Gravimetric Analysis

Definition Gravimetric analysis is a procedure of isolating and weighing an element or a definite compound of the element in as pure form as possible.

Advantages of Gravimetric Analysis

It is used to isolate the constituents & may be used in examination for the presence of impurities. It is accurate and precise when using modern analysis balances. Possible sources of error are readily checked since filtrates can be tested for completences of precipitation. Determinations can be carried out with relatively inexpensive apparatus.
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Disadvantages of Gravimetric Analysis It is generally more consuming method. timetime-

Any interfering agent must be removed prior to precipitation. Methods are often complicated and a slight mis-step in a misprocedure can often mean disaster for the analysis.

Types
Volatilization or Evolution or Ignition method Solvent extraction method Precipitation method Electro analytical method Chromatographic method

Volatilization or Ignition Method

Here the sample is directly ignited with or without some forms of prior treatment, or else the ignition follows a preliminary precipitation. In both instances, the residue obtained after ignition is weighed.

Volatilization or Ignition Method may be affected in several ways-ways-By simple ignition in air or in a current of an indifferent gas. By treatment with some chemical reagent whereby the undesired constituent is rendered volatile. By treatment with a chemical reagent whereby the desired constituent is rendered nonnonvolatile.

Slide 2 j1 A muffle furnace is a (usually) front-loading box-type oven or kiln for high-temperature applications such as fusing glass, creating enamel coatings and ceramics. They are also used in many research facilities, for example by chemists in order to bake the moisture out of a sample to ensure it is completely dry.
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Factors affecting the validity of Volatilization or IgnitionIgnitionTemperature

Temperature must be high enough to volatilize all except the desired heat-stable product. heatHigh temperatures can result in fusion of the metallic portion of the residue with the crucible. For example, Bismuth salts must not be ignited in metal crucibles.

Bismuth Subsalicylate
The total procedure is given by the following schematic diagram-diagram-Bismuth Subsalicylate Direct Ignition Ignition Reignited in presence of HNO3

Magnesium Trisilicate [ 2MgO. 3SiO2. X H2O ]

Magnesium Trisilicate [ 2MgO. 3SiO2. X H2O Diluted H2SO4 Soluble Magnesium Sulfate (MgSO4) Filtration Residue Silica (SiO2) Wash + Ignited

Precautions must be taken to ensure that the final residue is in the desired form and that all other nonvolatile matter is excluded. excluded.

Residue bismuth trioxide (Bi2O3)

Q. Explain why gravimetric analysis of Bismuth Subsalicylate requires some additional treatments.

Weighed Q. Explain why gravimetric analysis of Magnesium Trisilicate requires additional treatment with diluted H2SO4.

Solvent Extraction

Solvent Extraction
Solvent extraction is used principally for the determination of alkaloids in crude drugs, injections and tablets. Such methods are also applicable to the control of synthetic bases, their salts and preparations and to a number of nonbasic substances which may be readily isolated by extraction with an organic solvent.

Precipitation
Precipitation is the most important which is concerned in gravimetric analysis. The constituent being determined is precipitated from solution in a form which is so slightly soluble that no appreciable loss occurs when the precipitate is separated by filtration and weighed.
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Types
Extraction yielding a final product in the form in which it is present. Example: Caffeine and Sodium benzoate USP injection. Extraction which yields an acid originally present as a salt. Example: Thiopentone Sodium injection. Extraction yielding a base originally present as a salt. Example: Chloroquine phosphate USP and tablet USP. Extraction of natural product. Example: Alkaloid, storox USP for cinnamic acid.

Slide 11 j2 StorOx is a biorational broad spectrum bactericide/fungicide that was formulated for the treatment, prevention and control of plant pathogenic diseases on crops after harvest.
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Solubility product
The product of the equilibrium concentrations of the ions in a saturated solution of a salt.
1. 2. 3. 4.

Precipitation
Steps in Precipitation method:
Precipitation Filtration Washing Drying and ignition of the precipitate
Species analyzed Mg2+ Ca2+ Ba2+

Precipitation
Precipitated form Form weighed Mg(NH4)PO4.6H2 O CaC2O4.H2O BaSO4 Mg2P2O7 CaCO3 or CaO BaSO4 Some interfering species

Many metals except Na+ and K+ Many metals except Mg2+, Na+, or K+ Na+, K+, Li+, Ca2+, Al3+, Cr3+, Fe3+, Sr2+, Pb2+, NO3Ag+, NH4+ Many metals

Cr3+ Mn2+

PbCrO4 Mn(NH4)PO4.H2O Mn2P2O7

Precipitation
Factors Solubility: The precipitate must be so insoluble that no appreciable loss occurs when it is collected by filtration. Physical Nature: 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. Chemical Composition: The precipitate must be convertible into a pure substance of definite chemical composition. Temperature: Precipitates are more readily coagulated and hence more easily filtered if the solution is hot and dilute.

Precipitation
Factors Time: Time is very important for the following two reasons reasons A suitable length of time elapses between the addition of the precipitant and the removal of the precipitant. A time lapse also allows the precipitate to assume a form suitable for easy filtration.
Factors

Precipitation

pH: There are three main reasons for adjusting the pH of a solution prior to a gravimetric analysis analysis To ensure maximum precipitation. To prevent precipitation of undesirable compounds. To influence the physical state of the precipitate and to render it more amenable to filtration.

Precipitation
Factors Purity, Composition, Precipitation: and Stability of the

Coprecipitation should be avoided.

Causes General procedures to minimize coprecipitation. coprecipitation.

Final residue must be of known composition. Should be sufficiently stable. Hygroscopic or thermolabile residues are undesirable.