J. Phys. Chem.

1996, 100, 19911-19916 19911

Kinetics and Products of the Gas-Phase Reaction of SO3 with Water

Edward R. Lovejoy,* David R. Hanson, and L. Gregory Huey

NOAA Aeronomy Laboratory, 325 Broadway, Boulder, Colorado 80303
ReceiVed: August 8, 1996; In Final Form: October 7, 1996X

The kinetics of the gas-phase reactions of SO3 with H2O and D2O were studied over the temperature range
250-360 K in N2 with a laminar flow reactor coupled to a chemical ionization mass spectrometer. The SO3
loss is second order in the water concentration, is independent of pressure (20-80 Torr N2, 300 K), and has
a strong negative temperature dependence and a significant H/D isotope effect (kH2O 2kD2O). The yield of
sulfuric acid is 1.0 ( 0.5 per SO3 consumed. These observations are consistent with the rapid association of
SO3 and H2O to form the adduct H2OSO3 which reacts with water to produce sulfuric acid. The first-order
rate coefficients for loss of SO3 by reaction with H2O and D2O are given by kI(s-1) ) (2.26 ( 0.85) 10-43T
exp((6544 ( 106)/T)[H2O]2 and (9.45 ( 2.68) 10-44T exp((6573 ( 82)/T)[D2O]2, where T K and [H2O,
D2O] molecule cm-3. The errors are the uncertainty at the 95% confidence level for precision only. Analysis
of the temperature dependence of the SO3 loss yields an upper limit for the H2O-SO3 bond enthalpy of 13
kcal mol-1.

