Non-Aquous solvents

An inorganic nonaqueous solvent is a solvent other than water, that is not an organic
compound. Common examples are liquid ammonia, liquid sulfur dioxide, sulfuryl chloride
and sulfuryl chloride fluoride, phosphoryl chloride, dinitrogen tetroxide, antimony trichloride,
bromine pentafluoride, hydrogen fluoride, pure sulfuric acid and other inorganic acids. These
solvents are used in chemical research and industry for reactions that cannot occur in
aqueous solutions or require a special environment.

The Brønsted theory encompasses any type of solvent that can donate and accept H+H+ ions,
not just aqueous solutions. The strength of an acid or a base varies depending on the solvent.
Non-aqueous acid-base chemistry follows similar rules to those developed for acids and bases
in water. For example in liquid ammonia, the solvent autodissociates in the reaction:
This equilibrium is analogous to the autodissociation of water, but has a smaller equilibrium
constant (K ≈ 10-30). It follows by analogy to water that NH4+ is the strongest acid and NH2- is
the strongest base that can exist in liquid ammonia. Because ammonia is a basic solvent, it
enhances the acidity and suppresses the basicity of substances dissolved in it. For example,
the ammonium ion (NH4+) is a weak acid in water (K a = 6 x 10-10), but it is a strong acid in
ammonia. Similarly, acetic acid is weak in water but strong in ammonia. Solvent leveling in
fact makes CH3COOH and NH4Cl both strong acids in ammonia, where they have equivalent
acid strength.
Strong acids that are leveled in water have different acid strengths in acidic solvents such as
HF or anhydrous acetic acid. For example, acid dissociation of HX in acetic acid
(CH3COOH) involves protonating the solvent to make its conjugate acid (CH3COOH2+) and
the X- anion. Because CH3COOH2+ is a stronger acid that H3O+, the anion X- (which is a
spectator in water) can become a weak base in CH3COOH:
It follows that acidic solvents magnify the Brønsted basicities of substances that cannot
accept protons in water. Conversely, basic solvents magnify the acidity of substances that
cannot donate a proton to OH−.
The acidity and basicity of non-aqueous solvents is difficult to quantify precisely, but one
good relative measure is the Hammett acidity function, Ho, which is defined analogously to
pH according to the Henderson-Hasselbach equation:

For non-aqueous solvents, or for acidic or basic compounds in dissolved in solvents that do
not themselves dissociate, Ho is a rough measure of the pH of the solvent or compound in
question. Anhydrous HF and H2SO4 have Ho values of approximately -10 and -12
respectively.

Classification of solvents
1. Acid solvent
2. Basic or protophilic solvent
3. Amphiprotic solvent
4. Protonic or protic solvent
5. Non protonic/aprotic solvent
6. Coordinating solvent
7. Inert solvent
1. Acidic solvents: Solvents that have strong tendency to donate protons are called acidic
solvent because they are acidic in nature Example are H2SO4,HF and CH3COOH.
2. Basic or protophillic solvents Basic or protophillic solvents have strong tendency to
accept protons and are basic in nature Examples are ammonia, hydrazine,
ethylenediamine, etc
3. Amphiprotic solvents Solvents which neither have a strong tendency to gain nor lose
protons are called Amphiprotic solvents. Example: H2O ,CH3CH2OH ,CH3OH.The most
important nonaqueous solvents of this class are the lower alcohols methanol and
ethanol. They resemble water in their acid–base properties.But because of their lower
dielectric constants, facilitate processes producing ions to a much smaller extent. In
particular, the ion products of these solvents are much smaller (Ks = 10−17 for CH3OH
and 10−19 for C2H5OH, compared with 10−14 for water), and the dissociation constants
of molecular acids and bases are uniformly lower than in water by four to five powers of
10. Nitric acid, for example, which is almost completely dissociated in water (Ka about
20), has Ka = 2.5 × 10−4 in methanol. On the other hand, the equilibrium constants of
processes such as NH4 + + ROH  NH3 + ROH2 + and CH3CO2 − + ROH  CH3CO2H + RO−
are similar in all three solvents, since they do not involve any change in the number of
ions.
4. Protonic/protic solvents Solvents that could be a source of protons (H+ ions) are called
protonic or protic solvents. Some examples of protonic/protic solvents are water,
hydrogen flouride, tetraoxosulphate (VI) acid and hydrochloric acid. Protic solvents often
have hydrogen bound to oxygen (such as OH- ) or a nitrogen (as in amine).
Consequently, any solvent that contains H+ is called protic solvent.
5. Aprotic/non protonic solventsdo not contains ionizable hydrogen atom are called
nonProtonic Solvents. Example include SO2, N2O4, C6H6,CHCl3, CCl4. Most protic and
aprotic solvents that are commonly used are polar.
6. Coordinating solvent Based on the ability to coordinate with cation or anion, non-
aqueous solvents can be classified into the following two groups,
A. Coordinating solvents: Coordinating solvents are those solvents that have the ability
to coordinate with the metal ion or anions of the solute . Common example of
coordinating solvents are ammonia, sulphur (IV) oxide, nitro methane etc.
B. Non coordinating solvents: Solvents such are carbon tetrachloride and saturated
hydrocarbons cannot coordinate with metal ion or anion and are referred to as
noncoordinating solvents.
7. Inert solvents Solvents with low relative permittivities (or dipole moments) and very
weak acidic and basic properties are called inert solvents. Examples of inert solvents are
CH2Cl2, CHCl3 and benzene; inert solvents such as n-hexane andcyclohexane). Inert
solvent usually have low polarity and high permittivity. There are useful as solvents
where solvent interaction must be check. This is because their low permittivity, electrical
conductivity and dipole moment makes them to be less reactive.