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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
A B C D E F G H I J K
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.
TABLE I
&. VhLUES X-OH DPCI AND PscI ON DIFFERENT ADSORBCNTS
Adsorbmrl
Dlphcnylcarbahicle (DPCI)
Phenylscmlcnrbazldc (PSCI)
5 I
TABLE II
~*CLTING Po*Nrs, O/,JZ)PCI AND I?3X, A,,., AND LOG E-VALucs 017 sob115conlnlBRcxAL DPCI
SAMPLES
: 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
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
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