Module3 - Gravimetric Method of Analysis

MCHEM 122 -ANALYTICAL CHEMISTRY
Module 3 Gravimetric Analysis
Module Overview:
Measuring mass is the most fundamental of all analytical measurements, and
gravimetric analysis requires only base SI units, such as mass(g) and moles, and
defined constants, such as Avogadro’s number and the mass of 12C to
estimating the composition of materials.
In this module, you will learn how to carry out gravimetric procedures and perform
calculation in the determination of the amount of analyte present in the sample in
the form of precipitate or volatile components.
Module Outcomes:
In this module, students are expected to be able to:
 Determine the steps in gravimetric analysis
 Demonstrate appreciation of the method of gravimetric in calculating the

weight of a substance
 Calculate the percent weight of a substance using gravimetric factor
The topics are structured as follows:
Lesson 1 – Introduction to Gravimetric Analysis

Lesson 2 – Quantitative Application of Gravimetric Analysis
Are you ready? Then start the lessons.
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Lesson 1
Introduction to Gravimetry
Learning Outcomes:
1. Appreciate the principles of gravimetric method of analysis.
2. Define the basic terminologies used in gravimetry.
3. Appreciate the ways it is being applied in research and industry.
Time Frame: Week 11
Introduction:
Before we look more closely at specific gravimetric methods and their

applications, let’s take a moment to develop a broad survey of gravimetry by
discussing different gravimetric methods and terminologies. It is usually easier to
understand the gravimetric problems if the principle is really mastered, or a a new
method of analysis is easily understand when you can see its relationship to
gravimetric methods.
ACTIVITY
KWL Chart
Direction: Based on your experiences and understanding, write brief statement in
each column below.
K W H L
What I know or What I want to How I learn What I learn about
think I know about learn about gravimetric method gravimetric method
gravimetric method gravimetric method of analysis of Analysis
of analysis
ANALYSIS
In 100 words, discuss what you have written in the activity above.
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ABSTRACTION
Principles of Gravimetric Method of Analysis
Gravimetric methods are quantitative methods that are based upon determining
the mass of a pure compound to which the analyte is related.
Theodore W. Richards (1868 - 1928) and his graduate student at Harvard

developed or refined many of the techniques of gravimetric analysis of silver
and chlorine. These techniques were used to determine the atomic weights of
25 of the elements by preparing pure samples of the chlorides of the
elements, decomposing known weights of the compounds, and determining
the chloride content by gravimetric methods. From this work Richards became
the first American to receive the Nobel Prize in Chemistry in 1914.
Types of Gravimetric Method
1. Precipitation
In the precipitation methods, the species to be determined is precipitated

by a reagent that yields a soluble product (or a product of known
composition, or a product that can be converted to one of known
composition).
It involves isolation of an ion in solution by a precipitation reaction, filtering,

washing the precipitate free of contaminants, conversion of the precipitate
to a product of known composition, and finally weighing the precipitate and
determining its mass by difference.
2. Volatilization
In volatilization methods, a thermal or chemical energy is used to remove

volatile components of the sample. The analyte (or its decomposition
products) are volatilized at a suitable temperature. The volatilized species
are collected and weighed directly or weighed by difference.
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Example:
a. Determining the moisture content of food, thermal energy vaporizes the

H2O
b. The amount of carbon in an organic compound may be determined by
using the chemical energy of combustion to convert C to CO2
3. Electrogravimetry
In electrogravimetry, the analyte is deposited as a solid film on one

electrode in an electrochemical cell.
Example:
a. The oxidation of Pb2+, and its deposition as PbO2 on a Pt anode

b. Reduction of Cu and its electrodeposition on a Pt cathode in the
analysis of Cu2+
4. Particulate gravimetry
In particulate gravimetry, the analyte is determined following its removal

from the sample matrix by filtration or extraction.
Example:
The determination of suspended solids is one example of

particulate gravimetry
For all methods the analytes is reported as a weight percent:
analyte - chemical element or compound of interest
The Reaction in gravimetric method:

