• Nuclear Engineering and Technology
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• v.13 no.3
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• pp.145-152
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• 1981

Even though a lately reported method of high temperature exchange labelling of o-iodo-hippuric acid (Hippuran) in the absence of oxidizing agent was considered to be an attractive one, the exchange mechanism was somewhat unclear. In this study iodine isotope exchanges between o-iodohippuric acid (OIH) and radioiodide ($^{125}$ $I^{ }$) or between OIH and molecular radioiodine ($^{125}$ $I_2$) were carried out at two different temperatures. Rate constants and activation parameters were measured by applying a radio-paper chromatography technique. Since o-iodobenzoic acid is known as a by-product in the exchange labelling of OIH, data were also obtained for the OIB-iodide systems for comparison. The rate constant was increased in the order of OIB...$^{125}$ $I^{[-10]}$ >OIB...$^{125}$ $I_2$>OIH..$^{125}$ $I^{[-10]}$ >OIH...$^{125}$ $I_2$ and the activation parameters for OIH were generally larger than those for OIB :$\Delta$H$\neq$$_{OIH}$>$\Delta$H$\neq$$_{OIB}$, $\Delta$S$\neq$$_{OIH}$>$\Delta$S$\neq$$_{OIB}$. These results suggest that the mechanism of the high temperature exchange is predominantly nucleophilic even though some electrophilic character can also be involved depending upon reaction conditions. Such a fact may well be caused by a feasible formation of hydrogen bonding type transition state due probably to the ortho substituent effect of-CONHC $H_2$COOH. Thus, the high temperature exchange method is estimated to be quite effective for labelling Hippuran especially at a small research center where reducing agent-free $^{131}$ I is unavailable.ailable..

• Korean Journal of Materials Research
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• v.9 no.3
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• pp.327-332
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• 1999

The recovery activation energy, the order of reaction and the recovery rate constant were detemined by isochronal and isothermal annealing treatment to investigate the recovery behaviors of neutron irradiated Mn-Mo-Ni low alloy steels$(fluence: 2.3\times10^{19}ncm^{-2}, 553K, E\geq1.0 MeV)$. Vickers microhardness tests were conducted to trace the recovery behavior after heat treatments. The results were analyzed in terms of recovery stages, behavior of responsible defects and recovery kinetics. It was shown that recovery occurred through two annealing stages(stage I : 703-753K, stage n : 813-873K) with re$\infty$very activation energies of 2.5 eV and 2.93 eV for each stage I and n, respectively. From the comparison of unirradiated and irradiated isochronal anneal curves, a radiation anneal hardening(RAH) peak was identified at around 813K. Most of recovery have occurred during about 120 min irrespective of isothermal annealing temperatures of 743K and 833K. Recovery rate constants were determined to be $3.4\times10^{-4}min^{-1} and 7.1\times10^{-4}min^{-1}$ for stage I and II, respectively. The order of reaction was about 2 for both recovery stages. Comparing the obtained data with those of previously reported results on neutron irradiated Mn- Mo- Ni steels, the thermal recovery be­havior of the present material seems to occur by the dissociation of point defect clusters formed during irradiation, and by the recombination process of self-interstitials and vacancies from dissociated vacancy clusters.

• Bulletin of the Korean Chemical Society
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• v.2 no.3
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• pp.96-104
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• 1981

