Document oDDamaKjQxXV6oqbk07a41Eyg

2. --/ * <3 Monsanto Company Organic Chemicals Division St. Louis Research Department St. Louis Research Report No. 3067 FINAL REPORT ON ANALYTICAL CHEMISTRY AND SPECTROSCOPY INVESTIGATIONS - 1962 Part II - Special Studies Job No. 2*02-760.01-l`?d6-II January, 1964 Work done and written by: R. s. Keller 0. w. Ashworth B. Katlafsky M. W. Dietrich D. B. Hines C. H. Brackblll 0. Klnast 0. Hicks VtelMaWCTHUlVt.n* fiwiri DSW 167055 STLCOPCB4041213 r-^WMBRUR DISTRIBUTION OP REPORT NO. 3067 1. File 2. R. E. Killer 3. H. L. Hubbard - File 4. Duplicate File Central Technical Files 6. R. 1 delsman - J. F. Queeny Plant 7. V. j. Gresham - W. 0. Krummrlch Plant d. MCL - England - via D. Danna 9. MCL - England - via D. Tanna 10. Extra n. Extra 12. Extra i?. Extra 14. Extra This report contains confidential Information which Is the property of the Monsanto Company and which shall be disclosed only to authorized persons, The recipient ta held accountable for the filing and safe custody of the report which must be returned on demand. DSW 167056 STLCOPCB4041214 TABLE OP CONTENTS Page Wo. INTRODUCTION 1 GENERAL SlTWARY I ANALYTICAL STUDIES Section A - Aroclor 12*2 Product Variation - Infrared and Gee Chromatography Study 2 Section B - Penzlmldazollnea - N*IR Study of Substi tuted 10 Section C - Blollte Analytical Investigations 22 Section D Dlbutyl Phenyl Phosphate ~ Analysis of Reaction Products 54 Section E - Competitive Hydrocarbon Ester Fluids Identification of Inhibitors 55 Section F - Evaluation of Infotronlcs CRS-1 Inte grator for NN.r Signal Integration 42 Section 0 - Hethyl Lactate - NHB Determination In First Step Reaction Mixture 56 Section H Fentschlorophenol - X-Ray Diffraction Studies 57 Section I - *r&*Thenettdlne - Tientl f i cation of Con`tami rants 65 Section J Plasticizers and Other High Bolling Esters Identification 67 Section K - Resorcinol in Sodium Sulfite Solution Infrared Stuly of Rea*tion Rate 66 Section L - Solium Fheoate and Sodl :rr. Rtnzenesulfonate - Attenuated Total Reflectance Infrared Stuly 99 Section K - Resorcinol - Thin Layer "rromatography Investigations 111 Section N - Trlcosa.ne Oxidation Study - Infrared Analysis 114 Section 0 * Vanadium Ori de Components lr. ''atalyst mixtures liS DSW 167057 1. 1 VTROD'JCTJ-CN Special investigations were carried out by the Analytical Chemistry And Spectroscopy Group during 19b^? to support Organic Research Departrr.ent and Manufacturing department projects. The studies also included certain projects listed In the September ?9, 1961 FA ("nclassiried Anal. Chem. - 3a). SUMMARY Fifteen analytical studies covering Organic Division products were carried out to provide Information reeled for Research Department and Manufacturing Department projects. Chemical and Instrumental techniques were .-ed tot . show Aroclor 124? product variations . characterize the structure of substituted benzimidazolines . evaluate Blolite under use situations . show the composition of dlbutyl phenyl phosphate reaction products ............ .. ........ ... '~ . Identify Irhlbitors In competitive funct1 oral fluids measure m.Pth2.1,,j3cta* e In process reaction mixtures , show the crystal form and transition of pentachlorophenol . Identify contaminants In p-pher.et mine . measure reaction ''atea of reaoroir'-i in sodium sulfite solution . s^ow the oxidation products fore"! from trl_cosaoe . show the components ! ri vari, ji >m oxide catalyst mixtures . evaluate an Jjifptnpr. j os_?:RS_; nj-egr ator for NMR . set, up an anajyttrai sphere for identification and measurement of plastl cizers_ and *>* ner high ta iling esters . demonstrate the potential o'* jrfrared At^tentuatjsd TTot.s] Reflectance as an lost ream monitoring device tor sotTl urn jjfierate end sodljim benzenes"' `o1** r e demonstrate '."ye*" rl r'crr*.op''>ijhv t e/*hni qiues. DSW 167058 STLCOPCB4041216 SECTION A AROCLOR 1242 PRODUCT VARIATION - INFRARED AND OAS CHROMATOORAPHY STUDY ' ' Introduction Infrared absorption and OLPC (gas liquid partition chromatography) methods were used to study compositional variations between rive lots of Aroclor 1242 representing typical production material shipped to General Electric from the Anniston plant over a six month period. The study was Initiated to determine if abnormal variations were present and. If so, the cause of the difference. 1R and OLPC are complementary techniques for such a study, since IR can detect, gross Isomeric distribution differences and OLPC can Identify and measure the individual isomers. Summary An infrared and OLPC (gas-llquld partition chromatography) study of five normal production samples of Aroclor 1242 from Anniston showed that most of the variations In isomer content were small and random. However, one pronounced periodic variation was observed In the infrared spectra In the region of 14.5-14.4 microns which was shown by a combination of infrared and QLPC analysis to be the result of variations In the lower chlorination level isomers, namely the 2-chlorO, 2,2*-dlchloro and the 2,41-dlchloroblphenyls. Analytical Studies t Reserve samples of lots D-122, I>-i45 and D-185 were obtained from Anniston to represent normal production material. Since no sample of lot D-153,the subject of a recent General Electric complaint, was available,samples of lots D-lb2 and D-15>4 were substituted. Infrared spectra were run under conditions such that the gross infrared spectra could be compared rather than under special conditions to study a particular Isomer. The OLPC analysis was carried cut using a 150* x 0.020" stainless steel capillary column coated with silicone gum rubber and a flame ionization detector. A critical comparison of the IR spectra showed primarily the minor random variations expected for small differences in Isomer distribution. However, in the region of 14.J to l4.4 microns, two weak absorption bands were observed whose intensities varied periodically with lot number. The attached IR spectrum shows the superlmposltion of the spectra of the five lots of Aroclor 1242 studied run under conditions to amplify the difference. Examination of the spectra in the region DSW 167059 STLCOPCB4041217 of 14. J-14.4 microns shows that the intensity of tht absorption bands at these wavelengths Increases sharply from lot D-122 to D-14|j. The absorption reaches a maximum In lot D-lb? then tapei s off in lots D-1&4 and D-18&. The maximum variance observed betwian lots P-122 and D>1^2 was In terms of optical absorption units. Ths OLPC data for the five samples shows the random variations of Isomera also detected by IR. No variations In a single component was observed that could explain the difference found in the 1R spectra. The OLPC data is tabulated in Table I. Where possible, the OLPC fraction has been Identified as a particular isomer on the basis of retention time. Despite the fact that the positive Identification of the com ponents Involved In the observed periodic variation in the IR spectra could not be made, structural characteristics of the materials contributing to this variation could be assigned, based on Infrared Interpretation of aromatic absorption patterns. The chlorine distribution patterns In Aroclor 1242 fit the following general classes: Type I Type II Type III Type IV Of these four general classes of chlorine distribution patterns, only Types 1 and II (the monosubstltuted aromatics and the ortho dlsubstituted aromatics) produce absorption bands In the 14..3-14.4 micron region. Although it is possible to detect and differentla'.e the Types I and 11 materials In other regions of the IR spectra, lnterferencea and overlapping of bands prevents this i*n the bulK sample. ' DSW 167060 riaMtJ. - STLCOPCB4041218 4. In order to resolve this problem and identify the components causing the observed variance in the IR spectra, lot D-152 was fractionally distilled by Mr. Qeorge Ashworth under reduced pressure and four top fractions,representing a total of B.4jt of the charge, were Isolated for subsequent analysis. The OLPC analytical data which was conflrsted by IR analysis shows that the mono and dlchloroblphenyls having the type I and II structures postulated by IR inter* pretatlon of the bulk sample were the major contributors to the variation observed In the IR spectra of the bulk sample. The QLPC data Is tabulated In Table II. A combination of IR and OLPC analysis has demonstrated that the periodic variation observed In Aroclor 1242 lots D*122, D-145, D-15>2, D-1&4 and D-185 are the cumulative effects of variations primarily of the 2-chloro, 2,2'*dlchloro and the 2,4*-dichlorobiphenyls. 2/62 - R. . Keller, B. Katlafsky, E. M. Emery DSW 167061 STLCOPCB4041219 Table I AROCLOR 1242 Fractlon/Conponent 1 Biphenyl 2 Ortho 3) Meta 4)para 5 2,2l 6 2.5 7 (2,4 or 2,3 or 2,3*) 8 2,4* 9 (3,5 or 3,3*) 10 (5,4 or 2,5,2*) 11 4-4i 12 13 2,3,2* * 14) 15) 16) 2,5,4* 17) 18 3,4,2i 19 2,3,4 20 21 22 23 24 2256 3,4,4*, 27 28 29 30 31 32) 33 Lot D-?22 0.04 0.8 0.2 4.5 0.8 1.4 9-1 0.7 10.2 5.3 0.2 4.8 1.5 150 6.7 3.0 0.7 0.2 3.6 2.7 1-9 3.5 3*3 3-4 0.6 0.1 o.l 5.1 3.9 Lot Lot D-145 ..D-152 0.03 1.0 0.3 0.3 1.9 0.6 4.9 5-2 0.8 1.0 Lot D-154 0.2 1.8 0.5 4.8 1.0 1.8 9.6 0.8 10.0 5.7 0.5 5.8 1.8 1.9 10,3 0.6 9.4 5.2 0.3 5.1 1.5 1.8 * 9.6 0.7 9-5 5.3 0.4 5-2 1.4 14.9 6.6 3.0 0.7 '<t3.41. 2.4 1.5 3-3 3-2 3-2 0.7 0.1 0.05 4.6 3.5 13.7 6.0 2.7 0.6 0.2 3.4 2.4 1.7 33 3.1 3.1 0.6 0.1 0.05 4.9 3.7 14.1 6.1 2.7 0.7 f[3, .9 2 .6 1.8 3.4 3-0 3.3 0.6 0.1 0.05 5-1 4.0 Lot L-185 0.03 0.9 0.2 4.6 0,8 1.6 9.5 0.7 lo.l 5.4 0.5 5.7 1.6 15.0 6.6 3.0 0.7 0.2 3.5 2.6 1.8 3.3 3.2 3-4 0,8 C.l 0.1 4-9 3.8 rTSrrVJ DSW 167062 STLCOPCB4041220 6 rVJo1-ofor-^t-rVri to k *o v o cd~j t^vn * ? Fraotlon/CQttponant Lot D-122 0.2 2.7 0.? 0.5 0.2 0.05 0.2 0.4 0.2 0.8 0.1 0.6 0.3 Table I (cont'd) Lot Lot Lot D-145 D-152 D-154 0.1 2.4 0.3 0.5 0.2 0.05 0.2 0.3 0.2 0.8 0.2 0.4 0.4 0.2 2.6 0.3 0.1 0.5 0.1 0.3 0.5 0.3 1.1 0.1 0.3 0.3* 0.2 2.6 0.3 0.7 0.3 0.05 0.2 0.4 0.2 0.9 0.2 0.5 0.3 Lot P-I05 0.2 2.6 0.3 0.5 0.2 0.02 0.2 0.3 0.1 0.7 0.1 0.4 0.2 DSW 167063 STLCOPCB4041221 ARCPCLOR 1242 LOT D-I52 TOPPINQ EXPERIMENT Fraction/Component 1 Biphenyl 2 ortho 3) meta 4) para 5 2,2* 6 2,5 7(2 ,4 or 2,3 or 2,3*) 8 2,4i 9 (3,5 or 3,3*) 10(3,4 or 2,5,2i) 11 4,4* 12 13 2,3*2* 14) 15) 16) 2,5*41 17) 16 3,4,2* 19 2,3,4 20 21) 22) 23 24 25 26 3,4,4* 27 26 29 30 31) 32) 33 Starting F#1 F#2 F#3 F#4 Mat'l 1-9% 1-7% 2.?# 2.5% 0.3% 1.9 0.6 5-2 1.0 8.6% 29-7 6.5 36.8 2.8 0.6% 26.0 7.3 43.0 3-4 traoe traoe 7-1% 1.3% 5-9 4.1 41.3 36.O 5-6 6.6 1-9 10.3 0,6 9.4 5.2 0.3 5-1 1.5 2.9 11.5 0.3 4.2 14.1 0.3 6.9 27-4 i.l j 0-8 ,j 1.0 00 trace trace 3-5 0.8 o.l 0.3 0 9-2 35.0 1.5 * .7 1.2 0.1 0.4 0 13.7 trace trace 6.0 2.7 0.6 3-6 2.4 1.7 3-3 3.1 3*1 0.6 0.1 0.1 4-9 3.7 Residue 91.6% 0 0 trace 0.2 0.2 0.9 5-7 0.5 9-9 6.6 0.5 6.1 2.1 17.6 7.7 2.1 0.7 A.5 ?.l 2.0 4.1 3.8 3.8 0.7 0.1 6.1 *.5 DSW 167064 STLCOPCB4041222 VJl ro cs^-v>i m o 'O co-4 <j>v/i * r Fraction/Component Table II (cont*d) Starting F#1 F#2 Material _______ F#3 0.2 2.6 0.3 0.7 0.5 0.1 0.3 0.5 0.3 1.1 0.1 0.3 0.3 F#4 8 Residue 0.2 3.1 0.2 0.6 0.3 trace 0.3 0.4 0.2 1.0 0.1 *0.5 * instrument ehut down before this peak was eluted from the column. -fwr DSW 167065 STLCOPCB4041223 9- 100 SPECTRUM NO. SAMPLE_______ AZocur i2V2, ORIGIN. 1 ; ; i i , m ft : e0 purity PZoPUCTIQfJ Unties PHASE tiauip THICKNESS OOSnim. |ITD-I2Z `UffV-M 0 zliTJtM. s. LiTO-nS jJLT tMS* DATE </lg/tZ 8OPERATOR K~ remarks 78 % Trans. 40 S&t&iN fePfgtAAit - l\-l PRISM ~kcT . Xjf-- z *J mm RESOLUTION _3jL3C~ RESPONSE 2 0 GAIN JLjL SPEED 3Z H\ SUPPRESSION SCALE i 0 cm.^ _I_ M ICRons <[HHICAl charts ihc. sur/Aio * PR-1106 DSW 167066 STLCOPCB4041224 10. SECTION B NMR STUDY OF SUBSTITUTED BENZIHIDAZOLINONES Introduction Research to define the scope and limitation of 3,4,4,-trlchlorocarbanlllde (TCC) as a soap bacterlostat has established that TCC loses Its bacteriostatic activity when used In conjunction with hypochlorite bleach. A chemical study of the action of hypochlorite on TCC Indicated that this loss of bacteriostatic activity was due to the conversion of TCC to a trlchlorinated l-phenyl-2-benzlmldazolinone which Is biologically inactive. This NMR study was Insti gated to provide additional evidence for the proposed ring system, and to determine the location of the 5 chlorine atoms in this system. Summary Proton NMR Bpectra were obtained from the product isolated from the reaction of TCC with bleach, from a related monochloro compound obtained from the reaction of carbanillde with bleach, the mono acetate derivatives of these compounds, and appropriate reference compounds. Analysis of these spectra indicated the structure of the compound formed in the reaction of carbanillde with hypochlorite Ion to be - and the compound formed in the reaction of TCC with hypocnlorlte Ion to be - DSW 167067 n. Analytical Studies * Preparation of BenalalAaaollnones The benllmaxollnones desorlb'd above were prepared by the following reactions A 'J Moalecis PCI ? -01 0 (1) HD J Moles 0C1~ c-o ci' (III) 'These compounds are Bhown as o-acecate, but may be N-acetate. The benzimidazole derivatives*of II and IV were prepared by the following reactions - (in ,0 | CHCO* (IV) B. NMR Measurements All measurements were made on 0.50 M solutions In dimethyl acetamide unless otherwise state. Chemical shifts are reported relative to (CH)S1 (IMS) defined as S-10a(H7MS-H) ,, l.e. Peak area measurements, not reported, weiRP b.-. i*i' V DSW 167068 i.r.ttlri l''r-'^'(>vU STLCOPCB4041226 12. ,, made on all compound and reference peaks with a Varlan V-J521 Integrator, and are consistent with the proposed structural assignments to in all cases. C. Reference Compounds. The NMR parameters of the reference materials examined are giver In Table I. As Is shown the peaks due to the two rings In the l-phenyl-2-benzlmldazollnone are well separated. Unless complicated by spin-spin interactions, this should also be true for the chlorinated compounds In question. The acetate derivative displays a well separated peak for proton C, that nearest the introduced unsaturation. TABLE 1 NMR Data from Reference Compounds Compounds Chemical Shift (ppmj ab c f J (C D8 ) ci< Vnh* Cl<(3 -NH-</ ^jCI 7-05 6.57 }* oi--c 6.81 6.58 7.11 JAB ' 6'7 JAB " 9-0 Jab - 6.5, jac - 2 0> 6 .B(J Indicates the average peak displacement; in all sases but peak (A} of the last reference - a single narrow peak is observed. DSW 167069 STLCOPCB4041227 uwwtnmv .......... .. DSW 167070 STLCOPCB4041228 D. Proof of Structure of (II) 14. Other physical and chemical measurements indicate the atruoture shown above, with 1 ohlorins atom moleoule, bat the location of the chlorine as to ring and position on ring Is uncertain. Figure A)I. Aromatic proton spectrum of (II) Three peaks are seen In this spectrum. Based on their absorption positions the two high field peak3 are assigned to the benzimldazollnone ring and the lower field peak Is assigned to the phenyl ring. Area measurements of these peaks show J.O protons to 5-0 protons. This shows positively that the single chlorine atom is on the benzlmazolinone ring. However, because of uncertain Bpin-spin coupling, 'no definite assignment as to the ring position can be made. Figure B) Aromatic proton spectrum of (V) From measurements of peak area and chemical shift, peaks 4,5* and 7 are assigned to protons in the benzimidazole ring; the remaining peak Is aBBlgned to phenyl ring protons. The areas of peaks 4,5* and 7 are identical and correspond to 1 proton/peak. The analysis of* this first order spectrum for the benzimidazole ring protons leads directly to the Indicated assignment. Peak 4 is assigned as Indicated because of the large shift to lower field observed when unsaturation Is introduced one atom removed from this position. This then allows an unambiguous assignment of structure (II) as l-phenyl-6-chloro-2-benzlmldazolinone. H C-0 --N' Cl DSW 167071 STLCOPCB4041229 15. E. Froof of Structure of (IV) As in Structure (11) the problem is to assign th* position of the y chlorine etom* In th* two-rir.g system. Th* natura of the reaction la auch that there should be 2 chlorine atoma In 1 ring, and 1 chlorine atom In the other ring. Figure C) Aromatic proton spectrum (IV) Four peaks of varying area are seen In this spectra. Based on their absorption positions the high field peak Is assigned to the benzlmldazollnone ring? the remaining peaks are assigned to the phenyl ring. Area measurements of these peaks Indicate one chlorine atom/benzimldazollnone ring and two chlorine atoms/phenyl ring. No detailed analysis ss to substitution positions was attempted. . Figure D) Aromatic proton spectrum of (VI) Seven distinct absorption peaks are seen. No Interpretation is attempted but comparison to Figures B and C suggests a monochlorlnated benzimidazole ring and a dlchlorlnated phenyl ring. Area measurements are In agreement with this interpretation. F. Solvent Effects Before trying to build a convincing argument for the chlorine ring positioning necessary to explain spectra C and D, an attempt was made to utilize the slight variation In chemical shift of o, m, and p protons to be expected In various solvents. Since a strong Interaction between solvent and the N atoms Is likely as well as between the aromaclc TT electrons and solvent, noticable effects can be expected. These effects may remove the overlap of peaks thought to be present In spectra C and D. Spectra of IV and VI in several solvents were obtained. Solvent effects on the observed spectra were observed. The Bpectrum of VI in dloxane gave the best resolved spectrum; this spectrum Is shown as Figure E. DSW 167072 STLCOPCB4041230 16. Figure E) Aromatic proton spectrum of (VI) In dloxane ('*'.7 M). Comparlaon to spectrum B Indicates that peaks 4,5, and 7 are due to the aromatic protons in the benzimidazole ring while the remaining peaks are due to the phenyl ring protons. Determination of protons/peak by Integration and obstrvatlon of repetitive peak separations, indicating spin-spin coupling, shows that each ring exhibits a first order spectrum. The Interpretation of this spectrum Is Indicated. Calculations using the observed chemical shifts and coupling constants indicates the peak intensities in the phenyl ring spectrum are as predicted. This allows an unambiguous assignment of Structure IV as l-(3,4-dichlorophenyl'-6-chloro-2-benzlmidazolinone. 