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GRAVIMETRIC METHODS
OF ANALYSIS
ROSE ANN Z. TAMOLANG
UST FACULTY OF ENGINEERING
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Required Reading: Ch. 12

(Fund. Ana. Chem. by Skoog, West, Holler & Crouch, 9th ed., 2014)

A History of Gravimetric Analysis

Theodore W. Richards (1868 - 1928)
with his graduate students at Harvard University

developed and refined many of the techniques of

gravimetric analysis of silver and chlorine.
These techniques were used to determine the atomic
weights of 25 of the elements by preparing pure
samples of the chlorides of the elements, decomposing
known weights of the compounds, and determining the
chloride content by gravimetric methods. From this
work Richards became the first American to receive the
Nobel Prize in Chemistry in 1914.
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INTRODUCTION
Gravimetric Analysis
Gravi metric
(weighing measure)

To measure the purity

Most accurate analytical technique
It is an absolute method
Precise methods of macro quantitative analysis
Possible sources of errors can be checked
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Gravimetric Analysis
Quantitative determination of analyte concentration through
precipitation of the analyte, isolation of the precipitate, and
weighing the isolated product.

TYPES of GRAVIMETRIC METHODS of ANALYSIS

1. Precipitation methods
2. Volatilization methods
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PROCEDURE FOR GRAVIMETRIC

ANALYSIS

Analyte or
Sample

Precipitate
form
(insoluble
form)

Filtration
(separate
the
precipitate)

Drying

Igniting

Weighing

Calculations

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General Scheme of Gravimetric

Analysis
1. A weighed sample is dissolved
2. An excess of a precipitating

agent is added to this solution

dissolved
components
sample

3. The resulting precipitate is

filtered, dried (or ignited) and

weighed

precipitating agent

4. From the mass and known

composition of the precipitate,

the amount of the original ion
can be determined

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1. Precipitation Method
a.
b.
c.
d.
e.
f.
g.

Weighing of the sample

Moisture determination
Conversion of the analyte to a sparingly soluble salt (precipitate)
Filtration of the precipitate
Washing of the precipitate
Drying or ignition of the precipitate

Weighing of the converted form of the precipitate

Ca2+ + C2O42- CaC2O4(s) precipitate

CaC2O4(s) CaO(s) + CO (g) + CO2(g)
The weighed form is CaO

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2. Volatilization Method

a. Weighing of sample
b. Moisture determination
c. The analyte or its decomposition products are volatilized at
suitable temperature

d. The volatile product is then collected and weighed or alternately

the mass of the product is determined directly from the loss in
mass of the sample

NaHCO3(aq) + H2SO4(aq) CO2(g) + H2O(l) + NaHSO4(aq)

The mass of CO2 is determined by connecting a weighed

tube with adsorbent to the reaction vessel

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2. Volatilization Method

Figure 4-1 Apparatus for determining the sodium hydrogen carbonate content of
antacid tablets by a gravimetric volatilization procedure.

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Moisture Determination
Sample is weighed before and after drying the sample
This is done so that the composition of the sample does not
depend on the relative humidity and temperature at the time of
analysis

Done using heating the sample in a conventional oven, vacuum

oven, or by storing in a desiccators, microwave ovens, infrared
lamps
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Forms of water in solids

1)

Essential Water

-water of crystallization

Integral part of the water or crystalline structure of the compound in the solid
state (e.g. BaCl22H2O, CaC2O4 2H2O)
-water of constitution

Formed when a pure solid is decomposed by heat or other chemical treatment

( e.g. Ca(OH)2(s) CaO(s) + H2O(l) )
2) Non-essential water
-adsorbed water

Retained on the surface of solids

-occluded water

Liquid water entrapped in microscopic pockets spaced irregularly throughout

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solid crystals

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Drying and Ignition of Precipitates

After filtration, a gravimetric precipitate is heated until its mass becomes
constant.

Conversion of the precipitate into a suitable form for weighing

1. Drying in an oven (100 130oC)
2. Ignition in a furnace (1000oC)
e.g. conversion of CaC2O4 to CaO also for complete removal of water that is
occluded or very strongly adsorbed
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Criteria for Gravimetric Analysis

1.

