ANALYSIS OF TRACE METALS IN SODIUM BY FLAMELESS ATOMIC ABSORPTION

SPECTROPHOTOMETRY

T. R. Mahalingam, R. Geetha, A. Thiruvengadasamy

and C. K. Mathews
Reactor Research Centre
Kalpakkam India

INTRODUCTION

The determination of trace metals in sodium is usually carried

out by distilling off the sodium in vacuum and analysing the residue
by flame Atomic Absorption Spectrophotometry (1-3). The distillation
is done to avoid aspirating a highly concentrated solution which
would lead to problems such as clogging of the nebuliser and severe
spectral interference. Moreover distillation also serves as a
concentration step. A sample weight of 50 gms has been used for the
analysis of nuclear grade sodium (2). In our laboratory we have
followed the method of distillation and analysis by flame AAS for
the commercial sodium samples. But there are certain situations
where it is desirable to avoid the distillation step as in the case
of the analysis of volatile impurities such as Zn, Cd and Pb which
are lost partially or wholly during the distillation process.
Moreover use of small sample size is desirable especially while
analysing the primary sodium. With these objectives a direct method
to analyse sodium by AAS using the graphite furnace atomiser has
been developed in our laboratory. With the superior sensitivities
(10- 12 g) attainable with very small sample volumes (20 ~l) we have
found that it is possible to determine various impurities such as
Cu, Cr, Co, Mn and Pb directly by placing as low as 2 mg of the
sample in the graphite cuvette. By employing a suitable temperature
programme it has been possible to remove the bulk of the matrix
before atomisation, thereby minimising the matrix interference.
This paper describes the direct method developed in our laboratory
for the analysis of sodium and compares it with the distillation
cum flame AAS method.

329
H. U. Borgstedt (ed.), Material Behavior and Physical Chemistry in Liquid Metal Systems
© Plenum Press, New York 1982
330 T. R. MAHALINGAM ET AL.

EXPERIMENTAL

Apparatus

Atomic Absorption Spectrophotometer (Model IL-751) made by

Mis. Instrumentation Laboratory Inc., USA fitted with both flame
atomiser and the controlled temperature furnace atomiser (CTF 555)
has been used. It is a double-beam instrument having the D2 arc
background correction facility. The graphite cuvette temperature
is measured by a temperature sensor (tungsten alloy) which is in
contact with it and acts as a resistance thermometer. The sensor
forms part of an electrical bridge circuit, which in turn switches
off the operating current when the proper temperature is reached.
The temperature is indicated on a panel meter and the correctness
of the indication was tested by checking the melting points of pure
copper and tantalum in the cuvette.

Reagents

Demineralised water, double distilled in quartz distillation

assembly has been used for all experimental work. Electronic grade
nitric acid (BDH) was double distilled in quartz and used.

Stock standard solutions containing I mglml of the elements of

interest were prepared using highly pure metals or salts (99.9 % or
better). Dilutions were done with quartz distilled water and 0.1 N
acidity was maintained. Solutions were stored only in clean
polythene bottles.

Procedure
1. Sample Preparation:

All the laboratory-ware used were thoroughly cleaned

successively in 1:1 nitric acid and 10 % EDTA solution (left
overnight). Subsequently they were thoroughly washed with quartz
distilled water and the washings checked by flameless AAS before
they were used for either standards or samples. Washing with EDTA
helped especially in the reduction of the manganese blank which was
not getting removed by just acid cleaning.

"Nuclear grade" sodium supplied by Mis. Metaux Speciaux, West

Germany and the "commercial grade" sodium supplied by Mis. Alkali
Metals, Hyderabad were studied. These sodium samples were out and
weighed in an inert atmosphere glove box. For sampling the sodium
for the analysis of Cr, Co, Mn and Pb a clean knife made of high
pur1t1y copper was used. For the analysis of copper, a clean
stainless knife was used.

The distillation procedure is described elsewhere (2). Sodium

was sampled in tantalum crucibles and placed in a pyrex distillation