Fluid Phase Equilibria 331 (2012) 48–57

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Developing a feed forward neural network multilayer model for prediction of

binary diffusion coefficient in liquids
Reza Beigzadeh a , Masoud Rahimi a,∗ , Seyed Reza Shabanian a,b
a
CFD Research Center, Chemical Engineering Department, Razi University, Kermanshah, Iran
b
Dipartimento di Chimica, Materiali e Ingegneria Chimica, Politecnico di Milano, Italy

a r t i c l e i n f o a b s t r a c t

Article history: In the present study, a feed-forward artificial neural network (ANN) was developed to estimate the Fick
Received 3 March 2012 diffusion coefficient in binary liquid systems. It was found as a function of the mole fraction of one com-
Received in revised form 27 June 2012 ponent, diffusion coefficient at infinite dilution, viscosity, and molar volume of each component. These
Accepted 28 June 2012
values are easily accessible from literatures and handbooks. Data from 54 systems consisting of 851 data
Available online 6 July 2012
points were collected and the ANN was trained with one and two hidden layers using various numbers
of neurons. After selection of the best ANN, the results were compared with other models. The results
Keywords:
show that this model has a superior performance on estimating the Fick diffusion coefficient. In addition,
Diffusion coefficient
Binary system
a new ANN was developed to predict the Maxwell–Stefan (MS) diffusivity, based on which the Fick dif-
Artificial neural network fusion coefficient was calculated. The results show that direct prediction of the Fick diffusivity leads to a
Modeling higher accuracy compared with that of the indirect prediction. Moreover, in the direct calculation, there
is no need for the thermodynamic correction factor, which can be treated as a second advantage of this
method. The accuracy of the method was evaluated through data points of other systems, which were
not previously introduced to the developed ANN.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction gradient. The Maxwell–Stefan equations [2] use the gradient of

chemical potential as a driving force for diffusion as follows:
The diffusion phenomenon in liquid systems occurs in many
x2 J1 − x1 j2
industrial processes such as liquid–liquid extraction, leaching,  ∇ x1 = (2)
Ct Ð
chemical reactors, and distillation column. The calculation of
diffusion coefficients usually requires complicated and reliable pre- where Ð is the MS diffusion coefficient,  is the thermodynamic
diction methods and can be quite important for the mass transfer correction factor defined by the following relation:
rate determination.  
The diffusion phenomenon was described by two well-known ∂ ln 1
 = 1 + x1 (3)
theories: the Fick’s law [1] and the Maxwell–Stefan (MS) equations ∂x1
T,p·x2
[2]. The Fick’s law [1] is the most commonly used relation in which
the diffusive flux J relates to the concentration for a binary liquid Here,  1 is the activity coefficient of species “1” in the mixture.
solution as follows: Unlike gases, diffusion coefficients in liquids depends on
concentrations of components, and for non-ideal systems this
dependency is rather more complex [3]. In most prediction mod-
Ji = −Ct D∇ xi (1) els, the MS diffusion coefficient has been estimated, and the Fick
diffusion coefficient has been obtained by multiplying the MS dif-
fusivity and a thermodynamic correction factor (thermodynamic
where the index i denotes the ith species, Ct is total molar concen- non-ideality) [4,5]:
tration, D is the Fick diffusion coefficient, and xi is mole fraction
D= ·Ð (4)

Several models for the prediction of the MS diffusion coefficients

of binary liquid systems have been presented. However, some of
∗ Corresponding author at: Chemical Engineering Department, Razi University, them resulted in a prediction with a high error. Moreover, the used
Taghe Bostan, Kermanshah, Iran. Tel.: +98 8314274530; fax: +98 8314274542. variables in these models were rarely available in the literature.
E-mail address: masoudrahimi@yahoo.com (M. Rahimi). The Darken’s equation [6] involves coefficients of intra-diffusion

0378-3812/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fluid.2012.06.025
 R. Beigzadeh et al. / Fluid Phase Equilibria 331 (2012) 48–57 49

Table 1 the Fick diffusivity for each liquid system over a whole range of
Theoretical and empirical correlative models for prediction of mutual diffusion coef-
mole fraction of components via pure component properties.
ficients in binary liquid systems (all used thermodynamic correction factor).
ANN is an appropriate method for estimating complex functions
Model names Equations in order to evaluate equilibrium and transport properties such as
1 VLE, [24,25] solubility, [26,27] and thermal conductivity [28–30] for
Carman–Stein [16] D = m
· (x1 1 D2∞ ) · (x2 2 D1∞ )
Rathbun–Babb [13] D = (x1 D2∞ ) · (x2 D1∞ ) ˛ ˛ is a adjustable mixtures. The present study introduces a feed forward ANN model,
parameter that was optimized. trained by the Levenberg–Marquardt algorithm [31–33], to predict
According to the system type the Fick diffusion coefficient in several liquid systems. The exper-
Gainer [17] D = D1∞ x22 x11 kx1 
2 1/2
 M2 1/4  Evap·A 1/2 imental data over a range of concentrations for fifty-four systems
k= 1 M1 Evap·B
M is (including 851 data points) were collected from the literature to
molecular weight and Evap is energy develop the ANN model. Results were compared with other for-
of vaporization mulas and a satisfactory advantage was found. In addition, another
Bosse-LVS [18]  =1 
D
x x
 gE  ANN model was developed to predict the MS diffusivity, and the
m
(1 D2∞ ) 1 (2 D1∞ ) 2 exp − RT 
Fick diffusion coefficients were consequently found. The prediction
gE is excess Gibbs energy
  m −1⁄2
results from both methods were compared.
1−
Guerkan [19] D = D0 1 + K x1 x2 
D0 is

