Диссертация (1150232), страница 14
Текст из файла (страница 14)
The Hydrolysis of Cations.Krieger Publishing Company, Malabar, Florida. 489 pp86H— Häkkinen, P., Purokoski, S., Lajunen, K., 1986. A potentiometric study on the complexformation of germanic acid and germinate ion with sugar acids and disaccharides in aqueous solution.Finnish Chemical Letters 13, 93– 97.88KD— Kosova, T.B., Dem‘yanets, L.N., 1988. Behaviour of germanium dioxide in water andaqueous solutions at temperatures of 25– 300 °C. Russian Journal of Inorganic Chemistry 33, 1522–1527.98PS— Pokrovski, G.S., Schott, J., 1998.
Thermodynamic properties of aqueous Ge(IV) hydroxidecomplexes from 25 to 350 °C: implications for behavior of germanium and the Ge/Si ratio inhydrothermal fluids. Geochimica et Cosmochimica Acta 62, 1631– 1642.99Приложение Д. Кинетика изомерного перехода в водномгерманомолибденового ГПА в -форму (CGe = 3·10-4 моль/л)t, мин2,02,53,03,54,04,55,05,56,06,57,07,58,08,59,09,510,011,012,013,014,015,016,017,018,019,020,025,030,035,040,045,050,055,060,065,070,0растворерН = 2рН = 1,68рН = 0,88Aсред, отн.ед. t, мин Aсред, отн.ед.
t, мин Aсред, отн.ед.0,7232,00,7202,00,6000,7212,50,7172,50,6850,7183,00,7133,00,6980,7153,50,7103,50,7010,7104,00,7104,00,7000,7034,50,7034,50,6980,7005,00,7005,00,6960,6925,50,6925,50,6890,6896,00,6896,00,6850,6856,50,6856,50,6820,6807,00,6807,00,6760,6767,50,6767,50,6710,6738,00,6738,00,6700,6698,50,6698,50,6680,6639,00,6639,00,6620,6609,50,6609,50,6580,65710,00,65710,00,6560,65111,00,65011,00,6520,64512,00,64712,00,6460,63813,00,64012,70,6420,63114,00,63114,00,6350,62715,00,62715,00,6280,62316,00,62316,00,6260,61917,00,61917,00,6220,61318,00,61518,00,6160,61119,00,61119,00,6130,60920,00,60520,00,6110,59225,00,59225,00,5950,58930,00,58930,00,5840,57235,00,57235,00,5730,56540,00,56140,00,5660,55945,00,55945,00,5600,55650,00,55750,00,5570,55355,00,55455,00,5550,55060,00,55260,00,5530,55065,00,55265,00,5530,55070,00,55270,00,553β-100Приложение Е.Кинетическиеданныеобразованияβи-форм–4молибдогерманового ГПА (СGe = 3·10 моль/л) при различных значениях рНpHt, мин2,02,53,03,54,04,55,06,07,08,09,010,011,012,013,014,015,016,017,018,019,020,025,030,035,040,045,050,055,060,065,070,01,20,7220,7180,7140,7100,7060,7000,6960,6870,6800,6690,6630,6570,6470,6410,6360,6310,6270,6210,6150,6110,6070,6050,5920,5890,5720,5640,5590,5580,5570,5500,5500,55010,880,84Aсред, отн.ед.0,5630,1840,0850,6000,2320,1160,6290,2610,1370,6350,3110,1520,6390,3400,1680,6390,3600,1850,6390,3800,1960,6370,4240,2170,6340,4600,2330,6310,4710,2450,6300,4900,2580,6270,5220,2720,6260,5300,2800,6240,5390,2880,6230,5420,3010,6210,5500,3160,6180,5590,3250,6140,5640,3340,6120,5690,3420,6100,5720,3510,6080,5760,3600,6070,5780,3690,5950,5790,4040,5900,5800,4330,5840,5780,4520,5740,5760,4680,5680,5710,4820,5630,5600,4920,5600,5570,5000,5580,5530,5110,5580,5500,5180,5580,5490,5180,60,0830,0960,1090,1190,1310,1380,1470,1610,1710,1790,1870,1940,2080,2120,2170,2270,2310,2350,2390,2430,2490,2560,2680,2820,2930,3020,3110,3190,3250,3300,3370,344101Приложение Ж.
