J. Grebe and K.H. Homann: Blue-gren Chemiluminescencein the System C$-I2/O/H.

587

[u)]J. PeetersandC. Vinckier, 15th Symp. (Int.)on Combustion, The [23] I. T. N. Jones and K. D. Bays, Proc. R. Soc. London Ser. A,
Combustion Institute, Pittsburgh 1974, p. 969. 335, 547 (1973).
1211 I. Messing, T. Carrington, S. V. Filseth, and C. M. sadowski, [a]M. J. Howard and I. W. M. Smith, Chcm. Phys. Lett. 69, 40
Chem.Phys. Lett. 74, 56 (1980). (1980).
1221 J. Warnatz. 18th Symp. (Int.) on Combustion, The Combustion (Eingegangen am 22. Februar 1982) E 5144
Institute. Pittsburgh 1981, p. 369.

Blue-green Chemiluminescence in the System GH2/0/H.

Formation of the Emitters CH(A2A), G(d3Q) and C*H*
J. Grebe and K. H.Homann
Institut fUr Physikalische Chemie. Technische Hochschule Darmstadt, Petersenstr. 20. 6100 Darmstadt

Chemilumineszenz / Emksionsspektren / Freie Radikale / Kohlenwasemtoffe / Reaktionskinetik

A kinetic study of the chemiluminescenceof the emitters CH(A2A), C,(d'%) and C2H* in a mixture of acetylene, oxygen and hydrogen atoms
has been performed using a low pressure discharge flow reactor at 2.66 mbar and 298 K under largely varying initial conditions. The absolute
concentrations of the emitters could be quantitatively simulated and correlated to the simultaneous formation of higher hydrocarbons in this

C,H + 0 -
system when the following formation reactions of the excited species are assumed

- -
CH* + CO, k 7 10" cm3mol-l s-I

and
C + CH,
CH + CH, - Cz++ H,, -
k = 7 10" cm3mol-' s-l
C2H* + H,, k z 10"m3 mol-' s-l .
I Iirsc reactions are in particular accord with the dependence of the chemiluminescence on the concentration of free hydrogen atoms.

1. Introduction In addition to the banded spectra of CH(A ,A-X ,n)and

The combustion of hydrocarbons is accompanied by a visible
blue-green flame. Here the emitters CH(AzA) (=CH*) and
C2(d3&) (=C2*) have been identified some time ago but the
kinetics of their formation is still not explained. Many
elementary reactions have been proposed but none of them has
found general acceptance [l]. The direct proof of any reaction
mechanism is difficult to obtain because the precursors of the
chemiluminescence emitters are probably short-lived reactive
intermediates occurring in small concentrations so that they
cannot be detected.
The gas phase reaction system C,H,/O/H is an appropriate
model system for a new investigation of the blue-green
chemiluminescence because of the following reasons:
a) At room temperature it exhibits a chemiluminescence spec-
trum which is very similar to that of hot hydrocarbon/oxy-
gen flames 121. Therefore, any results should be comparable
to these hot systems.
b) Its main reactions are now quantitatively understood, partic-
ularly the formation of CO, C3H4 (propyne, allene) and
ca, 13~41.
c) Hydrogen atoms promote the formation of the higher hy-
drocarbons propyne and butadiyne as well as the formation
of the chemiluminescence emitters, this suggests the partic-
ipation of common intermediates e.g. CH, CHI, C2H, C3Hz
and C3H3.
d) Computed concentration-time-profiles of these intermedi-
ates can replace experimental profiles until the detection
methods are better developed.
The aim of this work is to test the hypothesis that some of the
above mentioned hydrocarbon radicals are direct precursors of
the chemiluminescence emitters.
C,(d3&-a3q) a quasicontinuous emission with a maximum
at 510 nm contributes considerably to the.blue-green emission
of the C2H2/0/H system. The emitter is an
excited C2H radical 12, 5 - 8). This emission is included in the
kinetic analysis. A second ultraviolet quasi-continuousemission
with a maximum at 300 nm has also been reported 191.
2. Experimental
2.1. Apparatus and Reaction Conditions
The apparatus has been described previously (41. We recall that the
kinetic experiments were performed by using a double discharge flow
system coupled to an optical cell for measuring visible and ultraviolet
chemiluminescence. The reactants (GH,. 0.H, 03 were diluted with
a carrier gas (85 Vo helium, 15Vo nitrogen) in ratios up to 3 percent. The
pressure was kept at 2.66 mbar (2 Torr), the temperature at 298 K.
Ratios of [C,H,],,/[O]o between 28 and 0.5 were used. The initial
concentrations are reported in the figures legends. Oxygen atoms were
generated by the titration reaction N + NO -. N, + 0.The equiva-
lence ratio of NO and nitrogen atoms was first obtained in the usual
manner. that is through extinction of Nj, NO*and NO3 chemilumines-
cence [lo]. Then C2H, was added and the NO flux was slightly adjusted
to minimize the CN(B '1' - X 'X+) emission [ll].
2.2. Emitter Concentrations from Absolute Chemiluminescence
Intensities
spectral resolution A 1 -
Fig. 1 shows a spectrum of the reaction system CzH 10 with a
1 nm. The transitions CH(A 3A-X ,lI.
B2Z--X211),C2(d3r$-a'rI,,)and theVaidya bandsofCHOare the
most prominent features of the spectrum. The OH (A '
Z - X ,n)
bands are weak in the absence of added 0,and masked by the CHO-
bands. TheCO(A'n-X'~,d3A-,a3n,e3E-a3~transitions[121
are also weak under the chosen reaction conditions and cannot be
distinguished here. The spectrum, however, shows a marked quasi-
.continuous emission which has received little attention up to now [2. 5.
91. The true distribution of intensity of the continuum determined by
the aid of a calibrated tungsten-ribbon lamp is given in Fig. 2. The

Ber. Bunsenges. Phys. Chem. 86, 587-597 (1982) - 0 Verkg Chemie GmbH, D-6940 Weinheim, 1982.
MnS - -
9021/RZ/MM 0587 S 02.50/0
588 J. Grebe and K. H. Homann: Blue-green ChcmilumineSeencein the System C2H2/0M.

measured at 516.5 nm (background of Cj). The integration included

the wavelengths between 410 and 750 nm but probably it did not cover
the complete range. Therefore, the concentrationsthat were calculated
from the corresponding absolute intensities may be too low. If other
unknown emitters were to contribute to the continuum at the larger
wavelengths, then they might be too high. The second quasi-continuous
emission in the range between 260 and 400nm has an absolute intensity
which was about 7% of the forementioned C2H* intensity. The
relations between the intensities of the continua and the times of
reaction were similar taking into account contributions of overlapping
emission at 306.5 nm due to OH* and CHO*.
Because of the possible accumulation of errors in the calculation of
the intensity calibration factor a maximum error of a factor of two or
three could be possible (in the case of C2H* this factor may even be
larger). The reproducibility of the measured intensities or concentra-
tions, respectively, for nominally equal reaction conditions is about
f 20%. The detection limit of CH*, Cy and C,H* was about I *

