ANALYTICAL CHEMISTRY

(BKF 1243)

CHAPTER 4
Gravimetric Methods of Analysis
CO1: Explain and describe the theory and application of analytical chemistry
CO3: Solve the problem related to analytical chemistry

By: Dr Farhan M. Said

PO1 Engineering Knowledge - Apply knowledge of mathematics, science, engineering fundamentals
and an engineering specialisation to the solution of complex engineering problems.
PO2 Problem Analysis - Identify, formulate, research literature and analyse complex engineering
problems reaching substantiated conclusions using first principles of mathematics, natural
sciences and engineering sciences.
PO4 Investigation - Conduct investigation into complex problems using research based knowledge and
research methods including design of experiments, analysis and interpretation of data, and
synthesis of information to provide valid conclusions.
 Topics Outline
• Overview of Gravimetry
• Calculations of results from
Gravimetric analysis.
• Application of Gravimetric methods.
 Topic Outcomes
• Explain and differentiate the theory and
practice of precipitate, volatilization and
particulate gravimetry

• Determine the quantitative, qualitative

application of gravimetric method
 Overview of Gravimetric

• Encompasses all technique in which the signal is a mass

or change in mass

• Measuring mass is the most fundamental of all analytical

measurements

• Gravimetric is the oldest analytical technique

 Using Mass as a Signal

• Determine analyte gravimetrically by :

- Directly:

1. determining its mass eg: weighting a solid waste

2. the mass of a compound containing analyte. eg:
aqueous ion, Pb2+, chemically converting it to a
solid form. Suspend a pair of Pt electrodes in
solution, Pb2+ ion in solution oxidizes to PbO2 and
deposits on the Pt electrode
 Cont’
- Indirectly

1. by measuring a change in mass due to its loss, eg :

heat the sample
2. The mass of a compound formed as the result of a
reaction involving the analyte, eg: using HgCl2 to
measure the mass of PO33- (HgCl2 is added, one
mole of PO33- produces one mole Hg2Cl2
 Types of Gravimetric Methods
• Precipitation gravimetry – which the signal is the mass of
a precipitate

• Electrogravimetry – which the signal is the mass of an

electrodeposit on the cathode or anode in an
elecrochemical cell

• Volatilization gravimetry – which the loss of a volatile

species gives rise to the signal

• Particulate gravimetry – which the mass of a particulate

analyte is determined following its separation from its
matrix
 Conservation of Mass

• analyte present in a sample be proportional to

the mass or change in mass
moles Pb2+ = moles PbO2

• removing analyte from its matrix

filter’s final mass – filter’s initial mass = g suspended solid

• Moisture content
sample’s initial mass – sample’s final mass = g H2O
 Why Gravimetry is Important

• Is one of techniques which measurements require only

base SI units.

• Estimating the composition of these materials often

involves a gravimetric analysis
 Gravimetry

• Precipitation Gravimetry

• Volatilization Gravimetry

• Particulate Gravimetry
 Precipitation Gravimetry

• Precipitant – a reagent that causes the precipitation of a

soluble species

• The precipitate is the product of a simple metathesis

reaction between the analyte and precipitant

• Any reaction generating a precipitate can potentially

serve as a gravimetric method
 cont’

• Theory and practice

• Quantitative applications

• Qualitative applications

• Evaluating precipitation gravimetry

 Theory and Practice (TnP)

Important attributes:

• First – the precipitate must be of low solubility, high

purity and of known composition

• Second – the precipitate must be in a form that is easy to

separate from the reaction mixture
 Solubility Considerations

• An accurate precipitation requires precipitate’s solubility

be minimal (accuracy > ±0.1%)
• Isolated precipitate must account for at least 99.9%of
the analyte
• Eg: Ag+ can be determined gravimetrically by adding Cl-
as a precipitant forming a precipitate of AgCl

