Mineral-water interface geochemistry. by Michael F. Hochella, and Art F. White, editors

Mineral-water Interface Geochemistry / M.f. Hochella, Jr. & A.f. White -- Atomic Treatment Of Mineral-water Surface Reactions / A.c. Lasaga -- Atomic Structure, Microtopography, Composition, And Reactivity Of Mineral Surfaces / M.f. Hochella, Jr. -- Surface Energy And Adsorption At Mineral-water Interfaces / G.a. Parks -- Surface Complexation Modeling In Aqueous Geochemistry / J.a. Davis And D.b. Kent -- Molecular Models On Ion Adsorption On Mineral Surfaces / G. Sposito -- Co-adsorption Of Metal Ions And Organic Ligands / P.w. Schindler -- Spectroscopic Studies Of Chemisorption Reaction Mechanisms At Oxide-water Interfaces / Gordon E. Brown, Jr. -- Mechanisms Of Growth And Dissolution Of Sparingly Soluble Salts / J.-w. Zhang & G.h. Nancollas -- Leaching Of Mineral And Glass Surfaces During Dissolution / W.h. Casey & B. Bunker -- Oxidative And Reductive Dissolution Of Minerals / J.g. Hering & W. Stumm. (cont.) Heterogeneous Electrochemical Reactions Associated With Oxidation Of Ferrous Oxide And Silicate Surfaces / A.f. White -- Spectroscopic Studies Of Adsorption/reduction Reactions Of Aqueous Metal Complexes On Sulphide Surfaces / G.m. Bancroft & M.m. Hyland -- Photo-redox Processes At The Mineral-water Interface / T.d. Waite. M.f. Hochella, Jr. And Art F. White, Editors ; Authors: G. Michael Bancroft ... [et Al.]. Includes Bibliographies. Page 1 Titles REVIEWS IN MINERALOGY VOLUME 23 MINERAL-WATER INTERFACE GEOCHEMISTRY M. F. HOCHELLA, JR. AND ART F. WHITE, editors Authors: Series Editor: Page 1 Titles MINERALOGICAL SOCIETY of AMERICA REVIEWS in MINERALOGY ------------_ ... __ .. _--_ ... __ .. _-_ ........ _- ......... _--------------------_ .. _----------- .... _ .. _-----------------------_ ... _---- v~~~~~~"="~:~ :!.~~~.~:.:-.~=~~ ~.ot:.~U',;;~~~3~n;~~: =-z:u:, .. ~ =. ~":N~~~1~~:strial ........ and meteoritic pyrox- :::::. 9,~~~~~:.:n~ EO:;2":s,~ ~~:; ii Page 1 Page 1 Titles REVIEWS in MINERALOGY Volume 23 MINERAL- WATER INTERFACE GEOCHEMISTRY FOREWORD PREFACE AND ACKNOWLEDGMENTS iv Page 2 Titles v Page 1 Titles vi Page 2 Titles vii Page 3 Titles Chapter 4 G. A. Parks SURFACE ENERGY AND ADSORPTION AT MINERAL/WATER INTERFACES: AN INTRODUCTION 139 The Kelvin equation and vapor pressures 140 The Freundlich-Ostwald equation 142 Highfield gradients enhance dissociation of electrolytes 147 Surface charge 147 Origins of charge 149 Electrified interfaces 152 Concentration dependence 154 Concentration dependence 157 Hydrolysis, polymerization, and precipitation 158 Competition and synergism between adsorbate and complexing ligands 158 Identifying sorption reactions: Clues to the composition and structure of surface complexes 159 Surface