Republic of the Philippines

Cagayan State University

College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

GRAVIMETRIC
METHODS OF
ANALYSIS

ACOB JIAN CARLO D.

BAGALAYOS, MARLON U.
BAYUCAN, PRINCESS
CUARESMA, SHERVIE
ROMERO, ROA KYLA

BSMLS 1E

GRAVIMETRIC METHODS OF ANALYSIS 1

 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

GRAVIMETRIC METHODS OF ANALYSIS

GRAVIMETRIC METHODS

- Quantitative methods that are based on determining the mass of a pure

compound to which analyte is chemically related.

TYPES OF GRAVIMETRY

PRECIPITATION GRAVIMETRY

- The analyte is separated from a solution of the samples as a precipitate and is

converted to a compound of known composition that can be weighed.
VOLATIZATION GRAVIMETRY

- The analyte is separated from other constituents of a sample by converting it to

a gas of known chemical composition. The mass of the gas then serves as a measure of
the analyte concentration..
ELECTROGRAVIMETRY

- The analyte is separated by deposition on an electrode by an electrical current.

The mass of this product then provides a measure of the analyte concentration.

TYPES OF ANALYTICAL BASED ON MASS

GRAVIMETRIC TITRIMETRY

-The mass of a reagent of known concentration required to react completely with

the analyte provides the information needed to determine the analyte concentration.
ATOMIC MASS SPECTROMETRY
- Uses a mass spectrometer to separate the gaseous ions formed from the
elements making up a sample of matter. The concentration of the resulting ions is then
determined by measuring the electrical current produced when they fall on the surface of
an ion detector.

GRAVIMETRIC METHODS OF ANALYSIS 2

 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

PROPERTIES OF PRECIPITATES AND PRECIPITATING AGENTS

Gravimetric Precipitating Agent- should react specifically or atleast selectively with the
analyte.
Specific Reagents- which are rare, react only with a single chemical species.
Selective Reagents- which are common, react with a limited number of species.
Ideal Precipitating Reagent would react with the analyte to give a product that is
1. Easily filtered and washed free of contaminants;

2. Of sufficiently low solubility that no significant loss of the analyte occurs during filtration
and washing;
3. Unreactive with constituents of the atmosphere;
4. Of known chemical composition after it is dried or, if necessary, ignited

FACTORS THAT DETERMINE THE PARTICLE SIZE OF PRECIPITATES

Colloidal Suspension – whose tiny particles are invisible to the naked eye (10-7- 10-4 cm
in a diameter)
Crystalline Suspension - temporary dispersion of such particles in a liquid phase
Relative Supersaturation
𝑸−𝑺
Relative supersaturation= 𝑺

Q= concentration of solute at any instant

S= equilibrium solubility

Note: when ( Q-S )/S is large, the precipitation tends to be colloidal, and ( Q-S )/S is small,
a crystalline solid more likely.

Nucleation is a process in which minimum number of atoms, ions, or molecules join

together to give a stabe liquid.

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 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

MECHANISM OF PRECIPITATE FORMATION

A precipitate forms in 2 ways

Nucleation- If nucleation predominates , a precipitate containing a large number of small

particles result.

Particle Growth- If growth predominates, a smaller number of larger particles is

produced.

 When a precipitate is formed at high relative supersaturation, nucleation is the

major precipitation mechanism and a large number of small particles is formed.
 Low relative supersaturation , the rate of particle growth tends to predominate and
deposition of solid particles occurs rather than further nucleation. Low relative
supersaturation produces crystalline suspensions.

EXPERIMENTAL CONTROL OF PARTICLE SIZE

 If the solubility of the precipitate depends on pH, larger particles can also be
produced by controlling pH. For example, large, easily filtered crystals of calcium
oxalate are obtained by forming the bulk of the precipitate in a mildly acidic
environment in which the salt is moderately soluble.
 The precipitation is then completed by slowly adding aqueous ammonia until the
acidity is sufficiently low for removal of substantially all of the calcium oxalate. The
additional precipitate produced during this step deposits on the solid particles
formed in the first step. Unfortunately, many precipitates cannot be formed as
crystals under practical laboratory conditions.
 A colloidal solid is generally formed when a precipitate has such a low solubility
that S in Equation 12-1 always remains negligible relative to Q.
 The relative supersaturation thus remains enormous throughout precipitate
formation, and a colloidal suspension results. For example, under conditions
feasible or an analysis, the hydrous oxides of iron(III), aluminum, and chromium(III)
and the sulfides of most heavy-metal ions form only as colloids because of their
very low solubilities.

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 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

COLLOIDAL PRECIPITATES

Individual colloidal particles are so small that they are not retained by ordinary filters.

Brownian motion prevents their settling out of solution under the influence of gravity.
Fortunately, however, we can coagulate, or agglomerate, the individual particles of most
colloids to give a filterable, amorphous mass that will settle out of solution.

