Vacuum Ultraviolet Photochemistry. VII.

Photolysis of nButane
H. Okabe and D. A. Becker

Citation: The Journal of Chemical Physics 39, 2549 (1963); doi: 10.1063/1.1734060
View online: http://dx.doi.org/10.1063/1.1734060
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THE JOURNAL QF CHEMICAL PHYSICS VOLUME 39, NUMBER 10 15 NOVEMBER 1963
Vacuum Ultraviolet Photochemistry. VII. Photolysis of n-Butane
H. OKABE AND D. A. BECKER
National Bureau of Standards, Washington 25, D. C.
(Received 5 July 1963)
The photolysis of n-butane has been carried out at room temperature at the Xe resonance lines. A few
photolyses have been done at the Kr resonance lines. The isotopic analyses of products-hydrogen, methane,
ethane, and ethylene-produced in the photolysis of mixtures of C.H10+C.DIO and of CHaCD,CD,CH
a
were made, in the presence and the absence of 10% NO, to obtain information on the detailed modes of
decomposition. From these results, it was concluded that, at the Xe lines: (1) Hydrogen is detached mainly
by a molecular process
(9)
and preferentially from the inside carbon atoms. (2) Methane, amounting to 5% of hydrogen, is produced
both from the methyl radical and probably from three different molecular processes. (3) Ethylene is pro-
duced chiefly by the molecular process
CHaCD2CD2CHa->2CH,CD2+2H. (5a)
(4) Ethane is produced by molecular elimination as well as the combination of methyl radicals
CHaCD,CD2CHa->CHaCDa+CHaCD,
2CH
a
->C,H
a

(3a)
(4)
Other unsaturated hydrocarbons are produced largely by molecular processes, whereas saturated hydro-
carbons are produced mainly from free-radical processes. Relative probabilities of the primary processes
are assessed.
INTRODUCTION
R
ECENT photochemical investigations in the
vacuum-ultraviolet region on methane,! ethane,2
propane,s and n-butane
4
have led to the conclusion
that the molecular detachment of hydrogen is an im-
portant primary process.
Recently, Beck and Niehaus
5
studied the modes of
dissociation of excited n-butane molecules produced by
200-eV electron impact in a mass spectrometer. It was
concluded that not only hydrogen but most other
products were formed primarily in intramolecular
processes. The present work was initiated to le1.rn
whether molecular processes are important in the
formation of products other than hydrogen in the
photochemical decomposition of n-butane.
To assess the importance of molecular processes, the
products were subjected to isotopic analysis and, in
addition, the NO scavenging technique was employed.
EXPERIMENTAL
Light Source
The Xe and Kr resonance lines were excited in a
2450-Mc/sec microwave discharge operated by a
Raytheon 125-W microtherm unit with a suitable wave-
guide. Separate light sources were made by introducing
pure Xe and Kr at approximately 1 mm Hg into the
1 B. H. Mahan and R. MandaI, J. Chem. Phys. 37,207 (1962).
'H. Okabe and J. R. McNesby, J. Chem. Phys. 34,668 (1961).
3 H. Okabe and J. R. McNesby, J. Chem. Phys. 37,1340 (1962).
4 M. C. Sauer, Jr., and L. M. Dorfman, J. Chem. Phys. 35,
497 (1961).
5 D. Beck and A. Niehaus, J. Chem. Phys. 37,2705 (1962).
lamp, each of which was provided with a LiF window of
1 mm thickness.
The emission spectra of the rare-gas resonance lamps
were taken by means of a McPherson 50-cm-radius
grating monochromator in conjunction with a sodium
salicylate-coated photomultiplier. The Xe discharge
lamp exhibited resonance lines at 1470 A and very
weakly at 1295 A (less than 5% of the intensity of
light at 1470 A). The resonance lines of the Kr lamp are
at 1236 and at 1165 A, the latter line being 25% of the
intensity of the former. These intensity ratios agree
reasonably well with those obtained previously by the
photo-ionization method.
s
Both spectra were accom-
panied by many impurity lines originating from water
which could be effectively reduced by baking the lamp.
The light intensity, calculated from the yield of hydro-
gen, assuming cJ>H,= 1, ranged from 7.6 to 28X 1014
quanta/sec.
