Gravimetric Methods

of Analysis
Chem 2105: Analytical Chemistry I
 DISCLAIMER
The contents of this presentation is not the original work of the
presenter and was derived from copyrighted materials, mostly from
the prescribed textbook (Skoog, et. al., Fundamentals of
Analytical Chemistry, 9e, 2014) for this subject. This presentation
and its contents was only provided for educational purpose of
Chem 2105 students of Central Philippine University. Any part of
this presentation must not be shared or disclosed to a third party
without the consent of the Chem 2105 instructor.
 Gravimetric Methods of Analysis

• Gravimetric methods are quantitative methods

that are based on determining the mass of a pure
compound to which the analyte is chemically
related.
 Gravimetric Methods of Analysis

• In 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.
 Gravimetric Methods of Analysis

• In volatilization methods, the analyte or its decomposition

products are volatilized at a suitable temperature.
• The volatile product is then collected and weighed, or,
alternatively, the mass of the product is determined
indirectly from the loss in mass of the sample.
 Gravimetric Methods of Analysis

• In electrogravimetry, the analyte is separated by deposition

on an electrode by an electrical current. The mass of this
product then provides a measure of the analyte concentration.
 Gravimetric Methods of Analysis

• In gravimetric titrimetry, the mass of a reagent of known

concentration required to react completely with the analyte
provides the information needed to determine the analyte
concentration.
 Gravimetric Methods of Analysis
• Atomic mass spectrometry uses a mass spectrometer to separate the
gaseous ions formed from the elements making up a sample of matter.
The concentration of the resulting ions is then determined by measuring
the electrical current produced when they fall on the surface of an ion
detector.
 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.
Precipitation Gravimetry
 Properties Of Precipitates
And Precipitating Reagents
• Ideally, a gravimetric precipitating agent
should react specifically, or if not, then
selectively with the analyte.
 Properties Of Precipitates
And Precipitating Reagents
• The ideal precipitating reagent would react with the analyte to give a
product that is
1. Readily filtered and washed free of contaminants
2. Of sufficiently low solubility so that no significant loss of the solid occurs
during filtration and washing
3. Unreactive with constituents of the atmosphere
4. Of known composition after it is dried or, if necessary, ignited
 Particle Size and Filterability of
Precipitates
• Precipitates made up of large particles are generally desirable in
gravimetric work because large particles are easy to filter and
wash free of impurities. In addition, precipitatesof this type are
usually purer than are precipitates made up of fine particles.
 Particle Size and Filterability of
Precipitates
• A colloid is a solid made up of particles having diameters
that are less than 10-4 cm.
• Colloidal particles show no tendency to settle from
solution, nor are they easily filtered.
 Particle Size and Filterability of
Precipitates
• The particles, with dimensions on the order of tenths of
a millimeter or greater, temporary dispersed in the liquid
phase is called a crystalline suspension.
• The particles of a crystalline suspension tend to settle
spontaneously and are readily filtered.
 Particle Size and Filterability of
Precipitates
• Crystalline suspension, are particles with dimensions on
the order of tenths of a millimeter or greater.
• The particles of a crystalline suspension tend to settle
spontaneously and are easily filtered.
 Particle Size and Filterability of
Precipitates
• What Factors Determine Particle Size?
• The particle size of a precipitate is influenced by such
experimental variables as precipitate solubility, temperature,
reactant concentrations, and the rate at which reactants are
mixed.
 Particle Size and Filterability of
Precipitates
• What Factors Determine Particle Size?
• The particle size is related to relative supersaturation, where

