Journal of Chromatographic Science, Vol.

42, March 2004

Qualitative Analysis of Cu2+, Co2+, and Ni2+ Cations

Using Thin-Layer Chromatography

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Soner Ergül*
Department of Chemistry, Faculty of Science and Literature, Balikesir University, 10100 Balıkesir, Turkey

Abstract The structures and abbreviations of the complexes of

M(DEDTC)2 (M = Cu, Co, and Ni) and M(PyDTC)2 (M = Cu and
The M(DEDTC)2 (M = Cu, Co, or Ni) and M(PyDTC)2 Co) with DEDTC and PyDTC ligands are given in Figures 1 and 2
(M = Cu or Co) complexes prepared by reactions of sodium (3). There are relatively less applications of TLC in the literature
diethyldithiocarbamate and ammonium pyrollidinedithiocarbamate about qualitative analysis of metallic cation mixtures (4–7).
with metal (II) nitrates are examined for qualitative analysis and In this study, M(DEDTC)2 and M(PyDTC)2 complexes are inves-
separation using thin-layer chromatography systems. These tigated on activated thin layers of silica gel 60GF254 (Si-60GF254)
complexes and their mixtures are spotted to the activated thin using two different mobile phases with respect to qualitative
layers of silica gel 60GF254 (Si-60GF254) with a 250-µm thickness. analysis of Cu2+, Co2+, and Ni2+ cations.
Pure toluene and a toluene–cyclohexane mixture (3:1, v/v) are
used as mobile phases for running of the complexes. These
chromatographic systems are successfully used for qualitative
analysis of corresponding metal cations and separation of Experimental
components in both M(DEDTC)2 and M(PyDTC)2 complex
mixtures.
Chemicals, reagents, and materials
Si-60GF254, NaDEDTC, NH4PyDTC, Ni(NO3)2, Cu(NO3)2, and
Co(NO3)2 chemicals were purchased from Merck (Darmstadt,
Introduction Germany).
Cu(DEDTC)2, Co(DEDTC)2, Ni(DEDTC)2, Cu(PyDTC)2, and
The qualitative and quantitative analysis of Cu2+, Co2+, and Ni2+ Co(PyDTC)2 complexes were prepared by the reactions of
cations in environmental media and various samples is chal- NaDEDTC and NH4PyDTC with Ni(NO3)2, Cu(NO3)2, and
lenging for analytical chemists because of the similarities in their Co(NO3)2. The toluene–cyclohexane mixture (3:1, v/v) and pure
properties. Thin-layer chromatography (TLC) is a rapid, easy, and toluene were used as the mobile phase. The layers of Si-60GF254
simple separation technique extensively used for organic species
but rarely used for inorganic cations. However, TLC has some
advantages compared with alternative methods. For instance,
components of mixture samples can be easily separated without
interference. In addition, several samples can be separated simul-
taneously using TLC, and the positions of spots that appear can be
determined with a number of different methods (1–3). Figure 1. Molecular structures for (A) NaDEDTC complexing agent and (B)
Ligands that contain N,S or O,S donor atoms are mostly used
for the separation of metals because these ligands form the coor-
dinatively saturated complexes with metals at high formation
rates. In addition, when the ligands of complexes are the same,
the chromatographic parameters of these complexes are affected
by electronic properties of metals. Dithiocarbamate ligands, such
as diethyldithiocarbamate (DEDTC) and pyrollidinedithiocarba-
mate (PyDTC), contain N,S donor atoms, and they form coordi-
natively saturated complexes with metals (3). Figure 2. Molecular structures for (A) NH4PyDTC complexing agent and (B)
M(PyDTC)2 complexes.
* Author to whom correspndence should be addressed: email [email protected].

