c 2011 Ismail Tosun

Chapter 11 Liquid-Liquid Equilibrium

When two liquids are mixed, depending on the temperature and/or composition, either they are completely miscible in each other and form a single phase, or they are partially miscible (or totally immiscible) in each other and form two separate phases. In the case of completely miscible, i.e., single phase, systems, the equations developed in Chapter 6 are applicable. In this chapter, we are interested in the case when a liquid is partially miscible (or totally immiscible) in another liquid. First, the reason for making liquids partially miscible in each other will be investigated. Then the procedure to determine the compositions in two separate liquid phases that are in equilibrium with each other will be described. Such equilibrium data are needed in various chemical and physical processes such as liquid-liquid extraction and tertiary oil recovery. 11.1 STABILITY OF MULTICOMPONENT LIQUID MIXTURES For thermodynamically allowable changes at constant temperature and pressure, the criterion (dG)T,P 0 (11.1-1)

indicates that all irreversible changes taking place at constant temperature and pressure must decrease the total Gibbs energy of the system. When the system reaches equilibrium, no further changes can occur and Gibbs energy reaches its minimum value. Let us consider the mixing of two liquids, 1 and 2, at constant temperature and pressure. The Gibbs energy of this binary mixture is e e Gmix = n1 G1 + n2 G2 + Gmix (11.1-2)

If the Gibbs energy of the mixture is lower than the summation of the Gibbs energies of pure liquids, then liquids 1 and 2 will be miscible (totally or partially) in each other. Otherwise, liquids 1 and 2 tend to remain unmixed like olive oil and water. The condition of miscibility is mathematically expressed as e e (11.1-3) Gmix < n1 G1 + n2 G2 or, in other words, Gmix < 0 (11.1-4) which is the criterion for miscibility (partial or complete). The Gibbs energy of mixing is given by e e e Gmix = Hmix T Smix | {z } | {z }
X Y

(11.1-5)

Since mixing increases the degree of disorder within the system, the entropy change on mixing, e Smix , is always positive. Thus, the term Y in Eq. (11.1-5) is always positive. The heat of 381

e Case (i): Exothermic mixing (Hmix < 0) e When Hmix < 0, interactions between unlike molecules are greater than those between like e molecules, i.e., negative deviation from Raoults law leading to i < 1. In this case, Gmix is negative for all compositions of components 1 and 2. Therefore, liquids are completely miscible in each other and form a stable single phase. This situation is illustrated in Figure 11.1.

e mixing, Hmix , is related to the energetic eects. In order to make a mixture of 1 and 2 from pure components, it is necessary to break 1-1 and 2-2 bonds and form 1-2 bonds1 . Depending on e the magnitude of the interactions between like and unlike molecules, Hmix may take positive or negative values. Therefore, it is necessary to consider the following two cases.

~ Hmix ~ TS mix

~ TS mix ~ Hmix

~ Gmix

~ Gmix

x1

x1

e Case (ii): Endothermic mixing (Hmix > 0) e When Hmix > 0, interactions between like molecules are stronger than those between unlike molecules, i.e., positive deviation from Raoults law leading to i > 1. In this case, examination of Eq. (11.1-5) indicates that the terms X and Y compete with each other and the magnitude e of the temperature decides the dominant term and, hence, the sign of Gmix . e e a) At low temperatures, Hmix T Smix and, as shown in Figure 11.2, this indicates that emix > 0. Therefore, liquids 1 and 2 tend to remain as two separate phases throughout the G whole composition range, i.e., liquids 1 and 2 are immiscible in each other.

e e e e Figure 11.1 Eects of Smix and Hmix on Gmix when Hmix < 0.

~ Hmix

~ Gmix

0
~ T S mix

x1

e b) When temperature is high enough so that Gmix < 0, we may encounter two dierent e emix Hmix , liquid phases mix with each other throughout the whole situations. When T S composition range as shown in Figure 11.3.
1

e e e e Figure 11.2 Eects of Smix and Hmix on Gmix when Hmix > 0 with e e mix T Smix . H

As stated in Section 6.3, while bond breaking is an endothermic process, bond formation is exothermic.

382

~ Hmix

0
~ Gmix

~ TS mix

x1

e e An interesting case may arise when T Smix > Hmix . Under these circumstances, variae tion in Gmix with respect to composition may result in more than one minimum, as shown in Figure 11.4. Examination of this case requires the following mathematical preliminaries.
~ Gmix

e e e e Figure 11.3 Eects of Smix and Hmix on Gmix when Hmix > 0 with e emix Hmix . T S

x1

A function f (x) is said to be a concave function in x if and only if the points on a chord connecting two points on a function lie beneath the function. On the other hand, a function f (x) is said to be a convex function in x if and only if the points on a chord connecting two points on a function lie above the function. Concave and convex functions are shown in Figure 11.5.
f ( x) Concave Function f ( x) Convex Function

e e Figure 11.4 Variation in Gmix with composition when Hmix > 0 with e emix > Hmix . T S

