JCK(Wiley) INTERACTIVE

Gas-Phase Reaction of NO3

Radicals With Isoprene:
A Kinetic and Mechanistic
Study
TORSTEN BERNDT, OLAF BÖGE
Institut für Troposphärenforschung e. V., Permoserstr. 15, 04303 Leipzig, Germany
Received 25 November 1996; accepted 27 February 1997

ABSTRACT: The gas-phase reaction of NO3 radicals with isoprene was investigated under flow
conditions at 298 K in the pressure range 6.8 , P(mbar) , 100 using GC-MS/FID, direct MS,
and long-path FT– IR spectroscopy as detection techniques. By means of a relative rate
method, the rate constant for the primary attack of NO3 radicals toward isoprene was deter-
mined to be (6.86 6 2.60) 3 10213 cm3 molecule21 s21.
The formation of the possible oxiranes, 2-methyl-2-vinyl-oxirane and 2-(1-methyl-vinyl)-
oxirane, was observed in dependence on total pressure.
In the presence of O2 in the carrier gas, the product distribution was found to be strongly
dependent on the reaction pathways of formed peroxy radicals. If the peroxy radicals mainly
reacted in a self-reaction, the formation of organic nitrates was detected and 4-nitroxy-3-
methyl-but-2-enal was identified as a main product. On the other hand, when NO was added
to the gas mixture and the peroxy radicals were converted via RO2 1 NO : RO 1 NO2 , the
formation of methyl vinyl ketone as the main product as well as 3-methylfuran and meth-
acrolein was observed.
From the ratio of the product yields if NO was added to the gas mixture it was concluded
that the attack of NO3 radicals predominantly takes place in the 1-position.
A reaction mechanism is proposed and the application of these results to the troposphere
are discussed. q 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 755– 765, 1997.

INTRODUCTION important role in the chemistry of the troposphere. For

Isoprene is one of the most abundant naturally emitted
hydrocarbons in the troposphere with a globally av-
eraged emission of 450 Tg a21 [1]. In general, on a
global scale, the emission of biogenic hydrocarbons
exceeds the emission of nonmethane hydrocarbons
with anthropogenic origin, 90 Tg a21 [2]. Thus, bio-
genic hydrocarbons, in particular isoprene, plays an
Correspondence to: T. Berndt
Contract grant Sponsor: Deutsche Forschungsgemeinschaft
International Journal of Chemical Kinetics, Vol. 29, 755– 765 (1997)
q 1997 John Wiley & Sons, Inc. CCC 0538-8066/97/100755-11
the initiation of the isoprene degradation process the
reactions with OH radicals, O3 , and NO3 radicals have
to be considered. Because of the fact that isoprene is
predominantly emitted by vegetation during daylight
hours the reaction with OH radicals should represent
a main degradation pathway, at least at daytime. In
field measurements, also at night, isoprene was de-
tected in considerable amounts [3] and therefore, the
night-time reaction initiated by NO3 radicals should
contribute significantly to the degradation of isoprene.
The determination of the rate constant of the reac-
tion of NO3 radicals toward isoprene was the subject short
of several investigations using different methods. A standard
long
JCK(Wiley)
756 BERNDT AND BÖGE
compilation is given in [4]. The overall uncertainty of
the rate constant at 298 K was estimated to be of a
factor of two demanding improvements.
Organic nitrates were identified as products of the
reaction of NO3 radicals with isoprene and 4-nitroxy-
3-methyl-but-2-enal represents the main component of
the product distribution [5 – 8].
2
O2NO
1 4
O NO3 1 trans-butene !: products
3
isoprene (with numbering 4-nitroxy-3-methyl-but-2-enal
of the carbon atoms)
The formation of this product must be discussed as a
result of a 1,4-addition (the first number presents the
position of the NO3 attack and the second number the
position for the O2 addition according to the given
numbering of the carbon atoms). Products of a 1,2-
addition, methyl vinyl ketone (MVK), and a 4,3-ad-
dition, methacrolein (MACR), were found in subor-
dinate yields, 0.035 for each [8]. However, in the
reaction of OH radicals and O3 with isoprene MVK
and MACR are formed with considerable yields [9].
Furthermore, in the reaction of NO3 radicals with mon-
oalkenes unsubstituted carbonyls are regarded as main
products formed after the break of the former double
bond which was attacked by the NO3 radicals [10,11].
The subject of this work is to determine the rate
constant for the reaction of NO3 radicals with isoprene
and to carry out comprehensive product studies in or-
der to get information about the reaction products
which can be expected under atmospheric conditions.
Special attention is given to the fate of the produced
peroxy radicals.
EXPERIMENTAL
Rate Constant NO3 1 Isoprene
For the determination of the rate constant a relative
rate method was used. The experimental setup was
equal to that described previously [12,13]. The exper-
iments were performed in a 2.13 cm i.d. quartz flow-
tube at 298 K. NO3 radicals have been produced in a
thermal prereactor located in a side tube by thermal
decomposition of N2O5 at ca. 400 K.
N2O5 1 M !: NO3 1 NO2 1 M (1)
At this temperature the reverse reaction is negligible.
The mixture of the organics, isoprene and trans-butene
as the reference substance, was introduced into the
flow tube through a moveable inlet. Typical initial
BATCH
concentrations for the organics were (4.3 – 6.1) 3 1012
molecule cm23. The yield of reacted isoprene was in
the range 21 – 71% and for trans-butene, 9.2 – 50%. N2
was used as the carrier gas at a total pressure of 6.8
mbar. The flow velocity varied from 2.8 to 5.5 m s21.
The following reaction pathways are considered
NO3 1 isoprene !: products (2)
(3)
and the ratio of the rate constants is given by:
k2 ln([isoprene]0 /[isoprene]t )
5 (I)
k 3 ln([trans-butene]0 /[trans-butene]t)
Concentrations have been obtained without NO3 rad-
ical production in the side tube, index “0,” as well as
with NO3 radical production, index “t.” The detection
unit served a GC – FID equipment (HP 5890) which
was directly connected with the flow tube by a vacuum
system. In order to terminate all radical processes, NO
was added to the gas stream of the transfer line to the
GC. The desired amounts of consumed reactants were
achieved by variation of the N2O5 flow through the
thermal prereactor and so by variation of the initial
NO3 radical concentration.
Product Studies
The equipment for the study of the product distribution
consisted of the same main components as mentioned
above. A detailed description is given in [14]. In con-
trast to the equipment for the determination of rate
constants, for GC analysis a GC – MS/FID system (HP
5890 with HP – MSD 5971) was used. For on-line FT –
IR detection, a 2050 cm3 cell with a White mirror
system (optical path length of 10 m) was attached to
the flow tube downstream the port for the GC sam-
pling. The FT – IR analysis was carried out by a Nic-
olet spectrometer (Magna 750) with a MCT detector
in the spectral range 1000 – 4000 cm21 by coadding of
200 scans and an instrumental resolution of 8 cm21.
Spectra were recorded when either only the N2O5 flow
was switched on and the thermal prereactor was cold
or all flows (N2O5 and isoprene) were set and the pre-
reactor was hot. In the resulting difference spectrum,
consumed N2O5 appeared as negative bands and all
products as positive bands. Furthermore, a mass se-
lective detector (HP – MSD 5971) connected to the
flow tube by means of an uncoated deactivated column
served as an on-line MS monitor. Spectra were re-
corded in the 70 eV electron impact mode. short
Isoprene and all reaction products with the excep- standard
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NO3 RADICALS WITH ISOPRENE 757

