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222 GRAVIMETRIC METHOD OF ANAL

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.

Fig. Method for the extract


and purification of N2

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

Introduction to gravimetry contd.


We call this a direct analysis because
the analyte itself is the object being
weighed.
What if the analyte is an aqueous ion,
such as Pb2+? In this case we cannot
isolate the analyte by filtration because
the Pb2+ is dissolved in the solutions
matrix
We can measure the analytes mass by
chemically converting it to a solid form.
If we suspend a pair of Pt electrodes in

our solution and apply a sufficiently


positive potential between them for a

troduction to gravimetry contd.

The Pb2+ ion in


solution oxidizes to
PbO2 and deposits on
the Pt electrode
serving as the anode.
The weight of Pt
anode before and
after applying the
direct
analysis potential, the
because
the difference in the two
material
being measurements gives
weighed contains the mass of PbO2 and,

troduction to gravimetry contd.

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

oduction to gravimetry contd.


Indirect analyte without its ever being
weighed. Again, as with the
determination of Pb2+ as PbO2(s), we take
advantage of the analytes chemistry. For

example, phosphite, PO33, reduces Hg2+


to Hg22+.
If HgCl2 is added in excess, each mole of
PO33 produces one mole of Hg2Cl2. The
precipitates mass, therefore, provides an
indirect measurement of the mass of

pes of Gravimetric Methods


direct determination of Cl by
precipitating AgCl. In electrogravimetry
the analyte is deposited as a solid film on
one electrode in an electrochemical cell.
The electrodeposition of Cu on a Pt
cathode, for example, provides a direct
analysis for Cu2+
When thermal or chemical energy is used
to remove a volatile species, we call the
method volatilization gravimetry.
The amount of carbon in an organic
compound may be determined by using

onservation of Massmoles Pb2+ = moles


An accurate
gravimetric analysis
requires that the
mass of analyte
present in a sample
be proportional to
the mass or change
in mass serving as
the analytical
signal. For all
gravimetric
methods this
proportionality

PbO2
moles PO33 = moles
Removing the
Hg2Cl2

analyte from its


matrix by
filtration or
extraction must
be complete
Filters final mass
filters initial mass
= g suspended
solid

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

Precipitation gravimetry is based on the


formation of an insoluble compound
following the addition of a precipitating
reagent, or precipitant, to a solution of the
analyte.
In most methods the precipitate is the
product of a simple metathesis reaction
between the analyte and precipitant;
however, any reaction generating a
precipitate can potentially serve as a
gravimetric method.
A precipitation gravimetric analysis must
have several important attributes. First, the

lubility Considerations

An accurate

precipitation
gravimetric method

requires that the


If this is the only
reaction considered,
precipitates
we would falsely
solubility be
conclude
that
the
minimal.
precipitates solubility,
Many total analysis
SAgCl, is given by
techniques can
routinely be
performed
To obtain this
withlevel
an of accuracy,
the
isolated
precipitate must
accuracy
of better
account
for at least 99.9% of the
than 0.1%.

ubility Considerations contd.

solubility losses may be minimized by


adding a large excess of Cl. In fact, adding
a large excess of Cl eventually increases
the precipitates solubility. To understand
why AgCl shows a more complex solubility
relationship than that suggested by
equation 2, we must recognize that Ag+

also forms a series of soluble chlorocomplexes

ubility Considerations contd.

The solubility of AgCl, therefore, is the


sum of the equilibrium concentrations for
all soluble forms of Ag+.
Substituting the equilibrium constant
expressions for reactions (3-5) into
equation (6) defines the solubility of AgCl
in terms of the equilibrium concentration

of
Cl
.

(7)

ubility Considerations contd.


