Unit 13

Last update : 1/5/2014 PRECIPITATION TITRATION Subjects

Objectives

At the end of this unit the student is expected to be able to :

1- Understand the fundamentals of precipitation titration .
2- Distinguish between Mohar’s , Volahard’s and Vajan’s method ?
3- Realize the advantages and disadvantages of precipitation titration .
4- Derive the precipitation titration curve .
5- Evaluate the precipitation titrations .
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Introduction

Thus far we have examined titrimetric methods based on acid–base, complexation,

and redox reactions . A reaction in which the analyte and titrant form an insoluble
precipitate also can serve as the basis for a titration. We call this type of titration
a precipitation titration. One of the earliest precipitation titrations developed at the end of
the eighteenth century was the analysis of K2CO3 and K2SO4 in potash. Calcium nitrate,
Ca(NO3)2, was used as the titrant, forming a precipitate of CaCO3 and CaSO4. The
titration’s end point was signaled by noting when the addition of titrant ceased to
generate additional precipitate. The importance of precipitation titrimetry as an analytical
method reached its zenith in the nineteenth century when several methods were
developed for determining Ag+ and halide ions.
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Titration Curves
A precipitation titration curve follows the change in either the analyte’s or the titrant’s
concentration as a function of the titrant’s volume. As we have done with other titrations,
we will show how to calculate the titration curve .
Calculating the Titration Curve :
Let’s calculate the titration curve for the titration of 50 mL of 0.05 M NaCl with 0.1 M
AgNO3. The reaction in this case is
Ag+(aq) + Cl−(aq) ⇌ AgCl(s)
Because the reaction’s equilibrium constant is so large
[ AgCl ] 1 1 1
K eq   
  
  10
 5.6 X 10 9
[ Ag ][Cl ] [ Ag ][Cl ] K sp 1.8 X 10

we may assume that Ag+ and Cl– react completely.

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Titration Curves

Step 1: Calculate the volume of AgNO3 needed to reach the

equivalence point : By now you are familiar with our approach to
calculating a titration curve. The first task is to calculate the
volume of Ag+ needed to reach the equivalence point. The
stoichiometry of the reaction requires that :

Moles Ag+ = moles Cl−

MAg X VAg = MCl X VCl
Solving for the volume of Ag+
Veq.p = VAg = (MCl X VCl )/ MAg=(0.05 M)(50 mL) / (0.1 M)=25
mL VIDEO VIDEO
You Tube My Channel
This means we need 25 mL of Ag+ to reach the equivalence point.
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Titration Curves

Step 2: Calculate pCl before the equivalence point by determining the

concentration of unreacted Cl- : Before the equivalence point the analyt , Cl–
, is in excess. The concentration of unreacted Cl– after adding 10 mL of Ag+,
for example, is :
[Cl−]= (initial moles Cl− − moles Ag+ added) / ( total volume in conical flask)
= (MClVCl − MAgVAg ) / (VCl+VAg) )
=(0.05 M)(50 mL)−(0.1 M)(10 mL) / (50 mL+10mL ) =2.5X10−2 M
which corresponds to a pCl of 1.60.
Note that before the equivalent point [Ag+ ] ≈ 0 and we can calculate its real
value from the Ksp expression ( 1,8x10-10 = (2.5X10-2 ) X [Ag+ ] .

Step 3: Calculate pCl at the equivalence point using the Ksp for AgCl to
calculate the concentration of Cl– :
 Unit 13
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Titration Curves
At the titration’s equivalence point, we know that the
concentrations of Ag+ and Cl– are equal. To calculate
the concentration of Cl– we use the Ksp expression
for AgCl; thus :

Ksp = [Ag+][Cl−] = (x)(x) = 1.8×10−10

Solving for x gives [Cl−] or [Ag+ ] as 1.3 X 10–5 M,
or a pCl of 4.89 and also pAg = 4.89

Step 4: Calculate pCl after the equivalence point by

first calculating the concentration of excess
AgNO3 and then calculating the concentration of Cl– Titration curve for the titration of 50 mL
using the Ksp for AgCl : of 0.05 M NaCl with 0.1 M AgNO3.
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Titration Curves
After the equivalence point, the titrant is in excess. We
first calculate the concentration of excess Ag+ and then
use the Ksp expression to calculate the concentration of
Cl–. For example, after adding 35 mL of titrant :
[Ag+] = (moles Ag+ added) − (initial moles Cl− ) /
(total volume )
= (MAgVAg − MClVCl ) / (VCl+Vag )
= (0.1 M)(35 mL)−(0.05 M)(50 mL) / (50 mL +
35.0 mL )
=1.18×10−2 M or pAg = 1.93
[Cl−] = Ksp / [Ag+] = 1.8X10−10 / 1.18×10−2
= 1.5×10−8 M or a pCl of 7.82 .
Additional results for the titration curve are shown in VIDEO
You Tube
the previous Figure.
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Argentometric Titrations

Argentometric Titrations :
Argentometry is derived from a latin word Argentum which means silver .
The most widely applicable precipitation titrations involve the use of silver nitrate with
chlorides, bromides, iodides, and thiocyanate. Since silver is always there,
precipitation titrations are referred to as Argentometric titrations. This implies that
this type of titration is relatively limited.
According to end point detection method, three main procedures are widely used
depending on the type of application. These are:
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Argentometric Titrations (Mohr’s Method )

Mohr’s Method :
This method utilizes chromate as an indicator. Chromate forms a
precipilate with Ag+ but this precipitate has a greater solubility than that
of AgCl, for example. 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.

