PHA 110 Analytical Chemistry I

Assist. Prof. Dr. Hürmüs REFİKER

Chapter 2 Gravimetric Methods of Analysis

Topics

 Gravimetric Methods of Analysis

Precipitation Gravimetry
Mechanism of Precipitate Formation
Colloidal Precipitates
Crystalline Precipitates
Coprecipitation Precipitates
Precipitation from Homogeneous Solution
Organic Precipitating Agents
Volatilization Gravimetry
Gravimetric Methods of Analysis

• Gravimetric methods of analysis are based on

mass measurements with an analytical balance,
an instrument that yields highly accurate and
precise data.

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Gravimetric Methods of Analysis

• Precipitation gravimetry,

the analyte is separated from a solution of the sample as a precipitate and is

converted to a compound of known composition that can be weighed.

• Volatilization gravimetry,

the analyte is separated from other constituents of a sample by converting it

to a gas of known chemical composition. The mass of the gas then serves as
a measure of the analyte concentration.

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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.

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Precipitation Gravimetry

• For example; a precipitation method for determining calcium in water is

one of the official methods. In this technique, an excess of oxalic acid,
H2C2O4, 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 + H2C2O4 → 2NH4+ + C2O4 2-

Ca2+ (aq) + C2O4 2- (aq) → CaC2O4 (s)

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Precipitation Gravimetry

• The CaC2O4 precipitate is filtered using a weighed filtering crucible, then

dried and ignited. This process converts the precipitate entirely to calcium
oxide. The reaction is

∆
CaC2O4 (s) → CaO (s) + CO (g) + CO2 (g)
Ca in water

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

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Properties of Precipitates

• 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.

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Properties of Precipitates

Selective Reagent AgNO3 (Silver nitrate)

The only common ions that it

precipitates from acidic solution
are Cl-, Br-, I-, and SCN- (Thiocyanate).

Specific Reagent Dimethylglyoxime

Precipitates only Ni2+ from alkaline

solutions.
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Properties of Precipitates

• 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.

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Particle Sizes of Precipitates

tiny particles are invisible to

Colloidal Suspensions the naked eye (10-7 to 10-4
cm in diameter). Colloidal
particles show no tendency
to settle
from solution and are
difficult to filter.

are particles with dimensions

on the order of tenths of a
millimeter or greater.
Crystalline Suspension Particles of the temporary
dispersion
of such particles in the liquid
phase tend to settle
spontaneously and are easily
filtered.
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Particle Sizes of Precipitates
A colloid consists of solid particles with diameters that are
less than 10-4 cm. In diffuse light, colloidal suspensions
may be perfectly clear and appear to contain no solid. The
presence of the second phase can be detected, however, by
shining the beam of a flashlight into the solution. Because
particles of colloidal dimensions scatter visible radiation, the
path of the beam through the solution can be seen by the
eye. This phenomenon is called the Tyndall effect.

The Tyndall effect. The photo shows two cuvettes: the one
on the left contains only water while the one on the right
contains a solution of starch. As red and green laser beams
pass through the water in the left cuvette, they are invisible.
Colloidal particles in the starch solution in the right cuvette
scatter the light from the two lasers, so the beams become
visible

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Particle Sizes of Precipitates

• Precipitate formation has been studied for many years, but the
mechanism of the process is still not fully understood. What is
certain, however, is that the particle size of a precipitate is
influenced by
• precipitate solubility,
• temperature,
• reactant concentrations,
• the rate at which reactants are mixed.

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Particle Sizes of Precipitates

• 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 relative
supersaturation, where

𝑸−𝑺
𝒓𝒆𝒍𝒂𝒕𝒊𝒗𝒆 𝒔𝒖𝒑𝒆𝒓𝒔𝒂𝒕𝒖𝒓𝒂𝒕𝒊𝒐𝒏=
𝑺
Von Weimarn
equation

Q = the concentration of the solute at any

instant
S = equilibrium
solubility
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Particle Sizes of Precipitates

• A supersaturated solution is an unstable solution that

contains a higher solute concentration than a saturated
solution. As excess solute precipitates with time,
supersaturation decreases to zero.

