GAS MIXTURES ON SOLID ADSORBENTS
by
Charles E. Speer
B. S., University of Texas 1949
6ubmitted in Partial Fulfillment of the Requirements for the Degree of Master of Science
from
Massachusetts Institute of Technology 1949
Signature redacted
Signature redacted
Super v or 7 -~ Head ot DepartmentWY
zKi4
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eitt rzo'1 alne.xIiOi p*I eziJ lo Ineim~fV1Ju Ialtsoz nl belclmjU4
*oneloa lo qe$88m lo 69,130(
i~oloririoeT lo eiwttztaaI alessvuoasM
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-io vxoqjia
;fn9mlrxsq9(l 'J'o bBOH 00,
qC)
Dept. of Chemical Engineering Mass. Institute of Technology Cambridge 39, Mass.
September 1, 1949
Professor Joseph S. Newell Secretary of the Faculty M.I.T.
Cambridge 39, Mass. Dear Sir:
The thesis entitled, "Correlation of Data for Ad-sorption of Binary Gas Mixtures on Solid Adsorbents," is hereby submitted in partial fulfillment of the re-quirements for the degree of Master of Science in Chemical Engineering.
Respectfully submitted,
Signature redacted
iii
TABLE OF CONTENTS
Page
I. Tables - - - - - -- -
---II. Figures - - - - - - - vi
III. Summary - - - - - - - - - - - - - - - - - viii
IV. Introduction - - - - - - - - - - - - - - - - - 1
V. Literature Survey - - - - - - - - - 3
VI. Thermodynamic Test of Data - - - - - - - - - - 5
VII. Solid Fugacity Functions - - - - - - - - - - - 25
VIII. Precision - - - - - 53
IX. Results - - - - - - - - - - - - - - - - - - - 54
X. Appendix - - - - - - - - - - - - - - - - - - - 55
A. Original Data - - - - - - - - - - - - - - 56
B. ?Functions - -- -- - - - - - - - - - - 66
C. solid Fugkcity Functions - - - - - --- - - 71
D. Sample Calculations -- - - - - - - --- 76
E. Nomenclature - - - - - - - - - - - ---- 77
iv
TABLES
Page I. Hydrocarbon Systems Analyzed - - - - 4
II. Broughton's Test of Data - - - - - - - - - 23
Original Data Ethylene-Propane-PCC -Ethane-Propane-PCC - -Isobutane-Butene-l - -Acetylene-Ethylene-PCC Ethylene-Propane-PCC Methane-Ethylene-CG - -Ethylene-Ethane-CG - -Ethylene-Propylene-CG -Ethylene-Propane-CG - -Propane-Propylene-CG -Propane-Propylene-GLC -Methane-Ethylene-SG - -Ethane-Ethylene-SG- - -Ethane-Propane-SG - -Isobutane-Butene-l - -Acetylene-Ethylene-SG -Propane-Ethylene-SG - -Ethylene-Propylene-SG -Propane-Propylene-SG -EthyleneoEthane-SG - -56 56 57 57 58 58 59 59 60 60 61 61 62 62 63 63 64 64 6b 65 (Functions AXXI. AXXII. AXXIII. AXXIV. AXXV. AXXVI. AXXVII. AXXVIII. AXXIX. AXXX. AXXXI. AXXXII. AXXXIII. AXXXIV. AXXXV. AXXXVI. AXXXVII. AXXXVIII. AXXXIX. Ethylene-Propane-POC -Ethane-Propane-PCC - -Isobutane-Butene-l-PCC Acetylene-Ethylene-PCC Ethylene-Propane-PCC -Methane-Ethylene-CG - -Ethylene-Ethane-CG - -Ethylene-Propylene-CG -Ethylene-Propane-CG - -Propane-Propylene-CG -Propane-Propylene-GLC -Methane-Ethylene-SG - -Ethane-Ethylene-SG - -Ethane-Propane-SG - - -Isobutane-Butene-l-SG Acetylene-Ethylene-SG -Propane-Ethylene-SG - -Ethylene-Propylene-SG -Propane-Propylene-SG -AXL. Ethylene-Ethane-SG - - - 66 - - - 66 - - - 66 - - - 66 - - - 67 - - - 67 - - -
69
