(472) Winefordner, J. D., Staab, R. A., ANAL. CHEM.36, 1367 (1964). (473) Ibid., p. 165. (474) Winefordner, J. D., Vickers, T. J., Ibid., 36, 161 (1964). (475) Winkler, M. H., Biochim. Biophys. Acta 102, 459 (1965). (476) Wood, B. T., Thompson, S. H., Goldstein, G., J . Immunol. 95, 225 (1965). (477) Woodring, 31. J., Fisher, D. H., Storvick, C. A., Clin. Chem. 10, 479 (1964). (478) Woolf, L. I., Advances in Clinical Chemistry 6 , p. 97, Sobotka and Stewart, eds., Academic Press, New York, 1963. (479) Wyllie, J. C., More, R. H., Haust, M. D., J . Pathol. Bacteriol. 88,335 (1964).
(480) Yamazaki, T., J . Phamn. SOC. Japan 83, 402 (1963). (481) Yanysheva, V. S., Zavodsk. Lab. 30, 23 (1964). (482) Yanysheva, V. S., Sazonova, Z. A., Metody Analiza Khim. Reaktivov i Preparatov, Gos. Kom. Sou. Min. SSSR PO Khim. 4 , 135 (1962). (483) Yates, C. M., Todrick, A., Tait, A. C., J . Pharm. Phamacol., 15, 432 (1963). (484) Yoshimatsu, Y., Kotani, T., Hira-
yama, U., Shokuhin Eiseigaku Zasshi
6 , 15, 19 (1965). (485) Zachariae, H., Acta Dermato-Venereol. 44, 219 (1964). (486) Zakharov, I. A., Aleskovskii, V. B., Zh. Analit. Khim. 20, 700 (1965).
(487) Zamochnick, S.B., Rechnitz, G. A., 2. Anal. Chem. 199, 424 (1963). (488) Zarembski, P. M., Hodgkinson, A., Biochem. J . 96, 717 (1965). (489) Ibid., p. 218. (490) Zarowin, C. B., Rev. Sci. Znstr. 34, 1051 (1963). (491) Zhorov, Yu. M., Panchenkov, G.
M., Gurevich, I. P., Venkatachalam, K. A., Khim. i Tekhnol. Topliv i Illasel
10, 61 (1965). (492) Zweig, G., Ed., “Analytical Methods for Pesticides, Plant Growth
Regulators, and Food Additives,” Vol. I, Principles, Methods, and General Applications, 1963; Vol. 11, Insecticides, Academic Press, New York, 1964.
Gas Analysis A. P. Hobbs, The Dow Chemical Co.,Midland, Mich.
T
covers the past two years (1964-1965) of published articles. Some of the methods of analysis have shown ingenuity and careful research. This may have resulted because of the routine analysis being done by instruments leaving the nonroutine analysis to be run by more complicated and time consuming methods. The authors have gone to all kinds of disciplines for solutions to their analysis problems. HIS REVIEW
HYDROGEN
The patent by Pfefferle (159) for an electrical resistant type detector for hydrogen gas is rather unique. The gas contacts an aluminum oxide coated palladium containing metal element supported on a suitable insulating member. The variat,ions in resistance in the electrical heated element are measured as the hydrogen content of the gas changes. Eisenstadt and Hoenig (51) have developed a similar chemisorption detector for hydrogen and have checked its sensitivity to other gases such as oxygen and nitrogen. They report strong response to oxygen and weak response to nitrogen. The determination of dissolved hydrogen in water has always been a problem. Faber and Brand (56) have worked out an indirect method in which the hydrogen is made to react by a catalyst of finely divided platinum or barium sulfate with excess oxygen dissolved simultaneously. If oxygen is deficient, it is supplemented by adding picric acid. The hydrogen content is determined by measuring the oxygen consumption. A maximum of 15 ml. of hydrogen per liter of water can be determined. If the Winkler method for 166 R
ANALYTICAL CHEMISTRY
dissolved oxygen is used, the lower limit for hydrogen content is 3 ml. per liter of water. By the o-toluidine method, down to 0.3 ml. of hydrogen per liter of water can be determined to within one per cent. An emission spectroscopy method for the determination of hydrogen in nitrogen was investigated by Dickinson and Wheeler (44). A quartz envelope electrodeless discharge tube excitation was used. The sample gas was passed through a cold trap to eliminate water and hydrocarbon vapors before entering the discharge tube. Using a grating monochromator with photomultiplier detection set a t 486.3 A., hydrogen can be determined down to -0.05% by volume. MOISTURE
For water in gaseous or liquid chlorine, Jaksic and Bulimbasic (94) describe the use of phosphorus pentoxide or magnesium perchlorate as the desiccants to be used. Istomin (93) as well as Johnson and Pohler (98) in their patent have used a film of phosphorus pentoxide as the absorbent for moisture in a gas. The film forms phosphoric acid with the water and is then electrolyzed back to phosphorus pentoxide. The amount of current used in the electrolysis is the measure of the water present. A capacity measurement system is used by Voelker and White (209) to determine moisture in hydrocarbon streams. The moisture cell is a concentric cylindrical capacitor with the annular space between the plates filled with granular activated alumina. A calibration curve is required for each hydrocarbon stream. A method of operation and the theory of a condensation hygrometer which automatically
records the measured values is given by Briot (22). He presents calibration curves and examples of application. The Karl Fischer method for water determination with a transitorized control circuit is described in detail by Francis and Sawyer (60). The transitorized control circuit features a time delay relay to discriminate against premature end points. Richter and Gillespie (166) have turned an old method into a new procedure for moisture determination in gases. The gas sample is passed through a column of calcium carbide which is made from carbon-14. The acetylene generated is passed over a Geiger-Mueller Counter; the count rate is a direct measure of the water content of the sample. Serak (181) describes an apparatus based on the psychrometric principle and measures the differences in temperature of two semiconducting thermistors serving as temperature detectors. Any kind of gas with an exactly defined content of moisture can serve as the carrier gas. OXYGEN
Apparatus to create absolute standards for oxygen determination by the Winkler method is described by Grasshoff (74). Countercurrents of water and air saturated with water vapor are used to obtain equilibrium. Great care is taken to prevent bubbling which causes oversaturation. Oxygen saturated water a t defined temperatures can be obtained after a few minutes and used as an absolute standard. The apparatus consists mainly of a large snake cooler within a thermostat, in which water runs down while air moves upward slowly, giving close contact a t a
large surface. Rabinovich and Sherman (164) have modified the Winkler’s method for determining dissolved oxygen in small liquid samples. The sampling and reaction are carried out in a 20-ml. medical syringe except for titration. Full strength solutions are added to the sample in the syringe from smaller syringes or from microburets equipped with injection needles. The mixture is ejected after reaction to 5-10 drops of the sulfuric acid in a beaker, avoiding contact between air and liquid before acidification. The iodine is then titrated with 0.001N sodium thiosulfate and starch solutions. A galvanic cell is used by Bazzan and Bordonali (15) to detect traces of oxygen in gases. They used the type cell of gas/Ag electrode, porous polyvinyl chloride sheet impregnated with 25% KOH/Pb electrode. The silver electrode is kept in the stream of gas. The amounts of oxygen and hydrogen in a gas mixture can be measured more accurately by passing a sample a t elevated pressure (20 atm.) through a humidifier, and then through a galvanic cell still a t elevated pressure and constant predetermined flow (56). A device is described rated for elevated pressures and including a means for transfer of the gas from the humidifier a t elevated pressure through the galvanic cell and a means to control gas flow velocity through the cell. Mackereth (129) describes an improved membrane-protected galvanic cell probe for oxygen concentrations in liquids or gases. Allsopp (4) and Pete et al. (157) describe variations of the Hersch Cell for oxygen determination. An electrode for polarographic estimation of oxygen in gases is described in Charlton’s (29) patent. The electrode is small enough to be inserted in an artery. Zakhar’evskii and Petrovskaya (214) have readapted a coulometric method for metals to the determination of oxygen. Two Russian patents (71, 72) are on a gas analyzer for oxygen, based on a measurement of the thermal conductivity of oxygen in a magnetic field. It consists of a gauge of two measuring chambers connected with each other, with thermoresistances as sensitive elements connected in a bridge measuring circuit and a solenoid, in whose weak magnetic field one of the chambers is placed. Goto and St. Pierre (73) measure the partial pressure of oxygen in carbon monoxide-carbon dioxide and argonoxygen mixtures by an oxygen concentration cell with a solid electrolyte. A recording apparatus is described by Burkert (26) for the determination of oxygen in boiler feed water. It depends on the reaction of nitric oxide with oxygen and water to form nitrous acid, and measures the change in conductivity brought about by this reaction.
