2576
Anal. Chem. 1982, 54, 2576-2582
(8) Dehnen, W.; Tominges, R.; ROOS, J. Anal. Biochem. 1973, 53. 373-383. (9) Niva, A.; Kumakl, K.; Nebert, D. W. Mol. Pharmacol. 1975, 1 1 , 399-408. (10) Beraud, M.; Galliard, S.; Derache, R. Chem.-Biol. Interact. 1980, 31, 103-112 .- - . .-. (11) Yang, C., S.; Strickhart, F. S. Biochem. Pharmacol. 1974, 2 3 , 3129-3138. (12) Ngo, T. T. Int. J . Biochem. 1979, 1 1 , 459-485. (13) Wlseman, A. J . Chem. Techno/.Biotechnol. 1980, 30, 521-529. (14) Cohen, W.; Barlcos, W. H.; Kastl, P. R.; Chambers, R. P. "Methods in Enzvmoioav"; Mosbach. K., Ed.; Academic Press: New York, 1976; Vol:44, pip 319-328. (15) Lee, M. L.; Hltes, R. A. Anal. Chem. 1976. 48, 1890-1693. (16) Rosenkranz, H. S.; McCoy, E. C.; Sanders, D. R.; Butler, M.; Kiriazides, D. K.; Mermeistein, R. Science 1980, 209, 2039-2043. (17) Kinoshita, N.; Shears, B.; Gelboln, H. V. Cancer Res. 1973, 33, 1937-1944. (18) Lowry. 0. H.; Rosebrough, N. J.; Farr, A. L.; Randall, R. J. J . Biol. Chem. 1961. 193,285-275. (19) Poilak, A.; Blumenfeld, H.; Wax, M.; Baughn, R. L.; Whitesides 0. M. J . Am. Chem. SOC. 1980, 102,8324-8336. (20) Giammarise, A. T.; Evans, D. L.; Butler, M. A,; Murphy, C. 6.; Kiriazides, D. K.; Marsh, D.; Mermelsteln, R. "Improved Methodology for Carbon Black Extraction", Sixth International Symposium on Polynuclear Aromatlc Hydrocarbons, Columbus, OH, Oct 1981. (21) Yang, Y.; D'Silva, A. P.; Fassel, V. A. Anal. Chem. 1981, 53, 894-899. (22) Yang, S. K.; Selkirk, J. K.; Plotkin, E. V.; Gelboin, H. V. Cancer Res. 1975, 35,3842-3850.
(23) Golan. M. D., Bucker, M.; Schmassmann, H. U.; Raphael, D.; Jung, R.; Blndel, U.; Brase, H. 0.; Tegtmeyer, F.; Frledberg, T.; Lorenz, J.; Stasiecki, P.; Oesch, F. Drug Metab. Dlspos. 1980, 8 , 121-126. (24) Camps, J.; Razzouk, C.; Roberfrold, M. B. Chem.-Biol. Interact. 1977, 16, 23-38. (25) Berezin, I . V.; Kllbanov, A. M.; Martinek, K. Russ. Chem. Rev. 1975, 44 (l), 9-25. (26) Thomas, D.; Brown, G. "Methods in Enzymology"; Mosback, Klaus, Ed.; Academlc Press: New York, 1976; Vol. 44, pp 901-929. (27) Goldman, R.; Goldstein, L.; Katchalski. E. I n "Biochemical Aspects of Reactions on Solid Supports"; Stark, G. R., Ed.; Academic Press: New York, 1971; pp 1-78. (28) Klibanov, A. M. Anal. Biochem. 1979, 9 3 , 1-25. (29) Oesch, F.; Jerlna, D. M.; Day, J. W.; Rice, J. M. Chem.-Biol. Interact. 1973, 6, 189-202. (30) Tadahlko. F.; Matsuyama, A.; Nagao, M.; Suglmura, T. Chem.-Blol. Interact. 1980, 32, 1-12. (31) Levin, W.; Ryan, D.; West, S.; Ayh, L. J. Biol. Chem. 1974, 249, 1747-1754. (32) Ingalls, R. G.; Squlres, R. 0.; Butler, L. G. Biotechnol. Bioeng. 1975, 17, 1627-1837.
