• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2009-2014
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Journal of the Korean Chemical Society
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• v.57 no.3
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• pp.365-369
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• 2013

With the wide application of ASP (alkaline-surfactant-polymer) flooding, the scaling becomes more and more serious, which is harmful to the oilfield and environment. In order to investigate the effects of HPAM on calcium carbonate crystallization, the crystallization behaviors of $CaCO_3$ in HPAM (Hydrolyzed polyacrylamide) solutions were studied and the composition and morphology of $CaCO_3$ crystal were investigated in different concentrations of polyacrylamide solutions. The crystal forms and morphologies of $CaCO_3$ were characterized by Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy. The results show that the crystallization of $CaCO_3$ is strongly influenced by the HPAM. The paper analyzed the internal cause, and the results show: The reasons leading to the change of morphology are carboxyl groups in polyacrylamide molecule and $Ca^{2+}$ in solution form chelates by coordination bond. And the chelates are adsorbed on the calcium hydroxide surfaces of solid-liquid interfaces so as to change the formation rate of calcium carbonate crystal nucleus. The research provides a reliable basis for the mechanism research of the scaling problem in the oil extraction process of ASP flooding and the adoption of scale inhibition and scale inhibitor.

• Journal of the Korean Chemical Society
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• v.32 no.3
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• pp.195-202
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• 1988

An electrochemical reduction on the 3-phenyl-4-nitrosydnone in acetonitrile solution has been studied by direct current, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. Before the cleavage of phenyl-N single bond a irreversible electron transfer-chemical reaction(EC) mechanism of nitro functional group proceeded to form amino (or-hydroxylamino) group by multielectron transfer which is followed to give phenyl hydrazine by single electron transfer-chemical reaction at the 2nd and 3rd irreversible reduction wave of high negative potential region. The cathodic half-wave potentials shown to be shift negative due to inhibitory effect of cetyl-trimethyl ammonium bromide micelle while reversible anodic peaks on the 2nd and 3rd reduction waves in the presence of NaLS at high negative potential region.

• Nuclear Engineering and Technology
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• v.36 no.6
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• pp.512-527
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• 2004

This paper describes the finite element (FE) analysis results of a 1/4 scale model of a prestressed concrete containment vessel (PCCV) by considering the tension stiffening effect, which is a result of the bond effect between the concrete and the steel. The tension stiffening model is assumed to be an exponential form based on the relationship between the average stress and the average strain of the concrete. The objective of the present FE analysis is to evaluate the ultimate internal pressure capacity of the PCCV, as well as its failure mechanism, when the PCCV model is subjected to a monotonous internal pressure beyond is design pressure capacity. With the commercial code ABAQUS, the FE analysis used two concrete failure criteria: a 2-dimensional axi-symmetric model with modified Drucker-Prager failure criteria and a 3-dimensional model with a damaged plasticity mod디. The results of our FE analysis on the ultimate pressure capacity and failure modes of PCCV have a good agreement with the experimental data.

• Journal of the Korean Applied Science and Technology
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• v.25 no.2
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• pp.115-122
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• 2008

The hydrosilylation is an addition reaction of Si-H bond to unsaturated double bonds, which provides a convenient mechanism to synthesize poly(dimethylsiloxane-co-methylsiloxane)copolymer having siloxy units in polymer backbone. In this study, Poly(dimethylsiloxane-co-methylsiloxane) copolymer was synthesized through the polymerization reaction of cyclopentasiloxane with poly(methyl-hydrogen) siloxane. Silicone-hydrogen functional group of the poly(dimethylsiloxane-co-methylsiloxane) copolymer was substituted to the alkyl groups by hydrosilylation. And their structure was analyzed with FT-IR, H-NMR and GPC instruments, respectively. Surface tension of the synthetic compounds is increased from 22dyne/cm to 25dyne/cm according to increase additional EO moles. The cmc which was evaluated by surface tension was ranged $10^{-5}$ to $10^{-4}mol/L$ and it was decreased according to increase of dimethyl siloxyl content. HLB number of these surfactants was evaluated 9.5 to 11.5 range. These silicone surfactants is applied to self-emulsifier defoamer and personal care products as surface tension depressant, emulsifier, foam control agent.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1136-1144
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• 1999

The collision-induced reaction of gas-phase atomic hydrogen with hydrogen atoms chemisorbed on a silicon (001)-(2×1) surface is studied by use of the classical trajectory approach. The model is based on reaction zone atoms interacting with a finite number of primary system silicon atoms, which then are coupled to the heat bath, i.e., the bulk solid phase. The potential energy of the Hads‥Hgas interaction is the primary driver of the reaction, and in all reactive collisions, there is an efficient flow of energy from this interaction to the Hads-Si bond. All reactive events occur on a subpicosecond scale, following the Eley-Rideal mechanism. These events occur in a localized region around the adatom site on the surface. The reaction probability shows the maximum near 700K as the gas temperature increases, but it is nearly independent of the surface temperature up to 700 K. Over the surface temperature range of 0-700 K and gas temperature range of 300 to 2500 K, the reaction probability lies at about 0.1. The reaction energy available for the product states is small, and most of this energy is carried away by the desorbing H2 in its translational and vibrational motions. The Langevin equation is used to consider energy exchange between the reaction zone and the bulk solid phase.

