Document 60wVZ318gmK3nYngBz61LDr4

MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS MATERIAL VCM reactor off gas (22R1) DEPT. 22 METHOD 602.275 May 26, 1964 Page 1 of 3 (WC) ANALYSIS REQUIRED Acetaldehyde CH3 CHO SAMPLE SIZE 2 liter glass sample bomb APPARATUS Special gas burette with compensating monometer 25 ml graduate Beckman Model "B" 3 ml pipette 20 ml cells REAGENTS Methyl Indole solution - 20 ml Cp HC1, 10 ml H 0, add 0.05 g methyl indole. PROCEDURE Introduce 100 ml of sample into modified burrell and adjust to atmospheric conditions by means of compensating manometer. Prepare a mixture of 22 ml of distilled H^O and 3 ml of oc methyl indole solution m a 25 ml graduate. Pass sample through scrubber after adjusting to atmospheric pressure. Allow solution to stand for 15 minutes before reading on Beckman using 20 mm cells and a wavelength of 550 uu with a distilled water blank. CBY 1002326 RSV0032029 METHOD 6C2.276 (WC) May 26, 1964 Page 2 or 3 CALCULATION e/ _TT _TT_ A> CIi^CHO -- CC Acetaldehyde from chart X 100 Volume of sample If 100 ml sample is used % CH^CHO = CC Acetaldehyde from chart See chart last page PREPARATION OF REAGENT SOLUTIONS See Solutions Manual CALIBRATION AND/OR CALIBRATIONS Prepare synthetics from known volumetric amounts of acetaldehyde at desired levels needed. SAFETY PRECAUTIONS Be sure mercury resevoir is in lowest elevated position on support when not in use so no pressure build-up results in a mercury spill Clean up any spilled mercury and dust area with sulfur. Breathing mercury vapors should be avoided. ANALYTICAL TIME 0.1 hour PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES FOR REPORTING Method is precise to nearest 40 ppm at high level of 80 to 900 ppm. Method is precise to nearest 20 ppm at low level of 10 to 100 ppm. Using a 100 ml sample, acetaldehyde can be read to nearest 10 ppm AcH. RCR/mlw 5/26/64 CBY 1002327 RSV0032030 METHOD 602.275 May 26, 1964 Page 3 of 3 (WC) ACETALDEHYDE CONVERSION CHART 550 mM , Distilled Water Blank Optical Density cc Acetaldehydi 25 mm 20 mm 0.128 0.198 0.296 0.407 0.540 0.650 O.988 0.102 0.157 0.237 0.326 0.432 0.520 0.791 - -................................ 0.008 ------- 0.016 ------- 0.029 ................................ - - 0.032 ------- 0.040 ------- 0.048 ------- 0.090 ACETALDEHYDE, LOW RANGE Wave Length: 550 Optical Density cc Acetaldehyde 25 mm 20 mm 0.14 0.115 0.10 0.084 0.071 0.057 0.042 0.030 0.016 0.12. 0.092 0.080 0.067 0.057 0.046 0.034 0.024 0.013 ------- 0.010 ------- 0.008 ................................................... - - 0.007 ------- 0.006 ................................................ 0.005 ------- 0.004 ------- 0.003 ------- 0.002 ------- 0.001 Using a 100 ml sample, the acetaldehyde can he read to the nearest 10 ppm AcH. If a 500 ml sample Is used the AcH concentration can he read to the nearest 2 ppm. Calculation: AcH = CC AcH from chart x 100 Volume Sample CBY 1002328 RSV0032031 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602,276 May 26, 1964 Page 1 of 3 (WC) MATERIAL VCM reactor off gas (22R1) ANALYSIS REQUIRED Acetaldehyde CH3CHO SAMPLE SIZE 2 liter glass sample bomb APPARATUS Special gas burette with compensating manometer 25 ml graduate Beckman Model "B" 3 ml pipette 20 ml cells REAGENTS Methyl Indole solution - 20 ml Cp HCl, 10 ml H^O, add 0.05 methyl indole. PROCEDURE Introduce 100 ml of sample into modified burrell and adjust to atmospheric conditions by means of compensating manometer. Prepare a mixture of 22 ml of distilled ^0 and 3 ml ofQ( methyl indole solution-in a 25 ml graduate. Pass sample through scrubber after adjusting to atmospheric pressure. Allow solution to stand for 15 minutes before reading on Beckman using 20 mm cells and a wavelength of 550 m/4 with a distilled water blank. CBY 1002329 RSV0032032 METHOD 602.276 (WC) May 26. 1964 Page 2 of 3 CALCULATION % ch3cho CC Acetaldehyde from chart X 100 Volume of sample If 100 ml sample is used % CH^CHO = CC Acetaldehyde from chart See chart last page PREPARATION OF REAGENT SOLUTIONS See Solutions Manual CALIBRATION AND/OR CALIBRATIONS Prepare synthetics from known volumetric amounts of acetaldehyde at desired levels needed. SAFETY PRECAUTIONS Be sure mercury resevoir is in lowest elevated position on support when not in use so no pressure build-up results in a mercury spill. Clean up any spilled mercury and dust area with sulfur. Breathing mercury vapors should be avoided. ANALYTICAL TIME 0.1 hour PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES FOR REPORTING Method is precise to nearest 40 ppm at high level of 80 to 900 ppm. Method is precise to nearest 20 ppm at low level of 10 to 100 ppm. Using a 100 ml sample, acetaldehyde can be read to nearest 10 ppm AcH. RCR/mlw 5/26/64 CBY 1002330 RSV0032033 METHOD 602. 276 (WC) May 26, 1964 Page 3 of 3 ACETALDEHYDE CONVERSION CHART 550 mAg Distilled Water Blank Optical Density cc Acetaldehyde 25 ram 0.128 0.198 0.296 O.W 0.540 0.650 0.988 20 nan 0.102 0.157 0.237 0.326 0.432 0.520 0.791 ' ------ - ------------------------- ------- ------- 0.008 0.016 0.029 0.032 0.040 0.048 0.090 ACETALDEHYDE. LOW RANGE Wave Length: 550 aU-C Optical Density cc Acetaldehyde 25 tnm 20 mm 0.14 0.115 0.10 0.084 0.071 0.057 0.042 0.030 0.016 0.12. 0.092 0.080 0.067 0.057 0.046 0.034 0.024 0.013 ------- ------------------- ------------------------------- 0.010 0.008 0.007 0.006 0.005 0.004 0.003 0.002 0.001 Using a 100 ml sample, the acetaldehyde can be read to the neareai 10 ppm AcH. If a 500 ml sample is used the AcH concentration can be read to the nearest 2 ppm. Calculation: i> AcH = CC AcH from chart x 100 TM Volume Sample CBY 1002331 RSV0032034 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.277 August 1, 1964 Page 1 of 2 (WC) MATERIAL Cooling Tower Water ANALYSIS REQUIRED Chromate Ion SAMPLE SIZE Pint Bottle APPARATUS 100 cc Graduated Cylinder 250 ml Iodine Flask 50 ml Burette REAGENTS 0.1 N Na2S203 20% H2S04 10% KI 1% Starch Solution PROCEDURE Using the graduated cylinder measure 100 cc of sample into the iodine flask, add 10 ml 20% H2S04 and 25 ml 10% KI. Titrate with 0.1 N Na2S23 until the intensity of the brown color begins to fade. Ada about 10 drops of starch indi cator and continue to titrate until the deep blue color just disappears. The color change at the end point is from the deep blue of the starch-iodine complex to a light bluegreen. CALCULATION ppm Cr04 = ppm Cr04 = Thio x NThio x 0.03867 x IQ6 100 Thio x NThio x 386.7 CBY 1002332 RSV0032035 METHOD 602.277 (WC} August 1, 1964 Page 2 of 2 PREPARATION OF REAGENTS See Solution Manual STANDARDIZATION AND CALIBRATION Refer to Solution Manual for standardization of 0.1 N Na_S_0,. 223 SAFETY PRECAUTIONS Use normal safety precautions vhen handling material. ANALYTICAL TIME Time required for this analysis is 0.1 hour. PRECISION The precision of this method is - 10 ppm at 700-800 ppm level. SCOPE The excess iodine liberated from the KI in an acidified solution is titrated with thio sulfate. RCR:ff 8/12/64 CBY 1002333 RSV0032036 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS MATERIAL Diesel oil from 22D3 ANALYSIS REQUIRED DEPT. 22 METHOD 602.278 May 14, 1964 Page 1 of 3 (WC) SAMPLE SIZE One-half pint APPARATUS 50 ml graduate cylinder Precision aquatrator for Karl Fischer moisture determinations consisting of two 25 ml automatic burettes with 100 ml reservoirs, magnetic stirrer with teflon covered stirring bar platinum electrodes, drying tubes and an electronic control box (purchased from W. H. Curtin and Company). 500 ml flat-bottom flask with two side arm necks (purchased from Scientific Glass Blowing Company). Water aspirator vacuum system REAGENTS Karl Fischer - reagent Standard water - methanol Product methanol CBY 1002334 RSV0032037 METHOD 6C2.278 (WC) May 14, 1964 Page 2 of 3 PROCEDURE 1. Remove previous sample from flask with aspirator. Add 20-30 ml of product MeOH to flask, and add Karl Fischer reagent m excess until Galvonometer holds at 15 to 20 micro-amps. The solution in the flasks will be brown in color at this point. 2. Back titrate with standard water until the brown color starts to fade, start dropwise addition of standard water until the Galvonometer needle swings toward zero. Allow time for reaction between drops. The flask is now dry. The solution in the reaction flask will be yellow at this point. 3. Add 25 ml of the oil to the flask by means of a graduate cylinder. Add Karl Fischer reagent m excess (see paragraph #1). 4. Back titrate to dryness with standard water (see paragraph #2). 5. Record total volume used of Karl Fischer and standard water. Record normalitites of solutions. Notes: 1. Be sure that automatic burettes are full before titrations start. 2. Protect burettes from atmospheric moisture with "Driente." CALCULATIONS HQ 2 (V Karl Fischer x N Karl Fischer) - (V Std H,,0 x N Std H^O x 100 V of Sample Used x Density of sample V = Volume m Milliliters N = Normality CBY 1002335 RSV0032038 METHOD 602.278 May 14, 1964 Page 3 of 3 (WC) PREPARATION OF REAGENT SOLUTIONS Refer to Solutions Manual STANDARDIZATION AND/OR CALIBRATIONS See Solutions Manual for detailed procedure for pre paring and standardizing Karl Fischer, and standard water solutions. SAFETY PRECAUTIONS Skin contact and breathing vapors should be avoided. ANALYTICAL TIME REQUIRED 0.1 hour PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES FOR REPORTING RESULTS Report to nearest .001%. Relative precision is + .002% at the .005% level. SCOPE The method is based on the reduction of iodine by sulfur dioxide m the presence of water pyridine and alcohol are present to react with the sulfur trioxide and hydroiodic acid formed during the iodine reduction. Peroxides and mercapbans interfere. Appreciable quantities of aldehydes and amines also interfere. Rapidity of analysis is essential as moisture from the air will cause an appreciable error. The method is applicable for determining % water m organic materials at all concentrations of H^O. Method range for this material and sample size is .002% to 1% H^O. RCR/mlw 5/14/64 CBI 1002336 RSV0032039 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.283(WC) August 12, 1964 Page 1 of 3 MATERIAL 22D7, D8, D9, DIO Bottoms ANALYSIS REQUIRED HO 2 SAMPLE SIZE One-half pint APPARATUS 50 ml graduate cylinder Precision aquatrator for Karl Fischer moisture determinations consisting of two 25 ml automatic burettes with 100 ml reservoirs, magnetic stirrer with teflon covered stirring bar platinum electrodes, drying tubes and an electronic control box (purchased from W. H. Curtin & Co.). 