INDEX Chloroform, deuterated 115 Chromatographic retention times . . 102 Chromatography, gas-liquid 100 Chromatography, gas-solid 100 Clusius-Dickel column 5 Clusters 269 CO, absorption spectra of 70 Computer calculations 159 Condensed phase isotope effects . . 100 Condensed states 246 Conductance 30-1 Convergence . 197 Copper isotopes, mobility of . . . . 261 Correlations with structures 180 Counter-current electromigration . . 259 Counter-current flow 9 Crossover phenomenon 177, 180 Cross-over temperature . . 196, 241, 244-5 Cross sections, neutron 2
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A
a vs. solvent 121 Absorption processes 99 Acetone, deuterated 115 Acetylene 112-3 Acid-base catalysis 33 Adsorbed diatomic molecules . . . . 74-5 Alcohol, deuterated 115 Alkali amides 25-38 dissociation of 29 Ammonia-hydrogen process 19 Ammonia, isotopic exchange between hydrogen and liquid . .25-38 Anharmonicity 103 vs. isotopic exchange equilibria 185-90 Anharmonic oscillator 186 Anomalous temperature dependence 149 Approximation methods 172-3 for isotope-exchange equilibrium constants 178-81 Aqueous solutions, electromigration in 248-62
D
B Bernoulli series 193-239 Best polynomials . .208-14, 231, 242, 245 BF3, molecular addition compounds of 41-55 Bigeleisen-Mayer approximation 161,224,226,238 Bond-bending frequencies 210 Bond-stretching frequencies 210 Born-Oppenheimer method 186, 190, 246 Boron isotopes, chemical fractionation of 40-55 1-Bromobutane 237
C Calutron 3,57 Carbon isotopes, photochemical separation of 65-71 Cartesian displacement coordinate 232 Cascade exchange column 143-5 Cascade theory 7 Characteristic frequency 151 Chebyshev polynomial 200-46 Chemical exchange 9 between oxides of nitrogen . . 119-46 fractionation of boron isotopes . . 40-55 isotope fractionation 192-247 reflux 17
Deuterated acetone alcohol chloroform olefins paraffins sugars Deuteroacetylene Diatomic molecules Dibenzoylmethane Diffusion, isotope factor of Dissociation of alkali amides Distillation Donor molecules vs. a Dual temperature process
115 115 115 115 115 116 112-3 185 59 267 29 8 130 15
£ Eigen-mobilities 252, 254 Eigenvalue 238 of a matrix 240 Electromagnetic separator 3 Electromigration, mass effect of . . 249 Electromigration in metals, salts, and aqueous solutions 248-62 Electro self-transport 250-2 Enrichment of lithium isotopes by extraction chromatography . .57-63 Entropy of isotope mixing 12 Equilibrium isotope effects 193 Equivalent isotopic isomers 195 Ethane-deuteroethanes 106
275
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276
ISOTOPE EFFECTS IN CHEMICAL PROCESSES
Exchange columns, cascade 143-5 distillation 21 equilibria among oxynitrogen compounds 148-83 equilibria, anharmonicity vs. isotopic 185-90 External mobilities 257 Extraction chromatography 60 enrichment of lithium isotopes by 57-63
FG-matrix method, Wilson 218, 237, 240-1, 243 FON0 151-180 Force fields 154 Fractionation, chemical isotope . 192-247 Free energy scale of isotopes 13 Frequency shifts 158
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2
Gallium 249-50 Gamma-bar method 150, 182, 193 Gas chromatography, isotope separation by 99-117 Gaseous diffusion 9 plant 13 Gas-liquid chromatography 100 Gas-solid chromatography . ; 100 Geometric mean, rule of 195 Go 186-90 G(u) expansion 193-4
H Haeffner-effect 248 Harmonic approximation . . 101, 192, 195 Heavy water 2,19-20 processes 19 Henry's Law constant 105 High-temperature approximation 150,160,178-81 cw-HONO 151-80 trans-HONO 151-80 HON0 151-80 Hydrogen 101 and liquid ammonia, isotopic exchange between 25-38 molecules, isotopically substituted 188 Hydrogens by adsorption at low temperatures, isotope and ortho-para separations of molecular 73-98 Hypergeometric function 200 2
I Ideal cascade 9,12 Internal coordinates 211 Ionic liquids, thermotransport in .264-73 Isothermal diffusion 266
Isotope and ortho-para separations of molecular hydrogens by adsorption at low temperatures 73-98 -effect calculations 148-83 effects 248 equilibrium 193 kinetic 193 quantum 250 on solution 99 vibrational contribution to . . 185 electromigration 248 exchange equilibrium constants 174,176,178-81 exchange reactions 119 factor of diffusion 267 fractionation, chemical 192-247 separation by gas chromatography . . . .99-117 laboratory scale 3 large scale 6 practice 1-23 process 40-55 Isotopes, free energy scale of . . . . 13 Isotopically substituted hydrogen molecules 188 Isotopic exchange between hydrogen and liquid ammonia 25-38 exchange equilibria vs. anharmonicity 185-90 hydrogen 79, 85, 87, 89, 97 J Jacobi polynomials
198-243 K
Kinetic isotope effects Kinetics
193 26-37
L Laboratory scale isotope separation 3 Large scale isotope separation . . . 6 Liquid ammonia 25-38 metals 268 nitrates 271 salts 270 Lithium complexes 58-9 Lithium isotopes 252-62 by extraction chromatography, enrichment of 57-63 mobility of 254-62 Low-temperature approximation . . 150,160,172,175,177-8,180 Low-temperature chromatograph 105
M Magnesium isotopes, mobility of . . Mass effect of electromigration . . .
