INORGANIC A N D ANALYTICAL CHEMISTRY

NEW ORGANIC REAGENTS FOR THE PHOTOMETRIC

DETERMINATION OF Ba, Sr, Ca, AND SO~"

T. V. Petrova, I. Khakimkhodzhaev, UDC 541.14+543.062+546.431+546.41

and S. B. Savvin

2 , 7 - B i s - a z o d e r i v a t i v e s of c h r o m o t r o p i e a c i d of the g e n e r a l t y p e

Xl OH OH X~
/ ! I \

H0sS S03H

Xj or X~:C00H ill, S03H [2--5], AsO3H2[i, 2], POaH~[6--9]

w e r e p r o p o s e d e a r l i e r a s r e a g e n t s f o r the a l k a l i n e - e a r t h e l e m e n t s , c h i e f l y f o r Ba and S r .

A s e r i e s of r e a g e n t s not c o n t a i n i n g s a l t - f o r m i n g s u b s t i t u e n t s in the o - p o s i t i o n to the a z o g r o u p , both

in one and in two b e n z e n e r i n g s , i . e . , X 1 = H, X~ = H o r o n l y X 2 = H, h a s a l s o b e e n s t u d i e d [10, 11]. T h e s e
r e a g e n t s g i v e h i g h l y s e n s i t i v e c o l o r r e a c t i o n s w i t h C a , S r , and B a , in t h i s r e s p e c t s u r p a s s i n g r e a g e n t s w i t h
salt-forming groups.
T h i s c o m m u n i c a t i o n p r e s e n t s the r e s u l t s of a s t u d y of c e r t a i n r e a g e n t s of t h i s g r o u p with X 1
= COOH a n d with v a r i o u s s u b s t i t u e n t s in the m - and p - p o s i t i o n s to the a z o g r o u p in one b e n z e n e r i n g .
E l e v e n r e a g e n t s with the g e n e r a l f o r m u l a

COOH OK OR
/ I I ~3

/\/%/\ ~ 5
K03S S03H

were synthesized. The ordinal numbers of the reagents in the text and in the tables correspond to the fol-
lowing positions of the substituents: (1) 4-H, (II) 4-NO2, (III) 3-NO2, (IV) 4-SO3H , (V) 3-SO3H, (VI) 4-As
9O3H2, (VII) 4-CH3, (VIII) 3-CH3, (IX) 4-OCH3, (X) 3-COOH, (XI) 4-Cl.

EXPERIMENT AL
The reagents were synthesized according to the procedures for synthesizing analogous compounds,
described in [2], by azo coupling (ratio of the components, concentration, alkalinity); the methods of isola-
tion and subsequent purification of the product were selected experimentally in each case. As a rule, the
product was isolated by acidification with conc. HCI, while purification was accomplished by repea~ed re-
precipitation of the product from weakly alkaline solutions by acidification or salting-out with NaC[. The
purity of the reagents was monitored by methods of paper chromatography (eluents: 20% solution of CaCI 2
in 1 N HCI, 1 N HCI, and 80% ethanol) and eleetrophoresis analogously to [12]. The product was c()nsidered
sufficiently pure in the case of the formation of a basic band on the chromatogram or electrophoretogram,
comprising no less than 95% in comparison with the others with respect to color intensity. The analysis
(determination of the percent content of the basic substance) was conducted according to the method of vana-
datometric titration of the aze and nitro groups, as well as potentiometric titration of the acid groups.
V. I. Vernadskii Institute of Geochemistry and Analytical Chemistry, Academy of Sciences of the
USSR. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 259-265~ Febru-
ary, 1970. Original article submitted September i0, 1968.

9 Consult~nts Bureau~ a division of Plenum Pu[~Zishin~ Corporation, 227 lI:'est ]Tth Street: New Yor~:=
N. Y. 10011. 4ll rights reserved. This article cannot De reproduced for any purpose u,hatsoeuer with, out
permission of t/~e publisher. A copy of this article is available from the publisher for $i5.00.

