Safer chemicals,

safer reactions
L195

L195

July 2006

July 2006

Electrolysis of molten
lead(II) chloride

Safer chemicals, safer reactions

The Thermite reaction

Microscale reduction of
copper oxide with hydrogen

Semolina particles on castor oil

illustrate the presence of an
electric field between
the two plates

Contents
1.

Introduction
1.1
1.2
1.3

2.

Safer spirit burners

D-i-y spirit burners
A review of procedures for measuring the energy content of fuels

Safer advanced-level organic chemistry

14
15
15

16

Phenylamine (aniline) reactions - a safer alternative

Phenol reactions - a safer alternative
Nitration of benzene - a safer alternative
A safer use of nitrated products
Reduction of nitrobenzene - a safer alternative
A safer solvent for the extraction of caffeine from tea
A safer reagent to oxidise alcohols to carboxylic acids

16
18
20
21
22
23
24

Hydrogen reactions - safer procedures

25

Hydrogen burning and exploding in air

Hydrogen/oxygen explosion
Hydrogen as a reducing agent

25
26
27

Diffusion of gases - a safer alternative

28

Diffusion into air

Diffusion into a vacuum

28
29

Exothermic reactions - safer procedures

9.1
9.2
9.3
9.4
9.5
9.6
9.7

10.
11.
12.

12
14

8.1
8.2

9.

7
8
8

Safer combustion of liquid fuels

7.1
7.2
7.3

8.

Current situation
Disposal strategy
School alternatives for the use of chlorinated hydrocarbons

12
13

6.1
6.2
6.3
6.4
6.5
6.6
6.7

7.

3
3

Safer mineral fibre

Heat-resistant paper

5.1
5.2
5.3

6.

Stock solutions
Suggested concentrations for various practical activities

Safer alternatives to asbestos

4.1
4.2

5.

1
1
2

Safer alternatives to chlorinated hydrocarbons

3.1
3.2
3.3

4.

Hazard information
Reducing risks
Reducing waste and safer disposal

Safer solutions
2.1
2.2

3.

Page
1

30

Ammonium dichromate(VI) decomposition

Iron/sulfur reaction
Sodium burning in chlorine
Thermite reaction
Fat-pan fire
Cigarette smoking machine
Sulfuric acid dilution

30
31
32
33
34
35
36

Electrolysis of molten salts

Crude-oil distillation
Cooling curves

37
39
40

12.1 Substances used for cooling curves

12.2 Manual logging for the cooling curve of naphthalene
12.3 Using a datalogger to monitor cooling

40
42
42

13. A safer procedure for the thiosulfate/acid reaction

Index
This guide replaces L195, Substitute Chemicals and Alternative Procedures, published in 1994.

43
45

Strictly Confidential - Circulation to Members and Associates only.

As with all CLEAPSS materials, members and associates are free to copy
all or part of this guide for use within their own establishments.

CLEAPSS 2003 (amended 2006; section 5)

CLEAPSS
Brunel University
Uxbridge UB8 3PH
Tel: 01895 251496 Fax: 01895 814372
E-mail: science@cleapss.org.uk
Web site: www.cleapss.org

L195
1.

Safer chemicals, safer reactions

Introduction

Many people in science education have blamed health & safety and environmental legislation
for removing some of the well-known demonstrations and activities from school chemistry.
This, they believe, has made chemistry less exciting. There is no doubt that hazard information
on chemicals and legislation has altered the approach to practical work (see Guide L196,
Managing Risk Assessment in Science). However, CLEAPSS has always maintained that almost all
standard demonstrations, such as the Thermite reaction, can still be carried out and have a
place in todays curriculum.

1.1

Hazard information

The Health and Safety Executive, through the CHIP Regulations1, publishes information concerning the level of hazards together with risk phrases2 for many substances used in industry.
This guidance is a result of carefully-controlled tests. Consequently, for example, the hazard for
copper(II) sulfate is harmful with the risk phrase R22: Harmful if swallowed. All suppliers adhere to this information.
If a chemical is not on the Approved Supply List, suppliers must provide hazard information
from data supplied to them by the manufacturer of the chemical. This can lead to confusing and
conflicting information. Thus, copper(II) chloride, which is not on the Approved Supply List, is
toxic in some catalogues but harmful in others.
A Materials Safety Data Sheet (MSDS) must be provided when the chemical is first supplied or
if the hazard data are changed. These sheets should be kept for reference. However, they are
not always helpful; some carry very little information (especially when the formulation is a
company secret!), while others have pages of information about animal tests, covering every
eventuality. There is also a difference between European and American-based suppliers, with
the latter often adopting an overcautious approach. It is useful to note that MSDSs apply to
industrial situations rather than to education where only very small amounts or dilute solutions
of these chemicals are used. MSDSs are also not risk assessments since they do not take into
account the circumstances in which the chemicals are used.

1.2

Reducing risks

This guide describes how control measures, required by the COSHH3 and Management of Health
and Safety at Work Regulations, allow procedures with hazardous chemicals to continue. Control
measures used to make procedures safer include substituting chemicals with a lower hazard
rating (see Table 1) and/or lower concentrations, reducing the scale of an operation and
ensuring that vapours are contained. In this document, the hazard of a solution is printed in
small capitals; if there is no reference to a hazard, it may be assumed that the solution has a low
hazard.

Table 1

The hazards of chemicals

Physico-chemical effect

Decreasing
risk

2
3

Health effects

FLAMMABLE

HARMFUL

IRRITANT

HIGHLY FLAMMABLE

TOXIC

CORROSIVE:

causes burns

EXTREMELY FLAMMABLE

VERY TOXIC

CORROSIVE:

causes severe burns

The Chemicals (Hazard Information and Packaging for Supply) Regulations 2002. Approved Supply Lists: Information for
the Classification and Labelling of Substances and Preparations Dangerous for Supply, HSE. This publication is updated
frequently and the ISBN number changes. Changes to the hazards of chemicals used in education are highlighted
in the CLEAPSS Bulletin, published three times a year.
A list of risk phrases can be found in the CLEAPSS Laboratory Handbook, section 7.8.
Control of Substances Hazardous to Health, 4th edition, Approved Code of Practice and Guidance, HSE Books, 2002, ISBN
0717625346.
1

CLEAPSS can only advise on the science involved in a proposed activity. Those with
responsibility for chemistry, when directing practical work, should assess the suitability of
rooms (eg, size and ventilation), experience of staff and behaviour of students when adapting
their employers risk assessments for the particular circumstances of the school or college. For
further advice, again see Guide L196.
Ideally, an activity should be modified so that there is no, or a reduced, need for personal protective equipment (PPE) as a control measure. Chemicals, or concentrations of solutions, should
be chosen so that, if possible, only safety spectacles need be worn as eye protection and that
there is no need to wear gloves. All PPE should be as comfortable as possible.
Another source of guidance4 on risk assessment in educational activities is Safety in Science
Education. This emphasises the dynamic nature of assessing risk rather than it being a static,
form-filling exercise. The guidance also states that the control measures arising from the assessment of risks should be included in the instructions for demonstrations and practical work.

1.3

Reducing waste and safer disposal

Any activity involving chemical changes will generate chemicals for disposal. Issues about disposal need to be considered when the activity is planned. Many schools have rows of shelves
full of chemicals no longer required by current courses or over-ordered in the past. These surplus chemicals may present hazards and certainly clutter up scarce space. They should be disposed of in a safe and responsible manner. Prep room clear-outs like this will normally involve
paying an authorised waste contractor - obtain at least three quotations5.
When planning an activity, in order to minimise waste disposal, consider:

arranging for the product of one reaction to be the starting material for the next (see sections 6.3,
6.4, 6.5);
reducing the scale of the procedure or even adopting microscale techniques6;
recycling the products, if possible.

Situations where recycling may be practicable include the following.

Recover, eg, silver, copper or nickel by electrolysis or displacement of the metal with iron.
Collect lead iodide from precipitation reactions and use later for electrolysis.
Collect copper sulfate crystals, crush, and use next year.
Wire-form copper oxide which has been reduced to copper can be reoxidised and reused or kept
for use as copper metal.
Recover solvents by redistillation, but not peroxidisable ones (eg, ethoxyethane, cyclohexene),
unless first tested for peroxides.

Waste products which are hazardous can often be treated to make them low hazard or at least
less hazardous; see the examples below.

Table 2

Treatment of waste

Waste chemical

Possible treatment

Acids or alkalis

Neutralise one with another. Aim to discharge to waste between pH 5 and 9. If there is
no surplus of one, soda ash and ethanoic acid are cheap materials.

Oxidising agents and

reducing agents

React one with another. Iron(II) sulfate, acidified with a little dilute sulfuric acid, is a
cheap general-purpose reducing agent.

Metal salts

It may be possible to precipitate, usually as the carbonate or hydroxide. Barium salts

could be precipitated as the (low hazard) sulfate. Chromium(VI) compounds, and other
salts in high oxidation states, may need reduction before precipitation.

For further information on the disposal of small amounts of waste products from chemical
reactions, see Hazcards.

4
5
6

Safety in Science Education, 1996, DfEE, The Stationery Office, ISBN 011270915X, sections 4.7.1 and 4.7.2.
See CLEAPSS leaflet PS5, Waste Disposal Contractors.
See CLEAPSS guide L216, Microscale Organic Chemistry.
2

2.

Safer solutions
Myths: All bench solutions must be removed from laboratories. You must only use 0.4 M7
solutions at KS3. Corrosive and toxic solutions must not be used at KS3.

All of the above statements are false. Many years ago, reagent bottles containing 2 M acids, alkalis and salt solutions, were often found on open shelves and benches within easy reach of
students for them to carry out qualitative analysis. Such situations can still be found but the
ready accessibility of hazardous solutions presents some risk. There may be valid reasons to
keep chemical solutions in a laboratory (eg, it is some distance from the prep room) but hazardous chemicals (ie, any with a hazard classification) should normally be locked in cupboards.
Any chemicals on open shelves should be low hazard unless the assessment of risk has shown
that students are sufficiently reliable to make an exception.
In its scheme of work for science at KS3, QCA suggested the use of 0.4 M acids and alkalis. The
advantage of using such concentrations is that none of the common acids or alkalis would be
CORROSIVE. Using guidance from the CLEAPSS Laboratory Handbook section 3, safety spectacles
could be used rather than goggles, which are the required form of eye protection when students
handle corrosive or toxic chemicals. Using the COSHH Regulations as guidance, a risk assessment for a procedure to be used by pupils should identify the minimum safe concentration of a
solution at which the desired effects of the reaction can be observed. For most purposes, 0.4 M
or even 0.1 M is adequate but, in certain cases, to obtain the desired reaction, more concentrated
solutions are required (eg, the preparation of hydrogen using the reaction between zinc and
hydrochloric acid). Guidance is given in Table 3 which relates an activity to a reasonable concentration of reactants. It is unlikely that, at KS3, schools will need to use concentrations stronger
than 0.4 M for sodium hydroxide and 2 M for hydrochloric acid. 1 M sulfuric8 acid may
occasionally be required. All of these are classified as IRRITANT, rather than CORROSIVE. There is
no justification in continuing to use 2 M solutions just because they always have been used in
the past.
Whether students are allowed to use corrosive and/or toxic solutions depends upon the risk
assessment, not only for the activity but also a consideration of the behaviour and number of
students in the class, the experience of the teacher, the size of room and its ventilation etc. Some
responsible students could use 1 M sodium hydroxide (CORROSIVE) at Y7 and others could even
make soap with 5 M sodium hydroxide at Y9, if the risk assessment was positive, but these are
likely to be exceptional cases.

2.1

Stock solutions

It is recommended that large volumes (eg, 10 litres) of the following stock solutions are
prepared for further dilution as and when required.

1 M sodium hydroxide (corrosive),

2 M hydrochloric acid and/or 1 M sulfuric acid (irritant).

Smaller volumes of more concentrated solutions may be required but these should be prepared
as needed. Diluted solutions of ammonia should be prepared just before use because the continual loss of gas from the solution reduces its concentration.

2.2

Suggested concentrations for various practical activities

Table 3 provides concentrations and guidance for various activities.

7
8

M is used as a convenient method of writing mol dm-3.

Sulfur is the British Standard spelling and has been used throughout this guide.
3

Table 3

Suggested concentrations for various practical activities

Activity

Suggested
concentration

Comments
(Hazards of these concentrations are shown. If no hazard is indicated, assume LOW HAZARD.)

Anion tests

0.1 M barium nitrate solution

0.05 M silver nitrate solution

Some texts advise that these anion tests should be carried out in acidic solution. Use 0.4 M nitric
acid (IRRITANT). 0.1 M barium chloride solution may be used but the nitrate appears to be safer to
use than the chloride.

Biuret test for proteins

0.1 M alkali (IRRITANT)

Carbonates reacting
with acids

0.4 M acids (IRRITANT)

This works on milk with 0.1 M sodium hydroxide (IRRITANT) (with 0.01 M copper(II) sulfate solution). Acidic foods may need a more concentrated alkali to neutralise the naturally-occurring
acids. See Recipe Card 13. Alkali solutions at this concentration have a limited shelf life due to
the reaction with atmospheric carbon dioxide.
All acids produce carbon dioxide. Comparison of different reactivity will depend upon whether the
acid is strong or weak and the solubility of the resulting salt, eg, calcium sulfate.

Carbon dioxide
preparation

2 M hydrochloric acid (IRRITANT)

Dilute sulfuric acid does not react with calcium carbonate as the marble chips become coated
with calcium sulfate. Use marble chips; precipitated calcium carbonate would react too quickly.

Crystal growth

Saturated salt solutions

Displacement reactions
of metal salts
Displacement reactions
with halogens

0.05 M silver nitrate solution

0.4 M solutions of other salts
0.02 M halogen solutions

Aluminium potassium sulfate (11.4 g), ammonium chloride (HARMFUL) (37 g), copper(II) sulfate
(HARMFUL) (32 g), potassium nitrate (OXIDISING AGENT) (32 g) and sodium chloride (36 g) can be
used. The solubility in g/100 ml at 20C is given in brackets. The crystals can be seen forming on
a microscope slide.
Always use magnesium ribbon, not the powder, with 0.1 M silver nitrate solution.

Electrolysis

0.4 M solutions of salts but use 0.1 M

silver nitrate solution

Much will depend upon current, type of electrodes and temperature but lower concentrations can
produce good results.

Heat of reaction
(displacement)

0.4 M copper(II) sulfate solution

Use zinc powder.

Heat of reaction
(neutralisation)

2 M nitric acid (CORROSIVE), 1 M

sulfuric, 2 M hydrochloric and 2 M
ethanoic acids (IRRITANTS)
2 M sodium and potassium hydroxide
solutions (CORROSIVE)
1 M sodium carbonate solution and
2 M ammonia (LOW HAZARD)

Mixing acids with alkalis should give a change in temperature of around 12C. This is more suitable for thermochemistry measurements. The use of 0.4 M solutions should produce a temperature increase of 2C which might not register on small thermometers.

Heat of reaction
(precipitation)

1 M copper sulfate (HARMFUL) and

1 M sodium hydroxide (CORROSIVE)
solutions

These concentrations are required to obtain a reasonable change in temperature.

Use a 0.5% (w/v) solution of iodine, 0.3% (w/v) solution of bromine (HARMFUL and IRRITANT) and
0.1% (w/v) solution of chlorine. Aqueous solutions of chlorine and bromine have a limited shelf
life. Cyclohexane can be used to remove the halogen from the aqueous layer to demonstrate its
presence more clearly (see Safer Alternatives to Chlorinated Hydrocarbons, section 3).

Table 3

Suggested concentrations for various practical activities (continued)

Activity

Suggested
concentration

Comments
(Hazards of these concentrations are shown. If no hazard is indicated, assume LOW HAZARD.)

Hydrogen collection

2 M hydrochloric acid or 1 M sulfuric

acid (both IRRITANT)

Add a few drops of 1 M copper(II) sulfate solution (HARMFUL) to the zinc/acid mixture. The copper
coating to the zinc catalyses the reaction. 5 ml of acid will produce 120 ml of hydrogen gas
(EXTREMELY FLAMMABLE).

Hydrogen collection
(large scale)

3 - 5 M hydrochloric acid (IRRITANT)

The addition of copper sulfate crystals produces copper on the surface of the zinc which catalyses the reaction.

Indicators with acids

and alkalis

0.1 M alkali (IRRITANT) and acid

solutions

More concentrated solutions of alkalis can alter the colour of an indicator when left for several
minutes. Alkali solutions at this concentration have a limited shelf life due to the reaction with
atmospheric carbon dioxide.

Lead/acid accumulator
simulation

0.4 M sulfuric acid

Use lead-foil electrodes. Car batteries use 5 M sulfuric acid (CORROSIVE).

