'''Chemical Engineering Design Library (ChEDL). Utilities for process modeling.
Copyright (C) 2016, 2017, 2018, 2019, 2020 Caleb Bell <Caleb.Andrew.Bell@gmail.com>
Permission is hereby granted, free of charge, to any person obtaining a copy
of this software and associated documentation files (the "Software"), to deal
in the Software without restriction, including without limitation the rights
to use, copy, modify, merge, publish, distribute, sublicense, and/or sell
copies of the Software, and to permit persons to whom the Software is
furnished to do so, subject to the following conditions:
The above copyright notice and this permission notice shall be included in all
copies or substantial portions of the Software.
THE SOFTWARE IS PROVIDED "AS IS", WITHOUT WARRANTY OF ANY KIND, EXPRESS OR
IMPLIED, INCLUDING BUT NOT LIMITED TO THE WARRANTIES OF MERCHANTABILITY,
FITNESS FOR A PARTICULAR PURPOSE AND NONINFRINGEMENT. IN NO EVENT SHALL THE
AUTHORS OR COPYRIGHT HOLDERS BE LIABLE FOR ANY CLAIM, DAMAGES OR OTHER
LIABILITY, WHETHER IN AN ACTION OF CONTRACT, TORT OR OTHERWISE, ARISING FROM,
OUT OF OR IN CONNECTION WITH THE SOFTWARE OR THE USE OR OTHER DEALINGS IN THE
SOFTWARE.
This module contains implementations of :obj:`thermo.utils.TDependentProperty`
representing enthalpy of vaporization and enthalpy of sublimation. A variety of
estimation and data methods are available as included in the `chemicals` library.
For reporting bugs, adding feature requests, or submitting pull requests,
please use the `GitHub issue tracker <https://github.com/CalebBell/thermo/>`_.
.. contents:: :local:
Enthalpy of Vaporization
========================
.. autoclass:: EnthalpyVaporization
:members: calculate, test_method_validity,
interpolation_T, interpolation_property,
interpolation_property_inv, name, property_max, property_min,
units, ranked_methods, Watson_exponent
:undoc-members:
:show-inheritance:
:exclude-members:
.. autodata:: enthalpy_vaporization_methods
Enthalpy of Sublimation
=======================
.. autoclass:: EnthalpySublimation
:members: calculate, test_method_validity,
interpolation_T, interpolation_property,
interpolation_property_inv, name, property_max, property_min,
units, ranked_methods
:undoc-members:
:show-inheritance:
:exclude-members:
.. autodata:: enthalpy_sublimation_methods
'''
__all__ = ['enthalpy_vaporization_methods', 'EnthalpyVaporization',
'enthalpy_sublimation_methods', 'EnthalpySublimation']
from chemicals import miscdata, phase_change
from chemicals.dippr import EQ106
from chemicals.identifiers import CAS_to_int
from chemicals.miscdata import lookup_VDI_tabular_data
from chemicals.phase_change import MK, PPDS12, SMK, Alibakhshi, Chen, Clapeyron, Liu, Pitzer, Riedel, Velasco, Vetere, Watson
from fluids.numerics import isnan
from thermo.coolprop import CoolProp_failing_PT_flashes, PropsSI, coolprop_dict, coolprop_fluids, has_CoolProp
from thermo.heat_capacity import HeatCapacityGas, HeatCapacitySolid
from thermo.utils import COOLPROP, DIPPR_PERRY_8E, HEOS_FIT, VDI_PPDS, VDI_TABULAR, TDependentProperty
CRC_HVAP_TB = 'CRC_HVAP_TB'
CRC_HVAP_298 = 'CRC_HVAP_298'
GHARAGHEIZI_HVAP_298 = 'GHARAGHEIZI_HVAP_298'
MORGAN_KOBAYASHI = 'MORGAN_KOBAYASHI'
SIVARAMAN_MAGEE_KOBAYASHI = 'SIVARAMAN_MAGEE_KOBAYASHI'
VELASCO = 'VELASCO'
PITZER = 'PITZER'
CLAPEYRON = 'CLAPEYRON'
ALIBAKHSHI = 'ALIBAKHSHI'
RIEDEL = 'RIEDEL'
CHEN = 'CHEN'
LIU = 'LIU'
VETERE = 'VETERE'
enthalpy_vaporization_methods = [HEOS_FIT, DIPPR_PERRY_8E, VDI_PPDS, COOLPROP, VDI_TABULAR,
MORGAN_KOBAYASHI,
SIVARAMAN_MAGEE_KOBAYASHI, VELASCO, PITZER, ALIBAKHSHI,
CRC_HVAP_TB, CRC_HVAP_298, GHARAGHEIZI_HVAP_298,
CLAPEYRON, RIEDEL, CHEN, VETERE, LIU]
"""Holds all methods available for the EnthalpyVaporization class, for use in
iterating over them."""
