Ultrahigh Resolution Chromatography

Widmer, H. Michael, 199. Lambert, B. J., 49. Yang, Frank J., 91. Laub, R. J., 49. Subject Index. A. Absolute retention, resolution enhancement, 28. Ab...
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Author Index Ahuja, S a t i n d e r , 1 C a l l i s , James B., 171 D a v i s , Joe Μ., 9 F j e l d s t e d , J . C , 121 Freeman, D a v i d H., 77 Giddings, J .Calvin, 9 G r o l i m u n d , K a r l , 199 I s h i i , D a i d o , 109 J a c k s o n , W. P., 121 J e n n i n g s , W a l t e r , 27 Kong, R. C , 121 L a m b e r t , B. J . , 49 Laub, R. J . , 49

L e e , M. L., 121 L o c h m u l l e r , C. Η., 37 R a n d a l l , L. G., 135 R i c h t e r , Β. Ε. , 121 R o b e r t s , W. L., 49 S c h u r e , Mark R. , 9 Simon, R i c h a r d , 59 S m i t h , C. Α., 49 T a k e u c h i , T o y o h i d e , 109 W e l l s , G r e g o r y , 59 Widmer, H. M i c h a e l , 199 Yang, F r a n k J . , 91

Subject Index Β

A Absolute r e t e n t i o n , r e s o l u t i o n enhancement, 28 Absorbance spectra, ethylbenzene, o-xylene, and £-xylene, I88f A c e t o n i t r i l e , solvent, RPLC, 83 Adsorption chromatography, C02-based SFC, 158-63 Adsorption surface, SFC, solvent i n t e r a c t i o n s , 149 A i r monitors, i n d u s t r i a l chromatography, 200 A l d i t o l acetates, chromatogram, 32f A l k y l groups, bonded, HPLC development, 82,83 Amides, enantiomeric, separation, 43,44f Amine compounds, RPLC, 84 Amino acids HPLC, 86,87f ion exchange, 81 ligand exchange, 4 Analysis time, column diameter reduction, 53 Anthracene, C02 density, SFC, 141 Anthraquinones, s u b s t i t u t e d , C02-based SFC, 157f Apparatus, micro HPLC, 110 Aromatic compounds, C02 density, SFC, 141 Aromatic heterocycles, n i c k e l c a t a l y s t separation, 46f Aromatic hydrocarbons, nitropolynuclear, bonded phase separation, 43

Back pressure, e f f e c t , C02-based SFC, 162,167 Band broadening HPLC, 2 TCD, 68 Band width, and p l a t e number, 38 Baseline peak, computer-simulated chromatograms, I8,20f Baseline separation, peak-counting methodology, 17,18 Benzenethiol, RPLC, 99f Benzo(e)pyrene, e x c i t a t i o n spectra, 191f,192f Bis(chloromethyl) ether, a i r monitor, 204f Bonded a l k y l f u n c t i o n a l groups, HPLC development, 83 Bonded counterions, ion exchange, 83 Bonded phase, s t a b l e , micro HPLC, 115 Bonded-phase columns, s t a b l e , r e s o l u ­ t i o n enhancement, 30 Butane chromatogram, small-volume TCD, 69f thick f i l m c a p i l l a r y GC, 211f

223

c Capacity factor vs. column diameter, 52-54 C a p i l l a r y column diameter reduction e f f e c t s , 49-57 SFC, van Deempter curves, 138-43 w a l l coated, e f f i c i e n c y , 205t wide-bore fused-glass, small-volume TCD, 72