Kavan et al. (102) have found that the addition of anthraquinone-2,6-disulfonic acid or its salts improves the adsorption capacity and speed of existing analytical reagents. An amperometric device for measurement of dissolved oxygen in oil-field water is described by Garst and McSpadden (66). The oxygen sensing electrode is a platinum disk cathode wet with a concentrated buffered ammonium chloride solution confined by a tightly fitting polyethylene membrane. Atomic oxygen density profiles in the 90-140 km. altitude region were obtained by analyzing the radiation intensity of chemiluminous XO trails deposited by rockets into the upper atmosphere (69). The trails consist of a very bright head glow and a dimmer afterglow. The head glow is believed to originate in the mixing zone around the NO jet expanding into the atmosphere. Oxygen atom densities are evaluated by applying the gas dynamic model to the radiation intensity of the head glow. The resulting altitude profiles indicate maximum oxygen atom densities in the 103-107 km. region. Davis (40) had described a spectrophotometric method for the determination of ozone dissolved in aqueous solution. The principle of the method is based on the absorption of ozone in alkaline potassium iodide solutions. Iodine is released on acidification and the chromophoric properties quantitated. The photometric method described by Bravo and Lodge (21) is based on the ozonolysis of 4,4’-dimethoxystilbene yielding under appropriate conditions one mole of anisaldehyde. The aldehyde formed can be determined by an extremely sensitive method. Gushchin (80) made a number of flights for the study of the possibility of using a helicopter for ozonometric observations. A filter type ozonometer was used in the measuring. It was possible to measure ozone with the sun as light source through the lifting propeller. The photoelectric system of the ozonometer was sufficiently inert that it did not react to “twinkling” caused by the rotating propeller. NITROGEN COMPOUNDS
Demmitt (43) described a continuous measurement of trace concentrations of ammonia in water. Justatown (99) gives the determination of ammonia in water and aqueous salt solutions on the basis of partial ammonia pressure measurements. Kear infrared spectrophotometric determination of ammonia, carbon dioxide, and water a t elevated temperatures and pressures is discussed by Koren and h d r e a t c h (112). Roskam and D. deLangen (172) give a simple colorimetric method for the determination of ammonia in sea water.
The ammonia in sea water is complexed by Ca and Mg with CDTA, adding OC1 and thymol-MezCO solution, and measuring the absorbance a t 630 mu. Fugas (62) has studied the determination of nitrogen dioxide in air by three modifications of the Griess-Ilosvay reagent. Sojecki et al. (184) give a continuous method of determining nitrogen dioxide in air. Grosskopf (77) describes indicator tubes for the detection of nitrogen dioxide in gases. Comer and Jensen (34) monitored by spectrophotometric measurement the concentration of combined NOZ-NzO4in air. Continuous measurement of nitrogen dioxide in air by means of absorption photometry has been made by Yanagisawa et al. (213). Filyanskaya (58) has used the linear-coloration method for determination of nitrogen dioxide in air. hlochizuki et al. (140) present a new method for measuring nitrous oxide. A rapid and inexpensive method of utilizing discharge light in a vacuum tube is given for measuring KzO concentration. NzO shows an afterglow which can be measured in the presence of other respiratory gases. Continuous determination of nitrogen oxides in air and exhaust gases is given by Ripley et al. (167). The main nitrogen oxide in automobile exhaust and polluted air is NO. Instruments determine only NOz, so to make them usable for determining KO, it must first be converted to NOz. This is accomplished by saturating glass fiber paper with a solution of KazCrzO-i and sulfuric acid and drying it. Anderson (5) gives a method for NO using KMnOc as an oxidizing agent. Semyachkova and Korskova (178) increase the precision of the determination of nitric oxide by mixing the sample with a weakly alkaline solution of sodium sulfate. The sulfonitric salt thus obtained is spectrophotometrically measured. The amperometric determination of nitrogen oxide in sulfuric acid towers is described by Helbig and Steinhauer (86). The Nz03containing sulfuric acid passes to electrodes. At one electrode a potential is established that is within the limits of the polarograph. The current observed is a measure of the “ 2 0 3 concentration. Ovcharenko (152) describes a colorimetric determination of nitrogen oxides in combustible gases. A standard scale was prepared for photocolorimetric plotting of nitrogen oxides calibration curve by using a photocolorimeter with a blue light filter. Filyanskaya (69) states that KO is oxidized to YO2,either with 5% KMnO? in 12% H3P04,or with silica gel powder impregnated with 0.85 ml. of this solution per gram. Because NOz does not react with the indicator, N O and NO2 are determined by passing the gas mixture through the sequence of indicatorVOL. 38, NO. 5, APRIL 1966
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oxidizer-indicator. For NO2 determination, silica gel having a layer of diphenylamine deposited by sublimination is used. The following oxidizing agents were tried for hydrazines (131) : KIO3, HIOs, I, BrC1, and KCr03. KI03 and HI03 proved to be useful for N2H4,but not for substituted hydrazines. Iodine could be used for NLHband monosubstituted but not for disubstituted hydrazines, while BrCl was not satisfactory for microdeterminations. Good results were obtained with KBrO8. This was applied to RTc”NH2, RXHN :R’, and RR‘XNH2. An adjustment has to be made for hydrazines which contain one Ohle or a benzodioxane or dihydrobenzofuran group. NOBLE GASES
Katural gas is analyzed by Demenkov (42) for helium by a mass-spectrometer with a hot-cathode electron source. Penchev and Pencheva (156) describe a simplified apparatus for the determination of helium in natural gases. It consists of two parallel capillary barometric tubes immersed in glass and connected a t the other ends with an adsorption vessel containing activated charcoal. The apparatus is evacuated by the cooling of charcoal with liquid oxygen or nitrogen. The cooled charcoal absorbs all the gases except helium and part of the neon. The amount of helium is determined from the difference in height of mercury in the capillary tubes interpreted from curves plotted for standard conditions. The effect of neon is determined and the correction for neon is made on the basis of the neon helium ratio, which is usually constant in gases from a given area. .4n apparatus patented by Dubansky et al. (48) affords simultaneous analysis of three samples for the determination of small amounts of noble gases, especially argon. The gases are determined manometrically after absorption and reaction of the other constituents by copper oxide, titanium, calcium, active carbon, and molecular sieves. Cermak and Herman (27) show that an atomic beam of noble gases, excited by electron impact, contains atoms in long-lived excited states with excitation energy close to the ionization potential. The atoms in these states can be detected by their ionization caused by an interaction with metallic surfaces and by ionizing reactions in collisions with polyatomic molecules. AIR POLLUTANTS
A program for estimating the contaminants produced by men and materials in spacecraft atmospheres is described by Solitario, Bialecki, and Laubach (185). By using a solution of diethylamine, triethanolamine, cop168 R
ANALYTICAL CHEMISTRY
per acetate, and ethanol, Zawadzki and Grabowski ($17) are able to determine carbon disulfide in concentrations of 0.01-0.08 mg./liter. Hydrogen sulfide was determined by using an absorbent medium consisting of ammonium molybdate ammonium sulfate, concentrated sulfuric acid, and distilled water. A review on application of spectroscopy, spectrophotometry, gas chromatography, conductometry, and coulometry to the detection and determination of toxic substances in industry is given by Bokhoven (16). Pavelka (155) describes a new absorption vessel for the determination of gaseous impurities in the atmosphere. An electrochemical sensor for detecting trace contaminants in air is reported by Eaton (50). A two-terminal electrochemical cell was used to detect trace amounts of an oxidizing agent in air. An investigation of the cell electrical parameters was made while the cell was in uncontaminated air, and while exposed to chlorine or nitrogen dioxide. An equivalent circuit was obtained. The cell, without any external power or circuitry, can detect concentrations below the threshold limit values for chlorine and nitrogen dioxide. The cell output can be increased by passing a small d.c. current through the cell This current also improves the cell recovery time. Horak et al. (90) have patented an indicator tube for continuous monitoring of hydrogen cyanide in the atmosphere. Two methods are described by Kudsk (116) for the determination of the mercury content of air. X field method of low accuracy uses titration with a chloroform solution of dithizone. The more accurate method is a spectrophotometric dithizone procedure. This can be used in the presence of up to 20 mg. of Cuf2. HALOGENS
