Chapter 6

Gravimetric Methods of Analysis

AC1_Chp 6 1
 Gravimetric Analysis
 Principle : methods based on measurement of
weight of an analyte or a compound containing the
analyte
 Types of Gravimetric Analysis
 Calculation of results

AC1_Chp 6 2
 Types of Gravimetric Methods
 Precipitation gravimetry - A gravimetric method
in which the signal is the mass of a precipitate
 Electrogravimetry - A gravimetric method in
which the signal is the mass of an electrodeposit on
the cathode or anode in an electrochemical cell
 Volatilization gravimetry (indirect method) - A
gravimetric method in which the loss of a volatile
species gives rise to the signal
 Particulate gravimetry (direct method) - A
gravimetric method in which the mass of a
particulate analyte is determined following its
separation from its matrix.

AC1_Chp 6 3
 Electrogravimetry

electrolysis

AC1_Chp 6 4
 Precipitation Gravimetry
 Gravimetry is among the most accurate and
precise methods of macroquantitative analysis.
 The analyte is selectively converted to an
insoluble form.
 The separated precipitate is dried or ignited,
possibly to another form, and is accurately
weighed.
 The weight of analyte in the desired form is
calculated from the weight of the precipitate
and a knowledge of its chemical composition
(stoichiometric mole relationships).

AC1_Chp 6 5
 Gravimetric Analysis – Precipitation
Gravimetry
What steps are needs
 Preparation of the solution (1)
 Precipitation (2)
 Digestion (3) (to make larger and more pure crystals)
 Filtration (3)
 Washing (3)
 Drying or igniting (3) (Drying removes the solvent and wash
electrolytes )
 Weighing (4)
AC1_Chp 6 6
 Example
An ore containing magnetite, Fe3O4, was
analyzed by dissolving a 1.5419-g sample in
concentrated HCl, giving a mixture of Fe2+ and
Fe3+. After adding HNO3 to oxidize any Fe2+
to Fe3+, the resulting solution was diluted with
water and the Fe3+ precipitated as Fe(OH)3 by
adding NH3. After filtering and rinsing, the
residue was ignited, giving 0.8525 g of pure
Fe2O3. Calculate the %w/w Fe3O4 in the
sample.
Fe(OH)3 900 - 1000 oC Fe2O3
precipitate weighted
compound
AC1_Chp 6 7
 Precipitation Gravimetry

 Soluble species + precipitant precipitate

Low solubility
High purity
Check for the
completeness of Known composition
precipitation Easy to separate from
the reaction mixture

Precipitant: a reagent that causes the precipitation of a

soluble species
AC1_Chp 6 8
 Precipitation Gravimetry - Impurities

 Inclusion A coprecipitated impurity in

which the interfering ion occupies a lattice
site in the precipitate.
 Occlusion A coprecipitated impurity
trapped within a precipitate as it forms.
 Adsorbate A coprecipitated impurity that
adsorbs to the surface of a precipitate.

AC1_Chp 6 9
 Precipitation

 Controlling Particle Size

 Coagulation - The process of smaller
particles of precipitate clumping together
to form larger particles.
 Digestion - The process by which a
precipitate is given time to form larger,
purer particles.

AC1_Chp 6 10
 Filtration - Filter paper

AC1_Chp 6 11
 Filtration

Isolate precipitate
Remove impurity

AC1_Chp 6 12
 Filtration - Filter paper

 The most common filtering medium is

cellulose-based filter paper
 Filter classified according to its filtering
speed, its size, and its ash content on ignition.

AC1_Chp 6 13
 Filtration - Filter paper

 For quantitative analytical procedures a low-

ash filter paper must be used. This grade of
filter paper is pretreated by washing with a
mixture of HCl and HF to remove inorganic
materials.
 Filter paper classed as quantitative has an ash
content of less than 0.010% w/w.
 Qualitative filter paper typically has a
maximum ash content of 0.06% w/w.

AC1_Chp 6 14
 Gravimetric Analysis
 Types of precipitates
 crystalline precipitate (0.2 – 0.6 g)
 colloidal precipitates (peptization, gelatinous) (0.05 –
0.3 g)
 The precipitation process (supersaturation)
 Impurities in precipitates
 Occlusion
 Surface Adsorption
 Check for the completeness of precipitation

AC1_Chp 6 15
 Example
2 2
Ba  SO4  BaSO4 
 Prepare sample
 Precipitate
 Filtrate and purify
 Weight

AC1_Chp 6 16
 Calculation of result
 Direct or indirect methods
 Solid sample
m'
m (g) sample % X  100
m
m’ (g) X analyte
m' V
Dilution % X   100
m v

 Liquid sample X ( g / L )  m '

1000
v

 Precipitation gravimetry
AC1_Chp 6 17
 Calculation of result
 Precipitation gravimetry
- Solid sample:
m (g): mass of
100 sample
% X  m ' F  m’ (g): mass of the
m compound weighed

M ( formular weight of analyte )

F  k
M ( formular weight of compound weighed )

BaCl 2 2Fe
Example F  F 
BaSO 4 Fe 2 O 3
:
AC1_Chp 6 18
 Calculation of Result
 Precipitation gravimetry
- Solid sample (dilution):

V 100
% X  m ' F  
v m

- Liquid sample:
V 1000
X ( g / L )  m ' F 
v1 v

AC1_Chp 6 19
AC1_Chp 6 20
AC1_Chp 6 21
 Example Ba 2   SO 4 2   BaSO 4 
dissolve
Weight m(g) BaCl2 . Filtrate, 100.0 (mL)
xH2O (sample) Take 10.00 (mL)
+ SO4 2-

600 oC
m’ (precipitate) BaSO4
m = 7.0420 g and m’ = 0.6726 g, calculate % Ba, % BaCl2
and determine x
0 . 6726 100 . 0 100
% Ba    137 . 34   54 . 96 %
233 . 40 10 . 00 7 . 0420
0 . 6726 100 . 0 100
% BaCl 2    208 . 25   85 . 22 %
233 . 40 10 . 00 7 . 0420
AC1_Chp 6 22
 Example (continue)
Ba 2
 SO 4 2   BaSO 4 

Calculate the volume of 0.20 M H2SO4 used to react with Ba2+

, (15% SO42- in excess)

3 0 . 6726
0 . 2  10  v ( mL ) 
233 . 40
v  14 . 41 mL
the volume of 0.20 M H2SO4 = 14.41 + 14. 41 x
15/100 = 16.57 mL = 17 mL

AC1_Chp 6 23
 Example (continue)

Calculate the volume of 40% H2SO4 (d = 1.305 g/mL) used to

make 1 liter of 0.20 M H2SO4.

40  1305
100  5 . 3265 M
98
5 . 3265  V  0 . 20  1000
V  38 mL

AC1_Chp 6 24