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Rate Constants and the Orders

Usually, the rate of a reaction is a function of the concentrations of reactants. For example, the rate of the reaction : 2 NO + O2 ! 2 NO2 has the form: rate = k [O2] [NO]2

The rate is proportional to the concentration of O2, usually written as [O2] and is proportional to the square of [NO], or [NO]2. The orders of 1 and 2 for [O2] and [NO] respectively has been determined by experiment, NOT from the chemical equation. The total order of this reaction is 3 (2+1). Note the rates and order in the following example reactions: H2 + I2 ! 2 HI H2 + Br2 = 2 HBr rate = k [H2] [I2] rate = k [H2] [Br2]1/2 (total order 2) (total order 1.5 or 1!)

In particular, note that orders are NOT determined from the stoichiometry of the reaction equation, but rather by experiment. Many reactions with a single mechanism often have a rate determined by their coefficients. If only [A] is varied in experiments, and the order [A] is n, then the rate has the general expression, rate = k [A]n In this expression, k is the specific rate constant, or the rate when [A] = 1.00. Again, the order n is not necessarily an integer, but its most common values are 0.5 (!), 1, 2, or 3. Cases in which n is a negative number are rare. Rate : This is often expressed mol/L•s or but may be k : The constant can be given or calculated mathematically with the units where n represents the order.

expressed in other units.

Concentration : [A] often means mol/ L but the concentrations may be expressed in other units. For a chemical reaction, we often determine the order with respect to a reagent by determine the initial rate. When more than one reactant is invovled, we vary the concentrations in a systematic way so that the effect of concentration of one of the reactants can be measured. Derive the rate law for the reaction A + B + C ! products from the following data, where rate is measured as soon as the reactants are mixed. Experiment 1 2 3 4 Solution: [A]o 0.100 0.200 0.200 0.100 [B]o 0.100 0.100 0.300 0.100 [C]o 0.100 0.100 0.100 0.400 rate 0.100 0.800 7.200 0.400

Assume the orders to be x, y, and z respectively for A, B, and C, we have rate = k [A]x [B]y [C]z From experiment 1 and 2, we have: k 0.1x 0.1y 0.1z 0.100 ------------------------- = -------k 0.2x 0.1y 0.1z 0.800 We choose 2 experiments where one concentration changes ([A] x2) and the others remain constant. The reaction rate is affected accordingly…

Therefore the reaction rate increases 8x if only the concentration of A increases 2x. 8 = 2x or x = (ln8 / ln2) = 3 or we see the exponent must be 3!?

By similar procedures, we get y = 2 and z = 1. Thus, the rate law is: rate = k [A]3 [B]2 [C]