coupling constant of CH3HgX on the chemical properties of
From
X. Evans et ai. (12) and Scheffold (13) reported a linear de-
crease in the magnitude of the coupling constant for CH3-
HgOzCR complexes in deuterochloroform with increase in
the aqueous solution PKA of the carboxylic acid. The cou-
pling constants reported for the carboxylic acid complexes
which were also studied in the present work (pivalic, acetic
and mono- and dichloroacetic acids) are -22 Hz larger in
aqueous solution. Similar solvent effects have previously
been reported ( 4 ) . Scheffold also reported a n approximately
linear decrease in the magnitude of the coupling constant for
CH3HgXcomplexes in pyridine solution, where X was a series
of inorganic anions, with increase in the logarithm of the
aqueous solution formation constant.
The chemical shift of the methyl protons in the CH3Hg02CR
complexes is also dependent on the formation constant of the
complex, increasing approximately linearly as the logarithm of
K, increases.
Probably the most useful correlation, however, is that shown
in Figure 8 between the formation constant of the complex
(12) D. F. Evans, P. M. Ridout, and I. Wharf, .I. Ckem. SOC.A ,
1968, 2127.
(13) R. Scheffold, Helc. Chim. Acta, 52,56(1969).
Simultaneous Spectrophotometric Determination
of Barium and Strontium Using Sulfonazo 111
Paul J. Kemp and Max B. Williams
Department of Chemistry, Oregon State University, Coroallis, Ore. 97331
An absorbance study of the barium and strontium com-
plexes of sulfonazo Ill revealed that there is no pH
sensitivity of the complexes in the pH range 2.6 to 7.7.
The addition of the chelons EGTA and CDTA at pH 6
eliminates the interference of most cations except cop-
per which has a light blue chelon complex. The use of
EGTA at pH 6.1 and CDTA at pH 5.8 permits the deter-
mination of barium and strontium. Simultaneous
equations derived from Beer’s law facilitate the
analysis. The working range for the method is from 1.0
to 3.0 x 10-SM (1.4 to 4.1 ppm) for barium and from 2.0
to 8.0 x 10-5 (1.8 to 7.0 ppm) for strontium. An aqueous
solution of sulfonazo Ill shows less than 1% decomposi-
tion in seven days. With periodic calibration, the
analytical reagent can be considered stable for several
months. Under these conditions, the determination is
accurate to within 2% of the actual concentrations.
The properties of the free reagent were also investi-
gated, and it was found that sulfonazo Ill could be
isolated at 99.7% purity by purification with ion ex-
change resins and carefully controlled drying. Pure
solid sulfonazo Ill decomposes sharply at 222’ C, is
soluble in water and water miscible alcohols, and is in-
soluble in nonpolar organic solvents.
THE QUANTITATIVE COLORIMETRIC DETERMINATION of small
amounts of barium and strontium has generally been a difficult
undertaking. Of the few methods which have been attempted,
some involve reagents which are unstable and fade rapidly ( I ) .
Some require the precipitation of barium or strontium as in-
(1) D. S. Russell, J. B. Campbell, and S. S. Berman, AM^. Cliim.
Acta, 25,81 (1961).
124 ANALYTICAL CHEMISTRY, VOL. 45, NO. 1, JANUARY 1973
and the acid ionization constant of the carboxylic acid.
a least-squares treatment of the data
PKA = 1.7310gKI - 1.05
Studies are in progress to test the applicability of this relation-
ship for predicting the formation constants of methylmercury
complexes with carboxylic acid groups of known KA’S in
peptides and proteins.
The results reported in this paper demonstrate that P M R is
a powerful and direct method for elucidating the solution
chemistry of methylmercury complexes. Similar studies are in
progress with model organic ligands containing other func-
tional groups present in biological molecules and with several
amino acids and peptides. Studies also are in progress on
the solution chemistry of methylmercury complexes with in-
organic ligands of interest in the environmental chemistry
of methylmercury.
RECEIVED for review June 19, 1972. Accepted August 25,
1972. This work was supported, in part, by a grant from the
National Research Council of Canada to D. L. R. and by a
Postdoctoral Fellowship from the National Research Council
of Canada to S. L.
soluble complexes (2) or chromates (3) with the subsequent
separation and redissolving of the precipitates. Others in-
volve the decrease in absorption of the complexing agent as