[docs]class EnthalpyVaporization(TDependentProperty):
'''Class for dealing with heat of vaporization as a function of temperature.
Consists of three constant value data sources, one source of tabular
information, three coefficient-based methods, nine corresponding-states
estimators, and the external library CoolProp.
Parameters
----------
Tb : float, optional
Boiling point, [K]
Tc : float, optional
Critical temperature, [K]
Pc : float, optional
Critical pressure, [Pa]
omega : float, optional
Acentric factor, [-]
similarity_variable : float, optional
similarity variable, n_atoms/MW, [mol/g]
Psat : float or callable, optional
Vapor pressure at T or callable for the same, [Pa]
Zl : float or callable, optional
Compressibility of liquid at T or callable for the same, [-]
Zg : float or callable, optional
Compressibility of gas at T or callable for the same, [-]
CASRN : str, optional
The CAS number of the chemical
load_data : bool, optional
If False, do not load property coefficients from data sources in files
[-]
extrapolation : str or None
None to not extrapolate; see
:obj:`TDependentProperty <thermo.utils.TDependentProperty>`
for a full list of all options, [-]
method : str or None, optional
If specified, use this method by default and do not use the ranked
sorting; an exception is raised if this is not a valid method for the
provided inputs, [-]
Notes
-----
To iterate over all methods, use the list stored in
:obj:`enthalpy_vaporization_methods`.
**CLAPEYRON**:
The Clapeyron fundamental model desecribed in :obj:`Clapeyron <chemicals.phase_change.Clapeyron>`.
This is the model which uses `Zl`, `Zg`, and `Psat`, all of which
must be set at each temperature change to allow recalculation of
the heat of vaporization.
**MORGAN_KOBAYASHI**:
The MK CSP model equation documented in :obj:`MK <chemicals.phase_change.MK>`.
**SIVARAMAN_MAGEE_KOBAYASHI**:
The SMK CSP model equation documented in :obj:`SMK <chemicals.phase_change.SMK>`.
**VELASCO**:
The Velasco CSP model equation documented in :obj:`Velasco <chemicals.phase_change.Velasco>`.
**PITZER**:
The Pitzer CSP model equation documented in :obj:`Pitzer <chemicals.phase_change.Pitzer>`.
**RIEDEL**:
The Riedel CSP model equation, valid at the boiling point only,
documented in :obj:`Riedel <chemicals.phase_change.Riedel>`. This is adjusted with the :obj:`Watson <chemicals.phase_change.Watson>`
equation unless `Tc` is not available.
**CHEN**:
The Chen CSP model equation, valid at the boiling point only,
documented in :obj:`Chen <chemicals.phase_change.Chen>`. This is adjusted with the :obj:`Watson <chemicals.phase_change.Watson>`
equation unless `Tc` is not available.
**VETERE**:
The Vetere CSP model equation, valid at the boiling point only,
documented in :obj:`Vetere <chemicals.phase_change.Vetere>`. This is adjusted with the :obj:`Watson <chemicals.phase_change.Watson>`
equation unless `Tc` is not available.
**LIU**:
The Liu CSP model equation, valid at the boiling point only,
documented in :obj:`Liu <chemicals.phase_change.Liu>`. This is adjusted with the :obj:`Watson <chemicals.phase_change.Watson>`
equation unless `Tc` is not available.
**CRC_HVAP_TB**:
The constant value available in [4]_ at the normal boiling point. This
is adusted with the :obj:`Watson <chemicals.phase_change.Watson>` equation unless `Tc` is not
available. Data is available for 707 chemicals.
**CRC_HVAP_298**:
The constant value available in [4]_ at 298.15 K. This
is adusted with the :obj:`Watson <chemicals.phase_change.Watson>` equation unless `Tc` is not
available. Data is available for 633 chemicals.