Кинетика образования β-формы германомолибденового ГПА вводно-спиртовом растворе при 16 об. % спирта, pH = 0,76 (СGe = 3·10-4 моль/л)t1, мин A1, отн.ед. t2, мин A2, отн.ед. t3, мин A3, отн.ед. Aсред, отн.ед.0,00,0000,00,0000,00,0000,0001,50,3571,50,3271,50,3580,3472,00,3972,00,3732,00,4140,3952,50,4502,50,4322,50,4600,4473,00,4913,00,4923,00,4940,4923,50,5243,50,5253,50,5260,5254,00,5584,00,5604,00,5610,5604,50,5744,50,5764,50,5750,5755,00,5945,00,5915,00,5970,5945,50,6105,50,6125,50,6140,6126,00,6376,00,6466,00,6400,6417,00,6477,00,6487,00,6490,6488,00,6658,00,6628,00,6580,6629,00,6809,00,6829,00,6850,68210,00,68910,00,70410,00,6920,69511,00,70011,00,70911,00,7090,70612,00,70612,00,71212,00,7110,71013,00,70913,00,71513,00,7140,71314,00,71214,00,71614,00,7170,71515,00,71615,00,71815,00,7230,71916,00,71716,00,71816,00,7250,72017,00,72017,00,71917,00,7250,72118,00,72218,00,71918,00,7260,72219,00,72219,00,71919,00,7270,72320,00,72220,00,72020,00,7270,72325,00,72225,00,72025,00,7270,72330,00,72230,00,72030,00,7270,72335,00,72235,00,72035,00,7270,72340,00,72240,00,72040,00,7270,72345,00,72245,00,72045,00,7270,72350,00,71050,00,70750,00,7130,71055,00,70555,00,70355,00,7050,70460,00,70060,00,70160,00,7000,70065,00,69665,00,69765,00,6980,69770,00,68970,00,69170,00,6950,692102Приложение З.
Кинетика образования α-формы германомолибденовогогетерополианиона в интервале значений рН от 0,84 до 0,64 (СGe = 3·10-4 моль/л)pH=0,84t, мин0,02,02,22,42,62,83,03,23,43,63,84,04,44,85,25,66,07,08,09,010,012,014,016,018,020,0pH=0,82pH=0,8pH=0,78АсредАсредАсредАсредt, минt, минt, минотн.ед.отн.ед.отн.ед.отн.ед.0,0000,5480,5500,5520,5530,5550,5570,5580,5590,5600,5600,5600,5610,5610,5610,5600,5610,5610,5610,5610,5610,5610,5610,5610,5610,5610,02,02,22,42,62,83,03,23,43,63,84,04,44,85,25,66,07,08,09,010,012,014,016,018,020,00,0000,5320,5380,5430,5460,5480,5500,5520,5520,5530,5540,5540,5550,5550,5550,5550,5550,5550,5540,5550,5550,5550,5550,5560,5560,5560,02,02,22,42,62,83,03,23,43,63,84,04,44,85,25,66,07,08,09,010,012,014,016,018,020,00,0000,4880,5000,5100,5170,5230,5280,5320,5360,5390,5400,5420,5440,5470,5470,5480,5480,5480,5490,5490,5490,5490,5500,5500,5490,5500,02,02,22,42,62,83,03,23,43,63,84,04,44,85,25,66,07,08,09,010,012,014,016,018,020,00,0000,4150,4330,4490,4630,4750,4850,4940,5010,5090,5150,5200,5270,5350,5390,5420,5450,5490,5490,5500,5490,5500,5510,5520,5520,553103pH=0,76t, мин0,02,02,22,42,62,83,03,23,43,63,84,04,44,85,25,66,07,08,09,010,012,014,016,018,020,0pH=0,72pH=0,68pH=0,64Асред t, мин Асред t, мин Асред t, мин Асредотн.ед.отн.ед.отн.ед.отн.ед.0,0000,3200,3390,3570,3740,3890,4020,4150,4260,4370,4470,4560,4710,4840,4960,5050,5130,5280,5360,5430,5470,5520,5540,5540,5540,5530,02,02,22,42,62,83,03,23,43,63,84,04,44,85,25,66,07,08,09,010,012,014,016,018,020,00,0000,1750,1900,2030,2160,2290,2410,2560,2640,2770,2850,2950,3140,3320,3480,3630,3780,4080,4340,4550,4720,4980,5190,5340,5390,5430,02,02,22,42,62,83,03,23,43,63,84,04,44,85,25,66,07,08,09,010,012,014,016,018,020,00,0000,0890,0970,1050,1120,1200,1270,1350,1420,1490,1560,1630,1770,1890,2020,2140,2260,2530,2780,3010,3280,3600,3910,4170,4380,4530,02,02,22,42,62,83,03,23,43,63,84,04,44,85,25,66,07,08,09,010,012,014,016,018,020,00,0000,0650,0710,0770,0830,0880,0940,1000,1050,1110,1160,1220,1330,1430,1530,1630,1760,1950,2170,2360,2560,2880,3230,3470,3720,392104Приложение И.
