Pharm.

Analytical Chemistry II
Dr. Khairi M. Salem

Friday, November 8, 2019 1

Principles: Precipitation Titrimetry Based on the reaction that
yield ionic compounds of limited solubility (insoluble
product) and considered as one of oldest analytical
methods. The reaction occur between the analyte and
precipitating agent such as AgNO3,, which applied for the
determination of halides like (Cl-, I-, Br- and F- and halid
like ions as (SCN-,CN-, and CNO-. Titremetric methods
used AgNO3 as precipitating agent termed as
Argentometric titrations.

Formation of precipitate: When the precipitate is formed ,

although it is insoluble, a very small amount of which
dissolve forming a saturated solution, and equilibrium is
established between molecules and it’s ions as follows:
AgCl AgCl Ag+ + Cl-
Solid ppt. Sat. solution Ions
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 [Ag+] [ Cl-] / AgCl = k
[Ag+] [ Cl-] = k
In such a saturated solutions of sparingly soluble
salts, the product of ionic concentration is constant
at a given temperature .this constant is called
(solubility product constant) Ksp or (S)
So [Ag+] [ Cl-] = Ksp or S
 The solubility product of a substance equals to the
product of molar concentration of ions involved.
 A precipitate is formed in a solution of sparingly
soluble salt, when the concentrating of it’s ions in
the solution exceeds the solubility limit.

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 Precipitation Titrimetric Methods
1. Mohr’s Method
2. Volhard's Method
3. Fajan's Method
Mohr’s Method: This method depends on the
formation of halid ppt. like AgCl, When
Chloride soluble salt as NaCl is titrated with
AgNO3 using sodium or potassium chromate
as indicator. The method is simple and direct
method.
Cl- + Ag+ AgCl ( white ppt.)
2Ag+ + CrO42- Ag2CrO4 (Red ppt.)

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 Although AgCl and Ag2CrO4 are insoluble in
water, the later is more soluble than the former
so Ag2CrO4 will not ppt. until all chlorides has
been removed from the solution to form AgCl(
White ppt.), then Ag2CrO4 will ppt as red ppt .
Which indicate the reaching of end point.

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 Factors affecting Mohr’s method:
 The amount of indicator used: Ag2CrO4 is ppt.
when it exceeds its solubility limit and a
moderate amount of ppt. indicator should used
about 1 ml of 5% solution of K2CrO4 for each 50
ml of solution…WHY ?
 If small amount of indicator is used the conc. Of
CrO4 is very small , and large amount of Ag+ is
required to reach the E.P ( The E.P comes too
late)
 If large amount is added which means high
conc. Of CrO4, an intensive yellow color of
solution will produced which may mask the E.P
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 2. Hydrogen ion concentration (pH effect)
 For successful use of chromate ion as indicator the
medium must be neutral or slightly alkaline with
pH between 6.5-9.0
 In alkaline solution pH above 9.0 silver hydroxide
might ppt. which effect the Ag+ required for Cl-
precipitation.
 In acidic media, the chromate ions changes to acid
chromate then to dichromate as follows:
 CrO4-2 + 2H+ 2HCrO4 Cr2O7 +H2O
3. Effect of Temperature: Silver chromate is more
soluble in hot water, so the titration must be carried
at room temperature.

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2.Fajan's Method (Adsorption indicator method)
Principle: This is a direct titration method for
determination of halides and halide like ions, which
uses certain dyes as internal adsorption indicator.
The adsorption indicators are organic compounds that
tends to be adsorbed onto the surface of the solid in
precipitation titration, which occurs near the
equivalence point, leading to the color change of the
ppt. and transfer the color to the solution.
Fluorescein is commonly used adsorption indicator for
the titration of Cl- ion with AgCl, fluorescein is
partially ionized in aqueous solution into hydronium
ion and fluoresceinate ion(- ve charged ion), that
have yellow green color, and produce intensive red
sliver salt when react with Ag.

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 The theory of action of adsorption indicators:
 When AgNO3 is added to Cl- solution, the ppt of AgCl is
colloidal and can therefore adsorb ions from solution, these
ions form primary adsorption layer and can hold a
secondary layer of oppositely charged ions from the solution.
 1. During the titration and before the equivalence point:

Cl- Cl- Na+

Cl- Na+
Cl- AgCl
-
Cl- Cl Na+

◦ Fig.1 Na+ Na+

 During the titration of NaCl with AgNO3, Cl- are in excess ,
primary adsorbed layer consists of Cl- with a secondary
layer of Na+ as shown in the Fig(1).

