Document Eqd4zqZLLem0Ve0kKYM6KNaRn

DOW CONFIDENTIAL INFORMATION R&D REPORT THE DOW CHEMICAL COMPANY CRI NUMBER LABORATORY REPORT CODE LAD-AR 93.05 DEPARTMENT RESEARCH AND DEVELOPMENT GEOGRAPHIC LOCATION LOUISIANA DATE ISSUED April 26, 1993 REPORT TITLE Accelerating Rate Calorimetry Testing of Process Leak Repair Sealants _48_ PAGES IN FULL REPORT for Chlorine Service (Steam & Process SP-2026, SP-CM, SP-300D, and -fcA;B NO. PROBLEM NO. an Experimental Sealant, SP-TFLO) 274 0000 AUTHOR'S LAST NAME AND INITIALS/MASTER NUMBER J. G. Schell (432167), G. P. Wagener (431616), G. J. Barrilleaux (430781) AUTHOR'S SIGNATURE REVIEWER'S AND/OR SUPERVISOR'S NAME R. D. Summers DESCRIPTIVE SUMMARY WITH CONCLUSIONS: RVISOR'S SIGNATURE A commercial process leak repair sealant (Steam & Process SP-2026) which was in service for approximately one year on a process chlorine vapor line showed strong evidence of having reacted with chlorine. This necessitated a search for a replacement sealant. Several commercial sealants were recommended by Steam and Process, Inc. and were submitted to the Louisiana Division (LAD) Reactive Chemicals lab for testing by Accelerating Rate Calorimetry (ARC). MSDS sheets which accompanied the sealants were used in eliminating three of the sealants submitted (SP-2000T, SP-1011, SP-2000). The basis for elimination was known reactivity of the listed organic ingredients with chlorine. The sealants which were tested (SP-2026, SP-CM, and SP-300D) all reacted with liquid chlorine. This prompted LAD Reactive Chemicals laD personnel to develop a new sealant. The new sealant is composed of Deacon Teflon Fiber 311 and a fully halogenated grease, Fluorolube GR 544. Compatibility with liquid chlorine has been confirmed by'ARC testing. A patent application has been filed on this work. The sealant is now designated as SP-TFLO and is available through Steam & Process, Inc. KEY WORDS Leak repair sealants, chlorine, Accelerating Rate Calorimetry, ARC PATENT STATUS: DISCLOSURE SUBMITTED &CASE FILED NO ACTION REQUIRED ARE THE MATERIALS DESCRIBED IN THIS REPORT ON YOUR COUNTRY'S INVENTORY-' (TSCA, EINECS. ELINCS. CEPA. ETC.) YES NO* WILL THIS PRODUCT BE SOLD/USED IN OTHER COUNTRIES? YES* 3 NO `CONTACT YOUR LOCAL REGULATORY COMPLIANCE PERSON AND/OR CHIEF PRODUCT STEWARD DISTRIBUTION: FORM NO C-4301 (REV 03/92) CRI - 566 MIDLAND. Ml CRI - FREEPORT.TX CRI - PLAQUEMINE. LA DEPARTMENT FILES | DISTRIBUTION LIST IS CONTINUED ' ON ATTACHED PAGE no A 022133 OONFTDFNTTAl 2 INTRODUCTION The production plants often use commercial sealants to temporarily repair leaks in process lines until the leaks can be permanently repaired. This subject is addressed in the Louisiana Division (LAD) Safety and Loss Prevention Standard S-317 "Leak Repairs to Operating Lines or Equipment." A commercial process leak repair sealant (Steam & Process SP-2026), which was in service for approximately one year on a chlorine vapor line at the LAD Chlorine Plant, showed strong evidence of having reacted with chlorine. This was a Reactive Chemicals concern because chlorine in contact with a sealant containing hydrocarbon constituents can generate sufficient exothermic activity to initiate an iron-chlorine fire which could easily lead to an environmental event. The reactivity of SP-2026 with chlorine necessitated a search for a replacement sealant. Several commercial sealants were recommended by Steam & Process, Inc. and were submitted to the LAD Reactive Chemicals lab for testing by Accelerating Rate Calorimetry. MSDS sheets which accompanied the sealants were used in eliminating three of the sealants submitted (SP-2000T, SP-1011, SP-2000). The basis for elimination was known reactivity of the listed organic ingredients with chlorine. The sealants which were tested (SP-2026, SP-CM, and SP-300D) all reacted with liquid chlorine. This prompted LAD Reactive Chemicals lab personnel to develop a new sealant. The new sealant is composed of Deacon Teflon Fiber 311 and a fully halogenated grease, Fluorolube GR 544. Compatibility with liquid chlorine has been confirmed by ARC testing. A patent application has been filed on this work. The sealant is now designated as SP-TFLO and is available through Steam & Process, Inc. EXPERIMENTAL Accelerating Rate Calorimetry The Accelerating Rate Calorimeter (ARC) was used to determine the compatibility of three commercial leak repair sealants (Steam & Process SP-2026, SP-CM, and SP300D) and our newly formulated sealant (SP-TFLO) with liquid chlorine. Prior to ARC testing, the commercial sealants were cured in air overnight (SP-2026 at 75 degrees C, and SP-CM and SP-300D at room temperature). SP-TFLO did not have to be cured. For each ARC run, a sample of the sealant was rolled into a narrow strip, frozen with liquid nitrogen, and then loaded through the 1/8 inch tube opening of the Hastelloy C ARC sphere. This was necessary due to the tackiness of the sealants. The ARC sphere was then chilled in liquid nitrogen and loaded with liquid chlorine. After the sphere was attached to the calorimeter, the sphere and contents were allowed to reach ambient temperature before the ARC run was started. Appendices A, B, C, and D contain copies of the ARC reports for the four runs with detailed experimental conditions, tables of the raw data (time, temperature, self-heat rate, pressure, and pressure rate), and plots. Dow Confidential no A OF'1] 34 CONF TDFNT T Al 3 Formulation of New Sealant SP-TFLO The weight ratio of Fluorolube GR 544 fully halogenated grease to Deacon Teflon Fiber 311 fibers was varied to determine the optimum weight ratio to make the leak repair sealant cohesive and pliable (Table I). RESULTS AND DISCUSSION SP-2026 + Chlorine (ARC 92-692) An exothermic reaction was detected at ambient temperature (21 degrees C) with an initial self-heat rate of 0.075 degrees C/minute and continued to 165 degrees C where the pressure reached 2632 psia and the system rupture disc burst. At this point, the self-heat rate had reached a maximum of 55.5 degrees C/minute. This heat rate is in excess of the system detection rate (20 degrees C/minute) and could have been higher. SP-CM + Chlorine (ARC 92-7081 An exothermic reaction was detected at ambient temperature (23 degrees C) with an initial self-heat rate of 2.075 degrees C/minute. This reaction was more exothermic than the previous run (ARC 92-692). The reaction continued to 130 degrees C where the pressure reached 986 psia and the system rupture disc burst. At this point, the self heat rate had reached a maximum of 391 degrees C/ minute. Again, the system is not accurate for self-heat rates exceeding 20 degrees C/minute and the actual rate could have been higher. Table I. Effect of Grease/Fiber Ratio on Cohesiveness of New Sealant Fluorolube Weight (q) Teflon Fiber Weight (g) Grease/Fiber Weight Ratio 1 Cohesiveness 1.00 2.00 1.0/2.0 poor 2.90 3.90 1.0/1.3 poor 2.70 2.70 1.0/1.0 good 5.65 2.82 2.0/1.0 good 7.10 2.34 3.0/1.0 good 9.04 2.26 4.0/1.0 good Dow Confidential DO A OP P'1 35 CONFTDFNTTAL 4 SP-30QD + Chlorine fARC 92-711) An exothermic reaction was detected at ambient temperature (22 degrees C) with an initial self-heat rate of 0.08 degrees C/minute and continued to 175 degrees C where a maximum pressure of 1361 psia occurred. The maximum self-heat rate of 2.35 degrees C/minute occurred at 169 degrees C. Other Commercial Sealants ARC testing of SP-2000T, SP-1011, SP-2000 was not performed since MSDS information listed organic ingredients which are known to