2 Ag+ + CrO42- = Ag2CrO4

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

solutions pH > 10 , silver will react with the
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Argentometric Titrations (Mohr’s Method )

hydroxide ions forming AgOH. In acidic solutions, chromate will be converted to

HCrO4- and the end point is delayed . 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. 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+ for the Ag2 CrO4 to form . This leads to a late equivalent point . To
correct for this error we can determine a blank .
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Argentometric Titrations (Volhard’s Method )

Volhard’s Method :
This is an indirect method used for determining the anions that precipitate with silver e.g Cl-
, Br- and I . For example an excess amount of standard Ag+ is added to the chloride unknown
solution containing Fe3+ as an indicator.
Ag+ + Cl- ↔ white precipitate of AgCl
The excess Ag+ is then titrated with standard SCN- solution
Ag+ + SCN- ↔ white precipitate of AgSCN
until a reddish color due to Fe(SCN)2+ complex formation is obtained which results from the
reaction:
Fe3+ + SCN- = reddish complex Fe(SCN)2+
The indicator system is very sensitive and usually good results are obtained.
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Argentometric Titrations (Volhard’s Method )

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 :
AgCl + SCN- ↔ AgSCN + Cl-
This means that , SCN- instead of reacting with the indicator it will react
with the AgCl precipitate . We have two ways to overcome this problem
:
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Argentometric Titrations (Volhard’s Method )

The first includes 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- . The second procedure involves filtration of the precipitate directly
after precipitation, which protects the precipitate from coming in contact
with the added SCN- solution and titrating the excess Ag+ in the filtrate .
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Argentometric Titrations (Volhard’s Method )

Advantages of Volhard’s method :

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 of Volhard’s method :

1- Can not be used in neutral or basic medium .
2- Time consuming .
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Argentometric Titrations (Fajan’s Method )

Fajan’s Method :
Fluorescein and its derivatives are adsorbed to the surface of colloidal AgCl. After all
chloride is used, the first drop of Ag+ will react with fluorescein (FI-) forming a reddish
color.
Ag+ + Fl- = AgF
Since fluorescein and its derivatives are weak acids, the pH of the solution should be
slightly alkaline to keep the indicator in the anion form but, at the same time, is not
alkaline enough to convert Ag+ into AgOH . Fluorescein derivatives that are stronger acids
than fluorescien (like eosin) can be used at acidic pH without problems. This method is
simple and results obtained are reproducible.
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Argentometric Titrations (Fajan’s Method )

How do adsorption indicators work ?

In the Fajans method for Cl– using Ag+
as a titrant, for example, the anionic dye
dichlorofluoroscein is added to the
analyt’s solution. Before the end point,
the precipitate of AgCl has a negative
surface charge due to the adsorption of
excess Cl–. Because dichlorofluoroscein
also carries a negative charge, it is
repelled by the precipitate and remains
in solution where it has a greenish- VIDEO
yellow color You Tube
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Evaluation of Precipitation Titrations

After the end point, the surface of the precipitate carries a positive surface
charge due to the adsorption of excess Ag+. Dichlorofluoroscein now adsorbs
to the precipitate’s surface where its color is pink. This change in the
indicator’s color signals the end point.

Evaluation of Precipitation Titration :

The scale of operations, accuracy, precision, sensitivity, time, and cost of a
precipitation titration is similar to those described elsewhere in this course such
as acid–base, complexation, and redox titrations. Precipitation titrations also
can be extended to the analysis of mixtures provided that there is a significant
difference in the solubility of the precipitates.
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Evaluation of Precipitation Titrations

The Figure on your right shows an

example of a titration curve for a
mixture of I– and Cl– using Ag+ as a
titrant.

Although precipitation titration is rarely

listed as a standard method of analysis,
it may still be useful as a secondary
analytical method for verifying other
Titration curve for the titration of mixture I– and Cl–
analytical methods using Ag+ as a titrant. Note that the end point for I–
is earlier than the end point for Cl– because AgI is
less soluble than AgCl.
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Summary

In this unit the fundamentals of precipitation titration have been

discussed and the calculations for the precipitation titration curves have
been investigated . The ideas , advantages and disadvantages of each of
Mohar’s , Volhard’s and Vajan’s methods have been studied . The
applications of precipitation titration are investigated .The general
aspects of this unit have been clarified with relative pictures , graphs and
videos .
Last update : 1/1/2016 PRECIPITATION TITRATION
Tutorial
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 ?

