Document 7MqLOrEgG1v16K011554gDG06

GAS DATA BOOK Sixth Edition Matheson MATHESON GAS DATA BOOK Copyright, 1980 by Matheson, Printed in the United States ot America. This book, or parts thereof, may not be reproduced in any form without the prior permission of Matheson. Library of Congress Catalog Card No. 80-83159 GGC 002245 VINYL CHLORIDE (Synonyms: Chlor ethen ; Chloroethylene) (Formula: CH2:CHCf or C,H3CI) PHYSICAL PROPERTIES (1) Molar Mass Molecular Weight............................................................................ One Mole of C2H3Ci.......................................................................... Specific Volume @21.1 C, 101.325 kPa.................................. Vapor Pressure @21.1 C............................................................... Boiling Point @ 101.325 kPa...................................................... Freezing Point................................................................................... Absolute Density, Gas @ 101.325 kPa @ 25 C......................... Relative Density, Gas @ 101.325 kPa @ 25 C (Air = 1)........... Density, Liquid @ -20 C............................................................. Critical Temperature.......................................................................... Critical Pressure............................................. Critical Volume ............................................................................ Critical Density................................................................................. Critical Compressibility Factor........................................... Latent Heat of Fusion @ 119.45 K .................................................. Flammability Limits In Air ... .................................. Dipole Moment, Gas........................................................................ Molar Specific Heat, Gas @ 101,325 kPa @ 25 C @ Constant Pressure .................................. ...................................... Molar Specific Heat, Liquid @ 0 C ............................... Viscosity, Gas @ 101.325 kPa @ 20 C...................................... Viscosity, Liquid @ -20 C ...................... Thermal Conductivity, Gas @ 101.325 kPa @ 25 C.................... Surface Tension @ -20 C............................................................. Solubility In Water @ 101.325 kPa (total pressure) @ 25 C .... Refractive Index, Liquid @ Saturation Pressure, n0 @ 25 C . Dielectric Constant, Liquid @ 27.2 C......................................... Autoignition Temperature ...................................... Flash Point . . ...................................................................... 0.062 499 kg 0.062 499 kg 387.0 dm3/kg; 6.2 ftVlb 336 kPa; 3.36 bar; 48.7 psia; 3.31 atm 259.35 K; -13.8 C; 7.2 F 119.45 K; -153.7 C; -244.7 F 2.620 kg/m3 2.21 0.972 kg/t 424.61 K; 151.5 C; 304.6 F 5 755 kPa; 57.55 bar; 834.7 psia; 56.8 atm 2.71 dm3/kg 0.369 kg/dm3 0.276 75.90 kJ/kg; 18.14 kcai/kg 4-22% (by volume) 4.837 x 10"30 C-m; 1.45 D 53.607 J/(mol-K) 78.449 J/(mol.K) 0.010 72 mPa-s; 0.010 72 cP 0.280 mPa*s; 0.280 cP 0.007 95 W/(m-K) 19.0 X 10-6 cal/ cm/(s-cm3-C) 23.1 mN/m; 23.1 dyn/cm 1.07 cm3/1.0 ml water 1.366 6.26 745.15 K; 472.0 C; 882.0 SF 195.15 K; -78.0 C; -108.4 F Description Vinyl chloride is a colorless, highly flammable gas having a pleasant, sweet odor in high concentrations. Vinyl chloride is toxic and carcinogenic; at this writing a TLV standard of 5 ppm has been established. It is shipped in cylinders, single-unit tank cars, and ton multiunit tank cars, and in tank trucks and ton multiunit tanks on trucks. It is readily liquefied and is reshipped in steel cylinders as a liquefied compressed gas under its own vapor pressure 234 kPa (34 psig) at 21.1 C. It is shipped with an inhibitor (phenol) to prevent polymerization in the cylinder. Specifications Vinyl chloride typically has a minimum purity of 99.9 mole% (liquid phase). Uses Vinyl chloride is used as an intermediate in organic synthesis and for the production of plastics by polymerization and co polymerization. Effects In Man and Toxicity (2) The 1979 ACGIH has established a Threshold Limit Value (TLV) of 5 ppm <10 mg/m3) for vinyl chloride. It has been reported that concentrations of above 1 000 ppm slowly produce mild disturbances such as drowsiness, blurred vision, staggering gait, and tingling and numbness