I REVIEW OF INDUSTRIAL APPLICATIONS
1
I I Ferrous Metallurgy I I
I I
H. F. BEEGHLY Jones & Laughlin Steel Corp., Pittsburgh 30, Pa.
for analysis of ferrous materials published in the period November 1, 1954, to October 30 1956, include few basic new procedures. They continue to reflect the need for more sensitive and precise analytical techniques as the performance requirements for metals become increasingly exacting. Work is being done to perfect simple, accurate methods for use in production control of the gas contents of metals. Progress has barely kept pace, however, with development and use of new, complex alloys which impose even more severe demands on analytical methods. Emission and x-ray spectrographic techniques and equipment for their use have contributed to the solution of some difficult problems associated with analysis of the more complex alloys. Vacuum emission and helium path x-ray equipment are extending the applicability of these methods. The former is now becoming a feasible means of analyzing for gases and other nonmetallics in ferrous metals by excitation either in vacuum or in an inert atmosphere. The latter is no longer limited to elements above atomic number 22, nor to relatively high limits of detection. Improved methods for isolating minor constituents have lowered the limits of detection very appreciably. As suitable mass spectrometric equipment becomes available, this method will be valuable for analyzing surface films and metals for their constituents. The flame photometer’s applicability has been extended by use of solvent extraction for isolation of metallic constituents and excitation in organic solvents. The reproducibility of results attained with a given method in different laboratories or in the hands of different operators and the nearness with which these values approach the actual amount of a constituent in a sample are important for evaluating a n analytical method (96, 101, 102, 120). Sources of error in colorimetry have been evaluated (135). Apparatus and manipulations for the application of micromethods to the ETHODS
638
ANALYTICAL CHEMISTRY
analysis of metals were described (91, 96). Ion exchange can be used as a basis for separating desired constituents from matrix elements which may interfere with estimation of the constituents by convenient techniques. Such elements as titanium, vanadium, molybdenum, rare earths, and gallium have been separated in this manner (1, 30,69, 110, 1%’ 1 4 0 . Solvent extraction for separation of metals has been used to an increased extent (41, 74, 105, 156, 157, 169, 172). A universal spectrographic method which uses a germanium dioxide filler and copper oxide and graphite as buffer to provide a common base for all materials has been described (80). Other descriptions include a procedure for preparing powder standards (68), a low voltage intermittent arc method for low concentrations of elements ($79, an alternating current spark point to plane technique for carbon, low alloy and stainless steels (76), a method for use of rotating disk specimens (44) and use of solutions to overcome segregation effects (51), and a comparison of plate response calibration methods (146). A curved crystal spectrometer was described with which concentration of from 5 to 20 y of such elements as columbium, cadmium, tantalum, thorium, and uranium can be determined in steel (17). These elements are first extracted from a 10-gram or larger sample. Other concentration techniques have been devised for concentrating minor constituents prior t o their quantitative determination (68, 199). An x-ray spectrograph designed for recording spectra of two specimens simultaneously on a photographic film has been described (18). A standard diffraction unit is used. Resolution good enough to separate the 2.10 A. manganese K , from the 2.08 A. chromium Kp line was attained. Tungsten, manganese, nickel, chromium, cobalt, iron, molybdenum, and vanadium in steel alloys were determined with the x-ray spectrometer (136). This method was applied t o
ore (147) and mineral analyses (3). Useful x-ray diffraction powder data for the analytical chemist were compiled and published (160). ACTIVATION AND TRACER METHODS
Activation and tracer techniques are finding increased use. To some extent their appIication in metals analysis has been limited by lack of ready access to suitable neutron sources. Many industrial laboratories lack the facilities for handling even the relatively low level activities necessary for use of these techniques. Both of these limitations are disappearing. A comparison of the sensitivity of activation analysis with that of other methods has been made (3,108). I n production of high purity iron, activation has been valuable in identifying impurities and determining their amounts (86). Activation was used in the determination of cobalt in steel (96). The cobalt was extracted as the thiocyanate with an isoamyl alcohol-ether solution after activation; then the activity of the cobalt was measured. I n the determination of columbium, a radioactive tracer of columbium-95 was added to provide a convenient method for checking on the recovery of columbium (111). I n a similar use, the oxygen-18 isotope was used for determining oxygen in metals (90). ALUMINUM
Aluminum was determined gravimetrically (47) or titrimetrically (48) following removal of most of the iron by extraction with dichlorodiethyl ether; the sodium salt of (ethylenedinitri1o)tetraacetic acid was added to complex the remaining iron. The ether had to be purified prior to use by steam distillation to obtain an effective extraction. A cellulose column was used to absorb the aluminum from a n ethyl methyl ketone-hydrochloric acid soIution (19). Iron passed through the column. The aluminum was then eluted from the column with 2N hydrochloric acid and determined polarographically.
