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[ ] : 15/5/15 1698 1677 1704 1721
3 3 4-17 18 19-23 24-45 46 46
. b , S lnP -1/T . . . ( ). , . 20bar. . (, ), 1bar 3-20bar . .
1 , , 1/T, lnP (1 )T1T1 (K)PP'1/T1lnP'd(1/T1)dlnP'
118,5391,532,020,002550,70313,26217E-60,0495
12940243,020,002491,105263,09398E-60,03311
138,5411,554,020,002431,391282,95277E-60,02488
14641965,020,002391,613432,84801E-60,01992
15242576,020,002351,795092,76817E-60,01661
159,5432,587,020,002311,948762,67299E-60,01425
16443798,020,002292,081942,61823E-60,01247
168441109,020,002272,199442,57095E-60,01109
1734461110,020,002242,304582,51362E-60,00998
1774501211,020,002222,399712,46914E-60,00907
1804531312,020,002212,486572,43654E-60,00832
184,5457,51413,020,002192,566492,38884E-60,00768
186,5459,51514,020,002182,640482,36809E-60,00713
1904631615,020,002162,709382,33243E-60,00666
192,5465,51716,020,002152,773842,30744E-60,00624
1954681817,020,002142,834392,28285E-60,00588
197,5470,51918,020,002132,891482,25866E-60,00555
2004732019,020,002112,945492,23485E-60,00526
2 , , 1/T, lnP (1 )T2T2(K)PP'1/T2lnP'd(1/T2)dlnP'
12039332,020,002540,70313,23731E-60,0495
132,5405,543,020,002471,105263,0408E-60,03311
141,5414,554,020,002411,391282,91019E-60,02488
14942265,020,002371,613432,80766E-60,01992
156,5429,576,020,002331,795092,71046E-60,01661
161,5434,587,020,00231,948762,64844E-60,01425
165,5438,598,020,002282,081942,60034E-60,01247
171444109,020,002252,199442,53632E-60,01109
1754481110,020,002232,304582,49123E-60,00998
1794521211,020,002212,399712,44733E-60,00907
182,5455,51312,020,00222,486572,40987E-60,00832
1864591413,020,002182,566492,37326E-60,00768
1894621514,020,002162,640482,34253E-60,00713
1924651615,020,002152,709382,31241E-60,00666
195,5468,51716,020,002132,773842,27798E-60,00624
197,5470,51817,020,002132,834392,25866E-60,00588
2004731918,020,002112,891482,23485E-60,00555
202,5475,52019,020,00212,945492,21141E-60,00526
3 , , 1/T, lnP (2 )T3T3(K)PP'1/T3lnP'd(1/T3)dlnP'
117,5390,532,020,002560,70313,2789E-60,0495
13040343,020,002481,105263,07865E-60,03311
13941254,020,002431,391282,94561E-60,02488
14641965,020,002391,613432,84801E-60,01992
15342676,020,002351,795092,75519E-60,01661
158,5431,587,020,002321,948762,6854E-60,01425
16443798,020,002292,081942,61823E-60,01247
168441109,020,002272,199442,57095E-60,01109
172,5445,51110,020,002242,304582,51927E-60,00998
1764491211,020,002232,399712,48015E-60,00907
1804531312,020,002212,486572,43654E-60,00832
1834561413,020,002192,566492,40459E-60,00768
1864591514,020,002182,640482,37326E-60,00713
1894621615,020,002162,709382,34253E-60,00666
1924651716,020,002152,773842,31241E-60,00624
1954681817,020,002142,834392,28285E-60,00588
1984711918,020,002122,891482,25387E-60,00555
2004732019,020,002112,945492,23485E-60,00526
4 , , 1/T, lnP (2 )T4T4(K)PP'1/T4lnP'd(1/T4)dlnP'
12039332,020,002540,70313,23731E-60,0495
132,5405,543,020,002471,105263,0408E-60,03311
141,5414,554,020,002411,391282,91019E-60,02488
