Abstract
The rate of decomposition of carbon disulphide in shock waves through CS
2
+ Ar mixtures has been studied spectroscopically between 2250 and 3350 °K. Mainly, the rate of appearance of CS has been measured, but in some instances it has been possible also to follow the rate of appearance of S
2
and the rate of disappearance of CS
2
. The rate obeys mixed second-order kinetics of the type –d[CS
2
]/d
t
=
k
∞
[Ar] [CS
2
] +
k
0
[CS
2
]
2
. The term that is second-order in [CS
2
] appears to correspond to a unimolecular decomposition of the CS
2
in which the collision partner is another CS
2
, rather than to a true bimolecular reaction.
k
0
is found to be about 20 times as large as
k
∞
. The rate constant for decomposition at infinite dilution in argon is given in Arrhenius form by
k
∞
= 10
15.9
exp ( – 81.8 kcal/
RT
) cm
3
mole
-1
s
-1
. The application of R. R. K. H. theory to this yields as the most probable result,
k
∞
= (
PZ
/3!) (96 kcal/
RT
)
3
exp ( – 96 kcal/
RT
), in which
P
is about 0.1. Thus four effective oscillators may be contributing energy to the decomposition process, the rate-determining step of which is likely to be a transition from the ground state to an excited singlet state at a crossing point located at an energy of about 96 kcal. In this respect CS
2
is an interesting contrast to CO
2
, where the transition is probably singlet-triplet. The firmness of these conclusions is limited by the scarcity of knowledge concerning excited electronic states of CS
2
.
Reference11 articles.
1. B enson S. W . i9 6 0 The foundations of chemical kinetics. N ew Y ork: M cGraw-Hill B ook C om pany.
2. Proc. Roy;Soc. A,1963
3. G urvich L. V . etal 1962 Thermodynamic properties of individual v o l. 2. U .S .S .R . A cad em y o f Science.
4. J;Quant. Spectr. Rad.,1963
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