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Volumetric and Gravimetric Analytical Methods for Organic Compounds. Walter T. Smith, William F. Wagner, and John M. Patterson. Anal. Chem. , 1964, 36...
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Volumetric and Gravimetric Analytical Methocds for Organic Compounds Walter T. Smith, Jr., William F. Wagner, and John

M . Patterson, Department of Chemistry,

U niversity of Kentucky, Lexington, Ky.

T

analytical methods discussed in this review have been selected from the literature which has become available to the reviewers from Kovember 1961 through November 1963. HE

DETERMINATION OF ELEMENTS

A review on recent developments in organic elementary analysis containing 65 references u'as prepared by hlitsui (129). Schoeniger has reviewed the field of quantitative organic elemental analysis, giving 262 references for the period 195&58 (170). Imaeda has written a review of the direct determination of oxygen in elementary analysis with 158 references (70). A review of the determination of fluorine in organic cornpounds including 49 references was prepared by Fumasaka (52). Boron. Boron and carbon were determined in alkyldecaboranes a n d related compounds by a wet combustion. Boron is oxidized to boric acid by alkaline persulfate, followed by titration with barium hydroxide in the presence of mannii,ol (41). Another procedure for organo boron compounds consists of measuring wit'h a p H meter in the presence of mannitol, the amount of boric acid formed by the oxidation of the compounds by sodium peroxide (90). Six procedures for determining boron in a wide variety of compounds containing carbon, hydrogen , nitrogen , oxygen, bromine, and phosphorus were studied. All procedures were complet'ed by titration of boric acid in the presence of mannitol. Adequate sharpness of end points may be achieved by appropriate selection of combustion procedures (152). Halides are discussed by l h i l e y and Gehring ( 2 4). Carbon and Hydrogen. Most of t h e methods reported are adaptations of p r w i o u s methods t,o spectral types of compounds. In the semimicro- and microdetermination of carbon ztnd hydrogen in substances containing mercury, the difficulties were removed by using a layer of silver spong. to absorb the mercwr\- in the cooler part of the combustion tube (145). The method using Co(I1, 111) oxide catalyst was adapted for compounds containing phosphoru: by mixing and

covering the sample with Co(I1, 111) oxide. For compounds containing arsenic, a platinum boat containing MgO at 500' is placed in the tube before the combustion catalyst ( 7 6 ) . Detailed studies of the combustion of a variety of compounds at different temperatures with an unpacked combustion tube show that for lOOyo combustion, a temperature over 750' C. is necessary. The combustion is a chain reaction. The vaporization section should be separated from the combustion zone by asbestos fibers (78). The carbon in alkyldecaboranes, nitramines, nitrosamines, nitric esters, and nitroaromatic compounds was determined by oxidation in an evacuated apparatus using a combustion fluid composed of chromic, iodic, phosphoric, and sulfuric acids (41). Hydrogen in highly fluorinated organic compounds was determined by combustion with oxygen in a layer of hlgO in a combustion tube. The water formed was determined either gravimetrically or by titration of HCl liberated by reaction of the water with pmethyl-p-ethylglutaroyl chloride (20). A gravimetric and a phototurbidimetric method were developed which are based on the interaction of the Si-Hbonds with HgClz to form Hg2Cl2 which may be weighed or measured in suspension photometrically (99). Urea is converted to N H 4 + and COz by heating for 5 to 10 minutes at 310' C. with 85yoH3PO4. The COz is absorbed in excess NaOH, which is back-titrated. N H 3 is distilled by a Kjeldahl-like proredure. The method is applicable also to biuret and ammonium carbamate (110).

The wet combustion method w i n g a mixture of H z C r 0 4 and H z S 0 4 a t 150" in oxygen was applied to the analysk of polymeric organoaluminosiloxanes. Carbon is determined gravimetrically as absorbed COz; silicon and aluminum are determined in the residual solution in the reaction flask (202, 204). The method has been applied also to the simultaneous determination of carbon and nitrogen as a substitute for the Kjeldahl digestion (200, 201). Halogens. T h r C-Cl bond in 0chloroethyl derivatives of organic phoiphorus acids is cleaved by boiling for 10 minutes in ethylene glycol

solutions of N a O H or K O H . T h e chloride is determined by the Volhard process (66). The reaction of some organic halides with thiosulfate forms the basis of an analytical method: RX Sz03-2+ RSz03- X-. The organic halide is added to a three- to fivefold excess of standard 0,LV Sz03-2, peroxide-free dioxane is added as solvent, and the mixture is heated for various times a t 25' to 60'. The solution is then titrated with a standard iodine solution (13). TWOsemimicromethods for the determination of halides make use of a sodium reduction in organic solvents. One uses higher alcohols as the solvent (225); the other uses a mixture of dioxane and methyl Cellosolve (150). Both use the Volhard method for the titration of the halide. A sodium reduction in xylene solvent was used for the determination of chlorine in tetrachloroalkanes (228). Halogens attached to a side chain of aromatic compounds may be determined by treating with 1 to 5Oj, hgKO3 in 95% alcohol. The precipitate may be weighed or the excess .$gr03 may be titrated with thiocyanate (133). The fluorine in organosilicon monomers and polymers having fluorinated radicals is released by a fusion of the sample with potassium in a bomb a t 900' to 950'. If chloride is present, it also may be determined. The silicon is determined from a separate aliquot of the solution from the fusion (26). A similar potassium fusion method was reported for the simultaneous determination of halides, sulfur, phosphorus, silicon, and nitrogen (35). The oxygen flask method waq used for the analysis of highly halogenated substances by mixing the sample with powdered sugar and absorbing the combustion products in an ammonia solution. The halides were titrated with silver nitrate (123). ii platinum-lined Parr oxygen calorimeter bomb is used for the quantitative decomposition of samples for the determination of fluorine, sulfur, and boron by conventional methods (14). The problem of burning large sample9 of heavy organic liquids and solidi to determine lo\$ concentration< of chlorine, phosphorus, and sulfur, wasolved by a special apparatu. com-

