ORGANOMETALLICS AND REACTIVE SPECIALTY ORGANICS SAFE HANDLING GUIDE

Transcription

1 ORGANOMETALLICS AND REACTIVE SPECIALTY RECOMMENDED PROCEDURES FOR THE TRANSPORT, TRANSFER AND USE OF ORGANOMETALLICS AND REACTIVE ORGANICS

2 DISCLAIMER IN PREPARING THIS GUIDE, FMC LITHIUM HAS UTILIZED THE BEST INFORMATION KNOWN AND AVAILABLE AT THE TIME OF PUBLISHING. FMC LITHIUM RECOGNIZES THAT OVER TIME, TECHNIQUES, METHODS AND EQUIPMENT RELATING TO THE SAFE HANDLING OF ORGANOMETALLICS AND REACTIVE SPECIALTY ORGANICS WILL EVOLVE, DATING THE INFORMATION WITHIN THIS GUIDE. Additionally, the information presented in this Guide has been written to address most typical situations, environments and facilities, based upon FMC Lithium s experiences. However, FMC Lithium recognizes that each customer s situation is different and necessitates specific solutions to fit those requirements. More information on most of our organometallics and reactive specialty organic products may be found on the appropriate new product data sheet (NPDS) that is shipped with each developmental sample. More information concerning our commercial products can be located online at by viewing the appropriate product data sheet (PDS) and/or material safety data sheet (MSDS). FMC Lithium seeks to provide up-to-date solutions to the questions or concerns that our customers may have. Please contact FMC Lithium to discuss your specific needs. ORGANOMETALLICS AND REACTIVE SPECIALTY

3 QUICK REFERENCE GUIDE APPLICATIONS Organolithium relative base strengths Page 4 PROPERTIES Flashpoints of solvents Page 8 PRODUCT SPECIFICATIONS FMC Lithium commercial products Page 12 LABORATORY Analytical methods Page 16 Safety Page 16 Laboratory set-up Page 18 SAFETY Hazards Page 20 First aid Page 22 Protective equipment Page 23 Fire fighting Page 23 DESIGN Storage and handling Page 26 Equipment design Page 26 Maintenance procedures Page 29 Disposal Page 29 SHIPPING Cylinder index Page 32 Valve index Page 33 USA: FMC LITHIUM TELEPHONE FAX EUROPE: FMC CHEMICALS TELEPHONE FAX JAPAN: ASIAN LITHIUM CORPORATION (ALCO) TELEPHONE FAX TAIWAN: FMC LITHIUM TELEPHONE FAX ORGANOMETALLICS AND REACTIVE SPECIALTY QUICK REFERENCE GUIDE UNLOADING AND SAMPLING Cylinder transfer schemes Page 58 Cylinder unloading Page 60 Drum transfer schemes Page 66 Drum unloading Page 68 CHINA: FMC LITHIUM TELEPHONE FAX INDIA: FMC INDIA PRIVATE LIMITED TELEPHONE FAX

4 TABLE OF CONTENTS INTRODUCTION APPLICATIONS PROPERTIES GENERAL PROPERTIES PRODUCT SPECIFICATIONS LABORATORY SAMPLING ANALYTICAL METHODS SAFETY SAFETY DESIGN EQUIPMENT DESIGN SHIPPING UNLOADING AND SAMPLING TRANSFER AND UNLOADING SCHEMES TABLE OF CONTENTS ORGANOMETALLICS AND REACTIVE SPECIALTY

5 INTRODUCTION 2 THIS GUIDE OUTLINES TECHNIQUES FOR THE SAFE HANDLING OF ORGANOMETALLICS AND REACTIVE SPECIALTY ORGANIC COMPOUNDS. FMC Lithium has a long history of creating, developing, manufacturing and safely handling organometallics and now, reactive specialty organics. We are recognized as the world s experts in the creation, development and production of alkyllithiums, aryllithiums, lithium amides, lithium alkoxides and metal hydrides used as strong hindered bases, nucleophiles and reducing agents. By naturally extending our organometallic expertise, we are creating lab-through commercial-scale quantities of custom organolithiums, organosilanes, organophosphines, substituted pyridines and boronic acids utilized as reagents and intermediates. Organometallics are the backbone in everything we do. Lithium metal plus one step creates many useful and well-known organolithiums. Lithium metal plus two steps creates organosilanes utilized as unique protecting groups and organophosphines used as ligands that increase catalyst turnover and efficiently produce high yields. Lithium plus three steps allows us to generate high regioselectivity on an aromatic ring by creating substituted pyridines and boronic acids via alpha lithiation, lithium-halogen exchange or directed ortho-metalation (DoM). FMC Lithium has five organics manufacturing and distribution facilities worldwide. This ensures reliable supply and quick response for our customers. We also have well-defined methods for the proper handling of pyrophoric materials, facilitating the safe, trouble-free transport, transfer and use of organics. We want you to be familiar with the precautions, equipment, and techniques needed to safely and confidently handle and utilize our reactive organics. Education and training are the most important elements in the safe handling of organometallics and reactive organics. Upon our customer s request, FMC Lithium provides consultation on the design of storage and dilution systems, as well as providing safety training to those that work with organometallics and reactive organics. We can also supply technical assistance, information on specific product properties, behaviors, methods and details of non-proprietary uses and applications. More information can be obtained from FMC Lithium on all organometallics and reactive organics. Product data sheets (PDSs), material safety data sheets (MSDSs) and technical application reviews are available at along with more specific information on our butyllithium products. ORGANOMETALLICS AND REACTIVE SPECIALTY INTRODUCTION PAGE 2 OF 71

6 3 WE WANT CUSTOMERS TO BE ABLE TO HANDLE AND USE OUR ORGANOMETALLICS AND REACTIVE ORGANICS SAFELY AND CONFIDENTLY. DESIGNING PROCEDURES FOR THE SAFE TRANSPORT, TRANSFER AND USE OF ORGANOMETALLICS AND REACTIVE ORGANICS IS A COLLABORATIVE EFFORT AT FMC. THE TECHNIQUES AND PROCEDURES DISCUSSED IN THE ORGANOMETALLICS AND REACTIVE SPECIALTY ORGANICS SAFE HANDLING GUIDE SHOULD BE UTILIZED BY PROFESSIONALS TRAINED AND EXPERIENCED IN WORKING WITH THESE COMPOUNDS. PAGE 3 OF 71 INTRODUCTION ORGANOMETALLICS AND REACTIVE SPECIALTY

7 APPLICATIONS 4 ORGANOLITHIUM REAGENTS FMC IS LOOKING BEYOND LITHIUM TO DEVELOP NEW ORGANOSILANES, ORGANOPHOSPHINES, BORONIC ACIDS, SUBSTITUTED PYRIDINES, ORGANIC INTERMEDIATES, AS WELL AS OTHER PRODUCTS THAT UTILIZE OUR ORGANOMETALLIC EXPERTISE IN THEIR SYNTHESIS. Lithium is in our name, but it is not the only product we manufacture and distribute. We are renowned experts in the development and production of alkyllithiums, aryllithiums, lithium amides, lithium alkoxides and metal hydrides used as strong hindered bases, nucleophiles and reducing agents. With high regioselectivity and ease of lithiation at virtually any position on an aromatic ring, custom intermediates, such as substituted pyridines and boronic acids, are created and produced via alpha lithiation, lithium-halogen exchange or directed ortho-metalation (DoM). The variation in base strength, nucleophilic character, steric properties and solubility offers a versatile palette of reagents to chemists developing a catalytic or synthetic process. In the mid-1980s, FMC recognized a need for more user friendly reagents in the marketplace. To fill this void, FMC developed lithium diisopropylamide (LDA) solutions and methyllithium (MeLi). FMC s LDA 9500 and LDA 9505 products are non-pyrophoric and eliminate the use of n-butyllithium to prepare LDA, a process that generates butane as a by-product which can present emissions issues. MeLi 9307 in THF/ cumene was developed to reduce the use of highly flammable diethyl ether as a solvent. Two additional non-pyrophoric products, lithium hexamethyldisilazide solutions and lithium tetramethylpiperidide were also added to FMC s line of lithium amides. FMC Lithium regularly publishes reviews on different aspects of organometallic and related chemistries in the Lithium Link publication, which is available at Hard copies of the publication may be requested on the website. Table 2.1 RELATIVE BASE STRENGTHS SPECIES pk a VALUE OF CONJUGATE ACID tert-butyllithium 53 sec-butyllithium 51 n-butyllithium 50 n-hexyllithium 50 Methyllithium 48 Phenyllithium 43 Lithium amide 38 Lithium tetramethylpiperidide 37.8 Lithium diisopropylamide 35.7 Lithium hydride 35 Lithium hexamethyldisilazide 29.5 Lithium t-butoxide 17 Lithium methoxide 15.2 Source: March, J., Advanced Organic Chemistry, Wiley Interscience, 5th Ed., 2001, p ORGANOMETALLICS AND REACTIVE SPECIALTY APPLICATIONS ORGANOLITHIUM REAGENTS PAGE 4 OF 71

8 5 APPLICATIONS FOR ORGANOMETALLIC REAGENTS, HIGHLY FUNCTIONALIZED LIGANDS AND COORDINATION COMPOUNDS INCLUDE PHARMACEUTICALS, AGRICULTURAL PRODUCTS, FRAGRANCES, POLYMERS, AND ELECTRONICS. FMC LITHIUM IS LOOKING BEYOND LITHIUM TO DEVELOP NEW INNOVATIVE PRODUCTS TO MEET THE DEMANDS OF AN EVOLVING MARKETPLACE. WE PRODUCE LABORATORY THROUGH COMMERCIAL-SCALE QUANTITIES OF CUSTOM ORGANOLITHIUMS, METAL HYDRIDES, ORGANOSILANES, ORGANOPHOSPHINES, SUBSTITUTED PYRIDINES AND BORONIC ACIDS USED AS REAGENTS AND INTERMEDIATES. PAGE 5 OF 71 ORGANOLITHIUM REAGENTS APPLICATIONS ORGANOMETALLICS AND REACTIVE SPECIALTY

