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rate is always
expressed as a
positive value
Reaction rate is measured in terms of the changes in concentrations
of reactants or products per unit time.
0.0 3.20x10-5
10.0 2.42x10-5
[C2H4]
20.0 1.95x10-5 rate = -
t
30.0 1.63x10-5 [O3]
=-
40.0 1.40x10-5 t
50.0 1.23x10-5
60.0 1.10x10-5
C2H4 + O3 → C2H4O + O2
[O2] increases just as fast as [C2H4]
decreases.
D[C2H4] D[O3]
Rate = - =-
Dt Dt
[C2H4O] [O2]
= =
t t
The average rate of the reaction is the change in concentration
of the reactant or product in a unit interval of time (the
specified interval Δt, being finite and measurable)
𝜟𝑨 𝒅𝑨
- = - = Instantantaneous rate
𝜟𝒕 𝒅𝒕
∆𝑡 → 0
The reaction slows down with time because the concentration of the
reactants decreases.
𝜟[𝑨] 𝒅[𝑨]
- = = Instantantaneous rate = slope
𝜟𝒕 𝒅𝒕
∆𝒕 → 𝟎
Instantantaneous rate =
(Average rate) ∆𝑡 → 0
Reaction Rates and Stoichiometry
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
-[C4H9Cl] [C4H9OH]
Rate = =
t t
What if the ratio is not 1:1?
H2(g) + I2(g) 2HI(g)
The mathematical expression for the rate, and the numerical value
of the rate, depend on which substance is chosen as the reference.
aA + bB cC + dD
𝒅[𝑨] 𝒅𝑩 𝒅[𝑪] 𝒅[𝑫]
Rate = - = - = + =+
𝒂𝒙𝒅𝒕 𝒃𝒙𝒅𝒕 𝒄𝒙𝒅𝒕 𝒅𝒙𝒅𝒕
The derived rate law for a reaction must be consistent with the
postulated chemical mechanism of the reaction!
The Procedure
2. Use initial rates from several experiments to find the reaction orders
If the rate does not change when [A] doubles, the rate does
not depend on [A], and the reaction is zero order with respect
to A.
Reaction Order Terminology
rate = k[O2]m[NO]n
initial reactant
concentrations (mol/L) initial rate
experiment O2 NO (mol/L.s)
1 1.10 x 10-2 1.30 x 10-2 3.21 x 10-3
rate 2 k[O2]2m[NO]2n
= ([NO] is held constant)
rate 1 k[O2]1m[NO]1n
rate 2 [O2]2m
= = ([O2]2 / [O2]1)m
rate 1 [O2]1m
1.99 = (2.00)m
m=1
Thus, the reaction is first order with respect to O2. When [O2]
doubles, the rate doubles.
rate 3 k[O2]3m[NO]3n
= ([O2] is held constant)
rate 1 k[O2]1m[NO]1n
n=2
But,
rate = k [(CH3)3CBr]
Differential form:
straight-line form
1 1
Rearrange, integrate: = kt +
A A 0
straight-line form,
1 1
= kt +
A A 0
The half-life (t1/2) for a reaction is the time taken for the
concentration of a reactant to drop to half its initial value.
NOTE: For a first-order process, the half-life does not depend on [A]0
A first order reaction is 35% complete at the
end of 55 minutes. What is the value of k?
2O3(g) 3O2(g)
O3(g) O2(g) + O(g) unimolecular
O3(g) + O(g) 2O2(g) bimolecular
The rate law for an elementary reaction can be deduced from the
reaction stoichiometry; reaction order equals molecularity for an
elementary step only
Give resonable explanations:
2O3(g) 3O2(g)
Mechanism
Slow A + B C
C + A D possible steps
D E + F
PROBLEM: The following two reactions are proposed as elementary steps in the
mechanism of an overall reaction:
PLAN:
We find the overall equation from the sum of the elementary steps. The
molecularity of each step equals the total number of reactant particles. We
write the rate law for each step using the molecularities as reaction orders.
SOLUTION:
An example:
The reaction NO2(g) + CO(g) → NO(g) + CO2(g)
has been proposed to occur by a two-step mechanism:
The rate law for the rate-determining step becomes the rate law for the
overall reaction.
Correlating the Mechanism with the Rate Law
rate2 = k2[NO2][F]
f = e-Ea/RT
From this equation, we can see that both Ea and T affect f, which
in turn influences reaction rate.
