ENGINEERING RESEARCH INSTITUTE THE UNIVERSITY OF MICHIGAN ANN ARBOR Semi-Annual Rep ort EFFECT OF GAMMA RADIATION ON VARIOUS PETROCHEMICAL REACTIONS July 1956, to January, 1957 Project Supervisors Joseph J. M artin Kenneth F.-Gordon Research Assistants William V. Dicke Richard C. Schwing Wayne D. Kuhn Dwight F. Decker Project 2420 STANDARD OIL COMPANY (INDIANA) WHITING, INDIANA

The University of Michigan * Engineering Research Institute TABLE OF CONTENTS P age List of Tables iii List of Figures iv Objective v Abstract vi I. Introduction II Summary of Results 1 A., Catalytic Cracking of Cetane 1 B o Para-Xylene Experiments 2 CO Ethyl Mercaptan Reactions 2 Do Alkylation and Copolymerization 2 III Catalytic Cracking of Cetane 3 A.o Discussion *of Results and Conclusions 3 Bo Results 4 C, Experimental Procedure 11 IV. P ara-Xylene Experiment s 11 A. Ethylene and Para-Xylene 11 (1) Discussion of Results and Conclusions 11 (2) Results 11 (3) Equipment and Procedure 13 Bo Propylene and Para-Xylene 13 (1) Discussion of Results and Conclusions 13 (2) Results 13 (3) Equipment and Procedure 13 Vo Ethyl Mercaptan Experiments 15 A. Discussion of Results and Conclusions 15 (1) Ethylene 15 (2) Propylene 17 B, Results 21 C, Equipment and Procedure 23 VIo Alkylation and Copolymerization 25 Ao Discussion of Results and Conclusions 25 B, Results 25 (1) Isobutane 25 (a) Ethylene 25 (b) Propylene 25 (c) Butylene 27 (2) N-Butane 27 (3) Aniline and Ethylene 27 (4) Butylene and Propylene 27 C. Procedure 28 VII, Appendix 30

The University of Michigan * Engineering Research Institute LIST OF TABLES No. Page Io Product Distribution and Average Molecular Weights of Gas Samples from Catalytic Cracks ing of Cetane 9 IIo Summary of Catalytic Cracking of Cetane 10 IIIo Ethylene and Para-Xylene Summary of Results 12 IV, Propylene and Para-Xylene Summary of Results 15 V o Ethylene and Ethyl Mercaptan Summary of 18 Results VI. Propylene and Ethyl Mercaptan Summary of 22 Results VII Summary - Alkylation Experiments 26

The University of Michigan * Engineering Research Institute LIST OF FIGURES Noo Page 1o Cetane in Product, Wt, percent of total feed, vso Space Velocity 5 2 Liquid Product Lighter than Cetane, Wto percent of total feed, vso Space Velocity 6 3, Carbon Deposit on Catalyst, Wt. percent per 100 grams of Feed, vs. Space Velocity 7 4. Gaseous Product, Wt. percent of total feed, vs. Space Velocity 8 5, Ethylene Loading Apparatus 14 6o Glass Vessels for Propylene-Para-Xylene Experiment s 16 7. Propylene-Ethyl Mercaptan Rate Study, 200C 19 8. Propylene-Ethyl Mercaptan Rate Study,- 500C 20 90 Propylene Loading Apparatus 24 10 Combination Gas Loading Apparatus 29 11, Density of Ethyl Mercaptan vs. Temperature 34 12. Liquid Density of Iso-butane at Saturated Pressure vs. Temperature OF, 35 13. Liquid Density of Propylene at Saturated Pressure vso Temperature ~Fo 36 14. Vapor Pressure of Various Liquids vso Temperature (Range, -1620C to +600C) 37 15. Vapor Pressure of Various Liquids vso Temperature (Range, -200C to 2400C) 38 iv

The University of Michigan ~ Engineering Research Institute OBJECT IVE The aim of this work is to explore the effects of gamma radiation on a number of chemical reactions which may be of interest to the petroleum and petrochemical industries. It is believed that these exploratory studies will lead to a better understanding of the mechanism of radiation-induced reactions. Also, such studies should eventually permit generalizatiens of radiation effects on many different chemical reactions.

The University of Michigan * Engineering Research Institute ABSTRACT Gamma radiation produced no appreciable effects on the catalytic cracking of cetane at a radiation level of 42 kilorep per hour. Small differences could have been masked by experimental and analytical variables. Para-Xylene inhibits the polymerization of ethylene by gamma radiation at pressures of 500-900 psig and at room temperature. Propylene in the presence of para-xylene does not react when irradiated o Ethylene reacts with ethyl mercaptan at pressures of 450-1500 psig and room temperature only when irradiated and forms predominately (90-98 ) 9 diethyl sulfide, Only under radiation will propylene react with ethyl mercaptan at temperatures of 20-50OC and pressures of 80-170 psig forming ethyl propyl sulfide (95-100 /%).o When 1:1 molal ratios of propylene and ethyl mercaptan are present, the reaction is of the first order with respect to total pressure. The reaction rate constant is dependent upon the dose rate, Experiments with isobutane-ethylene, i sobutane-propylene, isobutane-butylene, n-butane-ethylene, aniline-ethylene, and butylene-propylene indicate that there were no significant reactions in these mixtures using gamma radiation, vi

The University of Michigan * Engineering Research Institute I INTROIDUCT ION The following study of the effect of gamma radiation on various petrochemical reactions was undertaken for Standard Oil Company of Indianao The work was done under the auspices of the Engineering Research Institute of the University of Michigan, Project No. 2420. The present report is a continuation of the work reported in the annual report to Standard Oil Company of Indiana of August, 1955 to July, 1956, Effect of Gamma Radiation on Various Petrochemical Reactions, and covers the work period from July, 1956 to January lst, 1957o The program, in the six month period covered, consisted of four separate phaseso The first was a continuation and analysis of the catalytic cracking studies of cetaneo The second dealt with the reaction of para-xylene with ethylene and propylene using gamma radiation. The third phase consisted of a study of the effects of gamma radiation on the addition of ethyl mercaptan to ethylene and propyleneo The last phase consisted of the study of alkylation and polymerization effects of gamma radiation on: a) isobutane, ethylene b) isobutane, propylene c) n-butane 9 ethylene d) iso-butane, butylene e) butylene, propylene f) ethylene, aniline I Io SUMMARY OF RESULTS A, Catalytic Cracking of Cetane From the results of the experiments conducted, it is possible to conclude that the irradiated experiments showed no differences from the non-irradiated experiments greater than 3 ~/o, which is the probable experimental error. However, the work was not sufficiently uetailed or comprehensive to rule out the possibility that small effects could have been masked by experimental and analytical variables.

