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ME301 Lec 6 PDF
ME301 Lec 6 PDF
Temperature
Pressure
Concentrations of the reactants
N N
A general reaction can be written as:
i i i Mi
v '
i =1
M v ''
i =1
i i Mi
v M
i =1
v'
i
''
i =1
V1 = 3 V2 = 7 V3 = 4 V4 = 0 V5 = o V6 = 0
V1 = o V2 = 1 V3 = 4 V4 = 1 V5 = 2 V6 = 6
Elementary Reaction
A reaction seldom happens as the last example
Rather, it happens through collision of molecules and destruction of
existing bonds followed by creation of new bonds
A overall (global) reaction consists of several of such reactions
which are called Elementary Reactions.
Intuitively, the elementary reactions are mostly unimolecular
(where one molecule dissociate to form more-than-one species) or
bimolecular (where two molecules collide to form some other species)
aA + bB cC + dD
1 dC A 1 dC B 1 dCC 1 dC D
RR = = = =
a dt b dt c dt d dt
RR C H CO
For the general reaction aA + bB cC + dD ,
RR C Aa C Bb
Law of Mass Action
RR C C a
A
b
B
This is known as the Law of Mass Action and it states that
In general form,
RR Mi
C vi
M i Re ac tan ts
OR RR = k Mi
C vi
M i Re ac tan ts
For a global reaction, the rate of reaction have to found out on the basis of
the rate of reactions of the elementary reactions.
For a global reaction, the rate of reaction have to found out on the basis of
the rate of reactions of the elementary reactions.
Collision theory
Collision Theory
A chemical reaction occurs only when
RR = Z AB S exp( E / RT )
Probability of having an
Collision Steric (orientation) energy E @ temperature T
Frequency Factor
Collision Theory
By obtaining expressions for the collision frequency and steric factor form
the kinetic theory of gases, one can obtain RR in the following form.
RR = BT 0.5C Aa C Bb exp( E / RT )
A Constant
Comparing with the law of mass action RR = kC Aa C Bb , we get
A From experimental
observations, both A and E
slope = E / R can be found out from this
ln k plot.
1/ T
Rate coefficient
A From experimental
observations, both A and E
slope = E / R can be found out from this
ln k plot.
1/ T Note:
In nature, there are many quantities which
follow this kind of exponential rule In
general, this is called Arrhenius rule.
Rate coefficient
We know that the pre-exponential factor (A) is a weak function of temperature
High temperature
ln k Low temperature
1/ T