I

UCRL- 10886 UC-4 C h e m i s t r y TID-4500 (19th Ed. )

UNIVERSITY O F CALIFORNIA L a w r e n c e Radiation L a b o r a t o r y B e r k e l e y , California C o n t r a c t No. W- 740 5 -. eng- 48

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

VAPOR-LIQUID EQUILIBRIA FOR AQUEOUS SULFURIC ACID Contents Abstract

I

* . , .

v 1 3

1.

Introduction A, 3. P a r t i a l - P r e s s u r e Equation

11. Derivation of Equations

e

1 1 1 .

Dissociation Constant of H 2 S 0 (g) 4 T h e r m o d y n a m i c Data

.
, . .

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

.
.

P a r t i a l Molal P r o p e r t i e s T r i a l Calculations Heak Capacities

IV.

Calculation of P a r t i a l P r e s s u r e s A.
B.

. . .
. .
a a

.
e

Adjustment of High- T e m p e r a t u r e Partial Molal

1.
2.

Sulfuric Acid Azeotrope

98,li- and 100-70w Region

. .

. .
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

Acknowledgment Notation Appendix References

e

-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)

Partial p r e s s u r e (mm Hg)

H2

(74
10

H2s04 10-15 10-10

2x10-3

s03

25
100

20
7klO2 6x1 04

10-16 10-6 10-17 10-11 10-3

10-8

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 - ~

6x10-2 3 1.8XlQ 1 " 2X1O2

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

s u l t , b a s e d e s s e n t i a l l y on t h e m e a s u r e m e n t s of Burt' and of Daudt, i s the a c c e p t e d s t a n d a r d t h a t a p p e a r s in todayos r e f e r e n c e w o r k s .

- 2-

Method ( b ) , the calculational approach to p a r t i a l p r e s s u r e s , r e q u i r e s two types of t h e r m o d y n a m i c d a t a :

(1) pure-component data f o r two liquids and t h r e e g a s e s

and G o ) , and (H;98' '"298 P ( 2 ) p a r t i a l m o l a l d a t a for binary solutions F2989 and

(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

2 5 " C , t e s t e d f o r i n t e r n a l consistency, have been published by Giauque

et al.

who give f r e e e n e r g i e s , enthalpies, e n t r o p i e s , and heat c a .

pacities at 109 different s u l f u r i c acid c o n c e n t r a t i o n s f r o m 8.93 t o

~ O O T O W , In addition, Giguere' h a s obtained C o S o , (Fo - H g ) / T , and 0 PP (Ho - El ) / T f o r H2S04(g) f r o m s p e c t r o s c o p i c data., The l a t e r d a t a , 0 when coupled with Bodenstein and K a t a y a m a ' s K d a t a , provide a P t h i r d - l a w Ho l o r H2SQ4(g) and a n equation giving the t e m p e r a t u r e 298 dependence of K f r o m 2 5 to SOOC, P B a s e d upon t h e s e new d a t a , t h i s p a p e r p r e s e n t s a m e t h o d f o r

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

values have had t o be e s t i m a t e d by smoothing t e c h n i q u e s ,

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

m a d e f o r nonideal-gas b e h a v i o r , and 10 000 mm is viewed as the u p p e r l i m i t of applicability of the r e s u l t s .

11.. DERIVATION O F EQUATIONS

A,

P a r t i a l - P r e s s u r e Euuation

F o r any component i n a multicomponent m i x t u r e a t e q u i l i b r i u m ,

the p a r t i a l m o l a l f r e e energy of the v a p o r i s equal to the p a r t i a l m o l a l f r e e e n e r g y of the liquid:

q g g ) = F(P) (2) If t h e p r e s s u r e i s low enough s o that t h e v a p o r a c t s as a perfect gas,

Equation (3b) holds at any t e m p e r a t u r e and composition.

The

p a r t i a l p r e s s u r e under consideration is given by the sum of t w o t e r m s :

a pure-component t e r m , -AF"JR'L a function of. t e m p e r a t u r e only; and

a n activity t e r m y In a , a function oi both t e m p e r a t u r e and composition. In o r d e r t o evaluate t h e p r e s s u r e y e a c h t e r m m u s t be r e l a t e d to its s t a n d a r d - s t a t e value. T h e pure-component t e r m is evaluated as foPPows :
d

--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 ) .

;abr;cript shown a s 2 9 8 i s a c t u a l l y computed a s

--

The activity t e r m i s evaluated in a. s i m i l a r m a n n e r : In a =

- Fo RT '

'298 R(&8-$)-4J
298

s{[98
I T

298

Combining Eqs. (3b), (5), and, ( 7 ) , we obtain

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)

This g i v e s , upon combining G 1 9 G2' and G 3 ( T ) : 298 In p = A h T where

1 A = R (-a-tc p, 298

+ 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)

1 E = TRc F o r the sulfuric a c i d s y s t e m , p a r t i a l molal quantities a r e a v a i l a b l e f o r H 2 0 and f o r calculate p

H2 calculated f r o m

H2S04" Equation ( I l l ) was t h e r e f o r e u s e d to

and p H2S04

, and the p a r t i a l p r e s s u r e of SO3 w a s

psoj
3.

Kp 'H2S04 / p H 2 0

"

Dissociation Constant of H,S04(g)

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

The t e m p e r a t u r e dependence of K is obtained by e x p r e s s i n g AF71) P as a function of t e m p e r a t u r e : d dT

14a) The s t a n d a r d f r e e - e n e r g y c h a r g e for the r e a c t i o n i s t h e r e f o r e 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

Heat-capacity d a t a a v a i l a b l e i n the l i t e r a t u r e give t h e following function f o r

ACO

P(1)
=:

ACo P(1)

a ' t b ' T t .IT2 t d ' T - '

Use of t h i s t o evaluate t h e h e a t - c a p a c i t y i n t e g r a l i n Eqo (16) r e s u l t s i n the following equation f o r K :

.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

111, THERMODYNAMIC DATA

A, Pure-Component P r o p e r t i e s

The pure-component data r e q u i r e d in Eqs. (11) and (18) a r e l i s t e d i n Table I,

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)

a t 100C i n t e r v a l s f o r HZO(g) and S 0 3 ( g ) .

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:

Gigusre s t a b l e s 7 of ( F O - H i ) / T and ( H o - H i ) / T w e r e a l s o c o n v e r t e d t o the s a m e f o r m :

F O - H " ~ ~

f o r H2S04(g)

0 F0 -Ho

298.15 I T

HO

-H :

(20)

298

This p r o c e d u r e gave the following r e s u l t s :

500 600
700

44,03

74-32
761~2.2

62,73 63,93 65,19 66,46

0 0

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

Values of t h e r m o d y n a m i c p r o p e r t i e s a t 298.15 P r o p e r t y State Value

.-94.45

OK.

Units kcal/mole cal/mole-deg

Reference
~ ~~

s03

H0
SO

g g g

61,24 aZ13.90 b=6. 10X10-3 d=-3.22X105 -68.32 - 57.80 16.72 45.11

(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

a = 7.30 b = 2 46 x l 0 10.52 28.39

-193.91 -175.01 37.50 71.93

(9)

H2S04

H0
SO

(8) See text

(6) (7)

o c a : g C g P

Vaporization Dissociation

AHO

AS0 AHo(l) AS0( 1) 1)

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_.

By u s e of Eq, (22BUt h e r e f o r e , a value 0 f [ AHo

Eq, ( 1 ) c a n be calculated f r o m each K d a t a point: P
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

Table I P 19.29 19,39 22-14

24,40

308
400

500

600
700

26,08
2?,36

26"14 27.36

- 10-

Table 11.

