• Korean Chemical Engineering Research
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• v.57 no.4
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• pp.512-518
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• 2019

To develop a membrane electrode assembly (MEA) with lower Pt loading and higher performance in proton exchange membrane fuel cells (PEMFCs), it is an important research issue to understand interfacial structure of Pt/C catalyst and ionomer and design the catalyst layer structure. In this study, we prepared short-side-chain Nafion-based ionomer dispersion using propylene glycol (PG) as a solvent instead of water which is commonly used as a solvent for commercially available ionomers. Cathode catalyst layers with different ionomer content from 20 to 35 wt% were prepared using the ionomer dispersion for the fabrication of four different MEAs, and their fuel cell performance was evaluated. As the ionomer content increased to 35 wt%, the performance of the prepared MEAs increased proportionally, unlike the commercially available water-based ionomer, which exhibited an optimum at about 25 wt%. Small size micelles and slow evaporation of PG in the ionomer dispersion were effective in proton transfer by inducing the formation of a uniformly structured catalyst layer, but the low oxygen permeability problem of the PG-based ionomer film should be resolved to improve the MEA performance.

• Applied Chemistry for Engineering
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• v.22 no.4
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• pp.416-422
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• 2011

In this study, the effect of cosurfactant on the phase equilibrium and dynamic behavior was studied in systems containing NP7 nonionic surfactant solutions and nonpolar hydrocarbon oils. All cosurfactants used during this study such as n-pentanol, n-octanol and n-decanol acted as a hydrophobic additive and thus promoted the transition from an oil in water (O/W) microemulsion (${\mu}E$) in equilibrium with an excess oil phase to a three-phase region containing excess water, excess oil, and a middle-phase microemulsion and further to a water in oil (W/O) ${\mu}E$ in equilibrium with the excess water phase. The transition temperature was found to decrease with both increases in the chain length and amount of addition of a cosurfactant. Dynamic behavior studies under O/W ${\mu}E$ conditions showed that an oil drop size decreased with time due to the solubilization into micelles. On the other hand, both the spontaneous emulsification of water into the oil phase and the expansion of oil drop were observed under W/O ${\mu}E$ conditions because of the diffusion of surfactant and water into the oil phase. Under conditions of a three-phase region including a middle-phase ${\mu}E$, both the rapid solubilization and emulsification of the oil into aqueous solutions were found mainly due to the existence of ultra-low interfacial tension. Dynamic interfacial tension measurements have been found to be in a good agreement with dynamic behavior results.

• Journal of the Korean Chemical Society
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• v.29 no.5
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• pp.522-532
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• 1985

The reactions of p-nitrophenyldiphenylphosphate (p-NPDPP) with anions of benzimidazole (BI) and its 2-alkyl derivatives (R-BI) are strongly catalyzed by the micelles of cetyltrimethyl ammonium bromide (CTABr). On the other hand, the first order rate constants $(k'_{R-BI^-})$ and the second order rate constants $(k_{m(R-BI^-)})$ of the reactions mediated by R-$BI^-$in the micellar pseudophase are much smaller than those mediated by $BI^-$. In order to explain the slower rates of the micellar reactions mediated by R-$BI^-$, we compared the concentration-ratios ([R-$BI^-$]/[$BI^-$]) with the first order rate constant-ratios $(k'_{R-BI^-}/k'_{BI^-})$ and the second order constant-ratios $(k_{m(R-BI^-)}/k_{m(BI^-)})$ for the reactions taking place in the micellar pseudophase. The rate constant-ratios were much smaller than the concentration-ratios. For example in a 5 ${\times}10^{-4}$M butyl-BI solution, the two ratios were 0.089 and 0.430 (for the first order) respectively, and in a $10^{-4}$M butyl-BI solution the former was 0.100 (for the second order). This predicts that the reactivities of R-$BI^-$ in the micellar pseudophase are much smaller than that of $BI^-$. Based on the values of several kinetic parameters measured for dephosphorylation of p-NPDPP mediated by R-$BI^-$, a schemetic model is proposed. Due to the hydrophobicity and the steric effect of the alkyl substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long cetyl groups of CTABr. Consequently, the movements of R-$BI^-$ bound to the micelle should be restricted, leading to decreased collison frequencies between the nucleophiles and p-NPDPP. We refer this as an "anchor effect". This effect became more predominent when a larger alky group in R-BI was employed and when a greater concentration of R-BI was used.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.753-762
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• 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 the Korean Geotechnical Society
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• v.15 no.2
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• pp.153-164
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• 1999

The solubilization of BTEX was evaluated in aqueous surfactant solutions with and without several additives. Anionic surfactant(Sodium Dodecyl Sulfate, SDS) and nonionic surfactants (NEODOL(equation omitted)25-3 and $SOFTANOL\circledR-90$ were used as test surfactants. The effects of surfactant HLB(Hydrophile-Lipophile Balance) Number and hydrocarbon molar volume and polarity of BTEX on the MSR(Molar Solubilization Ratio), micelle-water partition coefficient of BTEX, and CMC(C,itical Micelle Concentration) were investigated. Optimizing treatment conditions applicable to enhanced solubilization was also studied by manupulating salinity or electrolyte control with additives of ethyl alcohol, hydrotrope, and electrolyte solution. The most effective surfactant for solubilization was found $SOFTANOL\circledR-90$, since HLB number of 13.6 is similar to those values of BTEX ranging between 11.4 and 12.2, which was also proved experimentally. Ethyl alchohol of 3% was the most effective additives in reducing CMC and improving solubilization among the conditions using SDS, NEODOL(equation omitted)25-3, and $SOFTANOL\circledR-90$ with three additives. The partitioning of BTEX between surfactant micelles and aqueous solutions was characterized by a mole fraction micelle-phase/aqueous phase partion coefficient, $K_m$. Values of log $K_m$. for BTEX compounds in surfactant solutions of this study range from 2.95 to 3.76(100mM SDS) and 2.95 to 3.49(117mM $SOFTANOL\circledR-90$. Log $K_m$ appears to be a linear function of log $K_{ow}$ for SDS and $SOFTANOL\circledR-90$. A knowledge of partitioning of BTEX in aqueous surfactant system can be a prerequisite for the understanding of the behavior of hydrophobic organic compounds in soil-water systems in which surfactants play a role in remediation of contaminated soil and facilitated transport.