• Journal of the Korean Chemical Society
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• v.34 no.5
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• pp.418-423
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• 1990

The protonation constants for the macrocyclic ligands 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloeicosane (NdienOdienH$_4$), 1,12,15-triaza-3,4;9,10-dibenzo-5,8-dioxa cycloheptadecane (NdienOenH$_4$), and 1,15-diaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloheptadecane (NenOdienH4) have been determined by the potentiometry in aqueous solutions (25$^{\circ}C$, I = 0.1, KNO$_3$). The stability constants for complexes formed in the aqueous solution (25$^{\circ}C$, I = 0.1, KNO$_3$) between the above ligands and the metal ions (Co(Ⅱ), Ni(Ⅱ), and Cu(Ⅱ)) have been measured by potentiometry. The rate of the ligand substitution reaction was measured spectrophotometrically by the addition of aqueous solutions of ethylenediamine to the solution of the complex. From the study of the temperature effect on the rate constant (k$_{obs}$), activation parameters (E$_a$,${\{Delta}H^{\neq}$, and ${\{Delta}S^{\neq}$) have been determined. The possible mechanism for the substitution reaction is proposed.

• Journal of Biosystems Engineering
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• v.35 no.5
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• pp.343-349
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• 2010

Rapid on-site sensing of nitrate-nitrogen and potassium ions in hydroponic solution would increase the efficiency of nutrient use for greenhouse crops cultivated in closed hydroponic systems while reducing the potential for environmental pollution in water and soil. Ion-selective electrodes (ISEs) are a promising approach because of their small size, rapid response, and the ability to directly measure the analyte. The capabilities of the ISEs for sensing nitrate and potassium in hydroponic solution can be affected by the presence of other ions such as calcium, magnesium, sulfate, sodium, and chloride in the solution itself. This study was conducted to investigate the applicability of two ISEs consisting of TDDA-NPOE and valinomycin-DOS PVC membranes for quantitative determinations of $NO_3$-N and K in hydroponic solution. Nine hydroponic solutions were prepared by diluting highly concentrated paprika hydroponic solution to provide a concentration range of 3 to 400 mg/L for $NO_3$-N and K. Two of the calibration curves relating membrane response and nutrient concentration provided coefficients of determination ($R^2$) > 0.98 and standard errors of calibration (SEC) of < 3.79 mV. The use of the direct potentiometry method, in conjunction with an one-point EMF compensation technique, was feasible for measuring $NO_3$-N and K in paprika hydroponic solution due to almost 1:1 relationships and high coefficients of determination ($R^2$ > 0.97) between the levels of $NO_3$-N and K obtained with the ion-selective electrodes and standard instruments. However, even though there were strong linear relationships ($R^2$ > 0.94) between the $NO_3$-N and K concentrations determined by the Gran's plot-based multiple standard addition method and by standard instruments, hydroponic $NO_3$-N concentrations measured with the ISEs, on average, were about 10% higher than those obtained with the automated analyzer whereas the K ISE predicted about 59% lower K than did the ICP spectrometer, probably due to no compensation for a difference between actual and expected concentrations of standard solutions directly prepared.

• Analytical Science and Technology
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• v.13 no.2
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• pp.173-178
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• 2000

A new open-chain ligand containing two phenol groups, 1, 14-Bis (2-hydroxybenzyl)-2, 6, 9, 12-tetraazatetradecane(bsated) was synthesized as its tetrahydrochloride salt and characterized by elemental analysis, mass, infrared and NMR. Its proton dissociation constants ($logK^n{_H}$) and stability constants ($logK_{ML}$) toward $Co^{2+}$, $Ni^{2+}$, $Cu^{2+}$ and $Zn^{2+}$ were determined at $25^{\circ}C$ and 0.10M($KNO_3$) ionic strength in aqueous solution by potentiometry. The X-ray structure of its copper (II) complex [Cu(bsated)]$(ClO_4)_2$ was reported: Monoclinic space group $P2_1/n$, $a=17.856(4){\AA}$, $b=17.709(1){\AA}$, $c=8.539(2){\AA}$, $V=2700(2){\AA}$ with Z=4. Electrochemical studies of [Cu(bsated)]$(ClO_4)_2$ complex in dimethyl sulfoxide (DMSO) solution containing tetrabutylammonium perchlorate (supporting electrolyte) were carried out by cyclic voltammograms (CV) and normal pulse voltammetry (NPV).

• Analytical Science and Technology
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• v.19 no.2
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• pp.131-141
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• 2006

Hydrobromic acid salt of a $N_2O_2$ tetradentate ligand, N,N'-bis(2-hydroxybenzyl)-ethylene-diamine ($H-BHE{\cdot}2HBr$) was synthesized. $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ and $CH_3O-BHE{\cdot}2HBr$ having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of $H-BHE{\cdot}2HBr$ were also synthesized. $Nap-BHE{\cdot}2HBr$ having naphthalen-2-ol instead of the phenol group was also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and the order of the calculated overall proton dissociation constants (${\log}{\beta}_p$) of each ligand was Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE. The order showed a similar trend to that of Hammett substituent constants(${\sigma}_P$). The order of the stability constants (${\log}K_{ML}$) was CO(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order in their stability constants (${\log}K_{ML}$) of each transition metal complex agreed well with that of the overall proton dissociation constants (${\log}{\beta}_p$).

