Equilibrium constant change with stoichiometric doubling (Callen)?

Click For Summary
SUMMARY

The equilibrium constant for a reaction with stoichiometric coefficients doubled is related to the original equilibrium constant by the equation K_d = K_s^2. The derivation involves the logarithmic relationship, where ln K_d(T) = 2 ln K_s(T), leading to the conclusion that K_d is the square of K_s. A common mistake arises from misapplying the exponential function, where exp(2 ln K_s(T)) simplifies to (exp(ln K_s(T)))^2, not e^2 exp(ln K_s(T)). This clarification resolves the confusion regarding the relationship between the two equilibrium constants.

PREREQUISITES
  • Understanding of equilibrium constants in chemical reactions
  • Familiarity with logarithmic and exponential functions
  • Basic knowledge of stoichiometry
  • Concept of ideal gases in thermodynamics
NEXT STEPS
  • Study the derivation of equilibrium constants in chemical thermodynamics
  • Learn about the properties of logarithms and exponentials in mathematical contexts
  • Explore stoichiometric relationships in chemical reactions
  • Investigate the implications of the ideal gas law on reaction equilibria
USEFUL FOR

Chemists, chemical engineers, and students studying thermodynamics and reaction kinetics will benefit from this discussion, particularly those focusing on equilibrium constants and stoichiometric relationships in reactions.

EE18
Messages
112
Reaction score
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?
 
Last edited:
Science news on Phys.org
##2 \ln x = \ln(x^2)##
 
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?
 
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##.
 
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.
 
EE18 said:
Oof, of course. ##\exp(2+\ln K_s(T)) =e^2K_s## which is of course not what we have here.
Right.
 

Similar threads

  • · Replies 19 ·
Replies
19
Views
3K
  • · Replies 6 ·
Replies
6
Views
2K
  • · Replies 3 ·
Replies
3
Views
2K
  • · Replies 23 ·
Replies
23
Views
3K
  • · Replies 22 ·
Replies
22
Views
6K
Replies
9
Views
4K
Replies
16
Views
4K
Replies
5
Views
2K
Replies
14
Views
3K