Metals reacting with

acids

0.4 M acids except 0.4 M nitric acid

(IRRITANT)

Oxygen preparation

20 vol hydrogen peroxide (IRRITANT)

Sulfuric and hydrochloric acids produce hydrogen gas with active metals but nitric acid behaves
differently, producing nitrogen oxides (TOXIC). 1 M sulfuric or 2 M hydrochloric acid (IRRITANT) are
required if the hydrogen is to be collected.
For large-scale preparation by the teacher or technician, it may be more cost effective and less
time consuming to start with 20 vol hydrogen peroxide and then to top up the reaction mixture
with 100 vol solution (CORROSIVE).

Precipitation reactions
and tests for cations

0.4 M solutions of alkalis (IRRITANT),

acids (some IRRITANT) and salts
1 M ammonia solution
0.3 M ammonium ethanedioate

The volume of solution to be tested should be no more than one fifth of the height of the test
tube. This avoids the test tube overflowing when the second reagent is added and allows agitation of the mixture without splashing over.
Ammonia solution should not be stored for long periods as ammonia gas (TOXIC) is lost and the
solution becomes progressively more dilute.
Ammonium ethanedioate is suitable for identifying calcium ions.

Rate of reaction
(calcium carbonate/acid
reaction

2 M hydrochloric acid (IRRITANT)

The loss in mass of calcium carbonate, when it is reacted with 100 ml of 2 M hydrochloric acid, is
4.4 g (loss of carbon dioxide to the atmosphere).

Rate of reaction
(hydrogen peroxide
decomposition)

A range of values from 2 vol to 20 vol

(IRRITANT)

Much will depend on what the investigation requires. Concentrations of hydrogen peroxide above
18 vol are considered IRRITANT. Hydrogen peroxide solution decomposes on storing (especially
when diluted from 100 vol) and the concentration decreases.

Rate of reaction
(thiosulfate/acid
reaction)

2 M hydrochloric acid (IRRITANT)

A range of sodium thiosulfate concentrations up to 0.2 M

Investigations at higher concentrations of acid can produce confusing results. Concentrations

above 0.2 M sodium thiosulfate mixed with acid may produce enough sulfur dioxide (TOXIC and
CORROSIVE) to cause a problem for asthmatics.

Table 3

Suggested concentrations for various practical activities (continued)

Activity

Salt preparation using

dilute acids with metal
hydroxide, metal oxides
or metal carbonate

Suggested
concentration
2 M hydrochloric acid (IRRITANT) or
1 M sulfuric acid (IRRITANT) with 2 M
alkalis (CORROSIVE) including
ammonia solution

Comments
(Hazards of these concentrations are shown. If no hazard is indicated, assume LOW HAZARD.)
10 ml of 2 M hydrochloric acid with 1 ml of 2 M sodium hydroxide solution will produce 1 g of
sodium chloride salt.
10 ml of 1 M sulfuric acid (IRRITANT) with copper(II) oxide (HARMFUL) or copper(II) carbonate
(HARMFUL) produces 2.5 g of copper sulfate crystals (HARMFUL). This will be quicker to carry out
compared to the use of 0.4 M acid because filtration, boiling and cooling will take less time.
Note that 1 M sodium carbonate solution has a lower hazard rating than 1 M sodium hydroxide
solution and may be preferable. However, the chemistry (for some students) may be considered
more complex.

Soap preparation

5 M sodium hydroxide solution

(CORROSIVE)

A risk assessment should be carried out to ascertain whether the students are capable of performing the procedure safely. Goggles or even face protection are obviously essential.

Sodium hydroxide solution with aluminium foil

1 M sodium hydroxide solution

(CORROSIVE)

Hydrogen (EXTREMELY FLAMMABLE) is produced.

Stoichiometry of
precipitation reactions
Sulfur dioxide test

1 M solutions of metal salts

These concentrations are required to obtain a measurable height of precipitate. Check hazard
rating of the salts to be used (see introduction to this section).
This concentration is still classified as TOXIC.

Testing for carboncarbon double bonds

1% potassium dichromate(VI)
solution
0.01 - 0.005 M bromine solution in
water [0.16 - 0.08% (w/v) solution]
0.001 M acidified potassium manganate(VII) solution

Titrations (volumetric,
coulometric)

0.1 M alkali (IRRITANT) and acid

solution

Alkaline solutions more dilute than 0.01 M are not suitable for accurate volumetric work as dissolved carbon dioxide interferes with the results. Solutions more concentrated than 0.5 M can be
used but evaporation of the solvent at the tip of the burette may cause flow problems.

The weaker solution should be used for the cracking of paraffin oil activity. Only use a 1 cm
depth of reagent in the test tube so that not much of the collected gas is lost by displacement.

3.

Safer alternatives to chlorinated hydrocarbons

Myth: You cannot use chlorinated hydrocarbons9 in schools.

3.1

Current situation

Table 4 illustrates the hazards of chlorinated solvents that have been used in school chemistry.

Table 4

Chlorinated hydrocarbons used in school chemistry

Substance

Hazard rating and OEL

(ppm)10

Risk11

School
use?

Comments

1,2-Dichloroethane

TOXIC, HIGHLY FLAMMABLE

R45, 11, 22,

36/37/38

No

(B pt is 84 C.) Formally used to

make Thiokol rubber. It is not
recommended for school use.

Dichloromethane
(Hazcard 28)

HARMFUL; Limited evidence of a

carcinogenic effect
100 (MEL) (LTEL)
300 (STEL)

R40

Yes

(B pt 40 C.) Used in paint strippers and brush cleaners. It can

be used with care by post-16
pupils. Although classified as a
category 3 carcinogen, the evidence has been challenged.

Tetrachloroethene
(Hazcard 99)

HARMFUL; Limited evidence of a

carcinogenic effect,

R40, 51/53

Yes

(B pt is 121 C.) This is not a

common school chemical but it
can be used with care by post16 pupils.

R26/27,
51/53

No

(B pt is 146 C.) It is not recommended for school use.

R23/24/25,
40, 48/23,
52/53, 59

No

(B pt is 77 C.) Ozone depleter

(not now available). This used to
be a common solvent in schools
especially for bromine. Schools
should dispose of existing stocks.

R20, 59

No

(B pt is 74 C.) A comparatively
safe substance but no longer
available as it is an ozone
depleter. Schools should dispose
of existing stocks.

R20/21/22

No

(B pt is 112 C.) A very expensive

chemical.

5 (MEL) (LTEL)

DANGEROUS FOR THE ENVIRONMENT

50 (LTEL), 100 (STEL)

1,1,2,2-Tetrachloroethane

VERY TOXIC, DANGEROUS FOR THE

ENVIRONMENT

Tetrachloromethane
(Carbon tetrachloride)
(Hazcard 100)

TOXIC; Limited evidence of a

1,1,1-Trichloroethane
(Hazcard 103)

HARMFUL,
DANGEROUS FOR THE ENVIRONMENT

1,1,2-Trichloroethane

HARMFUL

Trichloromethane
(Chloroform)
(Hazcard 104)

HARMFUL; limited evidence of a

carcinogenic effect
2 (Sk) (LTEL)

R22, 38, 40,

48/20/22

Yes

(B pt is 61 C.) It can be used in

a fume cupboard with care by
post-16 pupils.

Trichloroethene
(Hazcard 99)

TOXIC: category 2 carcinogen

R45, 36/38,
52/53,67

Only by
trained
staff

(B pt is 87 C.) It is used to test

filter fume cupboards by trained
employees. It should not be used
by pupils.

9
10
11
12

No OEL assigned
carcinogenic effect,
DANGEROUS FOR THE ENVIRONMENT

2 (Sk12) (LTEL)

200 (LTEL), 400 (STEL)

No OEL assigned

100 (LTEL).150 (STEL)

Chlorinated hydrocarbons are organic compounds in which one or more halogen atoms are substituted for a hydrogen atom.
See CLEAPSS Laboratory Handbook section 7.9.1 for information about Occupational Exposure Levels.
See CLEAPSS Laboratory Handbook section 7.8 for information about risk phrases.
Sk means that a chemical can be absorbed through the skin.
7

The chronic effects of most chlorinated hydrocarbons are still not fully understood but where
there may be a cause for concern, a R4013 risk phrase is given. The R45 risk phrase is given
where there is a more serious problem14. More details on carcinogenic hazards can be found in
Topics in Safety15, section 12.
This country has signed up to the Montreal protocol which forbids the sale of chemicals with a
R59 risk phrase (dangerous to the ozone layer) for general use. Schools cannot now legally buy
tetrachloromethane and 1,1,1-trichloroethane (see Hazcard 103). Trichloromethane (chloroform),
however, can still be bought from suppliers.
The COSHH Regulations state that the three substances discussed above cannot be used in diffusive applications such as surface cleaning and the cleaning of fabrics except for the purposes
of research and development or for the purpose of analysis. It is not clear how the word diffusive applies to a few millilitres in a test tube stoppered with a bung, as the rate of evaporation would be negligible. It would need, however, a court of law to rule on this!
Some chlorinated hydrocarbons, eg, dichloromethane, can be used, although of course there are
still hazards (see Table 4). Further legislation is anticipated and any alteration to this information will be provided in future editions of the CLEAPSS Bulletin.

3.2

Disposal strategy

After use as solvents, chlorinated hydrocarbons should be collected by the students or teacher
for disposal by a hazardous waste contractor. Unopened or nearly-full bottles of tetrachloromethane and 1,1,1-trichloroethane should also be included. Stocks of trichloromethane (see
Table 5) might also be disposed of because the inclusion of investigations of Raoults Law in 6th
form schemes of work is now highly unlikely.
Treatment for the removal of materials such as bromine and iodine from chlorinated solvents
can be achieved by washing the solvent with 1 M sodium hydroxide solution (CORROSIVE).
When the liquid is colourless, the aqueous layer should be removed and the solvent placed in
organohalogen waste bottles, suitable labelled, with their contents and the date. They should be
removed by a hazardous waste contractor within a year. This could be an expensive operation.
Test-tube washings can go down the foul-water drain with plenty of soapy water.
Recycling is also an option for larger volumes of solvents that can still be used legally. The
liquid would need to be stripped of contaminants, dried and redistilled for further use. This
procedure, however, takes time and should be carried out only by those with expertise in
organic chemistry.
Destruction of chlorinated hydrocarbon solvents, as opposed to non-chlorinated hydrocarbons,
is more involved16 and expensive. Any procedures that specify the use of organohalogen solvents should be reviewed to see if safer alternatives are available. If information in Table 7 does
not identify a suitable alternative, contact CLEAPSS.

3.3

School alternatives for the use of chlorinated hydrocarbons

The COSHH Regulations demand that if a safer alternative reagent is available for a certain activity, it should be used in preference to the more hazardous substance. Table 5 considers activities for which there appear to be no suitable alternatives.

13
14
15
16

Limited evidence of a carcinogenic effect: this phrase is associated with category 3 carcinogens.
See CLEAPSS Laboratory Handbook section 7.8.
Topics In Safety, 3rd edition, 2001, ASE, ISBN 0863573169.
Toxic dioxins may be formed during combustion and these need to be removed from the waste fumes.
8

Table 5

Activities for which there are no suitable alternatives

Activity

Comment

Investigating the hydrolysis of mono-substituted halogenoalkanes. (An activity

carried out on a test-tube scale.)

Mono-substituted butanes, which are usually used for this

activity, are not included in the Montreal protocol. The
washings may be disposed of down the foul-water drain
with plenty of water.

Investigating the negative deviation of

Raoults Law: mixtures of trichloromethane (TOXIC) with ethyl ethanoate
(HIGHLY FLAMMABLE).

There seems to be no satisfactory alternative to using

trichloromethane. See Hazcard 104. The mixtures need to
be kept in a labelled bottle for disposal by a licensed
contractor. However, it is most unlikely that this activity
will now be carried out in schools as the topic has largely
been removed from post-16 curricula.

Preparation of Thiokol rubber:

1,2-dichloroethane is used.

It is no longer recommended that this substance should

be made in schools17.

Chlorinated hydrocarbons were usually used as degreasing agents in industry. Examples of

alternatives available to industry are shown in Table 6.

Table 6
Name

Industrial solvents available to schools

Recommended
source18

Chemical

Hazard

Comments

Evolve
CH15

Breckland Scientific
Supplies or Timstar
6.95 for 500 ml.

A blend of hydrocarbons.
B pt about 170 C.

R10: FLAMMABLE.
R65: HARMFUL; May
cause lung damage if
swallowed.

Not suitable for dissolving

bromine. A 1% bromine solution decolourises within
minutes.

Lotoxane

Griffin and George

12.75 for 1 litre.

C11-13 branched
hydrocarbons.
B pt about 180 C.

Minimal.

Not suitable for dissolving

bromine.

Volasil
244

VWR (Merck)19
13.86 for 500 ml

Octamethylcyclotetrasiloxane.

Supplier quotes R53,

62: May cause longterm adverse effects
in the aquatic environment; possible risk
of impaired fertility.

Despite these hazard warnings, the substance is used

extensively in face creams
and shampoos. It dissolves
bromine but the solution
does not keep; see Table 7.

(CH3)8Si4O4

M pt 17.5 C
B pt 175.5 C.

Despite comments to the contrary in chemical catalogues, there is no single substitute for the
chlorinated hydrocarbons used in schools; different activities may need different alternatives.
It is necessary to review the activities for which chlorinated hydrocarbons are used in school
chemistry and identify suitable alternatives. Table 7 provides guidance. Of course, the suggested alternative may not work as well as the original chlorinated hydrocarbon!

17
18
19

Safety in Science Education, DfEE, 1996, The Stationery Office, ISBN 011270915X.
Addresses may be found in the index to the CLEAPSS Laboratory Handbook. Obtaining chemicals from other
suppliers often increases the price.
Merck Eurolab (formally BDH Ltd) is now trading as VWR International. Its telephone number is 0800 223344 but
schools may be referred to a local agent for VWR products.
9

Table 7

Activities for which there are suitable alternatives

Activity or substance

Substitute

Bromine solution in a non-aqueous

solvent; tetrachloromethane was the
best solvent because the solution
could be kept for a long time.

Cyclohexane can be used if it can be stored out of the light (eg,

in a dark bottle or a clear bottle in a labelled cardboard box).
However, plastic screw tops or bungs will be affected if stored
for over a month. In a clear bottle, noticeable deterioration will
occur within 2 days.
Volasil 244 can be used in clear bottles in the laboratory. A
3% (w/v) solution is stable overnight. A 1% (w/v) solution is
stable for several days but not for a week. Solutions that are
3% (w/v) or stronger should be used as quickly as possible. In
chemical terms, bromine opens the ring structure of Volasil to
initiate polymerisation. The resulting jelly is not easy to remove
from bottles.

Chromatographic separation of
aspirin, paracetamol and caffeine.

Ethyl ethanoate (HIGHLY FLAMMABLE) (10 ml) with a drop of

concentrated ethanoic acid (CORROSIVE).

Chromatographic separation of the

nitration products of phenol.

A 1:1 solution of ethoxyethane (EXTREMELY FLAMMABLE) and

petroleum ether (100-120 C) (HIGHLY FLAMMABLE). Rf value for
phenol is 0.60 with products at 0.72 and 0.41 plus other spots.

Degreasing agent (eg, lenses and

metals).

Lotoxane, Evolve CH15 & Volasil 244 can be used. However,

the rate of evaporation is slower than with 1,1,1-trichoroethane.

Displacement reactions of the halogens (ie, the addition of chlorine solution to potassium bromide solution.

Cyclohexane or Volasil 244 are suitable but, being less dense

than water, they form an upper layer. Cyclohexane is much less
expensive than Volasil 244. The collected waste can be treated
with 1 M sodium carbonate solution before recycling or disposal. See Hazcards 45 and 106 for disposal.

Distinguishing between soda and

borosilicate glass.

Propan-1,2,3-triol. Borosilicate glass disappears from view in

propan-1,2,3-triol (glycerol) because it has a similar refractive
index.

Distribution of ammonia between

trichloroethane and water.

Ethyl ethanoate (HIGHLY FLAMMABLE) may be used but the

concentration of ammonia solution must be 1 M or less.

Distribution of iodine between

tetrachloromethane and water or
potassium iodide solution.

Volasil 244. This is a complex system. Details can be obtained

from CLEAPSS.

Electric field patterns of semolina

grains trapped between layers of
1,1,1-trichloroethane and castor oil.

Castor oil can be used on its own without using a chlorinated

hydrocarbon at all. Small bottles of castor oil can be obtained
from a local pharmacist.

Enthalpy of formation of inter-molecular forces (hydrogen bonding)

between trichloromethane and ethyl
ethanoate molecules.

