Precipitation Titration

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 Precipitation titration

Introduction
 Two or more soluble species combine to form an insoluble product
that we call a precipitate Or the formation of a slightly soluble
solid from solution (the reverse of dissolution).
 A reaction in which the analyte and titrant form an insoluble
precipitate also can serve as the basis for a titration.
 This type of titration is a precipitation titration.

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 Introduction

 The first drop of titrant in excess will react with

an

indicator resulting in a color change and indicating

the end point of the titration

 Precipitation titrations

– are based upon reactions that yield ionic compounds of

limited solubility.
– The most important precipitating reagent is silver nitrate.

– Titrimetric methods based upon silver nitrate are

sometimes termed argentometric methods.

 The end point of a reaction in analysis by

precipitation methods can be determined by using indicators
 Illustration: In the determination of chloride, 50 ml of a 0.1M
AgNO3 solution would be required to completely react with 0.005
moles of chloride present in solution.

Analyt Titran
e Produc
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Limitation of precipitation titration

 Slow rate of reaction b/n the titrant & analyte

 Lack of suitable indicator for many pptn titration

 Difficult to obtain an accurate precipitate composition, the

co-precipitation effect is often occurred.
 A few number of ions such as halide ions (Cl-, Br-, I -) can
be titrated by precipitation method. (narrow application)

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 Solubility product
The factor governing the completness of a precipitation rxn
is the solubility of the ppt formed:

The more insoluble the ppt ⇨ the more complete is the

rxn at the equivalent point of the titration.

Solubility product, Ksp:

The equilibrium constant for the reaction in which a

solid salt
dissolves to give its constituent ions in solution.

It expresses the equilibrium between a solid and its

ions in solution.

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 Precipitation titration…

 Solubility product
o A saturated solution of a slightly soluble salt in contact
with an undissolved salt involves equilibrium like the
one below:

o So the equilibrium constant expression for the equilibria

above is:

o This equilibrium constant K s p is called a solubility-

product constant

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 cont...
Calculation of solubility product from solubility
If the solubility of AgCl is 0.0015g/L
[AgCl] = 0.0015/143.3 = 1.05x 10-5 M
AgCl
↔
Ag+ + Cl- SAgCl =

[Ag+] + [Cl-]
= 1.05x 10-5 x
1.05x 10-5
= 1.1 x 10-10
Ag2S ↔ 2Ag+ + S2- 6x10-50 = 4X3
Calculation of
X 2X X X3 = 1.5 x 10-50
solubility from
S Ag2S = [Agproduct
solubility +]2 [S2-] = 6x10- X = 2.47 x 10-17 M
50

The solubility of siliver

sulphide [2X]2water
in pure [X]
 Solubility of Ag2S =is2.47 x 10-17 M x 247.8 = 6.1 x 10-15g/L
6x10-50
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 cont...

Q. The solubility of calcium sulphate (CaSO4) is found to be 0.67 g/L. Calculate the
value of Ksp for calcium sulphate.

- No of mole of CaSO4

- For every mole of CaSO4 that dissolves, 1 mole of Ca2+ and 1 mole of SO4 are
2-

produced, there for;

- Hence:

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 Precipitation titration…
 precipitation Calculations
 If we have a given set of concentration conditions we can
calculate a solubility quotient, Q c , and compare it to the
Ksp
 The solubility quotient (often called the ion product)
has the same form as the solubility constant expression,
but the concentrations of the substances are not
necessarily equilibrium values

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 Precipitation titration…

 Factors affecting solubility of a precipitate

1. Temperature effect
 Most of inorganic salts increase its solubility by
increasing temperature.
 Exception-Hg 2 Cl 2 , MgNH 4 PO 4

2. Solvent effect
 Most of inorganic salts dissolve in water but not
in organic solvent.
 In order to form a precipitate,
the product formed should be insoluble in
the solvent.
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 Precipitation titration…

 Factors affecting solubility of a precipitate…

3. The Common Ion E ffec t
 Precipitate dissolves more easily in water than in
solution containing common ions.
 Consider-solution of AgCl in the presence of
NaCl
4. The pH effect
 Solubility of weak acid/weak base
salt depends on pH of the solution.

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 Argentiometric titration

 On the bases of the method used to identify the equivalent point,

argentiometric titration can be classified as:

1. Mohr method
 Potassium chromate is Used as indicator in the titration of chloride
ions with standard silver nitrate in neutral solution
 It gives a precipitate of red silver Chromate at the end point
 Cont.…
 But this precipitate has a greater solubility than that of AgCl

 Therefore, AgCl is formed first and after all Cl- is consumed, the
first drop of Ag+ in excess will react with the chromate indicator
giving a reddish precipitate.

