• Analytical Science and Technology
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• v.7 no.2
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• pp.213-224
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• 1994

Several isotopomers of cyclooctanone were prepared by selective deuterium substitution. Intrinsic isotope effects on $^{13}C$ NMR chemical shifts of these isotopomers were investigated systematically at low temperature. These istope effects were discussed in relation to the preferred boat-chair conformation of cyclooctanone. Deuterium isotope effects on NMR chemical shifts have been known for a long time. Especially in a conformationally mobile molecule, isotope perturbation could affect NMR signals through a combination of isotope effects on equilibria and intrinsic effects. The distinction between intrinsic and nonintrinsic effects is quite difficult at ambient temperature due to involvement of both equilibrium and intrinsic isotope effects. However if equilibria between possible conformers of cyclooctanone are slowed down enough on the NMR time scale by lowering temperature, it should be possible to measure intrinsic isotope shifts from the separated signals at low temperature. $^{13}C$ NMR has been successfully utilized in the study on molecular conformation in solution when one deals with stable conformers or molecules were rapid interconversion occurs at ambient temperature. The study of dynamic processes in general requires analysis of spectra at several temperature. Anet et al. did $^1H$ NMR study of cyclooctanone at low temperature to freeze out a stable conformation, but were not able initially to deduce which conformation was stable because of the complexity of alkyl region in the $^1H$ NMR spectrum. They also reported the $^1H$ and $^{13}C$ NMR spectra of the $C_9-C_{16}$ cycloalkanones with changing temperature from $-80^{\circ}C$ to $-170^{\circ}C$, but they did not report a variable temperature $^{13}C$ NMR study of cyclooctanone. For the analysis of the intrinsic isotope effect with relation to cylooctanone conformation, $^{13}C$ NMR spectra are obtained in the present work at low temperatures (up to $-150^{\circ}C$) in order to find the chemical shifts at the temperature at which the dynamic process can be "frozen-out" on the NMR time scale and cyclooctanone can be observed as a stable conformation. Both the ring inversion and pseudorotational processes must be "frozen-out" in order to see separate resonances for all eight carbons in cyclooctanone. In contrast to $^1H$ spectra, slowing down just the ring inversion process has no apparent effects on the $^{13}C$ spectra because exchange of environments within the pairs of methylene carbons can still occur by the pseudorotational process. Several isotopomers of cyclooctanone were prepared by selective deuterium substitution (fig. 1) : complete deuterium labeling at C-2 and C-8 positions gave cyclooctanone-2, 2, 8, $8-D_4$ : complete labeling at C-2 and C-7 positions afforded the 2, 2, 7, $7-D_4$ isotopomer : di-deuteration at C-3 gave the 3, $3-D_2$ isotopomer : mono-deuteration provided cyclooctanone-2-D, 4-D and 5-D isotopomers : and partial deuteration on the C-2 and C-8 position, with a chiral and difunctional case catalyst, gave the trans-2, $8-D_2$ isotopomer. These isotopomer were investigated systematically in relation with cyclooctanone conformation and intrinsic isotope effects on $^{13}C$ NMR chemical shifts at low temperature. The determination of the intrinsic effects could help in the analysis of the more complex effects at higher temperature. For quantitative analysis of intrinsic isotope effects, the $^{13}C$ NMR spectrum has been obtained for a mixture of the labeled and unlabeled compounds because the signal separations are very small.

• Journal of Korean Society of Environmental Engineers
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• v.39 no.8
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• pp.462-469
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• 2017

Eutrophication and shortage of phosphate ore raise the necessity of phosphate removal and recovery from wastewater treatment plants. Especially, a sludge treatment system containing highly concentrated phosphate should be targeted for phosphate removal and recovery. This study thus aimed to evaluate the capability of the struvite crystallization process for phosphate removal and recovery from a sludge treatment system of a wastewater treatment plant. Analysis on phosphate concentrations and masses in the sludge treatment system revealed that digested sludge and centrate have phosphate concentrations and masses, high enough to adopt the struvite crystallization process. Chemical equilibrium modeling indicated that the struvite crystallization reaction substantially occurred with pH higher than 8 and $Mg^{2+}$ concentration 1.2 times higher than its theoretical requirement. A series of batch tests with digested sludge and centrate indicated that the phosphate removal reaction by struvite crystallization followed a first-order kinetics and reached over 80% removal efficiency at equilibrium. Aeration in the batch tests was found to purge $CO_2$ in sludge or centrate and increase pH up to 8.7, without adding NaOH. Thus, we concluded that the struvite crystallization process could be an efficient and economical process for phosphate removal and recovery from a wastewater treatment plant.

