Answer to Question #106182 in Physical Chemistry for Bharti

Question #106182
proof that (x1 × d ln f1/d x1) + (x2 × d ln f2/d x1)=0 in chemical engineering thermodynamics
1
Expert's answer
2020-03-26T03:02:14-0400

Answer:

One of the formulations of Gibbs-Duhem equation is:

"\\Sigma{x_id\\bar{Z_i}} = 0,"

where "x_i" is the molar fraction of a component i and "\\bar{Z}_i" is the partial molar property of this component.

Fugacity is linked to the chemical potential "\\mu_i" in a following way:

"\\mu_i = \\mu_i^o + RT\\text{ln}f_i"

Therefore, the change of the chemical potential is:

"d\\mu_i = RT d\\text{ln}f_i"

When we substitute chemical potential in the equation of Gibbs-Duhem, we get:

"\\Sigma{x_id\\mu_i} = 0"

"RT\\Sigma{x_id\\text{ln}f_i} = 0, \\text{or } \\Sigma{x_id\\text{ln}f_i} = 0"

Let's use the obtained equation for a binary mixture:

"x_1d\\text{ln}f_1 +x_2d\\text{ln}f_2 = 0"

For an infinitesimal change of the composition of the mixture, we get:

"x_1d\\text{ln}f_1\/dx_1 +x_2d\\text{ln}f_2\/dx_1 = 0" .


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