CH2

Gravimetric Analysis

Chapter Overview

- Overview of Gravimetric Methods - Precipitation Gravimetry - Volatilization Gravimetry - Particulate Gravimetry - Key Terms - Chapter Summary

Gravimetry?
Gravimetry includes all analytical methods in which the analytical signal is a measurement of mass or a change in mass. Direct analysis - the total suspended solids in the water (filtration) - If the analyte is not a solid (Pb2+)??? convert it into a solid form

Indirect analysis

determination of a samples moisture content, How??

Indirect analysis, cont. We can determine an analyte indirectly without its ever being weighed (ex. PO33-)

If we add HgCl2 in excess, each mole of PO33- produces one mole of Hg2Cl2. The precipitates mass, therefore, provides an indirect measurement of the amount of PO33 in the original sample.

Why gravimetry is important???

Types of Gravimetric Methods

1. Precipitation Gravimetry
2. Electrogravimetry

3. Volatilization Gravimetry
4. Particulate Gravimetry

1. Precipitation Gravimetry

In precipitation gravimetry an insoluble compound forms when we add a precipitating reagent, or precipitant, to a solution containing our analyte. - Add precipitating reagent to sample solution - Reacts with analyte to form insoluble material - Precipitate has known composition or can be converted to known composition - Precipitate handling involves Quantitative collection (no losses) Isolation of pure product Measure mass of precipitate Calculation of original analyte content (concentration)

Solubility Considerations An accurate precipitation gravimetric method requires that the precipitates solubility be minimal

Solubility losses are minimized by carefully controlling the composition of the solution in which the precipitate forms.

requires an understanding of the relevant equilibrium reactions affecting the precipitates solubility

Example

If this is the only reaction considered

solubility losses may be minimized by adding a large excess of Cl

Ag+ also forms a series of soluble chloro-complexes, therefore:

Increasing the concentration of chloride, however, leads to an increase in the solubility of AgCl due to the soluble chlorocomplexes large excess of chloride must be avoided

Another important parameter that may affect a precipitates solubility is the pH of the solution in which the precipitate forms. hydroxide precipitates and precipitates containing basic or acidic ions

When the pH is greater than 12.4, the predominate phosphate species is PO43, and the solubility of Ca3(PO4)2 will be at its minimum because only the first reaction occurs. As the solution becomes more acidic, the solubility of Ca3(PO4)2 increases due to the contributions of the 3 other reactions.

Impurities Precipitation gravimetry is based on a known stoichiometry between the analytes mass and the mass of a precipitate. the precipitate must be free from impurities Any impurities present in the precipitates matrix must be removed before obtaining its weight. Co-precipitation

3 main mechanisms of co-precipitation (CPT)

inclusion Occlusion

And adsorption

Inclusions are difficult to remove since the included material is chemically part of the crystal lattice. The only way to remove included material is through reprecipitation, how???
Occlusions are minimized by maintaining the precipitate in equilibrium with its supernatant solution for an extended time. This process is called digestion. Surface adsorption is minimized by decreasing the precipitates available surface area. One benefit of digestion is that it also increases the average size of precipitate particles

The formation of these additional precipitates can usually be minimized by carefully controlling solution conditions - Interferents forming precipitates that are less soluble than the analyte may be precipitated and removed by filtration, leaving the analyte behind in solution. - either the analyte or the interferent can be masked using a suitable complexing agent, preventing its precipitation.

Controlling Particle Size

By carefully controlling the precipitation reaction we can significantly increase a precipitates average particle size. Precipitation consists of two distinct events: Nucleation: the initial formation of smaller stable particles of precipitate (Nuclei) Particle growth: Larger particles form combination of ions/molecules with the existing nuclei (when the rate of

particle growth exceeds the rate of nucleation)

solutes relative supersaturation, RSS, can be expressed as:

Q is the solutes actual concentration, S is the solutes expected concentration at equilibrium (solubility) When RSS is small, precipitation is more likely to occur by particle growth than by nucleation.

Temperature and pH are useful ways to increase the value of S. Conducting the precipitation in a dilute solution of analyte, or adding the precipitant slowly and with vigorous stirring are ways to decrease the value of Q.