213
 TABLE i. Speetrophotometrie Characteristics of Color Reactions
of Reagents with Elements

Reagent Element Conditions nrnXmaxMR, AX% nm n,lO

3ec~

II Cu pH 2,0--4,0; HzO 570 20 35

Th pH 1,6--2,0; IIzO 600, 650 100 26
La pH 2,0,--4,0; HzO 720 140' 110
IV La pH 3,0--4,0; 80% ethanol 600, 640 90 55
Th pH 1,5--2,0; H20 600, 650 ql,00 35
Cu pH 2,0--5,0; H20 570 20 27
V La pH 3,0--5,5; 8o% 600, 640 80 62
ethanol
Th pH 1,5--2,5; H~O 600, 650 90 43
Cu pH 3,0,--6,0; H20 570 10 26
VI Th pH 3,5--4,0; H20 600, 660 100 20
Cu pH 2,5--4,0; Hz0 580, 600 50 40
La pH 2,8--3,5; H20 650, 710, 150 50

* A~. = ~ m a x MR - - k m a x : R .

!
~J
/Z

/,J

t,0

~J
o,4

I
JO0 000 700 ~,, n m 5~Q 6gO 7~0 ~,.nm

Fig. 1 Fig. 2

F i g . 1. A b s o r p t i o n s p e c t r a of the r e a g e n t (IV) (1) and i t s c o m p l e x e s

with M g o r Ca (2) a n d B a (3) in75% e t h a n o l . [HR] = 2.5.10 -5 M, [M]
= 3.0.10 .4 M, pH 6 - 7 , c u v e t t e 10 ram.

F i g . 2. A b s o r p t i o n s p e c t r a of the r e a g e n t e a r b o x y n i t r a z o (II) i n w a -
t e r (1), i n 80% e t h a n o l (2), a n d i t s c o m p l e x e s with B a i n H20 (3) a n d
i n 80% e t h a n o l (4); with S r i n H20 (5) and 80% e t h a n o l (6). [HR] = 2.4
910" ~ M, [M] = 1.2.10-5 M, c u v e t t e 10 m m .

According to the analytical data, the percent content of the basic substance in the preparations corresponds
to: (I) 60.2%, (II) 74.7%, (III) 68.3%, (IV) 11.0%, (V) 86.4%, (VI) 89.0%, (VII) 54.1%, (VIII) 65,2%, (IX) 66.0%,
(X) 65.0%, (XI) 62.0%~
Only water of crystallization and salts of the alkali metals, which subsequently do not interfere, can be
present as impurities. To free it from possible impurities of Ca and other elements, the solution of the re-
agent, prepared by dissolving an exact weighed sample, was passed through a column with the cation-ex-
change resin KU-2 in the H-form and quantitatively eluted with water into a volumetric flask. The reagent
concentration was calculated according to the sample weight, considering the percent content of the basic
product in the dry preparation.

214
 !
.P 9
" 3
0,8 \
' /Z
I I

g~
/
/ ~ / I I I
.;~'%,'.. "-"f'~, I / f'3

" ' # 3

g4

1,37 Z,Tq- I],1/ }'b~ {zI

475 I7,5 Z~Z ~St" {3)
YUL7 6~0 700 ,~, nrn GO0 700 ~., m~_
Fig. 3 Fig. 4 Fig. 5
Fig. 3. Absorption s p e c t r a of reagent (VIII) in water (1), in 80% ethanol (2), and of its complexes with
Ca (6) and Ba (5) in w a t e r and Ca (3, 4) and Mg (7) in 80% ethanol. [HR] = 2.22.10 -5 M, [M] = 8.0.10 -5
M, pH 4 (1, 2, 5, 6), 5(3), 7 (4, 7), cuvette 10 mm.
Fig. 4. Absorption s p e c t r a of reagent (X) in w a t e r (1), in 80% ethanol (2), and of its complexes with Ca (3)
and Ba (5) in w a t e r and Ca (4) and Ba (6) in 80% ethanol. [HR] = 2.08.10 -~ M, [M] = 8.0.10 -5 M, pH 4.0 (1,
2, 3, 5), 7.0 (4, 6), cuvette 10 ram.
Fig. 5. Calibration c u r v e s for determining Ba, Sr, and sulfates.

