Talanta 48 (1999) 1085 – 1094

Spectrophotometric method for determination of vanadium

and its application to industrial, environmental, biological
and soil samples
M. Jamaluddin Ahmed *, Saera Banoo
Laboratory of Analytical Chemistry, Department of Chemistry, Uni6ersity of Chittagong, Chittagong 4331, Bangladesh

Received 28 May 1998; received in revised form 6 October 1998; accepted 7 October 1998

Abstract

The very sensitive, fairly selective direct spectrophotometric method for the determination of trace amount of
vanadium (V) with 1,5-diphenylcarbohydrazide (1,5-diphenylcarbazide) has been developed. 1,5-diphenylcarbohy-
drazide (DPCH) reacts in slightly acidic (0.0001 – 0.001 M H2SO4 or pH 4.0 – 5.5) 50% acetonic media with vanadium
(V) to give a red–violet chelate which has an absorption maximum at 531 nm. The average molar absorption
coefficient and Sandell’s sensitivity were found to be 4.23 × 104 l mol − 1 cm − 1 and 10 ng cm − 2 of Vv, respectively.
Linear calibration graph were obtained for 0.1 – 30 mg ml − 1 of Vv: the stoichiometric composition of the chelate is 1:3
(V: DPCH). The reaction is instantaneous and absorbance remain stable for 48 h. The interference from over 50
cations, anions and complexing agents has been studied at 1 mg ml − 1 of Vv. The method was successfully used in the
determination of vanadium in several standard reference materials (alloys and steels), environmental waters (potable
and polluted), biological samples (human blood and urine), soil samples, solution containing both vanadium (V) and
vanadium (IV) and complex synthetic mixtures. The method has high precision and accuracy (s = 9 0.01 for 0.5 mg
ml − 1). © 1999 Elsevier Science B.V. All rights reserved.

Keywords: Spectrophotometry; Vanadium determination; 1,5-diphenylcarbohydrazide; Alloy; Steel; Environmental; Biological

samples; Soil samples

1. Introduction crops and the entire agricultural system. High

Vanadium poisoning is an industrial hazard [1].
Environmental scientists have declared vanadium
as a potentially dangerous chemical pollutant that
can play havoc with the productivity of plants,
* Corresponding author. Fax: +880-31-610938/726310; e-
mail: vc-cu@spnetctg.com.
amounts of vanadium are said to be present in
fossil fuels such as crude petroleum, fuel, oils,
some coals, and lignite. Burning these fuels re-
leases vanadium into the air that then settles on
the soil. There are cases of vanadium poisoning,
the symptoms of which are nervous depression,
coughing, vomiting, diarrhoea, anaemia and in-
creased risk of lung cancer, that are sometimes

0039-9140/99/$ - see front matter © 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 9 1 4 0 ( 9 8 ) 0 0 3 2 9 - 4
1086 M.J. Ahmed, S. Banoo / Talanta 48 (1999) 1085–1094