von Weimarn Ratio

• Q is the concentration of the solute at any instant and S is its equilibrium

solubility.
 Particle Size and Filterability of
Precipitates
• What Factors Determine Particle Size?
• When (Q - S)/S is large, the precipitate tends to be colloidal;
when (Q - S)/S is small, a crystalline solid is more likely.
 Particle Size and Filterability of
Precipitates
• How Do Precipitates Form?
• Assume that precipitates form in two ways, namely by nucleation and
by particle growth.
• The particle size of a freshly formed precipitate is determined by
which way is faster.
 Particle Size and Filterability of
Precipitates
• How Do Precipitates Form?
• Nucleation is a process in which a minimum number of atoms, ions, or
molecules join together to produce a stable solid.
• Further precipitation then involves a competition between additional
nucleation and growth on existing nuclei (particle growth).
 Particle Size and Filterability of
Precipitates
• How Do Precipitates Form?
• The rate of nucleation is believed to increase enormously with
increasing relative supersaturation.
• In contrast, the rate of particle growth is only moderately enhanced
by high relative supersaturations.
 Particle Size and Filterability of
Precipitates
• How Do Precipitates Form?
• When a precipitate is formed at high relative supersaturation, nucleation
is the major precipitation mechanism.
• At low relative supersaturations, on the other hand, the rate of particle
growth tends to predominate.
• Low relative supersaturation produces crystalline suspensions.
 Particle Size and Filterability of
Precipitates
• Controlling Particle Size
• Experimental variables lead to crystalline precipitates include elevated
temperatures to increase the solubility of the precipitate, dilute
solutions, and slow addition of the precipitating agent with good
stirring.
• Larger particles can also be obtained by pH control, provided the
solubility of the precipitate depends on pH.
 Colloidal Precipitates
• Coagulate, or agglomerate, the individual particles of most
colloids to give a filterable, amorphous mass that will settle out
of solution.
 Colloidal Precipitates
• Coagulation of Colloids
• Coagulation can be hastened by heating, stirring, and adding an
electrolyte to the medium.
• The charge on a colloidal particle formed in a gravimetric analysis is
determined by the charge of the lattice ion that is in excess when the
precipitation is complete.
 Colloidal Precipitates
Coagulation of Colloids
• Adsorption is a process in which a substance (gas, liquid, or solid) is
held on the surface of a solid. In contrast, absorption involves
retention of a substance within the pores of a solid.
 Colloidal Precipitates
Coagulation of Colloids
• The charge on a colloidal particle formed in a gravimetric analysis is
determined by the charge of the lattice ion that is in excess when the
precipitation is complete.
 Colloidal Precipitates
Coagulation of Colloids
• The adsorption of ions on an ionic solid originates from the normal bonding forces
that are responsible for crystal growth.
• The kind of ions retained on the surface of a colloidal particle and their number
depend in a complex way on several variables. For a suspension produced in a
gravimetric analysis, however, the species adsorbed, and hence the charge on the
particles, can be easily predicted because lattice ions are generally more strongly held
than others.
 Colloidal Precipitates
Coagulation of Colloids
• The extent of adsorption and thus the charge on a given particle
increase rapidly as the concentration of a common ion becomes greater.
• Eventually, however, the surface of the particles becomes covered with
the adsorbed ions, and the charge becomes constant and independent of
concentration.
Figure 4-2 A
colloidal silver
chloride particle
suspended in a
solution of silver
nitrate.
 Colloidal Precipitates
Coagulation of Colloids
Attached directly to the solid surface is the primary adsorption layer, which
consists mainly of adsorbed silver ions. Surrounding the charged particle is a layer of
solution, called the counter-ion layer, which contains sufficient excess of negative
ions (principally nitrate) to just balance the charge on the surface of the particle. The
primarily adsorbed silver ions and the negative counter-ion layer constitute an electric
double layer that imparts stability to the colloidal suspension. As colloidal particles
approach one another, this double layer exerts an electrostatic repulsive force that
prevents particles from colliding and adhering.
Figure 4-3 Effect of AgNO3 and
electrolyte concentration on the
thickness of the double layer
surrounding a colloidal AgCl
particle in a solution containing
excess of AgNO3 .
Figure 4-4 The electric double layer of a
colloid consists of a layer of charge
adsorbed on the surface of the particle
(the primary adsorption layer) and a
layer of opposite charge (the counter-ion
layer) in the solution surrounding the
particle. Increasing the electrolyte
concentration has the effect of
decreasing the volume of the counter-ion
layer, thereby increasing the chances for
coagulation.
 Colloidal Precipitates
Coagulation of Colloids
• Coagulation of a colloidal suspension can often be brought about by
a short period of heating, particularly if accompanied by stirring.
• An even more effective way to coagulate a colloid is to increase the
electrolyte concentration of the solution.
 Colloidal Precipitates
Peptization of Colloids
• Peptization is a process by which a coagulated colloid returns to its
dispersed state.
 Colloidal Precipitates
Peptization of Colloids
• 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.
• Washing is needed to minimize contamination, but on the other, there is a risk of
losses resulting from peptization if pure water is used.
• The problem is usually solved by washing the precipitate with a solution containing
an electrolyte that volatilizes when the precipitate is dried or ignited.
 Colloidal Precipitates
Treatment of Colloidal Precipitates
• Colloids are best precipitated from hot, stirred solutions containing
sufficient electrolyte to ensure coagulation.
 Crystalline Precipitates
• Improving Particle Size and Filterability
• The particle size of crystalline solids can often be improved significantly by
minimizing Q, maximizing S, or both.
• The value of Q is can often be minimized by using dilute solutions and adding the
precipitating reagent slowly, with good mixing. Often, S is increased by precipitating
from hot solution or by adjusting the pH of the precipitation medium.
 Crystalline Precipitates
• Improving Particle Size and Filterability
• Digestion of crystalline precipitates (without stirring) for some time
after formation frequently 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.
 Coprecipitation
• There are four types of coprecipitation: surface adsorption, mixed-
crystal formation, occlusion, and mechanical entrapment.
• Coprecipitation is a process in which normally soluble compounds are
carried out of solution by a precipitate.
• Surface adsorption and mixed-crystal formation are equilibrium
processes, and occlusion and mechanical entrapment arise from the
kinetics of crystal growth.
 Coprecipitation
Surface Adsorption
• Adsorption is a common source of coprecipitation that is likely to
cause significant contamination of precipitates with large specific
surface areas, coagulated colloids.
 Coprecipitation
Surface Adsorption
Minimizing Adsorbed Impurities on Colloids.
• The purity of many coagulated colloids is improved by digestion.
• Regardless of the method of treatment, a coagulated colloid is always
contaminated to some degree, even after extensive washing.
 Coprecipitation
Surface Adsorption
Reprecipitation.
A drastic but effective way to minimize the effects of adsorption is
reprecipitation, or double precipitation.
 Coprecipitation
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.
• The extent of mixed-crystal contamination is governed by the law of
mass action and increases as the ratio of contaminant to analyte
concentration increases.
 Coprecipitation
Mixed-Crystal Formation
• 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.
• When mixed-crystal formation occurs, the interfering ion may have to be separated
before the final precipitation step. Alternatively, a different precipitating reagent that
does not give mixed crystals with the ions in question may be used.
 Coprecipitation
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.
• Occlusion is a type of coprecipitation in which a compound is trapped
within a pocket formed during rapid crystal growth.
 Coprecipitation
• Occlusion and Mechanical Entrapment
• Mixed-crystal formation may occur in both colloidal and crystalline
precipitates, whereas occlusion and mechanical entrapment are
confined to crystalline precipitates.
• 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.
 Coprecipitation
Occlusion and Mechanical Entrapment
• 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 is often remarkably helpful in reducing these
types of coprecipitation.
 Coprecipitation
Coprecipitation Errors
Coprecipitation can cause either negative or positive errors.
 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.
• Local reagent excesses do not occur because the precipitating agent
appears gradually and homogeneously throughout the solution and
reacts immediately with the analyte.
 Precipitation from Homogeneous Solution

