School of Chemistry Safety Manual

Please read the manual thoroughly and then complete the online Safety quiz prior to the final sign off of your Induction forms by the School of Chemistry Safety Officer(s).

<need link here>

Index1. Emergency Procedures

1.1 Building Evacuations2. General Safety Rules

2.1 Personnel Protective Equipment (PPE)2.1.1 Safety Glasses2.1.2 Laboratory Coats2.1.3 Footwear2.1.4 Gloves2.1.5 Hygiene

2.2 Overnight reactions2.3 Working Outside Normal Hours2.4 Visitors and Children

3. Safe Laboratory Practice3.1 Fume Cupboards3.2 Emergency Equipment3.3 Housekeeping3.4 Gas Cylinders3.5 Liquid Nitrogen

4. Safe Management of Chemical Substances4.1 Training4.2 ChemWatch4.3 Purchase of Hazardous Chemicals

4.3.1 Chemicals of Security Concern and Controlled Substances4.4 Risk Assessments4.5 Storage of Hazardous Chemicals

4.5.1 Segregation of Chemicals4.5.2 Storage in Laboratory Cupboards and Dangerous Goods Cabinets4.5.3 Refrigeration and Freezing4.5.4 Volatile Chemical Storage4.5.5 Transport of Chemicals4.5.6 Labelling of Decanted Chemicals and Chemical Research Samples

4.6 Chemical Spill Management4.6.1 Green Chemical Spill Kits

4.7 Disposal of Chemicals4.8 Information on Destruction of Wastes

4.8.1 Neutralisation of Sodium Metal Residues5. High Risk Chemical Substances

5.1 Hazardous Solvents

5.2 Explosive Substances5.2.1 Perchlorates5.2.2 Perchloric Acid5.2.3 Other Explosive Compounds

5.3 Carcinogenic Substances5.3.1 Scheduled Carcinogens5.3.2 Potential Carcinogens

5.4 Toxic Substances (Poisons)5.4.1 Cyanides5.4.2 Mercury and its Compounds

1. Emergency ProceduresYou should familiarize yourself with the EMERGENCY PROCEDURES booklet located beside each telephone. This booklet includes instructions for Emergency Evacuation.

In an emergency, use an emergency RED phone. If a Red Phone is not close by, call the emergency internal number 333 or 9905 3333 (mobile phone). In case of fire, you may also use the Fire Alarms located in various places throughout the School. Break the glass and press the alarm button. In the case of serious personal injury, First Aiders should assist with emergency treatment until medical personnel arrive.

Emergency Phone

1.1 Building EvacuationsAlert Signal: beep beep beep

Evacuation Signal: whoop whoop whoop

Leave the building via the nearest safe exit and proceed to the Assembly area as directed by the emergency wardens. DO NOT USE THE LIFT. Do not re-enter the building until directed by the building warden or the Fire Brigade.

Assembly points:

Building 19: <need map here> Building 23: <need map here> Building 86: <need map here>

2. General Safety Rules

2.1 Personal Protective Equipment2.1.1 Safety glassesLaboratory personnel and visitors MUST wear safety glasses at ALL TIMES in all laboratory areas that are signed. If prescription glasses are required, safety glasses must be worn over the top of prescription glasses. Glasses should fit tightly and be chosen for maximum eye protection.

Contact lenses should not be worn in laboratories because of the risk of chemicals being trapped under the lenses. If you have to wear contact lenses, you must also wear tight-fitting splash goggles.

2.1.2 Laboratory coatsLaboratory coats should be worn at all times in the laboratory, but not outside the building. They should preferably be made of 100% heavy-duty cotton. The use of pure polyester coats is prohibited. These are particularly dangerous because of their flammability and the low melting point of polyester.

2.1.3 FootwearClosed shoes only (never thongs or open sandals) should be worn in laboratory areas.

2.1.4 GlovesGloves must be worn as part of personal protective equipment when indicated by the risk assessment.

The Faculty of Science store carries several types of gloves (Latex, Nitrile, Neoprene), use the most appropriate protection as determined by your Risk Assessment.

Gloves MUST be removed before leaving the laboratory to prevent chemical contamination of other areas in the School.

2.1.5 HygieneLaboratory coats should be removed and hands washed before leaving the laboratory.

2.2 Overnight ReactionsEvery overnight experiment must be reported to the General Office by 4:00 pm and recorded in the overnight experiment book. The Office will notify Security that overnight experiments are being conducted.

Research students must have the apparatus checked and the card initialed by their supervisor, or a post-doctoral fellow if the supervisor is unavailable.

