EQUILIBRIUM

Law of mass action: Rate of reaction is proportional to product of effective concentrations of reactants, raised to a power = stoichiometric number of substance in the reaction. EQUILIBRIUM CONSTANTS: FOR THE REACTION aA(g) + bB(g) cC(g) + dD(g) Now, if B is made in solid Keq =

FACTORS AFFECTING EQUILIBRIUM CONSTANT:

Nature of components: For the reactions, N2 + O2 2NO, N2 + O2 2NO2

Kc is different coz of different products

phase, then the equilibrium constant: The diff b\w Keq Kc = and Kc is : Keq is defined [C]c[D]d for all reactants and products a [A]of their phase, while K is defined irrespective c only for variable components like gases & solutions and not for solids /pure liquids/solvents. Now, if the constant is expressed in terms of the partial pressures of the components, then,
Kp = (PC)c(PD)d (PA)a(PB)b

[C] [D] [A]a[

c d

Temperature: Variation Is

Stoichiometry: The Kc for these are different AND

N2(g) + 3H2(g) 2NH3(g) 1/2N2(g) + 3/2H2(g) NH3(g)

AND ALSO [n = (c + d) (a + b)]

Kp = Kc(RT)n,

Mode of writing equation: For the two, N2(g) + 3H2(g) 2NH3(g) (Kc1) 2NH3(g) N2(g) + 3H2(g) (Kc2) Kc1 = 1/Kc2 AND

If one of the components is in soln phase, then Kpc is defined taking the concentration of the solute in the soln. Kp, At least 1 component should be For gaseous and also, no component should be in soln. phase. PREDICTING DIRECTION OF ATTAINING EQUILIBRIUM: For this reaction quotient is taken = ratio of concentration of reacting species at any time other than equilibrium. Q = [C]c[D]d [A]a[B]b

DEGREE OF DISSOCITATION: The fraction of a mole of the reaction that underwent reaction = = No. of Moles of reactant dissociated No. of Moles present initially 2NH3(g) Moles initially Equilibrium 1 1x N2(g) 0 x + 3H2(g) 0 3x

[DONT TOUCH DIS PLACE ITS 4 ME ONLY TO PASTE SMTHIN]

x represents here. For a moles of ammonia initially, = x/a where x moles have dissociated. A LOT OF EXAMPLES OF HOMOGENOUS & HETEROGENOUS EQUILIBRIA AND THEIR DISCUSSIONS ARE GIVEN IN BRILLIANT. HAVE TO GO THRU THEM CAREFULLY AND NOTE Kp, Kc & WHETHER Kp = Kc Relation b\w Kc & G: G < 0 (+ve) G > 0 Reaction spontaneous & proceeds in forward direction Reaction nonspontaneous and

(ve) G = 0

proceeds in backward direction System at equilibrium and no reaction occurs (no more free energy for reaction)

Reaction proceeds in the direction leading to: More moles of gases Lesser moles of gases Addition of inert gas: When inert gas is added at constant volume, equilibrium is unaffected whether or not n = 0. When inert gas is added at constant pressure,

NCERT says this method to solve problems NO. STEP 1 Write balanced equation Make a table as above that also lists the 2 change in concentration, then use stoichiometry to express in terms of x. Substitute equilibrium concentration into 3 the equation for reaction to solve x. For quadratic eqns, choose a solution agreeing with the reaction(see NCERT for examples) 4 Calculate equilibrium concentrations from x calculated. 5 Substitute and check for errors in the given eqn 6 Temperature should be known at which equilibrium occurs If a reaction is expressed as the sum or 2 or 7 more reactions then the equilibrium const is given by the product of individual equilibrium reactions(example in Brilliant) If there are 2 equilibria in a container and 8 any component is common, then equilibrium concentration of common species is same in both equilibria Concentrations of pure solids, liquids and 9 solvents are constant, dont appear in equilibrium constant. 10 Remember the equation Kp = Kc(RT)n LE CHATELIERS PRINCIPLE: A change in a factor that determines the equilibrium condition causes the equilibrium to readjust itself so as to nullify that change. EFFECTS ARE: Change in no. of moles:

n = 0 n 0 Equilibrium Reaction proceeds in direction unaffected leading to more number of moles. Addition of a catalyst: Presence of catalyst doesnt alter the K or the position of equilibrium, but only helps a mixture to attain equilibrium faster. Change in temperature: Value of Kc is changed.

As The Temperature Increases H < 0 H > 0 Equilibrium constant Equilibrium constant for an exothermic for an endothermic reaction decreases reaction increases But practically, for an exothermic reaction, decreasing the temperature to very low slows the reaction and catalyst must be used

Changing more than 1 parameter: If more than 1 parameter is changed, find the changed value of the Q and Kc compare these two. Q = Kc No effect on reaction Q > Kc Net reaction moves in backward direction

Q < Kc Net reaction moves in forward direction

RELATION B\W VAPOUR DENSITY AND :

V.D = RT = RT 2P 2nRT

AND

= (D d) (n 1)d

RELATION B\W G0 AND Kc: Remember the

relations of G0 & Kc as before. G0 = RT ln(K) T in Kelvin. If R is in joules then G0 is also in joules and the same case for when R is in calories

If reactant is If product is added/product is removed added/reactant is removed Net reaction moves in Net reaction moves in forward direction backward direction to establish new equilibrium Change in volume: Increasing volume Decreasing volume