Homogeneous rate of recombination of hydrogen atoms

F. S. LARKIN'
Department of Physical Cliemistry, Lensfield Road, Cambridge, (Cambriclgeshire), Ellgland
Received June 8, 1967

The rate of decay of hydrogen atoms has been measured in a conventional type of discharge-flow
system at temperatures between 190-350 OK. The recombination fitted the equation

where Ic, is the first order surface rate constant. No three-body recombination for M = H was observed
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24

at the low levels of dissociation (2-5 %) employed. When the flow gases contained traces of water vapor
and (or) oxygen as impurities, the homogeneous rate constants (k,,,) had a small positive activation
energy which was due to the influence of a surface reaction between hydrogen atoms and the impurities.
In the absence of impurities, true homogeneous rate constants were obtained. A value of k,,,, = 4.6
+ 0.5 x 1015cm6 mole-' s-' was found at 291 OK. The temperature variation was approximately
T-'1' over the range 19G350 OK.
Canadian Journal of Chemistry, 46, 1005 (1968)

Introduction troscopy and Rink (15) and Kistiakowsky and

Most of the work on the rate of recombination
of hydrogen atoms was carried out between
1929-1940. Since then, very little work has been
done on this subject. The early investigators (1-9)
reported a wide range of values for the homoge-
neous rate constants at room temperature, and
opinions about the kinetics of recombination
varied considerably. Experiments were conduc-
ted in two ways, viz. by continually pumping
hydrogen along a cylindrical tube (dynamical
flow method) or by following the course of the
recombination in a closed reaction vessel (static
method). Most investigators found difficulty in
obtaining reproducible results because of rapid
wall recombination. Attempts were made to
poison surfaces, either by adding 2-3% water
vapor to the system (lo), or by coating the
surface with a suitable material such as syrupy
phosphoric acid (1 1). It is important to note that
the influence of these poisons on the kinetics of
recombination was not investigated. This is sur-
prising since it was known that passing water
vapor through an electric discharge generates
active species such as 0 and OH (12, 13). This
problem is discussed in the present work.
Recently, hydrogen atom recombination has
been studied at elevated temperatures (1000-
5000 OK) in shock tubes and hydrogen-air
flames. In the former method, Patch (14) mea-
sured atomic profiles by ultraviolet (u.v.) spec-
'Present address: Department of Physical Chemistry,
McGill University, Montreal, P.Q.
Gardiner (16) used an X-ray densitometer. None
of these workers was able to measure the tem-
perature coefficient of the rate constants,
but arbitrarily assumed a T-' dependence.
Sutton (17), however, has reported a T-' depen-
dence for the third bodies H, and Ar, using an
interferometer and drum camera technique.
Comparison of the constants obtained in shock
tubes with room temperature values indicates an
overall temperature dependence of approximate..
ly T-', in agreement with Sutton's results. In the
flame studies (18-20), the rate constants fit
between the room temperature and shock tube
results on the basis of a T-' temperature depen-
dence if the assumption is made that H,O is less
than an order of magnitude more efficient than -
H, as third body (see, for example, Dixon-Lewis,
Sutton, and Williams (18)).
In the present work, the rate of recombination
of hydrogen atoms has been reinvestigated in a
flow system between 190-350 OK.
Experimental
Experimental rate constants were measured in a con-
ventional type of flow system. Figure 1 shows the essential
parts of the apparatus which consisted of a discharge tube,
reaction tube, and isothern~alcalorimeter. Gases were
pumped through the reaction tube and a large stopcock
and trap by a single stage Edward's vacuum pump which
had a maximum pumping capacity of 420 I/min. A 10l bulb
was placed between the trap and pump t o ~11100ththe flow
pattern and pressure fluctuations. Hydrogen atoms were
produced by passing molecular hydrogen, either pure or
admixed with a n inert gas carrier, through a 100 watt 17
mc/s radiofrequency discharge. Gases were admitted
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 46, 1968
I THERMOSTATTED TROUGH
L-------------------------------------_I
FIG. 1. Diagram of the atomic flow system.
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24
from calibrated flowmeters into the discharge which was
established in an 8 mni i.d. quartz tube between two
aluminium foil electrodes (A). The products of the dis-
charge flowed into a pyrex glass reaction tube, of 2.5 cm
i.d. and 100 cm long, at thc upstream end of which was a
multiple hole inlet jet (B) for the introduction of reactants
with rapid mixing. The whole reaction tube was inclined
so that it could be immersed in a well-lagged copper
trough. This contained water for experiments at or above
room temperature; acetone was used below room teni-
perature. Hydrogen atom concentrations were measured
by means of a sliding isothernial calorinieter (C) which
was inserted into the reaction tube at the downstream end.
A Tygon sleeve provided the vacuum seal for the glass
tube carrying the leads to the head of the calorimeter. Two
calorimeters were used, each consisting of approximately
50 cm of 34 S.W.G. 13 % Rh/Pt wire, wound into a spiral.
Each spiral was connected to a separate Wlieatstone
bridge and they were niounted in tandem about 2-3 crn
apart so that the downstream calorimeter could be used
to determine the recombination efficiency of the first
spiral, which was always greater than 80%. Experiments
were generally conducted at total pressures between 2 and