Introduction
The gas-phase atmospheric oxidation of sulfur dioxide
produces sulfur trioxide:1-3
OH + SO2 + M f HOSO2 + M
HOSO2 + O2 f HO2 + SO3
The dominant atmospheric loss process for SO3 is reaction with
gas-phase water:
SO3 + H2O ff H2SO4
Sulfuric acid is an important precursor for atmospheric aerosol.4
SO3 also reacts efficiently with ammonia, producing a stable
adduct:5,6
SO3 + NH3 + M f H3NSO3 + M
It is possible that despite the low atmospheric NH3 concentra-
tions, H3NSO3 may play a role in particle formation because of
its very low vapor pressure and strong affinity for sulfuric acid.5
The reaction of SO3 with water has been studied extensively.
Castleman et al.7 performed fast-flow experiments with mass
spectrometric detection of SO3 and reported a second-order rate
coefficient of 9 10-13 cm3 molecule-1 s-1. Subsequent
calculations by Holland and Castleman8 suggested that SO3
forms an adduct with water:
SO3 + H2O + M f H2OSO3 + M
which isomerizes efficiently to H2SO4:
H2OSO3 + M f H2SO4 + M
Chen and Plummer9 applied a higher level of theory to the
SO3/H2O system and also concluded that the reaction of SO3
and water forms a relatively stable adduct H2OSO3, but found
that the isomerization of the adduct to H2SO4 is inhibited by a
* To whom correspondence should be addressed.
Also affiliated with Cooperative Institute for Research in Environmental
Sciences, University of Colorado, Boulder, CO 80309.
X Abstract published in AdVance ACS Abstracts, November 15, 1996.
S0022-3654(96)02414-8 CCC: $12.00
barrier. They postulated that the simple reaction of SO3 and
one water molecule to form H2SO4 is unlikely. Molecular beam
experiments by Hofmann-Sievert and Castleman10 demonstrated
that H2SO4 is a product of the reaction of SO3 with water
(1) clusters. Wang et al.11 studied the gas-phase kinetics of SO3
+ H2O by using a flow reactor with photofragment emission
(2) detection of SO3. They measured an upper limit of 6 10-15
cm3 molecule-1 s-1 for the bimolecular rate coefficient in 1-10
Torr of He at room temperature and concluded that the earlier
kinetic studies were influenced by heterogeneous chemistry. A
smaller upper limit of 2.4 10-15 cm3 molecule-1 s-1 was
(3) measured in 85 Torr of air subsequently by Reiner and Arnold12
using a flow reactor coupled to a chemical ionization mass
spectrometer. In a more detailed study, Reiner and Arnold13
report a pressure independent (23-195 Torr air) bimolecular
rate coefficient of (1.2 ( 0.2) 10-15 cm3 molecule-1 s-1 at
room temperature.
(4)
Recent high level theoretical studies by Hofmann and
Schleyer14 and Morokuma and Muruguma15 indicate that H2-
OSO3 is bound by about 8 kcal mol-1 relative to SO3 + H2O,
and the isomerization of the H2OSO3 adduct to sulfuric acid is
inhibited by a very large barrier (19 (ref 14) and 24 kcal mol-1
(ref 15) above SO3 + H2O). Morokuma and Muruguma15 find
that more facile paths to sulfuric acid exist when SO3 interacts
with two water molecules:
SO3 + (H2O)2 f H2SO4 + H2O (7)
(5) H2OSO3 + H2O f H2SO4 + H2O (8)
Their calculations suggest that the reaction with the water
(6) dimer (7) proceeds without a barrier, and the reaction of H2-
OSO3 with water (8) is inhibited by a small barrier of about 5
kcal mol-1. Morokuma and Muguruma15 also predict that the
(H2O)2SO3 species is bound by about 6 kcal mol-1 relative to
H2OSO3 + H2O but is separated from H2SO4 + H2O by a barrier
of about 10 kcal mol-1.
Recently Kolb et al.16 studied the SO3 + H2O reaction with
an atmospheric pressure turbulent flow reactor coupled to a
chemical ionization mass spectrometer. They report that the
loss of SO3 is second order in the water concentration and
1996 American Chemical Society
19912 J. Phys. Chem., Vol. 100, No. 51, 1996
increases significantly (>10 times) as the temperature is lowered
from 333 to 243 K. Kolb et al.16 postulate that a significant
fraction of the SO3 loss likely involves reaction with the water
dimer (reaction 7).
Matrix isolation studies have identified IR absorptions due
to the H2OSO3 complex.17-19 Bondybey and English18 report
that the complex is stable with respect to isomerization to H2-
SO4 at 5 K in a Ne matrix. From observed isotope shifts,
Schriver et al.19 conclude that the complexation involves charge
transfer with an O-S interaction. Phillips et al.20 have recently
measured the microwave spectrum of the H2OSO3 species in
the gas phase and obtained accurate stuctural information which
is in good agreement with the predictions of ab initio theory.14
Despite considerable theoretical and experimental effort, the
details of the mechanism of the reaction of SO3 and water are
still not resolved. In this work, measurements of the first-order
rate coefficient for the loss of SO3 in excess H2O and D2O as
a function of temperature (250-360 K, 50 Torr N2) and pressure
(20-80 Torr of N2 at 300 K) are presented. The SO3 loss is
second order in water concentration and has a strong negative
temperature dependence, little pressure dependence, and a
significant H/D isotope effect. These results are consistent with
the rapid formation of an H2OSO3 adduct (reaction 5) followed
by a slower reaction of the adduct with water (reaction 8) to
