VAPOR-LIQUID EQUILIBRIA FOR AQUEOUS SULFURIC ACID John Irving Gmitro and Theodore V e r m e u l e n J u n e 24, 1963
* . , .
v 1 3
1.
Introduction A, 3. P a r t i a l - P r e s s u r e Equation
1 1 1 .
.
, . .
5
7 7
A.
Pure-Component P r o p e r t i e s
1.
2.
3.
B.
H;9,
f o r H2S04(g)
P Constants in Equations
I )
Co f o r H2So4(g)
9
11 12 15 16 21 21
.
.
IV.
Calculation of P a r t i a l P r e s s u r e s A.
B.
. . .
. .
a a
.
e
1.
2.
. .
. .
0
. .
0 . .
Adjustment of Alpha, 10 t o 9 8 . 5 7 0 ~ ,
3. C.
. .
0
24 25 31
Results.
. .
V.
D i s c u s s i o n and Conclusions
~ ~
. . .
e
0
35
39 40 42 81
-V-
VAPOR- LIQUID EQUILIBRIA FOR AQUEOUS SULFURIC ACID John Irving G m i t r o a n d Theodore V e r m e u l e n L a w r e n c e Radiation L a b o r a t o r y and D e p a r t m e n t of C h e m i c a l E n g i n e e r i n g U n i v e r s i t y of California, B e r k e l e y , C a l i f o r n i a June 24, 1963
A S ST RAC T
The composition of t h e v a p o r phase o v e r s u l f u r i c a c i d h a s not b e e n m e a s u r e d e x p e r i m e n t a l l y b e c a u s e of the low volatility of H SO4. 2 A m e t h o d i s d e s c r i b e d f o r calculating t h e p a r t i a l p r e s s u r e s of HZO, H2S04, and SO b a s e d upon liquid- p h a s e p a r t i a l - m o l a l t h e r m o d y n a m i c 3 q u a n t i t i e s . T a b l e s and g r a p h s a r e provided which give t h e above p a r t i a l p r e s s u r e s f r o m -50 t o 400" C at t h i r t y - s i x c o m p o s i t i o n s between 10 a n d 100 weight-percent acid.
-1-
I, INTRODUCT'IOiu
The vapor phase o v e r sulfuric acid solutions is composed of w a t e r and s u l f u r i c a c i d , together with sulfur t r i o x i d e f r o m the d i s sociation of the acid: H2SO4(g) = H2O(g) -t SO3(g)
(1)
In p r i n c i p l e , the distribution of t h e s e t h r e e components a t v a r i o u s t e m p e r a t u r e s and a c i d concentrations can be d e t e r m i n e d by e i t h e r (a) experimental partial-pressure measurements o r (b) calculation of p a r t i a l p r e s s u r e s f r o m liquid-phase t h e r m o d y n a m i c data. Method ( a ) , although m o r e d i r e c t , is not fully applicable to the s u l f u r i c a c i d s y s t e m b e c a u s e of the Pow volztility of H2S04" A n idea of the p r o b l e m s involved m a y be had f r o m t h e following table (derived f r o m the p r e s e n t study), which gives o r d e r - o f - m a g n i t u d e v a l u e s f o r the various partial p r e s s u r e s : Concent r a t i o n Temperatur e
("C)
(74
10
s03
25
100
20
7klO2 6x1 04
300
50
25
100 300
8
32.10
4x1 o4
2
10-10
10-6
5x10-1
90
25 PO0 300
5~10-3 J O - ~
10-5
E x p e r i m e n t a l difficulties notwithstanding, the t o t a l v a p o r p r e s s u r e of s u l f u r i c a c i d , which i n m o s t c a s e s is due e n t i r e l y t o t h e p a r t i a l p r e s s u r e of H 2 0, was t h e subject of n u m e r o u s investigations between Greenewalt, who in 1925 a s s e m b l e d the available d a t a , 1845 and 1923,
reviewed 19 s e p a r a t e v a p o r - p r e s s u r e d e t e r m i n a t i o n s .
His final r e 3
- 2-
(H298, '298
or
P This type of a p p r o a c h was f i r s t used by Abe14 in 1946, b a s e d i n p a r t on work by S o d e n s t e i n and Katayama5 who had m e a s u r e d Eq. ( 1 ) at 300 to 5 0 0 C with 85 to 100
).
TOWaxid.
for P The c a l o r i m e t r i c K
data available a t t h a t t i m e w e r e incomplete, n e c e s s i t a t i n g c r o s s - c o r relations f r o m v a r i o u s s o u r c e s in o r d e r t o d e t e r m i n e p a r t i a l m o l a l and So for p2 H2989 298 H2S04(g) w e r e not available,, This l a c k n e c e s s i t a t e d t h e u s e of K quantities. M o r e i m p o r t a n t , values of C f o r Eq. (1) i n the calculation of p l i b r i u m m e a s u r e m e n t s down t o 25 C .
O
P which i n t u r n r e q u i r e d a n
H2S04 extrapolation of Bodenstein and Katayama' s h i g h - t e m p e r a t u r e equiSince 1946, additional data have b e c o m e available which m a k e t h e calculation of p a r t i a l p r e s s u r e s v i a method (b) c o n s i d e r a b l y m o r e r e l i a b l e . E x t r e m e l y complete t a b l e s of p a r t i a l m o l a l quantities a t
calculating the p a r t i a l p r e s s u r e s of H 2 0 , HZSO4? and S O 3 as functions of t e m p e r a t u r e and a c i d concentration, inaccuracy still remains, P a r t i a l molal heat-capacity
SO
that s o m e
Because of t h i s , no c o r r e c t i o n h a s been
A,
P a r t i a l - P r e s s u r e Euuation
The
--AH"
ZT
-7-
T h i s i n t e g r a t e s t o give
;>
--
-01
1 1 1 1 -
Any coefficient
2 9 8 - 1 5 ' K (25' C ) .
--
- Fo RT '
'298 R(&8-$)-4J
298
s{[98
I T
298
where
G2 = '298
- aH:98
R
Y
The evaluation of G ( T ) m a y be m a d e by using h e a t - c a p a c i t y 3 functions in a f o r m given in the l i t e r a t u r e . F o r t h e g a s , we have Cp(g) - a -t b T 3- c T and f o r the liquid
0
(9)
C =
P
(e ) -t a ( T p 298
298)
(10)
+ T+C+DT+ET',
- 298 a)
Y
(11)
-5-
B = 1 (-AH;98 -f 2 9 8 a
R
1 C = R (AS:98
- a - 298 b - 298 2
$-
'p,
298 + L ( F - F 0 ) 2 9 8 - r 2 g 8 1
A)
and p H2S04
psoj
3.
