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    Chemical KineticsOrdersII

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    Anthony Mafuta Mayilamene
    The document discusses chemical reaction rates and rate laws. It defines zero, first, and second order reactions based on how the reaction rate depends on reactant concentrations. A reaction is zero order if the rate is constant regardless of reactant concentrations. It is first order if the rate depends on the concentration of one reactant raised to the first power. It is second order if the rate depends on the concentration of one reactant raised to the second power, or the product of two first-order reactions. The document provides examples of determining reaction orders and rate constants from experimental data.

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    Chemical KineticsOrdersII

    Uploaded by

    Anthony Mafuta Mayilamene
    14 views17 pages
    The document discusses chemical reaction rates and rate laws. It defines zero, first, and second order reactions based on how the reaction rate depends on reactant concentrations. A reaction is zero order if the rate is constant regardless of reactant concentrations. It is first order if the rate depends on the concentration of one reactant raised to the first power. It is second order if the rate depends on the concentration of one reactant raised to the second power, or the product of two first-order reactions. The document provides examples of determining reaction orders and rate constants from experimental data.

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    2. Chemical KineticsOrdersII

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    The document discusses chemical reaction rates and rate laws. It defines zero, first, and second order reactions based on how the reaction rate depends on reactant concentrations. A reaction is zero order if the rate is constant regardless of reactant concentrations. It is first order if the rate depends on the concentration of one reactant raised to the first power. It is second order if the rate depends on the concentration of one reactant raised to the second power, or the product of two first-order reactions. The document provides examples of determining reaction orders and rate constants from experimental data.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    14 views17 pages

    Chemical KineticsOrdersII

    Uploaded by

    Anthony Mafuta Mayilamene
    The document discusses chemical reaction rates and rate laws. It defines zero, first, and second order reactions based on how the reaction rate depends on reactant concentrations. A reaction is zero order if the rate is constant regardless of reactant concentrations. It is first order if the rate depends on the concentration of one reactant raised to the first power. It is second order if the rate depends on the concentration of one reactant raised to the second power, or the product of two first-order reactions. The document provides examples of determining reaction orders and rate constants from experimental data.

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    © All Rights Reserved
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    of 17

    THE RATE LAW

    Orders of Chemical Reactions


    The Rate Law
     This states that the rate of a chemical reaction is directly
    proportional to the concentration of the reactants.
     For a reaction represented by the equation:
     2A + B → 2C,
     The rate law may be
     Rate = k[A]x [B]y

     K is the rate constant. It is constant at a particular temperature.


    The larger the value of K the faster the reaction.
     x is the order of the reaction with respect to reactant A
     y is the order of the reaction with respect to reactant B.The sum
    of the orders (x+y) gives the overall order of the reaction.

    Main Menu
    Order of Reaction
     The order of the reaction with respect to a particular reactant is
    the power to which the concentration term of that reactant must
    be raised in the experimentally determined rate equation.The
    order of a reaction cannot be deduced from balanced equation
    for the reaction.

     First order reaction:


     The rate of a first order reaction is directly proportional to the
    concentration of one reactant.
     A →Products
     Rate  [A]
     Rate = k[A]
     When the concentration of the reactant is doubled, the rate is
    also doubled.

    Main Menu
    Example of a first order reaction
     The decomposition of hydrogen peroxide is an example of a first
    order reaction.

    Main Menu
    Second order reaction:
     The rate of a second order reaction is directly proportional to the
    square of the concentration of one reactant, or the product of the
    concentration of two reactants each of which is first order.
     For a second order reaction involving one reactant,
     A → Products
     Rate = k[A]2
     Doubling the concentration quadruples the rate.
     A graph of rate against the square of the concentration gives a straight
    line.

    Main Menu
    Second order involving two reactants
     For a second order reaction involving two reactants each of which
    is first order, the rate is given by

     Rate=k[A][B]

     In this case doubling the concentration of one reactant doubles


    the rate but doubling the concentration of the two reactants
    quadruples the rate.

    Main Menu
    Pseudo-First order reaction

     This is a reaction that depends on the concentration of two


    reactants but the concentration of one is so much is excess that
    the rate of the reaction only depends on the concentration of the
    limiting reagent.
     For example, in the hydrolysis of esters (e.g. ethyl ethanoate), the
    water is so much is excess that the rate of the reaction only
    depends on the concentration of the ester.