the barium or strontium complexes or precipitates ( 4 , 5 ) . In
addition, most of the methods require prior separation of in-
terfering ions such as calcium, magnesium, and some of the
heavier metals (I, 5 ) .
The most promising of the complexing agents for barium
and strontium analysis are the sulfonazo dyes developed by
Savvin and his coworkers (6, 7 ) and investigated by Budesin-
sky and others (8-12). Of particular interest js the dye 2,7-
bis (2‘-sulfonophenylazp)-1,8-dihydroxy-3,6-naphthalenedi-
sulfonic acid (Figure 1) which was given the trivial name by
Budesinsky and Vrzalova of sulfonazo 111. These workers
~~
(2) E. R. Caley and C. E. Moore, ANAL.CHEM., 26. 939 (1954).
(3) I. M. Kolthoff and P. J. Elving, “Treatise on Analytical Chem-
istry,” Part 11, Volume 4, Interscience Publishers, New York,
N.Y., 1966, p 185.
(4) P. J. Lucchesi, S. Z. Lewin, and J. E. Vance, ANAL.CHEM.,
26,521 ( I 954).
(5) J. R. Dunstone and E. Payne, Analyst ( L o I ~ ~ o84,
I I 110
) , (1959).
(6) S. B. Savvin, Ju. M. Dedkov, and V. P. Markova. 2li. A17nl.
Khim., 17,43 (1962).
(7) S. B. Savvin, Ju. M. Dedkov: and V. P. Markova, Z. A m l .
Cliem.. 194,286 (1963).
(8) B. Budesinsky and D. Vrzalova, ibid., 210, 161 (1965).
(9) B. Budesinsky, ANAL.CHEM., 37, 1159 (1965).
(10) Z . Slovak, J. Fischer, and J. Borak, Talanra, 15, 831 (1968).
(11) B. Budesinsky, D. Vrzalova, and A. Bezdekova, Actrr Cliim.
Acad. Sci. Hung., 52, 37 (1967).
(12) B. Budesinsky and D. Vrzalova, Talanta, 13, 1217 (1966).
found the reagent to be an excellent indicator for use in the
titration of sulfate with barium (9) and also reported conditions
under which barium might be determined colorimetrically
although no analytical data were given (8). Later they simi-
larly investigated the behavior of barium and strontium with
dimethylsulfonazo I11 and rebated compounds (11).
Since sulfonazo I11 has now become commercially avail-
able and seems to be the most promising reagent for barium
and strontium determination, we have attempted t o use this in
a simple, direct simultaneous method for barium and stron-
tium determination in the presence of diverse metal ions
masked by the chelons, EGTA (ethylene glycol bis(P-amino-
ethyl ether)-N,N'-tetraacetic acid) and CDTA (trans-l,2-
diaminocyclohexane-N,N'-tetraaceticacid).
EXPERIMENTAL
Apparatus. Absorbance spectra were made on a Cary 15
recording spectrophotometer, using 1-cm matched silica
cells.
Reagents. Distilled water was deionized by passage
through an ion exchange monobed prepared by mixing
Amberlite IR-120 cation exchange resin (Hf form) and Dowex
1-X8 anion exchange resin (OH- form) together and then
through Dowex 50W-X4 cation exchange resin (H+ form)
followed by collection and storage in a borosilicate glass
carboy with minimal access to the atmosphere. The water
was found to be at pH 7.00 with a spec fic conductance of
4.0 x lo-' ohm-', and was used for all solutions. The
sulfonazo I11 was obtained from Aldrich Chemical Company,
Inc. and was purified by the method described below before
use. Standard barium, strontium, and calcium solutions
were prepared from their anhydrous carbonates (ACS rea-
gent). The magnesium solution was prepared from mag-
nesium carbonate trihydrate (CP) and solutions of other
metals were prepared directly from their reagent chloride
salts.
Purification of Sulfonazo 111. The commercial sulfonazo
111 proved to be quite impure and since attempts to follow
the purification procedure of Budesinsky and Vrzalova ( 8 )
gave inadequate purity and low yields, a more successful
method was devised. Five grams of raw sulfonazo I11 were
dissolved in 80 ml of water and filtered through Whatman
42 filter paper. The filtrate was treated with a little activated
carbon and filtered again through another piece of paper.
The second filtrate was passed slowly through a 30-mm i.d.
X 260-mm column prepared from freshly recharged 20-50
mesh Dowex 50W-X4 cation exchange resin (H+ form).
The resin eluate was evaporated to dryness using a water
ispirator to evacuate the drying flask at 65" C. The dried
material was dissolved in 30 ml of water, mixed with carbon,
and filtered as before. The resin was recharged and the
.hird filtrate was passed through the resin and water bath,
.hen taken to dryness in a vacuum oven 50 " C under 130 to
250 mm Hg pressure. The solid so obtained was dark purple
