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Interfacial tension

Interfacial or surface tension exists when two phases are present. These phases can be gas/oil,
oil/water, or gas/water. Interfacial tension is the force that holds the surface of a particular phase together
and is normally measured in dynes/cm. The surface tension between gas and crude oil ranges from near
zero to approximately 34 dynes/cm. It is a function of pressure, temperature, and the composition of
each phase.

Contents
[hide]

1 Approaches to determine gas/oil surface tension


2 Models to calculate surface tension
3 Water-hydrocarbon surface tension
4 Nomenclature
5 References
6 Noteworthy papers in OnePetro
7 External links
8 See also

Approaches to determine gas/oil surface tension


Two forms of correlations for calculating gas/oil surface tension have been developed.

The first form is a pseudocompositional black oil approach. Two components, gas and oil, are
identified, and techniques used with compositional models are used to calculate surface tension.

The second approach uses empirical correlations to determine surface tension.

Black oil correlations may provide less than accurate results because of the simplified characterization of
the crude oil. Generally, the heavy end components of a crude oil may be made of asphaltic and surface
active materials that have a measurable effect on surface tension.

With the compositional approach, surface tension is determined from the following equation proposed by
Weinaug and Katz. [1]

....................(1)

where the density terms are defined with units of g/cm3. Pi is the parachor of each component. This
property is a characteristic of pure components and is determined from surface tension measurements
where the density of the gas and liquid phases are known. Fig. 1[2] provides a relationship between
parachors and molecular weight.

Fig. 1 Hydrocarbon parachors.


[2]

Models to calculate surface tension


In 1973, Ramey[3] proposed a pseudocompositional method for calculating surface tension. The two
components are oil and gas. Gas is free to dissolve in the oil phase, and oil is free to vaporize in the gas
phase, which makes this method more versatile than the other methods discussed in this chapter. The
Weinaug-Katz equation is modified as

....................(2)

where the oil mole fraction in the oil phase is defined as

....................(3)

and the gas mole fraction in oil is

....................(4)

The mole fraction of oil and gas in the as phase is


....................(5)

and

....................(6)

The traditional assumption used with the black oil approach is that the oil vaporized in the gas phase, rv,
is zero. In this instance, yo= 0 and yg = 1, which simplifies Eqs. 5 and 6.

The average molecular weights of the oil and gas phases are defined as

....................(7)

and

....................(8)

Liquid and gas densities are defined with units of g/cm3:

....................(9)

and

....................(10)

Whitson and Brul[4] suggested the following parachor equations, which reproduce the graphical methods
suggested by Ramey:

....................(11)

and

....................(12)

In 1989, Asheim[5] presented another pseudocompositional correlation for surface tension. With the
assumption that no oil vaporizes into the gas phase, the resulting equation is

....................(13)

where the gas formation volume factor (FVF), Bg, is defined as


....................(14)

Asheim proposed the following equations to calculate the parachors for the oil and gas phases.

....................(15)

....................(16)

While this method appears different from that proposed by Ramey, it is identical for the Ramey case in
which no oil vaporizes into the gas phase. This method differs from Rameys method only by the
definition of the oil and gas parachors.

The Baker and Swerdloff[6][7] method was published in 1955. It was presented in the form of graphs for
estimating gas/oil surface tension (Fig. 2).

Fig. 2 Surface tension of crude oil at atmospheric pressure (after Baker and Swerdloff ).
[7]

Equations to calculate the dead oil surface tension at 68 and 100F are

....................(17)
and

....................(18)

Beggs[8] suggests that for temperatures greater than 100F, the value calculated for 100F should be
used. Similarly, if the temperature is less than 68F, the value calculated for 68F should be used. For
intermediate temperatures, surface tension is derived by linear interpolation as described by

....................(19)

At pressures greater than atmospheric pressure, gas is dissolved in the oil, which reduces surface
tension. Baker and Swerdloff provided the graphical correction factor shown in Fig. 3, which can be
reproduced mathematically by

....................(20)

The live oil surface tension is then derived from

....................(21)

Fig. 3 Effect of solution gas on crude oil surface tension (after Baker and Swerdloff ).
[7]
In 2000, Abdul-Majeed[9] presented an update to Baker and Swerdloffs correlation. Surface tension data
from 18 crude oils covering the temperature range 60 to 130F was used to derive Eq. 22, which Fig.
4 shows graphically.

....................(22)

Data acquired from 42 crude oil/gas systems was used to develop the live oil correction factor. These
data, shown graphically in Fig. 5, can be represented by

....................(23)

As with the Baker and Swerdloff method, the live oil surface tension is given by Eq. 21. Table 1 shows
the statistics provided by Abdul-Majeed comparing the results of the proposed method with the Baker
and Swerdloff method. Fig. 6 shows a comparison of the four methods for calculating interfacial tension.

Table 1

Fig. 4 Surface tension of crude oil at atmospheric pressure. (Reprinted from J. of Petroleum Science
and Engineering, Vol. 27, Abdul-Majeed and Abu Al-Soof, Estimation of Gas-Oil Surface Tension,
197, Copyright 2000, with permission from Elsevier.)