aA + rR -----> AaRr ppt
where:
– a is # of moles of analyte A
– r is # of moles of reagent R
– AaRr is a pure, insoluble precipitate which we can dry and weigh or
ignite to convert to something we can weigh
– Ppt is the precipitate
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Precipitation Methods
A. Properties of precipitates and precipitating agents.
1. The ideal precipitating agents is one that reacts with one and
only one analyte to produce a solid that is...
a. soluble (i.e., not lost during filtration and washing).
b. readily filterable and washes free of contaminates (i.e., not

a gelatinous mess).
c. unreactive to the atmosphere.
d. of known composition (or can be converted to something

of known composition).
2. Precipitate must be of low solubility, high purity, and of known

composition if its mass is to accurately reflect the analyte’s mass.
3. Precipitate must be in a form that is easy to separate from the

reaction mixture.
4. Precipitates with large particles size work best for filtration and
washing.
5. Colloidal suspensions (precipitates with particles sizes of 1-100

nanometers) are undesirable.
a. The particles do not settle out.
b. Filtration is difficult due to plugging of pores in the filter, or

passing through the filter.
6. Precipitate size can be controlled (to some extent) by the

conditions used to cause precipitation.
B. Factors that affects precipitation
1. pH
pH may affect a precipitate’s solubility if it contains an acidic or basic

anion.
example: As the solution becomes more acidic, the solubility of

Ca3(PO4)2 increases.
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2. Solvating ability of nonaqueous solvents (the poorer solvating power

even those that are polar, leads to a smaller solubility product).
C. Mechanism of precipitate formation.
The size of the precipitate’s particles determines the ease and success of
filtration. Smaller, colloidal particles are difficult to filter because they may
readily pass through the pores of the filtering device. Large, crystalline
particles, however, are easily filtered. By carefully controlling the
precipitation reaction we can significantly increase a precipitate’s average
particle size.
1. Two steps are involved in precipitation:

a. Nucleation: Initial formation of smaller stable precipitates in a
supersaturated solution capable of spontaneous growth.
Larger particles form when the rate of particle growth

exceeds the rate of nucleation.
b. Particle Growth: Deposition of ions/molecules on the surface of

the solid, nucleated particles.
2. In general, particle size is governed by the number of nuclei

formed:
a. Large supersaturation leads to more nuclei (and smaller particle

size) and often produce colloids.
b. Dilute solutions lead to fewer nuclei, more deposition on the

fewer nuclei and larger crystals.
3. Spontaneous nucleation is rare. Usually, you must induce nucleation to

provide a site to attract and hold ions/molecules by...
a. Scratching the side of the container.
b. Adding seed crystals.
4. Other experimental factors controlling precipitate size include...
a. Diffusion of ions/molecules to the surface of the growing crystal.

This is affected by stirring, temperature, the nature of the
ions/molecules, and concentration (low concentration is usually
best).
b. Deposition on the surface of the crystal. This is affected by

concentration, impurities on the surface of the crystal, growth
characteristics of the crystal and pH (if pH-dependent).
c. When first formed, precipitates usually exist as colloidal particles.
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d. The colloidal particles need to coagulate to increase the particle

size.
e. Coagulation is accomplished by heating, stirring. adding

electrolytes to negate surface charges.
f. Peptization should be avoided. (Peptization is the process by

which a coagulated precipitate is returned to its colloidal state.)
Peptization can be caused by...
1. Washing away electrolytes responsible for coagulation.
2. Washing away colloidal pieces of the precipitate.
g. Peptization can be minimized by washing a precipitate with a

solution of an electrolyte that is volatilized during an ensuing drying
step.
h. The bottom line on precipitation is...
1. Colloids are best precipitated from hot, stirred, dilute

solutions.
2. Filterability is improved if the coagulated colloid is digested

(heated for over an hour) in the mother liquid. (Digestion
expels water from the crystal, producing a denser, better
filtering precipitate.)
D. Problems Encountered With Obtaining A Pure Precipitate
A. Co-precipitation is the major problem.
1. Co-precipitation is the precipitation of an otherwise soluble

substance along with the insoluble material.
2. Co-precipitation may happen simultaneously or following the first

