CHAPTER 4: PRECIPITATION TITRATIONS
1 INTRODUCTION
Precipitation reactions and titrations are based on the formation of sparingly-soluble silver salts, e.g. as for the
reaction Cl (aq) + AgNO3 (aq) AgCl(s) + NO3 (aq) .
1.1 USES/APPLICATION
1. Determination of ions, e.g. Cl; Br; I; SCN (thiocyanate)
2. Determination of Ag+
1.2 TITRATION CURVE
Useful for choice of indicator, and determination of titration error.
Example: Titration curve
Derive a curve for the titration of 50.00 mL of 0.0050 M NaCl with 0.0100 M AgNO 3.
The problem solution requires calculation of pAg values at various additions of AgNO3 to NaCl
The curve is then generated by plotting pAg Vs. Volume AgNO3 added
This theoretical approach can give an idea for the best choice of indicator to be used in practice and prevent
or eliminate any titration errors
Reaction:
NaCl + AgNO3
AgCl(s) + NaNO3
1. Initial point at 0.00 mL addition of AgNO3:
pAg is indeterminate and cannot be calculated (no data for AgCl to work with)
2. After addition of 5.00 mL AgNO3:
Calculate [Cl], pCl and determine pAg from solubility product expression
(a). Number of moles NaCl initially:
nNaCl (initial) cNaClVNaCl (0.0050 mol.L 1 )(50.00 10 3 L) 2.500 10 4 mol (or 0.2500 mmol )
(b). Number of moles AgNO3 added:
nAgNO3 (added) c AgNO3 VAgNO3 (0.0100 mol.L 1 )(5.00 10 3 L) 5.000 10 5 mol (or 0.0500 mmol )
(c). Number of moles NaCl in excess:
nNaCl (excess) nNaCl (initial) n AgNO3 (added) 0.2500 0.0500 mmol 2.000 10 4 mol (or 0.2000 mmol )
(d). Concentration of Cl:
nNaCl (excess) 5.000 10 5 mol
[Cl ] [NaCl] 3.636 10 3 M
Vsolution 55.00 10 3 L
(e). pCl log [Cl ] log(3.636 10 3 ) 2.44
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(f). To find pAg, use solubility product expression:
AgCl(s) Ag Cl
[Ag ][Cl ] K sp 1.82 10 10
log [Ag ][Cl ] log 1.82 10 10
log [Ag ] log [Cl ] 9.74
pAg pCl 9.74
pAg 9.74 2.44 7.30
3. All points up to before the equivalence point (25.00 mL) can be calculated in a similar way,
substituting the appropriate volumes
4. At equivalence point, i.e. 25.00 mL AgNO3 added:
[Ag ] 2 1.82 10 10 , but [Ag ] [Cl ]
[Ag ] 1.82 10 10 1.349 10 5 M
pAg log [Ag ] log 1.349 10 5 4.87
5. After equivalence point, e.g. 26.00 mL of AgNO3 added:
Calculate [Ag+] in excess, then pAg
(a). Number of moles NaCl initially [same as in 2(a)]:
nNaCl (initial) cNaClVNaCl (0.0050 mol.L 1 )(50.00 10 3 L) 2.500 10 4 mol (or 0.2500 mmol )
(b). Number of moles AgNO3 added:
nAgNO3 (added) c AgNO3 VAgNO3 (0.0100 mol.L 1 )(26.00 10 3 L) 2.600 10 4 mol (or 0.2600 mmol )
(c). Number of moles AgNO3 in excess:
nAgNO3 (excess) nAgNO3 (added) nNaCl (initial) 0.2600 0.2500 mmol 1.000 10 5 mol (or 0.0100 mmol )
(d). Concentration of Ag+:
nAgNO3 (excess) 1.000 10 5 mol
[Ag ] [AgNO3 ] 1.316 10 4 M
Vsolution 76.00 10 3 L
(e). pAg log [Ag ] log(1.316 10 4 ) 3.88
ACH150X Chapter 4 (Precipitation Titrations) Summary Notes 2020 - 42 -
2 FACTORS INFLUENCING TITRATION CURVES
2.1 CONCENTRATION
An increase in analyte and reagent concentration makes the change in pAg at equivalence point more pronounced.
