UNIT III

GRAVIMETRIC ANALYSIS
Content:
1. Introduction
2. Principle
3. Types of Gravimetric Analysis
4. Steps involved in gravimetric analysis
5. Purity of precipitates: Co-precipitation and post precipitation
6. Applications of Gravimetry analysis
7. Estimation of barium sulphate

1. Introduction:
Gravimetric analysis was discovered by Theodore W. Richard at Harvard.
Definition: Gravimetric analysis or quantitative analysis by weight can be defined as a
technique of isolating and weighing an element or compound in its pure form.
Gravimetry is among the most accurate analytical techniques (but it is tedious). T. W.
Richards used it to determine atomic weights. He received the Nobel Prize in 1914 for his
work. Gravimetric analysis is one of the most accurate and precise methods of macro-
quantitative analysis.
Advantages of Gravimetric Analysis:
 Accurate and precise: Gravimetric analysis is potentially more accurate and more
precise than volumetric analysis.
 Gravimetric analysis avoids problems with temperature fluctuations, calibration
errors, and other problems associated with volumetric analysis.
 It is an absolute method i.e. it involves direct measurements without any form of
calibration.
Disadvantages
There are potential problems with gravimetric analysis that must be avoided to get good
results.
 Proper lab technique is critical
 Careful and time consuming
 Very clean glassware
  Very accurate weighing
 Co-precipitation
2. Principle:
In this process the analyte is selectively converted to an insoluble form. The separated
precipitate is dried or ignited, possibly to another form, and is accurately weighed. From the
weight of the precipitate and knowledge of its chemical composition, we can calculate the
weight of analyte in the desired form.

Fig.1: Gravimetric analysis apparatus

Principles and theories of gravimetric analysis are as stated below:
(i) Law of mass action and reversible reactions
(ii) Principle of solubility product, and
(iii) Common ion effect
3. Types of Gravimetric Analysis:
There are four types of gravimetric methods;
3.1. Precipitation method and
3.2. Volatilization method
3.3. Electrogravimetry
3.4. Thermogravimetry
3.1. Precipitation method:
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.
 Fig.2: Precipitation method in gravimetry
1) Weighing the sample to be analyzed
2) Dissolving the weighed sample in water
3) Addition of suitable precipitation reagent to form precipitate
4) Filtration and washing to collect the precipitate
5) Drying and weighing
Example for Precipitation: Calcium can be determined gravimetrically by precipitation of
calcium oxalate and ignition of the oxalate ion to calcium oxide.
Ca2+ + C2O42-→ CaC2O4
CaC2O4 → CaO + CO2 + CO
The precipitate thus obtained is weighed and the mass of calcium oxide is determined.
3.2. Volatilization method:
In this method the analyte or its decomposition products are volatilized (dried) and then
collected and weighed. Alternatively, the mass of the volatilize product is determined
indirectly by the loss of mass of the sample.

Fig.3: Volatilization method in gravimetry

Example for Volatilization: Water can be separated from most inorganic compounds by
ignition. The evolved water can then be absorbed on any one of several solid desiccants. The
weight of water evolved may be calculated from the gain in weight of the absorbent. Not all
insoluble precipitates are well suited for gravimetric analysis.
3.3. Electrogravimetry
It is a method used to separate and quantify ions of a substance, usually a metal. In this
process, the analyte solution is electrolyzed. Electrochemical reduction causes the analyte to
be deposited on the cathode. The mass of the cathode is determined before and after the
experiment, and the difference is used to calculate the mass of analyte in the original solution.
Controlling the potential of the electrode is important to ensure that only the metal being
analyzed will be deposited on the electrode.

Fig.4: Electrogravimetry assembly

The process is similar to electroplating.
3.4. Thermogravimetry:
Thermogravimetric is a method of thermal analysis in which changes in physical and
chemical properties of materials are measured as a function of increasing temperature or as a
function of time.

