Beruflich Dokumente
Kultur Dokumente
9. Nohl, A., Fast Capillary Chromatography, Spectra-Physics, 12. See, J.B., Fette, Seifen, Anstrichm. 85:72 (1983).
3333 North First Street, San Jose,CA (no date}. 13. Goh, E.M., and R.E. Timms, J. Amer. Oil Chem. Soc. 62:730
10. D'Alonzo, R.P., W.J. Kozarekand H.W. Wharton, J. Amer. (1985).
Oil Chem. Soc. 58:215 (1981). 14. Haefelfinger,P., J. Chromatogr. 218:73 (1981}.
11. Devinat, G., J.L. Coustille, J.L. Perrin and A. Prevot, Rev. Fr.
Corps Gras 30:463 (1983). [Received D e c e m b e r 13, 1985]
TABLE 1
R e a c t i o n Conditions Employed i n K i n e t i c Studies
Molar ratio Weight of reactants
of
Alcohol used alcohol/SBO Alcohol (g) SBO (g) Catalyst Temperature (C)a
t o determine if the shunt-reaction scheme was applic- 0.5% NaOBu- vs 1% NaOBu-catalyzed reactions was
able. Our computer p r o g r a m calculated a zero reaction unexpected. This difference probably resulted because
r a t e , clearly indicating that the s h u n t reaction did not the 0.5%- and l%-catalyzed reactions were run on
e x i s t for the BuOH reaction. Why was the transester- different scales (see T a b l e 1) and w i t h different reactors
ification of SBO w i t h MeOH different from that w i t h (see Experimental). The l a r g e r size of the 400-ml f l a s k
BuOH at the 6:1 m o l a r ratio? Two possible explanations may have permitted more vigorous agitation, w h i c h
can be proposed. The smaller size of the MeOH molecule could have influenced reaction rates. Had the reactions
relative t o that of BuOH could facilitate the simultane- been run u n d e r identical conditions, r a t e s for the
ous a t t a c k of MeOH on all t h r e e chains of the TG. Also, l%-catalyzed reactions should have been h i g h e r than
the greater polarity of the methoxy anion compared t o the those for the 0.5%-catalyzed reactions. A n u m b e r of
b u t o x y a n i o n m i g h t promote its a t t a c k on the ester kinetic studies have shown that reaction r a t e s increase
carbonyl according t o established mechanisms. w i t h increasing catalyst concentration (7,8,14).
R a t e constants. Rate constants were calculated by our E n e r g y o f activation. The relationship b e t w e e n
computer p r o g r a m for all reactions included in our reaction rate constant, k, and temperature is g i v e n by
kinetic s t u d y . The rate constants determined for the the integrated form of the Arrhenius equation: log,ok =
reaction of BuOH w i t h SBO at a 30:1 m o l a r r a t i o u s i n g (-Eo/2.303R)/T + C w h e r e E, is the e n e r g y of activation,
various catalysts are shown in T a b l e 2. Because the R the gas constant in calories mo1-1 d e g r e e-1, T the
forward and reverse reactions are not of the same kinetic absolute temperature and C a constant. From a plot of
o r d e r at a 30:1 m o l a r ratio, a direct comparison of t h e s e log k vs l/T, the slope can be determined. This slope is
rate constants c a n n o t be m a d e . The alkaline-catalyzed e q u a l t o (-E,/2.303R). Thus, E, = - 4 . 5 8 (slope).
reactions had much l a r g e r rate constants than the acid- We determined e n e r g y of activation in this m a n n e r for
catalyzed r e a c t i o n s for b o t h f o r w a r d and r e v e r s e most of the reactions. An e x a m p l e is s h o w n in F i g u r e 6
reactions, as expected. The h i g h e r rate constants for the for the acid-catalyzed butanolysis of TG t o DG at
77-117 C. L i n e a r regression analysis of t h e s e data gave
a slope of - 3 2 5 8 . 1 w i t h a correlation coefficient of
TABLE 2
Effect of Various C a t a l y s t Systems on Rate C o n s t a n t s
TABLE 3
Energy of A c t i v a t i o n (E.) Under Studied Conditions
E. (caYmol): reaction conditions
--0.9964. By u s i n g this slope in the equation E, = - 4 . 5 8 Proceedings o f the International Conference on P l a n t and
(slope), an Ea of 14,922 cal/mol was calculated for this Vegetable Oils as Fuels, American Society of Agricultural
Engineers, St. Joseph, MI, 1982, p. 117.
reaction. Correlation coefficients for the o t h e r five
3. Freedman, B., E.H. Pryde and W.F. Kwolek, J. Amer. Oil
reactions of BuOH/SBO, 30:1 catalyzed by 1% H2SO4 Chem. Soc. 61:1215 {1984}.
were - 0 . 9 9 1 8 , - 0 . 9 9 6 5 , - 0 . 8 9 1 8 , - 0 . 9 7 9 5 and 4. Freedman, B., W.F. Kwolek and E.H. Pryde, Ibid. 62:663
-0.9905. {1985}.
