Gravimetric Methods of Analysis

CHM202 Dr. S. Korfali

Types of Gravimetric Methods

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These analytical methods are performed by mass measurement Types of gravimetric methods (the first two methods are discussed in this chapter) Precipitation gravimetry: The analyte is separated from solution sample as a precipitate and converted to a compound of known composition that can be weighed. Volatilization gravimetry: The analyte is separated from other constituent of sample by conversion to a gas of known chemical composition. The mass of the gas then serves a measure of analyte concentration. Gravimetric Titrimetry (discussed in next chapter). Electrogarvimetry: Analyte separated by deposition on electrode by an electric current. The mass of this product then provides a measure of analyte concentration
Atomic Mass Spectrometry : uses mass spectrometer

Precipitation Gravimetry
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Analyte is converted to a precipitate by precipitating agent Precipitate is filtered Washed to free impurities Dried and converted to a product of known composition and weighed If necessary ignited to a compound of known composition and weighed. Example: a precipitation method for determining calcium in aqueous solution Excess oxalic acid (H2C2O4) is added to aqueous solution of sample. Ammonia is added to neutralize excess acid and causes essentially all of the calcium to precipitate as calcium oxalate 2NH3 + H2C2O4 2NH4+ + C2O42Ca2+ (aq) + C2O42- (aq) CaC2O4 (s) The precipitate is filtered using a weighed crucible, dried and ignited to convert calcium oxalate entirely to calcium oxide CaC2O4 (s) CaO(s) + CO (g) + CO2 (g) After cooling crucible and precipitate weighed, mass of calcium oxide determined and mass of calcium deduced

Properties of Precipitate and Precipitating Agent

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Ideally, a gravimetric precipitating agent should react specifically or selectively with analyte

Specific reagent (which are rare) reacts only with a single chemical species; e.g., dimethy1glycoxime is a specific reagent that precipitates only Ni2+ from alkaline solutions. Selective reagent (which are more common) reacts with only a limited number of chemical species; e.g., AgNO3 precipitates from acidic solution Cl ,Br- , I- , and SCN-. The ideal precipitating reagent would react with the analyte to give product that is:
easily filtered and washed free of contaminants; of sufficiently low solubility so that no significant loss of the analyte occurs during filtration and washing; unreactive with constituents of the atmosphere of known composition after it is dried or, or if necessary ignited

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In gravimetric analysis we aim at getting a precipitate or particle size that can be filtered and pure. Large particle size are more pure than small size due to surface area Large particle size are generally more desirable for gravimetric analysis

PARTICLE SIZE AND FILTERABILITY OF PRECIPITATES

Factors That Determine the Particle Size of Precipitate: The particle size of solids formed by precipitation varies enormously
Colloidal Suspensions : consist of tiny particles that are invisible to the naked eye (10 7 10 4 cm in diameter). Colloidal particles show no tendency to settle from solution, nor are easily filtered. Individual colloidal particles can be made to stick together to give filterable mass. Crystalline Suspensions: consist of particles with dimensions on the order > 0. 1 cm. Crystalline particles tend to settle spontaneously and are easily filtered. Scientists have studied precipitate formation for many years, But the mechanism of precipitation is not fully understood . Experimental variables that influence the particle size of a precipitate are:
1. precipitate solubility 2. temperature 3. reactant concentrations, and 4. rate at which reactants are mixed

The net effect of these variables can be accounted for, at least quantitatively, by assuming that the particle size is related to a single property of the system called Relative Supersaturation

Relative Supersaturation
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Relative Supersaturation = Q S S Q is the concentration of the solute at any instant S is its equilibrium solubility. Experimental evidence indicate that particle size of a precipitate varies inversely with relative supersaturation . To increase the particle size of precipitate, minimize the relative supersaturation during precipitate formation Precipitate tends to be colloidal, if (Q-S)/S is large (S is small) Precipitate tends to be crystalline, if (Q-S)/S is small MECHANISM OF PRECIPITATE FORMATION Precipitates form by nucleation and by particle growth Nucleation is a process in which a minimum number of atoms, ions, or molecules join together to give a stable solid particle. Although nucleation should theoretically occur spontaneously, it is usually induced, e.g., (1) dust particles, (2) scratches on the vessel surface, (3) or added seed crystals Further precipitation then involves a competition between additional nucleation and growth on existing nuclei (Particle growth)

MECHANISM OF PRECIPITATE FORMATION (Continued)

Particle Growth: involves the addition of more molecules to nucleus to form crystals If nucleation predominates, a large number of very fine particles result
If particle growth predominates, a smaller number of larger particles are obtained The rate of nucleation is believed to increase with increasing relative superstation. Thus when a preciptate is formed at high relative supersatration, nucleation is the major precipitation mechanism At low relative superaturation , the rate of particle growth tends to predominate and deposition of solid on existing particles occur to the exclusion of further nucleation, a crystalline precipitate forms Experimental variables that minimizes supersaturation and produce crystalline precipitates: A) elevated temperature to increase solubility (S) , lower Q-S/S B) Precipitate from dilute solution ( minimizes Q) C) Slow addition of dilute precipitating agent with effective stirring. This minimizes Q and local excesses of the reagent are prevented by stirring.

