DEPARTMENT OF CHEMISTRY

INORGANIC CHEMISTRY
ASSIGNMENT
SUBMITTED BY MAHNOOR
SUBMITTED TO SIR ASHRAF SHAHEEN
ROLL NO MCHF19MO04
SUBJECT IN ORGANIC CHEMISTRY
TOPIC NON-AQUEOUS SOLVENTS
(INTRODUCTION,
CLASSIFICATION, TYPES OF
REACTION IN NON-AQUEOUS
SOLVENTS, PHYSICAL AND
CHEMICAL PROPERTIES)
NON-AQUEOUS SOLVENTS

NON -AQUEOUS SOLVENTS

➢ CONTENTS:

1. INTRODUCTION TO SOLVENTS
2. CLASSIFICATION OF SOLVENTS
i. FIRST CLASSIFICATION
a) PROTIC OR PROTONIC SOLVENTS (acidic, basic and
amphoteric)
b) NONPROTIC OR APROTIC SOLVENTS
ii. SECOND CLASSIFICATION
a) Ionizing or polar solvents
b) Non ionizing or non- polar solvents
iii. THIRD CLASSIFICATION
a) Aqueous solvent (Water)
b) Non Aqueous solvents

3. NON- AQUEOUS SOLVENTS INTRODUCTION

4. IMPORTANCE
5. PHYSICAL PROPERTIES

i. Dipole moment
ii. Di-electric constant
iii. Electric conductance
iv. Density
v. Viscosity

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6. CHEMICAL PROPERTIES (TYPES OF REACTIONS)

i. ACID –BASE (NEUTRALIZATION REACTIONS)
ii. SOLVATION OR FORMATION OF ADDITION
COMPOUNDS (ADDUCTS)
iii. SOLVOLYSIS OR SOLVOLYTIC REACTIONS
iv. METATHETICAL OR PRESIPITATION REACTIONS
v. REDOX REACTION

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SOLVENTS

➢ INTRODUCTION:
In a very general sense, solvents are a class of chemical
compounds that allow chemistry to occur. The concept of a solvent has significant
ramifications because they serve as the matrix, medium, or carrier for solutes. They
are necessary in a number of processes, reactions, and systems. It means
that solvent molecules will surround the solute in such a way that a solution is
formed; in other words, a homogeneous system is generated in which the solute is
part of indistinguishable from the solvent network.

:
Fig 1: Interaction of solute particles with solvent particles . Water molecules surround
the solute particles in such a way that partial positive oxygen is attracted towards positive
side and partial positive hydrogen is attracted towards negative end.

Most of the chemical reactions familiar to us take place in aqueous

solution, since water, due to 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 non-aqueous medium. The classification of solvents is as
following:

➢ CLASSIFICATION OF SOLVENTS:
Solvents have been classified in a. number of ways depending on
their physical and chemical properties.
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1. FIRST CLASSIFICATION:
This is a common classification which is based on proton-
donation and proton-acceptance property of the solvents. On the basis of this
classification the solvents may be classified into three types:

i. Protic or Protonic solvents

ii. Non-Protonic or Aprotic solvents

PROTIC SOLVENTS:
Protic solvents are defined as following:
“The solvents that either lose protons or gain them or can show both
the tendencies are known as protic solvents”
Protic solvent is a solvent that has a hydrogen atom bound to
an oxygen (as in a hydroxyl group), a nitrogen (as in an amine group),
or fluoride (as in hydrogen fluoride). In general terms, any solvent that contains
a labile H+ is called a protic solvent. The molecules of such solvents readily donate
protons (H+) to solutes, often via hydrogen bonding. Water is the most common
protic solvent. Conversely, aprotic solvents cannot donate hydrogen. Major uses
of polar solvents are in paints, paint removers, inks, and dry cleaning.

Polar protic solvents are often used to dissolve salts. In general, these solvents have
high dielectric constants and high polarity.

CHARACTERISTICS:

Common characteristics of protic solvents are as follows:

• Solvents display hydrogen bonding.

