Extracting Metals From Scrap 8

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Extracting Metals from Scrap

A 507.12 ASS
A series presenting industry-related science practicals for schools
8. Extracting Metals from Scrap

Devised by Bill Harrison and David Wright, Pelsall School, Walsall Haydn Poulsom, Shelfield School, Walsall in association with Elkington Copper Refiners Ltd., Walsall, West Midlands
Published for The Standing Conference on Schools' Science and Technology by The Association for Science Education, College Lane, Hatfield, Herts. AL10 9AA
SCSST1985 ISBN 0 86357 026 7
ice Learning Centres
N12004
The 'Experimenting with Industry' publications are the product of a 'teachers into industry' project organized by The Association for Science Education on behalf of The Standing Conference on Schools' Science and Technology.
The Standing Conference on Schools' Science and Technology

The Standing Conference was established in 1971 to promote and encourage in the public interest the development of science and technology in schools. It is supported by the Department of Education and Science, the Department of Trade and Industry, the engineering profession, industry, and its member organizations.
The Association for Science Education

The Association's activities are totally directed towards the advancement of science education. Its membership of over 17,000 is drawn from teachers of science and others interested in science education, both in the UK and overseas.
Project Working Party

John Nellist General Adviser, Cumbria Chairman-elect, The Association for Science Education NS Education Consultants . Stuart Whitefoot ' Assistant Secretary, The Association for Science Education Development Manager, The Standing Conference on Schools' Science and Technology
Brian Nicholl Richard Turner
Series Editors
Brian Nicholl and Jenny Selfe, NS Education Consultants, 5 Dryden Street, London WC2.
Acknowledgements
The SCSST and ASE wish to acknowledge the work of the Teacher Fellows and the support given by Head Teachers and LEA advisory staff. Thanks are also due to the participating companies and, in particular, to the many individuals within those companies who gave so generously of their time and knowledge. The authors of 'Extracting Metals from Scrap'acknowledge the ideas and suggestions contributed during the early development of their project by Nigel Rainbow, formerly of Willenhall School, Walsall.
Extracting Metals from Scrap Experimenting with Industry
Foreword
The need to provide a framework which relates to everyday life, for science taught in schools, is now widely accepted. Much existing science practical work relates only to an academic syllabus, expects a single 'right' answer and provides very limited opportunity for experimental design, problem-solving and group working. The booklets in this series are based on the work of experienced science teachers who, during the summer of 1984, were linked with industrial companies as part of a project initiated by SCSST in collaboration with ASE. Their brief was to devise experiments drawn from industrial processes, which illustrate scientific concepts and show how they are applied in industry. This development was made possible by a generous donation from Lloyd's Register of Shipping. Experiments described in the booklets aim to replace, within the existing curricula, some of the present school practical work. They allow opportunity for pupils to conduct challenging investigations which enhance their understanding, and there is a problem-solving and openended element. The contribution of the teachers involved and the co-operation of the industrial firms who helped with the project is gratefully acknowledged. It is especially pleasing that medium-sized companies as well as major international groups were involved. The project has shown once again the value of effective links between schools and industry. Sir Geoffrey Alien, FRS Chairman SCSST
... '"
The Series
Further 'Experimenting with Industry' titles will be published during 1985, the complete series being detailed below. The teacher/industry partnerships which developed this material were widely distributed throughout England and in Wales. The industrial participants ranged from multi-national concerns well-known for their support of educational initiatives to companies in highly specialized areas of technology with little experience of such activities.
Title
1. Electrical Testing Bob Cheyne, St. John's School, Marlborough 2. Optical Fibres in School Physics Stephen Rutherford, Pimlico School, London 3. Industrial Use of Micro-organisms Steve Bowden, Whitchurch High School, Cardiff 4. Sugar Challenge Charles Dalleywater, Ramsey Ailwyn Community School, Ramsey 5. Chemicals for Agriculture Lyn Bossons, Biddick School, Washington 6. Brake Fluid and School Science James Dawber, Sharpies School, Bolton 7. Safety in Gas Appliances Peter Hancock, Dame Alice Owen's School, Potters Bar 8. Extracting Metals from Scrap Bill Harrison, Pelsall School, Walsall 9. Properties of Metals Hilary Laidler, Simon Balle School, Hertford 10. Electronics of Control Systems Virginia Lavender, Collingwood School, Camberley 11. Chemistry of Esters Don Linnell, The Bramhall High School, Bramhall 12. Physics of Fluid Flow Linda Scott, Pate's Grammar School for Girls, Cheltenham 13. PlantTissue Culture Tony Storr, Sharnbrook Upper School, Sharnbrook
Company
Square D Ltd., Swindon, Wiltshire GEC Hirst Research Centre, Wembley, London Nipa Laboratories Ltd., Pontypridd, Mid-Glamorgan British Sugar pic, Peterborough, Cambridgeshire
ICI Agricultural Division, Billingham, Cleveland Shell Chemicals, Carrington, Manchester British Gas Eastern Region, Potters Bar, Hertfordshire
Elkington Copper Refiners, Walsall, West Midlands British Aerospace, Stevenage, Hertfordshire Marconi Command & Control Systems, Camberley, Surrey Ciba-Geigy Industrial Chemical Division, Manchester Dowty Services Ltd., Cheltenham, Gloucestershire
Unilever pic, Bedford
Elkington Copper Refiners Limited