Unattended reaction form: <need link here>

2.3 Working Outside of Normal HoursNo one should undertake laboratory work outside normal working hours without a "buddy" (i.e. another person working in close proximity who can regularly check your safety every 30 minutes). The “buddy” must be a member of the School of Chemistry and must be suitably trained to deal with a chemical emergency situation should it arise.

TIME 0:00 - 9:00 9:00 - 17:00 17:00 - 24:00

Sunday After hours laboratory work - Low risk only - Buddy system applies

MondayTuesdayWednesdayThursdayFriday

After hours laboratory work - Low risk only - Buddy system applies

Normal working hours

After hours laboratory work - Low risk only - Buddy system applies

Saturday After hours laboratory work - Low risk only - Buddy system applies

Holiday After hours laboratory work - Low risk only - Buddy system applies

The "after hours book" (located near the Building 23S entrance) MUST be signed by anyone in School buildings between 19:00 and 07:00, and signed out on departure. Note that University First Aid facilities are NOT staffed outside official University working hours (8:45 am to 5:00 pm).

2.4 Visitors and ChildrenAll visitors to the School are asked to report to Chemistry Reception in the first instance. Visitors are only permitted to enter a laboratory in the company of a member of staff, and must wear safety glasses and appropriate footwear and clothing while there. Children are not permitted in any part of the School except under the supervision of an adult.

3. Safe Laboratory Practice

3.1 Fume cupboardsAll members of the School should read the Information sheet Use of Local Exhaust Ventilation Systems Part 1. Fume Cupboards

<https://www.monash.edu/ohs/information-and-documents/all-information-sheets/use-of-local-exhaust-ventilation-systems-fume-cupboards>

Fume cupboards must be kept clean and uncluttered at all times and not be used as a repository for unwashed equipment. Sashes should be kept clean and unobscured by writing, stickers, or signage.

Most fume cupboards have a yellow "Recommended Sash Height" sticker, and the sash should be kept at or below this level when in use. OHSE recommends that the performance be tested on a regular basis to ensure that the face velocity and flow distribution are satisfactory.

3.2 Emergency equipmentEvery laboratory should contain appliances to cope with fire or spill emergencies, including:

safety showers and eye-washers fire blankets fire extinguishers a fire bucket with clean, dry sand or vermiculite chemical spill kits.

The General Office must be notified immediately whenever one of these appliances is used so that it can be replaced or refilled.

Fire Safety Training is run as part of the Honour’s induction program in February each year.

3.3 Housekeeping Empty Winchesters, boxes of chemicals and sundry equipment must not be stored

on the floor or just inside doorways. Fume cupboards are not intended for use as storage space. They should contain only

equipment and chemicals actually in use or for use in the immediate future. Malodorous substances and non-flammable solvent residues awaiting disposal

should be kept in ventilated storage cupboards.

Workbenches should be kept in a clean dust-free condition and used only for short-term storage of samples and chemicals. They should not be used for storing dirty glassware.

Faulty taps, blocked sinks, faulty electric lighting and power, and other building faults, should be reported to the Reception Office immediately.

Cables and tubing should not be laid across open flooring. All safety showers and eyewash facilities must be regularly flushed and checked to

ensure they are fully functional. Any problems must be reported to the supervisor or Safety Officer immediately.

3.4 Gas cylindersPeople using gas cylinders must do the online Gas Cylinder and Cryogenic training course.

<https://www.monash.edu/staff-development/learning-activities/occupational-health/gas-cylinders-and-cryogenics>

All gas cylinders must be properly secured with a chain to prevent their falling and causing injury. They must only be moved on a trolley, and chained in position while doing so. Unused gas cylinders should not be stored in laboratories. Connections should be leak tested, and appropriate regulators used.

3.5 Liquid NitrogenThe School of Chemistry liquid nitrogen facility is located in the courtyard outside the west exit of the south wing of Building 23. Prior to using the facility, people must do the online Gas Cylinder and Cryogenic training course and be trained by the Safety Officer (or authorised person).

<https://www.monash.edu/staff-development/learning-activities/occupational-health/gas-cylinders-and-cryogenics>

The following safety equipment is available in the facility and their use is mandatory:

closed toe footwear eye protection (safety glasses or face shield) thermal gloves

4. Safe Management of Chemical Substances

All member of the School of Chemistry should read the Using Chemicals at Monash prior to commencing any laboratory work.

<http://www.monash.edu/__data/assets/pdf_file/0008/129617/using-chemicals.pdf>

4.1 TrainingMonash University has mandated that all staff associated with the School (with the exception of some administrative staff), including Monash academic staff, professional officers, adjunct partners, post graduate students and researchers MUST attend Hazardous Substances and Dangerous Goods Awareness training run by Staff Development Unit. Attendance can be booked online using the following link.