react with chlorine (acetic acid, silicone rubber, methanol, petroleum and vegetable oils). Formulation of New Sealant SP-TFLO After all the tested commercial sealants were found to be reactive with chlorine, a new formulation which would be non-reactive with chlorine was designed by the Reactive Chemicals lab. This sealant was composed of Deacon Teflon Fiber 311 fibers (polytetrafluoroethylene fibers) and Fluorolube GR 544 grease (a polychlorotrifluoroethylene grease). The weight ratio of Fluorolube GR 544 grease to Deacon Teflon Fiber 311 was varied to determine the optimum ratio to make the leak repair sealant cohesive and pliable. Grease/fiber weight ratios from 1.0/1.0 to 4.0/1.0 gave good cohesive, slightly flowable masses which were viscous and strong enough to contain the pressures within a line being repaired, and yet flowable enough to be pumped into place in a clamp. The actual weight ratio used to repair a leak would depend on the temperature and pressure of the line being repaired. The sealant (1.0/1.0 weight ratio) was prepared by Steam & Process, Inc. according to our formulation (named SP-TFLO) and tested by ARC for compatibility with liquid chlorine. SP-TFLO + Chlorine (ARC 92-715) There was no thermal activity detected up to 120 degrees C. Exothermic reactions were detected at 124, 139, 158, and 173 degrees C; however, the maximum self-heat rate of all these exotherms was only 0.03 degrees C/minute, which is just above the detection threshold of the ARC. These reactions were not sustained. The low 0.03 degrees C/minute self-heat rates may have resulted from minor contamination of the sealant during handling. The results of this test indicate that there is no significant exothermic reactivity between the SP-TFLO sealant and liquid chlorine. Thus, the compatibility of the SP-TFLO sealant with chlorine has been confirmed by ARC testing. Table II presents a comparison of the reactivities of the tested sealants with chlorine. The SP-TFLO sealant is now available through Steam & Process, Inc. It has been successfully used several times at the LAD Chlor-Alkali 2 production plant for the repair of leaking chlorine lines and the replacement of a leaking valve packing. Dow Confidential no A o?ci 3f> r.ONF TDFNT I Al 5 Table II. Reactivity of Sealants with Chlorine Leak Repair Sealant SP-2026 SP-CM SP-300D SP-TFLO Onset Temp (C) ambient ambient ambient - Maximum Self-Heat Rate (C/min) Temp (C) at Maximum Self-Heat Rate Chlorine Reactivity 55.5 165 reactive 391 130 reactive 2.35 169 reactive - - non-reactive CONCLUSIONS 1. ARC testing of commercial leak repair sealants SP-2026, SP-CM and SP-300D made by Steam & Process, Inc. indicate that they react with liquid chlorine at ambient temperature and are not suitable for leak repair of chlorine lines. 2. Commercial leak repair sealants SP-2000T, SP-1011, SP-2000 made by Steam & Process, Inc. are not suitable for leak repair of chlorine lines since the MSDS sheets for these sealants list organic ingredients which are known to react with chlorine. 3. A new leak repair sealant composed of Deacon Teflon Fiber 311 and a fully halogenated grease, Fluorolube GR 544, has been formulated by the LAD Reactive Chemicals lab. Compatibility with chlorine has been confirmed by ARC testing. The sealant is now designated as SP-TFLO and is available through Steam and Process, Inc. The SP-TFLO sealant has been successfully used several times at the LAD Chlor-Alkali 2 production plant for repair of leaking chlorine lines and a valve packing. ACKNOWLEDGEMENTS The authors would like to acknowledge and thank Clark Ponthier from the LAD Chlorine plant for his help and cooperation with this project. Dow Confidential do A o??137 CONF T DFNTTAl 6 Appendix A DOW CONFIDENTIAL INFORMATION ANALYTICAL REPORT Noah 3.17 RCL: 92-0692 Analytical Sciences, Louisiana Division, Dow Chemical Company TO: Clark Ponthier Chlorine Plant Charge # 25 TITLE: Accelerating Rate Calorimetry Study of Steam & Process SP-2026 Sealant + Chlorine AUTHOR(S) Gerald Barrilleaux Reviewed by Ran on: 03-24-92 at 09:25 -- Analyzed on: 03-24-92 at 16:38 ARC: ARC SYSTEM 2 SUMMARY The following results have been obtained by Accelerating Rate Calorimetry (ARC). Refer to data plots contained within this report for more detail. CAUTION: The following data were generated under specific phi factor conditions. These data should NOT be applied to larger scale operations without considering the effect of phi on the ARC results. Please contact Reactive Chemicals personnel for further interpretations and applications of these data. RCL: 92-0692 Steam & Process SP-2026 Sealant + Chlorine A 7.530 g sample was loaded into a No. 3.00, Hastalloy C ARC sample container which yields a phi factor of 1.50 assuming an average sample specific heat of 0.500 cal/g deg c. The sample atmosphere was Chlorine. The programmed step heating was initiated at 20 deg C with a heat step of 5.0 deg C. An exothermic reaction was detected at 21 deg C and 114.6 psia with a self-heating rate of 0.08 deg C/min. This exotherm was terminated at 165 deg C and a pressure of 2632 psi, due to reaching the specified pressure transducer limit of 2500 psi. If the exotherm had been allowed to continue, it may have reached significantly higher temperatures and/or pressures. Therefore, these data may not represent the full potential of this exothermic reaction. DO A 000138 OONF T DFNT T Al 7 DOW CONFIDENTIAL INFORMATION ---------------------------------- ACCELERATING RATE CALORIMETRY Noah 3.17------------------------------ Analytical Sciences, Louisiana Division, Dow Chemical Company RCL: 92-0692 -- Ran on: 03-24-92 at 09:25 -- Analyzed on: 03-24-92 at 16:38 Sample description: Steam & Process SP-2026 Sealant + Chlorine Steam & Process SP-2026, 3.00 g + Chlorine, 4.53 g Submitted by: Phone Number: Operator: Analyst: Clark Ponthier (504) 389-8167 Gerald Barrilleaux Gerald Barrilleaux From: Chlorine Plant Charge Number: 25 ARC: ARC SYSTEM 2 Experimental Conditions Tape Run number ---------------------------------------------------Container type -----------------------------------------------------Container material----------------------------------------------Container weight, Mb ----------------------------------------Sample weight, Ms ----------------------------------------------Total System Volume, Vb (approx) ---------------Sample Volume, Vs (approx) ---------------------------Head space volume, Vg (approx) -------------------Head space atmosphere----------------------------------------Container Heat Capacity, Cb -------------------------Heat Capacity of the sample, Cs (assumed) Starting temperature ----------------------------------------End temperature (specified) -------------------------End temperature (actual) --------------------------------Heat step ---------------------------------------------------------------Wait time---------------------------------------------------------------Isothermal wait time ----------------------------------------Calorimetic rate threshold ----------------------------Stirring rate -------------------------------------------------------- 692.00 3.00 Hastalloy C 18.899 g 7.530 g 10.000 mL 7.500 mL 2.500 mL Chlorine 0.100 cal/deg c g 0.500 cal/deg C g 20.0 deg C 175.0 deg C 164.9 deg C 5.0 deg C 10 min 0 min "D.020 deg C/min o RPM Thermal Ratio, Phi = 1 + (Mb Cb)/(Ms Cs) 1.50 RUN PREPARATIONS: A Hastelloy C ARC sphere was loaded with thin slices of SP-2026 sealant, chilled with liquid nitrogen and chlorine