E n e r g i e s of activation determined for o t h e r reactions 5. Markley, K.S., in F a t t y A c i d s , T h e i r Chemistry, Properties,
in our study r a n g e d from 8,000-20,000 cal/mol (Table 3). Production and Uses, edited by K.S. Markley, 2nd ed.,
O t h e r investigators have reported E ov a l u e s within this Interscience Publishers, New York, 1961, Part 2, p. 862.
6. Sridharan, R., and I.M. Mathai, J. Sci. Ind. Res. 33:183 {1974}.
r a n g e for other transesterification reactions (6,8,9-12). 7. Cotes, A.C., and L.A. Wanzel, Lat. A m . J. Chem. E n g . Appl.
Eo for the s h u n t reaction TG-GL had a v a l u e of 20 Chem. 4:126 11974).
kcal/mol. The spread of values seen in T a b l e 3 for Ea is 8. Davies, B., and G.V. Jeffreys, Trans. I n s t . Chem. E n g . 51:271
due partly t o experimental error. In addition, the {1973).
simplified m o d e l used in the e q u a t i o n log,oK = 9. Farkas, L., O. Schachter and B.H. Vromen, J. A m . Chem. Soc.
(-Eo/2.30R)/T + C may not be adequate t o account for 71:1991 11949}.
10. Baker, G.E., and R.R. White, Chem. E n g . Prog. S y m p . Ser. No.
all the variables involved. This m i g h t also explain why 4 48:75 (1952).
E o for some reverse reactions are g r e a t e r than those of 11. Ravindranath, K., and R.A. Mashelkar, J. Polym. Sci. Polym.
the corresponding forward reactions. F u r t h e r research is Chem. E d . 20:3447 {1982}.
n e e d e d t o develop a m o d e l that m i g h t provide a narrower 12. Tomita, K., and H. Ida, Polymer 14:55 (1973}.
r a n g e of E o values. 13. Pore, J., J.P. Houis and I. Rasori, Rev. Tech. Ind. Cuir 73:164
(1981).
14. Dufek, E.J., R.O. Butterfield and E.N. Frankel, J. A m e r . Oil
ACKNOWLEDGMENTS Chem. Soc. 49:302 {1972}.
15. Dufek, E.J., Ibid. 55:337 (1978}.
Haifa Khoury assisted in the laboratory and in manuscript 16. Butterfield, R.O., Ibid. 46:429 (1969}.
preparation; Wilma Bailey gave statistical assistance. 17. Reid, E.E., A m . Chem. J. 45:506 {1911}.
18. Formo, M.W., J. Amer. Oil Chem. Soc. 31:548 {1954}.
19. Koritala, S., R.O. Butterfield and H.J. Dutton, Ibid. 50:317
REFERENCES {1973}.
20. Vigeron, P.Y., S. Koritala, R.O. Butterfield and H.J. Dutton,
1. Freedman, B., E.H. Pryde and T.L. Mounts, J. Amer. Oil Ibid. 49:371 ~1972).
Chem. Soc. 61:1638 (1984}.
2. Freedman, B., and E.H. Pryde, in Vegetable Oil Fuels, [Received December 17, 1985]
Oleic, linoleic a n d linolenic acids were autoxidized more carboxyl groups in the decomposition of peroxides. H e
r a p i d l y t h a n their corresponding m e t h y l esters. Addition also said in this review (3) that this idea has been sup-
of s t e a r i c a c i d accelerated the rate of a u t o x i d a t i o n of ported by the work of Privett et al., in w h i c h addition of
m e t h y l linoleate a n d t h e d e c o m p o s i t i o n of m e t h y l linole- linoleic acid t o methyl linoleate peroxide accelerated its
ate hydroperoxides. Therefore, the higher oxidative rate decomposition. However, it was not c l e a r whether its
of F F A ' s than their m e t h y l e s t e r s c o u l d be due to t h e decomposition was promoted by the catalytic action of
c a t a l y t i c e f f e c t of t h e carboxyl groups o n the f o r m a t i o n the carboxyl group in linoleic acid or oxidized products
of free radicals by t h e d e c o m p o s i t i o n of hydroperoxides. of this acid, and the effect of F F A ' s on the autoxidation
Addition of stearic acid also accelerated the oxidative rate of esters has not been investigated.
of s o y b e a n oil. This result s u g g e s t s t h a t particular atten- In this paper, w e report the detailed data for the dif-
tion s h o u l d be p a i d to t h e F F A c o n t e n t t h a t a f f e c t s t h e ference in oxidative rates between F F A ' s and their methyl
oxidative s t a b i l i t y of o i l s . esters w i t h periodic measurement of the unoxidized
substrate content by GLC and POV, and elucidate the
catalytic action of the carboxyl group in F F A ' s on the
A few papers (1,2) have been published on the comparison autoxidation of oils by the use of stearic acid as a catalyst
of the oxidative rate of free f a t t y acids (FFA) and their which is not autoxidized u n d e r the conditions of the pres-
esters. H o l m a n et al. (2,3) reported that F F A ' s were ox- ent experiment.
idized more rapidly than their esters, and he suggested
that this effect probably was due t o participation of the
MATERIALS AND METHODS
*To whom correspondence should be addressed. P r e p a r a t i o n o f m a t e r i a l s . Oleic, linoleic and linolenic acids