Trifluoromethyl sulphur pentafluoride SF5CF3 :

the ultimate greenhouse gas

(Daresbury VUV photochemistry meeting, 11.9.03)

Richard Tuckett
Ray Chim, Clair Atterbury,
Drs Andrew Critchley, Gary Jarvis and Weidong Zhou

Drs Chris Mayhew and Richard Kennedy (Birmingham)

Dr Paul Hatherly, Dan Collins & Prof Keith Codling (Reading)
Staff at the Daresbury and Super-Aco, Paris synchrotron sources

[EPSRC ?]
 Physical and Chemical Properties of Greenhouse Gases

• Must absorb infra-red radiation in the range 5-25 µm (2000 – 400

cm-1). [The molecule must have one or more vibrational modes which
µ / dr is non-zero).]
have a dipole moment derivative ( i.e. dµ
• The amount of CO2 in the troposphere is almost saturated, through
its bending vibrational mode at 15 µm (667 cm-1). Therefore, infrared
absorption needs to occur in regions where CO2 and H2O do not
absorb.

• The greenhouse gas must have a long lifetime in the atmosphere.

(It must not be photodissociated by solar UV radiation in either the
stratosphere (200-300 nm) or the troposphere (300-500 nm). It must
not react with either the OH⋅⋅ free radical or O* atoms.)
• A serious greenhouse gas is one whose concentration is increasing
rapidly due to man’s activity.
 Examples of greenhouse gases,
and their importance to global warming
_________________________________________________________________________

Greenhouse gas CO2 CH4 CF2Cl2 SF5CF3

_________________________________________________________________________

Concentration / ppm 346 1.65 0.0003 < 10-6

∆Conc / % per year 0.4 1.0 5 6

Lifetime / years 100 10 110 ca. 1000

G’house Potential (GHP) 1 32 17000 18000

Contribn to GH effect / % 50 19 10 < 0.1

__________________________________________________________________

The Greenhouse potential (GHP) is quoted on a ‘per molecule’ basis. That is, the effect
on global warming of one molecule of GH gas. Also used is the ‘radiative forcing’ ;
SF5CF3 has the highest of any pollutant greenhouse gas, 0.57 W m-1 ppb-1.
 SF5CF3 : atmospheric background
• Sturges et al. [Science (2000) 289, 611] report observation of
SF5CF3 in the Antarctic. Believed to be anthropogenic.
• IR absorption measurements (Wallington) show it has the
highest radiative forcing per molecule of any greenhouse gas,
0.57 W m-1 ppb-1.
• Current concentrations are low (0.12 ppt), but growing at 6%
per annum
• Stratospheric profiles suggest it is long-lived. The value of the
SF5-CF3 bond strength is important to determine if this
greenhouse gas can be photolysed in the stratosphere. Or, is
the sink route determined by ionic processes in the
mesosphere ?

• Does SF5CF3+ behave as a perturbed SF6+, a perturbed CF4+,

or neither ?
• Measure ∆rHo0 (SF5CF3 → CF3+ + SF5+ e-) using TPEPICO
spectroscopy, as a route to determine the S-C bond strength.
DIE (SF5CF3) = Do0(SF5−CF3) + Adiabatic IE (CF3)
Dissociative Ionisation Energy (DIE) of AB-CD (SF5-CF3) : definition

ABCD+

Eavail
DIE AB+ + CD + e-
ENERGY

ν + Ethermal
hν
AIE (AB)

AB + CD
ABCD Do0 (AB-CD)
0
R (C F 3 -SF 5 )
R (AB-CD)
 Impulsive dissociation of polyatomic ions,
AB-CD+ → AB+ + CD
The impulsive release of energy as a bond breaks predicts a linear
relation between the translational KE release, <KE>T, and the
available energy (axial-recoil approximation) :
µ B,C
< KE > T = .E avail (K.R. Wilson, 1970)
µ AB,CD
Applicable if either fragment is atomic or molecular. At a photon
energy hν, the energy available to products is :