:almost black) with a metallic maroon iridescence. DTA and
TGA of this product revealed that the material contained
t.4 moles of water per mole of sulfonazo 111, and that the
;ulfonazo 111 decomposed exothermally at 222 OC. The solid
was observed to be very soluble in water, soluble in water
niscible alcohols, somewhat soluble in acidified aqueous
;elutions, and insoluble in nonpolar organic solvents such as
2enzene or chloroform.
The hydrated material was placed in a small open vial
Nhich was in turn placed inside a vacuum flask containing
VaOH pellets. The vacuum flask was heated to 120 to 125
T in a drying oven and connected to a vacuum pump which
-educed the pressure below 0.1 rnm Hg. The sulfonazo 111
rYas dried in this manner for 3.5 hours. The material so dried
was assayed by direct titration with standard base to an end
point at pH 6.80 after titration of four hydrogen ions. The
ANALYTICAL CHEMISTRY, VOL. 45, NO. 1, JANUARY 1973
Figure 1. 2,7-bis(2 '-sulfonophenyIazo)-1,8-dihydroxy-3,6-
napthalenedisulfonic acid ; formula C2?H18N1O1&; formula
weight 688.628; trivial name sulfonazo I11
equivalent weight of sulfonazo I11 in the assay is 172.16, and
vacuum dried material was found to be 99.7 sulfonazo 111
by weight. This purified sulfonazo 111 was used to prepare
all standard wlfonazo 111 solutions.
EGTA Buffer Solution at pH 6.1. EGTA (ethylene glycol
bis(p-aminoethyl ether)-N,N'-tetraacetic acid), 7.6 grams,
obtained from K and K Laboratories, were added to about
500 ml of water containing 5.4 grams of NaOH. When dis-
solved, 7.0 grams of maleic acid were added to complete the
buffering action and the solution was diluted to 1,000 ml with
water. If the EGTA is not added first with the NaOH, it is
extremely slow to dissolve.
CDTA Buffer Solution at pH 5.8. CDTA (trans-1,2-
diaminocyclohexane-N,N'-tetraacetic acid), 7.3 grams, ob-
tained from K and K Laboratories, was added to about 500
ml of water containing 5.4 grams of NaOH. Seven grams
of maleic acid were added and the solution was diluted to
about 950 ml. The pH was monitored while enough addi-
tional maleic acid was added, if necessary, to lower the pH to
5.8. Final dilution to 1000 ml and mixing were then com-
pleted.
Analytical Procedure. Solutions for spectrophotometric
measurements were prepared in 100-ml volumetric flasks.
Into flasks to be used as barium and strontium standards,
appropriate volumes of 2.00 X 10-*M stock solutions were
pipetted to give a final concentration range from 0.5 x 10-5M
to 10.0 X 10-"M. Into flasks used for analysis, 10.0-ml
aliquots of the synthetic samples were pipetted. Blank solu-
tions were prepared without cations.
Into each solution were pipetted 5.0 ml of the appropriate
chelon-buffer solution and 5.00 ml of 2.00 x 1 0 - 3 M ~ u l f o n a z ~
I11 stock solution. The flasks were then diluted to their
marks with water and mixed thoroughly. The differential
absorbance of each solution was then determined at 640 nm.
Due to the high color intensity of sulfonazo 111, it is diffi-
cult to pipet the stock solutions under normal laboratory
conditions. However, since sulfonazo I11 is fairly trans-
parent to red light, viewing the meniscus of a sulfonazo 111
solution in a pipet is relatively easy when held against a red
lamp or similar light source, such as an ordinary photographic
darkroom safelight.
RESULTS AND DISCUSSION
Spectral Characteristics. The absorption spectra of
sulfonazo I11 and its barium and strontium complexes cs.
H 2 0 are shown in Figure 2. The absorbance of free sulfon-
azo I11 follows Beer's law. The differential absorption spec-
tra of the barium and strontium complexes of sulfonazo 111
are presented in Figure 3.
Stoichiometric Ratio. The ligand-to-metal ratio of the
barium and strontium complexes of sulfonazo 111 was deter-
mined by the method of continuous variations. An isomolar
concentration of 1.000 X 10-4Mwas employed, and the re-
sultant curves are plotted in Figure 4. Blank solutions with
sulfonazo I11 at appropriate concentrations were used to ob-
tain differential absorbance measurements, the barium com-
* 125
Figure 2. Absorption spectra of sulfonazo Z
I11 and its barium and strontium complexes
"0;
A . 2.00 X l O - 5 . M sulfonazo 111. B. 2.00 X 0.5
10-3.W barium in 2.00 X 10-5M sulfonazo 111.
C. 2.00 x lO-3M strontium in 2.00 X lO-5M 0.3
sulfonazo 111

