EnergyConversion. Vol.10, pp. 29-32. PergamonPreu, 1970.

Printedin GreatBritain

The Distillation and Analysis of Propylene Carbonate

for Use in Non-Aqueous Electrolyte Batteries
STUARTG, MEIBUHR,tBERNARDE, NAGEL$and ROGERGATRELL§
(Received 28 July, 1968)

Introduction The vacuum p u m p was protected from organic vapors

Because of its relatively high dielectric constant and by using a dry-ice cold finger.
good solvent properties [1], propylene carbonate (PC)
is being used as the solvent in high energy density bat- Gas-liquid chromatographic analysis
teries [2-4]. Several multicell batteries using lithium as The operating conditions for the G L C analysis of PC
the negative plate material and PC as the organic solvent are given in Table 1.
have been built and tested [2, 5, 6]. This interest in
organic electrolyte batteries has caused an increase in Table 1. Analyticaleonditionsforgaschromatographic
analys~ofpropylenecarbonate
the number of investigations of electrochemical pheno-
mena in PC solutions. However, before PC can be used
Column 6 ft x 0.25 in. Stainless steel, 10 per cent carbo-
as the solvent in electrode kinetic studies, it must be as wax 20 M on 60--80 chromosorb W
pure as possible so that observed effects will not be Gases Helium --36 psig
traced to impurities. Hydrogen--15 psig
Air --22 psig
Although a number of publications briefly reported Temperature Detector (flame) 250°C
[7-13] a procedure for the purification of PC, only one Detector (thermistor) 250°C
published paper [14] is devoted exclusively to its purifica- Injection port ~ 110°C
Column 75-245°C at 8°C/min
tion and analysis. Several publications [7-10] relate that Operation Dual column--sample injected into Column A
PC was fractionally distilled under vacuum, but they Recorder 1.0 mV, 2 min/in.
fail to specify either the exact conditions for collecting Instrument F & M (Hewlett-Packard) Model 810 equipped
with flame ionization and thermal conductivity
the distillate or the composition of the desired fraction. detectors
This report describes the analysis of PC to identify
the impurities that remained after the distillation.

