VICTORIA JUNIOR COLLEGE

CHEMISTRY DEPARTMENT

CHEMISTRY PRACTICAL REVISION (9729/04)

Practical Exam Format

Duration: 2 h 30 min
Marks: 55 (20% weighting)

This paper will assess the following skill areas:

● Planning (about 15 marks out of 55)
● Manipulation, measurement and observation (MMO)
● Presentation of data and observations (PDO)
● Analysis, conclusions and evaluation (ACE)

Contents
1. Volumetric analysis (titration)
o Acid-base
o Redox
o Redox iodometric

2. Gas Collection
o Using water
o Using syringe

3. Gravimetric analysis (thermal decomposition)

4. Thermochemistry (Energetics)
o Non-graphical
o Graphical

5. Solubility & Solubility product

o Using filtration
o Using crystallisation

6. Chemical Kinetics
o Initial rate method
o Continuous method

7. Quantitative Analysis
o Inorganic compounds
o Organic compounds

8. Organic Synthesis & Purification

o Reflux
o Distillation
o Purification

1
1 Volumetric Analysis (titration)

1.1 Acid–base titrations and their end–points

Indicator Acid Alkali End–point pH range

Phenolphthalein colourless Pink pink/ colourless 8.2 – 10
Thymol blue yellow Blue green 8.0 – 9.6
Methyl orange red Yellow orange 3.2 – 4.4
Thymolphthalein colourless Blue pale blue/ 8.8 – 10.5
colourless

Phenolphthalein, thymolphthalein and thymol blue indicators can be used for SA–SB and WA–
SB titrations.
Methyl orange indicator can be used for SA–SB and SA–WB titrations.

1.2 Redox titrations involving MnO4–(aq) and their end–points

● Usually Fe2+ or hot C2O42– is titrated against KMnO4.

● No indicator is required because the first drop of permanent pale pink can be seen clearly
and sufficient to indicate the end-point of the titration.

Colour change

(a) MnO4– + 8H+ + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+ pale yellow to pale
Purple pale green colourless yellow pink / peach colour

(b) 2MnO4– + 16H+ + 5C2O42– → 2Mn2+ + 8H2O + 10CO2 colourless to pale

about 70oC pink

(c) 2MnO4– + 5H2O2 + 6H+ → 2Mn2+ + 8H2O + 5O2 colourless to pale

pink

1.3 Redox iodometric titrations and their end–points

● It involves the liberation of iodine from the reaction of an oxidising agent (e.g. IO3–, MnO4–
or Cu2+) and excess KI. I2 liberated is then titrated against S2O32–.
● 1 cm3 (half dropper full) of starch solution is added near the end point when [I2] is low, i.e.
when the solution is pale yellow.
● The end–point is reached when the deep blue colour is discharged, i.e. become colourless,
unless there are other coloured ions present. Always look out for a distinct colour change
at the end–point.
E.g. IO3– + 5I – + 6H+ → 3I2 + 3H2O
I2 + 2S2O32– → 2I– + S4O62–

1.4 Recordings and Choice of Titres

Precision
Pipette readings 1 decimal place e.g. 10.0 or 25.0 cm3
Burette readings 2 decimal places to nearest 0.05 cm3 e.g. 21.45 cm3
Mass readings 3 decimal places unless otherwise stated;
must weigh within given range.

2
 ● For titration table, you must record at least two consistent readings within ±0.10 cm3.

E.g. 1 2
23.70 23.75

● Show how the titre volume is obtained in the summary statement, even though it may seem
obvious; choose only consistent readings.

E.g. 1 Volume required = (23.70 + 23.75) / 2 = 23.73 cm3

E.g. 2 Volume required = (11.10 + 11.10) / 2 = 11.10 cm3

1.5 Calculations

● Indicate units in all calculations.

● Round off all the answers to 3 significant figures (unless stated otherwise).
● The following formulae are useful in calculating and justifying the amounts of chemicals
used.

o Amount of solutes for solids = mass (g) / molar mass (g mol–1)

o Amount of solutes for solutions = concentration (mol dm–3) x volume (dm3)

o Molar conc (mol dm–3) = mass conc (g dm–3) / molar mass (g mol–1)

o Dilution
E.g. Pipette 10.0 cm3 and dilute to 250 cm3 in a volumetric flask
CfVf = CiVi (number of moles of solute does not change)
Cf = CiVi / Vf

1.6 Percentage error of apparatus

● Uncertainty of an apparatus reading can be estimated by taking half of the smallest

division.

E.g. Uncertainty of a burette reading = ±0.05 cm3 (smallest division = 0.10 cm3)

● Percentage apparatus error = (uncertainty / value measured) x 100%, hence,

percentage error decreases for a larger value measured.

● If the titre volume is V cm3, % apparatus error = (2 x 0.05 / V) x 100%

Explanation: Since titre volume = final burette reading – initial burette reading, and
each burette reading contributes an uncertainty of ±0.05 cm3. Hence uncertainty of titre
value = 2 x ±0.05 cm3
1.7 Titration Planning

Your plan should include details of how a standard solution is prepared with details such as
mass of substance to be used or volume of a solution is to be used together with mention of
apparatuses utilized. This will then be followed by the essential details of the titration procedure.

A general procedure is given below:

• Preparation of standard solution (only where appropriate):

3
 - Weigh accurately the solid sample (state the mass used) and dissolve the entire solid
sample in a beaker first before transferring quantitatively into the standard or volumetric
flask.
- Top up to the mark with distilled water (or any other solution as instructed).
- Shake the mixture well to obtain a homogenous solution.

• Pipette 10.0 (or 25.0) cm3 of FA 1 into a conical flask. Add 2 to 3 drops of ___ indicator
(where necessary) into the conical flask.

• Titrate the mixture against FA 2 from the burette until a colour change is observed to obtain
the end–point.

• Repeat the titration as many times as necessary to obtain consistent results to within ±0.10
cm3.

Sequence: Prepare standard solution (if necessary)  pipette  titrate  repeat

Exercise 1: GCE A–Level 2010 Paper 2 Planning

We usually think of iron occurring in compounds in the +2 or +3 oxidation states. However, other
oxidation states of iron are possible; for example, potassium ferrate(VI), K2FeO4, contains iron in the
+6 oxidation state.

Solutions containing the FeO42– ion are dark red in colour. The FeO42– ion is a stronger oxidising agent
than the MnO4– ion. In acidic conditions, FeO42– ions are reduced to Fe3+ ions.

A student was given a solution, FA1, containing potassium ferrate(VI). She was asked to find the
concentration of FeO42– ions in FA 1 by titrating it against a standard solution of sodium ethanedioate,
Na2C2O4.

Ethanedioate ions are oxidised as shown in the following equation.

C2O42– → 2CO2 + 2e–

She tested the 0.100 mol dm–3 solution of Na2C2O4 provided. She found that 10 drops of FA 1, when
suitably acidified, required 32 drops of this Na2C2O4 solution for complete reaction. She correctly
decided that the concentration of this solution was too low and prepared a more concentrated solution
of Na2C2O4, FA2, for titration against the FA 1 solution.

(a) Construct a balanced equation for the reaction between FeO42– ions and C2O42– ions. [1]
FeO4 + 8H + 3e  Fe
2– + – 3+
+ 4H2O
Overall equation: 2FeO42– + 16H+ + 3C2O42–  2Fe3+ + 8H2O + 6CO2
ll: 2FeO42– + 3C2O42–+ 16H+→ 2Fe3++ 6CO2 + 8H2O
(b) Explain why the 0.100 mol dm–3 solution of Na2C2O4 first provided would have been unsuitable for
use in the student's titration. [1]
o Volume of Na2C2O4 required to reach end-point would exceed the capacity of the burette.
E.g. 25 cm3 of FA1 would need 3.2 x 25 = 80 cm3 of FA2.
OR
o A very small volume of FA1 has to be used so that the volume of FA2 needed at end-point
would not exceed the capacity of the burette. But too small a volume of FA1 used (e.g. less
than 10 cm3) would lead to a high percentage error in volume measured.

(c) Write a plan for the volumetric analysis of FA 1. You may use the reagents and apparatus normally
found in a school or college laboratory.

In your plan you should give:

4
 • details, including quantities, for the preparation of FA 2 from solid anhydrous Na2C2O4;
• essential details of the titration procedure. [7]

First, calculate a suitable mass of Na2C2O4 to prepare 100 cm3 of FA 2.

2
• Approximate [FeO42–] x volume of FeO42– = x [C2O42–] x volume of C2O42––––– (1)
3
• Since 10 drops of C2O42– reacted with 32 drops of FeO42–
2
Approximate [FeO42–] = [ x 0.100 x 32] ÷ 10 = 0.213 mol dm–3
3

• Let the volume of FeO42– needed to react with 25.0 cm3 of C2O42– be 25.0 cm3.

From (1), [C2O42–] = [ 3/2 x 0.213 x 25.0] ÷ 25.0

= 0.320 mol dm–3

• To prepare 100 cm3 of solution of 0.320 mol dm–3 Na2C2O4,

Mass of Na2C2O4 required = (0.320x0.100) x (23.0x2 + 12.0x2 + 16.0x4)

= 4.29 g
Procedure:
1) Weigh accurately about 4.29 g of Na2C2O4 in a small beaker.
2) Add distilled water to the beaker to dissolve Na2C2O4 and transfer the solution
quantitatively into a 100 ml volumetric flask. Make up to the mark with distilled water.
Shake the flask to give a homogenous solution. Label this homogenous solution as FA2.
3) Reweigh the empty beaker to find the exact mass of Na2C2O4 used.
4) Pipette 25.0 cm3 of FA2 into a conical flask and add to it 25 cm3 of dilute H2SO4 (an excess)
using a measuring cylinder.
5) Titrate FA2 in the conical flask against FA1 in the burette, swirling to ensure even mixing,
until a colour change is observed. Record the burette reading.
6) Repeat steps 4 – 5 until consistent readings within ± 0.10 cm3 are obtained.

Note: The sequence of setting up the standard solution, burette and conical flask is not important.
If you have placed pipetting 25 cm3 FA1 as the first step, it's also ok, but weighing and making standard solution
must come before setting up the burette.
Since the question asking for essential details of titration, we must provide the correct apparatus to use, as
well as the correct acid for providing the acidic medium. Sulfuric acid is a good choice because sulfate is stable
and does not get oxidised easily.

i) In the student's titration, she found that x cm3 of FA 1 reacted with exactly y cm3 of FA2 of
concentration M mol dm–3. Outline how you would use her results to determine the concentration
of FA 1. [2]
ŋ(FeO42–) ÷ ŋ(C2O42–) = 2 / 3
(CFA1 x X) / (M x y) =2/3
∴ CFA1 = (2My / 3x) mol dm–3

ii) Identify one potential safety hazard in this experiment and state how you would minimise this risk.
[1]
• Ethanedioate (or FeO42–) may be toxic so gloves must be worn when handling solutions
to avoid accidental ingestion of chemicals. OR

• H2SO4 or FeO42– may be corrosive, hence gloves and lab coat must be worn to avoid
contact with skin.

