Chapter 12:

Gravimetric Methods of Analysis

1/35
 Gravimetric methods: The quantitative methods that are based
on determining the mass of a pure compound to which the
analyte is chemically related.

• 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 that can be weighed.

• Electrogravimetry: The analyte is separated by deposition on

an electrode by an electrical current.

2/35
12A Precipitation gravimetry
 The analyte is converted to a sparingly soluble precipitate that is
then filtered, washed free of impurities and converted to a
product of known composition by suitable heat treatment and
weighed.
Ex. for determining the [Ca2+] in water:

2NH 3(aq) + H 2 C2 O 4(aq) → 2NH 4(aq)

+ 2-
+ C2 O 4(aq)
Ca 2+ + C2 O 2-4(aq) → CaC2 O 4(s)
filtered, dried, ignited
∆
CaC2 O 4(s)  → CaO(s) + CO(g) + CO 2(g)

After cooling, the precipitate is weighed and the mass is

determined.

3/35
12A-1 Properties of Precipitates and Precipitating Reagents

 A gravimetric precipitating agent should react specifically or at least selectively

with the analyte and give precipitates that is:
1. Enough particle size for retaining on filter paper
2. High purity (free of contaminants)
3. Low solubility that no significant loss of the analyte occurs during filtration
and washing
4. Unreactive with air (stable)
5. Known stoichimetric composition after it is dried or, if necessary, ignited

* Specific reagents: react only with a single chemical species.

Selective reagents: react with a limited number of species.

4/35
12A-2 Particle Size and Filterability of Precipitates
 Characteristics of Ion, colloid and particle
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 difficult to filter.
 At the other extreme are particles with dimensions on the order of tenths of a
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 easily
filtered.

Name Diameter Characteristics

Ion ~10-8 cm (A°) Dissolved
Colloid 10-7~10-4 cm (nm-µm) Suspended
Crystalline >10-4cm (µm) Settled from solution (filterable)
Precipitates consisting of large particles are generally desirable for gravimetric
work because these particles are easy to filter and wash free of impurities.
5/35
Factors That Determine the Particle Size 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, and the
* 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 relative supersaturation, where
Q -S
RSS =
S
Q: the concentration of the solute at any instant
S: the concentration solute at equilibrium Von Weimarn equation, 1925

6/35
 Relative supersaturation (RSS)
Q -S
- A supersaturated solution is an unstable RSS =
solution that contains a higher solute S
concentration than a saturated solution. As excess
solute precipitates with time, supersaturation
decreases to zero.

-Generally, precipitation reactions are slow so that, even when

a precipitating reagent is added drop by drop to a solution of
an analyte, some supersaturation is likely.
- 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. Thus, when (Q - S)/S is large, the precipitate tends
to be colloidal, and when (Q - S)/S is small, a crystalline solid is
more likely.

RSS Process Result

Large Nucleation dominate Smaller particles ( colloidal)
Small Particle growth dominate Larger Particle (Crystalline)
7/35
 Mechanism of Precipitate Formation
 Nucleation and Particle growth
• Nucleation: The initial formation process in which a minimum number of
atoms, ions, or molecules join together to give a stable solid.
• Often, these nuclei form on the surface of suspended solid contaminants,
such as dust particles
• Particle growth: The subsequent growth after nucleation.

 If nucleation predominates, a precipitate containing a large

number of small particles results, and
 if growth predominates, a smaller number of larger particles
is produced.
RSS Process Result
Large Nucleation dominate Smaller particles ( colloidal)
Small Particle growth dominate Larger Particle (Crystalline)
8/35
Experimental Control of Particle Size
(the lower RSS value the larger particles)
 Increase S:
 Heating to increase solubility
 pH adjustment (If the solubility of the precipitate
depends on pH)
 Adding complexing agent
 Decrease Q:
 Using dilute precipitating solution
 Adding precipitating agent slowly and stirring
 Using homogeneous precipitation technique
9/35
12A-3 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.
(When liquid starts to thicken and become solid, it coagulates)
( agglomeration: a large group of many different things collected or brought together)

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 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.
10/35
– an electric double layer:
•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.
• These layers 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 12.1 A colloidal silver chloride (AgCl) suspended in a solution of excess AgNO3

Adsorption: A process in which a substance (gas, liquid, or solid) is held on the surface of a solid.
Absorption: A process in which a substance within the pores of a solid.