produce sulfuric acid. The implications of these results to the
understanding of the atmospheric chemistry of SO3 are dis-
cussed.
Experimental Section
The kinetics of the SO3 + H2O reaction were studied by
measuring the concentration of SO3 at the exit of a high-pressure
laminar flow reactor as a function of the contact distance with
water vapor. SO3 was detected in the reactor effluent by
chemical ionization mass spectrometry (CIMS).
The flow reactor was a jacketed Pyrex cylinder with an
internal diameter of 3.1 cm and a length of 50 cm. Temperature-
regulated methanol (T < 270 K) or ethylene glycol (T > 270
K) was circulated through the jacket to regulate the reactor
temperature. The main carrier gas N2 was added with water at
the upstream end of the reactor. Typical N2 flows were about
20 STP cm3 s-1 (STP ) 273 K and 760 Torr) and the pressure
ranged from 20 to 80 Torr, giving, for example, an average
flow velocity of about 45 cm s-1 at 50 Torr and 300 K. The
entrance and mixing lengths21 were about 10 cm, and the
Reynolds number was about 40. Water was introduced into
the reactor by flowing N2 through a bubbler containing liquid
H2O or D2O. The bubbler was immersed in a water bath to
stabilize the temperature. The pressure was measured at the
exit of the bubbler with a capacitance manometer. The water
flow rate was calculated by assuming that the N2 leaving the
bubbler was saturated with water. Saturation was confirmed
by observing that the CIMS H2O signal was proportional to
the calculated water flow rate. The water-saturated N2 stream
passed through a Teflon membrane filter to remove particles
and mixed with the main N2 flow before entering the reactor.
The reactor pressure and temperature were measured in the
middle of the reaction zone with a capacitance manometer and
glass encased thermocouple, respectively. All of the flow
reactor effluent entered the CIMS through a Teflon fitting
equipped with a variable orifice to control the reactor pressure.
SO3 was added to the reactor through a movable inlet (0.25
in. o.d. Pyrex) which entered the upstream end of the reactor
on axis. SO3 was generated at the end of the inlet by passing
Lovejoy et al.
SO2 and O2 over a red-hot Nichrome filament (0.004 in.
diameter) fixed about 0.5 cm from the exit of the inlet. Typical
inlet flow rates were about 0.003 STP cm3 s-1 of SO2 and 0.1-
0.5 STP cm3 s-1 of O2. An aluminum cylinder (about 3 cm
long by 3 cm diameter) with a series of longitudinal passages
for gas transit was attached to the end of the inlet to enhance
the conduction of heat from the filament to the reactor walls.
Typically, 0.5-1 W was dissipated by the filament. With the
Al radiator in place, the hot filament caused < 3 C temperature
drop along the length of the reaction zone. The largest
temperature drops occurred for the lowest reaction temperatures.
The formation of aerosol in the reactor was examined by
measuring aerosol in the reactor effluent with an expansion
counter.22 For the conditions used in the present study no
aerosol was detected in the reactor effluent (<200 particle cm-3,
r < 0.1 m). These observations place an upper limit of 0.002
s-1 on the first-order rate coefficient for SO3 loss on aerosol,
which is significantly less than the measured rate coefficients.
The chemical ionization mass spectrometer used in the present
study has been described in detail previously.23 SO3 was
detected by the rapid fluoride transfer reaction with SiF5-:5,24
SiF5- + SO3 f FSO3- + SiF4 (9)
The high stability of the reagent ion SiF5- and the product
ion FSO3- allowed for operation of the ion-molecule reactor
at elevated pressure, which enhanced the sensitivity of the
detector. In the present study the ion-molecule reactor was
operated at about 5 Torr with a He flow rate of about 110 STP
cm3 s-1. For these conditions the SO3/SiF5- reaction time was
on the order of 0.1 s giving SO3 detection limits (s/n 1 for 1
s integration) of about 105 molecules cm-3 in the ion-molecule
reactor or 5 106 molecules cm-3 in the SO3/H2O reactor at
50 Torr pressure. In the present study, the initial (z ) 0 cm)
SO3 concentration in the neutral reactor was typically about 109
molecules cm-3. At these levels, secondary chemistry involving
SO3 reaction products is negligible. The maximum possible
first-order loss rate coefficient due to secondary chemistry is
about 0.1 s-1 (109 molecule cm-3 10-10 cm3 molecule-1 s-1)
which is significantly smaller than the values measured in the
present study.
Water was detected as the cluster ion with SiF5-:
SiF5- + H2O + M f SiF5-H2O + M (10)
SiF5- was generated by the rapid fluoride-transfer reaction
with SF6-:
SF6- + SiF4 f SiF5- + SF5 (11)
and SF6- was generated by the reaction of SF6 with thermal
electrons produced with a hot thoriated iridium filament.
Sulfuric acid and SO3 were detected by reactions with
BF4-BF3
BF4-BF3 + H2SO4 f BF4-H2SO4 + BF3 (12)
BF4-BF3 + SO3 f FSO3-BF3 + BF3 (13)
BF4-BF3 was generated by fluoride transfer from SF6- to
BF3:
SF6- + BF3 f BF4- + SF5 (14)
followed by clustering of BF4- with BF3:
Gas-Phase Reaction of SO3 with Water J. Phys. Chem., Vol. 100, No. 51, 1996 19913