Fig.5: Principle of thermogravimetry

4. Steps in a Gravimetric Analysis:
4.1. Preparation of the solution
4.2. Precipitation
4.3. Digestion
4.4. Washing and Filtration
4.5. Drying or ignition
4.6. Weighing
4.7. Calculation
4.1. Preparation of analyte solution:
Gravimetric analysis usually involves precipitation of analyte from solution. To prepare the
analyte solution, this may need:
 Preliminary separation to separate potential interferences before precipitating analyte
 Adjustment of solution condition (pH/temp/volume/concentration of test substance) to
maintain low solubility of precipitate& maximum precipitate formation. Example:
Calcium oxalate insoluble in basic Medium
 Most of the substances are readily soluble in water and can be used as such.
 Some required special treatment as treatment with HCl, HNO3, Aqua regia or fusing
with basic flux.
4.2 Precipitation process:
The precipitating reagent is added at a concentration that favors the formation of a good
precipitate. This may require low concentration, extensive heating (often described as
"digestion"), or careful control of the pH. A large excess precipitating reagent should be
avoided because this increases chances of adsorption on ppt. Test for completeness of
precipitation. No new precipitate should be formed after addition of drop of precipitating
agent.
4.3. Digestion of the precipitate:
Let precipitate stand in contact with mother liquor (the solution from which it was
precipitated). This process is called digestion, or Ostwald ripening. The small particles tend
to dissolve and precipitate on the surfaces of the larger crystals. Digestion make larger
crystals reduce surface contamination, reduce crystals imperfection.
4.4. Washing and Filtration:
Washing helps remove the co-precipitated impurities specially the occluded and surface
adsorbed. The precipitate will also be wet with the mother liquor which is also removed by
washing. Colloidal precipitates cannot be washed with pure water, because peptization
occurs. This is the reverse of coagulation. Note that: colloidal precipitates have double layer
of adsorbed primary and counter ions. The presence of another electrolyte during
precipitation will cause the counter ions to be forced into closer contact with primary layer,
thus promoting coagulation. Washing with water will dilute and remove foreign ions and the
counter ion will occupy a larger volume, with more solvent molecules between it and the
primary layer. This can be prevented by adding an electrolyte to the washing liquid. E.g.
HNO3 is used to wash AgCl. This electrolyte should be volatile at the temperature of drying
or ignition and must not dissolve the precipitate.
4.5. Drying or Ignition:
After filtration, a gravimetric precipitate is heated until its mass becomes constant. Drying at
110 to 120 °C for 1-2 hours is conducted. If the collected precipitate is in a suitable form for
its weighing (known, stable composition), it must be heated to remove water and to remove
adsorbed electrolyte from the wash liquid. Ignition (strong heating) at much higher
temperature is usually required if a precipitate must be converted to a more suitable form for
weighing. In this case, the weighed form of the precipitate might be different from the
precipitated form.