It is preferable to measure the enthalpy change when the intermolecular forces (hydrogen bonds) between ethanol molecules
are broken by the addition of cyclohexane.

Extraction of caffeine from tea or

limonene from orange peel.

Dichloromethane (HARMFUL). Another method of extracting

caffeine into an organic layer can be achieved by adding
enough sodium chloride to saturate the solution and then adding propan-1-ol (HIGHLY FLAMMABLE). The caffeine extracted will
contain sodium chloride and will need to be separated (see
section 6.6).

Hydrolysis of group IV halides:

Tetrachloromethane does not react
with water but silicon tetrachloride
does.

A (1:1:1) mixture of tetrachloroethene (HARMFUL), ethanol

(HIGHLY FLAMMABLE) and water, which are present in the same
phase, showed no changes in conductivity when left for a day.
This indicated that no hydrolysis had taken place. It is
questionable whether this is a valid substitution!

Iodine value determination of unsaturated fats.

Dichloromethane (HARMFUL) can be used. Tetrachloromethane was used to amplify the iodine during the titration of
Wijs solution against sodium thiosulfate solution.

10

Table 7

Activities for which there are suitable alternatives (continued)

Activity or substance

Substitute

Lead analysis using dithizone.

Methylbenzene (HARMFUL and HIGHLY FLAMMABLE) is an

alternative solvent for dithizone.

Molecules attracted to electrostatic

fields: an electrostatic field generated
by rubbing a plastic rod is brought
close to a liquid running out of a
burette. The direction of the flow is
deflected by the polarised molecules
attracted to the field. Tetrachloromethane shows no deflection.

Tetrachloroethene can be substituted for tetrachloromethane.

Dichloromethane and trichloromethane can still be used. The
burettes can be set up in a fume cupboard. However, a high
face velocity may well affect the observations so the fume
cupboard should be switched off while the demonstration is
carried out. If separate burettes are used, the liquids can be put
back into their bottles for further use.

Nylon preparation: solutions of 1,6diaminohexane in water and an acid

chloride in an immiscible solvent (it
used to be tetrachloromethane) are
brought together. The nylon polymer
forms at the interface of the two
liquids.

Cyclohexane, petroleum ethers, Lotoxane, Evolve CH15

and Volasil 244 can all be used as suitable alternative solvents
to dissolve the acid chloride. However, these solutions have to
be applied after the aqueous layer has been placed in the
beaker. Organic solvents are never completely free from tiny
amounts of water20 and a white solid in these solutions indicates
that the acid chloride has hydrolysed to the dicarboxylic acid
and will not form nylon. See Hazcard 100 for further experimental points. For disposal, stir the liquid, place the nylon in
waste paper and put it in the waste. See the relevant Hazcard
for the removal of the solvent waste.

Perspex cement use.

Dichloromethane (HARMFUL).

Tin(IV) iodide preparation. Tin and

iodine are heated under reflux in
1,1,1-trichloroethane.

Dichloromethane (HARMFUL) can be used but the boiling point

is lower. Tetrachloroethene (HARMFUL) may also be used.

20

Tetrachloromethane was the ideal solvent because water absorption is extremely small and solutions of acid
chlorides kept for years.
11

4.

Safer alternatives to asbestos

4.1

Safer mineral fibre

Machine-made mineral fibre21, used as a replacement for asbestos wool in school science, is still
an emotive issue because of fears that it might induce cancer as a result of inhaling airborne
fibres. Most mineral fibre, including Triton Kaowool Ceramic Fibre22 (a white fibre material
made by Thermal Ceramics UK Ltd23), is given an R40 rating (limited evidence of a carcinogenic effect) in the Approved Supply List (see footnote 1). This risk phrase indicates that it is a
category 3 carcinogen (substances which cause concern but as yet there is no direct evidence to
link them to human cancers). The following statement24 should be noted.
Man-made mineral fibres are coarser than asbestos fibres and do not split longitudinally into fibrils. Most currently available products do not readily release airborne fibres. Some fibres are fine
enough to be breathed in, but few will reach the deep lung and those that do will not persist as
they are generally much more soluble than asbestos. While there is limited evidence of an
increased lung cancer risk in workers producing mineral wool insulation in the early days of the
industry, there is no evidence of an increase in risk of mesothelioma.

Thermal Ceramics UK has also produced Superwool 607, a fibre which, when tested, did not
give results which warranted a R40 risk phrase and is safer to use. It is now available from
Philip Harris (cat. no. C5H71636, 500 g, 10.38), Scientific & Chemical Supplies (cat. no. MI020,
500g, 4.66) and Griffin Education (cat. no. SPW-607-010L, 5.5 m x 610 mm x 6 mm blanket,
14.18).
Ceramic fibre is useful because it is an inert material, which keeps reactants apart or retains
heavy vapours, dusts and powders and stops them entering the atmosphere. Some examples of
its use follow.

Keeping reactants apart

Retaining heavy vapours and dusts

Diagram A shows a common arrangement of

equipment used for passing steam over magnesium and cracking hydrocarbons or alcohols. It
is also known as the Arculus method. When heating nitrates and testing for oxygen, it has been
known for pupils to put glowing splints into molten
nitrate, accidentally at first and then on purpose, to
witness the very violent reaction. Placing mineral
fibre at the end of the ignition tube (Diagram B)
allows oxygen to diffuse through the fibre but
prevents the glowing splint from reaching the
molten nitrate.

The fibre allows gases or vapours to pass

through but retains dusts and powders. However,
the denser the gas the slower the rate of diffusion so hazardous vapours take a comparatively
long time to diffuse through the fibre.

Other reactants or
catalysts can be placed here

The arrangement in diagram B can be used

when heating ammonium chloride, ammonium
dichromate(VI) (see page 30), coal, iodine,
iron/sulfur mixtures (see page 31), metal
nitrates, potassium chlorate(V) and
potassium manganate(VII).

Substance to
be heated is
placed here

Mineral fibre is
placed in the
opening or
further down

The fibre absorbs

the liquid
Diagram B

Diagram A
21
22
23
24

This used to be called Man-Made Mineral Fibre (MMMF)!

Available from Griffin & George: T/3740/48 for 100 g: (look under T in the chemicals section of the catalogue.
From Beecroft: CC3500-52 for 100 g; CC3500-56 for 500 g; (look under Ceramic fibre wool).
Thermal Ceramics UK Ltd, Tebay Road, Bromborough, Wirral CH62 3PH. Tel 0151 334 4030, Fax 0151 334 1684,
Web site: www.thermalceramics.com.
Asbestos and Man-Made Mineral Fibres in Buildings: Practical Guidance, ISBN 0727728350, Thomas Telford Publishing, 2000, or from www.environmental-center.com/articles/article725/article725.htm.
12

4.2

Heat-resistant paper

Machine-made mineral fibres can be reconstituted into heat-resistant paper using an organic
acrylic binder. This binder should be burnt off in a fume cupboard before the paper is used.
After the burning process, the paper is more brittle and should be handled carefully, otherwise
it breaks up. If required, the paper should be shaped before the binder is burnt off.
Heat-resistant paper (2 mm thick) made from Superwool 607 (minimal hazard) is suitable for
use in schools and is now available from Scientific & Chemical Supplies (250 x 250 mm sheet,
cat. no. APS020010, 3.73; 50 mm x 10 m roll, cat. no. APS020020, 10.71) and Griffin & George
[but unfortunately only in bulk quantities (cat. no. SPW-607-P; pack of 5 rolls 20 m x 500 mm)].

The copper(II) oxide/zinc reaction

Wear eye protection.
Procedure

Cut a piece of 2 mm heat-resistant paper 80 x 40 mm. Fold it lengthways

in a V shape. Alternatively, use two sheets of 1 mm paper together.
In a fume cupboard, hold the paper in tongs to burn off the binder. Continue burning until black carbon left on the paper is burnt away, leaving a
white surface. The paper is quite brittle now so take care when handling it.
In two separate weighing boats (or other dry receptacles) measure 0.25 g
of copper(II) oxide and zinc powder respectively. Pour the contents of one
receptacle into the other and then pour back again. Do this several times
to ensure good mixing.
Place the mixture along the centre of the V in the paper.
Light a Bunsen burner and apply the flame directly to the solid. Remove
the flame immediately the reaction starts.
Have ready a 250 ml beaker containing 1 M sulfuric acid. Add the paper
and its contents to the beaker and heat to boiling.
The acid dissolves zinc oxide, unreacted zinc and unreacted copper(II)
oxide. Note the colour of the solid remaining.
Disposal: pour all contents of the beakers through a sieve to remove the
solids. The liquid can be diluted and poured down the foul-water drain.
The solids can be placed in the waste bin.

Burning calcium
This demonstration should be carried out by an adult with the students at least 3 m away, all
wearing eye protection. They should cover their eyes with open fingers to reduce some of the
light. A Bunsen burner flame using natural gas is not hot enough to light calcium but a kitchen
blowtorch25 works well.

Procedure

Make a 4 mm layer using four 40 x 40 mm pieces of 1 mm heat-resistant

paper26. There is no need to remove the binder.
Place them on a gauze supported by a tripod.
Wear a face shield. Wear thermal protective gloves.
Using forceps, place one or two granules of calcium on the paper.
Light the kitchen blowtorch and, holding it at arms length, apply it to the
calcium. Place the other hand in front of the eyes with open fingers. Ask
the class to do the same.
The calcium will ignite with a bright red flash.

A kitchen blowtorch
25

26

A kitchen blowtorch is available from a cooking gadget shop. It uses LPG from lighter fuel which gives a very hot,
narrow flame. (It can also be used to make holes in borosilicate test tubes, which converts them into combustion
tubes, and repair chipped borosilicate glassware.)
Two pieces of 2 mm thick Superwool 607 heat-resistant paper could be used.
13

5.

Safer combustion of liquid fuels

5.1

Safer spirit burners

Myths: Arent spirit burners banned? We have heard that explosions have occurred. We are
not allowed to use methanol as a fuel as it is toxic.

A few explosions have been reported but, so far, only with methanol, the most volatile of the
alcohols. For an explosion to occur, a mixture of air and alcohol vapour is required. The explosive range for methanol is between 7 and 37%, which is the widest range of all the alcohols; for
ethanol it is between 3.3 and 19%. We have been able to reproduce a small explosion by using a
burner with a wick much narrower than the hole through which it fits, leaving a gap between
the wick and the holder. If the spirit burner is only partially filled with methanol, there is an
air/methanol mixture in the vessel. As methanol rises up the wick and is ignited (with a lighted
splint), the flame backfires through the gap into the vessel, creating a small explosion. Spirit
burners, currently available for purchase, appear to be made of glass although you may have
older versions made of brass or zinc27.
Methanol is TOXIC by inhalation, skin absorption and if swallowed; it is also HIGHLY FLAMMABLE. The level of methanol in the atmosphere of the laboratory will be minimal during use of
the burners. If the experimental procedure is carried out correctly, there is no reason why
pupils should be exposed to vapour levels hazardous to health.
Table 8 describes the control measures that should be observed when buying and preparing
spirit burners for pupil use.

Table 8

Control measures for buying and preparing spirit burners

Control measure
Purchase spirit burners with
a capacity of 50 ml or less.
Make sure that the design is
suitable for the intended
purpose and the burner is
well constructed.

Use a small funnel to fill a

spirit burner.
Fill the spirit burner more
than half full.
Replace a wick with one of
the same diameter.
KS3 and 4 pupils should not
fill spirit burners.

Lighted spirit burners must

not be moved.

27
28

Comment
Many designs have a capacity of over 100 ml, eg, the five burners on
the left in the picture below. The burner on the far right was the smallest with a capacity of 50 ml.
Many spirit burners on the market are sold for aromotherapy and dinner
parties (eg, the four on the left in the picture). For some, their glass
construction is rather thin. The tops on some burners also do not fit
well. Of the spirit burners in the main suppliers catalogues, the design
on the right below is probably the best28. Quality control may well be a
problem with all designs, so examine new purchases carefully.

The openings on the burners are narrow and it is easy to spill highly
flammable liquid.
This will ensure that there will not be an explosive mixture of air and
alcohol vapour in the burner. If you have to use a large-capacity spirit
burner, eg, > 50 ml, partially fill it with a resin or with cotton wool.
Explosions occur when the flame travels down a narrow wick and
ignites the alcohol/air mixture in the burner.
It is good practice to have several burners filled, labelled accordingly
and ready for use. They should be refilled in the prep room before the
start of any practical. If methanol is to be used as a fuel, burners should
be filled in a fume cupboard with no sources of ignition near by. The
technician or teacher should wear eye protection.
Never hold in the hand a spirit burner about to be used. It should be
placed on the bench and lit only with a lighted spill or match. Once
alight, do not move a burner around the laboratory.

Old metal burners have exploded as well as those made of glass!

Available from Griffin & George, Beecroft and Timstar.
14

Table 8

Control measures for buying and preparing spirit burners (cont.)

Control measure
The holder in which the wick
fits should not be cracked or
severely chipped.

Comment
Many wick holders are made of porcelain which becomes chipped
because of poor handling by the maker or supplier, misuse in laboratories or thermal stress. The tops must be loose so the burner can be
refilled but many are so loose that they fall out when the burner is
tipped up, either by accident or on purpose. If very loose, it is possible
that there is a sufficient gap to ignite the alcohol in the container.
Misbehaviour in this activity could lead to serious consequences. The
teacher must be vigilant at all times during the activity. Perhaps the
technician, if given time, could help the pupils when they are using the
balance. Teachers with unruly pupils should consider performing a
demonstration or making a video of the procedure so that recordings of
the mass and temperature can be made by watching the recording.

Ensure good pupil

behaviour.

5.2

D-i-y spirit burners

Spirit burners could be made in house from small jars or bottles, previously used for jam or
ink. Examples are shown in the diagrams below. The volume of highly flammable liquid can be
reduced still further by partially filling the bottle with cotton wool or epoxy resin.
Cotton string wick
Super glue to fix
the glass to the lid

6 mm medium-wall borosilicate
tubing fed through a 6.2 mm hole
in the lid
1.5 mm expansion hole

Small jam jar

Ink bottle

35 mm

Resin

Highly flammable
liquid
40 mm

5.3

A review of procedures for measuring the energy content of fuels

Confusion arises when comparing the energy content of fuels, such as the alcohols, and in foods
(eg, burning peanuts or alternative materials29). Usually, the small amount of oil in a nut or
snackfood is used to heat water in a large test tube containing about 10-20 ml of water; a burning peanut can boil this volume of water30. This activity is a flawed technique, giving rise to
inaccurate estimates of energy content. Students should be asked how they could improve it,
eg, by surrounding the test tube with an empty tin to reduce draughts.
The information in Table 9 uses enthalpy of combustion data to estimate the temperature rise
when heating 250 g of water by burning 1 g of an alcohol.

Table 9 Temperature increase, on burning 1 g of alcohol to warm 250 g of water

Alcohol

Methanol

Ethanol

Propan-1-ol

Butan-1-ol

Pentan-1-ol

Hexan-1-ol

Heptan-1-ol

Increase

21.6 C

28.3 C

32.1 C

34.4 C

36.0 C

37.2 C

38.1 C

Greater accuracy is obtained in this activity when using a balance to 2 decimal places, an accurate thermometer marked with 1 intervals, a large volume of water, a small temperature rise
and protection from draughts.

29
30

See PS10, The Burning Peanut Investigation and Allergies to Nuts, CLEAPSS School Science Service, for further
information.
Anti-bumping granules should be added to the test tube containing water so that boiling water does not shoot out
and scald pupils.
15

6.

Safer advanced-level organic chemistry

6.1
Phenylamine (aniline) reactions - a safer alternative
Comment
Phenylamine (aniline) (TOXIC) has a short-term exposure limit (STEL) of 5 ppm

(20 mg m-3) and a long-term exposure limit (LTEL) of 2 ppm (10 mg m-3)31. It is
unlikely the STEL level would be reached in a laboratory where students are carrying out simple test-tube reactions with small amounts of material. However, there
are less hazardous aromatic amines available, which should be used in preference. Ethyl 4-aminobenzenecarboxylate (ethyl 4-aminobenzoate) is recommended
although it is labelled IRRITANT32 by some suppliers. It is used as a local anaesthetic to the skin (benzocaine) and is present in some throat sweets!

