Safer Chmeicals and Safer Reactions
Safer Chmeicals and Safer Reactions
Safer Chmeicals and Safer Reactions
safer reactions
L195
L195
July 2006
July 2006
Electrolysis of molten
lead(II) chloride
Microscale reduction of
copper oxide with hydrogen
Contents
1.
Introduction
1.1
1.2
1.3
2.
14
15
15
16
16
18
20
21
22
23
24
25
25
26
27
28
28
29
10.
11.
12.
12
14
8.1
8.2
9.
7
8
8
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
5.1
5.2
5.3
6.
Stock solutions
Suggested concentrations for various practical activities
5.
1
1
2
4.
Hazard information
Reducing risks
Reducing waste and safer disposal
Safer solutions
2.1
2.2
3.
Page
1
30
30
31
32
33
34
35
36
37
39
40
40
42
42
43
45
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.
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
Decreasing
risk
2
3
Health effects
FLAMMABLE
HARMFUL
IRRITANT
HIGHLY FLAMMABLE
TOXIC
CORROSIVE:
causes burns
EXTREMELY FLAMMABLE
VERY TOXIC
CORROSIVE:
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
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.
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.
React one with another. Iron(II) sulfate, acidified with a little dilute sulfuric acid, is a
cheap general-purpose reducing agent.
Metal salts
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.
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
7
8
Table 3
Suggested
concentration
Comments
(Hazards of these concentrations are shown. If no hazard is indicated, assume LOW HAZARD.)
Anion tests
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.
Carbonates reacting
with acids
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
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
Displacement reactions
of metal salts
Displacement reactions
with halogens
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
Much will depend upon current, type of electrodes and temperature but lower concentrations can
produce good results.
Heat of reaction
(displacement)
Heat of reaction
(neutralisation)
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)
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
concentration
Comments
(Hazards of these concentrations are shown. If no hazard is indicated, assume LOW HAZARD.)
Hydrogen collection
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)
The addition of copper sulfate crystals produces copper on the surface of the zinc which catalyses the reaction.
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
Oxygen preparation
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
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
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)
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)
Table 3
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
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.
Stoichiometry of
precipitation reactions
Sulfur dioxide test
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.
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)
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.
3.1
Current situation
Table 4 illustrates the hazards of chlorinated solvents that have been used in school chemistry.
Table 4
Substance
Risk11
School
use?
Comments
1,2-Dichloroethane
No
Dichloromethane
(Hazcard 28)
R40
Yes
Tetrachloroethene
(Hazcard 99)
R40, 51/53
Yes
R26/27,
51/53
No
R23/24/25,
40, 48/23,
52/53, 59
No
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
5 (MEL) (LTEL)
Tetrachloromethane
(Carbon tetrachloride)
(Hazcard 100)
1,1,1-Trichloroethane
(Hazcard 103)
HARMFUL,
DANGEROUS FOR THE ENVIRONMENT
1,1,2-Trichloroethane
HARMFUL
Trichloromethane
(Chloroform)
(Hazcard 104)
Yes
Trichloroethene
(Hazcard 99)
R45, 36/38,
52/53,67
Only by
trained
staff
9
10
11
12
No OEL assigned
carcinogenic effect,
DANGEROUS FOR THE ENVIRONMENT
2 (Sk12) (LTEL)
No OEL assigned
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
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
Comment
Table 6
Name
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.
Lotoxane
C11-13 branched
hydrocarbons.
B pt about 180 C.
Minimal.
Volasil
244
VWR (Merck)19
13.86 for 500 ml
Octamethylcyclotetrasiloxane.
(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
Activity or substance
Substitute
Chromatographic separation of
aspirin, paracetamol and caffeine.
Displacement reactions of the halogens (ie, the addition of chlorine solution to potassium bromide solution.
It is preferable to measure the enthalpy change when the intermolecular forces (hydrogen bonds) between ethanol molecules
are broken by the addition of cyclohexane.
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
Activity or substance
Substitute
Dichloromethane (HARMFUL).
20
Tetrachloromethane was the ideal solvent because water absorption is extremely small and solutions of acid
chlorides kept for years.
11
4.
4.1
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.
Other reactants or
catalysts can be placed here
Substance to
be heated is
placed here
Mineral fibre is
placed in the
opening or
further down
Diagram A
21
22
23
24
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)].
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
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.
5.1
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 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.
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.
Table 8
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.
5.2
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
Ink bottle
35 mm
Resin
Highly flammable
liquid
40 mm
5.3
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.
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.
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
17
6.2
Phenol reactions - a safer alternative
Comment
Phenol vapour has a maximum exposure limit (MEL) of 2 ppm for long-term exp-
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
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
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
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
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.
7.1
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
Controls and
hints
Glass tube
5 mm bore
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.
25
7.2
Hydrogen/oxygen explosion
Myth: The very loud bang can cause damage to the room and distress to pupils.
Comment
Procedure
Detergent solution in
a crucible
on wood blocks
t d or
a laboratory jack
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
Disposal
38
7.3
Comment
Procedure
Mineral fibre
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.
8.
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
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
9.
9.1
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
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
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.
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
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.
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
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.
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.
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
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
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
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
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
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
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.
Discussion
Hazard
M pt of salt (C)
M pt of metal (C)
Cadmium iodide
388
321
Lead(II) bromide
371
328
Lead(II) chloride
501
328
Lead(II) iodide
410
328
Lithium chloride
Harmful
610
1383
Tin(II) chloride
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
Terminal
ceramic block
RS, 426-351
Carbon
electrodes or
rods
Heat-proof mat
Heat source
(mini-Bunsen
burner)
Ammeter
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
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.
Comment
Procedure
o
0 - 350 C thermometer
75 x 10 mm test tubes
to collect the fractions
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
55
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 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
Name
Melting
point /C
1,4-Dichlorobenzene
53
Dodecanoic acid
45
Hexandecan-1-ol
49
2-Methylpropan-2-ol
26
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
Octadecanoic acid
70
Volasil 244
17
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
Temperature / C
40
Melting point
Time
41
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.
To datalogger
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
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 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
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
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
46