Kp 'H2S04 / p H 2 0
"
The equilibrium constant f o r the dissociation of H2S04(g), Kp. m a y be d e t e r m i n e d as a function of t e m p e r a t u r e , a s follows. The equilibrium or Eq. (1) is given by
-6-
a n d t h e e q u i l i b r i u m c o n s t a n t by
P(1)
=:
ACo P(1)
.wher e
In K = J ln(298/T) -t K/T P
t L/T t M t N T t QT
J =
a'/R,
K = dq/2R,
N = b'/ZR,
Q = cg/6R
Hz98 f o r H2S04(g)
The value of Ho l i s t e d in Table I f o r H2S04(g) was c a l c u 29$ l a t e d a s follows: Kelley h a s tabulated values of (Ho-Hz98) and
(So-S;98)
These were
u s e d t o c a l c u l a t e the f r e e - e n e r g y function:
f o r H2S04(g)
0 F0 -Ho
298.15 I T
HO
-H :
(20)
298
500 600
700
44,03
74-32
761~2.2
46,72
47,4L 48, P O
78.17
800
80-11
T h e s e v a l u e s allow the calculation of A ( F - H z 9 & ) / T f o r t h e dissociation of H z S 0 4 ( g ) , Eq. ( I ) . In addition, e a c h of S o d e n s t e i n d e t e r m i n a t i o n s 5 r e p r e s e n t s a n individual m e a s u r e P ment of AFO (1) J T , s i n c e and K a t a y a m a ' s K
- 8-
Table I. Component
OK.
Reference
~ ~~
s03
H0
SO
g g g
(8) (8)
(9)
co(a' P
Elo
cal/mole -deg cal/mole-deg" cal-deg/mole kcal/mole kcal/mole cal/mole-deg cal/mole-deg cal/mole-deg cal/mole - de g kcal/mole cal/mole -deg kcal/mole kcal/mole cal/mole-deg c a l / m o l e - de g
H 2
Q
g
(8) (8)
so
(8) (8)
V a po r i z at i on
A HO ASo
(9)
H2S04
H0
SO
o c a : g C g P
Vaporization Dissociation
AHO
a = 7,86 c a l / m o l e - d e g See text b=4 6 ~ 5 x 1 0 ' ~ cal/mole-degZ c=- 2.612X10-~cal/mole-deg~ 18.90 kcal/mole F r o m Ho(R, g) 34.43 c a l / m o l e - d e g F r o m So(Q , g) 22,76 kcal/msle See t e x t 34.42 c a l / m o l e - d e g See text a = 13.34 c a l / m o l e - d e g See t e x t b =- 37.59X10- c a l / m o l e - deg2 c = 2,612k10-5 c a l / m o l e - d e g 3 d = - 3.22X105 cal-deg/mole
= a t b T -t c T
I- dT-'
-___I_.
( I ' 298
for
298
-*(
F-H298
)I*
C
Then Ho , since f o r H2S04(g) c a n be calculated f r o m [ AHo ] 298 ( l ' 298 H i 9 8 v a l u e s a r e known EOP both H2 O ( g ) and SO,(g). Bodenstein and Katayama m e a s u r e d concentrations r a t h e r than p a r t i a l p r e s s u r e s , and p r e s e n t e d t h e i r r e s u l t s a s log K v s t e m p e r Table II lists values of AF" / T (1) by u s e of the conversion relation ature.
AFO
calculated f r o m t h e i r d a t a ,
/T = 61) =.
R In K
P 2,303 R log(K R T )
C
Application of Eq. (22) a t e a c h of t h e s e d a t a points gave a n a v e r a g e value of 2 2 7 6 0 c a l / m e l e f o r [AH' deviation was 285 call/mole,
; the s a m p l e s t a n d a r d 298 As shown in Table I , t h i s p r o c e d u r e
H;98 =
57.80
94,45
22,76
= -115.OE kcal/mole.
Go equation S0r H,SO,(g) listed i n Table I w a s s e l e c t e d P 0 7 as a n e m p i r i c a l fit t o the C data given i n t a b u l a r f0rm by Gigukre. P The m a t c h t O the data over the region of i n t e r e s t is shown below:
The
T ("Kb
298" I 5
C" P e f , 7 PY
C'?
1__1__
a9,29 19.35
22,19
t4,40
308
400
500
600
700
26,08
2?,36
26"14 27.36
- 10-
Table 11.
741
-3.75
633 653
7 25 682
653 621
- 3.27
-1.01 0-36 2,09
688
711 750 711 657
- 2.47
-3.32 -1.85 3.13
0.70
1.98
1.17 0.30
0,oo
596
6 29
-1.12
- 2,22
-3.35 -4.24
- 1.03
- 1.88
-1.03 0.50 1.55
2.60
1.52 0.99 0-31
710 747
- 2.48
-4.47
- 1.85
-3.68 -0.32 0.68
R e f e r e n c e 5.
The values of Co So, and f r e e - e n e r g y functions given by Gigu'ere P* w e r e calculated Prom s p e c t r o s c o p i c data, B e c a u s e of a n u n c e r t a i n t y i n accounting f s r t h e t o r s i o n a l oscillations of the s u l f u r i c a c i d OH g r o u p s , p r o p e r t i e s w e r e tabulated i n r e f e r e n c e 7 both with and without the t o r s i o n a l m o d e included, We have u s e d the v a l u e s which i n clude the contribution of the t o r s i o n a l o s c i l l a t i o n s ; t h i s gives a proba b l e unceIrta.iinty i n the H2S04(g) functions of 0 , 2 5 cal/mole-deg. 3, Constants i n Equations It is d e s i r a b l e for calculational p u r p o s e s t o s e p a r a t e out t h e pure-component t e r m s i n Eq, ( I l ) , since they a r e constant f o r all a c i d compositions. Upon evaluating t h e s e t e r m s f r o m the d a t a i n and
H2
where
E = constant, Term
AQ
Sf
H 2 0 value
H SO4 value 2
- 3.67340
-4143,s
- 3,95519
-7
74 1 3 , 3
C U
llB8
10,24353
7.03845 1 ~ 6 11 46Xl~1-~
-
("K) ("K)
0,618943xlo- 3
0 K
2. 19062X10-6
equation, Eq. (481,m a y b e evaluated P i m m e d i a t e l y , s i n c e t h e y a r e all pure-component t e r m s , Upon s u b stitution of t h e data i n Table I, we obtain the following K F equation
The c a n s t a n t s i n the
s03
In KP = J ln(298/T) t K/T where
J -
t L/T t M t NT t QT2,
(25)
K
M
- 6.71464, = - 8.10161X104,
~
L =
2
9643.04, 14.74965,
N = - 9.4577Y~o-~, Q = 2.19062XO- 6
The fit of t h i s equation t o Bodenstein and K a t a y a m a ' s d a t a i s shown i n Fig. 1, and to M. The constants shown f o r E q s , (24) and ( 2 5 ) give p r e s s u r e s in units of a t m o s p h e r e s ; f o r r e s u l t s in mm Hg, In 760 is added to C'
The p a r t i a l m o l a l p r o p e r t i e s r e q u i r e d i n Eq. (24) f o r the c a l a r e l i s t e d i n Table 111. T h e s e values L H 2 0 and H2S04 0 a r e f r o m t h e d a t a of Giauque e t a l . , who have c a r r i e d out a n extenculation of p s i v e r e s e a r c h on the t h e r m o d y n a m i c p r o p e r t i e s of aqueous s u l f u r i c acid. R e f e r e n c e 6 r e p r e s e n t s t h e final correla.tion of t h e available
1 1 data and gives t a b l e s of p a r t i a l m o l a l p r o p e r t i e s ; the v a l u e s in Table 1
w e r e interpolated d i r e c t l y f r o m t h e s e r e s u l t s . R e f e r r i n g to Table 111, we s e e that d a t a a r e lacking f o r a b e low 250/0w and f o r the p a r t i a l mo1a.l heat capacity of w a t e r i n anhydrous
acid.
-13-
3.1
CT
E E
v
3.C
1.3
I .4
1.5
1 0 ~( O 1K )~
1.6
I. 7
MU-31441
Fig. 1.
