Fluid Phase Equilibria 156 1999.

2133

Thermodynamic analysis of the mutual solubilities of normal alkanes

and water
)
Constantine Tsonopoulos
Exxon Research and Engineering, Florham Park, NJ 07932, USA

Abstract

Mutual solubility data for C 5 C 16 alkanes and water close to 298 K are investigated, along with calorimetric
heats of solution, as a function of the carbon number. The solubility of alkanes in water at 298 K drops steeply
with increasing CN carbon number., but the rate of decrease becomes significantly smaller for CN ) 11,
possibly suggesting a transition to a collapsed conformation that reduces contact of the alkane with water.
Calorimetric data for the heat of solution of normal alkanes and normal alkylbenzenes. in water strongly
suggest that the heat of solution is a linear function of temperature, in excellent agreement with solubility data,
and both calorimetric and solubility data indicate a minimum in solubility heat of solutions 0. at around 303 K
vs. 290 K for the alkylbenzenes.. The solubility of water in alkanes presents a much different picture from that
of alkanes in water. First, the solubility of water in alkanes at 298 K is fairly insensitive to CN, rising slightly
with increasing CN, while calorimetric measurements give a heat of solution that is nearly independent of
temperature and CN. Its magnitude, 35 kJ moly1 8.4 kcal moly1 ., is that of a normal hydrogen-bond energy,
suggesting that the dissolution of n water molecules leads to the breaking of n hydrogen bonds. The
temperature dependence of the solubility data is well represented by an equation that assumes a temperature-in-
dependent heat of solution that decreases slightly with increasing CN. q 1999 Elsevier Science B.V. All rights
reserved.

Keywords: Alkane solubility; Water solubility; Carbon number effect; Heat of solution

1. Introduction

Knowledge of the hydrocarbonrwater mutual solubilities is frequently important in the design and
operation of process equipment in refineries and petrochemical plants. Hydrocarbons, like other
pollutants, must be removed from refinery and petrochemical plant wastewater streams. Accordingly,

)
Tel.: q1-973-765-1380; fax: q1-973-765-1189; e-mail: ctsonop@fpe.erenj.com

0378-3812r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 9 9 . 0 0 0 2 1 - 7
22 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133

the solubility and volatility of the hydrocarbons are needed to trace their phase distribution through
the entire process sequence and to design separation equipment such as sour water strippers. for their
removal.
If the water present in a hydrocarbon mixture exceeds its solubility limit, a second liquid phase will
form, the free water phase, that can affect product specifications and equipment operation. Perhaps
the most common adverse process effect is corrosion. Even when a free-water phase does not form,
the solubility of water in hydrocarbons at 470 K and above is so high that the phase distribution of
water can affect both the operation of the equipment, say, a distillation tower, and the product quality.
Sometimes, however, a water-rich phase is formed intentionally, for example, to remove salts that
would otherwise deposit out. This case also requires the accurate prediction of the solubility limits.
The maximum temperature of interest in water pollution abatement is about 420 K, or even 470 K
in certain cases, which can be reached in sour water strippers. On the hydrocarbon-rich side, the
maximum temperature of interest is the three-phase critical end point temperature, the maximum
temperature at which the hydrocarbon-rich liquid phase can exist. As shown in Fig. 1, this is below
the critical temperature of the hydrocarbon.
In a series of publications w13x, we presented new mutual solubility data on C 6 C 12 hydrocarbons
and water, where we emphasized the high-temperature range. Here, we focus on temperatures closer

Fig. 1. P T diagram of n-decanerwater from Ref. w1x..

 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133 23

to 298 K generally, below 400 K. and examine both the mutual solubilities and the heats of solution
as a function of the carbon number. As a first step, we consider the C 5 C 16 normal alkanes along
with solubility of water in liquid ethane and propane. .

2. Mutual solubilities of alkanes and water

An example of the phase behavior of alkanerwater binaries is given in Fig. 1 for n-decanerwater
w3x. A point below the three-phase equilibrium curve represents equilibrium between one liquid phase
and the vapor, while a point above the line represents equilibrium between the hydrocarbon-rich and
water-rich liquid phases. All three phases are at equilibrium at P3 , the three-phase equilibrium
pressure. Because the mutual solubilities are only weakly pressure-dependent w1x, the mutual
solubilities are generally measured at P slightly above P3 if the vapor phase is of no interest..
As it will be shown later, the two mutual solubilities have a significantly different dependence on
carbon number, as well as on temperature; that is, the two heats of solution are drastically different.
The solubility of alkanes in water goes through a minimum where the heat of solution is zero. , while
that of water in alkanes increases monotonically with increasing temperature w13x. We will examine
the solubility and heat of solution separately for alkanes in water and water in alkanes. First we will
consider the solubility at 298 K, and then the heat of solution.

