Inorganic Chemistry 1

CHEMF214

Instructor-in-charge
Inamur R. Laskar

Chemistry of Aqueous & Non-aqueous solvents

Chemistry in Aqueous and Nonaqueous Solvents

Aprotic Solvents
Difference between protic & aprotic solvents: presence of
transferable H and the formation f onium ions
Classification of aprotic solvents: (a) non-polar, non-solvating and
dont undergo autoionization; e.g., cyclohexane, CCl4 etc; these are
used in calculating E, C parameters; (b) polar, do not autoionize,
basic solvents and capability to coordinate to strongly with cations
and other acidic centres; e.g., CH3CN, DMSO, dimethylacetamide,
SO2 ;
CoBr2 + 6DMSO
[Co(DMSO)6]2+
SbCl5 +CH3CN
CH3CNSbCl5
Donor number: Gutman has defined the donor number (DN) as a
measure of the basicity or donor ability of a solvent
It is defined as the negative enthalpy of reaction of a base with the
Lewis acid SbCl5, B + SbCl5
BSbCl5, DNSbCl5 = -H

Aprotic Solvents: Donor Numbers

Comparison of relative donor abilties (compare the donor number from
the Table)
No exact corelation between donor number and permittivity (check the
Table); this fact reveal that the solvation is not merely an electrostatic
interaction but that the solvation also involves the ability to form covalent
donor bonds
Gutman has extended the concept an acceptor number which measures
the electrophilic behavior of a solvent
Drago has criticized the donor acceptor concept because it accounts only
half of the information available of the Dragos four parameter equation

3rd group: Highly polar and autoionizing: highly reactive; difficult to store
as they react with moisture and other contaminants; some react silica
container and dissolve Ag and Au electrodes; e.g., BrF3 ; non fluoride salts
like oxides, carbonates, iodates and other halides are fluorinated
Sb2O3 + BrF3
BrF2+ + SbF6-; NOCl + BrF3
NO+ + BrF4-

Aprotic Solvents
Check the text book in page 256-257
NOClO4 behaves as acid whereas NaNO3
behave as base in N2O4 - explain

Some Question Answers

Q1. The dissociation constant of nitric acid in water is 20

whereas in methanol 2.5 x 10-4-why?
Q2. Silver perchlorate is significantly more soluble in benzene
than in alkane solvents. Account for the observation in terms
of Lewis acid base properties.
Q3. Of the donor-acceptor complexes (CH3)3N-SO3 and H3N-SO3
in the gas phase. (a) Which has the longer N-S bond?
(b) Which has the larger N-S-O angle?
Q4. Why were most of the metals used in early prehistory class
(b) (soft in HSAB terminology) metals?

Dipole moments
Permittivity

Methanol
1.7
32.7

Water
1.85
76

Amphoteric solvents
The most important nonaqueous solvents of this class are the lower
alcohols methanol and ethanol. They resemble water in their acidbase
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 = 1017 for CH3OH
and 1019 for C2H5OH, compared with 1014 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 = 2.5 104 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.