Module 4 – GRAVIMETRIC METHOD OF ANALYSIS

Two types of colloids:

Gravimetric analysis 1. hydrophobic - hates water
- is one of the most accurate and precise methods - sometimes called as sol
of macro-quantitative analysis - coagulation leads to curdy precipitate
- in this process, the analyte is selectively ex. AgCl
converted to an insoluble form 2. hydrophilic - loves water
- the separated precipitate is dried or ignited, - viscous in appearance
possibly to another form, and is accurately - coagulation produces gelatinous
weighed precipitate
- from the weight of the precipitate and a ex. Fe(OH)3
knowledge of its chemical composition, the
weight of analyte in the desired form can then be Crystalline suspension –the temporary dispersion of
calculated particles with diameters on the
order of tenths of a millimeter
Steps in Gravimetric Analysis or greater
- with particles that tend to settle
1. Preparation of the solution
spontaneously and are easily
2. Precipitation filtered
3. Digestion
4. Filtration Precipitate formation has been studied for many years, but
5. Washing the mechanism of the process is still not fully understood.
6. Drying/Igniting
7. Weighing What is certain, however, is that the particle size of a
8. Calculation precipitate is influenced by the following variables:
a) precipitate solubility
Ideally, gravimetric precipitating agent should react b) temperature
specifically or at least selectively with the analyte. c) reactant concentrations
Specific reagents - react only with a single d) the rate at which reactants are mixed
chemical species
- are rare The net effect of the above 4 variables can be accounted
Selective reagents-react with a limited number of for, at least qualitatively, by assuming that the particle size
species is related to a single property of the system called as
-are more common relative supersaturation.

In addition, the ideal precipitating reagent would react relative supersaturation = (Q-S)/S ← von
with the analyte to give a product that is: Weimarn ratio
1. easily filtered and washed free of contaminants;
2. of sufficiently low solubility that no significant loss of where Q – the concentration of the solute at any
the analyte occurs during filtration and washing; instant
3. unreactive with constituents of the atmosphere; S – equilibrium solubility
4. of known chemical composition after it is dried or, if
necessary, ignited. And based on experimental evidence, particle size is
inversely proportional to relative supersaturation:
Precipitates consisting of large particles are
Particle Size ∝ 1/Average Relative Supersaturation
- generally desirable for gravimetric work
- easy to filter and wash free of impurities So,
- usually purer than are precipitates that are made up of large (Q-S)/S → many small solid (colloidal)
fine particles → high surface area
→ nucleation predominates
Colloidal suspensions –are tiny particles invisible to the
naked eye (10-7 to 10-4 cm in small (Q-S)/S → fewer but larger crystals (crystalline)
diameter) → low surface area
- show no tendency to settle from → less impurities trapped in the crystals
Solution & are difficult to filter → particle growth predominates
Mechanism of Precipitate Formation • The charge on a colloidal particle formed in a
The effect of relative supersaturation on particle size can gravimetric analysis is determined by the charge of the
be explained if we assume that precipitates form in two lattice ion that is in excess when the precipitation is
ways: complete
a) nucleation → a few ions, atoms, or molecules
ex. When AgNO3 is first added to a solution
(perhaps as few as four or five) come together to
form a stable solid; containing Cl- ion, the colloidal particles are
negatively charged
• Often, these nuclei form on the surface of
→ because at this point, the lattice ion Cl- is in
suspended solid contaminants such as dust
excess
particles
But when an excess AgNO3 has been added
b) particle growth → growth of existing nuclei into
larger solid particles that precipitated out all Cl- then the colloidal
particles are positively charged → since the
Further precipitation is governed by the competition lattice ion Ag+ is in excess
between additional nucleation and growth of existing
nulei.
If nucleation predominates → large no. of small particles
results
If growth predominates → small no. of larger particles
is produced

Thus, the goal during precipitation is:

Source: Properties and Applications of Colloids - ScienceMotive
keep Q low and S high
Electric Double Layer:
1) Primary adsorption layer → attached directly to the
Steps taken to maintain favorable condition for solid surface
precipitation: 2) Counter-ion layer → to just balance the charge on the
1) precipitate from dilute solution (the 2 reagents surface of the particle
should be dilute)
→ this keeps Q low
2) add dilute precipitating agent slowly with stirring
→ this keeps Q low
3) precipitate from hot solution
→ this increases S
4) controlling pH or precipitate at low pH (if
precipitate is moderately soluble in mildly acidic
environment)
→ this increases S
• Precipitates that have very low solubilities, such as
many sulfides and hydroxides, generally form as colloids
ex. Fe(OH)3, Al(OH)3, PbS2, Ag2S Source: Chapter 12: Gravimetric Methods of Analysis - ppt video online
download (slideplayer.com)
• Colloidal suspensions are stable because all of the
particles of the colloids are either positively or
negatively charged and thus repel one another • Colloidal precipitates can be coagulated or
→ charges result from the cations or anions that agglomerated to give filterable, amorphous mass that
are bound or adsorb to the surface of the settle out of solution
particles
Coagulation – the process whereby particles with colloidal
• Lattice (an arrangement in space showing the positions dimensions are caused to form larger
of atoms, molecules, or ions in the structure of a crystal) aggregates
ions are generally more strongly held that others. - can be hastened by heating, stirring, and by
adding an electrolyte to the medium
• Heating - decreases the number of adsorbed ions and resulting to a denser mass, that is, easier to
thus the thickness of the double layer filter
- can cause the particles to also gain enough
Coprecipitation – is a process in which normally soluble
kinetic energy to overcome the barrier to
compounds are carried out of solution by a
close approach imposed by the
precipitate
double layer
- can cause either negative or positive errors
• Addition of a suitable ionic compound or an electrolyte
- increases the concentration of counter-ions in ex. In the determination of Ba by
the vicinity of each particle precipitation as BaSO4 (233.39g/mol),
occluded BaCl2 (208 g/mol) causes a
- decreases the volume of the solution that
negative error since the molar mass of
contains sufficient counter-ions to balance the
charge of primary adsorption layer BaCl2 is less than BaSO4

- shrinkage of the counter-ion as its net effect Four Types of Coprecipitation:

as depicted below a) Surface adsorption- is a process in which a substance
(gas, liquid, or solid) is held on the surface of a
solid
– often the major source of contamination in
coagulated colloids but of no significance in
crystalline precipitates
ex. AgNO3 in AgCl

