• EDISON SW 활용 경진대회 논문집
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• 제3회(2014년)
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• pp.347-358
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• 2014

본 논문에서는 양자 역학적 분자 동역학(Quantum Mechanical/Molecular Mechanical-Molecular Dynamics, QM/MM-MD)을 통해 수용액에 녹아 있는 Potassium Thiocyanate의 dynamics를 연구했다. Umbrella sampling technique을 활용하여 association/dissociation에 해당하는 Free energy surface를 구했다. 두 개의 Free energy minimum이 녹아 있는 두 이온의 center of mass 사이의 거리가 $4{\AA}$일 때와 $5{\sim}6{\AA}$ 부근일 때 나타났으며 $4{\AA}$일 때 더 안정 했다. 본 논문에서는 $4{\AA}$일 때를 Contact Ion Pair(CIP) $6{\AA}$일 때를 Dissociation Ion Pair(DlP)라고 칭했다. 이 minimum들이 무엇인 지를 밝혀 내기 위해 추가 연구를 수행하였다. Free energy 상에서 가장 안정 할 때(CIP) solute인 Potassium thiocyanate의 구조를 살펴 봤더니 Potassium ion은 Thiocyanate ion의 Sulfur보다 Nitrogen side를 선호하였다. 그 원인을 알아보기 위해 salvation shell의 구조를 Radial distribution function을 통해 살펴 봤더니 물 분자가 Nitrogen보다 Sulfur와 더 강한 상호작용을 하고 있었다. 그로 인해 Potassium ion이 Nitrogen을 선호한단 결과가 나온 것이다. 한편, 두 번째 minimum은 물 분자가 Potassium 이온과 Thiocyanate 이온 사이에 flexible하게 bridging을 하는 구조였다. 또한 단순 양자 계산을 통해서도 비슷한 구조를 얻을 수 있었다. 그러나 QM 계산은 0K에서 수행하는 것이기 때문에 엔트로피 효과가 없는 계산이지만 본 연구는 온도 300K로 실제 용매와 가깝게 수행함으로써 고정되어 있는 구조가 아니라 엔트로피와 엔탈피가 균형적으로 존재하는 실제 용액 속에서의 구조를 처음으로 보여주는 것이다.

• 약학회지
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• 제7권2_3호
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• pp.36-41
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• 1963

Cobalt thiocyanate ion에 미치는 영향을 연구하였다. Cobalt ion이 $NH_{4}CNS$ 용액에 의해서 생성되는 ion의 색의 transmittance는 확산에 의하여 적어지며, 황산존재하에서는 황산의 양과 Transmittance 사이에 비례적 관계가 있다. 염산 및 질산도 역시 Transmittance의 값에 영향을 미치기는 하나 염산의 경과에는 이 착 ion이 황산존재하보다 다소 불안정하며 질산에 의해서는 안정화가 극히 적어서 단시간내에 Perthiocyanuric acid로 인정되는 물질로 분해한다. 또한 그 Transmittance가 과량의 광산존재하에서 적어지는 현상으로 부터 $Co(SCN)^{2-n/_{$ n/의 n의 값이 커지는 것은 ether에 이행하는 SCN-을 Volhard 씨법으로 정량함으로서 확증하였다.

• Bulletin of the Korean Chemical Society
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• 제27권11호
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• pp.1832-1838
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• 2006

The present paper is focused on sorption concentration of silver (I) on some complex-forming ion exchangers in the initial thiocyanate form and subsequent determination of Ag(I) in the phase of anion exchanger AN-25 by diffuse reflectance spectroscopy. The sorption and kinetic characteristics of the sorbents were investigated. The apparent stability constants of thiocyanate silver complexes in the ion exchanger phase were calculated. The sorption-spectroscopic method is proposed for Ag(I) determination in aqueous solutions. The calibration curve is linear in the concentration range of 10-200 mg/L (sample volume is 10.0 mL) and the detection limit is 2 $\mu$g/mL. The presence of $Na^+,\;K^+,\;Mg^{2+}$ (macrocomponents) as well as of Ni (II), Co (II), Cu (II) do not hinder the determination of silver (I).

