Example 8.

1
A stream of liquid 1 flowingat 5mol/s anda stream of liquid 2 flowing at 3mol/s, both at 298K, are
mixed in a steady flow process. For this mixture the molar excess Gibbs energy is given by

In which the parameter A is given as a function of temperature in the form

Where T is in K

(a) How much heat must be added to or removed from the mixer so as to maintain the mixing
process isothermal?

(b) Suppose that the entering temperature of liquid 2 is increased from 298 K to 330 K and the
mixer is adiabatic. Determine the temperature of the stream leaving the mixer under these
conditions. Take pure component heat capacities asCP1 =35 J/molK and CP2 =50 J/molK.

Solution

(a) Considering the mixer as a system, the mass and energy balances are

And

The molar enthalpy of the mixture is given by

Substitution of Eqns (1) and (2) into Eqn (3) and using the relationship

Yield
The quantity can be determined from Eqn (8.2-19) as

Substitution of the numerical values gives

Thus, the amount of heat that must be removed from the system is calculated as

(b) Since the mixer is adiabatic, i.e. , Eqn (2) becomes

Where T represents the temperature of the stream leaving the mixer. The molar enthalpy of the
mixture,Eqn (3), is given by

Substitution of Eqns (1) and (8) into Eqn (7) and reaarrangement lead to

Since

Or

Solving for temperature gives T=329.2 K

Example 8.2
Huang et al. (2004) reported the following vapor-liquid equilibrium data for tetraethyl orthosilicate
(1)−ethanol (2) mixtures at 400 mmHg

T(K) x1 y1 T(K) x1 y1

336.5 0.0000 0.0000 378.2 0.9061 0.2211

337.9 0.1622 0.0144 398.7 0.9668 0.4953

339.5 0.2721 0.0205 410.0 0.9892 0.7370

344.4 0.5132 0.0352 419.2 1.0000 1.0000

360.8 0.8252 0.1170

The vapor pressures of pure components are given by the Antoine equation as

Where P is in mmHg and T is in K. Calculate the activity coefficients and express as a

function of composition.

Solution

At each temperature, vapor pressures are calculated from

The activity coefficients are then calculated by using Eqn (8.3-13), i.e.

Finally, the term is determined from Eqn (8.3-9) as

The results are tabulated below:

T(K) x1 y1

336.5 0.0000 0.0000 17.1 399.6 - 1.000 0

337.9 0.1622 0.0144 18.3 425.3 1.942 1.106 0.192

339.5 0.2721 0.0205 19.8 456.4 1.525 1.179 0.235

344.4 0.5132 0.0352 24.9 564.1 1.100 1.405 0.214

360.8 0.8252 0.1170 51.5 1098.0 1.102 1.841 0.186

378.2 0.9061 0.2211 1102.5 2083.0 0.952 1.593 -0001

398.7 0.9668 0.4953 211.1 4113.0 0.971 1.478 -0.016

410.0 0.9892 0.7370 303.4 5808.0 0.982 1.677 -0.012

419.2 1.0000 1.0000 400.9 7583.4 1.000 - 0

Using the procedure outlined in Example 6.15, is expressed as

White
Example 8.3
Using the data given in Problem 6.22, estimate partial molar excess volumes for a mixture of
methanol (1) and benzene (2) at 298K. Show that the exponential correction term in Eqn (8.3-29)
is almost unity.

Solution Partial molar volumes of methanol and benzene can be determined from Eqns (2) and ( 3)
of Problem 6.22, respectively, as

The use of Eqns (1) and (2) in Eqn (8.3-30) gives partial molar excess volumes as

Where the coefficients are given as

The calculated values of as a function of composition are given in the following

table:
 0.0 0.479 0 0.6 −0.023 0.010

0.1 0.114 0.017 0.7 −0.016 −0.003

0.2 −0.035 0.042 0.8 −0.012 −0.017

0.3 −0.071 0.053 0.9 −0.005 −0.056

0.4 −0.060 0.046 1.0 0 −0.171

0.5 −0.039 0.029

Note that is of the order of Taking , the exponential

term in Eqn (8.3-29) becomes

Comment: Assuming activity coefficients to be independent of pressure is plausible even at high

pressures.
Example 8.4
Derive Eqns (8.4-2) and (8.4-3).