5
2 Gas Collection

Chemists may wish to collect gases in the laboratory for a variety of reasons, including:

1) to identify an unknown gas evolved

2) to calculate the percentage purity of a solid sample (from which the gas is evolved)
3) to calculate the Mr of a solid sample (from which the gas is evolved)
4) to measure the rate of a reaction

The method of gas collection depends on 2 properties of the gas: (a) solubility in water; (b) density
of gas compared to air

Methods of Gas Collection:

(a) Downward Displacement of water [collect over water]

– Suitable for
● slightly soluble or almost
insoluble gases
● gases that have almost the
same density as air
– Examples are oxygen,
nitrogen, carbon monoxide,
carbon dioxide, and hydrogen

Delivery tube

Plastic basin
Heat

(b) Using a gas syringe dropping

funnel
– For collecting dry gases that
have almost the same
density as air
– For collecting and
measuring volume of gases
per unit time interval
[rate of reaction]
– Examples are oxygen or carbon
dioxide

6
Set-up with drying agent to collect Using liquid drying agent such as concentrated sulfuric acid
dry gases.

Using solid drying agent such as anhydrous CaCl2

7
2.1 Collection of data [heating + gas collection]
The order of measurements taken during the above experiment is:
o mass of empty tube
o mass of tube + contents before heating
o reading the initial volume and final volume on the measuring cylinder and
o mass of tube + residue after heating

2.2 Sources of errors and improvements

Sources of errors Suggested improvements

(i) Slightly soluble gas, such as CO2 Use syringe
dissolve in the water, resulting in
inaccurate volume of gas collected.

(ii) Measuring cylinder has a lower Use burette for higher precision
precision, resulting in a larger percentage
error for volume of gas collected over
water.

(iii) Reaction is exothermic; expansion of gas Measure the volume of gas evolved at a
takes place leading to an increase in later time when the temperature
volume of gas collected. This expansion in equilibrate (or no more change in gas
volume is not accounted for. volume)

(iv) When adding a solution to a solid, for e.g. Subtracting the volume of solution added
HCl(aq) to MgCO3(s), the volume of gas from the measured volume of gas.
measured includes air displaced by the
solution.

2.3 Gas Collection Planning

Your plan should include the pre–calculated mass of substance to be used that the total volume
of gas evolved should be about 50% to 80% of the capacity of gas syringe, measuring cylinder
or burette used to collect the gas.

Example: Decomposition of MCO3

Sample procedure using gas syringe:

1) Accurately measure XXX g of the sample in a boiling

tube.
2) Record the initial reading of the syringe.
3) Start heating the solid gently then strongly until the
plunger of the syringe does not move.
4) Allow time for the volume of the gas to equilibrate to
room temperature and pressure, or no more
movement of piston. Solid sample
5) Record the final reading of the syringe.
6) Repeat the experiment to check for reliability of results.

Gas syringe can be replaced by the downward displacement of water method using either
upturned measuring cylinder or burette.

8
Example 1: Planning an Experiment involving Gas Collection

In determining the molar gas constant, R, in the ideal gas equation, a student proposed the following
reaction of barium sulfite with 0.50 mol dm–3 dilute hydrochloric acid.

BaSO3(s) + 2HCl(aq) → BaCl2(aq) + SO2(g) + H2O(l)

By collecting the sulfur dioxide gas and measuring its volume and other variables in the ideal gas
equation, the molar gas constant, R, may be determined experimentally.

(a) Explain why dilute sulfuric acid should not be used.

• Dilute sulfuric acid should not be used because the impervious layer of insoluble
salt BaSO4 forming around the barium sulfite could stop the reaction prematurely.
[1]
(b) The student suggested collecting sulfur dioxide gas through the downward displacement
of water. Suggest why this is not a suitable method.

• SO2 is highly soluble in water; gas collected will be less than expected. [1]

(c) Draw a labelled diagram of the apparatus and the setup you would use to

• add the acid without loss of gas on mixing;

• collect and measure the volume of gas produced.

Your diagram should show how standard pieces of laboratory apparatus are assembled.
You should also show clearly how these pieces of apparatus are connected together.

[3]

(d) What is the maximum mass of barium sulfite that should be used in the experiment to
produce 100 cm3 of sulfur dioxide gas?

Assumptions:
• 1 mol of any gas occupies a volume of 24 dm3 at room temperature and pressure.
• All gas produced is collected and measured in your experimental setup.

Maximum volume of gas collected = 100 cm3

Amount of gas = 100 / 24000 mol = Amount of BaSO3
Mass of BaSO3 = 100 / 24000 x (137 + 32.1 + 3(16.0)) = 0.905 g [1]

9
(e) List, in the order in which they will be made, the measurements you would take during
the experiment.

You should
• ensure the completion of the reaction;
• make appropriate measurements of all the variables in the ideal gas equation.

List of measurements:
1. Weigh accurately about 0.905 g barium sulfite in a weighing bottle.

*Record the total mass of weighing bottle and the sample, m1. Transfer this into a
250 cm3 conical flask. Reweigh the emptied weighing bottle and record its mass m2.
The mass of barium sulfite sample used = m1 − m2

2. Measure the volume of acid used (ensure it is in excess) with appropriate equipment
(e.g. pipette or burette or measuring cylinder) and record as Vacid.
*Suggest > 16.7 cm3 of 0.50 mol dm−3 dilute HCl into the thistle funnel if 0.905 g of
BaSO3 is used

If 0.905 g of BaSO3 is used,

nBaSO3 = 0.905 / [137 + 32.1 + 3(16.0)] = 0.905 / 217.1 = 4.17 x 10–3 mol
nHCl / nBaSO3 = 2/1
nHCl = 8.34 x 10–3
VHCl = 8.34 x 10–3 / 0.50 = 16.7 x 10–3 dm3 = 16.7 cm3

3. Measure the maximum volume of gas collected by reading off the graduated gas
syringe when the piston stops moving.
*Record Vbefore = volume reading before experiment, Vafter = volume reading after
experiment. V = Vafter − Vbefore (−Vacid if thistle funnel is used)

4. Record temperature and pressure reading of the collected gas at the end of the
collection [using thermometer and barometer respectively]. [4]

(f) (i) Explain clearly why there is a discrepancy between the value of the molar gas
constant obtained in this experiment with the theoretical value of 8.31 J K–1 mol–1.

• SO2 is not an ideal gas (since the molecules experience a greater intermolecular
force of attractions or significant molecular volume) OR SO2 is soluble in water.

(ii) A teacher recommended the use of zinc metal instead of barium sulfite for this
experiment. Suggest how this change could improve the accuracy of the
experimental value of the molar gas constant, R.

• The reaction of acid and metal will product H2 gas. H2 deviates less from ideal
gas behaviour since the intermolecular forces of attraction between H2 molecules
are weaker than that between SO2 molecules.

OR [2]

• H2 is less soluble in water.

10
3 Gravimetric Analysis

3.1 Involving Thermal decomposition

Experiments that require heating techniques are carried out on solid samples of salts using
boiling tubes or crucibles.

Below are some examples of experiments that use heating techniques.

(i) To determine the relative molecular mass, Mr of X and calculate the percentage by mass of
water of crystallization in the salt, X.5H2O.
(ii) To determine the percentage by mass of sodium hydrogencarbonate in a mixture of sodium
chloride and sodium hydrogencarbonate.
(iii) To determine the percentage by mass of barium hydroxide in a hydrated sample of the
compound.

3.11 Collection of data and calculations

● Record mass readings to 3 decimal places (unless otherwise stated) and must weigh within
the stated range. E.g between 2.50 to 3.00 g means any mass within the range given.
But if asked to weigh accurately about 2.50g then need to weigh 2.50g ± 0.005
● Record all relevant mass readings. The last two mass readings obtained should differ
by < 0.05 g.
● Extend or modify the table provided if necessary.

Mass of tube and FA 1 after heating / g 21.980

21.754
21.738
Mass of empty tube / g 20.641
Mass of FA 1 after heating / g 1.097
Or

Mass of tube and FA 1 after heating / g 21.980 21.754 21.738

Mass of empty tube / g 20.641 20.641 20.641
Mass of FA 1 after heating / g 1.339 1.113 1.097

11
3.12 Calculations

● Give 3 decimal places for mass addition or subtraction.

Correct answers to 3 significant figures for other calculations involving multiplication or
division.
● Loss in mass after heating = mass of water of crystallisation (for hydrated sample without
undergoing thermal decomposition)
● Loss in mass after heating = mass of gases produced (for compound undergoing thermal
decomposition)

E.g. 2NaHCO3(s) → Na2CO3(s) + H2O(g) + CO2(g)

The data collected can be tabulated as shown.

mass of boiling tube mass of boiling

mass of empty mass of solid
and solid before tube and residue mass loss / g
boiling tube / g used / g
heating / g after heating / g
A B C B–A B–C

Use the letters in the table above to find

(i) the mass of NaHCO3 in the mixture,
[Ar: C, 12.0; H, 1.0; O, 16.0; Na, 23.0]

nH2O = nCO2 = n
mH2O + mCO2 = B – C = 18nH2O + 44nCO2 = 62n
n = (B – C) / 62
Amount of NaHCO3 = 2n = (B – C) / 31 mol
Mass of NaHCO3 in the mixture = 84 x (B – C) / 31 = 2.71(B – C)

(ii) the percentage by mass of NaHCO3 in the mixture.

Percentage by mass of NaHCO3 in the mixture

= [2.71(B – C) / (B – A)] x 100%
= [271 (B – C) / (B – A)] %

3.13 General procedure (choice of apparatus and amounts of chemicals used)

1) Weigh a clean and dry boiling tube.

2) Add a given amount of solid (about 5 g) into the tube and reweigh.
3) Heat the mixture strongly to decompose the solid. Heat the whole length of the tube to
prevent condensation and cracking of the tube.
4) Cool the tube before reweighing to find the mass of the tube and residue.
5) Repeat the heating, cooling and reweighing processes until constant mass is achieved
where consecutive mass difference is less than 0.050 g.

Example 2: Planning a Gravimatric Experiment

Sodium carbonate, Na2CO3, does not decompose on heating with a Bunsen burner. Sodium
hydrogencarbonate, NaHCO3, decomposes on heating.

2NaHCO3(s) → Na2CO3(s) + H2O(g) + CO2(g)

You are to design an experiment in which the percentage by mass of NaHCO3 in a mixture of NaHCO3
and Na2CO3 can be determined by heating and weighing alone.
12
The only apparatus available consists of a boiling tube and holder, a chemical balance and a Bunsen
burner.
You are to show how you would use the results of this experiment to determine the percentage by
mass of NaHCO3 in the mixture.

(a) Outline, step by step, the practical sequence for the method you would use to
• make appropriate weighings,
• decompose the sodium hydrogencarbonate in the mixture by heating,
• ensure that decomposition was complete.

Sequence of steps Answers

Find initial mass of empty boiling 1) Weigh the empty boiling tube.
tube.
Find total mass of tube and its 2) Add the mixture of NaHCO3 and Na2CO3 into the boiling
contents. tube, and reweigh the tube.

• Heat gently and then strongly 3) Heat the tube gently and then strongly to decompose
• Hold tube at 45oC angle to the salt.
allow even heating and escape 4) Hold the boiling tube at 45o angle to the flame to ensure
of CO2 and H2O vapour even heating of the salt, and to allow CO2 and water
evolved. vapour given off to escape from the tube.
Cool before weighing the tube and
5) Cool and weigh the tube and its contents.
its contents
Repeat till decomposition is
complete, i.e. constant mass is 6) Repeat steps 3 and 4 till the difference between
obtained consecutive mass readings is within ±0.050 g.
(mass difference = ±0.050 g)

(b) By considering the products of the decomposition, suggest a reason why a crucible, without a lid,
might be more appropriate than a boiling tube for this experiment. [1]

Water vapour would condense on the cooler part of the boiling tube and cracking it. However, in
a crucible, water vapour can escape easily without condensing.

(c) Prepare a table to show the masses you would measure and record during the experiment.
Include in your table any other masses you would calculate from the experimental results to
enable you to determine the percentage by mass of NaHCO3 in the mixture. Insert in your table
the letters A, B, C etc. to represent each mass. Use these letters to show how your calculated
masses are obtained e.g. E = B – A.

