Spectrochtmlca Acra Vol CA, pp 175 to 179 Pereamon Press Ltd.. 1979.

Prmted m Great lhta~n

Raman spectrum of propylene carbonate

G. J. JANZ. J. AMBROSE*, J. W. Courrst and J. R. DOWNN, JR:
Cogswell Laboratory, Rensselaer Polytechnic Institute, Troy, New York 12181, USA

(Received 27 July 1977; revised 12 December 1977)

Abstract-The Raman spectrum of propylene carbonate (4-methyl-1,3-dioxolan-2-one) has been re-

corded and analyzed. Vibrational assignments have been made for many of the observed frequencies
on the basis of comparison with accepted assignments for certain vibrational modes in other
compounds with close structural similarities.
The spectra of propylene carbonate (PC)-water mixtures have been studied over the entire con-
centration range at 80” and there seems to be little or no interaction except for partial disruption
of hydrogen bonding in water by PC. Raman soectra of solutions of LiC104 in PC and in PC-HI0
mixturesmdicate possible solvatibn of the Li+ ion.

In connection with studies of the solvation of ions [9]. For the last-named compound the normal fre-
by water in propylene carbonate (4-methyl-1,3- quencies of vibration were calculated using a
dioxolan-2-one) we have determined the Raman mechanical model.
spectrum of the compound and have made vibra-
tional assignments to most of the bands appearing yH3 CH3-0
in the spectrum. A normal co-ordinate analysis has \
not been made (a difficult problem for a complex F-0 CSO
\ / /
molecule with no symmetry), but analogies have been
drawn from the assignments made for similar molecules
by earlier investigators.
I
CH3-0
/
‘e-0

_
CH3-0

The i.r. spectrum of propylene carbonate (PC) has I II

been measured previously and is recorded in the
Sadtler collection [1] while the Raman spectrum has CH3 CH3
been the subject of only .one prior investigation [2].
The structural formula of PC is shown as formula I, CH -0 CH -CH,
below. ANGELL [3] has made detailed assignments on \ -\
e0 GO
ethylene carbonate (formula II), based on observations / /
of both i.r. and Raman spectra. More recently, CH3-CH3 CHs-CH,
DURIG et al. [4] examined the i.r. and Raman spectra III IV
of ethylene carbonate over the low frequency region
to study ring deformation, and they questioned CH3
certain of ANGELL’Sassignments. HALFS er al. [S]
studied the i.r. spectra of a series of cyclic carbonates,
YH -cH2 \
including Pe, with particular attention being paid
to the C=O stretching frequency. NYQUIST and
POXTS[6] have summarized the spectra of ethylene
I
CH2-CH;
/
‘CH2

carbonate and related compounds. RASMUSSENand

BRATTAIN[7] have studied the i.r. spectrum of II-
valerolactone (formula III), but the purity of the
sample was doubtful and discussion was limited to
the VC=O hand. Other structurally similar compounds
which have been studied are 3-methylcyclopentanone
(formula IV) [S] and methylcyclopentane (formula V)
* Present address : International Nickel Co., Mississauga,
Ontario, Canada.
t Visiting Professor, Rensselaer Polytechnic Institute,
1974-75; on leave from Lake Forest College, Lake Forest,
Illinois, U.S.A.
$ Present address: Dow Chemical Company, Midland,
Michigan, U.S.A.
V
EXPERIMENTAL
The PC employed in this investigation came from two
different sources: one sample, subjected to no further
treatment, came from Tyco Laboratories, and the other,
purchased from Burdick and Jackson, was of high purity,
distilled in glass. Samples from the latter source were
dried over Type 4A molecular sieves; Karl-Fischer titration
(photovolt Aquatest instrument) showed a water content of
less than 8Oppm. PC from the two sources gave identical
spectra; the Tyco sample was re-scanned five years after
having been sealed off, and the spectrum was identical
with that run earlier. The 5-year-old Tyco PC-water
sample. which has been heated to 80°C at one time. con-
176 G. J. JANZ er al.

cm-’

Fig. 1. The Raman spectrum of propylene carbonate.