Procedures for determining alumina, alunlinum nitride, and aluminum in steels were evaluated (77, 117). For the former, the aluminum insoluble in sulfuric acid containing hydrogen peroxide was used. Aluminum nitride was isolated with the ester-halogen method (12). Stilbazo [the diammonium salt of 4,4 ’- bis ( 3 ,4 - di h y d r o x y p h e n y 1a z o ) 2,2’-stilbenedisulfoiiic acid] was investigated for the photometric deterinination of aluminum in steel following removal of iron with the mercury cathode. Vanadium and titanium were rcbmoved as the cupferron complexes Iry extraction into chloroform (81). The Eriochronie Cyanine-aluminum cdor complex was found preferable to the aluniinon complex for steel (171) and was useful also for determining aluminum in pig iron (143). Aluminum was extracted into benzene as the oxinate from an ironcyanide complex and determined photometrically (86). Benzene was found to be a better extractant than chloroform.
micromethod for samples as small as 5 mg. has been devised (144). A capillary trap (76) method shows promise for determining very small quantities of carbon. There is growing evidence that the spectrographic determination of carbon will become feasible (26, 23, 167, 180). The Eggertz color method almost disappeared with development of niodern combustion apparatus. Konever, it was applied, with modern photometry: for studying effects of different heat treatments on the form of carbon in steel (119, 164). A procedure for preparation of manganese dioxide for use in removal of oxides of sulfur from products of combustion of steel in the carbon determination was described (104).
The search for methods for separating columbium from tantalum and for measuring the amounts of each has been active. Extraction of the thiocyanate complex of columbium (31, 37, 111, 116) and of the S-hydrouyquinolate with chloroform (67) have been investigated. Khen highest accuracy was desired a radioactive tracer, columbium-95, was added. Columbium in the range of 0.1 to 2 570 columbium pentouick vias determined by x-ray spectroscopy using molybdenum as an internal standard (169).
CERIUM
COPPER
As a basis for determining cerium and other rare earth elements in steel, the steel vas dissolved in aqua regia. The rare earths were converted to sulfates, chlorates, or chlorides and then separated by ion exchange (94).
Diethyl thiocarbamate and diquinolyl were evaluated for determination of copper in steel ( 2 5 ) . The latter was preferred. The absorption a t 940 mp of copper in a 6AVhydrochloric acid solution was made the basis for its determination in steel (38). Ferrous and stannous ions interfered; by use of ammonium persulfate to oxidize these ions, interference m s avoided. Copper in steel was determined by solution in an oxidizing acid, reduction mith sulfur dioxide, and adjustment of the pH to a range of 5 t o 6. The copper n a s then extracted with a solution of 2,2’-biquinoline in amyl alcohol containing citric acid (49). The copper content of the extract was estimated by means of its color intensity. Ethylenediamine was found to be a good reagent for preventing copper precipitation and adsorption of copper on iron (263). Glycocoll n-as also effective but less satisfactory. By formation of the copper-dithioovamide complex and potentiometric titration with a silver indicator electrode, copper in the 1 to 40 p.p.m. concentration range was determined (109). It also was determined polarographically (63). Lead and tin were determined in a similar manner.
