Chemistry 221

Chapter 13: Precipitation Titrimetry

Precipitation titrimetry, which is one of the oldest analytical techniques, is based on

reaction that yield ionic compounds of limited solubility. The number of precipitating

agents that can be used is limited because of the slow rate of formation of most

precipitates. The most widely used precipitation reagent is silver nitrate, and precipitation

titrimetry based on silver nitrate are known as argentometric methods.

Titration curves for precipitation reactions are very similar to those involving strong

acids and strong bases. Consequently, they can be derived in the exact same way. One

need only substitute the solubility product of the precipitate for the ion-product constant

for the water. The following diagram illustrates such a titration curve.
Clearly, one can see the resemblance of this curve to that of an acid/base titration shown

below.

Both have a sharp inflection point. Furthermore, it is evident that at pre-equivalence and

post-equivalence points, the p-function does not chance very much. At the equivalence

point in contrast, a small volume of titrant corresponds to a large p-function change.

Figure 3 below shows the effect of product solubility on the sharpness of the endpoint.

The change in the p-function at the equivalence point becomes greater as the solubility
product becomes smaller. In other words  p-function increases as the reaction between

the analyte and the silver nitrate becomes more complete.

The endpoint produced by a chemical indicator usually consists of a color change.

Once again, we see the relation between argentometric titrations and acid/base titrations,

as the requirements for an indicator for the titrations are analogous. These requirements

are namely: (1) the color change should occur over a limited range in the p-function of the

reagent or the analyte, and (2) the color change should take place within the steep portion

of the titration curve for the analyte. Three indicators that have widespread use in

argentometric titrations are the Chromate ion, Flourescein and Iron(III) ion.

The chromate ion is employed as an indicator in the Mohr method. Sodium chromate

can serve as an indicator for the argentometric titrations of chlorine, bromine and cyanide
ions, by reacting with silver to form silver chromate (Ag2CrO4). The brick red Ag2CrO4

precipitates at the equivalence point region and thus is a useful indicator. The Mohr

method has an inherent systematic error that is correctable. At reagent concentrations

lower than .1M, the chromate ion imparts an intense yellow color to the solution that

hinders the identification of the red silver chromate. As a consequence, excess silver

nitrate is required before precipitation can be detected and as a result, the volume is

skewed. The correction that is often made to account for this error is making a blank

titration of a chloride free suspension of calcium carbonate. This volume can then be used

to adjust the experimental results. The Mohr method will follow these reactions:

Ag+ + Cl- AgCl (s) white

2Ag+ + CrO4-2 Ag2CrO4 (s) red

The second popular indicator is Flourescein, an adsorption indicator used in the Fajans

method. An absorption indicator is an organic compound that tends to be absorbed onto

the surface of the solid in a precipitation titration. In the ideal scenario, the absorption

occurs near the equivalence point and results in a color change. Flourescein is a widely

used absorption indicator.

HO O OH

COOH
In aqueous solution partial dissociation into H3O and the negatively charged Flourescein

ion. The Flourescein forms a bright red silver salt. These types of indicators give a rapid,

accurate and reliable titration endpoint.

The third indicator used is Iron(III) ion, used in the Volhard method. In this method,

silver ions are titrated with a standard solution of thiocyanate ion, where Fe3+ serves as the

indicator imparting a red color to the solution. This titration must be carried out in an

acidic solution lest the Fe(III) precipitates out as a hydrated oxide. The reaction that

accompany the Volhard method are:

Ag+ + Cl- AgCl (s) white

SCN- + Ag+ AgSCN (s) white

Fe3+ + SCN- Fe(SCN)2+ red

The most important application of the Volhard method is for determing the presence of

halide ions. An excess of silver nitrate is added to the sample and back-titrated with a

standard thiocyanate solution.

Chapter 13 Questions
13-11 Titration of a .485 g sample by the Mohr method required 36.8 ml of standard .

1060M AgNO3 solution. Calculate the percentage of Cl in the sample.

13-12 A .1064 g sample of a pesticide was decomposed by the action of sodium biphenyl

in toluene. The liberated Cl was extracted with water and titrated with 23.28 ml of .03337

M AgNO3, using an adsorption indicator. Express the results of this analysis in terms of

percent aldrin C12H8Cl6

13-13 A 100 ml sample of brackish water was made ammoniacal and the sulfide it

contained titrated with 8.47 ml of .01310 M AgNO3 . The net reaction is

2Ag+ + S- Ag2S

Calculate the parts per million of H2S in the water.

13-14 A 2000 L water sample was evaporated to a small volume and treated with an

excess of sodium tetraphenylboron. The precipitated KB(C6H5)4 was filtered and then

redissolved in acetone. The analysis was completed by a Mohr titration, with 37.90 ml of .

03981 M AgNO3 being used. The net reaction is

KB(C6H5)4 + Ag+ AgB(C6H5)4 + K

Express the results of this analysis in terms of ppm of K.