- - - 67 - - - 68 - - - 68 - - - 68 - - - 68 - - - 69 - - - 69 - - - 69 - - - 69 - - - 70 - - - 70 - - - 70 - - - 70 AI. AII. AIII. AIV. AV. AVI. AVII. AVIII. AIX. AX. AXI. AXII. AXIII. AXIV. AXV. AXVI. AXVII. AXVIII. AXIX. AXX.Solid Fugacities AXLI. AXLII. AXLIII. AXLIV. AXLV. AXLVI. AXLVII. AXLVIII. AXLIX. AL. Ethane-Propane-PCC - -Isobutane-Butene-l-PCC Acetylene-Ethylene-PCC Methane-Ethylene-CG - -Ethylene-Ethane-CG - -Propane-Propylene-GLC -Isobutane-Butene-l-SG -Propane-Ethylene-SG - -Ethylene-Propylene-SG -Propane-Propylene-SG -71 71 72 72 73 73 74 74 75 75
vi FIGURES / Functions Page 1. Ethane-Propane-PCC - - - - 7 2. Isobutane-Butene-1-PCC - - - - 8 3. Acetylene-Ethylene-PCC - - - - 9 4. Ethylene-Propane-PCC - - - - - - - - - - - - -- 10 5. Methane-Ethylene-CG - - - - - - - - - --- - - - 11 6. Ethylene-Ethane-CG - - - - - - - - - - - - - - - 12 7. Ethylene-Propylene-CG - - - - - - - - - - - - - 13 8. Propane-Propylene-GLC - - - - - - - - - - - - - 14 9; Ethane-Ethylene-SG - - - - - - - - - - - - - - - 15 10. Ethane-Propane-SG - - - - - - - - - - - - - - - 16 11. Isobutane-Butene-1-SG - - - - - - - - - - - - - 17 12. Aoetylene-Ethylene-SG - - - - - - - - - - - - - 18 13. Propane-Ethylene-SG - - - - - - - - - - - - - - 19 14. Ethylene-Propylene-SG - - - - - - - - - - - - - 20 15. Propane-Propylene-SG - - - - - - - - - - - - -- 21 16. Ethylene-Ethane-SG - - - - - - - - - - - - - - - 22
Solid Fugacities vs. Pressure 17. Ethane-Propane-PCC - - - - - - - - - - - - - - - 28 18. Acetylene-Ethylene-PCC - - - - - - - - - - - - - 29 19. Methane-Ethylene-CG - - - - - - - - - - - - - - 30 20. Ethylene-Ethane-CG- - - - - - - - - - - - - -- 31 21. Isobutane-Butene-1-SG--- - --- 32 22. Ethylene-Propylene-SG - - - - - - - - - - - - - 33 23. ropne-Popyene-G -- - - - - -AA 23. Propane-Propylene-6O---3 Solid Fugacities vs. N 24. than-PrpanePCC- -- - -- -- -- - -- --3 24. Ethane-Propane-PCC---3 25. Acetylene-Ethylene-PCC - - - - - - - - - - --- 36 26. Methane- Ethylene-CG - - - - - - - - - - - - - - 37 27. Ethylene-Ethane-CG - - - - - - - - - - - - - - - 38 28. Isobutane-Butene-1-SG - - - - - - - - - - - - - 39 29. Ethylene-Propylene-SG - - - - - - - - - - - - - 40 30. Propane-Propylene-SG - - - - - - - - - - - - - - 41
vii
Solid Fugacities vs. N for Mixture Adsorption Only
Page Ethane-Propane-POC - -Acetylene-Ethylene-PCC Methane-Ethylene-CG Ethylene-Ethane-CG - -Isobutane-Butene-l-SG Ethylene-Propylene-SG Propane-Propylene-SG -42 43 44 45 46 47 48
Solid Fugacities vs. P for Mixture Adsorption Only
38. Adsorption on Carbon -
-39. Adsorption on Silica Gel - -- - -- - -- - - -- - - -- - - - -- - - 5049
31. 32. 33. 34. 35. 36. 37.
viii
SUMMARY
The object of this work was to find correlations based on sound thermodynamic principles which would permit prediction of the adsorption of binary gaseous mixtures on a solid from the adsorption isotherms of the pure gases only. Data concerning the adsorption of
twenty hydrocarbon mixtures were examined first by utilizing the thermodynamic requirements proposed by Broughton and then by considering the solid as a
component of the system and calculating the variation in its fugacity. Neither of these methods of analysis yielded a general correlation of the data. This was primarily due to the fact that both require extremely accurate data as the pressure of the gas being adsorbed approaches zero, and such data were not available.