ECR Ltd. is a secondary copper refining company which was first established, in Birmingham, in 1807. Its origins go back to Faraday's work on electroplating. ECR is now located near Walsall in the West Midlands and recently became part of the IMI Group. The company, which employs about 240 people, buys in some 60-80 000 tonnes/year of low-grade metal scrap and recovers copper, silver and other metals. The process developed by ECR is highly efficient in recovering a large percentage of by-product materials. For this reason, ECR's technology and experience is in demand worldwide and the company, as well as supplying equipment and plant, accepts consultancy contracts covering complete feasibility studies, consultancy on existing installations and the training of personnel.
IV Extracting Metals from Scrap Experimenting with Industry
Contents
Teachers' _
1. 2. 3. Industrial background Educational scope Notes on experiments Experiment 1: Experiment 2: Experiments: Experiment 4: Experiments: Experiments: Experiment?: Assaying a gunmetal alloy scrap for copper content Analysis of mixed furnace oxide Analysis of lead/tin alloy Electrolytic purification of copper Laboratory model of the commercial purification of copper Simulation of copper stripping and nickel recovery Analysis of the acidified copper(ll) sulphate electrolyte 1 6 6 6 7 8 8 9 10 11 12
4. Appendix: Relationships to 16+chemistry syllabus
Students' worksheets
Experiment 1: Experiment 2: Experiments: Experiment 4: Experiments: Experiment6: Experiment?: Determining the percentage of copper in gunmetal alloy scrap Analysis of mixed furnace oxide Analysis of lead/tin alloy Electrolytic purification of copper Laboratory model of the commercial purification of copper Simulation of copper stripping and nickel recovery Analysis of the acidified copper(ll) sulphate electrolyte 13 16 20 23 25 27 30
The material which follows may be reproduced without infringing copyright provided reproduction is for pupil-use only. The permission of the publishers must be obtained before reproducing the material for any other purpose. Information in this publication is accurate to the best of the knowledge of the publishers and is given in good faith. However, no warranty is given or is to be implied with respect to the accuracy of such information. The publishers cannot accept liability for any accident or injury arising out of the use or application of the information and experiments.
Teachers' guide
ECR is a secondary copper refinery, that is only scrap or secondary feedstock is used. The feedstock for the refinery ranges from low grade residues, including certain catalysts and industrial chemical wastes, generally with a lower copper limit of 5%, to clean copper turnings and other high grade scrap of 96% plus copper content. In between these two extremes are various refining materials mixed brasses, gunmetal scrap, radiators, irony copper, burnt wire, brazier materials, etc. The process used is shown in Figure 6 (p.5). Low grade materials are generally screened, with the screenings going directly to the blast furnace stockyard and the fine materials to the briquetting press. Here, the material is mixed with lime and water and pressed into briquettes about the size of a house brick.
Figure 1 Furnace charge
The blast furnace charge consists of briquettes, low grade scrap, slags, residues, irony copper, etc., the object being to achieve an overall copper content of approximately 35%. Coke is also added with the charge and air is introduced via the tuyeres. The furnace is operated on continuous tap and the molten copper and slag leaves the bottom of the furnace and flows into a holding furnace where the slag and metal are separated. The fume from the top of the furnace is passed through a filtering system which separates out the heavy particles, eventually allowing low grade zinc oxide to be recovered. The heavy particle fraction containing 15% - 20% copper is recycled to the blast furnace. The slag from the holding furnace is granulated and sold as shot blast material. After the blast furnace, the copper (black copper) contains about 80% copper, along with the bulk of the tin, lead, nickel and precious metals which have been charged to the blast furnace.
Figure 2 The blast furnace
The black copper is then transferred, still molten, to the converter. Coke and tin-bearing materials, together with a small amount of irony material, are added to the charge and the molten contents are air-blown via a row of tuyeres. During this process the bulk of the tin, lead and zinc is fumed off and collected in a bag house as converter oxide a mixture of tin, lead and zinc oxides. The slags are removed and recycled to the blast furnace. The converter oxides are further processed in the tin/lead plant to produce very high quality tin/lead ingots sold for solder manufacture and a higher grade zinc oxide.
Figure3 Converter furnace
The resulting copper from the converter is termed rough copper (96% Cu) and is transferred to the anode furnace. Here, high grade scrap is added and a fire refining operation carried out before the metal is cast as anodes (98.5% Cu). Again, the slag formed is recycled to the blast furnace.
Figure 4 Anode furnace Extracting Metals from Scrap Experimenting with Industry
FigureB Electrolytic tank house
The anodes are then transferred to the tank house for electrolytic refining to produce high purity cathodes. Currently, ECR operates on a 28-day cycle, that is each anode is used to produce two cathodes at 14-day intervals. After the 28-day cycle, the remainder of the anodes are returned to the anode furnace. The solution circulating in the electrolytic tanks has to be conditioned to control the copper and nickel contents and it is during this treatment that the crude nickel sulphate is obtained. After each 28-day cycle, the slimes which have accumulated in the vats are pumped off and dried and this material which contains the precious metals gold, silver, platinum and palladium is sold for recovery. ECR believes that under normal economic circumstances the optimum size for a secondary copper refinery is about 25 000 tonnes per year cathode production. Such a refinery allows optimum manning and staffing and economic use of equipment and does not create large logistic problems in respect of feedstock supplies. Ideally, such a plant would require approximately 100000 tonnes of material, averaging 25% copper content, per year. A practical input of copper scrap to produce 25 000 tonnes per year of electrolytic cathode would also provide the following by-products: (tonne/year) 230 - 280 300 - 350 1300- 1700 400 - 450 280 - 340 12000- 15000
Tin/lead ingot Anode slime Low grade zinc oxide High grade zinc oxide Impure nickel sulphate Granulated slag
35% - 40% tin 2.5% - 3.5% silver 50% - 60% zinc 75% - 80% zinc 22% - 23% nickel
Treatment of secondary copper and its alloys Flow sheet Alloys Furnace Residues Contaminated alloys Copper scrap Furnace
Ingots Srrii 3lter Cathode Wire bars Ingots I By-products Final slag
Wire bars Ingots
Low grade scrap Slags Residues Irony copper Coke
Blast furnace
Low grade ZnO fume Granulated slag
Black copper (80% Cu) Scrap (2-6% Sn) -<-
Experiment 1
Converter slag
Converter furnace
Experiment 2 Mixed Sn/Pb/Zn oxides Reduction furnace
- ZnO
Rough copper (96% Cu) Scrap ( + 90% Cu) I Anode furnace slag Anode furnace
Sn/Pb alloys -*-
Experiment 3
Anodes (93.5% Cu)
Experiments 4,5 & 7 Electrolytic refinery Nickel sulphate Experiment 6
Anode scrap
Figure 6
P.M. slimes
Cathodes
Although the pyrometallurgical processes carried out at ECR are of primary importance in the overall process, practical work in this area is not included in this series of experiments. These procedures are much more complex than, for example, the reduction of iron ore in the blast furnace and, in addition, the high temperatures required are difficult to produce in the school laboratory without costly furnace equipment. It should be noted that much of the assaying work at ECR involves the use of special instrumentation, particularly the atomic absorption spectrophotometer, and the use of chemicals which are difficult to handle in the school laboratory. For this reason, some of the experiments described here tend to parallel the ECR processes rather than to reproduce them.
Special note
2. E
The experiments which follow are aimed primarily at the 14-16 age group, i.e. pupils studying for CSE/O-level/16+ chemistry courses. However, they could also be used in CEE, 'Science in Society' or A-level courses but some modification would be heeded in the latter case. The practical work falls more or less into three categories: a) assaying/quality control of raw materials and products Experiments 1, 2 and 3; b) electrolysis processes Experiments 4, 5 and 6; c) process control/monitoring Experiment 7.
3. Notes on experiments
Experiment 1 Apparatus and chemicals
Gunmetal alloy 50% nitric acid (by volume), (10 cm 3/group) Sodium carbonate (solid) Beaker 100 cm 3 (2) Filterfunnel Filter pump & Buckner flask (if available) Ashless filter paper (preferably 11 cm diameter, 542 Whatman grade) Evaporating basin Measuring cylinder 10 cm 3 Tripod and gauze Bunsen burner Bench mat Goggles Use of top-pan balance (reading to second place) Access to fume cupboard and drying oven
Assaying a gunmetal alloy scrap for copper content Background notes

