Matlab-based Computer Program for the Prediction of Surface Tension of

A
Paraffin Hydrocarbons

Abstract

Surface tension of the liquid n-alkenes is one of the most dramatic examples of intermolecular forces. In designing
distillation towers, extraction units and internal towers such as bubble caps and trays, the prediction of surface
tension is critical as it has a significant influence on the transfer of mass and energy through interfaces.
Surface tension data are required wherever emulsification of foaming, droplet formation or wetting occurs. They are
also required in many equations of two-phase flow calculations and to determine the flow regime.

Petroleum engineers are particularly interested in surface tension in crude oil extraction to incorporate surfactants to
change the interfacial properties between crude oil and geological reservoir in order to improve production and
increase oil yields.

In this study, to estimate the surface tension of paraffin hydrocarbons as a function of molecular weight and temper
ature, a simple computer program using Arrhenius-type asymptotic exponential function.
The surface tension is measured for temperatures ranging from 250 to 440 K and molecular weights of paraffin hyd
rocarbons from 30 to 250. Because of its precision and consistent statistical context, the proposed numerical
methodology is superior, whereby the appropriate coefficients can be quickly replaced if more information are
available in the future. Estimates were found to be in excellent alignment with the literature's reliable data with an
average absolute deviation of less than 1.5%.

Introduction
Surface tension is an important property used in the design of fractionators, absorbers, two-phase
pipelines, petroleum reservoir engineering calculations, and it is an important property where foaming,
wetting, emulsification, and droplet formation are likely to occur [1][2]. Numerous methods have been
proposed to estimate the surface tension of pure liquids and liquid mixtures [3][4]. One of the simplest is
the empirical formula proposed by Macleod [5] which expresses the surface tension of a liquid in
equilibrium with its own vapor as a function of the liquid and vapor phase densities. However, Sugden [6]
[7] modified this expression as a function of a temperature-independent parameter, parachor, and indicated
a way to estimate it from molecular structure. Quayle [8] used experimental surface tension and density
data for numerous compounds to calculate the parachors of hydrocarbons. It has been shown that the
parachor is a weak function of temperature for a variety of fluids and within wide range of temperatures
[5][6][7][8], and thus it is generally
assumed to be a constant. The good performance and extreme simplicity of its analytical form have made
Macleod equation [5] a very popular method for surface tension calculation [9] [10][11][12][13].
Nevertheless, there are various shortcomings for the application of this equation: (1) the parachor is
actually a temperature-dependent parameter whose functional form with temperature was not known, (2)
the empirical nature of parachor poses difficulty in deriving a more accurate expression for it, and (3) the
absolute average percent deviation in surface tension prediction increases with increasing complexity of
the molecular structure of fluid under consideration [14].

Macleod's empirical expression for surface tension calculation has proven to work very well for many
substances and over a wide range of temperature. Nonetheless, deviations with respect to temperature are
generally observed. Thus, efforts should be made to derive the functionality of surface tension with respect
to temperature. The bottom-line is that methods of physical properties should be sought only in terms of
independent variables such as temperature, pressure, molecular weight, and concentration [15].
In view of the above mentioned issues, it is necessary to develop an accurate and simple method which is
easier than existing approaches less complicated with fewer computations for predicting the paraffin
hydrocarbons surface tension as a function of molecular weight and temperature using Matlab [16]
technical computing language. The paper discusses the formulation of such equations in a systematic
manner along with a sample example to show the simplicity of the model and usefulness of such tools.

Methodology for the Development of Novel Tool

The primary purpose of the present study is to accurately correlate the paraffin hydrocarbons surface tension as a
function of molecular weight and temperature. This is done by a simple method using an Arrhenius-type asymptotic
exponential function with a small modification of the Vogel-Tammann-Fulcher (VTF) equation (Vogel, [17]
Tammann and Hesse, [18] Fulcher [19]).
This is important, because such an accurate and mathematically simple method of the paraffin hydrocarbons surface
tension as a function of molecular weight and temperature is required frequently for the quick engineering
calculations to avoid the additional computational burden of complicated calculations. The VTF equation is an
asymptotic exponential function that is given in the following general form [15]:

E
ln f =ln f c − ………(1)
R ( T −T c )
In equation 2, f is a properly defined temperature-dependent parameter, the units for which are determined
individually for a certain property; fc is a pre-exponential coefficient, having the same unit of the property of
interest; T and Tc are the actual temperature and the characteristic-limit temperature, respectively (both given in
degrees Kelvin); E is referenced as the activation energy of the process causing parameter variation (given in units
of J/kmol); and R is the universal gas constant (R ) 8.314 J/(kmol K)). A special case of the VFT equation for Tc = 0
is the well-known Arrhenius equation [20].
For the purpose of the present application which involves the method of paraffin hydrocarbons surface tension as a
function of molecular weight and temperature e, the VTF equation has been modified in the following form by
adding second-order and third order terms [15]:

b c d
ln f =ln f c + + + …………(2)
( T −T c ) ( T −T c ) ( T −T c )3
2

In equation 2, Tc has been considered zero to convert equation 2 to the well-known Arrhenius equation [20] type. The
required data to develop this method includes the reported data [21][22] for the loss paraffin hydrocarbons surface
tension as a function of molecular weight and temperature. The following methodology has been applied to develop
this method.

Development of method

The required data to develop this method includes the reported data [21][22][25] for the loss of paraffin
hydrocarbons surface tension as a function of molecular weight and temperature. The following methodology has
been applied to develop this method. Firstly, surface tensions of paraffin hydrocarbons are correlated as a function
of temperature for several molecular weights then, the calculated coefficients for these equations are correlated as a
function of molecular weight. The derived equations are applied to calculate new coefficients for equation (9) to
predict surface tensions of paraffin hydrocarbons. Table 1 shows the tuned coefficients for equations (10) to (13) for
predicting surface tensions of paraffin hydrocarbons. In brief, the following steps are repeated to tune the method's
coefficients [26][27]:

1. Correlate the surface tensions of paraffin hydrocarbons as a function of temperature (T) for a given molecular
weight.
2. Repeat step 1 for other molecular weights.
3. Correlate corresponding polynomial coefficients, which were obtained for different temperature versus
molecularweight, a = f (M), b = f (M), c = f (M), d = f (M) [see equations (10)-(13)].
Equation 9 represents the proposed governing equation in which four coefficients are used to correlate the paraffin
hydrocarbons surface tensions as a function of temperature (T) for a given molecular weight where the relevant
coefficients have been reported in Table 1
b c d
ln σ =a+ + 2 + 3
T T T
Where,

B1 C1 D 1
a= A1 + + +
M M2 M3
B 2 C2 D 2
b= A2 + + +
M M2 M 3
B3 C 3 D 3
c= A 3+ + +
M M2 M3
B 4 C 4 D4
d= A 4 + + +
M M2 M3

These optimum tuned coefficients help to cover the temperatures in the range of 230 to 420 K and molecular weight
ranging between 30 and 240. The optimum tuned coefficients given in Table 1 can be further retuned quickly
according to proposed approach if more data are available in the future.

In this work, our efforts directed at formulating a method can be expected to assist engineers for rapid calculation of
surface tensions of paraffin hydrocarbons as a function of temperature (T) and molecular weight (M) using an
exponential function. The proposed novel tool developed in the present work is simple and unique expression which
is non-existent in the literature. Furthermore, the selected exponential function to develop the tool leads to well-
behaved (i.e. smooth and non-oscillatory) equations enabling reliable and more accurate predictions.