224

ULTRAHIGH RESOLUTION CHROMATOGRAPHY

C a p i l l a r y gas chromatography discussion, 4 l i q u i d phase, 30 C a p i l l a r y l i q u i d chromatography, open-tubular, immobilized s t a t i o n ary phases, 115 Capillary supercritical fluid chromatography, schematic diagram, 124f Carbon black e x t r a c t , c a p i l l a r y SFC, 128-129 Carbon dioxide pyrene i n , solute binary d i f f u s i v i t y , 138-43 solvent power, 145 use, c a p i l l a r y SFC, 128 Carbon dioxide based s u p e r c r i t i c a l f l u i d chromatography, d i s c u s s i o n , 135-68 Carbonylbis(J2-leucine) isopropyl e s t e r , enantiomeric amide separation, 44f Carboxylic a c i d s , RPLC, 84 Carrier-induced s e l e c t i v i t y , HPLC development, 85 C a r r i e r v e l o c i t y , l i n e a r , vs. column diameter, 55f C e l l volume, detector, narrow-bore packed-column HPLC, 100 Charge-transfer acceptor phases, polynuclear aromatic compounds, 45 Chemical industry, r o l e o f u l t r a h i g h r e s o l u t i o n chromatography, 199-221 C h i r a l recognition r a t i o n a l e , 4 C h i r a l separation, HPLC, amino a c i d s , 86 C h i r a l stationary phase, separation o f enantiomeric amides, 43 Chloroform C02-based SFC hormone mixture, 156f substituted anthraquinones, 157f xanthone and flavone, 158f C02 modifier, adsorption SFC, 158-63 Cholesteric e s t e r s , s t a t i o n a r y phases i n HPLC, 4 Chromatogram computer simulated, I 6 t numerical deconvolution techniques, 173f various, column diameter reduction, 56 Chromatography, various detectors, numerical deconvolution techniques, 174-93 C i g a r e t t e - l i g h t e r gas, t h i c k - f i l m c a p i l l a r y GC, 211f Coal powdered, use i n micro HPLC, 115 product, c a p i l l a r y SFC, 128 solvent-refined l i q u i d , SFC, 130f water e x t r a c t s , micro HPLC, 1 l 6 f

Coating, c a p i l l a r y columns, SFC, 122 Column, various, C02-based SFC, 167 Column diameter vs. capacity f a c t o r , 52-54 c a p i l l a r y , reduction e f f e c t s , 49-57 vs. i n l e t pressure, 53,55f r e s o l u t i o n enhancement, 28 Column e f f i c i e n c i e s , C02-based SFC, 135-68 Column length effects, industrial chromatography, 209 r e s o l u t i o n enhancement, 28 various e f f e c t s , 2 l 6 f Column peak capacity, peak-counting methodology, 17 Column performance, i r r e p r o d u c i b i l i t y , HPLC development, 83 Column preparation column diameter reduction, 51 micro HPLC, 110 Column r e - e q u i l i b r a t i o n , C02-based SFC, I60f Column s e l e c t i v i t y , HPLC development, 81 Column switching, r e s o l u t i o n enhancement, HPLC, 86 Column technology, c a p i l l a r y SFC, 122 Component density, computer-simulated chroma tograms, 19 Component number, computer-simulated chromatograms, 22 Component overlap, s t a t i s t i c a l model, 9-25 Computational procedure, Gaussian-component chromatograms, 14 Computer-simulated chromatogram component overlap model, 9-25 numerical deconvolution techniques, 173f Constrained least-squares a n a l y s i s , numerical deconvolution, 175 Contour p l o t s , two-dimensional chromatography, 194f Coronene, C02 density, SFC, 141 C r i t i c a l resolution computer-simulated chromatograms, 23 peak-counting methodology, 17 Current vs. temperature, small-volume TCD, 67f D Dead volume, HPLC, d i s c u s s i o n , 2 n-Decane, capacity factor vs. column diameter, 54f Deconvolution, numerical, 171-98 Density component, computer-simulated chromatograms, 19 c o n t r o l , c a p i l l a r y SFC, 123

225

INDEX Density—Continued mobile phase, C02-based SFC, 138-43 and temperature, simultaneous e f f e c t s , SFC, 143 Detection l i m i t , TCD, 63 Detector c a p i l l a r y GLC band broadening, 38 c a p i l l a r y SFC, 125 flow rate vs. peak shape, 71f r e s o l u t i o n enhancement, HPLC, 88 various HPLC, 4 i n d u s t r i a l chromatography, 219 narrow-bore packed-column HPLC, 100 numerical deconvolution techniques, 171-93 SFC, 6 w a l l temperature, modulated TCD, 74 Diameter, column, r e s o l u t i o n enhancement, 28 D i f f u s i v i t y , pyrene i n C02, 138-43 Dimensions and properties, column diameter reduction, 52t Dimethyl esters o f d i c a r b o x y l i c a c i d s , chromatogram, 35f 2,6-Dimethylphenol, temperature dependence o f Kovats i n d i c e s , 220f Diol functionality, size-exclusion chromatography, 83 Dodecanethiol, RPLC, 99f

