• Bulletin of the Korean Chemical Society
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• v.19 no.7
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• pp.776-779
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• 1998

Second-order rate constants have been measured spectrophotometrically for the addition reaction of a series of alicyclic amines to 3-butyn-2-one to yield their respective enamines at 25.0 'C. The reactivity of the amines increases with increasing the basicity of the amines. However, the Bronsted-type plot obtained exhibits a downward curvature as the basicity of the amines increases, i.e. βnuc decreases from 0.3 for low basic amines (pKa < 9) and to 0.1 for highly basic amines (pKa > 9). Such a curvature in the Bronsted-type plot is clearly indicative of a change in the reaction mechanism or transition state structure. From the corresponding reactions run in D2O, the magnitude of kinetic isotope effect (KIE) has been calculated to be about 0.8 for highly basic amines and 1.21 for weakly basic amines. The difference in the magnitude of KIE also supports a change in the reaction mechanism or transition state structure upon changing the basicity of the amines. Furthermore, the small KIE clearly suggests that H+ transfer is not involved in the rate-determining step, i.e. the addition reaction is considered to proceed via a stepwise mechanism in which the attack of the amines to the acetylene is the rate-determining step. The curvature in the Bronsted-type plot has been attributed to a change in the degree of bond formation between the amine and the acetylene.

• Bulletin of the Korean Chemical Society
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• v.18 no.5
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• pp.523-527
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• 1997

Apparent second-order rate constants (kapp) have been measured spectrophotometrically for the reaction of 2,4-dinitrophenyl benzoate (DNPB) with 6 secondary cyclic amines in H2O containing 20 mole% DMSO at 25.0±0.1 ℃. The Bronsted-type plot (log kapp vs. pKa) shows a break at pKa near 9.1, e.g. two straight lines with βapp values of 0.67 and 0.44 for the low basic (pKa < 9.1) and the highly basic (pKa > 9.1) amines, respectively. Using an estimated k2 value of 3×109 sec-1, all the other microconstants (k1, k-1 and K) involved in the present aminolysis have been calculated. The k value decreases with increasing the basicity of amines while k1 and K values increase with increasing the amine basicity, as expected. Good linear Bronsted-type plots have been obtained for these microconstants of the present aminolysis of DNPB. The magnitudes of the slope of the Bronsted-type plots, k1 and k-1 have been calculated to be 0.43 and - 0.24, respectively, indicating the k-1 step is about two folds less sensitive than the k1 step to the amine basicity. The K value has been calculated to be 0.66, which appears to be much smaller than the one for other aminolyses showing general base catalysis. The small K value has been attributed to the absence of general base catalysis in the present aminolysis of DNPB.

• Journal of the Korean Chemical Society
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• v.15 no.3
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• pp.147-152
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• 1971

On the baisis of the calculations by the two centre Huckel method for sigma electron system, the electronic structure of the various aliphatic amines including ammonia, and the relationship between the observed $pK_b$ and the change in the sigma electronic energy, ${\Delta}E{\sigma}$ in the course of protonation are discussed. A parallelism is observed between the $pK_b$ and the calculated ${\Delta}E{\sigma}$ of the amines. Also, it is observed that the electron densities of hydrogen atom directly bonded to nitrogen of the amines, likewise have a linear relationship with the $pK_b$. Therefore, the basicity of the aliphatic amines may be estimated qualitatively by means of the two center Huckel method.

• Journal of Welding and Joining
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• v.5 no.1
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• pp.57-63
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• 1987

A method which can be used for evaluating slag detachability is proposed in this study. The proposed method was intended to get an absolute value for slag detachability, to give consistent value for a given welded joint, and finally to be simple to test. With a test fig made in this study, an impact by dropping a steel ball (13Kg in weight) is applied on the back side of an as-welded plate having a slag layer on the weld bead. Such impact applied forces the slag to drop off from the bead surface. In order to make a quantitative evaluation the amount of slag removed was measured with increasing the number of drops. Using this method six kinds of fluxes were evaluated in terms of the effects of flux type, basicity and weding variables on the slag detachability. As an initial result of this test, it was found that welding heat input affects the detachability significantly. Most importantly the evaluation made using the presently proposed method gives the same order of ranking as that of the actual practice done by a welder.

