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Gas phase spectroscopic studies of small molecules labelled with 14C
Journal of Molecular Structure, 60 (1980) 243-248 0 Elsevler Scientific Publishing Company, Amsterdam-
GAS
PHASE
A.
SPECTqOSCOPIC
AYOUB+,
J.
Institute H-l 525
of
MINK
STUDIES
and
SYALL
YOLECULES
LABELLED
WITH
14C
?!l.GAL
Isotooes
Budapest,
OF
243
Printed in The Netherlands
of
the
Hungarian
Academy
of
Sciences,
Hungary
ABSTRACT Infrared
spectra
resolution were
the
(-0.5
from
the
analysed
structure
to
14C12
and
yield
CH2
were
values
for
measured
under
zeta
band
of a successive 14 band, ~7, of C2H6. of the perpendicular band,
perpendicular
Rotational
C2H6
cm -1) . Aoproximate
determined
for
14
of
analysis
values
of
wo,
B',
B"
and
and
series
u5,
medium origin
of
Q branches
14c12
of
CH2
was
D.
INTRODUCTION Yost
of
the
vibrational in
Only
(refs. In
3272
few
years
medium and
From
of
for
under
was
cm-l
investigated
contained
comoounds
have
the
with
so 13
stable
labelled
l4 CO
rotational
measured Two
(the
the A
abudance
lines
we
oerpendicular
obtained.
and
have
have
resolution.
1338
observed.
63
cases
compounds
14C
C
far
by
isotope
been
(ref.
1) .
studied
2-8).
intense
were
labelled
spectroscopy
a
recent
under
carbon
v3
at
86%
resolution of
the
1-O
5 rotational-vibratlonal
seectrum -1 cm
0.2
+Psrman~nt
(the
C2H2 at
bands
and
one
very
fundamental),
substance
were
vo,
B:
B"
and
with
an
isotopic
D
6). Infrared measurements -1 were also made enabling cm .
0.5
fundamental
constants
w5
structure
(ref. of
parallel
14
of
to
transition be
to
determined.
be
assigned,
The
observed
-1
of the calculated values. Isotopic abudance within 0.05 cm 14 the mid-infrared, the far infrared 86% CO (ref. 7). Besides 14 CO was taken under a much higher pressure (68 kPa)' with of
were also
cm -1
utilized
spectrum
respectively),
carrier-free
was
medium lines
intensity
ui+v; 726
infrared
rotatlonal-vibrational
relatively
about
medium
and
band
the
resolution. address:
From Physics
the
observed
Dept.,
14
Basrah
rotational University,
lines
Bo
Basrah,
and Iraq.
Do
244 were
determined
wave
spectra
and
obtained
lated
the
(a)
et
two
doubly
labelled
the
distance -I7 in LLCH
0
(C-C)
rs
distance
dipole
present
OE
Hirota
and
the
the
v5,
8).
B
rz
evaluated The
(ref. of
moments
perpendicular 14C12CH2,
both
(ref.
9)
ethanes,
includes
band,
~7,
under
medium
the
of
observed
micro-
12CD 3 and 12CH3 13CD 3 3' bond. They also calcuthe
Stark
measurement
14C2H6
the
13CH
of the C-C 17 LLCD From 3 3' the two species.
of
investlqation
al
and
(b)
resolution
effect,
they
of: the
(0.5
perpendicular
band,
,
cm -5
EXPERIVENTAL Both
:lCZH6
paring A
cm
of
14C2H6
0.7
k?a.
lution
as
reported
earlier
was A
of
the
lenght
pressure
Elmer-225
in
the
cell
as
FTS-14
Infrared
spectrometer
Fourier
RESULTS
AND
A
KBr
with
ore-
windows
70
kPa;
14c12cI-i 2 was
estimated
snectrometer
with
mid-infrared a
nartial
used.
of
transform
the
was
that
region,
similar
anodization
data
of
6).
cell
having
boxcar
transform
process
about
kPa,
the
the
was
and
oressure
a Perkin
resolution carried
as
a reso-
were
out
used
during
the
nrocessinq.
DISCUSSION
14C2H6
In
theg7
subband
perpendl;ular PK(J)
resolution and
and
band,Rthe
P,;(J)
The
.
RQK
0
--
A'(l-c)2-Bg c K.