7 nini Hg and at flow velocities between 250 and 1000
cm/s. The total pressure in the system was measured at
each end (D) of the reaction tube by silicone oil manom-
eters. Hydrogen atom concentrations of up to 5 % could
be obtained.
Cylinder gases were used throughout the flow experi-
ments. Commercial grade "high purity" hydrogen, argon,
"mineral" helium, and oxygen were obtained from the
British Oxygen Company. Deuterium of more than 99.9 %
purity was obtained from the "20th Century Electronics
Con~pany". In early experiments, hydrogen was passed
through a "Deoxo" unit at a pressure of 10 p.s.i. t o re-
move oxygen. Argon and helium were dried at atmos-
pheric pressure in glass-wool traps at -80 and -196 "C
respectively. The principal impurity in the inert gases was
oxygen (less than 0.01 %)which was not removed at first.
In later experiments, however, flow gases of much higher
purity were required. Hydrogen was deoxygenated as
before, but in addition passed through glass-wool and
molecular sieve traps (B.D.H. grade 4A) at -196 "C and
atmospheric pressure. Argon was dried at atmospheric
pressure in a PzO5 trap and then passed directly into a
silica gel trap at -80 "C t o remove oxygen impurities.
Further purification of the flow gases was effected by
passing the hydrogen, or hydrogen-inert gas mixtures,
I
through a "Deoxo" unit and liquid N2 trap just before
entering the discharge. This procedure reduced impurities
in the flow stream to a level of approximately 1 p.p.m.
Results and Discussion
In initial experiments, molecular hydrogen was
dissociated in unpoisoned reaction tubes, and in
this case it was always necessary to have some
water vapor in the hydrogen stream to obtain
sufficient dissociation (3-5 %). The water vapor
content was reduced to a suitably low level
(about 0.05 %) by passing the hydrogen through
a trap at -80 "Cjust before entering the discharge
on the low pressure side of the flow-controlling
needle valve. Atomic conceiltrations were mea-
sured over distances of up to 50 cm along the tube
at intervals from 2-7 cm. Table I shows some
typical values of [HI versus x, where x is the
distance from the discharge. The rate of recoin-
bination should be given by the equation
since the recombination on the surface (k,) is
first order (21, 22) and the second two terms
represent the recombination by the homogeneous
reaction H + +H +
M = H 2 M, where M is
the third body. Plots of [HI-' versus x were
smooth curves which were nearly linear when
the atomic flow rates, flow-stream velocities,
and total pressures were within the range 3-15
pmoles/s, 250-1000 cm/s, and 2-7 mm H g
respectively. Under these conditions, the effects
of pressure drop, axial diffusion, and heat
gradients were negligible (see Appendix). Experi-
mental measurements were made only when the
recombination was predominantly homogeneous.
The condition k,,,[H][M] > yc/2r (writing k,
 LARKIN: HOMOGENEOUS RATE O F R ECOMBINATION OF HYDROGEN ATOMS
=y ?/2r, where y is a surface recombination
constant, r is the tube radius, and Z is the mean
atomic velocity (23)) is easily satisfied within the
above experimental conditions for k , , , 1016
N the discharge. The data are taken
cm6 mole-, s-I (9), y N (21), and over the
temperature range 190-350 OK. In some cases,
after many runs, the reaction tube became ab-
normally catalytic so that surface reactions dom-
inated the recombination, and plots of [HIp1
versus x became sharp curves. When this hap-
pened, the tube was replaced by a new one which
had been carefully washed with distilled water.
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24
FIG.2. Plots of -d log,, [H]/dx versus [HI for dis-
sociated hydrogen. -d log,, [H]/dx (where x is the dis-
tance along the reaction tube and IS proportional to 1 ) is
given in arbitrary units, each of which is equal to 2 x
cm-'.
Values of -d(ln [H])/dt for various values of
[HI were found by measuring gradients of a plot
of In [HI versus t (or x). Plots of -d(ln [H])/dt
versus [HI were linear, showing that the last
term in eq. [l] is negligible and therefore no
significant third order recombination takes place
at these low atomic concentrations (2-5 % dis-
1007
TABLE I
A typical atomic flow profile for
dissociated hydrogen. x is the dis-
tance along the reaction tube from
from run 3 of Table 11
H x
(pmoles/s) (cm)
sociation). Figure 2 shows some of these plots
from which k,,, and y can be readily determined,
since eq. [l] becomes
During the course of this work, some 30 experi-
mental runs were made at temperatures between
190-350 OK, and 10 reaction tubes were dis-
carded. Table I1 shows the results of some typical
runs. The values of k,,,, were reproducible at a
given temperature and did not vary with pres-
sure. They are thus truly independent of the first
order surface reaction. Values of y vary con-
siderably from run to run, and these results are
therefore similar to those of Smallwood (1) and
Poole (24), who found that surfaces poisoned
with water vapor did not have a reproducible
catalytic activity.
In all further experiments, the reaction and
discharge tubes were poisoned with "Dri-film"
(a mixture of dimethyl-dichlorosilane and tri-
methyl-chlorosilane (25)). This poison forms a
very hard inert surface coating of low vapor
pressure and does not have the disadvantages of
phosphoric acid coatings which may have re-
actions with metals or absorb water vapor, etc.
In the poisoned system, argon (90 %)/hydrogen
mixtures could be dissociated to the extent of
3-5% even when the water vapor in the stream
was well below 0.05%, or excluded altogether.
Addition of water vapor increased the amount
of dissociation, but by less than before. It was
not necessary to renew reaction tubes during
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 46, 1968

