Tuesday, November 5, 2019

4 compounds in equilibrium with one another - determine their equilibrium concentrations


I know that if I have two compounds in equilibrium and I know $\mathrm{\Delta G}$, then I can use $$\mathrm{\Delta G=-RTlnK}$$ to determine the concentrations of the two components at equilibrium. I have 4 compounds that are all in equilibrium with one another \begin{aligned} \mathrm{\Delta G(1,4)} ~&= ~~~3.41~ \mathrm{kcal/mol}\\ \mathrm{\Delta G(3,1)}~&=-2.21~ \mathrm{kcal/mol}\\ \mathrm{\Delta G(2,3)}~&=-0.46~ \mathrm{kcal/mol}\\ \end{aligned}


I applied the equation sequentially and found that \begin{aligned}% [1]~&=~0.34\%\\ [2]~&=~29.1\%\\ [3]~&=~13.5\%\\ [4]~&=~57\%\\ \end{aligned}


Are those the correct concentrations? Is there an "easy" way to do it?



Answer



In case anyone else travels this road...


Using $\mathrm{\Delta G~=~-RTlnK_{eq}}$ and the 3 $\mathrm{\Delta G's}$ supplied above, we find that \begin{aligned} \mathrm{K^{1/4}_{eq}}~&=~0.003\\ \mathrm{K^{3/1}_{eq}}~&=~40.749\\ \mathrm{K^{2/3}_{eq}}~&=~2.163\\ \end{aligned} We also know that the concentrations of the 4 species must total to 1



$${[1] + [2] + [3] + [4] = 1}$$


so we have the following 4 equations and 4 unknowns \begin{aligned}% [1]~ &=~~~ 0.003 ~[4]\\ [3]~ &=~ 40.749 ~[1]\\ [2]~ &=~~~ 2.163 ~[3]\\ [1] + [2] + [3] + [4]~ &=~ 1\\ \end{aligned} solving for the 4 concentrations yields \begin{aligned}% [1]~ &=~~~ 0.23\%\\ [2]~ &=~ 20.27\%\\ [3]~ &=~~~ 9.37\%\\ [4]~ &=~ 70.13\%\\ \end{aligned}


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