<https://my.monash.edu.au/news-and-events/bookings/facsci/search/?category_id=-1&campus_id=-1&keywords=OHS&type=upcoming&sort=date&action_search=Search>

Please see Sarah Williams (School reception) for a cost centre and fund source as the School covers the cost of the training.

In addition, each research group/laboratory shall provide induction, instruction and or training on any SWI applicable to a task or process in which a hazardous chemical is used. This training MUST be recorded, dated and signed using the training record proforma (or similar worksheet) and be available to be viewed by OHS staff.

<http://www.monash.edu/__data/assets/pdf_file/0020/148601/training-records.pdf>

4.2 ChemWatchChemWatch is an online chemical management system and provides safety information including up to date MSDS(SDS), a chemical inventory for each laboratory, and printable labels for decanted chemicals and chemical samples. All university staff have access to the ChemWatch system via the link on the Monash University OHS website.

<https://www.monash.edu/ohs>

Each research group has a username and password for viewing and maintaining chemical stores and inventories. It is essential that all hazardous chemicals are entered into ChemWatch with the maximum quantity recorded and the Dangerous Goods classification manually entered if a ChemWatch MSDS(SDS) is not available.

Information on the use of ChemWatch can be obtained for the School Safety Officer(s). Users requiring further training can attend the courses run by Staff Development Unit which can be booked online using the following link.

<https://www.monash.edu/staff-development/learning-activities/occupational-health/chemwatch-msds>

Hardcopy MSDS’s (SDS’s) may be used in laboratories if required or are more convenient but MUST be labelled as “Uncontrolled Copy” and should be removed from the laboratory when no longer in use.

4.3 Purchase of Hazardous ChemicalsPrior to purchasing a hazardous chemical, consideration should be given to the possibility of substituting a chemical with less risk. Furthermore, the quantity purchased is to be kept to a minimum to reduce risks (eg of a chemical spill) and to avoid the cost associated with disposal of unwanted chemicals. The Monash Chemical Pre-purchase Checklist MUST be completed prior to ordering a new chemical that is either a hazardous substance or dangerous goods.

<http://www.monash.edu/__data/assets/pdf_file/0020/113726/chemical-checklist.pdf>

All chemicals purchases must be completed using a purchase order form, available from the School reception and have and accompanying MSDS(SDS) from the supplier. These will be signed off by the SoC Product Steward prior to forwarding to finance. Chemicals cannot be purchased online using a Monash credit card.

4.3.1 Chemicals of Security Concern and Controlled SubstancesSome readily available chemicals, including some commonly used in universities, can be used to make homemade explosive devices. These and other toxic chemicals that can be misused may require further authorisation and/or documentation (eg end user declaration) prior to receipt of the chemical. The university and staff are empowered by license to possess certain controlled substances, such as drug precursors or scheduled carcinogens (see below). These may require additional arrangements such as secure storage, record keeping, and general control in accordance with the relevant permit conditions. Please see the School Product Steward (Dr. Boujemaa Moubaraki) for further information.

4.4 Risk AssessmentsFor any process or experiment using hazardous chemicals, a risk assessment must be undertaken and recorded prior to the commencement of the chemical process. The relevant sections of Risk Management Worksheet (need link here) must be completed in consultation with Monash Risk Management Chemical document and the Introduction to the GHS.

<https://www.monash.edu/__data/assets/pdf_file/0019/126082/risk-management-program.pdf> <https://www.monash.edu/__data/assets/pdf_file/0004/189517/risk-management-chemical.pdf>

Depending on the complexity of the chemicals(s) or process, relevant staff, the School Safety Officer(s), or external experts should also be consulted. Finalised risk assessments must be reviewed at least every 3 years.

For chemical syntheses and synthetic chemistry research projects, a generic process risk assessment template and a generic safe work instruction are available (see below) which may be used for “ordinary” synthetic procedures performed on a regular basis. In situations where there is uncertainty about the degree of risk or there is a significant risk to health or of exposure or for more complex procedures, a more detail risk assessment should be completed and may involve additional information about health hazards and further control measures that may be required to minimise the risk.

< S:\Sci-Chem\School-Resources\Standard Operating Procedures\Generic risk assessment for small scale synthtic reactions.docx>

4.5 Storage of ChemicalsContainers or packages of chemicals may be stored in a range of configurations including:

general laboratory shelves or cupboards Dangerous Goods cabinets dedicated chemical stores storage areas for gas cylinders and cryogenic fluids bulk tanks or containers

In considering storage of hazardous chemicals, laboratory users shall refer to the best practice as specified in Australian Standards:

AS 1940-2004 The storage and handling of flammable and combustible liquids AS/NZS 2243.10:2004 Safety in laboratories – Part 10 Storage of Chemicals AS 3780-2008 The storage and handling of corrosive substances

Storage arrangements should be designed to minimise the risk of exposure (chemical spill) and reduce the potential fire risk (including the potential formation of toxic gases). See also: the Monash guidelines Storage of Dangerous Goods in Laboratories, Studios and Workshops.

