Dr.

Puspendra Kumar

GRAVIMETRIC ANALYSIS
PRECIPITATION TECHNIQUES
Precipitation method is a process of weighing an element in form of precipitates which is
separated by filtration from solution.
Factors affecting on precipitation method:
• Precipitates must be free from soluble impurities
• Precipitates must be insoluble in solution
• Precipitates must be readily separated from the solution by filtration
• Precipitates must be convertible into a pure compound by ignition or by simple
evaporation
Example: Gravimetric analysis of a sulphate or halides
Na2SO4 + BaCl2 → BaSO4 + NaCl
NaCl + AgNO3 → AgCl + NaNO3

THE COLLOIDAL STATE

Colloids are mixtures of solvent and suspended particles. Particles are too small to see but are
larger than molecules. Due to their small size they do not settle out of solution.
There are several types of colloid:
• Aerosol (gas + liquid or solid, e.g. fog and smoke),
• Foam (liquid + gas, e.g. whipped cream),
• Emulsion (liquid + liquid, e.g. milk),
• Sol (liquid + solid, e.g. paint),
• Solid foam (solid + gas, e.g. marshmallow),
• Solid emulsion (solid + liquid, e.g. butter),
• Solid sol (solid + solid, e.g. pearl).

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S. No. Dispersed Phase Continuous Phase Name

1. Gas Liquid Foam

2. Gas Solid Foam

3. Liquid Gas Aerosol

4. Liquid Liquid Emulsion

5. Liquid Solid Gel

6. Solid Gas Aerosol

7. Solid Liquid Sol

8. Solid Solid Solid sol

Properties of Colloids
• Brownian motion
Zig- zag movement of colloidal particles in a colloidal sol.

• Tyndall Effect (Reflection and light scattering)

Tyndall Effect is the ability of a Colloid to scatter light. The beam of light can be seen
through the colloid.

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Removal of Colloidal Particles

• Colloid particles are too small to be separated by physical means (e.g. filtration).
• Colloid particles are coagulated (enlarged) until they can be removed by filtration.
Methods of coagulation:
• Heating
eating (colloid particles move and are attracted to each other when they collide);
• Adding an electrolyte (neutralize the surface charges on the colloid particles).
• Dialysis: using a semipermeable membranes separate ions from colloidal particles.

Lyophilic colloids (solvent attracting) (solvent loving)

The particles in a lyophilic system have a great affinit
affinity for the solvent.
• If water is the dispersing medium, it is often known as a hydrosol or hydrophilic.
• readily solvated (combined chemically or physically, with the solvent) and dispersed,
even at high concentrations.
• Prepared simply by dissolving the material in the solvent being used e.g. dissolution of
acacia in water.
• Examples of lyophilic sols include sols of gum, gelatin, starch, proteins and certain
polymers (rubber) in organic solvents.
Lyophobic (solvent repelling)
ling) (solvent hating)
The particles resist solvation and dispersion in the solvent.
• The concentration of particles is usually relatively low.
• These colloids are easily precipitated on the addition of small amounts of electrolytes,
by heating or by shaking

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• Less stable as the particles surrounded only with a layer of positive or negative charge
• Once precipitated, it is not easy to reconstitute the sol by simple mixing with the
dispersion medium. Hence, these sols are called irreversible sols.
• Examples of lyophobic sols include sols of metals and their insoluble compounds like
sulphides and oxides. e.g. gold in water
Comparison of Solutions, Colloidal Dispersion & Suspensions
S. No. Solutions Colloidal Dispersions Suspensions
1. All particles are on Particles of at least one Particles of at least one
the order of atoms, component are large clusters of component may be
ions, or small atoms, ions, or small molecules, individually seen with a
molecules (0.1-1 nm) or are very large ions or low- power microscope
molecules (1-1000 nm) (over 1000 nm)
2. Most stable to Less stable to gravity Unstable to gravity
gravity
3. Most homogeneous Also homogeneous, but Homogeneous only if well
borderline stirred
4. Transparent (but Often translucent or opaque, but Often opaque but, may
often colored) may be transparent appear translucent

5. No Tyndall effect Tyndall effect Not applicable (suspensions

cannot be transparent)
6. No Brownian Brownian movement Particles separate unless
movement system is stirred
7. Cannot be separated Cannot be separated by filtration Can be separated by
by filtration filtration
8. Homogeneous

to
Heterogeneous

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SUPERSATURATION
Supersaturation can be achieved by adding more of a substance (to a solution) than can normally
be dissolved. This is a thermodynamically unstable state.
Zone 1 - Metastable zone.
• The solution may not nucleate for a long time but this zone
zone will sustain growth. It is
frequently necessary to add a seed crystal.
Zone 2 - Nucleation zone.
• Crystals nucleate and grow.
Zone 3 - Precipitation zone.
• Precipitate out in the solution.

