V O L U M E 2 6 , N O . 3, M A R C H 1 9 5 4 m m t :incl a s>),sequciit microdetermiriation. Flame photometry of the trace constituent, aft,er separation by ion-exchange chromatography, may also be a valuable approach t o the determination of a trace of one alkaline earth in the presence of large amounts of the ot'hers. -4wider column would permit the use of a larger sample but would also involve larger fractions of eluate for each constituent and would not aid in the determination of trace amount?. Further work is being done on the analysis of samples that contain traces of one alkaline eart'h and large amounts of other alkaline earths. IIydrochloric acid would be a desirable eluant because it could lie readily volatilized from each fract'ion. Unsatisfact,ory separations are obtained, however, iinless the eluant can complex q-ith alkaline-eart,h cations. Ammonium citrate has been used successfully (9!IO) for small amount's of the alkaline earths. \\lth t h r larger amounts of sample used in t'his work, however, citrate w a ~ unsatisfactory, brcausc it formed a precipitate with strontium and hariuni inside the column. T h e separation of c~nlciunifrom strontium is facilit'ated by the use of a n eluant which 1x1s a much greater c,oniplesing ability toward calcium than toward strontium. Lactate was chosen because it, is the hest in this respect (4j. I n some of the pre1iminar)- work, the alkaline earths were tlrtrrmiried in the eluate fractions by titration with ethylene(1i:iniinetetraacetic acid (Persene j. This method was rejected hrcause the end point was unsatisfactory, probably because of the presence of lactate. Hondii ( 5 ) has recently succeeded in separating magnesium, calcium, stront,ium, and barium by elution with ammonium ace-
611 tate, which permits the determination of the cations by Versene titration. His relative errors, however, are between 5 and 10 parts per thousand. After the data of Table I had been obtained, a sample of colloidal Dowex 50, lot number 3164-4, was made available by the courtesy of R. 11.Wheaton. An elution graph obtained with this resin indicated a better separation than that of Figure 1 Therefore the use of this resin should permit a quantitative separation with a shorter column and hence a smaller volume of eluate and less time. This resin was manufactured by a new process i l l ) ,which yields a more uniform product than has been available heretofore. LITERATURE CITED (1) -hsarsson, G. O., and Balder, .L, . ~ N A L .CHEM.,24, 1679 (1952). and Lindenbaum, S., Zhid., in (2) Beukenkamp, J., Rieman, W.,
press.
(3) Reyer, G. L., and Rieman, K., Ihid., 19, 35 (1947). (4) Cannan, R. K., and Kihrick, A , , J . .Ani. Chem. SOC.,60, 2314 (1938). (5) (6) (7) (8)
Honda, AI., private communication. Kobe, K. A . , and AZotsch, W.AI., ANAL.CHEM..2 3 , 1498 (19.51). Rieman, TV., and Lindenbaum, S.,I b i d . , 24, 1199 (1952). Sweet, R. C.. Rieman, K., and Beukenkamp, J., I h i d . , 2 4 , 952
(1952). (9) Tompkins, E . R., J . A m . Cheni. SOC.,70, 3520 (1948). (IO) Tompkins, E. R., Khym, J. X., and Cohn, W. C., J . Am. Chem. soc., 69, 2769 (1947) : -4tomic Energy Commission, Doczment
1998. (11) Wheaton, R. R I . , prkate communication. R E C E I Y E Df o r revieiv September 21, 1953. .-\ccepted January 7, 1954
Use of a Cation Exchange Resin for Total Anion Analysis Of Aqueous Solutions Containing Uranyl Ion H. 0. DAY, JR., J. S. GILL, E. V. JONES,and WILLIAM L. MARSHALL Chemistry Division, Oak Ridge N a t i o n a l Laboratory, O a k Ridge, Tenn. r
THE.
ion esc.hange analytical method for negative ions in water
1 i n ~ d v e sthe removal of cations by an ion exchange resin
and n snhrequent titration of the acid effluent. Some of t,he first ~ by Samuelson and coworkers. A4 work in this field ~ v i idone coniprrhf.nPive review of his ivork as n-ell as of other investigations is given i l l hi!: recent hook (2). In the preparatiori of uranyl salts by dissolving uranium trioxide i n rivid, it is neceam to obtain an accurate determination of the mole equivalent ra I of uranium to anion. The ion exchange method is useful in such analyses and has been extended to includr several anions of uranyl salts-namely. sulfate, nitrate, chloridt.. perchlorate. and dichromate. I t offers much promise 1iec:iuw 1 ~ 1 ' the speed and precision of analysis. EXPERIMEYTAL
Clear Ilowex 50, 200 to 400 mesh, with 12°/0 cross linkage, was treated u i t h a large excess of 351 sulfuric acid and washed free ot acid Tests showed that in this work more elaborate preparation of the resin such as alternate washings with ethyl alcohol, sodium hydroxide, and hydrochloric acid was unnecessary. The ion exchange column consisted of a n 18-cm. length of 2cm. borosilicate glass tubing containing a No. B Corning sintered-glass filter disk near the bottom. The tube was reduced in diameter just below the filter and joined t o an 18-cm. length of 2-mm capillary tubing The flow was controlled by a pinchcock on a short piece of rubber tubing attached to the capillary tube. About 16 ml. of x e t resin Tvere present in the column. Samples to be analyzed were prepared by dissolving 1 giani, Tveighed t o 0.1 mg., of specially prepared dry Mallinckrodt uianium trioxide (nitric acid impurity in the trioxide was less than 0.3 mole Vc) in a measuied volume of standard acid of the
anion under consideration. The sample was then diluted to 35 ml. and poured through the ion exchange column at the rate of 8 ml. per minute. The column was then washed sufficiently to produce a final effluent volume of 100 ml. The acid effluent was titrated with standard sodium hydroxide solution using a pH meter to detect the end point of reaction. The values obtained represented the total concentration of anion
Table I.
