Gravimetric Methods of Analysis

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.
We can, of course, measure an analytes mass directly by placing it on a balance and
recording its mass. For example, suppose you are to determine the total suspended solids in
water released from a sewage-treatment facility. Suspended solids are just that; solid matter
that has yet to settle out of its solution matrix. The analysis is easy. You collect a sample and
pass it through a preweighed filter that retains the suspended solids. After drying to remove
any residual moisture, you weigh the filter. The difference between the filters original mass
and final mass gives the mass of suspended solids. 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 Pb 2+ is dissolved in the
solutions matrix. We can still measure the analytes mass, however, 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 long enough time, we can force the reaction
(

()

( )

( )

to go to completion. The Pb2+ ion in solution oxidizes to PbO2 and deposits on the Pt
electrode serving as the anode. If we weigh the Pt anode before and after applying the
potential, the difference in the two measurements gives the mass of PbO2 and, from the
reactions stoichiometry, the mass of Pb2+. This also is a direct analysis because the material
being weighed contains the analyte. Sometimes it is easier to remove the analyte and use a
change in mass as the analytical signal. Imagine how you would determine a foods moisture
content by a direct analysis. One possibility is to heat a sample of the food to a temperature at
which the water in the sample vaporizes. If we capture the vapour in a preweighed absorbent
trap, then the change in the absorbents mass provides a direct determination of the amount of
water in the sample. An easier approach, however, is to weigh the sample of food before and
after heating, using the change in its mass as an indication of the amount of water originally
present. We call this an indirect analysis since we determine the analyte by a signal
representing its disappearance. We can also determine an analyte indirectly 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+. In the presence of
Cl a solid precipitate of Hg2Cl2 forms.
(

)
( )

()
(

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 PO33 present
in the original sample. Summarizing, we can determine an analyte gravimetrically by directly
1

determining its mass, or the mass of a compound containing the analyte. Alternatively, we
can determine an analyte indirectly by measuring a change in mass due to its loss, or the mass
of a compound formed as the result of a reaction involving the analyte.
Types of Gravimetric Methods
In the previous section we used four examples to illustrate the different ways that mass can
serve as an analytical signal. These examples also illustrate the four gravimetric methods of
analysis. When the signal is the mass of a precipitate, we call the method precipitation
gravimetry. The indirect determination of PO33 by precipitating Hg2Cl2 is a representative
example, as is the 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 oxidation
of Pb2+, and its deposition as PbO2 on a Pt anode is one example of electrogravimetry.
Reduction also may be used in electrogravimetry. 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. In
determining the moisture content of food, thermal energy vaporizes the H2O. The amount of
carbon in an organic compound may be determined by using the chemical energy of
combustion to convert C to CO2.
Finally, in particulate gravimetry the analyte is determined following its removal from the
sample matrix by filtration or extraction. The determination of suspended solids is one
example of particulate gravimetry.
Conservation of Mass
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 involves a conservation of mass. For gravimetric
methods involving a chemical reaction, the analyte should participate in only one set of
reactions, the stoichiometry of which indicates how the precipitates mass relates to the
analytes mass. Thus, for the analysis of Pb2+ and PO33 described earlier, we can write the
following conservation equations
moles Pb2+ = moles PbO2
moles PO33 = moles Hg2Cl2
Removing the analyte from its matrix by filtration or extraction must be complete. When true,
the analytes mass can always be found from the analytical signal; thus, for the determination
of suspended solids we know that
Filters final mass filters initial mass = g suspended solid
whereas for the determination of the moisture content we have
Samples initial mass samples final mass = g H2O

Why 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. Verifying a method
by analyzing a standard reference material, however, is common. Estimating the composition
of these materials often involves a gravimetric analysis.
Precipitation 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. Most precipitation gravimetric methods were developed in the
nineteenth century as a means for analyzing ores. Many of these methods continue to serve as
standard methods of analysis.
A precipitation gravimetric analysis must have several important attributes. First, the
precipitate must be of low solubility, high purity, and of known composition if its mass is to
accurately reflect the analytes mass. Second, the precipitate must be in a form that is easy to
separate from the reaction mixture.
Solubility Considerations
An accurate precipitation gravimetric method requires that the precipitates solubility be
minimal. Many total analysis techniques can routinely be performed with an accuracy of
better than 0.1%. To obtain this level of accuracy, the isolated precipitate must account for
at least 99.9% of the analyte. By extending this requirement to 99.99% we ensure that
accuracy is not limited by the precipitates solubility. Solubility losses are minimized by
carefully controlling the composition of the solution in which the precipitate forms. This, in
turn, requires an understanding of the relevant equilibrium reactions affecting the
precipitates solubility. For example, Ag+ can be determined gravimetrically by adding Cl as
a precipitant, forming a precipitate of AgCl.
(

( )

( )

If this is the only reaction considered, we would falsely conclude that the precipitates
solubility, SAgCl, is given by
[

( )

and that 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 chloro-complexes
(

( )

( )

( )

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 (35) into equation (6) defines
the solubility of AgCl in terms of the equilibrium concentration of Cl.
[

] (7)

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.