The desired substance must completely precipitate

from solution

In most determinations the precipitate is of such low solubility

that dissolution of the analyte is negligible

An additional factor is the "common ion" effect, further reducing

the solubility of the precipitate

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Criteria for Gravimetric Analysis

When Ag+ is precipitated from solution through the
addition of Cl-

Ag Cl AgCl (s )
the (low) solubility of AgCl is further reduced by
the excess of Cl- that is added, pushing the
equilibrium to the right (Le Chateliers Principle).
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Criteria for Gravimetric Analysis

2. The weighed form of the product should be of
known composition.
3.

The product should be "pure" and easily

filtered.

It is usually difficult to obtain a product that is "pure (i.e.,

one that is free from impurities)

Careful precipitation and sufficient washing may reduce

the level of impurities
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Properties of precipitates and

Precipitating Agents
Ideally, a gravimetric precipitating agent should react specifically or
at least selectively with the analyte

Specific reagents (rare) react only with a single chemical species

Selective reagents (more common) react with only a limited
number of species

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Characteristics of Ideal Precipitating

Reagents
1-Readily filtered and washed free of contaminants
2-Of sufficiently low solubility so that no significant loss of the solid
occurs during filtration and washing
3-Unreactive with constituents in the atmosphere
4-Of known composition after it is dried or ignited

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Types of Precipitates
1. Curdy
- coagulated suspensoids, e.g AgX (AgCl,AgBr, etc.)

2. Gelatinous
-coagulated emulsoids e.g. +3 metal hydroxides [Fe(OH)3, Al(OH)3].
- trap a too much water and many more impurities.

3. Crystalline
regularly shaped discrete particles; digested to form larger and purer particles at the
expense of smaller particles. e.g. alkaline earth sulfates, BaSO 4
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Formation of Precipitates

A precipitate is formed when the diameter of an aggregate of

atoms , ions or molecules is greater than 10-4 cm

ions in solution
10-8 cm

Colloidal
particles
10-7 to 10-4 cm

precipitate
>10-4 cm

Colloidal particles are electrically charged and resist combining to

form larger particles that will settle out of the solution

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Mechanism of Precipitation

1. Induction period
The time before nucleation occurs after the addition of
the precipitating agent to the solution
May range from milliseconds to several minutes

2. Nucleation
- Process in which minimum number of atoms, ions,
or molecules join together to give a stable solid
Homogeneous nuclei form due to fluctuation of
ion concentration
Heterogeneous particles form on foreign solids like
dust particles, or rough sides of the beaker
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Mechanism of Precipitation
3. Particle growth
Growth on the existing nuclei to form particles sufficiently large
enough to precipitate

Precipitate Formation vs. Particle Size

If rate of nucleation < rate of particle growth,
then fewer particles are finally produced which are
relatively large and purer
If rate of nucleation > rate of particle growth,
then many fine particles are finally produced
The particle size of a freshly formed precipitate is
determined by which way is faster

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Ideal Analytical Precipitation

In an ideal world, an analytical precipitate for

gravimetric analysis should consist of perfect

crystals large enough to be easily washed and
filtered.

The perfect crystal would be free from

impurities and be large enough so that it

presented a minimum surface area onto which
foreign ions could be adsorbed.

The precipitate should also be "insoluble" (i.e., low

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solubility such that loses from dissolution would

be minimal).

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Conditions for Analytical Precipitation

Von Weimarn showed that particle size of

precipitates is inversely proportional to the relative

supersaturation of the solution during precipitation

Relative supersaturation = (Q-S)/S

where :

large---colloidal
small--crystalline

Q is the molar concentration of the mixed reagents

before any precipitation occurs
S is the molar solubility of the product (precipitate)
when the system has reached equilibrium.

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Conditions for Analytical Precipitation

Addition of Precipitating reagent with effective stirring
(low Q)

- stirring avoids locally high concentrations of precipitating reagent.

