• Title/Summary/Keyword: Formation free energy

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Effect of Number and Location of Amine Groups on the Thermodynamic Parameters on the Acridine Derivatives to DNA

  • Kwon, Ji Hye;Park, Hee-Jin;Chitrapriya, Nataraj;Han, Sung Wook;Lee, Gil Jun;Lee, Dong Jin;Cho, Tae-Sub
    • Bulletin of the Korean Chemical Society
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    • v.34 no.3
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    • pp.810-814
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    • 2013
  • The thermodynamic parameters for the intercalative interaction of structurally related well known intercalators, 9-aminoacridine (9AA) and proflavine (PF) were determined by means of fluorescence quenching study. The fluorescence intensity of 9AA decreased upon intercalation to DNA, poly[$d(A-T)_2$] and poly[$d(G-C)_2$]. A van't Hoff plot was constructed from the temperature-dependence of slope of the ratio of the fluorophore in the absence and presence of a quencher molecule with respect to the quencher concentration, which is known as a Stern-Volmer plot. Consequently, the thermodynamic parameters, enthalpy and entropy change, for complex formation was calculated from the slope and y-intercept of the van't Hoff plot. The detailed thermodynamic profile has been elucidated the exothermic nature of complex formation. The complex formation of 9AA with DNA, poly[$d(A-T)_2$] and poly[$d(G-C)_2$] was energetically favorable with a similar negative Gibb's free energy. On the other hand, the entropy change appeared to be unfavorable for 9AA-poly[$d(G-C)_2$] complex formation, which was in contrast to that observed with native DNA and poly[$d(A-T)_2$] cases. The equilibrium constant for the intercalation of PF to poly[$d(G-C)_2$] was larger than that to DNA, and was the largest among sets tested despite the most unfavorable entropy change, which was compensated for by the largest favorable enthalpy. The favorable hydrogen bond contribution to the formation of the complexes was revealed from the analyzed thermodynamic data.

The Preparation of Dye-Sensitized Solar Cell Paste Used the Peroxo Titanium Complex and Characteristics by Annealing Temperature (과산화 티타늄 복합체를 이용한 염료감응형 태양전지용 페이스트의 제조 및 열처리 온도에 따른 특성)

  • Park, Hyunsu;Joo, Soyeong;Choi, Joon-Phil;Kim, Woo-Byoung
    • Journal of Powder Materials
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    • v.22 no.6
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    • pp.396-402
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    • 2015
  • The organic binder-free paste for dye-sensitized solar cell (DSSC) has been investigated using peroxo titanium complex. The crystal structure of $TiO_2$ nanoparticles, morphology of $TiO_2$ film and electrical properties are analyzed by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Electrochemical Impedance Spectra (EIS), and solar simulator. The synthesized $TiO_2$ nanopowders by the peroxo titanium complex at 150, 300, $400^{\circ}C$, and $450^{\circ}C$ have anatase phase and average crystal sizes are calculated to be 4.2, 13.7, 16.9, and 20.9 nm, respectively. The DSSC prepared by the peroxo titanium complex binder have higher $V_{oc}$ and lower $J_{sc}$ values than that of the organic binder. It can be attributed to improvement of sintering properties of $TCO/TiO_2$ and $TiO_2/TiO_2$ interface and to formation of agglomerate by the nanoparticles. As a result, we have investigated the organic binder-free paste and 3.178% conversion efficiency of the DSSC at $450^{\circ}C$.

Low-Temperature Chemical Sintered TiO2 Photoanodes Based on a Binary Liquid Mixture for Flexible Dye-Sensitized Solar Cells

  • Md. Mahbubur, Rahman;Hyeong Cheol, Kang;Kicheon, Yoo;Jae-Joon, Lee
    • Journal of Electrochemical Science and Technology
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    • v.13 no.4
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    • pp.453-461
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    • 2022
  • A chemically sintered and binder-free paste of TiO2 nanoparticles (NPs) was prepared using a binary-liquid mixture of 1-octanol and CCl4. The 1:1 (v/v) complex of CCl4 and 1-octanol easily interacted chemically with the TiO2 NPs and induced the formation of a highly viscous paste. The as-prepared binary-liquid paste (PBL)-based TiO2 film exhibited the complete removal of the binary-liquid and residuals with the subsequent low-temperature sintering (~150℃) and UV-O3 treatment. This facilitated the fabrication of TiO2 photoanodes for flexible dye-sensitized solar cells (f-DSSCs). For comparison purposes, pure 1-octanol-based TiO2 paste (PO) with moderate viscosity was prepared. The PBL-based TiO2 film exhibited strong adhesion and high mechanical stability with the conducting oxide coated glass and plastic substrates compared to the PO-based film. The corresponding low-temperature sintered PBL-based f-DSSC showed a power conversion efficiency (PCE) of 3.5%, while it was 2.0% for PO-based f-DSSC. The PBL-based low- and high-temperature (500℃) sintered glass-based rigid DSSCs exhibited the PCE of 6.0 and 6.3%, respectively, while this value was 7.1% for a 500℃ sintered rigid DSSC based on a commercial (or conventional) paste.

