• Korean Chemical Engineering Research
• /
• v.50 no.4
• /
• pp.666-671
• /
• 2012

Gas hydrates are inclusion compounds formed when small-sized guest molecules are incorporated into the well defined cages made up of hydrogen bonded water molecules. Since large masses of natural gas hydrates exist in permafrost regions or beneath deep oceans, these naturally occurring gas hydrates in the earth containing mostly $CH_4$ are regarded as future energy resources. The heat of dissociation is one of the most important thermal properties in exploiting natural gas hydrates. The accurate and direct method to measure the dissociation enthalpies of gas hydrates is to use a calorimeter. In this study, the high pressure micro DSC (Differential Scanning Calorimeter) was used to measure the dissociation enthalpies of methane, ethane, and propane hydrates. The accuracy and repeatability of the data obtained from the DSC was confirmed by measuring the dissociation enthalpy of ice. The dissociation enthalpies of methane, ethane, and propane hydrates were found to be 54.2, 73.8, and 127.7 kJ/mol-gas, respectively. For each gas hydrate, at given pressures the dissociation temperatures which were obtained in the process of enthalpy measurement were compared with three-phase (hydrate (H) - liquid water (Lw) - vapor (V)) equilibrium data in the literature and found to be in good agreement with literature values.

• KSBB Journal
• /
• v.11 no.2
• /
• pp.225-237
• /
• 1996

Intrinsic binding kinetics of of 125I-bovine serum albumin (125I-BSA) and immobilized monoclonal anti-BSA (MAb 9.1) were studied. Small non-porous polystyrene beads (0.5${\mu}$m diameter) were used as a solid support to minimize the mass transfer interference on rate measurements. We demonstrated both theoretically and experimentally that the binding reaction is kinetically controlled. Rate measurements show that the association reaction is of second order and the dissociation reaction is of first order. Between 4 and $37^{\circ}C$ the measured equilibrium constant agrees well with the equilibrium constant calculated from the rate measurements. The temperature effects on association are much greater than on dissociation; the activation energy for association is about 9Kca1/mole, as compared to 2Kca1/mole for dissociation. The use of small non-porous beads as a solid support in binding studies essentially avoids mass transfer limitations; such a system makes it possible to determine the intrinsic binding characteristics of any immobilized antibody on a solid surface.

• Tunnel and Underground Space
• /
• v.24 no.2
• /
• pp.143-154
• /
• 2014

In this study, we simulated both dissociation of gas hydrate and mechanical deformation of hydrate-bearing sedimentary formation using geomechanical model. The geomechanical model analysis consists of two distinct codes of TOUGH+Hydrate and FLAC3D. The model is characterized by the fact that changes of temperature, pressure, saturation and their influence on the consequent evolution of effective stress, stiffness and strength of hydrate-bearing sediments during gas production could be well simulated. We compared the results of simulation for two different production methods, and showed that combination of depressurization and thermal stimulation results in the enhancement of production rate especially at early stage. We also presented that the hydrate dissociation-induced geomechanical deformation in unconsolidated clay is much larger than that in sandstone.

• Journal of the Korean Chemical Society
• /
• v.45 no.5
• /
• pp.401-412
• /
• 2001

The geometrical parameters, vibrational frequencies, and dissociation energies for $H_{2n+1}^+$ (n=1~6) clusters have been investigated using high level ab initio quantum mechanical techniques with large basis sets. The equilibrium geometries have been optimized at the self-consistent field (SCF), the single and double excitation configuration interaction (CISD), the coupled cluster with single and double excitation (CCSD), and the CCSD with connected triple excitations [CCSD(T)] levels of theory. The highest levels of theory employed in this study are TZ2P+d CCSD(T) up to $H^+_g$ and TZ2P CCSD(T) for $H_{11}^+$ and $H_{13}^+$. Harmonic vibrational frequencies are also determined at the SCF level of theory with various basis sets and confirm that all the optimized geometries are true minima. The dissociation energies, $D_e$, for $H_{2n+1}^+$ (n=26) have been predicted using energy differences at each optimized geometry and zero-point vibrational energies(ZPVEs) have been considered to compare with experimental dissociation energies, $D_0$.

• Bulletin of the Korean Chemical Society
• /
• v.11 no.3
• /
• pp.221-224
• /
• 1990

A kinetic study of the heterobimetallic dimer disruption of $PPN+^aCrMn(CO)_{10}$- by ligand L(L = CO, $PR_3$) is described. The rate was determined in several aprotic solvents. The results indicated that the reaction of $PPN+^aCrMn(CO)_{10}$- with $PR_3$ is of first order with respect to [$PPN+^aCrMn(CO)_{10}$-] and the heterolytic Cr-Mn bond dissociation energy is approximately 27 kcal/mol.

