Document v1JEROR2Bge9MdyQBXym7G4jY

JNmNTO CHEMICAL COMPANY Hm)ROCARBONS DIVISION 'EX'AS CITY, TEXAS METHOD 602.296 (G.C.) April 26, 1962 Page 1 of 7 MATERIAL Vinyl Chloride Monomer (VCM) ANALYSIS Heavy-epd Impurities: MVA Ethyl Chloride 2-CPY Vinylidene Chloride (1, 1-DCY) t-1,2-DCY CB SAMPLE Liquid Sample in VCM Bomb APPARATUS P. E. Model 154-C Vapor Practometer equipped with gas inlet valve, or equivalent, valved for multi-column operation (See attached drawing.) Hydrogen Flame Ionization Detector - capable of detecting 2 x 10-10 moles of chlorinated compounds. Meeco Vaporizing Valve, Type IS, or equivalent, for flashing liquid VCM into gas sample loop of chromatograph. Flow-meter for determining rate of purge on sample loop. Recorder - L. & N. Speedomax Type G, or equivalent, with 1 second pen and 5 mv full-scale deflection. Recorder should be modified to switch to either the thermistor detector or the flame detector. CBY 1110243 RSV0031717 The Information contained herein is, to our best knowledge, accurate; but all recommendsons or BUggestionB are made without guarrite", &j ce the conditions of use are beyond our control. Konsent.0 dieclaims any liability for loss or damage incurred in connection with the use of the above." cby RSV0031718 METHOD 602.296 (G.C.) April 26, 1962 Page 2 of 7 REAGENTS AND SUPPLIES Aluminum Tubing - 3/16 inch O.D. Helium - 2 regulated supplies. Chromosorb - red, 30/60 mesh. Narcoil 40 - dinonyl phthalate from National Research Corp. Hydrogen - electrolytic grade. Air - well-filtered, clean supply. Ethyl chloride - commercial grade. 2-Chloropropene - Columbia Organic Chemical Co., purified by gas chromatography. 2-Chloro-l,3-butadiene - Monomer-Polymer, Inc., purified by gas chromatography. 1,1-Dlchloroethylene - Monomer-Polymer, Inc., purified by gas chromatography. Vinylacetylene - E. I. DuPont Co., purified by gas 'chromatography. Vinyl Chloride - Free of, or very low concentration of, impurities. Acetone - for column packing preparation. PROCEDURE A. Column Preparation 1. Mix 15 grams of Narcoil 40 with approximately 100 ml of acetone. 2. Pour mixture over 85 grams of 30/60 mesh chromosorb and add more acetone if necessary to make a slurry. 3. Mix continuously while evaporating the acetone. If available, use rotary-film evaporator with baffled flask for mixing. Apply heat from hot air gun and vacuum to flask to aid in evaporation. CBY 1110245 RSV0031719 "Ihe information contained herein is, to 'ur best knowledge, accurate; but all reecmmendat'onB or suggestions are made without guar.".tee, bj. ca the oondltions of use are beyond our control. Konssnto disclaims any liability for loss or damage incurred in conneotioa with the use of the above.* CBr 11102V6 RSV0031720 METHOD 602.296 (G.C.) April 26, 1962 Page 3 of T PROCEDURE (cont'd) 4. When the acetone Is evaporated, re-screen to remove fines and pack one 20-foot length and one 35-foot length of 3/16-inch tubing with the 30/60 mesh fraction. 5- Install the columns in the instrument as shown on the attached drawing. 6. Adjust the two helium pressures and restrictor valve to give the following flows: a. Column I: 75 ml/minute. b. Column II (wl'tla restrictor in flow, path): 85 ml/mln. c. Columns I &. II (in backflush position): 85 ml/mln. 7. Adjust temperature to 50 C. and allow Instrument and columns to reach equilibrium. 8. Light the hydrogen burner and adjust the hydrogen and air flows so as to yield maximum signal-to-noise ratio when MVA passes through it. 9. Turn on amplifier and recorder and set for maximum sensitivity. The Instrument should show no drift for at least five minutes before it is ready for use. B. Analysis 1. Purge the 5 cc sample loop for at least one minute with sample flashed through the Meco Vaporizing Valve, then inject the sample into the flowing carrier stream with the columns in Position A and the recorder turned to the thermal conductivity detector. The attenuator switch of the detector should be set on an attenuation of 2. The valve between the thermal detector and the flame detector should be in the vent position to prevent VCM from going to the flame detector. 2. Allow the sample to flow in Column I as shown in Position A for approximately three minutes (valve should be switched when recorder pen reaches 50# of full scale coming down on VCM peak). This allows the components lighter than VCM and most of the VCM to be vented-from Column I. CBY 1110247 RSV0031721 *The Information contained herein is, to r>r beat knowledge, accurate; but eix rpcoomendat ore or suggestions are made without guar, tea, ex cj the conditions of use are beyond our control. Monsanto disclaims any liability for lose or damage incurred in connection with the use of the above.