Document KJRKjvkDz60nLq2OOZzapBkO0

GUIDELINES FORA REACTIVE CHEMICALS PROGRAM The Dow Chemical Company August 1981 35870 A1 We would like to indicate to readers outside of Dow that the information and recommendations herein represent the most reliable Dow knowledge as of the date of printing. However, as we work with chemicals, new information updates our knowledge frequently. We stand ready at any time to discuss safety and handling problems that may be brought to us, but cannot foresee all of the uses and environments our products may be subjected to. We therefore cannot accept any responsibility for the acts of others who do not follow the handling technology outlined here. Readers are cautioned to satisfy themselves regarding the suitability of their safe handling knowledge for the purposes intended prior to use. DO A ^SS71 CONFTOFNTTAl CONTENTS PREFACE......................................................................................................................................... 1 PURPOSE......................................................................................................................................... 1 INTRODUCTION ............................................................................................................................ 2 OWNER'S RESPONSIBILITY....................................................................................................... A. Research................................................................................................................................... B. Production and PilotPlants.................................................................................................... C. Other Operations.................................................................................................................... D. Technical Service andDevelopment ................................................................................... 3 3 3 4 4 REACTIVE CHEMICALS COMMITTEES.................................................................................... A, Site or Location Committee ................................................................................................. B. Reactive Chemicals Advisory Board.................................................................................... 4 4 5 PROCESS REVIEWS...................................................................................................................... 5 REACTIVE CHEMICALS TESTING A. Thermodynamic Calculations. B. Thermal Stability .................................................................................................................... C. Shock Sensitivity.................................................................................................................... D. Flammability Tests.................................................................................................................. E. Interpretation............................................................................................................................ 6 7 8 9 DATA HANDLING ........................................................................................................................ 10 APPENDIX A. Definitions.............................................................................................................................. 11 B. Calculations for Chemical Hazards.................................................................................... 11 C. Atomic Groupings that Characterize Explosive Compounds.............................. 12 & 13 D. Considerations and Testing Diagrams.............................................................................. 14 E. Reactive Chemicals Testing Sites...................................................................................... 15 F. Reactive Chemical Hazard Data......................................................................................... 16 O) O) 00 A 135877 C0NFT8FNTT Al PREFACE Dow's Minimum Requirements for Safety and Loss Prevention state that: "Each location shall have an appropriate and active reactive chemicals program. Regular reviews of process reactive hazards shall be required as well as a thorough review of laboratory or pilot plant data prior to scaleup." This Guideline Fora Reactive Chemicals Program provides basic information upon which the Areas and their respective units or locations can build their own programs tailored to their own specific needs. PURPOSE The purpose of the Reactive Chemicals Program is to prevent chemical reactions which produce the conditions for or cause an uncontrolled or dangerous energy release which may result in or has the potential of resulting in injury or property damage. This can only be achieved by having a total understanding of the inherent energy stored in a compound or mixture and of the conditions under which the stored energy can be released. DO A 1.35873 GONFTDFNTTAl INTRODUCTION The control of chemical reactions is our business. Through the control of reactive chemicals we manufacture nearly all our products: polymers, inorganic, organic, and agricultural chemicals, and drugs. Normally we carry out these reactions without incident or mishap. However, occasionally chemical reac tions get out of control because we use the wrong raw material, change operating condi tions, have unanticipated time delays, have equipment failures, and because we don't always completely understand the chemistry of our process. Chemical reactivity is a very complex phenom enon and there are no substitutes for experi