Bodenstein and Katayama e q u i l i b r i u m d a t a for ~ ~ S 0 ~ = ( HZOtg) g ) -t S 0 3 ( g ) . a

741

-3.75

598 6 22 635 668 70 1 717 682

3.34 1.98 0.99 -0.68

633 653

0.85 0.75 -0.66 -1-78 -3.12 -1.78

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

646 660 664 693 708 731 7 56

1.17 0.30
0,oo

596

6 29

-1.12

610 635 653 655 680 707

2.87 1.06 0.20 0.09 -1.09 -2.37

611 629 647 660 6 89 714 689 658 637

3.24 2.08 1.12 0.54

- 2,22
-3.35 -4.24

- 1.03
- 1.88
-1.03 0.50 1.55

613 627 639 652 693 729 660 643

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

Table I, t h e following equation is obtained f o r calculating p pHzS04'

where

E = constant, Term
AQ
Sf

Units Dimensionless oK Damensisnle s s

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

- 12f o r the calculation of p

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'

A value of 1.98726 cal/mole-deg was u s e d f o r R , and 298.15

was u s e d w h e r e v e r 298 is indicated i n E q s . (11) and (18), B. Partial Molal P r o p e r t i e s

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.

E s t i m a t e d values of t h e s e v a r i a b l e s a r e given i n Sec. I V , fol-

lowing evaluation cuf the bulk of the data,

-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.

T h e fit o f Eq. ( 2 5 ) t o Bodenstein and Katayama's data.

. -

- 14 -

T a b l e 111. H2S04
(%w)

P a r t i a l m o l a l q u a n t i t i e s f o r s u l f u r i c a c i d at 298.15 " K ( f r o m Giauque"). Water Sulfuric a c i d

%m

10 20 25 30 35 40 45 50 55 60 65 70 72 74 76 78 80 82 84 86 88 90 91 92 93 94 95 96 97 98 98.48 99 99.5 99.8 99.9 100

a

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

CALCULATION O F PARTIAL PRESSURES

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

could be added to Eq. (10) to d e s c r i b e a s s u m e d heat-capacity-temE i t h e r choice

~

howeverg r e q u i r e s t h e a s s u m p t i o n s

i m p l i c i t i n smoothing the calculated r e s u l t s ; a f t e r s o m e c o n s i d e r a t i o n ,

it w a s decided t o adjust a, In a few c a s e s , m i n o r a d j u s t m e n t of o t h e r

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

p is shown i n Fig. 2 as a function of t e m p e r a t u r e ,

1 1 w e r e originally d e t e r m i n e d between Most of t h e a values of T a b l e 1

- 2 0 and + 2 5 " C ; a small n u m b e r w e r e b a s e d upon d a t a up to 8 0 C .

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
~

As explained below, a was adjusted s o that p a r t i a l p r e s s u r e s

i n the 200 to 4 0 0 C range w e r e consistent with the l o w - t e m p e r a t u r e

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.

Smoothed p a r t i a l p r e s s u r e s w e r e checked on activity-

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,
*-

Below 2 O O 0 C , r e s u l t s obtained by using a e i t h e r as

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

F o r example, following the d a s h e d 4 0 0 C c u r v e i n

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
!

=O from Giaugue et al,

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.

T e m p e r a t u r e coefficient of p a r t i a l m o l a l heat c a p a c i t i e s , m e a s u r e d at 2 5 " C , f r o m Giauque e t al. 6

-21 -

B,

Adjustment of High- T e m p e r a t u r e P a r t i a l Molal Heat Capacities The values of a

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.

Sulfuric Acid AzeotroDe F i g u r e 6 shows the p a r t i a l - . p r e s s u r e behavior at 2 5 C calculated

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)]

is u s e d i n Fig. 6 i n ordeT to expand the a z e o t r o p e region.

The p a p t i a l - p r e s s u r e behavior shown-

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 .

The concentration at which t h e

a z e o t r o p e o c c u r s , however, d e c r e a s e s a s the p r e s s u r e i n c r e a s e s . This

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

HZSOq (Tow) 98,790 98,704 98,645 98,597 98.557

p B m m Hg) 700 750 800 850 900 9 50

HZS04

(TOW)

9 8, 4 9 5 98,482 98,469 98,457 98,446 98.436 98,426

300
400
500 600

98524
98,509

98,479

6 50

IO00

Interpolation of Kunzler s d a t a gives a n a z e o t r o p e concentration of

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

c o n c e n t r a t i o n f o r the a t m o s p h e r i c - p r e s s u r e a z e o t r o p e ; the r e s u l t s of v a r i o u s e x p e r i m e n t e r s a r e as follows :

-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

98.39 98.33 98.3

338 338 3 17 331.7

98.5 98.5 98-54

-__-

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

F o r t h e 1 . 0 - a t m a z e o t r o p e , we t h e r e f o r e obtain p2sp3 0.92246 = p1 'P2

~

At t h i s a z e o t r o p e we a l s o have 760 = p1+p2+p3 , K = P1 P3/P, P Since t h e v a l u e of K at 3 2 6 C c a n be d e t e r m i n e d f r o m P Eq. ( 2 5 ) , t h e p a r t i a l p r e s s u r e s at t h e a z e o t r o p e c a n be d e t e r m i n e d by

0

combining Eqs. ( 2 8 ) , (29), and (30), E l i m i n a t i n g p 2 a n d p3, and using

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

The a values r e q u i r e d t o give the c o r r e c t a z e o t r o p e p

P= 760 mm

= 0.0160, 1 p2 = 338.1 mm, a 2 = 0.1249,

p3 = 188.8 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

both H 2 0 and H2S04r, I r r e g u l a r i t i e s w e r e smoothed visually and the

a r e q u i r e d to give the smoothed px-essure was calculated f r o m Eq. (26).

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

fill i n the portions between the m a x i m a and m i n i m a i n the a c u r v e s ,

Fig. '7, The above p r o c e d u r e was followed f o r calculating both a and a F o r e a s e of interpolation, p

H, 0 was smoothed onL

H2S04 weight - p e r c e n t c o o r d i n a t e s , and pHzSo4

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

w e i g h t - p e r c e n t s w e r e calculated a s fo'l L ows.

0 F o r s u l f u r i c a c i d , values oi (F-F 3 w e r e adjusted a t 99, 99.5,

99.8, and 9 9 . 9 7 0 ~ s o that p

H204

gave Raoult - L a w behavior a t 25 C

-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.

Average t e m p e r a t u r e coefficient of p a r t i a l m o l a l heat c a p a c i t i e s , between 25 and 400 C.

-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.

The heat capacity of aqueous s u l f u r i c a c i d at 2 5 C .

-28

96

97

98

99

100

IO I

Weight

percent

H , SO4
MU-31449

Fig. 9.

The heat capacity o f aqueous sulfuric acid n e a r 1005; H2S04.

( 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

P' behavior a t high t e m p e r a t u r e s ;

e,

added, a s indicated 4 and a w e r e adjusted to give a t the s a m e t i m 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

s o that t h e s e p r e s s u r e s 2 when extrapolated, gave a n acceptable boiling

point a t 10070 acid, Then

and a f o r HzO w e r e fitted to the r e -

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

10070 was l a r g e and

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

Table IV lists t h e t h e r m o d y n a m i c p r o p e r t i e s u s e d i n t h e c a l culation of p

0 and P H2S0

T h e values shown a r e i d e n t i c a l with

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

from Eqs. ( 2 4 ) and ( 2 5 ) , and the d a t a i n T a b l e I V , Complete t a b l e s of p a r t i a l p r e s -

d r c s ~ ~ ) iw n i Fi ~ g s . 10, 11, and 1 2 .

s u r e s a p p e a r i n t h e Appendix, t o g e t h e r with the F o r t r a n p r o g r a m u s e d

f o r t h e calculation.

-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.

DISCUSSION AND CONCLUSIONS

The p a r t i a l p r e s s u r e s p r e s e n t e d above a g r e e i n f o r m with t h o s e r e p o r t e d by Greenewalt' and Abel.

