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Topic: Activation energy and enthalpy of reaction  (Read 15528 times)

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Offline kirushanth

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Activation energy and enthalpy of reaction
« on: February 23, 2012, 02:50:06 PM »
Can we compare, in a reaction, the reaction enthalpy and the activation energy?

I guess we should have Activation energy>=Reaction enthalpy always...

Offline Schrödinger

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Re: Activation energy and enthalpy of reaction
« Reply #1 on: February 24, 2012, 04:42:56 AM »
I guess we should have Activation energy>=Reaction enthalpy always...
Yes. You could say that.

Eact is almost always positive. ( I do remember someone telling me that negative Eact has been reported)

In the case of exothermic reactions, enthalpy < 0 and Eact obviously is > enthalpy.

In the case of endothermic reactions, the transition state is at a higher level than the products. Hence once again, Eact > enthalpy
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Offline Enthalpy

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Re: Activation energy and enthalpy of reaction
« Reply #2 on: February 25, 2012, 12:00:55 PM »
Puzzling! I had always imagined an activation energy as positive.

I sniff a hidden question in the question:

The produced energy does not need to exceed the activation energy, because the reaction energy is measured between the initial and the final state, not from the energy peak.

And: you don't need the products to provide more than the activation energy to the reactants, because heat is a statistical value. If the activation energy is 1000K, the reaction can proceed at 300K - just at some lucky molecules at a time. Additionally, this energy can be provided by the initial temperature.

Think of an equilibrium: even with an activation energy, both reaction directions (hence H>0 and H<0) will proceed provided the hill isn't too high.

But a relation with the initial conditions, sure.

Offline jaspevacek

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Re: Activation energy and enthalpy of reaction
« Reply #3 on: February 28, 2012, 02:58:13 PM »
A negative Eact can occur in dilute gas phase. By lowering the temperature, you slow the molecules down so that when they contact, they stick and react rather than fly apart.

Offline Stepan

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Re: Activation energy and enthalpy of reaction
« Reply #4 on: February 29, 2012, 07:20:50 AM »
As far as I remember the negative activation energy is usually an artifact of some secondary processes, like: mass transfer, or reactor configuration or experiment setup. for a particular chemical reaction it is generally positive.

There is no simple way to estimate activation energy from enthalpy.  But is you study several similar reactions measured under the same conditions, let say:
Ethylene+H2
Propylene+H2
Butene+H2
..
you almost for sure can discover  some sort of empirical correlation between  activation energy and enthalpy: Ea=Constant+alpha*Delta(H). Often alpha is about 0.5. To observe this effect you need to be sure that the reaction is not affect by mass transfer of reagents (slow reaction, low conversion). 

Not sure what is the explanation of this correlation.

Offline juanrga

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Re: Activation energy and enthalpy of reaction
« Reply #5 on: March 02, 2012, 02:11:37 PM »
Can we compare, in a reaction, the reaction enthalpy and the activation energy?

I guess we should have Activation energy>=Reaction enthalpy always...

Interesting question. I cannot think of a counterexample and agree.
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