Abstract
In order to calculate accurately chemical-reaction equilibria of a system over a wide range of temperatures and pressures, one must account for the non-idealities of the system. In this work, a method is developed to predict accurately chemical-reaction equilibria and phase equilibria of a system using an equation of state to account for the nonidealities. The general formalism for a multicomponent system with multiple reactions is presented. Three widely used cubic equations of state are used to calculate the physical properties of the species. The proposed method is applied to the water-gas shift reaction, to the decomposition of methylcyclohexane, and to the reaction of carbon monoxide with hydrogen sulfide over a wide range of temperatures and pressures.
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Abbreviations
- a :
-
Molecular parameter in RKS and PR equations of state
- a :
-
Activity
- b :
-
Molecular parameter in RKS and PR equations of state
- c :
-
Shape parameter in ESD equation of state
- c i :
-
Concentration of i
- f :
-
Fugacity
- g :
-
Molar Gibbs free energy
- K :
-
Equilibrium constant
- M :
-
Total number of reactions
- n :
-
Total number of moles
- n i :
-
Number of moles of i
- P :
-
Pressure
- P l :
-
Product component l
- q :
-
Shape parameter in ESD equation of state
- R :
-
Gas constant
- R k :
-
Reactant component k
- T :
-
Temperature
- V :
-
Total volume
- v :
-
Molar volume
- x :
-
Mole fraction
- Y :
-
Energy parameer for the ESD equation of state
- Z :
-
Compressibility factor
- εj :
-
Extent of chemical reaction j
- η :
-
Reduced density
- μ i :
-
Chemical potential of component i
- ν i,j :
-
Stoichiometric coefficient of component i in reaction j
- φ i :
-
Fugacity coefficient of component i
- Ω i :
-
Expression defined in Eq. (15)
- i :
-
Component i
- j :
-
Chemical reaction j
- att:
-
Attractive
- 0:
-
Reference state
- 0:
-
Initial value
- rep:
-
Repulsive
- ^:
-
Property of component in the mixture
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Economou, I.G., Donohue, M.D. & Hunter, L.W. Equation-of-state calculations of chemical reaction equilibrium in nonideal systems. Int J Thermophys 14, 199–213 (1993). https://doi.org/10.1007/BF00507808
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DOI: https://doi.org/10.1007/BF00507808