Equilibruim - Revision

Dynamic equilibruim occurs when there is no further change in the concentrations of the reactants and products because the forward and backwards reactions are happening at the same rate.

The equilibrium constant, Kc

In general, for a reaction, xA + yB nC + mD

where x, y, n and m are stoichiometric amounts in the equation,

Kc

[C]n[D]m [A]x[B]y

HOWEVER, this only works for homogeneous equations (where all the reactants and products are in the same state). You do not include any term for a solid in the equilibrium equation. This only applies when the reaction is at equilibrium. The only things which will affect Kc are temperature and the equation itself. If the equation is written the other way around, then Kc will be different.

Kc

1 Kc

Units of Kc you have to cancel out the concentrations units, in the fraction of the equation. If the concentration is raised to a power, then the units also have to be raised to that power also.

The equilibrium constant, Kp

This is in terms of partial pressure, which is the contributions of each gas in a mixture to the total pressure. The partial pressure of a particular gas in a mixture is the same pressure it would exert if it were alone. Partial pressure = mole fraction x total pressure

Number of moles of a gas Total number of moles of gas In general, for a reaction,

xA

yB

nC

mD

where x, y, n and m are stoichiometric amounts in the equation,

Kp =

(pC)n(pD)m (pA)x(pB)y

Temperature, pressure and the reaction itself affect Kp. The Kp equation never includes anything but gases.

Relationship between the equilibrium constant and the total entropy change
Stotal = RlnK

Where R is the gas constant. If s-total increases, the value of K also increases. The magnitude of H/T always decreases as the temperature is increased. When the temperature increases for an exothermic reaction, -H/T becomes less positive which decreases the value of Ssurr. This causes both Stotal and K to decrease When the temperature increases for an endothermic reaction, - H/T becomes less negative. This causes both Stotal and K to increase.

Predicting the direction of change

Effect of Temperature change
For an exothermic reaction, an increase in temperature results in lowering the equilibrium constant. For endothermic reactions, an increase in temperature results in increasing the equilibrium Increasing the temperature favours the endothermic reaction, which also moves the position of equilibrium in that direction Increasing the temperature also increases the rate of reaction, which makes the reaction reach equilibrium faster

Effect of pressure change

Has no effect on the equilibrium constant If one side of the reaction has more moles on it, then increased pressure will move the position of equilibrium away from that side It will make the rate increase, so the reaction will reach equilibrium faster

Effect of adding a catalyst

This has no effect on either the equilibrium constant, or the position of equilibrium. It will increase the rate of reaction, so make the reaction reach equilibrium faster