• 한국물환경학회지
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• 제27권6호
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• pp.896-904
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• 2011

The features of the capture reaction of $CO_2$ by ammonia solution have been investigated along with the effect of temperature on the reaction based upon computer program-utilizing calculation and thermodynamic estimation. The stable region of $CO{_3}^{2-}$ was observed to increase with temperature and the change of the stable region of $CO{_3}^{2-}$ with temperature was greater than the temperature variation of the stable region of other carbonate species. The distribution diagram for $NH_4{^+}-NH_3$ system was constructed and the rise of temperature resulted in the decrease of the stability of $NH_4{^+}$ ion, which was thought to be due to the endothermic nature of its acidic dissociation. Considering the introduction of $Ca^{2+}$ ion in the carbon capture reaction by $NH_4{^+}$, the temperature was observed to be important in the determination of the order of reaction between carbonate ion and these cations. The removal process of $CO_2$ gas by ammonia solution was presumed to occur in open system and the temperature variations of the concentration of carbonate system species along with their total concentration were calculated for the proper control and design of the real process.

• Bulletin of the Korean Chemical Society
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• 제33권5호
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• pp.1547-1550
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• 2012

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of benzyl 2-pyridyl carbonate $\mathbf{3}$ and $t$-butyl 2-pyridyl carbonate $\mathbf{3}$ with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Substrate $\mathbf{4}$ is much less reactive than $\mathbf{3}$ and the steric hindrance exerted by the bulky $t$-Bu group in $\mathbf{4}$ has been attributed to its decreased reactivity. The Br${\o}$nsted-type plots for the reactions of $\mathbf{3}$ and $\mathbf{4}$ are linear with ${\beta}_{nuc}=0.57$ and 0.45, respectively. Thus, the reactions have been concluded to proceed through a concerted mechanism, although the current reactions were expected to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate $T^{\pm}$. It has been proposed that the rate of leaving-group expulsion is accelerated by the intramolecular H-bonding interaction in $T^{\pm}$ and the "push" provided by the RO group through the resonance interaction. Thus, the enhanced nucleofugality forces the reactions to proceed through a concerted mechanism. The reactivity-selectivity principle (RSP) is not applicable to the current reaction systems, since the reaction of the less reactive $\mathbf{4}$ results in a smaller ${\beta}_{nuc}$ than that of the more reactive $\mathbf{3}$. Steric hindrance exerted by the bulky $t$-Bu group in $\mathbf{4}$ has been suggested to be responsible for the failure of the RSP.

• Bulletin of the Korean Chemical Society
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• 제33권9호
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• pp.2971-2975
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• 2012

Second-order rate constants $k_N$ have been measured spectrophotometrically for nucleophilic substitution reactions of t-butyl 4-pyridyl carbonate 8 with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 8 is linear with ${\beta}_{nuc}$ = 0.84. The ${\beta}_{nuc}$ value obtained for the reactions of 8 is much larger than that reported for the corresponding reactions of t-butyl 2-pyridyl carbonate 6 (i.e., ${\beta}_{nuc}$ = 0.44), which was proposed to proceed through a forced concerted mechanism. Thus, the aminolysis of 8 has been concluded to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate $T^{\pm}$, in which expulsion of the leaving-group from $T^{\pm}$ occurs at the rate-determining step (RDS). In contrast, aminolysis of benzyl 4-pyridyl carbonate 7 has been reported to proceed through two intermediates, $T^{\pm}$ and its deprotonated form $T^-$ on the basis of the fact that the plots of pseudo-first-order rate constant $k_{obsd}$ vs. amine concentration curve upward. The current study has demonstrated convincingly that the nature of the leaving and nonleaving groups governs the reaction mechanism. The contrasting reaction mechanisms have been rationalized in terms of an intramolecular H-bonding interaction, steric acceleration, and steric inhibition.

• 공업화학
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• 제29권1호
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• pp.62-66
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• 2018

Styrenated phenol alkoxylate (SP-A)는 일반적으로 균일계 염기 촉매 하에서 styrenated phenol (SP)과 ethylene oxide (EO)로부터 제조되어진다. 그러나, 취급이 용이하지 않은 EO를 사용하려면 고압반응장치를 이용한 반응공정 제어가 필요하다. 또한, 균일계 염기 촉매를 사용하면 반응종결 후에 잔존하는 염기를 제거하기 위한 중화공정이 필요하고, 촉매와 생성물의 분리가 어렵다는 문제점이 있다. 따라서, 본 연구에서는 균일계 염기 촉매를 사용하지 않고 불균일계염기 촉매를 사용하여 SP와 ethylene carbonate (EC)의 반응으로부터 제조된 SP-A에 대하여 보고하고자 한다. SP-A의 제조에 사용된 불균일계 염기 촉매는 KOH를 $La_2O_3$에 담지시킨 후, 소성하여 얻었다. 또한, EO 대신 EC를 사용함으로써 고압반응이 아닌 상압반응 조건에서 SP-A제조가 가능하였다. 합성된 SP-A의 평균 분자량 크기는 반응조건에 따라서 매우 다양하게 나타났다. $KOH/La_2O_3$촉매 하에서 제조된 SP-A의 평균 분자량 크기는 반응온도, 촉매의 첨가량 및 EC의 첨가량을 조절함으로써 임의로 조절이 가능하였다.