Сравнение экспериментальной и теоретической кинетикиизомерного перехода германомолибденового гетерополианиона при рН=1,2(Ge = 3·10-4 моль/л)t1, мин0,02,02,22,42,62,83,03,23,43,63,84,05,06,07,08,09,010,011,012,014,016,018,020,024,028,032,036,040,045,050,055,060,0A1,отн.ед.0,0000,7500,7480,7460,7440,7420,7400,7370,7380,7350,7320,7290,7230,7140,7050,6980,6880,6790,6740,6670,6560,6460,6350,6220,6070,5950,5850,5770,5700,5640,5600,5600,560t2, мин A2, отн.ед. t3, мин A3, отн.ед. tтеор, мин Aтеор, отн.ед.0,00,0000,00,0000,00,0002,00,7482,00,7542,00,7492,20,7462,20,7532,20,7492,40,7452,40,7502,40,7482,60,7432,60,7492,60,7462,80,7422,80,7472,80,7443,00,7373,00,7463,00,7423,20,7363,20,7443,20,7413,40,7343,40,7413,40,7383,60,7323,60,7393,60,7363,80,7313,80,7373,80,7344,00,7304,00,7354,00,7325,00,7225,00,7245,00,7216,00,7126,00,7156,00,7117,00,7057,00,7067,00,7028,00,6968,00,6998,00,6939,00,6839,00,6929,00,68510,00,67710,00,68310,00,67711,00,67211,00,67511,00,67012,00,66712,00,66812,00,66314,00,65314,00,65714,00,65116,00,64516,00,64516,00,63918,00,63218,00,63518,00,63020,00,62120,00,62420,00,62124,00,60624,00,60924,00,60628,00,59328,00,59728,00,59432,00,58332,00,58932,00,58536,00,57536,00,58036,00,57840,00,56840,00,57440,00,57345,00,56245,00,56745,00,56750,00,55650,00,56450,00,56355,00,55355,00,55855,00,56060,00,55360,00,55860,00,558105Приложение К.
Экспериментальные и теоретические зависимости значенийоптических плотностей кремнемолибденовго и германомолибденового ГПА отвремениCSi = 3·10-4 моль/л, CGe = 0,6·10-4 моль/лt,мин АGe отн.ед. АSi отн.ед. AΣ отн.ед. Аэксп отн.ед.0,00,0000,0000,0000,0002,00,1070,7930,9000,9032,20,1070,7940,9010,9052,40,1070,7950,9020,9062,60,1070,7960,9020,9072,80,1060,7960,9020,9073,00,1060,7960,9020,9083,20,1060,7960,9020,9073,40,1050,7960,9020,9073,60,1050,7960,9020,9063,80,1050,7960,9010,9054,00,1050,7960,9010,9044,40,1040,7960,9010,9034,80,1040,7960,9000,9015,20,1030,7960,9000,9005,60,1030,7960,8990,9006,00,1020,7960,8990,8997,00,1010,7960,8970,8988,00,1000,7960,8960,8979,00,0990,7960,8950,89610,00,0980,7960,8940,89512,00,0960,7960,8920,89314,00,0940,7970,8910,89116,00,0930,7970,8890,89018,00,0910,7970,8880,88920,00,0900,7970,8870,88822,00,0890,7970,8860,88624,00,0880,7970,8850,88526,00,0880,7970,8840,88428,00,0870,7970,8830,88330,00,0860,7970,8830,88235,00,0850,7970,8820,88040,00,0840,7970,8810,87845,00,0830,7970,8800,87750,00,0830,7970,8790,87655,00,0830,7970,8790,87660,00,0820,7970,8790,876106t,мин0,02,02,22,42,62,83,03,23,43,63,84,04,44,85,25,66,07,08,09,010,012,014,016,018,020,022,024,026,028,030,035,040,045,050,055,060,0CSi = 1,16·10-4 моль/л, CGe = 1,8·10-4 моль/лАGe отн.ед.