W a v e l e n g t h in nm

I I I I I I i I I I., I 1
0.8 1 I\ 1
-
0.6
E
-0
0
- - 4
: 0.4 - - Figure 3. Differential absorption spectra of the bar-
@
n
a
- ium and strontium sulfonazo I11 complexes
0.2 -
0
.-c
L
- Blank. 2.00 X 10-5M sulfonazo 111. A . 2.00 X 10-aM
? 0--- barium in 2.00 X 10-5M sulfonazo 111. B. 2.00 X lO+M
r - - strontium in 2.00 x 10-~Msulfonazo111
i -0.2-

I I I I I

A series of solutions, 2.00 x 10-5M in sulfonazo I11 and

Table I. Absorbance Depression Effect of Various Salts on 2.00 X 10-4M in barium was prepared. To each 1.0 X
the Barium Sulfonazo I11 Complex, Measured at 640 nm 10-2M nonreactive salt was added and the differential ab-
Salt Depression, Salt Depression, sorbance of the complex was measured. A comparison of the
(1.0 x 10-2M) z
(1.0 x IO-ZM) Yo influence of the salts tested measured at 640 nm is made in
None 0 .O (C2H;)eNHSCl 22,O Table I. It is evident that the common univalent cations
LiCl 16,O (C2HJ4NBr 26.6 greatly depress the absorbance of the complexes, lithium hav-
NaCl 17.8 NaBr 19.2 ing the least effect of those tested. It is interesting to note
KC1 31.9 NaC10, 17.8
NHJCl 22.7 NaN03 19.2 that all of the ammonium salts, independent of the degree of
CHsNHsCl 23.4 NaOzCH 17.8 substitution or ionic size, have virtually the same effect on the
(CH&NHKl 22.0 Na02CCH3 17.8 complex. Common anions seem to have little effect.
(CH3)4NCI 22.0 A series of solutions, 2.00 x lO-5M in sulfonazo 111 and
2.00 x 10-jM in either barium or strontium was prepared.
Sodium acetate was added in concentrations from zero to 3.5
x 10-2M. The effect of the barium complex was measured
plex was measured at 640 nm, and the strontium complex was a t 640 nm, the effect on the strontium complex was measured
measured at 643 nm. The ligand-to-metal ratio was found to a t 643 nm, and the effect on the blank was measured at 634
be 1 :1 for both complexes. nm. The variation in the absorbance of the complexes and
Stability of Sulfonazo I11 and Its Complexes. The free of the blank with the concentration of sodium acetate is shown
sulfonazo I11 in aqueous solution showed some decomposition in Figure 5.
on standing at ordinary laboratory conditions, the absorbance Effect of pH on Sulfonazo I11 and Its Complexes. Solutions
decreasing less than 1 % in seven days to 6 % decrease in 44 of sulfonazo 111 prepared for p H effect studies were adjusted
days. A sample standing in strong sunlight for 44 days to the desired pH value by the dropwise addition of dilute HC1
showed a decrease of 14% in absorbance, while one placed or dilute NaOH. A Thomas p H combination electrode was
z
in darkness in a refrigerator for 44 days showed 4 decrease. used to measure the p H since it could be inserted into the solu-
The differential absorbance of the barium complex L'S. sul- tion inside the volumetric flask. The p H of the solution was
fonazo I11 showed a slight increase on standing a t ordinary adjusted before the final dilution to the mark, and the findl
laboratory conditions (3x in 97 days) while a similar stron- pH measurement was made after dilution and mixing.
tium complex decreased 4z. Solutions of 2.00 x 1 0 - 5 ~sulfonazo I11 were prepared
Effect of Sodium Ion and Nonreactive Salts. Solutions from p H zero to p H 14. The significant absorption spectra
of sulfonazo 111 and its barium and strontium complexes recorded for the solutions are presented in Figure 6. The
were prepared in the presence of a series of common cations absorbance curves are practically p H independant in the pH
and anions at constant concentration to determine their rela- range 2.6 to 7.7.
tive effects on the absorbance of the complexes. Another Solutions 2.00 x IO-SMin sulfonazo 111 and 2.00 X 10-4M
series was prepared using sodium acetate at varying concentra- in either barium or strontium were prepared from p H zero to
tions to determine the concentration effect on the absorbance. pH 14, and their differential absorption spectra were recorded

