General Procedure:

1. Weigh the sample to be analysed

2. Dissolve the sample in a suitable solvent, eg, water
3. Add an excess of the precipitating reagent to precipitate the analyte
4. Filter the mixture to separate the precipitate from the solution
5. Wash the precipitate to remove any impurities
6. Dry the precipitate by heating to remove water
7. Cool the precipitate in a dessicator to prevent the precipitate absorbing moisture from the
air
8. Weigh the cooled precipitate
9. Repeat the drying and weighing process until a constant mass for the precipitate is
achieved
10. Calculate the percent by mass of analyte in the sample

General calculation of the percent by mass of analyte in a sample:

1. Write the balanced chemical equation for the precipitation reaction

2. Calculate the moles of precipitate: moles = mass ÷ molar mass
3. Calculate moles of analyte from the balanced chemical equation using the mole ratio of
analyte : precipitate
(also known as the stoichiometric ratio of analyte to precipitate)
4. Calculate mass of analyte: mass = moles × molar mass
5. Calculate percent by mass of analyte in sample: (mass analyte ÷ mass sample) × 100

Sources of Error:

• 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

Worked Example

Problem 01
A 2.00 g sample of limestone was dissolved in hydrochloric acid and all the calcium present in
the sample was converted to Ca2+(aq).

Excess ammonium oxalate solution, (NH4)2C2O4(aq), was added to the solution to precipitate the
calcium ions as calcium oxalate, CaC2O4(s).

The precipitate was filtered, dried and weighed to a constant mass of 2.43 g.

Determine the percentage by mass of calcium in the limestone sample.

Answer:

1. Wite the balanced chemical equation for the precipitation reaction:

Ca2+(aq) + C2O42-(aq) → CaC2O4(s)

2. Calculate the moles of calcium oxalate precipitated.

moles(CaC2O4(s)) = mass ÷ molar mass

moles(CaC2O4(s)) = 2.43 ÷ (40.08 + 2 x 12.01 + 4 x 16.00)

moles(CaC2O4(s)) = 2.43 ÷ 128.10

moles(CaC2O4(s)) = 0.019 mol

3. Find the moles of Ca2+(aq).

From the balanced chemical equation, the mole ratio of Ca2+ : CaC2O4(s) is 1 : 1

So, moles(Ca2+(aq)) = moles(CaC2O4(s)) = 0.019 mol

4. Calculate the mass of calcium in grams

mass (Ca) = moles × molar mass

mass (Ca) = 0.019 × 40.08 = 0.76 g

5. Calculate the percentage by mass of calcium in the original sample:

%Ca = (mass Ca ÷ mass sample) × 100

%Ca = (0.76 ÷ 2.00) x 100 = 38%

Problem 02 A 0.4550-g solid mixture containing MgSO is dissolved in water and

4

treated with an excess of Ba(NO ) , resulting in the precipitation of 0.6168 g of BaSO .

3 2 4

MgSO4(aq)+Ba(NO3)2(aq)→BaSO4(s)+Mg(NO3)2(aq)

What is the concentration (percent) of MgSO in the mixture?

4

Solution
The plan for this calculation is similar to others used in stoichiometric calculations, the
central step being the connection between the moles of BaSO and MgSO through their 4 4

stoichiometric factor. Once the mass of MgSO is computed, it may be used along with 4

the mass of the sample mixture to calculate the requested percentage concentration.

The mass of MgSO that would yield the provided precipitate mass is
4

The concentration of MgSO in the sample mixture is then calculated to be

4

problem 03 What is the percent of chloride ion in a sample if 1.1324 g of the

sample produces 1.0881 g of AgCl when treated with excess Ag ? +

Ag+(aq)+Cl−(aq)→AgCl(s)Ag+(aq)+Cl−(aq)→AgCl(s)

Stoichiometry helps us determine how much substance is needed or is present. Things that can be measured are;

1. Reactants’ and Products mass

2. Molecular weight
3. Chemical equations
4. Formulas

Stoichiometric Coefficient
Stoichiometric coefficient or stoichiometric number is the number of molecules that participate in the reaction. If you look at any balanced reaction you
will notice that there are an equal number of elements on both sides of the equation. The stoichiometric coefficient is basically the number present in
front of atoms, molecules or ions.
Stoichiometric coefficients can be fractions as well as whole numbers. In essence, the coefficients help us to establish the mole ratio between
reactants and products.

Balanced Reactions and Mole Ratios

Atoms and molecules are extremely small in size and their numbers in a very small amount of a substance are very large. Therefore, to represent
atoms and molecules in bulk, a mole concept was introduced. One mole of any substance contains 6.022 x 10 23 numbers of that substance. This
number is also known as Avogadro’s number.
The mass of one mole of a substance in grams is called molar mass. The molar mass of one mole of a substance is numerically equal to the
atomic/molecular formula mass.
Let us take one example of a balanced chemical equation.
3Fe(s) + 4H2O(l) ⇾ Fe3O4 (s)+ 4H2 (g)
The quantitative information drawn from this balanced chemical equation is

1. 3 mole of Fe reacts with 4 moles of H2O to yield one mole of Fe3O4 and 4 moles of H2.
2. 168g ( 56×3) of Fe reacts with 72g( 18×4) of H 20 to yield 231g of Fe 3O4 and 8g of H2 gas.