charge 162 Proton stoichiometry 162 The last analysis 163 Fracture surface energy Chapter 5 J. A. Davis and D. B. Kent SURFACE COMPLEXATION MODELING IN AQUEOUS Page 4 Page 5 Titles x Page 6 Titles xi Page 7 Titles xii Page 8 Titles xiii Page 9 Titles xiv Page 10 Titles Chapter 13 G. M. Bancroft & M. M. Hyland SPECTROSCOPIC STUDIES OF ADSORPTION/REDUCTION ON SULPHIDE SURF ACES Chapter 14 T. D. Waite 560 Molecular orbital theory 563 Band theory 568 Effects of illumination 568 Charge carrier mobility 569 Surface states 571 Space charge layer, band bending and electron transfer 576 Morphology 577 Size 579 Substitutional doping 579 Surface modification 580 Attachment to supports 580 Intercalation offoreign species into semiconductors 581 Photodissolution of semiconducting minerals 584 Hydrogen peroxide production 586 Degradation of organic and inorganic pollutants 588 Charge transfer via adsorbed chromophores 589 Charge transfer via photoactive surface complexes xv Page 11 Page 1 Page 2 Titles 2 Page 3 Titles 3 Page 4 Titles 4 Page 5 Titles 5 Page 6 Titles 6 Page 7 Titles 7 Page 8 Titles 8 Page 9 Titles 9 Page 10 Titles 10 Page 11 Titles 11 Page 12 Titles 12 Page 13 Titles 13 Page 14 Titles 14 Page 15 Titles 15 ACKNOWLEDGMENTS REFERENCES Page 16 Titles 16 Page 1 Page 2 Titles 18 o Tables Table 1 Page 3 Titles 19 Page 4 Titles 20 (1) (2) KAI3Si30lO(OHh + Si02 ===} KA1Si308 + Al2Si05 + H20, (3) Page 5 Titles (4) 21 L 1 tremolite + 11 dolomite ~ 8 forsterite + 13 calcite + 9 CO2 + H20, Page 6 Titles (7) 22 Rate = DAd 'YA 'YB (C~ - C~) Rate = L Ad (Ceq - Ceq) , 8) (9) Rate = kA AA kB AB (C~ _ C:) . (10) (11) Tables Table 1 Page 7 Titles 23 ii.(x-P)=O, ii.x=k, Page 8 Titles 24 [uvw] = u d + vb + we, Page 9 Titles • 25 a. b. Page 10 Titles 26 Tables Table 1 Table 2 Page 11 Tables Table 1 Page 12 Titles 28 + - - . Page 13 Titles 29 t::.G = t::.Eo + t::.EI - T t::.So - T t::.SI . (19) e. Page 14 Titles 30 N (23) Page 15 Titles 31 Tables Table 1 Page 16 Titles 32 Reaction in water (a) (b) Page 17 Titles 33 (qI/V) q. Page 18 Titles 34 Tables Table 1 Table 2 Page 19 Titles 35 kT qt t Page 20 Titles 36 H20 + == Si- ~ H20ads• Si ~ == Si - OH H20 + == Si - OH ~ H20ads• Si - OH ~ = Si(OHh H20 + = Si(OHh ~ «o:» Si(OHh ~ -Si(OHh (34) H20 + -Si(OHh ~ u-o.;» Si(OHh ~ H4SiO:ds H4SiO:ds ~ H4Si04(aq) kI[H20ads. Si] = k2[H20ads. Si(OH)] = k3[H20ads. Si(OHh] (35) = k4[H20ads. Si(OHh] = k5[H4SiO~dS] . Stot = [== Si] + [== Si(OH)] + [= Si(OHh] + [-Si(OHh] (36) + [H4SiO~ds] + [H20ads• Si] + [H20ads. Si(OH)] + [H20ads• Si(OHh] + [H20ad8• Si(OHh] . Stot = [== Si] D (37) k3/{laH2o + k4/{laH2o + k5/{laH2o Rate = k5[H4SiO~ds] = kl[H20ads. Si] Page 21 Titles 37 kT q+ + q+ Page 22 Titles 38 t::.H:j: = t::.E:j: + .!." hv~ - .!. " hvreact • • Tables Table 1 Page 23 Titles 39 h 'Yt ' t::.st = R In ( qt /V ) «=tv E; = RT + t::.Ht , A = eTTe Page 24 Titles 40 fIelec weleC(r, R) E(R) weleC(r, R) , w = I: (-It P[ 'ljJI(l)a(l) 'ljJI(2)(3(2) ... 