Precipitation from hot solution (high S)

The molar solubility (S) of precipitates increases with an
increase in temperature

An increase in S decreases the supersaturation and increases

the size of the particle.

Precipitation from dilute solution (low Q)

This keeps the molar concentration of the mixed reagents low.
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Slow addition of precipitating reagent and thorough stirring

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keeps Q low.

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Colloidal Precipitates
Particle Size and Filterability of Precipitates
What Factors Determine Particle Size?
Colloidal particles show no tendency to settle from solution, nor are they
easily filtered.

The particles, with dimensions on the order of tenths of a millimeter or

greater, temporary dispersed in the liquid phase is called a crystalline
suspension.

The particles of a crystalline suspension tend to settle spontaneously and

are readily filtered.
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Colloidal Precipitates
Silver nitrate is added very slowly to an acidic solution
containing chloride. Silver chloride nuclei form with a
surface layer of ions. The charged AgCl particles (or
colloidal particles) repel each other.

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Colloidal Precipitates

In addition to the primary adsorbed silver ions, some nitrate

ions form an electrostatic layer around the nucleus.

These counter ions tend to aggregate around the

[AgCl:Ag]+ center because these centers have a net positive

charge (excess Ag+) and additional negative charge is
required to maintain electrical neutrality.

Counter ions are less tightly held than the primary adsorbed
ions and the counter ion layer is somewhat diffuse and
contains ions other than those of the counter ions.

These layers of charged ions associated with the surface of

the nuclei are known as the electric double layer.

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Colloidal Precipitates
Primary Adsorbed Ion
- The lattice ion that is in excess
- Held by chemical bond

- Fixed on the precipitate surface

Counter Ion
- Opposite in charge to primary adsorbed ion
- Held by electrostatic attraction
- Loosely held in solution surrounding precipitate
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Colloidal AgCl particle suspended in

a solution of AgNO3

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PRINCIPLES & STEPS INVOLVED IN

GRAVIMETRIC ANALYSIS
1. Preparation of the samples
solution

2. Precipitation process
3. Digestion (or) Ostwald
ripening

4. Filtration

5.
6.
7.
8.
9.

Washing
Drying
Igniting
Weighing
Calculation

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PREPARATION OF THE SAMPLE

SOLUTION
Factors to be considered during the preparation of sample
solution:
Volume of solution during precipitation
pH
temperature

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Volume of Solution during

precipitate
Solution condition (volume) must be adjusted to
maintain low solubility of precipitate

Excess volume of solution during precipitation leads the

precipitate to coagulate.

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pH
influence the solubility of the analytical precipitate
possibility of interference from other substance
Example: During Calcium oxalate precipitation
Insolube in basic medium

Soluble in acidic medium

REASON

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pH
influence the solubility of the analytical precipitate
possibility of interference from other substance
Example: 8-Hydroxy quinolone precipitating reagent
8-hydroxyl quinolone (oxine) used to precipitate a large number of elements = (precipitating reagent)
Precipitation occurs selective and controlled by pH
Example: in pH 4 condition
Aluminum ions can be easily precipitated at pH 4
Magnesium ion

Concentration of anion form of oxine is too low at pH 4 to precipitate Magnesium ion

Higher pH is required to shift the ionization step and precipitate the magnesium
If the pH is too magnesium hydroxide will precipitate causing interference.
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Temperature

Increase the
temperature

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Increase
the
solubility
of
precipitate

Precipitate
will be
dissolved or
coagulated

Making the
filtration
difficult

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PRECIPITATION PROCESS
Actually precipitate occurs in series of steps
Solution of precipitating
reagent added to

Sample solution

Precipitate formed

Example: AgNO3 + NaCl AgCl + NaNO3

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SUPERSATURATION
Supersaturation is one of the important parameter in precipitation process.
It plays vital role in gravimetry
Increase super saturation =
increase nucleation

Should we avoid super saturation &

nucleation?
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NUCLEATION individual ions / atoms / molecules

coalescence to from nuclei (small particles come together to form
particles)

Nucleation increases
Leads to more number of smaller size colloid to form crystal
Leads to adsorb the impurity
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NUCLEATION
Effects of Increase Nucleation
Initial nucleus will grow by the deposition of their precipitate particles
To form a crystal of certain geometric shape
Again the greater super saturation
More rapid crystal growth rate & colloidal precipitate formed
Increase the growth rate increased chance of imperfection in the crystal & surface area of
precipitate increase, this leads to easy trapping of impurities.

