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Ch 20 Volumetric analysis

Key knowledge
• Sources of acids and bases found in water (may include dissolved carbon
dioxide, mining activity and industrial wastes)
• Volume–volume stoichiometry (solutions only) and application of volumetric
analysis, including the use of indicators, calculations related to the preparation
of standard solutions, dilution of solutions and use of acid–base titrations to
determine the concentration of an acid or a base in a water sample
Key Terms – chapter 20
• accurate • equivalence point • standard solution
• acid mine drainage • indicators
• systematic error
• acid rain • mistake
• aliquot • parallax error • titration
• anhydrous • pH curve • titration curve
• average titre • pipette • titre
• burette • precise
• uncertainty
• concordant titres • primary standard
• dilution factor • quantitative analysis • volumetric analysis
• end point • random errors • volumetric flask
20.1 Sources of acids and bases
• • Natural and artificial processes • • Dissolved carbon dioxide tends to
affect the acidity of rainwater and make river water acidic.
waterways. • • In some rivers, the water is basic
• • Rainwater is naturally acidic due due to the reaction of dissolved
to the presence of dissolved carbon carbonate ions from limestone
dioxide. with water.
• • Waste gases such as sulfur • • Acid mine drainage is caused by
dioxide and nitrogen oxides that the oxidation of sulfur (found in
are produced by industry can cause coal or metal ores) to sulfuric acid.
acid rain. • • Toxic heavy metal ions are
• • Unpolluted water in rivers and leached from ores by acidic wastes
lakes has a natural pH between 6.5 produced by mines.
and 8.5.
20.2 Standard solutions
• • A substance is suitable for use as • • A standard solution is a solution
a primary standard if it: of an accurately known
• – is readily obtainable in a pure concentration.
form • • The concentration, in mol L–1, of
• – has a known chemical formula a prepared standard solution can
be determined by measuring the
• – is easy to store without mass of solid dissolved and the
deteriorating or reacting with the volume of solution prepared.
atmosphere
• – has a high molar mass to
minimise the effect of errors in
weighing
• – is inexpensive.
Worked example 20.2.1 CALCULATING THE
CONCENTRATION OF A STANDARD SOLUTION
PREPARED FROM A PRIMARY STANDARD
• Calculate the concentration of a standard • The molar mass (Mr) of NaCl is
solution prepared from 29.22 g of sodium • 23.0 + 35.5 = 58.5 g mol–1
chloride (NaCl) dissolved in a 1.00 L
volumetric flask.
• 1. Use the chemical formula to determine the
molar mass (M) of the compound.
29.22
• 2. Use the mass (m) and molar mass (M) of • n=
58.5
the compound and the formula to determine
the amount, in mol. • n = 0.502 mol
𝑚
• n=
𝑀𝑟
• 3. Use the amount, in mol, to determine the 0.502
concentration of the solution using the • c=
formula 1.00
𝑛 • c = 0.502 mol
• c=
𝑉
Worked example: Try yourself 20.2.1 CALCULATING
THE CONCENTRATION OF A STANDARD SOLUTION
PREPARED FROM A PRIMARY STANDARD
• Calculate the concentration of a standard
solution prepared from 117.0 g of NaCl
dissolved in a 500.0 mL volumetric flask.
• 1. Use the chemical formula to determine
the molar mass (M) of the compound.
• 2. Use the mass (m) and molar mass (M)
of the compound and the formula to
determine the amount, in mol.
𝑚
• n=
𝑀𝑟
• 3. Use the amount, in mol, to determine
the concentration of the solution using
the formula
𝑛
• c=
𝑉
20.3 Calculations involving acids and bases
20.3
• • Given the quantity of one of • 3 Use the mole ratios of
the reactants or products in a reactants and products in the
chemical reaction, the quantity balanced chemical equation to
of all other reactants and calculate the amount, in mol, of
products can be predicted by the required substance.
working through the following • 4 Convert the amount, in mol, of
steps. the required substance to the
• 1 Write a balanced equation for quantity required in the
the reaction. question.
• 2 Calculate the amount, in mol,
of the given substances.
Worked example 20.3.1 A SOLUTION
VOLUME–VOLUME CALCULATION
• What volume of 0.100 M sulfuric acid
reacts completely with 17.8 mL of
0.150 M potassium hydroxide?
• 1. Write a balanced full equation for
the reaction.
• 2. Calculate the amount, in mol, of the
substances with known volume and
concentration.
• 3. Use the mole ratio from the
equation to calculate the amount, in
mol, of the required substance.
• 4. Calculate the volume or
concentration required.
Worked example: Try yourself 20.3.1 A
SOLUTION VOLUME–VOLUME CALCULATION
• What volume of 0.500 M • 1. Write a balanced full equation
hydrochloric acid (HCl) reacts for the reaction.
completely with 25.0 mL of • 2. Calculate the amount, in mol,
0.100 M calcium hydroxide of the substances with known
(Ca(OH)2) solution? The salt volume and concentration.
formed in this acid–base
reaction is calcium chloride. • 3. Use the mole ratio from the
equation to calculate the
amount, in mol, of the required
substance.
• 4. Calculate the volume or
concentration required.
