HISTORY.md

v0.6.11

New Features

• The new minimum supported julia version is v1.10.
• Support for ForwardDiff v1.0.
• the following EoS now support parametric parameters:
  • SAFTgammaMie (including structSAFTgammaMie)
  • PCPSAFT (including HeterogcPCPSAFT and HomogcPCPSAFT)
  • CPPCSAFT
  • sPCSAFT (including gcsPCSAFT)
  • pharmaPCSAFT

Given a model with parametric parameters, one can now build another model with a different number type using the function Clapeyron.promote_model(::Type{T},model) where T <: Number.

• SAFTgammaMie: mixed segment paramters are now stored in the model parameters instead of inside the groups.
• Faster split_model
• Faster parameter instantiation, as now the sources and sourcescsv can be optionally nothing,and there is less copying of vectors.
• New Function: USCT_temperature. USCT_mix was renamed to USCT_pressure (The alias is still available, but it could be removed in future Clapeyron versions.)
• Estimation Framework: initial support for gradient optimization (using ForwardDiff) with parametric models.

Bug Fixes

• fixed CPA initialization with custom parameters.
• fixed CPA default locations.
• fixed ePCSAFT initialization with custom ideal models.
• general flash: support for pure supercritical states.
• fix bugs in noncondensable/nonvolatiles Fugacity solver.

v0.6.10

New Features

• Experimental: support for using ForwardDiff through some equilibria procedures in some restricted cases:

  • saturation_temperature
  • saturation_pressure
  • bubble_pressure (only helmholtz EoS, without non-volatiles)
  • bubble_temperature (only helmholtz EoS, without non-volatiles)
  • dew_pressure (only helmholtz EoS, without non-condensables)
  • dew_temperature (only helmholtz EoS, without non-condensables)
  • tp_flash (only helmholtz EoS, without non-condensables nor non-volatiles)
  • Pproperty
  • TProperty
  • X-Y flashes (single component helmholtz EoS)

  For example, this function now works without the need to propagate dual information through any iterative solvers:

  function ad_function(model,Q)
  
    z = Clapeyron.SA[1.0]
    p = 1e5
    T = 350.0
    k = 10
    h1 = 6200.0
    T1 = PH.temperature(model,p,h1,z)
    h2 = h1 + Q
    T2 = PH.temperature(model,p,h2,z)
    return -Q + (T - (T1+T2)/2) * k
  end
  model = PR("air")
  ForwardDiff.derivative(Base.Fix1(ad_function,model),500.0)

Bug Fixes

• Fix typo in composition return ChemPotDewTemperature
• incorrect scaling for second virial coefficient in the case of cubics
• fixing support for second order properties in activity + puremodel EoS calculation

v0.6.9

New Features

• pharmaPCSAFT now considers water and water08 for it's T-dependend hard-sphere diameter. Before, only water08 used the specialized behaviour, and water returned the stock PCSAFT parameters.
• speed improvements in MichelsenTPFlash and fugacity-based bubble/dew calculations

Bug Fixes

• Fix errors with the use of EoSSuperancillaries along with pharmaPCSAFT
• rachford-rice: Fix errors when there are NaN K-values corresponding to non-condensables or non-volatiles.
• tp_flash: Fix errors when there are NaN K-values corresponding to non-condensables or non-volatiles.
• typo in x0_sat_pure_spinodal

v0.6.8

New Features

• New function: partial_property, for calculating partial properties at constant pressure and temperature.
• New functions: widom_pressure,widom_temperature,ciic_pressure,ciic_temperature, that calculate the maxima of isobaric heat capacity at constant pressure (widom) or constant temperature (CIIC).
• New models: original UNIFAC 2.0 (ogUNIFAC2, from doi.org/10.1016/j.cej.2024.158667) and modified (Dortmund) UNIFAC 2.0 (UNIFAC2, from doi.org/10.48550/arXiv.2412.12962).
• Ideal models: now all ideal models (with the exception of BasicIdeal) support optionally setting molecular weights.
• Database: the behaviour of getparams(;return_sites) was changed. Now, all single parameters used when building the SiteParam will be removed from the result (if sites are built.). The removed parameters will also not be checked for complete specification (non-existing sites are made equivalent to zero sites).
• Estimation: more flexibility in setting indices.
• ReidIdeal: Parameters for a,b,c,d,e are now included in ReidIdealParam.

Bug Fixes

• Stability improvements in xy_flash.
• Stability improvements in bubble and dew points
• Fix K-value initialization when components are over JT temperature.
• Stability improvements for spinodal initialization, used for pure saturation pressure calculations.

v0.6.7

Bug Fixes

• Fixed bugs on the PH and PS modules.
• Symbolics.jl extension now compiles correctly.
• Stability improvements in xy_flash

v0.6.6

New Features

• New general formulation for flashes. the formulation supports any combination of P,T,H,U,S,V,vapour fraction (q),given that initial values are provided. the formulation can be accessed via calling the function Clapeyron.xy_flash(model,spec::FlashSpecifications,z,components0,fractions0,volumes0,T0)
• New methods: flashes based on the general formulation, with automatic initialization:
  • p-H flash: (ph_flash)
  • p-S flash: (ps_flash)
  • V-T flash: (vt_flash)
  • T-S flash: (ts_flash)
  • vapour fraction - T flash: (qt_flash)
  • vapour fraction - P flash: (qp_flash)
• New Flash method: GeneralizedXYFlash, the only available method for other flashes that are not P-T formulations.
• New method: Clapeyron.set_reference_state!(model::EoSModel,state::ReferenceState;verbose = false), that allows setting reference states for any model that supports it.
• flashes (with the exception of tp_flash) now return a FlashResult object. Clapeyron.tp_flash2 returns a FlashResult that is converted to the old format internally.
• New function: PProperty(model,T,prop,z,property), that calculates the pressure in T-X coordinates.
• Activity models and Composite-γ-ϕ Models can now be used to calculate caloric properties.
• Activity models and Composite-γ-ϕ Models have support for setting reference states.
• Better Base.show methods for some Clapeyron.jl structs
• Reference states are now shown for models.
• the default method for tp_flash was changed to MichelsenTPFlash

