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Development of Mathematical Model and MATLAB Tool for

Prediction of Surface Tension of Paraffin Hydrocarbon

SARTHAK BAPAT, R820217092 (500060816)


SHOBHIT KUMAR, R820217110 (500061160)
VISHESH SHARMA, R820217133 (500060287)
VIBHOR KUMAR PANDEY, R820217129 (500061012)
SHUBHAM VERMA, R820217112 (500061478)

Dr. Rahul Kumar


Department of Chemical Engineering

June-2020
I hereby declare that this submission is my own and that, to the best of my knowledge and
belief, it contains no material previously published or written by another person nor material
which has been accepted for the award of any other Degree or Diploma of the University or
other Institute of Higher learning, except where due acknowledgement has been made in
text.

SARTHAK BAPAT, R820217092 (500060816)


SHOBHIT KUMAR, R820217110 (500061160)
VISHESH SHARMA, R820217133 (500060287)
VIBHOR KUMAR PANDEY, R820217129 (500061012)
SHUBHAM VERMA, R820217112 (500061478)

2
CERTIFICATE

This is to certify that the thesis titled A MATLAB-based Computer Program for the
Prediction of Surface Tension of Paraffin Hydrocarbons, submitted by SARTHAK
BAPAT, R820217092 (500060816); SHOBHIT KUMAR, R820217110 (500061160);
VISHESH SHARMA, R820217133 (500060287); VIBHOR KUMAR PANDEY,
R820217129 (500061012); SHUBHAM VERMA, R820217112 (500061478) to the
University of Petroleum & Energy Studies, for the award of the degree of BACHELOR
OF TECHNOLOGY in Applied Petroleum Engineering is a Bonafede record of project work
carried out by him/her/them under my/our supervision and guidance. The content of the
thesis, in full or parts have not been submitted to any other Institute or University for the
award of any other degree or diploma.

Signature of mentor

Dr. Rahul Kumar


Department of Chemical Engineering

Date: 4 June, 2020

3
ACKNOLEDGEMENTS

This project would not have been successful without our mentor, Dr. Rahul Kumar, who
gave us an opportunity to do this work. We wish to express our gratitude for his abundantly
helpful and offered invaluable assistance, support and guidance throughout the study.
We would also like to thank Dr. Shailesh Kumar who provided resources and plans that
help us in our Project.
We would also like to thank Dr. Vamshikrishna Domala, Mr. Nitish Kumar Choudhary
(Halliburton Offshore Services), who provided resources and plans that help us in our
Minor Project, Dr. P. Vijay (Head of the Department, Chemical Engineering) who provided
us with an opportunity to develop the project.
Lastly but not the least, we would like to thank all those without whose support this project
could not have been a successful one.

4
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 during crude oil extraction
to incorporate surfactants so as 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 temperature, we code 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 hydrocarbons 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 is 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%.

5
TABLE OF CONTENTS

CERTIFICATE ..................................................................................................3

ACKNOLEDGEMENTS ...................................................................................4

ABSTRACT .......................................................................................................5

INTRODUCTION .............................................................................................9

LITERATURE REVIEW ................................................................................11

2.1 Vandermonde matrix ..............................................................................12

METHODOLOGY...........................................................................................16

3.1 Nomenclatures: .......................................................................................17

RESULTS AND DISCUSSIONS ....................................................................18

CONCLUSION ................................................................................................19

REFERENCES.................................................................................................22

6
LISTS OF TABLES

Table 1: Experimental data from literature.......................................................................... 13

Table 2: Surface Tension from Experimental data .............................................................. 15

Table 3: Tuned coefficients used in Equations 10 to 13 ..................................................... 20

7
LIST OF FIGURES

Figure 1: Surface Tension Phenomena .................................................................................. 9

Figure 2: Performance of model for prediction of surface tensions of paraffin

hydrocarbons using new proposed method .......................................................................... 21

Figure 3: Performance of model for prediction of surface tensions of paraffin

hydrocarbons in another viewpoint ...................................................................................... 21

8
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. Numerous
methods have been proposed to estimate the surface tension of pure liquids and liquid
mixtures. One of the simplest is the empirical formula proposed by Macleod 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 modified this expression as a function of a
temperature-independent parameter, parachor, and indicated a way to estimate it from
molecular structure. Quayle 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, and thus it is generally assumed to be a constant. The good performance and
extreme simplicity of its analytical form have made Macleod equation a very popular method
for surface tension calculation.