precipitation.
B. There are several mechanisms of co-precipitation. These include...
1. Surface adsorption.
Surface adsorbates may be chemically or physically adsorbed, and

is minimized by decreasing the precipitate’s available surface area.
Surface adsorbates also may be removed by washing the
precipitate.
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2. Occlusion.
Occlusions form in two ways
a. When physically adsorbed ions are surrounded by

additional precipitate before they can be desorbed or
displaced (. In this case the precipitate’s mass is always
greater than expected).
b. When rapid precipitation traps a pocket of solution within
the growing precipitate. Since the trapped solution
contains dissolved solids, the precipitate’s mass normally
increases. The mass of the precipitate may be less than
expected, however, if the occluded material consists
primarily of the analyte in a lower-molecular-weight form
from that of the precipitate.
Occlusions are minimized through the process called digestion

where the precipitate is maintain in equilibrium with its supernatant
solution for an extended time. Since the rate of dissolution and
reprecipitation are slow, the chance of forming new occlusions is
minimal.
3. Inclusion. The potential interfering ions whose size and charge are
similar to a lattice ion may substitute into the lattice structure by
chemical adsorption, provided that the interferent precipitates with the
same crystal structure. The probability of forming an inclusion is
greatest when the interfering ion is present at substantially higher
concentrations than the dissolved lattice ion. The presence of an
inclusion does not decrease the amount of analyte that precipitates,
provided that the precipitant is added in sufficient excess. Thus, the
precipitate’s mass is always larger than expected. Inclusions are
difficult to remove since the included material is chemically part of the
crystal lattice. The only way to remove included material is through
reprecipitation. After isolating the precipitate from the supernatant
solution, it is dissolved in a small portion of a suitable solvent at an
elevated temperature. The solution is then cooled to re-form the
precipitate. Since the concentration ratio of interferent to analyte is
lower in the new solution than in the original supernatant solution, the
mass percent of included material in the precipitate decreases. This
process of reprecipitation is repeated as needed to completely remove
the inclusion. Potential solubility losses of the analyte, however, cannot
be ignored. Thus, reprecipitation requires a precipitate of low solubility,
and a solvent for which there is a significant difference in the
precipitate’s solubility as a function of temperature (Harvey, 2000).
4. Mechanical entrapment. Two crystals grow together and trap a
species in the space between them.
5. Post precipitation. The precipitate causes a localized high
concentration of unwanted species.
6. Other species in solution precipitate under the conditions of the
analysis.
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Most precipitants are not selective toward a single analyte, there is

always a risk that the precipitant will react, sequentially, with more than
one species.
Interferents forming precipitates that are less soluble than the analyte
may be precipitated and removed by filtration, leaving the analyte
behind in solution. Alternatively, either the analyte or the interferent can
be masked using a suitable complexing agent, preventing its
precipitation.
IV. Filtering of precipitate
After precipitation and digestion are complete, the precipitate is separated from
solution by filtration using either filter paper or a filtering crucible.
Filter paper must be removed before weighing the precipitate, thus an ashless or
low-ash filter paper must be used to quantitative measure the final weight of the
precipitate.
Suction Filtration
 Filter flask
 Buchner funnel
 Filter paper
 Glass frit
 Filter adapter
 Heavy-walled
rubber tubing
 Water aspirator
Mother liquor
Folding of filter paper:
Source: (Harvey, 2000). The filter paper is fold into four parts and the torn
corner is placed to the outside(f).
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V. Drying and Ignition of Precipitates.

A. Drying removes any residual traces of rinse solution or the solvent(s) of
the mother liquid or any volatile impurities from which the precipitate was
formed.
B. Ignition converts the precipitate to a known composition called the

weighing form.
C. The temperature and method of drying/ignition depend on the method

of filtration, and the precipitate’s desired chemical form.
Example:
1. Around 200oC, calcium oxalate exists as the hydrate
CaC2O4.H2O.
2. Around 400oC, calcium oxalate exists as CaC2O4.
3. Around 700oC, calcium oxalate exists is converted to CaCO3.
4. Above 1,000oC, calcium carbonate is converted to CaO.
Higher temperatures require the use of a muffle furnace, or a Bunsen or

Meker burner, and are necessary when the precipitate must be thermally
decomposed before weighing or when using filter paper. To ensure that
drying is complete the precipitate is repeatedly dried and weighed until a
constant weight is obtained.
VI. Composition of the Final precipitate
It is required that the final precipitate have a well-defined composition.
VII. Typical Gravimetric Determinations.