.The University of Michigan * Engineering Research Institute B. Para-Xylene Experiments (1) Ethylene Ethylene will polymerize at pressures of 500-900 psig at room temperature in the presence of gamma radiation. It will not polymerize at these conditions without gamma radiation. However, this polymerization at the above conditions is inhibited by para-xyleneo Due to the small quantities of solid product recovered, a quantitative statement cannot be made. (2) Propylene Since no component boiling higher than p-xylene was found in the distillation of the liquid from the p-xylenepropylene reaction, it was concluded that gamma radiation produced no detectable polymer or addition product in the propylene and para-xylene mixture Co Ethyl Mercaptan Reactions (1) Ethylene Ethylene will not react with ethyl mercaptan at room temperature and pressures from 450-1500 psigo However, this reaction will take place with gamma radiation forming predominately diethyl sulfide at a conversion of from 90 to 98 per cent in 72 hours at a dose rate of 59 kilorep per hour, (2) Propylene Propylene will react with ethyl mercaptan at temperatures from 20-50~C and pressures of 80-170 psig only under the influence of gamma radiation. When 1:1 molal ratios of propylene and ethyl mercaptan are present9 the reaction is of the first order with respect to total pressure, The reaction rate constant is dependent upon the dose rate0 The liquid samples contained from 96-99.7 per cent ethyl propyl sulfide~ The reaction had a 95-100 per cent conversion of the ethyl mercaptan. Do Alkylation and Copolymerization Reactions with isobutane-ethylene, isobutane-propylene, isobutane-butylene, n-butane-ethylene, aniline-ethylene and butylenepropylene indicate that there were no significant reactions using gamma radiation at room temperature However, the work was not sufficient to draw any definite conclusionso The preliminary work did indicate that the small amount of products formed was due to polymerization of the olefin and not due to a reaction between the olefinic molecule and the saturated molecule.

The University of Michigan ~ Engineering Research Institute III CATALYTIC CRACKING OF CETANE A. Discussion of Results and Conclusions Fig0 1 is a plot of the percentage of unconverted cetane recovered in the liquid product, The data applies to both the irradiated and non-irradiated runs at different space velocities. The data can be used as a direct measure of the amount of cracking that took place. It can be seen from Fig. 1 that there is no evidence to indicate that gamma radiation either inhibits or promotes the cracking of the cetane molecule, Fig. 2 is a plot of the weight per cent of material lighter than cetane in the liquid product There is no trend to indicate that gamma radiation has changed the product distribution resulting from the catalytic cracking reaction. Fig. 3 is a plot of the carbon deposit on the catalyst per i00 grams of feed against space velocity. Again there is no trend to indicate that gamma radiation has an effect on the amount of carbon deposit on the catalyst0 Fig. 4 compares the gas produced at different space velocities It shows that in every case more gas was produced in the nonirradiated runs than in the corresponding irradiated runs at the same space velocityo Two hypotheses were postulated in an effort to explain this result: (1) The reaction mechanism for the irradiated runs tended to crack the cetane molecule near the center thereby producing a shift in product distribution resulting in less of the light gaseous hydrocarbon molecules and more of the heavier liquid molecules. (2) Gamma radiation promoted polymerization of the light olefins to produce heavier liquid compounds and thereby reducing the volume of gas, The analyses of the gas collected during the course of the runs as shown in Table I, indicate that the molecular weights and product distribution for the irradiated and non-irradiated runs at the same space velocity are nearly identical. These run gas analyses present the strongest evidence to refute the two proposed theories since for either proposed theory to be valid, the g a from the irradiated and non-irradiated runs must have different product distributions and also would be expected to have different molecular weights. From the results of runs conducted, it is possible to conclude that gamma radiation has no appreciable effect on catalytic crack

The University of Michigan * Engineering Research Institute ing. However, the work was not sufficiently detailed or comprehensive to rule out the possibility that small effects could have been masked by experimental and analytical variables~ o Re sul ts Table IL is a summary of the experimental conditions and results of the 23 catalytic cracking runso Of the 23 experiments, 11 were made with gamma radiationo The other twelve were used as control runs to better determine any effects of the radiation. The average temperature recorded in Table I was taken as the integral average of t he t emperature profile across the catalyst bed~ As can be seen from Table I, there was no significant pressure drop observed in any of the runs reported, The radiation dose reported was calculated as shown in the Appendix, pages 34 -35, of the Annual Report from August, 1.955 to July, 1956o The space velocity in the Table is defined as: weight of feed/hr0 weight of catalyst The data in the column headed, Material Lighter than Cetane, % was obtained from a liquid product analysis determined by gas chromatography by Standard Oil (Indiana)o Runs lc through 8c were conducted with 1.2 inches of catalyst bed0 However, it was decided tha. more accurate,,data could be obtained if more gas was formed during the run. Therefore, 3.6 inches of catalyst bed was used for runs 9c to 23c which resulted in decreased space velocitieso However, only rnns 16c through 23c are plotted in the following Figures 1 through 4 sinlce these were the only runs where consistent conditions were maintained. The data for these runs were collected after modifying the equipment,;o permit a uniform method of duplicating the irradiated and non-irradiated runso The temperature difference (max. 15~C) was neglected in making the plotso Considerable difficulties were encountered in maintaining constant-temperature conditions throughout the run due to irregular vaporization of the feed and to the comparatively short life of the catalyst, which does not permit a waiting period to reach steady state before the products are collectedo The first problem was corrected by introducing a glass-wool plug at the top of the reactor to obtain a better distribution of the feed. The latter was controlled by establishing a given temperature profile in the catalyst before each run was started, With these difficulties overcome, it can be noted (runs 18c-23c) that for runs at the same space velocity the temperature difference was only 10~Co The operation at different feed rates resulted in different temperature profiles in the catalyst bed and accounts for the range in average catalyst bed temperatures from 519 to 543~Co

The University of Michigan * Engineering Research Institute 70,0.60 60 LL 50 0 40 40 0 0 30 z z Iu 20 O Radiated O Non-radiated I0.... 0 1.0 2.0 3.0 4. 5.0 6.0 SPACE VELOCITY, W/ HR-W Figure lo Cetane in Product9 Wto %/ of Total Feed vso Space Velocity Runs 16c through 23c6 plotted _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _5 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

The University of Michigan Engineering Research Institute 30 LU MLI ur.0 25 0 L, 20 z 0 I,,,U I z I,1I5 LU 0 Radiated 0 * 0QC Non-radiated D I 10 L) 0 0 I0 e 0 5 0 0 1.0 2.0 3. 0 4.0 5.0 6.0 SPACE VELOCITY, W/HR-W Figure 2o Liquid Product Lighter than Cetane, Wt. % of Total Feed vso Space Velocity Runs 16c through 23 c6 plotted 6

The University of Michigan * Engineering Research Institute 1.6 _ 1.4 LU u 0 ~i.2 0 1.2 r | \ l | ~0O Radiated 0 I I Non-radiated n0.8.I Iz 0 0.6 0 0u z 0.4 0 0.2 100 grams of Feed vs. Space Velocity Runs 16c through 23c' plotted 7