Mass of empty boiling tube / g A

Mass of boiling tube and mixture before heating / g B
Mass of boiling tube and residue after heating / g C
Mass of mixture used / g B–A
Mass loss due to CO2 and H2O / g B–C

(d) Use the letters you have entered in (c) to show how you would process the results to find

(i) the mass of NaHCO3 in the mixture,

[Ar: C, 12.0; H, 1.0; O, 16.0; Na, 23.0]

2NaHCO3(s) → Na2CO3(s) + H2O(g) + CO2(g)

13
 Sequence of steps Answers
• Understand that mass loss is due to Mass loss
mass of CO2 + H2O = Mass of H2O + CO2 = B – C

• Convert mass loss to amount of H2O mH2O + mCO2 = B – C

or amount of CO2 18nH2O + 44nCO2 = B – C

• Show relationship between amount And nH2O = nCO2 = n

of H2O and amount of CO2
• Show relationship between amount Hence, 62n = B–C
of H2O or amount of CO2 and mass n = (B–C)/62
loss

• Show mole relationship of NaHCO3 nNaHCO3 = 2nH2O = 2nCO2 = 2n

& CO2 / H2O
• Find amount of NaHCO3 Mol of NaHCO3 = 2n
= 2(B – C)/62
= (B – C)/31

• Find Mr of NaHCO3 Mr of NaHCO3 = 84

• Multiply Mr and mole to get mass. Mass of NaHCO3 in the mixture

= (B – C)/31 x 84 = 2.71(B – C)

(ii) the percentage by mass of NaHCO3 in the mixture.

Sequence of steps Answers

• Take mass of NaHCO3 divide by Percentage by mass of NaHCO3 in the mixture
initial mass of mixture
• Multiply by 100 to get percentaage = [2.71(B – C) / (B – A)] x 100
= 271 (B – C) / (B – A) %

[4]
[Total: 12]

3.2 Involving Solubility of Salts

Example 3: To study the effect of temperature on solubility using gravimetric analysis

The solubility of calcium hydroxide in water, at a particular temperature, can be defined as the
maximum mass of calcium hydroxide that can dissolve in and just saturate 100 cm3 of water at
that temperature. It can be represented by the following equation:

mass of calcium hydroxide (in g)

solubility =
100 cm3 of water

A saturated solution is one in which no more solid can dissolve at a particular temperature.

When calcium hydroxide dissolves in water, the following equilibrium is established.

Ca(OH)2(s) + (aq) ⇌ Ca2+(aq) + 2OH–(aq) -------------------- (1)

This equilibrium takes about 30 minutes to establish.

You are to plan an experiment to investigate how the solubility of calcium hydroxide in water
depends on the temperature of the solvent.

14
In addition to the standard apparatus present in a laboratory, you are provided with the following
materials.

• 1 dm3 distilled water

• 50 g solid calcium hydroxide, Ca(OH)2
• water bath
• thermometer
• mass balance

(a) Give a step-by-step description of how you would

• prepare a saturated solution of Ca(OH)2 from distilled water,
• control the temperature of the experiment to be between 0 ºC to 50 ºC,
• separate the saturated solution from undissolved calcium hydroxide,
• obtain the mass of undissolved calcium hydroxide.

1. Measure 100 cm3 of deionized water using a measuring cylinder into a clean and
dry conical flask (or beaker).
2. Place the conical flask (or beaker) in a thermostatically controlled water bath
maintained at 10 °C and use a thermometer to monitor the temperature of the
solution inside the conical flask (or beaker).
3. Weigh accurately about 5.00 g of solid Ca(OH)2
4. Once the temperature inside the conical flask (or beaker) reaches 10 °C, transfer
the contents from weighing bottle into the conical flask (or beaker).
5. Using a glass rod, stir the mixture. Then leave the mixture to stand over a period
of 30 min for equilibrium to be established.
6. Weigh the emptied weighing bottle to obtain the actual mass of Ca(OH)2 used.
7. Weigh a dry filter paper.
8. Filter the reaction mixture using the weighed filter paper to obtain the
undissolved CaOH)2.
9. Dry the residue and filter paper by leaving it for some time under infra-red light
or in an oven.
10. Weigh the dry residue and filter paper.
11. Repeat steps 1 to 11 four more times at temperatures of 20 ºC, 30 ºC, 40 ºC, 50
ºC.
[6]

(b) Suggest how you may determine the solubility of calcium hydroxide from the experimental
results.

Mass of weighing bottle and Ca(OH)2 / g B

Mass of weighing bottle and remaining Ca(OH)2 / g C
Mass of empty weighing bottle / g A
Mass of Ca(OH)2 weighed out / g B–A
Mass of Ca(OH)2 added / g B–C

Mass of filter paper and residue /g E

Mass of filter paper /g D
Mass of residue (Ca(OH)2) / g E–D

Mass of Ca(OH)2 dissolved / g (B – C)– (E – D)

(𝐁𝐁−𝐂𝐂)−(𝐄𝐄−𝐃𝐃)
Solubility of Ca(OH)2 =
𝟏𝟏𝟏𝟏𝟏𝟏
[2]

[Total: 8]

15
4. Thermochemistry (Energetics)

4.1 Recordings and Calculations

● Temperature: 1 decimal place

● Mass reading: 3 decimal places (unless otherwise stated) and must weigh within the
stated range

● If measuring cylinders are used, volumes of solutions are measured in cm3 to nearest
whole number. All calculations should be rounded off to the number of significant figures
of the least accurate measurement.

● Balance the equations when necessary, including state symbols.

● Calculate the weighted average for the initial temperature of mixture if different volumes
of solutions are mixed, unless otherwise stated.
E.g. 60 cm3 NaOH (25.0 oC) mixed with 30 cm3 HCl (26.0 oC)
Initial Temperature = (60 x 25.0 + 30 x 26.0) / (60 + 30)
= 25.66 oC
= 25.7 oC

● Heat evolved / absorbed = V (cm3) x c (J g–1 oC–1) x∆T (oC)

(This is not ∆H. Do not include + or – signs since evolved or absorbed is mentioned. )

● Determine number of moles of the limiting reagent.

● ∆H = kJ mol–1 or J mol–1

● ∆H calculated must include ‘+’ or ‘– ‘ sign and the units.

16
4.2 Non–Graphical Determination of Enthalpy Change of Reaction

General procedure:
• Use a measuring cylinder to transfer an appropriate volume of limiting reagent (at least
20 cm3) into a polystyrene cup and measure the initial temperature.
• Use another measuring cylinder to measure an appropriate volume of the second solution
(excess or based on stoichiometric ratio in the balanced equation), measure its initial
temperature.
• Add the second solution into the polystyrene cup. Stir the mixture gently using the
thermometer provided and record the highest / lowest temperature reached.
• Rinse and dry the polystyrene cup.
• Repeat the experiment using a different set of volumes of reagents. Keep total volume of
mixture (not more than 120 cm3) constant for the different experiments for simpler
comparison.

Reason: Heat change = mc∆T.

Since total volume, m and c are the same for both experiments
Heat change ∝ ∆T

4.3 Determination of Enthalpy Change of Combustion of a Fuel

General Procedure:
• Use a measuring cylinder to introduce 100 cm3 into the copper calorimeter.
• Place the thermometer in the water and take its initial temperature.
• Place some XXX into the spirit lamp. Put a wick into it and weigh the spirit lamp and its
contents. Record the mass, m1.
• Place the spirit lamp under the calorimeter and light up the spirit lamp.
• Stir the water gently with the thermometer. (Do not let the thermometer touch the base of
the copper calorimeter.)
• When the temperature of the water has increased by about 5 oC, extinguish the spirit lamp.
• Weigh the spirit lamp and its contents immediately. Record the mass, m2.
• Read the highest rise in temperature and calculate the ∆T.
• Calculate the mass of XXX used (i.e. m1 – m2)
• Repeat the experiment to get reliable results.

17
4.4 Graphical Determination of Enthalpy Change of Reaction

● For slow reactions (i.e. more than 3 minutes)

Maximum temperature, Tmax

Tmax accounts for heat

loss to surroundings

∆Tmax

Note: For endothermic reactions, the shape of the graph will be flipped vertically.

General procedure:
• Use a XXX cm3 burette/pipette/measuring cylinder, introduce XXX cm3 of YYY solution
into a clean and dry styrofoam cup.
• Place the thermometer into the solution and start the stopwatch.
• At regular time interval of 0.5 min, record the temperature of the solution.
• Weigh accurately XXX g of solid YYY. Take note of the weight of the weighing bottle and
the salt.)
• Use a measuring cylinder, introduce XXX cm3 of YYY solution into the styrofoam cup at
the 3 minute point. / Introduce the solid into the cup at the 3 minute point.
• Stir gently with the thermometer.(Reweigh the emptied bottle)
• Do not record the temperature at the 3 minute point. But record the temperature at 0.5
min interval after the 3 minute point for about 10 minutes with continuous stirring.
• Repeat the experiment to get reliable results.

Note: The graphical method is more accurate as it takes into consideration the gain of
heat from/heat loss to the surrounding.

4.5 Thermometric Titration

● This method involves adding one reactant (the

titrant) continuously or stepwise to another
reactant. The enthalpy change(s) of the ensuing
reaction(s) causes a temperature change which,
when plotted versus volume of titrant, may be used
to find the titration endpoint(s) as shown below:

Note: The V shape will be flipped for

endothermic reactions.

18
 General procedure:
• Use a pipette/burette, introduce XXX cm3 of the YYY solution into a clean and dry
styrofoam cup.
• Place the thermometer into the solution and take note of the initial temperature of the
solution after some time.
• Use a burette, introduce 5.00 cm3 of YYY solution.
• Stir gently with the thermometer. Take note of the highest rise in temperature.
• Repeat steps (iv) to (v) until a total volume of 40 cm3 of YYY solution has been added.
• Plot a graph of temperature rise versus volume of YYY solution added. The intersection
point will give the volume of YYY solution that is needed to completely react with the
acid.
• Repeat the experiment to get reliable results.

4.6 Sources of Errors and Improvement

Commom sources of errors Suggested Improvements

(i) Excessive heat loss resulting in lower
measured ∆T may due to
• Insufficient lagging of the cup
• Presence of draughts
• Lag the cup to minimize heat transfer to the
surrounding
• Switch off the fans and stand the apparatus
in a metal shield to reduce heat loss due to
draughts

(ii) Slow response time of thermometer • Use a data logger with a temperature probe
results in inaccuracy in ∆T measured for more accurate measurement of ∆T

(iii) Heat absorbed by the thermometer and •
Styrofoam cup not accounted, resulting in
lower (higher) measured ∆T and hence
leading to less exothermic (more
endothermic) heat change and ∆H
Use a calorimeter with a pre–determined
heat capacity to take into account the heat
absorbed by the calorimeter

(iv) Error in volume transfer due to poor • Use more precise apparatus such as
precision of measuring cylinder resulting burette or pipette to give a more accurate
in inaccuracies in the calculations for heat measurement of volume of solution
change and ∆H

4.7 Thermochemistry planning

● Identify the limiting reagent, use a measuring cylinder or pipette to measure it. Use an
excess of the other reagent.
● Keep the total volume of reaction mixture the same for all the experiments so as to allow
for simpler comparison, i.e. in calculations, Q = Vc∆T, V is kept constant.
● Rinse the polystyrene cup thoroughly before carrying out the next experiment. Rinse
the measuring cylinder if it is contaminated with a solution of a different salt / concentration.
● Use reasonable volumes of solutions, e.g. 25 or 30 cm3 and NOT 2 cm3 or 300 cm3.
● State clearly, e.g. pour the second solution in one go quickly without spilling into the cup,
stir gently with the thermometer and note the highest (lowest) temperature reached.
● Include explanation or calculations on how the identities of the solutions are deduced.
Show clearly how the weighted average initial temperature is obtained.
19
Example 4: To identify 1 mol dm–3 NaOH, 1 mol dm–3 HCl and 1 mol dm–3 H2SO4

● Mix equal volumes, e.g. 20 cm3, of any two solutions. The one with ∆T= 0 contains the two
acids. Thus, NaOH can be identified.