<http://www.monash.edu/__data/assets/pdf_file/0008/148589/dangerous-goods-storage.pdf>

4.5.1 Segregation of chemicalsIncompatible chemicals must be segregated by distance or containment barriers sufficient to eliminate the risk of fire, explosion or accumulation of toxic gases or vapours from mixing of incompatible chemicals resulting from a leak or spillage etc. The principle source of guidance on conditions for safe storage and compatibility is the MSDS (SDS) for the relevant chemicals (see sections 7 and 10).

Examples include (but not limited to):

concentrated strong acids and alkali cyanides and acids strong oxidisers and flammable solvents

Chemical storage cabinets for specific Dangerous Goods classes (eg. Class 3, Class 5.1) shall not be used to store any other Dangerous Goods class.

Further information on the segregation of hazardous chemicals can be obtained from the Code of Practice for the Storage and Handling of Dangerous Goods, WorkSafe VIC, 2013 – Appendix 2.

4.5.2 Storage in laboratory cupboards and Dangerous Goods cabinetsLocal storage arrangements are to reflect the following principles (in addition to requirements prescribed elsewhere in this manual).

1. Quantities of hazardous chemicals should be kept to a minimum.2. Group the chemicals by chemical classification e.g. non-hazardous, hazardous

substance only, dangerous goods3. Segregate dangerous goods by class e.g. Class 3 Flammable Liquids, Class 6.1 Toxic

Substances, Class 8 Corrosive Substances4. Large quantities of dangerous goods should be stored in Australian Standard

compliant chemical storage cabinets e.g. 25 L of flammable liquids in a small Class 3 flammable liquid cabinet.

5. The sump of a Dangerous Goods chemical storage cabinet shall not be used for storage

6. Store smaller quantities of dangerous goods in laboratory cupboards or on shelving with solids positioned above liquids and the different DG classes segregated using a separate laboratory cupboards for each class or by using separate plastic spill trays or tubs

7. Check the incompatibility of common substances to identify any possible problems within dangerous goods classes (eg. concentrated strong acids and concentrated strong alkalis) and further segregate chemical as required (see above).

8. Non-hazardous chemicals and hazardous substances that are not dangerous goods can generally be stored together and sorted alphabetically.

Please consult the Monash guidelines for Storage of Dangerous Goods in Laboratories, Studios and Workshops for further information.

<http://www.monash.edu/__data/assets/pdf_file/0008/148589/dangerous-goods-storage.pdf>

4.5.3 Refrigeration and FreezingSolvents such as diethyl ether; pentane and carbon disulfide have flash points below -20 °C, and can form explosive mixtures with air even at freezer temperatures. A spark from a light switch, thermostat or fan may detonate these mixtures. Refrigerators and freezers used for chemical or sample storage should be custom built or modified appropriately so that all

electrical connections are external to the unit and there is no possibility of arcing. Signage indicating suitability for solvent storage must be affixed prior to use.

Refrigerators and freezers used for chemical storage, including aqueous solutions, must not be used for storage of food or drink for human consumption. Refrigerators for food storage of food must be labeled as such and must NOT be located in a laboratory.

Chemicals stored in refrigerators or freezers should be segregated according to their DG class. Containers of liquids should be placed in secondary spill containment.

4.5.4 Volatile chemical storageFume cupboards are not to be used for chemical storage. Malodorous volatile compounds (eg amines, sulphur compounds, phosphines etc) should be stored in a ventilated cabinet. Compounds should be segregated according to their DG class and liquids placed in secondary spill containment. Please consult the relevant MSDS for further information.

4.5.5 Transport of ChemicalsSafety baskets are available for carrying solvents and other chemicals from one location to another. They should be used at all times.

4.5.6 Labelling of Decanted Chemicals and Chemical Research SamplesUnder no circumstances must bottles containing chemicals be allowed to remain unlabelled. This rule applies to both proprietary lines and research samples. The minimum labelling requirements are:

Product name and concentration Date Name of generator DG class or diamond (or words that indicate the type and severity of the hazard)

For small containers of a research sample, the product name may be replaced with a sample number that refers to a laboratory notebook.

All labels MUST be legible to co-workers and emergency services.

Re-used containers MUST have the old label removed or totally covered.

Food and beverage containers are NOT permitted to be re-used for chemical storage.

