Gravimetric Analysis

Determination of Sulfur in Soluble

Sulfate

Hans Del Mundo

Teresa Dacalanio

GRAVIMETRY
gravimetric analysis
Is a quantitative methodbased upon
determining themass of a pure compound
to which the analyte is related
is one of a few analytical methods that do
not require standard solutionsas the
weight of precipitate is the only important
parameter in analyte determination

Types of Gravimetric Methods

1. Precipitation method
. the analyte is separated from a solution of
the sample as a precipitate and is
converted to a compound of known
composition that can be weighed

2. Volatilization method
the analyte is separated from other
constituents of a sample by conversion to
a gas of known chemical composition
the weight of this gas then serves as a
measure of the analyte concentration

Steps in Gravimetric Analysis

1.Preparation of the Solution:
- 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.

2.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, then nucleation
(formation of smallest molecules which can grow
into a large precipitate) starts to occur
(Induction period the time between mixing and
the appearance of precipitate)
- at this point, addition of extra precipitating agent
will either form new nuclei or will build up on
existing nuclei to give a precipitate.

-Von Weimarn ratio states thatthe particle size is

inversely proportional to a quantity called the
relative supersaturation

- 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:

a. Precipitation using dilute solutions to decrease

Q
b.Slow addition of precipitating agent to keep Q
as low as possible
c.Stirring the solution during addition of
precipitating agent to avoid concentration sites
and keep Q low
d. Increase solubility by precipitation from hot
solution
e.Adjust the pH in order to increase S but not a
too much increase as we do not want to loose
precipitate by dissolution
f.Usually add a little excess of the precipitating

3. 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 reprecipitation on larger ones resulting in
particle
growth
and
better
precipitate
characteristics. This process is calledOstwald
ripening.

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
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

4.Washing and Filtering the

Precipitate:
- the precipitate should be washed very well in order to
remove all adsorbed species which will affect the weight if
the precipitate
- should be careful not to use too much water since part of
the precipitate may be lost
- in case of colloidal precipitates we should not use water
as a washing solution since peptization would occur
instead, dilute nitric acid, ammonium nitrate, or dilute acetic
acid may be used

 It is a good practice to check for the presence of

precipitating agent in the filtrate of the final washing
solution because presence of precipitating agent means
that extra washing is required.

5. Drying and Ignition:

- the purpose of drying (heating at about 120-150oC
in an oven) or ignition at temperatures ranging from
600-1200oC is to get a material with exactly known
chemical structure and remove moisture and
volatile electrolytes
- this is done until the precipitate reaches a
constant weight

6. Weighing the Precipitate:

- the precipitate is preferred to be weighed in an
analytical balance for a more accurate result

7. Calculating the Results:

- the result of a gravimetric determination is usually
reported as a percentage of analyte:
% analyte = weight of analyte x 100 %
weight of sample

 The precipitate is seldom the analyte itself, but a

definite relationship between the two exists.
This relationship is called gravimetric factor
and is used to convert the known weight of the
precipitate to the corresponding weight of the
analyte

Impurities in Precipitates
1. Coprecipitation
. This is anything unwanted which precipitates with
the desired precipitate
. Coprecipitation occurs to some degree in every
gravimetric analysis (especially barium sulfate
and those involving hydrous oxides).
. Cannot be avoided - all you can do is minimize it
by careful precipitation and thorough washing.

2. Surface adsorption

when ion layers are not removed from the

precipitate
Unwanted material is adsorbed onto the surface
of the precipitate.
Digestion of a precipitate reduces the amount of
surface area and hence the area available for
surface adsorption.
Washing can also remove surface material.

3. Occlusion
This is a type of coprecipitation in which
impurities are trapped during particle growth. The
trapped materials can be water, analyte ions,
precipitating agent ions, or other constituents in
the medium.

4. Postprecipitation
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.

EXPERIMENTAL

Objectives
1) Determine the constant weight of a
precipitate.
2) Precipitate SO3 in a sample as BaSO4.
3) Calculate the % of SO3 in a sample from
the weight of barium sulfate.

The sample should be dried in an oven at 100 OC to 120OC. Weigh out accurately 0.3
g of sample and dissolve it in about 200 mL of distilled water and 1 mL of
concentrated hydrochloric acid. Prepare a 5 % solution of barium chloride by
dissolving 2.5 g of BaCl22H2O in 50 mL water. Calculate the volume of this solution
required to precipitate the sulfate in each sample, including a 10% excess. Measure
this volume of solution into a clean beaker using a graduated cylinder.
Weight of Sample A: 0.3086 g
5% BaCl2 solution:

