Gravimetric Method of Analysis

INTRODUCTION TO ANALYTICAL
CHEMISTRY
WHAT IS GRAVIMETRIC ANALYSIS??
Definition:
a precipitation or volatilization method based on
the determination of weight of a substance of
known composition that is chemically related to the
analyte

analyte - chemical element or compound of

interest
ADVANTAGES/DISADVANTAGES
Experimentally simple and elegant
Accurate
Precise (0.1-0.3 %)
Macroscopic technique-requires at least 10 mg ppt
to collect and weigh properly
Time-consuming (1/2 day?)
 T.W.RICHARDS
Every substance must be assumed to be impure,
every reaction must be assumed to be incomplete,
every method of measurement must be assumed to
contain some constant error, until proof to the
contrary can be obtained. As little as possible must
be taken for granted.
FUNDAMENTALS TYPES OF GRAVIMETRIC
ANALYSIS:

Physical gravimetry
Thermogravimetry

Precipitative gravimetric analysis

Electrodeposition
PHYSICAL GRAVIMETRY
Total solids (TS) is generally defined as all
matter in a water or wastewater sample
that is not water
Dissolved solids: all solids passing
through filter paper of a certain pore size
(e.g., 1.5 microns, Whatman #934AH)
Suspended solid: all solids retained filter
paper of a certain pore size (e.g., 1.5
microns, Whatman #934AH)
THERMOGRAVIMETRY,
PRECIPITATIVE GRAVIMETRIC ANALYSIS
Precipitation methods
Calcium in natural water

Volatilization methods
NaHCO3 in antacid tablets
GRAVIMETRY
Gravimetry : any method in which the signal is a
mass or change in mass
Direct methods determine the mass of the itself
- Ni(DMG)2
Indirect methods involve changes in the weight of
an analyte as a result of removing part of the
analyte and weighing by difference
- Moisture analysis
7 STEPS IN GRAVIMETRIC ANALYSIS
Dry and weigh sample
Dissolve sample

Add precipitating reagent in excess

Coagulate precipitate usually by heating

Filtration-separate ppt from mother liquor

Wash precipitate (peptization)

Dry and weigh to constant weight

REQUIREMENTS FOR SUCCESSFUL GRAVIMETRIC
DETERMINATION

Complete Precipitation of Desired Substance

Weighed form of the PPt should be a
stoichiometric compound of known composition
The PPt must be pure

The PPt must be easily filtered

PROPERTIES OF PRECIPITATES AND
PRECIPITATING AGENTS

The ideal precipitating agent will react

specifically or, if not, selectively with the analyte
Precipitate should be easily filtered and washed
free of contaminates
Precipitate should be essentially insoluble to
prevent washing loss
Precipitate should be unreactive with the
atmosphere
Precipitate should be of known composition
PARTICLE SIZE AND FILTERABILITY OF PRECIPITATES

colloidal suspensions (10-7~10-4 cm or 10-

6~10-4 mm)
ex: Fe(OH)3 (gelatinous)

curdy : ex: AgCl

crystalline (10-2~10 mm): ex: BaSO4

FACTORS THAT DETERMINE THE PARTICLE SIZE OF
PRECIPITATES

ppt solubility
temperature
reactant concentrations
rate at which reactants
are mixed
MECHANISM OF PRECIPITATION
Precipitation results from the competing
processes of
Nucleation - Fast combination of a few atoms,
often on the surface of dust particles. Very
difficult size to filter and separate
Particle Growth - occurs more slowly, and at
lower relative supersaturation of the solution.
The particle grows with the addition of ions of
the precipitate until the system comes to
equilibrium
NUCLEATION VS. CRYSTAL GROWTH
Rapid Nucleation
=Slow Crystal Growth

Slow Nucleation
=Rapid Crystal Growth
Ways to Promote Particle Growth
Raise the temperature
Increases solubility, decreasing supersaturation

Add precipitant slowly

Avoids localized supersaturation

Keep volume of solution large

Analyte and reagent concentrations are kept low
COLLOIDAL PRECIPITATES

Coagulation (or agglomeration) of colloids: converting

a colloid suspension into a filterable solid.

Adsorption: a process in which a substance (gas,

liquid or solid) is held on the surface of a solid. In
contrast, absorption, involves retention of a substance
within the pores of a solid.

Electric double layer:

Electric double layer:
Primary adsorbed layer
primary adsorbed ion:
1. lattice ions which in excess.
2. held by chemical bound
3. fixed on ppt surface
ex: AgCl in excess Ag+ AgCl:Ag+ (s)

Counter-ion layer
counter-ions
1. opposite charge of primary adsorbed ion
2. held by electrostatic attraction
3. loosely held in soln surrounding the ppt
ex: AgCl in excess AgNO3
AgCl:Ag+ NO3- (s)
ADSORBED IONS
Primary Adsorbed Ions
Primary adsorbed ions are ions of the precipitate
that are adsorbed on the surface of the macrosize
particle. As a result of the adsorption of these
ions, the surface of the macrosize particle is
charged.
Counterions

counter ions are Ions of opposite charge are

attracted to the region of the solution
surrounding the particle.
Precipitation Using an Electrolyte
Ionic compounds are usually precipitated in the
presence of an electrolyte; for AgCl

