• Bulletin of the Korean Chemical Society
• /
• 제16권6호
• /
• pp.498-503
• /
• 1995

The adsorption behaviors of two major components purified, endo Ⅱ and exo Ⅱ, from Trichoderma viride were investigated using microcrystalline cellulose with different specific surface area as substrates. Adsorption was found to apparently obey the Langmuir isotherm and the thermodynamic parameters, ΔH, ΔS, and ΔG, were calculated from adsorption equilibrium constant,K. The adsorption process was found to be endothermic and an adsorption entropy-controlled reaction. The amount of adsorption of cellulase components increased with specific surface area and decreased with temperature and varied with a change in composition of the cellulase components. The maximum synergistic degradation occurred at the specific weight ratio of the cellulase components at which the maximum affinity of cellulase components obtains. The adsorption entropy and enthalpy for respective enzyme system increased with specific surface area increase. The adsorption entropy was shown to have a larger value with enzyme mixture.

• 한국식품과학회지
• /
• 제9권2호
• /
• pp.165-169
• /
• 1977

용액의 열처리 온도까지의 온도 상승시간과 열처리 후 냉각시간이 무시될 수 있을 정도로 단시간이어서 고온에서의 측정이 가능한 연속 살균장치를 이용하여 열처리온도 $110^{\circ}C$와 $140^{\circ}C$범위 내에서 horseradish peroxidase의 열에 의한 불활성화 속도와 열역학적 자료를 측정 수집하였다. 그 결과 peroxidase의 열에 의한 불활성화 enthalpy, 146.4kJ/mol, free enegy of activation 113 kJ/mol, entropy of activation 82.9 J/mol.k를 얻었다. 본 실험에서 얻은 자료를 기초로하여 일반 미생물 살균 그래프와 비교하고 고온 단시간 살균공정(HTST)에서 효소의 불활성화에 충분한 열처리 시간을 고려해야함을 토론하였다.

• Bulletin of the Korean Chemical Society
• /
• 제32권12호
• /
• pp.4347-4351
• /
• 2011

The nucleophilic substitution reactions of ethylene phosphorochloridate (2) with X-pyridines are investigated kinetically in acetonitrile at $-20.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. Unusual positive ${\rho}_X$ (= +2.49) and negative ${\beta}_X$ (= -0.41) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_{ISOKINETIC}=6.6^{\circ}C$. The pyridinolysis rate of 2 with a cyclic five-membered ring is forty thousand times faster than its acyclic counterpart (3: diethyl chlorophosphate) because of great positive value of the entropy of activation of 2 (${\Delta}S^{\neq}$ = +49.2 eu) compared to negative value of 3 (${\Delta}S^{\neq}$ = -44.1 eu) over considerably unfavorable enthalpy of activation of 2 (${\Delta}H^{\neq}=28.4\;kcal\;mol^{-1}$) compared to 3 (${\Delta}H^{\neq}=6.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed.

• 한국환경과학회지
• /
• 제21권5호
• /
• pp.623-631
• /
• 2012

The adsorption behavior of Eosin Y on activated carbon (AC) in batch system was investigated. The adsorption isotherm could be well fitted by the Langmuir adsorption equation. The kinetics of adsorption followed the pseudo-second-order model. The temperature variation was used to evaluate the values of free energy (${\Delta}G^{\circ}$), enthalpy (${\Delta}H^{\circ}$) and entropy (${\Delta}S^{\circ}$). The positive value of enthalpy change ${\Delta}H^{\circ}$ for the process confirms the endothermic nature of the process and more favourable at higher temperature, the positive entropy of adsorption ${\Delta}S^{\circ}$ reflects the affinity of the AC material toward Eosin Y and the negative free energy values ${\Delta}G^{\circ}$ indicate that the adsorption process is spontaneous. With the increase of the amount of AC, removal efficiency of Eosin Y was increased, but adsorption capacity was decreased. And adsorption capacity was increased with the decrease of particle size. With the increase of the amount of AC, removal efficiency of Eosin Y was increased, but adsorption capacity was decreased. And adsorption capacity was increased with the decrease of particle size.

• Bulletin of the Korean Chemical Society
• /
• 제33권1호
• /
• pp.270-274
• /
• 2012

The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1c) with X-pyridines are investigated kinetically in acetonitrile at $-25.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 1c with a cyclic five-membered ring is $2.70{\times}10^5$ times faster than its acyclic counterpart (1a: phenyl ethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}$ = +26 eu) compared to negative value of 1a (${\Delta}S^{\neq}$= -24 eu) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=20.5kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=12.7kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed on the basis of greater selectivity parameters (${\rho}_X$ = -1.99 and ${\beta}_X$ = 0.41) with the strongly basic pyridines compared to those (${\rho}_X$ = -0.42 and ${\beta}_X$ = 0.07) with the weakly basic pyridines.

