ARGENTOMETRIC/ PRECIPITATION TITRATIONS

Q.1. What are precipitation Titrations?

Ans. Those chemical reactions that involves the formation of precipitates or sparingly soluble
salt are known as precipitation Titrations. These reactions are not numerous as compared to
acid base or oxidation-reduction reactions. These are limited to those involving the
precipitation of silver ions with anions like Halogens or thiocyanate (SCN-), because there is
lack of suitable indicators to detect end point and due to slow rate of reaction. The
composition of precipitate is not exactly known due to co-precipitation.

Q.2. Explain the theory involved in precipitation Reactions/Titrations.

Ans. Consider 50 ml of 0.1 M NaCl solution, titrated with 0.1 M AgNO3 solution.
Calculate Cl- conc. At intervals during titration and plot pCl vs ml of AgNO3.

p Cl- = - log [Cl-] Ksp for AgCl = 1x10 -10

i) At the start of titration:

[Cl-] = 0.1 mmol/ml = 10 -1

 - log [Cl-] = p Cl- = - log10 -1 = - (-1)
 p Cl- = 1.
ii) After the addition of 10ml of 0.1 M AgNO3 solution.
We have started with 50 ml x 0.1 mmol/ml = 5mmol of Cl-
& we have added 10 ml x 0.1 mmol/ml = 1 mmol of Ag+
Reaction takes place is as follows:
Ag+ + Cl- AgCl
(Solid)
-
Cl left in the solution = 40 ml of 0.1 M
Total volume of the solution becomes 50 ml + 10 ml = 60 ml.
 [Cl-] can be calculated by applying
N1V1 = N2V2
40 x 0.1 = 60 x [Cl-]
40 𝑋 0.1 4
 [Cl-] = = = 0.067 𝑀
60 𝑋 10 60
 p Cl- = - log [Cl-]
= - log [0.067] = 1.17
iii) After the addition of 49.9 ml of 0.1 M AgNO3 solution.
We have started with 50 ml x 0.1 mmol/ml = 5mmol of Cl-
& we have added 49.9 ml x 0.1 mmol/ml = 4.99 mmol of Ag+
Reaction takes place is as follows:
Ag+ + Cl- AgCl
(Solid)

0.1 M Cl- left in the solution = 0.1 ml

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 Total volume of the solution becomes 50 ml + 49.9 ml = 99.9 ml ≈ 100 ml.
 [Cl-] can be calculated by applying
N1V1 = N2V2
0.1 x 0.1 = 100 x [Cl-]
0.1 𝑋 0.1
 [Cl-] = = 10−4 𝑀
100
 p Cl- = - log [Cl-]
= 4.00
iv) At Equivalence point
At starting 50 ml x 0.1 mmol/ml = 5mmol of Cl-
Added 50 ml x 0.1 mmol/ml Ag = 5mmol of Ag+
 neither there is excess of Cl- nor Ag+ ions & concentration of each is given by square
root of Ksp AgCl
AgCl (Solid) Ag+ + Cl-
[Ag+] + [Cl-] = Ksp
[Ag+] = [Cl-]
[Cl-]2 = 1 x 10−10
OR [Cl-] = 1 x 10−5 OR pCl- = 5.00
v) After the addition of 60 ml of AgNO3
Started with 50 ml x 0.1 mmol/ml = 5mmol of Cl-
Added 60 ml x 0.1 mmol/ml Ag = 6 mmol of Ag+

Total volume = 50 + 60 = 110 ml

i.e. now we have excess of Ag+ in the solution = 10 ml of 0.1 M Ag

 [Ag+] can be calculated from N1V1 = N2V2

10 x 0.1 = 110 x [Ag+]
10 𝑋 0.1
[Ag+] = = 9.1 𝑋 10−3
110

pAg = 2.04

Since pAg + pCl = 10

 pCl = 7.96

Increase in pX (X = Cl, Br or I) at equivalence point is greatest for titration of iodide.

Because silver iodide is least soluble of these salts.

Value of K for titration reaction

Ag+ + 𝑋 − AgX (S)

1 1
𝐾= =
[𝐴𝑔+ ][𝑋 − ] 𝐾𝑠𝑝

Smaller the Ksp larger is the K value for the titration reaction.

