high ohmic resistance systems could not
be studied effectively.
0.9 0.8 0.7 b.6 0.S 0.4 0.3 0.2 0.1
E vs. S. C. E.
Figure 3. A.c. voltammetric scan of 2 X 1 O-3M KI in 75%
acetone-25% water with 0.25M HzS04 background elec-
trolyte using controlled potential (4)
4600 ohms cell resistance
10,000 ohms or less, and no difference ax. potential. The square wave re-
in the phase angle of the current was sponse is shown in Figure 2. Potential
noted. Resistances up to 100,000 ohms control results in rapid charging of the
did not change the peak height, but the double layer, and better separation of
total a x . current increased during part capacitive and faradaic currents than in
of the alternating cycle, which indicates noncontrolled systems.
some loss of control. Resistances above A solution of 2 i< 10-3AVKI and
500,000 ohms caused overloading of the 0.25M H2S04in a mixed solvent com-
amplifiers, and resulted in clipping of posed of 7 5 7 , acetone-25% water was
the sine-wave current. oxidized using potential control and the
The charging of the double layer scanning conditions previously de-
capacitance for the electrode system in scribed. The cell resistance as deter-
I N KC1 with an applied square wave mined by an a x . bridge was 4600 ohms.
was studied as an indication of the The resulting scan is shown in Figure
ability of the instrument to control the 3. Without potential control, such
Determination of Cesium as Permanganate
SIR: The solubility of cesium per- solve the residue in 1 ml. of water and
manganate in water a t temperatures a half immerse the vessel in a bath of
few degrees above 0” C. is lower than salted cracked ice. Add dropwise from
that of any other metal permanganate. a buret 6 ml. of 0.1X ammonium per-
At 1O C. a saturated solution has only a manganate while swirling the liquid in
the vessel. Allow the vessel to stand in
faint violet tint, and the solubility the bath a t least 10 minutes. Prior to
product of the salt a t this temperature beginning the precipitation, half im-
is 1.5 X This indicates the possi- merse in the same bath a micro wash
bility of practically quantitative pre- bottle containing about 25 ml. of pro-
ripitation, a t least in a sufficiently con- pionic acid. At the same time place a
centrated cesium solution a t a low weighed filter crucible in a small con-
temperature in the presence of a suffi- tainer near some dry ice so that the
ciently high concentration of per- entire crucible is cooled by carbon diox-
manganate. ide vapor. At the end of the cooling
period of a t least 10 minutes fit the
EXPERIMENTAL cold crucible to a suction apparatus,
and transfer the precipitate and solution
Evaporate the neutral solution, con- rapidly to the crucible with the aid of
taining not less than 5 mg. nor more successive I-ml. portions of the pro-
than 50 mg. of cesium, to dryness in a pionic acid. Wash the precipitate with
50-ml. beaker or Erlenmeyer flask. Dis- a few additional 1-ml. portions of pro-
CONCLUSIONS
The most important practical ad-
vantage of electronically controlled a x .
voltammetry is the application t o high
resistance systems, where conventional
a x . voltammetry is inapplicable.
Phase selective detection of the current,
as reported by Smith and Reinrnuth
(7), extends the utility even more.
LilERATURE CITED
(1) Bauer, H. H., Elving, P. J., ANAL.
CHEM. 30. 334 (1958).
I - - - ~
(2)-Bauer, H. H., Elving, P. J., Australian
J.Chem. 12,335 (1959).
. . Booman, G. L. ASAL. CHEM. 29,
(3)
213 (1957).
(4) Breyer, B., Gutmann, F., Hacobian,
S.. Australian J. Sci. Research Ser. A
4,‘597 (1951).
(5) Kelly, M. T., Fisher, D. J., Jones,
H. C., Maddox, W. L., Stelzner, R. JV.,
Laboratory Instruments Session,
I.S.A. Conference, Sen- York, Sept. 26,
1960.
(6) Philbrick, George A., Researches,
Inc., Boston, Mass., “GAP/R Elec-
tronic Analog Computers,” ‘‘L4pph.-
tions Manual for Philbrick Octal
Plug-In Computing Amplifiers,” and
catalog data sheets.
( 7 ) Smith, D. E., Reinmuth, W. H.,
ANAL.CHEM.32, 1892 (1960).
DONALD E. WALKER
RALPHS. ADAMS
Department of Chemistry
University of Kansas
Lawrence, Kan.
JOHN R. ALDEN
School of Electrical Engineering
University of Kansas
Lawrence, Kan.
RECEIVED for review October 21, 1960.
Accepted December 7 , 1960.
pionic acid and allow the suction to
continue until the precipitate appears
to be dry. Remove the crucible, touch
the bottom of it to a piece of filter
paper to remove any adhering propionic
acid, and place it in a drying oven main-
tained a t 110’ to 120’ C. Dry for
about an hour, cool, and weigh. Mul-
tiply the weight of the precipitate by
0.5270 to obtain the weight of cesium
or by 0.5593 to obtain the weight of
cesium as oxide. Instead of drying and
weighing the cesium permanganate,
some time may be saved by dissolving
the precipitate and titrating the solu-
tion. To do this, first dry the crucible
containing the precipitate briefly, place
it in a funnel leading to a 250-ml. beaker,
and dissolve the precipitate by adding
in successive small portions a solution
prepared by adding 2 ml. of concen-
trated sulfuric acid to 25.00 ml. of
VOL. 33, NO. 2, FEBRUARY 1961 309
standard 0.1N oxalic acid. Heat this solution by washing with 1-ml. portions cause they react rapidly with both pre-
solution to about 90" C. before use. of water. Heat the solution in the cipitate and reagent. Pure propionic
Transfer the last portions of oxalic acid beaker to 90' C. and back-titrate with acid is a fairly satisfactory wash liquid.
standard 0.1N potassium permanganate. It does not react appreciably in a shoi t
Thedifference between the volume of per-
manganate required and that required period of time a t a low temperature
Table 1. Effect of Concentration of for the blank titration of the oxalic acid with either precipitate or reagent, and
Reagent and Concentration of Cesium solution corresponds to the amount of cesium permanganate is practically in-
on Completeness of Precipitation cesium present. Each milliliter of soluble in it. Its somewhat disagree-
Vol- O.1OOON permanganate equals 2.66 mg. able physiological properties were not
Ratio umeof of cesium or 2.82 mg. of cesium oxide. found to be a serious obstacle.
of"( CsCl Differ- The results are as accurate as those ob- Unfortunately, this method is ap-
~ 1 1 0 solu-
~ Cesi~m,Mg. ence tained gravimetrically. plicable only when the ratio of cesium
to tion, Pres- Error,
CsCl M1. ent Found Mg. to rubidium is high, because rubidium
2 5.00 50.0 49.9 -0.1 RESULTS AND DISCUSSION causes a serious positive error due to
5 5.00 50.0 50 4 +0.4 coprecipitation, as would be expected
9 5.00 50.0 50.4 +0.4 Table I shows that satisfactory results from its low solubility. Potassium in-
can be obtained if the concentrations of terferes to a much smaller degree.
2 son 250 246 -n 4
reagent and cesium are both sufficiently Other metal ions except silver do not
7 5100 25.0 25:2 +0.2
9 5.00 25.0 25.0 0.0 high. Such results cannot be obtained interfere unless they reduce perinan-
by precipitation and filtration a t room ganate in neutral solution.
2 2.00 10 0 9.9 -0.1 temperature under any conditions of EARLER. CALEY
7 2.00 10.0 10.2 +0.2 concentration. Solutions of sodium or WALLACE H. DEEBEL~
9 2.00 10 0 10.0 0.0
lithium permanganate are also suitable Department of Chemistry
2 1.00 10.0 10.0 0.0 as reagents. A solution of cesium per- The Ohio State University
5 1.00 10.0 9.9 -0.1 manganate in water saturated a t the Columbus 10, Ohio
7 1.00 10.0 10.0 0.0 working temperature may be used as RECEIVED for review May 2, 1960. Ac-
2 1.00 5.0 4.6 -0.4 the wash liquid, but its use leads to cepted November 18, 1960. Division of
5 1.00 5.0 4.8 -0.2 slightly high results because of the pre- Analytical Chemistry, 137th Meeting,
7 1.00 5.0 5.1 t0.1 cipitation of cesium permanganate from ACS, Cleveland, Ohio, April 1960. Taken
it on contact with reagent still adher- from the Ph.D. thesis of Wallace H. Dee-
2 1.00 2.0 0.3 -1.7 bel, Ohio State University, 1957.
5 100 2.0 0.4 -1.6 ing to the precipitate. The usual or-
7 1.00 2.0 1.1 -0.9 ganic washing solvents such as acetone 1 Present address, Pittsburgh Plate Glass
or alcohol are entirely unsuitable be- Co., Pittsburgh, Pa.

