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gravimetry lecture ppt final

Gravimetric analysis is a quantitative method in analytical chemistry that determines the mass of an analyte through precipitation, isolation, and weighing of the resulting product. The process involves several steps including solution preparation, precipitation, filtration, washing, drying, and weighing, with careful attention to the properties and purity of the precipitate. Various methods such as precipitation, volatilization, and electrogravimetry are employed to separate the analyte, ensuring accurate measurement and minimal contamination.
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0% found this document useful (0 votes)
323 views87 pages

gravimetry lecture ppt final

Gravimetric analysis is a quantitative method in analytical chemistry that determines the mass of an analyte through precipitation, isolation, and weighing of the resulting product. The process involves several steps including solution preparation, precipitation, filtration, washing, drying, and weighing, with careful attention to the properties and purity of the precipitate. Various methods such as precipitation, volatilization, and electrogravimetry are employed to separate the analyte, ensuring accurate measurement and minimal contamination.
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Gravimetric Analysis

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

3. 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.
Steps Involved in Gravimetric Analysis

1. Preparation of the solution

2. Precipitation

3. Digestion of the precipitate

4. Filtration

5. Washing

6. Drying and ignition

7. Weighing

8. Calculation
1. Preparation of the solution/Dissolution

• 1st step – Sampling; Representative of bulk


• 2nd step - prepare the analyte 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.

Adding additional inert ions decreases the thickness of the secondary


adsorption layer. Because the particles can approach each other more closely,
they are able to coagulate.
3. Digestion of precipitate

Advantage- Digestion forces the small colloidal particles to


agglomerate which decreases their surface area and thus
adsorption.
4. Filtration of precipitate
• The precipitate is separated from the mother liquor.
• Filter paper classified according to its speed, its size, and its ash
content on ignition.
• Speed, or how quickly the supernatant passes through the filter
paper, depend on paper’s pore size.
• A larger pore – pass supernatant more quickly through the filter
paper, but does not retain small particles of precipitate.
Fast paper - retains particles larger than 20–25 mm,
Medium-fast - retains particles larger than 16 mm,
Medium - retains particles larger than 8 mm
Slow - retains particles larger than 2–3 mm.
• If the filtering speed is too fast, we may fail to retain some of the
precipitate, causing a negative determinate error.
• If speed is too slow- the precipitate may clog the pores.
• Filtration medium used are
– Filter papers
– Filter pulps
– Filter mats
– Crucible fitted with porous plate (Sintered
glass filters)
– Crucible to be used at high temperature
Proper procedure for transferring the
supernatant to filter paper cone
An alternative method is use of a filtering crucible.
example-
1. Fritted-glass crucible containing a porous glass disk filter.
Classified according to their porosity:
a) coarse- retaining particles larger than 40–60 mm
b) medium -retaining particles greater than 10–15 mm
c) fine - retaining particles greater than 4–5.5 mm

2. Gooch crucible - is a porcelain crucible with a perforated


bottom.
A glass fiber mat is placed in the crucible to retain the
precipitate.
Gooch crucible

