176
ANALYTICAL CHEMISTRY
(485) Tennant, D. &Whitla, I., J. B., and Florey, K., ~ A L CHEM., . 23, 1748 (1951). (486) Theorell, H., and Bonnichsen, R. K., Acta Chem. Scand., 5, 1105 (1951). (487) Thompsen, G., Naturwissenschaften, 39, 451 (1952). (488) Tiselius, A., Discussions Faraday Soc., 1953, No. 13, 29. (489) Tiselius, A., Endeavour, 11, 5 (1952). (490) Togni, G. P., and Meier, O., Experientia, 9, 106 (1953). (491) Tompkins, E. R., Analyst, 77, 970 (1952). (492) Tulpule, P. G., and Patwardhan, V. N., S a t w e , 169, 671 (1952). (493) Ulmann, M.,Pharmazie, 7, 787 (1952). (494) Vandenheuvel, F. A., and Hayes, E. R., ANAL.CHEM.,24, 960 (1952). (495) Van Etten, C. H., and Wiele, 11.B., Ibid., 25, 1109 (1953). (496) Venkatesh, D. S., and Sreenivasaya, AT., Current Sci. ( I n d i a ) , 20, 156 (1951). (497) Vishnyakov, A. P., Dobrovol’skii. D. S., Ermakov, N. V., and Tukachinskii, S. E., Doklady Akad. Nauk S . S . S . R . , 87, 1035 (1952). (498) T’oigt, K. D., and Beckmann, I., Acta Endocrinol., 13, 19 (1953). (499) Wachtmeister, C. A., Acta Chem. Scand., 6, 818 (1952). (500) Wade, H. E., and Morgan, D. hl., Nature. 171, 529 (1953), (501) Wael, J. de, Chem. Weeliblad, 49, 229 (1953). (502) Walker, P. hI. B., and Yates, H. B., Sumposia Soc. Ezptl. Biol., S o . 6, 265 (1952). (503) Wall, J. S.,A N ~ LCHEY., . 25, 950 (1953). (504) Wall, J. S., Wagenknecht, A. C., Newton, J. W.,and Burris, R . H., J. Bucteriol., 63, 563 (1952). (505) Weicker, H., Klin. Wochschr., 31, 161 (1953). (506) Wellington, E. F., Can. J . Chem., 31,484 (1953) (507) Wheaton, R. bI., and Bauman, W. C., Ind. Ena. Chem., 43, 1088 (1951). (508) Whittaker, V. P., and Wijesundeia. S., Bzochem. J . . 51, 348 (1952).
(509) Wickerstrom, rl., and Salvesen, B., J . Pharmacal., 4 , 631 (1952). (510) Wieland, T., and Bauer, L., Angew. Chem., 63, 511 (1951). (511) Wieland, T., and Feld, C., Ibid., 63, 258 (1951). (512) Wiggins, L. F., and Williams, J. H., .Vatwe, 170, 279 (1952). (513) Wilke, G., and Kircher, H., Deut. Z . Nervenheilk., 167, 529 (1952). (514) Williams, J. K.,Jr., Sreenivasan, .i.,Snug, S.,and Elvehjem, C. A., J . B i d . Chem., 202, 233 (1953). (515) Williams, R. J. P., Analyst, 77, 905 (1952). (516) Woernley, D. L., Cancer Research, 12, 516 (1952). (517) Woods, B. F., and Gillespie, J. M., Australian J . Biol. Sci., 6, 130 (1953). (518) Woolf, L. I., Nature, 171, 841 (1953). (519) Wooton, I. D. P., Biochem. J . , 53, 85 (1953). (520) Wooton, I. D. P., and Wiggins, H. S., Ibid., 55, 292 (1953). (521) Wunderly, C., Chimia (Swifz.), 7, 145 (1953). (522) Wunderly, C., ,Vature, 169, 932 (1952). (523) Wunderly, C., Gloor, E., and HBssig, il., Brit. J. Ezptl. PathoE., 34, 81 (1953). (524) Yamaki, T., Misc. Repts. Research S a t l . Inst. Resources, No. 17-18, 180 (1950). (525) Ylstra, J., Chem. Weekblad, 49, 1, 17 (1953). (526) Zager, S. E., and Doody, T. E.. Ind. Eng. Chem., 43, 1070 (1951). (527) Zbudovska, O., and Hais, I., Chem. Listy, 46, 307 (1952). (528) Zill, L. P., Khym, J. X., and Chenial, G. ll.,J . A m . Chem. Soc., 75, 1339 (1953). (529) Zimmermann, G., Z . anal. Chem., 138, 321 (1953). (530) Zimmermann, G., and Kludas. K . H.. Chem. Tech. (Berlin), 5, 203 (1953). (531) Zittle, C. A.. Advances in Enzymol., 12, 493 (1951). (532) Ibid., 14, 319 (1953). (533) Zwingelstein, G., Pacheco, H., and Jouanneteau, J. J.. Compt. rend., 236, 1561 (1953). (534) Zggmuntowiea, A. A., Wood, 31.. Christo, E.. and Talbot, N. B., J . Clin. Endocrinol., 11, 578 (1951).