6/62 - R. E. Keller, M. W. Dietrich DSW 167073 STLCOPCB4041231 cJjt IP ll 10 To TUr i*fH S'.M ^(J MMWl ft DSW 167074 STLCOPCB4041232 fAofbuS t\ ***** PAK f0StTK> (ft* -TV THS) DSW 167075 STLCOPCB4041233 K'J] DSW 167076 STLCOPCB4041234 os DSW 167077 STLCOPCB4041235 STLCOPCB4041236 22 SECTION C Introduction BIOLITE ANALYTICAL INVESTIGATIONS Basic data were needed to define the scope and limitations of Blolite as a bacteriostat. This study covered the following problems: 1. Development of method for ppm pentachlorophenol and/or Blolite on cloth. 2. Stability studies - a. Blolite In detergents. b. Coated Blolite In detergents. c. Experimental fungistat In detergent. 5. Retention studies - a. Blolite on cloth from Terg-O-Toireter washes. b. Blolite on cloth from full scale washing machine washes. A. Miscellaneous studies - a. Effect of sterilization of cloth on Blolite analyses. b. Stability of Blollte-detergent-water at l4o*F. c. Determination of Blolite by reduction with sodium biphenyl and measurement of the liberated chloride. Summary 1. A method has been developed for the determination of pc-nta- chloropher.ol and/or Blolite (2-chloroethyl pentachlorophenyl car bonate used aB a bacteriostat-funglstat) on cloth. The method Is based on the hydrolysis of Blolite to pentachlorophenol followed by extraction with chloroform and measurement by ultraviolet absorp tion in alkaline aqueous solution. The method sensitivity Is a few parts per million Blolite and the accuracy Is believed to be within 10# of the amount present. 2. Stability tests run at 80*F. In the humidity cabinet on 1# Blolite (99# assay and <100 mesh) In All showed that approximately 5>0# of the Blolite remained after two months. Approximately 70# remained after two months with 90# assay, 20-100 mesh Blolite In All, Fab and Tide. DSW 167079 A 1. STLCOPCB4041237 25. Accelerated stability tests (one week at 6o*C. which the soap manufacturers claim equivalent to a one-year shelf life) were run on l Blolite In Tide. The Biolite was coated with various materials which might prevent decomposition. A 10$C coating of polyvinyl alcohol Increases the stability of the Biolite in the presence of the detergent from to 80%. Accelerated stability tests shewed approximately the same decomposition for an experimental phenyl pentachlorophenyl carbonate as for Biolite. 5. The Terg-O-Tometer which Is used to determine the effective ness of various deterfents in laundering was used to evaluate Biolite in the detergents. Cloth laundered in the Terg-O-Tometer and air dried contained approximately IT ppm Biolite while the samples washed in an automatic washer and dried in a commercial drier contained 100 to lUo ppm Biolite. Cloth washed In the Terg-O-Tometer where the wash as well as all the rinse solutions are poured (filtered) through the cloth to simulate the full scale washer gave 60 to 160 ppm Biolite on the cloth. These findings indicate that the Terg-O-Tometer Is not equivalent to standard washing machines for studies of this type. The analysis of cloth from ten successive washes showed no build-up of Biolite. Three full scale washer experiments resulted in the following conclusions: (1) Less than 8 ppm (calculated as Blolite) Is present on cloth as pentachlorophenol after the wash, the first and second rinse and the air drying stepB. This represents about lH of the total Blolite present. (2) The pentachlorophenol content of the heat dried cloth increased to 20 ppm or about l8?S of the total Biolite present. (5) Upon sterilization, the pentachlorophenol Increases lr. the washed and dried samples to 60 ppm. About 70^ of the Blolite is hydrolyzed. This shows that the biological testing was carried out with cloth containing 70# pentachlorophenol and 50# Blolite. (4) The explanation for twice the Blolite content in heat dried samples in comparison to tne air dried samples Is not known. Analytical method error and/or difficulties in sampling due to the non-uniform distribution of the Blolite may account for this. DSW 167080 STLCOPCB4041238 24. 4. Analyses show that sterilization does not change the recovery of known amounts of Blollte added to cloth. Approximately 556 of the Blollte In detergent In wash solution Is decomposed In 10 minutes at l4o*F. The state of subdivision of the Blollte affects this decomposition. 1656 decomposition occurs In 10 minutes If the Blollte is added as a solution in acetone. The reduction of Blollte with sodium biphenyl and titration of the resulting chlorides with standard silver nitrate has been used as an Independent method to check the validity of the extractionultraviolet method. Both methods give essentially the same results for the analysis of cloth from washing teBts. Analytical Studies 1. Development of Method for ppm Pentachlorophenol and/or Blollte on Cloth 'r ~ Preliminary results were obtained using a method based on extraction of the clotn In a Soxhlet extractor with ethanol. The optical brlghtener offers serious interference with ultraviolet measurements. Attempts to effect purification by extraction pro cedures proved unsuccessful due to emulsions. Extraction of the pentachlorophenol from the cloth with chloro form In the presence of water eliminates most of the above difficulties. Quantitative extraction is slow because of the entrainment of the chloroform by the cloth and because equilibrium in the extraction is established slowly. This requires 5 minutes of vigorous shaking. To accomplish equilibrium on the Wrist Action Shaker, the samples must be shaken at least 1 hour 15 minutes and preferably 2 hours. All the pentachlorophenol is found In the chloroform layer so that If a known amount of chloroform has been added, quantitative analysis can be made on a measured aliquot. Blollte does not interfere if the solution Is acid. The chloroform solution is washed with 10 ml. 0,1 N sodium hydroxide and the ultraviolet absorption of the aqueous alkaline phase Is measured at J20 nyj. For the determination of Blollte and pentachlorophenol, the cloth Is moistened with 0.1 N 5056 methanol-foO-sodium hydroxide. After standing a few minutes, the hydrolyzed sample Is acidified and the pentachlorophenol extracted In the usual manner. There Is very little background interference using this procedure. The reproducibility of the method is believed to be within + 1056. The method is as follows: DSW 167081 STLCOPCB4041239 METHOD HO. 62-4 SCOPE Determination of Blollte and/or Pentachlorophenol on Cloth Method # 3 The method Is designed to determine the Blollte and/or pentachlorophenol present In cloth at the level of 5 ppm or higher. It la a modified and improved version of Method # 2 developed earlier. PRINCIPLE The pentachlorophenol la extracted with chloroform directly from the cloth suspended In water, the chloroform washed with water and finally with a small volume of dilute sodium hydroxide solution. The ultraviolet absorption of this alkaline solution is measured at J20 nju where sodium pentachlorophenate has maximum absorption. Blollte does not interfere. The cloth is moistened with alcoholic sodium hydroxide and the Blollte Is decomposed Instantly to pentachlorophenol. The total pentachlorophenol is determined. The Blollte is the difference between the total pentachlorophenol and the pentachlorophenol found directly. REA0ENTS Chloroform - A.R. Sodium Hydroxide - A.R. 50# Sol'n. Hydrochloric Acid - A.R. Methyl Orange Indicator Methyl Alcohol - A.R. APPARATUS Burell Wrist Action Shaker 1 - 250 ml. Separatory Funnel > - 125 ml. Separatory Funnels Cary Recording Spectrophotometer with 2.0 cm. Fused Silica Cells 8 or. Narrow Mouth Bottles with Polyethylene Closures Usual Laboratory Glassware STANDARD SOLUTIONS 0.1 N Sodljm Hydroxide - No. 1 - Add 2.6 ml. 50# sodium hydroxide to 500 ml. distilled water and mix thoroughly. No. 2 - Add 2.6 ml. 50# sodium hydroxide to 250 ml. distilled water and add 250 ml. methyl alcohol. DSW 167082 wammmm STLCOPCB4041240 METHOD HO. 62-A lPg.2) PROCEDURE A. Pentachlorophenol 1. Take a 5.0 g. sample of cloth and cut .Into suitable slza pieces or strips and place in a clean dry 8 oz. bottle. 2. Add 150 ml. of distilled water and 6 drops of 1-1 hydrochloric acid. 5. Add, by pipette, 2p ml. of chloroform and shake vigorously for 50 seconds or until cloth is dispersed throughout water and chloroform. 1*. Clamp in a horizontal position on the Wrist Action Shaker and shake with maximum shaking action for 1.5 hours (8 samples may be shaken at one time). 5. Remove the cloth from the bottle with the aid of a wire hook. Squeeze the cloth against the neck of the bottle during the withdrawal to minimize the amount of chloroform discarded with the cloth. 6. Transfer the contents of the bottle to a clean dry 250 ml. separatory funnel. . 7. Drain the clear chloroform layer Into a clean dry 25 ml. ~-aduate and record the volume to the nearest one tenth of a ml. 8. Place 25-50 ml. of dlBtilled water Into each of two 125 ml. separatory funnels. 9. Pipette 10 ml. of 0.1 N aqueous sodium hydroxide (sol'n. No. 1) Into a third 125 ml. clean dry separatory funnel. 10. Transfer the chloroform from the graduate Quantitatively, with the aid of a little chloroform, to the 1st wash water funnel, stopper and shake for 15 seconds. 11. Drain the chloroform into the second wash water funnel. 12. Add approximately 25 ml. of fresh chloroform to the first wash water funnel. 15. Shake both the first and second wash funnel for 15 seconds (these can both be shaken at the same time;. DSW 167083 STLCOPCB4041241 METHOD NO. 62-4 (Pgj) 14. Drain the chloroform In the second wash funnel Into the third funnel containing the sodium hydroxide (# 9 above). 15- Drain the chloroform from the first wash funnel Into the second wash funnel. 16. Shake the recond wash funnel and the third funnel containing the sodium hydroxide for 15 seconds (these can be shaken at the same time). 17. Discard the chloroform layer from the alkaline funnel. 1$. Transfer the chloroform from the second wash funnel to the third funnel containing the alkali. 19. Shake for 15 seconds, and discard the chloroform. 20. Apply vacuum to the top of the separatory funnel and open the bottom stopcock to allow air to bubble up through the solu tion for several minutes or until all the chloroform has been removed (odor). 21. Pour the solution Into a 2 cm. cell and measure the absorp tion In the range of 400 to 2?3 njp using distilled water In the reference. 22. Draw In the background which is a straight line extension of the curve from 400 to ?50 njp. The absorbance measured at the maximum of J20 tip Is corrected for the background from the curve at this wavelength and the difference used In calcu lating the results. Blollte and Pentachlorophenol - Total 1. Take approximately a 5 gram sample of cloth, weighed to the nearest 0.1 gram, cut Into suitable size pieces or strips and place In a clean dry 8 oz. bottle. 2. Add 10 ml. of 0.1 N sodium hydroxide In 50# methanol-water mixture (sol'n. No. 2Stir the cloth arojnd with a stainless steel spatula to make certain that the cloth Is thoroughly wet with the alcoholic sodium hydroxide solution. J, Rln3e off the spatula with water using a total volume of 150 ml. Add 1 drop methyl orar.ge Indicator solution. 4. Add approximately 6-10 drops 1-1 hydrochloric acid solution and shake. The indicator snould be red, showing the solution Is acid. 5. Proceed with the analysis starting with Procedure A, Penta chlorophenol, # ?. DSW 167084 STLCOPCB4041242 METHOD NO. 62-4 (pg. 4) CALCULATIONS ppm pentachlorophenol Vol. of Chloroform (0. D. at J20 - Sol1 n Extracted Vol.of 0.1 N NaOH O.D. at 320 of background) x ^ 23 ' x Taken In ml.______ x (Absorption coefficient** or " pentachlorophenol at 320 nyj) Cell length In cm. x TTwt. sample In g. 104 Corr. O.D. at 320 x 10 x 10* x fraction chloroform extracted 200 x 2.0 x 5-0 Corr. O.D. at 320 x 30 x chloroform fraction Absorption coefficient - (ryr0^`J`f^HngtK, cm.') PRECISION AND ACCURACY No data were obtained for statistical calculation of accuracy or pre cision. The five extracts give better than 90# recovery with known pentachlorophenol from cloth at the 30 ppm level. The reproduci bility is within 1 ppm at the 30 ppm level. The accuracy and repro ducibility are believed better than with Method # 1 and equivalent to Method # 2. DISCUSSION Pentachlorophenol can be quantitatively extracted from water solution by chloroform in one 13 second extraction. However, In the actual extraction of the pentachlorophenol from the cloth, only 60# is ex tracted In the one minute time. Quantitative extraction is obtained using 30 minute shaking. No intermediate shaking times have been run but a 3 minute shaking would probably give quantitative transfer from the cloth to the chloroform solution. In Bhaklng the cloth, water and chloroform, with 23 ml. chloroform, about 21 ml. of chloroform Is the mo3t that can be drained forward. This means that the practical recovery 13 only 83# of the amount present. Thus, two additional extractions are needed for quanti tative transfer of the pentachlorophenol. An alternative procedure could be used where an aliquot of the chloroform is washed and the pentachlorophenol transferred to the sodium hydroxide solution for UV measurement. This is the basis of the present method. DSW 167085 STLCOPCB4041243 METHOD NO. 62-4 -------- CpfTTJ-------- When extractions are shaken by hand, 5 win. Is sufficient for complete extraction whereas 1.5 hrs. Is required using the Burell Wrist Action Shaker. The shaking action must disperse the cloth throughout the solutions,otherwise the extraction will be incom plete In 1.5 hrs. The purpose of the 1 minute vigorous shaking Initially is to thoroughly disperse the sample before the mechanical shaking is started. s' v.`A fe ll Monsanto Chemical Company Organic Research Department St. Louis, Missouri 12/62 - 0. W. Ashworm, R. E. Keller DSW 167086 STLCOPCB4041244 BUSH 25- 2. Stability Studies a. Blollte In Detergents The stability of 1* Blollte In standard All and dry mix All was determined. The samples were prepared in Individual 8 oz. bottles by accurately weighing in 0.2 g. Blollte and adding 20.0 g. of the detergent. At the end of the test period, the entire sample was used for analysis. The dry mix All contained no brightener or perfumes. The control sample was kept tightly capped while the sample (cap removed),was placed In the humidity cabinet. The results of the first series are as follows. The Blollte used was 995* assay and less than 100 mesh. Percent Blollte In Sample Time of Standard All Dry Mix All !l Test Control Humidity Control -------Humidity 1 ; Initial 0.97 1!\ t' 1 day 2 days 0.91 0.88 ' 3 diys 0.87 i* 1 week 2 weeks 0.91 o.8l 1i 4 weeks B weeks 0.81 0.83 0.90 0.86 0.82 0.77 0.67 0.6? 