Figure 12-1 p284

The effective charge on two silver chloride particles
In Fig.12(a), The upper curve
represents a particle in a solution that
contains a reasonably large excess of
silver nitrate, and the lower curve
depicts a particle in a solution that has a
much lower silver nitrate content.
The effective charge can be thought
as a measure of the repulsive force
that the particle exerts on like
particles in the solution.
Note that the effective charge falls off
rapidly as the distance from the surface
increases, and it approaches zero at the
points d1 or d2.
Figure 12-2 Effect of AgNO3 and electrolyte concentration
on the thickness of double layer surrounding a colloidal
AgCl particle in a solution containing excess AgNO3.

12/35
  Coagulation of Colloids
* The upper portion of Figure 12-3 depicts two silver
chloride particles and their counter- ion layers as
they approach each other in the concentrated silver
nitrate just considered. Note that the effective
charge on the particles prevents them from
approaching one another more closely than about
2d1—a distance that is too great for coagulation to
occur.
* As shown in the lower part of Figure 12-3, in the
more dilute silver nitrate solution, the two particles
can approach within 2d2 of one another.
Ultimately, as the concentration of silver nitrate is
further decreased, the distance between particles
becomes small enough for the forces of
Figure 12-3 The electrical double agglomeration to take effect
layer of a colloid consists of a layer
of charge adsorbed on the surface of And a coagulated precipitate
the particle (the primary adsorption to appear.
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
A coagulated colloid
counter-ion layer, thereby increasing
the chances for coagulation. 13/35
Coagulation of a colloidal suspension can often be brought about by a short period of
heating, particularly if accompanied by stirring.
 Heating decreases the number of adsorbed ions and thus the thickness, of the
double layer. The particles may also gain enough kinetic energy at the higher
temperature to overcome the barrier to close approach imposed by the double
layer.
 An even more effective way to
coagulate a colloid is to increase the
electrolyte concentration of the
solution. If we add a suitable ionic
compound to a colloidal suspension,
the concentration of counter-ions
increases in the vicinity of each
particle. As a result, the volume of
solution that contains sufficient
counter-ions to balance the charge
of the primary adsorption layer
decreases. The net effect of adding
an electrolyte is thus a shrinkage of
the counter-ion layer, as shown in
Figure 12-2b. The particles can then
approach one another more closely
Figure 12-2 Effect of AgNO3 and electrolyte concentration and agglomerate.
on the thickness of double layer surrounding a colloidal AgCl
particle in a solution containing excess AgNO3. 14/35
  Peptization of Colloids
Peptization: The process by which a coagulated colloid reverts to its original
dispersed colloidal suspension state..
(When a coagulated colloid is washed, some of the electrolyte responsible
for its coagulation is removed, therefore, the repulsive forces as well as the
original colloidal state are reestablished.)
Solution: Use of Volatile electrolyte as washing solution, e.g., HNO3, NH4NO3, to
avoid peptization.
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 often 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.

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.

15/35
12A-4 Crystalline Precipitates
 Crystalline precipitates are generally more easily filtered and purified than are
coagulated colloids.
 Particle size of crystalline solids can often be improved significantly by
 minimizing Q (by using dilute solutions, and adding the precipitating reagent
slowly, with good mixing) or
 maximizing S (precipitating from hot solution or by adjusting the pH), or both.
 Digestion improves the purity and filterability of both colloidal and crystalline
precipitates.
 The improvement in filterability undoubtedly results from the dissolution and
recrystallization that occur continuously and at an enhanced rate at elevated
temperatures.
 Recrystallization apparently results in bridging between adjacent particles, a
process that yields larger and more easily filtered crystalline aggregates. This
view is supported by the observation that little improvement in filtering
characteristics occurs if the mixture is stirred during digestion.

16/35
12A-5 Coprecipitation
Coprecipitation:
 A process in which normally soluble compounds are carried out of
solution by a precipitate. It may resulted in impurities within the desired
precipitates.
 Coprecipitated impurities may cause either negative or positive errors.

 There are four types of coprecipitation:

surface adsorption,

 mixed-crystal formation,

occlusion, and

mechanical entrapment.

