Document oezzZnzxE25xwpx6pgzrbLvVg

Interoffice Communication to K, C. Hunt, Refining, Ponca City From J. J. Mangelinkx, Refining, Lake Charles Date September 19, 1977 Subject Sample Analyses We are sending via the company shuttle three charcoal tubes for Benzene Content, data sheets are attached. SAL 000009246 CONOCO INC. PONCA Cm, OKLAHOMA REFIN1NC TECHNICAL SERVICES LABORATORY PlL.: File: Date: LC ft 10 610.4 9/b/83 LABORATORY NO CHARGE: SUBJECT: 1-13-83 LC 49 Analysis of Samples For Para-Xvlene Study and Isomerization Unit Evaluation - Lake Charles Refinery DISCUSSION: Samples of Lake Charles No. 2 and No. 3 CRU reformate were received for TBP distillation and compositional, physical and octane analyses. The TBP fraction ation of each sample was done on an 8-plate still to produce IBP-250F OH cuts and 250F+ hot toms fractions. This work was done in connection with the Lake Charles para-xylene production study. In addition, samples of primary tower over head, No. 2 and No. 3 CTU light straight run and denuded casinghead were analyzed to provide data for the preliminary evaluation of a straight run isomerization unit at Lake Charles. PONA analysis including individual component breakdown through C8 hydrocarbons (excluding olefins) was run on all samples. The olefins are reported as C^'s, C5's and plus. Octanes (clear and leaded) were run on all samples including the TBP fractions. Trace determinations of F, Cl, S, H^S, Pb, As, H2O, basic/total nitrogen and oxygenated compounds were made on tne reformate samples, primary tower overhead and denuded casinghead. Analysis for carbonyl compounds and active oxygen require special sampling and preservation which will virtually necessitate on-site analysis The denuded casinghead contained an appreciable level of olefins, ie., 14.4 LV%. DATA: At tached. REFERENCE: Letter to K. C. Hunt from D. C. Griffith dated 8/9/83. Approved: Senior Technologist bp cc: (PWLL--DDFFMM))--RRHH--JJMM-WJVJ-MEO-JRU-DCG-USH-PAN-TGC-KCH-F Associate Technologist SAL 000009247 ' LABORATORY NO.: 1-13-63 9/6/B3 Page 6 Att. Lake Charlc Sample: Sample Sample Date: L.C. Sample No. : P.C. Sample No. : No. 3 Reformate 8/8/83 688-83 1566 No. 2 LSR 8/11/83 707-83 1579 Gravity, "API @60F 42.7 63.5 A5TM D-66 Dist. Corrected to 760 mm H8-, *F IBP 5X Recovered 103 Recovered 203 Recovered 303 Recovered 403 Recovered 503 Recovered 603 Recovered 703 Recovered 803 Recovered 903 Recovered 953 Recovered End Point X Recovered X Residue X Loss 91 148 153 204 227 248 266 282 29 9 306 338 361 388 98.0 1.5 0.5 109 147 157 172 182 193 203 212 220 230 244 254 264 98.5 1.5 -- No.3 LSR 8/11/83 706-83 157B 69.2 120 141 143 149 154 159 164 170 176 184 194 202 209 99.0 1.0 -- Pritnarv Tower Overhead 8/11/83 705-83 1577 86.5 88 100 102 105 107 111 113 118 122 129 139 144 149 98.0 0.5 1.5 R0NC RON -I- 3.17 M0NC MON -i- 3.17 gms. gras. TEL/gal.-------- -- TEL/gal.-------- Fluoride, ppm by Wt. Chloride, ppm bv Wt. Sulfur, ppm bv Wt. Hvdroy.en Sulfide, ppm bv Wt. Basic Nitrogen, ppm by Wt. Total Nitrogen, ppm by Wt. Lead, ppm by Wt. Arsenic, ppm bv Wt. Water, ppm by Wt. Bromine No. 65.0 85.0 64.0 85.1 68.0 87.6 67.4 87.8 76.4 93.4 74.2 92.8 <1 <1 50 <0.5 <0.5 <0.5 <0.01 <0.005 <10 -- Oxveenated Compounds . ppm bv Volume. ND indicates none detected Methanol Ethanol Isopropanol Acetone Methyl Ethyl Ketone Tert-butvl Alcohol Methyl tert-butyl ether ND(<100) NIH <10) ND( <10) ND( <10) ND( <10) ND( <10) ND( <10) Denuded Casinghead 8/11/83 704-83 1576 68.6 90 106 112 124 137 155 160 212 247 297 361 416 447 98.0 1.5 0.5 75.0 90.1 72.2 88.4 <1 <1 75 <n.5 11 12 0.03 0.03 <10 38 ND( <100) ND ( <10} ND( <10) ND( <10) ND( <10) ND( <10) ND< <10) ,g3fe:'iV'.W'W SKSeOi . ;; i. SAL 000009248 LABORATORY NO.: I-U-83 9/6/83 Page 5 Att. Lake Charles Sample: Sample Date: L.C. Sample No.: P.C. Sample No.: No.2 Reformate 8/11/83 703-83 1575 1BP-250*F OH Cut From No.. 2 Reformate 8/19/83 1575A TBP Diet. Yield, LVS -- 61.1 Gravity, "API @60*F 49-5 63.3 A.STM D-86 Dist. Corrected to 760 mm He-, IBP 52 Recovered 88 129 87 118 102 Recovered 147 129 202 Recovered 177 148 302 Recovered 40* Recovered 200 221 152 164 502. Recovered 240 185 602 Recovered 702 Recovered 260 279 196 207 802 Recovered 902 Recovered 298 321 218 229 952 Recovered 342 239 End Point 371 252 2 Recovered 98.0 98.0 2 Residue 1.5 1.0 X Loss 0.5 1.0 *F RONC 95.1 RON -r 3.17 gms. TEL Cal. 102.6 81.5 96.4 MONC MON 3.17 sms. TEL Gal. 85.0 93.0 76.0 93.5 : 50"F+Btms. From No. 2 Reformate 8/19/83 1575B 38.9 31.9 273 288 289 294 296 300 305 310 317 327 341 358 411 98.5 1.5 -- 110.3(1* 109.9*15 94.9(1) 96.2(1) No . 