Equation (7) explains the solubility curve
for AgCl shown in Figure 1. As Cl is added
to a solution of Ag+, the solubility of AgCl
initially decreases because of reaction 1.
Note that under these conditions, the
final three terms in equation (7) are small,
and that equation (1) is sufficient to
describe the solubility of AgCl.
Increasing the concentration of chloride,
however, leads to an increase in the
solubility of AgCl due to the soluble
chloro-complexes formed in reactions 35.

ubility Considerations contd.


0.00

Log(Solubility)

-1.00
-2.00
-3.00
-4.00
-5.00
-6.00
-7.00

Ag+ (aq)
6

AgCl (aq)AgCl2- (aq)


4
pCl

Figure 1: Solubility of AgCl as a function of pCl. The dashed


line shows the predicted SAgCl, assuming that only reaction 1
and equation (2) affect the solubility of AgCl. The solid line
is calculated using equation (7) and includes the effect of
reactions 35. A ladder diagram for the AgCl complexation

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

ffect of pH(2nd Example)

The solubility of Ca3(PO4)2 is


pH-dependent because
phosphate is a weak base.
The following four reactions,
therefore, govern the

solubility of Ca3(PO4)2.

ect of pH(2nd Example)contd.

Depending on the solutions pH, the


predominate phosphate species is either
PO43, HPO42, H2PO4, or H3PO4.

ect of pH(2nd Example) contd.

The ladder diagram for phosphate, shown


in Figure a, provides a convenient way to
evaluate the pH-dependent solubility of

ect of pH(2nd Example) contd.

When the pH is greater than 12.4, the


predominate phosphate species is PO43,
and the solubility of Ca3(PO4)2 will be at its
minimum because only (reaction 8)
occurs to an appreciable extent (Figure
b).
As the solution becomes more acidic, the
solubility of Ca3(PO4)2 increases due to
the contributions of (reactions 911).
Solubility can often be decreased by
using a nonaqueous solvent. A
precipitates solubility is generally greater

ect of pH(2nd Example) contd.

The poorer solvating ability of


nonaqueous solvents, even those that are
polar, leads to a smaller solubility
product. For example, PbSO4 has a Ksp of
1.6 108 in H2O, whereas in a 50:50
mixture of H2O/ethanol the Ksp at 2.6
iding
precipitate
1012 Impurities
is four orders in
of magnitude
smaller.
Precipitation gravimetry is based on a
known stoichiometry between the
analytes mass and the mass of a
precipitate. It follows, therefore, that the
precipitate must be free from impurities.

ding Impurities in precipitate contd.


Precipitation typically occurs in a
solution rich in dissolved solids, the
initial precipitate is often impure.
Any impurities present in the
precipitates matrix must be removed
before obtaining its weight.
The greatest source of impurities
results from chemical and physical
interactions occurring at the
precipitates surface.
A precipitate is generally crystalline,
even if only on a microscopic scale, with

ding Impurities in precipitate contd.


Those cations and anions at the surface
of the precipitate carry, respectively, a
positive or a negative charge as a result
of their incomplete coordination spheres.
In a precipitate of AgCl, for example,
each Ag+ ion in the bulk of the precipitate
is bound to six (6) Cl ions. Silver ions at
the surface, however, are bound to no
more than five (5) Cl ions, and carry a
partial positive charge (Figure 2).
Precipitate particles grow in size because
of the electrostatic attraction between
charged ions on the surface of the

ding Impurities in precipitate contd.


ClAg+

Surface silver ion


surrounded by 4
chloride ions

Bulk silver ion


surrounded by 6
chloride ions
Fig.2: Schematic model of AgCl showing
difference between bulk and surface atoms
of silver. Silver and chloride ions are not

ding Impurities in precipitate contd.

Ions common to the precipitate are


chemically adsorbed, extending the
crystal lattice.
Other ions may be physically adsorbed
and, unless displaced, are incorporated
into the crystal lattice as a co-precipitated
impurity. Physically adsorbed ions are less
strongly
Types
of attracted
Impurityto the surface and can
beInclusion:
displaced Potential
by chemically
adsorbed
1.
interfering
ions ions.
whose size and charge are similar to a
lattice ion may substitute into the lattice
structure by chemical adsorption,
provided that the interferent

pes of Impurity contd.