tion of the organic nitrates were analyzed with GC 2-chloro-3-methyl-but-3-enyl-acetate with sodium hy-
methods. Absolute calibrations were performed for droxide [17]. 4-Nitroxy-but-2-enal was prepared by
isoprene (6 10%), methyl vinyl ketone (MVK) bromination of 1-ethoxy-buta-1,3-diene [18] with N-
(6 10.4%), and 2-methyl-2-vinyl-oxirane (6 9.8%) bromosuccinimide in ethanol, treatment of the formed
using GC – FID, experimental uncertainties are given 1,1-diethoxy-4-bromo-but-2-ene [19] with silver ni-
in the brackets. For structurally similar compounds, trate in acetonitrile and liberation of the aldehyde with
methacrolein (MACR) and MVK as well as 2-(1- tartaric acid. The synthesis of 3-methyl-furan and 2-
methyl-vinyl)oxirane and 2-methyl-2-vinyl-oxirane, methyl-2-vinyl-oxirane are described elsewhere
the same response factors were used. The response [13,12]. Isoprene, methyl vinyl ketone, and meth-
factor of 3-methylfuran (MF) was determined with re- acrolein were commercially available (Aldrich). The
spect to the absolute calibration for isoprene according gases used had stated purities as follows: N2
to the method of “effective carbon number” [15]. (99.999%) and He (99.999%), Linde; and O2
Within the experimental errors, the response factors of (99.9995%) and NO (99.5%), Messer Griesheim.
MVK, MACR, and the oxiranes were in reasonable
agreement with those obtained with the “effective car-
bon number” method with respect to the absolute cal-
ibration for isoprene. The identification of all products RESULTS AND DISCUSSION
was achieved by their mass spectra and the retention
time of authentic samples. From the FT – IR analysis, Rate Constant NO3 1 Isoprene
the concentrations of N2O5 , NO2 , and organic nitrates According to eq. (I), the experimental data are given
were monitored by absorption peaks at 1246, 1629, in Figure 1. The plot shows a reasonable linearity, the
and 1284 cm21, respectively. An averaged cross sec- axis intercept is slightly positive but within two stan-
tion for the organic nitrates, s 5 (6.4 6 1.4) 3 10219 dard deviations of zero. The least-squares analysis
cm2 molecule21 (base 10), was taken from [6]. Be- yields a rate constant ratio k2/k3 5 1.76 6 0.14. Error
cause of insufficient sensitivity, formaldehyde could given represents two standard deviations. Using k3 5
not be determined with the desired precision using the 3.90 3 10213 cm3 molecule21 s21 with an overall un-
present equipment. Product yields were obtained with
respect to reacted isoprene. If isoprene was used in
excess (experiments with NO) the product yields were
obtained with respect to consumed NO3 radicals which
were derived from consumed N2O5 .
Reactions were conducted in the pressure range
6.8 – 100 mbar using He, N2 , or N2 /O2 mixtures as the
carrier gas. Initial isoprene concentrations were (7.1 –
8.7) 3 1012 molecule cm23 if product yields were de-
termined with respect to reacted isoprene or 9.3 3 1014
molecule cm23 if isoprene was used in excess. Initial
concentrations of NO3 radicals varied in the range
(2.0 – 10.8) 3 1012 molecule cm23. Flow velocities
varied from 0.74 to 1.33 m s21. Reaction conditions
were chosen so that the point for the GC-sampling the
disappearance of the NO3 radicals was complete with
$ 99%.