4.6 Chemical Spill ManagementEach laboratory should have a local system to prepare for chemical spills ensuring appropriate spill kits containing an absorbent material eg kitty litter, vermiculite, sand are readily accessible and regularly checked and restocked as necessary, and appropriate PPE is available to cater for foreseeable chemical spills. Workers should also consider specific hazards for highly dangerous chemicals eg concentrated strong acids and contingency plans in case of a spill as part of their risk assessment. Transferring or decanting hazardous

chemicals generally presents a far greater risk than static storage and particular care and attention should be applied to these processes.

For emergency situations, full or half face-masks have been placed in the corridors around the School to be used in place of Self Contained Breathing Apparatus. A filter should be attached to the mask prior to use (align the arrows on the cartridge towards the face mask).

Filter SR299-2R is suitable for: Organic acid vapours with boiling points above 650C. Inorganic gases and vapours such as chlorine,

hydrogen sulphide and hydrogen cyanide. Acid gas vapours such as sulphur dioxide and

hydrogen fluoride. Ammonia vapours and certain amines. Mercury vapour. All particulate matter.

4.6.1 Green Chemical Spill KitsThese large green kits are located in the corridors close to all laboratories. Ensure that you know where to find them and how to use their contents in the event of a spill.

For serious, large spills of a hazardous material, isolate the area, and call 333 (see also Emergency Procedures above)

4.7 Disposal of Chemical WasteUnwanted or waste chemicals and research samples should be destroyed chemically if possible and within the laboratory of generation. Otherwise properly labeled waste should be taken to the Faculty of Science Store as soon as possible for disposal through EPA licensed contractors such as Toxfree.

Procedure for disposal of Chemical waste through the Faculty of Science Store.

1. Print or email a complete inventory of the waste to be submitted including the following information:your name,waste type and quantity,DG class, cost centre and fund.

2. Waste MUST be in a sealed container and labelled with:your name, waste type and quantity, DG diamond.

3. Take the waste to the store during store hours and the staff will direct you.

Used solvents should be recovered for use if possible. Otherwise all waste solvents must be placed in a sealed container (recycled solvent bottles may be used provided that the existing label is completely removed or covered, alternative for larger volumes, 20L carboys are available from the Faculty of Science store).

Waste solvents should be separated under the following categories:

Halogenated Solvents (DG Class 6.1) Flammable solvents (DG Class 3) Carbon disulfide and other special cases must be stored separately and properly

labelled.

All waste solvent containers MUST be properly labelled with the name of the waste generator, the contents, the date and the relevant Dangerous Goods diamond affixed. Prior to disposal, waste containers must be stored according to their DG class and should have secondary spill containment.

The generation and storage of any potentially explosive mixtures, e.g. acetone and chloroform, is NOT permitted.

Waste classifications of some frequently generated waste streams are listed on the Monash University OHS website:

<https://www.monash.edu/ohs/information-and-documents/laboratory-safety/chemical-waste-disposal-ohs-information-sheet>

4.8 Information on destruction of wastesIf you are carrying out a chemical destruction or neutralization process prior to disposal for the first time, ensure that your supervisor or an experienced researcher is available to assist you. Adequate safety equipment such as fire extinguishers, breathing apparatus etc. should be on hand as determined by your Risk Assessment.

4.8.1 Neutralisation of sodium metal residuesSeveral fires have occurred in this School during destruction of sodium residues from drying solvents. The School has developed a standard Operating Procedure for the Quenching of Alkali Metals which is located on the Monash Shared drive (see below). This procedure MUST be followed without exception.

<S:\Sci-Chem\School-Resources\Standard Operating Procedures\SOP-Quenching of Alkali Metals.pdf>

The quenching of alkali metals is highly hazardous and should be performed during business hours only (9am-5pm weekdays).

The procedure should never be performed alone.

5. High Risk Chemical Substances

5.1 Hazardous SolventsExtra care should be exercised when using glacial acetic acid, N,N-dimethylformamide, dimethyl sulfoxide and other water-soluble polar solvents. These easily penetrate skin tissue, carrying any dissolved compounds with them. Glacial acetic acid can enter small cuts and cause painful blistering. Appropriate gloves should be worn in these instances. Hands should be washed when removing gloves. In addition, working conditions should be arranged to minimise ingestion of solvents by breathing.

Carbon disulfide is particularly hazardous because of its low auto-ignition temperature (100 °C). Its vapour can be ignited by contact with a hot steam bath.

5.2 Explosive Substances5.2.1 PerchloratesAll perchlorates should be treated as explosive unless otherwise known. Sodium perchlorate is not explosive but is a powerful oxidising agent and may make a significant contribution to the intensity of any fire. Ammonium perchlorate and many organic salts and heavy metal coordination complexes containing perchlorate ion may explode when heated. The localised heat associated with the preparation of Nujol mulls or KBr discs for infrared spectroscopy may be sufficient to cause an explosion.