13-21 A carbonate fusion was needed to free the Bi from .6423g sample containing the

mineral eulytite (2Bi2O3-3SiO2). The fused mass was dissolved in dilute acid, followed

which the Bi3+ was titrated with 27.36 ml of .03369 M NaH2PO4. The reaction is
 Bi3+ + H2PO4- BiPO4 + 2H+

Calculate the percentage purity of eulytite 1112 g/mol in the sample.

13-22 The theobromine (C7H8N4O2) in a 2.95 g sample of ground cocoa beans was

converted to the sparingly soluble silver salt C7H8N4O2Ag by warming in an ammonical

solution containing 25ml of .0100M AgNO3. After reaction was complete, all solids were

removed by filtration. Calculate the percentage of theobromine 180.1 g/mol in the sample

if the combined filtrate and washings required a back-titration with 7.69 ml of .0108M

KSCN.

13-23 A 20 tablet sample of soluble saccharin was treated with 20ml of .08181 M AgNO3.

After removal of the solid, titration of the filtrate and washings require 2.81 ml of .04124

M KSCN. Calculate the average number of mg of saccharin 205.17 g/mol in each tablet.

13-26 A 5.00nl aqueous suspension of elemental selenium was treated with 25 ml of

ammoniacal .0360 M AgNO3. The reaction is

6Ag(NH3)2+ + 3Se + 3H2O 2Ag2Se + Ag2SeO3 + 6NH4-

After this reaction was complete, nitric acid was added to dissolve the Ag2SeO3. The Ag+

from the dissolved Ag2SeO3 and the excess reagent required 16.74 ml of .01370 M KSCN

in a Volhard titration. How many milligrams of Se were contained in each ml of sample.

13-27 A 2.4414 g sample containing KCl, K2SO4 and inert materials was dissolved in

sufficient water to give 250 ml of solution. A Mohr titration of a 50.00 ml aliquot required

41.36 ml of .05818 M AgNO3. A second 50.00 ml aliquot was treated with 40.00 ml of .

1083 M NaB(C6H5)4. The reaction is:

 NaB(C6H5)4 + K+ KB(C 6H5)4 + Na+

The solid was filtered, redissolved in acetone, and titrated with 49.98 ml of AgNO3

solution. Calculate the percentages of KCl and K2SO4 in the sample

13-28 A 1.998 g sample containing Cl- and ClO4- was dissolved in sufficient water to give

250.0ml of solution. A 50.00 ml aliquot required 13.97 ml of .08551 M AgNO3 to titrate

the Cl-. A second 50.00 ml aliquot was treated with V2(SO4)3 to reduce ClO4- to Cl- :

ClO4- + 4V2(SO4)3 + H2O Cl- + 12SO4- + 8VO2+ + 8H+

Titration of the reduced sample required 40.12 ml of the AgNO3 solution. Calculate the

percentage of Cl- and ClO4- in the sample.

Chapter 13 Answers to Questions

36.8ml*.1060 * 1 / 1*.03543 / 1
13-11 * 100% = 28.5% Cl
.485g
 23.28ml*.03337 * 1 / 1 * 1 / 6
13-12 * 100% = 44.41%
.1064

8.47ml*.01310 * 1 / 2*.03408 / 1
13-13 * 106ppm = 18.9ppm
100mlH 2O * 1gH 2O

37.90ml*.03981 * 1 / 1 * 39.098
13-14 = 29.50mg
2.000

27.36ml*.03369 * 1 / 1 * 1 / 4 * 1112
. g / mM
13-21 * 100% = 39.90%
.64223

13-22 AgNO3 consumed: 25 * .0100 - 7.69*.0108 = .1169

.1669 * 1 / 1*.1801
* 100% = 1.02%
2.95

13-23 AgNO3 consumed: 20*.08181 - 2.81*.04124 = 1.52

152
. * 1 / 1*.20517 * 10^ 3mg / g
= 15.60 mg/Tablet
20

13-26 AgNO3 consumed: 25*.0360 - 16.74*.01370 = .6707

.6707 * 2 / 4 * 3 / 2 * 78.96
= 7.94mg/ml
5.00ml

13-27 mM KCl: 41.36 * .05818 * 1/1 = 2.406

mM K+: 49.98 * .05818 *1/1 = 2.908

2.908-2.406 *1/1 = .2508 mM K2SO4

 2.406*.07455
* 100%  36.73% KCl
2.4414 * 50 / 250

.2508*.17426
* 100%  8.951% K2SO4
2.4414 * 50 / 250

13-28 mM Cl = 13.97 * .08551 *1/1 = 1.195mM

mMCl + mM ClO4 = 40.12*.08551*1/1*1/1 = 3.431mM

mM ClO4 = 3.331 - 1.195 = 2.236 mM ClO4

1195
. *.03543
* 100%  10.59% Cl-
11998
. * 50 / 250

2.236*.09945
* 100%  55.65% ClO4-
11998
. * 50 / 250