b) Mixed-crystal formation – a contaminant ion replaces

an ion in the lattice of a crystal
- occurs with both colloidal suspensions and
crystalline precipitate
ex. PbSO4 in BaSO4 (formed from BaCl2
added to a solution
Source: Chapter 12: Gravimetric Methods of Analysis - ppt video online
download (slideplayer.com)
containing SO42-, Pb2+,
C2H3O2-);
MgKPO4 in MgNH4PO4;
Peptization - the process by which a coagulated colloid SrSO4 in BaSO4;
reverts back to its original dispersed state MnS in CdS
- occur when a coagulated colloid is washed c) Occlusion – a compound is trapped within a pocket
(to removed or minimized contamination) formed during rapid crystal growth
wherein some of the electrolyte responsible
for its coagulation is leached from the d) Mechanical entrapment – occurs when crystals lie
internal liquid in contact with the solid close together during growth and in so
particles doing trapped a portion of the solution in a
tiny pocket
- minimized by washing the precipitate with a
solution containing an electrolyte that • Both occlusion and mechanical entrapment is at a
volatilizes when the precipitate is dried or minimum when the rate of precipitate formation is
ignited low, that is, under conditions of low supersaturation
ex. AgCl is washed with dilute HNO3
• Digestion often reduces the effects of both
Digestion - is a process in which a precipitate is heated in occlusion and mechanical entrapment
the solution from which it was formed (mother
liquor) and allowed to stand in contact with
the solution for an hour or more thus
improving the filterability of the precipitate
- weakly bound water appears to be lost
Gravimetric Calculations – How Much Analyte is There? Consider the following:
(1) You need to determine the gram of chloride (Cl-) in a
In the technique of gravimetric analysis, the analyte is sample by weighing it as AgCl
converted to an insoluble form (precipitate), which is
weighed. From the weight of the precipitate formed and Cl- precipitating reagent › AgCl
the weight relationship between the analyte and the
precipitate, the weight of the analyte can be calculated. So
𝑔 𝐶𝑙
𝑔 𝐶𝑙− 𝑓 𝑤𝑡 𝐶𝑙 ( ) 1 𝑚𝑜𝑙 𝐶𝑙
𝑚𝑜𝑙 𝐶𝑙
= 𝑔 𝐴𝑔𝐶𝑙 x
Example 4-1 𝑔 𝐴𝑔𝐶𝑙 𝑓 𝑤𝑡 𝐴𝑔𝐶𝑙 (𝑚𝑜𝑙 𝐴𝑔𝐶𝑙) 1 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙
An iron ore was analyzed by dissolving a 1.1324-g sample
in concentrated HCl. The resulting solution was diluted where f wt means formula weight or molar mass
with water, and the iron(III) was precipitated as the
hydrous oxide Fe2O3 · xH2O by the addition of NH3. After And by rearranging, units in blue
filtration and washing, the residue was ignited at a high 𝑔 𝐶𝑙
1 𝑚𝑜𝑙 𝐶𝑙 𝐹.𝑤𝑡. 𝐶𝑙 ( )
temperature to give 0.5394 g of pure Fe2O3 (159.69 g/mol). g Cl- = g AgCl x x 𝑚𝑜𝑙 𝐶𝑙
𝑔 𝐴𝑔𝐶𝑙
1 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙 𝐹.𝑤𝑡. 𝐴𝑔𝐶𝑙 (𝑚𝑜𝑙 𝐴𝑔𝐶𝑙)
Calculate:
(a) the % Fe (55.847 g/mol); and
(b) the % Fe3O4 (231.54 g/mol) in the sample. which can be summarized as
1 𝐶𝑙
Solution: g Cl- = g AgCl x
1 𝐴𝑔𝐶𝑙
1 𝐶𝑙
Given data where can be called as the gravimetric factor
1 𝐴𝑔𝐶𝑙
Mass sample = 1.1324 g (GF) wherein Cl refers to the atomic mass of Cl and AgCl
Mass precipitate = 0.5394 g Fe2O3 refers to the formula mass of AgCl
Molar masses/Formula masses
g Fe
In a more general form,
a) % Fe = x 100
g sample f wt of substance sought 𝑎
GF = x (mol sought/mol weighed)
f wt of substance weighed 𝑏
1 𝑚𝑜𝑙 𝐹𝑒2𝑂3 2 𝑚𝑜𝑙 𝐹𝑒 55.847 𝑔 𝐹𝑒
0.5394 𝑔 𝐹𝑒2𝑂3 𝑥 𝑥 𝑥
159.69 𝑔 𝐹𝑒2𝑂3 1 𝑚𝑜𝑙 𝐹𝑒2𝑂3 𝑚𝑜𝑙 𝐹𝑒
= x 100 or
1.1324 g sample
𝑎 f wt of substance sought
%Fe = 33.32% GF = x
𝑏 f wt of substance weighed

g Fe3O4 where a and b are integers that make the formula

b) % Fe3O4 = x 100
g sample weights in the numerator and denominator chemically
0.5394 𝑔 𝐹𝑒2𝑂3 𝑥
1 𝑚𝑜𝑙 𝐹𝑒2𝑂3
𝑥
2 𝑚𝑜𝑙 𝐹𝑒3𝑂4 231.54 𝑔 𝐹𝑒3𝑂4
𝑥
equivalent.
159.69 𝑔 𝐹𝑒2𝑂3 3 𝑚𝑜𝑙 𝐹𝑒2𝑂3 𝑚𝑜𝑙 𝐹𝑒3𝑂4
= Note: The use of GF is just to simplify the calculation process!
1.1324 g sample
x100
Consider the following:
% Fe3O4 = 46.04%
(2) You need to determine the gram of chlorine gas (Cl 2)
in a sample by weighing it as AgCl
Gravimetric Factor
Cl2 precipitating reagent › 2AgCl
In gravimetric analysis, the analyte is almost always
weighed in a form different from what we wish to report. So
𝑔 𝐶𝑙2
𝑔 𝐶𝑙2 𝑓 𝑤𝑡 𝐶𝑙2 ( ) 1 𝑚𝑜𝑙 𝐶𝑙2
𝑚𝑜𝑙 𝐶𝑙2
Therefore, we need to calculate the weight of the desired = 𝑔 𝐴𝑔𝐶𝑙 x
𝑔 𝐴𝑔𝐶𝑙 𝑓 𝑤𝑡 𝐴𝑔𝐶𝑙 (𝑚𝑜𝑙 𝐴𝑔𝐶𝑙) 2 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙
substance from the weight of the gravimetric precipitate.