Nucleonics CHARLES L. GORDON National Bureau o f Standards, Washington, D. C.
T(w.
HIS article reviews the publications of the past 3 years
The most powerful new tool of nuclear science which is new to analytical chemistry still is the method of activation analysis. For instance, Debiesse (30) could determine as little as 0.57 of cobalt in nickel by irradiation in a flux of 6 X 109 neutrons per second per square centimeter. This requires the use of either a cyclotron or nuclear reactor, which are still far beyond the financial capacity of most analytical laboratories. Fortunately, the services of the Oak Ridge National Laboratory for this kind of analysis have been opened to outside groups (21). For research purposes it is still more desirable for the analyst to perform his own analyses, because unexpected developments can be pursued immediately and not after a report from some distant laboratory. Lower cost neutron sources include radium-beryllium incorporating from 25 mg. up t o 3 grams of radium, costing from $600 to $75,000, and producing neutron fluxes of from loz to lo6 neutrons per sq. cm. per second. hntimony-beryllium sources are available for about $150 for a flux of up to 10,000 neutrons per sq. cm. per second, but have a 60-day half life. The chart of activation cross sections as a function of half lives of the radioisotope produced was given by Meinke and Anderson (101) and can be used as a guide as to the possibilities of the method. METHODS OF ANALYSES AND SEPARATIONS
Activation Analysis. A review of the methods for determining the naturally occurring radioelements and the stable elements
was given by Sue (141 ). Elements that have been determined in this manner are: antimony (78),boron (141), bromine as bromide (151), cadmium (141), carbon (28), cerium (141), cobalt ( S ) , copper ( 2 , S), indium ( f O f ) , lithium ( f d f ) , manganese (S), nickel ( 3 ) ,rhodium (101), silver (101, 141 ), tantalum (85, 88), thallium (31), yttrium (141 ), zirconium (79), and uranium ( 6 7 ) . Meinke and Anderson (101) made a study of the use of low level neutron sources (about 100 neutrons per sq. cm. per second) for precise activation analysie. From a study of the thermal neutron activation cross sections and the half lives of the products of the activation, they suggest that only rhodium, iridium, indium, silver, and dysprosium can be detected by this method. They give the errors of estimation of 1% of silver, rhodium, or indium in a mixture as about 6.7, 4.8, and 3.6% probable errors, respectively. The pile method of activation analysis is said to be able to determine as little as 7 X 10-9 gram, with an accuracy of 10%. Samples can be analyzed for impurities by the pile method by arrangement with Carbide and Carbon Chemicals Corp. (103). Activation analysis has been used by Herr (75)to determine the isotopic composition of lithium in lithium carbonate. Samples of the unknown and a standard sample are placed on a photographic plate, irradiated with neutrons, developed, and evaluated photometrically. Indicator Analysis. Instead of measuring the activity of the element being analyzed, the element may react with some other radioelement or ion containing a radioactive element which can
