ANALYTICAL EDITION

I N D U ST RIAL
andENGINEERING
C H E MIS TRY
Harrison E. Howe, Editor

Organic Reagents in Inorganic Analysis’

F. FEIGL
University of Vienna, Vienna, Austria

A LTHOUGH the methods of chemical analysis have been

permanently influenced through the advances in all
fields of chemistry, this influence is not always immediate,
of nickel; its exceptional purity and definite composition, mak-
ing possible direct weighing, afford a direct determination of
small amounts of nickel; and above all-and this is its par-
since in chemical analysis thorough testing and criticism are ticular merit-it is highly specific in its action. The nickel-
necessary and long periods of time frequently elapse before diacetyldioxime reaction indicates for the first time, in that
new methods and procedures become established. This is it hints at the great reservoir of organic compounds, the pos-
also true of the more recently popularized investigation and sibility of a far-reaching simplification of difficult analytical
use of organic reagents. I n inorganic analysis, which is separations through the use of specifically acting organic
undoubtedly one of the oldest branches of chemistry, in- reagents.
organic reagents or purely inorganic reactions have, with a A survey of organic compounds for their use in solving
few exceptions, long dominated, even during a time when analytical problems indicates that much empirical research is
synthetic organic chemistry was experiencing striking necessary, but that certain guideposts and directing principles
triumphs tnrough the evolution of classical syntheses and are available for searching out new reagents or improving old
through the elucidation of constitution, etc., and an abundance reactions.
of compounds was available. Up to the end of the preceding
century only a few analysts devoted much consideration to Salt-Forming Properties and Inner Complex
Compounds

zy
organic reagents and then only where the value of such
reagents was immediately obvious. As pioneers must be First consideration must be given to the salt-forming
mentioned the French chemists, Denighs and Cazeneuve, with properties of the organic compound, which are due to the
whose names are associated analytical reactions frequently presence or the formation of definite acidic atomic groupings;
used. such salt-forming groups are the sulfonic (SOsH)-, sulfinic
The genuine beginning of a systematic research into the (A02H)-, carboxyl (CO0H)-, hydroxyl (OH)-, sulfhydryl
possibilities of organic reagents, however, occurred at a later (SH)-,oxime (NOH)=, and imine (NH)= groups, the
date. It was distinguished by the founding and development hydrogen atoms of which are replaceable by metal atoms.
of the chemistrv of the complex compounds by A. Werner and At the same time conditions must be such in the organic m o l e
his school, further by the improvement of microchemical cule that a complex compound can be formed through the
technic, and finally by the tendency toward rationalization saturation of the secondary valences of the metal atom con-
and simplification of analytical methods. Today it is generally tained as a neutral part in the molecule.
accepted that in the evaluation of analytical methods two In the analytical evaluation of the salt-forming ability of
criteria are determinative: the sensitivity and the specificity an organic compound, as high a sensitivity and specificity

zyxwvutsrqp
of the involved reactions. A comparison by both criteria of as possible are first to be desired, assuming the salt to possess
the effectiveness of inorganic and organic reagents shows that the necessary solubility relations (insolubility in water, solu-
the latter exhibit many intrinsic advantages. bility in organic reagents), and to have a color different from
Although organic substances had heen occasionally used that of the reagent. Although one of the above acid-forming
earlier for precipitations and color reactions [the precipita- groups is indispensable for salt formation, other atoms or
tion of metal oxalates, of hydroxides by organic baees, and the atomic groupings occurring in the molecule frequently exert
Griess reaction (60) for nitrous acid described in 1879, may be essential influences on the specificity of the salt formation as
mentioned], it was only in 1905 that the significance of organic well as on the color and the solubility of the salt concerned.
reagents in the analysis of inorganic eubstances was brought to It is important to observe that in all cases the metal not only
attention in an obvious and emphatic manner. This was by replaces the acidic hydrogen atom but also is bound to other
the nickel reagent, diacetyldioxime (dimethylglyoxime), atoms of the same molecule through the saturation of the
described by L. Tschugaeff, with which A. Rrunck carried out secondary valences of the metal atom (inner complex salt
a series of valuable separations. The Tschugaeff nickel formation). The conditions affecting the dependence of
reaction may still be considered as ideal in a certain sense. analytical effects on constitution are therefore important
Because of the intense color and insolubility of the nickel because, as is well known, condensation and substitution
salt, the reaction furnishes a sensitive method for the detection reactions frequently cause great changes in the structure of
Translation from the German by Harvey C. Diehl, University of Michi- organic molecules, thus modifying the salt-forming properties
gan. of the compounds, and this may be made profitable from an
401
402 INDUSTRIAL AND ENGINEERING CHEMISTRY

analytical viewpoint. In a survey of the analytical evaluation

of new reagents and the improvement of the activity of organic
reagents already known, it is of great significance that certain
VOL. 8, NO. 6

contrast to diacetyldioxime, is very soluble in water. The

zy
example of the dioximes indicates, therefore, that it is possible
to change the molecule of the organic reagent so that its
atomic groupings in organic compounds exert a very definite analytical value may be improved, if the specifically acting
influence on the solubility, color, etc., of the salts, so that group is known and maintained unchanged throughout the
it is safe to speak of the relation between certain atomic variations in the rest of the molecule.
groupings and specific activity. It should be pointed out here, This relation of analytically important properties to
however, that the reaction medium, as well as the definite particular and characteristic groupings is also shown by two
atomic groupings appearing in the molecule, is of great impor- copper reagents-namely, benzoinoxime ($0) ,CsHS-CH(OH)-
tance in the determination of the specificity of organic -C(NOH)-C&, and salicylaldoxime (ZZ?), C,&CH(NOH)-
reagents. Thus a reagent may be highly specific in acid solu- OH. The first reagent is specific for copper in ammoniacal
tion but in alkaline solution its uniqueness is lost or wholly solution, the latter furnishes a separation of copper in acetic
changed in nature. Furthermore, it is often possible, through acid solution; in both cases the organic copper compounds
the addition of certain compounds, to decrease the concentra- are suitable for direct weighing in either macro- or micro-
tion of disturbing ions so much that the trouble may be analytical procedures because of the high purity and definite

zyxwvutsrq
eliminated. composition of the precipitates. With both reagents there
As a starting point for these considerations we may select are produced inner complex copper salts corresponding to
the reagent already mentioned, diacetyldioxime. As is well Formulas 1 and 2.
known, the red insoluble nickel salt of diacetyldioxime is
interpreted as an inner complex compound according to the
formula
HsC-C-G-CHs
II II

zyxwvutsrq
zyxwvutsr
Not only diacetyldioxime but also numerous other syn-
dioximes of the general formula R--C(NOH)-C(N0H)-R
react in the same manner.
As nickel reagents, benzildioxime, COHE-C (NOH)-C-
(NOH)-CCH6, was recommended by Atack (4) and the more
soluble furildioxime, C4H30-C(N0H)-C(N0H)-C4H30,
was recommended by Soule (111). It appears at first, there-
fore, to be merely the atomic group
H
It has been shown that the atomic groupings active in
forming the complex compounds 1 and 2, -C(OH)-
C(N0H)- and
A/OH

zyx
-c-c-
HOI! &OH

which is responsible for the specificity for nickel; that this are responsible for the formation of the green or bright yellow-

zyxwvuts
is true only to a limited extent, however, is shown by the green Cu(l1) salts and that this function is quite independent
behavior of the dioximes, of the other groups attached to the molecule (28). Com-
paring the activity of benaoinoxime with the other acyloinox-

