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Thermodynamics

Question
CBSEENCH11006235

Is ∆H the only criterion for the feasibility of a process ? Comment.

Solution
No, it is a common observation that all systems tend to acquire a state of greater stability
through the decrease of energy, for example,
(i) Flow of water down a hill
(ii) Chemical reactions such as
straight C left parenthesis straight s right parenthesis space plus space straight O left parenthesis straight g right parenthesis space rightwards arrow space space CO subscript 2 left parenthesis straight g right parenthesis semicolon space space increment straight H space equals space minus 394 space kJ
straight H subscript 2 left parenthesis straight g right parenthesis space plus space 1 half straight O subscript 2 left parenthesis straight g right parenthesis space rightwards arrow space space straight H subscript 2 straight O left parenthesis l right parenthesis semicolon space increment straight H space equals negative 286 space kJ
In all these cases, the system tends to change from higher energy state to lower energy state. Now a process in which energy of the system decreases has a negative value of ∆H (Exothermic reaction). Thus, a tendency to acquire minimum energy (–∆H) may be taken as the cause of spontaneity.
Although for most of the spontaneous processes, ∆H is negative, yet it cannot be taken as the only criterion of spontaneity. There are many endothermic reactions (∆H is +ve) which occur spontaneously. For example,
(i) Ammonium chloride dissolves in water with the absorption of heat i.e. ∆H is +ve.
(ii) Water evaporates with the absorption of heat.
 
   straight H subscript 2 straight O left parenthesis l right parenthesis space rightwards arrow space space straight H subscript 2 straight O left parenthesis straight g right parenthesis semicolon space space increment straight H space equals space 40.6 space kJ space mol to the power of negative 1 end exponent
Again there are spontaneous reactions which do not go to completion even though ∆H throughout remains negative.
There are reactions where ∆H = 0 but still they are spontaneous. For example.
CH subscript 3 COOH left parenthesis l right parenthesis space plus space straight C subscript 2 straight H subscript 5 OH left parenthesis l right parenthesis space space rightwards arrow space space CH subscript 3 COOC subscript 2 straight H subscript 5 left parenthesis l right parenthesis space plus space straight H subscript 2 straight O left parenthesis l right parenthesis
Thus, we may conclude that negative value of ∆H is not the sole criterion for determining the spontaneity of the reaction.