• 한국환경과학회지
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• 제21권5호
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• pp.585-596
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• 2012

This study is mainly focused on micellar effect of cetyltrimethyl ammonium bromide(CTABr) solution including alkylbenzimidazole(R-BI) on dephosphorylation of isopropyl-4-nitrophenylphosphinate(IPNPIN) in carbonate buffer(pH 10.7). The reactions of IPNPIN with R-$BI^{\ominus}$ are strongly catalyzed by the micelles of CTABr. Dephosphorylation of IPNPIN is accelerated by $BI^{\ominus}$ ion in $10^{-2}$ M carbonate buffer(pH 10.7) of $4{\times}10^{-3}$ M CTABr solution up to 89 times as compared with the reaction in carbonate buffer by no benzimidazole(BI) solution of $4{\times}10^{-3}$ M CTABr. The value of pseudo first order rate constant($k_{\Psi}$) of the reaction in CTABr solution reached a maximum rate constant increasing micelle concentration. Such rate maxima are typical of micellar catalyzed bimolecular reactions. The reaction mediated by R-$BI^{\ominus}$ in micellar solutions are obviously slower than those by $BI^{\ominus}$, and the reaction rate were decreased with increase of lengths of alkyl groups. It seems due to steric effect of alkyl groups of R-$BI^{\ominus}$ in Stern layer of micellar solution. The surfactant reagent, CTABr, strongly catalyzes the reaction of IPNPIN with R-BI and its anion(R-$BI^{\ominus}$) in carbonate buffer(pH 10.7). For example, $4{\times}10^{-3}$ M CTABr in $1{\times}10^{-4}$ M BI solution increase the rate constant($k_{\Psi}=98.5{\times}10^{-3}\;sec^{-1}$) of the dephosphorylation by a factor ca.25, when compared with reaction($k_{\Psi}=3.9{\times}10^{-4}\;sec^{-1}$) in $1{\times}10^{-4}$ M BI solution(without CTABr). And no CTABr solution, in $1{\times}10^{-4}$ M BI solution increase the rate constant($k_{\Psi}=3.9{\times}10^{-4}\;sec^{-1}$) of the dephosphorylation by a factor ca.39, when compared with reaction ($k_{\Psi}=1.0{\times}10^{-5}\;sec^{-1}$) in water solution(without BI). This predicts that the reactivities of R-$BI^{\ominus}$ in the micellar pseudophase are much smaller than that of $BI^{\ominus}$. Due to the hydrophobicity and steric effect of alkyl group substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long alkyl groups of CTABr.

• 한국환경과학회지
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• 제19권5호
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• pp.565-575
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• 2010

This study is mainly focused on micellar effect of cetylpyridinium chloride(CPyCl) solution including alkylbenzimidazole(R-BI) on dephosphorylation of diphenyl-4-nitrophenylphosphinate(DPNPIN) in carbonate buffer(pH 10.7). The reactions of DPNPIN with R-BI$^{\ominus}$ are strongly catalyzed by the micelles of CPyCl. Dephosphorylation of DPNPIN is accelerated by BI$^{\ominus}$ ion in $10^{-2}M$ carbonate buffer(pH 10.7) of $4{\times}10^{-3}M$ CPyCl solution up to 100 times as compared with the reaction in carbonate buffer by no BI solution of $4{\times}10^{-3}M$ CPyCl. The value of pseudo first order rate constant($k^m_{BI}$) of the reaction in CPyCl solution reached a maximum rate constant increasing micelle concentration. Such rate maxima are typical of micellar catalyzed bimolecular reactions. The reaction mediated by R-BI$^{\ominus}$ in micellar solutions are obviously slower than those by BI$^{\ominus}$, and the reaction rate were decreased with increase of lengths of alkyl groups. It seems due to steric effect of alkyl groups of R-BI$^{\ominus}$ in Stern layer of micellar solution. The surfactant reagent, cetylpyridinium chloride(CPyCl), strongly catalyzes the reaction of diphenyl-4-nitrophenylphosphinate(DPNPIN) with alkylbenzimidazole (R-BI) and its anion(R-BI$^{\ominus}$) in carbonate buffer(pH 10.7). For example, $4{\times}10^{-3}M$ CPyCl in $1{\times}10^{-4}M$ BI solution increase the rate constant ($k_{\Psi}=1.0{\times}10^{-2}sec^{-1}$) of the dephosphorylation by a factor ca.14, when compared with reaction ($k_{\Psi}=7.3{\times}10^{-4}sec^{-1}$) in $1{\times}10^{-4}M$ BI solution(without CPyCl). And no CPyCl solution, in $1{\times}10^{-4}M$ BI solution increase the rate constant ($k_{\Psi}=7.3{\times}10^{-4}sec^{-1}$) of the dephosphorylation by a factor ca.36, when compared with reaction ($k_{\Psi}=2.0{\times}10^{-5}sec^{-1}$) in water solution(without BI). This predicts that the reactivities of R-BI$^{\ominus}$ in the micellar pseudophase are much smaller than that of BI$^{\ominus}$. Due to the hydrophobicity and steric effect of alkyl group substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long alkyl groups of CPyCl.

