2.

0 GRAVIMETRIC ANALYSIS

CONTENTS

2.1 Introduction
2.2 Particle size and filterability
2.2.1 What factors determine particle size ?
2.2.2 How do precipitates form ?
2.3 Colloidal precipitates
2.4 Obtaining a good precipitate
2.4.1 Coagulation of colloids
2.4.2 Peptization of colloids
2.4.3 Treatment of colloidal precipitates
2.5 Crystalline precipitates
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2.6 Coprecipitation
2.6.1 Surface adsorption
2.6.2 Mixed crystal formation
2.6.3 Occlusion and mechanical entrapment
2.7 Precipitation from homogeneous solution
2.8 Drying and ignition of precipitates
2.9 Gravimetric calculations
2.10 Applications of gravimetric methods
2.10.1 Inorganic precipitating agents
2.10.2 Organic precipitating agents
2.11 Examples of gravimetric analysis
2.12 Precipitation equilibrium : The solubility product
2
2.1 INTRODUCTION

Gravimetric analysis is a method whereby analytes or

solutes are converted to insoluble species (precipitate)
# Analyte : The constituents of interest in a sample
These precipitates are separated, dried and finally
weighed
From the weight and the chemical content, the weight of
the analyte in the sample can then be calculated

3
There are a few methods using gravimetric analysis
# Precipitation gravimetric
- involves the determination of analyte in the
sample by weighing the precipitate formed in
the solution
- e.g. : Direct determination of Cl- by precipitating
AgCl
# Electrogravimetric
- involves the exchange of metal ion in a solution
through electrochemistry to form metal and
deposited at the electrode

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# Thermogravimetric
- involves the measurement of weight change
during heating in air at a control rate
- the volatile product is then collected and
weighed, or, alternatively, the mass of the
product is determined indirectly from the loss in
mass of the sample
- e.g. : in determining the moisture content of
food, thermal energy vaporizes the H2O, the
amount of carbon in an organic compound may
be determined by using the chemical energy of
combustion to convert C to CO2
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Gravimetric analysis is based on the following reaction
# An analyte, A reacts with reagent, R to yield a
precipitate, which is less soluble
aA + rR AaRr 
# Example, Ca2+ can be determined by gravimetric
analysis through a reaction between Ca2+ and oxalate
ion (C2O42-). The CaC2O4 precipitate formed is then
heated to yield CaO as the reaction below :
Ca2+ + C2O42- CaC2O4 

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There are a few steps involved in gravimetric analysis :
# Preparation of solution
# Precipitation process
# Digestion
# Filtration
# Washing
# Drying
# Weighing
# Calculation

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2.2

Precipitates made up of large particles are generally

desirable in gravimetric work because large particles are
easy to filter and wash free of impurities
In addition, such precipitates are usually purer than are
precipitates made up of fine particles

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2.2.1 WHAT FACTORS
DETERMINE PARTICLE
SIZE ?
Colloidal suspensions
# Size range : 10-6 to 10-4 mm in diameter
# Colloidal particles show no tendency to settle down
from solution
# Difficult or impossible to filter

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Crystalline suspension
# Size range : 10-1 to 10 mm
# Tend to settle spontaneously
# Readily filtered
# Typically of higher purity than colloids
The size of the precipitation particle may be influenced by
# The temperature
# The concentration of the reactants
# The rate at which the reactants are mixed

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Properties of good precipitates :
# Higher purity
# Small surface area
# Large particle size
# Easy to filter / wash
# Insoluble precipitate

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# Experimental evidence indicates that the particle
size of a precipitate is inversely proportional to the
average RSS during the process of precipitation
- relative supersaturation (RSS)
- also known as von Weimarn ratio

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- where
Q = Concentration of solute at any time before
precipitation occurs and is the degree of
supersaturation
S = Solubility of precipitates at equilibrium
- If RSS is high  the precipitate tends to be
colloidal
- If RSS is low  the precipitate tends to form a
crystalline solid

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- We want to keep Q low and S high during
precipitation
- To obtain a pure and bigger precipitate size that
can be filtered, several steps are commonly
taken :
 Using dilute solutions and reagents
# By doing this, the particle growth process
will be slowed and impurities can be
avoided from been trapped in the crystal
 Slowly adding our precipitating reagent and
stir effectively
# This will give a minimum RSS thus slower
down the particle growth 14
 Precipitate from hot solution
# At high temperature, the equilibrium
process is faster
 Precipitate at a low pH
# This is to maintain quantitative
precipitation

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2.2.2 HOW DO PRECIPITATES FORM ?

