Solid Liquid Equilibria

Solid Liquid Equilibria is the interrelation of a solid material and its melt at constant vapor
pressure. It is the concentration relationship of a solid with a solvent liquid other than its melt
(McGraw-Hill, 2003).The prediction of solubility of a solid in a liquid is important for design of
separation processes that utilize either preferential dissolution or crystallization as a route to
purification of a species. (NPTEL, 2013)

Moreover, solid-liquid separation involves the separation of two phases, solid and liquid,
from a suspension. It is used in many processes for the: 1. recovery of valuable solid component (the
liquid being discarded); 2. liquid recovery (the solids being discarded); 3. recovery of both solid and
liquid; or 4. recovery of neither phase (e.g., when a liquid is being cleaned prior to discharge, as in
the prevention of water pollution). (Wakeman, 2011)

Thus, it is important in understanding unit operations specifically leaching, crystallization

3.4.1 Equilibrium Relationships

A. Leaching
Leaching is a liquid-solid operation. The two phases are in intimate contact, the solute(s)
can diffuse from the solid to the liquid phase, which causes a separation of the components
originally in the solid.
In this process it is assumed that there is sufficient solvent present so that all the solute in
the entering solid can be dissolved into the liquid, equilibrium is reached when the solute is
dissolved. It is also assumed that the solid is insoluble, and no adsorption will happen for the solute
in the solid. This solid-liquid stream is called the underflow or slurry stream. The liquid is called the
overflow stream. The concentration of oil or solute in the overflow stream is equal to that in the
liquid solution accompanying the slurry or underflow stream. Hence, on an xy plot the equilibrium
line is on the 45o line. (Geankoplis)
 1
xc, yc mass fraction solvent

0.5

(1)

0.3

(2)
(3)

0.5 1

xa, ya mass fraction solute

Figure 1 Underflow compositions for solid-liquid extraction

An "equilibrium stage" can be defined as one where the liquid adhering to the solids leaving
has the same composition as the liquid-extract phase leaving. It is then necessary to determine
experimentally the mass of adhering liquid per unit mass of insoluble solids. Such data can be
plotted on a ternary diagram, as shown in Figure 1. The resulting' curves are referred to as
"underflow loci" and do not represent true equilibrium conditions. The underflow may be
considered a mixture of inert solids and solution. The right-angle vertex represents pure inert solids
and the hypotenuse of the ternary diagram represents clear solutions. Any line joining a clear-
solution composition on the hypotenuse with the right angle intersects the underflow locus at the
underflow composition in equilibrium with the clear solution. Therefore, the portion of the line
from the hypotenuse to the underflow locus is an equilibrium tie line. (Foust, Wenzel, Clump,
Maus, & Andersen, 1959)

Underflow-Overflow for Ideal Leaching

Figure 2 depicts ideal leaching conditions where, in the underflow, the mass ratio of
insoluble solid to liquid, XA, is a constant, independent of the concentration, XB, of solute in the
solids-free liquid. The resulting tie line is vertical.

Figure 3 variable-solution underflow

Figure 3 depicts ideal leaching conditions when XA varies with XB. In both cases, the assumptions
are:
 an entering feed, F, free of solvent such that XB = 1;
 a solids-free and solute-free solvent, S, such that YA = 0 and YB =0;
  equilibrium between exiting liquid solutions in underflow, U, and overflow, V, such that
XB = YB; and
 a solids-free overflow, V, such that YA = 0.
A mixing point, M, can be defined for (F + S), equal to that for the sum of the products of the
leaching stage, (U +V). Typical mixing points, and inlet and outlet compositions,
are included in Figures2 and 3. In both cases, the inverse-lever-arm rule can be applied to line
UMV to obtain flow rates of U and V.
Ideal leaching calculations can be done algebraically or with diagrams. Let:
F = total mass flow rate of feed to be leached
S = total mass flow rate of entering solvent
U = total mass flow rate of the underflow, including solids
V = total mass flow rate of the overflow
XA = mass ratio of insoluble solid A to (solute B + solvent C) in the feed flow, F, or underflow
YA = mass ratio of insoluble solid A to (solute B + solvent C) in the entering solvent flow, S, or
overflow, V
XB =mass ratio of solute B to (solute B + solvent C) in the feed flow, F, or underflow, U
YB = mass ratio of solute B to (solute B + solvent C) in the solvent flow, S, or overflow, V

Example A.
In a Single-Stage Leaching of soybean oil from flaked soybeans with hexane, 100 kg of
soybeans containing 20 wt % oil is leached with 100 kg of fresh hexane solvent. The value of N for
the slurry underflow is constant at 1.5 kg insoluble solid/kg solution retained. Calculate the
amounts and compositions of the overflow V1 and the underflow L1 leaving the stage.
Solution:
The process flow diagram and known variables are as follows.

V1 V2=100 kg

X1 X2=0

Slurry Slurry

B= 100(1-20%) = 80 kg
B= 80 kg solid solid
L0=20kg L1
N0=B/L0=4 N1=1.5
YA0=1 YA1
To locate the point M, use the material balances:
L0 + V2 = 20 + 100 = 120kg = M

L0 YA + V2 x A = 20(1) + 100(0) = 20 = Mx A = 120x A

B = L0N0 = 20(4) = MNM

The point M is plotted along with V2 and L0. A vertical line is drawn to locate L1 and V1 in
equilibrium with each other. So,
N 1 = 1.5
y A = x A = 0.167
1 1
By using level-arm rule, we obtain L1=53.3 kg and V1=66.7 kg.