5.2.2 Perchloric AcidPerchloric acid is highly corrosive to living tissue and will react with many chemicals. It reacts violently with organic, metallic and non-organic salts to form products which may be shock sensitive and pose a risk of fire and explosion. When heated above 150 °C perchloric acid becomes a very strong oxidiser, is unstabe and may detonate. Vapours may contaminate work surfaces or ventilation ducts with perchlorate residues. Perchloric acid forms an azeotrope with water containing 72.5% HClO4. Aqueous solutions containing 72% or less perchloric acid are not in themselves explosive, but such solutions are strong oxidising agents at elevated temperatures.

Handling: Trained users must already be experienced in working with hazardous chemicals and follow documented safe work procedures. Only use perchloric acid in work areas equipped with eye wash and safety shower. Placard fume cupboards with PERCHLORIC ACID FUME CUPBOARD ONLY. ORGANIC CHEMICALS PROHIBITED (f/c No. 4, located in G31, building 19).

Storage: The storage of anyhdrous perchloric acid is not permitted. Store aqueous solutions only in the original container, separately from other chemicals in compatible secondary containment. Use only glass or plastic containers. Perchloric acid is highly

reactive with metals – do not use metal caps. If the bottle containing perchloric acid has turned dark or has a crystalline deposit around the neck or cap of the bottle – this is an explosion hazard. DO NOT open or move the bottle, but contact your supervisor or the School Safety Officers.

More information is available in AS 4326 2008 The storage of oxidising agents.

5.2.3 Other explosive compounds

These compounds are particularly dangerous and extra precautions must be taken if their preparation or use is required.

o-Nitrobenzoyl and benzyl chlorides (these explode violently upon distillation) diazonium xanthates (solutions used to prepare thiophenols) organic compounds containing pentavalent iodine picric acid (2,4,6-trinitrophenol) picramide (2,4,6-trinitroaniline) and esters of nitric acid (e.g, ethyl nitrate,

pentaerythritol tetranitrate) tetrazoles, pentazoles and their derivatives p-toluenesulfonyl azide and other low MW acyl and sulfonyl azides hydrogen azide,

hydrazoic acid, and diazomethane

5.2.4 Peroxidisable compoundsPeroxide formation in laboratory solvents and reagents has been the cause of many accidents over the years. It is important that you can recognise which compounds have the potential to form peroxides.

Organic compounds that can form allylic or benzylic radicals (cyclohexene and tetralin) or radicals stabilised by an adjacent oxygen (most ethers) are potential peroxide formers. Diisopropyl ether is particularly dangerous. Aldehydes can also form peroxides, although they are not normally a problem. In general, pure compounds are more subject to peroxide buildup.

Alkali metals and their amides are converted to peroxides on prolonged exposure to air.

Some compounds that form peroxides storage

Peroxide Hazard on Storage alone

Peroxide Hazard on Concentration (eg distillation, evaporation, etc)

Hazardous Due to peroxide Initiation of explosive polymerisation

DivinylacetyleneDiisopropyl etherVinylidene chloridePotassium metalSodium amide

Diethyl etherDioxanAcetal1,2-DimethoxyethaneVinyl ethersDicyclopentadieneMethylacetyleneDecahydronapthalene (Decalin)Tetrahydronapthalene (Tetralin)TetrahydrofuranCyclohexeneDiethylene glycolDimethyl ether (Diglyme)

Methyl methacrylateStyreneAcrylic acidAcrylonitrileButadieneTetrafluoroethyleneVinylacetyleneVinyl acetateVinyl chlorideVinylpyridineChloroprene

Testing and treatment for ethers containing peroxidesThe peroxide test reagent is prepared by mixing the following solutions in a ratio of 10:1:1 (AS/NZS 2243.2 - Appendix D)

ferrous ammonium sulfate (1% w/v solution) sulfuric acid (0.5 mol/L) ammonium thiocyanate (0.1 mol/L)

A red coloration on mixing approximately equal volumes of ether and reagent indicates the presence of peroxides. If peroxides are present, they can be removed by passing through a chromatography column containing activated alumina. About 80 g of alumina should be sufficient for a Winchester of ether. The ether should be tested before and after passing through the column.

5.3 Carcinogenic SubstancesThe following list of carcinogenic chemicals is not exhaustive. Chemicals that are structural analogues to known carcinogens should be handled carefully because adequate data on carcinogenicity of such analogues may never become available. It is prudent to regard all

chemicals belonging to certain chemical classes (e.g. polycyclic hydrocarbons, nitrosamines, aromatic amines, azo dyes, arsenic compounds) as presenting a carcinogenic hazard. Consequently some chemicals have been grouped into general classes to highlight the risk associated with the class of compound.

