A Colorimetric Method for the Determination of Sodium ERIC A. ARNOLD AND ALFRED R . PRAY, Case School of Applied Science, CleFeland, Ohio
F
OLLOTTING the publication of the method for the gravimetric determination of sodium as a hydrated triple salt, NaZn(UO&(CzHa0&.6HzO, by Barber and Kolthoff (1) and the corresponding magnesium salt by Caley and Foulk (S), a number of colorimetric methods based on the color conferred on the solution by the uranyl ion have been described in the literature.
uranium tetroxide found that if a solution of hydrogen peroxide is added to a solution containing the uranyl ion, a white amorphous precipitate forms which they took to be a hydrated uranium tetroxide. If. however, the solution is first made alkaline with sodium or ammonium carbonate and the hydrogen peroxide is then added, a true solution is formed which varies in color from an intense yellow to orange t o red, depending upon the concentration of the uranyl ion.
Caley and Foulk suggested dissolving the triple acetate in water and comparing the yellom ish solutions colorinietricallj , They mention that “best results are obtained when the solutions (known and unknown) show a fairly deep straw color”. This is equivalent to saying that the sensitivity is limited. I t has been suggested by Barrenscheen and Messinger ( 2 ) that a water solution of the triple acetate treated with potassium ferrocyanide gives a stable brownish red color due to a potassium uranyl ferrocyanide which may be used as the basis of a colorimetric method. This procedure has been criticized by several authors on the basis that the color intensity varies with such external conditions as temperature and excesses of reagents. Rosenheim and Daehr ( 4 ) while investigating the hydrates of
It occurred to one of the authors that this color might be made the basis of a coloriiiietric method for determining sodium. This method is basically only a method for estimating the triple acetate of sodium uranyl and zinc or magnesium acetate and therefore assumes all of the precautions and interferences of the methods of Barber and Kolthoff and of Caley and Foulk. Preliminary experiments using a Duboscq colorimeter indicated that the intensity-of color was somewhat dependent upon the amounts of ammonium carbonate and hydrogen peroxide used. At this time a Coleman spectrophotometer became available and the transmission curves shown in Figure 1 were taken. Curve A shows the transmission of a solution prepared by treating an amount of the triple zinc acetate equivalent to 0.308 mg. of sodium, with an excess of 3 per cent hydrogen peroxide and saturated ammonium carbonate solutions, and diluting the whole to 25 ml. Curve R is the same curve for a solution containing an amount of triple acetate equivalent to 1.300 mg. of sodium, again diluting the whole to 25 ml. Both curves show transmissions gf suitable size for yave lengths from 5200 A. to about 5500 A. Therefore, using a 30 mp fixed slit$ the spectrophotometer, a band at 5200 A . was chosen for all succeeding measurements. The procedure involved making a standard triple acetate solution in a knovm xeight of water and making comparison solutions from this by weight. The required amounts of 3 per cent hydrogen peroxide and saturated ammonium carbonate xere added and the whole was made up to a volume of 25 ml. in calibrated flasks. It is important to add the ammonium carbonate solution first, followed by the hydrogen peroxide. If the order is reversed, the amorphous precipitate ~
WAV€ LENGTH
(A.3
FIGURE 1 294
April 15, 1943
ANALYTICAL EDITION
295
Table I11 shows the effect of time on the per cent transmittance. Within the time necessary to make a colorimetric determination, there is no appreciable fading. This appears Sodium Saturated to be true in spite of the fact that on standing for Some time, Taken (NHdzCOa Transmittance the decomposition of the hydrogen peroxide is evidenced by ,wQ. M1. % the appearance of bubbles in the solution. But after shaking 0.5 0.03 71.0 0.03 84.5 1.0 to remove the bubbles, the transmittance appears to be un0.03 95.5 2.0 5.0 0.03 97.5 changed when measured in the spectrophotometer. 0.03 99.6 6.0 An attempt was made to determine the minimum amount 10.0 0.03 99.6 0.5 0.15 50.6 of sodium distinguishable by this method, by making a 55.2 0.15 1.0 0.15 58.8 3.0 number of pairs of solutions from the stock solution which 5.0 58.9 0.15 differed from each other by only small amounts of sodium. 13.8 0.5 0.3 14.2 1.0 0.3 Table IV shows some of these results. As the transmittance 14.2 3.0 0.3 14.2 5,O 0.3 decreases the sensitivity decreases but, by choosing a more appropriate wave band for the redder colors, this could be improved. OF HYDROGEN PEROXIDE OK TRAKSMITTANCE TABLE 11. EFFECT OF TRIPLE ACETATESOLUTIOKS
TABLEI, EFFECTOF AMXOTIUMCARBOSATE os TRASSMITTAKCE OF TRIPLE ACETATE SOLUTIOSS
Sodium Taken MQ.