A. Determination of chloride ion by precipitation with silver ion to form
AgCl.
B. Determination of sulfate ion by precipitation with barium ion to form

BaSO4.
C. Determination of nickel(II) ion by precipitation with dimethylglyoxime to

form the Ni(DMG)2 precipitate, a brilliant red-colored precipitate.
1. DMG precipitates Pd(II) as a yellow precipitate.
2. DMG also precipitates Bi(II) as a colorless precipitate.
D. 8-Hydroxyquinoline chelation of magnesium(II) (and other) ions in a pH-

dependent precipitation.
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E. Sodium tetraphenylboron forms salt-like precipitates with potassium or

ammonium ion in cold, mineral acid solutions.
1. Sodium tetraphenylboron is selective, but not specific for

potassium and ammonium ion.
2. Mercury(II), Ruthenium(II) and Cesium(I) interfere.
Requirements for a successful gravimetric method:
1. The separation process should be sufficiently complete so that the quantity

of analyte left unprecipitated is 0.1 mg or less in determining a major
constituent of a macro sample.
2. The substance weighed should have a definite composition and should be
pure, or very nearly so. Otherwise, erroneous results may be obtained.
‘Every substance must be assumed to be impure, every reaction must be

assumed to be incomplete, every method of measurement must be assumed
to contain some constant error, until proof to the contrary can be obtained. As
little as possible must be taken for granted.”( by T.W. Richards).
Summary of basic 7 Steps in Gravimetric Analysis

1. Dry and weigh sample
2. Dissolve sample
3. Add precipitating reagent in excess
4. Coagulate precipitate usually by heating
5. Filtration-separate ppt from mother liquor
6. Wash precipitate (peptization)
7. Dry and weigh to constant weight
Advantages/Disadvantages of Gravimetric Method of Analysis

1. Time-intensive
2. Practical alternative when working with few samples.
3. Does not require an analyst’s immediate supervision
4. Does not required sophisticated equipment, easy to maintain
5. Inexpensive
6. Available in most laboratories
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Jons Jacob Berzelius (1779 - 1848), considered the

leading chemist of his time, developed much of the
apparatus and many of the techniques of 19th century
analytical chemistry. Examples include the use of ashless
filter paper in gravimetry, the use of hydrofluoric acid to
decompose silicates, and the use of the metric system in
weight determinations. He performed thousands of
analyses of pure compounds to determine the atomic
weights of most of the elements known then. Berzelius
also developed our present system of symbols for
elements and compounds.
.
APPLICATION
Determination of Mg2+ in Water and Wastewater (Harvey, 2000)
Description of Method.
Magnesium is precipitated as MgNH4PO4 ⋅ 6H2O using (NH4)2HPO4 as the
precipitant. The precipitate’s solubility in neutral solutions (0.0065 g/100 mL in
pure
water at 10 °C) is relatively high, but it is much less soluble in the presence of
dilute
ammonia (0.0003 g/100 mL in 0.6 M NH3). The precipitant is not very selective,
so a preliminary separation of Mg2+ from potential interferents is necessary.
Calcium, which is the most significant interferent, is usually removed by its prior
Precipitation as the oxalate. The presence of excess ammonium salts from the
precipitant or the addition of too much ammonia can lead to the formation of
Mg(NH4)4(PO4)2, which is subsequently isolated as Mg(PO3)2 after drying. The
precipitate is isolated by filtration using a rinse solution of dilute ammonia. After
filtering, the precipitate is converted to Mg2P2O7 and weighed. Procedure.
Transfer a sample containing no more than 60 mg of Mg 2+ into a 600-mL beaker.
Add 2–3 drops of methyl red indicator, and, if necessary, adjust the volume to
150 mL. Acidify the solution with 6 M HCl, and add 10 mL of 30% w/v
(NH4)2HPO4. After cooling, add concentrated NH 3 dropwise, and while constantly
stirring, until the methyl red indicator turns yellow (pH > 6.3). After stirring for 5
min, add 5 mL of concentrated NH 3, and continue stirring for an additional 10 min.
Allow the resulting solution and precipitate to stand overnight. Isolate the
precipitate by filtration, rinsing with 5% v/v NH3. Dissolve the precipitate in 50 mL
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of 10% v/v HCl, and precipitate a second time following the same procedure.
After filtering, carefully remove the filter paper by charring. Heat the precipitate at
500 °C until the residue is white, and then bring the precipitate to constant weight
at 1100 °C.
Questions:
1. Why does the procedure call for a sample containing no more than 60 mg of
Mg2+?
2. Why is the solution acidified with HCl before the precipitant is added?
3. Why is the acid–base indicator methyl red added to the solution?
4. Explain why the formation of Mg(PO 3)2 in place of Mg2P2O7 increases the
mass of precipitate.
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5. What additional steps in the procedure, beyond those discussed in questions 2

