Analytical Chemistry

Chapter 12. Gravimetric Methods of Analysis

 Types of Gravimetry

➢ Precipitation methods:
➢ Volatilization methods: CO2, H2O
The analyte is separated from other constituents of a sample by converting
it to a gas of known chemical composition. The mass of the gas then serves as
a measure of the analyte concentration.
➢Thermogravimetric analysis
➢Electrogravimetry:
Metal ions are electro-reduced onto the cathode, and then the weight
difference before and after the electro-deposition is measured.
 Properties of Gravimetry

➢ Advantage—accurate, no standard solutions

needed!

➢ Disadvantage—complicated, time consuming, not

suitable for microanalysis
 Precipitation Gravimetry

➢ Precipitation methods:
The analyte is separated from a solution of the sample as a precipitate
and is converted to a compound of known composition that can be
weighed.

Precipitant R
Unknown
Precipitation form P1
analyte X

Weighting form P2
 Precipitation Gravimetry

Official method to determine calcium in water:

 Precipitation Gravimetry

Process of Precipitation Gravimetry:

Dissolution Precipitation
Unknown Precipitation
analyte X form P1
Filtering; Dry;
Wash Ignition
Weighting
form P2
 Precipitation Gravimetry

Process of Precipitation Gravimetry:

Precipitation form and weighting form can be the same or different.

 Precipitation Gravimetry

The ideal precipitating reagent would react with the analyte to

give a product that is:

(Precipitation form)
➢ easily filtered and washed free of contaminants;
➢ of sufficiently low solubility that no significant loss of the
analyte occurs during filtration and washing;

(Weighting form)
➢ unreactive with constituents of the atmosphere;
➢ of known chemical composition after it is dried or, if necessary,
ignited.( large MW)
 Solubility of Precipitates and its factors

Factors affecting solubility of precipitates are:

1. Common ion effect
2. Salt effect
3. Acid effect
4. Coordination complex
5. Other factors
 Solubility of Precipitates and its factors

1. Common ion effect—

decrease the solubility
 Solubility of Precipitates and its factors

2. Salt effect—
increase the solubility
 Solubility of Precipitates and its factors

3. Acid effect—
increase the solubility of salts with weak acid anion
 Solubility of Precipitates and its factors

3. Acid effect—
increase the solubility of salts with weak acid anion

CaC2O4(s) ↔ Ca2+ + C2O42-

C2O42- + H+ ↔ HC2O4- , H2C2O4

P260: Example 11-7

pH=4 s=7.0×10-5 M
pH=1 s=?
 Solubility of Precipitates and its factors

4. Coordination complex effect—

usually increase solubility
+ -
MA(s) M (aq) + A (aq)
nL

MLn

[ M + ] + [ M ( L) + ] + [ M ( L2 ) + ] +    + [ M ( Ln ) + ] = c M + = s
[ A− ] = s
 = K sp   M ( L )
K sp

s = K sp = K sp   M ( L )
 Solubility of Precipitates and its factors

4. A complicate system…

Common ion effect

Complex effect
 Solubility of Precipitates and its factors

5. Other factors—
➢ Temperature ΔG = ΔH – TΔS
➢ Solvent： e.g. Adding organic solvent will decrease solubility of
ionic precipitates. (compatibility principle)

➢Forming colloids: increase solubility

➢Particle size: (Ostwald ripening)

Ostwald ripening in Pd nanoparticles dissolved

in formaldehyde at 6 (a), 24 (b), 48 (c) and 72
hours (d). The small Pd particles are being
consumed as the larger ones grow bigger.
 Ostwald ripening

This thermodynamically-driven spontaneous process occurs because larger particles

are more energetically favored than smaller particles.

This stems from the fact that molecules on the surface of a particle are energetically
less stable than the ones in the interior. Consider a cubic crystal of atoms: all the
atoms inside are bonded to 6 neighbors and are quite stable, but atoms on the surface
are only bonded to 5 neighbors or less, which makes these surface atoms less stable.
Large particles are more energetically favorable since, continuing with our example,
more atoms are bonded to 6 neighbors and fewer atoms are at the unfavorable
surface. As the system tries to lower its overall energy, molecules on the surface of a
small particle (energetically unfavorable, with only 3 or 4 or 5 bonded neighbors) will
tend to detach from the particle, as per the Kelvin equation, and diffuse into the
solution. When all small particles do this, it increases the concentration of free atoms
in solution. When the free atoms in solution are supersaturated, the free atoms have
a tendency to condense on the surface of larger particles. Therefore, all smaller
particles shrink, while larger particles grow, and overall the average size will increase.
After an infinite amount of time, the entire population of particles will have become
one, huge, spherical particle to minimize the total surface area.
 Particle Size & Filterability of Precipitates