Effect of Heat Treatment on Microstructure and Mechanical Properties of Al-Zn-Mg-Cu-Si Sintered Alloys with and Without High-energy Ball Milling (Al-Zn-Mg-Cu-Si 소결합금의 미세조직과 기계적 특성에 미치는 열처리의 영향)

  • Junho Lee;Seonghyun Park;Sang-Hwa Lee;Seung Bae Son;Seok-Jae Lee;Jae-Gil Jung
    • Journal of Powder Materials
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    • v.30 no.6
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    • pp.470-477
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    • 2023
  • The effects of annealing on the microstructure and mechanical properties of Al-Zn-Mg-Cu-Si alloys fabricated by high-energy ball milling (HEBM) and spark plasma sintering (SPS) were investigated. The HEBM-free sintered alloy primarily contained Mg2Si, Q-AlCuMgSi, and Si phases. Meanwhile, the HEBM-sintered alloy contains Mg-free Si and θ-Al2Cu phases due to the formation of MgO, which causes Mg depletion in the Al matrix. Annealing without and with HEBM at 500℃ causes partial dissolution and coarsening of the Q-AlCuMgSi and Mg2Si phases in the alloy and dissolution of the θ-Al2Cu phase in the alloy, respectively. In both alloys, a thermally stable α-AlFeSi phase was formed after long-term heat treatment. The grain size of the sintered alloys with and without HEBM increased from 0.5 to 1.0 ㎛ and from 2.9 to 6.3 ㎛, respectively. The hardness of the sintered alloy increases after annealing for 1 h but decreases significantly after 24 h of annealing. Extending the annealing time to 168 h improved the hardness of the alloy without HEBM but had little effect on the alloy with HEBM. The relationship between the microstructural factors and the hardness of the sintered and annealed alloys is discussed.

A LiPF6-LiFSI Blended-Salt Electrolyte System for Improved Electrochemical Performance of Anode-Free Batteries

  • Choi, Haeyoung;Bae, YeoJi;Lee, Sang-Min;Ha, Yoon-Cheol;Shin, Heon-Cheol;Kim, Byung Gon
    • Journal of Electrochemical Science and Technology
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    • v.13 no.1
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    • pp.78-89
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    • 2022
  • ANODE-free Li-metal batteries (AFLMBs) operating with Li of cathode material have attracted enormous attention due to their exceptional energy density originating from anode-free structure in the confined cell volume. However, uncontrolled dendritic growth of lithium on a copper current collector can limit its practical application as it causes fatal issues for stable cycling such as dead Li formation, unstable solid electrolyte interphase, electrolyte exhaustion, and internal short-circuit. To overcome this limitation, here, we report a novel dual-salt electrolyte comprising of 0.2 M LiPF6 + 3.8 M lithium bis(fluorosulfonyl)imide in a carbonate/ester co-solvent with 5 wt% fluoroethylene carbonate, 2 wt% vinylene carbonate, and 0.2 wt% LiNO3 additives. Because the dual-salt electrolyte facilitates uniform/dense Li deposition on the current collector and can form robust/ionic conductive LiF-based SEI layer on the deposited Li, a Li/Li symmetrical cell exhibits improved cycling performance and low polarization for over 200 h operation. Furthermore, the anode-free LiFePO4/Cu cells in the carbonate electrolyte shows significantly enhanced cycling stability compared to the counterparts consisting of different salt ratios. This study shows an importance of electrolyte design guiding uniform Li deposition and forming stable SEI layer for AFLMBs.

Study on the Spheroidizing Mechanism of Graphite in Cast iron (part 1) (鑄鐵에 있어서의 黑鉛球狀化機構에 關한 硏究 (1))

  • Hyung Sup Choi;Ji Yung Chang
    • Journal of the Korean Chemical Society
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    • v.7 no.1
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    • pp.51-57
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    • 1963
  • It is well known that the graphite flakes become spherulite, when a suitable amount of nodulizing element, such as cerium or magnesium, is added to the cast iron. The change of graphite from flake to nodular shape improves not only the tensile strength but the ductility as well. However, the mechanism of spheroidization of graphite in cast iron has not yet been clearly understood, and various theories proposed by a number of investigators were such that it may be due to the special nucleation effect, prevention of flake formation by the adsorption of magnesium vapour on the graphite surface or file surface free energy difference between plain graphite and magnesium-adsorbed graphite. Regardless of the speculations of spheroidizing mechanism of the graphite in the cast iron, the final phenomenon comes to the conclusion that it may be due to the lack of wettability between graphite and iron matrix. In order to collaborate this fact through an experimental method, the authors have constructed a vacuum arc furnace for the wettability measurement as its first step. Our study and experiments were then directed to the comparison of the wettability between iron and graphite on the two cases (namely, the one where magnesium was preliminarily coated on the graphite surface and the other not coated), by means of contact angle measurements. The result was such that a significant difference of the contact angles has been shown between the above two cases. indicating the spheroidization of graphite which might have resulted from the lack of wettability between magnesium-adsorbed graphite and iron matrix.