was added via syringe. The sphere was kept cold and air-free until it was attached to the calorimeter. The ARC experiment was begun when the sphere temperature reached 19 degrees C. RUN COMMENTS: At approximately 165 deg. C the maximum self-heat rate of 55.5 d g. C/min was achieved. At this temperature, pressure reached 2632 psia and the system rupture disc burst. EXPERIMENTAL The specified amount of the sample is introduc d into the sample bomb which is in turn fitted to the calorimeter lid. The calorimeter is then 8 rapidly heated to the initial temperature after which either an isothermal age mode or a WAIT-SEARCH-HEAT sequence is entered to look for exothermic reaction self-heating. When less than the self-heat rate threshold is observed during the SEARCH mode or at th end of the isothermal age time, a heat step is applied to the calorimeter contents. A WAIT-SEARCH-HEAT process is repeated until the self-heat rate of the bomb exceeds the threshold rate at which time the reaction is allowed to proceed on its own under nearly adiabatic conditions. Detailed procedures for the ARC can be found in the CSI operating manual. GENERAL PRECAUTIONS Accelerating rate calorimetry offers a useful method for evaluating exothermic run-away processes. However, caution should be used when relating the ARC data to an actual plant process since phi for an ARC experiment is usually very different from phi for a large-scale reaction. In addition, special consideration is needed when kinetic complications are present in the ARC data. For example, the effects of autocatalysis or inhibitors can vastly change the runaway reaction in chemical storage situations. Consultation with Reactive Chemicals is recommended in the applications of ARC data to plant processes. Extrapolation of the data outsid the experimental range is generally unwise. Dow Confidential no a n?;>i4o <~ONF JDFNTTAI 9 DOW CONFIDENTIAL INFORMATION ---------------------------------- ACCELERATING RATE CALORIMETRY Noah 3.17---------------------------------- Analytical Sciences, Louisiana Division, Dow Chemical Company RCL: 92-0692 -- Ran on: 03-24-92 at 09:25 -- Analyzed on: 03-24-92 at 16:38 Sample description: Steam & Process SP-2026 Sealant + Chlorine Steam & Process SP-2026, 3.00 g + Chlorine, 4.53 g Submitted by: Phone Number: Operator: Analyst: Clark Ponthier (504) 389-8167 Gerald Barrilleaux Gerald Barrilleaux From: Chlorine Plant Charge Number: 25 ARC: ARC SYSTEM 2 DATA LIST Time (min) Heat Pressure Temperature Rate Pressure Rate (C) (C/min) (psia) (psia/min) START LISTING START Exotherm EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM 0.00 0.00 19.19 36.07 57.51 81.95 108.79 136.15 165.49 195.01 223.99 251.71 279.25 305.05 330.35 348.43 369.83 390.79 410.31 429.03 446.79 464.61 480.21 495.33 509.89 523.29 536.33 549.09 558.73 570.71 581.61 591.69 601.77 611.25 0.00 0.00 21.47 22.47 23.48 24.50 25.52 26.52 27.54 28.55 29.57 30.58 31.61 32.64 33.66 34.47 35.47 36.47 37.49 38.50 39.53 40.57 41.59 42.61 43.62 44.63 45.65 46.66 47.48 48.50 49.53 50.54 51.56 52.61 0.000 0.000 0.075 0.059 0.047 0.041 0.038 0.036 0.034 3.034 0.035 0.036 0.037 0.039 0.040 0.044 0.046 0.047 0.052 0.053 0.057 0.058 0.065 0.067 0.069 0.075 0.078 0.079 0.085 0.085 0.094 0.100 0.101 0.110 0.0 0.0 114.6 117.6 121.1 124.9 128.8 132.6 136.5 140.8 145.2 149.6 154.3 159.2 164.2 167.9 173.0 178.3 183.7 189.4 194.9 201.1 206.8 213.0 219.1 225.2 231.4 238.2 243.6 251.0 258.2 265.3 272.9 280.6 0.00 0.00 5.97 0.18 0.16 0.16 0.15 0.14 0.13 0.15 0.15 0.16 0.17 0.19 0.20 0.20 0.24 0.25 0.28 0.30 0.31 0.35 0.37 0.41 0.42 0.46 0.48 0.53 0.56 0.62 0.66 0.70 0.75 0.81 OO A 027141 CONFIDFNT TAi EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM 620.13 627.09 634.79 642.29 649.49 656.35 662.45 668.89 674.79 680.37 684.55 689.59 694.55 699.19 703.75 707.83 711.75 715.65 718.55 721.91 725.17 728.23 731.11 733.99 736.63 738.69 741.21 743.55 745.79 747.95 750.09 752.13 754.19 755.87 758.09 761.03 764.45 768.37 772.89 777.93 783.43 787.43 792.57 797.69 802.39 806.39 810.15 812.73 815.67 818.49 821.01 823.41 825.29 827.41 829.37 831.13 832.53 834.21 835.73 837.21 10 53.63 54.47 55.48 56.51 57.54 58.58 59.58 60.62 61.64 62.66 63.47 64.49 65.52 66.54 67.58 68.59 69.60 70.66 71.48 72.49 73.52 74.55 75.57 76.62 77.65 78.48 79.51 80.55 81.57 82.60 83.62 84.64 85.68 86.49 87.50 88.52 89.55 90.58 91.62 92.63 93.67 94.48 95.50 96.54 97.56 98.59 99.67 100.49 101.53 102.55 103.60 104.62 105.47 106.51 107.59 108.62 109.49 110.52 111.59 112.63 0.114 0.120 0.131 0.137 0.143 0.151 0.163 0.161 0.172 0.182 0.193 0.202 0.207 0.219 0.228 0.247 0.257 0.271 0.282 0.300 0.315 0.336 0.354 0.364 0.390 0.402 0.408 0.444 0.455 0.476 0.476 0.500 0.504 0.482 0.454 0.346 0.301 0.262 0.230 0.200 0.189 0.202 0.198 0.203 0.217 0.257 0.287 0.317 0.353 0.361 0.416 0.425 0.452 0.490 0.551 0.585 0.621 0.613 0.703 0.702 DOW CONFIDENTIAL 288.5 295.0 302.8 311.0 319.2 327.8 336.1 345.3 354.4 363.3 370.6 379.7 389.3 399.0 409.2 419.0 429.1 440.0 448.6 459.1 470.1 480.8 491.8 503.6 514.4 524.0 535.9 547.6 558.9 570.7 582.4 594.3 605.5 614.1 624.1 631.9 638.0 642.5 646.2 650.5 656.6 662.2 670.7 680.6 692.2 705.0 719.0 730.6 744.6 759.4 773.9 788.4 801.0 815.9 831.2 846.9 858.0 873.3 887.7 903.1 0.89 0.93 1.01 1.09 1.14 1.25 1.36 1.43 1.54 1.59 1.75 1.81 1.94 2.09 2.24 2.40 2.58 2.79 2.97 3.12 3.37 3.50 3.82 4.10 4.09 4.66 4.72 5.00 5.04 5.46 5.47 5.83 5.44 5.12 4.50 2.65 1.78 1.15 0.82 0.85 1.11 1,40 1.65 1.93 2.47 3.20 3.72 4.50 4.76 5.25 5.75 6.04 6.70 7.03 7.81 8.92 7.93 9.11 9.47 10.41 DO A 077147 CONFTDFNT T At {OTHERM -XOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM END LIST 838.25 839.45 840.77 841.77 842.97 844.05 844.85 845.85 846.79 847.71 848.53 849.31 849.87 850.57 851.09 851.69 852.23 852.77 853.17 853.55 853.97 854.37 854.69 854.97 855.27 855.57 855.81 856.05 856.29 856.53 856.77 856.93 857.13 857.29 857.41 857.57 857.69 857.77 857.87 857.97 858.05 858.13 858.19 858.25 858.31 858.35 858.41 858.43 858.47 858.49 858.51 858.53 858.53 0.00 113.48 114.57 115.66 116.49 117.61 118.65 119.47 120.53 121.56 122.60 123.63 124.68 125.53 126.62 127.47 128.56 129.60 130.67 131.57 132.51 133.57 134.66 135.62 136.53 137.59 138.68 139.56 140.52 141.54 142.59 143.66 144.49 145.66 146.69 147.54 148.76 149.78 150.52 151.52 152.61 153.57 154.64 155.51 156.49 157.63 158.48 159.99 160.58 161.97 162.80 163.76 164.87 164.87 0.00 0 .817 916.9 0 .908 930.1 0 .825 944.0 0 .830 955.0 0 .933 967.7 0 .962 980.0 1 .025 989.0 1 .060 1000.2 1 .095 1010.3 1 .130 1021.7 1 .256 1032.7 1 .346 1044.1 1 .517 1052.8 1 .557 1064.5 1 .634 1073.6 1 .816 1084.4 1 .925 1095.1 1 .981 1107.8 2 .250 1117.9 2 .473 1128.4 2 .523 1141.6 2 .725 1155.5 3 .000 1167.9 3 .250 1179.7 3 .533 1184.9 3 .633 1195.6 3 .666 1206.0 4 .000 1217.0 4 .250 1220.4 4 .375 1198.4 4 .458 1205.3 5 .187 1212.9 5 .850 1227.3 6 .437 1243.2 7 .083 1257.5 7 .625 1280.0 8 .500 1300.6 9 .250 1316.9 10 .000 1341.3 10 .900 1373.2 12 .000 1408.0 13 .375 1455.7 14 .500 1500.0 16 .333 1554.4 19 .000 1624.0 21 .250 1685.6 25 .166 1829.2 29 .500 1909.9 34 .750 2172.7 41 .500 2339.9 48 .000 2486.4 55 .500 2596.5 0 .002 2632.3 0 .000 0.0 13.27 11.00 10.53 11.00 10.58 11.39 11.25 11.20 10.74 12.39 13.41 14.62 15.54 16.71 17.50 18.00 19.81 23.52 25.25 27.63 31.43 .34.75 38.75 42.14 17.33 35.67 43.33 45.83 14.17 -91.67 28.75 47.50 72.00 99.37 119.17 140.62 171.67 203.75 244.00 319.00 435.00596.25 738.33 906.67 1160.00 1540.00 2393.33 4035.00 6570.00 8360.00 7325.00 5505.00 0.00 3.07 DOW CONFIDENTIAL Noah 3.17 Analytical DOU Scienc;egsa, CONFIDENTIAL INFORMATION Louisiana__p ij^h I on, Dou ChenicaI AR Company SELF-HEAT RATE 5* 4. Process SP-202J6arSaehatla(nat +)i CVhisoirdI Customer s onth|ar OpariTori Gerald Barr I I li Analyst: Gerald arr I I I ea aux PnT Factor: 1.50 100.0 - Exotherm" Search US. TEMPERATURE Pun Date: 03-24-92 lotted diets: 03-24-92 RCL: 72-0692 u me me t h; 50.0- c E U\ uae Kvaa a a x a 14 n O 31 Z3 Tl --' I> 33 Z~J \3) 3-> ^> 20. 