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 KAgCl = 1 x 1010 , KAgBr = 2 x 1012 , KAgI = 1 x 1016

Q.3. Write a note on solubility product.

Ans. For sparingly soluble salts (for which the solubility is less than 0.01 mol/ml) it is a
fact that the product of total molecular concentration of ions is a constant at constant
temperature. This product is known as Ks, the solubility product.

Eg. AB A+ + B-

Ks (AB) = [A+] + [B-]

In general for an electrolyte Ap Bq, which ionises into pAq+ & qBp- ions.

ApBq pAq+ + qBp-

Ks (ApBq) = [Aq+]p [Bp-]q

When excess of a sparingly soluble electrolyte for eg: AgCl is shaken with water, some of
it passes into solution to form a saturated solution of salt & reaction seems to cease.
Following equilibrium is actually present:

AgCl (S) Ag + + Cl –

Velocity of forward reaction depends only upon temperature & at any given temperature

V1 = K1 K1 is a constant.

At any given temperature, velocity of reverse reaction is directly proportional to activity of

each of the reactants.

 V2 = K2 x aAg+ x aCl- K2 is another constant

At equilibrium the two velocities are equal. V1 = V2

𝐾1
K1= K2 x aAg+ x aCl- or aAg+ x aCl- = = Ks (AgCl)
𝐾2

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 In very dilute solutions with which we are concerned, activities may be taken as
practically equal to concentrations.

 [𝐴𝑔+ ] [𝐶𝑙 − ] = constant

Solubility product relation applies only to saturated solutions of slightly soluble

electrolytes & with small addition of other salts.

In presence of moderate concentration of salts, ionic concentration & therefore ionic

strength of solution will increase. Therefore, it will lower the activity coefficient of both
ions & hence ionic concentration must be high to maintain solubility product constant.

Q.4. Solubility of Silver chloride is 0.0015 g/l. Calculate its solubility product.

Ans. Molecular weight of AgCl is 143.5,

0.0015
 Solubility of AgCl in mol/l = = 1.05 𝑋 10−5 mol/l
143

In a saturated solution, 1 mole of AgCl will give 1 mole of 𝐴𝑔+ & one mole of 𝐶𝑙 − .

 [𝐴𝑔+ ] = 1.05 𝑥 10−5 𝑚𝑜𝑙/𝑙

& [𝐶𝑙 − ] = 1.05 𝑥 10−5 𝑚𝑜𝑙/𝑙

Ks (AgCl) = [𝐴𝑔+ ] [𝐶𝑙 − ] = (1.05 𝑥 10−5 ) (1.05 𝑥 10−5 )

= 1.1 x 10−10 mol2/l2

Q.5. Describe the effect of acids on solubility of precipitates.

Ans. Let us suppose that HCl is added to aqueous suspension of such a salt.

Let MA is the salt of weak acid HA. Following equilibrium exists:

𝑀+ + 𝐴− + 𝐻 + ←→ 𝐻𝐴 + 𝑀+

If the dissociation constant of acid HA is very small, anion 𝐴− will be removed from the
solution to form un-dissociated acid HA. Therefore, more of salt will pass into solution to
replace anions removed in this way. & the process continues until equilibrium is reached
i.e. until [𝑀+ ] [𝐴− ]= K sp (MA) or if sufficient acid is present, until sparingly soluble salt has
dissolved completely. Eg. Solubility of Silver orthophosphate in dilute HNO3, is due to
removal of 𝑃𝑂43− as 𝐻𝑃𝑂42− & OR 𝐻2 𝑃𝑂43− .

𝑃𝑂43− + 𝐻 + 𝐻𝑃𝑂42−

𝐻𝑃𝑂42− + 𝐻 + 𝐻2 𝑃𝑂43−

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 Q.6. Write the effect of Temperature on solubility of precipitates.

Ans. Solubility of precipitates encountered in quantitative analysis increases in varying

degrees with rise in temperature with some substances influence of temperature is small
compared to others.

