The major reason is that many acids and bases

can’t 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 As the pKA increases,

it becomes more
pH

pKA 5 difficult to detect

the equivalence point.
pKA 4

pKA 3

KW [ HA ] [ OH- ]
KB = =
KA [ A- ]
KW [HA] [OH-] (10-4)2
= = = 10-7
KA [A-] 0.1
 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.

We’ll 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 Another amphiprotic solvent
the only aqueous base.
2 CH3COOH CH3COOH2+ + CH3OO-
Our acids and bases can’t be any stronger
pKHAC = 14.45
than these species.
Weak acids and bases have as an additional
While the pH range is similar to water,
limit incomplete ionization.
CH3COOH2+ is a stronger acid and CH3OO- is
It makes sense that many of our strong acids a stronger base.
are significantly different -- why would they be
of the same strength? It also has a lower dielectric constant.
As a result, strong acids will still dissociate Since acetic acid is less basic than water, it
completely but, because of the low dielectric does not level strong acids.
constant, tend to exist as as ion pairs.
This increases the number of acids and bases
Perchloric acid is the strongest acid in acetic we can titrate.
acid.
The expanded pH scale also helps somewhat.
[H+ HAc
-
] [ ClO4 ]
KA = [ HClO4 ]
= 10-4.87 Acetic still levels aliphatic amines and simple
aromatic amines.

This is the most common acid to use in non-

basic solvents (like acetic acid)

It also serves as an excellent example of what is

possible when using a solvent other than
pH

water.
HCl
While perchloric acid is more hazardous than HNO3
other acids, in acetic acid, it produces the
sharpest endpoint. HClO4

COO- COOH

HClO4 + HClO- +

COOH COOH