• In general, homogeneously formed precipitates, both colloidal and

crystalline, are better suited for analysis than a solid formed by direct
addition of a precipitating reagent.
 Precipitation from Homogeneous Solution

• Figure 12-5 Aluminum

hydroxide formed by the
direct addition of ammonia
(left) and the homogeneous
production of hydroxide
(right).
 Drying And Ignition Of Precipitates
• After filtration, a gravimetric precipitate is heated until its mass
becomes constant.
• 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.
Drying And Ignition Of Precipitates
 Drying And Ignition Of Precipitates
• Recording thermal decomposition curves is often called
thermogravimetry or thermalgravimetric analysis, and the mass vs.
temperature curves are called thermograms.
Drying And Ignition Of
Precipitates

Figure 4-7 Effect of

temperature on precipitate
mass.
 Calculating Results From
Gravimetric Data
• The results of a gravimetric analysis are generally computed
from the mass of sample and the mass of a product of known
composition.
 Calculating Results From
Gravimetric Data
• The results of a gravimetric analysis are generally computed
from the mass of sample and the mass of a product of known
composition.
 Example 12-2
• 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 Fe2O3 (159.69 g/mol).
Calculate (a) the % Fe (55.847 g/mol) and (b) the % Fe3O4 (231.54
g/mol) in the sample.
 Example
Percentage of the sought component in the sample using gravimetric method
could be solved by using this generalized equation

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑒𝑖𝑔ℎ𝑒𝑑 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 × 𝑔𝑟𝑎𝑣𝑖𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑎𝑐𝑡𝑜𝑟

%𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 = × 100
𝑚𝑎𝑠𝑠 𝑠𝑎𝑚𝑝𝑙𝑒

Gravimetric factor (G.F.) is the ratio between the compound and the element that
can be taken from that compound.
 Example
To calculate for a.) %Fe in the sample,
First we must know the mass of Fe2O3 that was obtained from the sample. The
mass of Fe2O3 was 0.5394 g based on the given
Then we need to determine the gravimetric factor of Fe and Fe2O3
𝑎 × 𝑀𝑊 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑠𝑜𝑢𝑔ℎ𝑡
𝐺𝐹 =
𝑏 × 𝑀𝑊 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑤𝑒𝑖𝑔ℎ𝑒𝑑
a and b are whole number that have values that are chemically equivalent
 Example
To calculate for a.) %Fe in the sample,
Looking at the given example it is shown that 2 moles of Fe (sought) is chemically
equivalent to 1 mole Fe2O3 (weighed). Thus the gravimetric factor could be express as
follows,
2 × 55.847
𝐺𝐹 =
1 × 159.69