0.46 0.98 0.89 0.82 0.84 0.74 0.58 0.?8 0.?1 0.87 0.85 0.84 0.78 0.65 0.61 0.33 The results indicate moisture may be a contributing f factor in the decomposition. fc A second series of tests were run using 90* Blollte (90# pentachloro - the balance being the tetrachloro analogue of Blollte; i'i with mesh size of 20-100. Several detergents were used in this series. The results are given in the following table. ! i Analyses of Blollte - Heavy-Duty Detergents Up Through Two Months ) (Containing 1# Blollte after 3 days, 1 week, 2 weeks, and 1 month at 80*P. in the humidity cabinet.) Percent Blollte ? day s 1 wk. 2 wks. 1 mo. 2 mo. All - 99% Blollte - 20-100 mesh All - 90% Blollte - 20-100 mesh Fab - 90% Blollte - 20-100 mesh Tide- 90* Blollte - 20-100 mesh Cllmalene - 90* Blollte - 20-100 mesh Beads 0'Bleach (1) - 90* Elo- llte - 20-100 mesh Snowy Bleach (2; - 90* Blollte - 20-100 mesh 0.97* 0.92 0.90 0.90 0.92 0.90 0.91 0.93* 0.65 0.91 0.90 0.92* 0.84 0.85 0.08 0.92 0.90 0.95 1.01 0.95 1.00 0.83* 0.77 0.79 0.84 0.69* 0.65 0.10 0.70 0.85 0.76 0.90 0.78 0.79 0.69 (1) Assay corrected by 0.20* as blank correction. (2; Assay corrected by 0.25* as blank correction. DSW 167087 STLCOPCB4041245 26. Die above results do not show as much decomposition as when the fine mesh (< 100) Blollte was used. The results at the two-month period show that the decomposition is approximately 70% < for all the detergents. The 464 obtained on the first series is pro bably due to the fine mesh else of the Blollte. b. Coated Blollte in Detergents . Dr. J. Baker had 90% Blollte coated with various coating agents at the Wisconsin Alumni Research Foundation. This Blollte was tested by an accelerated test used by the soap manufacturers. The sample Is heated at 140*P. (60*C.) for one week. It Is claimed that this test is equivalent to a one-year shelf life. The analytical data for this test using the method based on measurement of CO* are given In the following table. Heat Stability Studies Sample % Blollte % of In Detergent ___ Original Originally At t>6*C. Remaining Remarks 90% Blollte - 20-100 mesh 99% Blollte - 20-100 mesh 99% Blollte - <. 100 mesh Control - Blollte used In sub- sequent tests 5% Carbowax 6000 10$ Carbowax 6000 2.5% Methocel - Ethocel 5% Methocel - Ethocel 10% Methocel - Ethocel 2.5% Carbowax 6000 MethocelEthocel 5% Carbowax 6000 + MethocelEthocel 7.5% Carbowax 6000 MethocelEthocel 10% Carbowax 6000 + MethocelEthocel 2.6% Polyvinyl Alcohol 5% ,, Polyvinyl Alcohol 7.6% Polyvinyl Alcohol 10% Polyvinyl Alcohol 6% Sugar 10% Sugar 16% Sugar 20% Sugar 26% Sugar 1.00 1.00 1.00 1.00 0.96 0.90 0.975 0.95 0.90 0.975 0.95 0.925 0.90 0.975 0.95 0.925 0.90 0.95 0.90 0.65 0.80 0.75 5% Dextrin 600 0.95 S.T5" o.>9 0.24 0.36 0.3S 0.46 0.39 0.48 0.41 0.45 0.46 0.45 0.44 0.44 0.62 0.71 0.76 0.48 0.49 0.51 0.48 0.39 0.52 46 39 24 36 40 51 40 51 46 46 48 49 49 46 65 0.92) 77 0.93 84 0.91) 51 54 60 60 52 55 % Blollte in original formulation Coated Blollt Sticky-necessary to grind before formulatlng. DSW 167088 STLCOPCB4041246 27. One percent formulations in Tide of the 5, 7*5 and lOSf polyvinyl alcohol coated Blollte samples were analyzed by the regu lar procedure. The values obtained - 0.92 In place of 0.95; 0.95 vs. 0.925 and 0-91 In place of 0.90 - are In close agreement with the theoretical values. The other samples were not analyzed. The percentage of the coating was assumed to be correct and this value was used In determining the percentage of the original remaining. As a check on the uniformity of the coating, three Indi vidual samples (0.2 g.) of the lojf coated mateilal were weighed out, dissolved in approximately 25 ml. of alcohol and 10 ml. of 0.1 N sodium hydroxide were added. This hydrolyzed the Blollte to pentachlorophenol which was determined by measurement of its ultraviolet absorption with an appropriate dilution. The assay figures obtained by this method were 87.0, 86.0 and 86.Blollte. These are In close agreement as well as with the 90% nominal figure and the 91% obtained by the method Involving the measurement of carbon dioxide. Of the coated materials tested, polyvinyl alcohol appears to be the most piomlslng. There Is a trend showing less decomposition as the amount of the polyvinyl alcohol Is increased up to the \0% level. c. Experimental Funglstat In Detergent The accelerated teBt - one week at l4o*P, - was run on phenyl pentachlorophenyl carbonate in Tide. yy% of the funglstat remained after one week. This Is approximately the same as obtained for Blollte. 5. Retention Studies a. Blollte on Cloth from Terg-O-Tometer Washes Experimental washings were run In the Terg-0-Tometer to test the effect of part'cle size of the Blollte. An average value of 17+2 ppm Blollte was found on the cloth while cloth laundered In an automatic washer contains 50-100 ppm. Thus, the Terg-O-Tometer cannot be used to duplicate the results of a full scale washer. To check the deposition of Blollte on cloth by filtration, eleven circular swatches of cloth were washed in the Terg-O-Tometer but the samples were arranged on a Buchner funnel after each cycle In the same order and the solution poured through the swatches after the wash as well as after the first and second rinse. Blollte < 100 mesh was used on one test and 20-100 mesh material was used in a second experiment. The results are given in the following table. j DSW167089 ] STLCOPCB4041247 28. Cloth Sample No. Prom Top to Bottom ppm Total Blollte <100 Mesh 2o-ioO hesVi 1 84 166 2 46 131 10 30 61 11 31 60 The range of 60-166 ppm Is higher than the IT ppm obtained when the Terg-O-Tometer la operated In the usual manner. The data Indicate that Blollte Is retained for the cloth by a filtering action during standard washing machine tests. This work shows that the Terg-O-Tometer tests must be changed In order to simulate the retention of Blollte on cloth laundered In a standard automatic washer. b. Blollte on Cloth from Full Scale Washing Machine Teat3 The analysis of cloth from ten successive washes showed no build-up of Blollte with each successive wash. The average amount found was 6 ppm which Is so low that there is a large experimental error in the determinations. Only one-eighth the normal amount of Blollte was used In this series of experiments. (O.Sflf Blollte In detergent and 0.25# used in the wash.) The results of three full scale washer experiments carried out to show the retention of Blollte on cloth are summarized In the following table. DSW 167090 STLCOPCB4041248 Ij Cloth Sample Washer #1 Bants- chloro- Total phenol as as Blollte Blollte (ppm.) (ppm.) Wssher #2 Total as Blollte Sid. Method AV_a (ppm.) (ppm.) Std. Method (ppm.) Washer #3 Na bl- Re- phenyl ftV' analysis Method (PPm.) (ppm.) COCO Wash 1st rinse 2nd rinse 109 tI'Ic 54.142.61 5?,76,eo 75.73.61 86 + >8 72+~13 66+10 2nd rinse sterilized Air dried Ait dried sterilized 7 60,49 70,97 70,68,66 82,82,79^ 84 + 13 68 + 1 01+1 58,?S,36(2) 37 + 1 61,67 86 Air dried sterilized Of 110 84,66,70'^ 73 + 7 112,64,73 83 19 Air dried + sterilized 65 hra. at 76* 64,69 67+3 Heat dried Heat dried < sterilized 20 76 116 136,99,107 114 16 139,137.148^ 141 4 129 110 123,106,108 112 + 7 166,166,160 162 + 3 * 120 (1) Two eels of samples analyzed. (?) Re-ana lysis of the samples gave 13,9,7 ppm. total. (5) Re-analysls of the samples gave 9 ppm. Blollte - essentially all Blollte removed. VrOu l-iI'vJ ftl DSW 167091 STLCOPCB4041249 >0. Cloth from the first washing experiment was analyzed for both pentachlorophenol and Biollte. Samples taken up through the air dried step contained no more than 8 ppm pentachlorophenol or 7% of the total Biollte. The air dried sterilized sample contained 02 ppm pentachlorophenol or about 70% of the Biollte. The heat urled sample contained 20 ppm Biollte or 18# of the total Biollte. The fungistat activity of all samples were thus determined on cloth con taining 70% of the Biollte present aB pentachlorophenol as all samples were sterilized before running the biological testa. In Washer Test # 1 only one sample of each was analyzed. Tne erratic values make It difficult to draw conclusions. The air dried samplecontains about one-half the Biollte found in the steri lized sample and the heat dried and sterilized sample. Washer Test # 2, Involving triplicate samples, was made to determine the reproducibility of the sampling. The large difference between air dried and heat dried samples is again noted and unexplained. There is good agreement between the sterilized and unsterilized air dried samples. The reproduelblllty of the wash sample before rinsing Is poor. This value does not decrease rapidly with two rinses which shows the tenacity with which the Biollte Is held by the cloth. This cannot be called adsorption because, If it were, the amount on the cloth would be the same when using the Terg-O-Tometer under similar concentrations. The results of the third washer experiment show a maximum variation of four-fold between air dried and heat dried sterilized samples. Two additional samples of the air dried were run at a later date and the values of t>7 and 61 agree nicely but do not agree with the average of .37 + l obtained originally. A check of the analyti cal method disclosed no serious errors in the procedure. A very non-uniform deposition of the Biollte on the cloth might contribute materially to a non-representatlve sampling error. The analysis of an additional sample of heat dried cloth agreed better with the value obtained previously. The reduction of Biollte with sodium biphenyl and titra tion of the liberated chloride with standard sliver nitrate was developed and used as an independent method of analysis. Results showing 66 ppm and 120 ppm for air dried and heat dried samples from Run #3 confirm that the difference in Biollte content of air dried and heat dried clcth la real and that the dsta obtained with the extraction-ultraviolet method are of the correct order of magnitude. Samples of the air dried and heat dried cloth were re analyzed and only a 9mall amount of Biollte was found. This shows that all extractable Biollte was removed from the cloth by the analytical method. "Mmmmrnmmmm DSW 167092 STLCOPCB4041250 >1 4. Miscellaneous Studies a. Effect of Sterilization of Cloth on Blollte Analyses To determine the effect of sterilization on the analysis, a aeries of experiments were run where a known amount of Blollte was added In acetone solution to a swatch of cloth and this, In turn, was analyzed. The swatches used were unwashed, washed with water only and washed with Tide. Residual amounts of detergent or other Impuri ties left on the c^oth were considered as possible sources of trouble with the method. The results given In the following table show that reco veries are generally better than within +. 10# of the amount added with outside variations of + 20$. Effect of Sterilization of Cloth on Blollte Analyses Sample and Treatment Blollte Added as ppm Total Pentachlorophenol and Blollte Reported Bloll Plail in 1! M Clo11 th n n - Unwashed Unwashed Unwashed Unwashed - Sterilized Acetone Acetone - 11 t! H 11 11 M it ti n n H Sterilized - Unwashed - Unwashed - Sterilized - Unwashed - Unwashed - Sterilized - Washed with Water If - Washed with Water - If tl Acetone If - Washed with Water tl - Washed with Water - H 11 Sterilized N - Washed with Water n - Washed with Water - 11 Sterilized ti - Washed with Tide + l! ti Bleach - Washed with Tide + 11 i Bleach + Acetone - Washed with Tide + Bleach it - Washed with Tide + Bleach - Sterilized 11 n - Washed with Tide * Bleach ft ii - Washed with Tide * Bleach - Sterilized 0 0 0 0 50 50 100 100 0 0 50 50 100 100 0 0 50 50 100 100 4 5 4 5 49 57 94 105 0 0 66 56 122 107 0 0 67 56 116 75 DSW 167093 STLCOPCB4041251 32. b. Stability of Blollte-Dctergent-Water at l4p*P. A study to determine the extent of degradation of Blolite In All during the washing step at l4o*P. was carried out. In one experiment, the Blolite was added to the detergent-water solution (l) at 140*P. as a solid. In the second experiment, the Blolite was added In an acetone solution. Vhls wash solution turned turbid immediately and stayed turbid more than 10 minutes. This probably Is caused by excess Blolite precipitated in colloidal form which hydrolyzed faster than Blolite added as a solid, The results In the following table show that less than 5# of the Blolite would be decomposed In the normal 10-mlnute wash cycle. Percent Blolite Decomposed to Pentachlorophenol Time in Minutes Added as Solid Added In Acetone Solution 52 10 5 20 10 -30 15 40 22 50 29 60 32 90 46 120 57 11 16 24 31 38 44 48 66 74 c. Determination of Blolite by Reduction with Sodium Biphenyl and Measurement of the Liberated Chloride The sodium biphenyl method for the analysis of Blolite on treated cloth consists of the following operations. A 5.0 g. cloth sample (diced) Is covered with 30 ml. chlorine-free xylene and stirred for several minutes. A 10 ml. aliquot of sodium biphenyl reagent is added and the sample mixed 5 minutes. The excess sodium Is reacted with 1 ml. ethyl alcohol. Five ml, of fresh 3# hydrogen peroxide Is added and the sample is boiled 10 minutes. After cooling, 100 ml. acetone and 1 ml. Btrong sulfuric acid (l to 1 concentrated sulfuric acid to water by volume) are added. The sample Is stirred thoroughly and the solution is decanted off. The cloth 1b extracted four more times using for each extract 5 ml. of distilled water, 100 ml. acetone and 1 ml. 1 to 1 sulfuric acid. The separate extracts are collected and titrated with 0.0025 N 3llver nitrate to potentlometric endpoint using glasc-sllver electrode Bystem and an L & N expanded scale potentiometer. Analytical data obtained using thl3 procedure are reported In the following table. DSW 167094 STLCOPCB4041252 33. Sample 1. Xylene Solution of Pentachlorophenol Ml. Sodium Biphenyl 5.0 Equivalent Biol \e Added Found LiULdl iPHrol 100 98 100 98 Remarks CloII th Absle nt 2. Xylene Solution of Pentachlorophenol Plus 5.0 Orams Control Cloth 5.0 100 77 5.0 Oram Cloth Control Present ; 3- Same as Sample 2 10.0 100 93 5.0 Gram Cloth Control Present 1 4 Treated Cloth Air 10.0 i Dried, 3rd Washer i i i c ** Treated Cloth Heat 10.0 i Dried, Jrd Washer i 86 36,38,57,61 ppm Blollte by UV Method 120 129,137,146 ppm Blollte by UV Method This work was carried out to provide data for studies under Job No. 4162 - "Soap and Detergent Bacterlostats". Messrs. K. L. Godfrey, D. P. Roman, J. W. Baker, J. P. Speyrer and J. R Wiedemann carried out the Terg-O-Tometer and full scale washing tests, the special sample preparation. Including the sterilization studies, and the preparation of coated Blollte which are given in this report. 