. -
- 14 -
T a b l e 111. H2S04
(%w)
%m
2.00 4.39 5.77 7.30 9.00 10.91 13.06 15.52 18.33 21.60 24.44 30.00 32.08 34.33 36.78 39.44 42.35 45.56 49.09 53.01 57.39 62.31 65.00 67.87 70.93 74.21 77.73 81.51 85.59 90.00 92.25 94.79 97.34 98.92 99.46 100
~~~~
26.44 75.10 - 114.9 - 168.8 - 241.4 - 338.2 - 462.2 - 620.6 - 821.5 -1075.3 -1406.3 - 1836 -2038 - 226 1 -2508 -2783 -3090 -3427 -3789 -4167 -4557 -4960 -5165 -5375 -5595 -5830 -6090 -6390 -6741 - 7204 -7521 -7963 -8692 -9624 -10342 -12014
6.28 17.871 17.775 34.0 17.780 - 71.8 - 136.0 18.114 - 228.6 18.555 - 349.0 18.662 - 494.2 18.518 - 662.9 17.731 - 867.3 16.963 16.335 - 1125.0 15.173 - 1459 13.398 -1903 -2127 12.570 -2382 11.762 11.01 -2683 10.33 -3039 -3475 9.77 10.36 -4015 13.78 -4656 18.96 -5319 22.13 -5938 22.76 -6419 -6627 22.30 21.48 -6816 20.44 -6983 19.32 -7139 18.06 -7286 -7433 16.64 -7574 15.05 13.25 -7712 12.25 -7777 11.03 -7845 7.0 -7919 - 4.1 -8337 -15.3 -9355 -16125
- 15624 - 17078
0.0186 0.0178 0.0165 0.0249 0.0232 0.0153 0.0116 0.0006 -0.0207 -0.0296 -0.0358 -0.0330 -0.0182 0.0114 0.0568 0.1233 0.0666 -0.0120 -0.0346 -0.0398 -0.0427 -0.0436 -0.0428 -0.0405 -0.0368 -0.0314 -0.024 -0.019 -0.014 -0.008 -0.003 -0.001 0 -14115 -13373 - 12600 -11782 - 10906 -9995 -9045 -8054 -7G36 -5962 -4838 -4387 -3940 -3492 - 3046 - 2600 -2170 - 1766 1404 - 1086 -816 -699 -592.8 -495.2 -408.5 -323.5 -248.4 178.3 -114.3 - 85.3 - 54.6 - 26.00 - 9.32 - 3.50 0 -16279 - 15580 -14659 -13618 - 12527 - 1 1457 - 10445 -9437 -8405 -7320 -6158 -5664 -5144 -4601 -4025 -3394 -2705 -1994 - 1354 -851 -524 -405 - 309 -235.4 -176.3 - 129.6 - 92.1 - 64.5 - 44.6 - 38.9 - 33.8 - 30.6 - 24.2 16.7
22.18 25.65 25.70 20.97 15.93 14.90 15.92 20.62 24.44 26.95 30.69 35.34 37.17 38.80 40.17 41.27 42.08 41.37 37.57 32.65 29.99 29.54 29.81 30.22 30.67 31.10 31.50 31.86 32.17 32.43 32.52 32.61 32.76 32.95 33.04 33.20
- 0.0 26 8
-0.0 156 -0.0041 -0.0633 -0.0557 -0 .O 159 -0.001 1 0.0340 0.0895 0.1095 0.1220 0.1171 0.0935 0.0509 - 0.0069 -0.0830 -0.0270 0.0361 0.0511 0.0541 0.0557 0.0562 0.0558 0.0551 0.0543 0.0531 0.0520 0.0516 0.0514 0.0509 0.0509 0.0509 0.0509
~~
R e f e r e n c e 6.
IVY
In the calculation of p a r t i a l p r e s s u r e s f r o m the equations p r e s e n t e d i n Sec. 11, one depends upon r o o m - t e m p e r a t u r e heat-capacity m e a s u r e m e n t s on the solutions to predict t h e i r h i g h - t e m p e r a t u r e properties, Inherent in t h e method is the a s s u m p t i o n that the e x t r a p o In t h e p r e s e n t lation of the data will not g e n e r a t e significant e r r o r s .
c a s e , i t h a s been r e a l i z e d that the thermodynamic p r o p e r t i e s collected i n Sec. I11 might not give a perfect -a p r i o r i calculation of p a r t i a l p r e s s u r e s . Initial calculations tended to b e a r t h i s out. R e s u l t s t o t e m p e r a t u r e s near 200 " C w e r e s a t i s f a c t o r y , but at h i g h e r t e m p e r a t u r e s the calculated p a r t i a l p r e s s u r e s b e c a m e p r o g r e s s i v e l y m o r e e r r a t i c .
To c o r r e c t the o b s e r v e d i n c o n s i s t e n c i e s , it was decided t o adj u s t a, t h e t e m p e r a t u r e coefficient of the p a r t i a l m o l a l h e a t c a p a c i t y , The choice of a a s a c o r r e c t i o n t e r m was somewhat a r b i t r a r y . principle, either p e r a t u r e behavior, In
a could be changed, o r additional nonlinear t e r m s
howeverg r e q u i r e s t h e a s s u m p t i o n s
functions was a l s o n e c e s s a r y . The effect of a upon p a r t i a l p r e s s u r e c a n be given by a s i m p l i fied r e a r r a n g e m e n t of Eq. ( I 1 ) : log P log(P)a=o - Pa
P
(26)
w h e r e the f a c t o r
Above 2 0 0 " C , where F i g " 2 i n d i c a t e s t h a t a b e c o m e s a significant v a r i a b l e i n the p a r t i a l - p r e s s u r e equation (Eq v a l u e s of a will be s e e n to be inadequate,
(24) ) , the r e p o r t e d
By d e t e r m i n i n g a s u i t a b l e
a v e r a g e a f o r the r a n g e of 2 5 t o 400C, one can significantly alter h i g h - t e m p e r a t u r e p a r t i a l p r e s s u r e s without affecting the a l r e a d y s a t is f a c t o r y low-t e m p e r a t u r e v a l u e s
~
r e s u l t s and with the s u l f u r i c acid a z e o t r o p e and boiling-point data. C r o s s - p l o t s of log p v s Tow, T o r n , and 1/T w e r e used a s guides during
the calculation.
coefficient plots and examined f0r consistency by using the GibbsDuhem equation.
A,
T r i a l Calculations
, caland p H O H2S04 culated from Eq, (24) and p a r t i a l molal data. l i s t e d i n T a b l e 111. The
F i g u r e s 3 and 4 show trial values of p double s e t s of c u r v e s at 200C and above indicate r e s u l t s obtained by using ( a ) a as given i n Table 1 1 1 (dashed c u r v e s ) , and (b) a (solid c u r v e s ) . in (a) o r (b) w e r e p r a c t i c a l l y equivalent,
*-
It is not n e c e s s a r y t h a t the
p a r t i a l - p r e s s u r e c u r v e s be s m o o t h s but it is e s s e n t i a l t h a t t h e i r r i s e be monotonic; however, i t a p p e a r s significant that the c u r v e s at l o w e r t e m p e r a t u r e s a r e indeed r e l a t i v e l y smooth, F i g u r e 5 shows t h e v a l u e s of a l i s t e d i n Table 111, It c a n be s e e n that the e r r a t i c areas i n the calculated p a r t i a l p r e s s u r e s c o r r e s p o n d to th.e "peaks i n the a c u r v e s , Fig. 4 , the high value of p
It
and
"valleys
a t 47 O/OW, d e c r e a s i n g p r e s s u r e s H2S04 a r e the a t 847700~ through 7 4 7 ' 0 ~and ~ e x t r e m e l y high value of p H2S04 r e s p e c t i v e r e s u l t s of a low a a t 46.50/ow, i n c r e a s i n g v a l u e s of a t o
a m a x i m u m a t 74,50/0w, and a n abrupt m i n i m u m i n a at 84,5
YOW.