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

c o m p l e t e c o m p a r i s o n of his r e s u l t s was not p o s s i b l e , s i n c e h i s c o r -

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 .

is the m o s t a c c u r a t e of the c a l c u l a t e d H2 F o r t h i s calculation we have t h e pure-component

To t e s t

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

and E s t e r , l 5 a s s u m i n g that the s u l f u r i c acid s y s t e m acts as a H 2 0 / H 2 S 0 4 b i n a r y , This a s s u m p t i o n a p p e a r s s a t i s f a c t o r y except above

99 %myw h e r e it would have a negligible effect.

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 ,

E s t i m a t e d m e a n uncertainty i n p a r t i a l - p r e s s u r e v a l u e s , 0-150C 150-300C 10-80 80-100 300-400C 10-80 80-100 12 30 32 24 12 27

T e m p e r a t u r e range Composition r a n g e , Water Sulfuric a c i d Sulfur t r i o x i d e

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)

Refers to H 2 0 R e f e r s t o HZS04 R e f e r s t o SO3 R e f e r s t o p r o p e r t y at 298.15"K R e f e r s t o p r o p e r t y or Eq. ( l ) , t h e dissociation of H2SO4 (g1

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

F r e e energy Enthalpy Entropy Heat capacity Activity Activity coefficient

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-

Other Symbols p Partial pressure Total p r e s s u r e Temperature

P
t T

"C

Temperature, " K

K R
1

Equilibrium constant f o r t h e dissociation of HZSO (8)

Gas constant, 1.98726 cal/mole-deg R e f e r s t o liquid s t a t e R e f e r s to gas s t a t e

W e i ght - f r a c t i o n
10 0

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-

i n Eq. (24) at the weight-percents u s e d in T a b l e s A-I and A-11;

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.

Table A-V shows values of K

-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

U\t

Q 0

4 . 0
v )

I
W

I s .

m
LA
r(

m
0 0
N
UJ

. a re

it

m
0
J

Q
I -

O
t

W N

~.t-c~cc~rnrnw.-rN

..........

0 1

m
k n
e

N
4

rr:
I-0 V m 0

u w w UJ L d 0 r3 d LA Q 6 N N IC 0 9 N 9

!U

w
0

N 06
rl

c
3 :

...... .
0
d

N 0 t- N 0 m
i )

U I 4

m 0
d

VI*

rnD
v)

IC 0 I

a
VI

LJJ N N

m
0

C Y
N

' U
N

N.?b)dNmmW--rN

..........

6
LA

c3 w

a
4

-46 -

(3

2
U

r/)

o?.
0 .
LY

0
L 1

>
0

a
W

z
c
2
0

0
c
M

a
W -J

-47 -

J Q

I-

U I

6
c-1

co uv) n c
X C3

I
U I N Q
d

04.

Q O
X

cn I w

v )

1
0

d
0
L
L)

u
0 N

U I

cv

m
4

u cf
3

m 0
I

c
0 -I

UJ

v )

m
N

I n

CL

CL

CL 0

0
, l

> c
W

w m m
P-

c
2
0 V
0.

r-

w
0

-4

U
UJ

m
0
0
N
UJ

I Q U

a
N

I n

l n

8 0

-48-

N
(3

w
d

r-

3 \

w c3

.
P- d N

CD

a
d
W

0 I

c
Q

..........
d

LT, N d \f

LT.

u 6 rco
Q

w
w

a r: c
5

0
I

Lu

I Y

n
0
rT
NN

&

n
3

>
c?

w w w w w w w w w

Lu

w w w w

U I UJ

IU

1 1 1 1 1 1 1 1 Lu L U w Lu ' U UJ UJ Lu Lu

0 I

u
t -

w m
P

u1

o n

.
NN

e
0 I

43

m
6

. .

m
0
W I n

00

w
No3 \fPd d

o m

..

03
4

u
c3
UJ

-49

a c

rJ

J .-

I-

c.

-5G-

N
c3
Q ,

w r-

c3
N

0
N
N
f-l

(3

ac

PJ

cu
0

cn r-

Lu

d-ld+dl-lNNPJN O O O O O O O O O O

lu
0

w
N
d

w t Y n

0
N

oc

a >
C
Lu

+ Q
rb
Lu

In

c
3
0

z
c
V

Q O O O O O O W O O
1 1 1 1 l 1 1 1 1 1

~ ~ f . ; f . j m m m r n m c uN
0 I

2 0

w rCT
d

-51 -

rl

a c a

r-

IC N

(0 13

w UJ L u W Lu w n I n9 a 0 I Y Q .s 6 9 m 00Nl n m 4- rne I (3 d N m m 6 \+ I n

w w

OD I - f-. lc 9 9 9 -I 0 o 0 0 0 0 (3 0 1 I I 1 I I I 1 I
LLl N

I n

0 1
W Q fN
d

..... ..
Q -4 N & I - d N

e I-

mmmh mN
W

N NN N

0Q 000000 00 I I I I I I I I I I
I - co 4 a) 4 rl I n Q c3 tn d 0 & 6 cu 3 6 m Q) I n m & 0 \f N rr) I N 96 nI L n N

u 1w

w w w

co

I 111

0
d

0
1
d
p*:

0
U
c

0
N

W I 4

(3

I -

I
E

0
W 4

3
\f

UJ

O d r l d r l d d d d N

m
4
C

Q O O O O O O Q O O
0
N

.......... ...........

-52

ul
iz) I

n CI I I

P ?

0 c)

L-

IC

CY

r-

'-1

UJ W I n N LA

U I 9

r-i
e

N3

. ..
9
d
d

9N

*
Lu

a:
3

co
n .
t
3 0
e

uv)

Lu

c a

coo

94v ) N

c
3
c3

a: 0 u .
c

-4

cv

Lu 9 I -

cz

Y,

m w

cr:
a
l Y

e m
d d

d.4 d d

m
0
W

cor00 I t
' % I LLJ

Qlnin

a >
e

0
W

m
0

'W W
QUl

V m

w ' a 4-a,

000 I l l

Ln 0 I -

n
L '

a c

a ,c 3

mm m P . 4

z
U

..

cnm
. e

I n

4-

I-N

Nr-

LT

. . ..
r. f

Q N

wwUJ o w m

4.4-

u a
rl

*OD D d

rn

-I

3
V
0.

e
W

-53 -

Lu

.S c3 I

c
x
0

.-

..........
~

9 0 I n

oe
6 0
v)

N NN N NN 0 0a 00 0

00

LUwwwwwwwLiJLiJ N CI) m N or a3 N 4- d N

w w W W UJw N Q Q 6 * e N 9 mI - @In
9-4

. 4
0

P- r4N

. .* ~m
d

* +m
0

w w

w
d

a Y
N

9 6
e .

.. .
0

I n

I n

CY 0
u ,

*
c3

r
. ,
A
4

...............................
- .h d -IN m *In
a0

d 00 00000d 0 00 00 0 0 0 0 I I 1 I I I w w UJ w LL w w Lu UJ a 3 03 9 LA 4. 0 a3 a3 I mI n. Y I - 9 P- W m 43 O D 00 N O In4 0 N
d

I n

m w
3
OL

0000 I l l 1

9rlInm

d d

II -

v)

a :
0

u w w w w e w m
N O d b

0000000000 1 1 1 1 1 1 1 1 1 l

00

P-990 Q C C ~ W

....

