Iranian Journal of Science & Technology, Transaction B, Engineering, Vol. 29, No.

B5
Printed in The Islamic Republic of Iran, 2005
Shiraz University



A NEW AND A SIMPLE MODEL FOR SURFACE TENSION PREDICTION
OF WATER AND ORGANIC LIQUID MIXTURES
*



R. TAHERY AND H. MODARRESS
**

Dept. of Chemical Engineering, Amir Kabir University of Technology, P.O. Box: 15875-4413, Tehran, I. R. of Iran
Email: hmodares@aku.ac.ir

Abstract In this paper a new simple equation for surface tension prediction of binary aqueous-
organic solutions over the entire range of compositions is presented and used for the calculation of
surface tension of 15 binary aqueous-organic solutions. The overall average absolute deviation is
0.53%. The parameters of the new equation are calculated for the binary systems under study and
it is shown that in the temperature range used for surface tension calculations they are independent
of temperature and can be expressed in terms of the normal boiling point of organic compounds.

Keywords Surface tension, binary aqueous-organic solutions, surface tension coefficient

1. INTRODUCTION

Thermodynamic and transport properties are fundamental in the design of process units that involve fluid
flow and interface heat and mass transfer. Surface tension is one of the most interesting thermophysical
properties due to its manifestation in many of the naturally occurring phenomena, as well as in many
industrial applications. Surface effects have great importance in dealing with heterogeneous catalysis
applications. Moreover, processes like lubrication, corrosion and reactions in electrochemical cells are
also related to surface effects.
In fact, liquid-vapor interfaces are critical to the chemical engineering separation processes such as
gas absorption, condensation and distillation. In the past years, some equations have been derived in
various degrees of generality for the prediction of binary aqueous-organic solutions. Schuchowitzky [1]
and Belton and Evans [2] developed semi-empirical equations for ideal or nearly ideal solutions in the
bulk phase. However, these equations are empirical, and the constant terms have no apparent relation to
the properties of the pure components, therefore the calculation of surface tension is complicated.
Guggenheim [3] used a quasicrystalline model to derive an equation for the surface tension of regular
solutions as a function of the heat of mixing and simplified it for ideal solutions. Hoar and Melford [4]
developed a theoretical model for nonpolar solutions with the assumption that the bulk liquid and surface
layer behave like regular solutions and that the molecules approximate hard spheres, Sprow and Prausnitz
[5], by using the regular solution theory, derived an equation for predicting surface tension of binary
solutions. This equation applies only to solutions having zero excess volume and entropy. In the same
trend of investigation, Semenchenko [6] and Feinerman [7] developed equations for predicting the surface
tension of binary solutions. Goldsack and Sarvas [8] assumed ideal solution behavior in both bulk and
surface phases and obtained an equation for predicting surface tension of binary solutions.
Connors and Wright [9] derived an equation for calculating the surface tension of binary aqueous
organic solutions. Alvarez et al. [10-15] used Connors and Wright's [9] equation for modeling the surface
tension of binary aqueous solutions and computed model parameters for each solution. Lee et al. [16] used

Received by the editors April 12, 2004; final revised form August 6, 2005.

Corresponding author


R. Tahery / H. Modarress

Iranian Journal of Science & Technology, Volume 29, Number B5 October 2005
502
Connors and Wright's [9] equation for modeling the surface tension of 1,3-propandiol + Water. According
to their calculations, model parameters are temperature dependent. Zihao et al. [17] calculated the surface
tension of binary aqueousorganic solutions with an equation that was derived on the basis of the Wilson
equation. Zhibao and Benjamin [18] derived an equation based on the Davis theory [19] and calculated the
surface tension of some binary aqueous-organic solutions.
In this work a new equation is proposed and used for calculating the surface tension of binary
aqueous-organic solutions. The results show that the calculated surface tensions by this equation are in
better agreement with experimental data compared with similar equations.

