• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2443-2447
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate (7) and 4-nitrophenyl isonicotinate (8) with a series of cyclic secondary amines in $H_2O$ containing 20 mol % DMSO at $25.0^{\circ}C$. The Br${\o}$nsted-type plots for the reactions of 7 and 8 are linear with ${\beta}_{nuc}=0.90$ and 0.92, respectively, indicating that the reactions proceed through a stepwise mechanism with expulsion of the leaving group occurring in the rate-determining step. Comparison of the reactivity of 7 and 8 with that of 4-nitrophenyl benzoate (2a) and 4-nitrophenyl picolinate (6) has revealed that their reactivity toward the amines increases in the order 2a < 7 < 8 < 6, although the reactions of these substrates proceed through the same mechanism. Factors that control reactivity and reaction mechanism have been discussed in detail (e.g., inductive and field effects, H-bonding interaction, solvent effect, etc.).

• Bulletin of the Korean Chemical Society
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• v.12 no.5
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• pp.510-514
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• 1991

Second-order rate constants have been determined spectrophotometrically for reactions of S-p-nitrophenyl substituted thiobenzoates with various phenoxide ions and S-aryl substituted thiobenzoates with $HO^-$ ion. Thiol esters have been found to be more reactive than the corresponding oxygen esters toward phenoxide ions. The high reactivity of thiol esters relative to oxygen esters becomes insignificant as the basicity of the nucleophile increases. Furthermore, the highly basic $HO^-$ ion is less reactive toward thiol esters than oxygen esters. The significant dependence of the reactivity of thiol esters on the basicity of nucleophiles has been attributed to the nature of the HSAB principle. The present kinetic study has also revealed that the reactivity of thiol esters compared to oxygen esters is not so pronounced as expected based on the enhanced nucleofugicity of thiol esters. However, the effects of substituents in the nucleophile and in the acyl moiety of the substrate on rate appear to be significant. These kinetic results have led to a conclusion that the present reactions proceed via a rate-determining formation of a tetrahedral intermediate followed by a fast breakdown of it. The magnitude of the ${\beta}$ values shows no tendency either to increase or to decrease with the intrinsic reactivity of the reagents. The constancy of ${\beta}$ values in the present system is suggestive that the RSP should have limited applicability.

• Journal of the Korean Chemical Society
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• v.13 no.4
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• pp.373-377
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• 1969

In order to determine the monomer reactivity ratio in copolymerization of acrolein, the copolymerization of acrolein with styrene, methyl methacrylate and vinyl acetate respectively was studied. The Q and e value of acrolein in each copolymerization were also calculated from those of monomer reactivity ratios, but the calculated values were slightly different from each other. The Q and e of acrolein for the system of acrolein-styrene copolymerization were Q = O.64 and e = O.62 respectively. Relations among the Q and e value, the composition and structure of copolymers and the mean sequence length in copolymerization were also discussed for acrolein copolymers.

• Transactions of the Korean hydrogen and new energy society
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• v.20 no.3
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• pp.245-255
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• 2009

Effect of CO$_2$ concentration on reduction reactivity of oxygen carrier particles for chemical-looping combustor were investigated. Four particles, NiO/bentonite, OCN601-650, OCN702-1100, OCN702-1250, were used as oxygen carrier particles and two kinds of gases (CH$_4$, 5%, N$_2$ balance and CH$_4$ 5%, CO$_2$ balance) were used as reactants for reduction. For all oxygen carrier particles, higher maximum conversion, reduction rate, oxygen transfer capacity, and oxygen transfer rate were achieved when we used N$_2$ balance gas. OCN601-650 particle showed higher oxygen transfer rate for all gases than other particles, and therefore we selected OCN601-650 particle as the best candidate. For all particles, lower carbon depositions were observed when we used CO$_2$ balance gas.

• Bulletin of the Korean Chemical Society
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• v.31 no.8
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• pp.2135-2136
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• 2010

• Bulletin of the Korean Chemical Society
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• v.19 no.8
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• pp.875-878
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• 1998

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.421-422
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• 1993

• Bulletin of the Korean Chemical Society
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• v.22 no.10
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• pp.1127-1130
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• 2001

• Bulletin of the Korean Chemical Society
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• v.14 no.1
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• pp.149-151
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• 1993

• Bulletin of the Korean Chemical Society
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• v.15 no.3
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• pp.179-181
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• 1994