The University of Michigan * Engineering Research Institute 40 _ LU 30 LU U_j 0 iL_ 0 20 aO0 LU 0 I0 O Radiated o Non-radiated 0 1.0 2.0 3D 4.0 5.0 6.0 SPACE VELOCITY, W/ HR-W Figure 4. Gaseous Product Wt. a of Total Feed vs. Space Velocity. Runs 16c through 23c~ plotted 8

TABLE I, PRODUCT DISTRIBUTION AYTr AVERAGE MOLECULAR WEIGHTS OF GAS SAMPLES FROM CATALYTIC CRACKING OF CETANE Run Number 16c 17cr 18c 19c 20cV 21cY 22c 23c Space Velocity 3.73 3,71 5.58 1.86 1.87 5.58 0,933 0932 C6 Olefins and Napthenes 02 01ol 0.1 0.4 0.1 0.1 0.1 C5 Olefins and Napthenes 3,3 2,0 2.9 3.6 2.7 2,5 1.7 2-1 Normal Pentane 0ol 0.1 0.1 0.2 0.2 3 Isopentane 1 9 1 3 1.4 2.0 1.8 1.4 1.4 1.4 Normal Butane 2,6 2,5 1,8 2,1 1,8 2.0 2,2 1.9 Isobutane 5,3 5,7 5.1 5o3 503 4.6 5.2 5.5 Butenes 21.8 20*1 21*0 19,8 18,6 20.2 14,9 15.8 Propane 7o9 8,9 7,4 7.5 7o2 6,5 8,3 8,4 Propylene 30.6 33,4 33,6 28.5 31.0 33,2 28.4 26.9 Ethane 3o0 3,2 3.6 4.6 5,0 3.6 5.2 4.7 Ethylene 9.4 8.9 9 4 9.7 11,0 11.9 12.8 12.1 Methane 4e8 4.5 5o2 6.8 6.8 5o2 9.2 9.3 Hydrogen 9,2 9,2 8.3 9,8 8.7 8.4 10.5 11.5 Total 100,0 99.9 99.9 100.1 100.1 99.8 100.1 999 Specific Gravity 1.439 1.417 1,426 1.401 1.386 1.401 1.300 1.297 Average Molecular Weight 41,6 40.2 41.4 40.7 40 2 40.6 37.7 37.6

w, TABLE II. 8UMY~nY u~ CATALYTIC CRACKING UF ~R'I'ANE ~.~ Run Number lc 0 2c 3c F 4c 5c Date 5/24/56 5/25/56 5/28/56 5/29/56 5/31/56 Depth of bed, inches 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 Average Temp., ~C. 495 495 500 534 542 544 542 541 475 482 488 525 522 529 526 527 520 535 533 - - - 530 ~iddle of bed Temp., ~C. 500 500 505 539 547 549 549 543 475 495 492 532 527 534 531 531 525 534 526 527 533 519 519 3ottom of bed Temp., ~C. 506 520 494 - - - 481 499 547 538 463 471 487 515 abe 506 TopofbedTemp.,OC. 477 536 533 440 4o7 487 523 521 52~ 531 51~ ~ ~ ~ ~')....... ~...... o 52~ o ~ ~ o ~ o - ~ 42 - - 4 4 Aop...... 4 4 42 4 d. dose krep/hour _ - - 38 - 25120 20 2~ 25.20 - 25.2G 42 42 42,,~, Catalyst char~ed, ~m. 25.20 25.~0 25 20 25.20 7.75 7.59 5.27 7.96 7.82 8.17 o.01 8.11 25.02 24.56 25.13 25.20 2~.54 25.20 25.20 ~ Feed rate, cc/hour12C 120 120 120 120 120 120 120 120 120 120 120 122.4 122.2 122.1 122.6 1~2.9 61.05 61.15 183. 30.55 30.50 Totalrun time, hour 12~.3 1.0 0.~34 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0.0 1.0 2.0 2.0 1.0 2.0 2.0 Total feed, cc. 120 120 120 120 120 120 120 120 120 120 120 120 122.4 122.2 122.1 122.6 121.3 182.9 122.1 122.3 153.1 61.1 61.0 Total feed, ~m. 92.5 ~2.5 77.0 92.5 92.5 92.5 92.5 92.5 92.5 92.5 ~2.5 ~2.6 94.4 94.1 ~3.9 ~4.0 $3.5 141 93.9 94.3 141 47.1 47.0 Total feed, moles 0.409 0.4u9 0.340 0.40~ 0.4u9 O.409 0.4u~ ~.409 u.40~ 0.409 0.409 0.409 0.416 0.415 0.414 u.415 0.413 0.621 0.414 0.415 0.621 C.208 6.207 Space velocity, ~/hr/~ 11.29 11.20 1~.2~ 11.31 11.61 11.51 11.51 11.40 3.70 3.77 3.68 3.66 3.70 3.74 3.72 3.73 3.71 5.58 1.56 1.87 5.58 0.933 0.$32 93.5 92.0..... 55.4 2 ~ ~oau~.... ol.3 72.0 50.7' 01.4 62.15 60.75 67.27 116.7 5~.04 62.03 115.24 26.13 2~.~0 o a~ o o~,~ ooo o o~o ~o~ ooo o o~ ~o~ o~.~o ~ o oo~ o~ o~ o~o,Off gas~ SCF ~~~o~o~o~~ ~ ~ 0.0285 0.0154 0.025 0.05~5 C.C3~ O ~ ~eathered ras, SCF _ _ 0.011 0.0300 0.0143 0.0229 O.028.0121 0.O074 0.O~13 0.015 0.016 0.0475 SCF total ~as/.....le feed 6.~46 C.C64~ 0.06 0.~65 0.230 0100 01185 ~.223 0.431 0.364 0.0663 1.058 0.746 0.7~0 ~.941.752 0.618 1.30 1.12 0.609 1.50 1.67 Gm-mole ~as/-m31e feed t.eeo 0.~55 ~.072~ C.Ob 0.1~7 0.274 0.00 0.221 0.516 0.435 0.0793 1.265 0.o94.625 O.SW~ 1.125 ~.900 0.737 1.55 1.33 0.727 1.79 2.00 0.~66 ~:aterial-lighter than cetane, ~ 8 6 9 12 10 12 14 13 13 17 15 15 25 20 20 19 24 19 23 28 27 Catalyst: (gas chromatography) 1.157 ~.694 0.714 0.460 ~.476 0.194 Caroon on sample ~.003 0.511 C.175 C.~27 0.~38 ~.971.... latll...... 3.35 2.75.24 3.66 3.37 3.41 2.56.38 3.61 2.14 2.84 2.88 1.196 0.713 1.046 0.740 0.496 0.492 C.199 C.994 C.179 J.953 Carbon on ash C.526 3~.3 ~.962 50.8 42.2 41.7 - 42.9 42.5 40.9 40.8 41.6 40.2 41.0 40.4 3..9 Average molecular weight (off gas) 40.3 37.4 3.2 aa.m~ 44.4 42.9 - - - ~s. ~. ~.~ ~-~ ~.~ ~.~ ~'~ ~'~ ~'-~ ~.~ ~.~.05 ~.~ ~.~ ~-~ Jeathered gas, ~rms (mol.wt.56 assureed''' 0.64 0.50 2.2 2.0 1.4 1.7.5.7 1.C 1.25.3 Purge gas, gas?'~ ' 1.2 1.1 - 1.1 1.2 1.5 1.5 u.8 0.5 0.6 0.8 1.2 ""I:iaterial oalance, weight ~ 105 73.4 101.0 5~.3 ~6.0 o~.6 97.5 91,8 89.7 J6.0 67.5 91.0 ~e 26.8 22.7 3as oroduct$, weight ~ (input basis) 1~.5 14.65 17.0 17.7 14.7 2~.8 24.1 14.5 32.0 38.1 Liquid products, weifht / (input Sasls) 13.2 7.~5 12.~ 16.5 13.6 14.4 15.6 15.1 12.5 18.8 15.5 14.3 Cetane converted, weight / (input oasis) 40.0 27.3 27.6 ~3.5 ~7.3 32.1 3L.5 44.9 36.6 33.~ 47.5 52.3 Cetane converted, weight / (output basis) 36.8 37.3 27.6 4~.1 ~o.9 33.8 31.~ 47.~ 40.6 34.4 54.3 57.3 Spill ~ Purge gas - 200~ co of N9 oassed tD~ou~h reacting system after each run,~eathered ~as- ~ases evolved from liquid product on warming from O~C to 203C. ~ zr

