ANALYTICAL CHEMISTRY

PHARMACY PROGRAM
Second Year–Semester II

Dr. MOHAMED BABIKER

mohamedbabiiker@gmail.com
0910040080

Understanding, rather than mindless memorization, is the key to learning analytical chemistry
 Classification of Quantitative Analysis

Quantitative
analysis

Volumetri Gravimetric
c

Acid base Oxidation

Complexometric
Precipitation
titration Titration
reduction

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 Precipitation titration

Precipitation Titration:
• Type of volumetric analysis that depends on the
formation of a precipitate.
• Precipitating agent used in precipitation titration is
Silver Nitrate (Argentometric titration).

Application:
• Used for determination of halides (CI–, Br– and I–)
• Used for determination of thiocyanide and cyanide.
• Some compounds that form insoluble product with
silver nitrate.

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Requirements:
• The precipitate must be practically insoluble.
• The precipitate should be rapid.
• The reaction should go rapidly to completion and
should be quantitatively.
• Only one reaction should take place.
• The titration results should not be hampered by
adsorption (Co-precipitate) effects.
• The compounds must be ionic in nature.
• There should be no change or any harm in detecting
the end point.

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End point detection in precipitation titration:
1. Mohr's method: Formation of colored precipitate.

2. Volhard's method: Formation of colored

complex.

3. Fajan method: Formation of colored adsorption

compound.

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1. Mohr's Method (1856)
• Sample: CI–, Br– (Not for I– or SCN–).
• Type of titration: Direct titration.
• Standard Solution: Standard silver nitrate solution
(AgNO3).
• pH: Neutral or slightly alkaline (pH ~ 6.5−9).
• Indicator: I mL of 5% potassium chromate (K2CrO4)
solution.
• Color at end point: Brick red precipitate due to
formation of Silver chromate (Ag2CrO4).

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• Titration reaction:
CI– + Ag+ AgCI Ksp =1.8xl0-l0
sample titrant white ppt

• Endpoint reaction
2 Ag + + CrO4-2 Ag2CrO4 Ksp = 1.2 x l0-l2
titrant indicator brick red ppt

• Relies on Ksp differences for two insoluble silver salts.

• Ag2CrO4 (red) precipitated (ppt) in neutral pH solution, colour
forms just after AgCl formation.
• Chromate forms a ppt with Ag+ of larger solubility than of AgCl.
• Thus AgCl is formed first and after all Cl– is consumed, the
first drop of Ag+ will react with the chromate indicator giving a
reddish ppt.
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Limitations of Mohr's Method
1. Effect of pH: Mohr's method should be done in neutral
or slightly alkaline medium (pH ~ 6.5-9) because:
• At pH > 9: Ag+ will be precipitated as AgOH (brown to
black ppt): leading to consumption of the titrant and
masking of the end point color.
Ag+ + OH – AgOH (brown toblack ppt)

• While at pH < 6.5: Chromate ion (CrO4-2) changes into

acid chromate (HCrO4-1) then to dichromate (Cr2O7-2).
• Both HCrO4-1 and Cr2O7-2 form soluble salts with Ag+
and so no colored ppt will be formed at the end point.
2CrO4-2 + 2H+ 2 HCrO4-1 Cr2O7-2 + H2O

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2. Ag2CrO4 is more soluble than AgCl so that no
Ag2CrO4 will be precipitated until all CI– ions have
been precipitated as AgCl provided that CrO4-2
concentration should be adjusted to make Ag2CrO4
formed only at the end point and so to prevent error
in the end point, 1 ml of 5% K2CrO4 solution is
suitable based on solubility product.
• High concentration of K2CrO4 gives too soon (early)
end point.
• Low concentration K2CrO4 gives too late end point
because CrO4-2 will be insufficient and so a large
amount of Ag + (titrant) will be needed to precipitate
Ag2CrO4 and so the end point comes too late.
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3. I– and SCN– cannot be determined by Mohr's
method because the formed silver chloride and
silver thiocyanate strongly adsorb CrO4-2 on their
surfaces and so the precipitation formed at the
end point will be an adsorption compound which
is less colored and so less sharp endpoint will be
obtained.