TABLE 11
Values of kZpH2
and y. The hydrogen contained traces of water vapor as impurity
(about 0.05 %)

Run Temp. Total flow rate Pressure k Z I Hx, 10-l6

No. ("K) (pmoles/s) (mm Hg) (cmGri~ole-zs-') y x lo5
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24

TABLE 111
Values of kZ,,, and y. The argon/hydrogen mixtures contained traces of oxygen
as impurity (less than 0.01 %)

Run Temp. Total flow rate Pressure x 10-l6

kZVAr
No. ("K) (pmoles/s) (mm Hg) (cm6 s- ') y x lo5

these experiments since the catalytic activity was
always approximately constant. Table I11 shows
the rate constants obtained for argonlhydrogen
mixtures over the same temperature range as
before. In runs 6 and 7, the hydrogen was re-
placed by deuterium. Unfortunately, measure-
ments had to be made in haste because of a
limited supply of deuterium, and rate constants
could be only approximately estimated from
plots of [DI-l versus t. The values of y were
much more reproducible and they agree well with
those of Smith (21) and Wood and Wise (22) over
this temperature range.
The corresponding results obtained with
helium (90 %)/hydrogen mixtures dried at liquid
N, temperature are given in Table IV. Runs 7
and 8 were made with deuterium instead of hy-
drogen, and rate constants were estimated only
approximately from [Dl-' versus t plots, as
before.
The average room temperature values of the
homogeneous rate constants and their tempera-
ture variation for the three bodies are given in
Table V. The activation energies were determined
from simple In k,,, versus T-' plots. The present
value of k,,,, at room temperature is almost
identical with the value obtained by Steiner (9) in
a flow tube of the same diameter. The accom-
panying positive temperature coefficient raises
some difficulties, however. If recombination is
considered in terms of the "rigid sphere" model
of kinetic theory (26), and H z * is the first col-
lision "complex" formed (27), the effective
collision diameter of the hydrogen atom would
have to be more than 6 A to account for the
observed collision frequencies of -1017 cm6
mole-' s-l. The spectroscopic data on H z (28)
shows that Hz* becomes thermally unstable (at
room temperature) at atomic separations of more
than 4 A. I t is doubtful whether another model
for recombination could account for the high
collision frequencies. The most reasonable ex-
planation of the present results is that the homo-
geneous recombination was influenced by some
 LARKIN: HOMOGENEOUS RATE O F RECOMBINATION O F HYDROGEN ATOMS
TABLE IV
Values of k2,,, and y. The helium/hydrogen mixtures contained traces of oxygen
as impurity (less than 0.01 %)
Run Temp. Total flow rate Pressure kZ,HeX 10-l6
No. ("K) (pmoles/s) (mm Hg) (cm6 mole-2 s- I)
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24
unknown surface reaction (not the first order
reaction), since the observed positive activation
energy is similar to reported binding energies
(29) of physically adsorbed species at room tem-
peratures. This was the conclusion reached by
Amdur and Robinson (30), who obtained similar
results. The explanation may also partly account
for the large errors found in the temperature co-
efficients of Ic,,, since a plot of 111k,,, versus T-'
would not necessarily be linear in thls case. The
question of surface reactions requires further
discussion.
TABLE V
Values of k2,>,for three third bodies at 293 OK. The acti-
vation energies and temperature coefficients are given for
temperatures between 190-350 "K
k2.M x 10-16* Activation energy
M (cm6 mole-' s-') (kcal/mole)
*Alternatively the results can be expressed as:
101012 x T2.3f0.5 c m G rn0le-2 s-1.
2 . ~ 2
k::fiL =
1
1010+2 x T 2 ~ 4 I 0 . 5cm6 rn0le-2 S-1.
1011+2 x T1.8-10.5 cm6 rnOIe-2 S-1.
Surface Reactions
The possibility of additional surface reactions
besides the normal first order wall recombination
of hydrogen atoms, when hydrogen containing
traces of water vapor or oxygen is discharged,
was not considered by earlier workers in this
field. However, the early experiments of Geib
and Harteck (31, 32), and Rodebush and co-
workers (33, 34), show that when oxygen is
added to a stream of hydrogen atoms or water
vapor is dissociated in the discharge, other com-
plex surface reactions occur which produce
mainly H, and 0, at room temperature and
y x lo5
H,O, at liquid N, temperatures. Foner and
Hudson (35) have reported OH radicals coming
from the surfacein the H-0, system at room tem-
perature. There is some evidence (36, 37) for the
formation of higher oxides of hydrogen (H,O,
or H,O,) at liquid N, temperatures. During
experiments with the present flow system, a faint
but distinct glow could be seen on the walls of
the reaction tube when hydrogen was discharged.
The glow disappeared when all water vapor and
oxygen impurities were removed from the flow
