Solubility in silver amalgams and deviations from Raoult's law

Douglas Rennie Hudson

    Research output: Contribution to journalArticle

    Abstract

    The validity of direct determination of the solubility of silver in mercury is established from theoretical and practical considerations, and error due to using a sealed vessel is shown to be negligible. Values of solubility from room temperature up to 450°C., i.e., well above the boiling point of mercury at normal pressure, are reported. From liquidus data it is shown that solubility right up to the melting point of silver can be represented very closely by three straight lines: log10N = 0.67035 - 1134.7T-1. . . .up to 330°C. log10 N = 2.9065 - 2481.8T-1. . . .330° to 450°C. log10 N = 0.7441 - 918.2T-1. . . .450°C. to the melting point of silver Their intersections, however, have no relation to the peritectic formation temperatures of Ag5Hg4 at 276°C. and Ag5Hg8 at 127°C., and these points do not appear at all on the logarithmic curve. At low temperatures the solubility is about one-fortieth of that calculated from the elementary equation established by Schröder in 1893: log10 N = Hf/R(1/Tm - 1/T) or about one-hundredth if Hf is corrected for temperature variation. Possible explanations for this are unconvincing. The approximate expression derived from consideration of unlike atoms RT log10 (a1/N1) = KN22 (a being the Schröder solubility) fits the experimental curve very well up to 340°C. if K = 465, as calculated from solubility at the steam point; and even after its departure gives an analogous reversed-S curve. A roughly parallel curve holds for the solubility of silver in liquid tin. In the more exact expression RT log10 (a1/N1) = V1 (N2V2/N2V2 + N1V1)2 [P1/21 - P1/22]2 the observed solubilities lead to a figure of 14 for [P1/21 - P1/22] compared with approximate values of 23.8, 40.9, 47.3, 18.2, 39.1, derived from diverse physical properties. The deviation from theoretical solubility is thus only a half or a third of what might be expected from consideration of the internal pressures of the two metals. It is concluded that the mutual attraction within a pair of unlike atoms is greater than the geometric mean of corresponding attractions within pairs of like atoms, in sharp contrast to the behaviour of most organic molecules and to previous conjectures, on theoretical grounds. A convenient method is described for determining strain in glass vessels after blowpipe manipulation, by use of polarized light.

    LanguageEnglish
    Pages483-506
    Number of pages24
    JournalJournal of Physical Chemistry
    Volume49
    Issue number5
    Publication statusPublished - 1945

    Fingerprint

    Raoult law
    mercury amalgams
    solubility
    silver
    deviation
    attraction
    melting points
    vessels
    curves
    S curves
    atoms
    internal pressure
    liquidus
    steam
    boiling
    intersections
    polarized light
    manipulators
    tin
    physical properties

    Cite this

    Hudson, Douglas Rennie. / Solubility in silver amalgams and deviations from Raoult's law. In: Journal of Physical Chemistry. 1945 ; Vol. 49, No. 5. pp. 483-506.
    @article{4ec82639350846c48bbe2b959e0dd6e0,
    title = "Solubility in silver amalgams and deviations from Raoult's law",
    abstract = "The validity of direct determination of the solubility of silver in mercury is established from theoretical and practical considerations, and error due to using a sealed vessel is shown to be negligible. Values of solubility from room temperature up to 450°C., i.e., well above the boiling point of mercury at normal pressure, are reported. From liquidus data it is shown that solubility right up to the melting point of silver can be represented very closely by three straight lines: log10N = 0.67035 - 1134.7T-1. . . .up to 330°C. log10 N = 2.9065 - 2481.8T-1. . . .330° to 450°C. log10 N = 0.7441 - 918.2T-1. . . .450°C. to the melting point of silver Their intersections, however, have no relation to the peritectic formation temperatures of Ag5Hg4 at 276°C. and Ag5Hg8 at 127°C., and these points do not appear at all on the logarithmic curve. At low temperatures the solubility is about one-fortieth of that calculated from the elementary equation established by Schr{\"o}der in 1893: log10 N = Hf/R(1/Tm - 1/T) or about one-hundredth if Hf is corrected for temperature variation. Possible explanations for this are unconvincing. The approximate expression derived from consideration of unlike atoms RT log10 (a1/N1) = KN22 (a being the Schr{\"o}der solubility) fits the experimental curve very well up to 340°C. if K = 465, as calculated from solubility at the steam point; and even after its departure gives an analogous reversed-S curve. A roughly parallel curve holds for the solubility of silver in liquid tin. In the more exact expression RT log10 (a1/N1) = V1 (N2V2/N2V2 + N1V1)2 [P1/21 - P1/22]2 the observed solubilities lead to a figure of 14 for [P1/21 - P1/22] compared with approximate values of 23.8, 40.9, 47.3, 18.2, 39.1, derived from diverse physical properties. The deviation from theoretical solubility is thus only a half or a third of what might be expected from consideration of the internal pressures of the two metals. It is concluded that the mutual attraction within a pair of unlike atoms is greater than the geometric mean of corresponding attractions within pairs of like atoms, in sharp contrast to the behaviour of most organic molecules and to previous conjectures, on theoretical grounds. A convenient method is described for determining strain in glass vessels after blowpipe manipulation, by use of polarized light.",
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    Solubility in silver amalgams and deviations from Raoult's law. / Hudson, Douglas Rennie.