Experimental The areas under the chromatographic peaks were

measured with a K & E compensating polar planimeter
Distillation procedure with the tracer arm set at 20.42 and the pole arm set
Slightly yellow propylene carbonate, obtained from at 30.68. By measuring the area under the PC peak and
two sources, Aldrich Chemical Company and Jefferson assuming this value corresponded to 100 per cent, an
Chemical Company, was vacuum distilled. Ten-milliliter approximate value for the concentration of the impurities
fractions, each representing about 1 per cent of the total could be obtained.
quantity of PC charged to the distilling pot, were col- In one series of experiments, the kettle residue after
lected until approximately 30 per cent of the pot was 95 per cent of the pot charge was removed by distillation,
distilled. The pot residue and some of these 10-ml was chromatographed and the appropriate effluent was
fractions were analyzed by gas-liquid chromatography trapped with a Carle Solution Fraction Collector. The
(GLC).
The vacuum distillation was performed in all-glass Table 2. Analytical conditions for fraction identification
equipment obtained from the Todd Scientific company.
The 90-cm long, 1.2-cm dia. column was packed with
Gas chromatograph
glass helixes and had 53 theoretical plates at total Column 6.5 ft x 0.25 in. copper,
reflux [13]. The still head, when operated at a 50 : 1 Carbowax 4000
take-off ratio, gave approximately 20 ml of distillate per (modified for "on column injection")
Temperature 100-220°C (ballistic program)
hour. Generally, the column was operated at 3-4 m m Carrier gas Helium (90 ml/min)
of Hg pressure, yielding PC at a temperature of 84-86°C. Recorder 1-0 mV, 2 rain/in.
Instrument Perkin-Elmer Model 154D vapor fractometer,
thermistor detector
Fraction collection
t Electrochemistry Department Research Laboratories, General Instrument Carle Model 60 solution fraction collector
Motors Corporation, Warren, Michigan, U.S.A. Temperature 250°C
:~ Chemistry Department Research Laboratories, General Solvent Carbon tetrachloride
Motors Coroporation, Warren, Michigan, U.S.A. Pressurizing gas Argon at 4 psig
§ No longer with General Motors Corporation. Collection rate ~ 4 t~l./min
29
30 STUART G. MEIBUHR, BERNARD E. NAGEL and ROGER GATRELL
effluent was then transferred to a micro i.r.
analyzed using a Perkin-Elmer Model 621
spectrophotometer. The operating conditions
GLC separation and fraction collection of
shown in Table 2.
Results and Discussion
All chromatograms were obtained with the flame
ionization detector set at maximum sensitivity unless
otherwise stated.
(o) V
==
j
I I I I I I
o
(b)
o 6 ,o ,2 ,4 ,6
Retention times, rnin
Fig. 1. Chromatograms for propylene carbonate; (a) received
from Aldrich Chemical Company; (b) received from Jefferson
Chemical Company; curves C, "as received"; curves D, first
10 ml of distillate.
Figures l(a) and l(b) show the chromatograms of the
"as received" PC (curves C) and of the first 10 ml of
distillate (curves D) for material obtained from Aldrich
Chemical Company and Jefferson Chemical Company,
respectively. Two important differences are seen: (a) the
material from Jefferson Chemical Company contained
fewer impurities; and (b) those impurities that were
present were at a lower concentration, as evident from
the smaller area under the peaks. Analysis of each of the
thirty 10-ml fractions showed that the impurity level
was lower also in the Jefferson Chemical Company
sample than in the Aldrich Chemical Company sample.
Consequently, the further work described here has been
limited to PC obtained from Jefferson Chemical Com-
pany.
Some of the impurities that were identified by com-
paring the retention times of the pure material with the
retention times of peaks found in the chromatogram
of the distillate included propylene oxide, allyl alcohol,
and 1,2- and 1,3-propanediol. It was not important to
identify all of the peaks, only those that remained after
distillation.
In Fig. 2 is plotted the peak area (in arbitrary units,
using the thermal conductivity detector) for 1,2-pro-
cell and
infrared 200 •
for the
PC are
v
I00
0 f 2 3 4 5 6 7 8 9
Fraction number
Fig. 2. Change in peak area for 1,2-propanediol plotted against
the number of the distillate fraction.
I I
V
panediol (retention time = 14.1 min) against the fraction
number of the distillate. As is evident, the peak area
asymptotically approached zero. Similar results were
\ obtained with all other impurity peaks except the
post-PC peak that occurred at 18.3 min.
This peak area remained apparently unchanged for
all of the 30 fractions. Assuming the area under the
PC peak (Fig. 4 obtained using the thermal con-
2o ductivity detector) was 100 per cent, the area under
this post-PC peak corresponded to about 0.5 per cent.
These results are in disagreement with the results of
Jasinski and Kirkland [12] who found that neither of
the two post-PC peaks detected in their "as received"
sample was evident in the distillate. No explanation for
this discrepancy is immediately available.
Since the impurity causing the post-PC peak was
not removed by simple fractional distillation, its identi-
fication became important. Since it was a post-PC
rather than a pre-PC peak, its boiling point was assumed
to be higher than that of PC. Temperature programming
of the chromatographic column suggested that its boiling
point was around 245 °C at atmospheric pressure whereas
the boiling point of PC was estimated to be about
240°C. The literature value for the boiling point of PC
is 241.7°C [1]. Therefore, the actual boiling point of
the post-PC impurity may be closer to 247°C. Because
the impurity apparently had a higher boiling point
than PC, it was hoped that it could be concentrated in
the boiling kettle. Consequently, a 1000-ml sample of
PC was distilled until only about 50ml remained.
Analysis of this residue showed that the concentration
of the post-PC impurity was increased to about 5 per
cent.
Infrared analysis of the trapped chromatographic
effluent, which corresponded to the post-PC peak,
confirmed that the impurity was ethylene carbonate
(boiling point 248°C). In Fig. 3A is given the i.r. spectrum
for pure ethylene carbonate (EC) that was put through
 T h e D i s t i l l a t i o n a n d A n a l y s i s o f P r o p y l e n e C a r b o n a t e f o r U s e in N o n - A q u e o u s E l e c t r o l y t e Batteries 31

Wavelength, F

2.5 5 4 5 8 7 ..... 8, ~.... 9 I0 12 15 20 30 4 0 5 0

i i '''~'" : ~/J I L , I I ~l~

": ,7''!
-4-
I
Iti < !

