added enthalpy_mole(), entropy_mole().... capabilities to MargulesVPSSTP

Cantera/src/thermo/GibbsExcessVPSSTP.cpp

@@ -66,6 +66,7 @@ namespace Cantera {
     moleFractions_       = b.moleFractions_;
     lnActCoeff_Scaled_   = b.lnActCoeff_Scaled_;
     dlnActCoeffdT_Scaled_   = b.dlnActCoeffdT_Scaled_;
+    d2lnActCoeffdT2_Scaled_   = b.d2lnActCoeffdT2_Scaled_;
     dlnActCoeffdlnX_Scaled_ = b.dlnActCoeffdlnX_Scaled_;
     dlnActCoeffdlnN_Scaled_ = b.dlnActCoeffdlnN_Scaled_;
     m_pp                 = b.m_pp;
@@ -324,6 +325,7 @@ namespace Cantera {
     moleFractions_.resize(m_kk);
     lnActCoeff_Scaled_.resize(m_kk);
     dlnActCoeffdT_Scaled_.resize(m_kk);
+    d2lnActCoeffdT2_Scaled_.resize(m_kk);
     dlnActCoeffdlnX_Scaled_.resize(m_kk);
     dlnActCoeffdlnN_Scaled_.resize(m_kk);
     m_pp.resize(m_kk);

Cantera/src/thermo/GibbsExcessVPSSTP.h

@@ -578,6 +578,11 @@ namespace Cantera {
     //! log of theactivity coefficients of the species
     mutable std::vector<doublereal> dlnActCoeffdT_Scaled_;
 
+    //! Storage for the current derivative values of the 
+    //! gradients with respect to temperature of the 
+    //! log of theactivity coefficients of the species
+    mutable std::vector<doublereal> d2lnActCoeffdT2_Scaled_;
+
     //! Storage for the current derivative values of the 
     //! gradients with respect to logarithm of the mole fraction of the 
     //! log of theactivity coefficients of the species

Cantera/src/thermo/MargulesVPSSTP.cpp

@@ -408,6 +408,43 @@ namespace Cantera {
     }
   }
 
+      /// Molar enthalpy. Units: J/kmol. 
+    doublereal MargulesVPSSTP::enthalpy_mole() const {
+      int kk = nSpecies();
+      double hbar[kk], h = 0;
+      getPartialMolarEnthalpies(hbar);
+      for (int i = 0; i < kk; i++){
+	h += moleFractions_[i]*hbar[i];
+      }
+      return h;
+    }
+
+      /// Molar entropy. Units: J/kmol. 
+    doublereal MargulesVPSSTP::entropy_mole() const {
+      int kk = nSpecies();
+      double sbar[kk], s = 0;
+      getPartialMolarEntropies(sbar);
+      for (int i = 0; i < kk; i++){
+	s += moleFractions_[i]*sbar[i];
+      }
+      return s;
+    }
+
+    /// Molar heat capacity at constant pressure. Units: J/kmol/K. 
+    doublereal MargulesVPSSTP::cp_mole() const {
+      int kk = nSpecies();
+      double cpbar[kk], cp = 0;
+      getPartialMolarCp(cpbar);
+      for (int i = 0; i < kk; i++){
+	cp += moleFractions_[i]*cpbar[i];
+      }
+      return cp;
+    }
+
+    /// Molar heat capacity at constant volume. Units: J/kmol/K. 
+    doublereal MargulesVPSSTP::cv_mole() const {
+      return cp_mole() - GasConstant;
+    }
  
   // Returns an array of partial molar enthalpies for the species
   // in the mixture.
@@ -448,6 +485,44 @@ namespace Cantera {
     }
   }
 
+  // Returns an array of partial molar heat capacities for the species
+  // in the mixture.
+  /*
+   * Units (J/kmol)
+   *
+   * For this phase, the partial molar enthalpies are equal to the
+   * standard state enthalpies modified by the derivative of the
+   * activity coefficent wrt temperature
+   *
+   *  \f[
+   * ??????????? \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
+   * \f]
+   *
+   */
+  void MargulesVPSSTP::getPartialMolarCp(doublereal* cpbar) const {
+    /*
+     * Get the nondimensional standard state entropies
+     */
+    getCp_R(cpbar);
+    double T = temperature();
+    /*
+     * Update the activity coefficients, This also update the
+     * internally storred molalities.
+     */
+    s_update_lnActCoeff();
+    s_update_dlnActCoeff_dT();
+
+    for (int k = 0; k < m_kk; k++) {
+      cpbar[k] -= 2 * T * dlnActCoeffdT_Scaled_[k] + T * T * d2lnActCoeffdT2_Scaled_[k];
+    }  
+    /*
+     * dimensionalize it.
+     */
+   for (int k = 0; k < m_kk; k++) {
+      cpbar[k] *= GasConstant;
+    }
+  }
+
   // Returns an array of partial molar entropies for the species
   // in the mixture.
   /*
@@ -733,6 +808,7 @@ namespace Cantera {
     double RTT = GasConstant*T*T;
 
     fvo_zero_dbl_1(dlnActCoeffdT_Scaled_, m_kk);
+    fvo_zero_dbl_1(d2lnActCoeffdT2_Scaled_, m_kk);
     
     for ( iK = 0; iK < m_kk; iK++ ){
 
@@ -755,7 +831,9 @@ namespace Cantera {
 	g0 = -m_HE_b_ij[i] / RTT;
 	g1 = -m_HE_c_ij[i] / RTT;
 	