[lp" and
\
NOH imes of the general formula R-CH(OH)-C(NOH)-RI,
is found that for the formation of green insoluble copper salts
the OH- and NOH- groups in a-positions are necessary.
The green copper salts are stable towards ammonia, how-
ever, only if there are also present in the molecule atomic
it

I n these dioximes the specific activity of the dioxime groups groupings capable of occupying the free coordination positions
has been lost. The compounds behave as dibasic acids and of the copper atoms (Formula 1). Accordingly, cyclo-
yield yellow precipitates with almost all metal ions in neutral hexanolonoxime, for example, yields a green water-insoluble
solutions. The aromatic ring, therefore, destroys the specific copper salt of the formula
activity of the two oxime groups. The nickel specificity re- CHI 0
turns, however, when the double bonds of the aromatic rings
have been removed as is shown by the behavior of cyclo-
hexanediondioxime
CH2

@: E ci
which is, however, soluble in ammonia.
The use of benzoinoxime as a specific reagent for copper
has been pointed out; this reagent also precipitates copper
This compound, described by Wallach (I,%), yields a nickel from an ammoniacal solution in the presence of tartrate or
salt which can be differentiated from nickel diacetyldioxime glycerol, making possible the separation of copper from alumi-
only with difficulty; it is produced under the same conditions num, iron, and other metal ions preripitated by ammonia.
and it can be used analytically in the same manner. In mineral acid solution the precipitation of copper is im-
The dioxime just referred to also shows that the insolubility possible. Copper benzoinoxime is also soluble in mineral
of the nickel compound is in no way related to the insolubility acids. On the other hand, according to Knowles (76),
of the reagent in water, for cyclohexanediondioxime, in benzoinoxime is able to separate quantitatively molybdenum,
 zyxwv
zyxwvutsrq
NOVEMBER 15, 1936 ANALYTICAL EDITION

tungsten, and vanadium, the procedures being useful ana-

lytically. However, a true salt of molybdenum or tungsten
with benzoinoxime is not produced, but probably only addi-
sensitive detection of zirconium. A recent investigation by
Mayr (87) has shown that a-nitro-P-naphthol may likewise
be used for the separation and determination of cobalt.
403

zyxwvutsrqpo
tion compounds between molybdic or tungstic acid and Undoubtedly this again involves the formation of an inner
benzoinoxime of the nature of the so-called heteropoly acids. complex trivalent cobalt salt.
Salicylaldoxime, which precipitates copper quantitatively in Insoluble inner complex salts, in which the organic com-
an acetic acid solution, also, according to Holzer (70), ponent possesses the character of a dyestuff, as in the pre-
separates palladium, but not platinum, quantitatively from viously mentioned nitrosonaphtholates, are called color
acid solution, the precipitate also being suitable for weighing. lakes. The color lakes of alizarin and other hydroxyan-
Both 01the reagents mentioned therefore are not limited to thraquinones possess considerable analytical significance.
one element in their activity. Such reagents are designated Atack (5) was the first to point out that aluminum could be
as specific reagents and are differentiated from the so-called detected with great sensitivity by means of the red color
special reagents-that is, those which are characteristic for formed with alizarin8 (alizarin sulfonic acid). This is a
a single substance. It should be noted that only a very few question again of the formation of an inner complex salt
special reagents are available. However, in numerous cases corresponding to the coordination formula

zyxwvutsr
through a choice of suitable experimental conditions a limita-
tion of the activity of a specific reagent may result and the A1/3
practical effects of a special reagent be achieved.
I n a review of the specific activity of definite atomic group-
ings mention must be made of the cobalt reagent, a-nitroso-
/?-naphthol, described by Illinsky and von Knorre (71),
which forms a reddish brown inner complex cobalt (111)
salt
o=N--c0/3
Atack, Underhill and Petermann (119), and Yoe and Hill
(124) applied the alizarin reaction to the colorimetric deter-
mination of aluminum. Quinalizarin
O H 0 OH
and which is one of the oldest organic precipitation reagents
known. Also the isomeric /?-nitroso-or-naphtholate of cobalt
possesses an inner complex character which in color and solu-
bility is inappreciably different from the compound first men-
tioned. Both cobalt nitroso compounds have, until recently,
been used merely as precipitants, since the cobalt precipitates
formed in acetic a d d solutions do not have the theoretical also forms lakes, and Fischer (50)has recommended the beryl-
composition. Recently Mayr and Feigl (88) have succeeded, lium lake of quinalizarin for the detection and determinat.ion of
by converting the cobalt into the trivalent state before precipi- beryllium. The magnesium lake of quinalizarin, according
tation, in obtaining a pure Co(II1)-nitrosonaphtholatewhich to Hahn (63), is suitable for the sensitive detection and for
after drying is suitable for weighing, and furnishes, therefore, the colorimetric determination of magnesium.
a direct determination of cobalt. That the inner complex- Finally, there should be mentioned aurintricarboxylic acid,
forming groups are responsible for the cobalt affinity of both the yellpw solution of which gives a red aluminum lake,
of the nitrosonaphthols is shown by nitroso R-salt, probably corresponding to the coordination formula
N-OH

recommended by van Klooster (73) as a cobalt reagent, as Aurintricarboxylic acid was recommended as an aluminum
well as the behavior of 2-isonitroso-1-ketotetralin reagent by Hammett and Sottery (65) and wag later used by
0 Winter and co-workers (123) and by Roller (105) for the
colorimetric determination of aluminum.
There should also be emphasized the lake which aluminum
/\/\C=NOH forms with the dyestuff of fustic wood, the so-called morin,

investigated by Strauss and Ekkard (118). The latter com-

pound behaves toward cobalt salts in the same manner as the
nitrosonaphtholates. Iron and palladium are also precipitated
as inner complex salts by nitrosonaphthol and by this means
may be separated from the similar elements aluminum and
K
platinurn. It is to be noted that in acid solution zirconium observed by Goppelsroeder (69). The reagent produces with
yields with the isomeric nitrosonaphthols insoluble zirconyl aluminum salts in neutral or acetic acid solution an intense
compounds, (C10H602N)2(Zr0),of which that with the a-form green fluorescence, which is due to a neutral aluminum salt
is colored green-yellow, that with the B-form, red. The of morin, A1(C1~H907)3,in colloidal solution, and makes
latter is recommended by Bellucci and Savoia (7) for the possible the recognition of 0.005 y of aluminum (20, 108).
404 zy
zyxwvutsrqponmlk
zy INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 8, NO. 6

