1 20 j20 D M? D ù ù I k k Ss? u v A B   :  I k HW 20 M  ° Dy < ? M) D| ? 5| B = ? 1 ? B t ? ? E ? ¤s Ba es5  5 s ?5s 1. >"d?×? @?"d¥ £ ?D?B? pb s>"d¥ £ ?D?B? p WQU +=? × @"d¥ £ ?D?B? p s WQZguH +=?+?+? 2 2 1 2. ? úZ??? ú" ? BaC¥t ?ili [? úZ?¥?? 5b s?=? ú" ? B}V s0W¥MoT¨? ?? ú" ? C}V ?s0W MoT¨ B? C¥ ?′???D? Tμ1 [? úZ?¥??5 1 ∑∑ == = n i n j ijjiM ByyB 11  () 10 ijijij cij cij ij BB p RT B ω+=  6.1 0 422.0 083.0 pr ij T B ?=  2.4 1 172.0 139.0 pr ij T B ?=  cij pr T T T =  ( )( ) 5.0 1 cjciijcij TTkT ??=  cij cijcij cij V RTZ p =  ()[] 3 3131 5.0 Cjcicij VVV +=  ( ) cjcicij ZZZ += 5.0  ( ) jiij ωωω += 5.0 3. hsY[ £ ·3??? / £s ¥" ?1 èe ?ìa £ ?D?M1¥1" ?+?b s £ ·3??? / £s ¥" ? ^ìa £ ?D?K+?¥ = ? (1) £ ·3??¥AA ü?a%A ü?? A ü?o ^ìaù5? ü?8"?¥ ·4 ^ £7? ^  e¥μ ·4b (2) ?? / £s ¥" ? Lé  ^%8?A8?so ·"d?¥ ·3b ? ¥+? ^ ·3l ? ¥ V L??μ  ?ZE? è¨ T ? vEb 2 4. ?t? iFíd?d" ?¥?l Tb sd?l () iii fRTdypTd ? ln,, =μ  T?? 1 ? lim 0 = ? ? ? ? ? ? ? ? → i i p py f d" ?¥?l i i i py f ? ? =φ 5. h :??é#?-?é¥?l#?l Tb s :??é ^·]?]a/¥ ?X 8D? L @8¥ :<?é-μ ' ()( )pTMpTMM id ,, ?=′?  ?-?é ^·? L?tD]?]a? M]F?¥ ?X?t¥ :<?é-μ' id mm MM ?= E M 6. 1 I 1 K′E V[¨?Q ??t¥ A ü?9 ?$ sQ ??t V[í ? AT ^ ?X?t? ^ A ü?'Vr T?¥ 1= i γ  i v i φφ = ? a ??ú¥ f ?/ Pondingy0í ?1 1? ^  A ü?Vr T?e1 v i s i s i i iid i p p x y K φ φ == b?? T V[ A K′??D? ?a ?μ17DF?í1yN V[¥ K′E9 ?Q ?"d¥ A ü?b 7.  ?F?¥à Q# WilsonZ?? NRTLZ?¥a ??b s ?F??t?¥?]Fs ité? jté??s0W¥MoT¨ ??]]?s0W¥T¨ ?Ds ?s0W¥MoT¨ ?¥vl?]y N B ? ?s0??¥F?D?t?¥98F?μ ??]b ?? ?¥ iü?S ?F?b Wilson" ?Z?? a¨?AAsa 8"¥9 ?7 NRTLZ? àμNK???Z? ^ 3? ?¥" ?Z ? {ˉb 8. M?AM (¨d" ?9 ?¥ ? 4 ^ I 1$ s? d" ?¥9 ?Z?31ê4B?] H a¨? M?AM¥ ?Z ? O9 ?úM?b??Z?¥? Tˉ? ??9 ?1? ? 4b =a w?5  5 s ??B5s?=5s 1. hw? AM ü?¥1" Tb  ?AM¨" ?V U[ 3 Lewis-Randell?51 M¨d" ?V Ub  s? M ü?5μ l i v i ff ?? =  ?? TPH[ V[? d" ?¥? l TM?1 v ii v i pyf φ ?? =  ? T¥·H[ V[? " ?¥?l TM?1 iii l i xff γ Θ = ? 7S ? |1]?]a/¥BA8? ^μ () ? ? ? ? ? ? ? = Θ RT ppV pf s i l is i s ii expφ { ?M ü?5¤? () ? ? ? ? ? ? ? = RT ppV xppy s i l i ii s i s i v ii exp ? γφφ 2. V  T?é? a?¥L !?e?w? ?é:? pb sL? 1) a ?ù ? "? u?í "? u H· ?[ ( ) 1exp ≈ ? ? ? ? ? ? ? ? ? RT ppV s i l i b 2) ?8"?òFí ^]ss8a ¨Qs8a ;Ds8 ?Mí¥ ]"t * 1 A M ( V j1 ?X??t? Lewis-Randall ? 5μ i v i φφ = ?  ] H 1= i γ b 3) ?a/ M V j1 ?X 8? ^μ 1 ? = v i φ  1= s i φ b 8  ? ? A ü?8" ? ?@ 1235 i s ii xppy = '1 ?é: ? pb ?a9 ?5  5 s ??B5s?=5s? ?5s ? 15s 1. s n5 # ^? 273 K?? a/¥ 8 Ví ? j1 ?X 8b 13.31/ 2.2219 7.20/ln ? ?= Kt Pap s i 273K, p i s , l 473K, 3MPa, g 273K, p i s , ig 473K, 3MPa, ig H v ? ′ ?? 2 H ig H? H? 4 () () = ? ?= == 273 2 2 273 13.31 2.2219 1 ln TT s i T T Td pd -2824 () 48.23 1 ln =??=? Td pd ZRH s i v kJ·mol -1 ()6.150101.07.0 473 273 3- 473 273 =×+==? ∫∫ dTTdTCH ig p ig kJ·mol -1 V m =RT/p+10 -5 5 10 ? ?=? ? ? ? ? ? ? ? ? V T V T ()3010 5 1030 0 5 2 ?=?= ′ ? ∫ × ? dpH J·mol -1 11.1740 2 = ′ ???+?=?+= HHHHH ig vmm kJ·mol -1 2. ss??? ?/ (1) 19124 ? 1 2 11 1 1 1 1 1 1 =+?== ? = x x xx dx fd f MPa (2) 49124 ? 0 2 11 0 1 1 1 1 1 =+?== ? = x x xx dx fd k MPa (3) 2 11 1 3 1 2 11 11 1 1 364 364 ? xx x xxx xf f +?= +? ==γ (4) 2 11 1 3 1 2 11 11 1 1 75.05.11 4 364 ? xx x xxx xk f +?= +? ==′γ 3. s???Z? #? ê :?é??a ??? ?yN ?T?Z?? ? A?1 ?@ Gibbs-DuhemZ?b n5? ???a/¥ Gibbs-Duhem ^? ? @' 0 2211 =+ VdxVdx b=í8"S??M?¤ 0 2 2 2 1 1 1 =? dx Vd x dx Vd x ?X?¤ 1 1 1 2bxab dx Vd ??=  2 2 2 2bxab dx Vd ??= b? ^μ ()( )0 21 2 2 2 1 1 1 ≠?+?=? xxba dx Vd x dx Vd x yN?Vr T?? ?b 5 4. X? MF? y 1 , y 2 ,….,y n #? T p ]?a ? p#D-M ü?¥A MF? x 1 , x 2 , ….x n ¥9 ?V?b s9 ? m ?/