Fig. 1
2 . lo-'' and 3 - mol ~ r n - respectively.
~, This confirms the high
sensitivity of the chemiluminescencespectroscopy.
Chemiluminescence spectrum of the system CzHz/O; [C2HJo =
1 6 . lo-'', [O], = 2.0 . mol reaction time 1.5 ms. The
contribution of the quasicontinuous background due to C2H* is 3. Results
indicated (see text) 3.1. CH*
The left parts of Figs. 3 to 6 show experimental CH* concentration
time-profiles for a great many different initial conditions. The
concentrations [C2H2),, [Ole, [HIo and [O,), have been varied system-
1001 n atically. Fig. 3 shows CH* profiles for different (C2HJo..While at low
[C2HJo the emitting zone is very extended it shrinks wth increasing
[C2H2lO.The height of the maxima does not change much but the
maxima move towards the mixing region. The maxima of the CH*
profiles appear earlier than those of the OH* profiles and the decay is
faster by a factor of two than that of OH* (compare Ref. [4]).The area

Fig. 2
True distribution of intensity of the quasi-continuous chemilumines-
cence emission. The intensity shown is proportional to the number of
photons divided by the time and the wavelength interval

distribution shows two maxima at 300 nm and 510 nm, a minimum at

380 nm and an onset at about 260 nm. The continuum with the
maximum at 510 nm is also observed in the vacuum ultraviolet photo-
lysis of C2H2 and is ascribed to an electronically excited C2H radical
[S - 81. The continuum with the maximum at 300 nm has not yet been Fig. 3
identified. 11 may tentatively be attributed to an electronically excited Experimental and calculated (CH*] profiles for various [C2H&
C2H2because it is very similar to the C2H$ fluorescence spectrum (parameter: [C2H2]d1O-" mol cm-'). [Ole = 2.0 * lo-" mol cm-'
observed by Brus (131and by Hamai and Hirayama (141.

-.
Absolure intensities were determined by comparison with the known
NO$ intensiry of the reaction 0 + NO NO; as a standard 115, 161.
Emitter concentrations were calculated by multiplying the measured
absolute intensities by the lifetimes 7 of the excited emitter states
(r(CH(A2A)) = 570ns 117, 181, T(Cz(d 'n,)) = 120ns [19], T(C2H')
= 6400 ns 171). Since the shapes of the spectra of CH*. C j and C2H*
and therefore their energy distributions did not change significantlyin
the experiments the ratio of a prominent peak height to the integrated
band or continuum intensity was constant.
For the measurement of intensity-time-profiles small parts of the
spectrum near the chosen peak were recorded. The underlying emission
was subtracted.
CH (A2A-. X2n,0-0. 1-1, 2-2) intensities were measured at 431.4
nm (Q branch of the 0-0 band). The CH(AZh-XZn, 0-1) and
CH(BrZ- - X 211, 0-0) spectra contributed only 3.8 and 3.4 percent, 0 5 10 0 10 mr
respecrively. 10 the above mentioned bands and they were neglected.
The C,(d 'llg - A '&) intensities were measured at 516.5 MI (head of
the 0-0 band). Integration included the 1-0.0-0, 0-1 and 0-2 sequences
-
Fig. 4
Experimental and calculated [CH*] profiles for various [Ole
of the Swan svstem. The auasi-continuous emission of C,H* was &-
(parameter: [O]dlO-lo mol cm-'). (C2HJo = 9.9 . lo-'' mol cm-3
 J. Grebe and K.H. Homann:Blue-green Chemiluminescencein the System C2Hz/O/H. 589

c-
3-

2-

l t t'
O 5 10 0 5 10 ms

Fig. 7
Experimental and calculated [Cj] profdes for various [C2HJ0
(parameter: [CzHJdlO-'O rnol cm-4. [O], = 2.0 rnol

1Sh
:p
- / =
/

. /*-*-+-*--
01 I II I I
0 5 10 0 5 lo ms 0 5 10 0 5 10 ms

fig. 6 Fi.8
Experimental and calculated (CH.1 profdes for various [O& Experimental and calculated [ Q ] profdes for various [HI,
(parameter: [OJdlO-'omol cm-3. [ ~ H J ,= 2;4 ~ o - ~ ~ m ~ i c m(parameter
-~, [C HJ, = 2.43 10-'omol cm-3
-
[O], = 2.35 lo-' rnol cm-
[H]dlO-'o rnol
[O], = 2.15 10- rnol - m
under the CH* concentration-timee is roughly inversely propor- .re.
tional to [C2HJo. A variation of [O], in C2H2rich flames does not shift
the profile maxima of CH* (seeFig. 4). The CH* concentration is pro-
portional to [O];. The same is true when H atoms are added during
[O], variation (not shown). The effect of added H atoms is very similar
to that observed in the case of [OH*] (see Ref. [4]). According to Fig. 5
the CH* concentration at short reaction times increases and the
maxima move towards the mixing region. Obviously, the formation of
a CH* precursor is promoted by H atoms. The increase of CH* con-
centration per added H atoms is smaller than that of [OH*]. In q H z
rich flames a plot of CH* emission versus [HIo exhibits a maximum
while OH* is increasing monotonously (Fig. 11). The influence of
added O2is shown in Fig. 6. The CHI concentration decreases on 02
addition. If [OJo I[C2HJo the CH*intensity is about 2/3 of that
0 5 10 0 5 10 ms
without O2addition. A very similar decrease is observed in the case of
Cf and C2H* (see below) suggesting a common (not naxssarily direct)
precursor of CH*, C j and C2H which reacts rapidly with 0,.
Fig. 9
Experimental and calculated [q] profiles for various [C2HZI, in the
3.2. q* presence of constant [ao = 1.46 - mol cm-
(parameter: [GHJ,,/IO-lo mol [O], = 2.0 . rnol cm-3
The results of the variation of [CzHJQis shown in Fig. 7. The times
required for the C t profdes to reach thew maxima are generally longer
than those for OH*, CH* and C2H*. The decay of the Cf profiles is the system CzH2/0/H with particular regard to the effect of H atoms
slower than that of the CH* profiles. This is the reason why at greater [m]. The maxima of the profiles move towards the mixing region when
reaction times the green colour of the Cz emission dominates the blue increasing amounts of H atoms are present at the beginning of the
colour of the CH* emission. reaction.
The heights of the maxima of the C j profiles increase with increasing The CJ intensity at constant short reaction times increases linearly
[C2HJo but the areas under the profdes decrease. with H atom concentration while the other emissions change only
Fig. 8 shows the strong effect of H atoms on the Cf emission which slightly or decrease again at larger [HIo (see Fi. 11). Moreover, the
led to a systematicreinvestigationof the chemiluminesmt emissionsin increase of intensity due to [ao is highest for the C j chemilumines-
590 J. Grebe and I(. H. Homann: Blue-green Chcmiluminmce in the System C2H2/0/H.