UJ cp. 6
N

a . Q w
C w
Y

CL 0

4d 40
d 4d d

) r- I - b. r 6 (0 OD a 0 CP ( . i 0 0 0 0 0 d 0 C, c)

n P- 9 9 9 9 I nI O 00 0 0Q 0

c 0 V v) l a
c
3 0

I I I w w W w
I
9 P- N IC , N m 0a
40

rc
b

cr. r-

6 6
rl

z
I -

Z 0
0
Y

c n

.*

. . . . . . . . . . . . *. . .
a3
d
I 4

m
\t

co

w w
N6
.j 4

I U

9 a3
N

I n

W w w w I nQ d m n N I4 a2 co I nd NN 6 I

O V I a3
d . 4

w w w
din A N
. e

I I

W L I 1U I
d

a3 m
4

(v

ln d n :&

co

In+

0 Q F-Ln I 6 I n

a3

a)+ r - P - Q

n d Q I
W

l n

0
v)

a
W -J

. . . . . . . . . . . . . . . . . . . _. _. .*. . . .*. . . . .
d P - 4 - .j d Q-l 4 - d N Q d

w w w w w N O Q \ t POln 9 4 m

00000 000 I I I I I I I I

w w
ul
l n

0 I

PL Q c,

m . n cc

w m
Q

3 mMm 0000 0 0 I I I I 1 I I

m
4 7 ,

N PJ N N

c) 0 0

d N

6 f- 9 N IC N Pm r-l m d 0 6 IC N P- 6 a a3 Q . I m Ln rn d N 3

w w cu w w

w
4

I
W

N I nI n N 03 0 I 43 N e N 9 6
. ; f

w w

a
I -

...............................
V

-54-

? I d

E?

r)

T3

a I a
c

. J

w w

cn

6
h

IC
d

00Q 00 000 0 0 I 1 I I W Lu w w w
v\

0 0
UJ
d

w4

IC C> N

02

43 d

. .
I n Ln OI
N

L O ! nh

-4

IC

-4

.5 d

0 '

...............................
d
0 U

d 3
v)

l Y

Lu

a
0:
Q

a >

a a
I-

- 55-

c a
L

r- 9 9 9 I n 0 0 CI a 0 I I 1 I I W w W w W
4 Q f- N 'W 4 r- m d N 9 r4 c

co

n0 3I 4 6 i

I n 4rt D c3 0 D I I I I Lu w UJ W
d

D
I

*m m
Q

Ln

N VI Q) 9 d N 4-

. .

co

mm
ry N

a 3 m L> 6 9 6 d N

ww m

* VI
W

a 000O 0
Lu 6
9

m (\I N N N
I

N I

d d

v 4 d

* r* 9 VI ma , * * * m OD N m d W m .t
d

ww w
9
d

CX) Q 4

w m
o\

00 0 I 1 I W UJ W a3 4rll)

d
d

P-

0 00 0 00 00 I I I I Lu w w w 0 00 6 O 9 VI Q 9 d a3 6 9 . 4 N Nm

0
0

w
d

C O L)W

0 .
W

OL

r- 9
0
N

00 0000 0 0 0 0 I I I I I I I I 1 I

9 9

VI

I n

me

*d
N

m r- Q 0 0 0 r( Q m 4 N 0 VI 6 m 0) W d N m

e N In N m m m 6 in P-

IW W W U

w w ww w w

rt m m m m (v (v N N 0 0 0 Q 0 0 0 t) 0 I I I I I I I I I I
W W

4d d

d d

00 0

6 6

w w
d

v4

cv

I nd N

m m

a J

.*.
4

W Lu W w W w a3 0 d 0 00 m 00 9 co 9 9 0 N 4 J in N 0 m N r(

0 Q 0 0 c) Q I I I I I I
W

00 0

0
I
W

* 3. r9

r-

d N

m VI ab

N
r(

co
e

r4

U Iw W 9 dN n 6 0Q L b 9.4 6 m I n co N

111

ww
v4

I
W

. .

n J if d a J 0Q L n N P- m

nl

cr:
b

0
4

0 1 ~ o c o r r - r - 1 ~ ~ ~ ~
0000000000

m
0 I
W

>

+
9-I

w
4

0
L
CI

1c O3

I
4

-56-

0
0 I

w
c:,

N F)
e

m
0 I
01

VI
0

F -

Q 0

0
UJ 0

3
v) v )

CL

6
I n
4

w
d

n e
Q U

\t

m
W

0 I
.j

.
.

0
0

I -

;z 0

I
UJ N
d
-4 d

V
c
H

a
u1

C*

0
UJ

.j

0
M

-57-

0
W

a
I
a ,

cc

4 N

to uv)
u
aL
3

I I W W
0 LA

a 00 0 Q 000
u l

\f & 4- m

mmmm
I

a .

r!n.

6 VI
v\ & &

P-4
dy\

...........
(v

(v

.*. . . . . .
.N m LA 03 l - c

co m

W W W N c3

P- 0 I4 Q N N rl Q

w WW m In m

N 0 I

m
n
N

w
6
N
rl

.
.

I UJ

0 I

w
N

P-

cv

. I

VI

e
0 lA

9 & Q
I n

c
3 :

. . . . . . . . . . ....................
0 0

c
V

z
. I

Lu
( r

Pd

a
LU A

. .

0
0

m
I -

UJ
I n
Ln
d

W w
0

-58-

w
(3

-4

z
a
crl

0 I
Lu
P.4

.S
d
rl
0

cc
c
4

I,

a :
UJ

0
ole

OOOOOdOaoO
I 1 1 1 1 1 1 1 1 1

C O ~ t - r C Q 9 I n l A L n I n

0
0

p.

Y Z
W

60

UlwWwwWwwLuw

w
.S

c
3

d 9
d

0
-J

0 0

u .

I
Lu

N ch

a
c
O
t

03 t- I- 9 9 9 m Ln 00 0 a 0 0 0 00 I I I I I I I I 1 I

3 m 9 Q I- r- m VI 0 m m m N 99m 0 9 I- d 9 m N 9 3 0 d Nm d N I n4 t- rt
b o \ N co

IW W U

W W

w w w w

N
d

d d

0 000 0

O O O O O O O O O O
1 l 1 1 1 1 1 1 1 1

m
I-0 Vv)

a
u
3

c
3

w W rd n

I I w w
, d P

00 3
r(

I I I I I w w U Iw eo eo N 3 N
U I

w
0
d

m
( r

n 0 co ul 0 I t- d 3 rl N

9 rJ

6 \t

4.
I n

c
0

.
0 0 oc3roc> 0 0 0 0 1 1 1 1 1 1 1 1 1 1
O O O O 000 0 0 0

w
\t
OI
d

C
W
d

W U l W w w w w U J w w ~ W ~ U I w w ~ L u w L u w

0 I
lc
d

4m

-59-

d 0 I U I o*
W

aL

dN&P--Ii-(N*t96

a
aL

6it

.......... .
4
d

w c
S
. I

r :

6.;
N

0 N 9 it 4 9 6d

d d r( d a N N Iv 0 0 0 0 0 0 0 0 0 (3 I I I I I I I I I I w Lu w w w W w w w w . 9 a) m N rQ r- 4 3 I n m d 0 cd m 6d4

0
0 I

0
0:

.......... .
m m NN
4 96 d
Pd

w rr-

u .

0
N

0 000 I 1 I I
in N 9 9 9 w m a3 d m 03 d

I :

w w w w n in 4- N I

000 I I I

w
r(

- e= 0I 4 NQ
9
e
e

4 m rn m m m N 0 0 0 0 ci 0 n Q 0 0 I 1 1 I I I I I I I
0 m 4 N 0 6 m r- 9 0 in 9 OD & IC 404 m OI d 4 4 N r- 0 0 N m 9 6 cl N m 4 r- d
W

***
w w

w w

Lu

ww

0 I
Lu

.. . .

N N nd

.....

&
I n

4
d
8

rn
I-0
V W

0 Q 0 0000o a 0 I I 1 I I I I I I I

mm

NNNNNdd d

0
UJ

U I

n .
IC

w w w W d a d 9 n4 6 6 d P- m w 9 P- m e 60 m Ln d d nl e
W W
@

w Luw m Wm
* e

z c

3 :

... ... .
6 09 m 9 r(d N

N Fin 0

& P-

0
V
L
U

6 4 6 0 VI N

4
W -J

66
0
N

00 I I
W 0N
(v

0 c> 0 0 0 0 I I I I I I

r- r-

IC

.o a

m re

9 9

w w w w w w 6M 4 4 NN 4 m r60
d

000 0 0 I I I 1 I

n m a m m L
w w
L u

rl

. ..
9
d
rl

rn

w w 0Nm a r - .f N N w o 6 4 m m d 4 m in
0 .