2. THEORY

a) Background

Connors and Wright [9] considered binary solutions as a distinct two-phase system: the bulk phase and
surface phase. In their equation the surface tension of the solutions is written as an average of the surface
tensions of the pure components weighted by the total surface concentrations of the components. By using
Langmuir adsorption isotherm Connors and Wright derived a two parameter equation for the surface
tension of binary solutions.
Zihao et al. [17] proposed a surface tension equation based on the thermodynamic definition of
surface tension and the expression of Gibbs free energy. By using the Wilson equation to represent the
excess Gibbs free energy, a two parameter surface tension equation was derived for liquid mixtures.
Zhibao and Benjamin [18] developed a semi theoretical model for calculating surface tension of pure
liquids and binary mixtures based on the Davis theory [19].
In this work a new model is derived for binary aqueous-organic solutions. The essence of the theory is
described in the following section.

b) Derivation of the new model

For an ideal solution of organic compound (A) and water (W), the surface tension is presented as

Ideal A A W W
x x = + (1)

where
A
and
W
are the surface tensions of pure organic component and water respectively, and x is
the mole fraction.
Also, for an ideal solution a reduced surface tension can be defined as

*

W Ideal
Ideal
W A
(2)

By using Eqs. (1) and (2) it is shown that

*
Ideal A
x
= (3)

Similarly, for a real solution the reduced surface tension, *
Real
, is defined as

*
W Real
Real
W A

(4)

As for an ideal solution *
Ideal A
x
= , it is convenient to present *
Real
as

*
A Real
x

= (5)

A new and a simple model for surface tension prediction of

October 2005 Iranian Journal of Science & Technology, Volume 29, Number B5
503
where

is a new solution property defined as the surface tension coefficient and for an ideal solution it
is equal to unity. Therefore the excess reduced surface tension, which is the difference between reduced
surface tensions of real and ideal solutions, can be presented in the following form:

*
* *
Real Ideal

=
(6)

And therefore, by using Eqs. (3), (5) and (6) we obtain

*
( 1)
A
x

=


(7)

For the new property introduced as the surface tension coefficient, , we propose the following
simple functionality:

1
1
= +

W
W
ax
bx
(8)

where a and b are the parameters of this new surface tension equation for binary aqueous-organic
solutions. According to Eq. (8), as
W
0 x
the surface tension coefficient should tend to unity ( 1)
and also as
W
0 x
, the limiting value of surface tension coefficient is ( 1 a b ) /( 1 b ) + . By
combining Eq. (7) and Eq. (8) we obtain a more applicable form of the surface tension equation proposed
in this work as

*
1
1
1

= =

W
A
x b
ax a
(9)

Equation (9) shows that variation of
1) 1/(
versus 1/
W
x is linear and the parameters a and b can be
evaluated from the slope and intercept of this plot. Figure 1 shows, as examples, the linear variation of
1) 1/( versus
1/
W
x for binary aqueous solutions of formic acid, ethanol, methanol and
monoethanolamine (MEA). The values of a and b for each binary solution evaluated at 5C intervals from
slopes and intercepts of this plot are presented in Table 1. As it is seen from the results in Table 1, the
parameters a and b are independent of temperature. The same independency of temperature for the
parameters a and b of all binary aqueous solutions studied in this work is observed. The calculated
parameters, a and b, as average values for the studied temperature range are reported in Table 2. Also in
this table, the average absolute deviation percent (AAD %) in calculating surface tension of solutions by
the new equation and the (AAD %)s by the equations proposed by Connors and Wright [9], Zihao et al.
[17], and Zhibao and Benjamin [18] are reported. The lower AAD% values of surface tension calculated
by the new equation compared with those calculated by Zihao et al. [17] and Zhibao and Benjamin's [18]
equations indicate the accuracy of the new equation. However as it is seen from the results in the Table 2,
the (AAD %)s calculated by the Connors and Wright [9] equation are less than those calculated by the
new equation, but the superiority of the new equation is inherent in the fact that parameters a and b are
independent of temperature. It is worth noting that the parameters in the Connors and Wright [9] equation
vary with temperature, and therefore for each experimental data the specific parameters should be
calculated, thus reducing the predictability of Connors and Wright is [9] equation.
It is usual to correlate the surface tension of pure fluids in terms of characteristic substance properties
such as critical temperature, pressure and normal boiling point by utilizing the principle of correspondence
states. In this respect, the proposed correlation of Hakim et al. [20] for polar fluids and Brock and Bird
[21] for a number of substances ranging from noble gases to diatomic and simple inorganic molecules can
be mentioned.