reference diffusion coefficient. K = 0.17,

2. Methodology
m = 1.23
KT
 2x1 x2 
1/2
The ANNs can learn and recognize complicated non-linear
Cullinan [20,21] D= 1/3 1+ (2x1 x2 −1)
K is the
2m vm
functions, so they are widely used in various fields of chemical
Boltzmann constant, T is temperature
engineering. The ANNs consist of input and output layers and some
and v is solution molar volume
hidden layers comprising neurons. The neurons of each layer are
connected to the adjacent layers and the influence of this intercon-
nected structure is specified by the weight associated with them,
of the components. The Modified Darken’s function [3] was pro- which ultimately provide a logical relationship between input and
posed through this equation using the mutual diffusion coefficient output parameters. The number of neurons for the input and out-
of each component at an infinite dilution, which yields a liner rela- put layers should be determined by the number of input and output
tion between the MS diffusivity and concentration. variables, respectively. However, the number of neurons in the hid-
An equation was proposed by Vignes [7] in which Ð were found den layers is variable and it is important for a network optimization,
by obtaining the logarithmic relationship between the MS diffu- which will be explained in the subsequent sections.
sivity and concentration for several binary liquid systems. Leffler
and Cullinan [8] developed the Vignes equation [7] by incorporat- 2.1. Data acquisition and analysis
ing the effect of viscosity of solution and each pure component. The
proposed model was slightly more accurate than prior models. The The first step in developing an ANN is to collect adequate and
problem of applying this equation is the evaluation of solution vis- appropriate data from related references to train the network. In
cosity, as the viscosity data for solution within the whole range of the literature, the Fick diffusivity values for many systems in var-
concentration are not available for some systems. ious ranges of concentrations are available. The MS diffusivity can
Li et al. [9] improved the Darken’s model [6] using cluster theory be achieved by using Eq. (4) and employing the thermodynamic
[10] (movement of groups of molecules) as well as by developing correction factor, which is calculated by Eq. (3).
the prediction of concentration dependent intra-diffusion coeffi- In this study, the Wilson excess Gibbs energy model was
cients. The intra (tracer) diffusion coefficients are defined as the employed to calculate the thermodynamic correction factor, using
mobility of each component in the mixture. These are measur- the following relation [12]:
able by PFG-NMR [11] (pulsed field gradient nuclear magnetic
resonance) and can also be obtained from empirical relations. In x1 x1 21
 = 1− +
addition, they employed Wilson equations [12] in their model. x1 + 12 x2 x2 + 21 x2
Although many variables were used in the model, some are dif-
12 (1 − 12 ) 21 (1 − 21 )
ficult to obtain as they are not available in the literature. Therefore, − x1 x2 2
+ 2
(5)
the variables should be attained from empirical formulas, which (x1 + x2 12 ) (x2 + x1 21 )
may lead to some errors. where:
Many authors have used the thermodynamic correction fac-
v2 12 − 11 v1 21 − 22
tor ( ) with an empirical exponent of ˛ for the Darken model 12 = exp − , 21 = exp − (6)
v1 RT v2 RT
[6] which can be optimized for each type of system [11,13]. Some
other researchers have attempted to validate or expand  [14,15]. Here T is temperature, R is universal gas constant and ij is the
A number of the correlative models for the prediction of the mutual Wilson parameter. The Fick and MS diffusivity are the outputs of
diffusion coefficient are listed in Table 1. In some other methods, the first and second ANNs, respectively.
models without the thermodynamic correction factor term were The important parameters of each pure component, that affect
introduced [22,23]. the diffusion coefficient, are viscosity and molar volume, which can
In the liquid systems, the diffusivity varies markedly with con- be found in the literature [34,35]. The diffusion coefficient at infi-
centration through the interaction between molecules of each nite dilution is diffusivity of each component at an infinitely dilute
solution component, especially in more non-ideal systems. In many solution of the component and can be predicted using a correlation
research studies, it has been attempted to find the diffusion coef- provided by Wike and Chang [36] as well as other models in the
ficients in liquids as a function of solution and pure component literature [3,37]. However, these methods are not always appro-
properties. However, it is difficult to find the value of solution priate and sometimes lead to large errors. Therefore, when the
properties for various concentrations. The most convenient way diffusion coefficients at infinite dilution experimental data are not
to achieve diffusion coefficients is to develop the best function of available, the suitable method to obtain them is an extrapolation
pure component properties. The ANN model can be used to predict of experimental mutual diffusion coefficients.
50 R. Beigzadeh et al. / Fluid Phase Equilibria 331 (2012) 48–57

Table 2
Viscositya and molar volumeb of all compound types in temperature of systems used in the ANN input.

No. Component typec T (K)  (MPa s) 106 v (m3 mol−1 ) No. Component type T (K)  (MPa s) 106 v (m3 mol−1 )

1 Acetone 298 0.308 73.987 16 Hexadecane 298 3.05 293.303

313 0.268 74.462 17 Nitromethane 298 0.61 53.925
328 0.238 75.429 18 Diethyl ether 298 0.224 104.837
2 1-Propanol 293 2.26 74.751 19 Acetic acid 298 1.138 57.657
298 1.938 75.313 20 Chloroform 298 0.539 80.662
3 Cyclohexane 293 0.97 107.621 21 OMCTS 298 2.185 315.218
298 0.889 108.454 308 2.05 316.902
313 0.703 109.086 318 1.92 318.604
328 0.589 112.891 22 Chloroform 298 0.539 80.662
333 0.536 113.576 303 0.524 81.233
4 1-Chlorobutane 298 0.423 104.481 313 0.461 82.274
5 Ethyl acetate 293 0.442 97.374 323 0.425 84.011
6 Methanol 278 0.746 39.313 23 Water 278 1.503 18.02
293 0.59 40.302 283 1.307 18.002
298 0.551 40.66 293 1.05 18.056
313 0.451 41.183 298 0.89 18.074
7 Ethanol 293 1.195 57.877 313 0.66 18.111
298 1.08 58.838 328 0.501 18.501
313 0.831 59.216 346 0.389 18.864
331 0.609 60.618 24 Pyridine 293 0.941 79.998
346 0.476 61.427 25 3-Methylpentane 303 0.292 130.576
8 1-Butanol 293 2.962 91.057 26 n-Octane 298 0.506 163.16
298 2.551 91.96 303 0.472 188.43
9 n-Heptane 298 0.388 147.76 27 Dimethylformamide 278 1.067 75.909
313 0.333 148.68 28 Benzene 283 0.753 87.666
328 0.289 153.32 293 0.668 88.56
10 n-Hexane 298 0.295 131.573 298 0.648 89.065
308 0.271 133.406 308 0.614 89.371
11 Toluene 293 0.595 105.903 313 0.598 89.555
298 0.558 107.766 318 0.553 89.679
300 0.544 107.928 323 0.436 91.464
313 0.478 108.797 328 0.411 92.866
328 0.401 110.652 333 0.389 93.21
12 Dodecane 298 1.38 228.032 29 Carbondisulfide 293 0.365 59.992
308 1.165 230.813 30 Tetradecane 298 2.17 260.73
13 Bromobenzene 283 1.33 103.644 31 Ethylbenzene 313 0.529 124.467
298 0.985 105.47 32 N-Methylpyrrolidone 283 1.736 103.589
14 2-Butanol 298 3.085 91.846 313 1.058 106.305
15 Carbontetrachloride 283 1.127 94.31 33 Chlorobenzene 283 0.974 100.59
293 0.965 96.061 298 0.813 102.67
298 0.905 96.943 300 0.764 102.749
313 0.702 98.92 34 MEK 298 0.43 89.578
a
Data source from Ref. [34].
b
Taken from handbook [35].
c
OMCTS, octamethylcyclotetrasiloxane; MEK, methylethylketone.