3 Reformate 8/11/83 702-83 1574 lBr-25'i'F OH Cut From No.3 Reformate 8/22/83 1S74A :50"F+ t*rom \o. Reformat, 8/22/63 I574K -- 57.3 42.7 44.7 57.4 30.4 89 137 160 192 214 232 250 266 282 298 323 346 376 98.0 1.5 0.5 99.7 104.7 88.8 94.8 87 121 135 157 170 101 191 200 210 219 230 239 250 97.5 1.0 1.5 88.1 100.6 81.4 94.0 271 28b 288 290 294 297 30J 307 333 323 340 338 423 98.5 1.3 -- 112.7' 113.41 9b. S' 97.. Fluoride, ppm by Wt. cl Chloride, ppm by Wt. <1 Sulfur, ppm bv Wt. 0.2 Hydrogen Sulfide, ppm by Wt. <0.5 Basic Nitrogen, ppm by Wt. <0.5 Total Nitrogen, ppm by Wt. <0.5 Lead, ppm by Wt. <0. 01 Arsenic, ppm by Wt.<0.005 Water, ppra by Wt. <10 <2 <1 0.2 <0.5 <0.5 <0.5 <0.01 <0.005 <10 Oxveenated Compounds . dot bv Volume. ND indicates none detected Mechanol ND(<100) Ethanol NDC <10) Isopropanol ND( <10) Acetone ND( <10) Methyl Ethyl Hetone ND( <10) Ttrt-butyl Alto- hoi ND( <10) Methvl tert-butyl ether NDC <10) ND (< 100) ND ( <10) ND( <10) NDC < 10) NDC <1Q) ND( <10) NDC <10) Octanes vere run on blends of these samples and Ponca Citv base gasoline. Thu data reported is the calculated octane number of these samples ' .rt i-- SAL 000009249 TW LABORATORY NO.: 9/6/83 Page 4 Att. 1-13-63 Sample: Sample Dace: 1. C- Sample No. : P. C- Sample No. : Compositional Analysis. LV2 PARAFFINS. LVX Isobutane - dermal Butane Isopentane Normal Pentane 2,2 Dimethvlbutane 2,3 Dimethvlbutane 2-Methylpencane 3-Hethylpentane Normal Hexane 2,2 Dimethylpentane 2,4 Dimethylpentane 3,3 Dimethylpentane 2-Methylhexane 2,3 Dimethylpentane 3-Methylhexane 3-Ethylpentane Normal Heptane 2,2 Dimethylhexane 2,3 Dimethvlhexane 2,4 Dimethvlhexane 3,3 Dimethvlhexane 2,3 Dimethylhexane 3-Methyl, 3 Ethylpencane Other C8 Isoparaffins Normal Octane Co Paraffins, total C.n Paraffins, total Cll Paraffins, total Ci2+Paraffins, total Paraffins, Total NAPHTHENES. LV% Cyclopentane Methvlcyclopentane Cvclohexane 1,1 Dimethvlcyclopentane l-c-3 Dimethylcvclopentane l-t-3 Dimethylcvclopentane l-t-2 Dimethylcvclopentane l-c-2 Dimethylcvclopentane Me thvlcyr}ohexane Ethvlcvcleoentane 1,1,3 Trimethylcyclopcrtane l-t-2c-4 Trimethvlpentane l-t-2c-3 Trimethylpentane Other Co Naphthenes Cp Naphthenes^ total CIO Naphthenes, total Cji Naphthenes, total Cl2*Naph thenes, total Naphchenes, Total AROMATICS, LV% Benzene Toluene Ethylbenzene Para-Xylene Meta-Xvlene Ortho-Xylene Cg Aromatics, total Cio Aromacics, total Cll Aromatics, total Cl2^Aroinatics, total Aromatics, Total OLEFINS, LV% C6 Olefins, total Olefins, total C,+ Olefin:,, total Olefins, Total T * ,] 1,akc .Charles Denuded Casinghead 8/11/83 704-83 1576 .-- -'a Trace 1.7 19.8 12.6 0,75 0.91 3.90 4.22 0.18 0.39 0.11 1.23 0.59 1.18 0.04 2.10 0.15 0.16 0.14 0.07 0.11 0.20 1.23 0.94 2.0 2.4 1.9 2.0 63.14 0.53 1.69 1.84 0.12 0.28 0.31 0.43 0.14 2.46 0.15 0.11 0.16 0.16 1.35 1.3 1.5 1.2 0.9 14.63 1.30 1.33 0. 22 0.23 0.49 0.08 1.0 0.9 1.6 0.7 7.85 0,23 0.35 13.8 14.38 - .n no Wi - 092^ ,M 0000 9/6/83 Page 3 Art Sample: Sample Dace: L.C. Sample No.: P.C. Sample No.: Primarv Tower Overhead 8/17/63 705-83 1577 Lake Charles no. 2 cru LSR 8/17/03 707-83 1579 Compositional Analysis. LVS PARAFFINS. LVS Propane Isobueane Normal Butane Isopentane Normal Pentane 2,2 Dimethylbutane 2,3 Ddmethvlbutane 2-Methylpencane 3-Methylpentane Normal Hexane 2,2 Dimethylpentane 2,4 Dimethylpentane 3,3 Dimethylpentane 2-Methylhexane 2,3 Dimethylpentane 3-Methylhexane 3-Ethylpentane Normal Heptane 2,2 Dimethylhexane 2,5 Dimethylhexane 2,4 Dimethylhexane 3,3 Dimethylhexane 