CH EM. R ES. CH IN ESE U.

2005, 21 ( 2) , 209—212

Exten sion of Huron - V ida l- type M ix ing Rule to Three-

param eter Harm en s- Knapp Cub ic Equa tion of Sta te
3 3
HAN X iao 2hong , W AN G Q in, CH EN Guang 2m ing and CU I X iao 2long
I nstitu te of R ef rig era tion and C ry og en ics, Z hej iang U n iv ersity , H ang z hou 310027, P. R . C h ina

R eceived M ay 14, 2004

　 　 In th is p ap er w a s ex tended the HV 2typ e m ix ing ru les to H a rm en s2Knapp cub ic equa tion sta te ( H K
CEO S ). T he new HV 2typ e m ix ing ru le w ith H K CEO S w a s tested fo r V apo r2liqu id equ ilib rium (VL E ) of dif2
feren t po la r and nonpo la r system s. T he tested resu lts a re in good agreem en t w ith ex isting exp erim en ta l da ta
w ith in a w ide range of tem p era tu res and p ressu res. In com p a rison w ith the VDW m ix ing ru le, the new m ix 2
ing ru le gives m uch better p rediction s fo r the VL E of nonpo la r and po la r system s.
Ke yw o rds 　Equa tion of sta te, A ctivity coefficien t, V apo r2liqu id equ ilib rium , M ix ing ru le
A rtic le ID 　100529040 ( 2005) 2022209204

In troduction H K CEO S in o rder to have a bet ter p red ict ion cap a 2
T he ca lcu la t ion s fo r vapo r 2liqu id equ ilib rium b ility fo r h igh ly non idea l system s w ith a w ide range
(VL E ) a re often ca rried ou t by u sing the m ethod of tem p era tu res and p ressu res.
ba sed on the act ivity coefficien t m odel w h ich is Exten s ion of Huron - V ida l- type M ix ing Rule
very pop u la r due to the fact tha t the act ivity coeffi2 1 　 Three- param eter Harm en s- Knapp Cub ic Equa -
cien t m ethod ha s a good p red ict ion of VL E. Severa l tion of Sta te
cla ssica l VL E m ix ing ru les ba sed on the act ivity co 2 [5 ]
H a rm en s and Knapp gave H K EO S and it s
efficien t m odel have been p ropo sed by m any au 2 co rrespond ing p a ram eters acco rd ing to the crit ica l
tho rs in recen t yea rs . T he idea to link the e2
[ 1_ 3 ]
p a ram eters con ta in ing crit ica l acen t ric facto r and
qua t ion of sta te ( EO S ) to the excess G ibb s free en 2 eccen t ric facto r
ergy a t an infin ite p ressu re w a s first p resen ted by p = RTg (V - b) -
[1 ]
H u ron and V ida l . T hey a ssum ed tha t no excess ag [V + bcV - b2 ( c - 1) ]
2
( 1)
vo lum e ex isted a t an infin ite p ressu re lim it and the w here p is the p ressu re, V is the m o la r vo lum e, T
energy p a ram eters w ere determ ined by equa t ing the is the ab so lu te tem p era tu re, R is the genera l ga s
G ibb s free energy ca lcu la ted by the EO S to tha t by
con stan t, a , b and c a re the equa t ion s of sta te de2
a liqu id m odel. L a ter, m any p ub lica t ion s covered
p enden t p a ram eters, resp ect ively.
the m o re o r less sim ila r app roaches to co rrela te
2 　 The New Proposed M ix ing Rule Extended to
p ro 2
[ 2, 3 ]
non idea l m ix tu res. Fo r exam p le, M ichelsen
HK EO S
po sed M HV 1 and M HV 2 m ix ing ru les ba sed on the
B y defin ing d and e a s fo llow s:
zero p ressu re reference sta te, etc. B u t, m o st of the
d = (- bc +
2 2
b c + 4b c -
2
4b2 ) g
2 ( 2)
above 2m en t ioned m ix ing ru les w ere p ropo sed fo r
the tw o 2p a ram eter EO Ss. T here have been lit t le e = (- bc -
2 2
4b2 ) g
b c + 4b c -
2
2 ( 3)
litera tu re repo rt ing the app lica t ion of the m ix ing then eq. ( 1 ) can be exp ressed in the fo llow ing
ru les to th ree 2p a ram eter EO Ss . E sp ecia lly, there
[4 ]
fo rm :
ha s been no t any litera tu re repo rt ing abou t th ree 2 p = RTg (V - b) -
p a ram eter H K CEO S together w ith excess G ibb s a [ 1g (V - d ) - 1g (V - e) ] g( d - e) ( 4)
energy m odel up to da te. A s the th ree 2p a ram eter 　 　 F rom the ba sic therm odynam ic rela t ion sh ip s
H K CEO S po ssesses bet ter p erfo rm ance in ca lcu la t 2 and eq. ( 4) , the residua l G ibb s free energy funct ion
ing m o la r vo lum e of sa tu ra ted liqu id and vapo r even a t a con stan t tem p era tu re and p ressu re ( in the lim 2
in the crit ica l reg ion in com p a rison w ith tha t of the it, p →0) is exp ressed a s
tw o 2p a ram eter EO Ss such a s SR K and PR. In th is (A - A IG )
lim =
p ap er, the HV 2typ e m ix ing ru le w a s ex tended to p →0 RT