fatal [2]. Recently, vanadium has been noticed as

the index element in urban environmental pollu-
tion, especially air pollution [3]. Laboratory and
epidemiological evidence suggests that vanadium
may also play a beneficial role in the prevention
of heart-disease [4]. Shamberger [5] has pointed
out that human heart-disease death rates are
lower in countries where more vanadium occurs
in the environment. Vanadium in environmental
samples has been determined by NAA [6], ICP-
atomic emission spectrometry [7], AAS [8] and
spectrophotometry [10 – 22]. The first two meth-
ods are disadvantageous in terms of cost and
instruments used in routine analysis. AAS is of-
ten lacking in sensitivity and affected by matrix
conditions of samples such as salinity. Catalytic
solvent extractive methods are highly sensitive
but are generally lacking in simplicity. Hence its Fig. 1. Effect of the acidity on the absorbance V(V) DPCH-
accurate determination at trace levels using sim- system.
ple and rapid methods is of paramount impor-
tance.
produce a highly absorbent red–violet chelate
The aim of this study is to develop a simpler
product followed by direct measurement of the
direct spectrophotometric method for the trace
absorbance in aqueous solution. With suitable
determination of vanadium. 1,5-Diphenylcarbo-
masking, the reaction can be made highly selec-
hydrazide (DPCH) has been reported as a spec-
tive and the reagent blank solutions do not
trophotometric reagent for chromium [9] and
show any absorbance.
has previously been used for spectrophotometric
determination of vanadium [10] but this method
is solvent extractive, lengthy and time consuming
and lack selectivity due to much interference.
Pyridine and chloroform had been used as sol-
vents for this extraction which can be classified
as toxic and as environmental pollutants [3] and
have been listed as carcinogens by the Environ-
mental Protection Agency (EPA) [9a]. This pa-
per reports its use in a very sensitive, highly
specific non-extractive spectrophometric method
for trace determination of vanadium. The
method possesses distinct advantages over exist-
ing methods with respect to sensitivity [10–15],
selectivity [10 – 15,18 – 22], range of determination
[10–15], simplicity [10 – 13,17], speed [10,12,18],
pH/acidity range [10,17 – 22], thermal stability
[10–22], accuracy [10 – 15,22], precision [10–22]
and ease of operation [10 – 22]. The method is
based on the reaction of non-absorbent DPCH
in slightly acidic solution (0.0001 – 0.001 M sulfu- Fig. 2. Effect of reagent (DPCH:V(V) molar concentration
ric acid or pH 4.0 – 5.5) with vanadium (V) to ratio) on the absorbance of V(V)-DPCH system.
 M.J. Ahmed, S. Banoo / Talanta 48 (1999) 1085–1094
Fig. 3. Calibration graphs: A, 1–10 mg ml − 1 of vanadium (V) and B, 10 – 30 mg ml − 1 of vanadium (V).
2. Experimental
2.1. Apparatus
A Shimadzu (Kyoto, Japan) (model-160) dou-
ble-beam UV/VIS spectrophotometer and Jenway
(England, UK) (Model 3010) pH meter with a
combination of electrodes were used for the mea-
surements of absorbance and pH, respectively. A
Shimadzu (Model 5000) atomic absorption spec-
trometer equipped with a microcomputer-con-
trolled graphite furnace was used for comparison
of the results.
2.2. Reagents
All chemicals used were of analytical-reagent
grade or the highest purity available.
Doubly distilled de-ionized water and HPLC-
grade acetone, which is non-absorbent under ul-
traviolet radiation, were used throughout.
1087
2.2.1. DPCH solution, 4.12×10 − 4M
Prepared by dissolving the requisite amount of
DPCH (Merck Darmastadt, Germany) in a
known volume of distilled acetone. More dilute
solutions of the reagent were prepared as
required.
2.2.2. Vanadium (V) standard solutions
A 100-ml amount of stock solution (1 mg
ml − 1) of pentavalent vanadium was prepared by
dissolving 0.2269 mg of ammonium metavanadate
(Merck) in doubly distilled de-ionized water con-
taining 1–2 ml of nitric acid (1+ 1). More dilute
standard solutions were prepared from this stock
solution as and when required.
2.2.3. Vanadium (IV) stock solution
A 100-ml amount of stock solution (1 mg
ml − 1) was prepared by dissolving 390.7 mg of
purified grade vanadyl sulfate (Fisher Scientific) in
1088 M.J. Ahmed, S. Banoo / Talanta 48 (1999) 1085–1094

doubly distilled de-ionized water. The working reagent blank. The vanadium content in an un-
standard of vanadium (IV) was prepared by ap- kown samples was determined using a concur-
propriate dilution of this solution. rently prepared calibration graph.

