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    D Density of The Solution, The Same As That of Solvent When The Solution Is Dilute

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    mazhar
    The document discusses concepts related to soil chemistry analysis, including: 1) It defines the Davies equation, which is used to determine activity coefficients of equilibrium solutions in soil chemistry studies based on ionic strength. 2) It explains that ionic strength can be calculated from electrical conductivity measurements according to a relation proposed by Griffin and Jurinak. 3) It discusses the ionic activity product of water (Kw), which is the equilibrium constant for the dissociation of water into hydrogen and hydroxide ions in solution. The value of Kw is precisely determined from measurements of galvanic cells.

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    D Density of The Solution, The Same As That of Solvent When The Solution Is Dilute

    Uploaded by

    mazhar
    36 views1 page
    The document discusses concepts related to soil chemistry analysis, including: 1) It defines the Davies equation, which is used to determine activity coefficients of equilibrium solutions in soil chemistry studies based on ionic strength. 2) It explains that ionic strength can be calculated from electrical conductivity measurements according to a relation proposed by Griffin and Jurinak. 3) It discusses the ionic activity product of water (Kw), which is the equilibrium constant for the dissociation of water into hydrogen and hydroxide ions in solution. The value of Kw is precisely determined from measurements of galvanic cells.

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    The document discusses concepts related to soil chemistry analysis, including: 1) It defines the Davies equation, which is used to determine activity coefficients of equilibrium solutions in soil chemistry studies based on ionic strength. 2) It explains that ionic strength can be calculated from electrical conductivity measurements according to a relation proposed by Griffin and Jurinak. 3) It discusses the ionic activity product of water (Kw), which is the equilibrium constant for the dissociation of water into hydrogen and hydroxide ions in solution. The value of Kw is precisely determined from measurements of galvanic cells.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    36 views1 page

    D Density of The Solution, The Same As That of Solvent When The Solution Is Dilute

    Uploaded by

    mazhar
    The document discusses concepts related to soil chemistry analysis, including: 1) It defines the Davies equation, which is used to determine activity coefficients of equilibrium solutions in soil chemistry studies based on ionic strength. 2) It explains that ionic strength can be calculated from electrical conductivity measurements according to a relation proposed by Griffin and Jurinak. 3) It discusses the ionic activity product of water (Kw), which is the equilibrium constant for the dissociation of water into hydrogen and hydroxide ions in solution. The value of Kw is precisely determined from measurements of galvanic cells.

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    2 PHYSICAL AND CHEMICAL METHODS IN SOIL ANALYSIS

    D = dielectric constant = 78.54


    T = absolute temperature
    d = density of the solution, the same as that of solvent when the solution is dilute.
    Constant A2 accounts for variation of dielectric constant or a constant for a given electro-
    lyte.
    The activity coefficients of equilibrium solution in soil chemistry studies are often deter-
    mined using Davies equation (Amacher, 1984) namely,
    (− 0.502 z 2 I )
    log r = = 0.2I ...(1.1.4)
    (1 + I )
    where z is the valency of an ion and I is ionic strength of the soil solution. The ionic strength is
    calculated from the electrical conductivity (ECe) according to the relation proposed by Griffin
    and Jurinak (1973) namely,
    I = 0.0127 ECe ...(1.1.5)
    Note : In 1.0 mole kg–1 HCl (aq), mH+ = 1.0 mole kg–1 (the acid is fully ionised) and mean activity coeffi-
    cient is = 0.811 (Table value (At kms 1986) ; therefore, aH+ = 0.811 × (1.0 mol kg–1/m–) = 0.81, implying pH
    = 0.092 in place of the value pH = 0 which would have been obtained from the use of molality alone. There
    is also nothing mysterious about the concept of negative pH, for it, merely corresponds to an activity
    greater than unity. For example, in 2.00 mole kg–1 HCl (aq) where the mean activity coefficient is 1.011
    (Table value, Appendix VII), the hydrogen ion activity is 2.02, implying pH = – 0.31.
    In the pure state, water is dissociated to a very small extent and behaves as a weak
    electrolyte. The equilibrium constant of the dissociation, H2O H+ + OH–, is given by,
    a + . aOH−
    K= H ...(1.1.6)
    aH2O
    In the pure state, or in dilute solution, the activity of water aH 2O is constant and is taken
    to be unity.
    Hence, Kw = aH + . aOH − ...(1.1.7)
    The Kw is called the ionic activity product of water. Replacing activities with concentra-
    tions and activity coefficients
    Kw = C H + . f H + . CH − f H − = (C H + C H − ) f H + . f H + ...(1.1.8)
    or Kw = Kw′ f H + . fO H − ...(1.1.9)
    where Kw′ = C H . CO H − (1.1.9a) is called the ion product of water. In pure water or in dilute
    +

    solutions the activity coefficients f H + and fO H − are almost unity and so Kw ≈ Kw′. That is no
    appreciable error is involved in accepting ion product of water as its ionic activity product.
    At 25°C, the concentration of H+ ions in pure water has been found to be 1 × 10–7. Since
    CH+ = CO H − in pure water
    ∴ Kw′ = C H + . CO H − = (1 × 10–7)2 = 1 × 10–14 ...(1.1.10)
    The ionic activity product of water is very accurately derived, from e.m.f. measurement
    of suitable galvanic cells, such as
    Pt(H2) | KOH (aq.) KCl (aq.) | AgCl(s) | Ag ; (m1 and m2 are the molalities)
    (m1) (m2)
    in which the cell reaction is, AgCl (s) + ½H2 → Ag (s) + H+ + Cl–. The experimentally obtained
    value from e.m.f. determination of Kw was found to be 1.008 × 10–14 at 25°C. The ionic activity
    product of water at different temperatures are :

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