Bug Fixes

• TProperty fixes and stability improvements.
• stability improvements in calculation of bubble/dew initial points
• stability improvements when calculating Rachford-Rice iterations.
• fixes for setting reference states with cubic EoS, SAFT-γ-Mie and other custom EoS not created via @newmodel macros.
• fixes for some component names not being used in empiric EoS
• fixes for crit_mix

v0.6.5

New Features

• Experimental: Bulk properties for Pressure-Enthalpy and Pressure-Entropy, the syntax is the following:

  using Clapeyron: PH
  PH.entropy(model,p,h,z)
  PH.adiabatic_index(model,p,h,z,T0 = T0) #suplying an initial point for the temperature

  The calculation is done via Clapeyron.Tproperty. there are also PT and VT functions for parity.

Bug fixes

• fixes in calculation of spinodal with cubics.
• MultiFluid and SingleFluid errors when T_reducing != Tc.
• fix VT_identify_phase.
• fix GC-to-component asssociation mix when there are non-symmetric values.

v0.6.4

New Features

• New model: SAFT-VR-Mie with Gross-Vrabec quatrupolar contribution (SAFTVRMieGV)
• New model: Co-Oriented Fluid Functional Equation for Electrostatic interactions (COFFEE)
• Better support for evaluation of model properties at V == Inf (ideal gas limit)
• New method: adiabatic_index, that calculates the ratio between the isobaric and isochoric heat capacities.
• new API: has_fast_crit_pure, to indicate that models can calculate their pure critical point quickly. saturation initial guesses use the result of this function to decide if and when to call the crit_pure routine.
• speed ups in some pressure routines

Bug fixes

• MultiFluid and SingleFluid models did not use the correct gas constant.
• Fix mixing rule in SAFTVRMie.
• VT_identify_phase now returns :unknown for an unstable state input.
• Typos in TProperty for pure models.

v0.6.3

New Features

• New Activity model: Hard-constraint Neural Network for Consistent Activity Coefficient Prediction(HANNA). requires the loading of the auxiliary package ClapeyronHANNA.
• New ideal model: PPDS correlations (PPDSIdeal)
• New Function: reference_chemical_potential, to calculate the reference chemical potential used in activity coefficient calculations
• New Functions: activity and aqueous_activity. both functions use the ability to change reference chemical potentials.
• New Functions: spinodal_pressure and spinodal_temperature.
• New function: split_model_binaries, that returns a list of all binary combinations of an n-component model.
• New Saturation Method: CritExtrapolation, that calculates saturation volumes and pressures via extrapolation from the critical point.
• lb_volume now has a three-arg version: lb_volume(model,T,z).
• p_scale is now defined in terms of T_scale and lb_volume.
• Stability improvements for bubble/dew calculations.
• Speed improvements for single and multicomponent equilibria.
• Association solver is now faster for small association matrices.
• New association mixing rule: Mie-15 (:mie15,:dufal)
• Michelsen TP-Flash: in case of valid K values but single phase rachford-rice, the procedure will assume bubble or dew point as a first iteration.
• Joback: new submodule: JobackGC that provides all available properties using the joback correlations.
• SAFT-VR-Mie: speed improvements for calculation of association strengths.
• Cubics: Better initial point for single component saturation calculations.
• split_model now works for ClapeyronParam,Symbol,Number,AbstractString,Tuple,Missing and Nothing. before those could only be splitted if inside an EoSModel.
• StructGroupParam is deprecated, GroupParam has all the functionality of StructGroupParam.

Bug fixes

• SAFTgammaMie fixes.
• SingleFluid has improved initial points for liquid volume evaluation.
• miscelaneous database improvements.
• second_virial_coefficient for cubics was ignoring the translation.
• improvements to the initial point of SingleFluid.

v0.6.2

Bug fixes

• SAFTgammaMie fixes.

v0.6.1

Bug fixes

• tpd fixes.
• MultiPhaseTPFlash fixes.
• Association: all temporary storage is now initialized