V O L U M E 2 6 , NO. 1, J A N U A R Y 1 9 5 4 then be measured. Govaerts and Barcia-Goyanes (59, 60), used a solution of silver containing radioactive silver-110 to precipitate chromium as silver chromate. The activity of the precipitate then was directly related to the amount of chromium present by a standard curve. Molybdenum and vanadium were similarly determined. Goyanes and Serrano (8) determined aluminum, zinc, magnesium, and manganese by precipitation as the orthophosphate using radioactive phosphorus. Ballard, Stevens, and Zuehlke ( 7 ) used iodine-131 as radioactive iodide to convert the silver of a photographic image quantitatively to silver iodide and then determined the silver content by measuring the iodine-I31 activity. Langer (92) used radioactive silver as an end-point indicator in argentometric titrations. Carrier-Free Separations. The production and isolation of carrier-free radioisotopes were reviewed by Garrison and Hamilton (42). Hamilton and coworkers continued their series of publications on simple and quick separations with separations for: magnesium-27 from aluminum (69), cesium-185 and rhodium-183, and -184 from tungsten (@), beryllium-7 from lithium ( 7 0 ) ,scandium-44, -46, -47, and -48 from titanium (44),bismuth-204 and -206 from lead (45), manganese42 from chromium (71),palladium-103 from rhodium (52), iron-59 from cobalt (46), chromium-51 from vanadium (46), platinum-191 and -193 from osmium (4?), ruthenium-97 and -103 from molybdenum (d?), thallium-200, -201, and -202 from mercury (48),lead-203 from thallium ( 7 2 ) ,rhodium100, -101, -102, and -105 from ruthenium (49), iridium-188, -190, and -192 from osmium ( 7 3 ) ,gold-195, -196, -198, and -199 from platinum (60), and tungsten-188 from tantalum (51). The chemical separations of fission products were summarized by Wilkinson and Grummitt (149), and many papers on the individual separations are given in the volumes on the fission products of the National Nuclear Energy Series (86). Other Separations. The Szilard-Chalmers effect is utilized for preparing many carrier-free radioactive isotopes. The method, however, is not an analytical one, in that the separation is not complete (83). An innovation to the ion exchange separation was introduced by Berne (11) for the separation of bromide ions from bromate. The exchanger was silver oxide-coated diatomaceous earth, from which the bromide was eluted with a soution of sodium iodide and barium ions. The silver and barium ions wereremoved by another ion exchanger. One of the simplestpreparations of carrier-free isotopes was the production of a mixed solution of radiolead and radiobismuth. Broda et al. ( 1 7 ) caught thoron, in air bubbled through a concentrated solution of thorium nitrate, in 0.1N hydrochloric acid which then decayed to lead-212 and bismuth-212. Chemla and Sue (22) were able to enrich sodium-22 from a mixture of sodium-22 and sodium-24 as the chloride by depositing them on a crystal of sodium chloride and causing them to migrate under an electrical field. Barrett ( 9 ) studied the effect of an electric field on the collection of radioactive ions of bromine, technetium, and indium, After elimination of the radioactive ions carrying a negative charge, positive ions of bromine-80 produced by isomeric transition from boron-80* were collected on the aluminum windows by applying several hundred volts pkr centimeter potential to it. I n analyzing aerosols for radioactivity, Pauthenier and Challande (116) used an electrical method similar to the Cottrell dust precipitator to precipitate all the radioactive particles. A reverse innovation has been the work of Linder (94,95) and Ohmart (116) where the radioactive material has been used to produce a potential differencebetween two electrodes. MEASUREMEN?