A single crystal of sodium acetate added to a supersaturated solution of sodium acetate

in water causes the excess solute to rapidly crystallize from the solution.
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Particle Sizes of Precipitates

• Experimental evidence indicates that the particle size of a precipitate varies

inversely with the average relative supersaturation during the time when the
reagent is being introduced.

𝑸−𝑺
𝒓𝒆𝒍𝒂𝒕𝒊𝒗𝒆 𝒔𝒖𝒑𝒆𝒓𝒔𝒂𝒕𝒖𝒓𝒂𝒕𝒊𝒐𝒏=
𝑺
Large Small

the precipitate tends a crystalline solid is

to be colloidal more likely

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Particle Sizes of Precipitates

Colloidal Precipitates Crystalline Particles

Hard to filter (tiny particles) Easy to filter (large particles)
Stable precipitates More pure precipitates

The lower RSS value means larger particles.

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Experimental Control of Particle Size

How can we decrease the RSS?

Increase S;
• Heating to increase solubility
• pH adjustment (If the solubility of the precipitate depends on pH)
• Adding complexing agent
𝑸−𝑺
𝑹𝑺𝑺=
Decrease Q; 𝑺
• Using dilute precipitating solution
• Adding precipitating agent slowly and stirring
• Using homogeneous precipitation technique
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Experimental Control of Particle Size

Unfortunately, many precipitates cannot be formed as crystals under

practical laboratory conditions.
A colloidal solid is generally formed when a precipitate has such a low
solubility. The relative supersaturation thus remains enormous throughout
precipitate formation, and a colloidal suspension results.
For example, under conditions feasible for an analysis, the hydrous oxides of
iron(III), aluminum, and chromium(III) and the sulfides of most heavy-metal
ions form only as colloids because of their very low solubilities.

Precipitates that have very low solubilities, such as many sulfides and
hydrous oxides, generally form as colloids.

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Mechanism of Precipitate Formation

Nucleation Particle Growth

is a process in which a
minimum number of atoms, Predominate Predominate
ions, or molecules join s s
together to give a stable
solid.
Large number of Smaller number of
small particles larger particles

High
Low RSS
RSS

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Mechanism of Precipitate Formation

• For example, large, easily filtered crystals of calcium oxalate

are obtained by forming the bulk of the precipitate in a mildly
acidic environment in which the salt is moderately soluble. The
precipitation is then completed by slowly adding aqueous
ammonia until the acidity is sufficiently low for removal of
substantially all of the calcium oxalate.

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Colloidal Precipitates

• 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.

• 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.

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Colloidal Precipitates

• Colloidal suspensions are stable because all of the particles of the

colloid are either positively or negatively charged and thus repel one
another. The charge results from cations or anions that are bound to
the surface of the particles. We can show that colloidal particles are
charged by placing them between charged plates where some of the
particles migrate toward one electrode while others move toward the
electrode of the opposite charge. The process by which ions are
retained on the surface of a solid is known as adsorption.

• Adsorption is a process in which a substance (gas, liquid, or solid) is

held on the surface of a solid.
• Absorption is retention of a substance within the pores of a solid.
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Colloidal Precipitates

Attached directly to the

solid surface is the
primary
adsorption layer

Surrounding the charged

particle is a layer of
solution, called the
counter-ion layer
The primarily adsorbed silver ions
and the negative counter-ion layer
constitute an electric double layer
that imparts stability to the colloidal
suspension.

A colloidal silver chloride particle suspended in a solution of silver

nitrate.
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Colloidal Precipitates

• Peptization is the process by which a coagulated

colloid reverts to its original dispersed.
• Digestion is a process in which a precipitate is
heated in the solution from which it was formed
(the mother liquor) and allowed to stand in
contact with the solution.
• Mother liquor is the solution from which a
precipitate was formed.

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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 some extent.

• Digestion of crystalline precipitates (without stirring) for some

time after formation often yields a purer, more filterable
product. The improvement in filterability undoubtedly results
from the dissolution and recrystallization that occur
continuously and at an enhanced rate at elevated temperatures.
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Coprecipitation Precipitates

Coprecipitation is a process in which normally soluble

compounds are carried out of solution by a precipitate. There are
four types of coprecipitation;
• Surface adsorption
• Mixed-crystal formation
• Occlusion
• Mechanical entrapment.