v0.6.0

New Features

• New models: Electrolyte models are now supported! We have introduced the ESElectrolyte framework which will let users combine any electrostatic model (DH, MSA and Born) and relative static permittivity model with any of our supported equations of state. Due to this flexibility, we now support four existing SAFT-type electrolyte equations (with planned support for more):
  • ePCSAFT
  • SAFTVREMie
  • eSAFTVRMie
  • SAFTgammaEMie
• New method: Two new methods specific to electrolytes have been added: mean_ionic_activity_coefficient and osmotic_coefficient, along with their saturated variants.
• New method: MultiPhaseTPFlash, that solves multiphase,multicomponent TP-flash with automatic phase detection. this method is now the default when calling tp_flash with more than two components and helmholtz-based models.
• New method: Tproperty(model,p,prob,z,property) to calculate temperatures, given pressure and another property.
• New model: To model solubility of salts, SolidKs has been added in order to obtain the solubility of salts using the infinite-dilution approach as opposed to the pure-fluid approach using SolidHfus.
• additional method: x0_volume_liquid(model,p,T,z) and x0_volume_solid(model,p,T,z) can be overloaded to calculate liquid an solid volumes, using the pressure as information. They are defined as x0_volume_liquid(model,p,T,z) = x0_volume_liquid(model,T,z) and x0_volume_solid(model,p,T,z) = x0_volume_solid(model,T,z)
• tangent plane distance (tpd) calculations are now faster.
• VT_diffusive_stability now uses eigmin instead of the full eigen calculation.
• isstable now works on (P,T,z) space, for the (V,T,z) space, use VT_isstable. there are now (P,T,z) versions of each stability function.
• calculation of volumes,saturation pressures and critical points of CPA models now defaults to the inner cubic model when there is no association present.
• The default association implementation now uses a combination of accelerated successive substitution and newton optimization. While increasing allocations, the method is faster.
• the default volume implementation now uses implicit AD to support derivatives. instead of propagating derivative information through the iterative procedure. This allows workloads of the type: ForwardDiff.derivative(_p -> property(model,_p,T,z,phase = :l,vol0 = v0),p) to be efficiently calculated.
• Clapeyron.tpd code has been optimized. tpd has new keywords: break_first, that tries to return a negative tpd as early as possible, lle for only calculating TPD in liquid phases, strategy, that changes the search strategy between a K-value search (:wilson), a pure component search (:pure) or both strategies (default).
• Clapeyron.tpd now supports activity models (if the keyword lle is set to true)
• MichelsenTPFlash will now try LLE if the initial equilibrium type is not set and VLE fails.
• New EoS: modified Lee-Kesler-Plöcker with consistent parameters (LKPmod)
• New EoS: Lee-Kesler-Plöker-equation of state, Sabozin-Jäger-Thol enhancement (LKPSJT, enhancedLKP)

Bug fixes

• PCPSAFT: typo in unlike asssociation parameters

v0.5.11

New Features

• Support for reference states. A reference state is a point in V-T space where H = H₀ and S = S₀. Setting those have uses in Reaction equilibria and when comparing between different models.In particular, Reference states are stored in a ReferenceState <: ClapeyronParam in the ideal model parameters. The BasicIdeal model is, intentionally, the only ideal model in Clapeyron that does not have this struct and, as a consequence, it is not able to set reference states.
• Support for superancillaries via EoSSuperancillaries.jl. When the package is loaded, initial saturation points for cubics and PCSAFT are overloaded to use superancillary evaluations instead of the general x0_sat_pure function. in the case of PCSAFT models, it also speeds up the evaluation of crit_pure.
• New EoS: EOS-CG (2021) (EOS_CG), a reference model for humid gases and CCS mixtures.
• New EoS: Lee-Kesler-Plöcker (LKP)
• New EoS: Shomate ideal model (ShomateIdeal)
• database: PCPSAFT,gcPCSAFT and gcPCPSAFT are updated to use the values of Rehner (2023).
• new functions: helmholtz_free_energy_res,gibbs_free_energy_res,internal_energy_res, enthalpy_res
• database: ReidIdeal now uses the poling coefficients by default.
• database: JobackIdeal has support for more common group fragments used in gcPCSAFT.
• melting_temperature, sublimation_temperature does not allocate anymore. Note that the function can still allocate if the EoS model itself allocates.

bug fixes

• Incorrect value for CPA with water (#256)
• Bug in SAFT-VR-SW (#165)
• Bug in CP-PC-SAFT

v0.5.10

New Features

• Association models don't allocate anymore in the case of a single association site pair.
• saturation_pressure(model,T) (ChemPotVSaturation,IsoFugacitySaturation) does not allocate if the calculation does not require a critical point calculation. Note that the function can still allocate if the EoS model itself allocates. the same optimizations were applied to saturation_temperature (AntoineSaturation,ClapeyronSaturation), sublimation_pressure and melting_pressure.
• Bulk properties now accept a vol0 initial point for the volume solver.
• SAFT-VR-Mie uses a divided approach for calculating d: if θ = ℂ*ϵᵢ/T > 1, then it uses a 10-point gauss-laguerre integrator. Otherwise, the Assen method of finding a cut point and integrating the rest is used. A description of the method is found here: https://teqp.readthedocs.io/en/latest/models/SAFT-VR-Mie.html. the cut allows for better accuracy at higher reduced temperatures.

Bug fixes

• Peng-Robinson now uses more accurate Ωa and Ωb values
• CPA/sCPA now uses SI units as input.

v0.5.9

New Features

• New EoS: Solid SAFT-VR Mie (SAFTVRSMie)
• New EoS: Solid soft-SAFT (solidsoftSAFT)
• New property: sublimation pressure. sublimation_pressure(model::CompositeModel,T)
• New property: melting pressure. melting_pressure(model::CompositeModel,T)
• New property: sublimation temperature. sublimation_temperature(model::CompositeModel,p)
• New property: melting temperature. melting_temperature(model::CompositeModel,p)
• New property: triple point. triple_point(model::CompositeModel)
• CompositeModel was revamped to support more general equilibria. in particular it will be used to represent equilibria with Activity Models along with with Real Gases. As a result of these enhancements, CompositeModel now supports bubble_pressure,bubble_temperature,dew_pressure, and dew_temperature.
• DETPFlash supports LLE equilibria with activity models
• Bulk properties now accept a vol0 initial point for the volume solver.