The surface of the particle

will have a small positive charge
due to adsorption of excess silver
ions. The ionic atmosphere
surrounds the particle and has a
slight net negative charge.
For particle growth, colloidal
particles must collide to
coalesce. But the negative
atmospheres around the particles
repulse each other
electrostatically. Adding
electrolyte decreases the volume
of the ionic atmospheres,
allowing repulsion to be
EXPERIMENTAL FACTORS
FAVORING PARTICLE GROWTH

Elevated Temperatures- enhance solubility of the

precipitate
Dilute solutions
Slow addition of precipitating agent
Good stirring in heated solutions
Careful pH control (if solubility is dependent on
pH)
FACTORS AFFECTING PARTICLE SIZE
Von Weirman (1925):
V= k Q - S
S
V= Kec. Pembentukan endapan
Q= Kons.zat yang akan diendapkan
S= Kelarutan endapan
K= Konstanta
Q S = kelewatjenuhan pada saat endap mulai te rjadi,
S
 Q S = makin besar, inti kristal (nuklei) terjadi,
butir-butirendapan yang terbentuk makin halus
S makin besar, Q S = kecil, kristal semakin
sedikit dan endapan semakin besar
V= besar, terbentuk banyak nuklei, endapan
halus,
V= kecil, nuklei sedikit, endapan kasar
PENURUNAN KECEPATAN ENDAPAN:
Q S kecil
- Pengendapan dalam larutan encer

- Penambahan zat pengendap sedikit-demi sedikit

sambil terus diaduk
S Besar

- Larutan encer

- Pengendapan dalam larutan panas

- Pengaturan pH
GENERALY, TECHNIQUE TO MINIMIZE
RELATIVE SUPERSATURATION, ARE:
Precipitation from a very dilute solution (Q is
kept small)
C Slow addition of the precipitating reagent (Q is
kept small)
Precipitation from a hot solution ( Initially, S is
kept large. When Q is very small at the end of the
precipitation, S is reduced by cooling the
solution.)
C Precipitation from an acidic solution ( Initially,
S is kept large. When Q is very small at the end
of the precipitation, S is reduced by neutralizing
the solution.)
DIGESTION

Helps eliminate colloidal suspensions which are

difficult or impossible to filter
Digestion occurs when a precipitate is allowed to
stand in its heated solution
The solid re-dissolves and precipitates, along
with increased crystal growth
The resulting solid is usually more filterable and
purer
Minimizes coprecipitation
COPRECIPITATION

Coprecipitation is the process of otherwise

soluble material removed from solution during
precipitate formation.
Surface Adsorption - most pronounced on colloids
with large surface areas. Brings along surface
contamination. Reprecipitate.
Mixed-Crystal Formation- Replacement of one of
the ions in the crystal by another ion.
Occlusion - trapping of contaminants as a crystal
grows
Mechanical Entrapment - entrapment of foreign
substances when two adjacent growing crystals
grow together to form one
MINIMIZING COPRECIPITATION
Accomplished by carefully controlling solution
conditions
Precipitate less soluble interferent precipitates
and filter them
Mask analyte or interferent with a suitable

complexing agent to prevent precipitation

FILTRATION
Usually accomplished with filter paper or fritted
glass crucibles
Pore size should be chosen carefully to retain
analyte particles but not clog
Filter paper must usually be removed by ignition
but this requires a low ash paper
Filtering process begins by decanting the
supernatant liquid through the filter medium,
followed by the solid with wash
RINSING

Removes the remaining supernatant

Avoid solubility losses

Use of cold solvent often accomplishes this

goal
pH adjustment may be necessary for acids

and bases
A volatile inert electrolyte may be added to

the wash to avoid peptization

CALCULATION

% of analyte, % A

%A = weight of analyte x 100

weight of sample

weight of ppt directly obtained ->?A

 % A = weight of ppt x gravimetric factor (G.F.) x 100
weight of sample

G.F. = a FW[analyte]
b FW[precipitate]

G.F. = # gms of analyte per 1 gm ppt

 G.F. = a FW[analyte]
b FW[precipitate]

Analyte ppt G.F.

CaO CaCO3
FeS BaSO4
UO2(NO3)2.6H2O U3O8
Cr2O3 Ag2CrO4
 Analyte ppt G.F.
CaO CaCO3 CaO/CaCO3
FeS BaSO4 FeS/BaSO4
UO2(NO3)2 U3O8 3UO2(NO3)2/U3O8
Cr2O3 Ag2CrO4 Cr2O3/2Ag2CrO4

Naming is critically important (next class)

PROBLEMS

1. Considera 1.0000 g sample containing 75%

potassium sulfate (FW 174.25) and 25% MSO4.
The sample is dissolved and the sulfate is
precipated as BaSO4 (FW 233.39). If the BaSO4
ppt weighs 1.4900, what is the atomic weight of
M2+ in MSO4?
2. The iron content of an organometallic compound
was determined by treating a 0.4873-g sample
with HNO3 and heating to volatilize the organic
material.
After ignition, the residue of Fe2O3 was found to
weigh 0.2091-g.
What is the %w/w Fe in this compound?
3. Konsentrasi Ca2+ dalam sampel air ditentukan
dengan mengendapkan kation sebagai CaC2O4.
Endapan disaring, dicuci dan dibakar dalam krus yang
bermassa 26,6002 g. Massa krus dan CaO (56,077 g/mol)
adalah 26,7134 g. Hitung konsentrasi Ca (40,078 g)
dalam air dalam satuan gram/100 mL