2.2.4. Other solutions

Solutions of a large number of inorganic ions
and complexing agents were prepared from their
AnalaR grade or equivalent grade water soluble
salts. In the case of insoluble substances, special
dissolution methods were adopted [23].
All glassware was kept in nitric acid (1+ 1) for
at least a day and then was rinsed with de-ionized
water before use. Stock solutions and environ-
mental water samples were kept in poly (propy-
lene) bottles containing 1 ml of concentrated
nitric acid.
3. Procedure
To 0.1–1 ml of slightly acidic solutions contain-
ing 1–300 mg of vanadium (V) in a 10-ml cali-
brated flask was mixed with a 0.1 – 1.0 (preferably
0.5 ml) of 0.001 M H2SO4 (or pH 4.0 –5.5) fol-
lowed by the addition of 20 – 100-fold molar ex-
cess of DPCH solution (preferably 1 ml of
4.12×10 − 4 M). After 1 min, 5 ml of acetone
were added and the mixture was diluted to the
mark with de-ionized water. The absorbance was
measured at 531 nm against a corresponding
4. Results and discussion
4.1. Factors affecting the absorbance
4.1.1. Absorption spectra
The absorption spectra of the vanadium (V)-
DPCH system in 0.001 M sulfuric acid medium
was recorded using the spectrophotometer. The
absorption spectra of the vanadium (V)-DPCH is
a symmetric curve with maximum absorbance at
531 nm and average molar absorption of 4.23×
104 l mol − 1 cm − 1. DPCH did not show any
absorbance. In all instances measurements were
made at 531 nm against a reagent blank. The
reaction mechanism of the present method is as
reported earlier [24].
4.1.2. Effect of sol6ent
Of the various solvents (benzene, chloroform,
carbon tetrachloride, nitrobenzene, isobutyl alco-
hol, n-butanol, isobutyl methyl ketone, ethanol,
acetone and 1,4-dioxane) studied, acetone was
found to be the best solvent for the system. No
absorbance was observed in the organic phase
with the exception of n-butanol. In 509 2% (v/v)

Table 1
Determination of vanadium in some synthetic mixtures

Sample Composition of mixture (mg ml−1) Vanadium (V) (mg ml−1)

Added Founda Recovery 9 SDb (%)

A V(V) 0.50 0.50 100 90.0

1.00 0.99 99 9 0.5
B As in A+Zn(25)+Cd(25)+Ca(25)+tartrate 0.50 0.49 98 90.5
1.00 1.01 101 90.7
C As in B+Mn2+(25)+NO−
3 (25) 0.50 0.52 1049 1.0
1.00 1.02 102 90.8
D As in C+CrV1 (25)+NH+
4 (25) 0.05 0.05 100 90.0
1.00 1.02 102 9 0.6
E As in D+Co2+(25)+K(25) 0.50 0.54 108 91.5
1.00 1.06 106 91.3

