Professional Documents
Culture Documents
By
DR J. A. ADEKOYA
(Chemistry Department)
Office No P54
OUTLINE
Introduction to gravimetry
Types of Gravimetric Methods
Conservation of Mass
Why is Gravimetry Important?
Precipitation Gravimetry
Solubility Considerations
Avoiding Impurities
Introduction to gravimetry
Gravimetry encompasses all techniques
in which we measure mass or a change
in mass. When you step on a scale after
exercising you are making, in a sense, a
gravimetric determination of your mass.
Measuring mass is the most
fundamental of all analytical
measurements, and gravimetry is
unquestionably the oldest analytical
technique.
Introduction to gravimetry
contd.
For example,
To determine the total
suspended solids in water
released from a sewagetreatment facility.
Suspended solids are just
that; solid matter that has
yet to settle out of its
Fig. Filtration method
solution matrix.
For gravimetric
analy
collect a sample and pass
it
through a pre-weighed
filter that retains the
An easier
Foods moisture
approach,
content by a direct
however, is to
analysis. One
weigh the
possibility is to heat a
sample of food
sample of the food to a
before and after
temperature at which
the water in the sample heating, using
the change in
vaporizes.
its mass as an
If we capture the
indication of the
vapour in a preamount of
weighed absorbent
water originally
trap, then the change
in the absorbents mass present. This an
PbO2
moles PO33 = moles
Removing the
Hg2Cl2
y is Gravimetry Important?
The answer is that gravimetry is one of
only a small number of techniques
whose measurements require only base
SI units, such as mass and moles, and
defined constants, such as Avogadros
number and the mass of 12C.
The result of an analysis must
ultimately be traceable to methods,
such as gravimetry, that can be related
to fundamental physical properties.
Most analysts never use gravimetry to
validate their methods.
ecipitation Gravimetry
lubility Considerations
An accurate
precipitation
gravimetric method
of
Cl
.
(7)
Log(Solubility)
-1.00
-2.00
-3.00
-4.00
-5.00
-6.00
-7.00
Ag+ (aq)
6
Effect of pH
Another important parameter
that may affect a
precipitates solubility is the
pH of the solution in which
the precipitate forms. For
example, hydroxide
precipitates, such as Fe(OH)3,
are more soluble at lower pH
levels at which the
concentration of OH is small.
The effect of pH on solubility
is not limited to hydroxide
solubility of Ca3(PO4)2.
H3 C
CH 3
Under these
conditions,
3+
however,
any
Fe
N
N
HO
HO
that might be
Ni
present
nickel dimethylgloxime
precipitates as
Finally, since most precipitants are not
Fe(OH)3.
selective toward a single analyte, there is
always a risk that the precipitant will
react, sequentially, with more than one
species. The formation of these additional
precipitates can usually be minimized by
carefully controlling solution conditions.
Interferents forming precipitates that are
as a function of separating
precipitates
(Purification)
For example, due
to similarities in their
chemistry, a gravimetric analysis for
Ca2+ may be adversely affected by the
Methods of homogeneous
precipitation
(a)If the precipitates solubility is pHdependent, then the analyte and
precipitant can be mixed under
conditions in which precipitation does
not occur. The pH is then raised or
lowered as needed by chemically
generating OH or H3O+. For example, the
hydrolysis of urea can be used as a
source of OH.
The rate of hydrolysis, and thus the rate of
precipitate formation, can be controlled by
adjusting the solutions temperature
Advantage/Demerit of
homogeneous precipitation
large particles of precipitate that are
relatively free from impurities.
increasing the time needed to produce the
Advantage/Demerit of
homogeneous precipitation
OH-
Ag+
NO3- NO3
NO3-
Ag
AgCl
Cl+
ClAgCl
Ag
NO3AgClAgCl
Ag+
OHClAgClAgCl
Ag+
AgClAgClAgCl
ClAgClAgClAg
NO3+
Ag
AgClAgClAgCl
ClAgClAgCl
Ag+
Figure 3
NO3AgClAgClAg
Schematic
ClAgClAgCl
Ag+
model
of AgClAgCl
NO3OH+
Ag
the solid
Ag+
NO3solution
+
Ag
interface
- NO at
a
3
- OH
NO3
particle of
NO3AgCl in a
solution
Precipitate
Primary
adsorption
layer
Bulk solution
Secondar
y
adsorptio
n
Practical Example
Determination of Mg2+ in Water and
Wastewater
Description of Method: Mg is ppted as
MgNH4PO46H2O using (NH4)2HPO4 as the
precipitant. The precipitates solubility in neutral
solns (0.0065 g/100 mL in pure water at 10C) is
relatively high, but it is much less soluble in the
presence of dilute NH3 (0.0003 g/100 mL in 0.6 M
NH3). The precipitant is not very selective, so a
preliminary separation of Mg2+ from potential
interferents is necessary. Ca, which is the most
significant interferent, is usually removed by its
prior pption as the oxalate. The presence of
excess NH4+ salts from the pptant or the addition
Questions
1. Why does the procedure call for a sample
containing no more than 60 mg of Mg2+?
A sample containing 60 mg of Mg2+ will
generate approximately 600 mg, or 0.6 g, of
MgNH4PO46H2O. This is a substantial
amount of precipitate to work with during
the filtration step. Large quantities of
precipitate may be difficult to filter and
difficult to adequately rinse free of
impurities.
2. Why is the solution acidified with HCl before
the precipitant is added?
The HCl is added to ensure that
MgNH4PO46H2O does not precipitate when
uestions contd.
uestions contd.
5. What additional steps in the procedure,
beyond those discussed in questions 2
and 3, are taken to improve the
precipitates purity?
Two additional steps in the procedure help
form a precipitate that is free of
impurities: digestion and reprecipitation.
6. Why is the precipitate rinsed with a
solution of 5% v/v NH3?
This is done for the same reason that
precipitation is carried out in an
Quantitative Applications
Provides a reliable means for assessing
the accuracy of other methods of
analysis or for verifying the composition
of standard reference materials.
Inorganic Analysis
The most important precipitants for
inorganic cations are chromate, the
halides, hydroxide, oxalate, sulfate, sulfide,
and phosphate. A summary of selected
methods, grouped by precipitant, is shown
in Table 1.
EXAMPLE 1
An ore containing magnetite, Fe3O4, was
analyzed by dissolving a 1.5419 g sample
in concentrated HCl, giving a mixture of
Fe2+ and Fe3+. After adding HNO3 to oxidize
any Fe2+ to Fe3+, the resulting solution was
diluted with water and the Fe3+
precipitated as Fe(OH)3 by adding NH3.
After filtering and rinsing, the residue was
ignited, giving 0.8525 g of pure Fe2O3.
Calculate the %w/w Fe3O4 in the sample.
OLUTION Contd.