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"?8 V c b | p –V –T w ?g?? ü ? 5 V[¤?=?m?bm 2 2 ? 2 3 sY1m 2 1 g?¥ p –Tm? p –Vmb m 2 3 Bté¥ p –Vm m 2 2 Bté¥ p –Tm m 2 2 ?¥ ?HM ü? wL 6?La ??L? ?L ?L¥?? ^ ?M?bú? "???a ?¥ @8?1? "? @8e? @8b ?m 2 2V A?? B?'VA8 ? 8 àμ,VM? ?' ^vM¥V??il?¥MMb? "? @8¥?édè+ y;?]?A8??]? 8 VT1+ y¥Y | ·4?Q?oébít M ? ?¨? "? @8+ y?é 7?¥? "?s ?/ ??Q?/ ??1? |? "¥ £?b m 2 3 ^[? T1?M ¥ p –Vmbm?c  ??H??Lú? "??¥? ?L wL üái O?DM? ?M?bl? "??¥??L? ???sF??W £ ü 1 A ü? i u ????L?B? ??¥a ? '1?BtéN?/¥?? ab wL AC ? BC sY1?AML?? ML wL ACB c¥ u×1 A i u  P·sY1AM u? M ub ??L M u¥ £ ü ?"?¥ 6ú7?vM ? "?? HKa ê?B? Cb Vm 2 3 ? V[ A "???L "??  ^B? £ ü.? | q? w q??? , 3 ?D V U1 0= ? ? ? ? ? ? ? ? = C TT V p  2 1 0 2 2 = ? ? ? ? ? ? ? ? ? ? = C TT V p  2 2 T 2 1? 2 2??]té?? ? ? ì ?Z??¥ù?il×vb 2.2 8¥ ?Z? í ? @8 p –V -T1"¥f ? T1 ( ) 0,, =TVpf  2 3 T 2 3?1 ?Z? Equation of Satate EOS¨ ? ó" ü? ?/B @8¥a ?a :8a?-W¥1"b?y £ ?D? ?Z? μdè×1¥N′ ??? V U?<W¥S? = paVaT -W¥f ?1"7 O V[YV ?9 ?? ?°¤V L? ¤¥  e £ ?D?éb " -i¥ ?Z?s ?/+ ?  1 ?X 8 ?Z?  2 virial ? úZ?  3 ?Z? ?Z?  4 ? ? ?Z? 2.2.1 ?X 8 ?Z? L?s0¥vl ?]+??B"s0W?iMoT¨ ???"¥s0F?¥ 8 ?S ?X 8b?¥a ?/? L 8 V[?T ?X 8) ?[e?ù5b ?X 8 ?Z? ^Ke?¥ ?Z? RTpV =  2 4 μ Hy? !9? V[¨ ?X 8 ?Z?é?í ?¥ ?b 6? ? V[T1? ? L 8 ?Z? ^?? ?¥S-B? →p 0? ∞→V H ??? L 8 ?Z ????e1 ?X 8Z?b 2.2.2 ? úZ? ?Z? ?¨d9 ?Ds s0W¥T¨ ? μ?T L¥ ? ?$bZ?¥? T1 "+′+′+′+== 32 1 pDpCpB RT pV Z  2 5 "++++= 32 1 V D V C V B  2 6 "++++= 32 1 ρρρ DCB  2 7 4 T? )(BB ′ a )(CC ′ a )(DD ′ llsY?1?=a? ?a? 1ll? ú virial" ?b ?Z? 2 5j 2 7 |í k) ? H?]? T¥ virial" ?-Wi"/ ?1" RT B B =′  2 8a () 2 2 RT BC C ? =′  2 8b () 3 3 23 RT BBCD D +? =′  2 8c Vd9 ?Ds?= virial" ?V U ?s0 ·MoT¨?á¥D 8 ?X?¥ μs? ? virial" ?5Q? ??s0 ·MoT¨?á¥D 8 ?X?¥μs b e5 Z? 2 5j 2 7 (? ^í k[?B?y? Ll?K訥 ^= ¨ [¥? úZ? ? T1 V B Z +=1  2 9 pB′+=1  2 10a RT Bp +=1  2 10b LlV ü???? "??aa ??