• Bulletin of the Korean Chemical Society
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• v.15 no.7
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• pp.553-559
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• 1994

Dynamics of $CH_2CI$ group in ${\alpha},2,6$-trichlorotoluene dissolved in $CDCl_3$ was studied by observing various relaxation modes for $^{13}C$ under proton undecoupled condition. Partially relaxed $^{13}C$ spectra were obtained at $34^{\circ}C$ as a function of evolution time after applying various designed pulse sequences to this $AX_2$ spin system. It was found that nonlinear regression analysis of the relaxation data for these magnetization modes could provide the information about dipolar and spin-rotational auto-correlation and cross-correlation spectral densities for fluctuation of the $^{13}C-^1H$ internuclear vector in $CH_2Cl$ group. The results show that the effect of cross-correlation is comparable in magnitude to that of auto-correlation and the relaxation in this spin system is dominated by dipolar mechanism rather than spin-rotational one. From the resulting spectral density data we could calculate the bond angle ${\angle}HCH\;(105.1$^{\circ}$) and elements of the rotational diffusion tensor for $CH_2Cl$ group.

• Structural Engineering and Mechanics
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• v.72 no.4
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• pp.469-477
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• 2019

The understanding of tool-rock interaction mechanism is of high essence for improving the rock breaking efficiency and optimizing the drilling parameters in mechanical rock breaking. In this study, the tool-rock interaction models of indentation and cutting are carried out by employing the discrete element method (DEM) to examine the rock failure modes of various brittleness rocks and critical indentation and cutting depths of the ductile to brittle failure mode transition. The results show that the cluster size and inter-cluster to intra-cluster bond strength ratio are the key factors which influence the UCS magnitude and the UCS to BTS ratio. The UCS to BTS strength ratio can be increased to a more realistic value using clustered rock model so that the characteristics of real rocks can be better represented. The critical indentation and cutting depth decrease with the brittleness of rock increases and the decreasing rate reduces dramatically against the brittleness value. This effort may lead to a better understanding of rock breaking mechanisms in mechanical excavation, and may contribute to the improvement in the design of rock excavation machines and the related parameters determination.

• Bulletin of the Korean Chemical Society
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• v.15 no.2
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• pp.154-161
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• 1994

Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethylthioalkyl)phthalimides (alkyl=ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl). Photocyclizations occur in methanol in modest to high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from sulfur in the ${\alpha}$-silylmethylthioalkyl groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate ${\alpha}$ -silylmethylthio cation radicals and cyclization by radical coupling is proposed. In contrast, photoreactions of N-(trimethylsilylmethylthioalkyl)phthalimides in acetone follow different reaction routes to produce another cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon ${\alpha}$ to silicon and sulfur atoms via triplet carbonyl hydrogen abstraction pathway. The normal singlet SET pathway dominates this triplet process for photoreactions of these substances in methanol while the triplet process dominates the singlet SET pathway for those in acetone. The efficient and regioselective cyclization reactions observed for photolyses in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

• Bulletin of the Korean Chemical Society
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• v.15 no.2
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• pp.161-167
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates (3) with alkali metal ethoxides ($EtO^-M^+$) and butane-2,3-dione monoximates ($Ox^-M^+$) in ethanol at $25^{\circ}C$. The reactivity of the alkali metal ethoxides decreases in the order $EtO^-K^+> EtO^- > EtO^-Li^+$, indicating that $K^+$ ion behaves as a catalyst and $Li^+$ ion acts as an inhibitor for all the substrates studied. For the corresponding reactions of 3 with Ox^-M^+$, $Li^+$ ion also exhibits inhibitory effect for all the substrates, while, $K^+$ ion shows catalytic or inhibitory effects depending on the nature of substituents on the acyl and phenyl moieties. A study of substituent effect on rate has revealed that both EtO^- $and Ox^-$ systems have the same reaction mechanism. The different behavior shown by $K^+$ ion for the reaction of 3 with $EtO^-$ and $Ox^-$ would be attributed to a difference in charge polarization of S=O bond in the transition state between the two systems and/or a change in conformation of Ox^-K^+$.