Variable-pressure kinetic and equilibrium study of the complexation of the beryllium(II) ion with 4-isopropyltropolone in acidic aqueous solution

Masahiko Inamo, Koji Ishihara, Shigenobu Funahashi, Yves Ducommun, André E. Merbach, Motoharu Tanaka

    Research output: Contribution to journalArticle

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    Abstract

    Kinetics and equilibria for the formation and dissociation of the 1:1 complex of the beryllium(II) ion with 4-isopropyltropolone (Hipt) in acidic aqueous solution have been studied spectrophotometrically at various temperatures and pressures at an ionic strength of 0.100 M ((Na,H)ClO4). Equilibrium measurements gave the following results: K = [Be(ipt)+][H+][Be2+]-1[Hipt] -1 = 1.17 ± 0.06 (25.0°C), ΔH° = 2.4 ± 0.3 kJ mol-1, ΔS° = 9.2 ± 1.1 J K-1 mol-1, ΔV° = +5.3 ± 0.2 cm3 mol-1 (25.0°C). The reaction volumes for the proton dissociation of Hipt and for the complexation of Be2+ with ipt are -8.2 ± 0.5 and +13.5 ± 0.6 cm3 mol-1, respectively, at 25.0°C. The rate constants and activation parameters for formation and dissociation of the complex are as follows: kf = 58.1 ± 0.5 M-1 s-1 (25.0°C), kr = 49.8 ± 0.5 M-1 s-1 (25.0°C), ΔHf = 38.1 ± 0.4 kJ mol-1, ΔHr = 35.7 ± 0.4 kJ mol-1, ΔSf = -83.5 ± 1.3 J K-1 mol-1, ΔSr = -92.7 ± 1.2 J K-1 mol-1, ΔVf = 7.1 ± 0.2 cm3 mol-1 (25.0°C), ΔVr = -12.4 ± 0.2 cm3 mol-1 (25.0°C). The negative values of entropy and volume of activation indicate that the reaction proceeds with an associative mode of activation.

    Original languageEnglish
    Pages (from-to)1580-1583
    Number of pages4
    JournalInorganic Chemistry
    Volume30
    Issue number7
    Publication statusPublished - 1991

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    Beryllium
    beryllium
    Complexation
    Chemical activation
    activation
    dissociation
    Ions
    aqueous solutions
    Kinetics
    kinetics
    ions
    Ionic strength
    Protons
    Rate constants
    Entropy
    entropy
    protons
    beta-thujaplicin
    Temperature
    temperature

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Variable-pressure kinetic and equilibrium study of the complexation of the beryllium(II) ion with 4-isopropyltropolone in acidic aqueous solution. / Inamo, Masahiko; Ishihara, Koji; Funahashi, Shigenobu; Ducommun, Yves; Merbach, André E.; Tanaka, Motoharu.

    In: Inorganic Chemistry, Vol. 30, No. 7, 1991, p. 1580-1583.

    Research output: Contribution to journalArticle

    Inamo, Masahiko ; Ishihara, Koji ; Funahashi, Shigenobu ; Ducommun, Yves ; Merbach, André E. ; Tanaka, Motoharu. / Variable-pressure kinetic and equilibrium study of the complexation of the beryllium(II) ion with 4-isopropyltropolone in acidic aqueous solution. In: Inorganic Chemistry. 1991 ; Vol. 30, No. 7. pp. 1580-1583.
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    title = "Variable-pressure kinetic and equilibrium study of the complexation of the beryllium(II) ion with 4-isopropyltropolone in acidic aqueous solution",
    abstract = "Kinetics and equilibria for the formation and dissociation of the 1:1 complex of the beryllium(II) ion with 4-isopropyltropolone (Hipt) in acidic aqueous solution have been studied spectrophotometrically at various temperatures and pressures at an ionic strength of 0.100 M ((Na,H)ClO4). Equilibrium measurements gave the following results: K = [Be(ipt)+][H+][Be2+]-1[Hipt] -1 = 1.17 ± 0.06 (25.0°C), ΔH° = 2.4 ± 0.3 kJ mol-1, ΔS° = 9.2 ± 1.1 J K-1 mol-1, ΔV° = +5.3 ± 0.2 cm3 mol-1 (25.0°C). The reaction volumes for the proton dissociation of Hipt and for the complexation of Be2+ with ipt are -8.2 ± 0.5 and +13.5 ± 0.6 cm3 mol-1, respectively, at 25.0°C. The rate constants and activation parameters for formation and dissociation of the complex are as follows: kf = 58.1 ± 0.5 M-1 s-1 (25.0°C), kr = 49.8 ± 0.5 M-1 s-1 (25.0°C), ΔHf ‡ = 38.1 ± 0.4 kJ mol-1, ΔHr ‡ = 35.7 ± 0.4 kJ mol-1, ΔSf ‡ = -83.5 ± 1.3 J K-1 mol-1, ΔSr ‡ = -92.7 ± 1.2 J K-1 mol-1, ΔVf ‡ = 7.1 ± 0.2 cm3 mol-1 (25.0°C), ΔVr ‡ = -12.4 ± 0.2 cm3 mol-1 (25.0°C). The negative values of entropy and volume of activation indicate that the reaction proceeds with an associative mode of activation.",
    author = "Masahiko Inamo and Koji Ishihara and Shigenobu Funahashi and Yves Ducommun and Merbach, {Andr{\'e} E.} and Motoharu Tanaka",
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    T1 - Variable-pressure kinetic and equilibrium study of the complexation of the beryllium(II) ion with 4-isopropyltropolone in acidic aqueous solution