Counting. The measurement of radioactivity usually involves counting in some form. There is statistically an optimum distribution of the minimum counting time between each sample counting rate and the background counting rate which yields a
177 required degree of precision. A quick solution of the equations is given by Browning (19) in the form of easily used charts. Among the methods of presenting the radioactive material to the counter for analysis is the measurement from the surface of a solution. Goddu and Rogers (66) compared the count from solutions of silver in a lacquered aluminum dish with that from the same solutions in glass cups. The activity of the former decreased because of the plating out of the silver-111 from the solution onto the lacquer. Evaporation of liquid caused the activity of the latter to increase with time and showed the necessity of control of evaporation. Freedman and Hume (40)overcame the evaporation losses by covering the liquid with a thin film of lacquer. Preparation of coated foils was presented by Dodson et al. ( 3 3 ) . Spevack (135) applied for a patent on the method of introducing the radioactive material into an organic base which, after spreading on a foil, can be completely burned off, leaving the isotope as a compound of known composition. A comparison of counting methods used in determining iodine- 121 was made by Bruner and Perkinson (20). They found the flowgas type of proportional counter gave the highest sensitivity, but wet sample procedures give simpler and more stable counting systems. Filtration of the precipitated radioactively labeled material onto a glass frit with low shoulders was used by Pinajian and Cross ( 1 1 7 ) . A minimum “infinitely thick” sample is prepared. Dry solid particles such as ground rock or mineral were counted by Kulp (90) as a thick source with a sample tray filled to 2.7-mm. depth or as a thin source where the material was ground to pass a 300-mesh screen and dusted onto a silicone-grease-coated sample pan. The reproducibility of these films was within the statistical error of counting. A thin nylon support Fas used by Baker and Katz (6) to minimize back-scattering. Dust samples are usually collected by impingement on filter paper and the radioactivity measured by direct counting of the surface. Albrcio and Harley ( 4 ) found that penetration into the paper reduced the a-counting efficiency 30%, because of absorption of these particles by the paper. Siksna (134) determined variations in the ion content of air by making autoradiographs of the deposit collected on a brass disk when a t a negative potential of 4.5 kv. for 8 hours. Another method of presenting a solution in a flat surface to the counter was devised by Sear (167). He used a flat coil of thinwalled small-diameter polyethylene tubing to contain the solution. Raben and Bloembergen (119) introduced radioactive carbon in the form of soluble compounds directly into a liquid scintillator contained in a cell between two photomultiplier tubes. About 25% of the disintegratipna were counted. For the standardization of counting, laboratory standards are usually prepared. Several methods for making stable reproducible standards have been given (114,132, 133). Schweitzer and Nehls (126) recommend that each investigator prepare his own correction curves for self-absorption. The selfabsorption factor, F , for various p-ray emitters has been computed by Nervik and Stevenson ( f 1 S )as a function of the sample thickness. Other data on self-absorption and back-scattering have been obtained (83,36,37,55,66,85,125,130). Photographic Techniques. Half Iives can be determined photographically (120) by determining the activity by contact autoradiography a t different times during the decay of the material. Neutron flux densities were measured by loading the nuclear emulsion plate with boron-14 and lithium-6. Evaporating a solution of these isotopes in the form of lithium borate is used to obtain a high concentration of them in the emulsion. Haenny and Klement (66), using this technique and also loading the emulsion separately with the lithium or boron, determined their relative cross sections. Kaplan and Yagoda (82) used this technique for determining the neutron flux produced by cosmic radiation (neutron back-
ANALYTICAL CHEMISTRY
178 ground) which they found to be about 230 slow neutrons pel square centimeter per day. They suggest the use of this method for purposes of health monitoring. Braun (16) studied the factors affecting the length of the tracks in nuclear emulsions and found that a n error of not more than 0.5% was practical. Loading the plates affects the track length unpredictably. Shrinkage in the emulsion gives rise to a necessary correction in the track length. This shrinkage factor was found by Horan ( 7 7 ) to be a function of the angle of incidence and the usual correction should be restricted to angles of dip of less than 6' if the error of measurement is to be less than 2%. The horizontal a-ray ranges alone were found by Poole and Rlatthews (118) to be usable as a m a n s of determining thorium-uranium concentration ratios. They used the ratio of the number of tracks per square centimeter with horizontal ranges exceeding the maximum range of RaC' to the number of tracks with horizontal ranges between the maximum range of RaC' and the maximum range of ThA. For testing the resolution of autoradiographs, Stevens ( 1 3 7 ) toned photographic resolution test charts to