The reagents isolated and purified represent dark red powders, moderately soluble in water~ stable
in air in the absence of strong oxidizing and reducing agents. For the work we used 0.1% aqueous solutions
of the reagents. Instruments: SFD-2 spectrophotometer and LPU-01 potentiometer.
Color Reactions with the Elements. In addition to the alkaline earth elements, the reagents give color
reactions with a number of other elements as well: the rare-earth elements (pH 3-4 or 6-7), Th (pH ~2),
Cu (pH 2-4), reagents (II)-(V) also with AI (pH 5), reagents (VI) and (IX) with Pb (pH 5-6). Some of these
reactions can be used for the photometric determination of the elements. The speetrophotometrie charac-
teristics of the reactions are cited in Table I.
The molar extinction coefficients were calculated from the curves of saturation of the reagent with
the metal or for La with the reagent (II) also from the curves of saturation of the metal with the reagent.
It is interesting to note that the reagent (If), giving highly sensitive and contrasting reactions with La,
gives practically no color reactions with Y or Yb.
Photometric Determination of Ba Sr, and Ca. The basic speetrophotometric characteristics, of the
color reactions of Ca, Sr, and Ba were obtained. Under the conditions of the reactions of these elements,
as a rule, Mg does not give color reactions. We studied the influence of the pH, nature of the solvent, and
selectivity. The molar extinction coefficients were calculated from the curves of saturation of the
metal with the reagent, considering the absorption of excess reagent. The influence of the pH on the de-
velopment of the color of the complexes was studied at the absorption maximum (kmax) of the con~iplex at
a ratio of the initial concentrations of the metal and reagent equal to 1:2. The composition of the complexes
was determined according to the method of saturation (both of the reagent by the metal and of the metal by
the reagent) according to the method of isomolar series, and for reagent (IT) also according to the methods
of [13, 14].
It was noted that the development of color of the complexes in aqueous medium depends in most cases
on the concentration of the reacting components and on the time. In aqueous organic medium, the rate of
development of color is substantially greater than in aqueous medium; however, the solubility of the com-
pounds (especially in aqueous acetone medium) is lower. At a metal concentration exceeding the reagent
concentration, precipitates can also be formed in aqueous solutions. Exceptions are reagents (IV) and (V)
(with SOaH groups in benzene rings), the complexes of which are readily soluble in both aqueous and aqueous
organic medium.
As it follows from the data obtained, for the reagents under consideration two types of color reac-
tions are possible with alkaline-earth elements in neutral and weakly acid media, which depend both on

