Chapter 5

Gravimetric Methods of Analysis

• Measuring mass is the most fundamental of all
analytical measurements

• Gravimetric is the oldest analytical technique

 Overview

• 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
 Outline

Overview of Gravimetry

Precipitation Gravimetry

Volatization Gravimetry

Particulate Gravimetry
 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
 Why Gravimetry is Important
• Is one of only a small number of techniques whose
measurements require only base SI units.

• Estimating the composition of these materials often involves a

gravimetric analysis
 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
 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
 TnP – 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
Ag+ (aq) + Cl- (aq) AgCl (aq) Eq 8.3

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 AgCl 
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’
• The ladder diagram for phosphate, provides a convenient way
to evaluate the pH-dependent solubility of phosphate
precipitates
 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 n 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 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 impurty 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 nd 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