**GHARAGHEIZI_HVAP_298**:
The constant value available in [5]_ at 298.15 K. This
is adusted with the :obj:`Watson <chemicals.phase_change.Watson>` equation unless `Tc` is not
available. Data is available for 2730 chemicals.
**COOLPROP**:
CoolProp external library; with select fluids from its library.
Range is limited to that of the equations of state it uses, as
described in [3]_. Very slow but accurate.
**VDI_TABULAR**:
Tabular data in [4]_ along the saturation curve; interpolation is as
set by the user or the default.
**VDI_PPDS**:
Coefficients for a equation form developed by the PPDS, published
openly in [3]_. Extrapolates poorly at low temperatures.
**DIPPR_PERRY_8E**:
A collection of 344 coefficient sets from the DIPPR database published
openly in [6]_. Provides temperature limits for all its fluids.
:obj:`chemicals.dippr.EQ106` is used for its fluids.
**ALIBAKHSHI**:
One-constant limited temperature range regression method presented
in [7]_, with constants for ~2000 chemicals from the DIPPR database.
Valid up to 100 K below the critical point, and 50 K under the boiling
point.
**HEOS_FIT**:
A series of higher-order polynomial fits to the calculated results from
fundamental helmholtz equations of state as calculated with REFPROP
See Also
--------
chemicals.phase_change.MK
chemicals.phase_change.SMK
chemicals.phase_change.Velasco
chemicals.phase_change.Clapeyron
chemicals.phase_change.Riedel
chemicals.phase_change.Chen
chemicals.phase_change.Vetere
chemicals.phase_change.Liu
chemicals.phase_change.Watson
References
----------
.. [1] Poling, Bruce E. The Properties of Gases and Liquids. 5th edition.
New York: McGraw-Hill Professional, 2000.
.. [2] Bell, Ian H., Jorrit Wronski, Sylvain Quoilin, and Vincent Lemort.
“Pure and Pseudo-Pure Fluid Thermophysical Property Evaluation and the
Open-Source Thermophysical Property Library CoolProp.” Industrial &
Engineering Chemistry Research 53, no. 6 (February 12, 2014):
2498-2508. doi:10.1021/ie4033999. http://www.coolprop.org/
.. [3] Gesellschaft, V. D. I., ed. VDI Heat Atlas. 2nd edition.
Berlin; New York:: Springer, 2010.
.. [4] Haynes, W.M., Thomas J. Bruno, and David R. Lide. CRC Handbook of
Chemistry and Physics. [Boca Raton, FL]: CRC press, 2014.
.. [5] Gharagheizi, Farhad, Poorandokht Ilani-Kashkouli, William E. Acree Jr.,
Amir H. Mohammadi, and Deresh Ramjugernath. "A Group Contribution Model for
Determining the Vaporization Enthalpy of Organic Compounds at the Standard
Reference Temperature of 298 K." Fluid Phase Equilibria 360
(December 25, 2013): 279-92. doi:10.1016/j.fluid.2013.09.021.
.. [6] Green, Don, and Robert Perry. Perry's Chemical Engineers' Handbook,
Eighth Edition. McGraw-Hill Professional, 2007.
.. [7] Alibakhshi, Amin. "Enthalpy of Vaporization, Its Temperature
Dependence and Correlation with Surface Tension: A Theoretical
Approach." Fluid Phase Equilibria 432 (January 25, 2017): 62-69.
doi:10.1016/j.fluid.2016.10.013.
'''
name = 'Enthalpy of vaporization'
units = 'J/mol'
interpolation_T = None
"""No interpolation transformation by default."""
interpolation_property = None
"""No interpolation transformation by default."""
interpolation_property_inv = None
"""No interpolation transformation by default."""
tabular_extrapolation_permitted = True
"""Allow tabular extrapolation by default; values below 0 will be obtained
at high temperatures."""
property_min = 0
"""Mimimum valid value of heat of vaporization. This occurs at the critical
point exactly."""
property_max = 1E6
"""Maximum valid of heat of vaporization. Set to twice the value in the
available data."""
critical_zero = True
"""Whether or not the property is declining and reaching zero at the
critical point."""
ranked_methods = [HEOS_FIT, COOLPROP, DIPPR_PERRY_8E, VDI_PPDS, MORGAN_KOBAYASHI,
SIVARAMAN_MAGEE_KOBAYASHI, VELASCO, PITZER, VDI_TABULAR,
ALIBAKHSHI,
CRC_HVAP_TB, CRC_HVAP_298, GHARAGHEIZI_HVAP_298,
CLAPEYRON, RIEDEL, CHEN, VETERE, LIU]
"""Default rankings of the available methods."""