• Bulletin of the Korean Chemical Society
• /
• 제33권3호
• /
• pp.1037-1041
• /
• 2012

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (${\Delta}S^\neq=-2cal\;mol^{-1}\;K^{-1}$) over considerably unfavorable enthalpy of activation (${\Delta}H^\neq=18.0\;kcal\;mol^{-1}$). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted $S_N2$ mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, $k_H/k_D$ < 1.

• 대한화학회지
• /
• 제37권1호
• /
• pp.105-111
• /
• 1993

수용액내에서 란탄족 금속(III)이온과 광학 활성을 지닌 L-proline간의 안정도 상수(1:1)값들을 pH 적정 방법을 사용하여 이온강도 0.1M $NaClO_4$, 25$^{\circ}C$ 조건에서 구하였다. 안정도 상수값은 경란탄족과 중란탄족 금속 사이에 "gadolinium break" 현상을 나타내었으며, 리간드 산도와 안정도 상수값의 관계로 부터 L-proline이 두자리 리간드로 작용함을 알 수 있었다. 열역학적 함수값(${\Delta}H$, ${\Delta}S$)들을 같은 조건에서 엔탈피 적정 방법으로 구하였다. lanthanide(III)-L-proline 착물 형성은 흡열 반응 및 큰 엔트로피 변화량(${\Delta}S$)을 나타내었으며 엔트로피 변화량은 L-proline 고리의 견고성으로 인해 과량의 탈수 효과에 의한 것으로 판단되었다. lanthanide(III)-anthranilate 착물 형성의 열역학적 함수값과 비교하여 본 결과, L-proline의 헤테로 고리 질소 원자와 카르복실기가 결합에 참여하여 킬레이트를 형성하였으며, anthranilate와 L-proline착물의 엔탈피 변화량(${\Delta}H$) 차이는 두 리간드 내에 존재하는 질소 원자의 염기도 차이에 의한 것으로 판단되었다.

• 한국수산과학회지
• /
• 제24권5호
• /
• pp.340-344
• /
• 1991

각종 어육의 동결 및 가열과정 중의 이화학적 품질변화의 규명하고 저온저장 및 가열조건의 확립과 장치의 설계를 위하여 필요로하는 열물성과 변성온도를 DSC를 이용 측정함으로서 다음의 결과를 얻었다. 1. 어육의 발열반응개시온도는 냉각속도가 증가할수록 강하하였으며, 활성화에너지, 엔탈피 및 엔트로피는 냉각속도의 증가와는 상반되는 경향을 보였다. 동결잠열은 냉각속도에 관계없이 거의 -정한 값을 나타내었다. 2. 어육의 동결과정 중의 자유에너지의 변화는 냉각속도와 조성성분의 영향보다는 온도에 의한 영향이 큰 것으로 나타났다. 3. 어육속의 지질 및 단백질의 변성온도는 가열속도와 상관관계를 나타내었으며, 지질의 함양이 많을수록 변성온도가 낮게 나타났다. 변성엔탈피는 각각 0.04-0.13, 0.07-0.17cal/g 값을 얻었다.

• Bulletin of the Korean Chemical Society
• /
• 제34권3호
• /
• pp.810-814
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• 제20권3호
• /
• pp.345-351
• /
• 1999

The structures, the energetics, and the spectra of K+(H2O)3 have been studied at HF and MP2 levels with the basis set of triple-zeta plus two sets of polarization functions (TZ2P) for water molecules. Two structures considered are 3+0 (D3), and 2+1 (C2v). The 2+1 (C2v) has two hydrogen bonds between the primary hydration and the secondary hydration shell water molecules. They have similar binding energy and enthalpy. The most stable conformation of K+(H2O)3 is entropy driven as shown in Na+(H2O)5 and in Na+(H2O)6 cases. The 3+0 (D3) conformation is the most stable at 298 K and at 1 atm, based on Gibbs free energy changes (ΔGr). The thermal contributions to the enthalpy and the Gibbs free energy are corrected for the low frequency modes. The corrected ΔGr is in good agreement with the experimental value. Vibrational frequencies of two conformations are revealed as their characteristics.