MICROCHEMICAL JOURNAL 38, 101-10s (1988)

Determination of Microamounts of Tungsten(W) in Brines

Using Fluorescence Quenching of Rhodamine B Solutions
MOHAMMED AFFAN AND FADHIL JASIM

Department of Chemistry, College of Science, University of Baghdad, Jadriya, Baghdad, Iraq

Received November 12, 1987; accepted February 10, 1988
A spectrofluorometric method for the microdetermination of W(VI) in brines through
fluorescence quenching of rhodamine B (Rh B) aqueous solutions has been developed. The
dependence of quenching on pH concentration of ligand, salt background, analyte amount,
equilibration period, acetone-to-water ratio, and interferences has been discussed. The
tungstate ion forms a complex at pH 3-4 with Rh B with a metal-to-ligand molar ratio of I : I
and stability constant of log K = 5.8. Beers law is obeyed over the range l-12 ppm W(VI),
and 3-24 ppm W(VI) in an acetone-water solution. The sensitivity detection limit and
RSD% have been worked out using the established procedure. The recovery percentage for
two different concentrations of analyte has also been estimated. Q 1988 Academic press, IK.

INTRODUCTION
Murata and Yamauchi (I) were the first to observe that the extent of fluores-
cence quenching of 0.1% (w/v) Rh B aqueous solution is proportional to the
concentration of analyte metal. Neither performance parameters such as sensi-
tivity, detection limit, RSD%, etc., nor applications to the analysis of real samples
were offered. Using Rh B, Pollock (2) determined W in ores photometrically. A
detailed literature survey on this subject was published by Haddad (3), mentioning
the various Rh B analytical aspects. The method proposed here investigates a new
field of sample applications, that is, the determination of W(V1) in brines and rock
salts and works out performance (sensitivity. detection limit, and precision),
structure (L:M), and stability of complex data. The procedure is simpler and less
expensive than most current techniques, for instance, ETA (4) and ICP (5), par-
ticularly in such high NaCl background media where background interference is
very difficult to avoid. Microamounts of W(VI) can catalytically adversely affect
the electrolytic process of brine electrolyzed in the mercury cells, resulting in
deterioration of the yield of final products of electrolysis. Therefore the proposed
method is adequate to control the concentration of the analyte in real brine and
rock samples (Table 1).

EXPERIMENTAL
Appuratus. A Perkin-Elmer Model MPF-44B fluorescence spectrophotometer
and a Hitachi Model 056 X-Y recorder were used to carry out the fluorometric
measurements.

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102 AFFAN AND JASIM

TABLE 1
Concentration of W(V1) (ppm) in Brine and Rock Salt Samples
Semawa mines
Lake Sawa (rock salt) Fao marshesb
6.2 5.4 2.0
6.1 5.4 2.0
6.2 5.3 1.9
6.3 5.4 2.1
5.9 5.2 1.9

a Western part of Iraq.

b Southern part of Iraq.

The Rh B (0.020%, w/v) solutions were prepared by dissolving the appropriate

weights of the reagent in deionized water or in 20% (v/v) acetone.
Standard W(VZ) solutions. A stock solution of 1000ppm W(VI) was prepared by
dissolving the appropriate amount of Na,W04 * 2Hz0 (AnalaR BDH) in deionized
water. A series of standard W(V1) solutions was prepared by serial dilution of the
stock solution.
All the other reagents used were Fluka (AG Buchs) puriss grade.
All laboratory ware used was thoroughly cleaned in nitric acid (1: 1) and rinsed
with deionized water.
Procedure. 1. In a 25ml volumetric flask, place 5.00 ml of the clear brine
sample. Add 2.00 ml of 0.20% (w/v) Rh B solution and enough 0.1 M HCl to make
the final solution pH 34, mix, dilute to the mark with deionized water, shake, set
aside for 30 min, and measure the fluorescence (Table 2). To obtain reproducible
results sample and standard solutions should be subjected to the same analytical
procedure.
2. Using Table 2, linear calibration graphs of analyte are obtained either di-

TABLE 2
Optimal Instrumental Parameters for the
Determination of W(V1) in Brines
Parameter Setting
Wavelength (nm) AEX. = 353
Amu. = 594598
SBW (nm) 5
Atomosphere Static air
Scanning (nm min- ) 120
Response 1.2
Mode Energy
Dynode voltage -750
Signal gain 0.3
Scale expansion 1
Radiation AC
Temperature (C) 25
Recorder speed (cm min-) 1
 DETERMINATION OF TUNGSTEN(W) IN BRINE 103
rectly (Fig. 1) or by the method of standard additions (not shown for brevity). The
average of triplicate runs is usually taken. The concentration of analyte in samples
is calculated by regression from the graphs. Experiments have shown that deion-
ized water, standards, and brine samples read zero fluorescence; therefore fluo-
rescence of the reagent blank is due to Rh B only.
3. Samples of brine containing 3-24 ppm W(V1) are prepared as in (1) above but
using 0.020% (w/v) Rh B in 20% (v/v) acetone aqueous solution.
4. Rock salt is analyzed for W(V1) by preparing a brine which is 1~ in NaCl and
proceeding according to (1) above.
RESULTS AND DISCUSSION
Figure 2A shows that An, and peak heights vary with change of Rh B concen-
tration. A solution of 16 ppm Rh B gives maximum fluorescence at Ai+, = 598 nm.
Beyond this concentration the formation of the weakly fluorescent dimer, (Rh B)2,
begins (6-7), and quenching occurs (Fig. 2B). Changes of Rh B concentration
have no effect on the position of A,,. at 353 nm. Other excitation peaks give
scattered lights which deeply depreciate fluorescence power. Furthermore, the
addition of micro amounts of W(V1) to the ligand solution shifts AFlu.to 594 nm but
has no effect on A,,. at 353 nm.
The quenching capability of the analyte depends on the pH of the Rh B solution
and reaches maximum at pH 3-4, where zwitterion forms,

