Effects of Freezing Point Depression on Molecular Weight Determination of

Hydrocarbon Mixtures.

Ifeanyi A. Oguamah, M.Sc.1*; Jeffrey O. Oseh1; and Peter N. Yekeen2

1
Department of Chemical and Petroleum Engineering, Afe Bablola University, PMB 5454 Nigeria.
2
Department of Petroleum Engineering, Universiti Technologi, Malaysia.

*
E-mail: [email protected]
[email protected]
[email protected]

ABSTRACT Mixing rules are important in the characterization

of reservoir fluid as it is used in the development
The molecular weight of components of four equation of state and development of critical
hydrocarbon mixtures n-Nonane+n-Tetradecane, properties. Reservoir fluids are always composed
n-Hexane+n-Nonane, n-Hexane+Toluene, and of lighter gaseous / liquid component and heavier
Toluene+n-Tetradecane were determined by an (more solid C7+ components) and other heavier
experimental procedure based on freezing point components which are lumped together to form
depression. The results showed a marked as pseudo components. Kay’s rule [10] is the
improvement from the values obtained using the commonly used to determine the molecular
Kay’s mixing rule, for the molecular weight weight and properties of these multicomponent
determination of multicomponent mixtures. The fluids, properties are obtained by summing the
results also form the bases for the determination products of the component and the relative
of the critical properties of hydrocarbon mixtures. molar fraction for the group of components in a
multicomponent mixture.
(Keywords: freezing point depression, hydrocarbon
mixtures, mixing rule, molecular weight) Since estimates are used to determine the
molecular weight of binary and multicomponent
mixture, there are bound to be errors as the
INTRODUCTION number of components in a mixture increase.
Numerous inaccuracies results when using kay’s
Molecular weight determination of hydrocarbon mixing rule for real fluids [11]; therefore, there is
fluids is very important for the accurate estimation need for an accurate method of molecular weight
of thermodynamic properties [1], [2], [3], [4]. determination for multicomponent fluids. A
Petroleum reservoir fluids consist of thousands of number of techniques are available for the
different components, hydrocarbons and hetero- determination of molecular weight of
components. These components possess a wide hydrocarbons, these are based on the principle of
range of boiling point and molecular weight, [5]. boiling point elevation, freezing point depression,
[6] noted that the second step in characterization vapor phase osmosis or chromatography, and
of plus fractions, of multicomponent petroleum they further pointed out that freezing point
mixtures involves use of estimated specific gravity depression still remains the most preferred [12].
and molecular weight to estimate critical
properties required by equation of states. Freezing point depression is a colligative
property, along with vapor pressure lowering,
According to [7] accurate estimation of mixtures boiling point elevation and osmotic pressure it
depends on the estimation of properties of pure utilizes the theory of concentration determination
compound in the mixture. The molecular weight by freezing point and is defined as the difference
estimates can be easily obtained for a pure between the freezing point of solvent and the
component, unlike those of binary and freezing point of solution of the solvent and
multicomponent hydrocarbon mixtures which are solute. There is a linear relationship between the
usually obtained by the application of mixing rule freezing point depression constant (Kf) of a
[8], [5], [9]. solvent, the concentration of the sample and

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freezing point depression. The freezing point The range was then adjusted to 000 and a
depression varies for different pure solvents with second benzene sample is charged in and the
Kf of water at 1.86⁰C/mol and benzene at ΔFp is read.0.882g of Nonane was dissolved in in
5.12⁰C/mol. The Kf varies slightly with the 42g of Benzene and 2.5ml of the solution was put
concentration of sample and decrease with in a glass test tube, the same procedure as that
increasing concentration. of pure component was used to determine the
ΔFp the value was found to be 845. 4 binary
mixtures was then prepared at different
PREPARATION OF MIXTURES proportions of mole fraction ranging from 0.1 to
0.9 for each binary mixture, the same procedure
Mixtures were prepared from the pure
for pure components was used to determine the
components in nine different proportions, four
molecular weight of each binary mixtures.
mixtures were prepared which includes: Hexane +
n-Nonane; Hexane + Toluene; Toluene + n-
Tetradecane; n-None + n-Tetradecane; the total
RESULTS
weights of mixture were 0.889g, the pure
components were purchased from commercial
The Kay’s (1936) mixing rule for calculating the
sources, since the pure components where all
soluble in benzene, benzene was used as the molecular weight of mixtures was of the most
pure solvent. The pure component where used comprehensive and useful in this study. Mole
without further purification the goal was to fraction and molecular weight was reported for
measure the freezing point depression ΔFp of the the binary mixtures, the experimental, and
pure component mixtures calculated results of molecular weight of binary
mixtures, at different mole fractions for pure
The CRYETTE WR was used to determine the components and their binary systems are listed in
freezing point depression of various mixture and Tables 1-4.
thereafter their molecular weight was determined.