The v a r i a t i o n s in r o o m - t e m p e r a t u r e
v a l u e s with c o n c e n t r a -
tion, shown i n Fig. 5 , r e f l e c t the differences i n h e a t - c a p a c i t y b e h a v i o r P o s s i b l y the h y d r a t e c o m of the v a r i o u s hydrated f o r m s of HZSO 4" positions a r e not so distinct at t e m p e r a t u r e s o v e r 100 t o 2 0 0 C .
-17-
100
200
300
400
Temperature
("C1
MU-31442
Fig. 2. V a l u e s of P = ( l / a ) { l o g [ p/p(,=,)
]}
f r o m 25 t o 400"'C.
- 18-
IO
5
'om Giauge
2
0
Y-
I
O
h
(u
IO
5
CT
I E E
v
IO2
5
1
5' 0
Q)
L-
3
u) u) Q, L
IO
5
\ 25 O
t
60
.c L
0
a
0
I
5
2
lo- ' I
0
20
40
W e i g h t - percent
I
80
100
H,SO,
MU-31443
Fig. 3 .
Partial p r e s s u r e of w a t e r , t r i a l calculations.
-19-
lo4
!
IO
5
2
IO?
5
2
IO2
5
2
I
5
2
400C
30 lo-' I
20
40
60
80
IO0
Weight- p e r c e n t H,SO,
MU - 3 1 4 4 4
Fig. 4.
P a r t i a l p r e s s u r e of s u l f u r i c a c i d , t r i a l calculations.
-20
Moles H, 0 /mole
H , SO,
0 . 1f 0 . 1c
6.5
I
2
I
I
I
N
c
Y
0
Q,
-0
v
0.05
W -
0
L
r)
- 0.0 5
-0.IC
20
40
60
H , SO,
80
100
Weight - p e r c e n t
MU-31445
Fig. 5.
-21 -
B,
and a shown i n Fig. 5 w e r e a d H2S0 H2 j u s t e d s o that p a r t i a l p r e s s u r e s above Z&C w e r e consistent with lowtemperature results. Calculations w e r e c a r r i e d out s o a s t o i n s u r e a g r e e m e n t with sulfuric a c i d azeotrope and boiling-point data.
1.
f r o m Eqs, (24) and (25) with t h e smoothed constants eventually deduced] i n the vicinity of the s u l f u r i c a c i d a z e o t r o p e , A n a b s c i s s a s c a l e of -log
L 100-(ybw)]
pH2S04
nearly constant, at
PH~O d e c r e a s i n g r a p i d l y , and p
i n c r e a s i n g rapidly-continues
s03 h i g h e r t e m p e r a t u r e s and p r e s s u r e s .
w a s shown by Kunzler, l o who obtained the following data on the concent r a t i o n of constant-boiling s u l f u r i c a c i d at v a r i o u s p r e s s u r e s :
P (mm Hg)
100 200
HZS04
(TOW)
300
400
500 600
98524
98,509
98,479
6 50
IO00
OW a t
7 6 0 rnrn Hg, which w a s adopted f o r t h e p r e s e n t study. 4 Abel s u r v e y e d t h e available data on the t e m p e r a t u r e and
-22
IO -:
C
1 0 -
:
e
E E
IOC
1 0 5
I. d - 4 ~ i
70 80
90
95
98
99
99.5
99.8 ! 9
Weight - percent
H,S04
MU-31446
Fig. 6.
The s u l f u r i c a c i d a z e o t r o p e at 2 5 C .
-23-
3 26 330 338
-__-
In t h e p r e s e n t c a l c u l a t i o n s , it was decided t o b a s e h i g h - t e m p e r a t u r e p a r t i a l p r e s s u r e s on a t e m p e r a t u r e of 3 2 6 C for t h e 1,O-atm a z e o t r o p e , as wa.s done by Abel. 4' l 1 Although t h i s t e m p e r a t u r e i s r a t e d as t h e m o s t p r o b a b l e v a l u e , it is subject t o a n u n c e r t a i n t y of at l e a s t *5"C, At a n a z e o t r o p e t h e composition of t h e liquid is equal t o t h e composition of t h e v a p o r ( e , g. , i n m o l e - % u n i t s ) . R e f e r r i n g t o w a s t h e weight-fraction of s u l f u r i c a c i d at t h e a z e o t r o p e , a n d using t h e s u b s c r i p t s 1, 2, and 3 t o indicate H 2 0 , H2S04, a n d SO3, r e s p e c t i v e l y , we obtain 18.016~ 98.082 - 8 0 . 0 6 6 ~
I
p2
p3
( P , - P ~ ) I- ~ 2 + ~ 3
S = 0.92246, we obtain
(p,)2
+ pl[ Kp(l+S)-760(1-S)] -
760K = 0 , P
-24-
f r o m Eq. (31), p c a n be d e t e r m i n e d by 2 1 combining Eqs, (29) and ( 3 0 ) with the elimination of p3: 760-p,
Following evaluation of p
p2-
,1+(Kp/P1)
and 1 p2 can then be calculated f r o m Eq. (24), This p r o c e d u r e gave the following r e s u l t s f o r the sulfuric acid a z e o t r o p e : I n w t conditions t = 326"C, KP = 130.2 mm
P= 760 mm
p1
Results 233 .1 m m , a
~
TOW=98.48
2,
Adjustment of Alpha, 10 t o 98.5
OW
F i g u r e 7 shows the values of a calculated i n t h i s paper. The method of calculation used was suggested by the p r o p e r t y of a m e n tioned i n Sec. IV: a change i n a strongly affects h i g h - t e m p e r a t u r e p a r t i a l p r e s s u r e s without a l t e r i n g l o w - t e m p e r a t u r e values. c e d u r e u s e d was a s follows: The p r o -
(a) P a r t i a l p r e s s u r e s f r o m 25 t o 4 0 0 C w e r e calculated a t t e m p e r a t u r e i n t e r v a l s of 25"C, with a = 0 a t all weight-percents. (b) Starting a t 25"C, p r e s s u r e s w e r e plotted on log pv s - c o n c e n t r a t i o n and log p - v s - l / T coordinates. At e a c h 25" C i n t e r Up to
val, p r e s s u r e s at a = 0 w e r e checked against p r e s s u r e s calculated f r o m Eq. (26), by using a equal t o the a z e o t r o p e value. 150C t h e r e was no a p p r e c i a b l e difference. ( c ) At 1 5 0 C the difference between the p r e s s u r e s c a l culated with a = 0 and a equal to the a z e o t r o p e value was noticeable. The effect was a p a r a l l e l (downward) shift of the p r e s s u r e c u r v e ; no i r r e g u l a r i t i e s w e r e visible, equal to the a z e o t r o p e value, (d) By 200"C, i r r e g u l a r i t i e s o c c u r r e d i n the p r e s s u r e c u r v e s a t a c i d concentrations where a r e a c h e s a m a x i m u m o r a minimum, R e f e r r i n g t o Fig. 7 , t h e s e values w e r e 90, 8 2 , and 4ODJow f o r At subsequent 25C i n t e r v a l s , p r e s s u r e s w e r e calculated f r o m Eq. (26) by using the a p p r o p r i a t e
p and with
T h e s e new a values w e r e then u s e d f o r the next t e m p e r a t u r e i n t e r v a l . ( e ) The p r o c e d u r e of r a i s i n g t h e t e m p e r a t u r e by 25C and easing the a from the previous s t e p t o predict p r e s s u r e s at that t e m p e r a t u r e was continued, corrected. At 4 0 0 C the p r e s s u y e c u r v e s on the two c o o r d i n a t e s y s t e m s w e r e viewed a s a whole, and a n y d i s c r e p a n c i e s At t e m p e r a t u r e s o v e r 200C the net effect on a was t o
H2 on m o l e - p e r c e n t c o o r d i n a t e s .
