• Analytical Science and Technology
• /
• v.10 no.3
• /
• pp.187-195
• /
• 1997

Chemically modified electrodes(CMEs) for Ag(I) were constructed by incoporating 1,5,9,13-tetrathiacyclohexadecane([16]-ane-$S_4$) with a conventional carbon-paste mixture composed of graphite powder and nujol oil. Ag(I) ion was chemically deposited onto the surface of the modified electrode with [16]-ane-$S_4$ by immersion of the electrode in the acetate buffer solution(pH=4.5) containing $5.0{\times}10^{-4}M$ Ag(I) ion. And then the electrode deposited with Ag(I) was reduced at -0.3V vs. S.C.E. Well-defined stripping voltammetric peaks could be obtained by scanning the potential to the positive direction. The CME surface was regenerated with exposure to 0.1M $HNO_3$ solution and was reused for the determination of Ag(I) ion. When deposition/measurement/regeneration cycles were 10 times, the response could be reproduced with relative standard deviation of 6.08%. In case of differential pulse stripping voltammetry, the calibration curve for Ag(I) was linear over the range of $5.0{\times}10^{-7}{\sim}1.5{\times}10^{-6}M$. And the detection limit was $2.0{\times}10^{-7}M$. Various ions such as Cd(II), Ni(II), Pb(II), Zn(II), Mn(II), Mg(II), EDTA, and oxalate(II) did not influence the determination of Ag(I) ion, except Cu(II) ion.

• Analytical Science and Technology
• /
• v.7 no.3
• /
• pp.361-369
• /
• 1994

Voltammetric behavior of some light lanthanide ions($La^{3+}$, $Pr^{3+}$, $Nd^{3+}$, $Sm^{3+}$ and $Eu^{3+}$) in acetonitrile(AN) and dimethylformamide(DMF) has been investigated by direct current, differential pulse polarography and cyclic voltammetry. The reduction of $La^{3+}$, $Pr^{3+}$ and $Nd^{3+}$ in 0.1M TEAP proceeded directly to the metallic state through three-electron charge transfer of irreversible process where as $Sm^{3+}$ and $Eu^{3+}$ proceeded by charge transfer of two steps. As the results of the cyclic voltammetric investigation, the first step reduction of $Sm^{3+}$ and $Eu^{3+}$ were a quasireversible reaction, the second step reductions were an irreversible reaction. The cathodic peak currents of the differential pulse polarogram showed adsorptive properties at lower sweep rates and high concentrations of these metal ions. The peak potenital was shifted to a negative petential and the peak current decreased with the increase of percentage of water in AN. On the other hand, the peak potential was shifted to a positive potential and the peak current decreased with an increased percentage of water in DMF.

• Journal of the Korean Electrochemical Society
• /
• v.9 no.1
• /
• pp.19-28
• /
• 2006

The phase-shift method for determining the Langmuir, Frumkin, and Temkin adsorption isotherms ($\theta_H\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at a Pt/0.1 M KOH solution interface has been proposed and verified using cyclic voltammetric, differential pulse voltammetric, and electrochemical impedance techniques. At the Pt/0.1 M KOH solution interface, the Langmuir and Temkin adsorption isotherms ($\theta_H\;vs.\;E$), the equilibrium constants ($K_H=2.9X10^{-4}mol^{-1}$ for the Langmuir and $K_H=2.9X10^{-3}\exp(-4.6\theta_H)mol^{-1}$ for the Temkin adsorption isotherm), the interaction parameters (g=0 far the Langmuir and g=4.6 for the Temkin adsorption isotherm), the rate of change of the standard free energy of $\theta_H\;with\;\theta_H$ (r=11.4 kJ $mol^{-1}$ for g=4.6), and the standard free energies (${\Delta}G_{ads}^{\circ}=20.2kJ\;mol^{-1}$ for $k_H=2.9\times10^{-4}mol^{-1}$, i.e., the Langmuir adsorption isotherm, and $16.7<{\Delta}G_\theta^{\circ}<23.6kJ\;mol^{-1}$ for $K_H=2.9\times10^{-3}\exp(-4.6\theta_H)mol^{-1}$ and $0.2<\theta_H<0.8$, i.e., the Temkin adsorption isotherm) of H for the cathodic HER are determined using the phase-shift method. At intermediate values of $\theta_H$, i.e., $0.2<\theta_H<0.8$, the Temkin adsorption isotherm ($\theta_H\;vs.\;E$) corresponding to the Langmuir adsorption isotherm ($\theta_H\;vs.\;E$), and vice versa, is readily determined using the constant conversion factors. The phase-shift method and constant conversion factors are useful and effective for determining the Langmuir, Frumkin, and Temkin adsorption isotherms of intermediates for sequential reactions and related electrode kinetic and thermodynamic data at electrode catalyst interfaces.

• Analytical Science and Technology
• /
• v.12 no.1
• /
• pp.34-39
• /
• 1999

Estrone such as estriol and estradiol can not be determined by votammetric methods, because these are electrochemically inactive in the potential windows for mercury drop electrode. Nitro-derivatives of estrone are electro active and nitration of estrone is accomplished by heating the solution involving estrone and sodium nitrite in a water-bath at $100^{\circ}C$ for 30 min. Such nitro-derivatives are determined directly by voltammetry. The electrochemical behavior for nitrated estrone was investigated by cyclic voltammetry. The trace estrone was determinated by differential pulse adsorptive cathodic stripping voltammetry. Nitrated estrone gives a well defined voltammetric wave at ca. - 0.61 V (vs. Ag/AgCl electrode). The electrochemical reaction was irreversible process in sodium borate buffer at pH 11 and nitrated estrone was strongly adsorbed on the surface of mercury electrode. The optimal experimental conditions for the determination of nitrated esterone were found to be 0.05 M sodium nitrate, 0.01 M sodium borate, pH 11.0, and an accumlation potential of 0.10 V (vs. Ag/AgCl). The detection limit was as low as $1{\times}10^{-9}M$ for estrone with 2 min accumulation time.