RECEIVED for review June 7, 1982. Accepted September 20, 1982. This research was suported by the U.S. Department of Energy, Contract No. W-7405-Eng-82,Office of Health and Environmental Research, Physical and Technological Studies, Budget Code GK-01-02-04-3.
Determination of Transferable Hydrogen in Coal Liquids by Mass Spectrometry J. T. Swansiger," H. T. Best, D. A. Danner, and T. L. Youngless Gulf Science and Technology, Pittsburgh, Pennsylvania
15230
Two low-resolution mass spectral (LRMS) group type analyses have been callbrated to quantltate transferable hydrogen and to more accurately characterlre the aromatlc and hydroaromatlc specles In coal llqulds. The analysls for llght coal llqulds (50-300 "C) reports 20 aromatlc and hydroaromatic types lncludlng phenols and dlhydroxybenrenes, whlle the analysls for heavy coal llqulds (300-500 "C) reports 30 aromatlc and hydroaromatic species. The LRMS transferable hydrogen values were shown to be In good agreement wlth 13C NMR values for a serles of coal llquld dlstlllates and process oils.
Hydrogen donors are of fundamental importance in coal liquefaction. It has been shown that hydrogen donors in coal liquefaction are not necessarily the classical hydroaromatics and that coal free radicals can abstract hydrogen from many sources including naphthenes, alkyl aromatics, and dissolved hydrogen (1,2). However, hydroaromatics are of most interest due to their comparatively high reactivity as hydrogen donors. The 13C NMR technique of Seshadri et al. (3), which determines transferable hydrogen by using the hydroaromatic region of the spectrum, was used as the reference technique. The LRMS technique uses the percent transferable hydrogen for each hydroaromatic type to calculate the total transferable hydrogen. Both LRMS analyses are based on our previous work, which described a 17-component group type analysis for coal liquids ( 4 ) . However, attempts to use the early calibration matrix to calculate transferable hydrogen indicated that the LRMS data were consistently high with respect to 13C NMR. Since we considered 13C NMR to be more struc0003-2700/82/0354-2576$0 1.25/0
turally sensitive than the mass spectral group type analysis, agreement with 13C NMR data for transferable hydrogen should be indicative that appropriate calibration compounds and characteristic ions have been selected for the LRMS analyses. An advantage of the group type analyses is the detailed compositional data reported for aromatic and hydroaromatic types. By fitting the LRMS data to 13C NMR data, we feel that we have resolved most of the significant series overlaps and improved structural accuracy of the LRMS analyses. EXPERIMENTAL SECTION Sixteen narrow boiling fractions of a coal liquid product, covering a boiling range of 42-482 "C, were characterized by GC/MS, LRMS, and 13C NMR. The coal liquid was obtained from SRC-I1 processing of Powhatan No. 5 mine coal. The material fractionated was a blend of debutanizer bottoms and process solvent. Additional physical, chemical, and thermodynamic properties for these fractions are contained in a comprehensive report by Gray (5). The various characterization data for these fractions were used to support selection of calibration components in the LRMS group type analyses. Low-Resolution Mass Spectrometry. The LRMS calibration data and analyses were obtained on a CEC 21-103C mass spectrometer which has been updated by using Nuclide Corp solidstate electronics. The Nuclide components include the highvoltage power supply (HV-21), exponential scan generator (ESG-l),trap current regulator (ER-12/103), ion chamber temperature regulator (ST-3), electrometer amplifier/preamplifier (EA-lO/EAH-300),source divider (SC-103),and magnet control with temperature compensated Hall device (MR-13/ 103). The existing diffusion pump was replaced by a Leybold-Hereaus 220 L/s turbomolecular pump for improved source pumping. The only original parts of the spectrometer still in use are the magnet coils, analyzer, and ion source. The spectral data were acquired 0 1982 American Chemlcal Societv
ANALYTICAL CHEMISTRY, VOL. 54, NO. 14, DECEMBER 1982