The University of Michigan * Engineering Research Institute Co Experimental Procedure The equipment and procedure followed in the catalytic cracking studies are fully defined in the Annual Reporu, August, 1955 to July, 1956. Thedetails are listed on pages 26 through 27 of that report. Fig. 19, Catalyt4,- Cracking Unit Flow Diagram, of the above reportshows the same equipment 'hat was used for all catalytic cracking and Fig. 21, Catalyst Arrangement in Reactor without Spacer, is a diagram of the reactor used for experiments 9c through 23c, since it was desired to use a larger catalyst bed. The catalyst was obtained from Standard Oil of Indiana, No.3A5427 WOS, The radiation facilities for the experiments are described in detail on pages 1 through 4 in the above report. IV PARA XYLENE EXPERIMENTS A. Ethylene and Para-Xylene (1) Discussion of Results and Conclusions Ethylene will not polymerize by itself or in the presence of para-xylene at room temperature and at pressures from 500-900 psi0 However, at these conditions and with gamma radiation, ethylene does polymerize in the presence of para xylene or by itself. Table III indicates that this polymerization is inhibited by para-xylene. But due to the small quantities of solid product recovered, a quantitative statement cannot be made. (2) Results The run conditions and results are reported in Table III, In most cases a white emulsion was present in the liquid product after venting off the gas~ Most of the liquid was then distilled off at 1380C, the boiling point of para-xyleneo The remaining emulsion was then placed on a watch glass and allowed to evaporate, leaving a solid product. In the distillation there was no fraction obtained with a boiling point higher or lower than 1380C. The reactions containing ethylene, without para-xylene present, yielded a white fluffy polymer. The reactions containing para-xylene and ethylene yielded a dense polymer after distillation and solidification0 It will be noted in Table III that some products are listed as being brown in color, However, it is believed that the product was initially white and that the distillation was carried too far and c aused discoloration, The products are now being analyzed at the Standard Oil Laboratories in Whitingo 11

TABLE III. ETHYLENE & PARA-XYLENE, SUMMARY OF RESULTS Run Number 1 2 3 4 5 6 7 8 9 10 - Date 8/24/56 8/24/56 8/24/56 8/27/56 8/31/56 8/31/56 8/31/56 9/11/56 9/15/56 10/31/5 Volume of para- 25 0 12.5 0 25 12.5 3.0 0 70 35 = xylene, cc Ethylene, gm 11,2 5,15 8.0 12,6 21.65 18.20 14.73 15.3 11,4 27.5 |Initial pres- 530 510 509 875 810 810 810 810 760 870 ~ sure, psig 0 Initial Tem- 72 72 80 90 77 77 77 68 64 77 perature, ~F Final Pressure, 530 100 480 860 805 795 800 810 430 870 psig UFinal Tempera- 77,5 77o5 75,5 76 72 72 72 72 72 72 m ture Ethylene gas 3.8 5.15 4.35 12,6 9.25 10.8 12.4 15.3 1.31 27.5 phase, gm (recovered) Solid product, 0.1835 0.0912 0o33 0.2754 0.2178 0*2433 0.37 0*065 0.22 ( gm Dose, megarep 5.12 4.2 4.95 3.59 4.17 4.17 4.17 4.32 4.20 4*3 Gm product per 0.0163 - 0.0114 0.0262 0.0129 0.*0119 0.0165 0.0242 0.0057 0.0080% gm C2H4 charged Remarks brown brown white dense dense dense white brown whitev waxy solid soft white white white soft sludge solid solid powder solid solid solid powder

The University of Michigan * Engineering Research Institute (3) Equipment and Procedure A 100 cc stainless steel reactor equipped with a pressure gauge was used. This reactor is the same as shown on page 12, Fig0 7 of the Annual Report, August, 1955 to July, 1956. The reactor was filled with para-xylene by means of a pipette. The para-xylene and reactor were then cooled down to -760C. The ethylene loaded mechanism was attached as shown in Fig. 5 of the present report. After the reactor was cooled, a vacuum of approxi. mately 300 microns was established in the system. The desired amount of ethylene, as calculated from the pressure drop of the loading vessel, was then condensed into the reactor from the 300 cc loading vessel. The reactor was then closed and removed from the loading systemo Comparable reactions were run so that they would have a constant initial pressure with varying amounts of para-xylene and consequently, varying amounts of ethylene. The experiments were carried out at the temperature of the source room. B, Propylene and Para-Xylene (1) Discussion of Results and Conclusions Since no component was found in the liquid product distillation between that of p-xylene and 'the added high boiler, it was concluded that gamma radiation produced no detectable results on the propylene and para-xylene mixture. The experiments were discontinued. (2) Results The four para-xylene-propylene runs are listed in Table IV. The experiments were so designed that the only variable would be the amounts of propylene and para-xylene present. The radiation was held constant for each run. The vials were all irradiated at the temperature of the source room. An analysis of the liquid left in the glass vials after the propylene was allowed to vent off was attempted in a Podbielniak Column with cetane being added as a high boiling liquid. For reactions 1 -3 no component with a boiling point between p-xylene and ce anE was detected, Run 1 was not distilled but the p-xylene was allowed to evaporate ang a few drops of viscous liquid was obtained as a product. (3) Equipment and Procedure The 100 cc vials for the propylene and para-xylene experiments are the same as those described on page 5, Fig. 5, of the Annual Report, August, 1955 to July, 1956, The apparatus.shown 13

