secondary cells with lithium anodes and immobilized fused_salt

d (Sulfur]
dt
m i trogenj
dt
32.
E ks (Sulfur)
= kn (Nitrogen)
where llkg,17 rcks,lr and trknlr are rate constants for gasoline formation
and removal of sulfur and nitrogen respectively. There was no
change in the concentration of hydrogen in thc system during the
course of the reaction since the hydrogen p~ essure was maintained I
, constant throughout llqdrogen atoms may be involved in the rate-
determining step but %he ir concentration constitutes one of the
constant factors in the rate constant term and does not show up in
the rate equation. llowever. hydrogen actually takes part in the
hydrocracking rex tinos dnd , hence, @\he redc tions are considered
pseudo-f 1 I st order
The hydrocrack irig reactions under study follow true Arrhenius
temperature dependence (Figa~re 14) and the rate constants can be
represented b> eq?lations 4 to 6.
kg = 0 1567 x 106 e 17:600/RT hrs
k, = c? 2134 x LO5 e 14 500/RT hrs -1
(4 1
(5)
hn I 0 47jE x lo5 E 15.900/RT hrs..l
(6)
The following values c,f enthalpies and entropies of activation were
calculated by tht Eyri ng equatiorl plotbng log k’/T versus T (Figure
15)
AHg = 16,200 c al /mole, asg = 43 5 e.u.
Alls = 12,200 c al /mole, ASs = -44.9 e.u
411, = 14,QOO cal /mole, ASn = 45 9 e-u.
,
Linear relationship was found between kg, ks, and kn (Figure 16)
and can be represerited by equations 7 to 9
A major part of tile gasol iiie is expected to be formed by the crack-
ing of hydrocarbons, but a minor part comes from the decomposition
of some of tllt slilfur, oxygen. and nitrogen compounds. The yield
of gasoline thus tle.peritls, to some extent, on the removal of sulfur
and nitrogen and this may result in some sort of interrelationship
between kg, ks, and kll. The dissociation energies of the C-C, C-S,
and C-.X bonds may also have some influence on the above relation-
ship, especiall>- between k, and kn. However, the results presented
in this paper do not throw muc.li light on the effect of other tem-
perature and pressure conditions and equations 7 to 9 are not con-
sidered to be having much quantitative significance at this stage.
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