gases. If oxygen was added before or after the
discharge, the glow was considerably enhanced,
thus suggesting that oxygen promotes surface
reactions with hydrogen atoms. The role of im-
purities in the gas stream was investigated by
adding water vapor and oxygen before and after
the discharge, and observing the effect on the
hydrogen atom profiles in the reaction tube.
In these new experiments, atomic hydrogen
concentrations were normally measured with the
isothermal calorimeter, but when atomic oxygen
concentrations also became significant, the con-
centrations were determined pl~otometricallyby
measuring the intensities of the chemilumines-
cent HNO and NO, (air-afterglow) emissions.
The emission intensities were recorded on a
"Scalamp" galvanometer from the output side of
an E.M.I. type 9558-B photomultiplier cell
equipped with infrared (Wratten 88A) and green
(Wratten 61) transmission filters. The NO con-
centrations were kept constant and the readings
through the 61 and 88A filters were converted so
that they were directly proportional to [O] and
[HI respectively. This procedure has been de-
scribed in detail by Clyne and Thrush (38).
Addition of water vapor (maximum amount
was 10% of the total flow) through the inlet jet
 1010 CANADIAN JOURNAL OF
Values of k,,,, after addition of 0, or H 2 0 before the discharge
Flow rate of Flow rate of
Temp. *Ar/H2 02
("K) (pmoles/s) (~moles/s)
*Approximately 90% Ar in mixture.
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24
had no effect on the hydrogen atom profiles. The
only observable effectwas t o reduce the catalytic
activity of the calorimeter spirals and reaction
tube walls, by surface poisoning. Addition of
oxygen through the inlet jet accelerated the hy-
drogen atom recombination by the first order
reaction (39)
By adding known amounts of 0, (about 1 %) to
the products of a discharge through hydrogen in
an argon carrier, and by keeping hydrogen atom
concentrations below about 0.7%, the recom-
bination became predominantly first order so
that the rate constant for reaction [3] could be
measured. The results of this work and a com-
parison with the chemiluminescent measure-
ments of Clyne and Thrush have been published
previously (40). When oxygen or water vapor
was added before the discharge the recombina-
tion was also accelerated by a first order reaction,
which was presumably reaction [3]. In addition
to the reactions in the discharge which might
convert water to molecular oxygen, O H radicals
formed in the discharge yield oxygen by the rapid
reactions (41)
and
[5 1 O+OH=H+O?.
The second order homogeneous rate constants
k,,,, were unaffected, however. This is shown in
Table VI where the values of k,,,, were obtained
by plotting -d(ln [H])/dt versus [HI, as in pre-
vious experiments. Since the rate constant for
reaction [3] was measured, it was possible to
estimate the concentration of 0, in the flow
stream from the observed first order acceleration.
Table VII shows the galvanometer current
readings from the photomultiplier cell when
water vapor was added before and after the dis-
CHEMISTRY. VOL. 46, 1968
TABLE VI
Flow rate of O 2 in flow
Hz0 Pressure k2,Arx 10-l6 stream
(pmoles/s) (mm Hg) (cm6 mole-2 s-') (pmolesls)
TABLE VII
Emission intensities through the 88A and 61 Wratten
filters for addition of water vapor before and after the
discharge. The experimental conditions were: Argon flow
373 pmoles/s, H z flow 31 pmoles/s, total pressure (with-
out H 2 0 ) 4.04 mm Hg, temperature 293 OK. The asterisk
denotes H 2 0 addition before the discharge
Wratten Hz0 Dark Final
filter (pmoles/s) current current
charge. Nitric oxide was added through the inle
jet and emission intensities were measured 30 cm
further downstream. The readings through the
88A and 61 filter are proportional to [HI and [O]
respectively. The galvanometer current readings
are expressed in arbitrary units, each of which is
equal to 0.048 PA. The concentrations of hydro-
gen atoms were between 1-2% of the total flow.
The oxygen atom concentrations were very small
since the emission intensity due to them is
approximately 500 times stronger than the
corresponding intensity for hydrogen atoms (42).
All current measurements were made in a com-
pletely darkened room in which even the back-
ground infrared emission was negligible. The
dark currents are thus a good measure of the
intensity of the surface emission. It can be seen
that the surface emission was considerably en-
hanced when water vapor was added before the
discharge, but remained approximately un-
altered when it was added downstream (de-
creases a little, probably due to surface
poisoning). In general, there was an enhancement
of the surface emission whenever oxygen was
present in the flow stream, indicating a surface
 LARKIN: HOMOGENEOUS RATE O F RECOMBINATION O F HYDROGEN ATOMS

