MODULE

4
GRAVIMETRIC METHOD OF ANALYSIS

INTRODUCTION
This module provides a deeper discussion of the quantitative measurement of analyte based on the
mass of the constituents related to it. It explains the formation and growth of precipitates and
crystals and its importance in analytical chemistry and other areas. The students further learn the
techniques in controlling the sizes of crystals to obtain an easily filterable precipitates which are
free from contaminants.

INTENDED LEARNING OUTCOMES

At the end of the module, the following learning outcomes are expected to be acquired by the
students:
1. Understand the concepts and be familiar with the steps and techniques employed in
gravimetric method of analysis.
2. Execute calculation techniques used in stoichiometry and gravimetric method of analysis.
3. Acquire skills in laboratory technique required to perform and plan chemical analysis and
systematically collect and interpret data obtained in quantitative analytical process.
4. Understand the current trends and analytical techniques in gravimetric method of analysis.

CONTENT OVERVIEW
Indicative contents included the following topics:
1. Gravimetric method
2. Precipitates and precipitating agents
3. Calculations involved in gravimetric analysis
4. Application of gravimetric analysis

END OF THE MODULE TEST

The following are the assessment provided to evaluate students level of understanding after the
discussion of the modules:

Coursework (100 points )

Solving problems involving gravimetric method of analysis
 Table of Contents

MODULE 4. GRAVIMETRIC METHOD OF ANALYSIS .................................................... 3

4.1 GRAVIMETRIC METHOD ......................................................................................... 3

4.1.1 Types of Gravimeric Analysis .................................................................................. 3

4.2 PRECIPITATION GRAVIMETRY ............................................................................ 3

4.3 PRECIPITATES ............................................................................................................ 4

4.3.1 Properties pf precipitates and precipitating agents ................................................... 4

4.3.2 Particle size and filterability of precipitates .............................................................. 5

4.3.3 Factors that determine the particle size of precipitates ............................................. 5

4.3.4 Mechanism of precipitate formation ......................................................................... 5

4.3.5 Colloidal precipitate .................................................................................................... 6

4.3.6 Coagulation of colloids................................................................................................ 6

4.3.7 Peptization ................................................................................................................... 7

4.3.8 Crystalline precipitates ................................................................................................ 8

4.4 COPRECIPITATION .................................................................................................... 8

4.4.1 Surface adsorption ....................................................................................................... 9

4.4.2 Mixed crystal formation ............................................................................................ 10

4.4.3 Occlusion and Mechanical entrapment...................................................................... 10

4.5 DRYING AND IGNITION OF PRECIPITATES..................................................... 11

4.6 CALCULATION INVOLVED IN GRAVIMETRIC DATA ................................... 11

4.7 APPLICATIONS OF GRAVIMETRIC METHODS ............................................... 13

4.7.1 Inorganic precipitating agents ................................................................................... 14

4.7.2 Reducing agents ......................................................................................................... 15

4.7.3 Organic precipitating agents ...................................................................................... 15

4.8 END OF MODULE TEST ........................................................................................... 16

MODULE 4. GRAVIMETRIC METHOD OF ANALYSIS

4.1 GRAVIMETRIC METHOD

Gravimetric method is a quantitative methods that are based on determining the mass of a pure
compound to which the analyte is chemically needed.

4.1.1 Types of Gravimeric Analysis

Table 4.1 Types of Gravimetric Analysis

The analyte is separated from the solution of the sample as the

Precipitation Gravimetry precipitate and is converted into a compound of known
composition that can be weighed.
The analyte is separated from other constituents of a sample by
Volatilization Gravimetry conversion to a gas by conversion to a gas known as chemical
composition.
Analyte is separated by deposition on an electrode by an electric
Electrogravimetry current. The mass of the product then provides the measure of
analyte concentration.
The mass of reagent of known concentration required to react
Gravimetric Titrimetry completely with the analyte provides the information needed to
determine the analyte concentration
Uses mass spectrometer to separate the gaseous ion formed from
the elements making up a sample of matter the concentration of
Atomic mass spectrometry
the resulting ions is then determined by measuring the electrical
current produced when they fall on the surface of an ion detector.

