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Acid-Base Titrations in Nonaqueous Solvents

JOHN A. RIDDICK
Commercial Solvents Corp., Terre Haute, Ind.

CID-base t,itrations in nonaqueous media possess the accuracy, speed, and simplicity required for good analytical methods. The equipment is inexpensive and available in any analytical laboratory equipped to do aqueous titrations. The analytical possibilities are comparable to those of aqueous titrimetry (66). Recent applications of titrations in nonaqueous solvents have reduced greatly the cost of control and specification analyses (35). This sullject is being reyiewed for the first time. Unfortunately there is no index to acid-base titrations in nonaqueous solvents. The only means of making a survey of the litrrature a t the present time is to consult recent articles and their references. Many of tlie revieiv articles dealing with the theoretical :ispccts have extensive bibliographies. The hil~liography a t the end of this article is necessarily inconiplete hec:iuse of the difficulty in locating publications in this field. l l a n y of the earlier papers have been included because they contain significant historical material. E. J. Crane, editor of Cheniical Abstmcts, is studying suitable nieans for indexing this field. d bibliography of literature pertaining tri acid-hase titrations in nonaqueous solvents is being compiled 1)y Marion 11.Davis o f the National Bureau of Standards. The references given in this review may eerve as an i n , terini source of Iiackground material for persons interested in this field.
HISTORICAL

were probably the first to titrate acids and bases potentionietrically in an aprotic solvent. TIYO years later Lavine and Toennies (50) used the two color changes of thymol blue to distinguish between strong and weak acids in chloroform. Vorlander (16), in 1934, and Vorlander, Fischer, and Felicitas (76), in 1933, studied the titration of amines and alkaloids in chloroform. They propcsed the name aminometi~y for the titration of aminelihe s ~ ) ) stances in nonaqueous solvents. The procedure of S u d e a u and Branchen (59), in 1935, for the determination of amino acidE in acetic acid solutions was the first method of acid-hase titration i n nonaqueous systems to find wide acceptance.
TIIEORETICAL

Stoichiometric reactions in nonaqueous media take plare in solvents that may o r may not take part in the reaction. The solvents are divided into t x o classes. Aprotic Solvents. Thcse solvents arc inert and arc riot l i lieved t o take part in neutralization reactions. They hav or very ~niall dipole and do not readily form coniplexes. the saturated and benzene-type hydrocarbons and some of the halogenated hydrocarbons, such as carbon tetrachloride and chloroform, belong to this group. Amphiprotic Solvents. These solvents have an apptwial~lc: dipole moment, or have groups with dipoles such as p-dioxane. They are believed to take pa1 t in neutralization reactions in a manner similar to that of J-iater. Lower fatty acids, alcohols, and amines belong to this c1a.Q. There are t,hree nell-knoll-n theories that may be used t ( J cxplain neutralization reactions in any solvent system. Hydrogen Bond Theory. The hydrogcn bond, or hydrogen bridge, theory apparently vias propounded by hIcorc (67) in 6 1 ) . IVhile 1907. A discussion of the theory is given by Pauling ( the literature relating to this theory is voluminou~, it is not tlie one used mcst frequently to esplain the type of reactions gentmlly thought of as neutralization. Lewis Theory. Leviis proposed his theory of acids and t m e s (68) in 1923. According to this theory, a base is an electron donor and an acid is an electron acceptor, Seut,ralization reactions take place because of a molecule of more stable electronic configuration results from the sharing of one or more pairs of eiectrons. Lewis acids and bases include the coninionly acceptetl onrs plus such compounds a s aluminum chloride, stannic chloriilc, boron chloride, and copper(I1). A discussion o f thc Lemis thcciry, as well as other theories relating t o neutralization, \vas puhli.ihed b y Luder and Zuffanti (55). Brgnsted Theory. This theory R-as first published in 1923 ( 7 ) and later was amplified and clarified (6, 6). Brglnsted suheequcntly discussed the particular application of his theory to amphiprotic solvents (8). According to this theory an acid is a proton donor arid it h e a proton acceptor; thus A e R H+ acid base proton or using a familiar acid HCIeCIH+ acid base proton
~

The concept of electrolytic dissociation has dominated the field o f acid-base titrations for over half a century. At the turn of the century and until 1926 the theory was almcst universally accepted. It was realized by some that the theory was lilnited mainly to aqueous media and could not be applied to neutralizapointed tion reactions in other solvents. I n 1902 Kahlenberg (40) out several ionic type reactions that tcok place in benzene, a solvent in which ions did not exist according to the electrolytic dissociation theory. The following year Vorlander (74) reported the titration of aniline with hydrogen chloride in a benzenc system using p-dimethylaminoazobenzene (methyl yellow) as the indicator. He as studying color changes and structure of dyes and did not consider the analytical significance of his experiments. Folin and Weritworth (15), in 1910, published the first anillytical method of titrating in nonaqueous media. They found that t h e higher fatty acids could be tit,rnted with sodium alcoholate to a sharp end point in chloroform, carbon tetrachloride, benzene, or toluene. They believed their niethod represented a nciv departure in alkalimetry. Tivo years later Folin and Flanders (18) extracted hippuric acid from urine with chlorcforni and titrated it with scidiuni ethylate. The same years they (17) questioned the validity o f the theory of ionization Then applied to all solvent systems. I n 1923 Hantzscli (30) presented a study of the nature of acids that shon.ed a departure from the prevailing theory. I n the same year Br@nsted( 7 ) published the preliminary concept of his theory of acids and bases. Early the following year Lowry (53) independently published essentially the same theory. The first recognition of titrations in nonaqueous media appears t o be an electrometric procedure for the determination of acidity in oils published in the Proceedings of the American Society for Testing Materialu in 1925. I n the following years several mcdifications of this procedure were reported (10, 15, 65, 68, 6 5 ) . In 1927 Hall and Conant (26)and Conant and Hall (11) published their studies on super acids. LaMer and Downs (&I), in 1931,
41

It is apparent that when an acid loses a prot,on it becomes a h e .