Materials
Phillips research-grade butane was used. Butane-d
lo
was obtained from Merck and Company, Montreal,
Canada. It contained 6.8% butane-d
9
These gases were
purified by gas chromatography using a silica gel
column. Finally, the gas passed through P
2
0
5
and
ascarite to remove moisture and carbon dioxide. Bu-
tane-2,2,3,3-d
4
was synthesized from the photolysis of
99.3 atomic D percent 3-pentanone-2,2,4,4-d
4
which
was made by the exchange of ordinary ketone with
heavy water.6
6 J. R. McNesby, C. M. Drew, and A. S. Gordon, J. Phys.
Chern. 59, 988 (1955).
2549
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2550 H. OKABE AND D. A. BECKER
2000
1000
I
E
u
I
E

100
I-
Z
lU
<:;
L;:
LL
lU
0
U
z
2
I-
10
0..
a:
0
'"
II>
..:
1200 1300 1400 1500 1600
WAVELENGTH (A)
FIG. 1. Absorption coefficients of hydrocarbons. The absorp-
tion coefficient of methane was measured by Watanabe, Zelikoff,
and Inn.7
The butane obtained was twice purified chromato-
graphically with a silica gel column after which it did
not contain any detectable impurities 0.01 %). The
mass cracking pattern shows a good agreement with
that obtained by McNesby, Drew, and Gordon.
s
Nitric
oxide, obtained from Matheson Company, Inc., was
fractionated by bulb-to-bulb distillation at -160 to
-195C.
Measurement of Absorption
The absorption of various hydrocarbons was meas-
ured with a McPherson 50-cm-radius vacuum-ultra-
violet monochromator. The reciprocal linear dispersion
at the exit slit is 33 A/mm. A slitwidth of 30 /J. was
used. A hydrogen discharge lamp was used as a light
source. The absorption cell was 57.1 mm in length and
was provided with two LiF windows of 1 mm thickness.
The pressure was measured with an oil manometer and
an expansion method was used for pressures lower than
1 mm Hg. The absorption was measured in several
different pressure regions.
Procedure
A mercury-free reaction vessel of approximately 200
cc volume was attached to the lamp through a ground-
glass joint with Apiezon W wax. The hydrogen and
methane, noncondensable at liquid-nitrogen tempera-
ture, were transferred by means of a Toepler pump to a
calibrated volume and were analyzed with a CEC
21-620 mass spectrometer. When nitric oxide was
present, it was separated from hydrogen and methane
at - 210C. The condensable products were analyzed
with an F and M Model 720 gas chromatograph with a
1690 flame ionization detector. A lO-m squalane column
was used at 60C for the separation of C
2
through C
6
hydrocarbons except trans-butane-2, whose peak over-
lapped with that of butane. The latter separation was
achieved at room temperature by means of a 3-m
column of dimethyl sulfolane in series with a 3-m
column of di-n-butyl maleate, both on Chromosorb P,
in conjunction with a thermal conductivity detector.
When necessary, products were trapped for isotopic
analysis at liquid-nitrogen temperature after emerging
from a silica-gel column.
The references for the standard mass spectra of iso-
topic methanes, ethanes, and ethylenes used for the
analysis have already been given.
3
RESULTS
Absorption Coefficient
The absorption coefficients, k, defined as 1=
Ioexp(-kpx), where p is the pressure in atmospheres
at 25C and x the path length in centimeters, for various
hydrocarbons were measured in the vacuum ultraviolet
region and are shown in Fig. 1. The light intensity de-
creased below 1400 A because of the less efficient
reflectivity of the grating and an increasing amount of
absorption by the LiF window. The measurement was,
therefore, less reliable in this region. The absorption
coefficient of methane was measured by Watanabe,
Zelikoff, and Inn.7 The absorption coefficient and the
long-wavelength limit increase successively from me-
thane to butane. It is of interest to observe that the
absorption coefficient of n-butane-d
lO
is much smaller
than that of normal butane for the wavelength region
longer than 1340 A, whereas the relationship is reversed
for the region shorter than 1340 A. Butane appears to
have several absorption maxima. The coefficients at
1470 A are 600 and 350, respectively, for C
4
H
lO
and
C
4
D
lO
, which agrees well with those obtained by Sauer
and Dorfman.
4
Within the limit of the resolution of the
instrument ("-'1 A), the absorption appears to be con-
tinuous for all hydrocarbons measured over the entire
spectral region, indicating that the upper electronic
states are strongly predissociated.