4.2 PRECIPITATION GRAVIMETRY

In precipitation gravimetry, the analyte is converted to a sparingly soluble precipitate. This
precipitate is then filtered, washed free of impurities, converted to a product of known composition
by suitable heat treatment and weighed. For example, a precipitation method for determining
calcium in natural waters is recommended by the Association of Official Analytical Chemists.
Here, an excess of oxalic acid, 𝐻2 𝐶2 𝑂4 is added to an aqueous solution of the sample. Ammonia
is then added which neutralizes the acid and causes essentially all of the calcium in the sample to
precipitate as calcium oxalate. The reactions are

𝟐𝑵𝑯𝟑 + 𝑯𝟐 𝑪𝟐 𝑶𝟒 → 𝟐𝑵𝑯+ 𝟐−
𝟒 + 𝑪 𝟐 𝑶𝟒

𝑪𝒂𝟐+(𝒂𝒒) + 𝑪𝟐 𝑶𝟐−
𝟒 (𝒂𝒒) → 𝑪𝒂𝑪𝟐 𝑶𝟒 (𝒔)

The precipitate is filtered using a weighed filtering crucible, then dried and ignited. This
process converts the precipitate entirely to calcium oxide. The reaction is

𝑪𝒂𝑪𝟐 𝑶𝟒 → 𝑪𝒂𝑶(𝒔) + 𝑪𝑶(𝒈) + 𝑪𝑶𝟐 (𝒈)

 After cooling, the crucible and precipitate are weighed. And the mass of calcium oxide is
determined by subtracting the known mass of the crucible.

4.3 PRECIPITATES
Precipitates are insoluble ionic solid products of a reaction, formed when certain cations
and anions combine in an aqueous solution. The determining factors of the formation of a
precipitate can vary. Some reactions depend on temperature, such as solutions used for buffers,
whereas others are dependent only on solution concentration. The solids produced in precipitate
reactions are crystalline solids, and can be suspended throughout the liquid or fall to the bottom of
the solution. The remaining fluid is called supernatant liquid. The two components of the mixture
(precipitate and supernate) can be separated by various methods, such as filtration, centrifuging,
or decanting.

Fig. 4.1 Formation of precipitate in solution

4.3.1 Properties pf precipitates and precipitating agents

Ideally, a gravimetric precipitating agent should react specifically or at least selectively
with the analyte. Specific reagents which are rare react only with a single chemical species.
Selective reagents, which are more common, react with a limited number of species. In addition
to specificity and selectivity, the ideal precipitating reagent would react with the analyte to give a
product that is

1. easily filtered and washed free of contaminants:

2. of sufficiently low solubility that no significant loss of the analyte occurs during
filtration and washing;
3. unreactive with constituents of the atmosphere;
4. of known chemical composition after it is dried or, if necessary, ignited.

Few of any reagents produce precipitates that possess all these desirable properties.
4.3.2 Particle size and filterability of precipitates
Precipitates consisting of large particles are generally desirable for gravimetric work
because these particles are easy to filter and wash free of impurities. In addition, precipitates of
this type are usually purer than are precipitates made up of fine particles.

4.3.3 Factors that determine the particle size of precipitates

The particle size of solids formed by precipitation varies enormously. At one extreme are
colloidal suspensions, whose tiny particles are invisible to the naked eye (10 -7 to 10-4 cm in
diameter). Colloidal particles show no tendency to settle from solution and are not easily filtered.
At the other extreme are particles with dimensions on the order of tenths of a millimetre or greater.
The temporary dispersion of such particles in the liquid phase is called a crystalline suspension.
The particles of a crystalline suspension tend to settle spontaneously and are easily filtered.
Scientists have studied precipitate formation for many years. But the mechanism of the process is
still not fully understood. It is certain, however, that the particle size of a precipitate is influenced
by such experimental variables as precipitate solubility, temperature, reactant concentrations and
rate at which reactants are mixed. The net effect of these variables can be accounted for, at least
qualitatively, by assuming that the particle size is related to a single property of the system called
the relative super saturation, where

𝑸−𝑺
relative super saturation = (4.1)
𝑺

In this equation, Q is the concentration of the solute at any instant and S is its equilibrium solubility.