Solution Equation (8.4-1) can be expressed as

Where is the total number of moles. The total excess Gibbs energy, , is

From Eqn (8.3-18)

Alternate solution:

Substitution of Eqn (8.4-1) in to Eqns (8.3-19) and (8.3-20) leads to

Example 8.5
Mara et al. (1997) obtained the following set of vapor-liquid equilibrium data for the 1-propanol
(1) and 2-pentanol (2) system at 313.5K:

P(kpa)

0.2022 0.4332 3.189

0.4030 0.6784 4.154

0.6026 0.8282 5.097

0.8015 0.9278 6.026

If the two-suffix Margules equation represents this system, calculate the parameter A. The vapor
pressures of 1-propanol and 2-pentanol at 313.5K are 6.970 kPa and 2.261 kPa, respectively.

Solution
The parameter A in the two-suffix Margules equation is given by

Therefore, it is necessary to calculate as a function of composition from eqn (8.3-9),i.e.

The activity coefficients, on the other hand, are calculated by using Eqn (8.3-13), i.e.
The results are given in the following table:

0.2022 0.4332 0.980 1.002 −2.403 −0.015

0.4030 0.6784 1.003 0.990 −4.863 −0.020

0.6026 0.8282 1.005 0.975 −7.204 −0.030

0.8015 0.9278 1.001 0.969 −5.527 −0.035

Taking the arithmetic average of A gives

Alternate solution: The parameter A can also be determined by defining an “objective function”.
For example, an objective function, F, with respect to molar excess Gibbs energy is defined as

The value of A that minimizes the sum of the squares of the deviations is given by

Or

Substitution of the numerical values yields

A=− 0.025.
Example 8.6
Gabaldon et al. (1996) obtained the following set of data for the water (1) and n-propanol (2)
system at 0.6bar:

0.103 3.107 1.011 0.557 1.642 1.443

0.231 2.603 1.051 0.686 1.385 1.925

0.294 2.397 1.083 0.796 1.203 2.850

0.361 2.212 1.158 0.869 1.099 4.294

0.487 1.814 1.306

Estimate the Margules parameters A and B, and calculate the infinite dilution activity coefficients.

Solution

The molar excess Gibbs energy is calculated from Eqn (8.3-9), i.e.

And the values are given in the table below:

0.103 0.127 0.557 0.439

0.231 0.259 0.686 0.429

0.294 0.313 0.796 0.361

0.361 0.380 0.869 0.273

0.487 0.427

The plot of ( )/x1x2 versus x1 is shown below. The data fit astraight line with a correlation
coefficient 9 of 0.979. The slope and the intercept of the best straight line passing through the
data points are 1.309 and 1.150, respectively.

Therefore, the parameters are

 A=1.805 and B=0.655.

The use of Eqn (8.4-9) gives the infinite dilution activity coefficients as

9
A correlation coefficient measures the degree to which two variables are directly related. Its value changes from−1 to 1,−1 and 1 being perfect negative
and positive correlations, respectively.

Alternate solution:

The parameters A and B can also be determined by defining an objective function, F, as

The values of A and B that minimize the sum of the squares of the deviations are given bye

Once the differentiations are carried out, Eqns (1) and ( 2) take the form
Using matrix algebra, the parameters A and B can be determined from Eqns (3) and (4) as

Which are slightly lower than the previously calculated values.

The parameters A and B can be estimated from a single set of activity coefficient data as
Example 8.7
The following vapor-liquid equilibrium data are provided for a binary mixture of ethanol (1) and
acetone (2) by Campbell et al. (1987):

T(K) P(Kpa)

397.7 652.9 0.342 0.305

At 397.7K

The vapor phase obeys the virial equation of state with the following parameters:

If the liquid mixture is represented by the three-suffix Margules equation, estimate the
parameters A and B.

Solution

Once the activity coefficients, , are calculated at the given experimental data point, the
parameters A and B can be determined from Eqn (8.4-11). The starting point for the calculation of
activity coefficients is Eqn (8.3-12), i.e.
Since pressure is high, simplifying assumptions of this equation leading to Eqn (8.3-13) are no
longer valid. Therefore, activity coefficients are calculated from Eqn (1) as

From Eqn (5.3-5)

From Eqn (7.5-6)

The Poynting correction factors for ethanol and acetone are

Substitution of the numerical values into Eqn (2) gives the activity coefficients as
The use of Eqn (8.4-11) gives the parameters as

Comment: One should be cautious in using parameters based on a single set of experimental
data.