8
The absorption
coefficients of these and other hydrocarbons in the
region below 1200 A have recently been measured by
Schoen.
9
Analysis of Products
Products of the photolysis of butane at the Xe and
Kr resonance lines were found to be hydrogen, methane,
acetylene, ethylene, ethane, propylene, propane, bu-
tene-1, cis- and trans-butene-2, i- and n-pentane, hex-
anes, and small amounts of i-butane and allene. At the
Xe lines, the yields of all products, except acetylene,
7 K. Watanabe, M. Zelikoff, and E. C. Y. Inn, AFCRC Tech.
Rept. No. 53-23, 1953.
8 R. S. Mulliken, J. Chern. Phys. 3, 517 (1935).
9 R. 1. Schoen, J. Chern. Phys. 37, 2032 (1962).
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VACUUM ULTRAVIOLET PHOTOCHEMISTRY. VII 2551
TABLE I. Photolysis of n-butane at room temperature. Relative amounts of products.
Xe (14701) Kr (1236 1, weak 1195 1)
C,H
1O C,H10 +10% NO C,H
lO C,H1o +1O% NO
Products (10 mm Hg) (10 mm Hg) (10 mm Hg) (10 mm Hg)
Hydrogen 100 100" 100 54"
Methane 5 1.5 9.9 3.9
Acetylene 8 13 26.5 23.6
Ethylene 53 70 63.2 92.0
Ethane 33 17 34.0 22
Propylene 15 15 12.7 16
Propane 20 4 18.5 6
Allene 0.6 1 1.2 1.8
i-Butane 2.6 0 1.2 0.9
Butene-1 24 15 12.7 13.5
trans-Butene-2 29 25 11.5 15
cis-Butene-2 15 13 6.6 8
i-Pentane 11 0.4 7.7 1.2
n-Pentane 3 0.5 2.7 1.2
Hexanes 4 0.2 6.2 0
The yield is based on the rate of hydrogen production normalized to 100, wben NO is absent.
increased linearly with extent of reaction up to 5%
decomposition, whereas acetylene was linear up to 2%
after which the rate sharply increased. This indicates
that no secondary reactions are involved for the forma-
tion of products up to 2% decomposition. Relative
amounts of these products, normalized to hydrogen
= 100 in the absence of NO, are given in Table I. From
the Table, it can be seen that, at the Xe lines, the
yields of hydrogen and acetylene are relatively unaf-
fected by adding NO, whereas the yield of methane,
ethane, propane, i- and n-pentane, and hexanes
markedly decreases. The yield of ethylene increases
when NO is added. The rate of hydrogen production
does not change appreciably in the presence of 10% NO
at the Xe lines, whereas it decreases to almost half at
the Kr lines. The relative amounts of products are not
markedly affected by adding 1 atm of He. From the
absorption coefficients of N07 and of butane at the Xe
and Kr lines, the fraction of light absorbed by 10% NO
amounts at most to 1 %.
At the Kr lines, it can be seen that the yields of
hydrogen, methane, ethane, propane, i- and n-pentane,
and hexanes decrease markedly whereas the yields of
acetylene, propylene, and butenes increase slightly.
The yield of ethylene increases markedly. The formulas
obtained from the analysis are C
4
H
10

01
for the Xe lines
and C
4
H
lO

14
for the Kr lines showing excellent material
balance. This indicates only a very small extent of
polymerization, if any.
Table II gives the isotopic analysis of hydrogen and
methane with or without added NO in the photolyses of
mixtures of C4HIO-C4DIO and of CH
3
CD
2
CD
2
CH
3
at the
Xe and the Kr lines. The isotopic analyses of ethane
and ethylene are shown in Tables III and IV with and
without NO in the photolysis of mixtures of C
4
H
10
-
C
4
D
10
and that of CH
3
CD
2
CD
2
CH
3
at the Xe lines.
The isotopic analyses for ethylene and ethane were
less reliable than that for hydrogen and methane be-
cause of the air background at m/e= 28 and 32 as well
as somewhat ambiguous cracking patterns of reference
isotopic material on which the analysis must be based.