• Korean Chemical Engineering Research
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• 제47권3호
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• pp.373-379
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• 2009

고정층 반응기에서 cesium carbonate 흡착제를 사용하여 이산화탄소($CO_2$), 질소 및 수분의 혼합기체로부터 $CO_2$를 수착하여 $CO_2$-cesium carbonate의 반응속도론을 구하기 위하여 $CO_2$의 파과곡선을 측정하였다. 비촉매 불균일반응계에서 반응속도론을 해석하기 위하여 $CO_2$의 파과곡선을 사용하여 비활성화 모델로부터 반응속도론을 구하고 $CO_2$의 파과곡선의 비선형해석으로부터 비활성화 모델에서 수착속도상수와 비활성속도상수를 구하였다.

• 한국분말재료학회지
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• 제14권2호
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• pp.145-149
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• 2007

Nanocrystalline transient aluminas (${\gamma}$-alumina) were coated on core particles (${\gamma}$-alumina) by a carbonate precipitation and thermal-assisted combustion, which is environmentally friend. The ammonium aluminum carbonate hydroxide (AACH) as a precursor for coating of transient aluminas was produced from precipitation reaction of ammonium aluminum sulfate and ammonium hydrogen carbonate. The crystalline size and morphology of the synthetic, AACH, were greatly dependent on pH and temperature. AACH with a size of 5 nm was coated on the core alumina particle at pH 9. whereas rod shape and large agglomerates were coated at pH 8 and 11, respectively. The AACH was tightly bonded coated on the core particle due to formation of surface complexes by the adsorption of carbonates, hydroxyl and ammonia groups on the surface of the core alumina powder. The synthetic precursor successfully converted to amorphous- and ${\gamma}$-alumina phase at low temperature through decomposition of surface complexes and thermal-assisted phase transformation.

• 한국세라믹학회지
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• 제35권6호
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• pp.559-568
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• 1998

Studies of preparation condition and characteristics of AUC(ammonium uranyl carbonate) were carried out to optimize AUC process with different reactor sizes and precipitation methos. As results four types of precipitates with different chemical compositions and morphologies were obtained from the reaction of {{{{ {(NH }_{4 }) { }_{2 } {CO }_{3 } }} with {{{{ {UO }_{2 }( {NO }_{3 }) { }_{2 } }} solution. A phase diagram has been made and crystal structure and chemical composition of each phase have been characterized by using SEM X-ray IR and thermal analysis. It was found that ammonium uranyl carbonate {{{{ {(NH }_{4 }) { }_{4 } {UO }_{2 } {(CO }_{3 }) { }_{3 } }} with monoclinic crystal morphology could be syn-thesized when the mole ratio of in {{{{ {(NH }_{4 }) { }_{2 } {CO }_{3 }/ {UO }_{2 } {(NO }_{3 }) { }_{2 } }} in the solution was higher than 5 Also a mechanism and a precipitating condition on rounding of the AUC particle were examined in the course of the AUC pre-cipitation. The rounding of the AUC particle was possible only by external circulation using pump not by internal circulation using agitator.

• 한국세라믹학회지
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• 제33권3호
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• pp.332-338
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• 1996

This study was investigated on the recycle feasibility of the waste AC(Ammonium Carbonate) solution produ-ced in a commercial AUC(Ammonium Uranyl Carbonate) conversion plant. AUC particles were produced with the AC solution which was prepared with AC solid-agent instead of ammonia and carbon-dioxide gases. As the results particles of monoclinic shapes has been obtained regardless of the pH change if the carbonate concentration is sufficient in the mother liquore. Also a lot of twinned or aggregated particles were formed in case of the increase of pH in the reaction system but not affected in the change of temperature. Consequen-tly the characteristics of the particles which converted for AUC were produced withAC solution to UO2, particles specific surface area shape sintered density and others were similar to that of the particles which were produced with gases only when the pellets are fabricated in the nuclear fuel manufacturing process So the waste AC solution which is produced in the commercial AUC conversion plant is possible to recycle.