ence and good judgment in evaluating its potential hazards. Therefore, it is essential that a reactive hazard evaluation be made on all processes on a periodic basis that is supported with basic data on the reactive properties of the chemicals and their mixtures in question. This book outlines the Dow program to prevent injury and property damage by preventing uncontrolled chemical reactions. The require ments of the program are: The owner of a material or process is respon sible forobtaining sufficient information forsafe operation. Location managers should establish a know ledgeable working committee at the site to assist the owner in evaluation of potential reaction hazards. Screening tests should be performed to provide data on the reactivity of compounds and mixtures. Additional tests, calculations, and evalua tions should be run to obtain other relevant information whenever screening tests indi cate a potential hazard or if past experience dictates. All chemical processes should be reviewed on a periodic basis. New plant superintendents should review their processes with the site committee with in 90 days of assuming responsibility. Manufacturing and research people should be trained in the concept and execution of the Reactive Chemicals Program. Data on potential reaction hazards should be gathered and disseminated throughout Dow. Every incident and potential incident involv ing reactive chemicals will be investigated and reported including causes and correc tive actions. --2-- DO A 135874 CONFTDFNTTAL OWNER'S RESPONSIBILITY The keystone of Dow's Reactive Chemicals Program is owner responsibility. The owner of a material or process must obtain sufficient information about it to assure safe operation. This includes an understanding of the inherent energy stored in a compound or mixture and the conditions under which the stored energy may be released in a hazardous manner. The owner also has the responsibility to report all reactive chemicals incidents as soon as possi ble to site management and to the local Reac tive Chemicals Committee, but no later than 48 hours after the incident. In addition to these general responsibilities, owners in the various functions have more specific responsibilities as indicated in the sections which follow. A. RESEARCH The researcher, by the very nature of his work, must constantly deal with chemical reactivity and determine the appropriate time to obtain reactive chemicals data. Obviously, each reac tion mixture or minute quantity of unknown material cannot be subjected to extensive test ing for reaction potential. On the other hand, uncontrolled laboratory reactions which injure people and damage property must be prevented. The following general guidelines are designed to help the researcher minimize uncontrolled reactions in his work: Know the properties of the chemicals being used and their potential for uncontrolled reaction. Provide protection from the possibility of unexpected reactions with suitable labora tory facilities and shielding. Keep quantities of materials to a minimum, scaling up gradually with appropriate safety precautions. Obtain reactive chemical screening data as a research project progresses. When other persons or groups become in volved, be sure that adequate hazard infor mation is developed and transmitted to them. It is not possible to establish the exact point in a specific research project when the screening tests outlined inthisguideshould be used.The persons working directly on the project are the ones who can effectively evaluate and control this need. The Reactive Chemicals Committees have been established to help in this evaluation on request. No research project should be pilot planted unless a reactive chemicals review is held. A point considered most critical is when other parties become involved, since it is then that the researcher must assume responsibility for transmitting information to protect these people. This includes not only those within Dow, but those outside the Company as well. B. PRODUCTION AND PILOT PLANTS New Processes Raw materials, process streams, products and waste of any new process that has reached the pilot or production plant stage shall be reviewed and evaluated to determine if any potential reactive chemical hazards are involved. If insufficient data are available, then the materials should be subjected to screening tests. Further testing and calcu lation indicated by the screening program should also be done. Each Dow organiza tional group should require Reactive Chemi cals Committee concurrence before approv al of final capital authorizations. Established Processes All chemical processes will be reviewed be fore the Reactive Chemicals Committee at least once every two years unless a different schedule is determined by the Area manage ment. In addition, every new plant superin tendent should review his process with the Reactive Chemicals Committee within 90 days of assuming responsibility for a pilot or production plant. Prior to the review, the owner should evaluate his raw materials, process streams, products and waste to de termine if any potential reactive chemical hazards are involved. If insufficient data are available, then the materials should be sub jected to additional testing and evaluation. --3-- DO A CONFTDFNTTAl The review should include all auxiliary opera tions to the process such as: raw material and product storage; drum, tank car and truck loading; heat exchanger systems; and spills, accidents, etc. in transport. For a general out line of a process review, refer to the Process