+

+

VOL. 36, NO. 5, APRIL 1964

391 R

bining the features of the Schoeniger and Wickbold techniques (46). d procedure for the simultaneous determination of mercury and halogens has been report'ed (147). Metals. An improved method for the determination of manganese in organic compounds was achieved by digestion of the sample in H s S 0 4 with KHSO, and HgO. After complete combustion the M n + 2 was titrated with KYInO4by the T'olhard procedure (158). .I semimicro- and microprocedure for mercury uses a cornbustion in a stream of nitrogen. After absorption of the nitrogen oxides, halogens, sulfur, phosphorus, and arsenic compounds in a layer of the decomposition product of K M n 0 4 , the mercury is absorbed on silver sponge and weighed (146). A similar procedure may be used for the simultaneous determination of mercury and halogens (147). Nitrogen. h chromic acid oxidation procedure for organic nitrogen compounds, similar to that of Terent 'ev et al. (200-204), was studied by Jurecek and coworkers ( 7 5 ) . Carbon and hydrogen are oxidized to. C 0 2 and H20 ; aliphatic NOs- and SO-- groups, to H N 0 3 , and S- S to K2. Aromatic SOr- groups yield XH3and the amines form S H 3 with some b I e S H 2 and lIe2?JH. The S r is measured in a nitrometer: TH3 and the amines are distilled and titrated with standard acid, and the HXO1 is reduced to N H B by Devarda's alloy. Hydrogen peroxide may be used to oxidize the organic matter in nitrogen compounds by dropwise addition to the material acidified with concentrated sulfuric acid in a Kjeldahl flask (12%). .llthough not a generally applicable method for the determination of nitrogen, perchloric acid may be used to oxidize the organic matter. Perchloric acid alone or with periodic and vanadic acid does not oxidize ammonia. Previous difficulties wit,h the use of perchloric acid are due to the action of hy1)ochlorite on ammonia after dilution. If chlorine is removed promptly, good results may lie obtained with many cornpounds (132). The Kjeldahl method has been used for 5-nitrofurfural derivatives by preliminary reduction with HI,which was sui)erior to other reducing agents ( 4 2 ) . The use of the hypobromite procedure to eliminate the Kjeltiahl distillation \vas studied extensively to overcome the interferences of the various catalysts commonly used in the digestion (65). The Kjcldahl distillation may he climinnted by neutrdizing a n aliquot of thc rligrstcd samplr to the phenolphthalein ond point, first with 30Yc NaOH and then with 0,l.Y S a O H . Then 20 nil. of 0.l.Y S n O H iz added, thr aolution is lioilcd for an hour to 392 R

ANALYTICAL CHEMISTRY

drive off the ammonia, and the excess NaOH is back-titrated (33). ; i hollow, perforated, polyethylene stopper is placed in the neck of the Kjeldahl flask to break up excessive foam during a distillation (125). Simultaneous determination with carbon, hydrogen, and halides has been discussed (85, 110,200, 201). Phosphorus. -4 modifitd method for the determination of phosphorus in organic compounds inirolvcs t h e double precipitation of LIg:.KH4P04 and a mixed indicator of Eriochrome Black T and p-nitroso-S,S-dimethylaniline for complexometric titration ($29). semimicrodeterminat,ion of phosphorus is achieved by decomposition of the sample in a microbomb by sodium peroxide, followed by a titration wit,h uranyl acetate (96). Compounds of the general formula R2Si[OP(:O)lIe]O, are hydrolyzed to form the corresponding alkylphosphinic acids, \vhich are back-titrated with 0.1.1~alkali ( I O ) . .I wet combustion using concentrated sulfuric acid and K2S208 or H202 has been employed for the determination of phosphorus and silicon in organic compounds ( 1 f 5 ) . Simultaneous determination with halides has been discussed (3.5, 46). Silicon. Silicon may he determined in o r g a n o d i c o n compounds by dccomposition with hydrofluoric acid and precipitation of t h e fluorosilicic acid with benzidine (f 02). A semimicro- and microprocedure for silicon is based upon a decomposition wit,h potassium permanganate in a sealed glass tube a t 400" to ,500" for 1 hour to convert the silicon to silicon dioxide (2). Simultaneous determination with carbon, hydrogen, halides and phosphorus (26, 35, 115, 202, 204) has been discussed. Sulfur. Results for the detcrmination of sulfur in 18 organic compounds hy the Schoeniger flask method were statistically evaluated. There was no correlation between the standard deviation and the nature of the sulfur bonding (118). .in oxygen flask method was also uqed for the determination of sulfur by Ellison. The resulting sulfate was reduced hy a mixture of HI, HCI, and HzPOz to H r S which ww trapped in SaOH and titrated iodometrically (44). Sulfur has also lieen simultaneously determined with halides (f4,S5, 46). L\

FUNCTIONAL GROUPS

X e w t3evelopmcnts (116) and methods (2l.i) in functional grouli analysis have been revieived recently. The use of strong oxidizing agents (38) as a means

of analyzing organic molecules has heen discusscd. Instrumental and chemical

methods of functional group analysis have been compared by Veibel (214) and some industrial applications of functional group analysis have been described by Brancone (28). Acetyl Groups. T h e modified Kuhn-Roth method (60) for the determination of carbon-methyl groups has been extended to the determination of S-and 0-acetyl groups (61). Acetyl end groups in acetylated polyformaldehyde may be determined with a precision of 5 to 6% (97) by a n initial methanolysis, followed by saponification of the methyl acetate formed. Acid Halides. Both carbonyl and sulfonyl halides may be determined to within a n absolute error of ~ k 0 . 3 7 ~ by reaction of the halide with Excess standardized hexamethyleneimine in methanol (203). The excess reagent is back-titrated with methanolic hydrogen chloride to a methylene yellowmethyl red end point. hlorpholine and mercury(I1) acetate in a carbon tetrachloride-acetic acid solvent may be employed to determine acyl halides without' interference from hydrochloric or carboxylic acids ( 140). .\fter reaction of the morpholine with the acid halides, the excess is titrated with perchloric acid in acetic acid. . h i d chlorides in the presence of hydrochloric acid are estimated by first titrating the hydrochloric acid in the sample (which is dissolved in benzene) with aminopyrine to a dimethyl yellow end point (16). .\ second tit'ration with aminopyrine after methanolysis gives the acid halide content. Hydrolysis of acid chlorides with a n aqueous pyridine-tliosane solvent is the basis of analysis of these compounds ( 6 7 ) . Excess water is removed with acetic anhydride, the mixture neutralized with perchloric acid, and the chloride complesed with mercury(I1) acetate. The released acetate is titrated with perchloric acid. Acids. Most of thc recent direct titration proccdurcs for the dctcrmination of carboxylic acid3 involve the usc of nonaqucous solvcnts. I m provements in tho nwthod ustially involve n modification of the solvent sy.stcm or titrant. Onc such modification utilizes a mcthanol-l)c.iizcnt. solvent and a sodium mrthoxidc titrant (208) and another recommends the use of benzalkonium hydroxide in a dimethylformamide solvent (162). A n advantage of the latter method is that the system nced not be protected against CO, during titration. It has Iiern reportcd (209) that a direct titration of the carboxylic acids of higher molecular n-eight is inferior to the indirect method in which the acid i* refluxed with excess alkali, follon-ed h y hack-titration of the alkali.