BF4- + BF3 + M f BF4-BF3 + M (15)

SO3 reacted rapidly with BF4- to give FSO3-, which places

the fluoride affinity of SO3 at or above the fluoride affinity of
BF3, contrary to the accepted ordering.25
H2SO4 and SO3 were also detected by reaction with NO3-
HNO3:13,26

NO3-HNO3 + H2SO4 f HSO4-HNO3 + HNO3 (16)

NO3-HNO3 + SO3 f NO3-SO3 + HNO3 (17)

NO3-HNO3 was generated by the reaction of HNO3 with

SF6-:23

SF6- + HNO3 f NO3-HF + SF5 (18)

NO3-HF + HNO3 f NO3-HNO3 + HF (19)

Figure 1. FSO3- signal as a function of the reaction distance for a
Ultrahigh-purity N2 (99.9995%) and O2 (99.99%) were used range of [H2O] in 50 Torr of N2 at 330 K. [H2O] ) 0.0, 0.51, 1.03,
1.75, and 2.36 1016 molecules cm-3. A background signal of 18 Hz
for the reactor flows and for preparing mixtures of SO2
was subtracted from the data.
(99.98%). CIMS measurements (reaction 10) indicated that the
isotopic purity of the D2O sample (100 D2O/(D2O + HDO
+ H2O) was >90%.

Results and Discussion

The variation of the SO3 signal as a function of reaction
distance and water concentration at 330 K is shown in Figure
1. The first-order rate coefficient for loss of SO3 was derived
from the measured decays by employing the Brown27 algorithm
and using an SO3/N2 diffusion coefficient5 of 87(T/295 K)1.9
cm2 Torr s-1. The first-order decay of SO3 was independent
(<10% change) of the concentrations of SO2 (factor of 5
changes at 255 and 300 K) and SO3 (factor of 5 change at 255
K and a factor of 10 change at 300 K). The first-order rate
coefficients for SO3 loss are plotted in Figure 2 as a function
of H2O and D2O for a range of temperatures.
The first-order rate coefficient for loss of SO3 increases
nonlinearly with the concentration of water. Measurements of
the loss of SO3 in the presence of ammonia confirmed that the
first-order rate coefficient for SO3 loss in the presence of excess
NH3 increases linearly with NH3 concentration as observed
previously.5 Therefore, the curvature observed in the water data
is probably not due to systematic errors in the present
experimental procedure. Kolb et al.16 have observed similar
nonlinear behavior for the water reaction. They proposed that
a significant fraction of the SO3 is lost by reaction with the
water dimer (reaction 7). In this case, the SO3 loss rate can be
approximated by

