ANACHEM LEC: M6 GRAVIMETRIC METHODS

GRAVIMETRIC METHODS

 Are quantitative methods that are based on

determining the mass of a pure compound to
which the analyte is chemically related
 Method in which the analyte is converted to an
insoluble substance which is isolated and
weighed
 Based on the conversion of elements or ions
into a pure and stable compound after a
precipitate reaction which can be directly
weighed and quantified

TYPES OF GRAVIMETRIC METHODS

 Precipitate Gravimetry
 Volatilization
 Electrogravimetry

PRECIPITATE GRAVIMETRY
ANALYTE
 Analyte is separated from a solution of the
 The compound or species to be analyzed
sample as a precipitate and is converted to
in the sample or solution
a
 compound of known composition that can PRECIPITATE
be weighed.  The substance created after analyte is
 This is a type of method wherein the separated from the solution or sample
solution is heated to separate the analyte
as a precipitate and is converted to a PRECIPITATE REAGENT
compound of known composition that can
 Aka precipitant;
be weighed.
 used to separate the analyte in the solution

PROPERTIES OF PRECIPITATES AND

PRECIPITATING REAGENTS
 Ideally, a gravimetric precipitating reagent
should react specifically or at least selectively
with the analyte.
 In addition to specificity and selectivity, the
ideal precipitating reagent would react with
the analyte to give a product that is:
1. Readily filtered and washed free of
GENERAL STEPS
contaminants
2. Sufficiently low solubility
1. Analyte is converted to soluble precipitate.
3. Unreactive with atmospheric constituents
2. Filtration of the precipitate. 4. Of known composition after it is dried or
ignited
3. Washing the precipitate to free impurities.
4. Conversion into a product with known PARTICLE SIZE AND FILTERABILITY
OF PRECIPITATES
composition by heat treatment.
 Large particles (precipitates) – desirable
5. Final product is weighed WHY?
1. Easy to filter

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 ANACHEM LEC: M6 GRAVIMETRIC METHODS

2. Easy to wash free of impurities FORMATION

3. Purer than fine precipitates

FACTORS THAT DETERMINE PARTICLE NUCLEATION

SIZE
 “Start of new structure”
 A process in which a minimum number of
1. Precipitate solubility atoms, ions, or molecules join together to give
2. Temperature a stable solid.
3. Reactant concentrations  Nuclei form on the surface of suspended solid
4. Rate at which reactants are mixed contaminants (e.g. dust particles).
 Precipitate – large number of small particles
VON WEIMARN EQUATION
PARTICLE GROWTH

 “Continuing growth of structure”

  Q = concentration of solute  Competition between additional nucleation
 S = equilibrium solubility and growth on existing nuclei.
 Relative saturation:  Precipitate – small number of large particles
o Large = precipitate tends to be
colloidal
o Small = precipitate tents to be
crystalline precipitate

CONTROLLING THE PARTICLE SIZE

1. Increasing the Temperature

 Increase the solubility of precipitate (S)
2.Diluting the Solution
 Minimize the solute concentration (Q
3.Slow Addition of Precipitating Agent with Good
Stirring
 Minimize the solute concentration (Q) Difference between nucleation and particle
4.Large particles can be achieved by pH control growth

FIRST STEP TO GRAVIMETRIC  nucleation is the formation of a new structure

METHOD: whereas;
Precipitation  particle growth is the process of increasing the
 Is the process of forming an size of a pre-existing structure.; Also, particle
growth has three stages
insoluble compound.
o Nucleation
 Usually contains the desired ion of the o Coalescent coagulation
sample. o Agglomeration
 This is also the part where precipitating
agent is used.

