) iodide is treated with potassium iodide in presence of
liquid SO2?
(a) Potassium reduces nitrous oxide to N2 in presence of liquid NH3.
2K + N2O + NH3(l) → KNH2 + KOH + N2
(b) Mercury (II) iodide dissolves in potassium iodide due to the formation
of potassium tetraiodomercurate (II).
HgI2 + 2KI K2[HgI4]
EXAMPLE 4 Write conjugate acids for the following
 (a) NH2CONH2
(b) HNO3
(c) H2SO4
(a)
(b)
(c)
EXAMPLE 5 Identify conjugate acid base pair in the following
reaction

Conjugate acid base pair – I;  Acid I – HCl; Base I – Cl−

Conjugate acid base pair II ;  Acid II – ; Base II –
CH3COOH

EXAMPLE 6 Arrange the following in their increasing basic

strength & justify your answer. NH3, H2O, HF and Ne.
All these substances contain lone pair on at least one atom as shown below:

Thus, all the substances can act as lewis base. Now as the number of lone pair
increases, the tendency of the substance to donate the electron pair decreases
& hence basic strength decreases. Thus, the order of basic strength is
Ne < HF < H2O < NH3
EXAMPLE 7 Give reasons for the following:
(a) [Co(NH3)5F]2+ is stable while [Co(NH3)5I]2+ is unstable.
(b) Copper and silver occur in nature as their sulphides while
Magnesium and calcium occur as carbonates.
(a) NH3 and F– are hard ligands, while I- is a soft ligand. Thus,
[Co(NH3)5F]2+ with all hard ligands is more stable than [Co(NH3)5I]2+.
(b) Mg2+ and Ca2+ are hard acids, while Cu+ and Ag+ are soft acids. On the
 other hand CO32− is a hard base and S2− is a soft base. Thus, according
to HSAB principle Cu2S and Ag2S are stable. Similarly MgCO3 and
CaCO3 are stable to occur in nature.
EXAMPLE 8 LII reacts with CsF, but Csl cannot react with LiF.
Justify the statement.

According to HSAB principle, LiF is more stable than LiI, while CsI is more
stable than CsF. Thus LiI and CsF can react together, while LiF and CsI do
not react.

QUESTIONS
Q.1 Discuss the important characteristics of solvents.
Q.2 Discuss the classification of solvents in detail.
Q.3 Give an account of each of the following in liquid NH3.
(a) acid–base reaction
(b) Metathesis reaction
(c) Ammonolysis
(d) Complex formation reaction
Q.4 What do you mean by auto-ionisation? Illustrate your answer with the
help of suitable examples.
Q.5 Complete the following equations.
(a)
(b)
(c)
(d)
Q.6 Give reasons for the following:
(a) Acetamide is basic in water but acidic in liquid NH3.
(b) SbF6 behaves as an acid in HF.
(c) Alkali metals dissolve in liquid NH3 to give reducing solutions.
(d) Solution of KNH2 in liquid NH3 gives pink colour to
 phenolphthalein.
(e) Solution of Hg(ClO4)2 in HgCl2 is acidic.
Q.7 Predict the behaviour of each of the following in water, liquid NH3 and
liquid SO2.
(a) NH4Br
(b) CH3COONH4
Q.8 Discuss the following reactions in liquid HF and anhydrous H2SO4.
(a) acid–base reactions (b) Auto-ionisation
Q.9 Discuss the use of molten salts as a non-aqueous solvents in brief.
Q.10 Discuss the use of Ionic liquids as a reaction medium.
Q.11. Discuss Arrhenius theory of acids and bases and its application.
Q.12 Discuss Bronsted-Lowry concept of acids and bases. What are its uses?
Q.13 Discuss Lewis concept of acids and bases.
Q.14 Discuss solvent concept of acids and bases. What are its advantages?
Q.15 What do you mean by levelling and differentiating solvents?
Q.16 Explain your answer with the help of suitable examples.
Q.17 What is HSAB principle? What are its applications?
Q.18 Arrange the following in increasing order of acid strength with proper
explanation:
(a) HIO2, HBrO2, HClO2
(b) HF, H2O, NH3, CH4
Q.19 Give reason for the following :
(a) is stable but is unstable.
(b) CF4 is more stable than CH3F.

MULTIPLE-CHOICE QUESTIONS
1. NH4Br is reduced by Na in liquid NH3 to give
(a) NH3
(b) H2
(c) NaBr
(d) all of these
2. Cr2SO3 acts as a base in
 (a) H2SO4 anhyd.
(b) H2O
(c) SO2 (l)
(d) all of these
3. HClO4 in liquid HF acts as
(a) acid
(b) base
(c) amphoteric
(d) none of these
4. Iron dissolves in molten potassium nitrate to give
(a) Fe(NO3)2
(b) K2FeO4
(c) K3FeO4
(d) Fe2O3
5. The number of ions obtained by cryoscopic method in case of
BaF2CaBr2 and NaF in molten NaCl is
(a) 1, 2, 3
(b) 3, 2, 1
(c) 3, 3, 2
(d) 3, 3, 1
6. The conjugate base of NH2CONH2 is
(a)
(b) NH2CONH–
(c) H2O
(d) none of these
7. Which of the following is a Lewis base?
(a) Ne
(b) NH3
(c) H2O
(d) All of these
8. Which of the following is a soft base according to HSAB principle?
 (a) I2
(b) NH3
(c) Br−
(d) C6H6
9. Which of the following is least acidic?
(a) HF
(b) HI
(c) NH3
(d) CH4
10. Which of the following is most acidic?
(a) HIO2
(b) HBrO2
(c) HClO2
(d) HClO3