and 3, are taken to improve the precipitate’s purity?
6. Why is the precipitate rinsed with a solution of 5% v/v NH3?
CLOSURE
Congratulation. You have just finished Lesson 1. In this lesson, gravimetric

method of chemical analysis was introduced with its important terminologies.
The next lesson will introduce you to the quantitative application of gravimetric
analysis.
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Lesson 2
Quantitative Application of Gravimetric Analysis
Learning Outcomes:
1. Calculate amount and concentration of analyte by gravimetric method
of analysis.
2. Apply knowledge in conservation of mass in performing computation of
the amount of substance or analyte in gravimetry.
Time Frame: Week 12, Week 13
Introduction
Gravimetric calculations can be simplified by applying the principle of
conservation of mass. In this lesson example demonstrates the application of this
approach to the analysis of analyte.
ACTIVITY
Watch video on the conservation of mass. https://study.com/academy/lesson/the-
law-of-conservation-of-mass-definition-equation-examples.html
ANALYSIS
Questions:
1. What is conservation of mass?

2. According to video, the discovery of the conservation of mass led to what
important results?
3. Balance the following equation below:
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Final Final Balanced

Unbalanced Equation Reactants Products
Reactants Products Equation
H2 + O2 --> H2O
Al + O2 Al2O3
H2O2 --> H20 + O2
AgNO3 + Cu Cu(NO3)2 + Ag
Na + O2 --> Na2O
BaO + O2 BaO2
N2 + H2 --> NH3
K + N2 K3N
P4 + O2 --> P4O10
Fe + H2O --> Fe3O4 + H2
H2 + Fe3O4 Fe + H2O
C + H2 --> CH4
Na2SO4 + CaCl2 --> CaSO4 +
NaCl
C2H6 + O2 --> CO2 + H2O
(NH4)2CO3 Δ NH3 + H2O +CO2
4. The law of conservation of mass is seen in which type of chemical

equation?
5. What is an 'unbalanced chemical equation?'
ABSTRACTION
In gravimetry, the relationship between the analyte and the precipitate is

determined by the stoichiometry of the relevant reactions.
% of analyte, % A
% A = weight of analyte x 100

weight of sample
% A = weight of ppt x gravimetric factor (G.F.) x 100

weight of sample
GF= aFW[analyte]
bFW[precipitate]
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Example of Gravimetric Factor
Analyte ppt G.F