It was concluded that the LangmWir and the Magnus equations as extended to gaseous mixtures are not
generally applicable, that the Broughton criterion cannot be used for testing data or as a possible means of general correlation unless the data are extremely accurate at very low pressures, that there is no general correlation for the variation in the fugacity of the
solid adsorbent, and that the Van Laar type of equation cannot be applied in the form proposed by Cadogan and Chertow since the fugacity of the solid varies with the composition of the gaseous mixture.
For many years there has been much interest in the nature of the adsorption of gases on solids. Not only is adsorption of primary concern in many catalytic reaction processes, but also it may prove to be of conrsid'rable importance in the separation of petroleum refinery gases. It is the latter consideration that prompted this work.
The normal method of separating the hydrocarbons of petroleum is the distillation and rectification of the crude petroleum. Naturally this method depends on differences in the boiling points of the various com-ponents present. However, when the molecular weights of the compounds are nearly equal, these differences become too small to afford a practical separation in
this manner. In addition, the very low molecular weight compounds are gases at normal temperatures and pressures, and special high pressure or low temperature equipment would be required to use the distillation procedure at all. A reliable method of predicting the characteristics of selective adsorption would be of great value in
judging whether or not the distillation process could be replaced by an adsorption process.
The purpose of this work then was to analyze and correlate previously published data in such a manner
solid could be predicted from data on the separate
adsorption of the pure gases on the solid. In addition, it was proposed to derive these correlations from sound thermodynamic bases rather than from purely empirical considerations.
Most of the previous work done has been concerned with the adsorption of a single pure gas on a solid. Various empirical and semi-theoretical correlations have been presented for predicting the adsorption
iso-therms of specific systems, but no entirely general correlation has been found. Attempts to extend these theories to gaseous mixtures have not met with much success. One of the main difficulties encountered in these extensions has been the lack of experimental data for mixture adsorption. Such data are now available and show the lack of general applicability of these
extensions, the most important of which are the Langmuir
j2, the Magnus (?, and the Hill (5 equations .
Broughton jLhas also provided a thermodynamic means of testing such equations and he has shown that the Langmuir equation is correct only in a very special instance. Likewise, the Magnus equation proved to be generally inapplicable by this test. The Hill equation
is at present in such an impractical form that it could not be tested either by the Broughton criterion or by
LITERATURE SURVEY
Since the main interest in mixed adsorption lies in the possibilities of separation of hydrocarbons, it was thought desirable to confine the examination to hydrocarbon mixtures. A search of the literature
revealed that the only signifigant data were to be found in work recently done at the Massachusetts Institute of Technology. Most of this work was done by Cadogan (3) and Chertow (4 and their coworkers, and all of the data were summarized and presented by one or the other of these men. These two references were the only sources of data used for this analysis. Since the majority of the investigations were carried out at a temperature of 25*C and a pressure of one atmosphere, it was decided to further restrict the examination to data obtained under these conditions. All the data used in this work as original data were obtained from the smoothed curves presented in the references. Table I presents the
systems considered and Tables AI through AXX give the original data for them.
Table I
Hydrocarbon Systems Analyzed
Hydrocarbons Adsorbent Reference
Ethylene-Propane PCC+ (3) Ethane-Propane it Isobutane-Butene-1 " Acetylene-Ethylene (4) Ethylene-Propane "t Methane-Ethylene CG++ (3) Ethylene-Ethane It Ethylene-Propylene "t Ethylene-Propane "1 Propane-Propylene It Propane-Propylene GLC (4) Methane-Ethylene SG++++ (3) Ethane-Ethylene it I" Ethane-Propane " " Isobutane-Butene-1 t Acetylene-Ethylene (4) Propane-Ethylene It Ethylene-Propylene "t Propane-Propylene I Ethylene-Ethane "
+ Pittsburgh Coke and Chemical Co. Activated Carbon,
28/60 mesh.
++ Columbia G Activated Carbon, 8/14 mesh. +++ Godfrey L. Cabot Carbon Black.
THERMODYNAMIC TEST OF DATA
Broughton (1) presented a thermodynamic basis for the examination of binary mixture data but at the time of presentation, not enough data were available to test
it adequately. The initial step in the analysis then was the testing of the data for thermodynamic validity. Broughton showed that for a binary gas mixture maintained at constant temperature and at equilibrium at all times
fN,, Me
0 f Pa
where: N = the number of moles of gas adsorbed per unit weight of solid.