For more concentrated solutions (~0.1 M), easily-detectable endpoints are observed; the titration error is therefore
minimal. With solutions of 0.001 M or less (dilute solutions), the change in pAg is so small that endpoint
detection becomes difficult; a large titration error is thus to be expected.
10
A
8
B
6
potential equivalence point
pAg
endpoint
region
4
0 Figure 1: Titration curves for A,
0.00 10.00 20.00 30.00 40.00 50.00 mL of 0.0500 M NaCl with
Volume AgNO3 added (mL) 0.1000 M AgNO3, and B, 50.00
mL with 0.0100 M AgNO3
2.2 COMPLETENESS OF REACTION (Ksp VALUES)
The change in pAg at the equivalence point becomes greater as the solubility products become smaller, i.e. as the
reaction between the analyte and silver nitrate becomes more complete. By careful choice of indicator – one that
changes colour in the region of pAg from 4 to 6 – titration of chloride ion should be possible with a minimal
titration error.
The following sets of titration curves for halide ions provide an idea of the variation in shape; iodide ions form the
least-soluble salt, hence react more completely with silver ion and therefore have a sharper curve.
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16
I
14
12
Br
pAg
10
8 Cl
4
Figure 2: Effect of reaction
completeness on precipitation
2
titration curves. For each curve,
50.00 mL of a 0.0500 M solution
0 of the anion was titrated with
0.00 10.00 20.00 30.00 40.00 0.1000 M AgNO3. Smaller
Volume AgNO3 added (mL) values of Ksp give much sharper
breaks at the endpoint.
3 METHODS OF ENDPOINT DETECTION
Three types of endpoints are encountered in titrations with silver nitrate: (1) chemical, (2) potentiometric, and (3)
amperometric. The endpoint produced by a chemical indicator usually consists of a colour change or,
occasionally, the appearance or disappearance of turbidity in the solution being titrated. The requirements for an
indicator for a precipitation titration are that (1) the colour change should occur over a limited range in p-function
of the reagent or the analyte and (2) the colour change should take place within the steep portion of the titration
curve for the analyte.
The three most commonly-used methods involve:
1. Formation of a second coloured precipitate (Mohr method);
2. Formation of soluble coloured complex ion (Volhard Method); and
3. Adsorption indicators (Fajans Method)
3.1 MOHR METHOD
Uses include for the titration of chloride ion (Cl), and bromide ion (Br) with standard AgNO3. There are
typically two reactions involved, namely a main reaction involving the titration of the analyte ion, and an
indicator reaction, which shows the endpoint.
Main reaction: Cl (aq) + Ag (aq)
AgCl(s) (white precipitate)
Indicator reaction: 2Ag (aq) + CrO24 (aq)
Ag 2 CrO4 (s) (brick-red precipitate)
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The molar solubility of silver chromate is several times a greater that for AgCl; thus, AgCl tends to form first in
the titration mixture. By adjusting the chromate concentration to a suitable level, formation of silver chromate can
be slowed down until silver ion concentration in the mixture is equal to the theoretical equivalence point for the
titration of chloride. The [CrO 24 ] at equivalence point to initiate precipitation of Ag2CrO4 can be determined.
Example: Determination of [CrO42 ] at equivalence
For the main (precipitation) reaction AgCl(s)
Ag Cl , we know that [Ag ] [Cl ] at
equivalence point. Therefore, K sp 1.82 10 10 [Ag ][Cl ] [Ag ] 2 .