Figure 1: Surface Tension Phenomena

9
Nevertheless, there are various shortcomings in the application of this equation: (1) the
parachor is actually a temperature-dependent parameter whose functional form with
temperature is 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.

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.

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 technical computing language. This project 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.

10
LITERATURE REVIEW

The primary purpose of the project is to accurately correlate the surface tension of paraffin
hydrocarbons 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, Tammann and Hesse, Fulcher).

This is important, because such an accurate and mathematically simple method of estimating
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:

𝐸
ln 𝑓 = ln 𝑓𝑐 − ………(1)
R(𝑇−𝑇𝐶 )

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.

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:

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

In equation (2), Tc has been considered zero to convert equation (2) to the well-known
Arrhenius equation type.

𝑏 𝑐 𝑑
ln 𝑓 = ln 𝑓𝑐 + + + ……….(3)
𝑇 𝑇2 T3

The required data to develop this method includes the reported data 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.

11
2.1 Vandermonde matrix

Vandermonde matrix is a matrix with the terms of a geometric progression in each row, i.e.,
an m × n matrix (Horn and Johnson, 1991).

1 𝛼1 𝛼12 … 𝛼1𝑛−1
1 𝛼2 𝛼22 … 𝛼2𝑛−1
𝑉 = 1 𝛼3 𝛼32 … 𝛼3𝑛−1
⋮ ⋮ ⋮ ⋱ ⋮
2 𝑛−1
[ 1 𝛼𝑚 𝛼𝑚 ⋯ 𝛼𝑚 ]

OR

𝑗−1
𝑉 = 𝛼𝑖 ………(5)

For all indices i and j, the determinant of a square Vandermonde matrix (where m=n) can be
expressed as:

𝑑𝑒𝑡(𝑉) = ∏1≤𝑖<𝑗≤𝑛(𝛼𝑗 − 𝛼𝑖 ) ………(6)

The Vandermonde matrix evaluates a polynomial at a set of points; formally, it transforms


coefficients of a polynomial:

𝑎0 + 𝑎1 𝑥 + 𝑎2 𝑥 2 + ⋯ + 𝑎𝑛−1 𝑥 𝑛−1

to the values the polynomial takes at the point αi. The non-vanishing of the determinant of
the Vandermonde determinant for distinct points αi shows that, for distinct points, the map
from coefficients to values at those points is a one-to-one correspondence, and thus that the
polynomial interpolation problem is solvable with unique solution; this result is called the
unisolvence theorem (Fulton and Harris 1991). They are thus useful in polynomial
interpolation, since solving the system of linear equations Vu = y for u with V an m × n
Vandermonde matrix is equivalent to finding the coefficients ui of the polynomial(s).

𝑃(𝑥 ) = ∑𝑛−1 𝑗
𝑗=0 𝑢𝑖 𝑥 ……...(7)

For degree ≤ n−1 which has (have) the property:

𝑃(𝛼𝑖 ) = 𝑦𝑖 ; For i=1,…,m ……….(8)

The Vandermonde matrix can easily be inverted in terms of Lagrange basis polynomials:
each column is the coefficients of the Lagrange basis polynomial, with terms in increasing
order going down. The resulting solution to the interpolation problem is called the Lagrange
polynomial.