FA 1 & FA 1 & FA 2 &

FA 2 FA 3 FA 3

● Next, add NaOH to the two acids separately. Volume of NaOH used > 2 x volume of acid used,
i.e. the acid is the limiting reagent.

50 cm3
50 cm3
NaOH &
20 cm3 NaOH &
20 cm3 HCl
H2SO4

● NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l) ∆H1

2NaOH(aq) + H2SO4(aq) → Na2SO4(aq) + 2H2O(l) ∆H2

● The total volume used is the same for both experiments and heat evolved = mc∆T. Thus, m and
c are the same in both experiments and heat evolved α ∆T.

● It can be deduced that ∆T for 1 mol dm–3 H2SO4 is twice that of 1 mol dm–3 HCl since twice the
amount of NaOH is neutralised by H2SO4 as compared to that of HCl.

● Alternatively, using the acid used as the limiting reagent in each experiment, calculate the ∆H for
each acid.

● Hence, either ∆T or ∆H can be used for the identification of the acids, since the total volume used
in each experiment is the same.

20
Example 5: To identify 1 mol dm–3 NaOH, 1 mol dm–3 HCl and 2 mol dm–3 HCl

● Mix equal volumes, e.g. 20 cm3, of any two solutions. The one with ∆T = 0 contains the two
acids. Thus, NaOH can be identified.

● Next, add NaOH to the two acids separately. Volume of NaOH used > 2 x volume of acid used,
i.e. the acid is the limiting reagent.

50 cm3 NaOH 50 cm3 NaOH

& 20 cm3 & 20 cm3
1 mol dm–3 2 mol dm–3
HCl HCl

● NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(l) ∆H1

1 mol dm–3

NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(l) ∆H2

2 mol dm–3

● The total volume used is the same for both experiments and heat evolved = mc∆T. Thus, m
and c are the same in both experiments and heat evolved α ∆T.

● It can be deduced that ∆T for 2 mol dm–3 HCl is twice that of 1 mol dm–3 HCl since twice the
amount of NaOH is neutralised by 2 mol dm–3 HCl as compared to that of 1 mol dm–3 HCl.
● Using the acid used as the limiting reagent in each experiment, ∆H2 = 2 x∆H1. Hence, it is not
necessary to calculate ∆H.

Example 6 : Identifying Solutions by Comparing ∆T on mixing Two Solutions

You are provided with 150 cm3 of each of the three solutions FA 1, FA 2 and FA 3. You are required
to plan a simple experiment to identify the three solutions (FA 1 to FA 3).
The three solutions are:

1.00 mol dm–3 HCl 2.00 mol dm–3 HCl 1.00 mol dm–3 NaOH

You are provided with a thermometer and other common apparatus in the laboratory.
( NO pH indicators are provided )

(a) Write down the equation for the reaction involved between aqueous sodium hydroxide and
hydrochloric acid. [1]
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)

(b) Outline a step–by–step procedure to determine the identity of the solutions. [5]

Sequence of steps Answers

• Mention apparatus used.
• Use same volume of reagents. (FA1
+ FA2)
• Record initial temperature of
solution in the cup.
1. Using a measuring cylinder, add 25 cm3 of
FA 1 into a polystyrene cup and record its initial
temperature.
2. Using another measuring cylinder, measure
25 cm3 of FA 2 and record its initial temperature.

Mix the 2 solutions and record any 3. Add the 25 cm3 of FA 2 into the polystyrene cup
temperature change. containing FA 1, stir gently and record the
highest temperature reached, if any.

Clean the apparatus used. 4. Rinse the cup and measuring cylinders.
21
 Repeat experiment for another pair of 5. Repeat steps 1 to 4, this time replacing FA 2 with
solutions. (FA1 + FA3) FA 3.

Repeat experiment for last pair of 6. Repeat steps 1 to 3, this time replacing FA 1 with
solutions. (FA2 + FA3) FA 3.

Identify NaOH and the 2 acids. 7. From the above experiment, the pairs of solutions
with no temperature change must be the two
acids. The remaining solution must be NaOH.

• Measure a known volume of NaOH. 8. Use a measuring cylinder, measure 50 cm3 of

• Measure its initial temperature. NaOH and pour it into a polystyrene cup. Record
its initial temperature.

• Make the acid to be limiting reagent
by making the volume of acid used
to be half the volume of NaOH.
• Mix the 2 solutions.
• Measure highest temp reached.
Clean apparatus used.
Repeat experiment for the other acid.
9. Use a measuring cylinder, measure 25 cm3 of
one of the acids, and pour it into the cup. Record
the highest temperature obtained.
10. Rinse the polystyrene cup and measuring
cylinder.
11. Repeat steps 8 and 9 with the other acid.

(c) Illustrate how the identity of each of the solutions can be deduced based on the ∆T obtained in
the procedure above. [3]

Sequence of steps Answers

Write balanced equation of
reaction between NaOH & HCl NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)

Show relationship between ∆T Heat evolved by reaction = ∆Hneut x nH2O formed = mc∆T
and amount of H2O produced
As ∆Hneut and total volume of two mixtures used for both
experiments are the same,

⇒ ∆T α nH2O formed

Calculate amount of NaOH and

HCl used based on the volumes
used for each mixture in (b).
Hence, calculate the amount of
water produced from each
mixture in (b).
Amount of NaOH used = 50/1000 x 1 = 0.0500 mol
For 1 mol dm–3 HCl,
Amount of HCl used = 25/1000 x 1 = 0.0250 mol
⇒ Amount of water produced = 0.0250 mol
For 2 mol dm–3 HCl,
Amount of HCl used = 25/1000 x 2 = 0.0500 mol
⇒ Amount of water produced = 0.0500 mol

Explain that ∆T for 2 mol dm–3 As amount of H2O produced by 2 mol dm–3 HCl will be double
HCl will be twice that for 1 mol that produced by 1 mol dm–3 HCl,
dm–3 HCl.
Hence, ∆T for 2 mol dm–3 HCl is twice that for 1 mol dm–3 HCl.

22
 (d) State and explain one safety precaution to be noted in the procedure. [1]

• Polystyrene cup should be placed in a beaker to avoid toppling of the cup.

(e) Identify two areas to be noted to ensure the reliability of the result. Explain your answer. [2]

Any two below:

• Lagging is provided for the polystyrene cups to minimize the heat transfer with the
surroundings.
• Total volume of solution should be above 40 cm3 as too low a volume has a high error on
the temperature readings.
• Reaction mixture is stirred upon mixing to ensure thorough mixing of the two solutions and
faster completion of reaction.
• Experiments are conducted under draught–free conditions to prevent excessive heat loss
to the surroundings.
[Total: 12]

5 Solubility & Solubility product (Ksp)

5.1 Filtration Method

● Ensure that the stopper fits the reagent bottle well and a saturated solution is achieved as
indicated by the presence of undissolved solute.
● Shake the mixture well, intermittently for at least 10 minutes, to allow equilibrium to be
established before filtering the solution into a DRY conical flask.
● Determine the concentration of ions in the filtrate by titration.
● Record as in volumetric analysis (see section 1.1.4). Equations must be written with state
symbols.
● Substitute the total concentration, including those contributed by the common ion, in
calculating Ksp. Give the correct units for Ksp.

E.g. Total [OH–] = 0.0482 mol dm–3

[OH–] from NaOH = 0.0200 mol dm–3
[OH–] from Ca(OH)2 = 0.0482 – 0.0200 = 0.0282 mol dm–3
Since Ca(OH)2(s) ⇌ Ca2+(aq) + 2OH–(aq)
[Ca2+] = 0.0282 /2 = 0.0141 mol dm–3
Ksp = [Ca2+][OH–]2 = 0.0141 x (0.0482)2 = 3.28 x 10–5 mol3 dm–9

● Ksp is independent of concentration but it is dependent on temperature, i.e. Ksp is a

constant at a constant temperature.
● Solubility of a sparingly soluble salt is lowered in the presence of common ions and
increased during complex ion formation.

23
5.2 Crystallisation Method

You can watch the experiment at https://www.youtube.com/watch?v=XwA2m1fsXf4

● Ensure that the boiling tube is dry and clean before transferring the stated volume of
solvent (water) into it using a burette.
● Clamp the tube in a water bath and warm the water bath gently so as to avoid loss of
solvent.
● Gently stir the contents in the tube with the thermometer until all the solid has dissolved.
Then, remove the tube from the water bath for cooling.
● Stir and watch the solution carefully for the first appearance of fine crystals and note the
temperature at this point.
● Repeat the experiment, minimum 3 experiments, using different volumes of solvent.
Hence, the solubility of the solute at different temperatures can be obtained.

Explanation: Using same mass of solute in different volumes of solvent,

1) When volume is small, there is a high concentration of solute. Since solubility is high at
high temperature, first appearance of crystal will be at a relatively high temperature.

2) As more solvent is added, the solution is no longer saturated at the same temperature,
the crystal dissolves. As the solution cools, fine crystals will appear again as solubility
decreases at a lower temperature.

● Record mass readings as shown by the electronic balance (3 decimal places) unless
otherwise stated, must give the reading within the stated range.
● Record temperature readings to 1 decimal
place and volumes of solvent (water) to 2
Solubility /
decimal places since a burette is used.
g dm–3
● Solubility at T1oC / g dm–3
= mass of solid used / volume of solvent
T / oC
● Plot a graph of solubility against temperature. 25
The solubility of the solute at any temperature
can then be deduced.
● Major sources of errors inherent in the experiment are
 human reaction time in detecting the first deposition of fine crystals which leads to
inaccurate temperature recorded and
 evaporation of water from the tube which leads to inaccurate solubility calculated.

24
6 Chemical Kinetics

Differences between Initial rate and Continuous Methods

Initial rate method Continuous method

1. Do several experiments: 1. Do only 1 experiment
- Concentration change for reactant is - Concentration changes for reactant is left
controlled by you HOW? to nature;
- keep Vtotal constant so that volume of
reactant varied means concentration of
that reactant is changed.

2. Need to monitor the same observation or 2. Need to monitor changes in concentration by

measurement by measuring time taken. taking samples, quenched (if necessary) at
Rate α 1/t regular time intervals and analysing required
reactant.

3. Analyse results using inspection or plot graph 3. Analyse results by plotting graph of [reactant]
of Rate vs [reactant] to see shape. vs time to see shape.

(a) If straight line horizontal to [rxt] ⇒ 0 order (a) If get downward straight line graph ⇒
wrt reactant constant rate hence 0 order wrt reactant

(b) If straight line passing through origin, ⇒ 1st

order wrt reactant (b) If get a downward sloping curve, find 2 t1/2
and compare whether equal; if yes means
Or could be asked to calculate Vt and V2t and 1st order wrt reactant
see which is constant.

6.1 Initial Rate Method: (see example 2 for a sample procedure)

● Keep the total volume of the reaction mixture constant by adding varying amount of water
in each experiment. Thus, Vreactant 〈 [reactant] initial. Check if acidic or alkaline medium is
required for the reaction to proceed.
● When to stop the stopwatch depends on the physical change involved in the reaction.

E.g. For a reaction involving a colour change, you need to decide on the intensity or
occurrence of the colour to be observed and to be consistent for all the experiments.
If a precipitate is formed during the reaction, place the conical flask on a piece of
paper with printed words on it so that the precipitate formed will cover/ obscure the
words.
If a gas is evolved during the reaction, use a graduated syringe to measure the volume
of gas evolved.
If a change in pH occurs during the reaction, a suitable indicator can be used to detect
the change.
● If the colour change is immediate, e.g. 5I– + 6H+ → 3I2 + 3H2O, then a small fixed amount
of ‘delaying factor’ is necessary, e.g. S2O32–, in this case to react with a fixed amount of
I2 liberated.