In the present study, the extrapolation infinite dilution diffu-
sion coefficients were used in order to achieve greater accuracy. It
should be noted that, after preparing the network, the correspond-
ing relations [3,36,37] can be used to find these values.
In this study, the ANN input data were the mole fraction of the
first component in binary liquids, diffusion coefficients at infinite
dilution, viscosity, and molar volume of each component. In addi-
tion, the input and output data at various temperatures were used.
The employed viscosity and molar volume are listed in Table 2.
In the present work, all input data points were divided randomly
into three sections including: training (60%), validation (20%) and
test (20%) data sets. Table 3 gives the overall range of data points
employed in this work for developing the ANN model.
2.2. Preprocessing
where Xmax and Xmin are the extreme values of variable Xi .
2.3. ANN modeling and training
In this work, a feed forward neural network multilayer model
was applied to predict the liquid diffusivity. The MATLAB software
[38] was employed for the ANN modeling. Fig. 1 shows the layout of
the ANN architecture used in this work. In the ANN architecture, the
numbers of input and output neurons were determined according
to the problem definition. In this work, the input and output lay-
ers have seven and one neurons, respectively. Theoretical methods
Table 3
List of range of employed data.
Variable Range

As far as in training of the ANN, the input and output data have x1 0–1
1 (mpa s) 0.224–3.085
different physical units and range, it is often useful to normalize
2 (mpa s) 0.271–3.085
all the input and output data before training. Therefore, all data 103 v1 (m3 mol−1 ) 0.018–0.319
(Xi ) were normalized (Yi ) in the range of 0–1 using the following 103 v2 (m3 mol−1 ) 0.018–0.261
relation: 109 D1 ∞ (m2 s−1 ) 0.48–5
109 D2 ∞ (m2 s−1 ) 0.4–6.05
(Xi − Xmin ) 109 Ð (m2 s−1 ) 0.4–10.89
Yi = (7) 109 D (m2 s−1 )
(Xmax − Xmin ) 0.15–6.05
 R. Beigzadeh et al. / Fluid Phase Equilibria 331 (2012) 48–57 51

Fig. 1. The layout of the ANN architecture.

for determining the appropriate number of hidden layers are not process of the ANN was carried out using the Levenberg–Marquardt
available. Moreover, the number of neurons in each hidden layer back propagation algorithm. In this training method, connection
prior to training cannot be obtained theoretically. Therefore, the weights wij and biases bj are iteratively adjusted to minimize the
trial-and-error method is commonly used to design the ANN. output deviation (predicted by ANN) from the target values accord-
In the present study, the trial-and-error method was employed ing to Levenberg–Marquardt [30–32] optimization method. The
to attain the number of layers and neurons. For this purpose, a early stopping method was used to avoid memorizing the train-
MATLAB script [38] was written that creates and screens differ- ing data set. In this method, in case of a decrease in deviation of the
ent structure several times, such as: one and two hidden layers as predicted values without decrease in predicted values of the val-
well as various numbers of neurons in each hidden layer. Because idation data set, the training will be stopped. Moreover, the error
the initial weights may have a large effect on the convergence, runs values should be calculated for different network structures with
were repeated 100 times with different randomly generated initial different numbers of neurons in hidden layers with one and two
values. The results presented in this work are the best ones obtained hidden layers.
from this procedure.
An increase in the number of hidden neurons may cause over-
fitting that usually occurs when a model is complicated. The 2.4. Deviations
complicated neural network means that there is a large number
of neurons (with a large number of weights and biases) relative to In this work in order to select the best ANN architecture, the
the number of training data. In these networks, the optimal number average squared deviation (ASD) and the correlation coefficient (R)
of neurons should be determined. between the experimental and estimated values were used. The
Each neuron is connected to the neurons of the adjacent layer, average relative deviation (ARD) was applied to compare the results
whose information is transferred via the connection. Each of these with other methods using the following relations:
connections has a weight (wij ) and these weights indicate the
1  Exp
N
strength of the connection. The output of each neuron can be 2
ASD = (D − DPred ) (9)
obtained from the following equation: N
 n  i=1
 
yj = F wji xi + bj 
(8)
100 
N DExp − DPred 
i=1 ARD (%) = (10)
N DExp
Here yj is the output from jth neuron, xi is the output vector from i=1
ith to jth neuron, bj is the jth neuron bias, n is number of input vec-
tors to jth neuron, and F is the transfer function that transformed 
N
Exp Exp
the sum of the weights plus the bias to get the normalized output (DExp − DAve ) · (DPred − DAve )
values. There are many types of transfer functions. In this work the i=1
R=  (11)
“tansig” transfer function was used for the hidden layers and “pure- N Exp 2 N Pred ) 2
i=1
(DExp − DAve ) · i=1
(DPred − DAve
lin” function were considered for the output layer. The training
52 R. Beigzadeh et al. / Fluid Phase Equilibria 331 (2012) 48–57

Fig. 3. ASD values for different number of neurons in the first and second hidden
layers.

Table 4
Best ARD values of different training algorithm for ANN with 7-25-1 configuration.