Fig.6: Glass crucible Porcelain crucible Ashless filter paper

4.6. Weighing:
The precipitate cannot be weighed with the necessary accuracy in place on the filter paper;
nor can the precipitate be completely removed from the filter paper in order to weigh it. The
precipitate can be carefully heated in a crucible until the filter paper has burned away; this
leaves only the precipitate. (As the name suggests, "ashless" paper is used so that the
precipitate is not contaminated with ash.) . If you use Goosh crucible then after the precipitate
is allowed to cool (preferably in a desiccator to keep it from absorbing moisture), it is
weighed (in the crucible). The mass of the crucible is subtracted from the combined mass,
giving the mass of the precipitated analyte. Since the composition of the precipitate is known,
it is simple to calculate the mass of analyte in the original sample.
4.7. Calculation:
The results of a gravimetric analysis are generally computed from two experimental
measurements : the weight of sample and the weight of a known composition precipitate .The
precipitate we weigh is usually in a different form than the analyte whose weight we wish to
find . The principles of converting the weight of one substance to that of another depend on
using the stoichiometric mole relationships. We introduced the gravimetric factor(GF), which
represents the weight of analyte per unit weight of precipitate. It is obtained from the ratio of
the formula weight of the analyte to that of the precipitate, multiplied by the moles of analyte
per mole of precipitate obtained from each mole of analyte, that is,
5. Purity of precipitates:
An analyte compound that forms when precipitating reagents are added to a solution is
measured using the precipitation gravimeter. It is true thatmost gravimetric methods, which
generate precipitates as part of a metathesis reaction, can be used for analyzing samples by
gravimetry. Nevertheless, a gravimetric method could work with any reaction producing
precipitate. In the nineteenth century and earlier, many precipitationsgravimetric methods
were developed, often to analyze ore. A total analysis method typically provides better than
0.1% accuracy, which means that the analyte is represented by 99.99% of the precipitate.
Asthe requirement is extended to 99.99% of a precipitate's solubility, gravimetric analysis
accuracy will not be impeded. Some factors affecting the purity of the precipitates are
described below.
Co-precipitation:
Co-precipitation occurs to some degree in every gravimetric analysis (especially barium
sulfate and those involving hydrous oxides).This is a type of precipitation characterized by
the elimination of soluble compounds in a solution during precipitation. The term co-
precipitationdescribes a precipitation process where soluble compounds are removed from a
solution as precipitates form. This reaction contains a significantamount of contamination.
Multi-particle precipitation occurs when more than one soluble component evaporates
simultaneously from a singlesolution.Co-precipitation occurs when more than one component
precipitates at the same time. Using co-precipitation, catalysts consisting of more than
onecomponent are easily prepared. Most precipitates that separate from solutions don't
contain pure water but contain a greater amount of foreignsubstances, like mother liquor.
Precipitates may be infected with impurities, depending on their nature and the conditions
from which theyprecipitated. Co-precipitation is the process of contaminating precipitates
with substances that are normally soluble under precipitation conditions. Acompound which
becomes contaminated due to co-precipitation ought to be distinguished from one who
becomes contaminated due to chemicalprecipitation alone. In the presence of barium chloride
and potassium sulfate, co-precipitation is observed when the precipitated potassium
sulfatecontains greater or lesser amounts of barium sulfate, although it is freely soluble in the
given conditions. Reciprocity is primarily carried out throughtwo mechanisms, i.e. the
particles surfaces have an adsorption effect and fixation by the introduction of foreign ions
(and solvents). It can be minimized by careful precipitation and thorough washing.
Co-precipitation can be minimized by;
 Taking dilute and pure solution
 Use double precipitation
 Operations like digestion or aging
 Use of organic solvent
 Slow addition of reagent
 Stirring
 Proper temperature
Post-precipitation:
The term post precipitation describes a type of precipitation in which the undesirable
component precipitates after the desired component hasprecipitated. The term post
precipitation describes a type of precipitation in which the precipitate of the unwanted
compound appears after theprecipitate of the desired compound. This is low-level
contamination. It is the precipitation that forms a layer of precipitate upon that which
alreadyexists.In terms of contamination resulting from foreign materials in a precipitate, co-
precipitation is important. It is also possible to make a precipitate impurethrough a process
known as post precipitation. It appears that a first precipitate of the foreign substance
separates in a pure form and is thenfollowed by a second precipitate of the foreign substance
that is slightly soluble. There is therefore no co-precipitation in the second phase but onlypost
precipitation. During supernatants that are saturated, some components that crystallize very
slowly are liable to undergo post precipitation. Sometimes a precipitate standing in contact
with the mother liquor becomes contaminated by the precipitation of an impurity on top of
the desired precipitate.The process in which precipitation of some component (impurity)
occurs on the surface after its formation is called precipitation. It occurs with sparingly
soluble substances. The longer thee time for precipitate to stand, the greater is the error due to
due to this cause.
Post-precipitation can be minimized by;
 Complex formation
 Change in oxidation state
 Rapid filtration of precipitate
 Concentration of impurities
6. Applications of gravimetry analysis:
 Estimation of ceramic, metallurgic and minealogerical samples
 Analysis of industrial materials and ores
 Estimation of chloride in water, CO2 in water, SO in air
 Determination of gallium, niobium, tantalum, tungsten and many rare earth metals
 Determination of sulphates, chloride silica, iron, chromium and aluminum
 Determination of wood alcohols
 Analysis of thiamine hydrochloride, papaverine hydrochloride, amodiaquine
hydrochloride
 Estimation of gold in sodium aurothiomalate and Aurothioglucose