Ag  (aq)  Cl  (aq) AgCl (s) Eq 8.1

 Cont’
• If this the only reaction considered, falsely conclude that the
precipitate’s solubility, SAgCl, is


S AgCl  Ag  
 Cl 
K sp

Eq 8.2

• AgCl shows a more complex solubility relationship than that

suggested by eq 8.2. Ag+ also forms a series of soluble chloro-
complexes
K1 Eq 8.3
Ag+ (aq) + Cl- (aq) AgCl (aq)
2
Ag+ (aq) + 2Cl- (aq) AgCl2- (aq) Eq 8.4

3
Ag+ (aq) + 3Cl- (aq) AgCl32- (aq) Eq 8.5
 Cont’
• The solubility of AgCl, is the sum of the equilibrium
concentrations for all soluble forms of Ag+
SAgCl = [Ag+] + [AgCl(aq)] + [AgCl2-] + [AgCl32-] Eq 8.6

Solubility of AgCl in terms of the equilibrium

concentration of Cl-

S Ag Cl 
K sp
Cl 

 
 K1 K sp   2 K sp Cl    3 K sp Cl   2
Eq 8.7

As Cl- is added to a solution of Ag+, the solubility of AgCl

initially decreases because of reaction 8.1. increasing the
concentration of chloride, however leads to an increase
in the solubility of AgCl due to the soluble chloro-
complexes formed in reaction 8.3 – 8.5.
 Cont’
• pH also may affects the precipitate’s solubility. eg:
hydroxide precipitate (such as Fe(OH)3), more soluble at
lower pH, which the concentration of OH- is small.

• The effect of pH on solubility also affects precipitates

containing basic or acidic ions.

• Eg : Ca3(PO4)2 is pH dependent, consists of 4 reactions,

Ksp
Ca3(PO4)2(s) 3Ca2+ (aq) + 2PO43- (aq) Eq 8.8
Kb1
PO43-(aq) + H2O (l) HPO42-(aq) + OH-(aq) Eq 8.9
Kb2
HPO42-(aq) + H2O (l) H2PO4-(aq) + OH-(aq) Eq 8.10
Kb3
H2PO4-(aq) + H2O (l) H3PO4(aq) + OH-(aq) Eq 8.11
 Cont’

• Solubility can often be decreased by using a non-

aqueous solvent

• Precipitate’s solubility greater in aqueous solutions

because of the ability of water molecules to stabilize ions
through solvation

• Poorer solvating ability of non-aqueous solvents, even

those that are polar
 Avoiding Impurities
• Precipitate must be free from impurities

• Precipitate typically occurs in a solution rich in dissolved

solids

• A precipitate is generally crystalline, even if only on a

microscopic scale, with a well-defined lattice structure of
cations and anions

• Precipitate particles grow in size because of the

electrostatic attraction between charged ions on the
surface of the precipitate and oppositely charged ions in
solution
 Cont’
• One common type of impurity is an inclusion – a co-
precipitated impurity in which the interfering ion occupies
a lattice site in the precipitate
• Probability of forming an inclusion is greatest when the
interfering ion is present at higher concentrations than
the dissolved lattice ion

• However, inclusion does not decrease the amount of

analyte that precipitates and precipitate’s mass is always
larger than expected

• Can be removed through reprecipitation

 Cont’
• Second type of co-precipitated
impurity, Occlusions – impurity
trapped within a precipitate as it
forms

• Form in two ways –

1. occurs when physically adsorbed
ions are surrounded by additional
precipitate before they can be
desorbed or displaced- mass is
always greater than expected

2. occurs when rapid precipitation

traps a pocket of solution within
the growing precipitate-mass may
be less than expected
 Cont’
• Occlusions – a co-precipitated impurity trapped within a
precipitate as it forms
• Occlusions are minimized by maintaining the precipitate
in equilibrium with its supernatant solution for an
extended time – the process called digestion
• Digestion – the process by which a precipitate is given
time to form larger, purer particles
• Precipitate dissolves and reforms, ensures that occluded
material is eventually exposed to the supernatant
solution
• After precipitate complete, the surface adsorbates,
chemically or physically adsorbed, constitute a third type
of coprecipitated impurity.
• Adsorbates – a co-precipitated impurity that adsorbs to
the surface of a precipitate
 Cont’