3k BT Ei
E avail = hν − DIE (AB - CD) + +
2 i exp E i −1
k BT
Plot <KE>T vs. hν. Εxtrapolate to the photon energy where <KE>T
is zero, giving DIE (AB-CD). Hence obtain ∆fHo0 (AB+).
 Extrapolation method to determine
dissociative ionisation energy of ABCD
Mean KE release
into AB+ + CD

µB-C / µAB-CD)
Slope = (µ

ν + thermal
[hν
DIE (ABCD AB+ + CD + e-) energy of ABCD]
Multi-purpose coincidence apparatus (Daresbury)
127o Post-analyser

Threshold
Electron
Signal

Channeltron

+2 V
Electron
Lenses +10 V
+10 V
+20 V

+20 V
Paul Hatherly
Monochromatised
Synchrotron (Reading University)
Radiation
Mirror
Quartz
Window
PMT Meas Sci Tech (1992) 3 891
Lens

Sodium
-20 V Salicylate
Window
Filter
PMT Holder -96.5 V
Photoexcitation
Fluorescence Drift Flux Signal
Tube
Signal
-96.5 V
-96.5 V

MCPs

Photo-Ion
Signal
 Results for CF3+ / SF5CF3 :
[J. Phys Chem A (2001) 105, 8403]
1.0 • No parent ion is observed ;
SF5CF3 → SF5 + CF3+ + e- SF5CF3+ behaves as CF4+ and
Mean total KE release / eV

(∆rHo = 12.9 ± 0.4 eV) SF6+. But, lower ionisation

energy than both molecules ;
0.5 HOMO of SF5CF3 is S− − C σ-
bonding orbital.
• Single extropolation over the
complete Franck-Condon region
0.0 of the X state of SF5CF3+ yields :
TPES A DIE (SF5CF3 → CF3+ + SF5 + e-)
Threshold Photoelectron

= 12.9 ± 0.4 eV.

signal / arb. units

X
Do0(SF5−CF3) = 3.9 ± 0.4 eV.
• No excited states of SF5CF3 exist
below 8 eV [EELS, N J Mason,
0 J. Elec. Spec. (2001) 120, 27].
SF5CF3 is not broken down in
12 13 14 15 16 the stratosphere by UV
Photon Energy / eV photolysis. What happens to it ?
 Sink routes for SF5CF3 in the mesosphere (h > 60 km)

No excited states of SF5CF3 below 8 eV (λ = 155 nm), so it is not broken

down in stratosphere by UV photolysis. SF5CF3 must be removed by
reactions with small cations or electrons, or by Lyman-α
photodissociation, in the mesosphere ; such reactions must also produce
a dissociative fragment which is not re-cycled.

Rate = [SF5CF3]. (Σk ion[ion] ) molecules cm

+ ke[e−] + σ121.6J121.6 -3 s-1

( ……. ) is the sum of pseudo-first-order rate constants. Need to know rate

constants, concentrations of ions and electrons, and the solar flux in the
mesosphere.

Also, ideally need to know the products of these reactions to see whether they
remove SF5CF3 from the atmosphere.

Measurement of the products of ion reactions is much more facile than of

neutral reactions.
Selected Ion Flow Tube (SIFT) : D Smith and N G Adams (1980s),
now C A Mayhew et al. (School of Physics, Birmingham)

Determines rate constants and product ions for the reactions

A+ or A− + Β → C+ or C− + D
k has to be faster than ca. 10−12 cm3 molecule-1 s-1
 Typical results from SIFT experiments on SF5CF3
[Phys Chem Chem Phys (2002) 4 2206]
Ion Rate Coefficient Product Ion (/%) Proposed Neutral ∆rHo0
(/10-9 cm3 s-1) Products (/kJmol-1)