U \t . f it 00 00 I I I I

m m m m m m N NN N
w m
Lu w w NI - \t

UJ

w w w w m 9 a2 N
CO

0 0 0 0 0 0 0 c, 0 0 I I I I I I I I I I

0
I
9

... . . .... ...

d
d

. n r- .j r- 4 .+ N t r0

N 4

a m NI-40
0 .

noN

w w w w w w

4d

I -9Q 001 ry 4- 9 w

ma J

03

* r6N
9

w r w m
m
0 .

rl d N

u
c3
U I

0m O m 0m 0m 0m i n 4 .im m N Nd d I I I I I I I I I I

n 0 Ln 0 Ln Q VI 0 i
d d

NN

mm4 t

0m 0m n 9 9 l nL

0 Ln 0
OD
Q)

66

-60-

a e c a
I .

I nI n 4 & 4- 4- m Vl 0 0 0 0 c3 0 0 0 p3 0 I I I I I 1 I I I

0-4

w 0
4

.
C O

N 0Q Q 0 o ( 9 4- N a3 m m 06 e NI n I4 r( m
e e

w w w w w w w Lu w 0 Ln -4 N Ih t - .s c 3 0-4 0 QD d 9 4 rl m

... . .
a

w m OI
0
rl

C Y

uv)
a .
C

w PL
4 OL

U Iu 1w (c QD Ln Q QI m09 0 N 0 0-4 br 4 m 0-4 N n 4- f0

0 c> 0 0 C> 0 0 0 I I I I I 1 I 1 I

a 0 000e 3
I

4 r ) -41 00 0 0

0 0

w w w b. m m

Lu w W NW N N d In
d 0-4

d 4N

I n rl m 0 &

ww ww w w w 9I n N .s r- a3 -4 d m N m 4- 0 d
I n PI
0

I I

w
N
3 .

w
PI
0-4
I4

rl

0 Pd NN

m
9

3
C

I
4 4- 4- m m m rn N N 0 0 0 c3 0 CJ 0 0 0 I I I I 1 I I t I w UJ w w w w UI w w r- N rl d a 9 m Q rn W 9 9 m 03 a3 9 0 m m Ln I n 0-4 Q m 0 0 Q rl m 9 0-4 N m 9 0-4 0-4
1
0

rn
0

0
0 4 -

w
0.

0 I

w
I3

00
dv)
N

N N N 0-4 d 0-4 0 00 0 0 Q I I I I I I
W

rl rl

0
0
U
c

. . . . .
N

m
9

w ww w w N P- U l m (c I n m O m r- cb 0 d .s (c 0-4 N .s 9 CD 2 N n
a

000 I I 1

w w w co m 00
9

w
PI

N9 0

9m m

.. .
cn
m
0-4

0-4

a fx

0
N

m 0 I

0
2E

c)

x
c

v)

N d

n:

c3 In

a c.
c
Q

p:
0 .

.
1 4 N N I44

d 0

a >
c3
W

m
t-0

0 0 0 0 c3 I I I I I

urn

W m d d 4m a m m 03
P-rVr-

w w

L U W UJ

0 0 I

9
Q N

z
Y

3
2

t3

..

rum
I4rl e .

0 m

u
Y

0
c

- 4

. 4 4 4

0 0 0 0 ~ 0 0 0 0 0

o(0 In
N

u l w w w w w w w w w

00 0 I I t
UJ a3
I-(

0 0

9r
N

w w ocr-

w
@
I4

crm

m e

..

-6

1c

w
Q

m
t-

a
N

00 I 1
UJU

m 4

m
0 I

w m
m

0 I

co
OD

w U

I n

0
4

-61-

r-

0
VI

c>
0 3

tn

1 . .

Q N O O M * NbLn

9-o'

r-3m

m e
-m r-m

..

M 4

mm
*VI

..

*e
0
Ln

e m

r-

m e

m
4
I
I

o
0
M

NVI

I U
W

mRiVlNN9ONNLn

..........
4rrNNFl49lL

6 * r - o m * d r - b 4

Ln

m m ~ ~ . - r n r - r - o ad

9
o \

m
sl
I -

,-',
N Ln

clr
N

-62-

..........
+ N 4 9 C ? O U \ I - d

+ d ~ m m

Q
Ln

+
oc
N

I -

+
Lpt

e~*co.s(rmmom o ~ m m ~ m m r - ~ - m n o c3 o N 4 R + N O n o 0 000 . 4N 4 m
ro
0

01

..........

01

C 3

r - e m o m ~ r -

r-\tcrm.fmer-o~
4 - 4 4

..........

r - \ + m ~ m a m m m c ~ + ~ m e m r - m ~ m ( ~

co
d
0

Lo
N

10 c 4
W

z m

W Q I

cz
L-.

3
N

o m
u

o - m

...

I
r3

omrsr-m
c > r - m m ~ n d m d m ~ o o ~ m ~ L m . j m ~ r - a r - ~ ~ ~ + -.IN m M m N m Q . n t3

m.49

CJ

..........

mm
r-m

..

~m 301

(-3

01

N b
0
N IC

m m m e a c - m m
N0
LO

..........
m
rd IC M 9 A c) d VI 4-4NmOrP-OIN
d

01 01 IC

CJ Ln

3
W

0 0 0 0 0 0 0 3 0 0 O - N r c l d V I 9 C m c '
N N N N N N N N N N

0 0 d

-63

ao
6
Q,

drn

00
0 0

.. ..

n 0 6 3.4 +tu I 0 0 0 0 d dm s 000r ,00 00

aem

I n3 m

5 m

..

9
I . (

& 9

mm r- 4
. (

VI 3 W m l- OI VI

r-

3 r- m m m r- 0
d

a m

.-(IVI0
dN

..

3 d Qr-

N m N VI m o m9
.-(dd

...

N
I n

0
N

6
0 ,

4mQmlc
C3 0 0 d N

a
x
11

I
6

0 0 0 0 0

c)oo00
0

.....
r - 6 d N

~ m . n m m m m ~ d ~ m+ m.~mr-a-.-.~.immeo . j - 4 d d N N m

...........

N 3 b O N Q

.......
000000
v 0 0 0 0 0
0

O O O N l f W

o m o ~ m m o m r - r m.-(omodmr-od
N 3 9 W N 9 N C> 4 3

..........
.-(dNm*In

d m W W - + Q m 0 0 O d . i W r 0 0 0 '3 0 n .-( 0000000

M

a: 4 a
W
C

c w
w
CT
P

.......
d
. (

2 6

a : w
4

Nm m 0O d

00 0 0
0

Q C .

0C) 0 0

zm
0

z m

..

mmm
0 3W

N O

N N d r - rcrm Q e N 0 0 0 d m m 6 m 3r- 9

.. .... ..
4N

N m 63 m 4mm
CON I
d d

d 4

l-r-

+tu

n 3 3 a m *-I I N m 3 9 w.-( 3
d 4

....
3
F Q

;nQm

4.

o m

m 3 0 mrd Nrn m 3

d m mr-

. .4 4
d m

m
W

r-

9
. (

CD 0 N
4

r-

W
d

N.t

oo

0 (3

00

..

9 3 0 9 3 0 0 04 m 9
4

0000

..

m.d -ON m 3m a
d d w Q
+ N O 9

....

0 3

001
*I-

9 0 9

..

m
0
4

m m 9
mm
N 9

rn

m N
3 9

N O

..

N0

d N

m o

I n r - W 3 9 Q r - In r- m m N m r - m NLII N m m m e m a m O Nm m 4
d d d

.m. . . . .