• Surface adsorption is minimized by decreasing the

precipitate’s available surface area

• Another source of impurities occurs when other species

in solution precipitate under the conditions of the
analysis

• Solution conditions necessary to minimize the solubility

of a desired precipitate may lead to the formation of an
additional precipitate that interferes in the analysis
 Cont’

• Can be minimized by carefully controlling solution

conditions, either removed by filtration or masked using
a suitable complexing agent

• Also can separate an analyte from a potential interferent

or isolate and weigh both the analyte and the interferent
 Controlling Particle Size
• Precipitation consists of two distinct events, nucleation and
the subsequent growth of these particles
• Relative supersaturation – a measure of the extent to which
a solution, or a localized region of solution, contains more
dissolved solute than that expected at equilibrium (RSS)
• A solute relative supersaturation, RSS

QS
RSS  Eq 8.12
S

Q = solute’s actual concentration

S = solute’s expected concentration at equilibrium
Q – S = a measure of the solute’s supersaturation
when precipitation begins
 Cont’
Large value – indicates that a solution is highly
supersaturated, solution are unstable and high rates of
nucleation-small particle
Small value – precipitation is more likely to occur by
particle growth than by nucleation

• Homogeneous precipitation – a precipitation in which the

precipitant is generated in situ by a chemical reaction

• Two general methods, if pH dependent then the analyte

and precipitant can be mixed under conditions in which
precipitation does not occur. The pH is then raised or
lowered as needed by chemically generating OH- or
H3O+
 Cont’
• Second method – the precipitant itself is generated by a
chemical reaction.

• Eg : Ba2+ can be homogeneously precipitated as BaSO4

by hydrolyzing sulphamic acid to produce SO42-

• Advantage homogeneous precipitation – produce large

particle of precipitate that are relatively free from
impurities, however the process need time

• A precipitate’s particles are electrically neutral, they tend

to coagulate into larger particles.
 Cont’
• Coagulation – the process of
smaller particles of precipitate
clumping together to form larger
particles

• Cannot occur if the secondary

adsorption layer is too thick

• Can be induced in two ways:

– Increasing the concentration of
the ions responsible for the
secondary adsorption layer
– By heating the solution
 Cont’
• After precipitation and digestion are complete, separate
by filtration
Proper procedure to
transferring the
supernatant* to the
filter paper cone

Supernatant – the
solution that remains
after a precipitate
forms
 precipitation
complete
Digestion

Filtering the precipitate

Rinsing the precipitate

Drying the precipitate

Determine the composition of final precipitate

Procedure for filtering through a filtering
crucible. The trap is used to prevent
water from a water aspirator from
backwashing into the suction flask
 Quantitative Applications

• Inorganic analysis – most important precipitants for

inorganic cations are chromate, the halides, hydroxide,
oxalate, sulfate, sulfide and phosphate.
• Inorganic anions can be determined using the same
reactions by reversing the analyte and precipitant.
• Eg : chromate can be determined by adding BaCl2 and
precipitatingBaCrO4.
• Eg : sulfate is analyzed by precipitating BaSO4, using
BaCl2 as the precipitant
 Quantitative Application – cont’

• Organic analysis – several organic functional groups or

heteroatoms can be determined using gravimetric
precipitation methods

• Examples are outlined in Table 8.5

 Example 1

• An ore containing magnetite, Fe3O4, was analyzed by

dissolving a 1.5419 g sample in concentrated HCl, giving
a mixture of Fe2+ and Fe3+. After adding HNO3 to oxidize
any Fe2+ to Fe3+, the resulting solution was diluted with
water and the Fe3+ precipitated as Fe(OH)3 by adding
NH3. After filtering and rinsing, the residue was ignited,
giving 0.8525 g of pure Fe2O3. Calculate the %w/w
Fe3O4 in the sample.