Two cells for analysis of liquid chlorine by spectroscopy are given by Pross (263). The cells are made of type 316 stainless steel. One cell (1 cm. long) is equipped with calcium fluoride windows (55 mm. in diameter, 6-5 mm. thick) suitable for the infrared region 2.5-8.5 microns. The pressure plates securing the windows are held in place by Allen-type screws. The other cell (5 em. long) was fitted with sodium or potassium chloride windows (35 mm. in diameter and 20 mm. thick) suitable for the ranges 8-15 and 8-20 microns, respectively. The sealing pressure is provided by a chevron-type Teflon packing around the window, because sealing pressure perpendicular to the plane surface of the window leads to crystal cleavage. A continuous method of determining chlorine in air is given by Sojecki (183). An evaluation of the methods for de-
termining chlorine in air has been made by Kaszper and Kesy-Debroska (101). They state the best method is that of using o-tolidene and a spectrophotometer. Gobrecht et al. (68) suggests the use of a halogen leak detector for the determination of very small amounts of chlorine and halogen containing gases. Although they indicate the detection of dichlorodifluoro methane, a fluorine compound without any of the other halogens cannot be detected in this manner. Zavarov (215) gives a good method for the determination of free chlorine and sulfur dioxide in mixtures of chlorides and oxychlorides of sulfur. This is usually a very tricky separation and determination. Small amounts of chlorine in bromine can be determined spectrophotometrically if the methods of Utsumi et al. (199) are followed. The bromine and chlorine are reduced to the bromide and chloride ions. The bromide is volatilized, and the chloride ion is determined by the mercuric thiocyanate method. Fluorine gas can be analyzed by reaction of the fluorine with mercury a t room temperature (176). This coupled with infrared analysis of fluorine gas. Comer (34) describes an apparatus for the addition of mercury into a mixture of fluorine and oxygen for the analysis of fluorine. Kel-F polymer oil is added to bring the apparatus back to atmospheric pressure. The volume of mercury plus the volume of oil equals the volume of fluorine in the gas. Mixtures of fluorine and hydrogen fluoride are collected on silica gel wet with triethanolamine solution. Suvorova et al. (195) recommend the thoriumthoron method for the fluorine content of the collected material dissolved in water. Kerenyi and Kuba (104) have shown that in the colorimetric determination of chlorine dioxide the interfering influence of chlorine can be removed by the reduction with malonic acid. Gwiazdowski et al. (82) describe an absorber for the determination of HC1 in waste gases stemming from chlorination of organic compounds. The HC1 gas is absorbed in water, and as the density of the resulting solution exceeds a predetermined value, a float allows dilution to take place to maintain the density. A very sensitive method for the determination of chlorinated hydrocarbons in the air is described by Stier (191). The vapors are absorbed in toluene, the chlorine is split off with sodium biphenyl, and the chlorine is titrated amperometrically. Spectrometric determination of tetrachloroethylene in air is given by Dmitrieva (47). Determination of thionyl chloride in a mixture containing sulfur chlo-
rides and sulfur oxychlorides is given by Zavarov (216). The thionyl chloride is selectively hydrolyzed by the water of crystallization of ammonium alum in a cerbon tetrachloride suspension, to yield sulfur dioxide. The ultraviolet spectrophotometer is used by Crummett and h4cLean (39) to determine trace quantities of phosgene in gases. Bulcheva et al. (24) use indicator pipets for phosgene and diphosgene in air. SULFUR COMPOUNDS
A polarographic analyzer for continuous measuring of concentration of hydrogen sulfide in gases is described by Janda and Hrudka (96). The apparatus has as a novel feature a polarographic vessel containing carbon electrodes. The anode is the indicating electrode and is bored axially and provided with holes on the periphery which allow passage of the investigated gas with an indifferent electrolyte. Malkova and Radovskaya (130) use the molybdenum blue complex for the determination of small concentrations of hydrogen sulfide in the calibration of industrial gas analyzers for hydrogen sulfide. Buck and Stratmann (23) give a description of a modified impingement absorption cell for sampling of the air for determination of hydrogen sulfide by the molybdenum blue method. Baranenko and Krivosheeva (11)absorb the hydrogen sulfide in cadmium acetate and titrate the excess cadmium. Shul'gina et al. (182) have improved on the titration method for hydrogen sulfide. The methylene blue method has been studied by Mason (132) who recommends the use of assayed methylene blue instead of analyzed sulfide solutions. A carbon-steel cylinder lined with a baked phenolic resin is satisfactory for sample storage. Mercaptan sulfur in hydrocarbons is titrated potentiometrically by Hammerich and Gondermann (83). For determination of organic sulfur compound in gases, Koch and Paul (111) use specific absorbents for each of the sulfur compounds. Calcium chloride is used to absorb hydrogen sulfide which is determined by combustion or iodometrically. Mercaptans are absorbed in mercuric cyanide and are determined the same as hydrogen sulfide. The gas is then passed through silver nitrate where organic sulfides and disulfides are absorbed. Thiophenes are removed with 98% sulfuric acid and determined with isatin. Diethylamine removes carbon disulfide and carbonyl sulfide, which are determined by an Orion polarograph. An instrument is described by Nash (145) for measuring sulfur dioxide. Readings are taken by aspirating air into a small condensation cell contain-
ing dilute hydrogen peroxide. Estimation of sulfur dioxide in the polluted atmosphere of an industrial area with a simple apparatus is described by Mathur and Chaturvedi (133). The apparatus consists of a set of three bottles, an aspirator, and a funnel. The air is bubbled through solutions in the three bottles and is then titrated. Nelson (148) has studied the parameters of a continuous infrared gas analyzer for the determination of sulfur dioxide. Spectrophotometric determination of sulfur dioxide is made by Stephens and Lindstrom (188) by use of phenanthroline. The pararosaniline method is used by Lampadius (118) and Huitt and Lodge (92). Huitt and Lodge have studied the method to increase the sensitivity while Lampadius has used an apparatus in an airplane to check the air around factories. Kuczynski (115) discusses a method of calibrating sulfur dioxide gas analyzers. Tapfer (196) determines sulfur dioxide by oxidizing it to the sulfate and back-titrating the added excess of barium ions. Contaminated air reacts with acidified hydrogen peroxide solution in a countercurrent absorber to form sulfuric acid (123). The impedance of effluent is in inverse ratio to the sulfur dioxide concentration. Changes in impedance are detected by two parallel electrodes when the predetermined high frequency across them is disturbed. An indicator for sulfur dioxide consists of silica gel treated with potassium iodate, starch, and zinc chloride (17'9). There is a linear relation between the length of the colored layer and the sulfur dioxide concentration. Anodic voltammetry and ultraviolet spectrophotometry are used by Seo and Sawyer (180) for sulfur dioxide. A reliable and accurate automatic analyzer was developed by Laxton and Jackson (120) to determine concentration of sulfur trioxide in flue gas. The reaction between the sulfate ion and BaC6C1204is utilized in a colorimetric system to give continuous records. Sullivan and Warneck (194) bubble the sample through a solution of known barium content, the dissolved sulfur dioxide removed by flushing with argon and the remaining barium back-titrated. Lisle and Sensenbaugh (127) recommend the condensation method for sulfur trioxide in flue gases. The relation between acid dew point and sulfuric acid concentration is shown experimentally and agrees with the Muller curves. A determination of sulfur trioxide in a mixture with sulfur dioxide is made by absorption of the gaseous mixture in dry sodium chloride with subsequent dissolving of the absorbent in water (103). The solution thus obtained is back-titrated with an alkali metal