500 ml flat-bottom flask with two side arm necks (purchased from Scientific Glass Blowing Company). Water aspirator vacuum system REAGENTS Karl Fischer - reagent Standard water - methanol Product methanol PROCEDURE 1. Remove previous sample from flask with aspirator. Add 20-30 ml of product MeOH to flask, and add Karl Fischer reagent in excess until Galvonometer holds at 15 to 20 micro-amps. The solution in the flasks will be brown in color at this point. CBY 1002337 RSV0032040 METHOD 602.283 August 12, 1964 Page 2 of 3 2. Back titrate with standard water until the brown color starts to fade, start dropwise addition of standard water until the Galvonometer needle swings toward zero- Allow time for reaction between drops. The flask is now dry. The solution in the reaction flask will be yellow at this point. 3. Add 50 ml of the sample to the flask by means of a pipette. Add Karl Fischer reagent in excess (see para. #1}. 4. Back titrate to dryness with standard water (see para. #2). 5. Record total volume used of Karl Fischer and standard water. Record normalities of solutions. NOTES: 1, Be sure that automatic burettes are full before titrations start. 2. Protect burettes from atmospheric moisture with "Drierite." CALCULATIONS H2U (V Karl Fischer x N Karl Fischer) - (V Std H2O x N Std ^0 x 100 V of Sample Used x Density of Sample V = Volume in Milliliters N = Normality Density = 1.24 PREPARATION OF REAGENT SOLUTIONS Refer to Solutions Manual STANDARDIZATION AND/OR CALIBRATIONS See Solutions Manual for detailed procedure for pre paring and standardizing Karl Fischer, and standard water solutions. CfiY 1002338 RSV0032041 METHOD 602.283(WC) August 12, 1964 Page 3 of 3 SAFETY PRECAUTIONS Skin contact and breathing vapors should be avoided. ANALYTICAL TIME REQUIRED 0.1 hour PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES FOR REPORTING RESULTS Report to nearest .001%. Relative precision is + .002% at the .005% level. SCOPE The method is based on the reduction of iodine by sulfur dioxide in the presence of water pyridine and alcohol are present to react with the sulfur trioxide and hydroiodic acid formed during the iodine reduction. Peroxides and mercaptans interfere. Appreciable quantities of aldehydes and amines also interfere. Rapidity of analysis is essential as moisture from the air will cause an appreciable error. The method is applicable for determining % water in organic materials at all concentrations of H20. Method range for this material and sample size is .002% to 1% ^0. RCR:ff 8/12/64 CBY 1002339 RSV0032042 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.287 May 1, 1964 Page 1 of 4 (WC) MATERIAL Product Vinyl Chloride Monomer ANALYSIS REQUIRED Acetylene SAMPLE SIZE 100 ml APPARATUS 250 ml Erlenmeyer equipped as follows: The bottle is pro vided with a one hole rubber stopper. A three inch length of glass tubing is inserted through the stopper so that approximately one half of it extends through the top of the stopper. Attach 1-1/2 foot of rubber tubing to the glass outlet tube. 250 ml Gas Scrubbing bottle equipped with a capillary scrubbing tube of approximately 0.3 mm diameter that extends to within 1/2 inch of the bottom of scrubber. Beckman Model "B" Spectrophotometer One 250 ml graduated cylinder One 100 ml graduated cylinder REAGENTS Ilsovay's Solution - stock solution Solution "A" 10% CuNO ~ 3H 0 20% NH OH Tech. Isopropanol Distilled water 200 ml 80 ml 200 ml 580 ml CBY 1002340 RSV0032043 METHOD 602.287 May 1, 1964 Page 2 of 4 (WC) Solution "B" 15% Hydroxylamine Hydrochloride Solution "C" 1.0% Gelatin (Eastman Calf Skin) Note: 20% NH^OH ~ 710 ml concentrated NH^OH to 1 leter. PROCEDURE Into the gas scrubbing bottle, measure 110 ml "A", 40 ml "B" and 10 ml "C", and mix thoroughly. Chill a 100 ml graduated cylinder in the dry ice chest for 15 minutes. From the sample bomb, measure 100 ml vinyl chloride into the chilled graduated cylinder and transfer it quickly to the 250 ml Erlenmeyer flask. Stopper the flask with the stopper that is connected to the inlet tube of the scrubber with rubber tubing. Any Acetylide present will form copper acetylide , m the scrubber and the VCM will escape through the outlet tube of the scrubber. The entire procedure should be con ducted in the hood. After all the VCM has evaporated, determine the optical density of the Ilsovay's solution in the scrubber under the following conditions: Standard - Mixed Ilsovay's solution Wavelength - 540 mu Cell - 20 mm CALCULATIONS Refer the 0,,D,, reading to the attached graph for the ppm C2H2* Two determinations should agree within 1 ppm. PREPARATION OF REAGENTS See Solution Manual CBY 1002341 RSV0032044 METHOD 602.287 May 1, 1964 Page 3 of 4 (WC) STANDARDIZATION AND/OR CALIBRATION See detailed Section on Standardization and Calibration Acetylene in Liquid Oxygen - Method 602.136 (WC), page 7. SAFETY Use normal precautions with chemicals and glassware. Copper acetylide is quite explosive when dry. If any acetylide forms, destroy by dissolving in HC1 and flushing down the drain with copious amounts of water. ANALYTICAL TIME 0.2 hour PRECISION 95% confidence limits are + 0.5 ppm at the 1 ppm level. SCOPE Acetylene reacts with an ammonical copper solution (IlsovBty's solution) to form copper acetylide, the characteristic red copper acetylide is read Spectrophotometrically. CBY 10023^2 RSV0032045 RCR/mlw 5/1/64 1 METHOD 602.287 May 1, 1964 Page 4 of 4 (WC) ACETYLENE IN PRODUCT VCM Standard Wavelength Cell EE5L 1 2 3 4 5 6 Ilsovay's Solution 540 mu 20 mm O.D. 0.17 0.34 0.51 0.68 0.85 1.02 CBY 1002343 RSV0032046 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.288 May 14, 1964 Page 1 of 5 (WC) MATERIAL Product vinyl chloride and 22E11 ANALYSIS REQUIRED Determination of aldehydes SAMPLE SIZE Quart thermos bottle APPARATUS Beckman Model "B" Spectrophotometer 100 ml volumetric flask Coca-cola bottle and cap Bottle opener Ice pick 250 ml Erlenmeyer flask 100 ml graduated cylinder 25 ml graduated cylinder 1 ml pipette Triple beam balance REAGENTS Alpha - methyl indole solution Ammonium hydroxide (NH^OH) , (CP cone.) Acetaldehyde (CH^HO) CBY 1002344 RSV0032047 METHOD 602.288 (WC) May 14, 1964 Page 2 of 5 PROCEDURE Select a clean, dry Coca-cola bottle free from large scratches. Pipette 1.0 ml of concentrated NH OH into the bottle and add 10 ml H^O- Pour IOC ml of vinyl chloride into a which has been cooled in dry ice for Transfer to the Coca-cola bottle and immedia tely. 100 ml graduate at least 15 minutes. cap the bottle Shake the sealed bottle vigorously and place m the cabinet for one hour (CAUTION: Wear face shield while handling vinyl chloride). Puncture the cap with an ice pick and then remove cap. Allow the vinyl chloride to evaporate m the hood. When all of the vinyl chloride has evaporated, wash the contents of the bottle into a 100 ml volumetric flask with several portions of distilled water. The volume of distilled water shall not exceed 50 ml. Add 20 ml of >t- methylmdole solution to the washings. Shake to mix thoroughly and allow the solution to stand for 10 minutes. Dilute to 100 ml with distilled water and again shake thoroughly. Read the optical density of this solution on the Beckman "B" Spectrophotometer at 550 mu using 20 mm cells and distilled water as the blank. If the turbidity exceeds the range of the chart, repeat the analysis using a smaller volume of vinyl chloride. CALCULATIONS The results are read directly from the chart to the nearest part per million. Duplicate determinations should check within 2 ppm. See chart on last page of procedure. CBY 10023^5 RSV0032048 METHOD 602.288 (WC) May 14, 1964 Page 3 of 5 PREPARATION OF REAGENT SOLUTIONS Prepare fresh solutions daily by adding 60 ml con centrated CP HC1 to 30 ml of distilled water m a 250 ml Erlenmeyer flask. Then dissolve in this 0.15 + 0.05 grams of alpha methyl indole, STANDARDIZATION AND/OR CALIBRATIONS Chill a 5 ml Mohr pipette graduated in 0.1 ml increments to a temperature of 0C by placing m an ice chest. Wrap pipette with a paper towel to avoid moisture contamination. After ten minutes, remove and pipette 5 ml of technical grade acetaldehyde. Introduce 1.25 ml of this chilled acetaldehyde into a 1000 ml chilled volumetric flask containing distilled water. Make up to volume with distilled water and shake thoroughly. The contents of this flask contains 1000 ppm acetaldehyde. Call this Solution A. 10 millileters of A diluted to 1 liter water = 10 ppm AcH 5 millileters of A diluted to 1 liter water = 5 ppm AcH 1 millileter of solution A diluted to 1 liter = 1 ppm AcH Intermediate parts are obtained by diluting various parts of A to 1 liter. These aliquot portions are then run in a similar manner to that of the sample and the various scale readings recorded. Duplicate determinations should be run for a check. These scale readings will relate to the concentration of the acetaldehyde present. SAFETY PRECAUTIONS When depressurizing the VCM in the Coca-cola bottle, be sure that the ice pick is removed slowly and the bottle is kept m a safety cage and wearer has on a face shield. CBY 1002346 RSV0032049 METHOD 602.288 (WC) May 14, 1964 Page 4 of 5 ANALYTICAL TIME 0.2 hour PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES FOR REPORTING Report to nearest 1 ppm; duplicate determinations should check each other 1 ppm at 1 ppm level. SCOPE Alpha methyl indole reacts with aldehydes to form a turbidity. A measure (spectrophotometer) of turbidity determines the amount of aldehydes present. RCR/mlw 5/14/64 CBV 1002347 RSV0032050 METHOD 602.288 (WC) May 14, 1964 Page 5 of 5 ACETALDEHYDE IN SPECIFICATION VCM 20 mm Cells Beckman "B" Spectrophotometer Optical Density 0 0.027 0.028 - 0.082 0.083 - 0.136 0.137 - 0.190 0.191 - 0.245 0.246 - O.299 0.300 - 0.354 0.355 - 0.409 0.410 - 0.463 0.464 - 0.518 0.519 - 0.572 ppm AcH 0 1 2 3 4 5 6 7 8 9 10 CBY 1002348 RSV0032051 MONSANTO COMPANY HYDROCARBONS & POLYMERS DIV TEXAS CITY, TEXAS MATERIAL Product Vinyl Chloride ANALYSIS REQUIRED Determination of Iron in Vinyl Chloride SAMPLE 100 ml glass pressure sample bomb APPARATUS Beckman Spectrophotometer Dry Ice Chest Two, 250 ml Erlenmeyer Flasks 100 ml Graduated Cylinder 10 ml Graduated Cylinder 100 ml Volumetric Flask DEPT. 22 METHOD 602.289-A Rev. 7/5/66 Page 1 of 4 (WC) REAGENTS -10% Aqueous solution of Hydroxylamine hydrochloride -2 molor solution of C.P. sodium acetate (164 0.01 g m 1 liter of distilled water) -0.1% solution of brom phenol blue (0.1 g dissolved m 100 ml of 50% ethyl alcohol) -0.12% aqueous solution of o-phenanthroline -Alcohol water solution (25 parts 2B alcohol and 30 parts water) -Concentrated C.F. HCl PROCEDURE Place 25 ml of the alcohol-water solution in a 250 ml erlen meyer flask. From the sample bomb, previously cooled for