z% Ml.
Transmittance
TABLE IV. SEKSITIVITY OF COLORIMETRIC METHOD
% 12.7 13.7 14.8 14.9 58.6 63.8 63.8
Sodium
Difference Difference
referred to by Rosenheim and Daehr tends t o form. Because the ordinary hydrogen peroxide of commerce stabilized with acetanilide was not satisfactory, a fresh 3 per cent solution of this reagent was made each time by diluting 30 per cent perhydrol. Table I shows the effect of ammonium carbonate on the color. It can be seen that the transmittance varies somewhat with the amount of ammonium carbonate, but for the amounts of sodium taken for ordinary determinations, 6 ml. of a saturated solution seemed to be a sufficient excess to develop maximum color rapidly. Table I1 shows the corresponding variation for the number of milliliters of 3 per cent hydrogen peroxide. The standard conditions mere then chosen to give sufficient excess of each reagent-namely, 6 ml. The following experiments were run to test the fading of the color:
Difference
Transmittance
ivg.
70
0.308 0.316 0.008 0.675 0,686 0.011 1.24 1.25 0.01
63.2 67.8 4.6 47.2 48.3 1.1 23.2 23.8 0.6
Figure 2 shows the logarithm of the transmittance and Table V shows the data from which this curve was obtained. The few samples on which this method was tried out gave excellent results, as shown by Table VI.
The proper amounts of the stock solution of the triple acetate were weighed into 25-ml. volumetric flasks, to each flask sepa-
rately the ammonium carbonate and hydrogen peroxide were added, the solution was diluted to volume and the color comparison was made immediately. About 5 minutes were required for this and for the necessary adjustments on the spectrophotometer, so that the readings taken at zero time were in error about 5 minutes. TABLE111. EFFECT OF TIMEos TRA~YSYITTANCE OF TRIPLE ACETATESOLUTIONS Sodium
-uQ. 0.22 0.55 0.88 1,02 1.40
Time after Development Hour 0 2
4 0 2
0
1
1.66
21 0 1
1.90 2.09
'1
0 1
21 0
1
21
Transmittance
% 75.2 75.1 51.2 51.1 35.8 35.9 30.9 30.8 21.2 21.3 21.5 17.2 17.3 17.4 15.2 15.0 15.1 12.3 12.1 11.8
/O 00
02
I
04
0I 6
01 8
MG
OF
/O
/Z
SOD/UM
FIGURE 2
1 4
/6
/ 8 I
20
INDUSTRIAL AND ENGINEERING CHEMISTRY
296
TABLE V. TRAKSRZITTAWE Sodium
Transmittance
Sodium
Transmittance
MQ.
%
Mg.
%
0,223 0,308
75.2 63.2 51.2 35.8 30.9
1.30
23.2
0.548
0,879 1.02
TABLE 1'1.
1.40 1.66 1.90
2.09
EXPERIMENTAL RESULTS NarO
Sample
Present
B. S. flint clay 97 B. S. feldspar 70 B. S. opal glass 91
21.2 17.2 15.1 12.3
NarO Found
Vol. 15, No. 4
precipitated by the method of Barber and Kolthoff or of Caley and Foulk, with an excess of ammonium carbonate and hydrogen peroxide which develops a n orange t o red colored solution. When using a narrow wave band this color is proportional to the concentration of sodium ion in solution. The transmittance-concentration curve for thgse solutions has been run over the spectral range from 3700 A. to 7700 A. A wave band of 5200 A. was chosen for this comparison. Various factors affecting the stability of the color were investigated and are reported.