Bug fixes

• SAFTVRMie was allocating excesively because of unbound type parameter.
• typos in pharmaPCSAFT
• SanchezLacombe didn't set k correctly when passed as userlocations
• CPA, SAFT equation of state and other EoS that implement association,don't need to specify bondvol and epsilon_assoc, when using non-associating species.
• correct implementation of lb_volume for CPPCSAFT
• better implementation of lb_volume for pharmaPCSAFT

v0.5.8

New Features

• Base.getindex and Base.setindex with SingleParam, PairParam and AssocParam now works with strings. the strings are compared with the components (or groups) stored in each param. in particular AssocParam allows set/get index methods if you pass a Tuple{String,String}:

julia> model = PPCSAFT(["water","ethanol"],assoc_options = AssocOptions(combining = :esd))
PPCSAFT{BasicIdeal} with 2 components:
 "water"
 "ethanol"
Contains parameters: Mw, segment, sigma, epsilon, dipole, dipole2, epsilon_assoc, bondvol

julia> model.params.bondvol[("water","a"),("water","b")]
0.35319

julia> model.params.bondvol[("water","a"),("water","b")] = 0.36
0.36

julia> model.params.bondvol[("water","a"),("water","b")]
0.36

• PCPSAFT is defined (alias for PPCSAFT)
• New EOS: Critical-point based PC-SAFT CPPCSAFT (https://doi.org/10.1021/ie502633e)
• Experimental: new get_k/get_l/set_k!/set_l! defined for cubics

Bug Fixes

• bug in ether and aldehyde parameters in UNIFAC (ClapeyronThermo#225)
• more strict checks for saturation temperature and better initial point.

v0.5.7

New Features

• New EoS: Polar PCSAFT with Quadrupolar interactions (QPPCSAFT)
• New EoS: Group-Contribution simplified PC-SAFT (gcsPCSAFT)
• New EoS: Group-Contribution homosegmented polar PC-SAFT (gcPPCSAFT)
• Unitful.jl support has been moved into an extension.
• MultiComponentFlash.jl support via extension: you can pass model::EoSModel to MultiComponentFlash.flash_2ph. there is also a new MCFlashJL method that calls flash_2ph using the Clapeyron.tp_flash interface.
• custom types can be passed to the userlocations keyword argument, defining Clapeyron.can_nt(::datatype) = true and Clapeyron.to_nt(x::datatype)::Union{AbstractDict,NamedTuple}

Bug Fixes

• bug in pharmaPCSAFT mixing rules

v0.5.6

New Features

• Clapeyron.diagvalues now accepts x::Number (returning the same number)

Bug Fixes

• more flexible sites parser (#214). Before, some site names where hardcoded.

v0.5.5

New Features

• Polar PC-SAFT now uses the Esper et al. (2023) parameters.

Bug Fixes

• added promotion of types for solid solvers and pharmaPCSAFT (#212)

v0.5.4

New Features

• New Function: export_model, that allows exporting a current clapeyron model into a series of csv files.
• Metaheuristics.jl extension to allow passing a Clapeyron.Estimator to Metaheuristics.optimize (optimize(f,estimator,method))
• Clapeyron.Estimator now has a objective_form field.

v0.5.3

New Features

• Databases were standardized according to CAS. almost all components present in Clapeyron.jl databases are present in @DB/properties/identifiers.csv.
• COSMOSAC-2002 (COSMOSAC02),COSMOSAC-2010 (COSMOSAC10) and COSMOSAC-dispersion (COSMOSACdsp) can now read files from the NIST database found at https://github.com/usnistgov/COSMOSAC . to use those parameters, pass the keyword use_nist_database = true
• New model: doubly association perturbation theory (DAPT)
• New model: PCSAFT with association dependent hard sphere diameter (ADPCSAFT)
• New model: translated-and-consistent Peng-Robinson (tcPR)
• New model: translated-and-consistent Peng-Robinson, with Wilson and gE-res mixing rule (tcPRW)
• New model: translated-and-consistent Redlich-Kwong (tcRK)
• New Mixing Rule: residual (excess) gibbs energy mixing rule (gErRule)
• New model: consistent PR - Twu (cPR)
• New alpha function: Twu-88 (Twu88Alpha)
• New alpha function: soave-2019 (Soave2019Alpha)
• DETPFlash now supports the equilibrium = :lle option, to only find liquid phases.

v0.5.2

New Features

• Support for solid models (Clapeyron.sle_solubility, Clapeyron.slle_solubility and Clapeyron.eutectic_point).

Bug fixes

• eltype(::SAFTVRMieParam) is defined.

v0.5.1

New Features

• Experimental support models with diferent types of parameters (that aren't Float64). This allows, among other things, creating models that have uncertainty in their parameters, and track that uncertainty across property calculations. PCSAFT and SAFTVRMie support this. (uncertainty support via Measurements.jl + ForwardDiffOverMeasurements.jl for autodiff rules)
• Models built automatically via the @newmodel, @newmodelgc and newmodelsingle macros now allow to pass single components as a string (PR("water")). There is also more compatibility with Group Contribution models PCSAFT(["water" => ["H2O"=>1]],idealmodel = WalkerIdeal).
• minor inprovement on x0_sat_pure when the model cannot provide a virial coefficient.

v0.5.0

New Features

• rework of @newmodel, @newmodelgc and newmodelsingle macros. Now they also define the outer constructor. for a simple EoS that does not require transformation of parameters, you can now do:

@newmodel MyModel EoSModel MyModelParam
#define locations for your model, relative to the current database location
Clapeyron.default_locations(::Type{MyModel}) = ["models/mymodel"]
#define references
Clapeyron.default_references(::Type{MyModel}) = ["TODO"]

• new macro @newmodelsingleton, that defines "singleton" EoSModels.
• Rework of MultiParameter EoS. there are two new EoSModels that represent Empiric, Multiparameter EoS:
  • SingleFluid: for single component fluids
  • MultiFluid: for multicomponent fluids, with specific mixing and departure rules SingleFluid and MultiFluid constructors are capable of parsing CoolProp JSON single component files. furthermore, you can use the available CoolProp single fluid library by just importing CoolProp into the current working enviroment (using CoolProp).
• Cubic models that have an alpha dependent of the acentric factor, can be built by passing acentricfactor directly to userlocations, instead of alpha_userlocations (#188)
• New Function: RGas(model) and Rgas(), that gives the value of the gas constant used by the model. defaults to Clapeyron.R̄ = 8.31446261815324
• New model: HelmAct, to use multiparameter EoS + activity coefficient models as the departure.
• New model: XiangDeiters
• New model: TholLJ (used in LJRef)
• New model: EmpiricIdeal, the ideal part of a multiparameter model, to be used in conjuction with other EoS
• New model: AlyLeeIdeal
• New model: CPLNGEstIdeal (http://dx.doi.org/10.1016/j.jngse.2014.04.011)
• CSVs allow defining a sep keyword in the inline CSV options:

Clapeyron Database File
my parameters [csvtype = like, sep = ;]
species,Mw
1,3,5,7-CYCLOOCTATETRAENE;156.22368

Breaking changes

• IAPWS95, PropaneRef, Ammonia2023 are now of type SingleFluid{EmpiricAncillary}.
• GERG2008, EOS-LNG are now of type MultiFluid{EmpiricAncillary,AsymmetricMixing,EmpiricDeparture}
• @newmodel macros don't require defining external constructors anymore.
• SpecialComp (used by pharmaPCSAFT) is now a ClapeyronParam instead of an EoSModel

v0.4.13

New Features

• (Experimental) Initial Symbolics.jl support for bulk properties on EoSModel. In particular, all Activity models, cubic models, SAFT models without association, and empiric models are supported. for example, this is now supported:

@variables y(..)[1:4], n(..)[1:4]
mixture = UNIFAC(["water","ethanol","methanol","1-propanol"])
moles = [n(t)[i] for i in 1:4] #Clapeyron accepts mole amounts, so it is not necessary to perform transformations to mole fractions
bc_l = y(t, 0.0) .~ activity_coefficient(mixture, 1.0, 298.15, moles)

Bug Fixes

• automatic precompile is disabled in this version.

v0.4.12

New Features

• @registermodel macro is now a no-op. custom models that have a components::Vector{String} automatically support the printing interface and if they have model.params.Mw, they support molecular weight calculations.

• Cubic roots now use a real solver. this allows more stability and correctness in challenging EoS

v0.4.11

New Features

• The package now performs precompilation (via PrecompileTools.jl) of some commonly used functions and EoSModels. this will add more time at the installation of the package, in exchange with decreased loading times each time Clapeyron is loaded in a new julia session. you can turn on/off the feature with Clapeyron.precompile_clapeyron!(setting::Bool) (recomended in the case of developing the library). due to how precompilation is done, it is only done from julia 1.9 onwards.
• New EoS: NRTL with aspen paranetrization of τᵢⱼ : aspenNRTL
• split_model should be a little bit faster, and will perform correct splitting of group association models that use get_group_idx.

Bug fixes

• Combining rule for epsilon in SAFTgammaMie updated from √(ϵᵢ*ϵⱼ)*(σᵢ^3 * σⱼ^3)/σᵢⱼ^6 to √(ϵᵢ*ϵⱼ*(σᵢ^3 * σⱼ^3))/σᵢⱼ^3. the old behaviour can be obtained by passing the argument epsilon_mixing::Symbol to the model constructor. (#179)

v0.4.10

New Features

• MichelsenTPFlash now supports activity models, it also supports CompositeModel if they don't reach the multidimensional optimizer. with that, all combinations of 2-phase TP-Flash are supported in the following way:
  • Raoult: CompositeModel
  • Raoult with gas fugacity: CompositeModel(components, gas = EoSModel)
  • fugacity: any Helmholtz model
  • Activity + ideal gas: Activity(components, puremodel = IdealModel)
  • Activity + real gas: Activity(components, puremodel = EosModel) (ActivityModel(components) normally calls ActivityModel(components,puremodel = PR))
• RRTPFlash now supports acceleration, non-condensables, non-volatiles, activity models and CompositeModel. (the same operations that MichelsenTPFlash supports.)
• MichelsenTPFlash and RRTPFlash provide initial guesses for LLE equilibria. tp_flash(model,p,T,z,MichelsenTPFlash(equilibrium = :lle)) should suffice to calculate LLE flashes.
• UNIFAC models should be faster.

v0.4.9

New Features

• ideal_consistency(model,V,T,z) that checks if da0/dV + sum(z)/V is zero (or as close to zero as the Floating Point Format allows it.)

