Anal. Chem.
1986, 58, 2087-2088
stabilizer to regulate for constant power output from the MIP
power unit; and varying the depth of the plasma cavity for
optimal sample residence time in the plasma. This system
seems most suitable as a detector for high-performance liquid
chromatography and this possibility is currently under in-
vestigation in this laboratory.
ACKNOWLEDGMENT
The authors thank Sherritt Gordon Mines for the gift of
the MAK nebulizer and David Zellmer for drawing Figure 1.
Registry No. HzO, 7732-18-5; Cr, 7440-47-3; Mn, 7439-96-5;
In, 7440-74-6; V, 7440-62-2; Pb, 7439-92-1; Sr, 7440-24-6; Zr,
7440-67-7.
LITERATURE CITED
(1) Hieftje, G. M. Spectrochim. Acta, P a r t 8 1983, 388, 1465.
(2) Zander, A. T.; Hieftje, G. M. Appl. Spectrosc. 1981, 35. 357.
(3) (bode. S. R.; Baughman, K. W. Appl. Spectrosc. 1984, 38, 755.
(4) Beenakker, C. I. M.; -man, 6.; Boumans, P. w. J. M. spectr&/m.
Acta, Part B 1978, 338, 373.
CORRESPONDENCE
Homogeneous Precipitation of Nickel as the Dimethylglyoxime
Complex: Revisted
Sir: The gravimetric determination of nickel by precipi-
tation with dimethylglyoxime (DMG) to form the nickel di-
methylglyoxime complex (Ni-DMG) is one of the classical
methods in analytical chemistry (1-3). This method can use
either the direct precipitation of the complex from a basic
solution or the homogeneous precipitation using the hydrolysis
of urea to shift the p H of a slightly acidic solution to the
necessary basic conditions for precipitation. Recently, while
using the latter procedure for determining the nickel content
of samples of nickel ore, we obtained unsatisfactory results.
In some cases Ni-DMG precipitates were obtained contam-
inated with an unknown material. In others, large variations
were observed in the amount of complex formed in replicate
determinations. We had not encountered this before and to
our knowledge it has not been reported in the literature. This
note identifies the source of these problems.
EXPERIMENTAL SECTION
Procedure Used in Ore Analysis. Approximately 1.5 g of
each ore sample was dissolved in 20 mL of aqua regia and then
diluted to 200 mL with deionized water and the pH adjusted to
about 2. About 20 g of urea and 50 mL of a 1% dimethylglyoxime
solution dissolved in 1-propanolwere added to each solution. The
resulting solution was then gently heated to hydrolyze the urea
and precipitate Ni-DMG.
Visual inspection of replicate determinations on the same
sample after 0.5 h of heating suggested that in some instances
uneven amounts of Ni-DMG were being precipitated. This
situation was not rectified even on heating for several hours. Many
samples had replicates with quite obviously different amounts
of precipitate. The precipitate in all determinations was filtered
off by use of sintered glass crucibles and weighed. It was noticed
that some replicates, those with the smaller amounts of Ni-DMG,
were contaminated with a pale yellow, needlelike, crystalline
precipitate. We will refer to this material as compound A. The
larger crystals of compound A were removed from the finely
divided Ni-DMG. Samples of compound A were then analyzed
0003-2700/86/0358-2087$01.50/0
2087
Beenakksr, C. I. M.; Boumans, P. W. J. M. Spectrochh. Acta, Part8
1978, 338, 53.
Beenakker, C. I. M. Spectrochim. Acta, Part 8 1977. 328, 173.
Beenakker, C. I. M.; Spectrvchim. Acta, Part 8 1978, 318, 483.
Beenakker, C. I. M.; Boumans, P. W. J. M.; Rommers, P. philips Tech.
Rev. 1980, 39, 65.
Haas, D. L.; Caruso, J. A. Anal. Chem. 1984. 56, 2014.
Michkwicz, K. G.; Carnahan. J. W. Anal. Chem. 1985, 5 7 , 1092.
Urh, J. J.; Carnahan, J. W. Anal. Chem. 1985. 5 7 , 1253.
Deutsch, R. D.; Hieftje. 0.M. Appl. Spectrosc. 1985, 39, 214.
Deutsch, R. D.; Keilsohn, J. P.; Hieftje, G. M. Appi. Spectrosc. 1985,
39, 531.
Rezaalyaan. R.; Hieftje, G. M. Anal. Chem. 1985. 57, 412.
Isaaq, H. J.; Morgenthaler, L. P. Anal. Chem. 1975, 4 7 , 1748.