at 70 eV with an ionizing current of 10 pA. The accelerating potential was swept from 3200 to 400 V to give a scan rate of 20 min/decade. The ion source temperature was set to give a m / e 127/226 ratio of 0.75 for n-hexadecane,which corresponds to -250 "C and is regulated to k0.25 "C. The inlet is all glass with a gallium frit and is heated to 350 OC. The data were acquired by an Infotronics CRS-160 digitizer and transmitted via an IBM 7406 device coupler to an Amdahl470/V7B coniputer for processing. GC/MS. Capillary GC/MS data were obtained for aromatic cuts of distillate fractions 1-11 (42-372 "C) using a Varian 112s mass spectrometer. Sevleral of the distillates were also analyzed using a Finnigan 4510 GC/MS. The spectra were acquired at 70 eV with a scan rate of 2 s/decade. The capillary column was a 45 m X 0.025 cm WCOT fused silica with B SE-54 liquid phase. The GC was programmed from 30 to 250 "C at 2 OC/min with a helium flow rate of 2 mL/min. Distillate fractions 12-16 (326-450 "C) were not analyzed due to low volatility and poor chromatographic resolution of these fractions. High-Resolution Mam Spectrometry. High-resolution data were acquired for several high boiling distillate cuts using a Kratos MS-50 spectrometer. The data were acquired at 70 eV at a scan rate of 10 s/decade. Samlple introduction was through the all-glass heated inlet at 300 "C. A resolution of 10000 was used. l3C NMR. A Varian CIFT-20 multinuclear NMR spectrometer was used to determine transferable hydrogen values for selected narrow and wide boiling SRC-I1fractions. Chemical shifts were expressed as parts per million downfield from an internal MelSi lock. Separations. Aromatic fractions for GC/MS, LRMS, and NMR were separated by FIA (fluorescent indicator adsorption) or HPLC, depending on the boiling range of the sample. FIA (6) was applied to distillation cuts 1-10 boiling below 315 "C. The HPLC Sara (7) technique was used to separate the aromatics from distillates boiling above 315 "C. R E S U L T 8 AND DISCUSSION Calibration. The characteristic ions for each class are typically the (M)+ and (M - 1)+ ions. However, some of the series overlaps were resolved by using characteristic fragment (M - 15)+and (M - 28)' ions. Overlaps between the molecular ion series of the various group types are minimal due to the short (three to four carbons) alkyl chain lengths characteristic of most coal liquids. It should be recognized that alkyl substitution may also be process dependent. Application of the coal liquid matrices to a hydrotreated petroleum or shale oil based material may cause errors due to the long alkyl chain lengths typical of these materials. Most of the redundancies in the matrices were between aromatic and hydroaromatic types. Molecular ion plots of distillation cuts 6-16 were made with LRMS low ionizing voltage data to help resolve these redundancies. The molecular ion intensity vs. carbon number was plotted for each group type taking into account the distillate boiling range and the boiling point of the molecular type. The plots were used primarily to decide whether proposed compound types were consistent with the boiling range of each distillate cut and also to verify that the alkyl substitution patterns did not cause significant ion series overlaps. Figure 1 shows a typical molecular ion plot of the major components for cut 10 (1281-315 "C). The plot illustrates the typical alkyl substitution of SRC-I1 products. The unsubstituted homologue is usually the most abundant in the series with rapidly decreasing abundance for three to four carbon chains. GC/MS data were also used to support calibration compound selections. Distillation cuts 1-5 (42-175 OC) were shown to contain only low levels of hydroaromatics, while cuts 6-8 (190-270 "C)contained significant concentrations of indans. The GC/MS data foir cut 11 are shown in Figure 2 and Table I. In most cases, specific isomers were not identified and many peaks contained mixtures of several components, but the data were useful in resolving specific redundancies as described below.
2577
-
21
a
-.. m
0
.h
-m d
2000
-
10
11
12
13
14
15
16
17
18
Carbon #
Flgure 1. Molecular ion plots for cut 10, boiling range 281-315 OC.