DISCUSSION
Formation of Hydrogen
In agreement with Sauer and Dorfman
4
the isotopic
distribution of hydrogen produced in the photolysis of
mixtures of C4HIO-C4DlO at 1470 A shows that H2 and
D2 are the predominant species [Table II (A)].
The ratio H
2
/D
2
= 1.8 obtained at 1470 A also agrees
with this value which they attributed to the ratio of the
absorption coefficients. The ratio HdD2= 1.4 at the Kr
lines in the presence of NO, however, does not agree
with that of the absorption coefficients at the Kr lines.
If this is due to the presence of impurity lines of water
which could not be removed, their integrated intensity
must be almost as strong as that of the Kr resonance
lines to give the ratio of 1.4. This appears to be the case
since no great precaution was taken to remove the im-
purity lines for this experiment. For the photolysis at
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2552
Butane (mm Hg)
o
6.1
5.0
6.6
4.4
5.0
4.5
2.3
Butane
(mm Hg)
5.5
4.9
5.9
5.0
4.5
7.3
6.1
5.0
6.6
4.4
5.0
4.5
2.3
Nitric
oxide
(mm Hg)
o
o
o
0.4
0.5
H. OKABE AND D. A. BECKER
TABLE II. Photolysis of n-butane; isotopic analysis of hydrogen and methane.
Nitric
(A) Mixture of C,H]o-C,D]o
Hydrogen (percent)
oxide Exciting
(mm Hg) lines HD
o
o
o
o
0.5
0.6
o
0.4
Exciting
lines
Xe
Xe
Xe
Xe
Xe
Xe
Xe
Xe
Xe
Xe
Xe
Kr
Kr
0.8
62.2
59.8
61.1
62.4
59.8
49.8
53.5
2.9
8.0
7.3
7.5
6.3
6.4
16.4
9.5
96.3
29.8
32.9
34.4
31.3
33.8
33.8
37.0
38.2
44.0
52.8
49.3
56.3
36.5
53.4
(B) CH
3
CD
2
CD
2
CH
3
Hydrogen (percent)
H2 HD
25.
27.2
23.6
24.5
23.8
16.
16.9
15.7
15.5
16.2
59.
55.9
60.7
60.0
60.0
44.
38.3
37.
32.0
Methane (percent)
CH3D CH2D2 CD3H CD,
7.4 6.6 86.0
10.5 (17.5) 16.0 17.8
11.4 5.9 18.5 20.2
6.5 1.6 19.5 19.6
4.4 2.6 6.3 37.4
3.3 3.3 10.3 26.8
7.5 ~ 21.0 35.0
1. 1 3 .0 4. 5 38.0
Methane (percent)
CH3D CH2D2 CD3H
44.
43.0
50.
59.0
6.0
11.0
5.0
6.0
6.0
6.0
4.0
3.0
CD,
~
1.7
5.0
~
Amount of
methane and
hydrogen
(p,M)
0.62
2.67
3.87
2.14
1.2
2.88
0.57
0.5
Amount of
methane and
hydrogen
(p,M)
0.77
3.84
1.2
0.91
1.54
1470 A, approximately 7% HD was found after the
correction was made for HD coming from the C
4
D
10

This amount decreased slightly in the presence of NO.
The percent HD was 2, 5, and 7, respectively, when
mixtures of C
2
H
6
-C
2
D
6
.2 CaHs-CaDa,3 and C4HIO-C4DIO
were photolyzed at 1470 A. This increasing amount of
HD signifies a small but increasing extent of an atomic
process.
Butane (mm Hg)
6.1
5.0
5.0
4.4
6.1
5.0
5.0
4.4
Butane
(mm Hg)
5.5
5.9
5.2
That the molecular detachment of hydrogen at 1470
A does not take place randomly can be seen from the
photolysis of CH
3
CD
2
CD
2
CH
a
where the ratios
H
2
:HD:D
2
=25:15:60 were obtained. This indicates
TABLE III. Photolysis of n-butane at 1470 A; isotopic analysis of ethane.
Nitric oxide
(mmHg)
o
o
0.6
0.5
Nitric oxide
(mmHg)
o
o
0.4
C.Hs
46
54
51
59
Ethane (percent)
C2HSD C2H,D2 C2H3D3 C2D,H2 C2DsH
~ ~ 19 2 4
3 2 11 2 4
6 ~ 5 2 3
~ ~ 3 3 3
(B) CH
3
CD
2
CD2CH
3
Ethane (percent)
C2HS C2H,D2 C2
HaDa
52
31
12
26
38
20
22
31
68
29
24
34
31
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VACUUM ULTRAVIOLET PHOTOCHEMISTRY. VII 2553
TABLE IV. Photolysis of n-butane at 1470 A; isotopic analysis of ethylene.
