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MONOGRAFIA CHEMISORPCJA HAYWARD TRAPNELL

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KLIKNIJ ABY PRZEJŚĆ DO SPISU TREŚCI

KLIKNIJ ABY PRZEJŚĆ DO OPISU KSIĄŻKI

KLIKNIJ ABY ZOBACZYĆ INNE WYSTAWIANE PRZEZE MNIE PRZEDMIOTY ZNAJDUJĄCE SIĘ W TEJ SAMEJ KATEGORII

KLIKNIJ ABY ZOBACZYĆ INNE WYSTAWIANE PRZEZE MNIE PRZEDMIOTY WEDŁUG CZASU ZAKOŃCZENIA

KLIKNIJ ABY ZOBACZYĆ INNE WYSTAWIANE PRZEZE MNIE PRZEDMIOTY WEDŁUG ILOŚCI OFERT

PONIŻEJ ZNAJDZIESZ MINIATURY ZDJĘĆ SPRZEDAWANEGO PRZEDMIOTU, WYSTARCZY KLIKNĄĆ NA JEDNĄ Z NICH A ZOSTANIESZ PRZENIESIONY DO ODPOWIEDNIEGO ZDJĘCIA W WIĘKSZYM FORMACIE ZNAJDUJĄCEGO SIĘ NA DOLE STRONY (CZASAMI TRZEBA CHWILĘ POCZEKAĆ NA DOGRANIE ZDJĘCIA).


PEŁNY TYTUŁ KSIĄŻKI -
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ILUSTRACJE, MAPY ITP. -
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KLIKNIJ ABY PRZEJŚĆ DO WYBORU MINIATUR ZDJĘĆ

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CONTENTS

CHAPTER PAGE
Preface to Second Edition .. .. .. .. .. ix
Preface to First Edition .. .. .. .. .. xi
I. Introduction .. .. .. .. .. .. 1
II. Experimental Methods .. .. . . . . 17
III. Velocities of Adsorption .. .. .. .. 67
IV. Velocities of Desorption .. .. .. .. 141
V. Adsorption Isotherms .. .. .. .. 159
VI. The Heat of Adsorption .. . . .. . . 194
VII. Mechanisms of Chemisorption on Metals. . .. 226
VIII. Mechanisms of Ghemisorption on Semiconductors 257
IX. The Mobility of Adsorbed Layers .. .. .. 281
Index of Adsorption Systems .. .. . . .. 309
Subject Index .. .. .. .. .. .. 319




When the first edition of this monograph appeared in 1955, the subject of chemi-sorption was advancing rapidly. New methods of studying adsorption on metal filaments by using ultra-high vacua were being developed, and these led to many important discoveries concerning velocities and mechanisms of chemisorption on metals. The possibilities of infra-red spectra as a tool for identifying surface radicals were becoming apparent; and the fundamental mechanisms of chemisorption on semiconductors were being revealed.
These and other major advances have prompted the publication of this second edition. Much new data has been added, and the text has been largely rewritten with a new and up-to-date approach. The treatment is again selective, with emphasis placed on the more important and less controversial aspects. The book is clear and readable, and will provide the undergraduate with an excellent introduction to the subject of chemisorption. Research students and workers in industrial laboratories will find it a valuable summary of present knowledge.
Some reviews of the first edition
" The author writes very clearly on his subject and . . . the book should form an excellent text for honours students and budding research workers .... it is recommended to all physical chemists who wish to be brought up to date in a fascinating and important field of research." -D D E|ey jn 5c/e/7ce Progress
this is a very useful book, which should stimulate further interest in chemisorption and f.nd a place in the bookshelves of those interested in surface chemistry .... authored publisher are to be congratulated upon the result of their work.
-R. M. Barrer in the Journal of the Royal Institute of Chemistry
"... fascinating and readable and should prove of value to both students and research workers alike."
-Transactions of the Faraday Society
" This is an excellent book, clear, concise, and logical, containing a wealth of useful information .... It will no doubt find a wide use, noTonly by the research specialist but by all those interested in surface phenomena, as well as the honours degree student who wishes to probe a little more deeply into this fascinating sublet than perhaps his examination syllabus expects.
-G. R. Whalley in Technical Book Review
" Chemists interested in adsorption or catalysis, and even physical chemist?generally, owe a debt of gratitude to Dr. Trapnell for writing Sis uniqueandtimely volume .... The presentation is admirąb y lucid in general, even in areas of theory which are highly speculative. -Arthur F. Benton in the Journal of the American Chemical Society
CHEMISORPTION
D. O. HAYWARD, M.A., Ph.D.,
Lecturer in Chemistry, Imperial College of Science and Technology
and
B. M. W. TRAPNELL, M.A., Ph.D.,
Headmaster, Denstone College
SECOND EDITION
LONDON
BUTTERWORTHS
1964