two hours in the dry ice chest, measure out 100 ml of vinyl chloride into a chilled graduated cylinder. Add the vinyl chloride to the 250 ml erlenmeyer flask and allow to evaporate. Then swirl the flask to remove the last trace of vinyl chloride. A vented hood is needed for the above evaporation. CBY 10023^9 RSV0032052 METHOD 602.289-A (WC) Rev. 7/5/66 Page 2 of 4 Procedure (cont'd) Quantitatively transfer the residue to a 100 ml volumetric flask. Acidify the solution in the volumetric flask by adding two drops of concentrated hydrochloric acid. Add two drops of brom phenol blue to the flask and then add the 2 molar sodium acetate solution dropwise until the solution turns a faint blue. Next, add four ml of 10% hydroxylamine hydrochloride solution, and then 10 ml of 0.12% o-phenathrclme. Dilute to the mark with distilled water; mix well, and allow the solution to stand for at least 20 minutes. With the Beckman spectrophotometer measure the light trans mission at 510 mu, with visible light. CALCULATIONS Refer to the attached graph and report the iron concentration to the nearest 0.05 ppm. PREPARATION OF REAGENTS 10% aqueous hydroxylamine HC1 in 900 ml of distilled water. Store in P.E. bottle. - dissolve 100 g of the salt Be sure water is iron free. 2 molar sodium acetate - dissolve 164 gms of C.P. salt in one liter of distilled water. Mix. Store in clean bottle. .1% solution of brom phenol blue - dissolve .1 gm of the in dicator in 50 ml of EtOH. Dilute to 100 ml with distilled water. .12% of o-phenanthroline - dissolve .12 gms of o-phenanthroline in 100 ml distilled water. Alcohol water solution - Mix 455 ml of 2B alcohol and distilled water up to one liter. 1000 ppm Fe Standard - dissolve .1000 gms of C.P. iron wire in 10 ml of 20% HCl (iron free). Cool and dilute to 100 ml with distilled water. Mix. Keep for stock reagent. 10 ppm Standard - dilute 1 ml of 1000 ppm standard to 100 ml with demineralized water. Mix. Keeps only one or two days. CBY 1002350 RSV0032053 METHOD 602.289-A (WC) Rev. 7/5/66 Page 3 of 4 STANDARDIZATION AND/OR CALIBRATION To five 100 ml volume flasks add 0, 3, 5, 7, 10 ppm standard. These correspond to 0, 30, of Fe. and 50, 10 ml of the 70 and 100 pgms Follow the procedure outlined above from paragraph three on. Determine absorbance in 20 mm cells against the zero standard above at 510 mp. Plot the absorbances so obtained against the corresponding pgms of Fe. Draw m the best average line. Use this as a working curve or calculate a factor f from it such that f x absorbance = pgms Fe. SAFETY Handle VCM with caution. Keep vapors away from sparks and flames. Guard against cold burns, handle with gloves. Use normal pre cautions with chemicals, glassware, and electrical apparatus. ANALYTICAL TIME 1/2 hour PRECISION OF RESULTS & SIGNIFICANT FIGURES TO REPORT 95% confidence limits are + .1 ppm at a level of 1 ppm or + 10% of the level found. Report results to nearest .05 pFm. SCOPE VCM sample is evaporated leaving any iron in a non-freezing mixture of water and alcohol. The iron is reduced to valence two and reacted with 1,10 phenanthrolme to a red product analytical to iron at 510 mp. These are known interferences. REFERENCES Plastics Division Control Lab. procedure 112-70-3. Texas City C.L. Method 22-18-10, G.L. 4/22/54. 7/19/66 JMD:ff CBY 1002351 RSV0032054 0 1o H METHOD 602.189-A (WC) Rev. 7/5/66 Page 4 of 4 IRON IN VCM CALIBRATION CURVE Wave Length: Cell Length: Standard: Blank 510 mu 20 mm (with reagents) ppm Fe 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Optical Density 0-0.05 0.05-0.09 0.090-0.112 0.112-0.150 0.150-0.19 0.19-0.23 0.23-0.27 0.27-0.31 0.31-0.34 0.34-0.40 CBY 1002352 RSV0032055 MONSANTO COMPANY HYDROCARBONS & POLYMERS DIV. TEXAS CITY, TEXAS DEPT. 22 METHOD 602.291 Rev. 7/5/66 Page 1 of 8 (WC) MATERIAL Product Vinyl Chlorde, 22D7-OH, Rundown Tanks and Shipments ANALYSIS REQUIRED Dilatometenc Polymerization Rate SAMPLE VCM Bombs or Thermos Each test requires about 8 ml sample. Material should be clear and colorless, free of suspended material. APPARATUS Glass Dilatometer (See diagram) Safety Cage (See diagram) Sealing Apparatus (see diagram) Weighing boat to fit dilatometer 2 - 10 cc Hypodermic syringes 2 - 10" to 12" - 18 gauge hypodermic needles 1/4" Fiberoid gasket inserts (Scientific Glass Blowing, Houston,Texas) 250 ml Erlenmeyer Flask Batter Jar 9" x 4-1/2" (Insulated) Constant Temperature Bath (Model 111-MS, Scientific Development Co., State College, Pa.) Differential Termometer - (Harshaw Scientific Co. #H62540 - Beckman 0-5C) Timer Precision - readable to 0.1 sec. Cooling Bath Support (Circular wooden disc 1" thick and 6" m diameter with a 1-1/2" hole in center) REAGENTS Benzoyl Peroxide - Lucidol Acetone, C.P. Grade Dry Ice Dimethyl Formamide - plant grade, duPont CBY 1002353 PROCEDURE 1. In a weighing boat on an analytical balance, weigh out O.lOOO^ 0.0001 grams of benzoyl peroxide. To a clean. RSV0032056 METHOD 602.291 (WC) Rev. 7/5/66 Page 2 of 8 Procedure (cont'd) dry dilatometer, add the peroxide by placing the lip of the weighing boat to the flanged portion of the dilatometer and gently tapping the boat. 2. Place the dilatometer in the cooling bath of acetone and dry ice cooled to -30.0C. 5C. Cool the dilatometer in the bath for 2 minutes before filling. 3. Draw off 50 cc of the VCM sample into a chilled erlenmeyer flask. 4. To a 10 ml hypodermic syringe (without plunger), add 8 cc of Monomer through the open end of syringe. Insert needle^ into the dilatometer so that the tip is approximately 1/4" from the bottom of dilatometer. Regulate the flow of VCM with thumb until the level of Monomer reaches a point be tween 3 and 4 cm. If the 4 cm mark is exceeded, clean the dilatometer and start over. No pre-chillmg of the hypodermic is necessary. 5. Place a teflon gasket on the dilatometer flange and screw the " T" handle down far enough to touch the gasket. Then, back off one full turn on the "T" handle. A new gasket is used for each test. 6. Immediately place the instrument m the safety cage so that the readings are visible through the plexiglass window. Secure the hatches and observe the dilatometer for signs of the first bubbling to begin. The first bubble should appear in the dilatometer approximately one minute and 30 seconds after removing the dilatometer from the cooling bath. At the first sign of a bubble, or 90 seconds after removing the dilatometer from the cooling bath, whichever occurs first, tighten the ''T" handle immediately. The dilatometer can now be considered purged of air and the cage is ready to place in the bath. 7. Place the cage m the bath immediately after the light, indicating the start of heating, goes on. If it is off or already on, wait until it has just come on. CAUTION: If temperature reads high (51C or over), do not put cage in bath. CBY 1002354 RSV0032057 METHOD 602.291 (WC) Rev. 7/5/66 Page 3 of 8 Procedure (cont'd) 8. Immediately start timer. Shake the dilatometer with a rocking motion by use of the "T" handle for 60 seconds. At the end of this 60 seconds, take the first reading. Repeat the shaking for 70 to 110 seconds. 9. Take a reading as accurately as possible every 60/5 seconds for the first 600 seconds. Record all readings on the data sheet provided. 10. Read the dilatometer every 60 seconds between 3600 and 4200 seconds from the time of placement in bath. 11. Remove the cage from the bath, place m hood and slowly vent by turning "T" handle, thus relieving pressure. CAUTION; Do not loosen hatches until venting is complete. 12. Immediately after the dilatometer has been vented, take it out of cage, remove the "T" head and flush several times with C.P. Acetone, using another 10 cc syringe. When no more polymer can be freed with acetone, a flush is made with DMF. The dilatometer is then filled with DMF and allowed to stand for at least two hours to loosen and dissolve any remaining polymer. 13. Before reuse, the dilatometer is again flushed 5 to 6 times with C.P. Acetone. The sealing surface of the "T" head must also be cleaned. The instrument is air dried with an aspirator or Lab bench air. 14. Inspect the cleaned dilatometer for polymer. If not polymer free, the entire cleaning process must be repeated. CALCULATIONS Polyrate Ah x F w + 3.66 206.9 x wt. of BZO2 w. I Definition of terms used in formula. Ah *s difference in height of dilatometer reading between 3900 sec. and 300 sec. F = --^pfl x 100 = where .456 .456 1 - ___1_ dPvc dVCM C BY 1002355 corrected conversion = observed conversion + C RSV0032058 METHOD 602.291 (WC) Rev. 7/5/66 Page 4 of 8 Calculations (cont'd) C = 2069 (0.0177,-R) R = wt. of BZO2 or 0.1000 gram w - weight of monomer at peak height (300 sec.) II. Derivation of formula L~------------7-------------7-7 + vm x Dm x .456 x cm/ml 206.9 [0.0177 | Vm x Dm Vm - volume monomer Dm = density monomer w = VD, weight - volume x density Ah x 100 + 206.9 w x .4 56 x cm/ml 0177 . n,. Bzo2 wt. Ah x ml/cm x 100 .456____________ + 3.66 w F = ml/cm x 100 .456 206.9 x wt. BzO? wt. / Ah x w + 3.66 206,9 x wt. of BzCS w CBY 1002356 RSV0032059 METHOD 602.291 (WC) Rev. 7/5/66 Page 5 of 8 DATA SHEET - DILATOMETER RESULTS Sample New Standard________________ Date 9-17-59 Dilatometer No. ______5 Wt. F= 12.36gr polymer/cm. Benzoyl Peroxide______0.1000 gr. (1.9 cm VCM) (--30.0C) NOTE; Check for Calibration Chart Before Using Dilatometer First Ten Minutes Timer Rdg. Seconds Dil. Rdg, Cm. Last Ten Minutes Timer Rdg. Seconds Dil. Rdg. Cm. 60 120 180 240 300 360 420 480 540 600 7.80 9.20 9.38 9.40 9.40 9.39 9.37 9.34 3660 3720 3780 3840 3900 3960 4020 4080 4140 4200 7.45 7.37 7.31 7.29 7.10 7.07 7.02 6.98 (1) W = wt. of monomer 6.079 gr. From calibration chart at dilatometer reading for 300 seconds. (2) Ah = 9.42 (Dll. Rdg. @ 300 secs.) 7.22 (Dil. Rdg. - 2.20 cm. 3900 secs.) r2.20 12.36~i 1STx (F) .1000 206.9 x (3) Polyrate= + 3.66 - (wt. BZO2) = %/Hr. 6.079 6.079 W (W) Polyrate = 4.47 = 3.66 - 3.40 = 4.73 %/Hr. Analyst CBY 1002357 RSV0032060 METHOD 602.291 (WC) Rev. 7/5/66 Page 6 o f 8 DILATOMETER NO. CALIBRATION CHART 5 F = 12 .36 Height Cm 0 .1 15 6349 14 6300 6305 13 6252 6257 12 6204 6208 11 6155 6160 10 6107 6112 9 6059 6064 8 6011 6015 7 5962 5967 6 5914 5919 5 .2 6310 6261 6213 6165 6117 6069 6020 5972 5924 .3 6315 6266 6218 6170 6122 6073 6025 5977 5929 .4 6319 6271 6223 6175 6126 6078 6030 5982 5934 .5 6324 6276 6228 6179 6131 6083 6035 5987 5938 5890 .6 6329 6281 6233 6184 6136 6088 6040 5991 5943 5895 .7 6334 6286 6237 6189 6141 6092 6044 5996 5948 5900 .8 6339 6290 6242 6194 6146 6098 6049 6001 5953 5905 .9 6343 6295 6247 6199 6151 6102 6054 6006 5958 5909 Prepared by_ Date Analyst CBY 1002358 RSV0032061 METHOD 602.291 (WC) Rev. 7/5/66 Page 7 of 8 PREPARATION OF REAGENT SOLUTIONS None STANDARDIZATION AND/OR CALIBRATION See attached Addendum to Method 602.291. ANALYTICAL TIME 2,0 hours PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES FOR REPORTING 95% confidence limits = 0.4% Report to nearest 0.01% SCOPE This procedure provides a quantitative method for determining the polymerization rate of Vinyl Chloride Monomer by accu rately measuring the dilation of the Monomer due to polymeri zation under rigid test conditions. The dilation is converted to per cent polymer produced. SAFETY PRECAUTIONS 1. Filling the dilatometer with VCM must be done in the hood. 2. Do not seal dilatometer after filling until it has been locked in the cage. 3. Never use a bath that exceeds 51C temperature. 