a
Average of five analyses of each sample.
b
The measure of precision is the SD.
 M.J. Ahmed, S. Banoo / Talanta 48 (1999) 1085–1094
Table 2
Analysis of high-speed steel and alloys
Certified reference material (composition)
BAS-CRM 64b High-speed steel (Cr,Mo,Vand Tc)
BCS-CRM 241/1 High-speed steel (Cr,V,W,Co, Mn, C, Si, Pand S)
BCS-CRM 220/1 High-speed steel (C,Si,S,P,Mn, Mo,V,Ni,Cr,Co, W and Cu)
BAS-CRM 10g High tensil (Cu,Sn,Zn,Pb,Ni,Fe,Al,Mn, and V)
a
Average of five determinations.
acetonic medium, however, maximum absorbance
was observed; hence a 50% acetonic solution was
used in the determination procedure.
4.1.3. Effect of acidity
Of the various acids (nitric, sulfuric, hydrochlo-
ric and phosphoric) studied, sulfuric acid was
found to be the best acid for the system. The
absorbance was at a maximum and constant when
the 10 ml of solution (1 mg ml − 1) contained
0.1–1.0 ml of 0.001 M sulfuric acid (or pH 4.0–
5.5) at room temperature (2595°C). Outside this
range of acidity, the absorbance decreased (Fig.
1). For all subsequent measurements 0.5 ml of
0.001 M sulfuric acid (or pH 4.75) was added.
4.1.4. Effect of time
The reaction is very fast constant maximum
absorbance was obtained just after the dilution to
volume and remained strictly unaltered for 48 h.
4.1.5. Effect of reagent concentration
Different molar excesses of DPCH were added
to fixed metal ion concentration and absorbance
were measured according to the standard proce-
dure. It was observed that at 1 mg ml − 1 V-chelate
metal, the reagent molar ratio 1:20 and 1:100
produce a constant absorbance of the V-chelate
(Fig. 2). Greater excesses of reagent were not
studied.
4.1.6. Calibration graph (Beer’s law and
sensiti6ity)
The effect of metal concentration was studied
over 0.1–30 mg ml − 1 distributed in three different
sets (0.1–1.0, 1 – 10, and 10 – 30 mg ml − 1) for
convenience of measurement. The absorbance was
1089
Vanadium(%)
Certified value Founda SD
1.99 1.98 90.05
1.57 1.58 90.07
2.09 2.10 90.06
0.52 0.58 90.08
linear for 0.1–30 mg ml − 1 of vanadium at 531 nm
(Fig. 3). The molar absorption coefficient and the
Sandell’s sensitivity [25] were 4.23× 104 l mol − 1
cm − 1 and 10 ng cm − 2 of Vv, respectively.
4.1.7. Effect of foreign ions
The effect of over 50 ions and complexing
agents on the determination of only 1 mg ml − 1 of
Vv was studied. The criterion for an interference
[26] was an absorbance value varying by more
than 5% from the expected value for vanadium
alone. There was no interference from the follow-
ing: 1000-fold amount of sulfate, sulfite, nitrate,
perchloride, bromide, chloride, iodide, thio-
cyanide, Na, Mg, Ba,K, MnII, Zn, NH4+ , Ca or
Cd; 100-fold amounts of tartrate, fluoride, CoIII,
NiII or HgII; 10-fold amounts of EDTA, oxalate,
citrate, CrIII, PbII azide, persulphate, phosphate,
WVI, AsIII, AsV, Cs, MnVII,CrVI, FeII, FeIII, CN − ,
or UVI. EDTA prevented the interference of a 10-
fold amounts of Ag, Al, CuII or MoVI. The quan-
tities of these diverse ions mentioned were the
actual amounts added and not the tolerance lim-
its. A 50-fold excess of iron FeII and FeIII or CuII
could be masked with ammonium thiocyanate or
fluoride. During the interference studies, if a pre-
cipitate was formed, it was removed by
centrifugation.
4.1.8. Composition of the absorbance
Job’s method [27] of continuous variation and
the molar-ratio [28] method were applied to ascer-
tain the stoichiometric composition of the com-
plex. A V-DPCH (1:3) complex was indecated by
both methods.
1090 M.J. Ahmed, S. Banoo / Talanta 48 (1999) 1085–1094

4.1.9. Precision and accuracy this method is highly precise and reproducible.
The relative SD (n =5) was 1.5 – 0.0% for 1– The detection limit (3 SD of the blank) and
300 mg of vanadium in 10.0 ml, indicating that Sandell’s sensitivity (concentration for 0.001 ab-

Table 3
Determination of vanadium in some environmental water samples

Sample Vanadium, mg l−1 Recovery 9 SD (%) SDr (%)b

Added Founda

Tap water 0 1.6 90.1 0.31

100 101.05 99.9 9 0.2 0.35
500 502.0 100 9 0.1 0.42
Well water 0 8.0
100 107.0 99 90.3 0.19
500 509.0 100.2 90.4 0.39
Rain water 0 1.4
100 102.0 100.5 9 0.1 0.14
500 501.5 100 9 0.0 0.00
River water
Karnaphuli (upper) 0 11.2
100 112.0 100.7 9 0.3 0.18
500 511.0 100 9 0.0 0.00
Karnaphuli (lower) 0 14.4
100 115.0 100.4 90.2 0.3
500 513.0 99.7 90.4 0.37
Sea-water
Bay of Bengal (upper) 0 5.0
100 104.0 99 90.01 0.08
500 505.0 100 9 0.0 0.00
Bay of Bengal (lower) 0 6.0
100 106.0 100 90.0 0.00
500 507.0 100.2 90.05 0.08
Lake water
Kaptai (upper) 0 18.5
100 119.0 100.4 90.4 0.29
500 520.0 100.3 90.5 0.34
Kaptai (lower) 0 20.0
100 119.0 99 9 0.3 0.41
500 5021.0 100.2 90.2 0.32
Drain water
Karnaphuli Paper Millc 0 35.00
100 136.0 100.7 90.5 0.45
500 536.0 102.0 90.6 0.35
Steel Milld 0 75.0
100 176.0 100.6 9 0.3 0.08
500 580.0 100.9 9 0.5 0.15
Eastern refinerye 0 145.0
100 250.0 102.0 9 0.6 0.49
500 640.0 99.2 90.5 0.55