    AU - Inamo, Masahiko

    AU - Ishihara, Koji

    AU - Funahashi, Shigenobu

    AU - Ducommun, Yves

    AU - Merbach, André E.

    AU - Tanaka, Motoharu

    PY - 1991

    Y1 - 1991

    N2 - Kinetics and equilibria for the formation and dissociation of the 1:1 complex of the beryllium(II) ion with 4-isopropyltropolone (Hipt) in acidic aqueous solution have been studied spectrophotometrically at various temperatures and pressures at an ionic strength of 0.100 M ((Na,H)ClO4). Equilibrium measurements gave the following results: K = [Be(ipt)+][H+][Be2+]-1[Hipt] -1 = 1.17 ± 0.06 (25.0°C), ΔH° = 2.4 ± 0.3 kJ mol-1, ΔS° = 9.2 ± 1.1 J K-1 mol-1, ΔV° = +5.3 ± 0.2 cm3 mol-1 (25.0°C). The reaction volumes for the proton dissociation of Hipt and for the complexation of Be2+ with ipt are -8.2 ± 0.5 and +13.5 ± 0.6 cm3 mol-1, respectively, at 25.0°C. The rate constants and activation parameters for formation and dissociation of the complex are as follows: kf = 58.1 ± 0.5 M-1 s-1 (25.0°C), kr = 49.8 ± 0.5 M-1 s-1 (25.0°C), ΔHf ‡ = 38.1 ± 0.4 kJ mol-1, ΔHr ‡ = 35.7 ± 0.4 kJ mol-1, ΔSf ‡ = -83.5 ± 1.3 J K-1 mol-1, ΔSr ‡ = -92.7 ± 1.2 J K-1 mol-1, ΔVf ‡ = 7.1 ± 0.2 cm3 mol-1 (25.0°C), ΔVr ‡ = -12.4 ± 0.2 cm3 mol-1 (25.0°C). The negative values of entropy and volume of activation indicate that the reaction proceeds with an associative mode of activation.

    AB - Kinetics and equilibria for the formation and dissociation of the 1:1 complex of the beryllium(II) ion with 4-isopropyltropolone (Hipt) in acidic aqueous solution have been studied spectrophotometrically at various temperatures and pressures at an ionic strength of 0.100 M ((Na,H)ClO4). Equilibrium measurements gave the following results: K = [Be(ipt)+][H+][Be2+]-1[Hipt] -1 = 1.17 ± 0.06 (25.0°C), ΔH° = 2.4 ± 0.3 kJ mol-1, ΔS° = 9.2 ± 1.1 J K-1 mol-1, ΔV° = +5.3 ± 0.2 cm3 mol-1 (25.0°C). The reaction volumes for the proton dissociation of Hipt and for the complexation of Be2+ with ipt are -8.2 ± 0.5 and +13.5 ± 0.6 cm3 mol-1, respectively, at 25.0°C. The rate constants and activation parameters for formation and dissociation of the complex are as follows: kf = 58.1 ± 0.5 M-1 s-1 (25.0°C), kr = 49.8 ± 0.5 M-1 s-1 (25.0°C), ΔHf ‡ = 38.1 ± 0.4 kJ mol-1, ΔHr ‡ = 35.7 ± 0.4 kJ mol-1, ΔSf ‡ = -83.5 ± 1.3 J K-1 mol-1, ΔSr ‡ = -92.7 ± 1.2 J K-1 mol-1, ΔVf ‡ = 7.1 ± 0.2 cm3 mol-1 (25.0°C), ΔVr ‡ = -12.4 ± 0.2 cm3 mol-1 (25.0°C). The negative values of entropy and volume of activation indicate that the reaction proceeds with an associative mode of activation.

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