An additional method for increasing particle size Problem:

Surface adsorption of excess lattice ions, however, provides the precipitates particles with a net positive or negative surface charge. Electrostatic repulsion between the particles prevents them from coagulating into larger particles. Coagulation can be induced : by increasing the concentration of the ions responsible for the secondary adsorption layer or by heating the solution. One way to induce coagulation is to add an inert electrolyte, which increases the concentration of ions in the secondary adsorption layer

Filtering the Precipitate

filter paper or a filtering crucible or.

Rinsing the Precipitate

involves the use of cold solvents or rinse solutions containing organic solvents such as ethanol. Precipitates containing acidic or basic ions may experience solubility losses if the rinse solutions pH is not appropriately adjusted a volatile inert electrolyte is often added to the rinse water to prevent the precipitate from reverting into smaller particles that may not be retained by the filtering device. This process of reverting to smaller particles is called peptization. The volatile electrolyte is removed when drying the precipitate.

Drying and igniting the Precipitate

After filtration, a gravimetric precipitate is heated until its mass becomes constant. Ignition decomposes the solid and form a compound of known composition.

A temperature of 110 C is usually sufficient when removing water and other easily volatilized impurities.

Applications of Gravimetric Methods Gravimetric methods have been developed for most inorganic anions and cations as well as neutral species such as water, sulfur dioxide, carbon dioxide, and iodine. A variety of organic substances can also be easily determined gravimetrically. Examples: lactose in milk products, salicylates in drug formulations, nicotine in pesticides etc.

Organic Precipitants

Example 1: A 0.4960 g sample of a CaCO is dissolved in an acidic solution. The calcium is precipitated as CaC2O4H2O and the dry precipitate is found to weigh 0.6186 g. What is the percentage of CaO in the sample?

Exemple 2. The Ca in a 200.0-mL sample of a natural water was determined by precipitating the cation as CaC2O4. The ppt was filtered, washed, and ignited in a crucible with an empty mass of 26.6002 g. The mass of the crucible plus CaO (56.077 g/mol) was 26.7134 g. Calculate the con. of Ca (40.078 g/mol) in the water in units of grams per 100 mL. Example 3. An iron ore was analyzed by dissolving a 1.1324-g sample in c-HCl. The resulting solution was diluted with water, and the iron(III) was precipitated as the hydrous oxide Fe2O3 xH2O by the addition of NH3. After filtration and washing, the residue was ignited at a high temp. to give 0.5394 g of pure Fe2O3 (159.69 g/mol). Calculate (a) the % Fe (55.847 g/mol) and (b) the % Fe3O4 (231.54 g/mol) in the sample.

Example 3. An iron ore was analyzed by dissolving a 1.1324-g sample in c-HCl. The resulting solution was diluted with water, and the iron(III) was precipitated as the hydrous oxide Fe2O3 xH2O by the addition of NH3. After filtration and washing, the residue was ignited at a high temp. to give 0.5394 g of pure Fe2O3 (159.69 g/mol). Calculate (a) the % Fe (55.847 g/mol) and (b) the % Fe3O4 (231.54 g/mol) in the sample.

Example 4. An ore containing magnetite, Fe3O4, was analyzed by dissolving a 1.5419-g sample in concentrated HCl, giving a mixture of Fe2+ and Fe3+. After adding HNO3 to oxidize any Fe2+ to Fe3+, the resulting solution was diluted with water and the Fe3+ precipitated as Fe(OH)3 by adding NH3. After filtering and rinsing, the residue was ignited, giving 0.8525 g of pure Fe2O3. Calculate the %w/w Fe3O4 in the sample. Example. 5 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 sulfuric acid added. The mixture was then heated and held at boiling for 45 minutes. The precipitate (barium sulfate) was filtered off, washed and dried. Mass of precipitate obtained = 0.2533 g. Determine the identity of X.

Example. 5 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 sulfuric acid added. The mixture was then heated and held at boiling for 45 minutes. The precipitate (barium sulfate) was filtered off, washed and dried. Mass of precipitate obtained = 0.2533 g. Determine the identity of X.