• Korean Journal of Materials Research
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• v.5 no.5
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• pp.620-624
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• 1995

To study the acid and base properties of chemical-treated natural zeolite, FT-IR analysis was performed by the adsorption of pyridne and pyrrole and thermo-gravimetric analysis was done by the adsorption of NH$_{3}$. These solid catalysts have two acid sites, which are related to the Bronsted and Lewis acid sites, respectively. HIC-treatment led to the increased acidity and the maintained basicity.Acidity of NaHO-treatment samples also increased with thr NaOH-treatment but basicity decreased. The p-xylene selectivity on the chemical-treatment zelite was higher than that on the untreated zeolite.

• Journal of the Korean Ceramic Society
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• v.34 no.7
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• pp.677-684
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• 1997

The effects of fluxes on MgO coating materials for tundish were investigated. As the number of charge in continuous casting was increased, the basicity of tundish slag was decreased due to the increase of silica formed by dissolution from rice hull. As a result, the wear of magnesia lining was increased. In aggregates of MgO coating materials, magnesioferrite was formed by the reaction between magnesia and ferric oxide formed by the oxidation of molten steel, while matrix parts of MgO coating materials were worn by CaO-Al2O3-SiO2 compounds. Silica in rice hull extracted to the molten slag reduced basicity of slag and formed forsterite in the result of its reaction with magnesia lining. Also, fayalite was formed from the reaction between silica and ferric oxide and it caused the increment of magnesia lining's wear. The wear of magnesia lining by flux of CaO-SiO2 was larger than that of Cao-Al2O3 and calcia in the flux increased the wear of magnesia lining through the formation of rankinite.

• Resources Recycling
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• v.8 no.1
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• pp.44-51
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• 1999

Converter slag was reduced and modified by the simultaneous addition of carbon and waste foundry sand as a $SiO_2$ source. The basic properties such as phase distribution, composition, specific density, hardness. absorption of water and compressive strength of modified slags were measured. The Iron recovery was significantly affected by the basicity of slag. The properties of slow cooled-modified slags of basicity 1.34 arc very similar to the natural aggregates.

• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.632-636
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• 1992

Second-order rate constants have been determined spectrophotometrically for nucleophilic substitution reactions of p-nitrophenyl benzoate with various anionic nucleophiles including 6 ${\alpha}$ -effect nucleophiles. The logarithmic second-order rate constants for the aryloxides give a good Bronsted correlation with the respective basicity while the ones for p-chlorothiophenoxide and hydroxide exhibit significantly positive and negative deviations, respectivity, from the Bronsted linear line. The deviations are attributed to a solvation effect rather than a change in the reaction mechanism. The ${\alpha}$-effect nucleophiles except highly basic ones demonstrate significantly higher nucleophilicity (the ${\alpha}$ -effect) than would be predicted from the respective basicity. The effect of solvation and polarizability appears to be important for the ${\alpha}$-effect as well as for the reaction rate.

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.646-647
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• 1993

• Applied Chemistry for Engineering
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• v.21 no.1
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• pp.1-5
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• 2010

Cu(II)-organic complexes were synthesized with Lewis base organic ligands including diamine, aminothiol, and dithiol to determine the reactivity for DFP hydrolysis. Results show that the aminothiol catalyst enhances the hydrolysis of DFP in three folds compared to diamine type because aminothiol has higher basicity than diamine. Due to low solubility of Cu(II)(1,2-ethane dithiol)$(NO_3)_2$, it is impossible to compare directly the rates in homogeneous condition. However, the rate of dithol complex is even 1.6 times faster than that of the diamine type. The reactivity of zeolite for DFP hydrolysis is also evaluated. NaY type does not promote the hydrolysis, but RuNaY shows relatively lower reactivity than those of Cu(II)-organic ligands complexes.