In this experiment students are asked to determine the percentage of copper in a sample of gunmetal turnings. Such a sample could be delivered to ECR from a local engineering company as waste turnings from some machining process. In order to fix a price for the scrap it would be necessary for the analysts to assay the material for copper content. With this particular sample they would also determine the tin content. Assaying is a vital part of the work of the laboratory and small errors could cost the company large amounts of money. The gunmetal alloy used in this experiment contains approximately 87% Cu; 10% Sn; 1.5% Zn; 0.7% Pb; 0.3% Ni and small traces of other elements. The alloy was supplied by Bureau of Analysed Samples Ltd., Newham Hall, Newby, Middlesbrough, Cleveland TS8 9EA; catalogue no. BCS-CRM 207/2; cost (1985) 10.50 per 100 g. At ECR this sample of scrap would probably be dissolved in 50% nitric acid plus a few cubic centimetres of 30% hydrofluoric acid to eliminate the tin. The copper would then be determined by electrolytic deposition using platinum electrodes. For safety reasons in handling some of the above materials and because there are a number of electrolysis experiments in this series, a simple yet rough approximate method for use in the school laboratory was developed.
Points of guidance
In this experiment it is assumed that the gunmetal sample is primarily 90% Cu, 10% Sn. If students are aware of other elements present, they will need to accept these as sources of error. The advantage of choosing an alloy with tin is that the tin is precipitated out as Sn02 xH 2 0 in nitric acid, leaving the copper in solution. The idea then is to precipitate the copper as copper carbonate and then decompose to the oxide. It is suggested that the first part of the alloy into solution is carried out in teacher. Class samples can be placed hot plate can be made from a piece above two or three Bunsen burners. experiment to take the a fume cupboard by the on a hot plate. A simple of caste iron supported
When filtering out the SnO 2 xH 2 0 it may be necessary to filter twice in order to obtain a clear solution. Occasionally, after filtering out copper carbonate, the filtrate has a blue/green tinge. This may be due to the small amount of nickel present in the alloy. The copper carbonate should be washed thoroughly to remove all the solid sodium carbonate from it. If desired and particularly if extending the experiment to a sixth form activity it would also be possible to determine the tin content by burning down to Sn0 2 as for the copper determination. In a normal practical session it should be possible to reach the stage where the CuC0 3 has been filtered out. This can be dried in an oven or left to dry naturally until the next lesson, when it can be decomposed to the oxide. Students may note, alongside the black oxide, a feathery copper deposit. This is probably due to reduction of the oxide by the carbon in the filter paper.
-~
Apparatus and chemicals
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Analysis of mixed furnace oxides Background notes

In this experiment students are asked to determine the percentage of zinc oxide, lead(ll) oxide and tin (IV) oxide in a mixture. Such a mixture is produced by ECR from their converter furnace. A typical analysis is 30%-40% ZnO; 2%-25% PbO; 5%-25% Sn0 2 ; 2%-5% CuO. A suitable mixture for the students' experiment is 40% ZnO; 30% PbO; 30% Sn0 2 by mass. A 1 g sample of this mixture should produce 0.3 g Sn0 2 ; 0.39 g PbSO4 (0.36 g PbCI 2 ); 0.4 g ZnO. At ECR the routine analysis uses atomic adsorption, but for accurate work the lead and zinc are determined using EDTA, with Xyanol Orange as an indicator.
50% nitric acid (by volume), (20 cm 3/group) , Mixed oxides sample (40% ZnO; ; 30% PbO; 30% Sn0 2 by mass) :: (1 g/group) ; Sodium carbonate (powdered) (if Part II is attempted) ; Beaker 100 cm 3 (3) ipilterfunnel (2) { Ashless filter paper (preferably ; 11 cm diameter, 542 Whatman ; grade) Evaporating basin (3) K Measuring cylinder 25 cm 3 f Tripod : Bunsen burner : Bench mat Goggles Use of top-pan balance (to second place) Access to fume cupboard and drying oven
Points of guidance
It is suggested that the dissolution of the oxides is carried out in a fume cupboard by the teacher. Goggles should be worn. For details of a simple hot plate, see Experiment 1 (above). Keeping the filter papers in a desiccator for a few days should minimize any inaccuracy caused by loss of moisture from the filter papers. If Part II is used to determine the percentage of zinc oxide, ashless filter papers must be used.
Experiment 3 Apparatus and chemicals

Solder sample (see note) 50% nitric acid (by volume), (20 cm 3/group) Dilute sulphuric acid Ashless filter paper (preferably 11 cm diameter, Whatman 542 grade) Beaker 100 cm3 (2) Measuring cylinder 25 cm 3 Filter funnel (2) Evaporating basin (2) Tripod Gauze Bunsen burner Bench mat Goggles Use of top-pan balance (to second place) Access to fume cupboard and drying oven
Analysis of lead/tin alloy Background notes

