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Chemical Kinetics: Reaction

rates and Half-lives (part 2)
INSTR. JEREMIAH G. PEDRAL
Integrated rate Laws for First-Order, Second-Order, 2
and Zero-Order Reactions

 Firstorder reaction: a reaction whose rate depends on the reactant

concentration raised to the first power.
A ——> products
 Second order reaction: A reaction whose rate depends on the concentration of
one reactant raised to the second power or on the concentrations of two different
reactants, each raised to the first power.
 Zero order reaction: a reaction whose rate doesn’t depend on the concentration of
any reactants but relies on the rate constant.
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First order reaction

  
Given the following relationships:
and
We can say that,

Using calculus (see supplementary solutions to be given by the instructor), this expression is integrated
over time to obtain the integrated rate law for a first-order reaction:

 Where, is the concentration of A at t = 0, and is the concentration of A at any time t during an experiment.
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Second order reaction


  For a general second-order reaction, the expression including time is quite complex, so let's consider the
case in which the rate law contains only one reactant.

Integrating over time gives,

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Zero order reaction


  We have:

Integrating over time gives,

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Sample Problem
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Determining the Reaction Order from the Integrated Rate
Law

   integrated rate law can be rearranged into the form of an equation for a straight line, , where is the slope and is
An
the y-axis intercept.
 For a first-order reaction, we have:

a plot of vs. time gives a straight line with slope = and a y intercept
 For a simple second-order reaction, we have:

a plot of vs. time gives a straight line with slope and a y intercept =
 For a zero-order reaction, we have:
+
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Determining the Reaction Order from the Integrated Rate
Law

 Note:
 If you obtain a straight line when you plot In[reactant] vs. time, the reaction is first
order with respect to that reactant.
 If you obtain a straight line when you plot 1/[reactant] vs. time, the reaction is
second order with respect to that reactant.
 If you obtain a straight line when you plot [reactant] vs. time, the reaction is zero
order with respect to that reactant.
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Determining the Reaction Order from the Integrated Rate
Law
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Determining the Reaction Order from the Integrated Rate
Law
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Reaction Half-life

 is the time required for the reactant concentration to reach half its initial value. A half-life is expressed in time units
appropriate for a given reaction and is characteristic of that reaction at a given temperature.
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Half-life of a first order reaction

  From:

we can,
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Half-life of a second-order reaction


  The half-life of a second order reaction does depend on reactant concentration:

 the half-life is inversely proportional to the initial reactant concentration. This

relationship means that a second-order reaction with a high initial reactant
concentration has a shorter half-life, and one with a low initial reactant concentration
has a longer half-life. Therefore, as a second-order reaction proceeds, the half-life
increases.
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Half-life of a zero-order reaction


  the
half-life of a zero-order reaction is directly proportional to the initial reactant
concentration

 if a zero-order reaction begins with a high reactant concentration, it has a longer half-
life than if it begins with a low reactant concentration.
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Summary
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Sample Problem
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Sample Problem
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Sample Problem
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References

Brown, T.L., Lemay Jr., H.E., Bursten, B.E., Murphy, C.J., and Woodward, P.M. (2012) Chemistry: The Central Science,
12th Ed., USA: Pearson Education, Inc.

Brown, L.S. and Holme, T.A. (2011) Chemistry for Engineering Students, 2nd Edition, USA, Brooks/Cole, Cengage
Learning

Chang, R. (2010) Chemistry, 10th Ed., New York, McGraw Hill

Maron, S.H and Lando, J.B. (1974) Fundamentals of Physical Chemistry. Macmillan Publishing Co. Inc. New York, USA

Zumdahl, S.S, Zumdahl, S.A (2012) Chemistry An Atoms First Approach, Brooks/Cole, Cengage Learning