(1) The flow data of f (stress) and ${\dot{s}$ (strain rate) for Fe and Ti alloys were plotted in the form of f vs. -ln ${\dot{s}$ by using the literature values. (2) The plot showed two distinct patterns A and B; Pattern A is a straight line with a negative slope, and Pattern B is a curve of concave upward. (3) According to Kim and Ree's generalized theory of plastic deformation, pattern A & B belong to Case 1 and 2, respectively; in Case 1, only one kind of flow units acts in the deformation, and in Case 2, two kinds flow units act, and stress is expressed by $f={X_1f_1}+{X_2f_2}$where $f_1\;and\;f_2$ are the stresses acting on the flow units of kind 1 and 2, respectively, and $X_1,\;X_2$ are the fractions of the surface area occupied by the two kinds of flow units; $f_j=(1/{\alpha}_j) sinh^{-1}\;{\beta}_j{{\dot{s}}\;(j=1\;or\;2)$, where $1/{\alpha}_j\;and\;{\beta}_j$ are proportional to the shear modulus and relaxation time, respectively. (4) We found that grain-boundary flow units only act in the deformation of Fe and Ti alloys whereas dislocation flow units do not show any appreciable contribution. (5) The deformations of Fe and Ti alloys belong generally to pattern A (Case 1) and B (Case 2), respectively. (6) By applying the equations, f=$(1/{\alpha}_{g1}) sinh^-1({\beta}_{g1}{\dot{s}}$) and $f=(X_{g1}/{\alpha}_{g1})sinh^{-1}({\beta}_{g1}{\dot{s}})+ (X_{g2}/{\alpha}_{g2})\;shih^{-1}({\beta}_{g2}{\dot{s}})$ to the flow data of Fe and Ti alloys, the parametric values of $x_{gj}/{\alpha}_{gj}\;and\;{\beta}_{gs}(j=1\;or\;2)$ were determined, here the subscript g signifies a grain-boundary flow unit. (7) From the values of ($({\beta}_gj)^{-1}$) at different temperatures, the activation enthalpy ${\Delta}H_{gj}^{\neq}$ of deformation due to flow unit gj was determined, ($({\beta}_gj)^{-1}$) being proportional to , the jumping frequency (the rate constant) of flow unit gj. The ${\Delta}H_{gj}\;^{\neq}$ agreed very well with ${\Delta}H_{gj}\;^{\neq}$ (self-diff) of the element j whose diffusion in the sample is a critical step for the deformation as proposed by Kim-Ree's theory (Refer to Tables 3 and 4). (8) The fact, ${\Delta}H_{gj}\;^{\neq}={\Delta}H_{j}\;^{\neq}$ (self-diff), justifies the Kim-Ree theory and their method for determining activation enthalpies for deformation. (9) A linear relation between ${\beta}^{-1}$ and carbon content [C] in hot-rolled steel was observed, i.e., In ${\beta}^{-1}$ = -50.2 [C] - 40.3. This equation explains very well the experimental facts observed with regard to the deformation of hot-rolled steel..

• Journal of the Korean Chemical Society
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• v.32 no.5
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• pp.476-482
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• 1988

Kinetic studies and theoretical investigations were made to illustrate the mechanism of the aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3$, NO$_2^-$, NCS$^-$, $H_2O$) in $Hg^{2+}$ aqueous solution UV/vis-spectrophotometrically. The aquation of cis-[Co(en)$_2$YCl]$^{r+}$ have been found to be the second order for overall reaction as first order for each of substrate and Hg$^{2+}$+ catalyst. The reaction rate was increased in the order of Y=NH$_3$ < NCS$^-$- < $H_2O$ < $NO_2^-$, which are neighboring group of Cl. The step of bond formation was found to be the rate determining one, because the net charge of central metal ion run parallel with the observed rate constant. On the basis of rate determining step, kinetic data and the observed activation parameters, we have proposed the Id mechanism for the reaction system. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation.