~ I I l ;i-r--" 7
_ I i i!lj,
,
v- ~---7-1

iT i; IJ
!!' i,i~,
_ _-,~
i 77

iT~
I i
iii
-i71,,
--i .i ~ --~o; i i i
1 :/i, I~1 ;I
'

-~--~-1-
I I iii i I IT! ,
4000 3500 3000 2500 2000 1800 1600 1400 1200 I000 800 600 400 200
Wovenumber, cm-I
WovelenQth~ #1

2.5 . 3 4 5 6 7 8 9 I0 12 Ifl 20 50 4050

i "i ....... ! '~ ..... .... cr ",("i'1' '~"i~i
~I ' 1! 1,1'
'~ '1", ', ','I i~!",'! '''~'?'I'' 'I'i
100
,i ,~,l~i] " I "~"
i 1 .... ll~i- ii ~"~ Aiil I1 I,
~5-tt I tl I ! I I I ', ! I.l.~ ,"t I
d I ~ I iUl ,,( . . . . ,i .... Jl
I1! ~i [~1 nl
d!
i ' I I I I I I~ I ; ~ I
I
]
°11 III I
fit I I/.,
', ' 17
I t
'i I I I ~"' ! I II !-
I
g I
i i i i : ~ i i i i
IN ~--~-
~111- I!1'11!!~i I "! " Itlil
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!:"
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o
.... fJ_ !i '' I i Ii

,
,r ! s:
~i ': !i

o__11 I i i ~ i I i [ iTI : i ' I

1800
illtt!lt 1!
, , i
1600
, , ,
f400
, , ,
1200 iOOO 800 600 400 200
4ooo 5500 3000 2500 2000
Frequency, crn-I

Wavelength, #~

2.5 3 * 5 6 r e ....? .. ~o ..... !~ .......... ,p. . . . . . . 29 . . . . . . . ~ .4o5o

,ool~!i L ili';ill' I;/1~!/! il i'll,,",i; ......... ! " ' ' ~i-i

dT " ~ ' ' ~ I I ' "---V, [g ~ , - ] i [ la I T : ' ,

6o } t{ .... ~ I_ ' uH,'~ " i
_g , ~ , ~ I , : , . , ~ -77r I-~!-:CT i- - c - r
4o ,, t ,, , , , ~, _!!! i d ,i, itll
¢

4000 3500
Z {

3000
77J: .17755
2500
.... I ! i :

2000
;

1800
j
-_2 r +: !-!-r
! ]

1600
i '

1400
t e I

1200 [000
~>@~-i-4~-~
800 600
_._+

J2.a
400
! { 200

Frequency, crn-I

Fig. 3. infrared curies: A, pure ethylene carbonate; B, the trapped post-PC fraction; mid C, the traplled PC fraction.