Training algorithm ARD (%)

Trainlm 4.75
Traincgb 5.17
Trainb 7.30
Trainbr 7.28
Traingdm 9.79
Traingda 9.51

coefficient), the predicted MS diffusivity was expressed by the Fick

diffusivity using Eq. (4) in order to have a meaningful comparison.
Here, deviation in the Fick diffusivity prediction is fairly less than
deviation of the ANN prediction for the MS diffusivity.
Fig. 3 shows deviations in the network with two hidden layers
and various numbers of neurons in the first and second hidden lay-
ers for predicting the Fick diffusivity. It is well known that in the
ANN modeling, the overfitting starts to occur with increase in the
number of neurons. Therefore, the presented results show the dif-
ference between training and test errors despite a slight reduction
Fig. 2. ASD values for different number of hidden neurons in the ANN with in the overall deviation. Here, the ANN with a structure of 7-25-1
one hidden layer for Fick diffusion coefficient prediction. (a) Direct. (b) Using
Maxwell–Stefane diffusion coefficients.
(twenty-five neurons in hidden layer) and 7-10-7-1 (ten neurons in
first and seven neurons in second hidden layer, respectively) were
chosen as optimum topologies.
Exp Pred are the averages of the experimental and
Here DAve and DAve In addition to the Levenberg–Marquardt algorithm (trainlm),
predicted diffusion coefficients, respectively. other algorithms such as: traincgb (conjugate gradient back-
propagation with Powell–Beale restarts), trainb (batch training
3. Results and discussion with weight and bias learning rules), trainbr (bayesian regu-
larization back-propagation), traingdm (gradient descent with
In the present study, the ANN was developed to estimate the momentum back-propagation), and traingda (gradient descent
mutual diffusion coefficients in binary liquid systems using some with adaptive learning rate back-propagation), were used to train
variables as ANN input data. These data are accessible and the dif- the network. Table 4 shows the average relative deviation (ARD)
fusion coefficients are widely affected by them in liquid solutions. obtained for each algorithm. The reported errors in the table
In many studies, it has been tried to provide more accurate mod-
els with variables that are easily accessible. In this research, the Table 5
variables considered in the input of the network were selected Deviations of the selected ANN configurations for direct predicting of Fick diffusion
according to the models that have been previously presented. coefficients.
In this work, the application of ANN models with one and two ANN configuration Stage Data points ASD R
hidden layers were investigated. The ANN with different archi-
Training and validating 681 0.010 0.9963
tectures lead to different outcomes in each run, so there is more Testing 170 0.014 0.9933
7-25-1
possibility to reach the best answer with more runs. Fig. 2 shows Overall 851 0.011 0.9948
the lowest obtained ASD after several runs in terms of increase in Training and validating 681 0.007 0.9977
the number of neurons in one hidden layer for Fick and MS dif- 7-10-7-1 Testing 170 0.013 0.9939
Overall 851 0.008 0.9960
fusion coefficients. In the second case (prediction of MS diffusion
 R. Beigzadeh et al. / Fluid Phase Equilibria 331 (2012) 48–57 53

Table 6
Results of the ANN (7-25-1) compared with other methods.

No. Binary systems T (K) Number of data pointsa ARD (%)b D Ref.

ANN Darken Leffler–Cullinanc Li et al.d

1 Acetone 1-Propanol 298 11 3.7 11 17.6 [5]

2 Acetone 1-Butanol 298 12 3.5 6.8 12.2 [5]
3 Acetone Water 298 22 2.9 27.3 26.9 22.2 [40–42]
328 9 5.3 17.9 15.7
4 1-Propanol Water 298 9 12.4 36 25.1 [5]
5 cyclohexane Benzene 293 13 3.4 7.5 7.5 [40,43]
298 19 1.8 6 5.9 4.9
313 11 1.8 7.6 7.4
333 11 0.7 6.7 6.5
6 Acetone Benzene 298 15 2.6 5.3 5.7 1.9 [21,40,44]
7 1-Chlorobutane 1-Propanol 298 7 10.1 14.6 18.3 [5]
8 Ethanol Benzene 298 11 5.2 24.8 25.2 [41]
313 7 2.6 26.6 26.1
9 Methanol Benzene 293 11 8.4 18.8 17.2 13 [45]
10 Methanol Water 278 9 3.9 7.6 9.5 [46,47]
298 8 3.9 3.1 5.8
313 6 4.5 3.3 6.1
11 Acetone Chloroform 298 9 1.0 16.6 14.7 3.3 [40,42,48]
313 10 3.1 9.5 8.6
12 Ethanol Water 298 11 3.7 9.7 4 9 [42,49]
313 8 5.0 10.5 2.5
331 8 6.2 9.3 2.3
346 8 3.6 10.6 2.3
13 Carbontetrachloride Cyclohexane 298 10 4.7 0.9 0.7 0.8 [50]
313 11 2.6 2.9 2.8
14 Ethanol Carbon disulfide 293 12 5.7 25.3 26.2 16 [45]
15 1-Butanol Carbon disulfide 293 9 9.9 21.9 26 15.6 [45]
16 n-Heptane Tetradecane 298 22 1.5 5.8 3.7 [51]
17 Methanol Carbon tetrachloride 293 11 10.2 33.2 30.2 [52,53]
298 9 13.1 25.9 23.5 13.4
18 n-Hexane Carbontetrachloride 298 6 1.7 2.2 7.1 2.1 [54]
19 MEK carbontetrachloride 298 7 4.7 3.2 5.6 4.5 [55]
20 Acetone Cyclohexane 298 9 10.9 20.7 22 [56]
21 Toluene Cyclohexane 298 11 3.7 3.9 5.2 5.2 [50]
313 11 4.2 6 7.5
328 11 1.2 6.3 7.7
22 n-Hexane Toluene 298 9 3.3 0.3 2.6 7.5 [57]
23 Toluene Carbontetrachloride 298 9 1.9 2.1 1.1 0.8 [57]
24 Dodecane n-Hexane 298 11 3 5.4 4.5 1 [58]
308 12 1.4 5.2 4.9 0.8
25 Hexadecane n-Heptane 298 7 5.6 2.7 1.3 3 [58]
26 Bromobenzene Benzene 298 5 3.1 0.5 1.3 [59]
27 Chlorobenzene Bromobenzene 283 6 4.5 2.8 3.2 [60]
298 5 11.2 1.5 1.6 0.8
28 Toluene Chlorobenzene 300 5 5.8 1.6 1.2 1.1 [60]
29 Dodecane n-Octane 298 6 4 0.5 0.3 [46]
30 2-Butanol 1-Propanol 298 21 4.8 1.5 1.3 1.8 [47]
31 Carbontetrachloride Benzene 283 6 5.2 2 2.6 [60]
298 5 4.5 2.4 2.9 0.5
333 5 11.4 2.1 2.6
32 Acetone Carbontetrachloride 298 6 6.3 4.1 4.9 4.6 [41]
33 Nitromethane Benzene 298 11 5.4 7.8 7.3 [59]
34 Ethanol Chloroform 298 7 6.7 7.4 7.4 [61]
35 Ethanol Carbontetrachloride 298 10 8.1 27.3 34.3 16 [62]
36 Diethyl ether Chloroform 298 9 3.3 18 12.9 3.3 [63]
37 Acetic acide Carbontetrachloride 298 7 9 34 33.3 6.1 [21]
38 Chloroform Benzene 298 10 1.3 7.5 7.1 1.8 [50]
313 11 4.7 6.8 6.5
328 11 2.1 6.2 6
39 Chloroform Toluene 298 8 3 8.6 9.2 [64]
40 n-Hexane Benzene 298 11 1.2 3.3 5.4 5.7 [65]
41 OMCTS Carbontetrachloride 298 22 2.2 2.5 6.3 3.9 [66]
42 OMCTS Benzene 298 15 2.5 5.8 4.7 3.9 [66]
308 10 1.9 5.5 6.1 3.8
318 10 2 4.8 6.7 3.8
43 Chloroform Carbontetrachloride 298 12 1.8 4.1 4 3.6 [67]
44 n-Heptane Benzene 298 11 2.9 5.1 2.3 3.9 [50]
313 11 2.4 3.6 1.6
328 11 1.9 2 1.5
45 Methanol 1-Propanol 298 16 4 4.6 4.1 6.7 [68]
46 Methanol 2-Butanol 298 8 2.5 21.7 13.9 6 [68]
47 Heptane Ethylbenzene 313 6 2.5 2.7 3.6 [69]
48 Water N-Methylpyrrolidone 283 6 17.8 38.6 75.3 [69]
313 6 17.1 10.7 32.2
54 R. Beigzadeh et al. / Fluid Phase Equilibria 331 (2012) 48–57