For eg. Solubility of AgCl at 10°C = 1.72 BaSO4 at 10°C = 2.2

Solubility of AgCl at 100°C = 21.1 BaSO4 at 100°C = 3.9

Also, common ion effect reduces the solubility to such an extent that the temperature
effect which is otherwise appreciable becomes very small.

For eg. If an excess of Ag+ is added to a saturated solution of AgCl in water, the solubility
product [Ag+] [𝐶𝑙 − ] is exceeded & some of AgCl will be precipitated & equilibrium is
reached when product of Ag+ & 𝐶𝑙 − ion concentration is equivalent to solubility product.

Similarly, if 𝐶𝑙 − solution is added in excess to AgCl solution same effect will be seen.
Therefore, wherever possible it is advantageous to filter while solution is still hot. The rate
of filtration is increased. However, Magnesium Ammonium Phosphate & silver chloride
are usually filtered at room temperature to avoid appreciable solubility losses. Solution is
cooled to ice before filtration. Lead Chloride (PbCl2) is separated from Ag & HgCl2 in
analysis by treatment with hot water. Lead salt dissolves at elevated temperature and
leaves other two salts in precipitates.

Q.7. What is the role of solvent on solubility of precipitates.

Ans. Generally, inorganic salts have high solubility in water than in organic solvents.
Water has a large dipole moment (property of liquids) & is attracted to both cation &
anion from hydrated ion. The Hydrogen in water is completely hydrated i.e. H3O+.

In water solutions, all ions are to some extent hydrated & energy released by interaction of
ions & solvent helps to overcome the attractive forces to hold the ion in the solid lattice.

Ions in a crystal do not have so large attraction for organic solvents & hence solubility are
less than in water. The concept of low solubility in organic solvents can be utilized to
separate two substances which are quite soluble in water.

For eg. Dried nitrate mixture of Ca ++ & Strontium are separated by treatment with
mixture of alcohol & ether. CaNO3 dissolves & strontium nitrate do not.

Another eg. Potassium can be separated from Sodium by precipitating K2PtCl6 from an
alcohol- water mixture solvent. Solubility of most of the inorganic compounds is
decreased by addition of organic solvents like methanol, ethanol, propanol, acetone, etc.

Another eg: Addition of about 20 % by volume of ethanol renders the solubility of PbSO4
almost negligible. Therefore, making quantitative separation is possible.

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 Q.8. Explain the end point detection in precipitation titration by Mohr’s Method.

Ans. In this method the end point detection is marked with formation of colored
precipitates. It is used for determination of 𝐶𝑙 − & 𝐵𝑟 − . In the titration of for example 𝐶𝑙 −
with AgNO3 solution, a small quantity of K2CrO4 (potassium chromate) is added as
+
indicator. At end point chromate ions combine with Ag to form brick red colored
Ag2CrO4 precipitates.

𝐶𝑙 − + AgNO3 AgCl (Before the equivalence point)

Ag+ + K2CrO4 Ag2CrO4 (After the equivalence point)

Brick red ppt.
Explanation:

In the titration, we have two sparingly soluble salts that are produced.
One is AgCl with solubility (Ksol = 1.2 𝑋 10−10 ) & other one Ag2CrO4 with solubility
(Ksol = 1.7 𝑋 10−12 ) .
In titration of 0.1M NaCl with 0.1M AgNO3 in presence of few ml of K2CrO4 solution,
AgCl, a low solubility salt is produced. Since initially concentration of chloride (𝐶𝑙 − )
solution is high, therefore AgCl is precipitated first. At the first point where red
Ag2CrO4 is just precipitated both the salts (i.e. AgCl & Ag2CrO4 )will be in
equilibrium with the solution.

