Диссертация (1150101), страница 23
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Расчет по изопотенциалам NaCl.m – моляльность, моль/кг р-ля; ∆ – значения химического потенциала NaCl врастворах; x – мольная доля компонента раствора; 1 – вода; 1 – активность воды;Γ()– сольватационный избыток частиц i над j в окружении центральной частицыk.1)2)∆, = -4+−211Γ1(2)Γ1(+ Γ1(2)2)6,656,396,055,725,395,044,644,33,933,523,072,652,221,731,180,710,240,170,170,170,170,170,170,120,170,170,170,170,170,170,170,170,210,070,82070,83120,84180,85230,86280,87330,88380,89440,90490,91540,92590,93640,94700,95750,9680,97850,9891-0,67-0,62-0,57-0,56-0,54-0,42-0,49-0,57-0,44-0,37-0,35-0,35-0,29-0,18-0,24-0,060,240,330,380,430,440,46-13,990,5515,040,560,630,650,650,710,8210,55-40,25-100,73210,120,120,110,10,10,090,080,080,070,060,060,050,040,030,020,010,00431Γ2 (1)0,080,070,060,060,050,040,040,040,030,020,020,020,010,010,010,0008-0,001∆, = -3,5+−211Γ1(2)Γ1(+ Γ1(2)2)6,576,315,965,615,254,924,524,160,310,310,310,260,310,310,310,310,82070,83120,84180,85230,86280,87330,88380,8944-0,67-0,61-0,48-0,53-0,6-0,5-0,48-0,480,330,39-6,580,557,580,50,520,52210,120,110,110,10,090,090,080,071Γ2 (1)0,080,070,050,050,060,040,040,04- 164 -3,783,362,912,461,991,490,990,473)4)0,310,310,310,310,360,380,380,450,90490,91540,92590,93640,94700,95750,96800,9785-0,42-0,36-0,33-0,38-0,36-0,24-0,29-0,380,580,640,677,269,733,218,5416,290,070,060,050,040,040,030,020,010,030,020,020,020,010,010,010,003∆, = -3,0+−211Γ1(2)Γ1(+ Γ1(2)2)6,396,15,725,394,994,594,263,883,453,032,552,081,581,040,470,690,640,640,640,590,590,640,640,620,640,640,640,690,690,710,82070,83120,84180,85230,86280,87330,88380,89440,90490,91540,92590,93640,94700,95750,9680-0,51-0,52-0,55-0,46-0,4-0,57-0,58-0,4-0,39-0,37-0,29-0,34-0,28-0,16-0,16-5,43-2,480,45-2,78-2,723,833,82-0,760,6220,7144,072,153,46210,120,110,10,10,090,080,080,070,060,050,050,040,030,020,011Γ2 (1)0,060,060,060,040,040,050,040,030,020,020,010,010,010,0030,001∆, = -2,875+−211Γ1(2)Γ1(+ Γ1(2)2)6,346,015,685,34,874,544,163,743,362,892,411,941,420,90,280,780,760,730,730,730,730,730,710,730,730,730,780,780,830,830,82070,83120,84180,85230,86280,87330,88380,89440,90490,91540,92590,93640,9470,95750,9680-0,54-0,52-0,51-0,47-0,5-0,52-0,42-0,44-0,42-0,31-0,37-0,33-0,28-0,18-0,02-1,58-2,14-1,10,530,50,48-0,590,581,770,693,573,613,543,640,98210,110,110,10,10,090,080,070,070,060,050,040,030,030,020,011Γ2 (1)0,060,060,050,050,040,040,030,030,030,020,020,010,010,0030,00008- 165 -5)6)7)∆, = -2,75+−211Γ1(2)Γ1(+ Γ1(2)2)6,626,295,985,585,24,84,454,043,643,222,742,271,81,250,710,090,780,880,850,880,850,830,830,830,830,850,880,880,880,90,920,920,81020,82070,83120,84180,85230,86280,87330,88380,89440,90490,91540,92590,93640,9470,95750,968-0,84-0,69-0,56-0,5-0,43-0,48-0,49-0,45-0,46-0,43-0,35-0,3-0,26-0,23-0,12-0,029,533,630,450,47-1,8-0,450,510,551,563,092,150,71,732,771,880,98210,120,110,110,10,090,090,080,070,070,060,050,040,030,020,010,00161Γ2 (1)0,10,080,060,050,040,040,040,030,030,020,020,010,010,010,0020,00003∆, = -2,625+−211Γ1(2)Γ1(+ Γ1(2)2)6,56,25,875,495,114,684,283,883,53,072,582,131,611,090,470,951,021111,040,970,970,971,021,021,021,021,021,070,81020,82070,83120,84180,85230,86280,87330,88380,89440,90490,91540,92590,93640,9470,9575-0,81-0,67-0,53-0,52-0,53-0,41-0,37-0,47-0,51-0,42-0,32-0,28-0,22-0,2-0,195,722,31-0,310,482,07-0,69-2,250,532,652,740,680,720,782,975,15210,120,110,110,10,090,080,080,070,060,060,050,040,030,020,011Γ2 (1)0,090,080,060,050,050,030,030,030,030,020,010,010,010,0040,0016∆, = -2,5+−211Γ1(2)Γ1(+ Γ1(2)2)6,436,085,775,374,971,111,161,161,161,160,81010,82070,83120,84180,8523-0,7-0,66-0,56-0,49-0,463,692,040,440,510,54210,120,110,10,10,091Γ2 (1)0,080,070,060,050,04- 166 -4,544,163,743,312,892,391,891,40,850,248)9)1,161,161,211,161,161,191,161,161,191,190,86280,87330,88380,89440,90490,91540,92590,93640,9470,9575-0,47-0,53-0,42-0,34-0,39-0,28-0,23-0,27-0,16-0,050,532,230,57-1,111,720,71-0,341,871,980,950,080,070,070,060,050,040,030,030,020,00430,040,040,030,020,020,010,010,010,00240,0002∆, = -2,375211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)6,676,345,965,65,254,824,43,973,573,152,72,21,751,180,610,051,31,351,331,351,351,331,351,31,351,331,351,331,351,31,351,280,79970,81020,82070,83120,84180,85230,86280,87330,88380,89440,90490,91540,92590,93640,9470,9575-0,73-0,61-0,55-0,59-0,48-0,45-0,4-0,45-0,48-0,4-0,33-0,32-0,2-0,15-0,10,093,171,260,461-0,090,55-0,350,571,470,610,670,69-0,220,850,16-3,740,120,110,110,10,090,090,080,070,060,060,050,040,030,020,010,0010,090,070,060,060,050,040,030,030,030,020,020,010,010,00310,0011-0,0001+−∆, = -2,25211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)6,576,245,825,495,114,664,263,783,412,982,512,011,491,491,541,491,491,491,491,491,491,491,491,490,79970,81020,82070,83120,84180,85230,86280,87330,88380,89440,90490,9154-0,61-0,61-0,54-0,5-0,48-0,45-0,42-0,43-0,46-0,38-0,31-0,250,391,670,44-0,80,520,550,580,570,540,620,690,750,120,110,10,10,090,080,080,070,060,050,050,040,070,070,060,050,040,040,030,030,030,020,010,01+−- 167 -1,470,90,3310)1,491,491,490,92590,93640,947-0,18-0,15-0,140,820,850,860,030,020,01∆, = -2,125+−211Γ1(2)Γ1(+ Γ1(2)2)6,436,085,685,344,924,474,043,573,172,71,732,251,140,590,051,731,731,781,731,731,731,751,681,731,731,711,711,661,641,590,79970,81020,82070,83120,84180,85230,86280,87330,88380,89440,91540,90490,92590,93640,947-0,59-0,61-0,55-0,47-0,46-0,46-0,35-0,4-0,48-0,33-0,27-0,19-0,13-0,08-0,040,411,490,43-0,590,541,01-0,560,141,750,420,480,16-0,31-0,99-1,7911)0,0050,0020,001210,120,110,10,10,090,080,070,060,060,050,030,040,020,010,00091Γ2 (1)0,070,070,060,050,040,040,030,030,030,020,010,010,00260,00090,00003∆, = -2,0211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)5,915,495,114,734,233,833,312,892,461,961,370,80,241,921,971,971,971,971,941,921,921,941,921,871,871,820,81020,82070,83120,84180,85230,86280,87330,88380,89440,90490,91540,92590,9364-0,62-0,58-0,54-0,45-0,39-0,34-0,35-0,45-0,36-0,13-0,1-0,1-0,022,381,420,460,55-0,02-0,390,220,980,63-0,72-0,24-0,3-1,420,110,10,090,090,080,070,060,050,040,040,020,010,0040,070,060,050,040,030,020,020,020,020,0050,0020,0010,0001+−- 168 -12)∆, = -1,875211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)5,34,94,4943,553,072,552,11,560,950,432,22,22,22,162,182,162,162,162,132,112,010,82070,83120,84180,85230,86280,87330,88380,89440,90490,91540,9259-0,52-0,51-0,39-0,38-0,4-0,31-0,35-0,28-0,12-0,010,050,480,49-0,130,260,60,310,650,12-0,13-1,55-3,210,10,090,080,070,060,060,050,040,030,020,010,050,040,030,030,030,020,020,010,0030,0003-0,000413)+−∆, = -1,75211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)5,044,644,213,713,312,742,221,71,140,590,142,442,442,442,422,422,422,392,392,352,252,130,82070,83120,84180,85230,86280,87330,88380,89440,90490,91540,9259-0,52-0,5-0,4-0,41-0,37-0,24-0,26-0,2-0,020,040,0040,480,50,270,260,630,240,210,07-1,63-3,25-3,80,090,080,080,070,060,050,040,030,020,010,0030,050,040,030,030,020,010,010,010,0005-0,0004-0,0000114)+−∆, = -1,625211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)4,263,883,412,932,461,81,30,750,242,772,772,682,682,632,582,582,492,350,83120,84180,85230,86280,87330,88380,89440,90490,9154-0,54-0,36-0,29-0,32-0,12-0,16-0,160,070,130,46-0,7-0,62-0,1-0,70,04-0,68-2,96-3,890,080,070,060,050,040,030,020,010,0040,040,030,020,020,010,010,004-0,001-0,0005+−- 169 -15)∆, = -1,5211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)3,783,452,932,461,891,230,830,333,153,13,033,012,922,822,772,630,83120,84420,85230,86280,87330,88380,89440,9049-0,58-0,25-0,14-0,190,06-0,09-0,120,09-0,61-0,97-0,61-0,71-1,65-1,3-2,09-3,360,070,060,050,040,030,020,010,010,040,020,010,01-0,00210,0020,0018-0,000516)+−∆, = -1,375211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)3,413,312,892,411,961,470,80,383,63,533,443,323,253,132,993,150,82070,83120,84180,85230,86280,87330