3-104

METALS (3000)

3500-V A. Introduction
1. Occurrence and Significance

Vanadium (V) is the first element in Group VB in the periodic

table; it has an atomic number of 23, an atomic weight of 50.94,
and valences of 2, 3, 4, and 5. The average abundance of V in the
earths crust is 136 ppm; in soils it ranges from 15 to 110 ppm;
in streams it averages about 0.9 g/L, and in groundwaters it is
generally 0.1 mg/L. Though relatively rare, vanadium is found
in a variety of minerals; most important among these are vanadinite [Pb5(VO4)3Cl], and patronite (possibly VS4), occurring
chiefly in Peru. Vanadium complexes have been noted in coal

* Approved by Standard Methods Committee, 1997.

Joint Task Group: 20th EditionSee 3500-Al.

and petroleum deposits. Vanadium is used in steel alloys and as

a catalyst in the production of sulfuric acid and synthetic rubber.
The dominant form in natural waters is V5. It is associated
with organic complexes and is insoluble in reducing environments. It is considered nonessential for most higher plants and
animals, although it may be an essential trace element for some
algae and microorganisms. Laboratory and epidemiological evidence suggests that vanadium may play a beneficial role in the
prevention of heart disease. In water supplies in New Mexico,
which has a low incidence of heart disease, vanadium has been
found in concentrations of 20 to 150 g/L. In a state where
incidence of heart disease is high, vanadium was not found in
water supplies. However, vanadium pentoxide dust causes gastrointestinal and respiratory disturbances. The United Nations

VANADIUM (3500-V)/Gallic Acid Method

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Food and Agriculture Organization recommended maximum

level for irrigation waters is 0.1 mg/L.
2. Selection of Method

The atomic absorption spectrometric methods (3111D and E),

the electrothermal atomic absorption method (3113B), the in-

ductively coupled plasma methods (3120 and 3125), and gallic

acid method (3500-V.B) are suitable for potable water samples.
The atomic absorption spectrometric and inductively coupled
plasma methods are preferred for polluted samples. The electrothermal atomic absorption method also may be used successfully
with an appropriate matrix modifier.

3500-V B. Gallic Acid Method

1.

c. Minimum detectable concentration: 0.025 g V in approximately 13 mL final volume or approximately 2 g V/L.

General Discussion

a. Principle: The concentration of trace amounts of vanadium

in water is determined by measuring the catalytic effect it exerts
on the rate of oxidation of gallic acid by persulfate in acid
solution. Under the given conditions of concentrations of reactants, temperature, and reaction time, the extent of oxidation of
gallic acid is proportional to the concentration of vanadium.
Vanadium is determined by measuring the absorbance of the
sample at 415 nm and comparing it with that of standard solutions treated identically.
b. Interference: The substances listed in Table 3500-V:I will
interfere in the determination of vanadium if the specified concentrations are exceeded. This is not a serious problem for Cr6,
Co2, Mo6, Ni2, Ag, and U6 because the tolerable concentration is greater than that commonly encountered in fresh water.
However, in some samples the tolerable concentration of Cu2,
Fe2, and Fe3 may be exceeded. Because of the high sensitivity
of the method, interfering substances in concentrations only
slightly above tolerance limits can be rendered harmless by
dilution.
Traces of Br and I interfere seriously and dilution alone
will not always reduce the concentration below tolerance limits.
Mercuric ion may be added to complex these halides and minimize their interference; however, mercuric ion itself interferes if
in excess. Adding 350 g mercuric nitrate, Hg(NO3)2, per sample permits determination of vanadium in the presence of up to
100 mg Cl/L, 250 g Br/L, and 250 g I/L. Dilute samples
containing high concentrations of these ions to concentrations
below the values given above and add Hg(NO3)2.

