• 대한화학회지
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• 제43권1호
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• pp.85-91
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• 1999

Phenyl N,N-diethyl-P-benzylphonamidate 및 그 유도체들의 염기성 가수분해 반응속도 상수를 분광 광도법으로 측정하였다. 속도 상수로부터 열역학적 파라메타(Ea, ${\Delta}H^{\neq}$,${\Delta}S^{\neq}$)를 구하였고, 이탈기의 치환기 효과는 Hammett 식을 이용하여 얻었다. 이들 실험 자료에 의하면 가수분해 반응은 활성화 엔트로피가 양의 값이나 작은 음의 값을 갖고 카르보음이온 생성이 수반되는 해리반응 보다는 이중피라미드 중간체 또는 전이 상태를 경유하는 회합 메카니즘을 강력히 암시하고 있다. 반응속도론적 연구 결과에 의하면 치환 pheny N,N-diethyl-P-benzylphosphonamidates의 가수분해 반응은 회합성 메카니즘으로 진행됨을 알 수 있었다.

• 대한화학회지
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• 제20권6호
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• pp.479-485
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• 1976

방사성 브롬으로 표시한 브롬화 n-부틸을 사용하여 1,2,4-트리클로로벤젠용액 및 니트로 벤젠용액 내에서 브롬화칼륨과 n-브롬화부틸 사이에 일어나는 브롬교환 반응의 속도를 19,25 및 40$^{\circ}C$에서 측정하였다. 본 실험의 결과는 이 브롬 교환반응이 브롬화칼륨에 관하여 2차반응이고 n-브롬화부틸에 관하여 1차 반응임을 보여준다. $19^{\circ}C$에서의 반응속도상수 값이 1,2,4-트리클로로벤젠용액에서 $1.15{\times}10^{-4} l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$이고, 니트로벤젠용액에서 $4.21{\times}10-4 l2{\cdot}mole-2{\cdot}sec-1$임을 알았다. 그리고 반응속도상수와 온도와의 관계로부터 이 교환반응에 대한 활성화 에너지, 활성화 엔탈피 및 활성화 엔트로피 값을 계산하였다.

• 한국염색가공학회지
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• 제11권4호
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• pp.39-49
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• 1999

In order to study the properties of cochineal colors, uv-visible spectra of cochineal colors solution, dyeing properties on the wool in several dyeing conditions and thermodynamic parameters were investigated. UV-visible spectra of cochineal colors solution showed hypochromic effect with the lapse of irradiation time but bathochromic shift with decreasing acidity of solution and addition of metallic ions. The concentration of cochineal colors in wool fiber increased with the increase of dyeing temperature, time, and acidity of initial dyebath. The value of apparent diffusion coefficients and standard affinities of dyeing decreased with the increase of dyeing temperature. The standard heats of dyeing$(\Delta{H}^\circ)$ and variation of entropy$(\Delta{S}^\circ)$ increased with the increase of concentration of initial dyebath. The activation energy$(E_a)$ were calculated to be 1.399~2.595kcal/mol in condition of 6~1%(o.w.f) dyebath. Wool fabrics were dyed reddish blue by iron sulfate, copper sulfate, aluminum acetate and tannic acid, and red by tin chloride, respectively. Lightfastness of wool fabrics dyed by cochineal colors were increased by mordant treatment, especially copper sulfate and iron sulfate treatment.

• 한국안전학회지
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• 제6권3호
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• pp.12-20
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• 1991

The dielectric properties that effect to electric safety for unsaturated Pelvester resin were studied over the temperature range of 30-40［$^{\circ}C$］ and the frequency range of 110~3$\times$10$^{6}$ ［Hz］. According to the results of the study, it has been observed that two kinds of dielectric losses in electric safety were existed by the molecular movement of C-H and OH group. When the ,adio of hardener was 1.5［%］, the characteristics of specimens were excellent in view of the electrical materical. In the range of measuring frequency the dielectric constants and the dielectric losses were 3.5~5.5 and 10$^2$~10$^3$ respectly. The activation energy of loss spectrum in aspect of electric safety and the entropy appeared at the 30［$^{\circ}C$］ were 33.4［Kacl/mole］ and 54.9［cal/mole.deg］ respectly.

• 한국염색가공학회지
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• 제9권5호
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• pp.10-18
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• 1997

In order to study the properties of safflower yellow colors, thermodynamic parameters and dyeing properties on the silk in several dyeing conditions were investigated. The uv-visible spectra of safflower yellow colors in several solvents show hypsochromic shift with the polarity of solvent but bathochromic shift with increasing acidity of solution. The apparent diffusion coefficients and standard affinities of dyeing increased with the increase of dyeing temperature. The standard heat of dyeing(${\Delta}H^0$), entropy change(${\Delta}S^0$) and activation energy($E_{act}$) were calculated to be - 1.144kcal/mol, -7.498(5$0^{\circ}C$)~-3.804(9$0^{\circ}C$)cal/molㆍdeg and 0.123kcal/mol, respectively. The concentration of safflower yellow colors in the silk fiber increased with dyeing temperature, time, concentration of colors and acidity of initial dyebath. Silk fabrics were dyed bright yellow by pre-mordanting with tin chloride. Lightfastness of silk fabrics pre-mordanted by tin chloride was not excellent.