7. Estimation of Barium sulphate:

Method 1:
Aim & Objectives:
1. To experimentally analyze an unknown sulfate salt via a precipitation reaction, using
the techniques associated with Gravimetric Analysis to collect and weigh the
precipitate, and
2. To calculate the percentage by mass of SO−24 in the unknown sulfate salt via a
stoichiometric analysis of the collected precipitate, and then use this percentage to
identify the metal “M” present in the sulfate salt.
Theory:
The amount of sulphate is determined quantitatively as barium sulphate, BaSO 4 by
gravimetric analysis.
This determination consists of slowly adding a dilute solution of barium chloride to a hot
solution of the sulphate slightly acidified with concentrated HCl.
Ba2+ + SO2-4 ---> BaSO4 ?
The white precipitate is filtered off, washed with water, dried in the oven, and weighed as
barium sulphate. The percentage of sulphate is calculated from the weight of barium sulphate.
Principle:
Sulphate is precipitated as barium sulphate in hydrochloric acid medium by the addition of
barium chloride solution. The reaction is carried out near the boiling temperature. The
precipitate is filtered and washed to remove the chlorides, then dried or ignited and weighed
as BaSO4.
Gravimetric analysis is a quantitative method for accurately determining the amount of a
substance by selective precipitation of the substance from an aqueous solution. The
precipitate is separated from the remaining aqueous solution by filtration and is then weighed.
Assuming that the chemical formula for the precipitate is known and that the precipitation
reaction goes all the way to completion, then the mass of the substance in the original sample
can be determined.
In this experiment, the percentage by mass of sulfate in an unknown sulfate salt will be
determined by gravimetric analysis. First, a pre-weighed sample of the unknown sulfate salt
will be dissolved in water. Next, an excess of aqueous barium chloride is added to the
aqueous solution of the unknown salt. This will result in the precipitation of all the sulfate
ions as barium sulfate:
Metal sulfate (aq) + Barium chloride (aq) ⟶ Barium sulfate (s) + Metal chloride (aq)

The barium sulfate precipitate is collected by filtration, dried and weighed. Since barium
chloride is added in excess, and since the precipitation reaction goes to completion, we can
assume that the entire sulfate is transferred from the original unknown sample to the
precipitate. The mass of sulfate in the collected BaSO 4 precipitate can be calculated via its
percent composition.
This also yields the mass of sulfate in the original unknown since:
Mass of sulfate in the precipitate = Mass of sulfate in the unknown sample