The indirect method cannot be used for t h e determination of 5-bromovaleric acid if heating is employed ( 7 3 ) : since halogen displacement consumes t h e base. Expected values are obtained for t h e acid if heating is omitted. Very weak a(ids can be titrat'ed in aqueous solutions if a complexing ion is present ( 4 3 ) . I n thls way citric acid and acetylacetone cart be titrated in the presence of copper(I1) or magnesium ions. Weakly acidic cornpounds such as barbituric acids, sulfonamides, and alkaloid salts can be titrated with aqueous KOH or K'riOH to a thymol blue end point (134). The sample is dissolved in dimethylformamide for the titration. Acids which are e,isily oxidized are usually estimated by a n oxidimetric method. Formic, lactic, pyruvic, and maleic acids and acids structurally similar to these are quantitatively oxidized by potassium manganate (154). Ammonium vanadate and sulfuric acid mixtures oxidize oxalic, tartaric, citric, salicylic, and gdlic acids (but not unsubstituted monocarboxylic acids) and may be used as a. reagent' for their determination ( 4 5 ) . Organic acids whirh are easily decarboxylated or oxidized to form COn can be determined b:; titration of the COZ formed. Thus acetonedicarboxylic acid is decarboxylated by boiling a n aqueous solution and glyoxylic acid is oxidized by periodate (11 9 ) . The decarboxylati'm method has been extended to the analysis of p aminosalicylic acid 1'175), since this compound decarboxylates quantitatively in boiling acidic: solutions. Oxalic and mandelic acids may be titrated a t room temperature using ammonium hexanitratocerate(1V) as the oxidizing agent (59). For the determination of 0.02 to 2 mmoles, the relative error is about 11.5%. Potassium permang:tnate in 1 to % 1'2 XaOH has been suggested as a titrant in the determination of mandelic acid ( 169). Formate ion is oxidized readily by bromine chloride, while undissociated HCOOH is oxidized only very sloivly (17'4). The error in the determination of the HCOOH content of acetic acid was 0.5%. Formic acid or formates can be determined by oxid:ttion with hot HgCI, solution, using either a citrate buffer (120) or a sodirim acetate buffer (217).

Thc mrthods available for the analysis of tlicarbosylir arid> and their mixtures have brcn revienccl rccmtly (100). Tartaric acid may lie determined gravimetrically cithcr by precipitating thp arid' as the Icad s d t from aqueous media (164) or hy preripitating the

potassium bitartrate by adding E t O H (131). Salts of the carboxylic acids are best analyzed by nonaqueous titration methods. A direct t,itration using HCIOl in acetic acid with added acetic anhydride (24) or a n indirect titration using excess HCIOl in a methyl ethyl ketone solvent may be employed (103). The excess HC10, is determined by differential titration with tetraethylammonium hydroxide. .I cation-exchange resin has been utilized in the anal acetate in aqueous-alcohol solutions (15). The acid produced after exchange is titrated with standard base. Water-insoluble metal carboxylates of the type n-C4H9Sn(0)OCOCH3 are determined by treatment with hot 64YG H3P04(9). After addition of HzO and distillation, the carboxylic acid is titrated with standard S a O H in 95% E t O H to a bromothymol blue end point. Active Hydrogen. Gautier (55) reviewed t h e methods of analyzing compounds containing active hydrogens. A manometric technique, which is applicable to hydrogen atoms attached to oxygen or sulfur, involves treatment of the compound wit'h diborane in tetrahydrofuran (121, 166) to produce hydrogen. Similar methods make use of a LiAUHa reagent in tetrahydrofuran (144) or in ethyl ether (199). Dispersed sodium permits the selective determination of hydrogen in acids, alcohols, phenols, amides, a n d sulfonamides (130). The evolved hydrogen is measured by the pressure change after reaction in a constant volume apliaratus. Amines, aldehydes, ketones, eaters, and terminal acetylenes do not produce hydrogen. The reaction vessel used in the Zerewitinoff method has been modified (4)to avoid premature contact of the Grignard reagent with the sample. Malonic arid may be determined with a precision of 1% by the use of exress standard iodine at, 100" (216). The unreacted iodine is estimated by reaction with sodium thiosulfate. Sodium formate and acetaldehyde interfere. Fluorene has been estimated in crude mixtures by the cyanoethylation reaction followed by hydrolysis (104). The resulting acid was determined gravimetrically as the sodium salt. Alcohols. .Icylntion mcthods continue to bo t h e most frrquently usrd in alcohol dctcrminations. The Fritz-Schenk method (50) involving the HC104-catalyzed acetylation in pyridine has been e\tended to other primary and secondary alcohols (69) and phenols (98). Polyethylene glycols cannot be determined by this method.