in the feet and hands. The carcinogenicity of vinyl chloride has been established after notification that several workers who handled and used l^fathesonr GGC 002246 695 VINYL CHLORIDE vinyl chloride developed a rare form of liver cancer. Exposure of rats to vinyl chloride by inhalation at and below 500 ppm induced tumors, including angiosarcomas of the liver. Another series of experiments on the effect of exposure of rats, mice and hamsters to vinyl chloride at concentrations of 10 000; 6 000; 2 500; 500; 250; and 50 ppm have been carried out for varying periods of time. The experimental results so far re ported are that tumors have been observed in groups of animals exposed to vinyl chloride at concentrations as low as 250 ppm. Liquid vinyl chloride on skin contact may cause severe irritation and burns. First Aid Treatment Summon a physician at once for anyone who has been exposed to high concentrations of vinyl chloride vapor or its liquid state. Inhalation The victim, especially if he complains of dizziness, should be removed to an uncontaminated, well-ventilated room. Oxygen should be administered, by trained personnel only. The patient should be kept quiet and comfortably warm but not hot and a physician summoned. Skin Contact Remove contaminated clothes and shoes and wash the af fected areas with copious quantities of water followed by soap water solution. Eye Contact Irrigate the eyes immediately with copious quantities of water for at least 15 minutes, holding the eyelids apart during the irrigation to insure contact of the water with all tissues of the eyes and lids. An eye specialist should be called promptly. Precautions in Handling and Storage An effective educational and training program should be instituted to inform the workers of the hazards involved in handling and using vinyl chloride, and the first aid measures to be followed in the event of an emergency. Vinyl chloride should be used in a well-ventilated area, preferably a hood with forced ventilation. All lines and equipment to contain vinyl chloride should be grounded. Personnel handling vinyl chloride should wear safety shoes, chemical safety gogles and/or a full face shield, and rubber gloves. For respiratory protection, self-con tained breathing equipment, air-line gas masks and U.S. Bu reau of Mines approved cannister type gas masks should be available in emergencies. Instant-acting safety showers and eye fountains should be conveniently located near the site of the operation. Store and use cylinders of vinyl chloride in wellventilated area away from heat and alt sources of ignition such as flames and sparks. Do not use vinyl chloride around sparking motors or other non-explosion proof equipment. Do not store reserve stocks of cylinders of vinyl chloride with cylinders containing oxygen, chlorine, or other highly oxidizing or flam mable materials. In addition, the general rules listed in Appendix I should be observed. Leak Detection Leaks of vinyl chloride in lines and equipment may be de tected by applying soap water solution to the suspected sites; leaks will be indicated by bubble formation. Analytical Detection Matheson has available a Toxic Gas Detector, Model 8014K, for detection of 0.25-10 ppm vinyl chloride in the atmosphere (Model 8014-132SC detector tube). A 100-cm3 sample of the atmosphere is drawn into the detector tube which contains a chemical reagent that absorbs and reacts with vinyl chloride. A color stain is produced which varies in length with the concentration. The length of the stain is read directly off the detector tube scale. Disposal of Leaking Cylinders Leaking cylinders of vinyl chloride that cannot be corrected normally may be handled in the following manner. Put on an appropriate gas mask or self-contained breathing equipment and place the cylinder in a hood with forced ventilation. Attach an appropriate regulator and check valve to the cylinder valve outlet. Introduce the vinyl chloride at a moderate rate into an adequate amount of a suitable solvent such as carbon tetra chloride, chloroform, 1,2-dichloroethane, or chlorobenzene. The resulting solution can be fractionated for recovery of vinyl chloride. Materials of Construction Steel is a completely satisfactory material for handling vinyl chloride. Copper and its alloys should not be used as it might result in the formation of explosive acetylides from trace