Table 1: Molecular Weight Results of Nonane

METHODOLOGY (1) +Tetradecane (2) System for
Experimental and Kay’s Mixing Rule.
Mixtures of pure components were prepared with
various proportions of the pure component in the
Weight Weight (g) of ΔFp Experimental Kay’s
mixture. The freezing point depression of the pure
(g) of Tetradecane Milli- Result (1) mixing
components and binary mixture were measured Nonane (2) ⁰C +(2) Rule
using the CRYETTE Osmometer. The molecular (1)
weight of the mixture was then determined using 0 0.889 546 198.485 198.4
the equation.
0.0889 0.8001 549 197.401 191.386
0.1778 0.7112 600 180.622 184.372
0.2667 0.6223 608 178.245 177.358
Mw = (1) 0.3556 0.5334 576 188.148 170.344
0.4445 0.4445 648 167.242 163.33
0.5334 0.3556 709 152.853 156.316
EXPERIMENTAL PROCEDURE 0.6223 0.2667 720 150.518 149.302
0.7112 0.1778 758 142.972 142.288
The calibration was done by putting 2.5ml of
0.8001 0.0889 823 131.680 135.274
benzene in a glass tube, the bath temperature
0.889 0 845 128.252 128.260
control was set at 681 in other to get a bath
o
temperature of 1.5 C.The benzene sample was
charged into the refrigerator well when the bath
o
temperature indicator light blinked at 1.5 C. The
operate switch was set at operate position, while
o
the pure solvent Benzene froze at 1000 C (i.e.
display light shows 1000 after cycling).

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Table 2: Molecular Weight Results of Hexane (1) DISCUSSION OF RESULTS
+ Nonane (2) System for Experimental and Kay’s
Mixing Rule. Figures 1-4 were plotted from the Tables 1-4
above so that the variations can be established
Weight Weight ΔFp Experimental Kay’s from the research work and the literature using
(g) of (g) of Milli-⁰C Result Mixing the existing theories and mixing rules. In Figures
Hexane Nonane (1)+(2) g/mol Rule
1- 4 the plots followed a similar pattern for all the
(1) (2)
0 0.889 845 128.252 128.26 plots, all the experiments were conducted at
room temperature.
0.1778 0.7112 930 116.530 119.844
0.3556 0.5334 905 119.749 111.428
The plot of the experimental data and that of this
0.5334 0.3556 1070 101.283 103.012 study show great similarity with very slight
0.7112 0.1778 1121 96.675 94.596 deviation in Figures 2 and 3 while the Kay’s
0.889 0 1257 86.215 86.18 mixing rule value deviated greatly for all the four
plots, generally since the molecular weight
decreased with increasing mole fraction for all the
four plots, it can be stated that there was an
Table 3: Molecular Weight Results of Hexane (1) inverse relationship between the molecular
+ Toluene (2) System, for Experimental and Kay’s weight and the mole fraction.
Mixing Rule.
Significant deviations in the experimental
Weight Weight ΔFp Experimental Kay's molecular weight from the calculated molecular
(g) of (g) of Milli- Result (1) +(2) Mixing
Hexane Toluene ⁰C Rule weight for the four binary systems performed at
(1) (2) room temperature from this work implies that the
0 0.889 1176 92.154 92.140 Kay’s mixing rule does not give accurate results
0.178 0.711 1235 87.751 90.948 for molecular weight of mixtures. Experimental
molecular weight of the four binary systems did
0.356 0.533 1126 96.246 89.756
not change and therefore is superior to the
0.533 0.355 1315 82.413 88.564
estimated result
0.711 0.177 1230 88.108 87.372
0.889 0.000 1257 86.216 86.180

Table 4: Molecular Weight of Results of Toluene

(1) + Tetradecane (2) System, for Experimental
and Kay’s Mixing Rule.

