Activity Coefficient Estimation Methods - The University ：活度系数的估计方法-大学.pptVIP

Activity Coefficient Estimation Methods Bharat Chandramouli February 5, 2002 Activity Coefficient The activity coefficient is a measure of the non-ideality of mixing Two components, Enthalpic and Entropic Estimation/Measurement Activity coefficients in single component/simple mixtures easy to measure Activity coefficients in water or octanol can be calculated from solubility given sufficiently sensitive methods Need for estimation What about complex mixtures? What about dynamic systems with changing compositions? It becomes more practical to use estimation methods to approximate g in these cases Estimation Methods Group contribution methods are most common because they have predictive ability There are two group contribution methods commonly used for ?iom calculation from solubility parameters UNIFAC calculation UNIFAC The activity coefficient is calculated from two components UNIFAC The group contribution components consist of volume contributor -Rk surface area contribution -Qk interaction parameter between functional groups amk To calculate interactions, similar sub-groups are assigned to groups and interactions are between these groups Calculate activity coefficients by summing all contributions and interactions UNIFAC-Simple example Ethanol CH3-CH2-OH UNIFAC Methods Interaction parameters are fit from experimental data This work is still ongoing and many parameters still not available Hansen Solubility Parameter This method calculates activity coefficients from the solubility parameter Theory of cohesive energy developed by Hildebrand for dispersive systems and extended by Hansen for polar and hydrogen bonding Hansen Activity Coefficient The activity coefficient is given by The Size Effect Term i,omd is a measure of the effect of differing sizes of i and om on their entropy of mixing This was derived by Flory and Huggins using statistical thermodynamics For an infinitely dilute solution Cohesive Energy (Ecoh) Closely linked to the he