(A) Mixture of C,H1O-C,D
1O
Butane (mm Hg) Ethylene (percent)
Nitric oxide
C,H
IO C2D
1O
(mmHg) C
2
H, C,HaD C2H2D2 C2DaH C2D,
6.1 6.1 0 56.
",0 4 40
4.4 4.4 0.4 51. 6 3 40
5.0 5.0 0.6 52. 7 3 3 35
(B) CH
a
CD
2
CD2CH
a
Butane Nitric oxide
(mm Hg) (mm Hg)
4.9 0
5.9 0
2.2 0
5.2 0.4
4.5 0.5
the most favorable detachment takes place at the 2
and 3 positions although 2,2 and 2,3 hydrogen detach-
ment are indistinguishable. The next most favorable
detachment takes place at the end carbon atoms. It is,
however, not possible to differentiate 1,1 and 1,4
detachment processes. This result tends to generalize
the observation in the photolysis of propane that
hydrogen is preferentially expelled from the secondary
carbon atoms at 1470 A. The increased extent of an
atomic process at the Kr lines can be seen from the
photolysis of mixtures C4HlO-C4DIO where the HD in-
creased to 16%. The addition of 10% NO decreased
but did not completely inhibit the formation of HD
signifying NO does not scavenge all the atomic hydro-
gen. From the reduced rate of hydrogen production with
added NO at the Kr lines (Table I), at least 46% of the
hydrogen is formed from an atomic hydrogen precursor.
Formation of Methane
Methane is produced to the extent of 5% of hydrogen
at 1470 A. Table I shows that more than half the
methane is scavenged by NO indicating that its forma-
tion is partially by molecular elimination and partially
by a free radical process. The predominant isotopic
species produced in the photolysis of the mixture of
C4HIO-C4DIO are CH4, CHaD, CDaH, and CD4. When
NO is added, CH
4
and CD
4
are the main species [Table
II (A)]. This further supports the view that methane
is produced only partially by a molecular elimination.
Isotopic methanes from the photolysis of CH
a
CD
2
-
CD
2
CH
a
[Table IICB) ] are CH
4
and CH,D. The
addition of 10% NO decreases but does not eliminate
the production of CH
4
This suggests the following de-
Ethylene (percent)
C2HaD C2H
2
D2 C2DaH C
2
D,
14 70 4 12
25 65 9
30 59 5 6
12 78 4 6
28 52 3 17
compositions:
(la)
(lb)
(lc)
Similar reactions have been observed in the photolysis
of propane.
2
,

Formation of Ethane
Table III CA) shows that the isotopic ethanes pro-
duced in the photolysis of C4HIO-C4DlO at 1470 A are
mainly C
2
H
a
) C2HaDs, and C2Da while, in the presence
of NO, C2Ha and C2Da are the main species. The most
reasonable interpretation of this result is the formation
of ethane by the molecular process as well as by the
combination of methyl radicals. Table III (B) further
shows that C
2
H
a
, C
2
H4D
2
, and C2HaDa are the
main ethane species produced in the photolysis of
CH
s
CD
2
CD
2
CH
s
at 1470 A whereas, in the presence of
NO, C
2
HsDa becomes most important for the formation
of ethane.
(2)
(3a)
(4)
The following reaction is less important:
CHsCD2CD2CHrCHsCD2H+CH2CD2. (3b)
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2554 H. OKABE AND D. A. BECKER
TABLE V. Relative probabilities of the primary processes in the
photolysis of n-butane. Total probability = 100.
Relative probability
Molecular Xe Kr Equations
C,HIO->H2+C,H. 41 18 (9)
C,H1O->2C2H,+2H 12 20 (Sa)
C,H1O->CH,+C
a
H6
3 (1)
C,Hw-.CHa+ H +CaH6 7 7 (8)
C,HIO->C2H6+C2H, 2 0 (3)
C,HIO->C2H6+C2H2+ H2 6 15 (7)
Radical Process
C,Hlo->CHa+CaH7 ;;;24 "?,27 (2)
C,HIO---,C2H5+C2H5 ;;;7 ;;;;10 (Sb)
Table I shows that the rate of ethane formation de-
creased to nearly one-half in the presence of NO indi-
cating almost an equal probability of formation by
molecular elimination and by the combination of
methyl radicals.