d[SO3] Figure 2. First-order rate coefficient for SO3 loss in 50 Torr N2 as a

) -k7Kd[H2O]2[SO3] (20)
dt
where k7 is the second-order rate coefficient for reaction of SO3
with the water dimer and Kd is the equilibrium constant for water
dimerization. This equation is based on the assumption that
the water dimer is in equilibrium with the water monomer.
Equation 20 predicts an effective first-order rate coefficient for
SO3 loss in excess H2O given by
kI ) k7Kd[H2O]2 (21)
and a temperature dependence determined by the sum of the
activation energy for the SO3 + (H2O)2 reaction and the enthalpy
of water dimerization. In the present work, a strong negative
function of (a, top) [H2O] and (b, bottom) [D2O] for a range of
temperatures. The solid lines are fits of the data to kI ) DT exp(C/T)-
[H2O,D2O]2. The dotted lines are individual fits to kI ) B[H2O,D2O]2.
temperature dependence associated with an activation energy
of -13 kcal mol-1 was observed. The enthalpy of formation
of the water dimer is about - 4 kcal mol-1,28,29 which requires
the SO3 + (H2O)2 reaction to have an activation energy of -9
kcal mol-1. Such a large negative activation energy is not
physically reasonable for an elementary bimolecular reaction.
It is possible that the SO3 + (H2O)2 reaction is not a simple
elementary reaction and proceeds via the (H2O)2SO3 complex.
However, the contribution of the water dimer mechanism is
probably small because an SO3 + (H2O)2 rate coefficient (k7)
19914 J. Phys. Chem., Vol. 100, No. 51, 1996 Lovejoy et al.

of about 20 times the gas kinetic value is required to reproduce

the SO3 loss observed at 253 K in the present study. Even at
300 K, k7 must be approximately equal to the gas kinetic value
to reproduce the observed SO3 loss. This would be highly
unusual for a reaction which has a six-center transition state.15
The quadratic dependence of the SO3 loss on [H2O], and the
large negative temperature dependence are consistent with the
formation of the H2OSO3 adduct followed by reaction of the
adduct with water (reactions 5 and 8). For this mechanism,
the strong negative temperature dependence can be attributed
mostly to the enthalpy of adduct formation (reaction 5).
The kinetic data were analyzed based on the mechanism of
H2OSO3 adduct formation followed by adduct-water reaction
(reactions 5 and 8). When the adduct equilibration is much Figure 3. Summary of the energetics of the SO3 + H2O + H2O system.
more rapid than the adduct reaction with water, the first-order Enthalpies are estimated from the present study and calculated with
tabulated values (asterisk).30
losses of SO3 and H2OSO3 at times longer than the equilibration
time are given by

k8Ka[H2O]2
kI ) (22)
1 + Ka[H2O]

where k8 is the second-order rate coefficient for the reaction of

H2OSO3 with H2O and Ka is the equilibrium constant for H2-
OSO3 formation. The temperature dependencies of k8 and Ka
are expressed as

k8 ) Ae-Ea/RT (23)

