Competitive Adsorption of Polyvinylpyrrolidone with <I>n</I>-Alkyl Alcohols at the Mercury/Solution Interface
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概要
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Competitive adsorption of polyvinylpyrrolidone (PVP, \bar<I>M</I>=10000) with <I>n</I>-hexanol, <I>n</I>-pentanol, or <I>n</I>-butanol was examined by observation of the differential capacity at the mercury interface in 1 N sulfuric acid. Adsorption of PVP coexistent with alcohol hardly differed from the single adsorption<SUP>1)</SUP> controlled by its diffusion. The competitive adsorption curve of <I>C</I> (differential capacity) <I>vs.</I> <I>t</I><SUP>1⁄2</SUP> (adsorption time) was expected from the sum of the individual capacity depressions by the single adsorption at −0.5 or −0.6 V (SCE) and the expected curve of <I>C</I> <I>vs.</I> <I>t</I><SUP>1⁄2</SUP> was compared with the curve observed. The competitive behavior of alcohol coexistent with PVP was examined by the relation "θ<SUB>Alc</SUB><SUP>com</SUP> (coverage of coexistent alcohol) <I>vs.</I> <I>t</I><SUP>1⁄2</SUP>" at −0.5 or −0.6 V (SCE), where θ<SUB>Alc</SUB><SUP>com</SUP> was estimated from the difference between the differential capacities with and without PVP, in view of the fact that behavior of PVP is nearly independent of the coexistent alcohol. The results are discussed in terms of four types of models assumed for the competitive behavior of coexistent alcohols with different adsorbability. It is considered that the alcohol is replaced with PVP as soon as the latter reaches the interface by diffusion, the adsorption equilibrium of an alcohol being achieved immediately. The relation θ<SUB>Alc</SUB><SUP>com</SUP>=(1−θ<SUB>pvp</SUB>)θ<SUB>Alc</SUB> holds in the case of <I>n</I>-butanol coxistent with PVP, where θ<SUB>PVP</SUB>, θ<SUB>Alc</SUB>, and θ<SUB>Alc</SUB><SUP>com</SUP> are coverages due to the single adsorption of PVP and butanol and to the competitive adsorption of butanol, respectively. The tendency of alcohol to be replaced with PVP is inversely proportional to its adsorption coefficient. <I>n</I>-Butanol was most sensitive to the coexistence of PVP.
- 公益社団法人 日本化学会の論文
著者
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Iida Yasuo
Applied Electrochemical Laboratory, Graduate School of Science and Engineering, Waseda University
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Ohsaka Tetsuya
Applied Electrochemical Laboratory, Graduate School of Science and Engineering, Waseda University
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Yoshida Tadashi
Applied Electrochemical Laboratory, Graduate School of Science and Engineering, Waseda University
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