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**The Equilibrium Law
**

Le Chatelier’s principle gives us an idea of the direction of change, but, where concentrations

are involved, we can calculate precisely what happens using the equilibrium law.

**The Equilibrium Law states - At equilibrium the concentrations of the species in the reaction
**

system are constant.

For the general reaction mA + nB pC + qD

**Therefore [C]peq[D]qeq = a constant Kc
**

[A]meq[B]neq

**Kc is the Equilibrium constant.
**

Kc = [Right hand side]eq

[Left hand side]eq

[ ] refers to the concentration of the species.

e.g. For the equilibrium aA + bB cC + dD

**when the system has come to equilibrium, the ratio given by K c will be constant:
**

c d

[C] × [ D]

Kc = where [C] means concentration at equilibrium, normally in mol dm–3

a b

[A] × [ B]

(The main mistakes students make over this are to forget that the right hand side of the

equation goes on top, and to forget that concentrations are multiplied together, not added).

**Equilibria involving gases
**

For gases, it is often more convenient to express the equilibrium constant in terms of partial

pressures:

c d

P ×P

Kp = C D where PC is the partial pressure of C at equilibrium

PA × PB

a b

K p is called the pressure equilibrium constant.

**Note that the both types of equilibrium constant will have units, unless (c + d) = (a + b). They
**

therefore normally have different numerical values, for the same position of equilibrium.

-1-

if one gas makes up 15% by volume of the mixture (or 15% of the molecules) its partial pressure will be 0. For example aqueous sodium hydroxide solution having a concentration of 2 moldm-3.050 mol dm–3 (ii) total number of moles of gas = 0.00 dm3 vessel contains 0. the partial pressure of one gas is the pressure it would exert if it occupied the vessel alone. Example: a 4.15 × P.0.20 + 0. Concentration refers to number of moles of a substance dissolved in one dm3 of solution. or mole fraction.00 = 0.30 = 0.40 mol N 2 and 0. and together they have a partial pressure of 800 MPa. where P is the total pressure. This is represented as [NaOH(aq)] = 2 moldm-3.90 mole fraction of H 2 = 0.22 In a vessel containing a mixture of gases. -2- . then: partial pressure of nitrogen = ¼ × 800 = 200 MPa partial pressure of hydrogen = ¾ × 800 = 600 MPa. The total pressure in a mixture of gases is the sum of all the partial pressures.40 + 0. It follows that: partial pressure of A = mole fraction of A × total pressure For example. Calculate (i) the concentration of hydrogen. Mole fractions The mole fraction of a gas in a mixture is the fraction of the total number of moles of gas present: no. Note [ ] indicates a concentration.90 = 0. In a gas the proportion by volume is always the same as the proportion by moles. if one knows the number of moles of gas and the volume of the container: amount in moles concentration of gas = volume of vessel Units can be mol dm–3 or mol m–3 depending on how the volume of the vessel is specified. 0.20 ÷ 0. Answer: (i) concentration of hydrogen = 0. of moles of A mole fraction of A = total no.20 mol H 2 .30 mol Ar. of moles The sum of all the mole fractions must always be 1.20 ÷ 4. The same idea can be applied to a gas. If nitrogen and hydrogen are mixed in a 1:3 molar ratio.Partial pressure and concentration. (ii) the mole fraction of hydrogen.

CH 3 CO 2 H + C 2 H 5 OH CH 3 CO 2 C 2 H 5 + H 2 O Equilibrium amount/mol 0. When Kc for a reaction is known. The value of Kc is not altered by the addition of more reactants or products to an equilibrium mixture.0584 0. the relative portions of reactants and products at equilibrium can be calculated for any mixture of reactants used initially.1 (no units for esterification reaction) 0. Calculating K c and K p We normally find values for K c and K p from experimental data. Example 1: Calculate Kc for the esterification of ethanoic acid by ethanol given that for a 1dm3 of this homogeneous liquid equilibrium the amounts present are as shown below.0457 K c = [CH 3 CO 2 C 2 H 5 ] [H 2 O] [CH 3 CO 2 H] [C 2 H 5 OH] K c = 0. (A large value is any value >100).0437 = 4.0255 x 0.0255 0. If more products are added the system will move in the reverse direction to keep Kc constant.0245 0. it is a constant.0245 -3- . If more reactants are added the system will move in the forward direction to keep Kc constant. (A small value is any value <0.0584 x 0.01). If Kc is small the equilibrium mixture contains mostly reactants and the reaction has not proceeded very far.Values of K c and K p If Kc is large the equilibrium mixture contains mostly products and the reaction has nearly gone to completion.

