Chapter 12

Gravimetric Methods of Analysis

Gravimetric methods of analysis are based on the measurement of
mass. There are two major types of gravimetric methods:
• Precipitation methods: in this method the analyte is converted to a
sparingly soluble precipitate. This precipitate is then filtered,
washed free of impurities, and converted to a product of known
composition by suitable heat treatment, and the product is weighed.
• Volatilization methods: in this 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.

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 PROPERTIES OF PRECIPITATES AND
PRECIPITATING REAGENTS
A gravimetric precipitating agent should react specifically,
and selectively with the analyte.
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

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 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, such precipitates are usually purer than
are precipitates made up of fine particles.

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 What Factors Determine Particle Size?
The particle size of solids formed by precipitation varies enormously.
 At one extreme are colloidal suspension, 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, nor are they easily filtered.
 At the other extreme are particles with dimensions on the order of tenths of
millimeter 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 readily filtered.

• The particle size of a precipitate is influenced by experimental variables as

precipitate solubility, temperature, reactant concentrations, and the rate at which
reactants are mixed.
• The particle size is related to a single property of the system called its relative
supersaturation, where
relative supersaturation = (Q – S) / S
In this equation, Q is the concentration of the solute at any instant and
S is its equilibrium solubility.
 when (Q – S)/ S is large, the precipitate tends to be colloidal.
 when (Q – S)/ S is small, a crystalline solid is more likely Catalyst
How do Precipitates Form (Mechanism)?
Precipitates form in two ways, by nucleation and by particle growth.
The particle size of a freshly formed precipitate is determined by which
way is faster.

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
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 Controlling Particle Size
Experimental variables that minimize supersaturation and thus lead to
crystalline precipitates include:
elevated temperatures to increase the solubility of the precipitate
(S in Equation),
dilute solutions (to minimize Q), and
slow addition of the precipitating agent with good stirring.
The last two measures also minimize the concentration of the
solute (Q) at any given instant.
 Larger particles can also be obtained by pH control, provided the
solubility of the precipitate depends on pH.
 See example in p317

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 Colloidal Precipitates

Individual colloidal particles are so small that they are not retained by
ordinary filters.
Coagulation of Colloids the individual particles of most colloids to
give a filterable, amorphous mass that will settle out of solution.
Coagulation can be hastened )‫ (يُ ْس ِرع‬by heating, stirring, and adding
an electrolyte to the medium.
Colloidal suspensions are stable because all the particles present are
either positively or negatively charged. This charge results from
cations or anions that are bound to the surface of the particles. The
process by which ions are retained on the surface of a solid is known
as adsorption. We can readily demonstrate that colloidal particles are
charged by observing their migration when placed in an electrical
field.
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• Effect of AgNO3 and electrolyte concentration on the thickness of the double layer
surrounding a colloidal AgCl particle in a solution containing excessAgNO3.
• The effective charge (Q) can be thought of as a measure of the repulsive force that
the particle exerts on like particles in the solution. Catalyst
 Peptization of Colloids
Peptization refers to 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.
• Practical Treatment of Colloidal Precipitates
Colloids are best precipitated from hot, stirred solutions containing sufficient
electrolyte to ensure coagulation. The filterability of a coagulated colloid frequently
improves if it is allowed to stand for an hour or more in contact with the hot solution
from which it was formed. During this process, which is known as digestion, weakly
bound water appears to be lost from the precipitate; the result is a denser mass that is
easier to filter. Catalyst
 Crystalline Precipitates

• Crystalline precipitates are generally more easily filtered and

purified than coagulated colloids. In addition, the size of individual
crystalline particles, and thus their filterability, can be controlled to
a degree.
• The particle size of crystalline solids can often be improved
significantly by minimizing Q, maximizing S, or both in Equation.
Minimization of Q is generally accomplished by using dilute
solution and adding the precipitating from hot solution or by
adjusting the pH of the precipitation medium.
• Digestion of crystalline precipitates (without stirring) for some time
after formation frequently yields a purer, more filterable product.
The improvement in filterability results from the dissolution and
recrystallization.

