Pearson Chemistry 12 Queensland

Chapter 4 Volumetric analysis

4.1 Principles of volumetric analysis

Try yourself 4.1.1
CALCULATING THE CONCENTRATION OF A STANDARD SOLUTION PREPARED FROM A PRIMARY STANDARD

Calculate the concentration of a standard solution prepared from 117.00 g of sodium chloride (NaCl) dissolved in a
500.00 mL volumetric flask.

Thinking Working

Use the chemical formula to determine the molar The molar mass (M) of NaCl is
mass (M) of the compound. 22.99
m + 35.45 = 58.44 g mol−1
M
Use the mass (m) and molar mass (M) of the compound n=
117.00
m 58.44
and the formula n = M
to determine the number of moles.
= 2.00 mol

Use the number of moles to determine the concentration c=

2.00
n 0.5000
of the solution using the formula c = .
V
= 4.00 mol L−1

Try yourself 4.1.2

A SOLUTION VOLUME–VOLUME CALCULATION

Calculate the volume of 0.500 mol L−1 hydrochloric acid (HCl) that reacts completely with 25.0 mL of 0.100 mol L−1
calcium hydroxide (Ca(OH)2) solution. The salt formed in this acid–base reaction is calcium chloride.

Thinking Working

Construct a balanced full equation for the reaction. Ca(OH)2(aq) + 2HCl(aq) → CaCl2(aq) + 2H2O(l)

Calculate the number of moles of the substance with The volume and concentration of calcium hydroxide
known volume and concentration. solution are given, so you use n = cV (remember that
volume must be expressed in litres).
n(Ca(OH)2) = cV
= 0.100 × 0.0250
= 0.00250 mol

Use the mole ratio from the equation to calculate the The balanced equation shows that 2 mol of hydrochloric
number of moles of the required substances. acid reacts with 1 mol of calcium hydroxide.
n(HCl) 2
n(Ca(OH)2 )
=
1
2
n(HCl) = × n(Ca(OH)2)
1
2
= × 0.00250
1
= 0.00500 mol

Calculate the volume or concentration required. The volume of HCl is found by using n = cV.
n
V(HCl) =
c
0.00500
=
0.500
= 0.0100 L = 10.0 mL

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 Pearson Chemistry 12 Queensland
Try yourself 4.1.3
SOLUTION STOICHIOMETRY—A LIMITING REACTANT PROBLEM

30.0 mL of a 0.100 mol L−1 solution of sulfuric acid (H2SO4) is added to 40.0 mL of a 0.200 mol L−1 solution of
potassium hydroxide (KOH). The equation for the reaction that occurs is:
H2SO4(aq) + 2KOH(aq) → K2SO4(aq) + 2H2O(l)

a  Determine which reactant is the limiting reactant.

Thinking Working

Calculate the number of moles of each of the reactants n(H2SO4) = 0.100 × 0.0300
using n = cV. = 0.00300 mol
n(KOH) = 0.200 × 0.0400
= 0.00800 mol

Use the coefficients of the equation to find the limiting The equation shows that 1 mol of H2SO4 reacts with 2 mol
reactant. of KOH.
So H2SO4 is the limiting reactant (it will be completely
consumed).

b  Calculate the mass of K2SO4 that will be produced by this reaction.

Thinking Working

Find the mole ratio of the unknown substance to the From the equation coefficients:
limiting reactant from the equation coefficients: n(K 2SO4 ) coefficient of K 2SO4 1
= =
coefficient of unknown n(H2SO4 ) coefficient of H2SO4 1
coefficient of limiting reactant

Calculate the number of moles of the unknown substance n(K2SO4) = n(H2SO4) ×

1

using the limiting reactant: 1

1
n(unknown) = n(limiting reactant) × mole ratio = 0.00300 ×
1
= 0.00300 mol

Calculate the mass of the unknown substance using: Molar mass of K2SO4 = 174.26 g mol–1
m(unknown) = n(unknown) × molar mass m(K2SO4) = 0.00300 × 174.26
= 0.523 g