Clearly the equilibrium concentration of chloride is an important parameter if the

concentration of silver is to be determined gravimetrically by precipitating AgCl. In
particular, a large excess of chloride must be avoided.
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 precipitates, but also affects precipitates
containing basic or acidic ions. 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.

) ( )
(

()

(
(

( )
(

( )

()

()

Depending on the solutions pH, the predominate phosphate species is either PO43, HPO42,
H2PO4, or H3PO4. The ladder diagram for phosphate, shown in Figure a, provides a
convenient way to evaluate the pH-dependent solubility of phosphate precipitates. 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 in aqueous solutions because of the ability of water molecules to stabilize
ions through solvation. 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 1012 is four orders of
magnitude smaller.

Avoiding Impurities
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. Since 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 a well-defined lattice structure of
cations and anions. 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 precipitate
and oppositely charged ions in solution. 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 attracted to the surface and can be displaced by chemically
adsorbed ions.
Types of Impurity
One common type of impurity is an inclusion. Potential interfering ions whose size and
charge are similar to a lattice ion may substitute into the lattice structure by chemical
adsorption, provided that the interferent precipitates with the same crystal structure. 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 the included material is chemically part of
the crystal lattice. 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 re-precipitation is repeated as needed to completely remove the
inclusion.
Occlusions are a second type of co-precipitated 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
precipitation traps a pocket of solution within the growing precipitate. Since the trapped
solution contains dissolved solids, the precipitates mass normally increases. 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. Occlusions are
minimized by maintaining the precipitate in equilibrium with its supernatant solution for an
7

extended time. This process is called digestion and may be carried out at room temperature or
at an elevated temperature. During digestion, the dynamic nature of the solubility
precipitation equilibrium, in which the precipitate dissolves and re-forms, ensures that
occluded material is eventually exposed to the supernatant solution. Since the rate of
dissolution and re-precipitation are slow, the chance of forming new occlusions is minimal.
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. Surface adsorption is minimized by decreasing the precipitates
available surface area. One benefit of digestion is that it also increases the average size of
precipitate particles. This is not surprising since the probability that a particle will dissolve is
inversely proportional to its size. During digestion, larger particles of precipitate increase in
size at the expense of smaller particles. One consequence of forming fewer particles of larger
size is an overall decrease in the precipitates surface area. Surface adsorbates also may be
removed by washing the precipitate. Potential solubility losses, however, cannot be ignored.
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 in the
analysis. For example, the precipitation of nickel dimethylgloxime requires a pH that is
slightly basic. Under these conditions, however, any Fe3+ that might be present precipitates as
Fe(OH)3. Finally, since most precipitants are not 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 less soluble than the
analyte may be precipitated and removed by filtration, leaving the analyte behind in solution.
Alternatively, either the analyte or the interferent can be masked using a suitable complexing
agent, preventing its precipitation.
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 precipitating Pb2+ as PbSO4.
After filtering, the supernatant solution is treated with H2S. Because the solution is strongly
acidic, however, only CuS precipitates. After removing the CuS by filtration, the solution is
made basic with ammonia until Fe(OH)3 precipitates. Cobalt and nickel, which form soluble
amine complexes, remain in solution.
In some situations the rate at which a precipitate forms can be used to separate an analyte
from a potential interferent. For example, due to similarities in their chemistry, a gravimetric
analysis for Ca2+ may be adversely affected by the presence of Mg2+. Precipitates of
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 quantitative analysis for Ca2+ is feasible.
8

Finally, in some cases it is easier to isolate and weigh both the analyte and the interferent.
After recording its weight, the mixed precipitate is treated to convert at least one of the two
precipitates to a new chemical form. This new mixed precipitate is also isolated and weighed.
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 precipitate 1 = grams CaCO3 + grams MgCO3
Grams of mixed precipitate 2 = grams CaO + grams MgO
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 M
provide enough additional information to determine the amounts of both Ca2+ and Mg2+ in the
sample.
Controlling 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. The size of the precipitates
particles determines the ease and success of filtration. Smaller, colloidal particles are difficult
to filter because they may readily pass through the pores of the filtering device. Large,
crystalline particles, however, are easily filtered.
By carefully controlling the precipitation reaction we can significantly increase a precipitates
average particle size. Precipitation consists of two distinct events: nucleation, or the initial
formation of smaller stable particles of precipitate, and the subsequent growth of these
particles. 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.
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.