0 -- 10. 0---- 5. 0-- 2.0 -- 1.0 0.5-- 0. 2 -- 0. I -- 0.03 -- / / / 0.02- 0.01- t--f~ I I-4--1 --t--t--1--1--t-+~H |-I 20 40 60 / / / Noah J . 1 7 , DOU CONFIDENTIAL INFORMATION --------------------------- Analytical Sciences, Louiaiana uiviaion, Dou Chemical Company ARC ---------- ,, ,, TEMPERATURE ^'SrC IrSfiM*`2PrOC*" SP"2025.f:hi*?Jm>+1C9,dn" AnSiSStrG;A:7 isP?VlTS.ux PRTTactor: T ?^0 "*rr * 1 'u* US. TIME PLOT Run Date- 03 24 92 Plotted 6ata: ^3-24-92 S00 TMofhtr* Starch RCLi 92-0692 ll:s : fin? 450 400 350 u 300a v 9 +L*L93a 250 200- 150- 100 C ONF TDFNT TAI D 50X> 3\) 4------1------1------1------------1-----4----- 1 I----- 1 - & 400 600 -I----- h 800 1000 Noah J . 1/ DhU CONFIDENTIAL INFORMATION ,' Analytical Science., Louisiana division, Dou Chemical Company AR~ PRESSURE US. iEMPERATURE SM?'XRt ll?ttpYrCM* Sp-2025.fWj"?atm)ic?'f5Jne Customer: Clark Ponthlar Analyst: Garald Barr I I leeux Operator: Gerald Barr I I 1eaux Phi Factor: t.50 1 0000 --- Exotherm" Search Pun Date* 03-24-92 jotted Oate: 03-24-92 RCL: 92-0692 II me me : 0?:?5 1 5000 2000 1000- t/> 500- CL Lm3 a e 200 L (L 100- 50 3 33 ZTJ 3 --i o-n o z \) 20- X"> O>' 10- 4-^ H--I--I--I--t l Ill I f I HHiltH-+-I-H-H |~H- t-i III- HI- |-H-l liK H-l--I--H-H-f-j--f{--I--H- 20 40- 60 80 1A0 120 140 180 220 260 300 400 500 T b> M I ., | Noah 3.17 .. DOW CONFIDENTIAL INFORMATION Analytic*! Sclancuo. Lou I b ^na^T^i a i on. Dou Chsmlcal Company RCL: 72-0692 PRESSURE RATE CCSAARauunmCssap:ttoloIyemAmsRetef:crr.:_6:?s1ra0tr0IfCd0n.0VPBos,r.rnolrtt"llhj"j reausxp-E2x"o2t8shR.eT?rrm:Ps;|oc`?rt.oi,.nf, cp't5i 0arr 1. I I Isiux Search 500.0 US. TEMPERATURE Pun Date: 03-24-72 lotted Date: 03-24-72 Tl:: ; Mil? 200.0 100. 0 50.0 20. 0- E\ 10.0 W a. 5.0- +- O*' a 2. 0 aL3 a 1.0 aL Q. 0. 5- o To2| cO --zHO-ni< I> --\\o)) ~I> N^1 0. 2 0. 1- 0.05- V 0.02- 0.01- -I--I--I--I--|--I--I--1-4--) H-HH-1 -H I 20 40 60 I I I H l-H-H I H-l t-| --t--t- 100 2 20 260 300 -t--t--H- 400 500 Noah 3.17 Swr'XRi Cue t omor Ana Iuat: DOW CONFIDENTIAL INFORMATION Analytical Sciences. Lou i b i v i a i on , Dou Chemical Company RCLs 72-0672 PRESSURE US. TIME Pun Dates 03-24-72 lotted Oates 03-24- 72 TISS j fliil Hcn CL mL3 L a. n ~zon oz> --f x> a ^z o\> \) --I --k J> > ~X |~ , -I -- I 600 B00 1000 17 Appendix B DOW CONFIDENTIAL INFORMATION ANALYTICAL REPORT Noah 3.17 RCL: 92-0708 Analytical Sciences, Louisiana Division, Dow Chemical Company TO: Clark Ponthier Chlorine Charge # 25 TITLE: Accelerating Rate Calorimetry Study of Steam & Process SP-CM Sealant + Liquid Chlorine AUTHOR(S) Gerald Barrilleaux Reviewed by Ran on: 04-24-92 at 16:49 -- Analyzed on: 04-27-93 at 00:09 ARC: ARC SYSTEM 2 SUMMARY The following results have been obtained by Accelerating Rate Calorimetry (ARC). Refer to data plots contained within this report for more detail. CAUTION: The following data were generated under specific phi factor conditions. These data should NOT be applied to larger scale operations without considering the effect of phi on the ARC results. Please contact Reactive Chemicals personnel for further interpretations and applications of these data. RCL: 92-0708 Steam & Process SP-CM Sealant + Liquid Chlorine ^ A 6.330 g sample was loaded into a No. 3.00, Hastalloy C ARC sample container which yields a phi factor of 1.62 assuming an average sample specific heat of 0.500 cal/g deg C. The sample atmosphere was Chlorine. The programmed step heating was initiated at 20 deg C with a heat step of 10.0 deg C. An exothermic reaction was detected at 23 deg C and 134.0 psia with a self-heating rate of 2.08 deg C/min. The maximum self-heat rate observed during this exotherm was 391.00 deg C/min at 130 deg C with a pressure of 15 psi. The observed temperature rise for this exotherm was 142 deg C. Using a phi factor of 1.62, the estimated adiabatic temperature rise is 231 deg C and the heat of reaction is 116 cal/g of total sample. This calculation assumes that any PV energy change during the reaction was negligible. no a n??i49 CONFTDFNT TAi 18 DOW CONFIDENTIAL INFORMATION -------------------------------- ACCELERATING RATE CALORIMETRY Noah 3.17----------------------------- Analytical Sciences, Louisiana Division, Dow Chemical Company RCL: 92-0708 -- Ran on: 04-24-92 at 16:49 -- Analyzed on: 04-27-93 at 00:09 Sample description: Steam & Process SP-CM Sealant + Liquid Chlorine Steam & Process SP-CM, 3.50 grams + Liquid Chlorine, 3.98 grams Submitted by: Clark Ponthier Phone Number: (504) 389-8167 Operator: Gerald Barrilleaux Analyst: Gerald Barrilleaux From: Chlorine Charge Number: 25 ARC: ARC SYSTEM 2 Experimental Conditions Tape Run number -------------------------------------------------Container type ----------------------------------------------------Container material---------------------------------------------Container weight, Mb ---------------------------------------Sample weight, Ms ---------------------------------------------Total System Volume, Vb (approx) ---------------Sample Volume, Vs (approx) ---------------------------Head space volume, Vg (approx) -------------------Head space atmosphere---------------------------------------Container Heat Capacity, Cb -------------------------Heat Capacity of the sample, Cs (assumed) Starting temperature ---------------------------------------- End temperature (specified) -------------------------End temperature (actual) -------------------------------Heat step --------------------------------------------------------------Wait time --------------------------------------------------------------Isothermal wait time ---------------------------------------Calorimetic rate threshold ---------------------------Stirring rate ------------------------------------------------------- 708.00 3.00 Hastalloy C 19.719 g 6.330 g 10.000 mL 5.150 mL 4.850 mL Chlorine 0.100 cal/deg C g 0.500 cal/deg C g 20.0 deg C 250.0 deg C 165.9 deg C 10.0 deg C 10 min 0 min 0.020 deg C/min 0 RPM Thermal Ratio, Phi = 1 + (Mb Cb)/(Ms Cs) 1.62 RUN PREPARATIONS: A Hastelloy C ARC sphere was loaded with SP-Cm sealant by rolling the sealant into strands which were immersed into liquid nitrogen to facilitate insertion into the sphere. The sealant was then no longer tacky and could be forced down the neck of the sphere. The sphere and SP-CM was then chilled in liquid nitrogen and chlorine was added. The sphere was attached immediately to the calorimeter and allowed to gradually reach ambient temperature. RUN COMMENTS: Start temperature was set at 20 deg. C, slightly below ambient so that exotherm mode could be forced immediately after the run was started in order to monitor any exotherms near ambient temperature. At 47 minutes into the experiment a large self-heat rate occurred, 391 d g. C/minute. At this time, pressure was 986 psia and the rupture disc burst. DO A 027150 OONFTDFNTTAl 19 EXPERIMENTAL The specified amount of the sample is introduced into the sample bomb which is in turn fitted to the calorimeter lid. The calorimeter is then ' rapidly heated to the initial temperature after