• For low supersaturation primary nucleation is not widespread. Secondary nucleation

on existing crystals is more likely. Result is small numbers of large crystals
• For high supersaturation primary nucleation is widespread. This results in many
crystals of small size.
• Slow cooling with llow supersaturation creates large crystals
• Fast cooling from high supersaturation creates small crystals
• Agitation reduces crystal size by creating more dispersed nucleation
• Rate of cooling can affect purity of product.
product

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CO-PRECIPITATION
Co-precipitation is the carrying down by a precipitate of substances normally soluble under the
conditions employed.
In gravimetric analysis, which consists on precipitating the analyte and measuring its mass to
determine its concentration or purity, coprecipitation is a problem because undesired impurities
often coprecipitate with the analyte, resulting in excess mass. This problem can often be
mitigated by "digestion" (waiting for the precipitate to equilibrate and form larger, purer
particles) or by redissolving the sample and precipitating it again.
There are three main mechanisms of coprecipitation: inclusion, occlusion, and adsorption. An
inclusion occurs when the impurity occupies a lattice site in the crystal structure of the carrier,
resulting in a crystallographic defect; this can happen when the ionic radius and charge of the
impurity are similar to those of the carrier. An adsorbate is an impurity that is weakly bound
(adsorbed) to the surface of the precipitate. An occlusion occurs when an adsorbed impurity gets
physically trapped inside the crystal as it grows.

STEPS INVOLVED IN GRAVIMETRIC ANALYSIS.

In this technique, the analyte is converted to an insoluble form which can then be washed, dried,
and weighed in order to determine the concentration of the analyte in the original solution.
Gravimetry is applied to samples where a good precipitating agent is available.
The precipitate should be quantitative, easily washed and filtered and is of in suitable quantity
for accurate weighing. Therefore, gravimetry is regarded as a macro analytical technique.
Gravimetry is one of a few analytical methods that do not require standard solutions as the
weight of precipitate is the only important parameter in analyte determination.
Steps in a Gravimetric Analysis
After appropriate dissolution of the sample the following steps should be followed for successful
gravimetric procedure:
Preparation of the Solution:
This may involve several steps including adjustment of the pH of the solution in order for the
precipitate to occur quantitatively and get a precipitate of desired properties, removing
interferences, adjusting the volume of the sample to suit the amount of precipitating agent to be
added.

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Precipitation:
This requires addition of a precipitating agent solution to the sample solution. Upon addition of
the first drops of the precipitating agent, supersaturation occurs, and then nucleation starts to
occur where every few molecules of precipitate aggregate together forming a nucleous. At this
point, addition of extra precipitating agent will either form new nuclei or will build up on
existing nuclei to give a precipitate. This can be predicted by Von Weimarn ratio where,
according to this relation the particle size is inversely proportional to a quantity called the
relative supersaturation where
Relative Supersaturation = (Q – S)/S
The Q is the concentration of reactants before precipitation, S is the solubility of precipitate in
the medium from which it is being precipitated. Therefore, in order to get particle growth instead
of further nucleation we need to make the relative supersaturation ratio as small as possible.
The optimum conditions for precipitation which make the supersaturation low are:
• Precipitation using dilute solutions to decrease Q
• Slow addition of precipitating agent to keep Q as low as possible
• Stirring the solution during addition of precipitating agent to avoid concentration sites
and keep Q low
• Increase solubility by precipitation from hot solution
• Adjust the pH in order to increase S but not a too much increase as we do not want to
loose precipitate by dissolution.
• Usually add a little excess of the precipitating agent for quantitative precipitation and
check for completeness of the precipitation
Digestion of the Precipitate:
The precipitate is left hot (below boiling) for 30 min to 1 hour in order for the particles to be
digested. Digestion involves dissolution of small particles and re-precipitation on larger ones
resulting in particle growth and better precipitate characteristics. This process is called Ostwald
ripening. An important advantage of digestion is observed for colloidal precipitates where large
amounts of adsorbed ions cover the huge area of the precipitate. Digestion forces the small
colloidal particles to agglomerate which decreases their surface area and thus adsorption. You
should know that adsorption is a major problem in gravimetry in case of colloidal precipitate
since a precipitate tends to adsorb its own ions present in excess; Therefore forming what is

