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temverature
dependence
oftheratecoefficient
isthengiven
byk(100-400
K) = 1.84x 10-3
7'78
exp-(1014+13_96
/ T)cm3molecule
' s-.Whenk(T)isextrapolated
to 180-220
K, thereis
excellentagreementwith thevaluepredictedfrom atmospheric
modelsof thenighttimeNa
layer.Hencethismeasurement
has,to a first order,demonstrated
closureof the neutral
chemistrygovemingthe undersideof theNa layerabove80 km.
Ager and Howard [1987] were not able to observethis
1. Introduction
anupper
limittotheratecoefficient
ofk4(300
K)< 2 x 10-2
spcctromctry,respectively),the mcsosphcricchemistryof
sodiumhas had to bc unraveledthrough laboratorykinetic
studies of elementary reactions, coupled with modeling.
Significantprogresshasbeenmadeoverthe pastdecade,with
models that arc now able to reproducethe characteristic
featuresof the Na layer remarkablywell, over a range of
latitudesand seasons
[Helmerand Plane, 1993;McNeil et al.,
1995;Plane et al., 1998, 1999].
Thesemodelspredictthatbelow the peak of the Na layer at
about 90 km, the major sodium reservoir is sodium
bicarbonate (NaHCO3), formed through the following
sequence
of reactions:
above 80 km.
cm3molecule
- s-. Indeed,sodium
models[e.g.,Planeet al.,
1999] requirereaction(4) to be slow at mesospheric
temperatures,
but withinlimits,so thatNaHCO3providesa
Na+ ionscanbc observed
(by lidarandrocket-borne
mass temporaryreservoirratherthan a permanentsink for Na
Na + 03 -- NaO + 02
(1)
(2)
(3)
(4)
2. Experimental technique
Reaction (4) was studied by reacting NaHCO3 under
pseudo-first-order
conditionsin a known excessof atomicH,
using the stainlesssteel flow tube illustrated in Figure 1.
NaHCO3 was producedin situ via a sequenceof reactions.
Atomic Na vaporwas first entrainedin a flow of N2 from the
heatpipe oven and enteredthe flow tube (internaldiameterof
36.9 mm) at a point 600 mm upstreamof the spectroscopic
Copyright2001by theAmericanGeophysical
Union.
Papernumber2000JD900579.
0148-0227/01/2000JD900579509.00
1733
1734
I Sodium
I
Lamp
] Pump
Beam
Chopper
41 __l
N2 flow
Sodium
Oven II
Oat
oppr
Valve !iii)._ii'+
ll: insulation
fi_.
li Movable
Injector
i ]
N Bath NO H
Gas inlet
CO, CO.
NO
Temp
Pressure,
NO
QuadrupoleMass
Spectrometer
Figure 1. Schematicdrawing(approximatelyto scale)of the fast flow tube employedto studythe reaction
betweenNaHCO3 andH (PMT, photomultipliertube).
+0 , .............
CO2injoeted
H (+CO)injoeted
[ ...... I..................
lo+9
1735
Na
and diffusion
coefficients
listed
parameter
;2,thesumofthesquared
differences
between
the
10+$
0.000
0.010
0.015
Reaction time
0.020
/ s
Figure2. Modelsimulation
of the variationof sodium 3d, and8 showedno systematicdeviationasin Figure3a.
k4(307
K) = (5.2+ 2.5)x 10-3cm3molecule
-s- andk4(227
K) = (1.7+ 0.6)x10'13cm3 molecule
- s-,wherethequoted
uncertainty
in thereaction
timetrcac,
andthe;2valuesfrom
the model fit. The uncertaintyin the H atom concentration
was a significant componentof the propagatederror. On
average,this was 23%, althoughit ranged from 7 to 58%,
dependingon experimentalconditions.The final result is
OH + OH --> H20 + O
OH + O
--> 02
+ H
OH + H2 --> H20 + H.
