K2O-MgO-Al2O3-SiO2
Phlogopite data, consistent with the calorimetry of Circone & Navrotsky (1993), now agree perfectly with the experiments of Peterson & Newton (1990) for 2phl + 6q = 3en + 2san + 2H2O, but only marginally with the experiments of Wood (1976) on the same reaction. The agreement with the experiments of Bohlen et al. (1983) is less good. Eastonite data is provisional, and is based on the approximate compositions of biotite coexisting with phengite, sanidine and quartz at 5 kbar and 700°C in the diagrams of Massonne & Schreyer (1987), using the equilibrium 3mu + 2phl = 3east + 2san + 3q + 2H2O. A non-ideal mixing model for biotites was used (see notes).
The celadonite enthalpy was derived from the experiments of Massonne & Schreyer (1989) on the equilibria 2ta + 6mu + 4q/coe = 6 cel + 6ky + 2H2O. The resulting data are in reasonable agreement with the experiments of Massonne & Schreyer (1987) and Velde (1965) on the equilibria 3cel = phl + 2san + 3q + 2H2O and of Massonne & Schreyer (1987) on the equilibrium 3mu + 2phl = 3east + 2san + 3q + 2H2O. However, the calculated curve for the talc + muscovite breakdown curve ta + mu = phl + ky + 3q + H2O does not agree well with the experiments of Massonne & Schreyer (1989), signalling that thermodynamic modelling of phengites and aluminous biotites requires further work.
199) kals + san = 2lc (Scarfe et al., 1965; Lindsley 1966)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
0 - 4.0 600 628 27.75 28.87 620 14 3 (28.31 <-> 28.95)
0 - 6.0 675 700 28.43 29.43 678 14 cH = 28.54 (sd 0.27)
0 - 8.0 725 750 28.08 29.08 737 14 within bracket
0 - 25.0 22.0 1200 26.14 29.89 22.84 0.77 uH = 0.23, d/s = 0.9, h = 0.94
200) san + fo = lc + en (Luth, 1967)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
0 - 1.0 975 1005 16.84 17.53 1001 22 1 (16.91 <-> 17.46)
cH = 17.45 (sd 0.25)
within bracket
uH = 0.12, d/s = 3.0, h = 0.64
201) 2phl + 3en = 2san + 6fo + 2H2O (Luth, 1967)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
0 0 0.4 850 900 260.69 270.26 873 14 1 (261.86 <-> 268.37)
0 0 0.7 905 950 261.11 269.13 927 16 cH = 265.12 (sd 1.38)
within bracket
uH = 0.97, d/s = 4.2, h = 0.23
202) 2phl + san = 3lc + 3fo + 2H2O (Luth, 1967)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
0 0 0.4 900 950 315.99 328.96 906 10 1 (316.28 <-> 320.30)
0 0 0.7 940 960 315.64 320.58 947 12 cH = 317.47 (sd 1.43)
within bracket
uH = 1.33, d/s = 1.7, h = 0.41
* 2phl = kals + lc + 3fo + 2H2O (Luth, 1967)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
0 0 0.4 1000 1020 289.85 294.02 -4 996 14 ** NOT USED **
0 0 0.7 1050 1075 288.74 293.68 1051 14 cH = 288.93 (sd 1.44)
0 0 1.0 1150 1175 300.60 305.36 -61 1089 16
203) kals + 2en = san + 2fo (Wendlandt & Eggler, 1980)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
0 - 27.0 25.0 1170 -8.13 -6.32 25.05 1.15 1 (-7.99 <-> -6.46)
cH = -6.36 (sd 0.52)
too high but OK
uH = 0.47, d/s = 1.9, h = 0.36
* 5mu + 3clin = 5phl + 8ky + q + 12H2O (Bird & Fawcett, 1973)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
-1.00 0 7.2 632 640 1062.65 1067.95 -11 621 12 ** NOT USED **
-1.00 0 8.3 634 646 1060.44 1068.21 -8 626 12 cH = 1055.37 (sd 3.74)
* 5mu + 3clin = 5phl + 8ky + q + 12H2O (Massonne, unpub)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
-1.68 0 4.0 540 570 1018.19 1040.11 21 591 10 ** NOT USED **
-1.68 0 6.0 570 590 1030.12 1043.94 17 607 10 cH = 1055.37 (sd 3.74)
* 6mu + 2phl + 15q = 3crd + 8san + 8H2O (Seifert, 1976)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
1.46 0 1.0 520 530 846.34 853.58 12 542 6 ** NOT USED **
1.46 0 2.0 580 600 860.26 873.63 583 6 cH = 862.22 (sd 2.10)
1.46 0 3.0 630 640 868.31 874.64 -10 620 6
1.46 0 4.0 660 670 864.52 870.62 -4 656 6
1.46 0 5.0 685 700 858.63 867.51 691 6
* mu + clin + 2q = crd + phl + 4H2O (Seifert, 1970)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