"I: [C,H7
lo-" mot cmd

\o-
1L \ 16.0

61

0 n
O 5 10 0 5 10 ms 0 5 10 0 5 10 ms

Fig. 10 Fig. 12
Experimental and calculated [Ctl profiles for various [O]O Experimental and calculated [C,H*] profiles for various [C~HJO
(parameter: [O]dlO-lo mol cm-'). [C2H2], = 9.9 10-'omol (parameter: [C2H2]d10-'o mol cm-'). [O], = 2.0 10-lomol cm-'

nw* ---v---O 10"'mol cm-' 1

0.1 I
L

0 1
l j j
FS.I.2 Fig. 13
Fig. 11 Experimental and calculated [C,H*] profiles for various [C2H$, in the
Dependence of the chemiluminescence intensities on [HIo. The intensi- presence of a constant [HIo = 1.46 mo\an-
ties are divided by the values without H addition. (parameter: [CzHJdlO-10 mol cm-'). [O], = 2.0 * 10-lOmol
[C,H,], = 10.8. 10-'Omolcm -', [O], = 1.2 * 10-'Omol cm-',
reaction time 2 ms [CZH'I
lo-" mot cm-'
cence (Fig. 1 I ) . The influence of H2 accompanying H atoms can be
neglected, this was shown by independently varying [HJ.
Obviously. H atoms are particularly important for Cy formation. If
they are noi added from the beginning of the reaction the C$ formation
must wail until they are produced by the reaction 0 + C2H2. This
explains the compararively slow growth of the C; concentration with
time.
Fig. 9 shows the C; profiles for different [C2H,], when H atoms are
added. The maxima are shifted towards shorter reaction times for all
[C2HJo as can be seen by comparison with Fig. 7.
Without addition of H atoms the overall Cf concentration increases
approximately as [0]h6for the [C,HJ, used in Fig. 10. With addition
of H atoms it is proportional to [O], (not shown). What seems to be a
1-1
[0]h6dependence is probably in part a masked H dependence. Fig. 14
Experimental and calculated [C2H*]profiles for various [OI,
(parameter: [O]dlO-'O mol cm-'). [C,H2], = 9.9 * 10-'omol

The experimental C2H* profiles for different [CLHJOare shown in

the left part of Fig. 12. They exhibit maxima at slightly longer reaction
times than those of CH*. The decay is slower than that of CH*. The
maxima grow more strongly with increasing [C,HJ,.
The C2H* concentrations show the same dependence on [O], as
[OH*], i.e. -
[O],,(Fig. 14). compare Ref. [4]. The dependence on
[HIo is similar, too, but somewhat weaker than for OH* (see Fig. 11).
Again, the formation of C2H* is promoted by H atoms,especially at
short reaction times. Fig. 13 in comparison to Fig. 12 demonstrates the
influence of H atoms for different [C,HJo. Just as with C$ and CH*,
the C2H* concentration i s reduced to 2/3 of the value without 0,
addition when [OJo ( = [C2HJo) is added (Fig. 15).
It is worth noting that the continuum emission contributes 260% to
the total visible and UV emission of the atomic flame when
[C2H2]d[O]~ 2 2, the corresponding portions of CH*, C; and OH*
being ==25%, =6% and =9%. (The last value is somewhat arbitrary
because it depends on the 0,concentration chosen.) This important
 J. Grebe and K. H. Homann: Blue-green Chemiluminescencein the System C2H2/O/H. 591

Kistiakowsky et al. [21-231 explained the intense CH*

radiation that is observed in shock tube experiments with

C2H2+ O(or OH)

C2H +0
--
C2H2/02/Ar-mixturesby the sequence of reactions:
GH + OH(orH20)
CH* + CO
(41)
(42)
(The numbering of the reaction follows that of Ref. 131 and 141.)
Using a then accepted standard enthalpy of formation
A&Z(GH) = 490 kJ mol-‘ [24]reaction (42)was endothermic
by at least 20 kJ mol-I (if CH*=CH(A2A, u’ = 0). Kistia-
kowsky attributed the apparent energy of activation of the CH*
emission (about 100kJ mol-I) to reaction (42).At temperatures
around 2000 K, that is for the conditions of the shock tube
Fig. 15 experiments, reaction (42)should then be sufficiently rapid to
Experimental and calculated [C2H*] profiles for various [OJo
-
(parameter: [OJdl0-lo mol cm-3. [C2HJo = 18.5 1 0 - 1 0 m 0 1 ~ - 3 , generate the observed CH* photons per C2H2molecule
-
[O], = 2.1 10-lOmol Oxidized.
In a subsequent study of the room temperature reaction
contribution of G H to the blue-green emission of the C2H2/O/H system G H 2 / 0 by Arrington et al. [25] no significant
system under C2H2 rich conditions has been overlooked up to now. temperature dependence of the CH* emission was observed.
Therefore, these authors excluded the endothermic reaction
4. r n g d o n sequence (41)- (42)as a source of CH* chemiluminescence in
this reaction system.
4.1. Approach
However, this proposal was later modified by Brennen and
In two previous papers [3,4]it was shown that a quantitative Carrington [XI who postulated C2H radicals in vibrationally
description of the measured C3H4 (propyne, allene), C4H2 excited states, that is, a chemical activation instead of a thermal
(butadiyne) and OH (A22+) concentration-time-profiles is activation. The vibrationally excited C2Hradicals were assumed
possible for a considerable range of reaction conditions in to produce preferentially the vibrationally excited CH (A 2A,
addition to the main products CO and H atoms. An u’ = 2) state. The observed variation of the intensities
appropriate reaction mechanism consisting of about 27 originating from the u’ = 0 and u’ = 2 levels of the CH(A ’A)
elementary reactions was proposed. Our following analysis is state was explained on the basis of competition between
based on the assumption that the profiles of the involved vibrational de-excitation and chemical consumption of the CH*
reactive intermediates are reasonably well reproduced by the precursor C2H. The authors based their tentative explanation
model calculations. If the reaction mechanism is extended by on the assumption that the standard enthalpy of formation of
the assumed formation reactions of chemiluminescent species C2H should be 20 or even 50 kJ mol-1 higher than 490 kJ
which originate from the reactive intermediatesH, 0,OH, CH, mol-’, a value recommended by Cowperthwaite and Bauer
CHI, G H , C3H2 and C3H3hypothetical concentration-time- 1241.
profiles of the emitters can be computed. If the experimental Since that time several new experimental values of the
profiles are quantitatively reproduced by the computer model standard enthalpy of formation have been reported. The
calculations the assumed chemiluminescencereaction is said to following values are given in kJ mol-’: 510 [27],544 f 21 1281,
be consistent with the experimental results and it is likely that a 531.4 f 4.2 [29],544 [30],527 1311, 561 f 21 [32].If we take
correct kinetic explanation of the chemiluminescence effects an average of the above values (534 f 10 kJ mol-I), then the

Our proposals must naturally be consistent with observations C2H + 0 -

has been given. This is supported by the failures when using enthalpy of reaction for the step
other reactions that have also been proposed in the past.
CH* + CO
in similar reaction systems and with energetic considerations. is within its limits of error sufficient to populate the (A2A,
(42)