 In this method, neutral medium should be used since, in alkaline

solutions pH > 10 , silver will react with the solvent forming
AgOH.
 Cont.…
 In acidic solutions, chromate will be converted to HCrO4- and the
end point is delayed .
 The chromate ion conc. is too low to produce the ppt

 This can be avoid by neutralizing the acidic media using chloride

free like CaCO3 or NaHCO3
 In other words silver chromate solubility grows due to the
protonation of chromate anions, therefore, the pH of solution should
be kept at about 7.
 Cont.…
 There is always some error in this method because a dilute chromate

solution is used due to the intense color of the indicator.

 This will require additional amount of Ag+ (titrant)for the Ag2CrO4 to

form .

 This leads to a late equivalent point .

 To correct for this error we can determine a blank .

Mohr method
Disadvantage

 Sulfides, phosphates and arsenates will also be precipitated

 The end point is less sensitive with dilute solution

 Adsorbed ions of the sample become trapped & cause low results
Exercise 1
A 0.32 g sample containing KCl ( mw = 74.6 ) is dissolved in 50 mL of water
and titrated to the Ag2CrO4 end point, requiring 16.9 mL of 0.1 M AgNO3. A
blank titration requires 0.7 mL of titrant to reach the same end point. Report
the %w/w KCl in the sample ?

Answer
 Application:

1. NaCl given through IV infusion.

 in determination of the % w/v NaCl.

2. Potassium iodide
 KI can be determined by direct titration with AgNO3 using iodine & starch

as indictor.

KI + AgNO3 KNO3 + AgI(ppt)

 At the end-point excess silver nitrate reduce the indicator,

iodine, to iodide ion, destroyed the purple starch-iodine complex &

yellow
leaving soln.
a pale 21
 2.Volhard Method

 Most common and indirect method for determining halides or

halogen contents, like Cl- , Br- and I.

 Involves a residual titration of excess AgNO3 with a standard

thiocynate solution.
 So/n of ferric ammonium sulfate or ferric nitrate serve as
indicator & end point is appearance of red ferric thoicynate
complex.

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 Cont.….
 When excess of std. AgNO3 so/n is added in to so/n of
halide
preparation of silver halide occurs:-
– Ag+ (excess) + X- (analyte) ↔ AgX (ppt) + excess Ag+

• the excess AgNO3 is then back titrated with ammonium thiocynate

– Ag+ (remaining excess) + SCN- ↔ AgSCN (ppt)

• At the end point excess thiocynate react with Fe3+ and form
ferric thiocynate red complex.
– Fe3+ + SCN ↔ [FeSCN]2+ (red soluble complex)
 Cont.….
 The medium should be acidic to avoid the formation of Fe(OH)3 .

 If AgX is less soluble than AgSCN as in the case of I - and

Br , the excess Ag+ can be titrated in the presence of AgX
precipitate .
 But in the case of AgCl when SCN - is added just after
the equivalent point the following reaction will take place :
 Cont.….
 AgCl + SCN - ↔ AgSCN + Cl –

 This means that , SCN - instead of reacting with the indicator

it will react with the AgCl precipitate .
 Result: end point fades & over consumption of SCN- and
low value for the chloride analysis
 We have three ways to overcome this problem
 Cont.….
1. siliver chloride is filtered off before back titration.
2. Coating the silver chloride ppt with nitrobenzene. i.e, addition of
some organic solvent which is heavier and immiscible with water
such as nitrobenzene or chloroform , which covers the AgCl
precipitate in the bottom of conical flask and shields it from the
aqueous medium which contains the excess Ag+ that can be
titrated with SCN- .
3. Boiling the solution for 3 min, cooling and titration => enhance
aggregation of precipitates
 Advantages
1. The acidic environment give advantage for halide analysis
because anions such as carbonate , oxalate and arsenate that do
not form precipitate with silver in acidic medium ( but they do in
basic medium ) will not interfere with halides .
2 Give accurate results due to back titration .
 Limitations
1- Can not be used in neutral or basic
medium . 2- Time consuming .
Example:- The %w/w I- in a 0.6712gram sample was determined by a
Volhard titration. After adding 50 mL of 0.05619 M AgNO3 and allowing the
precipitate to form, the remaining silver was back titrated with 0.05322 M
KSCN, requiring 35.14 mL to reach the end point. Report the %w/w I-( mw
=
126.9 ) in the sample ?

Answer:
 Application

 Sodium chloride:-

• determination of the percentage of NaCl.

 Chlorbutol:-

• In the determination of the % of chlorbutol. Organically

combined chloride is converted by hydrolysis with NaOH to ionic
chloride w/c can be determine by volhards method in the presence of
nitrobenzene.

CCl3.C(CH3)2 .OH + 3NaOH → C(OH3)2 .C(CH3)2 .OH + 3NaCl

3NaCl + 3AgNO3 → 3NaNO3 + 3AgCl

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Reading assignment
1. Fajans Method
2. Mercuremetric method