Procedure for Determining Solubility Parameters of Crude Oils

Introduction
This documentation provides a detailed methodology for determining the solubility parameters
of crude oils, a crucial aspect in understanding their chemical behavior, particularly when
assessing compatibility with drag-reducing agents.

Phase 1: Preparatory Steps

1. Acquisition of Analytical Grade Solvents:
 Obtain a range of analytical grade solvents with well-documented solubility
parameters, such as benzene, toluene, methanol, and hexane.
2. Standardizing Sample Conditions:
 Equilibrate the crude oil sample to a controlled temperature (25°C) in a constant
temperature room or bath to minimize thermal variation effects.

Phase 2: Microcalorimetric Analysis

4. Preparation of Solution Mixtures:
 Create binary mixtures of the crude oil with each solvent in a volumetric flask.
Maintain a stoichiometric balance, ensuring the mole fractions are consistent.
5. Microcalorimeter Calibration:
 Perform a standard calibration procedure for the Differential Scanning
Calorimeter (DSC) or Isothermal Titration Calorimeter (ITC) as per the
manufacturer's guidelines.
6. Thermal Analysis of Mixtures:
 Sequentially introduce each binary mixture into the calorimeter.
 Record the endothermic or exothermic heat flow, denoting the heat of mixing
(ΔH_mix).

Phase 3: Data Computation

7. Solubility Parameter Calculation:
 Employ the Hildebrand-Scatchard equation for the solubility parameter:

Where,
δ=
√∆ H mix + RT
Vm

 δ: Solubility parameter of the crude oil.

 ∆ H mix :Heat of mixing, measured from the microcalorimetric analysis.
 R: Universal gas constant (8.314 J/(mol·K)).
 T: Absolute temperature in Kelvin at which the experiments are conducted.
 V m :Molar volume of the mixture.

8. Analyzing Solvent Compatibility:

 Analyze the interaction parameter (χ) between the crude oil and each solvent. A
lower χ value indicates better solubility compatibility.
 1 2
 To find χ, χ = .(δ 1−δ 2)
RT
 χ is the interaction parameter.
 R is the gas constant.
 T is the absolute temperature.
 δ1 and δ2 are the solubility parameters of the two components (crude oil and solvent).

Phase 4: Supplementary Group Contribution Analysis

9. Molecular Composition Assessment:
 If available, utilize Gas Chromatography-Mass Spectrometry (GC-MS) data of the
crude oil to determine its molecular composition.
10. Group Contribution Calculations:
 Apply the group contribution method (e.g., using the Van Krevelen approach) for
a detailed solubility parameter estimation, incorporating individual molecular
contributions.

References
 Christian, G. D. (2004). Analytical Chemistry (6th ed.). John Wiley & Sons.
 Connors, K. A. (2002). Thermodynamics of Pharmaceutical Systems: An Introduction for
Students of Pharmacy. Wiley-Interscience.
 Flory, P. J. (1953). Principles of Polymer Chemistry. Cornell University Press.
 Green, D. W., & Perry, R. H. (Eds.). (2008). Perry's Chemical Engineers' Handbook (8th
ed.). McGraw-Hill.
 Mirabella, F. M. (Ed.). (1996). Modern Techniques in Applied Molecular Spectroscopy.
John Wiley & Sons.
 Pavia, D. L., Lampman, G. M., Kriz, G. S., & Vyvyan, J. R. (2008). Introduction to
Spectroscopy (4th ed.). Cengage Learning.
 Riddick, J. A., Bunger, W. B., & Sakano, T. K. (1986). Physical Properties of Chemical
Compounds. American Chemical Society.