25
 6.1.1 Data Evaluation on Initial Rate Method

(i) By comparing 1/t

(ii) Calculating vnt
• For constant values of t, Vt or V2t, reaction is zero, first or second order wrt A
respectively.
• Alternatively, as rate = k[A]n, from the shape of the graph of 1/t or 1000/t against
volume of A obtained, the order n wrt A can be determined.
t = constant Vt = constant V2t = constant
Thus, V ∝ 1/t Thus, V2 ∝ 1/t
Thus, initial rate = constant
As V ∝ [A] & rate ∝ 1/t As V ∝ [A] & rate ∝ 1/t
regardless of the initial [A].
Hence, rate ∝ [A] Hence, rate ∝ [A]2
If rate is zero order wrt A. If rate is 1st order wrt A. If rate is 2nd order wrt A.

• A horizontal line will be • A straight line passing • A curve passing through the
obtained since rate = k. through the origin will be origin will be obtained since
obtained since rate = k[A]. rate = k[A]2.

1/t or 1000/t 1/t or 1000/t 1/t or 1000/t

2r 4r

r
r
0 0 0
Vol of A V 2V Vol of A V 2V Vol of A

6.2 Continuous method

*Only 1 reaction mixture prepared but sampling is done at regular time intervals

1. Remove samples from the reaction mixture at certain time intervals from the start of the
reaction. The time, t, indicates how long the reaction has progressed.
2. Pipette samples well before the quenching time, e.g. pipette sample before 2 minutes.
3. Quench the samples immediately at the specified time, e.g. at 2 minutes, such as adding
NaHCO3(s) or adding 100 cm3 of cold water.
Reason: To remove the acid catalyst or to slow down the reaction rate through dilution
(increase volume) and decrease in temperature.
4. Titrate the sample with a suitable titre to determine the [reactant]left or the [product]formed in
the sample.
5. Repeat steps 2 to 4 for different time, t.

The following [reactant]-time graphs are possible:

Zero order reaction First order reaction Second order reaction

Vtitre Vtitre Vtitre

x Constant t1/2

x/2
x/4
0 0 0
time, t t1/2 t1/2 time, t time, t
26
• Alternatively, volume of titre, Vtitre, used at specified time ∝ [product]formed at time t
• Rate of reaction is the gradient of the graph of titre volume (V) against time.

The following [product]-time graphs are possible:

Zero order reaction First order reaction Second order reaction

Vtitre Vtitre Constant t1/2 Vtitre

x
3x/4
x/2

0 0
time, t t1/2 t1/2 time, t 0 time, t

6.4 Kinetics Planning

You need to decide the most suitable method to adopt based on the context of the question.

● Use initial rate method if there is a colour change or precipitate formed (something
observable)
● Use titration or graphical method if one of the reactants or products can be determined by
titration, i.e. acid–base or redox titration.

Example 7
To determine the order of reaction with respect to HCl for the reaction between HCl(aq) and
Na2S2O3(aq) where sulfur is produced in the reaction.

● Limiting reagent is HCl(aq). Hence Na2S2O3(aq) must be in excess.

● Keep the total volume of the reaction mixture constant by adding varying amounts of water.
● Place the conical flask on a piece of paper with printed words as sulfur is formed during the
reaction.

20 cm3 H2O, 10 cm3 H2O, 0 cm3 H2O,

20 cm3 S2O32–, 20 cm3 S2O32–, 20 cm3 S2O32–,
10 cm3 HCl 20 cm3 HCl 30 cm3 HCl

t1 t2 t3

● If t is constant, then reaction is zero order with respect to HCl.

● If Vt is constant, where V = volume of HCl used, then reaction is first order with respect to HCl.
● If V2 t is constant where V = volume of HCl used, then reaction is second order with respect to
HCl.

27
Example 8: (Nov 2000)
To determine the order of the following reaction with respect to KI (aq).

H2O2(aq) + 2I–(aq) + 2H+(aq) → 2H2O(l) + I2(aq)

Vol. of Vol. of Vol. of Vol of Vol. of t/s Vt/ V2 t /

KI, V / H2SO4 / cm3 H2O / cm3 S2O32– / cm3 H2O2 / cm3 cm3 s cm6 s
cm3
25.0 25.0 50.0 10.0 50.0
50.0 25.0 25.0 10.0 50.0
75.0 25.0 0.0 10.0 50.0

● Use measuring cylinders for all volume measurements of solutions. Pipette or burette may be
used for the delaying factor, S2O32–. Addition of starch is recommended.
● Add the solution under study, i.e. KI, lastly in one go quickly without spilling and start stopwatch
at the same instant.
● Swirl the conical flask a few times, e.g. 3 times, and place it back on a white tile. Indicate clearly
when to stop the stopwatch, i.e. when the blue colour appears.
● Ensure constant volumes of S2O32–(aq) and H2O2(aq) are used in each experiment.
● If t = constant, then reaction is zero order with respect to KI.
If V t = constant, then reaction is first order with respect to KI.
If V2 t = constant, then reaction is second order with respect to KI.

Example 9: To determine the order of reaction between CH3COCH3 and I2 wrt CH3COCH3 and I2
respectively
H+ catalyst
• CH3COCH3 + I2 → CH3COCH2I + HI
• To determine the rate of reaction wrt I2, limiting reagent is I2 and CH3COCH3 is in large excess
to ensure that its concentration remain relatively constant as the reaction progresses.

1. Mix 50 cm3 of 0.02 mol dm-3 I2 solution, 25

cm3 of 1 mol dm-3 CH3COCH3 solution and 25
cm3 1 mol dm-3 H2SO4 (catalyst) in a conical At t, add 100
flask. Start timing. cm3 of ice water
2. Before time t, pipette a sample of the to quench the
reaction mixture. reaction.
3. At time t, add a large amount (100 cm3) of ice
water to the pipetted sample to quench
reaction.
Reason: To remove the acid catalyst or to
slow down the reaction rate.
4. Titrate the sample with Na2S2O3 to determine
the [I2]left in the sample.
5. Repeat steps 2 to 4 for different time, t.
6. To determine the order of reaction wrt I2 (see 6.2), plot the graph of Volume of titre, Vtitre,
used at specified time against time t.
7. To find order of reaction wrt CH3COCH3, a similar experiment can be by changing the
[CH3COCH3], e.g. double the original value.
 The initial rate can be found from the gradient of the tangent at t = 0 (for graph plotted in 6)
for both experiments.
• Order of reaction wrt CH3COCH3, n, can then be found from
n
(gradient)expt 1 [CH 3COCH 3 ]expt 1
= n
(gradient)expt 2 [CH 3COCH 3 ]expt 2

28
Exercise 2: GCE ‘A’ Level 2012 Paper 2 Planning

When an acidified solution of hydrogen peroxide is mixed with a solution containing potassium iodide,
starch and sodium thiosulfate, the colourless mixture suddenly turns dark blue after a few seconds.

This is one version of what are known as iodine clock experiments.

A teacher demonstrates this iodine clock experiment as follows.
She prepares two separate solutions, A and B.

Solution A contains starch (0.20 g), potassium iodide (50.00 g), sodium ethanoate (4.10 g) and sodium
thiosulfate (9.40 g) in 1.0 dm3 of water.

Solution B is a mixture of 500 cm3 of 1.5 mol dm–3 hydrogen peroxide and 500 cm3 of 1.0 mol dm–3
ethanoic acid.

She mixes 50 cm3 of solution A with 50 cm3 of solution B and, after about 20 seconds, the mixture
suddenly turns dark blue.

a) In acidic conditions, hydrogen peroxide and potassium iodide react to produce iodine.
Write an ionic equation for this reaction. [1]
H2O2 + 2H+ + 2I– → 2H2O + I2

b) Suggest why the reaction mixture contains both ethanoic acid and sodium ethanoate. [1]
It is a buffer solution hence the pH of the mixture would be maintained fairly constant
throughout the reaction so [H+] is constant.

c) Consider the description of the iodine clock experiment given above.

The order of the reaction with respect to the concentration of hydrogen peroxide may be determined
by performing a number of experiments and then graphically analysing the results.

Write a plan for such a series of experiments. In your plan, you should use the same proportions of
solution A and aqueous ethanoic acid as are described above.

Your plan should ensure that at least one of your experiments would be expected to take
significantly less than 20 seconds.

You may assume that you are provided with the following.

• solution A, having the concentrations of reagents given above

• 1.0 mol dm–3 ethanoic acid
• 7.5 mol dm–3 hydrogen peroxide solution
• deionised water
• the apparatus normally found in a school or college laboratory

Your plan should contain the following.

• the intended concentration of the stock solution of hydrogen peroxide to be used
• details for the preparation of this stock solution from the hydrogen peroxide solution provided
• appropriate quantities and concentrations of solutions
• all essential experimental details
• an outline of how the results would be used to determine the order with respect to the
concentration of hydrogen peroxide

You may find it useful to use 1/time to represent the reaction rate. [9]

Calculation of concentration of hydrogen peroxide to be used:

29
 Solution A Solution B Time
taken /s

H2O2 Ethanoic acid

Concentration, 1.5 1.0

mol dm-3

Volume used to 500 500

mix/cm3

Expt Vol of A used Vol of B used Vol of Time

H2O taken/s

1 50 25 25 0 20

2 (new) 50 25< 25 0 <20

Prepare a new solution B with concentration of H2O2 > 1.5 mol dm–3 since time taken is to be less than
20 seconds.
Proportion of solution A and ethanoic acid is to be kept the same!
Given 7.5 mol dm-3 H2O2 solution, what is the new concentration to dilute to?

[H2O2] in solution B = (500/1000 × 1.5) / 1dm3 = 0.75 mol dm-3

[H2O2] in mixture which gives reaction time 20 s = (50/1000 × 0.75) / 0.1 dm3 = 0.375 mol dm-3

[H2O2] in mixture which gives reaction time less than 20 s must be larger than 0.375 mol dm-3

Choosing a convenient value of 2 times the concentration ([H2O2]mixture= 0.75 mol dm-3), keeping the
total volume constant and same proportion of solution A and ethanoic acid (50 cm3 solution A to 25
cm3 ethanoic acid), maximum volume of H2O2 in the mixture is 25 cm3.
C1V1 = C2V2
[H2O2]stock solution = 100 (0.750) / 25 = 3.0 mol dm-3

Diluting the 7.5 mol dm-3 of H2O2 to 250 cm3 of 3.0 mol dm-3 of H2O2:
Volume of H2O2 required = 250 (3.0) / 7.5 = 100 cm3

A concentration of about 3 mol dm–3 solution of H2O2 could be prepared by using a measuring cylinder
to add 100 cm3 of the stock 7.5 mol dm–3 H2O2 and make up to 250 cm3 with distilled water using a
standard flask. The mixture must be shaken to ensure a homogeneous solution
Procedure:
1. Prepare 3.0 mol dm-3 H2O2 solution as described above
2. Using a 100 cm3 measuring cylinder, measure out 50 cm3 of solution A and pour into a 250 cm3
beaker.
3. Use a 50 cm3 measuring cylinder to measure out 25 cm3 of ethanoic acid and pour into the
same beaker.
4. Use another 50 cm3 measuring cylinder to measure out 25 cm3 of H2O2 solution. Pour solution
B into the beaker containing A and ethanoic acid. Start the stop watch at the same time. Swirl
the mixture.
5. Stop the stop watch when the mixture changes from colourless to dark blue.
6. Repeat with different volumes of A, ethanoic acid, H2O2 and water as indicated in the table
below. The water is measured with another measuring cylinder.
30
 Expt Solution A Volume of H2O2 Volume of Volume of water t 1/t
/cm3 / cm3 ethanoic acid/ cm3 /cm3 /s / s ―1

1 50 25 25 0

2 50 20 25 5

3 50 15 25 10

4 50 10 25 15

5 50 5 25 20

6. Plot a graph of 1/time vs Vol of H2O2. Graph should include the origin.
If the graph is a horizontal line, it is zero order wrt H2O2.
If it is a straight line passing through the origin, it is first order wrt to H2O2.
If it is a parabola/curve, it is second order (or higher) wrt to H2O2.

d) Identify one potential safety hazard in this experiment and state how you would minimise this risk.
[1]
H2O2 and ethanoic acid are corrosive chemicals, so gloves should be worn during the experiment to
minimise contact with the skin.