Finally, using the mass of sulfate along with the initial mass of unknown used, the percentage
by mass of sulfate in the original sample may now be calculated.
In order to obtain the best results, the collected BaSO4 crystals should be as large as possible.
This considerably aids the filtration process (larger crystals are less likely to be pass through
the filter paper), and it also minimizes the amount of impurities adsorbed onto the crystals
(smaller surface area).
In general, larger crystals are obtained when the rate of precipitation is as low as possible.
The rate of precipitation is minimized by slowly adding the BaCl2 solution to the aqueous
mixture containing the unknown salt while continuously stirring the mixture. The rate of
precipitation can be decreased even further by slightly increasing the solubility of the BaSO4.
This may be achieved by lowering the pH with 6M HCl and by increasing the temperature.
The resulting decrease in the yield of the BaSO4 is insignificant.
Chemicals: Unknown solid sulfate salt, 6M HCl, solution and 0.1 M BaCl2 solution
Equipment: 250-mL beaker, analytical balance, stirring rod, 100-mL graduated cylinder,
stand with ring clamp, wire screen, Bunsen burner, wash bottle with distilled water, crucible
and lid, crucible tongs, ash-less filter paper, large funnel, 500-mL Erlenmeyer flask, clay
triangle
Procedure and instructions:
 Weigh a clean, dry 250-mL beaker to the nearest 0.001 g using the analytical balance, and
record this mass on your lab report. Next, add 0.30 – 0.35 grams of your unknown sample
to the beaker. Record the combined mass of the beaker plus sample on your lab report.
 Add 50 mL of distilled water, followed by 20 drops of 6 M HCl(aq), to the sample in the
beaker. Stir the contents of the beaker until the sample has entirely dissolved. Leave the
stirring rod in the beaker.
 Obtain a stand with a ring clamp from the back of the lab. Place your wire screen on the
ring and the beaker containing your dissolved sample on the wire screen. Use the Bunsen
burner to heat the solution until it is nearly (but not quite) boiling. Turn the Bunsen burner
off before the solution boils. While heating the solution, measure out 25 mL of 0.1 M
BaCl2 (aq) using a 100-mL graduated cylinder. The graduated cylinder used should be
clean (rinse with distilled water) but does not need to be dry.
 Slowly add small portions of BaCl2 (aq) to the beaker containing the hot solution. You
should observe the formation of a white precipitate of BaSO4 (s). Stir the contents of the
beaker as you add the BaCl2 solution. The addition of the BaCl2 must be performed very
slowly – this step should take you at least 3 minutes to complete! When finished, rinse any
precipitate that remains on the stirring rod into the solution with a small amount of distilled
water, and then allow the precipitate to settle in the beaker for about 20 minutes.
 While the precipitate settles, prepare your crucible by heating it in the hottest part of the
Bunsen burner flame for about 2 minutes (use the crucible tongs, cradling the crucible as
demonstrated by the instructor – never pick up a crucible by pinching the walls). Repeat
with the lid. Place the hot crucible and lid on the metal base of the stand to cool. Once they
have cooled to room temperature weigh the crucible without the lid using the analytical
balance, and record this mass on your lab report. You do not need to weigh the lid.
 Obtain a piece of ash-less filter paper from your instructor and fold it into quarters. Open
the folded paper into a cone and place it into your large funnel. Wet the filter paper with a
small amount of distilled water so that it adheres to the funnel. Sit the funnel in the mouth
of a 500-mL Erlenmeyer flask, which will be used to collect the filtrate.
 After 20 minutes has passed, slowly pour the mixture containing the BaSO4 precipitate
down your stirring rod into the funnel. Be careful that the level of liquid in the funnel is
never more than three-fourths of the way to the top of the filter paper. When the transfer is
complete use your wash bottle (filled with distilled water) to rinse the residual precipitate
from the beaker and the stirring rod into the funnel.
 After all the liquid has drained from the funnel, wearing gloves very carefully press the top
edges of the filter paper together, and gently fold the filter paper into a compact package
that will fit into the crucible. It is important that you do not use too much force in order to
avoid tearing the filter paper. Place the folded filter paper into the crucible.
 Take your stand, ring clamp and Bunsen burner over to a fume hood. Place your clay
triangle on the ring and the crucible in the clay triangle for support. Gently heat the crucible
without the lid to remove the water. Once the paper appears to be dry (after several
minutes), heat the crucible more vigorously so that the filter paper begins to char (turning
from white, to brown, to black) – but not so vigorously that the filter paper bursts into
flame. If the filter paper bursts into flame you should cover it with the crucible lid to put out
the flame, then reduce the amount of heat and remove the lid. Continue to heat moderately
with the lid off until all of the filter paper has turned black.
 Once all the filter paper has turned black, vigorously heat the crucible without the lid in the
hottest part of the Bunsen burner flame so that the bottom of the crucible is red hot. The
center of the flame should now be directly on the crucible. The charred filter paper (carbon)
will gradually combust and be converted into CO2 gas. When the filter paper is entirely
combusted only the white BaSO4 should remain in the crucible. Continue to heat the
crucible vigorously until no charred filter paper remains. This should take 5 - 10 minutes.
 Allow the crucible to cool to room temperature (this takes at least 5 minutes). Weigh the
crucible without the lid and its contents on the analytical balance. Record this mass.
Place the crucible and its contents back in the clay triangle and heat vigorously with the lid
off for an additional 5 minutes. Then allow it to cool again and reweigh the crucible and its
contents without the lid. If the mass is within 0.005 grams, then record this mass on your lab
report. If the mass has decreased by more that 0.005 grams, then either the BaSO4 is still wet
or not all of the filter paper has combusted and you should repeat this step until you achieve a
consistent mass, making sure the crucible is in the hottest part of the flame.
Discard the BaSO4 in the proper waste container, then clean up as directed by your instructor.
Pre-laboratory Assignment: Gravimetric Analysis
Suppose that 0.323 g of an unknown sulfate salt is dissolved in 50 mL of water. The solution
is acidified with 6 M HCl, heated, and an excess of aqueous BaCl2 is slowly added to the
mixture resulting in the formation of a white precipitate.
1. Assuming that 0.433 g of precipitate is recovered calculate the percent by mass of
SO2−4 in the unknown salt.
2. If it is assumed that the salt is an alkali sulfate determine the identity of the alkali
cation.
(a) Preparation of porcelain Gooch crucible
1. Dry the porcelain, Gooch crucible in the oven at 110 - 120oC for 30 minutes.
2. Cool it in the desiccator.
3. Weigh the crucible, together with a piece of filter paper.
4. Repeat the above until constant weights are obtained.
Caution: Do not place the hot crucible directly on the bench top.
(b) Precipitation of BaSO4
1. Pipette 25 mL of the given sulphate solution into a 250 mL beaker.
2. Add 5 drops of concentrated HCl and about 50 mL of water.
Caution: Concentrated HCl is very corrosive, add in the fume hood.
3. Heat to boiling and, with vigorous stirring, add dropwise from a measuring cylinder 10
mL of 10% barium chloride solution.
4. Cover the beaker with a watch glass and digest (heat to just below boiling) for 20
minutes.
5. Test for complete precipitation by adding a few drops of BaCl2 to the clear supernatant
liquid.
(c) Washing and Filtration of BaSO4 precipitate
1. Decant the clear supernatant by filtration (use a weighed filter paper) at the vacuum
pump, using a pre-weighed crucible.
2. Wash and swirl the precipitate with about 20 mL of warm deionised water.
3. Use a 'rubber-policeman' to dislodge any particles on the beaker.
4. Allow to settle.
5. Decant the liquid through the filter paper.
 6. Repeat the washing and decanting at least 2 more times.
7. Discard the filtrate.
(d) Drying and weighing of BaSO4 precipitate
1. Dry the crucible in the oven at 150oC for about 1/2 hour.
2. Cool the crucible with BaSO4 precipitate in a desiccator for about 10 minutes.
3. Weigh the crucible when it is cooled down.
4. The difference between this weight and the empty crucible (plus filter paper) is the
weight of BaSO4 precipitate.
(Note: You may repeat Steps 1 to 4 until a constant weight of the precipitate is obtained.)
Calculations and Conclusions
Mass of empty 250-mL beaker
Mass of 250-mL beaker and unknown sulfate
Mass of unknown sulfate
Mass of empty crucible (without lid)
Mass of crucible (without lid) and barium sulfate
Mass of barium sulfate