which either an isothermal age mode or a WAIT-SEARCH-HEAT sequence is entered to look for exothermic reaction self-heating. When less than the self-heat rate threshold is observed during the SEARCH mode or at the end of the isothermal age time, a heat step is applied to the calorimeter contents. A WAIT-SEARCH-HEAT process is repeated until the self-heat rate of the bomb exceeds the threshold rate at which time the reaction is allowed to proceed on its own under nearly adiabatic conditions. Detailed procedures for the ARC can be found in the CSI operating manual. GENERAL PRECAUTIONS Accelerating rate calorimetry offers a useful method for evaluating exothermic run-away processes. However, caution should be used when relating the ARC data to an actual plant process since phi for an ARC experiment is usually very different from phi for a large-scale reaction. In addition, special consideration is needed when kinetic complications are present in the ARC data. For example, the effects of autocatalysis or inhibitors can vastly change the runaway reaction in chemical storage situations. Consultation with Reactive Chemicals is recommended in the applications of ARC data to plant processes. Extrapolation of the data outside the experimental range is generally unwise. DOVJ CONFIDENTIAL DO A 0??151 CONFTDFNT TAI ( 20 DOW CONFIDENTIAL INFORMATION -------------------------------- ACCELERATING RATE CALORIMETRY Noah 3.17----------------------------- Analytical Sciences, Louisiana Division, Dow Chemical Company RCL: 92-0708 -- Ran on: 04-24-92 at 16:49 -- Analyzed on: 04-27-93 at 00:09 Sample description: Steam & Process SP-CM Sealant + Liquid Chlorine Steam & Process SP-CM, 3.50 grams + Liquid Chlorine, 3.98 grams Submitted by: Clark Ponthier Phone Number: (504) 389-8167 Operator: Gerald Barrilleaux Analyst: Gerald Barrilleaux DATA LIST From: Chlorine Charge Number: 25 ARC: ARC SYSTEM 2 START LISTING START Exotherm EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM Heat Pressure Time Temperature Rate Pressure Rate (min) (C) (C/min) (psia) (psia/min) 0.00 0.00 9.01 9.51 9.99 10.41 10.93 11.33 11.81 12.19 12.65 13.15 13.53 13.91 14.33 14.75 15.11 15.53 15.89 16.23 16.63 17.03 17.37 17.81 18.17 18.59 19.03 19.39 19.79 20.29 20.69 21.19 21.69 0.00 0.00 23.35 24.42 25.48 26.35 27.47 28.37 29.46 30.35 31.42 32.55 33.46 34.38 35.44 36.53 37.46 38.53 39.46 40.35 41.43 42.50 43.38 44.48 45.39 46.45 47.54 48.42 49.38 50.50 51.35 52.44 53.53 0.000 0.000 2.075 2.140 2.208 2.071 2.153 2.250 2.270 2.342 2.326 2.260 2.394 2.421 2.523 2.595 2.583 2.547 2.583 2.617 2.700 2.675 2.588 2.500 2.527 2.523 2.477 2.444 2.400 2.240 2.125 2.180 2.180 0.0 0.0 134.0 142.3 148.5 150.9 159.5 166.2 173.3 178.7 185.1 192.0 198.3 204.0 211.1 218.4 225.0 232.7 239.5 246.1 254.0 261.8 268.6 277.5 284.5 293.0 301.6 308.7 316.3 325.7 333.2 342.2 351.0 0.00 0.00 14.87 16.60 12.92 5.71 16.54 16.75 14.79 14.21 13.91 13.80 16.58 15.00 16.90 17.38 18.33 18.33 18.89 19.41 19.75 19.50 20.00 20.23 19.44 20.24 19.55 19.72 19.00 18.80 18.75 18.00 17.60 qq oONF 1 DF NT T Al EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM 22.09 22.67 23.15 23.71 24.29 24.91 25.47 26.13 26.77 27.35 28.11 28.83 29.43 30.23 30.99 31.61 32.41 33.17 33.87 34.45 35.17 35.83 36.47 36.99 37.61 38.19 38.65 39.23 39.71 40.21 40.61 41.09 41.45 41.91 42.37 42.71 43.17 43.53 43.99 44.35 44.75 45.05 45.35 45.59 45.83 46.07 46.27 46.47 46.63 46.79 46.95 47.07 47.19 47.31 47.39 47.47 47.57 47.65 47.71 47.77 1 54.36 55.50 56.38 57.43 58.49 59.54 60.43 61.50 62.54 63.40 64.48 65.53 66.40 67.45 68.50 69.37 70.45 71.46 72.49 73.35 74.42 75.47 76.56 77.43 78.48 79.55 80.43 81.55 82.47 83.53 84.41 85.53 86.39 87.48 88.56 89.42 90.55 91.42 92.51 93.40 94.52 95.45 96.47 97.36 98.36 99.42 100.36 101.41 102.39 103.42 104.55 105.53 106.55 107.66 108.47 109.38 110.51 111.56 112.45 113.41 2 .075 1 .965 1 .833 1 .875 1 .827 1 .693 1 .589 1 .621 1 .625 1 .482 1 .421 1 .458 1 .450 1 .312 1 .381 1 .403 1 .350 1 .328 1 .471 1 .482 1 .486 1 .590 1 .703 1 .673 1 .693 1 .844 1 .913 1 .931 1 .916 2 .120 2 .200 2 .333 2 .388 2 .369 2 .347 2 .529 2 .456 2 .416 2 .369 2 . 472 2 .800 3 .100 3 .400 3 .708 4 .166 4 .416 4 .700 5 .250 6 .125 6 .437 7 .062 8 .166 8 .500 9 .250 10 .125 11 .375 11 .300 13 .125 14 .833 16 .000 357.9 367.6 375.5 384.5 393.5 402.8 411.2 421.1 430.3 438.2 448.6 458.3 466.2 477.0 486.9 495.5 506.0 516.7 526.8 535.4 546.5 557.2 567.6 576.4 587.4 598.2 606.7 617.8 627.7 638.0 646.6 657.3 665.4 675.6 686.2 693.5 703.1 709.8 719.3 728.1 739.7 749.6 760.8 770.7 781.6 793.5 805.2 817.9 828.6 840.7 853.5 863.7 874.5 886.3 894.6 903.0 914.2 924.3 932.4 941.4 DOW CONFIDENTIAL 17.25 16.72 16.46 16.07 15.52 15.00 15.00 15.00 14.37 13.62 13.68 13.47 13.17 13.50 13.03 13.87 13.13 14.08 14.43 14.83 15.42 16.21 16.25 16.92 17.74 18.62 18.48 19.14 20.62 20.60 21.50 22.29 22.50 22.17 23.04 21.47 20.87 18.61 20.65 24.44 29.00 33.00 37.33 41.25 45.42 49.58 58.50 63.50 66.87 75.63 80.00 85.00 90.00 98.33 103.75 105.00 112.00 126.25 135.00 150.00 DO A 02?153 CONFTDFNTTAI EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM END LIST 47.83 47.87 47.91 47.93 47.95 47.97 47.99 48.01 48.03 48.05 48.07 48.09 48.11 48.13 48.15 48.17 48.19 48.21 48.23 48.25 48.27 48.29 48.31 48.33 48.35 48.37 48.41 48.45 48.49 48.53 48.57 48.63 48.71 48.85 49.39 0.00 22 114.50 115.35 116.65 121.73 129.55 137.13 143.11 147.52 150.79 153.27 155.19 156.67 157.83 158.80 159.60 160.27 160.85 161.35 161.79 162.18 162.52 162.82 163.10 163.36 163.61 163.81 164.18 164.50 164.78 165.00 165.20 165.43 165.68 165.88 165.68 0.00 18.166 21.250 32.500 254.000 391.000 379.000 299.000 220.500 163.500 124.000 96.000 74.000 58.000 48.500 40.000 33.500 29.000 25.000 22.000 19.500 17.000 15.000 14.000 13.000 12.500 10.000 9.250 8.000 7.000 5.500 5.000 3.833 3.125 1.428 0.370 0.000 951.4 166.67 986.4 875.00 384.7 -1.504E+004 15.1 -1.848E+004 14.7 -20.00 14.6 -5.00 14.6 0.00 14.5 -5.00 14.4 -5.00 14.4 0.00 14.3 -5.00 14.3 0.00 14.3 0.00 14.3 0.00 14.2 -5.00 14.2 0.00 14.2 0.00 14.1 -5.00 14.1 0.00 14.1 0.00 14.1 0.00 14.0 -5.00 14.0 0.00 14.0 0.00 14.0 0.00 14.0 0.00 13.9 -2.50 13.8 -2.50 13.8 0.00 13.8 0.00 13.8 0.00 13.8 0.00 13.7 -1.25 13.5 -1.43 13.3 -0.37 0.0 0.27 DOW CONFIDENTIAL r)u A r r>Nr TDFNT 7A( Noah 3.17 i Analytical DON CONFIDENTIAL INFORMATION Sciencan, Louioiano Oivimon, Dou Chumicai ARC Company SELF-HEAT RATE US. TEMPERATURE Acnr'ARfc iJi?gnSProc8'SP_CM 5:rii?F+(94:,^'?30h,orlna Cub t omer : _C I arKi ponthjer Analuat: Gerald Barrilleaux ^jrjjtor: Garald BBarri I Ieaux PhT F ac t or: 1.62 Run Gate; 04-24-92 Plotted Date: 04-27-93 100.0- " Exotherm Search RCL : ? 2 - 0 708, r1 mu : 16:49 Time : 00:11 50.0 <\EJ TaaJ a oac a Ia <a/> n o z> TZ| O -*3<1 I> ti 3> 1> 'Jl -- 20.0 10.0 5.0 2.0 0.5 0. 2- I. 1 0.05 0.02 0.01 +--I--hH~ I --I - l - -f--I | i t I I 1 M I I 20 40 60 80 I I I I I I I I I I I I I I 1 1 I I II I I 1 I 1 1 I ini I I 100 120 li 0 180 2 20 260 30G lilt 40 0 500 UN)) Noah 3.17 00U CONFTOENTI* INFORMATION Analytical Sciencuu, Loui1tA1iia|nnk^ .Jt11uion, Uou Chuinical Companu TEMPERATURE sample ; Steam & ProciM SP-CM Sealant hlorlna ARC: ARC SYSTEM 2 tUfeeIght (am): 6.330 Customer: Clark. Ponthler Operator: Gerald BarriIleaux Ana I oat: Gerald Barn I laaux PhT Factor: 1.62 500 --u-frxbfKerin Search US. TIME PLOT Run Date: 04-24-72 Plotted Data: 04-27-73 RCL 2-07081 I I me : 16:47 time 00:22 450 400 350 300 TtaaJ 250 toC- 200 150- 100 n oa zo 50 22} 'oJ v> --< --i J> Ln Ch -I-----------i- I-- ---- -I 200 400 600 800 1000 Noah 3.17 .e D0U CONFIDENTIAL INFORMATION nn I ut I ca | Sciences, Lou i b ** ln' Dou Chemical Company RCL: 92-0708, PRESSURE US bi.iinp I e ARC; ARC Customer: J I ark Ana Iu>t: Gars Id Procaaa SP-Ch Sea Iaarnt Liquid Chlorine onth|ar MeI ah t Operat ( am 1. 