5.3.1 Scheduled CarcinogensCarcinogenic substances are hazardous substances that can cause cancer. Two schedules of carcinogenic substances are restricted under part 4.2 of the Occupational Health and Safety Regulations 2007.

Schedule 1 Carcinogens Schedule 2 Notifiable Carcinogenic Substances

2-acetylaminofluorene Acrylonitrile

aflatoxins Benzene

4-Aminodiphenyl 3,3-Dichlorobenzidine and its salts

Acrylonitrile Diethyl sulfate or Dimethyl sulfate

benzidine and its salts Ethylene dibromide fumigant

bis(chloromethyl)ether 4,4-Methylene bis(2-chloroaniline) (MOCA)

chloromethyl methyl ether 2-Propiolactone

4-Dimethylaminoazobenzene o-Toluidine and o-Toluidine hydrochloride

2-Naphthylamine and its salts Vinyl chloride monomer

4-Nitrodiphenyl

Scheduled Carcinogens are prohibited substances that can only be used in a licensed laboratory. If there are any of these chemicals in your laboratory, please contact the Product Steward (Dr. Boujemaa Moubaraki) or the Safety Officer as soon as possible, in order that WorkSafe Victoria be notified and the Hazardous Substances Regulations be complied with.

5.3.2 Potential CarcinogensChemicals considered to present a carcinogenic hazard to humans are listed below by their chemical name and Chemical Abstract Services number (CAS no.).