a
Average of five replicate determinations.
b
The measure precision is the relative SD.
c
Karnaphuli Paper Mill, Chandraghona, Chittagong
d
Chittagong Steel Mill, Patenga, Chittagong.
e
Eastern Refinery, North Patenga, Chittagong.
 M.J. Ahmed, S. Banoo / Talanta 48 (1999) 1085–1094 1091

Table 4
Concentration of vanadium in blood and urine samples

Serial No. Sample Vanadium, mg l−1 Sample sourceb

AAS Proposed methoda

1 Blood 9.0 10.0 91.5 Heart-diseases

Urine 2.5 2.8 91.2 Patient (male)
2 Blood 370.0 381.0 91.0 Lung cancer
Urine 75.0 85.0 9 1.5 Patient (male)
3 Blood 10.0 12.0 9 1.4 Normal
Urine 3.0 3.2 9 1.3 Adult (male)

a
Average of five determinations9SD.
b
Samples were from Dhaka Medical College Hospital.

sorbance unit) for vanadium (V) were found to till the brisk reaction subsided. The solution was
be 20 ng ml − 1 and 10ng cm − 2, respectively. The heated and simmered gently after addition of 5
result for total vanadium were in good agreement ml of concentrated HNO3 untill all carbides were
with certified values (Table 2). The reliability of decomposed. Then 2 ml of 1:1 (v/v) H2SO4 was
our V-chelate procedure was tested by recovery added and solution was evaporated carefully to
studies. The average percentage recovery ob- dense white fumes to drive off the oxides of
tained for addition of a vanadium (V) spike to nitrogen and then cooled to room temperature
some environmental water samples was quantita- (25–30°C). After suitable dilution with de-ionized
tive as shown in Table 3. The method was also
tested by analysing several synthetic mixtures
containing vanadium (V) and diverse ions. The
results of biological analyses by the spectrophoto-
Table 5
metric method were excellent agreement with Determination of vanadium in some surface soil samplesa,b
those obtained by AAS (Table 4). The precision
and accuracy of the method were excellent. Sl. No. Vanadium (mg Sample source
g−1)
4.2. Applications S1c 0.0295 Clevedon Tea Estate (Syl-
het)
4.2.1. Determination of 6anadium in synthetic S2 0.0401 Esturine soil (Karnaphuli)
mixtures S3 0.0215 Chittagong University
Several synthetic mixtures of varying composi- Campus
S4 0.0265 Karnaphuli Paper Mill
tions containing vanadium (V) and divers ions of S5 0.0198 Marine Soil (Bay of Ban-
known concentrations were determined by the gle)
present method using sodium tartrate as masking S6 0.0310 Steel Mill
agent. The results are shown in Table 1. S7 0.0295 Clevedon Tea Estate (Syl-
het)
S8 0.0229 Bangladesh Oxygen Com-
4.2.2. Determination of 6anadium in alloys and pany (BOC)
steels S9 0.0225 T.S.P. Complex
A 0.1 g amount of an alloy or steel samples S10 0.0570 Eastern Refinery
containing 0.52 – 2.09% of vanadium was weighed a
Mean = 0.03 (mg g−1)
accurately and placed in a 50 ml Erlenmeyer SD= 90.01
b

flask. To it, 10 ml of 20% (v/v) sulfuric acid was c

Composition of the soil samples: C, N, P, K, Na, Ca,
added, carefully covering with a watch-glass un- Mg, Fe, NO3, NO2, Zn, SO4, Mn, Mo, Co etc.
1092 M.J. Ahmed, S. Banoo / Talanta 48 (1999) 1085–1094

Table 6
Determination of vanadium (IV) and vanadium (V) speciation in mixtures

Sl. No. V (V):V(IV) V, taken (mg ml−1) V,found (mg ml−1) Error (mg ml−1)

V(V) V(IV) V(V) V(IV) V(V) V(IV)