PREFACE TO SECOND EDITION

The first edition of the book appeared eight years ago, and since then considerable advances have taken place, particularly in experimental techniques. The subject has always been very dependent upon the devising of sound and ingenious experiments, and the last decade has been most fruitful from this point of view. It has seen the investigation of surface layers by infra-red spectra, and developments in ultra-high vacuum techniques for use with metal filaments, in the field emission microscope, in electron diffraction techniques, and in magnetic methods. It has also seen the full realization of the importance of the semiconducting property in chemisorption on oxides. In addition, interesting new data have appeared using more established methods, such as the use of tracers, and the measurement of heats of chemisorption.
These developments have led to extensive advances in our understanding of fast chemisorptions on metals, of mechanisms of chemisorption on both metals and semiconductors, and of the mechanism of surface mobility.
A further point is that at the time of the first edition, no very adequate treatise on catalysis was available, and therefore it seemed useful to include two chapters showing how data relating to chemisorption could be applied to problems in catalysis. This gap in the literature has now been largely filled, making it possible for the present volume to be concerned purely with chemisorption.
The overall result is that in preparing a second edition a very considerable recasting of the first edition has been necessary. One additional change has also taken place. The first edition was a solo effort: the second edition has involved the use of double harness. Readers may like to know that wherever the English is incomprehensible the author is D.O.H., and that where the science is incorrect the author is unquestionably B.M.W.T.

D. O. Hayward
B. M. W. Trapnell
London,
October 1963




PREFACE TO FIRST EDITION

T. E. Lawrence says in one of his letters that books are meant to be written not to be read, meaning, I imagine, that the greatest good to come out of their publication is the clarity with which the author should see his subject as a result of writing about it. Nevertheless, this book has been written to fill a gap in the existing literature, and so is primarily for the reader. A number of interesting discoveries have been made in the subject of chemisorption during the last 15 years, which are in the main available to scientists only as original papers. Neither a selective, nor an exhaustive treatment of chemisorption as a whole is available, and while this has given me a clear field, I have been conscious of the danger of attempting both treatments at the same time. In general, I have concentrated on the aspects of the subject which seem to me best understood, so that my treatment aims to be selective.
Chemisorption is closely related to heterogeneous catalysis, and the latter is bound to crop up in any treatise on the former. However, too many important problems in catalysis are at present sub judice for more than a very interim report to be possible, and such mention as I have made is largely to show how knowledge gained from chemisorption studies can be applied to problems in catalysis, and vice versa.
It is a pleasure to acknowledge three especial debts of gratitude. The first is to Sir Eric Rideal, to whom, in common with many other of his pupils, I owe not only an abiding interest in my subject, but also a great deal more besides. The second is to Dr. F. G. Tompkins, who first suggested that I should write the book, and who has been a source of encouragement on other occasions. The third is to my wife, who, while finding chemisorption an incomparably dull subject, has nevertheless converted my untidy longhand to neat typescript, and accepted with equanimity such antics as my writing has involved.

