s m i p k . The platinuiii wire should be ivrapprtl so that the sample is supported
tlirouphout the entire combustion; (.:irkion particles are foi*medif any of the >:amplr drops to the bottom of tlw flask before 1)urning is coniplt.te. -1portion of the sample or a pieve of lo\~-a*h filter l i a p r is ~isodfor the ignition wick as >lion-n in Figure 1. To incrrasc. the : i b ~ o r ~ ) t i oofn radiant ~ n e r g y the < tip of t h r ivkk is t h c k e n e d \\-ith k a d pencil mplf 1ioldc.r is hooked ovcr the, Iiositioning roil. lowered into the fla-k, : t i i d the s;:tmple hcight adjusted that the wick is : n line with and (lirc~-tly :iliovr the projector bulb. . k i d , :tlkali, or water is a d d 4 to the Iiottoin of tlie flask tci dissolw the a521 :iItw c.oml)u*tion. T l i t ~ lialloon and :itlal)tc~are rcmoved, and the flask is fliidictl ant1 fillrtl with oxygen pas.
After the balloon is replaced and a safety shield is in position, the lamp is turned on until combustion is started. soon as combustion is complete, the Iilat,inuni wire is dropped t o the bottom of the flask in contact with the ash solvent. The flask, which may be cooled rapidly by spraying the outer Furface with Ivater. i i held iintil any aerosol disperses; then the a$h solution and the water used to rinse the balloon and tlie combustion flask are aspirated into a flask for analysis.
Iron in tlip form of ferric chloritic solution was added to n-oodpulp and Whatman S o . 10 filter paper. ‘Thcl ash ij-a> d i w ~ l v t din 20 nil. of 1:1 HCI. ant1 t h r iron tletc.rniiiied with 4 . i tliphen~-l-l,l0-phcnanthroline(batho~iheiiaiithrolinr.) using a modification of t h r I)roccdure of Gahler, Harnner. and ShiilxJrt ( 2 ) .
RESULTS
The apparatu. ha> been u w l for the analy4s of iron, cwpper, and chloride in woodpulp. Some of the iron rrcovery tlata are presented in Table I.
Rapid Scanning of Radioactive Thin layer Chromatograms Joseph Rosenberg anti Michael Bolgar, Organic Chemistry Department, Tracerlab Division, laboratory for Electroiiics, Inc., Waltham, Mass.
VOL. 35, NO. 10, SEPTEMBER 1963
1559
1000
900
1
800
,-
600
t
500
- p
W
2
z W
a
700
E
+
c
1250
0
5 5
100 -
1500'
t:
1000
9 0 a
750-
I
250
500
1
"
l
0-
3
A -
DISTANCE IN CM.
1
DISTANCE I N C M
Figure 3. Tracing of a chromatoplate of triolein-1 ,1 ',1 "-C14 (Tracerlab) Adsorbent. Anasil B (Analabs) Solvent. Ligroin-diethylether-acetic Development time. 50 minutes Full scale. 1000 c.D.m.
Figure4. Tracing of a chromatoplate of triolein-1,1 ',1 before purification Adsorbent. Anasil B (Analabs) Solvenl. Ligroin-diethylether-acetic Development time. 35 minuies Full scale. 2500 c.p.m.
acid, 90/10/1 v./v./v.
compounds. Thus it is a valuable adjunct to other proven methods vdiich serve the same function such as autoradiography (3) and liquid scintillation counting ( I , 4 ) of isolated chromatoplate vctioiiq. Depending on the coating thickness and the slit width and time constant of the scanner, the efficiency was about 2%. With more recent developments, including thinner windows, this should be markedly increased. A step chromatogram scanner can be used instead of the continuous scanner described
here. This will give a printed record of the counts of each segment and can be adjusted with preset time and preset counts to give great accuracy even n-ith minimum quantities of radioactivity. The scanning method qhould prove particularly hclpful in cases where rapid analysis is essential, as with compounds containing short-lil ed isotopes-Le., sulfur-35 and iodine-131. Any laboratory working with radioactivity and having a chromatogram scanner with a suitable slide can, with almost no additional espense. extend its
"XI4
acid, 90/10/1 v./v./v.
capabilities to TLC, since no modification of the scanning instrument i, necessary. I n addition, the TLC results are easily interpretable in ternis generally used with radioactivity. LITERATURE CITED
(1) Csallary, A . S., Draper, H. H., Anal. Biochem. 4, 418 (1962). ( 2 ) Lees, T. M., DeMuria, P. J., J . Chromatoo. 8. 108 11962). ( 3 ) Mangoid, H. 11.;J. d n z . Oil Chemist>' Soc. 38, 708 (1961). ( 4 ) Snyder, F., Stephens. N., d m d . Biochem. 4 , 128 (1962).
Preparation of Deuterated Solvents for Nuclear Magnetic Resonance Spectrometry P. J. Paulsen' and W. D. Cooke, Baker laboratory, Cornell University, Ithaca, EUTERATED CHLOROFORM and aceDtone are useful and sometimes indispensable solvents for studies involving proton nuclear magnetic resonance spectrometry. Unfortunately, these solvents are relatively expensive for routine use and it is common procedure either to use minimal volumes or recover the solvents for reuse. It should be noted, however, that 100 grams of deuterated chloroform, which costs approximately $100, contains only 40 cents worth of deuterium based on the cost of heavy water at $60 per kilogram (in 125pound lots). Deuterated chloroform can be produced a t high efficiency from heavy water by the following reaction
2CDCls
+ CO,
PROCEDURE
TKOhundred and sixty-five grams of hexachloroacetone (one mole), 40 ml. of heavy water (2 moles-100% excess), and 10 ml. of pyridine were added t o a dis1560
tillation flask. Two phases formed. On slow heating, a mixture of CDC13, DzO, and pyridine distilled out as the reaction proceeded. The CDCl3 was purified by a second distillation, dried over calcium sulfate, and redistilled. One hundred and ninety grams of deuterated chloroform were obtained a t a cost of approximately five cents a gram. The chloroform should be either stored under refrigeration to prevent decomposition, or stabilized with a small quantity of deuterated ethanol. The reaction chosen to prepare the deuterated acetone was as follows. CH3COCHl
+
C C ~ B C O C C ~DsO ~
ANALYTICAL CHEMISTRY
N. Y.
+ excess DzO LIOD__ CDaCOCD3
+ 6HD0
PROCEDURE
Fifty milliliters of analytical reagent grade acetone, 100 ml. of 99.7% deuterated heavy water, and 0.4 ml. of a saturated solution of LiOD in D20 are
mixed together. The LiOD solution can be prepared by reacting lithium wire with D2O until LiOD begins to precipitate. The mixture is left standing for 30 minutes. The acetone is then separated by distillation and the process is repeated using new 100-ml. portions of heavy water until the acetone has undergone four exchanges. The heavy water samples left from the first preparation can be reused with a new batch of acetone, and a fifth sample of heav! water added a t the end of the process to yield the same high purity deuterated acetone By extending the process, and limiting the number of distillations to fire, (discarding the heavy water with the highest hydrogen content after each preparation) the materials cost of onc batch of deuterated acetone equals the cost of 100 ml. of heavy water or about 20 cents per gram of deuterated acetone This procesr has been scaled u p by a factor of 10 in our laboratory. l Present address, Kational Bureau of Standards, Washington, D. C.