 Colloidal suspensions are often stable for indefinite periods and are not

Colloidal Precipitates

directly usable for gravimetric analysis because their particles are too small to be readily filtered. Fortunately by Coagulation or Agglomeration filterable solids are produced (coagulation or agglomeration is the process of converting a colloidal suspension into a filterable solid). Coagulation can be hastened (stability of colloidal suspensions can be decreased by) : A) Heating B) Stirring, and C) Adding electrolyte Why Colloidal suspension are stable and do not coagulate spontaneously? Colloidal suspensions are stable because the particles are either all positively charged or all negatively charged and thus repel one another This charge results from cations or anions that are bound to surface (adsorbed) The process by which ions are retained on surface of solid is known as adsorption For Example: When silver nitrate is first added to a solution Cl- Ions, the colloidal particles are negatively charged as a result of adsorption of some excess Cl- ions This charge becomes positive when enough silver nitrate has been added to provide excess Ag+ ions

Stability of Colloidal Particle-Continued

Above figure shows colloidal AgCl particle in a solution that contains excess of AgNO3 Attached directly to the solid surface is primary adsorption layer which consists mainly of adsorbed silver ions Surrounding the charged layer is a layer of solution called counter-Ion-Layer which contains sufficient excess of negative ions (primarily nitrate) to just balance the charge on the surface of the particle The primarily adsorbed silver ions and the negative counter-ion layer constitute an electrostatic double-layer that imparts stability to colloidal suspension As colloidal particles approach one another, this double layer exerts an electrostatic repulsive force that prevents particles from colliding and adhering

Peptization of Colloidal
Peptization is the process by which a coagulated colloid reverts to its original dispersed state. n When a coagulated colloid is washed, some of the electrolyte responsible for its coagulation is leached from the internal liquid in contact with the solid particles. n In working with coagulated colloids, washing is needed to minimize contamination; however, there is the risk of losses resulting from peptization if pure water is used. n The problem is commonly resolved by washing the precipitate with a solution containing an electrolyte that volatilizes during the subsequent drying or ignition step. For example AgCl is ordinary washed with dilute HNO3 . When precipitate becomes contaminated with acid, no harm results, since the nitric acid is volatilized during drying step. In summary : colloidal particles are best precipitated from hot , stirred solution containing sufficient electrolyte to ensure coagulation The filterability of coagulated colloidal frequently improves if it is allowed to stand for an hour or more in contact with hot solution from which it was formed (This process is called digestion)
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During this process (digestion), weakly bound water appears to be lost from
precipitate, the result is denser mass that is easier to filter.

Crystalline Precipitate
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Crystalline precipitate are generally more easily filtered and purified than are coagulated colloids The size of individual crystalline particles and their filterability can be controlled to a degree The particle size can be improved by minimizing Q and maximizing S Minimizing Q is generally accomplished by using : a) dilute solutions, b) adding the precipitating agent slowly and good stirring. Digestion of crystalline precipitate from hot solution (without stirring) for sometimes after formation frequently yields a purer more filterable product The improvement of filterability undoubtly results from dissolution and recrystallization at elevated temperatures
Recrystallization apparently results in bridging between adjacent particles, a process that yields larger and more easily filtered crystalline aggregate.

Coprecipitation-Impurities in Precipitates
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Coprecipitation is the process in which precipitates tend to carry down from the solution other constituents that are normally soluble, causing contamination of the precipitate. It is the phenomena in which otherwise soluble compounds are removed from solution during precipitate formation. It is important to understand that the solution is not saturated with the coprecipitated specie. Contamination of a precipitate by a second substance whose solubility product has been exceeded does not constitute coprecipitation. There are four types of coprecipitation

Types of Coprecipitation
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Surface Adsorption (equilibrium process) Mixed Crystalline Formation (equilibrium process) Occlusion (controlled by the kinetics of crystal growth) Mechanical Entrapment (controlled by the kinetics of crystal growth) Surface Adsorption Adsorption is a common source of coprecipitation and is likely to cause significant contamination of precipitates with larger surface area. It is a major source of contamination in coagulated colloids, but no significance in crystalline precipitate. The net effect of surface adsorption is carrying down soluble compound as a surface contaminant For example, the coagulated silver chloride in the gravimetric determination of chloride ion is contaminated with primary adsorbed silver ions with nitrate ions in the counter-ion layer
AgNO3 are normally soluble compounds are precipitated with silver chloride

Surface adsorption is reduced by proper precipitation technique, such as digestion and washing.