ARSENIC
Arsenic and phosphorus give the same color in the molybdenum blue method. By extraction with amyl alcohol, in 0.1- to 0.4N sulfuric acid, the phosphorus-molybdenum complex n-as removed, leaving the arsenic complex for photometric measurements (63). Arsenic in pig iron was determined by reduction to metallic arsenic and titration with iodine (84).
CHROMIUM
Chromium, after oxidation to perchromic acid with hydrogen peroxide, was extracted into ethyl acetate. The chromium content of the extract was measured on the basis of its absorption a t 385 mp (61). Iron, manganese, molybdenum, tungsten, and vanadium did not interfere. COBALT
BORON
S e w reagents for reaction with boron to form color complexes include tetrabroniochrysazin ( 179) and carminic acid (21). Quinalizarin continues to be used (97). The flame spectrum of boron has been made the basis for its determination (39). Spectrographic reference steels for the boron concentration range from 0.0001 to 0.0006% were prepared by vacuum melting high purity iron with addition of the proper quantities of Sational Bureau of Standards’ KO. 530 spectrographic standard (149). A method for determination of boron in this concentration range with an echelle spectrograph m s also described (139), CARBON
The determination of carbon in most ferrous metals is a simple, well established procedure. For very low carbon contents, the determination is exacting and better methods are being sought; evaluation of such methods has received the attention of a number of workers (10, 26, 163, 173). A semi-
The thiocyanate-cobalt complex has been the basis for separating cobalt from interfering elements. Chloroform in the presence of tetraphenylarsonium chloride and a 1 to 5 isoamyl alcohol-ether solution saturated 17-ith ammonium thiocyanate were used as extractants for cobalt (103). The cobalt content was then measured photometrically (78,103,128) or by means of the radioactivity of the cobalt-60 formed by irradiation of the specimen prior to formation of the thiocyanate complex (36). The cobalt-1-nitroso-2-naphthol complex n-as used for cobalt determination in steel (RS), and in ore (103). I n the latter, the presence of more than 307, iron interferes and must be removed; otherwise, for cobalt contents up to 37, on a 200-mg. sample, separations are not necessary. By collecting cobalt, manganese, nickel, and chromium on Dowex-1 anion exchange resin as chlorides and removing cobalt by elution with 4N hydrochloric acid, this element was isolated from high temperature steel alloys (70). The cobalt in the eluate
was deposited electrolytically from an ammoniacal solution and weighed. COLUMBIUM
GASES AND NONMETALLIC COMPOUNDS
Proper methods of sampling and sample preparation for gas analyses are very important. A bomb sampling method for collecting molten steel for the determination of oxygen (60) and a metal block mold sampling method for collecting molten steel for hydrogen analyses have been described (16). I n the latter case, storage for 24 hours in solid carbon dioxide was found permissible. Work has continued on determination of gases by microvacuum fusion (67). VOL. 29, NO. 4, APRIL 1957
639
Gas contents a t the level of 10 to 100 p.p.m. can be determined in approximately 3 hours. A method which utilizes a molten platinum bath in a graphite crucible shows promise for use with very small amounts of oxygen or with small specimens (154). The oxygen was liberated and converted to carbon dioxide in an argon atmosphere and condensed out in a capillary tube. A cylindrical carbon furnace was compared with an induction heater. It was found to permit operation a t higher temperatures and to permit complete recovery of oxygen by the vacuum fusion method from steels containing aluminum (145). High temperatures were necessary for determining oxygen in cast iron (151). The oxygen-18 isotope mas incorporated into a master alloy and added along with specimens of unknown oxygen content to avoid the necessity for quantitative recovery of oxygen from the specimen in the vacuum system (90). A method of continuous detection and determination of oxygen in gas streams with a sensitivity of the order of 0.0005 volume %, and a precision of =tO.OOOl volume % in common gases such as nitrogen, helium, and the rare gases was devised (127). A method based on reaction