tained spurious peaks at 1275 and 1375cm-’ in addition
to the normal peaks. We suspect these are due to hydrolysis
products of PC. To check this suspicion we added aqueous
HCI to the Burdick and Jackson sample, worked it back
and forth intermittently for several hours and reran the
spectra; the same spurious peaks appeared, confirming
that acid hydrolysis causes deterioration in a short time
at room temperature. FUJINAGAand lzursu [IO] quote the
acid decomposition products as propylene oxide, pro-
pionaldehyde, ally1 alcohol and carbon dioxide. Analytical
grade LiCIO, was recrystallized twice from water, then
dried in a porcelain dish first in a vacuum oven at 120”,
and then in a vacuum desiccator over PzOS.
The spectra were recorded with a Jarrell-Ash laser-
Raman spectrometer (Model 25-300) using an argon ion
laser as excitation source (5145A; 1.3 W maximum). The
spectral slit width for all spectra was Zcm-’ and the
frequency calibration of the instrument was checked using
a low pressure Hg-arc lamp; quoted frequencies should
be accurate to k lcm-’ for sharp peaks. Our spectro-
meter is interfaced with a PDP-15 computer for computer-
assisted signal averaging with seven functionally distinct
software subsystems for data acquisition, storage, redisplay
and contour analyses. A complete description is given
elsewhere [ll]. Infrared spectra were obtained with a
Perkin-Elmer 621 spectrophotometer. Curve analyses were
carried out with a duPont 310 Curve Analyzer. All spectra
were recorded at room temperature except for the Raman
spectra of the PC-H20 solutions which were recorded at
80°C to prevent phase separation.
RESULTS AND DISCUSSION
The PC Raman spectrum is shown in Fig. 1 and
tabulated in Table 1. The Raman and i.r. spectra are
very similar, with the most striking differences being
intensity differences, which are the result of different
selection rules for the two types of spectra.
Frequency assignments for several of these bands
have been made according to the logic outlined in
Table 2, based on comparisons of previously assigned
frequencies in structurally similar compounds. These
assignments are based mainly on the frequencies and
polarization dependence of the Raman spectrum. Two
of the assignments in Table 2 are discussed in more
detail below. The assignments presented in Table 2
agree quite well with those given by PETHRICK and
WILSON [2]. The main differences are for the 451
and 780cm-’ peaks where we prefer assignments in-
volving the carbonate group and they prefer assign-
ments involving the organic skeleton. While we feel
our assignments have a firmer basis it appears that
isotopic substitution studies will be required to indicate
a clear choice.
ANGELL[~] and DURIG er al. [4] both reported a
band at 717cm-’ in the Raman spectrum of liquid
 Raman spectrum of propylene carbonate 177

Table 1. Raman and i.r. spectra of propylene carbonate

R-n Frequency Relative Infrared _l Relative

cm-l Intensfty Frequency, cm Cntcnsity

191 v, d*

318 W, d
*
451 WY P

544 w. d
635 w(broad) 630

714 a* P 715

780 v-r, d 780

852 a* P 850

916 v* d 920

959 m* P 955
1054 d 1050
1068 w (broad)
1078 d 1070
1124 w, d 1120

1152 v* P .
1180 VW, d 1180 s

1228 v. d 1230 W

1341 v, d 1340 W

1354 v, d 1355 m

1394 w, d (2: 1390 m

m (broad), d 1450 W

m, d 1485 W

m(aaym) P 1790 VS

2665 w, PC?) 2500 W

2760 WS P 2760 W

2797 w* P

2884 s9 P 2880 w

2944 vss P 2930 s

2996 ve, P 2990 (1

* d = depolarized ; p = polarized.

ethylene carbonate, but the two groups of workers it to an Al skeletal bending mode of the five-membered
assigned it differently. ANGELL found it to be de- ring.
polarized and assumed it to be a C=O bending The 1787cm-’ frequency has been attributed to
vibration, while DURIG et al. found the band to be the -C+O stretch, an Al mode. CA.STINELet al. [14]
strongly polarized and assigned it to a skeletal observed G=O stretching frequencies in the i.r. at
bending mode. We observe a strongly polarized band 1732 and 1746 cm - 1for cyclopentanone and 1745 cm- ’
in the Raman spectrum of PC at 714cm-’ and assign for 3-methylcyclopentanone. The corresponding fre-
178 G. .I. JANZet trl.

