The rate-determining step: A reaction mechanism is a series of steps that, together, make up the overall reaction The rate-

- determining step is the slowest step in the reaction mechanism of a multistep reaction. The rate-determining step contains the reactants stated in the rate equation to the powers The Equilibrium Constant, Kc: If the overall equation of a reaction at equilibrium is aA + bB then the value for Kc would be Kc = [C]C x [D]D [A]A x [B]B Kc is the equilibrium constant in terms of concentrations. The concentration of each product and reactant is raised to the power of its balancing number in the overall equation. Units of Kc cC + dD,

Half Lives:
Module 1 Rates, Equilibrium and pH

Rates of Reaction:
Rate of reaction is the change in concentration of reactant/product over time Rate = change in concentration of reactant/product time As a reaction proceeds, concentrations of reactants decrease: fewer collisions take place per second between reactant particles the rate slows down Rate fastest initially 50 Gradient less steep and rate The gradient of the tangent at any point on a graph of experimental results shows the rate at that point. The value of the tangent at t=0 gives the initial rate of the reaction. The value of an increased concentration of product can also be calculated. E.G. The gradient of the red line = 50/20 = 2.5 mol dm-3s-1 20 Units = mol dm -3s-1

The half-life of a reactant is the time taken for the concentration of the reactant to decrease by half. The order of a reactant can be calculated by working out the half-life from a concentration-time graph.

The half-life decreases with time, as the concentration decreases at a constant rate.

The half-life of a first order reaction is constant, and remains the same no matter what the concentration

The half-life increases with time, as the concentration decreases rapidly but the rate of decrease then slows down.

The rate can also be determined by plotting a rate-concentration graph.

Orders and the Rate Equation:

The greater the concentration of a reactant, the larger the number of collisions per second, hence the faster the reaction. For any given reactant: Rate [A]x where x = the order of the reactant Zero Order First Order Second Order Initial Rates: Initial rate can be determined from a concentration-time graph by drawing a tangent at t =0 and calculating the gradient of the tangent. Alternatively the initial rate can be worked out experimentally by using 1/t. The rate constant, k: The larger the value of k , the faster the reaction: o o Second Order = k = rate = Third Order = k A fast reaction has a large value of k A slow reaction has a small value of k

If [A] is changed, the If [B] increases by 2 If [C] increases by 2 rate remains times, the rate also times, the rate increases The rate equation shows the relationship the rate of a2 reaction and the 2 unaffected. increases between by 2 times by = 4 times concentrations of the reactants raised to the powers of their orders. This can only be determined by experimental results. The rate constant, k, is the constant that links the rate of the reaction with the concentrations of the reactants. The overall order of a reaction is the sum of the individual orders. For Example the overall order of Rate [A]1[B]2, would be 1 + 2 = 3 Units of K: First order = k = rate = rate [A] [A]2[B] = s-1
1

The effect of temperature on k Increasing the temperature of a reaction gives more energy to the molecules, meaning more successful collisions. Hence the rate increases with temperature. If the concentrations of reactants remain the same but temperature increases then the rate constant, k , must increase as for example, Rate = k [A][B].

[A]2 = dm3mol-1s-1 = dm6mol-2s-