9 PROPERTIES 6 GENERAL PROPERTIES MANY ORGANOMETALLICS AND PHOSPHINES ARE PYROPHORIC OR VERY REACTIVE, IGNITING SPONTANEOUSLY UPON EXPOSURE TO AIR. Consequently, handling of these materials requires rigorous exclusion of air (oxygen) and moisture (see Design section, p. 24). Pyrophoricity usually diminishes as the concentration of these compounds decreases. It should be noted that most organometallics and some reactive organics at any concentration will react with air or moisture, releasing heat on contact. This may cause evaporation of the carrier solvent and lead to the material becoming more concentrated which could result in ignition. Pyrophoricity is tested in the USA according to DOT regulations, 49 CFR 173 Appendix E. Test results establish the likelihood of the material igniting on an inert support or charring a specific grade of filter paper. If the material ignites on the inert support or chars the filter paper under test conditions, the solution is deemed pyrophoric. As the concentration of some organometallics and reactive organics is steadily reduced, a point is reached when ignition or charring of the paper is no longer observed. The highest concentration that fails to ignite or char the paper is termed the non-pyrophoric limit. At concentrations below this limit, the solution may still be classified as spontaneously combustible or water reactive. Outside of the standard test conditions, pyrophoric behavior is increased by the presence of water or reactive materials. ORGANOMETALLICS AND REACTIVE SPECIALTY PROPERTIES GENERAL PROPERTIES PAGE 6 OF 71

10 7 SOME ORGANOMETALLICS AND REACTIVE ORGANICS ARE MORE REACTIVE THAN OTHERS AND HAVE A GREATER TENDENCY TO SELF-IGNITE WHEN EXPOSED TO OXYGEN, MOISTURE, CARBON DIOXIDE OR HEAT. AN FMC ENGINEER MONITORS AN ORGANIC REACTION IN THE KILO LAB. PLEASE VISIT OUR WEBSITE AT TO OBTAIN FURTHER INFORMATION ON THESE PRODUCTS INCLUDING SAFE HANDLING, PRODUCT DATA SHEETS, MSDSs AND RELATED TECHNICAL APPLICATION REVIEWS, OR CONTACT US DIRECTLY TO OBTAIN MORE SPECIFIC INFORMATION CONCERNING YOUR PARTICULAR NEEDS. PAGE 7 OF 71 GENERAL PROPERTIES PROPERTIES ORGANOMETALLICS AND REACTIVE SPECIALTY

11 PROPERTIES 8 BASED ON OUR KNOWLEDGE OF HANDLING ORGANOMETALLICS AND REACTIVE ORGANICS, THE FOLLOWING CHARACTERIZATIONS ARE OFFERED TO HELP JUDGE THE TENDENCY OF SOLUTIONS TO IGNITE SPONTANEOUSLY WHEN EXPOSED TO AIR OR ACCIDENTALLY SPILLED. CONCENTRATION Many of FMC Lithium s products are offered as solutions in hydrocarbon solvents. The hydrocarbon solvent is a definite fire hazard because the organometallic and reactive organic provides a potential ignition source. At low concentrations, the reaction of an organometallic and reactive organic exposed to air is less likely to produce sufficient heat to ignite the solvent. Higher concentrations increase the heat generated from the solutions when exposed to air, in turn, increasing the likelihood of spontaneous ignition. In some cases, a highly concentrated pyrophoric solution may be less pyrophoric than a moderately concentrated solution because it has a lower vapor pressure. In addition, more highly volatile solvents will evaporate quickly, concentrating the non-volatile organometallic or reactive organic while increasing the degree of pyrophoricity. RELATIVE HUMIDITY Most organometallics react vigorously with water, generating heat. The likelihood of ignition is proportionate to the amount of water present in the air on exposure. Humidity increases the likelihood of ignition. Spillage exposed to wet surfaces will most likely self-ignite. AIR SENSITIVE PHOSPHINES Some chemicals, such as tertiary organic phosphines are not water sensitive, but may still be pyrophoric. This is due to the oxidation of the phosphine with oxygen in the air. Oxygen must be rigorously excluded from containers of air sensitive phosphines. METAL HYDRIDES Metal hydrides release flammable hydrogen gas when exposed to water, humid air or other proton sources. This hydrogen evolution can be dangerous because of the chance for creating explosive mixtures with air and potential for rapid pressure increases in closed systems. For these reasons, water or protic solvents must be rigorously excluded from all vessels and lines. SOLVENT FLASHPOINT Solvents with low flashpoints also increase the likelihood of ignition, since less heat is needed to initiate combustion. Even when spills do not immediately ignite, the heat evolved accelerates the evaporation of the solvent and can lead to flashback fires or explosions. For example, flashpoints of common solvents increase as indicated in Table 3.1. Table 3.1 FLASHPOINTS OF SOLVENTS SOLVENT FLASHPOINT C pentane hexanes cyclohexanes tetrahydrofuran n-heptane -3.9 toluene 7.0 ethylbenzene 22.0 cumene 31.0 In summary, the following conditions may significantly increase the degree of pyrophoricity for all concentrations: contact with water or moist materials contact with reactive or combustible materials local overheating and solvents with low flashpoints Concentrations above the pyrophoric limit may or may not self-ignite when exposed to air or spilled. There is no certainty that all organometallic and reactive organic solutions will respond as stated. ORGANOMETALLICS AND REACTIVE SPECIALTY PROPERTIES GENERAL PROPERTIES PAGE 8 OF 71

12 THERMAL STABILITY Refer to the specific product data sheet for thermal stability data available at 9 SENSITIVITIES It is important to keep in mind when handling organometallics and reactive organics that their physical properties and subsequent behaviors vary. Organometallics and reactive organics can be air sensitive, water sensitive or both air and water sensitive. This is critical to know when determining how to safely handle these products. t-bu 3 P Me 3 P OXYGEN SENSITIVE n-buli t-bu 2 PCI DBM WATER SENSITIVE TBSCI t-bu 2 Si(OTf) 2 The above graphic depicts a few FMC products that are air sensitive, water sensitive or both air and water sensitive. PAGE 9 OF 71 THERMAL STABILITY PROPERTIES ORGANOMETALLICS AND REACTIVE SPECIALTY

13 PRODUCT SPECIFICATIONS 10 FMC LITHIUM OFFERS AN EXTENSIVE SELECTION OF ORGANOMETALLICS AND REACTIVE ORGANICS TO MEET OUR CUSTOMER S DIVERSE NEEDS. UPON REQUEST, WE ALSO PROVIDE CUSTOM FORMULATIONS AND SPECIFICATIONS FOR OUR COMMERCIAL ORGANOLITHIUMS. This section contains standard specifications for many of our specialty organic formulations, as well as other commercially available organometallics and reactive organics. FMC Lithium produces a wide variety of other organic reagents, highly functionalized ligands and coordination compounds used in organic synthesis applications for the pharmaceutical, agricultural products, fragrances and electronics markets. PLEASE VISIT OUR WEBSITE AT TO OBTAIN FURTHER INFORMATION ON THESE PRODUCTS INCLUDING SAFE HANDLING, PRODUCT DATA SHEETS, MSDSs AND RELATED TECHNICAL APPLICATION REVIEWS, OR CONTACT US DIRECTLY TO OBTAIN MORE SPECIFIC INFORMATION CONCERNING YOUR PARTICULAR NEEDS. ORGANOMETALLICS AND REACTIVE SPECIALTY PRODUCT SPECIFICATIONS PAGE 10 OF 71

14 11 MORE INFORMATION CONCERNING BUTYLLITHIUMS CAN BE FOUND IN FMC S BUTYLLITHIUM SAFE HANDLING GUIDE AVAILABLE AT OR BY CONTACTING FMC LITHIUM. AN FMC ENGINEER ADJUSTS A FILTER IN OUR SPECIALTY ORGANICS PLANT. FMC HAS NEARLY FIVE DECADES OF EXPERIENCE IN THE CREATION, DEVELOPMENT, MANUFACTURE, SAFE HANDLING AND TRANSPORT OF ORGANOLITHIUMS. PAGE 11 OF 71 PRODUCT SPECIFICATIONS ORGANOMETALLICS AND REACTIVE SPECIALTY

15 PRODUCT SPECIFICATIONS FMC LITHIUM COMMERCIAL PRODUCTS More specific information on each of the products listed here, along with many other products that FMC Lithium offers can be found on our website at and on our product data sheets. PRODUCT SPECIFICS CAS EINECS MW CONC. WW% SOLVENT DENSITY g/ml 20 C MOLARITY 12 n-butyllithium, NBL, n-buli Clear, pale yellow to Hexanes yellow solution 23 Hexanes Hexanes Cyclohexanes Heptane Isopar C Reddish solution 20 Toluene sec-butyllithium, SBL, sec-buli Yellowish solution Hexanes Cyclohexanes 84%, Hexanes 4% tert-butyllithium, TBL, tert-buli Yellow solution Heptane Methyllithium, MeLi 9307 Contains 7% mole Cumene 83%, MgMe 2 as a stabilizer THF 14% n-hexyllithium, NHL, n-hxli Phenyllithium, PhLi Lithium diisopropylamide, LDA9500 Lithium hexamethyldisilazide, LHS, LiHMDS Lithium t-butoxide, LTB Clear, yellowish solution Dark red to brown solution Hexanes Dibutylether 80%, Biphenyl 2%, Benzene 0.5% Orange to claret solution* THF 26%, Heptane 28%, Ethylbenzene 13% Yellow to brown solution* Yellow to brown solution** THF 64%, Ethylbenzene 12% THF 81%, t-butanol 0.35% Lithium methoxide, LiOMe Pale yellow solution Methanol 90%, LiOH 0.07% Dibutylmagnesium, DBM, (n-bu)(sec-bu)mg Tri-t-butylphosphine, TTBP t-butyldimethylchlorosilane, TBSCl Contains 10% mole dioctylmagnesium avg. 14 Hexanes viscosity improver 14 Heptane Solid and higher concentrations available** Stability (nb. generates HCl in contact with moisture)** Toluene Solid 0.83 NA * Custom formulations available ** Solid and custom formulations available NA = not available ORGANOMETALLICS AND REACTIVE SPECIALTY PRODUCT SPECIFICATIONS COMMERCIAL PRODUCTS PAGE 12 OF 71

