Solution properties of perfluorinated anionic surfactants with divalent counterion of separate electric charges

Jyunya Masuda; Hiromichi Nakahara; Satoru Karasawa; Yoshikiyo Moroi; Osamu Shibata

doi:10.1021/la7005474

Solution properties of perfluorinated anionic surfactants with divalent counterion of separate electric charges

Jyunya Masuda, Hiromichi Nakahara, Satoru Karasawa, Yoshikiyo Moroi, Osamu Shibata

Chemo-Pharmaceutical Sciences

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

Novel Surfactants of perfluorinated double long-chain salts with divalent counterion of separate electric charge, 1,1-(l,ωw-alkanediyl)bispyridinium diperfluorononanoate (C_nBP(FC₉)₂, n = 2, 4, 6, 8) were newly synthesized. Their solution properties were investigated by surface tension measurement over the temperature range from 298.2 to 313.2 K, where magnesium diperfluorononanoate (Mg(FC₉)₂) was employed as a reference surfactant with divalent counterion of concentrated electric charge. From change of surface tension with concentration, the critical micelle concentration (CMC), surface excess (Γ), apparent molecular surface area (A), and -log(concentration to reduce surface tension of water by 20 mN m^-1) (pC₂₀) were determined. The CMC values of C_nBP(FC₉)₂ decreased with increasing charge separation and with increasing temperature, where the values of C _nBP(FC₉)₂ were much smaller than those of Mg(FC₉)₂. In addition, the pC₂₀ values of the former were also much larger than those of the latter. These results indicate a strong influence of the extent of charge separation or the spacer length of the counterions upon surface activity of the fluorinated surfactants. The surface excess or the corresponding apparent molecular surface area monotonously changed with the spacer length (n ≤ 6), whereas the behavior for n = 8 was much different from the other C_nBP(FC₉)₂ due to conformational change in the in-between alkanediyl chain. The entropy changes (αs) for the surface adsorption or condensation were found to be mostly negative for C_nBP(FC₉)₂, where the changes approached zero with an increase in the charge separation. On the other hand, the changes for Mg(FC₉)₂ were positive over the whole concentration below the CMC. In addition, Brewster angle microscopy indicated no condensation of the present surfactants just at the air/solution interface.

Original language	English
Pages (from-to)	8778-8783
Number of pages	6
Journal	Langmuir
Volume	23
Issue number	17
DOIs	https://doi.org/10.1021/la7005474
Publication status	Published - Aug 14 2007

All Science Journal Classification (ASJC) codes

Materials Science(all)
Condensed Matter Physics
Surfaces and Interfaces
Spectroscopy
Electrochemistry

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10.1021/la7005474

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@article{80e84f4adb5543bc9b6b405ca30f8857,

title = "Solution properties of perfluorinated anionic surfactants with divalent counterion of separate electric charges",

abstract = "Novel Surfactants of perfluorinated double long-chain salts with divalent counterion of separate electric charge, 1,1-(l,ωw-alkanediyl)bispyridinium diperfluorononanoate (CnBP(FC9)2, n = 2, 4, 6, 8) were newly synthesized. Their solution properties were investigated by surface tension measurement over the temperature range from 298.2 to 313.2 K, where magnesium diperfluorononanoate (Mg(FC9)2) was employed as a reference surfactant with divalent counterion of concentrated electric charge. From change of surface tension with concentration, the critical micelle concentration (CMC), surface excess (Γ), apparent molecular surface area (A), and -log(concentration to reduce surface tension of water by 20 mN m-1) (pC20) were determined. The CMC values of CnBP(FC9)2 decreased with increasing charge separation and with increasing temperature, where the values of C nBP(FC9)2 were much smaller than those of Mg(FC9)2. In addition, the pC20 values of the former were also much larger than those of the latter. These results indicate a strong influence of the extent of charge separation or the spacer length of the counterions upon surface activity of the fluorinated surfactants. The surface excess or the corresponding apparent molecular surface area monotonously changed with the spacer length (n ≤ 6), whereas the behavior for n = 8 was much different from the other CnBP(FC9)2 due to conformational change in the in-between alkanediyl chain. The entropy changes (αs) for the surface adsorption or condensation were found to be mostly negative for CnBP(FC9)2, where the changes approached zero with an increase in the charge separation. On the other hand, the changes for Mg(FC9)2 were positive over the whole concentration below the CMC. In addition, Brewster angle microscopy indicated no condensation of the present surfactants just at the air/solution interface.",

author = "Jyunya Masuda and Hiromichi Nakahara and Satoru Karasawa and Yoshikiyo Moroi and Osamu Shibata",

year = "2007",

month = aug,

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doi = "10.1021/la7005474",

language = "English",

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T1 - Solution properties of perfluorinated anionic surfactants with divalent counterion of separate electric charges

