• Bulletin of the Korean Chemical Society
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• 제30권2호
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• pp.383-388
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• 2009

Rates of solvolyses of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone and 2,2,2-trifluoroethanol (TFE) are reported. For four representative solvents, studies were made at several temperatures and activation parameters were determined. The 30 solvents gave a reasonably precise extended Grunwald-Winstein plot, correlation coefficient (R) of 0.989. The sensitivity values (l = 1.29 and m = 0.64) of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) were similar to those obtained for diphenyl phosphorochloridate ($(PhO)_2$POCl, 2), diphenylphosphinyl chloride ($Ph_2$POCl, 3) and diphenylthiophosphinyl chloride ($Ph_2$PSCl, 4). As with the previously studied of 3~4 solvolyses, an $S_N$ pathway is proposed for the solvolyses of diphenyl thiophosphorochloridate (1). The activation parameters, ${\Delta}H^{\neq}\;(=11.6{\sim}13.9\;kcal{\cdot}mol^{-1})\;and\;{\Delta}S^{\neq}\; (=\;-32.1\;{\sim}\;-42.7\;cal{\cdot}mol^{-1}{\cdot}K^{-1})$, were determined, and they were in line with values expected for an $S_N$2 reaction. The large kinetic solvent isotope effects (KSIE, 2.44 in MeOH/MeOD and 3.46 in $H_2O/D_2$O) are also well explained by the proposed $S_N$2 mechanism.

• 한국군사과학기술학회지
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• 제14권3호
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• pp.364-371
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• 2011

This paper presents experimental results and derived experimental equations to investigate the turbulent wake characteristics generated by the self-propelled SUBOFF submarine model. A self-propelled SUBOFF model which was assumed as an axial-symmetric body was used to create wake, and a thin strut was mounted on the topside of the model. The experiments were conducted in a circulating water channel(CWC), and the hot-film was used to measure the turbulence in wake cross-section at the distance range of 0.0~2.0L from the model. The hot film anemometer measured turbulent velocity fluctuations, and the time-averaged mean velocity and turbulent intensity are obtained from the acquired time-series data. Measured results show well the general characteristics of turbulent intensity, kinetic energy and mean velocity distribution. Also, this paper presents derived experimental equations, which is extended result to the reference [1]. These experimental equations show well the general characteristics of the turbulent wake behind the self-propelled submerged body.

• 대한기계학회논문집B
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• 제22권2호
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• pp.221-228
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• 1998

In order to look into the comparative flow characteristics between a circular contraction duct and a circular expansion duct the both centerline turbulent structures have been investigated by the hot wire anemometry. Both of the contraction and the expansion have Morel type contours. Means, turbulences, and triple moments have been measured for the turbulent kinetic energy budgets along their centerlines. It is resulted that mean velocities of both have much deviated from theoretical values calculated by one-dimensional continuity considerations, and that for the same upstream condition, the expansion maintains the isotropy in general while the contraction maintains a severe anisotropy through the whole duct. The mean transport of the TKE along the expansion is willing to balance mostly with the dissipation in the TKE budgets while that along the contraction is balanced with the production in the turbulent kinetic energy equation.

• Bulletin of the Korean Chemical Society
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• 제34권2호
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• pp.615-621
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• 2013

Solvolyses of isobutyl chloroformate (4) in 43 binary solvent mixtures including highly aqueous media, water, $D_2O$, $CH_3OD$, 2,2,2-trifluoroethanol (TFE) as well as aqueous 1,1,1,3,3,3-hexafluoro-isopropanol (HFIP) solvents were performed at $45^{\circ}C$, in order to further investigate the recent results of D'Souza, M. $J^1$. et al.; solvolyses of 4 are found to be consistent with the proposed mechanism ($Ad_E$). The variety of solvent systems was extended to comprise highly ionizing power solvent media ($Y_{Cl}$ > 2.7 excepted for aqueous fluorinated solvents and pure TFE solvent) to investigate whether a mechanistic change occurs as solvent compositions are varied. However, in case of 18-solvent ranges having aqueous fluorinated solvent systems (TFE-$H_2O$ and HFIP-$H_2O$) and/or having $Y_{Cl}$ > 2.7 solvent systems, the solvent effect on reactivity for those of 4 are evaluated by the multiple regression analysis as competition with $S_N2$ - type mechanism. And in pure TFE and 97 w/w % HFIP solvents with high $Y_{Cl}$ and weak $N_T$, these solvolyses are understood as reactions which proceed through an ionization ($S_N1$) pathway.

• Carbon letters
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• 제8권3호
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• pp.199-206
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• 2007

The activated carbon produced from rubber wood sawdust by chemical activation using phosphoric acid have been utilized as an adsorbent for the removal of Cu(II) from aqueous solution in the concentration range 5-40 mg/l. Adsorption experiments were carried out in a batch process and various experimental parameters such as effect of contact time, initial copper ion concentration, carbon dosage, and pH on percentage removal have been studied. Adsorption results obtained for activated carbon from rubber wood sawdust were compared with the results of commercial activated carbon (CAC). The adsorption on activated carbon samples increased with contact time and attained maximum value at 3 h for CAC and 4 h for PAC. The adsorption results show that the copper uptake increased with increasing pH, the optimum efficiency being attained at pH 6. The precipitation of copper hydroxide occurred when pH of the adsorbate solution was greater than 6. The equilibrium data were fitted using Langmuir and Freundlich adsorption isotherm equation. The kinetics of sorption of the copper ion has been analyzed by two kinetic models, namely, the pseudo first order and pseudo second order kinetic model. The adsorption constants and rate constants for the models have been determined. The process follows pseudo second order kinetics and the results indicated that the Langmuir model gave a better fit to the experimental data than the Freundlich model. It was concluded that activated carbon produced using phosphoric acid has higher adsorption capacity when compared to CAC.