In this experiment students are asked to determine the percentage of tin and lead in a tin/lead alloy. Such an alloy is produced in the tin/lead plant. The converter oxide a mixture of tin, lead and zinc oxides is processed in the tin/lead house to produce very high quality tin/lead ingots which are sold for solder manufacture and a higher grade zinc oxide. Assaying of this alloy is another important part of the work of the laboratory at ECR. At ECR the alloy is analysed using atomic adsorption for routine work, but for accurate work the lead content is determined by EDTA, with Xyanol Orange as an indicator. Note.: A suitable sample is made to BS 219/1959 of 39%-40% Sn; 57.5% Pb; 2.5% Sb and small traces of other elements. However, any supply of soft solder sticks 40/60 tin lead will be satisfactory. Resin cored solder should not be used.
Points of guidance
The worksheet has been split into two parts. The first will give the percentage of lead present in the sample and, hence, the percentage of tin by subtraction assuming a pure tin/lead alloy. The second part will give the percentage of tin and, hence, the total percentage may not add up to 100% because of the other elements present in the alloy. It is suggested that the dissolution of the solder in 50% nitric acidshouldbedoneinafume cupboard by the teacher. Goggles should be worn. For details of a simple hot plate, see Experiment 1 (p.7). If the filter papers are left in a desiccator for 48 hours, the error in weighing the filter paper before and after drying is minimal. The drying oven is best set to about 95 C. The precipitation of lead chloride may be used as an alternative the precipitate is less finely divided. If the percentage of tin is to be found directly, the filter paper may have to be burned away to convert the hydrated tin(IV) oxide to anhydrous tin(IV) oxide. Heating in the drying oven for 30 minutes will sometimes do this dehydration.
Experiment 4
Electrolytic purification of copper

This experiment mirrors closely the standard electrolysis except that the electrolyte is acidified copper(ll) sulphate solution. At ECR this is carried out on a much larger scale a model is included as Experiment 5 and with a smaller current so that a much more regular deposition occurs. More details of the commercial process are given in Experiment 6.
Background notes

Copper cathode(copper sheet 1 cm wide and of suitable : length) Impure copper anode (suggest brass, copper-nickel [nickel silver], old pennies or even : copper sheet) ; Beaker (suggest 100 cm 3 ) Power supply (suggest 6 V) Connecting wires, ammeter and rheostat as necessary Beaker of water (for rinsing electrodes) Acidified copper(ll) sulphate solution (approx 1.5M H 2 S04, 0.75M CuS04 ) Use of top-pan balance (to second place)
Power source Ammeter
Copper wire supports
Figure 7
Points of guidance
These are listed under Experiment 5 (p.10). ; ' To prevent the electrodes touching the beaker, the top 1 cm could be bent over and suspended from stripped household ring main cable bus bars (see Figure 7).
Experiment 5
Laboratory model of the commercial purification of copper Background notes

Commercially, the tank house contains 30 anodes and 31 cathodes per cell and 20 cells to a tank. The cathodes are thin pure copper sheets and the anodes contain about 98% copper, with up to 1 % nickel as well as lead, tin, zinc, antimony, arsenic with small amounts of silver, gold, platinum and palladium. During electrolysis the nickel goes into solution, while the precious metals form solid compounds which are known as the anode slime. The nickel is recovered by stripping the copper from the solution (see Experiment 6), while the anode slime is sold to precious metal refiners. Any lead is precipitated in the slimes as lead sulphate.
Impure copper anodes
Copper covered wood
Connected to negative terminal
Connected to positive terminal
Copper wire bus bars
Plastic sandwich box
Pure copper cathodes
Figure 8
Acidified copper(ll) sulphate electrolyte

Clear, rigid plastic container (suggest lunch box) Wood strips, cut to slot on long sides of container (2) Thin copper sheet for contacts (see Figure 8 for arrangement) Insulation tape (see Figure 8) Pure copper cathodes (suggest copper sheet of suitable size, top bent over to act as a hook) j Impure copper anodes (same size j as cathodes, preferably copper- 3 nickel [nickel silver]) if Thick copper wire bus bars :1 (suggest household ring main f cable with insulation left on one | end see Figure 8) | Power pack with suitable ff ammeter and connecting wires J Acidified copper(ll) sulphate | solution (approx. 1.5M H 2 S04, I 0.75M CuS04 ) ;j
Points of guidance
The apparatus will need to run continuously for about a week at 0.1-0.2 A. This will enable students to see a noticeable thinning of the anode, a regular deposit of copper on the cathode and an appreciable colour change caused by nickel ions in the solution. Make sure that the bus bars have good electrical continuity and use the lid of the box to reduce evaporation.
Experiment 6
Simulation of copper stripping and nickel recovery Background notes

As the impure anodes contain nickel, the electrolyte becomes contaminated with nickel ions after several days. The electrolyte is pumped to a second, smaller tank house, where the copper ions are stripped from the electrolyte using lead anodes and pure copper cathodes. The copper content is regularly monitored (see Experiment 7).
10
When most of the copper has been removed, the remaining solution is largely nickel(ll) sulphate. This is then evaporated and crude nickel(ll) sulphate crystallizes out and is then sold.

:iCopper cathode (copper sheet 1 cm wide and of suitable length) Lead anode (lead sheet, as above, but at least 1 mm thick) Beaker (suggest 100cm 3 ) ;Larger beaker (suggest 150cm 3 ) Power supply (to provide current in the range 0.75-1.0 A) Connecting wires, ammeter and rheostat as necessary Beaker of water (for rinsing electrodes) Propanone (for cleaning electrodes) Copper(ll) sulphate-5-water crystals Nickel(ll) sulphate-6-water crystals ; M sulphuric acid Use of top-pan balance (to second place)
Points of guidance
Most of the copper should be removed if a current of about 0.8 A runs for 45 minutes. A spongey deposit forms on the cathode and, if treated carefully, very little, if any, falls off. Gassing occurs initially, but soon stops. During the experiment, the electrolyte changes colour from a blue-green to a lime green, reinforcing the fact that the copper is being removed. The nickel(ll) sulphate solution contains sulphuric acid, which is concentrated on evaporation to 4-5M. Students should be warned of the dangers of this. The crystals which are formed are a slightly different colour from the original nickel(ll) sulphate. This is probably due to the acid conditions. A lid placed over the cell is used to reduce acid spray.
Suggested additional demonstration