The hydroxyl number of poly(oxyalkylene polyols) (217) and of poly(oxyalky1ene ethers) (188) may be determined by a p-toluenesulfonic acidcatalyzed acetylation in ethyl acetate s o h t ion. Primary alcohols, secondary alcohols, and phenols can be determined by esterification using a known weight of stearic anhydride in boiling m-xylene (180). The excess anhydride is decomposed with H?O in the presence of sodium stearate or pyridine and the resulting stearic acid titrated with standard base a t the boiling point of the solution. The procedure is reported to be rapid and accurate. The KOH-catalyzed cyanoethylation of monohydric alcohols is the basis of their determination ( 138). The excess unreacted acrylonitrile is treated with sodium sulfite and titrated with standard HCI. Hydroxyl equivalent weights of polyoxyalkylene compounds are determined to an accuracy of 2% using phen>.l isocyanate (15 7 ) . After reaction with the sample, the excess isocyanate is treated with an excess of standard dihutylamine, which in turn is titrated with HC104 in niethyl Cellosolve. .I similar ~ ~ r o c ~ d uisr eused for the determination of unsaturated polyester resins containing hydroxyl groups (40). The exress phen\.l isocyanate is titrated with diisobutylamine to a bromophenol blue end point. -hid-dichromate solutions are extensively used in alcohol determinations. The major variations in the procedure involve the method used in analj excess dichromate or in the detection of the oxidation product. In one procedure, the excess dichromate is treated with a known escess of F e ( S H 4 S O J r , followed by back-titration with standard dichromate (17). Another method employs an iodometric titration to determine the unreacted dichromate ( 3 4 ) . High molecular weight alcohols are determined oxidimetrically using a solution of C r 0 3 in acetic acid (19). The oxidation products are estrarttd with ether and the carbonyl nunibel,.; determined. Nethanol and ethanol are oxidized quantitatively in dilute wlution by acidified KlIn04 cqtalyzerl by ( S H 4 ) J I o 0 4 at 25' ( l i s ) . Escess K l l n 0 4 is determined iodomet,rically. N o r e concentrated alcohol solutions are not oxidized quantitatively , llethanol, in the presence of formaldehyde and formic acid, is determined by the use of a series of selecdve oxidizing agents (1.93). Hypoiodite osidizcs formaldehyde; 1iyl)obromite oxidizes forinaldehytlr. and formic' arid : arid divhromate ositlize.: methanol, formaldehyde. and fomic' acid. Hytlrosycthyl glmul)s in rthylene VOL. 36, NO. 5 , APRIL 1964

393 R

oxide adducts can be determined to within a n error of 1 to 2% by refluxing with concentrated HI (207’). After heating, the mixture is titrated with NazS~03. The analytical methods available for the determination of hydroxyl groups in lignite have been compared critically (219). Aldehydes and Ketones. Most recent dcvclopments in t h e determination of aldehydes a n d ketones involve minor modifications of wc.11 established mrthods or t h e extension of these methods to new systems. Thus the S H z O H method is used to determine HCHO in resinous phenol mixtures (84), the cyanohydrin procedure is used to determine the carbonyl content of starch (168),and the dimedon precipitation method is used to determine the aldehyde content of air (39). Ketones in air samples are determined by condensations with furfural. Aldehydes can be determined in the presence of acetals (186) by using aniline to form the Schiff’s base and water. The water is titrated with the Fiscaher reagent (148) or with Mg3N2 (149) when ketones of the type MeCOR (where R is 4 C,) are present. Cyclic ketones interfere. Girard T reagent and 2,4-dinitrophenylhydrazine react with the methanol or ethanol solvent (53) when used in carbonyl determinations. tertl h t y 1 alcohol is recommended as a solvent for these reagents. Dichromic acid oxidation is used in the determination of trichloroacetaldehyde, paraformaldehyde, metaformaldehyde, acetaldehyde, and paraldehyde with a maximum error of 0.15% (87). Formaldehyde or acetone in aqueous alkaline solution is oxidized by IC1 (191). The excess IC1 is determined iodometrically. A reagent prepared by dissolving mercury in concentrated nitric acid is used to determine 5-nitrofurfural semicarbazone (95). After the precipitate has been removed from the reaction, the excess reagent is titrated with thiocyanate solution. Amides. Caprolactam, after a n initial hydrolysis, can be determined by a modified Van Slyke method (62). l‘he method gave results similar to the classical Tan Slyke method. Oxaniide in nitrocellulose is analyzed by an alkaline hydrolysis followed by an acidimetric titration of the arpmonia produced (12). Results are high and must be corrected. Thioacetamide can be determined to a precision of 0.250/, using a hypobromite oxidizing agent (36). Excess hypobromite is titrated with t,hiosulfate after the addition of KI. .-In indirect complexometric method may also he used (112). 394 R

ANALYTICAL CHEMISTRY

Mix 20 ml of 0.254.M Zn(SO& with

6 grams of NaOH, add 0.2 gram of sample, dilute with HzO to 200 ml., boil 5 to 10 minutes, filter the hot precipitate through a G4 Schott filter, wash with hot H20, neutralize with HCI, add p H IO ammonium buffer, and titrate with 0.2505M E D T A with Eriochrome Black T. The method may be extended to the analysis of thiourea. Directions for the bromometric estimation of urea to within 2% of theory have been recommended (180). The formation of an insoluble compound of composition 2COX2H4. Hg(XO3)2.3Hz0is the basis of a n analysis of urea (230). The sample is titrated with Hg(N03)2 to the appearance of a yellow precipitate when a drop of the solution is mixed with a saturated soda solution. Amines. A nonaqueous titration procedure can be used to determine piperidine with a n error of = t O , l i % (215). A solution of the base in acetic acid is titrated with HC104 in dioxane to a Methyl Yellow end point. Aziridinyl compounds (I) can be rapidly analyzed (167) by reaction with KSCN and p-toluenesulfonic acid in methanol followed by back- titration with K O H in methanol. CH3-CH

1

\X-R

I

CHz/ Diphenylamine has been recommended as a n indicator (197) for diaaotization titrations of aromatic amines. Kumerous compounds have been reported to give anomalous reactions in the Van Slyke amino nitrogen determination, resultingin erroneous analyses. Substances reacting in this way are certain amino acids (83), indole and derivatives (80), sulfonic acid amides (81), phenols (79), and pyrroline and oxazoline compounds (82). The dioxane-sulfur trioxide method of Terent’ev (198) has been extended to the determination of bases such as piperidine, pyridine, quinoline, and dimethylaniline with an average error of 1 to 2% (142). The method was not satisfactory for certain bipiperidine and bipyridine compounds. Mixtures of primary, secondary, and tertiary amines can be resolved by application of the differential reaction rate method (64). The reaction utilized in the method is that between primary and secondary amines and phenyl isothiocyanate. Tertiary amines are determined by difference. Mixtures of primary and secondary amines and Schiff’s bases can be analyzed by the application of a series of selective reactions (139). Total amine nitrogen was obtained by titration of the sample in a chloroform-methanol solvent using Taschiro indicator.

Secondary amines were determined acidimetrically after combining the primary amines with an exces~of 2,4penetanedione and the total of primary and secondary amines was determined alkalimetrically after converting them into the dithiocarbamic acids by reaction with CSz. Aniline in the presence of glycerol was determined by titration with K1h-03 after KBr and HC1 had been added to the sample (153). p-Phenylenediamine can be determined by oxidation with excess acidified S a V 0 3 solution, folloned by backtitration of the excess with FeSOa (166). X , X ’ - Disubstituted p - phenylenediamines can be converted into Wurster’s salts by the addition of chloranil or hydroquinone and these compounds can be determined by neutralization of the mixture with HC104 in nonaqueous solution (114). The reineckates of aliphatic amines can be determined by the following procedure (105). Decompose 0.2 mmole of the reinecka t e with 4 ml. of 10% potassium tartrate and 1 ml. of NaOH by heating 2 t o 3 minutes. Neutralize the clear green solution with 5147 acetic acid to phenolphthalein, dilute to 50 ml., add 3 drops of dichlorofluorescein, and titrate with 0.1N AgN03. The precipitate changes from white to pink a t the end point.