The probability of forming an inclusion is
greatest when the interfering ion is
present at substantially higher
concentrations than the dissolved
lattice ion.
The presence of an inclusion does not
decrease the amount of analyte that
precipitates, provided that the
precipitant is added in sufficient excess.
Thus, the precipitates mass is always
larger than expected.
Inclusions are difficult to remove since

Removing inclusion impurities


The only way to remove included
material is through re-precipitation.
After isolating the precipitate from the
supernatant solution, it is dissolved in a
small portion of a suitable solvent at an
elevated temperature.
The solution is then cooled to re-form the
precipitate. This process of reprecipitation is repeated as needed
to completely remove the inclusion.

pes of Impurity contd.

2.Occlusions are a second type of coprecipitated impurity, occurring when


physically adsorbed interfering ions
become trapped within the growing
precipitate.
.Occlusions form in two ways. The
most common mechanism occurs when
physically adsorbed ions are
surrounded by additional precipitate
before they can be desorbed or
displaced. In this case the precipitates
mass is always greater than expected.
.Occlusions also form when rapid

pes of Impurity contd.


The mass of the precipitate may be
less than expected, however, if the
occluded material consists primarily of
the analyte in a lower-molecular-weight
form from that of the precipitate.
Removing occlusion impurities
Occlusions are minimized by maintaining
the precipitate in equilibrium with its
supernatant solution for an extended
time.
This process is called digestion and may
be carried out at room temperature or at

pes of Impurity contd.

3.Surface adsorbates: After precipitation


is complete the surface continues to
attract ions from solution. These surface
adsorbates, which may be chemically or
physically adsorbed, constitute a third
type of co-precipitated impurity.
Removing adsorbate impurities
.Surface adsorption is minimized by
decreasing the precipitates available
surface area through digestion, larger
particles of precipitate increase in size at
the expense of smaller particles. Fewer
particles of larger size leads to decrease

pes of Impurity contd.


Inclusions, occlusions, and surface
adsorbates are called co-precipitates
because they represent soluble species
that are brought into solid form
along with the desired precipitate.
Another source of impurities occurs when
other species in solution precipitate
under the conditions of the analysis.
Solution conditions necessary to
minimize the solubility of a desired
precipitate may lead to the formation of
an additional precipitate that interferes

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

pes of Impurity contd.


Alternatively, either the analyte or the
interferent can be masked using a
suitable complexing agent, preventing its
precipitation.
Freseniuss analytical method
(purification of ppt)
The above mentioned approaches are
illustrated in Freseniuss analytical
method for determining Ni and Co in ores
containing Pb2+, Cu2+, and Fe3+ as potential
interfering ions. The ore is dissolved in a
solution containing H2SO4, selectively

Freseniuss analytical method


(purification of ppt) contd.
After removing the CuS by
filtration, the solution is
made basic with (2) NH3(aq)
until Fe(OH)3 precipitates.
Cobalt and nickel, which form
soluble amine complexes,
Rate
ofinformation
of a precipitate
remain
solution.

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

Rate of formation of a precipitate


as a function of separating
Precipitates of
precipitates
contd.
Ca(OH)2, however, form
more rapidly than precipitates of
Mg(OH)2.
If Ca(OH)2 is filtered before Mg(OH)2
begins to precipitate, then a
By weighing both the analyte
and
quantitative analysis for Ca2+ is
the
interferent.
feasible.
Finally,
in some cases it is easier to isolate and
weigh both the analyte and the interferent.
The mixed precipitate is treated to convert at
least one of the two precipitates to a new
chemical form.

