Equilibrium constant change with stoichiometric doubling (Callen)?

In summary: So, in summary, the equilibrium constant for a reaction which is the sum of this reaction with itself (doubled reaction) is 2 times the equilibrium constant for the same reaction when written with stoichiometric coefficients twice as large.
  • #1
EE18
112
13
Callen asks us (with respect to an ideal gas)
How is the equilibrium constant of a reaction related to that for the same reaction when written with stoichiometric coefficients twice as large? Note this fact with caution!
I had thought to proceed as follow. We have the definition for the singular reaction:
$$\ln K_s(T) = - \sum_j \nu_j \phi_j(T).$$
Now a reaction which is the sum of this reaction with itself (doubled reaction) has ##\nu_j \to 2\nu_j## so that its equilibrium constant obeys, by definition,
$$\ln K_d(T) = - \sum_j 2\nu_j \phi_j(T) = 2\ln K_s(T) \implies K_d = e^2K_s.$$
But when I look online it says the equilibrium constant should square in this case, ##K_d = K_s^2##. Can someone point out what I'm doing wrong?
 
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  • #2
##2 \ln x = \ln(x^2)##
 
  • #3
TSny said:
##2 \ln x = \ln(x^2)##
You are saying to use
$$\ln K_d(T) = 2\ln K_s(T) = \ln K^2_s(T)\implies K_d = K_s^2$$
which makes sense to me. I'm embarrassed to say I don't know what I'm doing wrong by using
$$\exp(\ln K_d(T)) = K_d = \exp(2\ln K_s(T)) = e^2 exp(\ln K_s(T)) = e^2K_s$$
which is different. What elementary algebra is being slipped under on me here?
 
  • #4
EE18 said:
You are saying to use
$$\ln K_d(T) = 2\ln K_s(T) = \ln K^2_s(T)\implies K_d = K_s^2$$
which makes sense to me. I'm embarrassed to say I don't know what I'm doing wrong by using
$$\exp(\ln K_d(T)) = K_d = \exp(2\ln K_s(T)) = e^2 exp(\ln K_s(T)) = e^2K_s$$
which is different. What elementary algebra is being slipped under on me here?
Note that ##\exp(2\ln K_s(T)) \neq e^2 \exp(\ln K_s(T))##.

Instead, ##\exp(2\ln K_s(T)) = [\exp(\ln K_s(T)]^2##. This follows from ##x^{ab} = (x^a)^b##.
 
  • #5
TSny said:
Note that ##\exp(2\ln K_s(T)) \neq e^2 \exp(\ln K_s(T))##.

Instead, ##\exp(2\ln K_s(T)) = [\exp(\ln K_s(T)]^2##. This follows from ##x^{ab} = (x^a)^b##.
Oof, of course. ##\exp(2+\ln K_s(T)) =e^2K_s## which is of course not what we have here.

My bad, and thanks for the clarification on this silly error.
 
  • #6
EE18 said:
Oof, of course. ##\exp(2+\ln K_s(T)) =e^2K_s## which is of course not what we have here.
Right.
 

1. What is the definition of equilibrium constant change with stoichiometric doubling?

The equilibrium constant change with stoichiometric doubling, also known as the Callen equation, is a mathematical relationship that describes how the equilibrium constant of a chemical reaction changes when the stoichiometric coefficients of the reactants and products are doubled. It is based on the principle of Le Chatelier's principle, which states that a system at equilibrium will shift in a direction that counteracts any imposed change.

2. How is the equilibrium constant affected by stoichiometric doubling?

When the stoichiometric coefficients of a chemical reaction are doubled, the equilibrium constant will also change. For a reaction in the form of aA + bB ⇌ cC + dD, the equilibrium constant K will be raised to the power of (c+d)/(a+b) in the Callen equation. This means that if the stoichiometric coefficients are doubled, the equilibrium constant will increase by a factor of K^(c+d)/(a+b).

3. What is the significance of the Callen equation?

The Callen equation is significant because it allows us to predict how changes in the stoichiometric coefficients of a reaction will affect its equilibrium constant. This is important in understanding the behavior of chemical reactions and predicting the outcome of reactions under different conditions.

4. Can the Callen equation be applied to all chemical reactions?

No, the Callen equation is only applicable to reactions that follow the law of mass action, which states that the rate of a chemical reaction is proportional to the product of the concentrations of the reactants. It also assumes that the reaction is taking place at a constant temperature and pressure.

5. How does the Callen equation relate to Le Chatelier's principle?

The Callen equation is based on Le Chatelier's principle, which states that a system at equilibrium will shift in a direction that counteracts any imposed change. In the case of stoichiometric doubling, the equilibrium constant changes in such a way that the shift in equilibrium will counteract the doubling of the stoichiometric coefficients. This is in line with Le Chatelier's principle, as the system is trying to maintain equilibrium by shifting in the opposite direction of the imposed change.

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