Enantiomers amino a c i d , HPLC, 87f separation, 43,44f EPA p r i o r i t y p o l l u t a n t , HPLC separation, 96f,104 Epoxide groups, micro HPLC, 111 Epoxy r e s i n oligomers micro HPLC gradient separations, 111 s t r u c t u r e , 114 Ethylbenzene absorbance spectra, I88f r e l a t i v e concentration vs. eigenvalues, 191f retention p r o f i l e s , I88f E x c i t a t i o n spectra, 9-methylanthracene and benzo(e)pyrene, 191f,192f Exposure l e v e l , maximum, various p o l l u t a n t s , 203t F

Factor analysis GC-MS data, 184 three-dimensional chromatography, 190 TLC, HPLC, and LC data, 186 Fast sampling valve i n l e t system, small-volume TCD, 66f Fatty a c i d s , methyl esters, chromatogram, 34f Filament resistance, small-volume TCD, 65 Ε Film thickness effects Earth gas, thick f i l m c a p i l l a r y i n d u s t r i a l chromatography, 209 GC, 211f various, 2 l 6 f Efficiency l i q u i d phase, r e s o l u t i o n column diameter reduction, 52 enhancement, 30 comparison, HPLC and GC, 5 vs. peak inversions, 215f equation, 203 TCD, 63 improvement, 207 Eigenanalysis, numerical deconvolution Flame-based detector HPLC, 4,6 techniques, 182 narrow-bore packed-column HPLC, 105 Eigenvalues vs. r e l a t i v e concentration, ethylbenzene, 191f Flame-ionization detector (FID) c a p i l l a r y GC, gasoline, 201f Electrochemical detectors, narrowc a p i l l a r y SFC, 128 bore packed-column HPLC, 100 detector band broadening, 68 E l e c t r o n i c time constant, TCD, 61 plate height vs. flow v e l o c i t y , 42f Electroosmosis and electrophoresis, SFC, 6 discussion, 6 Flame-photometric detector (FPD), Elution narrow-bore packed-column solvent gradient, micro HPLC, 111 HPLC, 105 temperature Flavone, C02-based SFC, 157 and column length, 213f Flow path redesign, e f f e c t , 39 and f i l m thickness, 21Of Flow rate Emission spectra, 9-methylanthracene e f f e c t , small-volume TCD, 68,70 and benzo(e)pyrene, 191f,192f narrow-bore packed-column HPLC, 105 Empirical r e s o l u t i o n s , computervs. response, small-volume TCD, 69f simulated chromatograms, 22

ULTRAHIGH RESOLUTION CHROMATOGRAPHY

226

Flow v e l o c i t y vs. plate height FID, 42f TCD, 41 f Fluorescence detector c a p i l l a r y SFC, 125 narrow-bore packed-column HPLC, 100 schematic diagram, 103f SFC, 6 Fluorescent materials, TLC multichan­ n e l detector, 6 Fluoroalcoholic bonded stationary phase, c h i r a l , HPLC, 4 Frontal d i s t o r t i o n , peak shape, s m a l l volume TCD, 72 Fourier transform IR (FTIR) detector HPLC, 4 narrow-bore packed-column HPLC, 102 Fused s i l i c a column g l a s s - c a p i l l a r y wide-bore, s m a l l volume TCD, 72 micro HPLC, 112f r e s o l u t i o n enhancement, 31 G Gas, various, t h i c k - f i l m c a p i l l a r y GC, 21 I f Gas chromatography-mass spectrometry (GC-MS) data, factor a n a l y s i s , 184 Gasoline c a p i l l a r y GC, 200 FID c a p i l l a r y GC, 201f Gaussian noise, computer-simulated chromatograms, 19,20t Glass c a p i l l a r y columns, wide-bore fused, small-volume TCD, 72 Golay equation, open-tubular column, 50,140 Gradient-elution method, continuous, micro HPLC, 111 Gradient separation, epoxy r e s i n oligomers, micro HPLC, 113f,H4f,1l8f Grob t e s t mixture, c a p i l l a r y GC, 207 H Hamburger, Helmut, HPLC development, 79 Hemoglobin v a r i a n t s , LC and HPLC, 78f Heterocycles, aromatic, n i c k e l c a t a l y s t separation, 46f Hexadecane, peak shape, small-volume TCD, 7 3 f Hexamethyldisilazane, column diameter reduction e f f e c t s , 51 Hexanethiol, RPLC, 99f High performance l i q u i d chromatography (HPLC)—See High pressure l i q u i d chromatography High pressure l i q u i d chromatography (HPLC) discussion, 2

