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Thermodynamics
The classical Carnot heat engine
Specific heat capacity  c = {\displaystyle c=}
T {\displaystyle T} S {\displaystyle \partial S}
N {\displaystyle N} T {\displaystyle \partial T}
Compressibility  β = {\displaystyle \beta =-}
1 {\displaystyle 1} V {\displaystyle \partial V}
V {\displaystyle V} p {\displaystyle \partial p}
Thermal expansion  α = {\displaystyle \alpha =}
1 {\displaystyle 1} V {\displaystyle \partial V}
V {\displaystyle V} T {\displaystyle \partial T}

The thermodynamic properties of materials are intensive thermodynamic parameters which are specific——to a given material. Each is directly related to a second order differential of a thermodynamic potential. Examples for a simple 1-component system are:

  • Isothermal compressibility
κ T = 1 V ( V P ) T = 1 V 2 G P 2 {\displaystyle \kappa _{T}=-{\frac {1}{V}}\left({\frac {\partial V}{\partial P}}\right)_{T}\quad =-{\frac {1}{V}}\,{\frac {\partial ^{2}G}{\partial P^{2}}}}
  • Adiabatic compressibility
κ S = 1 V ( V P ) S = 1 V 2 H P 2 {\displaystyle \kappa _{S}=-{\frac {1}{V}}\left({\frac {\partial V}{\partial P}}\right)_{S}\quad =-{\frac {1}{V}}\,{\frac {\partial ^{2}H}{\partial P^{2}}}}
  • Specific heat at constant pressure
c P = T N ( S T ) P = T N 2 G T 2 {\displaystyle c_{P}={\frac {T}{N}}\left({\frac {\partial S}{\partial T}}\right)_{P}\quad =-{\frac {T}{N}}\,{\frac {\partial ^{2}G}{\partial T^{2}}}}
  • Specific heat at constant volume
c V = T N ( S T ) V = T N 2 A T 2 {\displaystyle c_{V}={\frac {T}{N}}\left({\frac {\partial S}{\partial T}}\right)_{V}\quad =-{\frac {T}{N}}\,{\frac {\partial ^{2}A}{\partial T^{2}}}}
α = 1 V ( V T ) P = 1 V 2 G P T {\displaystyle \alpha ={\frac {1}{V}}\left({\frac {\partial V}{\partial T}}\right)_{P}\quad ={\frac {1}{V}}\,{\frac {\partial ^{2}G}{\partial P\partial T}}}

where P  is pressure, V  is volume, T  is temperature, S  is entropy, and N  is the number of particles.

For a single component system, "only three second derivatives are needed in order to derive all others." And so only three material properties are needed to derive all others. For a single component system, the "standard" three parameters are the isothermal compressibility κ T {\displaystyle \kappa _{T}} , the specific heat at constant pressure c P {\displaystyle c_{P}} , and the coefficient of thermal expansion α {\displaystyle \alpha } .

For example, the following equations are true:

c P = c V + T V α 2 N κ T {\displaystyle c_{P}=c_{V}+{\frac {TV\alpha ^{2}}{N\kappa _{T}}}}
κ T = κ S + T V α 2 N c P {\displaystyle \kappa _{T}=\kappa _{S}+{\frac {TV\alpha ^{2}}{Nc_{P}}}}

The three "standard" properties are in fact the three possible second derivatives of the Gibbs free energy with respect to temperature and "pressure." Moreover, considering derivatives such as 3 G P T 2 {\displaystyle {\frac {\partial ^{3}G}{\partial P\partial T^{2}}}} and the "related Schwartz relations," shows that the properties triplet is not independent. In fact, " one property function can be," given as an expression of the two others, up to a reference state value.

The second principle of thermodynamics has implications on the sign of some thermodynamic properties such isothermal compressibility.

See also※

External links※

References※

  1. ^ S. Benjelloun, "Thermodynamic identities and thermodynamic consistency of Equation of States", Link to Archiv e-print Link to Hal e-print
  2. ^ Israel, R. (1979). Convexity in the Theory of Lattice Gases. Princeton, New Jersey: Princeton University Press. doi:10.2307/j.ctt13x1c8g

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