What Is the Correct Symbol for Gibbs' Energy Under Standard Conditions?

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Discussion Overview

The discussion revolves around the correct notation for Gibbs' energy under standard conditions, particularly focusing on the symbols used (ΔGΘ, ΔGO, etc.) and their implications. Participants explore the definitions and relationships between Gibbs' free energy, enthalpy, and entropy, as well as the conditions under which these definitions hold true.

Discussion Character

  • Debate/contested
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • Some participants note that different symbols (μ∇, μΘ, μO) can represent chemical potential under standard conditions, depending on the temperature.
  • There is a question about whether ΔG should be denoted as ΔGΘ or ΔGO under standard conditions of 298.15 K and 1 bar pressure.
  • One participant asserts that ΔGΘ refers to the value of ΔG under standard conditions, raising the issue of whether the equilibrium constant K must equal 1 under these conditions.
  • Another participant emphasizes that K=1 at the standard state does not imply an equilibrium situation, suggesting that the standard state is often a theoretical construct.
  • Confusion arises regarding the definition of ΔGr° and its temperature dependency, with participants questioning if it can be simply defined as standard conditions of 298.15 K and 1 bar pressure.
  • Some participants clarify that ΔG° = ΔH° - TΔS° is valid for standard conditions, while ΔG = ΔH - TΔS is used for calculating when ΔG becomes negative with increasing temperature.
  • There is a discussion about the implications of K=1 and how it relates to ΔG and equilibrium, with some participants noting that ΔG° = 0 when K=1, but this does not necessarily indicate an equilibrium situation.

Areas of Agreement / Disagreement

Participants express differing views on the correct notation for Gibbs' energy and the implications of standard conditions. There is no consensus on the definitions and relationships discussed, indicating ongoing debate and uncertainty.

Contextual Notes

Participants highlight limitations in the definitions of standard conditions and the theoretical nature of the standard state, as well as the dependency of Gibbs' free energy on temperature, which complicates the discussion.

Big-Daddy
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My thermodynamics textbook says that chemical potential can take any of the following symbols: μ (condition-dependent), μ (standard), μΘ (standard) (superscript plimsoll line) and μO (standard), with which one of the latter 3 being used depending on the temperature chosen to define standard state.

I have seen that the notation typically used for ΔH under standard conditions of 298.15 K, 1 bar pressure is the ΔHΘ symbol (and ΔSΘ similarly). However, ΔGO is used to denote ΔG under standard conditions of 298.15 K, 1 bar pressure. Should this more correctly be ΔGΘ (so we write ΔGΘ=ΔHΘ-T·ΔSΘ, so the conditions are the same)? Or perhaps they are all actually O?

Also, does ΔGΘ for a reaction actually refer to the value of ΔG for that reaction under standard conditions of 298.15 K, 1 bar pressure? If so, wouldn't that mean that the equilibrium constant must be 1 under standard conditions (which is not necessarily true), as a result of ΔG=ΔGΘ+R·T·loge(Q) and now ΔG=ΔGΘ under such conditions? If not, what is the actual definition of ΔGΘ, and with regards to ΔG itself?
 
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To your second question. Yes, K=1 at the standard state, but this is not an equilibrium situation and the standard state is often only a theoretical construct which is impossible to realize experimentally.
E.g. you can't have a mixture of hydrogen and oxygen with partial pressure 1 bar of each component and total pressure being 1 bar, too.
 
DrDu said:
To your second question. Yes, K=1 at the standard state, but this is not an equilibrium situation and the standard state is often only a theoretical construct which is impossible to realize experimentally.
E.g. you can't have a mixture of hydrogen and oxygen with partial pressure 1 bar of each component and total pressure being 1 bar, too.

I'm getting confused now. How exactly is ΔGr° to be defined? I know that ΔGr°=ΔHr°-T*ΔSr°. But doesn't the ° symbol mean "standard conditions of 298.15 K and 1 bar pressure" or not - because if so then we may as well write ΔGr°=ΔHr°-298.15*ΔSr° and I'm sure this is wrong, because now let's look for the temperature at which K=1 (which should, according to what I showed in my OP, be 298.15 K, but is as I will show now indeterminate) through ΔGr°=-R*T*loge(K) and now ΔHr°-298.15*ΔSr°=-R*T*loge(K) and our system crashes: T=(ΔHr°-298.15*ΔSr°)/(-R*loge(K)), and far from 298.15 K, our answer will be undefined for K=1.

So the question becomes - what actually is ΔGr° with relation to ΔGr? Evidently it is incorrect to say "standard conditions of 298.15 K and 1 bar pressure" alone because clearly ΔGr° does exhibit temperature dependency due to the T variable in ΔGr°=ΔHr°-T*ΔSr°.
 
I would have to look up the details myself.
A very good reference on standard states is:


Klotz, Irving M. / Rosenberg, Robert M.
Chemical Thermodynamics
Basic Concepts and Methods
 
Big-Daddy said:
I'm getting confused now. How exactly is ΔGr° to be defined? I know that ΔGr°=ΔHr°-T*ΔSr°. But doesn't the ° symbol mean "standard conditions of 298.15 K and 1 bar pressure" or not - because if so then we may as well write ΔGr°=ΔHr°-298.15*ΔSr° and I'm sure this is wrong, because now let's look for the temperature at which K=1 (which should, according to what I showed in my OP, be 298.15 K, but is as I will show now indeterminate) through ΔGr°=-R*T*loge(K) and now ΔHr°-298.15*ΔSr°=-R*T*loge(K) and our system crashes: T=(ΔHr°-298.15*ΔSr°)/(-R*loge(K)), and far from 298.15 K, our answer will be undefined for K=1.

So the question becomes - what actually is ΔGr° with relation to ΔGr? Evidently it is incorrect to say "standard conditions of 298.15 K and 1 bar pressure" alone because clearly ΔGr° does exhibit temperature dependency due to the T variable in ΔGr°=ΔHr°-T*ΔSr°.
ΔG° = ΔH°-TΔS° This is the free energy change with standard conditions @ 298 K from elements
in their standard states. Where ΔG = ΔH-TΔS is for calculating when ΔG becomes negative with
increasing temperature. Also regarding solving for T when K =1 , its my understanding that its
when ΔG = 0 that K =1
 
If K=1 the logarithm vanishes and ##\Delta G=\Delta G^0##. K=1 in general does not correspond to an equilibrium situation (even less at fixed temperature so ##\Delta G## won't be 0. In contrast, ##\Delta G^0=-RT \ln K## holds only in equilibrium.
 
Last edited:
DrDu said:
If K=1 the logarithm vanishes and ##\Delta G=\Delta G^0##. K=1 in general does not correspond to an equilibrium situation (even less at fixed temperature so ##\Delta G## won't be 0. In contrast, ##\Delta G^0=-RT \ln K## holds only in equilibrium.
In post # 3 Big-Daddy is solving for T with ΔG° = ΔH° - TΔS° and ΔG°(298K) = -RTlnK
Standard free energy changes @ 298K. And in ΔG° = -RTlnK 'K' can have different values
and when K = 1 , ΔG° = 0 Not questioning your last post - just for clarification
 

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