base. To avoid errors due to the presence of sulfuric acid in the indicated mixture, the gas not absorbed is passed through water in which hydrogen chloride equivalent to half the sulfuric acid in the original gas mixture is then detected. Losikov et al. (128) recommend that in the water used to absorb sulfur dioxide and trioxide, that some antioxidant such as glycerol, P-naphthol, hydroquinone, and formaldehyde be added to the water. A new more satisfactory instrument for the continuous measurement of hydrogen sulfide and sulfur dioxide in a process stream is described in detail with an appropriate sketch (168). This is essentially a modified ultraviolet analyzer that includes a samplehandling system and a catalytic furnace capable of oxidizing hydrogen sulfide quantitatively to sulfur dioxide. A reference stream in which the hydrogen sulfide remains unchanged and another stream after the hydrogen sulfide has been oxidized are used. Omichi (150) and Bowden (20) use lead dioxide for capturing sulfur oxides. Omichi makes the barium chloranilate addition to the solution from the lead dioxide and measures the absorbance. Bowden measures the reaction of the sulfurous constituents of the air with a prepared lead dioxide surface. Lawrence (119) has studied the lead dioxide instrument and has modified it so that wind does not interfere. The modified instrument is less liable to errors and can be further modified to eliminate them completely. Kiboku (108) determines carbon disulfide by an oxidimetric estimation by use of potassium ferricyanide. DeFilippo and Preti (41) reacts carbon disulfide with morpholine to form insoluble morpholinium morpholinedithiocarbamate which may be weighed or titrated. Vlckova (208) determines carbon disulfide by the color reaction of dithiocarbamates with copper ions. An instrument to determine sulfur dioxide in air operates by absorbing sulfur dioxide in a starch-iodine reagent (149). The reagent is decolorized quantitatively and this change is measured photometrically and indicated on a galvanometer. This instrument was readily adapted for measuring other atmospheric pollutants by changing the reagent and optical filter. Pichl (160) describes a novel apparatus for quantitative determination of traces of sulfur or halogen. The determination is photometric for halogen and gravimetric for sulfur. A proposed modification for continuous turbidimetric determinations is shown. HYDROCARBON
A compound in a mixture of gases is determined quantitatively by noting the temperature change on the addition VOL. 38, NO. 5 , APRIL 1966
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of a t least a stoichiometric amount of a reagent which will react with the compound in question but not with the other gases. Glassbrook and Koenecke (67) have patented an apparatus to do this which consists of an open pipe packed with iron or steel wool. To the outer surface of each end of the pipe is soldered a constantin lead making an intimate electrical contact. These wires lead to a millivoltmeter where the temperature differential is measured. A side-tube just before the first lead admits the reagent. hlogilevskii and Dianova (141) appoach the analysis from a different angle. They contact the test gas with a series of bacteria cultures, each capable of selectively oxidizing one of the components of the test gas. Subsequently, the volume contraction is measured and the content of the oxidation products is determined. Elinson (62) suggests the holding of the hydrocarbon mixture a t the boiling point of each individual component starting a t the lowest boiling material. This may work satisfactorily for saturated hydrocarbon but not unsaturates a t just below room temperature boiling points. An apparatus consisting of two continuous chambers separated by a rubber membrane for the detection of hydrocarbon gases in air has been patented by Ray (166). Each chamber contains a bimetallic strip passing through the membrane with the positions of the metals inverted, one in the relation to the other. Each element is enveloped by an electric heatable platinium coil. One chamber is open to the test atmosphere and has the end of the bimetallic strip fixed by a setscrew; the other chamber is closed, and by the deflection of the strip an electric contact can be closed. When a hydrocarbon-containing gas is present in the test chamber, the unequal heating of the elements causes their deflection and the closing of the contact. A glowing platinum spiral is used by Chapala (28) to oxidize hydrocarbons to carbon dioxide. The carbon dioxide is absorbed in standard barium hydroxide, the excess of which is titrated with standard hydrochloric acid. Toluene vapors are determined by indicator tubes by Kozlayeva and Vorokhobin (11.3). Trace quantities of formaldehyde in air -were detected by a colorimetric method using chromotropic acid as given by Krynska (114). A polographic method is used by Rogaczewska (170) for determining acrylonitrile in air, Cobaltacobaltic oxide on active alumina is used as a catalyst by Osipova et al. (161) to oxidize methanol for its determination in air. The concentration of its oxidation products is a measure of the methanol present. The catalyst is used to ensure complete oxidation. Methylene chloride in air in the presence of other chlorinated hydro170 R
ANALYTICAL CHEMISTRY
carbons is determined by Gronsberg (79) by hydrolysis. The methylene chloride is hydrolyzed to formaldehyde which is determined coulometrically with chromotropic acid. For the determination of monochlorodimethyl ether in air, Vinogradova (207) carries out a decomposition hydrolysis t o give chloride ion and formaldehyde. The chloride ion is determined turbidimetrically by the use of silver nitrate and the formaldehyde is determined colorimetrically by using chromotropic acid solution. Vaistariene et al. (200) give the alcoholic silver nitrate method for the determination of acetylene in gases. The acetylene reacts with the silver nitrate to release nitric acid which is titrated with standard caustic. CARBON M O N O X I D E A N D CARBON DIOXIDE
Hesse (88) has improved the silica gel for carbon monoxide indication with better compounds and cheaper. The air to be tested is passed through a cobalt sulfate impregnated gel. Holders are described by Milhovitch (1.37) for stiffened cellulose impregnated with palladium chloride, hydrogen chloride, and aluminum sulfate. A two-pipet system consisting of a sulfuric acid-cuprous oxide suspension and ammoniacal cuprous solution is recommended by Jobahazi (97) for carbon monoxide analyses. A new photometric determination of carbon monoxide is based on its reaction with an aqueous solution of bis-(0-phenanthroline)-palladium chloride (25). The method is selective and under given conditions independent of the presence of other reducing gases. Levaggi and Feldstein (124) react carbon monoxide with an alkaline solution of the silver salt of p-sulfamoylbenzoic acid. Comparison of the absorbance of the collodial silver with a standard curve gives the amount of carbon monoxide. Roberts and Sawyer (169) developed a voltammetric method for the determination of dissolved carbon monoxide in caustic solution. Details of the activation process are discussed as well as effects of various supporting electrolytes. Muzyczuk (144) has modified the Glover method for precise determination of carbon monoxide in mine air for early detection of interior fires. Up to 10 p.p.m. carbon monoxide in oxygen or air can be determined by reduction of silver p-sulfamoylbenzoate in alkaline solution to a stable solution (30)* Carbon monoxide in blood is dissociated from carboxyhemoglobin by oxidizing the latter to methemoglobin with ferricyanide (32). The dissolved carbon monoxide is then extracted by bubbling oxygen through the solution