4. Do not unseal dialtometer head to relieve pressure unless it is locked in cage, in the hood, and the analyst is wearing proper protective equipment. 5. Vinyl Chloride Monomer is highly flammable. Keep away from all sources of heat or sparks. TECHNIQUE NOTES 1. A leakage test should be performed on each dilatometer once per week. The method is as follows: CBY L002359 RSV0032062 METHOD 602.291 (WC) Rev. 7/5/66 Page 8 of 8 Technique Notes (cont *d) a. Fill the dilatometer as per procedure eliminating the catalyst. b. Readings are taken according to procedure. c. If the Monomer level drops more than 0.05 cm during the hour, the dilatometer is unacceptable. The flange should be inspected for defects and, if possible, any defects eliminated. 2. The flushing of the dilatometer with acetone should be done immediately after venting to prevent polymer from solidi fying on walls of dilatometer and making the cleaning operation more difficult. 3. The fibroid packing in the sealing head should be examined before-each run. If the packing has been compressed to a point where the glass flange might be hitting the shoulder of the sealing head, replace the packing. REFERENCE Method 22-18-9A JMDjff 7/19/66 CBY 1002360 RSV0032063 DEPT. 22 ADDENDUM METHOD 602.291 (WC) ADDENDUM (REVISED) ) 5/27/67 DILATOMETER CALIBRATION Page 1 of 7 Each dialtometer is first checked to see if it meets the volume specifications; if it doesn't, it will be rejected. This is done byweighing (Note No.1) the volume of mercury (Note No.2) it holds when filled to the 3 cm, 7 cm & 15 cm levels. This weight of mercury is converted to milliliters by dividing by the density of mercury at room temperature. If these volumes m milliliters meet the specifi cations, the calibration can then proceed. The milliliters that the dilatometer will hold when filled to the 7 cm level is then subtracted from the milliliters it will hold when filled to the 15 cm level. This volume is the ml volume the dilatometer contains between the 7 cm and 15 cm levels. This volume is then divided by (15 cm-7 cm) 8 cm to determine the ml/cm for the region between 7 & 15 cm. The chart is prepared by multiplying the volume the dilatometer will hold when filled to the 7 cm mark by the density of VCM (.855). This figure represents the wt. of VCM the dilatometer holds when filled to 7 cm. This figure is placed on the chart at 7.0 cm. The ml/cm pre viously calculated is also then multiplied by .855 to give gm VCM/cm. This figure added to gms VCM at 7.0 cm gives the value for 8 cm, then added again gives the wt. at 9.0 cm, etc. The .1 cm increments across the chart are filled m by adding 1/10 of the gm/cm value across the chart at each increment. The "F" factor for the chart is obtained by dividing the ml/cm value by .456 and multiplying by 100. .456 x ioo = ' F" EXAMPLES 1. Checking volume specs when filled to 3 cm level (spec = 6.2 .2) a. Weigh dilatometer + holder b. Fill to 3 cm mark with mercury and re-weigh c. Wt. filled - wt. empty - wt. contained to 3 cm level d. Wt. contained divided by density of mercury (13.5217) = volume contained e. Volume contained should be 6.2 + 0.2 ) CBY 1002361 RSV0032064 ADDENDUM (REVISED) METHOD 602.291 (WC) 5/27/67 Page 2 of 7 Examples (cont'd) 2. Checking volume spec, between 3 cm and 7 cm level (spec = ,8 + .1) f. Add more mercury to the 7 cm level and re-weigh g. Wt. @7 cm - wt. @3 cm - Wt. contained between 3 cm & 7 cm h. Wt. between 3 cm and 7 cm divided by 13.5217 = Volume between 3 cm and 7 cm i. Volume between 3 cm and 7 cm should be .8 + .1 3. Checking volume spec, between 7 cm and 16 cm (spec = .0530-.0620 ml/cm) j. Add more mercury to the 15 cm level and re-weigh k. Wt. @ 15 cm - Wt. @7 cm = Wt. contained between 7 cm & 15 cm. l. Wt. between 7 cm & 15 cm divided by density (13.5217) = Volume between 7 cm & 15 cm. m. Volume between 7 cm & 15 cm divided by 8 cm (15-17) = ml/cm between 7 & 15 cm. n. ml/cm between 7 cm & 15 cm should be between .0530 & .0620 ml/cm ) 4. Calculating Calibration Chart o. Volume contained @3 cm (e) + volume contained between 3 cm and 7 cm (i) = total volume when filled to 7 cm level. p. Total volume @ 7 cm multiplied by density of VCM (.855) = Wt. VCM when filled to 7 cm level. q. Place wt. of VCM @ 7 cm on chart @ 7.0 cm. r. ml/cm between 7 cm & 15 cm (n) x density of VCM(.855) = Wt. VCM/cm s. Wt. @7 cm (q) + Wt. VCM/cm (r) = Wt. @8.0 cm t. Wt. @8.0 cm + Wt. VCM/cm = 9.0 cm, etc., up to Wt. @ 15 cm Wt. i 7.0 cm - Wt. VCM/cm = 6.0 cm wt. u. Wt. VCM/cm between 7 cm & 15 cm (r) divided by 10 = Wt. VCM/.lcm v. Add wt. VCM/.1 cm to chart across at each cm level. 5. Calculating " F" Factor w. Divide the ml/cm (n) by .456 and multiply by 100 ------^--------- x 100 = " F' .456 Note 1: Make all weighings on the same balance to the nearest 0001 gm. Note 2: Fill the dilatometer with a 10 ml syringe/12" #18 needle. ) cBY L002362 RSV0032065 Height Cm DIIATOMETER MO. CALIBRATION CHART & WORKSHEET F = ________________________ Prepared by Date 0 .1 .2 .3 .4 .5 .6 .7 .8 .9 15 14 13 12 11 10 _9 _8 7___________________________ 6 A. Total Wt. @ 3.0 cm (Permissive Ranqe (6.2 + .2) Wt. Dil. + Holder Wt- Hq @ 3 cm ~ 13-5217= ml @ 3 cm R. Total Wt 7.0 cm Total Wt.@ 3.0 Permitted Ranqe -8 .1 Wt Ho 3 to 7 cm 4 13.5217 ml 3 to 7cm C. Total wt.@15 cm Total wt. 7 on Permitted Ranqe 2.7 + .1 ml Wt Hq 7 to 15 cm 4-13.5217 = ml@7-15 ml @ 3-0 cin + ml 3--7 = ml @ 7 Enter Above x .855 = gms @7.0 ml 7.0-15.0 f8 = ml/cm Add up from 7.0 ml/cm t10 = across from 7.0, 8.0, etc. ml/1/10 cm Add (ml/cm) .456 x 100 - F Enter Above CBY 1002363 ADDENDUM ( 6 0 2 .2 9 1 ) -Eags J q. 7 RSV0032066 ADDENDUM METHOD 602.291(WC) Rev. S/21/SI Page 4 of 7 FITTING TUBE TO HOLDER COLLAR AND CHECKING FOR LEAKS Insert top flanged portion of the dilatometer through the unthreaded portion of the collar (metal). Place a fiberoid semicircle 1/4" gas ket into the upper threaded portion of the collar such that when in serted it will make a complete circle around glass stem. Push this circular conical shape gasket down to the unthreaded portion bypushing on all sides with the pointed end of a coopla (spatula). With one hand on the collar, and other hand on dilatometer neck, slowly twist and turn until top of flange will go no further and all portions of screw threads are visible through top of dilatometer. The readings on the stem should be m line with the small extensions on the collar, otherwise, when it is put in cage, the readings will not be visible to the clear side of cage (important) at this point the Fiberoid gasket should be firmly imbedded into the collar and ready to check for expansion. Onto the top edge of battery jar, 9" high by 4-1/2" wide, covered with 1 inch insulation, place a circular wood disk 1" thick and 6" m diameter and containing a 1-1/2" hole in midcenter. Through this opening, insert dilatometer so that collar rests on wood disk and readings on the dilatometer stem are visible through the 2-1/2" unin sulated portion. Fill the jar with acetone to a level so expansion bulb and reservoir are covered with the liquid. Add dry ice to ob tain a temperature of -30C (check with a -100 +50C toluol thermo meter.) Allow dilatometer to maintain this temperature for at least 2 minutes. It is now ready for filling with monomer. Drain or pour 50 ml of good grade VCM (85% PR) into a chilled erlenmeyer flask. When the base of dilatometer is down to the -3 0C reading, take a 10 ml hypodermic syringe, insert needle and add about 8 ml of VCM through the open end of syringe (no chilling of the syringe is necessary and the plunger is not used). Insert the needle into the dilatometer until it is about 1/4" from bottom of the reservoir. Regulate the boiling of the VCM by use of the thumb until an even flow is obtained through the needle. Fill the dilatometer to a level of about 3 cm. Remove from the dry ice bath, shake gently to remove any air bubbles (VCM will contract slightly^,. Immediately place teflon circular gasket on flange and screw the tee handle down but not enough to seal the instrument. Place instrument in safety cage so readings are clearly visible m plexiglass section of cage. Secure the latches and seal dilatometer by tightening the "T" head. CBY 1002364 RSV0032067 ADDENDUM METHOD 602.291(WC) Rev. 5/27/67 Page 5 of 7 The sealed instrument m the cage is now ready to insert into the bath at 50C + 0.05C. The following procedure should be followed: Do not put the instrument into the bath until the heat indicator light has just come on, also, do not place the instrument in the bath just because the light happens to be on when you are ready for insertion m the bath. Wait until you are sure the light has come on. Place the dilatometer in bath, start the timer, when the level reaches the upper tube, shake dilatometer by means of a rocking action by use of the "T" handle until 60 seconds has lapsed. Now record the reading and note the highest point the monomer reaches. This high point should not take more than 5 minutes to reach if there are no leaks. Record this maximum value which should be between 7 to 10 cm. If the maximum occurs after 5 minutes, the circulation rate of the water should be increased. Read the dilatometer every 10 minutes for 30 minutes. mum reading should be maintained. A drop indicates a sealing surface of the neck. The maxi flaw in the IMPORTANT - Cleaning of dilatometer. Polymer should be removed immediately after analysis by means of a hypodermic syringe and needle. C.P. Acetone is added to dila tometer, shaken and flushed several times and removed, then pro cess repeated with dimethylformamide. Allow to soak for about two hours in dimethylformamide. Remove, flush several times with C.P. Acetone and blow dry with air. The dilatometer is now ready for use. CBY 1002365 RSV0032068 SPECIFICATIONS: fl, 150 pslg pressure rating. B. 0.698" m 0.002" outside