A complexometric procedure utilizing a solution of CdIz in K I can be applied to the determination organic nitrogen compounds (296) such as aminazine, papaverine hydrochloride, quinine, and pachycarpine hydroiodide. 5,6-Dimethylbenzimidazole can be determined with an accuracy of +0.3% by either an iodometric method with precipitation in acid media and backtitration of excess iodine or by titration with HCIO, in chloroform with methyl red as indicator ( 2 1 ) . Comparable results in the determination of quaternary ammonium salts were obtained (211) by titration with either K&dI, (Marme’s reagent) or Na13Ph4. Compounds containing eightmembered carbon chains could not be titrated with Marme’s reagent. Sulfates of organic bases may be titrated directly with HC10, in acetic anhydride with crystal violet as the indicator (161). 130th a HC10, titration and a gravimetric determination as reineckates have been recommended for the determination of succinylcholine chloride and bromide (48). Amino Acids. T h r oxidation and decarboxylation of a-amino acids with ninhydrin form stoichiometric amounts of C 0 2 (119). The COz is absorbed in 13a(OH)z, the excess of which is titrated with HCI. p-Aminohippuric acid can be titrated with sodium nitrite solution in the

iiycsencc of HCI and K l h as catalyst (212). Orange IV is used as indicator. Carbodiimides. A t,itrimetric proccdurc Iusvd upon t h r reaction

RK:C:XR'

+

(COOHI2 RNHCON.HR'

+ CO + CO,

+

has been developed for the determination of carbodiimides (227). The samlile is refluxed with oxalic acid in dioxane for 45 minutes, followed by titration with sodium methoxide in benzene-methanol to a thymol blue end point. Carbon - Methyl Groups. T h e Kuhn-Roth method (206) for the determination of carlion-methyl groups was modified by carrying out the digestion in a bath and distilling the acetic acid directly from the reaction misture (60). The Kuhn-Roth method cannot be used for :In accurate determination of the number of carbonmethyl groups, nor for the determination of mebhyl groups in methylpyridines and other nitrogen heterocycles ( 4 7 ) . Diazo Compounds. Three new methods have been suggested for t h e determination of aromatic diazo compounds (205): the direct titration of a secondary aliphatic amine with the diazo compound with 13acid as indicator; the reaction of the diazo compound with a secondary aliphatic amine, steam distillation of the escess amine, and by acidimetric titration; and the reaction of the diazo compound with escess aromatic amine, followed by bromination of the excess amine after steam distillation. Esters. Dircctioris for t h e determination of saponification equivalents of phenolic esters have been reported (210). The carbobenzylos:,- group has been determined by hydrolyzing the compound in 6 to 7 N H2FiO4,absorbing the liberated CO2 in Ba(OH)? and backtitrating with HCI ( 1 e 4 ) . Ethers. A modified a p p a r a t u s and procedure for t h e determination of the methoxyl group have been described (222). Recent modifications in the Zeisel method involve variations in the detection of the alkyl iodide produced. In one such modification, the alkyl iodide is determined gravimetrically after absorption on a Molecular Sieve (228). Other modificzitions include reaction of the alkyl iodide with HI, followed by titration of the liberated I2 with Ka2S203(92) a:id reaction of the alkyl iodide with Ag5\:03in acetic acid (77). The high results obtained in the mrthoxyl determination in substituted quaternary trimethylammoniopyrimidine c*hloride is due to a cleavage of an .V-methyl groul) (86) hy HI. llolwriles rontaining os>.eth>.lrne