Figure 11.5 Concave and convex functions. Consider a function f that is dependent on a single variable x. Various possibilities exist for the variation of f (x) with x as shown in Figure 11.6. Note that the functions on the left (a and c) are convex, while the functions on the right (b and d) are concave. 383

f (x )

df >0 dx

d2f dx
2

>0

f (x )

df >0 dx

d 2f dx 2

<0

x (a) (b)

f (x )

df <0 dx

d2f dx
2

>0

f (x )

df <0 dx

d 2f dx 2

<0

x (c) (d)

Figure 11.6 Variation of the rst and second derivatives of convex and concave functions. The rst derivative of f (x), df (x)/dx, measures the rate of change of the function f (x). The second derivative of f (x), d2 f (x)/dx2 , measures the rate of change of the rst derivative, df (x)/dx. The signs of the rst and second derivatives of f (x) imply the following: df (x) > 0 Value of f (x) increases with increasing x (11.1-6) < 0 Value of f (x) decreases with increasing x dx d2 f (x) > 0 Slope of f (x) vs x tends to increase (11.1-7) < 0 Slope of f (x) vs x tends to decrease dx2 Note that the second derivative can be used to determine whether a function is concave or convex. The second derivatives of concave and convex functions are negative and positive, respectively. Let us consider a concave function of a single variable, f (x), and draw a chord joining any two points on the function as shown in Figure 11.7. The chord intersects the function at xA and xB . Let xc be any value between xA and xB such that xc = xA + (1 )xB where 0 1.
f ( x) f [x A + (1 )xB ] f( xB )

(11.1-8)

[x A + (1 )x B ]
f( xA )

xA

xC

xB

Figure 11.7 A concave function.

384

The equation of the chord is (x) = f (xB ) f (xA ) (x xA ) + f (xA ) xB xA (11.1-9)

When x = xA + (1 )xB , from Eq. (11.1-9) we have i h xA + (1 ) xB = f (xA ) + (1 ) f (xB ) Substitution of Eq. (11.1-11) into Eq. (11.1-10) gives f (xA ) + (1 ) f (xB ) < f xA + (1 ) xB

From Figure 11.7 it is apparent that h i h i xA + (1 )xB < f xA + (1 )xB

(11.1-10)

(11.1-11)

(11.1-12)

Now let us tackle the case shown in Figure 11.4 by drawing a common tangent line to the minima2 , as shown in Figure 11.8. The so-called common tangent rule states that when the composition of the mixture is between x and x , instead of having a homogeneous mixture, we 1 1 have two separate phases, and , that are in equilibrium with each other. The compositions of these coexisting equilibrium phases lie at the points of co-tangency, i.e., x and x . The 1 1 coexisting compositions are called binodal points. The reason for the phase separation can be expressed as follows.
Points of co-tangency (not minima)

~ Gmix

Inflection points ~ d 2 Gmix =0 dx12

Common tangent to the minima

x 1

x1

x1

Figure 11.8 Common tangent rule. Let x be the mole fraction of component 1 between x and x , i.e., 1 1 1 x = x + (1 ) x 1 1 1 where 0 1. Note that the solution of Eq. (11.1-13) for gives =
2

(11.1-13)

x x 1 1 x1 x 1

(11.1-14)

Keep in mind that drawing a common tangent to the minima does not imply joining the minimum points by a straight line.

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From the lever rule

x x 1 1 x1 x 1

n n + n

(11.1-15)

which states that the combined Gibbs energies of the two separate liquid phases are lower than the Gibbs energy of a homogeneous mixture. Since the system tries to minimize its Gibbs energy, over this composition range we have two separate phases of compositions x and x , 1 1 and the common tangent acts as a "tie line". e When x < x1 < x , there are two inection points at which d2 Gmix /dx2 = 0. The 1 1 1 e inection points are called spinodal points. Between the two inection points, Gmix is a 2 G emix /dx2 < 0. concave function with d 1 e Figure 11.8 shows the variation of Gmix as a function of composition at a xed temperature, say T1 . By using these data, it is possible to locate binodal and spinodal compositions on e a temperature-composition (or solubility) diagram, as shown in Figure 11.9. If Gmix versus x1 data are known at various temperatures, then it is possible to draw binodal and spinodal curves.
~ G mix T = T1

Comparison of Eqs. (11.1-14) and (11.1-15) reveals that the term represents the mole fraction of the -phase. According to Eq. (11.1-12) h i e e e (11.1-16) Gmix (x ) + (1 ) Gmix (x ) < Gmix x + (1 ) x 1 1 1 1