im purities of acetylene. Fittings and connections for 1.5 inch and larger pipe should be flanged or butt welded. Fittings and connections for 1 inch and smaller pipe may be threaded and the appropriate joint compound used. Garlock No. 7021, Vie inch thick asbestos gaskets, or equivalent are satisfactory for flanged connections. Teflon, lead, and carbon are also suitable. Cylinder and Valve Description Vinyl chloride is shipped in DOT approved, low pressure steel cylinders. Cylinders of vinyl chloride are equipped with steel or cadmium-plated brass valves having Compressed Gas Association (CGA) valve outlet connection No. 290. The valve outlet has a thread size of 0.745 inch, with left-hand external threads accepting a bullet-shaped nipple (see Figure 1 for an illustration of the valve outlet and its mating connection). Lec ture bottles have a special Vis inch-32 threads per inch, female outlet. OUTLET CONNECTION Fig. 1. CONNECTION 290 .745"-14 LH EXT. accepting a Bullet Shaped Nipple 696 GGC 002247 VINYL CHLORIDE Safety Devices The most commonly used device, and the one used by Matheson, is the spring-loaded safety relief valve. If the cylinder pressure becomes dangerously high usually due to overheat ing, the safety relief device will open (at about 2 590 kPa (375 psig)) and release gaseous vinyl chloride until the pressure again returns to a safe level. Recommended Controls Automatic Pressure Regulators Matheson regulator Model 13-290 is recommended for use with vinyl chloride. This single stage regulator has an anodized aluminum body, type 316 stainless steel internal parts, a dia phragm of FEP Teflon on Neoprene and a Teflon seat. It has a delivery pressure range of 28-240 kPa (4-35 psig). Low pressure regulator Model 71-290 is available for sensi tive and accurate low pressure control. The regulator has an oversized, pancake, aluminum body, type 303 stainless steel internal parts, a Teflon-faced Butyl rubber diaphragm, a Teflon seat, and a delivery pressure of 3.4-34.5 kPa (0.5-5.0 psig). Manual Controls Matheson needle valve Model 61-290, of type 303 stainless steel, is available for direct attachment to the cylinder valve outlet. This valve may be equipped with a variety of outlets, such as a connection hose, 'A" inch tube fitting, or '/* inch NPT male or female connection. It should be used only where manual flow control is needed and should not be used as a pressure control since it will not prevent pressure from building up if a system becomes clogged or if the system itself is closed. Stainless steel needle valve Model 32S or Model 59 is recom mended for use with lecture bottles. Flowmeters Matheson Series 7600 laboratory stainless steel flowmeter units with 150mm tubes and floats or Matheson Series 7200 laboratory stainless steel flowmeter units with 65 mm tubes with a single float are recommended for use where definite flow rates must be known. Electronic mass flowmeters, such as Matheson Series No. 8116 and No. 8160, should be used where accurate readings are required. Calibration is unaffected by temperature and pressure changes, and flow rates may be recorded from the instrument's electrical output. Electronic Mass Flow Controllers The Matheson Series 8240 of type 316 stainless steel and Series 8260 of type 316 stainless steel or monel are designed to control the flow of gas regardless of pressure and tempera ture changes. These mass flow controllers consist of a trans ducer, a control valve, a blind controller/power supply, a potentiometer, and a digital indicator. The transducer senses the gas flow and sends a signal to the power supply. This signal and one from the potentiometer are compared. If there is an imbalance, the power supply generates a signal for the control valve to reduce or increase the flow to correct the imbalance. The accuracy is 1.2%. Shipping Regulations Vinyl chloride, inhibited, is classified by the DOT as a flam mable compressed gas and is shipped with the "Red Gas Label". Commercial Preparation Vinyl chloride is made by the catalyzed addition of HCI to acetylene, by thermal decomposition of ethylene chloride, or by heating the latter with alcoholic caustic alkali. Chemical Properties Vinyl chloride is readily polymerized to polyvinyl chloride by a variety of methods. It also may be copolymerized with other unsaturated compounds. The Cf atom in vinyf chloride is unreactive in