Reviews section of this manual. Changes in Processes Changes are often made in processes which are considered small or minor but which could have major effects regarding potential reaction hazards. Often capital authoriza tions are not needed for these changes which could include: -- New supplier of raw materials and method of delivery. -- Equipment changes. -- Minor process changes. -- Automation or computerization. Managers of plants or pilot plants are to review any minor changes from a reactive chemical viewpoint. Significant process changes shall be reviewed by the Reactive Chemicals Committee before being imple mented. C. OTHER OPERATIONS Many Dow operations are not directly con nected with either the research laboratory or production plant. These may involve tank car and tank truck cleaning, bulk terminal opera tions, waste disposal facilities, power plants, etc.Theseand similaroperationsshould under go reactive chemical reviews similarto those of a production process. D. TECHNICAL SERVICE AND DEVELOP MENT TS&D employees have a product stewardship responsibility for the products Dow manufac tures and sells. As part of their stewardship activities they shall obtain and communicate pertinent reactive chemicals hazard informa tion to handlers and users of Dow products. REACTIVE CHEMICALS COMMITTEES A. SITE OR LOCATION COMMITTEE The manager of a division, site, location or organization shall establish a Reactive Chem icals Committee consisting of qualified tech nical peopleand give them the responsibility to coordinate all reactive chemicals functions at the location. The manager shall take a clear and firm stand with his line management defining his expectations for Reactive Chemicals includ ing methods of implementation and check points. When possible, the Committee should be com posed of representatives from Research, Engine ering, Production, Safety and Loss Prevention, Testing and any other appropriate function. The responsibilities of the Committees are to: Establish the program in their organizational groups within the framework of this guide. Collect and distribute hazard data from sources outside their organizational groups. Forward hazard data generated in their organizational groups to other Reactive Chemicals committees through CRI. Train people in the use of the Reactive Chemicals program. Provide data and consultation to owners and management concerning hazard evaluation of materials and processes. Coordinate programs for hazard review of existing materials and processes within their organizational groups. Investigate and report all reactive chemicals incidents. It is recommended that one member of the committee be designated chairman for admin istration of the program. It may be desirable for the committee at large sites to establish a sub committee or mini-committee so that process changes can be reviewed on very short notice without delaying the implementation of the desired change. --4-- D0 A 135876 CONFTDFNTTAL. B. REACTIVE CHEMICALS ADVISORY BOARD To assist the areas in their reactive chemicals programs a continuing committee appointed by Corporate Management has been desig nated the Dow Reactive Chemicals Advisory Board. The members of this Board include representatives from several groups and disci plines in the Company. The responsibilities of the Advisory Board are to: Determine company planning for the pro gram. Approve equipment and procedures for standardizing basic hazard evaluation tests. Develop methods for data handling. Coordinate and direct the efforts of all organizational groups in establishing their Reactive Chemicals Programs. PROCESS REVIEWS Process reviews should be conducted on new processes, periodically on existing processes, on changes planned forexisting processes and on changes in supervision. It is the owner's responsibility to arrange for these reviews with his local Reactive Chemicals Committee. While each process review will vary with the nature of the operation, a general outline of a reactive chemicals process review is as follows: Review the process chemistry, including principal reactions and expected side react ions along with their heat of reactions and pressure build up potential. Review the reactive chemicals test data for evidence of exotherms, shock sensitivity, or other evidence of instability or energy re lease potential. Examine the process of planned operation in detail with the aid of appropriate flow dia grams (instrumentation, pumps, etc. are very important). Look at upset conditions, delays which can occur, modes of failure, worst case situations, and other ways of abusing the chemical. Pay particular attention to redundancy and critical controls. Avoid reactive chemicals accidents by pro bing each phase of an operation from raw material receipts through product distribu tion for any point where a reactive chemicals accident could take place. Consider the consequences of not following procedures: i.e.,incorrect order of addition or stoichiometry, no agitation, etc. Carefully review start-up and shut-down pro cedures and the consequence of a time delay in any step of the process. Identify line of defense which will beemployed to avoid reactive chemicals accidents at each point. The owner of an operation should use "Worst Case'' thinking in evaluating the safety of his operation. At every point in the operation where an exothermic reaction may take place, the owner should conceive the worst possible combination of conditions which realistically could exist. This may include such conditions as loss of cooling water, wrong combination of