1.7.1: Compressions and Expansions- Liquids
The isothermal compressions of solutions and liquids have been extensively studied and the subject has a remarkable history. The term compression, symbol \(\mathrm{K}\) describes the sensitivity of the volume of a system to an isothermal change in pressure, \((\partial V / \partial p)\). Reference is usually made to the voyage made by HMS Challenger and the report of experiments undertaken by Tait into the compression of water [1-3]. Kell summarises various equations which have been proposed describing the isothermal dependence of the molar volume of water on pressure [4]; see also references [5,6].
The dependence of the volume of water(\(\ell\)) at low pressures and at a given temperature on pressure can be represented by equation (a) where \(\mathrm{A}\) and \(\mathrm{B}\) are constants.
\[[\mathrm{V}(\text { ref })-\mathrm{V}] / \mathrm{V}(\text { ref }) \, \mathrm{p}=\mathrm{A} /(\mathrm{B}+\mathrm{p}) \nonumber \]
Here \(\mathrm{V}(\text{ref})\) is the volume ‘at zero pressure’, usually ambient pressure (i.e. approx \(105 \mathrm{~N m}^{-2}\)). This equation often called the Tait equation [4] has the form shown in equation (b).
\[-\left(1 / \mathrm{V}^{0}\right) \,(\partial \mathrm{V} / \partial \mathrm{p})=\mathrm{A} /(\mathrm{B}+\mathrm{p}) \nonumber \]
\[\text { Alternatively [4] } \mathrm{V}=\mathrm{V}^{0}\{1-\mathrm{A} \, \ln [(\mathrm{B}+\mathrm{p}) / \mathrm{B}]\} \nonumber \]
The challenge of measuring the isothermal compression of liquids has been taken up by many investigators; e.g. references [7-12]. The isothermal compressions of a liquid \(\mathrm{K}_{\mathrm{T}}\) is defined by equation (d) [13].
\[\mathrm{K}_{\mathrm{T}}=-(\partial \mathrm{V} / \partial \mathrm{p})_{\mathrm{T}} \nonumber \]
The isothermal compressibility is given by equation (e) [14].
\[\kappa_{\mathrm{T}}=-\mathrm{V}^{-1} \,(\partial \mathrm{V} / \partial \mathrm{p})_{\mathrm{T}} \nonumber \]
For all thermodynamic equilibrium states, both \(\mathrm{K}_{\mathrm{T}}\) and \(\kappa_{\mathrm{T}}\) are positive variables. A related variable is the isochoric thermal pressure coefficient, \((\partial p / \partial T)_{v}\).[15]
We develop the story in the context of systems containing two liquid components. For a closed system containing \(\mathrm{n}_{1}\) and \(\mathrm{n}_{2}\) moles of chemical substances 1 and 2, the Gibbs energy is a dependent variable and the variables \(\left[\mathrm{T}, \mathrm{p}, \mathrm{n}_{1}, \mathrm{n}_{2}\right]\) are the independent variables. Temperature \(\mathrm{T}\) is the thermal potential; pressure \(\mathrm{p}\) is the mechanical variable. The number of thermodynamic variables necessary to define the system is established using the Gibbs Phase Rule [16]. For a closed system (at defined \(\mathrm{T}\) and \(\mathrm{p}\)) at thermodynamic equilibrium the composition/organisation is represented by \(\xi^{e q}\). The affinity for spontaneous change is zero consistent with the Gibbs energy being a minimum; equation (f).
\[\mathrm{A}=-(\partial \mathrm{G} / \partial \xi)_{\mathrm{T}, \mathrm{p}}^{\mathrm{eq}}=0 \nonumber \]
The Gibbs energy, volume and entropy of a solution at equilibrium are state variables. We contrast these properties with those properties which are associated with a process (pathway). Thus we contrast the state variable V with an unspecified compression of a solution. We need to define the path followed by the system when the pressure is changed. The Gibbs energy of a closed system at thermodynamic equilibrium (where the affinity for spontaneous change is zero and where the molecular composition/organisation is characterised by \(\xi^{e q}\)) is described by equation (g).
\[\mathrm{G}=\mathrm{G}\left[\mathrm{T}, \mathrm{p}, \mathrm{n}_{1}, \mathrm{n}_{2}, \mathrm{~A}=0\right] \nonumber \]
The same state is characterised by the equilibrium volume and equilibrium entropy by equations (h) and (i) respectively.
