The major reason is that many acids and bases cant be quantitatively in water at reasonable concentrations (~0.1M).

The problem occurs when the pKA or pKB of our material is > 7. The endpoint is not a sharp break so is very difficult to detect.

pKA 8 pKA 7 pKA 6 pH pKA 5 pKA 4 pKA 3 As the pKA increases, it becomes more difficult to detect the equivalence point.

KB =

KW KA

[ HA ] [ OH- ] [ A- ]

KW KA

[HA] [OH-] = [A-]

(10-4)2 0.1

= 10-7

With amphiprotic solvents, the solvent plays a significant role in determining the observed acid-base chemistry and titration curves. Non-ionizing solvents only act to transport on pairs. Aprotic solvents only contribute solubility. Well now look as several amphiprotic solvents.

This amphiprotic solvent is commonly considered the universal solvent High dielectric constant - 78.5 KW = 1.00 x 10-14 pH scale 0 - 14 Strong acids are considered to dissociate completely producing H3O+.

So H3O+ is the only aqueous acid and OH- is the only aqueous base. Our acids and bases cant be any stronger than these species. Weak acids and bases have as an additional limit incomplete ionization. It makes sense that many of our strong acids are significantly different -- why would they be of the same strength?

Another amphiprotic solvent 2 CH3COOH pKHAC = 14.45 While the pH range is similar to water, CH3COOH2+ is a stronger acid and CH3OO- is a stronger base. It also has a lower dielectric constant. CH3COOH2+ + CH3OO-

As a result, strong acids will still dissociate completely but, because of the low dielectric constant, tend to exist as as ion pairs. Perchloric acid is the strongest acid in acetic acid. KA =
[H+
HAc

Since acetic acid is less basic than water, it does not level strong acids. This increases the number of acids and bases we can titrate. The expanded pH scale also helps somewhat. Acetic still levels aliphatic amines and simple aromatic amines.

] [ ClO4 ] [ HClO4 ]

= 10-4.87

This is the most common acid to use in nonbasic solvents (like acetic acid) It also serves as an excellent example of what is possible when using a solvent other than water. While perchloric acid is more hazardous than other acids, in acetic acid, it produces the sharpest endpoint.

pH

HCl HNO3 HClO4

COOHClO4 + COOH HClO- +

COOH

COOH