MODULE 3

GRAVIMETRY
Principles

Solution reaction between analytes and reagents to give sparingly soluble products; filtration, drying or
ignition of precipitates; electrolytic deposition of metals; weighing.

Apparatus

Flasks, beakers, filter funnels, pipettes, filter crucibles, filter papers, oven, muffle furnace, chemical
balance, desiccator.

Applications

Extensive numbers of inorganic ions are determined with excellent precision and accuracy; widely used
in routine assays of metallurgical and mineralogical samples. Relative precision 0.1–1%.

Disadvantages

Requires careful and time-consuming procedures with scrupulously clean apparatus and very accurate
weighings. Coprecipitation cannot always be avoided. Gravimetry includes any analytical method in
which the ultimate measurement is by weight. The simplest form may merely be the drying or heating of
a sample in order to determine its volatile and non-volatile components, or possibly the sample might
be distilled and the residue and fractions of distillate weighed. Metals may be deposited electrolytically
and weighed (Chapter 6). Of far greater scope and importance is the controlled precipitation of an
analyte from solution, followed by the weighing of the precipitate. Subsequent attention will be
restricted to these precipitation methods. To be of gravimetric value, a precipitation process must fulfil
certain conditions. The precipitate must be formed quantitatively and within a reasonable time. Its
solubility should be low enough for a quantitative separation to be made. It must be readily filterable
and, if possible, have a known and stable stoichiometric composition when dried so that its weight can
be related to the amount of analyte present. Failing this, it must be possible to convert the precipitate to
a stoichiometric weighable form (usually by ignition). In both cases the weighed form should be non-
hygroscopic.

Precipitation Reactions

If it is remembered that a chemical reaction can be displaced by changing the state of the products
(Chapter 3) then, provided the solubility product of a precipitate is small, quantitative reaction can be
obtained. Practically, the precipitate may be formed directly on the addition of a reagent or on the
subsequent adjustment of solution conditions, e.g. pH. Precipitates may be of different chemical types,
e.g. salts, complexes, hydroxides, hydrous oxides, and precipitating agents are conveniently divided into
inorganic (Table 5.14) and organic (Table 5.15). The major areas of applications usually employ inorganic
precipitants for inorganic analytes.
the effect of potassium nitrate on the solubility of barium sulphate. The common ion effect (Chapter 3)
is a further important factor affecting solubilities. Addition of A or B to the above system (equation
(5.28)) will shift the equilibrium to the left and reduce the solubility of AB. In practice, this situation
would arise when an excess of a precipitating reagent has been added to an analyte solution. Such an
excess leads to the possibility of complexation reactions occurring which will tend to increase the
solubility of AB. For example, when aluminium or zinc is precipitated by hydroxyl ions, the following
reactions with excess reagent can occur
oxalates of calcium and magnesium for instance, both compounds have fairly low solubility products
(2.3 × 10–9 mol2 dm–6 for calcium oxalate and 8.6 × 10–5 mol2 dm–6 for magnesium oxalate). However, in
the case of the calcium salt, precipitation is complete within a few minutes whilst the magnesium salt
takes several hours. This difference in rates may even be used as a basis for the quantitative removal of
calcium from solution without interference from magnesium. In order to expedite precipitate formation
it is necessary first to look more closely at the processes by which precipitates are produced.
When a reagent is added to an analyte solution forming a sparingly soluble compound, the solubility
product for that compound is immediately exceeded and the solution is said to be supersaturated. The
relative supersaturation Rs is given by

where Q is the actual concentration of the solute and S is the equilibrium concentration. The rate at
which Q reduces to S determines the rate of precipitation. Precipitate formation takes place first by the
aggregation of small groups of ions or molecules, a process known as nucleation. It may occur either by
the chance aggregation of molecules or ions in a homogeneous nucleation process, or by heterogeneous
nucleation when aggregation is initiated by particulate impurities within the solution. Whilst the former
process depends exponentially on the relative supersaturation of the solution, the latter is largely
independent of it. After nucleation the precipitation continues by particle growth, with further ions or
molecules adding to the aggregates. The rate of particle growth will also be dependent upon the relative
supersaturation and on the surface area of the particles, but will not vary so dramatically as the rate of
homogeneous nucleation. The relation between these rates and the relative supersaturation is
summarized schematically in Figure 5.9.

