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Authors’ contributions
This work was carried out in collaboration among all authors. Authors AH and AMC designed the
study, performed the statistical analysis, wrote the protocol and wrote the first draft of the manuscript.
Authors AM and MA managed the analyses of the study and the literature searches. All authors read
and approved the final manuscript.
Article Information
DOI: 10.9734/IRJPAC/2019/v18i430098
Editor(s):
(1) Dr. Farzaneh Mohamadpour, Department of Organic Chemistry, University of Sistan and Baluchestan, Iran.
Reviewers:
(1) Jolanta Flieger, Medical University of Lublin, Poland.
(2) Pardon Kusaziwa Kuipa, Lupane State University, Zimbabwe.
(3) Ronald Bartzatt, University of Nebraska, USA.
Complete Peer review History: http://www.sdiarticle3.com/review-history/49066
ABSTRACT
Capillary electrophoresis (CE) has been developed as one of the powerful separation
techniques for the analysis of inorganic and organic ions in complex matrices in the recent past. In
aqueous samples, most of the inorganic ions are having weak absorption profiles in the UV-Vis
region of the spectrum. These low absorption profile ionic species are commonly detected by
indirect UV absorbance with the addition of an absorbing co-ion (chromophore) into the electrolyte.
The inorganic cations oftenly require an additional complexing agent to selectively alter their similar
mobilities and proper separation. The indirect detection at 214 nm was performed with α-
hydroxyisobutyric acid (α-HIBA)-4-aminopyridine background electrolyte (BGE) that has a
characteristic absorbance at 214 nm. The BGE was applied for the separation, analysis, and
validation of metal ions in water samples. The metal ions such as K+, Na+, Ca2+, Mg2+, Mn2+, Fe2+,
2+ 2+ 2+ 2+
Cd , Pb , Ni and Zn were separated successfully in this study. Also, the effect of electrolyte pH,
applied voltage and injection time for the separation of cations was investigated.
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effect of pH, applied voltage and injection on inversely related to the migration velocity [16,17,
peak area and migration time has been studied. 18]. At pH 4.5 the largest peak area response,
and consequently the highest sensitivity, were
3.2.2 Effect of pH of the background obtained for the cations. At pH below 4.5 a high
electrolyte noise and distortion in background was
observed. Likewise, cations like, Mg2+, Pb2+ and
Buffer pH has much influence on the separation 2+
Zn were not seen at pH lower than 4.5. This is
selectivity of metal and controls the improvement
because of the distortion of buffer solution and
of resolution of complexes [12,13]. The
the complexes formed are not stable.
electroosmosis flow (EOF) decreases with a
decrease in pH [14,15] owing to a reduced
dissociation of surface silanol groups. A 3.2.3 Effect of applied voltage
decrease in the pH of BGE results in an increase
in the difference of the migration times between The increase in the applied voltage increases in
two neighbouring cations. Changing the pH the velocity of the ion and consequently its
affects the selectivity and thus the peak area. A migration time. The relation betwe
between velocity of
pH range between 3 - 6.5 has been studied. Fig.