Examining equation 12 shows that we can minimize RSS by either decreasing the solutes
concentration or increasing the precipitates solubility. A precipitates solubility usually
increases at higher temperatures, and adjusting pH may affect a precipitates solubility if it
contains an acidic or basic anion. Temperature and pH, therefore, are useful ways to increase
the value of S. Conducting the precipitation in a dilute solution of analyte, or adding the
precipitant slowly and with vigorous stirring are ways to decrease the value of Q.
There are, however, practical limitations to minimizing RSS. Precipitates that are extremely
insoluble, such as Fe(OH)3 and PbS, have such small solubilities that a large RSS cannot be
avoided. Such solutes inevitably form small particles. 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.
An increase in the time required to form a visible precipitate under conditions of low RSS is a
consequence of both a slow rate of nucleation and a steady decrease in RSS as the precipitate
forms. 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. The precipitate initially forms under conditions of low RSS, leading to the nucleation
of a limited number of particles. As additional precipitant is created, nucleation is eventually
superseded by particle growth. This process is called homogeneous precipitation
There are two general methods used for homogeneous precipitation.
(a) If the precipitates solubility is pH-dependent, 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.

CO(NH2)2(aq) + H2O(l)

CO2(g) + 2NH3(aq)
NH4+(aq) + OH(aq)

NH3(aq) + H2O(l)

The hydrolysis of urea is strongly temperature-dependent, with the rate being negligible at
room temperature. The rate of hydrolysis, and thus the rate of precipitate formation, can be
controlled by adjusting the solutions temperature.
(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.
NH4+(aq) + H3O+(aq) + SO42(aq)

NH2SO3H(aq) + 2H2O(l)

Homogeneous precipitation affords the dual advantages of producing large particles of

precipitate that are relatively free from impurities. These advantages, however, may be offset
by increasing the time needed to produce the precipitate, and a tendency for the precipitate to
10

deposit as a thin film on the containers walls. The latter problem is particularly severe for
hydroxide precipitates generated using urea.
(c) A third method for increasing particle size deserves mention. When a precipitates
particles are electrically neutral, they tend to coagulate into larger particles. Surface
adsorption of excess lattice ions, however, provides the precipitates particles with a net
positive or negative surface charge. 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).

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.
Coagulation can be induced in two ways:
(i) by increasing the concentration of the ions responsible for the secondary adsorption layer.
One way to induce coagulation is to add 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. The amount of

11

electrolyte needed to cause spontaneous coagulation is called the critical coagulation

concentration.
(ii) by heating the solution. Heating the solution and precipitate provides a second way to
induce coagulation. As the temperature increases, the number of ions in the primary
adsorption layer decreases, lowering the precipitates surface charge. In addition, increasing
the particles kinetic energy may be sufficient to overcome the electrostatic repulsion
preventing coagulation at lower temperatures.
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. Filtering speed is a function of the papers pore size, which
determines the particle sizes retained by the filter. Filter paper is rated as fast (retains
particles > 2025 m), medium fast (retains particles > 16 m), medium (retains particles > 8
m), and slow (retains particles > 23 m). The proper choice of filtering speed is important.
If the filtering speed is too fast, the precipitate may pass through the filter paper resulting in a
loss of precipitate. On the other hand, the filter paper can become clogged when using a filter
paper that is too slow. Filter paper is hygroscopic and is not easily dried to a constant weight.
As a result, in a quantitative procedure the filter paper must be removed before weighing the
precipitate. This is accomplished by carefully igniting the filter paper. Following ignition, a
residue of noncombustible inorganic ash remains that contributes a positive determinate error
to the precipitates final mass. For quantitative analytical procedures a low-ash filter paper
must be used. This grade of filter paper is pre-treated by washing with a mixture of HCl and
HF to remove inorganic materials. Filter paper classed as quantitative has an ash content of
less than 0.010% w/w.
Rinsing the Precipitate
Filtering removes most of the supernatant solution. Residual traces of the supernatant,
however, must be removed to avoid a source of determinate error. Rinsing the precipitate to
remove this residual material must be done carefully to avoid significant losses of the
precipitate. Of greatest concern is the potential for solubility losses. Usually the rinsing
medium is selected to ensure that solubility losses are negligible. In many cases this simply
involves the use of cold solvents or rinse solutions containing organic solvents such as
ethanol. Precipitates containing acidic or basic ions may experience solubility losses if the
rinse solutions pH is not appropriately adjusted. When coagulation plays an important role in
determining particle size, a volatile inert electrolyte is often added to the rinse water to
prevent the precipitate from reverting into smaller particles that may not be retained by the
filtering device. This process of reverting to smaller particles is called peptization. The
volatile electrolyte is removed when drying the precipitate.