• broadcasting on AssocParam is defined (bondvol .= 1e-10 .* bondvol .^3)

• you can pass functions that build models instead of EoSModel types. for example, now you can do:

  function myvdW(components;userlocations = String[],verbose = false)
      return vdW(components;userlocations = userlocations,verbose = verbose,alpha = SoaveAlpha)
  end
  
  model = Wilson(["water","ethanol"];puremodel=myvdW)

Bug Fixes

• proper namespaces in @registermodel (#161)
• fixed bug in MichelsenTPFlash when using non-volatiles and second_order = false
• fixed bug when building UNIFACFVPoly

v0.4.8

New Features

• you can pass a named tuple to userlocations and its variants to build a model directly from those parameters (#156). for example, with PCSAFT:

julia> model = PCSAFT(["a1"],userlocations = (;
        Mw = [1.],
        epsilon = [2.],
        sigma = [3.],
        segment = [4.],
        k = [0.0;;], #matrix
        n_H = [1],
        n_e = [1],
        epsilon_assoc = Dict((("a1","e"),("a1","H")) => 1000.),
        bondvol = Dict((("a1","e"),("a1","H")) => 0.001)))
PCSAFT{BasicIdeal} with 1 component:
 "a1"
Contains parameters: Mw, segment, sigma, epsilon, epsilon_assoc, bondvol

• The dense option in AssocOptions is deprecated and it will be removed on 0.5.0. the sparse solver is not used anymore, the dense solver has performance advantages in all cases.

Bug Fixes

• bug in @registermodel (#157)

v0.4.7

bug fixes

• @newmodel,@newmodelsimple and@newmodelgc macros had a bug where some structs and types didn't have the proper namespace (#154)

v0.4.6

Bug fixes

fixed bug on Michelsen TP flash introduced in the last release.

v0.4.5

Bug fixes

DETPFlash now returns results sorted by increasing molar volume (heavy liquid ->light liquid -> vapour) (fixes #151)

v0.4.4

New Features

• New EoS: Ammonia2023, an Empiric EoS with a new term (https://doi.org/10.1063/5.0128269)
• Speed improvements on some Empiric EoS
• Estimation Framework: the method is now specified as a csv option instead of just the title.
• Estimation Framework: support for setting species to be estimated.

Bug fixes

• some references in the SAFTVRMie's csv were incorrect.
• recombine! now works with StructGroupParam.

v0.4.3

Bug fixes

• incorrect indexing of sites when doing group-to-component transformation (e.g SAFTgammaMie) with more than one association site per molecule.
• better error handling when incorrect group types are assigned.

v0.4.2

Bug Fixes

• Typo in assoc_translator field when creating assoc sites with groups that have multiple association groups.
• Correct initialization of β in rachfordrice

v0.4.1

New Features

• New Clapeyron Parameter StructGroupParam, that stores groups, as well as it's bonds between them, used in heteronuclear GC approaches
• New EOS: structural SAFT-γ-Mie (structSAFTgammaMie)
• New EOS: heteronuclear GC-PC-SAFT (gcPCSAFT)
• in some limited cases, split_model can now differenciate between group and component parameters inside a model

v0.4.0

New Features

• New estimation framework, to fit new model parameters from known data. at the moment of this release, it should support all SAFTs, Cubics, Activity models and models that don't require any special pre-computed cache.

• Base.transpose(model::EoSModel) is defined. now this is valid code:

T = 300:350
comp = ["water"]
models = [m(comp) for m in (PR,PCSAFT,SAFTVRMie)]
saturation_pressure.(transpose(models),T) #produces a 51×3 Matrix{Tuple{Float64, Float64, Float64}}:

Breaking Changes

• x0_sat_pure now returns Vl and Vv (in [m^3]) instead of log10(Vl) and log10(Vv).
• in databases, segment is used instead of m
• in databases, Vc is used instead of vc
• in databases, Pc is used instead of pc
• in databases, acentricfactor is used instead of w

v0.3.12

new features

• new EoS: RKPR (RKPR)
• new functions: cross_second_virial and equivol_cross_second_virial, to calculate B12, at specified z conditions, or by setting equivolumetric mixing.
• cubic EoS now support recombine!
• PenelouxTranslation and RackettTranslation now cache their results, resulting in a speed up when using volume translated EoS.
• Clapeyron.cite now accepts the optional argument out, that can be doi (current default, DOI) or :bib (for BibTeX)

Bug fixes

• various bug fixes in SAFT-VRQ-Mie. the Hard sphere term now performs the non-additive mixing rule for the multicomponent case. initializations with integer values are fixed.

v0.3.11

new features

• new EoS: PCSAFT with activity mixing rules (GEPCSAFT(components; activity)) (https://doi.org/10.1021/acs.iecr.2c03464)
• new EoS: UNIFAC-FV (UNIFACFV)
• new EoS UNIFAC-FV-poly (UNIFACFVPoly)
• getparams now supports inline csvs, custom locations and the ability to replace or swap out certain parameters, check getparams docs for more information
• new function: recombine! to recalculate combining and mixing rules after one parameter is modified. at the moment, SAFT and activity models have this defined.
• all quadratic mixing rules have an implace version (sigma_LorentzBerthelot(sigma,zeta) -> sigma_LorentzBerthelot!(sigma,zeta))
• AssocParam has getindex/setindex! methods defined.
• GroupParam has a new field, grouptype, to differenciate group parametrizations

Deprecations

• icomponents was removed, use Clapeyron.@comps or 1:length(model) instead
• PairParam.diagvalues was removed, use Clapeyron.diagvalues(param) instead

v0.3.10

New features

• dew_pressure and dew_temperature can now by calculated with ActivityModels. options available can be passed via the new methods ActivityBubblePressure, ActivityBubblwTemperature, ActivityDewPressure, ActivityDewTemperature. helmholtz-based models also support solving bubble_pressure and dew_pressure using those methods (http://dx.doi.org/10.1021/acs.iecr.1c03800).