Therefore, [Ag+] [𝐶𝑙 − ] = (Ksol(AgCl) = 1.2 𝑋 10−10

& [Ag+]2 [𝐶𝑟𝑂42− ] = Ksol (Ag2CrO4) = 1.7 𝑋 10−12 .
𝐾𝑠𝑜𝑙(𝐴𝑔𝐶𝑙) K sol (Ag2CrO4)
[Ag+] = =√
[𝐶𝑙−] [𝐶𝑟𝑂42− ]
[𝐶𝑙− ] 𝐾𝑠𝑜𝑙(𝐴𝑔𝐶𝑙) 1.2 𝑋 10−10
= = √1.7 = 9.2 𝑋 10−5 .
√𝐶𝑟𝑂42− √K sol (Ag2CrO4) 𝑋 10−12

Now, at equilibrium or equivalent point

[𝐶𝑙 − ] = √𝐾𝑠𝑜𝑙.𝐴𝑔𝐶𝑙 = 1.1 x 10−5

So if Ag2CrO4 is to be precipitated at above 𝐶𝑙 − concentration
[𝐶𝑙− ] 1.1𝑥 10−5
[𝐶𝑟𝑂42− ] = (9.2𝑥10−5 )2 = ( 9.2𝑥10−5 ) = 1.4 x 10−2 OR 0.014M

Therefore, Concentration of K2CrO4 should be 0.014M. Generally for practical purposes

more dilute solutions of K2CrO4 (0.003-0.005 M) is used. Because chromate solution of
0.01-0.02M concentration will give deep orange color to solution & it will be very
difficult to detect first appearance of Ag2CrO4. Titration error can be minimized by
performing a blank titration by measuring volume of standard AgNO3 solution required to
give the precipitable clor when added to distilled water containing same quantity of
indicator. This volume is subtracted from volume of standard solution used. This method
is not successful with iodide or thiocyanate because AgI or AgSCN adsorb chromate ions
so strongly that a false & indistinct end point is obtained.
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 Q.9. Discuss the principle used in titration of volhard’s method.
Ans. In this method there is formation of soluble colored compound. Here titration of
Ag+ in presence of free HNO3 (0.5-1.5M) with standard potassium (K) or NH4SCN
solution is done. Indicator used is a solution of Iron (III) nitrate or Iron (III) Ammonium
sulphate solution.
To Ag+ solution 𝑆𝐶𝑁 − (Thiocyanate) solution is added.
Ag+ + 𝑆𝐶𝑁 − AgSCN Ksol = 7.1 𝑥 10−13
First AgSCN precipitates. When above reaction is complete, slight excess of 𝑆𝐶𝑁 −
produces a reddish brown coloration due to formation of complex ion.

𝐹𝑒 3+ + 𝑆𝐶𝑁 − ←→ [𝐹𝑒𝑆𝐶𝑁 2+ ]
Reddish brown color
This method is used for determination of 𝐶𝑙 − , 𝐵𝑟 − , 𝐼 − in acid solution.
Method:
Excess of AgNO3 solution is added and excess is back titrated with standard thiocyanate
solution. Two equilibriums exists during the titration of excess of Ag+.
One is 𝐶𝑙 − + Ag+ AgCl
+ −
Other is Ag + 𝑆𝐶𝑁 AgSCN

[𝐶𝑙− ] 𝐾𝑠𝑜𝑙 (𝐴𝑔𝐶𝑙 ) 1.2 𝑥 10−10

∴ = = 7.1 𝑥 10−13 = 169
[𝑆𝐶𝑁 − ] 𝐾𝑠𝑜𝑙 (𝐴𝑔𝑆𝐶𝑁)

Q.10. What problem is encountered in Volhards method and how to overcome it.
A. When excess of Silver has reacted, then SCN may react with AgCl because AgSCN is
less soluble salt.
i.e. AgCl + 𝑆𝐶𝑁 − AgSCN + 𝐶𝑙 −
The above reaction takes place before the reaction occurs with iron (III) ions in the
solution & there is titration error.
Titration error with 𝐶𝑙 − is highest. For 𝐵𝑟 − is lower, & for 𝐼 − is still more lower, because
of solubility of 𝐵𝑟 − & 𝐼 − .

[𝐵𝑟 − ] 3.5 𝑥 10−13

= = 7.1 𝑥 10−13 = 0.5
[𝑆𝐶𝑁 − ]

It is important to prevent the reaction of 𝑆𝐶𝑁 − solution with AgCl.

