Frans_M_Everaerts_Isotachophoresis_378342.pdf

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SEPARATION OF ANIONIC SPECIES IN METHANOL 363 TABLE 16.2 QUALITATIVE INFORMATION (STEP HEIGHTS) FOR SOME ANIONS IN THE OPERATIONAL SYSTEM LISTED IN TABLE 16.1 The step heights H refer to the step height of the leading zone (173 rnrn is the step height from 0 to 70 pA for the zone of the leading electrolyte). Ionic species H(mrn) Ionic species Hhm) Acetic acid Acetic acid, phenyl Acetic acid, trichloro Adipic acid Azelaic acid Benzoic acid Benzoic acid, o-amino Benzoic acid, p-amino Benzoic acid, rn’-amino Benzoic acid, 5-bromo3,4-dihydroxy Benzoic acid, 2,4 dihydroxy Butyric acid Cacodylic acid Capric acid Caproic acid Caprylic acid Crotonic acid Hydrofluoric acid Formic acid Hippuric acid Lactic acid Lauric acid *Double step. 88 240 76 260 212 216 304 412 308 264 224 176 800 380 296 336 180 148 37 256 232 408 Linoleic acid Maleic acid Malic acid, dl Malonic acid Mandelic acid, dl Myristic acid Oleic acid Oxalic acid Palmitic acid Pelargonic acid Pimelic acid Pyruvic acid Salicylic acid Salicylic acid, acetyl Salicylic acid, sulpho Stearic acid Suberic acid Succinic acid Sulphanylic acid Sulphonic acid, 2-naphthalene Valeric acid 508 176 t 344* 244 120 + 188* 210 440 5 04 112 t 300* 480 360 264 96 + 298* 112 108 t 220* 108 508 280 224 200 162 2 74 acid. The isotachopherograms were measured I day after the preparation of the sample solutions. pK measurements on oxalic acid showed the disappearance of one pK step during the time involved. A fresh solution gave two pK values, while a 2-day-old solution gave only one. A large proportion of the methanol in the solutions of oxalic acid in methanol was evaporated off and, after the subsequent addition of water, the resulting solution was also measured in an aqueous operational system. Here the products of the old methanolic solution gave a higher step height than normal, while the product from the fresh methanolic solution gave the normal step height of oxalic acid in water. Old solutions of oxalic acid in methanol gave, after several hours in water, two step heights, but after about 1 day they gave only one step height (the normal step height of oxalic acid). It can be concluded from these experiments that oxalic acid undergoes spontaneous conversion into its monoester in methanolic solutions. Other dicarboxylic acids showed similar effects, but on a smaller scale. Dicarboxylic acids such as dihydroxymaleic acid showed a large number of step heights and it is clear that the analyses of such substances will be difficult. In Fig.16.2, the
i 3 T 364 SEPARATIONS IN NON-AQUEOUS SYSTEMS - - c_ t t t Fig.16.1. Isotachopherograms of the separation of dl-malic acid (A), oxalic acid (B) and a mixture of oxalic and dl-malic acids C. A: 1 = Chloride; 2 = dl-malate; and 3 = cacodylate. B: 1 = Chloride; 2, 3 = components that belong to the oxalate [the oxalate (2) and possibly an ester (3)] ; 4 = cacodylate. C: 1 = Chloride; 2 = oxalate; 3 = malate; 4 = the ester of oxalate and methanol (?); 5 = cacodylate. isotachopherogram of pure dihydroxymaleic acid is given. The terminator was cacodylic acid. The substances listed in Table 16.2 are almost all organic acids; in general, inorganic acids were sparingly soluble in methanol. Because of its lower dielectric constant, complex formation occurs to a much greater extent in methanol than in water, and also the greater effect of the activity coefficients and the decreasing effect on the mobility make methanol unsuitable for isotachophoretic experiments with inorganic ionic species. For the halides, however, which have almost identical effective mobilities in water and cannot be separated, some experiments were carried out in methanol. As with alkali metals (see section 16.3.1), the halides have greater differences in mobilities in methanol and can easily be separated. In Table 16.3, the absolute ionic mobilities and measured step heights in water and methanol are given. The leading electrolyte in water was 0.01 N hydrobromic acid and in methanol 0.01 N hydriodic acid. In Fig.16.3, the separation of the halides is shown, with sodium dihydrogen orthophosphate as terminator. In the sample used to obtain Fig.16.3, formate was added in order to have the possibility of comparing the step heights with those in Table 16.2. 16.3. SEPARATION OF CATIONIC SPECIES IN METHANOL USING A THERMO- METRIC DETECTOR Some cationic species were measured in three different systems, viz., the unbuffered system MHCl, listed in Table 16.4, and the buffered systems MKAC and MTMAAC listed in the Tables 16.5 and 16.6 respectively.
