• Macromolecular Research
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• 제14권2호
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• pp.132-139
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• 2006

The dispersion of organoclay in ethylene propylene diene terpolymer (EPDM) matrix was correlated with the rheological and swelling properties of nanocomposites. X-ray diffraction pattern (XRD) and transmission electron microscopic (TEM) analysis exhibited the disordered-intercalated structure of EPDM/organoclay nanocomposite. The extent of the disordered phase increased with increasing organoclay content up to a limiting value of 3 wt% after which equilibrium tended towards intercalation. The dispersion effect of organoclay in EPDM matrix was clarified by the physicochemical properties like rheological response and swelling thermodynamics in toluene. The increase in viscoelastic properties of EPDM nanocomposite with increasing organoclay content up to 3 wt%, followed by a subsequent decrease up to 4 wt%, was correlated in terms of the disordered and ordered states of the dispersed nano-clay sheets. Swelling measurements revealed that the change in entropy of the swelling increased with the increase in disorder level but decreased with the increase in intercalation level of organoclay in the disordered-intercalated nanocomposite. The increase in solvent uptake was comparable with the free volume in EPDM matrix upon inclusion of silicate particles, whereas the inhibition in solvent uptake for higher organoclay loading was described by bridging flocculation.

• Bulletin of the Korean Chemical Society
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• 제26권4호
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• pp.614-618
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• 2005

The complex of the composition LaL(N$O_3)_3\;(H_2O)_2$ is prepared by the reaction of La($NO_3)_3{\cdot}6H_2O$ with Nethylmorpholine in aqueous medium. The ligand is involved in the complex as a neutral species where the chelation occurs via the oxygen of the ligand moiety and the nitrate groups as bidentate ligand. The chemical structure of the studied complex is confirmed through IR, XRD, and thermal analysis data. The complexation equilibria of La(III) with N-ethylmopholine is studied in aqueous medium at ionic strength I = 0.1 mol${\cdot}dm^{-3}\;KNO_3$ and at 25, 35 and 45 ${^{\circ}C}$, respectively. The thermodynamic parameters $\Delta$G, $\Delta$H and $\Delta$S values were calculated to prove the association with the complex formation. It is clearly observed that the process is accompanied by absorption of heat, i.e. endothermic process, while the entropy does not change greatly attributed to the release of constant number of water molecules during chelate formation.

• Bulletin of the Korean Chemical Society
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• 제32권9호
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• pp.3355-3360
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• 2011

The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $-15.0^{\circ}C$. The studied substrate of 1,2-phenylene phosphorochloridate is cyclic five-membered ring of phosphorus ester, and the anilinolysis rate of 1 is much faster than its acyclic analogue (4: ethyl phenyl chlorophosphate) because of extremely small magnitude of the entropy of activation of 1 compared to 4. The Hammett and Bronsted plots exhibit biphasic concave upwards for substituent X variations in the nucleophiles with a break point at X = 3-Me. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) change from secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines to primary normal ($k_H/k_D$ > 1) with the weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the transition state (TS) variation from a predominant backside attack to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. The primary normal DKIEs are substantiated by a hydrogen bonded, four-center-type TS.

• Journal of the Korean Chemical Society
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• 제32권6호
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• pp.513-519
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• 1988

The effect of pressure and temperature on the stabilities of hexamethylbenzene-1,3,5-trinitrobenzene charge transfer complex in carbon tetrachloride has been investigated by spectrophotometric measurements. The absorption spectra of charge transfer complexes were measured at 25, 40, $50^{\circ}C$ under 1, 200, 500, 1000, 1400 bar in this experiments. The equilibrium constants of the complex were increased with pressure and decreased with temperature rising. The absorption coefficients were increased with pressure and temperature. Change of volume, enthalpy, free energy and entropy for the formation of complexes were calculated from the equilibrium constants. The red-shift observed at a higher pressure, the blue-shift at a higher temperature and the relation between pressure and oscillator strength were discussed by means of thermodynamic fuctions.

• Korean Journal of Air-Conditioning and Refrigeration Engineering
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• 제3권4호
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• pp.241-249
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• 1991

A quasi-three dimensional calculation method is presented on the basis of Wu's idea using finite element methods. In B-B flow the governing equations are cast into a single equation to overcome the restriction of the type of turbomachinery, and Kutta condition is exactly assured by introducing a combination of two kinds of stream functions. In H-S flow a dissipative force which is assumed to be opposed to the relative velocity is added to the governing equation for a consistent loss model. The entropy change along each streamline is then calculated by assuming that the dissipative force may be a force coming from laminar viscous stresses with inviscid velocity distributions. Both the flow solvers are combined to build a three-dimensional flow field through a few iterations. For an effect of the distortion of H-S flow surface the body forces are computed after each B-B flow calculation is finished. Mizuki's centrifugal impellers are tested numerically. The reliability of the numerical solution compared with experimental data is guaranteed.

