Dr.

Puspendra Kumar

PRECIPITATION TITRATION

PRECIPITATION REACTION
• Precipitation is the formation of a solid in a solution and solid formed is called the
precipitate.
• A precipitation reaction occurs when water solutions of two different ionic compounds
are mixed and an insoluble solid separates out of solution.
Eg:- KCl + AgNO3
 AgCl↓ + KNO3
(Cl- solution) (Precipitating agent) (Precipitate)

• The precipitation is itself ionic, the cation comes from one solution and anion from
another.
• Precipitation of ionic products forces the reaction to completion.
• The requirement for a reaction to be useful in titrimetric analysis are:
1. The precipitate must be practically insoluble
2. The precipitation reaction should be rapid and quantitative.
3. The titration result should not be hampered by adsorption (co-precipitation) effects.
4. It must be possible to detect the equivalence point during titration.
Other example
NaCl + AgNO3
 AgCl↓ + NaNO3

AgNO3

NaCl (aqueous solution)

AgCl (Precipitate)

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Solubility Products
• The solvent should compare with crystal forces and overcome them, which often means
that the solvent environment must be similar to that provided by the crystal structures.
• This is the basis for the simple rule “like dissolves like”, means solute-solute attraction
is overcome by solute-solvent attraction.
• During precipitation reaction, however, the opposite condition is aspired for, where the
intermolecular forces between molecules of product are high and solute-solute forcs
replace the solute-solvent forces.

• Consider an aqueous solution of a slightly soluble salt “BA” in equilibrium with excess
of solid at constant temperature.

BA(s)
 B+ + A-
Where; BA(s) represents the solid phase.

In dilute aq. Solution essentially no un-dissociated BA will be present in the solution.

Since activity of solid is constant, the equilibrium constant for eq. (1) may be written as

Ksp = [B+] [A-] -------------------------- (1)

Ksp = Solubility product (which is constant)
Solubility product is of important as it permits the calculation of one of the ion concentration if
the other is known.
A substance precipitates out when the product of the ionic conc. exceeds the Ksp value.

In the equation (1) solid BA will precipitates out, when the product of [A+] exceeds Ksp
i.e. Ksp < [B+][A-]

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EFFECT ON SOLUBILITY OF PRECIPITATE

(i) Effects of Acids
• the solubility of a salt will be increased by decrease in pH (or increasing acidity)
if the anion of the salt is the conjugate of weak acid.
Eg:- Consider the slightly soluble salt BA, the anion of which [A-] is the conjugate base
of a weak acid HA
Here, there will be two equilibrium in operation
BA (s)
 B+ + A- ------------------------- (1)
HA
 H+ + A- ------------------------- (2)

The [A-] from eq. (1) will shift the equilibrium (2) towards left
While, eq (1) will itself be shifted to right
Hence, solubility of BA is increased with increase in H+ (or decrease in pH)
The equilibrium expression are
Ksp = [B+] [A-] ------------------ (3)

Ka = [H+] [A-] / [HA] ------------------ (4)

Molar solubility of BA is equal to [B+] which is equal to the total conc. Of [A-]
i.e. the [A-] dissolved from BA and that which is present in HA.
s = [B+] = [A-] + [HA] ------------------- (5)
From equation 3, 4 and 5
s = [B+] = Ksp x (1+ [H+]/ Ka)
[B+]

s = √Ksp (1 + [H+]/ Ka) ------------------- (6)

Equation (6) relates molar solubility (s) to Ksp, Ka and [H+] ion concentration.

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(ii) Effect of temperature

• The solubility of the precipitation encountered in qualitative analysis increases with the
rise in temperature
• With some substances the influence of temperature is small, but with ethers it is quite
appreciate

Eq:- Solubility of AgCl at 100C is 1.72 mg/L and

1000C 21.1 mg/L
Solubility of BaSO4 at 100C is 2.2 mg/L and
1000C 3.9 mg/L

(iii) Effect of solvent

• The solubility of most inorganic compounds is reduced by the addition of organic
solvents such as methyl, ethyl and n-propyl alcohols

Eg:- The addition of about 20% by volume of ethanol shows the solubility of lead
sulphate (PbSO4) practically negligible. Thus permitting quantitative separation.

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ARGENTOMETRIC TITRATIONS
-Titration methods based upon utilizing AgNO3 (silver nitrate) as a precipitating agent.
-Silver ions is extremely useful in precipitation reactions including
• Halides (Cl-, Br- , I-)
• Pseudohalides (S2-, HS-, CN-, SCN-)
Requirements:-
1. The precipitate formation is stoichiometric.
2. Equilibrium should be attained rapidly.
3. The precipitate must be of low solubility in the solution.
4. Method to detect the stoichiometric point of the titration must be available.
Titration cause for argentometric methods.