Chemicals
N2O5 was prepared according to the method of David-
son et al. [16] by adding NO to a stream of about 7%
ozone in oxygen. The product was trapped at dry-ice
temperature and purified by subsequent trap-to-trap
sublimation under a continuous stream of ozone/oxy-
gen. 2-(1-methyl-vinyl)oxirane was synthesized from Figure 1 Plot according eq. (I) for the gas-phase reaction
3-methyl-but-2-enyl-acetate by chlorination with hy- of NO3 radicals with isoprene using trans-butene as the ref- short
pochlorous acid followed by treatment of the formed erence substance. standard
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JCK(Wiley) INTERACTIVE

758 BERNDT AND BÖGE

Table I Summary of Rate Constants for the Gas-Phase Reaction of NO3 Radicals with Isoprene Available in the
Literature and Obtained in the Present Study. SC: Smog Chamber, FT: Flow Tube, R: Relative Method, MS: Mass
Spectrometry, and LIF: Laser Induced Fluorescence
k2 [cm3 molecule21 s21] T[K] Technique Reference
(5.94 6 0.16) 3 10 213
295 6 1 SC–R Atkinson et al. [20,4]
(1.3 6 0.14) 3 10212 298 FT– MS Benter and Schindler [21]
(6.52 6 0.78) 3 10213 297 FT– LIF Dlugokencky and Howard [22]
(1.2 6 0.2) 3 10212 298 6 2 SC–R Barnes et al. [6]
(7.8 6 0.62) 3 10213 298 FT– MS Wille et al. [23]
Recommended value
6.78 3 10213 298 Atkinson [4]
(6.86 6 2.60) 3 10213 298 FT– R This study

certainty of 6 30% from [4], the obtained rate constant signed to 3-methylfuran (MF) and 2-(1-methyl-vi-
ratio can be placed on an absolute basis and it follows nyl)oxirane appeared.
k2 5 (6.86 6 2.60) 3 10213 cm3 molecule21 s21. In
Table I a summary is given for gas-phase rate con- O O
stants of the reaction of NO3 radicals with isoprene
from the literature together with the value obtained in 2-methyl-2-vinyl-oxirane 2-(1-methyl-vinyl)oxirane
this study. Using the relative method (R) under smog
Furthermore, in the presence of O2 , methyl vinyl ke-
chamber conditions (SC), the rate constants were
tone (MVK) was found in traces. Figure 2 shows de-
found in the range (5.94 2 12) 3 10213 cm3 mole-
tected oxirane yields with respect to converted iso-
cule21 s21. Approximately the same range, (6.53 2 13)
prene observed in He as well as in N2 using GC – FID.
3 10213 cm3 molecule21 s21, is covered if the rate con-
Added O2 did not influence the oxirane yields. The
stants were determined under flow tube conditions
concentrations of 2-(1-methyl-vinyl)oxirane were near
(FT) with the absolute method using mass spectrom-
etry (MS) or laser-induced fluorescence (LIF). There
is no obvious dependence of the magnitude of the rate
constant on experimental conditions or on the method
of determination. No reasons can be given for the dis-
crepancies. Atkinson [4] recommended a value of 6.78
3 10213 cm3 molecule21 s21 determined from a Ar-
rhenius expression (T 5 251 – 381 K) using absolute
rate constants by Dlugokencky and Howard [22]. The
value obtained in this study is in an excellent agree-
ment with this recommendation.