9
d

9
n l

-.
a
I

c',

a
6

4
W

0 m
O1

0 0 0 0 0 0 0 0 ~ m .DdOnJNrnOI-.i0,
0

mm . - r a ~ c ~ - d m ~ e I-aI-r.436 oo4mrmum 4N N 9b 0 0 <>C<'4 \t 00 r- m

.......... ..........
N l - NN

d4mmwmO16N
A d N S

m
9

- 64-

C)

0 I -

a
o o o r l ~ m m r o o o o o c> n r(

dm+ew*mr-

0
0 9

O O O O O O O O 0

..................
0 0 0 - 4 N m * Q O N
d

O - ~ ~ N I A O ~ N Q O .

.i~rnrcm~09mm(r m VI w m o r( m Q m m

I : I:
0:

o
M

3
v)

VI

w
d

o
.

a
d

c v )

a
a
D

IO

v a
V
-

c m 2.f w u w
w
Q .
0
L .

w 3 u
3
L o

a4
w
3

IO

........................

d 4 - 4

- I -

0
VI

a
w
J
I -

m a~

CJ
0
N

0
0
-4

_ ^ _ _ _ I -

_ _ _ I _ . -

-65-

0
N

6 c3
0

In

~ ~ n m m m oc)dmr-am o o a o o ~ m
0
d

O Q O Q 0 0 0

.......

u
0
0 ,

N.tdhml-m o o d ~ ~ m o 0 0 c3 0 4N
OOOC2DOO

.......
00

oor aoo
0

mt-mmmm -4 rt 0 .m

000000

m
1
u )

......

rm
h M

u l

o
0 9

w ct a

0 0 0 0 O d

00n

......
u
D 0

~ N ~ ro d N .c m

N
d

N 0

a
-

t
v
0

c t N

a CJD z m t - w

I O

w 2
2
Y

. a

o
o m

0 0 0
0
4

In
d

I -

z
0

G 0

0
0)

0
N
d

4 Lu I

NJ-G

00C C L J 0 03
9 ?-

m a

...

m m
9

e
t-

0
N

r-

a
w
0

0000000000

- 4 ~ m t m a t - m e v + ~ m . t m ~ t - v m o d r u m e m a r - m s
d 4 d d . - + - t + ~ d +N

0 ~ 0 0 0 0 0 0 0 0 0 0 ~ 0 0 0 ' 3 0 0 00 0 0 0 0 0 0 0 0 0
NNNNNNNNN

o ~ ~ m * ~ n ~ t om m mmmmmmmmmm J-

(3

ri

........
m I C h O V I * h \ , Q N A N ~ V I ~ ~ O d 4 r l N

N
IC

0
rl

0,

0 '

........

..........

m
~ Q O
rl

m m

a
0
o*

........
d

l n
9 N

co
h 1 9 9 m * ( r * m
0 13

VI
0 .

0 0 0 0N 4 m 0 000 00 0 0

........
m9hmmLn a m m ~ ~
00 VI l nh N 0 4h h 4 ~ N ~ . ~ Q C D O 4444

mm u

*m

* 0
v)

..........
) r (
~ m ~ m h m
-444

m
N

e
V

~
I

~
~

0.

m
I -

XUl

O Q N m m m N
~

0 0 4 9 0 1 4 e N 0 0

c m

Z @

m t n e l n m ~ - r n m ~ ~ ~
~ l

..........

rn m
0 9
h

V I:
Lu

n
0
I-.
h

' a
I

II
0
IC
0)

Lu

m m r0 0 0 0 l D 4 m IC O O Q O O 0 0 0
0

~ * ~ - m l n r ( ~ o o + m r - ~ u 1 ~

........

MI-NdP-39

m o d m o ~ m t n m a ~ ~ m l n m m m m ~ m ~ f f i l n ~ o o m r n ~ - ( ~ mm \ tl n Q O h I C 6 m r - 4 VI -4 N m . t VI 9 m <> m 9 Q'mhN9.49NP-m m
444

.......... ..........
4NNmm*\tVIVIS

- 4 ~ 4 m ~ m m m 0 r) .4 N 9 Q 4 m
0

0 0 0 0 0 4 m 9 00 0 o n t>v
0

. .9. . . . .

0 .

0
VI

0 '

+ O m P - N Q d V I O u j

o m m m o ~ o m ~ lm n

..........

m
0 9

rrNNNmm*elnm

d :

,
mI-Cc"ln4r-ln

r>-mlncrln.j-mP-.t

mmNmQ mm.-lnsmm1~01<~ 01 m m IC .o r- m N m c)

Q c '

..........

.-+~mlnm

9 m
m

m
l n

o.+Nm.tln9t-mcr

0000000000

0 3 0 0 0 0 O 0 0 0

N ry c u r d N N N N N N

o - ~ m * v l . n ~ - r n m 0
mm m m m
P,

0
. f

m mm m

-67-

V +

C,

...........
0

r . . . ! . . .

0
VI

..................
-

rlflVIa

S
UJ

0
VI l n

0000 0000 0000

0

...............
0 0 0 0 0 d N N * ~

dNmmmmO(rNC7

*mWOlN(rQO\lnln

(r
4

0000000000

3 m

cz

v)

000 000 000

0

4w.i

a
e

l
m
N

..............
0 0 0 0 0 0 d d N m
0000000000
0

Q ~ ~ ~ V I O Q Q Od-4N.ilCOLnNN

Po VI

3 . i

l - 0

x o

0
0 0

............
0000000000
0

mln(rln.if-r-VI.im 0 o o o d ~ m l n m ~ ( VI r

0 0 0 ~ 0 0 r 3 0 N~ ~

r u m m m m o ~ m d \ + m
0 0 0 0 d N M . i + 0

o
.

000000000d 0000000000
0

cz
d
3

u c l
m
J

0.i

ro
w
0

...........
d

. i

0 0 0 0 ~ , 0 0 0 00 000000000 0
0

l n m

..........
0 0 0 0 0 d N m
~ N ~ S ~ So 'N

0 0

00000000 0

00000000

.........
0

. i

dNmlnOONo'

6 0

o u c ~ o o c .0
c 3 0 0 0 0 0 0

0 0 0 0 0 d ~N

c
0

l n N

........
N m O C* 7r 0 - d 0 ~ Pd
00000 00000
0

0
N

......
0 0

d N m
000 000

0
0
rl

000
0

....
0

VI 0 0 0

0000300000

d ~ m \ t l n ~ + m n o ~ ~ m r t l n ~ r - o mdo ~ m . t l n . 6 r - m ~o d ~ m * m ~ r - m ( r0
d d - d d d d - i r l d

0000'300000

00000000(10
NNNNNNNNNN

0000000000

mnmmmmmmmmm

-68-

r)

N 0,

...............................
4 ~ m . t
0 . d ~

~ ~ ~ - - o r n m r n m ~ . i ,m *.

d d - i ~ ~ r n 4 m Q

0
d

..............................
d d N

m ~ s m d ~ m m m m r N n

d d d ~ ~ r n lv\t d m a ~ * m ~ m m ~ ~ H I - N ~ N O O0 O 0 0 0 0 0 0 00 0 0 0 0 d N * D Q 0 ~ w a \ t a * m m ~ m wI-m*000000 o o o o o o o ~ mm m \ t r n a s + e o m m~mm.ornmrt~-r 000000000 O U ~ N ~ V I ~ N m W m ~t n ~ m ~ u \ m m

0
0

......... .......... ..........

4 d r l N i U m

(m

m 9
\t

r n ~ t s w ~ * m m m m N

w LY
3
ul ul

m w

w
% !

0
Q

t - 3 K i m

IO

..........................
. .

d d r ~ m 4 m

I -

0 c:, 0 0 0 1 3 0 0

- N m F

0000
0

0
uJ 3

0 a 3

.... ..........
0 0 0 0 d N 4 9 1 3 Ln 00000000dd

m r u ~ ~ c l m e v l . - d 4 m VI 0 Q Q d V I 0 0

z c
Z
0

0 W N 9 9 F 1L 9

- d m m F m m o N m
0

C T

0
L

000o0-8(u5.001 c 0 0 L>0 0 0 0 0 n

m r-

..........