12

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. A temperature of 110 C is usually sufficient when removing water and other easily
volatilized impurities. A conventional laboratory oven is sufficient for this purpose. Higher
temperatures require the use of a muffle furnace, or a Bunsen or Meker burner, and are
necessary when the precipitate must be thermally decomposed before weighing or when
using filter paper. To ensure that drying is complete the precipitate is repeatedly dried and
weighed until a constant weight is obtained.
Composition of Final Precipitate
The quantitative application of precipitation gravimetry, which is based on a conservation of
mass, requires that the final precipitate have a well-defined composition. 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. For 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 ammonia. Instead, the
precipitate is dried at temperatures above 1000 C, where it decomposes to magnesium
pyrophosphate, Mg2P2O7.
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. Other nonstoichiometric compounds
form as a result of lattice defects in the crystal structure.
Practical Example
Determination of Mg2+ in Water and Wastewater
Description of Method: Magnesium is precipitated as MgNH4PO46H2O using (NH4)2HPO4
as the precipitant. The precipitates solubility in neutral solutions (0.0065 g/100 mL in pure
water at 10C) is relatively high, but it is much less soluble in the presence of dilute ammonia
(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. Calcium, which is the most
significant interferent, is usually removed by its prior precipitation as the oxalate. The
presence of excess ammonium salts from the precipitant or the addition of too much ammonia
can lead to the formation of Mg(NH4)4(PO4)2, which is subsequently isolated as Mg(PO3)2
after drying. The precipitate is isolated by filtration using a rinse solution of dilute ammonia.
After filtering, the precipitate is converted to Mg2P2O7 and weighed.
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.
13

Acidify the solution with 6 M HCl, and add 10 mL of 30% w/v (NH4)2HPO4. After cooling,
add concentrated NH3dropwise, 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
procedure. After filtering, carefully remove the filter paper by charring. Heat the precipitate
at 500 C.
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 the precipitant
is initially added. Because PO43is a weak base, the precipitate is soluble in a strongly acidic
solution. If the precipitant is added under neutral or basic conditions (high RSS), the resulting
precipitate will consist of smaller, less pure particles. Increasing the pH by adding base
allows the precipitate of MgNH4PO46H2O to form under more favourable (low RSS)
conditions.
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 NH3has been added to neutralize the HCl added at the beginning of the procedure.
The amount of NH3 added is crucial to this procedure. If insufficient NH3 is added, the
precipitates solubility increases, leading to a negative determinate error. If too much NH3 is
added, the precipitate may contain traces of Mg(NH4)4(PO4)2, which, on ignition, forms
Mg(PO3)2. This increases the mass of the ignited precipitate, giving a positive determinate
error. Once enough NH3 has been added to neutralize the HCl, additional NH3 is added to
quantitatively precipitate MgNH4PO46H2O.
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 Mg2P2O7. One mole of Mg2P2O7
weights 222.6 g. Two moles of Mg(PO3)2 weigh 364.5 g. Any replacement of Mg2P2O7 with
Mg(PO3)2 must increase the precipitates mass.

14

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 re-precipitation.
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 ammonical solution;
using dilute ammonia minimizes solubility losses when rinsing the precipitate.
Quantitative Applications
Although not in common use, precipitation gravimetry still provides a reliable means for
assessing the accuracy of other methods of analysis or for verifying the composition of
standard reference materials. In this section we review the general application of precipitation
gravimetry to the analysis of inorganic and organic compounds.
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. Many inorganic anions can be determined using the same
reactions by reversing the analyte and precipitant. For example, chromate can be determined
by adding BaCl2 and precipitating BaCrO4.
Table 1: Selected Gravimetric Method for Inorganic Cations Based on Precipitation
Analyte
Ba2+
Pb2+
Ag+
Hg22+
Al3+
Be2+
Fe3+
Ca2+
Sb3+
As3+
Hg2+
Ba2+
Pb2+
Sr2+
Be2+
Mg2+
Sr2+
Zn2+