• Journal of the Korean Chemical Society
• /
• v.37 no.5
• /
• pp.483-490
• /
• 1993

Voltammetric behavior of heavy lanthanide ions has been investigated by the DC, DPP and CV in acetonitrile solution. The reduction of $Gd^{3+}, Tb^{3+}, Dy^{3+}, Ho^{3+}, Er^{3+}, Tm^{3+} 및 Lu^{3+} proceed by three-electron change to the metallic state with totally irreversibility in 0.1M tetraethylammonium perchlorate. However, the reduction of Yb(Ⅲ) proceeds in two steps $(Yb^{3+} ＋ e^- \Leftrightarrow Yb^{2+} and Yb^{2+} ＋ 2e^- → Yb^0)$. The first reduction of Yb(Ⅲ) showed quasi reversible behavior, but the second reduction was irreversible in cyclic voltammetry. The cathodic peak current showed adsorptive properties in high concentration with lower sweep rate. The electroreduction of heavy lanthanides in water-acetonitrile mixture has been studied. In water-acetonitrile mixture, the negative shift of the peak potential and the decrease peak current were observed increasing water concentration. Also the Yb(Ⅲ) reduction to Yb(Ⅲ) has been deviated from quasi-reversible character with increase water amount. These results drive from the high solvation abilities of water which has high donor number.

• Analytical Science and Technology
• /
• v.23 no.1
• /
• pp.68-73
• /
• 2010

In order to develop the square wave voltammetric method determining cimetidine in an ampoule for injection, $5.00{\times}10^{-4}\;M$ cimetidine HCl solutions prepared with phosphate buffers of various pH values (3.01~8.97) were investigated by SWV. The well defined single peak due to the electrochemical reduction of -C=N-C$\equiv$N- in the structure of cimetidine moved towards the cathodic direction by -0.051V/pH as the pH values were increased indicating the involvement of hydrogen in its reduction. The calibration curves of cimetidine HCl in the concentration range between $1.00{\times}10^{-5}\;M$ and $5.00{\times}10^{-3}\;M$ prepared using three phosphate buffers yielded the slopes of 127,407nA/M (pH 3.01), 115,125nA/M (pH 5.00) and 111,287nA/M(pH 7.00) with excellent linearities of $R^2{\geqq}0.9997$. When one ampoule of Tagma Inj.$^{(R)}$ was analyzed by standard addition method by SWV, the within-day precision study (n=4) on the day of sample preparation resulted in the contents of cimetidine as $203{\pm}3.8\;mg$ (102% of the specified contents, RSD of 1.9%) and the inter-day precision (n=4) through 5 days was reasonable as 1.3% of RSD.

• Journal of the Korean Chemical Society
• /
• v.37 no.10
• /
• pp.881-887
• /
• 1993

A cobalt(II) ion-selective carbon-paste electrode (CPE) was constructed with ${\iota}$-sparteine. Cobalt(II) ion in aqueous solution was chemically deposited through the complexation with ${\iota}$-sparteine onto the CPE. The surface of CPEs were characterized by cyclic voltammetry and differential pulse voltammetry in an acetate buffer solution, separately. Exposure of the CPEs to an acid solution could regenerate surface to reuse it for the deposition. In more than 5 deposition / measurement / regeneration cycles, the response was reproducible and linear up to $5.0{\times}10^{-6}$M with linear sweep voltammetry. The peaks at 0.17V / 0.27V were correspond to the redox of Co(II)-SP complex deposited on CPE. The anodic peak of which appeared after scan over the cathodic peak of 0.17 V to more negative scan. In case of using the differencial pulse voltammetry (DPV), we have obtained the linear response $2.0{\times}10^{-7}$M with relative standard deviation ${\pm}5.6%$. The detection limit was $1.0{times}10^{-7}$M for 20 minutes of the deposition. We have also investigated the interference effect of various metal ions, which are expected to form the complex with the ligand on the electrode.

• Applied Chemistry for Engineering
• /
• v.32 no.6
• /
• pp.684-689
• /
• 2021

In this paper, we develop a cost effective and disposable voltammetric sensing platform involving screen-printed carbon electrode (SPCE) modified with the nanocomposites composed of multi-walled carbon nanotubes, polyelectrolyte, and tyrosinase for bisphenol A. This is known as an endocrine disruptor which is also related to chronic diseases such as obesity, diabetes, cardiovascular and female reproductive diseases, precocious puberty, and infertility. A negatively charged oxidized multi-walled carbon nanotubes (MWCNTs) wrapped with a positively charged polyelectrolyte, e.g., polydiallyldimethylammonium, was first wrapped with a negatively charged tyrosinae layer via electrostatic interaction and assembled onto oxygen plasma treated SPCE. The nanocomposite modified SPCE was then immersed into different concentrations of bisphenol A for a given time where the tyrosinase reacted with OH group in the bisphenol A to produce the product, 4,4'-isopropylidenebis(1,2-benzoquinone). Cyclic and differential pulse voltammetries at the potential of -0.08 V vs. Ag/AgCl was employed and peak current changes responsible to the reduction of 4,4'-isopropylidenebis(1,2-benzoquinone) were measured which linearly increased with respect to the bisphenol A concentration. In addition, the SPCE based sensor showed excellent selectivity toward an interferent agent, bisphenol S, which has a very similar structure. Finally, the sensor was applied to the analysis of bisphenol A present in an environmental sample solution prepared in our laboratory.