• Title/Summary/Keyword: Reaction kinetic

Search Result 1,260, Processing Time 0.025 seconds

Graft Copolymerization of Methyl Methacrylate on to Chloroprene Rubber (Chloroprene 고무에 대한 Methyl Methacrylate의 Graft공중합)

  • Park, Chan-Young;Kim, Byung-Kyu;Park, Tchun-Wook
    • Elastomers and Composites
    • /
    • v.26 no.2
    • /
    • pp.109-114
    • /
    • 1991
  • The graft copolymerization of chloroprene rubber with methyl methacrylate in toluene solution has been carried out varying the concentration of monomer, initiator, CR, reaction time, and reaction temperature, etc.. It is observed that the grafting reaction follows conventional kinetic behavior under the present experimental conditions. Identification of grafting on to chloroprene rubber was obtained through characterization of the graft copolymer by infrared spectrometer.

  • PDF

Preparation of Polyenaryloxynitriles from Dicyanovinyl Chloride and Diphenol Derivatives in the Presence of DABCO

  • Geum, Ne Ri;Gong, Myeong Seon
    • Bulletin of the Korean Chemical Society
    • /
    • v.21 no.11
    • /
    • pp.1111-1114
    • /
    • 2000
  • The kinetic study of the enaryloxynitriles via the nucleophilic vinylic substitution reaction of various phenol derivatives with 1-chloro-1-phenyl-2,2-dicyanoethene (1) was conducted in the presence of 1,4-diazabicyclo[2,2,2]octane (DABCO). Nucleo philic vinylic substitution of phenol derivatives with electrophilic olefins carrying sluggish leaving group involves a third-order reaction. The reaction was applied to solution polymerization of diphenol derivatives with p-bis(1-chrolo-2,2-dicyanovinyl)benzene (2), which yielded various polyenaryloxynitriles with moderate molecular weight.

Kinetic Studies on Nucleophilic Substitution Reactions of Alkane Sulfonylchlorides with Anilines in MeOH-MeCN Mixtures (메탄올-아세토니트릴 혼합용매에서 염화알칸술포닐과 아닐린의 친핵 치환반응에 대한 속도론적 연구)

  • Ikchoon Lee;Han Keun Kang;Hai Whang Lee
    • Journal of the Korean Chemical Society
    • /
    • v.29 no.5
    • /
    • pp.478-481
    • /
    • 1985
  • Nucleophilic substitution reactions between Alkanesulfonylchlorides and p-substituted anilines in methanol-acetonitrile mixture have been studied kinetically. Reactivities of substrates, substituent effects of nucleophile and solvent effects indicate that the studied reaction proceeds via $S_N2$. The kinetic results show that transition state of the reaction between i-PSC and anilines becomes looser as the composition of methanol increases.

  • PDF

AN ANALYSIS OF MOLDING AND CURING OF SMC BY THE FINITE ELEMENT METHOD

  • Kim, Naksoo-
    • Proceedings of the Korean Society for Technology of Plasticity Conference
    • /
    • 1992.03a
    • /
    • pp.177-200
    • /
    • 1992
  • A thermo-viscoplastic finite element program was developed to analyze the compression molding of SMC process. Deformation of the material was modelled by using the flow-rule. Heat balance during the process was coupled to the deformation. In the cure study, a kinetic model was adopted to describe the cure behavior. The numerical kinetic model was integrated with the thermo-viscoplastic numerical analysis by adding heat generation due to the chemical reaction of the workpiece in the heat transfer analysis. The integrated finite element program can simulate a whole sequential molding process including deformation, heat transfer, and chemical reaction. A practical SMC molding process with T-shaped substructure was simulated. The simulated results showed good agreements with experiments.

  • PDF

Kinetics and Mechanism of Anilinolyses of Ethyl Methyl, Ethyl Propyl and Diisopropyl Chlorothiophosphates in Acetonitrile

  • Barai, Hasi Rani;Hoque, Md. Ehtesham Ul;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.12
    • /
    • pp.3811-3816
    • /
    • 2013
  • Nucleophilic substitution reactions of ethyl methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D=0.66-0.99$) with 2, primary normal and secondary inverse ($k_H/k_D=0.78-1.19$) with 4, and primary normal ($k_H/k_D=1.06-1.21$) with 7. The primary normal and secondary inverse DKIEs are rationalized by frontside attack involving hydrogen bonded, four-center-type transition state, and backside attack involving in-line-type transition state, respectively. The anilinolyses of ten chlorothiophosphates are examined based on the reactivity, steric effect of the two ligands, thio effect, reaction mechanism, DKIE and activation parameter.

Kinetics and Mechanism of the Anilinolysis of Diethyl Thiophosphinic Chloride in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
    • /
    • v.32 no.7
    • /
    • pp.2306-2310
    • /
    • 2011
  • The nucleophilic substitution reactions of diethyl thiophosphinic chloride with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 55.0 $^{\circ}C$. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) invariably increase from secondary inverse ($k_H/k_D$ < 1) to primary normal (kH/kD > 1) as the nucleophiles change from the strongly basic to weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the gradual transition state (TS) variation from a predominant backside attack, via invariably increasing the fraction of a frontside attack, to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. A frontside attack involving a hydrogen bonded, four-center-type TS is substantiated by the primary normal DKIEs.