V
l

. .
UJ -J W

a
0

oo
0C
Q 0

d m

3 0

..

r-

N m 9 .4 0

oc o
0 N

(3 0 (3 C; 0 ,I,r-J 0

0000000000

..........
4

m m

0 rp 6 Q F tn

r-

-69 -

0
rl

9
rl

~ r n r - r - m m ~ ~ O O d * N O d t n ooaodmr-ln
0, 0 00 0 0

VI

m m

........
a 0 -4
0

cn
N

*
W

or
0,

.......
-4 m 0 r- 0 ,m 00dN.n.n

r-

13

l n

m m
o? 3
v)
v)

Q O O O O d
0

000000

......
m w o o
O C 3 N M

m
W

* N
-4dm
0
VI

L Y

n .
d

0000
0000
0

a
o?

GG4

.... ..........
*G-NOdr-tOI

u I -

m
d

0
v)

O O d N

4 4 o m

L m

0000

0000
0

I-W

.... ..........
c.> d N m G- w m w 0 9 0 0 0 0 0 4 m m 0 9
d d

m d m 4 m m S m 4 d

m
rW

w
V

ZG-

r-

o?

wmm
004

n .
0

000
000 0

I-.
I

00,
2

s m

... ..........
d

9
d

3
v)

m
N Q

II
0

0 0

00 00

r-

.. ..........
0 0 0 0 0 0 0 d N 4

-m.nmr-d.iI-G-m

4 d r C + O m N S N O

0 0 0 d N m m 9 w w

md ~ t t~ -w -m ~ a m o . n m m m NN*0woSmG-rG(L

..........

c
0
V V u Z

d m
00
0 0

+ + 9 v \ G - + N 6 9 0

o d m r - * w m m S N

Q O O O ~ N V I G - Q ~

0
9

?Y
0
N

0 0 0 Q 0 0 0 0 4 N

.......... ..........
d d

6
W W
d

r ( r l ~ m m w - i m

G-

I U
23 Lu
I
v\ OI

0 0 0
0

.......... ..........
_ . ~

m
W

m
U
I -

4 d N m m r - O

m
4

rnbrnWr-N4r-Wr-

0 0 0
4
0

o ~ o o o . + N m . D d

0 0 4 N v \ - 4 - 4 W W W

0 0 0 0 0 0 0 0 0 ~

..........
c)

r n ~ - ( ~ m o m m * o m

m w m ~ - m o ~ - a ~ ln r -

G-

o m w m o m m o * ~ - (L 4d-4NFrn*.nr-CC 0
4

..........

~ t ( r m w r n m t m +
0 0 0 d m ( L t Q ( L N

o c) o o

0000000000 0

.......... ..........
o
-4

t m

r-

d d N 4 V I

m
m

0000000000

0 w
0

4Nrn\trn.aP-WG-

04 0 0 r0 \lm 04 0 v0 \ .0 o0 r -0 w0 ~o ~ ~ m . f v \ a r - a ~ -

ooooooo0oo
N N N N N N N N N N

mmmmmmmmmm

-70-

I D

d 4

4 N

+
0

8 9

m
0

l n
9

r-.j m a
d

N m N

..
4

Q N

m*

r-

r-

mrc

.. ...... ..
mm0 m u ln0I m N N m c r urr- m m r - N
- I

dI4

9 9 NN

0 0 9

r- m l n r - m N m m N M d 9 mr-m m u

. 4

-N

mr-

N M

m m

9 Q

......
H N l n 0II-

QI L3 N

.. . . . . . .
01m

PI- m m

0I-l

mtn

m l n mrCJ 9 m e

e m

* 4

.-I4

N m

a
I

Ul

I -

rm

v,

a
(3

Ol

i 3
l n N

9 0
N

N d

mmm
t- m
9e

..........
N
( n

n -4 CT m \t 4

N \t \t 3 N

+.-INA\tlnQLn

mr m rr, r- J

0
0

-+

-71-

0
N
0,

m
N

I -

m
0
rl

..........

0 0 9

m
0

0
0,

..........
d

m
I n

ON.Dr-OdmdIn0
0
W

~ n m ~ m t n m * r n

OI

o o n d * c P 0 I m L n o

0 0 0 0 0 ( J d c r ) P - *

..........

m ~ I n r - \ t m mmmmr-twmr-hlo a m I n <> m N (2VI rd N m 3 9 P - O m 9 0

. .*. . . . . . . .
d d d N

e
w
!

3
u l

v,

* 0
(0

o?

a .

I :0

c3
W

a c
I-

z m

m
0 , dLn

InOD

....
r-9

m c

OI

*m m
I n
4

rlN

P- P9 9

*m

0
4

e w a
0
N

r- m
O

o* b *o mn mIn N 0 n04 N 3 P r- bIn P- 0, I

d

m e

t In

....

I N

@In

r-N

a ,
W

d mI n

* .

I -o
o)

9.4

9In
d N

..
m

9 9

m r - l-r44

N Inn 9 3

....
N m

I n N
I n

3 3 3
0N 9N

6 mcr r - m

9 0 3 0

r- m

I..I

rn m
h

0 0

0 00

OI *m 9 m mm

rl

.......... ..........
N
rl

4nJIna

m 0m . . t m ~ r - ~ r - \ + ~ r ~ m 4 N m VI m N m 9 9 c> d - i ~ m ~ n
3 mm

mm

m N Inr-

..

r-a

*m

0
W I f-

r-

03

\tmam+
3VIbIn9999
0
9 +

* u m ~ m d m ~ G c (3 N t m 01 ~n Nm m
0

..........

..........
O ~ ~ ~ N V I P

om

m N r~ r- N w. m LA r l d m s o m w c c u m

~ - d ~ m m t m + m

u
W

-72-

0)

00000NVI.4* 0000000.4N
0

o o d m

+'1*4-(mmNQ*3
WNNI-

cn

.........
4

m m
M
rl

cn m
NQ(c4QmI--0 0 0 .4 c> 3 N O 0 0 0 0 d N In 0 ooooooocr
0

........
*u

N Q I - N d m W Q 00 - 4 N w GO O O O A N * @ 00000000

N + W * V ~ Q ~ N

00.490mON
0 0 O O - t N M O

00000004 0

........
........

QI-OWW

( r O \ ~ O 4 N V I 9 0 9
~ 9 4 4 Q W W W O 3

..........

NI-mwmmwd oodJ74Mma0

00004NVIO (3 0 0 0 <J0 0 74

O G O 0 0 4 W 1 9 m 00~0000074

.........

r l \ t N N w - m * O 0 C) d m r - w a- 0 IC O O O O O ~ ~ W 0 0 Q 0 0 0 0G 4

.........
3

N Q I C * 9 3 4 d 0
ul

o o d - t o * m o m d VC,Ou-INtPcr 0n0c 3 0 3 '3 -4 N

0

........

0I

-73-

0 N

-m 00 00

..

w m 3 c . o
0 d N - m

<NU-4

.....

- m '3 c , a

c <. c

. .v.
U a J 0 . t

m e . n o c
4 N J l - C

.....
+.d

d m w " 000-

0000

.... ..... .....

~ m ~
O C +0.00. mm N C
0"Od.-

mJC.4.c

N *a C C I U ~
.DP -J 1N Nm N

.....

NC D C 0

.....
4

"OO-.Q

NCIJmQ , * Q N U m

0 0

O O - N I

oooc3u

.....

U a c Q -Q m Po O

.....

m * a c o
p N

vI-(NMO

? - ~ * m
OOOC'"

..... .....
* m ~ m
N Q

N V Q 3 ( h

0"l04N

N C m N F
YIC-4-N
-4-N

.....
mmooo

'3PrnCl
OO"-.U

00000

.....
m a ~

.....
3 d N

D-trrCN

QPNVIO

O d N Q N

n
N J c, e
> '

0000-

.....

