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Appendix F EXCERPTS FROM TITANIUM TETRACHLORIDE SPECIFICATIONS du Pont de Nemours & Co. ~ Inc. Specifications (Extracted from E. I. ium Tetrachloride) This description was originally prepared to assist users of du Pont titanium tetrachloride in planning sat e storage and handling procedure s. The excerpts presented below are based on du Pont experience. In planning sate storage and handling Titanium tetrachloride ~ TiC14) is manufactured by the chlorination o f t it anium-bearing ore s in the pre sence of coke as a reducing agent. Titanium tetrachloride is a colorless to light-yellow liquid with a pungent odor. Ti tanium tetrachloride is very susceptible to hydrolysis, and the liquid fumes strongly when exposed to moist air. The fumes are dense and persistent and consist of hydrochloric acid, f inely divided particles of titanium oxychloride and hydrated oxides of titanium. (Tables below give typical analysis and properties of TiC14 ~ Typical Analysis (percent ) TiC14 Tin Silicon Iron Vanadium Aluminum Chromium Copper Lead Ni ckel 99.5 0.05 0.02 O .0006 0.003 0.003 O .0003 O.0007 O .002 0.008 Chemical Properties Physical Properties Molecular weight Boiling point ~ 760 mm Hg ), C F Freezing point ~ C F Specific gravity @ 20C (68F) Weight per gallon, lb Vapor pressure, mm Hg @ 20C Viscosity, cP (mPa) ~ 20C Specific Heat ~ liquid), cal/g/ C J/kg/K 189.71 136.4 277.5 -25 -13 1.73 14.4 10 ().85 0.19 795 Ti tanium tetrachloride breaks down almost completely on solution in water converting into colloidally dispersed titanium oxyhydrates. The reaction of liquid TiC14 with water is extremely violent, almost explosive. The products in strong HC1 solution are clear at room temperature . 189

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# 190 TiCl4 dissolves in various alcohols (methanol ~ ethanol) forming salt-like solvates having good electrical conductivity. With the organic halides ~ TiC14 generally forms weakly conducting salt-like complexes. Health Hazard s Titanium tetrachloride is a powerful desiccant and contact with the liquid product will cause burns from both chemical and thermal effects. The vapor is also hazardous and is extremely irritating to the skin, eyes, nose and throat . Overexposure deco the vapor may cause burns to the eye s and lungs . Oregon Metallurgical Corporation Ticks Specification (Nov. 30, 1976) Scope: This specification covers titanium tetrachloride used in the production of titanium sponge . Color: yellow. The acceptable color of TiCl4 will be water white to light straw Chemical Compo sit ion: Chlorine TiCl4 Iro n Vanadium Ca rbon Silicon Ch romium Nickel Aluminum Tin Copper Manganese Sn, Cu. Mn: Quality: None 9 9.8 Percent 25 PPM 25 PPM 40 PPM lo PPM 25 PPM 25 PPM 25 PPM 50 PPM 50 PpH 50 PPM Total 100 PPM Vendor shall be responsible f or establishing and usi ng sampling procedures and methods for chemical analysis to afford reliable assurance of the acceptable quality levels.

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191 Timet Divison, TCMA TiC14 Specif ication The following tables are a tabulation of specifications for TIMET titanium te trachloride: Ca talyt ic Or ade Chemi stry Re port editMaximum Typical Physical Charac teri stic s Tin 10 ppm 6 ppmAPHA Color: 40 max. Aluminum 20 ppm 6 ppmClarity: no sign of turbidity Iron 10 ppm 5 ppm Vanadium 10 ppm 7 ppm Silicon 10 ppm 5 ppm Copper 5 ppm 2.5 ppm Chromium 5 ppm 3 pp~n Re sidue 160 ppm 90 ppm bother elements by special request . - Physical Properties of Titani~ Tetrachloride Reference Color ' Colorless Odor Sharp, fumes in air Molecular weight 18 9. 71 ( 1) Melting point -25 C (1) Boiling point 136 .4 C ~ 1 ) Specific gravity 20/20C 1.726 (1) Refractive index n25 1.61 (1) D Heat capacity, liquid 35~7 cal/deg mole, 25C (2) Heat capacity, gas 25e45 + Oe23 X 10-3T - 2~36 X 10-5T2 cal/deg mole (3) Heat of fusion 2e24 kcal/mole' - 25C (21~3 BTU/lb) (4) Heat of vaporization 8e346 kcal/mole, 136e4C (79~2 BTU/lb) (4) Heat of formation, liquid -192.1 kcal/mole, 25C (-1822.7 BTU/lb) (4) Free energy of formation, -175.9 kcalimole, 25C (-1669.0 BTU/lb) (4) liquid Ref. (1) Handbook of Chemistry and Physics, 48th Edition, 1967-1968. Ref . (2) Chemical Engineers' Handbook, John H. Perry, Third Edition. Ref. (3) Ke lley, K. K., "U. S. Bureau of Mines Bulletin 476. " (1949) . Ref . (4) Thermodynamic Properties of 65 Elements--Their Oxides, Halides, Carbides, and Nitrides, C. E. Wicks and F. E. Block, USBM Bulletin 605, 1963.

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Cabo t Corporation TiC14~ 192 ecif ications Grade I Grade II TiC14 9 9 . 8 % Min Co lor 5 0 APHA 200 APHA Turbidity Clear Clear . Chemical Analysis: Al 5 PPM Max. 5 PPM Max. Sb 5 .' 8' 5 8' t. As 10 " " 10 " " Bi 5 08 t. 5 88 88 Bo 5 88 8 5 8. '' C 40 8. 85 40 Or 5 ,. .. Co 5 " " 5 " " Cu Fe 10 8' '' 10 '. t' Pb 5 " " 5 " " Mg 5 se ~ 5 '' t' Mo '; 5 " " Ni 5 08 '. 5 08 .. Si 10 ~10 8' 8. Sn 10 8' 88 25 " " V 5 8' .' 10 " ''

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193 Data Sheet from Soviet TiC14 Specifications Impurity Content, Percent by Weight Impurity In technical Specifications In purified TiC14 for pure TiC14 TiC14 Grade 1, according to TU--39--69 VOC13 0.33 0.0034 0.0034 AlC13 a 0.02 0.005 0.005 SiC14 a 0.4 0.006 0.006 Si2OC16 a 0.04 - 0.003 FeC13 a 0.012 0.0029 0.0029 CC14 0.06 0.005 ~ CC13COC1 0.005 0.0005 0.0002 CS2 0.01 0.00002 0.00002 COS 0.009 - 0.00002 Oxygen (oxychlorides) 0.03 0.001 0.001 Si3O2Clg 0.007 - 0.002 C6C16 0.015 - - CO2 0.01 - - COC12 0.5 0.0005 0.00002 C12 0.05 - Arbitrarily, the amounts of Al, Fe, and total Si are limited. The allowable content of impurities in titanium tetrachloride going for the production of sponge titanium is no more than the following percent by weight: Impuri ty A1 at Fe V 0.004 COC12 C1 (free) O2 (oxychlorides) Grade O Grade 1 Grade 2 Grade 3 . ( percent by weight ) 0.0015 0.005 0.004 Trace 0.003 0.0005 0.001 0.003 0.007

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