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 Coprecipitation
Coprecipitation is the phenomenon in which soluble compounds are
removed from solution during precipitate formation.
There are four types of coprecipitation:
i) surface adsorption
ii) mixed-crystal formation
iii) occlusion
iv) mechanical entrapment
• Surface adsorption and mixed crystal formation are equilibrium
processes, whereas
• occlusion and mechanical entrapment arise from the kinetics of
crystal growth.

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 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.
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.

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 Minimizing Adsorbed Impurities on Colloids
The purity of many coagulated colloids is improved by digestion.
During this process, water is expelled from the solid to give a denser
mass that has a smaller specific surface area for adsorption.
Washing a coagulate colloid with a solution containing a volatile
electrolyte may also be helpful because any nonvolatile electrolyte
added earlier to cause coagulation is displace by the volatile species.
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. Exchange occurs, however between existing
counter ions and ions in the wash liquid.

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Reprecipitation

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

reprecipitation, or double precipitation.
• Here, the filtered solid is redissolved and reprecipitated. The first
precipitate ordinarily 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.
• Reprecipitation adds substantially to the time required for an
analysis.

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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%. Furthermore, the
two salts must belong to the same crystal class. For example,
MgKPO4, 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.

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 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.
• Mechanical entrapment occurs when crystals lie close together
during growth. Here, several crystals grow together and in so doing
trap a portion of the solution in a tiny pocket.
• Both occlusion and mechanical entrapment are at a minimum when
the rate of precipitate formation is low, that is, under conditions of
low supersaturation. Digestion is often remarkably helpful in
reducing these types of copreipitation. The rapid solution and
reprecipitation that goes on at the elevated temperature of digestion
opens up the pockets and allows the impurities to escape into the
solution.

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 Precipitation from Homogeneous Solution

Precipitation from homogeneous solution is a technique in which a

precipitating agent is generated in a solution of the analyte by a slow
chemical reaction.
Local reagent excesses do not occur because the precipitating agent
appears gradually and homogeneously throughout the solution and
reacts immediately with the analyte. As a result, the relative
supersaturation is kept low during the entire precipitation. 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.

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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.
• The temperature required to produce a suitable weighing form
varies from precipitate to precipitate.

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 Chapter 13
Titrimetric Methods
Titrimetric methods include a large and powerful group of quantitative
procedures based on measuring the amount of a reagent of known
concentration that is consumed by an analyte.
Volumetric titrimetry involves measuring the volume of a solution of
known concentration that is needed to react essentially completely
with the analyte.
Gravimetric titrimetry differs only in that the mass of the reagent is
measured instead of its volume.
In coulometric titrimetry, the ‘reagent’, is a constant direct electrical
current of known magnitude that consumes the analyte.

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 Defining Some Terms
A standard solution (or a standard titrant) is
a reagent of known concentration that is used
to carry out a titrimetric analysis.
A titration is performed by adding a standard
solution from a buret or other liquid-
dispensing device to a solution of the analyte
until the reaction between the two is judged
complete. The volume of reagent needed to
complete the titration is determined from the
difference between the initial and final
volume readings.
The equivalence point in a titration is
reached when the amount of added titrant is
chemically equivalent to the amount of
analyte in the sample.
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 Equivalence Points and End Points
• The equivalence point of a titration cannot be determined
experimentally. Instead, we can only estimate its position by
observing some physical change associated with the condition of
equivalence. This change is called the end point for the titration.
• Every effort is made to ensure that any volume or mass difference
between the equivalence point and the end point is small. Such
differences do exist, however, as a result of inadequacies in the
physical changes and in our ability to observe them.
• The difference in volume or mass between the equivalence point
and the end point is the titration error.
• Indicators are often added to the analyte solution to give an
observable physical change (the end point) at or near the
equivalence point. Large changes in the relative concentration of
analyte or titrant occur in the equivalence-point region. These
concentration changes cause the indicator to change in appearance.
Typical indicator changes include the appearance or disappearance
of a color, a change in color, or the appearance or disappearance of
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turbidity.
 Primary Standards
A primary standard is a highly purified compound that serves as a
reference material in all volumetric and mass titrimetric methods. The
accuracy of a method is critically dependent on the properties of this
compound. Important requirements for a primary standard are:
1. High purity
2. Atmospheric stability
3. Absence of hydrate water so that the composition of the solid does
not change with variation in relative humidity
4. Ready availability at modest cost
5. Reasonable solubility in the titration medium
6. Reasonably large molar mass so that the relative error associated
with weighing the standard is minimized.