1. Calculate the mass of sulfate in the unknown sample. Clearly show each step of your
calculation.
2. Calculate the percentage by mass of sulfate in the unknown sample.
3. Calculate the percentage by mass of the metal in the unknown sample.
Conclusion:
It can be deduced that the aims of the experiment were met out as expected. The mass of the
sulphate was found to be………
Method 2:
Aim & Objectives:
 To determine the amount of sulphate in an unknown sulfate sample
 To perform and develop skills in precipitation Gravimetric method of qualitative
analysis
Solution and Chemical:
 1+1HCl,
 0.05M BaCL2,
 0.1MHNO3,
 AgNO3 ,
 Unknown sample,
 Warm water
Apparatus:
 400ml beaker,
 10ml and 200ml measuring cylinder,
 Stirring rod,
 Heating plate,
 Desiccator,
 Analytical balance,
 Filter paper,
 Vacuum pump compressor
Introduction:
Gravimetric includes all analytical methods in which the analytical signal is a measurement
of mass or change in mass. There are four types of gravimetric method:
1. Precipitation gravimetry
2. Electrogravimetry
3. Volatilization gravimetry
4. Particular gravimetry
In precipitation gravimetry an insoluble compound forms when we add a precipitating
reagent or precipitant to a solution containing the analyte. In most methods the precipitate is
the product of a simple metathesis reaction between the analyte and precipitant, however, any
reaction generating a precipitate can potentially serve as gravimetric method. All
precipitation gravimetric analysis share two attributes.
  Firstly, the precipitate must be of low solubility, of high purity and of known
composition if its mass is to accurately reflect the analytes mass.
 Secondly, the precipitate must be separate from the reaction mixture. To provide
accurate result, solubility must minimal. Sulphate is widely distributed in nature and
may be present in natural water in concentration ranging from a few to several
thousand milligram/liter.
Sulphates are of considerable concern because they are indirectly responsible for two serious
problems often associated with the handling and treatment of water. Odour and sewer
corrosion problem result from the reduction of sulphate hydrogen sulphide under anaerobic
conditions.
Sulphate can be determined by Gravimetric method of with ignition of residue.
Gravimetric method with drying of residue: Gravimetric method with ignition of residue
Sulphate is precipitated in hydrochloric acid medium as barium sulphate by the addition of
barium chloride. The precipitation is carried out near the boiling point temperature and after a
period of digestion, the precipitate is filtered, washed with water until free of chloride, ignited
weighed barium sulphate.
If organic matter is not present in the sample first method can be done without igniting and
instead drying the residue and weighing.
Turbidimetric method: It is method of measuring sulphate is based upon the fact that barium
sulphate tends to precipitate in a colloidal form and that this tendency is enchance in presence
of sodium chloride – hydrochloric acid solution containing glycerol and other organic
compounds. The absorbance of barium sulphate solution is measured by nephelometer or
turbidmeter and the sulphate ion concentration determined by the comparison of the reading
with a standard curve.
Procedure:
250ml of the unknown sample is measured and put into 400ml beaker. Addition of 3ml
1+1HCl is poured into the 400ml beaker containing the unknown sample. The solution is
heated to near boiling point and slowly 80ml of 0.05M BaCl 2 is added with efficient stirring.
The mixture solution is left to digest for about 30minutes near boiling point. Afterward the
solution is allowed to settle for the precipitate to form at the basement. A few drops of BaCl 2
is added to the clear solution at the top of the precipitate check all the sulphate in the solution
is precipitated out. If not additional Bacl2 is added in excess to precipitate the sulphate out.
A filter paper of constant weight and cooled in a desiccator was weighed and its mass noted.
The precipitated BaSO4 was filtered using the weighed filter paper and drained in a suction
pump. The filter paper and the residue (BaSO4) were dried and weighed.
Calculation:
Mass of filter paper= ……………g
Mass of precipitate and fitter paper= ……………g
Mass of precipitate BaSO4 is = (Mass of precipitate and fitter paper - Mass of filter paper)
=XY g

