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Principles Of Gravimetric Analysis
In precipitation gravimetry, the analyte is converted to a sparingly soluble precipitate. This precipitate is then filtered, washed free of impurities, converted to a product of known composition by suitable heat treatment, and weighed. For example, a precipitation method for determining calcium in natural waters involves the addition of C2O42- as a precipitating agent :
Ca2+ (aq) + C2O42- (aq) → CaC2O4 (s)
The precipitate CaC2O4 is filtered, then dried and ignited to convert it entirely to calcium oxide:
CaC2O4 (s) → CaO (s) + CO (g) + CO2(g)
After cooling, the precipitate is weighed, and the calcium content of the sample is then computed.
Steps In Gravimetric Analysis
- Preparation of the Solution:
This may involve several steps including adjustment of the pH of the solution in order for the precipitate to occur quantitatively and get a precipitate of desired properties, removing interferences etc.
- Precipitation:
This requires addition of a precipitating agent solution to the sample solution. Upon addition of the first drops of the precipitating agent, supersaturation occurs, then nucleation starts to occur where every few molecules of precipitate aggregate together forming a nucleus.
At this point, addition of extra precipitating agent will either form new nuclei ( precipitate with small particles ) or will build up on existing nuclei to give a precipitate with large particles . The following factors determine a successful analysis by precipitation.
- The precipitate must be so insoluble that no appreciable loss occurs when it is collected by filtration. In practice this usually means that the quantity remaining in solution does not exceed the minimum detectable by the ordinary analytical balance, viz. 0.1 mg.
- The physical nature of the precipitate must be such that it can be readily separated from the solution by filtration, and can be washed free of soluble impurities. These conditions require that the particles are of such size that they do not pass through the filtering medium, and that the particle size is unaffected (or, at least, not diminished) by the washing process.
- The precipitate must be convertible into a pure substance of definite chemical composition; this may be effected either by ignition or by a simple chemical operation, such as evaporation, with a suitable liquid.
- .Digestion of the Precipitate:
The precipitate is left hot (below boiling) for 30 min to 1 hour in order for the particles to be digested. Digestion involves dissolution of small particles and reprecipitation on larger ones resulting in particle growth and better precipitate characteristics.
This process is called Ostwald ripening. An important advantage of digestion is observed for colloidal precipitates where large amounts of adsorbed ions cover the huge area of the precipitate.
Digestion forces the small colloidal particles to agglomerate which decreases their surface area and thus adsorption.
The precipitate often contains ions that where trapped when the precipitate was formed. This is mostly a problem for crystalline precipitates. If the trapped ions are not volatile, then their presence will corrupt the weighing step. Concentration of interfering species may be reduced by digestion. Unfortunately ,postprecipitation as we will see later will increase during digestion.
- 4. Washing and Filtering
Problems with surface adsorption may be reduced by careful washing of the precipitate. With some precipitates, peptization occurs during washing. Each particle of the precipitate has two layers , in primary layer certain ions are adsorbed and in the outer layer other ions of opposite charge are adsorbed . This situation makes the precipitate settle down .
If the outer layer ions are removed then all the particles will have the same charge so the particles will be dissonant . This is called peptization .This results in the loss of part of the precipitate because the colloidal form may pass through on filtration. ,
in case of colloidal precipitates we should not use water as a washing solution since peptization would occur. In such situations dilute volatile electrolyte such as nitric acid, ammonium nitrate, or dilute acetic acid may be used.
Usually, it is a good practice to check for the presence of precipitating agent in the filtrate of the final washing solution. The presence of precipitating agent means that extra washing is required.
Filtration should be done in appropriate sized Gooch or ignition ashless filter paper. After the solution has been filtered, it should be tested to make sure that the analyte has been completely precipitated. This is easily done by adding a few drops of the precipitating reagent to the filtrate ; if a precipitate is observed, the precipitation is incomplete.
5- Drying and Ignition:
The purpose of drying (heating at about 120-150 oC in an oven) is to remove the remaining moisture while the purpose of ignition in a muffle furnace at temperatures ranging from 600-1200 oC is to get a material with exactly known chemical structure so that the amount of analyte can be accurately determined .
The precipitate is converted to a more chemically stable form. For instance, calcium ion might be precipitated using oxalate ion, to produce calcium oxalate (CaC2O4) which is hydrophil , therefore it is better to be heated to convert it into CaCO3 or CaO . The CaCO3 formula is preferred to reduce weighing errors.
6-Weighing the precipitate :
The precipitate can not be weighed with the necessary accuracy in place on the filter paper; nor can the precipitate be completely removed from the filter paper in order to weigh it.The precipitate can be carefully heated in a crucible until the filter paper has burned away; this leaves only the precipitate. (As the name suggests, “ashless” paper is used so that the precipitate is not contaminated with ash.)
. If you use Gooch crucible then after the precipitate is allowed to cool (preferably in a desicator to keep it from absorbing moisture), it is weighed (in the crucible). The mass of the crucible is subtracted from the combined mass, giving the mass of the precipitated analyte. Since the composition of the precipitate is known, it is simple to calculate the mass of analyte in the original sample.