N2+ (15.58) 1.6 CF3+ (65) SF5 + N2 -258

[1.4] SF3+ (28) CF4 + F + N2 -248, -289
SF4+ (trace) CF4 + N2 -283, -345
SF4+CF3 (2) F + N2 ?
SF5+ (5) CF3 + N2 -185, -175

N+ (14.53) 2.2 CF3+ (80) SF5 + N -157

[1.9] SF3+ (17) CF4 + F + N -147, -187
SF4+ (trace) CF4 + N -181, -243
SF5+ (3) CF3 + N -84, -73

CO+ 1.6 CF3+ (75) SF5 + CO -107

(14.01) [1.4] SF3+ (22) CF4 + F + CO -96, -137
SF4+ (trace) CF4 + CO -131, -193
SF5+ (3) CF3 + CO -34 (± 43), -23 (± 46)

CO2+ 1.2 CF3+ (76) SF5 + CO2 -84

(13.77) [1.1] SF3+ (14) CF4 + F + CO2 -73, -114
SF4+ (8) CF4 + CO2 -108, -170
SF5+ (2) CF3 + CO2 -11 (± 43), 0 (± 46)
 Glass
Ω Resistors
10 MΩ Cylinder

63Ni
Collector
Source
Gate
1 Bar Buffer &
Sample Flow To MS
“Forward”
Flow

Jarvis et al. Int. J. Mass Spectrom. Ion Processes 205 (2001) 255-272
 −
e + SF5 CF3 → SF5 CF ( - *
3 ) → SF + CF3 -
5
Kennedy and Mayhew, Int. J. Mass Spectrom., (2001) 206, i-iv

kexp(298 K) = (7.7 ± 0.6) × 10-8 cm3 s-1

s-wave capture gives kthermal(298 K) = 3.2 × 10-7 cm3 s-1

-8
8.0x10
Note that the main product is
dissociative, SF5−.
ka (/cm molecule s )
-1 -1

-8
6.0x10

-8
4.0x10
3

-8
2.0x10

0.0
0.0 0.5 1.0 1.5
Mean Electron Energy (/eV)
Vacuum-UV absorption apparatus (SuperAco, Paris)
(H-W. Jochims ; Freie Universitat, Berlin)

Measure cross-sections in the range 10−19 to 10−16 cm2

Beer Lambert Law : I = Io exp(− −σcL)
 Vacuum-UV absorption spectrum of SF5CF3
(Chem. Phys. Letts., (2003) 367, 697)
1.4e-16

1.2e-16
photon resolution = 0.08 nm
Absorption cross-section (cm2)

σ (121.6 nm) = 1.3 ± 0.2 x 10−17 cm2

1.0e-16

8.0e-17

6.0e-17

4.0e-17

2.0e-17

0.0

5 10 15 20 25
Photon Energy / eV
 Possible products from e- attachment and Lyman-α excitation of SF5CF3
___________________________________________________________________________
Reaction ∆rHo0 / kJ mol-1 (eV)
Scheme A a Scheme B b
___________________________________________________________________________

SF5CF3 + e- (0 eV) → SF5- (-1282) + CF3 (-463) c -124 (-1.29) +9 (+0.09)

(-1621 or -1754)
→ CF3- (-639) + SF5 (-915) d +67 (+0.69) +200 (+2.07)

SF5CF3 + hν ν (10.2 eV) → SF5 (-915) + CF3 (-463) -741 (-7.68) -608 (-6.30)
(-1621 or -1754)
→ CF3+ (+409) + SF5- (-1282) -236 (-2.45) -103 (-0.94)

→ SF5+ (+29) + CF3- (-639) +27 (+0.28) +160 (+1.66)

________________________________________________________________________
Values in ( … ) are ∆fHo0 in kJ mol-1
a Scheme A assumes ∆ Ho (SF CF ) = -1621 kJ mol-1 (theory)
f 0 5 3
b Scheme B assumes ∆ Ho (SF CF ) = -1754 kJ mol-1 (experiment)
f 0 5 3