Generally, precipitation reactions are slow, so that even when a precipitating reagent is
added drop by drop to a solution of an analyte, some super saturation is likely. Experimental
evidence indicates that the particle size of a precipitate varies inversely with the average relative
super saturation during the time when the reagent is being introduced. Thus, when (Q - S)/S is
large, the precipitate tends to be colloidal; when (Q - S)/S is small, a crystalline solid is more likely.

4.3.4 Mechanism of precipitate formation

The effect of relative super saturation on particle size can be explained if we assume that
precipitates form in two ways; by nucleation and by particle growth. The particle size of a freshly
formed precipitate is determined by the mechanism that predominates.

In nucleation, a few ions, atoms, or molecules (perhaps as few as four or five) come
together to form a stable solid. Often, these nuclei form on the surface of suspended solid
contaminants, such as dust particles. Further precipitation then involves a competition between
additional nucleation and growth on existing nuclei (particle growth). If nucleation predominates,
a precipitate containing a large number of small particles results; if growth predominates, a smaller
number of larger particles is produced.
 Fig. 4.2 Mechanism of precipitate formation

The rate of nucleation is believed to increase enormously with increasing relative super
saturation. In contrast, the rate of particle growth is only moderately enhanced by high relative
super saturations. Thus, when a precipitate is formed at high relative super saturation, nucleation
is the major precipitation mechanism, and a large number of small particles are formed. At low
relative super saturations, on the other hand, the rate of particle growth tends to predominate, and
deposition of solid on existing particles occurs to the exclusion of further nucleation; a crystalline
suspension results.

4.3.5 Colloidal precipitate

Individual colloidal particles are so small that they are not retained by ordinary filters.
Moreover, Brownian motion prevents their settling out of solution under the influence of gravity.
Fortunately, however, we can coagulate or agglomerate the individual particles of most colloids to
give a filterable amorphous mass that will settle out of solution.

Fig. 4.3 Colloidal precipitate

4.3.6 Coagulation of colloids

Coagulation can be hastened by heating, by stirring, and by adding an electrolyte to the
medium. To understand the effectiveness of these measures, we need to look into why colloidal
suspensions are stable and do not coagulate spontaneously. Colloidal suspensions are stable
because all of the particles of the colloid are either positively or negatively charged. This charge
results from cations or anions that are bound to the surface of the particles. We can easily
demonstrate that colloidal particles are charged by observing their migration when placed in an
electrical field. The process by which ions are retained on the surface of a solid is known as
adsorption.

Fig. 4.4 Coagulation of colloids

4.3.7 Peptization
Peptization is the process by which a coagulated colloid reverts to its original dispersed
state. When a coagulated colloid is washed, some of the electrolyte responsible for its coagulation
is leached from the internal liquid in contact with the solid particles. Removal of this electrolyte
has the effect of increasing the volume of the counter-ion layer. The repulsive forces responsible
for the original colloidal state are then reestablished, and particles detach themselves from the
coagulated mass. The washings become cloudy as the freshly dispersed particles pass through the
filter.

Fig. 4.5 Coagulation of colloids

4.3.8 Crystalline precipitates
Crystalline precipitates are generally more easily filtered and purified than are coagulated
colloids. In addition, the size of individual crystalline particles, and thus their filterability can be
controlled to a degree.

Fig. 4.6 Crystalline precipitates in solvents

4.4 COPRECIPITATION

Coprecipitation is a phenomenon in which otherwise soluble compounds are removed from

solution during precipitate formation. It is important to understand that contamination of a
precipitate by a second substance whose solubility product has been exceeded does not constitute
coprecipitation
.

Fig. 4.7 Coprecipitation

There are four types of coprecipitation:

1. Surface Adsorption

An equilibrium process that is also the common source of coprecipitation which causes

significant contamination of precipitates with large specific surface areas but its effects

on purity are typically undetected due to the comparatively low specific surface area of

such solids.
 2. Mixed – crystal formation –

An equilibrium process which an ion in the lattice of a crystal is replaced by a

contaminant ion and this may occur both in colloidal and crystalline precipitates.

3. Occlusion

Is a type of co-precipitation in which a compound is trapped within a pocket formed

during rapid crystal growth.