Results

Figure 1 shows a snap shot of developed Matlab-based Computer Program. Figures 2 and 3 show the results from
the proposed method to predict the surface tensions of paraffin hydrocarbons for temperatures ranging between -40
to 150°C and molecular weights in the range of 30 to 240 in two different view points. Table 2 illustrates the
accuracy of proposed method for predicting the surface tension of paraffin hydrocarbons in comparison with some
reported data [21][22][25]. The accuracy of method in terms of average absolute deviation is 1.85%. Table 3
illustrates the accuracy of proposed method for predicting the surface tension of paraffin hydrocarbons in
comparison with some reported data in the literature [25][28][29][30][31]. The accuracy of method in terms of
average absolute deviation is around 1%. It is expected that our efforts in formulating a simple tool in this
investigation will pave the way for arriving at an accurate prediction of surface tension of paraffin hydrocarbons at
various conditions which can be used by practice engineers and scientists for monitoring the key parameters
periodically. The proposed tool has been developed using Matlab technical computing language [16] and it works
for temperatures in the range of 230 to 420 K and molecular weights of paraffin hydrocarbons ranging between 30
and 240. Typical example is given below to illustrate the simplicity associated with the use of proposed method for
rapid estimation of surface tension of paraffin hydrocarbons. The tool developed in this study can be of immense
practical value for engineers and scientists to have a quick check of surface tension on the paraffin hydrocarbons at
various conditions without opting for any experimental measurements. In particular, chemical and process engineers
would find the approach to be user-friendly with transparent calculations involving no complex expressions.

Conclusions:

In this work, simple-to-use equations, which are easier than existing approaches less complicated with fewer
computations and suitable for process and petroleum engineers, are presented here for the estimation of surface
tensions of paraffin hydrocarbons as a function of temperature and molecular weight. Unlike complex mathematical
approaches for estimating surface tensions of paraffin hydrocarbons, the proposed method is simple-to-use and
would be of immense help for process engineers especially those dealing with hydrocarbon processing.
Additionally, the level of mathematical formulations associated with the estimation of surface tensions can be easily
handled by an engineer or practitioner without any in-depth mathematical abilities. Example shown for the benefit of
engineers clearly demonstrates the simplicity and usefulness of the proposed tool. Furthermore, estimations are quite
accurate as evidenced from the comparisons with literature data (with average absolute deviation being less than
2%) and would help in attempting design and operations modifications with less time. The proposed method has
clear numerical background, wherein the relevant coefficients can be retuned quickly if more data are available in
the future.

Nomenclatures:

A: Tuned coefficient
B: Tuned coefficient
C: Tuned coefficient
D: Tuned coefficient
E: The activation energy of the process causing parameter variation (J/kmol);

f : a properly defined temperature-dependent parameter, the units for which are determined individually for a certain
property;

fc is a pre-exponential coefficient, having the same unit of the property of interest;

M: Molecular weight
T: Temperature, K
 Tc : The characteristic-limit temperature, K

R : The universal gas constant (R ) 8.314 J/(kmol K)).

σ : Surface tension, mN/m

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Table 1 Tuned coefficients used in Equations 10 to 13

Coefficient Value

A1 14.533851511745
B1 -3566.784747107000
C1 161252.099282700000
D1 -8926610.586578600000
A2 -9758.312966782200
B2 2781278.887969000000
C2 -106792648.261600000000
D2 6089647494.090800000000
A3 2927625.677876000000
B3 -760923940.983610000000
C3 24336871495.109000000000
D3 -1390354495061.200000000000
A4 -294822317.255080000000
B4 72074204865.329000000000
C4 -1966217568665.400000000000
D4 106898693167900.000000000000
 Table 2 Comparison of calculated surface tension with typical data