Weight Weight (g) ΔFp Experimental Kay's

(g) of of Toluene Milli- Result (1) Mixing
Hexane (2) ⁰C +(2) Rule
(1)
0 0.889 1176 92.154 92.140
0.178 0.711 1235 87.751 90.948
Figure 1: Comparison of the Molecular Weight of
0.356 0.533 1126 96.246 89.756
Tetradecane (1) + Nonane (2) System.
0.533 0.355 1315 82.413 88.564
0.711 0.177 1230 88.108 87.372
0.889 0.000 1257 86.216 86.180

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 CONCLUSION

The results show that the Kay’s Mixing rule does

not replicate accurately the measured values
obtained from the mixtures and therefore not
reliable for measuring critical properties from
molecular weight. A new correlation can be
developed for determining the molecular weight
of mixtures. This method will have an
improvement over the Kay’s mixing rule and give
Figure 2: Comparison of the Molecular Weight of more accurate value. Instead of limiting studies to
Hexane (1) + Nonane (2) Binary System. binary mixtures, research should be extended to
multicomponent systems and heavy hydrocarbon
systems.

More studies should be carried out using other

methods of molecular weight determination by
experimental methods other than freezing point
depression.

REFERENCES

1. Riazi, M.R. and T.E. Daubert. 1987.

“Characterization Parameters for Petroleum
Fractions”. Ind. Eng. Chem. Res. 26(4):755-759.

2. Stamataki, S.K. and K.G. Magoulas. 2001.

Figure 3: Comparison of Molecular Weight of “Characterization of Heavy Undefined
Hexane (1) + Toluene (2) Binary System. Hydrocarbon Fractions”. SPE International
Symposium on Oilfield Chemistry.

3. Sancet, G.F. 2007. “Heavy Fraction C7+

Characterisation for PR-EOS”. SPE PAPER
113026 Stu.

4. Pedersen, K.S. and P.L. Christensen. 2007.

Phase Behaviour of Petroleum Reservoir Fluids.
CRC Press: Boca Raton, FL. 81-83.

5. Danesh, A. 1997. PVT and Phase Behaviour of

Petroleum Reservoir Fluids. Elsevier Science:
B.V. Netherlands. 210-249.

6. Whitson, C.H. 1983. “Characterizing

Hydrocarbon Plus Fractions: SPE PAPER
23(4)”683-694. SPE -12233-PA.

7. Riazi, M.R. and T.A. Al-sahhaf. 1995. “Physical

Properties of n-alkane and n- hydrocarbons:
Fig. 4: Comparison of molecular weight of
Application to Petroleum Mixtures”. Ind. Eng.
Toluene (1) + Tetradecane (2) Binary System. Chem. 34:4145- 4148.

8. Ahmed, T. 2007. Equations of State and PVT

Analysis. 59-62. Gulf Publishing Company,
Houston, TX.

The Pacific Journal of Science and Technology –243–

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9. Isehunwa, O.S., G.A. Adetoyi, and I.A.Oguamah.
2013. “Experimental Determination of the
Molecular weight of Some Binary Mixtures and
Petroleum Liquids”. Canadian Journal of Pure and
Applied Science. 7(1):2271-2275.

10. Kay, W.B. 1936. “Density of Hydrocarbon Gases

and Vapour”. Ind. Eng. Chem. 28:1014-1019.

11. Kreglewski, A. 1967. “A Semi-Empirical Treatment

of Properties of Fluid Mixtures”. Proceedings of
the Thomas Alvin Boyd Lectures in Chemical
Engineering; Bulletin 201, Engineering
Experiment Station, Ohio State University,
Columbus, OH..

12. Isehunwa, O.S. and Falade, G.K. 2007. “Improved

Characterisation of Heptane plus Fractions of
Light Crudes”. SPE PAPER 111918-MS.

ABOUT THE AUTHORS

Ifeanyi A. Oguamah, is with the Department of

Chemical and Petroleum Engineering, Afe Bablola
University, PMB 5454 Nigeria. (Phone:
+2348026051219; e-mail: [email protected]).

Jeffery O. Oseh, is with the Department of

Chemical and Petroleum Engineering, Afe Bablola
University, PMB 5454 Nigeria e-
mail:[email protected]

Peter N. Yekeen, is with the Department of

Petroleum Engineering, Universiti Technologi,
Malaysia; e-mail: [email protected].

SUGGESTED CITATION

Oguamah, I.A., J.O. Oseh, and P.N. Yekeen.

2014. “Effects of Freezing Point Depression of
Molecular Weight Determination of Hydrocarbon
Mixtures”. Pacific Journal of Science and
Technology. 15(2):240-244.

Pacific Journal of Science and Technology

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