0
T

x1

Binodal curve

T1

Spinodal curve

x1

Figure 11.9 Liquid-liquid solubility diagram. The binodal and spinodal curves coincide at the critical solution ( or consolute) temperature, i.e., the temperature at which two partially miscible liquids become fully miscible. In other words, when the temperature is above the critical solution temperature, the mixture is completely miscible and forms a homogeneous phase. At temperatures below the critical 386

solution temperature, the mixture is partially miscible and the binodal curve is the boundary between the two-phase and one-phase regions. Within the two-phase region, the region between the spinodal and binodal curves is metastable, and the time it takes for the phase separation is not denite. On the other hand, within the spinodal curve, the mixture is unstable and phase separation takes place immediately. Since the end points of the spinodal curve represent inection points, then the condition of instability of liquid mixtures can be stated as e d2 Gmix dx1
2

<0

Condition of instability

(11.1-17)

where e e e GIM Gex Gmix mix = + RT RT RT N X e Gex = xi ln xi + RT

i=1

(11.1-18)

For a binary system, substitution of Eq. (11.1-18) into Eq. (11.1-17) gives e 1 d2 (Gex /RT ) + <0 2 x1 x2 dx
1

(11.1-19)

One should keep in mind that the criterion given by Eq. (11.1-4) is a necessary but not e sucient condition for complete miscibility of components. When Gmix (or Gmix ) is a convex function of composition with only one minimum, components are miscible in each other e over the entire composition range and form a homogeneous phase. When Gmix (or Gmix ) is a convex function of composition with more than one minimum, phase separation, i.e., formation of two (or more) phases, takes place. Example 11.1 In a binary liquid mixture of 1 and 2 at constant temperature and pressure, the molar excess Gibbs energy is expressed as h i e Gex = x1 x2 1.8 + 0.3 (x1 x2 ) 0.85 (x1 x2 )2 RT

Therefore, the concentrations at the spinodal points are obtained from the solution of the following equation: e 1 d2 (Gex /RT ) + =0 (11.1-20) 2 x1 x2 dx
1

Determine the region of instability. Solution

e Substitution of Gex /RT into Eq. (11.1-20) and dierentiation give

408 x4 852 x3 + 511 x2 67 x1 10 = 0 1 1 1

(1)

R The solution of Eq. (1) by MATHCAD gives x1 = 8.54 102 , x1 = 0.378, x1 = 0.682 and x1 = 1.114. Therefore, the limits of instability are given as

0.378 < x1 < 0.682 387

In other words, these are the mole fractions at the spinodal points. Comment: Equation (11.1-18) gives h i e Gmix = x1 ln x1 + x2 ln x2 + x1 x2 1.8 + 0.3 (x1 x2 ) 0.85 (x1 x2 )2 RT

e The variation of Gmix /RT versus x1 is given in the gure below.

0.043 0

0.1

G( x) 0.2

0.3 0.35 0 0.01 0.2 0.4 x 0.6 0.8 0.99 1

The common tangent rule gives the binodal compositions as x1 = 0.26 and x1 = 0.80.

The simplest function to express molar excess Gibbs energy as a function of composition is the one-constant Margules model, Eq. (8.4-1), e Gex = A x1 x2 RT (11.1-21)

Substitution of Eq. (11.1-21) into Eq. (11.1-18) gives

Note that

e Gmix = x1 ln x1 + x2 ln x2 + A x1 x2 RT d dx1 e Gmix RT ! = ln x1 x2 + A(x2 x1 )

(11.1-22)

(11.1-23)

e indicating that d(Gmix /RT )/dx1 = 0 at x1 = x2 = 0.5. On the other hand, the use of Eq. (11.1-21) in Eq. (11.1-19) indicates that phase splitting takes place when 1 1 (11.1-24) A> 2 x1 x2 The function 1/x1 x2 becomes + for pure components, i.e., either x1 = 1 or x2 = 1, and falls to a minimum value of 4 at x1 = 0.5. Therefore, a binary liquid mixture becomes unstable and exists as two separate phases when A > 2. From Eq. (8.4-4) A = ln i 388 i = 1, 2 (11.1-25)

Therefore, phase separation takes place when ln > 2 (or > 7.4). A plot of Eq. (11.1-22) i i e in the form of Gmix /RT versus x1 is presented in Figure 11.10 for various values of A, i.e., 0, 1, 2, 3, 4.
0.4 0.307 0.2 G ( x1, 1) G ( x1, 0) 0

G ( x1, 2) 0.2 G ( x1, 3) G ( x1, 4) 0.4

0.6 0.693 0.8 0 110

3

0.2

0.4 x1

0.6

0.8 0.999

e Figure 11.10 A plot of Eq. (11.1-22) in the form of Gmix /RT versus x1 with A being a parameter. The parameter of the two-sux Margules equation, A, is dependent on temperature. If A decreases with increasing temperature as shown in Figure 11.11-a, then the temperature corresponding to A = 2 is the upper critical solution temperature (UCST). At temperatures greater than UCST, a binary mixture becomes homogeneous. When A increases with increasing temperature as shown in Figure 11.11-b, then the temperature corresponding to A = 2 is the lower critical solution temperature (LCST). In this case, a binary mixture becomes homogeneous at temperatures less than LCST. If the variation of A with respect to temperature exhibits a maximum, then a binary mixture has both UCST and LCST as shown in Figure 11.11-c. Finally, if the variation of A with respect to temperature exhibits a minimum, then the corresponding solubility diagram is as shown in Figure 11.11-d. 11.2 LIQUID-LIQUID PHASE EQUILIBRIUM CALCULATIONS Consider a multicomponent mixture of k species distributed in two liquid phases, and . The condition of equilibrium states that the fugacities of each species in - and -phases must be equal to each other, i.e., b b fi (T, P, x ) = fi (T, P, x ) i i i = 1, 2, ..., k (11.2-1)