• 공업화학
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• 제30권5호
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• pp.562-568
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• 2019

Cylindrical shape extrudates of calcium silicate hydrate (CSH) were prepared using different percentages of polyvinyl alcohol (PVA) / sodium alginate (SA) mixtures as binders and an aqueous solution containing 6% $H_3BO_3$ and 3% $CaCl_2$ was used as a cross linking agent. As the quantity of alginate increases, the phosphate removal efficiency and capacity were decreased. Among four different extrudate samples, the sample prepared by 8% PVA + 2% SA showed the highest phosphate removal efficiency (59.59%) and capacity (29.97 mg/g) at an initial phosphate concentration of 100 ppm and 2.0 g/L adsorbent dosage. Effects of the adsorbent dosage, contact time and initial phosphate concentration on the sample were further studied. The removal efficiency and capacity obtained by a 4.0 g/L adsorbent dose at an initial phosphate concentration of 100 ppm in 3 h were 79.38% and 19.96 mg/g, respectively. The experimental data of kinetic and isotherm measurements followed the pseudo-second-order kinetic equation and Langmuir isotherm model, respectively. These results suggested that the phosphate removal was processed via a chemisorption and a monolayer coverage of phosphate anions was on the CSH surface. The maximum adsorption capacity ($q_{max}$) was calculated as 23.87 mg/g from Langmuir isotherm model.

• 대한전기학회논문지:시스템및제어부문D
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• 제51권9호
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• pp.431-437
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• 2002

Low hemolysis is one of the key factors in the production of successful rotary blood pumps. It is, however, difficult to identify the areas where hemolysis occurs. Computational fluid dynamics(CFD) analysis enables the engineer to predict hemolysis on a computer Fluid dynamics in five different axial flow pumps was analyzed 3-dimensionally using CFD software. The impeller was rotated at a speed which supplied a flow of 5L/min at a pressure difference of 100mmHg. Changes in the turbulent kinetic energy along streamlines through the pumps were computed. Reynolds' shear stress( (equation omitted) ) was calculated using the turbulent kinetic energy. Hemolysis was evaluated based on Reynolds'shear stress and its exposure time(t) : dHb/Hb=3.62$\times$10$^{-5}$ $t^{0.785}$$\tau$$^{2.416}$ . Hemolysis of the pumps was measured in vitro using fresh bovine blood to which citrate phosphate dextrose was added to prevent clotting. A pump flow of 5L/min was maintained at a pressure difference of 100mmHg for 3h. The normalized index of hemolysis(NIH) as measured. Reynolds' shear stress was high behind the impellers. The measured NIH and the calculated hemolysis(dHb/Hb) shoed a good correlation; NIH=0.0003(dHb/Hb) (r=0.90, n=6) in the range of NIH between 0.003 and 1.1. CFD analysis can predict the in vitro results of hemolysis as well as the areas where hemolysis occurs.ysis occurs.

• 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.

• 공업화학
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• 제26권2호
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• pp.210-216
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• 2015

석탄계 입상 활성탄을 사용하여 수용액으로부터 brilliant blue FCF 염료의 흡착에 대해 조사하였다. 회분식 실험은 흡착제의 양, 초기농도와 접촉시간과 온도를 흡착변수로 사용하여 수행하였다. 흡착평형자료는 Langmuir, Freundlich 및 Temkin 식을 사용하여 해석한 결과 Freundlich 식이 가장 좋은 일치도를 나타냈다. 평가된 Freundlich 상수(1/n = 0.129~0.212)로부터 이 흡착공정이 적절한 처리방법이 될 수 있음을 알았다. 흡착속도실험자료를 유사일차 및 유사이차 반응속도식에 적용해 본 결과는 유사이차반응속도식에 잘 맞는 것으로 나타났다. 음수값의 Gibbs 자유에너지(-4.81~-10.33 kJ/mol)와 양수값의 엔탈피(+78.59 kJ/mol)는 흡착이 자발적이고 흡열공정으로 진행된다는 것을 나타냈다.

• 공업화학
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• 제26권5호
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• pp.581-586
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• 2015

입상 활성탄을 사용하여 수용액으로부터 Safranin의 흡착에 대해 조사하였다. 회분식 실험은 흡착제의 양, 초기농도와 접촉시간과 온도를 흡착변수로 사용하여 수행하였다. 흡착평형자료는 Langmuir, Freundlich 및 Dubinin-Radushkevich식을 사용하여 해석한 결과 Freundlich식이 가장 좋은 일치도를 나타냈다. 평가된 Langmuir 분리계수, $R_L=0.183{\sim}0.254$와 Freundlich 분리계수, 1/n = 0.518~0.547로부터 이 흡착공정이 적절한 처리방법이 될 수 있음을 알았다. 흡착속도실험자료를 유사1차 및 유사2차 반응속도식에 적용해 본 결과는 유사2차반응속도식에 잘 맞는 것으로 나타났다. 음수값의 Gibbs 자유에너지(${\Delta}G=-3.688{\sim}-7.220kJ/mol$)와 양수값의 엔탈피(${\Delta}H=33.126kJ/mol$)는 흡착이 자발적이고 흡열공정으로 진행된다는 것을 나타냈다.