reactants, wrong position of valves, plugged lines, instrument failure, air leakage, loss of agitation, dead-headed pump, mishandled cata lyst, etc. An engineering evaluation should then be made of the consequences of the "Worst Case" conditions. Potentially serious consequences of a "Worst Case" situation may rule out practicing the operation. Usually, adequate means of avoid ing 'Worst Case" conditions and coping with the consequences can be devised. Where seri ous 'Worst Case" consequences are recog nized, the owner must identify and implement adequate lines of defense. These should start with preventive measures, followed by correc tive measures, then containment measures, and as a last resort, isolation techniques. Redundancy is essential for protection against reactive chemicals accidents. The owner should consult with his Reactive Chemicals Committee and his supervisor on the adequacy of his lines of defense. --5-- 00 A 135677 CONFIDENT! 61. Unreliability of protection systems must not be allowed to be a cause of an accident. Regular documented testing of all elements of pro tection systems is essential. This testing in cludes relief devices, critical instruments, and operator knowledge. REACTIVE CHEMICALS TESTING The Research and Development organization has the responsibility to provide facilities for the testing necessary to determine the poten tial hazards of chemicals and mixtures and to provide the technical expertise required to interpret the results of these tests. To provide basic reactive chemicals hazard data, the following thermal considerations and test guidelines have been developed. The de scriptions of tests are necessarily brief and incomplete. The owner should therefore con sult the Reactive ChemicalsTesting supervisor for details of the test, its significance and limitations, and for a detailed interpretation of the test results. (Note: Refer to Appendices D, E, and F.) A. THERMODYNAMIC CALCULATIONS The potential energy that can be released by a chemical or chemical system can be calculated by means of computerized thermodynamic calculations. These calculations are based on knowing the end products or assuming the end products that might be expected. If the chem ical or system has very little energy, any re action is generally non-hazardous. However, if the reaction products are known or expected to be gaseous, a high-pressure hazard is still possible.(Refer to Appendix B) Thermodynamic calculations should be made early in a hazard evaluation. However, when assumptions are made regarding end products, the calculations should be backed up by other tests such as the DTA and possibly ARC. B. THERMAL STABILITY The evaluation of thermal stability requires the determination of the temperature at which an exothermic reaction occurs, the rate of such a reaction as a function of temperature, and the heat generated per unit of material by the reaction. In many cases, if not most, infor mation on the pressure increases during the reaction are also essential, particularly for vent sizing. DTA and DSC scans are used for preliminary screening to determine whether an exotherm occurs and the approximate temperature and the heat generated. Because the temperature in these jtest devices] is |forced up at a fixed rate, the onset of reaction temperatures will be higher by 50 to 100C than the onset in a adiabatic device such as a plant reactor. Better and more correct thermal data are ob tained from test runs on an ARC or ARD. The temperature is raised stepwise and at a much slower rate than with the DTA or DSC. These devices are nearly adiabatic and thus more nearly approach plant reactor conditions. Another important advantage is the fact that the reaction pressure is monitored and re corded in both the ARC and ARD. DTA (Differential Thermal Analysis) DTA is a basic screening test, and is applied to all chemicals and mixtures unless the thermal stability has already been clearly established. In the test, a sample and an inert reference material are heated at a controlled rate in a single heating block. If an exothermic re action occurs, the sample temperature will rise at a faster rate than the reference tem perature. If the sample undergoes an endo thermic reaction or phase change, its tem perature will lag behind the reference temper ature. The test requires only a few milligrams of sample. The test is basically qualitative, and is in tended for identifying exothermic reactions. --6-- D0 a 135878 CONFIDENTIAL Reported temperatures, particularly the exo therm starting temperatures, are not reliable, since the reaction may be going at an appre ciable rate before it is detected. DTA should therefore be used as a screening test to deter mine what additional testing is needed. DSC (Differential Scanning Calorimetry) DSC may be used instead of, or in addition to, DTA as a basic screening test. The sample and inert reference material (air) are heated separately, in such a way that their temperatures are always equal. Energy input to each sample heater is measured. If an exothermic reaction occurs, the sample heater requires less energy than the refer ence heater, to maintain equal temperatures. If an endothermic reaction or phase change occurs, the sample heater requires more energy input than the reference heater. Although DSC is considered to be more quantitative than DTA, both tests have rough ly the same sensitivity. Onset-of-reaction temperatures reported by DTA or DSC will be higher than true onset temperatures as measured by an adiabatic device such as the ARC. The DTA/DSC measured onset tem