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Surface Adsorption

• Adsorption is a common source of coprecipitation and is likely

to cause significant contamination of precipitates with large
specific surface areas, that is, coagulated colloids.

• 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.

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Surface Adsorption

Minimizing Adsorbed Impurities of Colloids

• Washing a coagulated colloid with a solution containing a volatile electrolyte.

Washing generally does not remove much of the primarily adsorbed ions
because the attraction between these ions and the surface of the solid is too
strong.

• Digestion: during this process, water is expelled from the solid to give a denser
mass that has a smaller specific surface area for adsorption.

• Reprecipitation: In this process, the filtered solid is redissolved and

reprecipitated. The solution containing the redissolved precipitate has a
significantly lower contaminant concentration than the original, and even less
adsorption occurs during the second precipitation.
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Surface Adsorption

A coagulated colloid. This figure suggests that a coagulated

colloid continues to expose a large urface area to the solution
from which it was formed.

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Surface Adsorption

• A drastic but effective way to minimize the effects of adsorption

is reprecipitation. In this process, the filtered solid is
redissolved and reprecipitated.

• The first precipitate usually carries down only a fraction of the

contaminant present in the original solvent. Thus, the solution
containing the redissolved precipitate has a significantly lower
contaminant concentration than the original, and even less
adsorption occurs during the second precipitation.

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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%.

Similar ions can replace the analyte ion in the crystal

lattice during precipitation.

Example; Determination of SO42- as BaSO4

The presence of Pb (Lead) or Sr (Strontium)
will cause a mixed crystal containing either
PbSO4 or SrSO4.

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Mixed-Crystal Formation

• Mixed- crystal formation is a problem with both

colloidal suspentions and crystalline precipitates.

How can this problem be solved?

• Interfering ion may separated before the final precipitation

step.
• Different precipitating reagent that does not give mixed crystals
with the ions in question may be used

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Occlusion and Mechanical Entrapment

Occlusion
• A type of co-precipitation in which a compound (foreign ions in the
counter-ion layer ) is physically trapped or occluded within a precipitate
during rapid precipitate formation.

If crystal growth is too

rapid, some counter ions do
not have time to escape
from the surface.

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Occlusion and Mechanical Entrapment

Mechanical Entrapment
• A type of co-precipitation in which coprecipitated physically trap a pocket
of solution within a precipitate during rapid precipitate formation.

Two crystals grow together and

trap a species in the space
between them. These crystals lie
close together during growth.

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Occlusion and Mechanical Entrapment

• Mixed-crystal formation may occur in both colloidal and

crystalline precipitates, but occlusion and mechanical
entrapment are confined to crystalline precipitates.

Both occlusion and mechanical entrapment are at a minimum when the rate
of precipitate formation is low, that is, under conditions of low
supersaturation. In addition, digestion often reduces the effects of these
types of coprecipitation. Undoubtedly, the rapid dissolving and
reprecipitation that occur at the elevated temperature of digestion open up
the pockets and allow the impurities to escape into the solution

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Coprecipitation Errors

• Coprecipitated impurities may cause either negative or positive

errors in an analysis. If the contaminant is not a compound of
the ion being determined, a positive error will always result.

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Precipitation from Homogeneous Solution

• Homogeneous precipitation is a process in which a precipitate is formed by

slow generation of a precipitating reagent homogeneously throughout a
solution.
• Solids formed by homogeneous precipitation are generally purer and more
easily filtered than precipitates generated by direct addition of a reagent to
the analyte solution.

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Precipitation from Homogeneous Solution

• Homogeneous precipitation is a process in which a precipitate is formed

by slow generation of a precipitating reagent homogeneously throughout a
solution.

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Precipitation from Homogeneous Solution

• Urea is often used for the homogeneous generation of hydroxide ion.