The
spectrum
pO7
were
subband
IS
shown
fitted
by
(A'-A")
In
the -
feature
centres
are
for
R?K
Fig.
squares
Zb'(l-5)-8'1
The
observed
and
14C2H6
From
the
should
vop
Z,
are
summarrzed
experimental be
along
possible
2_B# with in
equation to
and
not is
resolved
given
method
RQ,
to -1
3.47398
cm-l
=
2979.330
cm-l
molecular
medrum
1
for
observed
=
give
constants
to
*Q7
the
and
"2,
to
values:
for
both
12 C2H6
1.
v7(eu)=2979.3+3.47098
determine
our
the
'1 branches
+ [(A'-A")-:B'-B")K2
cm
Table
in of
of
by:
= 0.015239
the
transitlons
a series
negative
1. The
least
A'(l-c)
R-branch
2[A-(l-5)-B'lK
(B'-B")
wo+
are
maln
+
positrve
P - and
RK(J)
and
The
measurement.
V’U
it
gas
Fourier
throughout
from
(ref.
was
0.8
DIOILAB -1 0.5 cm
measurements.
by-products
standard
estimated
inverse
(a)
were
optical
total
for
14CL2CH2
C2H2'
IO
The
and
the
molecular
Kco.ol5289 constants
v
o,
K2, A',
A",
245
-+E
246
5, however
B', B", and band origin forced and
to
is
make
of
the
somewhat
normally
perhaps dubious -1 cm (calculated
cm-l_
from
A
for
from
value
TABLE
the
large
Vo=2977.7896
approximate
derived
molecule).
range
Cole's
only
be
B0=0.06054
B'-
metry
can
value
a C-H
0.06 This
(2985.353
the
values
data
from
for
0.09.
band
for
zeta
‘*tomic
vibration
normal
ethane
the
We
and
the
geo-
obtainedthe
This
5 values
one
obtains 7.564 cm -1
by
(ref.
from
10).
1
Molecular
constants -1 (cm 1
bands
obtained
from
12C
v
A'(1-c)2-B'
+
the
v7
band
14
of
and
C2H6
other
14
H
26
C2H6
2986.729
2979.300~0.0770
2"CA' (l-I)-B'1
3.3530
3.4709
+0.0110
(A'--Al')-_(B’-B”)
kO.0030
0.0103
0.01528
V
2985.35
2977.789
co
0.128
0.096
2895.8
2886.1
2954.0
2947.5
v5(a2u) vB+vll
(b)
(a,u)
14C12CH
?
The 750
line positions are -1 region consists cm
Fonents lower and
falling
to
frequency the
to
fitting
using
the
line
positions V
This
gives
m the
=
should
a
be
transition
g-&. Table
in
bands.
assigned 14C12CH
C is
of
considerably
of
positIons
absorption
weaker to
v5
This
2'
of very
Yolecular 3 by
the
The
comthan
the
14C2H2 strong constants
a polynomial
equation: V
The
line
The
sets
are
fundamental
to
the
2.
close-lying
latter
same
-due
from
in Table
two
frequencies
The
the
band
evaluated
given of
higher
ones.
former
perpendicular were
are -1 cm
Ao=2.589
where
57=0.096, shifted
A'-
thus
for
work.
masses
is
is
and
present that
F+O.O96,
Using
origin
cm-11
for
the
assumption
stretching
to
in
m
- v.
are 728.33
(B'CB")m
reproduced +
2.2592
f
(B'-B")m2
-
satisfactorily m
constants,
- 0.002876
4Dm3
from m2
+
55
the x
expression:
10+m3
presented ln Table 3. 14 If B for 14C12CH is compared with B of and with the B, C2H2' values of 12C2H2 azd 13C2H2 (refs. 6, 111, a reasonable trend is observed.
rotational
+
247 = 1.766
B.
14C2H2 The
B" = X.0657
calculated
parameters served
TABLE
C2H2
cm-'
rotational
is 1.1293. which
14C2H2 constants
from
is in quite
= 1.1195
cm-l
B " = 1.1310
cm-l
%
masses
good
and
agreement
geometrical with
the ob-
B" value.
St is known from
13
cm-l
that
the present
the centrifugal experimental
distortion
data,
is not
constant accurate
D, determined enough.