boiling_methods = [RIEDEL, CHEN, VETERE, LIU]
CSP_methods = [MORGAN_KOBAYASHI, SIVARAMAN_MAGEE_KOBAYASHI,
VELASCO, PITZER]
Watson_exponent = 0.38
"""Exponent used in the Watson equation"""
custom_args = ('Tb', 'Tc', 'Pc', 'omega', 'similarity_variable', 'Psat',
'Zl', 'Zg',)
def __init__(self, CASRN='', Tb=None, Tc=None, Pc=None, omega=None,
similarity_variable=None, Psat=None, Zl=None, Zg=None,
extrapolation='Watson', **kwargs):
self.CASRN = CASRN
self.Tb = Tb
self.Tc = Tc
self.Pc = Pc
self.omega = omega
self.similarity_variable = similarity_variable
self.Psat = Psat
self.Zl = Zl
self.Zg = Zg
super().__init__(extrapolation, **kwargs)
def load_all_methods(self, load_data=True):
r'''Method which picks out coefficients for the specified chemical
from the various dictionaries and DataFrames storing it. All data is
stored as attributes. This method also sets :obj:`Tmin`, :obj:`Tmax`,
and :obj:`all_methods` as a set of methods for which the data exists for.
Called on initialization only. See the source code for the variables at
which the coefficients are stored. The coefficients can safely be
altered once the class is initialized. This method can be called again
to reset the parameters.
'''
methods = []
self.T_limits = T_limits = {}
self.all_methods = set()
CASRN = self.CASRN
if load_data and CASRN:
if has_CoolProp() and CASRN in coolprop_dict:
methods.append(COOLPROP)
self.CP_f = coolprop_fluids[CASRN]
T_limits[COOLPROP] = (self.CP_f.Tt, self.CP_f.Tc*.9999)
if CASRN in miscdata.VDI_saturation_dict:
Ts, props = lookup_VDI_tabular_data(CASRN, 'Hvap')
self.add_tabular_data(Ts, props, VDI_TABULAR, check_properties=False)
del self._method
if CASRN in phase_change.phase_change_data_Alibakhshi_Cs.index and self.Tc is not None:
methods.append(ALIBAKHSHI)
self.Alibakhshi_C = float(phase_change.phase_change_data_Alibakhshi_Cs.at[CASRN, 'C'])
T_limits[ALIBAKHSHI] = (self.Tc*.3, max(self.Tc-100., 0))
if CASRN in phase_change.Hvap_data_CRC.index and not isnan(phase_change.Hvap_data_CRC.at[CASRN, 'HvapTb']):
methods.append(CRC_HVAP_TB)
self.CRC_HVAP_TB_Tb = float(phase_change.Hvap_data_CRC.at[CASRN, 'Tb'])
self.CRC_HVAP_TB_Hvap = float(phase_change.Hvap_data_CRC.at[CASRN, 'HvapTb'])
if self.Tc is not None:
T_limits[CRC_HVAP_TB] = (self.Tc*.001, self.Tc)
else:
T_limits[CRC_HVAP_TB] = (self.CRC_HVAP_TB_Tb, self.CRC_HVAP_TB_Tb)
if CASRN in phase_change.Hvap_data_CRC.index and not isnan(phase_change.Hvap_data_CRC.at[CASRN, 'Hvap298']):
methods.append(CRC_HVAP_298)
self.CRC_HVAP_298 = float(phase_change.Hvap_data_CRC.at[CASRN, 'Hvap298'])
if self.Tc is not None:
T_limits[CRC_HVAP_298] = (self.Tc*.001, self.Tc)
else:
T_limits[CRC_HVAP_298] = (298.15, 298.15)
if CASRN in phase_change.Hvap_data_Gharagheizi.index:
methods.append(GHARAGHEIZI_HVAP_298)
self.GHARAGHEIZI_HVAP_298_Hvap = float(phase_change.Hvap_data_Gharagheizi.at[CASRN, 'Hvap298'])
if self.Tc is not None:
T_limits[GHARAGHEIZI_HVAP_298] = (self.Tc*.001, self.Tc)
else:
T_limits[GHARAGHEIZI_HVAP_298] = (298.15, 298.15)
if CASRN in phase_change.phase_change_data_Perrys2_150.index:
methods.append(DIPPR_PERRY_8E)
Tc, C1, C2, C3, C4, self.Perrys2_150_Tmin, self.Perrys2_150_Tmax = phase_change.phase_change_values_Perrys2_150[phase_change.phase_change_data_Perrys2_150.index.get_loc(CASRN)].tolist()