• 한국식품영양과학회지
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• 제21권1호
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• pp.49-53
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• 1992

십자화과 채소를 습열처리한 thiocyanate ion의 방출량은 열처리시간이 증가함에 따라 점차 증가하여 30분 열처리시 최대치를 나타내었으나, 건열처리시는 유의적인 변화가 없었다. 또한, 내생의 효소 myrosinase에 의한 자가분해시는 방치시간이 경과함에 따라 점차 증가하여 3시간 후에 최대치를 나타내었는데, 이는 습열처리시의 최대 방출량보다 많은 양을 나타내었으며, 시료별 방출량은 양배추, 배추, 무, 케일 및 겨자의 순으로 높게 나타났다. 열처리에 따른 indoleacetonitrile의 생성량은 시간이 경과함에 따라 증가함을 나타내었으며, 시료별 생성량은 양배추 및 무 순으로 높게 나타났다.

• Bulletin of the Korean Chemical Society
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• 제25권10호
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• pp.1484-1488
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• 2004

The thiocyanate-selective PVC membrane electrodes based on 5,10,15,20-tetrakis(2,4,6-trimethylphenyl)-porphyrinatomanganese(III) chloride [Mn(TMP)Cl] and 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinatomanganese(III) chloride $[Mn(Cl_8TPP)Cl]$ as ion carriers were investigated. The effect of ionophores, membrane compositions, plasticizers, and solution pHs on the response characteristics were studied. The Mn(TMP)Cl as an ionophore shows the best potentiometric sensitivity with a slope of -58.7 mV/decade and a detection limit of $log[SCN^-]$ = -6.90, and selectivity for thiocyanate over strong hydrophobic interfering anions such as ${ClO_4}^-$ and salicylate. The potentiometric response is affected by the electronic effect of the substituents and solution pHs. The presence of substituents with electron donating and more liphophilic characters around the ligated metal center produces an improved response toward $SCN^-$.

• Bulletin of the Korean Chemical Society
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• 제30권10호
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• pp.2303-2308
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• 2009

A thiocyanate poly(vinyl chloride) (PVC) membrane electrode based on [1,2-bis(diphenylphosphino)ethane]dihalopalladium( II), [(dppe)$PdX_2$, X = Cl ($L^1$), X = I ($L^2$)] as active sensor has been developed. The diiodopalladium complex, [(dppe)$PdI_2](L^2$) displays an anti-Hofmeister selectivity sequence: $SCN^-\;>\;I^-\;>\;{ClO_4}^-\;>\;Sal^-\;>\;Br^-\;>\;{NO_2}^-\;>\;{HPO_4}^-\;>\;AcO^-\;>\;{NO_3}^-\;>\;{H_2PO_4}^-\;>\;{CO_3}^{2-}$. The electrode exhibits a Nernstian response (-59.8 mV/decade) over a wide linear concentration range of thiocyanate ($(1.0\;{\times}\;10^{-1}\;to\;5.0\;{\times}\;10^{-6}$ M), low detection limit ($(1.1\;{\times}\;10^{-6}$ M), fast response $(t_{90%}$ = 24 s), and applicability over a wide pH range (3.5∼11). Addition of anionic sites, potassium tetrakis[p-chlorophenyl] borate (KTpClPB) is shown to improve potentiometric anion selectivity, suggesting that the palladium complex may operate as a partially charged carrier-type ionophore within the polymer membrane phase. The reaction mechanism is discussed with respect to UV-Vis and IR spectroscopy. Application of the electrode to the potentiometric titration of thiocyanate ion with silver nitrate is reported.