diameter at top. C. 6.2 ml. + 0.2 ml. volume at 3 cm. mark. D. 0.8 ml. +0.1 ml. volume between cm. and 7 cm. marks. E. 2.7 mm. + 0.1 mm. bore. Diameter from 0 to 3 cm. and from 7 to 15 cm. marks. ADDENDUM Method 602.291 (WC) Page 6 of 7 Standard Glass Pipe Flange (75 Taper) i! m NT /r t+ - Reservoir to Hold About 1 ml. :U VJ Oo : n : )e s1 ^-Graduations In centimeters with millimeter markings TWi *4 fMwd ik*r*n >1 Hm ptammif MetM>te OwmImI C*mat Ml it Ittttd wU iW tttftntd ttrtmitl thM l vM *M U n***dK(d, t#<>d tr tfttrwlw dliptwd *f. ArwcHy ar Indirectly, kid vill mH be Mied. I* wfcet* *r m *rt. t* IwriUtir *ny ind*rtwetin |* tfee ** m*fWm *f b ef y ^kmi wllhiiit enim nmieiM al M*ttit CttMidi Ctweewy lint ebtelned td tpwctllc n ** eweH ae TIm KCM^ttc* mt bn dftrln wilt be nmmwd w * etttebKk el tbe HbfiM. Monsanto Chemical Company PtASTICS DIVISION texas crry, Texas Control Lab mt VCM Polyrate *' TR M DILAT0METER: GLASS Prod. Technical Service Dept. unT APf im *pp* MTt HUK MM CML JBG p?9~ JRA 8^59 KTUU CIK. im TES 11-59 m Method 22-ii3-9A *uu Full Size w. U-Flg, 2 - Rev U-59 This Reservoir to be Located Between 4 cm, and 6 cm, marks ^--Etched Spot for Pencil Markings CSV 1002366 RSV0032069 t2S& 1 ISSS *tAi -a AS& sacs/ 7 a Are% SiAA C. Sl/>rPPT i irjuturas aWreMct Q/f-- i SOU i ikiilAUH c.i /&r -ny SAM, ...J RSV0032070 ADDENDUM METHOD 6 0 2 .2 9 1 (WC) Page 7 o f 7 \ MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY/ TEXAS DEPT. 22 METHOD 602.294 May 1, 1964 Page I of 2 (WC) MATERIAL Product vinyl chloride monomer ANALYSIS REQUIRED High boiling liquid impurities SAMPLE SIZE 100 ml APPARATUS Analytical balance 125 ml Erlenmeyer flask 100 ml graduated cylinder Dry ice chest Vacuum source REAGENTS None PROCEDURE Tare, to the nearest milligram, a clean, dry 125 ml Erlenmeyer flask. Place a 100 ml graduated cylinder the dry ice chest for a minimum of 15 minutes. in Pour 100 ml of vinyl chloride into the chilled graduated cylinder. Quickly transfer the sample to the 125 ml Erlen meyer flask. Allow the vinyl chloride to evaporate from the flask at room temperature. This must be done m the hood. After the last of the vinyl chloride has evaporated, allow the flask and residue to come to room temperature. Vacuum excess vapors. CBY 1002366 RSV0032071 METHOD 602.294 (WC) May 1, 1964 Page 2 of 2 Dry the outside of the flask carefully with a lint-free cloth. Then weigh the flask, and the residue contained in it to the nearest milligram, CALCULATIONS (wt. m g. of flask and residue) - (wt. 0.969 in g. of clean dry flask) = % high boilers PREPARATION OF REAGENT SOLUTIONS None STANDARDIZATION OR CALIBRATION None SAFETY PRECAUTIONS Observe general laboratory safety practices. Use normal precautions with chemicals, glassware. ANALYTICAL TIME 0.2 hours PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES FOR REPORTING RESULTS Report to nearest 0.05%. Duplicate samples should check within 0.05% of each other. SCOPE Vinyl chloride monomer weathers off and leaves high boiling impurities as residue which is weighed. NOTE Any phenol present will appear as high boilers and should be corrected for. RCR/mlw 5/1/64 CBy 1002.369 RSV0032072 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.297 May 26, 1964 Page 1 of 3 (WC) MATERIAL Product vinyl chloride ANALYSIS REQUIRED Determination of peroxides SAMPLE SIZE Quart thermos bottle APPARATUS Dry ice chest 100 ml graduated cylinder 250 ml Erlenmeyer flask Three 100 ml volumetric flask 25 ml graduated cylinder REAGENTS 5% ferrous sulfate solution prepared as follows: 10 0.01% Ammonium thiocyanate solution Ethyl alcohol 0.01 N sodium hydroxide solution 0.10% phenolphthalein solution CBV 1002370 RSV0032073 ) METHOD 602.297 (WC) May 26, 1964 Page 2 of 3 PROCEDURE Add 25 ml of 2B alcohol to a 250 ml Erlenmeyer flask, stopper and chill the contents in the dry ice chest for at least 15 minutes. At the same time chill a dry, stoppered 100 ml graduated cylinder. Measure into the chilled graduated cylinder 100 ml of vinyl chloride from the sample thermos jug, then transfer quickly to the chilled 250 ml flask containing the 2B alcohol. Allow the vinyl chloride to evaporate slowly at room temperature m the vented hood. After boiling has ceased, warm the flask slightly with the hands to effect complete evolution of vinyl chloride. Transfer the alcohol solution to a 100 ml volumetric flask. Rinse the Erlenmeyer flask with two 20 ml (approx.) portions of distilled water, and add rinsings to the volumetric flask. Add 3-4 drops of ferrous sulfate solution, and then 3-4 drops of the ammonium thiocyanate solution to the volumetric flask. Mix by swirling and then make up to 100 ml with distilled water and mix again. Note; A blank must be run simultaneously with the above analysis for comparison with the sample. It should be colorless. If the blank is not colorless, the sample must be discarded and a new one prepared with fresh reagents. Compare the color of the prepared sample to that of a solution prepared as follows: Add to a 100 ml volumetric flask 0.50 ml of 0.01 N sodium hydroxide and 0.10 ml of 0.10% phenolphthalein. Dilute to 100 ml with distilled water and shake. CALCULATIONS CBY 1002371 Report peroxides as positive or negative on the following basis ; If unknown is greater m color than standard, peroxides are positive. RSV0032074 METHOD 602.297 (WC) May 26, 1964 Page 3 of 3 If unknown is of color equal to, or less than the standard, peroxides are negative. PREPARATION OF REAGENT SOLUTIONS See Solutions Manual STANDARDIZATION AND/OR CALIBRATIONS None SAFETY PRECAUTIONS Vent sample m well ventilated hood. Handle sulphuric acid and caustic with care - avoid skin contact, wash from skin with water. ANALYTICAL TIME 0.2 hour PRECISION AND SIGNIFICANT FIGURES Not applicable SCOPE Peroxides in presence of caustic form a pink color. RCR/mlw 5/26/64 CBY 1002372 RSV0032075 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.298 May 25, 1964 Page 1 of 4 (WC) MATERIAL Product Vinyl Chloride ANALYSIS REQUIRED Polymerization Rate Test SAMPLE SIZE 40 ml (free of phenol) APPARATUS Coca-Cola soda water bottle (selected for freedom from scratches and chips) Bottle capper Crown bottle caps - cork lined Torsion balance - accurate to - 0.1 gram 100 ml graduated cylinder Analytical balance accurate to t 0.001 grams Ice water bath Hot water bath Dry ice chest Ice pick Water bath for tumbling bottles end over end at 50C + 0.5C - (Rate of 30-60 RPM recommended), Face shield Heavy leather gloves 1002373 Cylindrical metal cages RSV0032076 METHOD 602-298 (WC) May 25, 1964 Page 2 of 4 . REAGENTS Benzoyl peroxide Gelatin (Eastman Purified Calfskin Gelatin) Prepare a solution of 2.5 grams of gelatin in one liter of water. (This solution may be stored for a minimum of one week.) PROCEDURE Weigh 0.750 grams ilO.OQl grams of benzoyl peroxide and transfer to a clean dry coca-cola soda water bottle. Add 60 ml of the 0.25% gelatin solution to the bottle. Cool the bottle and contents in ice water for a minimum of ten minutes. Dry the outside of the bottle and weigh the bottle and bottle cap to 1 0.1 gram. Add vinyl chloride to the bottle from the sample bomb, previously cooled for two hours, until a slight excess over 30 grams has been added. Allow the excess over 30 grams to evaporate and cap the bottle. Recheck weight after capping. Weight of vinyl chloride should be 30.0 grams lo.3 gram. All work involving weighing and evaporation of vinyl chloride shall be done in the vented hood, and bottles secured in protective cages when not handling. Caution; The capping procedure and all handling of the sealed bottle thereafter shall be carried out while wearing a full face shield and leather gloves. Allow the bottle to warm to room temperature in the pro tective metal cages. Remove, place the bottle in the rack provided in the water bath and allow to tumble for 7 hours t 3 minutes at 50C + 0.5C. (Correct temperature control is very important.) - Make certain clamps holding rotating bottles are secure and in good working condition. CBY 1002374 RSV0032077 METHOD 602.298 (WC) May 25, 1964 Page 3 of 4 Remove the bottles from the bath, place in metal pro tective cages, place m a pail of water slightly above room temperature. Allow cool water to flow on bottles which lowers temperature gradually, then add ice and after ten minutes in ice water, place on its side m the dry ice chest. Be sure that the top of the bottle is slightly elevated to prevent plugging of the neck with ice. When the contents of the bottle are frozen, remove from chest, puncture the cap with an ice pick, and allow the bottle to warm to room temperature. Place bottle m the side rack holders of polymerization bath with small beakers over punctured hole (to prevent water from splashing into holes). Let stand m 50^0 bath for one hour. Dry the outside of the bottle and weight the bottle and contents. Note: Destroy coca-cola bottle at completion of test. CALCULATIONS % conversion = (Weight of bottle and polyvinyl chloride after test - weight of bottle and contents before adding vinyl chloride + 30) X 100 s- Sample weight PREPARATION OF REAGENT SOLUTIONS See Solutions Manual STANDARDIZATION AND CALIBRATION In order to standardize a sample of VCM of known content, it should be run routinely. SAFETY PRECAUTIONS Thermal shock of glass equipment should be emphasized. When VCM has been polymerized and removed from bath at temperature of 50C, it should be gradually cooled before placing in dry ice box, otherwise bottles will break, inflicting cuts. CBY 1002375 RSV0032078 METHOD 602.298 (WC) May 25, 1964 Page 4 of 4 Bottles should be put into polyrate b th cautiously in secure clamps. Slipping bottles could jam the rotary shaft and also cause bottles to break - tare shield should be worm when placing bottles m cr removing from bath. Unattended bottles should always be placed in protective metal cages. ANALYTICAL TIME Total elapsed time approximately 12 hours. PRECISION AND SIGNIFICANT FIGURES 95% confidence limits are it 3% at 85% level. Report to nearest whole number. SCOPE VCM monomer is converted into the VCM polymer by addition of benzoyl peroxide, gelative and controlled temperature changes. The amount of polymer formed is then weighed to determine polymerization rate. RCR/mlw 5/25/64 C.BY 1002376 RSV0032079 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.299 May 28, 1964 Page 1 of 3 (WC) MATERIAL Product vinyl chloride monomer ANALYSIS REQUIRED Phenol SAMPLE SIZE Quart thermos jug APPARATUS 250 ml Erlenmeyer flask 50 ml beaker 2 ml pipette 100 ml graduate Beckman Model "B" Spectrophotometer 50 mm absorption cells (matched pair) REAGENTS Millons reagent Prepare