self.Perrys2_150_coeffs = [Tc, C1, C2, C3, C4]
T_limits[DIPPR_PERRY_8E] = (self.Perrys2_150_Tmin, self.Perrys2_150_Tmax)
if CASRN in phase_change.phase_change_data_VDI_PPDS_4.index:
Tc, A, B, C, D, E = phase_change.phase_change_values_VDI_PPDS_4[phase_change.phase_change_data_VDI_PPDS_4.index.get_loc(CASRN)].tolist()
self.VDI_PPDS_coeffs = [A, B, C, D, E]
self.VDI_PPDS_Tc = Tc
methods.append(VDI_PPDS)
T_limits[VDI_PPDS] = (0.1*self.VDI_PPDS_Tc, self.VDI_PPDS_Tc)
if all((self.Tc, self.omega)):
methods.extend(self.CSP_methods)
for m in self.CSP_methods:
T_limits[m] = (1e-4, self.Tc)
if all((self.Tc, self.Pc)):
methods.append(CLAPEYRON)
T_limits[CLAPEYRON] = (1e-4, self.Tc)
if all((self.Tb, self.Tc, self.Pc)):
methods.extend(self.boiling_methods)
for m in self.boiling_methods:
T_limits[m] = (1e-4, self.Tc)
self.all_methods.update(methods)
@staticmethod
def _method_indexes():
'''Returns a dictionary of method: index for all methods
that use data files to retrieve constants. The use of this function
ensures the data files are not loaded until they are needed.
'''
return {COOLPROP : [CAS for CAS in coolprop_dict if (CAS not in CoolProp_failing_PT_flashes)],
VDI_TABULAR: list(miscdata.VDI_saturation_dict.keys()),
DIPPR_PERRY_8E: phase_change.phase_change_data_Perrys2_150.index,
VDI_PPDS: phase_change.phase_change_data_VDI_PPDS_4.index,
}
[docs] def calculate(self, T, method):
r'''Method to calculate heat of vaporization of a liquid at
temperature `T` with a given method.
This method has no exception handling; see :obj:`T_dependent_property <thermo.utils.TDependentProperty.T_dependent_property>`
for that.
Parameters
----------
T : float
Temperature at which to calculate heat of vaporization, [K]
method : str
Name of the method to use
Returns
-------
Hvap : float
Heat of vaporization of the liquid at T, [J/mol]
'''
if method == COOLPROP:
Hvap = PropsSI('HMOLAR', 'T', T, 'Q', 1, self.CASRN) - PropsSI('HMOLAR', 'T', T, 'Q', 0, self.CASRN)
elif method == DIPPR_PERRY_8E:
Hvap = EQ106(T, *self.Perrys2_150_coeffs)
# CSP methods
elif method == VDI_PPDS:
Hvap = PPDS12(T, self.VDI_PPDS_Tc, *self.VDI_PPDS_coeffs)
elif method == ALIBAKHSHI:
Hvap = Alibakhshi(T=T, Tc=self.Tc, C=self.Alibakhshi_C)
elif method == MORGAN_KOBAYASHI:
Hvap = MK(T, self.Tc, self.omega)
elif method == SIVARAMAN_MAGEE_KOBAYASHI:
Hvap = SMK(T, self.Tc, self.omega)
elif method == VELASCO:
Hvap = Velasco(T, self.Tc, self.omega)
elif method == PITZER:
Hvap = Pitzer(T, self.Tc, self.omega)
elif method == CLAPEYRON:
Psat = self.Psat(T) if callable(self.Psat) else self.Psat
Zg = self.Zg(T, Psat) if callable(self.Zg) else self.Zg
Zl = self.Zl(T, Psat) if callable(self.Zl) else self.Zl
if Zg:
if Zl:
dZ = Zg-Zl
else:
dZ = Zg
Hvap = Clapeyron(T, self.Tc, self.Pc, dZ=dZ, Psat=Psat)
# CSP methods at Tb only
elif method == RIEDEL:
Hvap = Riedel(self.Tb, self.Tc, self.Pc)
elif method == CHEN:
Hvap = Chen(self.Tb, self.Tc, self.Pc)
elif method == VETERE:
Hvap = Vetere(self.Tb, self.Tc, self.Pc)
elif method == LIU:
Hvap = Liu(self.Tb, self.Tc, self.Pc)
# Individual data point methods
elif method == CRC_HVAP_TB:
Hvap = self.CRC_HVAP_TB_Hvap