'ljJn(2n)(3(2n)] (51) 'ljJi = I: Cμi ¢>μ Page 25 Titles 41 III = I: c. I: (-l)P P[tPil (1 )a(l) ... tPin (2n )f1(2n)] , Page 26 Titles 42 Page 27 Titles 43 Page 28 Tables Table 1 Table 2 Page 29 Titles 45 Page 30 Titles 46 (1) (11) - 2u(r))/kT). Page 23 Titles 75 Page 24 Titles 76 SCREW DISLOCATION, STEP ONLY A.,/kT = -0.5 Page 25 Titles 77 Page 26 Titles 78 Rate = A (!l.μ)n Page 27 Titles 79 • " , ......... ------------- s: • ," I ,t ,',I ,/.' , ' '1 , -- - - - - _- - - --------- ----- -l.ol __ ~:::: _- - ,. o s: 6μ/kT Page 28 Titles 80 Page 29 Titles 81 Page 30 Titles 82 Page 31 Titles 83 Page 32 Titles 84 Page 33 Titles 85 Page 34 Page 1 Page 2 Titles 88 Page 3 Titles 89 Page 4 Titles 90 Page 5 Titles 91 Page 6 Titles k = [4mn [ s + c1>r + e V _ E II v.. h2 2 2 ' Page 7 Titles 93 Page 8 Titles 94 Page 9 Titles 95 Page 10 Titles 96 Page 11 Titles o Tables Table 1 Page 12 Titles 98 Page 13 Titles 99 Page 14 Titles 100 " I '" '" Tables Table 1 Table 2 Page 15 Page 16 Titles 102 - w - Z Fe Fe A. Fe o B. Fe o s 200 400 600 800 Page 17 Titles 103 Page 18 Titles 104 Page 19 Titles 105 Page 20 Titles 106 Page 21 Titles 107 Page 22 Titles 108 Page 23 Titles 109 Page 24 Titles 110 Page 25 Titles 111 Page 26 Titles 112 Page 27 Titles 113 Page 28 Titles 114 Page 29 Titles 115 Page 30 Titles 116 Page 31 Titles 117 Page 32 Titles 118 282 284 286 288 -,- Tables Table 1 Page 33 Titles 119 Page 34 Titles 120 : = exp [2Y'l] Page 35 Titles 121 14r----------------------- -.., ., ., Page 36 Titles 122 Page 37 Titles J 2:\ Page 38 Titles 124 c Page 39 Titles ENERGY (aV) ENERGY (e.V) 125 Page 40 Titles 126 Page 41 Titles 127 Page 42 Titles 128 Page 43 Titles 129 Page 44 Titles 130 Page 45 Titles 131 Page 46 Titles 132 Page 1 Titles CHAPTER 4 G. A. PARKS SURFACE ENERGY AND ADSORPTION AT MINERAL­ AY=d' (1) 3p (2) Page 2 Page 3 Titles 135 Page 4 Titles 136 0.05 r-----------,,---------I -25 o 25 Distance from boundary, nm Page 5 Titles 137 (6) i j Page 6 Titles 138 1 + d i j Page 7 Titles 139 i j InKS = InK + RIT L 'Yj (~) (16) InPs = InP +.1L GfW) Page 8 Titles 140 10r-------------------------. C • .o .._ a.. 4 o Y= 72.75 mJ/m2 droplets cavities Drop or cavity diameter, nm (19) Page 9 Titles 141 i i Page 10 Titles 142 Page 11 Titles 143 Page 12 Titles 144 Page 13 Titles o 145 o a. Tables Table 1 Page 14 Titles 146 Page 15 Titles 147 Page 16 Titles i'. I. • aum Page 17 Titles 149 Page 18 Titles 150 Page 19 Titles 151 o~,.._ ~ ~ ~ ~ ~ ..- M to) oS'S ~ i g z 0 ~ !