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Gibbs Free Energy
Michael DeDominicis
#1 Posted : Saturday, July 07, 2012 1:10:30 PM
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How does Gibbs deal with non-PV work if it has enthalpy in its equation, where enthalpy= U + PV? Perhaps I'm confused by what the PV term symbolizes in this equation. Dealing with the same PV term, I don't understand what is meant on page 56 in the Study Guide by dH= q (constant pressure, closed system at rest, and PV work only). If there was PV work being done why would the enthalpy equation have dropped the PV term? How does constant pressure eliminate this term?
mortezarazavi
#2 Posted : Monday, July 09, 2012 12:34:30 AM
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Hi

Lets expand that equation: Delta H = q - P(surr) Delta V + P (sys) Delta V. So instead of U i put q + w and w in this case is -P(surr) delta V. One important thing you need to pay attention to is that the sign of work on the surrounding is the opposite of the sign of work that is done on the system this is why one of the P delta V is negative and the other one is positive. So if the system is doing work on the surrounding the work done by the system is negative and the work done on the surrounding is positive etc. Now there are two cases where Delta H = q --> 1) when in a chemical reaction you go from liquid to solid or vice versa the volume does not change by much so Delta V can be assumed to be 0 therefore Delta H = q. 2) If pressure of the surrounding is equal to the pressure of the system (i.e. Psurr = Psys) then the two P delta V expressions cancel out and Delta H = q. In most of the MCAT questions Delta H = q and therefore for question 413 we know that delta G = delta H + T delta S and since delta H = q then this signifies a non-PV work.

Hope this helps.
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