Formation of Ethylene
Table I shows that NO does not inhibit the produc-
tion of ethylene. The small increase of ethylene appears
to be due to NO scavenging of atomic hydrogen which
would otherwise add to ethylene.
The main isotopic species in the photolysis of the
C
4
H
lO
+C
4
D
lO
mixture are C
2
H
4
and C2D
4
This com-
position does not appreciably change in the presence of
NO. This establishes the intramolecular formation of
ethylene. The isotopic analysis from the photolysis of
CH
3
CD
2
CD
2
CH
3
further proves that C
2
H
2
D
2
is the
most important species while C2H3D is less important.
The result can most reasonably be interpreted by
initial formation of an excited ethyl radical
CH3CD2CD2CHa---t2CH3CD2*, (5)
followed by the decomposition into ethylene
CH
a
CD
2
* ---tC
2
H
2
D 2+ H,
or collisional deactivation
M
CH
3
CD
2
* ---tCH
3
CD
2
.
(Sa)
(Sb)
By analogy with the methane detachment process (lc),
the molecular elimination reaction,

However, this process cannot be important since it
should give a large amount of CH
a
CD
2
H, whereas
experimentally C2HaD3 is the most important ethane
produced by molecular elimination. Furthermore,
Table I shows that the amount of ethane is one-fourth
that of ethylene in the presence of NO. Therefore, the
step (3b) must be a minor process. Step (3a) followed
by the isomerization of ethylidene, is also a minor
source of ethylene.
The formation of ethylene by the expulsion of two
methyl radicals (6)
CHaCD2CD2CHa---tC2D4+2CHa, (6)
is also a minor step since C
2
D
4
amounts, at most, to
17% of the total isotopic ethylenes. The estimation of
small amounts of C
2
D
4
is difficult because its mass 32 is
indistinguishable from that of background O
2
in the
mass spectrometer.
Other Processes
All unsaturated hydrocarbons, acetylene, ethylene,
propylene, allene, and butenes remained unchanged or
increased when NO was added except butene-1 which
decreased by 40%. It is reasonable to ascribe the forma-
tion of these products to the following molecular
processes:
acetylene: C4HIO---tC2H6+C2H2+H2; (7)
propylene: C4HIO---tCH4+CaH6 (1)
---tH +CH3+CaH6; (8)
butenes: C4H16---tH2+C4H8. (9)
Total yields of butenes are approximately one-half of
that of hydrogen. This deficiency of butenes could be
due to (1) further decomposition of excited butenes or
(2) addition of atomic hydrogen to form butyl radicals.
Further decomposition of both excited ethylenes,
formed in step (Sa), into hydrogen and acetylene is not
energetically possible at 1470 A since the over-all
process requires l1H = 242 kcal/mole.
Most saturated products, propane, i-butane, i- and
n-pentane, and hexanes were, on the other hand,
markedly reduced by the addition of NO. It follows
tha t these products are formed by free radical processes:
Propane: CH
a
+ C2Hs---tCaHs; (10)
i-butane: H+C3H6---ti-CaH7;
(11)
CH
a
+i-C
a
H
1
---ti-bu tane; (12)
pen tanes: H + C
4
H
8
---tC
4
H
9
, (13)
may also contribute to the formation of C
2
H2D
2
. The
process (Sa) is a major source of atomic hydrogen. An
alternate possibility is the intramolecular formation or
of ethylene
CH
a
+ C
4
H9---tC
s
H12,
C
2
H
s
+ C
a
H7---tC
s
H12;
(14)
(1S)
CHaCD 2CD2CHa---tCHaCD2H + CH
2
CD2. (3b) hexanes: (16)
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VACUUM ULTRAVIOLET PHOTOCHEMISTRY. VII
2555
CONCLUSION
Finally an assessment may be made of the relative
probabilities of the primary processes.
From the foregoing discussion, a set of processes is
proposed in Table V which accounts reasonably well
for the results.