4.1 KEY QUESTIONS

1 Weigh the solid primary standard on an electronic balance. Transfer the solid into a volumetric flask using a clean, dry
funnel. Rinse any remaining solid particles into the flask using deionised water. Half fill the flask with deionised water
and swirl vigorously to dissolve the solid. Fill the flask with deionised water to just below the calibration mark. Add
deionised water drop-by-drop up to the calibration line on the flask until the bottom of the meniscus touches the line.
Stopper and shake the solution to ensure an even concentration throughout.
2 The equivalence point is the point in the reaction at which equivalent amounts of acid and base have been mixed
according to the ratio given in the chemical equation. The end point is the point in the titration at which the indicator
changes colour.
3 Near the equivalence point, a very small addition of either the acid or the base in the burette can cause a large
change in pH. A sharp end point is one where the indicator changes colour (due to a large change in pH) with just
one additional drop of the solution being added from the burette. Selecting the indicator based on the expected
equivalence point enables for a sharp end point to be seen.
4 HNO3(aq) + KOH(aq) → KNO3(aq) + H2O(l)
n(HNO3) = cV = 0.100 × 0.0300 = 0.00300 mol
n(HNO3) = n(KOH), therefore n(KOH) = 0.00300 mol
n 0.00300
V(KOH) = c
= = 0.0150 L = 15.0 L
0.200

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 Pearson Chemistry 12 Queensland
5 NaOH readily absorbs moisture from the air and can therefore not be accurately weighed and used as a primary
standard as its concentration cannot be accurately determined from its mass.
m
6 n= = 2.042 = 0.01000mol
M 204.23
n
c= = 0.01000 = 0.2000mol L−1
V 0.050000

n n
7 c = v
= 0.500 =
0.250

n = 0.500 × 0.2500 = 0.125 mol

m = n × M = 0.125 × 105.99 = 13.25 g = 13.3 g
8 a H2SO4(aq) + 2KOH(aq) → K2SO4(aq) + 2H2O(l)
b n(KOH) = cV = 0.300 × 0.0100 = 0.00300 mol
n(H2SO4 ) = 1 n(H SO ) = 0.00300 × 1 = 0.00150
n(KOH) 2 2 4 2
0.00150
V (H2SO4 ) = = 0.0150L = 15.0 mL
0.100
9 a 2HNO3(aq) + Ca(OH)2(aq) → Ca(NO3)2(aq) + 2H2O(l)
b n(Ca(OH)2) = cV = 0.100 × 0.010 = 0.00100 mol
n(HNO3) = 2 × 0.00100 mol = 0.00200 mol
c(HNO3 ) = n
= 0.00200
mol L−1
= 0.133M
V 0.0150
10 The steepest part of the titration curve represents the equivalence point. This occurs in distinctly different pH ranges
that only overlap between pH 6.0 and pH 8.0. Therefore different indicators should be used—phenolpthalein for
titration 1 and methyl orange for titration 2.
11 a phenolphthalein
b pH decreases as the basic solution was in the conical flask; therefore, as acid is added H+ ions increase and
the pH lowers.
c The relative strengths of the acid and base being titrated determine the pH of the solution once the acid and base
have been mixed in the correct mole ratios. Therefore, the pH will be greater than 7 as NaOH is a stronger base
than the ethanoic acid.

4.2 Performing volumetric analysis

Try yourself 4.2.1
SIMPLE TITRATIONS

The concentration of a solution of barium hydroxide (Ba(OH)2) was determined by titration with a standard solution
of hydrochloric acid (HCl).
A 10.00 mL aliquot of Ba(OH)2 solution was titrated with a 0.125 mol L−1 solution of HCl. Titres of 17.23 mL, 17.28 mL,
17.40 mL and 17.21 mL of HCl were required to reach the end point.
Calculate the concentration of the barium hydroxide solution.

