• Journal of Environmental Science International
• /
• v.20 no.1
• /
• pp.119-126
• /
• 2011

In this study, reaction model and reactions rate accelerated by o-iodosobenzoate ion(IB$^{\ominus}$) on hydrolysis reaction of p-nitrophenyl valate(NPV) using ethyl tri-octyl ammonium mesylate(ETAMs) for quaternary ammonium salts, the phase transfer catalysis(PTC) reagent, were investigated. The effect of IB$^{\ominus}$ on hydrolysis reaction rate constant of NPV was weak without ETAMs solutions. Otherwise, in ETAMs solutions, the hydrolysis reactions exhibit higher first order kinetics with respect to the nucleophile, IB$^{\ominus}$, and ETAMs, suggesting that reactions are occurring in small aggregates of the three species including the substrate(NPV), whereas the reaction of NPV with OH$^{\ominus}$ is not catalyzed by ETAMs. Different concentrations of NPV were tested to measure the change of rate constants to investigate the effect of NPV as substrate and the results showed that the effect was weak. This means the reaction would be the first order kinetics with respect to the nucleophile. This behavior for the drastic rate-enhancement of the hydrolysis is referred as 'Aggregation complex model' for reaction of hydrophobic organic ester with o-iodosobenzoate ion(IB$^{\ominus}$) in hydrophobic quarternary ammonium salt(ETAMs) solutions.

• Proceedings of the Korean Environmental Sciences Society Conference
• /
• 2019.10a
• /
• pp.147-147
• /
• 2019

• Journal of Environmental Science International
• /
• v.14 no.2
• /
• pp.241-249
• /
• 2005

This study deals with micellar effects on dephosphorylation of diphenyl-4- nitrophenylphosphate (DPNPPH), diphenyl-4-nitrophenylphosphinate (DPNPlN) and isopropylphenyl-4-nitrophenyl phosphinate (IPNPlN) mediated by $OH^\Theta$ or o-iodosobenzoate ion $(IB^\Theta)$ in aqueous and CTAX solutions. Dephosphorylation of DPNPPH, DPNPIN and IPNPIN mediated by $OH^\Theta$ or o-iodosobenzoate ion $(IB^\Theta)$ is relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, much accelerated because CTAX micelles can accommodate both reactants in their Stem layer in which they can easily react, while hydrophilic $OH^\Theta\;(or\;IB^\Theta)$ and hydrophobic substrates are not mixed in water. Even though the concentrations $(>10^{-3}\;M)\;of\;OH^\Theta\;(or\;IB^\Theta)$ in CTAX solutions are much larger amounts than those $(6\times10^{-6}\;M)$ of substrates, the rate constants of the dephosphorylations are largely influenced by the change of concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACI is more effective on the dephosphorylation of substrates than CTABr due to easier expelling of $Cl^\Theta$ ion by $OH^\Theta\;(or\;IB^\Theta)$ ion from the micelle, because of easier solvation of $Cl^\Theta$ ion by water molecules. The reactivity of IPNPlN with $OH^\Theta\;(or\;IB^\Theta)$ is lower than that of DPNPlN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles.

• Journal of the Korean Chemical Society
• /
• v.38 no.10
• /
• pp.753-762
• /
• 1994

Dephosphorylation of diphenyl- or isopropylphenyl-4-nitrophenylphosphinate (DPNPIN or IPNPIN) mediated by $OH^-$ or o-iodosobenzoate ion ($IB^-$) are relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, very accelerated, because CTAX micelles can accommodate both reactants in their Stern layer in which they can easily react, while hydrophilic $OH^-$(or $IB^-$) and hydrophobic phosphinates are not mixed in water. Even though the concentrations (> $10^{-3}$ M) of $OH^-$(or $IB^-$) in CTAX solutions are much larger amounts than those ($6{\times}10^{-6}$ M) of phosphinates, the rate constants of the dephosphorylations are largely influenced by change of the concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACl is more effective on the dephosphorylation of DPNPIN (or IPNPIN) than CTABr due to easier expelling of $Cl^-$ ion by $OH^-$(or $IB^-$) ion from the micelle, because of easier solvation $Cl^-$ ion by water molecules. The reactivity of IPNPIN with $OH^-$(or $IB^-$) is lower than that of DPNPIN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles. The mechanism of reaction of IPNPIN with IB- ion concluded as 'nucleophilic' instead of 'general basic' by a trapping experiment and a measured kinetic isotope effect.

• Journal of Environmental Science International
• /
• v.15 no.5
• /
• pp.485-491
• /
• 2006

In the aqueous solutions the dephosphorylations of isopropyl phenyl-4-nitrophenyl phosphinate(IPNPIN) mediated by hydroxide$(OH^{\theta})$ and o-iodosobenzoate$(IB^{\theta})$ ions ate relatively slow, because of hydrophobicity of the substrate, and however it appears that $OH^{\theta}$ is inherently better nucleophile than $IB^{\theta}$, which is more soft ion. On the other hand, in cetyltrimetyiammonium bromide(CTABr) solutions which contain cationic micelles, the dephosphorylations of IPNPIN mediated by $OH^{\theta}$ or $IB^{\theta}$ ate very accelerated to 120 or 100,000 times as compared with those in the aqueous solutions. The values of pseudo first order rate constants reach a maximum with increasing. Such rate maxima are typical of micellar catalysed bimolecular reactions and the rise in rate constant followed by a gradual decrese is characteristic of reactions of hydrophobic substrates. In the cationic micellar solutions of CTABr, $IB^{\theta}$ accelerates the reactions much more than that $OH^{\theta}$ does. The reason seems that $IB^{\theta}$ which is more hydrophobic and soft ion than $OH^{\theta}$ is more easily moved into the Stern layer of the CTABr micelles than $OH^{\theta}$. In the anionic micellar solutions of sodium dodecyl sulfate(SDS), the dephosrhorylations of IPNPIN ate slower than those in aqeous solutions. It means that $OH^{\theta}$ or $IB^{\theta}$ cannot easily move and approach to the Stern layer of the micelle in which almost all the hydrophobic substrate are located and which has a negative circumstance.