1 1:1 1.00 1.00 0.99 0.98 0.01 0.02

2 1:1 1.00 1.00 1.00 1.00 0.00 0.00
3 1:1 1.00 1.00 0.99 0.98 0.01 0.02
Mean error: V(V) = 90.0067; V(IV) = 9 0.013
SD: V(V) = 9 0.0058; V(IV) = 90.011
1 1:5 1.00 5.00 0.99 4.98 0.01 0.02
2 1:5 1.00 5.00 0.98 4.98 0.02 0.02
3 1:5 1.00 5.00 0.99 4.99 0.01 0.01
Mean error: V(V) = 9 0.013; V(IV) = 9 0.016
SD: V(V) = 9 0.0058; V(IV) = 9 0.0058
1 1:10 1.00 10.00 0.98 10.99 0.02 0.01
2 1:10 1.00 10.00 0.99 10.98 0.01 0.02
3 1:10 1.00 10.00 0.98 10.98 0.02 0.02
Mean error: V(V) = 90.016; V(IV) = 9 0.016
SD: V(V) = 9 0.0058; V(IV) = 9 0.0058

water, the contents of the Erlenmeyer flask were
warmed to dissolve the soluble salts. The solution
was then cooled and neutralized with dilute
NH4OH in the presence of 1 – 2 ml 0.01% (w/v)
tartrate solution. The resulting solution was
filtered, if necessary, through a Whatman No. 40
filter paper into a 50-ml calibrated flask. The
residue (silica and tungstic acid) was washed with
a small volume of hot (1 +99) H2SO4 followed by
water and the volume was made up to the mark
with de-ionized water.
A suitable aliquot of the above solution was
taken into a 10-ml calibrated flask and the vana-
dium content was determined as described under
procedure using thiocyanide or fluoride as mask-
ing agent. The results are shown in Table 2.
The resulting solution was then quantitatively
transferred into a 25-ml calibrated flask and made
upto the mark with de-ionized water.
An aliquot 1 ml of this preconcentrated water
sample was pipetted into a 10-ml calibrated flask
and the vanadium content was determined as
described under procedure using thiocyanide or
fluoride as a masking agent. The results are
shown in Table 3.
Most spectrophotometric methods for the de-
termination of vanadium in natural and sea-water
require preconcentration of vanadium [29]. The
concentration of vanadium in nutral and sea-wa-
ter is a few ng ml − 1 in Japan [17]. The mean
concentration of vanadium found in US drinking
waters is 6 ng ml − 1 [29].