Conversely, a base accepting a proton becomes an acid. An acid or a base may be an ion or an electrically neutral molecule-for example: H2.0 $ H + -OH acid baee

42

ANALYTICAL CHEMISTRY
IC,H,Oz acid
$

H-

NH4+ S H acid HzO base

+ C2HyOJ base + h, base

+ H + S H30+ acid
H30+ acid

R a t e r acts both as an acid and a base and the equilibrium may be represented as H?O acid

+ base H20

+ -OH

base

An acid dissolved in water or acetic acid would reach the following equilibrium:

+ -C101 + base H20 e acid babe HCZHa02 + H?O H30+ + -C2H30? H?C2H302+ + T l O a HCIOI + HC2IIaOz
HClOi acid The Brginsted theory is believed by many to be compatible with both the hydrogen bond and Lewis theories. The acid and base reactions are usually explained on the basis of either Brpinsted or the Lewis theory. The Brpinsted and Lewis bases are the same. The difference between the two theories is that Lewis includes as acids, ions or molecules that form covalent bonds with a base such as boron trichloride, sulfur trioxide, and silver iodide. and the reaction product is not necessarily a salt. Brgnsted acids are limited to ions or molecules that donate a proton, or hydrogen ion. Lemis :acknowledged the usefulness of the Brpinsted acids as a subclass and suggested the name hydlogen acids or H-acids. There has been considerable discussion concerning the differences and likenesses of these two theories. Luder (54) has shown that proton donors must be included with electron acceptors. Kolthoff (44) suggested that the Brginsted definition remai; unchanged and that the larger group of acids be designated Le4is acids or proto acids. Davis and Schumann (13) suggested it is more logical to consider the Br$nsted acids as a special subclass. Bartlett and Dauben (2) concluded that Lewis and Brpinsted acidity does not run completely parallel and believed that one class of acids cannot be completely absorbed in the other. Ferreira (16) stated that the two processes are not thermodynamically equivalent and that Brginsted acidity cannot be included in the Lewis acidity. He concluded that the Lewis definition includes the Brpinsted acids but the two kinds must be studied separately Practically all acid-base titrations in nonaqueous solvents developed to date have been concerned nith Brpinsted or H-acids. The nonhydrogen acids have not been used as analytical reagents, nor have they been titrated with bases (except 17, footnote) mainly because indicators, potentiometric systems, or other means have not been found for indicating the equivalent point. Another factor that has deterred the development of their use is given by Davis and Schumann ( I S ): the fundamental principles governing acid-base reactions in various types of organic solvents are less understood than the principles governing these reactions in aqueous media and are considerably less familiar to the average chemist . The nature of the H-acids has been extensively studied by Hantzsch (29, 30) and Hantzsch and Voight (31). Bell (5)has discussed the use of the terms acid and base. The idea of super acids was advanced by Hall and Conant (2.5) and the strength of acids and bases was studied by Conant, Hall, and Werner (11, 12, 25, 26) in their studies in acetic acid. Hall has discussed this vrork and its significance ( 2 4 ) . Hammett and Dietz (28) believed that formic acid is more deserving of the term super acid than is acetic acid. There are too many difficulties encountered in using formic acid as a solvent. Among them i s its instability as a compound. Palit (60)proposed the use

of a gljcol-hydrocarbon solvent and postulated that a glycol increases the strength of an acid. The information on the strength of acids and bases in organic solvents is meager. Present knowledge indicates that the strength will have to be determined for each acid and base for each amphiprotic solvent used. Izmailov ($6)has reviewed the available information and arrived a t the same conclusion. He concluded that the variation of the strength of an acid or base from solvent to solvent is determined by the basicity of the solvent. The relative acidity of two acids will vary from solvent to solvent, and the variation of the ratio of their acidity will be greater the more different are the acids. Hammett and Deyrup (27)concluded that the relative strength of two bases of the same chaige type is independent of the medium in which they are compared. The relative strength of some acids and bases has been determined in a few solvents ( 2 , 12, 25, 26, ST, 79).
SOLVE3TS