2,3 Dimethylhexane 3-Methyl, 3 Ethylpentane Other Cg Isoparaffins Normal Octane Cg Paraffins, total Cio Paraffins, total On Paraffins, total Paraffins, Total NAPHTHENES. LV% Cyclopentane MethylcyclopenLane Cvclohexane 1,1 Dimethylcyclopentane l-c-3 Dimechylcyclopentane l-t-3 Dimechylcyclopentane l-t-2 Dimechylcvclopentane l-c-2 Dimechylcyclopentane Methvlcyclohexane Ethvlcvclopentane 1,1,3 Trimethylcvclopentane l-t-2c-4 Trimethylpentane l-t-2c-3 Trimethylpentane Other Cfi Naphthenes Cg Naphthenes, cotal Cio Naphthenes, total Naphthenes, Tocal AROMATICS, l.VX Benzene Toluene Ethylbenzene Para-Xylene Meta-Xylene Ortho-Xvlene Cg Aromatics, total Cjo Aromatics, total Aromatics, total Cl2 Aromatics, total Aromatics, Total OLEFINS, LVX C,- Olefins, total C5 Olefins, total C^*- Olefins, total Olefins, Total Torn! Trace 0.8 3.4 24.0 28.6 3.34 4.23 14.91 8.06 6.87 -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- 94,21 2.98 1.38 0.09 -- -- -- -- -- -- -- -- -- -- -- -- -- 1.12 -- -- -- -- -- -- -- -- -- 1.12 0.02 0.10 0. TO 0.22 'o.nn Trace 0.2 0.9 6.2 6.0 0.72 1.12 4.70 2.91 5.96 0.38 0.77 0.27 3.19 0.90 3.23 0.25 6.55 0.52 0.66 0.65 0.25 0.54 0.90 5.59 4.47 2.7 0.1 -- 60.63 0.53 3.22 4.11 0.80 0.90 1.03 1.42 0.50 8.91 0.52 0.62 0.51 0.51 6.73 . 1.17 0.02 31,50 1.61 3.85 0.45 0.40 1.17 0.33 0.06 -- -- -- 7.87 -- -- -- 1 00 . O0 No. 3 CTO LSR 8/11/83 706-83 1578 3.1 12.2 0.78 1.87 9.00 6.03 12.40 0.57 1.15 0.28 4.08 1.46 4.55 0.31 5.77 0.19 0.16 0.07 0.02 0.02 0.02 0.12 0_._02 -- -- 64.17 1.99 7.80 7.62 1.24 1.62 1.73 2.70 0.26 4.S5 0.39 0.23 0.12 0.12 0.14 -- -- 30.51 3.35 1.82 -- -- _____ _____ -- -- -- 5.17 -- 0.05 0. 10 0.15 inn.00 000009251 *** SAL m *i-^k RECOMMENDATIONS FOR SAMPLING AIK FOR THE SUBSEQUENT ANALYSIS OF THE BENZENE CONCENTRATION 1. Personal Sample Pump Calibration The pump must be calibrated with a charcoal sampling tube attached. The tips of the charcoal tubes can best be broken off by first scoring them with a small file. The opening should be at least one-half the internal diameter of the tube. The permissable total air volume range ^s0^^to551Herner sample. .Therefore, for an 8 hour sampling period we recommencTapproximately 50 cc's/minute sampling rate (maximum allowable flow is 114 cc's/minute). For a 15 minute sampling period, we recommend approximately 200 cc's/minute sampling rate (maximum allowable is 1 liter/minute). For the recommended low flows, the soap-bubble graduated tube flow measurement procedure is suitable for calibration. The atmospheric pressure and temperature must be recorded at the time of calibration. 2. ' Sampling Insure the personal pump is calibrated for the flow required for the sampling time period desired. Remove the white plastic guard from the clip-on-guard tube. Snap off the tips of the charcoal tube and insert the end with the shorter length of charcoal into the tubing connected to the pump. Replace the white plastic guard. Insure that the tube is in a vertical position for sampling. Start the pump and maintain for the desired sampling time period. At the end of the sampling period, remove the tube and immediately cap with the supplied plastic caps. Insure the cap is firmly in place and cannot be easily dislodged. Refer to the attached data sheet, and log all required information. Attach the sample charcoal tube to an ID tag. Insure that the data sheet and ID tag are identically identified. An example of how to attach the ID tag to the sample tube will be enclosed with the sampling tubes. 