COMPILATION OF GAS CHROMATOGRAPHIC DATA Editors: E Schupp III, Eastman Kodak Co., Rochester, N Y., and J S Lewis, Tennessee Eastman Co., Division of Eastman Kodak Co., Kingsport, Tennessee Sponsor: ASTM Committee E-19 on Gas Chromatography ASTM DATA SERIES PUBLICATION NO DS 25A List Price $40.00; 30 per cent discount to members 4! published by the AMERICAN SOCIETY FOR TESTING AND MATERIALS 1916 Race Street, Philadelphia, Pa 19103 © by American Society for Testing and Materials 1967 Library of Congress Catalog Card No 67-26106 Second Edition NOTE The Society is not responsible, as a body, for the statements and opinions advanced in this publication Printed in Philadelphia, Pa July, 1967 11 CONTENTS Introduction iv Description of Compilation iv Retrieval of Data vii Acknowledgment be References x Table 1—Codes for Liquid Phases Table 2—Codes for Solid Supports Table 3—Codes for Reference Materials Table A—Codes for Abstractors 13 Table 5—Codes for Type of Unorthodox Data 15 Table 6—Codes for Computer Operations 17 Table 7—Coden Abbreviations for journal Titles 19 Table 8—Gas Chromatographic Data Tabulated on Basis of Liquid Phase 27 Table 9—Gas Chromatographic Data Tabulated on Basis of Molecular Formula 295 in Introduction For the past several years an increasing amount of gas chromatographic data has been published for a wide variety of materials A system for compiling published data as well as privately generated data was developed by the Gas Chromatography Subcommittee of the Tennessee Eastman Company Analytical Committeef/].1 Data are coded in a standard form and are stored in IBM cards When desired, the retention data can be retrieved directly from the cards or from listings of the accumulated data which are produced periodically In 1962, ASTM Committee El9 on Gas Chromatography adopted the system developed by J S Lewis and his co-workers at the Tennessee Eastman Company The system was named the Tennessee EastmanASTM System Data in the system were published in 1963 as ASTM STP 343 The designation was later changed to DS 25, of which this is the second edition Task Group of Subcommittee I, ASTM Committee The italic numbers in brackets refer to the list of references on page XI E-19, was formed to evaluate the original system, to find methods for the accumulation of data from published and unpublished sources, and finally to keep the data in the system as current as possible.2 In 1965, a group of abstractors under the direction of William Hayles at the Rochester Institute of Technology was hired by ASTM to code retention data from the literature into the system At present, probably no more than 60 per cent of the published data have been included in this compilation Only the data abstracted through 1965 are included in the system at present However, ASTM has arranged further contracts with the Rochester Institute of Technology under which abstractors at the Institute will code gas chromatography data from the literature through 1967 Eventually, the data will be entered continuously and the system kept up to date - Present members of the task group are: O E Schupp III, chairman, Eastman Kodak Co.; R A Hively, secretary, Goodyear Tire and Rubber Co.; H G Collier, Pennsalt Chemicals Corp.; Irwin Hornstein, U S Department of Agriculture; S A Haddad, The Foxboro Co.; and J S Lewis, Tennessee Eastman Co Description of the Compilation The object of this compilation is to provide the gas chromatographer with the gas chromatographic conditions used for the separation of a wide variety of compounds and to facilitate the tentative identification of materials producing peaks on chromatograms Our ultimate aim is to have reference to all published articles which give conditions for the separation of compounds When this has been accomplished, references to all gas chromatographic separations will be readily available This book contains tabulations of gas chromatographic data printed from punched cards in a format which provides convenient means for rapid retrieval of data Most of the data were obtained from the literature, although some are unpublished data contributed by the laboratories of the Eastman Kodak Company, the Tennessee Eastman Company, and the Lockheed-California Company The use of commer- cial names or trademarks to designate some materials is for the convenience of compilers and users of this system and does not imply that they are recommended or preferred for any applications This volume contains all the retention data currently accumulated It differs from the first edition in that (1) the volume of data has about doubled, (2) the retention data include the retention index and capacity ratio, (3) a new format is used which will facilitate data retrieval, and (4) reference is made to chromatographic data for specific compounds which are in a nonstandard or unorthodox retention form Unorthodox retention data would include references to a journal where only the chromatogram is given, where nonlinear temperature programming is used, or where retention data are not in a form suitable for coding into the system In addition, the retention data have been examined by a computer using a program developed at Eastman Kodak Company [2] This program is designed to four things: (1) to determine if the correct value of the gas holdup was used in calculating the relative retentions when three or more n-alkanes are included in the data