perature depends upon the rate of temper ature scan and increases with increased scan rate. ARC (Accelerating Rate Calorimetry) This method determinestheself-heating rate of a chemical under near-adiabatic condi tions and will usually give a conservative estimate of the conditions for, and the con sequences of, a runaway reaction. The test is quantitative, but corrections must be made for thermal inertia of the sample container before the data can be applied to process systems. Activation energy, approx imate heat of reaction, and approximate reaction order are parameters which can usually be determined. Pressure data ob tained during an ARC run can sometimes provide information for vessel vent design. ARD (Adiabatic Runaway Device) The adiabatic runaway device is comparable to the ARC. The device consists of a 300 ml modified PARR-bomb, that has provisions for inert gas blanketing, preheating the react ants, monitoring the reaction temperature and pressure, and for agitation. Hence, the study of two-phase system reactions can be performed. C. SHOCK SENSITIVITY Shock sensitivity data are necessary to evalu ate the potential hazards in transporting and handling chemicals. Transportation here refers to both transporting materials through plant pipelines, valves, pumps, and to general trans porting and handling when shipping materials from one location to another by rail or truck. Shock sensitive materials react exothermally when subject to a pressure impulse. The im pulse may come from a hammer-like blow, such as used in the standard drop-weight test, or a compression, such as might be exper ienced in a dead-headed plant compressor or valve slamming shut. Normally, shock sensi tivity increases with an increase in temper ature. Materials which do not show an exo therm on the DTA or DSC are never shock sensitive. Drop-Weight Test This is used as a screening test, and should be applied to any materials known, or sus pected, to contain unstable atomic group ings (see Appendix C). The test measures the susceptibility of a chemical to decompose explosively when subjected to the impact produced by drop ping a weight onto a small sample in a metal cup. Solids and liquids are tested under slightly different conditions, but, in both cases, the weight and/or height can be varied, to give semi-quantitative results for impact energy. Results are not absolute, but can be used for comparing the instabilities of two or more chemicals under the conditions of the test. --7-- DO A 13S679 CONEI DENT T Al A negative result does not prove the absence of hazards, but does indicate stability, except under severe conditions. Confinement Cap Test This test is used to determine detonability of a material using a blasting cap as an initiator. The blasting cap is ignited to set up a shock wave in the sample in less than 1 millisecond. If the material detonates, it will add energy to the system, which will split the aluminum tube in which it is confined. The amount of splitting is compared to known explosive materials. Tests may be run at elevated temperatures. Adiabatic Compression Test In this test, high pressure is applied very rapidly to a liquid in a U-shaped steel tube. This compresses a gas (air or nitrogen) in the sealed arm of the tube, and heats it to a high temperature. Bubbles of the hot compressed gas are driven into the liquid and may cause explosive decomposition of the liquid, and rupture of the tube. Test temperature and pressure can be varied. The test is intended to simulate the "waterhammer" effect in pipes, and "sloshing" ef fects in transportation. The test is very sev ere, and gives "worst case'' results. Negative results therefore confirm the ab sence of a hazard. D. FLAMMABILITY Flammability tests evaluate the hazard present when an ignition source is available. These tests range from the determination of flash point, flammable limits, and autoignition to the very rapid and destructive burning in a dust explosion. From the point of view of the potential for a fire, the closed cup flash point determination is probably the most important. In a perfect closed cup test, the vapor pressure is in equilibrium with the liquid at the temperature of the test. At the flash point the vapor composition is at the lower flammable limit and, in fact, the lower flammable limit can be estimated from vapor pressure data (for a pure compound). Open cup flash points are generally higher, and thus less conservative, than closed cup determina tions. The value determined in an open cup test is subject to air movement at the open face of the cup and true vapor-liquid equilibrium prob ably does not occur. Autoignition temperatures should be used with care. The surface area, the time of exposure to a given temperature, the availability of the oxygen supply, and the adiabaticity of the system will all affect the temperature at which a material self-ignites. A general rule for dust explosions is that any combustible material, if in fine particle form, can result in a dust explosion. The maximum pressures produced in a dust explosion are typically of the order of 100 psig. The rates of pressure rise and the ease of ignition, however vary considerably from material to material. Flash Point The flash point is the lowest temperature at which the vapors can be ignited under the conditions defined by the test apparatus and method. Flash points are necessary for safety considerations in a Reactive Chemical Review and are required by government agencies before registering and transporting chemicals. There are a number of standard methods: a. Tag