• Solvents have acidic hydrogen (although they may be very weak acids such
as ethanol).
• Solvents dissolve salts.
❖ Cations by unshared free electron pairs.
❖ Anions by hydrogen bonding.

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Examples include water, most alcohols, formic acid, hydrogen fluoride,

and ammonia. Polar protic solvents are favorable for SN1 reactions, while polar
aprotic solvents are favorable for SN2 reactions.

Protic or Protonic solvents have hydrogen atom in their formula and are of
three types.

(a) Acidic (proto-genic) solvents.

(b) Basic (proto-philic) solvents.
(c) Amphi-protic solvents.

• Acidic solvents have strong tendency to donate protons. Examples are

H2S04, HF, CH3COOH, HCN etc.
• Basic or protophilic solvents have strong tendency to accept protons.
Examples are NH3, N2H4, NH2OH and amines.
• Amphi-protic or amphoteric solvents. These have hydrogen in their
formula and show dual character, can donate or accept protons
depending on the nature of reacting species, e.g., H2O, alchohols, liq.
NH3, CH3COOH etc. these can act both as acids and bases and
consequently are amphoteric in nature. Amphoteric solvents undergo
auto-ionization(self-ionization) in which a proton transfer between
two similar neutral molecules takes place and a cation-anion pair of
the solvent is obtained:

Acid Base Acid Base

+
+ –
H2O + H2O H3O HO

+ –
NH3 NH3 NH4 + NH2
+
+ -
CH3COOH + CH3COOH CH3COOH2 + CH3COO

NON-PROTIC SOLVENTS:
Aprotic or non-Protonic solvents are defined as following:

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“These may or may not have hydrogen in their formula and neither
donate nor accept protons”

Examples are C6H6, CHCI3, S02, CCI4, and BrF3 etc. Aprotic
solvents are solvents that lack acidic hydrogen. Consequently, they are
not Hydrogen donors. These solvents generally have intermediate dielectric
constants and polarity. Although discouraging use of the term "polar aprotic",
IUPAC describes such solvents as having both high dielectric constants and high
dipole moments, an example being acetonitrile. Other solvents meeting IUPAC's
criteria include pyridine, ethyl acetate, DMF, HMPA, and DMSO.

CHARACTERISTICS:

Common characteristics of aprotic solvents:

• solvents that can accept hydrogen bonds

• solvents that do not have acidic hydrogen
• solvents that can dissolve salts

The criteria are relative and very qualitative. A range of acidities are
recognized for aprotic solvents. Their ability to dissolve salts depends strongly on
the nature of the salt.

Polar aprotic solvents are generally incompatible with strong bases, such
as Grignard reagents or t-butyllithium. These reagents require ethers, not nitriles,
amides, sulfoxides, etc. The strong base may even deprotonate them (such as
methyl anion as a base having a pKaH of 50, and sulfoxides have pKa of
approximately 35.

2. SECOND CLASSIFICATION:
This classification is based on polar and non-polar nature of
the solvents. This classification is based on the fact that "like dissolves like”. Thus
this classification gives the following types of solvents:

i. Ionising or Polar solvents

ii. Non-ionising or non-polar solvents

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IONISING SOLVENTS:
Ionising solvents are polar or ionic in nature and hence dissolve ionic
compounds and initiate ionic reactions.

These exist as ions in their pure state and thus are weak conductors of
electricity. These have high values of dielectric constants. Because of their polar
nature they have strong tendency to form associated structures. Examples: H 20,
NH3, HF, S02 etc. These solvents undergo self-ionisation as shown below:

Acid Base Acid Base

+ –
HF + HF H2F + F
+2 -2
SO2 + SO2 SO + SO3

NON- IONIZING SOLVENTS:

These are non-polar or non-ionic in nature and hence dissolve only
non-polar or neutral compounds and do not initiate ionic reactions. These have low
dielectric constants. They have little associating and solvating tendency between
the solute and solvents. Examples: C6H6, CCI4 etc. These solvents do not undergo
self-ionisation.