High pressure l i q u i d chromatography (HPLC)—continued factor a n a l y s i s , 1 hemoglobin v a r i a n t s , 78f h i s t o r i c a l development, 77-88 micro, complex mixtures, 109-118 narrow-bore m i c r o p a r t i c l e packed, 91-105 packed column, van Deempter curves, 138-43 reversed phase, s e l e c t i v i t y t r i a n g l e , 149 and SFC, e f f i c i e n c i e s compared, 135-68 various columns, e f f i c i e n c y , 205t Hildebrand s o l u b i l i t y parameter, C02, 146 Hormones, modifier s e l e c t i v i t y , C02-based SFC, 156f Hydraulic systems, microbore column HPLC, 100,101f I Ideal chromatogram, numerical decon­ v o l u t i o n techniques, 177 Imaging spectrophotometer, block diagram, 192f Industry, chemical, r o l e o f u l t r a h i g h r e s o l u t i o n chromatography, 199-221 I n j e c t i o n , e f f e c t , C02-based SFC, 162 Injector narrow-bore packed-column HPLC, 97 new, i n d u s t r i a l chromatography, 217 I n l e t pressure vs. column diameter, 53,55f I n l e t system, fast-sampling valve, small-volume TCD, 6 6 f Instrumentation c a p i l l a r y SFC, 123 HPLC development, 79 Internal loop sampling valve, narrowbore packed-column HPLC, 9 8 f Ion-exchange chromatography amino a c i d s , 81 bonded counterions, 83 HPLC, carrier-induced s e l e c t i v i t y , 85 nucleotides and nucleosides, 82 Ion-pair chromatography, HPLC, discussion, 3 Ion suppression, RPLC, 84 I s o e l e c t r i c focusing (IEF), 6 Isomeric solutes, separation, 6 Isophenindamine, HPLC separation, discussion, 3

Κ Kovats i n d i c e s , i n d u s t r i a l chromatography, 212,2l6t

227

INDEX L

2-Methoxyethanol, C02-based SFC hormone mixture, 156f Laser-fluorometry detector, HPLC, 4 substituted anthraquinones, 157f Least-squares analysis xanthone and flavone, 158f computer-simulated xanthines, 153f chromatogram, 19-24 9-Methylanthracene, e x c i t a t i o n numerical deconvolution spectra, 191f,192f technique, 175,176f Methyl esters o f unsaturated f a t t y two-dimensional chromatography, 193t a c i d s , chromatogram, 34f Length, column, r e s o l u t i o n Methylene c h l o r i d e , C02 modifier, enhancement, 28 adsorption SFC, 158-63 Ligand-exchange chromatography Micro high pressure l i q u i d chromatog­ amino a c i d s , 4 raphy mechanism, HPLC, 86 complex mixtures separation, 109-118 Linear c a r r i e r v e l o c i t y vs. column gradient separation, 113f,1I4f,1I8f Microbore column diameter, 53,55f HPLC Linear v e l o c i t y discussion, 3 importance, SFC, 138-43 hydraulic system, schematic, 101f mobile phase, vs. p l a t e height, LC LC-MS i n t e r f a c e , schematic and SFC, 137 view, 220f optimum, s u p e r c r i t i c a l f l u i d s , 141 technology overview, 91-105 Liquid adsorption chromatography, Microparticle-packed narrow-bore s e l e c t i v i t y t r i a n g l e s , 150f HPLC, 91-105 Liquid chromatography (LC) Mobile phase c a p i l l a r y , open tubular, immobilized density, C02-based SFC, 138-43 stationary phases, 115 l i n e a r v e l o c i t y vs. plate height, LC factor a n a l y s i s , 186 and SFC, 137 hemoglobin v a r i a n t s , 78f SFC-MS, 131 Liquid chromatography-mass spec­ solvent power, C02-based SFC, 135-68 trometry (LC-MS), microbore, various schematic view, 220f c a p i l l a r y SFC, 128 Liquid phase C02-based SFC, 165 additive e f f e c t , NPLC, 84 Modifier, C02-based SFC, 152-63 r e s o l u t i o n enhancement, 30 Modulated detector, small-volume L i q u i d - s o l i d chromatography, solvent TCD, 72 c l a s s i f i c a t i o n , 149 Modulation frequency, TCD, 74 Liquid solvent Monitors, a i r , i n d u s t r i a l Snyder c h a r a c t e r i z a t i o n , 146 chromatography, 200 s u p e r c r i t i c a l compared to Monodetector chromatography, numerical conventional, 143-52 deconvolution techniques, 174-79 Multichannel detector M numerical deconvolution, 178-93 TLC, fluorescent materials, 6 Mass spectrometry (MS) Multidimensional detector, numerical c a p i l l a r y SFC, 131 deconvolution techniques, 187-93 detector Multiwavelength spectroscopic HPLC, 4 detection, 17 narrow-bore packed-column HPLC, 102 Ν i n d u s t r i a l chromatography, 220f micro HPLC, 115 Naphthalene numerical deconvolution C0 density, SFC, 141 techniques, 184 van Deempter curves, 138-43 Mass-transfer maximum, HPLC Narrow-bore packed-column HPLC, 93-95 development, 82 Nickel complex, separation o f nitrogen Matrix e f f e c t s , i n d u s t r i a l bases, 43,46f chromatography, 200 Nitrogen bases Maxima peak counting, computernickel-complex separations, 46f simulated chromatograms, 18-20 reversed-phase HPLC, 43 Methanol, solvent, RPLC, 83 2