126 e ANALYTICAL CHEMISTRY, VOL. 45, NO. 1, JANUARY 1973

 Table 11. Response of Sulfonazo I11 to Selected Cations
No. Cation A€&PPQ Xrnax AA1340

1 Ba(I1) 40,050 640 0.801

2 Sr(I1) 24,050 643 0.464
3 Ca(1I) 5,100 645 0.096

:::p-T$o
4 Mg(I1) 200 ... 0.004
5 Pb(I1) 35,850 650 0.560
6 Pd(l1) 31,500 617 0.100 Strontium
7 Cu(I1) 28,500 603 -0.042
8 Ni(I1) 10,100 646 0,188
9 Al(II1) 5,400 606 0.060
IO HdI) 4,300 647 0.076 0
11 Fe(1I) 3,350 648 0.058
12 Co(I1) 2,700 647 0.049 GI+ CL
13 Hg(II) 2,150 649 0.034
14 Zn(11) 2,100 645 0.039 Figure 4. Continuous variations plot for
15 Fe(111) 1 ,200 655 0.017 the complexes of barium and strontium
16 &(I) (25 . . 0.000 with sulfonazo 111. Total concentration
17 Cd(I1) <25 .. 0.000
18 Mn(I1) <25 ... 0.000 of metal plus ligand in each solution is
19 Sn(I1) Destroys Sulfonazo 111 1.000 X 10-4M. Barium solutions mea-
sured at 640 nm. Strontium solutions
a For comparison purpose. the subscript Acap,, denotes an ap-
parent ditrerential molar absorptivity. This assumes that in the measured at 643 nm
presence of a large excess of metal ion. the concentration of the
complex is approximately equal to the concentration of the ligand.
04 I I I , I I

Table 111. Differential Absorbances of Complexes of Sulfonazo

I11 in the Presence of EGTA and CDTA
-
pH = 6.0. Sulfonazo 111 = 2.00 X lO-5M
Cation EGTA CDTA
(2.00 x i o - 4 ~ ) (1.00 x 10-3.w) (1.00 x 1 0 - 3 ~ )
Ba(I1) 0.54 0.24
Sr(I1) 0.17 0.004
Ca(1I) 0.00 0.00