АSi отн.ед. AΣ отн.ед. Аэксп отн.ед.0,0000,0000,0000,0000,4250,3120,7360,7370,4250,3120,7370,7380,4240,3130,7370,7380,4240,3130,7370,7360,4230,3130,7360,7350,4220,3130,7350,7340,4210,3130,7340,7330,4200,3130,7330,7310,4190,3130,7320,7300,4180,3130,7310,7280,4170,3130,7300,7260,4150,3130,7280,7260,4130,3130,7260,7250,4110,3130,7250,7240,4090,3130,7230,7220,4080,3130,7210,7200,4030,3130,7170,7180,3990,3130,7120,7150,3950,3130,7090,7110,3920,3130,7050,7050,3850,3130,6980,6980,3790,3130,6920,6920,3740,3130,6870,6840,3690,3130,6830,6790,3650,3130,6780,6740,3620,3130,6750,6700,3580,3130,6720,6660,3550,3130,6690,6630,3530,3130,6660,6610,3510,3130,6640,6580,3460,3130,6590,6540,3430,3130,6560,6500,3400,3130,6530,6480,3380,3130,6520,6470,3370,3130,6500,6460,3360,3130,6490,645107Приложение Л.
Результаты определения оптической плотности для построениякалибровочного графика для определения кремния в виде [Si Mo12O40 ]8А, отн. ед.CSi∙104, моль/л0,000,450,901,351,802,252,703,153,604,05100,1110,2330,3860,5140,6200,7370,8461,0051,12320,1100,2370,3890,5090,6260,7350,8581,0121,11830,1090,2350,3920,5130,6190,7460,8450,9951,11740,1100,2400,3900,5100,6210,7400,8460,9991,120Асредотн.ед.00,1100,2360,3890,5120,6220,7400,8491,0031,120108Приложение М Результаты дифференциального спектрофотометрическогоопределения германия и кремния в совместном присутствииПриложение М.1 Результаты дифференциального спектрофотометрическогоопределения германия и кремния в совместном присутствии для систем ссодержанием германия 15 – 70 мол.%(20% Ge)t,Aсред,минотн.ед.0,00,0002,00,7222,20,7252,40,7272,60,7292,80,7293,00,7293,20,7293,40,7283,60,7283,80,7284,00,7274,40,7264,80,7265,20,7255,60,7246,00,7237,00,7218,00,7209,00,71910,00,71712,00,71514,00,71216,00,70918,00,70720,00,70522,00,70324,00,70126,00,70028,00,699Na2SiO3-GeO2(25% Ge)(30% Ge)t,Aсред,t,Aсред,минотн.ед.минотн.ед.0,00,0000,00,0002,00,9472,00,5252,20,9482,20,5262,40,9492,40,5262,60,9502,60,5272,80,9502,80,5263,00,9493,00,5263,20,9483,20,5263,40,9473,40,5263,60,9463,60,5253,80,9453,80,5244,00,9444,00,5244,40,9434,40,5244,80,9414,80,5235,20,9405,20,5225,60,9385,60,5226,00,9376,00,5217,00,9357,00,528,00,9328,00,5189,00,9299,00,51710,00,92710,00,51512,00,92312,00,51214,00,91914,00,50916,00,91616,00,50718,00,91418,00,50520,00,91120,00,50322,00,90922,00,50224,00,90724,00,50126,00,90526,00,50028,00,90428,00,499(70% Ge)t,Aсред,минотн.ед.0,00,0002,01,1112,21,1132,41,1122,61,1102,81,1093,01,1053,21,0983,41,0923,61,0913,81,0894,01,0864,41,0824,81,0785,21,0745,61,0696,01,0657,01,0578,01,0529,01,04710,01,03912,01,02414,01,01016,01,00318,00,99220,00,98422,00,97924,00,97126,00,96728,00,964109(20% Ge)t,Aсред,минотн.