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Sodium chloride estimation
Equipments:
 Burette and stand
 10 and 20 mL pipettes
 100 mL volumetric flask
 250 mL conical flasks
 I0 mL and 100 mL measuring cylinders.
Solutions needed:
 Silver nitrate solution: (0.1 mol L–I) If possible, dry 5 g of
AgNO3 for 2 hours at l00 oC and allow to cool. Accurately
weigh about 4.25 g of solid AgNO3 and dissolve it in 250
mL of distilled water in a conical flask. Store the solution in
a brown bottle.
 Potassium chromate indicator solution: (about 0.25 molL–I)
Dissolve 1 g of K2CrO4 in 20 mL distilled water.
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Titration:
1. Dilute seawater by pipetting a 20 mL sample into a
100 mL volumetric flask and making it up to the mark
with distilled water.
2. Pipette a 10 mL aliquot of diluted seawater into a
conical flask and add about 50 mL distilled water and
1 mL of chromate indicator.
3. Titrate the sample with 0.1 mol L–I silver nitrate
solution. Although the silver chloride that forms is a
white precipitate, the chromate indicator initially
gives the cloudy solution a faint lemon-yellow co|our.
4. Repeat the titration with further aliquots of diluted
seawater until concordant results (titres agreeing
within 0.1 mL) are obtained.
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Result Calculation
1. Determine the average volume of silver nitrate used
from your concordant titres.
2. Calculate the moles of silver nitrate reacting.
3. Use the following reaction equation to determine the
moles of chloride ions reacting.
Ag+(aq) + CI–(aq) AgCI(s)
4. Calculate the concentration of chloride ions in the
diluted seawater.
5. Calculate the concentration of the chloride ions in
the original undiluted sea water.
6. Calculate the concentration of sodium chloride in
the seawater in molL–I, gL–I and g/I00 mL (%).
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Example
Find the concentration of chloride in a 25 mL KCl
solution to which few drops of K2CrO4 were added,
if the end point required 20 mL of 1 M AgNO3.

Solution
The volume of the KCl solution is V1 25 mL
The volume of AgNO3 is V2 20 mL
The molarity of AgNO3 is M2 1 M
The Molarity of KCl is M1 ? M
M1 x V1 = M2x V2
M1 x 25 = 1 x 20 = 0.8 M

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2. Volhard's Method (1874)

• Sample: CI–, Br–,I– or SCN–.

• Type of titration: Back titration.
• Standard Solution: Standard ammonium
thiocyanate solution.
• pH: Acidic
• Indicator: ferric alum.
• Color at end point: Brick red ppt due to formation of
ferrous thiocyanate complex.

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Steps involved in Volhard's method
Step 1: Adding excess Ag+ into sample
Ag+ + CI– AgCl + left Ag+
Step 2: Removing AgCl by filtration/washing.
Step 3: Adding Fe3+ into filtrate (i.e., the left Ag+).
Step 4: Titrating the left Ag+ by SCN–:
Ag+ + SCN– AgSCN
Step 5: End point determination by red colored Fe(SCN)2+
complex (when all Ag+ has been consumed, SCN– reacts
with Fe3+)
SCN– + Fe3+ Fe(SCN)2+(aq)

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Example 1
A 30 mL solution of I– was treated with 50 mL of 0.365 M
AgNO3. AgI(s) was filtered off, and the filtrate (plus Fe3+)
was titrated with 0.287 M KSCN. When 37.6 mL had been
added, the solution turned red. How many milligrams of I–
were in the original solution?
Solution
The volume of the solution is 30 mL
The volume of AgNO3 is 50 mL

The molarity of AgNO3 is 0.365 M

The Molarity of KSCN is 0.287 M
The volume of KSCN is 37.6 mL
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The reaction is:
I– + AgNO3 AgI + NO3–
AgI + KSCN AgSCN + KI
The number of moles of AgNO3 can be given as:
Number of moles AgNO3 = Volume x Molarity
50 x10–3 L x 0.365 M = 0.01825 mol
Number of moles KSCN = 37.6 x10–3 x 0.287 = 0.01079 mol
The number of Ag+ in excess that is used to titrate I– can be
given as:
Number of moles of Ag+ =
Number of moles of AgNO3 – number of moles of KSCN
0.01825 mol – 0.01079 mol = 0.00746 mol
The mass of iodine in the original solution can be found as:
0.00746 mol x 126 = 0.9467 g
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Example 2

A 10 mL of a chloride sample was treated with 15 mL

of 0.1182 M AgNO3. The excess silver was titrated
with 0.101 M SCN– requiring 2.38 mL to reach the red
Fe(SCN)2+ end point. Find the concentration of
chloride.

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3. Fajan's method
• Fajan's method is the most recent and most accurate
silver halide method.
• It is based on the adsorption of adsorption indicators
on the surface of the positively charged silver chloride
particles formed in the precipitation titration when Ag+
ion is in excess.
• Sample: CI–, Br–, I– and SCN–.
• Type of titration: direct titration.
• Standard Solution: Standard silver nitrate solution.
• Indicator: Adsorption indicators like eosin, fluoroscein.
• Color at end point: Depending upon the use of indicator

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Summary
• Type of volumetric analysis that depends on the
formation of a precipitate.
• Mainly used for estimating halides with the help
of silver nitrate or ammonium thiocyanate.
• Different methods, Mohr's,Valhards and Fajans.
• Volhards method are carried out in acidic media
with back titration process.
• Fajans method is based on absorption indicator
method.
• Application mainly used to estimate sodium
chloride and potassium chloride in electrolytes.

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