How Do Entropy and Enthalpy Influence the Dissolution of Ionic Solids?

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Discussion Overview

The discussion revolves around the influence of entropy and enthalpy on the dissolution of ionic solids, exploring the conditions under which ionic solids dissolve, the roles of enthalpy changes, and the implications of entropy changes in the process. Participants examine theoretical aspects and seek clarification on concepts presented in textbooks.

Discussion Character

  • Exploratory
  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant suggests that for ionic solids to dissolve, the enthalpy change (\Delta H_{solution}) must be negative or possibly zero for equilibrium, and that this occurs when the enthalpy of hydration (\Delta H_{hyd}) for cations and anions exceeds the lattice energy (\Delta H_{LE}).
  • Another participant counters that the Gibbs free energy change (\Delta G_{solution}) must be negative for dissolution, not solely the enthalpy change.
  • There is mention of a scenario where a positive \Delta H_{solution} can still lead to dissolution if the entropy change is favorable, indicating a complex interplay between these thermodynamic quantities.
  • Concerns are raised about cases where a negative \Delta H_{solution} does not guarantee dissolution due to a decrease in entropy, as seen in the example of CaCO3.
  • Participants express uncertainty about the relationship between ionic charge, size, and entropy reduction during dissolution.
  • There is a call for clarification on the roles of entropy and enthalpy, as the textbook does not fully address these concepts.

Areas of Agreement / Disagreement

Participants exhibit disagreement regarding the primary conditions for dissolution, with some emphasizing the importance of enthalpy while others highlight the necessity of considering Gibbs free energy. The discussion remains unresolved as participants seek further clarification on these concepts.

Contextual Notes

Participants note that the textbook primarily discusses enthalpy changes without adequately addressing Gibbs free energy, which incorporates both entropy and enthalpy. This omission contributes to the confusion surrounding the dissolution process.

nobahar
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Hello!
If ionic solids are to dissolve, then \Delta H_{solution} has to be negative, (possibly 0? For equilibrium?). This can occur if \Delta H_{hyd} for both the cations and anions is greater than the \Delta H_{LE}. But the textbook also states that a positive \Delta H_{solution} can also result in the ionic solid dissolving if the entropy change, being positive, is favourable for it to do so. However, it also says that on some occasions, even if there is negative \Delta H_{solution}, the ionic solid will not dissolve because of an entropy decrease. The large attraction between the ions and, for example, water, is enough to reduce the entropy to a point where it is not a spontaneous process.

If \Delta H_{Hyd} is large enough that it is favourable for the ions to be 'pulled' from the lattice; won't this also mean that the ions have a stronger charge (or are smaller, or both) and so there will be a reduction in entropy in the process?

An example given in the textbook is of CaCO3, which will not dissolve even though, apparently, the \Delta H_{solution} is negative, because the entropy of the resulting solution is reduced, again to a point where there isn't a favourable change..

I don't know if this makes sense, as you may well be able to tell! Basically, can someone point me in the right direction or expand on this for me; that is, the role of entropy and enthalpy in the process? Since the textbook stops the discussion at this point. If the question isn't clear just let me know and I'll condense it!
Thanks.
Nobahar.
 
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nobahar said:
Hello!
If ionic solids are to dissolve, then \Delta H_{solution} has to be negative, (possibly 0? For equilibrium?).

No. \Delta G_{solution} must be negative not \Delta H_{solution}.

Basically, can someone point me in the right direction or expand on this for me; that is, the role of entropy and enthalpy in the process? Since the textbook stops the discussion at this point. If the question isn't clear just let me know and I'll condense it!
Thanks.
Nobahar.

Review the definition of gibbs free energy.
 
The textbook hasn't even mentioned free energy, it just states \Delta H.
I'll work on it. Thanks for the reply.:smile:
 
nobahar said:
The textbook hasn't even mentioned free energy, it just states \Delta H.
I'll work on it. Thanks for the reply.:smile:

Gibbs free energy takes into account both entropy and enthalpy , I am not quite certain where your confusion is on either , both of them describe universal tendencies ... you need to review both of the ultimate statements of entropy and enthalpy.
 

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