(!":l:I~~"9 6>& 0>6> 0>& 6> Inner-Sphere Surface Complex: K+ on Vermiculite Outer-Sphere Surface Complex: Ca(H20)~+ on Montmorillonite Page 11 Titles 187 Page 12 Titles 188 Page 13 Titles 189 (6) Page 14 Titles 190 Page 15 Titles 191 1.0 0.8 0.6 0.4 0,2 oL-------~-------L------~--------~------~ o piPe 1.0r---------.---------~----------.-------~ 0.4 0.3 0.1 0.2 Tables Table 1 Table 2 Page 16 Titles 192 =--+ Page 17 Titles 193 Page 18 Tables Table 1 Table 2 Page 19 Titles 195 Page 20 Titles 196 o 1l 1.0 .... o ~ Z 0.5 A o .. ~.~ ~.- . . B 15.0 5.0 10.0 Tables Table 1 Page 21 Titles pH Tables Table 1 Table 2 Page 22 Titles 0, 1M ll. O,3H 0 O,OIH 'V o o o o o pH Tables Table 1 Table 2 Page 23 Page 24 Tables Table 1 Page 25 Titles (a) (c) Tables Table 1 Page 26 Titles 202 Page 27 Titles 203 Page 28 Titles 204 Page 29 Titles 205 (9) Page 30 Titles 206 ------­ Page 31 Titles 201 [OH1) rH+-rOw=(cA -cB-[Hi + jfW ' q =cA -cB-[Hi + [OHl Page 32 Titles 208 Tables Table 1 Page 33 Titles 209 Page 34 Titles 210 !z « ~ Jd~ ~ ---- T--- . pH + Base t +.- .... ~.- ~A~l::i·~ _ 01 \ . Base .... t .. pH b c d e e Tables Table 1 Table 2 Page 35 Titles 211 Page 36 Titles 212 • " , , Page 37 Titles 213 Page 38 Titles 214 r, KL = [J"'I]rs ' r KL[J"'I] ] Page 39 Titles 215 Page 40 Titles 216 logC '%,--, Wi O"d H+ Na+ Counlerions OW CIO_;- Page 41 Titles 217 Page 42 Titles 218 =SOH;H =SOH+W , Page 43 Titles 219 Page 44 Titles 220 REV023C005_p221-260.pdf Page 1 Titles 221 c 7 5 o ... o :.: g'-12 9 7 Tables Table 1 Table 2 Table 3 Table 4 Page 2 Titles 222 Page 3 Titles I + Q ·H acrD '0 - aBit) '0 ~:+~P-H H+ SeD cf :>-O-P~ ?F ~P-H 223 Page 4 Titles 224 Page 5 Titles 225 Page 6 Titles 226 Page 7 Titles 227 Page 8 Titles 228 Page 9 Titles 229 B 0.01 M sulfate no sulfate 0.001 M sulfate Triple Layer Model A no sulfate 0.01 M sulfate 0.001M sulfate Diffuse Double Layer Model \)~., /.'" a ,,~\ 60 I- .~ .. ~/ \~~\~ \ .... ~~::?:, 0' I , , '-:===:" I 0' I , , "i'A::::::~ pH pH a: 60 ~ ~ ... o "#- pH pH ~r--------------------------, ~ A - 150 ~ -~- 8. I o~ - ] 0 ~ -50 ···~~~::::.::.:.:::.:=.::-::.=T -50 .................... Diffuse Double Layer Model "'\" [TriPle Layer Model Page 10 Titles 230 Page 11 Titles 231 Page 12 Titles 232 , Page 13 Titles 233 Page 14 Titles 234 Page 15 Titles 235 Page 16 Titles 236 Page 17 Titles 237 Page 18 Titles 238 r] X .1 H . Page 19 Titles 239 Page 20 Titles 240 Page 21 Titles 241 Page 22 Titles 242 Page 23 Titles 243 Page 24 Titles 244 Page 25 Titles 245 Page 26 Titles 246 Page 27 Titles 247 Page 28 Titles 248 Page 29 Titles 249 Page 30 Titles 250 Page 31 Titles 251 Page 32 Titles 252 Page 33 Titles 253 Page 34 Titles 254 Page 35 Titles 255 Page 36 Titles 256 Page 37 Titles 257 Page 38 Titles 258 Page 39 Titles 259 Page 40 Titles 260 Page 1 Titles MOLECULAR MODELS OF ION ADSORPTION Page 2 Titles 262 Page 3 Titles 263 -1 u>o u