4. Mechanical Entrapment

Happens when crystals are lying close together during growth. Here, several crystals

grow together and thus trap a portion of the solution in a tiny pocket.

Surface adsorption and mixed crystal formation are equilibrium processes, whereas
occlusion and mechanical entrapment arise from the kinetics of crystal growth.

In adsorption, a normally soluble compound is carried out of solution on the surface of a

coagulated colloid. This compound consists of the primarily adsorbed ion and an ion of opposite
charge from the counter-ion layer.

Mixed-crystal formation is a type of co-precipitation in which a contaminant ion replaces

an ion in the lattice of a crystal.

4.4.1 Surface adsorption

Adsorption is a common source of coprecipitation that is likely to cause significant
contamination of precipitates with large specific surface areas- that is coagulated colloids.

Fig. 4.8 Surface adsoption of precipitates

 Coagulation of a colloid does not significantly decrease the amount of adsorption because
the coagulated solid still contains large internal surface areas that remain exposed to the solvent.
The coprecipitated contaminant on the coagulated colloid consists of the lattice ion originally
adsorbed on the surface before coagulation and the counter ion of opposite charge held in the film
of solution immediately adjacent to the particle. The net effect of surface adsorption is therefore
the carrying down of an otherwise soluble compound as a surface contaminant.

4.4.2 Mixed crystal formation

In mixed-crystal formation, one of the ions in the crystal lattice of a solid is replaced by an
ion of another element. For this exchange to occur, it is necessary that the two ions have the same
charge and that their sizes differ by no more than about 5%. Furthermore, the two salts must belong
to the same crystal class. For example, MgKPO 4, in MgNH4PO4, SrSO4 in BaSO4 and MnS in
CdS.
The extent of mixed-crystal contamination increases as the ratio of contaminant to analyte
concentration increases. Mixed-crystal formation is troublesome because little can be done about
it. Separation of the interfering ion may have to be carried out before the final precipitation step.
Alternatively, a different precipitating reagent may be used.

Fig. 4.9 Mixed crystal formation of precipitates

4.4.3 Occlusion and Mechanical entrapment

When a crystal is growing rapidly during precipitate formation, foreign ions in the counter-
ion layer may become trapped or occluded, within the growing crystal. Because supersaturation
and thus growth rate decrease as precipitation progresses, the amount of occluded material is
greatest in that pail of a crystal that forms first.

Fig. 4.9 Occlusion and Mechanical entrapment of precipitates

 If crystal growth is too rapid, some counter ions don’t have time to escape from the surface.
Mechanical entrapment occurs when crystals lie close together during growth. Several crystals
grow together and in so doing trap a portion of the solution in a tiny pocket.

4.5 DRYING AND IGNITION OF PRECIPITATES

After filtration, a gravimetric precipitate is heated until its mass becomes constant. Heating
removes the solvent and any volatile species carried down with the precipitate. Some precipitates
are also ignited to decompose the solid and form a compound of known composition. This new
compound is often called the weighing form.

Table 4.2 Methods for Homogeneous Generation of Precipitating Agents

Precipitatin Elements
Reagent Generation Reaction
g Agent Precipitated
OH - Urea NH2 2 CO  3H2O  CO2  2NH4  2OH  Al, Ga, Th, Bi, Fe,
Sn
PO34- Trimethyl phosphate CH3O3 PO  3H2O  3CH3OH  H3PO4 Zr, Hf
C2O24 Ethyl Oxalate C2H5 2 C2O4  2H2O  2C2H5OH  H2C2O4 Mg, Zn, Ca
SO24 Dimethyl Sulfate CH3O2 SO2  4H2O  2CH3OH  SO24  2H3O Ba, Ca, Sr, Pb
CO 32 Trichloroacetic acid Cl 3CCOOH  2OH 
 CHCl 3  CO32  H2O La, Ba, Ra
H2S Thioacetamide* CH3CSNH2  H2O  CH3CONH 2  H2S Sb, Mo, Cu, Cd
Biacetyl + CH3COCOCH 3  2H2NOH  DMG  2H2O
DMG† Ni
hydroxylamine
HOQ‡ 8-Acetoxyquinoline§ CH3COOQ  H2O  CH3COOH  HOQ Al, U, Mg, Zn