16 PRODUCT CONTAINER TYPES KILOGRAMS OF PRODUCT CONTAINED This represents only a sample of the packaging options that FMC offers. THERMAL STABILITY LOSS/ DAY AT 20 C: AT 40 C %ASSAY RECOMMENDED STORAGE TEMPERATURE C 20 (18 L) 100 (90 L) 420 (405 L) 2500 L (2250 L) L (16750 L) L (31500 L) 55 GAL DRUM :0.01* < NA :0.011* < NA 0.012:0.10* NA :0.011 < NA :0.011 < NA :0.011 < NA 0.015: NA 0.05:0.32* NA 0.05:0.32* NA :0.05 <15, max 150 days NA NA : for 60 days NA NA <0.001:<0.002 < NA 0.22: , max 150 days NA 0.10:0.65 < TS < OPT OPT OPT OPT TS < OPT OPT OPT OPT TS < OPT OPT OPT OPT TS < NA NA TS < NA NA TS < NA NA NA NA TS <20 Available in 13.5kg (net) polypropylene pails only *at 35 C at 15 C TS = Thermally stable. Must be protected fromair and/or moisture. Proper packaging and storage conditions are critical. NA = not available OPT = optional (available upon special request) PAGE 13 OF 71 COMMERCIAL PRODUCTS PRODUCT SPECIFICATIONS ORGANOMETALLICS AND REACTIVE SPECIALTY

17 LABORATORY 14 SAMPLING OBTAINING ANALYTICAL SAMPLES OF ORGANOMETALLIC AND REACTIVE ORGANIC COMPOUNDS FROM SHIPPING CONTAINERS IS A HAZARDOUS PROCEDURE TO BE PERFORMED ONLY BY THOSE WHO HAVE BEEN PROPERLY TRAINED. Samples should be collected in a suitable handling area by trained personnel wearing appropriate protective clothing and eye protection. A suitable fire extinguisher should be available in the event of spillage. Samples can be collected using a hypodermic method or proprietary sampling system. Samples can be stored in septum-sealed glass bottles that have been cleaned, oven-dried, cooled and flushed with a dry inert gas such as nitrogen or argon. A hypodermic sampling needle should be attached to the container or transfer line and the shipping vessel slightly pressurized with nitrogen or argon. The container discharge valve should be opened slowly to allow liquid to flow into the sample bottle through the sampling needle, while venting the bottle through another needle. Using these procedures, a preliminary sample should be taken to flush the transfer line prior to taking the analytical sample. More information on sampling and sample handling is given in the Shipping section, p. 30. ORGANOMETALLICS AND REACTIVE SPECIALTY LABORATORY SAMPLING PAGE 14 OF 71

18 15 THE TECHNIQUES AND PROCEDURES DISCUSSED IN THE ORGANOMETALLICS AND REACTIVE SPECIALTY ORGANICS SAFE HANDLING GUIDE SHOULD BE UTILIZED BY PROFESSIONALS TRAINED AND EXPERIENCED IN WORKING WITH THESE COMPOUNDS. SAFETY IS PRIORITY ONE AT FMC. HEALTH, SAFETY, SECURITY AND ENVIRONMENTAL (HSSE) PERFORMANCE ARE CORE VALUES OF FMC AND IS MANAGED AS AN INTEGRAL PART OF THE BUSINESS. PAGE 15 OF 71 SAMPLING LABORATORY ORGANOMETALLICS AND REACTIVE SPECIALTY

19 LABORATORY 16 ANALYTICAL METHODS Depending on the type of material, FMC Lithium uses various methods of analysis on organometallic and reactive organic products. For phosphines, the use of 31 P NMR, acid/ base titration, and/or gas chromatography are essential. There are several methods used to assay the alkyllithium products, including Gilman (double titration) method 1, the modified Watson-Eastham titration 2 and infrared spectroscopy (FTIR) 3. Acid/base titration is also used for the analysis of several alkoxide compounds. Products such as lithium hexamethyldisilazide (LHS) use the 1,3-diphenylacetone - p-tosylhydrazone (DPTH) titration 4 as its main method of analysis. The EDTA titration of magnesium using a specific ion electrode is used for several organometallic reagents. The magnesium concentration is determined via compleximetric titration with EDTA in an ammonia solution. The sample is hydrolyzed in water, neutralized with nitric acid and buffered at ph 10. The solution is then titrated with a standard solution of disodium ethylenediaminetetraacetic acid (EDTA) using a copper electrode. At the endpoint, the magnesium has been complexed with EDTA, releasing the copper EDTA complex. Free copper is then detected by the electrode. For additional information on this method, please contact FMC Lithium. 1 Gilman, Haubein, J. Am. Chem. Soc., 1944, 66, Waston, Estham, J. Organometallic Chem., 1967, 15, 9. 3 Hardwick, P., PharmaChem, 2002, 6, Lipton, Michael F., Sorensen, Charles M., Sadler, Alan C. and Shapiro, Robert H., J. Organometallic Chem., 1980, 186, 155. For metal hydrides, assay is determined via a reduction with iodine or by gas evolution. To determine via reduction with iodine, the sample is mixed with excess iodine, allowed to react, then the excess is determined by titration with sodium thiosulfate. To determine via gas evolution, the sample is reacted in water to evolve hydrogen which is collected and measured. For additional information on these methods, please contact FMC Lithium. SAFETY When properly handled, organometallics and reactive organics provide unique properties that allow for precise control and enhanced performance. Appropriate measures should be taken to avoid human exposure via ingestion, contact with skin or inhalation. Refer to specific toxicology information on the appropriate MSDS available at or by contacting FMC Lithium. HAZARDS OF ORGANOMETALLIC AND REACTIVE ORGANIC COMPOUNDS These compounds are highly reactive materials. There are three principle hazards associated with these compounds: corrosivity to the skin, flammability and, in certain instances, pyrophoricity. The inherent corrosive nature of all classes of organometallics and reactive organics can cause chemical and thermal burns upon exposure. These compounds themselves are flammable and are typically supplied in an organic solvent which exacerbates the flammability. For safety reasons, it should be assumed that all formulations of organometallic compounds are pyrophoric unless otherwise designated. Pyrophoricity is defined as the property of a material to spontaneously ignite on exposure to air, oxygen or moisture. According to this definition, it is possible for a diluted formulation to be non-pyrophoric. However, local evaporation of a solvent can occur where transfers are made by pressure with an inert gas such as nitrogen or argon, resulting in the product reaching a pyrophoric concentration. The solvent in the formulation also influences pyrophoricity. The lower the flashpoint of the solvent, the greater the risk of spontaneous ignition. Environmental factors in the laboratory are also contributors. Higher relative humidity and temperature may increase the risk of ignition. The rate of decomposition of certain organometallics is primarily impacted by the storage temperature. Higher temperatures typically accelerate decomposition. Since the assay of these reagents can decline with storage, it is good practice to verify the assay prior to usage in an experiment. Reactions involving organometallics and reactive organics are commonly high energy exothermic processes. The addition rates of reactants should always be closely controlled. Appropriate thermochemical studies should be carried out when scaling up processes. Again, adequate thermochemical data must be obtained when developing such processes. ORGANOMETALLICS AND REACTIVE SPECIALTY LABORATORY ANALYTICAL METHODS PAGE 16 OF 71

20 There are three principle hazards associated with organometallics and reactive organics: corrosivity to the skin, flammability and pyrophoricity. Before any laboratory experiment with an organometallic or reactive organic compound is conducted, appropriate planning should be performed to safeguard personnel and property from these hazards. Metal hydrides release flammable hydrogen gas when exposed to water, humid air or other proton sources. This hydrogen evolution can be dangerous, because of the chance for creating explosive mixtures with air and the potential for rapid pressure increases in closed systems. For these reasons, water or protic solvents must be rigorously excluded from all vessels and lines. Additional information about individual products is included on the product data sheets available at or by contacting FMC Lithium. PLANNING AN EXPERIMENT In spite of these hazards, the reactivity of these compounds may be successfully harnessed with proper planning. Precautions must be taken against the principle hazards of organometallic and reactive organic compounds: corrosivity to the skin, flammability and pyrophoricity. The material safety data sheet (MSDS) contains recommendations for the safe handling and storage of specific compounds. There are a number of circumstances that must be avoided when handling organometallic and reactive organic compounds in the laboratory: exposure to personnel, air, oxygen, moisture, water, heat, source of ignition (spark) and fuel. Consulting the FMC Lithium MSDS prior to the commencement of an experiment that utilizes these types of compounds is strongly recommended. The first consideration in planning an experiment is choosing the proper environment. To minimize personnel exposure, it is highly advisable to conduct the experiment in an efficient fume hood. Combustible materials, such as solvents, flammable chemicals (reagents or samples), paper or cloth should be removed from the hood prior to the experiment. The fume hood must be equipped with a source of inert gas, such as nitrogen or argon. A delivery system is required to distribute the inert gas to the reactor. Typically, nitrogen is available in several grades from the supplier. For general laboratory use, the maximum acceptable moisture content is 5 ppm, and the maximum acceptable oxygen content is 8 ppm. Argon must be utilized in reactions where lithium metal is a reactant. When catalyzed by moisture, nitrogen reacts exothermically with lithium metal to form lithium nitride (Li 3 N). The glassware employed in the reaction must be free of moisture and oxygen before introducing the organometallic or reactive organic compound. The proper personal protection equipment (PPE) for handling these compounds should also be used. If adequate ventilation is not available, then a suitable respirator to protect against organic vapors and mists should be worn. Chemical splash goggles with a full-face shield are required for eye protection. Contact your FMC Lithium representative for guidance on glove selection for specific products. Glove selection should be guided by chemical protection and in-use factors such as temperature, glove thickness, length, dexterity, cut and abrasion resistance, and grip. Also, proper safety footwear should be worn. Details are provided in the specific product MSDS. Suitable fire extinguishers should always be available. A dry powder fire extinguisher is recommended for organometallic fires. For these types of fires, it is imperative NOT to use fire extinguishers that contain water, carbon dioxide or halogenated hydrocarbons. Most organometallics react violently with these three classes of extinguishing agents. REFER TO THE APPROPRIATE FMC LITHIUM MSDS CONCERNING FIRE EXTINGUISHER RECOMMENDATIONS FOR YOUR SPECIFIC MATERIALS. 17 PAGE 17 OF 71 ANALYTICAL METHODS LABORATORY ORGANOMETALLICS AND REACTIVE SPECIALTY