14942265,020,002371,613432,80766E-60,01992
156,5429,576,020,002331,795092,71046E-60,01661
161,5434,587,020,00231,948762,64844E-60,01425
165,5438,598,020,002282,081942,60034E-60,01247
171444109,020,002252,199442,53632E-60,01109
1754481110,020,002232,304582,49123E-60,00998
1794521211,020,002212,399712,44733E-60,00907
182,5455,51312,020,00222,486572,40987E-60,00832
1864591413,020,002182,566492,37326E-60,00768
1894621514,020,002162,640482,34253E-60,00713
1924651615,020,002152,709382,31241E-60,00666
195,5468,51716,020,002132,773842,27798E-60,00624
197,5470,51817,020,002132,834392,25866E-60,00588
2004731918,020,002112,891482,23485E-60,00555
202,5475,52019,020,00212,945492,21141E-60,00526
1 lnP, 1/T (1 )
2 lnP, 1/T (1 )
3 lnP, 1/T (2 )
4 lnP, 1/T (2 )
5 1 1
6 2 2
lnP lnP :[d(lnP)]2 =(1/P)2 (dP)2 => d(lnP)=1/P*dP :d(lnP) =(1/2,02)*0,1=0,0495 1/ 1/T :[d(1/T)]2 =(-1/T2)2 (dT)2 =>d(1/T)=(1/T2) (dT) :d(1/T)=(1/391,5)2 *0,5=3,2621*10-6 z z :z= 0,42498 + 2,13349*(/648) - 2,01927*(/648)2 :z= 0,42498 + 2,13349*(391,5/648) - 2,01927*(391,5/648)2=0,97689
5 zT1 (K)z1T2(K)z2T3(K)z3T4(K)z4
391,50,976893930,97617390,50,977363930,97617
4020,9714405,50,969334030,97082405,50,96933
411,50,96551414,50,963474120,96518414,50,96347
4190,960254220,9584190,960254220,958
4250,95565429,50,951984260,95485429,50,95198
432,50,94942434,50,94767431,50,95028434,50,94767
4370,94542438,50,944044370,94542438,50,94404
4410,94174440,938814410,94174440,93881
4460,936844480,93482445,50,937334480,93482
4500,932774520,930684490,93384520,93068
4530,92962455,50,926934530,92962455,50,92693
457,50,924734590,923064560,926384590,92306
459,50,92254620,919654590,923064620,91965
4630,91854650,916164620,919654650,91616
465,50,91556468,50,911974650,91616468,50,91197
4680,91257470,50,909524680,91257470,50,90952
470,50,909524730,906414710,90894730,90641
4730,90641475,50,903244730,90641475,50,90324
z
z1=0,93751S1 = 0,022017
z2=0,93511S2 = 0,022466
z3=0,93776S3 = 0,021847
z4= 0,93511S4 = 0,022466
H H : , d(lnP)/d(1/T) , R ,z 1 b =-4939,2345, R=8,314 (JK -1mol -1), z1=0,93751=38,90 103 J/mol cal/mol 1 cal = 4,184J=9,30* 103 cal/mol1 b =-5001,98183, R=8,314 (JK -1mol -1), z2=0,93511=38,89 * 103 J/mol cal/mol 1 cal = 4,184J=9,29* 103 cal/mol2 b =-4916,58824, R=8,314 (JK -1mol -1), z3=0,93776=38,33* 103 J/mol cal/mol 1 cal = 4,184J=9,16* 103 cal/mol2 b =-5001,98183, R=8,314 (JK -1mol -1), z4= 0,93511=38,89 * 103 J/mol cal/mol 1 cal = 4,184J=9,29* 103 cal/mol
Tb lnP-1/T P, :1 lnP = a + b(1/T1) a = 13,3848, b =-4939,2345 lnP= ln(1,0097)=0,00965 Tb1 =96,28 oC1 lnP = a + b(1/T2) a = 13,46441, b =-5001,98183 lnP= ln(1,0097)=0,00965 Tb2 =98,76 oC2 lnP = a + b(1/T3) a = 13,34236, b =-4916,58824 lnP= ln(1,0097)=0,00965 Tb3 =95,76 oC2 lnP = a + b(1/T4) a = 13,46441, b =-5001,98183 lnP= ln(1,0097)=0,00965 Tb4 =98,76 oC
S , S (1)1
1
2
2
(Tb), (Hu) (S) . .Tb (K)u (cal/mol)S (cal/mol*K)
370.399.26 * 10325
373.29.72 * 10326.04
lnP/(1/T) -. . . , . . 1 atm., Clausius-Clapeyron, . .