Closed Cup (A.S.T.M. D56) b. Tag Open Cup (A.S.T.M. D1310) c. Pensky-Martens Closed Cup (A.S.T.M. D93) d. Cleveland Open Cup (A.S.T.M. D92) e. Setaflash Closed Tester (A.S.T.M. D3278) For applicability and limitations of each test, consult the reactive chemicals testing super visor, or refer to the appropriate A.S.T.M. standards. In addition, A.S.T.M. E502 reviews the closed-cup methods, and discusses poten tial problems with testing mixtures. --8-- DO A 135880 OONFTDFNTTAl  Flammable Limits Flammable limits, or flammable range, are the upper and lower concentrations (in vol ume percent) of a vapor in air which can just be ignited by an ignition source. Above the upper limit and below the lower limit, no ignition will occur. Data are normally report ed for air at atmospheric pressure and at a specified temperature. Flammable limits may be reported for atmospheres other than air, and at pressure other than atmospheric pressure. The basic test apparatus consists of a cham ber into which a known concentration of vapor (gas) in air is introduced. After thorough mixing, ignition is attempted with a spark or a hot wire. A series of different concentrations are tested to establish the upper and lower concentration limits for flammability. Although normally run with fuel-air mixtures at ambient conditions, other oxidizing atmo spheres, diluent effects, and temperature and pressure variations can be studied. Flammable limits for most combustible gases and low-boiling liquids are known. Lower flammable limits can often be calculated reasonably accurately (see Appendix B), but calculations for upper flammable limits are less satisfactory. If testing is required, the essential consider ation is that the test temperature must be high enough to vaporize enough fuel. For the lower flammable limit, in air at atmospheric pressure, the minimum temperature is the closed-cup flash point. As a rough guide, the upper limit requires a temperature about 40C higher. Tests on mixtures must be run at a temper ature at which the sample is completely vaporized. If the vapor pressures of the components are widely different, results can be unreliable, and often cannot be related to the hazards under process conditions. Autoignition Temperature The ignition temperature of a substance, whether solid, liquid, or gaseous, is the minimum temperature required to initiate or cause self-sustained combustion, in air, with no other source of ignition. Ignition temperatures observed under one set of conditions may be changed markedly by a change of conditions. For this reason, ignition temperatures should be looked upon only as approximations. Some of the vari ables known to affect ignition temperatures are percentage composition of the vapor or gas-air mixtures, shape and size of the space where ignition occurs, and rate and duration of heating. Test results tend to be high, and are not to be used for establishing "safe" temperatures. Under process conditions, there is a potential for fuel-air mixtures to ignite at much lower temperatures, due to extraneous sources of ignition that are virtu ally impossible to eliminate Dust Explosion Combustible, dusty material, with particle size less than approximately 200 mesh, can explode if a sufficient concentration in air is present along with an ignition source. The standard test has been designed to determine the rates of pressure rise during an explosion, the maximum pressure reach ed, and the minimum energy needed to ignite the material. A more recently developed 20 liter volume test device provides more reliable data for the design of vent and explosion relief. E. INTERPRETATION Every test has its own interpretation due to test limitations and variations in test conditions. Therefore, a person knowledgeable about the tests should be consulted, preferably before testing is requested, and again for interpre tation of the test results. --9-- DO A 135881 CONFIDENTIAL When applying the results of these tests to the plant environment, it is essential to recognize that these tests are conducted on a small sample under specified conditions which do not include all aspects of the chemical envi ronment. Other important parameters are: a. Temperature-pressure variations. b. Temperature-time variations. c. Catalytic effects of contaminants. d. Catalytic effects of container material. e. Increased volume of system. f. Stronger initiation energy than used in test. g. Increased surface contact. Different environments exist in the laboratory, in the plant, in transportation, in storage, in field application, and in disposal. These factors can be expected to have significant effect on the reactive properties of any material. A large number of other tests and hazard evaluation techniques have been developed, both within Dow and by outside organizations. The owner of materials and processes should work with the site Reactive Chemicals Com mittee to determine what additional data are needed beyond those obtained from the basic screening tests. DATA HANDLING The owner of a material or process must obtain, maintain, and update the reactive chemicals data necessary for safe operation. Data may be obtained from: A. EXISTING DATA Technology Centers - The Technology Centers are maintaining files containing the reactive chemicals data pertaining to their plants. Central Report Index (CRI) -- Data on welldefined compounds or mixtures are sent to CRI for its files and may be obtained from them or your reactive chemicals analytical contact. A computerized alphabetical list (names and synonyms) is maintained by CRI and is