into a tonometer, and measured therein with an infrared analyzer. Feldstein (57) reacts carbon monoxide with an alkaline solution of silver sulfamoylbenzoate and measures the absorbance of the resulting collodial solution. To remove interfering reducing substances, the sample is passed through a mercuric sulfate impregnated silica gel tube prior to its entry into the reaction flask. Diebolt (45)uses neutron activation for the determination of carbon monoxide. The reagent is first irradiated before reaction and the radioactivity of the product is measured. Lemcke and Brauer (121) describe substitute materials to be used in a carbon monoxide alarm system. They give several materials that may be substituted for the present ingredients. An improved gas analyzer for determination of trace concentration of carbon dioxide employs the dependence of the time of formation of visible barium carbonate crystals in a film of barium hydroxide solution on the carbon dioxide content of the gas (158). The errors in the determination of carbon dioxide by the decrease in conductivity of caustic solutions can be minimized by using a t least 0.025N caustic, and flow rates can be increased by adding monoethanolamine or the enzyme carbonic anhydrase to the base solution (14). An indicator tube for immediate detection and determination of carbon monoxide in atmosphere is prepared from silica gel saturated with methyl vilolet 6B and hydrazine hydrate (126). An alcoholic solution of the dye forms with hydrazone a lenco compound which is decomposed by carbon dioxide and the dye regains its colored form. Gardiner (65) tested known and unknown concentrations of carbon dioxide in moist air in a BOC carbon dioxide analyzer, and with a photoelectric colorimeter. Known concentrations were determined with a Drager analyzer. Good results were obtained with tests of moist air containing gradually increasing concentrations of carbon dioxide with the BOC analyzer. Pasich and Przadka (154) has carried out in a simple glass apparatus consisting of an Erlenmeyer flask with tube, sample dish, and buret, the volumetric determination of the carbon dioxide developed by concentrated HC1. The sealing fluid was saturated sodium chloride solution. Even nonactive carbon dioxide could be determined, as in the Tillmana apparatus. Pribyl (162) uses an amperometric determination of carbon dioxide in aqueous solutions. Khitarov and Vovk (105) measure changes in electrical conductivity of the barium hydroxide solution during passage through it of gases containing carbon dioxide for determination of traces of carbon dioxide. Precipitation
of barium carbonate causes changes in electrical conductivity measured by the Wheatstone bridge method. Baranenko et al. (12) determine carbon monoxide by absorption under static conditions and carried out with a standard solution of barium hydroxide. A tuning fork vibrates a dual-wavelength filter in a miniature carbon dioxide sensor (211). Alternate passing of a wavelength, which represents the absorption band of carbon dioxide, and a reference wavelength provides a measure of the amount of carbon dioxide in an enclosed breathing atmosphere. The dual-wavelength filter is mounted on one tine of a vibrating tuning fork. The method of using fixed-wavelength filters, separated by an opaque area, permits small interference filters instead of the more complicated and bulky prism or grating monochromators. Toedt (197) determines carbon dioxide by passing the gas stream through an absorbing medium, which is able to bind carbon dioxide reversibly. Thus the content of carbon dioxide in the liquid is proportional to that in the gaseous phase. The carbon dioxide containing liquid is passed over a conductivitymeasuring arrangement. Moretti (142) proposes three methods of determining carbon dioxide content of the atmosphere. The three methods are: standard barium hydroxide solution and back titration of excess barium; mass spectrometer after the removal of water vapor; infrared using the peak a t 14 microns. Semikhatova and Ivanova (177) have modified the Worburg and Krippahl method to give a manometric determination of respiratory carbon dioxide. To explain the often observed changes in the measured carbon dioxide content of air caused by additional irradiation with colored light, or longer standing in the dark, or by preliminary heating of the air a t more than 50°C., Balcarczyk and Lanzel (10) made the assumption that these samples contain a light-sensitive and temperaturesensitive aerosol. To remove this aerosol, the air was filtered through asbestos and glass filters. The filtered air was no longer light-sensitive or temperaturesensitive, so that the removal of some substance producing these may be assumed. Spitzer and Kurka (186) give a detailed description of a direct conductimetric determination of carbon dioxide and ammonia in ammonia water. Gafford and Rosenbaum (64) have an apparatus for the photometric determination of carbon dioxide concentration in the atmosphere of a manned space vehicle. The color of a p H sensitive dye (e.g., bromocresol green) suspended in agar is used in the apparatus. Baranenko et al. (13) describe an apparatus for carbon dioxide
in hydrocarbons. Stamm (187) has modified and improved the apparatus for volumetric determination of carbon dioxide. Stetter (190) has made a study of the differences in different methods of analysis. Absorption in barium hydroxide and titration gave unreasonable variations. Infrared analysis fluctuated much less. Results obtained by the barium hydroxide method in the dark were higher than those obtained in the light, and agreed closely with those made by infrared. Infrared analyses indicate that all carbon dioxide was absorbed by the barium hydroxide. Presumably, in air samples exposed to light, part of the carbon dioxide absorbed in the alkaline solution was in a form not detectable by titration, probably as a colloid. Holm-Jensen (89) describes an improved gas absorption device for conductimetric micro determination of carbon dioxide. Vines and Oberbacher ($06) describe an adaption of the C. and K. method which is based on a change in pH brought about as carbon dioxide in an air stream is bubbled through buffered sodium carbonate until equilibrium is attained. This method is used for carbon dioxide determination in fruit and vegetable respiration studies. A mass spectrometer for routine analysis cannot be used directly for the analysis of high-purity carbon dioxide (198). The method for separation of impurities is described. G A S ANALYSIS
Equations were derived for calculating the composition of the gasified and nongasified parts of fuel during the combustion by using the gas analysis data (107). The theory is based on the division of the incomplete combustion products on a chemical and mechanical basis. The equation for calculating the heat losses due to incomplete combustion takes into account the fuel fractionation during the combustion. The effect of the fuel fractionation on the accuracy of the proposed method was evaluated. Experiments with diesel oil combustion in a laboratory combustion chamber showed that the theory is in good agreement with the experiment. The exhaust and blowby emissions of hydrocarbons and carbon monoxide from about 30 cars were measured using a bag sampling technique (189). This was done in conjunction with a 100-car survey performed to provide a base line for the evaluation of control devices. The bag sampling method and the transient integration method were in good agreement for the concentrations of hydrocarbons and carbon monoxide in exhaust gas. A flame ionization hydrocarbon detector gave read-