P*
=
the pressure of pure gas over the solid. P = the partial pressure of the gas in thebinary mixture over the solid. This equation can be further simplified to
NO
i-Vr
/;7?4.where: N* = the number of moles of pure gas adsorbed per unit weight of solid under a total pressure equal to the mixture pressure. = the ratio P/P*.
r = the ratio N/N*.
Thus, the graphical integration of ln
(
= $(r) for the two gases in a binary mixture should provide a means of determining the validity of the reported data, i. e., the ratio of the areas under the curves should be equal to the reciprocal of the ratio of the NO's.&
Figures 1 through 16 show these "L" functions for sixteen of the systems. Four of the systems so obviously violated this condition that the _ funtions were not
plotted. Tables AXXI through AXL give the calculated values of l and r for all twenty systems.
Fiur 1.4l F7 -4-444-4 ~4~L ~ I. _ I~L444- LJ4~ _ L A-A, _+_J I-4 - 44-i e- .... ._ .-4 .4- .+. m~ I- li p , -~ T --44-~-z r--4t f f-A ~ -4-t~ 7 -- ,
I
I
-
1* 1- t .. .... '-i 54F--i - T4 3-I 0. 0.+. . 0.1 0. lz 0.,3 0.,v 0.!s 0.4, 0.7 0. If 0. rf /0 Figure 1. r1c e -4 a -n P_ o"l-60--oRkne-t S --- --6 - --Figure 2. 2 - - -t-
-I
-I-- -- 4--Li: -t I - 4-LLLIJJW~1~ -j~J -t -0.3 .-. u olr c:Af
I
I
U
I
I
rt~T-I---7t1
0.1 c -- -t -4---- -4---- -- ICO-&~t
T - -t I--1-4 r~$ +- --A -a-IITIII-VbIzhIi
tI~fl-LW
- i - Inow 77 77- I--4 t- I - 4 -4j - --- - - 4 t --4
7 -- - -4-= ---4
i0 I ..~ .il ... .- . '-- --14 ITI 4+ OD~-- FK~4''4 ~-11 lid;t~ 11i ; 0 1 + IT I!,.~i Ir Fii~--' W!H- Hl k t++ Fi w'i' IjI i
4
I~i th C4--IsI * !-4-~ IL 4.-4-1 i44- T4 C , 1- ---KI)i I-ttt E i)V
~~iF~j r,17 1 F III:t ITIT N 11111
1!I
1
kI
iI
i
tT ii I I~~ J~ WilI 111111 +. I A+ 4~+ l.44 t44 11 141i r+i + I I r 4lII 47VH-T- 0 1-T ;!Ii f :if T I p!! , , , I ~ it I I M w II I*** I t I II f1 I 1!k 111 it -t-4 H--r t t ~~If 10
-44 I t WA~L I I go
Tt~
!tajjj
i
l
4-4 1 * + 1 1 L l 1 it~ _ 01111 -4t v Wi W 11 w N1J ' 0Iw_
Isw
91
w
ul
V1
%%-Figure 7.
1
-U - -- AR -; 7 -7:t -* V 74~ 3aI
-44
+ -IT 3a0 CD .5. iI . ~ I_ I 111 44-. itI ,iI I ,I II .1r 2 -% it I t 1111111t KrI I IK t if if 1 '3 1~ C 'I N. f%
Figure 9. 10
tt
-4-3-F ET 4- -- 4-4- - :T: 2 4. 4~I f t 4 - -E
i
::_ -+ -I
-4 t 040 Z..