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Journal of Chromatogaphy Library -
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Journal of Chromatography Library -
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Dedicated to Pr0f.Dr.h. A.I.M. Keul
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Contents Preface ..................
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CONTENTS IX 6.4.2. The d.c. method
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CONTENTS XI 12.2.2. Applications ..
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It is very well known that charged
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Chapter 1 Historical review SUMMARY
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HISTORICAL REVIEW 3 Independently i
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THEORY
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Chapter 2 Principles of electrophor
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MOVINGBOUNDARY ELECTROPHORESIS a S
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MOVINGBOUNDARY ELECTROPHORESIS 0 iu
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ISOTACHOPHORESIS 13 2.4. PRINCIPLE
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ISOTACHOPHORESIS 15 As the anionic
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ISOTACHOPHORESIS velocities, so tha
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ISOTACHOPHORESIS 19 d.t ’.t I Fig
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ISOTACHOPHORESIS 21 t Fig.2.8. Isot
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ISOELECTRIC FOCUSING 23 The four is
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DISCUSSION 25 Fig.2.11. Survey of t
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Chapter 3 Concept of mobility SUMMA
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IONIC MOBILITY AND IONIC EQUIVALENT
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EFFECTIVE IONIC MOBILITY 31 obtain
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EFFECTIVE IONIC MOBILITY 33 compari
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EFFECTIVE IONIC MOBILITY Fig.3.4. R
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DETERMINATION OF IONIC MOBILITIES 3
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DETERMINATION OF IONIC MOBILITIES 3
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Chapter 4 Mathematical model for is
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GENERAL EQUATIONS 43 anionic specie
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GENERAL EQUATIONS 4.2.1. Equilibriu
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GENERAL EQUATIONS 41 i Similar equa
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GENERAL EQUATIONS 49 Uthzone (U-llt
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GENERAL EQUATIONS 4.2.4. Modified O
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GENERAL EQUATIONS TABLE 4.2 REDUCED
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MATHEMATICAL MODEL FOR THE STEADY S
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VALIDITY OF THE ISOTACHOPHORETIC MO
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CHECK OF THE ISOTACHOPHORETIC MODEL
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CHECK OF THE ISOTACHOPHORETIC MODEL
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REFERENCES 81 Fig.4.17. Relationshi
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Chapter 5 Choice of electrolyte sys
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CHOICE OF THE SOLVENT 85 In general
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CHOICE OF THE SOLVENT TABLE 5.2 THE
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CHOICE OF THE SOLVENT pH and pKvalu
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CHOICE OF THE SOLVENT 91 TABLE 5.4
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CHOICE OF THE pH OF THE LEADING ELE
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CHOICE OF THE pH OF THE LEADING ELE
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CHOICE OF THE TERMINATING AND LEADI
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ADDITIONS TO THE ELECTROLYTE SOLUTI
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EXAMPLES Choice of solvent. Can wat
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EXAMPLES 103 solvent, hoping that a
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EXAMPLES TABLE 5.11 STEP HEIGHTS OF
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EXAMPLES TABLE 5.12 STEP HEIGHTS OF
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Fig.5.9. Isotachopherograms of the
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EXAMPLES II 4 3 Fig.5.11. Isotachop
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REFERENCES 113 Example I. As exampl
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INSTRUMENTATION
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Chapter 6 Detection systems SUMMARY
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THERMOMETRIC RECORDING 6.1.3. Combi
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THERMOMETRIC RECORDING Potential gr
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THERMOMETRIC RECORDING /2 Fig.6.1.