in well ventilated hood. PROCEDURE Evaporate 100 mis of sample m a 250 ml Erlenmeyer flask. When sample is completely evaporated, add 25 ml distilled H^O. Pipette 2 ml of Millons Reagent into flask. Boil for 1 minute on hot plate. Prepare a blank in the same manner, omit the sample. When solution has cooled, filter and read sample against blank on Beckman Model "B". Use 59 mm cells, sensitivity of 3, and wavelength of 440 mu. CBY 100237? RSV0032080 METHOD 602.299 (WC) May 28, 1964 Page 2 of 3 CALCULATIONS Multiply O.D. by 10 to obtain ppm phenol. to nearest 0.1 ppm. Report Note: Use of sensitivity of 3 is not normal for our procedures. Use setting of 3 to adjust instrument on blank. This will allow the use of much smaller slit and will give some improvement m reproducibility of results. PREPARATION OF REAGENT SOLUTIONS To 100 grams of fuming nitric acid, add 100 grams of mercury. Allow sufficient time for mercury to react and go completly in solution. Add 20 mis of distilled H^O while stirring mixture. Place in a glass stoppered container. STANDARDIZATION AND/OR CALIBRATIONS See Solutions Manual. SAFETY PRECAUTIONS Handle mercury with care, avoid breathing vapors and dust spilled mercury with sulfur. Mercury reacts vigorously with nitric acid liberating large quantities of toxic NO^ Perform the preparation of this reagent in the hood with good ventilation. ANALYTICAL TIME .2 hour CBY 1002378 METHOD 602.299 (WC) May 28, 1964 Page 3 of 3 PRECISION AND SIGNIFICANT FIGURES 95% confidence limit - 1 ppm at 5 ppm level. Report to nearest 1 ppm level. SCOPE Mercuric nitrate reacts with the phenol in the sample to produce a color complex. RCR/mlw 5/28/64 CBY 1002379 RSV0032082 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.301 Rev. 8/13/64 Page 1 of 4 (WC) MATERIAL Product VCM, 22D140H, Rundowns & Tank Cars ANALYSIS REQUIRED Water SAMPLE Glass Bomb APPARATUS 50 ml scrubbing cylinder w/fritted glass dip tube. Drying tube with drierite 25 ml pipette "Karl Fischer" titration apparatus Concentric ring union half to fit glass sample bomb and with 1/4" SS tubing. fitted REAGENTS Dry Methanol Karl Fischer reagent standardized Water in MeOH standardized PROCEDURE Preparation of sample bomb. - Vent any previous sample. Pump down to limit of mechanical vacuum pump. Transfer the bomb to a high vacuum system and pump down to 10-20 microns. Close off bomb to leave vacuum in it. (Do not use water aspirator vacuum for this work.) . ANALYSIS 1. Werigh bomb and sample to nearest 0.1 gm. Measure 25 ml of dry MeOH into the scrubber cylinder and cap. cey 1002380 RSV0032083 METHOD 602.301 {WC) Rev. 8/13/64 Page 2 of 4 2. Attach the adapter to the sample bomb and connect by rubber tubing to the fritted glass bubbler of the scrubbing bottle. 3. Insert the sample bomb so that liquid VCM may be withdrawn. Slowly open the valve on the bomb to allow VCM to bubble through the MeOH. 4. When sufficient liquid VCM has passed from the bomb.. {The sample weight should be greater than 10 gm. If it is less than this amount, discard the results and call for a resample.) 5. Remove tubing from the adapter and clamp shut. Warm to room temperature by setting the graduate in warm water. {Do all of this work to this point in a hood or well ventilated area) 6. Quickly determine the water in the 25 ml of MeOH used in a scrubber and in 25 ml of MeOH of the dry MeOH used by Method 602.204 (WC). CALCULATIONS >- [(Vsa - Vbl> fcf Fkf * % h2o= - V5a> sw FJ * 100 Sample Wt. If the same volume of Karl Fischer Reagent is used for both sample and MeOH blank, the above equation reduces to - n/ ,, {V_ - V ) F x 100 % H^O = blsa sw sw Sample Weight PREPARATION OF REAGENTS See method 602.204 (WC) STANDARDIZATION AND/OR CALIBRATION See method 602.204 (WC) CBY 1002381 RSV0032084 METHOD 602.301 (WC) * Rev. 8/13/64 Page 3 of 4 SAFETY The glass bomb containing the sample is pressure tested; however, it should not be subjected to sudden changes in temperature, and should be handled as carefully as possible. Do not remove the plastic shield. Check the sample as soon as it arrives to ascertain that there is an inch or so of vapour space above the liquid. VCM is volatile and flammable and an anaesthetic with toxic effects so that all venting operations should be done in a good hood away from fires. VCM has ignited from static and it was suspected that nylon clothing was the cause of the static. Such clothing should be avoided and the person running the test should ground themselves by touching a water faucet prior to handling material in the presence of VCM vapors. Use normal precautions in handling chemicals, glassware and electrical equipment. ANALYTICAL TIME 30 minutes PRECISION OF RESULTS AND SIGNIFICANT FIGURES 95% confidence limits are + 30 ppm at a level of 100 ppm. Report results to nearest 10 ppm. SCOPE This procedure is suitable for VCM products and similar light materials which contain no material that will interfere with Karl Fischer titration. REFERENCES Research Method TC - 2145 (Titr). 1-15-63 E.G. GK:ff 8/13/64 CBy 1002382 RSV0032085 METHOD 602.301 (WC) 8/13/64 Page 4 of 4 t>fty iO<| Tube CBY 1O0Z383 RSV0032086 22 -602 .302 4 MONSANTO CHEMICAL COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS METHOD 602.302 (W. C. ) April 25, 1963 Page 1 of 3 MATERIAL 22D15 Bottoms, 22D16 Bottoms, 22D15 Inlet Cooling Tower Water, VCM plant out fall water. ANALYSIS REQUIRED Total carbonyls as acetaldehyde SAMPLE 1 pt bottle APPARATUS pH Meter Glass electrode Calomel electrode Mag mix & mag bar 250 & 400 ml beakers 100 ml graduated cylinders 10, 25 ml pipettes 10 ml micro burette .01 ml subdivision with fine tip. REAGENTS .05N Sodium hydroxide solution (Standard) .5N hydroxylamine hydrochloride soln. .IN Sodium hydroxide solution approximate .IN HC1 solution approximate PROCEDURE Be sure that all equipment is clean dry and free from acetone. 1. Place 100 ml of hydroxyl amine hydrochloride solution into a 250 ml beaker. Adjust the pH to 3-8 with .IN NaOH. 2. To a 400 ml beaker add 15 ml of 22D15 or Dl6 Botts. Add 85 ml of distilled water. Adjust the pH to 3.8 with .IN caustic or acid. For D15 inlet and cooling tower water add 100 ml of sample and adjust the pH to 3.8. 3. Add the pH 3.8 hydroxyl amine HC1 solution to the sample beaker. Stir the mixture five minutes. 4. Titrate with .05N NaOH to a pH of 3.8. Record the volume, V used, and the exact normality N. CBY 100238A RSV0032087 METHOD 602.302 (W.E.) April 25, 1963 Page 2 of 3 5- Repeat this procedure using distilled water pH of 3.8. Allow the Plank to oximate 5 minutes then record the volume Vb and the normality Nacid or N necessary to bring the pH back to 3-8. base CALCULATIONS fV x Nacj_,j[ (V X N) Se amp,let V x N.ba_ se Sample weight blank blank x 44000 PPM ACH Dichromates are usually present in the water but do not interfere. PREPARATION OF REAGENTS See Reagents Manual STANDARDIZATION AND/OR CALIBRATIONS See Reagents Manual SAFETY Use normal precautions in handling glassware, chemicals, and electrical equipment. TIME 15 minutes PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES 95% confidence is - 20 PPM @ 100 PPM level. Report results to the nearest 10 PPM. SCOPE Aldehydes and ketones react with hydroxyl - amine HCL to form the ox like :C=0 + K2N0H-HCL --^ :C=N0H + H20 + HCL The liberated hydrochloric acid is molarly equivalent to the aldehydes 8r Ketones) present. The pH must be carefully adjusted to prevent titration of acid or base present in the sample. CBY 1002385 RSV0032088 METHOD 602.302 (W.E. ) April 25, 1963 Page 3 of 3 Hydroxyl Amine HCL deteriates slowly on standing and should be made up fresh every two weeks. 3 NH20H'HCL N2 + NH4C1 + 3 H2O. 4 NH2OH-HCL_^ N20 + 2NH4CI + 3H20. REFERENCES Research Method 2146 2/4/63 R.L.M. JMD/kh 2-26-63 CBY 1002386 RSV0032089 MONSANTO CHEMICAL COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.303(W.C.) August 15, 1963 Page 1 of 3 MATERIAL 22D15 Botts 22D16 Botts ANALYSIS REQUIRED Acetylene SAMPLE 1 Pint bottle APPARATUS 500 ml Erlenmeyer flask 25 ml cylinder 100 ml cylinder 1 ml pipette REAGENTS 20$ Ag NO^ solution agueous 95$ ethyl alcohol .05 N NaOH standardized Methyl red-methylene blue mixed indicator PROCEDURE Cool sample in ice chest to prevent loss of C2H2. Measure 20 ml of 20$ silver nitrate and 80 ml of EtOH into a 500 ml Erlenmeyer flask. Add 1 ml of the mixed Indicator and titrate to a color change from purple to grayish green color with .05 N NaOH. Add by cylinder 100 ml of 22D16 Botts or 25 ml of 22D15 Botts to another 500 ml Erlenmeyer flask. Add 1 ml of the mixed indicator and titrate to the gray/green end print. CBY 100238? RSV0032090 DEPT. 22 METHOD 502.303 (W.C.) August 15, 1Sd3 Page 2 of 3 PROCEDURE (Continued) Add the adjusted Ag N0o solution to the sample. Swirl for 0 minutes. Titrate to^a gray green end print. The end print is obscured by the solids for high acetylene content samples. Add the NaOH in small increments and let solids settle to check the color. When titration is complete add 20 ml of cone HCl and wash solid down drain. Add an additional 20 ml of KC1 and swirl around the flask to remove the solids. Pour 'waste down drain and rinse with tap water before placing on the cast. CALCULATIONS (v-N)NaQH x 1.3 x 104 Sample Weight ppm C2K2 PREPARATION OF REAGENTS 20% Ag N0j> dissolve 200 gms Ag NO3 to 500 ml of distilled water. Methyl red/methylene blue mixed indicator - dissolve .25 gms of methyl red and .125 gms of methylene blue in 250 ml of iso propanol, Shake well to dissolve. ,05 N NaOH see solutions manual. STANDARDIZATION AND/OR CALIBRATION See reagents manual. SAFETY Add cone HCl to the flask containing the sample and the Ag NO3 to release the acetylene from the silver acetyides formed. Do not let any of these solids dry else they will detonate violently. Pour waste, after HCl addition, down water drain. Use normal precautions handling glassware and chemicals. PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES Sample must be cooled in ice water and opened only just prior to running to prevent loss of acetylenes and aldehydes. confidence limits are + 25 ppm at 100 ppm level. Report to nearest ppm. CBY 1002388 RSV0032091 DEPT. 22 METHOD 602.303 (W.C.) August 15, 193 Page 3 of 3 SCOPE The acetylene present reacts with silver nitrate to form silver acetylide and 2 mols of nitric acid. C2H2 + 2 Ag > Ag2C2 + 2 HNO3 The silver acetylide precipitates out tending to make the reaction go to completion. In alcohols the precipitate is finer. All acidity must be neutralized prior to the mixing of Ag NO v.ith cample, ^ REFERENCES TC 2108 modified ASTM D 1020-61 modified JMD/ps 5-16-63 CgY 1002389 RSV0032092 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.304 May 26, 1964 Page 1 of 3 (GC) MATERIAL Product vinyl chloride monomer ANALYSIS REQUIRED Styrene oxide and phenyl acetaldehyde APPARATUS Gas chromatograph Hydrogen flame ionization detector Recorder REAGENTS Aluminum tubing - 3/16" O.D. Helium Hydrogen - electrolytic grade Air - clean supply (cylinder) Aprizon L. Dupont teflon T6 30-60 mesh N Hexane - phillips high purity Microsyringe Pipettes - 5, 10 ml VCM sample bomb9 - brown glass, 100 ml capacity Graduate 100 ml Boiling chips qb y 100Z390 RSV0032093 METHOD 602.304 May 26, 1964 Page 2 of 3 (GC) PROCEDURE L1. Pack the column 10 feet long with 5% apnzon on 30-60 T6 teflon. 