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Surface area of the precipitate increase =

the impurity adsorption increase

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Relationship between supersaturation &

nucleation
High relative supersaturation
Increase nucleation
Many small crystals
Colloidal particles form
High surface area
More adsorption of impurities
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Low relative supersaturation

Less nucleation
Fewer larger crystals
Crystalline particles form
Low surface area
Less adsorption of impurities
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Relationship between particle size and supersaturation

IN PRECIPITATION PROCESS
Von weimarn - discovered
Particle size of precipitate is inversely proportional to the relative supersaturation of
the precipitation process

Q = concentration of mixed reagents before no precipitation occurs

S = solubility of precipitate at equilibrium
This ration is called the Von Weimarn ratio
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Q value is low and S value is high during

precipitation
Precipitate from dilute solution. This keeps Q low.
Add dilute precipitating reagents slowly, with effective stirring. This also
keeps Q low. Local excess of the reagent are prevented by stirring.

Precipitate from hot solution. This increases S. The solubility should not be
too great or the precipitation will not be quantitative (with less than one
precipitate remaining). The bulk of the precipitate may be performed in the
hot solution, and then this solution may be cooled to make the precipitation
quantitative.
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Q value is low and S value is high during

precipitation
Precipitate at as low a pH is possible to maintain quantitative precipitation.
Many precipitates are more soluble in acid medium and this slows the rate of
precipitation. They are more soluble because the anion of the precipitate
combines with protons in the solution.

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Maintain crystalline precipitate & avoid

colloidal precipitate
Crystalline precipitate
Small or less number of large particles
Why should we avoid the colloidal precipitate?

more or large number of small particles (1-100 micrometer)

Difficult to wash and filter

Because colloidal precipitate may contain:
Hydrophilic particle (water loving) it forms viscous layer
Hydrophobic particle (water hating ) it forms gelatinous precipitate
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DIGESTION OF PRECIPITATE
Digestion is a process keeping the precipitate within the mother liquid (or solution
from which it precipitated) for a certain period of time to encourage
densification of nuclei.
During digestion, small particles dissolved and larger ones grow (Ostwald ripening)
This process helps produce larger crystal that are more easily filtered from solution

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OCCLUSION AND INCLUSION

OCCLUSION

INCLUSION

Trapping of impurities
with in the crystal.

Trapping of impurities with in the

crystal lattice

Example: Water may trapped Example:

in pockets when silver nitrate
K+ in NH4MgPO4
crystals are formed.

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Occlusion & inclusion

impurities are difficult
to remove.
Digestion may help
some but this is not
completely effective.
Purification by
dissolving and
reprecipitating my be
helpfuls

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SURFACE ADSORPTION
High relative
supersaturation

Increase
nucleation

Many small
crystals are
formed

More surface
area

More surface
adsorption

More
impurities
formed

More or large surface area in the precipitate leads to more surface adsorption & more impurites
It is reduced by proper precipitation
technique, digestion and washing
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POST PRECIPITATION
When the precipitate is allowed to stand in contact with mother liquor, a second
substance will slowly form a precipitate with precipitating agent

Example 1:
When calcium oxalate is precipitated in the presence of magnesium ions,
Magnesium oxalate does not immediately form precipitate because it tends to form
supersaturated solution.

