CHAPTER 6

GRAVIMETRIC
ANALYSIS

Dr Mohd Zahari Abdullah @ Rafie

CHM 256 UiTM Pahang
COURSE OUTLINE
CHAPTER OUTLINE
 GRAVIMETRIC ANALYSIS
1.
PRIN
CIPL
◻ The technique in ESamount
which the of an analyte (the ion
being analyzed) in a sample can be determined by converting the
analyte to some product [change of chemical states of the
analyte], where MASS of product can be measured
◻ Based on the MEASUREMENT OF MASS
◻ Used analytical balance (instrument that yield highly accurate and
precise data)
◻ Most ACCURATE METHOD of chemical analysis
GRAVIMETRIC ANALYSIS
SUCCESSFUL
REQUIREMENT
 PROCEDURE
Selectively
Preliminary treatment convert the
(Preparation of the solution analyte

Precipitation of precipitates
Precipitate
form
(Insoluble
form)
Digestion

Filtration (Separate the precipitate) and

Washing

Drying or/and Igniting

Weighing

Calculation of the amount of the element or

radical to be determined.
GRAVIMETRIC ANALYSIS
APPLICATIONS
To
determine

Inorganic anions
such as SO 2-, Cl-
4
 GRAVIMETRIC ANALYSIS
ADVANTAGES &
DISADVANTAGES
+ -
1. No CALIBRATIONS needed
2. No STANDARDIZATION required
3. RESULTS is calculated directly
from the experimental data1. Gravimetric analysis REQUIRED
obtained LONG EXPERIMENTAL HOURS due
4. LESS MESSY compare to other to steps of heating or drying of the
samples to form stable and weighing
methods and the RESULT obtained
form of precipitate
is very ACCURATE because
required only an accurate analytical
balance

5. Can be applied to macro

(large scale) samples
GRAVIMETRIC
2.
ANALYSIS
TYPE
S OF
MET
HOD
 TYPES
OF
METH
OD
1. PRECIPITATION
METHOD
DEFINITION
◻The analyte is converted to a SPARINGLY SOLUBLE

PRECIPITATE that is filtered, wash free from impurities,

which converted to a product of STABLE and KNOWN
COMPOSITION by suitable heat treatment. This product is
then weighed.
 1. PRECIPITATION
METHOD
EXAMPLE:
DETERMINATION OF Cl- IN
AQUEOUS SOLUTION
Precipitate occurs in series of steps:

Sample solution

Solution of precipitating reagent added

to
Precipitate formed Precipitate

Eg: AgNO3 + NaCl →AgCl + NaNO3

 1. PRECIPITATION
PROCESS: METHOD
DETERMINATION OF Cl- IN AQUEOUS
SOLUTION
 TYPES
OF
METH
OD
2. VOLATILIZATION
METHOD

DEFINITION
◻The ANALYTE or its DECOMPOSITION product are

volatilized at 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.
ILIZAT
ION
METHO
D
PROCESS
 PROCEDUR
ES OR
STEPS OF
GRAVIMET
RIC
ANALYSIS
1. PRELIMINARY
TREATMENT
• Preliminary treatment is the PREPARATION OF THE
SOLUTION that containing sample.
• Need to eliminate interfering materials.

PURPOSE :
❖ Adjustment to the solution conditions before precipitation.
❖ To maintain LOW SOLUBILITY of the precipitate.
❖ To obtain SUITABLE PRECIPITATE form for filtration.
FACTORS to be considered
PRE-TR
EATME
NT
pH influence:
1.SOLUBILITY of
precipitate
2.INTERFERENCES
from any
substances
 pH
Influence the solubility of the precipitate

Example: Calcium oxalate precipitation

• Insoluble in basic medium • Soluble in acidic medium

 VOLUME OF SOLUTION DURING
PRECIPITATION
• Solution condition (volume) must be
adjusted to maintain low solubility of
precipitate

• Excess volume of solution during

precipitation leads to precipitate will be
coagulate
 TEMPERATURE

Increase the temperature

Increase the solubility of the precipitate

Precipitate will dissolved or coagulated & Difficult to

filter.

**choose the best and appropriate pH during sample

preparation
2. Forming Precipitation
Precipitation gravimetric is an analytical
technique that uses a precipitation reaction to
separate ions from a solution.
The chemical that is added to cause
the precipitation is called the precipitant or
precipitating agent.
❑ A granular precipitate is very desirable in gravimetric
analysis because it presents a relatively small surface
area and less liable to contamination. It is easier to
filter granular than a gelatinous precipitate

❑ Precipitates made up of large particles are

desirable in gravimetric work because are easy to filter
and can minimize contaminants.
❑ The precipitate form should have low solubility in
the solution
 Types of Precipitates
1. Crystalline:
1. Large size (> 10--4cm)
2. Settle spontaneously
3. Easily filtered and purified
4. Low RSS

2. Colloidal Suspension:
1. Tiny with diameters of 10--7 to 10--4cm
2. Will not settle
3. Not easy to filter
4. High RSS
RSS-residuals supersaturation
 The ideal precipitating agent should react with the
analyte to give precipitates with the characteristic
of:

1. Consist of large crystals that can easily be

filtered and free of contaminants.
2. Sufficiently insoluble so that amount of analyte
lost during filtration and washing will be really
low.
3. Stable. Unreactive with constituents
atmosphere.
 Precipitation:
•Large particles in granular form can be
achieved by:

a.Precipitate from dilute solution

b.Add precipitating reagent slowly, stir effectively
c.Precipitate from hot solution
d.Precipitate at low pH
e.Lowering the temperature slowly
f. Adding organic solvent that can mix with
water
 Precipitation
Process

1. Precipitating Reagent (Precipitants)

Chosen for the ability to be selective and to form
highly insoluble precipitates (easily filtered) and of
reproducible stoichiometry

There are two types of precipitants:

oOrganic precipitant
oInorganic precipitant
 Common Inorganic Precipitant
Precipitant Analyte Precipitate Precipitate Weighed
Formed
NH4OH Al Al(OH)3 Al2O3
Fe Fe(OH)3 Fe2O3
HCl Ag AgCl AgCl
AgNO3 Cl AgCl AgCl
NaSO4 Ba BaSO4 BaSO4
BaCl2 BaSO4 BaSO4
Nucleation: individual ions/atoms/molecules to form nuclei (small particles
come together to form colloid particles.livate (induced) by adding dust particles,
scratches on the vessel surfaces and seed crystals.
Rapid cooling: Many nucleation sites
Slow cooling: Yields a few site on

❖❖Nucleati
crystals

on
 3. DIGESTION OF PRECIPITATE
Digestion is a process where the precipitate is re-dissolved and
precipitated out of a cleaner solution.

This process helps produce larger crystals that are more easily
filtered from solution
▪ Small particles are not retained by the ordinary filter
Digestion improves the purity and filterability of the
precipitate.
Digestion usually done at elevated temperature to
speed the process of agglomeration and
coagulation.

Digestion process is a phenomenon when a small

precipitate(particles <1µm) which presence in the
solution is allowed to grow to form a larger
crystals(colloidal particles) when heated
Very small particles with a larger specific area have a higher
surface energy and a higher solubility compared to larger
colloidal particles (1 – 100 micrometer)

The small particles tend to dissolve and reprecipitate on the

surface of the larger crystals

The small particles are coagulated of agglomerated using a

coagulant to give a filterable, amorphous mass that will settle out
of the solution

Small particles can be often coagulated by heating, string and

adding of electrolyte.
❑ Peptization is the process by which a coagulated
colloid reverts to its original dispersed state.

When a coagulated colloid is washed, some of them is

leached from the dispersion medium in contact with
the solid particles.

How to overcome? Wash with a solution containing an

electrolyte that volatilizes when the precipitates is
dried or ignited.

For the example the AgCl washed using nitric acid in

determination of AgCl.
 CONTAMINANT OF PRECIPITATES

Coprecipitation is a process in which soluble

compounds are removed from solution during
precipitate formation.

There are 4 types of coprecipitation:

1. Occlusion and Inclusion
2. Surface Adsorption
3. Isomorphous Replacement
4. Postprecipitation
 1. OCCLUSION & INCLUSION Occlusion
Inclusion
&

OCCLUSION INCLUSION impurities are

difficult to
Trapping of impurities Trapping of remove.
Digestion may
within the crystal. impurities help some but
this is not
Example : within the
completely
effective.
Water may trapped in Purification by
crystal dissolving &
pockets when silver reprecipitating
nitrate crystals are LATTICE. may be
Example : helpful
formed
Impurities K+ in NH4MgPO4
Inclusions, Occlusions, and Surface Adsorbates

Inclusion occurs when the impurity occupies a lattice site in the crystal
structure of the carrier.

Occlusion occurs when an adsorbed impurity gets physically trapped

inside the crystal as it grows
2. SURFACE ADSORPTION
High relative
supersaturation

Increase
nucleation
Many small crystals
formed
More surface area

More surface
adsorption

More impurities formed

Surface Adsorption
 Take one chalk & imagine that is large crystal. It have 4 surface area
Imagine this is a large crystal
It have less surface area

Imagine --break that chalk piece ,now the large crystal are become
small crystals. It have 8 surface area.

Supersaturation increase nucleation occur,precipitate will

become small crystal & convert into colloidal form &
increase the surface area
Story It have more surface area – chance to bind more
imagination impurities
to
understand
the concept

Surface area – 8
nos
Summary:
Methods to prevent and eliminate
Co--precipitation
Co-precipitation Method to minimize/
eliminate
• Digestion
• Washing with solution
Surface adsorption containing a volatile
electrolyte
• Reprecipitation
Occlusion/ Mechanical • Digestion
Entrapment • Use of dilute solution
• Slow addition of reagent
 4.Filtration and Washing

After precipitation has taken place, the

precipitate must be separated from the
supernatant solution(which normally
contains excess common ion) and other
constituents of the sample by filtration o
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 coarse or
gelatinous precipitates.
3. Filter paper grade No. 40 for medium size OR
crystalline precipitates.
❑ 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.
Many precipitates cannot be washed with pure water
because peptization occurs.
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)
 The characteristic of the washing liquid:

1.No solvent action on precipitate.