Types of precipitates:
Example Size
➢ Crystalline suspension Big
BaSO4
10-2 cm in diameter, easy 0.1 ~ 1 m
MgNH4PO4
to settle and filter.
AgCl

➢ Colloidal suspension
Fe2O3.nH2O 0.02 m
10-7to 10-4 cm in diameter,
difficult to settle and filter; Al2O3.nH2O Small
 Particle Size & Filterability of Precipitates

Factors that determine the particle size of precipitates：

Q is the concentration of the solute at any instant, and S is its

equilibrium solubility.

When (Q - S)/S is large, the precipitate tends to be colloidal,

and when (Q - S)/S is small, a crystalline solid is more likely.
 Mechanism of Precipitate Formation
Factors that determine the particle size of precipitates：

Particle
Nucleation growth
Ions

➢ At high relative supersaturation,

Nucleation rate > particle growth rate, small particles (colloidal) forms

➢ At low relative supersaturation,

Particle growth rate > nucleation rate, big particles (crystalline) is produced
 Mechanism of Precipitate Formation
Amorphous precipitate formation
 Mechanism of Precipitate Formation
Crystalline precipitate formation

SO4 Ba2+
SO4
2-
2- Ba2+ Ba2+SO4 2-
SO4
Ba2+ 2-
SO4 SO4
SO4 2- 2-
2-
Ba2+ Ba2+ Ba2+ Ba2+
SO4
SO4 2-
Ba2+
2- SO4
2- Ba2+
Ba2+ Ba2+ Ba2+
SO4 SO4
2- SO4 2- SO4
2- 2-
SO4
2-
SO4 Ba2+
2- SO4 SO4
Ba2+ 2- 2- SO4
Ba2+ Ba2+
2-

SO4
Ba2+ Ba2+ 2-
Ba2+
SO4 Ba2+ SO4
2- SO4 2- Ba2+
2-
 Mechanism of Precipitate Formation
Crystalline precipitate formation

2 SO42 SO 2 Ba2+
SO4 - Ba2+ Ba2+ 4 -
- SO42
Ba2+ -
SO42
-
2
SO4 Ba2+
Ba2+ - 2+ SO 2 Ba2+
2 Ba -4 SO42
SO4 2 -
Ba2+
- Ba2+ 2SO- 4 2+ Ba2+
SO4 Ba
-
Ba2+ SO4 2
SO42
- - SO42
-
SO42
-
SO4 2 Ba2+
- SO42 SO42
Ba2+ - - SO42
Ba2+ Ba2+
-

SO42
Ba2+ Ba2+ -
2 2 Ba2+
SO4 Ba2+ SO4
- SO42 - Ba2+
-
 Mechanism of Precipitate Formation
Crystalline precipitate formation
2 SO42 SO42 Ba2+
SO4 - Ba2+ -
-
Ba2+ SO42
-

Ba2+ SO42 Ba2+ SO42 Ba2+

- 2+ SO 2 - 2+
Ba -4
Ba
SO42 Ba2+
- Ba2+ 2SO- 42 2+Ba2+ 2
SO4 Ba SO4
- -
2
SO4 Ba SO4 2
Ba2+ SO42 2+
- 2+ SO 2 - 2+
- Ba 4 Ba SO42
- -
SO42
-
SO42
Ba2+
- SO42
-
Ba2+
SO4 2
Ba2+ Ba2+
-

2 Ba2+ SO42
SO4 - Ba2+
SO42 -
-
 Mechanism of Precipitate Formation
Crystalline precipitate formation
2 SO42 SO42 Ba2+
SO4 - Ba2+ -
-
Ba2+ SO42
-

Ba2+ SO42 Ba2+ SO42 Ba2+

- 2+ SO 2 - 2+
Ba -4
Ba
SO42 Ba2+
- Ba2+ 2SO- 42 2+Ba2+ 2
SO4 Ba SO4
- -
2
SO4 Ba SO4 2
Ba2+ SO42 2+
- 2+ SO 2 - 2+
- Ba 4 Ba SO42
- -
SO42
-
SO42
Ba2+
- SO42
-
Ba2+
SO4 2
Ba2+ Ba2+
-