F i g u r e 8 shows the heat capa.city sf s u l f u r i c acid a t 25"C, a s tabulated i n r e f e r e n c e 6 ; the p a r t i a l m o l a l h e a t c a p a c i t i e s a r e d e r i v e d f r o m t h e slope of t h i s c u r v e , The a v a l u e s shown i n Fig. 7 indicate t h a t at 4 0 0 C the wave between 15 and 45 Tow b e c o m e s m o r e pronounced, while t h e ' % u m p Y between ' 75 and 90
TOWi s
slightly broadened.
In the region between the a z e o t r o p e and 10070 a c i d a check of t h e activity coefficients showed t h a t a a d j u s t m e n t s alone would not give c o n s i s t e n t r e s u l t s o v e r the complete t e m p e r a t u r e range. was e s p e c i a l l y t r u e in the c a s e of p i n the high-weight - p e r c e n t region, This which changes v e r y l i t t l e H2S04 F u r t h e r m o r e , the s u l f u r i c a c i d
h e a t - c a p a c i t y data l i s t e d in r e f e r e n c e 6 show a c u s p at 10070 HZSO4' m a k i n g the p a r t i a l m o l a l heat c a p a c i t y of w a t e r i n d e t e r m i n a t e at that point, F i g u r e 9 s h o w s the poption of the h e a t - c a p a c i t y c u r v e (Fig., 8) between 96 and 102 Tow. The d a t a points a r e t h o s e of Kunzler and l2 6 Giauque which Ciauque s smoothed values (dashed c u r v e ) dv not folllow v e r y closely, The s o l i d i n r e f e r e n c e 6 below 9 8 - 5 Tow cuyve coincides with the d a t a l i s t e d and n e a r 101 TOW. R e s u l t s between t h e s e
-26 -
0.2 5
0.2c
0.1 5
N
c
Y
CT
Q,
'3
0.IC
E" . . 0
01 -
0.05
0
U
- 0.05
- 0. I C
i
MU-31447
Fig. 7.
-27
Moles H,O/mole
I
H, SO,
.o
6.5
P
D
V
Y
0.6
0.4
20
40
W e i g h t - percent
60
H,SO,
80
IO0
MU-31448
F i g . 8.
-28
96
97
98
99
100
IO I
Weight
percent
H , SO4
MU-31449
Fig. 9.
( b a s e d on two ions f o r m e d p e r molecule of by Young and Walrafen. 13) Then consistent H SO and a a t ?OO# p
e,
H2S0
w e r e v a r i e d t o give smooth activity-coefficient b e P h a v i o r between 98.5 and 1 0 0 7 0 ~ .R e f e r r i n g t o Fig. 9, t h i s p r o c e d u r e gave a h e a t capacity a t 10070, along with the 10070 i n t e r c e p t s of the s l o p e s of the heat-capacity curve taken at 99, 99.5, 99.8, and 9 9 . 9 7 0 ~ between 98,5 and 1000/0ww e r e then calculated H O by a s s u m i n g v a r i o u s %eat-capacity c u r v e s through t h i s region. P a r t i a l m o l a l heat c a p a c i t i e s w e r e calculated f r o m the 10070 i n t e r c e p t s d e terrnined above, and the a s s u m e d heat capacity; then p calculated by a s s u m i n g values of a. was H2 New heat-capacity c u r v e s and Values of p
w e r e obtained alphas w e r e a s s u m e d until consistent v a l u e s of p H2 at 99, 99.5, 99.8, and 9 9 . 9 7 0 ~ . The heat-capacity c u r v e was c h o s e n
sulting 100% p r e s s u r e s . T h i s p r o c e d u r e r e s u l t e d i n t h e heat-capacity c u r v e shown i n Fig. 9 f o r t h e 98.5- to 99.9-70w region and f o r the i n t e r c e p t and s l o p e a t 10070, The calculated value of below 100%. 100 to 101 positive, indicating t h a t the peak i n the h e a t - c a p a c i t y c u r v e o c c u r s The portions of the c u r v e between 99.9 t o 100 70w and d r a w n by a s s u m i n g a Gaussian-type v a r i a t i o n
(c ) 4 for P 5
TOW w e r e
a r o u n d t h e 10070 value. The v a l u e s of the p a r t i a l m o l a l p r o p e r t i e s f o r the 98-5- t o 100-TOW region a r e shown i n Table IV, below, The lOO($o values give
an a n h y d r o u s - a c i d boiling point of 2 7 2 " C , within t h e 27'0 t o 280C
r a n g e given i n the l i t e r a t u r e .
14
-30
o r3 o o o n o 0 Q Q
....................................
(3
fi5 (3 o
uooo
Q CJ
oo
~3
o c3 a o o o o o o o o o
0 0 0 a' 0 00 0
m0 . a clr
I - P- 0 O Nm 9 9m r- 9 m J m N 4 0
. . . . . . *. . .
* m
I
000
0m
rl
00 0000
0 0
Q d 0
e
n ,P - P- v\ d N l n \t
**
I
I
r l r l rl r l d 4 r l rl
n r-9 I
I
I I
Nl n9
n 4. . u , J l j . 0 N clr 0 OI ul 9 0 m r- 0 'm
d
N00
4.
e l n0 ,I n
Q rl
J Q m N rl rl I I I 1 I I
ul 4- m N 1 I I I
a ,a m P - m o N0 ,Q mN d l I I rl I I I I I I
0 .N
I
. .* * ....... *
m .o
clr r - Q ) S b
a +
-31-
C.
Results
0 and P H2S0
t h o s e given i n '$able 111, exce$ f o r t h e new values of a ( F i g . 7 ) a n d region. Partial t.ie o t h c r changes indicated above f o r t h e 99-to 100-TOW
, i-' . j : ~ u . r e s calculated
-32 -
1 0
lo5
-2oooc
IO
-150C
to3 -tow&-
20
40
Weight - percent
60
H2S04
80
100
MU R - I998
Fig. 10.
The p a r t i a l p r e s s u r e of
H 0 o v e r aqueous s u l f u r i c a c i d . 2
-33 -
Weight
.-
percent
H2S0,
M1 1R - I 9 B Y
-34
Weight - p e r c e n t
H , S O ,
MUR-2000
Fig. 1 2 .
T h e p a r t i a l p r e s s u r e of SO
o v e r aqueous s u l f u r i c acid.
-35-
V.
