Atkinson and his oo-workers^^ used nickel and stainless steel vessels for the pyrolysis of CgP^. Fluorides of manganese, chromium
and iron were formed in the stainless steel vessel, only the nicâcel and titanium components remaining unattacked. The nickel vessel, howBver, appeared satisfactoiy, and they found homogeneous gas phase reactions occurring in it.
Elementary fluorine can be handled in nickel and a nickel vessel was used for the preliminary woxic in the present investigation.
From the results of this w r k with CFg radicals end from the present investigation, it is possible to suggest the causes of the
apparent discrepancies in the attack of CFg radicals on glass and silica. Attack on tlie reaction vessel would appear to depend on the stationary concentration of CFg radicals. When some ea^^ reaction path is open to the CFg radioals, their oonoontration will be low;
this is tlie case in the woxk on GFgOHO vhere tlie CFg radicals readily abstract hydrogen from the parent aldel%rde, and in the work on
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GPgN a NCFg where CFg radioals add on to the parent oonpound. In neither oese is there attack of radicals on tlie wall. In the present investigation, it was possible for CFg radicals to react with iodine, toluene or hydrogen iodide and once again tliere was no serious attack on the glass.
However, in tlie daccBÇ)OSitions of CFgCOCPg and of HgCCFg)^, tlie only reaction open to a CF^ radical was abstraction of a fluorine atomo or a CFg radical to give CF^ or CgPg respectively. These reactions eqipear to be vexy difficult and do not occur readily; tliere is
therefore in these oases a hi^ stationary concentration of CP-o radicals and attack on the wall occurs.
It would appear that the activation energy for tlie attack of a CFg radical on glass or silica is such that the reaction proceeds at
o a measurable rate above about 500 C. Uniaolecular Reactions.
A first order reaction is one in vdiich the rate of reaction is proportional to the concentration of reactant.
^=1^ = k (A)
Althougil the rate depends on the first power of reactant
concentration, activation of the molecules takes place by a collision process. Tlie first simple theoiy about the mechanism of the
activation process was put forward sepairately by Clirlstiansen^^ and 70
Lindemenn ; Hinshelwood has been prominent in the development of tliese theories. There are also more elaborate theories which in
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some ways sooount better for tlie experimental results obtained and the subject has been critically reviewed at some length^.
All of these theories show that the concentration of molecules sufficiently active to decompose is not maintained at its equilibrium value at low pressures and that the rate of reaction therefore falls off as the concentration of reactant is lowered; the order of reaction clianges from being first order at high pressures to being second order at low pressures* Hwre are several reactions wliioh show this type of behaviour and tîiey have been used to verify the theories^.
These theories predict that the addition of an inert gas should activate reactant molecules by collision. Thus an inert gas should be capable of increasing the rate of reaction under conditions v&iere the rate lias fallen below its naxirmgn high pressure value. This has also been proved experimentally and it is possible to derive ^'efficiencies" of tliese inert gases in transferring energy to the
reactant molecules relative to the efficiency of the reactant itself^. On this basis, the efficienoy of a given inert gas naturally varies from reaction to reaction, but, as a general rule, tlie more complicated molecules are more efficient in transferring energy. Although the
efficiency of a gas varies from reaction to reaction, the limits of variation are usually within a factor of 10. In the present
investigation, inert gas efficiencies much lower tlian had been found by other workers were produced, and it was tliis vdhioh first made it
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was idiolly due to the ninGholwood-Llndemenn effect*
For the sake of ocopleteness, there is given in appendix (i) the foxroal Lindemenn mechanism end the method devised by Johnston^ which was used in this woxk to calculate inert gas efficiencies.
71
In 1928, Polanyi and Wigner reviewed tlio reactions then oonsidored to be unimoleoular and found that in tlie Arrhenius, equation
Jc - A
that the frequency factor A was of the oixler of 10^^ secs"*^. This value of 10^® secs*"^ is of the order of vibrational frequency of
most bonds and they suggested that A factors for unimolecular reactions 15 —1
should be of tlie order of 10 secs . Hone of the reactions cited by them is now considei^d to be a genuine unimolecular decomposition but most reactions now thought to be truly unimolecular do have A factors of between 10^ end 10^* There are coses, however, where
8 18
it is as low as 10 and reactions are reported with A as high as 10 . Steacie^ considers tliat many values of A a 10^^ liave not been found by a truly objective plot of the data, but nevertheless, A factors between 10^*® and 10^^*^ are regarded as "normal"*
Pond Dissociation Energies.
Chemical bonds are made and broken in chemioal reactions* Fium a laiowledgo of the strengths of bonds, it nd^it be possible to decide which medianism a reaction would follow and how fast it mi^t proceed.
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ooopound to coopound, and interesting relationships liave been found among bond dissociation energy, bond length and molecular environment.
The most cooxnon maasure of bond strength is the bond dissociation energy. The bond dissociation energy» D (X - Y) of a bor^ X - Ï is defined as the change in energy at ebsolute zero in the ideal gas state, ^ El for the reaction
X T > X + Y
the products being in their ground states. laethoda of PttwMlBlig Bond Snargles.
1) CaloriBiatrlo Itethode
If the heat cbsoibed vdien dissociation of a bond took place could be measured, this would give directly the bond dissociation energy of
tlie bond being brc^en. This has not so far been done, but the heat of reoodbination of atons or radicals has been measured in a few oases. D (H-H) has been measured in this way as 105 - 5,5 .
2) Thermal Methods
a) Equilibrium Methods
This depends upon the production of the stable equilibrium A B ^ A + B
at various temr eratures and the determination of the equilibrium constants. It has been done for several dlatomio molecules but is difficult to apply where free radicals are produced as these will probably react further.
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In this metliod, the activation energy for the process X y --- 5- X + Y
is found by measuring the rate at different temperatures. It is assumed that tliere is no activation energy for tlie reconbination