H3C

O
NH2
O
Ethyl 4-aminobenzenecarboxylate

Procedure

Solubility and pH
Add 2 ml of distilled water to a test tube followed by a small amount (0.02 g) of
ethyl 4-aminobenzenecarboxylate. Heat to boiling, add a few drops of fullrange indicator and allow the solution to cool.
Formation of salts
Add 0.02 g of ethyl 4-aminobenzenecarboxylate to 4 ml of 1 M hydrochloric
acid in a test tube. Warm the solution, if necessary, to dissolve the solid. Now
add 5 ml of 1 M sodium hydroxide solution (CORROSIVE).
Addition of copper(II) ions
Add 0.02 g of ethyl 4-aminobenzenecarboxylate to 2 ml of 0.1 M copper(II)
sulfate solution. Warm the mixture and then allow it to cool.
The addition of bromine water
Dissolve 0.02 g of ethyl 4-aminobenzenecarboxylate in 4 ml of 1 M hydrochloric acid in a test tube. Add 2 ml of bromine water (IRRITANT).
Ethanoylation
Place 0.5 g of ethyl 4-aminobenzenecarboxylate into a boiling tube and add
0.5 ml of ethanoic anhydride (CORROSIVE) in a fume cupboard. Note what happens during the reaction. In the fume cupboard, add 2 ml of water and heat to
boiling. Cool the solution in an ice bath with stirring and filter off the crude
solid. Add the solid to 4 ml of 50% ethanol/water mixture (HIGHLY FLAMMABLE),
recrystallise, filter and find the melting point of the solid when it is dry.
Diazotization and coupling reactions
Dissolve 0.25 g of ethyl 4-aminobenzenecarboxylate in 1 ml of 1 M hydrochloric acid in a boiling tube. Cool this solution in an ice bath. Dissolve 0.2 g of
sodium nitrate(III) (OXIDISING and TOXIC) in 1 ml of water in another boiling tube
and cool this solution. Dissolve 0.5 g of naphthalen-2-ol (HARMFUL) in 5 ml of
1 M sodium hydroxide (CORROSIVE). Add the ethyl 4-aminobenzenecarboxylate
solution to the sodium nitrate(III) solution and then add this mixture to the
naphthalen-2-ol solution.

Disposal

These procedures are carried out with minimum quantities and the materials can
be flushed down the foul-water drain.

31
32

See CLEAPSS Laboratory Handbook, section 7.9.1 for information on Occupational Exposure Limits.
R43: May cause sensitisation by skin contact (VWR International Ltd [formerly Merck Ltd]); R38: Irritating to the
skin (Aldrich): Minimal risk (Fisher).
16

Notes

CH3

CH 3

Br
O
O
H3C

H2N

O
NH

O
O
Br

I
Ethyl 4-amino-3,5dibromobenzenecarboxylate

CH3

II
Ethyl 4-(ethanoylamino)
benzenecarboxylate

O
H2N
O
Ethyl 4-aminobenzenecarboxylate

CH 3

O
N
N

OH

III

Ethyl 4-[2-(2-hydroxy-1-naphthyl)
hydrazino]benzenecarboxylate

Ethyl 4-aminobenzenecarboxylate is soluble in hot water. It cools to form long,

needle-shaped crystals. The solution has a neutral pH. As the ester group is electron withdrawing, the substance is a slightly weaker base than phenylamine. Ethyl
4-aminobenzenecarboxylate dissolves in 1 M hydrochloric acid and is precipitated
on addition of the alkali. The solution turns lime green on warming with copper(II)
ions indicating the formation of a complex ion with ethyl 4-aminobenzenecarboxylate acting as a ligand. The blue colour returns on cooling. With bromine water
added to ethyl 4-aminobenzenecarboxylate, a white precipitate (structure I) is
formed.
Ethyl 4-aminobenzenecarboxylate dissolves in ethanoic anhydride. As the reaction
proceeds, heat is evolved and another solid appears. It may be necessary to add
more water if the solid does not recrystallise on cooling. The melting point of the
product (structure II) should be 110 C. Diazotization of ethyl 4-aminobenzenecarboxylate and coupling with naphthalen-2-ol produces a red dye (structure III).
Azo dyes should not be isolated. The diazonium salt of ethyl 4-aminobenzenecarboxylate appears to be stable at room temperature but cooling is included so
that, in the procedure, students are less likely to be confused about reaction
conditions for phenylamine. Heating the diazonium salt results in only a small
amount of coupling, with a yellow dye being formed.

17

6.2
Phenol reactions - a safer alternative
Comment
Phenol vapour has a maximum exposure limit (MEL) of 2 ppm for long-term exp-

osure although it is doubtful that this level would be reached in a laboratory at

room temperature where only small amounts are being used33. Phenol is TOXIC in
contact with the skin and if swallowed and CORROSIVE, causing burns. It solidifies
into a lump when kept for long periods. It then becomes very difficult to remove
from the bottle.
However, there are less hazardous aromatic phenols available. Methyl 4-hydroxybenzenecarboxylate (methyl 4-hydroxybenzoate) has an IRRITANT warning from
Aldrich but other suppliers issue no hazard warnings. Unlike phenol, it does not
absorb water from the atmosphere.

CH3
O
OH
O
Methyl 4-hydroxybenzenecarboxylate

Procedure

Solubility and pH
Add 2 ml of distilled water to a test tube followed by 0.02 g of methyl 4hydroxybenzenecarboxylate. Heat to boiling, add a few drops of full-range
indicator and cool slowly.
Formation of salts
Add 0.02 g of methyl 4-hydroxybenzenecarboxylate to 2 ml of 2 M sodium
hydroxide solution (CORROSIVE). Warm the solution if necessary. Now add 3 ml
of 2 M hydrochloric acid (IRRITANT).
Addition of iron (III) ions
Add 0.02 g of methyl 4-hydroxybenzenecarboxylate to 2 ml of 0.01 M iron(III)
chloride solution.
Ethanoylation
Dissolve 0.5 g of methyl 4-hydroxybenzenecarboxylate in 4 ml of 2 M sodium
hydroxide solution (CORROSIVE) in a boiling tube. In a fume cupboard, add 1 ml
of ethanoic anhydride (CORROSIVE) and swirl the liquid round for a few minutes.
Note what happens during the reaction. Let the liquids settle, then place the
boiling tube in an ice bath. Decant off the liquid, add 8 ml of 50% aqueous
ethanol solution (HIGHLY FLAMMABLE) to the solid and remove from the fume
cupboard. Warm until the solid dissolves, cool in an ice bath (if the solid does
not form, scratch the sides of the container with a glass rod or spatula) and
filter off the solid. When the solid is dry, obtain its melting point.
The addition of bromine water
Add 0.02 g of methyl 4-hydroxybenzenecarboxylate to bromine water
(IRRITANT).
Nitration
Add 0.04 g of methyl 4-hydroxybenzenecarboxylate to 4 ml of 1 M nitric acid
(CORROSIVE). Heat the solution to boiling, allow it to cool slowly for 2 minutes
and then quickly in an ice bath. Filter off the solid. Dissolve the solid in 1 ml of
ethoxyethane (EXTREMELY FLAMMABLE) and use chromatography to analyse the
solution using silica plates (80 x 40 mm) alongside a reference solution of
methyl 4-hydroxybenzenecarboxylate. The chromatography solvent is a 1:1
hexane/ethoxyethane mixture (EXTREMELY FLAMMABLE) and the products
should be viewed under U-V radiation (do not look directly at the lamp).

Disposal

These procedures are carried out with minimum quantities and the materials can
be flushed down the foul-water drain.

33

See CLEAPSS Laboratory Handbook, section 7.9.1 for information on Occupational Exposure Limits. The value for
phenol was altered in EH/2002, Occupational Exposure Limits 2002, HSE Books, ISBN 0717620832.
18

Notes

CH3
O
OH
O

CH3

CH3 Br

O
O

OH
CH3

O
I

O
Br

Methyl 4-(ethanoyl)benzenecarboxylate

II

Methyl 2,6-dibromo-4-hydroxybenzenecarboxylate

Solubility and pH
Methyl 4-hydroxybenzenecarboxylate is soluble in hot water. It cools to form long,
needle-shaped crystals. The solution is acidic, giving pH values between 4 and 5.
As the ester group is electron withdrawing, the substance is a slightly stronger acid
than phenol.
Formation of salts
Methyl 4-hydroxybenzenecarboxylate dissolves in alkali and is precipitated on
addition of acid.
Addition of iron(III) ions
The solution turns violet as a complex is formed.
Ethanoylation
An emulsion forms and the solution becomes warm. The ester then separates from
the aqueous solution as the bottom layer. It solidifies on cooling. The melting point
of the ester (structure I) is 85 C.
The addition of bromine water
A white precipitate is formed. Structure II is a possible structural formula for the
product.
Nitration
A yellow solid is obtained. The chromatogram shows the nitro product (Rf = 0.62)
and the original product (Rf = 0.55). Other coloured products may be seen on the
chromatogram.

19

6.3
Nitration of benzene - a safer alternative
Comment
The use of benzene has been prohibited34 in places of work as it is a class 1 carcinogen. Methyl benzenecarboxylate (benzoate) (I), a suitable alternative, is HARMif swallowed but there is no evidence of carcinogenic, mutagenic nor teratogenic effects. There is little hazard information about the product, methyl 3-nitrobenzenecarboxylate (3-nitrobenzoate) (II), but no adverse effects have been
reported. The important risks remain with the use of concentrated acids.
FUL

H3C

H3C

conc H2SO4

HNO3

+
+

H2O

N
I

II

Procedure

Wear goggles or a face shield to guard against chemical splashes. Do not sit
down when handling concentrated acids. In a clean, 100 ml DRY conical flask,
add 10 ml of concentrated sulfuric acid (CORROSIVE) and cool it to below 10 C
in an ice bath.
Place about 4 ml of methyl benzenecarboxylate in a pre-weighed 10 ml measuring cylinder and obtain its mass. Add the liquid to the cold acid. Calculate the
mass of methyl benzenecarboxylate added to the acid.
Stir the mixture well in the conical flask and continue cooling it.
In another, DRY conical flask or boiling tube, prepare a mixture of 3 ml each of
concentrated sulfuric and nitric acids (both CORROSIVE) and cool this mixture in
an ice bath.
Using a dry dropping pipette, add the nitric/sulfuric acid mixture to the acidic
methyl benzenecarboxylate solution a drop at a time, swirling the flask,
controlling the addition so that the temperature stays in the range of 5 to 15C.
After the addition, allow the flask to stand at room temperature for 10 minutes.
Pour the liquid onto about 40 g of crushed ice in a beaker and stir until the
product solidifies.
Filter off the solid; suction filtration with a Bchner flask is quicker.
Wash the solid with three 5 ml portions of water.
Change the collection flask for a small, clean, dry flask and wash the product
with two portions of 5 ml ice-cold ethanol35 (HIGHLY FLAMMABLE). Keep the
filtrate for the extension.
To purify the main product by recrystallisation, transfer the solid to a 100 ml
conical flask, add 20 ml of ethanol and place the flask in a beaker of almost
boiling water from an electric kettle.
When the solid dissolves, remove the flask, filter the liquid into another conical
flask (suction filtration) and allow the solution to cool (in an ice bath if time is
short).
Filter off the solid, allow it to dry and find the mass of material formed and
hence the percentage yield of the reaction.
Find the melting point of the product.

Disposal

The product may be saved and recycled; see procedures 6.4 and 6.5.

Extension

Carry out thin-layer chromatography on the recrystallised product [use ethanol

(HIGHLY FLAMMABLE) to dissolve the solid] and the ethanolic filtrate, which will need
reducing in volume. Use ethoxyethane/hexane mixture (1:9 by volume) (HIGHLY
FLAMMABLE and HARMFUL) as the eluting solvent. After the chromatogram is developed, the spots can be located by using either ultra-violet radiation (do not look
directly at the lamp) or an atmosphere of iodine vapour (HARMFUL).

34
35

COSHH Approved Code of Practice and Guidance, 2002, HSE Books, ISBN 0717625346.
Ethanol should be cooled in a freezer in a plastic, screw-capped bottle.
20

6.4
A safer use of nitrated products
Hydrolysis of methyl 3-nitrobenzenecarboxylate to 3-nitrobenzenecarboxylic acid
Comment
Disposal of organic waste is a problem, so recycling the product from the previous

preparation saves money and helps protect the environment. This activity involves
the saponification of the ester to form the sodium salt of the acid, followed by
acidification to produce 3-nitrobenzenecarboxylic acid.
CH3
O

+
+

Na

HO

+ H3C

OH

Na

Sodium 3-nitrobenzenecarboxylate

O Na

+
+

Na

OH

3-nitrobenzenecarboxylic acid

The hazards of the product, 3-nitrobenzenecarboxylic acid, are not well established. It is suggested that it is treated as both a HARMFUL and IRRITANT substance.

Procedure

Disposal

Place 2 g of methyl 3-nitrobenzenecarboxylate in a 50 ml pear-shaped flask

and add 15 ml of 2 M sodium hydroxide solution (CORROSIVE) and an antibumping granule.
Attach a reflux condenser and warm the flask gently until the two layers mix
and then continue for another 10 minutes.
Pour the solution into a beaker, cool it in an ice bath and add 2 M hydrochloric
acid (IRRITANT) until the solution is acidic.
Filter off the product.
A small amount of crude 3-nitrobenzenecarboxylic acid can be recrystallised
from 3 ml of hot 0.5 M hydrochloric acid and its melting point can be found
(138-141 C).

Keep the solid to illustrate reduction to a primary amine and formation of an azo
dye (see procedure 6.5). Otherwise, store it with other organic waste for collection
by an authorised contractor.

21

6.5
Reduction of nitrobenzene - a safer alternative
Comment
The reduction of a nitro-group to the amine group is not an easy procedure. The

usual method involves reducing nitrobenzene to phenylamine, a procedure requiring a fume cupboard. The following method uses 3-nitrobenzenecarboxylic acid
prepared by the saponification of methyl 3-nitrobenzenecarboxylate (see 6.4). This
procedure can be carried out in the open laboratory.

OH

OH

Sn/Conc HCl

O
NH2

3-Nitrobenzenecarboxylic acid

3-Aminobenzenecarboxylic acid

Unfortunately, it is not possible to isolate the pure amino acid. The solid obtained
is the chloride salt of 3-aminobenzenecarboxylic acid. The presence of the substance can be illustrated by the formation of an azo dye and a copper complex.

Procedure

Disposal

Use a fume cupboard. Wear goggles. Place about 2 g of crude 3-nitrobenzenecarboxylic acid in a 50 ml pear-shaped flask. Add 5 g of tin and 10 ml of
concentrated hydrochloric acid (CORROSIVE).
Set up Quickfit apparatus for reflux. The pear-shaped flask should be surrounded by cold water in a beaker. Add an anti-bumping granule to the water.
Heat the water to boiling with a gentle Bunsen burner flame and note the
changes inside the pear-shaped flask. Once the solid has dissolved, continue
boiling for 10 minutes longer. After disconnecting the apparatus, pour the
contents into a 250 ml beaker and cool in an ice bath. In the fume cupboard,
add concentrated ammonia (CORROSIVE) until the solution is just alkaline.
Take care when handling hot glass in this step. Heat the beaker with the white
suspension to boiling to coagulate the precipitate [tin(II) hydroxide] and filter
the suspension. Collect the solution in a 250 ml conical flask. Wash the precipitate with a little water.
Boil off the water in the conical flask until about 5 ml of solution is left.
Cool the flask and the filtrate in an ice bath. When cold, swirl the flask and filter
off the solid product which is the chloride salt.
Azo dye formation On dissolving the chloride salt in dilute hydrochloric acid
and adding cold sodium nitrite solution, a diazonium salt is formed which
reacts with an alkaline solution of naphthalen-2-ol to give a red dye.
Copper(II) complex formation If the chloride salt is added to 2 ml of 0.1 M
copper(II) sulfate solution, a green complex is formed.

The materials can be added to water and flushed down the foul-water drain.

22

6.6
A safer solvent for the extraction of caffeine from tea
Comment
Chlorinated hydrocarbons have been used as the extracting agent for this activity.
In view of the hazards both to health and the environment of these substances,
use can be made of propan-1-ol which, when saturated with sodium chloride, is
immiscible with water36.

About 50 mg of caffeine can be extracted from two bags of tea. Slow evaporation
of a propanone solution of caffeine produces attractive, needle-shaped crystals.

Procedure

Wear eye protection. Boil pure water in a kettle.