Additional experiments which prove the proposed elementary u’ = 0 and u’ = 1) and the (B22-, u’ = 0) level. This is
reaction more directly are desirable. illustrated in Fig. 16. The relative population of the electroni-
cally excited CH* levels is roughly indicated by the length of the
4.2. CH* horizontal lines which represent the vibrational states of CH*.
4.2.1. &H + 0 + CH* + CO (42) Vibrational excitation of G H would only lead to the
The blue chemiluminescence of CHI is due to hydrocarbon production of about one tenth of the CH* radicals which are in
combustion, this is well known since it appears also in the inner the higher vibrational and rotational levels. The vibrational
cone of a Bunsen flame. Not all previously proposed ex- frequenciesof C2H, v, = 1848 cm-*, v2 = 650cm-I and v3 =
planations of the CH* emission can conveniently be discussed 3612 c m - I [33,341 correspond to vibrational quanta with the
on the basis of the approach chosen. The starting point of the energies 22.1, 7.8 and 43.2 kJ mol-’, respectively. That is to
discussion is the elementary reaction, which seems to be the say, the excitation of the lowest vibrational levels would be
most likely source for the formation of the chemiluminescent sufficient to fill the energy gap. An estimate based on steady
CH*. Some alternative proposals will be briefly discussed state approximations has shown that a ten percent fraction of
afterwards. vibrationally excited GH(+)radicals can easily be present under
these reaction conditions. Moreover, the calculated [C2Ht/ Table 1
C2H] ratio depends critically on the initial concentrations of 0 Supplementary reaction mechanism for CH* kinetics

and C,H, as postulated in Ref. 1261. The unknown bimolecular

Rate constant (298K) Ref.
rate constant for the de-excitation of vibrationally excited C,Ht No. Reaction
cm3rn01-1s-1
by the carrier gas helium was assumed to lie in the range
-
between 1 loll and 1 1012cm3mol-' s-l. (42) CzH + 0 + CH* + CO 7 . 101' this work
(43) CH* + CH (1.75. 106s-1) 117, 181
(9) CH+H +C+Hz 3 . 1013 this work
I Entholpy of Reaction I Eneqy Levas of CH (12) CH + 0 2 + products 1 .to13 141
(44)
(49 C2H + 0 2 -.
CH2 + 0 2 + products
products
.
1 10'2
3.3 * 1012
1381
I31

possible without making use of further assumptions. Table 1

Fig. 16
Enthalpy of reactions forming CH (negative sign omitted) and energy
levels of CH relative to CH(X '!I Y".= 0)
In the room temperature reaction system C,H,/O/H the
formation of C2H in vibrationally excited states or even in its
ground state by hydrogen abstraction from C2H, is not possible
(e.g. reaction (41)) because these reactions are all endothermic.
Homann and Schweinfurth [3] have proposed an exothermic
contains the supplementary reaction mechanism for formation
and consumption of the CHI radical. Some other reactions
which have to be added to the previously published reaction
mechanism are also listed for completeness since they are
important under some reaction conditions which were not
covered in the mass spectrometric work 131. Quenching of CH*
seems to be negligible under these conditions 126, 35 - 371.
The results of the model calculations are shown in the right
hand parts of Figs. 3 to 6. A comparison shows that the
characteristics of the experimental profiles (shape, dependence
on [C,HJo, [O],, [HI,, [OJ,are adequately simulated by the
computed profiles. The dependence on [HI, is a little too weak,
similar to that of its precursor CH (compare Ref. 141). The 0,
influence can be explained by assuming the consumption of
CH,, CH and C,H by 0,. the reaction with CH being the major
contribution.
The rate constant of the chemiluminescencereaction
C,H (or C,Hq +0 - CH* + CO (42)
was obtained by fitting the calculated CH* concentrationto the
experimental concentrations, the result is k4, = 7 . 10" cm3
mo1-ls-l.
The preceding discussion and the successful model
calculation have shown that reaction (42) allows a consistent
and quantitative description of the blue CH* chemilumines-
cence in the reaction system C,H,/O/H.
Let us now consider related reaction systems. The rotational
distributions in the CH(A 2A-X 'II, 0-0) band in the room
temperature systems C4H2/0 [MI and C302/H/0 141) are very
similar to those of the C,H2/0 system, which suggests an
identical formation step for CH* in all these cases. The CH*
emission in the C,H,/O reaction can probably be ascribed to
the following reaction sequence:

-
reaction path leading to C2H. The last step in this sequence is
the reaction
C3HZ + 0 - CZH + CO + H (13)
which is exothermic by at least 100 kJ mol-', this is consistent
C,H,
0
4 C3Hz
0
--* C2H
0
CH*
which is consistent with the dependence of the integrated CH*
intensity on [C4HJo and [O], as found by Schwanebeck [42].
with a vibrational excitation of C,H. Here AJf(C3H3 was This reaction is under further investigation.
estimated to be equal or larger than 500 kJ mol-'. In the reaction system C,O,/H C,H is a reactive intermediate
The preceding statements may be summarized as follows: according to Faubel and Wagner [43]. Therefore, the
The thermodynamic objections against the reaction
C,H +0 - CH* + CO (42)
appearance of CHI chemiluminescence after addition of 0
atoms [44]is easily understandable.
If reaction 1421takes place in the room temperature systems it
have been rejected completely. As both reactants of this should also occur in hot flames. The relatively higher popu-
hypothetical chemiluminescence reaction occur in the reaction lation of the CH(A 'A, u' = 2) and CH(B ,Z-) levels and the
mechanism proposed in Ref. [3]. model calculations are easily additional Occurrence of CH(C2Z+) [2] can probably be ex-
 J. Grebe and K. H.Homann: Blue-green Chemiluminescencein the System C2H2/O/H. 593

plained by a thermal excitation of the CH*precursor C,H. In 4.2.3.C0* + CH + CO + CH* (47)

these hot flames C2His probably also formed by H abstraction
from C,H, as may be seen from the C4H2 concentration profides
calculated by Warnatz [45].Flame model calculationsshould be
compared with absolute CH* intensity measurements from hot
flames in order to determine whether or not reaction (42) is
relevant under these reaction conditions.
Further confirmation of the postulated reaction (42)could be
obtained more directly through a photolysis experiment. Here
C,H radicals may be generated by the W photolysis of GH,,
C2HBr or C,HCN in the presence of 0 atoms. The CH*
intensity should then be proportional to [OI and [GH]. Such
experiments are desirable in order to obtain additional evidence the range between lo-" and lO-''mol ~ m - Marmo ~ .
for the proposals made here.
Becker and Bayes [48]have considered the formation of
electronically excited CHI by energy transfer from elec-
tronically excited CO*. If again we assume a steady state for
CH* the following equation can be used to calculate the CO*
concentration which is needed to explain the observed CH*
intensity:
By substituting our own [CH*l and [CHI values, and by
assumingalarge k,of 2 1014cm3mol-1s-l, then [CO*]liesin
et al. I491
have determined absolute intensities for the CO(A - X I Z + )