reported; (2) to recalculate, if necessary, the reported relative retentions using a gas holdup correction factor, when four or more n-alkanes are present; (3) to calculate retention indices; and (4) to calculate retentions relative to the nearest n-alkane whenever sufficient data are present Data found to be incorrect are discarded when they cannot be corrected Every precaution has been taken in the computer program to assure that the high quality of the data is retained Data are coded into the system into two types of punched cards The name-formula card (NFC) contains the compound name in standard punched card alphabet, molecular formula, and a cross-reference serial number The cross-reference serial number identifies a compound for which gas chromatographic data are coded and is the same for a given compound even though the compound may be named in various ways For instance, anthanthrene and dibenzo [def, mno] chrysene would both have the same serial number (471784) since these are two names for the same compound Serial numbers are assigned to compounds by arranging them in molecular formula sequence and assigning numbers to each compound in order The molecular formula sequence is determined first, by the number of carbon atoms, second by the number of hydrogen atoms, and thereafter, in alphabetical order by the number of atoms of each additional element The elements included in the NFC are bromine, chlorine, fluorine, iodine, nitrogen, oxygen, sulfur, and silicon Thus, C8H10 will appear before CeH12 and will have a smaller serial number, and C6H13Br will appear before C6H13CI and will also have a smaller serial number A survey of the listing of NFC (in Table 9) and the sequence of serial numbers and molecular formulas is essential to a complete understanding of the system The data-bibliography card (DBC) contains data which describe the gas chromatographic column used, retention data, bibliography reference, and the crossreference serial number The data which describe the column include: liquid phase (LP), solid support or active solid (SS), column temperature in deg C (T) , concentration of liquid phase (GLP), and the reciprocal of the slope of the semilogarithmic plot of net retention volume versus carbon number for n-alkanes (1/B) The retention data coded include: reference material (REF), relative retention, specific retention volume, or capacity ratio (REL-RET), and retention index (I) The bibliography reference includes codes for the journal, volume, page, and the year of the article coded, as well as company and laboratory codes for unpublished data Data-name cards (DNC) were added to the system after the publication of STP 343 and contain some of the data from the DBC and the name of the compound from the NFC The DNC is reproduced from both the DBC and the NFC However, these cards are not made for unorthodox data entries Once the decks of cards have been produced, they can be reproduced, sorted, and rearranged by means of conventional equipment for handling punched cards The cards can also be used to produce printed lists of all or part of the information stored in almost any order desired Tables and were prepared directly from the punched card decks Table contains the codes for the liquid phases arranged in numerical order These codes appear as LP in Tables and In addition, in Table 8, the first card listed for each block of data is the name of the liquid phase used A blank under the heading LP indicates that no liquid phase was used and that the code under SS is for an active solid material A zero under the heading LP indicates that a combination of liquid phases was used The specific combination might be found by referring to the source of data The codes for the solid support and/or active solid are listed in sequence by the code number in Table These codes appear under the headings SS in Tables and Identical or essentially identical solid support materials are often sold under different commercial names For simplicity and ease in using the system, similar materials are always given a common code designation For example, eight commercial materials are listed under SS code 50 For the data in Table where there is no code for the liquid phase, the first card for each block of data under the heading SS is the name of the active solid used Table is a list of the codes for the reference materials, also arranged in numerical order Codes for the reference material appear under the heading REF in Tables and The reference compounds are assigned an arbitrary adjusted retention time of 1.00 For code numbers up to and including 40, the number coded under REF refers to the corresponding number of carbon atoms in the n-alkane used as the reference compound When a V is listed under REF, the data coded under REL-RET are for the specific retention volume A "K" under REF indicates that the capacity ratio is listed under RELRET When the original retention data are recalculated by the abstractor as they are coded into the system, this is noted by a description code Table is a list of these codes They appear under the heading A in Tables and Table lists the codes for indicating the unorthodox form in which the data were published These codes appear in Table under the heading U Table lists the codes for indicating operations performed on the data by the computer used in upgrading the data These codes appear in Table under the heading