PRODUCT STUDIES

Formation of 2-Methyl-2-Vinyl-Oxirane and

2-(1-Methyl-Vinyl)Oxirane
First, a direct MS investigation was performed at a
total pressure of 20 mbar in He. Spectra were recorded
in the range 50 – 100 amu. Product peaks appeared at
m/z 5 53, 55, 56, 69, 83, and 84 being in reasonable
agreement with the reference spectrum of 2-methyl-2-
vinyl-oxirane. This result was confirmed by GC – MS
studies at 20 mbar in N2 in the absence as well as in
the presence of O2 (3.6 3 1017 molecule cm23). In each Figure 2 Observed oxirane yields (2-methyl-2-vinyl-oxi-
case, a strong signal attributed to 2-methyl-2-vinyl- rane and 2-(1-methyl-vinyl)-oxirane) in dependence on total short
oxirane was detected. In addition, weak signals as- pressure; carrier gases: He, N2 ; GC– FID analysis. standard
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JCK(Wiley) BATCH

NO3 RADICALS WITH ISOPRENE 759

the detection limit of this method and only at P # 20
mbar a determination seems to be serious. From all
available data, an averaged oxirane ratio [2-methyl-
2-vinyl-oxirane]/[2-(1-methyl-vinyl)oxirane] 5 5.34
6 1.02 can be given. The observed pressure depen-
dence of the oxirane yields can be described by a
model by Olzmann et al. [24]. Using this treatment,
the pressure dependence of the product distribution is
given by a competition between collisional stabiliza-
tion (k st ) and decomposition (k dec ) for the chemically
activated adduct radical formed after addition of NO3
radicals to isoprene. In principle, with increasing total
pressure the concentration of the carrier gas M in-
creases and the stabilization step ([M]k st ) becomes
more important in comparison to the decomposition
step (k dec). NO3 radicals should predominantly attack
isoprene in 1- and in 4-position. In each case, an ad-
duct radical with allylic structure is formed, while ad-
dition in 2- or 3-position yields adduct radicals without
resonance stabilization. The following reaction pattern
is considered:

NO3 1
ka kb

O2NO * *
ONO2
kdec a [M], kst a [M], kst b kdec b

O O
1NO2 O2NO 1NO2
ONO2

The asterisk stands for the chemically activated adduct

radical. As shown in Figure 2, if He was used as the
carrier gas, the detected yields of both oxiranes were
significant higher in comparison to N2 . He is a less
efficient collider than the more efficient N2 and {kdec /
([M] kst )}He . {k dec /([M]k st )}N2 for each pathway a
and b. The knowledge of the ratio (k dec a /k sta )/(k dec b /
k st b ) is necessary to determine the ratio k a/k b from
measured oxirane ratios. Under modified experimental
conditions further information was derived allowing
an approximate determination of k a/kb as pointed out
in a later section. Finally, it is to be noted that under
tropospheric conditions the oxirane formation is neg-
ligible.