3 3 To w hom co rrespondence shou ld be addressed. E 2m a il: hanxh@ 163. com

 2　　
10 CH EM. R ES. CH IN ESE U. V o l. 21

V = RTg
∑ x Κa g(b R T ) -
V P
am g - A E0 g
∫ ∫
RT ( bm R T ) = (R T ) +
lim - p dV - - dV = i
i i i i
p →0 V= ∞ V= ∞ V

lim - ln
p (V - b)
-
a
ln
V- e
=
( 1 - ∆) ∑ x ln (b gb )
i i m i Κm
g ( 12)
p →0 RT ( d - e) R T V - d
b = ∑x b
m i i i ( 13)
a
- Κi ( 5) 　　 In th is p ap er, w e a ssum e u i = um = 11235 [ 3 ].
bR T
A s the o rig ina l HV 2typ e m ix ing ru les do no t Eqs. ( 9) _ ( 13) together w ith the defined equa t ion s
cover the com b in ing ru le of p a ram eter c, in th is p a 2 fo r co rrespond ing p a ram eters eqs. ( 6 ) _ ( 8 ) con st i2
p er, on the ba sis of defin ing 7 i = c i - 1, and invok 2 tu te an in teg ra l set of the new m ix ing ru le fo r H K
ing eqs. ( 2) , ( 3) , eq. ( 5 ) is rea rranged by d ivid ing CEO S.
Fo r sim p licity, an em p irica l va lue ∆= 0136 is
[6 ]
it s bo th sides by a g ( bR T )
adop ted. In the lim it of zero p ressu re, w e a ssum e
Κi = ln u i+ 7 i + 1+ 1+ 67 i + 7 2
i
g
2 g E E
A 0 = G 0. Con sequen t ly, the act ivity coefficien t
u i+ 7 i + 1- 1+ 67 i + 7 2
i
g
2 g m odels can be u sed to ca lcu la te the excess G ibb s
[ 7_ 9 ]
free energy .
1+ 67 i + 7 2
( 6)
3　Fugac ity Coeff ic ien t
i

