Determination of Acetone
An
Ultraviolet Spectrophotometric Method G. L. BARTHAUER, F. V. JONES, AND A. V. METLER
Field Research Department, Magnolia Petroleum Company, Dallas, Texas
this wave length by plotting the so-called “optical densities” (log against the corresponding concentrations of acetone in 2,2,4-trimethylpentane showed no significant deviation from Beer’s law.
A method i s described for the determination of acetone in mixtures with diisopropyl ether, isopropyl alcohol, and low-molecular weight mono-olefins. Essentially the procedure involves suitable dilution of the sample with 9,!2,4-trimcthylpentane, followed by measurement of the optical density of the diluted material at 980 millimicrons.
2)
CALCULATION AND INTERPRETATION
The molecular extinction coefficient, k, of each compound was calculated from the foregoing data, using the familiar modified form of the Beer-Lambert equation,
IN
CONNECTION with the production of propylene by the catalytic dehydration of isopropyl alcohol, it was necessary to develop a rapid and accurate method for measuring acetone produced as a by-product of the main reaction. Low-molecular weight mono-olefins, diisopropyl ether, and unreacted isopropyl alcohol were also present in considerable quantities in the solutions to be investigated. From the standpoint of both rapidity and accuracy, a photometric method, based on the absorption of ultraviolet light by acetone, appeared to be the most promising approach to the problem. Hartley (4) has reported the complete absence 0.f ultraviolet bands (above the Schumann region) for isopropyl alcohol. Bielecki and Henri ( 1 ) detected a very slight continuous absorption for n-propyl alcohol but, in the light of subsequent work by Massol and Faucon ( 5 )who showed that the degree of absorption of a secondary alcohol was lower than that of the corresponding primary, it appeared that this absorption could be regarded as insignificant from an analytical viewpoint. Carr and Walker (8) have thoroughly investigated the ultraviolet spectra of mono-olefins in the low-molecular weight range. In no case does the absorption become significant above 260 millimicrons, a wave length well below the acetone absorption maximum. Despite a thorough search of the literature, no data on the absorption of diisopropyl ether were found. The absence of significant bands, however, has been proved experimentally. The absorption of ultraviolet light by acetone has been the subject of much study and the authors’ work has only verified previous reports (6-9).
I, =
IolO-k‘C
where 1 represents cell length (cm.), c the molar concentration, and I Oand Z, the incident and emergent light intensity, respectively. These data are shown in Table I. SYNTHETIC SAMPLES
.4 series of synthetic samples containing varying amounts of the pure components was analyzed for acetone content. Each sample
Table I.
Molecular Extinction Coefficients at 980 Millimicrons Concentration Transmittancy k Vel. % %
Compound
Acetone Olefin Diisopropyl ether Isopropyl alcohol
1 10
Table Alcohol
5.0 87.8 93.8 90.0
25 25
II. Synthetic Sample Data
Sample Composition Ether Olefin
%
Results Acetone found Error
Acetone
%
%
9.58 0.09 0.02 0.01
%
%
%
100
90
EXPERIMENTAL RE.4GEh-TS AND
80
EQUIPMENT.Acetone, Commercial Solvents
(C.P.). Diisopropyl ether, Eastman Kodak No. 1193. This material was purified by successive fractionation and chemical treatment until only a very faint trace of acetone remained. Isopropyl alcohol, Eastman Kodak No. 212, treated like the diisopropyl ether. 1-Octene, Connecticut Hard Rubber Company. Approximately 99%- pure, - of close-boiling - iso_ , the remainder consisting mers. 2,2,4-Trimethylpentane (Iso-octane), Rohm and Haas material, carefully purified prior to use by means of silica gel (8’). All spectral measurements were made with a Beckman DUV spectrophotometer equipped with a hydrogen discharge source. The wave-length scale was calibrated with a mercury vapor lamp to within t O . 1 millimicron just prior to use. Matched quartz cuvettes (10 mm.) were employed to contain the sample and the 2,2,4-trimethylpentane reference solution. SCANNING AND CALIBRATION. Figure 1 is a plot of experimentally obtained transmittancies against wave length for a solution of each component in the mixture. A band width of 0.5. millimicron was used throughout the entire wave-length range. As can be seen, acetone showed a broad band centered a t approximately 280 millimicrons. A calibration curve prepared at
70
-0 c
2
I O X I-OCTENE
60
c
Y)
0
-
5
50 40
m c
a
30
20
10
0 250
255
260
265
270
275
Wave
Figure 1.
354
280
Length,
285
290
m y
Experimentally Obtained Values
295
300
355
ANALYTICAL EDITION
June, 1946
was accurately diluted with 2,2,4trimethylpentane until the optical density obtained fell within the range of the calibration curve. Reference to the curve and the application of the appropriatje dilution factor readily permitted calculation of the acetone concentration in the original sample, All values shown in Table I1 were calculated from the equation of the best-fitting calibration line. This equation was obtained by the method of least squares. As can be seen from Figure 1, the rate of change of the extinction coefficient of acetone is small a t its absorption maximum. This would suggest the ready application of filter photometers for transmittancy measurements despite the relatively broad wave bands usually associated with such instruments.
spectral trausmittancy a t 280 millimicrons. The data indicate that a low-cost filter photometer may be employed for obtaining satisfactory transmittancy values. LITERATURE CITED
Bielecki, G., and Henri, V., Compt. rend., 155,456-8 (1912),. Carr, E. P.,and Walker, M. K., J. C k . Phys., 4,751-5 (1936). GrafT, M. M.,O’Connor, R. T., and Skau, E. L., IND. ENG. CHBM.,ANAL.ED.,16, 556-7 (1944). Hartley, W. N., J. Chem. SOC.,39, 153-73 (1881). Massol and Faucon, Bull. aoc. Aim., 11, 931-5 (1912). Purvis, J. E.,J. Chem. SOC., 127,9-14(1925). Rice, F. O.,Proc. Roy. SOC.,91,76 (1914). Walls, H. J., and Ludlam, E. B., Trans. Faraday SOC.,33,776-81 (1937).