Kaiser, H.; Meddings, B. Eastern Analytical Symposium, New York,
17-19 November 1982; Paper No. 120.
Ng, R. C.; Kaiser, H.; Meddings, B. Winter Conference on Plasma
Spectrochemistry, San Diego, CA, 2-6 January, 1984; Paper No. 16.
Winge, R. K.; Peterson, V. J.; Fassel, V. A. Appl. Spectrosc. 1979,
33. 206.
(19) Haas, D. L. University of Cincinnati, personal communication, 1983.
RECEIVED for review November 22,1985. Accepted April 21,
1986.
with a Du Pont 21-490B mass spectrometer. The resulting mass
spectrum showed a molecular ion at mass 170 and did not have
any peaks characteristic of the presence of the lfNi and 2Ni
isotopes. This suggested that compound A was not one of the
original constituents of the homogeneous precipitation analysis
and also not the expected product.
A series of simple experiments to determine those reactants
required for the production of compound A showed that it was
produced when urea and DMG were heated together in an acidic
solution. Subsequently,the optimum conditions for the synthesis
of compound A were investigated primarily in order to obtain
sufficient material for a complete analysis. Solutions were pre-
pared containing identical amounts of hydrochloric acid but
varying mole ratios of urea to DMG, including a control containing
only DMG. These solutions were heated for 4 h and were mon-
itored at 0.5 h intervals for the presence of DMG. The maximum
amount of compound A was obtained with solutions containing
the largest urea to DMG mole ratios. From these experiments,
approximately 1.5 g of compound A was obtained for investigation.
While the optimum conditions for the production of compound
A were being determined, it was also found that butane-2,3-dione
was produced when DMG was heated under acidic conditions both
with and without urea present. Butane-2,3-dionewas identified
in aliquots of the reaction mixture with gas chromatography/mass
spectrometry and by isolation and preparation of the semi-
carbazone derivative.
Analysis of Compound A. Compound A was found to be
remarkably insoluble in most common solvents. However, it was
slightly soluble in boiling water and the material was recrystallized
from hot water. It was subsequently found to be soluble in
trifluoroacetic acid (4). The recrystallized material melted at about
345 "C with decomposition. C, H, and N analysis (Galbraith
Laboratories, Inc.) yielded C, 42.46; H, 6.26; and N 33.08. The
mass spectrum of the compound showed major peaks at mass 170,
142,127,109,101,85,69,58 and 42. IR spectra (KBr disk in a
Perkin-Elmer Model 621 IR) showed major peaks at 3235 cm-I
(N-H stretch), 2970,2940,2860 cm-' (C-H stretch) 1720,1665
cm-' (C=O stretch), 1430, 1380 cm-' (C-H bend), 1160 cm-I
(C-N stretch), and 725 cm-' (N-H out-of-plane bending). The
0 1986 American Chemical Society
2088 Anal. Chem. 1986, 58.2088-2091
elemental analysis and the mas8 spectrum with an apparent
molecular ion at nupi 170 suggested a compound with the formula
C6H1&02 (C, 42.39; H, 5.93;N, 33.H). This combined with the
IR data suggested structure I for the compound: 3a,6a-di-
methyltetrahydroimidazo[4,5-d]imidazole-2,5-dione. Structure
I suggested ari alternative synthetical route using butane-2,3-dione
and urea in an aqueous acidic solution. This reaction was ex-
tremely facile and produced a crystalline proddct that had
ideritical mass spectra, IR spectra, C, H and N analysis and
melting point as compound A. A mixture melting point was
identical with that of the indivitld kterials. A literature search
revealed that compound A was a known compound, with it and
ita near derivatives having been breRafed from the corresponding
diketones and substituted ureas (4-9). We conclude that our
compound A has structure I. This was further confirmed by
comparing the proton N M R of compourid A and the synthesized
material run in deuterated trifluoroacetic acid using a JEOL
FXSOQ NMR spectrometer.
DISCUSSION
The acidic solution chemistry of DMG in the presence of
urea is obviously more complex than the hydrolysis of urea
to ammoriia and formation of Ni-DMG. We suggest that the
formation of compound A occurs as a result of the slow hy-
drolysis of DMG to butane-2,3-dione and its subsequent re-
action with urea. If the initial pH of the solution is approx-
Micro Carbon Electrode for Intracellular Voltammetry
Sir: Since the earlier studies of Adams group (1,2)elec-
trochemistry has proved to be a powerful method for the
determination of amine neurotransmitters and ascorbic acid
in vivo ( 3 , 4 ) . The most frequently used microelectrodes are
constructed from carbon paste or a single carbon fiber enclosed
in a glass micropipet. The carbon fiber either protrbdes
forming a cylindrical electrode of 250-500 pm length and 8
pm diameter or is cut on the end of the glass coat so that the
active surface is a single disk of 20-500 pm diameter (5-8).
