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Rate Equation

# Rate Equation

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08/03/2012

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Rate equation
The
rate law
or
rate equation
for achemical reactionis an equation that links the reaction rate with concentrations or pressures of reactants and constant parameters (normally rate coefficients andpartial reaction orders).
To determine the rate equation for a particular system one combines thereaction rate with amass balance for the system.
For a generic reaction
a
A +
b
B → C with nointermediate steps in its reaction mechanism (that is, anelementary reaction), the rate is given by where [A] and [B] express the concentration of the species A and B, respectively (usually in molesper liter (molarity, M));
x
and
are not the respective stoichiometric coefficients of the balancedequation; they must be determined experimentally.
is the
rate coefficient
or
rate constant
of thereaction. The value of this coefficient
depends on conditions such as temperature, ionicstrength, surface area of theadsorbentor light irradiation. For elementary reactions, the rateequation can be derived from first principles usingcollision theory. Again, x and y are NOT alwaysderived from the balanced equation.The rate equation of a reaction with a multi-step mechanism cannot, in general, be deduced fromthe stoichiometric coefficients of the overall reaction; it must be determined experimentally. Theequation may involve fractional exponential coefficients, or it may depend on the concentration of an intermediate species.The rate equation is adifferential equation, and it can beintegrated to obtain an
integrated rateequation
that links concentrations of reactants or products with time.If the concentration of one of the reactants remains constant (because it is a catalyst or it is in great excess with respect to the other reactants), its concentration can be grouped with the rateconstant, obtaining a
pseudo constant
: If B is the reactant whose concentration is constant,then
=
[
A
][
B
] =
'[
A
]
. The second-order rate equation has been reduced to a
pseudo-first-order
rate equation. This makes the treatment to obtain an integrated rate equation much easier.
Zeroth-order reactions
A
Zeroth-order reaction
has a rate that is independent of the concentration of the reactant(s).Increasing the concentration of the reacting species will not speed up the rate of the reaction.Zeroth-order reactions are typically found when a material that is required for the reaction toproceed, such as a surface or acatalyst,is saturated by the reactants. The rate law for a zeroth- order reaction is

where r is the reaction rate and k is the reaction rate coefficient with units of concentration/time. If, and only if, this zeroth-order reaction 1) occurs in a closed system, 2)there is no net build-up of intermediates, and 3) there are no other reactions occurring, it canbe shown by solving a mass balanceequation for the system that: If this differential equationisintegrated it gives an equation often called the
integratedzero-order rate law
.where represents the concentration of the chemical of interest at a particular time, and represents the initial concentration. A reaction is zeroth order if concentration data are plotted versus time and the result isa straight line. The slope of this resulting line is the negative of the zero order rateconstant k.The half-life of a reaction describes the time needed for half of the reactant to bedepleted (same as the half-lifeinvolved innuclear decay, which is a first-order  reaction). For a zero-order reaction the half-life is given by
Example of a zeroth-order reaction
ReversedHaber process:  It should be noted that the order of a reaction cannot be deduced from thechemical equation of the reaction.
edit

]
First-order reactions
A
first-order reaction
depends on the concentration of only one reactant(a
unimolecular reaction
). Other reactants can be present, but each will bezero-order. The rate law for an elementary reaction that is first order withrespect to a reactant A is
is the first order rate constant, which has units of 1/s.The
integrated first-order rate law
is A plot of
ln [
A
]
vs. time
gives a straight line with a slope of
.

The half-life of a first-order reaction is independent of the startingconcentration and is given by .Examples of reactions that are first-order with respect to thereactant:
Further Properties of First-Order Reaction Kinetics
The integrated first-order rate lawis usually written in the form of the exponential decay equation A different (but equivalent) way of considering first order kinetics is as follows: Theexponential decay equation can be rewritten as:where
Δ
p
corresponds to a specific time period and
n
is an integer corresponding tothe number of time periods. At the end of each time period, the fraction of the reactantpopulation remaining relative to the amount present at the start of the time period,
f
RP
,will be:Such that after
n
time periods, the fraction of the original reactant population willbe:where:
f
BP
corresponds to the fraction of the reactant population that willbreak down in each time period. This equation indicates that the fraction of the total amount of reactant population that will break down in each timeperiod is independent of the initial amount present. When the chosen timeperiod corresponds to , the fraction of the population thatwill break down in each time period will be exactly ½ the amount present at