Thinking Working

Construct a balanced chemical equation for the reaction. An acid is reacting with a metal hydroxide, or base, so the
products will be a salt and water:
2HCl(aq) + Ba(OH)2(aq) → BaCl2(aq) + 2H2O(l)

Determine the volume of the average titre. The titre of 17.40 mL is discarded as it is not concordant
(i.e. it is not within a range of 0.10 mL from highest to
lowest of the other titre volumes).
17.21 + 17.23 + 17.28
average titre =
3
= 17.24 mL

Calculate the number of moles of the standard solution n(HCl) = cV

that was required to reach the end point. = 0.125 × 0.01724
= 0.002155 mol

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 Pearson Chemistry 12 Queensland

Use the mole ratio in the equation to calculate the n(Ba(OH)2 ) 1

mole ratio = =
number of moles of the unknown substance that would n(HCl) 2
1
have reacted with the given number of moles of the n(Ba(OH)2) = × n(HCl)
2
standard solution.
1
= × 0.002155
2
= 0.001078 mol

Determine the concentration of the unknown substance. c(Ba(OH)2) =

n
v
0.001078
=
0.01000
= 0.108 mol L−1

Express your answer to the appropriate number of
significant figures.
The final result is rounded off to 3 significant figures
corresponding to the smallest number of significant
figures in the original data. Four significant figures are
used in the earlier steps of the calculation to avoid
rounding off errors.
Concentration of the Ba(OH)2 = 0.108 mol L−1

Try yourself 4.2.2

TITRATION THAT INVOLVES DILUTION

A commercial concrete cleaner contains hydrochloric acid (HCl). 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 mol L−1 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.

Thinking Working

Construct a balanced chemical equation. A dilute acid is reacting with a metal carbonate so the
products will be a salt, water and carbon dioxide gas:
2HCl(aq) + Na2CO3(aq) → 2NaCl(aq) + H2O(l) + CO2(g)

Using the concentration of the standard solution, n(Na2CO3) = cV

calculate the number of moles of the known substance = 0.2406 × 0.02000
that reacted in the titration. Remember that volume
= 0.004812 mol
must be expressed in litres.

Use the mole ratio in the equation to calculate the n(HCl)

=
2

number of moles of the diluted unknown solution that n(Na2 (CO)3 ) 1

reacted in the titration. n(HCl) =

2
× n(Na2CO3)
1
2
= × 0.004812
1
= 0.009624 mol

Calculate the concentration of diluted unknown solution V(diluted HCl) = 0.01868 L

reacting in the titration. n
c(HCl) =
V
0.009624
=
0.01868
= 0.5152 mol L−1

Multiply by the dilution factor to determine the Dilution factor =

250.0
= 25.00
concentration of undiluted concrete cleaner. 10.00
So undiluted c(HCl) = diluted c(HCl) × 25.00
= 0.5152 × 25.00
= 12.88 mol L−1

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 Pearson Chemistry 12 Queensland

4.2 KEY QUESTIONS

1 a potassium hydrogen phthalate

b i vinegar
ii deionised water
iii sodium hydroxide
2 Concordant titres are those within 0.10 mL of each other. In this case, 16.22 mL, 16.26 mL and 16.18 mL are
concordant titres.
3 a A burette delivers a precise variable volume of solution.
b A pipette delivers a precise known volume of solution.
c A standard flask is used to prepare a solution of known concentration.
4 Trials 2, 3 and 5 provide concordant titres.
25.46 + 25.38 + 25.42
average titre = 3
= 25.42 mL
5 n(KOH) = cV = 1.34 × 0.02298 = 0.03079 mol
n(H2SO4 )
= 1 , therefore n(KOH) × 1
= n(H2SO4) = 0.01540 mol
n(KOH) 2 2
n
= 0.01540 = 0.770 mol L−1
V 0.02000

6 a CH3COOH(aq) + NaOH(aq) → CH3COONa(aq) + H2O(l)

b n(NaOH) = cV = 0.995 × 0.02156 = 0.02145 mol
c n(NaOH) = n(CH3COOH) = 0.02145 mol
n
d c(CH3COOH) = = 0.02145 = 0.858 mol L−1
V 0.02500

7 n(Na2CO3 ) = cV = 0.5000 × 0.02500 = 0.01250 mol

n(HCl)
= 2 , therefore
n(Na2CO3 ) 1
n(HCl) = 2 × 0.01250 = 0.02500 mol L−1
n
c(HCl) = = 0.02500 = 1.045mol L−1
V 0.02392
250.0
dilution factor = = 10
25.00
concentration = 1.045 × 10 = 10.45mol L−1

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