Table I. GC/MS Data for Distillate Cut 11 peak no. 934 995 1035 1055 1089
1140 1177 1192 1213 1233 1250 1273 1314 1340 1 358 1420 1449 1489 1498 1518 1548 1569 1610 1628 1667 1717
component me thylfluorene dime thy1biphenyl te trahy drophenanthrene methyltetrahydrophenanthrene t hexahy drophenanthrene methylte trahy drophenanthrene phenanthrene dimethylfluorene t trimethylbiphenyl di- t trimethylfluorene t dimethylbenzindan di- + trimethylfluorene + dimethylbenzindan trimethylbenzindan t dimethylfluorene trimethylbenzindan t dimethylfluorene trimethylbenzindan t trimethylfluorene trimethylbenzindan methyltetrahy drophenanthrene methylhexahy drophenanthrene 3-methylphenanthrene 2-methylphenanthrene phenyl tetralin methylphenanthrene phenyltetralin methylphenyltetralin cyclohexylnaphthalene t methylcyclohexylnaphthalene cyclohexylnaphthalene t methylcyclohexylnaphthalene phenylnaph thalene dimethylphenanthrene dimethylphenanthrene t methylphenyltetralin -t methylcyclohexylnaphthalene
1755 1782 1826 1858 1880
1925 1961 1997
dimethylphenanthrene hexahydropyrene di-, tetra- t hexahydrofluoranthrene fluoranthrene propylphenanthrene methyl- + dimethylphenylnaphthalene propylphenanthrene pyrene
The significant overlaps were resolved in both analyses as follows:
2578
ANALYTICAL CHEMISTRY, VOL. 54, NO. 14, DECEMBER 1982
Table 11. Characteristic Ions for Light Coal Liquid Matrix characteristic ions Z no. type -28
benzopyrenes
- 24 -1 2 -16 -18 -22
chrysenes decahydropyrenes hexahydropyrenes tetrahy drofluoranthenes pyrenes/fluoranthenes
-20
phenylnaphthalenes
-10
octahy drophenanthrenes
-12 -14
hexahy drophenanthrenes tetrahy drophenanthrenes
-18
-16
phenanthrenes fluorenes
-14
biphenyls/acenaphthenes
-8
tetralins
-10
tetrahydroacenaphthenes
-12
naphthalenes
-6
indans benzenes
-6
dihy droxy benzenes
-6
phenols
-8
251, 252, 265, 266, 279, 280 227, 228, 241, 242 211, 212, 225, 226 207, 208, 221, 222 205, 206, 219, 220 201, 202, 215, 216, 229, 230 203, 204, 217, 218, 231, 232 185, 186, 199, 200, 2i3,214 183,184,197,198 154, 168, 182, 196, 210 177, 178,191, 192 165, 166, 179, 180, 193,194 91, 105, 153, 167, 181 104, 118, 132, 146, 160,174 129, 130, 157, 158, 171,172 128, 141, 142, 155, 156,169, 170 117, 131, 145,159 77, 78, 91, 92, 105, 106, 119, 120 109, 110, 123, 124, 137,138 93, 94, 107, 108, 121, 122, 135, 136
(1)Tetrahydrophenanthrene was resolved from a combination of biphenyls and acenaphthenes by using characteristic fragment ions. The group sums are tetrahydrophenanthrene = 154 168 182 196 210
+
+
+
+
Table 111. Characteristic Ions for Heavy Coal Liquid Matrix Z no.