Types of Coprecipitation
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Mixed Crystalline Formation

In mixed crystalline formation, one of the ions in crystal lattice of solid is replaced by an ion of another element For this exchange to occur, it is necessary that the two ions have same charge and their size differ by no more than about 5 %. The two salts belong to same crystal class For example BaSO4 formed by adding BaCl2 to a solution containing SO42- and Pb2+ (small amount, as impurity) is found to be severely contaminated PbSO4. Here Pb2+ replace some of Ba2+ ions in BaSO4 When mixed crystalline formation (isomorphous replacement) occurs very little can be done about it Precipitates in which mixed crystalline formation occurs are seldom used analytically

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Types of Coprecipitation
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Occlusion
When crystals are growing rapidly during precipitate formation, foreign ions in the counter-ion layer may become trapped or occluded within growing crystal

Because supersaturation and thus crystal growth rate decrease as precipitating progress, the amount of occluded material is greatest in the part of crystal that forms first

Mechanical Entrapment
Mechanical entrapment occurs when crystals lie close together during growth Several crystals grow together and in doing so trap a portion of solution in tiny pockets Both occlusion and mechanical entrapment are at minimum when rate of precipitate formation is low. That is under conditions of low supersaturation Occluded impurities are difficult to remove Digestion may help, but this not completely effective Purification by dissolving and reprecipitation may be helpful

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Precipitation from Homogenous Solution

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Homogenous precipitation is a process in which a precipitate is formed by slow generation of precipitating agent homogenously through out a solution Solids formed by homogenous precipitation are generally purer and more easily filtered than precipitates by direct addition of a reagent to analyte solution Urea is often used for homogenous generation of OH- : (H2N)2CO + 3H2O CO2 + 2NH4+ + 2OHUrea is valuable for the precipitation of hydrous oxides of some metals.

For example, hydrous oxides of iron (III) and aluminum formed by direct addition of base are of gelatinous masses that are bulky and difficult to filter. In contrast, when these same products are formed by homogeneous generation of hydroxide ions, they are dense, readily filtered, and have considerably high purity.

Drying and Ignition of Precipitates

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After filtration precipitates is heated until mass becomes constant. Heating removes solvent, any volatile specie carried down with precipitating, and adsorbed electrolyte from washed liquid Some precipitates are ignited to decompose solid to form compounds of known composition

Ignition at a much higher temperature is usually required if a precipitate must be converted to a more suitable from for weighing
For example :
MgNH4PO4 Mg2P2O7 (heated or ignited at 900 oC)

Volatilization Gravimetry
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The most common gravimetric methods based on volatilization are those for water and carbon dioxide (CO2) Analyte is transformed by reaction to produce water and/or carbon dioxide Water vapor is collected on any of several solid desiccants and its mass is determined from mass gain of desiccants Similarly CO2 by increase in mass of absorbent of CO2 like NaOH

Calculation Example
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Example 12-2
An iron ore was analyzed by dissolving a 1.1324 g sample in concentrated 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 temperature to give 0.5394 g of pure Fe2O3 (Molar Mass= 159.69 g/mol). Calculate (a) the percent Fe (Molar Mass =55.847 g/mol), and (b) the percent as Fe3O4 (Molar Mass = 231.54 g/mol) in the sample

Solution
a) nFe = 2nFe2O3 nFe2O3 = mass Fe2O3/ Molar Mass Fe2O3 = 0.5394 g / 159.69 g/mol = 3.3778x10-3 mol nFe = 2nFe2O3 = (2)(3.3778x10-3 mol)= 6.7556x10-3 mol
Mass Fe = (6.7556x10-3 mol)(55.847 g/mol) = 0.37728 g % Fe by mass = (mass Fe/ mass sample) x (100) = (0.37728 g /1.1324 g)x(100) = 33.32% b) nFe

= 3nFe3O4

nFe3O4 = nFe / 3 = 6.7556x10-3 mol / 3 = 2.25187 x 10-3 mol Mass Fe3O4 = (nFe3O4 )( Molar Mass Fe3O4)
= (2.25187 x 10-3 mol)(231.54 g/mol) = 0.521397 g
% Fe3O4 = (0.521397 g/ 1.1324 g)x(100) = 46.04 %