    In: Journal of Physical Chemistry, Vol. 49, No. 5, 1945, p. 483-506.

    Research output: Contribution to journalArticle

    TY - JOUR

    T1 - Solubility in silver amalgams and deviations from Raoult's law

    AU - Hudson, Douglas Rennie

    PY - 1945

    Y1 - 1945

    N2 - The validity of direct determination of the solubility of silver in mercury is established from theoretical and practical considerations, and error due to using a sealed vessel is shown to be negligible. Values of solubility from room temperature up to 450°C., i.e., well above the boiling point of mercury at normal pressure, are reported. From liquidus data it is shown that solubility right up to the melting point of silver can be represented very closely by three straight lines: log10N = 0.67035 - 1134.7T-1. . . .up to 330°C. log10 N = 2.9065 - 2481.8T-1. . . .330° to 450°C. log10 N = 0.7441 - 918.2T-1. . . .450°C. to the melting point of silver Their intersections, however, have no relation to the peritectic formation temperatures of Ag5Hg4 at 276°C. and Ag5Hg8 at 127°C., and these points do not appear at all on the logarithmic curve. At low temperatures the solubility is about one-fortieth of that calculated from the elementary equation established by Schröder in 1893: log10 N = Hf/R(1/Tm - 1/T) or about one-hundredth if Hf is corrected for temperature variation. Possible explanations for this are unconvincing. The approximate expression derived from consideration of unlike atoms RT log10 (a1/N1) = KN22 (a being the Schröder solubility) fits the experimental curve very well up to 340°C. if K = 465, as calculated from solubility at the steam point; and even after its departure gives an analogous reversed-S curve. A roughly parallel curve holds for the solubility of silver in liquid tin. In the more exact expression RT log10 (a1/N1) = V1 (N2V2/N2V2 + N1V1)2 [P1/21 - P1/22]2 the observed solubilities lead to a figure of 14 for [P1/21 - P1/22] compared with approximate values of 23.8, 40.9, 47.3, 18.2, 39.1, derived from diverse physical properties. The deviation from theoretical solubility is thus only a half or a third of what might be expected from consideration of the internal pressures of the two metals. It is concluded that the mutual attraction within a pair of unlike atoms is greater than the geometric mean of corresponding attractions within pairs of like atoms, in sharp contrast to the behaviour of most organic molecules and to previous conjectures, on theoretical grounds. A convenient method is described for determining strain in glass vessels after blowpipe manipulation, by use of polarized light.

    AB - The validity of direct determination of the solubility of silver in mercury is established from theoretical and practical considerations, and error due to using a sealed vessel is shown to be negligible. Values of solubility from room temperature up to 450°C., i.e., well above the boiling point of mercury at normal pressure, are reported. From liquidus data it is shown that solubility right up to the melting point of silver can be represented very closely by three straight lines: log10N = 0.67035 - 1134.7T-1. . . .up to 330°C. log10 N = 2.9065 - 2481.8T-1. . . .330° to 450°C. log10 N = 0.7441 - 918.2T-1. . . .450°C. to the melting point of silver Their intersections, however, have no relation to the peritectic formation temperatures of Ag5Hg4 at 276°C. and Ag5Hg8 at 127°C., and these points do not appear at all on the logarithmic curve. At low temperatures the solubility is about one-fortieth of that calculated from the elementary equation established by Schröder in 1893: log10 N = Hf/R(1/Tm - 1/T) or about one-hundredth if Hf is corrected for temperature variation. Possible explanations for this are unconvincing. The approximate expression derived from consideration of unlike atoms RT log10 (a1/N1) = KN22 (a being the Schröder solubility) fits the experimental curve very well up to 340°C. if K = 465, as calculated from solubility at the steam point; and even after its departure gives an analogous reversed-S curve. A roughly parallel curve holds for the solubility of silver in liquid tin. In the more exact expression RT log10 (a1/N1) = V1 (N2V2/N2V2 + N1V1)2 [P1/21 - P1/22]2 the observed solubilities lead to a figure of 14 for [P1/21 - P1/22] compared with approximate values of 23.8, 40.9, 47.3, 18.2, 39.1, derived from diverse physical properties. The deviation from theoretical solubility is thus only a half or a third of what might be expected from consideration of the internal pressures of the two metals. It is concluded that the mutual attraction within a pair of unlike atoms is greater than the geometric mean of corresponding attractions within pairs of like atoms, in sharp contrast to the behaviour of most organic molecules and to previous conjectures, on theoretical grounds. A convenient method is described for determining strain in glass vessels after blowpipe manipulation, by use of polarized light.

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