1.9.2

Orders, Rate Constants & Equations

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Rate Equations

You can calculate rates of reactions by finding their rate equations. These link the concentration of each reactant to the rate of the equation.

Physical basis

Physical basis

  • Reactions happen when molecules collide into one another.
    • In a reaction between molecule A and B, the rate will be proportional to the number of collisions between A and B.
  • If you double the concentration of B, you should have double the collisions between A and B.
    • So, you would expect the reaction rate to double.
  • In reality, this is an over-simplification because you have multiple steps in most reactions, which may or may not involve each molecule.
The rate equation

The rate equation

  • A rate equation is always written of the form:
    • Rate = k × [A]m[B]n
  • k is called the rate constant.
  • The numbers m and n tell you how the rate depends on the reactants.
    • They are called the order of the reaction with respect to each reactant.
The order of reaction

The order of reaction

  • Just as we define an order for the reactants, we define an overall order for the reaction.
  • The overall order is given by m + n.
    • You very rarely get any value above 2 for an order with respect to a reactant, or less than zero.
The rate constant

The rate constant

  • The rate constant k has a few key features:
    • It’s temperature dependent.
    • It has different units for different reactions.
  • The units of the reaction rate have to be concentration over time.
  • But the units of the product of the reactants are never that, so you need to assign units to k to sort it out.
    • The larger the rate constant, the faster the reaction.

Calculations of Rate Equations

You need to be able to do a whole bunch of calculations with rate equations.

Calculating the rate of reactions

Calculating the rate of reactions

  • The rate of a reaction can be calculated if you know its rate constant, the reactant concentrations, and the order of the reaction with respect to each reactant.
  • E.g. if a reaction obeys the equation:
    • Rate = k[A][B], where the rate constant is 0.5dm3mol-1t-1, and the reactant concentrations are both 2moldm-3
    • The rate is 2moldm-3 × 2moldm-3 × 0.5dm3mol-1t-1 = 2moldm-3t-1
Calculating the rate constant

Calculating the rate constant

  • You can be given a rate equation and told to calculate the rate constant given some concentration data.
    • E.g. the rate equation for the production of I-Cl is: Rate = k[I2]1[Cl2]1
  • Given that the concentrations of I2 and Cl2 are 1moldm-3, and the rate of reaction is 40moldm-3t-1, what is the value of k?
    • k = 40moldm-3t-1 ÷ (1moldm-3)2 = 40mol-1dm3t-1
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1.3

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1.6

Electrochemistry

1.7

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1.8

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1.9

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2

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3.4

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3.5

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3.6

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3.7

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3.10

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