7 Quantitative Analysis (QA)

7.1 Techniques

Manipulation Manipulative Skill Checklist

Solid sample Avoid using excessive solid
Place enough solid to cover the hemisphere of the test-tube
Solution sample Use 1–2 cm depth of the test-tube unless otherwise instructed
Test for gas Use a correct method for testing of gas (e.g. use a dropper or delivery tube to test
for CO2)

**You need to know what reagents when added would generate a gas!
Examples: Add acid to an unknown containing CO32− or SO32−; add acid to
a metal and add NaOH(aq) to NH4+ with heating.
Addition of Add reagent dropwise
reagent Add reagent until no further change is seen
Do not allow dropper used for transferring reagent to touch the sides of the test-
tube
Shake the test-tube to ensure mixing

**Do not follow instructions blindly. Consider the nature of the reagent being
used in each test and recall the positive test results, e.g. white ppt formed soluble
in excess NaOH(aq) indicates Zn2+ or Al3+ present. Always be prepared to test for
any gases that may be produced before adding in the reagent.

**You need to know what the reagent is meant for before adding so that you
can prepare the appropriate test for gas or look-out for the expected
observations!

31
 Filtration Filter the mixture into a test-tube with a proper technique (e.g. wet the filter paper,
no poking of the filter paper)

Filtrate must be clear. Otherwise, filter again. Use a fluted filter paper to increase
the speed of filtration.
Note: Clear DOES NOT imply colourless.

Heating Heat the substance with a proper technique (e.g. for solution, heat around the
meniscus to prevent mixture from spurting out; for solid, heat the whole length of
test-tube to prevent condensation leading to cracking)

When testing for gases during the heating or warming process, do not let the
litmus paper touched the test-tube.

**Heating is done either for thermal decomposition or driving off a gas that
is soluble in water like NH3.

**In general, if heating is required, liberation of a gas, e.g. CO2, is expected.

7.2 Confirmatory Tests for Gases

**Although all these observations can be found in the QA data sheet provided, it is good
to know them by heart and copy the observations full-scale.

gas test and test result

ammonia, NH3 turns damp red litmus paper blue
gives a white ppt. with limewater
carbon dioxide, CO2
(ppt. dissolves with excess CO2)
chlorine,Cl2 bleaches damp litmus paper
hydrogen, H2 “pops” with a lighted splint
oxygen, O2 relights a glowing splint
turns aqueous acidified potassium manganate(VII) from
sulfur dioxide, SO2
purple to colourless

7.3 Al foil: Test for NO2− or NO3−

Add excess NaOH(aq) followed by Al foil. Heat gently to test for ammonia gas, if any.

Hydrogen gas is always evolved and it is not necessary to record it.

How to differentiate NO2− from NO3−?

 Add dilute hydrochloric or sulfuric acid and warm. If brown NO2 gas (or fumes) is evolved,
then NO2− is present.

7.4 Recording

All observations should be useful in determining the anion(s) or cation(s) present or absent. Do
not record observations that are unnecessary, e.g. test-tube feels warm.

If ppt. may be formed in the test, record either (colour) ppt. formed or no ppt. formed.

32
 **If ppt. formed can be soluble in excess reagent, e.g. NaOH(aq), NH3(aq), H2SO4(aq) to
filtrate after adding NaOH(aq) or NH3(aq), record either (colour) ppt. formed soluble in
excess or (colour) ppt. formed insoluble in excess.

**When a reagent is added to the filtrate, e.g. H2SO4(aq) to filtrate after adding NaOH(aq)
or NH3(aq), do not shake first. Observe the appearance of ppt., if any. Then continue with
the addition of the reagent to the filtrate to confirm the solubility of the ppt. in excess reagent.

Example:
Test Observation Deduction
(a) Add aqueous sodium Pale blue ppt. insoluble in
hydroxide to FA1. excess NaOH(aq)

Filter the mixture and Pale blue residue and Cu2+ present
use the filtrate for test colourless filtrate obtained
(b).
(b) To the filtrate from (a), White ppt. formed, soluble in Al3+ or Zn2+ present
add dilute sulfuric acid. excess H2SO4(aq)

**Do NOT use terms such as no visible reaction, clear solution obtained, limewater turned
milky or chalky.

**For each gas evolved, state its confirmatory test, observations and identity. Identity of
gas is written under the observation column, not the deduction column.

Example:
Test Observation Deduction
Add a small spatula of solid Effervescence of CO2 gas gives FA 1 is acidic
sodium carbonate to FA 1. a white ppt. with lime water

**Be aware of the possibility of more than one coloured ion in the unknown. Thus, colour
mixing takes place and the ‘true’ colours of the ions are usually masked.

**Always write the observations immediately next to the tests carried out, and not anywhere
in the observation column. Similarly, write the corresponding deductions immediately next to
the observations.

7.5 Ions in QA Syllabus

coloured ions
Cations: Al 3+
NH4+ Ba2+
Ca 2+
Cr 3+
Cu2+ Fe2+ Fe3+ Mg2+ Mn2+ Zn2+

Anions: CO32− Cl− Br− I− NO3− NO2− SO42− SO32−

**Do take note that examiners are interested in deductions relating to ions listed in the
syllabus. Time and space are often wasted in listing ions which are not in the syllabus and
which are ignored by the examiners.

The substances to be investigated may contain ions NOT included in the above list. In such
cases candidates will not be expected to identify the ions but to draw conclusions of a general
nature (i.e. state whether the given ion is oxidising, reducing, acidic, basic or amphoteric,
etc.)

Example:
Test Observation Deduction
33
 To 2 cm depth of dilute Effervescence of H2 which FA 1 is a reducing
sulfuric acid, add a little “pops” with a lighted splint agent (FA 1 reduces
FA 1 and cautiously warm H+ to H2)
the mixture. OR FA 1 is a metal

7.6 Solubility of Salts

Ion General Solubility Rule

NO3− All nitrates are soluble for the cations in the A-Level QA syllabus
Cl−, Br−, I− All chlorides, bromides and iodides are soluble except Ag+ and Pb2+
SO42− All sulfates are soluble except Ca2+, Ba2+ and Ag+
CO32− All carbonates are insoluble except Na+, K+ and NH4+
OH− All hydroxides are insoluble except Na+ and K+
Ca(OH)2 is slightly soluble
Na+, K+, NH4+ All are soluble for the anions in the A-Level QA syllabus

34
7.7 **Tests for Cations

7.7.1 NaOH(aq)

• If warming is required after adding NaOH(aq), test for ammonia gas. A positive test
indicates that NH4+ is present.
• If warming is required after adding NaOH(aq) and Al foil, test for ammonia gas. A positive
test indicates that NO2− or NO3− is present.
• If NaOH(aq) is added to a solution, look out for the formation of any ppt., note its colour and
solubility in excess NaOH(aq).

Observation Deduction
White ppt. soluble in excess NaOH(aq) Al3+, Zn2+ present
Ca2+, Mg2+, Ba2+ (impure)
White ppt. insoluble in excess NaOH(aq)
present
Off-white ppt., rapidly turning brown on contact
Mn2+ present
with air, insoluble in excess NaOH(aq),
Pale blue ppt. insoluble in excess NaOH(aq) Cu2+ present
Grey-green ppt. soluble in excess NaOH(aq)
Cr3+ present
giving dark green solution
Green ppt., turning brown on contact with air,
Fe2+ present
insoluble in excess NaOH(aq)
Red-brown ppt. insoluble in excess NaOH(aq) Fe3+ present
No ppt. NH3 produced on heating NH4+ present

Example:
Test Observation Deduction
To 1 cm depth of FA White ppt. formed soluble in excess Al3+ or Zn2+ present
1, add NaOH(aq) NaOH(aq).
and warm gently Damp red litmus paper remained red, NH4+ absent
followed by adding no NH3(g) evolved on warming.
two pieces of
aluminium foil and NH3(g) evolved turns damp red litmus NO3− or NO2− present
continuing to warm paper blue on warming with Al foil.
gently.

7.7.2 NH3(aq)

If NH3(aq) is added to a solution, look out for the formation of any ppt., note its colour and
solubility in excess NH3(aq).

Observation Deduction
White ppt. soluble in excess NH3(aq) Zn present
2+

White ppt. insoluble in excess NH3(aq) Al3+, Mg2+ present

Off-white ppt., rapidly turning brown on
Mn2+ present
contact with air, insoluble in excess NH3(aq),
Blue ppt. soluble in excess NH3(aq) giving dark Cu2+ present
blue solution
Observation Deduction
35
 Grey-green ppt. insoluble in excess NH3(aq) Cr3+ present
Green ppt., turning brown on contact with air,
Fe2+ present
insoluble in excess NH3(aq)
Red-brown ppt. insoluble in excess NH3(aq) Fe3+ present
All above ions absent Ca2+, Ba2+,
No ppt.
Na+, K+, NH4+ may be present

7.7.3 For Acidic Aqueous Cations: Na2CO3(aq) / Na2CO3(s) / NaHCO3(aq) / NaHCO3(s)

• An aqueous solution containing either Al3+, Cr3+ or Fe3+ ions is acidic enough to react with
aqueous sodium carbonate or sodium hydrogencarbonate to produce carbon dioxide gas
together with the formation of a hydroxide precipitate.

• If Na2CO3(aq) or NaHCO3(aq) is added to a solution, look out for the formation of any ppt.
and note its colour. Also, look out for the evolution of CO2 gas due to the presence of high
charge density ions, Al3+, Cr3+, and Fe3+.

Cation Observation Deduction

aluminium, White ppt. Effervescence of CO2 which gives a
Solution is acidic
Al3+(aq) white ppt. with limewater
chromium(III), Grey-green ppt. Effervescence of CO2 which
Solution is acidic
Cr3+(aq) gives a white ppt. with limewater
iron(III), Red-brown ppt. Effervescence of CO2 which
Solution is acidic
Fe3+(aq) gives a white ppt. with limewater

7.8 **Tests for Anions

7.8.1 Dilute HCl / HNO3 / H2SO4

When the above acids are added to solid or aqueous samples, test for gas(es) evolved.
Vigorous effervescence is observed, i.e. bubbles can be seen, when either CO2 or H2 is
evolved.

Observation Deduction
SO2 turns aqueous acidified potassium manganate(VII)
SO32− present
from purple to colourless

Colourless NO → (pale) brown NO2 in air NO2− present

CO2 gives a white ppt. with limewater (ppt. dissolves with

CO32− present
excess CO2)

Exceptions:

Observation Deduction
H2 “pops” with a lighted splint
Reactive metal present
Note: If grey powder is given, test for H2(g).
White ppt. with dilute H2SO4 Ba2+ present

36
 7.8.2 AgNO3(aq)

Addition of AgNO3(aq) to an unknown solution can help infer the following about the solution.