elif method == CRC_HVAP_298:
Hvap = self.CRC_HVAP_298
elif method == GHARAGHEIZI_HVAP_298:
Hvap = self.GHARAGHEIZI_HVAP_298_Hvap
else:
return self._base_calculate(T, method)
# Adjust with the watson equation if estimated at Tb or Tc only
if method in self.boiling_methods or (self.Tc and method in (CRC_HVAP_TB, CRC_HVAP_298, GHARAGHEIZI_HVAP_298)):
if method in self.boiling_methods:
Tref = self.Tb
elif method == CRC_HVAP_TB:
Tref = self.CRC_HVAP_TB_Tb
elif method in [CRC_HVAP_298, GHARAGHEIZI_HVAP_298]:
Tref = 298.15
Hvap = Watson(T, Hvap, Tref, self.Tc, self.Watson_exponent)
return Hvap
[docs] def test_method_validity(self, T, method):
r'''Method to check the validity of a method. For CSP methods, the
models are considered valid from 0 K to the critical point. For
tabular data, extrapolation outside of the range is used if
:obj:`tabular_extrapolation_permitted` is set; if it is, the
extrapolation is considered valid for all temperatures.
It is not guaranteed that a method will work or give an accurate
prediction simply because this method considers the method valid.
The constant methods **CRC_HVAP_TB**, **CRC_HVAP_298**, and
**GHARAGHEIZI_HVAP** are adjusted for temperature dependence according
to the :obj:`Watson <chemicals.phase_change.Watson>` equation, with a temperature exponent as set in
:obj:`Watson_exponent`, usually regarded as 0.38. However, if Tc is
not set, then the adjustment cannot be made. In that case the methods
are considered valid for within 5 K of their boiling point or 298.15 K
as appropriate.
Parameters
----------
T : float
Temperature at which to test the method, [K]
method : str
Name of the method to test
Returns
-------
validity : bool
Whether or not a method is valid
'''
validity = True
if method == COOLPROP:
if T <= self.CP_f.Tmin or T > self.CP_f.Tc:
validity = False
elif method == DIPPR_PERRY_8E:
if T < self.Perrys2_150_Tmin or T > self.Perrys2_150_Tmax:
return False
elif method == CRC_HVAP_TB:
if not self.Tc:
if T < self.CRC_HVAP_TB_Tb - 5 or T > self.CRC_HVAP_TB_Tb + 5:
validity = False
else:
validity = T <= self.Tc
elif method in (CRC_HVAP_298, GHARAGHEIZI_HVAP_298):
if not self.Tc:
if T < 298.15 - 5 or T > 298.15 + 5:
validity = False
elif method == VDI_PPDS:
validity = T <= self.VDI_PPDS_Tc
elif method in self.boiling_methods:
if T > self.Tc:
validity = False
elif method in self.CSP_methods:
if T > self.Tc:
validity = False
elif method == ALIBAKHSHI:
if T > self.Tc - 100:
validity = False
# elif (self.Tb and T < self.Tb - 50):
# validity = False
elif method == CLAPEYRON:
if not (self.Psat and T < self.Tc):
validity = False
else:
return super().test_method_validity(T, method)
return validity
### Heat of Sublimation
GHARAGHEIZI_HSUB_298 = 'GHARAGHEIZI_HSUB_298'
GHARAGHEIZI_HSUB = 'GHARAGHEIZI_HSUB'
CRC_HFUS_HVAP_TM = 'CRC_HFUS_HVAP_TM' # Gets Tm
WEBBOOK_HSUB = 'WEBBOOK_HSUB'
enthalpy_sublimation_methods = [WEBBOOK_HSUB, GHARAGHEIZI_HSUB, CRC_HFUS_HVAP_TM,
GHARAGHEIZI_HSUB_298]
"""Holds all methods available for the EnthalpySublimation class, for use in
iterating over them."""
[docs]class EnthalpySublimation(TDependentProperty):
'''Class for dealing with heat of sublimation as a function of temperature.