3. Sample Tube Transmittal Back to TSL for Analysis Insure that the sample charcoal tubes are effectively capped. Break the tips off of a new charcoal tube and cap. This tube will be used as a blank for the analysis; please identify as blank. Package all tubes in such a manner that will insure that the caps will not become dislodged. Return to TSL within as short a period of time as practical. Consider that the analysis of the tube must be made within 14 days from the time the sample was taken. Allow 24 hours for analysis after arrival at TSL Submit a completed data sheet for each sample. These sheets will be returned to you for your records after we log the analysis data. We will retain a copy of each data sheet. SAL 000009168 /V J OL. H /Kr? -+J 1 U`- I" ORGANIC SOLVENTS IN AIR Physical and Chenical Analysis Branch Analytical Method Analyte: Organic Solvents (See Table 1) Matrix: Air Procedure: Adsorption on charcoal desorption with carbon disulfide, GC Date Issued: 9/15/72 Date Revised: 7/15/74 Method No: Range: P&CAM 127 For the specific compound, refer to Tables I&II Precision: 10.5% RSD Classification: See Table 1 1. Principle of the Method 1.1 A known volume of sir is drawn through a charcoal tube to trap the organic vapors present. 1.2 The charcoal in the tube is transferred to a snail, graduated test tube and desorbed with carbon disulfide. w 1.3 An aliquot of the desorbed sample is injected into a gas chromato graph. 1.4 The area of the resulting peak is determined and compared with areas obtained from the injection of standards. 2. Range and Sensitivity The lower 11mlt In mg/sample for the specific compound at 16 x 1 attenuation on a gas chromatograph fitted with a 10:1 splitter is shown in Table 1. This value can be lowered by reducing the attenuation or by eliminating the 10:1 splitter. 3. Interferences 3.1 When the amount of water in the air is so great that condensation actually occurs in the tube, organic vapors will not be trapped. Preliminary experiments indicate that high humidity severely' decreases the breakthrough volume. 3.2 When two or more solvents are known or suspected to be present in the air, such information including their suspected identities, should be transmitted with the sample; since with differences in polarity, one may displace another from the charcoal. 127-1 sal 000009l69 ,rccir P COMMUNICATION 3.3 It oust be emphasized that any compound which has the same retention time as the specific compound under study at the operating conditions described in this method is an inter ference. Hence, retention time data on a single column, or even on a number of columns, cannot be considered as proof of chemical identity. For this reason it is important that a sample of the bulk solvent(s) be submitted at the same time so that identity(ies) can be established by other means. 3.4 If the possibility of interference exists, separation conditions (column packing, temperatures, etc.) must be changed to circum vent the problem. 4. Precision and Accuracy 4.1 The mean relative standard deviation of the analytical method is 8%. (Ref. 11.4). 4.2 The mean relative standard deviation of the analytical method plus field sampling using an approved personal sampling pump is 10% (Ref. 11.4). Part of the error associated with the method is related to uncertainties in the sample volume collected. If a more powerful vacuum pump with associated gas-volume integrating equipment is used, sampling precision can be improved. 4.3 The accuracy of the overall sampling and analytical method is 10% (NIOSH's unpublished data) when the personal sampling pump is calibrated with a charcoal tube in the line. 5. Advantages and Disadvantages of the Method 5.1 The sampling device is small, portable, and Involves no liquids. Interferences are minimal, and most of those which do occur can be eliminated by altering chromatographic conditions. The tubes are analyzed by means of a quick,-instrumental method. The method can also be used for the simultaneous analysis of two or more solvents suspected to be present in the same sample by simply changing gas chromatographic conditions from isothermal to a temperatureprogrammed mode of operation. 5.2 One disadvantage of the method is that the amount of sample which can be taken is limited by the number of milligrams that the tube will hold before overloading. When the sample value obtained for the backup section of the charcoal trap exceeds 25% of that found otPttre~"tront section, the possibility of sample loss exists. During sample storage the more volatile compounds will migrate throughout the tube until equilibrium is reached (33% of the sample on the backup section). 