w here u i = V i gb.i Fo r the m ix tu res, T he genera l exp ression fo r the fugacity coeffi2
M
lim (A - A
IGM
)g (R T ) = - am Κm g( bm R T ) ( 7)
p →0 cien t of a sp ecies in a m ix tu re, Υi , needed fo r p ha se
　　T he fo llow ing com b in ing ru le is cho sen fo r the behavio r ca lcu la t ion s is com p u ted from
co rrespond ing p a ram eter 7 m : δ ∞
5p
∫
RT
R T ln Υ= - dV - R T ln z ( 14)
5n i
7 m = ( ∑i ∑j x ix j ( 7 i + 7
3g 3g 4g V
)g
4 4 3 V
j 2 ( 8)
　　T he m ix tu re fugacity coefficien t of H K CEO S
and thu s
can be ob ta ined by m ean s of eq. ( 14) :
cm = 7 m + 1 ( 9)
δ 1 5( n T bm )
Κm = ln u + ln Υi = - ln ( Z - B ) + -
V - b 5n i
1+ 7m + 1 + 67 m + 7 m2 g
2 g
am
5( n T d m )
-
5( n T em )
L
5( n T2 a ) 5n i 5n i -
1 + 67 m + 7 m2 g
2 g RT -
u+ 1+ 7m - 5n i K bm
am 5( n T d m ) 1 am 5( n T em ) 1
1 + 67 m + 7 m2 ( 10) -
R T bm K 5n i V - d m R T bm K 5n i v - em
w here um = v m g bm. Eq. ( 10 ) is the genera l exp res2 ( 15)
sion of severa l equa t ion s of sta te so lving p a ram eter
w ith
Κ, fo r exam p le, fo r SR K EO S, Κ= ln ( u + 1) g u ; fo r 2 015
K = ( cm + 4cm - 4)
PR EO S,
1 2Z + B ( cm + K )
Κ= ln u+ 1+ 2 g L=
K bm
ln
2Z + ( cm - K )
1- u- 2 g2 2 5( n T bm )
= bi
B a sed on the defin it ion of excess H elm ho ltz 5n i
1 5( n T am ) 5( n T bm ) 5( n TD )
2
free energy and upon the sub st itu t ion of the above
= RT D + bm
m en t ioned defined eqs. ( 8 ) _ ( 10 ) in eq. ( 7 ) , the n T 5n i 5n i 5n i
E
exp ression fo r A 0 is a s fo llow s: 1 ai bm
Κm R T ∑
D= Κix i - A E0 - R T ( 1- ∆) ∑x i ln
A 0g
E
(R T ) = - am Κm g ( bm R T ) + i b i i bi
5( n T D ) 1 ai
∑ x Κa g(b R T ) - ∑ x
i i i i i i i ln ( bm g
bi ) ( 11)
5n i
=
Κm R T ∑ i
Κi x i - A E0 -
bi
　 　 In add it ion, the tw o term s in th is equa t ion bm 5( n T Κm ) D
( 1- ∆) R T ∑x i ln -
have an effect on the size d ifference: the excess i bi 5n i Κm
G ibb s energy term and the loga rithm ic term em 2 5( n T d m ) 5( n T bm ) 5( n T cm )
= 015 - cm - bm +
body the effect of the size d ifference. To reduce 5n i 5n i 5n i
th is doub le coun t ing of the size d ifference, a new 5( n T bm ) bm 5( n T cm )
K + ( cm + 2)
p a ram eter ∆( 0< ∆< 1 ) is in t roduced in to eq. ( 11 ) , 5n i K 5n i
thu s the new HV 2typ e m ix ing ru le adap t ing to H K 5( n T em ) 5( n T bm ) 5( n T cm )
= 015 - cm - bm -
EO S is ob ta ined. 5n i 5n i 5n i
N o. 2 HAN X iao 2hong et a l. 　　
211

5( n T bm ) bm 5( n T cm ) In T ab le 1, ∆p and ∃ y a re the ca lcu la ted aver2

K + ( cm + 2)
5n i K 5n i age deriva t ion s of p ressu re and vapo r com po sit ion s
4　Activ ity Coeff ic ien t M odel resp ect ively:
T here a re m any act ivity coefficien t m odels fo r N ∑i g ( p cal - p exp ) g
∆p = 1g p exp g i ( 18)
ca lcu la t ing the excess G ibb s energy, such a s, the
N R TL m odel , the W ilson m odel , the U N I2
[7 ] [8 ] N ∑i g y cal - y exp g i
∃ y = 1g ( 19)
[9 ]
QU A C m odel and so on. In th is p ap er, A 0 in
E
　　T he new m ix ing ru le, coup led w ith H K CEO S
eq. ( 12) w a s ca lcu la ted by virtu r of the N R TL loca l and N R TL m odels, w a s tested fo r VL E of d ifferen t
com po sit ion m odel. po la r and nonpo la r system s, such a s cryogen ic m ix 2
Σj , i tu res: A r2N 2 , N 2 2O 2 , m ethane 2ethylene, and o ther
x j exp - Αj , i
m ix tu res: R 134a 2R 143a, R 134a 2R 600a, p rop ylene 2
E
G (T , p ) RT
= ∑x i ∑ Σj , i
RT Σk , i p rop ane, R 134a 2R 235fa, R 600a 2 R 235fa and R 322
i j
∑ k - Αk , i
x exp
RT
k
R 227ea. T he tested resu lt s a re show n in T ab le 1.
( 16) F rom T ab le 1, w e can see tha t w ith in a w ide range
Σi, i = 0 and Αi, i = 0. W here Αj , i Σj , i and Σi, j a re ad 2
, of tem p era tu res and p ressu res, the new HV 2typ e
ju stab le p a ram eters. To the g iven system in the p a 2 m ix ing ru le w ith H K CEO S is in bet ter ag reem en t
p er, it is recomm ended to u se Αj , i = 013. Σj , i and Σi, j w ith the ex ist ing exp erim en ta l da ta, and the aver2
a re d irect ly ad ju sted to VL E da ta w ith the a id of age deriva t ion s of p ressu re and vapo r com po sit ion s
the fo llow ing a lgo rithm by u sing the ob ject ive func2 a re a ll sm a ller. In com p a rison w ith the t rad it iona l
t ion: V an der W aa ls (VDW ) m odel, the new HV 2typ e
m ix ing ru le w ith H K CEO S can g ive ou t m uch bet 2
N