6,330 BsrriIlesux srri I Ieaux 10000 -------- ExoFhera Saarch TEMPERATURE Run Date: 04-24-92 Plotted Date: 04-27-93 T I me T i me 16:49 00:17 5000- 2000 1000 <t H 500 14 a. L3a aaL 200 -- 100 - // n 2t3| DV Z-t) 3> 71 3 Z \J ]> 'Ji - Nl t / 50 20-- - :J10 -M- -f-t M t I I I > I I I I I i 11111 i 20 40 60 80 100 0 1 40 I tLn> I I I I j II II I : I I I I I I 0 220 260 300 I I If l 400 500 iNoah 3.17 Analytical DOW CONFIDENTI INFORMATION Sciancaa. Luuiuian* IB ion. lloo Chemical ARC Company PRESSURE RATE US. TEMPERATURE SYST?ni`2PrOCaB" SP'Cn 5:r^Ft(atm,L:,^'f3gh,0r,ne CAunsatloymste:r:: G` Cerlraairl|kdd 1000. gPB`poannrrtthihIljleeerraux OPQhpTpe^rFragatrocortr:o: r; G raid 1.62 Exofharm Search BarriIleaux Run Data: 04-24 92 Plotted Data: 04-27-93 500.0 RCl 2-07CJ8| iI imn ae 16:49 00: 32 200.0 100.0 50.0 E\ Va\ am e eLL3e CL 26i Oz> z>* i> -2< \\o>) I> Ui ~ 30 20.010.0 5.0- rf 2.0 1.0 0.5- 0. 2 0. 1 0.05 0.02 0.01- I--I--I--t- j 20 Mil: 40 60 ii ini I mI I iI I j I I I I I I : i ' | i II I |' I I I l I I I I I I l I II iI I I i I 80 100 120 M0 160 220 260 300 4000 560 I5 CN Noah 3.17 Ana I ut i cii I noil CONFIDENTIAl INFORIWM [oil Sciuncuu. Lou i u i ana III i a i un. Uuu Lhumical ARC PRESSURE S.imp I < j>tBteaame ia. Pr rociai SP-CM ARC: ARC SYSTEM 2 Customer: Clark Ponthlar Analuat: Gerald BarrilTei Operator: Gerald Barrilleaux PnT Factor: 1.62 2500.0 Exofherm Search US. TIME Company Run Date. 04-24-92 Plotted Data: 04-27-93 RCI : 92 070U, T t me Tima 16: 49 00: 27 2250.0 2000.0 1750.0- 1500.0 i/i a. a 1250.0 L3 a a La a. 1000.0- 750.0 1J I l OO V zTl o -* 3> o Tl O Z---I( \\-->)* T> - vO 500.0 250.0- 0.0 -I-----f------ 1----- f200 i----- - 1 I --1- I - - - I r - 600 800 1000 28 Appendix C DOW CONFIDENTIAL INFORMATION ANALYTICAL REPORT Noah 3.17 RCL: 92-0711 Analytical Sciences, Louisiana Division, Dow Chemical Company TO: Clark Ponthier Chlorine Charge # 25 TITLE: Accelerating Rate Calorimetry Study of Steam & Process SP-300D + Chlorine AUTHOR(S) Gerald Barrilleaux Reviewed by Ran on: 04-30-92 at 13:50 -- Analyzed on: 04-30-92 at 15:35 ARC: ARC SYSTEM 2 SUMMARY The following results have been obtained by Accelerating Rate Calorimetry (ARC). Refer to data plots contained within this report for more detail. CAUTION: The following data were generated under specific phi factor conditions. These data should NOT be applied to larger scale operations without considering the effect of phi on the ARC results. Please contact Reactive Chemicals personnel for further interpretations and applications of these data. RCL: 92-0711 Steam & Process SP-300D + Chlorine A 7.670 g sample was loaded into a No. 3.00, Hastalloy C ARC sampl container which yields a phi factor of 1.48 assuming an averag sample specific heat of 0.500 cal/g deg C. The sample atmosphere was Chlorine. The programmed step heating was initiated at 21 deg C with a heat step of 10.0 deg C. An exothermic reaction was detected at 22 deg C and 111.0 psia with a self-heating rate of 0.08 deg C/min. This exotherm was terminated at 175 d g c and a pressure of 1361 psi, due to reaching the specified END TEMPERATURE of 175 deg c. If the exotherm had been allowed to continue, it may have reached significantly higher temperatures and/or pressures. Therefore, these data may not represent the full potential of this exothermic reaction. DO A 0P71A0 rONFTDFNTTAl 29 DOW CONFIDENTIAL INFORMATION ----------------------------------ACCELERATING RATE CALORIMETRY Noah 3.17--------------------------------- Analytical Sciences, Louisiana Division, Dow Chemical Company RCL: 92-0711 -- Ran on: 04-30-92 at 13:50 -- Analyzed on: 04-30-92 at 15:35 Sample description: Steam & Process SP-300D + Chlorine Steam & Process SP-300D + Liquid Chlorine Submitted by: Clark Ponthier Phone Number: (504) 389-8167 Operator: Gerald Barrilleaux Analyst: Gerald Barrilleaux From: Chlorine Charge Number: 25 ARC: ARC SYSTEM 2 Experimental Conditions Tape Run number----- ;--------------------------------------------Container type ----------------------------------------------------Container material----------------------------------------------Container weight, Mb ---------------------------------------Sample weight, Ms ----------------------------------------------Total System Volume, Vb (approx) ---------------Sample Volume, Vs (approx) ---------------------------Head space volume, Vg (approx) -------------------Head space atmosphere---------------------------------------Container Heat Capacity, Cb -------------------------Heat Capacity of the sample, Cs (assumed) Starting temperature ---------------------------------------End temperature --------------------------------------------------Heat step --------------------------------------------------------------Wait time --------------------------------------------------------------Isothermal wait time ---------------------------------------Calorimetic rate threshold ---------------------------Stirring rate ------------------------------------------------------- 711.00 3.00 Hastalloy C 18.389 g 7.670 g 10.000 mL 4.950 mL 5.050 mL Chlorine 0.100 cal/deg C g 0.500 cal/deg C g 21.0 deg C 175.0 deg C 10.0 deg C 10 min 0 rain 0.020 deg C/min 0 RPM Thermal Ratio, Phi = 1 + (Mb Cb)/(Ms Cs) 1.48 RUN PREPARATIONS: Since the SP-300D is a very tacky sealant, it was rolled into narrow strips and chilled in liquid nitrogen in order to load a Hastelloy C ARC sphere via the 1/8" inlet. Once a sufficient amount of sealant was loaded, the sphere and contents were chilled in liquid nitrogen and liquid chlorine was added. The sphere remained in liquid nitrogen until it was attached to the calorimeter. Air intrusion was prevented. RUN COMMENTS: The sphere was allowed to equilibrate to ambient temperature, 21 deg. C, which was also set as start temperature, before the experiment was begun. The analysis ended at the temperature set, 175 deg. C, although f self-heating was still increasing at this time. After cooling, pr ssure ^ was 609 psia at 25.6 deg. C. EXPERIMENTAL no a CONFTDFNTTAl 30 The specified amount of the sample is introduced into the sample bomb which is in turn fitt d to the calorimeter lid. The calorimeter is then rapidly heated to the initial temperature after which either an isothermal age mode or a WAIT-SEARCH-HEAT sequence is entered to look for exothermic reaction self-heating. When less than the self-heat rate threshold is observed during the SEARCH mode or at the end of the isothermal age time, a heat step is applied to the calorimeter contents. A WAIT-SEARCH-HEAT process is repeated until the self-heat rate of the bomb exceeds the threshold rate at which time the reaction is allowed to proceed on its own under nearly adiabatic conditions. Detailed procedures for the ARC can be found in the CSI operating manual. GENERAL PRECAUTIONS Accelerating rate calorimetry offers a useful method for evaluating exothermic run-away processes. However, caution should be used when relating the ARC data to an actual plant process since phi for an ARC experiment is usually very different from phi for a large-scale reaction. In addition, special consideration is needed when kinetic complications are present in the ARC data. For example, the effects of autocatalysis