CHAPTER 8: reactant concentrations and rate at

which reactants are mixed

GRAVIMETRIC METHOD ANALYSIS  RELATIVE SUPERSATURATION
 Based on the measurement of mass = Q – S / S; where Q is the concentration
TYPES: of the solute at any instant and S is its
1. PRECIPITATION METHODS – the analyte equilibrium solubility
is converted to sparingly soluble precipitate  When Q – S / S is large, precipitate tends
 This precipitate is then filtered, washed to be colloidal; when small, a crystalline
free impurities, and converted to a solid
product of known composition by  SUPERSATURATED SOLUTION unstable
suitable heat treatment, and the product solution that contain more solute than a
is weighed. saturated solution. Supersaturation is relieved
2. VOLATILIZATION METHODS – analyte or by precipitation of the excess solute
its decomposition products are volatized at  To increase the particle size of the precipitate,
a suitable temperature minimize the relative supersaturation during
 The volatile product is then collected and precipitate formation
weighed or alternatively, the mass of the  HOW DO PRECIPITATE FORM
product is determined indirectly from the  Assume that precipitates form in two ways
loss in mass of the sample namely by nucleation and by particle growth
 PROPERTIES OF PRECIPATES AND  The particle size of freshly formed precipitate is
PRECITATING REAGENTS determined by which is faster
Ideal precipitating reagent would react with the  NUCLEATION process in which a minimum
analyte to give a product that is number of atoms, ions or molecules join
1. Readily filtered and washed free of together to produce a stable solid
contaminants  Further precipitation then involves a completion
2. Of sufficient low solubility so that no between additional nucleation and growth on
significant loss of the solid occurs during existing nuclei (particle growth)
filtration and washing  The rate of nucleation is believed to increase
3. Unreactive with constituents of the enormously with increasing relative
atmosphere supersaturation
4. Of known composition after it’s dried or, if  In contrast, the rate of particle growth is only
necessary, ignited moderately enhanced by high relative
 PARTICLE SIZE AND FILTERABILITY OF supersaturations
PRECIPITATES  HIGH RELATIVE SUPERSATURATION and
 Precipitate made up of large particles are large number of very fine particles results to
generally desirable in gravimetric work because NUCLEATION; LOW RELATIVE
large particles are easy to filter and wash free of SUPERSATURATION and smaller number of
impurities large particles result to PARTICLE GROWTH;
 COLLOID: solid made up of particles having deposition of solid in existing particle result to
diameters that are less than 10-4 cm CRYSTALLINE SUSPENSION
 FACTORS DETERMINING PARTICLE SIZE  CONTROLLING PARTICLE SIZE
 Colloidal particles show no tendency to  Experimental variables lead to crystalline
settle from solution, nor are they easily precipitates include elevated temperature to
filtered increase the solubility of the precipitating agent
 Tyndall effect with good stirring
 The particles, with dimensions on the  Larger particles can also be obtained by pH
order of tenths of a mL or greater, control, provided the solubility of the precipitate
temporary dispersed in the liquid phase depends on pH
is called CRYSTALLINE  Precipitate having very low solubility generally
SUSPENSION- particles tend to settle forms colloid
and readily filtered  COLLOIDAL PRECIPITATES
 Particle size of a precipitate is influenced  BROWNIAN MOTION prevents their settling out
by experimental variables as of solution under the influence of gravity
precipitate solubility, temperature,