3. Solubility of alkanes in water

3.1. Solubility at 298 K

The solubility of liquid normal alkanes in water at 298 K drops steeply with increasing molar
volume, which is proportional to the carbon number. As shown in Fig. 2, the solubility goes from
about 10 parts per million by mole for pentane to less than 10 parts per billion by mole for decane
where the data w4x scatter between 1 and 7 mppb. . This steep drop in solubility with increasing
carbon number is approximately given by the equation

ln x hc s y3.9069 y 1.51894CN 1.
which was obtained by regressing the solubility data for 5 F CN F 9 by Shaw w4x.
Although the solubility continues to decrease with increasing carbon number for CN) 10, the data
plotted in Fig. 2 1 w58x suggest, the scatter notwithstanding, a significantly weaker CN dependence
for CN ) 11. This change has been attributed to the formation of micelles. The formation of such
colloidal suspensions can indeed raise significantly the apparent non-equilibrium. solubility w9,10x,

1
See additional information in Ref. w4x.
24 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133

Fig. 2. Solubility of normal alkanes in water at 298.15 K. Line calculated with Eq. 1..

but this could also result from a transition of the C 11 q normal alkanes to a collapsed conformation,
which would reduce contact of the alkane with water, and would thus make their solubility in water
higher than that predicted by Eq. 1.. Such a transition has been discussed for polymers in poor
solvents w11x, and Fig. 2 raises the speculation that it may start for alkanes in water at around
CN s 11.

3.2. Heat of solution

Generally, it is accepted that the heat of solution includes two effects: a positive heat of cavitation
and a negative heat of hydrophobic interaction between the alkane and water. These two effects
cancel each other at Tmin , the temperature at which the alkane solubility goes through a minimum,
with the heat of cavitation becoming the dominant effect at T ) Tmin .
 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133 25

The relationship between solubility and heat of solution is given by

E ln x i Dhi
ET / P
(
RT 2
2.

D h i , the heat of solution, is the difference between the enthalpy of the hydrocarbon i in solution and
the enthalpy of the pure hydrocarbon:

D h i s h i in solution. y h i pure hc . 3.
Thus, D h i s h Ei , the partial molar excess enthalpy of component i.
Gill et al. w12,13x have measured the heat of solution of C 6 C 9 normal alkylbenzenes and
cyclohexane in water from 288.15 to 308.15 K, using a flow-microcalorimetric technique. Gills
measurements have established that the heat of solution is a linear function of temperature; therefore,
the heat capacity of solution or the partial molar excess heat capacity. is constant. Such a linear
dependence is also assumed for the normal alkanes, although Gill et al. w13x only measured the heat of
solution at 288.15 and 298.15 K for n-pentane and n-hexane.
Integration of Eq. 2., where D h i is expressed as a linear function of temperature, leads to Eq. 4.
ln x hc s A q BrT q C lnT 4.
where D c p s RC s 8.31451C J Ky1 moly1. The predicted minima in the solubility where D h s 0.
and the values of D c p from the data of Gill et al. for pentane and hexane are compared in Table 1

with the results obtained from the analysis of the solubility data of Jonsson et al. w14x for C 5 C 8
normal alkanes in water, which confirm the linear dependence of D h on temperature. The agreement
is better than what would normally be expected, because only the highly precise solubility data of

Jonsson et al. were used in the comparison. Heats of solution measured calorimetrically and derived
from solubility data are compared in Fig. 3 from Ref. w2x..
The minimum in the solubility of C 5 C 8 alkanes in water is at around 303 K, with perhaps a slight
decrease in Tmin with increasing carbon number. The more extensive calorimetric data of Gill et al.
w12,13x for C 6 C 9 normal alkylbenzenes give a minimum at 291 K with a slight increase in Tmin
with increasing CN. , which is confirmed by the solubility data of Bohon and Claussen w15x, which
give Tmin s 290 " 1 K. Thus, the minimum in the liquid hydrocarbon solubility in water is very

Table 1
Comparison of calorimetric and solubility data
D c p J Ky1 moly1 . T K. at minimum solubility
Calorimetric Solubility Calorimetric Solubility
Pentane 400"70 399 303 303.0
Hexane 440"45 448 298 302.9
Heptane 474 302.5
Octane 495 301.8
Nonane 515a 303b
a
Extrapolated value.
b
Assumed average for alkanes.
26 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133

Fig. 3. Heat of solution of hydrocarbons in water from Ref. w3x..

definite, but the different affinity that alkanes and alkylbenzenes have for water possibly leads to a
different Tmin .