COAGULATION OF COLLOIDS

Coagulation- can be hastened by heating, by stirring and by adding electrolyte to the

medium.

Adsorption is a process in which a substance (gas, liquid, or solid) is held on the surface
of a solid.
Absorption is retention of a substance within the pores of a solid.

Primary adsorption layer- consists mainly of adsorbed silver ions

Counter-ion layer - Surrounding thecharged particle is a layer of solution, which

containssufficient excess of negative ions (principally 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
electric double layer that imparts stability to the 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 Colloids

Peptization is a process by which a coagulated colloid returns to its dispersed state.

Digestion is a process in which a precipitate is heated in the solution from which it was
formed (the mother liquor) and allowed to stand in contact with the solution.

Mother liquor is the solution from which a precipitate was formed.

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 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

COPRECIPITATION
- is a process in which normally soluble compounds are carried out of solution by a
precipitate.

FOUR TYPES OF COPRECIPITATION:

 SURFACE ADSORPTION,
 MIXED-CRYSTAL FORMATION
 OCCLUSION
 MECHANICAL ENTRAPMENT

Surface adsorption and mixed-crystal formation are equilibrium processes, and

occlusion and mechanical entrapment arise from the kinetics of crystal growth.

Surface Adsorption
Adsorption is a common source of coprecipitation and is likely to cause significant
contamination of precipitates with large specific surface areas, that is, coagulated
colloids. Although adsorption does occur in crystalline solids, its effects on purity are
usually undetectable because of the relatively small specific surface area of these solids.

 Adsorption is often the major source of contamination in coagulated colloids but of

no significance in crystalline precipitates.
 In adsorption, a normally soluble compound is carried out of solution on the surface
of a coagulated colloid. This compound consists of the primarily adsorbed ion and
an ion of opposite charge from the counter-ion layer.

Minimizing Adsorbed Impurities on Colloids

The purity of many coagulated colloids is improved by digestion. During this process,
water is expelled from the solid to give a denser mass that has a smaller specific
surface area for adsorption.

SPECIFIC SURFACE AREA is defined as the surface area per unit mass of solid and
usually has the units of square centimeters per gram.

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 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

REPRECIPITATION

A drastic but effective way to minimize the effects of adsorption is reprecipitation. In this
process, the filtered solid is redissolved and reprecipitated. The first precipitate usually
carries down only a fraction of the contaminant present in the original solvent. Thus, the
solution containing the redissolved precipitate has a significantly lower contaminant
concentration than the original, and even less adsorption occurs during the second
precipitation. Reprecipitation adds substantially to the time required for an analysis.

MIXED-CRYSTAL FORMATION

In mixed-crystal formation, one of the ions in the crystal lattice of a solid is replaced by an
ion of another element. For this exchange to occur, it is necessary that the two ions have
the same charge and that their sizes differ by no more than about 5%. Furthermore, the
two salts must belong to the same crystal class.
 Mixed-crystal formation is a type of coprecipitation in which a contaminant ion
replaces an ion in the lattice of a crystal.

The extent of mixed-crystal contamination is governed by the law of mass action and
increases as the ratio of contaminant to analyte concentration increases.
Mixedcrystalformation is a particularly troublesome type of coprecipitation because little
can be done about it when certain combinations of ions are present in a sample matrix.
This problem occurs with both colloidal suspensions and crystalline precipitates. When
mixed-crystal formation occurs, the interfering ion may have to be separated before the
final precipitation step. Alternatively, a different precipitating reagent that does not give
mixed crystals with the ions in question may be used.

Occlusion and Mechanical Entrapment

Occlusion is a type of coprecipitation in which a compound is trapped within a pocket

formed during rapid crystal growth.

Mechanical entrapment occurs when crystals lie close together during growth. Several
crystals grow together and in so doing trap a portion of the solution in a tiny pocket.

 Mixed-crystal formation may occur in both colloidal and crystalline precipitates, but
occlusion and mechanical entrapment are confined to crystalline precipitates.

GRAVIMETRIC METHODS OF ANALYSIS 7

 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

COPRECIPITATION ERRORS

Coprecipitated impurities may cause either negative or positive errors in an analysis.

1. If the contaminant is not a compound of the ion being determined, a positive error
will always result.
2. In contrast, when the contaminant does contain the ion being determined, either
positive or negative errors may occur.

 Coprecipitation can cause either negative or positive errors.

PRECIPITATION FROM HOMOGENEOUS SOLUTION

HOMOGENEOUS PRECIPITATION is a process in which a precipitate is formed by

slow generation of a precipitating reagent homogeneously throughout a solution.
Local reagent excesses do not occur because the precipitating agent appears gradually
and homogeneously throughout the solution and reacts immediately with the analyte. As
a result, the relative supersaturation is kept low during the entire precipitation. In general,
homogeneously formed precipitates, both colloidal and crystalline, are better suited for
analysis than a solid formed by direct addition of a precipitating reagent.

