Leveling Effect of Solvent

▪ All acids tend to become indistinguishable in strength when dissolved in strongly

basic solvents owing to the greater affinity of strong bases for protons.

▪ On the other hand, a strong acid exhibits more strongly acidic properties than a
weak acid when dissolved in a weakly basic solvent.

▪ For example, HBr and HI have indistinguishable acid strengths in water because
both transfer their protons essentially completely to give H3O+.

▪ However, in acetic acid, HBr and HI behave as weak acids because they transfer their
protons partially to water. Thus, their strengths in acetic acid can be distinguished.

▪ Any acid that is stronger than H3O+ reacts with H2O to form H3O+; therefore, no acid
can be stronger than H3O+ in H2O. Water is therefore said to have a leveling effect
that brings all stronger acids down to the acidity of H3O+.

1
 Leveling Effect of Solvent
▪ The same argument applies to bases in water.

▪ Any base that is stronger than OH‐ reacts with H2O to form OH‐; therefore, no base
can be stronger than OH‐ in H2O. Water brings all stronger bases down to the basicity
of OH-.

▪ For example, O2-, NH2-, OMe- and OEt- ions are all stronger bases than OH‐ ion.
Their strengths in water can not be distinguished because become completely
protonated in water.

▪ However, in liquid ammonia, O2-, NH2-, OMe- and OEt- ions behave as weak bases
because they become partially protonated in water. Thus, their strengths in liquid
ammonia can be distinguished.

▪ The leveling effect operates in any protonic solvent. In liquid ammonia, for example,
all acids are levelled to the strength of the ammonium ion, NH4+, and all bases are
leveled to the strength of the amide ion, NH2‐.

2
 Acid-Base Discrimination Window for Solvents
▪ All acids with pKa < 0 (corresponding to Ka > 1) display the acidity of H2Sol+ when
they are dissolved in the solvent HSol.

▪ All bases with pKb < 0 (corresponding to Kb > 1) display the basicity of Sol– in the
solvent HSol.

▪ Since pKa + pKb = pKsol, all bases with pKa > pKsol give a negative value for pKb and
behave like Sol– in the solvent HSol.

▪ Since any acid is levelled if pKa < 0 in HSol and any base is levelled if pKa > pKsol in
the same solvent, then the window of strengths that are not levelled in the solvent is
from pKa = 0 to pKsol.

▪ For water, pKw = 14. For liquid ammonia, pKam = 33. Thus, acids and bases are
discriminated much less in water than they are in ammonia.

3
 Acid-Base Discrimination Window for Solvents

▪ The window for dimethylsulfoxide (DMSO, (CH3)2SO) is wide because pKDMSO = 37.
Consequently, DMSO can be used to study a wide range of acids (from H2SO4 to PH3).

▪ Water has a narrow window compared to some of the other solvents shown in the
figure. One reason is the high relative permittivity of water, which favours the
formation of H3O+ and OH– ions.

4
 Solvent System Definition of Acids and Bases
▪ Autoionizaion reaction of water:

▪ An acid increases the concentration of H3O+ ions and a base increases concentration
of OH– ions.

▪ Similarly, autoionization reaction of some aprotic solvents, such as BrF3:

sol = solution in the non-ionized species (BrF3 in this case)

▪ Solvent System Definition: Any solute that increases the concentration of the cation
generated by autoionization of the solvent is defined as an acid and any solute that
increases the concentration of the corresponding anion is defined as a base.

▪ This definition is applicable to any solvent that autoionizes.