ед.30,00,69735,00,69540,00,69345,00,69250,00,69055,00,68960,00,689Na2SiO3-GeO2(25% Ge)(30% Ge)t,Aсред,t,Aсред,минотн.ед.минотн.ед.30,00,90330,00,49835,00,90135,00,49640,00,89940,00,49445,00,89745,00,49350,00,89650,00,49255,00,89555,00,49160,00,89460,00,491ТЭОС-GeO2(15% Ge)(35% Ge)t,Aсред,t,Aсред,минотн.ед.минотн.ед.0,00,0000,00,0002,00,9032,00,4352,20,9052,20,4362,40,9062,40,4372,60,9072,60,4372,80,9072,80,4373,00,9083,00,4373,20,9073,20,4373,40,9073,40,4363,60,9063,60,4363,80,9053,80,4364,00,9044,00,4354,40,9034,40,4344,80,9014,80,4345,20,9005,20,4335,60,9005,60,4326,00,8996,00,4327,00,8987,00,4318,00,8978,00,4299,00,8969,00,42810,00,89510,00,42712,00,89312,00,42414,00,89114,00,42216,00,89016,00,421(70% Ge)t,Aсред,минотн.ед.30,00,95935,00,95140,00,94245,00,93750,00,93355,00,93060,00,927ГСО-GeO2(45% Ge)t,Aсред,минотн.ед.0,00,0002,01,0222,21,0242,41,0252,61,0252,81,0243,01,0233,21,0223,41,0223,61,0223,81,0214,01,0204,41,0194,81,0185,21,0165,61,0156,01,0137,01,0108,01,0059,01,00210,00,99612,00,99014,00,98416,00,977(60% Ge)t,Aсред,минотн.ед.0,00,0002,00,7272,20,7282,40,7292,60,7302,80,7303,00,7293,20,7293,40,7283,60,7273,80,7274,00,7264,40,7264,80,7255,20,7245,60,7226,00,7207,00,7188,00,7159,00,71110,00,70512,00,69814,00,69216,00,684110ТЭОС-GeO2(15% Ge)(35% Ge)t,Aсред,t,Aсред,минотн.ед.минотн.ед.18,00,88918,00,42020,00,88820,00,41822,00,88622,00,41724,00,88524,00,41526,00,88426,00,41428,00,88328,00,41330,00,88230,00,41235,00,88035,00,41040,00,87840,00,40845,00,87745,00,40750,00,87650,00,40655,00,87655,00,40560,00,87660,00,405ГСО-GeO2(45% Ge)t,Aсред,минотн.ед.18,00,97320,00,96822,00,96424,00,96026,00,95828,00,95530,00,95235,00,94740,00,94345,00,93950,00,93655,00,93460,00,933(60% Ge)t,Aсред,минотн.ед.18,00,67920,00,67422,00,67024,00,66626,00,66328,00,66130,00,65835,00,65440,00,65045,00,64850,00,64755,00,64660,00,645111Приложение М.2 Результаты дифференциального спектрофотометрическогоопределения германия и кремния в совместном присутствии для систем ссодержанием германия 75 – 90 мол.%Na2SiO3-GeO2Aсред, отн.ед.Aсред, отн.ед.t, минt, мин(75% Ge) (90% Ge)(75% Ge) (90% Ge)0,00,0000,0009,00,7520,9002,02,22,42,62,83,03,23,43,63,84,04,44,85,25,66,07,08,00,8110,8100,8090,8080,8070,8050,8030,8020,8000,7980,7950,7910,7880,7840,7800,7760,7680,7590,9990,9960,9960,9950,9920,9880,9840,9810,9780,9750,9720,9650,9580,9510,9450,9390,9220,91310,012,014,016,018,020,022,024,026,028,030,035,040,045,050,055,060,00,7470,7370,7300,7230,7170,7120,7060,7020,6980,6950,6920,6870,6820,6780,6750,6730,6710,8880,8660,8510,8370,8230,8140,8040,7960,7900,7850,7810,7710,7650,7630,7600,7590,758.
![](https://s.studizba.com/z.php?f=/templates/si/i/noavatar.png&w=100&h=100&t=1"){kind=avatar}
