gravimetry lecture ppt final
gravimetry lecture ppt final
Gravi - metric
(weight - measure)
By
Dr. Ms. Priyanka Chaudhari
What is Gravimetric Analysis ?
• Gravimetric analysis is a method used in in analytical
chemistry for the quantitative determination of an
analyte (the ion being analyzed) based on its mass.
• Gravimetric analysis is a process of precipitation,
isolation and weighing of the isolated product. It is
mainly based on the measurement of the analyte.
• For example- Quantitative determination of
progesterone in progesterone injection.
• Measuring the solids suspended in the water sample –
Once a known volume of water is filtered, the collected
solids are weighed.
• From the weight & the chemical content , the weight of
the analyte in the sample can then be calculated.
• Gravimetric analysis is based on conversion of
ions/elements/radicals into a stable and pure compound through
precipitation, which can be directly weighed and quantified.
• Principle:
• The sample is dissolved in a solvent and then the precipitating
agent is added.
• Followed by the formation of the precipitate, it is filtered through
the filter paper.
• The obtained precipitate is commonly known as residue. This
residue is dried and weighed.
• For example
• Soluble sodium chloride is estimated by converting them into
insoluble silver chloride by adding silver nitrate reagent. The
precipitate of the silver chloride is isolated, purified and weighed.
The principle and theory involved in the gravimetric
analysis are the following:
I. Law of Mass Action and reversible reaction.
II. Principle of solubility product.
III. Common ion effect.
The separation of the sample is carried out by the following principle
methods: The methods involve changing the phase of the analyte to
separate it in its pure form from the original mixture and are
quantitative measurements
1. Precipitation gravimetry-
Analyte must first be converted to a solid (precipitate) by
precipitation with an appropriate reagent. The precipitates from
solution is filtered, washed, purified (if necessary) and weighed.
2. Volatilization gravimetry-
The analyte is separated from other constituents of a sample by
conversion to a gas . Analyte or its decomposition products are
volatilised (dried) and then collected and weighed The weight of this
gas then serves as a measure of the analyte concentration
2. Precipitation
4. Filtration
5. Washing
7. Weighing
8. Calculation
1. Preparation of the solution/Dissolution
• May need :
– preliminary separation to separate potential
interferences before precipitating analyte
–proper adjustment of solution condition i. e.
pH/temp/vol/conc of test substance, to maintain low
solubility of precipitate & max precipitate formation.
Eg Calcium oxalate insoluble in basic medium
2. Precipitation
• When a solution of precipitating agent is
added to sample solution, precipitate is form.
e.g NaCl + AgNO3 AgCl + NaNO3
• Proper choice of precipitant is based on the
specificity of reagent.
The precipitate formed during the analysis may be in
crystalline, curdy, gelatinous etc.
crystalline precipitate are in well shape as function of
composition of salt. (BaSO4)
Curdy precipitate are aggregates of small porous
particles.(AgCl) Gelatinous precipitates are jelly like and very
difficult to separate out.(Al(OH)3)
Properties of precipitates:
1. The precipitate formed should be insoluble.
2. The physical nature of the precipitate should
be such that it can be easily removed by filtration.
1. The precipitate should be stable to atmospheric
temperature. Unreactive to atm constituents.
2. Sufficiently low solubility i.e no significant loss of
analyte occur during filtration & washing.
3. The precipitate should be convertible to pure
compound of definite composition.
4. Should have constant known composition after drying
5. Have large crystals (easily filtered)
6. Be free of contaminants.
Mechanism of Precipitation
• The purity and filterability of the precipitate depends
upon the particle size of the precipitate.
• Precipitates form in two ways, by nucleation and by
particle growth.
A- Induction
• The time before nucleation occurs after the
addition of the precipitating agent to the solution
• May range from milliseconds to several minutes
B. Nucleation
• Is a process in which individual atoms, ions or
molecules join together to give a stable solid nuclei.
• It occurs after induction
• A small aggregates or nuclei of an atoms form.
• Excess ions from solution collect around the nuclei
• The nucleation can be spontaneous where it occurs on
its own or induced using a seed particle to get
nucleation
✓ Precipitation involves a competition between
additional nucleation and growth on existing nuclei
(particle growth).
✓ If nucleation predominates, a precipitate containing a
large number of small particles results; if growth
predominates, a smaller number of larger particles is
produced.
Mechanism of Precipitation
• In addition to the primary adsorbed silver ions, some
nitrate ions form an electrostatic layer around the
nucleus.
• These counter ions tend to aggregate around the
[AgCl:Ag]+ center because these centers have a net
positive charge (excess Ag+) and additional negative
charge is required to maintain electrical neutrality.
• Counter ions are less tightly held than the primary
adsorbed ions and the counter ion layer is somewhat
diffuse and contains ions other than those of the
counter ions.
• These layers of charged ions associated with the
surface of the nuclei are known as the electric double
layer.
C. Crystal growth
• Nuclei join together to form a crystal of a
certain geometric shape.
• After nucleation, growth occurs. large nuclei
grow at expense of smaller nuclei which
dissolve.
• More easily filtered large crystals are formed
Particle Size and Filterability of Precipitates
• Solubility of a precipitate increases with decreasing
particle size.
• Large particle size of precipitate is preferred.as as
easy to filter & washing to remove impurities
• It is pure.