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 Desirable Properties of standard Solutions
The ideal standard solution for a titrimetric method will:
1. Be sufficiently stable so that it is only necessary to determine its
concentration once.
2. React rapidly with the analyte so that the time required between
additions of reagent is minimized.
3. React completely with the analyte so that satisfactory end points
are realized.
4. Undergo a selective reaction with the analyte that can be
described by a balanced equation.

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 Establishing the Concentration of Standard solutions
The accuracy of a titrimetric method can be no better than the
accuracy of the concentration of the standard solution used in the
titration.
Two basic methods are used to establish the concentration of such
solutions. The first is the direct method in which a carefully weighed
quantity of a primary standard is dissolved in a suitable solvent and
diluted to a known volume in a volumetric flask. The second is by
standardization in which the titrant to be standardized is use to titrate
(1) a weighed quantity of a primary standard, (2) a weighed quantity
of a secondary standard, or (3) a measured volume of another standard
solution.

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 Expressing the Concentration of Standard Solutions

The concentrations of standard solutions are generally expressed

in units of either molarity c or normality cN. The first gives the
number of moles of reagent contained in one liter of solution, and
the second gives the number of equivalents of reagent in the same
volume.

M = moles/L
N = equivalents/L

Examples: 1-3

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 Some Useful algebraic Relationships
Most volumetric calculations are based on two pairs of
fundamental equations that are derived from definitions of
millimole, mole, and molar concentration. For the chemical
species A, we may write
mass A (g)
amount A (mol) =
molar mass A (g / mol)
mass A (g)
amount A (mmol) =
millimolar mass A (g / mmol)

We may derive a second pair from the definition of molar

concentration. That is,
 mol 
amount A (mol) = volume (L)  concentration A  
 L 
 mmol 
amount A (mmol) = volume (mL)  concentration A  
 mL 
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 Treating Titration Data

• Calculating Molaritles from Standardization on Data

• Calculating the Quantity of Analyte from Titration Data

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Examples: 4-9
 GRAVIMETRIC TITRIMETRY
• The mass of titrant is measured rather than the volume.
– Balance and a weighable solution dispenser are substituted for a
buret and its markings.

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 TITRATION CURVES

An end point is an observable physical change that occurs near the

equivalence point of a titration.
The two most widely used end points involve
1. changes in color due to the reagent, the analyte, or an
indicator and
2. a change in potential of an electrode that responds to the
concentration of the reagent or the analyte.
To understand the detection of end points and the sources of titration
errors, we will construct titration curves for the system under
consideration.
Titration curves consist of a plot of reagent volume on the horizontal
axis and some function of the analyte or reagent concentration on the
vertical axis.
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 Types of Titration Curves
• Sigmoidal curve, in which the p-
function of analyte (or sometimes the
reagent) is plotted as a function of
reagent volume.
• Linear segment curve, measurements
are made on both sides of, but well
away from, the equivalence point.
– Measurements near equivalence are
avoided.
– In this type of curve, the vertical axis
represents an instrument reading that is
directly proportional to the concentration
of the analyte or the reagent.

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Concentration Changes during Titrations

Ag+ + SCN- → AgSCN(s)

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 PRECIPITATION TITRIMETRY
• is based on reactions that yield ionic compounds
of limited solubility.
• Because of the slow rate of formation of most
precipitates, however, there are only a few
precipitating agents that can be used in titrimetry.
– Most widely used and most important precipitating
reagent is silver nitrate. It is used for halides, the
halide-like anions (SCN-, CN-, CNO-), mercaptans,
fatty acids, and several divalent and trivalent inorganic
anions. (Argentometric methods)

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 Precipitation Titration Curves Involving Silver Ion
• The most common method of determining the halide ion
concentration of aqueous solutions is titration with a standard
solution of silver nitrate.
• Product is solid silver halide.
• A titration curve for this method usually consists of a plot of pAg
versus the volume of silver nitrate added.
• To construct titration curves, three type of calculations are required,
each of which corresponds to a distinct stage in the reaction:
1. preequivalence,
2. Equivalence
3. postequivalence

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 The Effect of Concentration on Titration Curves

For the more dilute chloride solution,

the change in pAg in the equivalence-
point region would be too small to be
detected precisely with a visual
indicator.