or perpropionic acids, can be determined groups (CH2--CH,--O), when heated in the presence of Hp02by titration with HI liberate iodine which can be tiwit,h NazS2O3in the prehence of KI and trated with SazSz03(237). TiOS04 (109). The hydrogen peroxide Hydrazine Derivatives. Jsonicocan be determined by continuing the tinic acid hydrazide, semicarbaxide, titration with Na12&03 after t h e reaca n d benzoylhydrazine may be detion mixture has been heated a t 35" in termined b y a direct oxidimetric tithe presence of S a F , lIoO3, and K I . tration with K13r03 (methyl orange Phenols. A thcrmometric titraindicator) (218) or by an indirect comtion has been applied to a dctcwninaplesometric method using excess TI + 3 tion of phenols in the prccwice of in dilute H2SOlr folloived by titration amines and alcohols with a n accuracy with (ethylenedinitri1o)tetraacetic acid of + I % (143). The titrant n-as alkali. (22). An acylation procedure using mThe use of various osidizing agents, nitrobenzenesulfonyl chloride in aqueous including SaV03, chloramine T, KIO3, acetone alloms the determination of KT3r03, SaC10, and diethylenetetraphenols in the presence of alcohols with ammonium sulfatocerate, in the oxidia n accuracy of +39F ( 2 3 ) . Base is metric determination of hydrazine deadded to decompose the sulfonyl halide rivatives has been discussed and and the excess titrated acidimetrically. evaluated by Singh and Sahota (182). A method based upon the reaction 5 - Sitrofurfurylideneisonicotinoylof phenols with stnndard p-toluenehydrazine was determined in the presdiazonium chloride in XaZCO3solution ence of furfural using a Hg(KO& has been reported (206). Hesareagent, the excess being titrated with methylenimine is added to the reaction thiocyanate (94). misture, and the escess is distilled and Nitro Compounds. S i t r o comtitrated with HCI. pounds (and nitroso compounds) have The iodine chloride method has been been determined by heating with a applied to the analysis of heptylres.orchromic-sulfuric acid mixture a t 150' cinol ( 5 7 ) . followed by reduction to SH3 with o-Acylphenols after convewion to the Devarda's alloy (136). The S H 3 is osime can be determined by precipitadetermined acidimetrically tion of the osime with a copper salt, Kitro compounds containing the followed by a chelatometric titration of dinitrophenyl group can be titrated the escess copper ion (66). quantitatively in acetone or pyridine A nonaqueous titration a l l o w the with tetrabutylammonium hydroside in determination of p-acetamidophenol benzene-methanol (187). Compounds with a n error of less than i1o/c (5). .1 analyzed in this way included 3,5-(N0&solution of the C6H3COOR, 2 , 4 , 6 - ( ~ 0 2 ) r C B H z C O 2 ~ f edimethylformamide , sample is titrated with a benzeneand 2,4- (?;O2),C6H30R. methanol solution of sodium methoxide Oxiranes. A procrdure for the to a n azo violet end point. determination of propylene oxide is The bromometric methods for the based upon the titration of hydroside determination of tot'al phenol in efformed by rraction of t h e ouirane fluents have been evaluated (27). with NazSzO3or MgCI, (155). When Sulfides. Sulfides can be deterMgC1, is employed. the Mg(OH), is mined to bettrr t h a n 0.1% absolute determined with H2S04by a n indirect error by the following procedure (225). titration. Hydrochloric acid in methyl ethyl To the sample (2 to 10 mg.) dissolved ketone is reported to overcome shortin 4 ml. of acetic acid, add 2 ml. of comings of the customary methods in 15% HCI and titrate the solution with osirane determinations ( 7 4 ) . The 0 . 0 2 5 potassium bromide-potassium method has been applied to glycidyl bromate to a n indigo carmine end ethrrs, glycidal amines, and eposidized point. olefins. Ethanol interferes, and styrene On the basis of infrared spectroscopic oxide cannot be determined. studies it has been reported that the Peroxides. T h c u s c of acetyl thioprolongation of Zeisel reaction conditions glyrolatc in a n acctic acid-acidified does not constitute a reliable general ethmol-chloroform solvent prevents method for t'he determination of the air oxidation a n d rcaction of iodine alkyl sulfide group (8). with double bonds in the iodometric Sulfur-containing amino acids show detwmination of lipide perosides (37). widely differing reactivities in the Zeisel X double titration method has been method (6). Thus, methionine and propo5ed for the determination of ethionine are cleaved by HI in less than benzoyl peroside in CC1, in the 3 hours, while the S-methyl and Spresence of free chlorine (179). Iodoethyl derivatives of cysteine are not metric titration gives equivalents of clpaved after 7 hours. both benzoyl peroxide and chlorine. Polysulfides can be determined by The rhlorine is then titrated with reduct,ion with lithium aluminum methyl orange in acid media, and the hydride in tetrahydrofuran and h y p m x i d c d(>trrminetl by difference. weeping the liberated H,S in a cadmium Perarid. surh as I'erformic, peracetic, VOL. 36, NO. 5 , APRIL 1964

395

R

acetate solution (166). The CdS is titrated iodometrically. The method can be adapted to the determination of mixtures of mono-, di-, and polysulfides. Sulfonamides. Sulfonamides can be determined by a direct titration with chloramine-?' in a n acid medium in t h e presence of K13r and methyl orange (68) or by a complexometric method using copper(I1) sulfate (1). The excess copper is determined by titration wit'h disodium (ethylenedinitrilo) tetraacetate. Sulfonic Acids. Sulfonic acids which form water-soluble barium salts can be determined rapidly to within 1% by titration of the barium sulfonate with (ethylenedinitri1o)tetraacetic acid using a n Eriochrome Black T-sodium rhodizonate indicator (56) ' Sulfonated compounds such as dodecylbenzenesulfonic acid can be titrated in isopropyl alcohol with dodecyltrimethylammonium hydroxide (224). The determination of 2,6- and 2,7naphthalenedisulfonic acid is based upon their oxidation by HV03 to phthalic acid in strongly acid media (1'76). The vanadium(1V) ion equivalent to the oxidized acids is determined by titration with permanganate. Guaiacolsulfonic acid on oxidation with dilute nitric acid produces sulfuric acid which can be precipitated with benzidine (160). Titration of the precipitated salt with S a O H gives the sulfonic acid content in the sample. Thiols. Ethanolic solutions of thiols can be titrated directly with mercury(I1) salts using s-diphenylcarbazone as indicator ( 6 3 ) . Sodium o-hydroxymercuribenzoate with thiofluorescein indicator has been used for the titrimetric determination of aliphatic thiols (621) such as methanethiol, ethanethiol, thioglycolic acid, cysteine, and thiomalic acid ($4). Thioureas. Thiourea and its derivatives can be determined oxidimetrically with amylose indicators using as titrant' iodine trichloride (185),

bis-(ethy1enediammonium)sulfatocerate ( I S S ) , or potassium iodate (184). Unsaturation. il hydrogenation procedure for t h e determination of unsaturation utilizes a new active platinum metal catalyst' prepared in situ from t h e reaction of sodium borohydride with platinum salts (30). The hydrogen is also generated in situ from sodium borohydride. The method is reported to be rapid and precise. The analytical applications of iodine t,hiocyanate have been discussed (186). The bromine chloride method has been extended to the determination of maleic and fumaric acids in the presence of mercury(I1) sulfate (172). The excess bromine chloride is determined iodomctricall y. 396 R

ANALYTICAL CHEMISTRY

The differential reaction rate approach for the determination of mixtures has been extended to the alkenes, using either hydrogenation or bromination (180). The hydrogenation procedure is said to be more generally applicable. Iodine thiocyanate addition may also be utilized in the determination of alkene mixtures by the differential rate method (127). The various methods available for the titration of the double bond in acrylic derivatives have been examined critically (161). The morpholine method was found to be the best in the determination of acrylonitrile. Camphene has been determined by its reaction with acetic acid in the presence of a boron trifluoride catalyst (194). The excess acetic acid is determined titrimetrically. The addition of hydrogen chloride to tert-amylenes is the basis of its determination (88). .\fter reaction, the organic layer was saponified with standard KOH and the excess measured acidimetrically. A method for the rapid preparation of Hanus and K o b u r n solutions has been described (89). Impurities in the amyl alcohol solvent such as sec- or tert-amyl alcohol or glycerol or the use of too highly concentrated sulfuric acid lead to errors in the Gerber determination of fats (113).

