GRAVIMETRIC ANALYSIS

Chapter 6
At the end of the chapter, students should be able to:
 Explain the principle of Gravimetric analysis
 Identify types of gravimetric analysis
 Explain the steps involved in Gravimetric analysis
 Perform calculation on Gravimetric analysis
 Definition
Gravimetric Methods of Analysis
It is the quantitative determination of analyte concentration
through a process of precipitation of the analyte, isolation of
the precipitate, and weighing the isolated product.
Or
A method whereby the analytes or solutes are selectively
converted to an insoluble form (precipitate).
Criteria of gravimetric analysis

 Weighing process only.

 No standardization of solution.
 No calibration is needed, except for an accurate analytical
balance.
 In this method, the analyte is selectively converted to an insoluble
precipitate, which is then dried/ignited and later accurately
weighed
Concepts

1. Identify the insoluble form of the analyte

(soluble form insoluble form)
2. Separate the analyte from any constituents that may
interfere. (separate)
3. Wash the precipitate free of impurities and co-
precipitants. (dried)
4. Convert the precipitate to a reliable weighing form which
is stable. (weight)
Advantages

The advantages offered by gravimetric analysis are:

1) Accurate and precise (when using modern analytical
balances)
2) Possible sources of errors can be checked. Filtrates can
be tested for completeness of precipitation and precipitates
may be examined for the presence of impurities.
3) It is an absolute method. Direct measurement without any
form of calibration required.
4) Relatively inexpensive
5) Can be applied to macro (large scale) samples.
Disadvantages

• Required long experimental hours due to heating or

drying of the samples into stable and weighing form.
• Gravimetric analysis usually only provides for the
analysis of a single element, or a limited group of elements,
at a time.
• Gravimetric analysis is based only on the measurement of
mass.
6.2 Types of gravimetric analysis

a. Precipitation gravimetry
 the analyte is converted to an insoluble precipitate that is
filtered, washed free of impurities, and converted to a
product of known composition by suitable heat
treatment.
 This product is then weighed.
 Examples :
 Determination of the amount of calcium in water or milk.
 Determination of Fe content in Fe ore.
 b. Volatilization gravimetry
 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 weight of the product is
determined indirectly from the weight loss of
the sample.
Gravimetric analysis is applied in determination of:

1) Inorganic anions eg. SO4 2- , Cl- , etc.

2) Cations such as Fe2+ , etc
3) Neutral species in samples such as H2O, SO2 , CO2 , I2 ,
etc
4) Organic samples eg. Lactose in milk, cholesterol in
cereals.
a. Precipitation
gravimetry
STEPS
1. Preparation of the sample
2. Precipitation
3. Digestion
4. Filtration
5. Washing
6. Drying or igniting
7. Weighing
8. Calculation
Figure 1: Steps summary
Step 1. Preparation of the sample
🞂 Steps in preparing sample

2.Preliminary 3.pH of
1.Solid sample
separation to solution is
must be dissolved
separate adjusted to
in a suitable
interfering maintain low
solvent.
materials. solubility
Purposes of Solution Preparation

I. To ensure complete precipitation

II. To prevent co-precipitation of other ions that might be
present.
III. To maintain low solubility of the precipitate.
IV. To obtain the precipitate in a form suitable for filtration.
V. Proper adjustment of the solution condition may also
mask potential interferences.
Factors that must be considered when
preparing the solution

🞂 Volume of the solution during precipitation.

🞂 Concentration range of the test substance.
🞂 The presence and concentrations of other constituents.
🞂 Temperature
🞂 pH
 STEP 2. Precipitation
Precipitation – is the process by which a solid phase forms
and is carried out of solution when the solubility product of
a chemical species is exceeded
• Precipitate – a slightly soluble substance 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

Analyte +
Precipitating Supersaturation Precipitation
Agent
Precipitating agent
 Substance that affects the formation of suspension in
solution, that reacts specifically or selectively with the
analyte to form a precipitate.