TABLE 3500-V:I. CONCENTRATION AT WHICH VARIOUS IONS INTERFERE

THE DETERMINATION OF VANADIUM
Ion

Concentration
mg/L

Cr6
Co2
Cu2
Fe2
Fe3
Mo6
Ni2
Ag
U6
Br
Cl
I

1.0
1.0
0.05
0.3
0.5
0.1
3.0
2.0
3.0
0.1
100.0
0.001

IN

2. Apparatus

a. Water bath, capable of being operated at 25 0.5C.

b. Colorimetric equipment: One of the following is required:
1) Spectrophotometer, for measurements at 415 nm, with a
light path of 1 to 5 cm.
2) Filter photometer, providing a light path of 1 to 5 cm and
equipped with a violet filter with maximum transmittance near
415 nm.
3. Reagents

Use reagent water (see Section 1080) in preparation of reagents, for dilutions, and as blanks.
a. Stock vanadium solution: Dissolve 229.6 mg ammonium
metavanadate, NH4VO3, in a volumetric flask containing approximately 800 mL water and 15 mL 1 1 nitric acid (HNO3).
Dilute to 1000 mL; 1.00 mL 100 g V.
b. Intermediate vanadium solution: Dilute 1.00 mL stock
vanadium solution with water to 100 mL; 1.00 mL 1.00 g
V.
c. Standard vanadium solution: Dilute 1.00 mL intermediate vanadium solution with water to 100 mL; 1.00 mL
0.010 g V.
d. Mercuric nitrate solution: Dissolve 350 mg
Hg(NO3)2 H2O in 1000 mL water.
e. Ammonium persulfate-phosphoric acid reagent: Dissolve
2.5 g (NH4)2S2O8 in 25 mL water. Bring just to a boil, remove
from heat, and add 25 mL conc H3PO4. Let stand approximately
24 h before use. Discard after 48 h.
f. Gallic acid solution: Dissolve 2 g H6C7O5 in 100 mL
warm water, heat to a temperature just below boiling, and
filter through filter paper.* Prepare a fresh solution for each
set of samples.
4. Procedure

a. Preparation of standards and sample: Prepare both blank

and sufficient standards by diluting 0- to 8.0-mL portions (0 to
0.08 g V) of standard vanadium solution to 10 mL with water.
Pipet sample (10.00 mL maximum) containing less than 0.08 g
V into a suitable container and adjust volume to 10.0 mL with
water. Filter colored or turbid samples. Add 1.0 mL Hg(NO3)2

* Whatman No. 42 or equivalent.

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solution to each blank, standard, and sample. Place containers in

a water bath regulated to 25 0.5C and allow 30 to 45 min for
samples to come to the bath temperature.
b. Color development and measurement: Add 1.0 mL ammonium persulfate-phosphoric acid reagent (temperature equilibrated), swirl to mix thoroughly, and return to water bath. Add 1.0
mL gallic acid solution (temperature equilibrated), swirl to mix
thoroughly, and return to water bath. Add gallic acid to successive samples at intervals of 30 s or longer to permit accurate
control of reaction time. Exactly 60 min after adding gallic acid,
remove sample from water bath and measure its absorbance at 415
nm, using water as a reference. Subtract absorbance of blank from
absorbance of each standard and sample. Construct a calibration
curve by plotting absorbance values of standards versus micrograms
vanadium. Determine amount of vanadium in a sample by referring
to the corresponding absorbance on the calibration curve. Prepare a
calibration curve with each set of samples.

METALS (3000)

5. Calculation

mg V/L

g V (in 13 mL final volume)

original sample volume, mL

6. Precision and Bias

In a synthetic sample containing 6 g V/L, 40 g As/L, 250

g Be/L, 240 g B/L, and 20 g Se/L in distilled water,
vanadium was measured in 22 laboratories with a relative standard deviation of 20% and no relative error.
7. Bibliography
FISHMAN, M.J. & M.V. SKOUGSTAD. 1964. Catalytic determination of
vanadium in water. Anal. Chem. 36:1643.