Analytical Chemistry

NT10402

Week 9 Gravimetric method of analysis

Jahurul Haque, PhD

Faculty of Food Science and Nutrition
Universiti Malaysia Sabah
 Gravimetric Analysis
Introduction
1.) Gravimetric Analysis:
(i) A technique in which the amount of an analyte in a sample is
determined by converting the analyte to some product

 Mass of product can be easily measured

(ii) Analyte: the compound or species to be analyzed in a sample

(iii) Overall, gravimetry sounds simple.

 Advantages - when done correctly is highly accurate (most
accurate of all time); requires minimal equipment

 Disadvantage - requires skilled operator, slow.

Convert analyte into a solid, filter, weigh, calculate via a mole map
 Gravimetric Methods of Analysis
Gravimetric methods of analysis are based on the
measurement of mass. There are 2 major types of gravimetric
methods:

Precipitation methods: The analyte is converted to a

sparingly soluble precipitate. This precipitate is then filtered,
washed free of impurities, and converted to a product of
known composition by suitable heat treatment, and the
product is weighed.

Volatilization methods: The analyte or its decomposition

products are volatilized at a suitable temperature. 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.
Fig: Apparatus for determining the sodium hydrogen carbonate content of
antacid tablets by a gravimetric volatilization procedure.
 How to Perform a Successful
Gravimetric Analysis
• What steps are needed?
1. Sampled dried, triplicate portions weighed
2. Preparation of the solution
3. Precipitation
4. Digestion
5. Filtration
6. Washing
7. Drying or igniting
8. Weighing
9. Calculation
 Gravimetric Analysis
• Gravimetric Analysis – one of the most accurate
and precise methods of macro-quantitative
analysis.
• Analyte selectively converted to an insoluble
form.
• Measurement of mass of material
• Correlate with chemical composition
• Why?
• Simple
• Often required for high precision
 Gravimetric Analysis
• How?
• Quantitative collection of material of known
composition
– Precipitation of analyte with selective agent
– Volitization and collection of analyte
– w/o loss of material in handling/processing
– Free from solvent, impurities
• Determination of mass
– Direct or
– By difference
 Gravimetric Analysis
• Precipitation Techniques
– Add precipitating reagent to sample solution
– Reacts with analyte to form insoluble material
– Precipitate has known composition or can be converted
to known composition
• Precipitate handling involves
– Quantitative collection (no losses)
– Isolation of pure product
• Measure mass of precipitate
• Calculation of original analyte content
(concentration)
 Gravimetric Analysis

• Desirable properties of analytical

precipitates:
– Readily filtered and purified
– Low solubility, preventing losses during
filtration and washing
– Stable final form (unreactive)
– Known composition after drying or ignition
 Gravimetric Analysis
• Filterability of Precipitates:
• Colloidal suspensions
– 10-7 to 10-4 cm diameter
– Normally remain suspended
– Very difficult to filter
• Crystalline suspensions
– > tenths of mm diameter
– Normally settle out spontaneously
– Readily filterable
 Gravimetric Analysis
• Filterability of Precipitates:
– Precipitate formation affected by
– RELATIVE SUPERSATURATION(R.S.)
• R.S. = (Q-S)/S
S = Equilibrium Solubilty of Precipitate
Q = Instantaneous concentration of the
solute
• Larger Q leads to colloidal precipitates.
 Properties of precipitates and Precipitating
reagents
A gravimetric precipitating agent should react specifically,
and selectively with the analyte. The ideal precipitating
reagent would react with the analyte to give a product that is

1. easily filtered and washed free of contaminants;

2. of sufficiently low solubility that no significant loss of the

analyte occurs during filtration and washing;

3. unreactive with constituents of the atmosphere;

4. of known chemical composition after it is dried or, if

necessary, ignited
Example; AgNO3. The only common ions that it precipitates
from acidic solution are Cl-, Br-, I-, and SCN-.
 Particle Size and Filterability of
Precipitates

• 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.
What Factors Determine Particle Size?
• The particle size of solids formed by precipitation varies
enormously. At one extreme are colloidal suspension,
whose tiny particles are invisible to the naked eye (10-7 to
10-4 cm in diameter).