-20
type decahy drobenzochr ysenes
-22
octahydrobenzochrysenes
-24
hexahy dro benzochrysenes
- 26
tetrahydro benzochrysenes
-30 -1 8 -20 -22 - 24 - 26 -28
benzochr ysenes decahy drobenzopyrenes octahydrobenzopyrenes hexah ydrobenzopyrenes tetrahy drobenzopyrenes binaphth yls benzopyrenes
-1 2 -1 6 -1 8 -24 -12 -16
dodecahy drochrysenes octahydrochrysenes hexahy drochrysenes chrysenes decahy dropyrenes hexahy dropyrenes
-1 8
-22
tetrahydrofluoranthenes pyrenes/ fluoranthenes
-20
phenylnaph thalenes
-10
octahy drophenanthrenes
-1 2 -14
hexahy drophenanthrenes tetrahy drophenanthrenes
-1 8 -16
phenanthrenes fluorenes
-14
biphenyls/acenaphthenes te tralins
+ 105 + 153 + 167 + 181
-1 2
naphthalenes
(2) Indans and tetralins are resolved by using the group sums 104 118 132 146 160 174 tetralins = 117 131 141 159 indans =
-6
+
+ +
+ + + +
+
The basis for the tetrahydrophenanthrenes and tetralin group sums is strong (M - 28)+ions produced by CzH4splitting from the saturated ring. (3) The overlap of dihydropyrene and phenylnaphthalene is considered to be all phenylnaphthalene. GC/MS data indicated that phenylnaphthalenes were the more abundant component in distillate cut 11. (4) The overlap of dihydrophenanthrenes and fluorenes is considered to be all fluorenes. GC/MS showed substituted fluorenes in cut 11but no evidence of dihydrophenanthrene. (5) The overlap of dihydrobenzopyrene and binaphthyl is considered to be all binaphthyl. Cut 12 had poor chromatographic resolution and GC/MS could not confirm the dominate component. (6) The overlap of dihydronaphthalenes and tetrahydroacenaphthenes is considered to be all tetrahydroacenaphthenes. GC/MS data showed tetrahydroacenaphthenes in cut 8, while no dihydronaphthalenes were detected in cuts 7 or 8. Cronauer (8)noted that the abstraction of hydrogen from tetralin apparently proceeds through the
177,178,191,192 165, 166, 179, 180, 193,194 91, 105, 153, 167, 181
-8
tetrahydroacenaphthenes
91
287, 288, 301, 302, 315,316 285, 286, 299, 300, 313, 314 283, 284, 297, 298, 311,312 281, 282, 296, 296, 309, 310 277, 278, 291, 292 261, 262, 275, 276 259, 260, 273, 274 257, 258, 271, 272 255, 256, 269, 270 253, 254, 267, 268 251, 252, 266, 266, 279, 280 239, 240 249, 250, 263, 264 233, 234, 247, 248 227, 228, 241, 242 211, 212, 225, 226 207, 208, 221, 222, 235, 236 205, 206, 219, 220 210, 202, 215, 216, 229, 230, 243, 244 203, 204, 217, 218, 231, 232, 245, 24 6 185, 186, 199, 200, 213, 214 183,184,197,198 154, 168, 182, 196, 21 0
-10
biphenyl/acenaphthene =
characteristic ions
benzenes
104, 118, 132, 146, 160,174 129, 130, 157, 158, 171,172 . 128, 141, 142, 155, 156,169,170 77, 78, 91,.92, 105, 106,119,120
dihydronaphthalene intermediate but that the intermediate rapidly gives up its hydrogens and only minor concentrations of dihydronaphthalene were detected in the reaction products. (7) The overlap of hexahydropyrene and phenyltetralin could not be resolved. Both components occur in the SRC-I1 materials as indicated by the GC/MS data of cut 11. Characteristic ions for each analysis are shown in Tables I1 and 111. Definition of Transferable Hydrogen. Work by Cronauer et al. has shown that hydrogen donors are not necessarily hydroaromatics and that coal free radicals can abstract hydrogen from any available source (9). Transferable hydrogen, in terms of the mass spectral analysis, is considered to be due to the classical hydroaromatics. However, other structures can act as good or poor hydrogen donors in a comparative sense. Figure 3 shows how hydrogen donors are classified in the mass spectral analysis and the number of transferable hydrogens per molecule. It should be recognized that all of the structures shown can transfer hydrogen to some extent. Tetralin and octahydrophenanthrene are considered classical hydrogen donors with four and eight transferable hydrogens,
ANALYTICAL CHEMISTRY, VOL. 54, NO. 14, DECEMBER 1982
2579
100.1
I
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I
1 i00
1000 33:20
600 26: 4 0
1400 46:40
40: 00
1600 53: zu
1800 6 0 : 00
2000 56: 40
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SCAL TIME
Figure 2. Total ion current chromatogram fair cut 11. COMPONENT
STRUCTURE
--
TETRALIN
DONOR QUALITV
-
GOOD
No. TRANSFERABLE HYDROGENS
4 TETRALIN
METHYL INDAN
INDAN
Flgure 4. Rearrangement of tetralin. INDAN
MESITYLENE CH,
PHENANTHRENE OCTAHYDRO
PHENOL
A
POOR
0
POOR
0
QOOD
a
GOOD
1
CH,
&'
Figure 3. Hydrogen donor classification.