. 2H

g BaCl2

208.227 g

. 2H

= 2.9327 g BaCl2

1 mol BaCl2

. 2H

2O x

1 mol BaCl2

244.267 g
2O

2O in 50 mL solution

MW of Sample A (XSO4): 132.14 g/mol

g BaCl2

. 2H
. 2H

2O = 2.5 g BaCl2 x 1 mol BaCl2 x 1 mol BaCl2

XSO4 + BaCl2 -> XCl2 + BaSO4

2O = 0.3086 g x 1 mol A x 1mol SO4 2- x 1 mol Ba 2+ x

132.14 g

. 2H

x 1 mol BaCl2

2O

1 mol Ba 2+

244.267 g

1 mol BaCl . 2H

1 mol BaCl2

. 2H

= 0.57046 g BaCl2

1mol SO4 2-

1 mol A

1 mol BaCl2

2O

2O

mL BaCl2 solution = 0.57046 g BaCl2. H2O x 50 mL BaCl2 solution

2.9327 g BaCl2. H2O
= 9.7258 mL BaCl2 solution
10 % excess: 9.7258 mL x 1.1 = 10.6984 mL BaCl2 solution
Heat both sample solution and the solution of barium chloride nearly to boiling. Pour
the hot barium chloride solution quickly but carefully into the hot sample and stir
vigorously. Allow the precipitate to settle and test the supernatant liquid for
completeness of precipitation by adding a few more drops of barium chloride
solution.

After precipitation is complete, cover the beaker with a watch glass and allow the
precipitate to digest for 30 minutes, keeping the solution hot (80 to 90 OC) on a
steam bath, on a hot plate, or using a low flame.

Collect the precipitate using a funnel with filter paper (the slow type Whatman
No.42 should be used unless the precipitate has been unusually well digested, in
which case No. 40 may suffice).

Clean, rinse and heat to constant weight three crucibles and lids of the ordinary
porcelain. Use the highest temperature of the Tirrill burner.
Trial

Mass (Crucible w/ cover)

33.0255 g

33.0241 g

22.0232 g

22.0221 g

-----------

The solution must be hot at the

time of filtration. Decant the clear
supernatant solution through the
filter. Discard the clear filtrate so
that if the precipitate later runs
through the filter paper, only a
small volume need to be refiltered.

Then rinse the precipitate into the funnel with hot water. Remove any precipitate
from the walls of the beaker and rinse such particles into the filter paper with hot
water. If the filtrate is cloudy, it must be refiltered, in which case, the second
passage generally clears it up. Continue to rinse the precipitate in the filter paper
with hot water until a drop of silver nitrate solution added to a test portion of the
washings collected in a test tube shows that chloride is absent.

After washing is complete, transfer the paper and precipitate carefully to the
previously prepared crucible. Dry the precipitate slowly over a low flame or oven.
Then, increasing the heat, char the paper carefully and finally burn it off completely.
Ignite the precipitate for about 20 min at the highest temperature of the Tirrill
burner. The crucible should be uncovered and in a slanted position for free access
of air to prevent reduction of barium sulfate to barium sulfide.

Cool and weigh the crucible and its contents; then reignite for a second 20-min
period. Repeat this procedure until constant weight is attained.

Weight of precipitate = (Constant Weight of crucible + precipitate)

(Constant Weight of empty crucible)
Theoretical weight of precipitate: 0.1636 g (for Sample A)

Sulfur is usually reported as sulfur trioxide. Calculate the percentage of sulfur

trioxide in the unknown sample and report the results.

g SO3 = 0.3086g A x 1mol A x 1mol SO3 x 80.065g SO3

132.14g A 1mol SO4 1mol SO3
= 0.1870g SO3
% (w/w) SO3 = g SO3 x 100 %
g sample
= (0.1870g / 0.3086 g) x 100 %
= 60.60% SO3

Discussion
Slightly excess precipitating agent (BaCl2) was
used in order to ensure complete precipitation.
The precipitate was allowed to digest for 30
minutes in order to dissolve small particles and
reprecipitate larger ones for better precipitate
characteristics and easier filtration.
Heating the crucibles to constant weight ensures
the absence of impurities for a more accurate
measurement of the weight if the precipitate
later.
When washing the precipitate, it is important to
test the washings with AgNO3 solution to ensure
the absence of chloride ion that can affect the
weight of the precipitate.

Recommendations
Manage your time wisely most especially because of the
weighing part.
Be careful in handling the heated crucible and dont
touch it with your bare hands.
While forming the precipitate, add slowly the precipitating
agent and stir the solution vigorously to have a low
supersaturation ratio, thus to have a good precipitate.

References
Skoog, D., West, D., Holler, F.H., & Crouch, S. (2004)
Fundamentals of Analytical Chemistry 8th ed. USA
http://www.chem.tamu.edu/class/majors/tutorialnotefiles/gra
vimetric.htm
http://www.monzirpal.net/Chem
%202310/Contents/Gravimetric_Analysis.htm#_Steps_in_a
http://www.csudh.edu/oliver/demos/gravsulf/hhgrvslf.htm