• Colloidal particles show no tendency to settle from

solution, nor are they easily filtered.

• At the other extreme are particles with dimensions on the

order of tenths of millimeter or greater.

• The temporary dispersion of such particles in the liquid

phase is called a crystalline suspension.

• The particles of a crystalline suspension tend to settle

spontaneously and are readily filtered.
What Factors Determine Particle Size?
The particle size of a precipitate is influenced by
experimental variables as precipitate solubility,
temperature, reactant concentrations, and the rate at
which reactants are mixed.
The particle size is related to a single property of the
system called its relative supersaturation, where
relative supersaturation = (Q – S)/S… …(12-1)
Q is the concentration of the solute at any
instant and S is its equilibrium solubility.

When (Q–S)/S is large, the precipitate tends to be

colloidal.
When (Q–S)/S is small, a crystalline solid is more
likely.
 How do Precipitates Form?
• Precipitates form in two ways, by nucleation and by particle
growth.
• The particle size of a freshly formed precipitate is
determined by which way is faster.

• In nucleation, a few ions, atoms, or molecules (perhaps

as few as four or five) come together to form a stable solid.

• Often, these nuclei form on the surface of suspended solid

contaminants, such as dust particles.

• Further precipitation then involves a competition between

additional nucleation and growth on existing nuclei (particle
growth).
• If nucleation predominates, a large number of very fine particles
is produced.
• If particle growth predominates, a smaller number of larger
particles is obtained.
 Controlling Particle Size
• Experimental variables that minimize supersaturation and
thus produce crystalline precipitates include elevated
temperatures to increase the solubility of the precipitate (S
in Equation 12-1), dilute solutions (to minimize Q), and
slow addition of the precipitating agent with good stirring.

• The last two measures also minimize the concentration of

the solute (Q) at any given instant.

• If the solubility of the precipitate depends on pH, larger

particles can also be produced by controlling pH.

• For example, large, easily filtered crystals of calcium

oxalate are obtained by forming the bulk of the precipitate
in a mildly acidic environment in which the salt is
moderately soluble.
 Colloidal Precipitates
Coagulation of Colloids: Coagulation can be hastened by
heating, by stirring, and by adding an electrolyte to the
medium.
• Colloidal suspensions are stable because all the
particles present are either positively or negatively
charged.
• This charge results from cations or anions that are bound
to the surface of the particles.
• The process by which ions are retained on the surface of
a solid is known as adsorption.
• We can readily demonstrate that colloidal particles are
charged by observing their migration when placed in
an electrical field.
 Attached directly to the solid surface
is the primary adsorption layer,
which consists mainly of adsorbed
silver ions.

Surrounding the charged particle is

a layer of solution, called the
counter-ion layer, which contains
sufficient excess of negative ions
(principally nitrate) to just balance
the charge on the surface of the
particle.

The primarily adsorbed silver ions

and the negative counter-ion layer
constitute an electric double layer
that imparts stability to the colloidal
Figure 12-1: A colloidal silver suspension.
chloride particle suspended in
a solution of silver nitrate. As colloidal particles approach one
another, this double layer exerts an
electrostatic repulsive force that
prevents particles from colliding and
adhering.
 • The upper curve represents a
particle in a solution that
contains large excess of silver
nitrate, and the lower curve
has a much lower silver
nitrate content.

• The effective charge can be

thought of as a measure of
the repulsive force that the
particle exerts on like
particles in the solution.