using 2.00 x IO-jM sulfonazo I11 a t the appropriate p H value

as a reference. The effect of the p H of the solution on the
apparent differential molar absorptivities (Acnpp) of the bar-
ium and strontium complexes is shown in Figure 7. As in the
case of the sulfonazo 111reagent alone, the absorbances of the
barium and strontium complexes are independent of pH in the
range 2.6 to 7.7.
Effect of Foreign Ions. Solutions 2.00 X 10-jM in sul-
fonazo 111and 2.0 X 10-4Min cation concentration were pre-
pared for 19 cations, and the absorption spectra were recorded.
The response of sulfonazo 111t o the 19 cations was found to
be similar to the response to strontium and barium [except in
the case of Sn(II), Pd(II), Cu(II), and AI(III)] with respect to
the shape of the absorption spectrum, there being only minor
variations in the wavelength of the differential absorbance
maximum as shown in Table 11. The marked change in the
absorption spectrum brought about by the four exceptions
noted is also indicated in Table I1 by the wavelength of the
maximum differential absorbance, or, in the case of Sn(II),
the destruction of the sulfonazo 111.
Masking Interfering Cations. Solutions identical to those
used to produce Table I1 were prepared, each containing
10-3M of one of the chelons, EGTA or CDTA. The p H of
each solution was about 3.5. It was found that [except for
Ba(II), Sr(II), Ca(II), Cu(II), and Sn(I1)I the chelons eliminated
m y measurable efrect of the cations listed in Table I1 on sul-
Fonazo 111. The effect of Cu(I1) resulted from its formation
3f a blue chelon complex with both chelons which absorbs
ilightly in the 640- to 643-nm range. The effects of the alka-
Sodium A c o t a l e C o n c e n t r a t i o n (MXIO')
Figure 5. Effect of the sodium acetate
concentration on sulfonazo 111 and its
barium and strontium complexes
Blank. 2.00 X 10-5h.l sulfonazo 111 in
water. A . 2.00 X 10-3M sulfonazo 111
measured at 634 nm. B. 2.00 x 10-5M
barium in 2.00 X 10-jM sulfonazo 111
measured at 640 nm. C. 2.00 X 10-5M
strontium in 2.00 X lO-5M sulfanazo I11
measured at 643 nm
line earth ions resulted from the failure of the chelons to com-
plex the cations more extensively than did the sulfonazo 111.
It was determined that at or near p H 6, the chelons elimi-
nated the effect of Ca(I1) on sulfonazo 111and that the response
of sulfonazo 111 to barium and strontium in the presence of
EGTA was considerably different from jts response to barium
and strontium in the presence of CDTA a t this pH. This is
shown in Table 111. This effect pointed the way to a duel-
chelon determination for barium and strontium. Two sepa-
rate absorbances were measured at 640 nm, one using EGTA
a t p H 6.1 and the other, CDTA at p H 5.8. Simultaneous
equations derived from Beer's law then allowed the concen-
trations of barium and strontium to be calculated.
Accuracy. The analysis method was applied to several
synthetic preparations containing calcium, strontium, and

ANALYTICAL CHEMISTRY, VOL. 45, NO. 1, JANUARY 1973 0 127

 Table IV. Results of Analysis of Synthetic Samples
Barium Strontium
Present
~-
Found AV
____ Present Found Av
Sample x 104~ Error, x 104~ Error,
I 3.00 3.022 0.50 0.267
3.052 3.04 1.3 0.167 0.22 56
I1 2.00 2.034 2.00 1.904
2.021 2.03 1.5 1.904 1.90 5.0
111 1.OO 1.004 8.00 7.785
0.967 0.99 1.o 7.918 7.85 1.9
IVa 3.00 3.045 1 .OO 0.668
3.045 3.04 1.3 0.668 0.67 33
Va 2.00 2.031 2.00 1.971
1.985 2.01 0.5 2.105 2.04 2.0
VIb 1 .oo 1.067 8.00 8.186
1.044 1.06 6.0 8.119 8.15 1.9
a Samples IV and V are similar to Samples I and I1 but contain 4.00 x lO-4M calcium.
b Sample VI is the same as Sample 111 but contains 1.4 X 10-3M calcium.

AI
Figure 6. Absorption spectra of sulfonazo 111
a t selected p H values
Sulfonazo 111 is 2.00 X lO-5M in all solutions. A.
1.2M HCl. B. pH 2.6 to pH 7.7. C. pH 11).
D. pH12. E. 1.2MNaOH 02-

I I I 1 I
O200 300 400 500 600
W a v s l e n p l h in nm

EGTA
AACDTA - AAEGTA

1
0 2 4 6 8 1 0 1 2 1 4
LA ,-.
PH AEBaCDTA

Figure 7. Dependence of the apparent At 640 nm and our experimental conditions h B a E G T . 4 =