MISCELLANEOUS METHODS

This section does not include compounds that normally are reviewed in the Review of Applications Analysis appearing in AKALYTICALCHEMISTRI ( 6 ) , such as food, coatings, pesticides, petroleum, pharmaceuticals, and rubber Mixtures. The compo4tion of binary solutions of organic liquids where one liquid is considerably more waterinsoluble t h a n the other can b t dcterniined by titration n i t h water to the point of turbidity. Titration curves for benzene, toluene, xylene, mesitylene, and p-cymene in methyl, ethyl, and propyl alcohol are shown (32). Carbon tetrachloride and carbon disulfide in binary solutions with methanol, ethyl alcohol, isopropyl alcohol, dioxane, and acetone were determined by a phase titration using water as the titrant. The turbidimetric end point can be adapted to automatic methods (159). The reaction product. from the pyrolyii< of alcohol may be analyzed as follons: .icetic acid i i titrated n i t h barium hydroxide, ethyl acetate is saponified with 0.5.X- sodium hydroxide, ethyl acetate and acetaldehyde are estimated by oxidative saponification n l t h hydrogen peroxide in 0.5.Y sodium hydroxide, and dimethyl ketone and

acetal are estimat,ed by use of hydroxylamine before and after acid hydrolysis, respectively. Ethyl alcohol is estimated by quantitative oxidation with potassium dichromate (85). The method of Deckert-Lubatti was modified to determine ethylene oxide, acetaldehyde, and formaldehyde in a mixture. Potassium iodide with hydrogen iodide was used for ethylene oxide, hydroxylamine for total aldehydes, and Schiff's reagent for formaldehyde (163). A method employing several titrimetric procedures was used to determine methanol, formaldehyde, formic acid, and hydrogen peroxide simultaneously in the presence of iron salts (181). The methods of Zaugg and Garven were extended and modified in the determination of diethyl malonate and its homologs in mixtures (7%). The phosgene and hydrogen chloride impurities in chloroform may be determined by a combination of aqueous and nonaqueous titrations using aminopyridine as titrant (171). o-Phthalic acid may be extracted by water a t 55" from the iso- and terephthalic acids. The iso- acid may then be separated from the tere- acid a t a temperature of 90". Each fract,ion is then titrated with 0.2h' sodium hydroxide ( S I ) . Methods and procedures are described for the determination of cysteine, thioglycolic acid, cyanide, and dithioglycolic acid in the presence of one another (280). A method (Idf) was developed for the direct titration of mono-, di-, and triethylamines in a complex mixture of aliphatic hydrocarbons, acetonitrile, and resin-forming residue, based on the method of Wagers et ul. A procedure is described for t8he determination of ammonia, cyanide, nitrite, and nitrate in the hydrolysis products of organic nitrates (173). A mixture of partial glycerides obtained by heating linseed oil with glycerol in presence of sodium phosphate was analyzed by a combination of procedures (&@. Trialkyl or triaryl organotin hydroxides can be determined and differentiated from the corresponding oxides by a Karl Fischer titration. R3SnOH compounds consume 1 mole of iodine for each mole of tin, whereas (RsSn)zO compounds consunie 0.5 mole (107). A procedure is described for the determination of carboxyl, hydroxyl: methoxy, and carbonyl groups in Balkan coal (11). Organosilicon Compounds. Siliconhydrogen and silicon-phenyl groups may be determined by reaction wit'h excess standard 0.1M bromine in acetic. acid solution. Si-H reacts a t room temperature as follows:

SiH

+ 13r2

-*

SiBr

+ HBr

Si-Ph reacts in a hot solution as follows: SiPh

+ fir2

-+

9iBr

+ PhBr

T h e excess bromine in each case is determined iodometrically ( 4 9 ) . Procedures are given for the analysis of alkyl (aryl) chlorosilanes, alkyl (aryl) (alkoxy) aminosilanes, and silamines based on the titration in nonaqueous media (1U1). I n ether solution 1 mole of R,SiC14-. reacts with about 4- n moles of aniline, giving aniline hydrochloride, which forms a basis for analysis (195, 196). Diglyme is reported to be a better solvent t h a n dibutyl ether as a solvent for t h e gasometric determination of silinols by the lithium aluminum hydride method (28). The available methods of determining organometallic compounds were evaluated for estimation of organosilylmetallic compound,s. Organosilylmetallic compounds react with butyl bromide to give a n equivalent’amount of bromide which can be titrated by the Volhard method (68). Water. T h e water in furfural was determined from t h e pressure developed by acetylene in a closed bomb by t h e reaction of calcium carbide with the water (108). Unclassified. Ka.;er-soluble dithiocarbamates may be determined by reaction with a known a m o u n t of s t a n d a r d sulfuric acid, which is t h e n back-titrated with sodium hydroxide (177). The gravimetric method of Piekarski involving the use of the amine adduct of alkyl ketene dimers was modified so as to titrate the excess of diethylamine wit’h hydrochloric acid (71). Substituted chloroitcetanilides react with pyridine to give quat,ernary salts which are soluble in water, in which the chloride ions may be titrated by the I I o h r method (192). The titrimetric determination of hexamethylenetetramine by oxidation with dichromate of the formaldehyde obtained by the acid hydrolysis of the compound was investig;ated. T h e excess dichromate was determined iodometrically (98). The thermal decarboxylation method of determining uronic acid proposed by I’erlin was critically examined. The method does not compare favorably with the acid decarboxylation method (7). The analysis of -technical 1,l-bis (p-chlotopheny 1) - 2,2,2-trichloroet,hanol which may be contaminated with I , 1-his(p-chlorophenyl: - 2,2,2- trichloroethane is based o;i the dehydrohalogenation of the latter yielding one CI- and the hydrolysis of the former yielding 2 C1-, followed by a Volhard titration of the chloride (91).

Diethyl zinc may be determined by reaction with a standard solution of iodine in a closed flask under dry nitrogen, followed by a titration of the excess iodine with thiosulfate (135). Kojic acid is determined in pyridine solution by titration with O.lN potassium methoxide using azo violet indicator (111). Comparative studies of the determination of synthetic detergents in coinpounded products were made with llie toluidine, cetylpyridinium, Cetavlun, and benzidine methods. The first two methods give low results; the latter two give high results; none is sufficiently precise (26). LITERATURE CITED