4.2.2.q + OH - CH* + CO
W V transition under reaction conditions similar to o m . The
resulting CO(A'm concentration values (using 5.,
[SO])is about 3 - mol
= 10 ns
which is several orders of
The CH* emission of hot hydrocarbon/oxygen flames has magnitude below the required concentration range. Conse-
often been explained by the reaction quently, CO(A'l-9 can be excluded as an activator of CH*. The
excitation energy of metastable CO(a31-9 would also be suffi-
C,+OH- CH*+CO (46) cient to excite CH by energy transfer. The CO(a3Q concentra-
which was proposed and discussed in detail by Gaydon (see e.g. tions may be higher than those of CO(A'm but it seems quite
Ref. [I]). The reaction provides a sufficient amount of energy unlikely that they can be as high as the required to
to account for all the excited states of CH* without having to mol
postulate excited precursors. Porter et al. 1361 and Bulewicz et
-
al. [35] determined the quotient Y = [CH*]/[CJ [OH] in low 4.2.4. CHf + CHf + CH* + CH3 (48)
pressure C,H,/02 flames by spectroscopic methods. If the CH* Quickert [51] has proposed reaction (48) in order to explain
concentration is controlled by the reactions the experimental results of El-Dessouky [52]who studied the
C,+OH-
CH* - CH*+CO
CH
(46)
(43)
CH* chemiluminescence in the system C,HJO. Several
objections can be made against this proposal. Quickert
conceivablydid not notice the influenceof H atoms on the CH*
then Y = k,/k4, should be nearly independent of the flame emission although it was reported by Becker et al. [44].
parameters. This was confimed by these authors. A mean rate Quickert's reaction scheme cannot explain the promoting effect
.
constant k6 = 3.4 10l2an3mol-' s-I can be estimated [35, of H atoms and it would lead to a decrease in CH* emission,
461 from their data. Since the formation reaction of C2 is not this conflicts with experiment. The assumed precursor CH;
known no model calculation for the system GH,/O/H is would certainly be consumed by H atoms. Moreover, reaction
possible and Gaydon's hypothesis cannot be verified. There- (48) seems improbable because of energy and intensity
fore, only a rough semiquantitativeanalysis is possible. considerations. It has been questioned that the necessarily high
It follows from (46) and (43)and from a steady-state CH: concentrations should be attainable under the usual
treatment for CH*, which was verified by the computer analysis reaction and quenching conditions [q. Also, it appears
under all conditions studied, that unlikely that the considerable energy gap for the excitation of
CHI in reaction (48) can, to such an extent, be fdled by an ad
hoc postulated (electronic?) excitation of CH2(see Fig. 16).

By substituting our own values of [CH*] and [OH] the k4 value
cited above, and the known rate constant k43hypothetical [CJ
profiles can be calculated. For [O], = 2 * mol cm-3 and
[qHJdlO-'O mol an-3 = 4, 8, and 16, respectively, maxima
-
of [CJ profiles at t = 2 ms with the values of 4.4 lo-", 1.9 *
lo-" and 7.4 . mol can be obtained in this way.
These concentrations seem excessively large, particularly, if the
Czconsumption reaction C, + C,H2 + products (k = 5.8 lo" - fragment from C&H2cannot be a direct precursor of &*. The
cm3mol-' s-l [47])is taken into account. Therefore, we do not
consider reaction (46) a reasonable explanation of the CH*
chemiluminescence in the C,H2/O/H system. The rather weak
dependence of the quotient Yon experimental variables in hot
flames could be ascribed to a strong coupling of the CH*
precursors GH and 0 (proposed in 4.2.1.)to Gaydon's reac-
tants C, and OH.
4.3. q*
4.3.1. CHZ + C + q*+ H2 (49)
Some hypothetical reactions which may lead to electronically
excited q(d3"I, are Listed in the energy diagram of Fig. 17.
Those reactions that are consistent with thermodynamic
requirement are all in agreement with the postulate by Ferguson
[53]and by Fairbairn (541,which states that an intact C,H,
species CH,, CH and the C atom might be such precursors.
If a simple reaction path towards C atoms can be assumed in
the C2H,/O/H system then a computer analysis of the reaction
CH2 + C + G* + H2 (49)
is feasible. Several authors [I, 44. 55, 561 have proposed the
reaction
 594 J. Grebe and K.H.H o ~ M :Blue-grecn Chcmilumincscence in the System C2H2/0/H.

-
tions.. If it is not far from unity [CI remains between 2 10-13
Enthalpy of Rmction Encrgy Levels of C2 and 2 - mol cm-3 (without H addition). This is of the
same order of magnitude as the value reported by Fontijn and
600 Johnson [58, 59) for the C2H2/0/H system under similar
EnPrpy conditions as used here. The constant k,,was varied over a wide
kJ m0I-l range. In order to reproduce the correct simulation of the shape
V’ of the C, profiles by model calculations 5,should be greater
d ’Tlg than 1 10” mol-’ s - l . The best fit, k,, = 2 10” cm3 mol-’
- 5
s - l , is several orders of magnitude larger than a previous
estimate of Martinotti et al. [a] but is analogous to the rate
constant of the related reaction CH + C,H,: (klo + k l , ) =
3 1013cm3 mol-’ s-I. If the ratio (k49* k9)/ks1 is fitted to
a

about 1 . lOI4 cm3 mol-’ s - ’ the absolute C: concentration is

correctly simulated by the reaction model. By substituting those
values for k9 and k,, we obtain a value of 7.5 lo” cm3 mold’
s-I for k49 which is an unusually large rate constant for a
chemiluminescence reaction. Vibrational excitation of a minor
part of the CH, species (about 30%) is necessary to allow for
the production of C,(d ’Il.3 in vibrational states with D‘ > 1.
The right sides of Figs. 7 to 10 show computed C; profiles
which should be compared to the left sides of the same figures.
The shape of the profiles is reasonably well simulated for
[C,H,], variation (Fig. 7). The ratios of the profile maxima are
not exactly reproduced but the deviation is still within the limits
of experimental error. [C,H210 variation with simultaneous
addition of a constant [HI, shows a satisfactory agreement
between measurement and calculation, the deviation being
more pronounced at large [C,H,], values (Fig. 9). The
theoretical dependence on [O],without H addition is somewhat
stronger than in the experiment (Fig. 10). Both in the experi-
Fig. 17 ment and in the calculation it tends towards a proportionality to
Enthalpy of reactions forming C, (negative sign omitted) and energy [O], in the presence of initial H atoms (not shown).
levels of C, relative to C, (a 3nu, = 0 ) 13’’

The strongest argument for the C t formation kinetics

CH +H - C + H, (9)
as a source of C atoms. From an energetic point of view only
ground state C(3P)atoms can be generated by this reaction. The
reaction is analogous to reaction (4) and it fits well into the
reaction scheme. C atoms will preferentially be consumed by
C2Hz.The reactions with the other two major reactants H and
0 are trimolecular, and they are therefore slow under the
CH, (or CHD
proposed here is the correct explanation of the extraordinary
dependence on [HI, of the C,* chemiluminescence (Figs. 8 and
11). Two steps with participation of H atoms (reactions (4) and
(9)) are necessary. As H addition lowers the concentration of
one of the Cy precursors, CH,, the dependence on [HI, is not
quadratic but linear. Thus, the reaction
+C - Cy + H, (49)

conditions here applied. Table 2 contains the supplementary is supported by our model calculations.
reaction mechanism which has successfully been used as a In order to provide additional experimental evidence for the
model for the Cy chemiluminescence in the C,H,/O/H system. proposed reaction sequence
It may be helpful to offer some comments on the rate constants
of Table 2.