zyxwvuts
Although the morin reaction is the only fluorescent reaction
of metals with organic compounds used analytically up to
the present time, it is expected that still other examples will
be found.
The ammonium salt of nitrosophenylhydroxylamine,
C6H6N(NO)ONH4,recommended by Baudisch (6) in 1909
has been very wide!y used. This compound retains the name
“cupferron,” because it was first shown to be very suitable
for the separation of copper and iron from numerous other
oxine, too, the formation of inner complex salts depends on
the atomic groupings as set forth in the coordination rules
already given; accordingly the halogen derivatives of
hydroxyquinoline such as 5,7-dichloro- and 5,7-dibromo-
hydroxyquinoline are suitable for analytical purposes and
even present certain advantages over the parent compound.
Although hydroxyquinoline reacts with numerous metals,
the reagent can be utilized in the solution of numerous prob-
lems in gravimetric analysis if control is exercised over the
metals. Here also, an inner complex salt is formed according conditions of precipitation (8).
to the formula Two o-aminocarboxylic acids able to form inner complex
~ N - N compounds, which have been adapted recently to the pur-
--I I poses of gravimetric analysis, are anthranilic and quinaldinic
acids. By means of anthranilic acid Funk (63) and co-
o w 0 workers have carried out a series of gravimetric determinations
Me of divalent metals and have shown that through the bromo-

zyxwvutsrq
metric determination of anthranilic acid a volumetric deter-
Later it was shown, especially by American investigators,

zyxwvutsrq
mination of the metal is possible. Quinaldinic acid was used
that with control of the conditions of precipitation, a series by Rby and Bose (99) for the gravimetric determination of
of otherwise difficult separations of various metals can be copper, cadmium, and zinc. I n the analytical use of anthra-
effected and appreciably simplified. Thus the precipitation nilic and quinaldinic acids inner complex salts are formed ac-
of thorium (116) and the separation of gallium (93) from Al, cording to the formulas
Cr, In, Ce, and U, of uranium (6Q)from Al, Zn, Ca, and Mg,
of bismuth (96) from As and Sb, of tin (54,95) from Co, Ni, 0
Zn, Mn, As, Pb, and Sb, and finally the separation of zir-
conium (15) from A1 have all been made possible by cupferron.
I n all these reactions there are again formed inner complex
salts with the metal ion precipitated. These compounds are
suitable forms in which to precipitate the metal, but are not
satisfactory for weighing because the metallic compound is
always contaminated with some of the reagent which is in-
soluble in water. The solubility in water (or in ammonia,
alkalies, or acids) plays an important role in the practical Of organic reagents in which a sulfur atom is involved in the
use of organic reagents, especially for quantitative purposes. formation of inner complex compounds, there should first
When an alcoholic or acetone solution of an organic reagent be mentioned dithizone, thionalide, and rubeanic acid.
is added to an aqueous solution the problem is always com- Dithizone is the commercial name of a compound easily
plicated by the danger that the reagent will be thrown out as obtained, diphenylthiocarbazone,
such by the water, thus contaminating the precipitate, from
which it can be removed only with difficulty. In such cases
the conversion of the precipitate into a form suitable for H
s8; : : ; : ; :C
<
S
weighing, through ignition or other treatment, is necessary;
the essential advantage of a low percentage of the determined investigated by Fischer (51), which reacts with numerous
material in the weighed precipitate is, however, then lost. metals partly in the keto form as written, partly in the enol
An example of an organic reagent forming inner complex form
compounds which have a satisfactory solubility and the
theoretical composition is 8-hydroxyquinoline. This com-
pound, which goes under the commercial name of “oxine,”
was introduced into analytical practice by F. L. Hahn (1926)
and by R. Berg (1927). Oxine is very soluble in alcohol and Derived from either the keto or the enol form, inner complex
acetic acid and with numerous metals yields insoluble, for salts result corresponding to the coordination formulas
the most part brightly colored, inner complex salts corre-
sponding to the coordination formula

b-ihe
The metal salts of oxine as a rule may be dried a t 105” to
140” C. and weighed. The phenolic nature of the reagent,
moreover, makes possible a volumetric and a colorimetric
determination, the former through bromination of the oxine
with the formation of 5,7-dibromo-8-hydroxyquinoline,the
latter through the color reaction with phosphotungstomolyb- The first, produced in acid or neutral solution, is com-
dic acid, according to Folin and Denis (529, or through pletely insoluble in water, although easily soluble in organic
the coupling of the oxine with diazo oompounds in alka- solvents, yielding intensely colored solutions ; the latter form
line solution. These volumetric and colorimetric deter- is preferred for univalent metals, and is equally insoluble in
minations may be carried out either on the solution of the water but also insoluble in organic solvents. In spite of the
purified oxinate in acid or on the excess of reagent. With lack of specificity in its action, by standardization of the
 zyxwvutsrqpo
NOVEMBER 15, 1936 ANALYTICAL EDITION 405

zyxwvutsr
reaction conditions, dithizone furnishes numerous sensitive
and important tests and colorimetric quantitative procedures.
Thionalide is the commercial name of thioglycollic acid
P-aminonaphthalide, HSCH2C0.NHCloH,, recommended
these salts is exceeded only by the stability of the corre-
sponding cyanide complexes, as is shown by the facts that the
rubeanates are soluble in potassium cyanide solutions and are
not precipitated from solutions containing cyanide. The

zy
by Berg and Roebling (IO) as an analytical reagent. It is sensitivity of the detection of copper, nickel, and cobalt by
capable of forming inner complex salts corresponding to the means of rubeanic acid is very high; in the form of a spot

zyxwvu
coordination formula reaction as little as 0.006 y of copper, 0.012 y of nickel, and
Me 0.03 y of cobalt can be detected. I n a mixture of these three
,**'\s

zy
metals, the identification is still possible by means of a

zy
C~~H,--NH,~' capillary separation procedure and in this manner 0.05 y of
k d H 2 copper can be recognized in the presence of 20,000 times as
much nickel (43).
I n neutral solutions thionalide reacts as a derivative of A compound, capable of forming inner complex salts of
hydrogen sulfide with all heavy metals which are precipitated high sulfur content with heavy metals, is 2,5-dimercap-
by the sulfide ion. Noteworthy is the precipitation of metal tothiodiazol, discovered by Dubsky and co-workers (20)
ions from mineral acid solution: all metal ions up to Cd(I1)
I

This compound, functioning according to the tautomeric

and Pb(I1) are separated in the form of yellow or white equilibrium
precipitates. Although the depth of color of the heavy metal
sulfides is not carried over in spite of the sulfur linkage, the N-N
I, I, HN-N
sensitivity of the reaction is far greater than that of the sul- HS-8 8-SH _r S=c! 4-SH
fide precipitation. For example, in 5 ml. of solution arsenic
can be identified in a dilution of 1 to 100,000,000 by the Y $'
formation of a white precipitate. With thionalide also much
of the difficulty due to its lack of specificity may be overcome reacts in the mercapto form with numerous metals, forming
by control of the conditions of precipitation-for example, inner complex salts of the following form:
by precipitating from mineral acid solution, or from alkaline
solutions containing tartrate or cyanide. Of particular value HN-C=S
is the reaction with thallium in alkaline solutions containing
tartrate or cyanide, which is very specific and sensitive to a
dilution of 1 to 10,000,000.
Thionalide also affords certain quantitative determinations. Of particular interest is the color of the bismuth salt, which
The copper and mercury salts may be isolated as such and is deep red in contrast to the colors of other metal salts which
after drying a t 105" are suitable for weighing; moreover, the are white to yellow. Here again the specificity caused by the
organic component of the precipitate may be determined difference in color is based on the formation of an inner com-
iodometrically after removal of the excess reagent and the plex ring as pictmed above, and it is independent of the groups
metal content calculated accordingly. Thioglycollic acid, which can be easily introduced in place of the imino hydrogen
the parent compound of thionalide, has been recommended atom.
by Lyons (85) for the colorimetric determination of small
amounts of iron; it also shows the property characteristic Specificity in Normal Salts
of thionalide of forming insoluble inner complex salts. The
effect of the amino group introduced into the series thio- So far only those reagents have been mentioned which,
glycollic acid-thioglycollic acid analide-thioglycollic acid- because of the neighboring position of the salt-forming and
P-aminonaphthalide is shown by the increasing insolubility coordinating groups, have offered the possibility of forming