4-
'- -
065/0
0LS
Figure 10.1 al0 -4 - --4A 44--1 --- -4 .----4 4 1-r4 - -- - - - - -O 0.3 0. 4 0.5 .6 Or 0. 0r rf/,Ieor' l
fi-.-
---- --1 I- 4-Figure 11. I -t 4EE t o.3 --4-$
14 -4-T --4 I 'i ~- I - t-I -- Wi-t Wi-trl I a, t - ---0. *f or I-iuteie-I _________ ~ --- ----i I 0.5 0.4 -~- 4 - --I-
-A-- t TI-- ---- -T_--V
-- 4
-A--i --t + - 4 --+ 4 4 --~ 44 4-4-4-44 4 -I- 4----I 4--i-- ~
t
7 ----1--441 * It-~
14--
4---4
J,111t f IfiI i pi
LVVt
T t-T; 141.4z -I. 1+ I+ I l.lT ; f , A4 '4'.r I . I I IlI I 4+4~~ t ..L4 ~ ~+
I t 1,H li l l ' l lii- I ' I! II L iI i I i + 0iFigure 13.* I 0.1 aq~
19
I'
j 1. U~ 0 -+ - - - -- ------* ---6I 3 -3:7 -O ---4 9 -O o-310 -. Figure 14.0 ---. .. + . .J I-~-- -- -- - -- -f-44 H- -4 -L 0,4 05 MEN. -O . - -
To,
-it, "
-471
iH j11I~i I Itji ~ 4.$-* VV 4 I I I- I~ IL 101!HT id Hl I-, 'p E 0 0 'I 0) 116111 w I I w 1111 vi %14 W N %, I-I itI TII II. . t f Ii-4 l it l 11 1W l
W, li
Ii
Ih
~l111!1
PI l~ ~ 1lIIII i II N i Ii l , h 1 :1 1 11 111 111 '1jllii I 1111H 1 1 tI 11 1il !k 1 ll I 1 H I I! I it H I: i , I I Ii I Il t I I i I I i i 11 ;il Il , 1 I 1 1111 , -4--I i ttF
LLf, v1 i 4~~i ttr' i+t+4~ 1__7
Ip *4023
Table II presents the results of the graphical integration of the L functions.
Table II
Broughton's Test of Data System
Component A Component B Ads. Ethylene Ethane Isobutane Acetylene Ethylene Methane Ethylene Ethylene Ethylene Propane Propane Methane Ethane Ethane Isobutane Acetylene Propane Ethylene Propane Ethylene Propane Propane Butene-1 Ethylene Propane Ethylene Ethane Propylene Propane Propylene Pro pylene Ethylene Ethylene Propane Butene-1 Ethylene Ethylene Propylene Propylene Ethane PCC " " " " CG it tI it t GLC SG if it ift "I "t " "
%
Diff. o ~j NjOlnies 4(-J2+oo 7 A ->100 1.375 1.151 -16.3 3.56 4.20 18.0 0.786 0.593 -24.6 1.235 2.39 -93.5 0.413 0.276 -33.2 1.81 1.74 - 3.90 2.75 1.24 -55.0 ->100 Insufficient data. 1.759 1.823 Unreliable data. 0.1445 0.170 1.012 0.389 0.230 0.358 0.445 0.0566 0.0814 0.106 1.043 0.267 0.1825 0.3875 0.402 0.1315 - 3.6 -42.4 -37.6 3.06 -31.4 -20.6 9.08 - 9.67 132It can be seen that, according to this test, few of the data seem to be consistent with the thermodynamic requirements. This is due to the fact that the test requires high precision of the data in regions where
this is usually not obtainable. Most of the area under each curve is to be found at the end at which r approaches zero. At this end, the pressure is also approaching
zero and as this happens, the precision of the original data becomes very poor. In order to obtain values of Y
at low r's, it was necessary to extrapolate the original data to such low values of pressure that errors of 50% or more could easily be made. Even with careful ex-trapolation of the original data as far as possible, it was still necessary to extrapolate the ffunctions to zero r. With these extrapolations, which occur at such critical regions, it is not surprising that the correct area ratios are not obtained. It seems unlikely therefore, that this test can be used for more than a qualitative check unless extremely precise data for the critical regions are available. It can be used for this however, and on this basis the following systems seemed
doubtful enough to be neglected in subsequent examinations. Ethylene-Propane-PCC (3) Ethylene-Propane-PCC (4) Ethylene-Propylene-CG Ethylene-Propane-CG Propane-Propylene-'CG Methane-Ethylene-SG Ethane-Ethylene-SG (3) Ethane-Pr opane-SG Acetylene-Ethylene-SG Ethylene-Ethane-SG (4)
In spite of the difficulties ino lved in using this test, attempts were made to find simple empirical equations for the )'functions,.and in doing so, impose the condition of correct area ratios. It was thought that these functions might possibly be correlated by
such means. Such investigations showed that the wide diversity of the shapes of the curves prevented the
SOLID FUGACITY FUNCTIONS
In a further attempt to find a sound thermodynamic correlation, the possibility of a relation between the fugacity of the solid adsorbent when the pure gases are separately adsorbed and the fugacity of the solid adsor-bent when the gaseous mixture is adsorbed was investigated.
Consider the system of pure gas and solid as a binary one, i. e., include the normally neglected solid as a component. If
s-~ 2~ ,TtNg
P,T,Ns
where: N is the number of moles adsorbed. F is the molal free energy.