Table 2
CH, 3 CH - H
C

Supplementary reaction mechanism for Ct kinetics

followed by reaction (49), the reaction system CH,/H should be
studied as directly as possible.
Rate constant (298 K) Ref, The production of CHI (e.g. by UV photolysis) in the
No. Reaction
cm3 mol - I s . I presence of free H atoms should lead to an intense Ct
- --_I-

chemiluminescence if the reaction scheme is essentially correct.

(49)
(SO)
CH: + C
c: - c: --
C t + H:

+
7.5 . 1013
(8.33 . lo6 5 - 9
3 . 1013
this work
1191
Moreover, the measurement of C atom concentrations in the
CHJH and in the C,H,/O/H system would be desirable.
(9)
(51)
--
(’H
C L-
T H
C:H:
__
-
C H?
products 2 . 1013
this work
this work In the reaction system C3O,/H without 0 atom addition no
C,+ chemiluminescence is found [41]. Since CH radicals have
been detected in this system by laser induced fluorescence [41],
Quenching of C2 has been neglected (57, 35, 191. The ratio C atoms should be present, too, if reaction (9) takes place. If
k,/k,, determines the range of computed C atom concentra- reaction (49) is the true C; chemiluminescence reaction the
 J. Grebe and K. H. H o ~ M Blue-gren
: Chemiluminescencein the System C2Hz/0/H. 595

presence of CH, in the C302/H system must be excluded in because no rate constant is available. The computed profiles are
contradiction to a reaction scheme assumed by Faubel and shown in the right sides of Figs. 12to 15. Without addition of H
Wagner [43].Vice versa, reaction (49)must be excluded if CH2 atoms the dependence on [C2HJoand on [Olois adequately de-
is experimentallydetected in the C30z/H system. scribed by the assumed reaction scheme (Figs. 12 and 14). The
same is true for the [OJo dependence (Fig. 15). A [C,H2Io
4.3.2.CH + CH +q*+ H2 (52) variation in the presence of added [HIo shows increasing
There is strong evidence in the literature that reaction (52) deviations between calculation and experiment with decreasing
does not contribute significantly to Cy production, neither in C,H2 concentrations (Fig. 13). The theoretical rate constant of
hot C,H2/0, flames [35, 36, 611 nor in atomic flames with reaction (54) is about twice the value of the hard sphere
C,H2, CH2C0 and C3OZ [62,41].For example, no %* emission collision number. An error analysis has shown that an error of
was found in the C302/H system although CH radicals were 30% each in the GH* intensity calibration, quenching
present in sufficient concentrations [41].In the present work conditions, and in the calculated concentrations of CH, and
additional evidence against reaction (52)was obtained. If reac- CH could easily give rise to an error in kM by as much as a
tion (52) were the formation step for Cf its concentration would factor of 4.
be proportional to [CHI' and, because of the strong coupling Nevertheless, a rate constant in the order of magnitude of
between [OH*] and [CHI (see Ref. [41),also to [OH*I2. This is 10'' cm3 mol-I s-l would be required to explain the absolute
contradicted by our experiment. experimental CzH* intensity.
The CH2/H experiment proposed in chapter 4.3.1. is also
suitable for testing the hypothesis for C2H* formation. The C;
4.3.3.CH + C .+ q*+ H (53) emission should be accompanied by C2H* emission under the
This reaction and the C-atom kinetics of reactions (9) and same conditions because CH, and CH should be present simul-
(51) predict a quadratic dependence of [Cl]on [HI,. This is in taneously.
disagreement with the experiment. Also, the computed C; The species C2H*does not occur in the C302/H system but
concentrations differ from the experimental values by as much appears together with Cf after 0 addition [41].The argument
as an order of magnitude, particularly at the highest [CzHJo, at the end of section 4.3.1. is valid also for the excitation
even when ks3is chosen to be 1 1014cm3rno1-I s-'. reaction (54). As already mentioned, the intensity profiles of
the two continua measured at 516.5 nm and 306.5 nm, respec-
4.4. CzH* tively, were very similar. If the ultraviolet continuous emission
The only known process of formation for C,H* is the W V is indeed emitted by excited C,H; molecules a side channel of
photolysis of C2H, and C,HBr [5 - 7,631.The excitation energy reaction (54)
of CzH* is about 400 to 450 kJ mol-' relative to the ground CHZ + CH CZH; +H
+ (58)
state of C2H [6, 81. Energy transfer from CO(A I l l ) or
CO(a 311) to excite C2H2or C2Hitself can be excluded by simple could possibly explain the observed similarity in the kinetic
steady state calculations similar to those in 4.2.3. The CO* behaviour of the two continua.
concentration in the C,H2/0 system is not large enough to
explain the C2H*concentration found in the experiment. 4.4.2.CH + CH + GH* + H (59)
In the hypothetical reaction CH + CH + C2H* + H a
4.4.1. CHZ + CH + q H * + Hz (54) transient excited C2H: may be formed which has an excita-
Model calculationshave shown that reaction (54) might offer tion energy very similar to that used in the W V photodissocia-
an explanation of .the C2H*emission in the GH,/O/H system. tion experiments to excite CzH2and produce the CzH* emission
The enthalpy of reaction (A,.@ = -450 kJ mol'l, ground 15, 61. Therefore, we assumed this reaction to be a likely
state of C,H) is sufficient for the production of electronically candidate for the explanation of the C2H* emission in the
excited C,H*. Since this proposal is not quite as consistent with C2H2/O/H system. Model calculations. however, showed that
experiments as the proposals made for the CH* and C; chemi- reaction (59) is not consistent with the mechanism and the
luminescence some questions remain. Table 3 contains the experimental'results. For example, it predicts an [HI, depend-
ence which is much too strong and a C2H*concentration that it
too small by a factor 10 even when we choose ksp equal to
Table 3
Supplementary reaaion mechanism for C a b kinetics -
i 1014 ~ m mo1-1
3 S-1.

Rate constant (298 K) Ref.