nucleophilic substitution reactions. Vinyl chloride undergoes addition reactions similar to the olefins. The inhibitor in cylinder vinyl chloride may be removed by scrubbing with dilute caustic solution, or by fractional distillation. Thermodynamic and Detailed Physical Data Molecular Structure The planar vinyl chloride molecule has the following struc tural parameters: bond distances: 0=0 1.355 A (1.355 x 10_, m); C-CI 1.728 A (1.728 X 10_, m); C-H 1.078 A (1.078 x 10~' m); bond angles: C-C-C1121.1: C-C-H 126. The lack of reactivity of the chlorine atom in vinyl chloride, CH2=CHCI, is attributed to resonance involving the polanzed _ 4* structure ^ ^ f ^ The resonance effect is such that the chlorine atom is bound to the carbon atom by a linkage which has double bond character and the chlorine atom therefore is less labile than in the normal C-CI bond. Vinyl chloride has a dipole moment of 1.45 D. Infrared Spectrum See Figure 2 for the infrared spectrum of gaseous vinyl chloride. Vapor Pressure (S) The vapor pressure of liquid vinyl chloride up to 101.325 kPa (1 atm) is shown below. Temperature, K 167.55 182.35 189.45 197.45 206.35 212.05 219.95 231.85 245.15 259.35 Vapor Pressure kPa mbar 0.133 0.667 1.333 2.666 5.333 7.999 13.332 26.664 53.329 101.325 1.33 6.67 13.3 26.7 53.3 80.0 133 267 533 1 013.25 mmHg 1 5 10 20 40 60 100 200 400 760 The vapor pressure above 101.325 kPa (1 atm) is tabulated below (6). hiathesorr GGC 002248 697 9 Q> Fig. 2. Infrared spectrum of gaseous vinyl chloride; 10-cm path length cell, with KBr optics; cell pressure (complete scan) 5.333 kPa (40 mmHg) (8). VINYL CHLORIDE Temperature, K 283.15 293.15 303.15 313.15 323.15 333.15 343.15 Vapor Pressure kPa bar 254.326 343.492 466.095 583.632 733.593 924.084 1 137.880 2.54 3.43 4.66 5.84 7.34 9.24 11.38 atm 2.51 3.39 4.60 5.76 7.24 9.12 11.23 Latent Heat of Vaporization, AHv Temperature, K 213.15 233.15 259.35 AHv, kj/kg 388.8 376,2 357.29 VINYL CHLORIDE Thermodynamic Data Compressibility data for vinyl chloride are shown in Table 1. Thermodynamic Properties of Vinyl Chloride As Ideal Gas @ 25 C (7) Heat Capacity, C? Entropy, S Free Energy Function, (G|M - Eo)/298 Enthalpy Difference, - Ho Enthalpy of Formation, AH? Free Energy of Formation, AG? 53.723 J/(mol-K) 263.885 J/(mol-K) -224.221 J/(mol-K) 11.820 kJ/mol 35.564 kJ/mol 51.882 kJ/mol REFERENCES ' For extensive tabulations of the thermodynamic and physical properties of vinyl chloride, see W. Braker and A. L. Mossman, The Matheson Unabridged Gas Data Book. 7 9/5, Matheson, East Rutherford, New Jersey, 2 The Toxic Substances List, H. E, Christiansen, T. T, Luginbyhl, and B. S. Carroll, 7974, pp. LXXIX-LXXXI, Federal Register, Volume 39, No, 67, National Institute for Occupational Safety and Health, Rockville, Maryland. 3 Federal Register, Volume 39, No. 194, Oct. 4, 1974, National Institute for Occupational Safety and Health, Rockville, Maryland. * R. C. Ivey and M. I. Davis, J. Cham. Rhys. 57, 1909-1911, (1972). 5 Chemical Engineers' Handbook, 5th edition, R, H. Perry and C. H. Chilton, editors. 1973, p. 3-61, McGraw-Hill Book Co., Inc.. New York. New York. 6 J. T Rozlooskaya and M. I. Temkin, J. Appl. Chem. (U.S.S.R.) 19, 32 (1946). 7 D. 0. Wagman, ef a/., Selected Values of Chemical Thermodynamic Properties, 1968, p. 143, Natl. Bur. Stand. Tech. Note-270-3. U. S, Government Printing Office, Washington, D. C. 8 The Sadtler Standard Spectra, 1972, Sadtler Research Laboratories, Inc., Philadelphia, Pennsylvania. 3 W. Hayduk and H. Laudie, J. Chem. Eng, Data 19, 253-257, (1974). Mathesorf OGC 002250 699 1 VINYL CHLORIDE Table 1. COMPRESSIBILITY FACTORS Z, FOR GASEOUS VINYL CHLORIDE (9) Temperature, 273.15 K Pressure kPa atm z Temperature, 323.15 K Pressure kPa atm z 52.689 101.325 119.564 142.868 167.186 173.266 0.52 1.00 1.18 1.41 1.65 1.71 0.988 0.974 0.969 0.956 0.933 0.905 101.325 190.491 330.320 419.486 574.513 731.566 807.560 1.00 1.88 3.26 4.14 5.67 7.22 7.97 0.985 0.969 0.948 0.932 0.900 0.850 0.700 Temperature, 298.15 K Pressure kPa atm z Temperature, 348.15 K Pressure kPa atm z 101.325 144.895 169.213 230.008 298.909 345.518 369.836 395.168 1.00 1.43 1.67 2.27 2.95 3.41 3.65 3.90 0.981 0.975 0.969 0.961 0.945 0.916 0.888 0.846 101.325 228.994 345.518 447.856 615.043 812.626 1 033.515 1.00 2.26 3.41 4.42 6.07 8.02 10.20 0.988 0.972 0.954 0.939 0.911 0.869 0.808 GGC 00225/ 700 H$athesoir