2. Install the column in the gas chromatograph and condition the cc luinn of 100C. 3. iJeigh the sample bomb to the nearest 0.1 g and record the weight. 4. Chill the 100 ml graduate m an ice bath and add a boiling chip. Remove from ice bath and set m hood. 5. Transfer the contents of the sample bomb to the chilled graduate m 20-25 ml portions allowing the VCM to weather off between portions. 6. After all the VCM has been weathered off, rinse the graduate with 5.0 ml of hexane. 7. Inject 1M1 of the hexane solution into the chromatograph and measure the SO and pH AcH peak heights. 8. Calculate the SO and pH AcH concentrations as follows: wt% SO = Peak height X Calibration factor (wt%/dw) X 4^5 wt of sample wt% pH AcH = Peak height X Calibration (wt%/dw) X 4_J5 wt of sample factor 9. If non-detectable - report as^_0.2 ppm SO. If non-detectable - report asZ.0.2 ppm pH ACH PREPARATION OF REAGENT SOLUTIONS None CBY 1002391 RSV0032094 METHOD 602.304 (GC) May 26, 1964 Page 3 of 3 STANDARDIZATION AND/OR CALIBRATIONS 1. Prepare standard solutions of SO and pH AcH in hexane. A concentration of 0.005-0.01 wt% is satisfactory. 2. Inject 1 /,'1 of each solution into the chromatograph and measure the peak heights of SO and pH AcH. 3. Calculate the wt% SO and wt% pH AcH per division since the densities of hexane and VCM are different, convert to the correct calibration factor by multiplying by 0.718. SAFETY PRECAUTIONS No special precautions need to be observed other than those normally observed when handling gaseous hydro carbon samples. ANALYTICAL TIME The average time of analysis using this method should be 0.2 hour. Precision is i 10% relative at concentrations of t 0.005 to t 0.100%. Report results to nearest 0.1 ppm. SCOPE Styrene oxide (SO) and phenyl acetaldehyde (pH AcH) may be determined by a gas chromatographic method employing a single column arrangement. A sample is injected into a column of aprizon on T6 teflon and the SO and pH AcH measured by its peak height at the proper retention time. Since SO and pH AcH are both high boiling impurities, a vapor sample is not satisfactory. The sample is analyzed by injecting into the chromatograph the liquid residue after weathering off the VCM. RCR/mlw 5/26/64 CBY 1002392 RSV0032095 MONSANTO COMPANY HYDROCARBONS & POLYMERS DXV TEXAS CITY, TEXAS DEPT. 22 METHOD 602.308 (WC) January 17, 1967 Page 1 of 2 MATERIAL 22D6 Botts ANALYSIS REQUIRED ppm HC1 SAMPLE SIZE 1 pint bottle APPARATUS pH meter 50 ml burrette 1000 ml separatory funnel REAGENTS .1 N NaOH, standardized Distilled water PROCEDURE Add 250 ml of sample and 250 ml of distilled water to a 1000 ml separatory funnel. Shake vigorously with frequent venting for one minute. Let the phases separate. Discard the lower layer, drain top layer to a 400 ml beaker, add stirring bar and place on stirrer. Add electrodes. Titrate with .1 N NaOH to a pH of 7.0 CALCULATIONS V X N x 118 PREPARATION OF REAGENTS .1 N NaOH - dissolve 4.0 gms of NaOH m one liter of distilled water. Mix. CBY 1002393 RSV0032096 METHOD 602.308 Jan. 17, 1967 Page 2 of 2 (WC) STANDARDIZATION AND/OR CALIBRATION Check standardization of .1 N NaOH using standardette or Bureau of Standards certified (oven dried) potassium acid phthalate. Weigh about 1 gram of potassium acid phth to nearest .1 mgm. Checks in duplicate should be made. Titrate with the caustic to the equivalent point using phenolphthalein indicator or pH meter to pH 7.0 or any other suitable indicator. Call G wt. sample V - Vol .1 N NaOH used. CALCULATIONS _q____ 1000 N 204.1 X V PRECISION OF RESULTS AND SIGNIFICANT FIGURES No studies have been made of precision; however, this type of analysis should be about 10% relative of the amount present. Report results to the nearest whole ppm. SAFETY Use normal precautions handling laboratory equipment and reagents. ANALYTICAL TIME 1/2 hour SCOPE HC1 is absorbed out of sample into water and then titrated with .1 N NaOH. REFERENCES Unsigned pencil note in Dept. 22 Method Book JMD-.ff 2/6/67 CBY 1002394 RSV0032097 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS MATERIAL Unwashed EDC ANALYSIS REQUIRED HCL SAMPLE Pint bottle APPARATUS 50 ml Pipette 500 ml Iodine flask 250 ml Erlenmeyer flask 250 ml Graduate 100 ml Graduate DEPT. 22 METHOD 602. 321 April 29, 1964 Page 1 of 3 (WC) REAGENTS 0.03 N NaOH Methyl Red Indicator PROCEDURE 1. Add 150 ml of distilled water to a 500 ml iodine flask. Add 100 ml of sample to the water in the flask from a 100 ml graduate. CBY 1002395 RSV0032098 METHOD 602.321 April 29, 1964 Page 2 of 3 (WC) 2. Stopper the flask and shake vigorously for 1 minute. Allow layers to separate and pipette 50 ml of the water layer into a 250 ml Erlenmeyer flask. 3. Add 4-6 drops of methyl red indicator and titrate with 0.03 N NaOH to the yellow end point. CALCULATIONS ppm HCl or V x N x 3.65 x 150 x 10,000 NaOH NaOH ' Sample weight x 50 v. NAOH N,, x i0.95 x 10,000 NaOH _________ Sample weight For regular control samples the weight of 100 ml of EDC may be assumed to be 124 grams. PREPARATION OF REAGENTS See Reagents Manual STANDARDIZATIONS AND/OR CALIBRATIONS The 0.03 N NaOH is prepared and standardized by the solutions analyst. SAFETY Use normal precautions in handling glassware, chemicals, and electrical equipment. TIME REQUIRED 0.2 hour CBY 1002396 RSV0032099 METHOD 602,, 321 {WC) April 29, 1964 Page 3 of 3 PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES 95% confidence limits are i 5 ppm @ a level of 500 ppm. Report results to nearest ppm. SCOPE The HC1 is extracted by the water and an aliquot titrated with standard sodium hydroxide. REFERENCES Method No. 23-5-6 (4-19-54). GK/mlw 4/29/64 CBY 1002397 RSV0032100 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 23 METHOD 602.322 May 15, 1964 Page 1 of 3 (WC) MATERIAL Unwashed EDC ANALYSIS Cl^ (free chlorine) SAMPLE 1 pint APPARATUS 50 ml pipette 500 ml iodine flask 50 ml burette 100 ml graduate REAGENTS 0.1 N sodium thiosulfate (Na^S^O^) Starch indicator (1%) 1:1 HC1 solution KI solution (10%) PROCEDURE 1. Pipette 50 ml of sample into a 500 ml iodine flask containing 100 ml of distilled water. Add 5 ml of 1:1 HC1 and 25 ml of 10% KI solution to the flask, and shake vigorously for a few seconds. CSV 1002398 RSV0032101 METHOD 602.322 May 15, 1964 Page 2 of 3 (WC) 2. Add 1-3 ml starch indicator and titrate with 0.1 N sodium thiosulfate to the starch end point. As the end point is approached, stopper the flask and shake vigorously to insure complete extraction of Cl from the EDC layer. CALCULATIONS ppm Cl^ = (V) (N) (3.55) (10,000) Sample weight For regular control sample, the weight of 50 ml of EDC may be assumed to be 62 grams. PREPARATION OF REAGENTS See Reagents Manual STANDARDIZATION AND/OR CALIBRATIONS Standard solutions are prepared by solutions analysts and checked periodically. SAFETY Use normal precautions in handling chemicals, glassware, and electrical equipment. ANALYTICAL TIME 0.1 hour PRECISION OF RESULTS AND SIGNIFICANT FIGURES 95% confidence limits j[5 ppm at a leve of 5 0 ppm. Report results to the nearest ppm. C&Y 1002399 RSV0032102 ) METHOD 602.322 (WC) May 15, 1964 Page 3 of 3 SCOPE Chlorine liberates iodine from the KI and this free iodine is titrated with sodium thiosulfate. REFERENCES Method 23-5--1 (4-20-54) GK/mlw 5/15/64 ) J CbY 1002400 RSV0032103 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 23 METHOD 602.323 May 15, 1964 Page 1 of 3 (WC) MATERIAL Unwashed DCE ANALYSIS REQUIRED Fe SAMPLE 1 pint APPARATUS Pipettes, 1 ml, 2 ml 50 ml beaker 50 ml volumetric flask 500 ml volumetric flask Hot plate Beckman Model B Spectrophotometer REAGENTS Concentrated HC1 Ammonium thiocyanate solution, 10% in distilled water Bromine water saturated CBY 1002401 RSV0032104 METHOD 602.323 May 15, 1964 Page 2 of 3 (WC) PROCEDURE 1. Pipette 2 ml of sample into a 50 ml beaker and evaporate to dryness over a steam bath in a hood. 2. To the residue, pipette 2 ml of concentrated HC1, approximately 2 ml of distilled water and 2 to 4 drops of saturated bromine water. Boil the solution vigorously (m the hood) until the brown color of bromine gas is no longer visible. 3. Permit the beaker to cool and transfer the contents to a 50 ml volumetric flask. Wash the beaker several times with distilled water and transfer all washings to the volumetric flask. 4. Pipette 1 ml of ammonium thiocyanate solution into the volumetric flask and dilute to the mark with distilled water. 