215
the nature of the substituent in the benzene ring and on the pH and percent content of the organic sol-
vent. Reagents (IV)-(VI) form complexes with Mg, Ca, Sr, and Ba with absorption maxima at 580-590 and
640 nm (Fig. 1). The molar extinction coefficient of the complexes at 640 nm is of the order of 60-80.103.
The maximum development of color is observed at pH 7 in 80% alcohol or acetone. A reaction of this type
is also known for other reagents previously recommended for the determination of the alkaline-earth ele-
ments [1-9]. For reagents (1)-(Ill) and (VII)-(IX)complexes of a different type can be formed, possessing
more longwave absorption maxima, ~max 630-650 and 690-710 rim, while for the reagent (IX) a complex
possessing absorption maxima at 670 and 760 nm can be formed (Figs. 2-4). Such complexes are observed
only for Ca, Sr, and Ba and are not formed for Mg. The molar extinction coefficients for most of these
complexes are of the order of 120-160.103; maximum development of color is observed in aqueous medium
at pH 3-4, while the composition of the complexes corresponds to the ratio [M]:[HR] = 1:2. We observed
reactions of this type for the first time for bis-azo derivatives of chromotropic acid containing no salt-
forming substituents in the benzene rings in the o-position with respect to the azo groups [10, 11]. F o r the
reagents under consideration, two types of complexes can exist simultaneously (Xmax 580-590 and 640-650
nm, as well as 630-640 and 690-710 nm). Equilibrium depends on the value of the pH andthe percentcontent
of the organic solvent, which is evident from Figs. 3 and 4. The shift of equilibrium in the direction of f o r -
mation of the complex possessing a more shortwave Xmax increases in the series Ba < Sr < Ca. At pH .-~ 7
in aqueous organic medium, Ca in most cases is almost entirely bound into a complex of this type, whereas
Sr and especially Ba are more characterized by the existence of a complex possessing larger values of
Xmax. In aqueous medium the strength of the complexes possessing more longwave ~max increases in the
series Ca < Sr < Ba. Thus, when aqueous solutions are diluted to [M] = 0.6.10 -4 and [HR] = 1.2.10 -4 M, the
degree of dissociation of the complexes of Ca, Sr, and Ba are equal to: for reagent (If) 0.68, 0.30, and 0.13;
for reagent (VIII) 0.16, 0.15, and 0.06; for reagent (X) 0.40, 0.30, and 0.20, respectively. Complexes of Sr
and Ba in aqueous organic medium'are masked by sulfates at a stoichiometric ratio of the sulfate ions and
the metal. A substantial excess of sulfate is required for their masking in aqueous medium.
Considering the structure of the reagents, we can assume that the formation of two types of color r e -
actions is associated both with the participation of various analytical groups and with the state of the reagent
in solution. Complex formation is possible at the peridioxy, azoxy-, or carboxyazo groups. In this case the
reagent can interact both with the azoid and with the quinone hydrazone form. Possible structures of the
complexes are discussed in greater detail in [15, 16]. As can be seen from the values cited for the molar
extinction coefficients, most of the reagents considered give highly sensitive color reactions with Ca, St,
and Ba. In aqueous organic medium, these reagents are most interesting for the photometric determination
of Sr and Ba and have a sensitivity exceeding that of those known previously [3-5]. The possibility of photo-
metric determination of Sr and Ba was discussed in greater detail e a r l i e r for the reagent (If), which we
have called "carboxynitrazo." The maximum development of the color of complexes of Sr and Ba is observed
at pH 4-4.5. The molar extinction coefficient of the Ba complex is 142.103 that of the Sr complex 140.103.
The calibration curves are cited in Fig. 5.

The determination of Sr was conducted in 80~0 ethanol. When the percent content of ethanol is de-
creased, the rate of development of the color is sharply reduced- To construct the calibration curve, ali-
quot portions of a solution of strontium containing from 2 to 14 pg at 2 pg intervals were introduced into
25 ml volumetric flasks, along with 20 ml of ethanol and 0.5 ml of a 0.1% solution of the reagent; the mix-
ture was brought up to the mark with water and, after mixing, subjected to photometry at 710 nm.
Ba can be determined both in 80% or 40% ethanol and in 40% acetone. The construction of the calibra-
tion curve in 80% ethanol is analogous to the construction of the curve for Sr. To construct the curve in
40% ethanol we proceeded as follows. Aliquot portions of a solution of barium containing from 2.5 to 16 pg
were placed in 25 ml volumetric flasks, the total volume was brought up to ,.~10 ml with water, then 0.5 ml
of a 0.1~0 solution of the reagent was added, and mixed. After 10 rain, 10 ml of ethanol was added, the vol-
ume of the solution brought up to the mark with water, and after mixing, subjected to photometry at 710 nm
in cuvettes with l = 10 him (curve 1, see Fig. 5). A determination of smaller amounts of Ba, from 0.5 to 5.0
pg, is possible with photometry of the solutions in cuvettes with l = 30ram (curve 2). We studied the in-
fluence of other cations and anions on the color reactions of Sr and Ba. We used the concept of the selec-
tivity factor to evaluate their influence [17]. It was found that the reactions of Sr and Ba are more selective
with respect to anions than with respect to cations. The selectivity of the reaction of Ba in 40% ethanol is
greater than in 80% ethanol. When the same procedure is observed as in the construction of the calibration
curve, 300-fold amounts by weight of tartaric and citric acids, 150-200-fold amounts of sulfanilie acid and