F is the partial molal free energy. s refers to the solid.
g refers to the gas.
then, from basic thermodynamic relations
N'ds + NgdFg =
PT
- - - - - - - -(1)If, during the adsorption process, the total pressure is assumed to be held constant by a non-adsorbable gas that has a negligible effect on
Fs
and Fg, then therestriction of constant pressure may be neglected. Since dFsR RTdlnfs, where f is the fugacity, equation (1)
26
solid remain constant,
dlnfNs = -N dlnf T - - - - - - - - - (2) For the gas mixtures, i. e., ternary systems, similar reasoning shows that
dlnf = -NAdlnfA -NBdlnfBP,T - - - - (3).
Here one does not require the hypothetical non-adsorbable gas to maintain constant pressure. Since the pressures in question are all atmospheric or less, partial pres-sures may be substituted for the fugacities of the gases. Also, dlnP = d and dPA
=
-dPB' Uponsubsti-P
tution in equations (2) and (3), one obtains the final equations
dlnfNs s:n ~~J---(4)= - dP
dlnfjs
-(N,
- NM dPA T - - - - - - - - - - (5) Equation (4) applies to the binary system and equation (5) applies to the ternary system.Graphical integration should then reveal ln fgs or f N as a function of Pg for the binary systems and
as a function of PA for the ternary systems. If the fugacity functions of the solid in the ternary systems
could be related to the fugacity functions of the solid in the binary systems and if the empirical relation that NA is linear in NB be assumed (4), then the
character-istics of mixture adsorption could be predicted from data on pure gas adsorption alone.
Figures 17 through 23 show fs= (Pg) for pure gases and fI = '(PA) for the mixtures. Figures 24
through 30 show the fugacities of the solid as functions of N. Figures 31 through 37 show the fugacities of
the solid in the mixtures as functions of N on a larger scale and Figures 38 and 39 diow ln f s = ( The numerical values from which these curves were plotted may be found in Tables AXL through AL. The basis for all calculations was the assumption that the fugacity of the pure solid is 1.0. In three cases the functions
i N for the pure gases were so lacking in precision at g
low pressures that the fugacity of the solid for pure gas adsorption could not be calculated. For these
cases the fugacities of the solid in the ternary systems were calculated by arbitrarily assigning a fugacity of
1.0 to the solid when one of the pure gases is adsorbed under a pressure of one atmosphere. Since the basis
of calculation in now different from the original one, the numerical values of the fugacity of the solid are incorrect. However, the shapes of the curves are cor-rect and are shown in Figures 38 and 39.
- -. Figure 17. v~ i*-~~ -Md~dL +1 I mm t, pet F -- -j
A
i 4 .4 .4/4-t ~ 4~4$& +-~Th4~.-W4T-J F4iI- +-4~A- -I-i 4-4-4 -[-LJ4-44H+14-1 i 4 4++ A+ IA iF-lt + -4--4 J .- t-4-4 4 44~4~ 4-44-4-i+4+ 44-If - Ii f4 H, 4 T _v t r-i I. y_ -, _ i4 -1 -1-
4-.,-4.
441
;
--H'44" 0 c1I fOb4T44H+"It
I I - t 0 4-! o.q 0. b 7 I 4- LL .. . 1.4 77-17
2
:4H 14 P-41 1 i 1 i 1 P -++* + t-t+ Ct2A,4. 4,4 4r+ wwmj 7H4 -~I -I 4 4 -f 4--I-- -4-A-~ ## -4-h -+ -4-4-L4 :t, ]A-f-ti 4- 4 f4i rr/~e9~v TW
Figure 19. 4 I- A- 14--~ I. 4-J-4 4-+ 4-+ L -4+ -.--44 4-4-'4 44 T 11 -7-t 4@ U +4 -t t-- 'a-7 -1jTi 4 4 71 "--4 --- 1
-Ii~I4.
