Analytica Chimica Acta

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437
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The determination of molybdenum by atomic absorption spectroscopy

KIRKBRIGHT, SMITH AND WEST have recently reported the determination of

molybdenum in alloy steels’ and of niobium and tantalum” with a nitrous oxide-
acetylene flame. These authors did not find interference from foreign ions, either bc-
cause of the presence of large concentrations of the matrix element iron which causes
severe depression of molybdenum absorptionl, or because of a rather selective ex-
traction of molybdenum(V1) as its oxinate from a medium containing both EDTA
and fluoride. Earlier work on the determination of aluminum3 and vanadium” in
nitrous oxide-acetylkne flames indicated that the presence of certain ions caused con-
siderable enhancement in the absorption signal of these metals. This observation
prompted us to ascertain the effect of various ions on the determination of molyb-
denum in aqueous samples. The results indicated that numer,ous ions interfere. This
communication describes the details of this investigation and a simple and rapid
procedure is proposed to overcome the interferences.

Apparatacs
A Perkin-Elmer (Model 303) atomic absorption spectrophotometer was used
for absorption measurements. The standard burner head on the Perkin-Elmer ‘burner
mount was replaced by a nitrous oxide-acetylene burner head with a slot length of 3
in and a width of 0.015 in. In addition to the two-stage regulators on the gas tanks,
pressure gauges were used in the nitrous oxide lines and a flow meter was used in the
acetylene line. A Perkin-Elmer hollow-cathode lamp was used as radiation source.

Reagents
A stock solution containing I mg/ml of molybdenum(V1) was prepared by dis-
solving 1.840 g of ammonium molybdate tetrahydrate in I 1 of distilled water. Stan-
dard working solutions were prepared by appropriate dilution of the stock solution.
Solutions for interference studies were prepared from reagent-grade chemicals.

TABLE I
OPERATING CONDITIONS

Wavelength: 3232.6 A Nitrous oxide

Slit: 0.3 mm (2 A) Atomizer: 35 p.s.i.
Lamp, current: 35 mA Auxiliary: 15 p.9.i.
Acctylcnc: 5 l/min.

Operating conditiom
The optimum operating conditions listed in Table I were established with a
zo-p.p.m. solution of molybdenum. Absorption measurements were made at the
rose-red inner cone of the flame about I cm above the burner head. Water WV first
sprayed to set the zero of the instrument and, while the standard molybdenum

Anal. Chim. Acta, 44 (1969) 437-439

 438 SHORT COMMUNICATIONS

solution was aspirated, the burner position was adjusted to give maximum absorption.
Under these conditions the sample uptake was about 4 ml per min and the sensitivity
was I p.p.m. of molybdenum for I% absorption.

Interferewe stwi?ies
DAVIDIhas reported the suppressing effect of certain ions in the molybdenum
absorption in an air-acetylene flame which were completely eliminated by the ad-
dition of aluminum chloride. MOSTYN AND CUNNINGHAM~ later recommended the use
of ammonium chloride as an interference-suppressing agent for the analysis of molyb-
denum in ferrous alloys. Our examination of the effect of various foreign ions in a
nitrous oxide-acetylene flame showed that most ions affect molybdenum absorption.
The ions examined and their effect on molybdenum absorption are shown in Table II.
The cations were added as chlorides or nitrates, or, in certain instances, as sulfates,
and the anions as sodium or potassium salts. In these investigations the concentration
of molybdenum was 20 p,pm. and that of interferent 200 p.p.m.

TABLE II
INTERFERENCES FROM VARIOUS SUBSTANCES ON MOLYBDENUM ABSORPTION

(Molybclcnum: 20 p.p.m.)
- ----
Iatevfercd Absorption Interfevent A bsorptio9b Inter/event A hovption
(a00 p.p.m.) C%) (a00 p.p.m.) (% ) (200 p.p.m.) (%)

None 19.8 HCOa- 23.5 Ccl 2+ 13.3

Br- 22.6 HAsO.~=- 24.5 Hga3’ 19.7
I- 22.4 Li+ 19.8 H@+ 19.0
F- 16.7 Ns+ 20.0 Sna+ 18.4

zw-
SO&
19.6
23.8
22.9
I<+
La&+
ca=+
19.8
23.3
8.7
Fe3+
Cr3+
Pb”’
23.6
20.8
22.6
s’