Your answer :

Our answer
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Answer 1 :
To find the moles of titrant reacting with the sample, we first need to correct for the
reagent blank thus :
VAg=16.9 mL−0.7 mL = 16.2 mL

(0.1 M AgNO3)X(0.0162 L AgNO3)=1.62×10−3 moles of Ag+ = moles of KCl

weight KCl = 1.62X10-3 X 74.6 = 0.12 g .

% KCl = ( 0.12/ 0.32 ) X100 = 37.5

 PRECIPITATION TITRATION
Tutorial
Exercise 2 : The %w/w I– in a 0.6712-g 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– ( aw = 126.9 ) in the sample ?

Your answer :

Our answer
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Answer 2 :
There are two precipitates in this analysis: AgNO3 and I– form a precipitate of AgI, and
AgNO3 and KSCN form a precipitate of AgSCN. Each mole of I– consumes one mole of
AgNO3, and each mole of KSCN consumes one mole of AgNO3; thus
moles AgNO3 = moles I− + moles KSCN
Solving for the moles of I– we find :
moles I− = moles AgNO3 − moles KSCN
moles I− = MAg X VAg − MKSCN X VKSCN
moles I− = (0.05619) X (0.05000) −( 0.05322)×(0.03514) = 9.393X10-4

The %w/w I– in the sample = [(9.393×10−4 mol I−) X 126.9 aw I−) / ( 0.6712 )] X 100 = 17.8
 PRECIPITATION TITRATION
Tutorial
Exercise 3 : 400 mg of a butter was heated and some water was added . After shaking
and filtration ,10 ml 0.2 M Ag+ solution , some HNO3 , drops of Fe3+ solution and some
nitrobenzene were added to the Filtrate . The excess Ag+ in the aqueous layer was
titrated with 0.1 M SCN- standard solution . If the volume of SCN- at the equivalent point
was 15 mL , calculate the percentage of NaCl ( mw = 58.5 ) in the butter sample ?

Your answer :

Our answer
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Answer 3 :
mmoles NaCl = mmoles Cl- = total mmoles Ag+ - excess mmoles Ag+
= 10 X 0.2 - 15 X 0.1 = 0.5
 PRECIPITATION TITRATION
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Exercise 4 : The sulphide contents of 100 mL of a water sample was titrated with a standard
solution of 0.01 M AgNO3 according to the following reaction equation :
2 Ag+ + S2- ↔ Ag2S
If the volume of AgNO3 solution at the equivalent point was 8.5 mL , calculate the
concentration ( ppm ) of H2S ( mw = 34 ) in the water sample ?

Your answer :

Our answer
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Answer 4 :
mmoles H2S = mmoles S2- = mmoles Ag+ X 1/2
= 8.5 X 0.01 X 1/2 = 0.0425
[ 0.0425 (mmoles) X 32 (mw) ] mg
ppm H 2 S  3
X 100  1360 mg / L
100 (mL) X 10 ( L)
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Exercise 5 : In the titration of 25 mL of 0.05 M of AgNO3 solution with 0.02 M
KSCN solution , calculate the molar concentration of Ag+ in the conical flask
solution after the following additions of titrant KSCN solution : (1) 30 mL (2) at
equivalent point (3) 100 mL ? Ksp ( AgSCN ) = 1.0 X 10-12

Your answer :

Our answer
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Answer 5 : Veq.p. = (25 X 0.05 ) / 0.02 = 62.5 mL (3) After equivalent point :
(1) Before equivalent point :

(2) At equivalent point :

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Exercise 6 : A 2.0 gram sample containing Cl- ( aw = 35.5 0 ) and ClO4- (mw= 99.5 ) was
dissolved in sufficient water to give 250 mL of solution. A 50 mL aliquot required 14.0 mL
of 0.09 M AgNO3 in a Mohr’s titration. A 25.00 mL aliquot was then treated with
V2(SO4)3 to reduce the ClO4- to Cl-, following which titration required 40 mL of the
same silver nitrate solution. Calculate the percent of Cl- and ClO4- in the sample ?

Your answer :

Our answer
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Answer 6 :
mmoles Cl - in 50 ml = 14 X 0.09 = 1.26
1.26
mmoles Cl - in 250 ml  X 250  6.3
50
Wt. Cl  in sample  6.3 X 35.5  223.65 mg  0.2237 g
 0.2237 ( g )
% Cl in sample  X 100  %11.2
2. 0 ( g )

mmoles ClO 4 in 50 ml  (40  14 ) X 0.09  2.34
 2.34
mmoles ClO 4 in 250 ml  X 250  11.7
50

Wt. ClO 4 in sample  11.7 X 99.5  1164 mg  1.164 g
 1.164 g
% ClO 4 in sample  X 100  %58.2
2.0 g
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