i 4t/1 1 4 * - 4 .* ~ ..~ ~ I~.4-1-4 L-4-t 1 idrPu
-L4-4..LLL.A..iLZ~~iJA.74jLLV7 4: 7 Vi ~- -. t- -4 ~ ______ l T TTITYT4 t t1 4i 4--+ -t-~ 1t IT 4# 44 4T 44 i - - -4-44-444I4,----4- 4 ~- I... . .-... . I -.4. IJ.L244-. 1 LW 7V T 1 A
-4-
-~-'~~~~1 L 1 4
t-14 I i-t~v 4 .'44- I 4-4-~ -~.4- I ~ -.-.--,-.-I----. -- ~ I ~ ... 4 4 .4-J .~LJ4 .L LLL4. I LI. 41
i 4-- I - _ 7]~ 14 -4T I4 I -4 ~T.ft+ -T 141 *1-rt , HL -4-_0 -- f 44-~424F-T E LU. 74.5 7T1 1 T7~7 V 4. t 11 4.4.11 Ill T4 11 4. * I 4-,-rt-t.-4-44
4+4---/
4 ~ 4 4-~ 4 -'-44 ..- 4-9-4 4 ~ 4 s-.-.. ~ J&.4-..4I~...LL...LLL~...LLLLLLLLL 4.. V" --tt r*. Ti4f -4 - AFI _i J _4 _ 4t 1-t 7. .4 +4 . -WI _ 4 + JIlT 1~-'-~~ ~44~,. F t ~- 21 TI -44-,-I 4-"-" 7. -4. - ~ tr ~ i -f-44 : -t4-4--t-r1--t-4-$-+4-t4*4 rt-I~h.FH-+4.-41- IJ44,444I44LL 0.8 -T t__ _ .A : 4 o.2af. o-6petylneor / &vf hia-FE) a "
1W
I
I- tt 4-. #14 KI
: r 4-J t ft 12p,+ L4 41 -4Th~t -4-,---- -. -i-i-Hi3 0
~72~ 14-
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Unfortunately, no correlation could be found for predicting the fugacity of the solid in ternary systems from pure gas isotherms only. This may be due to the enormous difference in the range of values for the solid fugacity when under the pure gases and when under the mixture. This can be easily seen in Figures 24 through 30. If, for example, the fugacity of the solid when NA moles of A and NB moles of B were adsorbed at one time
(ternary system) were some function of the fugacities of the solid when NA moles of A and NB moles of B were adsorbed separately (binary systems), the fugacities
in the binary systems would have to be extremely accurate as they would be so much larger than those in the ternary system. It may be possible to find a correlation similar to this but involving only those portions of the curves for the binary systems which lie in the same range of fugacity values as those for the ternary system. For example, the fugacity of.the solid in the ternary system may be a function of the fugacities-of the solid in
the binary systems at points where the moles adsorbed in the binary systems are equal to the total moles ad-sorbed in the ternary system. This would require that the data for one of the binary systems extend to pres-sures higher than one atmosphere.
Lacking a correlation between the adsorption of the pure gases and the adsorption of the mixtures,
considerable aid could still be obtained if the shapes of the solid fugacity functions for various ternary systems could be related to one another. If the shapes of these functions could be accurately predicted, then the slopes of these curves at various points could be used to find 1A A) if the empirical relation that NA is linear
in NB could still be assumed. Chertow has shown that this relation is within engineering accuracy in most cases. Here again, no such relation could be found. These solid fugacity functions are not of the types generally foiund in engineering work since all attempts to rectify the curves failed completely.
It might be well to mention here that the Van Laar type of relation proposed by both Chertow and Cadogan should not be correct, if the solid is to be considered as a component of the system as it certainly should be. The tacit assumption which must be made in order to apply their equation correctly is that the fugacity of the solid in ternary systems at constant pressure is not affected by changes in the composition of the gaseous mixtures. This is clearly not the case. An attempt was made to apply a similar type of equation to the adsorption of the pure gas with the intention of extending it to the ternary system by analogy to the original Van Laar extension.
However, no satisfactory equation could be found, the difficulty lying in the fact that ln P approaches-oo as P approaches zero. No means could be found to make this
PRECISION
Basically, the investigations carried out in this work were done in the light of the thermodynamic
equilibria requirements of the systems. Both the ori-ginal Broughton proposal and the idea of solid fugacity are seriously hampered by the lack of precision of the data in the most critical regions, viz. when the pres-sure approaches zero. This is probably the primary reason for the failure of the two methods of attack. As mentioned before, at pressures lower than 50 or 60 millimeters of mercury, an error of five millimeters would be magnified enormously when the Y or functions
are integrated. The last type of curve is not quite so bad as the first in this respect, since the total area under the curve is distributed more evenly over the
RESULTS
The results of the work done are mainly negative and may be summed up as follows:
1. It was found that the extension of Langmuir's for-mula is sound only when the moles of pure materials adsorbed in a complete monomolecular layer are equal. 2. The Magnus mixture equation is generally inapplicable. 3. The Hill equation is not in a usable form.