ings from 1.4 to 2.1 times larger than the nondispersive infrared analyzer when measuring exhaust samples. The total concentration of gas, dispersed and dissolved in a liquid (e.g., a viscous solution), is determined by measuring the change in the conductivity of a control liquid which is flowing through two cells of a transformer in which different pressures are maintained (136). Gas-laden liquid is introduced into an evacuated chamber of known volume, and its gas content is calculated from the observed increase in pressure (86). Clifton (31) describes physical and chemical measures with stress on the detection and estimation of atmospheric sulfur dioxide. For surveys of atmospheric pollution, an apparatus was used in which smoke was trapped on white filter paper while sulfur dioxide was oxidized with hydrogen peroxide to sulfuric acid. The sulfuric acid was estimated by titration with an indicator changing color at pH 4.5 to avoid titrating any acidity due to carbonic acid. Cox and Criddle (37) describe an apparatus utilizing a special absorption vessel in conjunction with an automatic titrimeter, a photoconductivity cell to count drops, a helical potentiometer, and a recorder. Vasak (206) uses a polarographic determination for arsenic hydride (arsine), Continuous analysis of gases and vapors in a double ionization chamber is described by Matousek (134). The apparatus has the measuring electrode common for both chambers which are divided partially or only by the electric field. Procedures for amperometric titration are described by Liplavk (125). With a polarograph or simple electric measuring device, an apparatus can be easily constructed for any type of amperometric titration. The automatic determination of total mercaptan sulfur in natural gas for batchwise or continuous operations is described (192). A known amount of gas is passed through a scrubber containing a water solution of silver nitrate to which has been added a small amount of Silver-110 (110Ag). Because the sulfur in hydrogen sulfide requires twice as much silver as mercaptan sulfur, all the hydrogen sulfide is removed prior to scrubbing. Other sulfides do not interfere if a dilute silver nitrate solution is used in which an aqueous solution of silver nitrate is mixed with 11oAg in dilute nitric acid to give 50 pg. of silver nitrate per milliliter containing 0.05 pc. of 11OAg/ml. The total silver nitrate should be 10-100 pg./ml. with a maximum of 0.05N in nitric acid. Azen and Zashkvar (7) give a method of detection of components in gaseous mixtures. VOL. 38, NO. 5, APRIL 1966
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A method is given for estimating the proportion of a paramagnetic gas in a gas mixture (122). A chamber is filled with the gas unit and an external sinusoidal, alternating magnetic field is applied. The magnetic susceptibility of the paramagnetic gas is a function of the temperature. Therefore, a local change of the temperature in the chamber will cause a change of the magnetic field. From the simultaneous change of the field and the temperature gradient, a measurable pressure change will result. With this pressure change and/ or a comparison with a gas mixture of known composition the content of paramagnetic gases is calculated. Gas streams containing known concentration of trace gases suitable for the calibration of gas analyses are conveniently prepared by electrolytic methods (87). Dvorak (45) describes an apparatus for the detection and analysis of gases and vapors. In the apparatus, the tested compound enters the space between two electrodes in which there is a corona discharge. The magnitude of the current between the electrodes indicates the concentration or the presence of the investigated compound. Russkikh (173) gives rapid methods to indicate the pressure of dangerous concentration of phosgene, chlorocyanogen and bromocyanogen, HCN, arsine, and pyridine. Strips of ashless filter paper were impregnated with the appropriate reagents, placed in a glass tube, and air was pulled through. The intensity of the colors obtained and the length of the columns formed were compared to an artificial standard scale of water colors on graph paper. Yanagisawa et al. (212) determine dust constituents in air. Suspended dust particles whose diameters are larger than 3 microns and the smaller ones are collected with a filter paper dust collector and a small hand-made a x . dust precipitator connected in series, by passing the air through these. The filter paper was ashed, weighed, fused with sodium carbonate, and extracted with HC1. The contents of Al, Mg, and Fe in the extracted solution were determined by emission spectrographic analysis with the soak-up electrode. The dust precipitated on an electrode of the precipitator was rinsed in methanol under ultrasonic oscillation, weighed after evaporating the solvent, and treated by the above procedure. An apparatus and method are described (153) for the automatic analysis of reducing gases. The novel feature is that the absorbed part of the analyzed gas is treated with an excess of the oxidizing agent arising in the absorption solution by electrolysis a t constant current intensity. The concentration of the unreacted amount of the oxidation agent is measured by an ampero172 R
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ANALYTICAL CHEMISTRY
metric method at constant potential. The unreacted part of the oxidation agent enters a layer of active carbon serving as the cathode of an electrolytical generation system. The absorption solution freed of the oxidation agent is then used for repeated absorption of the analyzed gas. A method (117) for the analysis of a gas mixture comprises treating a stream of the gas with a predetermined volume of liquid a t predetermined intervals of time, the liquid selected reacting with one or more components of the gas mixture and changing color, the color change being measured by photoelectric cells. The apparatus includes a device for fine adjustment of the gas pressure, the device being a bellows or another elastic body with a variable volume, in continuous communication with an oiled filled overpressure bottle into which projects an open dip-tube connected to the gas supply line, the liquid being supplied to the gas stream by means of a measuring rotary valve, which is alternately cut off from and connected with the gas supply. An improved Omegatron mass spectrometer (203) was used t o determine the nature and amount of gases which are released during the operation of a television picture tube. A coulometric cell (105) which allows the measurement of gaseous electrolysis products is described. The cell was tested with a standard Fe+* solution. Elskens et al. (53) describe an apparatus based on selective adsorption of gases permitting very rapid determinations in the field. ilnalyses of fumarolic gases from Stromboli are given. Gases and vapors are analyzed continuously (202) by measuring the physical chemical properties of the sample before and after selective condensation of the investigated component, provided its vapor pressure is sufficiently different from that of the rest of the analyzed mixture. The thermal effect caused by high-frequency discharge in a capillary tube filled with gas a t 15-200 mm. Hg is measured with a thermocouple on the surface and allows the determination of admixtures in gases (138). Characteristic mass spectra of gases (8),solvents, and oils used in highvacuum systems were recorded. In several tests, these results were used to determine the source of leaks. Pines (161) gives the precision of methods for determining some toxic substances in air with the aid of a Pulfrich photometer. The standard deviation of a single determination in air on a Pulfrich photometer increased continuously with the absorption. Relative standard deviation decreased with absorption. The relative precision, unlike in spectrophotometers, increased with the absorption. For con-
centrations for which Beer's law is not valid but the precision is high, precise and accurate results can be obtained by introducing corrections. Romand and Berneron (171) states that sensitivity of spectrographs may be increased by using photoelectric receivers without windows. These tubes have photocathodes of gold or nickel and dynodes of copper-beryllium, The ultraviolet photons emitted by the sample fall on the cathode directly. Thus a higher photoelectric yield and a higher ratio signal/background is reached, for these receivers are insensible to visible light. Bothe and Adler (19) discuss the physical principles and development possibilities of an apparatus for the analysis of gases and vapors by nuclear radiation. The apparatus is especially suitable for the determination of traces of electronegative gases such as oxygen, water, and halogens in inert gases. Diebolt (46) reports the results obtained in a study in three parts: (1) The rare gases were separated on activated carbon a t constant pressure by a programmed increase of column temperature and determined by counting of radioactivity (125). Xe not previously used for radioactive detection of Xe provides very good sensitivity. (2) Reduction of palladium chloride by carbon monoxide was measured by determining the activity of the reduced palladium with a sensitivity correspondml. CO. (3) HzO in a ing to 2 X gas is determined by the activation of HC1 formed from the hydrolysis of an acyl chloride, but because of residual water in the apparatus the minimum detectable concentration is 0.01 mg./ liter gas.