Example 2:
Copper sulfide will precipitate in acid solution in the presence of zinc ion but eventually zinc
sulfide will precipitate

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ISOMORPHOUS REPLACEMENT
Two compounds are isomorphs it means same type of formula crystallize in similar
geometric forms and same lattice dimensions
So one ion can replace another crystal easily
Example:

In the precipitation of Mg2+ as magnesium ammonium phosphate, K+ has nearly

same ionic size as NH4+ and can replace it to form magnesium potassium phosphate
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WASHING & FILTERING THE

PRECIPITATE
Co precipitate impurities, especially these on the substance can
be removed by washing the precipitate after filtering
Precipitate will be wet by mother liquor that can also be removed
by washing
Many precipitate cannot be washed with pure water because
peptization occurs (reverse of coagulation)
Example: HNO3 and NH4NO3 are used for washing AgCl
precipitate
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DRYING AND IGNITING THE

PRECIPITATE
Precipitate must be in suitable form for weighing

Precipitate must be pure, stable, of certain known composition

Remove water efficiently; electrolytes in washing solvent.
Appropriate chemical changes during heating
Example:

AgCl drying in over 100 deg C 130 deg C to remove physically bound water
Higher temperature is necessary if water is trapped in crystals / chemically bound water / or
ensure appropriate chemical changes

CaCaO4 CaO 1100 deg C

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WEIGHING & CALCULATIONS

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APPLICATIONS:
Extensive numbers of inorganic ions are determined with excellent precision and
accuracy

Routine assays of metallurgical samples

Relative precision 0.1 to 1%
Good accuracy

DISADVANTAGES
Careful and time consumin
Scrupulously clean glassware
Very accurate weighing
coprecipitation
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More Terminology
Adsorption is a process in which a substance (gas, liquid, or solid)
condenses onto the surface of a solid

The electric double layer of a colloid consists of a layer of charge

associated with the surface of the particles and a layer with a net opposite
charge in the solution surrounding the particles

A colloid is a finely divided particle (typically with diameters from 10 nm

to 1 mm) that forms a stable dispersion within a medium (air or liquid)

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Types of Colloids
1. Emulsoids
lyophilic (has strong affinity for the solvent, hydrophilic if the sovent is
water) also called gels (hydrogels if the solvent is water); high Temp. is
required for dehydration

2. Suspensoid
lyophobic (has only a small affinity for the solvent); water retained by
coagulation is easily removed by heating above 100oC
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Colloidal Precipitates
Coagulation of Colloids

Coagulate, or agglomerate, the individual particles of most colloids to give a

filterable, amorphous mass that will settle out of solution.

Coagulation can be hastened by heating, stirring, and adding an electrolyte to the

medium.

The charge on a colloidal particle formed in a gravimetric analysis is

determined by the charge of the lattice ion that is in excess when the
precipitation is complete.
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Colloidal Precipitates
Coagulation of Colloids
Coagulation can be hastened by:
1. Heating for a short period of time with stirring, and
2. Adding an electrolyte to the medium
The charge on a colloidal particle formed in a gravimetric analysis is determined
by the charge of the lattice ion that is in excess when the precipitation is
complete.
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Colloidal Precipitates
The electric double layer of a colloid
consists of a layer of charge adsorbed on
the surface of the particle (the primary
adsorption layer) and a layer of opposite
charge (the counter-ion layer) in the
solution surrounding the particle.
Increasing the electrolyte concentration
has the effect of decreasing the volume of
the counter-ion layer, thereby increasing
the chances for coagulation.
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Colloidal Precipitates
Coagulation of Colloids
Coagulation of a colloidal suspension can often be brought about by a
short period

of heating, particularly if accompanied by stirring.

An even more effective way to coagulate a colloid is to increase the

electrolyte concentration of the solution.

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Colloidal Precipitates
Peptization of Colloids
Peptization is a process by which a coagulated colloid returns to its
dispersed state.

A procedure where the precipitate is washed and filtered, but part of the
precipitate reverts to the colloidal form because supporting electrolyte is
gone.
AgCl (s) AgCl (colloid)

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Improving Particle Size and Filterability

Digestion (Aging)
Heating the precipitate within the mother liquor (or

solution from which it precipitated) for a certain period of

time to encourage densification of nuclei.