If copper-nickel anodes are used in Experiment 5, these can be removed at the end of that experiment and replaced by ones made of lead sheet, allowing stripping to occur in situ. If copper-nickel anodes are not used, a previously made electrolyte containing nickel ions can be substituted instead. The colour change can be demonstrated quickly (without good adhesion of copper) if a higher current is used.
Experiment 7
^Apparatus and chemicals
Burette (2 or 3) (see note) Beaker (suggest 100cm 3 ) Funnel Conical flask (suggest 250 cm 3 ) Wash bottle of distilled water 0.2M sodium hydroxide solution (exactly) 0.1M sodium thiosulphate solution (exactly) Solid potassium iodide Methyl red indicator (water soluble) Starch indicator Acidified copper(ll) sulphate solution (approx. 0.15M H 2 SO4, 0.075M CuS04 ) Dilute ethanoic acid with dropper
Analysis of the acidified copper(il) sulphate electrolyte Background notes

At regular intervals it is necessary to test the tank-house electrolyte for acidity and copper content to maintain the electrical conductivity and to prevent gassing. At least once a day the titration outlined in this experiment takes place, but on the full-strength electrolyte. Note: The experiment is quicker with two burettes, but it may be necessary to use one cleaned between titrations. It is suggested that, in addition, a teacher's burette is used to dispense the electrolyte; alternatively, the students could use a pipette, with a pipette filler.
Points of guidance
The end point with the methyl red indicator is fairly straightforward (pink to orange) but the end point in the copper estimation is more difficult to see, being partly masked by the methyl red coloration and the iodine suspension. It may be worthwhile to demonstrate the copper estimation before the students attempt it. The copper estimation is not part of the 16+ syllabus, but it contains some interesting chemistry from which more-able students will benefit.
11
4. Appendix
Relationships to 16+ chemistry syllabus
Experiment 1
Action of acids on metals/alloys; action of acids on carbonates; neutralization; precipitation of insoluble carbonates; thermal decomposition of carbonates; calculations involving the mole.
Experiment 2
Action of acids on metal oxides; precipitation of insoluble salts (PbSO 4 , ZnC0 3 ); thermal decomposition of carbonates; calculations involving the mole.
Experiment 3
Action of acids on metals/alloys; formation of insoluble salts; calculations involving the mole.
Experiments 4 & 5
General electrolysis; purification of copper.
Experiment 6
General electrolysis; selective deposition; choice of electrodes (inert anode); crystallization; calculations involving the mole.
Experiment 7
Neutralization; volumetric theory and practice; calculations; use of indicators; estimation of copper (probably A-level); calculations involving the mole; formation of insoluble salts. These relationships are summarized in the table which follows.
Chemistry concepts covered

Concept Action of acids on: metals/alloys metal oxides carbonates Neutralization Precipitation of salts Thermal decomposition of: hydrates carbonates Calculations involving the mole General electrolysis: purification of copper selective deposition choice of electrodes (inert anode) Crystallization Volumetric theory and practice Use of indicators Copper estimation (l 2/thiosulphate)
12
Experiment 1
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Students' worksheets
The following experiments were developed by a group of teachers working with engineers and scientists at Elkington Copper Refiners Ltd., in Walsall. The experiments demonstrate some of the industrial practices used in a large secondary refining plant. It is hoped that from this practical work you will understand something of the ways in which the science you learn at school is applied to the solution of real industrial problems.
Experiment 1
Determining the percentage of copper in a sample of

The sample of gunmetal alloy scrap contains mostly copper, but has a significant amount of tin. Take a clean, dry 100 cm 3 beaker and label it. Accurately weigh it and then carefully add about 0.5 g of the gunmetal sample. Weigh the beaker and contents. Mass of beaker + sample Mass of beaker Mass of sample Take your beaker, with sample, to the fume cupboard, where your teacher will add 10 cm 3 of 50% concentrated nitric acid. Q. What did you see occurring in the beaker? 9
Q.
Why use a fume cupboard?
When the reaction slows, your teacher will cover the beaker with a watch glass and bring it to the boil on a hot plate. Q. What do you now notice about the solution?
Continue the boiling for a few minutes until all of the alloy has dissolved and no more gas is evolved. Your teacher will then remove the beaker from the hot plate and allow it to cool. Make sure you are wearing goggles, then carefully take the cool beaker to your bench. Carefully add distilled water to your sample up to the 25 cm 3 on the beaker. Gently bring the solution to the boil and continue for no more than a minute. Allow it to cool. Q. Look carefully at your solution and describe what you see.
13
Q.
Do you have any idea what this solid could be?
Filter the solution into a 100 cm 3 beaker, making sure to wash out any solid left in the beaker, and also to wash the residue in the filter paper. Use distilled water from a wash bottle. Q. Why is it necessary to wash the residue?
Q.
Where is the copper now?
Q.
Where is the tin now?
Put the residue in the filter paper to one side in case your teacher wants you to work on it later. Take the filtrate and treat it in the following way. Make sure that you have at least 50 cm 3 of filtrate in your beaker; if not, make it up to that amount with distilled water. Now, carefully add a spatula load at a time of solid sodium carbonate to your solution, and stir. Q. Why is effervescence occurring?
Carry on adding the sodium carbonate until no further effervescence occurs and a thick green gelatinous precipitate is formed. Q. What is this precipitate?
Q.
Write down a word and symbol equation for the reaction.
Filter off the precipitate using ashless filter paper and a filter pump, if available. This will be quicker than the ordinary method. Wash the residue thoroughly with distilled water in order to wash out any undissolved sodium carbonate. Make sure you get as much as possible of the solid out of the beaker otherwise it will cause an error in your calculations. If your filtrate comes through as a blue solution, you have not precipitated all of the copper. You must add a little more sodium carbonate and filter and wash again.
14 Extracting Metals from Scrap Experimenting with Industry
You must now dry the residue. This can be done either by placing the residue in an oven or simply by leaving it to dry out for the next lesson. You are now ready to decompose your copper compound by heating it. Weigh an evaporating basin. Place your sample still in the filter paper in the basin and put the basin, with sample, onto a tripod and gauze and heat from below. After a little while, set the paper alight and allow it to burn away to ash. Then heat strongly from below for a few minutes until the residue is completely black. Heat again from above to burn away any remaining filter paper and to ensure complete thermal decomposition. Allow to cool, and then weigh. Mass of evaporating basin + residue Mass of evaporating basin Mass of residue Q. = = = g g q
What is the black compound produced on heating?
Q. Write a word and symbol equation for the thermal decomposition of your copper compound.
Calculation 1 mole of CuO contains ............... mole of Cu atoms ............... g of CuO contains ............... g of Cu atoms /. ............... g of residue contains ............... g of Cu .". ......x...... g of original gunmetal contains ......y...... g of Cu .". % of Cu in gunmetal alloy = x/y x 100% = ............... % Cu
15
Experiment 2
Analysis of mixed furnace oxide Part 1