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THERMOMETRIC RECORDING T t l Fig.6.
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THERMOMETRIC RECORDING 7 127 It-- I
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THERMOMETRIC RECORDING a concentrat
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HIGH-FREQUENCY CONDUCTIVITY DETECTI
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CONDUCTIVITY DETECTION 133 Fig.6.9.
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CONDUCTIVITY DETECTION 135 The d.c.
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CONDUCTIVITY DETECTION 137 Hi V 1kR
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CONDUCTIVITY DETECTION Fig.6.12. Co
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CONDUCTIVITY DETECTION Fig.6.14. Th
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CONDUCTIVITY DETECTION 143 6.4.4. T
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CONDUCTIVITY DETECTION 145 contact
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CONDUCTIVITY DETECTION 147 We can n
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CONDUCTIVITY DETECTION 149 N.Y., U.
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CONDUCTIVITY DETECTION 151 achieved
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UV ABSORPTION METER 153 -_-.- +- R
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UV ABSORPTION METER Fig.6.22. Contr
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W ABSORPTION METER r +15V -15V Mod
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W ABSORPTION METER 159 TABLE 6.4 PR
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W ABSORPTION METER 230 240 2% m zm
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to Mod (Fig 6.24) oscillator I sync
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UV ABSORPTION METER 165 dicular to
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Fig.6.31. Isotachopherograms for th
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UV ABSORPTION METER 169 50 Fig.6.33
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ADDITIVES TO THE ELECTROLYTES 171 6
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ADDITIVES TO THE ELECTROLYTES 173 e
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ADDITIVES TO THE ELECTROLYTES 175 a
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ADDITIVES TO THE ELECTROLYTES 177 o
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ADDITIVES TO THE ELECTROLYTES 179 d
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ADDITIVES TO THE ELECTROLYTES 181 T
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ADDITIVES TO THE ELECTROLYTES Fig.6
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ADDITIVES TO THE ELECTROLYTES 185 F
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ADDITIVES TO THE ELECTROLYTES 1 2 3
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ADDITIVES TO THE ELECTROLYTES 189 n
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COATING OF THE MICRO-SENSING ELECTR
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DETECTION LIMITS 193 electric drivi
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DETECTION LIMITS 195 Fig.6.48. Infl
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DETECTION LIMITS 197 TABLE 6.6 SURV
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CONCLUSION 199 average length of a
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REFERENCES 201 seen. Again it is cl
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Chapter 7 Instrumentation SUMMARY T
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INJECTION SYSTEMS I! I n Fig.7.1. P
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INJECTION SYSTEMS Fig.7.3. Exploded
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INJECTION SYSTEMS Fig.7.5. Injectio
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COUNTER ELECTRODE COMPARTMENTS 21 1
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COUNTER ELECTRODE COMPARTMENTS Even
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COUNTER ELECTRODE COMPARTMENTS 21 5
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EQUIPMENT the large bore, a more di
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EQUIPMENT 219 belonging to three cl
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EQUIPMENT 221 signal of the thermoc
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EQUIF'MENT 223 No effect on the res
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EQUIPMENT 225 Fig.7.14. Electrophor
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EQUIPMENT Fig.7.16. Photograph of t
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EQUIPMENT 229 mounted equiplanar, w
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COUNTER FLOW OF ELECTROLYTE 231 ins
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COUNTER FLOW OF ELECTROLYTE p High
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COUNTER FLOW OF ELECTROLYTE Fig.7.2
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COUNTER FLOW OF ELECTROLYTE 231 aro
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COUNTER FLOW OF ELECTROLYTE p high
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COUNTER FLOW OF ELECTROLYTE 24 1 7.
