Biochemistry

Download Advances in Catalysis, Vol. 6 by W.G. Frankenburg, V.I. Komarewsky, E.K. Rideal (Eds.) PDF

By W.G. Frankenburg, V.I. Komarewsky, E.K. Rideal (Eds.)

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One way of accomplishing such alteration is by modifying the configuration about the double bond. I n general, as with oleic acid, the packing of chains with cis double bonds is never perfect, while the trans compounds, on the other hand, fit together very closely (Fig. 10). The latter should lead to an even more marked reduction in rate for trans componnds a t high film pressures, the hydrocarbon chains CATALYSIS AND REACTION K I N E T I C S AT LIQUID I N T E R F A C E S 19 rendering the double bonds quite inaccessible t o the permanganate.

T h a t is to say that there is free access of molecules in the aqueous phase to the ester groups, as in Fig. 12. Ethyl valerate, on the other hand, because it is not digested, must be in the configuration in which the hydrocarbon sheath below the water surface makes reaction more difficult (Fig. 11). Still longer acid chains seem t o adopt the former arrangement again. Further investigation of the orientation in these surface layers may well yield information of great importance on the exact steric relationship necessary between the ester molecules and the active centers on the surface of hydrolytic enzymes.

This complicated the kinetics of the reaction to such a n extent that it was found necessary t o work under conditions such that the laurate ions were more rapidly expelled. Without this precaution, the negative potential which built up on the interface considerably retarded the reaction by offering a barrier t o the approaching catalytically active hydroxyl ions. , I systematic study of the kinetics of desorption of lauric acid away from interfaces has recently been completed (Saraga, 31,32). If S represents the total area of the air-water interface, from which desorption is CATALYSIS AND REACTION KINETICS AT LIQUID INTERFACES 17 proceeding at constant surface pressure, the process, after a n initial period of fast solution, obeys the equation: dS/dt = (xiii) -kS The mechanism seems to be that equilibrium is set up between the monolayer and the solution immediately below; the slow step is the diffusion of material through this saturated layer, a fraction of a millimeter thick, into the bulk of the solution.

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