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Topic: equilibrium constant affected by pressure?  (Read 15817 times)

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Offline maakii

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equilibrium constant affected by pressure?
« on: March 11, 2007, 04:46:23 AM »
I don't understand one part about the equilibrium constant Kp. If I am not wrong, Kp tells you about the extent of the reaction at equilibirum, i.e. the proportion of products to reactants. If products >>reactants, then Kp is large. If reactants >>products, kp is small.

Now i understand that adding a catalyst will not change the kp, as the ratio of products to reactants remain unchanged. Also, the rates of the forward and backwards reactions are equally increased.

For exothermic reactions, increasing temperature will shift equilibrium to the left, and Kp decreases.

However, why does pressure not affect the equilibrium constant? For a reaction

N2 + 3H2 -> 2NH3

Increasing pressure favours the forward reaction. And when equliibrium is reached again, there should be an increase in the proportion of products to reactants, and looking at the extent of reaction, we should see that it lies furthur to the left, and thus Kp should increase.

But why does it not?

Offline xiankai

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Re: equilibrium constant affected by pressure?
« Reply #1 on: March 11, 2007, 04:21:43 PM »
Quote
i.e. the proportion of products to reactants.

in terms of partial pressures.

Quote
But why does it not?

the apparent increased value for Kp is offset by the increase in pressure term in the calculation of partial pressure.
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Offline charco

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Re: equilibrium constant affected by pressure?
« Reply #2 on: March 12, 2007, 02:44:37 PM »
If you consider a gaseous system at equilibrium then the total number of moles is constant, the temperature is constant and so according to the gas laws if you wish to increase the pressure you MUST change the volume (decreasing it).
Concentration is given by moles/volume so you therefore change (increase) the concentrations as well. If the moles on either side of the equilibrium are unequal then the concentration must increase by unequal amounts temporarily giving proportions that are not now equal to Kc. The system then responds to RESTORE the value of Kc and in doing so moves towards the side of fewer moles.

You can demonstrate this with simple maths.

In the equation: A <==> 2C
let the [A]=a and the [C]=b

Kc = b2/a

if the pressure is then doubled (by halving the volume) then the concentraton of C becomes 2b and the concentration of A becomes 2a

the ratio [products]2/[reactants] now equals 4b2/2a

which is precisely double the original ratio. The system is not at equilibrium as this ratio does not have the value of Kc and so restores the value of Kc by reducing the [products] and increasing the [reactants].

In other words the system moves towards the side of fewer moles to restore the value of Kc.

In all of this I have used Kc but the same logic can be applied to Kp. It's just easier to visualise with Kc that's all.

Offline maakii

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Re: equilibrium constant affected by pressure?
« Reply #3 on: March 12, 2007, 08:54:49 PM »
Thanks, I get it now  :) you've been a great *delete me*

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