of bromine and carbon a t 825" C. with the specimen to liberate the oxygen as carbon dioxide was developed. The monoxide was converted to carbon dioxide, purified, absorbed, and weighed (35). The apparatus mas sensitive to quantities of oxygen of the order of 0.3 y. The method was designed initially for use on titanium but has shown promise for determining oxygen in steels, particularly where oxygen is present in comparatively large amounts. Oxygen has been determined spectrographically in steel by excitation in a hydrogen atmosphere Ivith an intermittent spark (52). Methods for analyzing ferrous metals for gases were reviewed (107, 125). A simple emcuable closed tube in which the specimen a t 400" C. is held a t an initial pressure of 0.01 mm. of mercury was used for the determination of hydrogen (11). Increase in pressure ITas related to the hydrogen liberated from the specimen. Results agreed with those obtained by vacuum fusion within =k 5%. The evolution of hydrogen between 20" and 1150" C. was found to be virtually complete from white cast iron in 2 hours a t the upper limit of the a phase (650" to 750" C.) and a t temperatures of 1000" C. and more (6). Between 750" and 1000" C. or below 650" C., part of the hydrogen remained in the specimen. For gray cast iron, evolution was not complete a t temperatures 640
ANALYTICAL CHEMISTRY
up to 1000" C. At each temperature, there was a period of rapid evolution followed by a much slower one. The soluble and insoluble nitrogen in hydrochloric acid was measured in cast iron. The proportion of hydrochloric acid-insoluble nitrogen was found to increase when aluminum or titanium was added to the iron (165). No effect was observed when boron was added. When iron was removed by precipitation n-ith sodium hydroxide and centrifuging, the nitrogen content measured by direct nesslerizing was lower than values obtained by vacuum fusion (88). Centrifuging acid solutions to separate insoluble nitrogen compounds gave low values for steel when the aluminum content was above 0.2 to 0.3% (162). By steam distillation, results without centrifuging were independent of the aluminum content. This was because aluminum nitride was decomposed by alkali but not by acid. Nitrogen in austenitic steels was determined by burning the specimen in a direct current arc a t 220 volts and 16 A. in a carbon dioxide atmosphere (140). The CN-3883.56 A. band and the Fe-3865.53 A. line mere used. Results rvere reproducible to f 10%. Vacuum distillation with a slow stream of air bubbling through the alkaline solution gave a very rapid distillation (57). The polarographic determination of nitrogen utilizing the reduction product of ammonia and phthalaldehyde was found to be feasible (123). Ronmetallic compounds are of importance when they occur as corrosion products, as scales resulting from gasmetal reactions a t elevated temperatures, and as the product of reactions within the metal occurring as a result of deoxidation, heat treatment, or reaction in service. Methods for identifying products of such reactions and for determining the amount of a given compound formed are inadequate. Efforts to isolate such constituents selectively and quantitatively have been successful in some instances. Electrolytic (99, 112) and selective chemical methods of isolation were tried (46, 73, 113, 131, 132, 150, 176). A critical review of such methods was published (14).
X-ray spectroscopy (237) and electron diffraction (115) methods have been helpful in identifying surface films. LEAD
By reaction of lead with sodium sulfide, lead in steel was determined turbidimetrically (32). Polarographic methods and x-ray spectroscopy have been applied (53).
MAGNESIUM
Magnesium is a common constituent of cast iron. Methods for its determination include spectrographic (86, 165), those based on color reactions (66) and on titration Kith chelating agents (66, 154). There is evidence that small pieces rather than drillings should be used to obtain a representative sample of magnesium containing cast iron (34). MANGANESE
The 400.3-mp line was used for the determination of manganese m-ith the flame photometer ($3). An aliquot containing less than 100 p.p.m. of manganese mas used. Manganese in spiegeleisen (54) and in steel (89) was determined by titration with (ethylenedinitri1o)tetraacetic acid.