Formation of Organic Nitrates

Using FT – IR spectroscopy, the formation of organic
nitrates observed indicated by absorption at 1284 cm21
and 1666 cm21. Figure 3 represents typical spectra re-
corded at a total pressure of 100 mbar in pure N2 as
well as with [O2 ] 5 1.09 3 1018 molecule cm23; [iso-
prene]0 5 7.3 3 1012 molecule cm23, reacted isoprene
ca. 35%. Negative bands arising from reacted N2O5
were compensated by addition of the spectrum of the
Figure 3 Typical FT–IR spectra recorded using pure N2
reference substance. In contradiction to the observa- as carrier gas as well as with [O2 ] 5 1.09 3 1018 molecule
tions of Barnes et al. [6] and Skov et al. [7], in the cm23. Negative bands arising from reacted N2O5 are com-
presence of O2 , no indication for the formation of per- pensated: P 5 100 mbar; [isoprene]0 5 7.3 3 1012 molecule
oxynitrates was found. This fact is probably caused by cm23; and reacted isoprene ca. 35%. The spectrum recorded short
a much lower concentration level of all reactants, es- in pure N2 has been displaced vertically 0.0045 units. standard
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JCK(Wiley)
760 BERNDT AND BÖGE
pecially NO2 , in our experiments. Using [O2 ] $ 1015
molecule cm23, a band located at 1717 cm21 appeared
and with increasing O2 amount up to ca. 1016 molecule
cm23, the band intensity grew in the same way as the
band intensity of the organic nitrates was going down.
Further addition of O2 did not show an effect. The
position of this band is typical for an absorption of an
a,b-unsaturated carbonylic substance. Taking into ac-
count that the attack of NO3 radicals predominantly
takes place in the 1-position, as pointed out later, 4-
nitroxy-3-methyl-but-2-enal has to represent a main
product. This observation is in full agreement with the
results of Skov et al. [7]. As a result of our experiments
at 100 mbar with [O2] $ 1016 molecule cm23, a nitrate
yield of ca. 0.9 with respect to reacted isoprene was
found. An attempt to prepare an authentic sample of
O2NO
k24a [O2], k 4a
O2NO
O2
The reaction of this radical with O2 results in the for-
mation of a tertiary peroxy radical via reaction (4a) or
a primary peroxy radical via reaction (4b). If the cor-
responding reverse reactions (2 4a) and (2 4b) pro-
ceed with relevant rate an establishment of an equilib-
rium each has to been taken into account as observed
in the reaction of allyl radicals C3 H5 with O2 [25,26].
Under the experimental conditions employed, the self-
reaction of formed peroxy radicals should be favored,
NO was absent and the reaction with NO3 radicals
should be of minor importance. The self-reaction of
primary peroxy radicals is much faster in comparison
to tertiary peroxy radicals [27], for instance:
k(CH3O2 1 CH3O2 )/k(t-C4 H9O2 1 t-C4H9O2 ) ca.
12000. Therefore, the self reaction of primary peroxy
radicals from pathway (4b) should be the most impor-
tant loss process in this system. The cross reaction,
k(CH3O2 1 CH3O2 )/k(t-C4H9O2 1 CH3O2 ) ca. 120
[27], should not be significant. This consideration as-
sumes that allylperoxy radicals show the same behav-
ior as described for nonallylperoxy radicals. Accord-
ingly, with a dominance of pathway (5) the formation
of 4-nitroxy-3-methyl-but-2-enal as a main product
can be explained. Concerning pathway (5), Skov et al.
[7] as well as Kwok et al. [8] discussed the formation
BATCH
4-nitroxy-3-methyl-but-2-enal was not successful.
From the FT – IR spectrum of the structurally identical
4-nitroxy-but-2-enal the ratio of absorptions due to the
nitrate group and the carbonylic group was determined
being in a reasonable agreement with the ratio of these
absorptions from our product spectra.
On the other hand, if the attack of NO3 radicals in
4-position is considered, the formation of 4-nitroxy-2-
methyl-but-2-enal as well as 4-nitroxy-2-methyl-but-
1-en-3-one is possible. A contribution of signals of
these substances to the observed absorptions can not
be ruled out. For the discussion of the path-
ways leading to the detected main product, further re-
actions of the collisionally stabilized adduct radical
from the attack of NO3 radicals in 1-position are con-
sidered:
k24b [O2], k4b
O2NO
O2
self
k5 reaction
O2NO 1 (xHO2)
O
of the corresponding oxy radical as a intermediate re-
acting immediately with O2 forming HO2 and the ob-
served 4-nitroxy-3-methyl-but-2-enal. The occurrence
of this oxy radical as a product of pathway (5) under
different experimental conditions of this study is dis-
cussed later.
Products of the attack of NO3 radicals toward iso-
prene in 4-position and the consecutive reaction with
O2 are a secondary peroxy radical after 4,3-addition
and a primary peroxy radical after 4,1-addition and the
formation of 4-nitroxy-2-methyl-but-1-en-3-one and
4-nitroxy-2-methyl-but-2-enal, respectively, is pos-
sible.
Product Formation in the Presence of NO
All experiments were performed at a total pressure of
100 mbar with [O2 ] 5 1.09 3 1017 molecule cm23;
isoprene was used in excess (9.3 3 1014 molecule
cm23) and product yields were obtained with respect
to consumed NO3 radicals. It was assumed that each
removed N2O5 produced one NO3 radical and wall loss
processes as well as the reaction with NO2 were neg-
ligible. In this way, the stoichiometry D[N2O5 ]/D [iso- short
prene] 5 1 : 1 follows. By consideration of simulta- standard
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JCK(Wiley) BATCH

NO3 RADICALS WITH ISOPRENE 761

neous measurements of the disappearance of N2O5 and

the organics (1,3-cyclohexadiene, furan) under com-
parable conditions in former studies [14,28], this treat-
ment appears to be justified. Two sets of reactions
were conducted:
Set A: NO was added together with isoprene
through the inlet. Figure 4 represents the observed
product yields in dependence on added NO; [NO3 ]0 5
(9.5 2 10.8) 3 1012 molecule cm23. It is clearly shown
that with increasing NO content in the gas mixture the
nitrate yield, mainly 4-nitroxy-3-methyl-but-2-enal,
decreased and instead of it methyl vinyl ketone
(MVK) as the main product as well as 3-methylfuran
(MF) and methacrolein (MACR) in minor amounts
were identified. MVK is the product from a 1,2-addi-
tion,
NO
O2NO 2NO2
O2NO
O2 O
O
1 CH2O 1 NO2 (6)

MACR from a 4,3-addition Figure 4 Product yields in dependence on initial NO con-

centration if NO was added together with isoprene through
the inlet.
NO
ONO2 2NO2
ONO2
O2 O