B. M. W. Trapnell Oxford, September 1954




INDEX OF ADSORPTION SYSTEMS

Adsorbates are listed alphabetically. The adsorbents are
arranged under each adsorbate according to group number
in the Periodic Table, in the order metals, carbon, oxides.
ACETYLENE Many metals
chemisorption fast, slow or
non-existent, 75, 231 K
compound formation, 232 Ni
infrared data, 254
surface radicals, 254 Cu, Au, Al
nature of adsorption, 232 Cu, Au (cont.)
heat of adsorption, 206
AMMONIA
W, Fe, Ni
heat of adsorption, 205, 305 surface coverage, 247 surface radicals, 247, 248 velocity of adsorption, 74, 75 ....
Vf (cont.)
ammonia decomposition, 168, 247
Pt
ammonia decomposition, 169
c .
heat of adsorption, 79, 80, 200
BARIUM Mo, W
mobility in field emission microscope, 285, 286
CAESIUM W
desorption kinetics, 148-150, 155
CAESIUM- cont.
W—cont.
dipole-dipole interactions, 15,
222
dipole moment, 15, 222, 236 heat of adsorption, 201, 213 isostere, 190, 191 mobility, 293, 294 second layer formation, 127,
191, 192 sticking probability, 111, 112,
122, 123, 127 thermionic emission, 40
CARBON DIOXIDE Ba
sticking probability, 131 Ti
heat of adsorption, 205 sticking probability, 131 surface coverage, 245 - surface radicals, 244, 245 sZr
fast chemisorption, 75 : i Nb, Ta
fast chemisorption, 75 heat of adsorption, 205 surface radicals, 244, 245 Ta (cont.)
surface coverage, 245 Cr
fast chemisorption, 75 heat of adsorption, 205 Mo, W
fast chemisorption, 75 heat of adsorption, 205 isotopic exchange with carbon
monoxide, 244 surface coverage, 245 surface radicals, 244, 245
CARBON DIOXIDE-cont. W [cont.)
dissociative adsorption, 206
mobility in field emission microscope, 245, 286, 287, 291 Mn
heat of adsorption, 205, 245 Fe, Co, Ni
fast chemisorption, 75
heat of adsorption, 205
surface coverage, 245
surface radicals, 244, 245 Ni [cont.)
infrared data, 245
radioactive tracer technique, 34 Rh, Pd, Pt, Cu, Zn, Cd
inactive in chemisorption, 75 Hg
rapid, strong adsorption, 78, 79 Al
activated adsorption, 75
nature of adsorption, 233 C
activated chemisorption, 82
heat of adsorption, 79, 80 Cr2O3, Mn2O3, ZnO, Mn2O3. Cr2O3, ZnO.CraO3
heat of adsorption, 197
non-activated adsorption, 84 Mn203(corcz.)
carbonate ion formation, 272 CoO, NiO
heat of adsorption, 85
surface coverage, 85 NiO [cont.)
infrared data, 272, 273 Cu2O
isotopic exchange with oxygen ions of oxide, 83
CARBON MONOXIDE K
no chemisorption, 75 Ca
chemisorption, 231 Ba, La
fast chemisorption, 75 Ba(cotó.)
sticking probability, 131 Ti
conductivity data, 230
CARBON MONOXIDE-cont. Ti—cont.
heat of adsorption, 205, 305 sticking probability, 131 Zr, Nb, Ta, Cr
fast chemisorption, 75 Mo
infrared data, 243
second layer formation, 303,
304
sticking probability, 131 surface coverage, 241 velocity of adsorption, 303, 304 W
activated adsorption, following
fast chemisorption, 76 different binding states, 146,
147, 215-217, 243, 244 entropy of adsorbed layer, 301,
302 field emission data, 127, 128,
286-291
heat of adsorption, 205, 305 infrared data, 243 ionic character of surface bond,
206, 207
isotherms, 191, 192 mobility, 286-291, 301, 302,
305 sticking probability, 115-117,
122, 123
surface coverage, 241 velocity of desorption, 146, 147,
156, 215-217 Mn
fast chemisorption, 75 Fe, Co, Ni
fast chemisorption, 75 infrared data, 243 mobility, 305-307 surface potential data, 306, 307 Fe, Ni [cont.)
activated adsorption following
rapid chemisorption, 76-
78, 133-135 conductivity data, 230 heat of adsorption, 205 ionic character of surface bond,
206, 207
surface coverage, 241 Fe [cont.), powder adsorbent activated chemisorption, 69
CARBON MONOXIDE-cont. Fe[cont.), powder adsorbent—cont.
isotopic exchange of CO, 244 Ni [cont.)
bond energy, 234
heat of reaction, 209
radioactive tracer technique, 34
sticking probability, 131 Rh, Pd, Pt
fast chemisorption, 75
infrared data, 242, 243
surface coverage, 241
Pd [cont.)
activated adsorption on powder, 69
heat of adsorption, 305 Pt [cont.)
isobar for foil, 68
velocity of desorption, 154 Cu, Ag, Au
fast adsorption, 75
mobility, 306, 307
surface potential, 306, 307 Cu. Au [cont.)
entropy of adsorbed layer, 301, 302
heat of adsorption, 206
nature of adsorption, 232
Cu [cont.)
activated adsorption on powder, 69
heat of adsorption, 195, 234
infrared data, 232, 234
poisoning, 215 Zn, Cd, In, Sn, Pb
no adsorption, 75 Al
activation energy of adsorption, 76
C
activated adsorption, 82
isotherm, 170 Cr2O3
fast adsorption, 83, 85
heats of adsorption, 83, 85, 197
reversibility, 269
surface radicals, 271 MnO
heat of fast adsorption, 85
MnO.Cr2O3
activated adsorption, 69, 86
CARBON MONOXIDE-cont.
Mn2O3, Mn2O3.Cr2O3 heats of adsorption, 197 surface radicals in irreversible adsorption, 269, 271
CoO, NiO
heats and surface coverages for fast adsorption, 85
NiO [cont.)
conductivity data, 263
Cu2O
conductivity data, 272 heat of adsorption, 85, 197 isotopic exchange, 83, 272 reversibility, 269, 270, 272 surface coverage, 85 surface radicals, 269, 272 two types of adsorption, 258
CuO
surface radicals, 271
ZnO, ZnO.Cr2O3
heats of adsorption, 85, 197 non-activated adsorption, 84, 85
ZnO [cont.)
reversibility, 84, 85, 271 surface radicals, 269, 271
ZnO.Cr2O3 [cont.) reversibility, 269 surface radicals, 269
CARBON TETRACHLORIDE
Hg
chemisorption, 79
CHLORINE
Ni, Cu
kinetics of high temperature
reaction, 121, 122 C
heat of adsorption, 79, 80, 200
CHLOROFORM
Hg
chemisorption, 79
CYCLOHEXANE
Ni
dissociative adsorption, 250,
251