convert the silver to silver iodide, with the latter containing iodine-131. Coating such charts with layers of known thicknesses of gelatin gives measurements on the loss of resolution when the radioactivity is located beneath the surface as in histological specimen. Three microns separation seriously reduced the sharpness of the image. Gomberg ( 6 7 ) claimed that the resolution of the wet process emulsion was about 1 micron and used a technique of producing the emulsion on the radioactive specimen. Rasch (121) used an emulsioncoating technique to render visible the radioactive centers of alloys. A method for the discrimination between particle tracks and fog (as by gamma radiation) is by underdevelopment. Gailloud and Haenny (41) found that by choosing a surface developer and adjusting the pH, by the addition of acetic acid, to as low as 6.8 would give discrimination against y r a y fog produced by 200 roentgens. Cosyns, Dilworth, and Occhialini ( 1 7 ) measured the effect of lowering the temperature on the sensitivity of nuclear emulsions with the intent to eliminate cosmic-ray tracks appearing in stored film. Significant but not complete elimination was observed. For weak sources of radioactivity Ader ( 1 )immersed a capillary tube containing the sample in a liquid photographic emulsion. The number and length of the tracks after development were used to determine the amount of radioactivity. Walker (144) analyzed high-energy protons by means of a stack of photographic plates separated from each other by thin aluminum foils. MISCELLANEOUS TYPES OF DETERMINATIONS
Pressure, Temperature. Ecker ( $ 4 ) used mercury-203, producing its r e m i t t i n g daughter thallium-203, to measure the density of the mercury inside a mercury arc. Then knowing the pressure, he determined the temperature from the gas equation of state. Conversely, Dainton and Kimberley (19)used the activity of phosphorus-32 to determine the vapor pressure of white phosphorus a t a given temperature. Solubility. A double precipitation method of determining the solubility of a compound with radioactive indicators was published by Neiman et al. (118). I n one example they precipitated copper thiocyanate in a 50% solution of zinc sulfate a t 20°, with copper-64 as the indicator. The procedure in the simplest form is as follows: T o a solution containing a millimoles of inactive ions A and an unknown amount of radioactive ions A with an activity of c counts per minute, add the reagent D necessary for the precipitation of the compound B of unknown solubility and bring the volume of the solution to 1) ml. Then filter off and determine the activity of the precipitated compound as i l counts per minute. To the filtrate which contains the activity representing the solubility of B, add a millimoles of inactive A and the reagent
D and again bring the volume to 2' ml. (evaporation). Again filter off this precipitate and determine its activity as il. If the unknown solubility is z millimoles per milliliter, the amount of B remaining in solution after the first precipitation is xu millimoles and the amount in the precipitate is ( a zu) millimoles. The activity of the first precipitate is il = C ( a xu)/a. After the second precipitation the solution again contains xu millimoles of B and the precipitate contains ( a xu - 50) = a millimoles of B. The activity of the second precipitate is is = cxv/(a xu). The absolute activity of the two precipitates is not found but, their ratio, ill&= p, can be easily determined and the solubility z = a(-4 - 8)/2u.
-
+
+
Surface. Hershenson and Rogers ( 7 6 ) studied the errors in volumetric analysis arising from adsorption using a 50-pl. Kirk pipet. They found that the percentage of the silver introduced into the pipet and adsorbed on its walls increased from about 0.25% with 1M silver solution to 1.7% with 10-6M solutions. An ordinary I-ml. pipet having nearly the same ratio of surface to volume gave values which agreed with those of the 50-p1. pipet. Long and Willard ( 9 7 ) ext,ended their previous work ( 7 4 ) on the sorption of ions on soft glass to determine whether the sorption process is a simple exchange process. Using sodium-24 (15-hour half life) as a preliminary adsorbed ion on soft glass and then immersing in sodium-22 (3-year half life), they were able to determine that the amounts sorbing and desorbing with time were approximately constant, though not necessarily a t equal rates. To study the leaching of sodium directly from the glass, they irradiated the 1-inch square glass specimens with thermal neutrons and found that the fraction of sodium leached from its surface by 0.1N nitric acid (water was nearly equally effective) was approximately 1.1 X 10-b. Willard (150) reports the results of tests of bromine vapor in contact with glass, in which it was found that ordinarily a monolayer of bromine was attached to the glass after 30 minutes, but if the exposure was conducted a t a higher temperature, 150' t o 1 7 5 O , three times as much bromine was adsorbed. The bromine remained on the samples even after evacuation for half an hour and standing in air for 24 hours. Beischer (10) used carbon-14-tagged stearic acid monolayers t o apply radioactive tracer to the surface of various materials. On heating and causing thermal diffusion on the surface, different amounts of chemical reaction of the stearic acid with various parts of the surface are caused by variations in the structure of the surface. Radioautographs