respectively. Phenols are also considered as good hydrogen donors due to the labile ]protonof the hydroxy group. Kamiya (IO) suggested that phenolics may also affect coal liquefaction by several other mechanisms including scission reaction of ether linkages, swelling of coal particles due to affinity for oxygen types, and solvation of oxygen types by hydrogen bonding. Compounds which ar'e not hydroaromatic are still susceptible to hydrogen abstraction. Mesitylene is considered as a
poor hydrogen donor; however, hydrogens can be abstracted from the methyl groups to form mesityl radicals which can dimerize or react at other available sites ( I ) . Structures containing five-membered saturate rings (indans, acenaphthenes, etc.) appear to be relatively common in coal liquids. These structures are considered to be poor hydrogen donors. Figure 4 shows one of the rearrangement reactions of tetralin to form indan. The indan products are noted to resist hydrogen transfer as compared to tetralin (1). The isomerization of six-membered rings complicates the quantitation of hydrogen transfer, since it may not be reasonable to consider the tetralin/naphthalene ratio as transferred hydrogen (2). Total Ionization Calibration. The low-resolution calibration data were obtained on a total ionization basis. Total ionization may be defined as the sum of all ion intensities per unit quantity of a compound. The principle of total ionization was used by Crable and Coggeshall(12) to provide calibration data for high molecular weight mass spectrometry. This principle is based, in part, on the work of Otvos and Stevenson (13),who studied ionization cross sections by electron impact. Their interpretation of the cross section data was that the total ion current is nearly constant when referred to liquid volume. Hood (11) also applied the work of Otvos and Stevenson by converting a mass spectrum to standard conditions of sample volume and instrument senstivity by determining a standard total ionization which is an ion sum per unit of liquid volume.
2580
* ANALYTICAL CHEMISTRY, VOL.
54, NO. 14, DECEMBER 1982
It should be noted that the sources of calibration spectra varied, including in-house, literature, extrapolated, and estimated from other hydroaromatics. The heavy coal liquid matrix is shown in Table VI. LRMS Transferable Hydrogen. The transferable hyis calculated by using the equation drogen (Ht)
Table IV. Standard Addition Tests for Various Compound Types % in
%ana- % difflyzed erence
% coal liquid added
compd type phenylnapthalene octahydrophenanthrene tetralin fluorene phenol
5.4
5.4
10.5
0.3
2.3
3.8
4.8
1.3
3.0 8.3 5.2
6.7 5.2
10.1
0.4 0.2 0.2
13.3 13.7
8.7
where fl is the weight fraction of aromatics in the sample (this is provided by the separation technique and adjusts Ht to the total sample), Hfis the weight percent transferable hydrogen for each hydrogen donor (Hf is calculated by dividing the atomic weight of transferable hydrogens by the molecular weight of the unsubstituted hydrogen donor, for example, Hf(tetra1in) = 4/132 = 0.0303), and f is the weight fraction of each hydrogen donor in the aromatic cut (this is produced by the mass spectral analysis). Ht is calculated based on the percent of each hydroaromatic group type and does not consider the alkyl substitution which would lower Ht slightly. Phenolics are included as hydrogen donors due to the labile protons of the hydroxyl groups. Three hydroaromatic types were excluded from the Htcalculation since high-resolutionmass spectral data showed interferences from oxygenated (furan, ether) types. The three classes with the most significant interferences were hexahydrobenzopyrene, hexahydrochrysene, and decahydropyrene. Components containing five-membered saturate rings are also excluded since they are considered to be poor hydrogen donors. Table VI1 shows typical group type data for two light SRC-I1process oils using the 20-componentmatrix, and Table VI11 shows data for two heavy SRC-I1 process oils using the 30-component matrix. I3C NMR Transferable Hydrogen. Hydroaromatics are quantitated in the aromatic fractions by the resonance positions between 10 and 50 ppm. This assignment of the chemical shift values is based on the 13C NMR of model hydroaromatic compounds (17). Some components that are poor hydrogen donors have spectral lines in the hydroaromatic region. These include compounds with five-membered saturate rings such as fluorenes, indans, and acenaphthenes. The contribution of unsubstituted acenaphthene is corrected by referencing the peak integral at 119 ppm and subtracting an equal integral at 30 ppm within the hydroaromatic region.