127-2 SAL 000009170 1>- u.r u>-< -J w 1 v- . 5.3 Furthermore, the precision of the method is limited by the reproducibility of the pressure drop across the tubes. This drop will affect the flow rate and cause the volume to be imprecise, because the pump is usually calibrated for one tube only. 6. Apparatus 6.1 An approved and calibrated personal-sampling pump for personal samples. For an area sample any vacuum pump whose flow can be determined accurately at 1 liter per minute or lessj 6.2 Charcoal tubes: glass tube with both ends flame sealed, 7 cm long with a 6-mm O.D. and a 4-mm I.D., containing 2 sections of 20/40 mesh activated charcoal separated by a 2-mm portion of urethane foam. The activated charcoal is prepared from coconut shells and is fired at 600**C prior to packing. The absorbing section contains 100 ng of charcoal, the backup section 50 mg. A 3-ra portion of urethane foam is placed between the outlet end of the tube and the backup section. A plug of silylated glass wool is palced infront of the absorbing section. The pressure drop across the tube must be less than one inch of mercury at a flow rate of 1 ipm. 6.3 Gas chromatograph equipped with a flame ionization detector. 6.4 Column {20 ft x 1/8 in) with 10% FFAP stationary phase on 80/100 me9h, acid-washed DMCS Chromosorb W solid support. Other columns capable of performing the required separations may be used. 6.5 A mechanical or electronic integrator or a recorder and some method for determining peak area. 6.6 Glass stoppered micro tubes. The 2.5-mi graduated microcentrifuge tubes are recommended. 6.7 Hamilton syringes: 10 vl* and convenient sizes for making standards. 6.8 Pipets: 0.5 mi delivery pipets or 1.0 mi type graduated in 0.1 mi increments. 6.9 Volumetric flasks: 10 mi or convenient sizes for making standard solutions. 7. Reagents 7.1 Spectroquality carbon disulfide (Matheson Coleman and Bell) 127-3 SAL 000009171 7.2 Sample of the specific compound under study, preferably chromatoquality grade. 7.3 Bureau of Mines Grade A helium. 7.4 Prepurified hydrogen. 7.5 Filtered compressed air. 8. Procedure 8.1 Cleaning of Equipment. All glassware used for the laboratory analysis should be detergent washed and thoroughly rinsed with tap water and distilled water. 8.2 Calibration of Personal Pumps. Each personal pump must be * calibrated with a representative charcoal tube in the line. fThis will minimize errors associated with uncertainties in the sample volume collected. 8.3 Collection and Shipping of Samples 8.3.1 Immediately before sampling, the ends of the tube should be broken to provide an opening at least one-half the Internal diameter of the tube (2mm). 8.3.2 The smaller section of charcoal is used as a back-up and should be positioned nearest the sampling pump. 8.3.3 The charcoal tube should be'vertical! during sampling. 1 8.3.4 Air being sampled should not be passed through any hose or tubing before entering the charcoal tube. 8.3.5 The flow, time, and/or volume must be measured as accurately as possible. The sample should be taken at a flow rate of 1 lom nr leas to attain the total sample volume required. The 'minimum and maximum sample volumes that should be collected for each solvent are shown In Table 1. The minimum volume quoted must be collected if the desired sensitivity is to be achieved. 8.3.6 The temperature and pressure of the atmosphere being sampled should be measured and recorded. 8.3.7 The charcoal tubes should be capped with the supplied plastic caps Immediately after sampling. Under no circumstances should rubber caps be used. I,BL! 127-4 $41. 009l7. 8.3.8 One tube should be handled in the sar.e manner as the sample tube (break, seal, and transport), except that no air is sampled through this tube. This tube should be labeled as a blank. 8.3.9 Capped tubes should be packed tightly before they are shipped to minimize tube breakage during shipping. 