%
%
0.33 2.38 8.48
0.33
Literature Cited
8.47
(1) Barber, H. H., and Kolthoff, I. M., J. Am. Chem. SOC.,50, 162531 (1928); 51, 3233-7 (1929). (2) Barrenscheen, H. K., and Messinger, L., Biochem. Z., 189, 308-13 (1927). (3) CaleY, E.Re, and Foulk, C. w.9 J. Am. Chem. floc., 51, 1664-74 (1929). (4) Rosenheim, A., and Daehr, H., 2.anorg. allgem. Chem., 181, 17782, especially 178 (1929).
2.36
A few experiments showed that the triple magnesium acetate gave similar results, but no particular advantages mere noted.
Summary A method for 'Odium has been which depends on treating a solution of the triple acetate,
PRWSENTED before the Division of Analytical and Micro Chemistry a t t h e 104th Meeting of the AMERICAN CHEMICAL SOCIETY, Buffalo, N. Y.
A Molecular Still Designed for Small Charges JOHN R. MATCHETT' AND JOSEPH LEVINE, U. S. Bureau of Narcotics Laboratory, Washington, D. C.
T
HE active principle of marihuana is contained in a
viscous, high-boiling oily mixture, the active components of which have not as yet been obtained in crystalline form (except cannin, 1 ) . I n working with material of this character, i t is frequently desirable to distill small amounts of i t under high vacuum, either for the purpose of fractionating or simply to separate i t from nonvolatile matter. The still described herein was devised to afford a convenient means for carrying out this operation. With the dimensions indicated, i t has proved satisfactory for distilling from 0.25 to 5 grams of oil. Two fractions of distillate may be collected and the still residue need not exceed 0.15 gram. Transfer losses are avoided, since the distillate is collected directly in tubes in which i t may be retained until used in subsequent operations. It does not pass through any ground joints, thus avoiding the possibility of contamination with lubricant. No provision has been made for determination of the distillation temperature. I n distillations of this type, ebullition 1 Present
address, Western Regional Research Laboratory, Albany, Calif.
does not take place. The temperature is not a constant, b u t a variable related to the pressure and the rate of distillation; hence i t is more satisfactory to characterize products by such properties as refractive index, rotation, and the like.
Apparatus The apparatus is illustrated in the accompanying figure. It consists of a 35-mm. tube, A , 175 mm. inlength, through which a 14-mm. tube, B, is sealed so that its axis lies about 6 mm. above that of the outer tube, A. The still pot, C, is formed by two transverse creases, D,in the outer tube, 45 mm. from each end, extending to within 3 mm. of the central tube. To the end chambers formed by the creases are sealed 24/40 T ground joints, E , in which the receivers, F , are supported as indicated, by suitable lengths of glass tubing. To the central tube are sealed, as illustrated, lengths of glass rod, G , leading from apoint outside the transverse creases, but as near them as possible, to a point from which distillate will drip directly into the receivers. Filling and cleaning are provided for by a tube, H , bearing a 24/40 joint sealed to the top of the still. From the closure of this tube a length of 8-mm. tubing, I , leads t o the vacuum system. Construction of the device involves considerable strains in the glass and the annealing accordingly must be thorough. The authors have found an ordinary muffle furnace convenient for the purpose.
Operation In operation a suitable charge is placed in the still pot, and the
apparatus is set level and gradually evacuated while the charge is gently warmed. After thorough degassing, the still is tipped (9) a little toward one end, full vacuum is applied, and the charge is heated until distillation proceeds at a suitable rate. Distillate accumulates on the condenser and follows it t o the sealed-on glass rod, whence it is diverted to the receiver. The condenser is maintained at such a temperature that distillate flows along it smoothly and does not tend to form large drops which might fall off outside the still ot but before reaching the tip which carries it t o the receiver. xfter one fraction has been collected, the still is tipped toward the other end and the second fraction collected in the same way. The still has been successfully heated by means of a small flame placed some distance below it. A properly designed electric heater might prove more satisfactory.
Literature Cited (1) Haagen-Smit et al., Science, 91, 602 (1940). (2) Holmes, IND. ENG.CHEM.,ANAL.ED.,13, 61 (1941).