The effect of RSS on particle size can be explained if we assume

that precipitates form in two ways
# Nucleation
- The mechanism when a small number of ions,
atoms, molecules initially unite
- Two mechanism  spontaneous and induced
# Particle growth
- The three dimensional growth of a particle
nucleus into a larger crystal

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NUCLEATION

Spontaneous nucleation will occur on its own

Examples of induced nucleation - on dust particles, scratches on
the vessel surface, added seed crystals of the precipitate

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PARTICLE GROWTH

Once a nucleation site formed, other ions are attracted to the site
This will result in the formation of large, filterable particles
If done properly, it also reduces contaminates since they don’t ‘fit
in’ to the crystal structure

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Nucleation and particle growth are competing processes although
at least some nucleation must initially occur
predominate

RSS  Nucleation Particle growth

Solution

predominate Nucleation Particle growth

RSS 

We want particle growth to be the predominate factor in

precipitate formation
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Rate of nucleation is, e  RSS
The higher the degree of RSS, the greater the rate of nucleation
Rate of particle formation is  RSS
# If RSS is large  nucleation is favored and
colloidal suspensions tend to be formed
# If RSS is small  particle growth will predominate
resulting in crystalline precipitates

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 Ag+ + Cl-

Nucleation

RSS  RSS 

Particle

Counter ion
Particle
layer
growth
Nucleation
predominant
Particle growth
predominant

Colloidal precipitate Crystalline precipitate 21

The goal is to form crystalline precipitates, so, RSS must be
minimized
This can be done by :
# Increasing S
- Elevate temperature
- pH control
# Decreasing Q
- Use dilute solutions
- Slowly add reagents
- Stirring the solution

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2.3 COLLOIDAL
PRECIPITATES

As an example, we’ll use the following precipitate

formation through out

AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3 (aq)

# NaCl will be our precipitating reagent

# AgCl tends to form colloidal (amorphous)
precipitates

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Initially, there is very little free chloride in the solution due
to the excess of Ag+
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The outer layer of the precipitate contains both Ag+ and Cl-
which tends to attract additional Ag+ to the surface 
primary absorbed layer

# This primary layer is simply an extension of the

precipitate but we’ve run out of Cl-
# The counter ion in excess (nitrate) is attracted to
this layer by electrostatic forces  maintains
electrical neutrality
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# Since the overall structure tends to appear
negative to the solution, it attracts water molecules
that move with the particle

# At high silver concentrations, we have a higher

charge on the precipitate  this results in a larger
particle

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 # The problem is even worse when the counter ion is
large
Net result
# At high silver concentrations and with large counter
ions, we tend to form stable colloids
# The charged structures have difficulty approaching
each other since they are similarly charged

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 2d1

High [Ag+]

Double layer
Particle (counter ion layer,
NO3- ion)

Low [Ag+]

2d2 28
 # 2d1 < 2d2
- easier to approach each other to form
crystalline precipitate
- a filterable precipitate formed
Note : The same type of problem will occur when chloride
is in excess  towards end of precipitation
It would seem that the solution is to keep the
concentration of Ag+ low at all times

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This is impossible to do!
As Ag+ is added, we create locally
high concentrations even when
using dilute solutions
Since we can’t eliminate the
problem, we need ways to
minimize its effect

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2.3 OBTAINING A GOOD PRECIPITATE