Effective Collisions
Not all collisions that occur with energy equal to, or exceeding, the
activation energy lead to products.
k = A e –Ea /RT
A = frequency factor
Ea = activation energy
R = gas constant (8.3145 J/K·mol)
T = temperature (in K)
K = rate constant of the reaction
Linear Form of Arrhenius Equation:
y = mx + b
k2 Ea 1 1
ln = - -
k1 R T2 T1
Catalysis: Enhancing Reaction Rates
Catalyst: A substance that speeds up a reaction without being
consumed itself.
Catalysts provide New faster paths by which reaction can proceed.
This can be done in a variety of ways:
Ce +4 + Mn ++ → Ce +3 + Mn +3
Ce +4 + Mn +3 → Ce +3 + Mn +4
Mn +4 + Tl + → Tl +3 + Mn ++
Uncatalyzed reaction:
A + B product
Catalyzed reaction:
A + catalyst C
C + B product + catalyst
A catalyst does not affect either ΔH The catalyzed and uncatalyzed reactions
or the overall yield for a reaction. occur via different pathways.
Types of Catalysts
Heterogeneous Catalyst
1. Most often involves gaseous reactants being adsorbed on
the surface of a solid catalyst.
2. Adsorption and activation of the reactants.
3. Migration of the adsorbed reactants on the surface.
4. Reaction of the adsorbed substances.
5. Escape, or desorption, of the products.
One of the outstanding example of the heterogeneous catalysis is the
hydrogenation of unsaturated organic compounds.
H2 + C2H4 → C2H6
The reaction is slow at moderate temperature in the gas phase. The same
reaction is fast if carried out at the surface of the metal because these metal can
absorb large quantities of hydrogen , apparently by incorporating it in the
metallic lattice as hydrogen atoms. The process is represented by:
𝟏
H2 + M → M . H
𝟐
Where M . H represents the pool of atomic hydrogen in the metallic lattice. Thus
hydrogenation takes place as:
at surface
2 M . H + C2H4 C2H6
𝒅[𝑰]
i.e. =0
𝒅𝒕
𝒅[𝑶𝟐]
The experimental rate law is: = k[N2O5]
𝒅𝒕
The mechanism is:
K1
Step 1: N2O5 k-1
NO2 + NO3
k2
Step 2: NO2 + NO3 NO + O2 + NO2
k3
Step 3: NO3 + NO 2NO2
NO3 and NO are the intermediates . let us find their steady state
concentrations by using SSA.
For NO3,
This is as the same form as the experimental rate law. The relation
between the experimental rate constant K and rate constants for the
individual elementary steps is:
𝑲𝟏
K =
𝑲 𝟏
+ 𝟐 𝑲𝟐
−
Enzyme Catalysis
Active site
or
Not a substrate
substrate binding site
(not always exactly synonymous,
latter could be just a part of the active site)
Michaelis-Menten equation
In1913, Michaelis- Menten proposed a mathematical model of the
reaction. It involves an enzyme, E, binding to a substrate, S, to form
a complex, ES, which in turn releases a product, P, regenerating the
original enzyme. This may be represented schematically as
K1 [E][S] = (k -1 + k2)[ES]………………..(2)
This equation might be solved for [ES], but it also contains ,which is
unknown. We can write the enzyme conservation equation.
[E0] = [E] + [ES]…………………….(3)
𝒌−𝟏+𝒌𝟐
km = 𝒌𝟏
The lower the Km, the more poorly it dissociates. That is, the more
TIGHTLY it is held by the enzyme
And the greater the Km, the more readily the substrate dissociates,
so the enzyme is binding it poorly
From equation (5), by taking the reciprocal of both sides, we have
the another common form of the Michaelis-Menten rate law:
𝟏 𝟏 𝒌𝒎
= + ………………(6)
𝑽 𝒌𝟐[ 𝑬𝟎] 𝒌𝟐[ 𝑬𝟎] [𝑺]
Condition 1
At sufficiently low substrate concentration: [S] ˂˂ Km
Condition 2
V = k2 [E0]
This rate law equation shows that the rate is zero order
with respect to substrate concentration.
Question
???????
Give the physical reason behind reaction rate which
changes from first to zero order with respect to substrate
concentration as the substrate concentration is increased.
Understanding Km
Consider the
Vo that is equal
to 50% of Vmax