Observation Deduction
White ppt. (AgCl) soluble in NH3(aq) Cl− present
Pale cream ppt. (AgBr) partially soluble in NH3(aq) Br− present
Yellow ppt. (AgI) insoluble in NH3(aq) I− present
Note: All the above ppt. are insoluble in dilute HNO3.

7.8.3 Ba(NO3)2(aq) or BaCl2(aq)

Addition of Ba(NO3)2(aq) or BaCl2(aq) to an unknown solution can help infer the following
about the solution.

Observation Deduction
White ppt. insoluble in excess dilute strong acids SO42− present
White ppt. soluble in excess dilute strong acids SO32− present

How to differentiate SO32− from SO42−?

 Add dilute hydrochloric or nitric acid to the solution and warm. If pungent SO2 gas is
evolved which decolourises acidified KMnO4(aq), then SO32− is present.

7.9 **Colour of halogens

halogen colour of element colour in aqueous solution colour in hexane

greenish yellow
chlorine, Cl2 pale yellow pale yellow
gas
reddish brown gas
bromine, Br2 orange orange-red
/ liquid
black solid / purple
iodine, I2 brown purple
gas

7.10 **Redox reagents: Br2(aq) / KBr(aq) / KI(aq) / CuSO4(aq) or Cu2+(aq) / KMnO4(aq) /

FeCl3(aq) (NOT found in Data Booklet)

Yellow solution turned colourless when Br2(aq) is added to an unknown solution indicates
presence of reducing agent since Br2 has been reduced to Br−.

• Addition of KBr(aq) to an unknown solution can help infer the following about the solution.

Observation Deduction
Aqueous layer turns orange Oxidising agent
Organic layer turns orange-red present

37
 • Addition of KI(aq) o ann unknown solution can help infer the following about the solution.

Observation Deduction
Oxidising agent
Brown solution OR black ppt. in brown solution OR violet gas
present
Aqueous layer turns brown Oxidising agent
Organic layer turns purple present
White ppt. (CuI) in brown solution, brown solution decolourised
Cu2+ present
on adding Na2S2O3(aq)

• Addition of CuSO4(aq) or Cu2+(aq) to an unknown solution can help infer the following about
the solution.

Observation Deduction
White ppt (CuI) in brown solution, brown solution decolourised −
I present
on adding Na2S2O3(aq)
Reducing agent
Pink or red-brown ppt. (Cu), blue solution gradually decolourises
present

• Decolourisation of purple acidified KMnO4(aq) when added to an unknown solution indicates

presence of reducing agent.
• Yellow solution turned pale green when FeCl3(aq) is added to an unknown solution indicates
presence of reducing agent since Fe3+ has been reduced to Fe2+.

7.11 Heating test

Heating of a solid sample should be done last if its residue is not needed to continue in
other tests. After concluding the identities of the anion(s) or NH4+ present, do the heating test
last to deduce the gases evolved.

Test for the gas(es) evolved.

Observation Deduction
NH3 evolved NH4+ present
CO2 evolved CO32− present
SO32− present
SO2 evolved SO42− possibly present if unknown is
Fe(NH4)2(SO4)2
NO2 and O2 evolved NO3− present
X2 and O2 evolved XO3− (X: Cl, Br or I) present

Observe the colour of residue.

Observation Deduction
Yellow when hot, white when cold Zn2+ present
Red-brown or brown Fe compound present
Black Cu, Mn compound present
Above compounds absent. Na+, K+,
White
Ba2+, Ca2+, Mg2+ compound present

38
7.12 Organic QA

**Candidates should also be familiar with simple organic reactions, e.g. test-tube reactions
indicating the presence of unsaturation, alcoholic, phenolic and carboxylic groups.

**Certain functional groups can be identified from the chemical tests shown in the table.

Test Observation Deduction

Shake compound with
aqueous bromine.
Add solid phosphorus
pentachloride to
compound.
Add sodium metal to
compound.
(a) Rapid decolourisation of
orange bromine.
(b) Rapid decolourisation of
orange bromine with
formation of white ppt.
White fumes (HCl gas) formed.
Effervescence of hydrogen gas
which gave a “pop” sound with
a lighted splint.
C=C, phenol or phenylamine
present
Phenol or phenylamine
present
Alcohol present if compound
is neutral
OR Carboxylic acid present if
compound is acidic
Alcohol, phenol or carboxylic
acid present

Add aqueous NaHCO3 Effervescence of carbon Carboxylic acid present

OR Na2CO3 to
compound.
Warm compound with
acidified potassium
dichromate(VI) solution.
dioxide gas which gave a white
ppt. with limewater.
Colour of solution changed Primary alcohol, secondary
from orange to green. alcohol or aldehyde present

Add 2,4- Orange ppt. formed. Carbonyl compound present

dinitrophenylhydrazine or
Brady’s reagent to
compound.
Heat compound with Silver mirror / grey ppt. formed. Aldehyde present
Tollens’ reagent or
Ag(NH3)2+(aq).
Heat compound with Brick-red ppt. formed. Aliphatic aldehyde present
Fehling’s reagent or
alkaline Cu2+(aq).
Heat compound with I2 Yellow ppt. (CHI3) formed. Compound with CH3CH(OH)–
and NaOH(aq). or CH3CO– group present
Boil compound with NH3 evolved which turned red Amide or –CN (nitrile) present
aqueous sodium litmus paper blue.
hydroxide.
Heat compound with White ppt. (benzoic acid) Benzene with side-chain
acidic KMnO4 (or alkaline formed. present
KMnO4 and acidify
products)
Add silver nitrate solution White ppt. formed immediately Acid chloride present
to compound. in strongly acidic solution.
Boil compound with (a) White ppt. formed. chloroalkane present
NaOH(aq); acidify (b) Pale cream ppt. formed. bromoalkane present
products with HNO3, then
(c) Yellow ppt. formed. iodoalkane present
add aqueous AgNO3.

39
7.13 **QA Planning

• Some assessment of planning skills or evaluating evidence and procedures may be

incorporated in a question on qualitative analysis.
• Use only the reagents provided. Do not use any other chemicals that are not in the given list.
• Always keep the number of reactions to a minimum. The last unidentified solution can be
deduced from the given list without performing a confirmatory test for it.
• Use chemical names, symbols, when describing positive observations. Be clear in your
description, e.g. state that the ppt. is soluble in excess of which reagent and the location of
the ion at the specified stage when necessary.

7.14 Examples

**Example 1 (Cationic separation)

Given a mixture of Zn2+(aq) and Mg2+(aq). Separate the cations as a precipitate of its carbonate.
Reagents provided: NaOH(aq), NH3(aq), HNO3(aq), HCl(aq), Na2CO3(aq)

Step Observations Location of each

(1) Add excess NaOH(aq) and
filter. Keep the filtrate for
(3).
(2) Dissolve the residue in
HNO3(aq) and add
Na2CO3(aq) to the solution
obtained.
(3) Add HNO3(aq) to the filtrate
from (1). Then add
Na2CO3(aq).
cation
White ppt. insoluble in Mg2+ in ppt., Zn2+ in
excess NaOH(aq) filtrate
White residue and
colourless filtrate
obtained
White residue dissolved Mg2+ in ppt. as
in HNO3(aq) to give a MgCO3
colourless solution
White ppt. formed when
Na2CO3(aq) added
White ppt. formed and Zn2+ in ppt. as
dissolved in excess ZnCO3
HNO3(aq)
White ppt. formed when
Na2CO3(aq) added

**Example 2 (Anionic separation)

Given a mixture of Cl–(aq) and I–(aq). Separate the anions as separate precipitate.
Reagents provided: NaOH(aq), NH3(aq), HNO3(aq), HCl(aq), AgNO3(aq)

Location of each
Step Observations
anion
(1) Add excess AgNO3(aq). Yellow ppt. formed I– in ppt.

(2) Add excess NH3(aq) to the Yellow ppt. insoluble in I– in ppt.

mixture in (1) and filter. excess NH3(aq)
Colourless filtrate collected Cl– in filtrate

(3) Add HNO3(aq) to the filtrate White ppt. reappeared Cl– in ppt.
obtained in (2).

40
Example 3
You are provided with the following solutions:
• lead nitrate, Pb(NO3)2 N.B. Pb2+ ion not in syllabus
• sodium sulfate, Na2SO4
• iron(III) chloride, FeCl3
• sodium nitrate, NaNO3
• sodium hydroxide, NaOH

(a) Fill in the spaces in the table below to show the expected observations when pairs of
solutions are mixed.

Pb(NO3)2 Na2SO4 FeCl3 NaNO3 NaOH

white ppt.
soluble in
Pb(NO3)2 white ppt. white ppt. no ppt.
excess
NaOH(aq)

Na2SO4 no ppt. no ppt. no ppt.

red–brown
ppt. insoluble
FeCl3 no ppt. in excess
NaOH(aq)

NaNO3 no ppt.

NaOH

(b) One of the solutions can be identified just by observation. Identify the solution and explain
how this is possible.
FeCl3(aq) as it is a yellow solution while the rest are colourless.
..................................................................................................................................

(c) Using these solutions alone, plan the steps which will enable you to identify these
compounds. Record the expected observations and the deductions.

step expected observation deduction

1 Add samples of other 4 One test–tube gave a white ppt. Pb(NO3)2
solutions to separate test– insoluble in excess present
tubes containing FeCl3. One test–tube gave a red–brown NaOH present
ppt. insoluble in excess

Two test–tubes gave no ppt. NaNO3 or

Na2SO4 present
2 Add Pb(NO3)2 to two test– One test–tube gave a white ppt. Na2SO4 present
tubes, one with NaNO3 and
one with Na2SO4.
One test–tube gave no ppt. NaNO3 present

41
 **Example 4 (Organic QA)

There are four test-tubes containing each of the following compounds.

OH O
OH CHO
CH3
COOH
CHO
3-hydroxybenzaldehyde 2-hydroxybenzoic acid acetophenone cinnamaldehyde

(a) Predict what you would expect to observe when each of the four compounds is subjected
to the four tests separately.

2,4-DNPH Tollens’ neutral

compound bromine water
reagent reagent FeCl3(aq)
OH
Orange Br2 water
Orange ppt. Silver mirror Violet
turned colourless;
formed observed colouration
white ppt. formed
CHO
OH No silver Orange Br2 water
No ppt. Violet
mirror turned colourless;
observed colouration
COOH observed white ppt. formed

O
No silver No color
Orange ppt. Br2 water
CH3 mirror change
formed remained orange
observed observed

CHO No color
Orange ppt. Silver mirror Orange Br2 water
change
formed observed turned colourless
observed

Exercise 3

(b) You are required to plan the steps which will enable you to identify the chemicals present in
each of the solutions. You may use ONLY the reagents as shown in the table and no others.
You should aim to use the minimum number of reactions. Record the expected
observations and the deductions.

step expected observation deduction

1. Add bromine water to • Br2 water remained orange Acetophenone present
each of the solutions. in one solution.
• Orange Br2 water turned Cinnamaldehyde present
colourless in one solution.
• Orange Br2 water turned 3-hydroxybenzaldehyde or
colourless and white ppt. 2-hydroxybenzoic acid present
formed in two of the
solutions
2. Add 2,4-DNPH to each of • Orange ppt. formed. 3-hydroxybenzaldehyde present
3-hydroxybenzaldehyde
and 2-hydroxybenzoic • No orange ppt. formed 2-hydroxybenzoic acid present
acid.

42
(c) (i) At room temperature, 2-hydroxybenzoic acid exists as a white solid while acetophenone
exists as a liquid. Explain the relative difference in the melting points of the 2 compounds.

Hydrogen bonding exists between 2-hydroxybenzoic acid molecules while acetophenone

molecules are held together by weaker permanent dipole-permanent dipole
interactions. Hence, more energy is needed to separate 2-hydroxybenzoic acid
molecules.