SUMMARY
Acetone may be determined in the presence of alcohols, ethers, and mono-olefins of low molecular weight by measurement of the
Washburn, E. W., “International Critical Tables”, Vol. V, pp. 369, 371, 374, 376, 377, New York, McGraw-Hill Book Co., 1929.
Amperometric Titration of Chloride, Bromide, and Iodide Using the Rotating Platinum Electrode H. A.
LAITINEN, W,
P. JENNINGS,
AND
T. D. PARKS’, Noyes Chemical Laboratory, University of Illinois, Urbana, 111.
Chloride, bromide, and iodide can be titrated rapidly in dilute solution with silver nitrate, using a rotating platinum electrode as the indicator electrode in amperomebic titrations. Wide variations in the concentration of acid or salts present do not affect the results. A tendency toward low results is obsened with increasing dilution. Chloride can be titrated in IO’’ N solution in 75% acetone, bromide in 50% acetone, and iodide in water.
T
HE use of a rotating platinum electrode in amperometric
titrations (4) of arsenite with bromate (6), silver with chloride ( 6 ) ,and mercaptans with silver (5) has been described. Halides can be titrated in a simple manner by measurement of the diffusion current of silver ions during the course of the titration. The end point is determined graphically from a plot of current against titration volume. Salomon (7, 8, 9) made a study of “galvanometric titrations” using two silver electrodes in dilute potassium chloride with an e.m.f. of 0.1 volt applied across the electrode. When the potassium chloride was titrated with silver nitrate, practically no current flowed until an excess of silver had been added. The end point was taken as the point where the sudden current increase occurred. The dead-stop end point of Foulk and Bawden (1) is based upon the sudden polarization or depolarization of one or both electrodes of an electrolytic cell in the presence of the first small excess of reagent. Both the galvanometric and dead-stop end points are very similar in, principle t o the amperometric end point. However, the important new feature of the amperometric titration is that the current is measured in general on a diffusion current region of a current-voltage curve. On such a region, the current is independent of the potential of the electrode because of an extreme state of concentration polarization a t the indicator electrode. Since the concentration of material undergoing electrode reaction is maintained a t a value practically equal to zero, the current is limited by the supply of fresh material to the electrode surface by diffusion. The rate of diffusion, and hence the current, is proportional to the concentration of diffusing substance in the bulk of the solution. By using a rotating electrode, the didusion layer thickness is decreased, thereby increadng the sensitivity and the rate of attainment of a steady diffusion state. It is
’ Present address, Shell Development Co., Emeryville, Calif,
evident that a titration curve of diffusion current against volume of reagent is, in general, a straight line. (Strictly speaking, a correction for dilution is necessary to attain a linear relation between current and volume of reagent, but by working with a reagent which is tenfold more concentrated than the solution being titrated, the correction becomes negligibly small.) I n titrating halides with silver, the potential of the rotating electrode is made negative enough t o plate out silver ions, leaving the layer of solution next to the electrode depleted of silver ions. The potential, however, must not be negative enough to give a n appreciable current due t o the reduction of dissolved oxygen. The range of permissible potential is strictly limited, as i s evident from an examination of the current-voltage curves of silver-ion reduction and oxygen reduction using a silver-plated electrode (6). The potential of the saturated calomel electrode happens to lie in the permissible range, so that it is necessary only to short-circuit the rotating electrode through a suitable current measuring instrument to a saturated calomel electrode of relatively large area. Titrations in ammoniacal medium are carried out a t a more negative potential, to deposit the complex diammine silver ions. Fortunately; the reduction curve of oxygen is shifted t o more negative potentials in ammoniacal solution, and all that is necessary is t o substitute for the saturated calomel electrode a reference electrode of more negative potential. I n the previous work on the amperometric titration of silver with chloride (6), a large irregularly fluctuating current was observed even in the presence of a large excess of chloride where the silver ion concentration should be very low. This current was attributed t o a depolarization of the platinum cathode by colloidally dispersed silver chloride particles. It was found that the abnormal current could be decreased by flocculating the precipitate by the addition of electrolyte, and eliminated by the addition of gelatin. The gelatin causes the precipitate to become peptized by protective colloid action, but the gelatin-coated particles no longer are reducible a t the cathode. The gelatin also changed the character of the plated silver from a coarsely crysts.lline to a finely divided, adhering deposit. With the coarsely deposited silver, a slowly drifting diffusion current was observed, while electrodes plated in the presence of gelatin gave constant diffusion currents for long periods of time. The drifting effect is unimportant in amperometric titrations if a freshly cleaned platinum electrode is used.
