Analysis of divalent metal dialkyldithiocarbamates by gaschromatography and mass spectrometryCitation for published version (APA):Krupcik, J., Leclercq, P. A., Garaj, J., & Masaryk, J. (1979). Analysis of divalent metal dialkyldithiocarbamates bygas chromatography and mass spectrometry. Journal of Chromatography, A, 171(1), 285-304.https://doi.org/10.1016/S0021-9673%2801%2995308-7

DOI:10.1016/S0021-9673%2801%2995308-7

Document status and date:Published: 01/01/1979

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Journal of Ckronrarography, 171 (1979) 285-3634 IQ ?Skevier Sciedtk Publkhhg Compay, Amsterdam - Printed in The N&e&&

-c_-

-Departmerit of Analyticd Cke%istry, Fa&Ity of Chemical Tecknology, Slovuk rectqzxat untversJry* 880 37 Bratisigva (Czechoslovakia)

P. A. LECLERCQ

Laboratory of hsfmmental Analysis, Eindkoven University of Techdogy, l%dkoven (Tke Netherlands)

2nd

J. GARAJ and J. MASARYK

Department o-f Anaiyticd Ckemistry, Faculty of Chemical Tecknology, Slovak Techrricai University, 880 37 Bratidava (Czeckoslovakia)

(First received May llth, 1978; revised manuscript received October 19th. 1978)

SUMMARY

The influence of various gas chromatographic supports, coated with SE-30 as stationary phase, on the qualitative and quantitative analysis of Ni(II) and Zn(II) dithiocarbamates was investigated. Retention indices were correlated with the struc- tures of the compounds studied. Cu(II), Co(H) and Cd(U) dialkyldithiocarbamates decomposed during analysis under the applied conditions. Special emphasis was given to the quantitative analysis of Ni(Ii) and Zn(H) bis(N,N-dialkyldithiocarba- mates).

Basic conditions were established for the separation of Ni@I)‘bis(N,N-dia&yL dithiocarbamates) on glass capillary columns - coated with polydimethylsiloxane stationary phases (OV-101 and SE-30). The maid problem in the successfuI analysis of these compounds in glass capillary columns was found to be adsorption on the column wall.

Electron-impact positive-ion mass spectra of Ni(II) and Zn(II) bis(N,N-di- alkyIdithiocarbamates) are discussed in detail. From the mass spectra of these corn- pounds, general fragmentation pathways were derived. All of the dithiotibamates studied showed molecular ions, the intensity of which decreased with irmcre=ing size of the alkyl substituent.

INTRODUCI’IQN

Successfuf analyses of metal chelates containing a dialkytdithiocarbamate ligand by gas chromatography have been recently publishedLd. We have previously de- .

scribed the separation of nickel and zinc bis(N,N-diethyldithiacarbamates)’. Zn(II), Cd(II), I’b(II), H&II), Ni(II), Pd(I1) and Ft(II) bis(N,N-diethyldithioczxbamates) have

285 ;. , J. KRUtifK; P. A. LECLERCQ, 3. GARAJ, J. MASARYK

been analysed by gas chromatography 3*4. The separation of a mixture of Ni(II), Zn(II) and Cd(H) bis(N,N-diethyl$.hiocarbamates) was also described by Tavlaridis and Neeb5. For the determination of metals in water, Tavlaridis and Neeb proposed the gas chromatographic analysis of chelates containing a di(trifluoroethyl)dithio- carbamate ligand6. Fluorinated diethylditbiocarbamatetes are more volatile and show better thermal stability above 473 “K than do the corresponding diethyldithiocarba- mates. A mixture of Zn, Ni, Cd, Sb and Bi bis~,Ndi(trifluoroethyl)dithiocarba- mates! has been successfully analysed by gas chromatography_

For the analysis of metal dithiocarbamates by gas chromatography, columns packed with non-polar stationary. phases (silicone greases and elastomers) on s&n- ized support materials based on Chromosorbs have been used excIusively’“.

The mass spectra of metal N,N-dialkylditbiocarbamates have not yet been studied systematically’*7-‘6, and only a few mass spectral data have been reported on some dithiocarbamates of the bivaIent metals Cu’, Zn7J2J3 and Ni2*“. Detailed frag- memation patterns are not found in the literature.

The aim of the present work was to study the probkms encountered in analyses of divalent metal dialkyldithiocarbamatcs by gas chromatography_ Special emphasis is given to the quantitative analysis of Ni(II) and Zn(II) bis(N,N-clialkyl- dithiocarbamates).

Another objective of the work was to explore the basic conditions for tbc separation of Ni(I1) bis(N,N-dialkylditbiocarbamates) by capillary column gas chro- matography. Finally, the mass spectra of Ni(I1) and Zn(II) bis(N,N-dialkyldithio- carbamates) are discussed in detail.

EXPERIMENTAL- . .

Preparatfon of divalent metal dialkyldititiocarbamates Dialkyldithiocarbamate chelates of divalent metals were prepared using the

procedure described previously2. The chelates used are listed in Table I. The purity of the compounds obtained was checked by elemental anaiysis and mass spectrometry.

Gas chromatograpiiy A Carlo Erba (Milan, Italy) gas cbromatograph (Fractovap Model 2308)

equipped ‘with a flame-ionization detector (FID) and a stream splitter, allowing the use of capillary columns, was used.

Glass packed columns of Ien_& 60-200 cm and I.D. 3 mm were used. The support materials applied are listed in Table II. Glass capillary columns coated with OV-101. and SE-30 as stationary phases were prepared according to a previously de- scribed procedure”. The glass capillary columns used are listed in Table III. Capillary columns were coated using the dynamic plunger methodI’ and the modified static metiodlq.

Nitrogen was used as the carrier gas in all experiments. Samples of dithio- carbamates were dissolved in chloroform (1 mg in 1 ml). n-Alkanes were dissolved in n-hexane (1 mg in 1 .ml). Solutions were injected with a lO-,ul Hamilton microsyringe-

Peak asymmetry was measured at one tenth of the peak beightzO_ Retention times were measured with a stop-watch. A digital integrator (Autolab, Model-6300) was used to measure ‘peak areas for quantitation.

304 J. KRUPCfK, P .A. LECLERCQ, J. GARAJ, J. MASARYK

ACKNOWLEDGEMENT

This work was partially supported by a Scientific Exchange Agreement (S.E.A.)

gant.

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