Discussion:
The solution was digested to break the bonds in the unknown sample in order to make the
sulphate in the solution free to precipitate with the BaCl 2 to form BaSO4. The completeness
of the precipitate is check by adding BaCl2 to the clear solution on the surface of the
precipitate if no cloudiness is not form then it indicate that there is no sulphate left out in the
solution. Either wise excess BaCl2 must be added to precipitate the sulphate. The Barium
sulphate precipitate was washed with warm distilled water to free the Cl - ion in the
precipitate. The precipitate freeness of Cl - ion is tested by performing qualitative test of Cl.
This is done by 1ml of 0.1M HNO3 into the filtrate collected during the washing and drops of
Ag NO3 is added in drop wise, if AgCl precipitate is formed then it indicates that the Barium
sulphate precipitate needs further washing . if not the then precipitate and the filter paper is
dried and weighed it mass noted as ……..g HCl was added to the sample solution to prevent
the precipitation of barium salts of weak
Precaution:
1. The precipitate was digested to increase the average particle size and reduce
coprecipitation.
2. BaCl2 was added slowly amidst effective stirring to reduce relative supersaturation.
3. Completeness of the precipitation was tested for after each digestion by adding drops of
BaCl2.
4. The container that contained BaSO4 was washed with warm water to remove the Cl- salt
present. 5. The filter paper and the precipitate were well dried to ensure accurate weight
measurement.
6. The experiment was carried out at a near boiling point temperature to increase the
solubility of the precipitate at equilibrium and reduce relative supersaturation.
Conclusion:
It can be deduced that the aims of the experiment were met out as expected. The mass of the
sulphate was found to be………
 MULTPILE CHOICE QUESTIONS