Several steps can be taken to help precipitate a colloid and reduce

impurities
Any steps taken must address two competing process
# Coagulation
- The process of smaller colloidal particles of
precipitate clumping together to form larger
particles

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# Peptization
- When a coagulated colloid reverts to its dispersed state

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2.4.1 COAGULATION OF
COLLOIDS

The two common approaches for causing a colloid to

coagulate are heating and adding an electrolyte to the
solution
# Heating the colloid while stirring
- This significantly decreases the number of
absorbed ions per particle
- This reduces the size of the counter ion layer,
making it easier for the particles to approach
each other

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# Increasing the electrolyte concentration of the
solution
- An unrelated, non-interfering ionic compound
(e.g. H+) can be added to the solution
- This reduces the volume of solution that
contains sufficient ions of opposite charge to
neutralize the particle
- The result is that a smaller structure is formed

H+ H+ will neutralize the

NO3 -
counter ion layer

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2.3.2 PEPTIZATION OF COLLOIDS

Peptization refers to the process by which a coagulated colloid

reverts to its original dispersed state
If we’ve gone to the trouble of making a coagulated colloid, we
don’t want to loose it in our attempt to clean it up
Washing a colloid to remove excess counter ion or trapped
impurities can result in peptization
There are several common approaches that can be used to
address this problem

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2.3.3 TREATMENT OF COLLOIDAL
PRECIPITATES

Use a volatile electrolyte

# A relative volatile salt can be used to wash the
precipitate
# This displaces the less volatile, excess counter ion
# Heating the precipitate (during drying) will remove
the volatile electrolyte
# Example for AgCl
- Wash with HCl
- Drying precipitate at 110oC will remove HCl

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Digestion and aging
# Digestion
- The process by which a precipitate is given time
to form larger, purer particles
- Heating the solution for about an hour after
precipitate formation
- This helps to remove weakly bound water
# Aging
- Storing the solution, unheated, overnight
- This allows trapped contaminates time to ‘work
their way out’
# Both can result in a denser precipitate that is
easier to filter

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2.4 CRYSTALLINE PRECIPITATES

This type of precipitate is much easier to work with

# They are easier to filter and purified
# You have greater control over the precipitation
process
In general, the best approach is to slowly form your precipitate
using warm, dilute solutions
Allow it to then digest without stirring

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2.6 COPRECIPITATION

When an otherwise soluble compound is precipitated

along with your analyte
This does not include materials that would normally be
insoluble
There are four types of coprecipitation
# Surface adsorption equilibrium
# Mixed-crystal formation processes
# Occlusion Arise from the
# Mechanical entrapment kinetics of crystal
growth

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2.6.1 SURFACE ADSORPTION

The surface of our precipitate will contain some primary

absorbed ions
As a result, counter ion will also be present
# Example – In our AgCl, the precipitate will
commonly contain some nitrate
Occurs with colloidal and crystalline precipitates
Worse for colloids because the surface area is
significantly larger

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AgCl example
# If nitrate is coprecipitated, our results will be too
high
- Nitrate weights more than chloride
# Further, the results will be variable since the
surface area may differ from sample to sample
# A lower weight counter ion will result in our results
being too low

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Dealing with surface adsorption
# Washing
- This may help but not much
- The attraction of the counter ion is usually too
strong, so you only get a limited exchange
# Washing with a volatile electrolyte
- This is a better approach since the excess can be
removed during drying
- For AgCl, washing with HCl is a reasonable
approach

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# Reprecipitation
- The filtered precipitate is dissolved and then
precipitated a second time
- Only a small portion of the contaminate makes it
into the second solution
- The second precipitate will be purer
- This approach is one of the last result since it
significantly adds to the analysis time

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2.6.2 MIXED-CRYSTAL
FORMATION

If similar ions are present, they can replace our analyte

ion in the crystal lattice during precipitation
Similarly ions have the same charge and have sizes within
5% of our ion
Example – determination of SO42- as BaSO4
# The presence of Pb or Sr will cause a mixed crystal
containing either PbSO4 or SrSO4
This is a problem with both colloidal and crystalline
precipitates
# There is no easy solution to minimize the problem
# When encountered, the only choices are to remove
the interferences prior to precipitation or to select
a different reagent 44
2.6.3 OCCLUSION AND
MECHANICAL
ENTRAPMENT