21 LABORATORY SAFETY Ar or N 2 Ar or N 2 B D F J K H Ar or N 2 Ar or N 2 18 LABORATORY SET-UP A typical inerted reaction apparatus outfitted for cannula transfer is illustrated schematically in Figure 5.1. The reactor (E) is equipped with a mechanical stirrer (F), a pressure-equalizing addition funnel (G) with a septum (J), and a Claisen adapter (C) fitted with a thermometer (D) to measure internal temperature and a dry ice condenser (B). The inert gas line (argon or nitrogen) is attached to the outlet of the condenser (B), which is connected via a T fitting to a bubbler filled with mineral oil (A). In the event of partial vacuum, this bubbler monitors the positive flow of inert gas through the system and prevents the inflow of air into the reactor. A second inert gas line is employed for the reagent bottle of organometallic. The mineral oil bubbler (L) on this side has a clamp on the outlet to facilitate transfer via the cannula (H). A C E G I L M Figure 5.1 LABORATORY APPARATUS FOR CANNULA TRANSFER The reaction vessel (E) and the air and water sensitive reagent sample (I) should each be placed in a metal bowl. This serves as a catch pan for the reactive solution in the event either breaks. In addition, the metal bowl surrounding the reaction vessel can be employed to hold the cooling medium for a cryogenic reaction. This cooling medium should be a hydrocarbon that will not react with the reaction mixture (such as hexanes or heptane). More traditional cooling bath materials such as acetone or 2-propanol may react violently with organometallic and reactive organic solutions. A Mineral Oil Bubbler (Outlet) B Dry Ice Condenser C Claisen Adapter D Thermometer E Three-Neck Round Bottom Flask F Stir Shaft attached to a mechanical stirrer G Addition Funnel H Cannula I Air and Water Sensitive Reagent Sample J Septum K Glass Bottle L Mineral Oil Bubbler (Inlet) M Valve ORGANOMETALLICS AND REACTIVE SPECIALTY LABORATORY SAFETY PAGE 18 OF 71

22 Two basic techniques are utilized for the transfer of organometallic and reactive organic solutions in the laboratory syringe and cannula. TRANSFER TECHNIQUES Two basic techniques are utilized for the transfer of organic solutions in the laboratory syringe and cannula. The volume of the transferred solution determines which technique should be employed. The cannula technique 5 is ideal for transferring larger volumes. The cannula transfers the solution from the sample bottle to the reaction apparatus that has been purged and dried along with the other equipment prior to use. Inert gas (argon or nitrogen) drives the solution from the sample bottle through the cannula to the reaction apparatus. Solvent is then flushed through the cannula and it is removed. The laboratory apparatus for a cannula transfer is illustrated in Figure 5.1. DISPOSAL OF ORGANOMETALLIC COMPOUNDS Small residues of these compounds can be safely quenched in a fume hood. An inert solvent such as heptane should be used to dilute pyrophoric materials to less than 5 wt%. The solution should then be added via funnel to a well-stirred, 2-Molar solution of 2-propanol in heptane. The temperature of this quenched solution needs to be monitored with an internal thermometer and maintained at 50 C or below. This can be accomplished by controlling the feed rate of the organic solution or with an application of an external cooling bath of dry ice/heptane. The resultant solution of lithium isopropoxide in heptane can then be disposed with similar flammable, hazardous waste. Containers of organometallic reagents that are beyond their recommended storage retention period and conditions may have developed significant quantities of solids. These materials should be properly collected and sent out for disposal by an approved waste disposal route and method. This minimizes laboratory personnel s exposure to the hazards of quenching large volumes of organometallic compounds and their decomposition products. Small samples of metal hydride solutions should be sent to an approved waste handler. REFER TO THE APPROPRIATE PRODUCT DATA SHEETS FOR THERMAL STABILITY DATA AVAILABLE AT OR BY CONTACTING FMC LITHIUM. 19 The syringe technique is typically used for relatively small volumes of organometallic and reactive organic solutions (less than 50 ml). The technique is similar to the cannula technique, however, a dried syringe is used in place of the cannula. 5 Schwindeman, J. A., Woltermann, C. J., and Letchford, R. J., Safe Handling of Organometallic Compounds in the Laboratory, Chemical Health and Safety, 2002, 9, 3. PAGE 19 OF 71 SAFETY LABORATORY ORGANOMETALLICS AND REACTIVE SPECIALTY

23 SAFETY 20 HAZARDS DESPITE THE INHERENT HAZARDS OF THE MATERIAL, ORGANOMETALLIC AND REACTIVE ORGANIC COMPOUNDS HAVE BEEN HANDLED IN INDUSTRIAL ENVIRONMENTS FOR MANY YEARS. Carefully designed facilities, knowledge of proper handling techniques and thorough training of operations personnel using clearly written procedures will overcome these hazards. The hazards associated with the hydrocarbon carrier solvent should also be considered. For example, organometallics and reactive organics may be rendered non-pyrophoric when diluted with compatible hydrocarbons, however it is important to remember that the reactive component remains air and moisture sensitive under these conditions. It is important to refer to the appropriate product data sheet for carrier solvent information. Organometallics and reactive organics should always be handled in the same way as the formulated product stored and transferred in conventional chemical process equipment that has been designed to exclude air and moisture. Organometallics will react with water, oxygen, carbon dioxide and materials such as alcohols and carboxylic acids. Violent reactions can also occur with certain halogenated hydrocarbons such as carbon tetrachloride or chloroform. The complete combustion of organometallics results in the formation of metal oxide, carbon dioxide and water. If the combustion is incomplete, carbon monoxide can be generated. Reactive organics such as phosphines may react violently with oxygen and other chemicals and should be handled with the same degree of care as organometallics. Metal hydrides release flammable hydrogen gas when exposed to water, humid air or other proton sources. This hydrogen evolution can be dangerous because of the chance for creating explosive mixtures with air and the potential for rapid pressure increases in closed systems. For these reasons, water or protic solvents must be rigorously excluded from all vessels and lines. For more specific product information, please refer to the appropriate product data sheet and/ or material safety data sheet that can be found at Customers may also contact us directly concerning any questions that may exist pertaining to their particular requirements. ORGANOMETALLICS AND REACTIVE SPECIALTY SAFETY HAZARDS PAGE 20 OF 71

24 21 STRICT ADHERENCE TO SAFETY PROCEDURES GREATLY REDUCES THE RISK OF FIRE. CONTROL ROOM OPERATORS MONITOR CONDITIONS IN OUR MANUFACTURING FACILITY TO MAINTAIN THE SAFETY OF FMC PERSONNEL AND EQUIPMENT. THE TECHNIQUES AND PROCEDURES DISCUSSED IN THE ORGANOMETALLICS AND REACTIVE SPECIALTY ORGANICS SAFE HANDLING GUIDE SHOULD BE UTILIZED BY PROFESSIONALS TRAINED AND EXPERIENCED IN WORKING WITH THESE COMPOUNDS. PAGE 21 OF 71 HAZARDS SAFETY ORGANOMETALLICS AND REACTIVE SPECIALTY

25 SAFETY 22 SAFETY FMC Lithium highly values safety and is pleased to share its expertise in the handling of organometallic and reactive organic compounds. In keeping with our commitment to Responsible Care, we provide technical assistance to customers including: safety guides, brochures, CDs/DVDs and online information consultation on facility design demonstrations of safe use, handling and control of organometallics and reactive organics on-site assistance and advice regarding unloading procedures FIRST AID Organometallics, reactive organics and their solutions can cause severe burns. Many organometallics react quickly with body moisture, giving off heat and producing caustic by-products. Auto-ignition is also possible. Concentrated solutions react immediately with moisture on the skin or in the eye to produce severe thermal and chemical burns. Diluted solutions cause less harmful burns, but should be treated with the same precautions as any thermal or chemical burn. The solvent component may affect the skin or eye, causing thermal burns if ignition occurs. Complete first aid equipment should be stocked in the handling area. Fire blankets and quick-drench eyewash safety showers should be available. All injuries from organometallic and reactive organic exposure should be given appropriate medical attention. Guidance on treatment of exposure is given in the MSDS and is summarized here. In all cases, medical advice should be sought. EYE CONTACT (EXTREMELY SERIOUS) Treatment Summary» Flush with plenty of water: 15 minutes» Lift upper / lower lids intermittently» Seek medical attention immediately SKIN CONTACT Treatment Summary» Flush with plenty of water: 15 minutes» Remove contaminated clothing» Wash clothing with soap and water» Seek medical attention immediately INHALATION Treatment Summary» Escape to fresh air» Give artificial respiration if breathing stops» Seek medical attention immediately, especially if breathing discomfort occurs PLEASE SEE THE APPROPRIATE FMC LITHIUM MSDS FOR ADVICE AND ASSISTANCE. THE TECHNIQUES AND PROCEDURES DISCUSSED IN THE ORGANOMETALLICS AND REACTIVE SPECIALTY ORGANICS SAFE HANDLING GUIDE SHOULD BE UTILIZED BY PROFESSIONALS TRAINED AND EXPERIENCED IN WORKING WITH THESE COMPOUNDS. ORGANOMETALLICS AND REACTIVE SPECIALTY SAFETY SAFETY PAGE 22 OF 71