• Polymer(Korea)
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• v.28 no.2
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• pp.143-148
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• 2004

${\alpha}$,$\omega$-Hydrogen polyorganosiloxane(HPMDMS) prepolymer was prepared from equilibrium polymerization ofoctamethylcyclotetrasiloxane, 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethyl-cyclotetrasiloxane, and 1,1,3,3-tetramethyl disiloxane as an end-blocker in the presence of tetramethylammonium siloxanolate as a catalyst. Polyorganosiloxane modified with dimethylacrylamide(APMDMS) was prepared by hydrosilylation of HPMDMS with dimethylacrylamide in the presence of Pt catalyst, and followed by coordination of metal oxide (APMDMS-MO), such as NiO and FeO, to the amide moieties of the resulting polymer. The chemical structures of HPMDMS and APMDMS were confirmed by FT-IR and $^1$H-NMR analysis. Liquid silicone rubber containing metal oxide composite (LSRMO) was prepared by compounding APMDMS-MO, ${\alpha}$,$\omega$-vinylpolydimethylsiloxane, and a catalyst in a high speed dissolver. The thermal conductivity of LSRMO composite was determined to be 0.29 W/mK, and the volume resistivity exhibited a lower value than that of LSR composite. The mechanical and thermal properties of LSRMO and LSR composite were measured by UTM and TGA.

• Journal of the Korean Wood Science and Technology
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• v.40 no.1
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• pp.10-18
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• 2012

A high airtightness is required for the residential spaces constructed recently to save cooling and heating energy through improving insulation performance. Because the chances to release steam formed by human activity in building and inflow of water vapor in outdoor air to residential space are reduced, the natural humidity control performance of interior materials has become more important. In this study, hygroscopic performance of thermo-physically treated wood (Pinus koraiensis) was estimated. At various relative humidity condition, the water vapor adsorption and desorption rates of wooden materials were measured as well as equilibrium moisture content. Effects of roughness and surface microstructure as physical factors and functional groups as chemical factors on the hygroscopicity were analyzed. It is expected that the results from this study and further study of measuring moisture generation in residential spaces could contribute to install a system for evaluating the hygrothermal performance of wooden building.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.19 no.12
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• pp.592-599
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• 2018

The kinetics and thermodynamics of the adsorption of acid blue 40 from an aqueous solution by activated carbon were examined as a function of the activated carbon dose, pH, temperature, contact time, and initial concentration. The adsorption efficiency in a bathtub was increased at pH 3 and pH 11 due to the presence of sufonate ions ($SO_3{^-}$) and amine ions ($NH_2{^+}$). The equilibrium adsorption data were fitted to the Langmuir, Freundlich and Temkin isotherms. The results indicated that the Langmuir model provides the best correlation of the experimental data. The separation factor of the Langmuir and Freundlich model showed that the adsorption treatment of acid blue 40 by activated carbon could be an effective adsorption process. The adsorption energy determined by the Temkin equation showed that the adsorption step is a physical adsorption process. Kinetics analysis of the adsorption process of acid blue 40 on activated carbon showed that a pseudo second order kinetic model is more consistent than a pseudo second order kinetic model. The estimated activation energy was 42.308 kJ/mol. The enthalpy change (80.088 J/mol) indicated an endothermic process. The free energy change (-0.0553 ~ -5.5855 kJ/mol) showed that the spontaneity of the process increased with increasing adsorption temperature.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.5 no.1
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• pp.91-99
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• 2007

It was intended in this study to investigate the effects of various parameters on the chemical reaction or mass transfer yield in a tubular-type nuclear waste treatment equipment. Since such equipments, as a tubular reactor, multistage solvent extractor, and adsorption column, accompany chemical reaction or mass transfer along the fluid-flowing direction, mathematical modeling for each equipment was carried out first. Then their behaviors of the chemical reaction or mass transfer were predicted through computer simulations. The inherent major parameters for each equipment were chosen and their sensitivities. affecting the reaction or mass transfer yield were analyzed. For the tubular reactor, the effects of axial diffusion coefficient and reaction rate constant on the reaction yield were investigated. As for the multistage solvent extractor, the backmixing of continuous phase and the distribution coefficient between fluid and solvent were considered as the major parameters affecting the extraction yield as well as concentration profiles throughout the axial direction of the extractor. For the adsorption column, the equilibrium constant between fluid and adsorbent surface, and the overall mass transfer coefficient between the two phases were taken as the major factors that affect the adsorption rate.