• Plots of titration curves are normally sigmoidal curves consisting of pAg (or pCl) vs
volume of AgNO3 solution added.
• The titration curve is normally broken down in three regions for calculation and a
function for pAg determination-
(1) Pre equivalence region
(2) Equivalence point
(3) Post equivalence region

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Eg: calculated the [Ag+][Cl-] and pAg in a titration of 20.0 ml of 0.1M AgNO3 with
0.1M NaCl.
Titrant added PAg
0.0 1.0 (pre equivalence region)
10.00 1.48 (pre equivalence region)
20.00 4.87 (equivalence region)
25.00 7.79 (post equivalence region)

0 ml titration added (NaCl)

At the start of the titration [Ag+] = 0.1M; pAg = -log [Ag+]
=-log 0.1= 1
+
10 ml titrant added (NaCl); Ag started= 20 x 0.1M = 2.0 mol
Cl- added= 10 x 0.1= 1.0 mol; So, Mol Ag+ left= 2.0-1.0= 1.0 mol
Volume of solution = 20+10 =30 ml
Ag+ = 1mol / 30mol = 0.0333; pAg = -log 0.0333 = 1.48

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At equivalence point, titrant (NaCl) added= 20 ml

Mol of Ag+ started = 20 x 0.1M = 2.0ml
Mol of Cl- added= 20 x 0.1M= 2.0 mol
So, [Ag+] = [Cl-]= S and
Ksp= [Ag+] [Cl-] = S2 = 1.8 x 10-10 M2
So S2= 1.8 x 10-10M2,
S= √(1.8 x 10-10)
S = 1.34 x 10-5
pAg= pCl= -log 1.34 x 10-5
= 4.87
After addition of 25 ml of titrant (NaCl)
pAg= 7.79
So, high reagent conc. Give sharper, end point
Indicators for argentometric titrations are skeletal to produce a color change at or near the
equivalence point
End point can be determined by Mohr’s volhor’s or Fajan’s method.

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TITRATION INVOLVING AMMONIA AND POTASSIUM THIOCYANATE

THIOCYANATOMETRY
• In this type of titration SCN- is the titrant
• Titrant:- Ammonia or potassium thiocynate
• Both are secondary standard
• So both requires standardization by primary standard ( AgNO3)
AgNO3 + NH4SCN  AgSCN + NH4NO3
AgNO3+ KSCN  AgSCN+ KNO3
• Indicator:- Iron III salts is used as indicator in this type of titration
Fe3+ + SCN-  [Fe (SCN)]2+
Example:
NH4Fe(SO4).12H2O (Iron salt or Ammonium Iron III sulphate)
Medium of titration :- In presence of Nitric acid
Analyte (Determinate substances) titrand which contains silver:-
Eg:- Colloid silver (Kollargol)
Silver nitrate
Advantages:- in very acidic solution

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MERCUROMETRY
This is a precipitation reaction (titration) which Hg22+ is the titrant.
2 Cl- + Hg22+  Hg2 Cl2↓
2 I- + Hg22+  Hg2I2 ↓
Titrant:- Hg2(NO3)2 secondary standard.
So, it requires standardization by using primary standard solution (NaCl)
Hg2 (NO3)2 + NaCl  Hg2Cl2 + NaNO3
Indicators
(1) Solution of Iron (III) thiocyanate it shows from reddish color to colorless at the end
point.
2Fe(SCN)2+ + Hg22+  Hg2(SCN)2↓ + 2Fe3+
(2) 1-2% spirit diphenylcarbazone it shows blue colur at the end point.
Analyte (determinate substances)/ titrand
Eg:- Chlorides, Iodides
Medium: Very acidic
Advantages: Titration is very acidic medium
Titration is cheap
Disadvantage: Mercury (I) salts are very toxic.

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GAY LUSSAC'S METHOD

• The fact that occurrence of turbidity accompanies precipitation reaction is made use of in
this method.
• After the equivalence the precipitation reaction cease and extra drop will not result in
turbidity.
• The procedure may be exemplified by the titration of AgNO3 with standard sodium
chloride (NaCl) in the presence of free nitric acid and a small quantity of pure barium
nitrate (to assist the progress of coagulation).

• Weight out accurately 0.4g of AgNO3 in a well stopped bottle.

• Add about 100ml of water, a few drops of conc. HNO3 and a small crystal of barium
nitrate [Ba(NO3)2]

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• Titrate with standard 0.1M NaCl by adding 20ml at once, stoppering the bottle, and
shaking vigorously until the precipitation of AgCl (Silver chloride) has coagulated and
settled. (The process added by the barium nitrate )
• Upper layer is clear.
• Still the silver ions are in excess, so continue to add NaCl solution, 1ml at a time,
stoppering and shaking after each addition till no turbidity is produced.
• Note the volume of NaCl consumed; consider it’s as pilot reading.
• Repeat the titration, adding 1ml less than the pilot reading initially and continue adding
0.02ml after that.
• The end point can be determined within a drop.