Chemical name CAS No. Tested by

Acetamide IARC

Acetaldehyde 75-07-0 IARC 2B, NTP

2-Acetylaminofluorene 53-96-3 OSHA, NTP

Acrylonitrile 107-13-1 OSHA*, IARC 2A

Acrylamide 79-06-1 IARC 2A, NTP

Adriamycin 23214-92-8 IARC 2A, NTP

Aflatoxins IARC 1, NTP

p-Aminoazobenzene 60-09-3 IARC 2B

o-Aminoazotoluene 97-56-4 IARC 2B, NTP

4-Aminobiphenyl 92-67-1 NTP

Arsenic compounds# OSHA*, IARC 1, NTP

o-Anisidine 90-04-0 IARC 2B

Azathioprine 446-86-6 IARC 1, NTP

Benzene 71-43-2 OSHA*, IARC 1, NTP

Benzidine (and derivatives) 92-87-5 OSHA, IARC 1, NTP

p-Cresidine 120-71-8

Beryllium (and compounds) 7440-41-7

N,N-bis (2-Chloroethyl)-2-naphthylamine 494-03-1

Bis(chloromethyl) ether 432-88-1

1,4-Butanediol dimethanesulfonate 55-98-1

Butyrolactone 36536-46-6 IARC 2B

Cadmium (and compounds) 7440-43-9 OSHA*, IARC 1, NTP

Chlorambucil 305-03-3 IARC 1, NTP

Carbon tetachloride IARC 2B, NTP

4-Chloro-o-toluidine 6164-98-3 IARC 2A

4-Chloro-o-phenylenediamine 95-83-0 IARC 2B, NTP

Chromium VI compounds# IARC 1, NTP

Cisplatin 15663-27-1 IARC 2A, NTP

Cyclophosphamide 6055-19-2 IARC 1, NTP

Daunomycin 20830-81-3 IARC 2B

2,4-Diaminoanisole 615-05-4 IARC 2B

2,4-Diaminotoluene 95-80-7 IARC 2B, NTP

Dianiline derivatives eg 3,3'-Dichloro-4,4'-diaminodiphenylether

28434-86-8 IARC 2B

4,4'-Methylene bis (2-chloroaniline) 101-14-4

4,4'-Methylenedianiline 101-77-9 IARC 2B, NTP

4,4'-Methylene bis (2-methylaniline) 868-88-0

4,4'-Oxydianiline (4,4'-diaminodiphenyl ether) 101-80-4 IARC 2B

4,4'-Thiodianiline 139-65-1 IARC 2B

1,2-Dibromo-3-chloropropane 96-12-8 OSHA*, IARC 2B, NTP

Diethyl sulfate 64-67-5 IARC 2A, NTP

Diethyl hydrazine 1615-80-1 IARC 2B

1,1-Dimethyl hydrazine 57-14-7 IARC 2A, NTP

1,2-Dimethyl hydrazine 306-37-6 IARC 2A

Dimethylcarbamoyl chloride 79-44-7 IARC 2A, NTP

Dimethyl sulfate 77-78-1 IARC 2A, NTP

1,4-Dioxane 123-91-1 IARC 2B, NTP

Epichlorohydrin 106-89-8 IARC 2A, NTP

Ethylene dibromide 106-93-4 IARC 2A, NTP

Epoxides eg Diepoxybutane 1464-53-5 IARC 2A, NTP

Ethylene oxide 75-21-8 OSHA*, IARC 1, NTP

Propylene oxide 75-56-9 IARC 2B, NTP

Formaldehyde 50-00-0 OSHA*, IARC 2A, NTP

Hexamethylphosphoramide 680-31-9 IARC 2B, NTP

2-Naphthylamine 91-59-8 OSHA

Nickel (and compounds)# IARC 1, NTP

Nitrosocompounds eg Bis(chloroethyl) nitrosourea 154-93-8 IARC 2A, NTP

1-(2-Chloroethyl)-3-cyclohexyl-1-nitrosourea 13010-47-4 IARC 2A, NTP

N-Ethyl-N-nitrosourea 759-73-9 IARC 2A

N-Methyl-N'-nitro-N-Nitrosoguanidine 70-25-7 IARC 2A, NTP

N-Nitrosodimethylamine 62-75-9 IARC 2A, NTP

Polycyclic aromatic h/c eg Benz(a) anthracene 56-55-3 IARC 2A, NTP

Benzo(a) pyrene 50-32-8 IARC 2A, NTP

Dibenz (a,h) anthracene 189-64-0 IARC 2A, NTP

Styrene 100-42-5 IARC 2B

Styrene oxide 96-90-3 IARC 2A

o-Toluidine 95-53-4 IARC 2B, NTP

Treosulfan 299-75-2 IARC 1

Tris(2,3-dibromopropyl)phosphate 126-72-7 IARC 2A, NTP

Vinyl chloride 75-01-4 OSHA*, IARC 1, NTP

# Evidence of carcinogenicity applies to the group of chemicals as a whole and not necessarily to all individual chemicals.IARC - International Agency for Research on Cancer, NTP - National Toxicology Program, OSHA - Occupational Safety & Health Administration, OSHA* - indicates substances for which OSHA has promulgated standards for health in addition to carcinogenicityClass 1 -- Known human carcinogen Class 2A -- Probable human carcinogen Class 2B -- Possible human carcinogen Class 3 -- Not classifiable for human carcinogenicity Class 4 -- Probably not carcinogenic to humans

5.4 Toxic Substances (Poisons)Medicines and poisons are classified into Schedules (1 to 9) and listed in the Australian Standard for the Uniform Scheduling of Medicines and Poisons (SUSMP). Legislative controls for ‘scheduled’ medicines and poisons vary according to the risks associated with substances listed in each schedule. These controls relate to possession, storage, use, supply, prescription, administration, destruction, recording of transactions, manufacture plus labelling and packaging requirements.

5.4.1 CyanidesThe use of cyanides is regulated under the Drugs, Poisons and Controlled Substances Regulations (Part V - Special Poisons - arsenic, cyanide, strychnine). All users within the School must conform to the National Occupational Health and Safety Commission's Guidelines (pdf 56.9kb) on the safe use of cyanides as well as the School's own policy.

5.4.2 Mercury and its compoundsMetallic mercury can present a significant toxic challenge to people who are exposed to it. Although mercury is relatively non-toxic if ingested (it has low water solubility and normally passes through the digestive system, and little is absorbed) inhalation of mercury vapour poses a major health hazard. Approximately 80% of mercury vapour is rapidly absorbed and distributed in all major organs. Health effects include damage to the kidneys, lungs and central nervous system. Because of its toxicity and the difficulty of cleaning up spills (very small droplets of mercury may be hard to see but if left unattended will slowly evaporate) the use of metallic mercury should be kept to a minimum. Any large spillage of mercury should be reported to the Safety Officer and an Incident Report submitted.

Wear PPE during clean-up: lab coat or gown to protect your clothes from contamination and impervious disposable gloves - PVC or rubber gloves, or double glove with surgical type gloves. If it's a large spill also wear a mask or respirator.

The suspected spill area should isolated to prevent entry using suitable warning notices. Cover the spill area with sulphur powder or zinc dust or a propriety product like Mercurisorb and then all the material should be swept up and the waste placed in a sealed and appropriately labelled container (Toxic 6.1 DG diamond) to be disposed of using the normal procedures through the Faculty of Science store. Note: Powdered zinc should be handled carefully as it represents a fire hazard and should NOT be used in combination with sulphur powder as this can create an explosion risk.

All mercury compounds should also be treated as hazardous. Dialkylmercury compounds are extremely dangerous - a single drop on the skin can cause death.