A variety of organic liquids have been used as solvents for acidbase determination. Solvents, as such, have not received very much consideration or study. Hall and Conant (25) and Conant, Hall, and Werner (11, 12, 26) investigated acetic acid as asolvent. KO other solvent has received so extensive a study, Moss, Elliott, and Hall (58) made a study in ethylenediamine. They concluded that any outstanding progress in the field will probably depend first on a drastic departure from conventional solvent titrant combinations. Palit (60) proposed a G-H solvent for the estimation of weak acids: . . G stands for any glycol type solvent and H represents any solvent for hydrocarbons, such as hydrocarbons themselves, alcohols, chlorinated hydrocarbons, etc. This solvent was developed during Palits (61, 62) and Palit and McBains (63) study of solvents for soaps. Ruehle (66) studied potentiometric titrations of acids in 2methoxyethanol (methyl Cellosolve), acetone-butyl alcohol mixtures, anisole (methyl phenyl ether) and p-dioxane-n-butyl alcohol mixtures. Gordy (23) determined the basicity of 26 solvents by determining the shift in the infrared OD band when the compound was mixed with CH3OD. The basicities can be quantitatively estimated relative to benzene, equal to zero. The choice of a solvent depends on the nature of the substance to be determined. The solubility, the reaction product with the titrant, and a means of determining the equivalence point of the reaction are important considerations. There is considerable evidence that mixed solvents may be supeiior to a single solvent in general solvent pov er and in sharpness of the color changeof indicators o r in the potentiometric break. Kilson (77) found that the indicator end point n as sharper in acetic acid-hydrocarbon mixture than in acetic acid alone. Palit ( 6 0 ) found mixed solvents preferable. Fritz used a Ride variety of solvents for his studies, and he and Lisicki (22) found that for the titration of m o d carboxylic acids and other moderately acidic compounds benzenemethanol was the preferred solvent. Most analytical methods have been developed using acetic acid as the solvent. (The adjective glacial has been omitted in this review. Acetic acid refers only to glacial or anhydrous acetic acid.) Several authors used acetic acid or a mixture of acetic acid and other solvents (4, 32-34, 59, 56, 59, 70, 77). The alcohols have found wide use for the determination of acids and bases (IO, 15, 38, 68, 69, 80). Chloroform has been used (14, 32, 41, 50,51), but generally because of its specific solvent poner for the system under study, Fritz has demonstrated that a variety of solvents may be used (82). Other solvent systems are reported ( 17-20).

INDICATORS AND ELECTRODES

Kolthoff (4.8) proposed a definition of an indicator for acid-base titration in any solvent system, as [weak acids or weak bases, the

V O L U M E 2 4 , NO. 1 , JANUARY 1952


acid form of which has a different color from the basic form. The principles and use of indicators in water (47) may be used as a guide to the development of a like system of indicators for nonaqueous solvents. Kolthoff (43) stated that the present choice of indicators i more than adequate to satisfy all the needs 01aqueous media, but not for nonaqueous media. Davis and Schumann ( I S ) stated, Although academic studies have thron n considerable light on the subject . . there is a great need for further investigation of acid-base phenomena in various solvents . . Before acid-base measurements in organic solutions can be performed as readily as those in aqueous solutions, it will be necessary to provide a series of indicators ranging from strongly acidic to strongly basic compounds. There is no absolute ciiterion of acidity o r basicity in nonaqueous solutions. Acids and bases of unlike nature may undergo a change in the relative position of their respective strengths in different solvents. All information reported to date has concerned the H-acids of BrZnsted. S o information is available for the non-H-acids of Lewis, such as boron trifluoride, aluminum chloride or antimony trichloride. A satisfactory means has not been found to determine absolute acid or base strengths in a variety of solvents. S e w electrode systems that do not have liquid junctions, or whose liquid junction is small and can be estimated reliably, must be developed. Potential measurements have been made with the calomel-glass electrode system in acetic acid. These measurements cannot beinterpolated into any absolute values for strengths of acids or bases. Some studies of indicators have been made in specific solvents. Conant and Hall ( 1 2 ) studied ten indicators of two structural types in acetic acid. Kolthoff and Gauss (45, 46) determined the thermodynamic ionization constants of several indicators in both methyl and ethyl alcohols. It was found that the indicators had about the same ionization constants in both alcohols. Davis and Schumann ( I S ) studied the behavior of bromophthalein magenta with different classes of organic bases in several aprotic solvents, I n addition to the usual use of indicators in acid-base titrations, they may be used for quantitative comparison of base strength and for measurement of the relative strengths of organic acids. Tomicek (70) observed that p-aminophenylbenzenesulfonamide, 1-naphthyl-Bsulfonamide, and 1-naphthyl-7-sulfonamide in acetic acid solution fluoresced in ultraviolet light. These compounds produced so strong a fluorescence and such a marked change a t the equivalent point that they could be titrated visually with perchloric acid under ultraviolet light. The fluorescent color change was used as the indicator. Methods for acid-base titrations have been reported which employ the following indicators: modified methyl orange (xylene cyanol) (20),methyl red (20, 60), thymol blue (22, 60, 62, 58), methyl violet (21, 33, 39, 7 7 ) , 1-naphtholbenzein ($2, SS, 69, 7 0 ) , bromocreeol yellon ( S 8 ) , ciyetal violet (66, 59, 67, YO), phenolphthalein (58), benzyl auramine (59), methyl orange (60), and cresol red (70). Hall and Conant (25) based their work in acetic acid on measurements with the chloranil electrode. Most of the early potentiometric measurements were made ubing a lithium chloride bridge. Clarke, Wooten, and Compton (10) appeared to be the first to use both electrodes in the titration vessel. Fritz and Lisicki (22) used a pH meter and glass-antiniony electrodes. Rlarkunas and Riddick (56) used a calomelglass electrode system in acetic acid. Moss, Elliott, and Hall (58) used the antimony-antimony system in ethylenediamine, and found that the glass-antimony system was not suitable. Palit (60) used the calomel-glass electrodes in the G-H solvent. Ruehle ( 6 6 ) studied potentiometric titrations in a number of amphiprotic solvents with the saturated calomel-quinhydrone electrodes. Seaman and Allen ( 6 7 ) used a glass-calomel system with the calomel electrode immersed in saturated potassium

43
chloride. The calomel electrode was connected to the titration vessel by a bridge of acetic acid saturated with lithium chloride Tomicek (70) compared the quinhydrone, chloranil, and glasscalomel electrodes. Virasoro (7s)studied titration with calomelagar, silver, and silver-silver chloride in butyl alcohol.
TITRANTS