Table 2. Vibrational assignments for propylene carbonate

% Assignment Basis of Assignment Related to Reference I

-

191 out-of-plane ring analogy to ethylen 141

-1
bending (puckering), carbonate, 217 cm ;
B2 cyclopentanone, 236 cm-l; c 41
and methylcyclopentane c.93
at 227 cm-l.

451 ethylen _f carbonate, [41

(degenerate?) 525 cm ; cyc lopentanone ,
472 cm-l

bending, A,

714 skel;tal bending analogy to ethylene

mode, Al carbonate, 717 cm-l r41
780 L 0 out-of- characteristic of
II plane dialkyl carbonates (61
C skeletal
/ 1
0 0
deformation

as2 symmetric ring cyclopentane, 890 cm ;

-1
vibration methylcyclopentane, 890 cm-l.

959 0
_0_:_0_
fi61
syasnetric stretching, Al

1054 -C- 0- ring c5 1

1180 3 stretch

1228
f: [6 1
‘O-C-O-
asymmetric
stretch, B
1
1354
1394
-CH3 symmetric
-ON2 wag
deformation
7,.
Ii3 1

-CH3 asymmetric deformation

?+
1456

1486 -OCH2 deformation

i
1787 -C-O stretch cyclopentancme; Cl41
3-methylcyclopentanone;
A1
ethylene carbonate C51
1805 Combination of
852 and 959 ? r18’1

C-H stretch El31

quency in cyclic carbonates can be expected to be HALES et al. [S] observed bands in the i.r. spectrum
somewhat higher than in the analogues just mentioned of ethylene carbonate. The splitting of this band was
because the -C=O distance in these compounds attributed [3] to the Fermi resonance effect since the
has been shown, by X-ray analysis, to be unusually first overtone of the skeletal breathing vibration (or
short [1.5]. The Raman spectrum of ethylene carbonate symmetrical ring vibration) is 1780cm-‘. Fermi
in water r3] gives bands at 1770cm-’ and 1806cm-‘. resonance between these components is not possible
 Raman spectrum of propylene carbonate
in PC because the symmetrical ring vibration occurs
at a much lower frequency, viz. 852cm- ‘. The asym-
metric peak at 1787cm-r can be resolved into two
components at 1787cm-’ and 1806cm-‘. The 1805
cm-’ frequency may be a combination band (e.g.
852 + 959cm-I). Roth components are strongly
polarized and Fermi resonance may account for the
huger than expected intensity of the combination
band. FORTUNATO et al. [18] give a similar assign-
ment for ethylene carbonate.
It is worth mentioning that, in a series of several
solutions made up with water, ranging from 11.8 MPC
down to 0.83 M PC, there was no indication of inter-
action of PC with water-i.e. there was no dis-
placement of PC peak positions nor distortion of
band contours. There was evidence, however, that PC
brings about a partial breakdown of hydrogen bonding
in water, in that the 3550cm- ’ band of water in-
creases inordinately in intensity relative to the
324Ocm- ’ band in samples containing higher pro-
portions of PC. WALRAFEN[16], in his careful study
of the i.r. spectrum of water at different temperatures,
attributed the 355Ocm-’ band to “unbound” water
and the 324Ocm-’ band to hydrogen-bonded water.
A 1 M solution of LiClO, in PC and in PC-H20
showed small, but significant changes in the contours
of the PC bands at 7141~1~’ and 1787cm-’ bands,
suggesting possible solvation of the Li’ ion by PC, in
keeping with NMR studies on the system LiC104-
HzO-PC by COGLEY et al.[IT]. The investigation of
the phenomenon has not been carried beyond these
initial observations since the effect seems too diffuse
to yield quantitative results.
Acknowledgemenrs-This work was made possible, in large
part, by support received from the National Science
Foundation, Washington, D.C.
REGISTRY NUMBERS
Propylene carbonate (4-methyl-1,3-dioxolan-2-one [108-
32-71J
179
Ethylene carbonate (1,3-dioxolan-2-one) [96-49-l]
y-Valerolactone (dihydro-5-methyl-2-(3H)-furanone) [108-
29-21
3-M&hylcyclopentanone [ 1757-42-21
Methylcyclopentane [96-37-71
Lithium Perchlorate [7791X)3-9]
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