Table 6 (Continued)

No. Binary systems T (K) Number of data pointsa ARD (%)b D Ref.
c d
ANN Darken Leffler–Cullinan Li et al.

49 Carbontetrachloride Carbondisulfide 293 11 2.5 1.6 2.5 [70]

50 Cyclohexane Carbondisulfide 293 10 5.1 11.4 8.5 1.7 [70]
51 Toluene Carbondisulfide 293 12 2.2 8.2 5.4 [70]
52 Pyridine Water 293 9 10.1 57.2 48 [70]
53 Toluene Benzene 298 11 2.1 2.7 2.2 3.6 [50]
313 11 4.2 3.3 2.8
54 Chloroform Acetic acid 298 21 1.8 34.3 34.1 11.3 [71]
55 n-Propanol Carbontetrachloridee 293 11 5.6 14.3 14.3 [71]
56 n-Butanol Carbontetrachloridee 293 11 2.9 38 38 [71]
57 3-Methylpentane Chloroformee 303 6 5 3.6 4.5 [72]
58 n-Octane Chloroforme 303 6 1.9 2 3.2 [72]
59 Dimethylformamide Watere 278 10 6.2 13.7 23.8 [73]
60 Cyclohexane Ethylacetatee 293 11 7.1 6.2 6.8 5.4 [43]
a
Number of data points without considering the extrapolation dilution diffusion coefficients.
b
The average relative deviation is given by Eq. (10).
c
In this method the solution viscosity calculated by Eq. (12).
d
Deviation values extracted from the results presented in Ref. [9], blanks have not been reported.
e
Binary system not used in the training of the proposed ANN.

illustrate that using the Levenberg–Marquardt algorithm leads to The results reveal that the ANN led to satisfactory results in
the lowest error. comparison with other methods.
Deviations of the training, validation and testing stages of the The Wilson parameters were used to calculate the  , extracted
selected topologies are reported in Table 5. Acceptable differences from vapor–liquid equilibrium data [74,75]. Dilution diffusion coef-
between testing and training data sets of the ASD values can be ficients were extracted from experimental data or in the absence of
found in this table. This means that the network was suitable for experimental results they were extrapolated as shown in Table 7.
predicting data points that are not used in the training data set. The temperature was not considered as input variable but its effect
On the other hand, the results of the developed ANN for on them is quite obvious.
predicting the MS diffusivity leads to higher errors compared with In a typical research, usually the mutual diffusion coefficient
the direct method of predicting the Fick diffusivity. This drawback prediction models were provided and then a diagram of diffu-
can be related to failure in obtaining accurate thermodynamic sion coefficients versus concentration for better illustrating the
correction factor values. Here, the Wilson excess Gibbs energy prediction results was presented. Fig. 4 illustrates the experi-
model was used to calculate the thermodynamic correction mental diffusion coefficients and results of the ANN prediction
factor. The applied Wilson parameters in this model were fitted for Acetone–Chloroform system at 298 K. The mole fractions of
against vapor–liquid equilibrium experimental data to obtain this system were selected between 0 and 1 with 0.01 intervals
activity coefficients. Nevertheless, a low error level in the activity (0:0.01:1). This demonstrates an acceptable ability of the network
coefficients leads to a large error level in the first derivatives of prediction in the whole range of concentrations. In this figure, the
the activity coefficients [37,39]. Therefore, an error occurs for ANN outcomes were compared with those obtained from other
calculating  , especially when  is close to zero. The reason is that methods (modified Darken [3], Leffler–Cullinan [8] and Li et al. [9]).
with low changes in its value, the diffusion coefficient will change The presented results indicate satisfactory predictions by ANN.
significantly. Therefore, this error is inevitable in models that use Fig. 5 indicates a comparison between the predicted results from
the activity coefficients. In this work, it was tried to predict the Fick the ANN and the experimental values. This figure shows that the
diffusion coefficients with low prediction errors and without any
need for the calculation of the thermodynamic correction factor.
Table 6 shows the average relative deviations of the predicted
results from the ANN (with one hidden layer) compared with
the experimental data for predicting the Fick diffusivity of each
solution. The extrapolation dilution diffusion coefficients are not
employed in the data presented in this table. Moreover, the Net-
work capability in estimation of the Fick diffusion coefficients in
other systems (unknown for the ANN) was investigated. Refer-
ring to Table 6, it can be found that the prediction results for
these systems are quite acceptable. The total average relative devi-
ation for all experimental data points for the ANN results is 4.75%,
while this value is above 11% for the modified Darken [3] and
Leffler–Cullinan [8] models. Deviations of the modified Darken [3]
and Leffler–Cullinan [8] models were calculated, but deviation val-
ues of the Li et al. [9] model are reported directly from their work.
The mixture viscosity used for the Leffler–Cullinan [8] model was
calculated by an empirical formula as follows [9]:

1
= · [(1 v1 )x1 + (2 v2 )x2 ] (12)
v
Fig. 4. A comparison among predicted and experimental binary Fick diffusion coef-
v = x1 v1 + x2 v2 (13) ficients acetone–chloroform at 298 K.
 R. Beigzadeh et al. / Fluid Phase Equilibria 331 (2012) 48–57 55

Table 7
Infinite dilution diffusion coefficients used in the ANN input.