Perchloric acid is the strongest acid in organic solvents and has been found t o be the most suitable acid titrant in acid type amphiprotic solvents. Perchlorates have a more favorable solubility than the salts of any other acids. Hydrochloric acid is unsuitable in many solvents because of its high fugacity and the insolubility of many chlorides. Sulfuric acid introduces complications, including unfavorable solubility of sulfates. Lavine and Toennies ( 5 1 ) found that perchloric acid slowly hydrolyzed acetonitrile and titrant solutions of perchloric acid in acetonitrile could not be used unless freshly prepared and standardized. Perchloric acid in acetic acid has been used for the determination of a wide variety of materials ( 4 , 20, 21, SZ-Sq, 39, 66, 69, 70, 7 7 ) . The most widely used bases for amphiprotic solvents, particularly the alcohols, are alkali metal alkoxides and alkali metal hydroxides. Potassium hydroxide appears to be more suitable than sodium hydroxide. The sodium or potassium alkoxides are more generally used (22, S8,50,51). Palit ( 6 0 )used sodium hydroxide in the G-H solvent. Moss, Elliott, and Hall (68) found sodium aminoethoxide (HdXCH2CH20Na) t o be a suitable titrant in ethylenediamine. Wooten and Ruehle (80)found that solutions of both potassium hydroxide and sodium butoxide in butyl alcohol were oxidized by the oxygen in the air. It was concluded that butyric acid was formed because titrations of strong acids such as picric, dichloroacetic, and trichloroacetic in butyl alcohol gave two inflection points. Weak acids such as acetic and phenylacetic gave only one inflection point because butyric acid is of about the same strength. Commercial butyl alcohol shov, ed the inflection points with picric acid with freshly made titrant. Freshly made titrant from purified butyl alcohol showed only one inflection point with picric acid. Further work showed that butanolic solutions of sodium butoxide are more stable than those of potassium hydroxide. The butoxide solution can be kept in a reducing atmosphere when protected from light. There is no acid that is as satisfactory for use in aprotic solvents as perchloric acid is for amphiprotic solvents. The first known reported acid-base titration in nonaqueous solvents was with hydrogen chloride in benzene. This solution changed titer too rapidly to be practical. The sulfonic acids have found wide acceptance because they are nonvolatile and stable, and have a favorable solubility. p-Toluenesulfonic acid in chloroform n-aa used by Dietzel and Paul ( 1 4 ) . Its use was confirmed by Khait (41). Trautner and Neufeld ( 7 1 ) and Trautner and Shaw (72) further studied the use of this acid. Trautner and Shaw developed a method for producing a pure, dry acid. Purified p toluenesulfonic acid monohydrate was heated a t 120 C. a t reduced pressure. Air dried over phosphorus pentoxide was bled into the drying chamber t o maintain the pressure a t 10 mm. The product is relatively nonhygroscopic and can be kept in a wellstoppered bottle. This acid appears to be the most satisfactory acid for most titrations in aprotk solvents, but a t present it is necessary to purify and dehydrate the commercial product before use ( I S ) . Trichloroacetic, d-camphorsulfonic, and picric acids have been used as titrants t o demonstrate the applicability of bromophthalein magenta as an indicator in aprotic solvents ( I S ) . Derivatives of guanidine appear to be the most satisfactory base titrants in aprotic solvents. Davis and Schumann ( 1 s )have shown that l,&diphenyl-, di-o-tolyl-, and dicyclohexylguanidine appear t o be the strongest bases in benzene. The latter is too difficult to dissolve to be practical. It is fairly soluble in chloroform but reacts with the solvent, particularly when warmed.

44
STANDARDS

ANALYTICAL CHEMISTRY
bases in acetic acid Markunas and Riddick ( 5 6 ) report a reproducibility of about 0.2%. This conclusion was based on the results of titration of substances that act as strong bases in a survey analysis of about 400 compounds. Other investigators report the same order of accuracy and precision in acetic acid (59, 70). Semimicro- and microtitrations in acetic acid have about the same range of error as similar titrations in aqueous solutions ($9). Fritz ( 2 0 )used perchloric acid in p-dioxane and ethyl ether and obtained results comparable to those made in a similar manner in aqueous solutions. Clarke, Wooten, and Compton ( 1 0 )studied the reproducibility of potentiometric titrations in butyl alcohol using potassium hydroxide in butyl alcohol as the titrant. Five aliquots of NBS benzoic acid solution were titrated. The volunies of titrant used were 17.34, 17.34, 17.39, 17.37, 17.36 ml.; average 17.36 ml.; range 0.05 ml.; standard deviation 10.022 ml. The error in titrations in the G-H solvent is of the same order as reported by others for routine type determinations (60). Davis and Schumann (13) made a series of experimental semimicro titrations in benzene to demonstrate the applicability of the indicator bromophthalein magenta. The reproducibility reported was good.
METHODS

The standards suitable for aqueous solutions are generally suitable for nonaqueous solutions. Diphenylguanidine prepared according to Carlton ( 9 ) has been used by several investigators. Its favorable solubility makes it particularly adaptable for standardizing acids in aprotic solvents. Fritz (30) standardized perchloric acid in p-dioxane with diphenylguanidine. Two compounds that were known to be of high purity were titrated Tyith the standard acid. The following is a summary of the results:
Determinations 2,2-Bip).ridine Brucine 4 3 Mean. % 99.44 99.97 Range % 0.19 0.19 Ilean Deviation,