This is a mixture of zinc oxide, lead(ll) oxide and tin(IV) oxide. Weigh a clean, dry 100 cm 3 beaker. Add about 1 g of the mixture and reweigh the beaker. Mass of beaker + sample Mass of beaker empty Mass of sample = = = g g g
Take your beaker to the fume cupboard, where your teacher will add 20 cm 3 of 50% nitric acid. When the reaction stops, the beaker is covered with a watch glass and boiled gently for two minutes (still in the fume cupboard). Q. Why is a fume cupboard used?
The white tin(IV) oxide has not dissolved. Q. Write down the two word equations and the two chemical equations for the dissolution of the zinc oxide and the lead(ll) oxide.
Q.
Why was a watch glass used?
When cold, filter off the undissolved tin(IV) oxide into a weighed filter paper. Wash all the white solid into the filter paper. Keep the filtrate. Weigh an evaporating dish and add the filter paper plus tin(IV) oxide and place in a drying oven. Mass of filter paper (dry) Mass of evaporating dish Mass of evaporating dish + filter paper = = g g g
Now weigh the evaporating dish, dry filter paper and dry oxide. Mass of dish + filter paper + tin(IV) oxide Mass of dish + filter paper Mass of tin(IV) oxide
16
= = =
g g g
Percentage of tin(IV) oxide in the sample = mass of tin oxide/mass of sample x 100% = .............../............... x 100% = ............... % of tin(IV) oxide
Add dilute sulphuric acid to the filtrate to precipitate the lead as white lead sulphate. Q. Write down the word equation and then the chemical equation for the formation of the precipitate.
Filter off the precipitate into a weighed filter paper, carefully washing all the white solid out of the beaker. Keep the filtrate if your teacher has told you to do Part II of this worksheet. Weigh an evaporating dish and add the filter paper plus the precipitate and place it in a drying oven. Mass of filter paper Mass of evaporating dish Mass of evaporating dish + filter paper Weigh the evaporating dish, plus dry contents. Mass of dish + filter paper + lead sulphate Mass of dish + filter paper Mass of lead sulphate No. of moles of lead sulphate (PbS04 ) = mass of lead sulphate/mass of 1 mole of lead sulphate = .............../............... = ............... moles of lead sulphate = = g g g = = = g g g
1 mole of lead sulphate (PbSO4 ) is formed from 1 mole of lead(ll) oxide .'. no. of moles of lead(ll) oxide is ............... mole .". mass of lead(ll) oxide = no. of moles x mass of 1 mole
= ............... x ............... g
= ............... g of lead(ll) oxide

Extracting Metals from Scrap Experimenting with Industry 17
Percentage of lead(ll) oxide - mass of lead(ll) oxide/mass of sample x 100% = ............... / ............... x 100% = ............... % of lead(ll) oxide
If Part II is not to be carried out, then work out the percentage of zinc oxide in the mixture as follows: Percentage of zinc oxide - 100 - (% of tin(IV) oxide + % of lead(ll) oxide) = 100 - (............... + ...............) = ............... % of zinc oxide .*. composition of the mixture is ....... % ZnO; ....... % PbO; ....... % SnO2
Part II
Add powdered sodium carbonate to the filtrate, a little at a time, until there is no more effervescence. Continue to add the powder until no more zinc carbonate is precipitated. Q. Write down the word equations and the chemical equations for the two reactions.
Filter off the white precipitate into an ashless filter paper, making sure that all the white powder is washed into the filter paper. Wash the precipitate twice to dissolve out any sodium carbonate. Weigh an evaporating dish and place the filter paper plus contents in the dish in a drying oven. Burn off the filter paper, when dry, and heat strongly to decompose the zinc carbonate into zinc oxide. Q. Write down the word equation and chemical equation for the reaction.
Weigh the cold dish and zinc oxide. Mass of dish + zinc oxide Mass of dish Mass of zinc oxide = = g g q
18
Percentage of zinc oxide in the sample mass of zinc oxide/mass of sample x 100% - .............../ ............... x 100% = ............... % zinc oxide The analysis of the mixed oxide is ....... % ZnO; ....... % PbO; ....... % Sn0 2 Q. Does this add up to 100%?
19
Experiment 3
Analysis of lead/tin alloy Part I