Fig:12-2 Effect of AgNO3 and

electrolyte concentration on the
thickness of the double layer
surrounding a colloidal AgCl
particle in a solution containing
excess AgNO3.
 Peptization of Colloids
• Peptization refers to the process by which a
coagulated colloid reverts to its original dispersed state.
• When a coagulated colloid is washed, some of the
electrolyte responsible for its coagulation is leached
from the internal liquid in contact with the solid
particles.
• Removal of this electrolyte has the effect of increasing
the volume of the counter-ion layer.
• The repulsive forces responsible for the original
colloidal state are then reestablished, and particles
detach themselves from the coagulated mass.
• The washings become cloudy as the freshly dispersed
particles pass through the filter.
 Crystalline Precipitates
• Crystalline precipitates are generally more easily filtered and
purified than are coagulated colloids. In addition, the size of
individual crystalline particles, and thus their filterability, can
be controlled to some extent.

• The particle size of crystalline solids can often be

improved significantly by minimizing Q, maximizing S, or
both in Equation.

• Minimization of Q is accomplished by using dilute

solution and adding the precipitating from hot solution or
by adjusting the pH of the precipitation medium.

• Digestion of crystalline precipitates (without stirring) for

some time after formation frequently yields a purer, more
filterable product. The improvement in filterability results
from the dissolution and recrystallization.
 Coprecipitation
Coprecipitation is a process in which normally soluble
compounds are carried out of solution by a precipitate.

There are 4 types of coprecipitation:

i) surface adsorption,
ii) mixed-crystal formation,
iii) occlusion
iv) mechanical entrapment

Surface adsorption and mixed crystal formation are

equilibrium processes, whereas occlusion and mechanical
entrapment arise from the kinetics of crystal growth.
Minimizing Adsorbed Impurities on Colloids
• The purity of many coagulated colloids is improved by
digestion. During this process, water is expelled from
the solid to give a denser mass that has a smaller
specific surface area for adsorption.

• Washing a coagulate colloid with a solution containing a

volatile electrolyte may also be helpful because any
nonvolatile electrolyte added earlier to cause coagulation
is displace by the volatile species.

• Washing does not remove much of the primarily

adsorbed ions because the attraction between these ions
and the surface of the solid is too strong. Exchange
occurs, however between existing counter-ions and ions
in the wash liquid.
 Mixed-Crystal Formation
• Mixed-crystal formation is a type of coprecipitation in which
a contaminant ion replaces an ion in the lattice of a crystal.
• In mixed-crystal formation, one of the ions in the crystal
lattice of a solid is replaced by an ion of another element.
• For this exchange to occur, it is necessary that two ions have
the same charge and that their sizes differ by no more than 5%.
• Furthermore, the two salts must belong to the same crystal
class. For example, MgKPO4, in MgNH4PO4, SrSO4 in
BaSO4, and MnS in CdS.
• The extent of mixed-crystal contamination increases as the
ratio of contaminant to analyte concentration increases.
• Mixed-crystal formation is troublesome because little can be
done about it.
• Separation of the interfering ion may have to be carried out
before the final precipitation step. Alternatively, a different
precipitating reagent may be used.
Occlusion and Mechanical Entrapment
• When a crystal is growing rapidly during
precipitate formation, foreign ions in the counter-ion layer
may become trapped, or occluded, within the growing
crystal.
• Mechanical entrapment occurs when crystals lie close
together during growth. Several crystals grow together and
in so doing trap a portion of the solution in a tiny pocket.
• Both occlusion and mechanical entrapment are at a
minimum when the rate of precipitate formation is low,
that is, under conditions of low supersaturation.
• Digestion is helpful in reducing these types of
copreipitation. The rapid solution and reprecipitation that
goes on at the elevated temperature of digestion opens
up the pockets and allows the impurities to escape into the
solution.
Precipitation from Homogeneous Solution
• Precipitation from homogeneous solution is a technique in
which a precipitating agent is generated in a solution of
the analyte by a slow chemical reaction.

• Local reagent excesses do not occur because the

precipitating agent appears gradually and homogeneously
throughout the solution and reacts immediately with the
analyte.