The University of Michigan * Engineering Research Institute PRESSURE GAUGES RUPTURE DISK VENT KNOWN VOLUME LOADING CYLINDER ETHYLENE CYLINDER DEWAR FLASK DRY ICE BATH REACTOR Figure 5. Ethylene Loading Apparatus 14

The University of Michigan * Engineering Research Institute in Fig. 6 was used to load the vials with propylene and paraxylene The first step in the procedure was to evacuate the complete system to a pressure of 150 microns. The desired amount of propylene was then condensed in the vial at a temperature of -76~C (dry ice-chloroform-carbon tetrachloride mixture). Para-xylene was then injected into the vial by means of a syringe through the rubber serum stopper on one of the lead-out ports of the glass vial utilizing the vacuum of the system. The vial was then glass sealed with a flame and removed from the system, The amount of propylene condensed was calculated from the specific gravity of liquid propylene at this temperature and the volume of the vial, Recovery was attempted by breaking open the glass vials and letting the propylene evaporate, The para-xylene was then colle cted, TABLE IVo PROPYLENE & PARA-XYLENE Run Number lp 2p 3p 4p Date 9/6/56 9/6/56 9/7/56 9/7/56 Volume p-xylene, 7,5 15 22o5 0 cc at 76~F Volume of propylene, 22.5 15 7,5 26 cc at -760C(-1030F) Dose, megarep 9,0 9,0 9o0 9.0 V ETHYL MERCAP TAN EXPERIMENT S Ao Discussion of Results and Conclusions (1) Ethylene A study of the structure of ethyl mercaptan and ethylene indicates that any of the following reactions or combinations thereof are possible: C2H5SH + C2H4-> C2H5SC2H5 2C2H5SH ~- C2H5S-SC2H5 + H2 C2H5SC2H5 + C2H4-> C4H9SC2H5 nC2H4 -) (C2H4-)n 15

The University of Michigan * Engineering Research Institute PYREX TUBE to TUBE n If 15-CC VIAL 100-cc VIAL SEALEDVIAL Figure 60 Glass Vessels for PropylenePara-Xylene 16 ____ ____ ___ ____ ___ ____ ___ 16_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

The University of Michigan ~ Engineering Research Institute However, from the analysis of the liquid products, it can be seen that the addition of ethylene to ethyl mercaptan tended to form diethyl sulfide (C2H5-S-C2H5)o This reaction was definitely predominate even though a very small amount of the ethyl mercaptan did react with itself forming ethyl sulfide. However, the latter reaction only resulted in from 0.5 per cent to 7.0 per cent of the sample. It should also be noted in Run No. 3 that 10 per cent of the liquid sample was the compound C6H14S, believed to be C4H9SC2H5 There is no explanation as to why there is a greater amount of this higher sulfur zompound formed in this case as compared to the other runs (per cent of higher sulfur compounds are listed in the miscellaneous column). It should be noted here that the reaction will not take place without gamma radiation~ A reactor was filled under the test conditions and allowed to stand for three days. During this time there was no reaction9 However, when the reactor was irradiated, a reaction took place0 It is concluded, therefore, that for ethylene to react with ethyl mercaptan at room temperature, the reaction must be initiated by gamma radiation. However, the data given in Table V do not permit other conclusions since there were not sufficient experiments conducted. (2) Propylene Rate studies were made on the addition of propylene to ethyl mercaptan at temperatures of 200C and 500C. The results are shown in Table VI and in Fig. 7 and 8. The graphs are plots of the concentration of propylene vs the radiation time for experiments No. 4 and 5 in Table VIo The concentration was calculated from the pressure of the reaction at different radiation times. (See Appendix-Sample Calculations, page 31)0 The log concentration versus radiation time for both runs plot as a straight line, indicating a first order reaction, depending on the concentration of the mercaptan. It is believed that the reaction rate constant,is not a strong function of temperature but is dependent' on dose rate, The latter is supported by the fact that without radiation there was no reaction. If temperature had an effect on the reaction rate constant, it would be expected to increase the constant, not decrease it as the data shows. However, the discrepancies in the two reported reaction rate constants, 0.0371 l/hr as compared to 0~0326 l/hr, is believed to be due to the fact that the reactor received different dose rates caused by the necessity of a constant temperature bath for the 500C reaction (59K-rep/hr and 40K-rep/hr respectively) The log concentration versus radiation time plot for Run No. 5 was a straight line with a reaction rate constant of 0~0326 l/hr for the first part of the reaction and a straight line of different. slope with a reaction -rate constant of 0.0213 1./hr for the latter part of the run~ The change in rate constants 17

TABLE V, ETHYLENE + ETHYL MERCAPTAN, SUMMARY OF RESULTS Run Number 1 2 3 4 5 6 7 Date 9/18/56 9/18/56 9/19/56 9/26/56 9/28/56 9/29/56 10/9/56 " 1.Ethyl mercaptan charged, gms)S.G.=0.915 -750~C) 183 18.3 18.3 18.3 18.3 18.3 22.8 2.Ethylene charged,gms 23.8 11.9 0 20.0 35.0 0 3,Moles C2H4/moles C H SH 2.90/1 1.44/1 - 2.43/1 4.25/1 - 4.Vented gas,gms(MW=28~ 10.72 5.58 6.78 0 10.3 26o0 0 o 5.Liquid product, gmins 27.20 24.30 19.45 151l 23.45 22.94 18.64 6,Initial pressure, psig 620 490 460 0 610 1450 0 m 7,Final pressure,psig 480 270 350 0 460 750 0 8,Temperature,OF 70 70 70 70 70 70 70 9,Dose, megarep 4,2 4.2 4.2 4.2 4,2 4.2 4.2 m l0.Liquid product analysis (mole / ) H Ethylene _ _ o0, Ethyl mercaptan * 3,5 W9,0 Ethyl sulfide 97o5 97.0 79.0 97,0 87.0 - Ethyl Disulfide 1.25 2.0 7 - 0.5 1-2 -. Miscellaneous* * 1o25 1.00 10,0 0 2.5 1-2 11 % Recovery of reactants g 99 - 82.5 88 92 - A value.7,250 6,900 - 7,050 7,100 No analysis made due to contamination * Reactor had to be vented to relieve pressure ~; Indicates higher molecular weight sulfur compounds 9-. C

The University of Michigan * Engineering Research Institute Propylene - Ethyl Mercaptan Rate Study, 20 OC 1.0.9.8 ~<1:~~~~ [%_ k-.0371 1/hr co.7 0.6..5 _ _ N Lu F.4 - ' 4 - 1 0. M. 0 z 0.2 I — z 0 0 3 6 9 12 15 18 21 24 RADIATION TIME, HRS Figure 7. Run No. 4 Propylene and Ethyl Mercaptan 1/1 mole ratio at 200C Dose rate 59 K-rep/hr. 19