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called a primary ion layer which attracts ions from solution forming a secondary or counter ion
layer. Individual particles repel each other keeping the colloidal properties of the precipitate.
Particle coagulation can be forced by either digestion or addition of a high concentration of a
diverse ions strong electrolytic solution in order to shield the charges on colloidal particles and
force agglomeration. Usually, coagulated particles return to the colloidal state if washed with
water, a process called peptization.
Washing and Filtering the Precipitate:
It is crucial to wash the precipitate very well in order to remove all adsorbed species which will
add to weight of precipitate. One should be careful nor to use too much water since part of the
precipitate may be lost. Also, in case of colloidal precipitates we should not use water as a
washing solution since peptization would occur. In such situations dilute nitric acid, ammonium
nitrate, or dilute acetic acid may be used. Usually, it is a good practice to check for the presence
of precipitating agent in the filtrate of the final washing solution. The presence of precipitating
agent means that extra washing is required. Filtration should be done in appropriate sized Goosh
or ignition filter paper.
Drying and Ignition:
The purpose of drying (heating at about 120-150 oC in an oven) or ignition in a muffle furnace at
temperatures ranging from 600-1200 oC is to get a material with exactly known chemical
structure so that the amount of analyte can be accurately determined.
Precipitation from Homogeneous Solution:
In order to make Q minimum we can, in some situations, generate the precipitating agent in the
precipitation medium rather then adding it. For example, in order to precipitate iron as the
hydroxide, we dissolve urea in the sample. Heating of the solution generates hydroxide ions from
the hydrolysis of urea. Hydroxide ions are generated at all points in solution and thus there are no
sites of concentration. We can also adjust the rate of urea hydrolysis and thus control the
hydroxide generation rate. This type of procedure can be very advantageous in case of colloidal
precipitates.
Impurities in Precipitates
Occlusion: Some constituents of the precipitation medium may be trapped in the crystal
structure resulting in positive or negative errors. The trapped materials can be water, analyte
ions, precipitating agent ions, or other constituents in the medium. Slow addition of precipitating

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agent and stirring may avoid occlusion but if it does occur, dissolution of precipitate and
repracipitation may have to be done.
Inclusion: If the precipitation medium contains ions of the same charge and size as one forming
the crystal structure of the precipitate, this extraneous ion can replace an ion from the precipitate
in the crystal structure. For example, in the precipitation of NH4MgPO4 in presence of K+
ammonium leaves the crystal magnesium ammonium phosphate and is replaced by K+ since both
have the same charge and size. However, the FW fro NH4+ is 18 while that of K+ is 39. In this
case a positive error occurs as the weight of precipitate will be larger when K+ replaces NH4+. In
other situations we may get a negative error when the FW of the included species is less than the
original replaced species.
Surface Adsorption: This always result in positive errors in gravimetric procedures. See
previous discussion on colloidal precipitates.
Post-precipitation: In cases where there are ions other than analyte ions which form precipitates
with the precipitating agent but at much slower rate then analyte, and if the precipitate of the
analyte is left for a long time without filtration then the other ions start forming a precipitate over
the original precipitate leading to positive error. Examples include precipitation of copper as the
sulfide in presence of zinc. Copper sulfide is formed first but if not directly filtered, zinc sulfide
starts to precipitate on the top of it. The same is observed in the precipitation of calcium as the
oxalate in presence of magnesium.
Gravimetric Calculations
The point here is to find the weight of analyte from the weight of precipitate. We can use the
concepts discussed previously in stoichiometric calculations but let us learn something else.
Assume Cl2 is to be precipitated as AgCl, then we can write a stoichiometric factor reading as
follows: one mole of Cl2 gives 2 moles of AgCl. This is in fact what is called the gravimetric
factor (GF) where we can substitute for the number of moles by grams to get:
GF for Cl2 = 1 mol Cl2/2 mol AgCl = FW Cl2/2 FW AgCl = x g analyte/y g precipitate
Weight of substance sought = weight of precipitate x GF
One can also consider the problem by looking at the number of m moles of analyte in terms of
the m moles of the precipitate where for the precipitation of Cl2 as AgCl, we can write
Cl2 = 2 AgCl
mmol Cl2 = 1/2 mmol AgCl