4.6 CALCULATION INVOLVED IN GRAVIMETRIC DATA

Gravimetric analysis problems are simply stoichiometry problems with a few extra steps. To
calculate the amount of the analyte in the sample:

mass of final form

% analyte = x GF x 100 (5.2)
mass of sample

Where GF is the gravimetric factor

molar mass of analyte x mol of analyte

𝑮F = mass of final final form
x y mol of final form
(5.3)
CHE 401 : ANALYTICAL CHEMISTRY

Some useful tips for gravimetric analysis experiments and calculations are:

 Double check stoichiometry and make sure equations are balanced.

 When removing volatiles from a sample, make sure to dry to constant mass.
 Always tare your glassware.

Example 4.1

The calcium in a 200.0-mL sample of natural water was determined by precipitating the
cation as CaC2O4. The precipitate was filtered washed and ignited in a crucible with an empty
mass of 26.6002 g. The mass of the crucible plus CaO (50.077 g/mol) was 26.7134 g. Calculate
the concentration of Ca (40.078 g/mol) in water in units of grams per 100 mL of the water.

The mass of CaO is

26.7134 g - 26.6002 g = 0.1132 g

The number of moles Ca in the sample is equal to the number of moles CaO or

1 𝑚𝑜𝑙 𝐶𝑎𝑂 1 𝑚𝑜𝑙 𝐶𝑎

𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐶𝑎 = 0.1132 𝑔 𝐶𝑎𝑂 × ×
56.077 𝑔 𝐶𝑎𝑂 𝑚𝑜𝑙 𝐶𝑎𝑂
−3
= 2.0186 × 10 𝑚𝑜𝑙 𝐶𝑎

𝑔 𝐶𝑎
2.0186 × 10−3 𝑚𝑜𝑙 𝐶𝑎 × 40.078
𝑐𝑜𝑛𝑐. 𝐶𝑎 = 𝑚𝑜𝑙 × 100 𝑚𝐿
200 𝑚𝐿 𝑠𝑎𝑚𝑝𝑙𝑒
𝑔
= 0.04045
100 𝑚𝐿

Example 4.2
An iron ore was analyzed by dissolving a 1.1324-g sample in concentrated HCl. The
resulting solution was diluted with water and the iron (III) was precipitated as the hydrous oxide
Fe2O3 • xH2O by the addition of NH3. After filtration and washing, the residue was ignited at a
high temperature to give 0.5394 g of pure Fe 2O3 (159.69 g/mol). Calculate (a) the % Fe (55.847
g/mol) and (b) the % Fe3O4 (231.54 g/mol) in the sample.

For both parts of this problem, we need to calculate the number of moles of Fe 2O3. Thus,
1 𝑚𝑜𝑙 𝐹𝑒2 𝑂3
𝑎𝑚𝑜𝑢𝑛𝑡 𝐹𝑒2 𝑂3 = 0.5394 𝑔 𝐹𝑒2 𝑂3 ×
159.69 𝑔 𝐹𝑒2 𝑂3
= 3.3778 × 10−3 𝑚𝑜𝑙 𝐹𝑒2 𝑂3

(a) The number of moles of Fe is twice the number of moles of Fe 2O3

2 𝑚𝑜𝑙 𝐹𝑒 𝑔 𝐹𝑒
𝑚𝑎𝑠𝑠 𝐹𝑒 = 3.3778 × 10−3 𝑚𝑜𝑙 𝐹𝑒2 𝑂3 × × 55.847
𝑚𝑜𝑙 𝐹𝑒2 𝑂3 𝑚𝑜𝑙 𝐹𝑒

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CHE 401 : ANALYTICAL CHEMISTRY

= 0.37728 𝑔 𝐹𝑒
0.37728 𝑔 𝐹𝑒
% 𝐹𝑒 = × 100% = 33.32%
1.1324 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒

(b) As shown by the following balanced equation, 3 mol of Fe 2O3 are chemically equivalent to 2
mol of Fe3O4. That is,

1
3 Fe2 O3 → 2 Fe3 O4 + O2
2
2 mol Fe3 O4 g Fe3 O4
𝑚𝑎𝑠𝑠 Fe3 O4 = 3.3778 × 10−3 mol Fe2 O3 × × 231.54
3 mol Fe2 O3 mol Fe3 O4
= 0.52140 g Fe3 O4

0.52140 g Fe3 O4
% Fe3 O4 = × 100% = 46.04%
1.1324 g sample

Exercise 4.1

A 0.2356-g sample containing only NaCl (58.44 g/mol) and BaCl 2 (208.23 g/mol) yielded
0.4637 g of dried AgCl (143.32 g/mol). Calculate the percent of each halogen compound in the
sample.