APPARATUS
Handa et al. (84) have devised an apparatus for the preparation of standard gas mixtures. rllthough this was devised for gas chromatographic determination of a minute amount of gas sample, it may be used for other places where a standard gas mixture is desired. Erikson (64) has devised an apparatus to separate gases from transformer oils. Rings of filter paper are stacked around a rod and compressed by a spring so that the liquid film between the sheets is Radovskaya, T. L., Izmeritel’n. Tekhn. 1964 ( 5 ) , 50. (131) Marzadro, AI., DeCarolis, A., Rend. Isf. Super Sanita 26 (8-9). 629 (1963). (132) Mason, D. ll.,Hydrocarbon Process Petrol. Refiner 43 ( l o ) , 143 (1964). (133) JIathur, J. S., Chaturvedi, G. K., J . Indzan Xed. Assoc. 41 ( l l ) , 5j6 (1963). (134) Alatousek, S., Czech. Patent 106,916 (March 15, 1963). (135) JlcPherson, P. M., U. S. Patent 3,161,769(Dee. 15, 1964). (136) Rlikhhn, I. A,, Perepelkin, K. E., U.S.S.R. Patent 160,362(Jan. 16, 1964). (137) hlllhovitch, S., French Patent 1,374,529(Oct. 9, 1964). (138) Llirtov, B. A., Starkova, A. G., Zavodsk. Lab. 30, 575 (1964). (139) Mshurov, E. A., Lab. Delo 1964 (lo), 579. (140) Mochizuki, M., Ota, Y., Kamimura, I-., Lhyamota, Y., Japan J . Physzol. 14 (6), 599 (1964). (141) lIogilevskii, G. A,, Dianova, E. V., U.S.S.R. Patent 68,628 (July 22, 1964). (142) Noretti, &I., Rzc. Sci., Rend. Sez. A5, 223 (1964). (143) Xiueller, P., German Patent 1,186,243(Jan. 28, 1965). (144) Jluzyczuk, J., Arch. Gornzetwa 7 (2), 201 (1962). (145) Sash, T., Air Water Pollutzon 8 ( 2 ) , 121 (1964). (146) kebe,‘ W.,Molinski, S., Chemik 17, 243 (1964). (147) Nechuskin, A. >I., Belash, P. M., Belov, V. F., Sarkisov, A. L., Izv. Vysshikh. Zavedenii, Xeft i Gas 7 ( l l ) , 89 11964). (148)‘Selsbn. G., Proc. Fertiliser Soc. No. 79, 66 (1963). (149) Nicols, P. N. R., Chem. Ind. London 1964, 1654. (150) Omichi, S., Bunseki Kagaku 13 (4), 339 119641. (151) bsipova, K. D., Popov, €3. I., Skomorokhova, N.G., U.S.S.R. Patent 165,677 (Oct. 26, 1964). (152) Ovcharenko, A. P., Khim. Prom., Nauk-Tekhn. Zb. 1963 (4), 59. (153) Palmer, T. H., German Patent 1,171,643 (June 4, 1964). (154) Pasich, J., Przadka, T., Farm. Polska 15, 195 (1959). (155) Pavelka, F., Mikrochim. Ichnoanol Acta 1964 (6), 1121. (156) Penchev, N. P., Pencheva, E. N., Izv. Geol. Inst. Bular, Akad. Nauk 12,
257 (1963). (157) Pete, O., Zugravescu, P. Gh., Sandulescu, D., Rev. Chim. 15 (12), 759 (1964). VOL. 38, NO. 5, APRIL 1966
175 R
(158) Petukhov, S. S., Gustov, V. F., Tr. Vses. Nauchn.-Zssled. Znst. Kislorodn. Mashinostr. No. 7, 120 (1963). (159) Pfefferle, w. c., S. Patent 3,138,948 (June 30, 1964). (160) Pichl, E., Erdoel Kohle 17 (6), 474
u.
(1964). (161) Pines, I., Chem. Anal. 9 (2), 179 (1964). (162) Pribyl, Rf., Collection Czech. Chem. Commun. 28,2158 (1963). (163) Pross, A. W., Can. Spectry. 9 (8) 143, (1964). (164) Rabinovich, V. A,, Sherman, E. E., Rol Mikroorganizmov v Obrazov ZhelezoMergantsevykh Ozern. Rud, Akad. Nauk SSSR, Lab Gidrogeol Probl. 1964, 8.
(165) Ray, W. A., German Patent 1,155,270 (Oct. 3, 1963). (166) Richter, H. G., Gillespie, A. S., Jr., NASA Accession No. N64-19, 1923; Rept. No. ORO-591 Avail. OTS. (167) Ripley, D. L., Clingenpeel, J. M., Hurn, R. W., Air Water Pollution 8 (8-9), 455 (1964). (168) Risk, J. B., Murray, F. E., Can. Pulp Paper Znc. 17 (lo), 31 (1964). (169) Roberts, J. L., Jr., Sawyer, D. T., J . Electroanal. Chem. 7 (4), 315 (1964). (170) Rogaczewska, T., Chem. Anal. 9 (3), 417 (1964). (171) Romand, M. J., Berneron, M. R., Puhl. Group. Avan. Methods Spectrog. 1963 (4), 327.