Example 8.8
For a binary mixture of carbon tetrachloride (1) and n-propanol (2), Carley and Bertelsen (1949)
obtained the following data from VLE experiments under atmospheric pressure:

0.058 2.90 1.03 0.441 1.64 1.29 0.818 1.10 2.73

0.141 2.51 1.06 0.522 1.50 1.40 0.851 1.07 3.05

0.300 2.00 1.15 0.683 1.24 1.84 0.950 1.013 5.54

Which model, three-suffix Margules or van Laar, better represents the activity coefficients of this
system?

Solution

The molar excess Gibbs energy is calculated from Eqn (8.3-9), i.e.
 If the system is represented by the three-suffix Margules equation, then the plot of
versus should yield a straight line. In Figure (a), the correlation coefficient of the best
straight line passing through the data points is 0.698. The scatter of the data indicates that the
representation of this binary system by the three-suffix Margules equation is rather poor.

On the other hand, if the activity coefficients are represented by the van Laar model, then the plot
of x1/ versus x1/x2 should yield a straight line.

As shown in Figure (b), the result is a straight line with a correlation coefficient of 0.998, indicating
that the system is best represented by the van Laar model. The slope and the intercept of the
straight line are 0.473 and 0.852, respectively. Therefore, the parameters are
Example 8.9
For a binary system of thiophene (1) and n-hexane (2), Sapei et al. (2006) reported = 1.82 and
= 2.49 at 338.15K. If this system is represented by the Wilson equation, evaluate the
parameters and , and express activity coefficients as a function of mole fractions.

Solution

The use of Eqn (8.4-23) gives

Then the parameter can be estimated from Eqn (8.4-24) as

Thus, Eqns (8.4-19) and (8.4-20) take the form

The numerical values of the activity coefficients are given in the table below:

0.1 1.677 1.004 0.6 1.162 1.248

0.2 1.547 1.019 0.7 1.098 1.387

 0.3 1.431 1.046 0.8 1.047 1.599

0.4 1.329 1.089 0.9 1.013 1.933

0.5 1.239 1.153

Example 8.10
A binary liquid mixture consists of 40mol% n-pentane (1) and 60% benzene (2). Calculate the
activity coefficients at 318K by using the regular mixture theory. Solution From Table 8.1

The volume fractions of n-pentane and benzene are calculated from Eqn (8.5-4) as

The use of Eqns (8.5-2) and (8.5-3) yields

Comment: It is implicitly assumed that the liquid volumes are independent of temperature.
Example 8.11
Estimate the activity coefficients of a binary liquid consisting of 73 mol % acetone (1) and 27%
benzene (2) at 332.4K.

Solution
The structural formulas of acetone and benzene are shown below.

Note that while acetone has one CH3 group and one CH3CO group, benzene has six ACH groups.
From Table 8.2

Thus, values are

• Combinatorial Activity Coefficient

The molecular volumes and surface areas are calculated from Eqn (8.6-4) as

r1 = (1)(0.9011)+(1)(1.6724)=2.5735,

r2 = (6)(0.5313)=3.1878,
q1 = (1)(0.848)+(1)(1.488)=2.336,

q2 = (6)(0.400)=2.400.

The volume and surface area fractions as well as the parameter are calculated from Eqn (8.6-3)
as

Thus, the combinatorial part of the activity coefficients is calculated from Eqn (8.6-2) as
• Residual Activity Coefficient
Interaction parameters should be considered between the main groups.

The subgroups CH3 (k = A), CH3CO (k = B), and ACH (k = C) belong to CHx, CH2CO, and ACH main
groups, respectively. Hence, from Table 8.3

From Eqn (8.6-9)

For pure acetone (i=1), the mole fractions of groups CH3 and CH3CO are

The group area fractions in pure acetone are calculated from Eqn (8.6-7) as
Contributions of groups CH3 and CH3CO in pure acetone are calculated from Eqn (8.6-6) as

Since only one main group exists in benzene

Now, contributions of the functional groups to the residual activity coefficient, , should be
calculated. The use of Eqn (8.6-8) gives the group mole fractions in solution as
The area fractions are calculated from Eqn (8.6-7) as

Substitution of the numerical values into Eqn (8.6-6) gives

Similarly,

From Eqn (8.6-5)

(1)(0.2782−0.389)+(1)(0.2692−0.135)=0.0234,
 = (6)(0.0216−0)=0.1296.