DIMETHYL BUTANE
Ni
dissociative adsorption, 250,251
DIMETHYL SULPHIDE Pd
magnetic data, 229
ETHANE
Many metals
adsorption fast or slow, 74, 75 W, Fe, Ni, Rh
surface radicals, 250 Ni (cont.)
cracking and isotopic exchange, 249
infrared data, 250
magnetic data, 230, 250 Fe2O3, NiO
chemisorption, 278 NiO (cont.)
surface radicals, 278 ZnO.Cr2O3
heat of slow adsorption, 86
ETHYLENE
Most metals
adsorption fast, slow or nonexistent, 75
Ta
heat of adsorption, 205,213,305
Cr
heat of adsorption, 205
W, Fe, Ni, Rh
heat of adsorption, 205, 305
W (cont.)
heat of adsorption, 213, 305 sticking probability, 120 surface radicals, 252, 253
Ni (cont.)
hydrogénation, 215, 251 infrared data, 253, 254 magnetic data, 230, 252 surface radicals, 251-254
Cu, Au
entropy of adsorbed layer, 301,
302
heat of adsorption, 206 nature of adsorption, 232
ETHYLENE—cont. Ag
influence of oxygen impurity,
71 Al
nature of adsorption, 232
Cr2O3
activated adsorption, 69, 86 CoO, Cu2O, ZnO, ZnO.Cr2O3
heat of fast adsorption, 85
HYDROGEN K
influence of oxygen impurity, 71
no chemisorption on clean
metal, 75 Ca
activated adsorption or contamination, 74—76 Ba
sticking probability, 131 Ti, Zr, Nb
fast chemisorption, 75 Ta
fast chemisorption, 75
heat of adsorption, 203, 214,
305 Cr, Mo
fast chemisorption, 75
heat of adsorption, 203 Mo (cont.)
atomization, 119, 120
second layer formation, 119
sticking probability, 119, 120,
122, 123, 131 W
activated adsorption on powder, 69, 71
atomization, 117, 118
bond energy, 234
contamination and slow adsorption, 71
dipole-dipole interactions, 222
dipole moment, 222, 239
entropy of adsorbed layer, 301, 302
field emission data, 127, 286-291
HYDROGEN- cont. W—cont.
heat of adsorption,
calculated, 202, 203, 208 experimental, 72, 146, 180, 181, 186, 187, 195, 203, 213,214 ionic character of surface bond,
206, 207
isobar for powder, 71, 72 isotherms, 159, 160, 179-181,
183-187 mobility, 286-291, 301, 302,
305 secondary binding states, 145,
146, 218, 239 slow uptakes following fast
adsorption, 76, 77 sticking probability, 117-119,
122, 123
surface coverage, 73, 237 surface potential, 234 velocity of desorption, 145, 146,
154-156 Mn
activated adsorption, 75, 76 heat of adsorption, 203 Fe
activated adsorption on powder, 69
conductivity data, 240 heat of adsorption,
calculated, 203, 208 experimental, 203 variation with coverage, 213, 214, 302, 303, 305 hydrogen-deuterium exchange,
71
isobar for powder, 69, 70 isotherms, 188, 189 secondary binding states, 240 slow uptakes following fast adsorption, 76, 78, 133-135 surface potential data, 306,
307 Co
fast chemisorption, 75 surface potential data, 306, 307 Ni
activated adsorption on powder, 69
HYDROGEN- cont. Ni—cont.
calculation of activation
energy, 110
conductivity data, 51, 230 contamination and slow adsorption, 71
dipole-dipole interactions, 222 electron diffraction data, 129,
130 entropy of adsorbed layer, 299-
301
field emission data, 286-291 heat of adsorption,
calculated, 110, 203, 208,
209 experimental, 110, 194,
203 variation with coverage,
213, 214, 305 ionic character of surface bond,
206, 207
isobar for powder, 13, 68 magnetic data, 54, 229 mobility 286—291, 299-301,
305-307
secondary binding state, 126 slow uptake following fast chemisorption, 76-78, 133-135
sticking probability, 129, 130 surface coverage, 237, 238 surface potential data, 234, 306,
307 Rh
heat of adsorption, 203, 214 ionic character of surface bond,
206, 207 Pd
heat of adsorption, 203, 305 slow uptake following fast chemisorption, 76 Pt
infrared data, 239
secondary binding state, 126,
238, 239
surface potential data, 238, 239 Cu, Ag, Au
adsorption of hydrogen atoms,
75 233
mobility, 306, 307 no adsorption of molecules, 75
HYDROGEN- cont. Cu, Ag, Au—cont.
surface potentials and bond
energies, 234
Cu (cont.) powder adsorbent activated adsorption, 69 fast adsorption, 70 heat of adsorption, 70, 195 isotherm, 181-183 Ag (cont.)
influence of oxygen impurity,
71 no adsorption on clean metal,
75 Zn, Cd, AI, Pb
adsorption of atoms, 233 no adsorption of molecules, 75 Hg
rapid adsorption, 78, 79 In, Sn
no adsorption of molecules, 75 Si
activated adsorption of molecules, 269 Ge
activated adsorption of molecules, 75, 76, 269 adsorption of atoms, 26 electron diffraction data, 60 C
activation energy of adsorption,