ú? 1.5MPa H¨=¨ [¥? úZ? V[ ?ú ?1V U 8¥ p –V -T1"?a ?ú? 5.0MPa H31¨÷¨¥? úZ?b ? úZ??? V[¨? p –V -T1"¥9 ?7 O V[?s0 £ ?D ?¨? ú" ? ó " 8¥Ta 2 ?a £ ???éb 2.2.3 ?Z? ?Z? ?Z? ?Z? ^·Z? VZ 718  ᥠ?QZ? Tb? ?Z? ?3 p ?μ?úú?? tˉ? sy????b  1 van der Waals  ?Z? 2 V a bV RT p ? ? =  2 11 ?Z? ^?B? a¨? L= 8¥ ?Z?D ?X 8 ?Z?M1 ?F ? ? ? a ? b ? ìsYV?s0W¥? ??s0' &8¥?Y V[V @8¥ p-V-T L ? E?¤?9 V[?Bté¥ "? ? 9 ?¤?b  2 Redlich-KwongZ? Redlich-KwongZ?e? RKZ? ? T1 )( 5.0 bVVT a bV RT p + ? ? =  2 12 T? a b1 RK? ?D @8¥+?μ1 V[¨/ T9 ? 5 cc pTRa /42748.0 5.22 =  2 13a cc pRTb /08664.0=  2 13b RKZ?¥9 ? ?1 van der WaalsZ?μ?v¥4ú V[1? ?1¨?d? ? D???t?? <?#cμ _o¥??t ˉ?á 3?v¥ êμb1 éB?4ú RKZ?¥ú ?v  P¨S?L4 ÷¥ ?Z? ?Z?b  3 Soave-Redlish-Kwang Z? 1972 M 1 4ú RKZ??té#?A8 p –V –T9 ?¥ ?b Soave RKZ?é ? ?é?1 RKS  SRK SoaveZ?bZ?? T1 ( ) ()bVV Ta bV RT p + ? ? =  2 14 ? () ( ) ( )TpTRTaTa cc αα ?=?= /4278.0 22  2 15a cc pRTb /08664.0=  2 15b [ ] 2 5.0 )1(1)( r TmT ?+=α  2 15c 2 176.0574.1480.0 ωω ?+=m  2 15d T? ω1 ê?y0b RKSZ?4ú ?té#cμ _oté¥ p –V –T9 ?úb ÷?1¥ ^?Z? ?A8 á¥9 ??÷ ?b 1 L? ?¨9 ? p3 RKZ?? RKSZ?9 V[V U?/ ? T ? ? ? ? ? ? + ? ? = h h B A h Z 11 1  2 16a Z B V b h m ==  2 16b T? RT bp B =  2 16c 5.22 TR ap A =  RKZ?  22 TR ap A = (RKSZ? )  2 16d ?¨  ?Z? V[é?Y}9 ?b  4 Peng RobinsonZ? RKZ?? RKSZ?9 ? "?a êy0 Zc?A8 á H??C?v¥ êμ1  ???B üA¥?@ Peng Robinson? 1976 M4  e ì¥Z?e? PRZ?b ( ) ()()bVbbVV Ta bV RT p ?++ ? ? =  2 17 6 ? () () ( )TpTRTaTa cc αα ?=?= /45724.0 22  2 18a cc pRTb /07780.0=  2 18b [] 2 5.0 )1(1)( r TkT ?+=α  2 18c 2 26992.054226.13746.0 ωω?+=k  2 18d PR Z?9 ??? aa?A8 á?Z ?μ÷z¥ ?b ?9 ^y?M ü? 9 ??K訥Z?-Bb  5 ?Z? ?Z?¥Y¨? T B , ?Z? ?Z? V[| V U1 ?/¥? T ))(( )( bVbV Ta bV RT p σε ++ ? ? =  2 19 T?? ? ε? σ 1B ?  ?μ¥té (M] ? ? b ^té¥? ???] ¥ ?Z??μ?]¥?f ? )(Ta b ?Z?Z?? Te?Z??B?oμ ?? ? O? ? V¨Bté "??é? ê?y 09 ?b??Z? ^8¥ ?QZ? T#3 ?Z?Z? V[¤? ??8?bZ?¥ P ¨? ?1 p |Z?¥8? ^B?