3.THIRD CLASSIFICATION:
Third classification includes the following:

i. Aqueous solvent
ii. Non- aqueous solvent

The solvents other than water are called non-aqueous solvents. The groups
obtained as a result of self-ionisation of H20 and non-aqueous solvents are
analogous to each other, e.g., H3O+and OH- groups obtained from the self-
ionisation of H20 are analogous to NH4+ and NH2 - groups respectively resulted
from the self-ionisation of liq. NH3. This is called parent solvent concept and a
large number of chemical reactions have been correlated in terms of this concept.

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NON-AQUEOUS SOLVENTS

➢ INTRODUCTION:
Most of the chemical reactions familiar to us take place in
aqueous solution, since water, due to 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 non-aqueous medium.

A large no of non-aqueous solvents have been discovered in the last few

years. These solvents have sizeable values of their dielectric constant and hence
dissolve many substances. Examples of such solvents are anhydrous liq. NH3, liq.
SO2, HF and N2O4.

IMPORTANCE:
The importance of solvents is described as following:

Most of the chemical reactions take place in aqueous solutions. The reacting
substances should be in a dispersed condition i.e., as ions, atoms or molecules) in a
suitable medium (SOLVENT') before appreciable interaction can take place. It is
rather unfortunate that we usually lay stress on reacting substances only arid ignore
the importance of the solvent on the course of a chemical reaction.

By changing the solvent, the reactants may give altogether different products
or even the course of a chemical reaction may be reversed. e.g. NH 4CI and LiN03
do not react in aqueous solution but give a precipitate of LiCl in liq. NH3.So
solvent is of great importance by every respect. Similarly AgNO3 and BaCl2 react
in aqueous solution to give ppt. of AgCl, but in water the reverse reaction occurs.
Following is given the examples of such reactions:

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aq.sol
NH 4Cl + LiNO 3 No reaction

But in liq. ammonia they react to form LiCl and

NH4NO3:
NH 4Cl NH3
+ LiNO 3 LiCl + NH 4NO 3

AgNO3 and BaCl2 in aq. sol react to form ppt

of AgCl:
H2O
2AgNO 3 + BaCl 2 2AgCl + Ba(NO 3)2

But in liq. ammonia reverse reaction takes

place:
NH3
2AgCl + Ba(NO 3)2 BaCl 2 + 2AgNO 3

➢ PHYSICAL PROPERTIES:
Some of the physical properties of some ionising solvents are given in
Table 1.1

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Table 1.2

1.Dipole moment:
Dipole moment is defined as following:

“The product of charge and distance between the two charges is called
dipole moment.”

Greater is the polarity of the bond, greater will be the charge separation and higher
will be the dipole moment. Solvents having higher values of dipole moment
dissolve the polar substances (i.e. solutes) readily. This is because of the fact that
greater the polarity of a solvent molecule, greater is the solvation energy released
on dissolution of a solute.

Dipole moment value of solvent also gives an idea about the extent
of association in the liquid state and hence its liquid temperature range.

2.Dielectric constant
Columbic force of attraction, F between a cation and anion in an ionic crystal
is given by the expression:

𝒒+ 𝒒−
𝑭=
𝑫𝒓𝟐
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Where q+ and q- = charges on the cation and anion respectively, r=

distance between the cation and anion and D=a constant called dielectric constant
which depends on the nature of the solvent in which the ionic crystal is kept. The
above expression shows that for the same values of q+, q- and r, if F is small, D
will be large, i e., a solvent having a high value of D will reduce F. In other words
a solvent with a high value of D will weaken the force holding the ions of ionic
crystal together and ultimately will dissolve the ionic crystal in it, e.g. water which
has greater value of dielectric constant (=78.5) than liq. NH3( = 22.0) is a better
solvent for dissolving ionic compounds like NaCl.

