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1 (6.)lausius lapeyon ln p A (6.) A 6- (6.) Antoine ln p A (6.) ( + ) A p o p o lausius lapeyonp o lnp o / atm kpa
2 A p o [kpa][k] [] (6.) 4.0atm ln p [ kpa] A ( + ) A ln p ln( ) K lausiuslapeyon dq du P dv dqdu+pdv (6.3) dq ds dqds (6.4) (6.3)(6.4) duds-pdv (6.5) H HU+PV (6.6) (6.6) dhdu+pdv+vdp (6.7) (6.7)(6.5) dhds+vdp (6.8) (Gibbs)G HS GH-S (6.9) (6.9) dg dh-ds-sd (6.0)
3 (6.8)(6.0) dg VdP -Sd (6.) dg VdP Sd (6.) p equilibium mol(gibbs) GmGm V Gm L Gm V Gm L m dpd Gm V dgm V Gm L dgm L dgm V dgm L (6.3) () mol dgm V Vm V dpsm V d (6.4) dgm L Vm L dpsm L d (6.5) (6.3) dp d V m V m L m L m S S (6.6) V V Sm V Sm L Sv,m Hv,mHv,m V L H V,m S V,m S m S m (6.7) (6.6)(6.7) dp d H V,m V ( V V m L m (6.8) ) (6.8),000 Vm V Vm L pvmr 3
4 V V m V L m V L m p (6.9) R (6.9)(6.8) dp d H V,m p (6.0) R Hv,mHv,m(6.0) ln p A (6.) A Hv,mR A,, 4 Langmui 3 [] - [] P [mmhg] lausius-lapeyon A A 50 lnpa/ 4
5 []P [mmhg]lnp [mmhg] / [K - ] yx yx yx 5
6 yx A 50 Antoine 4.. Riedelhek-Stiel 6 Riedel equation calculate vapo pessue as follow, c : itical empeatue Pc : itical Pessue b : boiling Point / itical empeatue measue empeatue / itical empeatue Antoine viscosity 6
7 hapmanenskog M 6.69 (3.7) δ Ω η v [P][]M[K] v A E Ω v + + (3.8) * D F* k * (3.9) k ( ω) (3.30) (3.30) 6 (3.8) AF A D0.7730E.678F ηξ e 4. + e 0. (3.3) ηξ ( ) Z 5 / 4 (3.3).5 4 / 5 / 3 ηξ ( ) Z (3.33) M 6 P 3 (3.34) (3.34)Z [P] [ 3.0] 0 8.8K 5.MP a(50.4atm) [] 8.8KP 50.4atmM8.05 (3.4) 7
8 M 6 P 3 (8.05) (8.8) 6 (50.4) (3.38) η e e ξ e e µ P Reichenbeg a * η [ ( )] 6 a* (3.35) M a* (3.36) n i i i Mn i I i 3 3 0) i i H () 3.59 H () 6.47 F 4.46 H().67 l 0.06 () H 7.68 OH() 7.96 H() 5.53 O() 3.59 H().78 O().0 H 7.4 HO() 4.0 () 5.4 OOH() 8.65 H () 6.9 OO() 3.4 HOO() H().6 NH 9.7 () 0.3 NH()
9 () 5.90 N() 4.97 N 8.3 S() 8.86 [. E. Poling, J. M. Pausnitz and J. P. O onnell, he Popeties of Gases and Liquids 5th edit., p.9.3, McGaw-Hill (000)] [ 3.] K [] K (3.36) a* M (60.) a * 9.5 n i i i (3.4) η a * [ ( )] [ (0.807 )] µ P (homas) L η L log θ / ρ L η []ρ [g/cm 3 ] [K]θ L [. E. Poling, J. M. Pausnitz and J. P. O onnell, he Popeties of Gases and Liquids 5th edit., p.9.3, McGaw-Hill (000)] 9
10 homas g/cm 3 [] c θ θ η L log / η 0.43 cp η cp Oick-Eba η L ln A + θ ρ LM η L []ρ L [g/cm 3 ] A, A, Oick-Eba [K]M 0
11 [. E. Poling, J. M. Pausnitz and J. P. O onnell, he Popeties of Gases and Liquids 5th edit., p.9.3, McGaw-Hill (000)] 5. Fick dn J D dx Jnx D 5.. oltzmann hapmanenskog D M, 3 M + M π A A k M AM 6 nπσ A A M / Ω D f D A, n,k, Ω D
12 σ A A, Fulle-Schettle-Giddings 3.75 M A + M 0 M AM DA / 3 / 3 P[( v) A + ( v) ] / [K][atm] v, Fulle-Schettle-Giddings [. E. Poling, J. M. Pausnitz and J. P. O onnell, he Popeties of Gases and Liquids 5th edit., p.9.3, McGaw-Hill (000)] Fulle-Schettle-Giddings MPa v H 7 OH v v 3( ) + 8( H ) + ( O) (3H7OH) M p 60 Fulle-Schettle-Giddings 3.75 M A + M 0 M AM DA / 3 / 3 P[( v) A + ( v) ] /