CaO CaCO3 CaO/CaCO3
FeS BaSO4 FeS/BaSO4
UO2(NO3)2 U3O8 3UO2(NO3)2/U3O8
Cr2O3 Ag2CrO4 Cr2O3/2Ag2CrO4
Sample Problems
1. An iron ore sample weighing 0.4852-g is dissolved in acid, and iron is

oxidized to the +3 state and then precipitated as hydrous oxide,
Fe2O3.xH2O. The precipitate is filtered, washed, and ignited to Fe2O3,
which is found to weigh 0.2481 g. Calculate the percentage iron (Fe) in
the sample:
The reaction :
2Fe3+ + Fe2O3 . xH2O Fe2O3(s)
amount Fe = amount Fe2O3 x a mol Fe

b mol Fe 2O3
Based on the reaction: 2 mol Fe3+ produce 1 mol of Fe2O3(s)
Amount of Fe = wt Fe
MW Fe
Amount of Fe2O3 = wt Fe2O3

MW Fe2O3
wt Fe = wt Fe2O3 x 2 mol Fe
MW Fe MW Fe2O3 1 mol Fe2O3
Wt Fe = wt Fe2O3 x 2 molFe
MW Fe MW Fe2O3 1 mol Fe2O3
Wt Fe = wt Fe2O3 X 2 X (MW Fe)

MW Fe 2O3
Wt Fe = 0.2481g x 2 x 55.85 g/mole

159.69 g/mole
Wt Fe = 0.1735 g
2. The thermogram shows the change in mass for a sample of calcium

oxalate monohydrate, CaC2O4 ⋅ H2O. The original sample weighed
24.60 mg and was heated from room temperature to 1000 °C at a rate
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of 5 °C min. The following changes in mass and corresponding

temperature ranges were observed: Loss of 3.03 mg from 100–250 °C
Loss of 4.72 mg from 400–500 °C Loss of 7.41 mg from 700–850 °C
Determine the identities of the volatilization products and the solid
residue at each step of the thermal decomposition.
Given:
Sample, CaC2O4.H2O, Initial weight = 24.60mg
a. The loss of 3.03 mg from 100–250 °C
b. Loss of 4.72 mg from 400–500 °C
c. Loss of 7.41 mg from 700–850 °C
Solution:
a. 3.03 x 100 = 12.31%
24.60
FW (CaC2O4 ⋅ H2O )= 146.11g/mol
0.1232 × 146.11 g/mol = 18.00 g/mol
In terms of CaC2O4 ⋅ H2O, this corresponds to a loss of 18.00 g/mol.
This suggests the loss of H2O. The residue is CaC2O4
b. 4.72 X 100= 19.19%
24.60
0.1919x 146.11g/mol = 28.03g/mol
In terms of CaC2O4, this corresponds to the lost of CO
The residue is CaCO3
c. 7.41 x 100= 30.12%

24.60
0.3012 x 146.11g/mol = 44.00g/mol
In terms of CaCO3, this corresponds to the lost of CO2
The residue is CaO
3. A 0.7203 g sample containing chloride is dissoved and the chloride

precipitated as AgCl. The precipitate is washed, dried, and found to
weigh 0.4026g. Calculate the percentage of chloride in the sample.
Solution:
%Cl = 0.4026g AgCl( AW Ag/ FW AgCl) x100
Wt sample
% Cl= 0.4026g AgCl ( 35g/mol/143.32g/mol) x100
0.7203
% Cl= 13.65
4. A 0.3516g sample of a commercial phosphate detergent was ignited at

a red heat to destroy organic matter. The residue was then taken up in
hot HCl which converted the P to H3PO4. The phosphate was
precipitated as MgNH4PO4.6H2O by addition of Mg2+ followed by
aqueous NH3. After being filtered and washed, the precipitate was
converted to Mg2P2O7 (222.57g/mole) by ignition at 1000oC. This
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residue weighed 0.2161g. Calculate the %P (30.974g/mole) in the