zyxwvuts
of the metal salts (9).Rubeanic acid has recently been recom- the so-called inner complex salts. As pointed out, such inner
mended by Rky and R&y (100, 101) as a qualitative reagent complex compounds are frequently characterized by an
for copper, cobalt, and nickel. This compound, which is the abnormal solubility and by a deep coloration. These two
diamide of dithioxalic acid, exists in solution in equilibrium properties frequently contribute a high sensitivity to methods
with its tautomeric (aci), diimido, form, according to for the detection and determination of metals but, on the
other hand, at times leave something to be desired with
SG-NHZ
A
S -NH2
*
HS-C=NH
HS--L=I\"
S-C=NH
* 2 H + + [ S- =NH ] -- respect to specificity. This is readily understood, inasmuch as
the ability of nitrogen, oxygen, and sulfur atoms to coordinate
in the formation of inner complex salts is not specific in action
The acid form yields colored insoluble nickel, cobalt, and but is exerted toward numerous metal atoms, as is shown by
copper salts corresponding to inner complex compounds of the numerous examples in that great class of substances, the
formula ammines and aquo compounds.
c c I n attempting to arrive a t a state in which the greatest
possible number of specific reagents is available, those organic
compounds which are merely capable of forming normal
heteropolar salts should also be investigated for their analyti-
cal applications. Actually such compounds are frequently
These complex salts are produced when the concentration of highly specific in their activity. Thus it has long been known
the aci form of the rubeanic acid is so great that the solubility that arsenic acid precipitated white insoluble zirconium arse-
product of the rubeanate formed is exceeded; as is seen from nate from zirconium salts in solutions strongly acid with nitric
the above equation, this occurs when the hydrogen-ion con- or hydrochloric acids. Rice, Fogg, and James (103) were the
centration is diminished by the addition of sodium acetate, first to find that this property of arsenic acid was also char-
ammonium acetate, or alkalies. The copper, nickel, and acteristic of organic derivatives of arsenic acid-for example,
cobalt compounds, precipitated quantitatively from strongly phenylarsonic acid. This acid makes possible the determina-
ammoniacal solution, when once formed, are insoluble in tion of zirconium and its separation from titanium and
dilute mineral acids; this is in harmony with the idea that calcium. Thorium, which is very similar to zirconium, is
these compounds are inner complex salts. The stability of precipitated by phenylarsonic acid only in solutions
406 INDUSTRIAL AND ENGINEERING CHEiMISTRY
buffered with acetate; this makes possible the determination
of zirconium and thorium in the presence of each other by the
same reagent. That the -AsO(OH)z group alone is respon-
zyx
zy
VOL. 8 , NO. 6

the violet silver salt of which permits the identification of

silver in a dilution of 1 to 5,000,000, the most sensitive
method known for silver up to the present time (36). p-Di-
sible for the activity of the organic derivatives of arsenic acid methylaminobenzalrhodanine has the advantage of yielding
has been proved by Arnold and Chandlee (3) who showed an insoluble silver salt but the disadvantage that the reagent
that n-propylarsonic acid was equally satisfactory as a reagent must be used in alcohol or acetone solution. Accordingly the
for the quantitative estimation of zirconium. It should be reagent is excellent for qualitative purposes but is not usable
noted that p-n-butylphenylarsonic acid also precipitates iron for gravimetric determinations, because the reagent is
quantitatively ( 1 7 ) . thrown down by water and cannot be quantitatively removed
Phenylarsonic acid, in which substitutions have been made from the precipitate of silver salt. A survey of the possibilities

zyxwvutsrq
zyxwvutsrq
in various positions and in various manners, has been shown of improving the reagent shows, however, that rhodanine
by Feigl and his co-workers to function just as the parent also condenses with sulfonated aldehydes-for example, with
compound (27, 46). This made possible the introduction of a o-benzaldehydesulfonic acid yielding a sulfonated benaal-
group which contributed color to the molecule with subsequent rhodanine which is readily soluble in water, alkalies, and acids
improvement in the sensitivity of the reaction. An example (3s)*
of this is p-dimethylbenzeneazophenylarsonic acid (27,46) by Among the organic heavy metal compounds which do not
means of which 0.1 y of zirconium can he detected by a spot belong to the group of inner complex compounds must be
reaction. Further examples of the specific activity of more mentioned the cadmium salt of mercaptobenzothiazole
simply built organic compounds are indicated by the salt-
forming properties of sulfinic acid, RSOSH, and the analogous
seleninic acid, RSe02H. It has been long known (116) that

zyxw
benzenesulfinic acid and ferric salts in mineral acid solutions
yield a difficultly soluble, orange-yellow precipitate of the
formula Fe(02SCJ35)3. Other aromatic sulfinic acids behave
in II. similar manner, substitution in the aromatic nucleus
having no effect. The analogous aromatic seleninic acids, NHs
according to Feigl and Anger (M), also form insoluble yellow According to Spacu and KuraF; (112) this compound is pro-
ferric salts. This same work has also shown that tin (IV), duced by precipitation from an ammoniacal cadmium solution
ceric (IV), thorium (IV), and uranium (IV) salts are precipi- with mercaptobenzothiazole in the form of a yellow precipitate
tated in strongly acid solutions by sulfinic and seleninic acids. which is sufficiently pure to permit direct weighing in gravi-
The sulfinic and seleninic acids, therefore, exhibit a noteworthy

zyxwvutsrqp
metric work. The reagent is of particular value for the separa-
specificity in action and this activity is again Iocalized in tion of cadmium from copper, since copper is precipitated in
particular groups. In contrast to the arsonic acids mentioned acid solution, cadmium being determined quantitatively in
previously, in which it was irrelevant whether the arsonic the filtrate from the copper precipitate.
group was coupled with aromatic or aliphatic residues, a Even among the alkali and alkaline earth metals the for-
direct combination of the sulfinic or seleninic groups with an mation of normal salts may make possible a differentiation of
aromatic ring is necessary (38). Of the compounds C&k%"
CsH,CH2S02H, and CJ3,S02H, only the first has the power similar metals, as shown by the following examples. By
means of rhodizonic acid
of precipitating the above metal ions from acid solution.
According to experiments to be reported later, it seems
possible to use sulfinic acid for the quantitative macro- and
microdetermination of the metals mentioned above (as well
as for molybdenum and tungsten) and for their separation
from other metals.
A further example of the specific action of certain atomic
groupings in which no complex formation is involved is the barium and strontium may be detected in the presence of
heterocyclic compound rhodanine magnesium and the alkali metals according to Feigl (26),
and by maintaining certain experimental conditions barium
HN CO may also be identified in the presence of calcium and stron-
tium, and strontium in the presence of barium and calcium.
A satisfactory reagent for gravimetric analysis has been found
in picrolonic acid
and its derivatives, which were investigated by Feigl (30).
The imino hydrogen atom of rhodanin is replaceable by silver,
mercury, gold, and palladium, producing a precipitate of
yellow metal rhodanine compounds in acid solution. Because
of the reactivity of the hydrogen atoms of the CH2 group in I
the rhodanine molecule, condensation with numerous alde- NO8
hydes and ketones is possible and all the derivatives so ob-
tained have the same properties as the parent compound which forms insoluble salts of high molecular weight and of
with respect to its precipitating ability. Thus, by the intro- definite composition; the reagent was first recommended by
duction of a chromophore group, colored silver salts can be Kisser (78) for the microchemical identification of potassium
obtained. Such a reagent is p-dimethylaminobenzalrhodanine and has since been used for the gravimetric estimation of
potassium (IN), calcium (8,21),lead (66),and thorium (67).
HN CO According to Poluektoff (97) potassium can be identified by
r7 means of the water-soluble sodium salt of p-dipicrylamine,
owing to the formation of an orange-yellow precipitate of
the following formula:
NOVEMBER 15, 1936 ANALYTICAL EDITION 407