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 Journal of Chromatographic Science, Vol. 42, March 2004

were prepared using a Loughborough-Griffin & George TLC Results and Discussion
Unikit (Leicestershire, England). All the chemicals were of
analytical grade.
The challenger Cu2+, Co2+, and Ni2+ cations in the qualitative
Synthesis of M(DEDTC)2 complexes and quantitative analysis require to be separated satisfactorily.
Prepared were 0.10 mol/L solutions of metal nitrates TLC is extensively used for organic species but has potential usage
[Cu(NO3)2, Co(NO3)2, Ni(NO3)2 ] at pH 5.5–6.0 (adjusted by acetic for inorganic cations. In this context, TLC has been examined for
acid–sodium acetate buffer). From these solutions, a 1.0-mL qualitative analysis of Cu2+, Co2+, and Ni2+ cations via forming
aliquot was poured into a beaker and 1.0 mL of 0.1 mol/L fast and stable complexes. For this purpose, in choosing DEDTC
NaDEDTC solution was added to it and then was shaken. Four and PyDTC ligands, neutral M(DEDTC)2 and M(PyDTC)2 com-
milileters of pure chloroform was added to the beaker and was plexes were prepared.
shaken for 1 min. This mixture was tranfered into a separatory DEDTC and PyDTC ligands with N,S donor atoms formed the
funnel and shaken. The phases were allowed to separate for 5 min. coordinatively saturated stable complexes with the cations cited.

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The aqueous phase was separated from the chloroform phase and Because of these properties, they cannot interact chemically with
discarded. Subsequently, the chloroform phase containing the the stationary and mobile phases in TLC systems. The formation
complex was dried by treating with anhydrous Na2SO4. The dried rates of complexes are very high, which also means saving time.
phase was used as sample for TLC applications. Furthermore, these complexes are colored and can be easily visu-
alized in the chromatograms.
Synthesis of M(PyDTC)2 complexes In this work, to prepare M(DEDTC)2 and M(PyDTC)2 com-
Prepared were 0.10 mol/L solutions of metal nitrates [Cu(NO3)2 plexes, aqueous solutions of Cu2+, Co2+, and Ni2+ at pH 5.5–6.0
and Co(NO3)2] at pH 5.5–6.0 (adjusted by acetic acid–sodium (adjusted by acetic acid–sodium acetate buffer), were treated with
acetate buffer). From these solutions, a 1.0-mL aliquot was DEDTC and PyDTC solutions. The reason for working at pH < 7
poured into a beaker, and 1.0 mL of 0.1 mol/L NH4PyDTC solu- was to keep the cations in solution as stable complexes. The com-
tion was added to it and then was shaken. Four milliliters of pure plexes were extracted to the chloroform phase at pH < 7 to ensure
chloroform was added to the beaker and shaken for 1 min. This preconcentration and cation selectivity via complexation.
mixture was transferred into a separatory funnel and shaken. The Moreover, as the result of organic phase extraction, the chro-
phases were allowed to separate for 5 min. The aqueous phase was matographic tailing and, hence, scattering of Rf values were pre-
separated from the chloroform phase and discarded. Sub- vented. The chloroform was used as the organic phase because of
sequently, the chloroform phase that contained the complex was its complex solubility and solvent volatility advantages.
dried by treatment with anhydrous Na2SO4. The dried phase was For TLC applications, pure toluene and a toluene–cyclohexane
used as sample for TLC applications. mixture (3:1, v/v) were used as the mobile phases because of their
low polarities. In addition, these solvents were chemically inert
Preparation of thin-layer plates for the complexes and surface of the thin layer. Silica gel was used
Slurries of Si-60GF254 in water (1:2, w/v) were spread onto
cleaned glass plates (7.5 × 15 cm) with a thickness of 250 µm
most frequently as the adsorbent for the separation of coordina-
tively saturated complexes (3). Thus, Si-60GF254 was chosen as
using a spreader kit. Nonactive plates were obtained by keeping the stationary phase.
the plates at room temperature for 12 h. They were activated by The samples used were solutions of M(DEDTC)2 and
heating in an oven at 110ºC for 2 h. For TLC applications, M(PyDTC)2 complexes in chloroform. As an exception, peculiar to
activated plates were used. this study, Ni(PyDTC)2 was not used for TLC applications.
Ni(PyDTC)2 does not reach the required concentration in the
TLC applications
chloroform phase by virtue of its low solubility, hence it was
Two-microliter aliquots from each of the complex solutions and
impossible to observe its spot on the chromatograms with the
their mixtures were spotted onto a straight line 2.0 cm up to the
naked eye. The solubilities of M(PyDTC)2 and M(DEDTC)2 in chlo-
bottom of the plate with micropipettes. The original spots on the
layers were dried at room temperature for 3 min. Two developing
chambers with 10- × 50- × 20-cm dimensions were used for run-
ning. Sixty milliliters of the toluene–cyclohexane mixture (3:1,
v/v) was poured into one chamber and 60 mL of toluene into the
other. The chambers were closed with the lids and allowed to
stand for 15 min to ensure the saturation of air in each chamber
with solvent vapors. The activated plates that contained spotted
samples were then carefully immersed into the developing cham-
bers. The plates were taken out of the chambers when the solvent
fronts reached 5.5 cm. The solvent fronts on the plates were
marked with a pencil, and the plates were dried. After all of these
steps, the migration distance of the solvent (Zf), the migration Figure 3. Chromatograms of the complexes and their mixtures: (1)
distance of each spot (Zx), and the width (W) were measured. The Cu(DEDTC)2; (2) Co(DEDTC)2; (3) Ni(DEDTC)2; (4) the mixture of 1, 2, and 3;
retention factor (Rf, from Rf = Zx/Zf) and theoretical plate number (5) Cu(PyDTC)2; (6) Co(PyDTC)2; and (7) the mixture of 5 and 6.
[N, from N = 16(Zx/Wx)] were calculated (1,9).

