Problem 2.6.1

 

Acetylene is produced at 2573 degrees Kelvin or 2200 degrees centigrade.  Two moles of carbon (s) react with one mole of hydrogen to produce one mole of acetylene.

Energy of formation (delta G) and enthalpy of formation (delta F) values are given at 298 degrees K for this reaction.  Heat capacity is given as a function of temperature described as a plus b T plus c T2.   Values of a, b, and c are provided for carbon, hydrogen and acetylene.

 

What is the value of equilibrium constant at this temperature?

 

Solution:

 

Delta G is equal to minus RT log (K), where delta G is given by delta H minus T delta S.  Delta H is given by delta H0 plus aT plus b/2 T2 plus c/3 T3.  Delta S is given by delta S0 plus a log (T) plus b T plus c/2 T2.  There is only one unknown, so these constants, delta H0 or delta S0 can be found by using the values provided at 298 degrees Kelvin.  However, we need to find values of a, b, and c for the reaction mixture.  Then, we can calculate delta H and delta S at 2573 degrees Kelvin, thus enabling us to find the value of delta G and K.

 

Values of the constants a, b, and c for the reaction mixture is calculated by writing the chemical reaction and calculating the weighted value.  It is conventional to consider the value positive for the products (as being produced) and negative for the reactants (as being consumed).  For example, the weighted value of constant a is equal to minus 2 (2 moles of Carbon) time 1.1 minus 1 (1 mole of hydrogen) time 6.88 plus 1 (1 mole of acetylene) time 8.28 is equal to minus 0.8 calories per mole per degree Kelvin.  Similarly, the value of b and c for the reaction mixture can be calculated.

 

With a, b, and c calculated for the reaction mixture, integration constant delta H0 is equal to delta H298 minus (a ×298 plus b/2 ×2982 plus c/3 ×2983).  This is equal to 54,395 calories per mole.  Delta H at any other temperature, 2573 in this case, is then calculated using the formula delta H0 plus aT plus b/2 T2 plus c/3 T3.  Delta H is calculated to be 55,330 calories per mole.

 

Delta S at 298 degrees can be obtained using the values of delta H and delta G at 298 degree Kelvin.  Delta S is given as (delta H minus delta G)/T and its value is 14.074 calories per mole per degree Kelvin.  So, the integration constant, delta S0, is equal to delta S298 minus (a log (T) plus bT plus c/2 T2).  This is equal to 18.378 calories per mole per degree Kelvin.  Delta S at any temperature, 2573 in this case, is thus calculated using the formula delta S0 plus a log(T) plus b T plus c/2 T2.  Delta S is calculated to be 14.384 calories per mole per degree Kelvin.

 

Delta G is thus equal to 55330 minus 2573×14.384 or 18,320 calories per mole.

 

This gives a value of K, exp(minus delta G/(RT)), as 0.0278.