-0.29 0 1.0 485 505 378.96 385.75 504 4 ** NOT USED **
-0.29 0 2.0 515 535 380.47 386.81 531 6 cH = 385.43 (sd 0.85)
-0.29 0 5.0 595 625 385.50 394.13 595 6
-0.29 0 6.0 625 645 388.63 394.25 -11 614 6
-0.29 0 7.0 650 660 390.45 393.20 -18 632 6
204) 6cel + 6ky + 2H2O = 2ta + 6mu + 4coe (Massonne & Schreyer, 1989)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
-2.11 0 41.0 39.0 750 -224.93 -215.52 -0.89 38.11 1.87 5 (-223.36 <-> -213.80)
-2.54 0 41.0 39.0 670 -227.53 -218.02 -1.40 37.60 1.84 cH = -211.31 (sd 4.43) 3
0.42 0 36.0 34.0 770 -221.73 -212.14 -0.17 33.83 1.84 too high but OK
-1.25 0 36.0 34.0 666 -213.94 -204.22 35.46 1.82 uH = 3.67, d/s = -1.8, h = 0.58
1.22 0 36.0 34.0 587 -236.77 -226.94 -3.15 30.85 1.77
2.41 0 31.0 29.0 754 -215.41 -205.61 30.16 1.81
4.00 0 31.0 29.0 685 -230.15 -220.25 -1.79 27.21 1.77
1.63 0 31.0 29.0 601 -214.40 -204.39 30.38 1.77
205) 6cel + 6ky + 2H2O = 2ta + 6mu + 4q (Massonne & Schreyer, 1989)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
3.11 0 26.0 24.0 742 -216.30 -204.67 2.86 28.86 1.58 4 (-226.73 <-> -218.36)
5.46 0 26.0 24.0 656 -236.61 -224.87 25.35 1.54 cH = -232.78 (sd 4.43) 3
3.49 0 26.0 24.0 573 -223.30 -211.45 1.61 27.61 1.54 too low but OK
8.66 0 21.0 19.0 728 -233.63 -221.81 20.86 1.54 uH = 2.52, d/s = -3.9, h = 0.42
6.63 0 21.0 19.0 647 -216.10 -204.16 2.81 23.81 1.53
14.52 0 16.0 14.0 663 -247.76 -235.74 -0.49 13.51 1.52
* 3cel = phl + 2san + 3q + 2H2O (Massonne & Schreyer, 1987)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
1.94 0 21.0 19.0 645 150.54 159.65 -1.80 17.20 1.05 ** NOT USED **
3.60 0 16.0 14.0 649 161.59 171.13 14.66 1.02 cH = 167.96 (sd 2.38)
4.92 0 11.6 9.6 590 164.03 174.01 10.81 0.98
5.73 0 11.6 9.6 590 158.25 168.23 9.65 0.96
5.29 0 11.6 9.6 689 175.57 185.81 1.53 13.13 1.00
8.28 0 8.0 6.0 650 165.65 176.69 7.57 0.91
10.83 0 6.0 4.0 700 162.46 174.87 5.09 0.81
* 3cel = phl + 2san + 3q + 2H2O (Velde, 1965; Massonne & Schreyer, 1987)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
7.67 0 2.0 375 390 165.66 167.64 3 393 28 ** NOT USED **
5.68 0 4.5 440 480 172.40 178.79 -28 412 26 cH = 167.96 (sd 2.38)
206) 3mu + 2phl = 3east + 2san + 3q + 2H2O (Massonne & Schreyer, 1987)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
-2.10 0 6.0 4.0 700 192.91 203.77 4.97 4.04 1 (193.78 <-> 202.90)
cH = 198.34 (sd 10.40) 2
within bracket
uH = 1.16, d/s = 4.7, h = 1.00
* ta + mu = phl + ky + 3q + H2O (Massonne & Schreyer, 1989)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
0.06 0 10.0 595 623 91.18 92.95 17 640 24 ** NOT USED **
0.28 0 15.0 662 675 91.18 91.92 37 712 26 cH = 94.02 (sd 0.72)
0.49 0 20.0 723 732 90.69 91.16 55 787 30
0.70 0 25.0 771 790 89.25 90.16 81 871 32
207) 3clin + 3phl + 23q = 3mu + 8ta + 4H2O (Massonne & Schreyer, 1989)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
-1.63 0 9.6 562 297.89 601 46 2 (304.51 <-> 309.22)
-1.63 0 14.0 544 308.49 505 44 cH = 303.23 (sd 2.91) 3
-0.91 0 10.6 639 305.24 -17 622 50 too low but OK
-0.91 0 13.0 619 309.72 566 48 uH = 1.69, d/s = 1.0, h = 0.13
208) 2phl + 6q = 3en + 2san + 2H2O (Bohlen et al., 1983)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
0 0.66 5.0 775 805 213.31 217.58 17 822 20 1 (213.77 <-> 217.12)
cH = 219.95 (sd 1.37) 2
too high
uH = 0.74, d/s = 2.9, h = 0.13
209) 2phl + 6q = 3en + 2san + 2H2O (Peterson & Newton, 1990)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
0 0.73 2.5 745 765 218.51 221.69 754 18 1 (218.76 <-> 221.43)
cH = 219.95 (sd 1.37) 2
within bracket
uH = 0.82, d/s = 1.9, h = 0.20
* 2phl + 6q = 3en + 2san + 2H2O (Wood, 1976)
ln_K x(CO2) P(kbar) T(C) H(low) H(high) miss calc 2sd summary
0 0 0.3 0.3 750 222.88 225.11 0.08 0.43 0.08 ** NOT USED **
0 0 0.5 0.4 790 225.83 228.19 0.25 0.72 0.15 cH = 219.95 (sd 1.37)
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