4. Logically, the Van Laar type equation applied in the form proposed by Chertow and Cadogan is incor-rect since the fugacity of the solid changes with mixture composition.
5. It is unlikely that the Broughton equation can be used to test data, though it is of great value in
testing proposed correlation formulae.
6. It is unlikely that a relation can be found between the fugacity of the solid under the pure gases and the fugacity of the solid under the gaseous mixtures. 7. It may be possible to relate the variation in the
fugacity of the solid under mixtures to various types of systems.
.56
Table AI.
Original Data for the System Ethylene-Propane-PCC Carbon at 25*C
(Cadagon)
Pure Ethylene Pure Propane Mixture (P* 1 atm.)
Ps mI. Hg. 13 60 100 203 300 356 500 645 760 N, mmols. 0.301 0.667 1*25 1.90 20275 2.48 2.67 2.79 2.88 2.96 3.08 3.20 3.30 3.38 m . Hg., 4 19.5 50 100 150 200 250 300 350 400 500 600 700 800 N, mmols. 3.15 3.03 2.79 2.79 2.52 2.37 Xe Ye 0.067 0.110 0.239 00239 0.439 0.601 Table AII.
Original Data for the System Ethane-Propane-PCC Carbon at 25*C (Cadagon) Pure Ethane N, mmo ls. 00167 0.381 0.625 0.925 1.16 1.35 1.62 1.82 2.06 2.21 2.41 P, . mm. Hg. 12.5 37.0 69.5 128 180 230 312 399.5 512 59705 751.5 Pure Propane N, P, mmols. mm. Hg. 0.301 0.667 1.25 1.90 2.275 2o48 2067 2.79 2.88 2.96 3.08 3020 3.30 3.38 4 19.5 50 100 150 200 250 300 350 400 500 600 700 800 Mixture (P= 1 atm.) N, Mmols. 3.23 3.19 3.12 3.06 3.00 2.95 2.85 2.77 2.71 2064 2057 2049 2.45 X, Et. 0.050 0.100 0.150 0*200 0.250 0.300 0.400 0.500 00600 0.700 0.800 0.900 0.950 Y,9 Et. 0.385 0.505 0.570 0.615 0.653 00683 0.735 0.785 0.840 0.883 0.938 0.967 0.984 N, Mmo 1s. 0.187 0.639 0.82 1.198 1.42 1.555 1.79 2.004 2.14 00409 0.553 0.782 0.786 0.914 0.949
Table AIII.
Original Data for the System
Isobutane-Butene-l-PCC Carbon at 2500 (Cadagon) Pure Isobutane N, P, nmiols. mm. Hg. 0.312 1.46 2.27 2.46 2.67 2.79 2.87 2.93 3.05 3.14 3.23 3.31 3.33 2.5 23.5 70.5 100 150 200 250 300 400 500 600 700 747 Pure Butene-1 N, mmols. 2.08 2.40 2.73 2.95 3.10 3.22 3.30 3*47 3.59 3*69 3,78 3.83 P, mm. Hg. 21 50 100 150 200 250 300 400 500 600 700 748.5 Mixture (P= 1 atm.) N, mmols. 3.82 3.80 3.75 3.70 3*66 3*60 3.55 3*50 3.45 X,9 Iso. 0.070 0.100 0.200 0.300 0.400 0.500-0*600 0.700 0.800 Y,9 Iso. 0.140 0.174 0.305 0.408 0.505 0*600 0*693 0.773 0.862 Table AIV.
OrigLnal Data for the System Acetylene-Ethylene-PCC Carbon at 25*C (Chertow) Acetylene Pressure, mm. Hg. Pure 760 723 690 645 580 458 363 274 200 135 83 45 30 20 10 Mixture 760, 744 734 717 688 632 572 513 453 383 308 218 165 113 55 Ethylene N, Pressure, mm. Hg. mmols. Pure Mixture
2.14 2.05 2.00 1.95 1.90 1.80 1.60 1.40 1*20 1.00 0.80 0.60 0.40 0.30 0*20 0.10 760 682 645 605 570 505 385 290 213 150 103 69 41 29 20 10 760 715 693 670 645 578 518 440 372 305 243 183 120 89 60 32 N, mmols. 2.04 2.00 1.96 1.90 1.80 1.60 1.40 1.20 1.00 0.80 0.60 0.40 0.30 0.20 0.10