Weigh a clean, dry 100 cm 3 beaker. Add about 1 g of the alloy filings and weigh the beaker and contents. Mass of beaker + alloy filings Mass of beaker Mass of alloy filings = = = g 9 g
Take your beaker to the fume cupboard, where your teacher will add 20 cm 3 of 50% nitric acid. When the reaction stops, the beaker is covered with a watch glass and boiled gently for two minutes (still in the fume cupboard). Q. Why is the fume cupboard needed?
The white precipitate is hydrated tin(IV) oxide. Q. Why was the watch glass used?
(Note: If Part II of this experiment is to be carried out, an ashless filter paper must be used.) Filter the cold solution through an ashless filter paper. Carefully wash all the precipitate into the filter paper. Place the filter paper in a weighed evaporating dish in a drying oven.
Dilute sulphuric acid is added to the filtrate to precipitate the lead as lead sulphate. Q. Write down the word equation and then the chemical equation for this reaction.
Filter off the white powder into a weighed filter paper and carefully wash all the powder into the filter paper. Place the filter paper in a weighed evaporating dish and dry in a drying oven. Mass of filter paper Mass of evaporating dish Mass of evaporating dish + filter paper = = g g g
20
When dry, reweigh the evaporating dish and contents. Mass of evaporating dish + filter paper + lead sulphate Mass of evaporating dish + filter paper Mass of lead sulphate = = = g g g
No. of moles of lead sulphate (PbSO4) - mass of lead sulphate/mass of 1 mole of lead sulphate = ............... / ............... = ............... mole of lead sulphate
1 mole of lead produces 1 mole of lead sulphate /. mole of lead weighs: (at. mass of lead x no. of moles) g = ............... x ............... g = ............... g .*. percentage of lead in the alloy - mass of lead/mass of alloy filings x 100% - .............../..........,.... x 100% Percentage of lead is............... %
If Part II of this experiment is not being done, then percentage of tin = (100 - percentage of lead) % - (100 - ...............) % Percentage of tin is ............... %
Take the evaporating dish, plus filter paper containing hydrated tin(IV) oxide, and place it on a tripod and gauze. Burn off the filter paper and reweigh. Mass of evaporating dish + tin(IV) oxide Mass of evaporating dish Mass of tin(IV) oxide .*. no. of moles of tin(IV) oxide (Sn0 2 ) - mass of tin(IV) oxide/mass of 1 mole of tin(IV) oxide = .............. / ............... = ............. mole of tin(IV) oxide
Extracting Metals from Scrap Experimenting with Industry 21
Part II
= = =
g g g
1 mole of tin produces 1 mole of tin(IV) oxide .*. mass of............... mole of tin weighs: (at. mass of tin x no. of moles) g
= (............... x ...........,...)g
Percentage of tin in the alloy mass of tin/mass of alloy filings x 100% = .............../ ............... x 100% Percentage of tin is ............... % Q. Do the two percentages add up to 100%? Explain your answer.
22
Electrolytic purification of copper

Pour the electrolyte into the beaker until it is about 1 cm from the top. Weigh the cathode and anode separately and record their masses. Mass of cathode Mass of anode
g g
Figure 1
Connect the cathode and anode to the ammeter and power supply as shown in Figure 1. Make sure that the pure copper cathode is connected to the negative (black) terminal of the power supply, and the impure copper anode is connected to the positive (red) terminal. Place the cathode and the anode into the electrolyte. They must not touch each other or the beaker. Switch on the power supply so that the ammeter reads a current of 1 A. Q. After about five minutes what change do you notice:
i) at the anode;
23
ii) at the cathode; iii) in the electrolyte?
Q. After a further 30 minutes, look carefully at the anode, cathode and electrolyte and explain any changes: i) at the anode; ii) at the cathode; iii) in the electrolyte.
Switch off the power supply and carefully remove the anode and cathode. Wash them by dipping them into the beaker of water, dry them, then reweigh them. Mass of cathode Mass of anode Q. = = g g
Explain any change in the mass of the cathode.
Q.
Explain any change in the mass of the anode.
At the beginning of the experiment, the anode was impure copper. Q. What has happened to the copper?
Q.
What has happened to the impurities?
24
Laboratory mode! of the commercial purifecalion of cooper

Your teacher will demonstrate how copper is purified commercially, using the apparatus shown in Figure 1.
Impure, copper anodes
Copper covered wood
Connected to negative terminal
Connected to positive terminal
Copper wire bus bars
Plastic sandwich box
Pure copper cathodes
Acidified copper(ll) sulphate electrolyte Figure 1
Q.
Why are so many electrodes used?
Q.
How are the cathodes connected to the power supply?
Q.
At what voltage is the cell operating?
Q.
Why is this voltage chosen?
25
The apparatus will be left set up for a suitable length of time. Q. How long was it left set up?
Q.
Why was this time chosen?
Q.
Describe the changes:
i) at the cathode; ii) at the anode; "
iii) in the electrolyte.
Q.
Explain these changes.
'..
In the commercial process, the electrolyte is analysed regularly for acid and copper content. Q. Why is this necessary? :.
26
Simulation of copper stripping and nickel recovery

Accurately weigh about 2.5 g of copper(ll) sulphate crystals. Record the mass and put the crystals in a small beaker. Mass of copper(ll) sulphate = g
Weigh about 2.5 g of nickel(ll) sulphate crystals and add these to the beaker. Add about 50 cm 3 of M sulphuric acid to the beaker and stir carefully until all the crystals have dissolved. Add more acid until it is about 1 cm from the top of the beaker. Clean the cathode and anode with propanone, weigh them separately and record their masses. Mass of cathode (copper) Mass of anode (lead)
g g
Figure 1
Make up a cell as shown in Figure 1, with the copper connected to the negative (black) terminal of the power supply and the lead connected to the positive (red) terminal. They should not touch each other or the beaker.
27
Q. Describe, as accurately as you can, the colour of the electrolyte.
Switch on the power supply so that the current flowing is about 0.8 A. Q. What do you see:
i) at the cathode; ii) at the anode?
Leave the apparatus set up for about 45 minutes then switch off. Carefully remove the cathode and anode, wash them by dipping them in water, then leave them to dry. When dry, record their masses. Mass of cathode Mass of anode Q. Describe the appearance of: = = g g
i) the cathode; ii) the anode; iii) the electrolyte.
Q.
Explain what has happened to the cathode.
Q.
Explain what has happened to the anode.
Q.
Explain what has happened to the electrolyte.
Pour the electrolyte into a larger beaker and boil it gently until crystals start to appear (that is when 12-25 cm 3 is left). Stop heating immediately, and leave to cool. Warning: The liquid in the beaker is a concentrated acid. Treat it carefully and wear goggles when heating.
Q.
Describe the crystals formed.
At the beginning of the experiment, the electrolyte contained copper and nickel. Q. Where is the copper now?
Q.
Where is the nickel now?
The mass of copper in your original sample of crystals can be calculated. The relative molecular mass of copper(ll) sulphate 5 - water (CuSO4 . 5H 20) is 250, and the relative atomic mass of copper = 64. Mass of copper in crystals = mass of crystals x (64/250) - ............... x (64/250) = ............... g Q. How much of the original copper did you strip from the electrolyte?
29
Experiment 7
Analysis of the acidified copper(ll) sulphate electrolyte