In terms of activity coecients, Eq. (11.2-1) takes the form (T, P, x ) x fi (T, P ) = (T, P, x ) x fi (T, P ) i i i i i i or (T, P, x ) x = (T, P, x ) x i i i i i i i = 1, 2, ..., k (11.2-3) In each phase, the mole fractions are related to each other by the following equations:
k X i=1

(11.2-2)

x = 1.0 i

and

k X i=1

x = 1.0 i

(11.2-4)

389

Simultaneous solution of Eqs. (11.2-3) and (11.2-4) gives the coexistence curve for the twophase system.
T A TWO PHASES 2 ONE PHASE TWO PHASES T* (UCST) ONE PHASE

T * (UCST) A TWO 2 ONE PHASE PHASES

(a)

x1 T TWO PHASES

T (LCST) T (LCST) A
*

ONE PHASE x1

(b) T UCST

ONE PHASE

TWO 2

PHASES

TWO PHASES

ONE PHASE LCST LCST A UCST T

ONE PHASE x1

(c)

TWO PHASES

TWO PHASES 2 ONE PHASE

LCST ONE PHASE UCST TWO PHASES

UCST

LCST

T (d)

x1

Figure 11.11 Four dierent types of solubility diagram. For a binary system, Eqs. (11.2-3) and (11.2-4) become ! x 1 1 ln = ln 1 x1 ! 1 x 2 1 = ln ln 2 1 x1 390

(11.2-5)

(11.2-6)

In practice, one encounters two types of liquid-liquid equilibrium calculations: When compositions are known, Eqs. (11.2-5) and (11.2-6) can be solved for the parameters of an activity coecient model. When parameters of an activity coecient model are known, Eqs. (11.2-5) and (11.2-6) can be solved for the compositions in - and -phases. Example 11.2 Diethyl ether (1) and water (2) form two partially miscible liquid phases. At 308 K and atmospheric pressure, Villamanan et al. (1984) reported the following compositions of the two phases: and x = 0.9500 x = 0.01172 1 1 If the system is represented by the three-sux Margules equation, estimate the parameters A and B. Solution Substitution of Eqs. (8.4-6) and (8.4-7) into Eqs. (11.2-5) and (11.2-6), respectively, gives 2 i h x 1 2 2 2 A (1 x1 ) 1 x1 + B (1 x1 ) (4 x1 1) (1 x1 ) (4 x1 1) = ln (1) x1 h 2 i 1 x 1 A (x )2 x + B (x )2 (4 x 3) (x )2 (4 x 3) = ln 1 1 1 1 1 1 1 x1 (1 x )2 (1 x )2 1 1 (x )2 1 (x )2 1 (1 x )2 (4 x 1) (1 x )2 (4 x 1) 1 1 1 1 (x )2 (4 x 1 1 3) (x )2 (4 x 1 1 3) 1 (2)

The use of matrix algebra gives the parameters A and B as A B

or A= where

ln x1 (3) 1 x1 ln 1 x1 X ( ) 6 (x + x 1) 1 1 2 (x x )3 1 1 and B= (x + x ) ( ) + 2 1 1 2 (x x )3 1 1 1 x 1 (4)

x 1

X = (x + x )(4x + 4x 3) 4x x 1 1 1 1 1 1

Substitution of the numerical values into Eqs. (4) and (5) gives A = 3.854 and 391

= ln

x 1 x 1

= ln

1 x 1

(5)

B = 0.683

Comment: The use of Eq. (8.4-9) gives = 93.4 1 and = 23.8 2

As stated in Section 8.3, activity coecients are greater than unity when components repel each other, i.e., unlike interactions are weaker than like interactions. When i (or ) is very i much greater than unity, it is more likely that phase separation will take place.