TABLE VIII
Typical atomic flow profiles and values of kz.,,,, kZVH2,
and y obtained in Ar/H2
mixtures containing less than 1 p.p.m. H 2 0 and O 2 impurities

Run 1 Run 2
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24

Run Temp. Total flow rate Pressure k,,,, x 10-l5

No. ("K) (pmoles/s) (mm Hg) (cm6 mole-' s- ') y s lo5

Run Temp. Total flow rate Pressure k Z V Hx2 lo-"

No. (OK) (~moles/s) (mm Hg) (cm6 mole-' s-I) y x lo5

reaction between hydrogen atoms and oxygen

(or their reaction products).
Further recombination experiments were con-
ducted with very pure flow gases in which water
vapor and oxygen impurities were reduced to
approximately 1 p.p.m. Under these conditions,
dissociation became very difficult. Hydrogen
could not be dissociated to any measurable
extent (a problem that other workers have
reported (43, 44)). Argonlhydrogen mixtures
could be dissociated to the extent of 2-3 % if the
discharge was kept cool by air jets. The extent of
dissociation and surface recombination became
very dependent on the nature and temperature of
the surface under these conditions. Plots of
-d(ln [H])/dt versus [HI were good straight
lines (see Fig. 3) and fitted eq. [2]. Table VIII
shows typical atomic concentration profiles ob-
tained under these new conditions, together with
the values of k,,,, and y calculated from several
runs. In runs 1 4 , the hydrogen content of the
mixture was between 4 6 % . In run 5, the con-
tent was more than 90 %, so that a value of k2,,z
could be estimated. k,,,, was taken as 4.6 x
10" cm6 molec2 s-' for this calculation.
The rate constants (k,,,) found here are sig-
nificantly lower than those obtained in flow FIG.3. Typical plots of -d log, , [H]/dxversus [HI for
streams containing traces of water vapor or the recombination of hydrogen atoms in an argon carrier
oxygen impurities. Moreover, lc,,,, has a tem- (x is the distance along the reaction tube and is propor-
tional to t ) . The flow gases contained less than 1 p.p.m.
perature coefficient of approxin~ately T-lt2 O 2 and H,O impurities.
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 46, 1968

TABLE IX
Comparison of present rate constants with those from shock tube and flame
studies

Temp.
Method ("K) Ref.
Flow ;?stem 213 Ar 5.7k0.8 Preseg work
29 1 Ar 4.6+0.8

Hydrogen-air
flamzs 1273 Nz, HZ,etc 5.0 18
1500 4.0 19
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24