,88380,8944-0,33-0,29-0,060,10,03-0,09-0,17-0,33-1,1-1,18-2,11-2,52-2,23-3,84-5,31-1,10,050,050,040,030,020,010,010,050,01740,0130,0023-0,0029-0,00060,00090,00120,017417)+−∆, = -1,125211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)2,892,512,081,560,990,520,384,053,963,863,673,533,393,150,82070,83120,84180,85230,86280,87330,8838-0,33-0,29-0,060,10,03-0,09-0,17-1,1-1,18-2,11-2,52-2,23-3,84-5,310,050,050,040,030,020,010,010,01740,0130,0023-0,0029-0,00060,00090,001218)+−∆, = -1211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)2,982,514,434,240,81010,8207-0,02-0,08-2,39-2,080,050,050,00120,0035+−- 170 -2,061,581,040,4719)4,13,963,843,670,83120,84180,85230,8628-0,11-0,050,070,17-1,8-1,67-2,02-2,530,040,030,020,010,0040,0015-0,0013-0,0014∆, = -0,875211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)1,991,420,950,384,434,294,13,960,82070,83120,84180,85230,010,020,050,07-1,51-2,03-2,14-1,740,030,020,020,01-0,0004-0,0005-0,0008-0,000320)+−∆, = -0,75211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)1,731,350,850,284,864,624,384,190,81020,82070,83120,84180,0040,090,170,16-2,93-2,98-2,68-2,340,030,020,020,01-0,0001-0,0022-0,0026-0,000821)+−∆, = -0,625211Γ1(2)Γ1(+ Γ1(2)2)211Γ2 (1)1,040,7104,914,674,460,81020,82070,8312-0,050,160,37-2,94-2,59-2,250,020,0100,0009-0,00210+−- 171 -ПРИЛОЖЕНИЕ В.
ЗНАЧЕНИЯ СОЛЬВАТАЦИОННЫХ ИЗБЫТКОВ ДЛЯНЕВОДНЫХ РАСТВОРОВ ЭЛЕКТРОЛИТОВВ.1. NaCl, NaBr и NaI.m – моляльность, моль/кг р-ля; γ – коэффициент активности растворенноговещества; x – мольная доля компонента раствора; 1 – растворитель; 2 –растворенное вещество; Γ()– сольватационный избыток частиц i над j вокружении центральной частицы k.Таблица В.1.1 - 1 – H2O; 2 – NaClmγ±1±+−Γ+(1)+ Γ+(1)0,10,20,30,40,50,60,70,80,911,21,41,61,822,533,544,555,560,7780,7350,710,6930,6810,6730,6670,6620,6590,6570,6540,6550,6570,6620,6680,6880,7140,7460,7830,8260,8740,9280,9860,00180,00360,00530,00710,00880,01060,01230,0140,01570,01740,02070,0240,02730,03050,03360,04130,04880,0560,0630,06980,07630,08270,0889555277,5185138,7511192,579,2969,3861,6755,546,2539,6434,6930,8327,7522,218,515,8613,8812,3311,110,099,250,0840,0840,0810,0730,0580,0430,0350,020,002-0,009-0,034-0,063-0,094-0,126-0,161-0,214-0,275-0,329-0,379-0,424-0,465-0,498-0,512+−Γ1(+)+ Γ1(+)-46,46-23,23-15-10,14-6,44-3,97-2,75-1,42-0,150,491,582,513,263,94,464,765,085,225,265,245,165,034,731 +−(Γ+ Γ−(1))2 +(1)-0,458-0,458-0,459-0,463-0,471-0,479-0,483-0,49-0,499-0,504-0,517-0,532-0,547-0,563-0,58-0,607-0,637-0,665-0,69-0,712-0,732-0,749-0,756- 172 -Таблица В.1.2 - 1 - CH3OH; 2 – NaClmγ±1±+−Γ+(1)+ Γ+(1)0,010,020,040,060,080,10,120,140,160,180,20,6730,5580,4460,3670,3290,3010,280,270,2580,2510,2430,00030,00060,00130,00190,00250,00320,00380,00440,00510,00570,006331251562,5781,25520,83390,63312,5260,42223,21195,31173,61156,250,3690,420,6680,7490,6290,650,4510,3920,3880,3550,427+−Γ1(+)+ Γ1(+)-1153,89-656,39-522,09-390,02-245,76-203,01-117,55-87,61-75,83-61,67-66,651 +−(Γ+ Γ−(1))2 +(1)-0,315-0,29-0,166-0,126-0,185-0,175-0,274-0,304-0,306-0,322-0,287Таблица В.1.3 - 1 – H2O; 2 – NaBrmγ±1±+−Γ+(1)+ Γ+(1)0,10,20,30,40,50,60,70,80,911,21,41,61,822,533,540,7820,7410,7190,7040,6970,6920,6890,6870,6870,6870,6920,6990,7060,7180,7310,7680,8120,8650,9290,00180,00360,00530,00710,00880,01060,01230,0140,01570,01740,02070,0240,02730,03050,03360,04130,04880,0560,063555277,5185138,7511192,579,2969,3861,6755,546,2539,6434,6930,8327,7522,218,515,8613,880,0790,0750,0680,0480,0260,0130,0004-0,017-0,031-0,054-0,089-0,11-0,147-0,188-0,222-0,274-0,335-0,397-0,426+−Γ1(+)+ Γ1(+)-43,64-20,73-12,63-6,62-2,84-1,22-0,031,21,943,024,134,375,115,86,166,086,216,295,911 +−(Γ+ Γ−(1))2 +(1)-0,461-0,463-0,466-0,476-0,487-0,493-0,5-0,509-0,516-0,527-0,545-0,555-0,574-0,594-0,611-0,637-0,668-0,698-0,713Таблица В.1.4 - 1 – CH3OH; 2 – NaBrmγ±1±+−Γ+(1)+ Γ+(1)0,010,020,040,060,080,10,7450,6850,6080,5580,5270,4920,00030,00060,00130,00190,00250,003231251562,5781,25520,83390,63312,50,1370,170,2340,2530,3330,258+−Γ1(+)+ Γ1(+)-427,43-265,86-183,05-131,95-129,9-80,681 +−(Γ+ Γ−(1))2 +(1)-0,432-0,415-0,383-0,373-0,334-0,371- 173 0,120,140,160,180,20,40,60,811,50,4820,4620,450,4330,4210,3530,3190,30,2890,2660,00380,00440,00510,00570,00630,01250,01850,02440,03010,0438260,42223,21195,31173,61156,2578,1352,0839,0631,2520,830,2310,2970,3410,4060,3320,3040,2540,1750,15040,165-60,16-66,35-66,68-70,48-51,84-23,77-13,21-6,84-4,7-3,44-0,385-0,351-0,329-0,297-0,334-0,348-0,373-0,412-0,425-0,417+−Γ1(+)+ Γ1(+)1 +−(Γ+ Γ−(1))2 +(1)-0,367-0,313-0,251-0,292-0,327-0,299-0,359-0,376-0,402-0,471Таблица В.1.5 - 1 – C2H5OH; 2 – NaBrmγ±1±+−Γ+(1)+ Γ+(1)0,010,020,040,060,080,10,120,140,180,20,6010,5190,4110,3590,3330,3140,2960,290,270,2680,00050,00090,00180,00270,00370,00460,00550,00640,00810,00921741087543,5362,33271,75217,4181,17155,29120,78108,70,2670,3750,4990,4160,3460,40270,2820,2470,1960,057-579,92-407,59-271-150,6-93,95-87,55-51,02-38,38-23,71-6,25Таблица В.1.6 - 1 – H2O; 2 – NaImγ±1±+−Γ+(1)+ Γ+(1)0,10,20,30,40,50,60,70,80,911,21,41,61,822,533,50,7870,7510,7350,7270,7230,7230,7240,7270,7310,7360,7470,7630,780,7990,820,8830,9631,0530,00180,00360,00530,00710,00880,01060,01230,0140,01570,01740,02070,0240,02730,03050,03360,04130,04880,056555277,5185138,7511192,579,2969,3861,6755,546,2539,6434,6930,8327,7522,218,515,860,0670,05670,0370,018-0,005-0,025-0,044-0,064-0,082-0,101-0,136-0,173-0,202-0,234-0,278-0,347-0,409-0,433+−Γ1(+)+ Γ1(+)-37,13-15,75-6,78-2,470,62,363,464,465,085,626,296,8677,27,727,697,576,871 +−(Γ+ Γ−(1))2 +(1)-0,467-0,472-0,482-0,491-0,503-0,513-0,522-0,532-0,541-0,551-0,568-0,587-0,601-0,617-0,639-0,673-0,705-0,717- 174 -Таблица В.1.7 - 1 – CH3OH; 2 – NaImγ±1±+−Γ+(1)+ Γ+(1)0,010,020,040,060,080,10,120,140,160,180,20,40,60,811,522,533,540,7830,7580,7110,6980,6980,7010,710,7380,7290,7640,7890,9121,0921,211,3561,67222,3872,7853,1843,630,00030,00060,00130,00190,00250,00320,00380,00440,00510,00570,00630,01250,01850,02440,03010,04380,05670,0690,08050,09150,101931251562,5781,25520,83390,63312,5260,42223,21195,31173,61156,2578,1352,0839,0631,2520,8315,6312,510,428,937,810,0480,0730,0710,019-0,015-0,049-0,145-0,082-0,142-0,269-0,217-0,265-0,312-0,336-0,381-0,418-0,481-0,526-0,548-0,576-0,593+−Γ1(+)+ Γ1(+)-150,44-114,54-55,73-10,15,6815,2437,7218,2527,6746,6533,8320,716,2513,1411,928,727,516,575,715,144,631 +−(Γ+ Γ−(1))2 +(1)-0,476-0,463-0,464-0,49-0,507-0,524-0,572-0,541-0,571-0,634-0,608-0,633-0,656-0,668-0,691-0,709-0,74-0,763-0,774-0,788-0,796Таблица В.1.8 - 1 – C2H5OH; 2 – NaImγ±1±+−Γ+(1)+ Γ+(1)0,010,020,040,060,080,10,120,140,160,180,20,40,60,811,522,50,5520,4820,4340,4190,4120,4060,410,4160,4210,4270,430,5250,6280,7480,8371,1321,4761,9140,00050,00090,00180,00270,00370,00460,00550,00640,00730,00810,0090,01770,02620,03430,04210,06060,07770,093521741087543,5362,33271,75217,4181,17155,29135,88120,78108,754,3536,2327,1821,7414,4910,878,70,2420,2070,1310,0720,059-0,003-0,079-0,096-0,108-0,1002-0,169-0,293-0,378-0,401-0,44-0,521-0,587-0,617+−Γ1(+)+ Γ1(+)-525,18-225,53-71,21-26,26-15,90,6914,3314,8714,6712,118,3915,9313,7110,899,567,546,385,361 +−(Γ+ Γ−(1))2 +(1)-0,379-0,396-0,434-0,464-0,471-0,502-0,54-0,548-0,554-0,55-0,585-0,647-0,689-0,7-0,72-0,76-0,793-0,808- 175 -Таблица В.1.9 - 1 – BuOH; 2 – NaImγ±1±+−Γ+(1)+ Γ+(1)0,010,020,040,060,080,10,120,140,160,180,20,40,60,810,5340,4540,3490,2960,2550,240,220,2090,1960,1910,1860,1930,2550,3330,4340,00070,00150,00290,00440,00590,00730,00870,01020,01160,0130,01440,0280,04080,0530,06461349674,5337,25224,83168,63134,9112,4296,3684,3174,9467,4533,7322,4816,8613,490,3030,4380,6380,84370,6330,5760,6510,6520,5030,2740,071-0,312-0,492-0,566-0,596+−Γ1(+)+ Γ1(+)408,68295,53215,03189,68106,7577,6673,1962,8242,3920,554,78-10,53-11,06-9,54-8,051 +−(Γ+ Γ−(1))2 +(1)-0,349-0,281-0,181-0,078-0,183-0,212-0,174-0,174-0,249-0,363-0,465-0,656-0,746-0,783-0,798В.2.
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