Example 11.3 Estimate the compositions of the coexisting liquid phases in a mixture of npentane (1) and sulfolane (2) at 374.11 K. The system is represented by the NRTL model and Ko et al. (2007) reported the following parameters: 12 = 2.329 Solution From Eq. (8.4-27) h i G12 = exp( 12 ) = exp (0.3)(2.329) = 0.497 Therefore, activity coecients dened by Eqs. (8.4-29) and (8.4-30) become " # 2 1.158 0.727 2 ln 1 = (1 x1 ) 1.061 + 0.727 + 0.273 x1 (1 0.503 x1 )2 ln 2 = x2 1 " 0.497 2.329 1 0.503 x1 2 0.771 + (0.727 + 0.273 x1 )2 # h i G21 = exp( 21 ) = exp (0.3)(1.061) = 0.727 21 = 1.061 = 0.3

(1)

(2)

Substitution of Eqs. (1) and (2) into Eqs. (11.2-5) and (11.2-6), respectively, results in two highly nonlinear equations given by (1 x )2 1.061 1 0.727

0.727 + 0.273 x1 (1 x )2 1.061 1 0.497 !2 +

!2

1.158 + (1 0.503 x )2 1 0.727 !2 +

1.158

0.727 + 0.273 x1

(1 0.503 x1 )2

= ln

x 1
x1

(3)

(x )2 2.329 1

(0.727 + 0.273 x1 )2 !2 1 x 0.497 0.771 1 = ln (x )2 2.329 + (4) 1 2 1 0.503 x1 (0.727 + 0.273 x1 ) 1 x1 1 0.503 x1

0.771

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Simultaneous solution of Eqs. (3) and (4) requires a numerical technique3 . Using MATHR CAD x = 0.234 and x = 0.920 1 1 It is much easier to determine compositions graphically by drawing a common tangent to the e minima of Gmix /RT versus the x1 curve. The molar excess Gibbs energy for the NRTL model is given by Eq. (8.4-26). Thus, the molar Gibbs energy change on mixing is given by e Gmix = x1 x2 RT 0.771 1.158 + x1 + 0.727 x2 x2 + 0.497 x1 + x1 ln x1 + x2 ln x2 (8)

e The values of Gmix /RT as a function of x1 are given in the table below: x1 0.00 0.05 0.10 0.15 0.20 0.25 0.30 e Gmix /RT 0 0.093 0.123 0.135 0.137 0.132 0.124 x1 0.35 0.40 0.45 0.50 0.55 0.60 0.65 e Gmix /RT 0.114 0.104 0.093 0.083 0.074 0.067 0.062 x1 0.70 0.75 0.80 0.85 0.90 0.95 1.00 e Gmix /RT 0.059 0.059 0.060 0.062 0.063 0.056 0

e The gure shown below shows the variation in Gmix /RT with composition. The equilibrium compositions in the two-phase region can be determined by drawing a line tangent to the minima with the result x = 0.23 and x = 0.92. 1 1
0.026 0

0.05

G x.1

( )
0.1

0.137 0.15 0 0.01 0.2 0.4 x.1 0.6 0.8 0.99 1

Liquid-liquid equilibrium separations are analogous to the ash calculations mentioned in Chapter 9. Consider a binary liquid mixture with a solubility diagram as shown in Figure 11.12-a. Initially the temperature is at T1 and the overall mole fraction of component 1 is z1 . This liquid mixture enters a separation tank with a molar ow rate of F as shown in Figure
3

Newtons method for solving nonlinear systems of equations is explained in Problem 11.6.

393

11.12-b. Phase separation is initiated4 within the tank by decreasing temperature to T2 . The molar ow rates of the resulting - and -phases are L and L , respectively. Throughout the process, the pressure is kept constant at a value above the bubble point pressure of the mixture so that no vapor phase is present.
T1

T L F L

L , x1

T2

F1 z1

-Phase -Phase

L , x 1 0
x1

z1 x1 (a)

x1

(b)

Figure 11.12 Liquid-liquid ash problem. The overall and component material balances around the separation chamber are given by F = L + L F zi = L x + L x i i i = 1, 2 (11.2-7) (11.2-8)

For component 1, combination of Eqs. (11.2-7) and (11.2-8) leads to x z1 L 1 = F x1 x 1 (11.2-9)

Using the solubility diagram given in Figure 11.12, Eq. (11.2-9) can also be obtained by the application of the lever rule. From the equilibrium relation given by Eq. (11.2-3) ! 1 x1 = (11.2-10) x 1 x1 = 1 x1 1 1 Substitution of Eq. (11.2-10) into Eq. (11.2-9) and rearrangement yield 1 z1 1 x = 1 L 1 1+ 1 F 1
4

(11.2-11)

Thermodynamics is not concerned with the question of "How long will it take for the phase separation to take place?"