Precipitant Precipitate Formed Precipitate Weighed

(NH4)2CrO4
BaCrO4
BaCrO4
K2CrO4
PbCrO4
PbCrO4
HCl
AgCl
AgCl
HCl
Hg2Cl2
Hg2Cl2
NH3
Al(OH)3
Al2O3
NH3
Be(OH)2
BeO
NH3
Fe(OH)3
Fe2O3
(NH4)2C2O4
CaC2O4
CaCO3 or CaO
H2S
Sb2S3
Sb2S3
H2S
As2S3
As2S3
H2S
HgS
HgS
H2SO4
BaSO4
BaSO4
H2SO4
PbSO4
PbSO4
H2SO4
SrSO4
SrSO4
(NH4)2HPO4
NH4BePO4
Be2P2O7
(NH4)2HPO4
NH4MgPO4
Mg2P2O7
KH2PO4
SrHPO4
Sr2P2O7
(NH4)2HPO4
NH4ZnPO4
Zn2P2O7

15

Methods for other selected inorganic anions are summarized in Table 2. Methods for the
homogeneous generation of precipitants are shown in Table 3.

Table 2: Selected Gravimetric Methods for Inorganic Anions Based on Precipitation

Analyte
Precipitant Precipitate Formed Precipitate Weighed

CN
AgNO3
AgCN
AgCN

I
AgNO3
AgI
AgI

Br
AgNO3
AgBr
AgBr

Cl
AgNO3
AgCl
AgCl

ClO3
FeSO4/AgNO3
AgCl
AgCl

SCN
SO2/CuSO4
CuSCN
CuSCN
2
SO4
BaCl2
BaSO4
BaSO4
Table 3: Reactions for the Homogeneous Preparation of Selected Inorganic Precipitants
Precipitant

Reaction
(

(
(

)
)

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.
SOLUTION
This is an example of a direct analysis since the iron in the analyte, Fe3O4, is part of the
isolated precipitate, Fe2O3. Applying a conservation of mass to Fe, we write
3 moles Fe3O4 = 2 moles Fe2O3
Using formula weights, FW, to convert from moles to grams in the preceding equation leaves
us with

16

which can be solved for grams of Fe3O4 and %w/w Fe3O4 in the sample.

The simultaneous analysis of samples containing two analytes requires the isolation of two
precipitates. As shown in Example 2, conservation of mass can be used to write separate
stoichiometric equations for each precipitate. These equations can then be solved
simultaneously for both analytes.
EXAMPLE 2
A 0.6113 g sample of Dow metal, containing aluminum, magnesium, and other metals, was
dissolved and treated to prevent interferences by the other metals. The aluminum and
magnesium were precipitated with 8-hydroxyquinoline. After filtering and drying, the
mixture of Al(C9H6NO)3 and Mg(C9H6NO)2 was found to weigh 7.8154 g. The mixture of
dried precipitates was then ignited, converting the precipitate to a mixture of Al2O3 and MgO.
The weight of this mixed solid was found to be 1.0022 g. Calculate the % w/w Al and % w/w
Mg in the alloy.
SOLUTION
This is an example of a direct analysis in which the two analytes are determined without a
prior separation. The weight of the original precipitate and the ignited precipitate are given by
the following two equations
g Al(C9H6NO)3 + g Mg(C9H6NO)2 = 7.8154
g Al2O3 + g MgO = 1.0022
containing four unknown terms. To solve this pair of equations, we must find two additional
equations relating the four unknowns to one another. These additional equations describe the
stoichiometric relationships between the two compounds containing aluminum and the two
compounds containing magnesium and are based on the conservation of Al and Mg. Thus, for
Al we have
2 moles Al2O3 = moles Al(C9H6NO)3
Converting from moles to grams and solving yields an equation relating the grams of Al2O3
to the grams of Al(C9H6NO)3
(

)
(

17

)
(

)
(

For Mg we have
Moles MgO = moles Mg(C9H6NO)2
(

)
(

)
(

)
(

Substituting the equations for g MgO and g Al2O3 into the equation for the combined weights
of MgO and Al2O3 leaves us with two equations and two unknowns.
. (1)

g Al(C9H6NO)3 + g Mg(C9H6NO)2 = 7.8154

0.11096 g Al(C9H6NO)3 + 0.12893 g Mg(C9H6NO)2 = 1.0022 (2)

Multiplying the first equation by 0.11096 and subtracting the second equation
Gives
0.01797 g Mg(C9H6NO)2 = 0.1350
which can be solved for the mass of Mg(C9H6NO)2.
g Mg(C9H6NO)2 = 7.5125 g
The mass of Al(C9H6NO)3 can then be calculated using the known combined mass of the two
original precipitates.
7.8154 g g Mg(C9H6NO)2 = 7.8154 g 7.5125 g = 0.3029 g Al(C9H6NO)3
Using the conservation of Mg and Al, the %w/w Mg and %w/w Al in the sample can now be
determined as in Example 1, where AW is an atomic weight.
Moles Mg = moles Mg(C9H6NO)2