By weighing both the analyte and


the interferent.contd.
For example,
A mixture containing Ca2+ and Mg2+ can be
analyzed for both cations by first isolating a
mixed precipitate of CaCO3 and MgCO3.
After weighing, the mixed precipitate is
heated, converting it to a mixture of CaO
and MgO.
Thus
Grams of mixed ppt 1 = grams CaCO3 +
grams MgCO3

By weighing both the analyte and


the interferent.contd.
Although these equations contain four
unknowns (grams CaCO3, grams MgCO3,
grams CaO, and grams MgO), the
stoichiometric relationships between CaCO3
and CaO
Moles CaCO3 = moles CaO
and between MgCO3 and MgO
Moles MgCO3 = moles MgO
provide enough additional information to
determine the amounts of both Ca2+ and

ntrolling Particle Size


Following precipitation and digestion, the
precipitate must be separated from the
supernatant solution and freed of any
remaining impurities, including residual
solvent. These tasks are accomplished by
filtering,
rinsing, and
drying the precipitate.
Precipitation consists of two distinct
events: nucleation, or the initial
formation of smaller stable particles of
precipitate, and the subsequent growth
of these particles.

trolling Particle Size contd.


Larger particles form when the rate of
particle growth exceeds the rate of
nucleation
A solutes relative supersaturation,
(RSS) can be expressed as

where Q is the solutes actual


concentration, S is the solutes expected
concentration at equilibrium, and Q S is
a measure of the solutes supersaturation
when precipitation begins.

trolling Particle Size contd.


A large, positive value of RSS
indicates that a solution is highly
supersaturated. Such solutions are
unstable and show high rates of
nucleation, producing a precipitate
consisting of numerous small particles.
When RSS is small, precipitation is
more likely to occur by particle growth
than by nucleation.
equation shows that we can minimize
RSS by either decreasing the solutes
concentration or increasing the

trolling Particle Size contd.

and adjusting pH may affect a


precipitates solubility if it contains an
acidic or basic anion.
Conducting the precipitation in a dilute
solution of analyte, or adding the
precipitant slowly and with vigorous
stirring
are ways to
the value
of
tical
limitations
todecrease
minimizing
RSS
Q.
Precipitates that are extremely insoluble,
such as Fe(OH)3 and PbS, have such small
solubilities that a large RSS cannot be
avoided.

cal limitations to minimizing RSS co


In addition, conditions that yield a small
RSS may lead to a relatively stable
supersaturated solution that requires a
long time to fully precipitate. For
example, almost a month is required to
form a visible precipitate of BaSO4 under
conditions in which the initial RSS is 5.
One solution to the latter problem is to
chemically generate the precipitant in
solution as the product of a slow
chemical reaction. This maintains the
RSS at an effectively constant level. This

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

ods of homogeneous precipitation c

(b) The second method of homogeneous


precipitation involves the precipitant itself
being generated by a chemical reaction.
For example, Ba2+ can be homogeneously
precipitated as BaSO4 by hydrolyzing
sulphamic acid to produce SO42.

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

and a tendency for the precipitate to


deposit as a thin film on the containers
walls. This problem is particularly
severe for hydroxide precipitates
generated
using urea. precipitation c
ods
of homogeneous
(c) Surface adsorption of excess
lattice ions When a precipitates particles
are electrically neutral, they tend to
coagulate into larger particles. This
method provides the precipitates particles
with a net positive or negative surface

ods of homogeneous precipitation c


Electrostatic repulsion between the
particles prevents them from coagulating
into larger particles. Consider, for
instance, the precipitation of AgCl from a
solution of AgNO3 using NaCl as a
precipitant.
Early in the precipitation, when NaCl is
the limiting reagent, excess Ag+ ions
chemically adsorb to the AgCl particles,
forming a positively charged primary
adsorption layer (Figure 3).