394

A similar development for x gives 2

Addition of Eqs. (11.2-11) and (11.2-12) results in 1 2 z1 z2 1 2 + =1 L 1 L 2 1+ 1 1 + 1 F F 1 2

2 x = 2 L 2 1+ 1 F 2

z2

(11.2-12)

(11.2-13)

which is analogous to the equations developed for ash calculations, i.e., Eqs. (9.3-19) and (9.3-20). At a given z1 and F , calculation of L (or L ), x , and x requires the following iterative 1 1 procedure: 1. Assume x and calculate x from Eq. (11.2-10). Note that the solution of Eq. (11.2-10) is 1 1 not straightforward since may be a highly nonlinear function of x . 1 1 2. Calculate L /F from Eq. (11.2-9). 3. Substitute the values into the left-hand side of Eq. (11.2-13) and check whether the summation is equal to unity. 11.3 DISTRIBUTION OF A SOLUTE BETWEEN TWO IMMISCIBLE LIQUIDS Consider two immiscible solvents forming two separate phases, and . Let component 1 be the solute which is distributed between the two phases. Under equilibrium conditions b b f1 = f1 (11.3-1) (11.3-2)

or

x = x 1 1 1 1

The distribution of a solute between the - and -phases is quantied by the partition coecient or distribution coecient, K1 , dened as
K1

x 1 x 1 1 1

(11.3-3)

The use of Eq. (11.3-2) in Eq. (11.3-3) results in

K1 =

(11.3-4)

On the other hand, the material balance for the solute is written as n1 = n x + n x 1 1 = n K1 + n x 1 395

(11.3-5)

Example 11.4 An organic acid is to be extracted from a 20 mol % acid and 80% hexane mixture by liquid-liquid extraction using water at 298 K. It is required to estimate the moles of water per mole of this mixture for removing 90% of the acid from the hexane. Assume that hexane and water are completely immiscible and that the phases leaving the extractor are in equilibrium. The following data are given at 298 K: For organic acid (1) - hexane (2) mixture: For organic acid (1) - water (3) mixture: Solution e Gex /RT = 0.012 x1 x3 e Gex /RT = 0.2 x1 x2

Let and be the hexane and water phases, respectively. Choosing 100 mol of acid-hexane mixture as a basis, nal amounts of acid and hexane in the -phase are n = 80 mol 2 n = (20)(0.1) = 2 mol 1 Thus, 2 = 0.02439 82 From the given data, the activity coecients of acid in the - and -phases are i i h h = exp 0.2(1 x )2 and = exp 0.012(1 x )2 1 1 1 1 x = 1 The condition of equilibrium is expressed as x = x 1 1 1 1 or i i h h x exp 0.2(1 x )2 = x exp 0.012(1 x )2 1 1 1 1

Substitution of the numerical values gives i i h h (0.02439) exp 0.2(1 0.02439)2 = x exp 0.012(1 x )2 1 1 20 2 n

The solution gives x = 0.02917. Therefore, the number of moles of the -phase is 1 0.02917 = n = 617 mol

The number of moles of water is n = 617 18 = 599 mol 3 The desired molar ratio is 599 = 5.99 mol of water per mol of acid-hexane mixture 100

396

11.3.1 Octanol-Water Partition Coecient Octanol [CH3 (CH2 )7 OH] and water are partially immiscible and the distribution of an organic compound i between these two phases is known as the octanol-water partition coecient, Kiow , i.e., co i (11.3-6) Kiow = w ci Since Kiow values may range from 104 to 108 (encompassing 12 orders of magnitude), it is usually reported as log Kiow . Octanol-water partition coecients of various substances are given in Table 11.1. Table 11.1 Octanol-water partition coecients of various substances5 . Substance Methanol Chloroform Benzene 1,1,2,2-Tetrachloroethane 1,1,1-Trichloroethane Naphthalene Hexachlorobenzene Chemical Formula CH3 OH CHCl3 C6 H6 C2 H2 Cl4 CH3 CCl3 C10 H8 C6 Cl6 log K ow 0.77 1.97 2.13 2.39 2.49 3.29 6.18

Cells are mainly made of lipids and they are generally modeled as a lipid bilayer model, with a long hydrophobic (water disliking) chain and a polar hydrophilic (water liking) end. The reason for choosing n-octanol is the fact that it exhibits both a hydrophobic and a hydrophilic character, and its carbon/oxygen ratio is similar to that of lipids. In other words, n-octanol mimics the structure and properties of cells and organisms. Since octanol-water partition coecient quanties how a substance distributes itself between lipid and water, it is extensively used to describe lipophilic (lipid liking) and hydrophilic properties of a particular substance. In that respect, it is one of the key physical/chemical properties, such as vapor pressure and solubility in water, used to assess the impact of agricultural and industrial chemicals on the environment. For example, polychlorinated biphenyls (PCBs) have low solubilities in water and high octanol-water partition coecients. If PCBs are accidentally released into the lake, then they are most probably found in higher concentrations in the sediment layer. 11.4 STEAM DISTILLATION If two immiscible liquids are placed in a tank, the one with the lower density oats on the top layer and solely contributes to the pressure in the vapor phase. The liquid with the higher density has no contribution to the pressure in the vapor phase since it is located in the lower layer. Therefore, when we talk about the vapor-liquid-liquid equilibrium (VLLE) calculations, we are implicitly assuming that the liquid phases are continuously agitated in such a way that there will be droplets of both liquids on the surface, which is in contact with the vapor phase.
Compiled from US National Library of Medicine, Hazardous Substances Data Bank (HSDB), http://toxnet.nlm.nih.gov. See also A Databank of Evaluated Octanol-Water Partition Coecients (LOGKOW), http://logkow.cisti.nrc.ca/logkow/index.jsp.
5