12/62 - R. E. Keller, D. B. Hines, 0. W. Ashworth DSW 167095 STLCOPCB4041253 SECTION D Pai NMR Analysis of Process Reaction Products Introduction In the development of the new dlbutyl phenyl phosphate process, analytical methods were needed to evaluate the two major Bteps of the process: (1) POCl* + phenol, and (2) (0O)POC1 + butanol. In both cases several by-products are formed along with the major product. A method was needed to characterize the reaction mixtures and to determine the yield of the desired product. Summary P31 NMR methods were developed to analyze mixtures from both steps In the process. Several by-products were Identified. Major and minor components were determined quantitatively. The following components were Identified In the reaction mixtures examined: P0C1*, (0O;POC1*, (0O)*POC1, (0O)SPO, (BuO)jPO, (BuOM0O)PO, (BuO;(0O)PO and two pyro compounds. The developed methods will measure 0-100# of a given component, and are considered accurate to about _+ 2# absolute [based on total phosphorus containing compounds). However, It was not found possible to analyze accurately for both P0C13 and (0O)POC1* since the P31 NMR peaks of these materials overlap. A combined analysis of these materials can be made. The developed methods provide a fast, comparatively accurate, non destructive method for quantitative analysis of sample mixtures of phosphorus compounds. The various components are Identified by Inspec tion of the spectra. The method is unaffected by components which do not contain phosphorus. Analytical Studies The developed methods are based on the difference in chemical shift of the various phosphorus containing components. In a mix ture these components were Identified using chemical shift data ob tained from the pure materials. Quantitative analysis was performed by measurement of the area of each peak, the area being proportional to the concentration of the component. Samples from the laboratory and pilot plant were examined, covering both steps of the process. The data obtained were used to optimize yields and to determine the nature and quantity of Impurities present. Data and additional details can be found on Analytical Data Sheets filed in the Analytical and Spectroscopy Oroup. DSW 167096 STLCOPCB4041254 METHOD NO. 62-32 NMR Determination of Reaction Products from the Dlbutyl Phenyl Phosphate Process A, Step I - Reaction of POCls with Phenol SCOPE This method describes a phosphorus NMR procedure for the determina tion of the amounts of the various phosphorus components formed in the reaction of P0C1* with phenol. The phosphorus components can be determined to about 2 mole % (of the total phosphorus compo nents) In the range 0-1005*. PRINCIPLE The P31 NMR Bpectrum of a typical reaction mixture (see Figure 1) contains peaks for each of the phosphorus containing components pre sent. These peaks were identified by reference to spectra of the pure materials. The concentration of each component is determined by measuring the area of the peak associated with each component and comparing to the area of all peaks in the spectrum. APPARATUS AND REAGENTS High-Resolution NMR Spectrometer capable of measuring Psl (a Varian HR-60 was used). Equipment for measuring area such as a planlmeter or electronic Integrator. PROCEDURE 1. Instrument Settings Choose optimum settings to give 3lgnal display most convenient for the integration method to be used. 2. Calibration No calibration is necessary. DSW 167097 STLCOPCB4041255 METHOD NO. 62>32 Ipg. 2) ?. Sample Analysis Pill S mm. thin walled NMR cells with sample (add CCI4 to reduce viscosity If necessary). Adjust spectrometer for maximum homo geneity and minimum drift. Introduce sample and record spectrum (and integral). Add H*P04 capillary to sample, rerun and obtain spectrum with scale calibration. Calibrate spectra and Identify components by chemical shift values. Determine area of each component by means chosen. Sum up areas of all peaks In spectrum. Determine the mole |( of a given component using the equation: Mole # X Area X 1 ,^ nx ' Total"Area * 100 where n - number of phosphorus atoms per molecule Total Area Area 1 ni where 1 * the phosphorus compounds present If both P0C1 and (0O)POCla are present, the amounts of these components are reported as a sum of the two concentrations, since the peaks of these species are incompletely resolved. Area measurements were made by planimeter In the examples reported here. D* Step II - Reaction of (0O)POC1 with Butanol SCOPE This method describes a phosphorus NMR procedure for the determina tion of the amounts of the various phosphorus components formed In the reaction of (0O;POC1* with butanol. The phosphorus components can be determined to about + 2 mole % absolute (of the total phos phorus components) in the range 0-100#. PRINCIPLE See Section A. A NMR spectrum obtained from a typical sample Is shown In Figure II. APPARATUS AND REAQENTS See Section A. DSW 167098 STLCOPCB4041256 PROCEDURE 1. Instrument Settings See Section A. 2. Calibration No calibration is necessary. 3. Sample Analysis See Section A. METHOD NO. 62-32 -------Cpg."71----- Monsanto Chemical Company Organic Chemicals Division St. Louis Research Department 12/62 - M. W. Dietrich, R. E. Keller DSW 167099 STLCOPCB4041257 DSW 167100 STLCOPCB4041258 EET-HOS .VC. e2-32 VPS- 3. ///< J DSW 167101 STLCOPCB4041259 ">S SECTION E Jdent 1 f 1 cat t on of Tr.hl tttors in Competitive Hydroca,-ton Ester Fluids I"*rodjctlon This 3tudy was undertaken to characterize the oxidation inhi bitors present, in competitive turbofan fluids. The information was needed to better select an Inhibitor for a Monsanto C4o alkane product. . The techniques applied in the identification were column chroma rographv, ultraviolet absorption spectroscopy, infrared spectroscopy and nuclear magnetic resonance spectroscopy Summary Esso, Texaco and Socony turboban fluids were found to contain one or more components with an aromatic secondary amine structure. The findings suggest components of the type - P i H N (A 196) Ana 1 y11cal Studies Following Is a chart of the work carried out. } ( Also attached are the ultraviolet spectra of the three turbofan fluids examined and the typical ultraviolet spectra of the suggested components. i i : fI i f' 1' i[ iI DSW 167102 STLCOPCB4041260 Experimental Competitive Turbofan Fluids _____ L--7>g Esso Structure Data for Inhibitor Texaco' ' L-793 Socony___ Column Chromatography Ultraviolet. Material "Per Se" Two aromatic inhibitors -------- -------- Spectra characteristic of - Spectra characteristic of " H ----- H 1) ^y- M-R .-v Speotre ohareeterletH of a mixture of H n R-R_<^ N-R U) Aromatic system (aliphatic aroma tic tertie*-y amine) (hi#ubatituted eromn tic secondary amine "ort-ho" position - n > Aromatic system :n> phenyJ.ene diamine type) Infrared Chromatographic Predion# R R A-196 NKR Chromatograph!c Fraction* and Material "Per Sa" 17.) Aromatic a) Mulri--#yst,em elth e pare nM trl-euhji atltutlnn. -j b) Multi system - all S trl subBtlt.utlon e) Heterocyclic nitro gen system. Ho-prl. nr sec. amine -carbonyl or ether oxygen. Tuo aromatic proton One aromatic proton One aromatic proton algnal, signal#, X and 11. signal, 1. but different from 1 and 11. II, ratio aromatic Signal strength Indicates hydrogen to aliphatic 1/5 amount prtaent In hydrogen, at least 3/l. L- 79? and L-7*>2 Conclusion! The fluids contain one or more components as Inhibitors with an aromatic secondary amine structure. Th findings suggest components of the type ' ` DSW 167103 STLCOPCB4041261 STLCOPCB4041262 STLCOPCB4041263 STLCOPCB4041264 STLCOPCB4041265 L; ! l'1 fi ' ft STLCOPCB4041266 SECTION P Evaluation of Infotronlcs CRS-1 Integrator for NMR Signala *2. Introduction The Infotronlcs CRS-1 Digital Chromatograph Readout System is designed for Integration of signals obtained from a gas chromatograph. It has been found to be very satisfactory in this use. Since It possesses potential advantages of speed and accuracy over other methods presently available for integration of NHR signals. It has been evaluated for this use. Summary The Infotronlcs Corporation Model CRS-1 Digital Chromato graph Readout System has been evaluated as a method of Integrating N**R signals. This instrument was evaluated with and without signal preampllfication using both the signal taken directly from the Varlan HR-60 NMR spectro meter and the base line stabilized signal obtained from the Varlan Model V-?5?l integrator. Two major limitations In usefulness of this Instrument, were found. Difficulty In zeroing the integrator before Integration was observed when using the signal obtained directly from the NMR spec trometer as well as a tendency of the zero position to drift. These difficulties were minimized by using the base line stabilized signal from thr Varlan Integrator. The Becond limitation observed was a tendency to discriminate against peaks with a low signal to noise ratio. In a sample containing both a strong and a weak peak, the weaker peak may either be omitted, or an improperly low integral value recor ded. With sufficiently concentrated samples of high signal to noise ratio, this instrument was found to perform well, being both accurate and rapid. r y * \ : _ I * - DSW 167109 STLCOPCB4041267 *5. Analytical Studies A. Description of the Infotronlcs Integrator The Infotronlcs Model CRS-1 Integrator is designed specifically as an adjunct to laboratory gas chromatographs. The instrument Is intended to produce a printed record of the areas of the chromatographic per'.'s, with the time of emergence of each peak shown opposite the recorder area. Input to the integrator Is an electrical voltage of pO milli volts nominal maximum (100 millivolts Is permissible); the time integral of the Input voltage Is produced, the recorded value being 100 times the value of the integral In millivolt-seconds. Positive input voltages only are integrated. Structurally, the Integrator Includes two components, the integrator proper and the printer which produces a printed tape listing the Integrals of successive peaks. Functionally, the Integrator component In turn contains two principal elements, an integrating unit and a peak-sensing unit. The integrating unit comprises a voltage-tofrequency converter and a counter; the peak detector 1b essentially a differentiating element which detects changes of slope indicative of the start, top and end of a peak. The sequence of operations of the integrator and printer is as follows: Input Operation Start of peak (positive slope exceeding selected level). Start counting. Top of peak (zero slope). Transfer time reading to printer. End of peak (negative slope less than selected level). Transfer accumulated count to printer, print count and time. Controls for operating the integrator manually are also provided, and the printer Includes a control for manual printing of total counts for a serleB of peaks. B. Connection of the Integrator to the NKR Spectrometer The radio frequency unit of the NMR spectrometer provides outputs for both oscilloscope and recorder. Tne arrangement of these (when using phase detection of the radio frequency signal).is shown in Figure 1. DSW 167110 STLCOPCB4041268 The total resistance in scries with the spectrometer output is less at the oscilloscope terminal than at the recorder terminal, so the CRS-1 Integrator was first connected directly to the oscilloscope terminal. Initial trials, with the voltage-frequency converter and slope deteotor InputB of the Integrator connected together, showed an apparent large zero offset. This was found to be caused by an alternating voltage present in the slope detector input. (The slope detector includes a magnetic amplifier energized at the line frequency.) Connection of a capacitor across the slope detector .r lr.'.put served to bypass the alternating valta&a present here, but to avoid excessive damping of the oscilloscope it was necessary to add a resistance In series, as shown in Figure 2(a). Because the input resistance of the voltage-frequency converter is 100 kilobits t and thef input resistance of the slope detector is 2 to po kllohns, depending upon the sensitivity setting, the result of using this circuit was a decrease of integrator sensitivity combined with an apparent decrease of recorder and oscilloscope sensitivity. A similar result was obtained by connecting the integrator directly to the recorder terminal of the spectrometer; the shunt capacitance at that terminal (see Figure 1; provided the required a.c. bypass. A possible means cf avoiding a.c. feedback from the slope detector and simultaneously reducing loading cf the spectrometer output circuit was to place an isolating amplifier between tne voltagefrequency converter and the slope detector. A transistor emitter follower was tried, as shown in Figure 2(c;; it was effective for isolating the slope detector from the integrator input circuit, but the transistor base current was sufficient to produce an objectionable offset of the zero of the voitage-frequer.ey converter. A more elaborate isolating amplifier v.as tried in the form of a Leeds and Horthrup h'o. 965^-2 electrcric D-C null detector. It was connected as shown in Figure 2(c>. The 1 megohm resistor in series with the input to the null cetector served to reduce the sensitivity of this unit to tr.e required level. It also slowed the response of the null detector; a voltage divider migr.t have been preferable for reducing the input voltage*. Ir. general, how ever, performance of the apparatus assembled as in Figure 2(c) was satisfactory. Because the null a-.tector hat beer. tor. owed from tne manufacturer and had to be returned after a short time, some alternative amplifier was sougr.t. V. . > y.,The alternative chosen v;as the use of a Leeds and %*V^ i *" 1:;' o. 7^01 pH meter as a preamplifier. The connections were as shewn in Figure y. The good linearity ar.d low output reoittar.ee of the pH meter permitted it to be used to drive both tne voltage-frequency converter ar.d the slope detector. As set up, the range cf the pH meter was * 50 millivolts. A range perhaps twice t.-.is wide v;ould have teen Tetter to prevent tne meter being driven off-scale on large peaks. In other respects, performance of the pH meter as a preamplifier was satisfactory. DSW 167111 STLCOPCB4041269 *5. With all of the circuits tried. It v:as difficult to obtain a suitable compromise between sensitivity to small peaks and sensitivity to r.oise. The effect of large amounts of damping was not tried in the present work, but presumably the discrimination between noise and spectral peaks could be improved by use of greater damping with correspondingly slower sweep rates. A filtered output Is available from the spectrometer at the recorder terminal, as indicated ir. Figure 1. To make the test use of this output, it would be necessary to apply a preamplifier because of the high Internal resistance of the spectrometer and the low resistance or the integrator. C. Evaluation 1. General Comments All measurements were made with the zero of Ir.fotronics integrator adjusted so as to give a counting rate of <10 counts/sec. (manu facturer's recommendation). The effect of higher zero settings is discussed later. By recording the CH.- quartet in CKaCHaOH at various sweep rates, the resolution of ti.. Integrator was determined to be better than one peak every 2.0 seconds. Tne manufacturer reports one peak every 1.5 seconds and that resolution car. be improved considerably if data Is recorded on magnetic tape. Accurate phase settings appear unnecessary, see Figure ^. 2. Operation without Preampllflcatlor. . With the Infotronlco integrator connected to the recorder output of the HR-60 spectrometer a sample was examined which contained two peaks in tire area ratio 6.0/1.0. Signal intensity was varied by adjusting n?. The results obtained are given in Table I; increasing total count indicates increasing signal. Table T Effect of Signal r-^er.slty or. Accuracy Total Counts on Integrator 13.000 + cOO '5,000 + 1,500 53.000 " 2,000 162,000 + 10,000 Observed Area Ratio* Infotronics Integrater Tlar.imeter ' <="=> 5-9? + 0.^5 5.63 + 0.20 6.o3 ------ 5-55 i 0.30 ------- * Actual area ratio 6.00 When the base line stabilized signal obtained from the Varian V-5521 Integrator (spectrum position) was used as in input signal for the Ir.fotronics integrator, the same biasing against weak peaks was observed. pSW 167112 mar .inifnTni>'j>iiwfin Wiatuu STLCOPCB4041270 5, Operation with Preampllficatlon a. pH Meter At low counting rates (weak signals) the same bias against weak peaks was observed. At high counting rates a bias against strong peaks va6 observed apparently due to over loading of the pH meter. For these reasons, no detailed study was mads. b. D. C. Null Meter A synthetic mixture was prepared containing components of 61.1, 50.0 and 6.9 mole percent phosphorus. Signal Intensity was varied by adjusting tit, signal to r.olse ratio was varied by adjusting the frequency response. Representative spectra are found In Figures p-8; the data obtained are summarized In Table II (attached;. The results obtained are considerably better than those obtained with no preamplification, but the bias against weak signals remains. To determine the effect of background level on accuracy, the relative areas of several of tne multiple! components in the P31 spectrum were obtained at various background readings. n.s the background was increased, the area ratio decreased approaching the correct area ratio (with and without back1 ground subtraction). However, at the high background level needed to obtain the correct area ratio, the background was a major part of the total count. Since peaks with different line widths would have different backgrounds, no simple method is available to accurately subtract the contribution of the background from the observed count. Surcested Operating Procedure a. Connoct recorder output of HR- 0 to input of a preamplifier, b. Cor.nect output of preamplif ic-r to input of Infotrcnics integrator. c. After warn-up of equipment, adjust zero sotting of Infotronlcs integrator to give a.counting rate of less than ten counts/second (adjusting the red probe paddles if necessary;. d. Switch function control switch of Infotronlcs integrator to automatic (integration). e. Record spectrum and integral. ess total button on calculator. (If spurious peak3 are recorded. Just the sensitivity control of the Ir.fctronics integrator to ve decreasing sensitivity and repeat steps c-f., DSW 167113 STLCOPCB4041271 Ut` *7 E. Fusibility and Recommendations Under the operating conditions investigated* the Xnfotronlcs CRS-1 Integrator Is not satisfactory as an lnstrunent for general use In Integrating NMR signals. In certain cases of samples with strong signals* its operating speed may prove useful in obtaining area measurements from a large set of similar sasples (where Its accuracy on one of the samples can be Independently determined). 