intense red, water-soluble complex ion (111) which is stable

toward dilute acids. This complex belongs to the hexam-

zyxwvutsr
zyxwvutsrq
mine type, since the six coordination positions of the iron atom
are occupied by the nitrogen atoms of the three molecules of
the organic base. Of especial interest is the great sensitivity
and stability of the ferrous dipyridyl and ferrous phenan-

zyxwvutsrqp
This reaction is specific for potassium in the presence of the throline reactions, by means of which it is pomible to detect
elements of groups 4 and 5, with the exception of rubidium and even traces of ferrous salts (and therefore ferric by reduction).
cesium, and only large amounts of ammonia must be pre- The reactions have been made the basis of a very sensitive
viously removed. The identification of the NHd group is now colorimetric determination of iron by Feigl and Hamburg
possible by direct salt formation. This is by means of the (42) but the procedure is difficult to carry out. I n both re-
sensitive reaction proposed by Riegler (104) involving p- agents the activity is due to the presence of the group
nitrodiazobenzene .
o~N-CI>-N~C~
nitrosamine
Vd
and alkali yielding the red ammonium salt of p-nitrophenyl-
but the activity of this group is appreciably influenced by
O~N-~-N=N-ONH, substitution in the aromatic ring, as is shown by the examples,
6,6’-dimethyl-2,2’-dipyridyl (I), 6,6’-diamino-2,2’-dipyridyl

zyxwvutsr
Only slightly investigated from an analytical viewpoint
up to the present time are the reactions of complex metallic
acids with organic bases. A few examples will indicate that
this field is capable of expansion: (Bib)- is precipitated by
cinchonine (84) and oxine (II), [Cd(CNS)J -- is precipitated
by pyridine (lor), and cadmium can be determined volu-
metrically by means of &naphthoquinoline (11). Recently
(11),and 2(2-pyridyl)-quinoline (111).

I I1

0-0s
Krumholz and Krumholz (80) discovered a specific and sensi-
tive test for zinc in the reaction of a basic styryl dye with

zyxwvuts
--.

zyxwvutsr
[Zn(CNS)d] N N
Finally it must be pointed out that normal salt formation
with organic compounds plays an important role in the I11
identification and estimation of anions. Well known are the
gravimetric and volumetric methods for the determination of In spite of the apparently minor substitution, these com-
sulfate and tungstate by means of the organic base benzidine pounds are incapable of forming the red ferrous complex.
(74, Qq) and of nitrate by the base nitron (16). Thelatter has It should be observed that o,a‘-dipyridyl and a,a‘-phen-
recently been applied by Geilmann and Voigt (56) to the anthroline also form adctition compounds with other metals,
gravimetric determination of perrhenate. The salt formation although in acid solution a color reaction occurs only with
with methylene blue is the basis of the best macro- and iron and to a slight extent with copper, cobalt, and nickel
microdetermination of perchlorate ( l e ) , and Allen and Fur- ions. A great excess of reagent should be added, if necessary,
man (1) have recently recommended triphenyl tin chloride, in the identification or determination of iron in the presence of
(CsH&SnC1, for the gravimetric determination of fluorine, the metals mentioned.
the insoluble fluoride having the nature of a normal salt. A very characteristic example of the activity of an organic
reagent as a neutral conptituent is given by the well-known
Neutral Constituents in Complex Salts and potassium xanthate reaction for molybdenum, investigated
Adsorption Compounds by Malowan (86) and by Koppel (79). There is produced the
compound MoO,[SC(SH) (OC2H5) 12 in which the xanthic acid
All the organic reagents mentioned previously, because of functions as a neutral constituent. The activity here is
their acidic character or the additional presence of groups associated with a definite atomic grouping, for it has been
possessing residual valence, have had the power of forming shown that other xanthates react in the same manner as
normal salts or inner complex salts. Experience shows, ethyl xanthate. The activity of benzoinoxime toward molyb-
however, there are many compounds of useful nature which dates and tungstates, which are precipitated in acid solution
do not possess hydrogen atoms replaceable by metals, but as mentioned earlier, appears to involve the addition of ben-
which, by means of secondary valence forces alone are able zoinoxime to molybdic or tungstic acids.
t o form addition products with inorganic compounds. This There should finally be listed the identification of sodium
addition t o the metal of one or more molecules of the organic as sodium zinc uranyl acetate (77), in which it is assumed
reagent as a “neutral constituent” may produce insoluble or that the cause of the insolubility is the high molecular weight
characteristically colored complex compounds. Of this type of the compound [NaZn(UO2),](CH&00)9 9Hz0.
of reaction we have all too few examples. Thus, a,a’-dipyridyl In all the complex compounds previously mentioned there
(I) and a,a’-phenanthroline (11) were found by Blau ( I S ) has always been a stoichiometric relation between the organic
t o yield with ferrous salts the component and the metal atom involved. Combinations of
organic components by auxiliary valences in nonstoichiometric

0-0<IR3
N
I
N

N N
ratios, such as the so-called adsorption compounds, are also
of importsnce in analytical chemistry. The oldest known is
the iodine-starch reaction, which is used for the identification of
iodine and of oxidizing substances and has numerous applica-
tions in volumetric analysis. Similar to the starch reaction is
the colored adsorption compound formed by the action of
I1 iodine or bromine on a-naphthoflavone (102).
408 zy
zyxwvutszy
zy INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 8 , h.0. 6

converted to nickel diacetyldioxime by reaction with di-

acetylmonoxime and then with a nickel salt, and identified
and estimated as such (48, 68). Hydroxylamine may also
be converted to yellow copper salicylaldoxime by reaction
with salicylaldehyde and copper acetate (31) and in this
manner be identified and determined quantitatively even in
The coloration of magnesium hydroxide by various dyes or the presence of hydrazine (92).
alkaline solutions of dyes, which is used analytically, is again