MOHR'S METHOD
• The falls under the category of determining the end point by formation of colored
precipitate and is used, for the determination of chlorides and bromides is a neutral
solution.

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• Titrant:- AgNO3 (Secondary standard solution ) so AgNO3 is standardized by primary

standard solution of NaCl ( measured volume ).
• AgNO3 + NaCl  AgCl + NaNO3
• Indicator:- 5% Potassium chromate (K2CrO4) which forms reddish brown precipitate.
2AgNO3 + K2CrO4  Ag2CrO4 + 2KNO3
• Determination substance:- Chloride , Bromide.
• Medium:- pH range 6.5 - 10.3
• Usage: Quantitative definition of NaCl , KCl , NaBr , KBr etc.
• Let us consider the titration of 0.1M NaCl with 0.1M AgNO3 in the presence of few ml of
dilute K2CrO4 solution as indicator.
• As AgNO3 is added AgCl will precipitate first.
• We usually expect the salt with smaller solubility product to precipitate first, but this true
only if both salts dissociate to yield the same number of ions.
• Also chloride ions in this case are in great excess of that of chromate ions.
Ksp AgCl = 1.8 x 10-10
As the equivalence point is reached, no Ag+ or Cl- is in excess.
• But , now additional drop of AgNO3 will react with CrO42- to precipitate as
Ksp Ag2CrO4 = 1.2 x 10-12
Restriction of usage of Mohr's Method
• It’s impossible to use titration in acidic solution otherwise it will produce silver
hydroxide.
• It’s impossible to use titration in the presence of ammonia ions (Due to ligand formation).
• It is impossible to use titration in the presence of reduces which reducers which reduce
chromate ions CrO42- to Cr3+ ions.
• It's impossible to use titration in the presence of many anions (PO43-, S2- etc) which gives
the painted precipitate of silver ions.

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 Dr. Puspendra Kumar

VOLHARD METHOD
In this method formation of a solute color compound at the end point.
Silver ion is titrated with thiocynate in as acid solution using ferric ion as an indicator.
Titrant: AgNO3 (Silver Nitrate)
NH4SCN (Ammonium thiocyanide)
KSCN (Potassium thiocyanide)
AgNO3 is standardized by NaCl (Primary standard solution).
NH4SCN and KSCN is standardized on standardize solution of AgNO3
AgNO3 + NH4SCN  AgSCN + NH4NO3
AgNO3 + KSCN  AgSCN + KNO3

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 Dr. Puspendra Kumar

Indicator:
Iron (III) salt is used as indicator in presence of nitric acid to from the reddish colored
complex
[Fe (SCN]2+
i.e NH4 Fe(SO4)2.12H2O
Ammonium ion (III) sulphate or ferric ammonium sulphate or iron Alum.
Fe3+ + SCN-  [Fe (SCN)]2+
Medium:- In presence of nitric acid .
Determinate Substance: Halogenides, Thiocyanide, Cyanides, Sulphides, Carbonates,
Chromate, Oxalates, Arsenates etc.
• The titration is done in acidic pH medium to present precipitation of iron hydroxides,
Fe(OH)3

FAJAN'S METHOD
• K.Fajan, through his studies on nature of adsorption, introduced a useful type of indicator
for precipitation titration.
• Such indicators are adsorbed on the surface of the precipitation at the equivalence point
and this absorption is accompanied by a color change.
• These indicator are either
• Acid dyes; eg:- Fluorescein, Eosin etc. or
• Basic dyes: eg:- Rhodamine series.
• Titrant:- AgNO3 (Secondary standard solution) so standardized on primary standard
solution of NaCl (by a measured volume).
• Medium: pH :- 6.5-10.3 (For chloride)
pH :- 2.0-10.3 (For Bromides & Iodides)
• Indicators: Dichlorofluoroscein (for Chlorides)
Eosine (For Bromides & Iodides)

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Mechanism of Indicator action:-

• The property of a colloidal precipitate to adsorb its own ions which are in excess, is made
use of in the case.
• When a NaCl solution is titrated with AgNO3 the AgCl precipitate will adsorb chloride
ions which are initially in excess.
• This the primary adsorbed layer will be formed by chloride ions, which in taken will hold
the secondary adsorbed layer of oppositely charged Na+

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Pink Color
• At the equivalence point, Ag+ ions in excess and hence AgCl ions adsorb Ag+ ions
as primary adsorb later and NO3- as secondary adsorb layer.
• Now, If the Na+ salt of Fluorescein is also present in the solution then the
negatively charged fluorescein ions would be adsorbed instead of NO3- as
secondary adsorbed layers and this adsorption occurs alongwith a change to pink
colored complex of Ag+ and fluorescein ions.

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