(7)
(8)
4. Theoretical
(9)
(10)
Calculations
NaHCO3
+ H -->Na+ H20+ CO2 AH0
= -27.9kJmol' (4')
-->NaCO3
+ H2
/kH0
= +3.8kJmol- (4")
AH0
=+4.1kJmol'. (4"')
thendetermined
by usinghybriddensityfunctional/HartreeFock B3LYP theorywith the high-level6-31l+G(2d,p) basis
set (which has both polarizationand diffusefunctionsadded
to the atoms). Figure4 illustratesthesegeometriesand their
respective
energybarriers(includingzero-pointenergies
).
This showsthat the pathwayto produceNa + H2CO3,
downthelengthof thetube. Whena flow of atomicH (and althoughessentiallythermoneutral
within the expected
CO) was switchedon, a small sodiumsignal ([Na].) was uncertainty
of +8 kJ mol' at the CBS-Qlevelof theory
recorded. The ratio [Na]./[Na]0 was then measuredas a [Foresman and Frisch, 1996], has the lowest barrier.
functionof [H] to produceonedataset;thewholeprocesswas Furthermore,the expectederrorusingB3LYP/6-31l+G(2d,p)
then repeatedat a different injector distance(or reaction theory
is +13kJmol- [Foresman
andFrisch,1996],sothat
time).
the energybarriersof channelsin Figures4a and4b aremuch
An approximateanalytical solutionof the kinetics due to too high within this uncertaintyfor these channelsto be
gasphasereactionsand wall lossesshows that for a fixed significantlyopen at the low temperatures
consideredhere
1736
0.00
Model
Experiment
'
-0.01
-0.01
-0.02
'
-0.03
,-
-0.02
!
-0.03
b,
a,
-0.04
-0.04
le+13
2e+13
3e+13
le+13
4e+13
3e+13
[H] atomcm
[H] atomcm
0.00
0.00
2e+13
-3
-3
-0.01
--
-0.02
-0.03
.. -0.01
.Z, -0.02
-0.04
'
-0.03 d,
-0.05
le+13
2e+13
3e+13
[H]atom
cm
-3
5e+12
le+13
[H]atom
cm
-3
(kHloss)
andreaction
time(t)' (a)kmoss
= 598s-1,t = 0.018s; (b)kmos,
= 497s-,t = 0.011s; (c) kmo,,
= 391
-1
s , t = 0.014s; (d)kmo,s
= 598s-1,t = 0.013s. Errorbarsareshown
onlyin Figure3aforthesakeof clarity.
(notethatif the Figure4b channelwere open,thenthiswould
not be observedin our experimentunlessNaCO3reactedwith
H to regenerateNa, rather than recombiningto yield
NaHCO3). TST was then appliedto the Figure4c channelby
using the molecularparameterslisted in Table 2, together
with a correctionfor tunneling of H throughthe reaction
barher,assumed
to be a symmetricalEckartbarher[Steinfeld
et al., 1989].
5. Discussion
RateCoefficienta
Source
2.8x 1040exp
(-1590/T)
NaO
2.0 x 10-l
1.1x 10-9exp(-1100/T)
1.1x 10-9exp(-1400/T)
1
1
2.0 x 1040
1.3x 10-27
(200/r)
1.9x 10-28
(200/r)
1.9x 10-3exp(-840/T)
1.26x 10-exp(-7600/T)
152x (300/T)
4'8s
141x (300/T)
4.8s
134x (300/T)4.8s
120x (300/T)
4'8s
1
1
3
4
5
5
6
7
+ H --> Na+OH
--> HCO+M
H + N20 --> OH + N2
Diffusion
of Na
Diffusion
of NaO
Diffusion
of NaOH
Diffusion of NaHCO3
aUnits:bimolecularreactions,cm3 molecule
' s'l; termolecular
reactions,cm
molecule
-2s4;diffusion
coefficients,
torrcm2s4.
bSources:
1, PlaneandHelrner[1994]; 2, Kolbet al. [1992]; 3, Warnatz
[1984]; 4, Hanson and Salirnian [1984]; 5, Measuredusing the techniqueof
Helmer and Plane [1993]; 6, measuredby using the photolysisof NaOH as a
spectroscopic
marker; 7, calculatedfrom gas kinetictheory [Helrnerand Plane,
1993] by usinga theoreticaldipolemomentfor NaHCO3 of 6.9 debye[Rajasekhar
and Plane, 1993].