In view of the high precision of Jonssons solubility data and their agreement with calorimetric
data., an extrapolation was made to nonane on the basis of the following assumptions:

D h s 0 at 303 K

D c p s 515 J Ky1 moly1

The value of A in Eq. 4. was determined with the solubility value calculated with Eq. 1..
Selected data for the solubility of C 5 C 9 normal alkanes w1,2,14,1620x and the values calculated
with Eq. 4. with the parameters given in Table 2. are compared in Fig. 4. Although there is

Table 2
Solubility of normal alkanes in water with Eq. 4.
Alkane A B C
Pentane y333.59719 14 537.472 47.97436
Hexane y374.90804 16 327.128 53.89582
Heptane y396.93979 17 232.298 56.95927
Octane y415.7563 17 975.386 59.55451
Nonanea y433.434 18 767.82 61.940
a
Extrapolated; see text and Table 1.
 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133 27

Fig. 4. Solubility of C 5 C 9 normal alkanes in water from 273 to 413 K. Lines calculated with Eq. 4. and the parameters in
Table 2.

considerable scatter in the data, Eq. 4. with parameters based only on the data of Jonsson et al. w14x
for C 5 C 8 and extrapolated for C 9 . , does reasonably well up to around 400 K.

4. Solubility of water in alkanes

4.1. Solubility at 298 K

The solubility of water in liquid alkanes at 298 K presents a much different picture from that of
alkanes in water. Unlike the sharp drop in solubility with increasing CN shown in Fig. 2, the
solubility of water in normal alkanes is fairly insensitive to CN, rising slightly with increasing CN.
28 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133

Fig. 5 includes data for water in liquid ethane and propane from Parrish et al. w21x, in C 5 C 8 from
Polak and Lu w22x, in C 6 from Roddy and Coleman w23x, and in C 7 C 16 from Schatzberg w24x. The
dependence of the solubility of water on CN is given by
y79.6677 y 6.6547CN
ln x w s 5.
9.5470 q CN
The solubility of water in n-hexadecane is only 60% greater than that in n-pentane, unlike the larger
than four orders of magnitude difference between the solubility of these hydrocarbons in water Fig.
2..

4.2. Heat of solution

The relationship between solubility and heat of solution is given by Eqs. 2. and 3.. However, here
h i is the enthalpy of water in solution and h i is the enthalpy of pure liquid water. An important

Fig. 5. Solubility of water in normal alkanes at 298.15 K. Line calculated with Eq. 5..
 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133 29

Table 3
Solubility of water in normal alkanes with Eq. 6.
Alkane A B D h w kJ moly1 .
Pentane 6.951930 y4381.365 36.4
Hexane 6.698073 y4291.186 35.7
Heptane 6.76126 a y4290.7. b 35.7. b
Octane 6.839365 y4290.165 35.7
Decane 6.476563 y4179.296 34.7
Hexadecane 6.418156 y4089.393 34.0
a
Determined with the solubility of water at 298.15 K from Eq. 5. and the interpolated value for B.
b
Interpolated values.

difference is that the heat of solution for water in alkanes is always positive and is nearly the same for
all alkanes.

Fig. 6. Solubility of water in n-octane. Line calculated with Eq. 6. and the parameters in Table 3.
30 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133

Nilsson w25x measured the heat of solution for water in C 7 C 12 normal alkanes at 298 K and
concluded that, within experimental uncertainty, it is independent of CN and equal to 34.9 " 1.1. kJ
moly1. What is striking about this large value for the heat of solution is that its magnitude is close to
that of the hydrogen-bond energy. Typical values for the energy of a normal hydrogen bond range
between 20 and 40 kJ moly1 5 to 10 kcal moly1 .. Thus, not surprisingly, the magnitude of the heat
of solution suggests that dissolution of n water molecules leads to the breaking of n hydrogen bonds,
which to a good approximation is independent of both carbon number and temperature. As a result,
the solubility and the heat of solution of water in alkanes have only a weak dependence on carbon
number and temperature.
Among hydrocarbons, alkanes have the least affinity for water. That is, they must have the smallest
in absolute sense. heat of hydrophobic interaction. Since this makes a negative contribution to the
heat of solution, the heat of solution of water in other hydrocarbons should be less than that in
alkanes. Indeed, Nilssons w25x calorimetric measurements in benzene give D h s 24.4 kJ moly1. This
difference of ; 10 kJ moly1 between benzene and alkanes is a measure of the difference in the