Influence of Column Support on Separation of Fatty Acid

Methyl Esters by Gas Chromatography
SIR: We reported the use of a poly
(vinyl acetate) (PVA) liquid phase on
Chromosorb, 30-60 mesh, for the separa-
tion of fatty acid methyl esters (4).
Subsequently, batches of Chromosorb
R and SV (both diatomaceous earth
products) when used as supports for
PVA gave separations of widely varying
efficiencies. Homing, Moscatelli, and
Sweeley (S), following the procedure of
Howard and Martin (6), reported that
screened Celite 545, 60-80 and 80-100
mesh, acid-washed, dried, treated with
vapors of dimethyldichlorosilane, and
esters on PVA, supported on "silanized" nitrogen saturated with dimethyldi-
30-60 mesh Chromosorb R and Celite chlorosilane through a 100-gram batch
545 and on waterproofed glass micro- of the support for approximately one
beads, 30-60 mesh, is given in Table I. hour, Chromosorb R required a very
Although the Celite 545 fractions can much longer exposure time to the vapors
be pretreated satisfactorily by passing of dimethyldichlorosilane. Best results
Table 1. Separation Factors, Retention Volumes, and Theoretical Plates (9-Foot
Column) for Fatty Acid Methyl Esters on Poly(viny1Acetate)
Column Support
Chromosorb R,
T = 205' C. Celite 545, Glass Microbeads,
Reten-
~

T = 205" C. T = 168" C.
then washed with methanol, gave a tion Reten- Reten-
superior column support for polyester- vol- Separa- Theoret- tion Separa- Theoret-' tion Separa- Theoret-
type liquid phases. More recently, Methyl ume, tion ical volume, tion ical volume, tion ical
Hishta et al. (1, 2 ) suggested the use of Ester ml. factor plates ml. factor plates ml. factor plates
microbeads as the solid support for Laurate 452 0.23 1190 248 0.23 640 85 0.1G 16
liquid substrates, in the order of 0.25% Myristate 798 0.41 1600 444 0.41 910 177 0.33 32
Palmitate 1438 0.73 1760 803 0.73 950 366 0.69 34
by weight, to separate high boiling com- 1.00 1820 1097 1.00 1470 530 1.00 73
pounds at a rapid rate and a t relatively Margarate 1962
Stearate 2580 1.32 1925 1450 1.32 1500 750 1.41 94
low column temperatures. Oleate 2890 1.47 2050 1633 1.48 1735 850 1.60 139
A comparison of the separations ob- Linoleate 3370 1.72 2120 1913 1.75 2035
tained for several fatty acid methyl

310 ANALYTICAL CHEMISTRY