• Bulletin of the Korean Chemical Society
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• 제24권12호
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• pp.1775-1780
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• 2003

A continuous flow system has been developed to determine trace Cu(II), Mn(II), Ni(II) and Zn(II) in a large volume of water samples by a solvent sublation technique. The mixed solution of 1,10-phenanthroline(phen) and thiocyanate ion was used as ligands for the formation of their ternary complexes. The continuous system was constructed in this laboratory with a peristaltic pump, a mini shaker, three mixing bottles and a flotation cell by connecting each part with a polyethylene tube. The flotation conditions such as the flow rate of sample solution and the injection rates of ligand, buffer and surfactant solutions have been investigated to obtain the best sublation efficiencies. Each solution flowed into the flotation cell through each polyethylene tube by the peristaltic pumps. The ternary complexes were floated and extracted into MIBK in a flotation cell of 2 L by bubbling a nitrogen gas. The absorbances of extracted analytes in MIBK were directly measured by graphite furnace-AAS. The concentrations of 1,10-phenanthroline and thiocyanate ion were $2.6\;{\times}\;10^{-3}$ M and $2.3\;{\times}\;10^{-2}$ M in the mixed solution, respectively. The pH of sample solution was adjusted to 5.0 with a buffer solution and 1%(m/v) sodium lauryl sulphate solution was added as a surfactant to support the effective flotation of the complexes. The $N_2$ gas was bubbled at 30 mL/min for 90 minutes for 20 L of sample. Reproducible results of less than 10% RSD and recoveries of 80-120% could be obtained in real samples.

• 약학회지
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• 제10권4호
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• pp.1-6
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• 1966

Various thiocyanatoammine chromium complex salts are prepared by the known methods and the Rf. value of these complex salts are determined by four developers. These four developers were used in the paper chromatographical work of cobalt complex salts by Yamamoto in 1954. It was also found that the developer A (Ch$_{3}$OH, acetone, NH$_{4}$OH) gave best results of these four developers and the decending development gave better results than ascending development in this experiment. In the case of decending development using developer A, it is found that the Rf. value is increased with the number of thiocyanate radical. The reason of this curious results can be explained that the thiocyanate radical in the complex ion is more active for the organic solvent than ammine radical. Shifting of electrons to the central metal and the charge of the complex ion can also effect ot the Rf. value but much questions are remained for the explanation of the above curious phenomenon. Separation of mixed sample is also studied for various mixture of the above complex salts. In the case of the mixture of hexammine and diammine complex salt, the clear separation is possible but in almost all other mixed sample, the results are not clear. Therefore it can be said that the results of this work can be used in the qualitative analysis of the individual complex salts, except the mixed sample of hexammine and diammine complex salts.

• 대한화학회지
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• 제14권3호
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• pp.213-219
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• 1970

In the presence of hydrogen peroxide, the effects of temperature and pH to the catalytic reaction velocity of cupric -thiocyanate and the quantities of reduction products adsorbed on the D.M.E. have been studied by polarographic method. According to these experiments, the following empirical equation has been derived for the relation among temperature $T_i$, concentration of hydrogen ion $pH_i$ and adsorbed cuprous-thiocyanate in moles/$cm^2Z_{ij}$, and rate constant log$K_{ij}$ $$log\;K_{ij}=\frac{1}{T_i}\{A(pH_j)+B\}+C(pH_j)+D$$ $$Z_{ij}=\frac{1}{T_i}\{{\alpha}(pH_j)^{\frac{1}{2}}+{\beta}\}+{\gamma}(pH_j)^{\frac{1}{2}}+{\delta}$$ where, A,B,C,D and {$\alpha},{\beta},{\gamma},{\delta}$ are constants. The Calculated values by both equations are well agreed with empirical values within 8% in the error.

• 대한화학회지
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• 제29권6호
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• pp.623-628
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• 1985

산성용매에서 몰리브덴-옥살산 결합의 고리열림이 일어난 다음 티오시안산과 반응하는 속도를 460nm에서 분광학적으로 측정하였다. 산성용매에서 몰리브덴-옥살산의 해리와 이 해리된 착물과 티오시안산의 반응속도를 티오시안산 및 수소이온농도에 따라 연구하였다. 몰티브덴에 결합된 옥살산리간드에 양성자첨가가 되고 이 양성자 첨가된 착물은 티오시안산이온과 반응을 빠르게 한다. 이들 결과에서부터 산성용매에서 옥살산리간드의 치환은 몰리브덴닐산소의 트란스에 결합된 산소의 결합이 끊어지는 과정과 관련되는 해리메카니즘에 의해서 설명할 수 있다.