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Infinite Dilution
M. F. Gautreaux, Jr., and Jesse Coates
Louisiana State University, Baton Rouge, Louisiana
Vapor-liquid equilibrium data out this paper. Usually at the tem- dilution is of aid in the determina-
are frequently correlated in terms perature and pressure of t h e sys- tion of vapor-liquid equilibrium in
of activity coefficients. An activity tem the pure component will be these regions. Similarly the activ-
coefficient, y, is a thermodynamic either liquid or vapor, and one of ity coefficient a t infinite dilution is
quantity which is related t o the the standard states will be hypo- important because its logarithm
fugacity, f, of a component in thetical. generally appears a s a constant in
solution by an expression such as As the mole fraction of com- empirical equations which relate
Equation (1): ponent one approaches zero in solu- log y and % ( I ) . The coefficient is of
tion, its activity coefficient ap- interest to the scientist who is at-
flL proaches a definite limit. Tliis tempting to relate the structures
Yli. = --- (1) limiting value is frequently ter,ried of pure components and the non-
%I f I, the activity coefficient of rom- idealities of solutions. This rela-
Subscript 1 refers t o component ponent one at infinite diintion. tion is probably most easily made
one; subscript L refers to the The condition of infinite dilution a t infinite dilution where there is
liquid phase. [An equation anal- will be designated by the subscript absolutely no interaction among
ogous to Equation (1) could be z1= 0. Thus solute molecules in solution(l0).
written for component one in t h e Thus the partial molal excess free
vapor phase.] The subscript 0 energy a t infinite dilution is ob-
refers to the chosen standard state. tained ( 3 ) directly from Equation
It is convenient to choose pure (3) :
liquid and pure vapor a t the tem- This coefficient is of considerable
perature and pressure of the sys- practical and theoretical interest. (GE = K T l n y) (3)
tem for liquid- and vapor-phase I n extractive and azeotropic dis- 2=0
standard states, respectively. These tillations important components The partial molal excess enthalpy
standard states are used through- frequently appear in very low con- a t infinite dilution is obtained by
_ _ ~ ~ _ centrations in the liquid phase. determining the rate of change of
M. 17. Chutreaux, Jr., is at present with
E t h y l C ~ ~ r p w a t i o i il,i n t o n Kuuge, Louisiana. The activity coefficient a t infinite the coefficient with temperature :
(YIIJ," equals
I. Isobaric temperature-liquid
composition diagram?
RT RT
11.
And the partial molal excess en- No assumptions will be made con- where K is the familiar equilib-
tropy can then be obtained from cerning the idealities of the vapors rium vaporization ratio.
or the vapor-phase solutions. Nor Equation (8) is an exact thermo-
will the assumptions be made of a
(eE=%"- TSE)
==[I
(5) negligible heat of mixing and of a
dynamic relation for (ylL/y lv)
xl=O. It is independent of the
negligible effect of temperature on number of components under con-
Activity coefficients a t infinite activity coefficients. Relations will sideration and applies to both con-
dilution have been calculated i n a be derived f o r utilization of vapor- stant temperature and constant
variety of ways, perhaps most fre- ljquid equilibrium data, isobaric pressure data. However, Equation
quently from van Laar or similar temperature-composition diagrams, (8) involves determinations of y
constants obtained after vapor- and isothermal pressure-composi- and x in equilibrium at low values
liquid equilibrium data were cor- tion diagrams. Usually i t is sim- of y and x. These determinations
related. For example, the van Laar pler experimentally to obtain the are experimentally difficult.
constant A is related to the activity two diagrams. Further derivations will be made
coefficient of component one ( 3 ) by t o obtain ( y I L I y I v ) x I = 0 in terms
the equation of information available from the
DERIVATION OF EQUATIONS more easily obtained isobaric tem-
At equilibrium, f l L= flv, Equa- perature-composition diagrams and
tion (7) results: isothermal pressure-composition di-
agrams. A binary system will be
If vapor-liquid equilibrium data considered.
a r e available in the region x1 = 0, When a n equation for component
graphical extrapolation by eye of two analogous to Equation (7) is
ylL to x1 = 0 is often used t o obtain utilized,
( y l L ) a l = 0. Carlson and Colburn As x1 approaches zero, the right-
( 1 ) suggest using an isothermal hand member (RHM) approaches
pressure-composition diagram or the form 010. Applying L'Hospi-
an isobaric temperature-composi- tal's rule yields
tion diagram and calculating a n
"apparent" activity coefficient
which may be extrapolated to x1 =
0 to obtain (ylr,)xI = 0.
1
11. Isothermal pressure-composition diagram
TABLE3.-EXACT EQUATIONS
FOR CALCULATING K1 AT z1 = 0
1
11. Isobaric temperature-vapor composition diagram
RT RT
-__
R?'
*All terms evaluated a t conditions corresponding to x1 = 0.