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A~alyfzca Cinmrca Acfa

544 EIscv1er IutllslIing Conlpdny, Alllstcrclarn


Printed in The Netherlands

The purity of commercial diphenylcarbazide

Diphenylcarbazlde (DPCI) and diphenylcarbazone (DPCO) are frequently


used in analytical chemistry for spot tests, metal complexing and other routme ,
procedures. KXUMHOLZ AND KRUMHOLZI, however, have shown that commercially
available DPCO is an equimolar mixture of DPCI and DPCO. They described a
mcthocl for separating the components based upon a greater solubihty of DPCO
in sodium hydroxide.
Earlier, the DPCI reagent, preparccl by heatmg urea with an excess of phenyl-
Ilydrazine, was found2 to be an addition compound of DPCI and phenylsemlcarbaztde
(PSCI). Howcvet, accordmg to the method of CAZENIXJVE AN11 MOHIZAU~, no PSCI
is formecl on reacting phenylhydrazine with either diphenyl or gualacol carbonate
instead of urea. Therefore, disslmllar reagents have been used in studies of Cr-DPCI
complexes4--fl, which probably explains the controversial results published so far
It is also known that the purity of the DPCI reagent seems to be a major factor
governmg the colour intensity of these complexes 13. On the other hand, the results
obtained by extracting with isopentanol these complexes formed by clther the pure
or the double compound appeared to be quite sm~ilarl4.
The purpose of the present work was therefore to investigate the compositmn
01 commercial DPCI obtamecl from several sources, and where the reagents were
impure, to separate the components by column chromatography.

A&aratus. Glass plates were used for thm-layer chromatography. The


analytical separations were performed wrth a column of 20 cm length and 4 cm dla-
meter. A 1-1 separatory funnel provided with a pressure-regulation tube was placed
at the top of the column. The lower portion, fitted with a porous dtsk of sintered
glass (PI), was closed by a glass stopcock. The fractions were collected with a Serva
Model 63 fraction collector (Heidelberg). Preparative-scale separations were performed
with columns of Go cm length and 7 cm diameter, equipped with a 2-l scparatory
funnel and a pressure-regulation tube. The eluents were nitrogen-pressurized. A
2-way stopcock at the bottom of the column permitted either sampling or collection
of the effluents, The collectors were placed in a glove bag (model X-17-17 IZR,
Cheltenham, Pa ) which was also nitrogen-pressurized. The column and accessories
were placed in a dark room,
Melting points were determined with a Mettler FPI Melting and Uorling Point
Apparatus (Zilrich, Switzerland). The ultraviolet spectra (methanol) were obtained
with a l3eckman DK 2A Spectrophotometer. The infrared spectra (KBr disks) were
recorded on a Perkln-Elmer Model 225 Spectrophotometer.
Matevials. The followmg DPCI samples were mvestigated. (A) DPCI, prepared
in the laboratory by reaction of diphenyl carbonate and phenylhydrazinc; (13)
UDH Analar, Poole, G.B.; (C) Matheson, Coleman and Bell, Norwood, U.S.A.;
(D) Fluka purum (reagent grade), Buchs, Switzerland; (IX) Schuchardt I;* -163,
Mtincllen, W. Germany; (17) BDH, Spot Test Reagent, (G) UCB (reagent grade),
Brussels, Belgium; (I-1) lLIerck (reagent grade), Darmstadt, W. Germany; (I) Uaker
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Analyzed Reagent, 13aker Chemicals, Deventer, The Netherlands, (J) Carlo Erba
RP, Milano, Italy, and (I<) as (A) but with UY~Umstead of diphenyl carbonate.
The following adsorbents were used: (I) polyamide powder TLC G (Perlon) ,
(II) polyamide powder TLC II (Nylon II); and (III) TLC 66 (Nylon 66). All were
obtained from Machercy-Nagel GmbH., W. Germany.
The t.1 c. plates were either hand-made from one part of polyamide powder
(I-III) and five parts of methanol, or commcrctal (DC-Alufolien Polyamid II, 17254,
Merck, Darmstadt) The column adsorbent was M & N polyamide powder (column
chromatography grade).
Chromalograjhc fwocedzrres A solvent system A (water-methanol-acetic acid
I 3 : 0.04) was used for thin-layer and chromatographic separations Thin-layer
chromatography wan, performed by the classical ascending technique. The spots
wcrc detected by n-radiation with light at 366 nm for several hours However, instant
detection was also possible when commercial t.1 c. plates were used by means of
light at about 254 nm.
The column adsorbent was washed several times wltll methanol before use,
The column was charged with about S mg of DPCI and eluted at a rate of one drop
per 7-8 sec. The effluents were collected at intervals of xoo see ancl monitored with
the spectrophotometer at a wavelength of ZSO nm. The first component was elutecl
with a 5-fold aqueous dilution of solvent system A whereas the seconcl component
was elutccl with undiluted A.
The experiments were repeated on a preparative scale to permtt ldentiflcation
of the first component by other technique5 The column was charged with about 1.5 Q
of DPCI Sample, and again nitrogen-pressurized. The effluents were collected with
the use of a glove bag, and evaporated to dryness with a I3iichl Rotavapor at 28.
The precipitate was dissolved in water and allowed to crystallize m the cold A seconcl
crystallization m methanol was performed on a steam bath. Carbon tetrachloride
was added slowly to start crystallization.
Since the components appeared to be both air- and light-sensitive, particularly
when in solution. it was necessary to chromntograph in the dark and in an atmosphere
of nitrogen. Samples which were kept m the dark and under nitrogen did not 1oTe
colour for several months.