2
Observed
lzne position
of the calculated
of V5 band
frequencies
J
are
of
The fractional.. parts 2" in parentheses vat. cm -1
14C1*CH
given
P(J)
R(J)
(730.59) 732.75
<0_83)
735.00
(0.08)
723.75
(0.801
737.25
(0.32)
721_50
(0.531
739.50
(0.55)
719.25
(0.25)
741.75 744.00
(0.771 (3.9%)
717.00 714.75
(6.97) (0.68)
746.20
(0.19)
712.45
(0.39)
748.40
10.39)
710.15
(0.10)
750.60
(0.58)
707.85
(0.81)
752.80
(0.76)
705.55
(0.51)
755.00
(4.93)
703.25
(0.21)
12
757.20
(0.09)
700.90
(0.90)
13
759.30
(0.24)
698.55
(0,591
14
761-40
(0.38)
696.20
(0.28)
I5
763.50
(0.52)
16 17
765.60
(0.63)
767.70
10.74)
18
769.80
f0.84)
(726.09)
248
TABLE
3
Calculated
rotational
acetylenes
(cm --l)
constants
obtained
from
w5
14C12CH2 v5
728.33
+ 0.056 0.00220
band
of
l*C
14C2H2 726.39
+ 0.016
1.0636
+
0.0219
B'
1.1282
2
B"
1.1311
+ 0.0220
1.0639
+
0.0219
4D
(-55.1
;
(-14.3
2
13.2)X+
12_7)10-6
labelled
REFERENCES i 2 3 4 5 6 7 8 9 10 11
and I. Laullcht, s. Pinchas Infrared spectra of labelled compounds, Academic Press, London, Ch.5, pp.201-209, (1971). A.H. Nielsen and R.T. Lagemann, J. Chem. Phys., 22 (1954) 36. W. Sterzel and E_ Chorinsky, Spectrochim. Acta., 24A (19681 353. B.H. Baxter and A.F.C. Horsler, Nature, 204 (1964) 675. R.M. Hammacker and J.P. Walters, Spectrochim. Acta 20 (1964) 1311. J_ Mink and G. KemQny, Spectrochim. Acta., 33A (1977) 277. A. Ayoub, G. Kemeny and F. Kling, J. Mol. spectry (in press), J. Mink, J. Mink, A. Ayoub, G. Kemeny, R. Krem6 anti F. Kling, Spectrochim. Acta (in press) _ K. Matsumura, M. Imachi, M. Fujio, Y. Tsuno and C. E. Hirota, Efatsumura, J. Chem. Phys., 66 (19771 2660. A.R.H. Cole, W.J. Lafferty and R.J. Thibault, J. Mol. Spectrosc., 29 (1969) 365. W.J. Laffferty and R-I_ Thibault, J. Mol. Spectrosc., 14 (1964) 79.
GAS
PHASE
A.
SPECTqOSCOPIC
AYOUB+,
J.
Institute H-l 525
of
MINK
STUDIES
and
SYALL
YOLECULES
LABELLED
WITH
14C
?!l.GAL
Isotooes
Budapest,
OF
243
Printed in The Netherlands
of
the
Hungarian
Academy
of
Sciences,
Hungary
ABSTRACT Infrared
spectra
resolution were
the
(-0.5
from
the
analysed
structure
to
14C12
and
yield
CH2
were
values
for
measured
under
zeta
band
of a successive 14 band, ~7, of C2H6. of the perpendicular band,
perpendicular
Rotational
C2H6
cm -1) . Aoproximate
determined
for
14
of
analysis
values
of
wo,
B',
B"
and
and
series
u5,
medium origin
of
Q branches
14c12
of
CH2
was
D.
INTRODUCTION Yost
of
the
vibrational in
Only
(refs. In
3272
few
years
medium and
From
of
for
under
was
cm-l
investigated
contained
comoounds
have
the
with
so 13
stable
labelled
l4 CO
rotational
measured Two
(the
the A
abudance
lines
we
oerpendicular
obtained.
and
have
have
resolution.
1338
observed.
63
cases
compounds
14C
C
far
by
isotope
been
(ref.
1) .
studied
2-8).
intense
were
labelled
spectroscopy
a
recent
under
carbon
v3
at
86%
resolution of
the
1-O
5 rotational-vibratlonal
seectrum -1 cm
0.2
+Psrman~nt
(the
C2H2 at
bands
and
one
very
fundamental),
substance
were
vo,
B:
B"
and
with
an
isotopic
D
6). Infrared measurements -1 were also made enabling cm .
0.5
fundamental
constants
w5
structure
(ref. of
parallel
14
of
to
transition be
to
determined.
be
assigned,
The
observed
-1
of the calculated values. Isotopic abudance within 0.05 cm 14 the mid-infrared, the far infrared 86% CO (ref. 7). Besides 14 CO was taken under a much higher pressure (68 kPa)' with of
were also
cm -1
utilized
spectrum
respectively),
carrier-free
was
medium lines
intensity
ui+v; 726
infrared
rotatlonal-vibrational
relatively
about
medium
and
band
the
resolution. address:
From Physics
the
observed
Dept.,
14
Basrah
rotational University,
lines
Bo
Basrah,
and Iraq.