Tb(dT)2= [1/(P-a)]2 (db)2 + [(b/P)*(1/(a-lnP)2)]2(dP)2 + [b/(lnP-a)2]2(da)21 : (dT1)= 6,55 P=1,0097 mbara=13,3848da=0,078b=4939,2345db=35,83511 : (dT2)= 6,07 P=1,0097 mbara=13,4644da=0,0595b=5001,9818db=27,47062 : (dT3)= 6,14 P=1,0097 mbara=13,3424da=0,0628b=4916,5882db=28,8493
2 : (dT4)= 6,07 P=1,0097 mbara=13,4644da=0,0595b=5001,9818db=27,4706 u (du)2=R2[z2(db)2 + b2(dz)2]1 : (d1)= 226,0081 cal/molP=1,0097 mbarz=0.9375db=35,8351b=4939,2345dz=0,02201 : (d2)= 229,3880 cal/molP=1,0097 mbarz=0.9351db=27,4706b=5001,9818dz=0,022522 : (d3)= 219,6603 cal/molP=1,0097 mbarz=0.9378db=28,8493b=4916,5882dz=0,02182 : (d4)= 229,3880 cal/molP=1,0097 mbarz=0.9351db=27,4706b=5001,9818dz=0,0225 S(dS)2=[/(b)2]2 * (dTb)2 + (1/Tb)2 * (d)21 : (dS1)= 0,75 cal/(mol*K)P=1,0097 mbar=9300 cal/molTb=369,28 KdTb= 6,55 Kd= 226,0081 cal/mol1 : (dS2)= 0,73 cal/(mol*K)P=1,0097 mbar=9290 cal/molTb=371,76 KdTb= 6,07 Kd= 229,3880 cal/mol2 : (dS3)= 0,72 cal/(mol*K)P=1,0097 mbar=9160 cal/molTb=368,76 KdTb= 6,14 Kd= 219,6603 cal/mol2 : (dS4)= 0,73 cal/(mol*K)P=1,0097 mbar=9290 cal/molTb=371,76 KdTb= 6,07 Kd= 229,3880 cal/mol
1 1 2 2
z0,9375 0,02200,93500,02250,93780,02180,93510,0225
Tb369.286.55 K371,766,07 K368.766.14 K371.766.07 K
9300226.00 cal/mol9290229.39 cal/mol9160219.66 cal/mol9290229.39 cal/mol
S25.150.75cal/(mol*K)24.990.73cal/(mol*K)24.840.72cal/(mol*K)24.990.73cal/(mol*K)
, . . , , . , . ( ) . S, . . : : 0,1bar : 0,5 o C : 1009,7 +-0,2 mbar : 25,5 +-0,5 o C
. . , . , .
1 . lnP 1/T . . 2 (5) (1), H. ( z z r) . cal/mole. . 3 1. . ; ; 4 . ; ; z. ; . z=1, , (u) (S) :
(u) H : , d(lnP)/d(1/T) , R ,z cal/mol 1 cal = 4,184J1 b =-4939,2345, R=8,314 (JK -1mol -1)u = 9,81 * 103 cal/mol1 b =-5001,98183, R=8,314 (JK -1mol -1)u = 9,94 * 103 cal/mol2 b =-4916,58824, R=8,314 (JK -1mol -1)u = 9,77 * 103 cal/mol2 b =-5001,98183, R=8,314 (JK -1mol -1)u = 9,94 * 103 cal/molS S 1 u = 9,81 * 103 cal/molb = 369.28 KS = 26.56 cal/mol*K1 u = 9,94 * 103 cal/molb = 371,76 KS = 26.74 cal/mol*K2 u = 9,77 * 103 cal/molb = 368,76 KS = 26.49 cal/mol*K2 u = 9,94 * 103 cal/molb = 371,76 KS = 26.74 cal/mol*K
, (Hu) (S). (cal/mol)S(cal/mol*K)
9.26 * 10325
z=19.87 * 10326,38
9.72 * 10326.04
z=1. , ( ) , . .