L
MOLYBDENUM
Ion exchange resins have been useful in separating molybdenum from iron prior to its determination (4, 126). A sulfuric acid solution to which hydrogen peroxide was added gave a solution from which titanium, nickel, copper, and manganese were held on the resin while vanadium, tungsten, and molybdenum passed through. The titanium ion was used to catalyze formation of the molybdenum thiocyanate formed by reduction with stannous chloride in a sulfuric acid solution (29, 148). The intensity of the color of the complex was measured in the aqueous solution (178). This complex was developed in the presence of butyl Cellosolve and intensity of the color measured without extraction. A cellulose column was used for separation of molybdenum from iron and other interfering elements (59). I n this case a sulfuric acid-phosphoric acid solution was passed through the column. Molybdenum was then eluted from the cellulose with acetylacetone; cobalt, copper, chromium, iron, manganese, nickel, and vanadium remained behind. The amount of molybdenum was estimated by means of the thiocyanate color complex. NICKEL
Conditions for precipitation of nickel with dimethylglyoxime without interference from copper or cobalt were studied (8). Nickel dimethylglyoxime extraction from interfering elements with chloroform was made the basis for determination of nickel (33, 121, 129). PHOSPHORUS
The effects of temperature variation
and other variables on reproducibility with the vanadomolybdiphosphate method were studied (7, 50, l S S , 142). It was found that sulfuric acid solutions are not sensitive to temperature variation, as was the case when other acids were used. The spectrographic determination of phosphorus was described (30). A reproducibility within & 3% of the phosphorus content present was obtained (95). SILICON
The molybdenum blue reaction of silicon was utilized for its determination. Ferrous ammonium sulfate in the presence of oxalic acid (5) and stannous oxalate (55, 79, 114, 177) were used as reducing agents. Chromium, cobalt, iron, and nickel were removed prior to development of the molybdenum blue color in another procedure (118). Titrimetric methods based on formation of the potassium silicofluoride complex were found satisfactory (42, 168). SLAGS AND REFRACTORIES
The rotating electrode method for spectrographic analysis of slag has been used with cuprous oxide or cobalt nitrate as internal standards (15). For determination of calcium (168) and iron (40) in slags, flame photometry has been used. Titration with (ethylenedinitri1o)tetraacetic acid has been adapted t o determination of magnesium (66) and calcium (170). The latter was designed for use in titrating the calcium oxide extracted from slag with n 2% sugar solution. Methods for decomposing slags prior to analysis were revien-ed (72). SULFUR
In the gravimetric method, coprecipitation with basic chromium compounds was avoided by use of hydroxylamine in place of baking to remove residual nitrate (9). The method was recommended for all highly alloyed steels except those high in titanium, I n another procedure intended for plain carbon steels, iron was removed by extraction with isoamyl nlcohol, the sulfur precipitated with barium chloride, the barium sulfate dissolved with ammonium hydroxide in an ewess of EDTA added and the excess backtitrated with magnesium chloride ( I S ) . A cation exchange resin was used to separate sulfur from interfering elements (17 4 ) . -4study was reported of the precipitation of sulfur from homogeneous solution mith thioacetamide (161). TELLURIUM
Following precipitation with sodium
diethyldithiocarbamate, tellurium was separated from iron by extraction with benzene or chloroform a t p H 3.3. The tellurium mas estimated on the basis of the intensity of its color (64). TIN
Experiments were conducted to find a suitable quantitative method for use of the tin-cacotheline color complex. (62).
An evaluation of different methods for estimating the amount of iron-tin alloy on steel (166) and of coatings, including tin, on metals by x-ray methods were described (181). TITANIUM
By coprecipitation, titanium m.s separated from interfering elements and its reaction with peroxide to form the yellow pertitanyl complex used for its estimation. I n one method, (ethylenedinitri1o)tetraacetic acid and magnesium sulfate were added and the solution was made ammoniacal (152). The (ethylenedinitri1o)tetraacetic acid held interfering elements in solution while the magnesium hydroxide acted as a carrier for the titanium. I n another, zirconium was precipitated as the arsenate and carried the titanium down with it (130). A double precipitation was necessary. Elements such as chromium, molybdenum, and vanadium were left in solution.
