INDUSTRIAL A N D ENGINEERING CHEMISTRY
412
Table Mercaptan CaHi7SH CioHziSH CizHzsSH CirHzaSH CiaHaaSH
I. Molecular Weight of Primaiy Mercaptans Mercaptan Sulfur Calcd. Found
%
%
21.91 18.39 15.84 13.91 12.40
21.00 18.15 15.74 13.80 12.35
Molecular Weight Calcd. Found 146.3 174.3 202.4 230.4 258.5
146.5 175.2 202.3 232.8 260.6
RSH % 98.0 99.2 99.3 100.2 100.4
inercaptides were precipitated as solids which could be filtered and washed (with 707, alcohol) without centrifuging. Unfortunately, even the loa-temperature technique did not permit filtration without centrifuging when applied to primary mercaptans. The accuracy of the modified method for tertiary mercaptans was not established, although the precision was comparable to that of the primary mercaptan method.
VoI. 18, No. 8
tans were prepared from carefully fractionated alkyl bromides which were obtained from alcohols derived from fats. The samples were believed to be of the correct molecular weight, but it wm suspected that they contained small amounts of nonmercaptan impurities. The results are given in Table I. Each result is the average of a t least three determinations. From the results in Table I it is concluded that the method yielde the correct molecular weight to an accuracy of 1 to 2 units of rnolecular weight (0.5 to 1%). Duplicate determinations in general were reproducible to * 1 unit of molecular weight, LITERATURE CITED
(1) . . Kolthoff. I. M.. and Harris. W. E.. IND.ENQ.CHEM..ANAL.ED.. 18, i 6 i (1946). (2) Tamele, M. W., and Ryland, L. B., Ibid., 8, 16 (1936).
A C C U R A C Y AND PRECISION
A series of straight-chain primary mercaptans containing eight to sixteen carbon atoms per molecule was analyzed. The m m a p -
THISinvestigation was carried out under the sponsorship of the Offioe od Rubber Reserve, Reconstruction Finance Corporation, in connection with the G~~~~~~~~~ synthetic Rubber program.
Determination of A c i d in the Presence of Aluminum R. P. GRAHAM’, Columbia Of the methods proposed for estimation of free acid in aluminum salts, probably the most satisfactory are those in which the acid is titrated with standard alkali after conversion of the aluminum into a stable complex ion. From the Craig procedure, which involves the fluoride complex, an accurate method has been developed for the determination of acid in solutions in which the concentration of acid is high with respect to that of aluminum. A volumetric method for the analysis of hydrous alumina, embodying the improved procedure, i s described.
L
ITERATURE and data relative to the determination of acid in the presence of aluminum salts have been in existence for nearly a hundred years. [References to much of the early literature on the subject are given by Beilstein and Grosset ( I ) , Ivanov (io),and Kolthoff and Furman (id).] Because of the industrial importance of aluminum sulfate, most of the work has been devoted to the study of methods of determining free acid in samples of this salt. The direct titration of the free acid in aluminum sulfate by means of standard base has been widely advocated. Indicators that have been recommended as suitable for use in such a titration in the presence of the salt include Congo red ( d f ) , methyl orange (alone, d, and with Martius yellow, 19), thymol blue (8), sodium alizarin sulfonate ( l 7 ) ,and the coloring matter of peonies (17). Procedures employing differential back-titrations for the determination of both aluminum and free acid in aluminum sulfate have also been suggested (2, 6). In some of the methods the use of titration reference standards containing pure aluminum sulfate a t the appropriate concentration is recommended; such a procedure should be regarded as essential because the pH of a solution of a pure aluminum salt is dependent on the concentration (and on the temperature and on the nature of the anion). The outstanding disadvantage of methods involving a titration in the presence of the aluminum salt is that, because of hydrolysis of the aluminum ion, the indicator does not undergo a sharp color change. Other procedures, in which the aluminum is precipitated before the titration of the free acid, have been proposed. In particular, methods based on the insolubility of ammonium alum in ethyl alcohol (1, Ii) and on the precipitation of aluminum by potasI
Present address, McMaater University, Hamilton, Ontario, Canada.