In both c a s e s the c l o s e s t a g r e e -
ment o c c u r s at low t e m p e r a t u r e s and low a c i d concentrations w h e r e the o b s e r v a b l e vapor p r e s s u r e is predominantly due t o p H 2 0 At higher t e m p e r a t u r e s Greenewalt * s t o t a l - p r e s s u r e c o r r e l a t i o n s gave slightly higher p r e s s u r e s than those r e p o r t e d h e r e . r e l a t i o n s w e r e t e r m i n a t e d at 1 atm. Abel u s e d a K equation and a n azeotrope composition difP f e r e n t f r o m those used i n this work, His r e s u l t s , while not d i r e c t l y c o m p a r a b l e to those p r e s e n t e d h e r e , show the s a m e t r e n d s in v a p o r p r e s s u r e behavior as do Figs. 10, 1 1 , and 12, d a t a now available, By r e f e r r i n g to the method j u s t d e s c r i b e d f o r adjusting a , At 2 5 " C , however, h i s calculated p r e s s u r e s a r e not i n a g r e e m e n t with the t h e r m o d y n a m i c
it b e c o m e s a p p a r e n t that p
vapor p r e s s u r e s .
v a p o r - p r e s s u r e data to aid i n adjusting a i n the low-%w r a n g e s with the a z e o t r o p e d a t a f o r calculating a in the high-yow region, the r e l i a b i l i t y of p f o r which we have only a z e o t r o p e d a t a , t h e H2S0 ' Gibbs-Duhem equation w%s applied i n the f o r m suggested by Redlich
F i g u r e 1 3 shows t h e
r e s u l t of t h i s t e s t a t 2 0 0 C ; the positive (left-hand) a r e a is 86.5 u n i t s and the negative (right-hand) a r e a is 87.5 u n i t s , which i n d i c a t e s t h a t m a y be a t r i f l e high in the low-weight-percent region, T h i s pH2S04 u n c e r t a i n t y a p p e a r s t o l i e within t h e a c c u r a c y of t h e p r e s e n t c a l c u l a t i o n s , and h a s not been f u r t h e r adjusted. R e g a r d l e s s of the calculational method u s e d f o r a , p r e s s u r e s c a l c u l a t e d a t low t e m p e r a t u r e s ( w h e r e a i s not a significant v a r i a b l e ) a r e a s a c c u r a t e as the avaiiable t h e r m o d y n a m i c d a t a allow, Changes
-36 -
20
40
60
80
1 0 0
Mole - p e r c e n t
H2S04
MU.31450
Fig. 13.
T h e r m o d y n a m i c - c o n s i s t e n c y t e s t a t 2 0 0 " C.
- 37i n a p t o c o r r e c t the h i g h - t e m p e r a t u r e p r e s s u r e s , affected the r e s u l t s up to 1 0 0 C by no m o r e than 2 7 ' 0 , The r e l a t i v e a c c u r a c y of the p a r t i a l p r e s s u r e s calculated i n diff e r e n t t e m p e r a t u r e and composition regions e s t i m a t e d qualitatively f r o m the foregoing c o n s i d e r a t i o n s , i s shown i n Table V. It i s f e 1t that t h e r e a l utility of the r e s u l t s p r e s e n t e d h e r e depends not upon t h e i r absolute a c c u r a c y but r a t h e r upon t h e i r i n t e r n a l consistency and upon the v e r s a t i l i t y of the calculational method. When additional data b e c o m e available, p a r t i c u l a r l y i n t h e 1 .O -atm a z e o t r o p e region, they m a y be i n c o r p o r a t e d into the general f r a m e w o r k of the calculation and the effect upon calculated r e s u l t s d e t e r m i n e d .
I
~
-38-
Table V ,
TOW
10-80 8 0 - 1 0 0
f
470
8 4
8
20
22
*loyo
*lWO
16 8
18
-39-
ACKNOWLEDGMENT T h i s work r e p o r t e d h e r e i n was c a r r i e d out at the L a w r e n c e Radiation L a b o r a t o r y under the a u s p i c e s of t h e U. S , Atomic E n e r g y Commi s s ion
-40-
NOTATION Superscript B
o (lower-case
-.
pV~h' R fe )f e r s to v a l u e s a t s t a n d a r d s t a t e R e f e r s to p a r t i a l m o l a l quantity
(overscore)
Subscripts
IL
2
3 298
( 1)
O(zem) R e f e r s t o p r o p e r t y a t 0 O K
Thermodynamic Functions
F
H
S G
a
P a r t i a l Molal Functions
(F-FO)
Relative p a r t i a l m o l a l f r e e e n e r g y
E cP
a .
Partial m o l a l enthalpy
P a r t i a l m o l a l h e a t capacity T e m p e r a t u r e coefficient of
a = d
P'
/dT
-41-
P
t T
"C
Temperature, " K
K R
1
7 0w
T o r n Male-fraction KlOO
-42-
APPENDIX
Tables A- I through A-111 p r e s e n t the detailed r e s u l t s calculated f r o m E q s , ( 2 4 ) and (25) and the p a r t i a l m o l a l p r o p e r t i e s l i s t e d i n Table I V , Table A-I contains the l o w - t e m p e r a t u r e r e s u l t s ; io e. , t h o s e r e s u l t s unaffected by changes i n a, p e r c e n t s shown i n Table IV. Table A-11 p r e s e n t s g e n e r a l i z e d r e s u l t s f r o m 0 t o 4 0 0 C . P a r t i a l p r e s s u r e s of H 0, H2S04, and SO3 plus t h e t o t a l p r e s s u r e a r e 2 shown i n Subtables ILA, LIB, TIC, and IID, respectively. Tabulated p r e s s u r e s a r e rounded to four significant f i g u r e s and t e r m i n a t e d at 4 -4 10 and 10 mm Hg. Table A-1.11 is included as a quick r e f e r e n c e s o u r c e and summ a r y of r e s u l t s . Abbreviated lists of p a r t i a l p r e s s u r e s a r e P r e s s u r e s a r e rounded -2 to t h r e e significant f i g u r e s and a r e t e r m i n a t e d at IO4 and 10 mm Hg; r e s u l t s a r e shown f r o m -50 to 390"C, T a b l e s A-IV and A-V among t h e above t a b l e s , a r e included to aid i n interpolation Table A-IV l i s t s the v a l u e s of t h e c o n s t a n t s p r e s e n t e d i n Subtables IIIA, IIIB, and IIIC. P a r t i a l and total p r e s s u r e s a t
5OC i n t e r v a l s between -50 and t 1 0 0 " C a r e tabulated f o r t h e
36 weight-
f r o m -50 t o 390C, P The F o r t r a n listing of the p r o g r a m u s e d to c a l c u l a t e t h e p r e s s u r e s l i s t e d i n Table A-I1 is included as Table A-VI. Similar p r o g r a m s
w e r e w r i t t e n t o produce T a b l e s A-I and A-111.
-43 -
A 0 Lu N
) L
m m \ t r n r r ~ . - c + ~ o
NNNNNNNNNN
m
d
m
pc
u
m
VI
I
4
w
I 0
C
I -
V
(3
-44-
m
I 7
-I
Lu
b-
~ - ~ . - I I ~ - I N N ~ ui n . $
:>
.......... .