4.2.3. Determination of 6anadium in 4.2.4. Determination of 6anadium in biological

en6ironmental water samples
Each filtered environmental water sample (1000
ml) was evaporated nearly to dryness with a mix-
ture of 1 ml of concentrated H2SO4 and 5 ml of
concentration HNO3 in a fume cupboard and was
then heated with 10 ml of de-ionized water in
order to dissolve the salts. The solution was then
cooled and neutralized with dilute NH4OH in the
presence of 1 – 2 ml of 0.01% w/v tartrate solution.
samples
Human blood (20–50 ml) or urine (30–50 ml)
was taken into a 100-ml micro-Kjeldahl flask. A
glass bead and 5 ml of concentrated nitric acid
were added and the flask was placed on the
digester under gentle heating. When the initial
brisk reaction was over, the solution was removed
and cooled. Sulfuric acid (1 ml of concentrated)
was added carefully followed by the addition of 1
 M.J. Ahmed, S. Banoo / Talanta 48 (1999) 1085–1094
ml of 70% perchloric acid and heating was contin-
ued to dense white fumes, repeating nitric acid
addition if necessary. Heating was continued for
at least 1/2 h. and then cooled. The content of the
flask was filtered and neutralized with dilute
NH4OH in presence of 1 – 2 ml of 0.01% (w/v)
tartrate solution, transferred quantitatively into a
10-ml calibrated flask and made upto the mark
with de-ionized water.
A suitable aliquot of this preconcentrated solu-
tion was pipetted out into a 10-ml calibrated flask
and the vanadium content was determined as
described under procedure using thiocyanide or
fluoride as masking agent. The results of biologi-
cal analyses by the spectrophotometric method
were found to be in excellent agreement with
those obtained by AAS. The results are shown in
Table 4.
The abnormally high value for the lung cancer
patient is probably due to the involvement of high
vanadium concentrations with As and Zn. Occur-
rence of such high vanadium contents are also
reported in cancer patients from some developed
countries [2]. The low value for the heart-disease
patient is probably due to a low vanadium con-
centration in the environment. There is an inverse
correlation between human heart-disease and
vanadium concentration in the environment [29].
4.2.5. Determination of 6anadium in soil samples
An air-dried homogenized soil sample (100 g)
was weighed accurately and placed in a 100-ml
Kjeldahl flask. The sample was digested in the
presence of an oxidizing agent following the
method recommended by Jackson [30]. The con-
tent of flask was filtered through a Whatman No.
40 filter paper into a 25-ml calibrated flask and
neutratized with dilute ammonia in the presence
of 1–2 ml of 0.01% (w/v) tartrate solution. It was
then diluted up to the mark with de-ionized water.
Suitable aliquots 1 – 2 ml was transferred into a
10-ml calibrated flask and a calculated amount of
0.001 M sulfuric acid needed to give a final acidity
of 0.0001–0.001 M H2SO4 (or pH 4.0 –5.5) was
added followed by 1 – 2 ml of 0.01% (w/v) thio-
cyanide or fluoride solution as masking agent.
Vanadium was then determined by the above
procedure and quantified from calibration graph
1093
prepared concurrently. The results are shown in
Table 5.
4.2.6. Determination of 6anadium (IV) and
6anadium (V) speciation in mixtures
Suitable aliquots (1–2 ml) of vanadium (IV+
V) mixtures (preferably 1:1, 1:5, 1:10) were taken
in a 25 ml conical flask. A few drops of 0.001 M
sulfuric acid and 1–3 ml of 1% (w/v) potassium
permanganate solution was added to oxidize the
tetravalent vanadium. 5 ml of water was added to
the mixtures and heated on the steam bath for
10–15 min. with occasional gentle shaking and
then cooled to room temperature. Then 3–4
drops of freshly prepared sodium azide solution
(2.5% w/v) was added and heated gently with
further addition of 2–3 ml of water, if necessary,
for 5 min. to drive off the azide cooled to room
temperature. The reaction mixture was transferred
quantitatively into a 10-ml volumetric flask, 1 ml
of 4.12 × 10 − 4M DPCH reagent solution was
added followed by addition of 0.5 ml of 0.001 M
H2SO4, it was made up to the mark with de-ion-
ized water. The absorbance was measured after 1
min. at 531 nm against a reagent blank. The total
vanadium content was calculated with help of the
calibration graph.
An equal aliquot of the above vanadium (IV+
V) mixture was taken in a 25 ml beaker, 1 ml of
0.01% (w/v) tartrate was added to mask vanadium
(IV) and neutralize with dilute NH4OH. The con-
tent of the beaker was transferred in to a 10-ml
volumetric flask, then 0.5 ml of 0.001 M sulfuric
acid solution was added followed by addition of 1
ml of 4.12× 10 − 4 M DPCH and made up to a
volume with de-ionized water. After 1 min the
absorbance was measured against a reagent
blank, as before. The vanadium concentration
was calculated in mg l − 1 or mg ml − 1 with the aid
of a calibration graph. This gives a measure of
vanadium (V) originally present in the mixture.
This value was substracted from that of the total
vanadium to get vanadium (IV) present in the
mixture. The results were found to be highly
reproducible. Occurrence of such reproducible re-
sults are also reported for different oxidation
states of vanadium [31]. The results of a set of
determination are given in Table 6.
1094 M.J. Ahmed, S. Banoo / Talanta 48 (1999) 1085–1094
5. Conclusion
The proposed method using DPCH not only is
one of the most sensitive methods for the determi-
nation of vanadium but also is excellent in terms
of selectivity and simplicity. Therefore this
method will be successfully applied to the moni-
toring of small amounts of vanadium in environ-
mental, biological and soil samples. No extraction
step is required and hence the use of organic
solvents, which are generally toxic pollutants, is
avoided.
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