• 한국염색가공학회지
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• 제6권2호
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• pp.40-46
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• 1994

In order to study the properties of cochineal color, variation of uv, visible spectra by pH, dyeing properties on the silk in several dyeing conditions and thermodynamic parameter were investigated. Cochineal colors had an unusual to pH, especially had instability in alkali condition. An increase in the dyeing temperature and in time resulted in an increase in the dye content of silk fibers. Concentration of cochineal color in the silk fiber was related to pH and the maximum exhaustion of cochineal colors showed at about pH 3. The value of apparent diffusion coefficients and standard affinities of dyeing increased with the increase of dyeing temperature. The standard heats of dyeing(ΔH°), variation of entropy(ΔS°) and activation energy(E/sub act/) were caculated to be -1.72kcal/mo1, -3.77cal/mo1ㆍdeg and 1.26kcal/mo1, respectively. Silk fabrics were dyed bright red by tin chloride, reddish purple by copper sulfate, and bluish gray by iron sulfate, respectively. Lightfastness of silk fabrics mordanted by metal ion was weak.

• Corrosion Science and Technology
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• 제5권5호
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• pp.160-167
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• 2006

S-Acetyl Isothiourea Acetate (S-AITA) was synthesized in the laboratory and this influence on the inhibition of corrosion of mild steel in 1.11 N hydrochloric and 1.12 N sulphuric acids was investigated by weight loss and potentiostatic polarization techniques at 303K, 353K and 403K. These results were confirmed by the impedance technique. The inhibition efficiency increased with increase in concentration of inhibitor and decreased with rise in temperature from 303K to 403K. The maximum inhibition efficiency of S-AITA was found to be 99.95% (0.5% of S-AITA) at 303K in sulphuric acid. The adsorption of this compound on the mild steel surface from the acids has been found to obey Temkin's adsorption isotherm. The potentiostatic polarization results revealed that S-AITA was a mixed type inhibitor. Some thermodynamic parameters i.e., activation energy (Ea), free energy of adsorption (${\Delta}G_{ads}$), enthalpy of adsorption (${\Delta}H$) and entropy of adsorption (${\Delta}S$) were also calculated from weight loss data.

• Bulletin of the Korean Chemical Society
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• 제8권4호
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• pp.233-235
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• 1987

The kinetics of the 1,3-dipolar cycloaddition of p-substituted 3-phenylsydnones 1a-d with DMAD have been investigated. The reaction rates over a temperature range $100-140^{\circ}C$ were measured by UV spectrometry. The reactions found to be second-order overall, insensitive to the dielectric constants of the solvents, and characterized by a large entropy of activation. These findings are consistent with the rate-determining step involving the formation of cyclic transition state 1 and the reaction proposed to be concerted.

• Bulletin of the Korean Chemical Society
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• 제17권2호
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• pp.138-142
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• 1996

The transition metal carbonylate, PPN+(${\eta}^5-MeCp)Mn(CO)_2Cl^-$ undergoes a novel ligand substitution reaction with PR3 (R=Me, Et, OEt, $C_6H_5$ in THF at elevated temperatures (40 $^{\circ}C$ up to 60 $^{\circ}C)$ under the pseudo-first-order reaction conditions (usually 20-fold excess of PR3 with respect to metal carbonylate concentrations) where chloride is displaced by PR3. The reaction follows overall first order dependence on [(${\eta}^5-MeCp)Mn(CO)_2Cl^-$]; however, the negative entropy changes of activation (${\Delta}S^{\neq}$=-19.3 e.u. for $P(OEt)_3$; ${\Delta}S^{\neq}$=-16.4 e.u. for $PPh_3$) suggest the existence of the intermediate, ((η3-MeCp)Mn(CO)2(THF)Cl-, which eventually transforms to the product (${\eta}^5-MeCp)Mn(CO)_2(PR_3)$.

• 대한화학회지
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• 제27권3호
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• pp.201-207
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• 1983

테트라히드로퓨란-물 이성분계에서 용매화전자와 벤젠간의 반응속도 상수를 광분해법으로 측정하였으며, 이때 온도 범위는 $-18{\circ}C{\sim}+51{\circ}C$이였다. 속도 상수를 Arrhenius식에 따라 도시하여 얻은 활성화 에너지는 테트라히드로퓨란 함량이 증가할 수록 감소하였다. 물의 함량이 증가하면 이성분계의 점성도는 감소하고, 또 반응속도 상수도 감소하였으므로 용매화전자의 반응은 확산지배가 아니다. 활성화엔탈피 변화와 이차반응속도 상수는 테트라히드로퓨란의 함량이 39, 49, 75M%일 때 각각 4.90, 2.80 및 $-0.3kcal{\cdot}M^{-1}$과 $8.86{\times}10^8,\;5.14{\times}10^8$ 및 $1.43{\times}10^8M^{-1}sec^{-1}$이었다. 활성화반응 파엔탈피변화, 활성화엔트로피 변화에서 얻은 등속도 온도는 본 실험온도보다 낮은 $244{\circ}K$로 이것은 라메터가 활성화엔트로피 변화라는 것을 의미한다. 활성화 에너지에 대한 용매효과로부터 용매화전자$({e_s}^-)$와 벤젠(B)간의 반응과정 중에 ${e_s}^-+B{\rightleftharpoons}B^-$ 단계는 테트라히드로퓨란 함량이 증가할수록 더욱 더 발열반응성으로 진행되었다.