 Precipitating agent is a causative substance that affects

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
 Characteristic of precipitant/
precipitating agents

Readily dissolved in
the solution medium

Selective, only produce the

A number of organic reagents
desired precipitate.
yield precipitates with metal
Precipitant should be
ions which are coarse and
specific i.e. it should give a
bulky and therefore easy to
precipitate with one
handle for gravimetric 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 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
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. i.Precipitate from dilute solution

II. ii.Add precipitating reagent slowly and stir
effectively
III. iii.Precipitate from the hot solution
IV. iv.Precipitate at a low pH
V. lowering the temperature slowly
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.

 Impurities (contamination of precipitates)
 Impurities may form during precipitation-

co-precipitation
DIFFERENCES BETWEEN PRECIPITATION
AND CO-PRECIPITATION
CO-
PRECIPITATION PRECIPITATION

The process by
The process in
which a solid
which normally
phase forms and
soluble
is carried out of
compounds are
solution when
carried out of
the solubility
solution during
product of a
the formation of
chemical species
precipitate
is exceeded.
Contamination of precipitates
1. Coprecipitation of other ions occurs during the formation of
the target analyte precipitation :
 Coprecipitation throughout the body of the precipitate.
 foreign ions present during precipitation may be incorporated into
the crystal structure of the precipitate particles throughout their
growth

 Coprecipitation at the surface of the precipitate.

 the impurity is found on the surface of the precipitate and it occurs
especially with gelatinous precipitate.

2. Post-precipitation of other ions. This type of contamination

occurs after the formation of the precipitate.
Types of co-precipitation
a)Inclusions: impurities are randomly distributed throughout
the precipitate.
b)Occlusions : impurities are localized within the interior of
the precipitate
c)Surface adsorbates: impurities are localized on the
precipitate’s exterior or *cubic surface
d)Mechanical entrapment
How to reduce/remove the impurities?
 a) Inclusions : By re-precipitation
 After isolating the precipitate from its supernatant
solution, dissolve it by heating in a small portion of a
suitable solvent. Then allow the solution to cool,
reforming the precipitate.
 Repeat the process of reprecipitation until the inclusion’s
mass is insignificant.
 The filtered solid precipitate is redissolved and then
reformed from the new solution. Because the
concentration of impurity in the new solution is lower,
the second precipitate contains less co-precipitated
impurity.
 Continue…

🞂 (b) Occlusions and mechanical entrapment: By digestion

🞂 •Digestion–process maintaining the precipitate in equilibrium
with its supernatant solution for an extended time.
🞂 A process in which a precipitate is heated in the presence of the
solution from which it was formed (the mother liquor).
🞂 Digestion improves the purity and filterability of the precipitate.

🞂 •During digestion, the dynamic nature of the solubility–

precipitation equilibrium, in which the precipitate dissolves and
reforms, ensures that the occlusion is re-exposed to the
supernatant solution.

🞂 (c) Surface adsorbates : By decreasing the precipitate’s

available surface area
 STEP 3 Digestion
•A process in which a precipitate is heated (without stirring)
for 1 hour in the presence of the solution from which it was
formed (the mother liquor).

🞂 •Advantage–improves the purity and filterability of the

precipitate.
🞂 Digestion involves dissolution of small particles and re -
precipitation on larger ones causing the particles to grow
even larger
🞂 resulting in particle growth and better precipitate
characteristics. This process also known as Ostwald
ripening.
 Filtration & washing
STEP 4

🞂 •After precipitation has taken place, the precipitate must

be separated from the supernatant solution and other
constituents of the sample by filtration technique.
🞂 •Filtration using filter paper is used to collect all the
precipitate formed.
 🞂 Various grades of filter paper :
🞂 1.Filter paper grade No. 42 for FINE precipitates.
🞂 2.Filter paper grade No. 41 for COURSE OR
GELATINEOUS precipitates.
🞂 3.Filter paper grade No. 40 for MEDIUM SIZE OR
CRYSTALLINE precipitates.
A precipitate may be separated by filtering it through:
•Ashless Filter Paper –leave very little ash when it burnt.
•Sintered Glass –able to stand temperature up to 500 oC.
•Sintered Porcelain –able to stand temperature up to
1000oC.
 Washing
step 5
🞂 The object of washing the precipitate is to remove the impurities
contaminating the precipitate as completely as possible. In the
process of washing only surface impurities will be removed.