12
Temperature (°C) Molecular weight Hydrocarbon Reported surface
tension (mN/m)

-40 30 C2 H 6 8.5
0 30 C2 H 6 3.25
20 30 C2 H 6 1.25
-25 44 C3 H 8 13
30 44 C3 H 8 6
100 44 C3 H 8 0.5
5 44 C3 H 8 9
-30 58 n − C4 H10 18.5
10 58 n − C4 H10 13.5
80 58 n − C4 H10 5.5
-20 72 n − C5 H12 20.5
10 72 n − C5 H12 17
50 72 n − C5 H12 12.5
150 72 n − C5 H12 3
-20 86 n − C6 H14 22.5
-10 86 n − C6 H14 21.5
80 86 n − C6 H14 12
145 86 n − C6 H14 6
0 100 n − C7 H16 22
40 100 n − C7 H16 18
120 100 n − C7 H16 10.5
160 100 n − C7 H16 7
-20 114 n − C8 H18 25
0 114 n − C8 H18 23.5
150 114 n − C8 H18 9.5
-15 142 n − C10 H 22 27
0 142 n − C10 H 22 26
125 142 n − C10 H 22 15

-15 184 n − C13 H 28 29


155 184 n − C13 H 28 15
-5 198 n − C13 H 28 28.5
125 198 n − C13 H 28 18.5
-10 240 n − C17 H 36 29.5
130 240 n − C17 H 36 20

Table 1: Experimental data from literature

13
Experimental
Temperature (°C) Molecular Hydrocarbon surface tension References of experimental
weight (mN/m)

30 72 n − C5 H12 14.94 Jasper and Kring, [25]

10 72 n − C5 H12 17.15 Jasper and Kring, [25]

20 72 n − C5 H12 16.05 Jasper and Kring, [25]

0 72 n − C5 H12 18.25 Jasper and Kring, [25]

10 86 n − C6 H14 19.42 Jasper and Kring, [25]

0 86 n − C6 H14 22.1 Jasper and Kring, [25]

50 86 n − C6 H14 15.34 Jasper and Kring, [25]

30 86 n − C6 H14 17.38 Jasper and Kring, [25]

0 100 n − C7 H16 22.28 Queimada et al, [28]

10 100 n − C7 H16 21.12 Jasper [29]

20 100 n − C7 H16 20.21 McLure et al [31]

30 100 n − C7 H16 19.27 Jasper [29]

40 100 n − C7 H16 18.50 Rolo et al, [30]

50 100 n − C7 H16 17.44 Rolo et al, [30]

60 100 n − C7 H16 16.5 Rolo et al, [30]

40 114 n − C8 H18 19.81 Jasper and Kring, [25]

100 114 n − C8 H18 13.76 Jasper and Kring, [25]

70 114 n − C8 H18 16.84 Jasper and Kring, (1955)

50 142 n − C10 H 22 21.12 Jasper and Kring, [25]

0 142 n − C10 H 22 25.66 Jasper and Kring, [25]

70 142 n − C10 H 22 19.23 Rolo et al, [30]

30 142 n − C10 H 22 22.98 Jasper [29]

14
20 170 n − C12 H 26 25.46 Jasper and Kring, [25]

100 170 n − C12 H 26 18.49 Jasper and Kring, [25]

20 184 n − C13 H 28 26.13 Jasper and Kring, [25]

70 184 n − C13 H 28 21.86 Jasper and Kring, [25]

40 198 n − C14 H 30 25.06 Jasper and Kring, [25]

80 198 n − C14 H 30 21.77 Jasper and Kring, [25]

50 240 n − C17 H 36 25.87 Jasper and Kring, [25]

Table 2: Surface Tension from Experimental data

15
METHODOLOGY

The required data to develop this method includes the reported data 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, known 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:

• Correlate the surface tensions of paraffin hydrocarbons as a function of temperature (T)


for a given molecular weight.
• Repeat step 1 for other molecular weights.
• Correlate corresponding polynomial coefficients, which were obtained for different
temperature versus molecular weight, a = f (M), b = f (M), c = f (M), d = f (M).
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 + + + ……..(9)
𝑇 𝑇2 𝑇3