No. Reaction 4.5. Conclusion
cm3moi-1s-1
Our hypothesis that higher hydrocarbons and the chemilu-
(54) +
CH2 CH + C2H' + H2 4.3 1014
a this work minescence emitters might have common precursors seems to be
(55) C2H* + C2H (1.56. 10's-I) I7 valid. The chemiluminescence reactions listed below are
(56) C2H* + N2 + products 1.8 . 1013 171
(57) +
C p * C2H2 products .
1.2 1014 I3 consistent with the findings in the system C2H,/O/H and they
give a quantitative description of the measured concentration-
time profiles of CH(A 2A), C2(d 3fl)and C,H*. A schematic
appropriate supplementary reactions for formation and representation of the combined hydrocarbon forming and
consumption of C,H*. Quenchingof C2H*by He was neglected chemiluminescencemechanism is given in Fig. 18.
5% J. Grebe and K. H.Homann: Blue-grem Chlemiluminescencc in the System C@2/0M.
Fig. 18
Reaction scheme of the reaction system C2H2/O/H. The chemilumin-
escence reactions postulated in this work are indicated by heavy
bars. Dashed arrows without superscripts mean reaction with C2H,.
(Compare the complete reaction scheme for C,H, and C3H, formation
in Fig. 13 of Ref. [3])
The blue CH+chemiluminescence is consistently explained by
the reaction
C2H(and C2H3 + 0 - C H* + CO,
about one tenth of the C2H radicals being vibrationally excited.
(42)
The green C; chemiluminescence is produced by the reaction
CHZ(andCH3 +C + Cf + H2 (49)
CH +H -
assuming the formation of C atoms in the reaction
C + H,.
The quasi-continuous emission o f electronically excited C2H* is
(9)
probably the result of the reaction
CH, + CH - C2H* + H2. (54)
Rate constants may be estimated from model calculations for
the proposed chemiluminescence reactions.
We are indebted to Dr. J. Warnatz who cared for the computer
program and to Dr. H. Schweinfurth for valuable discussions. The
work received financial support by the Deutsche Forschungsgemein-
schaft and the Fonds der Chemischen Industrie. We gratefully
acknowledge this help.
References
111 A. G. Gaydon, The Spectroscopy of Flames, 2nd edition,
Chapman and Hall, London 1974.
[2]R. E. Ferguson and H. P. Broida, 5th Symp. (Int.) on
Combustion, p. 754,Reinhold, New York 1955.
131 K. H. Homann and H. Schweinfurth, Ber. Bunsenges. Phys.
Chem. 85, 569 (1981).
(41 J. Grebe and K. H. Homann, Ber. Bunsenges. Phys. Chem. 86.
581 (1982).
151 K. H. Becker, D. Haaks. and M. Schilrgers, Z. Naturforsch. A 26.
1770 (1971).
161 H.Okabe. J. Chem. Phys. 62. 2782 (1975).
(7)K. Henrich, Diplomarbeit, Bonn 1976.
181 S. Shih, S. D. Peyerimhoff, and R. J. Buenker, J. Mol. Spectrosc.
74, 124 (1979).
191 A. Fontijn, J. Chem. Phys. 44,1702 (1966).
[lo]M. A. A. Clyne, in: B. P. Levitt. Gas Phase Reactions of Small
Molecules, p. 247, Plenum Press, London. New York 1973.
[ll]A. Fontijn, J. Chem. Phys. 43, 1829 (1965).
I121 K. H.Becker and K. D. Bayes, J. Chem. Phys. 48, 653 (1968).
1131 L. E. Brus, J. Mol.Spectrosc. 75, 245 (1979).
[14]S. Hamai and I. Hirayama. J. Chem. Phys. 71, 2934 (1979).
[15] A. Fontijn, C. B. Meyer, and H. I. Schiff, J. Chem. Phys. 40.64
(1964).
[la]D. L. Baulch, D. D. Drysdale, D. G. Horne, and A. C. Lloyd,
Evaluated Kinetic Data for High Temperature Reactions, Vol. 2,
Butterworths. London 1973.
[17]A. P. Baronavski and J. R. McDonald, Chem.Phys. Lett. 56,369
(1978).
[18]M. Clerc and M. Schmidt, Faraday Discuss. Chem. Soc. 53. 217
(1972).
[19] T. Tatarczyk. E. H. Fink, and K. H. Becker, Chem. Phys. Lett.
40, 126 (1976).
[20]K. H. Homann, J. Warnatz, and Ch. Wellmann. 16th Symp.
(int.) on Combustion, The Combustion Institute, Pittsburgh
1977,p. 853.
1211 C. W. Hand and G. B. Kistiakowsky, J. Chem. Phys. 37, 1239
(1962).
[22]G. P. Glass,G. B. Kistiakowsky. J. V. Michael, and H. Niki, J.
Chem. Phys. 42, 608 (1%5).
1231 G. P. Glass,G. B. Kistiakowsky, J. V. Michael, and H. Niki,
10th Symp. (Int.) on Combustion, The Combustion Institute,
Pittsburgh (1965),p. 513.
[24]M. Cowperthwaite and S. H. Bauer. J. Chem. Phys. 36, 1743
(1962).
[25]C. A. Arrington, W. Brennen, G. P.Glass,J. V. Michael, and H.
Niki, J. Chem. Phys. 43, 1489 (1965).
1261 W. Brennen and T. Carrington, J. Chem. Phys. 46, 7 (1967).
(271 S. W. Benson, Thermochemical Kinetics, J. Wiley and Sons. New
York 1976.
128) J. R. Wyatt and F. E. Stafford, J. Phys. Chem. 76, 1913 (1972).
[29] H. Okabe and V. H. Dibeler, J. Chem. Phys. 59, 2430 (1973).
(301 D. K. Sen Sharma and J. L. Franklin, J. Am. Chem. Soc. 95.
6562 (1973).
(311 Th. Just and P. Frank, Ber. Bunsenges. Phys. Chem. 81. 1119
(1977).
[32] B. K. Janousek, J. I. Brauman, and J. Simons, J. Chem. Phys.
71, 2957 (1979).
[33]M. E. Jacox, Chem. Phys. 7. 424 (1975).
[341 H. J. Spangenberg, I. BOrger, H. Hoffmann, and G. Magel, Z.
Phys. Chem. (Leipzig) 259, 531 (1978).
[35l E. M. Bulewicz, P. J. Padley, and R. E. Smith, Proc. R. Soc.
London 315, 129 (1970).
[36]R. P. Porter, A. H. Clark, W. E. Kaskan, and W. E. Browne,
11th Symp. (Int.) on Combustion, The Combustion Institute,
Pittsburgh 1%7, p. 907.
1371 G. Ndaalio and J. M. Deckers. Can. J. Chem. 45, 2441 (1%7).
[381 C. Vinckier and W. Debruyn, J. Phys. Chem. 83, 2057 (1979).
[391 W. Lange and H. Gg. Wagner, Ber. Bunsenges. Phys. Chem. 79.
165 (1975).
I401 J. Grebe. Diplomarbeit. Darmstadt 1975.
1411 H. H. Brenig, Dissertation, Wuppertal 1981.
1421 W. Schwanebeck, Diplomarbeit, Darmstadt 1973.
I431 C. Faubel and H.Gg. Wagner, Ber. Bunsenges. Phys. Chem. 81,
684 (1 977).
(441 K. H. Becker, D. Kley. and R. J. Norstrom, 12th Symp. (Int.)on
Combustion, The Combustion Institute, Pittsburgh 1%9, p. 405.
I451 J. Warnatz, in: Workshop on Soot in Combustion Systems, Le
BischenbergIFrance 1981,Plenum, London, in press.
1461 M. F. Golde and B. A. Thrush, Adv. At. Mol. Phys. 11, 361
(1975).
1471 V. M. Donnelly and L. Pasternak, Chem. Phys. 39, 427 (1979).
1481 K. H. Becker and K. D. Bayes, J. Chem. Phys. 48, 653 (1968).
I491 F. F. Marmo, J. P. Padur, and P. Warneck. J. Chem. Phys. 47,
1438 (1967).
I501 R. Elmhof and F. H. Read, Chem. Phys. Lett. J J . 326 (1971).
1511 K. A. Quickert, J. Phys. Chem. 76, 825 (1972).
[521 M. A. H.El-Dessouky, Dissertation, GOttingen (1970).
1531 R. E. Ferguson, J. Chem. Phys. 23,2085 (1955).
I541 A. R. Fairbairn. 8th Symp. (Int.) on Combustion, Williams and
Wilkins. Baltimore 1962,p. 304.
[551 J. Peters, J. F. Lambert, P. Hertoghe. and A. van Tiggelen, 13th
Symp. (Int.) on Combustion. The Combustion Institute, Pitts-
burgh 1971. p. 321.
 M. Braun, A. Hofzumahaus. and F. Stuhl: VUV Flash Photolysis Study of the Reaction of HO 597