zyxwvutsrqpo
The activation of boric acid by polyvalent alcohols such as
probably an adsorption phenomenon; probably salt formation mannite, glycerol, etc., has been long known ( I d ) . The man-
with the dye occurs on the free surface of the magnesium nite- or glycerol-boric acid formed, in contrast to pure boric
hydroxide, as all the dyes found to be suitable are acidic in acid, acts as a monobasic acid of such strength that it liberates
character. Recommended for the identification of small carbon dioxide from carbonates and may be titrated directly
amounts of magnesium are alkaline solutions of the dyes using phenolphthalein as indicator. This synthesis of boric
quinalizarin (64); titan yellow (76), and p-nitrobenzeneazo- acid complexes with polyvalent alcohols, the constitution
a-naphthol (27). There should also be mentioned in this of which has been investigated by J. Boeseken, may be used
connection the convenient differentiation of magnesite from for the volumetric determination of boric acid (19, 67).
dolomite described by Feigl (35),based on the coloration of Hahn (62) has recently worked out a very sensitive method
magnesite by diphenylcarbazide. The phenomena associated of detecting traces of boric acid. An analogous intensification
with the coloration of crystalline and gelatinous precipitates of acidity through combination with polyvalent alcohols also
have not yet been adequately investigated, although it is as- occurs with telluric (106)and germanic acids (118)and Poluek-
sumed that a series of specific colorations may be found for toff (98) has very recently shown that a volumetric determina-
use in analytical chemistry. tion of germanium is possible by this means.
Adsorption compounds between inorganic and organic Inorganic substances can also be employed indirectly in the
substances are also applicabIe t o quantitative analysis. Thus, synthesis of characteristic organic compounds, chiefly because
Moser (92) has shown that Fe, Al, Cr, Sn, Zr, Ti, and Th are of their oxidizing or reducing properties. Thus, by means of
precipitated in acetic acid solutions by tannin; and that certain oxidizing agents colorless benzidine is easily con-
tungsten is quantitatively precipitated from a sulfuric acid verted into a blue meriquinoid oxidation product
solution of a tungstate by tannin. Apparently the precipita-
tion involves the formation of adsorption compounds between

zyxwvutsrqpon
tannin and the hydrolysis products of the metal salts. The
adsorption compounds formed by certain organic dyes have
found important application in volumetric analysis as adsorp-
tion indicators which have proved of excellent utility in the
determination of end points, an application discovered by This change is produced by higher metal oxides, oxidizing
K. Fajans and later investigated by numerous other workers and autoxidizing substances, and certain easily reduced
(78)* complex compounds. By this means benzidine becomes a
reagent for manganese (24, SS), cerium (as), lead (18),
Organic Synthesis Involving the Substance copper (47), thallium (24), phosphoric acid (34, 36, 37),
to Be Determined cyanide (110), silicate (45), persulfate (89), and chromate
(114). Similar to benzidine are 2,7-diaminofluorene (109) and
Fundamentally different in principle from all the examples tetramethyldiaminodiphenyl methane (117) which also form
previously considered for use as analytical reagents is colored meriquinoid compounds. According to unpublished
the procedure in which the substance to be identified or experiments it is possible by color reactions to identify
determined is converted by synthesis into characteristic selenium by the oxidizing effect of selenium dioxide on organic
organic compounds. This conversion may be carried out in compounds. Tin and vanadium may be identified by the re-
various ways. First, it may be accomplished by the direct ducing action of their lower valence states on cacotheline, a
synthesis of an organic compound. An example of this is brucine derivative. This reaction, which was shown to be

zyxwvuts
the well-known qualitative and quantitative method of very sensitive by Gutzeit (61) and Ephraim (E?),consists in
Griess (60) for nitrous acid, in which sulfanilic acid is diazo- a very characteristic color change from yellow to violet.
tized by the nitrous acid, and then coupled with a-naphthyl- Finally, inorganic substances may be involved in organic
amine with the production of color. The great variation
syntheses because of their catalytic activity, or on the other
possible in the amine and in the coupling component used in- hand inorganic reactions may be catalytically accelerated by
dicates that the formation of the -N=X-- group is essential. organic materials. Such cases have been but seldom observed

zyxwvuts
The identification and determination of hydrogen sulfide and described, but that it is possible in principle has been
by the synthesis of methylene blue from p-aminodimethyl- shown by Feigl and his co-workers. The reaction 2NaN3
aniline, hydrogen sulfide, and ferric chloride, according to
Fischer (49),may also be cited. Further examples are the
+ +
Iz = 2KaI 3N2 is accelerated by carbon disulfide, in-
volving the intermediate action of sodium azidodithiocar-
well-known fluorescein test for bromides, in which red tetra- bonate; this makes possible not only the very sensitive detec-
bromofluorescein (eosin) is formed (65),the identification of tion of carbon disulfide but also a direct iodometric determina-
sulfurouP acid by the decoloration of malachite green (121), tion of azides (39). The acceleration of the reaction
and the sensitive detection of boric acid by means of hydroxy-
anthraquinones (44)in which an inner complex boric acid ester
is formed. By means of the latter reaction, through the q ; H z +B r a+
addition of a 0.01 per cent solution of quinalizarin in concen-
trated sulfuric acid to a drop of the unknown solution, as
little as 0.067 of boron may be identified. Hydrazine may
be detected by condensation with benzaldehyde or even better
with salicylaldehyde forming insoluble aldazines @ I ) ,
qi:-O +HBr

C&cCH=N-N=CH-Cas, and the precipitate may be by alkali iodides, first described by Goldberg (58), makes
weighed directly, after purification, Hydroxylamine can be possible the specific identification of iodides (41). According
NOVE.MBER 15, 1936 zyxwv
zyxwvutsrqpo
zyxwvu ANALYTICAL EDITION 409

zyxwvu
to unpublished experiments a very sensitive test for iodide 2. The reactions of inorganic substances with organic

zy
and bromide seems possible by their catalytic effect on reagents can be divided into the following types: (a) forrna-
colored organic compounds. tion of normal salts, (b) formation of inner complex salts,
(c) formation of complex compounds with organic components
Masking Reagents as neutral constituents, ( d ) formation of adsorption com-
As organic reagents should also be considered certain types pounds, ( e ) direct synthesis of organic compounds lacking the
of compounds the addition of which limits the activity of characteristics of salts, (f) participation as oxidizing or reduc-
other reagents. As is well known, the concentration of a ing agents in the synthesis of organic compounds, and (9)
given ion in solution may be so diminished by the addition of catalytic activity in the synthesis of organic compounds.
substances which unite with the ion t o form complex salts 3. A methodical investigation of all the types of reactions
that an ion product sufficient to form a precipitate or cause a gathered under (2) promises to yield new and valuable
color reaction is no longer obtained. Thus we speak of the reagents. Few of the reactions considered up to the present
“masking” of a reaction, and call the reagent responsible for time have been of types (a), (c), or (g), especially catalytic
the disappearance of the ions necessary for the reaction, the reactions and those reactions which yield fluorescent sub-
“masking reagent.” There are numerous organic compounds stances.
capable of acting as masking reagents. The precipitation of 4. The effectiveness of the reagents of all the types
heavy metal ions as hydroxides is largely prevented by the gathered under (2) depends on the specific atomic groupings
alkali salts of hydroxy acids and by polyhydroxy compounds contained in the molecule. With a knowledge of the specific
such as tartrate, citrate, glycerol, mannite, and various sugars. activity of definite groups it is possible to work systematically
Occasionally the masking may be so complete that the forma- toward the improvement of the reagents.

