EXPERIMENT 3 : THE GRAVIMETRIC DETERMINATION OF CHLORIDE

1.0 Objectives

After completing the experiment, the students should be able to:

1. List down the important factors which effect the crystallinity/size of precipitate.
2. Describe the steps to be taken to ensure that the precipitates formed are large and easily
filtered and avoid poetization.
3. Carry out the gravimetric experiment confidently.
4. Calculate the theoretical yield of a product.
5. Calculate the percentage yield of a product.

2.0 Introduction

Gravimetric methods are among the most accurate and precise methods of quantitative
analysis. These advantages are counterbalanced by the fact that they are often time
consuming, require considerable attention to detail and are limited to sample size and
concentrations which yield a weighable quantity on a conventional analytical balance. While
many gravimetric methods have been at least partially replaced by newer, faster techniques,
there remain several situations where the only suitable analytical techniques are gravimetric.
Addition of a solution containing silver ion [usually an aqueous silver nitrate (AgNO 3)
solution to a dissolved sample containing chloride ion will quantitatively precipitate the
chloride ion as solid silver chloride (AgCl), due to the small solubility product constant of
silver chloride (ksp= 1.82 x 10-10)). The precipitate may be isolated from solution by filtration,
the material dried, weighed and the percent chloride (% Cl -) calculated from the
stoichiometry of the reaction:

Ag+ (aq) + Cl - (aq) +Ag AgCl (s)

Organic precipitating reagents contain functional groups that combine with inorganic ions
toform insoluble salts. The organic reagent may contain groups such as carboxyl or hydroxyl
that ionize to form anions that combine with cations to form insoluble salts. In this reaction,
the bonding is also electrovalent. Some organic reagents contain nitrogen or oxygen that can
combine with metal ions by forming covalent or coordinate bonds. Other organic reagents
may contain two or more functional groups that can combine with a single cation to form a
ring structure. Such a reagent would be called a bidentate ligand if it contained two
functionalgroups, a tridentate ligand if it contained three, and so forth. The product formed
between a cation and some multidentate ligand to form a ring structure is called a chelate.
The three major requirements for a good gravimetric analysis are that (a) the reagent will
react only with the analyte of interest to form a precipitate, (b) it forms one and only one
product with the analyte and (c) that the analyte precipitates quantitatively from solution, that
is, >99.99%.

In addition to possible interferences common to all gravimetric methods, the presence of any
other halide will cause high results since they produce a silver halide which is even more
insoluble than silver chloride. Also, silver chloride is light sensitive and excessive
photodecomposition will produce erroneous results, according to the reaction:

AgCl(s) 2Ag(s) + Cl2 (gas)

The precipitate becomes violet-purple, due to the presence of finely divided silver metal, and
results will be low. If silver ion (Ag +) is present, in addition to the above, the following
reaction will also occur as a result of the photodecomposition reaction:

3Cl2(g) + 3H2O + 5Ag 5AgCl(s) + ClO3 + 6H+

If this reaction predominates, the results will be high. To minimize such errors, it is
recommended that unnecessary exposure to light be avoided. Gravimetric analysis, if
methods are followed carefully, provides for exceedingly precise analysis. In fact, gravimetric
analysis was used to determine the atomic masses of many elements to six figure accuracy.
Gravimetric provides very little room for instrumental error and does not require a series of
standards for calculation of an unknown. Methods also do not require often expensive
equipment. Gravimetric analysis, due to its high degree of accuracy, when performed
correctly, can also be used to calibrate other instruments in lieu of reference standards.

3.0 Apparatus
Analytical balance
400 cm3 beaker
Burette
Funnel and filter paper
Crucible
Test tube
Policeman
25 cm3 graduated cylinder

4.0 Procedure
1. 0.3g dried NaCl weighed and transferred into 400 cm 3 beaker. Sample
dissolved with 100 cm3 of distilled water.

2. With good stirring, 0.2M AgNO3 added to each of cold sample until AgCl
coagulated.
3. Two crucibles cleaned and dried in the oven. When cooled, each crucible
weighed with 2 pieces of filter papers.

4. The precipitates washed with a solution of 6M HNO 3 per liter of distilled water.
5. The precipitates dried at 110 C for 1 hour and stored in a dessicator while
they cooled.