Transesterification reaction variables that affect yield and purity of the product esters from cottonseed, peanut, soybean and sunflower oils include molar ratio of alcohol to vegetable oil, type of catalyst (alkaline vs acidic), temperature and degree of refinement of the vegetable oil. With alkaline catalysts (either sodium hydroxide or methoxide), temperatures of 60 C or higher, molar ratios of at least 6 to 1 and with fully refined oils, conversion to methyl, ethyl and butyl esters was essentially complete in 1 hr. At moderate temperatures (32 C), vegetable oils were 99% transesterified in ca. 4 hr with an alkaline catalyst. Transesterification by acid catalysis was much slower than by alkali catalysis. Although the crude oils could be transesterified, ester yields were reduced because of gums and extraneous material present in the crude oils.

Transesterification of soybean oil (SBO) and other triglycerides with alcohols, in the presence of a catalyst, yields fatty esters and glycerol. Di‐ and monoglycerides are intermediates. Reactions are consecutive and reversible. Rate constants have been determined for each reaction with a computerized kinetic program. The effects of the type of alcohol, 1‐butanol or methanol (MeOH); molar ratio of alcohol to SBO; type and amount of catalyst; and reaction temperature on rate constants and kinetic order were examined. Forward reactions appear to be pseudo‐first order or second order depending upon conditions used. Reverse reactions appear to be second order. At a molar ratio of MeOH/SBO of 6:1, a shunt reaction was observed. Energy of activation was determined for all forward and reverse reactions under a variety of experimental conditions from plots of log k vs 1/T. Values ranged from 8–20 kcal/mol.

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Cetane numbers (C#} for the homologous series of straight-chain, saturated n-alcohols, C5-C12 and C14, were determined according to ASTM D 613. Measured C# ranged from 18.2-80.8 and increased linearly with carbon number {CN). Regression analyses developed equations that related various physical properties or molecular characteristics of these alcohols to calculated C#. The degree of relationship between measured and calculated C# was expressed as R 2. The decreasing order of the precision with which these properties correlated with C# was: boiling point (bp) > melting point imp) > CN > heat of combustion {HG) > refractive index (UZ0v} > density (d). This ranking was based upon R 2 (0.99-0.96) and the Average % Error (2.8-7.2%). C# were also determined for straight-chain homologs of saturated methyl esters with CN of 6, 10, 12, 14, 16 and 18. C# ranged from 18.0-75.6 and increased eurvilinearly with CN. Equations were also developed that related physical properties of these esters to C#. The precision with which these properties correlated with C# was: bp > viscosity iV} > heat of vaporization {HV) > HG > CN > surface tension (ST) > mp > n20D> d. R 2 ranged from 0.99 for bp to 0.98 for d. Equations for the alcohols were linear or quadratic, while equations for the esters were linear, quadratic or cubic based upon statistical considerations that included a Student's t-test. With related physical properties and these equations, accurate predictions of C# can be made for saturated n-alcohols and methyl esters.

A rapid quantitative capillary gas chromatographic method has been developed for studying transesterification of soybean oil (SBO) to fatty esters. Standard solutions containing methyl linoleate, mono-, di-and trilinolein were analyzedwith a 1.8 m X 0.32 mm SE-30 fused silica column. The effect of carrier gas flow on reproducibility was determined. Prior to analysis, mono-(MG) and diglycerides (DG) were silylated with N,O-bis(trimethylsilyl) trifluoroacetamide.Tridecanoin was usedas an internal standard. From plots of area and weight relationships, slopes and intercepts for all four compound classes were determined. Agreement between the measured and calculated compositions of the standard solutions was good; the overall standard deviation was 0.4. Slopes and intercepts also were determined for SBO and its methyl and butyl esters. Complete separation of ester, MG, DG and triglyceride was obtained in 12 min by temperature programming from 160 to 350 C. This method of analysis gave excellent results when used in a kinetic study of SBO transesterification.

Gross heats of combustion (HG) have been measured for three classes of fatty esters and two classes of triglycerides (TGs). The esters included saturated methyl esters, Me 6:0–22:0; saturated ethyl esters, Et 8:0–22:0; and unsaturated methyl esters, Me 12:1–22:1, Me 18:2 and Me 18:3. The TGs included the saturated TGs, C 8:0–22:0, and unsaturated TGs, C 11:1, C 16:1, C 18:1, C 18:2, C 18:3, C 20:1 and C 22:1. HG were measured in a Parr adiabatic calorimeter according to a modification of ASTM D240 and D2015. Linear regression analysis (LINREG) yielded equations that related HG to carbon number (CN) or chain length, electron number (EN) or number of valence electrons and molecular weight (MW). Calculated HG values from CN, EN, or MW were nearly identical. Thus, any one of these three variables can be used to predict HG satisfactorily. R squared values for all equations were 0.99. Equations for correlating HG of saturated or unsaturated TGs with molecular characteristics of these molecules have not been reported. With LINREG, we developed equations that permitted predictions of HG from structures of the saturated and unsaturated TGs. Equations for predicting HG of methyl and ethyl esters were compared to those in the literature and were found to be more accurate and precise.

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