Moles Al = moles Al(C9H6NO)3

(
(
(

)
)

(
(

)
(

)
)

(
)

)
(

18

In an indirect analysis the precipitate does not contain the analyte, but is the product of a
reaction involving the analyte. Despite the additional complexity, a stoichiometric
relationship between the analyte and the precipitate can be written by applying the
conservation principles.
EXAMPLE 3
An impure sample of Na3PO3 weighing 0.1392 g was dissolved in 25 mL of water. A solution
containing 50 mL of 3% w/v mercury(II) chloride, 20 mL of 10% w/v sodium acetate and 5
mL of glacial acetic acid was then prepared. The solution containing the phosphite was added
dropwise to the second solution, oxidizing PO33 to PO43 and precipitating Hg2Cl2. After
digesting, filtering, and rinsing, the precipitated Hg2Cl2 was found to weigh 0.4320 g. Report
the purity of the original sample as %w/w Na3PO3.
SOLUTION
This is an example of an indirect analysis since the isolated precipitate, Hg2Cl2, does not
contain the analyte, Na3PO3. The stoichiometry of the redox reaction in which Na3PO3 is a
reactant and Hg2Cl2 is a product was given earlier. It also can be determined by using the
conservation of electrons. Phosphorus has an oxidation state of +3 in PO33 and +5 in PO43;
thus, oxidizing PO33 to PO43 requires two electrons. The formation of Hg2Cl2 by reduction
of HgCl2 requires 2 electrons as the oxidation state of each mercury changes from +2 to +1.
Since the oxidation of PO33 and the formation of Hg2Cl2 both require two electrons, we have
Moles Na3PO3 = moles Hg2Cl2
Converting from moles to grams leaves us with

which can be solved for g Na3PO3 and %w/w Na3PO3 in the sample.

19

Thermogravimetry
The products of a thermal decomposition can be deduced by monitoring the samples mass as
a function of applied temperature (Figure 4).

Figure 4: Thermogram for CaC2O4H2O.

The loss of a volatile gas on thermal decomposition is indicated by a step in the thermogram.
As shown in Example 4, the change in mass at each step in a thermogram can be used to
identify both the volatilized species and the solid residue. Thermogram is a graph showing
change in mass as a function of applied temperature.
EXAMPLE 4
The thermogram in Figure 4 shows the change in mass for a sample of calcium oxalate
monohydrate, CaC2O4 H2O. The original sample weighed 24.60 mg and was heated from
room temperature to 1000 C at a rate of 5 C min. The following changes in mass and
corresponding temperature ranges were observed:
Loss of 3.03 mg from 100250 C
Loss of 4.72 mg from 400500 C
Loss of 7.41 mg from 700850 C
Determine the identities of the volatilization products and the solid residue at each step of the
thermal decomposition.
SOLUTION
The loss of 3.03 mg from 100250 C corresponds to a 12.32% decrease in the original
samples mass.

In terms of CaC2O4 H2O, this corresponds to a loss of 18.00 g/mol.

0.1232 146.11 g/mol = 18.00 g/mol
20

The products molar mass, coupled with the temperature range, suggests that this represents
the loss of H2O. The residue is CaC2O4.
The loss of 4.72 mg from 400 500 C represents a 19.19% decrease in the original mass of
24.60 g, or a loss of
0.1919 146.11 g/mol = 28.04 g/mol
This loss is consistent with CO as the volatile product, leaving a residue of CaCO3.
Finally, the loss of 7.41 mg from 700850 C is a 30.12% decrease in the original mass of
24.60 g. This is equivalent to a loss of
0.3012 146.11 g/mol = 44.01 g/mol
suggesting the loss of CO2. The final residue is CaO.
Once the products of thermal decomposition have been determined, an analytical procedure
can be developed. For example, the thermogram in Figure 4 shows that a precipitate of
CaC2O4 H2O must be heated at temperatures above 250 C, but below 400 C if it is to be
isolated as CaC2O4. Alternatively, by heating the sample to 1000 C, the precipitate can be
isolated as CaO. Knowing the identity of the volatilization products also makes it possible to
design an analytical method in which one or more of the gases are trapped. Thus, a sample of
CaC2O4 H2O could be analyzed by heating to 1000 C and passing the volatilized gases
through a trap that selectively retains H2O, CO, or CO2.
EXAMPLE 5
A 101.3 mg sample of an organic compound known to contain Cl is burned in pure O2 and
the combustion gases collected in absorbent tubes. The tube used to trap CO2 increases in
mass by 167.6 mg, and the tube for trapping H2O shows a 13.7-mg increase. A second sample
of 121.8 mg is treated with concentrated HNO3 producing Cl2, which subsequently reacts
with Ag+, forming 262.7 mg of AgCl. Determine the compounds composition, as well as its
empirical formula.
SOLUTION
Applying the principle of conservation of mass to carbon, we write
moles C = moles CO2
Converting from moles to grams, and rearranging to solve for milligrams of carbon gives