Pour about 50 ml of boiling water onto two tea bags in a 250 ml beaker. Let
this stand for 5 minutes.
Stir and squeeze the tea bags with a glass rod to extract the tea solution.
(Take care: hot glassware.) Decant the solution into a 250 ml conical flask
leaving the bags behind. Add about 20 ml of boiling water to the bags, stir and
squeeze with the rod and again decant the solution into the conical flask.
Add approximately 16 g of sodium chloride and heat the solution to boiling on
a tripod and gauze.
While hot, add approximately 1 g of calcium hydroxide to the tea solution.
Prepare an ice bath and cool the flask and its contents. Try not to disturb the
precipitate, which is very fine.
Place about 0.5 g of Superwool 37 (or other mineral fibre) in the neck of a
filter funnel and slowly add the cold, cloudy tea liquid. A clear solution should
come through. This can be further filtered in the normal way if required.
Pour the solution into a separating funnel and add 15 ml of propan-1-ol
(HIGHLY FLAMMABLE) and replace the stopper. (Note which layer is which!)
Agitate the funnel to dissolve the caffeine into the propan-1-ol layer.
Remove the stopper and drain off the lower, aqueous layer into a conical flask.
Now drain the propan-1-ol layer into another flask.
Return the aqueous layer to the separating funnel and add a further 10 ml of
propan-1-ol. Repeat the separation and draining processes, combining the
propan-1-ol which contains caffeine, tannins and some sodium chloride into
one flask.
(Wear goggles.) Return the combined propan-1-ol solution to the separating
funnel and this time add 25 ml of 2.5 M sodium hydroxide solution (CORROSIVE). This will remove the sodium chloride and remaining tannins from the
propan-1-ol. Repeat the agitation action, drain off the unwanted aqueous layer
and drain the propan-1-ol layer into another conical flask.
Add anhydrous sodium sulfate and swirl. All water will be removed when the
liquid is clear and the sodium sulfate is free flowing.
Decant the solution into a clean, pear-shaped flask and set up for distillation.
Distil until there is about 5 ml of propan-1-ol left. Remove the remaining
alcohol and caffeine with a Pasteur pipette into a weighed, glass Petri dish and
allow the alcohol to evaporate overnight. It could be warmed gently on a hot
plate.
Scrape the solid into a test tube. Add about 2 ml of propanone (HIGHLY FLAMMABLE), swirl and decant the liquid into another Petri dish. Allow the propanone
to evaporate in a working fume cupboard.

Disposal

Tea bags can be placed in the waste. The waste sodium hydroxide solution should
be washed away with plenty of water down the foul-water drain.

Controls and
hints

The version from which this method is adapted stated that the washing with
sodium hydroxide solution removed sodium chloride as well as the tannins from
the propan-1-ol solution but we were not totally convinced by this; hence the
washing with propanone.

36
37

The method is adapted from the following article: Hampp, Andreas, The Extraction of Caffeine from Tea: A Modification of the Procedure of Murray and Hansen, J. Chem. Educ, 1996, 73 1172.
See section 4.1 of this guide.
23

6.7

A safer reagent to oxidise alcohols to carboxylic acids

Myth: As chromium(VI) compounds are carcinogenic, this procedure is now not allowed.

Comment

Preparative oxidation reactions are usually carried out with sodium dichromate(VI)
dissolved in sulfuric acid of various concentrations. Chromium(VI) compounds are
all deemed TOXIC as they are carcinogens. The risk to health is extremely low as
the route is via inhalation and there is not much chance of breathing in aerosols of
chromium(VI) compounds in the school laboratory. Poor mixing of concentrated
sulfuric acid with water causes a more common accident. This standard procedure
is not banned but a less hazardous reagent can be used. The reaction can be
represented by the following equation.
4MnO-4(aq) + 3C6H5CH2OH(l) 3C6H5COOH(aq) + 4MnO2(s) + 4OH-(aq) + H2O(l)
The product, benzenecarboxylic acid, is neutralised by sodium carbonate to form
the benzenecarboxylate ion, which is soluble in water. After filtering off the manganese(IV) oxide and removing the unreacted manganate(VII) ion, the addition of
hydrochloric acid produces benzenecarboxylic acid. Yields of 55% of crude benzenecarboxylic acid were obtained but rose to 73% on reducing the volume of
filtrate.

Procedure

Wear eye protection. On a weighing boat, place 1.5 g of potassium manganate(VII) and 0.5 g of sodium carbonate.
Carefully pour this into a 50 ml pear-shaped flask and add 20 ml of water.
Swirl the mixture so that the solids dissolve.
Stand the pear-shaped flask in a beaker and tare it on a balance. Add about
0.5 ml of phenylmethanol and note the reading on the balance. This is the
mass of starting material. Add an anti-bumping granule to the flask.
Set up the pear-shaped flask for reflux. Lower the flask into a 400 ml beaker
on a tripod and gauze.
Add water to the beaker to about the 300 ml level. Add a couple of antibumping granules to the beaker. (Your teacher should examine the equipment
before you proceed.)
Light the Bunsen burner, place it below the gauze and let the water boil for at
least 15 minutes. Keep the water level topped up.
After 15 minutes, when the Bunsen burner is turned off, turn off the cooling
water to the condenser and raise the pear-shaped flask. Using a thick cloth,
remove the very hot beaker containing water.
Using the cloth, remove the clamp from the boss and pour the reaction mixture
through filter paper to remove the manganese(IV) oxide. Note the time when
the reaction has stopped. Collect the filtrate in a conical flask. The solution is
purple because of unreacted potassium manganate(VII).
Add a magnetic stirrer bar and place the flask on a magnetic stirrer. As it stirs,
add a little sodium metabisulphite. Add this steadily until the solution clears.
Wear safety goggles. IN A FUME CUPBOARD, place a pH meter in the mixture, add drops of concentrated hydrochloric acid until the pH is less than 2.
(Take care: sulfur dioxide, a TOXIC gas, is produced.)
Place the solution IN THE FUME CUPBOARD, and heat to boiling. This
removes sulfur dioxide and dissolves precipitated benzenecarboxylic acid.
Remove the flask from the fume cupboard and allow it to cool to room temperature; ice can be used to accelerate cooling.
Filter off the benzenecarboxylic acid crystals.
More benzenecarboxylic acid can be obtained by boiling the filtrate until half
the original volume remains. Again, cool and filter off the crystals.
Place the benzenecarboxylic acid in 5 ml of water in a test tube, heat to
boiling, filter and collect the filtrate in a 100 ml beaker. On cooling, the crystals
of benzenecarboxylic acid can be filtered off, dried in an oven and the melting
point can be measured.

Disposal

The pear-shaped flask must be rinsed in water immediately. Any stains can be
removed with sodium metabisulfite solution in the fume cupboard.

Controls and
hints

A stirring rod can be used in place of a magnetic stirrer but it is not as efficient.
There is scope for more research with this reagent at school level.
24

7.

Hydrogen reactions - safer procedures

7.1

Hydrogen burning and exploding in air

Myth: Hydrogen is explosive and cannot be used in schools.

Comment

When hydrogen has been prepared or used on a large scale, demonstrators have
sometimes failed to flush out all the air from a gas generator, so that impure hydrogen is collected and ignited, resulting in several accidents. Many chemicals, eg,
methane and ethanol, explode when ignited in the presence of air but the range of
ratio of air to chemical is often quite narrow. However, mixtures of hydrogen and
oxygen explode over a wide range (4 to 77%). The ignition temperature of hydrogen is reduced by the presence of metals and their compounds, [eg, copper(II)
oxide].
With the procedure and apparatus below, hydrogen can be safely prepared and
burnt with the inevitable final explosion.

Procedure

Rubber tubing

Hoffman clip
Clamp

Hydrogen in

1 litre plastic
soft drinks
bottle cut off
at the bottom

Filling the chamber

Controls and
hints

Glass tube
5 mm bore

Burning the hydrogen

Fill the explosion chamber (a 1 litre, plastic, soft drinks bottle) with water by
opening the Hoffman clip and sucking up the water until it is just below the
glass tube in the bung. Tighten the clip sufficiently that the level does not drop.
Unless a hydrogen cylinder is available, generate hydrogen with at least
100 ml of 3 M hydrochloric acid and granulated zinc, adding about 5 ml of 1 M
copper(II) sulfate solution to increase the speed of reaction. The volume of
dead space in the generator must be less than 1 litre to ensure that all the air
in the generator has been expelled.
Pass hydrogen into the explosion chamber until it is full of gas. If the hydrogen
is prepared chemically, a considerable volume of air will also come over. As
there must be no air in the chamber, keep the delivery tube under water and,
after opening the Hoffman clip, lift out and invert the chamber so the air/
hydrogen mixture is lost. Refill the chamber with water, reset as above and
continue to collect pure hydrogen in the chamber. (If a hydrogen cylinder is
used, this step is not required.)
When bubbles escape from the chamber, it will be full of pure hydrogen.
Remove the generator away from the equipment.
Light a Bunsen burner about 1 metre from the apparatus.
Slowly lift the clamp up the retort stand raising the bottle out of the trough, retighten the boss on the clamp stand and remove the trough. Hydrogen is
retained because it is less dense than air.
Light a spill and hold this in one hand while the rubber tubing is removed from
the glass tube with the fingers of the other hand. Ignite the hydrogen at the top
of the tube with the spill. Move away to a safe distance.

If a chemical generator is used, see Hazcard 48.

Make sure the glass tube does not protrude through the bung. If it does, it collects
water which blocks the passage of gas when the clip and rubber tube are removed. If the glass tube is too narrow, it may not support the flame as it backfires
into the chamber.
Practice the demonstration before performing it. It does require some co-ordination! Do not become over-ambitious, using larger explosion chambers. The
explosion is quite loud enough!

25

7.2

Hydrogen/oxygen explosion
Myth: The very loud bang can cause damage to the room and distress to pupils.

Comment

If carried out on a large scale in glass apparatus, exploding large volumes of

hydrogen and oxygen in their stoichiometric ratios can shatter windows and glass
apparatus and the noise can cause deafness.
The function of risk assessment is to adjust the procedure to avoid these events.
Soap bubbles make a useful alternative means of holding the gases. Using the
method below ensures that there is no flying glass and the explosion is loud
enough for a laboratory.
Two holes are drilled with a very fine drill bit through the rubber bung that fits the
wide-necked, 100 ml bottle. A wider hole is bored though the bung which is then
fitted with glass tubing38. Two copper wires are fed through the bung and the
nickel-foil electrodes are soldered onto the wire.
The glass tubing is bent into shape using a non-luminous Bunsen burner flame to
melt the glass and being careful not to heat the bung.

Procedure

Nickel electrode soldered

onto copper wire

Detergent solution in
a crucible
on wood blocks
t d or
a laboratory jack

0.2M sodium sulfate solution

Pour the 0.2 M sodium sulfate solution into the 100 ml bottle so it reaches the
very top.
Have a beaker handy to collect the overspill as the bung containing the
electrodes is inserted into the neck of the bottle. The overflow rises up the
delivery tube and empties into the beaker.
Connect the copper wires to the low-voltage supply (6-8 volts is a suitable
setting) and pass current until no more solution is pushed out of the bottle into
the beaker. All this can be prepared earlier and the current turned off.
Place the crucible filled with 50% liquid detergent solution on the laboratory
jack or wooden blocks so that gases from the bottle will bubble through. Switch
on the current to collect bubbles of gas.
Switch off the current, lift the bottle so that the tube is clear of the crucible and
move the crucible closer to an ignited Bunsen burner.
Light a splint with the Bunsen burner flame and apply to the bubbles on the top
of the crucible.

Controls and
hints

Wear eye protection.

The Bunsen burner required for this demonstration should be at least 1 m from the
bottle.
The first gas sample may not explode with a loud crack as air might be present, so
repeat the procedure.
The glass tubing should be flush with the bottom of the bung.
The electrolyte is 0.2 M sodium sulfate solution rather than sulfuric acid. More
advanced students will appreciate that water molecules are being oxidised and
reduced at the electrodes to form oxygen and hydrogen.
This method uses nickel electrodes in place of platinum which are expensive and
difficult to solder. However, the nickel anode does oxidise during the process if the
electrolysis cell is left on for long periods. The solution becomes green and
nickel(II) hydroxide precipitates out.

Disposal

All solutions can be poured down the foul-water drain.

38

Use 6 mm medium-wall thickness borosilicate glass tubing.

26

7.3

Hydrogen as a reducing agent

Myth: A teacher was prosecuted for carrying out this reaction so it must be banned.

Comment

Using large-scale apparatus to reduce copper(II) oxide (HARMFUL) with hydrogen

(EXTREMELY FLAMMABLE), an experienced teacher ignited the hydrogen before all
air had been flushed through. The ensuing explosion sprayed glass and acid, contained in the hydrogen generator and drying bottle, over the students and himself,
none of whom were wearing eye protection. No safety screens were used and the
students were too close to the demonstration. The teacher was successfully prosecuted by the HSE because of his gross negligence in not using basic safety procedures. However, the procedure he used is not banned but it is seldom performed
these days.
Since this accident, safer alternatives to hydrogen, including methane and/or passing methane through ethanol, have been used as the reducing agent. However,
this complication can detract from the chemistry to be taught and confuse the
pupils. In this microscale version, the dead space has been reduced to a minimum and a borosilicate glass tube is used as the combustion tube. Mineral fibre
plugs prevent spray reaching the copper(II) oxide and the copper(II) oxide falling
out of the tube. The black copper(II) oxide becomes red as copper is formed.
Water, the other product of the reaction, condenses further up the tube.

Procedure

Mineral fibre Copper(II) oxide

Mineral fibre

Apply heat with a mini-Bunsen

burner or spirit burner
Hydrogen
generator

To make the hydrogen generator, bore a rubber bung that fits a specimen
bottle (eg, 40 x 25 (d) mm) and insert a 6 mm medium-wall borosilicate glass
tube, so that it is flush with the bottom of the bung. Bend the glass tube to 90
using a Bunsen burner flame and allow it to cool.
To make the combustion tube, use a micro-spatula to place copper(II) oxide
inside a straight 6 mm medium-wall borosilicate glass tube and add a little
mineral fibre39 to each end, poking it down the tube.
Use rubber tubing to connect the combustion tube to the bent glass tube.
Place 8 ml of 1 M sulfuric acid (IRRITANT), 1 ml of 0.1 M copper(II) sulfate and
zinc granules in the specimen tube. Place the specimen tube in a clamp. Insert
the bung, with the combustion tube attached.
Wait for 30 s so that hydrogen fills the combustion tube and expels the air.
Light the mini-Bunsen burner (adjusting the flame to just non-luminous) or
spirit burner with ethanol as the fuel.
Heat the copper(II) oxide in the combustion tube. As the colour of the solid
changes, move the flame further along the combustion tube until all the
copper(II) oxide has reacted.
Continue passing hydrogen over the copper until the combustion tube has
cooled and tip out the copper metal onto white paper.

Controls and
hints

Wear eye protection. Copper(II) sulfate is added to catalyse the zinc/acid reaction.

Disposal

Pour the solution in the specimen tube down the sink with lots of water. Keep the
zinc granules for future use in hydrogen generators.

39

The microscale approach will require extra dexterity by students, teachers and
technicians! Using a flex-cam, this procedure could be demonstrated and shown
on a television screen.

See section 4.1.

27

8.

Diffusion of gases - a safer alternative

Myth: Bromine is banned. It is too dangerous to handle.

8.1
Diffusion into air
Introduction
Bromine (VERY TOXIC and CORROSIVE) (see Hazcard 15) has caused a number of

accidents to both teachers and technicians, with serious burns to the skin or breathing difficulties. Bromine is not banned but if it is to be used, a knowledgeable colleague should be in the vicinity to provide assistance in case of an accident. Any
person handling bromine for the first time, or who does not handle it regularly,
should receive training from an experienced colleague.
Nitrogen dioxide (VERY TOXIC and CORROSIVE) is a heavy, brown gas. Despite the
similar hazard warnings, there is a lower risk of serious injury with nitrogen dioxide
than bromine and the gas provides a safer alternative. A known volume of concentrated nitric acid (CORROSIVE) is added to an excess of copper turnings to produce
enough nitrogen dioxide so that a gas jar of known volume is nearly filled. Another
gas jar of air is placed over a gas jar of nitrogen dioxide. Over the next 20 minutes,
the brown gas diffuses into the upper jar.

Procedure
Clamp

Copper turnings
Fig i

Fig ii

Fig iii

Using water and a 250 ml measuring cylinder, establish the volume of the gas
jar. Do not use this wet gas jar for the following demonstration.
Using a retort stand, boss and clamp, adjust the fitting of a dry inverted gas jar
over another dry gas jar of the same size and set it to one side.
Place at least 1 g, but no more than 2 g, of copper turnings in the gas jar (fig i).
Knowing that 8 ml of concentrated nitric acid produces 1000 cm3 of nitrogen
dioxide at room temperature and pressure, estimate the volume of acid needed
to just fill the gas jar with gas. Wearing eye protection and suitable gloves,
place 1 ml less than the estimated volume of nitric acid (CORROSIVE and OXIDISING AGENT) in a 10 ml measuring cylinder. Empty the contents of the measuring cylinder into the gas jar with copper and watch the brown gas rise (fig ii).
Once the reaction stops, invert the second jar over the jar containing the gas.
Clamp this jar into position with care (fig iii). Diffusion takes place in 20 minutes.