R. Tahery / H. Modarress

Iranian Journal of Science & Technology, Volume 29, Number B5 October 2005
504
















Fig. 1. The variation of 1) 1/( versus 1/
W
x for indicated aqueous solutions at 25C ();
30C (); 35C (); 40C (); 45C (); 50C (). The points are the
experimental data and the lines are the calculated values of 1) 1/(

Table 1. The surface tension coefficient parameters ( a , b ) as expressed by Eq. (8) at 5C intervals

MEA Methanol Ethanol Formic acid Temp
(C)
a b a b a b a b
20 * * 0.8497 0.8624 0.9279 0.9552 0.7600 0.8421
25 0.6264 0.9459 0.8484 0.8632 0.9291 0.9547 0.7573 0.8428
30 0.6281 0.9459 0.8468 0.8637 0.9276 0.9552 0.7609 0.8413
35 0.6282 0.9453 0.8440 0.8645 0.9277 0.9551 0.7590 0.8421
40 0.6252 0.9462 0.8406 0.8669 0.9264 0.9557 0.7565 0.8433
45 0.6255 0.9457 0.8382 0.8681 0.9259 0.9564 0.7559 0.8441
50 0.6239 0.9461 0.8346 0.8698 0.9267 0.9560 0.7557 0.8436

* Surface tension experimental data at 20C for Water + MEA (Monoethanolamine) solution is not available.

In this work, for calculated parameters a and b obtained from the slope (1/ a ) and the intercept
( / b a) of the plot of 1) 1/( versus1/
W
x , a simple correlation in terms of reduced boiling point
/
=
br b c T T T
can be proposed, where
b T
and
c T
are the normal boiling point and critical temperature
of the organic compound, respectively. This correlation can be represented by the following equation

0.05 0.05
/ 0.9253( / ) 0.0069
br
a a
T

= (10)

The correlation factor for linearity of Eq. (10) is 0.998 for the 15 binary aqueous solutions named in Table
2 and the characteristic parameter in Eq. (10) can be expressed as:

0.0133( ) 0.281
br T = (11)

Also, the average ratio of
0.5
0.05
) ( / b a for parameters a and b of the studied solutions is

0.5
0.05
/ 0.9823 b a = (12)

The average standard deviation of
0.5
0.05
) ( / b a values for each binary solution from the average value
0.5
0.05
/ b a is 0.0208. And as it is generally convenient to represent the deviation of surface tension of a
solution from ideal behavior in terms of
E
, the excess surface tension, in the following form [10-15]:

0
1
2
3
4
5
6
7
1 2 3 4 5 6 7
1/xW
1
/
(

1
)
MEA
Formic Acid
Methanol
Ethanol
0
0.2
0.4
0.6
0.8
1 1.1 1.2 1.3 1.4
A new and a simple model for surface tension prediction of

October 2005 Iranian Journal of Science & Technology, Volume 29, Number B5
505
( )
E A A W W
x x

= + (13)

By using Eqs. (2), (4), (8) and (9) we can write

( )
1

A W W A
E
W
x a x
bx
(14)

Dividing both sides of Eq. (14) by ( )
W A

, we obtain a reduced surface tension deviation in the
following form

*
1

A W
E
W
x a x
bx
(15)

Table 2. Surface tension parameters ( a , b ) for the new equation and the average absolute
deviations percent (AAD %) calculated by various surface tension equations
for 15 binary aqueous-organic solutions

Compound
Temp.
(C)
a b (AAD%)
1
(AAD%)
2
(AAD%)
3
(AAD%)
4
n
Data
source
Monoethanolamine (MEA) 25 - 50 0.6264 0.9459 0.04 0.03 0.36 n.a. 13 12
Diethanolamine (DEA) 25 - 50 0.6676 0.9557 0.02 n.a. n.a. n.a. 11 11
Triethanolamine (TEA) 25 - 50 0.9507 0.9582 0.03 n.a. n.a. n.a. 11 11
N-Methyldiethanolamine
(MDEA)
25 - 50 0.8118 0.9653 1.46 1.04 1.51 n.a. 14 14
1-Amino-2-propanol (MIPA) 25 - 50 0.6943 0.9638 0.59 n.a. n.a. n.a. 12 18
3-Amino-1-propanol (AP) 25 - 50 0.6871 0.9152 0.36 n.a. n.a. n.a. 12 18
2-Amino-2-methyl-1-
propanol (AMP)
25 - 50 0.8332 0.9794 0.17 0.09 0.72 n.a. 14 12
Formic acid 20 - 50 0.7557 0.8436 0.30 0.24 0.39 0.84 14 13
Acetic acid 20 - 50 0.7916 0.9561 0.22 0.12 0.79 1.19 14 13
Propionic acid 20 - 50 0.9090 0.9855 0.31 0.22 0.95 2.53 14 13
Methanol 20 - 50 0.8346 0.8698 0.42 n.a. 0.72 1.07 14 10
Ethanol 20 - 50 0.9267 0.9560 0.57 n.a. 0.91 1.68 14 10
1-Propanol 20 - 50 0.9777 0.9933 1.60 n.a. 1.94 3.15 14 10
2-Propanol 20 - 50 0.9711 0.9832 1.45 n.a. 2.75 1.97 14 10
1,3-Propandiol 25 - 50 0.7085 0.8952 0.45 n.a. 6.55 n.a. 7 15
Overall average AAD% 0.53% 0.29% 1.60% 1.77%