• Korean Journal of Food Science and Technology
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• v.22 no.7
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• pp.799-801
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• 1990

Of the several methods proposed for decreasing toxicity of Paralytic shellfish poison(PSP) from intoxicated shellfish, heat treatment has been most popular, although a large percentage of the incidents of PSP illness have been related to the ingestion of cooked shellfish. The purpose of this study was to determine the kinetics of PSP destruction at various temperatures. The homogenate of intoxicated blue mussel(Mytilus edulis) was heated at temperature ranging from $90\;to\;121^{\circ}C$ and toxicities measured in samples heated for various time intervals. The rate constant(k) per second was $3{\times}10^{-4},\;at\;90^{\circ}C,\;4.98{\times}10^{-4},\;at\;100^{\circ}C,\;7.38{\times}10^{-4},\;at\;116^{\circ}C,\;and\;8.38{\times}10^{-4},\;at\;121^{\circ}C,\;$. By the Arrhenius equation, the decimal reduction time(D-value) was $121min.\;at\;90^{\circ}C,\;82min,\;at\;100^{\circ}C,\;58min.\;at\;116^{\circ}C\;and\;53min.\;at\;121^{\circ}C$. The z-value, activation energy($E_a\;and\;Q_{10}$) was $72^{\circ}C,\;3.9{\times}10^7(J/kg\;mol)$ and 1.39, respectively.

• Elastomers and Composites
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• v.21 no.1
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• pp.13-19
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• 1986

The effects of several vulcanizing accelerators on the determination of kinetic parameters of natural rubber vulcanizate was studied by DSC. Kinetic parameters were determined by means of the calculation procedures of Borchardt-Daniels and Oscillating Disk Rheometer (ODR) cure curve analysis, using both DSC exothermal thermogram and ODR cure curve. In order to examine the credibility in the DSC method the same compound which was und for DSC method was used for the comparison with the results of ODR data. Upon this method, kinetic rate constant (k), and Arrehenius parameter (Ea, ko, n) have been determined for rubber compounds via a new method using DSC thermogram and ODR cure curve. In the comparison of DSC and ODR results, kinetic parameters has shown good agreements between two results. Consequently, from the present studies, it is shown that the DSC thermoanalytical method can provide an alternate new method of kinetic study of rubber vulcanization.

• Journal of Radiation Protection and Research
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• v.26 no.1
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• pp.7-12
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• 2001

Sintered LiF:Mg,Cu,Na,Si thermoluminescence (TL) pellets were developed for application in radiation dosimetry. In the present study, the TL dosimetric properties of LiF:Mg,Cu,Na,Si TL pellets have been investigated for emission spectrum, dose response, energy response, and fading characteristics. LiF:Mg,Cu,Na,Si TL pellets were made by using a sintering process, that is, pressing and heat treatment from TL powders. Photon irradiations for the experiments were carried out using X-ray beams and a $^{137}Cs$ gamma source at the Korea Atomic Energy Research Institute (KAERI). The average energies and the dose were in the range of 20-662 keV and $10^{-6}-10^{-2}\;Gy$, respectively. The glow curves were measured with a manual type TLD reader(System 310, Teledyne) at a constant nitrogen flux and a linear heating rate. For a constant heating rate of $5^{\circ}C\;s^{-1}$, the main dosimetric peak of glow curve appeared at $234^{\circ}C$, the activation energy was 2.34 eV and frequency factor was $1.00{\times}10^{23}$. TL emission spectrum is appeared at the blue region centered at 410 nm. A linearity of photon dose response was maintained up to 100 Gy. The photon energy responses relative to $^{137}Cs$ response were within ${\pm}20%$ at overall photon energy region. The fading of TL sensitivity of the pellets stored at the room temperature was not found for one year.

• Clean Technology
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• v.25 no.3
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• pp.198-205
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• 2019