differential molar absorptivities of the
21,502, AEB~CDTA= 10,034, AESrEGTA = 5,125, and AESCDTA
barium and strontium sulfonazo I11
= 995. Using these values, Equations 3 and 4 become:
complexes on the p H of the solution
~ (5.151 AACDTA - A A E G T A ) ( x
C B= ~ . 10-'))M
~~~ (5)
barium. The calibration curves are shown in Figure 8 and csr = (AAEGTA- 2.143 AAc~~.4)(3.341X w 4 ) M (6)
the analytical results are given in Table IV.
Computations of Barium and Strontium Concentrations. Since 10-ml aliquots of the synthetic samples were used ir
From Beer's law a system containing both strontium and 100-ml volumetric flasks for analysis, the results obtained us.
barium may be described as follows: ing Equations 5 and 6 were multiplied by ten to obtain thr
concentration of barium or strontium in the original samplr
AAEGTA = AEBaEGTACBa + AES~EGTACS~ (1) solution.
Structure of Complexes. The structure of the sulfonazc
AACDTA = AEBaCDTACBa t AESrCDTACSr (2) 111 complexes has been proposed by Budesinsky (13)and is the
only proposed structure for such complexes t o adequatel!
From these two equations, it is possible to derive equations
by which the concentration of barium and strontium may be
calculated. They are: (13) B. Budesinsky, T u h t u , 15, 1063 (1968).

128 ANALYTICAL CHEMISTRY, VOL. 45, NO. 1, JANUARY 1973

explain a 1 :1 ligand-to-metal complex ratio. The sulfonazo
I11 complex presumably involves the sulfonazo I11 as a quadri- 0.8 I I I I I I I I I I
I
dentate ligand occupying the four equatorial sites of an octa-
hedral complex in a square plane. Only four oxygen-con- 0.7
taining groups are coordinated to the metal ion (See Figure 1;
two hydroxy groups and two sulfonic groups) and the azo
nitrogens are not involved. The remaining two sites of the 0.6
0
octahedral complex are presumably coordinated by solvent c
0
molecules. 0.5
Table I and Figure 5 indicate the significant effect of uni- 0
v)
valent cations on the differential absorbance. It becomes evi- n
dent that analyses must be performed under conditions which - 0.4
a
will not be greatly affected by the intrusion of extraneous uni- .-
c
0

valent cations. Consequently, the chelon-buffers were pre-

pared to contain 0.13M sodium ion, giving a 6.5 X 10-3M
5 0.3
0)
sodium ion concentration in the solutions for spectropho- .-
r

tometric measurements. This allows a n intrusion of as much a 0.2

as 2 x lO-*M extraneous sodium ion without causing more
than 1 % change in the differential absorbance of the com-
plexes. If appreciable other univalent cations are present,
calibration should be done in the presence of these ions.
The studies of the effect of pH on sulfonazo I11 and its com-
plexes reveal a pH range from 2.6 to 7.7 in which the complexes
are unaffected by changing pH. Considering that the end
point of the titration of sulfonazo TI1 with standard base oc-
curs at pH 6.80 for four replaceable hydrogens and that the
free sulfonazo 111 spectrum does not show measurable change
in the pH range 2.6 to 7.7. it would seem evident that the ligand
species present in this pH range is H?L4-, so that the com-
plexes of barium are presumably of the composition MHLZ-.
Beer's law plots of EGTA complexes of barium and stron-
tium (Figure 8) became nonlinear at lower concentrations than
do the corresponding CDTA complexes. For the determina-
tion of barium and strontium using simultaneous equations,
strict linearity is necessary. It was found that the practical
upper limits where EGTA complex nonlinearity begins are 3.0
X lOPM(4.1 ppm) barium and 8.0 x 10n5M(7.0ppm) stron-
tium in the solutions used for spectrophotometric measure-
ments. The analysis data (Table IV) indicate that the lower
analytical limit for barium is 1.0 X 10-5M (1.4 ppm) and for
strontiuniis 2.0 x 10-5M(1.8 ppm).
Within these limits, and following the procedure described,
the method should have an error of less than 2 z of the mea-
surement made, provided that standardization is made on the
sulfonazo I11 stock solution weekly.
Another consideration of significance is that in the absence
of' interferences, the sensitivity of measurements with sulfon-
0.1
0
2 4 6 8 1 0
c, (X106 M )
Figure 8. Calibration of sulfonazo I11 for the
determination of barium and strontium using
chelon-buffers
Sulfonazo III is 1.000 X 10+M and the differential
absorbance is measured at 640 nm
azo 111 may be increased considerably. The analysis of bar-
ium alone or strontium alone in the absence of calcium may be
done at pH 3 where the effect of the chelons on Ba(I1) and
Sr(1I) is negligible, but the chelons retain their ability to com-
plex all of the other interfering cations listed in Table 11. The
advantage of the lower pH value is that the sodium ion con-
centration can be lowered considerably which increases the
sensitivity of sulfonazo I11 to barium and strontium. The
combination of the two effects (reduction of' chelon cornplexa-
tion and reduction of sodium ion interference) can increase
the sensitivity by almost a factor of two.
for review May 26, 1972. Accepted August 30,
RECEIVED
1972.

ANALYTICAL CHEMISTRY, VOL. 45, NO. 1, JANUARY 1973 129