×1ì?b  ?9 ?V üúa/ ?X 8 ?Z?'? ? a¨ RKZ?9 ?9?{ ??v ¥μM ? a RKSZ?ú?zb 2.2.4 ? ? ?Z? De?¥ ?Z?M1? ? ?Z? V[÷ z¥ TapS? = ?1 í ??]t "¥ p-V-T1" ?  ?? ^Z?? Tˉ9 ? 4?yT ??vb  1 Benedict Webb RubinZ? 1940 M ?Z?9 ??1 ó ^Q# ?t¥A8? 8 £ ?D?é HμN′b )exp()1()()( 223 2 632 2 0 00 γργρραρραρρ ?+++?+??+= T c abRT T C ARTBRTp  2 20 T? ρ1 á γα?,,,,,, 000 cbaCBA ? 8?è ??Bté¥ p-V-T ? ?? a ? ??bQ ? £ ?D?é9 ?? BWR Z?9 ?ú?ú??Z?? ?¨?c £8 "b [4ú BWRZ??? u×¥9 ?ú1 "¥ Starling? |4  11?è ?¥ Starling T ? BWRS T  2 Martin HouZ? 1955 M ?Z? ^ 1955 M Martin ? q?áSD??? *4¥e? MH Z?b  a??1 MH-55?Z? b1 4ú?Z?ú á u¥ú ? 1981 M?? *? q??|?Z?¥ a¨S? ?Z?AM u?1 MH-81?Z?b MHZ?¥Y T1 7 ∑ = ? = 5 1 )( )( i i i bV Tf p  2 21 T? )/475.5exp()( ciiii TTCTBATf ?++=  52 ≤≤ i  RTTf =)( 1  )1=i T? bCBA iii ,,, ¥1Z?¥è ? VVBté "?? ?#?? a wL ¥B? ? p¤b MH 81? ?Z? ?] H¨? aA MZ? ?ú a¨S?< ?¨? ? d?à <?¥té ? NH 3 aH 2 O 0 8 H 2 aHe?9 V?¨????y? !9?¤?<W P¨b 2.3 1 ?e ?# ?¨ 2.3.1 1 ?e ? 1 ?e ? a1M]¥1 ?/ ?μ¥téVCM]¥?éb van der Waals4¥e?1 ?e ?Z? ^ rrrr TVVp 8)13)(/3( 2 =?+  2 22 e?? ?e ?ü ^ ? ?? ?e ?V ?1 ??]¥ @8? μM]¥1??1a ? H5 μváM]¥a êy0b i O  ê ? ?X 8¥?M]b ??e?1 ?e ??e? @8 ?bada_ ^dè ?¥b?ü ^=? ?a ê y0m¥G b oμò? 8¥ "?a êy0 Z c M?¥Hq/e?1 ?e ?? ??ì? ?b7 "?a êy0 Z c  0.2j0.3 S? =M?i? ^B?è ?b VnS£?4¥e?1 ?e ?o ^B?í ?¥1"o a¨? o?d?¥e?s0b? z1 ?e ?¥?¨S? ?4ú9 ?ú¥μrZE ^e?1 ?e ? =? ?1 ?e ?¥1" T?? ?? ? ? ?b 2.3.2 ?? ?1 ?e ? Ba[ Z c 1? ?? ?¥1 ?e ? Lydersen ? |[ Z c T1? ?? ?|a êy0V U1 ),,( crr ZpTfZ =  2 24 Lydersen ? |?  ?Qa?a ?aa ;?aμ X?ta?sít? £ =¥ 82??]A8D 8¥ p –V –T?é? "??é ? T a êy0m M?¥9 ?a êy0 Z1 )27.0( ' ?+= c ZDZZ  2 25 8 ? Z′1 ? p¥ @8¥a êy0 Z1 27.0= c Z H @8¥a êy0b D1 27.0≠ c Z H¥n?" ? ? ì? ^ r T a r p ¥f ? V[VM?¥m?°b ?e ??ZE??¨? @8a êy0¥9 ?] H? V¨?A81 á¥9 ? ? ? 1?¨ T )27.0( ?+=′ c ZDρρ  2 26 =a[ ê?y0 ωT1? ?? ?¥? ?e ? " [ c Z T1? ?? ?? Pitzer? |4¥ ê?y0 ω¤? dè<W¥ P¨b Bté¥ ê?y0 ^? té¥? a ??l¥b L?CB ? @81?? a ¥ ?D1?