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 Coagulate or agglomerate, individual particles  Process in which normally soluble compounds
of most colloids to give a filterable, amorphous are carried out of solution by a precipitate
mass that will settle out solution  FOUR TYPES: surface adsorption, mixed-
crystal formation, occlusion and mechanical
entrapment
 COAGULATION OF COLLOIDS  Surface adsorption and mixed-crystal formation
 Coagulation can be hastened by heating, are equilibrium process, whereas occlusion
stirring and adding electrolyte to the medium and mechanical entrapment arise from the
 The charge of the colloidal particle fromed kinetics of crystal growth
gravimetric analysis is determined by charge of  SURFACE ADSORPTION
the lattice ion that is in excess when the  Adsorption is a common source of
precipitation is complete coprecipitation that is likely to cause significant
 ADSORPTION: process in which a substance is contamination of precipitates with large specific
held on the surface of the solid; ABSORPTION: surface areas, coagulated colloids
retention of the substance within the pores of a  Coagulation of a colloid doesn’t significantly
solid decrease the amount of adsorption
 The charge on a colloidal particle performed in  The net effect of surface adsorption is therefore
a gravimetric analysis is determined by the the carrying down of an otherwise soluble
charge of the lattice ion that is in excess when compound as a surface contaminant
the precipitation is complete  MINIMIZING ADSORBED IMPURITIES ON
 Coagulation of a colloidal suspension can be COLLOIDS
often be brought about by short period of - The purity of many coagulated colloids is
heating, particularly if accompanied by stirring improved by digestion
 More effective way to coagulate a colloid is - Regardless of the method of treatment, a
increase the electrolyte concentration of the coagulated colloid is always contaminated
solution to some degree, even after extensive
 PEPTIZATION OF COLLOIDS washing
 PEPTIZATION is a process by which a  REPRECIPITATION
coagulated colloid returns to its dispersed state. - A drastic but effective way to minimize the
 TREATMENT OF THE COLLOIDAL effects of adsorption is reprecipitation, or
PRECIPITATES double precipitation
 Colloids are best precipitated from hot, stirred  MIXED-CRYSTAL FORMATION
solution containing sufficient electrolyte to - One of the ions in the crystal lattice of a solid
ensure coagulation is replaced by an ion of another element
 DIGESTION: process in which a precipitate is - The extent of mixed crystal contamination is
heated for an hour or more in the solution from governed by the law of mass action and
increases as the ratio of contaminant to
which wit was formed; weakly bound water
analyte concentration increases
appears to be lost from the precipitate, the
results is a denser mass that is easier to filter  OCCLUSION AND MECHANICAL
 MOTHER LIQUOR: solution from which a ENTRAPMENT
precipitate forms - When a crystal is growing rapidly during
precipitate formation, foreign ions in the
 CRYSTALLINE PRECIPITATES
counter-ion layer may become trapped, or
 Generally more easily filtered and purified than
occluded, within the growing crystal
coagulated colloids - Occlusion is a type of coprecipitation in which
 IMPROVING PARTICLE SIZE AND a compound is trapped within a pocket formed
FILTERABILITY during rapid crystal growth
 The particle size of crystalline solids can often - Mixed crystal formation may occur in both
be improved significantly by minimizing Q, colloidal and crystalline precipitates, whereas
maximizing S, or both occlusion and mechanical entrapment are
 Digestion of crystalline precipitates (without confined to crystalline precipitate
stirring)for some time after formation frequently - MECHANICAL ENTRAPMENT occurs when
yields a purer, more filterable product crystals lie close together during growth
 COPRECIPITATION - Both occlusion and mechanical entrapment are
at a minimum when the rate of precipitate
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 formation is low, that is, under conditions of low  VOLATILIZATION METHODS
supersaturation - Two most common gravimetric methods
- Digestion is often remarkably helpful in reducing based on volatilizations are those for water
these types of coprecipitation and carbon dioxide
 COPRECIPITATION ERRORS - WATER is quantitatively eliminated from
- can cause either negative or positive errors many inorganic sample by ignition
 PRECIPITATING FROM HOMOGENEOUS - Direct determination, it is collected on any
SOLUTION several solid desiccants and its mass is
 - HOMOGENOUS PRECIPITATION is a determined from the mass gain of the
process in which a precipitate is formed by slow desiccants
generation of precipitating reagent - INDIRECT METHOD, water is determined
homogenously throughout a solution by the loss of mass sample during heating is
 - In general, homogeneously formed less satisfactorily because it must be
precipitates, both colloidal and crystalline, are assumed that water is only component of
better suited for analysis than solid formed by volatilized
direct addition of a precipitating reagent - CARBONATES are ordinarily by acid to
 Urea used for homogenous generation of give CO2, which is readily evolved from
hydroxide ion solution by heat
 DRYING AND IGNITION OF PRECIPITATES - The mass of CO2 is established from the
- After filtration, a gravimetric precipitate is increase in the mass of solid absorbent
heated until its mass becomes constant\ - Absorbent tube must contain desiccant to
- Some precipitate are ignited to decompose prevent loss of the evolved water
the solid and form a compound of known - Sulfides and sulphite can also be
element called the weighing form determined by volatilization
- Temperature required to dehydrate a - Classical method for determination of C and
precipitate completely maybe as low as 100 H in organic compounds is a gravimetric
oC or as high as 1000 oC procedure in which the combustion products
- THERMOGRAVIMETRY or THERMAL (H2O and CO2) are collected selectively on
GRAVIMETRIC ANALYSIS: recording weighed absorbents. The increase in mass
thermal decomposition curves serves as analytical parameter
- THERMOGRAMS: mass vs temp curve
 CALCULATING RESULTS FROM
GRAVIMETRIC DATA
- Computed from two experimental
measurements: the mass of sample and
mass of the product of known composition
Gravimetric methods do not require a
calibration or standardization step because
the results are calculated directly from the
experimental data and molar masses
 ORGANIC PRECIPITATING AGENTS
- TWO TYPES OF ORGANIC REAGENTS:
1. Slightly soluble non-ionic products called
coordination compounds
2. Products in which the bonding between the
inorganic species and the reagent iis largely
ionic
- Organic reagents typically yield soluble
coordination compounds typically contain
atleast 2 functionaal group
- Functional group are located in the molecule
such that a 5 or 6 membered ring results from
the reaction. Reagent that form this kind of
compounds are called chelating agents, and
their products are called chelates
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