or inhibitors can vastly change the runaway reaction in chemical storage situations. Consultation with Reactive Chemicals is recommended in the applications of ARC data to plant processes. Extrapolation of the data outside the experimental range is generally unwise. Dow Confidential DO A 077 \ t'7 CONF TDFNT I Al 31 DOW CONFIDENTIAL INFORMATION ---------------------------------- ACCELERATING RATE CALORIMETRY Noah 3.17--------------------------------- Analytical Sciences, Louisiana Division, Dow Chemical Company RCL: 92-0711 -- Ran on: 04-30-92 at 13:50 -- Analyzed on: 04-30-92 at 15:35 Sample description: Steam & Process SP-300D + Chlorine Steam & Process SP-300D + Liquid Chlorine Submitted by: Clark Ponthier Phone Number: (504) 389-8167 Operator: Gerald Barrilleaux Analyst: Gerald Barrilleaux DATA LIST From: Chlorine Charge Number: 25 ARC: ARC SYSTEM 2 START LISTING START Exotherm EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM. EXOTHERM EXOTHERM EXOTHERM EXOTHERM Heat Pressure Time 'Pemperature Rate Pressure Rate (min) (C) (C/min) (psia) (psia/min) 0.00 0.00 13.41 28.97 47.11 67.43 87.59 108.55 127.87 147.87 167.39 185.31 204.13 218.15 236.71 254.27 271.41 288.65 304.57 320.67 335.37 347.41 361.13 374.53 387.37 399.03 410.51 421.75 432.77 443.45 453.29 460.97 470.33 0.00 0.00 22.17 23.21 24.21 25.21 26.23 27.26 28.26 29.31 30.34 31.35 32.36 33.17 34.22 35.26 36.26 37.29 38.31 39.34 40.36 41.18 42.20 43.24 44.25 45.26 46.27 47.28 48.31 49.31 50.33 51.17 52.20 0.000 0.000 0.078 0.066 0.055 0.049 0.050 0.049 0.051 0.052 0.052 0.056 0.053 0.057 0.056 0.059 0.058 0.059 0.064 0.063 0.069 0.068 0.074 0.077 0.078 0.086 0.087 0.089 0.093 0.093 0.103 0.109 0.110 o.o 0.0 111.0 114.5 118.8 123.4 128.2 133.4 138.3 143.7 149.1 154.3 160.0 164.4 170.5 176.5 182.5 188.8 195.0 201.6 208.0 213.5 220.1 227.0 234.0 240.8 247.9 255.3 262.9 270.8 278.5 284.9 293.0 0.00 0.00 8.28 0.22 0.24 0.23 0.24 0.25 0.25 0.27 _ 0.28 0.29 0.30 0.31 0.33 0.34 0.35 0.37 0.39 0.41 0.44 0.46 0.48 0.51 0.55 0.58 0.62 0.66 0.69 0.74 0.78 0.83 0.87 CONFTDFNTTAt EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM 479.33 487.37 495.63 503.23 510.53 517.73 524.17 529.47 535.55 541.59 547.11 552.33 557.55 562.67 567.31 570.99 575.47 579.79 583.95 587.93 591.81 595.57 599.17 602.01 605.53 609.07 612.37 615.65 618.95 622.37 625.19 628.77 632.53 636.23 640.23 644.37 647.75 652.31 657.27 662.73 668.67 675.91 684.91 696.05 705.87 719.73 734.85 751.69 769.61 787.73 804.13 818.97 833.53 846.23 855.35 865.91 875.51 884.51 892.37 899.31 32 53.21 54.22 55.25 56.27 57.29 58.33 59.37 60.19 61.22 62.25 63.27 64.30 65.32 66.34 67.36 68.18 69.18 70.21 71.25 72.28 73.32 74.34 75.36 76.17 77.20 78.24 79.25 80.29 81.32 82.36 83.18 84.22 85.27 86.31 87.36 88.36 89.19 90.23 91.24 92.26 93.28 94.31 95.33 96.36 97.18 98.21 99.23 100.24 101.24 102.27 103.28 104.28 105.33 106.36 107.18 108.20 109.22 110.25 111.25 112.25 0.112 0.125 0.124 0.134 0.139 0.144 0.161 0.154 0.169 0.170 0.184 0.197 0.195 0.199 0.219 0.222 0.223 0.238 0.250 0.258 0.268 0.271 0.283 0.285 0.292 0.293 0.306 0.317 0.312 0.304 0.290 0.290 0.279 0.281 0.262 0.241 0.245 0.228 0.203 0.186 0.171 0.142 0.113 0.092 0.083 0.074 0.067 0.059 0.055 0.056 0.061 0.067 0.072 0.081 0.089 0.096 0.106 0.114 0.127 0.144 301.3 309.2 317.9 326.3 334.8 343.7 352.3 359.7 368.5 377.9 387.1 396.4 406.0 415.9 425.5 433.5 443.6 453.8 464.0 474.6 485.0 495.5 506.1 514.9 525.7 536.7 546.8 557.0 567.1 577.4 585.7 595.4 604.9 614.8 624.3 632.9 640.9 650.8 660.6 670.5 680.1 690.3 699.9 709.7 717.7 727.5 736.8 744.6 752.2 758.8 764.9 770.4 775.8 781.7 786.6 792.1 797.7 803.5 809.4 816.6 Dow Confidential 0.92 0.98 1.05 1.11 1.16 1.24 1.34 1.40 1.45 1.56 1.67 1.78 1.84 1.93 2.07 2.17 2.25 2.36 2.45 2.66 2.68 2.79 2.94 3.10 3.07 3.11 3.06 3.11 3.06 3.01 2.94 2.71 2.53 2.68 2.38 2.08 2.37 2.17 1.98 1.81 1.62 1.41 1.07 0.88 0.81 0.71 0.62 0.46 0.42 0.36 0.37 0.37 0.37 0.46 0.54 0.52 0.58 0.64 0.75 1.04 DO A CONFTDFNT T Al EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM 905.25 910.33 915.05 919.45 923.63 926.75 930.69 934.59 938.07 941.19 944.31 947.25 950.13 952.29 955.05 957.51 959.87 962.13 964.29 966.29 967.85 969.77 971.57 973.25 974.53 976.01 977.53 978.93 980.01 981.33 982.57 983.53 984.61 985.57 986.57 987.29 988.21 989.05 989.75 990.53 991.27 991.87 992.59 993.29 993.81 994.43 995.03 995.61 996.07 996.61 997.05 997.57 998.07 998.47 998.97 999.37 999.77 1000.25 1000.65 1001.13 33 113.28 114.30 115.32 116.35 117.37 118.19 119.22 120.24 121.26 122.27 123.28 124.32 125.35 126.17 127.21 128.25 129.28 130.29 131.34 132.36 133.19 134.24 135.29 136.34 137.18 138.18 139.25 140.29 141.17 142.26 143.34 144.26 145.29 146.32 147.37 148.20 149.25 150.33 151.21 152.27 153.33 154.19 155.27 156.35 157.19 158.25 159.30 160.36 161.24 162.30 163.17 164.25 165.38 166.27 167.37 168.28 169.22 170.34 171.23 172.33 0.173 824.2 0.200 832.8 0.216 841.2 0.234 849.3 0.244 857.4 0.262 863.4 0.261 870.7 0.261 877.5 0.293 886.3 0.323 894.7 0.323 903.6 0.353 911.4 0.357 919.0 0.379 925.2 0.376 933.5 0.422 941.5 0.436 949.6 0.446 958.9 0.486 967.4 0.510 976.4 0.532 983.4 0.546 993.0 0.583 1003.0 0.625 1012.9 0.656 1021.0 0.675 1030.6 0.703 1041.3 0.742 1052.1 0.814 1060.4 0.825 1072.5 0.870 1084.4 0.958 1094.5 0.953 1106.4 1.072 1117.3 1.050 1129.8 1.152 1139.0 1.141 1151.2 1.285 1163.1 1.257 1173.0 1.358 1184.7 1.432 1195.8 1.433 1204.5 1.500 1212.7 1.542 1220.6 1.615 1226.8 1.709 1236.2 1.750 1246.3 1.827 1253.8 1.913 1257.4 1.962 1261.9 1.977 1271.1 2.076 1282.2 2.260 1292.6 2.225 1299.9 2.200 1310.0 2.275 1317.0 2.350 1324.0 2.333 1332.0 2.225 133-8.1 2.291 1345.4 Dow Confidential 1.28 1.69 1.78 1.84 1.94 1.92 1.85 1.74 2.53 2.69 2.85 2.65 2.64 2.87 3.01 3.25 3.43 4.12 3.94 4.50 4.49 5.00 5.56 5.89 6.33 6.49 7.04 7.71 7.69 9.17 9.60 10.52 11.02 11.35 12.50 12.78 13.26 14.17 14.14 15.00 15.00 14 .'50 11.39 11.29 11.92 15.16 16.83 12.93 7.83 8.33 20.91 21.35 20.80 18.25 20.20 17.50 17.50 16.67 15.25 15.21 DO A 0??1 OONFTOFNTT EXOTHERM EXOTHERM EXOTHERM END LIST 1001.53 1002.01 1002.21 0.00 173.27 174.39 174.84 0.00 2.350 1351.5 2.333 1358.1 2.250 1361.4 0.000 0.0 15.25 13.75 16.50 1.36 Dow Confidential HO A CONFTDFNTTA1 Noah 3.17 40 Appendix D DOW CONFIDENTIAL INFORMATION ANALYTICAL REPORT Noah 3.17 RCL: 92-0715 Analytical Sciences, Louisiana Division, Dow Chemical Company TO: Clark Ponthier Chlorine Plant Charge # 25 TITLE: Accelerating Rate Calorimetry Study of Steam & Process SP-TFLO + Liquid Chlorine AUTHOR(S) Gerald Barrilleaux Reviewed by Ran on: 05-28-92 at 07:55 -- Analyzed on: 05-28-92 at 15:53 ARC: ARC SYSTEM 1 SUMMARY The following results have been obtained by Accelerating Rate Calorimetry (ARC). Refer to data plots contained within this report for more detail. CAUTION: The following data were generated under specific phi factor conditions. These data should NOT be applied to larger scale operations without considering the effect of phi on the ARC results. Please contact Reactive Chemicals personnel for further interpretations and applications of these data. RCL: 92-0715 Steam & Process SP-TFLO + Liquid Chlorine A 8.140 g sample was loaded into a No. 3.00, Hastalloy C ARC sample container which yields a phi factor of 1.46 assuming an average sample specific heat of 0.500 cal/g deg C. The sample atmosphere was Chlorine. Isothermal aging of the sample was begun at 21 deg C. An exothermic reaction was detected at 139 deg C and 793.4 psia with a self-heating rate of 0.03 deg C/min. The maximum self-heat rate