(172) Roskam, R. Th., delangen, D., Anal. Chim. Acta 30, 56 (1964). (173) Russkikh, A. A., Novoe V Oblasti Sunit.-Khim. Analiza 1962, 162. (174) Ryhage, R., ANAL.CHEM.36, 759 (1964). (175) Saltzman, B. E., Mendenhall, A. L., Jr., ANAL.CHEM.36, 1300 (1964). (176) Seaver, R. E., NASA Doc. N62-14, 862 (1962). (177) Semikhatova, 0. A., Ivanova, T. I., Fiziol, Rust. 12, 175 (1965). (178) Semyachkova, A. F., Korskova, M. R., U.S.S.R. Patent 158,448 (Oct. 19, 1963).
(179) Senkevich, 0. V., Klassovskaya, N. A., U.S.S.R. Patent 161.966 . (Am. . _ 1, 1964): (180) Seo. E. T.. Sawver. D. T.. J.’Electroanal. Chem. 7 (3“).i84 ~-~ 11964).’ (181) Serak, L., Hybasek, P., Czech. Patent 105,758 (Nov. 15, 1962). (182) Shul’gina, E. M., Arutyunova, A. Kh., Blyumshtein, A. E., NeftepereraI
~
\
,>
\ - -
botka i Neftekhim. Nauchn.-Tekh. Sb. 1964 (3), 26. (183) Sojecki, W., Prace Central. Znst. Ochrony Pracy 14 (43), 199 (1964). (184) I5id., p. 209. (185) Solitario, W. A., Bialecki, A., Laubach, G., Chem. Eng. Progr. Symp. Ser. 60 (52), 188 (1964). (186) Spitzer, Z., Kurka, Z., Paliva 43
(12), 364 (1963). (187) Stamm, W., German Patent 1,168,122 (April 6, 1964). (188) Stephens, B. G., Lindstrom, F., ANAL.CHEM.36, 1308 (1964). (189) Stephens, E. R., Pattison, J. N., ACS, Division of Water Waste Chemistry Preprints 1963 (March, April) 321. (190) Stetter, G., Oesterr, Akad. Wiss., Math-Naturw.Ki., Sitzber 172,79 (1963). (191) Stier, A., Intern. Arch. Gewerbepathol. Gewerbehyg. 20, 337 (1963). (192) Stout, J. W., Jr., Early, E., Proc. Operating Sect., Am. Gas Assoc. 1962,
CEP-62-2. (193) Strafelda, F., Dolezal, J., Czech. Patent 104,676 (Aug. 15, 1962). (194) Sullivan, J. O., Warneck, P., Microchem. J . 8 (3), 241 (1964). (195) Suvorova, S. N., Vorob’ev, A. hf., Rabovskii, G. V., Gigiena i sunit. 28 (lo), 48 (1963). (196) Tapfer, D., Egeszsegtudomany 7 (4), 322 (1963). (197) Toedt, F., German Patent 1,177,377 (Sept. 3, 1964). (198) Tsuchiya, M., Tachikawa, T., Shitsuryo Bunseki l l (23), 117 (1963). (199) Utsumi, S., Ito, S., Machida, W., Okutani, T., Bunseki Kagaka 14, 12 (1965).
(200) Vaistariene, K., Dolgopol’skii, I. M., Kriauciunas, J., Lietuvois T S R Mokslu Akad. Darhai, Ser. B 1946,
No. 4, 79. (201) Vana, J., Vojir, V., Lichtenberg, F., Sekerka, B., Czech. Patent 104,374 (July 15, 1962). (202) Vana, J., Srein, K., Czech. Patent 106,163 (Jan. 15, 1963). (203) Van der Waal, J., Nuovo Cimento, +%.p~l. 1 (2), 760. (204) Van Meerten, R. J., Netherlands Patent 110,554 (Jan. 15, 1965). (205) Vasak, S’., Collection Czech. Chem. Commun. 24, 3500 (1959). (206) Vines, H. M.,Oberbacher, M. F., Proc. Florida State Hort. SOC.76, 312 (1963). (207) Vinogradova, V.A., Novoe v Oblasti Sunit.-Khim. Analiza 1962, 158. (208) Vlckova, Z., Prace Ustavu Vyskum Paliv 7, 257 (1964). (209) Voelker, R. E., White, C. N., ZSA Proc. Ann. Inst. Autom. Conf. Exhibat 18, Pt. 2 (1963).
(210) S’ojir, V., Lichtenberg, F., Sekerka, B., S’ana, J., Czech. Patent 109,125 (Nov. 15, 1963). (211) Wigotsky, V. W., Design News 19, 38 (1963). (212) Yanagisawa, S., Hashimoto, Y., hfitsuzawa, S., Bunseki Kagaka 12, 1040 (1963). (213j -Yanagisawa, S., Mitsuzawa, S., Hirose, A., Arai, M., Zbid., p. 1037. (214) Zakhar’evskii, hf. S., Petrovskaya, I. A,. Vestn. Leninar. Univ. 19 (221, . . 1964.’ (215) Zavarov, G. IT., Zavodsk Lab. 30, 25 (1964). (216) Ibid., p. 409. (217) Zawadzki, S., Grabowski, Z., Prace Central. Znst. Ochrony Pracy 14 (43), 185 (1964). (218) Zimina, K. I., Polyakova, A. A., Khmel’nitskii. R. A.. Razdelenie i Analiz Ugiedodorodnykh Gazov, Akad. Nauk SSSR, Znst. Neftekhim. Sinteza, Sb. Staki 1963, 214.
Ion Exchange Robert Kunin, Rohm and Haas Co., Philadelphia, Pa.
T
review on the analytical chemistry of ion exchange follows the format introduced in 1962 excluding those topics that are specifically related to ion exchange chromatography which will be incorporated in another review. Since most all applications of ion exchange are in a sense chromatographic processes, the author has arbitrarily omitted from this review those analytical chromatographic separations involving the columnar separation of closely related species requiring a multitude of theoretical plates. This review covers the period from November 1963 to November 1965. HIS
REVIEWS
Several ion exchange reviews of a general nature which were published recently are of considerable interest to t h e analytical chemist. Reichenberg 176 R
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(7A) and Tremillon (8A) have reviewed some of the more important theories and principles of ion exchange. Dorfner (6A) has written, in German, a book on the properties and applications of ion exchangers. A Russian book describing the properties of ion exchange materials has been written by Chmutov ( 5 A ) ,a Soviet authority in the field. Of particular interest is the monograph by Amphlett ( 1 A ) on inorganic exchangers, an area of renewed interest. It is indeed unfortunate, however, that most of the recent workers in this area have ignored the extensive work of Sante Mattson and his students who published extensively in the United States and Sweden from 1926 to 1946. Of interest is the book by Cassidy and Kun ( S A ) on redox polymers. This monograph contains a comprehensive treatment of the nature, preparation, and applications of crosslinked redox
polymers which may be of considerable interest to the analytical chemist. Of direct interest to the analytical chemist are the recent reviews by Chernobrov ( 4 A ) and Walton (9A). Brinkman and DeVries (29) have reviewed the use of liquid ion exchangers in analytical chemistry. THEORY
Numerous studies are in progress in which attempts are being made to quantitatively account for the selectivity of ion exchange substances, particularly with respect to changes in the physical and chemical structures of the exchanger. Extensive thermodynamic studies were conducted by Boyd et al. (4B) and by Soldatov and Starobinets (29B-SZB) on the sulfonated styrenedivinylbenzene cation exchangers of varying degrees of crosslinkage. Other selectivity investigations on similar