No.a T (K) 109 D1 ∞ 109 D2 ∞ No. T (K) 109 D1 ∞ 109 D2 ∞

(m2 s−1 ) (m2 s−1 ) (m2 s−1 ) (m2 s−1 )

1 298 1.13 3.18 28 300 1.75 2.26

2 298 0.94 2.79 29 298 1.74 1.13
3 298 1.28 5.08 30 298 0.58 0.4
328 1.82 6.05 31 283 1.45 1.03
4 298 1.05 0.69 298 1.89 1.41
5 293 1.94 1.65 333 2.42 1.77
298 2.1 1.89 32 298 2.16 3.64
313 2.65 2.45 33 298 2.96 2.04
333 3.45 3.29 34 298 2.31 1.66
6 298 2.75 4.13 35 298 5 1.5
7 298 1.22 3.3 36 298 2.13 4.48
8 298 2.91 1.75 37 298 1.42 1.28
313 3.73 2.93 38 298 2.24 2.86
9 293 3.8 2.45 313 2.88 3.55
10 278 0.88 1.46 323 3.56 4.25
298 1.56 2.19 39 298 2.54 2.71
313 2.09 2.65 40 298 2.29 4.75
11 298 2.34 3.62 41 298 0.72 0.82
313 2.92 4.33 42 298 1.15 1.09
12 298 1.24 1.13 308 1.35 1.34
313 1.7 1.64 318 1.58 1.63
331 2.4 2.36 43 298 1.4 2
346 2.95 3.1 44 298 1.79 3.92
13 298 1.49 1.26 313 2.28 4.74
313 1.92 1.61 328 2.79 5.62
14 293 4 2.4 45 298 0.75 1.97
15 293 2.15 0.75 46 298 0.48 1.73
16 298 0.94 2.07 47 313 2.45 3.7
17 293 2.1 2.1 48 283 0.81 0.68
298 2.53 2.3 313 1.38 1.53
18 298 1.49 3.9 49 293 3 2.36
19 298 1.55 3.01 50 293 2.85 2.58
20 298 2.22 4.05 51 293 2.5 2.6
21 298 1.57 2.42 52 293 0.75 1.33
313 1.91 3.07 53 298 1.85 2.55
328 2.41 3.8 313 2.39 3.24
22 298 2.48 4.34 54 298 1.44 1.85
23 298 1.48 2.14 55 293 1.1 0.88
24 298 2.73 1.41 56 293 0.8 0.78
308 3.06 1.67 57 303 2.28 4.53
25 298 1.76 0.75 58 303 2.03 3.08
26 298 1.23 1.87 59 278 0.63 1.24
27 283 1.01 1.31 60 293 2.56 1.83
298 1.33 1.72
a
System numbers of Table 6.

Fig. 5. Comparison between predicted and experimental diffusion coefficients. (a)

ANN predicted values for all data points are quite close to the exper-
imental data values. Moreover, this figure illustrates the results of
the comparison between the modified Darken [3] model and the
experimental results (Fig. 5b). The results show that the ANN is able
to estimate the Fick diffusion coefficients values in a more efficient
way compared with the modified Darken [3] model.
The developed three-layered ANN (7-25-1) in this work pro-
vides the weights, which are listed in Table 8. Using the parameters
(W, b) presented in Table 8, the diffusion coefficients can be calcu-
lated from the following equation:
⎧   7  ⎫
⎨25
 ⎬
D = Fp Wkj Ft Wji Xi + bj + bk
⎩ ⎭
j=1 i=1
where X is the input value of the network, W is the weight, b is the
bias, ‘i’, ‘j’ and ‘k’ refer to the input, hidden, and output layer, respec-
tively. F is the transfer function that is used to get the normalized
output values from the neurons. In this study, the “tansig” trans-
fer function was considered for hidden layers and the “purelin”
ANN model and (b) Darken model.
transfer function was used for the output layer. These functions
can be defined as follows:
ex − e−x
Ft (x) = (15)
ex + e−x
Fp (x) = x (16)
Here x is the independent variable of the functions. This proce-
dure can be used to introduce diffusion coefficients in user defined
subroutines in many practical computer codes such as Computa-
tional Fluid Dynamics (CFD) code. Using precise values of diffusion
(14) coefficients can give more efficient results in field mass transfer in
liquid solutions.
One can say that, if the binary diffusion coefficients of any
system are available, a polynomial interpolation (D versus xi )
would do well in predicting the dropped data points. However,
for this purpose one equation should be fitted for each sys-
tem. The presented ANN in this work introduces a technique
to avoid curve fitting of a large number of polynomials, any of
which can be useful just for one system. Here, the developed
56 R. Beigzadeh et al. / Fluid Phase Equilibria 331 (2012) 48–57

Table 8
Connection weights and biases.

Neuron W1 b1 b2 = 5.007

x1 D1 ∞ D2 ∞ v1 v2 1 2 W2

1 −2.120 −8.358 3.659 4.427 −4.128 −1.302 −1.409 9.552 −0.549

2 1.359 1.019 1.875 1.242 1.099 3.094 1.078 −4.503 0.794
3 −2.945 −1.523 4.656 −3.580 −1.255 5.541 5.546 −1.134 −0.147
4 −1.458 −1.457 −1.139 6.758 −3.908 1.021 −4.168 2.040 −2.100
5 1.462 3.327 −0.883 2.533 3.815 −1.786 0.105 −2.947 −2.731
6 0.999 −1.221 −0.840 −0.111 −1.508 −3.343 −3.153 1.259 0.947
7 3.053 1.708 −1.150 3.559 0.600 4.294 −3.279 −3.382 0.101
8 0.635 −4.953 −2.306 −0.301 −2.993 −4.967 2.389 7.816 1.808
9 1.829 3.974 3.265 −0.244 0.452 1.638 1.593 3.398 4.699
10 1.629 0.225 1.601 −1.690 −0.667 −1.250 −3.086 1.810 0.539
11 −0.208 7.144 −2.261 0.366 −0.726 5.589 0.056 1.630 −2.397
12 −1.030 0.269 1.660 −1.631 0.391 2.634 −1.068 0.294 −1.644
13 −2.676 1.016 0.278 −2.965 1.757 4.088 −4.292 −0.333 −0.324
14 −1.187 −1.608 3.470 1.808 0.758 −1.746 4.572 −0.761 0.260
15 −1.480 −3.016 0.595 −2.623 −3.356 1.755 0.214 2.819 2.872
16 −0.152 −4.312 3.772 −2.957 −6.054 −2.703 −0.530 5.465 0.935
17 −0.045 6.534 −1.375 1.724 −12.774 3.282 3.756 −5.768 −3.972
18 −2.747 2.643 −5.354 4.942 −2.004 −3.131 −3.719 5.113 0.206
19 −0.734 1.257 −1.827 1.413 0.723 0.257 −0.794 −1.448 3.266
20 −0.722 0.126 −1.006 1.129 0.759 1.019 −0.606 0.183 1.569
21 −0.520 0.294 1.539 −2.321 0.798 2.115 0.780 −0.216 2.819
22 1.580 1.078 1.136 −7.089 4.037 −0.977 4.180 −1.969 −2.071
23 −5.422 2.690 0.660 2.114 −11.316 2.041 −3.094 −1.639 0.287
24 −0.237 −0.572 2.825 0.204 −7.381 −1.600 0.474 0.988 0.240
25 −55.145 2.080 0.430 −6.647 1.108 0.664 0.042 −3.453 10.033