70

0.08 0.06

Benzoic acid of reagent grade or Kational Bureau of Standards standard sample has been used for standardizing bases (23, 38, 6s). Sodium carbonate was one of the first substances to be used for standardizing nonaqueous acid solutions and still finds wide acceptance ( 4 , 36, 67, 70, 77). Potassium acid phthalate is a reliable standard for perchloric acid in acetic acid. Seaman and Allen ( 6 7 ) studied this standard both potentiometrically and with crystal violet indicator. They standardized a solution of perchloric acid potentiometrically with both NBS potassium acid phthalate and sodium carbonate prepared acvording to Kolthoff and Sandell (48). A difference of 9 parts in 11,000 was found between the averages. The data are given in the next section. Markunas and Riddick ( 5 6 ) standardked perchloric acid with the same standard in a study of the scope of titrimetry in acetic acid. The two papers appeared almost simultaneously.
ACCURACY A h D PRECISION

The accuracy and precision of acid-base titrations in nonaqueous solvents are of the same order as analogous titrations in water. Seaman and Allens potentiometric standardizations of perchloric acid with potassium acid phthalate and sodium carbonate illustrate both the precision and accuracy obtainable with careful technique (67). Their data follow:
NalCOa X
0.11747 0.11730 0.11748 0.11749 0.11730 0.11745 Average Ranwe Stadard, deviation 0.11743 0 00019

The coefficient of expansion of nonaqueous solvents is considerably greater than that of water. For precise results, the titrant must be kept and used a t a constant temperature or a temperature correction must be applied. Seaman and illlen ( 6 7 ) assumed that perchloric acid solution in acetic acid had the same coefficient of expansion a8 acetic acid-namely, 0.0011 per 1 Titrations in Acetic Acid. The potentiometric and indicator methods given by Markunas and Riddick ( 5 6 ) are essentially those used by Sadeau and Branchen ( 5 9 ) ,Blumrich and Bandel ( 4 ) , Seaman and Allen ( 6 1 ) ,Kahane ( 3 9 ) ,and Fritz (21).

c.

KHCaHaOi. S
0.11762 0.11753 0.11747 0.11747 0.11764 0.11740 0.11752 0 00024 f0.00009

POTESTIOMETRIC METHOD. . 4 sample containing about 3.5 milliequivalents of the material to be analyzed is weighed into a 250-ml. tall-form beaker, without spout, and dissolved in 30 ml. of acetic acid, warming if necessary. The mixture is then cooled and titrated potentiometrically. IXDICATOR METHOD.The same weight of sample as required for the potentiometric method is wei hed into a 250-ml. Erlenmeyer flask and dissolved in 30 ml. acetic acid. One drop of crystal violet solution (1% in acetic acid) is added and the solution is titrated with 0.1 N perchloric acid in acetic acid to a blue green color. The range of color change for crystal violet is rather broad. In order to become familiar with the end-point color, several potentiometric titrations with indicator present should be made.

07

*0.00008

All compounds do not titrate sharply in a nonaqueous system. This is a familiar situation in the aqueous system. The accuracy of titrating such compounds may be increased by either potentiometric titrations or the use of a reference buffer solution containing the indicator. The buffer solution is prepared to have the same indicator color as that of the pure compound a t its equivalent point when titrated. Methyl nicotinate when titrated with perchloric acid in acetic acid give a sluggish end point. Seaman and Allen (67) prepared two reference buffer solutions of different chemical composition for the titration of methyl nicotinate. The base was carefully punfied by fractional distillation and the apparent purity, determined by titration in aqueous solutions, was found to be 100.2 and 100.3%,; water by the Karl Fischer method, 0.02%. Titration to the standard buffer color KO. 1: 100.3, 100.2, 100.1, 100.0,100.2, 100.5%; average 100.2%; range 0.5%; standard deviation 1 0 . 2 . Values for standard buffer N o . 2 were 99.9, 100.2, 100.3$&; average 100.1%; range 0.4%; standard deviation =t0.2%. For routine types of analysis for substances that act as strong

S.4LTS OF CARBOXYLIC ACIDS. The major limitation for the determination of salts of carboxylic acids is their solubility in acetic acid. Most carboxylic acid salts of lithium, sodium, potassium, ammonium, primary, secondary, and tertiary amines, and quaternary salts of amines have sufficient solubility to be titrated ( 4 , 56, 70). Some salts of calcium can be titrated ( 5 6 ) . AErlISES. Amines, their derivatives and similar compounds, and their carboxylic acid salts can be determined (4, 56, 10). Blumrich and Bandel (4) report an acetylation method for the determination of tertiary amines in a mixture of amines. AhiINo ALCOHOLS. This class of compounds can be titrated readily (56). OXAZOLIXES. The only known successful method for analyzing oxazolines is by titration in acetic acid ( 5 6 ) . AmNo ACIDS. Nadeau and Branchen ( 5 9 ) demonstrated the practicability of determining amino acids by studying eleven representative ones. AMIDES OF CARBOXYLIC ACIDS. These compounds as well as acetylated amines cannot be determined ( 4 ) . CHLORIDES, BROMIDES, NITRATES, AND SULFATES. These Salts of the alkali metals, ammonia, and amines have been titrated by

V O L U M E 2 4 , NO. 1, J A N U A R Y 1 9 5 2
Higuchi and Concha (33, 34), using a modification of the method given above (56). Sulfates presented considerable difficulty because of their insolubility in acetic acids. Some of the compounds analyzed were sodium, potassium, ammonium, procaine, and histidine chlorides, ammonium, sodium, and pilocarpine nitrates, codeine and histamine phosphate, and quinine sulfate. QUINIKE. Quinine in mixtures can be extracted from a n ammoniacal solution with chloroform, the chloroform evaporated, and the alkaloid dissolved in acetic acid and titrated. A method is given for the separation and determination of a mixture of quinine and strychnine ( 3 2 ) . ALKYLENE OXIDES. These oxides react with aniline hydrochloride in acetic acid, liberating aniline which can be titrated

