HALOGEN ATOM REACTIONS

I. T H E ELECTRICAL DISCHARGE AS A SOURCE OF HALOGEN ATOMS1

ABSTRACT
A number of surface poisons have been found to prevent the rapid recombination of chlorine,
bromine, and iodine atoms. Hence these atoms can now be obtained in large conce~ltratio~is
in a flow system.
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A chemical titration procedure for both CI and Br atoms has been developed and has been
used t o test all isothermal calorimetric detector which can measure the atom concentration
along a reaction tube. 'The detector was used t o establish the surface recombination coefficient
(?) for chlorine atoms ( 4 x 1 0 - 9 and bromine atoms (6x10-j) on osyacid-covered surfaces.

INTRODUCTION
The electrical discharge has proved a valuable source of hydrogen, nitrogen, and
oxygen atoms. In the last few years many of the species produced in the discharge have
been identified. In addition, a variety of methods of following the cor~centrationof the
atomic species in a flow system have been described (1, 2, 3, 4). As a result, rate constants
for a large number of elementary reactions of these atoms are being reported in the
literature. Unfortunately, workers have had less success with halogen atoms in a flow
system. T h e statement made in 1933 by Schwab (5) that bromine atoms recombine on
For personal use only.

every collision with the walls, and chlorine atoms survive fewer than 20 collisions
irrespective of the wall materials, seems to have discouraged further work with these
species in a flow system.
Recent developments in the theory of atom recombination (6, 7) point to the need for
a system capable of studying the low pressure recombination of halogen atoms. In
addition, there remain a considerable number of elementary halogen atom reactions
which are in need of direct measurements. For this reason we have re-examined the
possibility of obtaining halogen atoms in a flow system.

EXPERIMENTAL
Chemicals
iVIatheson Company chlorine was dried with silica gel and purified by distillation.
Reagent grade bromine was dried with phosphorus pentoxide, and purified by distillation.
Air was removed from reagent grade iodine by sublimation in vacuum. NOCl from Mathe-
son Company was purified only by trap-to-trap distillation. All other gases and chemicals
were of reagent grade purity and were used without purification.
Apparattis
A conventional pyrex flow system with a linear flow velocity between 100 and 400
cm per sec was used. Inert gas flows were controlled with Edwards needle valves, and
measured with conventional capillary-U-tube flow meters. All mercury was isolated
with a layer of octyl phthalate. C12, Br?, NOC1, and IC1 gases were contained in 22-liter
bulbs. A constant pressure was maintained with the appropriate freezing bath. Flow
was controlled by glass capillaries only, and measured with I-12S04-filled flow meters.
All stopcocks in the halogen flow system were greased with Kel-F grease.
lillanziscript recei-ded Augz~st18, 1961.
Co7rlribiition from the Departnze7zt of Cltemistry, U?ziversity of British Columbia, Vancor~ver8 , B.C.
Can. J. Chem. Vol. 39 (1961)

2556
 OGRYZLO: HALOGEN ATOM REACTIONS. I 2557

T h e discharge tube and reaction tube a r e shown in Fig. 1. T h e discharge tube was
constructed of quartz t o prevent breakage while the tube was being heated. I t was made
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nickel coil

platinum supports

water jacket

vacuum jacket
For personal use only.

detector leads 3 L9'

FIG. 1. Discharge tube, reaction tube, and movable detector assembly.

removable t o facilitate cleaning since contamination occurred most often in this region.
T h e jacket was used t o cool the tube with a stream of air while the discharge was on.
A 100-watt, 2450-inegac~~cle generator was used t o create the discharge.
T h e reaction tube was 50 cm long and had a diameter of 2.1 cm. I t was surrounded
b y a water jacket for temperature coiltrol a n d a vacuum jacket t o prevent a temperature
gradient froill forilliilg when the tube is operated a t other than room temperature.
 2558 CANADIAN JOURNAL O F CHEMISTRY. VOL. 39. 1961

T h e halogen gas (at flows between 0.5 and 45 pmoles/sec) could be introduced a t A
(Fig. 1) together with inert carrier gases such as argon and helium ( a t flows between 5
and 1.50 pmoles/sec). Other gases could be introduced after the discharge a t B. Another
opening a t C made it possible to clean the reaction tube and apply different coatings to
the reaction tube walls, without affecting the walls leading to the reaction tube. These
coatings (hereafter called "poisons") were usually applied in the following manner. T h e
cleaned vessel was filled with a hot, concentrated ICOI-I solution and allowed to stand for
30 minutes. T h e vessel was then tl~oroughlywashed with distilled water and filled with
a lOy0solution of the poison in water. This solution was allowed to stand for 1 hour and
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then drained. Finally, the system was evacuated for about 2 hours. During this period
the discharge tube and reaction tube were heated to 250" C and 80" C respectively.
Figure 1 also shows the method which was used for moving both a coil of wire and a
wrede gauge along the reaction tube. T h e movable vacuum-tight juilctioil is provided
by pressing a tygon tube against a glass tube with two O-rings. T h e glass tube is greased
with Kel-F grease. No leaking occurred, and the slight degassing of the grease is of no
consequence a t this point in the flow system. The racli. and pinion arrangement described
previously ( 3 ) was also used for supporting the wire-coil but it cannot be used with a
inovable wrede gauge.
The principle of the isotherinal-caloriinetric atom detector (hereafter called the
"detector") used in this worli. has already been described (3). I t requires that the atoms
in a gas stream recolnbine on a metal wire, raising its temperature to a value 1'.The heat
For personal use only.

