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JOURNAL OF MOLECULAR SPECTROSCOPY 17, 341-347 (1965)

Infrared and Raman Spectra of Fluorinated Ethanes


Part XVIII. 1 ,l,l,2-Tetrafluoroethane *

J. RUD NIELSEN AND C. J. HALLEY+

Department of Physics, University of Oklahoma, Norman, Oklahoma

The infrared absorption spectrum of gaseous CFI-CFH, between 309 and


6969 cm-r has been obtained with a Perkin-Elmer model 112 double-pass
spectrometer equipped with CsBr, NaCI, and LiF prisms. The Ramen spectrum
of the liquid at -70C has been photographed with a three-prism glass spectro-
graph of reciprocal linear dispersion 15 d/mm at 4358.%.The vibrational funda-
mentals are tentatively assigned as follows: Species a: 2934, 1464, 1427. 1298,
1103, 972, 343, 665, 549, 408, and 225 cm-r; species a: 3013, 1182, 665, 539, 352,
225, and 129 cm-l. The two lowest fundamentals are taken from previous work
by Danti and Wood.

I. INTRODUCTION
Although t,he infrared spectrum of CFs--CFHZ undoubtedly has been obtained
in more than one laboratory, the only published data appear to be those found
in a paper by Danti and Wood (1) dealing with the far infrared spectrum and the
barrier to internal rotation. No Raman spectral data have been reported. In the
present paper the infrared spectrum of gaseous CF3--CFH2 between 300 and
6000 cm- and the Raman spectrum of the liquid will be reported, and an at-
tempt will be made to assign the vibrational fundamentals.

II. EXPERIMENTAL RESULTS

The sample of 1 , 1 , 1,2_tetrafluoroethane was prepared in the laboratory of


Professor J. D. Park at the University of Colorado. No information was available
about its purity. The infrared absorption spectrum of the gas at room tempera-
ture was obtained with a Perkin-Elmer model 112 double-pass spectrometer
equipped with CsBr, NaCl, and LiF prisms and a l-m cell. The Raman spectrum
of t.he liquid at - 70C was photographed with a three-prism glass spectrograph
of reciprocal linear dispersion 15 A/mm at 4358A. An attempt to obtain the
Raman spectrum of the gaseous phase yielded only the two strongest bands. No
polarization measurements were made. The infrared spect,rum is reproduced in
Fig. l-3. The Raman data are listed in Table I.
* This work has been supported by the U. S. Atomic Energy Commission under Contract
No. AT-(40-l)-1074.
t Present address: Oklahoma Baptist University, Shawnee, Oklahoma.
341
80

60

40

20
c
.P
x 0
.- I
.c 14 I5 16 17 22 23 24 25 26 27 28 ;
2 angth in Microns
0
i Wwe Numbers in cm-l

CF3-CH2F

L*IORATOI
UNIVERSITY OF
OKL4HOMA

-we I rnnth ;n ~irrc.n.


FIG. 1. Infrared absorption spectrum of gaseous 1,1,1,2-tetrafluoroethane. Cesium bromide prism.
Wave Numbers in cm-f

v
Wave length in Microns
6
c Wave Numbers in cm-t
E
8100

%
CF3-CH2F
80
SOURCE
AND ,I,11

J.D. PARK

NOCI

,ABOATOII
UNIVERSITY OF
OKLAHOMA

Wave Length in Microns

FIG. 2. Infrared absorption spectrum of gaseous l,l, 1,2-tetrafluoroethane. Sodium chloride prism.
Wave Numbere in cm-t
3500 3000 2500

80

60

40

20

._6
.-D 0
E 1.5 2.0 2.5 3.0 3.5 4.0 485
z Wave Length in Microns
e Wave Numbers in cm-t
I-
z 2000 1900 I600 1700 1600
(UIOO I
COMPOUND

E
ti CFy CH2F
80 A r7lmm
SORCs
Mm SlTl
I

J.D. PARK

LiF
L*lol*ToI
UNIVERSITY OF
OKLAHOMA
0
5.0 5.5 6.0 6.5
Wave Length in Microns

FIG. 3. Infrared absorption spectrum of gaseous l,l, 1,2-tetrafluoroethane. Lithium fluoride prism.
SPECTRA OF 1, 1 , 1,2-TETRAFLUOROETHANE

TABLE I
RAMAN SPECTRUMOF 1,1,1,2-TETRAFLUOROETHME LIQUID AT - 70C

Wave number Description& Interpretation

358 cm-r W a fundamental


410 s, sh a fundamental
466 VVW 2 x 225 = 450 A?
534 W a fundamental
548 m a fundamental
663 W a + a fundamentals
823 VW 2X410=82OA
839b vs, sh a fundamental
968 W a fundamental
1028 vvw
1063 VW 2 X 534 = 1074 A?
1081 m, d a fundamental
1178 w, d a fundamental
1200 VW 539 + 665 = 1294 ?
1290 m, d a fundamental
1428 VW, d a fundamental
1461 s, sh a fundamental
2832 W 2 X 1428 = 2856 A
29QOc VS a + a fundamentals

BThe following abbreviations are used: s strong, m medium, w weak, v


very, sh sharp, and d diffuse.
b In the Raman spectrum of gaseous CF3CFH2 a strong sharp band was found
at 841 cm-r.
0 In the Raman spectrum of gaseous CF&FH, a strong sharp band was
found at 2984 cm-r.