Occlusion
# If crystal growth is too rapid, some counter ions
don’t have time to escape from the surface

counter ions

Rapid
precipitate
formation

45
Mechanical entrapment
# When rapid growth traps a pocket of solution
# While the solvent can be removed, the trapped
ions will remain after drying

rapid growth
and merging of
particles

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The best way to deal with these problems is to slow things
down
# Using dilute, warm solutions during precipitation
gives counter ions time to leave and helps break
up pockets
# Digestion and aging the precipitate provides
additional times for this to occur as well

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2.7 PRECIPITATION FROM
HOMOGENEOUS
SOLUTION

When a precipitation reagent is added as a solution to or

analyte there will always be locally high concentrations
# This is responsible for many of our problems
regardless of how slowly we add the reagent or
how fast we stir
# Precipitation from homogeneous solution is an
approach that can avoid this problem

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Basis
# Our reagent is added in an unreactive form to our
sample solution
# This permits a complete mixing of all materials
# Some property of the solution is changed to slowly
convert the reagent to a reactive form
# The solution slowly and uniformly changes – no
locally high concentrations

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Example
# Urea – (NH2)2CO

(NH2)2CO + 3H2O  CO2 + 2NH4+ + 2OH-

- Process is controlled by heating the solution just

below boiling
- Used for the precipitation of Al, Ga, Th, Bi, Fe and
Sn as hydroxides

50
2.5 DRYING AND IGNITION OF
PRECIPITATES

After filtration, the precipitate must be dried to constant weight

# Removes excess solvent
# Drives off any volatile species
In some cases, the precipitate is heated to a point where it
decomposes to a stable form for weighing
Thermobalances can be used to determine optimum drying and
temperatures

51
Effect of temperature on precipitate mass

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- H2O
- CO

- CO2

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2.9

The precipitate we weigh is usually in a different form

than the analyte whose weight we wish to report
The principles of converting the weight of one substance
to that of another are using stoichiometric mole
relationships
We introduced the gravimetric factor (GF), which
represents the weight of analyte per unit weight of
precipitate

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#

GF = f wt analyte (g/mol) X a (mol analyte/mol ppt)

f wt ppt (g/mol) b
= g analyte/g precipitate

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 EXERCISES

(1) Using the chemistry formula, write the gravimetric factors for :

Analyte Precipitate
(a) P Ag3PO4
(b) K2HPO4 Ag3PO4
(c) Bi2S3 BaSO4
(d) Mg Mg2P2O7
(e) Cr2O3 BaCrO4
(f) Na2B4O7.10H2O B 2 O3
(g) Fe3O4 Fe2O3

56
In gravimetric analysis, we are generally interested in the
percent composition by weight of the analyte in the
sample, that is :

% substance sought = wt of substance sought (g) X 100%

wt of sample (g)

57
We obtain the weight of substance sought from the
weight of the precipitate and the corresponding weight
per mole relationship

Weight of substance sought (g)

= wt of ppt (g) X f wt substance sought (g/mol)
f wt ppt (g/mol)
X a (mol substance sought/mol ppt)
b
= wt of ppt (g) X GF (g sought/g ppt) 58
Calculations are usually made on a percentage basis

%A = gA X 100%
gsample

We can write a general formula for calculating the

percentage composition of the substance sought

% sought = wt of ppt (g) X GF (g sought/g ppt) X 100%

wt of sample (g) 59
 EXERCISES

(1) Orthophosphate (PO43-) is determined by weighing as ammonium

phosphomolybdate (NH4)PO4.12MoO3. Calculate the percent P in
the sample and the percent P2O5 if 1.1682 g precipitate (ppt) were
obtained from a 0.2711 g sample. Perform the % P calculation
using the gravimetric factor

60
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(2) An ore is analyzed for the manganese content by converting the
manganese to Mn3O4 and weighing it. If a 1.52 g sample yields
Mn3O4 weighing 0.126 g, what would be the percent Mn2O3 in the
sample ? The percent Mn ?