published periodically under the title "Re active Chemicals Index." Copies are avail able from CRI. Literature -- Reactive Chemicals data may be obtained for many materials from the tech nical literature and suppliers literature. B. NEW DATA Data on new or unknown chemicals or mixtures may be obtained by submitting a sample to the reactive chemicals testing group in your area. It is very important to realize that every test has its own interpretation due to test limitations and variations in test conditions. Therefore, a person knowledgeable about the tests should be consulted for interpretation of the test results. If an owner obtains new data from a reactive chemicals testing group or from a supplier, a copy should be forwarded to the appropriate Tech Centerforits reviewandfiles. Inaddition, data generated on well-defined materials should be sent to CRI in Midland by the reactive chemicals testing groups. 10- DO A 10588? CONF TDFNTT At. APPENDIX A DEFINITIONS A reactive chemicals incident is defined as a chemical reaction which produces the conditions for or causes an uncontrolled or dangerous energy release which may result in or has the potential for resulting in injury or property damage. The owner, for the purpose of reactive chemicals, is the Dow person directly responsible for the safety of the particular material, process, or related operations. APPENDIX B CALCULATIONS FOR CHEMICAL HAZARDS Although some of these calculations can be done by hand, the capability for computerized calculations is available at Physico-Chemical Research, Midland and Analytical Services, Texas. Heats of Reaction, Combustion, Polymerization, and Decomposition. These are computed simply from stoichiometric coefficients and A Hf for the reactants and products. Unknown A Hf values can often be estimated with sufficient accuracy for rough applications by using methods such as: Group increments (see Stull, Westrum & Sinke). Benson's method, Chem. Rev.69, 279 (1969). Handrick's A He method (Reid & Sherwood's book discusses this and other methods). When A Hr0 cannot be estimated satisfactorily, we try to estimate A Hr directly by means of a similar "model" reaction which is known. Equilibrium Composition (Conversion to Products) Prediction. This capability has many varied uses. It can direct research away from the blind alleys of infeasible reactions. It should be used more by those wanting to maximize production. Here is a yardstick by which to measure actual processes. Do they approach the predicted conversion to products? What are the effects of variables such as T, P, and initial composition? Our predictions are computed with a modified form of the chemical equilibrium program described by Cruise, J. Phys. Chem. 68, 3797 (1964). Gases, liquids, and solids are considered simultaneously. Calculations may be done isothermally or adiabatically. The method minimizes A G. Reactive Hazard Prediction The chemical equilibrium program is used in the adiabatic mode to calculate temperatures, heats, and (crude) pressures for decomposition and oxidation. Stull (Chem. Eng. Prog., Loss Prevention, Vol 4, p. 16, 1970) showed that these parameters are rough measures of potential reactive hazard. Also available is the ASTM program, CHETAH, a program used for the estimation of explosive hazard. Flammability Limit Prediction Lower flammability limits of vapors may be predicted quickly, including the effects of initial temperature and inert diluents such as N2 and C02 . The limiting oxygen content necessary for flame propagation can also be predicted. The method applies to total pressures near atmospheric, to both pure and mixed fuels, and is not limited to oxygen as the oxidizer. When the fuel vapor-pressure curve is known, we can also predict flash points. The chemical equilibrium program is used to calculate adiabatic flame temperatures as a function of volume percent of fuel. The predicted lower limit is the fuel percent corresponding to a threshold temperature. The same criterion sometimes yields rough values of the upper flammability limit, but there are complications in this fuel-rich region. -- 11 D0 A T35883 CONFIDENTIAL APPENDIX C ATOMIC GROUPINGS THAT CHARACTERIZE EXPLOSIVE COMPOUNDS Chemicals containing the following atomic groupings are known by experience to be unstable or explosive: BOND GROUPINGS -C^C- -OC--Metal -C=C-X N=N \/ ft >N2 >C~N=0 ^c-no2 NC/N2 / \io2 ^c-o-n=o ^c=o-no2 A A____r'' ,C=N--0--Metal NO, -C-F i N02 ^N--Metal ^N-N=0 ^N--NO, ~C--N=N--C^* ^C-N=N--0--C^- ^C--N=N--S--C^ ^C-N=N-0-N=N-C=: ~C--N=N--S--N=N--C^ CLASS_______ Acetylenic Compounds Metal Acetyl ides Haloacetylene Derivatives Diazirines Diazo Compounds Nitroso Compounds Nitroalkanes, C--Nitro and Polynitroaryl Compounds Polynitroalkyl Compounds Acyl or Alkyl Nitrites Acyl or Alkyl Nitrates 1, 2-Epoxides Metal Fulminates or aci-Nitro Salts Fluorodinitromethyl Compounds N--Metal Derivatives N-Nitroso Compounds N--Nitro Compounds AZO Compounds Arenediazoates Arenediazo Aryl Sulphides Bis-Arenediazo Oxides Bis-Arenediazo Sulphides -- 12 -- po CONF Atd1f3n5tSt&a41 ' \l/ \ / 1 2 1 I \J7\I/ BOND GROUPINGS CLASS C-N=N--N--C i R(R-H,--CN,--OH,--NO) --N=N--N=N-- C-O-O-H C-O-O-C^ 0-- O--Metal 0--0--Non-metal 1- `Cr--02 N3 1-- c-n2 0 Trizaenes High-Nitrogen Compounds Tetrazoles Alkylhydroperoxides, Peroxyacids Peroxides (Cyclic, Diacyl, Dialkyl), Peroxyesters Metal Peroxides, Peroxoacid Salts Peroxoacids Amminechromium Peroxocomplexes Azides (Acyl, Halogen, Non-Metal, Organic) Arenediazoniumolates c-n2+s" --N+--OHZ $c-n2+z" [N-Metal]+Z Ar-Metal--X X-Ar--Metal N-X -nf2 -0-X Diazonium Sulphides and Derivatives, 'Xanthates' Hydrazinium Salts, Oxosalts of Nitrogenous Bases Hydroxylammonium Salts Diazonium Carboxylates or Salts Aminemetal Oxosalts Halo-Arylmetals Halogen Azides N-Halogen Compounds N-Haloimides Difluoroamino Compounds N,N,N-Trifluoroalkylamidines Alkyl Perchlorates Chlorite Salts Halogen Oxides Hypohalites Perchloric Acid Perchloryl Compounds (The list of structures is taken from "Handbook of Reactive Chemical Hazards, CRC Press.) -- 13 -- DO 0 13S88S OONFTDFTNTIAl APPENDIX D CONSIDERATIONS AND TESTING DIAGRAMS This outline is the owner's general guide for determining a potentially hazardous operation. Interpretation of results and need for additional testing should be determined in consultation with Analytical personnel and the Reactive Chemicals Committee. & o :o 0) i y* >- 0rt0' t APPENDIX E REACTIVE CHEMICALS TESTING SITES LOCATIONS 7t*oV///<v^T/// 'V'/VtOi/V/^. //dc;r?' /// /#/ TECHNIQUE Differential Thermal Analysis (DTA) / z `l J76c/ s AMOUNT NEEDED T * Vo / ^ // /Cac//^^ A few milligrams X X XX XX X X X / / 7vVv-s 4/ ^7^z $/ ^/ 03y y y az X XX X XX XX X X XX Differential Scanning Calorimetry (DSC} Accelerating Rate Calorimetry (ARC) Adiabatic Runaway Device (ARD) Drop Weight cn Test I Cap Confinement Test Adiabatic Compression Test Auto ignition Temperature Flash Point A few milligrams 5-10 Grams 100-200 Grams A few milligrams 4 Grams A few Grams A few milligrams 100 Grams XX X XX XX X X X XX X XXX X XX XX X XX X X XX X X X X XX XX X XX XX XX XX XXX X XX XX XX XXX XXX X XX X XX XXX X X X X XX X XX Flammable Limits A few Grams XX XX Dust Explosion A few Grams XX X X Ignition Energy A few Grams X High Pressure Flammability A few Grams XX Constant Temperature Stability Test 100-500 Grams Only thermostated bath oven needed except when determining validity of ARC or ARD extrapolation which requires near adiabatic conditions. Quantity needed for single test - Check with location for quantity needed for test procedure. Methods available on 5/81. Check with your facility for latest information on equipment available. AHPtNUIX h DOW CONFIDENTIAL REACTIVE CHEMICAL HAZARD Material name iu$* C r i n*me ii AvAiiAbitl ( MOLECULAR FORMULA PROPERTIES AND PRECAUTIONS SAMPLE purity DATA PHYSICAL STATE REFERENCE NUMBER DATE OF ISSUE LATEST REVISION DATE DQW REGISTRY NO STRUCTURAL FQRMUL A, COMPOSITION COMPONENTS & IMPURITIES RELATED TO WHAT PHOCESS OR PRODUCT* source of Sample (location, building, reactor etc > STAGE OF DEVELOPMENT (LAB SCALE, PILOT PLANT,! OWNER OR ORIGINATOR OF REQUEST FOR TESTING NAME BLOG. LOCATION CHARGE NO. PHONE NO. LABORATORY SCREENING TESTS WARNING1 Data based on laboratory test conditions; use caution in extending to different environments. DSC DDTA RATE OF TEMP INCREASE THERMAL ANALYSIS MAXIMUM TEST TEMP TYPE EXO FNDO START OC MIN. c PEAK C END C c TEST METHOD size Solid-Liquid DROP-WEIGHT IMPACT SENSITIVITY (DW) TEST TEMP. C HEIGHT cm WEIGHT Kg number OF TESTS POSITIVE NEGATIVE TEST WEIGHT (1 SAMPLE ATMOSPHERE COMMENTS IH50 E&0> NITROGEN Q AIR oxygen Dother---------------------------- TEST RUN 0Y TEST DATE FLASH POINT <FP) COMMENTS, FOLLOW UP SPECIAL PRECAUTION TEST REFERENCE TEST RUN BY TEST REFERENCE TEST RUN BY FLAMMABLE LIMITS (FL) LIMITS-VOL. % LOWER UPPER PRESSURE PSIA or mmHg TEMP. C IGNITION SOURCE TEST RUN BY TEST DATE AUTOIGNITION TEMPERATURE (AT) TEST RUN BY TEST DATE TEST REFERENCE c F TEST REFERENCE * FORM C-110VO PRINTED R-7-7* ACCELERATING RATE COLORIMETERY (ARC) REPORT NO, --------------- DO A 135888 CONFIDENTIAL WALKER ADIABATIC RUNAWAY DEVICE (ARD) REPORT NO -- 16 -- SEE REVERSE SIDE BACK OP FOBM C-I100 PB1NTED B-7-7t 17 -- DO A 135889 OONFTDFNTTAL CORPORATE SAFETY AND LOSS PREVENTION PUBLICATIONS MINIMUM REQUIREMENTS Minimum Requirements for S&LP Security - Minimum Requirements & Guidelines GUIDELINES Guidelines for Data Processing Centers Guidelines for Contractor Safety Guidelines for Safety & Loss Prevention Audits Guidelines for Office Safety Guidelines for Personal Protective Clothing & Equipment Guidelines for Emergency Planning Guidelines for A Motor Vehicle Accident Prevention Program Guidelines for Safety on Non-Dow Premises Guidelines forfor S&LP Reporting, 3rd Edition Guidelines for Accident Investigation Guidelines for Dow Hearing Conservation Program Fire and Explosion Index, 5th Edition Guidelines for Warehouse Rating Distribution Emergency Response System Guide** Procedural Guide for Determining Dust Hazard Potential Air Travel - Policy and Guidelines Guidelines for Safe Sample Shipping Guidelines for a Reactive Chemicals Program Guidelines for Handling Dow Proprietary Intormation Guidelines for Personal Safety & Security at Hotels/ Motels and Other Off-Premises Facilities PRACTICES Loss Prevention Principles Operations Practices OTHERS Fundamentals of Fire and Explosion - By Daniel R. Stull Topical Index of S&LP Standards & Specifications S&LP Audio/Visual Listing The Office Safety Handbook Traveler's Safety Advisory - Hotels/Motels/Conventions S&LP Data Base - LTI Statistics & Learning Experience PD/BI Statistics & Learning Experience Publications available from: Corporate Safety and Loss Prevention 2030 Dow Center - Midland (517) 636-3358 or-6821 **US Area Distribution Guide January 1979 February 1980 August 1977 November 1979 March 1980 December 1979 May 1981 June 1979 April 1981 December 1980 March 1981 July 1981 July 1979 October 1980 March 1980 1979 May 1978 April 1980 April 1981 August 1981 July 1981 July 1981 Continuous December 1979 January 1978 August 1980 1977 1981 00 A 135890 CONFIDENTIAL