¥? ??í ?°L1"' ? ? ? ? ? ? ? ? ?= r s r T p 1 1log α  2 27 ? c s s r p p p = ??]¥ @8 α μ?]¥′b?e? @8 bada_¥ ?μ? a ? ? ]BH°L 7 O?°LYV r T =0.7 1log ?= s r p ?B?b?ó? @81? a wL¥ê?¨ r T =0.7¥ @8Dbada_ e? o?s0¥ s r plog ′-μ ?V?b Pitzerü?Bμ′?l1 ê?y0 ω' )7.0(00.1log =??= r s r Tpω  2 28 yN ?? @8¥ ω′ ( V?? @8¥ "?? c T a "?a ? c p ′# r T =0.7 H¥ ?? a s p ? ??bbada_? ?e? o? @8¥ ω" 07d o? @8¥ ωV?té s0¥ ê?'d o?s0 ê ? o?¥?b Pitzer4¥ ?? ?1 ?e ? V[V ?1 ? ?μ ωM]¥ @8 ?)M]¥ r T a 9 r p / a êy0 ZA?M?ba êy0 Z¥1" T1 )1()0( ZZZ ω+=  2 29 T? )0( Z a )1( Z ? ^ r T a r p ¥f ?b V?M?¥m°b Pitzer 1" T?d? D?¥ 8 ?4 V L¥2Tμ %3< ?¨? ? 8 Hμ19v? 5 j 10%7??? 8? 0 8 P¨ H??÷F?ib 2.3.3 ?R? ?Z? ?ì ?R? ?Z? ^·¨1? ? r T a r p a r V }9M  TapaVh ? ?Z?? 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T ??Q?F? x?t p –V –T?é¥?Y?1ù??t ?Z?¥1ob 2.4.1 ??5 ? ?X 8¥?t a ??8DF?¥1"sYV U? Dalton sa? p? Amagats8? p ii pyp =  2 40 ii ynVV )(=  2 41 ?? L 8?? 8BFs¥d ?X?#???? ¥d ?X? P¤sa? p ?s8? píE ?1 í ? 8?t¥ p –V -T1"b " -<W?¨¥ZE ^| ?Z ??¥è ?[V U?F? x[#Bté? ?[¥f ???f ?1"?T1??5b ??]¥ ?Z?μ?]¥??5bùs a?¥??59 ? ?Z??¥è ?[ P  ? ?1 í ?? L @8?t¥ p –V -T1"èè ^9 ?? £ ?D?é¥1 11 ob 2.4.2 8?t¥′ E "?? ? ?T¨? ?e ?) ? 8?t¥ p –V -T1"üA? #? ??3 %?t¥ "??éù5b V[|?t j1LX¥Bté|′ EBté¥ "?? ??T′ E "?? ?b?"L V[ü a¨?Bté¥1 ?ZE?¨??t bKe?¥ ^ Kay ?5b? ?5|?t¥′ E "?? ?V U? ∑∑ == i ciipc i ciipc pypTyT  2i42 T? pc T  pc p sY?1′ E "??D′ E "?a ?b ci T  ci p sYV U?t? i Fí ¥ "??? "?a ? y i 1 iFí?t?¥ :s qb ?i′ E "??D′ E "?a ?i? ^?t? L¥ "?? ? ? ì?? ^ ?D  ¥? ?1  P¨Bté¥ p –V -T1"é?9 ? H?¨¥? ? àμ ??t ?ilb? t? ?μFs¥ "??? "?a ?-1[/S? = 2/5.02/5.0 <<<< cjcicjci ppTT Kay?5D  e?ˉ¥?5M1 ?¤ ?′¥μY?? 2 b Prausnitz Gunn4B?e?¥?é?5| pc T ˉ¨ Kay?5 pc p V U1 ∑ ∑ ? ? ? ? ? ? = i cii pc i cii pc Vy TZyR p  2 43 ?t¥ ê?y0 M ω B? VV U1 ∑ = i iiM y ωω  2 44 T? i ω V U?t? iFí¥ ê?y0b [ +? T0V U¥??5? àμ #?FíW¥MoT¨? ?byN?t?? 5 (? ???Q??t¥?