Colloidal suspension Crystalline suspension
➢ Size range- 10-6 – 10-4 mm ➢ Size range- 10-1 – 10 mm
➢ Tiny particles, invisible to ➢ Large particles
naked eyes ➢ Well settle spontaneously
➢ No tendency to settle ➢ Readily filtered
➢ Difficult or impossible to ➢ High purity than colloids
filter
Curdy precipitate
Crystalline precipitate
Gelatinous precipitate
Supersaturation- more than maximum amount of
dissolved solute
Controlling Particle size
A measure of relative supersaturation or supersaturation ratio(RS)
• If RS high- get excessive nucleation,
lots of small crystals,
large surface area
• If RS low- get larger,
fewer crystals,
small surface area
• Experimental variables that minimize supersaturation and thus
lead to Crystalline precipitates include -
• Increase S- elevated temperatures to increase the solubility of
the precipitate
• Minimise Q- dilute solutions , Slow addition of the precipitating
agent with good stirring.
• Larger particles can also be obtained by pH control, provided the
solubility of the precipitate depends on pH
Colloidal Precipitates
• Colloidal suspensions are stable because all the
particles present are either positively or
negatively charged. This charge results from
cations or anions that are bound to the surface of
the particles. The process by which ions are
retained on the surface of a solid is known as
adsorption.
• Coagulation of Colloids:-
• Coagulation can be speed up by heating, stirring,
and adding an electrolyte to the medium.
(a) Coagulation does not happen due to the electrostatic
repulsion between the two positively charged particles.
Two methods for coagulating a precipitate of AgCl
(b) Decreasing the charge within the primary adsorption layer, by adding
additional NaCl, decreases the electrostatic repulsion, allowing the particles to
coagulate.
Platinum Crucible
Heating upto 500 ° C
Silica Crucible
Drying upto 1000 °C
Porcelain Crucible
Sintered Glass
Crucible
Fast Medium Slow
Speed Speed speed
No.31 No.30 No.32
No.41 No.40 No.42
No.54 No.52 No.52
5. Washing the precipitate
2.
Mechanism
Inclusion
4.Mechanical of co-
Entrapment precipitation or Mixed
crystal
formation
3.
occlusion
1. Surface adsorption
• Is a common source of co-precipitation
• Unwanted material is adsorbed onto
the surface of the precipitate.
• It causes significant contamination of the
precipitates having large surface area-coagulated
colloids.
• Large surface area in the precipitate---more
adsorption—more impurities
• Coagulation of a colloid does not significantly
decrease the
• amount of adsorption
How to minimize adsorption ?
The adsorption process can be overcome by the
desorption (reversible process)
Effect of
Effect of
concentrati
temperature
on
Effect of
Effect of
nature of
precipitatio
adsorbed
n condition
ion
Minimizing adsorbed impurities
• Decreasing the precipitate’s available surface area.
• How ?-
• Digestion of a precipitate reduces it.
• It increases purity of coagulated colloids. Washing with
solution of volatile impurities may also helpful.
• It increases the average particle size.
• Because the probability of a particle completely
dissolving is inversely proportional to its size, during
digestion larger particles increase in size at the expense
of smaller particles.
• Washing can remove impurities bound to the surface.
Reprecipitation
✓ Double precipitation.
✓ Here, the filtered solid is redissolved and
reprecipitated.
✓ The first precipitate ordinarily 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.
• Another type of impurity is an interferent that forms an
independent precipitate under the conditions of the
analysis.
• For example, --the precipitation of nickel
dimethylglyoxime requires a slightly basic pH. Under
these conditions, any Fe3+ in the sample precipitates
as Fe(OH)3.
• We can minimize the formation of additional
precipitates by carefully controlling solution conditions.
• If an interferent forms a precipitate that is less soluble
than the analyte’s precipitate, we can precipitate the
interferent and remove it by filtration, leaving the
analyte behind in solution.
• Alternatively, we can mask the analyte or the
interferent to prevent its precipitation
2. Inclusion/ Mixed Crystal Formation
(Isomorphous replacement)
• How to overcome ?
• Mechanical entrapment is low when the rate of precipitate
formation is slow
• Digestion also helpful
• The rapid solution and reprecipitation that goes on at the
• elevated temperature of digestion opens up the pockets and allows
the impurities to escape into the solution.
Precipitation from Homogeneous Solution
• Precipitation from homogeneous solution is a technique in
which a precipitating agent is generated in a solution of
the analyte by a slow chemical reaction.
• 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.
Post Precipitation
• Sometimes when the precipitate is allowed to stand in
presence of mother liquor the second substance will
form the precipitate with the precipitating reagent.
• The process by which an impurity is deposited after the
precipitation of the analyte (desired substance) is
termed as post precipitation. Longer the precipitate
remain in the mother liquor solution, greater is the
chance for post precipitation.
• Example : if Mg2+ is present as an impurity along with
Ca2+ , then there during the synthesis of calcium
oxalate, there are chances of the post precipitation of
Magnesium oxalate.
• This can be avoided by maintaining a high pH.
• In this case, as the name suggests the primary precipitate separates
out in a pure form and the second phase of the foreign substance
which is slightly soluble forms afterwards.
• The second phase is therefore, not coprecipitated but
postprecipitated.
• Postprecipitation can occur only when the supernatant is
supersaturated, with respect to some component which crystallizes
fairly slowly.
• Example-
• H2S is passed through a 0.2 N H2SO4 solution containing Cu2+ ions
and a little amount of Zn2+ ions.
• Copper sulphide will precipitate first without carrying zinc. Means
no any coprecipitation.
• If the precipitated copper sulphide is left with zinc ions in solution
zinc sulphide is precipitated at the copper sulphide precipitate.
To avoid postprecipitation