ZIRCONIUM
Hahn dissolved zirconyl oxide in ammonium hydroxide and measured the absorption a t 250 mp as a basis for estimation of zirconium with mandelic acid (71). The nitrate ion interferes. Aluminum up to 100 mg., iron up to 10 mg., or magnesium up to 20 mg. did not interfere. The reaction between the zirconyl ion and phthalic acid Fyhich gives a very finely divided precipitate was made the basis for a simple photometric determination of zirconium (98). The suspension is said to be very stable and t o follow Beer’s law up to 125 p.p.m. of zirconium. The reaction of zirconium with sodium alizarin sulfonate in the presence of perchloric acid and acetone was used for estimation of zirconium (106‘). Aluminum interferes, Tributyl phosphate was used for extraction of zirconium from interfering elements and this extract utilized for estimation of zirconium (100). LITERATURE CITED
TUNGSTEN
Tungsten in the range from 4 to 18% in steel was determined by x-ray spectroscopy (45). The intensity of the thiocyanate complex of tungsten formed in a phosphoric-sulfuric acid solution of steel in vhich the iron n-as reduced n-ith stannous chloride was related to the amount of tungsten present (24,68). Titanium trichloride was added to form a yellow color. VANADIUM
An Amberlite IR-120 resin column m s used for absorbing iron while allowing vanadium to pass through the column (93). Hydrogen peroxide was added to form the pervanadyl color complex, the intensity of which was measured a t 440 mp as a basis for estimation of vanadium content. In another colorimetric method the colored product of the reaction of vanadium with benzohydroxamic acid was used as the basis for its determination (175). The color n-as measured in a 1-hexane solution. Iron must be absent. T’anadium was titrated with ferrous sulfate amperometrically using an H-type polarographic cell and a rotating platinum electrode (138).
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641
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I
I REVIEW OF INDUSTRIAL APPLICATIONS
I
I 1 Fertilizers I I
1
J. A. BRABSON Division o f Chemical Development, Tennessee Valley Authority, Wilson Dam, Ala.
T
literature pertaining to the analysis of fertilizers over the biennium ending Aug. 15, 1956, is reviewed here. This review extends a series of such reviews, the last having appeared in April 1955 (IS). Many creditable publications are not mentioned here; the coverage is limited mostly to articles that, in the author’s opinion, are outstanding in their contribution t o the solution of problems encountered in the analysis of fertilizers. HE
OFFICIAL METHODS
The fertilizer section of the 8th (1955) edition of the Association of Official Agricultural Chemists (AOAC) “Official Vethods of Analysis” ( 2 ) is revised considerably. The most drastic changes are made in the methods for nitrogen. An improved Kjeldahl method for nitrate-free samples replaces three methods for organic and ammoniacal nitrogen. TWOKjeldahl methods for sam-
ples containing nitrates are combined into a single procedure. New methods adopted as official include methods for water-soluble and acid-soluble boron, a wet digestion method for potash, and methods for water-soluble magnesium. Older methods for acid-soluble calcium, free sulfur, and acid-forming or base-forming quality are granted official status. New methods adopted as “first action” are for carbonate carbon, acidinsoluble ash, and nitrogen activity index of urea-formaldehyde compounds. The distillation method for boron is discontinued. SAMPLING AND SAMPLE PREPARATION
The problem of sampling solid fertilizers and of preparing the samples for analysis received attention in a collaborative study (69) and in statistical treatment of data from a n earlier study (61). The results of the two recent studies
support the riffling technique as a means for the reduction of composite samples to samples of laboratory size. The advantages of riffling were borne out also in a British study of the effect of sampling on fertilizer analysis (76). AMMONIACAL
SOLUTIONS FERTILIZERS
AND
LIQUID
The introduction of liquid fertilizers has created sampling problems, especially with products containing uncombined ammonia. Fudge (35) discussed the problems of sampling these solutions and recommended for consideration a procedure that involves introduction of the sample under dilute sulfuric acid in a pressure flask. The sample is then transferred t o a volumetric flask, and aliquots are analyzed by official methods. WATER
The determination of water is compliVOL. 29, NO. 4, APRIL 1957
643