17/35
Surface Adsorption:
 The impurity is chemically or physically adsorbed onto the surface of precipitates
 Adsorption is the major source of contamination in coagulated colloids but of no
significance in crystalline precipitates.
 Minimizing Adsorbed Impurities on Colloids
 Washing a coagulated colloid with a solution containing a volatile electrolyte
 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.

18/35
 Mixed-Crystal Formation:
 A type of coprecipitation in which a contaminant ion replaces an ion
in the lattice of a crystal.
Ex. SrSO4 in BaSO4
MgKPO4 in MgNH4PO4
MnS in CdS
 Mixed-crystal formation may occur
in both colloidal and crystalline precipitates

 Problem solving:
• Change to another more selective precipitating agent
• Reprecipitation

19/35
  Occlusion:
 A type of co-precipitation in which a compound (foreign ions in the counter-ion layer )
is physically trapped within a precipitate during rapid precipitate formation.
 Problem solving: Digestion

Digestion: The process which has a waiting time

to achieve desired outcome.
(The solubility–precipitation is in a dynamic
equilibrium, digestion ensures the occluded
material is eventually exposed to the supernatant
solution.)

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

 Problem solving: Digestion

Mixed-crystal formation may occur in both colloidal and

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

20/35
 12A-6 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 larger in size

Example 1: Urea, for generating OH– as precipitant (Al(III), Fe(III))

CO(NH2)2(aq) + 3 H2O(l)  CO2(g) + 2 NH4+(aq) + 2 OH–(aq)
* Generation rate can be controlled by temperature
Example 2: For generating SO42– as precipitant
NH2SO3H(aq) + 2H2O(l)  NH4+(aq) + H3O+(aq) + SO42–(aq)
* Generation rate can be controlled by pH

21/35
 12A-7 Drying and Ignition of Precipitates
 A gravimetric precipitate is heated until its mass becomes constant.
 Heating removes the solvent and any volatile species carried down with the ppt.
 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 dehydrate a precipitate

completely may be as low as 100°C or as high as 1000°C

 Moisture is completely removed from silver chloride at

temperatures higher than 110°C, but dehydration of
aluminum oxide is not complete until a temperature
greater than 1000°C is achieved.

 The thermal curve for calcium oxalate is considerably

more complex than the others

 Recording thermal decomposition curves is called

thermogravimetric analysis, and the mass versus
temperature curves are termed thermograms.

Figure 12-6 Effect of temperature

on precipitate mass. 22/35
12B Calculation of results from gravimetric data

23/35
24/35
25/35
 Gravimetric factor: A gravimetric factor is an algebraic
expression that converts grams of a compound into grams of
a single element. It is the ratio of the formula weight (FW) of
the substance being sought to that of the substance weighed.
Example 1. Fe is sought, Fe2O3 is weighed:

Example 2. Fe3O4 is sought, Fe2O3 is weighed:

26/35
27/35
28/35
12C Applications of gravimetric methods
12C -1 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.

29/35
12C-2 Reducing Agents
(convert an analyte to its elemental form form for weighing)

30/35
 12C-3 Organic Precipitating Agents
Some organic reagents react with metal ions then produce insoluble coordination cmpds.
 Reagents that form coordination compounds of this type are called chelating agents, and
their products are called chelates.
 Those metal chelates are relatively nonpolar and have low solubilities in water.
 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.

31/35
Magnesium complex with 8-hydroxyquinoline.

32/35
Nickel dimethylglyoxime is
spectacular in appearance.
As shown in color
plate 7, it has a beautiful
vivid red color.

33/35
sodium tetraphenylborate.

34/35
12C-4 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.
 Many of the reactions shown can also be used for volumetric and spectrophotometric
determinations.

35/35
12C-5 Volatilization Gravimetry
 The two most common: determining water and carbon dioxide.
 Water is quantitatively distilled from many materials by heating.
 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.
 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.
 determination of the sodium hydrogen carbonate content of antacid tablets

Figure 12-8 Apparatus for determining the sodium hydrogen carbonate content of antacid tablets
by a gravimetric volatilization procedure.

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

36/35
 12C-5 Volatilization Gravimetry

 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.

37/35
 Homework (Due 06/03/2018)
Chapter 12, Questions and Problems
12-1, 12-2, 12-4, 12-5, 12-7, 12-9-(a,c,e), 12-10, 12-12, 12-18, 12-20

12-22, 12-25, 12-29, 12-30, 12-33

End of Chapter 12

38/35