sample.
Solution:
gP = 0.2161g Mg2P2O7 x 30.974 g/mole P x 2mole P
222.57g/mole Mg 2P2O7 1mole Mg2P2O7
g P = 0.06015 g
%P = 0.06015 g x 100 = 17.11%
0.3516g
APPLICATION
Determination of Si in Ores and Alloys
Description of Method.
Silicon is determined by dissolving the sample in acid. Dehydration of the
resulting solution precipitates silicon as SiO 2. Because a variety of other insoluble
oxides also form, the precipitate’s mass does not provide a direct measure of the
amount of silicon in the sample. Treating the solid residue with HF results in the
formation of volatile SiF4. The decrease in mass following the loss of SiF 4
provides an indirect measure of the amount of silicon in the original sample.
Procedure.
Transfer a sample of between 0.5 and 5 g to a platinum crucible along with an
excess of Na2CO3, and heat until a melt is formed. After cooling, dissolve the
residue in dilute HCl. Dehydrating silicon to SiO 2 is accomplished by evaporating
the solution to dryness on a steam bath and heating the residue for 1 hour at 110
°C. Moisten the residue with HCl, and repeat the dehydration. Remove any acid-
soluble materials from the residue by adding 50 mL of water and 5 mL of
concentrated HCl. Bring to a boil, and filter through #40 filter paper. Wash the
residue with hot 2% v/v HCl followed by hot water. Evaporate the filtrate to
dryness twice, and, following the same procedure, treat to remove any acid–
soluble materials. Combine the two precipitates, and dry and ignite to a constant
weight at 1200 °C. After cooling, add 2 drops of 50% v/v H 2SO4 and 10 mL of HF.
Remove the volatile SiF4 by evaporating to dryness on a hot plate. Finally, bring
the residue to constant weight by igniting at 1200 °C.
Questions
1. According to the procedure, the sample should weigh between 0.5 and 5 g.
On what basis should a decision on the amount of sample be made?
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2. Why are acid-soluble materials removed before the dehydrated residue is

treated with HF?
3. Why is H2SO4 added with the HF?
CLOSURE
Congratulation. You have just finished Lesson 2. In this lesson, you learned how
to calculate the concentration of the analyte by manipulating the formula and
considering the conservation of mass principle.
Module Summary
In this module we learned the principles and terminologies in gravimetric method

of analysis. We also learnt how to calculate the amount of analyte present in the
sample.
Module Assessment
Gravimetric Method Problem Set

1. Write the gravimetric factors ( using chemical formula) for each of the
following.
Sought weighed gravimetric

factor
a. Al Al2O3
b. Cl AgCl
c. Zn Zn2P2O7
d. MoS3 BaSO4
e. Na2B4O7.H2O B2O3
f. P2O5 Mg2P2O7
g. Pb(C2H5)4 PbCrO4
h. SO3 BaSO4
2. What weight of silver chloride precipitate can be produced from an

800-mg sample containing 14.5% CaCl2?
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3. The sulphur in a 0.8245-g sample is converted to sulphate, and the

sulphate precipitated as BaSO4. The precipitate is washed, ignited,
and found to weigh 0.3084 g. Calculate the S% and SO3.
4. What will 628 mg of Zr(HPO4)2 weigh after ignition to ZrP2O7?
5. A fertilizer advertised as 8-8-8 generally means that it contains 8% total

nitrogen, 8% P2O5 and 8% K2O. Calculate the percentage of P and K
in the fertilizer.
6. A 1.000-g sample of ultrapure silicon was treated with an oxidizing

agent and the resulting SiO2, after proper collection and drying,
weighed 2.1387-g. Calculate the %Si in the sample.
7. A sample of brass weighing 712 mg was dissolved and treated in such

a way as to successfully precipitate SnS2, CuS, ZnNH4PO4.H2O and
PbSO4. Each precipitate was collected and ignited producing the
following weights: 83.2 mg of SnO 2, 700.5mg CuO, 50.6 mg Zn2P2O7
and 36.3mg of PbSO4. Calculate the percentage of each metal in the
brass. Does this account for all of all sample?
8. The sulphate in a 674.3 mg sample was determined by a gravimetric