5 z r /z , /z . z. u/z Tr u/z . u . . Tr Tr = /c c=648oK.1 1 2
2
u/z . 6 8 ; lnP 1/ ; , . ; (8), (7).(2)=1 + + dT (7)(2)(1) + (T2 1) (8) , : , [ 25-100C, = -10cal.(deg.mole)-1]. , . , . , , . , (7), (8). lnP 1/ . , lnP = a + b(a/T). : b= - (u/R). -(u/Rz) 1/. ,d(-u/R))/d(1/T) =d(-TS/R)=(-S/R)/(-1/T2) = (S/R)*T2 >0 , ().
71 = b 1/2(b2-b1) = -4638,3 300,9
1
= b 1/2(b2-b1) = - -5002,0 300,0
2
= b 1/2(b2-b1) = -4916,6 296,5155
2
= b 1/2(b2-b1) = - -5002,0 300,0
5 u/z (u/z)2 . .
8 . .
9 . Trouton; . (S), Trouton Svap = vap / Tboiling 24,99 cal /mol*K . , Svap , Trouton 88 J /mol*K 21,03 cal / mol*K ([footnoteRef:1]). . . , . [1: ]
10 . 1) . , , : P=PA*PB,, (1atm 760Torr). , 760 Torr 760 T 760Torr. , ..,, : WA/WB = PA/PB * MA/MBwA, wB= PA, PB= ,= B B B
2) Henry . . , , , , . , . () . , , . . .
3) . , , , . , . .
4) 100 C . , , . ( ). . , . 5-15 psi ( - 15 psi = 1,034 bar). . , . , 15 psi, 125 C . , .
12 ; . . S . u=(u+1/2) , u=0,1,2 u=0 . , . 0 S=k lnW k: Boltzmann & W: H2O 2 S=k ln (3/2)N = 3,4J/(mol*K) 0 3,4 J/(mol*K) 0 .
13 (118-200C). 1/(-1) ln(P, Bar) .ToCP(KPa)1/T(K-1)ln(P,Bar)
118186,230,002560,62181
119192,280,002550,65378
120198,480,002540,68552
121204,850,002540,71711
122211,380,002530,74849
123218,090,002530,77974
124224,960,002520,81075
125232,010,002510,84161
126239,240,002510,8723
127246,660,00250,90284
128254,250,002490,93315
129262,040,002490,96333
130270,020,002480,99333
131278,20,002481,02317
132286,570,002471,05281
133295,150,002461,08231
134303,930,002461,11163
135312,930,002451,14081
136322,140,002441,16982
137331,570,002441,19867
138341,220,002431,22736
139351,090,002431,25587
140361,190,002421,28423
141371,530,002421,31246
142382,110,002411,34054
143392,920,00241,36844
144403,980,00241,3962
145415,290,002391,42381
146426,850,002391,45126
147438,670,002381,47858
148450,750,002381,50574
149463,10,002371,53277
150475,720,002361,55966
151488,610,002361,58639
152501,780,002351,61299
153515,230,002351,63944
154528,960,002341,66574
155542,990,002341,69192
156557,320,002331,71797
157571,940,002331,74386
158586,870,002321,76963
159602,110,002311,79527
160617,660,002311,82077
161633,530,00231,84614
162649,730,00231,87139
163666,250,002291,89649
164683,10,002291,92147
165700,290,002281,94632
166717,830,002281,97106
167735,70,002271,99565
168753,940,002272,02014
169772,520,002262,04449
170791,470,002262,06872
171810,780,002252,09283
172830,470,002252,11682
173850,530,002242,14069
174870,980,002242,16445
175891,80,002232,18807