The fact that Hood's equation includes a density term implies that total ionization is an ion sum per unit weight. Other workers (14-16) have indicated basic disagreement with the results of Otvos and Stevenson. The importance of understanding the principle of total ionization is whether an analysis based on this calibration technique provides results as weight or volume percent. Since there are conflictir g data in the literature, we are proposing that analyses based on total ionization should be reported in weight percent. This is based on our experience with naphtha/reformate calibrations where application of density factors converted the data to volume percentages which fit separations data. Light Coal Liquid Analysis. The analytical matrix considers 20 group types including 18 hydroaromatic/aromatic types and two phenolic types. The analysis is intended for aromatic fractions from samples boiling between 50 and 300 "C. FIA appears to be the most suitable separation technique in this boiling range, but it should be noted that some polars will be eluted with the aromatic cut unless removed by a prior acid/base extraction. The most abundant polars are phenolics which are included in the analysis, while the relatively low concentration of nitrogen types should have little effect on the analysis, provided that their low abundance has been independently demonstrated. Response of the analysis to the standard addition of various components is shown in Table IV. The light coal liquid matrix is shown in Table V. Heavy Coal Liquid Analysis. The analytical matrix includes 30 hydroaromatic/aromatic types and is intended for aromatic cuts from samples boiling between 300 and 500 OC. Table V. Light Coal Liquid Matrix In
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,01531 31531 .!I791 12217 31535 ,31761 ,CC228 9133 C5UCl .C2641 X3bL 30157
C
a
v)
3
0
I-
I
z z W
E
.c1424 ,011067 0338C
0
I
W 8
z z
L
z W
z
I
>
V
0
z
4
> I 4
n
a
,02619 39C50 04033 .C6614
Mi57 0c3:7
4
z
v)
I-
a
3
E
c"
I-
L
4
4
z
4
z
W
L I
3
P
v)
z W U
3
8
v)
u)
C 0 0 C C C
3 57950 ,05446 ,c5537 C0302
C ,01826
C
1
0
0
0
c
0
0
0
0
0
0
1
0 C 0
C C C 0 0
3
0
C
3
3
C
0
0 3
0 0
C
0
0
C 0
3 3
C 0
0 0
0 3 05251 48458 ,31232
02248 ,00522 00136
3
3
0
3 0
0 0
15338
0
0 0
C C
0
0
03400
C
3 0
3 3
3
3
.ma 0
0 .25Ul5 C
C C
Ai450 0 ,C1500
s
0 .%730
3
0
31474 C
0 263C3
ANALYTICAL CHEMISTRY, VOL. 54, NO. 14, DECEMBER 1982
Table VI. Heavy Coal Liquid Matrix
2561
--
e
E 1
v1
x
c
ill
I 219 I 211
0
x
0
22,
2
1233:
1
1
O
3
3
O
3
I
id5 I 20. I 2CJ
c
x I85 x 181
c
X
0 3
x
1%
I 165 I si I !31
3 0 J
0 C 12330
x
c 0
I I
121 118 77
,02303
3 I
c
0 05003
0 3 C i
0
0
0
0
c
:
X
0
0 0 0 0
0
u
0 3
C
0 3
0 0
0 0
0 0
N
5
0 0
0 0 0
0 0 0
0 0
0
0
0
0 0
0 0
0 3
0 0
0
0
0
0
0
3
0 0
0
0
0 0
0 0
0
0
0
c
0 0
0 0 0 0 3 0 0 0 0
0
0
c
3
1 ! 1
i
3
2
0 0 0 0
0
0
0
0
0
0
0
0
0
."