The University of Michigan ~ Engineering Research Institute 0....,C 0 / o 0 Z 0.C 0 >. X1 @Y C C _Oo / 2000Z 0 OD to N. SISVG 310W IO/'N1Ad0lId AO N0UVIiiN3N0 Figure 8. Run No. 5 - Propylene and Ethyl Mercaptan Dose rate 4K-rep/hr, 20

The University of Michigan ~ Engineering Research Institute is believed to be caused by accidently moving the reactor during its radiation time resulting in a decreased dose rate and thereby causing a lower reaction rate constant, Two reactors were loaded and run under test conditions without radiation, one at 20~C and one at 500~C for a two day period without any evidence of a reaction. However, when these same reactors were radiated a reaction took place. It was concluded, therefore, that the reaction between propylene and ethyl mercaptan will take place in the temperature range of 20-50~C only when initiated by gamma radiation, The addition of propylene to ethyl mercaptan takes place almost exclusively with the propylene adding to the sulfur atom. The liquid samples analyzed indicated that the ethyl propyl sulfide formed from this reaction constituted from 96-99,7 per cent of the liquid sample while other sulfur compounds completed the total. Bo Results The results of the seven experiments with ethylene and ethyl mercaptan are reported in Table V, The five experiments with propylene and ethyl mercaptan are given in Table VIo The ethylene experiments were conducted with constant amounts of ethyl mercaptan and constant radiation time, However, in the propylene experiments these quantities were varied. In addition the temperature of Runs 4 and 5 of the propylene experiment was varied to study the possible rate effectso A distillation was attempted on the liquid product from Run No. 1 of the ethylene experiments, Since approximately 90 per cent of this product was distilled over in a boiling range from 84 to 95~C, a reaction was indicated, The boiling point of ethyl mercaptan is 37?C. o Another distillation was attempted on the liquid product from Run No. 4 of the ethylene experiments. This run consisted of radiating pure ethyl mercaptan, and the distillation showed that all the product distijlled over at 37~Co The liquid products of Runs No. 3 and 4 of the propylene experiments were also distilled, All the liquid from Run No. 3 distilled at a constant temperature of 1140~Co Six cc of the liquid from Run Noo 4 distilled at 370~C (the boiling point of ethyl mercaptan) and 36 cc distilled in a temperature range of 116-119~Co This boiling point range corresponds to the boiling points of the possible addition products of the reaction. In most of the ethylene experiments there was a certain amount of solid poly-ethylene found in the liquid:product, There

TABLE VI PROPYLENE & ETHYL MERCAPTANSUMMARY OF RESULT S Run Number 1 2 3 4 5 - Date 10/6/56 10/7/56 10/17/56 11/3/56 11/13/56 = l.Ethyl mercaptan charged9 gms 1908 8o94 19o0 29.4 29, 2,Propylene charged, gms 13o45 25 2 28ol 20.2 20, 3,Molar ratio, Propylene 1/1 4o17/1 2.18/1 1/1 1/! Mercaptan 4,Liquid product9 gms 32o21 13.00 27.75 40002 4800 5,Gas' vented, gms(MoW=4201) 0 22o5 14.3 8o04 0O175 6.Initial pressure, psig 8000 100 80 168 7,Final Pressurepsig 0 60 0 43 20.7 ~ 8,Dose, mengarep 4'.2 4o2 4.2 1.37 300 9oTemperature, (0C) 21 21 21 20 50 10o % Recovery of reactants, t3o gmso products/gms feed 96.8 104 8902 97 98.5 11.Liquid product analysis (mole %) m Ethyl disulfide 1,3 0o3 = Ethyl propyl sulfide 96.0 997 Miscellaneous ~ 200 A value 4,200 3,020 3,080 79420 5.750 -* Indicates higher molecular weight sulfur compounds L~~~~~~~~~~~~~~~~~~~

The University of Michigan * Engineering Research Institute was no attempt made to recover the solid product from the liquid~. The complete product was sent to the Standard Oil Laboratories at IW liting for analysis. C o Equipment and Procedure The experiments were carried out in the same 100-cc stainless steel pipe reactors as mentioned earlier and shown on page 12, Fig. 7, of the Annual Report The procedure for loading was to first evacuate the system to approximately 300 microns and then immerse the reactor in a liquid nitrogen bath. In the ethylene experiments, ethylene was condensed in the reactor from the 275 cc loading vessel as shown in Fig~ 50 After the desired amount of ethylene, as calculated from the pressure drop of the loading vessel, was condensed9 the reactor and its cooling bath were removed from the loading systemo A rubber serum stopper attached to a glass tube was then cohnected to the reactor. Ethyl mercaptan was introduced into the reactor from a syringe utilizing the vacuum in the reactor at liquid nitrogen temperature. The procedure for loading propylene was very similar in that the system was first evacuated and then immersed in a dry ice bath. The desired amount of propylene was then condensed in the calibrated vial as shown in Figo 9o The dry ice bath on the calibrated vial was removed and the propylene was allowed to condense in the reactor. Ethyl mercaptan was introduced into the reactor in the same manner as for the ethylene experiments. The amount of ethylene charged was calculated from the pressure drop of the loading vessel as shown in the Appendix. The accuracy of this measurement is believed to be approximately + 10 per cent. The accuracy of the propylene loading measurement are considered better since they wvere based on liquid volume measurements at a known specific gravity. The ethyl mercaptan was cooled to 0~C before any attempt was made to work with the compound, A rubber serum stopper was attached to the top of the bottle containing the compound, and the ethyl mercaptan was withdrawn using a syringe~ After the reactor was irradiated, it was cooled in a dry ice batho The reactor was then allowed to warm to room temperature while the gas was vented through a wet test meter and measured. A gas sample was taken at dry ice temperature and at room temperature for the ethylene series. 23

PRESSURE VACUUM GAUGE RUPTURE DISK 1~~~~~~~~~ VENT OQ DEWAR FLASK W DRY ICE BATHD DEWAR FLASK cO GRADUATE ~ to GRADUATE DRY ICE BATH rrl REACTOR aQ w (1 70 U) *:3 Figure 9. Propylene Loading Apparatus

