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Topic: Relation between reaction rate and equilibrium  (Read 9987 times)

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Offline NYM

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Relation between reaction rate and equilibrium
« on: November 29, 2006, 04:16:12 PM »
Does anybody know a relation(i.e. formula etc.) between the reaction rate and equilibirum?

Thanks.

Offline Yggdrasil

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Re: Relation between reaction rate and equilibrium
« Reply #1 on: November 29, 2006, 04:44:30 PM »
Consider the reaction:

A + B <--> C + D

With forward rate constant k1 and backward rate constant k-1.  Write out the expression for the forward reaction rate and the backward reaction rate.  Then recall that at equilibrium the forward reaction rate is equal to the backward reaction rate.  From there you can derive an expression of the equilibrium constant (remember K = [D][C]/[A]) in terms of the forward and backward rate constants.

Offline mdlhvn

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Re: Relation between reaction rate and equilibrium
« Reply #2 on: November 29, 2006, 09:06:38 PM »
Consider the reaction:

A + B <--> C + D

With forward rate constant k1 and backward rate constant k-1.  Write out the expression for the forward reaction rate and the backward reaction rate.  Then recall that at equilibrium the forward reaction rate is equal to the backward reaction rate.  From there you can derive an expression of the equilibrium constant (remember K = [D][C]/[A]) in terms of the forward and backward rate constants.

------In a easy way, the equilibrium constant of this reaction Keq=k-1/k1

Offline NYM

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Re: Relation between reaction rate and equilibrium
« Reply #3 on: November 30, 2006, 02:07:52 AM »
Then recall that at equilibrium the forward reaction rate is equal to the backward reaction rate.

Hmm, not really. Could you elaborate a bit?
I don't see why v1 = v2, where v1 = forward reaction rate and v2 = backward reaction rate.

Offline Yggdrasil

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Re: Relation between reaction rate and equilibrium
« Reply #4 on: November 30, 2006, 03:45:16 AM »
Well, at equilibrium the net change of reactants and products is zero.  Since the forward rate of reaction gives the rate at which reactants are transformed to products and the backward rate gives the rate at which products are transformed to reactants, if these two rates are not equal then the net rate of change of products and reactants will be nonzero.

As an example, consider a situation where I hand you 2 boxes per minute.  If you hand me 2 boxes per minute, then the number of boxes we have stays the same and our system is in equilibrium.  However, if you hand me 3 boxes per minute, boxes will accumulate on my side.  Since the number of boxes on my side increases with time, this system is not at equilibrium.

Offline Borek

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Re: Relation between reaction rate and equilibrium
« Reply #5 on: November 30, 2006, 04:28:41 AM »
if these two rates are not equal then the net rate of change of products and reactants will be nonzero

and the concentrations/amounts of substances will be changing - thus system will be not a equilibrium.
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Offline NYM

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Re: Relation between reaction rate and equilibrium
« Reply #6 on: November 30, 2006, 01:03:09 PM »
Thanks, everybody!

Offline NYM

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Re: Relation between reaction rate and equilibrium
« Reply #7 on: November 30, 2006, 03:50:48 PM »
Wait a second -

under "Equilibrium reactions or opposed reactions" at http://en.wikipedia.org/wiki/Rate_law

Why isn't k1 = k2?
If v1 = v2, then k1 = k2, right?

Please explain :)

Offline Borek

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Re: Relation between reaction rate and equilibrium
« Reply #8 on: November 30, 2006, 04:32:54 PM »
Why isn't k1 = k2?
If v1 = v2, then k1 = k2, right?

No. For the reaction

A + B <--> C + D

v1 = k1[A]

and

v2 = k2[C][D]

v1 & v2 depend on the concentrations, so your conclusion that if v1=v2 then k1=k2 is faulty.
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Offline Yggdrasil

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Re: Relation between reaction rate and equilibrium
« Reply #9 on: November 30, 2006, 06:43:13 PM »
v1 = k1[A]

and

v2 = k2[C][D]

And, at equilibrium, v1 = v2, so you can write:

k1[A] = k2[C][D]

Rearranging you can get

[C][D]/[A] = k1/k2

Since [C][D]/[A] is defined to be the equilibrium constant for the reaction that Borek poste, Keq, we have derived the expression that:

Keq = k1/k2

where k1 is the forward rate constant and k2 is the backward rate constant

Offline thienanh

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Re: Relation between reaction rate and equilibrium
« Reply #10 on: December 01, 2006, 07:37:19 AM »
v1 = k1[A]

and

v2 = k2[C][D]

And, at equilibrium, v1 = v2, so you can write:

k1[A] = k2[C][D]

Rearranging you can get

[C][D]/[A] = k1/k2

Since [C][D]/[A] is defined to be the equilibrium constant for the reaction that Borek poste, Keq, we have derived the expression that:

Keq = k1/k2

where k1 is the forward rate constant and k2 is the backward rate constant
Ok, this is only true with a simple reaction. There are some reactions don’t obey this. What’s about the complicated reactions, how can we write the rate reaction if we don’t know about its mechanism?

Offline NYM

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Re: Relation between reaction rate and equilibrium
« Reply #11 on: December 01, 2006, 02:45:39 PM »
All right, that's all for now, thanks!

Offline Yggdrasil

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Re: Relation between reaction rate and equilibrium
« Reply #12 on: December 01, 2006, 04:33:11 PM »
Ok, this is only true with a simple reaction. There are some reactions don’t obey this. What’s about the complicated reactions, how can we write the rate reaction if we don’t know about its mechanism?

You are correct, this expression does work only for elementary reactions.  For reactions where we don't know the mechanism, I don't think there is a way to relate the equilibrium constant to the rate of reaction (especially since we wouldn't be able to get any true rate constants if we don't know the actual mechanism!).

Offline zeifer_roth

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Re: Relation between reaction rate and equilibrium
« Reply #13 on: December 04, 2006, 06:41:22 AM »
errrrrr... sorrry i don't really know the exact formula.. but 1 know a general concept bout it.. "the faster the reacrion rate the lower is the equilibrium conversion"...

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