diff --git a/doc/sphinx/cti/reactions.rst b/doc/sphinx/cti/reactions.rst index 6bd361f77..2aabcf111 100644 --- a/doc/sphinx/cti/reactions.rst +++ b/doc/sphinx/cti/reactions.rst @@ -144,6 +144,7 @@ should be handled. negative orders for a global reaction only if the ``negative_orders`` override option is specified for the reaction. + Reactions with Pressure-Independent Rate ======================================== @@ -458,6 +459,42 @@ used:: coverage=[['H(S)', a_1, m_1, E_1], ['PT(S)', a_2, m_2, E_2]])) +Additional Options +================== + +Reaction Orders +--------------- + +Explicit reaction orders different from the stoichiometric coefficients are +sometimes used for non-elementary reactions. For example, consider the global +reaction: + +.. math:: + \mathrm{C_8H_{18} + 12.5 O_2 \rightarrow 8 CO_2 + 9 H_2O} + +the forward rate constant might be given as [#Westbrook1981]_: + +.. math:: + k_f = 4.6 \times 10^{11} [\mathrm{C_8H_{18}}]^{0.25} [\mathrm{O_2}]^{1.5} + \exp\left(\frac{30.0\,\mathrm{kcal/mol}}{RT}\right) + +This reaction could be defined as:: + + reaction("C8H18 + 12.5 O2 => 8 CO2 + 9 H2O", [4.6e11, 0.0, 30.0], + order="C8H18:0.25 O2:1.5") + +Special care is required in this case since the units of the pre-exponential +factor depend on the sum of the reaction orders, which may not be an integer. + +Normally, reaction orders are required to be positive. However, in some cases +negative reaction orders are found to be better fits for experimental data. In +these cases, the default behavior may be overridden by adding +``negative_orders`` to the reaction options, e.g.:: + + reaction("C8H18 + 12.5 O2 => 8 CO2 + 9 H2O", [4.6e11, 0.0, 30.0], + order="C8H18:-0.25 O2:1.75", options=['negative_orders']) + + .. rubric:: References .. [#Gilbert1983] R. G. Gilbert, K. Luther, and @@ -477,3 +514,7 @@ used:: .. [#Kee1989] R. J. Kee, F. M. Rupley, and J. A. Miller. Chemkin-II: A Fortran chemical kinetics package for the analysis of gas-phase chemical kinetics. Technical Report SAND89-8009, Sandia National Laboratories, 1989. + +.. [#Westbrook1981] C. K. Westbrook and F. L. Dryer. Simplified reaction + mechanisms for the oxidation of hydrocarbon fuels in flames. *Combustion + Science and Technology* **27**, pp. 31--43. 1981. diff --git a/interfaces/cython/cantera/ctml_writer.py b/interfaces/cython/cantera/ctml_writer.py index 47ee358b0..9ecd06e95 100644 --- a/interfaces/cython/cantera/ctml_writer.py +++ b/interfaces/cython/cantera/ctml_writer.py @@ -1128,6 +1128,10 @@ class reaction(object): An optional identification string. If omitted, it defaults to a four-digit numeric string beginning with 0001 for the first reaction in the file. + :param order: + Override the default reaction orders implied by the reactant + stoichiometric coefficients. Given as a string of key:value pairs, + e.g. ``"CH4:0.25 O2:1.5"``. :param options: Processing options, as described in :ref:`sec-reaction-options`. May be one or more (as a list) of the following: 'skip', 'duplicate', 'negative_A', 'negative_orders'.