26 In fighting chemical fires, there are three primary concerns: to stop any flow of fuel to the fire, isolate and extinguish the blaze and avoid chemical exposure. PROTECTIVE EQUIPMENT Engineering protection, in particular safe design should always be the primary protection against chemical exposure. Personal protection equipment (PPE) should be used to reduce the risk of exposure, but should never be the sole method of protection. If adequate ventilation is not available, then a suitable respirator to protect against organic vapors and mists should be worn. Chemical splash goggles with a full-face shield are required for eye protection. Contact your FMC Lithium representative for guidance on glove selection for specific products. Glove selection should be guided by chemical protection and in-use factors such as temperature, glove thickness, length, dexterity, cut and abrasion resistance, and grip. Proper safety footwear should be worn. Immediate access should be available to quick-drench eyewash and safety showers. Further details are provided in the appropriate MSDS, available from FMC Lithium. More detailed advice on protective clothing for unloading and sampling is given in the Shipping section, p. 30. PLANT For plant operations where large quantities of organometallics and reactive organics are being handled, body protection is provided by a long-sleeved, two-piece suit made of PVC laminate, Nomex or other suitable material. Suitable gloves and safety footwear should also be worn. Minimum head protection should include safety glasses, face shield and hard hat. All protective clothing and equipment should allow freedom of movement and be easily shed in case of spills onto the clothing. FIRE FIGHTING Strict adherence to safety procedures reduces the possibility of fire, but the risk is ever present. Organometallic and reactive organic fires give noxious fumes that induce choking. Full personal protection equipment (PPE) including self-contained breathing apparatus is required for fire fighting in enclosed areas. In fighting chemical fires, there are three primary concerns: to stop any flow of fuel to the fire, isolate and extinguish the blaze and avoid chemical exposure. Should a fire occur, stop the flow of fuel to the fire by closing discharge valves and depressurizing containment vessels. Immediate action should be taken to localize and confine the fire. Any unaffected containers of flammable materials in the area should be moved to safety. Dry chemical fire extinguishants (Ansul, Purple-K, Plus Fifty B or Monnex ) are preferred for fighting organometallic and reactive organic fires. Fires should be smothered with powder, beginning at the periphery and working to the inside. Even after the flames are extinguished, reactive materials will remain for some time. Allow a sufficient interval for complete oxidation before cleanup. Disturbing the powder crust prematurely may cause smoldering and re-ignition. Solvent vapors from hot or smoldering spills can reignite. Proper ventilation is very important. It is imperative NOT to use extinguishers containing carbon dioxide, chlorinated hydrocarbons or water on organometallic fires. Spilled metal hydride solutions should be covered with solid fire extinguishant, such as limestone, and quenched or disposed according to local regulations. Customers should address fire suppression in their own facilities by consulting their safety and engineering staffs, as well as local fire safety authorities to best protect a specific facility and its employees. 23 PAGE 23 OF 71 PAGE CATALOG 23 OF SUBSECTION 71 FIRE FIGHTING CATALOG SECTION SAFETY ORGANOMETALLICS SPECIALTY ORGANICS AND SAFE REACTIVE HANDLING SPECIALTY GUIDE

27 DESIGN 24 OVERVIEW THIS SECTION PROVIDES GUIDELINES FOR THE DESIGN OF ORGANOMETALLIC AND REACTIVE ORGANIC COMPOUNDS HANDLING FACILITIES AND INCLUDES EQUIPMENT RECOMMENDATIONS BASED ON MANY YEARS OF OPERATIONAL EXPERIENCE. The design of organometallic and reactive organic compounds handling facilities must account for the highly reactive nature and properties of the materials. The pyrophoric nature of some of the solutions presents different hazards than those of common hydrocarbons. ORGANOMETALLICS AND REACTIVE SPECIALTY DESIGN OVERVIEW PAGE 24 OF 71

28 25 PROPERLY DESIGNED STORAGE AND HANDLING FACILITIES CAN REDUCE THE RISK OF AN ORGANOMETALLIC AND REACTIVE ORGANIC FIRE AND SUBSEQUENT DAMAGE. FMC LITHIUM S TANK FARMS ARE DESIGNED TO ADDRESS THE SAFETY OF PERSONNEL AND THE SURROUNDING ENVIRONMENT. THE TECHNIQUES AND PROCEDURES DISCUSSED IN THE ORGANOMETALLICS AND REACTIVE SPECIALTY SHOULD BE UTILIZED BY PROFESSIONALS TRAINED AND EXPERIENCED IN WORKING WITH THESE COMPOUNDS. PAGE 25 OF 71 OVERVIEW DESIGN ORGANOMETALLICS AND REACTIVE SPECIALTY

29 DESIGN STORAGE AND HANDLING EQUIPMENT DESIGN 26 Properly designed storage and handling facilities can significantly reduce the potential of a fire and subsequent damage. Storage facilities should be isolated from the main building and offices. Facilities should be sheltered and well ventilated. Ideally, these facilities should have fixed or mobile fire extinguishing systems, as well as containment and drainage to reduce the risk of fire propagation. All vessels, piping, valves and seals should be constructed of suitable materials that are capable of localizing a potential fire. Such action to restrict damage will allow rapid and effective repairs. Containers should be inspected upon arrival to identify damage that may have occurred during transit. Full and empty organometallic and reactive organic containers should be stored in an environment appropriate to the specific product to prevent contamination or degradation. Storage areas may need to be temperature controlled, well ventilated, and/or diked as needed. Outdoor bulk storage tanks should be located away from main facilities and separated from one another by a distance sufficient to prevent any fire from spreading to adjacent tanks. Each storage tank should be cordoned by a robust containment system, high enough to contain the largest possible spill. The ground should be sloped to carry liquid spillage away from tanks and staff. Like storage areas, handling areas should be isolated and equipped with suitable fixed or mobile fire protection. Handling areas and laboratories should also be well-ventilated to dissipate solvent vapors. Please refer to the specific product data sheet and/or MSDS for guidance and recommendations. Provision for maintenance and inspection of equipment and instruments should be implemented into the design at an early stage. More detailed information on the design of handling and storage facilities is available by contacting FMC Lithium. LEVELS OF PROTECTION Systems for handling organometallics and reactive organics should use several diverse and independent levels of protection. Protective systems should be designed to fail safe and, whenever possible, to remain effective in the event of power failure. Appropriate levels of redundancy and the role of preventative maintenance systems should be included. Administrative protections (i.e. those based upon human actions) should not be relied upon to offer significant levels of protection. The greatest risk reductions are achieved by implementing automated systems and equipment that prevent human error from causing an incident. The simple use of air-driven actuated valves that close upon alarm or loss of air pressure can significantly mitigate the impact of an incident. For example, the use of plastic (nylon) air lines that melt rapidly in the presence of flame or flametriggered isolation devices should be considered. FMC Lithium also recommends the use of quantitative or semi-quantitative methods to assess the reliability of designs for organometallic and reactive organic installations. MATERIALS OF CONSTRUCTION Organometallic and reactive organic compounds are not directly reactive with most materials used in the routine construction of a chemical plant. If a leak occurs, these compounds will generate heat in significant quantities. This fact should be taken into consideration when initiating construction. ORGANOMETALLICS AND REACTIVE SPECIALTY DESIGN STORAGE AND HANDLING PAGE 26 OF 71

30 Systems for handling organometallics and reactive organics should use several diverse and independent levels of protection. Protective systems should be designed to fail safe and to remain effective in the event of power failure. As a result, materials like PTFE or plastics that will deform or be destroyed by extreme heat should only be used in situations where suitable design allowance can be made. For example, installations using PTFE hoses should be designed to allow the hose to be pressure tested before use and to ensure remote isolation can be achieved, preferably by automatic means in the event of a leak. should be checked for quality by methods that are accurate, specific and reliable in the operating environment. Organometallics are often very reactive and therefore, compatibility with other reagents used in the plant should be considered. Opening the wrong valve or improper cleaning may lead to an unexpected exothermic reaction. 27 PTFE hoses should always be subject to routine preventative inspection. The choice of a gasket material (e.g. PTFE, Viton ) will be dictated by its compatibility with the organic solvents present. In the event of a leak or fire, gasket material may be destroyed, allowing the leak to spread. A fire may therefore damage the integrity of other local process lines. The use of steel/graphite gaskets, which retain their efficacy in the event of fire, is recommended. Phosphines can degrade plastics. Materials of construction should be determined to be compatible prior to use. Most ferrous materials (iron and steel) will have surface oxide layers that also contain absorbed oxygen. Upon initial contact, organometallics and reactive organics react by generating heat. When commissioning storage facilities, it is advisable to first flush the equipment with solvent and then with a diluted solution of the compound to achieve this pickling stage in a controlled manner. Aluminium should not be used as a material of construction in contact with lithium or other metal alkoxide solutions in alcohol, since aluminum reacts with the alcohol to form aluminum alkoxide and hydrogen. Over time, enough hydrogen pressure can be generated to cause rupture of the vessel. For this reason, aluminum should never be used as a material of construction for organometallic solutions in alcohols. Glass components, in particular sight glasses always present a risk of breakage and subsequent leakage. If such components are to be used, it is recommended that each example should be subjected to a rigorous design evaluation to assess the risks presented and the protective systems that should be provided, if an alternative cannot be found. CONTAMINATION Contamination of equipment that handles organometallic and reactive organic compounds should be considered at the design stage. Moisture and oxygen are ever-present contaminants that, in sufficient quantities can cause violent reactions. Process gases and solvents PIPEWORK Pipework should be designed with minimum flanges as they are possible sources of leakage. Judgment must be exercised to allow suitable scope for maintenance work, including in-situ cleaning and decontamination. Precautions should be taken to avoid lines being left fully flooded with liquid, as this can result in leaks due to thermal expansion. Connection to reactive services should be avoided and the risk of contamination considered. As with any flooded liquid system, thermal expansion, driven by sunlight or other incidental heat can generate significant pressures. Lines carrying organometallic and reactive organic solutions should be designed to ensure that they are fully-draining and cannot be left flooded and locked-in. If this is not possible, then designed vapor traps should be included in the pipework to prevent unacceptable overpressures from occurring. More detailed information on the design of handling and storage facilities is available by contacting FMC Lithium. PAGE 27 OF 71 EQUIPMENT DESIGN DESIGN ORGANOMETALLICS AND REACTIVE SPECIALTY