• There is support for γ-ϕ equilibria on bubble_pressure and dew_pressure with activity models, that is:, solving yᵢϕᵢp = γᵢp₀ᵢϕ₀ᵢ𝒫ᵢ

• New Correlation models: LeeKeslerSat, DIPPR101Sat for saturation pressure and temperature, COSTALD, RackettLiquid,DIPPR105Liquid, for saturated liquid volume.

• New models: Second Virial models (AbbottVirial,TsonopoulosVirial and EoSVirial2)

• New model: CompositeModel, used to hold saturation, liquid and vapor correlations. For example, instantiating an Activity Model, that uses Peng-Robinson for a gas model, DIPPR 101 for saturation and COSTALD for liquid volume, with a wilson activity coefficient, can be written as:

  julia> com = CompositeModel(["water","methanol"],liquid = COSTALD,saturation = DIPPR101Sat,gas = PR)
  Composite Model:
  Gas Model: PR{BasicIdeal, PRAlpha, NoTranslation, vdW1fRule}("water", "methanol")
  Liquid Model: COSTALD("water", "methanol")
  Saturation Model: DIPPR101Sat("water", "methanol")
  
  # Wilson activity model, using the composite model as the pure model
  julia> model = Wilson(["water","methanol"],puremodel = com)
  Wilson{CompositeModel{PR{BasicIdeal, PRAlpha, NoTranslation, vdW1fRule}, COSTALD, Nothing, DIPPR101Sat, Nothing}} with 2 components:
  "water"
  "methanol"
  Contains parameters: g, Tc, Pc, ZRA, Mw
  

• Improved initial points for bubble_temperature and dew_temperature.

• MichelsenTPFlash no uses an accelerated successive substitution method.

Bug fixes

• cross-association weren't counted in some cases.
• incorrect initialization on FugBubbleTemperature
• Clapeyron.lnϕ uses the specialized algorithm for volume instead of the general one.

v0.3.9

New features

• New combining rules that are done at model creation time instead of runtime: :cr1 and :esd/elliott. the old elliott combining rule was renamed to elliott_runtime (it is only used on PharmaPCSAFT, where is required)

Bug fixes

• crit_pure on CPA was failing (#112, #113)
• error on bubble/dew pressure/temperature when using the v0 starting point (#113)
• crit_pure was slower than expected on julia 1.8
• add error path on SingleParam when all data is missing

v0.3.8

New features

• bubble_pressure, bubble_temperature, dew_pressure, and dew_temperature can now support custom methods. (subtyping BubblePointMethod or DewPointMethod). the default methods are now named ChemPotBubblePressure, ChemPotBubbleTemperature,ChemPotDewPressure,ChemPotDewTemperature. you can provide some or all necessary initial conditions to those new methods:

  res = bubble_pressure(model,T,x,ChemPotBubblePressure(;y0;p0;vol0))
  

• New bubble/dew methods based on isofugacity conditions: FugtBubblePressure, FugBubbleTemperature,FugDewPressure,FugtDewTemperature.

• All bubble methods now support leaving some components out of the bubble phase,via the nonvolatiles keyword, supported by all available bubble solvers. similarly, all dew methods support the noncondensables keyword to leave some components out of the dew phase.

• MichelsenTPFlash can support both nonvolatiles and noncondensables.

• SingleParam and PairParam support indexing and broadcasting. PairParam has a modified indexing scheme, where param[i] will return the diagonal elements, param[i,j] will return off-diagonal elements. setindex! on PairParam is symmetric by default, that is, param[i,j] = k will also set param[j,i]. you can opt out of this by doing param[i,j,false] = k

• New function: diagvalues, for obtaining a vector view of the diagonal elements of a Pair or Single Parameter.

• New functions: VT_gibbs_free_energy_res and VT_helmholtz_free_energy_res

• New saturation method: saturation_temperature(model,p,::SuperAncSaturation)

• index_reduction(model,x::AbstractVector{Bool}) will return a reduced model, according to the true values of the vector x. Passing another vector will perform the index reduction based on non-empty values, as usual.

• Initial (and optional) support for solid phase volume solving, via x0_volume_solid

• New EoS (experimental): AnalyticalSLV, that supports solid, liquid and vapour phases in one continous helmholtz functional.

• the database parser is faster and has better verbose reporting.

• SAFTVRMie and SAFTGammaMie should be a little faster on single component evaluations

Bug Fixes

• activity_coefficient and fugacity_coefficient now works with SVector #104
• there was a bug on calculating the length of GC models that went under split_model

Deprecations

• model.params.param.diagvalues is not longer used in the codebase and it will be removed at the next breaking version. use diagvalues(model.params.param) or model.params.param[i] instead.