• Using either value for ∆fHo0 (SF5CF3), it is energetically possible to form

dissociative products from both zero-energy electron attachment (SF5−) and
Lyman-α α photodissociation (CF3 + SF5 or CF3+ + SF5−). Both processes are
therefore sink mechanisms for removal of SF5CF3 from the atmosphere.
Thermal electron attachment rate constants, absorption cross-sections
at 121.6 nm, and atmospheric lifetimes for CF4, SF6 and SF5CF3
________________________________________________________________

Perfluoro compound ke (298 K) / cm3 s-1 σ121.6 / cm2 lifetime / yrs

___________________________________________________________________

CF4 < 10−16 < 8 x 10−22 > 50000

SF6 2.3 x 10−7 1.76 x 10−18 > 800

SF5CF3 7.7 x 10−8 1.3 x 10−17 ca. 1000

___________________________________________________________________

SF5CF3 is behaving as a perturbed SF6, not as a perturbed CF4, molecule.

For SF6, the dominant process for its removal is electron attachment in the
mesosphere to form SF5-. Assume the same is true for SF5CF3.
 Rate of a multi-step process is determined by the slowest step

A B C
k1 k2
(transport) (chemical removal)

If k1 » k2, transport of pollutant into the troposphere from point of

production is fast. The lifetime is then determined by the chemical
processes that remove B at a rate k2.

• Lifetime = (k[OH])−1 where k is the rate constant for reaction of the

pollutant, P, with the OH radical : OH + P → H2O + (P-H)
__________________________________

If k1 « k2, then transport of the pollutant into the region of the earth’s
atmosphere where chemical removal occurs is rate-determining.

• Chemical lifetime = (ke[e-])−1, assuming that the removal of SF5CF3

is dominated by electron attachment. This gives a lifetime of 3.6 h.
This is much too small, because most of SF5CF3 does not reside in the
mesosphere.
Globally-averaged loss frequency,
<k>global = Σ kiniVi / Σ niVi seconds-1

ki pseudo-first-order rate constant for region i

ni number density of pollutant in region i
Vi volume of region i

Need 3-D model of the atmosphere for values of ni

Meterology provides the different values of ki

Atmospheric lifetime = 1 / <k>global. For both SF6 and

SF5CF3, this is ca. 800-1000 years.

Once a molecule has got to the mesosphere, it makes

very little difference what the rate constants are for the
different processes (ion-molecule reactions, e-
attachment, Lyman-α α abspn) to determine <k>global !
 Lifetime of SF5CF3 in the earth’s atmosphere
• SF5CF3 most likely to be removed in the mesosphere (h > 60 km) by
−α),, electrons or ions.
reactions with photons (especially Lyman−
• Rate constants and products from reactions of SF5CF3 with a large
number of small cations have been measured in a Selected Ion Flow Tube.
Concentrations of cations are too low for ion-molecule reactions in the
mesosphere for these reactions to contribute significantly to loss process.
• Just consider electron attachment and Lyman-α
α photodissociation.
SF6 SF5CF3
k(electron attachment) / cm3 s−1 2.3 x 10−7 7.7 x 10−8 (i.e. 3.0 times slower)
σ (121.6 nm) / cm2 1.76 x 10−18 1.3 x 10−17 (i.e. 7.4 times bigger)
• Fractional loss of SF6 by electrons vs. photons = 1998 / 1 [Morris et al., J
Geophys Res D (1995) 100 1287]. Therefore loss of SF5CF3 by electrons vs. photons
= 90 / 1. Per molecule, quantum yield for electron attachment = 0.99, for
photodissociation = 0.01. ‘Chemical’ lifetime dominated by e- attachment.
• ‘Atmospheric’ lifetime is dominated by global climate that transports
SF5CF3 to the mesosphere. Model dependent. Typically, τ ≈ 1000 years.