Acid-base indicators: The materials used as indicators in acid- base titrations are, very weak organic acids or bases.

The conjugate pair of such cpds. exhibit different colors.

Acid Base Titrations

HIn + H2O acid color In + H2O base color

In- + H3O+ base color InH+ + HOacid color

pKHIn

Consider HIn case;

HIn + H2O = In- + H3O+ Ka = [In- ][H+ ] ; [HIn] [HIn] [H+ ] = K a [In- ]
[H+]

For the eye to detect a color change,

[HIn] [In- ]
must change by at least 100 times. [H+] must change at least by 100.

During the acid base titration changes, i.e. pH (low to high...); and varies rapidly at the end point. As the pH changes rapidly the quotient in the latter equation should change rapidly as well. Thus the ratio,

pH= (-log[conc]); must change by 2 at the eq. pt. If HIn is in an acidic solution it exists as Hin; color = acid color. (ratio =10) If HIn is in a base, it exists mainly as In; color =base color. (ratio = 0.1)

[HIn] [In- ]
will change rapidly, giving a color change.

HIn + H2O = In- + H3O+ K HIn = [In- ][H+ ] ; [HIn] [HIn] [H+ ] = K HIn [In- ] pH = pK HIn + log [In- ] [HIn]

pH (acid) =pKHIn + log(1/10) = pKHIn - 1 pH (base) =pKHIn + log(10) = pKHIn +1 color change range = pKHIn 1
pH range of indicator.

This range can change with temperature, ionic strength, solvents, colloidal particles, etc.

A dibasic species HA=A

CO3-2,0.1M
HA H2A=HA H2A
Charge omitted

CO3-2,0.1M + HCO3- ,0.1M

More basic site neutralized earlier

More basic site neutralized earlier

pK1=2.85 pK2=5.70

To get sharp pH drops the pK ~ 3 or higher

Stronger acid/base, higher concentrations ~ sharper end points

Chem. Educator 2002, 7, 339.346

pK1=3.13 pK2=4.76 pK3=6.40

!! !!

Chem. Educator 2002, 7, 339.346

Amino acids:
CH3 H2N H COOH
H3N+ H
Zwitterion electrically neutral
CH3 H3N+ H COOH H3N+ H CH3 COOH2N H CH3 COO-

Potential proportional to pH

Titrating mixtures of acids

CH3

CH3 = H3N+ H COO-

CH3 COO-

H3N+ H

COOH

pK1a=2.34

H2

A+

amphiprotic

CH3 H3N+ H COO= H2N

CH3 COOH

pK2a=9.87

amphiprotic

A-

H2A+

HA amphiprotic

A-

Isoionic point (pH): pH of pure neutral polyprotic acid (neutral zwitterion) in aqueous solution. A solution of pure amino acid (HA) is amphiprotic. The pH of such an amphiprotic species of formal concentration F is given by;

Additional Equations

H2A+ H2A+

HA + H + A + 2H +

Ka1 Ka1Ka2 Kw

H 2O
MB:

OH + H +

[H+ ] =

K1aK 2aF +K1aK w K1a +F

C HA = [H 2 A + ] + [HA] + [A ]

Note: [H2A+] [A- ], in general; with [H+] from above they can be calculated using the pKa values.

CB

[H + ] + [H 2 A + ] = [OH - ] + [A ]

Isoelectric point (pH): pH at which average charge on the polyprotic acid is zero. i.e. [H2A+] = [A- ], because zwitterion/amphiprotic species is neutral. Eg. For alanine of 0.10M; [H2A+]= 1.6810-5, [A-]= 1.7610-5

Calculation of Isoelectric point:

[ H 2 A] =

[ HA][ H + ] K1a

[ A- ] =

K 2 a [ HA] [H + ]

isoelectric condition; [ H 2 A] = [ A- ] [ HA][ H + ] K 2 a [ HA] = [ H + ]2 = K1a K 2 a K1a [H + ] pH = pK1a + pK 2 a 2

So needed to add a little acid, in this example.

Pure enzyme isoionic point

O H
Enzyme ribonuclease 124 amino acid sites 16 protonates, 20 lose protons, rest buried.

NH3 H O

S S

O C O

Titratable acid/base groups and pK caclulated from plot

pH curve

Gran Plot: Acid-base titrations

1st Derivative

2nd Derivative