zyxwvutsrq
zyxwvutsr
tion of many inner complex salts may not occur-for example, 5. Distinction must be made between specific reagents
precipitations with oxine or color reactions with thionalide. and special reagents. The former react in a definite manner
Through deliberate selection of suitable masking reagents toward various substances, while the latter are limited in
it has already been possible to secure wide applications for activity to a single substance. Up to the present there are
these reagents. Sulfosalicylic acid was recommended by only a few good special reagents. For practical purposes,
however, the activity of specific reagents can be adequately

zyxwvutsrqp
Moser (00,Ql) as a precise, fractional masking agent. The
masking of certain refictions of mercury, copper, nickel, and limited by the careful control of conditions, the use of mask-
cobalt by cyanide and thiocyanate has been known for a long ing reagents, etc., t o make them widely applicable.
time. The alkali salts of many organic acids are used as 6. In view of the simplification of colorimetric methods
buffers for the regulation of hydrogen-ion concentration. A and the improvement in accuracy of colorimetric measure-
characteristic example in the analysis of anions is that sug- ments by means of the photoelectric colorimeter, an in-
gested by Kurtenacker (81,82, 83) in which sulfite is masked creasing significance must be attributed to the discovery
by the addition of formaldehyde, forming sulfoxylates which of new color reactions and of peptizing agents for insoluble but
are stable toward iodine, making possible an excellent iodo- colored precipitates.
metric titration of thiosulfate in the presence of sulfite. 7 . Associated with the vast numbers of organic compounds
Of greater importance are organic compounds which can available for use in analytical chemistry is the danger of an
be used as protective colloids in the preparation of stable unnecessary increase in the number of organic reagents. In
sols of insoluble metal salts for colorimetric purposes. For this work, therefore, only those reactions should be described
this purpose gelatin, egg albumin, dextrin, and gum arabic which display significant improvements in sensitivity and

zyxw
have long been used. Researches with V. Anger, which have specificity or have a bearing on the theory of specific affinity.
not yet been completed, indicate that the water-soluble cellu-
lose ethers are excellent and versatile peptizing agents. With Literature Cited
the development and improvemen3 of colorimetric methods Allen, N., and Furman, N. H., J . Am. Chem. SOL, 54, 4625
by the use of the photoelectric cell, color reactions with or- (1932).
ganic reagents and the dispersion of insoluble compounds Alten, F., and eo-workers, Biochem. Z., 265, 85 (1933).
Arnold, F. W., and Chandlee, G. C., J . Am. Chem. Soc., 57,
with the help of organic substances will doubtless receive 8 (1935).
increasing attention. Atack, F. W., Analyst, 38, 316 (1913).
Finally, brief mention should be made of the use of organic Atack, F. W., J . SOC.Chem. Ind., 34, 936 (1916).
liquids (principally alcohol and acetone) as solvents for Baudisch, O., Chem.-Zlg., 33, 1298 (1909)
Bellucci, I., and Savoia, G., Brit. Chem. Abstracts, 126, 788
certain reagents and as addition reagents to complete the pre- (1924).
cipitation of materials from aqueous solutions. Of great Berg, R., “Das o-Oxychinolin (Oxin),” Stuttgart, F. Enke,
significance also are solvents immiscible with water, such as 1935.
ether, amyl alcohol, carbon tetrachloride, etc., which can be Berg, R., and Roebling, W., Ber., 68, 403 (1935).
Berg, R., and Roebling, W., 2. angew. Chem., 48, 430, 597
used for the extraction of certain substances and their con- (1935).
centration into smaller volumes. The extraction of dithizon- Berg, R., and Wurm, O., Ber., 60, 1664 (1927).
ates by immiscible solvents has made possible the detection Biot, Compt. rend., 14, 49 (1842).
and determination of many heavy metal salts by the organic Blau, I?., Monatsh., 19, 647 (1898).
Bolliger, A., 2. anal. Chem., 94, 403 (1933).
reagent dithizone. Furthermore, substances which are not Brown, J., J. Am. Chem. Soc., 39, 2358 (1917).
soluble in organic liquids can sometimes be concentrated at the Busch, M., Ber., 38, 861 (1905).
water-organic liquid interface by shaking with immiscible Craig, K. A., and Chandlee, G. C., J . Am. Chem. Soc., 58, 1278
organic liquids and by this means rendered visible in small (1934).
Denighs, G., “PrBcis de chimie analytique,” 4th ed., p. 72,
amounts. Paris, Maloine et fils, 1913.
Summary and Review Dodd, S. S., Analyst, 55, 23 (1930).
Dubsky, J., and co-workers, 2. anal. Chem., 98, 184 (1933).
1. Organic reagents have an increasing analytical signifi- Dvorsak, R., and Reich-Rohrwig, W., Ibid., 86, 98 (1931).
cance, since their use greatly increases the specificity and Ephraim, F., Ber., 63, 1928 (1930).
the sensitivity of analytical reactions, introducing a simplifica- Ephraim, F., Helv. Chim. Acta, 14, 1266 (1931).
Feigl, F., Chem.-Ztg., 44, 689 (1920).
tion and rationalization of analytical methods, particularly Feigl, F., Mzkrochemie, 2, 188 (1924).
in microchemical analysis. Feigl, F., Oesterr. Chem.-Ztg., 22, 124 (1919).
 410
I
zy
zyxwvutsrqponmlkjihgfedc INDUSTRIAL AND ENGINEERING CHEMISTRY
Feigl, F., “Qualitative Analyse mit Hilfe von Ttipfelreak-
tionen,” 2nd ed., Berlin, Julius Springer, 1935.
Ibid., pp. 79-87.
Ibid., p. 237.
Ibid., p. 91.
New Pork, John Wiley & Sons, 1928.
(79) Koppel, J., Chem.-Ztg., 43,77 (1919).
VOL. 8, NO, 6
(78) Kolthoff, I. M., and Furman, N. H., “Volumetrio Analysia,”

(80) Krumholz, P.,and Krumholz, E., Mikrochemie, 19, 47 (1935).

(81) Kurtenacker, A., 2. anal. Chem., 64,56 (1924).
Ibid., p. 272.

zyxwvutsr
(82) Kurtenacker, A,, 2. anorg. allgem. Chem., 141,297 (1924).
Ibid., pp. 273-275. (83) Ibid., 161,201 (1927).
Feigl, F., 2. anal. Chem., 60,24 (1921). (84) LBger, E.,2. anal. Chem., 28,374 (1889).
Ibid., 61,454 (1922). (85) Lyons, E., J. Am. Chem. SOC.,49, 1916 (1927).