Ka ) 1.362 10-22Te-G/RT ) 1.362 10-22TeS/Re-H/RT

(24)
where the units of Ka are cm3 molecule-1 and G is the Gibbs
free energy change for H2OSO3 adduct formation (G ) H
- TS).
The temperature-dependent kI data for H2O and D2O were
fit to eq 22 to determine values for A, Ea, and H. The entropy
changes for H2OSO3 and D2OSO3 formation from SO3 + H2O
and D2O were fixed at -0.027 kcal mol-1 K-1 based on the
Hofmann and Schleyer14 value for the entropy of H2OSO3, and
tabulated values30 for the entropies of SO3 and H2O. The best
fits were achieved with H + Ea ) -13 kcal mol-1 and H >
-11 kcal mol-1, which indicates that for the conditions of the
present study only a small fraction of the SO3 is tied up as H2-
OSO3 (i.e., Ka[H2O] , 1). In this case eq 22 reduces to kI
k8Ka[H2O]2, and the temperature dependence is given by the
exponential of the sum H + Ea. Fits of the data to this
simplified expression gave kI(s-1) ) (2.26 ( 0.85) 10-43T
exp((6544 ( 106)/T)[H2O]2 and (9.45 ( 2.68) 10-44T exp-
((6573 ( 82)/T)[D2O]2 where T K and [H2O, D2O]
molecules cm-3. The errors are the uncertainty at the 95%
confidence level for precision only. The fits are the solid lines
in Figure 2. These observations suggest an upper limit for
the H2O-SO3 bond enthalpy of about 13 kcal mol-1 which is
consistent with the recent ab initio values from Hofmann and
Schleyer14 and Morokuma and Muguruma15 (about 8 kcal
mol-1). It should be noted that the Morokuma and Muguruma
calculation underestimates the stability of H2SO4 by 8 kcal
mol-1 whereas Hofmann and Schleyer are within 2 kcal mol-1
of the accepted experimental value.
In the context of the proposed mechanism, the -13 kcal
mol-1 activation energy is the sum of the enthalpy of H2-
OSO3 formation from SO3 + H2O and the activation energy of
the H2OSO3 + H2O reaction. The limit on the H2O-SO3 bond
enthalpy then also implies a limit on the activation energy for
the reaction of the H2OSO3 adduct with water of Ea < 0 kcal
mol-1. This value contradicts the theoretical results of Moro-
Figure 4. k8Ka/T as a function of 1/T. H2O (filled circles), D2O (filled
squares), Kolb et al.16 (open circle).
kuma and Muguruma,15 which predict a 5 kcal mol-1 barrier.
A small negative activation energy would suggest that the
reaction H2OSO3 + H2O f H2SO4 + H2O is not a simple
elementary bimolecular reaction but may involve a weakly
bound intermediate such as (H2O)2SO3 (see Figure 3). It is
possible that there is significant tunneling involved in this
reaction which may explain why the experimental barrier is
significantly lower than that predicted by ab initio methods.
Preexponential factors (A, eq 23) of 1.3 10-15 cm3
molecule-1 s-1 for the H2OSO3 + H2O reaction and 5.5 10-16
cm3 molecule-1 s-1 for the D2OSO3 + D2O reaction are
calculated from the fit results and the entropy changes for H2-
OSO3 and D2OSO3 formation (-0.027 kcal mol-1 K-1, see
discussion above). The preexponential factors are small, which
is consistent with the highly constrained six-center transition
state predicted by Morokuma and Muguruma.15
The kI vs [H2O,D2O] data (Figure 2) were also analyzed by
fitting the individual temperature curves to the expression kI )
B[H2O,D2O]2, and then plotting the logarithm of B/T vs 1/T to
determine H + Ea from the slope. The dashed lines in Figure
2a and b are the individual fits to kI ) B[H2O,D2O]2, and log-
(B/T) are plotted vs 1/T in Figure 4. This analysis yields kI(s-1)
) 3.95 10-43T exp(6397/T)[H2O]2 and 8.15 10-44T exp-
(6619/T)[D2O]2 where T K and [H2O,D2O] molecules
cm-3.
To quantify the possible contribution of the water dimer
reaction 7, the data were also fit to the expression kI ) (a1T
exp(c/T) + a2T exp(2013/T))[H2O]2 , which assumes that there
are two parallel reaction channels, one with an effective
activation energy of -4 kcal mol-1 (the H2O dimerization
enthalpy28,29). This expression fit the data as well as the one
Gas-Phase Reaction of SO3 with Water
Figure 5. First-order rate coefficient for SO3 loss as a function of
[H2O] at 300 K in 20 (squares), 40 (triangles), and 80 Torr N2 (circles).
channel expression, and indicated that a -4 kcal mol-1 channel
could contribute 0.2% at 250 K, 4% at 300 K, and 30% at 360
K.
The variation of the first-order loss of SO3 due to H2O at