8.3.10 Sasplesof the suspected solvent(s) should be submitted to the laboratory in containers furnished by MOSR for such purpose. These liquid bulk samples should not be transported in the sane container as the samples or blank tube. If possible, a bulk air sample (at least 50i air drawn through tube) should be shipped for qualitative identification purposes. 8.4 Analysis of Samples . 8.4.1 * Preparation of Sanples. In prepratioa for analysis, each charcoal tube is scored with a file in front of the first section of charcoal and broken open. The glass wool is removed and discarded. The charcoal in the first (larger) section is transferred to a small stoppered test tube. The separating section of foam is removed and discarded; the second section is transferred to another test tube. These tvo sections are analyzed separately. 8.4.2 . Desorption of Sanples. Prior to analysis, cr.e-half ml of carbon disulfide is pipetted into each test tube. (All work with carbon disulfide should be performed in a hood because of its high toxicity.) Tests indicate that desorption is complete in 30 minutes if the sample is stirred occasionally during this period. The use of graduated glass-stoppered, nicrocentrifuge tubes is recommended so that one can observe any apparent change in volume during the desorption process. Carbon disulfide is a very volatile solvent, so volume changes can occur during the desorption process depending on the surrounding temperature. The initial volume occupied bv the charcoal plus the Q.Smt CS* should be noted and corres ponding volume adjustments should be cade whenever necessary just before GC analysis. 8.4.3 GC Conditions. The typical operating conditions for the gas chromatograph are: 1. 85 cc/min. (70 psig) helium carrier gas flow. 2. 65 cc/min. (24 psig) hydrogen gas flow to detector. 3. 500 cc/min. (50 psig) air flow to detector. 4. 200*C injector temperature. 127-5 SAL 000009173 5. 200C manifold temperature (detector) 6. Isothermal oven or column temperature - refer tc Table 1 for specific compounds. 8.4.4 Injection. The first step in the analysis is the injection of the sample into the gas chromatograph. To eliminate difficulties arising from blowback or distillation within the syringe needle, one should employ the solvent flush . injection technique. The 10 uZ syringe is first flushed with solvent several times to wet the barrel and plunger. Three raicroliters of solvent are drawn into the syringe to increase the accuracy and reproducibility of the injected sample volume. The needle is removed from the solvent, and the plunger is pulled back about 0.2 u to separate the solvent flush from the sample with a pocket of air to be used as a marker. The needle is then immersed in the sample, and a 5-pZ aliquot is withdrawn, taking ir*to consideration the volume of the needle, since the sample in the needle will be completely injected. After the needle is removed from the sample and prior to injection, the plunger is pulled back a short distance to minimize evap oration of the sample from the tip of the needle. Duplicate injections of each sample and standard should be made. No more than a 3%_d.ifference in area is to be expected. 8.4.5 Measurement of area. The area of the sample peak is measured by an electronic integrator or some other suitable form of area measurement, and preliminary results are read from a standard curve prepared as discussed below. 8.5 Determination of Desorption Efficiency 8.5.1 Importance of determination. The desorption efficiency of a particular compound can vary from one laboratory to another and also from one batch of charcoal to another. Thus, it is necessary to determine at least once the percentage of the specific compound that is removed in the desorption process for a given compound, provided the same batch of charcoal is used. The Physical and Chemical Analysis Branch of N10SH has found that the desorption efficiencies for the compounds in Table 1 are between 81% and 100% arid vary with each batch of charcoal. 