🞂 Washing and rinsing of the precipitate with appropriate

electrolyte is done to:
🞂 i. Insure quantitative transfer of the precipitate to the filter paper or
crucible.
🞂 ii.insure purity of the filtrate
🞂 iii.prevent the process known as peptization (The process whereby the
precipitate reverts back to a colloidal state and is lost).

🞂 Washing: One should be careful nor to use too much water since
part of the precipitate may be lost.
🞂 Some of the precipitates have a tendency to become
colloidal and passing through the filter paper. Such a
tendency is frequently observed with gelatinous or
flocculated precipitates.
🞂 How to do correct washing?
🞂 Washing is required because precipitating reagents is
usually added in excess.
🞂 Since the precipitate form is usually not 100 % insoluble,
therefore great care is taken during washing and do not
wash the precipitate too long.
🞂 The most important factor is how much washing solution is
needed or how many times you need to wash the precipitate
🞂 The best way is to wash the precipitate a few times NOT to
wash once with total same volume of washing
solution(better 3x10mL than 30mL once)
🞂 In a nut-shell the wash solution should have the
following characteristics.
🞂 i) it should not have any dissolution action upon the
precipitate but remove the foreign impurities easily,
🞂 ii)it should not form any volatile or insoluble product
with the precipitate,
🞂 iii) it should be easily volatile at the temperature of
drying of the precipitate, and
🞂 v) it should not contain any substance which is likely to
interfere with subsequent determinations in the filtrate.
🞂 In general, pure water is ideally used
 Step 6
Drying or ignition
🞂 Drying in oven
🞂 •After filtering, the gravimetric precipitate is heated until
its weight become constant.
🞂 •Purpose of drying –to remove water/solvent and any
volatile species carried down with the precipitate and to
remove the wash electrolyte.
🞂 •Drying (in oven) can be done by heating at 110oC to
120oC for 1 to 2 hours (for the precipitate which is in a
form suitable for weighing).
 🞂 Ignition in furnace
🞂 •Some precipitates must be ignited (in furnace) at higher
temperature (600-1200oC) to decompose the solid and
form a compound of stable and known composition.

🞂 E.g. CaC2O4 CaO (1100oC)

 Step 7 Cooling & weighing

🞂 After heating, the precipitate is cooled in a desiccators to

avoid weight gain due to re adsorption of atmospheric
water.
🞂 Desiccant –is a drying agent that has a high affinity for
water and water vapor.
🞂 E.g. desiccant : calcium sulfate, calcium chloride, silica,
magnesium perchlorate
🞂 The process of heating, cooling and weighing is repeated
until a constant weight is achieved or the difference
between two consecutive weighing is not more than
0.0002 g.
GRAVIMETRIC CALCULATIONS
🞂 The weighing form of the precipitate is weighed using
a sensitive analytical balance
🞂 In gravimetric analysis, the moles of analyte is a multiple
of the moles of precipitate formed (the moles of analyte
contained in each mole of precipitate).
🞂 The gravimetric factor (GF) is the appropriate ratio of
the formula weight of the analyte to that of the formula
weight of precipitate:

/
/
 GRAVIMETRIC FACTOR, GF

Weight of analyte = Gravimetric factor x weight of weighing form.

In gravimetric analysis, composition of the analyte
usually expressed in percent
3O4

Or GF= RAM Mn/1

RMM Mn3O4/ 3