Consists of one temperature-dependent method based on the heat of
sublimation at 298.15 K.
Parameters
----------
CASRN : str, optional
The CAS number of the chemical
Tm : float, optional
Normal melting temperature, [K]
Tt : float, optional
Triple point temperature, [K]
Cpg : float or callable, optional
Gaseous heat capacity at a given temperature or callable for the same,
[J/mol/K]
Cps : float or callable, optional
Solid heat capacity at a given temperature or callable for the same,
[J/mol/K]
Hvap : float of callable, optional
Enthalpy of Vaporization at a given temperature or callable for the
same, [J/mol]
load_data : bool, optional
If False, do not load property coefficients from data sources in files
[-]
extrapolation : str or None
None to not extrapolate; see
:obj:`TDependentProperty <thermo.utils.TDependentProperty>`
for a full list of all options, [-]
method : str or None, optional
If specified, use this method by default and do not use the ranked
sorting; an exception is raised if this is not a valid method for the
provided inputs, [-]
Notes
-----
To iterate over all methods, use the list stored in
:obj:`enthalpy_sublimation_methods`.
**WEBBOOK_HSUB**:
Enthalpy of sublimation at a constant temperature of 298.15 K as given
in [3]_.
**GHARAGHEIZI_HSUB_298**:
Enthalpy of sublimation at a constant temperature of 298 K as given in
[1]_.
**GHARAGHEIZI_HSUB**:
Enthalpy of sublimation at a constant temperature of 298 K as given in
[1]_ are adjusted using the solid and gas heat capacity functions to
correct for any temperature.
**CRC_HFUS_HVAP_TM**:
Enthalpies of fusion in [1]_ are corrected to be enthalpies of
sublimation by adding the enthalpy of vaporization at the fusion
temperature, and then adjusted using the solid and gas heat capacity
functions to correct for any temperature.
See Also
--------
References
----------
.. [1] Gharagheizi, Farhad, Poorandokht Ilani-Kashkouli, William E. Acree
Jr., Amir H. Mohammadi, and Deresh Ramjugernath. "A Group Contribution
Model for Determining the Sublimation Enthalpy of Organic Compounds at
the Standard Reference Temperature of 298 K." Fluid Phase Equilibria 354
(September 25, 2013): 265-doi:10.1016/j.fluid.2013.06.046.
.. [2] Haynes, W.M., Thomas J. Bruno, and David R. Lide. CRC Handbook of
Chemistry and Physics, 95E. Boca Raton, FL: CRC press, 2014.
.. [3] Shen, V.K., Siderius, D.W., Krekelberg, W.P., and Hatch, H.W., Eds.,
NIST WebBook, NIST, http://doi.org/10.18434/T4M88Q
'''
name = 'Enthalpy of sublimation'
units = 'J/mol'
interpolation_T = None
"""No interpolation transformation by default."""
interpolation_property = None
"""No interpolation transformation by default."""
interpolation_property_inv = None
"""No interpolation transformation by default."""
tabular_extrapolation_permitted = True
"""Allow tabular extrapolation by default; values below 0 will be obtained
at high temperatures."""
property_min = 0
"""Mimimum valid value of heat of vaporization. A theoretical concept only."""
property_max = 1E6
"""Maximum valid of heat of sublimation. A theoretical concept only."""
ranked_methods = [WEBBOOK_HSUB, GHARAGHEIZI_HSUB, CRC_HFUS_HVAP_TM,
GHARAGHEIZI_HSUB_298]
obj_references = pure_references = ('Cpg', 'Cps', 'Hvap')
obj_references_types = pure_reference_types = (HeatCapacityGas, HeatCapacitySolid, EnthalpyVaporization)
custom_args = ('Tm', 'Tt', 'Cpg', 'Cps', 'Hvap')
def __init__(self, CASRN='', Tm=None, Tt=None, Cpg=None, Cps=None,
Hvap=None, extrapolation='linear', **kwargs):
self.CASRN = CASRN
self.Tm = Tm
self.Tt = Tt
self.Cpg = Cpg
self.Cps = Cps
self.Hvap = Hvap
super().__init__(extrapolation, **kwargs)
def load_all_methods(self, load_data=True):
r'''Method which picks out coefficients for the specified chemical
from the various dictionaries and DataFrames storing it. All data is
stored as attributes. This method also sets :obj:`Tmin`, :obj:`Tmax`,
and :obj:`all_methods` as a set of methods for which the data exists for.