During digestion, small particles dissolve and larger

ones grow (Ostwald ripening). This process helps
produce larger crystals that are more easily filtered
from solution
DT

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Homogeneous Precipitation
The precipitant is slowly added by a chemical reaction.
Ex. Urea decomposes slowly in boiling water to produce OH O

+
H2N

3H2O CO2 + 2NH4+ + 2 OH-

NH2

The Gradual OH production enhances the particle size of Fe(III)

formate to precipitate
O

H
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+ OH- HCO2- + H2O

OH

3HCO2- + Fe3+ Fe(HCO2)3n H2O (s)

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Purity of Precipitates
1. Co-precipitation Error
is the precipitation of an unwanted species along with your analyte of
interest;
occurs to some degree in every gravimetric analysis;
A major factor for precipitations of barium sulfate and those involving hydrous
oxides

and cannot be avoided, but can be minimized by careful precipitation and

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a thorough washing of the precipitate.

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Purity of Precipitates
a. Surface adsorption
Unwanted material is adsorbed onto the surface of the
precipitate

Contamination by adsorption causes significant error only in

cases in which the precipitate has a very large surface area.

Digestion of a precipitate reduces the relative surface area

and, therefore, the area available for adsorption of
impurities.

Washing can remove impurities bound to the surface.

Gelatinous precipitates, such as hydrous oxides, usually

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cannot be washed free from adsorbed impurities.

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a type of occlusion
Occurs when a precipitate grows in such a manner that there
are holes or pockets in the crystal.
These contains solvent (water) with the dissolved impurities
that were present as the crystal formed.
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Purity of Precipitates
b. Occlusion
impurities or foreign ions in the
counter-ion layer may become
trapped , or occluded within the
growing crystal.

c. Mechanical Entrapment

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Purity of Precipitates
d. Mixed crystal formation
In mixed-crystal formation, one of the
ions in the crystal lattice of a solid is
replaced by an ion of another element

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Purity of Precipitates
2. Post-precipitation Error

- Process in which an impurity is deposited after

precipitation of the desired substance.
Example.
Post precipitation of magnesium oxalate occurs if
a precipitate of calcium oxalate is allowed to
stand too long before being filtered.

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Applications
Extensive numbers of inorganic ions are determined with excellent
precision and accuracy.

Routine assays of metallurgical samples.

Disadvantages
Careful and time consuming.
Scrupulously clean glassware.
Coprecipitation errors

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Advantages
Accurate and precise.
Possible sources of
errors can be checked.
Relatively inexpensive
Does not require a
calibration or
standardization step

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Applications
Other Inorganic Ions

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Applications

Organic Precipitating Agents

Numerous organic reagents have been developed for
the gravimetric determination of inorganic species

8-Hydroxyquinoline (oxine)
O
Mg 2+ + 2

Mg

+ 2H+

N
O

OH

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Selectivity

through pH control

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Applications
8-Hydroxyquinoline (oxine)
Metal

pH

pH

Initial Ppt.

Complete

Metal

pH

pH

Initial Ppt.

Complete

Ppt

Ppt

4.7 9.8

Manganese

4.3

3.7

5.2 9.4

Molybdenum

2.0

3.6 7.3

4.5

5.5 13.2

Nickel

3.5

4.6 10.0

Calcium

6.8

9.2 12.7

Thorium

3.9

4.4 8.8

Cobalt

3.6

4.9 11.6

Titanium

3.6

4.8 8.6

Copper

3.0

>3.3

Tungsten

3.5

5.0 5.7

Iron(III)

2.5

4.1 11.2

Uranium

3.7

4.9 9.3

Lead

4.8

8.4 12.3

Vanadium

1.4

2.7 6.1

Magnesium

7.0

>8.7

Zinc

3.3

>4.4

Aluminium

2.9

Bismuth
Cadmium

Rose Ann Tamolang

5.9 9.5

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Applications
Organic Precipitating Agents

Dimethylglyoxime
CH3
Ni2+ +

2 CH3

CH3

N N

HO

OH

Weakly alkaline conditions

Nickel salt cherry red

CH3

O N N O
H
H + 2H+
Ni
O N N O
CH3

CH3

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2016/2/29

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