2 Ba2+ SO42
SO4 - Ba2+
SO42 -
-
 Mechanism of Precipitate Formation
Crystalline precipitate formation

SO42- Ba2+ SO 2- 4
2-
Ba2+ SO4 Ba2+
SO42- Ba2+ SO42-
2-
Ba2+SOSO 2- 4 Ba
2+
2+
SO42-
4 Ba
Ba 2+ SO42- Ba2+
SO42- Ba2+ SO 2- 4
2-
Ba2+ SO4 Ba2+
SO42- Ba2+ SO42-
2-
Ba2+SOSO 2- 4 Ba
2+
2+
SO42-
4 Ba
Ba 2+ SO42- Ba2+
SO42- Ba2+ SO 2- 4
2-
Ba2+ SO4 Ba2+
SO42- Ba2+ SO42-
 Mechanism of Precipitate Formation
Experimental Control of Particle Size

To obtain big particles, relative supersaturation needs to be lowered

➢ Q is can often be minimized by using dilute solutions and adding

the precipitating reagent slowly, with good mixing.

➢ S is increased by precipitating from hot solution or by adjusting

the pH of the precipitation medium.
 Colloidal Precipitates

➢ Coagulation of Colloids
➢ Peptization of Colloids

Surface adsorption

Electric double layer

 Colloidal Precipitates

➢ Coagulation of Colloids
 Colloidal Precipitates

➢ Coagulation of Colloids
 Colloidal Precipitates

➢ Peptization of Colloids

Washing is needed to minimize contamination, but there is a risk of losses

resulting from peptization if pure water is used.

The problem is usually solved by washing the precipitate with a solution

containing an electrolyte that volatilizes when the precipitate is dried or ignited.
 Coprecipitation

Coprecipitation is a process in which normally soluble compounds

are carried out of solution by a precipitate.

➢Surface adsorption—(colloid, digestion & wash)

➢Mixed-crystal formation (pre-separation) e.g. BaSO4&PbSO4
➢Occlusion (crystalline, digestion)
➢Mechanical entrapment – (crystalline, digestion)
 Coprecipitation

➢ Surface adsorption—(colloid)
 Coprecipitation

➢ Surface adsorption—(colloid)
 Coprecipitation

Minimizing adsorbed impurities on Colloids

➢ Digestion: water is expelled from the solid to give a denser

mass that has a smaller specific surface area for adsorption.

➢ Washing: washing with an acidic solution converts the counter-

ion layer largely to hydrogen ions so that both chloride and
hydrogen ions are retained by the solid.

➢ Reprecipitation
 Coprecipitation

➢ Mixed-Crystal Formation
e.g. BaSO4&PbSO4
(pre-separation)

➢ Occlusion
(digestion)

➢ Mechanical Entrapment Mechanical entrapment occurs when

crystals lie close together during growth.
(digestion) Several crystals grow together and in so
doing trap a portion of the solution in a
tiny pocket.
 Precipitation from Homogeneous Solution

Precipitation from homogeneous solution is a technique in which a precipitating

agent is generated in a solution of the analyte by a slow chemical reaction.

The precipitating agent appears gradually and homogeneously throughout the solution,
so that the relative supersaturation is kept low during the entire precipitation.
 Precipitation from Homogeneous Solution

Precipitation from homogeneous solution

➢ Hydrous oxides of iron(III) and aluminum, formed by

direct addition of base, are bulky and gelatinous
masses that are heavily contaminated and difficult to
filter.
➢ In contrast, when these same products are produced
by homogeneous generation of hydroxide ion, they are
dense, are easily filtered, and have considerably higher
purity.
Precipitation from Homogeneous Solution
 Drying and Ignition of Precipitates

Heating removes the solvent and any volatile species carried down with the precipitate.

Note the vastly different temperatures required

to produce an anhydrous precipitate of constant
mass.

Moisture is completely removed from silver

chloride at temperatures higher than 110°C,
but dehydration of aluminum oxide is not
complete until a temperature greater than
1000°C is achieved. Aluminum oxide formed
homogeneously with urea can be completely
dehydrated at about 650°C.
Drying and Ignition of Precipitates
Calculation of Results from Gravimetric Data
Calculation of Results from Gravimetric Data
Calculation of Results from Gravimetric Data
Calculation of Results from Gravimetric Data