zyxwvutsrq
Ibid., 72, 113 (1927). (86) Malowan, S.,2. anorg. Chem., 108,73 (1914).
Ibid., 74, 387 (1928). (87) Mayr, C., 2.anal. Chem., 98,402 (1934).
Ibid., 77, 299 (1929). (88) Mayr, C., and Feigl, F., Ibid., 90,15 (1932).
Feigl, F., and Anger, V., unpublished work (see also disserta- (89) Monnier, A., Ann. chim. anal., 20, 237 (1916).
tion of Anger, V., Vienna, 1936). (90) Moser, L.,Ber., 58,380 (1925).
Feigl, F., and Chargaff, E., 2. anal. Chem., 74, 376 (1928). (91) Moser, L.,Monatsh., 43,679 (1922); 55, 14 (1930).
Feigl, F., and co-workers, Ber., 58, 2294 (1925). (92) Ibid., 53,39 (1929).
Feigl, F., and FrRnkel, E., 2. anal. Chem., 91,12 (1933). (93) Moser, L.,and Brukl, A., Ibid., 51, 325 (1929).
Feigl, F., and Hamburg, H., Ibid., 86, 7 (1931). (94) M%lier,W. J.,Ber., 35, 1587 (1902).
Feigl, F.,and Kapulitzas, H. J., Mikrochemie, 8, 239 (1930). (95) Pinkus, A., and Claessens, J., Bull. soc. chim. belg., 36, 413
Feigl, F., and Krumholz, P., Ibid., Pregl Festschrift, 1929, 77. (1927).
Ibid., 82. (96) Pinkus, A., and Demiers, J., Ibid., 37, 267 (1928).
Feigl, F.,Krumholz, P., and Rajmann, E., Mikrochemie, 9,395 (97) Poluektoff, N. S.,Mikrochemie, 14,265 (1933-34).
(1931).

zyxwvutsr
(98) Poluektoff, N. S.,2. ana2. Chem., 105,24 (1936).
Feigl, F., and Neuber, F., 2. anal. Chem., 62,375 (1923). (99) Rby, P.,and Bose, M. K., Ibid., 95,400 (1933).
Feigl, F., and Schwarz, R., unpublished work. (100) Rky, P., and Rhy, R. M., J. SOC.Chem. Ind., 3, 118 (1926).
Fischer, E., Ber., 16,2234 (1883). (101) Rlty, P., and Rky, R. M., 2. anal. Chem., 79,94 (1929).
Fischer, H., 2. anal. Chem., 73,45 (1922). (102) Reith, J. F., Pharm. Weekblad, 60, 1097 (1929).
Fischer, H., 2. angew. Chem., 47,658 (1934). (103) Rice, A. C.,Fogg, H. C., and James, C., J . Am. Chem. Soc., 48,
Folin, O.,and Denis, W., J. Biol. Chem., 22, 305 (1915).

zyxwvutsrqp
895 (1926).
Funk, H., 2. anal. Chem., 91,332 (1933); 93,240 (I 933); 96, (104) Riegler, E.,Chem.-Zlg., 21,rep. 307 (1897).
385 (1934). (105) Roller, P.S.,J. A m . Chem. SOC.,55,2437 (1933).
Furman, N. H., IND. ENG.CHEM.,15, 1071 (1923). (106) Rosenheim, A., and Weinheber, A., 2. anal. Chem., 69, 226
Ganassini, D., BoU. chim. farm, 43, 152 (1909). (1911).
Geilmann, W., and Voigt, A., 2. anal. Chem., 193, 311 (1930).
Giimour, B.,Analyst, 46,3 (1921); 49,576 (1924). (107) Rotter, G., Ibid., 64,102 (1924).
Goldberg, J., Ber., ‘40, 4541 (1907). (108) Schantl, E.,Mikrochemie, 2, 174 (1924).
Goppelsroeder, F., 2.anal. Chem., 7,195 (1868). (109) Schmidt, J., and Hinderer, V.. Ber., 65, 87 (1932).
Griess, P.,Ber., 12,427 (1879). (110) Sievert, A., and Hermsdorff, A., 2. angew. Chem., 34, 3 (1921).
Gutzeit, G., Heiv. Chim. A d a , 12,720 (1929). (111) Soule, B.A., J . Am. Chem. SOC.,47,981 (1925).
Hahn, F. L.,Compt. rend., 197, 762 (1933). (112) Spacu, G., and KuraB, M., 2. anal. Chem., 102, 108 (1935).
Hahn, F. L.,Mikrochemie, Pregi Festschrift, 1929, 127. (113) Strauss, F., and Ekkard, W., Ann., 444, 154 (1924).
Hahn, F. L.,and co-workers, Ber., 57, 1394 (1924). (114) Tananaeff, N.A., 2. anorg. allgem. Chem., 104,327 (1924).
Hammett, L. P.,and Sottery, C. T., J. A m . Cham. SOC.,47, (115) Thomas, J., J . Chem. SOC.,95,344 (1909).
142 (1925). (116) Thornton, W. M., Chem. News, 114, 13 (1916).
Hecht, F., and co-workers, 2. anal. Chem., 95,162 (1933). (117) Trillat, A., Ann. chim. a n a l , 8 , 408 (1903).
Hecht, F.,and Ehrmann, W., Ibid., 100, 87 (1935). (118) Tschakirian, A.,Compt. rend., 187,229 (1928).
Hirschl, W. N., and Verhoeff, J. A., Chem. Weekblad, 20, 319 (119) Underhill, F. P., and Petermann, F. I., Am. J. Physiol., 90,
(1923). 1 (1929).
Holladay, I. A., and Cunningham, T. R., Trans. A m . Electro- (120) Volmar, J., and Leber, M., J. pharm. chim., [SI 17, 125, 366,
chem. Soc., 43,329 (1924). 427 (1930).
Holzer, H., 2. anal. Chem., 95,398 (1933). (121) Votodek, E.,Ber., 40, 414 (1907).
Illinsky, M., and Knorre, G. v., Ber., 18, 699 (1885). (122) Wallach, O.,Ann., 437,148 (1924).
Kisser, J., Mikrochemie, 1, 25 (1923). . . Winter,
(123) 0.B., and co-workers, J. Am. Chem. Soc., 51, 2721,
2964 (1929).
Kiooster, H. S. v., J . A m . Chem. SOC.,43, 746 (1921).
Knorre, G.v., Ber., 38, 783 (1905). (124) Yoe, J. H., and Hill, W. L., Ibid., 50, 748 (1928).
Knowles, H.B.,Bur. Standards J . Research, 9,1 (1932).
Kolthoff, I. M., Chem. Weekblad, 24, 254 (1927). RECEIVED September 8, 1936. This paper was prepared for the .IneIytioal
(77) Kolthoff, I. M., 2. anal. Chem., 70,398 (1927); Barber, H. H., Edition upon special request to Dr. Feigl, professor at the University of
and Kolthoff, I. M., J . A m . Chem. Soc., 50, 1625 (1928). Vienna, because of his extensive contributions to this subject.

Anticipating the demand which will arise for reprints of this article, the Mack Printing Company,
Easton, Pa., will accept orders for reprints until January 1, 1937. Units of 50 copies can be supplied
in the 6 x 9 size with covers for $6.00. Single copies, 20 cents, postage paid. Bulk shipments
will be made by express collect.

Problems in Analysis

F ACTS which are ascertainable only through analysis of

compounds and mixtures are basic t o most of the work done
in chemistry and chemical engineering. Research of a high
As a service both t o industry and t o these research analysts,
we shall be pleased t o receive and publish such problems. It
should be understood that those who decide t o work upon them
order is carried on in analytical procedure in many laboratories. will let us know, so that we in turn may help establish contacts
While the majority of such workers have a field of particular in- between those interested in such research problems and those
terest, there are nevertheless a number of men of ability, espe- who would like t o follow u p the work in order t o render possible
cially those directing the research of others, who would be glad assistance, and t o be certain that some progress is made toward
to know of problems in analysis which would be of interest t o publishable results.
industry and upon which they might like t o work. [EDITOR]