Mikroehimiea Acta [Wien] 1969, 768--771

Department of Chemistry, Andhra University, Waltair, India

A New Spot Test for Cerium(IV)

By
U. Murali Krishna and K. Sreeramam*
(Received ~ovember 8, 1968)

Of the tests described by Feigl 1 for the detection of cerium the benzidine
test is not directly applicable in the presence of 5[n(II), Co(II), Cu(tI),
Ag(I) as well as chromates and other oxidizing agents, and the limit of
identification is increased from 0.18 #g to 70#g in the presence of a large
amount of iron(III). The hydrogen p e r o x i d e - a m m o n i a test is not applicable
in the presence of coloured ions and iron(III). The test with ammoniacal
silver nitrate is inapplicable in the presence of Mn(II), F e ( I I I ) and Co(H).
The spot teslu described by Rao and Satyanarayana 2 involves careful
a d j u s t m e n t of p~ to 11 -~ 0.5; t h e y stated t h a t no characteristic colour
was observed below p~ 6 and above p~ 13.
Pa88erini and Michelotti a proposed a test for cerium based on the red
colonr produced when methylene blue is added to an acidified solution
of cerium(IV), b u t the coloured product was reported to be transitory.
Reed a claimed t h a t better results could be obtained by using the reagent
in alkaline solution; however, the colour reaction was carried out with
40 ml of the solution under examination. I n this paper we describe a
new procedure for the detection of cerium(IV) employing methylene blue
as reagent. The rose-red colour produced is stable for more t h a n 12 hours.

Experimental
Reagents
(a) Methylene blue reagent (0.1~ 50 mg of methylene blue (!Vledieinal,
E. Merck, Germany) dissolved in 50 ml of water is treated with 4 ml of sodium
perehlorate solution (36o/0) and the mixture is stirred for 10 minutes. The
precipitate is collected on a G-3 sintered glass funnel and washed with 0.1 ~o
sodium perchlorate solution. It is then dissolved in 30 ml of perchlorie acid
(sp. gr. 1.47) and the solution is made upto the mark in a 50-ml graduated

* Present address: Chemistry Department, Andhra University, Post-

graduate Centre, Guntur, India.
U. M. Krishna and K. Sreeramam: A New Spot Test for Cerium(IV) 769

flask with water. More dilute solutions of the reagent employed in the procedure
are prepared by appropriate dilution with perchloric acid of strength present
in the stock solution.
(b) Cerium(IV) solution: 0.05N solution is prepared from cerium(IV)
ammonium nitrate (G.R. grade) in 1 N nitric acid; 0.05 N solution of
cerium(IV) sulphate in 1 _N sulphuric acid from cerium dioxide. The latter
solution is standardised according to the procedure of Willard and Young 5.
Either of these solutions may be employed with practically no difference
in the test.
(c) Nitric acid (sp. gr. 1.42) : A. R. quality (colourless) supplied by S. Merck
(India).
All other reagents employed are of analytical reagent grade.

Procedure
On the Spot plate. 0.1 ml of nitric acid and 0.05 ml of 0.005~o methylene
blue solution are placed on a spot plate and throughly mixed by means
of a glass rod. To this reagent 0.05 ml of the test solution containing
cerium(IV) are added and mixed. A rose-red colour is produced and the
intensity is unaltered for at least 12 hours. If instead an orange yellow
colour is observed [as is usually the case with concentrated cerium(IV)
solutions], 0.05 ml of 0.2 N iron(II) is added; the rose-red colour is then
imminent.
The intensity of the colour produced in the test can be increased
by using a more concentrated solution of methylene blue, when dealing
with solutions of cerium(IV) of strength more than 0.01 N.
Limit of identification: 7 ~g.
Dilution limit : I : 30 000.
In the Test T~tbe. The reagent is first prepared by adding 0.1 ml of
methylene blue (0.01%) to 2 ml of (i : 1) nitric acid in a test tube. To
this 0.05 ml of the test solution are added and the contents are thoroughly
mixed. A permanent rose-red colour is formed immediately. When the
test solution contains more than 0.05 N cerium(IV), an orange yellow
colonr appears in place of the usual rose-red colour; in such eases 1 to
2 drops of 0.2 N iron(II) solution are added and the usual rose-red colour
is obtained immediately. The intensity of the rose-red eolour obtained
in the test has been found to be unaffected by the excess of iron(II)
employed to reduce the unreacted yellow cerium(IV) in the test to
eolourless ~erium(III).
Limit of identification: 20/~g of cerium(IV) in a total volume of 2.0 ml.
Inter[erences. We have carried out experiments to investigate the
interferences of other inorganic ions with the eolour reaction for cerium(IV)
in the above procedures. A cerium(IV) solution prepared from cerium
dioxide containing 40% cerium and the remaining 60% other materials
including the associated rare-earths and thorium has been found to
770 U.M. Krishna and K. Sreeramam: [Mikroehim. Aeta