\[\mathrm{V}=\mathrm{V}\left[\mathrm{T}, \mathrm{p}, \mathrm{n}_{1}, \mathrm{n}_{2}, \mathrm{~A}=0\right] \nonumber \]
\[\mathrm{S}=\mathrm{S}\left[\mathrm{T}, \mathrm{p}, \mathrm{n}_{1}, \mathrm{n}_{2}, \mathrm{~A}=0\right] \nonumber \]
We use two intensive variables, \(\mathrm{T}\) and \(\mathrm{p}\), in the definition of extensive variables \(\mathrm{G}\), \(\mathrm{V}\) and \(\mathrm{S}\). When the pressure is increased by finite increments from \(\mathrm{p}\) to (\(\mathrm{p} + \Delta \mathrm{p}\)), the volume changes in finite increments from \(\mathrm{V}\) to (\(\mathrm{V} + \Delta \mathrm{V}\)). For an important pathway, the temperature is constant. However to satisfy the condition that the affinity for spontaneous change \(\mathrm{A}\) is zero, the molecular organisation/composition \(\xi\) changes. The volume at pressure (\(\mathrm{p} + \Delta \mathrm{p}\)) is defined using equation (j).
\[\mathrm{V}=\mathrm{V}\left[\mathrm{T},(\mathrm{p}+\Delta \mathrm{p}), \mathrm{n}_{1}, \mathrm{n}_{2}, \mathrm{~A}=0\right] \nonumber \]
In principle we plot the volume as a function of pressure at constant temperature, \(\mathrm{n}_{1}\), \(\mathrm{n}_{2}\), and at ‘\(\mathrm{A} = 0\)’. The gradient of the plot defined by equation (h) yields the equilibrium isothermal compression, \(\mathrm{K}_{\mathrm{T}}(\mathrm{A}=0)\); equation (k)
\[\mathrm{K}_{\mathrm{T}}(\mathrm{A}=0)=-(\partial \mathrm{V} / \partial \mathrm{p})_{\mathrm{T}, \mathrm{A}=0} \nonumber \]
\(\mathrm{K}_{\mathrm{T}}(\mathrm{A} = 0)\) characterises the state defined by the set of variables, \(\left[\mathrm{T}, \mathrm{p}, \mathrm{n}_{1}, \mathrm{n}_{2}, \mathrm{~A}=0\right]\).
We turn our attention to another property starting with a system having a volume defined by equation (h). The system is perturbed by a change in pressure from \(\mathrm{p}\) to (\(\mathrm{p} + \Delta \mathrm{p}\)) in an equilibrium displacement. However on this occasion we require that the entropy of the system remains constant at a value defined by equation (i). In principle we plot the volume \(\mathrm{V}\) as a function of pressure at constant \(\mathrm{n}_{1}\), \(\mathrm{n}_{2}\), at ‘\(\mathrm{A}=0\)’ and at a constant entropy defined by equation (i). The gradient of the plot at the point where the volume is defined by equation (g) yields the equilibrium isentropic compression \(\mathrm{K}_{\mathrm{S}} (\mathrm{A}=0)\); equation (l) where isentropic = adiabatic and ‘at equilibrium’.
\[\mathrm{K}_{\mathrm{S}}(\mathrm{A}=0)=-(\partial \mathrm{V} / \partial \mathrm{p})_{\mathrm{S}, \mathrm{A}=0} \nonumber \]
The equilibrium state characterised by \(\mathrm{K}_{\mathrm{S}}(\mathrm{A}=0)\) is defined by the variables \(\left[\mathrm{T}, \mathrm{p}, \mathrm{n}_{1}, \mathrm{n}_{2}, \mathrm{~A}=0\right]\). In other words an isentropic volumetric property describes a solution defined in part by the intensive variables \(\mathrm{T}\) and \(\mathrm{p}\). Significantly the condition on the partial derivative in equation (l) is an extensive variable, entropy. For a stable phase \(\mathrm{K}_{\mathrm{S}}\) is positive.
The arguments outlined above are repeated with respect to both isobaric equilibrium expansions \(\mathrm{E}_{\mathrm{p}}(\mathrm{A}=0)\) and isentropic equilibrium expansions, \(\mathrm{E}_{\mathrm{S}}(\mathrm{A}=0)\); equations (m) and (n).
\[\mathrm{E}_{\mathrm{p}}(\mathrm{A}=0)=-(\partial \mathrm{V} / \partial \mathrm{T})_{\mathrm{p}, \mathrm{A}=0} \nonumber \]
\[\mathrm{E}_{\mathrm{S}}(\mathrm{A}=0)=-(\partial \mathrm{V} / \partial \mathrm{T})_{\mathrm{S}, \mathrm{A}=0} \nonumber \]
The (equilibrium) volume intensive isothermal \(\kappa_{\mathrm{T}}\) and isentropic \(\kappa_{\mathrm{S}}\) compressibilities are defined by equations (o) and (p) .
\[\kappa_{\mathrm{T}}=-(1 / \mathrm{V}) \,(\partial \mathrm{V} / \partial \mathrm{p})_{\mathrm{T}}=\mathrm{K}_{\mathrm{T}} \, \mathrm{V}^{-1} \nonumber \]
\[\kappa_{\mathrm{s}}=-(1 / \mathrm{V}) \,(\partial \mathrm{V} / \partial \mathrm{p})_{\mathrm{s}}=\mathrm{K}_{\mathrm{s}} \, \mathrm{V}^{-1} \nonumber \]
In 1914 Tyrer reported isentropic and isothermal compressibilities for many liquids [9]. Equations (q) and (r) define two (equilibrium) expansibilities, isentropic and isobaric, volume intensive properties.