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COUNTER FLOW OF ELECTROLYTE I I 31
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COUNTER FLOW OF ELECTROLYTE max. 15
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APPLICATIONS
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Chapter 8 Introduction SUMMARY In t
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INTRODUCTION 25 1 the various ionic
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Chapter 9 Practical aspects SUMMARY
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DISTURBANCES CAUSED BY H+ AND OH 25
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DISTURBANCES CAUSED BY H+ AND OH- 2
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DISTURBANCES DUE TO CO, 263 Electro
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ENFORCED ISOTACHOPHORESIS 265 t T T
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WATER AS TERMINATOR 267 function of
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PURIFICATION OF THE TERMINATOR 7 4
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REFERENCES 271 AS an example, the c
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Chapter 10 Quantitative aspects SUM
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THERMOMETRIC MEASUREMENTS 215 vj c
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THERMOMETRIC MEASUREMENTS TABLE 10.
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CONDUCTIMETRIC MEASUREMENTS factor
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CONCLUSION 28 1 Tables 10.3-10.5 wa
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Chapter 11 Separation of cationic s
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SEPARATION USING A THERMOCOUPLE AS
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I SEPARATION USING A THERMOCOUPLE A
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SEPARATION USING CONDUCTIVITY AND U
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Chapter I2 Separation of anionic sp
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SEPARATION USING A THERMOMETRIC DET
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SEPARATION USING A THERMOMETRIC DET
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SEPARATION USING CONDUCTIVITY AND W
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Chapter 13 Amino acids, peptides an
Page 328 and 329: AMINO ACIDS TABLE 13.1 OPERATIONAL
Page 330 and 331: AMINO ACIDS 8- ?- 6- 5- 4- 3- 2- f-
Page 332 and 333: AMINO ACIDS 317 TABLE 13.5 STEP HEI
Page 334 and 335: AMINO ACIDS Fig.13.3. Schematic dia
Page 336 and 337: AMINO ACIDS TABLE 13.6 DETERMINATIO
Page 338 and 339: SEPARATION OF PROTEINS IN AMPHOLYTE
Page 350 and 351: SEPARATION OF SMALL PEPTIDES reprod
Page 352 and 353: Chapter I4 Separation of nucleotide
Page 354 and 355: SEPARATION USING A THERMOMETRIC DET
Page 356 and 357: SEPARATION USING A THERMOMETRIC DET
Page 358 and 359: SEPARATION USING CONDUCTIVITY AND U
Page 360 and 361: SEPARATION USING CONDUCTIVITY AND U
Page 362 and 363: Chapter 15 Enzymatic reactions SUMM
Page 364 and 365: ENZYMATIC CONVERSION OF GLUCOSE (FR
Page 370 and 371: ENZYMATIC CONVERSION OF PYRUVATE 35
Page 376 and 377: Chapter 16 Separations in non-aqueo
Page 380 and 381: SEPARATION OF CATIONIC SPECIES IN M
Page 388 and 389: EXPERIMENTS IN AQUEOUS METHANOLIC S
Page 390 and 391: Chapter I7 Counter flow of electrol
Page 392 and 393: INTRODUCTION 317 In various operati
Page 394 and 395: EXPERIMENTAL 0% 10 % a b 60 % a b a
Page 396 and 397: EXPERIMENTAL 381 caused by the coun
Page 398 and 399: CONCLUSION 383 c t r ’r; I I"
Page 400 and 401: APPENDICES
Page 402 and 403: Appendix A Simplified model of movi
Page 404 and 405: PROCEDURE OF COMPUTATION A.3. PROCE
Page 406 and 407: EXPERIMENTAL 39 1 TABLE A1 THEORETI
Page 408 and 409: DISCUSSION E I I Fig.A2. Graphical
Page 410 and 411: Appendix B Diameter of the narrow-b
Page 412 and 413: Appendix C Literature 1897-1966 F.
Page 414 and 415: LITERATURE 399 B.P. Konstantinov an
Page 416 and 417: LITERATURE 401 1971 L. Arlinger, Is
Page 418 and 419: LITERATURE 403 1973 L. Arlinger and
Page 420 and 421: LITERATURE 405 A. Chrambach and J.S
Page 422 and 423: LITERATURE 407 M. Coxon and M.J. Bi
Page 424 and 425: Symbols and abbreviations SYMBOLS A
Page 426 and 427: SYMBOLS AND ABBREVIATIONS SUPERSCRI
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Subject index A Absorption meter, U
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SUBJECT INDEX 41 5 Detection limit
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SUBJECT INDEX 41 7 --_ , separation
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