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The Studies on Formation of Aggregates of Dyes-Surfactant System in Aqueous Solution (수용액에서 색소-계면활성제 계의 회합 생성에 관한 연구)

  • Choi, Ho Soeb;Kim, Heung-Tu
    • Journal of the Korean Chemical Society
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    • v.39 no.3
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    • pp.143-149
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    • 1995
  • At low concentration a simplified model of organic dye-surfactant system has been used to evaluate. By applying the resultant three parameter equation to the experimental data, values for the equilibrium constants for the ion-pair formation $(K_O)$, surfactant molecule addition to aggregates $(K_S)$ and dye aggregation reactions $(K_D)$ could be calculated and changes of free energy have obtained from its values. $K_O$ and K_S$ values were larger than those expected electrostatic interaction indicatihng a hydrophobic contribution and the $K_D$ values were about 10~20 times higher than those found for association in pure aqueous solutions which can be ascribed to the screening effect of the electrostatic repulsion.

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Effect of milling on the electrical properties of Ba(Fe1/2Ta1/2)O3 ceramic

  • Mahto, Uttam K.;Roy, Sumit K.;Chaudhuri, S.;Prasad, K.
    • Advances in materials Research
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    • v.5 no.3
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    • pp.181-192
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    • 2016
  • In this work effect of high energy milling on the structural and electrical properties of $Ba(Fe_{1/2}Ta_{1/2})O_3$ (BFT) ceramic synthesized using standard solid-state reaction method were investigated. X-ray diffraction studies indicated that the unit cell structure for all the samples to be hexagonal (space group: P3m1). FTIR spectra also confirmed the formation of BFT without any new phase. The milled (10 h) BFT ceramic showed the formation of small grain sizes (<$2{\mu}m$) which is beneficial for dielectric applications in high density integrated devices. Besides, the milled (10 h) BFT ceramic sample exhibited superior dielectric properties (enhancement in ${\varepsilon}^{\prime}-value$ and reduction in $tg{\delta}-value$) compared to un-milled one. Impedance analysis indicated the negative temperature coefficient of resistance (NTCR) character. The correlated barrier hopping model (jump relaxation type) is found to successfully explain the mechanism of charge transport in present ceramic samples.

The Characteristics and Formation of Tungsten Nano-Powder by Ultrasonic Spray Pyrolysis Method (초음파분무열분해법에 의한 나노 텅스텐 분말의 형성 및 특성에 관하여)

  • Lee, Ho-Jin;Yoon, Jung-Hyun;Choe, Jean-Il
    • Journal of the Korean institute of surface engineering
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    • v.41 no.4
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    • pp.174-179
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    • 2008
  • Nanosize tungsten powder was synthesized by ultrasonic spray pyrolysis method through a solution containing ammonium metatungstate hydrate $[(NH_4)_6W_{12}O_{39}{\cdot}H_2O]$ and reduction treatment. It was expected the improvement of mechanical properties due to increasing surface free energy and surface activity. Starting solutions with each concentration, reaction temperature and reduction treatment were significantly influenced on the formation of tungsten size and phase. It was found that particle size was decreased with concentration of starting solution and surface tension were decreased. The particle size was increased at thermal decomposition temperature above $600^{\circ}C$ by neck growth of interparticles. Tungsten particles were formed by reduction reaction in atmosphere of hydrogen gas at the temperature above $700^{\circ}C$.

Theoretical Estimation of Stoichiometry for Biodegradation of Hazardous Organic Compounds (유해유기물질에 대한 미생물 분해 반응식의 이론적 예측)

  • 우승한;박종문
    • Journal of Soil and Groundwater Environment
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    • v.8 no.2
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    • pp.70-77
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    • 2003
  • Theoretical estimation of overall stoichiometry for the microbial degradation of hazardous organic compounds is described. Half-reaction method based on microbial energetics was used in the theoretical estimation. In addition to the half-reaction method, other theoretical methods such as intermediate formation, oxygenation reaction, and estimation of the standard free energy of formation by group contribution theory were also applied. As a case study, the application of these methods was demonstrated for the estimation of microbial kinetics in the biodegradation of phenanthrene which was chosen as a model hazardous organic compound along with glucose and hexadecane. The cell yield, oxygen requirement, nitrogen requirement, and mineralization ratio could be estimated from the overall stoichiometry. It is believed that these theoretical estimation methods are useful tools for practical design and assessment of bioremediation of soil and groundwater contaminated with hazardous organic compounds.