81, 108, 109 desorption, 19 heat of adsorption, 81, 200 TiO2, V2O3, V2O5
hydrogen-deuterium exchange,
266, 267 V2O3 (cont.)
activated adsorption, 69, 86 Cr2O3
activated adsorption, 69, 86 heat of adsorption, 14, 83, 196,
197, 276 hydrogen-deuterium exchange,
71, 83, 266, 267, 276 isotherm, 192 MnO
activated adsorption, 69 hydrogen-deuterium exchange,
266, 267 MnO.Cr2O3
kinetics of adsorption, 95, 96
HYDROGEN-cont. MnO.Cr2O3—cont.
isosteric heat of adsorption, 69
isotherm, 178, 179 Mn2O3
heat of adsorption, 197
mechanism of adsorption, 277 Fe2O3, CO3O4, NiO
hydrogen-deuterium exchange,
83, 266, 267 NiO (cont.)
extent of adsorption, 258 Cu2O
conductivity data, 263
heat of adsorption, 197
hydrogen-deuterium exchange,
266, 267 CuO
hydrogen-deuterium exchange,
266, 267 ZnO
activated adsorption, 69, 70,
84,86
boundary-layer theory, 261 conductivity data, 84, 85, 261,
265, 277 hydrogen-deuterium exchange,
83, 265-267
effect of doping on, 264 isobar, 69, 70 mechanism of adsorption, 265,
267, 268
velocity of adsorption, 96, 217 ZnO.Cr2O3
heats of adsorption, 86, 197,
276 A12O3
activated adsorption, 69, 84, 86
hydrogen-deuterium exchange,
83, 268 Ga2O3, GeO2
hydrogen-deuterium exchange,
266, 267
HYDROGEN SULPHIDE
W, Ni
fast adsorption, 75
METHANE
Ti, Ta, Cr, Mo, W
velocity of adsorption, 74, 75
METHANE- cont.
W (cont.)
sticking probability, 120 surface radicals, 248, 249
Fe, Co, Ni
activated adsorption, 74-76,248 surface radicals, 248, 249
Rh, Pd
velocity of adsorption, 74, 75
C
activation energy of adsorption, 82
NITROGEN K
no adsorption, 75 Ca, Ba
activated adsorption, 74-76 Ba (cont.)
sticking probability, 108 La, Ti, Zr, Nb, Ta
fast chemisorption, 75 Ti (cont.)
sticking probability, 131 Ta (cont.)
activated adsorption following fast adsorption, 76, 133-135 heat of adsorption, 205, 208,
213 ionic character of surface bond,
206, 207
surface coverage, 246 Cr
activated adsorption following fast adsorption, 76, 133-135
surface coverage, 246 Mo
sticking probability, 131
surface coverage, 246
velocity of adsorption, 303,
304 W
activated adsorption following
fast adsorption, 76 activated adsorption on powder, 69, 71, 72
entropy of adsorbed layer, 301 field emission data, 127, 128, 286-291
NITROGEN- cont. Vf—cont.
heat of adsorption,
calculated, 205, 208 experimental, 145, 195,
205, 212, 304, 305 ionic character of surface bond,
206, 207
isotherm, 183, 185 isotopic exchange, 247 mobility, 286-291, 301 secondary binding states, 115,
145, 247 sticking probability, 30, 112-
115, 122-125 surface coverage, 246 velocity of desorption, 144, 145,
154-156 Fe
activated adsorption,
on powder, 69, 75, 104-
106
following rapid chemisorption, 76, 133-135 entropy of adsorbed layer, 301,
302 heats of adsorption, 196, 205,
245, 246 ionic character of surface bond,
206, 207
isotherm, 186-188 mobility, 301, 302 surface coverage, 245, 246 velocity of adsorption, 104-106 velocity of desorption, 143, 144,
155, 156 other metals
not adsorbed, 75 Cr2O3
heat of adsorption, 83 surface radicals, 277
NITROUS OXIDE Fe2O3
activity in decomposition, 258 CoO, NiO
heats of adsorption, 85, 86
slow and fast adsorptions, 85,86 Cu2O, AI2O3
activity in decomposition. 258
OXYGEN
All metals except Au
fast chemisorption, 75 Ti, Nb, Ta, Cr
surface coverage and oxidation, 240 Mo
heat of adsorption, 205, 305 ionic character of surface bond,
206, 207
kinetics of slow uptake following adsorption, 133-135 surface coverage, 240 W
field emission data, 127, 128,
286-191 heat of adsorption, 73, 148, 205,
208, 305
heat of reaction, 209 ionic character of surface bond,
206, 207
kinetics of slow uptake following fast adsorption, 133-135
mobility, 286-291,305 rate of formation of oxide,
121
secondary binding state, 241 sticking probability, 112, 120-
124
surface coverage, 73, 240 velocity of desorption, 18, 22,
147, 148, 154, 156 Mn, Fe, Co, Ni
surface coverage and oxidation,
240 Fe (cont.)
desorption from filament, 18 surface dipole and oxidation,
135 Ni (cont.)
conductivity data, 230 desorption from filament, 18 electron diffraction data, 129,
130
magnetic data, 229, 230 sticking probability, 129 surface dipole and oxidation,
135 Rh, Pd, Pt
heat of adsorption, 205, 208 surface coverage, 240, 241
OXYGEN-cow;. Rh (cont.)
ionic character of surface bond,
206, 207