31 DESIGN 28 EQUIPMENT DESIGN PUMPS One of the greatest dangers of handling organometallics and reactive organics is loss of containment. If centrifugal pumps are used, the sealing system should be carefully evaluated as protective systems against leakage may be required. Protective systems should be installed on the seal assembly. Magnetically-driven or canned pumps are suitable, but protection against dry running or overheating is required. It should be noted that some alkyllithiums decompose to produce solid lithium hydride if overheated. This may affect magnetically-driven pumps. FLEXIBLE HOSES Flexible hoses should be designed to meet at least the same pressure standards as associated pipework or vessels. If they are routinely disconnected, the facility design should allow for them to be inspected and pressure tested regularly or before each usage. Such hoses must be monitored for damage or deterioration and changed regularly as part of a routine preventative maintenance program. FIRE PROTECTION The consequences of fire should always be considered in the design of any installation handling organometallics and reactive organics. Equipment should be suitably segregated and associated systems, such as instrument cabling should be safely located in such a manner that damage can be easily repaired. Suitable systems, such as thermal imaging, UV detection, or more routine methods like particulate or ionizing detectors should be used to give early warning of leaks or fire. If the risk of fire is high and the consequences of such an event would be detrimental, then fire protection should be used. This may be in the form of protective cladding and/or fixed extinguishing systems. The use of water sprinkler systems on organometallic and reactive organic commercial installations must be carefully evaluated as the presence of water may cause other hazards. More details on fire protection are given in the Safety section, p. 20 or by contacting FMC Lithium. INSTRUMENTATION Mass flow meters are effective with organometallic solutions. However, care must be taken at the design stage to ensure that material is not left stagnant for long periods of time. Routine thermal decomposition could lead to solids formation which may affect the accuracy of the instrument. Vibration tuning fork level switches are effective as independent high level trips that minimize risk in the event of power failure. STORAGE FACILITIES Organometallic and reactive organic solution storage vessels should be separately contained in a bund or dike capable of holding at least 110% of the volume of the tank. Ideally, the bund should allow for any leakage to be directed away from the tank into a separate pit to avoid flame impingement on the tank or its supports. Fire protective insulation should be used. If refrigeration is used, the cooling fluids should be compatible to avoid any reaction taking place in the event of leakage. ORGANOMETALLICS AND REACTIVE SPECIALTY DESIGN EQUIPMENT DESIGN PAGE 28 OF 71

32 All personnel should be fully trained in both operations and fire-fighting techniques. All equipment should be subject to regular preventative maintenance. Water, glycol and brines are not considered suitable cooling media for organometallics and some reactive organics. The vessel should be maintained with an inert atmosphere of nitrogen or argon and protected against local pressure changes. External fire protection in the form of enhanced lagging should be considered to protect both the equipment and structural steel in the event of a prolonged fire. Spray-applied, concrete based systems provide good fire protection, but may be difficult to inspect for preventative maintenance purposes. UNLOADING FACILITIES Loss of containment is a major concern when handling organometallics and reactive organics. The unloading of these types of materials should therefore be subject to considerable design scrutiny. The number of operations should be minimized by selecting the most suitable concentration and pack size available. Personnel should be fully trained in both operations and fire-fighting techniques. The aforementioned design provisions should be considered with particular notice to the details about pipework, gaskets and flexible hose design. NITROGEN BLANKETING, PURGING AND VENTING SYSTEM Nitrogen should be piped to all lines and tanks to blanket and purge the system. A supply of dry nitrogen should be maintained for blanketing, purging and displacement of organometallics and reactive organics. The nitrogen that is utilized should contain less than 5 ppm of moisture and less than 8 ppm of oxygen. Continuous purging of organometallic and reactive organic storage tanks is not recommended. A pad of about 5 psig (3 bars) of nitrogen should be applied and the tank should be blocked when not in service. Normal process venting and excess nitrogen from blanketing and purging should be directed through a seal tank and flame arrestor to vent. The emergency relief system should vent directly to the appropriate dry emergency flare header or predetermined air space. Also, the vent system should be designed to drain any liquids condensed in the system toward the vent rather than backward into the system. MAINTENANCE PROCEDURES Where possible, installations for handling organometallics and reactive organics should be designed to minimize maintenance. Preparations should be made to flush pipework and equipment with solvent and/or mineral oil, as well as to sample and analyze for residual activity before containment is broken. In areas of high ambient temperature, lines should be lagged to minimize degradation. All equipment should be subject to regular preventative maintenance. DISPOSAL Disposal should be handled according to local and federal laws and regulations. More detailed information on the design of handling and storage facilities is available by contacting FMC Lithium. 29 PAGE 29 OF 71 EQUIPMENT DESIGN DESIGN ORGANOMETALLICS AND REACTIVE SPECIALTY

33 SHIPPING 30 TRANSPORT CONTAINERS ORGANOMETALLICS AND REACTIVE ORGANICS ARE SHIPPED IN A VARIETY OF CONTAINERS DEPENDING ON THE NEEDS OF THE CUSTOMER. SIZES RANGE FROM LABORATORY BOTTLES TO BULK TRAILERS AND TANK CARS. Transport regulations require that organometallic cylinders be filled to no more than 90% of capacity. The cylinders may arrive slightly pressurized with dry nitrogen or argon and are equipped with a dip tube for pressure unloading with dry inert gas. UN rated drums are nitrogen purged before and during filling. Glass containers can be fitted with a septum that allows the air sensitive products to be removed by syringe. Detailed sampling procedures are provided in Laboratory, p. 18 and Unloading & Sampling sections, p. 58. Design, construction and maintenance of shipping containers are based on International Maritime Dangerous Goods (IMDG) code, US Department of Transportation (DOT) and European Road and Rail (ADR/RID) regulations as prescribed for the shipment of spontaneously combustible, flammable and dangerous when wet liquids. ISO containers and when applicable, smaller portable tanks must also meet the standards of the International Maritime Organization (IMO), the International Standards Organization (ISO), the International Convention for Safe Containers (CSC) and the International Union of Railways (UIC). In addition to periodic testing performed in accordance with these regulations, containers and all valves and fittings are also examined prior to each shipment. Organometallic and reactive organic solutions are generally classified for transport as one or more of the following: > Class 4.2 Substances liable to spontaneously combust > Class 4.3 Substances which, in contact with water, emit flammable gases > Class 8 Corrosive substances > Class 3 Flammable substances Specific details, UN numbers and proper shipping names for individual organometallics and reactive organics can be found in the relevant MSDS at Refer to the appropriate product data sheets for available packaging configurations located on ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAGE 30 OF 71

34 31 ALL CONTAINERS, VALVES AND FITTINGS ARE EXAMINED PRIOR TO EACH SHIPMENT AND ALSO PERIODICALLY TESTED. ALL TRANSPORT CONTAINERS, INCLUDING FMC S 30,000 LITER TANK TRUCKS HAVE PRESSURE RELIEF DEVICES. THE TECHNIQUES AND PROCEDURES DISCUSSED IN THE ORGANOMETALLICS AND REACTIVE SPECIALTY ORGANICS SAFE HANDLING GUIDE SHOULD BE UTILIZED BY PROFESSIONALS TRAINED AND EXPERIENCED IN WORKING WITH THESE COMPOUNDS. PAGE 31 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

35 SHIPPING PLEASE CONTACT FMC LITHIUM FOR REQUIREMENTS RELATED TO YOUR PARTICULAR SAMPLE, GEOGRAPHY, AND SHIPPING REGULATIONS. 32 ORGANOMETALLICS AND REACTIVE ORGANICS SAMPLE REQUEST PACKAGING OPTIONS SPECIAL CYLINDER INDEX 125 ml Bottle 500 ml Bottle 1 L Bottle 5.0 gal Metal Pail 6.5 gal Plastic Pail Type 5 Cylinder Type 10 Cylinder GLASS SAMPLE BOTTLES Page 34 METAL PAIL Page 36 LAB PACK Page PLASTIC PAIL Page 36 ORGANOMETALLICS AND REACTIVE ORGANICS REGIONAL STANDARD PACKAGING OPTIONS NAFTA EUROPE JAPAN ASIA 55 Gallon Drum x x x x Type 20 Cylinder x x x x Type 100 Cylinder x x x x Type 420 Cylinder x x x Type 480 Cylinder x x Liter ISO x x x x Liter Tank Truck x TYPE 5 Page 38 TYPE 10 Page 39 CUSTOM PACKAGING OPTIONS ARE AVAILABLE UPON REQUEST. PLEASE CONTACT FMC LITHIUM CONCERNING YOUR SPECIFIC ORGANOMETALLICS AND REACTIVE ORGANICS PACKAGING REQUIREMENTS. ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS DETAILS PAGE 32 OF 71

36 STANDARD CYLINDER INDEX APPLICABLE VALVE INDEX GALLON DRUM Page 37 TYPE 20 Page 40 TYPE 100 Page 41 GAS VALVE: SINGLE PORT CYLINDERS Page 48 GAS VALVE: DUAL PORT CYLINDERS Page 49 TYPE 420 Page 42 TYPE 480 Page 43 DISCHARGE VALVE: POYNTON Page 50 DISCHARGE VALVE: CONBRACO Page LITER ISO Page 44 AVERY HARDOLL COUPLINGS Page LITER TANK TRUCK Page 46 In the pages that follow, typical tare and gross weights are given for different pack sizes. The weights are affected by cylinder type, valving, product solvent, and product. PAGE 33 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

37 LAB PACK 125ML BOTTLE SPECIFICATIONS» 125 ml narrow mouth glass bottle with Teflon liner in cap, overpacked in can and box, UN certified 500ML BOTTLE SPECIFICATIONS» 500 ml narrow mouth glass bottle with Teflon liner in cap, overpacked in can and box, UN certified 34 LAB PACK SPECIFICATIONS» 125 ml Bottle» 500 ml Bottle» 1 L Bottle» Gallon metal container» 7" x 24" 4mil Barrier Bag» 7" x 7" Vermiculite Pillow» 10" x 18" Vermiculite Pillow» Loose Vermiculite» Corrugated Insert» Corrugated Outer Box Complete Lab Pack instructions are available from FMC Lithium upon request 1L BOTTLE SPECIFICATIONS» 1 L narrow mouth glass bottle with Teflon liner in cap, overpacked in can and box, UN certified GALLON METAL CONTAINER SPECIFICATIONS» Gallon metal container with lid and arm lock ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAGE 34 OF 71