Controls and
hints

If the above procedure is followed, a fume cupboard is not required because nitrogen dioxide, being heavier than air, remains in the gas jar. Gloves are not required
when an automatic pipettor is used.

Disposal

If possible, move the gas jars to a fume cupboard. Add water to each gas jar and
pour the contents down a foul-water drain, adding more water. Unreacted copper
turnings can be dried and reused. If there is no fume cupboard in the room, carefully insert gas-jar lids to cover both jars. Seal with sellotape and remove to a fume
cupboard.

Extension

The demonstration can be performed along with a similar set up using bromine to
show that gases diffuse at different rates. To fill a 1 litre gas jar, use no more than
2 ml of liquid bromine. Adjust the volume of bromine liquid to the capacity of the gas
jar that is available. It takes time for bromine to vaporise. Use a fume cupboard,
wear goggles or a face shield and nitrile or latex chemical-resistant gloves40. A
bucket of 1 M sodium thiosulfate solution should be available in case bromine
splashes onto the skin or is spilled.

40

See PS50, Gloves as Personal Protective Equipment (PPE), CLEAPSS School Science Service.
28

8.2
Diffusion into a vacuum
Introduction
In school laboratories, bromine gas diffusion kits41 are often not available, unused
or broken. Vacuum pumps are very heavy, difficult to use by untrained staff and
very noisy. For this demonstration, a hand-operated pump is all that is required to
reduce the pressure in one of the containers. Schools with redundant Quickfit
apparatus can use round-bottom flasks in place of thick-walled borosilicate glass
bottles. Nitrogen dioxide (VERY TOXIC and CORROSIVE) is a safer alternative to
bromine.

Procedure

Prepare tubing, stopcocks and suitable size bungs to fit thick-walled bottles, as
shown in the diagram below.
The bottles, with their screw tops removed, should be clamped about the neck
to hold them steady. Do not place the stopper into Bottle A.

To a hand-operated
vacuum pump

Stopcock X

Stopcock Y

Controls and
hints

2 x 500 ml
thick-walled
bottles

Nitrogen dioxide

(Wear eye protection and chemically-resistant gloves42.) In bottle A, place 1 g

of copper turnings and add 3.5 ml of concentrated nitric acid (CORROSIVE and
OXIDISING AGENT).
When the reaction is over, place the bung into Bottle A and arrange the equipment as shown in the diagram. Ensure that stopcock Y is closed and stopcock
X is open.
Connect the hand pump and withdraw air from Bottle B. Close stopcock X and
disconnect the pump.
Open stopcock Y and the brown flask diffuses quickly into Bottle B.

Students should wear eye protection. There is a very remote risk of an implosion
occurring so a safety screen should be placed between the demonstration and the
pupils. The demonstrator should wear a face shield. If the instructions above are
followed, there is no reason to use a fume cupboard to prepare the gas as it is
heavier than air and stays in the bottle.
Hand-operated vacuum pumps43, such as that illustrated below, can be obtained
from most educational science equipment suppliers for 60-65.

Disposal

The screw tops for these bottles can be replaced and the bottles removed to a
fume cupboard where water is added to each, into which the gas dissolves. The
liquid can be flushed down the foul-water drain.

Extension

This procedure may be repeated with bromine but great care is required (see
Hazcard 15).

41
42
43

Bromine diffusion kit, Philip Harris, cat. no. COA42286, 174.

See PS50, Gloves as Personal Protective Equipment (PPE), CLEAPSS School Science Service.
See R45, Vacuum Pumps, CLEAPSS School Science Service, for further information.
29

9.

Exothermic reactions - safer procedures

9.1

Ammonium dichromate(VI) decomposition

Myth: Ammonium dichromate(VI) is a banned substance in schools.

Introduction

The statement above is false. The health hazard rating for all chromium(VI) compounds has been altered from IRRITANT to TOXIC. They are now classified as class 2
carcinogens with the R49 risk phrase: may cause cancer by inhalation. It is unlikely, however, that technicians, teachers and even students would inhale ammonium
dichromate(VI) (EXPLOSIVE, TOXIC and DANGEROUS FOR THE ENVIRONMENT). The
warning is principally aimed at those in the chrome-plating industry where some
workers could be breathing the material as an aerosol for 8 hours or more a day.
This small-scale version is based on an idea from SSERC44 and originally designed for a school with no fume cupboard.

Procedure
Spatula

Mineral fibre plug

Large borosilicate
test tube, 150 x 25 mm

Position of clamp

1 g of ammonium
dichromate(VI)
Heat

The apparatus and material are set up as above with the mineral fibre (see
section 4.1) only loosely plugging the tube.
Ammonium dichromate is heated with a Bunsen burner, which is removed
once the reaction starts.

Controls and
hints

Eye protection should be worn. Wear gloves when dispensing ammonium

dichromate(VI) (see Hazcard 7). The spatula is placed over the end of the boiling
tube just in case the mineral fibre has been packed too tightly and may be ejected.
Experience has shown that, with practice, if the demonstration is repeated, a fume
cupboard is not required as suggested in Hazcard 7. However, it may be considered prudent that if students do this experiment in Y12+, it is carried out in a fume
cupboard.

Disposal

Use forceps to pull out the mineral fibre. Put this and the chromium(III) oxide, that
has formed, into a plastic bag and place this in the normal waste.

Extension

The reaction can be initiated with very warm air from a hot-air gun used for paint
stripping. The setting needs to be very high. Using the hot-air gun shows that the
Bunsen burner flame is not penetrating the test tube as some students believe!
The boiling tube with ammonium dichromate(VI) and plug can be placed in a
beaker on a balance to find their mass. After the reaction, and the apparatus is
cooler, the mass can be measured again. Although there is a noticeable increase
in the bulk of solid, the mass has decreased.
Could the procedure be adapted to investigate the mass loss and compare it with
the equation below? Water that condenses in the mineral fibre has to be removed
by more heating.

(NH4 )2 Cr2O7(s) Cr2O3(s) + N2(g) + 4H2O(g)

44

Scottish Schools Equipment Research Centre. This is a similar organisation in Scotland to the CLEAPSS School
Science Service.
30

9.2

Iron/sulfur reaction
Myth: We cannot do this activity as it affects asthmatics in the class.

Comment

If the procedure (see Hazcard 96) is not carried out carefully, sulfur burns in air to
form sulfur dioxide, a TOXIC and CORROSIVE gas. Any advice suggesting that this
activity can be carried out using open-ended equipment, such as bottle tops or
heat-resistant paper, should not be followed. Also, if test tubes are too full, sulfur
vapour will escape and ignite to form sulfur dioxide.
When the iron/sulfur mixture is heated, the sulfur melts and reacts with the iron
exothermically to form iron(II) sulfide. This is an important experiment and is one of
the few that pupils can do themselves that demonstrates visibly that the properties
of a compound are different from its constituent elements.
The procedure should be carried out in borosilicate test tubes as a demonstration
or in prepared smaller ignition tubes by pupils (see Hazcard 96). Mineral fibre (see
section 4.1) stops sulfur vapour leaving the test tube and possibly catching fire.

Procedure

125 x 16 mm borosilicate test tube

Mineral fibre plug
Position of clamp or holder
2 g of iron/sulfur mix

Heat

Controls and
hints

Prepare a mixture containing iron powder and sulfur powder in the ratio 7:4 by
mass.
Place 2 g of the mixture in the borosilicate test tube.
Insert a mineral fibre plug in the mouth of the tube and clamp the test tube at
the opening.
Heat the powder mixture strongly but extinguish the Bunsen burner as soon as
the reaction starts.

Wear eye protection. Ensure the room is well-ventilated.

Iron powder mixed with either finely-powdered roll sulfur or flowers of sulfur can be
used. If fine sulfur powder is mixed with iron filings, separation can occur and a
consistent mix is not obtained.
Borosilicate glass must be used.
The reaction can be initiated using a hot-air paint stripper at about 550 C. This
answers comments from some students who believe the flame penetrates the
glass!
The reaction can be carried out on a microscale using a 75 x 10 mm test tube
(ignition tube). This must never be more than one-quarter full and even 0.2 g of the
mixture is sufficient for a good display.
The product can be tested with acid quite safely even though hydrogen sulfide
(TOXIC) gas is produced. This would have to be done in a fume cupboard unless a
microscale procedure45 is used.

Disposal

The test tube should be allowed to cool and placed in the glass bin.

Extension

Unfortunately, there does not appear to be a foolproof method of making nonmagnetic iron(II) sulfide. Fowles46 suggested using a mixture containing 1.5 times
as much sulfur as iron but this does not appear to work either. Partington47
suggested that the product is only feebly magnetic. Perhaps weak magnets should
be used?

45
46
47

Microscale Chemistry, J Skinner, Royal Society of Chemistry, ISBN 1870343492. This book was sent to all schools in
the UK by the RSC.
Lecture Experiments in Chemistry, G Fowles, Bell, 3rd edition, 1947. This book may still be on a shelf somewhere in
the school, in libraries or in second-hand bookshops.
A Textbook of Inorganic Chemistry, J R Partington, MacMillan, 6th Edition, 1950.
31

9.3
Sodium burning in chlorine
Comment
When sodium, burning on a steel deflagrating spoon, is placed into an atmosphere
of chlorine, brown iron(III) chloride is produced as well as sodium chloride. The
appearance of the brown fumes does not convince pupils that sodium chloride is
produced. The method described here is therefore preferable.

An inverted gas jar of chlorine is placed over sodium burning in air on the flat face
of a brick. The sodium burns with an intense yellow flame and a colourless solid
(sodium chloride with some sodium oxide) forms on the side of the gas jar.

Procedure

Inverted gas jar

of chlorine
Gas jar coated with
sodium chloride
Clean sodium
Sodium burns
intensely

Gas jar lid

Brick

Disposal

Controls and
hints

Wear eye protection. Prepare a gas jar of chlorine (TOXIC) by the large-scale
method (see Hazcard 22). The gas does not have to be specially dried. This
may be done earlier and stored in a fume cupboard. Place a lid on the gas jar.

Wear eye protection. Cut a piece of sodium (a 6-8 mm cube is sufficient) and
remove the oil by squeezing the sodium between absorbent paper.

Place the sodium on the flat side of a brick in a fume cupboard.

Direct a non-luminous Bunsen burner flame onto the sodium so that it melts
and any remaining oil burns off.

When the sodium finally burns with a small yellow flame, quickly remove the lid
and place the gas jar over the burning sodium.

Allow the apparatus and chemicals to cool to room temperature. Wash the gas jar
with water. Immerse the brick in water in a bowl of cold water. This will remove any
unreacted sodium; wear face protection in case unused sodium is below the crust
of salt and then reacts with the water.
If a brick is not available, a porcelain crucible lid supported on a small bed of sand
can be used but the lid may break during the reaction.
When sodium is heated, it melts and a black crust of carbon forms. On further
heating, the carbon burns away leaving sodium burning with a small yellow flame.
Because chlorine falls out of the inverted gas jar as the gas jar is placed over the
burning sodium, it is better to carry out the procedure in a fume cupboard and a
safety screen is not then required.
If too much sodium is used, there may be a lot of unused sodium surrounded by
crust on the brick. This will be very reactive when the brick is immersed in water.
A cube of sodium with sides of 10 mm will react with 500 ml of chlorine at room
temperature.

32

9.4

Thermite reaction
Myth: With sparks billowing everywhere, this dangerous experiment must be banned.

Comment

This procedure has not been banned. However, some teachers have had accidents when performing the procedure outside in a strong breeze; the powders blew
into the flame, caught fire and caused burns to the hand and/or face. Siting the
demonstration in a fume cupboard has caused damage to the cupboard. The
underwater method described here is performed on a bench and does not produce
many fumes. It produces a result within seconds of setting it off because the water
cools the iron down very quickly.

There have been occasional reported explosions when using methods

similar to this. It is essential not to exceed the stated quantities and
that the demonstrator and students are protected by safety screens.

Procedure
Magnesium ribbon
Fluted filter paper
Igniter mixture
Thermite mixture

Pip-clay traingle

Tripod
1 litre beaker

Water layer

Sand layer
Heat-proof mat

Eye protection and a laboratory coat (it can become messy at the end) should
be worn by the demonstrator. Students should stand further than 4 m from the
reaction and wear eye protection. Safety screens must be used.
Fold two 12 cm diameter circles of filter paper into fluted cones and place one
inside the other.
Into a 1 litre, thick-walled beaker, pour sand until it is one third full and then
add water until it is two thirds full.
Wear eye protection. Place the beaker on a bench mat and set up the equipment as shown in the diagram above. Add 12 g of Thermite mixture [9 g of
iron(III) oxide and 3 g of aluminium powder (medium grade)] to the fluted filter
paper.
Make a depression in the Thermite mixture with a spatula and place the igniter
mixture [0.2 g of magnesium powder and 2 g of barium nitrate (a ratio of 1:10)]
into this.
Insert a magnesium ribbon fuse upright into the igniter mixture. It must extend
above the fluted filter paper. Light the magnesium fuse with a Bunsen burner
flame and retreat.
Once the reaction has stopped, remove the beaker and decant the water down
the sink and retrieve the iron formed with a magnet. Wash the iron under a tap
of running water.
It may be possible to extract some shiny iron from the spongy bits of metal and
demonstrate that it conducts an electric current.

Controls and
hints

The bench should be clear of combustible materials and protected with a sheet of
hardboard or mats. Pupils should not look directly at the glare of the burning magnesium but
cover their eyes with their fingers slightly apart. The demonstrator must have room to move
quickly away to a safe distance. Do not use potassium manganate(VII) and hot glycerol to
initiate the reaction in this version because the filter paper catches fire. Do not use any
copper oxides, chromium(VI) oxide, lead oxides or manganese(IV) oxide.

Disposal
Extension

Leave the sand in a tray to dry and use again.

Chromium(III) oxide or manganese(II)dimanganese(III) oxide (Mn3O4) can be used instead
of iron(III) oxide.
33

9.5

Fat-pan fire
Myth: This activity is not mentioned in the National Curriculum, so there is no need to
demonstrate it!

Comment

Many activities are not directly mentioned. However, the following statement
occurs in all Breadth of Study sections of the National Curriculum: recognise
that there are hazards in living things, materials and physical processes, and
assess risks and take action to reduce risks to themselves and others. This
demonstration can be performed whenever combustion is discussed.
The HSE wishes to encourage the teaching of any aspect of science that reduces
accidents in the home, at work and during leisure. On average there are 16,000
chip-pan fires a year - thats almost two every hour. Apart from the damage they
cause to peoples homes, these fires also injure around 3,000 people a year48. The
extent of the injuries sustained is also a drain on NHS funds.

Procedure

Cooking oil
25 mm diameter tall
nickel crucible

Pipe-clay triangle

Heat

Heat proof mat

Controls and
hints

48

Place mats on the bench to protect it from hot burning fat. The nickel crucible
is wedged firmly and upright in the pipe-clay triangle on the tripod. The wires of
the triangle may need to be bent over the tripod; it must not tip when the flame
is smothered. Safety screens are positioned to protect the pupils and the
demonstrator, who should wear a face shield and heat-resistant gloves. Pupils
must not be closer than 4 metres and must wear eye protection. Make sure
the equipment is not sited below a light fitting. Have ready a wooden test-tube
holder, attached to a meter rule; this should hold a test tube containing about
5 ml of water.
3 ml of cooking oil is poured into the crucible and a lighted Bunsen burner is
placed beneath it.
Once the oil catches fire, extinguish the flame by a) switching off the gas supply to the Bunsen burner and b) placing a small square of hardboard or aluminium over the crucible. This simulates placing a tray over a burning chip pan
to remove the oxygen from the fire. The demonstrator should explain that a
damp tea-towel would also extinguish the fire but is unsuitable, in this demonstration, as it could knock the apparatus off the tripod.
The square is removed. The Bunsen burner is lit again and the cooking oil
reignites. Switch off the gas supply to the Bunsen burner but this time hold the
metre rule to which the test tube containing water is attached and, at arms
length, add the water to the burning oil. This will cause a ball of fire to rise
about a metre, effectively demonstrating the hazard of attempting to put out a
fat-pan fire with water.

The procedure described is hazardous and risks are made acceptable only by
adherence to the restrictions and precautions advocated.
The demonstrator should practice the procedure beforehand, with a colleague
present, until confidence is gained.
The activity must be done only as a teacher demonstration. The demonstration
must not be done in a fume cupboard. The quantities prescribed must not be
exceeded; do not be tempted to use more cooking oil. This is as good as it gets! A
squat crucible must not be used as it ejects the hot fat sideways. A porcelain
crucible is not safe as it is liable to break.

Data from the West Sussex Fire Brigade web site (www.wsfb.co.uk/safety/chippan.html) from where a video can
be downloaded. It illustrates the use of a damp tea towel to extinguish the flame.
34

9.6

Cigarette smoking machine

Myth: The strict non-smoking rule in the school prevents us from using a smoking machine.