300 K as a function of pressure is shown in Figure 5. The
first-order SO3 loss at 300 K changed by less than 10% over
the pressure range 20-80 Torr N2. Reiner and Arnold13 also
reported no significant pressure dependence for the SO3 loss
over the range 23-195 Torr of air. The lack of pressure
dependence is consistent with the assumption that the SO3 +
H2O T H2OSO3 equilibration is rapid relative to the H2OSO3
loss by reaction with water, so that the rate-limiting step is a
pressure-independent reaction of H2OSO3 with water. On the
basis of the lack of a pressure dependence, a lower limit of 1
10-14 cm3 molecule-1 s-1 can be assigned to the rate
coefficient for the association reaction of SO3 and H2O in 20
Torr N2 at 300 K (reaction 5). This is consistent with the rapid
association observed for SO3 and NH3 (k ) 2 10-12 cm3
molecule-1 s-1 in 20 Torr of N2 at 295 K).5
The present measurements of the first-order rate coefficient
for loss of SO3 due to reaction with H2O in 50 Torr of N2
interpolated to 295 K are about 5 times smaller than the values
measured by Kolb et al.16 at 295 K and atmospheric pressure
(see Figure 4). This discrepancy is probably not due to a
pressure effect since in the present work the first-order loss
increased by less than 10% for a factor of 4 increase in pressure.
This weak pressure dependence has also been documented by
Reiner and Arnold.13 The first-order SO3 rate coefficients
measured in the present work are in good agreement with the
Reiner and Arnold13 data. For example, at 298 K with [H2O]
) (1-10) 1015 molecules cm-3, the present work predicts
effective bimolecular rate coefficients of (0.2-2) 10-15 cm3
molecule-1 s-1 which encompass the value measured by Reiner
and Arnold13 for similar water concentrations ((1.2 ( 0.2)
10-15 cm3 molecule-1 s-1 ).
The quadratic dependence of the SO3 loss on [H2O] first
reported by Kolb et al.16 is reproduced in the present study. In
contrast, Reiner and Arnold13 fit their data to a linear [H2O]
dependence. The source of this discrepancy is unknown.
The variation of SO3 and H2SO4 as a function of reaction
distance and [H2O] are shown in Figure 6. The chemical
ionization schemes used in the present work probably do not
distinguish between the isomers H2SO4 and H2OSO3. However,
on the basis of the interpretation of the present measurements,
the fraction of SO3 in the form of the adduct is small ([H2-
OSO3] < 0.25[SO3] at 253 K, <0.01[SO3] at 273 K, etc.).
Additionally, any adduct entering the CIMS will probably
dissociate rapidly and be detected as SO3 due to the large
dilution from the neutral reactor to the flowing afterglow
J. Phys. Chem., Vol. 100, No. 51, 1996 19915
Figure 6. Variation of FSO3-BF3 (filled symbols) and BF4-H2SO4
(open symbols) as a function of reaction distance at 300 K for a range
of [H2O] ) 0 (diamonds), 3.2 (triangles), 6.4 (squares), and 9.7 1015
molecules cm-3 (circles). Background signals (FSO3-BF3 ) 80 Hz
and BF4-H2SO4 ) 1700 Hz) were subtracted from the data. The lines
are fits to the data.
combined with a short adduct lifetime (less than 10 ms in 5
Torr of He). The solid lines in Figure 6 are a fit to the data
based on a simplified mechanism of first-order loss of SO3 to
the wall and to reaction with H2O giving H2SO4. A large
fraction of these data was taken in the mixing region, and it is
not possible to extract kinetic information from these data. At
longer reaction times the alternate SO3 detection schemes
(BF4-BF3, NO3-HNO3) gave kinetic results similar to those
of the SiF5- scheme. The fits to the SO3 loss and H2SO4
appearance yielded an H2SO4 wall loss which was about 60%
of the diffusion-limited value. The fits also yielded a value of
5.9 for the product of the H2SO4 yield and the CIMS detection
sensitivity of H2SO4 relative to SO3. It is likely that BF4-H2SO4
and FSO3-BF3 were in equilibrium with the BF4-BF3, because
of the relatively high levels of BF3. In this case the relative
detection sensitivities are difficult to estimate because the
thermodynamics of ion-molecule reactions 12 and 13 are not
known. Product experiments utilizing the NO3-HNO3 detec-
tion scheme gave essentially identical SO3 loss and H2SO4
appearance profiles as the BF4-BF3 experiments. The
NO3-HNO3 studies gave a product of the H2SO4 yield and the