The t l.c. results (171~: I) confirm that most DPCI samples were a mixture
of two components. All elutlon patterns (Fig. 2) obtamed with small columns were
quite similar for samples D-T<. The first component was identified as PSCI by
infrared spectroscopy (Fig. 3). The lip-values for dlffcrent adsorbents were as shown
in Table I.
The amount of PSCI (about 40%) present in some commercial samples wa\
estimated by spot calorimetry according to the fluorescence quenching technique.
However, the ultraviolet spectra (Fig. 4) of both components are quite similar, as
may be expected for hydrazide derivatives. I3oth compounds display an aniline-
spectrum with maxima around 232 and ZSO nm. The strong absorbance band of
PSCI (a,,, 230.5 nm) does not coincide with the corresponding band of DPCI
(A,,, 234 o nm). On the other hand, both molecules absorb at 280 nm. This band
may be attributed to the phenylhydrazo chromophore, so that an e-value twice that

.4?inl Clht Ada, jjr (1970) 544-548


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546

A B C D E F G H I J K

l71g J. Thin Iaycr chromatograms (plate b) of samples A-K on Polyamide I I.

l71g 2. Elution pnttcxn of sample D wvlth an analytical column (Polynmidc 6)

L-.--L_ 1 I I I I I I I. y
4000 3000 2000 1600 1200 000 400
Frequency (cm-l)
Fig. 3. The infrarccl spectrum of phenylscmlcarbazldc (ICBr).

of PSCI may be expected for DPCI. The reference e-values for DPCI and PSCI
were determined from commercial samples which were purified as described above.
The percentages of DPCI and PSCI were calculated by linear interpolation between
these values. The results are given in Table II.

Anal. Chim. Ada, 51 (1970) 544-548


SHORT COMMUNICATIONS 547

TABLE I
&. VhLUES X-OH DPCI AND PscI ON DIFFERENT ADSORBCNTS

Adsorbmrl

Dlphcnylcarbahicle (DPCI)
Phenylscmlcnrbazldc (PSCI)

5 I

2bL- 250 275 300


Wavelength (nm)

Fig. 4 The ultrnvwlct spcctr,r (methanol) of tllphcnylcnrbazldc (sold IKIC) g~xdpllcnylscmlc.7rbazIdc


(clottccl Irllc)

TABLE II
~*CLTING Po*Nrs, O/,JZ)PCI AND I?3X, A,,., AND LOG E-VALucs 017 sob115conlnlBRcxAL DPCI
SAMPLES

Snmples MP / DPCI / PSCI Annx Log E

A x71.0 100 0 234 43.51


280 3 497
172 0 100 0

: 171.2 IO0
I3 164 9 3:
E 164 5 2 34
P 1.64 7 64 36
.
163 9 63 37
Z 163 2 65 3.5
I rG2 I 69 31
J 16.37 GO 40
I< 1G4 I G2 38
PSCI 8 170 5 0 100 23r 4 056
280 3,173

0 Commercial phcnylscmlcarbazlclc (IMerck) purded as dcscrlbed m the text

Most commercial DPCI reagents are approximately equlmolar rnlxtures of


DPCI (61%) and PSCI (39%), when prepared by heating urea with phenylhydrazine.
By reaction of dlphenyl carbonate, instead of urea, with phenylhydrazine, no PSCI
is formed.

A~zal.CJ~tnr Acta, 51 (rgyo) 544-548


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548

We thank Dr. A R. 1;. ChlxNULER for hts help in preparmg thus ntanuscript.
We arc also grateful to Mrs. J VERMYLEN-DE WXNTBR for recording the U.V. spectra.

G. J. WILLE~GS
R. A. LONTIE*

w. A, ~EIH-PAUL

1 3
2 c.
3 1
t I
.5A
CJA
7M

Preparation and use of electrodeless discharge tubes for the atomic


absorption spectrophotometry of some alkali metals

Most atomic absorption methods for the determination of alkali rnctals have
used spectral-dtscharge lamps as light sources although hollow-cathode lamps are
commercially available. ALT)OUS et at.1 recently dcscrrbed the preparation of electrode-
less discharge tubes for these elements ; the metals were used as the lamp charge
for the sodmm and potassium tubes and for magnesium, whereas the chloride was
preferred for hthium. Attack on the tube walls by the metallic vapours was mmimised
by usmg a two-ply glass for the tube envelopes, the inner layer being a sodium va-
pour-resistant glass, but the preparation of the tubes then requrred considerable
care. The applicability of these tubes to atomic absorption spectroscopy was not
discussed.
This communication describes the preparation of electrodeless discharge tubes
for lithium, sodium and potassium by a straightforward method in silica tubing with
various compounds as the lamp charges. Over So tubes were prepared and tested for
atomic absorption spectrophotornetry. in addition to single element tubes, analyti-
cally useful tubes were prepared for combinations of the alkali metals; these were

Anal CJ~tiz.R&z, 51 (rgyo) 548-553