ALGORITHM

Figure 1 and Figure 2 shows the Algorithm of the Data Reduction and Vapor-Liquid Equilibrium
that were used in the MATLAB program on discussing the isothermal vapor-liquid equilibrium of
cyclohexanone + hexanal at 313.15K.

Figure 1. Date Reduction Algorithm

 Figure 2. Vapor-Liquid Equilibrium Algorithm

For the Data Reduction, Iterative Optimization was used for the parameter estimation of Non-
Random Two-Liquid Activity Coefficient (NRTL) Model, which uses Particle Swarm Optimization as a
minimization technique, Gamma-Phi Approach of Binary Mixture and Excess Gibbs Free Energy for the
Experimental Values. The MATLAB program starts with declaring values of the Antoine constants for the
calculation of vapor pressure, and experimental data and physical properties for the calculation of
fugacity coefficient, vapor mole fraction, and excess Gibbs free energy. Initial bounds and guess are set
for the iterative optimization which are used to optimize the objective function by determining the
minimum function of the solutions or particles taking into consideration the particle’s position,
movement speed, and updates from other solutions. If the calculated objective is less than ε , the values
for the estimated parameters are stated, which will be use for the calculation of excess Gibbs free
energy. However, if the objective is not less than ε , the parameters will be re-initialize using the
minimization technique. The results will be used to plot the model of the experimental G E and γ i vs.
Mole Fraction in the Liquid-Phase ¿ ¿).

The Vapor Liquid Equilibrium are expressed in terms of fugacity coefficient, and the technique is
based on the Durem’s theorem (“for any closed system formed initially from given masses of prescribed
chemical species, the equilibrium state is completely determined when any two independent variables
are fixed”). Virial Equation of State was used to derive the fugacity of the binary mixture. The MATLAB
program starts with declaring values of the Antoine constants for the calculation of vapor pressure,
NRTL parameters for the activity coefficient, and experimental data and physical properties for the
calculation of fugacity coefficient, vapor mole fraction, and excess Gibbs free energy. Values were set for
malar fraction which is 0.0001:0.0001:0.9999 and 1 for the fugacity coefficient. If the calculated Pcalc is
less than ε , the values for the vapor molar fraction and Pcalc are declared. If the values of Pcalc and
y i ,calc are iterated to molar fraction, the excess Gibbs free energy are calculated and re-initialize using
the minimization technique. The results will be used to plot the model of the Experimental Pcalc vs Mole
Fraction in the Liquid-Phase x i and the Vapor-Phase y i.
CONCLUSION

The thermodynamic behaviors and the vapor-liquid equilibrium of cyclohexanone + hexanal at

313.15K were determined using an isothermal Vapor-Liquid Equilibrium technique. Using gamma-phi
modeling of the binary mixture in low-pressure system of Vapor-Liquid Equilibrium Modeling, Virial
Equation of State model was used for the vapor phase non-ideality and Non-Random Two-Liquid Activity
Coefficient model was used for the liquid phase non-ideality. The fugacity coefficient of pure species and
of the species in mixture was determined using the Virial EOS and the Activity Coefficient Model for
binary mixtures was determined using the NRTL Parameters. For the Vapor-Pressure Modeling, Antoine
Equation was used to determine the vapor pressure of the system. The estimated parameters of NRTL
model shows the reliability of the model and it was used to correlate the VLE data. The binary system
demonstrates positive deviations for the ideality of vapor-liquid equilibrium and azeotrope were not
present in the calculation. And lastly, the estimated parameters in the process simulation and design can
be used for the separation of the binary mixture (cyclohexanone + hexanal).

The results proves…..

The figures shows…..

From OT

• The vapor-liquid equilibrium behaviors of cyclohexanone + hexanal were determined.

• VLE data for the binary system was determined using a static-analytic technique [1].
• The binary system exhibited less non-ideality which is attributed to the similarity of intermolecular
forces between the two weakly polar compounds. The result revealed that the binary system has slight
positive deviations from Raoult's Law.
• The NRTL-HOC activity coefficient model correlated the VLE data.
• No azeotropes were formed in the investigated binary system.
• The parameters estimated in the study can be utilized in the process simulation and design for the
separation of cyclohexanone and hexanal mixture