relative detection sensitivity (H2SO4/SO3) equal to 3.1. In these
experiments the ions were probably not in equilibrium, and the
relative sensitivities should be given to a good approximation
by the ratio of the rate coefficients for the ion molecule detection
reactions (kH2SO4 3.0kSO3),13,24,26 giving an H2SO4 yield of 1.0
( 0.5/SO3 consumed. The uncertainty in the yield reflects the
estimated uncertainty in the relative CIMS sensitivities for H2-
SO4 and SO3. These product results are consistent with the
observations by Reiner and Arnold.13
The first-order loss of SO3 due to reaction with D2O was
approximately 2 times slower than with H2O and exhibited the
same strong negative temperature dependence. These observa-
tions are in accord with the proposed mechanism involving
formation of an H2OSO3 adduct (with a negligible isotope effect)
followed by reaction of the adduct with water (with a significant
primary isotope effect). The large isotope effect for the adduct-
water reaction is consistent with the ab initio six-center transition
state15 in which two O-H bonds are being formed and two
O-H bonds are being broken.
Summary
Measurements of kinetics of the gas-phase reactions of SO3
with H2O and D2O were performed over the temperature range
250-360 K in N2 by varying the contact between SO3 and water
19916 J. Phys. Chem., Vol. 100, No. 51, 1996
in a laminar flow reactor coupled to a chemical ionization mass
spectrometer. Low SO3 concentrations eliminated complications
due to secondary and heterogeneous chemistry. The following
observations regarding the chemistry of the gas-phase reaction
between SO3 and water were quantified: the loss of SO3 is first
order in [SO3], second order in [H2O] and [D2O] and indepen-
dent of pressure (20-80 Torr of N2, 300 K) and has a strong
negative temperature dependence and a significant H/D isotope
effect (kH2O 2kD2O). The yield of sulfuric acid is 1.0 ( 0.5/
SO3 consumed. The present data are consistent with the rapid
association of SO3 and H2O to form the H2OSO3 adduct which
reacts with water to produce sulfuric acid. In the context of
this proposed mechanism, analysis of the temperature depen-
dence of the SO3 loss yields expressions for the first-order rate
coefficient for SO3 loss as a function of temperature, as well as
an upper limit for the H2O-SO3 bond enthalpy of 13 kcal mol-1.
It is also deduced that the H2OSO3 + H2O reaction may have
an apparent negative activation energy consistent with the
formation of an intermediate (H2O)2SO3 complex. The energet-
ics derived from the present study are in reasonable agreement
with recent predictions of ab initio calculations.
Atmospheric Implications
The atmospheric lifetime of SO3 with respect to reaction with
water will be highly variable due to the strong temperature
dependence of the reaction and the quadratic [H2O] dependence.
However, SO3 will generally be short lived throughout the
atmosphere. In the troposphere the SO3 lifetime will be very
short due to high water concentrations (e.g., a lifetime of about
1 10-4 s at 273 K with 2 Torr of H2O). Other SO3 loss
processes will not compete with the water reaction. For
example, the aerosol scavenging lifetime of SO3 in a dense cloud
is greater than 10 s. Steady-state SO3 concentrations will be
very low in the troposphere. Assuming an SO3 production rate
from SO2 oxidation of 2 103 molecules cm-3 s-1 ([SO2] )
2 109 molecules cm-3, [OH] ) 1 106 molecules cm-3,
273 K, k(OH+SO2) 1 10-12 cm-3 molecule-1 s-1 3) yields
a steady-state SO3 concentration of 0.2 molecule cm-3. In the
stratosphere, the SO3 lifetime will be longer because of lower
water levels (e.g., about 100 s for [H2O] ) 5 1012 molecules
cm-3 and 220 K). Aerosol scavenging will generally not be
able to compete (SO3 lifetime of several hours for background
aerosol loadings) with the water reaction in the stratosphere
except for volcanically perturbed conditions (lifetime of hun-
dreds of seconds).
Acknowledgment. The authors acknowledge useful discus-
sions with K. R. Leopold, D. Worsnop, J. T. Jayne, R. Bianco,
Lovejoy et al.
and C. J. Howard. This work was supported in part by the
NOAA Climate and Global Change Program.
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