NOa- 21.5 Srs+ 2.7 Sbs+ 22.8

HPOJa- 2G.8 BZl.=+ 13.2 cc4* 12.3

seonn- 21.4 M@‘* 19.8 uo+ 23.6
TeOa+ 22.8 Mna+ 19.8 Al=+ 27.3
VV04=- x9.8 coa+ 21.4 Ti4+ 27.2

IhO,+ 19.6 Ni3+ 23.5 Zr4+ 24.8

von- 21.G ma+ 23.2 BC3’ 27.0
SiOP 25.0 cu=+ 24.3
coca- 23.5 %n3+ 23.7

The effect of acids was examined by adding 5 ml of the appropriate concen-

trated acid to the solution followed by dilution to xoo ml with distilled water. Both
perchloric and acetic acids enhanced the absorption by about 30%, whereas sulfuric
acid interfered by reducing the sensitivity by about 25 o/O.Hydrochloric acid and nitric
acid’showed little affect on molybdenum absorption.
An examination of Table II indicates that most ions caused an enhancement
in molybdenum absorption. The few ions that showed suppressing effect included Caa+,
Baz+, Sre+, Cd2+ and Ce+. It is also evident from Table II that the presence of ions

Anal. Chicn. ,Actn, 44 (1969) 437-439

SHORT COMMUNICATIONS , 439

such as Al3+ and Ti4+ which readily form stable oxides in the flame, caused maximum
enhancement of molybdenum absorption. Later experiments confirmed that the in-
terferences from these ions were not additive, as no further enhancement was noticed
when more than one refractory metal ion was present in the sample. Although, in
these instances, the enhancement in sensitivity could be attributed to the competitive
reaction to form stable oxides, as was noticed in the case of aluminums and vanadium”,
the reason for an enhancement in the presence of most other ions was not clear.
An attempt was next made to determine the interfering effect of various ions
on molybdenum absorption in the presence of a refractory metal ion. Aluminum was
chosen for examination as it is readily available and has already been shown to be
effective in overcoming the interferences in air-acetylene flame+. Although it was con-
firmed experimentally that 50 p.p.m. of aluminum is sufficient to produce maximum
enhancement of molybdenum absorption, a higher concentration of aluminum (IOO
p.p.m.) was present when the effect of various ions was re-investigated. The concen-
tration of molybdenum and interferents were, as before, 20 p.p.m. and 200 p.p.m.
respectively. None of the ions listed in Table II showed any effect on molybdenum
absorption when the absorption values were compared to solutions containing iden-
tical concentrations of molybdenum and aluminum in the absence of extraneous ions.
The interfering effect of the few ions that were found to suppress molybdenum ab-
sorption also disappeared in the presence of aluminum.

The results of this investigation indicated that the determination of molyb-

denum in nitrous oxide-acetylene flame was subject to interference from several ex-
traneous ions and compounds. Depending upon the ion present, the interference was
either an enhancement or a depression in the molybdenum absorption. However, the
method could be made more selective by the addition of aluminum to the samples.
The sensitivities in the absence and presence of aluminum were respectively I p.p.m.
and 0.8 p.p.m. of molybdenum for 1% absorption.

This work was supported by the US. Public Health Service Grant AP 00128
from the National Center for Air Pollution Control, Bureau of State Services.

Coates Chemical Laboratory, T. V. RAMAKRISHNA

Louidhna State Ukx&ty, PHILIP w. WEST
Batoti Rouge, La. 70803 (U.S.A.) J. W. ROBINSON

I G. F. KIRKBRIGHT, A. M. SMITH AND T. S. WEST, Analyst, 91 (1966) 700.

2 G. F. KIRKBRIGHT, M. K. PETERE AND T. S. WEST, Analyst, gr (1966) 705.
3 T. V. RAMAKRISHNA, P. W. WEST AND J. W. ROBINSON, Anal. Chim. Act% 39 (1967) 81.
4 S. L. SACHDEV, J. W. ROBINSON AND P. W. WEST, Ana2. Chim. Acta. 37 (1967) 12.
:D. J. DAVID, Atialyst, 86 (x96x) 730.
6 R. A. MOSTYN AND A. F. CUNNINGHAM, Anal. Clrem., 38 (x966) 121.

(Received August xzth, 1968)

Anal. Claim. Acta. 44 (1969) 437-439