The University of Michigan ~ Engineering Research Institute VIe ALKYLATION AND COP OLYMERIZATION A. Discussion of Results and Conclusions The results of the various alkylation and copolymerization experiments are shown in Table VII. It should be noted from the table that there were no significant reactions with gamma radiation, The small amount of products formed seem to be a result of the olefin, for example ethylene, polymerizing by itself without any reaction with the saturated molecule. Also, in the case of propylene and butylene, it is believed that the residues left in the reactor were polymnerization products of the olefins, The large amount of product reported in the aniline-ethylene experiment is the weight of the aniline that was originally charged into the reactor and then recovered, The only copolymerization experiment reported, butylenepropylene, showed no significant results, It is believed that further work on the alkylatiQn reactions must be conducted before any conclusions can be reached. B. Results (1) Isobutane (a) Ethylene Ethylene and isobutane, 20 gms and 22.1 ginms respec tively, were loaded into the reactor, This corresponds to a mole ratio of ethylene to isobutane of 1.87:1. The reaction received a dose of 6.9 megarep at room temperature, 700F, the pressure remained constant at 510 psigo A white, fluffy product was recovered that weighed 2.3 grams and resembled polyethylene, It had a melting point of 1270C. In addition another isobutane-ethylene experiment was made. Since there was an error made in loading, it: is not known how much isobutane was loaded with the 17.2 gms of ethylene. The reaction received 82 hours of radiation at an unknown dose rate which is indeterminate due to moving of the reactor, A solid was recovered weighing 0,21 gms and having a melting point of 123-127~Co (b) Propylene Two experiments were run at approximately 1:1 mole ratio. The first experiment contained 20.4 grams of isobutane and 14,9 grams of propylene and was held at 80 psig at 70~F. The mixture received a dose of 8,67 megarep. There was no liquid product o 25

The University of Michigan * Engineering Research Institute TABLE VIIo SUMMARY ALKYLATION EXPERIMENTS Olef ins Ethylene Prop ylene Butylene Run 1 Run 2 Run 1 Run 2 Run 1 1. Isobutane Amount of 1-C4Hl0 loaded 22,1 20~4 26~8 21,2 Amount of olefin loaded 20 17o2 14o9 18o2 20o3 Mole ratio 1,87/1 1/1 1/1 1/1 Temperature (OC) 20 20 20 110 20 Pressure (psig) 510 80 2400 Radiation (megarep) 6 9 867 Product recovered (gm) 2.3 0o21 - Description white, white, oily small fluffy fluffy resi- amt, of solid solid due liquid 2o N-Butane Amount of n-C4H10 loaded 22.2 Amount of olefin loaded 19o8 Mole ratio 1/1 Temperature (OC) 20 Radiation (megarep) 9,5 Liquid product recovered 0.55 Description white, fluffy solid 3. Aniline Amount aniline loaded Amount of olefin loaded 19,7 Temperature (OC) 20 Pressure 970 Radiation (megarep) 4o2 Liquid product 22o84 Description dark red liquid (pure aniline) 4. Butylene Butylene loaded 14,1 Amount of olefin loaded 10o6 Mole ratio 1/1 Temperature (OC) 100 Pressure 405 Radiation (megarep) 2.19 Li quid product Description small amto viscous liquid 26

The University of Michigan * Engineering Research Institute The second experiment contained 18o2 grams of propylene and 26.8 gms of iso-butane and was conducted at a temperature of 1100~C and at a pressure of 2400 psig. This received an unknown amount of radiationo An oily residue was left on the side of the reactor but there was not a sufficient quantity of it for recovery (c) Butylene One experiment was conducted with butylene and iso-butane in 1:1 mole ratioo The reactor contained 21.2 gms of isobutane and 20.3 gms of butyleneo After radiation, a small amount of camphorous smelling liquid was detected on the walls of the reactoro (2) n-Butane One experiment was carried out with 19.8 gms of ethylene and 22.2 gms of n-butane0 The reaction was conducted under ambient conditions add received a dose rate of 9,5 megarep. A white flaky solid was recovered that resembled polyethylene. The product weighed 0.55 gmso There was no liquid product present (3) Aniline and Ethylene Twenty five cc of aniline was loaded into the stainless steel reactor. Then 19.7 gms of ethylene was charged into the reactor with a resulting pressure of 970 psig at 20~Co The experiment was conducted at ambient conditions and received a total dose of 4.2 megarep. A dark red liquid product was recovered that weighed 22.84 gmso However, 'it is believed that all of the product was pure aniline, Another experiment was conducted by irradiating pure anilineo In this case also a red liquid was recovered that distilled over at the boiling point of pure aniline. (4) Butylene and Propylene An experiment to determine the copolymerization effects of propylene and butylene was al'so madeo A 1:1 mole ratio of the two materials (10,6 gm of propylene and 14.1 gms of butylene) was heated to 1000~C with a resulting pressure of 405 psigo The reaction received a dose of 2.19 meg& repo After venting the reactor, a small amount of viscous liquid was found at the bottom of the reactor, However, the amount was insufficien for recovery, In addition, there appeared a very small amount of brownish solid material attached to the sides of the reactor. 27

The University of Michigan ~ Engineering Research Institute Co Procedure The stainless steel bombs were used as reaction vessels. The system was as shown in Figure 10o The comolete system was first evacuated to a pressure of 300 micronso The reaction vessel and calibrated vial were then immersed in a dry ice bath. The calculated amount of reactant was condensed in the calibrated vialo The dry ice bath was then removed from the vial, and the reactant was allowed to condense in the reaction vessel. This procedure was followed for each of the two reactants.

- - ~~~~~~~~~~~~~~I PRESSURE GAUGEs - vACUUM 3 -— 1 r ---- 2UPTURE DISK VENT ' 0 KNOWN VOLUME — LOADING CYLINDER D) l | DEWAR FLASK I /PROPYLENE, DRY ICE BATH _ 1 -LN-BUTANE, GRADUATE DEWAR FLASK m ISOBUTANE, DRY ICE BATH OR MIXED REACTOR BUTENES.R C ETHYLENE I. CYLINDER Figure 10. Combination Gas Loading Apparatus

The University of Michigan * Engineering Research Institute APP ENDIX A Sample calculations for Run No. 16c (Catalytic Cracking of Cetane) Average reaction temperature was determined by the integral of the temperature profile, i.e., the average through out the reaction zone. Off gas. vol. 0.362 S.CoFo (SoC,F, at 600C and 1 atmosphere) Off gas M.W, = 41.6 (Determined from mass spec. analysis) Off gas weight = 0.362 SoCF. x 1.197 gm moles SC.F ox 41,6 gm = 18.1 gm gm mole Weathered gas vol. = 0.0285 SoCoFo Weathered gas MoWo = 58 (assumed) Weathered gas weight = 0o0285 SoCoF. x 1.197gm moles x SoC.Fo 58 a = 2.0 gm gm mole Purge gas vol = 2000 cc (at 748 mm and 830C)= 0.0623 S*CoFo Purge gas composition = 35.4 wt %~/ organic material + 64.6 ' Nitrogen Ave. M,W, of organic material = 45.6 (from mass spec.) Weight organics in purge gas=0.0623 S.C.F. x 0.354 x 1.197 gm moles x 45.6 gm mole 2 gm S.CF, gm mole Liquid product weight = 68.8 gins Total product weight = 18.1+2.0+1.2+68.8=90 gms Total feed = 94.0 gms Material balance = 9002 x 100 = 96.0 94.0 Gas product t % (input basis)= 181+2.0+1 x 100=22.7% 30