liberated is then ineasured by observing the electrical current necessary to raise the
wire temperature to the same value 1'. For successful operation the following require-
ments must be met:
( I ) the thermal conductivity must be the same in the presence and absence of atoms;
(2) all the atoms must be recombined;
(3) no other species capable of heating up the detector can be present.
The first coildition is easily satisfied in a gas siinply subjected to an electrical discharge
if the atoms recombine on almost every collision with the wire. T h e second condition can
be satisfied by a suitable enlargement of the detector coil. T h e third condition can be
verified by an independent atom measuring device which is insensitive to such species.
A wrede gauge was coilstructed with four 10-micron pinholes. T h e pressure difference
across the pinholes was measured with an inclined oil-manonieter.

RESULTS A N D DISCUSSION
Fluorine
An attempt was made to pass F ? through an electrical discharge. However, the gas
was found too difficult to handle in a flow system and the experiment could not be
con~pleted.
Chlorine
Our first attempts to produce C1 atoms by passing a stream of the gas through a
discharge in a pyrex and quartz tube were unsuccessful. A thin silver mirror which
provides a sensitive test for halogen atoms by its discoloration showed no change 1
centimeter away from the discharge. Dry wall coatiilgs of polythene, teflon, NaC1,
NaOH, and Al(0H)a did not help to produce any detectable atoms.
On the other hand, when 1-13PO4, I-12S04,I-13As04, I-I3BO:{, and IHC1O4 were used to
"poison" the wall, immediate discoloration of the silver mirror occurred when the dis-
charge was initiated. The absence and presence of atoms with these surface poisons
was then verified with a wrede gauge. T h e atom concentrations measured with the gauge
 OGRUZLO: HALOGEN ATOM RE.4CTlONS. I 2559

were then compared with those measured by the detector using platinum, silver, cobalt,
arld nickel coils. The atom concentrations ineasured along the reaction tube by all inethods
were proportional to each other. I-Iowever, the wrede gauge and platinum detector
yielded a i11uc11lower value for the atom concentration than the Ag-, Co-, and Ni-covered
detectors. The rapid atom recombination 011 the glass of the wrede gauge may account
for the low value obtained with this instrument. A low catalytic activity for platinum
has been observed previously (8) and would account for the low value obtained with
this surface. Cobalt and silver detectors possess a number of other disadvantages. They
are attacked by halogen atoms and the catalytic activity of the halide is somewhat
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lower than that of the metal. More troubleson~e,however, is the forn~ationof some volatile
compound that distills onto the walls a t temperature above 100" C. Not only does niclrel
not possess these difficulties, but it also has a larger temperature coefficient of resistivity.
Complete removal of the atoms by the nickel coil was checked by placing a second
detector immediately after the first. A 90-cm length of 30-gauge nickel wire wound into
a double spiral and extended to a length of 1 cin was found to be effective i l l removing
the atoms a t pressures u p to 4 m m I-Ig. At higher pressures it was difficult to prevent
the atoms froin being swept past the detector unless it was extended to about double
this length.
Some typical chlorine atom flows measured 25 cm after the discharge are given in
Table I.
'I'ABLE I
For personal use only.

Flow, in p~llolesper second

F'ressure,
nlrll of Ijg Inert gas CI? CI

Clremical l'itrations
Chemical titration of oxygen and nitrogel1 atoms has been facilitated by the fact
that many of these reactions are accompanied by light einissioil. Both reactions con~monly
used for nitrogen and oxygen atoins
N+NO + S?+O

and
O+NO1+ NO+O?
make use of the light-emitting reaction

to observe the equivalence point of the titration. We have not found any useful light-
emitting reaction in our work with halogen atoms, and hence a different equivale~lce
indicator must be used.
We have found the following reaction most useful for titration of chlorine atoms:
CI + NOCl --r NO + CI?.
Subsequent reactions
C1+ NO +M -r NOCl + &I
Cln + 2NO 4 2NOCI
 2560 CANADIAN JOURNAL O F CHEMISTRY. VOL. 39, 1961

are considerably slower under conditions present in the flow system. Figure 2 gives the
atom flow measured by the detector as a function of the NOCl flow introduced through
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NOCl or 1CI flow ( p moles/ s e e )

FIG.2. Chlorine atom titration curves with NOCl (open circles) and with ICl (closed circles).

stopcock B in Fig. I. The detector was placed 2 centimeters beyond the NOCl inlet.
T h e agreement between the original chlorine atom flow ineasured by the detector and
For personal use only.

the NOCl flow necessary to remove all the atoms is excellent.