45
with antimony-glass electrodes was used. Lithium chloride was added to reduce the resistance of the solution. CARBOXYLIC ACIDS. Salicylic, benzoic, p-aminobenzoic, and stearic acids can be successfully titrated, ACID CHLORIDES AND ANHYDRIDES. These behave as strong monobasic acids. 3,5-Dinitrobenzoyl chloride, benzoyl chloride, and phthalic anhydride have been titrated. ENOLS.Methone (dime t hylcyclohexanedione) was reported. Monobutylamine. This solvent was used by Fritz and Lisicki (82) to titrate weakly acidic compounds. The titrant was the same as the one used for the methanol-benzene system. Antimony-glass electrodes were used. ENOLS.Acetylacetone was reported. PHENOLS. Phenol was reported. Pyridine as Solvent. The general use of pyridine is the same as for butylamine ( 2 2 ) . HYDROXYLAIII.\IOSIU~I SALTS. The hydrochloride has been successfully titrated in this solvent. Alcohols. COMMERCI.4L DIMETHYL SULFATE. A procedure for the determination of methyl hydrogen sulfate and sulfuric acid in commercial dimethyl sulfate dissolved in methanol has been reported ( 3 8 ) . Acidity of O i l s . This subject mas one of the first applications of titrations in nonaqueous solvents ( 1 ) and has received considerable attention ( I O , 68). Chloroform. F o l k and coworkers (17-19) studied acid-base titrations in nonaqueous systems. ACIDS. -411classes of acids can be titrated with sodium ethylate in organic solvents. Those acids not readily soluble in chloroform can be dissolved in 10 ml. of absolute alcohol m d diluted to 100 ml. with chloroform. ALKALOIDS. p-Toluenesulfonic acid in chloroform \vas used as the titrant and methyl yellow as the indicator. Specific directions have been given for the determination of alkaloids in drugs and alkaloidal preparations ( 1 4 ) . Khait ( 4 1 ) has refined and extended the work of Dietzel and Paul ( I d ) for the extraction and determination of alkaloids. AMINES. Dietzel and Paul (14) have determined aliphatic and aromatic primary, secondary, and tertiary amines by the titrimetric procedure used for alkaloids. Hexamethylenetctrainine titrates as a monoacid base. EFFECT OF WATER. This subject has received little quarititative attention. Rlarkunas and Riddick ( 5 6 ) found that large amounts of water in acetic acid gave high results, but amounts u p to approximately 1.5% of the original solvent (about 30 nil.) did not affect the accuracy of the determination. Fritz (21) found that about 3% can be tolerated. From the description of the solvents reported by the different workers it can be concluded that water is more harmful in aprotic than in amphiprotic systems. I t appears that some titrants can be used in benzene or chloroform saturated with water. The linlits of water reported by Riddick and blarkunas and by Frita appear to be the limits for other amphiprotic solvents. Unless definite proof has been obtained, it is advisable to keep the water content lo~v.
LITERATURE CITED

(4).
S I C O T I S I C ACID, NICOTINAMIDE, ASD

RELATED CO~fPOCNDS.

Kahane (39) has developed micro- and semicro methods. He applied the titration in acetic acid as part of a method for analyzing crude products containing nicotinic acid, nicotinamide, and sodium, calcium, and ammonium nicotinates. SGLFONAMIDES. The behavior of eight sulfonamides when titrated in acetic acids was studied by Tomicek (70). The stronger bases may be titrated with crystal violet a8 indicator; the weaker ones are best titrated potentiometrically. Sulfonamides derived from naphthalene were titrated by using their distinct change in fluorescence a t the equivalent point. B.ASICNITROQEN IX OILS. Wittmann (78) has deecribed a rapid, exact potentiometric determination of basic nitrogen in hydrocarbons and hydrogenated coal oils. The oil does not have to be completely soluble in the acetic acid, as the basic nitrogen compounds are immediately extracted into the acid phase. An accuracy of h 0 . 2 mg. of ammonia per liter can be obtained. Wilson ( 7 7 ) described a method for trace organic bases in aromatic and aliphatic hydrocarbons using 0.02 perchloric acid and methyl violet indicator. He found that the presence of a hydrocarbon increased the sharpness of the end point. The end point nil. is sharp to 3~0.02 G-H Solvent. The mixture Palit (60) found most suitable was a 1 to 1 mixture of ethylene glycol or propylene glycol and isoprop)-1 alcohol. The proportion of isopropyl alcohol can be varied from 15 t o 70% v. Perchloric acid was found most suitable as the titrant. Methyl red was the preferred indicator, although methyl orange could be used. A pH meter with glass and calomel electrodes was used for potentiometric titrations. The G-H mixture was regarded by Palit as an almost universal solvent for alkali metal salts of monobasic organic acids. ALKALI METAL SALTS OF A~ONOCARBOXYLIC :ICIUS. Sodium salts of acetic, propionic, butyric, benzoic, cinnamic, mandelic, oleic, and stearic acids titrated satisfactorily. AMINES. Strychnine and brucine titrated with the sharpest end point, that for aniline was fairly sharp, and the error for quinoline, naphthylamine, p-toluidine, and pyridine was too large for this solvent to be of practical use. MIXEDACIDS. Acid mixtures such as nitric and acetic, sulfuric and acetic, gave tvio and three inflection points, respectively, on the titration curve when titrated with sodium hydroxide. S.4LTS OF INORGAXIC ACIDS. Salts of the general formula XOOSa, where X is any negative element, are highly soluble in the G-H solvent and can be titrated accurately. Such salts include metaborates, aluminates, nitrites, nitronates, hypophosphites, hyposulfites, sulfinates, and chlorites. In addition borates, silicates, arsenates, etc., can be titrated. BORIC ACID. This is a strong acid in the G-H Eolvent. A4LKaLI IN SOAP. Free alkali in soap can be readily measured. EQUIVALEKT WEIGHT. The equivalent weight of high molecular weight fatty acids may be determined by a modification of the basic procedure. Methanol-Benzene (1 to 1). Fritz and Lisicki ( 2 2 ) reported titrating several classes of compounds in this solvent using a sodium methylate-solvent mixture as the titrant. A pH meter