You will have available either a pipette or a burette containing the diluted cell electrolyte. Carefully run exactly 25 cm 3 of this into a conical flask. Add three drops of methyl red indicator. Q. What colour does the liquid go?
Use a funnel to fill a clean burette to above the zero mark with 0.2M sodium hydroxide solution. Carefully run this liquid out into a beaker until the bottom of the meniscus is resting on the zero mark. Carefully run the sodium hydroxide solution from the burette into the liquid in the conical flask. After a while you will notice a change in colour in the indicator around the area where the solution is being run in. Swirl the flask slowly until the new colour disappears. When the colour takes a long time to disappear, wash around the inside of the conical flask with distilled water, then add the sodium hydroxide solution slowly until the colour changes with one drop added. Q. What colour is the liquid now?
Make a note of the volume of sodium hydroxide solution used. Do not thow away this liquid. You will need it for the next part of the experiment. Volume of sodium hydroxide solution used = cm 3
Add dilute ethanoic acid drop by drop until the acid colour returns. Weigh out 0.3 g of solid potassium iodide and add it to the liquid in the conical flask. Q. To what colour does the liquid change?
Fill a clean burette with 0.1M sodium thiosulphate solution as described above. Run about 10 cm 3 of this solution into the liquid in the conical flask and add five drops of starch indicator. The liquid should now be purple in colour. Wash around the inside of the conical flask with distilled water, then add more sodium thiosulphate solution, a drop at a time, until the purple colour disappears, leaving a pink liquid. Make a note of the volume of sodium thiosulphate used. Volume of sodium thiosulphate used = cm 3
You may now use your results to calculate the mass of sulphuric acid and copper in the original sample.
Calculation 1: mass of sulphuric acid

Q. Write down the equation for the reaction between sulphuric acid and sodium hydroxide.
Mass of H 2 SO4 = (volume of NaOH used/volume of H 2 S04 used) x (molarity of NaOH/2) x (molecular mass of H 2 S04 ) = ............... x 1/25 x 0.2/2 x 98 = ............... gdrrT 3 Full-strength electrolyte contains 10 times this mass = ............... gdrrT 3
Calculation 2: mass of copper

The chemistry of this is complicated but you do not need to know it at this stage. Mass of copper = (volume of Na 2 S 2 O 3 used/volume of CuSO4 used) x (molarity of Na 2 S 2 O 3 ) x (at. mass of Cu) = ............... x 1/25 x 0.1 x 64 = ............... gdm 3 Full-strength electrolyte contains 10 times this mass = ............... gdm" 3
31
Experimenting with Industry

A series presenting industry-related science practicals for schools, developed as part of a 'teachers into industry' project organized by The Association for Science Education on behalf of The Standing Conference on Schools' Science and Technology.
Title
1. Electrical Testing 2. Optical Fibres in School Physics 3. Industrial Use of Micro-organisms 4. Sugar Challenge 5. ChemicalsforAgriculture 6. Brake Fluid and School Science 7. Safety in Gas Appliances 8. Extracting Metals from Scrap 9. Properties of Metals 10. Electronics of Control Systems 11. Chemistry of Esters 12. Physics of Fluid Flow 13. Plant Tissue Culture
Company
Square D Ltd., Swindon, Wiltshire GEC Hirst Research Centre, Wembley, London Nipa Laboratories Ltd., Pontypridd, Mid-Glamorgan British Sugar pic, Peterborough, Cambridgeshire ICI Agricultural Division, Billingham, Cleveland Shell Chemicals, Carrington, Manchester British Gas Eastern Region, Potters Bar, Hertfordshire Elkington Copper Refiners, Walsall, West Midlands British Aerospace, Stevenage, Hertfordshire Marconi Command & Control Systems, Camberley, Surrey Ciba-Geigy Industrial Chemical Division, Manchester Dowty Services Ltd., Cheltenham, Gloucestershire Unilever pic, Bedford
Available from: The Association for Science Education College Lane, Hatfield AL10 9AA
Printed in England by Inprint of Luton Ltd. 95-115 Windmill Road, Luton, Beds.

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Experimenting k k . . ...

Extracting Metals from Scrap

A series presenting industry-related science practicals for schools

8. Extracting Metals from Scrap

ice Learning Centres

The Standing Conference on Schools' Science and Technology

The Association for Science Education

Project Working Party

Brian Nicholl Richard Turner

Extracting Metals from Scrap Experimenting with Industry

Extracting Metals from Scrap Experimenting with Industry

Unilever pic, Bedford

Elkington Copper Refiners Limited

4. Appendix: Relationships to 16+chemistry syllabus

Figure 1 Furnace charge

Figure 2 The blast furnace

Figure3 Converter furnace

FigureB Electrolytic tank house

Extracting Metals from Scrap Experimenting with Industry

Wire bars Ingots

Low grade scrap Slags Residues Irony copper Coke

Low grade ZnO fume Granulated slag

Black copper (80% Cu) Scrap (2-6% Sn) -<-

Experiment 2 Mixed Sn/Pb/Zn oxides Reduction furnace

Anodes (93.5% Cu)

Experiments 4,5 & 7 Electrolytic refinery Nickel sulphate Experiment 6

Extracting Metals from Scrap Experimenting with Industry

Assaying a gunmetal alloy scrap for copper content Background notes

Apparatus and chemicals

Analysis of mixed furnace oxides Background notes

Extracting Metals from Scrap Experimenting with Industry

Experiment 3 Apparatus and chemicals

Analysis of lead/tin alloy Background notes

Electrolytic purification of copper

Extracting Metals from Scrap Experimenting with Industry

Apparatus and chemicals

Power source Ammeter

Copper wire supports

Laboratory model of the commercial purification of copper Background notes

Extracting Metals from Scrap Experimenting with Industry

Impure copper anodes

Copper covered wood

Connected to negative terminal

Connected to positive terminal

Copper wire bus bars

Plastic sandwich box

Pure copper cathodes

Acidified copper(ll) sulphate electrolyte

Apparatus and chemicals

Simulation of copper stripping and nickel recovery Background notes

Extracting Metals from Scrap Experimenting with Industry

Apparatus and chemicals

Suggested additional demonstration

Analysis of the acidified copper(il) sulphate electrolyte Background notes

Extracting Metals from Scrap Experimenting with Industry

Chemistry concepts covered

Determining the percentage of copper in a sample of

Why use a fume cupboard?

Extracting Metals from Scrap Experimenting with Industry

Do you have any idea what this solid could be?

Where is the copper now?

Where is the tin now?

Write down a word and symbol equation for the reaction.

What is the black compound produced on heating?