Note : demonstrates the direct analysis of a single analyte

Answer: 53.44%
 Example 2

• A 0.6113 g sample of Dow metal, containing aluminum,

magnesium, and other metals, was dissolved and
treated to prevent interferences by the other metals. The
aluminum and magnesium were precipitated with 8-
hydroxyquinoline. After filtering and drying, the mixture of
Al(C9H6NO)3 and Mg(C9H6NO)2 was found to weight
7.8154 g. The mixture of dried precipitates was then
ignited, converting the precipitate to a mixture of Al2O3
and MgO. The weight of this mixed solid was found to be
1.0022 g. Calculate the %w/w Al and %w/w Mg in the
alloy.

Answer: Al 2.91%, Mg 95.55%

• An indirect analysis the precipitate does not contain the
analyte, but is the product of reaction involving the
analyte.
 Example 3

• An impure sample of Na3PO3 weighting 0.1392 g was

dissolved in 25 mL of water. A solution containing 50 mL
of 3% w/v mercury(II) chloride, 20 mL of 10% w/v sodium
acetate and 5 mL of glacial acetic acid was then
prepared. The solution containing the phosphite was
added dropwise to the second solution, oxidizing PO33-
to PO43- and precipitating Hg2Cl2. After digesting, filtering
and rising, the precipitated Hg2Cl2 was found to weigh
0.4320 g. Report the purity of the original sample as
%w/w Na3PO3.
 Qualitative Applications

• Precipitation gravimetry can also be applied to the

identification of inorganic and organic analytes, using
precipitants such as those outlined in Tables 8.1, 8.2, 8.4
and 8.5
• Since this does not require quantitative measurements,
the analytical signal is simply the observation that a
precipitate has formed.
• Largely replaced by spectroscopic methods of analysis
 Evaluating Precipitation Gravimetry
• Scale of operation – governed by the sensitivity of the
balance and the availability of sample

• Accuracy – macro-major samples, relative errors of 0.1-

0.2% are routinely achieved. Limitations – solubility
losses, impurities in the precipitate and the loss of
precipitate during handling

• Precision – depends on the amount of sample and

precipitate involved. Smaller amounts, relative precisions
1-2ppt, larger amounts, extended to several ppm
 Cont’

• Sensitivity – relate the signal (g of precipitate) to the

absolute amount of analyte in the sample

• g precipitate = k x g of analyte

k, method’s sensitivity, determined by the

stoichiometry between the precipitate and the
analyte
 Cont’
• Eg : determination of Fe as Fe2O3. Conservation of
mass for Fe, 2 x moles Fe2O3 = moles Fe

• Converting moles to grams and rearranging

1 FW Fe2O3
g Fe2O3    g Fe
2 AW Fe
• k is equal to

1 FW Fe2O3
k 
2 AW Fe
 Cont’

• Selectivity : due to chemical nature, precipitants are

usually not selective for a single analyte
• Time, cost and equipment – are time-intensive and rarely
practical when analyzing a large number of samples.

• Does not require an analysts’s immediate supervision,

practical for a few sample

• Few equipments needed, inexpensive, routinely

available in laboratories, and easy to maintain.
 Volatilization Gravimetry

• Second approach to gravimetry – thermally or chemically

decompose a solid sample

• Volatile products of the decomposition reaction may be

trapped and weighed to provide quantitative information

• Thermogravimetry – a form of volatilization gravimetry in

which the change in a sample’s mass is monitored while
it is heated
 Volatilization Gravimetry

• Theory and practice

• Quantitative applications
 Theory and Practice

• Requires the products of the decomposition reaction be

known

• For organic compounds, volatilization is accomplished by

combustion, and the products are gases such, CO2,
H2O, N2

• Inorganic compounds, identification of volatilization

products depend on the temperature at which the
decomposition is conducted
 Cont’