The titration of chlorine atoms with NOCl was carried out over a variety of experi-
mental conditions. technique used was to set the NOCl flow a t some value in excess
of the chlorine atom flow and then decrease the NOCl flow until atoiils began to reach
the detector. This NOCl flow was then recorded as the chlorine atom flow ineasured by
titration. In all experiments carried out a t a total pressure below 4 mm Hg the atom
concentration measured by the two methods did not differ by more than 5%. However,
the detector readings fell below those of the NOCl titration a t higher pressures. This
confirms the previous observation that a t the higher pressures atoins are swept by the
detector without being recombined.
I t should be emphasized that though the detector is being used in the titration, the
method is still an independent quantitative measuremelit. This is underlined by the fact
that a glass-covered thermistor probe is even more effective in observing the end point
of the titration.
Surface Recombination
With the nickel detector, the atom conce~ltrationwas measured along the reaction
tube. At a total pressure not greater than 0.3 mm IHg (due mostly to the carrier gas) the
gas phase recon~binationis slow and can easily be corrected for. Though not unequivocally
determined, the wall reaction appears to be of first order in chlorine atoins and can be
written
CI + wall k ," 1/2 Cla + wall
+

for which we have calculated a value of 0.8 sec-I for kw a t 10' C with all the oxyacids
used. T h e more ineaningful recombination coefficient (r),therefore, has a value of about
4 x 10-j.
A considerably greater value was obtained until the marked effect of a sinall amount
of water froin the surface poison in the discharge was noted. T h e water not only greatly
 OGRYZLO: HALOGEN ATOM REACTIONS. I 2561
increased the atom concentration but also caused a sharp increase in the rate of recom-
bination of the atoms.

Bromine
The experi~nentsdescribed in the previous section were repeated with bromine. The
results may be summarized as follows:
(I) No bromine atoms were detected in a stream of electrically discharged bromine
unless the surfaces were coated with one of the oxyacids used for chlorine atoms.
(2) Bromine atoms can also be titrated with NOCl by the same technique used for
chlorine atoms. T h e agreement between the atoms measured by titration and those
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measured with a nicltel detector was satisfactory below a total pressure of about 4 nun I-Ig.
(3) Water vapor increases both the bromine atoms obtained from the discharge and
the rate a t which they are removed by r e c o ~ n b i ~ ~ a t i o n .
(4) The value of the surface recombination coefficient (r) was found to be about
6 X 10-j a t 10" C for all the oxyacids used as surface poisons.
Iodine
T o date we have had no success in obtaining iodine atoms from electrically discharged
I?. The difficulty seems to lie in the hot region immediately after the discharge because
we have found that the atoms can be maintained if they are created outside the discharge.
The closed circles in Fig. 2 give the pseudo-chlorine atom concentration obtained
when ICI is added to the same stream of chlorine atoms usecl in the NOCl titr a t'(on.
For personal use only.

The fast reaction occurring is

Subsequent reactions of iodine atonls are somewhat slower. ?'he breali in the curve
probably represents the complete titration of chlorine atoms. This point is in reasonable
a g r e e ~ n e ~with
it the end point of the NOC1 titration. Beyond this point on the curve
the tletector must be obtaining its heat from the recombination of iodine atoms. The
fact that the heat obtained a t the end point is not 36/58 of that originally obtained fro111
the chlorinc atoms may be due to the more rapid gas phase recombination of iodine
atoms, urhich could bc observed by ~novingthe detector along the tube. This rapid gas
phase recombination made it too difficult to estimate the wall recombination rate.
Nevertheless, it is a p ~ ~ a r e nthat
t the absence of atoms from electrically discharged
iodine vapor must be due to an even more rapici recombination in the hot region of the
discharge.

COSC1,USlON
T h e isothermal calori~netricdetector has been shown to be capable of measuring
accurately the concentration of both chlorine and bro~lline atoms in a flow systenl
operating in the pressure range from 0.3 m m I-Ig to 4 mm Hg. T h e wall recombination
coefficient (r) has been shown to be sufficiently snlall to allow the use of this halogen
atom source for kinetic studies. A number of reactions have been studied with this
flow systenl and will be presented elsew11e1-e.

i\CI<NO\\'LEDG&IENNI'S
The author wishes to thanli the National Research Council of Canada and the Presi-
dent's Research Fund a t this University for financial assistance.
 CANADIAN JOURNAL OF CHEMISTRY. VOL. 39. 1961

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