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(3) Aftalion, H., Keim, B.,Steresru, lI,, Rev. Chim. (Bucharest) 11, 49 (1960). (4) Albu. C., Analele I’niv. “C. I . Parhon,” Ser. Stiint. N a t . 9, No. 26, 195-8 (1960). (5) .4licino, J. F.,Jlicrochem. J . , Symp. Ser. 2, 567-9 (1962). (6)ANAL.CHWM. 35, llR-201R (1963). (7) Anderson, D. 31. W . , Garbutt, S., Smith, J. F . > Talanta 9, 680-97 (1962). (8) Anderson, D. l f . W., Zaidi, S. S. H., * Ibid., 9, 611-1.5 (1962). (9) Anderson, H. H., ASAL. CHEM.34, 1340-1 (1962). (10) Andrianov, K. A , , Khananashvili, 1’. M.,Taail’eva, T. Y.,Zhur. ilnal. K h i m . 16. 738-9 (19611. (11) Angelova, G.,‘ I z v . ‘ Jnst. Obshcha A’eorg. Khint. Org. K h i m . , Riilgar. Akad. Nauk 8, 181-91 (1961). (12) Apatoff, J. R., Cohen, J., U. S. Dept. Corn., Office Tech. Services,

( 2 6 ) Bondarevskaya, E. A . , Kreshkov, A . P., Syavtsilo, S. lr., ICuznetsova, 1‘. AI,, l’r. Koniis. p o .lnalit. K h i m . d k a d . .Voiik SSSR, Inst. Grokhirra. i Analit. K h i m . 13, 24-7 ( 1 963). (27) Borkowski, R., P:lsyiikien.irz, J., Koks, SjTtola, GOZ4 ( 2 ) , 9 - 7 (19;)g). (28) Branrone, I,. AI., .Ific.rochenz. J., S y m p . Spy. 2, 605-81 (1062). (29) Brett, R. .4., .Vaticre 197, 484-5

(1963). (30) Brown, H . C., Sivasaiik:iran, IC., Brown, C. A , , J . Org. (’hem. 28, 214-15 (1963). (31) Rutina, I. 17., Plyusriin, T., G., Shevvhenko, S . A . , Izv. Sibirsk. Otd. A k a d . .Yauk S S S R 1962. S o . 6. 6%-77 ( 3 2 ) Caley, E. R.,Habbiush, A.,-AAAI,. CHEM33, 1613-16 (1961). ( 3 3 ) Chsng, K., H u a Hsueh Tiinn Pao 1960, So. 6,3-5,

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(lOG2).

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VOL. 36, NO. 5 , APRIL 1964

397 R

Barton, R., ASAI,. CHEM.33, 269-71 ( 19

164) 1 547 (63) 1

Ibir (66) 1 273 (67) 1 44, 61-:

168) Ihad Inst. 2, 2'5-32 (1960). (69) Il'ina, A. I.: Sedavnyaya, Y. G., 3lnslob.-Zhir. Prom. 27, S o . 10, 31-3 (1961). (70) Imaeda, K., .\'agoya Shiritszi Daigaku Yakugakitbit Kitlo 9, 1-34 (1961). (71) Inmi, I., Waknbayashi, T., Yoshino, SI., Komiya, S., Kotera, K., Yakagakii 8, 279-82 (1959). ( 7 2 ) Inuedy, J., Giniesi, O., Acta f'him. A c o d . Sei. Hung. 31, 347-56 (1962). (73) Isenberg, S , , Settle, hI. A . , Chemist Analyst 50, 111 (1961). (74) Jung, G., Kleeherg, JV., Kunststofe 51, 714-15 (1961). ( 7 5 ) Jurecek, Sl,, Sovak, \'., Kozak, P., Talanta 9, 72-3 (1962). (76) Jurecek, XI., Wankova, B., Taborska, I., Palatova, XI.] Sb. Ved. Praci, Vysokn Skola Chem.-Technol., Pardubice 1961, P t . 2, 09-114. 177) Kainz., G.,. Xikrochim. Acta 1960, \~

I

2b4-60.

~

(78) Kainz, G., Horwatitsch, H., Z. .Anal. Chem. 184, 363-70 (1961). (75)) Kainz, U.,Huber, H., Mikrochim. .Icta 1959, 891-902. (80) Ibid., pp. 003-7. 181) Ibid.. 1960. 38-43. Ibid.l pp. 24-5-33, Kainz, G., Kasler, F., Ibid., 1960,62I

I.

L. Ya., K h i m . i Tekhnol. Goryuch. Slanlseu i Produktov ikh Perernbotki 1962, S o . 11, 290-.5. (85) ,Kamath, S . R., Sharnia, M. M., J. Scz. I n d . RES. ( I n d i a ) 20D, 200-1 (1961). (86) Karpitschka, S . , Jlikrochim. Acta 1961,738-40. (87) Karpov, 0. S . , Tr. Komis. pa '4nnlit. K h i m . A k a d . .Yazik S S S R , Inst. Geokhim. i .Analit. K h i m . 13, 132-7 (1963). (88) Karpov, 0. S . , Z h . Analit. K h i m . 17, 1029-30 (1962). (89) Kartha, A . R. S., J . Sci. I n d . Res. ( I n d i a ) 21B, 555-6 (1962). (90) Kato, S., Kirnura, K., Tsuzuki, Y., .Yippon Kagaku Zasshi 83, 1039-41 (1962). (91) Katz, D., Z. .4nal. Chem. 195, 2b8-62 (1063). (92) Klimova, V. A , , Zahrodina, K . S., _J _m -s t . Aknd. .Yaiik SSSR. Otdel. K h i m . .\a?ik 1961, 2234-5 (93) Iiloucek, B , Gasparic, J , Obruha, K , Collectzon Czechoslov Chem Commun 28 (6)1606-9 (1963) 104) Kolusheva. A , 9in'o. S , Farmatszva ' ( S o f i a ) 1961,'So:4, 17-25.' ($15) I b i d . , So. 5 , 25-9. (06) Kondo, A , , Bunseki Kagaku 9, 41618 (1960). (97) Kosinska, V.,Feign, E., Plasticheskie .Ila.?sy 1961,SO.6,8-9. (98) Kovalenko, P. Y . , I'ch. Z a p . 1r'ostozsk.-nu-Donu Gas. I.nio. 41, So. (84) Kslde,

'

0 , K3-93 (1958). ( 0 9 ) Kreshkov, -4. P., Bork,

V. A., Shvykovo, L. A , , Kaaodsk. L a b . 28, 1Al-1 (1062). (100) Kreshkov, A . P., Bykova, E. S . , Smolova, S . T., Lakokrasochyne J l a /erioly i ikh Primenenie 1963, S o . 1, 45-51, (101) Kreshkov, A. P., Ilrozdov, V. A , Vlasova, E. G., and Kuhiak, S., Vestn.

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ANALYTICAL CHEMISTRY

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