kinetics of slow uptake following fast adsorption, 133-135
mobility, 305, 306 Pt (cont.)
isobar for foil, 68 Ag, Au
activated adsorption on powders, 69 Au (cont.)
no chemisorption on film, 75 Al
surface coverage and oxidation,
240 Hg
rapid, strong adsorption, 78,
79 Si, Ge
kinetics of slow uptake following rapid adsorption, 108, 133-135
sticking probability, 106, 107 surface coverage, 268 Ge (cont.)
electron diffraction data, 60 C
activation energy for adsorption, 80 desorption, 19 heat of adsorption, calculated, 200 experimental, 68, 79, 80, 194, 195, 198, 200, 213 physical adsorption and chemisorption, 68, 80 MgO
activation energy for adsorption, 86
Cr2O3
activation energy for adsorption, 86
heats of adsorption, 83, 196, 197
surface radicals, 258 MnO
heat of adsorption, 85 Mn2O3, Mn2O3.Cr2O3
heats of adsorption, 197
OXYGEN- cont. Fe2O3
activation energy for adsorption, 86 CoO
heat of activated adsorption, 86 NiO
activation energy for adsorption, 86
heat of adsorption, 85 Cu2O
activated adsorption, 86 conductivity data, 269, 273 heat of adsorption, 86, 197 kinetics of adsorption, 103, 104 penetration of oxide lattice,
274-276 ZnO
activated adsorption, 84, 86 boundary-layer theory, 262 conductivity data, 261 depletive chemisorption, 8, 258,
261, 263
desorption, 273, 274 heat of adsorption, 86 isotopic exchange, 83, 274 mechanism of adsorption, 258,
265, 273, 274 photo effects, 265 two types of adsorption, 258 ZnO.Cr2O3
heat of adsorption, 85, 197
PENTANE
Ni
surface radicals, 250, 251
POTASSIUM W
dipole moment, 236 heat of adsorption, 201 mobility, 295
POTASSIUM- cont. Au
rate of deposition, 132
PROPANE
Ni
surface radicals, 249
SODIUM Mo
mobility, 285, 286 W
activation energy for desorption, 148, 149 dipole moment, 222, 236 heat of adsorption, 201 mobility, 285, 286, 294, 295
SULPHUR DIOXIDE Pt
kinetics of oxidation, 169 Cu2O
heat of adsorption, 85 surface radicals, 277
THORIUM
Mo
mobility, 285, 286
W
activation energy for desorption, 148
dipole moment, 15, 236 field emission data, 283-286 mobility, 283-286, 292, 293 velocity of desorption, 143, 148
WATER C
heat of adsorption, 79, SO A12O3
activated adsorption, 69
SUBJECT INDEX
Absolute reaction rate theory, 97-
102, 151-153 comparison with experiment,
104-108, 154-156 Absorption definition of, 5 distinction from adsorption, 5, 6,
70,81 following rapid chemisorption,
70, 76-78 types of, 5
Accommodation coefficients, 48 change on adsorption, 71, 72, 112,
241 criterion for a clean surface, 21,
50
measurement of, 48-50 Activated chemisorption, 3, 4, 13,
90,91
carbon, on, 68, 80-82 following rapid chemisorption,
76-78, 132-135
kinetics of, 81, 90-108, 132-135 metals, on, 13, 68, 69, 74-78,
104-108, 132-135 oxides, on, 68-70, 84-86, 95, 96,
103, 104 surface contamination, and, 70-
72
theory of, 68-71 Activation energy for chemisorption, 87-89 calculation of, 108-110 variation with coverage, 69, 80, 81, 93-95, 103-106, 132-135 desorption, 11,141-150,215-217,
272
heat of adsorption, and, 11, 83, 84,141,144-148,212,216, 217 variation with coverage, 142-
144, 149, 150 surface diffusion, 6, 7
experimental values of, 287, 288, 291-295, 301
Activation energy for—cord. surface diffusion—cont.
variation with crystal face,
286-291
Adsorption, definition of, 1 Ammonia
decomposition, 168, 169, 247
nitrogen exchange, and, 247 synthesis, 10, 11 Atomization of hydrogen 117-120
Band theory of solids, 7, 8
metals, application to, 226-228 oxides, application to, 259, 260
Boundary-layer theory, 261-263 successes and limitations, 264-269
Brunauer-Emmett-Teller isotherm, 34, 197, 198, 237
Carbon monoxide oxidation, 169,
264, 265 Chemisorption
activation energy for, see Activation
energy for chemisorption definition of, 2 distinction from, absorption, 5, 6 physical adsorption, 2-4, 68-
70, 80, 197, 198 heat of, see Heat of chemisorption surface radicals in, see Surface
radicals in chemisorption Condensation coefficients calculation of, 97-103 definition of, 91
experimental values of, 105-108 Contact potential difference, 44-47,
148
Co-ordinate surface bonds, 234, 235 Covalent chemisorption, 8, 9 carbon surfaces, at, 200, 201 metal surfaces, at, 202-208, 228-
234
oxide surfaces, at, 257, 258, 265-273, 276-279
rf-character of metal bond, 210-212 rf-electrons, importance in chemi-sorption, 210-212 227-234, 267