12/62 - K. W. Dietrich, M. M. Trump* R. E. Keller DSW 167114 STLCOPCB4041272 Table II Data Obtained Osins D. C. Hull It:ter HR-50 Instnur'ciit Setting 55 db In., !IA 4 70 Ob In., HR - 4 53 <5b in., HR - 1 70 db in., HR - 1 A 61.1 A r*\iA l D 30.0 _C_ 8.9 Snnole Conpojtltlon , 13y lmotronicA Integrator A BC te.2 l.j 29-7 0.7 8.1 0.8 63.4 + 0.6 30.2 0.8 6.4 0.5 62.8 1.2 30.4 0.8 6.8 0.6 67.1 0.4 29*7 0.4 3.3 0.2 By Plonlmctor ABc 64.9 25.1 10.0 60.7 30.8 8.4 60.0 29.7 10.3 63.7 26.6 9.7 U i 09 DSW 167115 STLCOPCB4041273 yig. 1. Output Circuit of V^ll ffoftloproiuenc/ Uoit (KR Phaso Do toe tor). DSW 167116 STLCOPCB4041274 50 -vWAt+OM 4x*r + O- ^ c#s-t /** -<2> 0 j5 A> /<n> ^4/^ V/cA Aj j/ox- Jrttrtr * stop* vV/<r,Aw. o M> o- ^ ^ tv a/^// /r~ mj */rtrt'S' . pig. 2. Clrcultn for avoiding feedback of a.c. from slope detector Into integrator. DSW 167117 STLCOPCB4041275 Vlg. 3* Connection of pH neter a* preamplifier. DSW 167118 STLCOPCB4041276 STLCOPCB4041277 |(rF Kkiw^oiHi >tKH rK/ioxfo DSW 167120 STLCOPCB4041278 STLCOPCB4041279 STLCOPCB4041280 SECTION 0 NMR Determination of Methyl Lactate In Plrst Step Reaction Mixtures Introduction In the development of a synthetic lactic acid process. It was found that an analytical method was needed to determine the methyl lactate (KL) In first step reaction mixtures. NMR spectra of the pure materials, as well as typical reaction mixtures, were obtained and analysed. It was found that an NMR peak specific for the methyl of the ester in the presence of methyl alcohol and residual lactonltrlle could be used for analytical purposes. Summary A method was developed based on the measurement of the area of the methyl peak of the ester in ML. The weight percent ML Is determined from a calibration curve obtained from area measurements of standard mixtures of ML and methyl alcohol. With this method it is possible to determine the weight % ML covering the range 0-100* with an accuracy of about + l absolute. Other methyl esters are the only components expected to Interfere with this method. The method developed is preferred to a gas chromatography pro cedure when precise data are required. The NMR method is less rapid than the gas chromatography procedure and it will probably not be the method of choice where many samples and the need for lesB precise results are Involved. Analytical Studies t'o analytical studies were carried out. The VPC method developed was chosen for routine analysis for the reasons given above. The NMR method will be used to provide more accurate data when needed, such as confirmation of doubtful VPC results. DSW 167123 STLCOPCB4041281 T METHOD NO. 62-2? NMR Determination of Methyl Lactate In First Step Reaction Mixtures SCOPE This method describes a proton NMR procedure for the determination of the concentration of methyl lactate in reaction mixtures con taining methyl lactate, methanol, and Impurities at relatively low concentration levels. The methyl lactate can be determined to about + ljf absolute in the range O-lOOjC. PRINCIPLE The proton NMR spectrum of methyl lactate (see Figure I) contains peaks for the OH, H and two types of CHs present In methyl lactate. The same spectrum (OH peak shifted) Is observed for reaction mix tures containing methanol and Impurities (see Figure II). ThiB analysis Is based on the peak area of the methyl group of the ester. The other peaks in the methyl lactate spectrum cannot be used since Impurities expected to be present would interfere In these measurements (other methyl esters would interfere with the measurement described). APPARATUS AND REAGENTS High-Resolution NMR Spectrometer (a Varlan HR-60 was used). Methyl Lactate - Reference of at least 98# purity. Methanol - reagent grade. Synthetic mixtures covering the concentration range of interest. The mixtures used were: Welfiht,.^ Methyl Lactate Methanol ?5-0 40.2 4?. 9 47-9 51.7 54.9 65.0 59.8 56.1 52.1 48.3 45.1 DSW 167124 STLCOPCB4041282 METHOD HO. 62-22 ------- CpgTTJ--------- PROCEDURE A Instrument Settings The settings given are for a Varlan HR-60 Spectrometer equipped with V-5521 integrator and a Mostly Autograph X-Y Recorder. V-4511 Rp Unlti 80 db In Recorder Level: Maximum Receiver Oaln: 5 Frequency Response: WL0 Detector V-J521 Integrator: Input Level: 650 Output: Coarse X.l Pine X.l Frequency Response: 20 cps Autograph XY Recorder: X: 100 sec. full scale Y1 500 mVo - full scale Slow Sweep Unit: Increase 1 x 100 Sample: 5 mm., spinning B. Calibration Pill precision NMR cells (Varlan or equivalent) with the prepared synthetic mixtures. Adjust the spectrometer carefully for maxi mum homogeneity and minimum drift. Using the reference mixture with highest concentration methyl lactate, record the Integral curve. Make any adjustments neceasary so that this Integral Is near recorder full scale. Also, make any adjustments neces sary to optimize the appearance of the Integral curve. In sequence, run the set of standard mixtures making spectro meter adjustments when necessary. Obtain as many Integral traces for each sample as needed to give the desired measure of precision. On each Integral trace, draw parallel lines through the base line before and after integration of the ester methyl peak in methyl lactate. Measure the distance between these baselines for each trace with an accurate ruler. Calculate the standard deviation (If desired) for each standard mixture. On coordinate paper, plot the areas of each sample against the percent, by weight, methyl lactate. Draw the best smooth curve through these points. The working calibration curve set up for the method Is shown In Figure III. DSW 167125 STLCOPCB4041283 METHOD NO. 62-22 ------- CpgT-5?--------- C. Sample Analysis Prepare staples, obtain and analyze spectra by the procedure described for the synthetic mixtures, (if the samples and standards are run on different days, one or more of the standard mixtures should be re-run and the results compared to those obtained previously. If necessary, appropriate corrections In the areas obtained for the samples should be made.) Compute the peak area for each sample and equate this to the weight percent methyl lactate using the calibration curve. Monsanto Chemical Co. Otganlc Research Department St. Louis, Missouri 8/62 - M. Dietrich, R. E. Keller DSW 167126 STLCOPCB4041284 K#*t tk lOMitic "w-M 5-G I */<: t/>y t o o IV'I V-1 n DSW 167127 ' vyl jvl | ;il vl STLCOPCB4041285 ) tm *tToVvf*tDvT4ol*fH. i iNtit |o 3d&H94Ti(&0 >V- (fv ?o 7orU U.t) HETHC3 NO. i.2 -2 2 t 1 , > .* % r1 DSW 167128 STLCOPCB4041286 DSW 167129 STLCOPCB4041287 SECTION H X-Ray Diffraction Studies of Pentachlorophenol Introduction Caking and sublimation problems with plant pentachlorophenol were thought to be caused by crystalline form transitions. X-ray diffraction studies with a Norelco X-ray Diffractometer were carried out to provide basic data about the crystal forms and their transformation. Special sample preparation techniques were developed to overcome particle size and preferred orientation problems. A heated sample holder operating In the range of 25-100*C. was constructed to permit direct measurement of crystal transitions too rapid to be followed by Intermittent sampling. Summary Results show that different diffraction patterns are given by pentachlorophenol When held above or below the transition tempera ture of approximately 6o*C. The transition Is reversible. The more complex diffraction pattern of technical pentachlorophenol Indicates the presence of one or more crystalline Impurities. Quantitative measurements in the 29 range of 52.0* to >4.5 were used to evaluate effects on the transition rate by chemical Impurity, storage form, storage temperature, and crystal seeding. These studies indicate that the crystal change In Itself Is not the cause of caking of technical "Penta" In storage. Details of this work not reported here appear In Research Progress Report **304, No. 1, entitled, "Pentachlorophenol" by M. E. Olbbs, R. W. Bucknell and D. B. Hines. DSW 167130 STLCOPCB4041288 Analytical Studies A. Development of Techniques 1. x-ray diffraction studies by pressed disk techniques Problem of sample preparation were encountered In Initial X-ray powder diffraction experiments with prntachlorophenol. The crystals are soft and it Is difficult to grind them to the fine powder (200 mesh or smaller) required for powder diffraction work. The crystals are also highly susceptible to align ment along crystal planes (preferred orientation). Accurate determineticn of relative intensity of the various diffraction peaks necessary for quantitative analysis depends on uniformly small particles with completely random orientation. . It was found that 1?0 mesh "Penta" powder could be pressed into smooth, dense disks at pressures as high as 16,000 pounds per square lnoh, the maximum pressure developed by the laboratory Carver Presa. Three grams of powder pressed in s 1 J/B" diameter, non-evacuable die gave a disk approximately 2 mm. thick. This disk can be substituted for the specimen holder in the Norelco Piffractometer and its pattern readily measured. This technique, however, produced diffraction patterns exhibiting extreme preferred orientation with all peaks highly suppressed except for the one at 12.2* 20. Putting this technique on a quantitative basis appeared rather difficult, and alternative solutions were explored. However, the pressed disks look promising for future applications as a means of increasing sensitivity for a minor component or perhaps in the suppression of the diffraction pattern of an lntarferrlng component. 2. X-ray diffraction studies with nujol mulls of pentachlorophenol ' The problems of particle size reduction and preferred orientation in "Penta" diffraction samples were largely DSW 167131 STLCOPCB4041289 59- overcome by preparation of a mull of Penta and NuJol. The mull la prepared by weighing 0.2 grama Nujol Into a 2 ml. eteinleai ateel W1Q-L-BUQ grinding vial. Penta la added equivalent to exactly 5.5 timea the weight of Nujol. Prilled Penta may be ueed directly In pre paring the mull but flaked Penta waa pre-ground on a Wiley intermediate mill to 40 mesh. After the grinding vial la charged, two 1/4" stainless steel jails are added. The vial la capped and the contents ground for 5 minutes in a model 2110B WIG-L-BUO. The contents of the vial after grinding are transferred to a Norelco standard aluminum powder diffraction specimen holder and a plane sample surface Is prepared by pressing with a microscope slide or other smooth flat-surfaced object. The diffraction pattern Is recorded using the following instrument settings on the Norelco Diffractometer and Electronic PaneIt 55 kilovolts, 25 milllamperes, medium mlllisnpere range control, 2 ratemeter scale factor, 0.8 multiplier, 4 time constant, proportional counter, 1675 counter voltage. If the total diffraction pattern is of interest the sample is scanned over a 20 angle range of 10-50* at a rate of la per minute. For measurement of the ratio of the two crystalline forms present, the 20 regions of 52.0 to 54.5 are recorded at a scan rate of 1/4* per minute. The peak height ratio of the intensity peak at 52.7* 20 to the peak at 55.0* 20 was used as an empirical representation of the amount of the higher temperature crystal form present. The work necessary to put the method on an absolute basis was considered Impractical because of the difficulty of preparation of standards with known ratios of crystalline forms. 3. X-ray diffraction studies at variable temperature conditions In the exploration of means to accelerate the crystal form transition, a study was made of the transition rate at temperatures Just below the transition temperature. A heated specimen holder. Fig. 1, was constructed to permit measurement of the change m diffraction pattern with time as the temperature was varied. The special DSW 167132 STLCOPCB4041290 holder was milled from a solid 5/8" x 1 5/8 type 2024-T^ rectangular aluminum alloy bar. The holder la heated with a Watlow 0IE2A Cartridge Heater. 100 watt, 115 volt, available from the Watlow Slectrlo Kfg. Co., St. Louis, Mo. The raised "island" in the sample cavity prevents flssuring of molten samples upon solidification and also houses a No. 50 tefloninsulated, iron*Constantine thermocouple probe. The temperature is registered on an Leeds and Northrup Speed-0-Max Model H recorder equipped with a 0-200*0. lron-constantlne scale. Electrical connection of heater and thermocouple were made through a hole drilled in the diffractometer x-ray scatter shield. Pig. 2. Experimental Findings 1. Confirmation of crystalline form transition Preliminary experiments carried out with pure pentachlorophenol and with Monsanto and Reichhold technical "Penta" confirmed that exposure of Penta to a temperature of 75*C. for several hours or melting it gives a product with a changed diffraction pattern. Examination of samples undergoing transition shows several intensity peaks characteristic of both crystal forma and their ratio changes with time. The two regions in the pattern where this change Is most evident Is the 20 range of 11.5 to 1?.0# and 52.0 to 5**.5*. The 11.5* to 15.0* region had limited use In quantitative measure ment because intensities here seemed more affected by sample surface reproducibility. However, this region was favorable for study of samples showing marked preferred orientation such as pressed disks or solidified melts because of the greater sensitivity. 2. Effects of purity on transition rate Study of transitions at room temperature of solidified melts of pure pentachlorophenol and technical "Penta" from Reichhold and Monsanto exhibited sharp rate differences. Pure pentachlorophenol underwent essentially complete transition in about 4 hours where as Monsanto and Reichhold Penta still showed sub stantial amounts of the high temperature form after 1* and 20 days respectively. DSW 167133 STLCOPCB4041291 wr**. 1 61. 5. Effects of storage form on transition rate Monsanto Pents stored as flakes at room temperature showed essenttVMy no transition from the high temperature form In a five day period following flaking. But a portion of the same sample ground to a 40 mesh powder Immediately after flaking underwent nearly complete transition at room temperature in the same five day period. , Monsanto flaked Penta stored for '*9 months oontalned small amounts of the high temperature form. Nujol mulls on pure pentachlorophenol In the high temperature form showed nearly complete transition within the forty five minute period required to prepare the mull and obtain its diffraction pattern. Transition of a solidified melt of this same material took four hours. 4. Exploration of practical methods to accelerate crystal 7mTranHHon--------------- ^-------------------------------------------- The study of the transition rate of pure pentachlorophenol In the high temperature form showed essentially no change In 5 hours time while maintained at 55 v. which Is Just below the transition temperature. This same sample underwent nearly complete transition at room temperature In about four hours. 5. Transition of Monsanto Prilled "Penta" Preshly prilled Monsanto "Penta" showed only slight transition from the high temperature form over a 50 hour test period signifying that this physical form does not appreciably accelerate the crystal form transition. c. Future Applications of X-ray Diffraction Techniques This Investigation Illustrates several X-ray dlffraotlon techniques that can be used to Investigate crystal structure problems of the type described In this report. DSW 167134 STLCOPCB4041292 .TSBSHNI 62. X. The powder diffraction pattern is characteristic of a pure crystalline material and is useful in a) making identification, to) determination of purity, c) examina tion for crystalline changes brought about by decompo sition or reaction to form different crystalline pro ducts, d) following appearance or disappearance of a crystalline phase, e) measuring transformation of a given substance to a different crystalline form, f) formation of solid solutions or amorphous phases, etc 2. Measurement of selected diffraction pattern intensities ' often permits quantitative measurement of one or more crystalline components, the extent of a crystal form transition, rates of changes of crystalline phases and transition temperatures. 