Melting point of 2-hydroxybenzoic acid is above room temperature while that of

acetophenone is below room temperature.

(ii) Solid 2-hydroxybenzoic acid can dissolve in acetophenone to

give a colourless organic layer. Assume that both organic
compounds are totally insoluble in water, plan an experiment
which will enable you to separate the two organic compounds
when mixed together.

Hint: Separating funnel can be used to separate two immiscible

liquids.

expected
step deduction
observation
1. Add NaOH(aq) to the test- Two layers The organic layer will contain
tube containing both (organic and acetophenone while the aqueous
organic compounds. aqueous) layer will contain the salt of
2. Separate both layers seen. 2-hydroxybenzoic acid.
using a separating funnel.
3. Add HCl(aq) to the White solid White solid is 2-hydroxybenzoic acid.
aqueous layer. formed.
4. Filter the white solid
formed, wash it with
distilled water and dry the
solid.

(iii) Using the listed chemical reagents only, how would you verify that each of the organic
compounds separated is not contaminated with the other compound?

Add 2,4-DNPH to 2-hydroxybenzoic acid solution. If it is contaminated with acetophenone,

orange ppt. will be seen.

Add neutral FeCl3(aq) to acetophenone. If it is contaminated with 2-hydroxybenzoic acid,

violet colouration will be seen.

43
8 Organic Synthesis & Purification

By and large, organic compounds contain mainly covalent bonds. Covalent bonds are typically
harder to break, which is why organic reactions happen at a relatively slower rate than inorganic
reactions.

Inorganic are faster because the reactants are already in ionic form so ready to bond and form
products. In organic reactions, bond breaking has to take place prior to bond formation.

Hence synthesis of organic compounds are often carried out under reflux.

8.1 Reflux

A reflux is performed in a chemical reaction so that a solution may be heated to a boiling point
without losing the solvent to evaporation. If you heat any liquid to its boiling point, the inevitable,
and inherent, consequence is evaporation, leading to loss of solvent.

Hot

Figure 1: Reflux set-up

Reflux involves heating the chemical reaction for a specific amount of time, while continually
cooling the vapour produced back into liquid form, using a condenser. The vapours produced
above the reaction continually undergo condensation, returning to the flask as a condensate. The
reaction is carried out in two-neck round bottom flask using a hot plate for heating.

8.2 Distillation

Distillation and reflux are two lab techniques that use the same equipment (with different
arrangement of condenser) to boil and condense a solution, but their purposes are different.
Distillation separates components of a mixture, while reflux helps complete a reaction.

Figure 2: Distillation set-up

44
8.3 Purification

Why is purification necessary in organic synthesis?

Purification of organic compounds is important because, organic compound made in the laboratory
contains impurities.

There are 2 common methods of purification depending of the physical state of the organic
compounds.

(i) Solid product: filtration  recrytallisation  melting point determination

(ii) Liquid product: separation  drying  distillation

8.31 Purification of Organic Solid Products

Organic solids formed are impure due to incomplete reaction. The reaction mixture is filtered to obtain
the impure solid product to be purified later through recrystallisation followed by melting point
determination of the crystals.

Use a suitable solvent in Heat up solution Product will appear as

which the organic product to dissolve both crystals as the solution
is soluble when hot but product and cools leaving behind the
insoluble when cold. impurities. impurities. The solution is

Pure organic solids have a very sharply defined melting point range. Hence the purity of the product
can be determined through determination of its melting point using a thiele tube (see Figure 3).

The melting point of an organic solid can be determined by introducing a tiny amount into a small
capillary tube, attaching this to the stem of a thermometer centred in a heating bath, heating the
bath slowly, and observing the temperatures at which melting begins and is complete.

Figure 3: Melting point determination using a Thiele tube filled with oil

45
8.31 Purification of Organic Liquid Products

Organic liquids are impure when aqueous reagents are used. A separating funnel is used to separate
the organic product from the aqueous solution. The mixture is washed with water to remove
unreacted aqueous reactants.

Figure 4: Separating liquid organic product and removing aqueous impurities.

Removal of water
After separating, the organic liquid is dried with an anhydrous ionic salt with have high affinity for
water molecules (through ion-dipole bond formation).

Figure 5: Drying the organic liquid

Removal of unreacted acids

Solid Na2CO3 can be added to remove unreacted acids. Effervescence of CO2 will be seen.

Removal of organic impurities using distillation

The mixture is filtered is obtain the organic liquid which is further distilled at the boiling point range
of the organic compound to obtain the pure product.

Distillation is used to identify and purify organic compounds. In the process of purification, we
separate a compound from another material by exploiting their boiling points. When different
compounds in a mixture have different boiling points, the mixture separates into its component parts
when it is distilled.

When distilling, the solution is heated so that the component with the lowest boiling point evaporates
first, leaving the other solutes behind. By changing the distillation temperature, many different
substances can be separated according to their different volatilities.

46
 Figure 6: Distillation of organic liquid

Exercise 4

In an experiment to prepare 1-bromobutane, 10.0 g of sodium bromide, 10 cm3 of water and 6.00 g
of butan-1-ol were placed in a double-neck round-bottomed flask fitted with a reflux condenser. 18.0
g of concentrated sulfuric acid was slowly added to it over a period of 10 min, with the flask standing
in a cold water bath, after which mixture was refluxed for 45 min. The apparatus was cooled and the
condenser was rearranged for distillation which was carried out until no more oily droplets were
collected.

The distillate with two liquid layers were separated in a separating funnel. The upper aqueous layer
was discarded and the lower organic layer was returned to the separating funnel where it was shaken
with concentrated hydrochloric acid. After separation, the lower organic layer was again returned to
the separating funnel where it was shaken with aqueous sodium hydrogen carbonate.

The organic layer was then transferred to a small conical flask and allowed to stand over anhydrous
sodium sulfate until it became clear. Finally, the 1-bromobutane was decanted from sodium sulfate
into a round bottom flask, and purified by distillation. The liquid boiling between 101 and 103 oC was
collected in a measuring cylinder.

a) Write a balanced equation for the reaction between solid NaBr and concentrated H2SO4 with
state symbols.

NaBr(s) + H2SO4(l)  HBr(g) + NaHSO4(aq)

b) Write a balanced equation for the reaction between butan-1-ol and hydrogen bromide.

CH3CH2CH2CH2OH + HBr  CH3CH2CH2CH2Br + H2O

c) Why was concentrated sulfuric acid added slowly?

Concentrated acids tend to react exothermically so a longer time will prevent rapid rise
in temperature.

d) Why was the mixture boiled for 45 min?

This is to allow the reaction to go into completion.

e) What is the purpose of boiling under a reflux condenser?

This is to avoid losing volatile products by vapourisation during boiling.

f) Name three compounds that were likely to be present in the distillate.

1-bromobutane, butan-1-ol and water

47
g) What was the purpose of shaking the distillate with concentrated hydrochloric acid?

React with butan-1-ol to remove it.

h) Suggest why concentrated hydrochloric acid would be particularly effective for the purpose you
have given in (g).

HCl being a strong acid will protonate butan-1-ol to form ionic CH3CH2CH2CH2OH2+ and
Cl_ ions, and both are soluble in water.

i) Why was crude 1-bromobutane shaken with sodium hydrogen carbonate and what precaution
must be taken at this stage?

NaHCO3 will neutralise unreacted HCl to remove it.

The pressure in the set-up must be released often due to production of CO2 gas.

j) What is the purpose of standing 1-bromobutane over anhydrous sodium sulfate?

To dry 1-bromobutane or remove water from it.

k) Why was 1-bromobutane decanted from sodium sulfate before the final distillation?

To separate 1-bromobutane from sodium sulfate which contained water.

l) Calculate the percentage yield if 5.8 cm3 of 1-bromobutane was obtained in this experiment.
Density of 1-bromobutane is 1.30 g cm─3

Amount of NaBr used = 10/102.9 = 0.0972 mol

Amount of H2SO4 used = 18/98.1 = 0.183 mol
Amount of butan-1-ol = 6/74 = 0.0810 mol
Hence, the limiting reactant is butan-1-ol

Mole ratio of butan-1-ol : 1-bromobutane = 1 : 1

Theoretical mass of 1-bromobutane formed = 0.081 x 137.9 = 11.2 g
Experimental mass of 1-bromobutane = 1.3 x 5.8 = 7.54 g
Percentage yield = 7.54/11.2 = 67.3%

48
Exercise 5

The Finkelstein reaction allows 1–iodopropane to be synthesized from 1–bromopropane and

sodium iodide, using dry propanone as a solvent.

CH3CH2CH2Br + NaI ⇌ CH3CH2CH2I + NaBr

(a) Table 1.1 shows the solubilities of sodium bromide and sodium iodide in propanone.
Table 1.1

solubility at 25 °C
compound
in g / 100 g of propanone

sodium bromide 0.00841

sodium iodide 39.9

Use this information in Table 1.1, explain why the Finkelstein reaction produces a very high
yield of CH3CH2CH2I.

The NaBr that is formed has a very low solubility in propanone. By Le Chatelier’s
Principle, the equilibrium position of the Finkelstein reaction will shift to the right to
counteract the low concentration of NaBr in propanone. This results in a very high
yield of CH3CH2CH2I.
[1]

(b) The preparation of 1–iodopropane is described as follows:

1–bromopropane, excess sodium iodide and propanone solvent are mixed and then
heated under reflux conditions for around thirty minutes.

The crude product is then distilled to produce pure 1–iodopropane.

Table 1.2 gives the boiling points and densities of 1–bromopropane, 1–

iodopropane and propanone.
Table 1.2

compound boiling point / oC density / g cm–3

1–bromopropane 71.0 1.35

1–iodopropane 102.6 1.75

propanone 56.0 0.784

[Ar: C, 12.0; H, 1.0; O, 16.0; Br, 79.9; I, 126.9; Na, 23.0]

(i) Assuming that the Finkelstein reaction goes to completion, calculate the volume
of 1–bromopropane and mass of sodium iodide you would need to prepare at
least 10.0 g of pure 1–iodopropane. Show your working clearly.

Amount of CH3CH2CH2I = 10.0 ÷ 169.9 = 0.0589 mol

Amount of CH3CH2CH2Br = 0.0589 mol
Mass of CH3CH2CH2Br = 0.0589 x 122.9 = 7.23 g
• Volume of CH3CH2CH2Br = 7.23 ÷ 1.35 = 5.36 cm3
Amount of NaI = 0.0589 mol
• Mass of NaI = 0.0589 x 149.9 = 8.82 g

49
 • Excess NaI should be used to obtain at least 10g of 1-iodopropane.
Hence, 15 g of NaI and 6 cm3 of 1-bromopropane will be used.
[3]

(ii) Write a plan for the preparation of at least 10.0 g of pure 1–iodopropane.

You may assume that you are provided with:

• liquid 1-bromopropane,
• solid sodium iodide,
• 25.0 cm3 liquid propanone,
• the equipment normally found in a school or college laboratory.

In your plan, you should include details of:

• the quantities of the reactants calculated in (b)(i),
• the apparatus you would use, including well-labelled diagrams of the
assembled apparatus,
• the procedure you would follow to obtain pure 1–iodopropane.

1. Weigh 15 g of NaI and place it in a dry two-neck round bottom flask.

2. Use a dropping funnel, transfer 6 cm3 of CH3CH2CH2Br and 25 cm3 of propanone into
the flask.
3. Set up the reflux apparatus using a hot-plate for heating.
4. Boil the mixture under reflux for 30 min.

Figure 1: reflux set-up

5. Cool the apparatus and rearrange the condenser for distillation.

6. Carry out the distillation and collect the fraction at the range of 102.6 ± 2 °C to obtain
pure 1-iodopropane

Figure 2: Distillation

[8]
[Total: 12]

50