Frans_M_Everaerts_Isotachophoresis_378342.pdf

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CHECK OF THE ISOTACHOPHORETIC MODEL 77 true value, but there is a linear relationship between dTth and the real difference in temperature [22] (see Chapter 6). As a linear relationship between the conductivity of a zone and the temperature inside the capillary tube can be expected over a limited traject, a linear relationship can also be expected between the conductivity of the zones and the temperature detected by means of a thermocouple. This relationship is used to check the theory. In this section, some calculations of the parameters of the different zones are made and the results are compared with those obtained in some experiments. Calculations were made both for anions and cations, correcting for the influence of activity coefficients, relaxation and electrophoretic effects and different temperatures in the zones. The temperatures in the zones were estimated from the thermocouple signals and the temperatures in the capillary tube [22] . Calculations were made for the cations BaZ+, Caz+, Mg2+, Fez+, k?, Ag and Na+. These cations were chosen because the slope of the function A. = KJc* agrees reasonably well with the expected slope according to the Onsager relationship. If other influences such as complex formation occur, the decreasing effect on the mobility should be greater and the calculations would not be valid as the computer program does not deal with effects such as complex formation. For the anionic calculations, acids were chosen for which data such as ionic mobilities and pK values were readily available [ 13, 19,23,24] . The concentrations, pH values, step heights and zone resistances are given in Table 4.6 for cations in the system WKAC (see Table 11.3) and in the Tables 4.7 and 4.8 for anions in the systems histidine hydrochloride and imidazole hydrochloride (see Tables 12.1 and 12.2) respectively. Firstly, calculations were made with no corrections. The relationship between the experimentally measured step heights and the uncorrected calculated conductivities of the zones are given in Figs.4.l5a, 4.16a and 4.17a. Although one continuous relationship would be expected, two distinguishable curves are obtained for these relationships. This can be understood easily, as follows. If the zone resistances are computed without applying corrections for the Onsager relationship, there will be deviations from the real electrical resistances actually present. The zone resistances calculated will be smaller than the actual resistances because relaxation and electrophoretic effects, which decrease TABLE 4.6 SOME EXPERIMENTAL AND CALCULATED VALUES FOR CATIONS IN THE OPERATIONAL SYSTEM AT pH 5.4 (SEE TABLE 11.3) A values are given in C’ cm-I. Cation K+ &+ Na+ BaZ+ Ca ’+ Mg" Fe 2+ l/h. los without corrections 0.874 1.029 1.272 1.013 1.077 1.210 1.188 i/h 10' with corrections 0.8930 1.0440 1.2825 1.1152 1.1818 1.3215 1.2969 - Calculated concentration of the ionized part (mole/ 1) 0.0100 0.0094 0.0086 0.0048 0.0046 0.0044 0.0045 PH Step height (mm) 5.39 220 5.36 260 5.32 302 5.36 264 5.35 284 5.33 3 14 5.33 3 12
78 MATHEMATICAL MODEL FOR ISOTACHOPHORZSIS TABLE4.7 SOME EXPERIMENTAL AND CALCULATED VALUES FOR ANIONS IN THE OPERATIONAL SYSTEM AT pH 6 (SEE TABLE 12.1) Ionic species l/h. lo3 l/h. lo3 Calculated PH Step height without with concentration of (mm) correc- correc- the ionized part tions tions (molell) Acetic acid Benzoic acid rn-Nitrobenzoic acid pNitrobenzoic acid Capric acid Caprylic acid Chloric acid Crotonic acid Formic acid Glycolic acid Hydrofluoric acid Iodic acid Lactic acid Nicotinic acid Nitric acid Nitrous acid Methacrylic acid Pelargonic acid Picric acid 0-Chloropropionic acid Salicylic acid Sulphamic acid Sulphanilic acid Isovaleric acid Adipic acid Maleic acid dl-Malic acid Malonic acid Oxalic acid Pimelic acid Succinic acid Sulphuric acid Tartaric acid Tartronic acid 2.036 2.504 2.561 2.560 3.075 3.064 1.230 2.414 1.474 1.996 1.468 1.977 2.268 2.526 1.120 1.115 2.295 3.100 2.648 2.283 2.334 1.623 2.483 2.660 1.543 1.689 1.402 1.257 1.098 1.626 1.511 0.996 1.257 1.203 *Concentration of the monovalent anions. **Concentration of the divalent anions. 2.195 2.689 2.749 2.764 3.246 3.235 1.349 2.591 1.608 2.160 1.600 2.142 2.450 2.697 1.225 1.219 2.469 3.286 2.832 2.461 2.512 1.766 2.672 2.831 1.869 1.900 1.655 1.520 1.331 1.972 1.759 1.204 1.521 1.458 0.0082* 0.0078 0.0078 0.0078 0.0070 0.0070 0.0097 0.0078 0.0092 0.0084 0.0092 0.0085 0.0081 0.0076 0.0099 0.0099 0.0080 0.0070 0.0077 0.0081 0.0080 0.0090 0.0078 0.0075 0.0045** 0.0030 0.0027* 0.0042 0.0047 0.0049 0.0044 0.0013 0.0038* 0.0050 0.0047 0.0048 6.12 6.13 6.13 6.13 6.19 6.19 6.04 6.14 6.06 6.10 6.06 6.09 6.11 6.16 6.03 6.03 6.12 6.20 6.14 6.12 6.13 6.07 6.13 6.16 6.06 6.1 1 6.07 6.04 6.03 6.07 6.09 6.02 6.04 6.04 - 366 430 440 44 2 51 1 510 243 416 276 360 277 358 39 1 436 220 21 7 404 494 446 399 408 304 420 460 334 312 286 280 236 345 304 224 280 256
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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
Page 42 and 43: Chapter 3 Concept of mobility SUMMA
Page 44 and 45: IONIC MOBILITY AND IONIC EQUIVALENT