 Solids formed by homogeneous precipitation are generally purer and more easily
filtered than precipitates generated by direct addition of a reagent to the analyte
solution.
 In contrast, when these same products are produced by homogeneous generation
of hydroxide ion, they are dense, are easily filtered, and have considerably higher
purity.
 Hydrous oxide precipitates of aluminum formed by direct addition of base and by
homogeneous precipitation with urea. Homogeneous precipitation of crystalline
precipitates also results in marked increases in crystal size as well as
improvements in purity.

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 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

REPRESENTATIVE METHODS BASED ON PRECIPITATION BY

HOMOGENEOUSLY GENERATED REAGENTS

Thermogravimetric Analysis- Recording thermal decomposition curves

Thermograms- mass versus temperature curves
Gravimetric Factor- Combined constant factors in a gravimetric calculation
Chelates- products by chelating agent

- Cyclical metal-organic compounds in which the metal is a part of one or more five or six
members

GRAVIMETRIC METHODS OF ANALYSIS 9

 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

APPLICATIONS OF GRAVIMETRIC METHOD

Gravimetric methods
– have been developed for most inorganic anions and cations, as well as for such
neutral species as water, sulfur dioxide, carbon dioxide, and iodine.
– do not require a calibration or standardization step (except coulometry)
– method of choice when only one or two samples are to be analyzed because it
requires less time and effort than a procedure that requires preparation of
standards and calibration.
– most widely applicable of all analytical procedures
Organic substances that can be determined gravimetrically:
 lactose in milk products
 salicylates in drug preparations
 phenolphthalein in laxatives
 nicotine in pesticides
 cholesterol in cereals, and
 benzaldehyde in almond extracts
INORGANIC PRECIPITATING AGENTS

* These reagents typically form slightly soluble salts or hydrous oxides with the analyte
GRAVIMETRIC METHODS OF ANALYSIS 10
 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

– Boldface type indicates that gravimetric analysis is the preferred method for the
element or ion. The weighed form is indicated in parentheses.
– † A dagger indicates that the gravimetric method is seldom used. An underscore
indicates the most reliable gravimetric method.
REDUCING AGENTS
– reagents that convert an analyte to its
elemental form for weighing.

ORGANIC PRECIPITATING AGENTS

– are significantly more selective in their
reactions than are most of the
inorganic reagents

2 TYPES OF ORGANIC REAGENTS

1. One forms slightly soluble nonionic products called Coordination compounds
2. One forms products in which the bonding between the inorganic species and the
reagent is largely ionic

Chelating Agents
• Organic reagents that yield sparingly soluble coordination compounds typically
contain at least two functional groups
• Each of these functional groups is capable of bonding with a cation by donating a
pair of electrons
• The functional groups are located in the molecule such that a five- or six-
membered ring results from the reaction
Chelates
– products of chelating agents
Metal chelates
– are relatively nonpolar and, as a consequence, have solubilities that are low in
water but high in organic liquids.
– these compounds possess low densities and are often intensely colored.

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 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

Widely used chelating reagents

8-Hydroxyquinoline

Dimethylglyoxime

Sodium tetraphenylborate

ORGANIC FUNCTIONAL GROUP ANALYSIS

GRAVIMETRIC METHODS OF ANALYSIS 12

 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

VOLATILIZATION GRAVIMETRY
Two most common methods are those for determining water and carbon dioxide
Ex.
Determination of the sodium hydrogen carbonate content of antacid tablets.

1. This reaction is carried out in a flask connected first to a tube containing CaSO4
that removes water vapor from the initial reaction stream to produce a stream of
pure CO2 in nitrogen.
2. These gases then pass through a weighed absorption tube containing the
absorbent Ascarite II,8 which consists of sodium hydroxide absorbed on a
nonfibrous silicate. This material retains carbon dioxide by the reaction
2NaOH + CO2 Na2CO3 + H2O
3. The absorption tube must also contain a desiccant such as CaSO4 to prevent loss
of the water produced by this last reaction.
4. Hydrogen sulfide or sulfur dioxide evolved from the sample after treatment with
acid is collected in a suitable absorbent.
5. Finally, the classical method for the determination of carbon and hydrogen in
organic compounds is a gravimetric volatilization procedure in which the
combustion products (H2O and CO2) are collected selectively on weighed
absorbents. The increase in mass serves as the analytical variable.

GRAVIMETRIC METHODS OF ANALYSIS 13

 Republic of the Philippines
Cagayan State University
College of Allied Health Sciences
Andrews Campus ,Caritan Tuguegarao City, Cagayan

GRAVIMETRIC METHODS OF ANALYSIS 14