Is Decreased Internal Energy Essential for Spontaneous Reactions?

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Discussion Overview

The discussion revolves around the relationship between internal energy and spontaneity in chemical processes, specifically questioning whether a decrease in internal energy is essential for spontaneous reactions. The scope includes theoretical considerations and conceptual clarifications related to thermodynamics.

Discussion Character

  • Debate/contested
  • Conceptual clarification

Main Points Raised

  • Some participants assert that a spontaneous process is typically accompanied by a decrease in internal energy, referencing that ΔH and ΔG are negative for spontaneity.
  • Others challenge this by stating that ΔH does not have to be negative for a spontaneous process, citing the example of ammonium nitrate solution, which is endothermic yet spontaneous.
  • One participant notes that while exceptions exist, most spontaneous processes do involve a negative ΔH.
  • Another participant emphasizes the relationship between stability and internal energy, suggesting that lower internal energy correlates with greater stability.
  • It is mentioned that the spontaneity of a reaction is linked to the second law of thermodynamics, highlighting the importance of entropy changes in both the system and surroundings.
  • A participant explains that for isothermal reactions, transferring heat from the system to the surroundings can increase the entropy of the surroundings, thus favoring spontaneity.

Areas of Agreement / Disagreement

Participants express differing views on the necessity of a decrease in internal energy for spontaneity, with some arguing that it is essential while others provide counterexamples of spontaneous endothermic processes. The discussion remains unresolved regarding the role of internal energy in spontaneity.

Contextual Notes

There are unresolved assumptions regarding the definitions of internal energy, enthalpy, and entropy, as well as the conditions under which these relationships hold true. The discussion does not clarify the specific scenarios or limitations of the claims made.

utkarshakash
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Homework Statement


Why a spontaneous process is accompanied by a decrease in internal energy?


Homework Equations



The Attempt at a Solution


I know that ΔH and ΔG will be negative for a spontaneous process
 
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utkarshakash said:

Homework Statement


Why a spontaneous process is accompanied by a decrease in internal energy?


Homework Equations



The Attempt at a Solution


I know that ΔH and ΔG will be negative for a spontaneous process

ΔH does not have to be negative for a spontaneous process. Solution of ammonium nitrate is spontaneous, and that is a process that takes in a lot of heat from its surroundings, Many processes are endothermic and spontaneous.
 
JohnRC said:
ΔH does not have to be negative for a spontaneous process. Solution of ammonium nitrate is spontaneous, and that is a process that takes in a lot of heat from its surroundings, Many processes are endothermic and spontaneous.
I know exceptions exist but in most of the cases it is negative. But I don't know why internal energy has to be negative
 
Remembered that Stability is inversely proportional to Internal Energy, if you asked that question.

As JohnRC pointed, ΔH need not be negative. It's only ΔG = ΔH - TΔS. See, even if ΔH is positive, a sufficient temperature of the system, accompanied by increase in entropy, can easily make ΔG negative.
 
AGNuke said:
Remembered that Stability is inversely proportional to Internal Energy, if you asked that question.

Why is it so?
 
Its a generally observed trend. Everything is stable when they are relaxed (Low energy state).

You are not comfortable standing while lifting a water filled bucket, are you? (High energy state as you need energy to keep the bucket lifted).
 
utkarshakash said:
Why is it so?

The spontaneity of a reaction is related to whether the reaction satisfies the second law of thermodynamics; that is, whether the reaction increases the total entropy of the universe. Obviously, the change of entropy of the system is an important component of the spontaneity. The change of entropy of the surroundings is the other important component. For an isothermal reaction, any reaction that transfers heat from the system to the surroundings will increase the entropy of the surroundings (you can think of this as energy confined to the system being liberated to the larger surroundings). Thus, a decrease in internal energy of the system, which for isobaric processes means that heat is transferred to the surroundings, will favor spontaneity.
 

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