ANN works similar to a box that contains many polynomial equa- List of symbols
tions. One can enter the system type and mole fraction of each
component and find the diffusion coefficient value with a high
precision.
bj bias
C molar concentration (mol m−3 )
D Fick diffusion coefficient (m−2 s−1 )
4. Conclusions Ð Maxwell–Stefan diffusion coefficient (m−2 s−1 )
Di ∞ diffusion coefficient at infinite dilution of species i
This study presents a novel method for mutual diffusion coef- (m−2 s−1 )
ficients prediction in binary liquids. An artificial neural network F transfer function
scheme was developed to estimate the mutual diffusion coeffi- gE excess Gibbs energy (J mol−1 )
cients in binary liquid systems. The variables such as diffusion J molar flux (mol m−2 s−1 )
coefficients at infinite dilution, viscosity, molar volume, and mole M molecular weight
fraction of each component were used as the network inputs. Data n number of input vectors
of 54 binary liquid systems consisting of 851 data points were col- N number of data points
lected and divided randomly into three sections including; training R universal gas constant (8.314 J mol−1 K−1 )
(60%), validation (20%), and test (20%). The ANNs with different T temperature (K)
architectures were used to predict the Fick and Maxwell–Stefan v molar volume (m3 mol−1 )
diffusion coefficients. The optimum number of neurons for one wij weight
and two hidden layers was selected by the trial-and-error method. x independent variable
From this study, it can be concluded that the direct prediction of the xi mole fraction of component i/output vector from ith neu-
Fick diffusivity is more appropriate than the prediction using MS ron
diffusivity. The high precision in estimating liquid diffusion coef- X network input
ficients and no need to calculate the thermodynamic correction yj neuron output
factor are the reasons, which support this conclusion. The pre-
diction results of the ANN with one hidden layer (7-25-1) was
presented and compared with the prediction results from other Greek letters
models. For this ANN architecture, the total average squared devi-  activity coefficient
ation of 0.01 and the total average relative deviation of 4.75% were  thermodynamic factor
obtained.  dynamic viscosities (pa s)
From this study, it can be concluded that the artificial neural net- Wilson’s parameter
works can be a solution to problems with complex relationships  Wilson’s parameter
between diffusion coefficients and concentration in binary liquid
systems, even for strongly non-ideal systems. The presented ANN in Subscripts
this work introduces a technique to find diffusion coefficient values 1 2 component 1 and 2 in solution
with a high precision by introducing the system type and mole frac- i component i/input layer
tion of each component instead of sophisticated polynomial fitting j hidden layer
for each individual system. k output layer
 R. Beigzadeh et al. / Fluid Phase Equilibria 331 (2012) 48–57
Superscripts
Ave average
Exp experimental
Pred predicted
References
[1] A. Fick, Pogg. Ann. 94 (1855) 59–89.
[2] J. Stefan, Sitzungsber. Akad. Wiss. Wien. 63 (1871) 63–124, Abt. II.
[3] B.E. Poling, J.M. Prausnitz, J.P. O’Connell, The Properties of Gases and Liquids,
McGraw-Hill, New York, 2001.
[4] S. Rehfeldt, J. Stichlmair, Fluid Phase Equilib. 256 (2007) 99–104.
[5] S. Rehfeldt, J. Stichlmair, Fluid Phase Equilib. 290 (2010) 1–14.
[6] L.S. Darken, Trans. Am. Inst. Min. Metall. Eng. 175 (1948) 184–201.
[7] A. Vignes, Ind. Eng. Chem. Fundam. 5 (1966) 189–199.
[8] J. Leffler, H.T. Cullinan, Ind. Eng. Chem. Fundam. 9 (1970) 84–88.
[9] J. Li, H. Liu, Y. Hu, Fluid Phase Equilib. 187–188 (2001) 193–208.
[10] E.L. Cussler, AIChE J. 26 (1980) 43–51.
[11] C. D’Agostino, M.D. Mantle, L.F. Gladden, G.D. Moggridge, Chem. Eng. Sci. 66
(2011) 3898–3906.
[12] G.M. Wilson, J. Am. Chem. Soc. 86 (1964) 127–130.
[13] R.E. Rathbun, A.L. Babb, I&EC Proc. Des. Dev. 5 (1966) 273–275.
[14] Y.D. Hsu, Y.P. Chen, Fluid Phase Equilib. 152 (1998) 149–168.
[15] Y.D. Hsu, M. Tang, Y.P. Chen, Fluid Phase Equilib. 173 (2000) 1–21.
[16] P.C. Carman, L.H. Stein, Trans. Faraday Soc. 52 (1956) 619–627.
[17] J.L. Gainer, Ind. Eng. Chem. Fundam. 9 (1970) 381–383.
[18] D. Bosse, H.-J. Bart, Ind. Eng. Chem. Res. 45 (2006) 1822–1828.
[19] T. Guerkan, AIChE J. 33 (1987) 175–176.