\[\alpha_{\mathrm{s}}=(1 / \mathrm{V}) \,(\partial \mathrm{V} / \partial \mathrm{T})_{\mathrm{s}}=\mathrm{E}_{\mathrm{S}} \, \mathrm{V}^{-1} \nonumber \]
\[\alpha_{p}=(1 / V) \,(\partial \mathrm{V} / \partial \mathrm{T})_{p}=\mathrm{E}_{\mathrm{p}} \, \mathrm{V}^{-1} \nonumber \]
Rowlinson and Swinton state that the property \(\alpha_{\mathrm{S}}\) is ‘of little importance’ [17]. The isobaric heat capacity per unit volume \(\sigma\) is the ratio \(\left[\mathrm{C}_{\mathrm{p}} / \mathrm{V}\right]\). A property of some importance is the difference between compressibilities, \(\delta\); equation (s).
\[\delta=\kappa_{\mathrm{T}}-\kappa_{\mathrm{S}}=\mathrm{T} \,\left[\alpha_{\mathrm{p}}\right]^{2} \, \mathrm{V} / \mathrm{C}_{\mathrm{p}}=\mathrm{T} \,\left[\alpha_{p}\right]^{2} / \sigma \nonumber \]
The property \(\sigma\) is given different symbols and names; e.g. volumetric specific heat. Here we identify \(\sigma\) as the thermal (or, heat) capacitance. The property \(\varepsilon\) is the difference between isobaric and isentropic expansibilities; equation (t).
\[\varepsilon=\alpha_{p}-\alpha_{s}=\kappa_{T} \, \sigma / T \, \alpha_{p} \nonumber \]
The Newton–Laplace equation is the starting point for the determination of isentropic compressibilities of liquids using sound speeds and densities; equation (u).
\[u^{2}=\left(\kappa_{\mathrm{s}} \, \rho\right)^{-1} \nonumber \]
The isentropic condition on \(\kappa_{\mathrm{S}}\) means that as a sound wave passes through a liquid the pressure and temperature fluctuate within each microscopic volume but the entropy remains constant.
Footnotes
[1] P. G. Tait, ‘Voyage of HMS Challenger’ (Physics and Chemistry), 1888, Volume II, Part IV, 76pp.
[2] P. G. Tait, ‘Scientific Papers’, The University Press, Cambridge, 1898, Volume I, p.261.
[3] See also N. E. Dorsey, Properties of Ordinary Water Substance, Reinhold, New York , 1940, pp. 207-253.
[4] G.S Kell, Water A Comprehensive Treatise, ed. F Franks, Plenum Press, New York, 17972, Volume 1, pp. 382-383.
[5] J. H. Dymond and R. Malhotra, Int. J. Thermophys., 1988, 9 ,941.
[6] A. T. J. Hayward, Brit.J. Appl. Phys., 1967, 18 ,965.
[7] G. A. Neece and D. R. Squire, J.Phys.Chem.,1968, 72 ,128.
[8] J. H. Hildebrand, Phys.Rev.,1929, 34 ,649.
[9] D. Tyrer, J. Chem. Soc., 1914, 105 ,2534.
[10] H. E. Eduljee, D. M. Newitt and K. E. Weale, J.Chem.Soc.,1951,3086.
[11] L. A. K. Staveley, W. I. Tupman, and K. R. Hart, Trans. Faraday Soc.,1955, 51 ,323.
[12] D. N. Newitt and K.Weale, J.Chem. Soc.,1951,3092.
[13] \(\mathrm{K}_{\mathrm{T}}=\left[\mathrm{m}^{3}\right] /\left[\mathrm{N} \mathrm{m}^{-2}\right]=\left[\mathrm{m}^{3} \mathrm{~Pa}^{-1}\right]\)
[14] \(\mathrm{K}_{\mathrm{T}}=\frac{1}{\left[\mathrm{~m}^{3}\right]} \, \frac{\left[\mathrm{m}^{3}\right]}{[\mathrm{Pa}]}=\left[\mathrm{Pa}^{-1}\right]\)
[15] \((\partial \mathrm{p} / \partial \mathrm{T})_{\mathrm{V}}=\left[\mathrm{Pa} \mathrm{K}{ }^{-1}\right]\)
[16] Phase Rule; \(\mathrm{P} = 1\); \(\mathrm{C} = 2\). Hence \(\mathrm{F} = 3\). Then we define \(\mathrm{T}\), \(\mathrm{p}\) and mole fraction composition.
[17] J. S. Rowlinson and F. L. Swinton, Liquids and Liquid Mixtures, Butterworths, London, 3rd edn., 1982, pp 16-17.