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The Distillation and Analysis of Propylene Carbonate For Use in Non-Aqueous Electrolite Batteries Meibuhr1970
The Distillation and Analysis of Propylene Carbonate For Use in Non-Aqueous Electrolite Batteries Meibuhr1970
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v
ionization detector set at maximum sensitivity unless
I00
otherwise stated.
(o) V
0 f 2 3 4 5 6 7 8 9
Fraction number
==
Fig. 2. Change in peak area for 1,2-propanediol plotted against
j
the number of the distillate fraction.
I I I I I I I I
o
(b) 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
Wavelength, F
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1 :/i, I~1 ;I
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4000 3500 3000 2500 2000 1800 1600 1400 1200 I000 800 600 400 200
Wovenumber, cm-I
WovelenQth~ #1
,
,r ! s:
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Wavelength, #~
4000 3500
Z {
3000
77J: .17755
2500
.... I ! i :
2000
;
1800
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1600
i '
1400
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1200 [000
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800 600
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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 first 30 per cent of the pot charge that distills is discarded,
because they are caused by the CC14 solvent. and the next 60 per cent is collected and used. The
A separate experiment was performed to determine remaining 10 per cent in the pot is also discarded.
whether there was a change in concentration of EC Propylene carbonate that has been distilled in this
with the fraction of material that distilled. Pure EC manner exhibited chromatograms similar to the one
and pure PC were mixed in the ratio of 2 : I and vacuum shown in Fig. 4. Curve A is for the flame ionization
distilled. Fractions representing about 3 per cent of the detector, and curve B is for the thermal conductivity
pot charge were collected and analyzed by GLC. The detector. The flame detector showed that a small pre-PC
results, shown as percentages of EC or PC in each impurity was present in concentrations below 20 ppm.
fraction, are listed in Table 3. These results confirm This impurity was 1,2-propanediol. Neither this com-
that EC is concentrated in the kettle residue. Although pound nor ethylene carbonate (the post-PC impurity)
there appears to be a gradual increase in EC as more is expected to affect adversely the electrochemical
distillate is removed, no significant change in EC in the studies.
distillate could be detected when the initial concentration
was low (as it is in the "as received" PC).
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,
0 2 4 6 8 I0 12 14 [6 18 20 22
105 (1968).
Retention times, rain
Ill] R. F. Nelson and R. N. Adams, J. electroanal. Chem. 13,
184 (1967).
Fig. 4. Clu~mato~'ams for PC timt is sal~equeafly used in [12] V. Gutmarm, M. Kogelnig, and M. Michlmayr, Monat. Chem.
electrochemical studies. Curve A, flame ionization detector; 99, 693 (1968).
curve B, thermal conductivity detector. [13] J. N. Butler, Anal. Chem. 39, 1799 (1967).
[14] R. J. Jasinski and S. Kirkland, Anal. Chem. 39, 1663 (1967).
Method o f distilling P C [15] F. Todd, Modern Fractional Distillation Equipment for the
Propylene carbonate, which will be used for subsequent Laboratory. Literature from the Todd Scientific Company
electrochemical studies, is distilled in this manner: the (1964).