III. INTERPRETATION

The CF,CFH2 molecule may be assumed to have the symmetry C,, and the
18 normal vibrations divide themselves into 11 of species a and 7 of species a.
The principal moments of inertia of the molecule have been calculated by Danti
and Wood (1). They found the values 99.4, 186.4, and 187.0 amu A2, showing
that the molecule is very nearly a symmetrical top. From the theory of Gerhard
and Dennison (2) it is found that parallel infrared bands should have a P-R
branch separation of approximately 15 cm-l and that the zero branch should
have an intensity equal to 26 per cent of that of the entire band. Perpendicular
bands should be fairly broad with only an indication of P&R structure. Infrared
bands of species a should be perpendicular, whereas bands of species a should
have hybrid contours. Unfortunately, only the infrared bands at 352, 408, and
843 cm-1 have so well-resolved contours that their species are revealed with
certainty. For this reason, and because of the absence of Raman polarization
data, the assignment of the vibrational fundamentals given here must be regarded
as in part tentative.
346 NIELSEN AND HALLEY

The strong infrared bands at 3013 and 2984 cm-i can with confidence be in-
terpreted as a and a fundamentals, respectively, associated with asymmetrical
and symmetrical C-H stretching. In the Raman spectrum of gaseous CF&FH2
only the a fundamental is observed, while in the Raman spectrum of the liquid
the two bands appear to be unresolved, giving rise to a single maximum at
2990 cm-l.
The infrared band at 1464 cm-i has a strong and sharp counterpart in the
Raman spectrum. It is undoubtedly an a fundamental involving mainly CH2
deformation, The four strong infrared bands at 1427, 1298, 1182, and 1103 cm-l
must be interpreted as fundamentals associated largely with C-F stretching.
Three of these should belong to species a and one to species a. All of the cor-
responding Raman bands are quite diffuse, as are most Raman bands arising
from C-F stretching. However, the bands at 1178 and 1428 cm-i are more
diffuse and weaker than the other two Raman bands, and one of these two most
likely represents the a fundamental. Somewhat arbitrarily the former has been
so assigned.

TABLE II
FUNDAMENTAL
VIBRATIONALFREQUENCIESOF 1 ,1,l ,2-TETRAFLUORETHANE

Species Infrared (gas)a Raman (liquid)8

a 2984 5 299Obvs
a 1464 8 1461 s, sh
a 1427 s 1428 VW, d
a 1298 vs 1290 m, d
a 1103 vs 1081 m, d
a 972 vs 96Sw
a 843 vs 839 vs, sh
a 665 vs 663 w
a 549 vs 548 m, sh
a 408 m 410 s, sh
a 225d -
a 3013 vs 2990 vs
a 1182 vs 1178 w, d
arr 665 vs 663 w
a 539 m 534 w
a 352 s 358 s
a 225d -
a 120d -

8 For abbreviations used, see footnote to Table I.


b In the Raman spectrum of gaseous CFaCFHz the measured wave number
was 2984 cm-r.
c In the Raman spectrum of gaseous CF3CFH2 the measured wave number
was 841 cm-r.
d This band was observed by Danti and Wood (1).
SPECTRA OF 1,1,1,2-TETRAFLUOROETHANE 347

The very strong infrared band at 972 cm-l has a weak but sharp counterpart
in the Raman spectrum. It is interpreted as an a fundamental probably arising
from a vibration involving mainly CH2 wagging. The very strong infrared band
at 843 cm-l has a contour which indicates that it is a parallel band. It is very
sharp and intense in the Raman spectra of both liquid and gaseous CF&FHz.
It certainly represents an a fundamental. The corresponding vibration may be
characterized as largely C-C stretching.
The deformation of the CF, group may be expected to give rise to an a fun-
damental near 600 cm-l and to a and a fundamentals near 550 cm-. The in-
frared bands observed at 665 and 549 cm-l are identified as the a fundamentals
in question. With less certainty because of its sharp appearance in the Raman
spectrum, the band at 539 cm-i is assigned as the corresponding a fundamental.
Of the remaining two a fundamentals one can be identified unambiguously
with the infrared bands at 408 cm-1 which has a contour typical of parallel bands.
The lowest a fundamental has been tentatively identified with the band at 225
cm- of indistinct contour observed by Danti and Wood (1). The vibrations
associated with these two fundamentals may be characterized as rockings paral-
lel to the symmetry plane.
Of the remaining four a fundamentals, two can be assigned with certainty.
The strong infrared band at 352 cm-1 has perpendicular contour and a fairly
diffuse counterpart in the Raman spectrum. It must be an a fundamental asso-
ciated with rocking perpendicular to the symmetry plane of the molecule. The
infrared band at 120 cm-l observed by Danti and Wood (1) also is undoubtedly
an a fundamental associated with a torsional motion.
There appears to be little basis for assigning the two remaining a fundamen-
tals. One of them, associated with out-of-plane rocking, probably lies below the
wave-number range studied in the present work. Since the band at 225 observed
by Danti and Wood has no typical contour, it is assumed tentatively that it
represents overlapping a and a fundamentals. The last a fundamental is either
very weak in both spectra or is also masked by one of the other fundamentals.
We have assumed, somewhat arbitarily, that it overlaps the a fundamental at
665 cm-l. It is possible, however, that it lies higher and is represented by one of
the very weak bands near 770, 885, and 1065 cm-. The assigned vibrational
fundamentals are listed in Table II.
RECEIVED May 15,196s

REFERENCES

I. A. DANTI AND J. L. WOOD, J. Chem. Phys. 30, 582 (1959).


2. S. L. GERHARD AND D. M. DENNISON, Phys. Rev. 43, 197 (1933).