The reaction can be expressed by the equation

(H2N)CO + 3H2O CO2 + 2NH4+ + 2OH-

• This hydrolysis proceeds slowly at temperatures just below

100°C, with 1 to 2 hours needed to complete a typical
precipitation. Urea is particularly valuable for the precipitation
of hydrous oxides or basic salts

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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.

Effect of temperature on precipitate mass.

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Calculation of Results from Gravimetric Data Example 1

42
Example 2

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Example 2 cont’d

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Example 3

45
Example 3 cont’d

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Example 3 cont’d

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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 determined
gravimetrically.

48
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.

49
Reducing Agents

List of several reagents

that convert an analyte
to its elemental form
for weighing.

50
Organic Precipitating Agents

• There are two types of organic reagents: one forms slightly

soluble nonionic products called coordination compounds,
and the other forms products in which the bonding between the
inorganic species and the reagent is largely ionic.

• Some organic reagents react with metal ions then produce

insoluble coordination compounds.
• Reagents that form coordination compounds of this type are
called chelating agents, and their products are called chelates.

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Organic Precipitating Agents

• Metal chelates are relatively nonpolar and, as a consequence, have

solubilities that are low in water but high in organic liquids. Usually, these
compounds possess low densities and are often intensely colored.
Because they are not wetted by water, coordination compounds are easily
freed of moisture at low temperatures.

This chelate picture is heme, which is a part

of hemoglobin, the oxygen- carrying
molecule in human blood. Notice the four
six-membered rings that are formed with
Fe2+.

52
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.

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Dimethylglyoxime

• Dimethylglyoxime is an organic precipitating agent of unparalleled

specificity. Only nickel(II) is precipitated from a weakly alkaline solution.
The reaction is;

54
Dimethylglyoxime

When dimethylglyoxime is added to a slightly basic solution of Ni2+(aq),

shown on the left, a bright red precipitate of Ni(C4H7N2O2)2 is formed as seen
in the beaker on the right.

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Sodium Tetraphenylborate

• Sodium tetraphenylborate, (C6H5)4B2Na1, 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.

56
Organic Functional Group Analysis

• Several reagents react selectively with certain organic functional groups

and thus can be used for the determination of most compounds
containing these groups

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Volatilization Gravimetry

• The two most common gravimetric methods based on volatilization are

those for determining water and carbon dioxide.
• Sulfides and sulfites can also be determined by volatilization. Hydrogen
sulfide or sulfur dioxide evolved from the sample after treatment with acid
is collected in a suitable absorbent.
• Finally, the classical method for the determination of carbon and hydrogen
in organic compounds is a gravimetric volatilization procedure in which the
combustion products (H2O and CO2) are collected selectively on weighed
absorbents. The increase in mass serves as the analytical variable.

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Volatilization Gravimetry

NaHCO3 (aq) + H2SO4 (aq) → CO2 (g) + H2O (l) + NaHSO4 (aq)

Apparatus for determining the sodium hydrogen carbonate content of antacid tablets by a gravimetric
volatilization procedure.
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Assigned Problems

1. Explain the difference between a colloidal and a crystalline precipitate.

2. Define adsorption.

3. Treatment of a 0.2500-g 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.

4. What mass of Cu(IO3)2 can be formed from 0.650 g of CuSO4 · 5H2O?

5. The mercury in a 1.0451-g sample was precipitated with an excess of paraperiodic acid, H5IO6:

5Hg2+ + 2H5IO6 → Hg5(IO6)2 + 10H+

The precipitate was filtered, washed free of precipitating agent, dried, and weighed, and 0.5718 g
60
was recovered. Calculate the percentage of Hg 2Cl2 in the sample.
REFERENCES

TEXTBOOK
• Fundamentals of Analytical Chemistry by Skoog D. A., West D. M.
and Holler F. J., 7 th Edition, Saunders College Publishing, Harcourt
Brace & Company, Orlando, Florida, 1996.

• Fundamentals of Analytical Chemistry by Skoog D. A., West D. M.,

Holler F. J., Crouch S.R. 9 th Edition, Brooks/Cole, Cengage Learning,
Belmont, USA , 2014.

• OPEN INTERNET SOURCES

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