ANALYTICAL CHEMISTRY

PREPARED BY: MS. MARIELL C. DAGATAN

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 LEARNING OBJECTIVES:

Construct a pyramid model on the

Define what is Gravimetric
Analysis; General Steps in Gravimetric
Analysis

Order the general steps in

Gravimetric Analysis

Cite the factors affecting the

Identify the different types of
solubility of precipitates
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precipitates and solubility products

 GRAVIMETRIC ANALYSIS
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 LESSON SUB- TOPICS

TYPES OF
GRAVIMETRIC PRECIPITATES AND
SOLUBILITY
ANALYSIS
PRODUCTS

GENERAL STEPS FACTORS AFFECTING

IN GRAVIMETRIC SOLUBILITY OF
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PRECIPITATION
ANALYSIS
 GRAVIMETRIC
ANALYSIS
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 What is Gravimetric Analysis?
Gravimetric analysis is a method in
analytical chemistry that uses mass
measurements of analytes to make
quantitative assessments of the lab's
procedures.
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 PRINCIPLE OF GRAVIMETRIC ANALYSIS

The mass of an ion in a pure compound can be

determined and then used to find the mass percent of the
same ion in a known quantity of an impure compounds.
 The ion to be studied should be completely precipitated

 The precipitate should be in a pure form.

 The obtained precipitate should filter out easily

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 GENERAL STEPS IN
GRAVIMETRIC
ANALYSIS
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 Steps followed in the Gravimetric Analysis

PREPARATION SEPARATION WEIGHING COMPUTATION

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 Steps followed in the Gravimetric Analysis

The most used method that is employed for isolating

the desired constituent from a solution of a sample,
is precipitation
The precipitate obtained is separated by filtration,
washed free of soluble impurities, dried in a
desiccator or oven, or ignited to remove moisture,
and then weighed
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 Ten (10) detailed steps used in performing
gravimetric analysis experiment:
Step I: Weigh the sample to be analyzed
Step 2: Dissolve the sample in a suitable solvent,
eg, water.
Step 3: Add an excess of the precipitating reagent
to precipitate the analyte
Step 4: Filter the mixture to separate the
precipitate from the solution (3)
Step 5: Wash the precipitate to remove any
impurities (4)
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 Ten (10) detailed steps used in performing
gravimetric analysis experiment:
Step 6: Dry the precipitate by heating to remove
water
Step 7: Cool the precipitate in a desiccator to prevent
the precipitate absorbing moisture from the air.
Step 8: Weigh the cooled precipitate
Step 9: Repeat the drying and weighing process until
a constant mass for the precipitate is achieved
Step 10: Calculate the percent by mass of analyte in
the sample
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 Sources of Error in Gravimetric Analysis:

• Incomplete precipitation results in a value for the percentage

of analyte in the sample that is too low.

• Incomplete drying of the sample results in a value for the

percentage of analyte in the sample that is too high

•Other ions in the sample may also be precipitated resulting in a

value for the percentage of analyte in the sample that is too high
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 TYPES OF
PRECIPITATES
AND SOLUBILITY
PRODUCTS
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 What is Precipitation and a Precipitate?

Precipitation is the formation of a solid in

a solution during a chemical reaction

When the chemical reaction occurs the

solid formed is called the precipitate.
can be determined by using the solubility
rules for common ionic solids
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 Properties of Precipitates

Precipitates are insoluble ionic solid products of a reaction,

formed when certain cations and anions combine in an aqueous
solution
The remaining fluid in a precipitate reaction is called supernatant
liquid (or just the supernate).
The two components of the mixture (precipitate and supernate)
can be separated by various methods, such as filtration,
centrifuging, or decanting.
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 Properties of Precipitates

The use of solubility rules require an understanding of the way

that ions react. Most precipitation reactions are single
replacement reactions or double replacement reactions. A
double replacement reaction occurs when two ionic reactants
dissociate and bond with the respective anion or cation from the
other reactant. The ions replace each other based on their
charges as either a cation or an anion.
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 Solubility Rules
1. Salts formed with group 1 cations and NH+4NH4+
cations are soluble. There are some exceptions for
certain Li+Li+ salts.
2. Acetates (C2H3O−2C2H3O2−), nitrates (NO−3NO3−),
and perchlorates (ClO−4ClO4−) are soluble.
3. Bromides, chlorides, and iodides are soluble.
4.Sulfates (SO2−4SO42−) are soluble with the
exception of sulfates formed with Ca2+Ca2+, Sr2+Sr2+,
and Ba2+Ba2+.
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 Solubility Rules