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The Effect of Reaction Completeness on Titration Curves

Clearly, the change in pAg at the equivalence

point becomes greater as the solubility
products become smaller, that is, as the
reaction between the analyte and silver nitrate
becomes more complete.
By careful choice of indicator -one that changes
color in the region of pAg from 4 to 6- titration of
chloride ion should be possible with a minimal
titration error.
Note that ions forming precipitates with Ksp
much larger than ~10-10 do not yield
satisfactory end points.
*You can derive a useful relationship for silver
chloride,
-log Ksp = -log([Ag+][Cl-]
= -log[Ag+] - log[Cl-]
pKsp = pAg + pCI
= -log(1.82 X 10-10) Catalyst
9.74 = pAg + pCI
 Titration Curves for Mixtures of Anions
• The methods developed in the previous section for deriving titration
curves can be extended to mixtures that form precipitates of
different solubilities.
• Silver chloride has greater Ksp than silver iodide
 AgCl does not begin to precipitate until well into the titration.

• How much iodide is precipitated before appreciable amounts of

silver chloride form.

• So for all practical purposes, AgCl forms only after 25.00 mL of titrant have been
added in this titration. At this point, the chloride ion concentration is
approximately
Substituting into the previous equation yields
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 Indicators for Argentometric Titrations
1. chemical, Three chemical indicators, consists of a color change or,
occasionally, the appearance or disappearance of turbidity in the solution being
titrated.
• The requirements for an indicator for a precipitation titration are that
1. the color change should occur over a limited range in p-function of the
reagent or the analyte
2. the color change should take place within the steep portion of the
titration curve for the analyte.
The titration of iodide with any indicator providing a signal in the pAg range of about 4.0 to
12.0 should give a satisfactory end point. In contrast, the end-point signal for the reaction of
chloride ions would be limited to a pAg of about 4.0 to 6.0.
2. potentiometric, end points are obtained by measuring the potential between
a silver electrode and a reference electrode whose potential is constant and
independent of the added reagent. (Figures 13-3, 13-4, and 13-5)
3. amperometric, end point, the current generated between a pair of silver
microelectrodes in the solution of the analyte is measured and plotted as a
function of reagent volume.

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Chemical indecators

1. Chromate Ion; The Mohr Method

Sodium chromate can serve as an indicator for
the Argentometric determination of chloride, bromide,
and cyanide ions by reacting with silver ion to form a
brick-red silver chromate (Ag2CrO4) precipitate in the
equivalence-point region.

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2. Adsorption Indicators: The Fajans Method
An adsorption indicator is an organic compound that tends to be
adsorbed onto the surface of the solid in a precipitation titration.
Ideally, the adsorption (or desorption) occurs near the equivalence
point and results not only in a color change but also in a transfer
of color from the solution to the solid (or the reverse).e.g.,
Fluorescein
The fluoresceinate ion forms an intensely red silver salt. Whenever this dye is used
as an indicator, however, its concentration is never large enough to precipitate as
silver fluoresceinate.
In the early stages of the titration of chloride ion with silver nitrate, the colloidal
silver chloride particles are –ve charged because of adsorption of excess chloride
ions. The dye anions are repelled from this surface by electrostatic repulsion and
impart a yellow-green color to the solution. Beyond the equivalence point, however,
the silver chloride particles strongly adsorb silver ions and thereby acquire a +ve
charge. Fluoresceinate anions are now attracted into the counter-ion layer that
surrounds each colloidal silver chloride particle. The net result is the appearance of
the red color of silver fluoresceinate in the surface layer of the solution surrounding
the solid.
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3. Iron(lII) Ion; The Volhard Method
Silver ions are titrated with a standard solution of thiocyanate ion:

lron(III) serves as the indicator. The solution turns red with the first slight excess of
thiocyanate ion:

The titration must be carried out in acidic solution to prevent precipitation of iron(III) as the
hydrated oxide.

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Applications of Standard Silver Nitrate Solutions

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