O be a product of an 1,4-addition via reaction (8). This

1 CH2O 1 NO2 (7)
and MF can be discussed as a product from a 1,4- or
4,1-addition; for example, 1,4-addition:
NO
O2NO 2NO2
O2
O2NO
O the corresponding oxy radicals as intermediate prod-
1 NO2 1 H2O (8)
O an aldehyde from the corresponding peroxy radical
Elementary steps leading to the formation of MF are
uncertain. In [29] a mechanism for the formation of
MF from the analogous reaction of OH radicals with
isoprene is proposed. As mentioned in an earlier sec-
tion MF was also detected in the absence of NO in-
dependent on O2 concentration with a yield # 0.04.
However, in the presence of NO, a further pathway
exists forming MF via the corresponding oxy radical
after 1,4- or 4,1-addition. Taking into account that the
primary attack of NO3 radicals predominantly takes
place in 1-position, as pointed out later, the addition-
ally formed MF in the presence of NO should mainly
opens the question, if oxy radicals are produced in the
absence of NO in significant amounts from the self-
reaction (5) MF should be formed in very high yields
under this experimental condition. Unlike this, MF
was only observed in traces. Two possible explana-
tions can be discussed: (i) The formation of the organic
nitrate, 4-nitroxy-3-methyl-but-2-enal, as a result of
the self-reaction (5) does not proceed with a release of
ucts. The elementary steps leading to 4-nitroxy-3-
methyl-but-2-enal are uncertain. To our knowledge, in
the literature there is no example for the formation of
with a yield of ca. 0.9 in a direct way and: (ii) In the
reaction of the peroxy radical with NO in reaction (8)
as well as in the self-reaction (5) the corresponding
oxy radical is formed, but with a different amount of
excess energy. The reaction of the peroxy radicals with
NO is more exothermic, D H 300(RO2 1 NO : RO 1
NO2 ) 2 D H 300(RO2 : RO 1 0.5 O2 ) 5 2 13.7 kcal
mol21 [30]. It is possible that for oxy radicals with a
higher amount of excess energy a decomposition step
is favored in competition with collisional stabilization.
The oxy radicals formed as an intermediate in reaction short
(8) are more excited than those from the self-reaction standard
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JCK(Wiley) BATCH

762 BERNDT AND BÖGE

(5) and a decomposition step can initiate the formation

of MF in reaction (8). Whereas, the oxy radicals from
the self-reaction (5) are close to the ground state or
collisional stabilization is dominant and so the pre-
dominant fate is the reaction with O2 forming 4-ni-
troxy-3-methyl-but-2-enal and HO2 . Wallington et al.
[31] investigated the reactions of CF3CFHO radicals
in the presence of O2 . It was observed that the decom-
position of CF3CFHO radicals was much more im-
portant than the reaction with O2 when the CF3CFHO
radicals were generated via the reaction CF3CFHO2 1
NO than when they were generated via the self-reac-
tion of CF3CFHO2 radicals. For the explanation of this
experimental finding, different amounts of excess en-
ergy of the CF3CFHO radicals arising from the differ-
ent formation pathways are given.
If NO is added to the reaction gas in the initial state
of the reaction, in competition to the reaction with per-
oxy radicals, the reaction of NO with NO3 radicals has
to be considered describing an additional loss process
for NO3 radicals.

NO 1 NO3 !: 2 NO2 (9)
As pointed out in the beginning of this section, these
experiments were conducted with an excess of iso-
prene and product yields were obtained with respect
to consumed NO3 radicals. However, if reaction (9)
plays a significant role, from the measured product
concentrations only lower limits for the product yields
can be obtained. With initial concentrations of
[NO]0 5 9.9 3 1012 molecule cm23 and [isoprene]0 5
9.3 3 1014 molecule cm23, a ratio of the initial reaction
rates r20/r90 5 2.5 follows, k 2 5 6.86 3 10213 cm3
molecule21 s21 from this study and k9 5 2.6 3 10211
cm3 molecule21 s21 from [4]. Using this simple treat-
ment, only ca. 70% of the NO3 radicals should react
with isoprene. If even in the beginning of the reaction
further loss processes for NO are significant (RO2 1
NO : RO 1 NO2 ), more than 70% of the NO3 rad-
icals have to react with isoprene. Product yields at
[NO]0 5 9.9 3 1012 molecule cm23 (nitrate: 0.47 6
0.1, MVK: 0.26 6 0.03, MF: 0.085 6 0.01, MACR:
0.035 6 0.005, 2-methyl-2-vinyl-oxirane: 0.04 6
0.005) amounted to a C-balance of 0.89 6 0.15. The
given errors were obtained from the corresponding un-
certainties of the GC response factors and the cross
section in the FT – IR analysis. The found C-balance
indicates that a interference from reaction (9) was not
so critical using [NO]0 # 1013 molecule cm23. Because
of the relatively high uncertainties of the product
yields, especially for the organic nitrate, it is impos-
sible to decide if interferences from other reactions
influence the product yields.
Figure 5 Yields of NO2 (attributed to the reaction RO2 1
NO : RO 1 NO2 ) and nitrates (mainly 4-nitroxy-3-methyl-
but-2-enal) in dependence on initial NO concentration if NO
was added after completeness of NO3 radical consumption
at t 5 39 ms.
Set B: Using isoprene in excess (9.3 3 1014 mole-
cule cm23), the NO3 radical consumption via reaction
(2) is complete with . 99% after 10 ms. In this set of
experiments, NO was added by means of a capillary
after the completeness of reaction (2); t NO addition 5 20 –
49 ms, [NO3 ]0 5 (6.4 – 6.8) 3 1012 molecule cm23.
Figures 5 and 6 show detected product yields in de-
pendence on added NO with tNO addition 5 39 ms. After
NO addition, for peroxy radicals there is a competition
between the self-reaction via reaction (5) and the re-
action with NO forming the corresponding oxy radi-
cals and consequently the stable oxidation products
MVK, MF, and MACR via reaction (6), (8), and (7),
respectively. Consequently, with increasing amounts
of added NO the yield of the nitrates, mainly 4-ni-
troxy-3-methyl-but-2-enal, decreased up to a constant
value. A further increase of added NO did not show
an effect, (cf, Fig. 5). The remaining nitrates were
mainly attributed to reaction (5) proceeding up to the
point of NO addition. This interpretation was proven
by variation of the time of NO addition; [NO] 5 (4.6 –
5.4) 3 1013 molecule cm23, t NO addition 5 20 and 49 ms
with nitrate yields of 0.17 and 0.36, respectively.
Yields of NO2 formed via RO2 1 NO : RO 1 NO2 short
were determined from the N-balance. standard
long
JCK(Wiley) BATCH

