Ideal solutions and excess functions

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Presentation transcript:

Ideal solutions and excess functions Part V

problem The data in Table 11.2 are experimental values of VE for binary liquid mixtures of 1,3-dioxolane(1) and isooctane(2) at 298.15K and 1 atm. (a) Determine from the data numerical values for a, b, and c in:

Numerical problem: find the values of a, b, and c that best fit to the given set of data a = 3448; b = -3202; c = 244.62

(b) Determine the maximum value of VE and the value of x1 at which this occurs. dVE/dx1 = 0 and solve for x1 VEmax = 536.29 cm3/mol ; x1 =0.353

c) From the results of part (a) find expressions for Prepare a plot and discuss its features

Slopes 0 as x1->1 Maximum in one pmp agrees with minimum at the other, inflection point for VE Where the VE has a maximum the pmps cross.

Temperature dependence of excess properties

example If CPE is a constant, independent of T, find expressions for GE, SE, HE for an equimolar solution of benzene(1)/n-hexane(2) at 323.15K, given the following excess-property values for an equimolar solution at 298.15 K CPE = -2.86 J/mol K; HE = 897.9 J/mol; GE = 384.5 J/mol

From Also,

using the values at 298.15K We already know the value of a = -2.86 (equal to CPE) From HE obtain c =1,750.6 From GE obtain b = -18.0171 Now calculate GE, SE, HE at 323.15 K

problem Given the following data for equimolar mixtures of organic liquids. Use all the data to estimate values of GE, HE, and TSE for the equimolar mixture at 25oC At T = 10oC, GE =544 and HE =932.1 At T = 30oC, GE = 513.2, HE =893.4 At T = 50oC, GE = 494.2, HE = 845.9 Energies are in J/mol

Assume CpE is constant (a) Then HE = aT + c Use the three sets of HE data and get the best values of a and c; a= -2.155; c = 1544 With a and c get b for each set of GE data; then take b average. Finally calculate GE, HE, TSE at 25oC using the a, b, and c parameters