858 Short communications

RESULTS AND DISCUSSION

From Table I it can be seen that with increasing concentration of the hydrochloric acid from
0.01 to 05M, in the absence of ethyl alcohol, sorption decreases, but when the acid concentration is
further increased from 05 to 4,OM, an increase in the sorption of molybdenum is observed. This
behaviour can be explained by the change of anionic molybdenum to a cationic form with acidity
according to the equation
MoO,~- + 4H+ + MoO,~+ + 2H,O.
Between 3 and 4M hydrochloric acid, an average of 45 % of MoOz2+ is sorbed.
The next experiments were carried out under the same conditions, with the difference that a
gradually increasing quantity of ethyl alcohol was added to the system, in order to investigate its
influence. It was found (Table I) that the variation of sorption with acidity was similar to that from
aqueous solutions, but that at a given acidity the adsorption generally increased with the percentage
of ethanol.
This phenomenon can be explained in the following way. The dielectric constant of the solvent
decreases as the percentage of ethanol increases, so the resin will swell to a lesser degree. The distortion
of the resin is leas and the selectivity greater. In this case also, water molecules in the hydration shell
of the ions are displaced by ethanol and this leads to increased sorption.

Department of Analytical Chemistry D. A. SHISHKOV

Mining and Geological Institute L. G. SHISHKOVA
Soja, Bulgaria

Sununa~-The sorption of molybdenum(V1) onto Ku-2 x 8 cation-

exchange resin in the hydrogen form from hydrochloric acid (0.01-4M)
in the presence and absence of ethanol (20-80x) has been investigated.
ZlrPammenfassuag-Es wurde die Zusammenwirkung unter dem
Molybdiin (VI) und dem Kationaustauscher Ku-2 x 8 mit H-Kation in
Zusammenhang mit der HCl-Konzentration (von 0,014N) in Ab- und
Anwesenheit von Athylalkohol in der Konzentrationsgrenze 20-80x,
untersucht.
R&sum~L’auteur examine l’attitude du molibdbne (VI) dans les
echangeurs de cations Ku-2 x 8 en forme H, par rapport a la con-
centration de l’acide chlorhydrique (de 0,Ol a 4N) en absence et en
presence de l’alcohol ethylique dans les limites de 20 1 80%.

REFERENCES
1 G. Wiegner and H. Jenny, Kolloid. Z., 1927, 42, 268.
2 G. Wiegner and J. Mtlller, Pjanz Dung., 1929,14A, 332.
BT. Kressman and E. Kitchener, J. Chem. Sot., 1949, 1211.
4 I. P. Alimarin, E. P. Tsintsevich and I% P. Usova, Vestn. Mosk. Univ. Ser. IlKhim., 1961, Nr. 2,31.
5 J. Korkisch and S. Urubay, Talanta, 1964, 11, 721.
6 J. Korkisch and F. Tera, Z. analyt. Chem., 1962,186,290
7 J. Korkisch and G. E. Janauer, Talanta, 1962, 9, 957.
BI. P. Alimarin, E. P. Tsintsevich and L. G. Shishkova, Vest. Mosk. Univ. Ser. II Khim., 1964.
@J. Korkisch, I. Hazan and G. Arrhenius, Talanta, 1963, 10,865.
lo C. K. Mann and C. Z. Swanson, Analyt. Chem., 1961, 33,459.

Potentiometric titration of quatemary ammonium iodide salts

(Received 26 April 1965. Accepted 12 June 1965)

BECAUSE of the importance of some quaternary ammonium iodide esters, such as the choline or
thiocholine iodide esters, as substrates for cholinesterase, there developed a need in these laboratories
for a simple, rapid method of accurately determining the purity of such compounds.
 Short communications 859