4.7 APPLICATIONS OF GRAVIMETRIC METHODS

Gravimetric methods have been developed for most inorganic anions and cations, as well
as for such neutral species as water, sulfur dioxide, carbon dioxide, and iodine. A variety of organic
substances can also be easily determined gravimetrically. Examples include lactose in milk
products, salicylates in drug preparations, phenolphthalein in laxatives, nicotine in pesticides,
cholesterol in cereals, and benzaldehyde in almond extracts. Indeed, gravimetric methods are
among the most widely applicable of all analytical procedures.

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CHE 401 : ANALYTICAL CHEMISTRY

4.7.1 Inorganic precipitating agents

Table 4.3 lists common inorganic precipitating agents. These reagents typically form
slightly soluble salts or hydrous oxides with the analyte. As you can see from the many entries for
each reagent, few inorganic reagents are selective.

Table 4.3. Some Inorganic Precipitating Agents

Precipitating Agent Element Precipitated*

Be (BeO), Al (Al2O3), Se (Se2O3), Cr (Cr2O3) †, Fe (Fe2O3),
NH3(aq)
(Ga2O3), Zr (ZrO2), In (ln2O3), Sn (SnO2), U (U3O8)
Cu (CuO) †, Zn (ZnO, or ZnSO4), Ge (GeO2), As (As2O3, or As2O5),
H2S
Mo (MoO3), Sn (SnO2) †, Sb (Sb2O3), or Sb2O5), Bi (Bi2S3)
(NH4)2S Hg (HgS), Co (CO3O4)
Mg (Mg2P2O7), AI (AlPO4), Mn (Mn2P2O7), Zn (Zn2P2O7), Zr
(NH4)2HPO4
(Zr2P2O7), Cd (Cd2P2O7), Bi (BiPO4)
H2SO4 Li, Mn, Sr, Cd, Pb, Ba (all as sulfates)
H2PtCl6 K (K2PtCl6, or Pt), Rb (Rb2PtCI6), Cs (Cs2PtCI6)
H2C2O4 Ca (CaO), Sr (SrO), Th (ThO2)
(NH4)2MoO4 Cd (CdMoO4) †, Pb (PbMoO4)
HCl Ag (AgCl), Hg (Hg2CI2), Na (as NaCl from butyl alcohol), Si (SiO2)
AgNO3 Cl (AgCl), Br (AgBr), I(AgI)
(NH4)2CO3 Bi (Bi2O3)
NH4SCN Cu [Cu2(SCN)2]
Ru, Os, Ir (precipitated as hydrous oxides; reduced with H2 to
NaHCO3
metallic state)
HNO3 Sn (SnO2)
H5IO6 Hg [Hg5(IO6)2]
NaCl, Pb (NO3)2 F (PbClF)
BaCl2 SO24- (BaSO4)
MgCl2, NH4Cl PO34- (Mg2PO7)

*Boldface type indicates that gravimetric analysis is the preferred method for the element
or ion. The weighed form is indicated in parentheses.
†A dagger indicates that the gravimetric method is seldom used. An underscore indicates
the most reliable gravimetric method.
From W. F. Hillebrand, G. E. F. Lundell, H. A. Bright, and J. I. Hoffman, Applied
Inorganic Analysis, New York: Wiley. 1953.