Fig. 7. Solubility of water in n-heptane. Line calculated with Eq. 6. and the parameters in Table 3.
 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133 31

respective heats of hydrophobic interaction with water. X-ray diffraction data suggest that water
forms weak hydrogen bonds to the aromatic p electrons of an aromatic compound in the solid state
w26x..
If we assume that D h is constant, then D c p s 0 and integration of Eq. 2. gives
ln x w s A q BrT 6.
This simple equation, with the parameters in Table 3, fits the data remarkably well to within ; 30 K
of the three-phase critical temperature, as can be seen in Fig. 6 for water in n-octane w2,22,2730x. 2
To fit x w up to the three-phase critical temperature, 539 K, it is necessary to use the more complex
equation derived in Ref. w2x; Eq. 6. .. In agreement with the calorimetric data, the parameters B
s 8.31451D h. are very slightly dependent on CN and give an average D h s 35.3 " 0.8 kJ moly1.

However, the solubility data which are not as smooth as those of Jonsson et al. w14x for alkanes in
water. suggest that D h decreases slightly with increasing CN.
Finally, Fig. 7 shows that the interpolated parameters for water in n-heptane see Table 3. fit
reasonably well the widely scattered solubility data 2 w22,24,2729,3133x, especially considering
that the data of Black et al. w27x and Englin et al. w29x for water solubility in other hydrocarbons have
always been found to be too high see also Fig. 6. . Essentially no information is available for water in
C 9 and C 11 C 15 alkanes, except for the data of Schatzberg at 298 and 313 K w24x.

5. Conclusions and recommendations

There is good agreement between solubility and calorimetric measurements, for both the solubility
of alkanes in water and of water in alkanes. At 298 K, Fig. 2 clearly demonstrates that the solubility
of alkanes in water decreases steeply with increasing carbon number, although around CN s 11 there
appears to be a transition to a much slower solubility decrease with CN, possibly due to folding of the
C 11 q alkanes. On the other hand, the solubility of water in alkanes at 298 K increases only slightly
with CN Fig. 5..
There are two contributions to the heat of solution: a positive heat of cavitation and a negative heat
of hydrophobic interaction. On the water-rich side, there is a definite minimum in the solubility
around 303 K Fig. 4. , where the two contributions cancel each other. The heat of solution either
measured calorimetrically or derived from solubility data. is a linear function of temperature Fig. 3. ,
thus, giving a constant heat capacity of solution.
The solubility of water in alkanes increases monotonically with temperature Figs. 6 and 7.. To an
excellent approximation, the heat of solution of water in alkanes is a constant that changes only
slightly with CN, because it is primarily influenced by the breaking of hydrogen bonds in water. The
resulting two-parameter equation for the solubility of water in alkanes is very satisfactory to within
about 30 K of the three-phase critical end point temperature Fig. 6..
It is hoped that the recommendations reached here on the mutual solubilities of alkanes and water
Eqs. 1., 4. 6. ; Tables 2 and 3. will be useful both in engineering application and theoretical
investigations. In the latter case, having a relatively clear picture on how the mutual solubilities
depend on carbon number and temperature may facilitate the development of molecular models and

2
Data and later references are given in Ref. w4x.
32 C. Tsonopoulosr Fluid Phase Equilibria 156 (1999) 2133

simulations that will explain at least some of the observations summarized in the previous paragraphs.
It may then be possible to predict with some confidence the mutual solubilities of water with heavier
or branched alkanes, as well as with other classes of hydrocarbons.

6. List of symbols

A, B, C parameters of Eqs. 4. and 6.

CN number of carbon atoms
cp heat capacity
h enthalpy heat.
hi partial molar enthalpy
h Ei partial molar excess enthalpy
P pressure
R gas constant
T absolute temperature
Tmin temperature of minimum hydrocarbon solubility
x liquid mole fraction
Greek letters
D cp heat capacity of solution
Dh enthalpy heat. of solution
Subscripts
hc property of hydrocarbon
w property of water

Acknowledgements

The author is grateful to Exxon Research and Engineering, for permission to publish this paper, and
to John L. Heidman, for suggesting Eq. 5. and other helpful comments.

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