3. The special techniques of sample preparation devised should be useful in future studies of organic crystalline matter. 4. The production of diffraction patterns tinder variable temperature conditions should have future utility. D. Acknowledgements Acknowledgement is gratefully given to the following persons for helpful suggestions and support in this problem: 1. W. M. Trump for recommendation of heating and temperatuie measurement components. 2. To A. J. Blndbeutel for construction of the heated sample holder. 3. V. V. Saeger for suggestions pertaining to preparation of pressed disks of pentachlorophenol. 4. E. D. Plerron and R H. Munch for suggestions on sample preparation by the Nujol Mull Technique. 12/62 - D, B. Hines, R. E. Keller 1 DSW 167135 \ STLCOPCB4041293 X-RAV 6iPrAcrio)j hmVrO SAMfifi ' ~Jk..................................................' 6>. f ' 1*/ 1 . .,.. . l, * Y_ SAMPi.e Weil. (A) |WnJ rt**>^* v/Mk r^k . THERMOCOUPLE. VsJ&UL (fc) * ENb (HlSOkp,.*) ./elv-.,rN WE.ATE.fc (LAETtt&fcfc VitLL (.) AFRON'n C*/,* ***> * SCALE*. 1 IMCH I .. . . 1 ""' ^c::r_ "ni1 "f_mm`- --Jl .. V (A) te) SI&E. (C) rr w- (6)r n i ii To* S s I I ) DSW 167136 STLCOPCB4041294 64. i FI!Gr*. X-R/\y sc/irr&fc uofciPtO\X16K) DSW 167137 STLCOPCB4041295 SECTION 1_ ldtnti 1 lcatlon of Contaminants In para-Phcnctldine *5. JntrcHlncllon In tin- continuous hydrogenation of -phenotldlne, a precipitate wi:-. formed that caused a quality problem In the W.O.K. -phenetldlne. f.n;> 1 y 1.1 i-ai attempts to identify the organic structures of the con t. mil miniin the -phi netldlne were made by application of Infra red spectrorcopy. Those Identifications were attempted using a sample of polymer extracted from -phenetidlne that had been returned from Nltro. Summary Solid atate Infrared spectra (as KBr discs) showed the following structural characteristics of contaminants In -phcnutldl; 1. Secondary amine 2. Aromatic nucleus .5. Aliphatic hydrop.in *i. Kthoxy group l>. pn r a -: u> :.t 1 tut.i d i on-t I.! c and the possible additional structures- 1. nltro group 2. 1,2,4-trlsubstltuted aromatic ring. Other techniques - NMR, thin layer chromatography - were unsuc cessful. Analytical Studies para-rhenctldlne Contaminant Sample - Polymer from pata-Phenciidlne. ^/2^/ii2, R. Schubert (from material returned from Nltro;. Solubl llty - Estimated less than soluble In water, b<n..cn<., chloroform, acetone, acetone -* HC1, dloxane, benzene, DMF and tetiahydrofuran. Molecular Weight - Average molecular weight range Is to 600 using Menzieu apparatus and boiling toluene. DSW 167138 STLCOPCB4041296 m 06. Number of Components - At least 5 or ** as determined by nolubl1lty And thin layer chromatography. Structures pounrt - Determined by Infrared using KBr pressed discs of the samples. Ffo satisfactory solvent was found for a nuclear magnetic resonance study. n (lj "N-, secondary amine aromatic nucleus i '?/ -C-H, aliphatic hydrogen i- -0-C*H*, ethoxy group 0` p^ra-substituted aromatic Possible Additional Structures . 6 i NO?, nltro group , !,?, t.ri substitute d aromatic rir.g I?'6? * R. . Keller, P. Katlafsky t DSW 167139 STLCOPCB4041297 umMmmwmmmwmmmamm SECTION J 67. Identification of Plasticizers and Other High Bolling Esters Introduction A meeting of Research Supporting Technical Services personnel was held to discuss our current ability to analyze mixtures of plasticizers. The conclusions drawn also apply to other high boiling e3ters such as functional fluid base stocks. The three techniques having wide applicability are infrared absorption spectroscopy, nuclear magnetic resonance spectroscopy, and gas chromatography. The purpose of this discussion was to make certain that the Organic Research Department personnel were well oriented with respect to the advantages and limitations of each technique. Because it was felt that the information presented at the meeting would be of Interest to others, this report was drafted for dis tribution to staff members, group leaders and individual chemists in the plasticizer, resin materials and functional fluids appllcatlur. and process groups. Summary Infrared absorption spectroscopy, gas-liquid partition chroma tography (OLPC) and nuclear magnetic resonance iNMR; are powerful tools for detecting, identifying, characterizing, and measuring plasticizers. Each method has Its advantages and limitations. This report is offered as a guide to those working the plasticizer field in selecting the best physical analytical method of analysis to fit a particular problem. Analytical Studies The plasticizers in common use at present can be divided into the following classes: 1. Phthalate Esters 2. Isophthalate Esters 5. Terephthalate Esters 4. Phthalyl Olycolate Esters 5. Benzoate Esters 6. Kaleate Esters 7e.. Fumarate t3ters Adipate Esters 9- Azelate Esters 10. Sebacate Esters 11. Citrate Esters 12. Acetyl Citrate Esters 1?. Phosphate Esters 14, Sulfonamides lb. Chlorinated Hydrocarbons (Aroclcrs 16. Hydrocarbons 17. Polyesters 18. Epoxy Compounds Table I ll3ts the common members of each class showing those of Monsanto origin, those of competitive origin, and the number of competitive producers of each (data taken from the Encyclopedia of Modern Plastics, Vol. 59, No. i-a, 1962). DSW 167140 STLCOPCB4041298 68. Type Phthlates TABLE X COMMON PLASTICIZERS Monsanto Origin Competitive Origin di-methyl di-ethyl dl-butyl dl-2-ethylhexyl (DOP) dl-laooctyl (DIOP) di-lsodecyl (DIDP) dl-phenyl dl-cyclohexyl dl-trldecyl butylbenzyl (S-160) butyloctyl (S-165) lsohexylbenzyl (S-260) isooctylbenzyl (S-261) Isodecylbenzyl (S-262) No, of Competitors 10 11 28 25 21 22 none 6 7 4 2 -- -- -- DSW 167141 STLCOPCB4041299 69. I Table I (contM) Type Monsanto Origin Competitive Origin (methylearbltyl) benzyl(S-26?) . dlcapryl Isophthalates butylcyclohexyl butyIphenoxyet hy1 ethyleneglycol bis-(butyl) none Terephthalates di-2-ethylhexyl none dl-2-ethylhexyl No. of Competitors 6 2 E-15(ethyl-phthalyl ethyl glycoiate) B-l6(butylphthalyl butyl glycoiate) M-17(methylphthalyl ethyl glycoiate) none dletnyleneglycol dibenzoate dipropyleneglycol dlbenzoate ethyleneglycol dlbenzoate 1 J 1 DSW167142 STLCOPCB4041300 TO. Type Adipates Haleates Fumarates Azelates Sebacatas Table 1 (confd) Monsanto Origin Competlve Origin dl-2-ethylhexyl (DOA) dl-lsodecyl (D1DA) di-n-octyl-n-decyl dl-lsobutyl dlbutyl dloctyl dlbutyl dioctyl none none dl-2-ethylhexyl dl-isooctyl dl-lsobutyl dlbutyl dioctyl dl-lsooctyl WilWiilWtl No. of Competitors 23 17 14 8 5 1 3 3 10 7 2 14 14 10 DSW 167143 STLCOPCB4041301 71. Table I (coat'd) Type Monaanto Origin Competitive Origin No. of Competitors Citrates none triethyl 2 Acetyl Citrates tri-n-butyl 3 none Phosphates acetyl trlethyl acetyl trl-n-butyl acetyl tri-(2-ethylhexyl) 1 1 1 trlphenyl 8 trlcresyl S-l4o(cresyldiphenyl) S -141 (2 -e thylhexyldlpheny1) 12 7 S-144(isoctyl diphenyl) Sulfonamides $-l-H(N-cyclohexyl-ptoluene sulfonamide) none S-3(N-ethyl-p-toluene sulfonamide) none S8(N-ethyl>o,p~toluene sulfonamide) none S-9(o,p-toluene sulfonamide) none N-butyl benzenesulfonamide 1 DSW 167144 STLCOPCB4041302 72 Table 1 (confd) J&CB.P Monsanto Origin Chlorinated Hydrocarbons Aroclor 1221 Aroclor 1232 Aroclor 1242 Aroclor 1248 Aroclor 1254 Aroclor 1260 Aroclor 1262 Aroclor 1268 Aroclor 4469 Aroclor 5442 Aroclor 5460 Hydrocarbons Aroclor 2565 KB-20 HB-40 dodecylbenzene Competitive Origin mlBC Ko. of Competitors none none none none none none none none none none none none none 1 DSW 167145 STLCOPCB4041303 7>. Type Table I (contd) Monsanto Origin ' Competitive Origin Mo. of Competitors Polyesters S-405)1#J-butanediol S-409)adlplc acid S-4ll}polyesters mlsc. Epoxy Compounds epoxldlzed soy bean oil epoxy tailstea* epoxy tetrahydrophthalates 20 4 2 epoxy stearates mlsc 5 11 DSW167146 STLCOPCB4041304 7*. A. Infrared Absorption Spectroscopy Tn general. Infrared absorption spectra offer a rapid method of determining the class type of an unknown plasticizer (parent acid of the eBter3 type, sulfonamides, phosphates, etc.). The absorption patterns are very consistent for a given class and 3erve as proof for Identification purposes. Identifica tion of a particular compound within a class requires a critical comparison of the spectrum of an unknown material with that of a reference spectrum. Often the positive Identification of a given compound In a class is not possible because unless the IR spectrum Is obtained under special conditions, the small differ ences that exl3t are not easily discernible. For example, the spectra of dllsooctyl and dllsodecyl phthalete are practically Identical. For mixtures, each case must be considered almost indi vidually. However, the following general rules will apply: DSW 167147 STLCOPCB4041305 75. 1. For mixtures of two or more compounds in a class (l.e., butylbenzyl, k dibutyl and difcenzyl phthalates) infrared will not detect or . differentiate the components, only indicate that a phthalate la present. 2, In mixtures of plasticizers or different classes (i.e., fumarates and maleates) infrared spectra will often, but not in every case, be useful in detecting the presence of each of the several classes of plasticizers present. 3- Hydrocarbons in the presence of the other classes of plasticizers cannot be detected directly. Quantitative analysis of such a mixture will give a differential measurement of the hydrocarbon. A qualitative Infrared absorption scheme is attached which can be used to identify the majority of the plasticizer classes on the basis of the presence or absence of key abeorptlon bands in the spectrum. A bar graph le attached showing the characteristic absorption patterns for each plasticizer class. The wave length in microns for these characteristic bands are: 1. Phthalates 5.8 S`J-e.9 9-3-9.4 9-6-9.7 13,4-13.5 14.2-14.3 Isophthalates 5.8-5.9 l .7-7-9 (usually a doublet) .1 8.6 8.8 9-1 9-5 0 13.7-13.8 14.1 3. Terephthalates 5.8-5.9 7.9-8.0 (doublet) 8.|-9.1 (doublet) 13'.7 DSW 167148 STLCOPCB4041306 76. 4. Phthalyl Qlycolatcs 6-7-5.8 im 8.9 9.3 9.6-9.7 1?.5 14.3 5. Benzoates 5.8-5.9 7.6 j.8-7-9 9*0 9-5 9-7 14.0-14.1 6. Kaleates 5.75-5.8p 6.1 Broad band with four distinct peaks at: 7.7 -7-8 8.0 -8.1 8.25-8.35 8.6 -8.7 7. Fumarates 5.75-5.85 6.1 Broad band with two peaks at: 7.7-7.8 7.9-8.0 8.2 Broad band with two peaks at: 8.5-8.6 8.7 10.2 8. Adipates 5.75-5.85 8.0 -8.1 8.5 -8.6 (usually most Intense) 8.8 DSW 167149 STLCOPCB4041307 9 Azelates 5.75-5.85 8.0 8.5 -8.6 0.8 9.1 10. Sebacateg 5.75-5.85 8.0 -8.1 8.5 -8.6 8.85-8.95 11. Citrates 2.9 -5.0 5.75-5.85 8.4 -8.5 8.9 -9.0 12. Acetyl Cltratea 2.9 -5.0 (weak) 5.75- 5.85 7.75- 7-85 6.15-8.25 8.45-8.55 8.75- 8.85 13. Phosphate3 No band In 5.7-6.0 region. 7.7- 7.8 10.3-10.6 14. Sulfonamides 3.0 ,, No band in 5*7-6.0 region. 15. & 16. Hydrocarbons and Chlorinated Hydrocarbons No absorption in 5.7-6.0 region. No strong absorption in 7.5-9*0 region. 77. DSW167150 STLCOPCB4041308 m 78. 17. Polyesters Spectra of polyesters resemble those of the parent acid derivatives (i.e., adipic acid polyesters spectra will resemble those of the simpler adipates). 18. Epoxy Compounds Insufficient data available to characterize this class. DSW167151 STLCOPCB4041309 Bund at 5-7-5 1 Present cajwoxtIc ACID units r Present Absent Band at 7^6-7.8 ________ I_____ ~I Absent Band At 9.6-2O.5 r Present FHOSMUTM ~] Absent LSOIPHOB DBS HtWtOCASBOW AR0CL0R3 Wavslength in aiorons - bands are usually the strongest In the speotru*. 3 sc DSW 167152 STLCOPCB4041310 CHARACTERISTIC IKTRARED ABSORTJOH BANDS or rusTicizzR s *j PltWALATKS i | ISOrHTHAUTBS 4 ^ TKRXFHTHAUTM 1 nrnuLYL olycoutes ! Ibxnzoatks i i MAUUTES I < nCOIUTBS , ! ADIPATES 'J ' 4ZEUTSS $ S8BACATK3 , ' CITRATES - term citrates JnrosmTB i ___ 1.7?1__ 61___ I_alilfll______ till___ _______________ Oil___. yj _________________ 1 ______L . . 1 Ll i ................................................. !. J 1 j____"______Li__ 1_ 1 i: 1. 1- I ..... 1 1 . . 1............................ _1 __________ 1....... J 1 _ . ^SOLfONAKIDES .. t i M2 51 JO ' 61 rl `el 1 d 'iol WAVELF.N3TH IN KIORCWr n 1 'l 'i,l 'ml J5| I DSW 167153 STLCOPCB4041311 81. B. Nuclear Magnetic Resonance Spectroscopy Nuclear magnetic resonance Is a useful analytical tool for determining the structure of unknown compounds and for determining concentrations of components present In a mixture. A particular NMR measurement Is sensitive to only one nuclear species; at present, the Organic Research Department is equipped to perform analysis of proton, phosphorus, and fluorine containing compounds. In struc tural determination, use Is made of the position (chemical shift; and the multiplicity of an absorption. The absorption position la characteristic of the molecular environment of particular nuclei; the peak multiplicity gives Information concerning the presence or absence of nearby magnetic nuclei. NMR Is useful as a quantitative tool since the area observed for an NMR absorption is directly proportional to the number of nuclei giving rise to the absorption. In using NMR for structure elucidation of plasticizers, a given plasticizer class cannot be assigned a characteristic absorp tion pattern which Is unique to that class, as Is possible with infrared spectroscopy. Instead, the chemical shifts of the peaks observed In the NMR spectrum are used to Identify the structural groups present. Using this Information, together with peak multi plicity and relative peak areas, a definite structural assignment can often be made. , The approximate absorption intervals of the structural groups commonly found In commercial plasticizers are Indicated in attached figure. If more than one proton type Is present, the indicated absorption Is due to the underlined proton type. The second attached figure Is a graphical representation of the NMR spectra of > series of phthalate esters showing their characteristic chemical shit ';s and peak multiplicity; no attempt was made to repre sent relative p*.ak ares . quantitatively In this figure. The com pounds listed ars ZV.7, dimethyl phthalate; DEP, diethyl phthalate; DBP, dibutyl phthalate; DIOP, dlisooctyl phthalate; r*?r, diphenyl phthalate; and S-160, butyl benzyl phthalate. There are several limitations to the Information obtainable by NMR. In mixtures, or very complex molecules, because of the finite line width of the observed NMR signals. It is not always possible to distinguish between structural groups having similar chemical shifts. Also, in general, It Is not possible to dis tinguish between a pure compound and a mixture of compounds contalninlng the same structural groups. f -i 1 DSW167154 STLCOPCB4041312 PROTON CKBQCAL 8BJ7T3 OF GROUPS FOUND IN COMMON PLA3T1CXZXRS (POlLC-f?^ 8 ' 4-U..* -----1 at. I-------- 1 1 33 foo .J. <ti>7 4 00 _S.CLO 30 ?3J tw Chemlsil Shift to it tOr.c KCJt* I---------1 K-at* I------* / 47 JOC 0^5 DSW 167155 J STLCOPCB4041313 PRCTON NMR SPKCffU OF SOKE PHTOALATK *1 s* . Al S-? M ,i. Ai f?: A '1. I V-*%- cJl J_ Ytt SCO TUT *90 _L tJ*00O _L_ *3J ZOO Chemical Shift to (CHs)4S1 at Come 3-160 P II MOP .I P*Vt K*y cer SKP cJk vm U7 100 0 pm * t<*S 8 DSW 167156 STLCOPCB4041314 84. C. Cas Chromatography The following table summarizes our present capability In gas chromatography with respect to plasticizers. This represents the scope of our present experience and rot necessarily the limits of capability of peg chroma*ogrgphy. r*ir+her experimenta tion and development of *hla technique may llkelv broaden its applications to plasticizers. >/6} B. Katlsfsky, Tietrlch, E. Eme"v, W. E. Koerner, R. E. 'elle- DSW 167157 STLCOPCB4041315 Plasticizer Systems Dlalkyl Phthslates Dlalkyl Fumaratea and Maleates Alkyl Phosphates Di.?kyl Succli-'tes, Adipates, Sebacatea, ato. Oaa Chromatogra,hy Capability In Plasticisers Advantages I.Resolution Of mixed eaters from the corresponding aymmetrlcal eaters [e.g., lsooctylbenzyl and butyl-2ethylhexyl). 2,0eneral resolution of a mixture of DOP, DIOP, D1DP, S-100, TCP, dlbutyl-, dibenzyl- and dltrldecylphthalates Limitations Estimated Time Required per Sample Elapsed on Instrument (min.) Mtn-mln. JO JO 1.Detn. of unreacted esters In blafumarates. 