Heat capacity

The heat capacity is defined as the differential of heat with respect to the temperature Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle T} ,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle C := \frac{\delta Q}{\partial T} = T \frac{\partial S}{\partial T}}

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Q} is heat and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle S} is the entropy.

At constant volume

From the first law of thermodynamics one has

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \left.\delta Q\right. = dU + pdV}

thus at constant volume, denoted by the subscript Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle V} , then Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle dV=0} ,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle C_V := \left.\frac{\delta Q}{\partial T} \right\vert_V = \left. \frac{\partial U}{\partial T} \right\vert_V }

At constant pressure

At constant pressure (denoted by the subscript Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle p} ),

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle C_p := \left.\frac{\delta Q}{\partial T} \right\vert_p =\left.\frac{\partial H}{\partial T} \right\vert_p= \left. \frac{\partial U}{\partial T} \right\vert_p + p \left.\frac{\partial V}{\partial T} \right\vert_p}

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle H} is the enthalpy. The difference between the heat capacity at constant pressure and the heat capacity at constant volume is given by

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle C_p -C_V = \left( p + \left. \frac{\partial U}{\partial V} \right\vert_T \right) \left. \frac{\partial V}{\partial T} \right\vert_p}

Adiabatic index

Sometimes the ratio of heat capacities is known as the adiabatic index:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \gamma = \frac{C_p}{C_V}}

Excess heat capacity

In a classical system the excess heat capacity for a monatomic fluid is given by subtracting the ideal internal energy (which is kinetic in nature)

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle C_v^{ex} = C_v - \frac{3}{2}Nk_B}

in other words the excess heat capacity is associated with the component of the internal energy due to the intermolecular potential, and for that reason it is also known as the configurational heat capacity. Given that the excess internal energy for a pair potential is given by (Eq. 2.5.20 in ):

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle U^{ex} = 2\pi N \rho \int_0^{\infty} \Phi_{12}(r) g(r) r^2 ~{\rm d}{\mathbf r}}

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Phi_{12}(r)} is the intermolecular pair potential and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle g(r)} is the radial distribution function, one has

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle C_v^{ex} = 2\pi N \rho \int_0^{\infty} \Phi_{12}(r) \left. \frac{\partial g(r)}{\partial T} \right\vert_V r^2 ~{\rm d}{\mathbf r} }

For many-body distribution functions things become more complicated .

Rosenfeld-Tarazona expression

Rosenfeld and Tarazona used fundamental-measure theory to obtain a unified analytical description of classical bulk solids and fluids, one result being:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle C_v^{ex} \propto T^{-2/5}}

Liquids

The calculation of the heat capacity in liquids is more difficult than in gasses or solids . Recently an expression for the energy of a liquid has been developed (Eq. 5 of ):

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle E = NT \left( 1 + \frac{\alpha T}{2}\right) \left( 3D \left( \frac{\hbar \omega_D}{T} \right) -\left( \frac{\omega_F}{\omega_D} \right)^3 D\left( \frac{\hbar \omega_F}{T}\right) \right)}

where Failed to parse (Conversion error. Server ("https://wikimedia.org/api/rest_") reported: "Cannot get mml. Server problem."): {\displaystyle \omega _{F}} is the Frenkel frequency, Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \omega_D} is the Debye frequency, Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle D} is the Debye function, and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \alpha} is the thermal expansion coefficient. The differential of this energy with respect to temperature provides the heat capacity.

Solids

Debye

A low temperatures on has

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle c_v = \frac{12 \pi^4}{5} n k_B \left( \frac{T}{\Theta_D} \right)^3}

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle k_B} is the Boltzmann constant, Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle T} is the temperature and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Theta_D} is an empirical parameter known as the Debye temperature.

See also

• Heat capacity of an ideal gas
• Yang-Yang anomaly

References

Related reading

• William R. Smith, Jan Jirsák, Ivo Nezbeda, and Weikai Qi "Molecular simulation of caloric properties of fluids modelled by force fields with intramolecular contributions: Application to heat capacities", Journal of Chemical Physics 147 034508 (2017)