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Journal of Chromatographic Science, Vol. 42, March 2004

roform were higher compared with the solubility of Ni(PyDTC)2 the cations in sample with NaDEDTC. Although TLC application
in chloroform. As seen from Figure 3, M(DEDTC)2 and using pure toluene as the mobile phase is more successful than a
M(PyDTC)2 could be easily identified because of their distinctive toluene–cyclohexane mixture (3:1, v/v) because of the higher N
colors. values belonging to complexes, either of the mobile phases can be
Chromatograms of M(DEDTC)2 and M(PyDTC)2 complexes used successfully for qualitative analysis of cations and separation
on activated Si-60GF254 layers with pure toluene and a of M(DEDTC)2 complexes as to the relative N values.
toluene–cyclohexane mixture (3:1, v/v) are shown in Figure 3. As As a final evaluation of data in Table I regarding qualitative anal-
appear in these, the spots of complexes and their mixtures were ysis and separation of Cu(II), Ni (II), and Co(II) complexes, it can
developed without any tailing or decomposition and were sepa- be said that the best TLC application is performed on an activated
rated into their components. This chromatographic property is Si-60GF254 layer with pure toluene as the mobile phase.
peculiar to coordinatively saturated dithiocarbamate complexes. Additionally, the DEDTC ligand is more successful than the
Rf and N values for these complexes are given in Table I. PyDTC ligand.
As seen from Table I, for the TLC application using pure In view of the contributions to chromatographic separation of

