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solubility and phase relations ofprccipitatcs in high temperature waler (Alexander and LUll, 1989; Lindsay, 1989; Greenberg and Moller, 1989; Pitzer, 1986) but more information was needed before equilibrium models could be developed for this system. The main source orimn in a boiler system is magnetite, Fe1IFeJll204' which acts as a protective coating on carbon steel components and also exists as loose deposits in the boiler tube. Ziemniak and Opalka (1992, 1993) reported results for the solubility of SIHP with magnetite as the iron source but did not measure the hydrogen concentrations needed for their thermodynamic calculations. Quinlan (1996) avoided this problem by using excess hematite, Fe 1ll 20J' instead ofmagnetite to measure the solubility ofsrnp according to the reaction: 3 Fe llI 203(S) + 26 Na+(aq) + 12 HPoi·(aq)+ 2 OH·(aq) "'"' 6 NaJFelll(P04)T(N
introduced from stainless steel vessels and piping, and from Inconellubing. Ziemniak el at (1989) invcstigated the solubility/phase behaviour of nickel oxide in alkaline sodium phosphate solutions at elevated temperatures. Nickel oxide becomes soluble in high lemper.l.Iure aqueous solutions according 10 the following reaction: NiO(s) + 2 If'(aq) = Nr1(aq) + HzO(I) (1.40) 1be dissolved nickel(I1) ion becomes stabilized in aqueous solutions by lhe fannalian of hydroxo-complcxes where the nickel can become surrounded by an inner hydration sphere ofsix water molecules. As the pH ofthe solution rises, dissociation occurs as follows: Ni(OH)z(aq) + H20(1)'" Ni(OHh"(aq) + H\aq) The overall nickel oxide dissolution reaction becomes the following: NiO(s) + (2-n)H·(aq) ... Ni(OH)/·"(aq) + (l-Il)H20(1) 26 (1.41) (1.42) (1.43) (1.44)
Page 4: 1"'1 National Library of Canada Bib
Page 8: y thcnnally dc
Page 11 and 12: Gregory for his kindness and making
Page 15: LIST OF TABLES Table 1.1 Corrosion
Page 21 and 22: single crystals ofquartz (Nacken, 1
Page 23 and 24: phosphate control in the 19&Os was
Page 25: the standard Gibbs energies and ent
Page 36: consist ofortnophospllatcs. The bou
Page 41 and 42: 2 FcIlFc[[J204(S) + 26 Na+(aq) + 12
Page 46: where 11 equals the ionic state ofh
Page 49: '", g :£ 30
Page 55: 1.10 Project Objectives The objecti
Page 61 and 62: II - "7 /'7"7L 41 J n
Page 65 and 66: 2.3.2 Single Crystal X-Ray Dif'frac
Page 67 and 68: 2.4 Synthesis and Characterization
Page 69 and 70: Several solid starting materials we
Page 75 and 76: FeUlNTA(aq) + HPOl(aq) + NH/(aq) __
Page 77 and 78: All runs lasted up to to days at a
Page 79 and 80: 0.0 l--l_-L_l-....J.._-L_l-....J..-
Page 81 and 82: dissolution orSNHP and allowed the
Page 83 and 84: (a) (b) Figure 3.1a and b: Scanning
Page 87 and 88: and the equilibrium constant for ma
Page 89 and 90: groups. Oxidizing agents were previ
Page 91 and 92: and reacted with aqueous sodium pho
Page 94 and 95:
(al (b) Figure 3.5a and b: Scanning
Page 97 and 98:
Figure 3.7: Scanning electron micro
Page 99:
Table 3.1: Positional parameters fo
Page 104:
Figure 3.10: Scanning electron micr
Page 107 and 108:
pattern is listed in Table A.LI3. E
Page 109:
4.0 SOLUBILITY AND REACTION KINETIC
Page 117 and 118:
Table 4.1 Experimental C
Page 119:
Table 4.3 Standard slale properties
Page 126 and 127:
Table 4.6 HKF equation ofstate coef
Page 128 and 129:
Equilibrium constants are listed in
Page 130:
Table 4.9 Equilbrium constants for
Page 136:
Table 4.10 Standard state propertie
Page 142 and 143:
lower NalP04 mole ratio than the re
Page 144:
Broadbent D., Lewis G.G., and Wetto
Page 147 and 148:
Marshall W.L. (1982) Two-liquid-pha
Page 150 and 151:
Welton E.A.M. (1981) Phase equilibr
Page 152 and 153:
APPENDIX I: Powder X-ray Diffractio
Page 154 and 155:
TABLE A.l.l: X-Ray Diffraction Resu
Page 157 and 158:
TABLE A,I.3 (continued) Quinlan JCP
Page 159 and 160:
TABLE A.1.4 (continued) Quinlan (19
Page 162 and 163:
TABLE A.l.S (continued) JCPDS Quinl
Page 164 and 165:
TABLE A.1.6 (continued) Quinlan (19
Page 168 and 169:
TABLE A.L8 (continued) Boudin JCPDS
Page 170 and 171:
TABLE A.I.9 (continued) Product RGH
Page 172 and 173:
TABLE A.I.IO (continued) Ziemniak a
Page 174:
TABLE AJ.11 (continued) Zicmniak an
Page 177 and 178:
TABLE A.T.I2 (continued) Zicmniak a
Page 180:
TABLE A.I.13 (continued) Ziemniak a
Page 183:
Experimental A colorless irrcg.plal
Page 188 and 189:
Slfuc!ure Solution Refinemenl Funct
Page 190 and 191:
111
Page 192 and 193:
TABLE A.1II.1: Summary of ICP ES Re
Page 194 and 195:
TABLE A.lll.2: KinclicData Time m(N
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TABLE A.III.2 (continued) Time m(Na
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TABLE A.lll.2 (continued) Time m(Na
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TABLE A.lIl.l (continued) Time m(Na
Page 202:
TABLE A.III.3 (continued) t "C m(p0
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