Gravimetric Methods

Gravimetry:
“Gravimetric includes all analytical methods in which the analytical signal is a
measurement of mass or a change in mass”
Mass is the most fundamental of all analytical measurement. Gravimetry is our oldest
quantities analytical technique.

Types of Gravimetric Methods:

There are four types of the gravimetric methods;
1. Precipitation Gravimetry

2. Electro Gravimetry
3. Volatilization Gravimetry
4. Particulate Gravimetry

1.Precipitation Gravimetry:
“When the signal of the measurement of precipitate, we call this method
precipitation gravimetry”
For example:
 Direct determination of chloride ion(Cl¯) by precipitating silver chloride (AgCl).
 Indirect determination of Poᴣ²¯ by precipitating Hg₂Cl₂.

2.Electrogravimetry:
“In electro gravimetry, we deposit analyte as a solid film on an electrode in an electro
chemical cell”
For example:

 Deposition of lead oxide (Pbo₂) at a platinium anode.

 Reduction of copper ion (Cu²⁺) to copper at a pla nium cathode.

3.Volatilization Gravimetry:
“When we use thermal or chemical energy to remove a volatile specie, we call
this method volatilization gravimetry “

For Example:
 In determination of moisture content of bread, we use thermal energy to vaporize
the water in sample (bread).
 To determine the amount of carbon in an organic compound, we use chemical
energy of combustion to convert it into Co₂.

4.Particulate Gravimetry:
“In this method, we determine the analyte by seperating it from sample matrix
(mixture)using a filtration or extraction process”.
For Example:
 Determination of total suspended solids in solution or water.

Importance of Gravimetry
1. Gravimetry is one of the most important technique being included in definitive
techniques.
2. Gravimetry is important because it uses measurements based on SI units such as
Mass or mole.
Defined constant.

Avogadro’s Number.
Mass of C₁₂.
3. Gravimetry is important because using this, we must be able to take the result of
analysis.
4. Using this technique, we can folate our measurements to fundamental physical
properties.

Precipitation Gravimetry
In this method, when we add precipitant to solution containing analyte. In most
methods the product is precipitate.
However, any reaction generating a precipitate can potentially serve as Gravimetric
method.

Theory and Practice:

All precipitation gravimetric analysis shares two important attributes.
First, the precipitate must be of;
Low solubility
High purity
Known composition

Accurate analyt’s mass

Second, the precipitate must be easy to separate from reaction mixture.
Avoiding Impurities
Precipitate must have low solubility and free from impurities. The greatest source of
impurities is the result of chemical and physical interactions occurring at the
precipitate’s surface. A precipitate is generally crystalline with a well-defined lattice
of cations and anions. Those cations and anions at the precipitate’s surface carry,
respectively, a positive or a negative charge because they have incomplete
coordination spheres.

Example
In Agcl precipitate each silver ion in the precipitate’s interior is bound to six chloride
ions. A silver ion at the surface, is bound to no more than five chloride ions and carries
a partial positive charge. The presence of these partial charges makes the precipitate’s
surface an active site for the chemical and physical interactions that produce
impurities.

Impurities which may present in precipitates

1. Inclusion
Trapping of impurities within the crystal lattice. An inclusion does not decrease the
amount of analyte that precipitates, provided that the precipitant is present in
sufficient excess. Thus, the precipitate’s mass is always larger than expected. E.g.
K+ in NH4MgPO4.

2. Occlusion
Trapping of impurities within crystal. an occlusion is localized. An occlusion usually
increases a precipitate’s mass; however, the mass is smaller if the occlusion
includes the analyte in a lower molecular weight form than that of the precipitate.
E.g. Water may have trapped in packets when silver nitrate crystals are formed.
occlusion and inclusion impurities are difficult to remove; digestion may help but
not completely effective. Purification by dissolving and reprecipitation may be
helpful.

3. Surface Adsorption
Unwanted material I adsorbed on to the surface of precipitate. Digestion of
precipitate reduces the amount of surface area and hence the area available for
surface adsorption. a. We can remove surface adsorbates by washing the
precipitate, although the potential loss of analyte cannot be ignored.