(AAD%)
1
, (AAD%)
2
, (AAD%)
3
and (AAD%)
4
refer to the average absolute deviations percent based on Eq. (9), and
Connors and Wright [9], Zihao et al. [17] and Zhibao and Benjamin [18] equations.
n: Number of experimental data
n.a.: Not available
In the next section the proposed equations, Eqs. (4), (5) and (8), are applied to 15 binary aqueous-
organic solutions and the results are compared with those obtained by application of similar equations
proposed by Connors and Wright [9], Zihao et al. [17], and Zhibao and Benjamin [18].

3. RESULTS AND DISCUSSION

The calculated parameters a and b of Eq. (9) for 15 binary aqueous-organic solutions are reported in Table
2. In Fig. 1, the values of 1) 1/( versus 1/
W
x have been plotted for aqueous solutions of methanol,
ethanol, formic acid and monoethanolamine (MEA) at different temperatures. The points indicate the
experimental values of 1) 1/( obtained by inserting the experimental data in Eqs. (4) and (5). The lines
R. Tahery / H. Modarress

Iranian Journal of Science & Technology, Volume 29, Number B5 October 2005
506
indicate the calculated 1) 1/( by inserting in Eq. (9) the fixed values of the parameters a and b as
reported in Table 2. For all 15 binary aqueous-organic solutions studied in this work similar plots can be
presented. Figure 2 shows the surface tension coefficient ( ) versus
W
x for aqueous solutions of formic
acid, acetic acid, propionic acid, methanol, ethanol, 1-propanol, 2-propanol, monoethanolamine,
diethanolamine, and triethanolamine at 25C. The points indicate the surface tension coefficient is
obtained directly by inserting the experimental data in Eqs. (4) and (5). The lines indicate the calculated
surface tension coefficient by using the fixed values of the parameters a and b as reported in Table 2 in
Eq. (8). As it can be seen from this figure, the surface tension coefficient for the studied solutions
increases nonlinearly with the mole fraction of water. This is the expected trend since according to Eq. (8)
as
W 0
x
the surface tension coefficient should tend to unity ( 1). Also according to Eq. (8)
for
W
x
1
, the limiting value of surface tension coefficient is ( 1 a b ) /( 1 b ) + . By using the
values of parameters a and b in Table 2, the values of at
W
x
1
are equal to 146.93, 63.69 and
23.74 for 1-propanol, propionic acid and triethanolamine (TEA) respectively. In Fig. 2 a large deviation
from linearity is observed for
W
x
1
. This indicates that, even the presence of a very small amount of
organic compound causes a large deviation from ideal behavior due to adsorption of the organic
compound on the liquid-water surface. Also from Figure 2, it is obvious that surface tension coefficient
( ) for the ternary amine is larger than that of secondary and primary amines and the deviation from
ideal behavior depends on the molecular structure of the amines. The deviation from ideal behavior
increases from methanol to 1-propanol and from formic acid to propionic acid. This is seen from values of
the surface tension coefficients ( ) for alcohols and organic acids presented in Fig.2. By plotting the
excess surface tension (
E
) versus
W
x in Fig.3, the deviation from the ideal behavior for aqueous
solutions of methanol, ethanol, 1-propanol and 2-propanol at 20C is also shown. The points indicate the
excess surface tension
E
is obtained directly by using experimental data in Eq. (13). The lines indicate
the calculated
E

by inserting the fixed values of parameters a and b as reported in Table 2 in Eq. (14).