NO3 RADICALS WITH ISOPRENE 763

HO2 1 NO !: OH 1 NO2 (10)

radicals and so a OH/isoprene chain reaction was ini-

Figure 6 Yields of MVK, MF, MACR, and oxirane (2-
methyl-2-vinyl-oxirane) in dependence on initial NO con-
centration if NO was added after completeness of NO3 rad-
ical consumption at t 5 39 ms.
[NO2 ]from NO 5 [NO2 ]total
2 (2 D[N2O5 ] 2 [nitrate]) (II)
In the absence of NO additions, observed products
(NO2 and nitrates) fulfilled the N-balance with
104.5 6 6.6% confirming this approach. As shown in
Figure 5, with increasing NO additions increased the
yield of NO2 being due to the reaction of NO with RO2
radicals but no saturation level was found. That indi-
cates that HO2 radicals probably were formed via re-
action (5) taking place up to the point of NO addition.
HO2 radicals reacted with NO forming OH
tiated representing an additional pathway for the for-
mation of NO2 , MVK, MF, and MACR [9]. This fact
is shown in Figure 6. After the strong rise of the prod-
uct yields arising predominantly from the NO3 radical
reaction up to [NO] ca. 2.5 3 1013 molecule cm23,
further increase of the NO additions yielded a slight
rise attributed tentatively to the OH/isoprene reaction.
In Figure 6, yields for 2-methyl-2-vinyl-oxirane (oxi-
rane) are also given, indicating that the oxirane for-
mation was not affected by added NO as expected
from the pathways leading to the oxiranes.
A determination of product yields from the NO3
radical reaction with isoprene, if peroxy radicals were
mainly converted via RO2 1 NO : RO 1 NO2 , at
[NO] ca. 2.5 3 1013 molecule cm23 seems to be useful.
Under these conditions, the interference from the OH /
isoprene reaction should be unimportant. Table II
compiles the product yields together with the result
from set A at [NO] 5 9.9 3 1012 molecule cm23. Ex-
periments with variable times of NO additions gave
reasons for the assumption that the formation of ni-
trates is of minor importance if the dominant fate of
the peroxy radicals is the reaction with NO. The result
of an extrapolation for nitrate yield 5 0 is enclosed in
Table II. Given C-balances were obtained with the as-
sumption that for each MVK and MACR one formal-
dehyde was formed. The extrapolation for nitrate
yield 5 0 places the results of both sets of the exper-
iment on a comparable basis. Resulting product yields
were found to be in a reasonable agreement. Therefore,
the following yields can be given; MVK: 0.51, MF:
0.17 – 0.18, MACR: 0.07 – 0.10, 2-methyl-2-vinyl-ox-
irane: 0.04, resulting in a C-balance of 0.79 – 0.83 with
a uncertainty of ca. 10% each. The agreement of the
results of both sets of the experiments indicates that
the influence of reaction (9) in the experiments of set
A was of minor importance.