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(mg Cl2/FW Cl2) = 1/2 (mg AgCl/FW AgCl)

FILTER PAPERS
Filter paper is a semi-permeable paper barrier placed perpendicular to a liquid or air flow. It is
used to separate fine solids from liquids or air.
Ashless filter paper is mainly used for gravimetric methods in quantitative chemical analysis. It
has a base weight of 80 g/m2.
CRUCIBLES
A crucible is a container that can withstand very high temperatures. While crucibles historically
were usually made from clay, they can be made from any material that withstands temperatures
high enough to melt or otherwise alter its contents.
A crucible is a cup-shaped piece of laboratory equipment used to contain chemical compounds
when heated to extremely high temperatures. Crucibles are available in several sizes and
typically come with a correspondingly-sized crucible cover (or lid).
When heated over a flame, the crucible is often held inside a pipeclay triangle which itself is held
on top of a tripod.
Crucibles and their covers are made of high temperature-resistant materials, usually porcelain,
alumina or an inert metal. One of the earliest uses of platinum was to make crucibles. Ceramics
such as alumina, zirconia, and especially magnesia will tolerate the highest temperatures. More
recently, metals such as nickel and zirconium have been used. The lids are typically loose-fitting
to allow gases to escape during heating of a sample inside. Crucibles and their lids can come in
high form and low form shapes and in various sizes, but rather small 10–15 ml size porcelain
crucibles are commonly used for gravimetric chemical analysis. These small size crucibles and
their covers made of porcelain are quite cheap when sold in quantity to laboratories, and the
crucibles are sometimes disposed of after use in precise quantitative chemical analysis.

THERMOGRAVIMETRIC ANALYSIS
Measures changes in weight in relation to changes in temperature.
The measured weight loss curve gives information on:
• Changes in sample composition.
• Thermal stability

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• Kinetic parameters for chemical reactions in the sample

A derivative weight loss curve can be used to tell the point at which weight loss is most apparent
Example: Decomposition of calcium oxalate monohydrate
Sample size: 1 – 100 mg (typically 5 – 20 mg)
Heating / cooling rate: 1 – 50 ºC / min
Calcium oxalate monohydrate, a standard material often used to demonstrate TGA perfor
performance.
Exhibits three weight losses with temperature in an inert atmosphere (e.g. N2)

Decomposition of calcium oxalate monohydrate

Absolute confirmation of the decomposition process is possible when the gaseous by products
are identified as they evolve, eg. by mass spectrometry (MS).
Common gaseous components originating from inorganic materials that decomposes before the
melting point:
H2O, CO, CO2, SOx, NOx, Cl2, F2, CH3OH etc.

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Factors affecting the TG curve

• Heating rate (Increases the temperature at which sample decomposition occurs.)
• Sample size
• Particle size of sample (Affects the progress of the reaction)
• Packing
• Crucible shape
• Gas flow rate
ORGANIC PRECIPITANTS
• There are several inorganic ions that can be precipitated by adding organic reagents
and these are called organic precipitants. Most of them combine with cations to form
chelate rings.
• Molecular weights of organic pecipitants are generally high. Hence, the molecular
weights of the corrsponding chelate compounds are also high.Thus, even a small
amount of metal gives relatively greater amounts of precipitates.So, it is possible to
analyse much smaller quantities of metals.
Requirements to precipitants:
• It is desirable, that a precipitant was volatile compound.
• A precipitant should be specific – to precipitate a defined ion in the presence of
others ions.
• Organic precipitants: Dimethylgloxime, Oxalic acid, α-nitrozo-β-naphtol, Cupferron,
Cupron, Sodium tetraphenylborate, Nitron.
• Inorganic precipitants: Alkalis or ammonia, Hydrogen sulphide or sulphides,
Sulphatic acid, Phosphatic acid
Advantage of organic precipitants
• Solubility of precipitate with organic precipitants is less.
• Precipitates with organic reagents are crystal.
• Precipitates with organic reagents are more pure as on their surface impurity are less
adsorbed.
• Organic precipitant have higher selectivity and specificity.

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• The gravimetric factor at definition with organic reagents on much less so, accuracy of
definition increases.

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