228

ULTRAHIGH RESOLUTION CHROMATOGRAPHY

Peak inversions vs. f i l m thickness, 215f i n d u s t r i a l chromatography, 212 Peak overlap numerical deconvolution techniques, 177,182 s i n g l e component, 9 Peak shape vs. detector flow r a t e , 71f hexadecane, small-volume TCD, 73f Peak variance, observed, TCD, 68 Pentacene, C02 density, SFC, 141 Pentylsulfonate s a l t , carrier-induced s e l e c t i v i t y , HPLC, 85 Petroleum product, commercial, chromatograms, 57f pH, e f f e c t , HPLC, 84 Phase r a t i o column diameter reduction, 52 TCD, 63 Phenindamine, HPLC separation, discussion, 3 Phosphorus-selective detector, HPLC, 4 Plate height vs. flow v e l o c i t y , FID and TCD, 4 l f 0 vs. mobile phase l i n e a r v e l o c i t y , LC and SFC, 137 Octanethiol, RPLC, 99f van Deempter curve, 137 1-0ctanol, temperature dependence o f Plate number Kovats i n d i c e s , 220f column diameter reduction, 52 Octylammonium s a l t , carrier-induced enhancement, 38 s e l e c t i v i t y , HPLC, 85 r e s o l u t i o n enhancement, 28 One-dimensional chromatography, Polar compounds, NPLC, 84 numerical deconvolution Polarity techniques, 174-79 C02, 152 Open-tubular columns take-up solvent, e f f e c t , C02-based c a p i l l a r y LC, 115 SFC, 162 Golay equation, 50 P o l a r i t y index, solvent microbore HPLC, 92,93t c l a s s i f i c a t i o n , 147 Polychlorobiphenyl (PCB), separation, Overlap, component, s t a t i s t i c a l model, 9-25 micro HPLC, 117f Polydimethylsiloxane stationary phase, column diameter reduction e f f e c t s , 51 Ρ Polynuclear aromatics, pyrene bonded phase, 47f Packed column Polystyrene oligomers, SFC, 126f choice o f l i q u i d phase, 30 Precolumn, micro HPLC, 111 HPLC and SFC, 135-68 Pressure Packing m a t e r i a l s , micro HPLC, 111 back, C02-based SFC, 162,167 Peak broadening i n l e t , vs. column diameter, 53,55f mechanism, numerical deconvolution Pressure-drop r e s t r i c t i o n , c a p i l l a r y techniques, 177 SFC, 123 narrow-bore packed-column HPLC, 102 Pressure program, c a p i l l a r y SFC, 123 Peak capacity P r i o r i t y p o l l u t a n t , EPA, HPLC d e f i n i t i o n , 12 separation, 96f,104 r e s o l u t i o n enhancement, HPLC, 86 P r o b a b i l i t y d i s t r i b u t i o n , component Peak counting overlap, 11 computer-simulated Program r a t e s , r e s o l u t i o n chromatograms, 18-26 enhancement, 28 methodology, 15 Peak d i s t o r t i o n , C02-based SFC, 161 ^ - P r o l i n e , amino acid Peak f i d e l i t y , TCD, 61 separation, 87f N i t r o g e n - s p e c i f i c analyses, c a p i l l a r y SFC, 128 Nitropolynuclear aromatics bonded phase separation, 43 pyrene bonded phase, 47f Nitrous oxide, use, c a p i l l a r y SFC, 128 Noiseless baseline peak study, computer-simulated chromatograms, I8,20f 1-Nonanal, temperature dependence o f Kovats i n d i c e s , 220f Nonnegative least-squares a n a l y s i s , numerical deconvolution, I80f Nonuniformity, column, HPLC development, 83 Normal-phase adsorption, solvent c l a s s i f i c a t i o n , 149 Normal-phase high pressure l i q u i d chromatography (NPLC), solvent s e l e c t i o n , 83 Nucleotides and nucleosides, i o n exchange separation, 82 Numerical deconvolution, super r e s o l u t i o n , 171-98