176913,030,002232,2116
177934,640,002222,23499
178956,660,002222,25828
179979,090,002212,28145
1801001,90,002212,30448
1811025,20,00222,32747
1821048,90,00222,35033
18310730,002192,37304
1841097,50,002192,39562
1851122,50,002182,41814
1861147,90,002182,44052
1871173,80,002172,46283
1881200,10,002172,48499
1891226,90,002162,50708
1901254,20,002162,52908
1911281,90,002162,55093
1921310,10,002152,57269
1931338,80,002152,59436
19413680,002142,61593
1951397,60,002142,63734
1961427,80,002132,65872
1971458,50,002132,67999
1981489,70,002122,70116
1991521,40,002122,72222
2001553,60,002112,74316
z z :z= 0,42498 + 2,13349*(/648) - 2,01927*(/648)2
2
T(K)z
3910,97713
3920,97666
3930,97617
3940,97568
3950,97518
3960,97467
3970,97415
3980,97362
3990,97308
4000,97253
4010,97197
4020,9714
4030,97082
4040,97023
4050,96963
4060,96903
4070,96841
4080,96778
4090,96715
4100,9665
4110,96584
4120,96518
4130,9645
4140,96382
4150,96313
4160,96242
4170,96171
4180,96099
4190,96025
4200,95951
4210,95876
4220,958
4230,95723
4240,95645
4250,95565
4260,95485
4270,95405
4280,95323
4290,9524
4300,95156
4310,95071
4320,94985
T(K)z
4330,94899
4340,94811
4350,94722
4360,94633
4370,94542
4380,94451
4390,94358
4400,94265
4410,9417
4420,94075
4430,93978
4440,93881
4450,93783
4460,93684
4470,93583
4480,93482
4490,9338
4500,93277
4510,93173
4520,93068
4530,92962
4540,92855
4550,92747
4560,92638
4570,92529
4580,92418
4590,92306
4600,92193
4610,9208
4620,91965
4630,9185
4640,91733
4650,91616
4660,91497
4670,91378
4680,91257
4690,91136
4700,91014
4710,9089
4720,90766
4730,90641
z .=0,947093 0,020937
H H : , d(lnP)/d(1/T) , R ,z b =-4781,00604, R=8,314 (JK -1mol -1), z=0,947093=37,65 103 J/mol cal/mol 1 cal = 4,184J=9,00* 103 cal/mol TblnP = a + b(1/T) a = 12,8583, b =-4781,00604 lnP= ln(1,01325)=0,01316 Tb =372 = 99,2 oC Tb = 99.63 oC SS=H/Tb =9,00* 103 / 372 = 24,19 cal/(mol*)
14 -5oC -5oC cp=37,3 J K-1*mol-1 273=6,01 kJ/mol C=2,09 J/g*K, C=4,18 J/g*K.
S=H/T :2 = 1 +Cp (T2-T1)
: 268 =273 +Cp (T2-T1) =6,01*103 (J/mol) +4,18 (J/g*K) * 18 (g/mol) *(263-273)(K)268 = 5257,6 J/mol :268 =273 +Cp (T2-T1) =6,01*103 (J/mol) +2,09 (J/g*K) * 18 (g/mol) *(263-273)(K)268 = 5633,8 J/mol
: S=H/T = ( - ) / = 376,2 (J/mol) / 263 (K) = 1,404 J/Kmol
15 [8] . (13). 3 1. V=Vg (Vg>>Vl)1. PVg=RT (z=1 )1. Clausius-Clapeyron -
: lnP=-(/R)*(1/T) + c lnP 1/ . , . , 2 . , . 3 Clapeyron, . V = Vg - Vl, Zg = PVg/RT :
= RZg (1-Vl/Vg) (1) Vg >> Vl 1- Vl/Vg = 1, (1) : = RZg . Vg = Vl 1- Vl/Vg = 0, (1) = 0,. Vg