This can easily be done from the knowledge that the moles And by rearranging, units in blue
of analyte is a multiple of the moles of precipitate formed
𝑔 𝐶𝑙2
(the moles of analyte contained in each mole of 1 𝑚𝑜𝑙 𝐶𝑙2 𝐹.𝑤𝑡. 𝐶𝑙2 (
𝑚𝑜𝑙 𝐶𝑙2
)
precipitate). g Cl2= g AgCl x x 𝑔 𝐴𝑔𝐶𝑙
2 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙 𝐹.𝑤𝑡. 𝐴𝑔𝐶𝑙 (𝑚𝑜𝑙 𝐴𝑔𝐶𝑙)
which can be summarized as Solution
Given data
1 𝐶𝑙2 Volume sample = 200.0 mL
g Cl2 = g AgCl x
2 𝐴𝑔𝐶𝑙
Mass of CaO precipitate = 26.7134g – 26.6002g =0.1132g

Ca
Consider the following: ?g Ca (in 200mL) = 0.1132 g CaO x
CaO
(3) You need to determine the gram of chloride (Cl-) and 40.078
chlorine gas (Cl2) in a sample by weighing it as PbCl2 = 0.1132 g CaO x g Ca/g CaO
56.077
?g Ca (in 200mL) = 0.0809 g
2Cl- precipitating reagent › PbCl2
And by ratio and proportion,
0.0809 g Ca = ? g Ca
and Cl2 precipitating reagent › PbCl2 200 mL 100 mL

then, ?g Ca (in 100 mL) = 0.0809 g Ca (100/200)

2 𝐶𝑙−
g Cl- = g PbCl2 x and ?g Ca/100 mL sample = 0.04045 g Ca in 100 mL sample
1 𝑃𝑏𝐶𝑙2

1 𝐶𝑙2
g Cl2 = g PbCl2 x
1 𝑃𝑏𝐶𝑙2 Example 4-3
Calculate the weight of barium (137.3 g/mol) and the
weight of chlorine (35.45 g/mol) in 25.0 g BaCl2 (208.2
Here are some other examples of gravimetric factors:
g/mol).
sought weighed Gravimetric Factor
SO3 BaSO4 SO3 Solution
BaSO4 Ba
(base the a & b values on S and not the O; ?g Ba = 25.0 g BaCl2 x
BaCl2
O is more common compared to S)
137.3
𝟐 Fe3O4 = 25.0 g BaCl2 x g Ba/g BaCl2
Fe3O4 Fe2O3 208.2
𝟑 Fe2O3
(2/3 to have a balance # of total Fe which is 6 ?g Ba = 16.5 g
for both numerator and denominator)

Fe 𝟐 Fe and
Fe2O3 2 Cl
Fe2O3 ?g Cl = 25.0 g BaCl2 x
BaCl2
MgO Mg2P2O7 2MgO 2 x 35.45
𝑀𝑔2𝑃2𝑂7 = 25.0 g BaCl2 x g Cl/g BaCl2
208.2
(base the a & b values on Mg w/c is common
to both sought and weighed substances) ?g Cl = 8.51 g
P2O5 Mg2P2O7 P2O5
𝑀𝑔2𝑃2𝑂7
(base the a & b values on P w/c is common to Example 4-4
both sought and weighed substances)
SO3 1 x f wt SO3 Aluminum in an ore sample is determined by dissolving it
Note: A GF of just means where 1/1 are the a/b
BaSO4 1 x f wt BaSO4 and then precipitating with base as Al(OH)3 and igniting to
values to balance the # of S.
Al2O3 (101.96 g/mol), which is weighed. What weight of
aluminum (26.982 g/mol) was in the sample if the ignited
precipitate weighed 0.2385 g?
Example 4-2
The calcium in a 200.0-mL sample of a natural water was Solution
determined by precipitating the cation as CaC 2O4. The 2 Al
?g Al = 0.2385 g Al2O3 x
Al2O3
precipitate was filtered, washed, and ignited in a crucible
with an empty mass of 26.6002 g. The mass of the 2 x 26.982
= 0.2385 g Al2O3 x g Al/g Al2O3
101.96
crucible plus CaO (56.077 g/mol) was 26.7134 g. Calculate
the concentration of Ca (40.078 g/mol) in water in units ?g Al = 0.1262 g
of grams per 100 mL of the water.
Example 4-5 LECTURE – Assignment 4
An ore is analyzed for the manganese content by Show all solutions. Five (5) points each unless specified.
converting the manganese to Mn3O4 and weighing it. If a Deadline: Oct 23/24, 2023 (Mon/Tues)
1.52 g sample yields Mn3O4 (228.8 g/mol) weighing 0.126 1. Calculate the weight of sodium present in 50.0 g
g, what would be the percent Mn2O3 (157.9 g/mol) in the Na2SO4.
sample? The percent Mn (54.94 g/mol)?
2. Calculate the gravimetric factors for: (1 pt each)
Given Substance sought Substance weighed GF
Mass Mn3O4 precipitate = 0.126 g As2O3 Ag3AsO4 ?
Mass ore sample = 1.52 g FeSO4 Fe2O3 ?
gX SiO2 KAlSi3O8 ?
%X = x 100
g sample CaO CaCO3 ?
g sought
weight of precipitate (g)x GF (g precipitate) Cr2O3 Ag2CrO4 ?
% sought = x 100 K3PO4 K2PtCl6 ?
g sample