• model.icomponents is not longer used in the codebase and it will be removed at the next breaking version. 1:length(model) or Clapeyron.@comps instead.

v0.3.7

New features

• You can now define custom saturation (temperature or pressure) solvers, via subtyping SaturationMethod. The default solver is now named ChemPotVSaturation.
• New methods for saturation pressure: IsoFugacitySaturation, ChemPotDensitySaturation, SuperAncSaturation (for cubics)
• All saturation methods support passing the crit keyword, to allow using precomputed critical points.
• All saturation methods that use a non linear solver support passing convergence options.
• The default solver for saturation_temperature was changed (now named AntoineSaturation). The new model is much faster and with a similar reliability. the old one is available via ClapeyronSaturation.
• New method for TP-Flash: MichelsenTPFlash
• New function: tpd, that tries to find all negative tangent plane distances
• New function: lle_init, that tries to find good LLE starting points, via tpd
• New function: x0_saturation_temperature(model,p), that returns starting points for saturation_temperature.
• New function: x0_psat(model,p), that returns starting points for IsoFugacitySaturation.
• New function: antoine_coef for reduced antoine coefficients. used to accelerate initial points, if available.
• New function: cite(model) returns all references used in the evaluation of a model.
• bubble_temperature, dew_temperature, lle_temperature, azeotrope_temperature and vlle_temperature methods now iterate directly over the extended-with-temperature non linear system that their pressure cointerparts.
• Cubics were revamped and generalized even more. those changes opened the way to introduce more non-standard cubics, all while being compatible with the initial guess procedures, advanced mixing rules and other Clapeyron optimizations for cubics.
• New cubic EoS: Clausius
• New cubic EoS: Berthelot
• New cubic EoS: Patel-Teja (PatelTeja)
• New cubic EoS: Patel-Teja-Valderrama (PatelTeja)
• New cubic EoS: Kumar-Upadhyay two parameter EoS (KU)
• New mixing rule: Modified Wong-Sandler (ModWS)
• SoaveAlpha now works with vdW and PR (returning the same value of PRAlpha)
• New EoS: Perturbed, truncated and shifted LJ EoS (PeTS)
• SPUNG is now a constructor for the new ECS model.
• volume now accepts a vol0 initial point.
• PCSAFT should be a little bit faster for single component cases

v0.3.6

New Features

• ZeroResidual model (a_res = 0)

Bug fixes

• HVRule uses the original rule instead of the modified one.
• ismissingvalues is preserved when a combining rule is applied. this allows us to track inputed parameters vs calculated ones.

In particular, this release is the one used in the Clapeyron.jl paper. and it's results should be reproducible by locking the version to v0.3.6.

v0.3.5

New Features

• new functions: VT_mass_density, VT_mol_density
• vdW, RK and PR models and variants use now ABCubicParam. vdWParam, RKParam and PRParam are now just aliases to ABCubicParam.
• Roots.jl updated to 2.0

Fixes

• fixes to UNIFAC models
• fixes to split_model on groups

v0.3.4

New Features

• New EoS: Enhanced Predictive Peng Robinson 1978 (2022) (EPPR78)
• New EoS: Quantum Corrected Peng Robinson (2022) (QCPR)
• New EoS: Modified PCSAFT with T-dependent σ for water (passing water08) and k0 + k1T mixing rule (pharmaPCSAFT).
• New function: index_reduction(model,z) that removes components with compositions near zero. useful to reduce the dimensionality on multicomponent solvers.
• New function: isstable(model,V,T,z) to check for stability at the input conditions.
• New function: gibbs_duhem(model,V,T,z) to check if the Gibbs-Duhem relations holds for the input model at the specified conditions.
• New function: kij_mix and pair_mix for arbitrary pair combining rules
• volume solver can now perform aditional stability checks by passing phase = :stable, before only mechanical stability checks were done.
• association solver supports Elliot rule for combining rules, passed via assoc_options(combining = :elliott)
• association solver supports dense association matrix, passed via assoc_options(combining = :dense_nocombining)
• Faster crit_pure, saturation_pressure
• Faster GERG2008 and EOS_LNG
• some cubic α-functions are faster for single component models
• improved initial saturation point for cubics
• CPA and sCPA now accept AssocOptions
• new mixing SLKRule for SanchesLacombe
• easier constructors for some empty models: NoTranslation() instead of NoTranslation(NoTranslationParam())

Error fixes

• GC models can now be splitted in arbitrary component subsets
• absolutetolerance fields removed from almost all EoS (except COSMO models)
• second_virial_coefficient now works with SanchezLacombe
• some starting points for softSAFT (original) and BACKSAFT were wrong. ``softSAFT2016` was not affected.
• volume_compress now accepts integer pressures, they are converted internally.
• volume for cubics now propagates the pressure type

v0.3.3

New Features

• gibbs_solvation(model,T) : For calculation of the solvation energy in a binary model
• speed up for activity coefficients and excess gibbs free energies for NRTL, Wilson, UNIQUAC and UNIFAC
• new EoS model: softSAFT2016, that uses the LJ helmholtz energy from thol et al. (2016)
• new utility function: correct_composition_derivative, that returns ∑xᵢμᵢ - G. it should be zero or near zero for correctly written models.

Error Fixes

• fix error in parameters for softSAFT
• fix errors in use of units. tests added.
• fix error on isobaric expansivity.

v0.3.2

• fixes in volume solver
• fixes in initial guesses for MultiFuidModel and CPA
• all multicomponent solvers now accept an initial guess

v0.3.1

Model fixes;

• WSRule
• MonomerIdeal new functions: assoc_site_matrix(model::Union{SAFTModel,CPAModel},V,T,z) to instantiate the association matrix ReidIdeal(model::JacobianIdeal) to obtain a Reid ideal model from a Joback Ideal model faster crit_pure on cubics

v0.3.0

• Differential Evolution and Rachford-Rice Tp-flash algorithms have been implemented
• AssocOptions has been added to all SAFT equations
• Further speed-up to cubics
• sat_pure has been renamed saturation_pressure
• Numerous new multi-component VLE functions have been added (dew_pressure, bubble_temperature, VLLE_temperature etc.)
• New models: Full CPA, sCPA and ogUNIFAC