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7 views11 pages

Temp - On .RX

Uploaded by

Dr/mahmoud Ahmed abdeen
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPTX, PDF, TXT or read online on Scribd
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13.

5 The Effect of Temperature on


Reaction Rate
How Temperature Effects Reaction Rate
• The rate of a chemical reaction, in general, are highly sensitive to
temperature.

• The temperature dependence of the reaction rate is contained in the


reaction constant, K (which is a constant when temperature is constant).

• An increase in temperature = an increase in K.  generally.

• Arrhenius equation: shows the relationship between the rate constant


(k) and the temperature in kelvin (T).

k=A where R is the gas constant: 8.31 J / mol K


A is a constant called the frequency factor (or pre-
exponential factor, and E is the activation energy.
Explanation of the Activation Energy Part of
The Arrhenius Equation
• Activation energy (Ea): The energy barrier, or
hump, that must be overcome for the reactants to
be transformed into products.

• The diagram to the right


is a PE diagram, which
represents the change
in potential energy
throughout the course
PE Diagram Explained
• In the diagram below, the hill that forms as you proceed
from left to right is known as the activation energy of the
forward reaction. At the top of the hill, the reactant
particles
go through a high energy
intermediate state known
as the activated complex
(or transition state). The
higher the Ea, the slower
the reaction rate (at a given
Frequency Factor and Exponential Factor
• Frequency factor (A): the number of times that the reactants
approach the activation barrier per unit time.

• There are many instances when the particles collide and the
reactant(s) approach the activation barrier, but most approaches are
unsuccessful in overcoming the amount of energy necessary for the
reaction to occur.

• The exponential factor: a number between 0 and 1 that represents


the fraction of particles that have enough energy to overcome the
activation energy on a given approach. The exponential factor
depends on both temperature and the activation energy of the
reaction.
Let’s Try a Practice Problem!
Reaction A and reaction B have identical frequency
factors. However, reaction B has a higher activation
energy than reaction A. Which reaction has a greater
rate constant at room temperature?

Reaction A has a higher rate constant, since it has a


lower activation energy; therefore the exponential
factor is larger at any given temperature, making the
rate constant larger. (With a larger rate constant and
the same initial concentration, the rate will be faster).
The Collision Model: A Closer Look at
Frequency Factor
• In a collision model, a chemical reaction occurs after a
sufficient energetic collision between two reactant particles.

• In collision theory, each collision = an approach to the


activation barrier of the reaction. So, the number of
collisions of reacting particles should be the frequency
factor, however it’s not that simple.

• In most, if not all gas phase reactions, two factors have to be


considered: 1.) collision frequency, and 2.) orientation
factor.
The Collision Model: A Closer Look at
Frequency Factor (continued)
• The collision frequency: the number of collisions per unit time.
(remember, both temperature and pressure affect the number of collisions
made possible in the gas phase).

• The orientation factor: a number usually between 0 and 1 that represents


the number of collision with proper orientation that allows the reaction to
occur.
– A small orientation factor (one that approaches 0) means that the orientation
requirements for this for the reaction are very stringent, that is, the molecule has
to be aligned in a very specific way for the reaction to occur.

• There are also reaction where particles don’t even need to collide for a
reaction to occur: example K(g) + Br2(g)  KBr(g) + Br(g). The transfer of
electrons here can occur without a collision. This is known as a harpoon
Let’s Try Another Practice Problem!
Which reaction would you expect to have the smallest
orientation factor?

(a) H(g) + I(g)  HI(g)


(b) H2(g) + I2(g)  2HI (g)
(c) HCl(g) + HCl(g)  H2(g) + Cl2(g)

(c) HCl(g) + HCl(g)  H2(g) + Cl2(g), since here the reactants are
assymetrical and must therefore collide in such a way that a
hydrogen atom is in close proximity to another hydrogen atom.
Therefore, we expect (c) to have the smallest orientation factor.
13.5 pgs. 641-642 #’s 57,58, 71 and 72
Read 13.6-13.7 pgs. 622-632

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