of the surface can be taken and the quantitative amount of activity determined. The opposite technique of making the metal radioactive and applying the stearic acid to it was used by Bowden and Moore (13). Westermark and Erwall (148) used autoradiographs of the preferentially sorbed phosphorus-22 or lead-217 on minerals t o outline phase areas and noted that lead has a higher sorption of lead-217 than has antimony. Milutinovic and Novakov (102) studied the surface areas of powders by comparing the amount of iodine exchanged with the powder and the amount of iodine exchanged on the powder material when fused into small spheres of determined surface urea. A slight difference was noted with iodine-128 as an indicator whena maximum of 6GY0 of the chlorine in lead chloride was exchanged with potassium iodide, whereas mith untagged iodine the msximum was 6470. Isotopic Effects, In studies on the relative rates of hydrolysis of urea Schmitt, Llyerson, and Daniels (124) found that of the isotopes of carbon, carbon-14 wtcted the slowest and carbon-13 more slov,-ly than did carbon-12. The carbon-14, and to lesser cxtent carbon-13, accumulated in the last fraction to decompose. Stevens, Pepper, and Lounsbury(138) found the carbon-14 effect,to be more t,han double the carbon-13 effect,. Lindsay, Bourns, and Thode (96) found the probability of the rupture of a carbou-12carbon-I2 bond to be 2y0 greater than that of a carbon-13-c~bon-12 bond. Gilman, Dunn, and Hammond (53) found a very large difference in t,he silicon-hydrogen bond. When the normal
V O L U M E 26, N O . 1, J A N U A R Y 1 9 5 4 hydrogen and the deuterium compounds of PhaSiH were hydrolyzed, the deuterated compound reacted nearly six times faster than the normal. Isotopic Exchange. Harris (68) analyzed the rate characteristics of isotopic exchange and noted that the influence of the isotope effect is determined by the exchange mechanism. Karamyan (83) studied the Szilard-Chalmers method of separation of radioisotopes made by the (n, y) reaction, and found that there is not complete separation. S4FETY
Considerations regarding the safety of the analyst using radioactive isotopes involve: removal of deposited activities from contaminated surfaces, such as the apparatus used or the person of the analyst; removal of activities from the air; removal of activities from the laboratory wastes; and protection of the analyst from the radiations during the analysis. Surface Decontamination. One method of removing the reyidual surface activities after using apparatus is by coating the apparatus with a strippable film such as paraffin as used by Beischer (10). The other method is to remove the activities by chemical treatment. DeMent ( 3 6 ) sprayed the surface with a solution of sodium trisilicate. On converting this to silicic acid by application of hot mineral acid followed by washing with water, the contaniinants were removed. Kunkel (89) tested a number of cleaners and found silicon tetrachloride especially effective for noncorrodable surfaces. For removal from the skin, a mixture of titanium dioxide and a weak solution of hydrochloric acid was effective. Gregory (62) found a mixture of powdered wood and soap powder effective in removing substances containing uranium and radium from the hands. The Subcommittee on Waste Disposal and Decontamination has prepared a handbook on decontamination in laboratories (106). For very difficultly removable hand contamination immersion in strong hydrochloric acid for a short time is feasible, provided there are no scratches or other lesions in the skin. Tompkins, Bizzell, and Watson (142) tested various methods of removal using radioactive phosphate, barium, and iodide solutions. Waste Disposal. The Subcommittee on Waste Disposal and Decontamination of the National Committee on Radiation Protection has prepared several handbooks in this field. The handbook on recommendations for waste disposal of phosphorus32 and iodine131 for medical users (107) gives calculations on the permissible amounts of these activities which may safely be disposed to the sewer. Sample calculations for this type of disposal were also given by Kittrell (86). The sewage must be treated to remove or reduce the permissible amounts of radioactive isotopes allowed to pass into the effluent. Ruchhoft and others (162) studied the use of food wastes to s u p port zoological organisms which remove radioactive elements by adsorption. They (123) found biological methods remove only 9570 of the activity. Grune and Eliassen (63) noted that phosphorus-32 in concentrations of up to 10 mc. per liter did not affect the biological oxygen demand value. Ruchhoft (123), however, says that biological treatment is not satisfactory for the removal of phosphorua-32, which is isotopically diluted by the constituents of sewage nor is it applicable to soluble isotopes t h a t are not utilized or readily adsorbed on the biological floc. The detection and determination of the amount of radioactive materials in waste streams were discussed by Fields and Pyle (39) and by Kochtitzky and Placak (87). Other methods of waste disposal involve concentrating and storage. It has already become necessary to increase the storage capacity for radiochemical wastes and this has been accomplished by reducing the volume of the wastes by means of a 300-gallonper-hour evaporator as described by Browder (18). McCullough (99) extends the evaporation to reduce the solids t o a 5 to 10% moisture content.