00000

.....

c - r ~ m o
NQU.OJ

.. . .
4
Q I

.. .....
mmm"
3mcmLp

c,

0 0 0 - N

e*m.Dm
d - N m

.....

4 4 N N m

QOYINN

uoooo
PmNd-4
4 N m J L n

.....
.....

CV\VION

mmmmm w

a m c m m

m c 4

_I

,2rrNLnOI

.....
N - N ~ O

0 3 >'33

- c m m o

00mm.n
JLnQ0t-P

.....
m

...

m m m ~ o .

000

muam:

- m u

NC Q C Ln P

c 9 m - e
m0r-e.r C ' N Q m
O " O O 3

J Q ~ Z Z
m m o O O

.-. . .'-..
c,
-4n.

o 3 0c m

..

.....

o * o m m
r - m c o

..... .....
--Ne

C P

~ . m

m m - a -

0l.Yr-om

0
9

F 4

*-. 0 C? C W V . . N U ~

.....
a

a ~ m m . t

mnaOP*
0 - m m v

O O O O N

.....
O I I

m o o 0 0
N N

.....
N ~ ~

d 4 N

Foum'n
d 4 - N

"0000
I

m \ t m ~ -

- 74-

0 0
A

NL o n n0 0 .

000

...
.> *
CNCG-4

omminm
or--09

.....

R1.wmmn.n 0 N 0 U

N N m m 4
fi

VIoou4 4FUPVI

..... .....
NVIDQN

0 0) .

0 00

... .....
-mm0.9
0000-

m m Q C c

- c * o c

C-0.4-

..... .....
9 C O " C

m m ~ m m
0 N J 0 0> ..
0 . .

oC#o

...

N N m m J

O V I N ~ U

*m"29r-

ON0.O.Y

..... .....
-"-mu
X U " 9 N

mr--r-N
VI
[F 0

IUr.Jmm.3 U J

uVI99r-

COINVIrn
- 4 4

r-mmwm

.....

d m Y N N 4mVI9rN ~ J

.....
O

m m o c m

A N m m 4

m
0 .
NU 0 0<? C, C G

aoooJ Q Q O N

.....

mor-039 r - f N m h
- N m J m

.....
9.Y

0.4-01c

.....

4 r > . n 3 r UVlvIQO

r-

3
0) 9

0 - m 0a (3

000

. . . . . .. :. . . . . . .-. . .
-RIvcm c, c c c
N m NCI 3 N U C N

TC r- <' L - Y Qmdmng

.....
3 3 4
4 4 3

VINC-30.

OGOO-

4 0 - c m

..... .....
mr-

3 N N m - 9

m o - m m

a m c ~ m

>
4

0 '3

<,

...
c. c
'2

LT J

mmor-m 9 m G C
- 3

.....
N

m m u J m

-4mL.90 u m m r - ~

.....

0
N 40.

0 v0 u
00

.. .....
muam*
B-NUb

0.-00
.Yr-".dN

00000

..... .....
QNNJO.

J~nr-0.d

m O 0 . N m
" - A N N

" l N 1 3

9-um0.
',-NmVI

-0
70. Lu U

O n O O O

.....

" CPN9Nm
r--m--'m
- 3 N N

.....

Lnm*m*-mi)ON
d d " " N

..... .....
9 - m m m
N -

LnPN-OO
N ~ U

w o 0 . c m n
3 I + .
W O

3 . m 0

u
r0

0
C

. a

C.

0 0

. .3 .u . .. oco
N r(,

-t VI rC > C > O O ?

-75-

0 N

J h J * d

OOdNLn

"
0
0

00000

.....
0 N 0

- - c m r

- - ~ m l n
U m C e a N O C , d r n *

-em+*

..... .....
c
C b P d m
h

< >Y .

, t

"+NN

' 3 0 0 0 0
-4.4-N
N

.....
~ J N ~

NCmQ-4 - m a b m

m
0) b

00000

.....
-0

"-NUN

U 4 N C C

.....

""lmuQ
N J

.....

m u a h -

0.0.NCJ

0
b

"mm

00'2-N

00000

.....
- m m o
C a G O -

N4JLnP

W3W "N "N m.D 0.40.0Q

.....
. . I . ,

c0.mo.o

.....

FNt7.d.O "NN"1-3
Q

Ln

0 9 .

130T3"

.... .....
- m m o *
(3 3 0 4 . .

m0lr.m
Q N I Q N

N J Q 0 . 3

"

Cr-mcm

.....
.....
d"..

0
. 0
Q .

- m a 0 00
0 0 0

...
-m 00
O L

PNQOLn 4 d N N

0 . 0

" " J m c a m o m s

( Lu 5

s s

o r .
0
1

.......
L70"Nb I,' CC'

mwr-0.0.

1
0

"
0
0

a
I

.
Q

......
mmor-m
C?LI-("N

03000

m U
L

e
L

u
-

v) v) Lu

O
.
N

Oc.0

C -

o
v

.Yo1
N )

000

...
~

z
-

C O Z b

=?

x0

w u

: Y O

OL c m 6 - 1
0 2 : " w

n.
n
3

o
m

u
3

- I o
- ~ m ( n
0
O O D O

x .

v)

i c n

0000

..............
c - ~ N - mcommm u - - N ~ ~ n r o
00000
000""
+N

30

IC 0

0 0

............
m r . o m N
C>'3'303
C ~ N

dNll3?1\

00000

00000

u
I

0
.

" N N m 0000
OC,0"

....
d

0
J 2

C '

0
N

0 0
4

-76Table A-IV.
WT PCT 10.0
COMPa

Constants for partial-pressure equations.

0

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

SULFURIC ACID PARTIAL

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

REFERENCES 1. 2. 3. 4. C. H. Greenewalt, Ind. Eng. Chem, 17, 522 (1925).

B. C. B u r t , J. Chem. SOC. 85, 1339 (1904).

W. Daudt, Z , physik. Chem. ( F r a n k f u r t ) 106, 225 (1923).

E. Abel, J , Phys. Chem. 50, 260 (1946). M. Bodenstein and M. Katayama, Z . E l e k t r o c h e m . 15, 244 (1909).

5. 6.
7.

W, F. Giauque, E . W. Hornungp J, E. K u n z l e r , and T oR. Rubin,

J.Arn. Chem. SOC. 82, 6 2 (1960). P . A , Gigukre and R. Savoie, J. A m - Chem. SOC. 85, 287 (1963). National B u r e a u of Standards C i r c u l a r 500, 1952.
KO K. KelEey, U,S. B u r e a u of Mines Bulletin 584, 1960.

8.

9.

PO. J . E . K u n z l e r , Anal. Chem. 25, 93 (1953).

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).

T h i s r e p o r t was p r e p a r e d a s a n a c c o u n t o f Government s p o n s o r e d work. N e i t h e r t h e U n i t e d S t a t e s , n o r t h e Comm i s s i o n , n o r a n y p e r s o n a c t i n g on b e h a l f o f t h e Commission:

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.

A s u s e d i n t h e a b o v e , p e r s o n a c t i n g on b e h a l f o f t h e C o m m i s s i o n i n c l u d e s a n y e m p l o y e e o r c o n t r a c t o r o f t h e Comm i s s i o n , or e m p l o y e e o f s u c h c o n t r a c t o r , t o t h e e y t e n t t h a t s u c h e m p l s y e e or c o n t r a c t o r o f t h e C o m m i s s i o n , o r e m p l o y e e o f s u c h c o n t r a c t o r p r e p a r e s , d i s s e m i n a t e s , or p r o v i d e s a c c e s s t o , a n y i n f o r m a t i o n p u r s u a n t t o h i s employment or c o n t r a c t w i t h t h e C o m m i s s i o n , o r h i s employment w i t h s u c h c o n t r a c t o r .