• Journal of the Korean Chemical Society
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• v.56 no.5
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• pp.583-590
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• 2012

The HF (Hollow fiber) extraction method was optimized to analysis seven species of pesticides in aqueous sample and analyzing samples by GC/MS. Hollow fiber extraction showed good efficiency when it was conducted under these conditions: organic solvent was toluene and agitation speed was 1200 rpm. The 15% concentration of NaCl was optimized when it was experimented between 5% and 25%. The equilibrium time was determined at 15 minutes. The pH 5 showed the best effect on the extraction efficiency. The linearities of calibration curves of seven species were good with correlation of regression ($r^2$) over 0.995 when they were experimented over a concentration range of $5{\mu}g/L$ to $50{\mu}g/L$. The analytical data exhibited the detection of limits (LODs) range of $0.37{\mu}g/L$ to $1.23{\mu}g/L$ and the limit of quantification (LOQs) range of $1.19{\mu}g/L$ to $3.91{\mu}g/L$. The optimized HF-LPME extraction method provides a simple and effective preparation and requires small amount of organic solvents and samples compared to conventional pre-treatment methods.

• Applied Chemistry for Engineering
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• v.31 no.2
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• pp.179-186
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• 2020

In this study, chitosan/zeolite composites were prepared by using basalt-based zeolite impregnated with aqueous chitosan solution for the adsorptive separation of CO₂. The prepared composites were characterized by scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption analysis. In addition, the adsorption equilibrium isotherms for CO₂ and N₂ were measured at 298 K using a volumetric adsorption system, and the results were analyzed by applying adsorption isotherm equations (Langmuir, Freundlich, and Sips) and energy distribution function. It was found that CO₂ adsorption capacities were well correlated with the structural characteristics of chitosan and zeolite, and the ratio of elements [N/C, Al/(Si + Al)] formed on the surface of the composite. Moreover, the CO₂/N₂ adsorption selectivity was calculated under the mixture conditions of 15 V : 85 V, 50 V : 50 V, and 85 V : 15 V using the Langmuir equation and the ideal adsorption solution theory (IAST).

• Journal of the Korean Society for Aeronautical & Space Sciences
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• v.46 no.8
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• pp.652-661
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• 2018

It is necessary to resolve the absolute velocity as well as Mach number to reflect the high temperature effect in high speed flow. So this region is classified as high enthalpy flows distinguished from high speed flows. Many facilities, such as arc-jet, shock tunnel, etc. has been used to obtain the high enthalpy flows at the ground level. However, it is difficult to define the exact test condition in this type of facilities, because some chemical reactions and energy transfer take place during the experiments. In the present study, a quasi 1D code considering the thermochemical non-equilibrium effect is developed to effectively estimate the test condition of a shock tunnel. Results show that the code gives reasonable solution compared with the results from the known experiments and 2D axisymmetric simulations.

• Journal of Environmental Science International
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• v.20 no.2
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• pp.241-249
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• 2011

In this research, equilibrium of adsorption and kinetics of As(V) removal were investigated. The coal mine drainage sludge(CMDS) was used as adsorbent. To find out the physical and chemical properties of CMDS, XRD (X-ray diffraction), XRF (X-ray fluorescence spectrometer) analysis were carried out. The CMDS was consist of 70% of goethite and 30% of calcite. From the results, an adsorption mechanism of As(V) with CMDS was dominated by iron oxides. Langmuir adsorption isotherm model was fitted well more than Freundlich isotherm adsorption model. Adsorption capacities of CMDS 1 was not different with CMDS 2 on aspect of amounts of arsenic adsorbed. The maximum adsorption amount of two CMDS were respectively 40.816, 39.682 mg/g. However, the kinetic of two CMDS was different. The kinetic was followed pseudo second order model than pseudo first order model. Concentrations of arsenic in all segments of the polymer in CMDS 2 does not have a constant value, but the rate was greater than the value of CMDS 1. Therefore, CMDS 2, which is containing polymer, is more effective for adsorbent to remove As(V).