13 D A / 3 / 3 [ ] / cm /s 0.03 cm /s < V V D ρ ( Dρ ) o Mathuhodos D ρ β c 5 ρ P P / M Pc β 5 / 6 c / 3 P c, c atm,k 5.. :, D A D A. (Stokes-Einstein ). D A R 6πη A, A D A Wilke-hangStokes-Einstein 3
14 D A φm / 8 ( ) 0.6 η VA D A A,cm /s M,KV A A,cm3/mol yn-alus V b V c V c SchoedeLe as [. E. Poling, J. M. Pausnitz and J. P. O onnell, he Popeties of Gases and Liquids 5th edit., p.9.3, McGaw-Hill (000)] cP73.8cm3/mol 4
15 Wilke-hang D A φm / 8 ( ) 0.6 η VA / 8 ( ) cm /s 6 c p c V c (Lydesen) [K] (3.4) ( p) ( ) M p [atm] (3.5) V 40 + v [cm 3 mol - ] (3.6) M[K] 760mmHg[gmol - ] pv 3- pv 3 ) p v H H H H H H H H
16 H F l I OH() OH() O() O() O() O() HO() OOH() OO() O() NH NH() NH() N() N() N NO SH S() [R.. Reid, J. M. Pausnitz and. K. Shewood, he Popeties of Gases and Liquids 4th edit., McGaw-Hill (977)] [ 3.3] P c c V c [] H 3 (H ) 6 OHM p V H H OH ( 0.0 ) ( ) p ( 0.7 ) ( ) ( 0.06 ).649 v ( 55 ) ( 55 6 ) ( 8 ) K 6
17 ( ) { (0.) P M 6.0 (( P) ) (( ) ) 9.4atm V c 40 v cm 3 mol } 608K c Pc Vc KP44.5 atmv74 cm 3 /mol KP63. atmv68 cm 3 /mol.3 itical Popeties Estimation Please input functional goup numbe and push calc button. If molecule contains ing, please select (R) fagment. 3.3 P c c V c [] H 3 (H ) 6 OHM H 3 H 6OH,6, b449.96kp alc.c,pc,vc c, KPc, basvc 446.6cm3/mol 3.3 7
18 8
19 SI SI m kg s K mol A cd SI SI SI SI N m kg s- Pa m- kg s- (N m-) J m kg s- W m kg s-3 (J s-) A s V m kg s-3 A- (J A- s-) m kg s-3 A- (V A-) S m- kg s- A (-) F m- kg s- A s4 (A s V-) Hz s- 3 SI p n m c d k M G 9
20 F mol- K J K- R J K- mol dm3 atm K- mol cal K- mol- L mol- H J s G m s m s m3 mol- 5 3) ln p A p [ kpa ] [ K ] ( + ) A [K] n n n p Gmehling J.et al. DEHEMA hemisty Data Seies.Vol.,Pat-8( ) 0
21 6 8) P c [MPa] c [K] V c [cm 3 mol] (O) (O ) (H O) (NO ) (SO ) (HF) (Hl) (H) (HI) (HN) (H S) (NH 3 ) (H 4 ) ( H 4 ) ( H 6 ) ( 3 H 8 ) ( 6 H 6 ) ( 6 H ) ( 6 H 5 H 3 ) ( 0 H 8 ) (H 3 OH) ( H 5 OH) ( 6 H 5 OH) (H 3 HO) ((H 3 )O) (H 3 OOH) (H 3 OOH 3 ) (H 3 OO H 5 ) (H 3 ) O ( H 5 ) O ( 6 H 5 NH ) (l 4 ) R.. Reid, J. M. Pausnitz and. E. Poling, he Popeties of Gases and Liquids, 4th edit., Appendix, McGaw Hill (987)
22 4-8) p,m a + a + a3 + a4 3 ( p,m [JK mol ], [K] ) a a0 3 a30 5 a40 8 O O S l F H Hl HF HO HS I N NH NO NO O SO SO R.. Reid, J. M. Pausnitz and. E. Poling, he Popeties of Gases and Liquids, 4th edit., Appendix, McGaw Hill (987)N()() p.ii-39(984)
23 4-93K 4) J mol - K - H3 H H H H H H H H l l O O OH O O HOH HOH OH OH ONO H HN H N N N N SH H F I O > O H R.. Reid, J. M. Pausnitz and. E. Poling, he Popeties of Gases and Liquids, 4th edit., Appendix, McGaw Hill (987) 3
24 50 A atm0.35 kpa ln p [kpa] A ( [K] + ) ln p [kpa] A ( [K] + ) ( ) p 0.3 kpa 0.5 atm -. atm A ln( ) ( 39.74) A ln p ln( ) K atm kpa A p o [kpa] [K] 4.00atm ln p [ kpa] A ( + ) A ln p ln( ) K 7.9 4
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