• The loss of a volatile gas on thermal decomposition is

indicated by a step in the thermogram

• Thermogram – a graph showing change in mass as a

function of applied temperature
 Example 8.4

• The thermogram for CaC2O4.H2O shows the change in

mass. The original sample weighed 24.60 mg and was
heated from room temperature to 1000 0C at a rate of 5
0C min. the following changes in mass and

corresponding temperature ranges were observed:

• Loss of 3.03 mg from 100 – 250 0C
• Loss of 4.72 mg from 400 – 500 0C
• Loss of 7.41 mg from 700 – 850 0C
• Determine the identities of the volatilization products and
the solid residue at each step of the thermal
decomposition.
 Equipment

• The weight of a solid residue is determined following

either thermal decomposition at a fixed temperature or
combustion
• Accomplished using a Bunsen or Meker burner, a
laboratory oven or a muffle furnace, with the volatile
products vented to the atmosphere
• Weight of the sample and the solid residue are
determined using an analytical balance
• Decomposition of the sample is conducted in a closed
container, and the volatilized gases are carried by a
purge-gas stream through one or more selective
absorbent traps
 Quantitative Applications

• Inorganic analysis – determining the inorganic ash

content of organic materials, such as polymers and
paper, is an example of a direct volatilization gravimetric
analysis.
• Indirect analyses based on the weight of the residue
remaining after volatilization are commonly used in
determining moisture
 Cont’

• Organic analysis –the combustion products are passed

through preweighed tubes containing appropriate
absorbents – provides a direct indication

• Also used to determine biomass in water and

wastewater
 Cont’

• Quantitative calculations – by applying the principle of

conservation of mass to carbon

• See example 8.5 for direct volatilization gravimetric

analysis (determination of a compound’s elemental
composition)

• See example 8.6 for indirect volatilization gravimetric

analysis (the change in the sample’s weight is
proportional to the amount of analyte)
 Example 8.5

• A 101.3 mg sample of an organic compound known to

contain Cl is burned in pure O2 and the combustion
gases collected in absorbent tubes. The tube used to
trap CO2 increase in mass by 167.6 mg, and the tube for
trapping H2O shows a 13.7 mg increase. A second
sample of 121.8 mg is treated with concentrated HNO3
producing Cl2, which subsequently reacts with Ag+,
forming 262.7 mg of AgCl. Determine the compound’s
composition, as well as its empirical formula.
 Evaluating Volatilization Gravimetry

• The scale of operation, accuracy and precision of

gravimetric volatilization methods are similar to that
described precipitation gravimetry

• Direct analysis (DA) - Sensitivity is fixed by the analyte’s

chemical form following combustion or volatilization.
• DA – based on the residue’s weight following
combustion or volatilization is possible when the residue
only contains the analyte of interest
 Cont’

• Indirect analysis, (IA)– sensitivity can be improved by

carefully choosing the conditions for combustion or
volatilization so that the change in mass is as large as
possible.
• IA – only feasible when the residue’s change in mass
results from the loss of a single volatile product
containing the analyte
 Particulate Gravimetry

• Two approaches :
• filtration – solid particulates are separated from their gas,
liquid or solid matrix, and
• Extraction – can be extracted from its matrix with a
suitable solvent
 Quantitative Applications

• Microbiological testing of water

• Total airborne particulates are determined using a high-
volume air sampler
• Grain size distributions for sediments and soils are used
to determine the amount of sand, silt and clay present in
a sample
 Quantitative Calculations

• A 200.0 mL sample of water was filtered through a

preweighed glass fiber filter. After drying to constant
weight at 105oC, the filter was found to have increased in
mass by 48.2mg. Determine the total suspended solids
for the sample in parts per million
 Evaluating Particulate Gravimetry

• Uses the same balances as other gravimetric methods

• Also capable to achieve similar levels of accuracy and
precision