* CBY 11102*8 RSV0031722 METHOD 602.296 (G.C.) April 26, 1962 Page 4 of 7 PROCEDURE (cont'd) 3. Just before MVA is eluted from Column I, switch the valve to Position B. This allows everything behind the VCM peak to be backflushed onto Column II where they are separated and then flow to the detector. Sometime after backflushlng and prior to the backflushed VCM being eluted from Column II, switch the recorder to the flame detector and the valve between the thermal detector and the flame detector to the position such that the flow is through the flame detector. 4. Record all peaks eluted from Column II, A typical chromatogram is attached. CALCULATIONS The concentration of each component is calculated as follows: 1. Measure the peak height and width at one-half the peak height using a scale of 50 divisions to 1 inch. 2. Calculate the area of each peak according to the following equation: area = peak height x peak width at one-half peak height x attenuation 3. Calculate the concentration of each component as follows; Concentration= peak area x factor PREPARATION OP REAGENT SOLUTIONS None necessary. CALIBRATION 1. Prepare synthetics of MVA, ethyl chloride, 2-CPY, 1,1-DCY, trans-l,2-DCY, and CB in VCM to cover the concentration range of intrest. At least two synthetics Bhould be pre pared in each concentration range. Synthetics should be prepared in clean, stainless steel bombB of any convenient size. The pressure should be sufficient to permit extended use of the mlx'.ures. The blending Bystem used must be completely free of leaks and all kinds of foreign materials. CBY 1X102M RSV003I723 "The Information contained herein Is, to our best knowledge, accurate; but all recommendaV ore or suggestions are made without guarantee, t>i cs the conditions of use are beyond our control, Itonsonto disdains any liability for Iobb or damage incurred In connection with the use of the above.* CBY 1110250 RSV0031724 METHOD 602.296 (G.C.) April 26, 1962 Page 5 of 7 CALIBRATION (cont'd) 2. Analyze the synthetic mixtures as described under the Procedure for Analysis. 3. Calculate the factor for each component according to the following equations. factor - concentration (ppm) of component in synthetic peak height x peak width at one-half peak height x attenuation SAFETY PRECAUTIONS No precautions need be observed other than those normally observed when handling volatile chlorinated compounds under pressure. ANALYTICAL TIME The average analytical time for this analysis should be 1.0 hour. PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES FOR REPORTING RESULTS 9556 confidence limits of this method is 55^ of the amount present. Report results to two significant figures. SCOPE This method is designed only for heavy-end Impurities in VCM, although the components analyzed for could be detected In other materials if the proper point is selected for backflushing. EDC may be determined in VCM using the front column only. In this case allow the sample to run through Column I with the eluted components being vented until after VCM has been almost completely eluted, then switch the flow through the flame detector. Calibration for this should be made separately. REFERENCES Monsanto Research Method TC-1157 (GC). TGL/ob 5-8-62 CBY 1110251 RSV0031725 The' Information contained herein is, to our best knowledge, accurate; but all recommendations or suggestions are made without guarantee, ei oe the conditions of use are beyond rur rjntrol. Konsanto disclaims any liability for lose or damage incurred in connection with the use of the above.* CBV I!1025' RSV0031726 hNY-'VvVY-V- Poairiow A W- ft _! V, V* MT Ti>*eHTPetTM^ Vir- Posiriofj B cz::d l{w *r C-HA+tfJSL 71 j Hfi T* VL AiTUftTOR. Vi " Mall. 8-PokT \Sal\/ Vi- Cike-Le Seal. &eui #&*t Vit-v? Vii" _W/*y 6}*.s Vii-t/ff \4- AJebvle V'M-ve Ci - C.0L.UH1J .X C2 - Co LV.HH UL Helium Heq</latoK Q,,Z~ /kes&uAE GrtuQSS ,0-6,0^ Vf- ClAiLf S>Al_ 4--foKT V/'LWe MAEpTHr iOl D2 Page 6 o f 7 60 6, 2 .296. 1962 (G .C . CBV 1110253 /=/ <} v/i .7: RSV0031727 The information contained herein is, to cur best knowledge, accurate; but t.l recommends!'one or suggestions are made without gv<- ii, tj. .ce the conditions of use are beyond our control. Monsanto disclaims any liability for loss or damage incurred In connection with the use of the above.* CB'f H1025* RSV0031728 METHOD 602.296 (O.C.) April 26, 1962 Page 7 of 7 1 CBY 1110255 RSV0031729 "The Information contained herein is, to our best knowledge, accurate; but all recoramendat'one or suggestions are made without guarriTee, 6i ce the conditions of use are beyond our control. Monsanto disclaims any liability for loss or duiuage incurred In oonnection with the use of the above.* CBY 1110256 X RSV0031730