COLLOIDAL PRECIPITATES
MECHANISM OF PRECIPITATE

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 ANACHEM LEC: M6
COLLOID
 Mixture that has particles that are able to
remain evenly distributed throughout the
solution; substances remain dispersed
and do not settle to the bottom of the
container
BROWNIAN MOTION OR MOVEMENT
 Particles in both liquids and gases
(collectively called fluids) move randomly.
 prevents settling out of solution under the
influence of gravity.
 Larger particles can be moved by light, fast-
moving molecules.
 Named after the botanist Robert Brown, who
first observed this in 1827
COAGULATION OF COLLOIDS
 Coagulation can be hastened by heating,
stirring, and adding an electrolyte to the
medium.
 Colloidal suspensions are stable because all of
the particles of the colloid are either positively
or negatively charged and thus repel one
another
ADSORPTION
 process in which a substance (gas, liquid, or
solid) is held on the surface of a solid
ABSORPTION
 retention of a substance within the pores
of a solid.
1.PRIMARY ADSORPTION LAYER - layer
attached directly to the solid surface
GRAVIMETRIC METHODS
2.COUNTER-ION LAYER - sufficient excess
of negative ions to balance out the charge
present on the surface of the particle
3.ELECTRIC DOUBLE LAYER - provides
stability to the colloidal suspension
In the given example, it shows a colloidal
Fe(OH)3 particle in a solution that contains an
Primary Adsorption layer + Counter-ion layer
= Electric double layer
excess ions. Its primary adsorption layer consists
mainly of adsorbed iron (Fe3+) ions. While its
counter-ion layer is the excess negatively-charged
ions around the primary layer. The orange part is
what consists its electric-double layer.
PEPTIZATION OF COLLOIDS
 “reverse of coagulation”
 The process by which a coagulated colloid
reverts to its original dispersed state.
 When coagulated colloids returns to its
original state, counter-ion layer is lessened,
thus, particles detach themselves to the
coagulated mass again.
 Peptization is done through washing the
precipitates but that makes the washings
cloudy and freshly dispersed particles pass
When colloidal particles meet each other, this
electric double layer brings an electrostatic
repulsive force that prevent these particles from
colliding and adhering.
through the filter.
 Washing helps in minimizing contamination
but a risk of losing particles is also noted. So,
the proper type of washing agent must be
used.
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 A good washing agent usually contains
electrolytes so as not to harm the forces or
charges present around the particle
Precipitation from Homogeneous Solution
 Technique where in precipitating agent is
formed in a solution of the analyte by a slow
chemical reaction.
 Usually done after digestion – gradual adding
of precipitating agent instead of directly
pouring it into the solution.
 Why gradually? Solids formed by
homogeneous precipitation are generally purer
and more easily filtered than precipitates
generated by direct addition of a reagent to the
analyte solution
COPRECIPITATION
 Process in which normally soluble compounds
are carried out of solution by a precipitate.
 Removal of soluble compounds in the solution
during ppt formation
 Adsorption is a common source of
coprecipitation and is likely to cause
significant contamination of precipitates with
large specific surface areas.
 Washing helps remove these adsorbed
compounds attached on precipitates. But,
regardless of the method of treatment, a
coagulated colloid is always contaminated to
some degree, even after extensive washing.
 Four types:
 Surface adsorption
 Mixed-crystal formation
 Occlusion
 Mechanical entrapment
GRAVIMETRIC METHODS
Colloidal particles show no tendency to settle from
solution and are difficult to filter. To trap these
particles, the pore size of the filtering medium
must be so small that filtrations take a very long
time.
REPRECIPITATION
 Process where the filtered solid is
redissolved and reprecipitated to minimize
the effects of adsorption.
 This is usually done in between filtration
and washing. Filtering and washing the
solution back-and-forth significantly lowers
the contaminant concentration and less
adsorption occurs.
 Reprecipitation adds substantially to the
time required for an analysis. However, it
is often necessary for such precipitates as
the hydrous oxides of iron (III) and
aluminum, which have extraordinary
tendencies to adsorb the hydroxides of
heavy-metal cations such as zinc,
cadmium, and manganese
DRYING AND IGNITION OF
PRECIPITATES
 Process where a gravimetric precipitate is
heated until its mass becomes constant.
 Heating removes the solvent and any volatile
electrolytes carried down with the precipitate
 Some precipitates are also ignited to
decompose the solid and form a compound of
known composition. During this step, moisture
is completely removed from the precipitates.
 These precipitates form a new compound and
is often called as the weighing form
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 ANACHEM LEC: M6 GRAVIMETRIC METHODS

o weighed form
(that is, a
factor ensuring
consistency
between the
result and
chemical
standards);
 Gravimetric Factor
(GF) – the
stoichiometric ratio of
the analyte to the
weighed form.
 Mathematically, GF is calculated as
the ratio of the atomic weight of the
analyte to the molecular weight of the
weighed form.
VOLATILIZATION

 The analyte is separated from other

constituents of a sample by converting it to a
gas of known chemical composition.
 The mass of the gas then serves as a measure
of the analyte concentration.

ELECTROGRAVIMETRY
 Therefore, the smaller is GF, the
smaller will be the amount of
 The analyte is separated by deposition on an analyte per unit mass of weighed
electrode by an electrical current.
form that can be quantified and the
highest will be the sensitivity of the
gravimetric method

 The mass of this product then provides a
measure of the analyte concentration.
GRAVIMETRIC METHODS
 A dimensionless quantity used as a
proportionality constant between the
analyte weight and the gravimetric
weighing;
 A traceability link between atomic
weights (chemical standards) and
the
PROBLEM # 1
The calcium in a 200.0-mL sample of a natural
water was determined by precipitating the cation
as CaC2O4. The precipitate was filtered, washed,
and ignited in a crucible with an empty mass of
30.1270 g. The mass of the crucible plus CaO was
32.0525 g. Calculate the concentration of Ca in
water in units of grams per 100 mL of the water.
(Molar mass: Ca= 40.08g/mol ; O= 16.00g/mol)
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a. Mass (g) of FE present in the

sample

b. Percent (%) Fe present in the

sample

PROBLEM # 2

An iron ore was analyzed by dissolving a 1.4321-g

sample in concentrated HCl. The resulting solution
was diluted with water, and the iron (III) was
precipitated as the hydrous oxide Fe2O3 · H2O by c. Gravimetric factor of Fe/Fe203
the addition of NH3. After filtration and washing,
the residue was ignited at a high temperature to
give 0.5295 g of pure Fe2O3. (Molar mass: Fe=
55.85g/mol ; O=16.00 g/mol) Calculate the
following:

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