Heating upto 250 °C

Glass Fibre disc

Platinum Crucible
Heating upto 500 ° C
Silica Crucible
Drying upto 1000 °C

Sintered Glass Crucible


Heated upto 200 °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

• After filtering the precipitate, the impurities on the surface


of the precipitate can be removed by washing.
• Precipitate washed to remove all adsorbed species that
would add to the weight of the precipitate.
• Washed with too much water, 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.
• Electrolytes like dilute nitric acid, ammonium nitrate, or
dilute acetic acid may be used.
• Checking of presence of precipitating agent in the filtrate of
the final washing solution is essential.
• Loss of analyte is minimized by using several small
portions of rinse solution instead of a single large
volume.
• Testing the used rinse solution for the presence of
impurities is another way to guard against over
rinsing the precipitate.
• For example,
• Presence of Cl– , a residual ion in the supernatant,
can be tested using AgNO3.
• After collecting a small portion of the rinse solution,
we add a few drops of AgNO3 and look for the
presence or absence of a precipitate of AgCl. If a
precipitate forms, then we know that Cl– is present
and continue to rinse the precipitate.
6. Drying & Ignition
– The purpose is to get a material with exactly known chemical
structure so that the amount of analyte can be accurately
determined.
Heating at about- 120-150 °C in an oven
Ignition - at 600-1200 in a muffle furnace
– Precipitate is dried to remove residual traces of rinse solution
and any volatile impurities.
– The temperature and method of drying depend on the
method of filtration and the precipitate’s desired chemical
form.
– Fritted-glass crucibles- dried in an oven at temperatures
below 200 °C.
– The glass fiber mats used in Gooch crucibles can be heated to
a maximum temperature of approximately 500 °C.
• Precipitate must be in suitable form for
weighing.
• Precipitate must be pure, stable, of certain
known composition.
• Remove water efficiently; electrolytes in
washing solvent.
• Appropriate chemical changes during heating.
• A constant weight must be obtained- achieved
when the process of heating, cooling and
weighing is repeated.
7. Weighing & calculation
• In the usual gravimetric analysis, the precipitate is weighed
and from this value the weight of the analyte in the sample is
calculated with the help of a gravimetric factor.
• After the precipitate is allowed to cool (preferably in a
desiccator to keep it from absorbing moisture), it is weighed
(in the crucible).
Purity of Precipitate
• Precipitate must be free from impurities
• When the ppt is separated out from solution it is always
not preferably pure and may be contaminated even
after washing.
• Source of impurity- chemical & physical interactions
occur at precipitate surface.
• The amount of impurities depends on nature of
precipitate and condition of precipitation.
• Explain by two concepts-
1. Coprecipitation 2. Post precipitation
Coprecipitation… (simultaneous precipitation of
impurities with main analyte from the solution.)

• Co-precipitation means incorporation of foreign ions into a


ppts having a common ion or an ion of identical size or charge
with any ion of the ppt.
• Unwanted/undesired species co-precipitated along with your
analyte of interest; resulting in excess mass of the final
product.
• Occurs to some degree in every gravimetric analysis;
• Observed in precipitations of barium sulfate and those
involving hydrous oxides
How problem overcome ?
• Cannot be avoided but can be minimized by careful
precipitation and a thorough washing of the precipitate.
1. Surface
adsorption

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)

Desorption- is the process in which the adsorbed


ion from the surface of the precipitate enter into
the solution.
Factors affecting adsorption-desorption

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)

• In which one of the ions in the crystal lattice of the solid is


replaced by an ion of another element.
• Two compounds are isomorphs – it means same type of
formula and crystallize in similar geometric forms & same
lattice dimensions.
• Example- In the precipitation of Mg2+ as magnesium
ammonium phosphate, K+ has nearly same ionic size as
NH4+ and can replace it to form magnesium potassium
phosphate
• If such change should occur, then both the ions must have
the same charge and their sizes must not differ by more
than about 5%.
Inclusion
• It is trapping of impurities with in the crystal lattice.
• A potential interfering ion whose size and charge is
similar to a lattice ion, may substitute into the lattice
structure, & this interferent precipitates with the same
crystal structure
• The probability of forming an inclusion is greatest when
the concentration of the interfering ion is substantially
greater than the lattice ion’s concentration.
• Inclusion is difficult to remove since it is chemically part
of the precipitate’s lattice.
• The only way to remove an inclusion
is through reprecipitation.
• After isolating the precipitate from
its supernatant solution,
• Dissolve it by heating in a small
portion of a suitable solvent.
• Then allow the solution to cool,
reforming the precipitate.
• Because the interferent’s
concentration is less than that in the
original solution, the amount of
included material is smaller.
3. Occlusion
• When a crystal is growing rapidly during
precipitate formation, foreign ions/impurities
in the counter-ion layer trapped, or occluded,
within the growing crystal.
• occlusion is localized within the precipitate’s
lattice structure.
How to minimize occlusions ?
• By maintaining the precipitate in equilibrium
with its supernatant solution for an extended
time. This process is called a digestion
4. Mechanical Entrapment
• occurs when the crystals lie close together during growth.
• several crystals grow together and in so doing trap a portion of the
solution in a tiny pocket.