Fig the ion (V), migration time (µ) and the applied
2 shows a plot of peak area as a function of pH. voltage (E) [19] is given by:
Table 1. The migration time, peak area and corrected peak area of metal ions at a
concentration of 10 ppm (n = 6)
Metal ion Migration time, min (RSD) Peak area, (RSD) Corrected peak area, (RSD)
+
K 7.99(±1.74%) 3.65E-05(±6.74%) 4.57E-06(±6.50%)
06(±6.50%)
Ca2+ 10.04(±2.79%) 3.87E-05(±7.13 %) 3.86E-06(±5.26%)
06(±5.26%)
+
Na 10.41(±2.83%) 6.47E-05(±4.85%) 6.22E-06(±
06(± 4.72%)
2+
Mg 10.77(±3.03%) 3.43E-05(±7.64%) 3.19E-06(±6.48%)
06(±6.48%)
Mn2+ 11.07(±3.16%) 0.000138(±8.05%) 1.25E-05(±5.44%)
05(±5.44%)
2+
Fe 11.38(±3.36%) 2.01E-05(±4.85%) 1.76E-06(±3.70%)
06(±3.70%)
Cd2+ 11.69(±3.51%) 7.20E-05(±5.86%) 6.17E-06(±2.97%)
06(±2.97%)
2+
Pb 11.83(±3.81%) 1.67E-05(±12.04%) 1.42E-06(±11.83%)
06(±11.83%)
2+
Ni 12.023(±3.84%) 1.32E-04(±8.46%) 1.10E-05(±5.72%)
05(±5.72%)
Zn2+ 12.21(±3.94%) 1.20E-04(±8.36%) 9.85E-06(±5.27%)
06(±5.27%)
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Fig.1b. The reproducibility (within runs) of metal ions over three runs using the same
+ 2+ +
experimental conditions as in Fig. 1a. Peaks according to sequence: 1 = K , 2 = Ca , 3 = Na , 4
2+ 2+ 2+ 2+ 2+ 2+ 2+
= Mg , 5 = Mn , 6 = Fe , 7 = Cd , 8 = Pb , 9 = Ni , 10 = Zn
Fig.1c. The reproducibility of metal ions over three runs (between runs) using the same
+ 2+ +
experimental conditions as in Fig. 1a. Peaks according to sequence: 1 = K , 2 = Ca , 3 = Na , 4
2+ 2+ 2+ 2+ 2+ 2+ 2+
= Mg , 5 = Mn , 6 = Fe , 7 = Cd , 8 = Pb , 9= Ni , 10 = Zn
0.00018 Ca
0.00016
0.00014 Na
0.00012
Mg
0.0001
0.00008 Mn
0.00006
0.00004 Fe
0.00002 Cd
0
4.3 5.3 6.3 7.3 Pb
Ni
pH
Zn
Fig. 2. The effect of pH of the background electrolyte on peak area. Experimental conditions
are the same as in Fig.1a
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Hailemichael et al.; IRJPAC, 18(4): 1-9, 2019; Article no.IRJPAC.49066
45 K
Migration time (min) 40 Ca
35 Na
30
25 Mg
20 Mn
15
Fe
10
5 Cd
0 Pb
9.6 14.6 19.6 24.6 29.6
Ni
Applied voltage (kV) Zn
Fig. 3. The effect of applied voltage on migration time. Experimental conditions are the same
as in Fig.1a
K
Peak Area (anonymous)
0.0002
0.00018 Ca
0.00016 Na
0.00014
0.00012 Mg
0.0001
0.00008 Mn
0.00006 Fe
0.00004
0.00002 Cd
0
0.18 0.28 0.38 0.48 Pb
Ni
Injection time (min)
Zn
Fig. 4. The effect of injection time on peak area. Experimental conditions are the same as in
Fig. 1a
A change in the applied voltage has direct effect sensitivity of the instrument is low. At higher
on the migration time. The migration time injection time the peak area was increased.
between the neighbouring cations changes when Therefore, in this study, 0.3 min for metal
the applied voltage changes from 10 to 30 kV. separation and 0.2 min for the calibration curve
From the above considerations, a positive was used to reduce overlapping. The plot of peak
voltage of 25 kV was selected for further area versus injection time is shown in Fig. 4.
experiments.
3.2.5 Validation of the method
3.2.4 Injection time 3.2.5.1 Limit of detection (LOD)
The signals obtained were, in general, Table 2 shows with hydrodynamic injection for 24
proportional to the injection time for metals s, at pH 4.5, with respect to each metal ion the
investigated. However, peak broadening was following LOD was found. Lower limits of
found to occur at long injection time, leading to detection was obtained by injecting greater
poor separation [20,21]. The effects of varying volumes, but at the expense of peak efficiency
injection time to 0.2, 0.3, 0.4 and 0.5 min was [22]. A higher limit of detection LOD was
studied. High injection time was used since the obtained for Ca2+.
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Hailemichael et al.; IRJPAC, 18(4): 1-9, 2019; Article no.IRJPAC.49066
(a)
(b)
(c)
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(d)
+ 2+ + 2+
Fig. 5. Calibration curve of (a) K , (b) Ca , (c) Na , (d) Mg
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Hailemichael et al.; IRJPAC, 18(4): 1-9, 2019; Article no.IRJPAC.49066
Peer-review history:
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