University, N e w York,
N. Y.
sium ferrocyanide (10,M)have been recommended. I n some of these procedures the acid is titrated in the presence of the precipitated aluminum; in others the precipitate is first removed by filtration. The precipitation methods are troublesome and rather inaccurate. Certain other methods that have been studied (18,14,16, Bd) are, like the foregoing ones, subject to criticism on one ground or armther. e The most satisfactory methods for this determination, and the ones that have wide applicability to aluminum salts in general, achieve removal of the interference of aluminum by combining it in the form of a complex ion. The free acid may then be determined by titration with standard alkali; the iodometric method has also been proposed (8). Complexes that have been suggested as sufficiently stable to prevent significant hydrolysis of the aluminum ion are those formed with oxalate (8, 9) and fluoride ions [a method has been investigated (24) that depends on the prevention, by the use of the citrate complex, of one third of the hydrolysis normally arising from aluminum on titration with hydroxide]. The technique involving the formation of a fluoride complex is recommended by, among others, Scott (18), Rosin (16), and Thorpe (22). The fluoride method for the determination of free acid was probably first proposed by Craig (6). The aluminum salt is dissolved ,in water, potassium (6, l e ) , or sodium fluoride (16, $2) solution (previously adjusted to be neutral to phenolphthalein), is added in sufficient excess to convert the aluminum into the hexafluoaluminate complex, and the free acid is then titrated by means of standard alkali to a phenolphthalein end point. Bromothymol blue has also been used ( 7 ) as an indicator in connection with the fluoride method. A method for the simultaneous determination of free acid and aluminum ion, making use of the flnoride complex,,has been proposed recently (20). M O D I F I C A T I O N O F FLUORIDE M E T H O D
In the course of a study of the reactivity of hydrous alumina toward acids, it was necessary to determine the decrease in the normality of a number of acid solutions,that had been in contact with hydrous alumina for various periods of time. The aluminum concentration of the solutions to be analyzed varied from 0 to a maximum value of approximately 0.03 M , nhereas the acid
ANALYTICAL EDITION
August, 1946
Table
I.
Accuracy of Conventional‘ Fluoride M e t h o d
Canon. of Al+++ Canon. of F - , Recover) Moles/L:ter Moles/Liter Molar ratio, Titer of HC1 of Acid x 104 X 102 F-/Al+-+ (-tO.OOOl A’) (*O.l%) 98.0 42 12.5 30 0.0939 97.7 83 25 30 . 0.0936 96.1 100 30 30 0.0921 0 “Conventional” means a method in which the fluoride is added before the start of the titration. Details of such a method&.&, concentration of base employed for the titration-vary from one worker to another (6,16,18 )
Table
II. Accuracy of Improved Fluoride M e t h o d
Concn. of Extent of Al++Molar Neutralization Moles/Li’ter Ratio, T h e n K F Added Titer of HCI X 10‘ F-/.41+++ (10.1%) (tO.OOO1 N ) 97.0 0,0947 111 30 98.5 0,0953 111 30 111 99.5 0.0959 30 0.0959 67 99.5 60 0,0958 30 67 99.5 0.0959 99.5 15 67
Recovery of Acid ( * O . l % l 98.9 99.5 100.1 100.1
100.0 100.1
concentration, in general, ranged from initial values of 0.2 or 0.1 iV to normalities little more than half of t,hese figures. Thus, although qualitatively the problem was similar to that of determining free acid in aluminum salts, the concentrat’ion ratios of acid to aluminum encountered in this work were relatively high. Experiments using sulfuric, hydrochloric, nitric, or oxalic acid, together with dissolved aluminum chloride, showed that the conventional fluoride method (in which the fluoride is added before the alkalimetric titration) is not quantitatively accurate when the concentration of acid is high with respect to that of aluminum. For example, Kith an acid concentration of 0.07 N , an aluminum concentration of 5.6 X 10-3 M , and a potassium fluoride concentration of 1.7 X 10-1 M, the acid recovery was found with these acids t o vary from 97.6 to 98.6’%. The data in Table I further illustrate the degree of inaccuracy encountered. (The mole ratio of acid t’o aluminum in t’hese experiments was several hundred times that encountered in aluminum salts where the mole ratio of free acid to aluminum may be of the order of 0.01.) The solutions used in these titrations were prepared by adding to 20.00 ml. of standard hydrochloric acid solution sufficient aluminum chloride hexahydrate (recrystallized from an analyzed ’ grade salt) and 1 Af potassium fluoride solution (previously adlusted so as to give a very faint pink shade in the presence of phenolphthalein-i.e., neutral to phenolphthalein-and then stored in a wax-lined bottle) to give the concentrations noted in the table. The solutions were titrated in a paraffined beaker by means of standard 0.1 sodium hydroxide solution to a phenolphthalein end point. The indicator blanks on water, potassium fluoride, and aluminum chloride plus potassium fluoride were identical. The concentration of hydrochloric acid in the 20.00ml. samplc (determined in both the absence and presence of potassium fluoride) was 0.0958 * 0.0001 A:. a+7
