INTRODUCTION TO ANALYTICAL METHODS FOR ENVIRONMENTAL

CHEMICAL ANALYSES: APPLICATION AND FUNDAMENTALS

1.1 Introduction to Chemical Analysis

Chemical analysis is the determination of the physical properties or chemical composition of samples
of matter. Chemical analysis, which relies on the use of measurements, is divided into two categories
depending on the manner in which the analyses are performed. 

Classical analysis, also termed wet chemical analysis (wet chemistry), consists of
those analytical techniques that use no mechanical or electronic instruments other than a balance. The
method usually relies on chemical reactions between the material being analyzed (the analyte) and
a reagent that is added to the analyte. Wet techniques often depend on the formation of a product of
the chemical reaction that is easily detected and measured.

 Instrumental analysis, which forms the majority of all chemical involves the use of an instrument,
other than a balance, to perform the analysis. A wide assortment of instrumentation is available to the
analyst. In some cases, the instrument is used to characterize a chemical reaction between the analyte
and an added reagent; in others, it is used to measure a property of the analyte. Instrumental analysis
is subdivided into categories on the basis of the type of instrumentation employed.

1.2 Gravimetric methods of analysis

Learning Outcomes
a) explain the principles upon which gravimetric analyses are based (refer to precipitation and
volatilisation methods).
b) Describe properties and mechanisms for ideal precipitations
c) Discuss particle size, colloidal suspensions, coagulation and colloidal co-precipitations
d) Distinguish between colloidal and crystalline precipitates
e) describe the function of various pieces of apparatus used in gravimetric analyses (refer to
suction flasks, suction funnels, silica crucibles, sinter glass crucibles and oven / furnaces).
f) perform calculations on data obtained from gravimetric analyses
g) cite example applications of the use of gravimetric analysis in environmental chemical
analysis.

Gravimetric analysis describes a set of methods in analytical chemistry for the quantitative
determination of an analyte based on the mass of a solid. The methods are classified into Precipitation
Gravimetry and Volatilisation Gravimetry

Precipitation Gravimetry: An insoluble compound forms when a precipitating reagent,

or precipitant, is added to a solution that contains the analyte. In most cases the precipitate is the
product of a simple metathesis reaction between the analyte and the precipitant; however, any reaction
that generates a precipitate potentially can serve as a gravimetric method.
All precipitation gravimetric analyses share two important attributes. The precipitate must be
 of low solubility,
 of high purity,
 of known composition if its mass is to reflect accurately the analyte’s mass, and
 be easy to separate the precipitate from the reaction mixture.
These describe the ideal properties of an ideal precipitation.

In precipitation gravimetry, the analyte must first be converted to a solid by precipitation with an
appropriate reagent. The precipitate can then be collected by filtration, washed, dried to remove traces
of moisture from the solution, and weighed. The amount of analyte in the original sample can then be
calculated from the mass of the precipitate and its chemical composition.

Volatilisation Gravimetry: In this method for gravimetric analysis, a sample is thermally or

chemically decomposed, and the resulting change in its mass is measured. In other cases, we can trap
and weigh a volatile decomposition product of the decomposition process. Because the release of a
volatile species is an essential part of these methods, they are classified collectively as volatilization
gravimetric methods of analysis.
If thermal decomposition is performed on the sample, the change in the sample mass will be
monitored as a function of temperature, this is a process called thermogravimetry.

As an example, in order to determine the number of moles of water of crystallisation present in a

hydrated salt, the sample would be heated to remove the water and the difference in mass can then be
used to determine the amount of water present and thus the number of moles of water needed for one
mole of the anhydrous salt.

1. Tick the method more suitable for the determination of the amount of water present in a sample of
hydrated magnesium sulphate? precipitation volitilisation

2. State briefly what steps one would take to determine the amount of water in a sample of hydrated
magnesium sulphate
……………………………………………………………………………………………………………
……………………………………………………………………………………………………………
……………………………………
3. Imagine you are given a sample of sea water and asked to determine the amount of chloride ions
present. You decide to use the precipitation method, suggest a suitable reagent to use to form the
precipitate……………………….

Worked Example
A certain barium halide exists as the hydrated salt BaX2.2H2O, where X is the halogen. The barium content of
the salt can be determined by gravimetric methods. A sample of the halide (0.2650 g) was dissolved in water
(200 cm3) and excess sulphamic acid added. The mixture was then heated and held at boiling for 45 minutes.
The precipitate (barium sulphate) was filtered off, washed and dried. Mass of precipitate obtained = 0.2533 g.
Determine the identity of X.
Answer:
Molar Mass of barium sulphate = 137.34 (Ba) + 32.06 (S) + (4 x 16.00) (O) = 233.40
Number of moles = mass / RMM = 0.2533 / 233.40 = 1.09 x 10 -3
This is the number of moles of barium present in the precipitate and, therefore, the number of moles of barium
in the original sample. Given the formula of the halide, (i.e. it contains one barium per formula unit), this must
also be the number of moles of the halide. From this information we can deduce the relative molecular mass of
the original halide salt:
RMM = mass / number of moles
= 0.2650 / 1.09 x 10-3 = 244.18
The relative atomic mass of 2 X will be given by the RMM of the whole salt - that of the remaining
components; So RAM of 2 X = 244.18 - 173.37 = 70.81
2 X = 70.81, so X = 35.41.
The RAM of chlorine is 35.45 which is in good agreement with the result obtained and hence the halide salt is
hydrated barium chloride and X = Chlorine

Additional Examples
1. A compound of Iron and Chlorine is soluble in water. An excess of Silver Nitrate was added to precipitate the
chloride ion as silver chloride. If a 134.8 mg sample of the compound gave 304.8 mg of AgCl, what is the
formula of the compound?

2. A 2.00g sample of limestone was dissolved in hydrochloric acid and all the calcium present in the sample was
converted to Ca2+(aq). Excess ammonium oxalate solution, (NH4)2C2O4(aq), was added to the solution to precipitate
the calcium ions as calcium oxalate, CaC2O4(s). The precipitate was filtered, dried and weighed to a constant
mass of 2.43g. Determine the percentage by mass of calcium in the limestone sample.
Note: Ca2+(aq) + C2O42-(aq)  CaC2O4(s)
Ca = 40, N = 14, C = 12, H = 1, O = 16, Ag = 108, Cl = 35.5, Fe = 56

Uses of gravimetric analysis in quality control

Measurement of the “essential” elements in plant foods (phosphorus, for example, is converted into the
insoluble salt, magnesium ammonium phosphate)
Estimation of pollutants in the air, such as sulphur dioxide (by conversion to insoluble barium sulphate)
Estimation of sulphur dioxide (used to prevent microbial spoilage) in soft drinks, such as orange juice.
Estimation of chloride ions in water supplies (by conversion to insoluble silver chloride).

Unlike precipitation gravimetry, which rarely is used as a standard method of analysis, volatilization
gravimetric methods continue to play an important role in chemical analysis. Several important
examples are discussed below.

Inorganic Analysis

 Determining the inorganic ash content of an organic material, such as a polymer

 determination of dissolved solids in natural waters and wastewaters
 Moisture content determination
 Determination of silica in waters, wastewaters, and rocks.

Organic Analysis

 elemental analysis of organic materials for the mass of carbon and hydrogen in the sample.
 Determination of alkaline metals and earths in organic materials.
 Determination of biomass in waters and wastewaters.