C Table contains a list of standard four-letter abbreviations for journal titles (CODEN) [3] used in the system The CODEN assignments appear under the heading JRNL in Table When BOOK is coded under JRNL, this indicates that the data were taken from a book The particular book has a four-letter code under VOL in Table The titles and authors of the various books are given under the CODEN BOOK in Table Table is a tabulation of the gas chromatographic data from the data-name cards arranged in the following sequence: liquid phase (LP), column temperature in deg C (T), reference material (REF), and retention data (REL-RET) The heading at the top of each page in Table refers to the data coded in that particular column Reading from left to right, under LP are the codes for the liquid phase used which are identified in Table Also, the first entry for each new liquid phase is the name or names of liquid phase For example, the first entry in Table for LP 150 is the name squalane Thus, squalane is the liquid phase for all the data coded under LP 150 Under liquid phase code 163, the first two entries are Apiezon Grease L and Perkin-Elmer Column Q Thus, liquid phase code 163 is for Apiezon Grease L which is sometimes referred to in the literature as Perkin-Elmer Column Q Under the heading SS are the codes for the solid supports used which are identified in Table For data where no code is given under LP in Table the first entry under SS is the name of the particular active solid used Under REF are the codes for the various reference materials used which are identified in Table For numbers up to and including 40, the number listed refers to the corresponding number of carbon atoms in the n-alkane used as the reference compound The retention data are listed under the heading REL-RET When a V is listed in the column headed REF, the specific retention volume is coded under the heading REL-RET When a K is coded in the column headed REF, the capacity ratio is listed under the heading REL-RET The data under the heading T is the column temperature in deg C Under the heading A is listed a description code identified in Table 4, which is used by the abstractor when original retention data are recalculated as it is coded into the system The data under heading I are the retention indices Retention index is the preferred retention parameter [4,5] It is defined relative to the retention of n-alkane», and represents the hypothetical (whole number plus interpolated decimal fraction) n-alkane which would have an identical retention multiplied by 100 Retention index, relative retention, and net retention volume are related as follows: log VNX - log VNZ (1) log VN(Z + i) — log VN, When flow rate is constant, relative retentions can be substituted for net retention volumes /* = 100 [z + -)-• log rXl, \ •(2) logrc+i),,/' h = too u + logBrXll\) •(3) VN = net retention volume x = a compound with a retention between that of the first and second n-alkane standards Z = number of carbon atoms in the first n-alkane standard rx,z = relative retention of compound x with respect to the first n-alkane standard (s + 1) = number of carbon atoms in the second n-alkane standard Ix = isothermal retention index of compound x IPT = linear PTGC retention index VNX = net retention volume of x VNZ = net retention volume of the first n-alkane standard VN («+ i) = net retention volume of second n-alkane standard = relative retention of the second >"(»+ i).« n-alkane with respect to the first B = the slope of semilogarithmic plot of net retention volume versus n-alkane carbon number It should be based on n-alkane retentions that are about a decade apart h = 100 [z + where: VI Equation can be extended to linear programmed temperature gas chromatography (PTGC) by rewriting it thus: IPT £* 100 (Z + VNX V ' VN ' ) (4) In linear PTGC, any one retention parameter (volume, time, chart distance, or temperature, with or without correction for gas holdup) can be substituted for VN Equations and are preferred for calculating I for storage into the system, since n-alkanes with retentions which bracket the retention of the compound for which I is to be calculated are used Equation is used for correlation of data over a wide range of retentions, and for extrapolation of data outside of the range for which experimental measurements are available for the n-alkanes The data under GLP are the concentration of liquid phase used The number coded is the parts LP to 100 parts SS, by weight The other headings in Table refer to the compound name and the cross reference serial number The cross reference serial number is given in Table so that the same data can be located in Table For example, in Table under LP code 163 at 100 C are listed four different retention values for 2-butanone The serial number of 2-butanone is 72100 By looking in Table under SER NO 72100, the bibliography reference for these four values can be obtained Table is a tabulation of the merged NFC and DBC in order of the cross reference serial number Each NFC for a given compound is listed and is followed by all the DBC for that compound in order as in Table Unorthodox data entries are also included in Table The headings at the top of each page refer to the data in the DBC rather than the name and formula of the compound Table contains all the data listed in Table except the compound names; it also contains more data than Table The code