T (°C) M.W. Hydrocarbo Calculated surface Reported surface tension, Absolute Deviation
n tension, mN/m mN/m [21][22][25] (Percent)
-40 30 C2H6 8.3807 8.5 1.42
0 30 C2H6 3.3424 3.25 2.84
20 30 C2H6 1.2596 1.25 0.77
-25 44 C3H8 12.4146 13 4.5
30 44 C3 H 8 6.1366 6 2.28
100 44 C3 H 8 0.5038 0.5 0.76
5 44 C3 H 8 9.0881 9 0.98
-30 58 n - C4 H10 18.993 18.5 2.66
10 58 n - C4 H10 13.4477 13.5 0.39
80 58 n - C4 H10 5.4803 5.5 0.36
-20 72 n - C5 H12 20.2792 20.5 1.08
10 72 n - C5 H12 16.8039 17 1.16
50 72 n - C5 H12 12.888 12.5 3.01
150 72 n - C5 H12 3.0746 3 2.49
-20 86 n - C6 H14 22.8144 22.5 1.39
-10 86 n - C6 H14 21.2765 21.5 1.04
80 86 n - C6 H14 12.1473 12 1.23
145 86 n - C6 H14 5.7473 6 4.39
0 100 n - C7 H16 22.0295 22 0.13
40 100 n - C7 H16 18.3431 18 1.9
120 100 n - C7 H16 10.0459 10.5 4.32
160 100 n - C7 H16 6.6563 7 4.91
-20 114 n - C8 H18 25.9898 25 3.96
0 114 n - C8 H18 23.4982 23.5 0.01
150 114 n - C8 H18 9.1783 9.5 3.5
-15 142 n - C10 H 22 27.204 27 0.75
0 142 n - C10 H 22 26.257 26 0.98
125 142 n - C10 H 22 15.048 15 0.32
-15 184 n - C13 H 28 28.969 29 0.1
155 184 n - C13 H 28 15.421 15 2.8
-5 198 n - C13 H 28 28.668 28.5 0.58
125 198 n - C13 H 28 18.43 18.5 0.38
-10 240 n - C17 H 36 30.076 29.5 1.95
130 240 n - C17 H 36 20.637 20 3.18
Average absolute deviation, percent 1.85
 Table 3 Comparison of calculated surface tension with typical experimental data
T (°C) M.W. Hydrocarbon Calculated surface Experimental surface References of Absolute
tension, mN/m tension, mN/m experimental Deviation
(Percent)
30 72 n - C5 H12 14.99 14.94 Jasper and Kring, [25] 0.33
10 72 n - C5 H12 16.8 17.15 Jasper and Kring, [25] 2.04
20 72 n - C5 H12 15.93 16.05 Jasper and Kring, [25] 0.75
0 72 n - C5 H12 17.7 18.25 Jasper and Kring, [25] 3.01
10 86 n - C6 H14 19.23 19.42 Jasper and Kring, [25] 0.97
0 86 n - C6 H14 22.03 22.1 Jasper and Kring, [25] 0.32
50 86 n - C6 H14 15.46 15.34 Jasper and Kring, [25] 0.78
30 86 n - C6 H14 17.44 17.38 Jasper and Kring, [25] 0.34
0 100 n - C7 H16 22.03 22.28 Queimada et al, [28] 1.12
10 100 n - C7 H16 21.08 21.12 Jasper [29] 0.19
20 100 n - C7 H16 20.18 20.21 McLure et al [31] 0.15
30 100 n - C7 H16 19.28 19.27 Jasper [29] 0.05
40 100 n - C7 H16 18.34 18.5 Rolo et al, [30] 0.87
50 100 n - C7 H16 17.36 17.44 Rolo et al, [30] 0.46
60 100 n - C7 H16 16.33 16.5 Rolo et al, [30] 1.04
40 114 n - C8 H18 19.81 19.71 Jasper and Kring, [25] 0.51
100 114 n - C8 H18 13.76 14.01 Jasper and Kring, [25] 1.78
70 114 n - C8 H18 16.84 16.86 Jasper and Kring, (1955) 0.12
50 142 n - C10 H 22 21.12 21.07 Jasper and Kring, [25] 0.23
0 142 n - C10 H 22 25.66 25.67 Jasper and Kring, [25] 0.04
70 142 n - C10 H 22 19.23 19.7 Rolo et al, [30] 2.38
30 142 n - C10 H 22 22.98 22.95 Jasper [29] 0.13
20 170 n - C12 H 26 25.46 25.35 Jasper and Kring, [25] 0.43
100 170 n - C12 H 26 18.49 18.28 Jasper and Kring, [25] 1.15
20 184 n - C13 H 28 26.13 25.99 Jasper and Kring, [25] 0.54
70 184 n - C13 H 28 21.86 21.63 Jasper and Kring, [25] 1.06
40 198 n - C14 H 30 25.06 24.82 Jasper and Kring, [25] 0.96
80 198 n - C14 H 30 21.77 21.35 Jasper and Kring, [25] 1.97
50 240 n - C17 H 36 25.87 25.38 Jasper and Kring, [25] 1.89
Average absolute deviation, percent 0.88
Figure 1 : Performance of model for prediction of surface tensions of paraffin hydrocarbons using new proposed method

Figure 2 : Performance of model for prediction of surface tensions of paraffin hydrocarbons in another viewpoint
nsion, mN/m

on, (m N )/m