Geophysical Research Letters
Supporting Information for
HCFC-133a (CF3CH2Cl): OH Rate Coefficient, UV Absorption Spectrum, and Atmospheric
Implications
Max R. McGillen,1,2 François Bernard,1,2 Eric L. Fleming,3,4 and James B. Burkholder,1
1
2
Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric
Administration, Boulder, Colorado, USA.
Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado, USA.
3
NASA Goddard Space Flight Center, Greenbelt, Maryland, USA.
4
Science Systems and Applications, Inc., Lanham, Maryland, USA.
Contents of this file
Figure S1
Tables S1 to S5
Additional Supporting Information (Files uploaded separately)
Caption for Datasets S1
Introduction
This supporting information includes tabulated data used to prepare Figures 1 and 2 in the
manuscript (i.e. rate coefficient data, experimental conditions and UV cross section data),
which is intended for quantitative use or comparisons with any future work. Also included is the
infrared spectrum of HCFC-133a, which was used for calculating radiative efficiency.
1
Figure S1. Infrared spectrum of HCFC-133a (CF3CH2Cl).
2
Table S1.
[OH]0c
[HCFC-133a]d
k' range
(s-1)
k(T)e
5.56
Photolysis
Laser
Fluenceb
1.9
0.3
0.79–14.2
320–760
0.34 ± 0.03
H2O2
6.68
1.9
2.9
0.86–10.1
165–730
0.61 ± 0.02
8.6
H2O2
25.4
1.5
8.5
1.41–12.0
415–1060
0.56 ± 0.05
9.6
H2O2
15.9
1.5
5.4
0.79–10.2
T
(K)
P
(Torr)
v
(cm s-1)
Photolysis
Precursor
233
103
7.8
(CH3)3COOH
253
108
7.3
253
201
253
88
[Source]a
300–850
0.60 ± 0.05
Global k(253 K)
0.59 ± 0.01
274
111
8.1
H2O2
4.83
1.9
2.1
0.86–8.79
150–790
0.81 ± 0.04
296
101
10.9
H2O2
5.09
0.8
0.9
0.65–7.01
140–750
1.00 ± 0.08
296
92
9.6
(CH3)3COOH
11.7
1.5
0.4
0.61–7.55
490–1160
1.00 ± 0.06
296
94
10.5
H2O2
16.4
1.5
5.5
0.57–6.84
335–1000
1.11 ± 0.07
Global k(296 K)
1.10 ± 0.02
375–1470
1.62 ± 0.06
324
100
11.9
H2O2
352
93
13.9
H2O2
15.3
352
198
6.2
H2O2
11.8
379
93
14.1
H2O2
379
52
22.3
379
199
7.0
15.8
1.3
4.6
0.56–5.55
1.3
4.5
0.52–4.76
380–1730
2.23 ± 0.05
1.6
4.2
1.49–7.38
550–2060
2.34 ± 0.03
Global k(352 K)
2.30 ± 0.03
350–2160
3.07 ± 0.09
12.6
1.3
3.7
0.47–4.71
H2O2
21.3
1.6
7.7
0.31–3.97
505–1570
2.86 ± 0.09
H2O2
8.99
1.6
3.2
0.98–6.61
460–2290
3.23 ± 0.05
Global k(379 K)
3.10 ± 0.03
a units of 1013 molecule cm-3, b
units of mJ cm-2 pulse-1, c units of 1010 molecule cm-3 [OH]0 = Precursor cross section at 248 nm x
Precursor OH quantum yield x Laser Fluence, d units of 1016 molecule cm-3, e units of 10-14 cm3 molecule-1 s-1 and quoted
uncertainties are 2σ measurement precision.
Table S1. Experimental conditions and obtained rate coefficients for the OH + CF3H2Cl (HCFC-133a) reaction
1
Table S2.
σ(λ,T) (10-22 cm2 molecule-1)a
Wavelength
(nm)
323 K
294 K
–
184.95
601 ± 25
192.5
319 ± 2
304 ± 8
195
216 ± 2
197.3 ± 0.4
197.5
139.4 ± 0.8
128.7 ± 0.7
200
91.9 ± 0.7
83.8 ± 0.3
202.5
60.4 ± 1.2
53.5 ± 0.3
205
38.8 ± 0.5
33.3 ± 0.3
207.5
24.9 ± 0.2
21.2 ± 0.2
210
15.9 ± 0.1
13.32 ± 0.09
215
7.09 ± 0.05
5.93 ± 0.04
220
3.51 ± 0.04
2.93 ± 0.02
225
1.93 ± 0.04
1.545 ± 0.009
230
0.957 ± 0.019
0.768 ± 0.008
235
0.447 ± 0.022
0.370 ± 0.008
240
0.221 ± 0.016
0.164 ± 0.004
a Quoted uncertainties are 2σ measurement precision.
but was included to represent the precision of the fit.