Methods to prevent the above problem:
1. By filtering off AgCl; produced before back titrating the remaining unreacted Ag+
against 𝑆𝐶𝑁 − solution. But at this stage precipitates of AgCl will be contaminated with
adsorbed Ag+. Therefore, the suspension of AgCl is boiled for few minutes. This boiling
results in coagulation of AgCl & this removes the adsorbed ions of Ag+ before filtration.
Then the cooled filtrate is titrated.
2. By use of coagulant: After the addition of AgNO3 to halide solution, KNO3 is added
as coagulant & then suspension is boiled for 3 minutes. Then cooled & titrated

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 immediately. This results in desorption of Ag+ that are adsorbed & on cooling re-
adsorption is prevented by presence of KNO3.
3. Use of Immiscible liquid:
An immiscible liquid is added to coat AgCl particles & thereby protect them from
interaction with 𝑆𝐶𝑁 − solution. Eg. Liquid like nitrobenzene (1 ml for each 50 mg of 𝐶𝑙 − )
is added to suspension & is shaken well to coagulate precipitate before back titration.
Q.10. Describe the principle involved in titration by Fajans Method.
Ans. Adsorption of colored organic compounds on the surface of a precipitate may induce
electronic shift in molecule that alters its color. This phenomenon is used to detect the end
point of precipitation titration of Ag+ salts. The mechanism was shown by K. Fajan’s.
Organic compounds are used as adsorption indicators.
In titration of 𝐶𝑙 − with Ag+ before equivalence point colloidal particles of AgCl are
negatively charged because of adsorption of 𝐶𝑙 − ions from solution.

Before the equivalence point adsorbed 𝐶𝑙 − forms primary layer which makes colloidal
particles to be negatively charged. These attract positively charged ions from the solution
to form a more loosely held secondary layer. After the equivalence point excess of Ag+
ions (positively charged) displace negatively charged 𝐶𝑙 − ions from primary layer &
particles become positively charged. Anions in the solution are attracted to form the
secondary layer.
 A precipitate tends to adsorb most readily those ions that form an insoluble compound
with one of the ions in the lattice. Therefore, Ag+ ions or 𝐶𝑙 − will be more readily
absorbed by AgCl precipitate than say 𝑁𝑂3− or Na+ ions.
 Fluorescein which is a weak organic acid represented by HFl when added to flask, the
anions 𝐹𝑙 − is not adsorbed by colloidal AgCl as long as 𝐶𝑙 − ions are in excess.
But once the Ag+ are in excess, 𝐹𝑙 − ions are attracted to surface of positively charged ions
particles.

i.e. Ag+ 𝐹𝑙 −
AgCl
(PINK in color)
−
Ag+ 𝐹𝑙

The resulting aggregate is pink in color & color change is so intense that it serves as
visual indicator.

Q.11. What are the conditions that govern the choice of suitable adsorption indicator.
Ans. Following are the conditions that govern the choice of suitable adsorption indicator:

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 1. The precipitate should separate in colloidal condition. Large quantities of neutral salts,
multivalent ions are avoided due to their coagulating effect. Solution should not be too
dilute because amount of precipitate formed will be small & color change is not sharp.
2. Ions of indicator must be of opposite charge to the ion of precipitating agent.
3. Indicator ion should be strongly adsorbed immediately after the equivalence point.
But not too strongly adsorbed by precipitate.
Eg. Eosin (Tetrabromo fluorescien) added to 𝐶𝑙 − --- Ag+ titration. The adsorption of
indicator ion may be a primary process & takes place before equivalence point is reached.

Fluorescein can be used in pH range of 7 to 10.

Dichloro Fluorescein can be used in pH range of 4 to 10.

Disadvantage:
a) AgX (silver halide) are sensitive to action of light by a layer of adsorbed dyestuff
(indicator). Therefore, titration should be carried out with a minimum exposure to
sunlight.
b) Only 2 x 10 - 4 to 3 x 10 – 3ml of dye/ mol of AgX is added.
c) Preparation of Fluorescein indicator: Dissolve 0.2 g fluorescein in 100 ml of 70% ethanol.
Or Sodium fluoresceinate in 100 ml of Water.

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