Spindel; Isotope Effects in Chemical Processes Advances in Chemistry; American Chemical Society: Washington, DC, 1969.
261 249
277
INDEX
Matrix, eigenvalue of a 240 Mercury ion mobilities 251 Metals, electromigration in 248-62 Metals, liquid 268 Methane 101 -deuteromethanes 108,111,114 Minimum reflux cascade 9 Minimum stage cascade 9 Mobility of isotopes . . .251-62, 271, 273 Modulating coefficients 196-203 Molecular addition compounds of B F 41-55 Molecular forcefieldsand geometries 151 Molten halides 256 Moments, method of 196 Monatomic liquids, thermotransport in 264-73
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3
N Neutron cross sections N-exchange equilibria Nitrates, liquid Nitrogen-15 Nitrogen, chemical exchange between oxides of Nitrogen isotopes Nitrox process NO N0 N0 N0 " N0 " NOBr NOC1 N0 C1 NOF N0 F Normal-mode vibrational frequencies Nuclear energy 15
2
2
+
2
3
2
2
2 151 271 119-46 119-46 245 14 151-79 151-78 151-80 151-78 151-78 151-78 151-78 151-78 151-78 151-78 156-8 2
O Oak Ridge electromagnetic separator plant 3-4 O-exchange equilibria 151 Olefins, deuterated 115 Orthogonal expansions 198 Orthogonal polynomial methods 192-247 Oxygen isotopes 116-245 Oxynitrogen compounds, exchange equilibria among 148-83 Oxynitrogen species 153, 181 ls
Perturbation theory calculation Photochemical separation of carbon isotopes Polyatomic systems Polynomial, Chebyshev Polynomial methods, orthogonal Polynomials, best Polynomials, lacobi Potassium isotopes, mobility of
. . . 186-7 65-71 216 200-46 192-247 208-45 198-243 . . . 260
Q Quantum correction Quantum isotope effect (5uasi-lattice
195, 235 250 251
R Range of expansion 203 Reduced partition function 13 ratio 192 Reflux 13 ratio 10 Riemann zeta function 201,205 Rubidium isotopes 249-50,262 mobility of 260 Rule of the geometric mean 195 Rule of the mean 234,238
S Saddle-point energy 270 Salts, electromigration in 248-62 Salts, liquid 270 Salt, stages of a 256 Savannah River plant 18, 20-1 Secular equations 211 Separation factor 8 Separation potential 12 Separation practice, isotope 1-23 Separative duty 12 Separative work 12 Single stage enrichment factor, a 120-1, 127 Sodium isotopes, mobility of 260-1 Solvent carrier exchange system . 119-46 Solvent vs. a 121, 128 Spindel and Taylor process 14 Spin isomerization 101 Stage 9 Stages of a salt 256 Sugars, deuterated 116 Surface heterogeneity 90 Symmetrized coordinates 241
P
T
Paraffins, deuterated 115 Partition-function ratios 158, 162-71 reduced 192 temperature-extrapolations of . . 173 PEEP 241
Tau method 202 Taylor expansions 193 Temperature-dependence anamolies 241 Temperature-extrapolations of partition-function ratios 173
Spindel; Isotope Effects in Chemical Processes Advances in Chemistry; American Chemical Society: Washington, DC, 1969.
278
ISOTOPE EFFECTS IN CHEMICAL PROCESSES
Thallium Thermal diffusion excitation of vibration fl r e
u x
257 4,264 150, 160 2g
W Wilson FG-matrix method . . . 151, 218, 237, 240-1, 243 Z Zero-point energy 197 approximation . . 150, 160, 172-80,193
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Thermotransport in monatomic and ionic liquids 264-73 Trace of matrix 196, 240 Trail plant 19-20 Tributyl phosphate 59 Tri-m-octylphosphine 59 Two-body collisions 253
V Vapor pressure isotope effect . . . . 100 Vibrational contribution to isotope effects . . 185 frequencies, normal-mode 15b-o zero-point energy of the molecule 185
Spindel; Isotope Effects in Chemical Processes Advances in Chemistry; American Chemical Society: Washington, DC, 1969.