.4lthough thtl molar ratio F-/Ali+T n’as constant in thwe experiments, the percentage of acid recovered decreased v-ith increasing concentration of aluminum. This effect is very possibly due to increased occlusion of acid by the larger amount of alkali fluoaluminate precipitate a t the higher aluminum concentrations. That the percentage recovery of acid is also a function of the molar ratio F-/Al+++ was shown in a series of similar experiments; with this ratio varying from 7 t o 30, and with the concentration of aluminum 0.01 M , t,he recovery varied from 99.1 to 96.17 0 . If the low values obbained for acid in the presence of aluminum are due to losses by occlusion, this effect should be greatly lessened by adding the potassium fluoride, not a t the beginning of the titration, but a t a stage corresponding to almost complete neutralization of the acid. This modification of the method leads to accurate determinations of free acid in the presence of aluminum, as shon-n by t,he data in Table 11.
473
At least with the concentrations used in the above experiments, the efficiency of the acid recovery is independent of the molar ratio F-/Al+++ when the potassium fluoride is added a t a stage of the titration corresponding to 99.5% neutralization. (A minimum molar ratio of 6 is, of course, necessary to convert t h e aluminum ion to AlFb---.) Other experiments-for example, with oxalic acid and aluminum chloride-have confirmed the above finding that quantitative determinations of the acid may be carried out in the presence of aluminum, if addition of the potassium fluoride solution is delayed until neutralization is within a few tenths of 1% of completion. In practice, one or tm o trial determinations will be necessary in order to ascertain the point a t which the neutral potassium fluoride solution should be added. The writer has found it convenient to add the potassium fluoride a t the start of the first trial titration (titrations are carried out in paraffin-lined beakers), and from the value obtained for the acid titer, tentatively assuming it to represent 98y0 of the true titer, to calculate the volume of alkali corresponding to 99.5% neutralization. The potassium fluoride is added after the addition of this volume of alkali in the titration of the second aliquot, and if the end point is not ohtained within 0.5% of this value, the potassium fluoride point of addition is further adjusted before titrating remaining aliquot samples. VOLUMETRIC ANALYSIS OF HYDROUS ALUMINA
When hydrous alumina is prepared by precipitation from an aluminum salt, it is normally contaminated with the anion of the salt used. No such anion, however, is present in aluminas prepared by the interaction of amalgamated aluminum metal with distilled water. If a weighed quantity of such a pure hydroue alumina is dissolved in an excess of standard acid, and the e x c m determined using the fluoride method to eliminate the interference of the aluminum, then the equivalents of aluminum present are given by the equivalents of acid neutralized. [For volumetric methods for aluminum, making use of the fluoride complex, see Snyder (20)and the references given by him, and the paper by Chernov and Nekrasov (4.1 From the aluminum content, the composition of the alumina in terms of Al2O8.zH?0is readily determined. The calculation is facilitated by the use of the readily derived relationship: 6000 w P.11‘. = ~
(z
- y)S
where P.lt’. = formuli weight of A120a:~H20 = weight of hydrous alumina sample w = normality of standard alkali used .V = nil. of standard alkali required to titrate volume 2 of acid used for dissolution of sample = ml. of standard alkali required to titratc. excess y acid after complete dissolution The following procedure was used: A 0.23-gram sample of pondered pure hydrous alumina was weighed to + O . l mg. and transferred to a 12.5-ml. Erlenmeyer flask, 50.00 ml. of standardized 0.4 X sulfuric acid were added, and the .mixture was boiled gently until solution was complete. During the dissolution period, which required 2 to 3 hours, the volume of the acid solution was maintained essentially constant (by additions of water), until toward t,he end when it was allowed
Table 111.