Very little has been reported in the literature on the titration of quatemary ammonium halide
salts. Pifer and Wollish’ described the notentiometric titration of the bromide and chloride salts of
quaternary ammonium compounds in &tic acid with perchloric acid as titrant. The reaction was
based on the conversion of the halide salt of the quatemary compounds to the corresponding acetate,
using mercury(H) acetate in acetic acid. The acetate of the organic base was then titrated with
O.lM perchloric acid in dioxan. No iodide salts were tried by these authors.
Izmailovand Vail4 reported the titration of mixtures of an inorganic iodide salt, such as ammonium
iodide or potassium iodide, and an organic iodide salt, tetramethylammonium iodide, with silver
nitrate in acetone or acetonitrile. Sharp inflection points were observed, but large deviations were
obtained in the case of tetramethylammonium iodide.
Attempts to use the method of Pifer and Wollish for the titration of iodide compounds yielded
low results (l-2% deviation), because of the oxidation of iodide to iodine during heating of the
sample for dissolution in acetic acid. Preliminary experiments indicated that the sample could be
easily dissolved in methanol first, followed by addit?on of acetic acid and mercury(II) acetate, and
finally titrated with perchloric acid. Various organic iodides, such as tetrabutylammonium iodide,
triethylmethylammonium iodide and tetrapropylammonium iodide (0.024.20 g) were analysed
with a relative standard deviation of about 0.2%, with an accuracy (compared to results obtained
using the Kolthoff modification of the Winkler method3 or the Liepert procedure*) of better than
0.17%. However, the thiocholine iodide esters could not be determined because of large drifts in
potential. These drifts are caused by hydrolysis, by the acids used, of the esters to the thiols and the
corresponding acid. In the titration of acetylcholine iodide, spot tests with the reagent bis-dithio-
nitrobenzoate& indicated the presence of thiol. It was found, however, that these compounds could
be titrated with silver nitrate in aqueous solution, using a silver indicating electrode with deviations
of about @2x. Using this technique, 2-20 mg of propionyl choline iodide, butyryl thiocholine
iodide, 2-(iV,N,iV-diethyhnethylammonium) ethyl butyrate iodide,2-(N,iV,N-diethylmethylammonium)
ethyl benzoate iodide, tetrabutylammonium iodide, and the pyridinium iodide, Camino-l-methyl-
pyridinium iodide, were analysed with an accuracy of about 0.2 %.
The procedure that was used in the potentiometric titrations with perchloric acid was as follows:
a sample of the salt, containing 0.2-2.0 mg, is dissolved in 2 ml of anhydrous methanol. Five ml of
acetic acid are added, followed by 2 ml of the mercury(H) acetate reagent, then the resulting solution
is titrated with O.lM perchloric acid-dioxan solution from a Xi-ml microburette, using the mV-scale
of the potentiometric instrument.

Defensive Research Division G. G. GUILBAULT

Chemical Research and Development Laboratories B. c. ?-'YSoN
Edgewood Arsenal, Md., U.S.A. D. CROWNOVER

Summary-A potentiometric titration is described for quaternary

ammonium iodide compounds based on a modification of the method
of Pifer and Wollish. By this technique, 0.2-2-O mg of these com-
pounds can be titrated with a deviation of 0.2% and an accuracy of
0.17 %. Thiocholine iodide esters cannot be titrated because of hydro-
lysis by the titrant, but they can be determined by titration with silver
nitrate with a deviation and accuracy of 0.2 %.

Zusammenfassnn~-Eine potentiometrische Titration ftlr quartlre

Ammoniumjodide wird beschrieben, die auf einer Modifikation der
Methode von Pifer und Wollish beruht. Mit dieser Methode k6Me.n
0,2-2,0 mg dieser Verbindungen mit einer Abweichung von 0,2% und
einer Richtigkeit von 0,17x titriert werden. Thiocholinjodid-Ester
konnen nicht titriert werden, da der Titrant hydrolysiert wird, aber sie
lassen sich durch Titration mit Silbemitrat mit einer Abweichung und
Richtigkeit von 0,2 % bestimmen.