In a particular system, the nature of the precipitated particles will be determined by the relative rates of
nucleation and particle growth. Where nucleation predominates, small particles are produced and a
colloid may

result, whereas a predominance of particle growth will form a more tractable precipitate. From the
practical standpoint, the difference (Q–S) should be controlled and kept to a minimum. On mixing
reagent and analyte solutions it is difficult to avoid a momentarily high (Q–S) value (in the region where
the two first make contact), especially if S is small. Furthermore, a low value of S is necessary for
quantitative precipitation, so that a situation often arises in which the rate of homogeneous nucleation
vastly exceeds that of particle growth. Consequently, the analyst frequently has to cope with colloidal
precipitates or suspensions. Where S is larger, crystalline precipitates are more readily obtained.
Colloidal suspensions occur as a result of electrical repulsions between particles which prevent
agglomeration. These repulsive forces develop from ions adsorbed onto the surface of the precipitate
which cause the formation of an electrical double layer. The adsorbed layer will contain an excess of the
precipitate ion which predominates in solution whilst the diffuse counter ion layer will contain an excess
of oppositely charged ions to maintain the overall electrical neutrality of the solution. In the familiar
example where Cl– has been precipitated as AgCl by the addition of an excess of silver nitrate, the
adsorbed layer will contain an excess of Ag+, and the counter ion layer an excess of and OH–. Adsorption
can be diminished by heating or by the addition of a highly charged strong electrolyte. This allows
coagulation of the precipitate to proceed, but it must be remembered that if a filtered precipitate of this
type is being washed the particles can be dispersed again as a colloid and pass through the filter. This
effect, known as peptization, may be prevented by using hot washing solutions containing a suitable
electrolyte. Precipitates formed by colloid agglomeration are amorphous and porous with very high
surface areas. In almost all cases, precipitates are improved by heating them in contact with the solution
before filtration. This is known as digestion and will promote the formation of larger particles with a
reduced surface area, and more ordered arrangements within crystals. Thus both the surface adsorption
and occlusion of impurities will be reduced.

Purity of Precipitates Steps are normally taken to prevent the simultaneous precipitation of materials
other than the desired analyte species. Incorporation of impurities into the precipitate may however
occur by coprecipitation or post-precipitation. The former arises during the formation of the precipitate,
and the latter after it has been formed. The various modes of coprecipitation are summarized in Table
5.16.

Post-precipitation involves the deposition of a sparingly soluble impurity of similar properties to the
precipitate on the surface of that precipitate after it has been formed. It is particularly a problem where
similar materials are being separated on the basis of their different rates of precipitation, e.g. calcium
and magnesium oxalates or zinc and mercury sulphides. Coprecipitation can be reduced by the normal
practical procedures of precipitation from hot dilute analyte solutions, followed by digestion of the
precipitate. Inclusion phenomena when they occur are very difficult to overcome and it may be
necessary to remove the impurity ion before precipitation. At the same time the degree of post-
precipitation will be increased by digestion and where this form of contamination is paramount rapid
filtration is essential. The extent to which coprecipitation may affect an analysis is well illustrated by the
familiar precipitation of barium sulphate. Substances that may appear as impurities in this precipitate
include sulphuric acid, alkali metal sulphates, ammonium sulphate, iron(III) sulphate, barium phosphate,
barium carbonate, barium chloride, barium nitrate and barium chlorate. The excellent precision and
accuracy often claimed for analyses based on this precipitate undoubtedly result from a compensation
of errors.
Practical Gravimetric Procedures A typical gravimetric analysis procedure may be divided into five
stages: sample pretreatment; precipitation; filtration; drying and ignition; weighing. The operations
involved in the various stages are summarized by Table 5.17. Two aspects, however, need slight
amplification. Firstly, the possible generation of the precipitating agent within the solution in a
homogeneous precipitation procedure should be considered. This method, in which the precipitation is
generated within the solution, has the advantage of preventing local high concentrations of reagent and
thus promoting particle growth as well as minimizing the occlusion of impurities. Some homogeneous
precipitation reactions are shown in Table 5.18. Secondly, the filtration method must be selected to fit
the treatment of the precipitate. Where the material is merely to be dried and weighed, a sintered glass
crucible is generally the most satisfactory. If an ignition step is to be used, however, the precipitate may
be collected on a filter paper and transferred to a silica or platinum crucible for ignition or filtered on an
asbestos pad in a Gooch crucible. Sintered silica crucibles are also used for these precipitates.
minimum solubility. The presence of ammonium salts and hydrogen ions increases the solubility so that
the precipitant (NH4)3PO4 must be added in only small excess, and the pH must be maintained high (pH
= 11–12). Supersaturation is an additional problem, and quantitative precipitation is only achieved after
the mixture has been allowed to stand for an extended time, e.g. overnight.
(c)— Precipitate Purity H3PO4, NH4H2PO4, (NH4)2HPO4, (NH3)3PO4, Mg(H2PO4)2, MgHPO4, Mg3(PO4)2, basic
Mg phosphates, Mg(OH)2, MgCl2 and NH4Cl are all possible contaminants. Of these only NH4Cl which is
volatile and MgHPO4 which ignites to Mg2P2O7 are of no consequence. Amongst the rest are a number of
compounds (including the precipitant itself) which have crystallinity similar to the precipitate, and are
coprecipitated by isomorphic inclusion. The magnitude of the coprecipitation problem is such that, to
overcome it, dissolution and reprecipitation of the initial precipitate is required. This is done by using
the minimum amount of dilute hydrochloric acid and a very small amount of ammonium phosphate.
Concentrated ammonia solution is then added to complete the reprecipitation.

