TITRIMETRIC ANALYSIS

Topic 4
PRECIPITATION TITRATION

1st March 2011

DrSabiha/CHM421/Dec 10-Apr11

Fajans Method
The end-point technique
adsorption indicator.

based

on

Limitation
The samples should not be acidic.
Application in the determination of
neutral to slightly acidic samples only.

At end point (Fajans Method) :

AgCl precipitates will adsorb excess Ag+
and that this adsorbed Ag+ will contribute
excess positive charges on surface of
precipitate. The excess positive charges are
neutralized by a negatively-charged ions
present in solution usually a dye (D)
(indicator) in the above titration.
if AgD is coloured, the white precipitate
will turn colour just past the end point.

The best indicator is FLUORESCEIN (weak acid)

Indicator ionising slightly in water to form
flouresceinate :

HFn

H+ + Fnyellow green

C20H12O5

at the end point :

Ag+ + FnAgFn (red precipitate)
Silver Fluoresceinate (AgFn) is a red precipitate.
RED or
PINK COLOUR is seen AT THE END-POINT.
Prior to the end-point, the solution is yellow-green
due to
the Fn- ions.

Volhard Method (indirect method)

The samples can be acidic or alkaline.
Volhard method is used to determine cation Ag+ as well
as anion Br- , I- and Cl- . A halide ion is added with
standard AgNO3 in excess and then the extra Ag+ is
back titrated with standard KSCN with Fe3+ ion as
the indicator.
Principle:
X- + Ag+
AgX ( white ppt )
(excess)
The extra Ag+ ion is back titrated with KSCN.

In back titration :
Ag+ + SCN-

AgSCN ( white ppt )

The indicator used is Fe3+ ion which will form a complex with
SCN- at the end point.
The end point of the titration is shown by the colour of the
soluble complex [Fe(SCN)]2+ which is red in colour.
End-point:
Fe3+ + SCN-

[Fe(SCN)]2+
a red soluble complex

Chloride Determination by Volhard Method.

More difficult than Mohr Method because AgCl is
more soluble than AgSCN precipitate in extreme pH
conditions.
Therefore, at the end point the following reaction occurs
in the back titration.
AgCl(ppt) + SCNSCN(ppt) + ClTo avoid this difficulty:
1. Add a very high concentration of indicator (0.2 M) of
Fe3+ so that [Fe(SCN)]2+ is formed before a significant
SCN- is added (and has the chance to react with AgCl).
2. Remove AgCl precipitate by filtration.
3. Add a few mL of nitrobenzene to coat the surface of
the AgCl precipitate to prevent it from reacting with
SCN-.

Calculation examples :
Example 1
25.0 ml of silver nitrate solution was precipitated
with excess sodium chloride solution. 0.4335 g of
silver chloride was formed. If 25.40 ml of the same
silver nitrate solution required 17.30 ml potassium
thiocyanate solution to reach the end-point.
Calculate the concentration of silver nitrate and
potassium thiocyanate.

Ag+ + ClAg+ + SCN-

AgCl (ppt)
AgSCN

Calculate no of mol AgCl = 3.0209 x 10 -3 mol

From Stoichiometry mol of AgCl = mol of AgNO3
Molarity of AgNO3 = 0.1208 M#
mol AgNO3 = 0.1208 x 0.02540
= 3.0683 x 10 -3 mol
From Stoichiometry mol of AgCl = mol of AgNO3 = mol KSCN
Molarity of KSCN = 3.0683 x 10 -3 mol
0.01730 L
= 0.1774 M#

Example 2
7.5124 g of sample X which contain 45.5% Br- is
dissolved in a 250 mL volumetric flask. 25.0 mL
of the above solution is being titrated with
0.1235 M AgNO3 solution.
1. Suggest what method can be used in the above
titration?
Name a suitable indicator that can be used to
detect the end point.
Calculate the volume of silver nitrate used at
end-point.

1. Mohr method
2. Chromate, CrO423. Br- + Ag+ = AgBr
g Br- = 7.5124 x 0.455 = 3.4181 g
Mol Br- = 0.0428 mol.
Molarity Br- solution = 0.1711 M
Mmol Br- = 0.1711 x 25.0 =4.2775 mmol
= mmol of AgNO3
Volume of AgNO3 = 34.64 mL#

The arsenic in a 1.035g sample of a pesticide was converted to H3AsO4 by

suitable treatment. The excess acid was then neutralised and 30.0 mL of
0.0650 M AgNO3 was added to precipitate the arsenic quantitatively as
Ag3AsO4. The excess Ag+ in the filtrates, and washings from the precipitate
were titrated with 9.50 mL of 0.1000 M KSCN.
Ag+(aq) + SCN-(aq) AgSCN(s)
Calculate the percentage of As2O3 in the sample.

4th January 2011

DrSabiha/CHM421/Dec 10Apr11

12

H3AsO4 + 3AgNO3 Ag3AsO4 + 3HNO3

Initial mol Ag+ = 40x10-3Lx0.085M
= 3.4x10-3 mol
Excess mol Ag+ =11.27x10-3Lx0.1M
= 1.127x10-3 mol
Reacted mol Ag+ = 3.4x10-3 mol - 1.127x10-3 mol
= 2.273x10-3 mol
From reaction above, H3AsO4 =2.273x10-3 mol
3
= 7.577x10-4 mol
All arsenic in H3AsO4 originated from As2O3
Mol As2O3=7.577x10-4 molx2
= 1.515x10-3 mol
Mass of As2O3 in the sample = 1.515x10-3 molx197.8432
= 0.2998g
Percent As2O3 in the sample = 0.2998 x 100
1.223
= 24.51%

4th January 2011

DrSabiha/CHM421/Dec 10Apr11

13