• Journal of Magnetics
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• 제10권4호
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• pp.142-144
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• 2005

The Magnetization behaviour has been measured for amorphous $Fe_{80-x}Mn_xZr_{10}$ (x = 4,6,8,10) alloys. The Curie temperature decreased from 236 K to 195 K with increasing Mn concentration (x = 4 to x = 10). The magnetization measurements were conducted at temperatures above the Curie temperature in the paramagnetic region. In all samples, the magnetic properties showed superparamagnetic behavior above $T_c$ where the mean magnetic moment of the superparamagnetic spin clusters decreased with increasing temperature. A large magnetic entropy change, ${\Delta}S_M$, which is calculated from H vs M curves associated with the ferromagnetic-paramagnetic transitions in amorphous, has been observed. With Mn concentration increasing, ${\Delta}S_M$ decreases 1.04, 0.95, 0.87 J/kg K at 222, 210, 195 K (the Curie temperature), respectively.

• Macromolecular Research
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• 제16권6호
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• pp.539-543
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• 2008

Many natural proteins self-assemble in complex ways, either to fulfill their biological function or introduce particular properties, such as high strength and toughness. We report the morphological transition in water from a spherical to rod-like shape of Bombyx mori silk fibroin by reducing the pH. Transmission electron microscopy, scanning electron microscopy, and dynamic light scattering were used to characterize the dilute solutions of silk fibroin in an aqueous environment, and provide direct visualization of the transformation of spherical micelles at pH 6.8 to nanofibrils at pH 4.8. This change in morphology occurred as a result of the stretching entropy due to the formation of $\beta$-sheets, which was analyzed using circular dichroism spectroscopy. This study demonstrates the self-assembly of silk fibroin as a function of pH.

• Bulletin of the Korean Chemical Society
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• 제4권3호
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• pp.115-119
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• 1983

The ionic association constants (K) of 2, N-dimethyl pyridinium iodide (2NDMPI) in 95 volume percentage ethanol-water mixture were determined by a modified UV and conductance method at $20^{\circ}C{\sim}50^{\circ}C$ under 1 to 2000 bars. The K values increase with increasing pressure and decrease with temperature. The total partial molar volume change (${\Delta}V$) has relatively small negative value and the absolute ${\Delta}V$ value decrease with increasing pressure and temperature. The ion size (a) and solvation number (n) of 2NDMPI were about 5 $\AA$ and changed from 1 to 3 with decreasing temperature. Other thermodynamic parameters such as enthalpy (${\Delta}H^{\circ}$) and entropy (${\Delta}S^{\circ}$) for the equilibrium of the 2NDMPI were evaluated. From all the parameters mentioned above, we came to conclusion that the electrostriction effect of 2NDMPI in the ethanol-water mixture is enhanced with increasing pressure and decreasing temperature.

• Bulletin of the Korean Chemical Society
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• 제14권4호
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• pp.515-519
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• 1993

The retention behavior of proteins was investigated by using hydrophobic interaction chromatography (HIC), comparing to the results obtained in reversed-phase chromatography (RPC) described in the previous paper. A SynChropak propyl column was employed with 0.05 M phosphate buffer (pH 7.0) containing sodium sulfate. Conformational changes were recognized by examining Z values as a function of sodium sulfate concentration over a range of temperature between 5 and 65$^{\circ}C$. Z values did not change significantly at the range of the temperature showing the consistent ${\Delta}H^{\circ}$ and ${\Delta}S^{\circ}$ values. The sign and the magnitude of ${\Delta}H^{\circ}$ and ${\Delta}S^{\circ}$ of proteins in HIC were compared with those obtained in RPC. The signs of ${\Delta}H^{\circ}$ and ${\Delta}S^{\circ}$ of proteins in HIC were all positive, while those of proteins in RPC were all negative. These results suggested that the retention of proteins in HIC and in RPC were entropy-driven and enthalpy-driven process, respectively. From the two different investigations, it was concluded that the retention mechanism of RPC and HIC was based on the same fundamental principle in which separation is dependent on hydrophobicity, but the retention behavior of the proteins in HIC is clearly different from that observed in RPC.

• Journal of the Korean Magnetics Society
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• 제5권5호
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• pp.753-757
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• 1995

Systematic studies on the crystal structure and magnetic properties of light rare earth element(RE) compounds with Pb, $REPb_{2}$, have been carried out. Their crystal structure has been identified to be a $MoSi_{2}$-type. The values of the effective magnetic moment for $CePb_{2},\;PrPb_{2}\;and\;NdPb_{2}$ are respectively very close to the theoretical values of $RE^{3+}$. These three compounds are antiferromagnetic and exhibit a metamagnetic transition. The magnitude of the Neel temperature is proportional to two-thirds of the de Gennes factor. The magnetic entropy change for $NdPb_{2}$ is contrast to the value for $CePb_{2}$ heavy-fermion compound, comparable to the theoretical value. The magnetic contribution to the temperature dependence of resistivity for $PrPb_{2}$ is given by a form of -lnT in a wide temperature range, implying the Kondo system in analogy with $Cepb_{2}$.