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Thermodynamics

Question
CBSEENCH11006262

What is free energy change? Show that the change in free energy is equal to useful work done.
or
prove that –∆G = w(useful work)

Solution

(i) The overall criterion of a process to occur spontaneously i.e. driving force is expressed in terms of free energy change (∆G).
Free energy change (∆G) is related to enthalpy change (∆H) and entropy change (∆S) as ∆G = ∆H – T∆S [Gibbs-Helmoltz equation] For a spontaneous process, ∆G should have negative value.
(ii) According to first law of thermodynamics,
increment straight U space equals space straight q plus straight w
where q is heat absorbed by the system. ∆U is the change in internal energy and w is the work done on the system.
If we are to determine the work a system can do, then w should be taken as – w.
therefore space space space space space increment straight U space equals space straight q minus straight w
or space space space space space space space straight q space equals space increment straight U space plus straight w
Now w includes expansion as well as non-expansion work. 
straight q space equals space increment straight U space plus space straight w subscript exp space plus space straight w subscript non minus exp end subscript space space space... left parenthesis 1 right parenthesis
But work due to expansion at constant temperature is given by P∆V.
therefore space space space straight w subscript exp space equals space straight P increment straight V
wnon-exp is also called useful work because this type of work can be used for useful effect e.g. electrical work.
therefore space space equation space left parenthesis 1 right parenthesis space becomes
therefore space space space space space space space space space space space straight q space equals space increment straight U space plus space straight P increment straight V space plus space straight w subscript non minus exp end subscript
or space space space space space space space space space space space space straight q space equals space increment straight H space plus space straight w subscript non minus exp end subscript
space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space open square brackets because space increment straight H space equals space increment straight U space plus space straight P increment straight V close square brackets
But space space space space space space space increment straight S space equals space straight q subscript rev over straight T
space therefore space space space space space space space space straight q subscript rev space equals space straight T increment straight S
Substituting this value in (2), we have,
                       space straight T increment straight S space equals space increment straight H plus space straight w subscript non minus exp end subscript
or     increment straight H space minus space straight T increment straight S space equals space minus straight w subscript non minus exp end subscript
       But space increment straight G space equals space increment straight H minus space straight T increment straight S
space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space space open square brackets Gibb apostrophe straight s space Helmoltz space equation close square brackets
therefore space space space space increment straight G space equals space minus straight w subscript nonexp
or space space space space space space minus increment straight G space equals space straight w subscript nonexp
This means that decrease in free energy of a system (–∆G) is a measure of the non-expansion or useful work done by the system in a process or –∆G = wuseful work