Fig. 5 Effect of solution gas on surface tension of crude oils. (Reprinted from J. of Petroleum
Science and Engineering, Vol. 27, Abdul-Majeed and Abu Al-Soof, Estimation of Gas-Oil Surface
Tension, 197, Copyright 2000, with permission from Elsevier.)

Fig. 6 Comparison of surface tension calculations methods.

Water-hydrocarbon surface tension


The surface tension of a water-hydrocarbon system varies from approximately 72 dynes/cm for
water/gas systems to 20 to 40 dynes/cm for water/oil systems at atmospheric conditions. In 1973,
Ramey[3] published methods to evaluate the surface tension of water-hydrocarbon mixtures.
Unfortunately, this work was for liquid hydrocarbons and did not extend into the gas-phase region. A later
publication by Firoozabadi and Ramey[10] provided a more generalized correlation suitable for use with
gas and liquid hydrocarbons. Surface tension data from pure components ranging from n-dodecane to
methane were plotted as shown in Fig. 7. The surface tension function used for the y-axis is

....................(24)

while the density difference between the water and hydrocarbon phase is plotted on the x-axis. The data
in Fig. 7 can be represented by

....................(25)

Fig. 7 Generalized correlation for water/hydrocarbon surface tension. [This material is being used
with permission from the Petroleum Society. The author thanks the Petroleum Society for the use of
this material and reminds the recipients that no other copies may be made without the expressed
written consent of the Petroleum Society. Firoozabadi, A. and Ramey, H.J.: Surface Tension of Water-
Hydrocarbon Systems at Reservoir Conditions, Journal of Canadian Petroleum Technology (May-
June 1988) 41.]

Solving for surface tension, the relationship becomes


....................(26)

This equation requires that the pseudocritical temperature of the oil and gas phases be calculated to
evaluate reduced temperature. Riazis[11] relationship for liquid hydrocarbons can be modified to yield

....................(27)

Suttons[12] equation for pseudocritical temperature can be used for the gas phase:

....................(28)

When the pressure increases and gas dissolves into the oil phase, the composition of that phase
changes. The pseudocritical temperature of the mixture can be evaluated by calculating the mole fraction
of each component present in the oil. For the oil component, we have

....................(29)

while the gas mole fraction in oil is

....................(30)

The pseudocritical temperature of the mixture is then the mole fraction weighted average pseudocritical
temperature of each component:

....................(31)

This work serves as a guide for estimating the surface tension between water and hydrocarbons.
Firoozabadi and Ramey recommended that a single point measurement for oil water systems be
obtained so that the curve in Fig. 7 could be appropriately adjusted. Fig. 8 shows an example of results
for oil/water and gas/water systems derived from this method.

Fig. 8 Water/hydrocarbon surface tension.

For methane-brine systems, Standing[4] has indicated that the surface tension will increase according
to Fig. 9. The relationship in Fig. 9 can be approximated by

....................(32)

Fig. 9 Methane/brine surface tension correlation.


[4]

Nomenclature
Bg = gas FVF, ft3/scf

Bo = oil FVF, bbl/STB

Kw = Watson characterization factor, R1/3

Mg = gas molecular weight, m, lbm/lbm mol

Mgo = gas/oil mixture molecular weight, m, lbm/lbm mol

Mo = oil molecular weight, m, lbm/lbm mol

Mog = oil-gas mixture molecular weight, m, lbm/lbm mol

p = pressure, m/Lt2, psia


pb = bubblepoint pressure, m/Lt2, psia

T = temperature, T, F

Tcg = gas pseudocritical temperature, T, R

Tcm = mixture pseudocritical temperature, T, R

Tco = oil pseudocritical temperature, T, R

Tr = reduced temperature, T

Tsc = temperature at standard conditions, T, F

xg = gas "component" mole fraction in oil

xo = oil "component" mole fraction in oil

yg = gas "component" mole fraction in gas

yo = oil "component" mole fraction in gas

g = gas specific gravity, air=1

ghc = gas specific gravity of hydrocarbon components in a gas mixture, air=1

gs = separator gas specific gravity, air=1

o = oil specific gravity

Z = gas compressibility factor

g = gas density, m/L3, lbm/ft3

o = oil density, m/L3, lbm/ft3

go = gas/oil surface tension, m/t2, dynes/cm


od = dead oil surface tension, m/t2, dynes/cm

P = parachor

Pg = gas parachor

Pi = parachor of each component

Po = oil parachor

Rs = solution GOR, scf/STB

psc = pressure at standard conditions, m/Lt2, psia

h = hydrocarbon density, m/L3, g/cm3

= dead oil surface tension at 68F, m/t2, dynes/cm

hw = hydrocarbon/water surface tension, m/t2, dynes/cm

w = water density, m/L3, g/cm3

h = hydrocarbon density, m/L3, g/cm3

Csw = salt concentration in water, ppm

rv = vaporized oil/gas ratio, STB/scf

xi = component i mole fraction in oil phase

yi = component i mole fraction in gas phase