Comment

A smoking machine is a popular demonstration showing the tars and other products formed by the combustion of cigarette tobacco. However, there are health and
safety issues. The passive smoking of the fumes from a couple of cigarettes
should have a negligible effect on the health of staff and students, especially in a
well-ventilated room. Even so, the demonstration is best carried out in a nonworking fume cupboard with the sash pulled down. This heightens the dramatic
effect and makes it less likely that the demonstration would be considered a
breach of a schools no-smoking policy. The tars are usually trapped on cotton
wool or, preferably, a less-compact material such as white-coloured mineral wool
(see section 4.1). The tars that collect present the main hazard, as these are likely
to contain carcinogens which could be absorbed through the skin or inhaled.
One published scheme suggests that tar-soaked wool is passed around a class for
pupils to smell. Risks from only a brief inhalation will be small and may be outweighed by the deterrent effect of the odour on potential or actual smokers. However, the risks of skin contact must be stressed. The wool should be placed in a
small beaker or other container and the activity only carried out if the teachers risk
assessment indicates that students will behave responsibly.

Cigarette

Procedure

To hand pump
Glass tubing
to hold the
cigarette
Cotton wool or
mineral fibre

Water, Universal
indicator or lime
water solution

Set up the equipment in a fume cupboard as shown above.

Attach a hand-operated vacuum pump and a cigarette to the equipment.
Light the cigarette and use the pump to give regular sucks on the cigarette.
When finished, pour a small amount of water on the cigarette to extinguish it
and switch on the fume cupboard. Remove the cotton wool or mineral fibre
with a spatula. Do not touch it.

Controls and
hints

Carry out the procedure with a filter cigarette. Then repeat using
another cigarette with its filter cut off and fresh cotton wool or fibre.
49
Hand-operated vacuum pumps , such as that illustrated, can be
bought for about 60-65. These are preferred since the water supply in
some laboratories is insufficient to operate a filter pump.
If the fume cupboard is on during the pumping procedure, incoming air
causes the cigarette to burn too quickly when not being smoked.
Limewater or universal indicator solution can be added to the boiling tube to illustrate the
formation of acidic gases or presence of carbon dioxide.

Disposal

The apparatus should be disassembled in a fume cupboard and great care taken
to avoid skin contact with the tars. Protective gloves (preferably nitrile) should be
worn and the tar-soaked material placed in a plastic bag, which is then sealed
before disposal in the refuse. There is little point in going to great lengths to clean
the apparatus, if it is used only for this demonstration. Wiping with a paper towel,
perhaps moistened with a solvent such as ethanol (HIGHLY FLAMMABLE), should be
adequate. The contaminated towel can be added to the bag containing the wool.
The apparatus should be stored in a box or sealed plastic bag to contain the smell.
As an alternative to disassembly, some technicians may consider disposing of the
entire, unopened side-arm test tube - if the departments finances permit the
regular purchase of replacement glassware etc.

49

See R45, Vacuum Pumps, CLEAPSS School Science Service, for further information.
35

9.7
Sulfuric acid dilution
Comment
The energy released when concentrated sulfuric acid is added to water is consid-

erable. The temperature can rise so rapidly that the solution may boil and hot acid
is sprayed out of the container, causing serious burns. The use of an ice/water
mixture, in place of water at room temperature, makes this procedure safer. The
diluted solution produced is already at about room temperature and ready for use.
The control measure makes use of the latent heat of fusion of water. The method
is suitable for making bulk solutions of 1 or 2 M sulfuric acid. It is suggested that
1 litre at a time is made up and the diluted solution is added to labelled bottles.
The method also makes use of plastic 1 or 2 litre laboratory polypropylene measuring jugs which are much easier to handle than measuring cylinders of similar
volume. Accuracy is not compromised to the extent that it will affect the results of
student experiments, if the volume of acid is first measured in a measuring cylinder. The following method also makes use of a magnetic stirrer, not mentioned in
Recipe Cards. Conventional stirring is acceptable but more time should be spent
to ensure that there are no regions of concentrated acid in the jug.

Although the use of ice has been suggested in Recipe Cards50 for over 10 years,
this safer procedure is still not widely used.

Procedure

To make 1 litre of dilute sulfuric acid

Wear a face shield and a laboratory coat. Wear gloves which protect from
chemical splash.
Pour a suitable volume of concentrated sulfuric acid into a labelled DRY
beaker. This avoids the difficult operation of pouring the acid from a heavy
2.5 litre bottle into a measuring cylinder.
Pour from the beaker the required volume of the concentrated sulfuric acid into
a DRY measuring cylinder.
Pour any unused concentrated acid back into the correct bottle and replace
the cap.
Place a magnetic stirrer bar into a 1 litre measuring jug followed by 50 ml of
pure water and then ice (made from pure water) so that the beaker is
approximately 2/3rds full. Place the jug on a magnetic stirrer.
Start the stirrer. Gently pour about a third of the volume of the acid in the
measuring cylinder onto the ice in the measuring jug.
Repeat with a second and third portion of acid and keep stirring. The ice
should now have melted. Stop the stirrer.
Continue adding pure water to the jug until the required volume is reached.
Restart the stirrer.
Stop the stirrer and decant the solution via a funnel into a labelled bottle.

Disposal

Rinse out all equipment, especially any used to hold concentrated sulfuric acid.

Controls and
hints

Pure water should be placed in the freezer the night before. The ice can then be
crushed51.
Apparatus, used to hold concentrated sulfuric acid, must be dry before use.
Ice sometimes stops the magnetic stirrer from turning so some initial help may be
required with a glass rod. However, stir gently as the glass stirrer might break.

50
51

See CLEAPSS Recipe Card 69.

See Bulletins 103 and 108 for tips on making crushed ice.
36

10. Electrolysis of molten salts

Comment

Table 10

The electrolysis of molten lead(II) bromide to form lead and bromine is not always
convincing. The procedure is time consuming, it requires a substantial amount of
material and it has to be carried out in a fume cupboard so pupils may not see the
apparatus clearly. Table 10 shows substances that have been proposed for investigations of the electrolysis of molten salts. The discussion that follows the table
considers the pros and cons of the use of each salt.

Low melting point anhydrous salts

Anhydrous salt

Discussion

Hazard

M pt of salt (C)

M pt of metal (C)

Cadmium iodide

Toxic, Dangerous for

the environment

388

321

Lead(II) bromide

Toxic, Dangerous for

the environment

371

328

Lead(II) chloride

Toxic, Dangerous for

the environment

501

328

Lead(II) iodide

Toxic, Dangerous for

the environment

410

328

Lithium chloride

Harmful

610

1383

Tin(II) chloride

Harmful and Irritant

247

231

Zinc chloride

Corrosive

262

732

Cadmium salts are not recommended as suitable for schools because they are
category 2 carcinogens, mutagens and teratogens.
Lead(II) bromide and iodide dissociate on heating, which rather defeats the object
of the activity. When the other salts are heated, there is no evidence of dissociation.
Tin(II) chloride undergoes electrolysis but although molten tin is seen being produced at the cathode, no chlorine is detected. However, white fume appears. A
possible explanation is that the chlorine reacts with tin(II) chloride and/or tin to
form tin(IV) chloride.
Lithium chloride has to be heated in a small crucible, not a glass vial. Chlorine can
be detected. However, removing and demonstrating the presence of lithium metal
is not easy.
The melting point of lead is lower than that of lead(II) chloride so the metal is
obtained as convenient globules at the end of the procedure although they are
difficult to extract from the melt.
It is easy to extract the zinc from zinc chloride because the salt is soluble in water.
Once electrolysis is finished and the apparatus is cool, the addition of water
dissolves the unreacted salt to leave granules of the metal behind.
A small-scale investigation using lead(II) or zinc chloride can be carried out on the
open bench. If the procedure lasts for no more than 15 minutes with a current of
less than 0.5 A, the volume of chlorine obtained is less than 56 cm3 at room temperature and pressure. This averages out at a level of 0.23 ppm of chlorine in the
room. The odour is detectable but the concentration is much lower than the Occupational Exposure Standard52 of 2 ppm (STEL).
The method outlined overleaf uses microchemical techniques which need rehearsal. The equipment required is listed in Table 11. Chlorine from the vial is sucked
into a Pasteur pipette and bubbled through 0.1 M potassium iodide solution which
turns brown, with the liberation of iodine. Alternatively, damp starch iodide paper
can be held with tongs above the vial.

52

See CLEAPSS Laboratory Handbook section 7.9.1 for information about Occupational Exposure Levels.
37

Table 11

Special equipment
Item

Supplier53

Specimen bottle
54
or vial

Eg, Griffin & George,

TUL-490-062E

Do not use soda glass. A 48 x 25 mm (h x d)

vial made from neutral borosilicate glass is
satisfactory.

Terminal
ceramic block

RS, 426-351

These are now made from Steatite. (15 A

3-way with 2 x 5 mm diameter holes.)

Carbon
electrodes or
rods

Eg, Timstar Laboratory Suppliers

EL06886

The tops need to be ground down to a point

(see the magnified picture below) with glass
paper to fit into the connectors in the ceramic
block.

Heat-proof mat

Available from all

suppliers

This is used to protect the block from the heat

of the Bunsen burner. Cut the mat down to a
reasonable size. Drill two holes (0.52 mm
diameter) and 13 mm apart to allow the carbon
rods through.

Heat source
(mini-Bunsen
burner)

Eg, Scientific and

Chemical Supplies,
BRN 030010 or
Harris, COA57265

Heat the vial from under the gauze, not the

ceramic centre. This provides more heat to
melt the salts.

Ammeter

Available from all

suppliers

A meter with a range of 0 - 1 A should be

used.

Procedure

Terminal block

Comment

Low-voltage supply

Heat-proof
mat
4 mm plugs

Specimen
bottle or vial
Carbon rod as
electrode
Gauze

Zinc chloride or
lead(II) chloride

Terminal block

Heat (mini-Bunsen burner)

Disposal

53
54

Place 6 g of anhydrous zinc or lead(II) chloride in the vial. Set up the apparatus on the gauze (supported on a tripod) as shown in the diagram. Support
the vial in a clamp.
Place the mini-Bunsen burner below the gauze (it will need raising on a block
of wood). Light the Bunsen burner. The zinc chloride may produce a little
hydrogen chloride (TOXIC and CORROSIVE). Lead(II) chloride requires a hotter
flame than zinc chloride to keep molten; adjust accordingly.
Adjust the L-V supply to deliver a current of about 0.2 - 0.5 A.
Using a Pasteur pipette, withdraw some of the atmosphere above the molten
salt and bubble the gas through 0.1 M potassium iodide solution in a small test
tube. Alternatively, hold a damp piece of starch iodide paper, using tongs,
close to the neck of the vial.
After about 10 minutes, switch off the electrical supply, turn off the Bunsen
burner and carefully adjust the clamp to lift the electrodes out of the melt.
When cool, examine the solidified lead(II) chloride for globules of lead. Hot
pure water can be added to dislodge the unreacted lead(II) chloride from the
metal globule. With solidified zinc chloride, add pure water to dissolve the salt.

The zinc solutions can be disposed of down the foul-water drain. Keep the solidified lead(II) chloride for disposal at a future date by an authorised contractor.

Addresses can be obtained from the CLEAPSS Laboratory Handbook, section 1.

Some suppliers catalogues list these under tubes and others under bottles.
38

11. Crude-oil distillation

Comment: This experiment used to work really well until the use of crude oil was banned.

Comment

The Control of Substances Hazardous to Health (Amendment) Regulations 1991

banned benzene and any solutions containing more than 0.1% benzene from use
except in industrial production. Crude oil and petrol may contain up to 5% benzene
and the use of these are governed by these Regulations although they do not
apply to the use of petrol in garages nor to emissions in exhaust fumes. Benzene
is a class 1 carcinogen.
Alternative recipes55 for crude oil cannot directly reproduce the original results of
crude-oil distillation. When real crude oil was distilled, there was a pronounced
change in colour with the different fractions. There was also a pronounced change
in viscosity from the free-running light fractions to the thicker, heavier fractions.
The lighter fractions also burned with a less-smokier flame than the heavier
fractions. Only the latter property can be shown when examining the fractions
produced in distilling the alternative recipe. However, the demonstration does
illustrate the principle of fractional distillation.

Procedure
o

0 - 350 C thermometer

Side-arm boiling tube

75 x 10 mm test tubes
to collect the fractions

Mineral fibre with

6 ml of crude oil

1 ml of water in a
test tube to compare volumes
(Optional)
Block of wood to
hold the test tubes

Heat

Wear eye protection. Place a tuft of mineral fibre (see section 4.1) in the sidearm boiling tube and add 6 ml of crude-oil substitute.
Set up the apparatus as shown in the diagram.
Warm the boiling tube gently up to 100 C, collecting the distillate in the first
small test tube (75 x 10 mm).
Place the delivery tube into the second small test tube and heat the boiling
tube to 150 C. Repeat with fractions to 200, 250 and 300 C.

Controls and
hints

Side-arm boiling tubes produce more consistent results than boiling tubes fitted
with bungs with two holes, one for the thermometer and one for the delivery tube.
The length of rubber tubing between the delivery tube and the side arm should be
as short as possible to minimise the distillate collecting in the tubing.
The bulb of the thermometer should be level with, or just below, the sidearm.
Small test tubes are used to collect the fractions, as it is easier to see the results.
To show that the first fraction burns with a less-smoker flame than the heavier
fractions, make sure that the boiling-point range of the first fraction does not
exceed 100 C.

Disposal

The mineral fibre can be placed in the waste. The hydrocarbons should be mixed
with an equal volume of detergent and flushed down a foul-water drain.

Extension

Using a 1 ml graduated pipette, place 1 ml of water in a small test tube of the

same size as those used to collect the fractions. Measure the height of water in the
tube. Note down the heights of each fraction collected in the distillation. Estimate
the volume of each fraction obtained and find what percentage of the original oil is
not distilled.

55

See Recipe Card 20.

39

12. Cooling curves

Myth: Naphthalene, used in moth balls, is banned from school laboratories.

Naphthalene is not banned. The CHIP Regulations56 have recently included guidance about the
hazards for naphthalene (see Table 12). However, this information may take time to reach suppliers of chemicals in the UK. In addition, some American suppliers may continue to suggest
that naphthalene could be a carcinogen. The HSE had quoted an occupational exposure standard57 for naphthalene of 10 ppm LTEL and 15 ppm STEL but this has recently been withdrawn
while more research is being carried out. When further guidance is announced, it will be
reported in the CLEAPSS Bulletin. The STEL value for naphthalene can be reached in school
laboratories if 15 groups of pupils all melt naphthalene in open boiling tubes. The odour of
naphthalene can be detected at very low levels (0.08 ppm); some people find it unpleasant and
complain of headaches at moderate levels of exposure. Mineral fibre plugs (see section 4.1) can
be used to reduce the amount of vapour that escapes into the air.

12.1

Substances used for cooling curves

Substances suggested for cooling curves are listed in Table 12. It is unwise to use paraffin wax,
as it is not a pure substance.

Table 12

Substances used for cooling curves

Name

Melting
point /C

1,4-Dichlorobenzene

53

R36: IRRITATING to the eyes. Long-term exposure limit is 25 ppm;

short-term exposure limit is 50 ppm; detectable odour level is
0.18 ppm. Odours can be reduced by using a mineral fibre or
cotton wool plug. A very good cooling curve is obtained.

Dodecanoic acid

45

Also known as lauric acid. Minimal hazard. It stays at the melting

point temperature for a very long time.

Hexandecan-1-ol

49

Also known as cetyl alcohol. Minimal hazard. Cools slowly after it

reaches the melting point temperature.

2-Methylpropan-2-ol

26

Also known as tert-butyl alcohol. R11, 20: HIGHLY FLAMMABLE and

HARMFUL by inhalation. Long-term exposure limit is 100 ppm;
short-term exposure limit is 150 ppm. Requires an ice bath for
cooling. Very good results can be obtained. The ice can be used
to cool the liquid down.

Naphthalene

80

R22, 50, 53: HARMFUL if swallowed, DANGEROUS FOR THE ENVIRONMENT. Odours can be reduced by using a mineral or cotton wool
plug at the opening of the boiling tube. Excellent results can be
obtained.

Phenyl 2-hydroxybenzenecarboxylate

41

Also known as phenyl salicylate or salol. Minimal hazard. It

exhibits pronounced supercooling58.

Octadecanoic acid

70

Also known as stearic acid. Minimal hazard. It stays at the melting

point temperature for a long time.

Volasil 244

17

Minimal hazard. Very good results can be obtained. Requires a

salt/ice bath for cooling.