AU - Masuda, Jyunya

AU - Nakahara, Hiromichi

AU - Karasawa, Satoru

AU - Moroi, Yoshikiyo

AU - Shibata, Osamu

PY - 2007/8/14

Y1 - 2007/8/14

N2 - Novel Surfactants of perfluorinated double long-chain salts with divalent counterion of separate electric charge, 1,1-(l,ωw-alkanediyl)bispyridinium diperfluorononanoate (CnBP(FC9)2, n = 2, 4, 6, 8) were newly synthesized. Their solution properties were investigated by surface tension measurement over the temperature range from 298.2 to 313.2 K, where magnesium diperfluorononanoate (Mg(FC9)2) was employed as a reference surfactant with divalent counterion of concentrated electric charge. From change of surface tension with concentration, the critical micelle concentration (CMC), surface excess (Γ), apparent molecular surface area (A), and -log(concentration to reduce surface tension of water by 20 mN m-1) (pC20) were determined. The CMC values of CnBP(FC9)2 decreased with increasing charge separation and with increasing temperature, where the values of C nBP(FC9)2 were much smaller than those of Mg(FC9)2. In addition, the pC20 values of the former were also much larger than those of the latter. These results indicate a strong influence of the extent of charge separation or the spacer length of the counterions upon surface activity of the fluorinated surfactants. The surface excess or the corresponding apparent molecular surface area monotonously changed with the spacer length (n ≤ 6), whereas the behavior for n = 8 was much different from the other CnBP(FC9)2 due to conformational change in the in-between alkanediyl chain. The entropy changes (αs) for the surface adsorption or condensation were found to be mostly negative for CnBP(FC9)2, where the changes approached zero with an increase in the charge separation. On the other hand, the changes for Mg(FC9)2 were positive over the whole concentration below the CMC. In addition, Brewster angle microscopy indicated no condensation of the present surfactants just at the air/solution interface.

AB - Novel Surfactants of perfluorinated double long-chain salts with divalent counterion of separate electric charge, 1,1-(l,ωw-alkanediyl)bispyridinium diperfluorononanoate (CnBP(FC9)2, n = 2, 4, 6, 8) were newly synthesized. Their solution properties were investigated by surface tension measurement over the temperature range from 298.2 to 313.2 K, where magnesium diperfluorononanoate (Mg(FC9)2) was employed as a reference surfactant with divalent counterion of concentrated electric charge. From change of surface tension with concentration, the critical micelle concentration (CMC), surface excess (Γ), apparent molecular surface area (A), and -log(concentration to reduce surface tension of water by 20 mN m-1) (pC20) were determined. The CMC values of CnBP(FC9)2 decreased with increasing charge separation and with increasing temperature, where the values of C nBP(FC9)2 were much smaller than those of Mg(FC9)2. In addition, the pC20 values of the former were also much larger than those of the latter. These results indicate a strong influence of the extent of charge separation or the spacer length of the counterions upon surface activity of the fluorinated surfactants. The surface excess or the corresponding apparent molecular surface area monotonously changed with the spacer length (n ≤ 6), whereas the behavior for n = 8 was much different from the other CnBP(FC9)2 due to conformational change in the in-between alkanediyl chain. The entropy changes (αs) for the surface adsorption or condensation were found to be mostly negative for CnBP(FC9)2, where the changes approached zero with an increase in the charge separation. On the other hand, the changes for Mg(FC9)2 were positive over the whole concentration below the CMC. In addition, Brewster angle microscopy indicated no condensation of the present surfactants just at the air/solution interface.

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Solution properties of perfluorinated anionic surfactants with divalent counterion of separate electric charges

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