(1) Am. SOC. Testing Nuterials, Proc., 25, Part 1, 282 (1925). ( 2 ) Bartlett, P. D., and Dauben, H. J., Jr., J . .4m. Chem. Soc., 62,

1339 (1940). (3) Bell, R. P., Quart. Revs. (London), 1, 113 (1947). (4) Blumrich, K., and Bandel, G., Angew. Chem., 5 4 , 374 (1941). (5) Br@nsted,J. K., Chem. Revs., 5, 231 (1928). (6) Brgnsted, J. N., J . Phys. Chem., 30, 777 (1926). (7) Br@nsted, J. N., Rec. trar. chim., 42, 718 (1923). ( 8 ) Br@nsted, J. N., 2. physik. Chem., A169, 52 (1934). (9) Carlton, C. A., J . Am. C h a . SOC., 44, 1469 (1922). (10) Clarke, B. L., Wooten, L. A . , and Compton, I<. G., 1x0. EN@. C H E Y . , A N A L . ED., 3, 321 (1931). (11) Conant, J. B., and Hall, S . F., J . Ani. Clrern. Soc., 49, 3063 (1927). (12) Conant, J. B., and Werner, T. H., Ibld., 52, 4436 (1930).

46

ANALYTICAL CHEMISTRY
(51) Lavine, T. F., and Toennies, G., J . B i d . Chem., 101, 727 (1933). (52) Lewis, G. N., Valence and Structure of Atoms and Molecules, New York, Chemical Catalog Co., 1923. (53) Lowry, T. M., Trans. Faraday Soc., 20,13 (1924). (54) Luder, W. F., Chem. Revs., 27, 547 (1940). (55) Luder, W.F., and Zuffanti, S., Electronic Theory of Acids and Bases, New York, John Wiley & Sons, 1946. (56) Markunas, P. C., and Riddick, J. A., ANAL. CHEM.,23, 337 (1951). (57) Moore, T. S., J . Chem. Soc., 1907, 1373, 1379. (58) Moss, M. L., Elliott, J. H., and Hall, R. T., ANAL.CHEM., 20, 784 (1948). (59) Nadeau, G. F., and Branchen, L. E., J . Am. Chem. Soc., 57,1336 (1935). . R., TSD. ENQ. CHEX.,ANAL. ED., 18, 246 (1946). (60) Palit, S (61) Palit, S.R., J . I n d i a n Chem. Soc., 19, 271 (1942). (62) Palit, S.R., Oil & Soap, 23, 72 (1946). Palit, S. R., and McBain, J. W.. I n d . Eng. Chem., 38, 741 (1946). Pauling, L., Nature of the Chemical Bond, 2nd ed., Ithaca, N. Y., Cornell University Press, 1940. Ralston, R. R., Fellows, C. H., and Wyatt, S. K., IND. ENG. CHEM.,ANAL. ED.,4, 109 (1932). Ruehle, A E., Ibid.. 10, 130 (1938). Seaman, W., and Allen, E., ANAL. CHEM., 23,592 (1951). Seltz, H., and McKinney, D. S., I n d . Eng. Chem., 20, 542 (1928). Selts, H., and Silverman, L., IND. Eso. CHEM., ANAL.ED., 2, 1 (1930). Tomicek, O., Collection Csechoslov. Chem. Communs., 13, 116 (1948). Trautner, E. RI.,and heufeld, C. E., Australian Chem. I n s t . J . & Proc.. 13.70 (1946). Trautner, E. M., and Shaw, F. H., Ibid., 12, 232, 405 (1945). Virasoro, E., aev. facultad Guim. ind. y agr. (Univ. nacl. litoral, Santa Fe, UVJ.), 19, No. 32, 102 (1950). Vorlander, D., Ber., 36, 1485 (1903). (75) Ibid., 67B, 145 (1934). (76) Vorlander, D., Fischer, J., and Felicitas, W., Ibid., 66B, 1789 (1933). (77) Wilson, H. N., J . SOC. Chem. Ind. (London), 67, 237 (1948). (78) Wittmann, G., Angew. Chem.. A60,330 (1948). (79) Wooten, L. il., and Hammett, L. P., J . Am. Chem. SOC., 57,2289 (1935) (80) Wooten, L. A., and Ruehle, A. E., IND. EX. CHEY.,A N A L .ED., 6, 449 (1934).
I
I