Thus, [Ag ] 1.82 10 10 1.349 10 5 M
For the indicator reaction Ag 2 CrO4 (s)
2Ag (aq) + CrO42 (aq) , K sp 1.1 10 10 [Ag ]2 [CrO42 ]
1.2 10 12 1.2 10 12
[CrO42 ]
Thus, [Ag ] 2
(1.349 10 5 )2
6.633 10 3 M
3.1.1 Importance of pH
The Mohr method must be done in nearly neutral solutions, i.e. pH 7 – pH 10, because chromate ion is the
conjugate base of the weak chromic acid. Consequently, in more acidic solutions, the chromate ion concentration
is too low to produce the precipitate near the equivalence point.
In acidic media the following reaction occurs:
2CrO24 + 2H
Cr2 O72 H2O
chromate indicator dichromate
Therefore, the equilibrium is shifted to the right and [CrO42-] decreased and larger [Ag+] is required for endpoint
detection. This leads to over-titration.
In a strongly alkaline (basic) medium the following reaction occurs.
2Ag + 2OH
2AgOH(s)
Ag 2 O(s) + H 2 O
The Ag+ is precipitated as its oxide.
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3.2 VOLHARD METHOD
The Volhard method is an indirect or back-titration method in which an excess of a standard solution of silver
nitrate is added to a chloride containing sample solution. The excess silver is then back-titrated using a
standardized solution of potassium- or ammonium thiocyanate with ferric ion as an indicator. The percentage
chloride ion in the original sample is then calculated from the titration data collected.
3.2.1 Application/Uses
It is typically used for the indirect determination of halide ions (by way of back-titrations).
3.2.2 Reactions
There are typically three reactions involved, namely a main reaction involving the titration of the analyte ion, a
back-titration with excess Ag+ with thiocyanate ion, and an indicator reaction, which shows the endpoint.
Main reaction: Cl (aq) + Ag (aq)
AgCl(s) (white precipitate)
Back-titration reaction (excess Ag+): Ag (aq) + SCN (aq)
AgSCN(s) (white precipitate)
Indicator reaction: Fe 3
(aq) + SCN
(aq)
Fe(SCN) 2
(s) (soluble red complex ion)
3.2.3 Precautions
When excess Ag+ has reacted, the thiocyanate may react with AgCl.
Main reaction: Cl (aq) + Ag (aq)
AgCl(s) (white precipitate)
Reaction with excess SCN : AgCl (s) + SCN (aq)
AgSCN (s) + Cl
The reaction above may occur before reaction with indicator thus leading to titration error. Reaction between
SCN and AgCl can be prevented in two ways:
(a). AgCl can be coagulated and filtered before back-titration; and
(b). Add nitrobenzene to titration mixture, which “coats” the AgCl particles and prevent reaction with SCN
3.3 FAJANS METHOD
Adsorption indicators: an organic compound that is adsorbed on the surface of the solid formed during a
precipitation titration. Ideally, the adsorption occurs near equivalence point and results not only in a colour
change, but also a transfer of colour from the solution to the precipitate, e.g. fluorescein (organic dye);
dichlorofluorescein (titration of Cl with AgNO3).
Consider the titration of Cl with AgNO3. The anionic form of the adsorption indicator (fluorescein, C 20H14O5) is
used to locate the endpoint. With the first excess of titrant, the indicator forms a complex with the silver ions in
the counter-ion layer and imparts a red colour to the precipitate. The particles of the precipitate should be kept in
colloidal state in order to obtain satisfactory colour change. Therefore, dextrin is added to stabilize the silver
chloride (AgCl) particles against coagulation.
ACH150X Chapter 4 (Precipitation Titrations) Summary Notes 2020 - 46 -
Reaction:
Cl (aq) + Ag (aq)
AgCl(s) (colloidal precipitate)
Explanation:
1. In an aqueous solution, flourescein partially dissociates into H+ and negative flourescein ions
[C20H13O4OH].
C20 H13O 4 OH [C 20 H13O 4 O]
(yellowish-green)
2. Before equivalence point
The dye is not appreciably adsorbed before equivalence point. Before equivalence point the dye anion is repelled
from the surface of the AgCl particles, owing to the negative charge resulting from absorbed chloride ions.