2,Detn. of unreacted alcohol and other impurities, J.Resolution of mixed esters from the corresponding symmetrical esters. Do not resolve the higher maleates from the corresponding fumarates. ike can resolve the albutyl and diethyl, but not the dl-2-ethylhexyl and dllsohexyl). JO JO Resolution of most mixed phosphates, Buch ac the methylphenyl and butyl-phenyl series. Cannot as yet resolve the 2-cthylhexyl-phenyl series (S-lH,,. The same capability should apply In general as with the dlalkyl phthalates. 10 JO CD DSW 167158 STLCOPCB4041316 SECTION K 86. Infrared Study of the Reaction Rate of Resorcinol In Sodium Sulfite Solution Introduction The literature reports that resorcinol In the presence of sodium bisulfite Is sulfonated in several Intermediate steps to yield sodium l,5~dlhydroxy-l,5,5~cyclohexanetrlsulfonate and m-phenol sodium sulfonate as stable end products. Confirmation of this side reaction and reaction rate data Mere needed to optimize process conditions and minimize resorcinol losses In the acidification and quenched liquor storage steps of the resorcinol process. Summary An extraction procedure and Infrared absorption method were developed for the measurement of resorcinol In saturated sodium sulfite solutions which provided analytical data to calculate rate constants. In the temperature range of 50 to 105*6. and the pH range of 6 to 12 the data Indicated that at constant pH the reac tion rate Increased with temperature, and at constant temperature, the rate Increased with acidity. Under the tentative operating conditions of pH 7.o and 50*C., resorcinol Is sulfonated In a saturated sodium sulfite solution at a rate of l.o per hour. NMK analysis of samples of resorcinol In a saturated sodium sulfite solution refluxed at pH 7.0 showed that sodium l,5-dlhydroxy-l,5>5cycl^hexanetrlsulfonate and sodium nr-phenol sulfonate were the sulfonai'on products formed. Analytical Studies A. Infrared Spectroscopy Infrared absorption methods were used to study the disappearance of resorcinol In aqueous solutions saturated with sodium sulfite. This study was requested to provide reaction rate data as a function of ph and temperature to assist In optimizing process conditions and to minimize losses of resorcinol In the acidification and quenched liquor storage stages of the resorcinol process. The literature J. N. Uflmtseb, Zhur. Prlktad. Khlm. , 20, 1199 (19^7J7 reports that resorcinol,In the presence of sodlunfTisulflte, Is sulfonated. The sulfonatlon proceeds through several steps and 1.5- dlhydroxy-5-(1,5-cyclohexadlene sodium sulfonate) and 2,5-dihydroxy2.5- (cyclohexene disodium sulfonate; have been identified as Inter mediate products. The stable end products of the reaction are 1,5dlhydroxy-l,5,5-cyclohexanetrisulfonate and m-phenol sodium sulfonate. DSW 167159 STLCOPCB4041317 87. Infrared methods were Investigated to measure the resorcinol directly in aqueous solution. Attenuated Total Reflectance techniques proved unsatisfactory due to the poor long term stability of the optical bench settings which resulted in poor reproducibility. Direct transmission measurements of the solutions using thin cells with Irtran-2 windows were ruled out because measurements of either the 6.7 micron C-C ring stretching band or the 7.8 micron 0-1! deformation band showed interference from intermediate products. An extraction method using isopropyl ether was used to Isolate the resorcinol from the reaction mixture. The resulting ether solution was analyzed directly using conventional infrared transmission techniques to determine the resorcinol concentration. In the procedure used to Isolate the resorcinol from the reaction mixture, a ?0.0 _+ 0.0? gram aliquot of the reaction mixture was cooled to room temperature in a water bath and the pH adjusted to 6.0 by bubbling In sulfur dioxide (SO*) and using a pH meter. (In this study the reaction mixtures contained approximately 4# resorcinol and. were saturated with sodium sulfite.) The solution was transferred to a 7b ml. separatory funnel, the beaker was rinBed with 10 ml. of isopropyl ether and the ether was transferred to the funnel. The system was shaken for 30 seconds, the phases permitted to separate and then shaken for anadditional 30 second period. The ether layer was filtered through a cotton plug containing a layer of anhydrous sodium sulfate Into a ?h ml. volumetric flask. The water layer was extracted In turn with a second 10 ml. portion of Isopropyl ether and finally with, a 5 ml. portion of solvent. The funnel was rinsed with a small portion ol Isopropvl ether ar.d the rinsings were added to the filter. The Isopropyl ether volume in the flask was aoj *ated by adding additional ether dropwlse to the filter. Arrhydrous 3odlun. sulfate added to the f'asK e.n<1 the mixture shaken. A portion cl Isopropyl ethersolution was transferred to a ? dram vial containing a fresh portion of anhydrous sodium sulfate and shaken. This solution was decanted and equilibrated with finely ground sodium chloride In another 2 dram vial. Resorcinol recoveries of 9?-93Sf were obtained by this extraction and drying procedure. The dried isopropyl ether solution was transferred to a 0.08? mm. rock salt Infrared cell and the infra;ud spectrum was obtained using a 0.C76 mm. solvent compensating cell through the region of ID.1.10.7 microns. Measurements were made at 10-38 microns and a background correction measured at 10.DO microns to determine the resorcinol concentration. The instrument ccr.il t ions used werei , : : : ; 1 ' ; I ' ' : ' ; , ; 1 , , i : i1' DSW 167160 STLCOPCB4041318 88. Instrument: Optics: Slit Program: Attenuator Speed: Scanning Speed: (lain: Suppression: Chart Scale: Sample Cell: Reference Cell: Solvent: Perkln-Elmer Model 221 Double Beam Infrared Spectrophotometer MaCl prism 990 4 seconds full scale deflection 4 minutes/micron 4 0 10 cm./micron 0.082 mm. 0.076 mm. Isopropyl Ether The resorcinol-sodium sulfite reaction was run under the following conditions: 4 6 7 6 9 10 12.5 Temperature 70* 50 50, 70 and 90 5* 7 , 90, 105.5 CReflux) 105.5 105.5 The large excess of sodium sulfite present in the reaction mixture does not buffer the solution. As the reaction of resorcinol proceeds, the pH rises approximately 0.5 to 0.5 pH units when about 25$ of the resorcinol has reacted. A plot vf the analytical data,In the form of the logarithm of the rt*or/*inol concentration as a function of time for pH ranges of 6-12.5 and temperatures of 50-105.5*C., shows that the reaction is first order with respect to resorcinol. These plots are shown In Figures 1-4. Plots of the resorcinol loss as a function of time under the conditions Indicated above are shown in Figures 3-8. The rate constants calculated for each pH and temperature condition studied by: H Temperature Rate ConstantA Rate Percent' 6 7 8 7 8 7 9 9 10 12.5 50*C. 30*C. 00..001l0810/ho11 ur 50*C. 0.0044 tl 70*C. 70'C. 0.0504 0.0114 It n 90*C. 0.118 H 90*C. 0.0445 105-5 C.{Reflux)0.141 It 105.5 c. " 0.0900 tt 105.5*C. " 0.0017 1.80/hour 1.01 0.44 <1 5.04 ir 1.14 11.8 4.45 i tt ti 14.1 tt 9.00 tt 0.17 M DSW 167161 STLCOPCB4041319 89. (A) Rate Constant k 2.303 . taA{ 5 where Ci concentration at time tx and C* - concentration at time t* (B) Rate Percent - 100 k - percent resorcinol reacting per hour. A graphical plot of the rate constant vs. pH ia shown In Figure 9. The data obtained at 103 .5*C. are curvilinear and suggest the data for the lower temperatures are also actually curvilinear with an extrapolation to a common zero point. The data obtained under acid conditions of pH Aat 70*C. are somewhat confusing. After one hour under these conditions, the resorcinol concentration is reduced about Ilf. During the next three hours the resorcinol is regenerated so that at the end of four hours the resorcinol concentration is the same as the zero time sample. If bisulfite is the active reactant species in this reaction, then at pH 4,where the equilibrium should be shifted entirely to the suinte ion form, some other complexing mechanism must be operating. Since resorcinol is regenerated under these conditions, the resorcinol complexmust- beloosely coupled. B. NMR Spectroscopy Analysis of NMR spectra obtained from samples of resorcinol in saturated aqueous Ne*SO solution Indicate the following trans- formation1. Resorcinol (A) --(a) n30*-^ (C> r:.v rates of these reactions Increase with Increased tempersture. Three samples taken from a solution under reflux tondltions at pH ? indicate the following approximate compositions: 3 hr. 24 hr. 72 hr- reflux reflux reflux ~50* A, `,0# P ,*,90# P, 10# * ,^70# P, 30# C < Analysis of'"the NMR spectra and ielaved reference materials Indicate that (B) is sodium J , 3*dl hydroxy 1 ,3. 5*cvclohexanetrl sul fonate or some closely related material, and (?) is sodium m-phenol Bulfonate. Intermediate compounds between resorcinol and (B) and between (B) and (C) may exist. '1 \ 12/62 - B. Katlafsky, M. Dietrich, H. E. Keller '} i* f, || j. ji j: i >; | ! ; : j ? J j? . j. " j : i : i DSW 167162 STLCOPCB4041320 1 STLCOPCB4041321 anr 1- STLCOPCB4041322 F\vg 3 DSW 167165 STLCOPCB4041323 F>6u/? V STLCOPCB4041324 lM,r.. i*ifVhfMt |up 1irl TWttI*if,*IME il n Ji.TiB .M fiE /?C A /*r R e s e t* trJoL R /)C T & b i I; DSW167167 r-,, b I i; 'i i STLCOPCB4041325 11 n*i Fi^u/ef STLCOPCB4041326 < 1 Figure "7 STLCOPCB4041327 * irto imi (HeM 3*JH1* DSW 167170 STLCOPCB4041328 iOikmothi %m(H jibd 11 t 3#n y > DSW 167171 STLCOPCB4041329 SECTION L 99- Attenuated Total Reflectance Infrared Study of Sodium Phenate and Sodium Bensenesulfonate Introduction Conventional infrared analytical methods for laboratory and plant process aqueous streams have been limited by the Intense water absorp tion which makes It necessary to use extremely thin cells. Problems in plugging or deposits of foreign material in cells of this type in process stream applications result In serious analytical errors. A new infrared technique, known as Attenuated Total Reflectance (ATR), Is based on Infrared spectra obtained by surface absorption and is independent of sample thickness. The latter feature permits design of sampling cells of sufficient thickness to overcome the sampling problems associated with the normal transmittance techniques. Sodlua bensenesulfonate (NaBS) and sodium phenate solutions were investi gated to demonstrate the analytical feasibility of this technique, slnoe better control methods for these materials in phenol process streams oould result in improved phenol yields. Summary ATR infrared studies of aqueous solutions of sodium phenate and sodium bensenesulfonate (NaBS) have demonstrated this technique would be a specific and practical method for monitoring certain phenol process streams. Sodium phenate and NaBS In the concentration range of 10-35# can be measured to within 0.5# absolute. In NaBS streams, the components NaiS0, Na*S0*, Na?H, Na*C0* and sodium phena*e would Introduce only negligible errors In measuring NaBS. In s'.dlum phenate streams, small corrections could be made for the ?Vitrlbution of NaOH and NaS0 to the sodium phenate measurement. The Connecticut Instrument Corporation ATR equipment used In this work should be replaced by a structurally more stable unit for use as a plant stream analyser. Analytical Studies ` Attenuated Total Reflectance (ATR) Infrared methods were Investi gated to determine the feasibility of this technique for monitoring aqueous NaBS (sodium bensenesulfonate) and sodium phenate process streams in the phenol prooess. Excellent results obtained with laboratory scale equipment warrants a recommendation to Dr. Fowler's Instrumentation Group to oonslder construction of an instrument using the ATR prlnolple as a process stream analyser. r fv > >. DSW 167172 STLCOPCB4041330 100. ATR spectra were obtained using a Connecticut Instrument- Corpora tion Model ATR-1 attachment on a Perkln-Rlmex Model 221 Infrared Spectrophotometer. Silver chloride, silicon and Irtran-2 (Eastman Kodak) prisms were Investigate!. A silver chloride prism was used first., since this was available as a component of the basic ATR-l kit. NaBS gave no difficulty, but sodium phenate reacted with the silver chloride, leaving a deposit on the back face of the prism. A heml-cyllnder made from zone refined silicon In which the diametrical face acts as the reflecting surface was obtained by Dr. Fowler from the Inorganic Division. Surface oxidation on the exposed faces of the silicon resulted in intense absorption bands in the regions of Interest for NaBS and sodium phenate making this optical material unusable for this application. Eastman Kodak's Irtran-? optical material is Infrared transparent in the regions of Interest and Is relatively unaffected by caustic materials. Two Irtran-? prisms were obtained from the Connecticut Instrument Corporation end have been used with out any adverse effects In this study. The angle of Incidence relative to the reflecting face of the prism was found to have a large effect on the intensity of the absorption bands observed. The bands became more Intense as the angle of Incidence became nr and an angle of 4*, the minimum angle that can be set up wir.n the ATR-1 unit., was used. The phenol process streams of Interes* have, t he following typical compositions: Process St 5SriSftB5 Pherate Slurry Temperature Component Water NaBS Sodium phenate Sodium sulfite Sodium sulfate Sodium chloride Sodium hydroxide Sodium carbonate Diphenyl sulfone Na dibenzeneBulfonate Na dihydroxybenzene Na ophenylphenol Tars 9,5* t i*9 76 44.68 0.06 0.41 4.51 0.05 C. 15 0.06 0.25 0 06 - --------. ... -- 100* t 44 5? 51.50 ..... 0.55 ?.65 0.07 0.25 0.C8 0->4 0.06 ----------- -- ' 1?0* Am- 26.J0 0.23 29.90 34.82 2.76 1.54 3-60 0.4i 0.05 0.03 0.16 DSW 167173 STLCOPCB4041331 .101 Since no provision Is made for thermostatlng the ATR-1 unit or the liquid! ATR cells, the laboratory studies were made at room ten* perature. Solubility limitations at room temperature lowered the concentration ranges in which NaBS and sodium sulfite could be studied. Water solutions in the following concentration ranges were prepared for the principle components in these streams: NaBS Sodium phenate Sodium sulfite Sodium sulfate Sodium hydroxide Sodium carbonate 1005* 1005* 10-20* 1-8* 0.2-1* Two ATR units were set up to permit running the spectra of the solutions against water in the reference unit to compensate the water absorption. The ATR spectrum of water is shown in Pigure 1 of Progress Report 2-02-760.01-4285, No. 16. The following ATR and Infrared spectrophotometer parameters were used in this study: ATR prism Angle of Incidence Solvent Compensator Slit program Scanning speed Chart scale IR instrument Irtran-2 40* Water Water 980 1 minute/micron 10 cm./micron Perkin-Elmer Model 221 Spectral Results \. Sodium Phenate ATR absorption bands are found at 6.77 microns for the phenyl ring and at 7.90 microns for the Ar-0 stretching absorption. Either band Is suitable for analytical purposes. However, serious errors due to the presence of sodium sulfite would be Introduced to measure ments made at 6.77 microns while at 7-90 these effects would be small. Pigure 1 shows the superimposed spectra of a series of aqueous solu tions of sodium phenate. Figure 2 Is a plot of the optical density at 7-90 microns for these solutions versus the sodium phenate con centration (all measurements are made relative to the water blank at this wave). A linear function Is obtained showing that Beer's Law Is obeyed at this wavelength. DSW 167174 STLCOPCB4041332 10?. 2. NaBS ATR absorption bands are round at 8.5? microns for the sul fonate group and at 8.90 microns for what la probably due to a vibration of the aromatic ring. Either band could be used to set up an analytical method, but m this system the presence of sodium sulfate would produce serious errors In measurements made at 8.9 microns. The Interference due to the sulfate would be small for the 8.&2 micron band. Figure 3 shows the superimposed spectra of a series of aqueous solutions of NaBS. Figure 4 is a plot of the optical density of the 8.52 micron band versus the concentration of NaBS (all measurements are relative t-o the water blank at this wavelength). A linear function Is obtained showing that Beer's Law Is obeyed at this wavelength. 3- Sodium Sulfate and Sodium Sulfite Figures 5 and 6 sho/ the superimposed spectra of a series of aqueous solutions containing 1-5# sodium sulfate and 10-20# sodium sulfite. At the analytical wavelengths (7-90 and 8.52 microns). It can be seen that interference errors would be small. 