4. Co-Precipitation
This is anything unwanted which precipitates with the thing you do want. Co-
precipitation occur to some degree in gravimetric analysis. If an interferent forms
a precipitate that is less soluble than the analyte’s precipitate, we can precipitate
the interferent and remove it by filtration, leaving the analyte behind in solution.
 Controlling the particle size
Precipitation consists of two distinct events: nucleation, the initial formation of
smaller stable particles of precipitate, and particle growth. Larger particles form
when the rate of particle growth exceeds the rate of nucleation.

 Relative supersaturation of solute

RSS= Q-S/S
where Q is the solute’s actual concentration and S is the solute’s concentration at
equilibrium.
A solution with a large, positive value of RSS has a high rate of nucleation,
producing a precipitate with many small particles. we can minimize RSS by
decreasing the solute’s concentration, Q, or by increasing the precipitate’s
solubility, S. A precipitate’s solubility usually increases at higher temperatures, and
adjusting pH may affect a precipitate’s solubility if it contains an acidic or a basic
ion.

 Homogenous precipitation
A visible precipitate takes longer to form when RSS is small both because there is
a slow rate of nucleation and because there is a steady decrease in RSS as the
precipitate forms. the precipitate forms under conditions of low RSS, initial
nucleation produces a small number of particles. As additional precipitant forms,
particle growth supersedes nucleation, resulting in larger precipitate particles. This
process is called homogeneous precipitation.
Two general methods are used for homogeneous precipitation. If the
precipitate’s solubility is pH-dependent, then we can mix the analyte and the
precipitant under conditions where precipitation does not occur, and then
increase or decrease the pH by chemically generating OH– or H3O+ . For example,
the hydrolysis of urea is a source of OH.

What factors determine particle size?

 Colloidal particles show no tendency to settle from solution, nor they easily
filtered.
 The particles with the dimensions on the order of tenths of a millimeter or
greater, temporary disproved in the liquid phase is called crystalline
suspension.
 The particle size is influenced by such experimental variable such as
precipitate solubility, temperature, reactant concentrations, and the rate
of which reactants are mixed.
How do precipitates formed?
Assume that precipitates formed in two ways i.e. Nucleation, Particle growth.