Do
244 were
determined
wave
spectra
and
obtained
lated
the
(a)
et
two
doubly
labelled
the
distance -I7 in LLCH
0
(C-C)
rs
distance
dipole
present
OE
Hirota
and
the
the
v5,
8).
B
rz
evaluated The
(ref. of
moments
perpendicular 14C12CH2,
both
(ref.
9)
ethanes,
includes
band,
~7,
under
medium
the
of
observed
micro-
12CD 3 and 12CH3 13CD 3 3' bond. They also calcuthe
Stark
measurement
14C2H6
the
13CH
of the C-C 17 LLCD From 3 3' the two species.
of
investlqation
al
and
(b)
resolution
effect,
they
of: the
(0.5
perpendicular
band,
,
cm -5
EXPERIVENTAL Both
:lCZH6
paring A
cm
of
14C2H6
0.7
k?a.
lution
as
reported
earlier
was A
of
the
lenght
pressure
Elmer-225
in
the
cell
as
FTS-14
Infrared
spectrometer
Fourier
RESULTS
AND
A
KBr
with
ore-
windows
70
kPa;
14c12cI-i 2 was
estimated
snectrometer
with
mid-infrared a
nartial
used.
of
transform
the
was
that
region,
similar
anodization
data
of
6).
cell
having
boxcar
transform
process
about
kPa,
the
the
was
and
oressure
a Perkin
resolution carried
as
a reso-
were
out
used
during
the
nrocessinq.
DISCUSSION
14C2H6
In
theg7
subband
perpendl;ular PK(J)
resolution and
and
band,Rthe
P,;(J)
The
.
RQK
0
--
A'(l-c)2-Bg c K.
The
spectrum
pO7
were
subband
IS
shown
fitted
by
(A'-A")
In
the -
feature
centres
are
for
R?K
Fig.
squares
Zb'(l-5)-8'1
The
observed
and
14C2H6
From
the
should
vop
Z,
are
summarrzed
experimental be
along
possible
2_B# with in
equation to
and
not is
resolved
given
method
RQ,
to -1
3.47398
cm-l
=
2979.330
cm-l
molecular
medrum
1
for
observed
=
give
constants
to
*Q7
the
and
"2,
to
values:
for
both
12 C2H6
1.
v7(eu)=2979.3+3.47098
determine
our
the
'1 branches
+ [(A'-A")-:B'-B")K2
cm
Table
in of
of
by:
= 0.015239
the
transitlons
a series
negative
1. The
least
A'(l-c)
R-branch
2[A-(l-5)-B'lK
(B'-B")
wo+
are
maln
+
positrve
P - and
RK(J)
and
The
measurement.
V’U
it
gas
Fourier
throughout
from
(ref.
was
0.8
DIOILAB -1 0.5 cm
measurements.
by-products
standard
estimated
inverse
(a)
were
optical
total
for
14CL2CH2
C2H2'
IO
The
and
the
molecular
Kco.ol5289 constants
v
o,
K2, A',
A",
245
-+E
246
5, however
B', B", and band origin forced and
to
is
make
of
the
somewhat
normally
perhaps dubious -1 cm (calculated
cm-l_
from
A
for
from
value
TABLE
the
large
Vo=2977.7896
approximate
derived
molecule).
range
Cole's
only
be
B0=0.06054
B'-
metry
can
value
a C-H
0.06 This
(2985.353
the
values
data
from
for
0.09.
band
for
zeta
‘*tomic
vibration
normal
ethane
the
We
and
the
geo-
obtainedthe
This
5 values
one
obtains 7.564 cm -1
by
(ref.
from
10).
1
Molecular
constants -1 (cm 1
bands
obtained
from
12C
v
A'(1-c)2-B'
+
the
v7
band
14
of
and
C2H6
other
14
H
26
C2H6
2986.729
2979.300~0.0770
2"CA' (l-I)-B'1
3.3530
3.4709
+0.0110
(A'--Al')-_(B’-B”)
kO.0030
0.0103
0.01528
V
2985.35
2977.789
co
0.128
0.096
2895.8
2886.1
2954.0
2947.5
v5(a2u) vB+vll
(b)
(a,u)
14C12CH
?