Worked example 20.3.2 SOLUTION
STOICHIOMETRY: A LIMITING REACTANT PROBLEM
• 20.0 mL of a 1.00 M LiOH solution
is added to 30.0 mL of a 0.500 M
HNO3 solution.
• The equation for the reaction that
occurs is:
HNO3(aq) + LiOH(aq) → LiNO3(aq) + H2O(l)
• (a) Which reactant is the limiting
reactant?
• (b) What mass of LiNO3 will the
reaction mixture contain when the
reaction is complete?
(a) Which reactant is the limiting reactant?
(b) What mass of LiNO3 will the reaction mixture
contain when the reaction is complete?
Worked example 20.3.2: Try yourself SOLUTION
STOICHIOMETRY: A LIMITING REACTANT PROBLEM
• 30.0 mL of a 0.100 M H2SO4
solution is mixed with 40.0 mL of
a 0.200 M KOH solution.
• The equation for the reaction
that occurs is:
H2SO4(aq) + 2KOH(aq) → K2SO4(aq) + 2H2O(l)
• (a) Which reactant is the limiting
reactant?
• (b) What will be the mass of
K2SO4 produced by this reaction?
20.4 Volumetric analysis
• • Volumetric analysis is an analytical • • The end point is the point at which the
technique for determining the indicator changes colour.
concentration of a solution by titrating it • • Indicators used in acid–base titrations
against a solution of known concentration must have a sharp end point.
(a standard solution) and volume.
• • Volumetric flasks, pipettes and burettes • • The end point in an acid–base titration
are accurately calibrated pieces of must be at or close to the equivalence
glassware used in volumetric analysis. point.
• • The point during a titration at which the • • Three concordant titres are usually
reactants are present in equivalent obtained during volumetric analysis.
amounts, as indicated by the coefficients Concordant titres lie within 0.10 mL from
in the equation for the reaction, is called highest to lowest of each other.
the equivalence point. • We calculate the mean (average) titre
when there are 3 concordant titres. This
may mean lots of extra titres.
20.5 Calculations in volumetric analysis
• FIGURE 20.5.1 This flow chart
summarises the steps in the
calculation of the concentration
of an unknown substance using
the data from a titration in
which the standard solution was
in the burette.
20.5 Calculations in volumetric analysis
• • The concentration of acidic or basic • • Accuracy refers to how closely a
solutions can be determined by measurement agrees with the true
volumetric analysis. value.
• • Dilution of the unknown solution is • • Precision refers to how closely a set
sometimes required to obtain of measurements are to each other.
manageable titre volumes. • • A systematic error produces a
• • The mole ratio in a balanced constant bias in a measurement,
chemical equation allows the amount, which cannot be eliminated by
in mol, of a species in the equation to repeating the measurement.
be calculated from the amount, in • • A random error has an equal chance
mol, of any other species. of being greater or lower than the
• • All quantitative measurements true value.
involve an error and have an
uncertainty associated with them.
Worked example 20.5.1 SIMPLE TITRATIONS
• The concentration of hydrochloric
acid was determined by titration
with a standard solution of sodium
hydroxide.
• A 25.00 mL aliquot of HCl was
titrated with a 1.00 M solution of
sodium hydroxide. Titres of 25.05
mL, 22.10 mL, 22.05 mL and 22.00
mL were required to reach the end
point.
• What is the concentration of the
hydrochloric acid solution?
Worked example: Try yourself 20.5.1 SIMPLE
TITRATION
• The concentration of a solution of
barium hydroxide (Ba(OH)2) was
determined by titration with a
standard solution of hydrochloric
acid.
• A 10.00 mL aliquot of Ba(OH)2
solution was titrated with a 0.125
M solution of HCl.
• Titres of 17.23 mL, 17.28 mL and
17.21 mL of HCl were required to
reach the end point.
• What is the concentration of the
barium hydroxide solution?
Worked example 20.5.2 TITRATION THAT
INVOLVES DILUTION
• A commercial concrete cleaner
contains hydrochloric acid. A 25.00 mL
volume of cleaner was diluted to
250.0 mL in a volumetric flask.
• A 20.00 mL aliquot of 0.4480 M
sodium carbonate solution was placed
in a conical flask. Methyl orange
indicator was added and the solution
was titrated with the diluted cleaner.
The indicator changed permanently
from yellow to pink when 19.84 mL of
the cleaner was added.
• Calculate the concentration of
hydrochloric acid in the concrete
cleaner.
Worked example: Try yourself 20.5.2
TITRATION THAT INVOLVES DILUTION
• A commercial concrete cleaner
contains hydrochloric acid. A 10.00 mL
volume of cleaner was diluted to
250.0 mL in a volumetric flask.
• A 20.00 mL aliquot of 0.2406 M
sodium carbonate solution was placed
in a conical flask. Methyl orange
indicator was added and the solution
was titrated with the diluted cleaner.
The indicator changed permanently
from yellow to pink when 18.68 mL of
the cleaner was added.
• Calculate the concentration of
hydrochloric acid in the concrete
cleaner.
Chapter review – all questions pp. 541-542
Complete Unit 2 AOS 2 Review pp.543-549