38 LAB PACK 125ML BOTTLE 500ML BOTTLE 1L BOTTLE TWIST TIE 7" x 24" 4 MIL BARRIER BAG LOOSE VERMICULITE 35 7" x 7" VERMICULITE PILLOW 10" x 18" VERMICULITE PILLOW ARM LOCK LID GALLON METAL CONTAINER CORRUGATED INSERT CORRUGATED OUTER BOX COMPLETE LAB PACK INSTRUCTIONS ARE AVAILABLE FROM FMC LITHIUM UPON REQUEST. PAGE 35 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

39 PLASTIC PAIL AND METAL PAIL METAL PAIL mm D x mm H 11 3/4" D x 13 3/4" H Crimped top PLASTIC PAIL 317.5mm D x 469.9mm H 12 1/2" D x 18 1/2" H Plastic safety ratchet lock 36 METAL PAIL SPECIFICATIONS» 5.0 gal black, open head steel pail, 24 GA body, 24 GA bottom, 20 GA top, g108 gasket in top, cover lugs crimped at 90 degrees» Each pail UN approved for the material it contains PLASTIC PAIL SPECIFICATIONS» 6.5 gal life latch white pail and cover w/gasket» Red safety ratchet lock on lid to keep the cover on the pail securely» Each pail UN approved for the material it contains Lid Red safety ratchet lock on lid to keep the cover on the pail securely ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAGE 36 OF 71

40 55 GALLON DRUM " Openings as specified on order 11" 11/16 33" 1/16 I.D. 3/4" Tri-sure flange/plug 34" 3/8 22" 1/2 I.D. 11" 11/16 1/2" 23" 19/32 I.D. 11" 11/16 5/8" HEIGHT DIMENSIONS +/- 1/8" ALL OTHER DIMENSIONS +/- 1/16" 22" 1/2 2" Tri-sure flange/plug SPECIFICATIONS» Maximum shipping volume: 54 gallons, liters» Typical tare weight: 41.9 lbs» Drums are selected as appropriate to the service use and UN approved for the material it contains» Must ship at 100% of maximum fill volume STANDARD CONFIGURATION» Small bung: 0.75" NPT pipe fitting» Large bung: 2" NPT pipe fitting 37 PACK TYPE MAX. FILL VOLUME GALLONS LITERS 55 Gallon Drum CONSTRUCTION 1.1mm Nominal thickness cover 1.04mm Min., 1.1 mm nominal thickness bottom & body 1.04mm Min. welded side seam; round (triple) seam top & bottom chime; two expanded rolling hoops 2" & 3/4" Tri-sure flanges, plated w/4s gaskets (epdm/black buna) or approved equivalent Color Drum top, body & bottom painted white (ral 7047) PAGE 37 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

41 TYPE 5 CYLINDER 76.2mm 3" Outage 38 SPECIFICATIONS» Maximum shipping volume: 5 liters» Typical tare weight: 5 kg» Typical gross weight: 9 kg Can ship up to maximum fill volume with no minimum volume required 304.8mm mm 12" + 1/4" mm mm 8 5/8" + 1/4" STANDARD VALVE CONFIGURATION» Single port: gas pattern valve with dual gas inlet and product outlet 165.1mm 6.5" O.D. Fusible Plug Nitrogen In 203.2mm 8" O.D. Superior Valve Product Out 15 Direction of valve outlet VALVE PACK TYPE MAX. FILL VOLUME LITERS Type 5 5 PAGE 48 ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAGE 38 OF 71

42 TYPE 10 CYLINDER 91.44mm 3.6" Outage mm mm 17 5/16" + 1/4" mm mm 13 3/4" + 1/4" SPECIFICATIONS» Maximum shipping volume: 9.5 liters» Typical tare weight: 9.5 kg» Typical gross weight: 15 kg Can ship up to maximum fill volume with no minimum volume required 39 STANDARD VALVE CONFIGURATION» Single port: gas pattern valve with dual gas inlet and product outlet mm 7 1/4" O.D. Fusible Plug Nitrogen In mm 8 7/8" O.D. Superior Valve Product Out 15 Direction of valve outlet VALVE PACK TYPE MAX. FILL VOLUME LITERS Type PAGE 48 PAGE 39 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

43 TYPE 20 CYLINDER Protective Cowl 40 SPECIFICATIONS» Maximum shipping volume: 18 liters» Typical tare weight: 10 kg» Typical gross weight: 22 kg Can ship up to maximum fill volume with no minimum volume required 310mm 12.09" 470mm 18.33" Overall Height STANDARD VALVE CONFIGURATION» Single port: gas pattern valve with dual gas inlet and product outlet Superior Valve Product Out Nitrogen In UNLOADING For unloading information, please see valve information on page 48. Also note, that it is necessary to vent the cylinder and apply argon or nitrogen pressure, approximately psi through the product outlet valve in order to transfer. If you experience any difficulties, please contact FMC Lithium sales service for more information. Fusible Plug VALVE PACK TYPE MAX. FILL VOLUME LITERS Type PAGE 48 ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAGE 40 OF 71

44 TYPE 100 CYLINDER Superior Valve Product Out 368.3mm 14 1/2" Nitrogen In Fusible Plug SPECIFICATIONS» Maximum shipping volume: 90 liters» Typical tare weight: 36 kg» Typical gross weight: 104 kg Can ship up to maximum fill volume with no minimum volume required STANDARD VALVE CONFIGURATION» Single port: gas pattern valve with dual gas inlet and product outlet mm 49 15/16" w/cap Installed UNLOADING For unloading information, please see valve information on page 48. Also note, that it is necessary to vent the cylinder and apply argon or nitrogen pressure, approximately psi through the product outlet valve in order to transfer. If you experience any difficulties, please contact FMC Lithium sales service for more information mm 14" OD VALVE PACK TYPE MAX. FILL VOLUME LITERS Type PAGE 48 PAGE 41 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

45 TYPE 420 CYLINDER Heat Fusible Relief Plug Superior Valve Poynton Valve Superior Vent/Pressure Valve Fitted with Protection Plug Pressure Vent Connection 1/2" NPT Left Hand Thread Superior Product Valve Fitted with Protection Plug Product Connection 1/2" NPT Left Hand Thread 42 SPECIFICATIONS» Maximum shipping volume: 405 liters» Typical tare weight: 250 kg» Typical gross weight: 530 kg Can ship up to maximum fill volume with no minimum volume required STANDARD VALVE CONFIGURATION» Dual port: gas pattern valve for vent and gas pattern valve for discharge Hinged Cover 345 I.D. of Cowl VIEW IN DIRECTION OF ARROW - A A Superior Valve Conbraco Valve Lifting Lugs Valve Protection Cowl 762mm 29.72" 1575mm 61.43" Typical 400mm 15.6"CTRS 250mm x 150mm 9.75" x 5.85" Rectangular Hollow Sections VALVES PACK TYPE MAX. FILL VOLUME LITERS Type PAGE 49 PAGE 50 PAGE 52 ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAGE 42 OF 71

46 TYPE 480 CYLINDER cm 92" SPECIFICATIONS» Maximum shipping volume: 1880 liters» Typical tare weight: 1000 kg» Typical gross weight: 2150 kg Can ship up to maximum fill volume with no minimum volume required cm 42" STANDARD VALVE CONFIGURATION» Dual port: ball valve for vent and ball valve for discharge UNLOADING Check the cowling for any moisture or water prior to initiating the unloading process. This area should be dry cm 10 1/4" PACK TYPE MAX. FILL VOLUME LITERS Type PAGE 43 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

47 LITER ISO 44 SPECIFICATIONS:» Shipping volume: liters» Typical tare weight: 7.5 t refrigerated, 7.0 t insulated, 6.5 t uninsulated» Typical gross weight: 20.5 t refrigerated, 20 t insulated, 19.5 t uninsulated Must ship from % of maximum fill volume Walkway C Products and their applicable international transport regulations determine the type of ISO selected for shipment STANDARD VALVE CONFIGURATIONS:» Vent and discharge - flanged» Vent and discharge - Avery Hardoll coupling D B A All top fitting protection boxes have hinged covers 6058mm " Rear 2591mm " 2438mm 95.08" ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAGE 44 OF 71

48 LITER ISO PACK TYPE MAX. FILL VOLUME LITERS L ISO L ISO DESIGN CRITERIA FOR L ISO Maximum Gross Weight kg Tare Weight 6000 kg (EST) Design M.A.W.P BAR Test Pressure 10 BAR External Design Pressure 1 BAR Design Temperature -20 C to 100 C Pressure Vessel Code ASME VIII DIV Equivalent THK mm M.S. US DOT 49 CFR ADR Calculation 21 BAR Pressure Material Vessel: SA Shell: 10.0mm Ends: 12.0mm Approvals ADR/RID, IMO1, IM101, AAR600, TC, CSC, TIR, UIC & LLOYDS LIST OF CONNECTIONS REF SIZE DESCRIPTION A 3.12"/80mm Product Discharge and Fill B 1.56"/40mm Vent Nitrogen C 0.975"/25mm Pressure Indicator D 3.12"/80mm Pressure Relief and Rupture Disk 45 PAGE 45 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

49 30000 LITER TANK TRUCK 46 SPECIFICATIONS:» Shipping volume: liters max.» Typical tare weight: 10 t» Typical gross weight: 30 t Baffled. Can ship up to maximum fill volume with no minimum volume required cm 8' STANDARD VALVE CONFIGURATIONS:» Liquid outlet: 2" fire safe ball valve / 2" ANSI 300# flange» Vent outlet: 1 1/4" fire safe ball valve / 11/4" ANSI 300# flange» Safety feature: Fisher express flow valve / emergency release handles» Rear Valves (Top offloading) Elevation: 8'-10' 317.5cm 10'-5" Access Platform Ladder 5.08cm 2" Apollo Ball Valve 1.27cm 1/2" Apollo Ball Valve (Plugged) 3.18cm 1 1/4" Apollo Ball Valve 1.27cm 1/2" Apollo Ball Valve (Plugged) 5.08cm 2" 300# Blind FLG. R.F. F&D cm 1 1/2" 300# Blind FLG. R.F. F&D 1 LIQUID VALVE 2 VAPOR VALVE ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAGE 46 OF 71

