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Reaction Rates and Temperature Arrhenius Theory: CHEM 102 T. Hughbanks

The document discusses Arrhenius theory and the Arrhenius equation. It explains that: 1) The Arrhenius equation describes how reaction rate constants (k) depend on temperature, activation energy (Ea), and other factors. 2) Raising the temperature increases the reaction rate because more molecules will possess energies greater than the activation energy barrier. 3) The Arrhenius equation can be used to calculate how much a reaction rate will accelerate when temperature is increased, as demonstrated with an example.

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63 views12 pages

Reaction Rates and Temperature Arrhenius Theory: CHEM 102 T. Hughbanks

The document discusses Arrhenius theory and the Arrhenius equation. It explains that: 1) The Arrhenius equation describes how reaction rate constants (k) depend on temperature, activation energy (Ea), and other factors. 2) Raising the temperature increases the reaction rate because more molecules will possess energies greater than the activation energy barrier. 3) The Arrhenius equation can be used to calculate how much a reaction rate will accelerate when temperature is increased, as demonstrated with an example.

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IAS India
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© © All Rights Reserved
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Reaction Rates and Temperature;

Arrhenius Theory

CHEM 102

T. Hughbanks

Arrhenius Theory

−Ea
k = Ae RT

k is the rate constant! T is the temperature in K!

Ea is the activation energy! R is the ideal-gas constant


(8.314 J/K!mol)!

In addition to carrying the units of the rate constant, “A”


relates to the frequency of collisions and the orientation of a
favorable collision probability!

Both A and Ea are specific to a given reaction.!

In order for the reaction


to proceed, the reactants
Potential Energy!

must posses enough


energy to surmount a
Eact! reaction barrier. !

∆HRXN!

Reaction Progress!
Energy profile for a reaction

“activated complex”

Rate-determining

Ea

Energy

Quantity

reactants

∆Erxn

products

Thermodynamic Quantity

“Reaction Coordinate”

The reverse direction...



“activated complex”

Rate-determining

for reverse reaction

Energy

“products”

Ea(reverse)

∆Erxn

“reactants”

Thermodynamic Quantity

“Reaction Coordinate”

Ea, The Activation Energy

  Energy of activation for forward reaction:

Ea = Etransition state - Ereactants

  Areaction can’t proceed unless reactants
possess enough energy to give Ea.

  ∆E, the thermodynamic quantity, tells us
about the net reaction. The activation energy,
Ea , must be available in the surroundings for
the reaction to proceed at a measurable rate.

The temperature for a


system of particles is
described by a
distribution of energies.

At higher temps, more


particles have enough
energy to go over the
barrier.
E > Ea!
Since the probability of a
E < Ea! molecule reacting
increases, the rate
increases.
The orientation of a molecule during collision can have a
profound effect on whether or not a reaction occurs. !

The reaction
occurs only when
the orientation of
the molecules is
just right…!

In some cases, the reactants must have proper


orientation for the collision to yield products. !

This reduces the


number of collisions
that are reactive!!
Arhenius discovered that most reaction-rate data
obeyed an equation based on three factors:!
(1) The number of collisions per unit time.!
(2) The fraction of collisions that occur with the
correct orientation.!
(3) The fraction of the colliding molecules that
have an energy greater than or equal to Ea.!

Temperature Dependence of the Rate Constant:!


Increasing the temperature of a reaction generally speeds
up the process (increases the rate) because the rate
constant increases according to the Arrhenius Equation.!

Rate (M s-1) = k [A]x[B]y!

−Ea
k = Ae RT

As T increases, the value of the exponential part of the


equation becomes less negative thus increasing the value of k.!
Temp. and Rate Acceleration

Arrhenius Equation

  Arrheniusnoted that reaction rates could be


understood to depend on Ea and T with the
exponential form:

k = A exp(– Ea/RT)

  Or, in logarithmic form:

lnk = lnA – (Ea/RT)

using base 10 logs: [logk = logA - (Ea/2.303RT)]

Arrhenius Eqn., Alternative Form

  Taking two measured values of the rate (at


two different temperatures) one can write:

lnk 1 = lnA – (Ea /RT1)

lnk 2 = lnA – (Ea /RT2)

lnk 2 – lnk 1 = – (Ea /R)[(1/T2) – (1/T1)]

ln(k 2/k 1) = – (Ea/R)[(1/T2) – (1/T1)]

Arrhenius Eqn., Graphical Form



A “best fit” to many data is better!

lnk = -(Ea/R)(1/T) + lnA



Arrhenius Equation, Example

  Ifa reaction has an activation energy of 50 kJ/


mol, then how much should the rate of the
reaction accelerate if the temperature is raised
from 300 K to 310 K?

Arrhenius Equation, Example



  Ifa reaction has an activation energy of 50 kJ/
mol, then how much should the rate of the
reaction accelerate if the temperature is raised
from 300 K to 310 K?

ln(k 310/k 300) = - (Ea/R)[(1/T2) - (1/T1)]

- (50,000 J/mol)/(8.314 J/mol K)•

[(1/310K) – (1/300K)] = 0.647

k 310 = e0.647k 300
roughly, rate doubles


=1.9k 300
for every 10 ˚C.

Catalysts - lowering Ea. Mechanism may change.

Ea(uncatalyzed)

Energy

reactants
Ea(catalyzed)

∆Erxn

products

“Reaction Coordinate”

Pt

Catalytic Converters, 2NO → O2+N2

Pt

surface

MnO2

2H2O2 → 2H2O + O2

Iodine-Catalyzed Isomerization of cis-2-Butene



Iodine-Catalyzed Isomerization of
cis-2-Butene

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