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2. After reaching the equivalence point:
After the equivalence point has reached , Ag+ are in excess so
that Ag+ forms the primary layer with NO3- adsorbed as
secondary layer.(Fig.2)
3. If fluorescein is also present in solution, fluoresceinate ion
has higher or strong adsorbing property than the NO3-
ion (Fig. 3)
In - In -
Ag+ NO3 NO3
Ag+ In -
Ag+ NO3 Ag+ Ag+
Ag+ AgCl NO3
Ag+ In -
Ag+ Ag+ NO3 Ag+ AgCl
Ag+ Ag+ In - NO3
NO3
In -
Fig. 2
Fig.3

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 Factors affecting Fajan’s method:
1. H+ Concentration: (pH of the Medium)
The optimum condition of the pH is 7-10, because
Fluorescein
Is weak acid and dissociated in the mentioned pH range to
form fluoresceinate ion which is responsible for the color
change at the E.P due to the adsorption on AgCl surface.
Eosin is more stronger acid , so low pH value around pH of
3 to 4, can dissociate Eosin to Eosinate ion , which produce
red color at the E.P.
2. The effect of temperature: Room temperature is
recommended to carry out the experiment, high temp. may
effect the dissociation of the indicator and the E.P.

Friday, November 8, 2019 11

3. Volhard's Method (Formation of colored complex):
PRINCIPLE: The Method involves Indirect titration for
halides which depends on the reaction of halide ion with
excess of AgNO3
In nitric acid medium and the excess of Ag+ is determined
by the titration with potassium thiocyanate using ferric
alum as indicator
Ag+ + Cl - AgCl (white ppt)
Ag+ + SCN- AgSCN (White ppt)
SCN - + Fe3+ Fe(SCN)2+ (Red color)
The Ferri thiocyanate is soluble complex which has
highly intensive red color which indicate the end
point.

Friday, November 8, 2019 12

 Factors affecting Volhard's Method :
1. The volume of indicator: The reaction is very
sensitive, so the volume of indicator is not critical even
small volume (0.1 ml of 0.1N solution is sufficient to
produce Red color of soluble complex.
2. PH of the medium: HNO3 is used to acidify the
medium and prevent the precipitation of Fe3+ and Ag+
As hydroxides in alkaline media.
3. Temperature: increasing the temperature more than
the room temperature will enhance the HNO3 to bleach
(remove) the complex color at the E.P

Friday, November 8, 2019 13

In the Precipitimetry titration curves we plot the exponent of the
concentration (PCl or PAg) against the volume of precipitimetric agent
(ml)

PCl PAg
Vol. of AgNO3 (ml)
Vol. of AgNO3 (ml)

Example: If 0.1N of AgNO3 solution is added to 100ml of 0.1N

NaCl solution, given that the Ksp AgCl = 1.1X10-10 or Pksp
= 9.96. Calculate the Cl- concentration at :
1. The beginning and before adding AgNO3
2. After adding 50 ml of AgNO3
3. After adding of 90 ml of AgNO3
4. At the equivalence point (adding 100 ml of AgNO3
5. After the equivalence point (adding 101 ml of AgNO8, 2019
Friday, November 3 14
1. AgNO3 = 0 ml ( at the beginning & before adding AgNO3)
and Cl- concentration = 0.1 = 10 -1
 So PCl = -log Cl- = 1

2. After adding 50 ml AgNO3 :

The conc. Of Cl- is 50 ml of 0.1N in dilution of 150ml
Cl- = (100X0.1) – (50X0.1) / 150 = 50X0.1 / 150 = 1/30 =
3.3X10-2
So PCl = -log (3.3X10-2) = 1.48
3. After adding 90 ml AgNO3 :
The conc. Of Cl- is 10 ml of 0.1N in dilution of 190ml
Cl- = (100X0.1) – (90X0.1) / 190 = 10X0.1 / 190 = 1/190 =
5.3X10-3
So PCl = -log (5.3X10-3) = 2.28

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 4. At the equivalence point (After adding 100 ml AgNO3)
Here there is No Excess of Cl- or Ag+ , but conc. Solution of
AgCl to form insoluble salt.
[Ag+][Cl-] = Ksp = 1.1 X10-10
At the equivalence point [Ag+] = [Cl-] = Ksp = 1.1 X10-10
= 1.05 X10-5 So PCl = -log 1.05 X10-5 = 4.98 = 5.0
5. After the equivalence point (After adding 101 ml AgNO3)
1 ml of Ag+ in excess
Ag+ = (101 x 0.1) – (100 x 0.1)/201 = 0.1/201= 5 X10-4
P Ag+ = - log 5 X10-4 = 3.3
PCl = Pksp – PAg = 9.96-3.3 = 6.66

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 Pharmaceutical Applications
 As quantitative volumetric technique,
Precipitation can be applied in the analysis of
many drug formulations containing halides or
halide like ions such as:
 Determination of the concentration of oral
dehydration salts which contain NaCl and KCl
salts.
 Determination of the concentration of infusion
solution containing Chloride salts.
 Determination of certain multivitamin and
salts dosage forms

Friday, November 8, 2019 17