When NaCI is dissolved in water; the positive ions Na+ ions are attracted
by the negative dipolar end of H20 and the negative ions CI- ions are attracted by
the positive end of H20 molecules and thus NaCI passes into H20 and Na+ and Cl-
Ions removed from the ionic crystal. It is imperative that in order to have a solute
dissolve in an ionic solvent the solute itself must be ionic. This explains why a
non-polar substance does not dissolve in ionic solvents like water. The dissolution
of an ionic compound in a polar solvent occurs only when the energy of solvent ion
or the ions exceeds the lattice energy of the crystal.

It should be noted that solvent-solute interaction leading to solubility is

more involved than would appear from a series of dielectric constants alone."
Other factors that might influence, in specific cases, are ion-dipole, dipole-dipole,
and hydrogen bonding and even pi complexes interactions.

RELATION BETWEEN DIELECTRIC CONSTANT AND SOLUBILITY:

As columbic force is given by following expression:

𝐜 + ×𝐚− 𝒄+ ×𝒂−
F= =
𝐊𝐫 𝟐 𝑲(𝒓+ +𝒓− )𝟐

Here K is di- electric constant. The above equation shows that F and K are
inversely proportional to each other. This means that if value of K for solvent is
high, the force between ions of solute is very low and hence solvent will dissolve
the solute quickly and hence solvent of high dielectric constant has increased
ability to dissolve ionic or polar compound.

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3.Electrical conductance:
These solvents are self-ionising; hence electrical conductance gives an idea
about the extent of such ionisation. Greater is the ionisation, easier it is for acid-
base reactions to occur in the solvent.

4.Viscosity:
Viscosity is an important property of a liquid solvent. Some solvents are
highly fluid, e.g. water, low molecular weight alcohols, liq. NH3, while some are
viscous e.g. anhydrous HF, SO2 etc.

5.Density:
Density is also very important physical property. Density is defined as
below:

SOLVENT DENSITY(g/mol)

Water 1.0 at (4◦C)

Ammonia 0.68 at b.p

Sulphur 17.4 at (6◦C)

dioxide

➢ CHEMICAL PROPERTIES:
Chemical properties include chemical reactions that occur in solvents. Following
are chemical reactions that occur non-aqueous solvents:

1. NEUTRALIZATION REACTION:
The reaction in which acid combines with base and form salt
and water is known as neutralization reaction.

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Neutralization occurs in non- aqueous solvent in such a way:

“That compound containing or making available acidic specie

combines with compound containing or making available basic specie to form salt
and solvent”

Neutralization reaction can also be defined as the combination of

solvent cation and solvent anion to form the un-ionized solvent. Following are the
examples of neutralization reaction in liq.NH3 and liq. SO2:

EXAMPLES:

Neutralization reaction in liq. NH3:

Acid Base Salt Solvent
liq.NH3
NH 4Cl + KNH 2 KCl + 2NH 3

Actually the above reaction takes place through following

steps:

liq.NH3 + –
NH 4Cl NH4 + Cl
liq.NH3 + –
KNH 2 K + NH2

liq.NH3 + – –
NH 4Cl + KNH 2 K + Cl +
+
NH4 + NH2

Other Examples:
liq.NH3
NH 4X + NaNH 2 NaX + 2NH 3
liq.NH3
2NH 4X + PbNH PbX2 + 3NH 3

liq.NH3
3NH 4X + BiN BiX3 + 4NH 3

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Neutralization reaction in liq. SO 2:

Acid Base Salt Solvent

Cs 2SO 3 liq. S02
SOCl 2 + 2CsCl + 2SO 2

Actually the above reaction take place in the

following steps:
liq. S02 +2 -
SOCl 2 SO + 2Cl
liq. S02 + +2
Cs 2SO 3 2Cs + SO 2

SOCl 2+ Cs 2SO 3 liq. S02 + - +2 -2

2Cs Cl + SO + SO 3

0ther Examples:
liq. S02
SO(SCN) 2 + K2SO 3 2K(SCN) + 2SO 2

SOBr 2 +[N(CH 3)4] 2SO 3 liq. S02 2[N(CH 3)4]2Br + 2SO 2

2. FORMATION OF ADDITION COMPOUNDS/SOLVATION:

Solvation reaction is defined as following:

“The reaction in which a solute(cation, an anion or a

neutral molecule) react with one or more molecules of solvent to form product
in which the solute and solvent species are attached to each other by a H-bond
or coordinate bond, the reaction is known as solvation reaction.”

