[ ] : 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