CHAPTER 6

CONTINUE...
GRAVIMETRIC
ANALYSIS
JAMIL MOHAMED SAPARI

Faculty of Applied Sciences, Kuala Pilah Campus,

UiTM Cawangan Negeri Sembilan

STEPS INVOLVED IN GRAVIMETRIC ANALYSIS

1. Preparation
of the sample 6. Drying or
7. Weighing
Igniting

2. Precipitation 5. Washing 8. Calculation

3. Digestion 4. Filtration
 STEP 2. Precipitation
A precipitation reaction refers to the process/formation of an
insoluble salt (solid forms) when two solutions containing soluble
salts are combined. The insoluble salt that falls out of solution is
known as the precipitate.

Precipitate
slightly solublesubstance /
insoluble ionic solid with a
known composition or it
can be converted to one of
known composition.
Characteristics of precipitate:
i. Readily filtered and purified.
ii. Low solubility, preventing losses of the
analyte during filtration and washing.
iii. Stable/Unreactive with constituents of
atmosphere.
iv. Known chemical composition after drying or
ignition.
FORMATION OF PRECIPITATE
Precipitation

Supersaturation

Analyte +
Precipitating Agent
PRECIPITATING AGENT
• Substance that effects the formation of suspension in solution, that react specifically or
selectively with the analyte to form a precipitate.
✓ Precipitating agent is a causative substance that effect the formation of suspension in
solution
Or the one that causes the formation of a precipitate
Two types of precipitating agents:
 Organic precipitants
 Inorganic precipitants
 Readily dissolved in the
solution medium

A number of organic reagents yield Selective, only produce the

precipitates with metal ions which desired precipitate. Precipitant
are coarse and bulky and therefore should be specific i.e. it should
easy to handle for gravimetric give a precipitate with one
work. particular ion

organic precipitants have high

molecular weights and yield a
relatively large amount of the
precipitate with a small amount of the
metal ion (analyte).
The cation, its
precipitating
agent and the
precipitation
reactions are
given in tabular
form as follows:
Precipitation Reactions of some Anions
 Types
of Precipitant,
Precipitate Formed
& Precipitate
Weighed
 Types of precipitates
(i) Crystalline (small number of large particles)

• Large size(>10-4 cm ).
• Settle spontaneously thus easily filtered and purified.
•A granular precipitate is very desirable in gravimetric analysis,
because it presents a relatively small surface area and is thus
less liable to contamination, as well as being easier to filter than
a gelatinous precipitate.
• Precipitates made up of large particles are desirable in
gravimetric work because large particles are easy to filter and
wash free of impurities.
• The precipitate form should have low solubility in the solution.
Crystalline precipitate
 (ii) Colloidal suspension
• Colloidal particles are tiny particles (powdery) and have
diameters from 10-7 cm to 10-4 cm.
• Will not settle and are not easily filtered.

*Crystalline precipitate settle rapidly, where as colloidal precipitate

remain suspended in solution
 Size of particles
• The particle size obtained depends on:
Relative SuperSaturation (RSS) = Q – S
S
where Q = [solute] at any instant
S = [solute] equilibrium

High (large) RSS

• concentrated solution
• nucleation process wins , colloidal precipitates formed
Low (small ) RSS
• dilute solution
• particle growth wins ,crystalline solid formed
 Nucleation
• The process of forming a nucleus.
• the initial process that occurs in the formation of a crystal from a
solution,
• in which a small number of ions, atoms, or molecules become arranged
in a pattern characteristic of a crystalline solid, forming a site upon
which additional particles are deposited as the crystal grows.

Particle growth
 New phase increase in size, and consists in the addition of new atoms,
ions, or polymer strings into the characteristic arrangement of a
crystalline
 The action of crystal growth yields a crystalline solid
whose atoms or molecules are typically close packed, with fixed
positions in space relative to each other.
Mechanism of precipitation
 Precipitate

Spontaneous

Particle growth

Nucleation
Mechanism of precipitation
(cont.)
 Nucleation sites
✓ Rapid cooling causes many nucleation sites, while
✓ Slow cooling yields a few crystals
✓ Thus influenced the structures of precipitate:

i. Many nucleation sites–fine (small-grain) structure = colloidal suspension

ii. Few nucleation sites, many particle growth–coarse (large-grain) structure = crystalline ppt
Ways to favour the formation of larger particles of precipitate:

i. Precipitate from dilute solution

ii. Add precipitating reagent slowly and stir effectively

iii. lowering the temperature slowly

iv. Precipitate at a low pH

v. Precipitate from the hot solution

Precipitation process
Properties of good precipitates
Sufficiently insoluble (low solubility) to avoid loss
during washing.

Consist of large crystals so that they are easily filtered

and washes free of impurities

Stable, do not easily react with the constituents of the

atmosphere.

Has known chemical composition after it is dried or

ignited.