Note that units are ignored in the equation since both the numerator and
denominator would have the same units thus resulting to cancellation and a
dimensionless quantity
 Example
To calculate for a.) %Fe in the sample,
Since the mass of the weighed compound was known so as the mass of the sample and
the gravimetric factor was determined then based on the equation that was previously showed
if follows that,
2 × 55.847
0.5394 𝑔 ×
%𝐹𝑒 = 1 × 159.69 × 100% = 𝟑𝟑. 𝟑𝟐%
1.1324 𝑔
 Example
To calculate for b.) %Fe3O4 same procedure could be followed
As you could see 2 mole Fe3O4 (sought) is chemically equivalent to 3 moles
Fe2O3(weighed) thus it follows that the gravimetric factor is
2 × 231.54
𝐺𝐹 =
3 × 159.69
The %Fe3O4 would then be
2 × 231.54
0.5394 𝑔 ×
%𝐹𝑒 = 3 × 159.69 × 100% = 𝟒𝟔. 𝟎𝟒%
1.1324 𝑔
 Applications Of Gravimetric Methods
• Gravimetric methods have been developed for most inorganic
anions and cations as well as for such neutral species.
• A variety of organic substances can also be readily determined
gravimetrically.
• Gravimetric methods do not require a calibration or
standardization step because the results are calculated directly
from the experimental data and molar masses.
 Inorganic Precipitating Agents

• These reagents typically form slightly soluble salts or

hydrous oxides with the analyte.
• Most inorganic reagents are not very selective.
 Organic Precipitating Agents
• Numerous organic reagents have been developed for the
gravimetric determination of inorganic species.
• One forms slightly soluble nonionic products called coordination
compounds; the other forms products in which the bonding
between the inorganic species and the reagent is largely ionic.
 Organic Precipitating Agents
• Organic reagents that yield sparingly soluble coordination
compounds typically contain at least two functional groups. Each
of these groups is capable of bonding with a cation by donating a
pair of electrons. The functional groups are located in the
molecule such that a five- or six-membered ring results from the
reaction. Reagents that form compounds of this type are called
chelating agents, and their products are called chelates.
 Organic Precipitating Agents
• Chelates are cyclical metal-organic compounds in which the metal
is a part of one or more five- or six-membered rings.
• 8-Hydroxyquinoline and dimethylglyoxime are two widely used
chelating reagent. Sodium tetraphenyl borate is a near-specific
precipitation agent for potassium and ammonium.
 Organic Precipitating Agents
• 8-Hydroxyquinoline
 Organic Precipitating Agents
• 8-Hydroxyquinoline
• The solubilities of metal 8-hydroxyquinolates vary widely from
cation to cation and are pH dependent because 8-
hydroxyquinoline is always deprotonated during a chelation
reaction. Therefore, we can achieve a considerable degree of
selectivity in the use of 8-hydroxyquinoline by controlling pH.
 Organic Precipitating Agents
• Dimethylglyoxime
• Dimethylglyoxime is an organic precipitating agent of
unparalleled specificity. Only nickel(II) is precipitated
from a weakly alkaline solution.
 Organic Precipitating Agents
• Dimethylglyoxime
 Organic Precipitating Agents
• Dimethylglyoxime
• This precipitate is so bulky that only small amounts of
nickel can be handled conveniently. It also has an
exasperating tendency to creep up the sides of the
container as it is filtered and washed. The solid is
conveniently dried at 110°C and has the composition
C8H14N4NiO4.
 Organic Precipitating Agents

• Sodium Tetraphenylborate and Dimethylglyoxime

• Sodium tetraphenylborate, (C6H5) 4B-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.
 Organic Precipitating Agents

• Sodium Tetraphenylborate and Dimethylglyoxime

• The precipitates have stoichiometric composition and contain
one mole of potassium or ammonium ion for each mole of
tetraphenylborate ion. Only mercury(II), rubidium, and cesium
interfere and must be removed by prior treatment.
 Volatilization Methods

• The two most common gravimetric methods based on

volatilization are those for water and carbon dioxide.
• In direct determination, water vapor is collected on any
of several solid desiccants, and its mass is determined
from the mass gain of the desiccant.
 Volatilization Methods

• The indirect method in which the amount of water is

determined by the loss of mass of the sample during
heating is less satisfactory because it must be assumed
that water is the only component that is volatilized. This
assumption can present problems, however, if any
component of the precipitate is volatile.
 Volatilization Methods

• An example of a gravimetric procedure involving

volatilization of carbon dioxide is the determination of
the sodium hydrogen carbonate content of antacid
tablets. A weighed sample of the finely ground tablets is
treated with dilute sulfuric acid to convert the sodium
hydrogen carbonate to carbon dioxide
Figure 12-8 Apparatus for determining the sodium hydrogen carbonate content of
antacid tablets by a gravimetric volatilization procedure.