5. Mix the solution well and read the optical density m a 10 mm cell at a wave length of 475 m/fagainst distilled water. (If the O.D. is greater than 0.5, repeat the procedure using a 500 ml volumetric flask and 10 ml of ammonium thiocyanate reagent.) CALCULATIONS Determine the ppm Fe in the sample from the chart attached to Method 602.272 (WC). If the alternate procedure was used, multiply the ppm obtained from the chart by 10. In either case, multiply the ppm Fe by 0.94 to correct for the difference in densities of HC1 and DCE. PREPARATION OF REAGENTS 1. Ammonium thiocyanate solution 10% in distilled water Add 50 gm of ammonium thiocyanate to 450 ml of distilled water and mix until dissolved. CBY 1002402 RSV0032105 METHOD 6C2.323 (WC) May 15, 1964 Page 3 of 3 2. Saturated bromine water - Add bromine liquid to a small quaniry of water (100 ml) so that an excess of bromine remains in solution. STANDARDIZATION AITO/OR CALIBRATIONS See Method 602.272 (WC). SAFETY Use normal precautions in handling all chemicals, glass ware and electrical equipment. Handle all bromine in the hood. ANALYTICAL TIME 0.2 hour PRECISION OF ANALYSIS AND SIGNIFICANT FIGURES 95% confidence limits are 5 ppm at a level 50 ppm. Report results no the nearest 5 ppm. SCOPE Iron in the sample is oxidized no the +3 state and complexed with ammonium thiocyanate. The optical density of this colored complex is then read on a Spectrophotometer. REFERENCE Method 23-5-7 (9-24-52) Research Notebook Ho. 366, pg. 17398-17399. GK/mlw 5/18/64 CBY 1002403 RSV0032106 MONSANTO COMPANY HYDROCARBONS DIVISION TEXAS CITY, TEXAS DEPT. 22 METHOD 602.329 May 1, 1964 Page 1 of 4 (PT) MATERIAL 22D9 OH, Product EDC ANALYSIS REQUIRED Distillation SAMPLE 1/2 pint bottle APPARATUS Flask - 200 ml side tube distilling flask Specification - ASTM D850-45T. Thermometer - range 70 to 120C - ASTM D850-45T. Condenser - straight glass tube 600 to 610 mm in length, 12 mm inside diameter ASTM D850-45T. Receiver - graduated cylinder - 100 ml ASTM D850-45T. Support for flask - a sheet of 1/8 to 1/4" hard asbestos board 6 inches square with a circular hole m the center, 1 inch m diameter. Heater - Bunsen burner fullyadjustable. PROCEDURE 1. Carefully measure 100 ml sample m 100 ml graduate at room temperature and transfer to the distillation flask draining the cylinder at least 15 seconds. After draining, place the cylinder, without rinsing, under the lower end of condenser tube to receive the distillate. C6Y L002404 RSV0032107 METHOD 602.329 May 1, 1964 Page 2 of 4 (PT) Assemble the flask, thermometer and condenser. Adjust the thermometer m such position that the top of the bulb is level with the lowest point of juncture between the side tube and the neck, and the thermometer is vertical and centrally located in the neck of the flask. Heat the flask slowly, especially after ebullition has begun, so as to allow the mercury column of the ther mometer to become fully expanded before the first drop distills over. Regulate the rate of heating so that the ring of condensing vapor on the wall of the flask reaches the lower edge of the side arm m not less than 90 seconds, and preferably 120 seconds from the start of the rise of the vapor ring. The total time from the start of heating until the first drop falls into the receiver should not be less than 5 nor more than 10 minutes. When distillations starts, ad}ust the receiver to allow the condensate to flow down its inner wall to prevent loss by spattering; then adjust the heat to continue dis tillation at the rate of 5 to 7 ml per minutes. (About 2 drops per second). Maintain this rate and continue the distillation to dryness. The total yield of distillate shall not be less than 97%. Record the temperature reading when the first drop of distillate falls into the receiving cylinder (I.B.P.). Take additional readings at 5% - 50% - 95% and dry point. The "dry point" is the temperature at which the liquid just disappears from the bottom of the flask. Withdraw the heat immediately to prevent a super heated dry point. The sampite to be tested shall be transparent and free of separated water or cloudiness. It may be removed by filtration in which case the following precautions shall be taken CBY 1002405 RSV0032108 MONSANTO COMPANY HYDROCARBONS . POLYMERS DIV TEXAS CITY, TEXAS DEPTS 22 & 899 METHOD 602.430(WC) Feb. 10, 1967 Page 1 of 2 MATERIAL Cooling Tower Water Shell Water ANALYSIS REQUIRED Chromates (CrO,^) SAMPLE SIZE 1 pint bottle APPARATUS Hellige comparator (13 MM) Cat #E1031, Calgon Corp. Cr04 color disc 2 - #E1100, 13MM square cells 15 ml cylinder with glass stopper, marked 5, 10 & 15 ml 100 ml volumetric mixing cylinder. REAGENTS Calgon Chromate Reagent A Calgon Chromate Reagent B with dipper PROCEDURE The instrument is limited to 10 ppm CrO^. Any water containing more than this amount will need to be diluted with chromatefree water. Filter the sample if it is turbid. Add 5 ml of filtered sample (or dilution) to a mixing cylinder. Add 10 ml of Reagent A and mix. Add 1 dipper-full of Reagent B. Stopper and mix vigorously 10 seconds. Wait 5 minutes and again mix vigorously for 10 seconds. Ten minutes after adding Reagent B, fill one of the 13 MM tubes with the prepared sample and insert in the center hole of the viewer. Fill a second tube with unprepared sample 5 ml (or dilution) diluted to 15 ml with distilled water. CBY 1002406 RSV0032109 METHOD 602.329 May 1, 1964 Page 3 of 4 (PT) Use a soft paper through which the sample filters rapidly, avoid drafts, cover the funnel with a watch glass and filter at least 200 ml. Dehydration (that is removal of dissolved water) is not permissible. CALCULATIONS Correct the observed temperature for thermometer inaccuracy and barometric deviations from 760 mm 0C. Add 0,,043C for each mm below 760 mm 0C. Subtract 0.043C for each mm above 760 mm 0C. The thermometer shall be standardized for partial immersion and no emergent stem correction is necessary. These corrections should be made at I.B.P., 5%, 50%, 95% and dry point. PREPARATION OF REAGENTS None STANDARDIZATION AND/OR CALIBRATIONS The thermometer should be calibrated for partial immersion and no emergent stem correction is necessary. SAFETY EDC should be handled only with adequate ventilation and large quantities should be handled m a hood. Maintain proper precautions of handling combustible materials around an open flame. Make sure the distillation system is vented properly to prevent build-up of dangerous pressures. CBY 1002407 RSV0032110 METHOD 602.430(WC) Feb. 10, 1967 Page 2 of 2 Procedure (cone'd) Flace this second tube in the out slot. Place the 10 ppm Cr04 color disc m place. Turn the wheel to obtain the nearest color match between the sample and standard. Read the ppm CrO^ from the comparator. CALCULATIONS Diride ppm CrO^ read by the aliquot fraction of sample m the dilution. rnm cro - EFEILiLr.?.4 (wheel? x._100 ^ 4 ml sample diluted PREPARATION OF REAGENTS Use purchased reagents STANDARDIZATION AND/OR CALIBRATION None required ANALYTICAL TIME .2 hours SAFETY No hazards are involved PRECISION OF RESULTS & SIGNIFICANT FIGURES TO REPORT No precision studies have been made; however, the same water should check to + 1 ppm at a level of 10 ppm CrO^j. results to nearest ppm Cr04. Report SCOPE Chromates are reacted with carbozide reagent and read on a prepared color scale. No interferences are normally encoun tered m cooling tower water. REFERENCES Calgon Co. procedure 308-B CBY 1002^06 JMDtff 10/10/68 RSV0032111 METHOD 602.329 May 1, 1964 Page 4 of 4 (PT) ANALYTICAL TIME 0.5 hour PRECISION OF RESULTS AND SIGNIFICANT FIGURES TO REPORT Results of duplicate analyses should not vary more than 0.2PC. Report results to the nearest 0.2C scale reading. SCOPE The observed temperatures at initial boiling point and cer tain fractional distilled volumes are recorded. REFERENCES Method No. 22-21-2 ASTM D 850-47 ASTM D 850-45T (RNG 11-18-58) GK/mlw 5/1/64 CBV lO02'0' RSV0032112 701.00 JOB DESCRIPTIONS - SUPERVISORS 22-701.00 701.10 ^ 701.20 701.30 J OPERATING SUPERVISOR He supervises the day-to-day as well as the month-to-month operations of Departments 21, 22, and 23 in the manufacture of the VCM product from raw materials. He is responsible for the safe operation of the departments to produce quality product in the scheduled quantities at economical costs. He is responsible for suggesting schedules for major repairs and improvements to the unit. He assists in developing improvements to the present operating methods and equipment by requesting Process and Research studies as needed. He co-ordinates the activities of these departments with the balance of the plant establishing procedures for the more routine co-ordinating jobs. He will designate major operating rate brackets, supply levels, and raw material levfels. ASSISTANT OPERATING SUPERVISOR He assists the Qperating Supervisor in the day-to-day safe operation of the unit to produce quailty product in -scheduled quantities and at economical costs. He is responsible for trouble shooting during mechanical or chemical difficulties, for production problems and, for maintaining adequate records and for the preparation of routine operating reports. He is responsible for the level of training of members of his group. By formal and/or informal training programs he should raise this level as high as possible. He is responsible to initiate requests for raw materials, and supplies needed for the production rates designated. He is responsible that the is kept high so that there production interruptions. level of maintenance will be a minimum of of his area unscheduled SHIFT SUPERVISORS (WHEN NECESSARY) He supervises the shift-to-shift operation of designated groups of equipment of the Departments 21,22, and 23. He applies his efforts toward operating the unit at the conditions designated, the obtaining of the desired quality 3/28/62 1- - CBY 1002AL1 RSV0032113 22-701.30 701.40 I of Intermediates and product, and the safety of personnel and the equipments E[hen designated conditions cannot be held he is responsible to report the situation to his supervisor. When possible he will determine the cause of the difficulty and recommmend corrective action. He will initiate (or have the Chief Operator write) minor work orders, necessary emergency repairs and preventative maintenance. As a representative of Production, he will follow up on maintenance requests and on maintenance progress so as to keep to a minimum any interruptions and interference to good operations. He will take an active part in training the operators so that job knowledge and job performance will he high. TECHNICAL ASSISTANTS Assigned to definite duties in the operat ng department, such as manufacturing of a complex nature, start-up of new equipment and operating difficulties. Recoreds, studies, and directs the more technical aspects of such work without direct responsibility over hourly employees. i 3/28/62 2- - CBY 100241.2 RSV0032114 ) 22-702.00 70WD0 DEPARTMENT 22 (VCM) ORGANIZATION CHART > ) 3/28/62 1- - CBY 1002A13 RSV0032115 RSV0032116 RSV0032117 RSV0032118 RSV0032119 irtttu_______ r-UB'G ON'WKI I JLA-iPQ'JtS. TTM-M2 IMM.NO P-ZIFD-*fr> ttt.MV RSV0032120 RSV0032121 RSV0032122 RSV0032123 RSV0032124 I I I I I I I U-uii RSV0032125 RSV0032126 RSV0032127 JUI-?d a 41 r - ' \V-V fr C vli --/' ;jjgZ -------- .<S.V' i-f'cuzckt* iO'/aAwa / 7(~iMfi|fr*rif ,** _ /K.A*V/1 si^r . t-a, J-Jffl&ffc&<Q&..`**i>. *V '- ` ^J!!!!!!!!i,!liOTi,ililIlIlIlI|ll!li,llilil ' 1 _, ffT!!!!!!I!!I!iilIIliliJiI ' RSV0032128 RSV0032129 MAR RSV0032130 RSV0032131 tu *1 RSV0032132 |C.HilXUP iCHtPoH ttu SS Sf. t '*WiK DtM mmm ft*. n Ml M* *. ,,rc; 1 *1tW 1 . M tu ru 1 4ltl 4( 1 ***tb 1- Wt ! Hi Ml IH w t K 4E>*.**r- ( im tl 1 l MIK 4 inti, kti`44 m* kmuB *.1 IU 11*1 w * e* U K 1T*U 4 I - *u. h 1 w a TC M* s* 4l > mu lit * fcTUtL U1 U.I 1 - 4 * tIUk 4 miu [-*'* 1**tk .> <. " fc fc 4^ -L V"-- Yf''* `" . _X_| ..1 i1 t*y lot- m* ?it>i *remz----------- CBY 1002432 It*..-it RSV0032133 <r>/< RSV0032134 RSV0032135 HMl.yMCw*W OU.tfcSl- RSV0032136 r r' Mt. a RSV0032137 ( I I RSV0032138 0-30 RSV0032139 RSV0032140 r-- r- C* Utt I 2 RSV0032141 RSV0032142 o 34 RSV0032143 RSV0032144 0 s/~ RSV0032145 j>j>-S&J as? RSV0032146