1650 6.0 20
Shock tube

compared with the T2.4 coefficient found pre- (18-20), assuming that all the abundant species
viously. Clearly, the positive temperature co- in hydrogen-air flames give similar values of
efficient and the high values of Ic,,,, obtained in Ic,,,. This assunlption seems reasonable in
flow streams containing impurities are the result view of the value of k,,,,, found here and
of surface reactions, and the present values of because the only extensive data on temperature
k,,, are the true rate constants. Figure 4 shows coefficients of a recombination reaction (iodine
a plot of log,, k,,,, versus log,, T and com- atoms) for a wide range of third bodies (45,46)
pares the new rate constants with the shock tube show that the rate constailts for different third
data (14, 15, 17). The general agreement is good, bodies become more similar as the temperature
although the overall temperature dependence of is raised. It is also interesting to note that the
k,,,, seems to be closer to the T-' form used by values of y in Table VIII are in good agreement
the shock tube workers in the interpretation of with Smith's data (21) for water vapor poisoned
their data than the T-'I2 dependence observed in surfaces over the same temperature range.
the present experiments. The present values of
Ic,,,, were obtained by measuring gradients of
plots of log,, [HI versus x and the limits of
error given in Table VIII were found from the
slopes that could be drawn through plots of
-d log,, [H]/dx versus [HI (see Fig. 3). The
rather large error limits associated with k,,,,
will strictly allow the temperature dependence to
lie anywhere between TO-T-', and the T -
dependence given here is only an approximate
value. It should be noted that only in Sutton's
experiments (17) was a T-' dependence of k,,,,
observed.
The values of k,,,, were not changed within
the accuracy of the experiments, when up to 10 %
water vapor was added after the discharge. These
observations were confirmed by measurements
of HNO emission. It was concluded that k,,,,, is
not greater than 5 x 10" cm6 mole-' s-I at
293 OK. Table IX compares the present results FIG.4. Plot of log,, k z , a rversus log,, T.Compari-
son of present room temperature data with shock tube
and the shock tube data with the flame studies data (see Rink (15), Patch (14), and Sutton (17)).
 LARKIN: HOMOGENEOUS RATE O F RE(:OMBINATION O F HYDROGEN ATOMS
The Reconzbination of Deuterium Atoms
Attempts were made to measure the rate of
recombination of deuterium atoms by dissociat-
ing Ar (90%)/D2 mixtures and comparing the
atomic decay profiles with those for hydrogen
atoms under identical conditions. These profiles
were also compared with those for argon/
hydrogen mixtures which contained traces of
oxygen impurities (less than 0.01 %). The experi-
ments were made in a new flow tube of slightly
larger internal diameter (2.8 cm). Figure 5 shows
some plots of -FA In [HI versus [M]j"[H] dx
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24
- --;d In [H]/dx = lc, f Ic,,,[H][M]
(rewriting
as -vA In [HI = Slc,dx +k,,,[M]S [ ~ l d x ,
where !is the mean linear flow velocity). The
plots were curved in pure flow streams, but were
linear in those containing impurities. The sensi-
tivity of the experiments was poor, owing to the
large proportion of surface recombination. The
decrease in the rate constant with increasing pres-
sure in pure flow streams indicates that some of
the surface recombination is second order (lc,").
k,,, was obtained by plotting [MI-' versus k,"/
[MI f kz,M after obtaining the values of the
second term from plots of -5d In [H]/dx versus
[HI. 5 v a l ~ ~ofe k,,,, = 4.5 0.5 x 1015 cm6
mole- s-I (290 OK) was obtained for hydrogen
atoms, in excellent agreement with the previous
values. No accurate value of k,,,, for deuterium
atoms could be calculated because of the poor
sensitivity of the results. However, comparison
with the data for hydrogen atoms shows that the
rate constant is smaller and probably lies be-
'
0HYDROGEN ATOMS WITHOUT IMPURITIES
@DEUTERIUM 11
HYDROGEN 11 WITH II
O 0 1.00 2.00 3.00
FIG. 5. Plot of -?A In [HI (and -:A In [Dl) versus
[MIHHldx (and EMlJ[Dldx).
1013
tween 1-4 x 1015 cm6 mole-' s-I (293 OK). In
the flow stream containing impurities, the value
of k,,,, for hydrogen atoms increased to 6.8 +
0.5 x 1015 cm6 molep2 s-I (293 OK).
It is not clear why there is some second order
surface recombination in these experiments
which was not observed previously. A likely
explanation is that the surface of the tube was in-
completely poisoned, as indicated by the high
level of surface recombination, and some im-
purities were adsorbed on the active surface.
Therefore, this is probably a direct observation
of the second order surface recombination which
falsifies the homogeneous rate constants.
Appendix
The exact mathematical description of the
flow method of following fast recombination
reactions is extremely complicated when the
effects of surface reactions, radial and axial
diffusion, and viscous flow are taken into ac-
count. Recently, Kaufman (23) has summarized
the limiting conditions whereby the effects of
diffusion and viscous flow can be neglected for a
system undergoing first order homogeneous re-
combination. This treatment can be readily
adapted for the case of second order recombina-
tion and allowances can be made for the distur-
bances arising from the introduction of the iso-
thermal calorimeter.
( a ) Pressure Drop
The most serious pressure drop in the present
work occurred with Ar/H2 mixtures. Assuming
Poiseuille flow for a pressure of 3 mm Hg and a
path length of 40 cm, the drop exceeds 1% for
flows faster than about 875 cm/s. The introduc-
tion of the isothermal calorimeter caused an in-
creased pressure drop (47), and for a cylindrical
calorimeter of 0.8 cm diameter, the flow velocity
must be reduced below 405 cm/s for a pressure
drop of less than 1 %. The pressure drop arising
from the recombination of atoms along the tube
is less than 1 % for 2-3 % dissociation.
( b ) Dzffsion
In the absence of radial convection and radial
diffusion effects, the condition for negligible
axial diffusion for a homogeneous reaction of
order n is Dk,,[H:In-'/'v2 << 1 (where D is the co-
efficient of diffusion, k, the nt%rder rate con-
stant, and !the mean linear flow velocity). The
 1014 CANADIAN JOURNAL O F CHEMISTRY. VOL. 46, 1968