179 Ion exchange is another method of concentrating the radioactive wastes. Ayres (6) studied this method and noted a further increase in concentration by a factor of 16 on ashing the organic exchangers. Machis and Geyer (98) noted that ashing of phosphorus-32 residues can be expected to produce an ash of sufficiently high activity to constitute a dust hazard in some instances. A review of radioactive-dust removal equipment was given by Bralove (14, 16). Corey, Perry, and Schwartz (66)used a gascleaning system together with a molten flux of sodium hydrovide under the grate in an incinerator to concentrate the wastes in an easily disposable solid matrix. Decontamination of waste water solutions and decontamination of drinking water are essentially the same problem. Lacy (91 ) used powdered metal slurries to sdsorb the radioactive materials to a safe tolerance level for drinking purposes after coagulation and filtration. A method for electrodialyzing solutions to separate wastes, including radioactive materials, was patented by Juda and McRae (81). Filtration systems for decontaminating water are described, among others, by Lauderdale and Emmons (93) and by Straub (139,140). Standards. A method of making Geiger-counter measurenieiits in the calibration of a large number of standards, which reduces the time required by 70%, was reported by Seliger (169). The method utilizes the statistical technique of the Latin square. 4-n counting in the standardization of radioisotopes by pill box, spherical, and cylindrical counters was studied (131). These Xeglect of the fractional different counters agreed within 1%. back-scattering from thin films was found not to affect the accuracy limits of this method (100). For such low-energy pemitters as cobalt-60 extreme precautions are required to eliminate sdf-absorption errors. General References. A iiumber of texts of interest to analysts working with radioactive chemicals appeared during the past 3 years (12, 24, 66, 38, 54, 61, 64, 80, 84, 104, 128, 136, 143). Three supplements to the collection of nuclear data have been published (166-147). The safety limits for personnel protection are being summarized by the National Committee on Radiation Protection and published a8 handbooks by the National Bureau of Standard8 (105-111, 156). LITERATURE CITED
.%der, &J. I.phys. , radium, 13, 110 (1952). Albert, P., Caron, M., and Chaudron, G., Compt. rend., 233, 1108 (1951). Ibid., 236, 1030 (1953). AlOrcio, J. R., and Harley, J. H., Nucleonics, 10, No. 11, 87 (1952). Ayres, J. .4.? I n d . E n g . Chem., 43, 1526 (1951). Baker, R. G.. and Kats. L.. .VtLcZeonics. 11. KO.2. 14 (1953). Ballard, A. E., Steven’s, G. W. W., and Zuehjke, ‘C. PSA Journal, 18B,27 (1952). Barcia-Goyanes, C., and Serrano, E. S., Bol. radioacticidad (Madrid),24, 34 (1951). Barrett, P. T., Proc. Roy. Soc. (London), A218, 104 (1953). Beischer, D. E., J . P h y s . Chem., 57, 134 (1953). Berne, E., Acta Chem. Scand., 5 , 1260 (1951). Rleuler, E., and Goldsmith, G. J., “Experimental Sucleonics,” New York, Rhinehart Publishing Co., 1952. Bowden, F. P., and Moore, A. C., Trans. Fararluv Soc., 47, 900 (1951). Bralove, -1.L., Nucleonics, 8, S o . 4, 37 (1951). Ibid., No. 5, p. 60. Braun, H., J . phys. radium, 13,347 (1952). Rroda, E., Fabitschowits, H., and Schonfeld, T., Monatsh., 83, 452 (1952). Brorder, F. hT.,I n d . Eng. Chem., 43, 1602 (1951). Browning, W.E., Jr., NucZeonics, 9, S o . 3, 63 (1951). Bruner, H, D., and Perkinson, J. D., Jr., Ihid., 10, No. 10, 57 (1952). C l e m . Eng. News, 30, 3306 (1952). Chemla, hf., and Sue, P., Compt. rend., 236,2397 (1953). Christian,.D., Dunning, W. W., and Martin, D. S.,Jr., Nucleonics, 10, No.5,41 (1952). Cook, J. B., and Duncan, J. F., “AIodern Radiochemical Practice,” London, Oxford University Press. 1952.
w.,
180
ANALYTICAL CHEMISTRY
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[End of Review Section]
literature Problems in Analytical Photometry M. G . MELLON, Purdue University, Lafayette, h d .