If the reactants and products are in gaseous form, then the molar volume is taken into consideration. One mole of any gas occupies 22.4 Litres.
CH4(g) + 2O2(g)⇾ CO2(g)+ 2H20 (g)
In the above reaction, 22.4 Litres of CH4 reacts with 44.8 (2 x 22.4) litres of 0 2 to yield 22.4 Litres of CO2 and 44.8 litres of H2O

Limiting Reagent
In a chemical reaction, it is possible that one of the reactants is present in excess amount. Some of these excess reactants will, therefore, be left over
when the reaction is complete; the reaction stops immediately as soon as one of the reactants is totally consumed.
The substance that is totally consumed in a reaction is called the limiting reagent.
Let us take one example of a chemical reaction to understand limiting reagent concept.
N2 + 3H2 ➝ 2NH3
Suppose we have one mole of N2 reacting with one mole of H2. But from the balanced chemical equation, one mole of N 2 requires three moles of H2.So,
the limiting reagent in this reaction is H2.

Stoichiometry in Chemical Analysis

Stoichiometric calculations which follow a quantitative analysis methodology is often used by chemists to determine the concentrations of substances
present in a sample. There are basically two main types of analysis. We will discuss them below.

1. Gravimetric Analysis
In analytical chemistry, the gravimetric analysis describes the quantitative determination of analyte based on the mass of the solid. The gravimetric
analysis gives the most accurate results out of all other analytical analysis as the weight of a substance can be measured with great accuracy
compared to other fundamental quantities.
Gravimetric analysis can be generalized into the following types.

1. Precipitation gravimetry – It involves isolation of ion in solution by a precipitation reaction, filtering, washing the precipitate free of
contaminants, and finally weighing the precipitate and determining its mass by difference.
2. Volatilization gravimetry – volatilization gravimetry involves separating components of a mixture by heating or chemically decomposing
the sample.
3. Electrogravimetry – It involves the electrochemical reduction of metal ions at the cathode and simultaneous deposition of ions on the
cathode. The cathode is weighed before and after electrolysis and the weight, difference corresponds to the mass of analyte initially present
in the sample.

2. Volumetric Analysis
The volumetric analysis involves the quantitative measurement of substance in terms of volume.
Principle: In volumetric analysis, a known volume (V 1) of the substance whose concentration (N1) is known is reacted with the unknown volume (V2) of
the solution of the substance whose concentration(N 2) is to be calculated. The volume, V 1 is noted at the endpoint of the reaction. The concentration
N2 is calculated using the following equation.
N1x V1 = N2 x V2
The endpoint of such reaction is indicated by a change in colour or precipitation etc.
Terms involved in volumetric analysis;

1. Titration – The process of finding out of the volume of solution required to react completely with the volume of another solution is called
titration.
2. Titrant – The solution of known strength is called titrant.
3. Titrate – The solution whose concentration is to be estimated.
4. Indicator – Indicators are reagents which change their colour when the reaction is complete.

Stoichiometry Problems With Solutions

1. Calculate the mass of sodium hydroxide required to make 500ml of 0.10 M solution.
Solution:
The molar mass of NaOH = 40g
Volume of NaOH= 500ml = 0.5 L
Molarity = 0.10M
Molarity = moles / volume in litres
⇒ weight of NaOH = molarity x molar mass of NaOH x volume
= 0.10 x 40 x 0.5
= 2g
2. How much volume of 11M HCl has to be diluted with water to prepare 3 M 400 ml HCl?
Solution:
M1 = 11M
M2 = 3M
V1 = ?
V2= 400ml
Now, M1 x V1= M2 x V2
⇒V1= (3×400)/ 11
= 109 ml
3. How many carbon atoms are present in 0.5 moles of oxalic acid (C 2H2O4)?
Solution :
1 mole of oxalic acid = 6.022 x 10 23
number of oxalic acid
0.5 mole of oxalic acid = 6.022 x 10 23 x 0.5 number of oxalic acid
Since there are 2 carbon per oxalic acid,
Therefore number of carbon atoms in 0.5 mole of oxalic acid = 6.022 x 10 23
x 0.5 x 2
= 6.022 x 10 23

4. 0.5216g of a solid mixture containing Na 2SO4 is dissolved in water and treated with an excess of BaCl 2, resulting in the precipitation of
0.6168g of BaSO4. What percentage of the mixture was BaS0 4?
Solution:
Na2SO4 + BaCl2 → BaSO4 + 2NaCl
233g of BaSO4 is obtained from 142g of Na 2SO4
So, 0.6168g of BaSO4 is obtained from = (142×0.6168) / 233
= 0.37g
Since the mass of solid mixture is 0.5216g
Therefore, the percentage of BaSO 4 is solid mixture = (0.37/0.5216) x 100
= 70.34%
5. A solution containing 5g of KOH and Ca(OH)2 is neutralized by an acid. If it consumes 0.3g equivalents of the acid, Calculate the
composition of the solution.
Solution:
Let mass of KOH present in mixture = x
Mass of Ca(OH)2 = (5-x)g
Eq. mass of KOH = 56; Eq. mass of Ca(OH)2 = 74/2
Gram equivalent of KOH + Gram equivalent of Ca(OH)2 = gram equivalent of acid
+ = 0.1
⇒ x = 3.83g
Mass of KOH in the sample = 3.83g
Percentage of KOH = (3.83/5) x 100
= 76.6%
Percentage of Ca(OH)2 = x100
= 23.4%