worst cases of axial diffusion in the present ex-
periments arose with pure hydrogen at low linear
velocities. For C =. 500 cm/s, a total pressure of
5 mm Hg, and 1.5-2.5 % dissociation, the error
in the measured rate constant for hydrogen atoms
is between 1 and 2 % (taking k 2 = 1016 cm6
mole-2 s-' and D = 2.0 cm2/s at 1 atm). Axial
diffusion becomes increased when the isothermal
calorimeter is introduced into the reaction tube.
The rapid removal of atoms on the calorimeter
surfaces may cause a large perturbation in the
atomic flow profile and falsify the measured rate
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24
(a), (b), (c), and (d). Under a typical set of ex-
perimental conditions, the total error in the rate
constant measurements was found to be approx-
imately 20 %.
Acknowledgments
The author is indebted to Dr. B. A. Thrush
and Dr. M. A. A. Clyne for helpful discussions.
The research was supported by a studentship and
later a fellowship from the Science Research
Council, London (England).

constants. Rate constants of second order or 1. H. M. SMALLWOOD. . J. Am. Chem. Soc. 51, 1985
above are validly determined by calorimetry if (1929).
the condition for negligible axial diffusion is 2. H. M. SMALLWOOD. J. Am. Chem. Soc. 56, 1542
(1934).
-,-
satisfied. \ - -
~

3. H. SENFTLENBEN and 0. REICHEMEIER. Ann. Physik,

(c) Radial Concentration Gradients
Radial concentration gradients are only negli-
gible when diffusion is sufficiently rapid to
destroy the gradients caused by viscous flow and
surface recombination. Kaufman's (23) approxi-
mate formula for radial concentration gradients
modified for second order recombination shows
that the worst cases of gradients in the present
work occurred with high atomic concentrations
(2-3% dissociation) in argon carriers (D --1.0
cm2/s at 1 atm) and at high pressures (5 mm Hg).
In these cases, the concentration variations were
between 1-2%, but in most experiments they
were below 112 %.
(d) Heat Gradients
For small heat gradients, the effects of radial
convection and heat radiation can be neglected.
A calculation based on Fourier conduction
shows that in experiments with Ar/H2 mixtures
at total pressures of 5 mm Hg and with 1.5-2.5 %
dissociation, the maximum temperature differ-
ence in a cross section of the reaction tube was
from 10-15 OC (taking the conductivity co-
efficient as 3.9 x cal cm-' s-l deg-I at
6, 105 (1930).
4. W. STEINER and F. W. WICKE. 2. Physik. Chem.
Lei~zip.Bodenstein-Festband. 817 (1931).
5. I. AMDUR and A. L. R ~ B ~ N S O N . ~ . ' ~ n l . ' ~ h eSoc.
m.
55. 1395 (1933).
6. L.' FARKL a h H. SACHSSE.2. Physik. Chem.
Leipzig, B27, 111 (1934).
7. I. AMDUR. J. Am. Chem. Soc. 57,856 (1935).
8. I. AMDUR. J. Am. Chem. Soc. 60,2347 (1938).
9. W. STEINER.Trans. Faraday Soc. 31, 623 (1935).
10. R. W. WOOD. Proc. Roy. Soc. London, Ser. A, 97,
455 (1920).
11. H. VON WARTENBERG and G . SCHULTZE.2. Physik.
Chem. Leipzig, B2, 1 (1929).
12. W. H. RODEBUSH and M. H. WAHL. J. Cheln. Phys.
1, 696 (1933).
13. A. A. FROST and 0. OLDENBERG. J. Cheln. Phys. 4,
642, 781 (1936).
14. R. W. PATCH. J. Chem. Phys. 36, 1919 (1962).
15. J. P. RINK. J. Chem. Phys. 36,262 (1962).
16. G. P. KISTIAKOWSKY and W. G. GARDINER, JR. J.
Chem. Phys. 35, 1765 (1961).
17. E. A. SUTTON. J. Chem. Phys. 36,2923 (1962).
18. G. DIXON-LEWIS, M. M. SUTTON,and A. WILLIAMS.
Discussions Faraday Soc. 33, 205 (1962).
19. W. E. KASKAN.Con~bust.Flame, 2, 229 (1958).
20. E. M. BuL~wrczand T. M. SUGDEN. Trans. Faraday
SOC.54, 1855 (1958).
21. W. V. SMITH. J. Chenl. Phys. 11, 110 (1 943).
22. B. J. WOODand H. WISE. J. Phys. Chem. 66, 1049
(1962).
23. F. KAUFMAN.Progr. Reaction Kinetics, 1, 1 (1961).
24. H. G. POOLE. Proc. Roy. Soc. London, Ser. A, 163,
404 (1 937).
- .,.
\--