éb?FsμY?v¥?t- ? μ?Fí¥" d[# V[??1= t¥"d (? a¨b 2.4.3 8?t¥?=? ú" ? ? úZ? ^B? ? ??Z? ?? ú" ?Q?s0W¥?oT¨ ??=? ú" ? B Q? ?s0W¥?oT¨b?B 8?μ]B?s0W¥?oT¨???t7 y?=? ú" ? B ??1Q?M]s0-W¥MoT¨] H?1Q??] ??¥ ? s0?oT¨¥?Yb?d9 ?D V[? 8?t¥?= Virial " ?1 ∑∑ = ij ijjiM ByyB  2 45 T? y}V?tòFí¥ :s q B ij }VFí i? j-W¥MoT¨b A ? i? jM] 12 V U] ?s0T¨?5V Us ?s0T¨ O B ij " B ji b?=í?tZ 7 T1 22 2 2122111 2 1 2 ByByyByB M ++=  2 46 B 12 }V?t?é?1?-?=? ú" ?¨[/ü T9 ?b () )1()0( BB p RT B ij cij cij ij ω+=  2 47 T? ()0 B ? ^1? T r ¥f ?b Prausnitz9 ?ò "?? ?4 ?/¥??5 cjciijcij TTkT )1( ?=  2 48a 3 3/13/1 2 ? ? ? ? ? ? ? ? + = cjci cij VV V  2 48b 2 cjci cij ZZ Z + =  2 48c cij cijcij cij V RTZ p =  2 48d 2 ji ij ωω ω + =  2 48e T? k ij ?1=í?oT¨? ?b?]s0¥?oT¨?1 ?1??Y?t¥?é ?i ?s0 H?Y÷vbyN | ì? k ij 11?b?à? ?¤?B?9 ? k ij ¥Y ¨1 ó TB?YV L¥ p –V –T ? M ü? ? E?¤?b k ij ¥ ?′DF??t¥ téμ1B? 0j0.2-Wbí ?9 ?? k ij V[ |T1 ,b ¨ ?R??=? ú" ?9 ? 8?ta êy0¥?? ^ 9 ?Bté ?R??=? ú " ?¨ T 2i48aj 2 48e9 ?ò??o "?? ?} ? T 2 459 ??- ?=? ú" ? ?a P¨ T 2 459 ??t¥ B M Ka¨/ T9 ??t¥a êy0b RT pB Z M +=1  2 49 Vn 8?ta êy0¥9 ? ????? ?????dèZL1 V[I?9 ? ????b 2.4.4?t¥ ?Z? ?Z? ?| 8?t′ E1B?Btéü V[|Bté¥ ?Z??¨? 8?t¥ p-V-T 9 ??b?]¥ ?Z??¨??t p-V-T 9 ? H??¨?]¥??5B? ?Z?9 V P¨?]¥??5bv ? ?Z? (?¨ü¥??5??5¥a  o ?? Ll ?_b ?Z? ?Z? van der Waals RK RKS PRZ?¨??t HZ??? ? a 13 ? bè?¨[/¥??5 ∑∑ = ij ijjiM ayya  2 50a ∑ = i iiM byb  2 50b ]"?=í?t?1 22 2 2122111 2 1 2 ayayyaya M ++=  2 51a 2211 bybyb M +=  2 51b Vn M a ? ??-[ ij a 7 M b ¥9 ??oμBFí? ? àμ?-[b?-[ ij a V[¨/ T9 ? ( ) ijjiij kaaa ?= 1)( 5.0  2 52 T?¥ k ij 1=í?oT¨? ?B?? L ? E? V[¤???tòFs?é dèMí H V[í ? | k ij " 0b Prausnitz? |yp¨/ T9 ??-[ a ij cij cija ij p TR a 5.22 ? =  2 53 T??- "?? ?¥9 ? ˉ ??¨ T 2 48aj 2 48eb YV9 ?¤??t? ? M a , M b aü V[ ?¨ ?Z? ?Z?9 ??t¥ p –V -T 1"?  e £ ?D?é b ? ?"  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