Q.1. Which analytical method is based on the weight of the PPT?

a) Acid base Titration
b) Complexometric Titration
c) Precipitation titration
d) Gravimetry
Q.2. Which sentence is false about gravimetric analysis?
a) It is used for inorganic ion
b) It is used to assay barium sulphate
c) It is used to assay of aluminium
d) Relative precision 3 to 4%
Q.3. Which sentence is true about a gravimetric analysis?
a) Relative precision 3 to 4%
b) It is expansive method.
c) It is not used to to barium sulphate assay
d) It is used to assay of Al
Q.4. How many types of gravimetric analysis?
a) One
b) Two
c) Three
d) Four
Q.5. Volatilization method is…….
a) Precipitation of solutions
b) Vaporizations of solutions
c) A and B
d) Bone of the above
Q.6. Precipitation method is……
a) Precipitation of solutions
b) Vaporizations of solutions
c) A and B
d) Bone of the above
7. For a gravimetric analysis to be successful.....
a) The ratio of anion to cation in the substance being investigated must be 1:1.
 b) The anion of the substance being investigated must be precipitated.
c) Either the cation or the anion of the substance being investigated must be
precipitated.
d) Both the cation and the anion of the substance being investigated must be
precipitated.
Q.8. Which is incorrect statement for gravimetric?
a) Precipitates must be free from soluble impurities
b) Precipitates must be insoluble in solution
c) Precipitates may not be readily separated from the solution by filtration
d) Precipitates must be convertible into a pure compound by ignition or by simple
evaporation
Q.9. What is the colour of barium sulphate precipitate in the reaction of barium
chloride and sodium?
a) White
b) Brown
c) Black
d) Red
Q.10. What are the steps of gravimetric analysis?
a) Preparation of a solution containing a known weight of the sample
b) Separation of the desired constituent
c) Weighing the isolated constituent
d) All of above
Long Answer Questions:
Q.1. What is gravimetric titration? Explain the principle and applications of precipitation
titration.
Q.2. Explain the steps involved in the Gravimetric analysis in detail.
Short Answer Questions:
1) What is co-precipitation?
2) Explain post-precipitation and how to avoid it?
3) What are the types of gravimetric analysis?
KEY ANSWERS
Q.1. d Q.2. d Q.3. b Q.4. a Q.5. a
Q.6. c Q.7. c Q.8. c Q.9. a Q.10.