The adsorption equilibrium, kinetic, and thermodynamic parameters of brilliant green adsorbed by coconut based granular activated carbon were determined from various initial concentrations ($300{\sim}500mg\;L^{-1}$), contact time (1 ~ 12 h), and adsorption temperature (303 ~ 323 K) through batch experiments. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin, Harkins-Jura, and Elovich isotherm models. The estimated Langmuir dimensionless separation factor ($R_L=0.018{\sim}0.040$) and Freundlich constant ($n^{-1}=0.176{\sim}0.206$) show that adsorption of brilliant green by activated carbon is an effective treatment process. Adsorption heat constants ($B=12.43{\sim}17.15J\;mol^{-1}$) estimated by the Temkin equation corresponded to physical adsorption. The isothermal parameter ($A_{HJ}$) by the Harkins-Jura equation showed that the heterogeneous pore distribution increased with increasing temperature. The maximum adsorption capacity by the Elovich equation was found to be much smaller than the experimental value. The adsorption process was best described by the pseudo second order model, and intraparticle diffusion was a rate limiting step in the adsorption process. The intraparticle diffusion rate constant increased because the dye activity increased with increases in the initial concentration. Also, as the initial concentration increased, the influence of the boundary layer also increased. Negative Gibbs free energy ($-10.3{\sim}-11.4kJ\;mol^{-1}$), positive enthalpy change ($18.63kJ\;mol^{-1}$), and activation energy ($26.28kJ\;mol^{-1}$) indicate respectively that the adsorption process is spontaneous, endothermic, and physical adsorption.

• Journal of the Korean Chemical Society
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• v.23 no.5
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• pp.329-337
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• 1979

The water-vapour transmission ratios (WVTR) of the various commercial polymer films have been investigated at the constant pressure and relative humidity (RH). Water proofnesses, the reciprocals of WVTR for the various samples, were determined using a cup device and maintaining the sample films at a constant temperature ($40{\pm}1^{\circ}C$) and a constant R. H ($90{\pm}2%$) for 24 hours. The following order of the relative proofness was observed; oriented polypropyrene (O.PP) > high density polyethylene (HDPE, Inflation) > high density polyethylene (HDPE. T-die) > casted polypropylene (C. PP) > nonoriented polyester (N. PET) > low density polyethylene (LDPE) > oriented polyester (O. PET) > rigid polyvinyl chloride (Rigid PVC) > semirigid polyvinyl chloride (Semirigid PVC) > nonrigid polyvinyl chloride (Nonrigid PVC) > oriented nylon (O. Nylon) > nonoriented nylon (N. Nylon). And water proofness order was also observed to decrease with the temperature rising; HDPE (T-die) > C. PP > O. PET > LDPE > O. Nylon. The activation energies of LDPE, HDPE (T-die), C. PP, O. PET and O.Nylon films were 12.0, 11.1, 11.4, 11.7, 14.1 kcal/mole, respectively. The WVTR's of the films were increased with the polarity of polymer and the addition of plasticizer in PVC, decreased with the increase of the film thickness and mechanical orientation. The WVTR's of the laminated films O. PP/LDPE, N.Nylon/LDPE, C.PP/LDPE were also more dependent on the film thickness than the WVTR's of the single films.

• Applied Chemistry for Engineering
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• v.5 no.5
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• pp.764-771
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• 1994

Electrochemical synthesis of conductive polypyrrole films was carried out in nucleophilic solvent containing p-toluenesulfonic acid or bezensulfonic acid as supporting electrolyte and dopant. Also characteristics of degradation and improvement of mechanical properties were studied. The conductivity, tensile strength and elongation of the films obtained in dimethyformamide/p-toluenesulfonic acid had the highest value of 10-40S/cm, $25N/mm^2$ and 10%, respectively. The optimum condition of electrochemical synthesis was $2mA/cm^2$ for constant current method and 0.9V for constant potential method containing 0.5M pyrrole and 0.5M p-TSA. The obtained films showed good stability in air and electrode characteristics of secondary battery by reversibility in doping and undoping. The degradation process was 1st order reaction at various temeprature. The activation energy and rate constant of degradation reaction were $1.01JK^{-1}mol^{-1}$ and $3.1{\times}10^{-7}min^{-1}$ respectively at $25^{\circ}C$. For the improvement of mechanical properties, composition of polypyrrole films with various host polymer were investigated and increase of tensile strength and elongation was confirmed.