Wednesday, March 27, 2019

Why are Kc and Kp interchangeable in the free energy-equilibrium equation?



In this equation that relates Standard free energy and the equilibrium constant:


\Delta Gº=-RT \ln K_{eq}


My textbook (and my teacher) say both K_p (constant related to pressure) and K_c (constant related to concentration) can be used in the place of K_{eq}.


When using the equation that relates K_p with K_c



K_p=K_c(RT)^{\Delta n}


We would get two different \Delta Gº values, which shouldn't be possible.


My question is, why can we use both constants if their values are different?



Answer



The equilibrium constant is defined by activities:


enter image description here


The activity of a species in a liquid solution can be approximated to: a=c/c^0 where c is the concentration of the species and c^o is the standard concentration (1M). This approximation leads to K_{eq}=K_c. The activity of gasses is called fugacity and it can be approximated to: f=p/p^0 where p is the pressure of the gas and p^0 is the standard pressure (1 bar). This leads to K_{eq}=K_p. Therefore, if a reaction takes place in e.g. water, one should use K_c, but if the reaction takes place in the gaseous state, K_p should be used when calculating dG.


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