     CH3COOCH2CH3 + H2O = CH3COOH + CH3CH2OH

    Main Menu
    Zero order reaction
     Zero order reaction:This a reaction in which the rate of the
    reaction is constant no matter the initial concentration of the
    reactants.That is it does not depend on the concentration of any
    reactant. Enzyme catalysed reactions are typical examples of zero
    order reactions.
     Rate = k[A]0 in implies that
     Rate = k

    Main Menu
    Determination of the Order and rate
    constant of a Reaction
    This involves three main steps
     1. Experimental measurement of the initial rates
     2. Calculation of the orders of the reaction from the rate data
     3. Deduction of the rate constant from the rate equation or
    from a graph using the rate plotted against concentration.

    Main Menu
    Graphical Method
    a) Measure the concentration of the reactant over a period of time
    b) Plot concentration against time
    c) Draw tangents to curve at various times
    d) Calculate the slopes (gradients) at various times. These represent the
    initial rates.
     Plot the gradients against the corresponding concentrations

    Deductions
     i. If a straight line is obtained passing through the origin the reaction is
    first order and the slope of this curve is the first order rate constant.
     ii. If a straight line is not obtained by plotting the rates against the
    concentration, plot the rates against the square o f the concentration. If
    a straight line is obtained through the origin then the reaction is second
    order and the slope is the second order rate constant.
     iii. If plot of rate against concentration gives a straight line parallel to the
    x-axis then the reaction is zero order.

    Main Menu
    Deductions from initial rates
    experimental data
     a. If the rate is doubled when the concentration of one reactant is
    doubled while the concentrations of others are held constant,
    then the reaction is first order with respect to that reactant.
    Similarly when the concentration of a reactant is tripled, and the
    rate is tripled, then the reaction is first order with resp to that
    reactant.
     b. If the rate is quadrupled when the concentration of a reactant
    is doubled while those other reactants are held constant then
    reaction is first order with respect to that reactant. Similarly
    when the concentration of a react is tripled and the rate increase
    nine-fold, then the reaction is second order with respect to the
    reactant.
     c. If the rate remains the same when the concentration of a
    reactant is doubled while the concentrations of others are held
    constant, then the reaction is zero order with respect to that
    reactant.

    Main Menu
    Example
     The following data were obtained for the reaction.
     A + B → 2D
    Expt [A]/moldm-3 [B]/moldm-3 Rate/moldm-3s-1
    1 0.20 0.20 5x10-4
    2 0.40 0.20 10x10-4
    3 0.10 0.10 6.1x10-5
    4 0.10 0.20 2.5x10-4

    a) Write the general rate equation


    b) Deduce the order of the reaction with respect to A and B and
    hence the overall order of the reaction
    c) Write the rate law expression
    d) Calculate the value of the rate constant using experiment 1,
    clearly indicating the units.

    Main Menu
    Example 2
     Consider the following data for the reaction
     2NO(g) + Cl2(g) → 2NOCl(g)
    Expt [NO] [Cl2] Initial Rate/moldm-3s-1
    1 0.01 0.01 2.5x10-3
    2 0.01 0.02 5.0x10-3
    3 0.02 0.02 5.0x10-3

     a) Deduce the orders with respect to NO an Cl2


     (b) Calculate rate constant using experiment 1, clearly indicating
    the units.
     (c) Deduce the rate when the initial concentration of NO is
    0.8moldm-3 while that of Cl2 is 0.60moldm-3

    Main Menu
    Example 3
     The following data were obtained for the reaction
     A + B → Products
    Expt [A]/moldm-3 [B]/moldm-3 Rate/moldm-3s-1
    1 0.1 0.1 1.2
    2 0.1 0.2 4.8
    3 0.2 0.2 9.6

     (a) Deduce the orders of the reaction with respect to A and B


    and hence the overall order.
     (b) Write the rate equation for the reaction
     (c) Calculate the rate constant using experiment 1, clearly
    indicating the units.

    Main Menu
    Example 4
     Consider the data below for the reaction A+ B → Products

    Experiment [A] [B] Rate/moldm3s-1


    1 0.10 0.20 5x10-4
    2 0.20 0.20 1x10-3
    3 0.20 0.40 4x10-3

     Deduce the orders of the reaction with respect to A and B.


     Deduce the overall order of the reaction.
     Calculate the rate constant using experiment 1, clearly indicating
    the units.

    Main Menu
    Example 5
     Consider the data below for the reaction X →Y + Z
    Experiment [X] Rate moldm3s-1

    1 0.15 0.01

    2 0.30 0.04

    3 0.60 0.16

     Deduce the order of the reaction with respect to X


     Write the rate equation for the reaction
     Calculate the value of the rate constant and indicate its units.

    Main Menu
    END

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