INDEX

229

2-Propanol, C02-based SFC hormone mixture, 156f substituted anthraquinones, 157f xanthines, 154f Properties and dimensions, column diameter reduction, 52t Protein HPLC r e s o l u t i o n enhancement, 88 two-dimensional e l e c t r o p h o r e s i s , 6 Pyrene, solute binary d i f f u s i v i t y i n C02, 138-43 Pyrene bonded phase, polynuclear and nitropolynuclear aromatics, 47f R Rank a n a l y s i s , three dimensional, 195f Rank a n n i h i l a t i o n numerical deconvolution, 186 two-dimensional chromatography, 193t Recycle chromatography c a p i l l a r y gas chromatography, 4 r e s o l u t i o n enhancement, 28 schematic, 29f Relative concentration vs. eigenvalues, ethylbenzene, 191f Relative r e t e n t i o n , r e s o l u t i o n enhancement, 28 Resolution between maxima, peak-counting methodology, 18 definition, 1 dimensions, I44t d i s c u s s i o n , 203-207 SFC, 136-43 enhancement d i s c u s s i o n , 27-35 HPLC, 86 i n t e r a c t i o n s , 37-47 Response vs. flow r a t e , s m a l l volume TCD, 69f Retention p r o f i l e s ethylbenzene, 188f o-xylene, and p_-xylene, I88f Reversed-phase high pressure l i q u i d chromatography (RPLC) nitrogen bases, 43 s e l e c t i v i t y t r i a n g l e , I49,150f solvent s e l e c t i o n , 83 sorbents, 82 S Sample capacity HPLC development, 82 TCD, 63 Sample i n t r o d u c t i o n , c a p i l l a r y SFC, 123

Selectivity c a p i l l a r y SFC, 128 c a r r i e r induced, HPLC development, 85 discussion, 206 HPLC development, 81-83 improvement, 207 mapping, solvent c l a s s i f i c a t i o n , 147 modifier, C02-based SFC, 153-62 t r i a n g l e s , various, 150f Sensitivity TCD, d e f i n i t i o n , 60 vs. temperature, small-volume TCD, 67f Separation techniques, new, i n d u s t r i a l chromatography, 217 S i l a n o l groups, removal, HPLC columns, 83 S i l i c a , SFC mobile phase, 152 S i l i c a column C02 m o d i f i e r s , SFC, 158-63 fused, r e s o l u t i o n enhancement, 31 g l a s s - c a p i l l a r y wide-bore fused, small-volume TCD, 72 S i l i c a d e r i v a t i v e s , HPLC development, 82 Single-component peaks, overlap, 9 Size exclusion chromatography, HPLC s e l e c t i v i t y , 82 Small-bore packed-column HPLC, 93t,94 Snyder p o l a r i t y ranking, solvent power, I45f Snyder solvent c l a s s i f i c a t i o n , SFC systems, 146-52 Solute, various, modifier-C02 mobile phases, 159t Solute binary d i f f u s i v i t y , pyrene i n C02, 138-43 Solute capacity f a c t o r s , column diameter reduction, 52 Solute s o l u b i l i t y vs. solvent power, I45f Solute-solvent i n t e r a c t i o n s , solvent c l a s s i f i c a t i o n , 147 Solvent l i q u i d , Snyder c h a r a c t e r i z a t i o n , 146 s u p e r c r i t i c a l f l u i d , comparison to conventional l i q u i d , 143-52 take-up, p o l a r i t y e f f e c t , C02-based SFC, 162 Solvent-gradient e l u t i o n , micro HPLC, 111 Solvent power, mobile phase, C02-based SFC, 135-68 Solvent-refined coal l i q u i d , SFC chromatogram, 130f