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toluene as the mobile phase, the Rf values of Cu(PyDTC)2 and the cations and their complexes, in addition to effects of mobile
Co(PyDTC)2 were 0.44 ± 0.02 and 0.15 ± 0.01; the N values phases and ligands considered previously, the effect of metals
belonging to these complexes were 1024 and 114, respectively. must be taken into account.
For the TLC application using the toluene–cyclohexane mixture According to Table I, the Rf values of Cu(DEDTC)2,
(3:1, v/v) as the mobile phase, Rf values of Cu(PyDTC)2 and Co(DEDTC)2, and Ni(DEDTC)2 complexes in pure toluene as the
Co(PyDTC)2 were 0.18 ± 0.01 and 0.04 ± 0.01; the N values of the mobile phase were 0.55 ± 0.03, 0.18 ± 0.01, and 0.36 ± 0.02,
complexes were 400 and 16, respectively. Based on these results, respectively. Rf values of Cu(PyDTC)2 and Co(PyDTC)2 complexes
TLC applications using two different mobile phases, Cu(PyDTC)2 in pure toluene as the mobile phase were 0.44 ± 0.02 and 0.15 ±
and Co(PyDTC)2, were developed with different Rf values and sep- 0.01, respectively. Although the ligands and the mobile and sta-
arated chromatographically. Furthermore, the positions of their tionary phases are the same, the great and significant difference
spots were determined from the chromatograms in Figure 3 by in the Rf values of either group complexes results from the differ-
the naked eye. As a result, a mixture containing Cu2+ and Co2+ ence in the electronic structures of the metal atoms. For example,
ions could be analyzed qualitatively using TLC following the com- for pure toluene as the mobile phase, Rf values of Cu(DEDTC)2,
plexation of the cations in sample with NH4PyDTC. On the other Cu(PyDTC)2, and Co(DEDTC)2 were 0.55 ± 0.03, 0.44 ± 0.02, and
hand, TLC application using pure toluene as the mobile phase is 0.18 ± 0.01, respectively. The Rf difference of Cu (II) complexes is
more successful than a toluene–cyclohexane mixture (3:1, v/v) 0.11, whereas the Rf difference of Cu(DEDTC)2 and Co(DEDTC)2
because of the higher N values belonging to complexes. is 0.37. The difference stems from that the metal of complexes is
According to Table I, for the TLC application using pure toluene higher than those from ligand. Although the charges, radii, and
as the mobile phase, the Rf values of Cu(DEDTC)2, Co(DEDTC)2, charge densities of Cu2+ and Co2+ in aqueous solutions were close
and Ni(DEDTC)2 were 0.55 ± 0.03, 0.18 ± 0.01, and 0.36 ± 0.02; to each other, their d9 and d7 electronic configurations, respec-
the N values belonging to these were 1600, 178, and 711, respec- tively, lead to different physical and chemical properties of the
tively. For the TLC application using a toluene–cyclohexane mix- complexes. This relation is valid for the other metals and their
ture (3:1, v/v) as the mobile phase, the Rf values of these were 0.33 complexes in a toluene–cyclohexane mixture (3:1, v/v) mobile
± 0.02, 0.07 ± 0.01, and 0.18 ± 0.01; the N values of these were phase, as well.
1296, 64, and 400, respectively.
Based on these results, for TLC applications using two different
mobile phases, the Rf values of M(DEDTC)2 complexes were suffi-
ciently different from each other and were separated chromato- Conclusion
graphically. In addition, the positions of their spots were
determined on the chromatograms given in Figure 3 with the This study shows that it is possible to analyze qualitatively and
naked eye. Thus, a mixture that contains Cu2+, Ni2+, and Co2+ can to separate satisfactorily a mixture of Cu2+, Ni2+, and Co2+ cations
be analyzed qualitatively using TLC following the complexation of using TLC following the complexation of the cations with DEDTC
ligand.
Table I. Rf and N values of M(DEDTC)2 and M(PyDTC)2 Cu(DEDTC)2, Co(DEDTC)2, and Ni(DEDTC)2 complexes do not
Spots on Activated Si-60GF254 Layers Using Pure Toluene interact chemically with the stationary and mobile phases in TLC
and a Toluene–Cyclohexane Mixture systems. Because the formation rates of complexes are very high,
the application was carried out in a short time. These complexes
Running I* II† I‡ II were colored and are easily visualized in the chromatograms.
Complex time Rf ( ± SD) Rf ( ± SD) N N Color For TLC applications using two different mobile phases,
Cu(PyDTC)2 and Co(PyDTC)2 were developed with different Rf
Cu(DEDTC)2 12 0.55 ± 0.03 0.33 ± 0.02 1600 1296 Brown
Co(DEDTC)2 12 0.18 ± 0.01 0.07 ± 0.01 178 64 Green
values and were separated chromatographically. A mixture that
Ni(DEDTC)2 12 0.36 ± 0.02 0.18 ± 0.01 711 400 Green contains Cu2+ and Co2+ ions was analyzed qualitatively using TLC
Cu(PyDTC)2 12 0.44 ± 0.02 0.18 ± 0.01 1024 400 Brown following the complexation of the cations in sample with
Co(PyDTC)2 12 0.15 ± 0.01 0.04 ± 0.01 114 16 Green NH4PyDTC. TLC application using pure toluene as the mobile
phase was more successful than with a toluene–cyclohexane mix-

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 Journal of Chromatographic Science, Vol. 42, March 2004

ture (3:1, v/v) because of the higher N values belonging to the simple activities for undergraduate students. J. Chem. Edu. 73:
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