3 Kinetika Reaksi 2018 (Part 1)
3 Kinetika Reaksi 2018 (Part 1)
3 Kinetika Reaksi 2018 (Part 1)
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An irreversible reaction is one that proceeds in
only one direction and continues in that direction
until the reactants are exhausted.
A reversible reaction is the one that can
proceed in either direction, depending on the
concentrations of reactants and products relative
to the corresponding equilibrium concentrations.
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−r A =k C αA C βB
Problem 3.1.
What is the reaction rate law for the reaction
if the reaction follows an
elementary rate law? What is rB? What is rC?
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Calculate the rates of A, B, and C in a CSTR
where the concentrations are CA = 1.5 mol/L, CB
= 9 mol/L and kA = 2 (L/mol)(1/2)(1/s).
Reversible Reactions
The net rate of formation of any species is equal
to its rate of formation in the forward reaction
plus its rate of formation in the reverse reaction:
ratenet = rateforward + ratereverse
At equilibrium, ratenet 0 and the rate law must
reduce to an equation that is thermodynamically
consistent with the equilibrium constant for the
reaction.
Example: Consider the exothermic,
heterogeneous reaction
At low temperature, the rate law for the
disappearance of A is
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reaction (A + B C) is
then we need to assume a form of the rate law
for the reverse reaction that satisfies the
equilibrium condition. If we assume the rate law
for the reverse reaction (C A + B) is
then:
and:
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From Appendix C we know that for a reaction at
equilibrium:
At equilibrium, rnet 0, so:
Problem 3.2.
Write the rate law for the elementary reaction
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In summary on reaction orders, they cannot be
deduced from reaction stoichiometry. They must
be determined from experiments.
Rate Constant, k
k is the specific reaction rate (constant) and is
given by the Arrhenius Equation:
k = A e−E / RT
Where:
E = activation energy (cal/mol)
R = gas constant (cal/mol∙K)
T = temperature (K)
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A = frequency factor (units of A, and k, depend
on overall reaction order)
( Concentration )1−n
[ k ]=
Time
E 1
ln k =ln A−
R T( )
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The larger the activation energy, the more
temperature sensitive k and thus the reaction
rate.
E 1 1
k T =k T exp
2 1
[( −
R T1 T2 )]
The activation energy can be thought of as a
barrier to the reaction. One way to view the
barrier to a reaction is through the reaction
coordinates. These coordinates denote the
energy of the system as a function of progress
along the reaction path. For the reaction
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Progress along reaction path
We see that for the reaction to occur, the
reactants must overcome an energy barrier or
activation energy EA.
Thus, the activation energy is a measure of the
minimum energy that the reacting molecules
must have in order for the reaction to occur.
Why is there an Activation Energy?
(1) the molecules need energy to distort or
stretch their bonds in order to break them and to
thus form new bonds
(2) as the reacting molecules come close
together they must overcome both steric and
electron repulsion forces in order to react
All the molecules don’t have the same energy,
rather there is distribution of energies where
some molecules have more energy than others.
f ( E , T ) describes this distribution of the energies of
the molecules.
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fraction of molecules with energies
f ( E , T ) dE=¿
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