ULTRAHIGH RESOLUTION CHROMATOGRAPHY

230

Sorbent s e l e c t i v i t y , HPLC development, 81-83 Spectrophotometer, multichannel imaging, numerical deconvolution techniques, 192f,193 Split injection narrow-bore packed-column HPLC, 98f technique, TCD, 63 Spreading c o n t r i b u t i o n s , small-volume TCD, 72 S t a i n l e s s - s t e e l g l a s s - l i n e d tubing, TCD, 68 Stationary phase c a p i l l a r y SFC, 123 modification and r e s o l u t i o n enhancement, 39 s e l e c t i o n s , HPLC development, 82 thickness, TCD, 63 various, HPLC, 4 S t a t i s t i c a l a n a l y s i s , computer- simu­ lated chromatograms, 18-26 S t a t i s t i c a l theory, component overlap, 11 Steroids, free underivatized, fused s i l i c a columns, 34f Substituted anthraquinones, modifier s e l e c t i v i t y , C02-based SFC, 156 Sugars NPLC, 84 TMS d e r i v a t i v e s , chromatogram, 32f S u p e r c r i t i c a l f l u i d chromatography (SFC) c a p i l l a r y , schematic diagram, 124f van Deempter curves, 138-43 C02 based, discussion, 135-68 discussion, 121-132 s e l e c t i v e t r i a n g l e s , 150f solvents, 143-52 Τ Temperature and density, simultaneous e f f e c t s , HPLC, 143 dependence, Kovats i n d i c e s , 217 detector w a l l , modulated TCD, 74 e f f e c t , C02-based SFC, 162 elution and column length, 213f and f i l m thickness, 210f r e s o l u t i o n enhancement, 28 small-volume TCD vs. current and s e n s i t i v i t y , 67f vs. filament resistance, 65 various, C02-based SFC, 167 Tetracene, C02 density, SFC, 141 Tetrahydrofuran, solvent, RPLC, 83 Theoretical background, model o f component overlap, 11-14 Theoretical considerations, i n d u s t r i a l chromatography, 203-207

Theoretical plates c a p i l l a r y GC, 5 c a p i l l a r y SFC, 122 vs. column diameter, 52,54f column diameter reduction, 52 enhancement, 38 HPLC, 4 resolution enhancement, 28 Thermal conductivity detector (TCD) comparison o f band shape, 40f modulated, 72 plate height vs. flow v e l o c i t y , 42f small volume, c a p i l l a r y gas chromatography, 59-76 Thermionic detector, narrow-bore packed-column HPLC, 105 Thin-layer chromatography (TLC) factor a n a l y s i s , 186 multichannel detector, 6 Three-dimensional data array, 189 Three-dimensional rank a n a l y s i s , 195f Time s c a l e , measure o f r e s o l u t i o n , 2 Tube diameter, e f f e c t , small-volume TCD, 70 Tubing, micro HPLC, 115 Turbulent volumetric time constant, 61 Two-dimensional chromatography contour p l o t s , 194f numerical deconvolution techniques, 179-87 Two-dimensional electrophoresis, proteins, 6 ϋ

Undecane, temperature dependence o f Kovats i n d i c e s , 220f Unweighted least-squares a n a l y s i s , computer-simulated chromatograms, 23 UV detector c a p i l l a r y SFC, 125 SFC, 6 UV-visible detector, narrow-bore packed-column HPLC, 100 V van Deempter curves HPLC, 206 t h e o r e t i c a l , 31f various, 138-43 van Deempter r e l a t i o n s h i p , packed column, 137 Velocity l i n e a r c a r r i e r , vs. column diameter, 53,55f optimum l i n e a r , SFC, 141 V i s u a l i n t e r p r e t a t i o n of peaks, 25 Vitamin B12 synthesis, HPLC development, 79

231

INDEX X

Volume reduction, systematic, 39 Volumetric time constant, TCD, 61,70 W Water content, e f f e c t , RPLC, 83 Water extracts from c o a l , micro HPLC, 1 l 6 f Waters, James, HPLC development, 79 Weighted least-squares a n a l y s i s , computer-simulated chromatograms, 22,24f Woodward, R. B., HPLC development, 79

Xanthines, modifier s e l e c t i v i t y , C02-based SFC, 153-57 Xanthone, C02-based SFC* 158f Xylene, absorbance spectra and retent i o n p r o f i l e s , I88f

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