Dehydrogenation of cyclic paraffins, 279 Depletive chemisorption on oxides,
8, 261-263 Desorption
activation energy of, see Activation
energy for desorption velocity constant, see Velocity constant of desorption Diffusion of contaminants to surface,
21,22 Dipole moment of surface bond, 15,
203
bond type, and, 228, 236 calculation of bond energies, and,
203, 208 change in work function, and, 39,
236
interaction forces, and, 15, 16, 222 ionic character of bond, and, 208 values for gases on metals, 222,
228 variation with coverage, 15, 16,
238, 239
Doped oxides and catalytic activity, 264, 265
Electrical conductivity change on adsorption metals, 230, 240 oxides, 261-263, 265, 268, 269,
272, 273, 277 measurement of, 51-53 Electron diffraction data
experimental method, 58-60 sticking probabilities, and, 107,
129, 130 surface configuration, and, 129,
130
Electron spin resonance, 55 Electronic structure of oxides, 258-
260 Elovich equation, 93-97, 108, 132-
135
Endothermic chemisorption, 1 Entropy of adsorbed layer, 1, 296-302
Evaporated carbon films, 23, 24, 82 Evaporated metal films
experimental methods with, 23-25,27,28,34-38,41,44,46, 47, 51, 57, 58 oriented and non-oriented, 215
Ferromagnetism, influence on
chemisorption, 233 Field emission microscope, 42, 43 surface diffusion, and, 61, 62,
282-292
work function changes on adsorption, and, 42, 43, 127-129 Flash filament technique, 30-32 Formic acid decomposition, 168 Fow ler-Nordheim equation, 42 Free energy of adsorption, 1, 297 Freundlich isotherm, 169-171 applications to experimental data,
135, 170, 180-185 assumptions of, 174 derivation of, 171-173 method of testing, 174, 175
Geometric factor in adsorption, 108-
110,252 Gibbs adsorption equation, 161,164,
171
Heat of adsorption, 1, 11, 13-15 calorimetric and isosteric heats,
198, 199
calorimetry, by, 14, 35-38 Clausius-Clapeyron equation,
from, 13, 14 rates of desorption, from, 144-148,
195 Heat of chemisorption,
adsorption isotherms, and, 161,
172-178, 180-182, 186-189 calculated values for,
carbon, 108, 109, 200, 201 metals, 201-208 experimental values for,
gases on carbon, 79-81, 200 gases on metals, 3, 72, 73, 145, 146, 148, 194-196, 203, 205, 206, 208, 234, 245, 246
Heat of chemisorption—conl. experimental values for—cont. gases on oxides, 14, 83, 85, 86,
196, 197, 272, 276, 277 metal vapours on metals, 201 heat of reaction, and, 208, 209 metal ^-character, and, 211, 212 mobility, and, 286, 291, 293, 294 Periodic Number, and, 212 variation with amount adsorbed, 14, 15, 172-178, 181, 182, 212-223 gases on metals, 180, 181, 186,
187, 189, 212-214, 222 gases on oxides, 14, 15, 263 metal vapours on metals, for,
213, 222
mobility, and, 302-306 oxygen on carbon, for, 213 variation with
stoichiometry of oxide, 196, 197 surface impurity, 195 temperature, 195, 196, 302, 303 time, 277
type of sample, 194, 195 velocity of desorption, and, 11, 83,84,141,144-148,212,217 Heat of physical adsorption, 3, 68,
69, 197, 198 Heterogeneity, 6
fall in heat of adsorption, and,
214-218
Freundlich isotherm, and, 172,173 Temkin isotherm, and, 177 velocities of adsorption, and, 91-
95
velocities of desorption, and, 142 Hydrogen atoms, chemisorption of,
75, 233
Hydrogen-deuterium exchange, metals, on, 10, 11,71,236,237 oxides, on, 71, 83, 264-268 Hydrogénation of ethylene, 215, 251, 252
Infrared spectroscopy,
chemisorbed species, of, 216, 234,
239, 242, 243, 245, 253, 254,
272, 273 experimental methods, 55-58
Interactions between particles in
adsorbed layers depolarization, and, 15, 16 fall in heat of adsorption, and, 14,
15, 214, 218-222 magnitude of, 222 statistical theory of, 93, 156, 157,
218-221
Ion bombardment cleaning of surfaces, 21, 22
Ionic bonds in adsorption, 8, 9 metals, on, 201, 202, 236 oxides, on, 261, 262, 265, 269-277 Ionization gauges, limitations of,
26,32 Isobars, adsorption, 12, 13, 68-72,
77
Isosteres, adsorption, 12,13,190,297 Isotherms, adsorption, 12, 159, 160,
178-192
five types of, 159, 160 Freundlich, see Freundlich isotherm general expressions for, 189, 190 Langmuir, see Langmuir isotherm Temkin, see Temkin isotherm Isotopic exchange reactions of carbon dioxide, 83, 244, 273 carbon monoxide, 83, 244, 272 ethane, 10, 249 hydrogen, see Hydrogen-deuterium