dissolved in 0.Example 2.1 mol of A is mixed with 0.26/0.2704 Note that the number of moles is divided by the total volume (0.1 0.02 (since 1 A → 3 D. and allowed to come to equilibrium. In the reaction given below.06/0.06 D.02 0.33atm Kp = 1.16 × 0.5) to obtain the concentration.06 therefore: 0. we know: 0. K c .5 dm3 of water.04 × 0.1-0.02/0.04 0. 0. when the amount of D is found to be 0.08/0. Find the equilibrium constant.5) × (0.60 × 10–3 mol dm–3 0.02 A → 0.3 mol of B.3 0 0 At equilibrium. 0.67atm2 0.33atm what is the value of K p for the reaction at this temperature? N 2 O 4 (g) 2NO 2 (g) Kp = p2NO 2 (g) pN 2 O 4 (g) Kp = 0.04 B → 0.5) × (0. Example 3: If at 55oC the partial pressure of nitrogen dioxide in an equilibrium mixture is 0.5) Kc = 2 = 2 [A] × [ B] (0. and 0.06 mol.36atm -4- . 3 3 [C] × [ D] (0. A + 2B C + 3D At start: 0. 0.001728 = = 1.5) 0.67atm and the partial pressure of dinitrogen tetraoxide in the mixture is 0.3-0.02C is formed).06 D .

Some equilibrium reactions involve only substances in the same phase e. Find Kp.60 0.4 1. at 180°C and 2.00 At equilibrium 0. all aqueous solutions or all gases. Expressions for K c and K p do not include values for solid and pure liquid phases in heterogeneous reactions. the phosphorus pentachloride is found to be 40% dissociated.40 partial pressures 0.40 0. For example. PCl 5 (g) PCl 3 (g) + Cl 2 (g) At start 1. -5- .571× 0. These are homogeneous reactions.571atm 0.Example 4: In the dissociation of phosphorus pentachloride. the heterogeneous reaction between iron and steam.6 0.40 mol mole fractions 0.380 atm PPCl5 0.40 1.00 0.571 Kp = = = 0.g. Consider 1 mole of reactant.6 0.00 0.40 — total 1. a pure liquid and a gas or a solid and a gas.571atm PPCl3 × PCl2 0.g.4 0. These constant vapour pressures are incorporated into the value of K p .00 atm pressure. These are heterogeneous reactions.40 1. Some equilibrium reactions involve substances in different phases e.40 1.857atm 0.857 Values for solid and liquid phase in Kc and Kp.40 1. 3Fe (s) + 4H 2 O (g) Fe 3 O 4 (s) + 4H 2 (g) Kp = p4H 2 p4H 2 O Solids do not appear in the expression because their vapour pressures remain constant ( at a constant temperature) as long as there is some of each solid present (same applies for liquids).4 0.4 ×2 ×2 ×2 1.40 0.

The effect of temperature on Kc and Kp. nor in the presence of catalysts.Finding equilibrium partial pressures given Kp values.position of equilibrium moves to right. Temperature fall: .45atm pNO 2 (g) = 0. K p and K c become bigger.position of equilibrium moves to right. The equilibrium constant is only affected by temperature. Temperature fall: . K c . They only affect the time needed for the system to reach equilibrium. it does not change if concentrations or pressures are varied.33atm = 0.position of equilibrium moves to left.36atm for the reaction. The effects are the same as predicted by Le Chateliers principle. Catalysts do not alter the equilibrium constant (K p or K c ) or the position of equilibrium. K p and K c become smaller. -6- .33atm and K p at 55oC is 1.67atm.position of equilibrium moves to left. K p and the position of equilibrium are affected by temperature in endothermic and exothermic equilibria. K p and K c become bigger Endothermic reactions: Temperature rise: .36atm * 0. Example: What is the partial pressure of nitrogen dioxide in an equilibrium mixture if the partial pressure of dinitrogen tetraoxide in the mixture is 0. Exothermic reactions: Temperature rise: . N 2 O 4 (g) 2NO 2 (g) Kp = p2NO 2 (g)/ pN 2 O 4 (g) p2NO 2 (g) = Kp * pN 2 O 4 (g) = 1. K p and K c become smaller.

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