25. J-P. WITTKEand R. H. DICKE. Phys. Rev. 103, 620

273 OK and k 2 = 1016 cm6 molep2 s-I). In
hydrogen and helium carriers, the temperature
differences were only about 1/10 of this.
(e) Total Experimelztal Errors
The reliability of the experimental values of
the rate constants was assessed by estimating the
total systematic and random errors. The random
errors were estimated by the method outlined by
Benson (48). The systematic errors were esti-
mated by calculations such as those outlined in
(1956).
26. S. W. BENSON.The foundations of chemical kinetics.
McGraw-Hill Book Co.. New York. 1960. n. 156.
27. M. E u s u ~and K. J. LA~DLER. Trans. ~ a r a d Soc. a~
59, 2750 (1963).
28. G. HERZBERG.Molecular spectra and n~olecular
structure. Vol. 1. D. Van Nostrand Co., New York.
1951. Appendix.
29. K. E. SHULER and K. J. LAIDLER.J. Chenl. Phys. 17,
1212 (1949).
30. I. AMDUR and A. L. ROBINSON.J. Am. Chenl. Soc.
55, 2615 (1933).
31. K. H. GEIBand P. HARTECK.Chem. Ber. B65, 1551
(1932).
 LARKIN: HOMOGENEOUS RATE OF RECOMBINATION OF HYDROGEN ATOMS 1015
32. K. H. GEIBand P. HARTECK.Z. Phvsik. Chem. 40.
- - F. S. LARKIN and B. A. THRUSH. Discussions Fara-
Leipzig, A170, 1 (1934). day Soc. 37, 112 (1964).
33. W. H. RODEBUSH, C. W. J. WENDE, and R. W. CAMP- 41. F. KAUFMAN and F. P. DEL GRECO. 9th Symp.
BELL. J. Am. Chem. Soc. 59, 1924 (1937). Combustion, Cornell Univ., Ithaca, N.Y., 1962, p.
34. W. H. RODEBUSH and M. H. WAHL. J. Chern. Phys. 659 (1963).
1, 696 (1933). 42. M. A. A. CLYNE. Private communication. 1964.
35. S. N. FONER and R. L. HUDSON. J. Chern. Phys. 23, 43. T. M. SHAW. J. Chern. Phys. 31,1142 (1959).
1974 (1955).
,-- , 44. F. C. COFFIN. J. Chern. Phys. 30, 593 (1959).
36. N. I. KOBOZEV, I. I. ~ K ~ R ~ K L. H I.~ NEKRASOV,
D ~ V , 45. D. BUNKER and N. DAVIDSON.J. Am. Chem. Soc.
and E. I. MAKAROVA. Zh. Fiz. Khim. 31, 1843 80, 5085, 5090 (1958).
(1957). 46. G. PORTER and J. A. SMITH. Proc. Roy. Soc. Lon-
37. J. A. WOJTOWICZ, F. MARTINEZ, and J. A. ZASLOW- don, Ser. A, 261,28 (1961).
SKY. J. Phys. Chern. 67, 849 (1963). 47. D. H. ATHERTON.Trans. ASME, 48, 145 (1926).
38. M. A. A. CLYNE and B. A. THRUSH. Proc. Roy. Soc. 48. S. W. BENSON.The foundations of chemical kinetics.
London, Ser. A, 275, 544 (1963). McGraw-Hill Book Co., New York. 1960. p. 87.
39. M. A. A. CLYNE and B. A. THRUSH. Proc. Roy. Soc.
Can. J. Chem. Downloaded from cdnsciencepub.com by 177.27.2.36 on 02/11/24

London, Ser. A, 275,559 (1963).