A
S A result of many decades of work, the chemist now pos-
sesses a considerable number of different kinds of analytical methods, by means of which he has been able to accumulate a wealth of information concerning both the qualitative and the quantitative composition of vast numbers of substances. Classical examples of such procedures are the widely known processes of gravimetry and titrimetry. Another of these processes, now also widely used, is absorptiometry. I n this type the physical property measured is the capacity of a given sample system to absorb radiant epergy. Because the literature for this area is extensive, fairly involved, and widely scattered, i t has seemed worth while to present some of the library problems encountered by the author during more than two decades of such work. A ndte of explanation of the methods may help in understanding the nature of the literature relating to them. First of all, the word “absorptiometric” is used in a general way to include two different types of procedures based upon the absorption of radiant energy. The first kind may be designated as comparometric, since a quantitative determination consists in comparing the intensity of the color of the unknown with that of a standard. Generations of chemists have used the terms “colorimetry,” “colorimetric,” and “colorimeter” here, most often with reference to standard series and balancing techniques. Such usage usually disregards physicists’ reservation of these terms for the measurement of color as color, without regard for the nature of the colorant or its amount. The second kind may be designated as photometric, which includes the use of both filter photometers and spectrophotometers. With these instruments one actually measures, in percentage or some related term, the absorptive capacity of the sample for given n a v e lengths of radiant energy. As the spectral region of 0.2 to 25 microns is a t present analytically most useful, the discussion is thus limited. Also, the emphasis is on photometry and its applications. Like most other methods of chemical analysis, photometric methods generally involve both chemistry and physics. The chemistry concerns the transformations required to produce a system fit for measurement. Representative common operations and processes are fusion, dissolution, oxidation-reduction, complexation, volatilization, precipitation, extraction, electrodeposition, and adsorption. The physics concerns the final operation of measurement-that is, principles and uses of the photometers. Much of the relevant chemistry has a long background. Spectrophotometers, in a t least primitive form, go back nearly a cen-
tury. Current applications have become very extensive and diverse. Consequently, only the general nature of the literature for each part of the total problem is considered. In general, the references cited are among the most important. If desired, they will lead the way to others. CHEMISTRY
Few desired constituents can be mearmred as such in the usual environment in which they occur. The chemistry of concern t o us is that which is applicable and necessary to make measurement possible. I n general, the kind of information needed, as far as it is collected and systematized, is to be found in the great treatises and in monographs. Subsequent to the time of their publication, one must turn, of course, to abstracting journals and thence to the original sources, such as periodicals, bulletins, and patents. For the general chemistry of organic compounds and their reactions, the incomparable source is the Beilstein treatise (49). The newer Elsevier (4) and Grignard (16)treatises are valuable complements to the Beilstein set, as is the set by Heilbron and Bunbury (17). As one turns from these comprehensive works to those more specialized, perhaps certain monographs are next in importance Thus, the ring index of Patterson and Capell (4%)serves for quick checking of particular structural types of organic compounds. Compilations such aa those of Yoe and Sarver (5J), Mellan (sa), and Welcher (61) summarize much information on organic reagents. Still more specialized is Martell and Calvin’s discussion of metal chelate compounds (3%). For inorganic chemistry the five treatises of most general value are those of Gmelin (59), Mellor (98),Friend ( l a ) ,Pascal (41),and Abegg and Auerbach ( 1 ) . There is often a long time lag in parts of these sets, the least serious perhaps being in the Gmelin set. Useful works specifically analytical are the new Fresenius and Jander (10) and the relatively old Rudisiile (45) treatises. The monograph of Hillebrand and Lundeli ( 1 9 ) is invaluable in being critical and up to date. The spectral range of 0.2 to 25 microns covers the nonvacuum ultraviolet, the visible, and the as yet analytically usable infrared regions. Very largely our interest in chemical transformations concerns the preparation of systems for measurement in the visible region-that is, colored solutions. Important requirements of such systems, and of reactions used for producing the solutions, have been summarized elsewhere (86). -4specific problem may emphasize the complexity of some of the