The size and form of these dlectrodes make them inadequate
for intracellular measurements. Yet there is no doubt that
much could be learned if measurements could be performed
inside individual cells. In this paper we report a technical
method to prepare a needle-tip micro carbon electrode with
a tip diiuneter ranging f r o b 0.5 to 2 pm which works in ox-
idation as well as in reduction. This microelectrode could be
implantd for several hours into identified neurons of Aplysia
witbout damaging them or affecting their electrophysiological
properties. We tested this new microelectrode by studying,
by differential p& voltammetry (DPV), the penetration into
a neuron of two electroactive drugs (antipyrine and metro-
nidazole, respectively, in oxidation and reduction) and by
measuring endogenous intracellular ascorbic acid.
0003-2700/86/0358-2088$01 S O / O
imately 2-3, the hydrolysis of urea will rapidly increase the
pH to 4.5 and Ni-DMG will be precipitated quantitatively
without being contaminated with compound A (even if a small
amount of A is produced, it is soluble enough to stay in so-
lution). If the initial solution is more acidic than pH 2-3, then
both compound A and Ni-DMG will be formed; if the solution
is very acidic, only compound A will be formed. Each of these
results has been observed.
CONCLUSION
We attribute this problem to an inadequate control of the
initial pH of the Ni2+ solutions prior to addition of urea and
DMG. We suggest that when the homogeneous precipitation
method in the determination of Ni is used,the pH be carefully
adjusted to lie between 2 and 3. Obviously the problem does
not arise if urea is omitted from the analysis.
Registry No. I, 28115-25-5;Ni, 7440-02-0; dimethylglyoxime,
95-45-4; urea, 57-13-6; butane-2,3-dione, 431-03-8.
LITERATURE C I T E D
(1) Tschugaeff, L. BBr Dtsch. Chem. as.1905, 3 8 , 2520.
(2) Tschugaeff, L. 2.Anorg. Chem. 1905. 4 6 , 144.
(3) Brunck, 0.Z . Angew. Chem. 1907, 20,824.
(4) Butler, A. R.; Hassain, I J. Chem. Soc., Perkin Trans 2 1981,
, 310-16.
(5) Biltz, H. Ber. Dtsch. Cbem. Ges. 1908, 41, 167-173.
(6) Seekles, L. R e d . Trav. Chim. Pays-Bas 1927, 48, 77-84.
(7) Imidazole and Its Derlvatives ; Hofmann, K., Ed.; Interscience: New
York, 1953;pp 227-232.
(8) Kuhling, D. Justus Liebigs Ann. Chem. 1973, 263-277.
(9) Suvorova, L. 1.; et al. Izv Akad. Nauk SSSR, Ser. Khim. 1979, 6 ,
1306-13 13.
J e n s Hemmingsen
David Larkin*
Thomas M a r t i n
Department of Chemistry
Towson State University
Towson, Maryland 21204
RECEIVED
for review January 13, 1986. Accepted April 14,
1986.
EXPERIMENTAL SECTION
Working and Reference Microelectrodes. The working
microelectrodes were prepared with carbon fibers (external di-
ameter 5-12 pm, Le Carbone Lorraine) sealed to a copper wire
with graphite powder in polyester resin (Figure 1A).
The sharpening and insulation of the carbon fiber bear some
similarities to the preparation of microplatinum electrodes used
in oxygen determination (9, IO).
The carbon fiber was electropolished (Figure 1A) by dipping
the extreme tip onto the surface of an half-saturated solution of
sodium nitrite containing detergent, TWEEN 40 (Sigma). A
similar technique as been described earlier (11). An alternating
current (50 Hz, 2-6 V) was passed through the solution between
the carbon fiber and a platinum macroelectrode. Under these
conditions, the carboli dissolved away slowly. At the end of this
treatment, the carbon fibei. had a very sharp tip in the range of
0.4-1.5 p m diameter.
A soda glass tube, 1 mm o.d., was heated locally and pulled
down to a diameter slightly larger t h d that of the carbon fiber.
A hook was made on the end of the pipet. The carbon fiber was
pushed down inside the tube uhtil the end of the copper wire was
blocked against the taper on the inside of the capillary tube (Figure
1B). The copper wire was fixed to the glass with adhesive and
the glass tube was placed in a de Fonbrune microforge, point
downward, and a small weight (about 10 mg) was hung on the
0 1986 American Chemical Society