Page 46 and 47: EFFECTIVE IONIC MOBILITY 31 obtain
Page 48 and 49: EFFECTIVE IONIC MOBILITY 33 compari
Page 50 and 51: EFFECTIVE IONIC MOBILITY Fig.3.4. R
Page 52 and 53: DETERMINATION OF IONIC MOBILITIES 3
Page 54 and 55: DETERMINATION OF IONIC MOBILITIES 3
Page 56 and 57: Chapter 4 Mathematical model for is
Page 58 and 59: GENERAL EQUATIONS 43 anionic specie
Page 60 and 61: GENERAL EQUATIONS 4.2.1. Equilibriu
Page 62 and 63: GENERAL EQUATIONS 41 i Similar equa
Page 64 and 65: GENERAL EQUATIONS 49 Uthzone (U-llt
Page 66 and 67: GENERAL EQUATIONS 4.2.4. Modified O
Page 68 and 69: GENERAL EQUATIONS TABLE 4.2 REDUCED
Page 70 and 71: MATHEMATICAL MODEL FOR THE STEADY S
Page 84 and 85: VALIDITY OF THE ISOTACHOPHORETIC MO
Page 94 and 95: CHECK OF THE ISOTACHOPHORETIC MODEL
Page 96 and 97: REFERENCES 81 Fig.4.17. Relationshi
Page 98 and 99: Chapter 5 Choice of electrolyte sys
Page 100 and 101: CHOICE OF THE SOLVENT 85 In general
Page 102 and 103: CHOICE OF THE SOLVENT TABLE 5.2 THE
Page 104 and 105: CHOICE OF THE SOLVENT pH and pKvalu
Page 106 and 107: CHOICE OF THE SOLVENT 91 TABLE 5.4
Page 108 and 109: CHOICE OF THE pH OF THE LEADING ELE
Page 110 and 111: CHOICE OF THE pH OF THE LEADING ELE
Page 112 and 113: CHOICE OF THE TERMINATING AND LEADI
Page 114 and 115: ADDITIONS TO THE ELECTROLYTE SOLUTI
Page 116 and 117: EXAMPLES Choice of solvent. Can wat
Page 118 and 119: EXAMPLES 103 solvent, hoping that a
Page 120 and 121: EXAMPLES TABLE 5.11 STEP HEIGHTS OF
Page 122 and 123: EXAMPLES TABLE 5.12 STEP HEIGHTS OF
Page 124 and 125: Fig.5.9. Isotachopherograms of the
Page 126 and 127: EXAMPLES II 4 3 Fig.5.11. Isotachop
Page 128 and 129: REFERENCES 113 Example I. As exampl
Page 130 and 131: INSTRUMENTATION
Page 132 and 133: Chapter 6 Detection systems SUMMARY
Page 134 and 135: THERMOMETRIC RECORDING 6.1.3. Combi
Page 136 and 137: THERMOMETRIC RECORDING Potential gr
Page 138 and 139: THERMOMETRIC RECORDING /2 Fig.6.1.
Page 140 and 141: 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 CONDUCTIVITY AND W
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Chapter 13 Amino acids, peptides an
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AMINO ACIDS TABLE 13.1 OPERATIONAL
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AMINO ACIDS 8- ?- 6- 5- 4- 3- 2- f-
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AMINO ACIDS 317 TABLE 13.5 STEP HEI
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AMINO ACIDS Fig.13.3. Schematic dia
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AMINO ACIDS TABLE 13.6 DETERMINATIO
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SEPARATION OF PROTEINS IN AMPHOLYTE
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SEPARATION OF SMALL PEPTIDES reprod
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Chapter I4 Separation of nucleotide
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Chapter 15 Enzymatic reactions SUMM
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ENZYMATIC CONVERSION OF GLUCOSE (FR
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ENZYMATIC CONVERSION OF PYRUVATE 35
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Chapter 16 Separations in non-aqueo
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SEPARATION OF ANIONIC SPECIES IN ME
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SEPARATION OF CATIONIC SPECIES IN M
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EXPERIMENTS IN AQUEOUS METHANOLIC S
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Chapter I7 Counter flow of electrol
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INTRODUCTION 317 In various operati
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EXPERIMENTAL 0% 10 % a b 60 % a b a
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EXPERIMENTAL 381 caused by the coun
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CONCLUSION 383 c t r ’r; I I"
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APPENDICES
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Appendix A Simplified model of movi
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PROCEDURE OF COMPUTATION A.3. PROCE
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EXPERIMENTAL 39 1 TABLE A1 THEORETI
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DISCUSSION E I I Fig.A2. Graphical
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Appendix B Diameter of the narrow-b
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Appendix C Literature 1897-1966 F.
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LITERATURE 399 B.P. Konstantinov an
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LITERATURE 401 1971 L. Arlinger, Is
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LITERATURE 403 1973 L. Arlinger and
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LITERATURE 405 A. Chrambach and J.S
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LITERATURE 407 M. Coxon and M.J. Bi
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Symbols and abbreviations SYMBOLS A
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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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