exchange nitrogen, 247 oxygen, 83, 274
Langmuir isotherm,
assumptions of, 165, 166 catalytic reactions, application to,
167-169
derivation of, 161-165 experimental data, application
to, 178-180, 182, 183 methods of testing, 166, 167 Lifetime of adsorbed particle on
surface, 151
Localized and non-localized adsorption, 6, 7, 110,281
Magnetic susceptibility, 53
change on adsorption, 228-230,
252 measurement of, 53, 54
Mercury, adsorption on, 78, 79 Metal filament adsorbents
experimental methods with, 18, 19, 21-23,29-32,38,40,41, 48-50
nature of, 110, 111 Metals, theory of, 226-228 Microbalances, 32, 33 Mobility, see also Surface diffusion, condensation coefficients, and,
99-102, 105-108 entropy of adsorption, and, 296-
302
heat of adsorption, and, 302-306 surface potential, and, 306, 307 velocity constants of desorption,
and, 150-155
Molecular beams, 118, 119, 121, 122 Monolayer and multilayer adsorption, 1, 4, 159
Nitrous oxide decomposition, 85,
264
Non-activated chemisorption metals, on, 71-75, 110-132 oxides, on, 82-85
Non-uniform surfaces, see Heterogeneity Nuclear magnetic resonance, 55
Orientation of metal films and
catalytic activity, 214 Outgassing of adsorbents, 18, 21-23,
79 Oxidation of metals, 76, 121, 135,
240
Parahydrogen conversion, 80
Partition function of adsorbed molecules, 99-102, 152-155, 163, 164 variation with coverage, 173
Peierls equation, 156, 157
Percentage ionic character of surface bonds, 206, 207
Photodesorption, 265
Photoelectric emission, 40, 41, 294
Physical adsorption, 2
distinction from chemisorption,
2-4, 68-70, 80, 197, 198 heat of, see Heat of physical adsorption
Poisoning of catalysts, 215, 234, 235 Polanyi-Wigner equation, 150 Potential energy curves, 88, 89, 133,
134
Powder adsorbents, experimental methods with, 18-21, 27, 34-36, 51-57
Precursor states to strong chemisorption, 90, 112, 114,115,119, 123-127, 134
Quantum mechanical treatment, adsorption velocities, of, 102, 103 desorption velocities, of, 151
Radioactive tracer techniques, 34 Roughness factor for adsorbent surfaces, 24, 31, 73, 111
Saturation magnetization,
change on adsorption, 54, 229,
230
measurement of, 54 Semiconductivity, see Electrical conductivity Statistical factor in adsorption and
desorption, 92, 93, 156, 157 Statistical mechanics,
adsorption isotherms, and, 163,
164 [;
adsorption velocities, and, 97-102 desorption velocities, and, 151-
153 Sticking probabilities, 86-88, 91,
110-132'
measurement of, 30-32 gases on metals, values for, 106-
108, 111-123, 129-131 metal vapours on metals, values
for, 111, 112, 131, 132 Sublimation energy and heat of
adsorption, 202, 204, 210 Sulphur dioxide oxidation, 169
Surface areas
evaporated films, of, 24, 237, 238 measurement of, 34, 35 metal filaments, of, 72, 73, 111 Surface bonds
co-ordinate, see Co-ordinate surface
bonds
covalent, see Covalent chemisorption ionic, see Ionic bonds in adsorption nature of, 7-9
secondary states of binding on metals, 115, 126, 144-147, 216, 217, 238-246 Surface collision number, 18, 32, 86,
87
Surface diffusion, see also Mobility activation energy for, see Activation energy for surface diffusion gases on metals, of, 286-292 metal vapours on metals, of, 283-
286, 292-295 Surface electron states, 223, 227,
228
Surface potentials, 228, 233, 234 dipole moments, and, see Dipole
moment of surf ace bond measurement of, 38-48 mobility, and, 306, 307 variation with coverage, 238, 239,
306, 307
Surface pressure, 164, 171 Surface radicals in chemisorption carbon, on, 108, 109, 200 metals, on, 9, 10, 72, 73, 201-206,
236-254 oxides, on, 9, 10, 269-279
Surface tension, change on adsorption, 78
Temkin isotherm,
application to experimental data,
185-189
derivation of, 176, 177 method of testing, 178 Thermionic emission, 40, 147, 148;
292, 293 Thermomolecular flow, 27
Ultra-high vacuum techniques, 26 Uniform surfaces, 6
derivation of isotherms, and, 165,
176, 177, 189 velocities of
adsorption on, 91,93, 94 desorption on, 141, 142
Velocity constant of desorption calculation of, 150-153 experimental values of, 149. 150,
154, 155
variation with coverage, 149, 150,
155, 156
Work function, 8, 9, 15, 38
heat of adsorption, and, 201, 203,
204
measurement of, 38-48 variation with crystal face, 39, 47



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