Fo = ∑ i
( y 1, exp - y 1, cal) 2i + ( y 2, exp - y 2, cal) 2i
ter p red ict ion s fo r VL E system s.
( 17)
Results and D iscuss ion
Table 1　Correla tion results for d ifferen t system s obta ined w ith HK CEO S and the new m ix ing rule
T em p eratu re H K+ VDW m ix ing ru le H K+ the new HV 2typ e m ix ing ru le
System N R ef.
rangesg
K ∆p (% ) ∃y ∆p (% ) ∃y
R 143a g
R 134a 273115_ 313115 27 513216 010824 218467 010231 [ 10 ]
R 143a g
R 152a 303115_ 313115 12 613215 010894 411503 010113 [ 10 ]
E thano lg
w ater 423115_ 473115 15 1713215 010156 216201 010046 [ 11 ]
M ethano lg
w ater 321191_ 373115 36 1813121 010315 518696 010048 [ 12 ]
A cetoneg
w ater 298115_ 423115 22 1113124 010456 516681 213262 [ 12 ]
Carbon d iox ideg
ethylene 252195 12 613215 010105 517770 010039 [ 12 ]
R 134a g
R 600a 293166_ 303168 19 310498 010056 410421 010018 [ 13 ]
R 134a g
R 235fa 283196_ 303168 15 210023 010032 113084 010062 [ 13 ]
A cetoneg
m ethano l 373115_ 423115 25 713215 010188 510532 010135 [ 12 ]
M ethyl2acetate
M TB g 353115_ 373115 11 013243 010212 010847 010023 [ 14 ]
P rop yleneg
p rop ane 260195_ 329185 23 218939 010156 312166 010056 [ 12 ]
M ethyl2acetateg
ethyl2acetate 353115_ 373115 8 812535 010203 012597 010016 [ 14 ]
M ethano lg
T EGDM E 293115_ 393115 36 1113243 010325 514569 010138 [ 12 ]
M ethaneg
ethylene 186125_ 206125 19 310035 010124 215863 010097 [ 12 ]
A rg
O2 90115_ 110115 36 019823 010103 016917 010048 [ 15 ]
N 2g
O2 70115_ 77165 30 315123 010087 516259 010036 [ 15 ]
R 32g
R 227ea 283120_ 323121 21 815967 010121 510274 010086 [ 16 ]
H yd rogen su lfideg
p rop ane 243115_ 288115 19 1513638 010291 317637 010177 [ 12 ]
R 600a g
R 235fa 303168 12 017100 010195 011954 010037 [ 13 ]
A cetoneg
m ethylacetate 293115_ 313115 33 017416 010105 111125 010070 [ 12 ]

Conclus ion
T hough m u lt i2p a ram eter EO Ss cou ld no t be
w idely u sed in m any ca lcu la t ion s in the p a st, w ith
the qu ick developm en t of com p u ter techno logy,
they can be w idely u sed fo r their ow n m erit s now.
How ever, m any m ix ing ru les a re p ropo sed fo r the
tw o 2p a ram eter CEO Ss. T ak ing the advan tages of
m u lt i2p a ram eter EO Ss, w e g ive the new HV 2typ e
m ix ing ru le adap t ing to th ree 2p a ram eter H K CEO S
ba sed on equa t ing the excess G ibb s free energy
from a p ha se act ivity coefficien t m odel to the co rre2
spond ing term from an EO S in the lim it of zero
 2　　
12 CH EM. R ES. CH IN ESE U.
p ressu re. T he new HV 2typ e m ix ing ru le, coup led
w ith H K CEO S, ha s been tested by 20 b ina ry sys2
tem s includ ing m any cryogen ic m ix tu res, the test 2
ed resu lt s revea l tha t it is m o re accu ra te than VDW
m ix ing ru le in a w ide range of tem p era tu res and
p ressu res. A s the new m ix ing ru le is sim p le, accu 2
ra te and on ly tw o in teract ion p a ram eters a re need 2
ed, it enab les the m u lt i2p a ram eter EO Ss to be u se2
fu l in the p ract ica l ca lcu la t ion s.
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