The products obtained as a result of solvation reactions are called solvates.

The solvation reaction taking place in water, liq. NH3, alcohol, hydrazine and ether
are known as hydration, ammoniation, alchoholation, hydrazination and
etheration respectively and the solvates obtained in these reactions are called
hydrates, ammoniates, alcoholates, hydrozinates and etherates respectively.

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The attachment of the solvent molecule to the solute species may be through
ion-dipole, hydrogen bonding or coordinate bonding. In the last type of bonding
the solvent may act as a Lewis base or as a Lewis acid depending on the acceptor
or donor property of the solute respectively, e.g.,

Solute Solvent Solvates

(Lewis acid) (Lewis base) (adducts)

SO3 + 2NH 3 SO 3.2NH 3 (1:2 adduct)

SiF4 + 2NH 3 SiF4.2NH 3 (1:2 adduct)

BF 3 + NH3 BF 3.NH 3 (1:1 adduct)

+ -
KI + 4SO 2 K [(SO 2)4I] (1:1 adduct)

3. SOLVOLYSIS OR SOLVOLYTIC REACTION:

Solvolysis is defined as following:

“ Solvolysis or solvolytic reactions are those in which the solvent

is split into two parts and one or both parts get attached to a solute
molecule or ion. ‘’

In solvolysis reactions the concentration of either cation or anion is

increased which is characteristic of auto-ionisation of the solvent. The
solvolysis reactions taking place in water, liq. NH3 and alcohol are called
hydrolysis, ammonolysis and alcoholysis respectively. Examples of solvolysis
reactions in NH3, SO2 and HF are following:

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+
SiCl 4 + 8NH 3 Si(NH 2)4 + 4NH 4 + 4Cl -

PCl 5 + SO2 POCl 3 + SOCl 2

AlCl 3 + 2NH +
AlCl 2(NH 2) + NH4 + Cl
-
3

4. PRECIPITATION REACTION:
One of the familiar chemical reactions is the formal ion of a
precipitate when two solutions are mixed together Tile formation of precipitate
depends upon the solubilities of various products formed in a particular solvent
and these depend critically on the solvation energies of the ions, considered in
that solvent. Hence the precipitation reaction mainly depends on the nature of
the solvent used in the reaction. Examples of precipitation reactions are written
as following:

liq. NH3
NH 4Cl + KI KCl + NH 4I
liq. SO2
PbF 2 + LiSO 4 PbSO 4 + 3LiF
liq.HF
KClO 4 + TiF TiClO 4 + KF
5. REDOX REACTION:

Redox reaction is defined as following:

“Redox reaction is defined as reaction in which oxidation

and reduction occurs simultaneously”

In general same type of redox reaction occurs in non-aqueous medium as

occur aqueous medium however a solvent may be susceptible to redox reaction
for example water is susceptible to reduction, hence strong reducing agent
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whose electrode potential are above Hydrogen in electrode potential series

cannot be used in aqueous system. However, oxidation reactions can easily be
carried out in aqueous medium. The reverse is true for NH3. It is stable to
reduction hence, susceptible to oxidation. Thus water is suitable medium for
oxidation and NH3 is suitable medium for reduction. However SO2 is inert
towards redox reactions so, it serves as suitable medium for both oxidation and
reduction.

liq. NH3 6NH3

6KMnO4 + 6KNH2 6K2MnO4 +
liq. SO2
5SbCl5 + 6KI 2K3[SbCl6] + SbCl3 + 3I2
liq. HF
5HIF 6 + 6Ag 6AgIF6 + HI + 6HF

“THE END”

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