under the heading U in Table is identified in Table and indicates the unorthodox form in which the data were published As a rule very little or no retention data are given where a code is listed under the heading U The main reason for listing unorthodox data is so the user can obtain a bibliography reference for the chromatography of that material Data under O-RM and OLD-RR are the data that were originally coded into the system These data were transferred here by the computer during the operation coded under column heading C Table also contains the code for unpublished data which have been donated to the system Under the heading N/P an N or P is listed for unpublished data The N refers to data from a notebook and the P refers to data from a procedure or company report As a rule, additional information other than that coded on the DBC is not available when an N or P is listed under the heading N/P However, the company donating the data is identified by codes under the heading CO and LAB An A under CO is for data from the Eastman Kodak Company, a B under CO is data from the Tennessee Eastman Company, and an L under CO is for data from the Lockheed-California Company Retrieval of Data This section deals with the use of the compiled data for the tentative identification of compounds and for the selection of columns for the separation of two or more compounds Other uses of the lists of data will undoubtedly be obvious to persons engaged in gas chromatographic work Probably the greatest use of the system is to determine if data have been reported for a particular compound Often it is very helpful to refer to published data for hard-to-handle compounds such as isomers and unstable materials Retention data are not always available in articles dealing with these materials For this reason, codes for unorthodox data have been added to the data-bibliography cards Table can be used to illustrate the use of an unorthodox data code referring to the separation of isomers The data are listed in sequence by the serial number Retention data are given for serial numbers 435250 and 435260 which are for cw-traw-farnesol and trans-trans-(ameso\, respectively Retention data are not given for the cis- cis- (435254) and trans-cis- (435258) isomers* However, the unorthodox data code C under the heading U indicates that retention times are given but no value for the gas holdup is given for these isomers (see codes in Table 5) Anyone working with all four of these isomers should refer to JOCE, Vol 28, p 1086 (1963) JOCE is the CODEN for Journal of Organic Chemistry (see CODEN in Table 7) Suppose data on 3,3-dimethyl-l-butene which has a molecular formula of C0H12 are desired The NFC in Table show that the serial numbers for compounds with a molecular formula of C0H12 run from 154500 to 156700 The serial number for 3,3-dimethyl-lbutene is 156000 All the DBC for this compound are listed following the molecular formula and name of the compound Perhaps, it would be of interest to examine the first two entries under SER NO 156000 The first item, at 25 C, has a liquid phase code of 160 which, from Table 1, is for liquid paraffin, or Nujol Code R under the heading A indicates that the relative retentions were recalculated to a new reference material However, when the computer examined the block of data in which 3,3-dimethyl-l-butene was contained, it was found that either separation factors were reported (code A under heading U from Table 5) instead of relative retentions or an incorrect gas holdup was used The computer transferred the data which were initially coded in the card to a new location under the headings O-RM and OLD-RR Thus, the old data in the card were relative to nonane (9 under O-RM) and had a separation factor of 0.010 The second item, at 37 C, was obviously reported by the same author for the same liquid phase as the first item, Nujol The code B under the heading C signifies that the relative retention, 0.95 relative to pentane, and retention index of 495 were calculated by the computer and the reciprocal slope 2.1863 (calculated using log to base 10) under the heading 1/B was computed from the Antoine equation (see Table 6) The old values which were coded into the system are retained in the listing under O-RM and OLD-RR as a relative retention of 0.014 relative to nonane Other data in Table can be analyzed in a similar manner It has been shown that data listed as in Table can be used to determine if chromatographic data are reported for a given compound by searching through the list for the molecular formula of the compound in question Lists of data arranged in sequence as in Table are also useful for the selection of the liquid phase for separating a mixture of two or more substances For example, consider finding a column which will give the best separation for ethyl alcohol (boiling point 78 C) and ethyl acetate (boiling point 77 C) The data for ethyl alcohol are found under SER NO 19300, and the data for ethyl acetate are found under SER NO 74200 Both compounds contain retention data on over 60 liquid phases Hexadecane (LP code 120) is the first liquid phase which is common to both solutes Ethyl alcohol has a retention of 0.55 relative to pentane, and ethyl acetate has a retention of 0.59 relative to hexane Changing from a higher reference w-alkane to a lower one is easily done by using the following equations if the 1/B value is given: r