• As a result, the relative supersaturation is kept low during

the entire precipitation. In general, homogeneously formed
precipitates, both colloidal and crystalline, are better suited
for analysis than a solid formed by direct addition of a
precipitating reagent.
Representative methods based on precipitation by
homogeneously generated reagents are given in Table 12-1.
 Drying and Ignition of Precipitates
• After filtration, a gravimetric precipitate is heated until
its mass becomes constant.

• Heating removes the solvent and any volatile species

carried down with the precipitate.

• Some precipitates are also ignited to decompose the

solid and form a compound of known
composition. This new compound is often called the
weighing form.
• The temperature required to produce a suitable
weighing form varies from precipitate to
precipitate.
 • Figure 12-6 shows mass loss as a
function of temperature for
several common analytical
precipitates.

• Heating 3 of the precipitates—

silver chloride, barium sulfate,
and aluminum oxide—simply
causes removal of water and
perhaps volatile electrolytes.

• Moisture is completely removed

from AgCl at higher than 110°C,
but dehydration of Al2O3 is not
complete until a tem greater than
1000°C is achieved.

• Al2O3 formed homogeneously

Figure 12-6 Effect of temperature on with urea can be completely
precipitate mass. dehydrated at about 650°C.
 Gravimetric Analysis
Precipitation Analysis

1.) Principals:
(i)

Reagent + Analyte Solid Product (collect and measure mass)

(ii) Desired Properties of Solid Product

 Should be very insoluble
 Easily filterable (i.e., large crystals)
 Very Pure
 Known and constant composition

Few precipitates have all of these properties, but in most cases

appropriate techniques can help optimize these qualities
 Gravimetric Analysis
Precipitation Analysis

2.) Solubility:
(i) The solubility of a precipitate can be decreased by:
 Decreasing temperature of solution
 Using a different solvent
- usually a less polar or organic solvent (like dissolves like)

Solubility vs. pH Solubility vs. Common Ion Effect Solubility vs. Temperature
 Gravimetric Analysis
Precipitation Analysis

3.) Filterability:
(i) Want product to be large enough to collect on filter:
 Doesn’t clog filter
 Doesn’t pass through filter
(ii) Best Case: Pure Crystals

Worst Case: Colloidal suspension

 Difficult to filter due to small size
 Tend to stay in solution indefinitely  suspended by Brownian motion
Brownian Motion - usually 1-100 nm in size

Whether crystals or colloids are obtained depends on conditions used in the precipitation
 Gravimetric Analysis
Precipitation Analysis

4.) Process of Crystal Growth:

(i) Two Phases in Crystal Growth
Crystal Growth Nucleation – molecules in solution come together randomly and form
small aggregates

Particle growth – addition of molecules to a nucleus to form a crystal

 Gravimetric Analysis
Precipitation Analysis

4.) Process of Crystal Growth:

(ii) Nucleation and Particle growth always compete for molecules/ions
being precipitated.
 If nucleation is faster than particle growth:
- a large number of small aggregates occur giving colloidal suspensions

 If particle growth is faster than nucleation:

- only a few, large particles form giving pure crystals

Want to

Convert to

Colloidal suspension Crystal formation

 Gravimetric Analysis
Precipitation Analysis

4.) Process of Crystal Growth:

(iii) Rates of nucleation vs. particle growth depends on:
 Amount of precipitation solute present
 Described by a quantity known as the Relative Supersaturation (R)

R  (Q  S )
S
S = concentration of solute in solution at equilibrium
Q = actual concentration of solute added to solution

Colloidal Particle

(iv) If R is large,
 Large relative amount of solute in solution
 Favors nucleation and colloid formation

(v) In gravimmetry based on precipitations, a small value of R (~1.0) is

desired in order to favor large crystal growth
 Gravimetric Analysis
Precipitation Analysis