• Transactions on Electrical and Electronic Materials
• /
• v.14 no.6
• /
• pp.329-333
• /
• 2013

SiOC films were prepared by capacitively coupled plasma chemical vapor deposition, and the correlation between the binding energy by X-ray photoelectron spectroscopy and Arrhenius equation for ionization energy was studied. The ionization energy decreased with increase of the potential barrier, and then the dielectric constant also decreased. The binding energy decreased with increase of the potential barrier. The dielectric constant and electrical characteristic of SiOC film was obtained by Arrhenius equation. The dielectric constant of SiOC film was decreased by lowering the polarization, which was made from the recombination between opposite polar sites, and the dissociation energy during the deposition. The SiOC film with the lowest dielectric constant had a flat surface, which depended on how carbocations recombined with other broken bonds of precursor molecules, and it became a fine cross-linked structure with low ionization energy, which contributed to decreasing the binding energy by Si 2p, C 1s electron orbital spectra and O 1s electron orbital spectra. The dielectric constant after annealing decreased, owing to the extraction of the $H_2O$ group, and lowering of the polarity.

• Journal of Radiation Protection and Research
• /
• v.36 no.4
• /
• pp.190-194
• /
• 2011

After the first report that electrons with sub-ionization energy of DNA could cause single strand breaks or double strand breaks to DNA, there have been various studies to investigate the mechanisms of DNA damage by low-energy electrons. In this paper, we examined the possibility of using X-ray photoelectron spectroscopy (XPS) to analyze the dissociation patterns of the molecular bonds by electron irradiation on DNA thin films and tried to establish the method as a general tool for studying the radiation damage of biomolecules by low energ yelectrons. For the experiment, pBR322 plasmid DNA solution was formed into the films on tantalum plates by lyophilization and was irradiated by 5-eV electrons. Un-irradiated and irradiated DNA films were compared and analyzed using the XPS technique.

• Bulletin of the Korean Chemical Society
• /
• v.28 no.9
• /
• pp.1485-1488
• /
• 2007

Photodissociation dynamics of cyanamide (NH2CN) at 212 nm has been investigated by measuring rotationally resolved laser induced fluorescence spectra of CN fragments exclusively produced in the ground electronic state. From the spectra, rotational population distributions of CN as well as translational energy releases in the products were obtained. The measured average rotational energies of CN were 12.4 ± 0.5 and 11.6 ± 0.5 kJ/ mol for v'' = 0 and v'' = 1, respectively and the center of mass average translational energy release among products was 41.8 ± 6.4 kJ/mol. The observed energy partitioning was well represented by statistical prior calculations, from which it was suggested that the dissociation takes place on the ground electronic surface after rapid internal conversion.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2015.08a
• /
• pp.109.1-109.1
• /
• 2015

Understanding the reaction mechanisms and structures underlying the adsorption of biomolecules on semiconductors is important for functionalizing semiconductor surfaces for various bioapplications. Herein, we describe the characteristic behavior of a primary nucleobase adsorbed on the semiconductor Ge(100). The adsorption configuration of guanine, a primary nucleobase found in DNA and RNA, on the semiconductor Ge(100) at an atomic level was investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. When adsorbed on Ge(100) at room temperature, guanine appears dark in STM images, indicating that the adsorption of guanine on Ge(100) occurs through N-H dissociation. In addition, DFT calculations revealed that "N(1)-H dissociation through an O dative bonded structure" is the most favorable adsorption configuration of all the possible ones. We anticipate that the characterization of guanine adsorbed on Ge(100) will contribute to the development of semiconductor-based biodevices.

• Journal of the Korean Vacuum Society
• /
• v.7 no.s1
• /
• pp.20-24
• /
• 1998

Photploymer films are widely used in printing and electronic industries, and their usage is expanding to encompass holography, data storage and data processing, optical waveguides and compact disks, etc. One of widely used photoplymerization initiator, 20chloro-hexaarylbiimidazole (o-Cl-HABI), is studied by laser flash photolysis in dichloromethane solution in the absence and presence of the visible light photosensitizing dye, 2, 5-bis[(2, 3, 6, 7 -tetrahydro- 1H, 5H -benzo [i, j,] quinolizin -1-yl) methylene]-cyclopenta-none, (JAW). In the presence of JAW, an increase in triarylimidazolyl radicals L.formation is observed in relative to the absence of JAW. The mechanism of this photosensitizing dissociation is concluded as the dissociation of the o-Cl-HABI radical anion formed by the electron transfer from excited singlet state of JAW to o-Cl-HABI. The observed formation of L.radicals exhibits a linear dependence on o-Cl-HABI concentration. The rate constant of electron transfer obtained from this dependence is equal to (1.0$\pm$0.2) x $10^9 M^{-1}s^{-1}$. No reaction between the excited triplet state of JAW and o-Cl-HABI is found.