Precipitation Titration

Precipitation titration
 based on reactions that yield ionic compounds of limited
solubility.

 slow rate at which most precipitates form, limits the

number of precipitating agents that can be used in
titrations

Argentometric Titrations
 Uses silver nitrate as precipitating reagent in the
determination of the halogens, the halogen-like anions,
mercaptans, fatty acids, and several divalent inorganic
anions
 Titration Curves for a Single Ion
 derived in a way  consist of a plot of pAg
analogous to the methods versus volume of the silver
for titration involving reagent (usually AgNO3)
strong acids and strong
bases

 only difference is that

solubility product of the
precipitate is substituted
for the ion-product
constant for water
Titration Curves
Titration Curves
Titration Curves
 Titration Curves
Effect of Concentration on Titration Curves
 Titration Curves
Effect of Reaction Completeness on Titration Curves

• solubility product (Ksp) of the titration product affects the sharpness of the end
point of titration experiments

Example: titration using AgNO3

• change in pAg at the equivalence point becomes greater as the solubility

products become smaller (reaction between the analyte and silver nitrate
becomes more complete)

• By choosing an indicator that changes color in the pAg region of 4 to 6, titration

of chloride ions should be possible with a minimal titration error

• ions forming precipitates with solubility products much larger than about 10-10
do not yield satisfactory end points.
 Titration Curves
Effect of Reaction Completeness on Titration Curves
 Titration Curves
End Points for Argentometric Titrations:
1. Chemical
 Chemical indicators produce a color change or
occasionally the appearance or disappearance of
turbidity in the solution being titrated
2. Potentiometric
 the potential difference between a silver
electrode and a reference electrode is measured
as a function of titrant volume
3. Amperometric
 the current generated between a pair of silver
electrodes is measured and plotted as a function
of titrant volume
 Titration Curves
Requirements for an
indicator for a
precipitation titration:

1. the color change

should occur over a
limited range in p-
function of the titrant or
the analyte

2. the color change

should take place
within the steep
portion of the titration
curve for the analyte
Indicators for Precipitation Methods:

1. Formation of a nonturbid supernatant solution (Gay-Lussac’s

Equal Turbidity Method)

2. Formation of a colored complex ion (Volhard method)

3. Formation of a colored secondary precipitate (Mohr Method)

4. Formation of a colored adsorption method (Fajan’s Method)

 VOLHARD METHOD
• silver ions are titrated with a standard solution of thiocyanate
ion and Iron (III) serves as the indicator

• titration must be carried out in acidic solution to prevent

precipitation of iron (III) as the hydrated oxide.

• Fe (III) concentration greater than 0.2 M imparts sufficient

color to the solution to make the detection of the thiocyanate
complex difficult because of the yellow of iron (III)

• lower concentrations (usually about 0.01 M) of iron are

employed
 Volhard Method
Application of Volhard Method:
 Used for titrating Ag+ and the determination of Cl-
(requires a back-titration)

 First, Cl- is precipitated by excess AgNO3

Ag+ (aq) + Cl-(aq)  AgCl(s) Ksp = 1x10-10
 Excess Ag+ is titrated with standard KSCN in the
presence of Fe3+
Ag+(aq) + SCN-(aq)  AgSCN(s) Ksp = 1x10-12
 When Ag+ has been consumed, a red complex forms
Fe3+(aq) + SCN-(aq)  FeSCN2+(aq)
 Volhard Method
Application of Volhard Method:
Acidic pH :
 prevent Fe(III) → Fe(OH)3(s)
 carbonate, oxalate & arsenate do not interfere whose
silver salts are soluble in acidic media but slightly soluble
in neutral media
 AgCl is more soluble than AgSCN
 in chloride determinations the reaction AgCl(s) + SCN- 
AgSCN(s) + Cl– occurs to a significant extent near the end
of the back-titration
 causes the end point to fade and results in
overconsumption of thiocyanate ion. The resulting low
results for chloride
 Error can be overcome by filtering the silver chloride
before undertaking the back-titration or addition of
nitrobenzene
 Volhard Method
Application of Volhard Method:

Determination of bromide, iodide and thiocyanate via indirect

method

 Ksp AgBr = 5.0 x 10-13

 Ksp AgI = 1.0 x 10-16

 In the determination of iodide, ferric indicator is only added

after an excess of silver nitrate has been added
2I- + Fe3+  I2 + Fe2+
 Mohr Method
Used for determination of Chloride and bromide
Indicator chromate ion CrO42- (brick red
silver chromate at equivalence
point)
Medium neutral or faintly alkaline
 Mohr Method
 has to be performed at a neutral or weak basic solution of
pH 7-9 (or 6-10)
 In a lower pH (acidic solution)
CrO42-(aq) + 2H+(aq)  Cr2O7-2 (aq) + H2O
 In a higher pH (basic solution)
2Ag+ (aq) + 2OH- (aq)  Ag2O(s) + H2O

 iodide and thiocyanate cannot be determined successfully

 silver iodide and silver thiocyanate adsorb chromate ions
so strongly that a false and indistinct end point is obtained
Mohr Method
 Fajans Method
 2 facts of adsorption effects on colloidal precipitates:

 finely divided precipitates tend to adsorb on the ions present

in the solution (particles becomes electrically charged)

 Precipitated salt tends to adsorb ions common to itself (AgCl

adsorbing either silver or chloride ion)

 uses an adsorption indicator (Fluorescein) that tends to

adsorbed onto the surface of the solid in a precipitation titration
 Fajans Titration
-O O O

Cl Cl

CO2-

Dichlorofluorescein
 green in solution but pink when adsorbed on
AgCl
 Fajans Titration
Titration of AgNO3 with neutral solution of AgCl in the presence of fluorescein dye
(yellow):

1. At the start of the titration, AgCl is precipitated in the presence of excess silver.
2. AgCl adsorbed silver ions: (AgCl)Ag+ + NO3-
3. adsorbed silver ions unite with fluoresceinate ions forming reddish pink
compound
4. When equivalence is overstepped, the precipitate is in excess chloride, silver is
precipitated as AgCl and precipitate adsorbed chloride ion: (AgCl)Cl- + Na+
5. Fluorescienate ions are liberated and forms back the fluorescein (yellow)
6. Transition of reddish pink to yellow is taken as the endpoint