behave in the same way as the one free from these elements, thus showing
t h a t these materials do not interfere with the eolour reaction.
Chromium(VI), molybdenum(VI), uranium(VI), vanadium(V), vana-
dium(IV), ehromium(III), aluminium(III), iron(III), eopper(II), manga-
nese(II), niekel(II), zine(II), and silver(I) do not interfere even though
t h e y are present in 200-fold excess in either procedure; although there is
eolour masking initially due to some of these ions, the addition of iron(II)
later obviates the difficulty. Cobalt(II) does not interfere upto 100-fold
concentration. Manganese(VII) interferes. Chloride, sulphate, acetate,
perchlorate do not interfere even at 2000-fold concentration. Phosphate
at this concentration does not interfere; however, one has to wait for
about 30 seconds for the colour to appear. Much larger amounts of
phosphate completely hinder the colour formation. Since the reagent
itself contains a high concentration of nitric acid, it is obvious t h a t
nitrate even at such high concentration does not interfere.

Discussion
The intensity and stability of the rose-red coloured species formed
in the test are at the m a x i m u m at the optimum nitric acid concentration
prescribed in the text. However, moderate variations in the concentration
of the acid in the test does not affect the sensitivity of the test. The
intensity of the colour is also dependent on the concentration of both
cerium(IV) and methylene blue but when dealing with very small quanti-
ties of cerium(IV), a somewhat higher concentration of methylene blue
is detrimental since the intense blue colour of the unreaeted methylene
blue masks the rose-red colour. A similar masking effect due to excess
of cerium(IV) after reaction with methylene blue, however, can be
overcome by reducing the excess of the former with an excess of
iron(II).
Willard and Young ~ employed methylene blue as an indicator in the
titration of oxalate and arsenite with cerium(IV) sulphate in the presence
of iodine monoehloride. At the end point the indicator is changed to
pink, which in 5-10 seconds changes to permanent blue shade. The
transitory red product reported by Passerini and Michelotti 3 in their
test is presumably the same as the one encountered by g[illard and
Young in their titration. The rose-red eoloured product reported by
us is different from the one reported by earlier workers both in its stability
with time and resistanee to reducing agents like iron(II). I n the absence
of nitric acid, the transitory red produet is formed from methylene blue
and cerium(IV) which, however, cannot be stabilised b y the immediate
increase in the concentration of nitric acid. Further work relating to
this aspect is in progress.
1969/4] A New Spot Test for Cerium(IV) 771

Summary
A N e w Spot Test /or C e r i u m ( I V )
A new colour reaction for the detection of cerium(IV) which can be
carried out both in a test tube and on a spot plate has been described.
The test solution is treated with methylene blue in nitric acid solution (1 : 1)
to form a rose-red colour. This simple procedure has an advantage over
the existing tests in that it is applicable in the presence of oxidising agents
like chromium(VI), vanadium(V), nitrate, perchlorate and of coloured
ions like copper(II), cobalt(II), nickel(II), chromium(III), iron(III),
vanadium(IV), uranium(VI).
Zusammenfassung
Eine neue, sowohl in der Eprouvette wie auf der Tiipfelplatte ausfiihrbare
Farbreaktion zum Nachweis yon Cer(IV) wurde angegeben. Die Probel6sung
wird mit salpetersaurer Methylenblaul6sung behandelt und gibt eine rosarote
F~rbung. Die Reaktion hat gegenfiber bekannten Tests den Vorteil, in
Gegenwart yon Oxydationsmitteln wie Cr(VI), V(V), NO3-, C104- bzw.
in Anwesenheit gef~rbter Ionen wie Cu(II), Co(II), Ni(II), Cr(III), Fe(III),
V(IV) oder U(VI) anwendbar zu sein.

References
1 •.Feigl, Spot Tests, 5th Ed. Amsterdam: Elsevier. 1958. pp. 210-212.
2 V. P. Rao and D. Satyanarayana, Z. analyt. Chem. 197, 409 (1963).
a L. Passerini and L. Michelottr Gazz. chim. Ital. 65, 824 (1935).
4 R. A . Reed, Analyst 63, 338 (1938).
5 H . H . Willard and P. Young, J. Amer. Chem. Soe. 50, 1322, 1372 (1928).