Back Titration (Indirect Titration)
• It is generally a two-stage analytical technique
• A titration method where the concentration of an
analyte is determined by reacting it with a known
amount of excess reagent.
• The remaining excess reagent is then titrated
with another second reagent.
• The second titration's results show how much of
the excess reagent was used in the first titration
and the original analyte's concentration can then
Back Titration (Indirect Titration)
Back titrations are used when:
• One of the reactants is volatile, e.g. ammonia.
• A particular reaction is too slow
• Direct titration would involve a weak acid - weak
base titration in which the end-point is very
difficult to observe
• The analyte is in solid form or an insoluble salt,
e.g. calcium carbonate
• The analyte may contain impurities which may
interfere with direct titration.
• Analytical Techniques are the methods used for the
qualitative and quantitative determination of concentration
of a compound by using various techniques
• Analytical methods for rapid determination of chemicals,
biomolecules or cells are of growing interest in various
fields such as environmental control, drug development,
health protection, forensics and biotechnology
• Analytical techniques are procedures or a methods how to
analyse
• analytical techniques are methods used to identify, isolate
or quantify chemicals or materials, or to characterize their
physical properties.
• techniques are defined as the chemical or physical
principles employed to study a substance
• It is the study of the separation, identification, and
quantification of the chemical components of natural and
Gravimetric titrimetry
Gravimetric Titrimetry
• The mass of the standard reagent is measured.
• The ion being analysed is completely precipitated.
The precipitate must be a pure compound.
Gravimetric analysis is based on conversion of
ions/elements/radicals into a stable and pure
compound through precipitation, which can be
directly weighed and quantified.
• Eg. BaCl2 + H2SO4 BaSO4 + 2HCl
• Filtered and dried and put in weighing crucible and
ignited. SO4 in BaSO4 is released as SO2 gas Ba is
left as residue.
.
Basics: Weight amount of Analyte solution is taken It is
precipitated using suitable reagent Precipitate produced is a
pure and stable compound.
Wt. of Analyte = [Wt of precipitate x gravimetric factor]
Wt of sample
% of Analyte = Wt. of analyte x 100
% A = weight of ppt x gravimetric factor (G.F.) x 100
weight of sample •
G.F. = FW[analyte] / FW[precipitate]
Advantage:
Analysis is done accurately by using sensitive and moderate
balance. Direct measurement of the compound is done so no
calibration is required. It is an absolute method.
Gravimetric Analysis (GA)
GA = Quantitative Analysis by
weight
GA is the process of isolating and
weighing an element or a definite
compound of the element in as pure
form as possible.
Major Types of Gravimetric
Methods:
1. Precipitation Method
2. Volatilization Method
Types of Gravimetric Methods
Precipitation Methods:
Analyte is converted to a sparingly soluble precipitate.
Precipitate is → filtered → washed (to remove impurities)
→ converted to a product of known composition by suitable
heat treatment → the product is weighed.
Volatilization Methods:
Analyte or its decomposition products are volatilized
at a suitable temperature.
The volatile product → collected → weighed or the
mass of the product is determined indirectly from the
loss in mass of the sample.
Precipitation Methods
Dissolve Sample
↓
Add Precipitating Agent
↓
Precipitation of Constituent
↓
Separation by Filtration
↓
Washing (to remove soluble
salt)
↓
Drying
↓
Weighing
Precipitation Methods: Examples
Ex-1: Determination of lead (Pb+2)
Pb2+ + 2Cl- → PbCl2(s)
Mass of PbCl2 is then determined
Calculate the amount of Pb+2 in original solution
Ex-2: Determination of Silver
Ag+ + Cl- (excess) → AgCl (s)
Criteria for Successful Analysis of
Precipitation Method
Precipitate must be insoluble so that no appreciable
loss occurs during washing and filtration
Easily Filterable; particle should not pass through
the filtering medium and should not be affected by
washing process.
Pure (free from impurities)
The precipitate must be a pure substance of
definite/known chemical composition
Criteria for Successful Analysis of
Precipitation Method
Filterability:
Particles must to be large enough to collect on filter
Crystals
Doesn’t clog filter
Doesn’t pass through filter
Best Case: Pure Crystals
Worst Case: Colloidal/Flocculated Suspension
Flocculated
Difficult to filter due to small size suspension
Tend to stay in solution indefinitely
(suspended by Brownian motion)
Usually 1-100 nm in size
Colloidal
Solution
Criteria for Successful Analysis of
Precipitation Method
Precipitation Process
Process of Crystal Growth: Two Phases
(i) Nucleation: molecules in solution come together
randomly and form small aggregates
(ii) Particle growth: addition of molecules to a
nucleus to form a crystal
Criteria for Successful Analysis of
Precipitation Method
Precipitation Process
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
Crystal formation
Criteria for Successful Analysis of
Precipitation Method
Precipitation Process
Rates of nucleation vs. particle growth depends on
the amount of precipitation solute present
Relative Supersaturation (R) R Q S
S
S = solubility of precipitate in the medium from which it is being precipitated
Q = concentration of reactants before precipitation
Particle Size 1/R
When R is large, the precipitate tends to be colloidal;
When R is small, a crystalline solid is more likely
Criteria for Successful Analysis of
Precipitation Method
The optimum conditions for precipitation which make the
supersaturation low are
1. Increase temperature of solution
Increases S
Increase amount of solute that can be in solution at equilibrium
2. Add precipitating reagent slowly with stirring
Avoids local high concentrations of precipitant
Avoids 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
Gravimetric Volatilization Method:
Example
Determination of the sodium hydrogen carbonate
content of antacid tablet by a gravimetric
H2SO4 (aq) → CO2 (g)+ H2O (l)+ NaHSO4(aq)
NaHCO3 (aq)+method
volatilization
GA: Advantages
Accurate and precise, when using modern
analytical balances.
Possible sources of error are readily checked,
since filtrates can be tested for completeness of
precipitation and precipitates may be examined for
the presence of impurities.
It is an absolute method, i.e. one involving direct
measurement without any form of calibration being
required.
Relatively inexpensive
GA: Disadvantages
Time-consuming
Any interferrents must be removed prior to
precipitation
Method is not very sensitive; Only suitable for high
concentrations
Applicable to Limited group of elemental analysis
Volatilisation: Water eliminated in a quantitative
manner from many inorganic substances by ignition
is an example of a direct determination. It is
collected on a solid desiccant and its mass
determined by the gain in mass of the desiccant
Determination of the amount of water by measuring
the loss in mass of the sample during heating is an
example of an indirect method. (Water of
crystallization)
Exercise
When an sample of impure potassium chloride
(0.4500g) was dissolved in water and treated with an
excess of silver nitrate, 0.8402 g of silver chloride
was precipitated. Calculate the percentage KCl in
the original sample.
MW of AgCl = 143.32
MW of KCl = 74.55
Ans: 97.12%
Example
A mixture of mercurous chloride (FW 472.09) and
mercurous bromide (FW 560.99) weighs 2.00 g. The
mixture is quantitatively reduced to mercury metal (At wt
200.59) which weighs 1.50 g. Calculate the % mercurous
chloride and mercurous bromide in the original mixture. •
ANS: 0.5182 g
1.50 = 2 * 200.59 * x + 2 * 200.59( 2 − x )
472.09 560.99
Rearranging and solving:
0.8498 + 0.7151 2( ) − x = 1.50 x = 0.5182g