Kinetic Studies on the Ligand Substitution Reactions of Cyanocobalt(II) Complexes in Micellar Solutions (미셀용액에서 Cyanocobalt(II) 착물의 리간드치환 반응에 대한 속도론적 연구)

  • Ahn, Beom-Shu
    • Journal of the Korean Applied Science and Technology
    • /
    • v.26 no.3
    • /
    • pp.370-378
    • /
    • 2009
  • Kinetic studies on the ligand substitution reactions of cyanocomplexes were performed in several micellar solutions. It showed the observed rate constants was found to be independent of the entering ligand concentration at high concentration of cyanopyridine and pyrazinecarboxylate. We could see also that in nonionic and anionic micellar solutions no influence of changes in the surfactant concentration on the observed rate constants was found. Taking into account the hydrophilic nature of the cobalt complex, the cobalt complex molecule was expected to be located in the aqueous phase of the micellar systems, where the reaction would take place. In cationic micellar solutions, a small increase in the observed rate constant was found when the cationic surfactant concentration increased. After reaching a maximum, the rate constant decreased on increasing surfactant concentration and subsequently it reached a plateau, where the observed rate constant was independent of changes in the surfactant concentration.

Interactions between Hydrodesulfurization of Thiophene and Hydrodenitrogenation of Pyridine and the Kinetic Analysis (수첨탈황과 탈질반응에서 Thiophene과 Pyridine의 상호영향과 그 속도론적 해석)

  • 박종희;한창훈;김경림
    • Journal of Korean Society for Atmospheric Environment
    • /
    • v.4 no.1
    • /
    • pp.13-22
    • /
    • 1988
  • Interactions between hydrodesulfurization of thiophene and hydrodenitrogenation of pyridine and the kinetic analysis were studied over $Ni-W/\gamma-Al_2O_3$ catalysts and this study was made at temperatures ranging from 473-673 K and at total pressures ranging from 10-25 $\times 10^5$ Pa. Hydrodesulfurization of thiophene was inhibited by presence of pyridine at all temperatures studied, and the rate of pyridine hydrodenitrogenation was slower than that of thiophene hydrodesulfurization in the operating conditions. Pyridine hydrodenitrogenation was also inhibited by the presence of thiophene at low temperatures but was enhanced by the thiophene at temperatures higher than 613K. Thiophene reaction rate was determined by multiple linear regression analysis using Langmuir-Hinshelwood-Hougen-Watson model and the result was given to be $r = kP_T^p_H/(1+K_Tp_T+K_Pp_P)^2$. At each temperature, reaction rate constants and absorption equilibrium equilibrium constants were determined and the activation energy was 12.98 kcal/gmol from Arrhenius plot.

  • PDF

Cure Kinetics of Epoxy/Diamine System Modified with Malononitrile by Barrett Method and Integral Method (Malononitrile에 의해 개질된 Epoxy/Diamine계의 경화반응 속도론: Barrett Method와 Integral Method)

  • Cheon, In-Suk;Don, Yun-Seung;Sim, Mi-Ja;Kim, Sang-Uk
    • Korean Journal of Materials Research
    • /
    • v.4 no.5
    • /
    • pp.574-580
    • /
    • 1994
  • This study is about cure kinetics of DGEBA/MDA/MN(malononitrile) system by Barrett method and Integral method using DSC dynamic run. Curing behavior was shown through DSC and the heat change involved in a reaction could be measured directly with DSC. The kinetic parameters such as activation energy, pre-exponential factor and reaction order were given by Barrett method and Integral method obtained in an assumption that the area of DSC enthalpic analysis curve was propotional to the enthalpic change.

  • PDF

Analysis of Flame Generated Turbulence for a Turbulent Premixed Flame with Zone Conditional Averaging (영역분할조건평균법에 근거한 난류예혼합화염내 난류운동에너지 생성에 관한 연구)

  • Im, Yong-Hoon;Huh, Kang-Yul
    • 한국연소학회:학술대회논문집
    • /
    • 2003.12a
    • /
    • pp.49-56
    • /
    • 2003
  • Mathematical formulation of the zone conditional two-fluid model is established to consider flame-generated turbulence in premixed turbulent combustion. The conditional statistics of major flow variables are investigated to understand the mechanism of flame generated turbulence. The flow field in burned zone shows substantially increased turbulent kinetic energy, which is highly anisotropic due to reaction kinematics across thin flamelets. The transverse component of rms velocities in burned zone become larger than axial component in the core of turbulent flame brush. The major source or sink terms of turbulent kinetic energy are the interfacial transfer by the mean reaction rate and the work terms by fluctuating pressure and velocity on a flame surface.

  • PDF