Titration -inalysis for Anion after Removal of t-raniuni B
.I Uranium taken, meq. 6.943 7.175 7,597 5,243 5.158 5.519 4.083 4 822 4.149
Anion taken, meg. 5 . 1 6 4 SO4-5.340 SOa-5 . 6 6 0 SOa-4.882 S o h - 4.806 SO&-5.138 S O A - 4 . 5 6 6 SO4-5 , 3 8 2 Sod--
C -4nion found. nieg.
(C
- B)
X
5 174 332 3 660 4 878 4 808 5 132 364 a 382 4 632
+ O . 194
+
+0.042 -0.117 -0.044
3.998 T O s 3 998 S O ] 4.010 XO34 027 C1-
3 990 4 003 4 003
-0.200 +o 123 - 0 173
4.027 C14.027 C1-
4 022 4 020 4 052
-0.124 -0.174 -0.124
4 800 4 040 3 202
3 991 c10,3 991 C1013 991 (2101-
3 990 3 990 3 Y86
- 0 025 - 0 025 - 0 123
2 416 2.017 1 6rn
2 063 CrlO:-2.063 CrzOi-2.063 Cr20;--
2.067 2.069 2.066
T O 194 +o 291 +0.145
4 811 4 021 3 219 4 808 4 016 3 202
4.630
e
.-\Yerage deviation
"0
I3 +0.:23 +O 1 7 i -0.082
n +i).013
=
0 126u;
ANALYTICAL CHEMISTRY
612 present in the original solution. The effiuents coiitaining dichromic acid were titrated to the second end point n-hich corresponded to the chromate rather than the dichromate ion. At the above flow rate through the column the resin capacity a-as about 3 to 4 meq. per cubic centimeter of wet resin. .I wmple could be analyzed in approximately 20 minutes including titration time. The resin was regenerated easily by washing with 3M sulfuric acid followed by distilled water. Using the procedure described, nine samples were an:dyzeti for sulfate. The mole equivalent ratio of sulfate to uranium was varied from 0.75 to 1.12. Additional analyses were made in the same manner a t approximately 0.83, 1.0, and 1.25 equivalents of anion per equivalent of uranium; the anion was, in succession, nitrate, chloride, perchlorate, and dichromate. The expeeriment:iI data are given in Table I.
of anion present was about =tO.l5%. Investigations by other groups at this laboratory (1, 3 ) have indirated equal success with uranyl fluoride solutions. The bulk of this investigation was carried out with the above mentioned resin; however, later work has shown that elution times can be shortened by using a snialler mesh resin. LITERLTURE CITE11 (1) 1I;dgci.ton J. H.. et a [ . , .Inalytical (’hemistry Division, Oak Ridge Xational Laboratory, Oak Ridge, Te:in., private com-
munication, 1952. ( 2 ) Samuelson, O., “Ion Exchangers in .In:tlytical Chemistq,” Sen-
York, John TViley 8: Sons, 1953. I,. d.,et al., .Ina!ytical Chemistry Division, T-12 Plant, Oak Ridge, Tenn., grirate communication, 1952.
(3) Stephens. DISCUSSION
T h e nver:tye dcviution of tlic icsultq from the actual amount
R E C E I V EfD o r review lfarcli 2 6 . 1953.
Accepted riugust 20. 19.53.
Preparation and Properties of 4,7-Dimethylindan JACOB ENTEL Coal Research Laboratory, Carnegie Institute of Technology, Pittsburgh,
infrared and ultraviolet spectra and other physical proper1 ties of synthetic 4,i-dimcthylindan are reported, and are a useful supplement to the table of properties which have been
I
THE
I
Pa. I
I
I
I
5 2 q -.
I
-
givcn for 10 previously described methylated indans ( 1 ) . No further work is contemplated on this series of compounds. 20
EXPERIJIEYTLL
--
.-
-
w
Three hundred sixty grams of 4,7-dimethyl-l-indanone, prepared as described by Hart and Tebbe (a), was reduced as described by Plattner and WVSP(3). The resulting product was carefully fractionated in a column of 20 theoretical plates to yield 273 grams or 62% of theory of 1,i-tliniethylinclaii.
” 0
I 1.5
-
j ~~
-~~
Physical Properties of 4,i’-Dimethyliiidan
B.P., C. 2 2 7 . 6 a t 745.5 mni.
71’D”
1.5321
da”
Specific Refraction
0.9478
0.3273
Molar - Refraction Olisd. Calcd. 47.80
w i t h t (3). ported h o s e The p r e vinfrared i o u s l y and reultraviolet spectra of 4;T-dimethylindan are shown in Figures 1 and 2. The methods for the determination of these properties have been described ( I ) .
ACKNOWLEDGMEST
!+ ,t 4,7- OIMETHYLINDAN
Table I .
~ o n i l ~ u i i dIvhich , are sliown in Table I, are in agreement
10220
260
300
47.20
The “heart cut” of this fractionation was used for measurcments of physical properties. The physical properties of this
Figure 1. Infrared Spectrum of 4,?-Uimethylindan
The assistance of Joseph B. Sinisic and Daniel T. Muth is gratefully acknowledged.