3. Beyond equivalence point
AgCl becomes positive charged due to strong adsorption of excess Ag+ ions. The dye anion ([C20H13O4OH]) is
held in the counter-ion layer. The net result is the appearance of the red colour on the surface of the precipitate.
The colour change is due to adsorption and not a precipitate silver flourescein ([C20H13O4OH] Ag+).
3.3.1 Requirements of Precipitate and Indicator
1. Colloidal precipitate to maximize the quantity of indicator absorbed (dextrin is to prevent coagulation of the
AgCl precipitate, by the formulation of a protecting colloid).
2. Indicator ion and precipitating agent (Ag+) must have opposite charge.
3. The indicator dye must be strongly held in the counter-ion layer by the primary adsorbed ion.
4. The pH of the solution must assure that the ionic form of the indicator predominates (either basic, neutral or
slightly acidic)
3.3.2 Advantages
1. Rapid
2. Accurate
3. Reliable
3.3.3 Disadvantages
1. Limited application
2. Colloidal precipitate
3. pH of solution must be controlled
4. Many adsorption indicators sensitize silver-containing precipitates toward photodecomposition, which may
cause difficulties, and is therefore done in absence of direct sunlight
ACH150X Chapter 4 (Precipitation Titrations) Summary Notes 2020 - 47 -
TUTORIAL 4: PRECIPITATION TITRATIONS
1. A 25.00 mL sample of a 0.100 M solution of the salt NaBr was titrated with 0.1000 M AgNO3 forming the
precipitate AgBr (Ksp = 5.2 1013).
(a). Write the equation for the above reaction;
(b). Calculate the value of pAg after the addition of 20.00 mL of AgNO 3; (Answer : pAg 20.00 10.33)
(c). Calculate the value of pAg at equivalence point; (Answer : pAg eq 6.14)
(d). Calculate the value of pAg after the addition of 30.00 mL of AgNO 3. (Answer : pAg 30.00 1.00)
Make a rough sketch of the titration curve for this titration
2. Calculate the p-function of the cation (pBa) for 40.0 mL of 0.032 M BaCl2 with 0.005 M Na2SO4 at the
equivalence point. (Ksp for BaSO4 = 1.1 1010) (Answer : pBa 4.98)
3. For the Mohr titration of the anion X to produce solid AgX, the Ksp = 9.8 109, what should be the value of
[CrO 24 ] at the equivalence point to start the precipitation of Ag 2CrO4 at that point?
(Ksp for Ag2CrO4 = 1.29 1012) (Answer : [CrO42 ] 1.31 10 4 M)
4. When titrating for the chloride in a brine solution, a Volhard titration is used. Give the reason for the
addition of the following reagents, and supply the necessary reactions:
(a). AgNO3;
(b). HNO3;
(c). nitrobenzene;
(d). KSCN;
(e). Fe3+.
5. A 250 mg sample of a pure chlorinated aromatic compound with a molecular weight of 261.4 was
decomposed, converting the bound chlorine to Cl. The resulting solution required 21.70 mL of 0.1322 M
AgNO3 for titration of the chloride ion.
(a). Calculate the percentage chloride in the compound; (Answer : %Cl 40.68%)
(b). Determine the number of chlorine atoms in each molecule of the aromatic compound.
6. The bismuth in 0.7405g of an alloy was precipitated as BiOCl and separated from the solution by filtration.
The washed precipitate was dissolved in nitric acid and treated with 10.00 mL of 0.1498 M AgNO 3, causing
the precipitation of AgCl. The excess AgNO3 required 12.92 mL of 0.1008 M KSCN for titration. Calculate
the % Bi in the sample. (Answer : %Bi 5.54%)
7. A 25 mL portion of saline solution was acidified with dilute nitric acid and treated with 25 mL of 0.2149 M
AgNO3. After addition of a few milliliters of nitrobenzene, the solution required 26.40 mL of 0.1322 M
KSCN for titration. Calculate the molar concentration of NaCl in the saline
solution. (Answer : [NaCl] 0.07532 M)
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