the GLC column and trapped in a manner identical to single broad band. This shift may be the result of slight
that used for the kettle residue. Figure 3B shows the thermal degradation during the GLC analysis. The
i.r. spectrum for the post-PC fraction, and Fig. 3C absorption bands near the frequencies 1545 (strong),
gives the spectrum for the PC fraction; both of these 1245 and 1210 doublet (moderate), 1000 and 975 doublet
fractions were trapped from the kettle residue.
T a b l e 3. R e s u l t s o f distilling a 1 : 2 m i x t u r e o f E C : P C
The significant differences between the spectra of PC
and EC are shown between 1000 and 2000 cm -1. Pro- Fraction number EC (~) PC (~)
pylene carbonate has characteristic absorption bands at Pot charge 34.8 65.2
1050, 1110, and 1170 cm -1. The spectrum for EC does 1 9.0 91.0
2 23-0 77.0
not have the middle band of the CH-CHa triplet, and
3 25.5 74.5
there is a slight shift in frequency; the remaining absorp- 4 24.8 75.2
tion bands are located at 1075 and l l e 0 c m -1. When 7 27.0 73.0
11 30.7 69.3
the spectrum of pure EC (not shown) is compared with
15 34.6 65.4
the spectrum obtained from the GLC effluent (Fig. 3A), 18 34.0 66'0
it is noted that the sharp double band in the CHz--CH2 21 35.9 64.1
Pot residue 57.8 42.2
stretching region (2800-3000cm -1) is replaced by a
32 STUART G. MEIBUHR, BERNARD E. NAGEL and ROGER GATRRIJ~
(moderate), and 760 cm -1 (strong) may be ignored
because they are caused by the CC14 solvent.
A separate experiment was performed to determine
whether there was a change in concentration of EC
with the fraction of material that distilled. Pure EC
and pure PC were mixed in the ratio of 2 : I and vacuum
distilled. Fractions representing about 3 per cent of the
pot charge were collected and analyzed by GLC. The
results, shown as percentages of EC or PC in each
fraction, are listed in Table 3. These results confirm
that EC is concentrated in the kettle residue. Although
there appears to be a gradual increase in EC as more
distillate is removed, no significant change in EC in the
distillate could be detected when the initial concentration
was low (as it is in the "as received" PC).
0 2 4 6 8 I0 12 14 [6 18
Retention times, rain
Fig. 4. Clu~mato~'ams for PC timt is sal~equeafly used in
electrochemical studies. Curve A, flame ionization detector;
curve B, thermal conductivity detector.
Method o f distilling P C
Propylene carbonate, which will be used for subsequent
electrochemical studies, is distilled in this manner: the
first 30 per cent of the pot charge that distills is discarded,
and the next 60 per cent is collected and used. The
remaining 10 per cent in the pot is also discarded.
Propylene carbonate that has been distilled in this
manner exhibited chromatograms similar to the one
shown in Fig. 4. Curve A is for the flame ionization
detector, and curve B is for the thermal conductivity
detector. The flame detector showed that a small pre-PC
impurity was present in concentrations below 20 ppm.
This impurity was 1,2-propanediol. Neither this com-
pound nor ethylene carbonate (the post-PC impurity)
is expected to affect adversely the electrochemical
studies.
References
[1] Propylene Carbonate Technical Bulletin. Jefferson Chemical
Company.
[2] R. Jasinski, Electrochem. Technol. 6, 28 (1968).
[3] R. Jasinski, Electroanal. Chem. lnterfacial Electrochem. 15,
89 (1967).
[4] K. H. M. Braeuer, Proc. 20th Ann. Power Sources Conf.
p. 57. Atlantic City, N.J. (1966).
[5] H. N. Seiger and A. E. Lyall, Paper No. 680454, presented at
the Mid-Year Meeting of the Soc. of Auto. Eng., Detroit,
Mich., May 20--4, 1968.
[6] H. N. Seiger, S. Charlip, A. E. Lyall, and R. C. Shair, Power
Sources Conf. 21, 45 (1967).
[7] M. L. B. Rao, J. electrochem. Soc. 114, 14 (1967).
[8] A. N. Dey, J. electrochem. Soc. 114, 823 (1967).
[9] A. N. Dey, J. electrochem. Soc. 115, 160 (1968).
[10] M. L. B. Rao and R. W. Holmes, Electrochem. Technol. 6,
20 22
105 (1968).
Ill] R. F. Nelson and R. N. Adams, J. electroanal. Chem. 13,
184 (1967).
[12] V. Gutmarm, M. Kogelnig, and M. Michlmayr, Monat. Chem.
99, 693 (1968).
[13] J. N. Butler, Anal. Chem. 39, 1799 (1967).
[14] R. J. Jasinski and S. Kirkland, Anal. Chem. 39, 1663 (1967).
[15] F. Todd, Modern Fractional Distillation Equipment for the
Laboratory. Literature from the Todd Scientific Company
(1964).