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I, 1995
J. D . O l s o n "~
KEY WORDS: azeotrope: G~: H~; S~; heat of mixing; n-heptane; hydrogen-
bonding; mixture thermodynanfics; l-propanol: vapor-liquid equilibria; wlpor
pressure.
I. I N T R O D U C T I O N
[ 1 - 3 ] and between 423 and 573 K [4]. This work reports pressure
temperature-liquid mole fraction {PT.x) data and derived G E, H E, and S ~
between 380 and 445 K.
2. M E A S U R E M E N T S
2.1. Materials
2.2. Procedure
3. R E S U L T S
Table I. I ('o,rmm,d)
:t x, TIK) P (kPa)
"Fable I. r ('ontmued;
Table I. ~ Contimwdl
x, P1423.15 K
(423.15 K ) .-l(zl ) B(z,) C'(zj ) (kPa)
' h~g P(z I) = .4(z t 1 - B(z I) [ T + C'(z I)]: log = b a s e I(I. P(z I) = k P a . T = K.
standard rms erro," fro,n the least-squares fit is reduced with the addition
of each of the four constants. The pressure residuals from the four-constant
least-squares fit display no systematic trends and the overall rms error is
reduced to the expected level of experimental error ( ~ 0.2 % ). Derived Px
data between 373.15 K and 463.15 K were analyzed in a similar I:ashion
to produce G E data that could be analyzed with the G i b b s - H e i m h o l t z
equation to produce H ~ and T S E data as described in Section 4.
0 0 155.614
I 4625.3 4.077
2 4622.1 67.036 4.(133
3 4583.3 71.985 437.54 1.950
4 4573.6 3(1.534 494.(10 267.86 1.402
$411 16 1-14
222 Olson
4. D I S C U S S I O N
700
650
600
550
~2
500
y, calculated
400 • [4]
350 '
x 1 , Yl(calc)
1400
1200
1000
0
E
0
w 800
[] [11 \
<3 [31
A [21
• [4]
600
O This work
4 0 0 I . . L J I ~ ~ ~ ~ I ~ ~ ~ = I ~ ~ ~
T, K
Fig. 2. Equimolar excess Gibbs energy of mixing (G I~) vs temperature for
I-propanol ( 1 ) + n-heptane (2).
H v = _ T 2( O g / O T), (4)
224 Olson
3500
~__ Gz
Hz
3000
TS E
2500
O
E
-~ 2000
g 1500
w ~
1000
500
0' ~ ' i i i i
v
X1
Fig. 3. Excess functions of mixing at 423.15 K for I-propanol I)+
n-hepl;,ne ( 2 ).
283.17 11.25 2
293.15 I).26 2
3(13.15 (I.28 2
31)3.15 0.26 I
313.15 11.29 I
323.15 (I.32 I
333.15 0.36 I
333.15 IL37 3
398.15 0.57 This work
423.15 0.64 This work
423.15 062 4
448.15 11.7(1 This work
448,. 15 11.62 4
473.15 IL62 4
498.15 11.62 4
ACKNOWLEDGMENT
J. E. Mathena skillfully obtained the experimental data.
REFERENCES
I. H. C. van Ness. C. A. Soczek. G. L. Pcloquin, and R. k. Machado. J. Clwm. L)Lt~. Data
12:217 119671.
226 Olson