Activity coefficients can be calculated from Eqn (8.6-1) as

= 0.01486 + 0.0234 = 0.03826 = 1.039,

= 0.09883 + 0.1296 = 0.22843 = 1.257.

Example 8.12
Alonso et al. (2004) reported the following isothermal VLE data for a binary mixture of methanol
(1) and n-hexane (2) at 313.15K:

(a) Determine the infinite-dilution activity coefficients by using the Lagrange three-point formula.
(b) Determine the parameters in the Wilson equation and estimate the vapor phase composition
for the given x1 values.

Solution

(a) It is first necessary to calculate the activity coefficients from Eqn (8.3-13), i.e.

For example, let us calculate and values for the following data set:

P(Kpa)

68.759 0.2273 0.4794

From the given data, at 313.15 K.

The activity coefficients are

The calculated values of the activity coefficients as a function of composition are given in the table
below:

The values of the liquid phase mole fractions and the activity coefficients to be used in Eqns (8.7-
5) and (8.7-6) are given below:
Therefore, the infinite-dilution activity coefficients are calculated as

(b) The use of Eqn (8.4-23) gives

The parameter can be estimated from Eqn (8.4-24) as

One values are calculated from Eqn (8.4-19) at each value, the gas phase composition is
determined from
And the results are tabulated below:

Example 8.13
Using the result obtained in Example 8.12, i.e = 0.078 and = 0.112, estimate infinite
dilution activity coefficients using Eqn (8.7-7).

Solution

The term can be determined from Eqn (8.3-9), i.e.

The calculated values are given below:

Using the procedure outlined in Example 6.15, is expressed as

With

The use of Eqn (8.7-7) gives the infinite dilution activity coefficients as

Example 8.14
In a binary liquid system, the activity coefficients of the components are proposed in the form

Are these equations thermodynamically consistent?

Solution
The given activity coefficient expressions should satisfy the Gibbs-Duhem equation, Eqn (8.8-4),
i.e.
The derivatives of the activity coefficients are

Therefore, the left-hand side of Eqn (1) becomes

Which is different from zero.Therefore, the given equations are thermodynamically inconsistent.

Comment:

In cases in which the Gibbs-Duhem equation is satisfied, it is also necessaryto checkwhether

→ 1 as → 1.

Example 8.15
The following isothermal VLE data are reported by Hiaki et al. (1998) for a binary system of 2-
methyl-2-propanol (1) and octane (2) at 343.15K. Check whether the experimental data are
consistent.
Solution

The plot of versus is given below.

Fitting a fifth-order polynomial to the data points yields

Thus,

From Eqn (8.8-11)

Note that ln( 1/ 2) = 0 when x1 =0.4659. Therefore, the positive and negative areas are
The use of Eqn (8.8-12) gives

Therefore, the data are consistent.

Example 8.16
The following isobaric VLE data are reported by Huang et al. (2004) for a binary system of
tetraethyl orthosilicate (1) and ethanol (2) at 24kPa. Check whether the experimental data are
consistent.

Solution

The minimum and maximum temperatures are

The use of Eqn (8.8-16) gives

Fitting a fifth-order polynomial to the data points yields

Thus,

Note that . Therefore, the positive and negative areas are

The use of Eqn (8.8-12) gives

From Eqn (8.8-15)

|D−J|< 10, (8.8-15)

Therefore, the data are consistent.

Example 8.17
Kirss et al. (2005) reported the following binary Wilson parameters as a function of temperature:

where 1, 2, and 3 representmethyl butyl ketone, nonane, and cyclohexanol, respectively. For a
ternary system, the experimental data at 408.88 K and 80 kPa indicate the liquid phase
composition as

x1 =0.128 x2 =0.256 x3 =0.616.

(a) Determine the activity coefficients in a ternary mixture of methylbutyl ketone, nonane, and
cyclohexanol.

(b) Estimate the vapor phase composition in equilibrium with the liquid.

Data:

The vapor pressures of the components are given by

where T is in K and Pvap is in kPa.

Solution

(a) At 408.88K, the binary Wilson parameters are

Substitution of the numerical values into Eqn (8.9-2) gives the activity coefficients as

(b) At 408.88 K, the vapor pressures are

The use of Eqn (8.3-13) gives the vapor phase compsition as