4. Sodium Hydroxide and Sodium Carbonate Figure 7 shows the spectra of 7.8* sodium hydroxide and i# sodium carbonate in the spectral region of Interest. Sodium hydroxide produces no finite absorption band but merely depresses the background. Its presence would have about equal effect at 7.90 or 8.52 microns. Sodium carbonate produces an absorption band peaking at 7.25 microns which tapers off to a point where Its presence would introduce only s Blight error In measurements at the two analytical wavelengths. Prom the ATR spectra of sodium phenate and NaBS obtained under laboratory conditions. It can be seen that both materials coyld be easily measured to + 0.5# absolute. Calculations were made 'to deter mine the approximate error that would be introduced by the presence of sodium Bulfate, sodium sulfite, sodium hydroxide and sodium carbonate at the concentration levels present In a .typical stream m the measurement of sodium phenate and NaBS. The results are: NaBS Measured at 8.5? 44# NaBS Stream 0.4# sodium sulfite 0.?# sodium hydroxide 0.06# sodium carbonate 0.06# sodium phenate Isequivalent to 0.006# NaBS Isequivalent to 0.06# NaBS isequivalent to 0.02# NaBS Isequivalent to 0.01# NaBS DSW 167175 STLCOPCB4041333 103. 5*0 NaBS Stream 0.60 sodium sulfite Is equivalent to 0.010 NaBS 0120 sodium hydroxide Is equivalent to 0.060 NaBS 0.060 sodium carbonate la equivalent to 0.030 NaBS 2.70 sodium sulfate - negligible contribution . Sodium Phenate Measured at 7.90 Microns Phenate Slurry .60 sodium sulfite is equivalent to 0.50 phenate 3>60 sodium hydroxide is equivalent to 1.00 phenate O.*0 sodium carbonate is equivalent to 0.10 phenate 2.80 sodium sulfate - negligible contribution 0.20 NaBS - negligible contribution These calculations, even If the approximations were In error by a factor of 2, show that a NaBS stream analysis by an ATR method would not be affected by the presence of the other compo nents in the system. Corrections would be necessary in a phenate slurry stream to correct for errors Introduced by the presence of sodium hydroxide and sodium sulfite. The results obtained In this Investigation Indicate that ATR Infrared methods are feasible for the analysis of NaBS and sodium phenate streams in the phenol process. Presently available commercial equipment, however, would not be practical for long term use unless frequent calibration checks were made. The optical bench and the optical mounts of the ATR-1 unit from Connecticut Instrument Ccrporatlon are not sturdy enough for long term stability. The design and construction of a more rugged ATR unit should be Inves tigated for application as a plant stream analyzer. 8/62 - B. Katlafsky, R. E. Keller (_ r T\ ' DSW 167176 STLCOPCB4041334 seenrofraodoonis ZZl.Z91.MSa (SNOOW) H19N313AV/A -<fY not 1 on 'AT DENSITY <*r. la 1 IMO tH| CM MMl -fc I DSW 167178 i s STLCOPCB4041336 106. WAVELENGTH (MOONS) T DSW 167179 STLCOPCB4041337 DSW 167180 I STLCOPCB4041338 lod. WAVELENGTH (MICRONS) DSW 167181 STLCOPCB4041339 109 .A it i \ WAVELENGTH (MIRONS) i DSW 167182 STLCOPCB4041340 110 WAVELENGTH (MICRONS) w DSW 167183 STLCOPCB4041341 SECTION H Thin Layer Chromatography - Evaluation m. Introduction and Summary Thin layer chromatography (TLC) Involving the uoe of an adsor bent spread In a thin layer on a glass plate has been given a preliminary evaluation. Results obtained with silicic acid as the adsorbent show that mixtures of resorcinol, pyroeateehol, phenol, hydroqulnone and phlorogluclnol can be separated Into components and Identified within 45 minutes using 10% n-butanol In benzene as the eluant. Semi-quantitative estimations can be made by visual Inspection. The prime advantages over paper chromatography appear to be speed and Increased resolution. Water consent of the adsor bent is a significant variable that must be controlled. As with paper chromatography, accurate quantitative measurements may prove to be difficult. Analytical Studies The thin films on glass plates used for TLC may be prepared with a number of supports including silica gel 0, aluminum oxide, Kieselguhr Q and cellulose powder. The films for this work were prepared with the "Desaga" apparatus designed by Stahl. The samples are applied to the film with a Hamilton micro!iter syringe with sample volume ranging from 1 to 20 microliters. The chromatographic separation Js dependent- upon the amount of moisture In the film and upon the mobile solvent used. In the work with resorcinol, dry plated produced poor separation and tailing. The freshly prepared wet plates were put in a desiccator containing a dish of water to control the moisture. This technique will keep the film sufficiently wet for a few days. As In paper chromatography, the selection of a suitable solvent is based on knowledge of solu bilities, partition coefficients and finally by trial and error. In the case of resorcinol, 5% n-butanol In benzene (vol./vol.)was us*-d for our paper chromatography work. The amount of n-butanol was varied and it. was found that 10% n-butanol In benzene gave the best separations using the silica gel TLC scheme. The separated components were detected by color development with a coupling agent (~nltrobenzene diazonlum fluoroborate) followed by alcoholic potassium hydroxide. The TLC chromatograms are difficult to keep and are somewhat fragile. A solution to this problem is the transferral of the chromatogram to paper with a Xerox 914 copier. Figure I shows a Xerox copy of a chromatogram of Individual components and an equal mixture of the resorcinol and related components. DSW 167184 STLCOPCB4041342 112. The TLC procedure requires about 45 minutes total elapsed time per chromatogram as compared with 3-4 hours per paper chromatogram. The sensitivity appears greater than that, obtainable using paper. Preliminary work on quantitative measurements shows that the froblems common to paper chromatograms also exist with TLC schemes. Removal of the spot can be accomplished easily with a razor blade. Elution of the component can be made with a suitable solvent for subsequent ultraviolet analysis or similar measurement. However, the microgram quantities normally separated make It necessary to use very sensitive methods for measurement. Work at higher concentration levels showed that bands Instead of spots could be separated with the purpose of producing larger concentrations of separated compo nents. Area measurements for quantitative determinations apparently can be carried out with about the same accuracy obtainable with paper chromatography. No specific area measurements were carried out as a part of this study. Work is underway on determining the feasibility of Infrared attenu ated total reflectance as a means of identifying separated components directly on the silica gel. l?/62 - 0. Hicks, H. E. Keller I; DSW 167185 i STLCOPCB4041343 Plfiurc 1 TLC Chromatogram for Rcrorclnol and Related Components (copied with Zerox 91^ copier) SOLVED - 10 Butyl Alcohol in Benzene CARRIER - Silica Gel G Preparation - 1 part silica Gel/2 parts water, film prepared ano held 1 hour at room temperature conditions. DEVELOPMENT TIME - 50 Minutes SPOT DEVELOPMENT - p-Nltrobenzene diazonium fluorohorate followed oy alcoholic K0H. "-1 K*1 .0 f /T\ i i O' .` ', . J n, ij v ' * >. ' . .i V/ X ' ' V' 'W- Phenol '0 Py*?CCATEC|!fl). 1 * , 11 o . RSOC1NOL- C.) HY SRc'W* /w/jr:ii j * ! - ; . .! PHU&C&LVC INOL ` . . . i cc::pc:?ei?ts 1. Resorcinol, 500V in 10 microliters acetone. 2. Phloroglucinol,500 V in10 microliters acetone. S' Pyrocatechol, " "" " " ;r. Hydroqulnone, 5. Phenol, .,6. Equal mixture " " "" "" " " " " of 1, 2, h and 5# " total DSW 167186 STLCOPCB4041344 SECTION N Evaluation of Trlcosane Oxidation Study by Infrared Analysis . 11*. Introduction * Basie structure data were needed to assist In the selection of an oxidation Inhibitor for Trlcosane. Arrangements were made to examine a C40 alkane that had been analyzed In the laboratory using the Dornte apparatus by a differential Infrared absorption procedure. Summary Infrared data were collected from five Dornte oxidation runs. The samples were analyzed as capillary films in 0.2 mm. cells using the starting material for compensation. Samples were taken periodically during the laboratory run until the Infrared absorp tion went off-scale. Optical densities were plotted graphically for five wavelength positions representative of the functional groups formed during the oxidation. The family of curves show that the various functions form at somewhat independent rates. Saturated ketones Increase at a fairly steady rate. Alcohols rise rapidly Initially. Type III olefins rapidly reach a maximum and eventually attenuate to a small fraction of the peak value. Analytical Studies Ketone, alcohol and the olefin, RRC-CHa, form Immediately and become the dominant structures early In the oxidation. Near the peak of olefin production a wide variety of oxidized products appear and esters become significant. There Is no evidence for conjugated ketones or aldehydes. Infrared does not provide good evidence for peroxides. None are evident. Eventually a wide variety of carbonyls appear. Unsaturation occurs almost entirely In the Type III form, plus a minor amount of trans olefin. One gas Bample from the laboratory oxidation run was analyzed. The carbon monoxide content of the gas collected from the apparatus was six times as great as the carbon dioxide content. Methane, ethylene and propylene each amounted to about one tenth the carbon dioxide content. An unknown alcohol of more than three carbons appeared In trace quantity. DSW 167187 STLCOPCB4041345 115 Function -0-H -C-0 -C-0 -C-0 -C-H Table of Wavelengths Studied Wavelength Structure 2.9? microns Alcohol hydroxyl 6.82 Saturate ketone and eater carbonyl 8.62 Ester C-0 9.50 Alcohol and ether C-0 11.30 Type III olefin 12/62 - 0. Kinast, R. E. Keller i f j. l l i, } DSW 167188 STLCOPCB4041346 SECTION O 116. Vanadium Oxide Components In Catalyst Mixtures Introduce on Vanadium can form In addition to V*09, V204 and V*0* other lesser known oxides with empirical formulas that are Intermediate between V*Os and V0 and V|0 and V#Os. X-ray diffraction data Indicate the possibility of six oxides between V*0 and VtO and one between V2(>4 and V*09. Since these Intermediate oxide compounds could be present In conventional vanadium oxide catalyst mixtures, methods for detecting and Identifying these species would be helpful. In addition, characterisation and correlation of composition with activity would be useful In the design of better catalysts. An Infrared study was Initiated to elucidate the chemical bondln;. In a series of Intermediate oxides. Summary Infrared solid state spectra were obtained for V20a, V*0* and Vv0 dispersed In KBr In the 2-35 micron region. Subsequent studies show that radical spectral differences exist for prepared Intermolecular complexes Including V20*.3, VaOs.$), V0.4, VOs. V*0.* and V*0.9^. This work corroborated X-ray diffraction data and Indicates new chemical compounds are produced In the systems V20s-V*04 and Va04-Vt0s after heating. Analytical Studies Vanadium Is known to form,In addition to the common oxides V*0, V*04 and V209, a series of Intermediate or suboxides on heating the systems: n VOj + m V(0 or n V.C* + m V209 where n and m are lntergers. Since these suboxides have catalytlcal application potentials, an Infrared study was Initiated to detect and characterizes these oxides. The oxide systems studied were prepared by Dr. F. H. Munch and Included: VC09 ' V*04.s (V*04 + Va0s V40tJ V204.ss (2V,04 + V0s - Ve0x9j V*04.* (7V*04 + 3V09 - V2o04s) V*04. (fcV204 + V209 VXoO VaOi i (9V*04 + V209 * V2o04X i VB04 DSW 167189 M H*1, I w li I k. I4" r* S'- ft :1 m m & STLCOPCB4041347 117. V03. V0,. v*09. V.03. VaO. VtO,. V0,. V*03. VaO,. VaO. VaO,. VaO, tV#03 + 9Va04 - VaoO*) (V*0S + 4V,0* - VloOx.) (5V03 + 7V*04 - Vat>0*7) 7 (v,0s + 2V*04 - V*014) (2V303 + 3Vt04 - VxoOia) VaO* + V,04 - V40T) (?Va03 2V*04 - V1o0it) 3 (2V*03 + V,04 - VeOio) (7V*03 + 5V0* " V>o033) (4V*03 + V04 - Vlo0x*j (9VaO, + V.04 - VtoO,i) The infrared spectra were obtained In the 2-55 micron region for the oxides dispersed In KBr (potassium bromide) and pressed Into thin discs. The most significant data were obtained In the rock salt region (2-15 microns). The Infrared absorption data observed In this region for the vanadium oxide systems are repre sented In bar graph form In Figures I and II. A. Va04-Va0 System (Figure I) Vanadium pentoxlde (V*03) has a very Intense, clearly defined absorption spectrum with absorption bands at 9-SO and 12.50 microns. The tetroxlde (V*04) shows a very weak, broad band at about 9.6 microns and a slightly stronger band at about 13 microns. The Infrared spectra of the oxides obtained having the empirical formu lae V04.a, V*04.3, V04. and V*04.i indicate that these materials are mixtures of V04 and VgO*. The spectrum obtained for the material having the empirical formula V*04.33 shows radical changes compared to those of V04 and V305. Two weak bands of approximately the same intensity appear at 8.65 and 3.90 microns and a stronger band at 11.24 with a shoulder at 11.70 microns are observed. No absorption Is found at 9-90 or 12.50 microns, indicating that no V*0s is present. This spectral evidence supports X-ray diffraction data that the vanadium oxide having the empirical formula V*04.33 Is a new chemical entity. B. Va0s-Vg04 System (Figure II) Vanadium trioxlde (v303j is pract.lally opaque throughout the spectral region studied and Bhows cnly an extremely weak absorp tion band at about 10 microns. The tetroxlde (V304),as noted before, has a weak band at about 15 microns and a very weak, broad band peaking at about 9-6 microns. The molecular complexes corresponding to the empirical formula*1 of V303.3, V303.t, VgOs-e-r, Vj>03.3, Va03. and V*03.x produce Infrared spectra that are devoid of character. Indicating that these are merely mixtures of the V303 and Vg04 enti tles. The species V?0*., V3o3. and V03. have a medium intensity DSW 167190 STLCOPCB4041348 116. band at 10.03 microns and V0S. has a strong band at 14.0 microns. Absorption at these wavelengths Is absent In both V0 and V0 Indicating that these four entitles are new chemical compounds. This data supports the conclusion drawn from X-ray detraction data for these materials. The species corresponding to the empirical formula V0.aa has Infrared absorption bands at both 10.03 and 14.0 microns. Although the spectral data can be Interpreted either as indicating a new chemical entity or to Indicate a mixture of the V0.3 and VaOa. species. X-ray diffraction data clearly indicate that V0s.s la a new chemical compound. The appearance of an absorption band in the 10 micron region In the VaO*., V*0a.*, V*03.4 and V0a.ss species Is Interpreted as indicating that these suboxides have some V0 bonding. This conclusion Is based on data compiled in the reference text: 0. Her2berg, "Spectra of Diatomic Molecules", 2nd edition, pp. 501-381 (Van Nostrand, New York, 1950) In this compilation, spectral data observed for the electronic states of diatomic molecules are used to calculste the vibrational constants for the system. These constants can be used In turn to calculate the vibrational frequency (infrared absorption) of the system. This frequency Is conventionally reported in terms of reciprocal centimeters, cm."1 (cm."1 - 104 x the reciprocal of the wavelength In microns). The vibrational frequency calculated for the M*0 entity of vanadium and Its neighbors In the first row of transition elements In the periodic table are: M (*0) Prequency In cm."1 Se 96U T1 1004 V 100? Cr 886 Mn 8?1 Fe 870 Co No data Nl No data The observed Infrared data for Va09 and the suboxides V*04.s, VfO*.*, V*0j.e and Va03. are: Oxide Prequency in cm. V*0, V*04 . V0a.39 V03.4 Va03.9 VaOa.a 1021 112?, 1156 995 995 995 995 DSW 167191 STLCOPCB4041349 119. The close agreement between the observed infrared absorption frequency and the calculated frequency for the V-0 vibration is Interpreted to Indicate that the suboxldes V04., V90.4< V0.* and VaO. contain some V-0 bonds. This Infrared study has confirmed X-ray diffraction data that a minimum of five suboxldes can be obtained by heating stoichlo metric quantities of V*0 and V*0 and one between V*0* and V|0. The observed Infrared data have been interpreted to indicate the presence of V-0 bonding in five of these suboxldes. Further work would be required with known oxide systems to fully characterize the oxygen bridge bond In the vanadium oxides. 12/62 - B. Katlafsky, R. E. Keller DSW 167192 STLCOPCB4041350 P u if *1 .140 t *t DSW 167193 STLCOPCB4041351 h I l\ U t. . XL . 121. T O IH t t W O t.H C DSW 167194 - STLCOPCB4041352