Ch 6 Precipitation Titrations, Sec 6-5 and 6-6

Titration of a Mixture

e.g. A mixture of Cl- and I- is titrated with

Ag+. Which halide precipitates out first?
Ksp AgCl = 1.8 x 10-10, Ksp AgI = 8.3 x 10-17
Measuring the Titration Curve in
Precipitation Titrations
Fig 6-5
 Extracting Results From Figure 6-5

In curve (a) in Figure 6-5, 40.00 mL of

unknown solution containing both I- and Cl-
were titrated with 0.0845 M Ag+. Calculate the
Molarity of each ion.
There are three common types of precipitation
titrations -
1. Mohr Method - CrO42- indicator

(yellow to red)
2. Volhard Method - back titration of excess
Ag+ with SCN-, Fe3+ indicator

(clear to red)
3. Fajans Method - adsorption indicator =
dichlorofluorescein anion (pink at
endpoint)
 Mohr Method

Titration of a halide (Cl-, Br-, I-) with AgNO3 to

form a precipitate using K2CrO4 as the indicator.

e.g. Ag+ + Cl- → AgCl

eq. pt. color change to red
The indicator combines with excess Ag+ at the eq. pt. Before the
eq. pt., the solubility of the Ag-halide precipitate must be less
than the Ag-indicator, otherwise the latter would precipitate out
during the titration!
2 Ag+ + CrO42- → Ag2CrO4(s) red
Ag+ + Cl- → AgCl(s) white
1
 Ksp  11
S AgCl   1 1   Ksp  1.8x1010  1.3x105
 1 1 
1 1

 Ksp  21  2.0x10-12 

3
S Ag2CrO4   1 1      7.9x105

 2 1   4 
 Volhard Method

1. Excess AgNO3 is added to precipitate out all of

the halide.
2. The excess Ag+ is back-titrated with KSCN using
Fe3+ as the indicator
e.g. Ag+ + Cl- → AgCl(s)
added in excess
then Ag+ + SCN- → AgSCN(s)
excess titrant
after the endpoint -
Fe3+ + SCN- → FeSCN2+

[Cl-] = total Ag+ - amount backtitrated

 Fajans Method

The indicator adsorbs onto the colloid particles

after the eq. pt. and changes color to pink.

Adsorption Indicator - Dichlorofluorescein

before the eq. pt. the lattice ion in
excess is the halide (Cl- etc) so the
colloid is negatively charged
after the eq. pt. the lattice ion in
excess is the titrant Ag+ so the
colloid is positively charged and
then the negative adsorption
indicator will bind and change color.