50 30000 LITER TANK TRUCK cm to cm 32'-5" to 33'-8" 200.7cm 84" I.D cm 10' 6" 45.72cm 1' 6" Spare Tire Carrier 1 2 See Detail PACK TYPE MAX. FILL VOLUME LITERS L Tank Truck PAGE 47 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

51 GAS VALVE: SINGLE PORT CYLINDERS IN-LINE ARRANGEMENT Safety lug (g) 1/4 BSP remove to attach gas line Inert Gas Valve B Main Valve A 0.885" 14NGO-LH Internal Left-Hand Thread 1/4 BSP 48 TECHNICAL AND DIMENSIONAL ILLUSTRATION» Superior valve» Standard compressed gas valve (CGA)» Valve illustration shown as shipped on Type 20 cylinders from US locations due to Department of Transportation regulations. Customer must remove the fusible safety plug and add fittings and valve for addition and regulation of the dry inert gas. 1/4 BSP TEE Safety Lug (F) 1/4 BSP fusible at DEG C Inert Gas Passage Solution Passage 3/4 BSP Solution Outlet Standard male adapter assembly (al) (Shown attached; safety plug (l) has been removed) Dip Pipe 6mm (1/8 ) N.B. 5mm BORE S.S "-14 NGO-LH-INT. 3 7/8" Fusible Safety Plug 3/4"-14NGT Annular opening that communicates with the cylinder vapor space 1 3/8" Diptube ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAGE 48 OF 71

52 GAS VALVE: DUAL PORT CYLINDERS A Manual Valve Operation 2 Spring Disk Diaphragms A B PTFE Plugged Seat Spring (note orientation) Fusible Safety Plug Liquid Connection 1/2" NPT Left-Hand Thread TECHNICAL AND DIMENSIONAL ILLUSTRATION» Superior valve» Standard compressed gas valve (CGA) 49 Valve Body Dip Pipe 6mm 1/8" N.B. 5mm bore SECTIONAL EXPLODED VIEW OF VALVE B A Manual Valve Operation 2 Spring Disk Diaphragms PTFE Plugged Seat Spring (note orientation) Liquid Connection 1/2" NPT Left-Hand Thread B Valve Body Dip Pipe 6mm 1/8" N.B. 5mm bore SECTIONAL EXPLODED VIEW OF VALVE PAGE 49 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

53 DISCHARGE VALVE: POYNTON 110mm 69mm 50 TECHNICAL AND DIMENSIONAL ILLUSTRATION» Poynton valve used in Europe» Full port opening» Exclusive design» Locking mechanism 60mm 22mm Spring Loaded Locking Device 1/4 Turn Open/Close Lever Operation Valve Inlet and Outlet Port Diameter 10mm Dip Pipe 10mm (3/8") N.B mm Bore 3/4" BSP Taper into Cylinder 7/8" UNF Left-Hand Thread for Product Connection SECTION THROUGH VALVE Clear Unobstructed Product Flow ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAPGE 50 OF 71

54 DISCHARGE VALVE: POYNTON Cap and Chain 50mm 51 Closed Position Open Position 50mm PAGE 51 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

55 DISCHARGE VALVE: CONBRACO 3.93" NGO-LH-INT 52 TECHNICAL AND DIMENSIONAL ILLUSTRATION» Conbraco valve used in the USA» Exclusive design» Locking mechanisms 3.12" 1.56" 3/4" NPT 1.92" 3/8" NPT ORGANOMETALLICS AND REACTIVE SPECIALTY SHIPPING TRANSPORT CONTAINERS PAGE 52 OF 71

56 AVERY HARDOLL COUPLINGS 160mm 6.24" 215mm 8.39" TECHNICAL AND DIMENSIONAL ILLUSTRATION» Cobham Fluid Systems, Limited» Avery valve» Dry-break coupling mm 4.10" 190mm 7.41" 2 - HOSE UNIT 3 IN BSP CCMY 8254 Material 316 Stainless Steel Weight 4.8 kg Max. Working Pressure 150psi Max. Coupling Pressure 60 psi PAGE 53 OF 71 TRANSPORT CONTAINERS SHIPPING ORGANOMETALLICS AND REACTIVE SPECIALTY

57 UNLOADING AND SAMPLING 54 ANY PROCEDURE WHICH CAN RESULT IN A BREAK OF CONTAINMENT WITH ORGANOMETALLIC OR REACTIVE ORGANIC MATERIALS MUST BE UNDERTAKEN WITH CARE AND DUE ASSESSMENT OF THE RISKS INVOLVED. Unloading or sampling, by definition, involves a break in containment. All equipment should be suitably designed for the task, and all personnel should be thoroughly trained in the procedures and hazards. Provided these factors are fully considered, the risk can be managed and the quality of the product unaffected. ORGANOMETALLICS AND REACTIVE SPECIALTY UNLOADING AND SAMPLING PAGE 54 OF 71

58 55 THE FUNDAMENTALS OF UNLOADING ARE THE SAME FOR ALL CONTAINERS. THE TYPE OF VALVING AND THEIR LOCATIONS ON THE CONTAINER DIFFER. AN FMC ENGINEER BLEEDS THE CONTAINER PRESSURE THROUGH THE VENT VALVE PRIOR TO TRANSFERRING THE PRODUCT. THE TECHNIQUES AND PROCEDURES DISCUSSED IN THE ORGANOMETALLICS AND REACTIVE SPECIALTY ORGANICS SAFE HANDLING GUIDE SHOULD BE UTILIZED BY PROFESSIONALS TRAINED AND EXPERIENCED IN WORKING WITH THESE COMPOUNDS. PAGE 55 OF 71 UNLOADING AND SAMPLING ORGANOMETALLICS AND REACTIVE SPECIALTY

59 UNLOADING AND SAMPLING 56 PROTECTIVE EQUIPMENT Advice on protective clothing is provided in the MSDS, which should always be available and accessible. Eye, skin and foot protection should be worn for all operations involving organometallics and reactive organics, regardless of the quantity involved. All protective clothing should be flame retardant and easy to remove in the event of a spill onto the clothing. More information is given in the Laboratory Section, p. 14. Safety helmets, face shields and/or goggles should be worn in plant environments where large quantities of organometallics and reactive organics are being handled. Flame-proof garments can offer more protection, but may be cumbersome and difficult to remove in an emergency. Personal protective clothing should not be relied upon. Systems should be designed to prevent spillage from occurring and to minimize operator presence as a more effective method to improve safety. Please refer to the appropriate FMC Lithium MSDS concerning your specific product. Available at or by contacting FMC Lithium. LABORATORY / GLASS SAMPLE BOTTLES APPARATUS AND EQUIPMENT: All volumetric glassware is class A 10 ml Luer-Lok syringe Small rubber stopper (size 00 is sufficient) to seal the syringe needle Rubber septum (similar to Aldrich: Z10, 145-1, 14x30 mm) Two #18 gauge needles; one 2" and one 6" A tubing system with mineral oil bubbler, to deliver Argon (Ar) to the apparatus (see diagram) Dry oven at 105 C Desiccator, with indicating silica gel REAGENTS Mineral oil, heavy Argon (Ar) or Nitrogen (N 2 ) All equipment should be oven dried for at least 1 hour and then allowed to cool in a desiccator. ORGANOMETALLICS AND REACTIVE SPECIALTY UNLOADING AND SAMPLING PROTECTIVE EQUIPMENT PAGE 56 OF 71

60 Eye, skin and foot protection should be worn for all operations involving organometallics and reactive organics, regardless of the quantity involved. All protective clothing should be flame retardant and easy to remove in the event of a spill onto the clothing. Attach a dry 6" needle to a dry syringe and lightly coat the plunger with mineral oil from a paper towel. Work the plunger in and out of the barrel with a twisting motion. Place a small rubber stopper onto the end of the 6" needle attached to the syringe. Carefully pierce a 14x30 mm rubber septum with the 2" needle. This needle appears over the sample in the diagram. Attach the hose shown in the diagram to the 2" needle passing through the rubber septum. Start a slow flow of argon through the system. Regulate flow by closing off all lines, except the line to the bubbler. Open the line to the sample. Make sure sample argon line is open. Carefully remove the cap from the sample bottle while sweeping with a flow of argon from the septum prepared above. Quickly, yet carefully, attach the septum to the sample bottle. Repeat these instructions in reverse to replace the original cap. Figure 9.1 LABORATORY / GLASS SAMPLE BOTTLE ARRANGEMENT A Ar A Sample B Syringe C Mineral Oil Bubbler B C Ar Excess argon fed to the sample is vented through a mineral oil bubbler via the argon manifold. Remove the stopper from the end of the needle and insert the 6" needle attached to the syringe through the septum over the sample solution. Flush the syringe twice with argon by inserting the needle into the headspace of the sample and pulling up a full syringe of headspace gas and expelling in the outside air. Re-insert the syringe needle into the sample bottle and pull up required sample into syringe. Slowly withdraw the needle from the sample into the headspace. Pull up about 0.1 ml of headspace gas. This prevents spillage when pulling the needle from the septum. Re-seal the needle with the rubber stopper. The sample is now ready for analysis. SAMPLING PROCESS LINES Process lines may be sampled using dried, purged sample bottles and a modification of the needle/syringe techniques described above. FMC Lithium has found that more representative samples may be obtained safely by using proprietary dry break sampling systems that are installed in the process line. These systems allow controlled removal of samples and provide safe systems of carriage and discharge into laboratory glassware. 57 Please contact FMC Lithium for more details. PAGE 57 OF 71 SAMPLING PROCESS LINES UNLOADING AND SAMPLING ORGANOMETALLICS AND REACTIVE SPECIALTY