The 750
line positions are -1 region consists cm
Fonents lower and
falling
to
frequency the
to
fitting
using
the
line
positions V
This
gives
m the
=
should
a
be
transition
g-&. Table
in
bands.
assigned 14C12CH
C is
of
considerably
of
positIons
absorption
weaker to
v5
This
2'
of very
Yolecular 3 by
the
The
comthan
the
14C2H2 strong constants
a polynomial
equation: V
The
line
The
sets
are
fundamental
to
the
2.
close-lying
latter
same
-due
from
in Table
two
frequencies
The
the
band
evaluated
given of
higher
ones.
former
perpendicular were
are -1 cm
Ao=2.589
where
57=0.096, shifted
A'-
thus
for
work.
masses
is
is
and
present that
F+O.O96,
Using
origin
cm-11
for
the
assumption
stretching
to
in
m
- v.
are 728.33
(B'CB")m
reproduced +
2.2592
f
(B'-B")m2
-
satisfactorily m
constants,
- 0.002876
4Dm3
from m2
+
55
the x
expression:
10+m3
presented ln Table 3. 14 If B for 14C12CH is compared with B of and with the B, C2H2' values of 12C2H2 azd 13C2H2 (refs. 6, 111, a reasonable trend is observed.
rotational
+
247 = 1.766
B.
14C2H2 The
B" = X.0657
calculated
parameters served
TABLE
C2H2
cm-'
rotational
is 1.1293. which
14C2H2 constants
from
is in quite
= 1.1195
cm-l
B " = 1.1310
cm-l
%
masses
good
and
agreement
geometrical with
the ob-
B" value.
St is known from
13
cm-l
that
the present
the centrifugal experimental
distortion
data,
is not
constant accurate
D, determined enough.
2
Observed
lzne position
of the calculated
of V5 band
frequencies
J
are
of
The fractional.. parts 2" in parentheses vat. cm -1
14C1*CH
given
P(J)
R(J)
(730.59) 732.75
<0_83)
735.00
(0.08)
723.75
(0.801
737.25
(0.32)
721_50
(0.531
739.50
(0.55)
719.25
(0.25)
741.75 744.00
(0.771 (3.9%)
717.00 714.75
(6.97) (0.68)
746.20
(0.19)
712.45
(0.39)
748.40
10.39)
710.15
(0.10)
750.60
(0.58)
707.85
(0.81)
752.80
(0.76)
705.55
(0.51)
755.00
(4.93)
703.25
(0.21)
12
757.20
(0.09)
700.90
(0.90)
13
759.30
(0.24)
698.55
(0,591
14
761-40
(0.38)
696.20
(0.28)
I5
763.50
(0.52)
16 17
765.60
(0.63)
767.70
10.74)
18
769.80
f0.84)
(726.09)
248
TABLE
3
Calculated
rotational
acetylenes
(cm --l)
constants
obtained
from
w5
14C12CH2 v5
728.33
+ 0.056 0.00220
band
of
l*C
14C2H2 726.39
+ 0.016
1.0636
+
0.0219
B'
1.1282
2
B"
1.1311
+ 0.0220
1.0639
+
0.0219
4D
(-55.1
;
(-14.3
2
13.2)X+
12_7)10-6
labelled
REFERENCES i 2 3 4 5 6 7 8 9 10 11
and I. Laullcht, s. Pinchas Infrared spectra of labelled compounds, Academic Press, London, Ch.5, pp.201-209, (1971). A.H. Nielsen and R.T. Lagemann, J. Chem. Phys., 22 (1954) 36. W. Sterzel and E_ Chorinsky, Spectrochim. Acta., 24A (19681 353. B.H. Baxter and A.F.C. Horsler, Nature, 204 (1964) 675. R.M. Hammacker and J.P. Walters, Spectrochim. Acta 20 (1964) 1311. J_ Mink and G. KemQny, Spectrochim. Acta., 33A (1977) 277. A. Ayoub, G. Kemeny and F. Kling, J. Mol. spectry (in press), J. Mink, J. Mink, A. Ayoub, G. Kemeny, R. Krem6 anti F. Kling, Spectrochim. Acta (in press) _ K. Matsumura, M. Imachi, M. Fujio, Y. Tsuno and C. E. Hirota, Efatsumura, J. Chem. Phys., 66 (19771 2660. A.R.H. Cole, W.J. Lafferty and R.J. Thibault, J. Mol. Spectrosc., 29 (1969) 365. W.J. Laffferty and R-I_ Thibault, J. Mol. Spectrosc., 14 (1964) 79.