Hazards and comments

Pupil boredom and broken thermometers are problems with this activity. Both stirring (which
evens out the temperature gradients in the melt) and taking readings every 30 seconds over
56
57
58

The Chemicals (Hazard Information and Packaging for Supply) Regulations 2002.
See CLEAPSS Laboratory Handbook section 7.9.1 for information about Occupational Exposure Levels.
The substance exists as a liquid below its melting point. This is known as a metastable state and the introduction
of crystals initiates solidification, with energy released as heat. Glass is another example of a supercooled liquid,
which becomes opaque on crystallisation. Fortunately, the process occurs very slowly (look at medieval stainedglass windows in churches which become opaque when crystallisation is present).
40

20 minutes or longer can contribute to accidents and silly behaviour by students (eg, knocking
over the beaker of boiling water or interfering with stopclocks).
Plotting the curve on graph paper is sometimes seen as a time-wasting procedure. The use of
dataloggers and spreadsheets to manipulate results can be valuable for this procedure.
The cooling curves of the compounds in Table 12, obtained by using a datalogger, are shown
below.
The curve for naphthalene provides the best example. The curve for 1,4-dichlorobenzene is
satisfactory. The cooling curves for Octadecanoic acid and Hexandecan-1-ol are complicated by
the strong intermolecular bonding between the molecules. Hence, the cooling is very slow in
comparison with naphthalene.
o

Temperature/ C
100

Hexadecan-1-ol
Naphthalene

80

Octadecanoic acid

60
1,4-Dichlorobenzene
40

Dodecanoic acid

20
2-Methylpropan-2-ol

Volasil 244
0

Time

Cooling curves for various substances

Temperature / C
40

Melting point

The melt cools below

its melting point but is
still a liquid.

At this time, some

crystals were added.
30

Time

Cooling curve for phenyl 2-hydroxybenzenecarboxylate (salicylate)

which exhibits pronounced supercooling

41

12.2 Manual logging for the cooling curve of naphthalene

Procedure
Wear eye protection.

Half fill a 150 x 25 mm test tube with

naphthalene crystals (on melting, the
liquid level will drop considerably).
Insert a 0-110 C thermometer (spirit
type is suitable).
Insert cotton wool around the thermometer as shown in the diagram.
Support a 250 ml beaker on a tripod
and gauze. Half fill with pure water59
and add a few anti-bumping granules.
Clamp the boiling tube in the beaker.
Place a Bunsen burner underneath and
light the gas.
Heat the water to boiling.
When all the naphthalene has melted,
raise the test tube out of the water.
Stir gently with the thermometer and
take readings every 30 s. Once
solidification begins, stop stirring but
continue to take readings.

Cotton wool. It slows

down diffusion of
naphthalene to
the atmosphere

Heat on a
tripod and gauze

Disposal

In a fume cupboard, melt the solid to remove the thermometer but save the test
tubes for the next time that they are used.

Extension

Obtaining the cooling curve of several substances can lead to a discussion about
different molecular environments and intermolecular attractions.
The supercooling effect is another interesting extension. Phenyl 2-hydroxybenzenecarboxylate can exist as a liquid below its melting point. If seeded with some
crystals, solidification takes place, with heat released, and the temperature rises to
the melting point. See the graph on the previous page.

12.3 Using a datalogger to monitor cooling

Wear eye protection.
Procedure

To datalogger

Place 6 g of the reagent in a 48 x

25 mm (h x d) borosilicate vial60
(size is not too critical) and add a
Temperature
small magnetic stirrer bar.
sensor
Fit a cap with a small hole in the
centre. The diameter of the hole
Plastic cap
should be slightly less than the
with hole
Vial
diameter of the sensor so the
Sample under
equipment can be held above a
Stirrer bar
test
magnetic stirrer by clamping the
sensor.
Magnetic stirrer
Heat the specimen tube on a hot
Magnetic stirrer
plate until the solid is molten.
Place the specimen tube on the bench and lower the temperature sensor
through the hole and into the molten liquid. Clamp the sensor and move the
equipment so that the vial is held above the magnetic stirrer but not touching it.
Start logging data over a period of 20 minutes.
Remove the sensor (it often just pulls out).
Place a little propanone (HIGHLY FLAMMABLE) on a tissue and clean the sensor.

Disposal

59
60

The solids can be kept in their labelled vials and reused at a future date.

If pure water is used, it will not go cloudy on boiling and the beaker will not need cleaning afterwards. This may
not be a problem in soft-water areas.
See Table 11.
42

13. A safer procedure for the thiosulfate/acid reaction

Comment: So much sulfur dioxide is given off at higher temperatures that we have had to
give up this activity.

Comment

The reaction between sodium thiosulfate solution and dilute hydrochloric acid (both
MINIMAL HAZARD) produces sulfur dioxide, a TOXIC and CORROSIVE gas, and colloidal
sulfur as a precipitate. The gas can induce an asthmatic attack in some pupils. The
release of gas is a particular problem if the activity involves studying the effect of
increasing the temperature of the reaction. In addition, the precipitate sticks to the
glass and, unless the container is washed immediately, it becomes difficult to
remove. This version of the procedure attempts to minimise the effects of sulfur
dioxide, by reducing the volume of sodium thiosulfate solution used. It also uses a
stop bath containing sodium hydrogencarbonate solution to avoid the production of
sulfur dioxide after measurements have been taken. A simple water bath avoids
the need for a Bunsen burner as long as there is hot water (about 50-60 C) in the
laboratory. At temperatures above 55 C, the reaction time is so short that the
results are unreliable.
By using cold water (kept in a refrigerator overnight) in the water bath, the procedure can be carried out at temperatures below ambient. The reaction time is longer
although the water bath becomes warmer as time passes. Temperature readings
can be taken before and after and the average used in the results. This is an extra
complication and is discussed in the Extension notes overleaf.

Special
equipment

The vials. Their capacity should exceed 10 ml, eg, 48 x 25 mm (h x d) vials from
Griffin & George, TUL-490-062E.
The water bath. Use a microwavable plastic61 container (capacity 500 cm3) with
lid. Holes can be made by pushing into the lid a very hot metal disc a little larger
than the diameter of the vials, eg, a coin, or a cork borer62. Unused holes can be
stoppered with bungs. If a 1 litre container is used as the water bath, test tubes
can be inserted in place of vials.
The water bath can be used for any procedures which require a more or less
steady temperature and do not take too long to complete.

The vials are placed in the container. Hot or

cold water can be added to adjust the temperature.
Up to six holes can be placed in the lid.

The capped vial is placed

horizontally on the tile and
held in place with Blutac.
The mark is viewed from above.

Monitoring the reaction

A black mark is made
with a suitable pen on
a white tile.

The stop bath: Another plastic container should be filled with 5% sodium hydrogencarbonate solution to which a small volume of universal indicator solution is
added. The vials with the reactants are placed in this bath to stop the reaction and
absorb sulfur dioxide gas. Use the colour of the indicator to check that the solution
has not become acidic. If it does, add more sodium hydrogencarbonate.

61
62

They are usually made of polypropylene and can be obtained from supermarkets or other general stores.
For this task, use an old borer, no longer employed to make holes in corks or bungs. Heating a cork borer will
soften the metal and ruin it for its normal use.
43

Procedure

Extension

On a white tile, draw a black line with a suitable marker pen.

Wear eye protection.
Using a 10 ml measuring cylinder, pipette or burette, place 10 ml samples of
0.1 M sodium thiosulfate solution into 6 glass vials. Place a cap on each vial.
Have ready a thermometer and the apparatus to deliver quickly 1 ml of 1 M
hydrochloric acid. A 10 ml measuring cylinder, burette, syringe or graduated
pipette could be used.
Remove the cap from a vial, add 1 ml of 1 M hydrochloric acid to the sodium
thiosulfate solution, start a stop clock, cap the vial and place it horizontally on
the white tile over the black mark. It is held in place with Blutac. Note the time
when the black mark can no longer be seen when viewed from above. Take
the vial off the white tile, remove the cap and quickly insert a thermometer to
note the temperature. Immerse the vial and its contents in the stop bath
solution.
Fill the water bath with warm water from a tap or kettle (50-60 C).
Insert a vial of sodium thiosulfate solution into the water bath. Remove the cap
and stir the solution with a thermometer until the temperature increases to
about 6 C above room temperature. Remove the vial from the water bath.
Repeat the instructions in the 5th bullet point to obtain a second set of
readings.
Insert a third vial of sodium thiosulfate solution into the hot water bath.
Remove the cap of the vial and stir the solution with a thermometer until the
temperature increases to about 12 C above room temperature. Remove the
vial from the water bath.
Repeat the instructions in the 5th bullet point to obtain a third set of readings.
Obtain two further readings at higher temperatures. Do not exceed 55 C.
Remove all the vials from the stop bath and rinse them out with water.

Empty the water bath. Half-fill it with cold water which has been stored in a refrigerator overnight and insert a vial containing sodium thiosulfate solution. Remove
the cap and stir the solution with a thermometer until the temperature drops to
about 6 C below room temperature. Remove the vial from the water bath.
The rate of reaction is proportional to the reciprocal of the time taken for the black
mark to disappear. At KS4, it should be possible to plot this value against the
temperature to show that, for every rise of 10 C, the rate of reaction doubles. An
example is shown below with results obtained using the method described here.
Two results below room temperature were obtained. An Excel spreadsheet can be
used to manipulate the results and produce a chart.
0.07
0.06
0.05

1/Time
-1
(sec )

0.04
0.03
0.02
0.01
0
0

10

15

20

25

30

35

40

45

Temperature (C)

In Y12 or 13, the procedure can be used to find the energy of activation of the
reaction using the Arrhenius equation. These results gave an energy of activation
of 54.4 kJ mol-1.

Disposal

All solutions can be disposed of down a foul-water drain.

44

Index
1,1,1-Trichloroethene ............................................... 7
1,1,2,2-Tetrachloroethane ........................................ 7
1,1,2-Trichloroethane ............................................... 7
1,2-Dichloroethane ............................................... 7, 9
1,4-Dichlorobenzene .............................................. 40
2-Methylpropan-2-ol ............................................... 40
Acids/metals reactions.............................................. 5
Ammonium chloride dissociation ............................ 12
Ammonium dichromate(VI) decomposition....... 12, 30
Aniline reactions ..................................................... 16
Anion tests................................................................ 4
Arculus method....................................................... 12
Asbestos, alternatives to ........................................ 12
Azo dye formation............................................. 16, 22
Barium nitrate ........................................................... 4
Benzene nitration, safer alternative ........................ 20
Biuret test ................................................................. 4
Bromine diffusion.................................................... 28
Bromine solution..................................................... 10
Cadmium iodide...................................................... 37
Caffeine extraction from tea ............................. 10, 23
Calcium, burning..................................................... 13
Carbon dioxide preparation ...................................... 4
Carbonates reacting with acids............................. 4, 5
Carbon-carbon double-bond test .............................. 6
Castor oil ................................................................ 10
Cation tests .............................................................. 5
Cetyl alcohol ........................................................... 40
Chlorinated hydrocarbons, alternatives to ................ 8
Chromatographic separation of aspirin etc and
nitration products of phenol .................................... 10
Cigarette smoking 'machine'................................... 35
Coal decomposition ................................................ 12
Concentrations of solutions ...................................... 3
Cooling curves.................................................. 40, 42
Copper(II) oxide/zinc reaction................................. 13
Cracking hydrocarbons or alcohols ........................ 12
Crude-oil distillation ................................................ 39
Crystal growth........................................................... 4
Cyclohexane..................................................... 10, 11
Degreasing agent ................................................... 10
Diazotization ..................................................... 16, 22
Dichloromethane .......................................... 7, 10, 11
Diffusion demonstrations .................................. 28, 29
Displacement reactions of metal salts ...................... 4
Displacement reactions of the halogens............. 4, 10
Distribution of ammonia & iodine between solvents10
Dithizone ................................................................ 11
Dodecanoic acid ..................................................... 40
Electric field patterns .............................................. 10
Electrolysis of molten salts ..................................... 37
Electrolysis of salt solutions...................................... 4
Electrostatic fields................................................... 11
Energy content of fuels........................................... 15
Enthalpy of formation of inter-molecular forces ...... 10
Ethanol ................................................................... 10
Ethanoylation.............................................. 16, 18, 19
Ethoxyethane.......................................................... 10
Ethyl 4-aminobenzenecarboxylate.......................... 16
Ethyl ethanoate....................................................... 10
Evolve CH15....................................................... 9, 10
Exothermic reactions .............................................. 30
Extraction of caffeine and limonene.................. 10, 23
Fat-pan fire ............................................................. 34
Fuels, burning......................................................... 14
Glass, distinguishing soda and borosilicate. ........... 10
Halogen displacement reactions............................... 4
Heats of reaction ...................................................... 4
Heat-resistant paper ............................................... 13

Hexandecan-1-ol.....................................................40
Hydrogen bonding...................................................10
Hydrogen burning ...................................................25
Hydrogen collection ..................................................5
Hydrogen exploding ................................................25
Hydrogen peroxide decomposition............................5
Hydrogen reduction of copper(II) oxide...................27
Hydrogen/oxygen explosion....................................26
Hydrolysis of group IV halides ................................10
Hydrolysis of methyl 3-nitrobenzenecarboxylate.....21
Hydrolysis of mono-substituted halogenoalkanes .....9
Indicators ..................................................................5
Iodine sublimation ...................................................12
Iodine value determination of unsaturated fats. ......10
Iron/sulfur reactions ..........................................12, 31
Lauric acid ..............................................................40
Lead analysis ..........................................................11
Lead(II) bromide......................................................37
Lead(II) chloride ......................................................37
Lead(II) iodide .........................................................37
Lead/acid accumulator simulation.............................5
Limonene extraction................................................10
Liquid fuels, burning................................................14
Lithium chloride.......................................................37
Lotoxane .......................................................9, 10, 11
Magnesium/steam reaction.....................................12
Metal nitrates, decomposition .................................12
Metals/acids reactions ..............................................5
Methanol .................................................................14
Methyl 3-nitrobenzenecarboxylate hydrolysis .........21
Methyl 4-hydroxybenzenecarboxylate.....................18
Methylbenzene........................................................11
Methyl benzenecarboxylate ....................................20
Mineral fibre ............................................................12
Molarities of solutions ...............................................3
Naphthalene .....................................................40, 42
Neutralisation reactions ............................................4
Nitrates, heating......................................................12
Nitration reactions .......................................18, 19, 20
Nitrobenzene reduction, safer alternative ...............22
Nitrogen dioxide diffusion........................................28
Nylon preparation....................................................11
Octadecanoic acid ..................................................40
Oxidation of alcohols...............................................24
Oxygen preparation ..................................................5
Perspex cement ......................................................11
Petroleum ether ................................................10, 11
Phenol reactions .....................................................18
Phenyl 2-hydroxybenzenecarboxylate ....................40
Phenyl salicylate .....................................................40
Phenylamine reactions............................................16
Potassium chlorate(V) decomposition.....................12
Potassium dichromate(VI).........................................6
Potassium manganate(VII) decomposition. ............12
Precipitation reactions.......................................4, 5, 6
Propan-1-ol .............................................................11
Propan-1,2,3-triol ....................................................10
Raoults Law .............................................................9
Rates of reaction.......................................................5
Recycling chemicals .................................................2
Reduction of a nitro-group ......................................22
Salol........................................................................40
Salt preparation.........................................................6
Silver nitrate..............................................................4
Soap preparation ......................................................6
Sodium burning in chlorine .....................................32
Sodium hydroxide and aluminium .............................6
Solutions, concentrations of......................................3
Solutions, stock.........................................................3
45

Spirit burners .......................................................... 14

Stearic acid............................................................. 40
Stoichiometry of precipitation reactions .................... 6
Sulfur dioxide test ..................................................... 6
Sulfuric acid dilution................................................ 36
Superwool 607 .................................................... 12
Tert-butyl alcohol .................................................... 40
Tests for anions and cations................................. 4, 5
Tetrachloroethene......................................... 7, 10, 11
Tetrachloromethane...................................... 7, 10, 11
Thermite reaction.................................................... 33
Thiokol rubber........................................................... 9
Thiosulfate/acid reaction..................................... 5, 43
Tin(II) chloride......................................................... 37
Tin(IV) iodide preparation ....................................... 11
Titrations................................................................... 6
Trichloroethene................................................... 7, 11
Trichloromethane.................................................. 7, 9
Triton Kaowool ..................................................... 12
Unsaturation, testing for............................................ 6
Vacuum pumps................................................. 29, 35
Volasil 244 .............................................. 9, 10, 11, 40
Waste disposal and treatment .................................. 2
Wijs solution........................................................... 10
Zinc chloride ........................................................... 37

46