ods of homogeneous precipitation c


NO3Ag

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

ods of homogeneous precipitation c


Anions in solution, in this case NO3 and
OH are attracted toward the surface,
forming a negatively charged secondary
adsorption layer that balances the
surfaces positive charge.
The solution outside the secondary
adsorption layer remains electrically
neutral. Coagulation cannot occur if the
secondary adsorption layer is too thick
because the individual particles of AgCl
are unable to approach one another
closely enough.

ods of homogeneous precipitation c


Coagulation can be induced in two ways:
(i) By increasing the concentration of the ions
responsible for the secondary adsorption
layer. By addition of an inert electrolyte, which
increases the concentration of ions in the
secondary adsorption layer. With more ions
available, the thickness of the secondary
absorption layer decreases. Particles of
precipitate may now approach one another
more closely, allowing the precipitate to
coagulate.
(ii) Heating the solution and precipitate provides
a second way to induce coagulation.
Increasing the particles kinetic energy may be

ods of isolation and purification of p


Filtering the Precipitate: After precipitation
and digestion are complete, the precipitate
is separated from solution by filtration
using either filter paper or a filtering
crucible. The most common filtering
medium is cellulose-based filter paper,
which is classified according to its filtering
speed, its size, and its ash content on
ignition
Rinsing the Precipitate: Filtering removes
most of the supernatant solution. Residual
traces of the supernatant, however, must
be removed to avoid a source of

ods of isolation and purification of p


Drying the Precipitate: Finally, after
separating the precipitate from its
supernatant solution the precipitate is
dried to remove any residual traces of
rinse solution and any volatile impurities.
The temperature and method of drying
depend on the method of filtration, and
the precipitates desired chemical form.
Composition of Final Precipitate
The quantitative application of
precipitation gravimetry, which is based
on a conservation of mass, requires that

mposition of Final Precipitate

Precipitates containing volatile ions or


substantial amounts of hydrated water are
usually dried at a temperature that is
sufficient to completely remove the volatile
species.
Example one: standard gravimetric
method for the determination of
magnesium involves the precipitation of
MgNH4PO4 6H2O. Unfortunately, this
precipitate is difficult to dry at lower
temperatures without losing an
inconsistent amount of hydrated water and

position of Final Precipitate contd.


Example 2: An additional problem is
encountered when the isolated solid is
nonstoichiometric. For example,
precipitating Mn2+ as Mn(OH)2, followed by
heating to produce the oxide, frequently
produces a solid with a stoichiometry of
MnOx, where x varies between 1 and 2. In
this case the nonstoichiometric product
results from the formation of a mixture of
several oxides that differ in the oxidation
state of manganese.
Example 3: Other nonstoichiometric

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

Procedure: Transfer a sample containing no more


than 60 mg of Mg2+into a 600-mL beaker. Add 23
drops of methyl red indicator, and, if necessary,
adjust the volume to 150 mL. Acidify the solution
with 6 M HCl, and add 10 mL of 30% w/v
(NH4)2HPO4. After cooling, add concentrated NH3
dropwise, and while constantly stirring, until the
methyl red indicator turns yellow (pH>6.3). After
stirring for 5 min, add 5 mL of concentrated NH3,
and continue stirring for an additional 10 min.
Allow the resulting solution and precipitate to
stand overnight. Isolate the precipitate by
filtration, rinsing with 5% v/v NH3. Dissolve the
precipitate in 50 mL of 10% v/v HCl, and
precipitate a second time following the same

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.

3. Why is the acidbase indicator methyl red


added to the solution?
The indicators color change, which occurs
at a pH of approximately 6.3, indicates
when sufficient NH3 has been added to
neutralize the HCl added at the beginning of
the procedure.
4. Explain why the formation of Mg(PO3)2 in place
of Mg2P2O7 increases the mass of precipitate?
The desired final precipitate, Mg2P2O7, contains
two moles of Mg, and the impurity, Mg(PO3)2,
contains only one mole of Mg. Conservation of
mass, therefore, requires that two moles of
Mg(PO3)2 must form in place of each mole of

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.

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