diff --git a/doc/sphinx/yaml/phases.rst b/doc/sphinx/yaml/phases.rst index aed82bfed7..c3cc8f86e9 100644 --- a/doc/sphinx/yaml/phases.rst +++ b/doc/sphinx/yaml/phases.rst @@ -265,7 +265,7 @@ entropy, and heat capacity of each species may depend on its coverage and the coverage of other species in the phase. Full details are :ct:`described here `. The majority of coverage dependency parameters are provided in the species entry as -:ref:`described here `. +:ref:`described here `. Additional fields: diff --git a/doc/sphinx/yaml/species.rst b/doc/sphinx/yaml/species.rst index 93fd41ab58..16f3c974fb 100644 --- a/doc/sphinx/yaml/species.rst +++ b/doc/sphinx/yaml/species.rst @@ -36,6 +36,12 @@ The fields of a ``species`` entry are: Mapping containing the species transport model specification and parameters. See :ref:`sec-yaml-species-transport`. +``coverage-dependencies`` + Mapping where keys are the names of other species whose coverages affects + thermodynamic properties of this species. The map values are the dependency entries + including ``model`` and model-specific parameters as :ref:`described here + `. + ``sites`` The number of sites occupied by a surface or edge species. Default is 1. @@ -135,6 +141,7 @@ Example:: 2.486903333E-06, -9.705954110E-11, 1.437538881E-15, 4.938707040E+06, -1.672099740E+03] + .. _sec-yaml-shomate: Shomate polynomials @@ -205,6 +212,7 @@ Example:: s0: -3.02 cal/mol/K cp0: 5.95 cal/mol/K + .. _sec-yaml-piecewise-gibbs: Piecewise Gibbs @@ -423,6 +431,7 @@ Additional fields: ``data`` Vector of 4 coefficients for a cubic polynomial in temperature + .. _sec-yaml-eos-peng-robinson: Peng-Robinson @@ -481,98 +490,6 @@ Additional fields: coefficients for binary interactions between the two species. -.. _sec-yaml-coverage-dependent-surface-species: - -Coverage-dependent Surface --------------------------- - -A model where species thermodynamic properties are calculated as a function -coverage as :ct:`described here `. - -Additional fields: - -``coverage-dependencies`` - Mapping where keys are the name of species whose coverage affects - thermodynamic properties of the node-owner species. The map values are - the dependency entries including ``model``, model-specific parameters, - ``heat-capacity-a``, and ``heat-capacity-b`` that correspond - to an individual dependency between the node-owner species and keyed species. - -``model`` - Dependency model for coverage-dependent enthalpy or entropy. It should be - one of the four: ``linear``, ``polynomial``, ``piecewise-linear`` - or ``interpolative``. The ``model`` and model-specific parameters are grouped - as follow. - - ``linear``: ``enthalpy``, ``entropy`` - - ``polynomial``: ``enthalpy-coefficients``, ``entropy-coefficients`` - - ``piecewise-linear``: ``enthalpy-low``, ``enthalpy-high``, ``enthalpy-change``, - ``entropy-low``, ``entropy-high``, ``entropy-change`` - - ``interpolative``: ``enthalpy-coverages``, ``enthalpies``, ``entropy-coverages``, - ``entropies`` - -``enthalpy`` or ``entropy`` - Slope of the coverage-dependent enthalpy or entropy used in the ``linear`` - model. - -``enthalpy-coefficients`` or ``entropy-coefficients`` - Array of polynomial coefficients in order of 1st, 2nd, 3rd, and 4th-order - used in coverage-dependent enthalpy or entropy calculation with the ``polynomial`` - model. - -``enthalpy-low`` or ``entropy-low`` - Slope of the coverage-dependent enthalpy or entropy for the lower coverage - region used in the ``piecewise-linear`` model. - -``enthalpy-high`` or ``entropy-high`` - Slope of the coverage-dependent enthalpy or entropy for the higher coverage - region used in the ``piecewise-linear`` model. - -``enthalpy-change`` or ``entropy-change`` - Coverage that separates the lower and higher coverage regions of the - coverage-dependent enthalpy or entropy used in the ``piecewise-linear`` model. - -``enthalpy-coverages`` or ``entropy-coverages`` - Array of discrete coverage values used in coverage-dependent enthalpy - or entropy used in the ``interpolative`` model. - -``enthalpies`` or ``entropies`` - Array of discrete enthalpy or entropy values corresponding to the coverages - in ``enthalpy-coverages`` or ``entropy-coverages``, respectively, used in the - ``interpolative`` model. - -``heat-capacity-a`` or ``heat-capacity-b`` - Coefficient :math:`c^{(a)}` or :math:`c^{(b)}` used in the coverage-dependent - ``heat capacity`` model. - -Example:: - - coverage-dependencies: - OC_Pt: {model: linear, - units: {energy: eV, quantity: molec}, - enthalpy: 0.48, entropy: -0.031} - C_Pt: {model: polynomial, - units: {energy: J, quantity: mol}, - enthalpy-coefficients: [0.0, -3.86e4, 0.0, 4.2e5], - entropy-coefficients: [0.8e3, 0.0, -1.26e4, 0.0]} - CO2_Pt: {model: piecewise-linear, - units: {energy: kJ, quantity: mol}, - enthalpy-low: 0.5e2, enthalpy-high: 1.0e2, - enthalpy-change: 0.4, - entropy-low: 0.1e2, entropy-high: -0.2e2, - entropy-change: 0.4, - heat-capacity-a: 0.02e-1, heat-capacity-b: -0.156e-1} - O_Pt: {model: interpolative, - units: {energy: kcal, quantity: mol}, - enthalpy-coverages: [0.0, 0.2, 0.4, 0.7, 0.9, 1.0], - enthalpies: [0.0, 0.5, 1.0, 2.7, 3.5, 4.0], - entropy-coverages: [0.0, 0.5, 1.0], - entropies: [0.0, -0.7, -2.0]} - - .. _sec-yaml-species-transport: Species transport models @@ -630,3 +547,152 @@ Example:: diameter: 3.458 polarizability: 1.6 rotational-relaxation: 3.8 + + +.. _sec-yaml-species-coverage: + +Species coverage dependencies +============================= + +The coverage-dependent surface species formulation calculates coverage-dependent +correction factors to the ideal surface phase properties. Used in conjunction with the +:ref:`coverage-dependent-surface ` phase model. +Full details are :ct:`described here `. + +Fields of a species ``coverage-dependencies`` map entry used by all models are: + +``model`` + String specifying the model to be used. Required. Supported model strings are: + + - ``linear`` (:ref:`details `) + - ``polynomial`` (:ref:`details `) + - ``piecewise-linear`` (:ref:`details `) + - ``interpolative`` (:ref:`details `) + + +.. _sec-yaml-species-coverage-linear: + +Linear dependency model +----------------------- + +``enthalpy`` + Slope of the coverage-dependent enthalpy. + +``entropy`` + Slope of the coverage-dependent entropy. + +Example:: + + coverage-dependencies: + O_Pt: + model: linear + units: {energy: eV, quantity: molec} + enthalpy: 0.48 + entropy: -0.031 + # + other entries (optional) + + +.. _sec-yaml-species-coverage-polynomial: + +Polynomial dependency model +--------------------------- + +``enthalpy-coefficients`` + Array of polynomial coefficients in order of 1st, 2nd, 3rd, and + 4th-order used in coverage-dependent enthalpy calculation. + +``entropy-coefficients`` + Array of polynomial coefficients in order of 1st, 2nd, 3rd, and + 4th-order used in coverage-dependent entropy calculation. + +Example:: + + coverage-dependencies: + OC_Pt: + model: polynomial + units: {energy: J, quantity: mol} + enthalpy-coefficients: [0.0, -3.86e4, 0.0, 4.2e5] + entropy-coefficients: [0.8e3, 0.0, -1.26e4, 0.0] + # + other entries (optional) + + +.. _sec-yaml-species-coverage-piecewise-linear: + +Piecewise-linear dependency model +--------------------------------- + +``enthalpy-low`` + Slope of the coverage-dependent enthalpy for the lower coverage region. + +``entropy-low`` + Slope of the coverage-dependent entropy for the lower coverage region. + +``enthalpy-high`` + Slope of the coverage-dependent enthalpy for the higher coverage region. + +``entropy-high`` + Slope of the coverage-dependent entropy for the higher coverage region. + +``enthalpy-change`` + Coverage that separates the lower and higher coverage regions of the + coverage-dependent enthalpy. + +``entropy-change`` + Coverage that separates the lower and higher coverage regions of the + coverage-dependent entropy. + +``heat-capacity-a`` + Coefficient :math:`c^{(a)}` used in the + :ct:`coverage-dependent heat capacity ` model. + +``heat-capacity-b`` + Coefficient :math:`c^{(b)}` used in the + :ct:`coverage-dependent heat capacity ` model. + +Example:: + + coverage-dependencies: + CO2_Pt: + model: piecewise-linear + units: {energy: kJ, quantity: mol} + enthalpy-low: 0.5e2 + enthalpy-high: 1.0e2 + enthalpy-change: 0.4 + entropy-low: 0.1e2 + entropy-high: -0.2e2 + entropy-change: 0.4 + heat-capacity-a: 0.02e-1 + heat-capacity-b: -0.156e-1 + # + other entries (optional) + + +.. _sec-yaml-species-coverage-interpolative: + +Interpolative dependency model +------------------------------ + +``enthalpy-coverages`` + Array of discrete coverage values used in coverage-dependent enthalpy. + +``entropy-coverages`` + Array of discrete coverage values used in coverage-dependent entropy. + +``enthalpies`` + Array of discrete enthalpy values corresponding to the + coverages in ``enthalpy-coverages``. + +``entropies`` + Array of discrete entropy values corresponding to the + coverages in ``entropy-coverages``. + +Example:: + + coverage-dependencies: + C_Pt: + model: interpolative + units: {energy: kcal, quantity: mol} + enthalpy-coverages: [0.0, 0.2, 0.4, 0.7, 0.9, 1.0] + entropy-coverages: [0.0, 0.5, 1.0] + enthalpies: [0.0, 0.5, 1.0, 2.7, 3.5, 4.0] + entropies: [0.0, -0.7, -2.0] + # + other entries (optional)