4.) Process of Crystal Growth:

(vi) Methods for Minimizing R
1. Increase temperature of solution
- increases S
- increase amount of solute that can be in solution at equilibrium
2. Add precipitating reagent (precipitant) slowly while vigorously
mixing solution
- avoids local high concentrations of solution
- avoid nucleation and colloid formation
3. Keep volume of solution large
- keep concentration of analyte and precipitating reagent low
4. Control S through chemical means
- by adjusting pH
- adding complexing agents
- example: precipitation of Ca2+ with C2O42-

2- + -
Note: As pH ([H+]) C2O4 + H HC2O4
changes, the solubility Ksp
of CaC2O4 changes 2-
+ C2O4 CaC2O4(s) (Calcium oxalate)
Ca2+
 Gravimetric Analysis
Precipitation Analysis

5.) Homogeneous Precipitation:

(i) Precipitating agent is generated directly in solution by means of a chemical
reaction.
 Ideal case for precipitations
- agent is generated uniformly throughout the solution
- excess are avoided

 Example:

As OH- is produced, pH gradually increases  precipitates a number of compounds (CaC2O4)

 Gravimetric Analysis
Precipitation Analysis

5.) Miscellaneous Notes on Precipitation:

(i) Most ionic compounds are precipitated in the presence of some added
electrolyte
 e.g. 0.1 M HNO3
 Allows the small nucleation aggregates to better overcome any
charge repulsion and promotes particle growth

(ii) Impurities may also be present in the crystal

 Known as co-precipitation
 Creates errors in gravimetric analysis

(iii) Types of Impurities

 Impurities adsorbed to crystal surface
 Gravimetric Analysis
Precipitation Analysis

5.) Miscellaneous Notes on Precipitation:

(iii) Types of Impurities
 Impurities absorbed or trapped within pockets in the crystal
 Occlusion

 Impurities similar to the analyte or reagent

 Impurities placed in the crystal instead of analyte
 Gravimetric
Precipitation Analysis
Analysis
5.) Miscellaneous Notes on Precipitation:
(iv) Impurities are undesirable
 Change the chemical composition of the precipitate
 Causes errors in the analysis

(v) Ways to Minimize Impurities

1. Keep R small
- large pure crystals decrease occlusions and adsorbed impurities
2. Digestion allowing precipitate to stand in mother liquor
(precipitating solution), usually while being heated
- promotes removal of impurities from crystal
- increases size of crystals
3. Wash precipitate, redissolve the precipitate in fresh solvent and
reprecipitate
- helps decrease all types of impurities
Color  Impurity
4. Add a masking agent to solution
- keeps impurities from precipitating, but not analyte

Masking agent + CPCH  Solid product

Mg2+
precipitant
Mn2+ + 6CN-  Mn(CN)64-
 Gravimetric Analysis
Precipitation Analysis

5.) Miscellaneous Notes on Precipitation:

(vi) Washing Precipitates
• Precipitates from ionic compounds

• - need electrolyte in wash solution
• - keep precipitate from breaking up and redissolving (peptization)

 • Electrolyte should be volatile

-removed by drying

- HNO3, HCl, NH4, NO3, etc.

• Example:
 • AgCl(s) should not be washed with H2O, instead wash with dilute HNO3

 (vii) Drying/Igniting Precipitates

 Many precipitates contain varying amounts of H2O
- adsorbed from the air (i.e. hygroscopic)
Precipitates are dried for accurate, stable mass measurements
Precipitates are also ignited to convert to a given chemical form
 Gravimetric Analysis
Scope of Gravimetric Analysis

1.) Accurate
2.) Inexpensive
 Only major equipment is
balance
3.) Method is more tedious than
other approaches
 must carefully consider how to
minimize potential
interferences