Direct Titration 32.66 32.64 32.66
Sodium Hydroxide Re uired to Titrate Sulfuric A c i d after Various Treatments
Titration after Boiling 2 hours 3 hours 32.65 32.63 32.65 32.63 ... 32.63
Titration after Addition of AlCla equivalent 15 ml. to 0.15 gram of of neutral of 2and M KF 15 A. 2 M KF 32.65 32.68 32.67 32.67
...
...
474
INDUSTRIAL AND ENGINEERING
t o decrease to approximately 25 ml. The solution was cooled to room temperature and the excess sulfuric acid present was titrated by means of standard alkali according to the improved fluoride method, using 15 ml. of 2 M potassium fluoride solution (neutral to phenolphthalein).
Table IV. Analyses of Hydrous Aluminas by Volumetric and Gravimetric Methods
Formula weights Average formula weight Average z in AlnOs, xH~O
Samde 1
SamDle 2
Gravimetric Volumetric
Gravimetric Volumetric
156.7 157.1 156.7 156.9
157.3 157.5 157.4
...
142.7 142.2 142.2 142.3
143.7 143.7 143.7 143.9
156.9
157.4
142,4
143,8
3.1
3.1
2.2
2.3
Tests showed that quantitative acid recovery mas obtained for conditions similar to those of an analysis. In these control experiments, a constant volume of 0.3930 A’ sulfuric acid, diluted to 35 ml., was titrated by means of approximately 0.3 N sodium hydroxide after the treatments noted in Table I11 (the figures in this table refer to the number of milliliters of sodium hydroxide solution required).
A comparison of the results obtained using the volumetric method outlined above with those given by the gravimetric procedure (ignition to constant vieight in platinum, using a Fisher blast burner) is given in Table I\‘. Both alumina samples had been prepared, one (sample 1)a t room temperature and the other a t an elevated (95 O to 100” C.) temperature, by the interaction of amalgamated aluminum with distilled water. The filtered hydrous oxide was allowed t o stand for a f e r days, then pulverized, and finally dried to constaht weight in air a t 25 O C. The precision of the volumetric method is excellent, and the
CHEMISTRY
Vol. 18, No. 8
values obtained are in very good agreement with those given by the standard gravimetric ignition procedure. LITERATURE CITED
Beilstein, F., and Grosset, Th., 2. anal. Chem., 2 9 , 7 3 (1890). Bellucci, I., and Lucchesi, F., Gaze. chim. itaZ., 49, I , 216 (1919). Birstein, G., and Kronman, J., PrremysZ Chem., 18, 317 (1934). Chernov, V. A., and Nekrasov, N. S., Zavodskaya Lah., 10, 375 (1941).
Craig, T. J. I., J . Soc. C‘hem. I n d . , 30, 184 (1911). Davis, H. L., J . Phys. Chem., 36, 1449 (1932). Drossbach, P., 2. anorg. Chem., 166, 225 (1927). Feigl, F., and Krauss, G., Ber., 58B,398 (1925). Hahn, F. L., and Hartleb, E., 2. anal. Chem., 71, 225 (1927). Ivanov, V.
s., Chem.-Ztg., 37, 805, 814 (1913).
Keane, C. A., and Thorne, P. C. L., “Lunge and Keane’s Technical Methods of Chemical Analysis”, 2nd ed., Vol. 11, p. 374, London, Gurney and Jackson, 1928. Kolthoff, I. M. (with Mensel, H.), and Furinan, N. H., “Volumetric Analysis”, Vol. 11, pp. 175-7, h‘ew York, John Wiley & Sons, 1929. Kullerud, G., Paper Trade J., 92, No. 21, 47 (1931). Moody, S. E., Am. J . Sci., 22, 483 (1906). Muller, E., and Muller, F., Z . anal. Chem., 73, 47 (1928). Rosin, J., “Reagent Chemicals and Standards”, pp. 22, 28, h’ew York, D. Van Nostrand Co., 1937. Sabalitschka, Th., and Reichel, G., Arch. Pharm., 263, 193 (1925).