Called on initialization only. See the source code for the variables at
which the coefficients are stored. The coefficients can safely be
altered once the class is initialized. This method can be called again
to reset the parameters.
'''
methods = []
self.T_limits = T_limits = {}
CASRN = self.CASRN
CASRN_int = None if not CASRN else CAS_to_int(CASRN)
if load_data and CASRN:
if CASRN_int in miscdata.webbook_data.index and not isnan(float(miscdata.webbook_data.at[CASRN_int, 'Hsub'])):
methods.append(WEBBOOK_HSUB)
self.webbook_Hsub = float(miscdata.webbook_data.at[CASRN_int, 'Hsub'])
if self.Tm is not None:
T_limits[WEBBOOK_HSUB] = (self.Tm, self.Tm)
else:
T_limits[WEBBOOK_HSUB] = (298.15, 298.15)
if CASRN in phase_change.Hsub_data_Gharagheizi.index:
methods.append(GHARAGHEIZI_HSUB_298)
self.GHARAGHEIZI_Hsub = float(phase_change.Hsub_data_Gharagheizi.at[CASRN, 'Hsub'])
if self.Cpg is not None and self.Cps is not None:
methods.append(GHARAGHEIZI_HSUB)
T_limits[GHARAGHEIZI_HSUB_298] = (298.15, 298.15)
if CASRN in phase_change.Hfus_data_CRC.index:
methods.append(CRC_HFUS_HVAP_TM)
self.CRC_Hfus = float(phase_change.Hfus_data_CRC.at[CASRN, 'Hfus'])
if self.Tm is not None:
T_limits[CRC_HFUS_HVAP_TM] = (self.Tm, self.Tm)
else:
T_limits[CRC_HFUS_HVAP_TM] = (298.15, 298.15)
self.all_methods = set(methods)
@staticmethod
def _method_indexes():
'''Returns a dictionary of method: index for all methods
that use data files to retrieve constants. The use of this function
ensures the data files are not loaded until they are needed.
'''
return {}
[docs] def calculate(self, T, method):
r'''Method to calculate heat of sublimation of a solid at
temperature `T` with a given method.
This method has no exception handling; see :obj:`T_dependent_property <thermo.utils.TDependentProperty.T_dependent_property>`
for that.
Parameters
----------
T : float
Temperature at which to calculate heat of sublimation, [K]
method : str
Name of the method to use
Returns
-------
Hsub : float
Heat of sublimation of the solid at T, [J/mol]
'''
if method == GHARAGHEIZI_HSUB_298:
Hsub = self.GHARAGHEIZI_Hsub
elif method == WEBBOOK_HSUB:
Hsub = self.webbook_Hsub
elif method == GHARAGHEIZI_HSUB:
T_base = 298.15
Hsub = self.GHARAGHEIZI_Hsub
elif method == CRC_HFUS_HVAP_TM:
T_base = self.Tm
Hsub = self.CRC_Hfus
try:
Hsub += self.Hvap(T_base)
except:
Hsub += self.Hvap
else:
return self._base_calculate(T, method)
if method in (GHARAGHEIZI_HSUB, CRC_HFUS_HVAP_TM):
try:
# Cpg, Cps = self.Cpg(T_base), self.Cps(T_base)
# Hsub += (T - T_base)*(Cpg - Cps)
Hsub += self.Cpg.T_dependent_property_integral(T_base, T) - self.Cps.T_dependent_property_integral(T_base, T)
except:
Hsub += (T - T_base)*(self.Cpg - self.Cps)
return Hsub
[docs] def test_method_validity(self, T, method):
r'''Method to check the validity of a method. For
tabular data, extrapolation outside of the range is used if
:obj:`tabular_extrapolation_permitted` is set; if it is, the
extrapolation is considered valid for all temperatures.
It is not guaranteed that a method will work or give an accurate
prediction simply because this method considers the method valid.
Parameters
----------
T : float
Temperature at which to test the method, [K]
method : str
Name of the method to test
Returns
-------
validity : bool
Whether or not a method is valid
'''
validity = True
if method in (GHARAGHEIZI_HSUB_298, GHARAGHEIZI_HSUB, CRC_HFUS_HVAP_TM, WEBBOOK_HSUB):
validity = True
else:
return super().test_method_validity(T, method)
return validity