(a)
1737
Temperature/ K
30O
200
.'
150
Tranlition
State
Theor
le-13
(b)
Experiment
le-14
-_...... /
. Mod.
el.[7la.
neeta,.,
19,99],...".'"",%.
0.003
AE#0-30.6kJmo1-1
(c)
0.004
0.005
0.006
0.007
Temperature-1
/ K-1
Figure 5. Arrhenius plot for the reaction NaHCO3 + H,
illustratingthe experimentalpoints from the presentstudyat
227 and 307 K, transition state theory fitted to the
experimentalpoints (solid line) with upper and lower limits
(dashedlines), and model predictionsof the rate coefficient
fromthe seasonal
behaviorof thesodiumlayerat 40N[Plane
et al., 1999] and during Januaryat the SouthPole [Plane et
al., 1998].
Table 2. Calculated
MolecularParameters
at theB3LYP/6-31l+G(2d,p)Levelof Theory
Molecule
Rotational
Constants,Vibrational
Frequencies,
cm4
GHz
NaHCO3
H2CO3
NaHCO3 + H -->
Na + H2CO3
transition state
112,248,333,570,581,700,833,1008,1237,
1389,1659,3802
522,548,595,602,800,975,1156,1298,
1817,3800,3802
387i, 85,106,249,329,557,593,679,822,
1018,1232,1383,1638,3789
1459,
910,
1738
110
I
105
Lidar measurement
100
,.
..
<
Model (bestfit)
95
Model
(lower
limit
to
k4)
90
85
Model(upperlimittok4)
8O
1000
2000
3000
4000
5000
Na concentration/cm
'3
Figure6. Verticalprofilesof thenighttime
annualaverage
Na layerat 40N: lidarmeasurements
at UrbanaChampaign(Illinois)andFort Collins(Colorado)[Planeet al., 1999](thicksolidline) compared
with model
predictionsusingthe temperature-dependent
expression
for k4(thin solidline) and upper/lowerlimits to k4
(dashedlines)from equation(11).
Now,
however, we
have used a
laser
photofragmentation
technique[Rajasekharet al., 1989] to
measurethe NaHCO3 photolysiscrosssectionto yield Na.
The onsetof photolysisoccursat wavelengthsbelow 240 nm,
providinga significantalternativepathwayto reaction(4) for
converting NaHCO3 to Na during daylight.
The
photodissociation
coefficient
(JNaCO3
1 x 104S'z) is large
Pa., 1998.
enoughto reducethe value of k4 at 140 K requiredin the
Hanson, R. K., and S. Salimian, Survey of rate constantsin the
model,thusremovingthe discrepancy
in Figure5.
N/H/O system, in CombustionChemistryedited by W. C.
Figure6 illustratesthe sensitivityof a sodiummodel[Plane
GardinerJr., Springer-Verlag,
New York, 1984.
et al., 1999] to the uncertaintyin k4. The modelwas usedto Helmer,M., andJ. M. C. Plane,A studyof the reactionNaO2+ O -
calculate
themonthlynighttimeNa layerat 40N,fromwhich
16,855, 1995
(Colorado),bothat closeto 40N[Planeet al., 1999]. This Plane, J. M. C., The chemistryof meteoriticmetalsin the upper
atmosphere,
Int. Rev.Phys.Chern.,1O,55-106, 1991.
Plane,J. M. C., and M. Helmer, Laboratorystudiesof the chemistry
of meteoricmetals, Researchin ChemicalKinetics, vol. 2, edited
by R. G. Comptonand G. Hancock,ElsevierSci., New York,
1994.
R. M.
1739