Thus, the %w/w C in the sample is

21

The calculation is then repeated for hydrogen

moles H = 2 moles H2O

and for chlorine

moles Cl = moles AgCl

Adding together the weight percents for C, H, and Cl gives a total of 100.01%. The
compound, therefore, contains only these three elements. To determine the compounds
empirical formula, we assume that we have 1 g of the compound, giving 0.4515 g of C,
0.0151 g of H, and 0.5335 g of Cl. Expressing each element in moles gives 0.0376 mol C,
0.0150 mol H, and 0.0150 mol Cl. Hydrogen and chlorine are present in a 1:1 molar ratio.
The molar ratio of C to moles of H or Cl is

Thus, the simplest, or empirical, formula for the compound is C5H2Cl2.

Tutorial Questions
1.
Calcium is determined gravimetrically by precipitating it as CaC2O4 H2O, followed
by isolating the precipitate as CaCO3. The sample to be analyzed is dissolved in 10
mL of water and 15 mL of 6 M HCl. After dissolution, the resulting solution is heated
to boiling, and a warm solution of excess ammonium oxalate is added. The solution is
maintained at 80 C, and 6 M NH3 is added dropwise, with stirring, until the solution
22

2.

3.

is faintly alkaline. The resulting precipitate and solution are removed from the heat
and allowed to stand for at least 1 h. After testing the solution for completeness of
precipitation, the sample is filtered, washed with 0.1% w/v ammonium oxalate, and
dried at 100120 C for 1 h. The precipitate is then transferred to a muffle furnace
where it is converted to CaCO3 by drying at 500 25 C until a constant weight. (a)
Why is the precipitate of CaC2O4 H2O converted to CaCO3? (b) In the final step, if
the sample is heated at too high of a temperature, some CaCO3 may be converted to
CaO. What effect would this have on the reported %w/w Ca? (c) Why is the
precipitant, (NH4)2C2O4, added to a hot, acidic solution rather than to a cold, alkaline
solution?
Aluminum can be determined gravimetrically by precipitating as Al(OH)3 and
isolating as Al2O3. A sample containing approximately 0.1 g of Al is dissolved in 200
mL of H2O and 5 g of NH4Cl and a few drops of methyl red indicator is added
(methyl red is red at pH levels below 4 and yellow at pH levels above 6). The solution
is heated to boiling, and 1:1 NH3 is added dropwise till the indicator turns yellow,
precipitating Al(OH)3. The precipitate is held at the solutions boiling point for
several minutes, filtered, and washed with a hot solution of 2%, w/v NH4NO3. The
precipitate is then ignited at 10001100 C, forming Al2O3. (a) Cite two ways in
which this procedure has been designed to encourage the formation of larger particles
of precipitate. (b) The ignition step must be carried out carefully to ensure that
Al(OH)3 is quantitatively converted to Al2O3. What effect would an incomplete
conversion have on the reported %w/w Al? (c) What role do NH4Cl and methyl red
indicator play in this procedure? (d) An alternative procedure involves isolating and
weighing the precipitate as the 8-hydroxyquinolate, Al(C9H6ON)3. Why might this be
a more advantageous form of Al for a gravimetric analysis?
Iron can be determined gravimetrically by precipitating as Fe(OH)3 and igniting to
Fe2O3. The sample to be analyzed is weighed and transferred to a 400-mL beaker
where it is dissolved in 50 mL of H2O and 10 mL of 6 M HCl. Any Fe2+ that is
present is oxidized to Fe3+ with 12 mL of concentrated HNO3. After boiling to
remove the oxides of nitrogen, the solution is diluted to 200 mL, brought to boiling,
and Fe(OH)3 is precipitated by slowly adding 1:1 NH3 until the odour of NH3 is
detected. The solution is boiled for an additional minute, and the precipitate is
allowed to settle to the bottom of the beaker. The precipitate is then filtered and
washed with several portions of hot 1% w/v NH4NO3 until no Cl is found in the wash
water. Finally, the precipitate is ignited to constant weight at 500550 C, and
weighed as Fe2O3. (a) If the ignition is not carried out under oxidizing conditions
(plenty of O2 present), the final product will contain some Fe3O4. What effect would
this have on the reported %w/w Fe? (b) The precipitate is washed with a dilute
solution of NH4NO3. Why is NH4NO3 added to the wash water? (c) Why does the
procedure call for adding NH3 until the odour of ammonia is detected? (d) Describe
how you might test the filtrate for Cl.