8.5.2 Procedure for determining desorption efficiency. Activated charcoal equivalent to the amount in the first section of the sampling tube (100 mg) is measured into a 5era, 4-mm I.D. glass tube, flame-sealed at one end (similar to commercially available culture tubes). This charcoal must be from the same batch as that used in obtaining the samples and can be obtained from unused charcoal tubes. The open end is capped 127-6 SAL 000009174 vith Parafilm. A known amount of the compound is injected directly into the activated charcoal vith a nicroliter syringe, and the tube is capped with more Parafilm. The account injected is usually equivalent to that present in a 10-liter sample at a concentration equal to the federal 1 standard. At least five tubes are prepared in this manner and allowed to stand for at least overnight to assure complete abosrption of the specific compound onto the charcoal. These five tubes are referred to as the samples. A parallel blank tube should be treated in the same manner except that no sample is added to it. The sample and blank tubes are desorbed and analyzed in exactly the sane manner as the sampling tube described in Section 8.3. 4 Two or three standards are prepared by injecting the same volume of compound into 0.5 mi of CSt vith the sa?e svringe used in the preparation of the sample. These are analyzed with the samples. The desorption efficiency equals the difference between the average peak area of the samples and the peak area of the blank divided by the average peak area of the standards, or Area sample Area blank desorption efficiency = Area taniard 9. Calibration and Standards It is convenient to express concentration of standards in terms of tag/0.5 mi CS2 because samples are desorbed in this amount of CS2* To minimize error due to the volatility of carbon disulfide, one can inject 20 times the weight into 10 mi of CS2- For example, to prepare a 0.3 mg/ 0.5 mi standard, one would inject 6.0 mg into exactly 10 nl of CS2 in a glass-stoppered flask. The density of the specific compound is used to convert 6.0 mg into microliters for easy measurement with a microliter syringe* A series of standards, varying in concentration over the range of interest, is prepared and analyzed under the same GC conditions and during the same time period as the unknown samples. Curves are estab lished by plotting concentration in pg/0.5ro. versus peak area. NOTEl Since no internal standard is used in the method, standard solutions must be analyzed at the same time that the sample analysis is done. This will minimize the effect of known day-to-day variations and variations during the same day of the FID response. 127-7 SAL 000009175 10. Calculations 10.1 The weight, in mg, corresponding to each peak area is read from the standard curve for the particular compound. No volume corrections are needed, because the standard curve Is based on mg/0.5 ml CS2 and the volume of sample injected is identical to the volume of the standards injected. 10.2 Corrections for the blank must be made for each sample. Correct mg = mgg - mgb where: mgs " 8 found in front section of sample tube mgb ** mg found in front section of blank tube A similar procedure is followed for the backup sections. 10.3 The corrected amounts present in the front and backup sections of the same sample tube are added to determine the total measured amount in the sample. 10.4 This total weight is divided by the determined desorption efficiency to obtain the total mg per sample. 10.5 The volume of air sampled is converted to standard conditions of of 25C and 760 mm Hg. P 298 V8 * V * 760 T+273 where: V " volume of air in liters at 25eC and 760 mm He 5b V " volume of air in liters as measured P Barometric pressure in mm Hg T Temperature of air in degree centigrade 10.6 The concentration of the organic solvent in the air sampled can be expressed in mg per which is numerically equal to pg per liter of air . * .. total mg (Section 10.4) x 1000 (ue/me') mg/m-* " pg/t " -------------- --------------------- ~------------------------------ Vs 10.7 Another method of expressing concentration is ppm, defined as p of compounds per liter of air ppm pi of compound/V6 where: ppm pi of compound Vs 24.45 MW 24.45 " molar volume at 25*C and 760 mm Kg MW * molecular weight of the compound (Table 1) 127-8 SAL 000009176 V 11. References 11.1 White, L.D., D.G. Taylor, P.A. Mauer, and ?..Z. Kupel, "A Convenient Optimized Method for the Analysis of Selected Solven Vapors in the Industrial Atmosphere," Ar~r. ~r*d. h-jc. Assoc. J. 31:225 (1970) . 