397

A pure liquid starts to boil when its vapor pressure equals the surrounding pressure. For example, using the values given in Appendix C, the vapor pressures of toluene and water are expressed as 3096.52 vap ln Ptoluene = 9.3935 T 53.67 3816.44 vap ln Pwater = 11.6834 T 46.13 vap is in bar and T is in K. The normal boiling point temperatures of pure toluene where P and pure water are
sat Ttoluene = 53.67 + sat Twater = 46.13 +

3096.52 = 383.78 K 9.3935 ln 1.01325

3816.44 = 373.15 K 11.6834 ln 1.01325 In the case of immiscible liquids, each component contributes to the vapor pressure of the mixture. The total pressure is simply the sum of the vapor pressures of each component, i.e.,
k X i=1

P =

Pivap

Immiscible mixture

(11.4-1)

Since toluene and water are essentially immiscible as liquids, Eq. (11.4-1) is expressed as 3816.44 3096.52 + exp 11.6834 = 1.013 exp 9.3935 T 53.67 T 46.13 The solution of the above equation gives T = 357.48 K. Thus, under atmospheric pressure, a toluene-water mixture boils at 357.48 K, lower than the boiling points of pure toluene (383.78 K) and water (373.15 K). High boiling point liquids at atmospheric pressure, i.e., essential oils6 , waxes, and complex fats, may decompose at high temperatures and cannot be puried by distillation. Since oils are usually insoluble in water, then the mixture of oil and steam boils at a temperature well below the boiling point of pure oil. Therefore, to decrease the boiling point, steam is directly injected into the distillation column. When the resulting vapor is condensed, the two immiscible liquid phases are separated easily. Such a process is called steam distillation.

REFERENCES
Abedinzadegan, M. and A. Meisen, 1996, Fluid Phase Equilibria, 123, 259-270. Abraham, M.H., G.S. Whiting, R. Fuchs and E.J. Chambers, 1990, J. Chem. Soc. Perkin Trans., 2, 291-300. Baudot, A. and M. Marin, 1996, J. Membrane Science, 120, 207-220. Furuya, T., T. Ishikawa, T. Funazukuri, Y. Takebayashi, S. Yoda, K. Otake and T. Saito, 2007, Fluid Phase Equilibria, 257, 147-150.
6

Essential oils are the concentrated extracts of plants and herbs.

398

Ko, M., J. Im, J.Y. Sung and H. Kim, 2007, J. Chem. Eng. Data, 52, 1464-1467. Lipinsky, C.A., F. Lombardo, B.W. Dominy and P.J. Feeney, 1996, Advanced Drug Delivery Reviews, 23, 3-25. May, W.E., S.P. Wasik, M.M. Miller, Y. B. Schult, C.J., B.J. Neely, R.L. Robinson, K.A.M. Gasem and B.A. Todd, 2001, Fluid Phase Equilibria, 179, 117-129. Van Ness, H.C. and M.M. Abbott, 1982, Classical Thermodynamics of Nonelectrolyte Solutions, McGraw-Hill, New York. Villamanan, M.A., A.J. Allawl and H.C. Van Ness, 1984, J. Chem. Eng. Data, 29, 431-435.

PROBLEMS
Problems related to Section 11.1 11.1 Show that an ideal mixture always forms a homogeneous phase over the entire composition range. 11.2 Start with Eq. (8.4-18) and show that e d2 (Gex /RT ) dx1
2

2 12 x1 (x1 + 12 x2 )2

2 21 x2 (x2 + 21 x1 )2

(1)

for the Wilson model. Since Eq. (1) is always positive (Why?), conclude that the Wilson model cannot be used to predict phase separation. 11.3 For a binary liquid mixture of water (1) and diacetyl (2), Baudot and Marin (1996) reported the following activity coecients at innite dilution = 3.3 1 = 13 2 303 < T < 323

Estimate the spinodal compositions if the system is represented by the three-sux Margules model. (Answer: x1 = 0.531 and x1 = 0.799) 11.4 When compositions, i.e., x and x , are known, the parameters of an activity coecient 1 1 model can be estimated by solving Eqs. (11.2-5) and (11.2-6). a) If the system is represented by the two-sux Margules model, show that i h ) ln (1 x )/(1 x ) 1 1 ln(x1 /x1 A= = (1 x )2 (1 x1 )2 (x x )(x + x1 ) 1 1 1 1 b) If the system is represented by the van Laar model, show that A= (X Y )(X + )2 (Y + )2 2 (X + Y ) + 2 Y + X (2 Y + ) 399 (2)

(1)

where X= x 1

B=

(X Y )(X + )2 (Y + )2 2 (X + Y ) + 2 Y + X (2 Y + ) x 1 1 x1

(3)