2.Dissolve impurities easily.
3.Easily evaporates at drying temperature of
precipitate.
4.Contains no substance that will interfere with
subsequent determinations of the filtrate.
5.In general, pure water is ideally used.
 EXAMPLE
A precipitate form of an analyte contain 1.0 g
contaminant. Suppose after washing the
precipitate with 50.0 mL of washing solution, the
precipitate hold 1.0 mL of the washing solution.
Compare how much contaminant remain in the
precipitate after one washing (50 mL) or 5 times
(10 ml each washing) ?
Method A
If we used 1 x 50 mL washing solution.
Amount of contaminant remain in the precipitate
= 1/50 x 1.0 = 0.02 g
Method B

If we use 10 mL x 5 times:
After first washing
= 1/10 x 1.0 = 0.1 g

After second washing and so on…….

= 1/10 x 0.1 = 0.01 g

Therefore after five washing

= 1/105 x 1.0 g
= 0.00001 g.
 5.Drying and ignition
❑ After filtering, the gravimetric precipitate is heated
until its weight become constant.
Drying usually be done by heating at 110°C to 120°C
for 1 to 2 hours.
Heating removes the solvent, adsorbed electrolytes
and any volatile species that is carried down with
the precipitate.
Some precipitates must be ignited to decompose the
solid and form a compound of stable and known
composition.
This new compound is often called the WEIGHING
FORM.
 6. Weighing the dried precipitate

❑ The weighing form of the precipitate is weighed using a

sensitive analytical balance
❑Two Methods to calculate the amount of analyte in the weighing
form:

1. Chemical Factors
2. Gravimetric Factors
 CHEMICAL FACTORS

The calculation of the weight of a constituent in a

given precipitate follows directly from the proportion:
Mn Ap : nM = W : x

Mn Ap is the molecular weight of the precipitate

◻

M is the atomic weight or molecular weight of the element

◻

n is the number of atomic weights of M in the molecular weight Mn

◻

Ap
W is the weight of precipitate
◻
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:
 BY USING
GRAVIMETRI
C FACTOR
METHOD
 BY USING
Gravimetric Factor, Gf GRAVIMETRI
C FACTOR
METHOD
Analyte, A Weighed as solid Gf
(weighing form)

Cl AgCl FW (Cl)/1
= 0.2474
FW(AgCl)/1
Fe Fe2O3 FW (Fe) / 1
= 0.6994
FW( )/2
Fe 2 O3
FW (P)/ 1
P Mg2P2O7 = 0.2783
FW( )/2
Mg2
P2O7
Fe3O4 Fe2O3 FW (F )/3
e3O4 = 0.966
FW (F )/2
e22O
FW (P
3
O5)/2
P 2O 5 Mg2P2O7 = 0.6378
FW ( )/2
Mg2
P2 O7
Weight of analyte = Gravimetric factor x weight of weighing
form.
Gravimetric factor
◻ In gravimetric analysis, composition of the
analyte usually expressed in percent
 Example of Gravimetric Calculation
Example 1: Determination of Fe2+
1.0 g of an iron compound, after suitable treatment, yielded 0.1565 g
of ferric oxide. Calculate the percentage of iron in the compound.

Method 1
Mn Ap / nM = w/
Fe2O3 / 2Fex= 0.1565
/ x = 0.1565 / x
160 : 2 x 56

x = 112/160 x 0.1565 = 0.1095

g
% Analyte (A) in sample

= weight of A (analyte) x 100%

weight of sample

= 0.1095 x 100%
1.00

= 10.95 %(w/w)
 BY USING
Using the gravimetric factor: GRAVIMETRI
C FACTOR
Fe in Fe2O3 = 0.6994 METHOD
Weight of Fe
= Gravimetric factor x weight of weighing form
= 0.6994 x 0.1565 = 0.1095 g
GF = FW (Fe) / 1
=
0.6994
FW( )/2
g of Fe Fe2 O3

% of Fe = x 100%
g sample

= 0.1095 x
100%
1.00
Example 2
Calculate the percentage of bromide in a sample
weighing 354 mg that yields a dried precipitate of AgBr
BY USING
weighing 187 mg. GRAVIMET
RIC
FACTOR
GF= FW (Br)/1= 0.4255
METHOD
FW(AgBr)/1

Weight of Br
= Gravimetric factor x weight of AgBr
= 0.4255 x 187 mg
= 79.6 x 10 -3 g
 Example 3
In one gravimetric analysis, the aluminum in a
1.2 g sample of impure NH4Al(SO4)2 was precipitated as
hydrous Al2O3.xH2O . The precipitate was filtered and
ignited at 10000C to give anhydrous Al2O3 which weighed
0.1798 g. Calculate the % Al in the sample.
Method 1
Example 4

Solution
Step 1: identify analyte and precipitate
Step 2: identify mass sample and mass precipitate
Example 5
Answer