observed during this exotherm was 0.03 deg C/min at 139 deg C with a pressure of 793 psi. The observed temperature rise for this exotherm .was 8 deg C. Using a phi factor of 1.46, the estimated adiabatic temperature rise is 12 deg C and the heat of reaction is 6 cal/g of total sample. This calculation assumes that any PV energy change during the reaction was negligible. Additional exotherms were detected at 32, 124, 159, and 173 d g C. no A OPP1 ~?P CONFTDFNTTAl 41 DOW CONFIDENTIAL INFORMATION ---------------------------------- ACCELERATING RATE CALORIMETRY Noah 3.17------------------------------- Analytical Sciences, Louisiana Division, Dow Chemical Company RCL: 92-0715 -- Ran on: 05-28-92 at 07:55 -- Analyzed on: 05-28-92 at 15:53 Sample description: Steam & Process SP-TFLO + Liquid Chlorine Sealant SP-TFLO + Chlorine Submitted by: Clark Ponthier Phone Number: (504) 389-8167 Operator: Gerald Barrilleaux Analyst: Gerald Barrilleaux From: Chlorin Plant Charge Number: 25 ARC: ARC SYSTEM 1 Experimental Conditions Tape Run number ----- --------------------------------------------Container type ----------------------------------------------------Container material---------------------------------------------Container weight, Mb ---------------------------------------Sample weight, Ms ---------------------------------------------Total System Volume, Vb (approx) ---------------Sample Volume, Vs (approx) ---------------------------H ad space volume, Vg (approx) -------------------Head space atmosphere---------------------------------------Container Heat Capacity, Cb -------------------------Heat Capacity of the sample, Cs (assumed) Starting temperature ---------------------------------------End temperature --------------------------------------------------Heat step --------------------------------------------------------------Wait time --------------------------------------------------------------Isothermal wait time ---------------------------------------Calorimetic rate threshold ---------------------------- Stirring rate ------------------------------------------------------- 715.00 3.00 Hastalloy C 18.820 g 8.140 g 10.000 ttiT. 5.000 mL 5.000 wiT. Chlorine 0.100 cal/deg C 0.500 cal/deg c 21.0 deg C 175.0 deg C 10.0 deg C 10 min 0 min 0.020 deg C/min 0 RPM Thermal Ratio, Phi = 1 + (Mb Cb)/(Ms Cs) 1.46 RUN PREPARATIONS: The Teflon/Fluorolube material was formulated according to recommendations by G. Wagener, G. Barrilleaux, and J. Schell to Clark Ponthier. Loading into the Hastelloy C ARC sphere was accomplished by first rolling the sealant into thin strands and then freezing in liquid nitrogen. After loading of the sealant was completed, the sphere was immersed in liquid nitrogen and chlorine was added. The sphere was immediately attached to the calorimeter and allowed to gradually reach ambient temperature where the experiment was started. TCLo + 3.1, RUN COMMENTS: After, cool-down, pressure was 243 psia at 24.3 deg. C. EXPERIMENTAL no A 077173 CONFTDFNTTAl The specified amount of the sample is introduced into th sample bomb which is in turn fitted to the calorim ter lid. Th calorim ter is then 42 rapidly heated to the initial temperature aft r which either an isothermal age mode or a WAIT-SEARCH-HEAT sequenc is entered to look for xothermic reaction self-heating. When less than the self-heat rate threshold is observed during the SEARCH mod or at the end of the isothermal age time, a heat step is applied to the calorimeter c ntents. A WAIT-SEARCH-HEAT process is repeated until the self-heat rate of the bomb exceeds the threshold rate at which time the reaction is allowed to proceed on its own under nearly adiabatic conditions. Detailed procedures for the ARC can be found in the CSI operating manual. GENERAL PRECAUTIONS Accelerating rate calorimetry offers a useful method for evaluating exothermic run-away processes. However, caution should be used when relating the ARC data to an actual plant process since phi for an ARC experiment is usually very different from phi for a large-scale reaction. In addition, special consideration is needed when kinetic complications are present in the ARC data. For example, the effects of autocatalysis or inhibitors can vastly change the runaway reaction in chemical storage situations. Consultation with Reactive Chemicals is recommended in the applications of ARC data to plant processes. Extrapolation of the data outside the experimental range is generally unwise. Dow Confidential no A 0PP174 CONF TDFNT TAI 43 DOW CONFIDENTIAL INFORMATION ---------------------------------- ACCELERATING RATE CALORIMETRY Noah 3.17------------------------------ Analytical Sciences, Louisiana Division, Dow Chemical Company RCL: 92-0715 -- Ran on: 05-28-92 at 07:55 -- Analyzed on: 05-28-92 at 15:53 Sample description: Steam & Process SP-TFLO + Liquid Chlorine Sealant SP-TFLO + Chlorine Submitted by: Clark Ponthier Phone Number: (504) 389-8167 Operator: Gerald Barrilleaux Analyst: Gerald Barrilleaux DATA LIST From: Chlorine Plant Charge Number: 25 ARC: ARC Heat Pressure Time 'Temperature Rate Pressure Rate (min) (C) (C/min) (psia) (psia/min) START LISTING START Exotherm EXOTHERM EXOTHERM START Exotherm EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM START Exotherm EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM START Exotherm EXOTHERM EXOTHERM EXOTHERM EXOTHERM EXOTHERM START Exotherm EXOTHERM EXOTHERM EXOTHERM 0.00 0.00 132.90 181.37 0.00 562.76 598.66 643.11 689.89 735.07 747.58 0.00 800.68 836.61 873.31 905.09 946.07 989.81 1035.89 1086.69 1136.61 0.00 1196.18 1242.50 1298.41 1357.26 1393.87 0.00 1452.05 1498.63 1530.45 0.00 0.00 32.21 32.99 0.00 124.10 125.16 126.21 127.25 128.10 128.29 0.00 139.36 140.42 141.50 142.36 143.41 144.44 145.48 146.50 147.32 0.00 158.50 159.51 160.54 161.55 162.11 0.00 173.24 174.25 174.86 0.000 0.0 0.000 0.0 0.019 146.4 0.016 149.4 0.000 0.0 0.031 687.3 0.029 695.8 0.023 701.7 0.022 707.7 0.018 712.5 0.015 713.7 0.000 0.0 0.032 793.4 0.029 801.9 0.029 809.5 0.027 815.4 0.025 822.9 0.023 830.2 0.022 838.1 0.020 844.3 0.016 848.9 0.000 0.0 0.026 926.3 0.021 933.4 0.018 939.8 0.017 946.1 0.015 949.6 0.000 0.0 0.027 1018.5 0.021 1024.3 0.019 1026.9 0.00 0.00 1.10 0.06 0.82 1.41 0.24 0.13 0.13 0.11 _ 0.10 0.95 1.50 0.24 0.21 0.19 0.18 0.17 0.17 0.12 0.09 0.75 1.30 0.15 0.11 0.11 0.10 0.68 1.18 0.12 0.08 no A 077175 OONFTDFNTT Al Cf LOUISIANA B. W. Bailey C. B. Carpenter B. Cisneros S. Corbino K. D. Diamond J. W. Gross T. M. Gunn S. F. Hanrahan J. E. Henry R. D. Hudson D. S. Jones V. E. McMurray C. D. Messelt W. S. Milligan M. T. Mitchell J. C. Monroe C. J. Ponthier R. D. Summers R. D. Thornhill B. M. Williams B.G. Witt Patent Department CRI (5) Distribution List - 3301W - 6605 - 2510 - 3801 - 1901 - 2511 - 1701 - 3305 - 1501 - 3601 - 3502W - 8601 - 6601 - 5301 - 807 - 3305 - 2601 - 2510 - 2601 - 2509 - 2502 - 2507 - 2507 FREEPORT W. H. Cook W. W. Henslee *L. M. Kroposki D. J. Leggett D. C. Schulz W. E. Shewbart *S. F. Spangenberg G. L. Stevens CRI (1) MIDLAND J. S. Kelyman M. V. Koch' J. B. Powers CRI (1) PITTSBURG C. N. Harris J. D. Moseley FORT SASKATCHEWAN W. B. Ell H. W. Vandenbom *R. A. Wagner - 158 - 91A - 158 Summary Only SARNIA A. R. McDowell B. A. Prine STADE H. B. *E. L. H. J. F. J. W. Bleichert Dreher Nau Schollemann Steinmetzer - A-1230 - A-915 - B-1225 - B-1216 - B-101 - B-101 - B-1225 - A-1230 - B-1210 - 566 - 1897 - 1897C - 566 - 463 - 463 - 1010 - 53 - C-5 - C4-1 - A4 - G 5-2 - C4-1 DO A OPP181 f.ONF TOFNTTAl