g Mn2O3 3. The aluminum content of an alloy is determined

% Mn2O3 = x 100 gravimetrically by precipitating it with 8-hydroxyquinoline
g sample

3 𝑀𝑛2𝑂3
(oxine) to give Al(C9H6ON)3. If a 1.021 g sample yielded
0.126 𝑔 𝑀𝑛3𝑂4 𝑥 2 𝑀𝑛3𝑂4 0.1862 g of precipitate, what is the percent aluminum in
= x 100 the alloy?
1.52 g sample
3 𝑥 157.9 𝑔 𝑀𝑛2𝑂3 4. A method to measure soluble organic carbon in
0.126 𝑔 𝑀𝑛3𝑂4 𝑥
2 𝑥 228.8 𝑔 𝑀𝑛3𝑂4 seawater includes oxidation of the organic materials to
= x 100
1.52 g sample with followed by gravimetric determination of the trapped
by a column of NaOH-coated asbestos. A water sample
% Mn2O3 = 8.58%
weighing 6.234 g produced 2.378 mg of CO2 (44.010
and g/mol). Calculate the ppm carbon in the seawater
g Mn 5. What weight of sample containing 8.00% Fe3O4 must
% Mn = x 100
g sample be taken to obtain a precipitate of Fe(OH)3, that, when
3 𝑀𝑛 ignited to Fe2O3, weighs 150 mg?
0.126 𝑔 𝑀𝑛3𝑂4 𝑥 𝑀𝑛3𝑂4
= x 100 6. A 0.3516 g sample of commercial phosphate detergent
1.52 g sample
was ignited at a red heat to destroy the organic matter.
0.126 𝑔 𝑀𝑛3𝑂4 𝑥
3 𝑥 54.94 𝑔 𝑀𝑛 The residue was taken up in hot HCl, which converted the
228.8 𝑔 𝑀𝑛3𝑂4
= x 100 P to H3PO4. The phosphate was precipitated as
1.52 g sample
MgNH4PO4•6H2O by addition of Mg2+ followed by aqueous
% Mn = 5.97% NH3. After being filtered and washed, the precipitate was
converted to Mg2P2O7 by ignition to 1000⁰C. This residue
weighed 0.2161 g. Calculate the % P in the sample.
References:
Books 7. A mixture containing only AgCl and AgBr weighs 2.000
1. Christian, G.D. (2004) Analytical Chemistry, 6 th ed., g. It is quantitatively reduced to silver metal, which
John Wiley & Sons, Inc. weighs 1.300 g. Calculate the weight of AgCl and AgBr in
the original mixture.
2. Harris, D.C. (2007) Quantitative Chemical Analysis, (You may see Anal Chem by Christian p. 324 and Skoog et al. p. 293 for similar
7th ed., W.H. Freeman. problems)

3. Skoog, D.A., West, D.M., Holler, F.J. and Crouch, S.R

(2014) Fundamentals of Analytical Chemistry, 9th ed.,
Cengage Learning.
Links
Slide 1 (iyte.edu.tr)
Microsoft Word - Chapter 12 Gravimetric Methods of
Analysis.doc (kmu.edu.tw)
1-5 Weeks Gravimetry.pdf (ankara.edu.tr)