0 I4 3 IC r \ l IC TI c-l
IF
m
4
a cz:
w t Y
m Ln m
m
UJ
a nc
Lu
h
w
I -
3 0
..........
m
0
a N r
m b
I n
.
e
d d d C'J
w
( r
eo
0C
NN N N N N 3 ~ 0 0 0 0
~ ~ m m m m m m m m m
i3000000000
a
W
I )
a
c
c
v , v ,
Ln
c3
t9
N N N N N N N d d d
to
r*?
w w w
LLt
w w w w UJ w
uv) a c
-45
m
0
J
c n c
IC
*
I
it 9
N
d
m
t-0
0 ,
urn
I 3 :
0
' A . a
P-
e
e
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m r . o m N
C>'3'303
C ~ N
dNll3?1\
00000
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u
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0
.
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OC,0"
....
d
0
J 2
C '
0
N
0 0
4
-76Table A-IV.
WT PCT 10.0
COMPa
2 0 .o
25.0
O 30 .
35.0 4 0 .O 45.0 50.0 55.0 60 -0 65.0 70.0 72.0 7 4 .O 76.0 78.0
1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2
1
2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2
1
80.0
82.0 84.0 86.0 88.0 90 - 0 91.0 92.0 93.0 '34.0 95.0 96.0 97.0 98.0 98.5 99.0 99.5 99.8 99.9
2 1 2 1 2
1
2 1 2 1
2 1
100.0
2 1 2
A 0.982730E 0 1 -0.128982E 02 0.377200E 0 1 -C.134*325 0 2 0.377451E 0 1 -0.139775E 02 0.105427E 02 - 0 . 2 2 3 5 8 9 E c12 0.112147E 3 2 -0.308963E 6 2 0.112686E 02 -0.323148E 02 0.111961E 0 2 02 -0.310513E 3.997490E 01 -0.237353E 0 2 0.898832E 0 1 -9.189624E 02 C.799717E 01 -0.167992E 0 2 O.621220E 0 1 -0.126668E 02 0 . 3 6 6 8 6 7 E 01 -G.627602 0 1 0.235183E 01 -0.340476E 01 0 . 1 3 4 5 0 6 E 01 -0.934196E 30 -0.3a3569~-~0 0.170559E 0 1 01 -0.172599E 0.390946E 0 1 C1 -0.370810E 0.611742E 51 -0.386130~ 01 0.651030E 0 1 I). 4 1 0 1 8 7 E - 0 0 0.159751E 0 1 0 . 0 0 4 2 8 2 E 01 -0.537919E 0 1 0.122635E 0 2 -0.a81814~ 01 0.127306E 02 -0.949468E 01 0.118990E 02 -0.920879E 01 0.105862E 02 -0.870240E 0 1 0 . 3 0 1 2 6 1 E 01 -0.817590E 01 0.754884E 0 1 -0.7h5944E 61 0.631467E 0 1 01 -0.733815E 0 . 4 9 2 4 9 8 E 01 -0.694696E 01 G.329972E 0 1 -0.668594E 31 0.1C4367E 01 -0.642i308E 0 1 0.903753E-01 01 -0.632778E - 0 . 1 4 0 5 4 5 E 01 -3.614434E 01 -0.489211E 0 1 -0.577858E 01 -0.185363E 02 -0.540286E 01 - 0 . 2 9 2 7 3 0 E G2 -0.538282E 01 0.212753E 02 -0.548803E 01
-0.749883E -0.163377E -0.749838E -O.l612;77E -0.751815E -0.156870E -0.769003E -0.136193E -0.786989E -0.114447E -0 e 794653E -0 1U60 69E -0.799799E -0.103334E -0.784179E -0.112673E -0.773996E -0.117582E -0.767477E -0.117496E -0.748958E -0.121003E -0.720067E -0.128171E -0.705497E -0.131338E -0.692787E -0.1336276 -0.680995E -0.135858E -0.670814E -0.137073E -0.661987E -0.137794E -0.691302E -0.134380E -0.812890E -0.120627E -0.998894E -0.103316E -0.111674E -0.936625E -0.115263.E -0.906709E -G. 114725E -0.907@09 -0.113104E -0.912802E -0.110819E -0.920323E -0.108581E -0.928274E -0.136536E - 0 . 9 3 3 7 14E - 0 . 1 0 4 139E -0.940360E -0.131233E -0.945287E -0.972137E - 0 . 9 5 0 1 OOE -0.953695E -0.951834E -0.921465E -0.954960E -0.834654E -0.961414E -0.564741E -0.968278E -0.408354E -0.968466E -0.186024E -0.966251E
04 05 04 C5 t 4 05 04
05
04 05 04 05 04 05 04 05 04 05 04 05 04 05 04 C5 04 05 04 05 04 05 04 05 04 05 04 05 04 05 04 05 05 04 05 04 G5 04 05 04 05 04 05 04 05 04 05 04 fi5 04 04 04 04 C4 04 04 04 04 04 04 04 04 05 04
C 0.258356E 0.272789E 0.257519E 0.302233E 0.257511E 0.303210E 0.259365E 0.276911E 0.261922E 0.247785E 0.262859E 0.238974E 0.262492E 0.241423E 0.258706E 5.264C27E 0.254900E 0.282963E
02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02
0.251806E
0.295357E 0.2460G9E 0.313991E 0.237319E 0.336749E 0.233523E 0.345232E 0.229998E 0.3522t2E 0.227125E 0.357492E 0.225073E 0.360834E 3.224429E 0.361787E 0.230825E 0.353843E 0.252743E 0.329540E 0.2836L9E 0.303G9OE 0.333436E 0.283583E 0.307922E 0.283356E 0.305658E 0.281681E 0.301178E 0.283916E 0.295050E 0.286586E 0.288080E 0.289216E 0.279833E 0.291875E 0.270105E 0.294321E 0.258560E 0.2965Y8E 0.244C17E 0.298651E 0.234732E 0.299497E 0.219462E 0.300430E 0.1~2543 0.301802E 0.114842E 0.303035E 0.883038E 0.303121E 0.414274E 0.302846E
02
02 02 02 02 02 02
02
02 02 02 02 02 02 02
02
02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 02 ~ 02 02 02 01 02 02 02
0 0.816702E-,2 -C. 2 2 1 0 3 3 E - 2 1 0.816732E-42 -O.258773E-u1 @.816702E-i2 -0.268838E-01 O 9 1 7 3 4 3 E -8.1 2 -0.369479E-jl 3.992824E-22 -0.470120E-31 0-992824E-,2 -3.4852 16E-J 1 0.972824E-32 -0.472636E-Dl 0.854443E-bZ -0.3a9637~-,1 0.753802E-L2 -0 3 4 1 8 J ~ E - 0 1 0 . 6 4 3 5 8 1 E-02 -0.3267CbE-i 1 3.439298-~2 -0.288966E-31 0.162535E-Lt2 -3*221333E-:1 0.115738E-53 -0.188325E-J1 -0.139386E-u2 -0.163648E-il -0.315510E-GZ -O.l2794DE-~~l -0.516792E-C2 -0.103264E-Jl -0.768395E-w2 -0.700714E-32 -0.843875E-wZ -0- 574913E-02 -0.416151E-S2 -0.107812E-01 0.426718E-C2 -0.183293E-Jl 0 867G23E-02 -0.218517E-01 0.892183E-uZ -0.226;65E-d1 0.791542E-32 -0.223549E-01 0.640 5 8 1 E-52 - 3 2 1 8 5 17E-u 1 0.464459E-32 -0.213485E-01 0.313497E-32 -0.208453E-jl 0.2 1 2 856E- \r2 -0.206443E-32 0.996347E-03 -0.202918E-dl -0.387468E-03 -0.201156E-31 -0.265189E-02 -0.198892E-L1 -0.340670E-C2 -0.198 I 3 7 E - 5 1 -0.441311E-u2 -0.196124E-21 -0.592273E-02 -0.191847E-31 -0.188551E-bl -o.i~73ia~-ji -0.316114E-31 -0.187067E-01 0.129223E-51 -0.188325E-ul
-77-
0 I 0 I 0 I 0 I 0 I 0 0 0 0
wlLwwLiJuJ111urw
mmmdodtQmm
a m * + \ t c a ~ o ~ o ~ m ( r r - m m ~ ~ d 6 O + ~ N S N ~ O N mmdN.tmmww aoooooooa
.........