I561 J. Peeters and C.Vinckiet, 15th Symp. (Int.)on Combustion, The 1611 R. Bleekrode and W. C.Nieuwpoort, J. Chm. Phys. 43, 3680
Combustion Institute, Pittsburgh 1974, p. 969. (1965).
157) S. J. h o l d , G. H.Kimbell, and D. R. Snelling, Can. J. Chan. [a21 K. H. Becker and D. Kley. Chem. Phys. Lett. 4, 62 (1969).
53, 2419 (1975). 1631 J. R. McDonald, A. P. Baronavski, and V. M. Donnelly, Chem.
[58]A. Fontijn and S. E. Johnson, J. Chem. Phys.59, 6193 (1973). Phys. 33, 161 (1978).
1591 A. Fontijn, private communication Nov. 1980.
[a01 F. F. Martinotti. M. J. Welch, and A. P. Wolf, J. Chem. Soc., (Eingcgangen am 22. Februar 1982) E 5145
Chem. Commun. 115 (1968).

VUV Flash Photolysis Study of the Reaction of HO with H02 at 1 atm and 298 K
M. b u n , A. Hofzumabaus, and F. Stuhl
Physikalische Chemie I, Ruhr-UniversitBt, D-4630 Bochum, W.-Germany

mie Radikale / Gase / Photochemie / Reaktionskinetk

Equal concentrations of HO and H were generated by flash photolysing small amounts of H,O diluted in N, at a pressure of about one
atmosphere. Using sensitive detection by resonance absorption, the HO radicals were monitored in the presence and in the absence of 0,.In the
presence of 0,.the radicals were found to disappear significautly faster than in the absence of 0,.This enhanced decay is attributed to the fast
reaction of HO with HO,. Using simple kinetic arguments and computer modeling,the rate constant, kl,for the title reaction is estimated to be
1.1 * 10-'ocm3s-1(+25~;
-35%).

Introduction has recommended a value greater than 4 1O-I' cm3 s-l. It is

Previously, the kinetics of the reaction of HO radicals with
CO has been investigated in our laboratory at total pressures of
up to loo0 mbar N2 [l]. At that time the rate constant of this
reaction was found to depend on total pressure when small
amounts of 0,were added to the reaction system. Since then we
have improved the experimental arrangement and are now able
to generate larger concentrations of HO the decay of which can
be followed for longer times with higher precision. With this
more sensitive method the HO radicals were observed to decay
non-exponentially in the presence of excess CO and 0,.
Subsequent computer modeling indicated that reactions of HO,
can play an important role in this system. We have therefore
begun a reinvestigation of the flash photochemistry of H,O in
the presence and in the absence of 0,. In the presence of O,, the
reaction of HO with HO, was found to be dominant. This
photolysis system hence presents an opportunity for the study
of this important radical radical reaction.
The reaction of HO with HO, is of importance to the under-
standing of combustion processes and of atmospheric
chemistry. A significant feature of the reaction
HO + HOZ + HzO + 0, (1)
is the termination of two reactive radicals in HO,(HO + H0&
chain reactions [Z].
The kinetics of reaction (1) has been previously investigated
by a number of research groups [3-181. While the values
measured for the rate constant of this reaction range from
-
2 lo-" to 2 - cm3 s - l , no review or evaluation [19-25]
Note Added in proof:
Another study 137)dcalii with Reaction (1) at pressures of He and Ar
ranging from 75 to 730 Tom has appeared since the submission of the
present paper. The value for the rate constant at 1 atm pressure (kl =
1.2 i 0.4) - cm3 I-') determined in this study is in very good
agreement with that of the present investigation.
interesting to note that the smaller values of &l have been
obtained in flow systems at low total pressures while the larger
values have been determined in irradiation systems at pressures
of about one atmosphere.
In the present investigation, equal amounts of H and HO
were generated by photolysing H,O in N, at a pressure of about
one atmosphere. The absolute concentration of HO was deter-
mined by time resolved absorption spectroscopy. Decays of HO
were monitored in the absence and in the presence of 0,. In the
absence of O,, the major removal steps for HO are found to be
the termolecular reactions of HO with H and HO. In the
presence of 0,, H atoms are rapidly converted to HO, which in
turn reacts dominantly with HO. It will be shown that the fast
removal of HO in the presence of 0, supports a fast rate con-
stant, k,, for reaction (1).
Experimental
Vacuum UV flash photolysis of H20was used to generate H and HO
in the presence of Nz at a pressure of about lo00 mbar and at a
temperature of (298 i 2 K). The apparatus has been described
previously in detail [ll.For the present experiments, new LiF windows
(Harshaw) with higher vuv transmission were used to generate initial
concentrations of HO ranging from 1 * 10" to 7.3 10" ~ m - ~ .
Since some of the relevant reactions in the present system proceed
according to second order the accurate determination of the absolute
radical concentration is very important. In t h e experiments, HO
radicals were detected using absorption of light from an HO resonance
lamp [it2q. The absorption light path was 11.2 m. The wavelength of
detection was centered at 308.2 nm (HO(AZZ++X'll); Q1(3)line)
using a spectral resolution of about 0.2 nm.
Absolute concentrations of HO were calculated according to the
relationship given by Golden et al 1261. Values of oscillator strengths
-
of single rotational lines, fJ"Jlwere estimated usingfoo = 7.05 lo-'
[zal and line strengths, SJJW,givm by Goldman and Gillis [27.For IOW
rotational quanta, the mrresponding temperature of the HO emission
spectrum was measured to be 600 K. The rotational partition function
was calculated to be Qra(298K) = 40.5. With this data, the following

Ber. Bunsenges. Phys. Chem. 86.597-602 (1982) - 0 Verlag Chemie GmbH, D-6940Weinheim, 1982.
o005-9021/82/0707-0597 S 02.50/0