Dr.G.Rajkumar M.Sc., Ph.D., NET., SET.
Assistant Professor of Chemistry
Vivekananda College
Tiruvedakam West – 625 234
Madurai
Tamil Nadu
E-mail:
[email protected] Mobile No: 9500869470
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Non-aqueous solvents: Classification of solvents – reactions in non-aqueous solvents
with reference to liquid NH3 and liquid SO2.
NON-AQUEOUS SOLVENT
An inorganic non-aqueous solvent is a solvent other than water that is not
an organic compound.
Ex: Liq. NH3, Liq. SO2, Liq. HF POCl3, N2O4, SbCl3, BrF5, , etc.
Advantages:
Determination of organic acids and bases which have a limited solubility in
water.
Organic acids and bases that are insoluble in water are soluble in non-aqueous
solvent.
Organic acid, which is of comparable strength to water, can be titrated easily in
non-aqueous solvent.
By the proper choice of the solvents or indicator, the biological ingredients of a
substance whether acidic or basic can be selectively titrated.
Disadvantages:
Expensive
Volatile
Toxic
Removal of water is necessary, can take water (humidity) from the air.
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Classifications of Solvents
A) Proton donor/acceptor
i) Protic or protonic solvents
a) Acidic or protogenic – They have a tendency to donate protons.
Ex: H2SO4, HCl, HF, CH3COOH
b) Basic or protophilic - They have a tendency to accept protons.
Ex: NH3, Amines
ii) Aprotic or non-protonic solvents – These may or may not have hydrogen in
their formula and neither donate nor accept protons.
Ex: C6H6, CHCl3, SO2, CCl4
iii) Amphoteric – These have hydrogen in their formula and donate or accept
protons depending on the nature of reacting species. i.e. these can act as acids
and bases.
Ex: H2O, CH3COOH
B) Like dissolves like
i) Polar or ionizing solvents:
Ionizing solvents are polar or ionic in nature and hence dissolve ionic
compounds. They have a high value of dielectric constant. They undergo
autoionization.
Ex: H2O, NH3, SO2
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ii) Non-polar or non-ionizing solvents:
Solvents which do not ionize at all are non-ionizing solvents. It dissolves any
non-polar or neutral compounds. They have a low value of dielectric constant.
They do not undergo autoionization.
Ex: C6H6, CCl4
C) Aqueous/non-aqueous
i) Aqueous - Water
ii) Non-aqueous – the solvents other than water are called non-aqueous
solvents.
Ex: liq. HF, liq. SO2, liq. NH3
Liquid NH3
Physical Properties
i) NH3 gas can be liquefied, however, due to its extremely low boiling point;
liquid ammonia must be stored at low temperature and high pressure.
ii) Liquid range is -77.7 to -33.3o C
iii) The liquid boils at −33.3 °C, and freezes at −77.7 °C to white crystals.
iv) Dielectric constant of ammonia is 22 at − 33℃. Therefore liq. NH3 is a poor
solvent of ionic substances.
v) The extent of auto ionisation of liq.NH3 is less than that of water. This is clear
from its low specific conductance and lower ionic product.
Chemical properties
Autoionization of liq. NH3
On autoionization, liq. ammonia gives ammonium ions (NH4+) and amide ions
(NH2−).
1) Acid-base reactions
Substance that produces ammonium ions (NH4+) in liq. NH3 behave as acid,
while those produces amide ions (NH2−) behave as base.
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2) Protolysis
Some compounds like urea, acetamide, sulphamide etc., which are incapable
of donating protons to water can readily donate proton to NH3 in liquid ammonia.
Hence these compounds act as acid in liq. NH3.
3) Precipitation reaction
It involves double decomposition, due to difference in the solubilities of
various substances in water and liq. NH3.
Liq. NH3 is better in precipitation reaction than water.
In aqueous medium,
In liq. NH3,
4) Ammonolysis
The solvolysis reaction of liq. NH3 is called ammonolysis reactions.
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5) Complex Formation Reactions
These reactions are similar to the reactions occurring in the aqueous system.
Alkali metal in liq. NH3
The alkali metals dissolve in liquid ammonia giving deep blue solutions which
are conducting in nature.
Ammoniated electrons are responsible for blue colour of the solution. The
electrical conductivity is also due to the ammoniated cations and ammoniated
electrons.
When concentration of metal increased, the colour changes to bronze and
shows metallic appearance.
These solutions are good conductor and show strong reducing properties.
These solutions are paramagnetic and the paramagnetic character decreases
with increasing concentration.
As concentration of solution increased, ammoniated cations & electrons
associate, resulting in a decreased conductivity.
Strong reducing character of these solutions is due to the presence of readily
available electrons.
Advantages of liquid NH3 as a solvent
i) Organic compounds are generally more soluble in liquid ammonia than in
water.
ii) Solutions of alkali metals in liquid ammonia are strong reducing agents. These
solutions are used extensively in synthetic inorganic and organic chemistry.
iii) Solvolytic reactions are less important in liquid ammonia than in water,
iv) The tendency for solvolysis is less in liq. NH3 than in water.
v) Liq. NH3 act as an excellent medium for ammonolytic reactions.
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vi) The stronger bases can exist in liquid ammonia than are available in aqueous
solution.
vii) Ammoniated salts dissolved in liq. NH3 find application in preparative
chemistry.
Disadvantages of liquid NH3 as a solvent
i) Liquid range of liq. NH3 is very low (− 77℃ to − 33℃). Therefore a low temp
and high pressure is required.
ii) Liq. NH3 has offensive odour & hygroscopic in nature. Therefore reactions are
to be carried out in sealed tubes.
iii) The reaction medium requires a special technique as it has an offensive odour.
LIQUID SO2
Liq. SO2 is a non-protonic solvent, because it does not contain any hydrogen
atom.
Physical properties
Liq. Range (-75.5 to -10.2℃)
Dipole moment 1.61 D
Its dielectric constant is small (15.6 at 0℃) .Therefore it’s a good solvent for
covalent compounds.
STRUCTURE OF SO2
AUTOINOZATION
Autoionization of liq. SO2 gives thionyl ion (SO2+) and sulphite ions (SO32−).
1) Acid-Base Reaction:
Compound which gives SO2+ is acidic and substances which gives SO32−act
as base.
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2) Neutralization reaction:
Neutralization is a chemical reaction in which an acid and a base react
quantitatively with each other to give a salt.
3) Solvolytic Reactions:
Binary halides such as PCl5, UCl6, WCl6 undergo solvolysis in liq. SO2.
Ammonium acetate is solvolysed in liq. SO2.
4) Precipitation Reaction or Metathetical reaction:
A large number of precipitation reactions can be carried out in liquid SO2
due to selective solubilities of compounds.
5) Organic Reactions :
A large number of organic compounds are soluble in liq.SO2, because it is
relatively inert solvent.
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A) Sulphonation reaction
B) Friedel-Craft reaction
C) Substitution reaction
Advantages:
i) Low cost and easy handling.
ii) It has low boiling point and this allows its easy evaporation. ie, removal from
the reaction mixture.
iii) Liquid SO2 is an inert solvent.
iv) It has unusual solvating powers for both covalent and electrovalent
compounds.
v) It is used as dilutent for the super acid medium (HSO3F-SbF5) which helps in
reducing its viscosity without affecting its acidity.
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