11.2 Young, D.M. and A.D. Crowell, Physical Adsorption of Cases, Buttervorths, London, 1962, pp. 137--1-6. 11.3 Federal Register, 37 (`202), 22139-22142 (October IS, 1972). 11.4 NIOSR Contract: HSM-99-72-98, Scott Research Laboratories, Inc., "Collaborative* Testing of Activated Charcoal Sampling Tubes for Seven Organic Solvents," pp. 4-22, 4-27 (1973). * SAL 000009177 conoco SAL 0000091' \ 00 Organic Solvent \cetone Senzene Carbon tetrachloride Chloroform Dichloromethane P-Dioxane Ethylene dichloride Methyl ethyl ketone Styrene Tetrachloroethylene 1,1,2-trichloroethane 1,1,1-trichloroethane (Methyl Chloroform) Trichloroethylene Toluene Xylene TABLE I PARAMETERS ASSOCIATED WITH P&CAB ANALYTICAL METHOD NO. 127 './uxC.* JT.JD -- Sample Volume (L) Method Detection limit #\ Classification (mg/sample)^.^^Ttininium^ } Maximum'1 GC Column Temperature(C) Molecular Weight D 0.5 7.7 60 58.1 GLB> 0.5- 53 90 78.1 A 0.20 10 60 60 154.0 A 0.10 0.5 13 80 119 D 0.05 0.5 3.8 85 84.9 A 0.05 1 18 100 88.1 D 0,05 1 12 90 99.0 B 0.01 0.5 13 80 72.1 D 0.10 1.5 34 150 104 B 0.06 1 25 130 166 B 0.05 10 97 150 133 B 0.05 0.5 13 150 133 A 0.05 1 17 90 131 B 0.01 0.5 22 120 92.1 A 0.02 0.5 31 100 106 (a) Minimum volume, in liters, required to measure 0.1 times the OSHA standard (b) These are breakthrough volumes calculated with data derived from a potential plot (reference 11.2) for activated coconut charcoal. Concentrations of vapor in air at 5 times the OSHA standard (reference 11.3) or 500-,ppm, whichever is lower, 25C, and 760 torr were assumed. These values will be as much as 502 lower for atmospheres of high humidity. The effects of multiple contaminants have not been investigated, but if is suspected that less volatile compounds may displace more volatile compounds (See 3.1 and 3.2) Cc I TABLE 11 CHEMICALS WHICH HAVE GREATER THA>: 80': DESORPTION EFFICIENCY BUT HAVE NOT RFF.N THOROUGHLY TESTED BY NTOSH Class E (Proposed) Acrylonitrile Tsobutyl acetate Allyl glycidyl ether Isobutyl alcohol h-Amyl acetate Isoctane 2-Butoxyethanol Isoohorone n-Butyl acetate Isopropyl acetate n-Butyl alcohol Isopropyl glycidyl ether n-Butylglycidyl ether 2,6-Lutidine Chlorobenzene Methyl acetate Cyclohexane Cyclohexanone Methyl acrylate Methyl n-butyl ketone o-Dichlorobenzene Methyl ethyl ketone p-Dichlorobenzene Methyl isobutyl ketone Diethyl ether Methyl methacrylate N,N-Dimethyl aniline o-Methyl styrene Epichlorohydrin p-Mathvl styrene 2-Ethoxylethyl acetate n-Oc tane Ethyl acetate 3-Octanone Ethylbenzene Pentane Ethyl butyl ketone 2-Pentanone Fufural / Heptane o-pir.ene n-Propvl acetate Hexane Isoamyl acetate 1,1,2,2-Tetrachloroethane Tetrahydrofuran Trichlorotrifluoroethane (Freon 113) Recommended Sample Size 101 127-11 SAL 000009179 CONTINENTAL OIL COMPANY PONCA CITY, OKLAHOMA REF ININS TECHNICAL SERVICES LABORATORY LABORATORY NO. CHARGE: SUBJECT: E-74-77 LC 49 Benzene Content of Gasoline Streams and Blends Refinery LC :U: 552.1 92i ete: 5-19-77 series ANALYTICAL DATA: Sample Number PC 1839 PC 1340 PC 1841 PC 1842 PC 1843 PC 1844 PC 1819 PC 1846 PC 1847 PC 1848 PC 1849 PC 1850 LC 640-77 LC 641-77 LC 642-77 LC 643-77 LC 644-77 LC 645-77 LC 646-77 LC 647-77 LC 643-77 LC 649-77 LC 650-77 LC 651-77 Sample .Regular Gasoline C Premium Gasoline ^ \Unleaded Gasoline Coker Gasoline Thermal Gasoline TCC Gasoline No. 1 L.S.R. No. 2 L.S.R. Denuded Casinqhead No. 1 Reformate No. 2 Reformate Primarv Tower Over REFERENCE: Letter from J. J. Mangelinkx to K. C. Hunt dated 5-12- V:I .L 3enzene 1,1 Tr 1.5 / G. 9 1.0 2.3 Approved: Senior Technologist b? / cc: GAO-DRU-JRU-MEO-KCH-F 77j, L: Jil l .-.ssc:-.E*e Cnemist 0000 0918