method. If the precipitate consisted of 214.4 mg of BaSO 4 and 9.7 mg
of Ba(PO4)2 before ignition, calculate the following: a) apparent %S, B)
true %S
9. A commercial algaecide containing an organocopper compound was
treated with concentrated nitric acid and evaporated to dryness. After
dissolution of the residue, the copper was precipitated with alpha-
benzoic oxime. If the sample weighted 15.443-g and the precipitate of
Cu(C14H12NO2)2 weighted 0.6314-g, calculate the %Cu in the algaecide.
10. What size sample which contains 180% Fe 3O4 should be taken for
analysis in order to obtain a precipitate of Fe2O3 which weighs 0.400g?
21 | P a g e
References
(n.d.). Retrieved from
https://courses.lumenlearning.com/introchem/chapter/strong-acid-weak-
base-titrations/
Hanna Instruments. (n.d.). Retrieved from
https://www.hannanorden.se/literature/Titration%20Introduction.pdf
Harvey, D. (2000). Modern Analytical Chemistry. United States: The McGraw-Hill
Companies, Inc.
https://courses.lumenlearning.com/introchem/chapter/strong-acid-weak-base-
titrations/. (n.d.).
https://study.com/academy/lesson/the-law-of-conservation-of-mass-definition-
equation-examples.htm
22 | P a g e

Module3 - Gravimetric Method of Analysis

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MCHEM 122 -ANALYTICAL CHEMISTRY

Module 3 Gravimetric Analysis

In this module, students are expected to be able to:

 Determine the steps in gravimetric analysis

 Demonstrate appreciation of the method of gravimetric in calculating the

 Calculate the percent weight of a substance using gravimetric factor

The topics are structured as follows:

Lesson 1 – Introduction to Gravimetric Analysis

Are you ready? Then start the lessons.

Time Frame: Week 11

Before we look more closely at specific gravimetric methods and their

Theodore W. Richards (1868 - 1928) and his graduate student at Harvard

Types of Gravimetric Method

In the precipitation methods, the species to be determined is precipitated

It involves isolation of an ion in solution by a precipitation reaction, filtering,

In volatilization methods, a thermal or chemical energy is used to remove

a. Determining the moisture content of food, thermal energy vaporizes the

In electrogravimetry, the analyte is deposited as a solid film on one

a. The oxidation of Pb2+, and its deposition as PbO2 on a Pt anode

In particulate gravimetry, the analyte is determined following its removal

The determination of suspended solids is one example of

For all methods the analytes is reported as a weight percent:

analyte - chemical element or compound of interest

The Reaction in gravimetric method:

A. Properties of precipitates and precipitating agents.

a. soluble (i.e., not lost during filtration and washing).

b. readily filterable and washes free of contaminates (i.e., not

c. unreactive to the atmosphere.

d. of known composition (or can be converted to something

2. Precipitate must be of low solubility, high purity, and of known

3. Precipitate must be in a form that is easy to separate from the

5. Colloidal suspensions (precipitates with particles sizes of 1-100

a. The particles do not settle out.

b. Filtration is difficult due to plugging of pores in the filter, or

6. Precipitate size can be controlled (to some extent) by the

B. Factors that affects precipitation

pH may affect a precipitate’s solubility if it contains an acidic or basic

example: As the solution becomes more acidic, the solubility of

2. Solvating ability of nonaqueous solvents (the poorer solvating power

C. Mechanism of precipitate formation.

1. Two steps are involved in precipitation:

Larger particles form when the rate of particle growth

b. Particle Growth: Deposition of ions/molecules on the surface of

2. In general, particle size is governed by the number of nuclei

a. Large supersaturation leads to more nuclei (and smaller particle

b. Dilute solutions lead to fewer nuclei, more deposition on the

3. Spontaneous nucleation is rare. Usually, you must induce nucleation to

a. Scratching the side of the container.

b. Adding seed crystals.

4. Other experimental factors controlling precipitate size include...

a. Diffusion of ions/molecules to the surface of the growing crystal.

b. Deposition on the surface of the crystal. This is affected by

c. When first formed, precipitates usually exist as colloidal particles.

d. The colloidal particles need to coagulate to increase the particle

e. Coagulation is accomplished by heating, stirring. adding

f. Peptization should be avoided. (Peptization is the process by

1. Washing away electrolytes responsible for coagulation.

2. Washing away colloidal pieces of the precipitate.

g. Peptization can be minimized by washing a precipitate with a

h. The bottom line on precipitation is...

1. Colloids are best precipitated from hot, stirred, dilute

2. Filterability is improved if the coagulated colloid is digested