(13) Davis, M. M., and Schumann, P. J., J . Research Natl. Bur. Standards, 39, 221 (1947). (14) Dietsel, R., and Paul, R., Arch. Pharm., 273, 507 (1935). (15) Evans, R. N., and Davenport, J. E., IND. ENQ.CHEM., ANAL. ED.,3, 82 (1931). (16) Ferreira, R. de C., J . Chem. Phys., 19, 794 (1951). (17) Folin, O., and Flanders, F. F., J . Am. Chem. Soc., 34,774 (1912). (18) Folin, O., and Flanders, F. F., J . Bid. Chem., 11, 257 (1912). (19) Folin, O., and Wentn-orth, A. H., Ibid., 7, 421 (1909-10). (20) Fritz, J. S., ANAL. CHEX.,22, 578 (1950). (21) I M . , p. 1028. (22) Fritz, J. S., and Lisicki, N. RI., Ibid., 23, 589 (1951). (23) Gordy, W., J . Chem. Phys., 7, 93 (1939). (24) Hall, N. F., Chem. Rers., 8, 191 (1931). (25) Hall, N. F., and Conant, J. B., J . Am. Chem. Soc., 49, 3047 (1927). (26) Hall, N. F., and Werner, T. H., Ibid., 50, 2367 (1928). (27) Hammett, L. P., and Deyrup, A. J., Ibid., 54, 2721 (1932). (28) Hammett, L. P., and Dietz, N., Jr., Ibid., 52, 4795 (1930). (29) Hantssch, A., Ber., 60B, 1933 (1927). (30) Hantssch, A., Z . Elektrochem., 29, 221 (1923). (31) Hantzsch, A., and Voight, W., Ber., 62B, 975 (1929). (32) Herd, R. L., J . Am. Pharm. Assoc., 31, 9 (1942). (33) Higuchi, T., and Concha, J., J . Am. Pharm. Assoc., Sci. Ed., 40, 173 (1951). (34) Higuchi, T., and Concha, J., Science, 113, 210 (1951). (35) I n d . Eng. Chem.. 43, No. 8, 186 (1951). (36) Izmailov, N. A., Zhur. Fiz. K h i m . , 24, 321 (1950). (37) James, J. C., and Knox, J. G., Trans. Faraday Soc., 46, 254 (1950). (38) Jurecek, M., Chem. Listy, 44, 134 (1950). (39) Kahane, E., Bull. soc. chim. France, 18, 92 (19*51). (40) Kahlenberg, L., J. Phys. Chem., 6 , 1 (1902). (41) Khait, G. Ya., Farmatsiya, 8, 26 (1945). CHEM., 21, 101 (1949). (42) Kolthoff, I. M., ANAL. (43) Ibid., 22, 65 (1950). (44) Kolthoff, I. M., J . Phys. Chem., 48, 51 (1944). (45) Kolthoff, I. M., and Gauss, L. S., J . Am. Chem. Soc., 60, 2516
11Q.181. \__--,.

(46) Ibid., 62. 249 (1940). (47) Kolthoff, I. hi., and Rosenblum, C., Acid-Base Indicators, New York. Macmillan Co., 1937. (48) Kolthoff, I. M., and Sandell, E. B., Textbook of Quantitative Inorganic Analysis, p. 518, New York, Riaemillan Co., 1937. (49) LahIer, V. K., and Downs, H. C., J . Am. Chem. Soc., 53, 888 (1931). (50) Lavine, T. F., and Toennies, G., Am. J . M e d . Sci., 185, 302 (1933).

RECEIVED Xorember 1, 1931.

AMPEROMETRIC TITRATIONS
H. A. LAITINEN
University of Illinois, Urbana, I l l .

ROM the number of papers that have appeared since the first review in 1949 (@), it is evident that the amperometric titration method is gaining momentum and is rapidly attaining maturity as a widely accepted analytical method. Several general and review papers have been published (3, IO, 23, S I , 32, 35, 40,59, 65, 80).
APPARATUS AND METHODOLOGY

Delahay (14), Ringbom ( 6 7 ) ,and Gentry and KerTson (91) described circuits suitable for amperometry. Heyrovskj. (28) has suggested an oscillographic technique for end-point detection. Rius and Serrano (69) used a milliammeter with the dropping mercury electrode in the titration of solutions of relatively high concentration. Parks and Lykken (60) have described the adaptation of amperometric titrations to operations on a reduced scale. Laitinen and Burdett ( 4 3 ) designed a cell with a shielded dropping electrode for the continuous passage of nitrogen during a titration. Berman, Saunders, and Winder (2) suggested a vibrating mercury electrode for polarographic measurements with

moving solutions, but did not apply it to amperometric titrations. Elofson and Mecherly (17) designed a special cell for use a t low temperatures. Vibrating platinum electrodes have been used by Harris and Lindsey ( 2 7 ) and by Rosenberg, Perrone, and Kirk (70). Vyakhirev ( 7 9 ) used lead electrodes for the titration of sulfate with lead. Tomicek, Blazek, and Roubal ( 7 7 ) performed amperometric titrations with bromine in glacial acetic acid. Lyalikov (50) titrated silver nitrate with potassium hydroxide in fused nitrate, using a platinum indicator electrode. Fused potassium nitratepotassium hydroxide mixtures proved superior to fused potassium hydroxide as a reagent because of their less hygroscopic character. A technique somewhat related to the amperometric and deadstop methods has been recently devised by Reilley, Cooke, and Furman (64), and named the derivative polarographic titration. The electromotive force necessary for the passage of a constant, predetermined current is measured. This quantity is related to the slope of the current-voltage curve a t the zero current point. Ringbom (68) has devised a technique involving the use of amperometric indicators. A small amount of polarographi-

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