273 K
253 K
233 K
213 K
–
–
–
–
293 ± 2
271 ± 3
265.0 ± 0.6
262 ± 2
185 ± 1
176 ± 5
166.3 ± 0.8
163 ± 1
121 ± 1
111 ± 2
106.3 ± 0.8
102.8 ± 0.4
76.3 ± 0.7
70.9 ± 0.4
68.3 ± 1.2
65.6 ± 0.5
48.4 ± 0.4
44.4 ± 0.5
43.0 ± 0.3
40.9 ± 0.3
31.0 ± 0.3
28.3 ± 0.2
26.7 ± 0.5
25.2 ± 0.3
18.9 ± 0.3
17.3 ± 0.2
16.2 ± 0.1
15.1 ± 0.3
12.23 ± 0.04
11.1 ± 0.3
10.1 ± 0.2
9.3 ± 0.3
5.07 ± 0.09
4.89 ± 0.08
4.83 ± 0.08
4.0 ± 0.1
2.49 ± 0.03
2.46 ± 0.21
2.42 ± 0.07
2.2 ± 0.2
–
1.370 ± 0.013
1.28 ± 0.06
1.47 ± 0.09
–
–
0.708 ± 0.010
0.618 ± 0.014
–
–
0.323 ± 0.011
0.290 ± 0.015
–
–
–
0.131 ± 0.014
In some cases, the least significant digit may not be statistically significant,
Table S2. UV absorption cross sections, σ(λ,T), for CF3H2Cl (HCFC-133a) measured in this work
2
Table S3.
wavenumber (cm-1)
102.072
180.483
343.569
349.727
519.766
523.553
625.256
787.342
848.642
898.716
1108.06
1153.00
1258.93
1284.93
1343.84
1452.43
3052.12
3121.67
intensity (cm molecule-1)
4.65 × 10-19
2.11 × 10-19
1.81 × 10-19
7.94 × 10-20
2.70 × 10-19
7.96 × 10-19
3.91 × 10-18
3.76 × 10-18
4.08 × 10-18
1.58 × 10-18
1.73 × 10-17
3.99 × 10-17
1.77 × 10-17
2.37 × 10-17
1.56 × 10-17
3.72 × 10-18
1.22 × 10-18
5.48 × 10-21
Table S3. Calculated infrared frequencies made at MP2-6-311G(2d,p), no wavenumber scaling
1
Table S4.
Integrated Band Strength (cm molecule-1)
a
Integration
This worka
Etminan et al., 2014
Range (cm-1)
780–920
(9.08 ± 0.02) × 10-18
9.02 × 10-18
1070–1530
(1.16 ± 0.003) × 10-16
1.12 × 10-16
-18
2970–3010
(1.14 ± 0.003) × 10
–
Quoted uncertainties are 2σ of the measurement precision.
Table S4. Infrared integrated band strengths, S, for CF3CH2Cl at 298 K from this work
(spectrum given in Dataset S1) and the literature.
Table S5:
Lifetime (years)
Radiative efficiency (Wm-2ppb-1)
GWP (20 years)
GWP (100 years)
GWP (500 years)
This work
4.45
0.155a
1317c
378c
115c
Etminan et al. [2014]
4.3
0.15b
1220
340
96
a
Calculated using a parameterized method reported in Hodnebrog et al. [2012].
radiative transfer model (NBM).
c GWPs are for well-mixed gases. The difference between our GWP values and those of
Etminan et al. [2014] is primarily due to our slightly higher radiative efficiency and
longer lifetime.
b Calculated using a narrow-band
Table S5: Atmospheric lifetime and radiative efficiency of HCFC-133a and its GWP over
the 20, 100 and 500 year time horizons. The values from the present work are
compared with those reported by Etminan et al. [2014].
Data Set S1. Infrared spectrum data for HCFC-133a, provided as wavenumber and cross section
(cm2 molecule-1 [base e])
2