The use of an organic precipitant may be exemplified by reference to the employment of

8hydroxyquinoline (Oxine), to determine aluminium. Aluminium oxinate, Al(C9H6NO)3, can be
quantitatively precipitated from aqueous solutions between pH = 4.2 and pH = 9.8. Due to the non-
selective nature of Oxine as a reagent many other metals are also precipitated within the same range.
To achieve a separation of aluminium from these other elements pH control may be employed. Thus an
acetic acid solution, buffered to pH = 5 by sodium acetate, will provide a medium for the separation of
aluminium from troublesome contaminants such as Be, Mg, Ca, Sr and Ba. Ammoniacal solution (pH = 9)
will enable a separation from As, B, F and P to be made, and if used in conjunction with H 2O2 from Cr,
Mo, Nb, Ta and V as well. Selectivity is further enhanced by the use of masking agents such as cyanide,
tartrate or EDTA. By careful control of these parameters aluminium may be separated, and few
interferences are observed if the precipitation is carried out from an ammoniacal-cyanide-EDTA
solution. When large amounts of Ca or Mg are present the homogeneous precipitation procedure (Table
5.18) is usefully employed at pH = 5. The precipitate is readily filtered and may be weighed after drying
at 150°C as the anhydrous compound.

Applications of Gravimetry

Gravimetric methods provide precise and accurate results and have found a wide utility in chemical
analysis for many years. They are best suited to the determination of major constituents in samples
because of the practical limitations in accurately weighing quantities of less than 0.1 g. The analysis of
rocks, ores, soils, metallurgical and other inorganic samples for their major components has depended
very much on gravimetric methods. Gravimetric procedures are, however, usually time consuming and
demanding, with the result that there is a steady trend towards the use of quicker, instrumentally based
methods. Notable for its impact in recent years on these traditional areas has been X-ray fluorescence
analysis (Chapter 8). Nevertheless gravimetric methods are still very much needed to calibrate these
newer procedures. Table 5.14 and 5.15 give a good indication of the scope of gravimetry.

Further Reading

Cooper, D. & Doran, C., Classical Methods, Vol. I, Wiley, Chichester, 1987. Mendham, J., Dodd, D. &
Cooper, D., Classical Methods, Vol. II, Wiley, Chichester, 1987. Skoog, D. A. & West, D. M., Fundamentals
of Analytical Chemistry (4th edn), CBS College Publishing, New York, 1982. Jefferey, G. H., Bassett, J.,
Mendham, J. & Denney, R. C. (eds) Vogel's Textbook of Quantitative Inorganic Analysis (5th edn),
Longman, London, 1989.