1 x 1

Y =

c) Abedinzadegan and Meisen (1996) studied liquid-liquid equilibrium of diethanolamine (1) and octadecane (2) mixtures and reported the following solubility values at 492 K and atmospheric pressure: and x = 0.9924 x = 0.0959 1 1 If the system is represented by the van Laar model, estimate the parameters A and B. (Answer: c) A = 2.607 B = 4.933) 11.5 A mixture of acetonitrile (1) and n-hexadecane (2) forms two partially miscible liquid phases. Liquid-liquid equilibrium data on such systems are needed for the design of the oxidative desulfurization process. Furuya et al. (2007) obtained the following NRTL parameters at 333 K: 21 = 0.2818 = 0.2 12 = 4.852 a) If the composition of acetonitrile in the acetonitrile-rich phase is 0.994, estimate its composition in the n-hexadecane-rich phase. b) Are the like interactions stronger or weaker than the unlike interactions? (Answer: a) 0.168) 11.6 Using the Newtons method as described in Section 9.4.1, rearrange Eqs. (3) and (4) of Example 11.3 in the form f1 (x, y) = (1 x)
2

= ln

x 1

x1

= ln

1 x 1 1 x1

(4)

"

# 2 1.158 0.727 + 1.061 0.727 + 0.273 x (1 0.503 x)2 " # 2 y 1.158 0.727 = 0 (1) + ln (1 y)2 1.061 0.727 + 0.273 y x (1 0.503 y)2

f2 (x, y) = x

"

# 2 0.771 0.497 + 2.329 1 0.503 x (0.727 + 0.273 x)2 " # 2 0.771 0.497 1y 2 = 0 (2) y 2.329 + ln 1 0.503 y 1x (0.727 + 0.273 y)2 x = x 1 and x = y 1 (3)

where a) Choose x(0) = 0.2, y(0) = 0.9, and = 1 105 to begin iterations for the solution of this system. b) For the rst iteration, i.e., k = 1, show that Eq. (9.8-3) takes the form 4.49971 102 1.834147 0.310829 1 = (4) 5.73517 102 0.461743 2.953479 2 400

c) Solve Eq. (4) to obtain 1 = 2.85810 102 x(1) = x(0) + 1 = 0.228581 and 2 = 2.38867 102 y (1) = y (0) + 2 = 0.923887

d) Since max ' 0.03 > , continue iteration with e) Show that when k = 5 x(5) = 0.233811

y(5) = 0.920410

Keep in mind that good initial estimates are extremely important in numerical solutions. 11.7 Innite dilution activity coecients of various liquids in benzene at 293 K are given as follows: Component Acetone 1.77 Acetonitrile 3.21 Carbon tetrachloride 1.13 n-Hexane 2.21

Arrange these substances in order of decreasing solubility in benzene. Problems related to Section 11.3 11.8 Since the solubility of water in n-hexadecane is 0.0059 mole fraction and that of nhexadecane in water is 0.0072 mole fraction at 298.15 K, the n-hexadecane-water system is regarded as a system containing the two pure solvents. Consider a solute (1) that is partitioned between n-hexadecane (-phase) and water (-phase). The following data are provided: Component n-Hexadecane Water The condition of equilibrium states that x = x 1 1 1 1 (1) ( kg/ m3 ) 770.20 997.05 Molecular Weight 226.44 18.02

a) The hexadecane-water partition coecient, K1 , is dened as the molar concentration of the solute in the n-hexadecane phase to the molar concentration of the solute in the water phase, i.e., c (2) K1 = 1 c 1 Combine Eqs. (1) and (2) to obtain = 16.3 K1 1 1

(3)

If the solute is innitely dilute in this system, note that Eq. (3) takes the form
= 16.3 K1 1 1

(4)

If the innite-dilution activity coecient of solute in n-hexadecane and the hexadecane-water partition coecient are known, then Eq. (4) can be used to estimate the innite-dilution activity coecient of solute in water. b) The innite-dilution activity coecient of toluene in n-hexadecane is given as a function of temperature as follows (Schult et al., 2001): 401

Temperature ( K)

323.2 0.941

343.2 0.870

353.2 0.846

373.2 0.808

The hexadecane-water partition coecient of toluene is (Abraham et al., 1990) K = 575.4 Express the innite-dilution activity coecient in the form ln = A + B T

and estimate the innite-dilution activity coecient of toluene in water at 298 K. (Answer: 9660) 11.9 Consider two liquid phases, and , in which the -phase is almost pure 1 and the -phase is almost pure 2. a) Using the condition of equilibrium show that = 1 1
x1

and

= 2

1 x2

(1)

Therefore, determination of solubility enables one to estimate the innite-dilution activity coecient. This method, known as inverse solubility, is suitable for organics that are sparingly soluble in water, i.e., xi < 103 . b) The solubility of benzene (2) in water (1) at 298.15 K is reported by May et al. (1983) as x2 = 0.4129 103 Estimate the innite-dilution activity coecient of benzene in water. (Answer: 2422)

402