The relative probabilities of each step are based on
the following equalities:
Step (9) = ("molecular" hydrogen) - (acetylene),
Step (Sa) =tx (total ethylene) XO.7(fraction of eth-
ylene which is C
2
H
2
D
2
),
Step (1) = "molecular" methane,
Step (8) = (propylene) - ("molecular" methane),
Step (3) = ("molecular" ethane) - (acetylene),
Step (7) = acetylene,
Step (2) = ;,2X ("ethane" by combination) + (pro-
pane) ,
Step (5b) =;,B(butane by combination of ethyl)+
! X (propane) ,
where B=!:(propane)2/(ethane by combination).
The relative probabilities of radical processes are a
lower limit since association reactions among methyl
and ethyl radicals are only considered.
From Table V it is evident that, at shorter wave-
lengths, a process to produce the atomic hydrogen
and ethylene becomes important as well as that to
produce acetylene. Contrary to the Beck and Niehaus
resultS by electron-impact study, the radical process is
also significant in the decomposition of butane. How-
ever, it is evident that molecular processes play im-
portant roles in the formation of hydrogen, ethane, and
some unsaturated products, whereas other saturated
products are mainly formed by free radical processes.
THE JOURNAL OF CHEMICAL PHYSICS VOLUME 39, NUMBER 10 15 NOVEMBER 1963
Sulfur and Silicon Isotope Effects in Fluorine Nuclear Magnetic Resonance Spectroscopy
R. J. GILLESPIE AND J. W. QUAIL
Department of Chemistry, McMaster University, Hamilton, Ontario, Canada
(Received 14 June 1963)
Satellites due to fluorine on S33 have been observed in the Fig NMR spectrum of sulfur hexafluoride.
Values of the S3LF coupling constant and of the S33 isotope effect on the fluorine chemical shift have been
obtained from the spectrum. We have also observed a S34 isotope effect on the fluorine chemical shift of sulfur
hexafluoride and other sulfur-fluorine compounds. A Si
29
isotope effect on the fluorine chemical shift has
been observed for silicon tetrafluoride.
INTRODUCTION
I
SOTOPE effects on the chemical shift in fluorine
NMR spectra have been observed in the systems
F-Si29 (Si2S) ,1 F-C-D (H),2 F-C13 (CI2),3-8 and F-C-C13
(C12).8-S In every case the fluorine resonance is ob-
served at higher field when the fluorine is attached di-
rectly or indirectly to the heavier nucleus. Similar, but
considerably smaller effects have been observed in pro-
ton magnetic resonance spectra.9-11 The Si29-F isotopic
shift was observed by Tiers! in the single case of the
SiF
6
2- ion and was only just large enough to be observ-
able. Since it is considerably smaller than the CILF
1 G. V. D. Tiers, J. Inorg. Nucl. Chern. 16, 363 (1961).
2 G. V. D. Tiers, J. Am. Chern. Soc. 79, 5585 (1957).
3 G. V. D. Tiers and P. C. Lauterbur, J. Chern. Phys. 36, 1110
(1962) .
4 G. V. D. Tiers, J. Phys. Soc. Japan 15, 354 (1960).
5 G. V. D. Tiers, J. Chern. Phys. 35,2263 (1961).
6 G. V. D. Tiers, J. Phys. Chern. 66, 945 (1962).
7 J. Bacon and R. J. Gillespie, J. Chern. Phys. 38, 781 (1963).
8 N. Muller and D. T. Carr, J. Phys. Chern. 67,112 (1963).
9 G. V. D. Tiers, J. Chern. Phys. 29, 963 (1958).
10 G. V. D. Tiers, J. Phys. Chern. 64, 373 (1960).
11 H. S. Gutowsky, J. Chern. Phys. 31, 1683 (1959).
isotope shift, Tiers suggested that there is a strong
inverse dependence of the isotopic shift on the bond
length. We have now studied another example of a
Si
2L
F isotope effect and have observed and measured
S33-F and S3LF isotopic shifts for the first time.
RESULTS
Sulfur Isotope Effects
Naturally occurring sulfur consists of four stable iso-
topes; the generally accepted natural abundances and
the nuclear spins are as follows:
95.06%
0.74%
4.18%
0.0136%
I=O,
I=O.
The only stable isotope with a nuclear spin is S33 and
this isotope also has an electric quadrupole moment.
The quadrupole moment, combined with the very low
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