Table II Product Yields Obtained from Set A: NO (9.9 3 1012 molecule cm23) was Introduced Together with
Isoprene, Set B: NO (2.5 3 1013 molecule cm23) was Added after Completeness of NO3 Radical Consumption, t 5
39 ms. Oxirane Stands for 2-Methyl-2-Vinyl-Oxirane. The Given Errors were Obtained from the Corresponding
Uncertainties of the GC Response Factors and the Cross Section in the FT–IR Analysis
Set A Extrapolation Nitrate 5 0 Set B Extrapolation Nitrate 5 0
MVK 0.26 6 0.03 0.51 6 0.05 0.36 6 0.04 0.51 6 0.05
MF 0.085 6 0.01 0.17 6 0.015 0.13 6 0.015 0.18 6 0.02
MACR 0.035 6 0.005 0.07 6 0.01 0.07 6 0.01 0.10 6 0.01
Oxirane 0.04 6 0.005 0.04 6 0.005 0.04 6 0.005 0.04 6 0.005
Nitrate 0.47 6 0.1 – 0.28 6 0.06 –
short
C-balance 0.89 6 0.15 0.79 6 0.08 0.88 6 0.13 0.83 6 0.085
standard
long
JCK(Wiley)
764 BERNDT AND BÖGE
A rough estimate for the ratio of the rate constants
ka/kb for the primary attack of NO3 radicals toward
isoprene in 1- and in 4-position was performed using
the ratio of the product yields of MVK (1,2-product)
and MACR (4,3-product) and the assumption MVK/
MACR 5 MFfrom 1,4-addition /MFfrom 4,1-addition. As pointed
out in an earlier section, under the used conditions
(100 mbar), the decomposition of chemically activated
adduct radicals is negligible. Therefore, a determina-
tion of ka/kb from the oxidation products seems to be
feasible. From both sets of experiments follows: ka/kb
5 5.1 – 7.4. However, the C-balance was found to be
incomplete. Other to date unknown products can in-
fluence this result. Skov et al. [7] reported a ratio
ka/kb 5 3.5 whose is in disagreement with the value
presented here.
It is to be noted that in general the NO2 concentra-
tions calculated via eq. (II) were about twice as high
as the sum of the concentrations of MVK, MF, and
MACR. Taking into consideration the formation path-
ways for these species via reaction (6), (8), and (7),
respectively, a 1 : 1 correlation was expected. Obvi-
ously, there were other peroxy radicals in addition to
those being necessary for the formation of the ob-
served main products MVK, MF, and MACR. A pos-
sible contribution from the oxidation of NO by O2 in
the homogeneous phase as well as at the walls was
checked under the present experimental conditions and
can be ruled out. The interference from the OH/iso-
prene reaction is too small in order to explain this dis-
crepancy.
APPLICATION TO THE TROPOSPHERE
The experiments of this study showed that the product
distribution from the reaction of NO3 radicals toward
isoprene is strongly dependent on the pathways of
formed peroxy radicals. Under conditions of the real
troposphere, reactions with NO, NO3 , HO2 , and all
available peroxy radicals as methylperoxy radicals
(CH3O2 ) or acetylperoxy radicals (CH3C(O)O2 ) in-
cluding the self-reaction have to been taken into con-
sideration. A compilation of rate constants for reac-
tions of a series of peroxy radicals till then is given in
[27]. From recently published works, also data for the
self-reaction of allylperoxy radicals and the reaction
with HO2 , CH3O2 , and C2 H5O2 are available [32,33].
Furthermore, rate constants for the reaction of NO3
radicals with CH3O2 and C2 H5O2 were obtained indi-
cating that this pathway represents an additional
source of the corresponding oxy radicals at night-time
[34,35].
For produced peroxy radicals from the reaction of
BATCH
NO3 radicals with isoprene, in [7] an attempt is made
to estimate the lifetimes with respect to the above men-
tioned pathways under tropospheric conditions. Ac-
cording to it, the reaction with NO3 radicals via
RO2 1 NO3 !: RO 1 NO2 1 O2 (11)
was found to be dominant. This result was confirmed
by a modeling study by Kirchner and Stockwell [36].
In the considered scenarios, for all types of peroxy
radicals, the reaction with NO3 radicals via reaction
(11) was the main loss process.
The used equipment is not suitable to conduct the
reaction with an excess of NO3 radicals, necessary for
the initiation of reaction (11). The reaction with NO
produces the corresponding oxy radicals in the same
way as the NO3 radical reaction via
RO2 1 NO !: RO 1 NO2 . (12)
If the rate constants of the reactions of NO3 radicals
with the various C5-peroxy radicals are nearly equal
as found for the reaction with NO [32], an application
of our experimental results to conditions, in which re-
action (11) is dominant, seems to be possible and
MVK, MF, and MACR should represent main prod-
ucts.
It is to be noted, reaction (12) is more exothermic
than reaction (11), D H 300(RO2 1 NO : RO 1 NO2 )
2 D H 300(RO2 1 NO3 : RO 1 NO2 1 O2 ) 5 2 5.8
kcal mol21 [30]. According to a different excess en-
ergy, the fate of oxy radicals and finally the product
distribution can be influenced by the way of formation
of the oxy radicals, as pointed out by Wallington et al.
[31].
Under tropospheric conditions, the formation of ox-
iranes in this system is negligible.
The financial support of the Deutsche Forschungsgemein-
schaft is gratefully acknowledged. The authors thank I. Kind
for carrying out the experiments for the determination of the
rate constant.
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