Scott, W. IT., and Furman, N. H., “Standard Methods of Chemical Analysis”, 5th ed., 5’01. I, pp. 16-17, New York, D. Van Nostrand Co., 1939. Simmons, J. R., Analyst, 65, 456 (1940). Snyder, L. J., IXD. EXG.CHEM.,A N ~ LED., . 17, 37 (1945). Thorpe, E., “Dictionary of Applied Chemistry”, 3rd ed., Vol. I , p. 173, London, Longmans, Green & Co., 1921. Thorpe, J. F., and Whiteley, SI. d.,“Thorpe’s Dictionary of Applied Chemistry”, 4th,ed., Vol. 11, p. 646, London, Longmans, Green & Co., 1938. Tolkachev, S. A., and Titova, Yu. G., J . Applied Chem. (U.S.S.R.), 8, 1282 (1935). White, A. H., J . Am. Chem. Soc., 24, 467 (1902). Zschokke, H., and Hiuselmann, L., Chem.-Ztg., 46, 302 (1922).
Colorimetric Determination of Cobalt in Metallurgical Products with Nitroso R Salt R. S. Y O U N G , E. T. PINKNEY, AND R. DICK Nchanga Consolidated Copper Mines, Ltd., Chingola, Northern Rhodesia
T
H E routine determination of small qiantities of cobalt in metallurgical products by the standard a-nitroso-6-naphthol gravimetric method is unsatisfactory. For materials ranging in cobalt content from 0.005 t o 0.2%, the large initial sample and the resulting separations involving several reprecipitations render the gravimetric procedure exceedingly time-consuming and subject to the errors inherent in all lengthy analytical manipulations. A colorimetric procedure based on the red color formed by nitroso R salt in the presence of cobalt under certain conditions has been used in recent years for determining very small quantities of this element in biological materials ( 3 ) . Hayviood and Wood (1) have described a photometric method for cobalt in steels, using nitroso R salt. These procedures are based on the fact that the colored complexes formed by most of the common elements with nitroso R salt, except cobalt, are destroyed bv nitric acid. The full development of the color with cobalt is attained in the presence of sodium acetate, and such variables as quantity of nitric acid and of nitroso R salt, time of boiling, etc., have an influence on the development of the color. In this laboratory several important modifications have been introduced to suit the requirements of complex ores and metallurgical products, to widen the applicability of the previous methods, and to save time and material. While the details of this pro-
cedure were worked out for final color measurements in a Spekker photoelectric absorptiometer, any other colorimetric means of determining concentrations in solutions, by photoelectric or visual colorimeters or Sessler tubes, can be employed. PROCEDURE
REAGENTS.Cobalt sulfate, 0.2385 gram of cobalt sulfate heptahydrate dissolved and made up to 1 liter with water. Xitroso R salt, 1 gram dissolved in water and made up to 500 ml. Spekker acid, 150 ml. of phosphoric acid (sp. gr. 1.75) and 150 ml. of sulfuric acid (sp. gr. 1.84) made up to 1 liter with water. Sodium acetate, 500 .grams of sodium acetate trihydrate dissolved and made up to 1 liter R-ith water. C-4LIBRATION GRAPH. T O 0, 1, 2, 3, €!Le., Up to 11 ml. Of standard cobalt sulfate solution are added 2 ml. of Spekker acid, 10 ml. of nitroso R salt solution, and 10 ml. of sodium acetate solut,ion. A blank is made by adding 2 ml. of Spekker acid and 10 ml. of sodium acetate solution but omitting the nitroso R salt. The blank and the standard solutions are brought to the boil on a hot plate, 5 ml. of nitric acid are added, and the solutions are boiled for a t least 1 minute and not more t,han 2 minutes. The standards and blank are then cooled and diluted t o 100 ml. with water. The absorption of the standards is measured on the Spekker photoelectric absorptiometer using 1-cm. cells and Hilger blue filters No. 6. The blank is set on 1.0 and the differences obtained are plotted against the weights of cobalt taken. ~
