Volume change for the formation of magnesium sulfate ion pairs at various temperatures

Millero, Frank J.; Masterton, William L.

doi:10.1021/j100606a010

Cited by 42 publications

(13 citation statements)

References 24 publications

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“…A t any rate, the agreement is still sufficiently good that we would not expect an error much larger than 1 J k-I mol-I in +, resulting from errors in densities and The order of magnitude of the C : -(MgSO,') (-200 J K-' mol-') when compared with the heat capacity of solid MgSO, (96 J K-' mol-l) (22) and C:(Mg2+,S0$-) (-286.4 J K-' mol-l) indicates that the ion pair still has about 80% of its hydration contribution remaining. This would suggest that these ion pairs still strongly interact with water, in agreement with volume and compressibility measurements (15,23).…”

Section: 4supporting

confidence: 82%

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Apparent Molal Volumes and Heat Capacities of some Sulfates and Carbonates in Water at 25 °C

Perron¹,

Desnoyers²,

Millero³

1975

Can. J. Chem.

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The densities and volumetric specific heats of Na2SO4, K2SO4, MgSO4, Na2CO3, NaHCO3, and NaOH were measured up to an ionic strength of 1 in water at 25 °C with a flow densimeter and a flow microcalorimeter. From these data, the heat capacity for the formation of the ion pair MgSO40was evaluated as 84.9 J K−1 mol−1. There is an anomalous increase in the apparent molal heat capacities of Na2CO3 at low concentration but the apparent molal volumes are normal. This anomaly can be suppressed with NaOH. Attempts to account quantitatively for this behavior by an hydrolysis correction were not successful.

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Section: 4supporting

confidence: 82%

“…and co-worker (15). We have no reasons to believe that the present measurements are less reliable than the others.…”

Section: 4contrasting

confidence: 57%

Apparent Molal Volumes and Heat Capacities of some Sulfates and Carbonates in Water at 25 °C

Perron¹,

Desnoyers²,

Millero³

1975

Can. J. Chem.

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“…The nature of ion pairs formed in divalent metal sulfate solutions is complicated 35,36 and their presence in appreciable amounts can have substantial effects on observed Y(m) values at low m, producing an unreliable extrapolation to infinite dilution. 32,33,37 While attempts have been made to quantitatively incorporate ion association into the estimation of Y o values, 38,39 the extra (mostly unknown) parameters required and the numerical correlations among them have discouraged their widespread application. For the present salts, the Y o was instead obtained by summation of literature values for M 2+ (aq) and SO4 2-(aq) ions.…”

Section: Standard Molar Valuesmentioning

confidence: 99%

Volumes and Heat Capacities of Cobalt(II), Nickel(II), and Copper(II) Sulfates in Aqueous Solution

et al. 2020

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Densities and isobaric volumetric heat capacities of aqueous solutions of the sulfate salts of cobalt(II), nickel(II) and copper(II) have been measured at 298.15 K and 0.1 MPa using vibrating tube densimetry and Picker flow calorimetry, respectively, at concentrations in the range 0.01 ≲ m/mol•kg -1 ≲ 1.5. These data were used to derive the corresponding apparent molar volumes, V, and apparent molar isobaric heat capacities, Cp.Where comparisons were possible the present V results were in good agreement with literature data. No Cp data appear to have been reported previously for any of these salts. The variations of V and Cp with concentration were well correlated using the Pitzer formalism combined with values of V o and Cp o estimated from literature data. Both V and Cp for all three salts show remarkable similarities and can be shown to lie on a common line by applying fixed addends over almost the whole concentration range studied.

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“…(5)) the meaning of partial molar volume of the dissolved component at infinite dilution, it must be viewed as an empirical parameters, as the con- At infinite dilution, partial molar volumes of the dissolved compound obey the additivity principle?, i .e. (7) the values ¢~ for ions being given in published tables, e.g. ?…”

Section: Theoreticalmentioning

confidence: 99%

Density estimates of binary aqueous solutions

Söhnel

Novotný

Šolc

1983

Collect. Czech. Chem. Commun.

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Two methods are given for assessment of density of binary aqueous solutions of electrolytes; one is based on partial molar volume of the dissolved electrolyte at inflnite dilution, and the other is based on additivity of apparent molar volumes at a give n concentration. The density estima tes of aqueous solutions by mea ns of the two methods are compared with experimental values for some electrolytes of the type 1-1 to 4 and 2-2. In a ll the cases the es tima tes agree with experimental densities up to concentration s of the saturated sol utions.In technical, technological, and physico-chemical calculations of processes takin g place in aqueous solutions it is often necessary to know density of the aqueous solution in question. Ex perimental data on densities of binary aq uco us sol utions in broad tempcrature a nd concentration range are available for about 200 syste ms only. For about 200 other systems values are published concerning one or two temperatures. All other compounds belong eit her to systems not measured at all, or information on densities is only very limited.From practical point of view it is desirable to asses den sities of binary systems not yet measured. The present paper gives two methods of th e assessment based on physico-chemical characteristics of the solutions. THEORETICALThe previous reports) -3 showed that concentration-temperature dependence of densities of binary aqueous solutions is expressed well by Eq. (1) within the range from o to 100°C up to the saturation concentration.(1)The parameters (X and [3 of the Masson's equation 4 (2) can be obtained from the constant A through F of Eq . (1) with the use of Eqs (3) and (4), and physical meaning is given by Eqs (5) and (6).

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Volume change for the formation of magnesium sulfate ion pairs at various temperatures

Cited by 42 publications

References 24 publications

Apparent Molal Volumes and Heat Capacities of some Sulfates and Carbonates in Water at 25 °C

Apparent Molal Volumes and Heat Capacities of some Sulfates and Carbonates in Water at 25 °C

Volumes and Heat Capacities of Cobalt(II), Nickel(II), and Copper(II) Sulfates in Aqueous Solution

Density estimates of binary aqueous solutions

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