0
4
8
12
16
20
0 0.2 0.4 0.6 0.8 1
x
W

MEA
DEA
TEA
Formic Acid
Acetic Acid
Propionic Acid
Methanol
Ethanol
1-Propanol
2-Propanol

Fig. 2. The variation of versus
W
x
for indicated aqueous solutions at 25C. The points
are the experimental data and the lines are the calculated values of

A new and a simple model for surface tension prediction of

October 2005 Iranian Journal of Science & Technology, Volume 29, Number B5
507

















Fig. 3. The variation of
E
versus
W
x for indicated aqueous solutions 20C. The points
are the experimental data and the lines are the calculated values of
E


Figure 4 shows the variations of both excess reduced surface tension
*
and reduced surface
tension
*

, versus
A
x for aqueous solution of formic acid at 20 and 50 C. The points are obtained by
using the experimental data in Eqs. (5) and (7). The lines indicate the calculated
*
and
*

, by inserting
the fixed values of the parameters a and b as reported in Table 2 in Eqs. (5) and (7). Figure 5 shows the
same variations as Fig. 4, which,
*
and
*

versus
A
x for aqueous solution 2-amino-2-methyl-1-
propanol (AMP) at 20 and 50 C.


Formic Acid + Water
0
0.2
0.4
0.6
0.8
1
0 0.2 0.4 0.6 0.8 1
x A

(*)real 20C
(*) 20C
(*)real 50C
(*) 50C
Ideal Solut ion

AMP + Water
0.0
0.2
0.4
0.6
0.8
1.0
0 0.2 0.4 0.6 0.8 1
x A

(*)real 20C
(*) 20C
(*)real 50C
(*) 50C
Ideal Solut ion

Fig. 4. The variations of
*

and
*

versus
W
x for
aqueous solution of formic acid. The points
are the experimental data and the lines are
calculated values of
*

and
*

Fig. 5. The variations of
*

and
*

versus
W
x for
aqueous solution of 2-Amino-2-methyl-1-propanol
(AMP). The points are the experimental data
and the lines are the calculated
values of
*

and
*


Figure 6 illustrates the agreement between the experimental values of the surface tension for the
aqueous solution of monoethanolamine (MEA) at 25, 35, 45C and the calculated values. The points are
experimental data and the lines are obtained by inserting the fixed values of the parameters a and b as
-50
-40
-30
-20
-10
0
0 0.2 0.4 0.6 0.8 1
x W

E
(
m
N
/
m
)
1-Propanol
2-Propanol
Ethanol
Methanol
R. Tahery / H. Modarress

Iranian Journal of Science & Technology, Volume 29, Number B5 October 2005
508
reported in Table 2 in Eqs. (5) and (8). Figure 7 shows the same variation as Figure 6, that is,
versus
A
x for aqueous solution triethanolamine (TEA) at 25, 35, 45C.

MEA+Water
45
55
65
75
0.0 0.2 0.4 0.6 0.8 1.0
x
A

(
m
N
/
m
)
25C
35C
45C

TEA+Water
35
45
55
65
75
0.0 0.2 0.4 0.6 0.8 1.0
x
A

(
m
N
/
m
)
25C
35C
45C


Fig. 6. The variations of versus
A
x for aqueous
solution of monoethanolamine at 25, 35, 45C.
The points are experimental data and
the lines are calculated values
Fig. 7. The variations of versus
A
x for aqueous
solution of triethanolamine at 25, 35, 45C.
The points are experimental data and
the lines are calculated values

4. CONCLUSIONS

A new surface tension equation is proposed for binary aqueous-organic solutions, which is different from
the existing equations proposed by the other authors. The parameters of this equation have been calculated
for 15 binary aqueous-organic solutions. A new property named surface tension coefficient is defined
and calculated for the studied solutions and is used as an indication of deviations from ideal behavior. The
overall AAD% for the correlation of surface tensions by the new equation is obtained as 0.53%, which is
lower than the AAD% obtained by two similar equations proposed by other workers (Zihao et al. [17] and
Zhibao and Benjamin [18]). Although comparing with the AAD% obtained by one of the equations
(Connors and Wright [9]), the new equation has a slightly higher AAD%, it is superior due to the fact that
its parameters are independent of temperature, and therefore it has higher predictability.

NOMENCLATURE

AAD Average absolute deviation
a and b Coefficients of Eq. (9)
n Number of experimental data
T Temperature (K)
x
Mole fraction
Greek symbols
Surface tension coefficient defined by Eq. (5)
Characteristic parameter defined by Eq. (11)
A new and a simple model for surface tension prediction of

October 2005 Iranian Journal of Science & Technology, Volume 29, Number B5
509
Surface tension (mN/m)
Excess reduced quantity
Superscripts
* Reduced quantity
Subscripts
A Organic component
Br Reduced quantity at boiling point
C Thermodynamic properties at critical point
E Excess property
W Water
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