(Rh B)+ (Rh B)

as a fluorescent bright red dye that could be easily quenched by a heavy para-
magnetic element with intercrossing system character such as W(V1) and utilized
for its analysis. A reaction mechanism is proposed as follows:

pH 34
NazW04 + 2HCl ---, HzW04 + 2NaCl (1)
H2W04 Z$ W03 * HZ0 = (W03 . OH)- + H+ (2)
(W03 . OH)- + (Rh B)+ + (Rh B WO3 OH)
Solution Salt form Nontluorescent (3)
(fluorescent) 1: 1 complex
This is consistent with our findings (using the mole ratio method) (6) that Rh B at
pH 34 forms a violet-purple nonfluorescent 1: 1 complex with tungsten(V1) which
absorbs at A,,. = 560 nm.
The fluorescence quenching is directly proportional to W(V1) concentration
over the range 1-12 ppm (Fig. 1). If a Rh B solution containing 20% (v/v) acetone
104 AFFAN AND JASIM

8C
100

90

30
20
20

10

0
560 640 012345678 9 10 11 12
A, nm. W(W), ppm
FIG. 1. Calibration graph of W(V1). (A) Peak heights of fluorescence quenching of Rh B aqueous
solutions using 1-12 ppm W(V1); (B) adherence to Beers law.

were used in the procedure the linear range of the calibration graph would be
pushed to 3-24 ppm W(VI).
This enhanced fluorescence power could be attributed to the increasing polarity
of the acetone-water solution which in turn increases the number of the fluores-
cent Rh B+ thus providing the conditions for higher analyte concentration to be
involved.

B
A 1001 31\5Q4

110.

Q) 90.
E

556 630 8 16 24 32 40 48 56 64
X,nm RhB. ppm
FIG. 2. Effect of various concentrations of Rh B aqueous solution (excitation, 353 nm) on (A)
position of XnU. and (B) intensity of fluorescence; the numerals seen in (A), 1 to 6, represent the peak
heights and positions of various concentrations of the six Rh B solutions shown in (B).
 DETERMINATION OF TUNGSTEN(W) IN BRINE 105
The presence of up to 1 M NaCl has no effect on AFlu., XEx,, and the intensity
of Rh B solution used in the established procedure; but higher concentrations
cause quenching and therefore the measured solution should be 1 M or less with
respect to NaCl.
Linearity is improved in the presence rather than absence of NaCl with the
subsequent improvement in sensitivity of the method.
Equilibrium conditions of fluorescence quenching are reached within 30 min
and remain so for at least 48 h.
Atmospheric oxygen has no effect on the results. The fluorescence signal re-
mains the same before and after deaerating with nitrogen.
The following ions which might be present in the salt background of brine or
rock salt are tolerated to the extent of concentration (ppm) given in parentheses:
Ca*+ (loo), Mg*+ (loo), V5+ (loo), Ni*+ (loo), Kf (loo), Cu*+ (loo), Zn*+ (loo),
Ba*+ (lOO), Cd*+ (IOO), Cl- (1 M), Bti- (0.05 M), SOT (0.1 M), CHJlOO- (0.2
M), and Na+ (1 M). Mo(V1) beyond 28 ppm is masked by adding to the measured
solution 2 ml of 0.1 M oxalic acid; Fe(II1) is masked by adding 1 ml of freshly
prepared 10% (w/v) ascorbic acid.
W(VI)-Rh B Chelate Complex
The mole ratio and continuous variation methods were used to investigate the
structure of the above chelate. Both methods indicate a CL/C, of 1. The condi-
tional stability constant of the W(VI)-Rh B chelate complex is found to be equal
to log K = 5.8.
CONCLUSION
The proposed method is simple because it requires no physical or chemical
pretreatment. It utilizes inexpensive reagents. It is sensitive with a very low
detection limit (0.2 ppb). The RSD% (precision) for eight standard solutions, each
containing 4 ppm W(V1) and subjected to the established procedure, was found to
be 1.306%. Almost similar results were obtained for other concentrations (1-12
ppm W(V1)). It does not depend to a large extent on pH and salt background of the
sample. It requires a short time to reach equilibrium (30 min). Beers law is
obeyed over the range l-12 ppm, and in the presence of acetone it extends to 3-24
ppm with the same precision and sensitivity. Using the method of standard addi-
tions the recovery percentages for 3 and 10 ppm W(V1) were found respectively
to be 98.7 and 100.2%. Structures and stability constant (apparent) were deter-
mined. The method could be adopted for the microdetermination of iron and
molybdenum in brines and rock salts.
REFERENCES
1. Murata, A.; Yamauchi, F. J. Chem. Sot. Japan, 1956, 77, 1259-1262.
2. Pollock, J. B. Analysf (London), 1958, 8, 516-522.
3. Haddad, P. R. Talanta, 1977, 24, 1-13.
4. Salvin, W. Graphite Furnace AAS. Perk&Elmer Corp., 1948.
5. Mclaren, J. W.; Berman, S. S.; Boyko, V. J.; Russel, D. S. Anal. Chem. 1981, 53, 1802-1806.
6. Rohatgi, K. K. J. Mol. Spectrosc., 1968, 27, 545-548.
7. Urrecha, I.; Castano, P. J. Chem. Sot. Faraday Trans. II, 1978, 6, 1094-1097.