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2.10 APPLICATIONS OF
GRAVIMETRIC METHODS

Gravimetric methods have been developed for most

inorganic anions and cations as well as for such neutral
species as water, SO2, CO2 and iodine
A variety of organic substances can also be readily
determined gravimetrically
Indeed, gravimetric methods are among the most widely
applicable for all analytical procedures

66
2.10.1 INORGANIC
PRECIPITATING
AGENTS

SOME INORGANIC PRECIPITATING AGENTS

Precipitating agent Element precipitated
Ag+ (AgCl), Hg2+ (Hg2Cl2)
(NH4)2S Hg2+ (HgS), Co (Co3O4)
H2C2O4 Ca2+ (CaO), Sr2+ (SrO), Th (ThO2)
HNO3 Sn (SnO2)
BaCl2 SO42- (BaSO4)

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2.10.2 ORGANIC
PRECIPITATING
AGENTS

Tend to be more selective

#
- Reacts with over 20 different metallic cations

- pH can be used to control selectivity

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#

- Will only form complexes with

Pd  yellow, weak complex
Ni  bright red, very stable complex
- Since Pd is not very common, DMG is considered
specific for Ni
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#
- Example  determination of carbonates
- A sample is heated to constant weight, driving
off CO2
- CO2 is collected in a known NaOH solution,
forming Na2CO3
- You can then do a titration

70
 2.11

Some commonly employed gravimetric analyses

Substance Precipitate Precipitate Interferences
analyzed formed weighed
Fe Fe(OH)3 Fe2O3 Many. Al, Ti, Cr, etc
Fe cupferrate Fe2O3 Tetravalent metals
Al Al(OH)3 Al2O3 Many. Fe, Ti, Cr, etc
Al(ox)3* Al(ox)3 Many. Mg does not interfere in
acidic solution
Ca CaC2O4 CaCO3 or All metals except alkalis and Mg
CaO
Mg MgNH4PO4 Mg2P2O7 All metals except alkalis
Zn ZnNH4PO4 Zn2P2O7 All metals except Mg
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2.12 PRECIPITATION
EQUILIBRIA : THE
SOLUBILITY PRODUCT

When substances have limited solubility and their

solubility is exceeded, the ions of the dissolved portion
exist is equilibrium with the solid material
When a compound is referred to as insoluble, actually not
completely insoluble but is slightly soluble
# It’s can be expressed by following reaction

AgCl (AgCl)aq Ag+ + Cl-

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It is difficult to measure the undissociated molecule
However, ionized form can be measured via a compound’s
solubility and chemical availability
Hence, overall equilibrium constant for the above
stepwise equilibrium can be written as solubility product,
Ksp

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# A nonsymmetric salt such as Ag2CrO4 would have a Ksp
as follows

Ag2CrO4 2Ag+ + CrO42-

Ksp =

PbCl2 Pb2+ + 2Cl-

Ksp =

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Criteria for precipitation

MA (s) M+ + A -
Ksp = [M+][A-]

 [M+][A-] > Ksp precipitation should occur

[M+][A-] < Ksp precipitation can not occur
(unsaturated solution)
[M+][A-] = Ksp a solution is saturated

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 EXERCISES

(1) The Ksp of AgCl at 25 oC is 1.0 x 10-10. Calculate the

concentrations of Ag+ and Cl- in a saturated solution of AgCl, and
the molar solubility of AgCl.

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(2) What must be the concentration of added Ag + to just start
precipitation of AgCl in a 1.0 X 10-3 M solution of NaCl ? Given Ksp
for AgCl = 1.0 X 10-10.

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(3) Calculate the molar solubility of PbSO4 and compare it with that of
PbI2. Given Ksp for PbSO4 = 1.6 X 10-8 and PbI2 = 7.1 X 10-9.

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