Table 27-1Representative gravimetric analyses

 Gravimetric Analysis

• Calculations of analyte content requires

knowledge of :
• Chemistry
• Stoichiometry
• Composition of precipitate
 Gravimetry and Solution Equiliria
• Thermal Conversion to Measurable Form
• Removal of volatile reagents & solvent
• Extended heating at 110 to 115 OC
• Chemical conversion to known stable form
• CaC2O4(s) CaO(s) + CO(g) + CO2(g)
• Volatilization & trapping of component
• NaHCO3(aq)+ H2SO4(aq)  CO2(g)+ H2O +
NaHSO4(aq)
 Gravimetric Calculations
• Gravimetric Factor (GF):
• GF = (fwt analyte (g/mol)/fwt
precipitate(g/mol))x(a(moles analyte/b(moles
precipitate))
• GF = g analyte/g precipitate
• % analyte = (weight analyte (g)/ weight sample
(g)) x 100%
• % (w/w) analyte (g) = ((wt ppt (g) x GF)/wt
sample) x 100%
 Gravimetric Errors
• Unknown Stoichiometry:
• Consider Cl- determination with AgNO3
• Ag+ + Cl-  AgCl
• Ag+ + 2 Cl-  AgCl2
• Gravimetric Factor:
• GF = fwt analyte/fwt precipitate x moles
analyte/moles precipitate
• Calculation for Cl- = wt. Ppt * GF
 Alternative Gravimetry Technique
• Homogeneous Precipitation
• What?
– Precipitating agent generated slowly by chemical reaction in
analyte solution
• Why?
– Precipitant appears gradually throughout
– Keeps relative supersaturation low
– Larger, less-contaminated particles
• How?
– (OH-) by urea decomposition
– (NH2)2CO  2 OH- + CO2 + 2 NH4+
– (S=) by thioacetamide decomposition
– CH3CSNH2 H2S + CH3CONH2
 Precipitation Equilibria:
The Solubility Product
• Solubility of Slightly Soluble Salts:
• AgCl(s)(AgCl)(aq) Ag+ + Cl-
• Solubility Product KSP = ion product
• KSP = [Ag+][Cl-]
• Ag2CrO4(s)  2 Ag+ + CrO4 2-
• KSP = [Ag+]2[CrO4 2-]
 The molar solubility depends on the stoichiometry of the salt.
A 1:1 salt is less soluble than a nonsymmetric salt with the same Ksp.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Precipitation Equilibria:
The Common Ion Effect
• Common Ion Effect
• Will decrease the solubility of a slightly
soluble salt.
The common ion effect is used to decrease the solubility.
Sulfate concentration is the amount in equilibrium and is equal to the BaSO4 solubility.
In absence of excess barium ion, solubility is 10-5 M.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Fig. 10.3. Predicted effect of excess barium ion on solubility of BaSO4.

 Diverse Ion Effect on Solubility:
• Presence of diverse ions will increase the
solubility of precipitates due to shielding of
dissociated ion species.
• KSPo and Activity Coefficients
• AgCl(s)(AgCl)(aq) Ag+ + Cl-
• Thermodynamic solubility product KSPo
• KSP = aAg+ aCl- = [Ag ]ƒAg+ [Cl-]ƒCl-
o . + .

• SP SP Ag+ Cl-
K o= K ƒ .ƒ
.
• KSP = KSP /(ƒAg+ ƒCl)
o
 Ksp = Ksp0/fAg+fSO42-
Solubility increases with increasing ionic strength as activity coefficients decrease.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
Predicted effect of increased ionic strength on solubility of
BaSO4. Solubility at zero ionic strength is 1.0 x 10-5 M.
 Gravimetric calculation using spreadsheet.
Cell B3 calculates %Fe from g. Fe2O3 (Cell D2) and g. sample (Cell B2).

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Using Exel Solver to calculate solubility.
Enter the formula (=s2/Ksp) in Cell E4 (don’t enter =1; that goes in Solver).
The value of s (Cell C4) is changed iteratively until the formula equals 1.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)