0
vooooooooo
0 c3 0 0 0 0 0 0 0
( 3 . . . . . . . . .
ad8tm&(r&o.&m
I1
U l o O O O O CJ 0 0
d d ~ ~ r n r n
000000000
.........
o - n & ~ o d ~ m m
+oaoooooo
I I I I I
nl+r-am-4m-1~.0 Y N N Q S d O O b N
111uJuJuJuJuruJuI111
mSamlndwoca
W N F m - 4 N d d \ t
000000000
v 0 0 0 0 0 0 0 0 O O O O O O O O O O
.........
U 0 000 0 0 00 0
0
O O O Q O O O O O
wowooooooo
I
.........
- 4 + ~ ~ m m
cJ\t-4~-4a-t~da
000000000
vo o
0
a m
1 1 1 0 0 0 0 0 0 0 ' 3 0
......... .........
aoooooo
rnolnolnom
0000000
. . - I A N N ~ ~
-75-
-79-
C
110 C C Y T I N L F r
% K I T E CliTPUT T A P L IKT 1
3,50,
AKP,~jkP,CKP,DKP,EKP,FKP, ( T T ( K ) ,XKP(K),K=l.
C
3 1 5 P l I t J V K ) = G.0 C C T O 360
C
3 2 0 G = G+l.O M = ;<Ib!TF(G) GO T O ( 3 ? 0 , 3 3 5 , 3 4 0 , 3 4 5 ) , M 3 2 5 t- = 0,0001 GO 10 350 3 3 0 I- = O . C O 1 GC T O 3 5 0 3 3 5 I- = 0 . 0 1 GO T O 3 5 0 7 4 0 I- = 0.1 GO TC 3 5 0 3 4 5 k = 1.0
_ .
I _ -
-80-
TASLE A-VI.
355 P(I,J,K) = P(IpJ,K)+H 360 CONTINLE
(CONT.)
V
V
V
C
CO 400C K = l , I < T IF (TT(K)1 4001,4C02,4002 = T T ( K ) - C.5 4001 TT(k) G O TO 4 0 0 0 4002 TT(K) = T l ( K ) + C.5 4000 I T T l K ) = T T l K I
r o ~ O O C1 = 1 , 4 PM = 2 J X = J1 6 0 0 0 J Y = J X + 11 IF (JY - J4) 5000~6005y6010 6010 J Y = J N 6 0 0 5 PM = 1 5 0 0 0 G O TfJ ~ 5 0 0 5 ~ ~ 0 1 0 ~ 5 ~ 1 ,5 I ~ 5 0 2 0 ~ 5 0 0 5 d R I T E ClJTPlJT TAPE 3 , 5 0 0 4 5006 FOLMAT ( l H 1 , 3 0 X , 5 5 H T A B L E A - I I A , CONTINUED. 1, PM P C . 1 GO TU 7 0 0 0 5 0 1 0 W R I T E CUTPUT TAPE 3 9 5 0 1 1 CONTINUED. 5 0 1 1 FORMAT ( l H l , Z h X ~ 6 3 H T A B L E A-118, l P K E S S U K E , M M HG.) G O TI1 7 0 0 0 5 0 1 5 W R I T E C U T P b T TAPE 3 , 5 0 1 6 5 0 1 6 FORMAT ( l H 1 , 2 5 X , 6 5 H T A B L E A-IIC, CONTINUED1 L PRESSURE, F1M HG.) GO TO 7000 5 0 2 0 W K I r F GUTPUT TAPE 3 1 5 0 2 1 5 9 2 1 FORYAT ( l H 1 , 3 4 X 9 4 7 H T A B L E A - I I D , CONTINUED.
1)
CJATER P A R T I A L PRESSURE
SULFUR T R I O X I D E P A K T I A
TOTAL PRESSURE,
MM HG.
7 0 0 0 W R I T E OUTPUT TAPE 3 9 7 0 0 5 , ( W ( J ) , J = J X , J Y ) 7 0 0 ' 5 FOKPAT ( l H 0 , S H U E G C , 4 t % , Z O H W E I G H T PEKCENT H 2 S C 4 / 5 X , 1 2 F 9 . 1 ) PMM = 2 K1 = 1 K2 = 0 7 0 1 0 K 2 = K 2 + 10 I F (K2 - KT) 7015~7020,7025 7 0 2 5 K2 = K J 7 0 2 0 MKM = I 7 0 1 5 W K I T E CUTPUT TAPE 3 , 7 0 3 O , ( I T T L K ) , ( P ( I , J , K ) 9 J = J X , J Y ) , K = K l , K 2 ) 7 0 3 0 FORMAT ( l H O , I 4 , 3 X , l Z F 9 ~ 4 / ~ l X , I 4 , 3 X ~ l 2 F 9 . 4 ) ) KL = K2 + 1 GO T O ( 7 0 3 5 9 7 0 1 0 1 , P P M 7 0 3 5 J X = JY + 1 G3 T O ( R 0 0 0 , 6 0 0 0 ) , P M 8 C O O COIVT I N L E
C
I F (NPROBS-IPROB)
600~600~100
600 CALL E X I T
END
5. 6.
7.
8.
9.
11 G. N. Lewis and M. Randall, T h e r m o d y n a m i c s and t h e F r e e E n e r g y 0 f Chemical Substances, 1st ed. (McGraw-Hill Book Company, Inc, , New York, 1923), p. 554. 12. J. E. Kunzler and W. E", Giauque9 J. A m . Chem. SOC. 74, 3472
(1952).
13. T. F. Young and G. E. Walrafen, T r a n s . F a r a d a y SOC. 57, 34
(1961). 14. W. W. Duecker and J , R. West, The Manufacture of Sulfuric Acid (Reinhold Publishing Corporation, New York, 1959), p. 434.
15. 0, Redlich and A. T. a s t e r , Ind. Eng. Chem. 40, 341 (1948).
A.
Makes any w a r r a n t y o r r e p r e s e n t a t i o n , e x p r e s s e d o r implied, with respect t o the accuracy, completeness, or u s e f u l n e s s o f t h e i n f o r m a t i o n c o n t a i n e d i n t h i s r e p o r t , o r t h a t t h e u s e o f any i n f o r m a t i o n , appar a t u s , m e t h o d , or p r o c e s s d i s c l o s e d i n t h i s r e p o r t may n o t i n f r i n g e p r i v a t e l y owned r i g h t s ; or Assumes a n y l i a b i l i t i e s w i t h r e s p e c t t o t h e use o f , or f o r damages r e s u l t i n g from t h e u s e o f a n y i n f o r m a t i o n , a p p a r a t u s , m e t h o d , or p r o c e s s d i s c l o s e d i n this report.
B.