216
 urotropin, and 4000-fold amounts of salicylic acid do not interfere with
T A B L E 2. P h o t o m e t r i c D e t e r -
the determination of 3.4 pg of Sr; 150-300-fold amounts of the alkali ele-
m i n a t i o n of SO~" in T a p W a t e r
ments are permissible. The determination of 5.4 pg Ba in 80% ethanol
9 [SO~" found,
Water ta~en, lmg/Hte r (av- Standard is not hindered by 500-600-fold amounts of oxalates, salicylates, and
ml ]erage)* i deviation nitrates, as well as 1200-fold amounts of citrates; 350-400-fold amounts
of the alkali metals are permissible. The determination of 5.4 pg Ba in
0.5 17,1 • 0,032 40% ethanol is not hindered by 1000-1500-fold amounts of nitrates, ci-
0.4 ;'/,3 :tO,07! trates, and urotropin, 3000-fold amounts of oxalates, 6000-fold amounts
0.3 17.2 :z:0.078
of tartaric and salicylic acids, and 140-fold amounts of fluorides. The
* Of q parallel determinations. presence of 600-700-fold amounts of alkali metals, 26-fold content of
Mg, 70-fold content of Zn 2+, and 250-fold content of Mn 2+ is permissible.
There may be an increase in the selectivity in the presence of salicylic
and oxalic acids. In the presence of salicylic acid, 175-fold amounts of A1 and 80-fold amounts of Fe 3+ do
not interfere with a determination of Sr (in comparison with nine- and fourfold amounts, respectively); 45-
fold amounts of Fe 3+ (instead of sixfold) do not interfere with the determination of Ba in 40% ethanol.
Photometric Determination of Sulfates. As a result of the extremely high sensitivity of the determin-
ation of barium, the reagents are of interest for the photometric determination of small quantities of sul-
fates. Let us cite a method of photometric determination of sulfates in a mixture of water, ethanol, and
acetone, using the complex of Ba with the reagent carboxynitrazo as the indicator. For the construction of
the calibration curve, from 0 to 2 ml of a 0.0001 M solution of Na2SO4, 8-10 ml of water, 1 ml of a 0.0002
M solution of BaCl2, and 0.5 ml of a 0.1% solution of the reagent were introduced into 25 ml volumetric
flasks, and thoroughly mixed. After 15-20 rain, 12.5 ml of a mixture of acetone and ethanol (5:1) was added,
the mixture brought up to the mark with water, mixed again, and subjected to photometry after i h, at 710 nm.
The calibration curve is cited in Fig. 5 (curve 4).
The proposed method was verified on the determination of sulfates in tap water. The water to be
analyzed was preliminarily passed through a column with the cation-exchange resin KU-2 in the H-form for
purification from interfering cations; the first portions of water were discarded, The results of the deter-
mination are cited in Table 2.
Reagents (IV), (V), and (VI), which give a color change with greater contrast than the reagents rec-
ommended earlier [2-4] may be of some interest for the volumetric determination of sulfates. However,
the reagents (IV), (V), and (Vl) are less selective with respect to phosphates and fluorides, which lowers
their analytical value.

CONCLUSIONS
i. Eleven bis-azo derivatives of chromotropic acid, containing a COOH group in the o-position to the
azo group in one of the benzene rings and NO2, SO,H, AsO3H2, COOH, CH3, CI, and OCH 3 groups in the
m- and p-position to the azo group, were studied as reagents for Ca, Sr, Be, and sulfates.
2. Most of the compounds considered are highly sensitive reagents for Sr, Ba, and sulfates.
3. The possibility of a photometric determination of St, Ba, and SO 2- with a reagent containing a NO 2
group in the p-position to the azo group, i.e., earboxynitrazo, was demonstrated.

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2. S. B. Savvin, Arsenazo III. Methods of Photometric Determination of Rare and Actinide Elements [in
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217
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1325 (1969).
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218