Where,

𝐵1 𝐶1 𝐷1
a = 𝐴1 + + + ……..(10)
𝑀 𝑀2 𝑀3
𝐵2 𝐶2 𝐷2
b = 𝐴2 + + + ……..(11)
𝑀 𝑀2 𝑀3
𝐵3 𝐶3 𝐷3
c = 𝐴3 + + + ……..(12)
𝑀 𝑀2 𝑀3
𝐵4 𝐶4 𝐷4
d = 𝐴4 + + + ……..(13)
𝑀 𝑀2 𝑀3

16
These optimum tuned coefficients help to cover the temperatures in the range of 230 K 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.

3.1 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: a pre-exponential coefficient, having the same unit as 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)

17
RESULTS AND DISCUSSIONS

Surface Tension is a very important property of any fluid and its determination is very
important for evaluating the characteristics of the fluids and equipment design. In the case
of crude oil, proper estimation of the surface tension of oil-gas systems is important in a
number of reservoir engineering calculations. The surface tension is required to predict the
capillary pressure of the oil in a porous solid. The surface tension also influences the
relative gas/liquid phase permeabilities.

For determination of the surface tension of the paraffin hydrocarbon we tried to develop a
mathematical model to determine the error less value of the without using any experimental
method to calculate the value of surface tension. The modern-day method we are using like:
capillary rise method, drop weight method, dynamic method, etc. require expensive
equipment and also include blacklisted errors and majority of them are human errors which
cannot be excluded and often requires corrections which are time consuming but the program
which we are focusing to develop will result in less than 2% error and also gives result in
less than 2 seconds of run time.

The final equation in derived using the above shown method and we arrive to the following
result for the calculation of surface tension:

𝑏 𝑐 𝑑
ln 𝜎 = 𝑎 + + 2+ 3
𝑇 𝑇 𝑇
Where,

𝐵1 𝐶1 𝐷1
a = 𝐴1 + + 2+ 3
𝑀 𝑀 𝑀
𝐵2 𝐶2 𝐷2
b = 𝐴2 + + 2+ 3
𝑀 𝑀 𝑀
𝐵3 𝐶3 𝐷3
c = 𝐴3 + + 2+ 3
𝑀 𝑀 𝑀
𝐵4 𝐶4 𝐷4
d = 𝐴4 + + 2 + 3
𝑀 𝑀 𝑀

As per our further plan we are going to develop a tool using MATLAB for this mathematical
model to determine the surface tension in Seconds. For the development of the tool we have
gone through the various research papers and obtain the value of Surface tension of different
paraffin Hydrocarbons at different temperatures and molecular weights.

In future we are going to use these available data to develop a MATLAB tool and find the
value of tuned coefficients in the equation provided above.
18
CONCLUSION

The above developed tool using the Mathematical model developed and surface tension data
form the literature is expected to have an error less than 2% and is very useful in pre-
assessment of the surface tension and can be used to generate more accurate value if we can
obtain more data in future.

Cost analysis of the above tool leads to the conclusion that the developed tool is highly
economical in nature and will be free of cost for lifetime, once developed. In the case of
equipment, the standards of the equipment can’t be improved without rigorous efforts.
However, the scope of improvement for this tool is excellent as data becomes more abundant
in the future. Any data obtained will be helpful for improving the accuracy.

Up to Mid-Semester Review we have done the literature review for the topic and developed
a mathematical model which represents the surface tension at different Molecular weights
and temperature, and we collected the data for the surface tension for of paraffin hydrocarbon
at different molecular weights and temperature.

The expected error is less than 2% of the real value, which will be quite comparable if we
see the economics of the tool and it is flexibility in respect to error reduction in future.

19
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 3: Tuned coefficients used in Equations 10 to 13

20
Figure 2: Performance of model for prediction of surface tensions of paraffin hydrocarbons using new proposed method

Figure 3: Performance of model for prediction of surface tensions of paraffin hydrocarbons in another viewpoint

21
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