23

4.

The amount of iron and manganese in an alloy can be determined by precipitating the
metals with 8-hydroxyquinoline, C9H7NO. After weighing the mixed precipitate, the
precipitate is dissolved and the amount of 8-hydroxyquinoline determined by another
method. In a typical analysis, a 127.3 mg sample of an alloy containing iron,
manganese, and other metals was dissolved in acid and treated with appropriate
masking agents to prevent interference from other metals. The iron and manganese
were precipitated and isolated as Fe(C9H6NO)3 and Mn(C9H6NO)2, yielding a total
mass of 867.8 mg. The amount of 8-hydroxyquinolate in the mixed precipitate was
determined to be 5.276 mmol. Calculate the %w/w Fe and %w/w Mn in the alloy.

5.

A 0.8612 g sample of a mixture consisting of NaBr, NaI, and NaNO3 was analyzed by
adding AgNO3 to precipitate the Br and I, yielding a 1.0186 g mixture of AgBr and
AgI. The precipitate was then heated in a stream of Cl2, converting it to 0.7125 g of
AgCl. Calculate the %w/w NaNO3 in the sample.

VOLUMETRIC ANALYSIS
Almost any chemical reaction can serve as a titrimetric method provided that three conditions
are met. The first condition is that all reactions involving the titrant and analyte must be of
known stoichiometry. If this is not the case, then the moles of titrant used in reaching the end
point cannot tell us how much analyte is in our sample. Second, the titration reaction must
occur rapidly. If we add titrant at a rate that is faster than the reactions rate, then the end
point will exceed the equivalence point by a significant amount. Finally, a suitable method
must be available for determining the end point with an acceptable level of accuracy.
These are significant limitations and, for this reason, several titration strategies are commonly
used. A simple example of a titration is an analysis for Ag+ using thiocyanate, SCN, as a
titrant.
Ag+(aq) + SCN(aq)

AgSCN(s)

This reaction occurs quickly and is of known stoichiometry. A titrant of SCN is easily
prepared using KSCN. To indicate the titrations end point we add a small amount of Fe3+ to
the solution containing the analyte. The formation of the red coloured Fe(SCN)2+ complex
signals the end point. This is an example of a direct titration since the titrant reacts with the
analyte. If the titration reaction is too slow, a suitable indicator is not available, or there is no
useful direct titration reaction, then an indirect analysis may be possible.
Suppose you wish to determine the concentration of formaldehyde, H2CO, in an aqueous
solution. The oxidation of H2CO by I3
H2CO(aq) + 3OH(aq) + I3(aq)

HCO2(aq) + 3I(aq) + 2H2O(l)

is a useful reaction, except that it is too slow for a direct titration. If we add a known amount
of I3, such that it is in excess, we can allow the reaction to go to completion. The I3
remaining can then be titrated with thiosulfate, S2O32.
I3(aq) + 2S2O3 (aq)

S4O62(aq) + 3I(aq)
24

This type of titration is called a back titration.

Titrating a Weak Acid with a Strong Base
For this example lets consider the titration of 50.0 mL of 0.100 M acetic acid, CH3COOH,
with 0.100 M NaOH. Again, we start by calculating the volume of NaOH needed to reach the
equivalence point;
thus
Moles CH3COOH = moles NaOH
MaVa = MbVb
(

)(

Before adding any NaOH the pH is that for a solution of 0.100 M acetic acid. Since acetic
acid is a weak acid, we calculate the pH using the method;
H3O+(aq) + CH3COO(aq)

CH3COOH(aq) + H2O(l)
[

][

( )( )

]
[

At the beginning of the titration the pH is 2.88.

Adding NaOH converts a portion of the acetic acid to its conjugate base.
CH3COOH(aq )+ OH(aq)

H2O(l) + CH3COO(aq)(1)

Any solution containing comparable amounts of a weak acid, HA, and its conjugate weak
base, A, is a buffer. We can calculate the pH of a buffer using the HendersonHasselbalch
equation.
[
[

]
]

The equilibrium constant for reaction (1) is large (K = Ka/Kw = 1.75 109), so we can treat
the reaction as one that goes to completion. Before the equivalence point, the concentration of
unreacted acetic acid is
[

and the concentration of acetate is

[

25

For example, after adding 10.0 mL of NaOH the concentrations of CH3COOH and CH3COO
are
[

]
[

)(

)
(

(
)(

giving a pH of

26

)(
)