Nucleation
 It is a process in which a minimum number of atoms, ions or molecules are joined
together to produce a stable solid.
 If nucleation predominates, a precipitate containing a large number of
small particle result.
 If particle size predominates, a smaller number of larger particle is formed.
 The rate of nucleation is believed to increase enormously with increasing
Relative Super saturation.
 Larger particles can also be obtained by pH control, Provided the solubility
of the precipitate depends on ph.
Quantitative Applications
 Precipitation gravimetric is reliable means for assessing the accuracy of
other method of analysis.
 It can be used for the analysis of inorganic and organic compounds.
Inorganic Analysis
 Majority of inorganic precipitants show poor selectivity for the analyte. On
the other hand, some organic precipitants are selective for one or two
inorganic ions.
 Precipitation gravimetric is used as a standard method for the
determination of SO42- ions in water and waste water analysis. BaCl2 in an
acidic solution (PH of 4.5 to 5) is used for precipitation to prevent the
possible precipitate of BaCO3 or Ba3(PO4)2 and near the boiling point of
solution. Precipitate is digested at 80-90oc in nearly two hours. Ash less
filter paper pulp is added to the precipitate to add in filtration after
filtering. The precipitate is ignited to constant weight at 800 oC then ppt. is
filter through a fine porosity fritted glass crucible (without adding filter
paper pulp) and dried to constant weight at105oC . There are varieties of
errors including occlusion of Ba(NO3)2 ,BaCl2 and alkali sulphate.
Organic Analysis
 Mostly organic functional groups or heteroatoms can be determined using
precipitation gravimetric method.
 Determination of alkoxy functional groups is an indirect analysis.
 Quantitative Calculations
 Mathematical relationship between analyte and ppt. is always given by
stoichiometry of a precipitation reaction.
 Example: -
 Treatment of analyte R-X with HNO3 with Ag+ then firstly AgNO3 precipitant
will be formed. After reaction AgX precipitates will be formed.
 Quantitative Applications
 Precipitation gravimetric is reliable means for assessing the accuracy of
other method of analysis.
 It can be used for the analysis of inorganic and organic compounds.
Inorganic Analysis
  Majority of inorganic precipitants show poor selectivity for the analyte. On
the other hand, some organic precipitants are selective for one or two
inorganic ions.
 Precipitation gravimetric is used as a standard method for the
determination of SO42- ions in water and waste water analysis. BaCl2 in an
acidic solution (PH of 4.5 to 5) is used for precipitation to prevent the
possible precipitate of BaCO3 or Ba3(PO4)2 and near the boiling point of
solution. Precipitate is digested at 80-90oc in nearly two hours. Ash less
filter paper pulp is added to the precipitate to add in filtration afterfiltering.
The precipitate is ignited to constant weight at 800 oC then ppt. is filter
through a fine porosity fritted glass crucible (without adding filter paper
pulp) and dried to constant weight at105oC . There are varieties of errors
including occlusion of Ba(NO3)2 ,BaCl2 and alkali sulphate.
Organic Analysis
Elemental analysis is the most important application of volatilization gravimetery.
During combustion process with oxygen many carbon and hydrogen products such as
water and carbon dioxide released through the use of preweighed tube containing
selective absorbent provides a direct analysis for the mass of carbon and hydrogen in
organic material.
For example,Alkaline earth metals in organic material can be determined by adding
H₂SO₄,to sample before combustion.
Volatilization gravimetery is used to determine biomass in water and waste
water.Biomass act as an indicator to detect the total mass of organism with in a
sample of water.
Quantitative Calculation
In some cases Quantitative calculation gives the results with out using balanced
chemical equation.
eg. Determination of inorganic ash in a polymer but in some cases stoichiometry of
any relevant reaction is used.
In indirect volatization gravimetric analysis,change in sample weight is proportional to
the amount of analyte.
Evaluation Volatization Gravimetery
The sensitivity of a direct analysis is fixed by the analyte’s chemical form.We can
improve the sensitivity of an indirect analysis by choosing condition that give the
largest possible change in mass.
For example,CaC₂O₄.H₂O is more sensitive in change in mass when ignite at 100°c than
when it ignite at 300°c.
Selectivity is not a problem foe a direct analysis if we use a selective absorbent.
Particalate Gravimetry
Precipitation and volatilization gravimetric methods require that the analyte,ppt in a
chemical reaction.
e.g,we convert a soluble anaylte into a insoluble from that precipates from solution.
Theory and Prective
There are two methods of seperating particalate analyte from its metrix:
(1) Filtration
(2) Extraction
To separate solid from thie matrix we use gravity or apply suction from a vacuum
pump to filiter the sample.
Type of filtration depends upon size of solid particles.Filter for liquid sample are
constructed by following material, “cellulose fiber” glass fiber,ptfe,cellulose,nitrate,
cellulose filter fiber paper range in pore size from 300µm to 2-3µm.
Extration
Extraction are a way to separate a desired substance when it is mixed with others.
The mixture is brought into contact with a solvent in which the substance of interest
is soluble,but the other substance present are insoluble.
We can extend particulate gravimetry to the analysis of gass phase analytes.Solutes
and poorly filterable solid by ex-tracting them with a suitable solvent.
Type:
(Mechanism for solid state extraction )
(a) Adsorption onto a solid substrate.
(b) Absorption into a thin polymer film or chemical
film coated on a solid substrate.
(c) Metal-liquid complexation in which the liquid is
Covalently bounded to the solid substrate using on organic lether
(d) Antibody antigen binding in which the receptor is
Covantely bounded to the solid substrate using an organic lether.
Quantitative Application:
 Particulate gravimetry is important in the environment analysis of water air and
soil samples.
 The microbiological testing of water also uses particulate gravimetry.
 Total air-borne particulate are determined using a high volume air samples
equiped with either cellulose fiber or glass fiber filters.
 Grain size distribution for sediments and solid are used to determine the amount
of sand silt and clay in sample.
 Several standard quantitative analytical methods for agricultural product are
based on measuring the sample mass following a selective solvent extraction.
Quart crystal microbalances equippod with thin film polymer films or chemical
coatings have found numerous quantitative application in environmental analysis.
Evaluate Particulate Gravimetry:
The scale of operation and detection limit for particulate gravimetery can be ex-
tended beyond that of other gravimetric methods by increasing the size of the sample
taken for analysis.This is usually impracticable for other gravimetric methods because
of the difficulty of manipulating a larger sample through the individuals steps pf the
analysis.