[20] H.T. Cullinan, AIChE J. 31 (1985) 1740–1741.
[21] D.K. Rollins, K.S. Knaebel, AIChE J. 37 (1991) 470–474.
[22] F.A.L. Dullien, A.F.A. Asfour, Ind. Eng. Chem. Fundam. 24 (1985) 1–7.
[23] C.H. He, Ind. Eng. Chem. Res. 34 (1995) 2148–2153.
[24] C.A. Faúndeza, F.A. Quieroa, J.O. Valderrama, Fluid Phase Equilib. 292 (2010)
29–35.
[25] V.D. Nguyen, R.R. Tan, Y. Brondial, T. Fuchino, Fluid Phase Equilib. 254 (2007)
188–197.
[26] M. Safamirzaei, H. Modarress, Fluid Phase Equilib. 309 (2011) 53–61.
[27] M. Lashkarbolooki, B. Vaferi, M.R. Rahimpour, Fluid Phase Equilib. 308 (2011)
35–43.
[28] A.Z. Hezave, M. Lashkarbolooki, S. Raeissi, Fluid Phase Equilib. 314 (2012)
128–133.
[29] H. Kurt, M. Kayfeci, Appl. Energy 86 (2009) 2244–2248.
[30] R. Eslamloueyan, M.H. Khademi, S. Mazinani, Ind. Eng. Chem. Res. 50 (2011)
4050–4056.
[31] K. Levenberg, SIAM J. Numer. Anal. 16 (1944) 588–604.
[32] D. Marquardt, SIAM J. Appl. Math. 11 (1963) 431–441.
[33] M.T. Hagan, Menhaj, IEEE Trans. Neural Netw. 5 (1994) 989–993.
[34] D.S. Viswanath, T.K. Ghosh, D.H.L. Prasad, N.V.K. Dutt, K.Y. Rani, Viscosity of
Liquids: Theory, Estimation, Experiment, and Data, Springer, Dordrecht, 2007.
[35] R.H. Perry, D.W. Green, Perry’s Chemical Engineers Handbook, seventh ed.,
McGraw Hill, New York, 1997.
57
[36] C.R. Wilke, P. Chang, AIChE J. 1 (1955) 264–270.
[37] R. Taylor, R. Krishna, Multicomponent Mass Transfer, Wiley & Sons Inc.,
NewYork, 1993.
[38] www.mathworks.com, The Mathworks Inc., 2010.
[39] A. Wild, Multicomponent diffusion in liquids, Ph.D. Thesis, TU, Munich, VDI-
Verlag, Düsseldorf, 2003.
[40] D.W. McCall, D.C. Douglass, J. Phys. Chem. 71 (1967) 987–997.
[41] D.K. Anderson, J.R. Hall, A.L. Babb, J. Phys. Chem. 62 (1958) 404–409.
[42] M.T. Tyn, W.F. Calus, J. Chem. Eng. Data 20 (1975) 310–316.
[43] T.M. Aminabhavi, P. Munk, J. Phys. Chem. 84 (1980) 442–446.
[44] H.T. Cullinan Jr., H.L. Toor, J. Phys. Chem. 69 (1965) 3941–3949.
[45] K. McKeigue, E. Gulari, AIChE J. 35 (1989) 300–310.
[46] Z.J. Derlacki, A.J. Easteal, A.V.J. Edge, L.A. Woolf, Z.J. Roksandic, Phys. Chem. 89
(1985) 5318–5322.
[47] Y.E. Lee, S.F.Y. Li, Eng. Data 36 (1991) 240–243.
[48] P.C. Carman, J. Phys. Chem. 71 (1967) 2565–2573.
[49] B.R. Hammond, R.H. Stokes, Trans. Faraday Soc. 49 (1953) 890–895.
[50] S.A. Sanni, P. Hutchison, J. Chem. Eng. Data 18 (1973) 317–322.
[51] H.Y. Lo, J. Chem. Eng. Data 19 (1974) 236–241.
[52] V. Sanchez, M. Clifton, J. Chem. Eng. Data 23 (1978) 209–212.
[53] D.K. Anderson, A.L. Babb, J. Phys. Chem. 67 (1963) 1362–1363.
[54] D.L. Bidlack, D.K. Anderson, J. Phys. Chem. 68 (1964) 206–208.
[55] D.K. Anderson, A.L. Babb, J. Phys. Chem. 66 (1962) 899–901.
[56] A.Z. Tasic, B.D. Djordjevic, S.P. Serbanovic, D.K. Grozdanic, J. Chem. Eng. Data 26
(1981) 118–120.
[57] R.K. Ghai, F.A.L. Dullien, J. Phys. Chem. 78 (1974) 2283–2291.
[58] J.C. Shieh, P.A. Lyons, J. Phys. Chem. 73 (1969) 3258–3264.
[59] L. Miller, P.C. Carman, Trans. Faraday Soc. 55 (1959) 1831–1837.
[60] C.S. Caldwell, A.L. Babb, J. Phys. Chem. 60 (1956) 51–56.
[61] H. Lemonde, Ann. Phys. 9 (1938) 539–644.
[62] B.R. Hammond, R.H. Stokes, Trans. Faraday Soc. 52 (1956) 781–786.
[63] D.K. Anderson, A.L. Babb, J. Phys. Chem. 65 (1961) 1281–1283.
[64] A.A. Asfour, Mutual and intra-(self-) diffusion coefficients and viscosities of
binary liquid solutions at 25.00 ◦ C, Ph.D. Thesis, University of Waterloo, Water-
loo, Ont, Canada, 1979.
[65] K.R. Harris, C.K.N. Pua, P.J. Dunlop, J. Phys. Chem. 74 (1970) 3518–3529.
[66] K.N. Marsh, Trans. Faraday Soc. 64 (1968) 894–901.
[67] C.M. Kelly, G.B. Wirth, D.K. Anderson, J. Phys. Chem. 75 (1971) 3293–3296.
[68] F.O. Shuck, H.L.J. Toor, Phys. Chem. 67 (1963) 540–545.
[69] G. Chen, Y. Hou, H.J. Knapp, Chem. Eng. Data 40 (1995) 1005–1010.
[70] M.A. Slddiqi, W. Krahn, K.J. Lucas, Chem. Eng. Data 32 (1987) 48–50.
[71] V. Vitagliano, A. Zagari, R. Sartorio, J. Chem. Eng. Data 18 (1973)
370–372.
[72] R.L. Rowley, S.C. Yi, D.V. Gubler, J.M. Stoker, J. Chem. Eng. Data 33 (1988)
362–366.
[73] G. Guarino, O. Ortona, R. Sartorio, V. Vitagliano, J. Chem. Eng. Data 30 (1985)
366–368.
[74] J. Gmehing, U. Onken, Vapor–Liquid-Equilibrium Data Collection, DECHMA
Chemistry Series, Frankfurt, 1977.
[75] M. Hirata, S.K. Ohe, Nagahama Computer Aided Data Books of Vapor–Liquid
Equilibrium, Elsevier, Tokyo, 1975.