5. Salts containing silver, lead, and mercury (I) are

insoluble.
6. Carbonates (CO2−3CO32−), phosphates
(PO3−4PO43−), sulfides, oxides, and hydroxides
(OH−OH−) are insoluble. Sulfides formed with group 2
cations and hydroxides formed with calcium, strontium,
and barium are exceptions.
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 Net Ionic Equations
The net ionic equation is the chemical equation that
shows only those elements, compounds, and ions that
are directly involved in the chemical reaction.
AB(aq)+CD(aq)→AD(aq)+CB(s)
The first step to writing a net ionic equation is to separate
the soluble (aqueous) reactants and products into their
respective cations and anions
A+(aq)+B−(aq)+C+(aq)+D−(aq)→A+(aq)+D−
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(aq)+CB(s)
 Net Ionic Equations
Since they go through the equation unchanged, they can
be eliminated to show the net ionic equation

B−(aq)+C+(aq)→+CB(s)

If all products are aqueous, a net ionic equation cannot be

written because all ions are canceled out as spectator ions.
Therefore, no precipitation reaction occurs
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 Equilibrium and non-Equilibrium Conditions
The ion product (Q) of a salt is the product of the
concentrations of the ions in solution raised to the same
powers as in the solubility product expression.
An ion product can in principle have any positive value,
depending on the concentrations of the ions involved.
Only in the special case when its value is identical
with Ks does it become the solubility product. A solution in
which this is the case is said to be saturated.
[Ag+]2 [CrO2−4]=2.76×10−12
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 Equilibrium and non-Equilibrium Conditions

Ksp} = [A+]a [B-]b

Where,

Ksp = solubility product constant

A+ = cation in an aqueous solution
B- = anion in an aqueous solution
a, b = relative concentrations of a and b
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 Equilibrium and non-Equilibrium Conditions

There are three possible conditions for an aqueous

solution of an ionic solid:
 Q<Ksp The solution is unsaturated, and more of the
ionic solid, if available, will dissolve.
 Q=Ksp. The solution is saturated and at equilibrium.
 Q>Ksp. The solution is supersaturated, and ionic solid
will precipitate
 
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 Undersaturated and supersaturated solutions

If the ion product is smaller than the solubility

product, the system is not in equilibrium and no
solid can be present. Such a solution is said to be
undersaturated. A supersaturated solution is
one in which the ion product exceeds the solubility
product.
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 Undersaturated and supersaturated solutions
How to know the saturation status of a solution?
Qsp/Ksp Status
Product concentration too high
>1 for equilibrium; net reaction
  proceeds to left.
=1 System is at equilibrium; no net
  change will occur.
<1 Product concentration too
low for equilibrium; net
reaction proceeds to right.
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 FACTORS
AFFECTING
SOLUBILITY OF
PRECIPITATION
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 Temperature

Basically, solubility increases with temperature. It

is the case for most of the solvents. The situation
is though different for gases. With increase of the
temperature they became less soluble in each
other and in water, but more soluble in organic
solvents.
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 Polarity

In most cases solutes dissolve in solvents that

have a similar polarity. Chemists use a popular
aphorism to describe this feature of solutes and
solvents: "Like dissolves like". Non-polar solutes
do not dissolve in polar solvents and the other
way round.
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 Pressure
 Solid and liquid solutes

For majority of solid and liquid solutes, pressure does not affect
solubility.

 Gas solutes

As for gasses the Henry's law states that solubility of gas is

directly proportional to the pressure of this gas. This is
mathematically presented as: p = kc, where k is a temperature
dependent constant for a gas.
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 Molecular size
The larger the molecules of the solute are, the larger is
their molecular weight and their size. It is more difficult it
is for solvent molecules to surround bigger molecules. If
all of the above mentioned factors ale excluded, a
general rule can be found that larger particles are
generally less soluble. If the pressure, and temperature
are the same than out of two solutes of the same
polarity, the one with smaller particles is usually
more soluble.
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 Stirring increases the speed of dissolving

Stirring only increases the speed of the

process - it increases move of the solvent
what exposes solute to fresh portions of it,
thus enabling solubility. As molecules in
liquid substances are in constant move, the
process would take place anyway, but it
would take more time.
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