The University of Michigan ~ Engineering Research Institute Liquid lighter than cetane, wt % = 20 % from liquid analysis Liquid lighter than cetane = 0.20 x 68.8 gms = 13.8 gms. Liquid products, wt % (input basis) =l38x 100=14.7 % Cetane converted = 13.8 + 18.1 + 2.0 + 1.2 = 35.1 gms Cetane converted, wt % (input basis)100 = 37.3 % Cetane converted, wt % (output basis)-=35.2x 100= 38.9 % 9002 B. Sample Calculations for Ethyl Mercaptan and Propylene Rate Study No, 2 C2H5SH + CH2 CH2 Rad >C2H5SC2H5 1. Activity Coefficient P = Total Pressure, psia Pv= Vapor Pressure, psia r = Activity Coefficient Xp= Xm = Mole fraction propylene and mercaptan P = [rPvx at 500~C Vapo Pressure C3H6 = 297 psia Vapo Pressure C2H5SH= 23.8 psia When equal mole quantities of C3H6 and C2H5SH were loaded into a reactor at 50~C the observed pressure was 182 psia. 182 = (r x 297) (.5) + (2308) (05) r=1.14(arbitrarily assuming activity coefficient for ethyl mercaptan = lo0) 2. Mole % C3H6 and C2H5SH at any time (a) It was assumed that the only reaction was an addition between C3H6 and C2H5SH and that the vapor pressure of the product is negligibleo 31

The University of Michigan ~ Engineering Research Institute (b) After 1510 minutes of radiation the pressure was observed to be 110 psiao 96 = (279) (1,14) (X) + 23,8 (X) X = mole % C3H6 and C2H5SH = 0.304 3., Conversion and Concentration of C3H6 and C2H5SH a = 1 = initial number of moles of C3H6 and C2H5SH y = moles of C3H6 and C2H5SH reacted n = moles of C2H5SH C2H5SH + C2H4 >C2H 5-S- C2H5 a-y a-y y At any time, the total number of moles = 2a-y X = 2-y 2a-y 0.304 = 2-y y = 0.563 = % conversion n =.5 o- 563 (.5) = 0.218 4. Order of Reaction and Rate Constant (a) If 1st order reaction dn t k n t time, hr k = rate constant, hr. upon integrating log n = -kt + I Since a plot of log n vso t was a straight line, the reaction is 1st order 32

The University of Michigan ~ Engineering Research Institute (b) Rate Constant -k = slope of log n vs t or log Q= kt no = initial C2H5SH = 0,500 n 00500 k 1510 log o21 - -151 60 k = 0.0328 hr-1 C Ethylene Loading Calculation Volume of measuring vessel = 274 cco = 0.00968 ft3 Initial pressure of measuring vessel = 600 psig Final pressure of measuring vessel 300 psigo Temperature during loading = 60~F Volume per pound of C2H4, V9 taken from Chem. Eng. Handbook by Jo H, Perry 600 psigo = 615 psiao = 41.8 atmospheres from Perry's Handbook: at 41.8 atm and 60~F V-1 = O0208 ft3/lb Initial wt. of C2H4 charged 0968 ft 00465 lb. V1 0.208 ft3/lb 300 psig = 315 psia = 21.4 atmospheres from Psrryts Handbook: at 21,4 atmospheres and 60~F V2 = Oo540 ft3/lb. Final wt, of C2H4 charged - - 0,00968 ft3 lb V2 0.540 ft'5/lb wt, of C2H4 charged in reactor = (0o0465 lb-0o0179 lb) 454 l = 13.0 gm 33~~~~

1.00 Formula from International Crit. Tables dt =0.8623-10-3(1.077)t + 0'6(2.25) t2+ 109x 10.9t3 t= C Accurate in range 00-80@.90 E E W, z.80 LU.70 -100 -90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 TEMPERATURE IN 'C Figure 11. Density of Ethyl Mercaptan vs. Temperature

.80.70 rI II.60 E50 E l E ~F- D.3,.2C Critical point W =I.30 -200 -100 0 +100 +200 4 Figure 12. Liquid Density of Iso-Butane @ Saturated Pressure vs. Temperature -2 00 - 00from Handbook of Butane Propane Gases +00 200 300 ~F- Data from Handbook of Butane Propane Gases

.80 1...70 C '.60 E =r.50 lo E E 0)- mL m.40..30 Lt Critical point.20... '".10' " -200 -100 0 100 20 0 TEMPERATURE OF Figure 13. Liquid Density of Propylene Saturated Pressure vs. Temperature ~F - Data from Handbook of Butane Propane Gases

0~~~~~~~~~~~~~~~~~~~~~~~~~~~ I0 1000 '"_ // E -OOOO_ ~~E~~~~ ~~ ~/ - 1 1 Lfl I~~~~~~~l S~~~~~~~~I IA Isobutene & 1-Pentene Ds~~~~~ I<~~~ -Bute1<~~~~~~~~~~~~ n~ Xthyl m erca 0tA ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~& pentane 100 \ / X AX A.t'./,. x -162 -160 -155 -1 50 -145 -140 -135 -130 -125 -120 -115 -110 -105 -100-95-90-85-80-75-70 -60 -50 -40 -30-20-10 0 20 40 60 /TEMPERATURE IN ~C Figure 14. Vapor Pressure of Various Liquids vs. Temperature (Range:-1620C to +600C) Data from Indo Engo Chemo 39, 518-550 (1947). I~~~~~~~~~~~~~~~~~~~Ehln

1000 900 800 700' 600 500 Ethyl mercapt an.~~~~ ~ ~~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~.< 400 -20 -10 0 121-Pentene | r Fiue1eVprPesrrfVaiu iud eprtr (Rne-20Ct,20C 0)300 I U. 0 0 200 ' E 200 p-Xylene E / niline z D 100 _ _ _ __,,' 90 _ _ _ LU 80 a. 70 LU 60 50 0 _ _=_ _ _ __ -- - - - - - - kA 40 30, - 20 - 10~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~-20 -10 0 10 20 30 40 50 60 70 80 90 100 120 140 160 180 200220 240 TEMPERATURE IN *C Figure 15. Vapor Pressure of Various Liquids vso Temperature (Range:-200C to 240) Data from Ind. Engo Chem. 39, 518-550 (1947).

UNIVERSITY OF MICHIGAN 3 111015 03095 007811111111 3 9015 03095 0078

Production Notes Form Univ. of Michigan Preservation/MOA 4 Project MOA4 ID#: ll " 7 2/- Shipment#: Call #: Date Collated: / Collated by: _ _ _ _ _ Total # of Pages:.LYes No K.W. ' 4 jf Foldouts/Mapsr: Yes o Bookplates/Endsht< Yes 1o Missing Pages:tN Yes No / Irregular Paginaion: Yes No OthayProduction Notes:. /g f/ ) 5.>, ' k.A~es No NLJ -rr\ X){o3Z