• 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

• A shorter period of digestion particularly under warm


condition is to be carried out.
• The ppt. Should be filtered as quickly as possible so
that the ppt does not remain in contact with a
mother–liquor for a long time
Sr. no Co-precipitation Post-precipitation
1 It occurs because impurities are It occurs in second stage. When
present in solution in soluble precipitation is left for longer
form. It occurs easier during time in mother liquor.
isolation of precipitation of
analyte.
2 Increases with agitation of Decreases with agitation of
solution solution
3 Decreases if precipitation digest Increases if precipitation digest
for longer time at elevated for longer time at elevated
temperature temperature
4 The extent of contamination is The extent of contamination is
high low
5 Ex- contamination of BaSO4 by Ex-Contamination of Ca.oxalate
KMNO4 impurities whiich is by Mg as it reacts slowly with
present in solution in the oxalic acid
soluble form
Gravimetric Estimation of Barium
Objective: To estimate the amount of barium in the whole of
the given solution of barium chloride.

The Gravimetric Estimation of Barium:


The given barium chloride solution is made up to a definite volume. A
measured volume of it is then treated with dilute sulphuric acid and
barium precipitated as barium sulphate.

The precipitated barium sulphate is separated and weighed. The mass


of Barium in the whole of the given solution is calculated knowing that
233.36 g of barium sulphate contains 137.36 g of barium.
Procedure:
1. The given barium chloride solution is made up to 100mL in a standard flask.
2. 20mL of solution is pipetted into a 250 mL beaker.
3. About 5mL 2N HCl is added and diluted to 150mL with distilled water.
4. The solution is heated to boiling and a hot solution of 4N H2SO4 (10 - 15mL) is added
drop by drop with constant stirring, till the precipitation is complete.
5. The solution containing the precipitate is heated in a water bath for 5 minutes.
6. The precipitate is allowed to stand for an hour.
7. The clear solution is decanted through an ashless filter paper (whatman No. 40).
8. The precipitate is washed with hot distilled water to free sulphate ions.
9. The particles adhering to the sides of the beaker and glass rod are removed by a
policeman.
10. Finally the precipitate is washed once again.
11. The dried filter paper is folded and placed in a crucible which has been previously
weighed.
12. The filter paper with the precipitate is first incinerated on a Bunsen burner by a low
flame and then transferred to an electric burner.
13. The crucible is transferred to desiccator and cooled.
14. When cold, the crucible is weighed.
15. Heating, cooling and weighing are repeated till concordant values are obtained.
Calculation:
• Mass of crucible + lid = a g

• Mass of crucible + lid + Bariumsulphate = b g

• Mass of Bariumsulphate = (b-a) g.

• 233.36 of barium sulphate contain 137.36 g of barium.

• Mass of barium in (b-a) g of Bariumsulphate =

• Therefore, Mass of Barium in the whole of the given solution =


Result:

• Mass of Barium in the whole of the given solution = ------------ g.


Advantages of Gravimetric Analysis
• Accurate and precise
• Possible sources of errors can be checked:
Gravimetric analysis avoids problems with
temperature fluctuations, calibration errors, and
other problems associated with volumetric analysis.
• It is an ABSOLUTE method.
• Relatively inexpensive
Disadvantages
✓Proper lab technique is critical
✓Careful and time consuming.
✓Scrupulously clean glassware.
✓Very accurate weighing.
✓Coprecipitation.

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