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CHE 401 : ANALYTICAL CHEMISTRY

4.7.2 Reducing agents

Table 4.3. Some Reducing Agents Employed in Gravimetric Methods

Reducing Agent Analyte

SO2 Se, Au
SO2 + H2NOH Te
H2NOH Se
H2C2O4 Au
H2 Re, Ir
HCOOh Pt
NaNO2 Au
SnCl2 Hg
Co, Ni, Cu, Zn, Ag, In, Sn, Sb, Cd,
Electrolytic reduction
Re, Bi

4.7.3 Organic precipitating agents

Numerous organic reagents have been developed for the gravimetric determination of
inorganic species. Some of these reagents are significantly more selective in their reactions than
are most of the inorganic reagents listed in Table 5-2.

8-HYDROXYQUINOLINE (OXINE)
Approximately two dozen cations form sparingly soluble chelates with 8-
hydroxyquinoline. The structure of magnesium 8-hydroxyquinolate is typical of these
chelates.

DIMETHYLGLYOXIME
Dimethylglyoxime is an organic precipitating agent of unparalleled specificity.
Only nickel (II) is precipitated from a weakly alkaline solution. The reaction is

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CHE 401 : ANALYTICAL CHEMISTRY

SODIUM TETRAPHENYLBORATE
Sodium tetraphenylborate. (C6H5)4 B-Na+, is an important example of an organic
precipitating reagent that forms salt-like precipitates. In cold mineral acid solutions, it is a
near-specific precipitating agent for potassium and ammonium ions. The precipitates have
stoichiometric composition and contain one mole of potassium or ammonium ion for each
mole of tetraphenylborate ion: these ionic compounds are easily filtered and can be brought
to constant mass at 105oC to 120°C. Only mercury (II), rubidium, and Cesium interfere
and must be removed by prior treatment.

4.8 END OF MODULE TEST

Answer the following problems.

1. Treatment of a 0.2500 gram sample of impure potassium chloride with an excess of AgNO 3
resulted in the formation of 0.2912 g of AgCl. Calculate the percentage of KCl in the
sample.

2. The aluminium in a 0.910 gram sample of impure ammonium aluminium sulphate was
precipitated with aqueous ammonia as the hydrous Al 2O3• H2O. The precipitate was
filtered and ignited at 1000C to give anhydrous Al 2O3 which weighs 0.2001 gram. Express
the result of this analysis in terms of
a. % NH4Al(CO4)2
b. % Al2O3
c. % Al

3. What mass of Cu(IO3) can be formed from 0.500 gram CuSO4 • 5H2O?

4. What mass of KIO3 is needed to convert the copper in 0.200 gram in CuSO 4 • 5H2O to
Cu(IO3)2?

5. What mass of AgI can be produced from a 0.512 gram sample that assays 20.1% AlI3?

6. Precipitate used in gravimetric determination of uranium include Na 2U2O7 (634.0 g/mol),

(UO2)2P2O7 (714.0 g/mol), and V2O5-2UO3 (753.9 g/mol). Which of these weighing forms
provides the greatest mass of the precipitate from a given quantity of uranium?

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CHE 401 : ANALYTICAL CHEMISTRY

7. A 0.2121 gram sample of organic compound was burned in a stream of oxygen and the
CO2 produced was collected in a solution of barium hydroxide. Calculate the percentage
of carbon in the sample if 0.6006 gram of BaCO3 was formed.

8. A 5.000 grams sample of pesticide was decomposed with metallic sodium in alcohol and
then liberated v/chloride ion was precipitated as AgCl. Express the results of this analysis
in terms of percent DDT (C14H9Cl5) based on the recovery of 0.1606 gram of the AgCl.

9. Ammoniacal nitrogen can be determined by treatment of the sample with chloroplatinic

acid; the product is slightly soluble ammonium chloride palatinate
H2 PtCl6 + 2NH4 + → (NH4 )2 PtCl6 + 2H+

The precipitate decomposes on ignition, yielding metallic platinum and gaseous products:
(NH4 )2 PtCl6 → Pt(s) + 2Cl2 (g) + 2NH3 (g) + 2HCl

Calculate the percentage ammonia in a sample if 0.2115 gram gave rise to 0.4693 gram of
platinum

10. A series of sulphate samples is to be analysed by precipitation as BaSO4. If it is known

that the sulphate content in these samples ranges between 20% and 55%, what minimum
sample mass should be taken to ensure that a precipitate mass no smaller than 0.200 gram
is produced? What is the maximum precipitate weight to be expected if this quantity of
sample is taken.

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