• Journal of the Korean Chemical Society
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• v.39 no.7
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• pp.538-542
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• 1995

The stability constant and the thermodynamic parameters of the hydrazide Schiff base ligands such as N,N'-oxalylbis(salicylaldehydehydrazone)(OBSH), N,N'-malonylbis(salicylaldehydehydrazone)(MBSH), and N,N'-succinylbis(salicylaldehydehydrazone)(SBSH) with dioxouranium(Ⅵ) ion have been determined by potentiometry in 95% DMF solution at various temperatures. The order of stability constants increased SBSH

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1738-1742
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• 2005

In this study a novel triiodide ion-selective electrode based on a charge transfer complex of iodine and Bis(2-hydroxyacetophenone)butane-2,3-dihydrazone (ICT), as a membrane carrier was prepared. The electrode has a linear dynamic range between 1.0 ${\times}$ $10^{-2}$ and 5.0 ${\times}$ $10^{-7}$ M, with a Nernstian slope of 58. 99 ${\pm}$ 0.3 mV $decade^{-1}$ and detection limit of 3.0 ${\times}$ $10 ^{-7}$ M. The potentiometric response of the proposed sensor is independent of the pH of the solution in the pH range of 3.0-10.0. The electrode possesses the advantages of short conditioning time, fast response time, and especially, very good selectivity over a large number of common organic and inorganic anions. The electrode can be used for at least 6 months without any considerable divergences in the potentials. It was used as an indicator electrode in potentiometric titration of triiodide ion with thiosulfate.

• Bulletin of the Korean Chemical Society
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• v.27 no.6
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• pp.899-902
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• 2006

The complexation of N,N'-4,5-(ethylenedioxy)benzenebis(salicylideneimine), (salphen$H_2$) with uranyl ion was studied in acetonitrile solution spectrophtometrically, and the formation constant of the resulting 1 : 1 complex was evaluated. The salphen$H_2$ ligand was used as an ionophore in plasticized poly(vinyl chloride) (PVC) matrix membrane sensor for uranyl ion. The prepared sensors exhibited a near Nernstian response, 28.0-30.9 mV/decade for uranyl ion over the concentration range $1.0\;{\times}\;10^{-2}$ to $1.0\;{\times}\;10^{-6}$M with a limit of detection of $3.2\;{\times}\;10^{-7}$ M. The proposed electrode could be used at a working pH range of 1.5 - 4.0.

• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1418-1422
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• 2006

In this work the construction of a novel poly(vinyl chloride) membrane sensor based on 2,2'-dianiline disulfide (DADS) as a neutral carrier, o-nitrophenyloctyl ether (NPOE) as a plasticizer and sodium tetraphenyl borate (NaTPB) as an anionic site with unique selectivity towards Tm(III) ions is reported. The electrode has a linear dynamic range between $1.0\;{\times}\;10^{-6}$ and $1.0\;{\times}\;10^{-2}$ M, with a nice Nernstian slope of 19.5 ${\pm}$ 0.3 mV per decade and a detection limit of $4.0\;{\times}\;10^{-7}$ M at the pH range of 4.8-8.5. It has a very fast response time (<15 s) in the whole concentration range, and can be used for at least 4 weeks without any considerable divergence in the electrode potentials. The proposed sensor revealed comparatively good selectivity with respect to most common metal ions, and especially lanthanide ions. It was used as an indicator electrode in the potentiometric titration of Tm(III) ions with EDTA and in direct determination of concentration of Tm(III) ions in binary mixtures. It was also applied in determination of fluoride ions in mouth wash preparations.

• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.401-405
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• 2010

The Schiff base 1,2-bis(E-2-hydroxy benzylidene amino)anthracene-9,10-dione has been synthesized and explored as ionophore for preparing PVC-based membrane sensors selective to the copper ($Cu^{2+}$) ion. Potentiometric investigations indicate high affinity of these receptors for copper ion. The best performance was shown by the membrane of composition (w/w) of ionophore: 1 mg, PVC: 33 mg, DOP: 66 mg and KTpClPB as additive were added 50 mol % relative to the ionophore in 1 ml THF. The proposed sensor's detection limit is $2.8{\times}10^{-7}$ M over pH 5 at room temperature (Nernstian slope 31.76 mV/dec.) with a response time of 15 seconds and showed good selectivity to copper ion over a number of interfering cations.

• Bulletin of the Korean Chemical Society
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• v.30 no.9
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• pp.1956-1962
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• 2009

The binding abilities of two multidentate tripodal amine catechol ligands, cis,cis-1,3,5-tris[(2,3-dihydroxybenzylamino) aminomethyl]cyclohexane (TMACHCAT, $L^1)\;and\;N^1,N^3,N^5$-tris(2-(2,3-dihydroxybenzylamino) ethyl)cyclohexane-1,3,5-tricarboxamide (CYCOENCAT, $L^2$) with Ga(III) and In(III) have been investigated by potentiometric and spectrophotometric methods in an aqueous medium of 0.1 M KCl at 25 ${\pm}\;1\;{^{\circ}C}.$ The ligands $L^1\;and\;L^2$ formed various monomeric species $MLH_3,\;MLH_2$, MLH and ML (M = $Ga^{+3}\;and\;In^{+3}$) and showed potential to form strong encapsulated tris(catechol) type complexes. The coordination modes, binding ability and selectivity of the ligands towards Ga(III) and In(III) have been discussed with the help of experimental evidences, and supported with molecular modeling calculations.