R6sunG--On d&it un dosage potentiomttrique d’iodures de composes

ammonium quatemaires, base sur une modification de la mdthode de
Pifer et Wollish. Par cette technique, on peut doser 0,2-2.0 rnE de ces
composes, avec un &art de 0,2% & une precision de 0,17 %. L& esters
de l’iodure de thiocholine ne neuvent etre doses nar suite de l’hvdrolvse
par l’agent de dosage, mais‘ on peut les titre; au moyen dd nit&e
d’argent, avec un &art et une precision de 0,2 %.
6
860 Short communications

REFERENCES
1 C. W. Pifer and E. G. Wollish, Analyt. Chem., 1952, 24, 300.
a N. A. Izmailov and E. I. Vail. Ukrain. Khim.. 1957.23.662.
s I. M. Kolthoff and N. H. Furman, Volumetric’Analy&, Vol. II. J. Wiley and Sons, New York, 1929.
p J. Liepert, Mikrochemie, Preglfestschrift, 1929, 226.
5 G. L. Ellman and K. D. Courtney, Biochem. Pharmacol.. 1961,7,88.

A phosphorimetric investigation of several representative alkaloids of the

isoquiuoline, morphine and indole groups
(Received 17 May 1965. Accepted 12 June 1965)

THE quantitative determination of the alkaloid content of crude drugs, plants and biological fluids is
important for many legal and medical reasons. Since its first suggested use as a means of chemical
analysis by Keirs, Britt and Wentworth,’ phosphorimetry has been applied successfully in a number
of areas*-h and shown to be a powerful method when coupled with proper separation methods.4-B In
this study, the phosphorescence emission and excitation peaks of a number of alkaloids in neutral,
basic and acidic ethanol at 77°K are given. In addition, the phosphorescence decay times and
approximate limits of detection in ,ug,/ml of ethanol are given for the same alkaloids. Because of the
great sensitivity of phosphorimetry for many of the alkaloids, phosphorimetry as a measurement
technique should have use in the analysis of trace concentrations of these alkaloids in a variety of
materials.
EXPERIMENTAL

A spectrophotofluorimeter (Aminco-Bowman No. 4-8202, American Instrument Co., Inc., Silver

Spring, Md., U.S.A.) with a phosphoroscope (Aminco-Keirs No. C27-62140, American Instrument
Co., I&., U;S.A.), a potted RCAiP28 phdtomultiplier tube, a 200-W mercury-xenon arc lamp and
with an X-Y recorder (No. 1620-814, American Instrument Co., Inc., U.S.A.) was employed for all
measurements. All studies were performed at constant slit width (slit arrangement #4).’

Reagents
The solvent used was distilled technical grade ethanol. 5 The acidic and basic ethanolic solutions
were prepared by adding 2 drops of concentrated hydrochloric acid and concentrated sodium
hydroxide, respectively, to 10 ml of the ethanolic solution containing the sample. Stock neutral,
acidic and basic ethanolic solutions, containing a concentration of 1 mg of each of the followmg
alkaloids/ml of solvent, were prepared: papaverine hydrochloride, morphine alkaloid, morphine
sulphate, strychnine phosphate, brucine alkaloid, yohimbine hydrochloride, codeine alkaloid,
narcotine alkaloid, apomorphine hydrochloride, narceine alkaloid and thebaine alkaloid. All drugs
used in this investigation were U.S.P. grade. All volumetric glassware was cleaned thoroughly
according to directions specified by the manufacturer.8

Procedure
Dilute solutions of each alkaloid were prepared by successive dilution of the stock solution
to give ethanolic solutions having concentrations from 1 mg/ml to 0.1 pg/ml. Excitation and emission
spectra and decay curves were recorded with the X-Y recorder. The relative intensity (meter reading
in percentage transmittance times the coarse meter multiplier with fine sensitivity remaining constant
for all measurements) of each of the ethanolic solutions was measured on the photomultiplier micro-
photometer. The limit of detection was taken as that concentration which produced a signal on the
meter of 5 units above the background phosphorescence signal if the meter multiplier was adjusted
to give the maximum background signal, The decay time was the time for the emitted light to fall
to l/e of its initial intensity. The limits of detection of all compounds except morphine sulphate and
narcotine alkaloid were measured in neutral ethanol. Because morphine sulphate and narcotine
alkaloid were only slightly soluble in neutral ethanol, their limits of detection were measured in acidic
ethanol. Ethanol was used as the solvent because it froze to a clear glass at liquid nitrogen tempera-
tures with less than 5% of water8 and it was a good polar solvent. All the alkaloids studied were