-	dlnActCoeffdT_Scaled_[iK] += (delAK*XB+XA*delBK-XA*XB)*(g0+g1*XB)+XA*XB*(delBK-XB)*g1;
+	double temp = (delAK*XB+XA*delBK-XA*XB)*(g0+g1*XB)+XA*XB*(delBK-XB)*g1;
+	dlnActCoeffdT_Scaled_[iK] += temp;
+	d2lnActCoeffdT2_Scaled_[iK] -= 2*temp/T;
       }
     }
   }
@@ -793,6 +871,13 @@ namespace Cantera {
     }
   }
 
+  void MargulesVPSSTP::getd2lnActCoeffdT2(doublereal *d2lnActCoeffdT2) const {
+    s_update_dlnActCoeff_dT();
+    for (int k = 0; k < m_kk; k++) {
+      d2lnActCoeffdT2[k] = d2lnActCoeffdT2_Scaled_[k];
+    }
+  }
+
   // calculate the change of the log of the activity coefficients wrt change in state: dT, dX
   /*
    * This function will be called to calculate gradient of the 

Cantera/src/thermo/MargulesVPSSTP.h

@@ -525,7 +525,18 @@ namespace Cantera {
      */
     virtual void getChemPotentials(doublereal* mu) const;
 
-  
+      /// Molar enthalpy. Units: J/kmol. 
+    virtual doublereal enthalpy_mole() const;
+
+      /// Molar entropy. Units: J/kmol. 
+    virtual doublereal entropy_mole() const;
+
+    /// Molar heat capacity at constant pressure. Units: J/kmol/K. 
+    virtual doublereal cp_mole() const;
+
+    /// Molar heat capacity at constant volume. Units: J/kmol/K. 
+    virtual doublereal cv_mole() const;
+
     //! Returns an array of partial molar enthalpies for the species
     //! in the mixture.
     /*!
@@ -564,6 +575,28 @@ namespace Cantera {
      */
     virtual void getPartialMolarEntropies(doublereal* sbar) const;
 
+    //! Returns an array of partial molar entropies for the species
+    //! in the mixture.
+    /*!
+     * Units (J/kmol)
+     *
+     * For this phase, the partial molar enthalpies are equal to the
+     * standard state enthalpies modified by the derivative of the
+     * activity coefficent wrt temperature
+     *
+     *  \f[
+     *   ???????????????
+     *   \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
+     *                              - R \ln( \gamma_k X_k)
+     *                              - R T \frac{d \ln(\gamma_k) }{dT}
+     *   ???????????????
+     *  \f]
+     *
+     * @param cpbar  Vector of returned partial molar heat capacities
+     *              (length m_kk, units = J/kmol/K)
+     */
+    virtual void getPartialMolarCp(doublereal* cpbar) const;
+
     
     //! Return an array of partial molar volumes for the
     //! species in the mixture. Units: m^3/kmol.
@@ -604,6 +637,19 @@ namespace Cantera {
      */
     virtual void getdlnActCoeff(const doublereal dT, const doublereal * const dX, doublereal *dlnActCoeffdT) const;
 
+    //! Get the array of temperature second derivatives of the log activity coefficients
+    /*!
+     * This function is a virtual class, but it first appears in GibbsExcessVPSSTP
+     * class and derived classes from GibbsExcessVPSSTP.
+     *
+     *  units = 1/Kelvin
+     *
+     * @param d2lnActCoeffdT2  Output vector of temperature 2nd derivatives of the 
+     *                         log Activity Coefficients. length = m_kk
+     *
+     */
+    virtual void getd2lnActCoeffdT2(doublereal *d2lnActCoeffdT2) const;
+
     //! Get the array of temperature derivatives of the log activity coefficients
     /*!
      * This function is a virtual class, but it first appears in GibbsExcessVPSSTP

Cantera/src/thermo/SpeciesThermoFactory.cpp

@@ -829,7 +829,7 @@ namespace Cantera {
 					  f0->name() + " and " + f1->name());
 	}
       }
-      else if (nc >= 2) {
+      else if (nc > 2) {
 	const XML_Node* f0 = tp[0];
 	if (f0->name() == "NASA9") {
 	  installNasa9ThermoFromXML(speciesNode["name"], spthermo, k, tp);

Cantera/src/thermo/ThermoPhase.h

@@ -859,7 +859,7 @@ namespace Cantera {
 
     /// Molar internal energy. Units: J/kmol. 
     virtual doublereal intEnergy_mole() const {
-      return err("intEnergy_mole");
+      return enthalpy_mole() - pressure()* molarVolume();
     }
 
     /// Molar entropy. Units: J/kmol/K. 
@@ -869,7 +869,7 @@ namespace Cantera {
 
     /// Molar Gibbs function. Units: J/kmol. 
     virtual doublereal gibbs_mole() const {
-      return err("gibbs_mole");
+      return enthalpy_mole() - temperature()*entropy_mole();
     }
 
     /// Molar heat capacity at constant pressure. Units: J/kmol/K.