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あいねさわなか
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2 .... = 1) 2) Ca + CO CaCO 3)

4 温泉水からの鉱物生成指宿温泉での鉄鉱物の生成霧島丸尾温泉でのシリカ鉱物の生成

5 湧水からの鉱物生成

6 Dissolution of anorthite Ca 2 2 O 8 + 8H + Ca H 4 O 4 Reaction of Ca ions Ca 2+ + CO 2 + H 2 O CaCO 3 + 2H + Calcite Reaction of ions H 2 O (OH) 3 + 3H + Gibbsite Reaction of H 4 O 4 ions H 4 O 4 O 2 + 2H 2 O Amorphous silica Reaction of and H 4 O 4 ions H 4 O 4 +H 2 O 2 2 O 5 (OH) 4 + 6H + Kaolinite Reaction of Ca,, and H 4 O 4 ions Ca H 4 O 4 6Ca ( )O 10 (OH) H 2 O + 44H + Smectite Dissolution of fayalite (olivine) Fe 2 O 4 + 4H + 2Fe 2+ + H 4 O 4 Dissolution of ferrosilite (pyroxene) FeO 3 + 2H + + H 2 O Fe 2+ + H 4 O 4 Oxidation of Fe 2+ 4Fe 2+ + O 2 + 4H + 4Fe H 2 O 4Fe e - 4Fe 3+ O 2 + 4e - 2O 2-2O H + 2H 2 O Precipitation of Fe 3+ Fe H 2 O Fe(OH) 3 + 3H + Ferrihydrite Crystalization of Fe 2 O 3 2Fe(OH) 3 Fe 2 O 3 + 3H 2 O Hematite

= [ 3+ ] / [H + ] 3 log [ 3+ ] = logk - 3pH (OH) 3 + H 2 O (OH) 4 - + H + K =

7 (1), O 2 + 2H 2 O H 4 O 4 K = [H 4 O 4 ] / [O 2 ][H2O] 2 = [H 4 O 4 ] log [H 4 O 4 ] = logk (OH) 3 + 3H H 2 O K = [ 3+ ][H 2 O] 3 / [(OH) 3 ][H + ] 3 = [ 3+ ] / [H + ] 3 log [ 3+ ] = logk - 3pH (OH) 3 + H 2 O (OH) H + K = [(OH) 4 - ][H + ] / [(OH) 3 ][H 2 O] = [(OH) 4 - ][H + ] log[(oh) 4 - ] = logk + ph

8 . (1) 2 2 O 5 (OH) 4 + 6H H 4 O 4 + H 2 O K = [ 3+ ] 2 [H 4 O 4 ] 2 / [H + ] 6.. Equilibrium states logk = H = kcal Data from Minteq.dat IAP = [ 3+ ] 2 [H 4 O 4 ] 2 / [H + ] 6.. Actual states SI = log(iap/k) SI > 0 (IAP > K) Precipitation of kaolinite SI < 0 (IAP < K) Dissolution of kaolinite SI = 0 (IAP = K) Equilibrium of kaolinite with solution

9 (2) 2 2 O 5 (OH) 4 + 6H H 4 O 4 + H 2 O Product / % Formation rates of kaolinite DURATION / Sx10 6

10 aa + bb cc + dd (Reaction rate) v = d[a]/dt, v = d[b]/dt v = d[c]/dt, v = d[d]/dt (Reaction order) v = d[a]/dt = - k[a] [B] v = d[c]/dt = k[c] [D] + : k : + = = = = = n n

11 aa + bb cc + dd 0 v = - k[a] [B] = - k 1 v = - k[a] [B] = - k[a] 2 v = - k[a] [B] = - k[a][b] Conc. / M Conc. / M Conc. / M Time / Day Time / Day Time / Day

12 0 v = - k[a] [B] = - k k = 1/t(a 0 - a t ) k t = (a 0 - a t ) Units = mol l -1 S -1 1 v = - k[a] [B] = - k[a] k = 1/tIn(a 0 /a t ) kt = In(a 0 /a t ) Units = S -1 2 v = - k[a] [B] = - k[a][b] k = 1/t(a 0 - a t /a 0 a t ) kt = (a 0 - a t )/a 0 a t Units = l mol -1 S -1 k =1.157 x 10 6 mol l -1 S -1 k = x 10 6 S -1 k = x 10 6 l mol -1 S -1 kt kt kt Time / Sx10 6 Time / Sx10 6 Time / Sx10 6

13 k = A exp (-E/RT) Ink = InA - E/RT.. logk = loga - E/2.303RT.. k :, A :, E : R :, T : In k A) B) Ink/(1/T) = -E/R In k a = -E/R E = - ar = - a x (Kcal/mol) 1/T 1/T

14 Rate constants of the three chemical reactions Temp (C) Temp (K) 1/T Ink (0 order) x x x x x x x x 10 6 Ink (1st order) x x x x 10 6 Ink (2nd order) x x x x 10 6 In k (x 10 6 ) 2nd order 1st order 0 order 1/T (x 10-3 ) k = A exp (-E/RT) Ink = InA - E/RT a = Ink/(1/T) = -E/R E = - ar = - a x (Kcal/mol) Activation energy of the three chemical reactions 0 order 1st order 2nd order a x x x 10 9 E (Kcal/mol) x x x 10 9

15 Fe 2+ 1) Oxidation of pyrite 2FeS 2 + 2H 2 O + 7O 2 2Fe SO H + 2) Oxidation of Fe 2+ ions Fe 2+ + O 2 + 4H + 4Fe H 2 O 3) Formation of schwertmannite 8Fe 3+ + XSO (16-2X)H 2 O Fe 8 O 8 (OH) 8-2x (SO 4 ) X + (24-2X)H + Rate of Fe 2+ oxidation (nger and Stumm, 1970) dm Fe 2+/dt = - (2.91e e12 a 2 OH- PO2)m Fe 2+ PHREEQC mulation of Fe 2+ oxidation Equilibrium with PO2 Rate constant A1: K = x 10-8 (s -1 ) A2: K = x 10-8 (s -1 ) A3: K = x 10-8 (s -1 )

00) îSìyçzï®äwÇÃäÓëb-1.pdf

00) îSìyçzï®äwÇÃäÓëb-1.pdf (1) 16 Si 4+, Al 3+, Fe 3+, Fe 2+, Mg 2+, Ca 2+, Na +, K +. O 2-, OH -, F - nm m. - ) CaAl 2 Si 2 O 8 + 8H + Ca 2+ + 2Al 3+ + 2H 4 SiO 4 2Al 3+ + 2H 4 SiO 4 + H 2 O Al 2 Si 2 O 5 (OH) 4 + 6H + ph ph -