Chapter 4
Chapter 4
Chapter 4
Chemical Kinetics
A → B
𝑪𝟒 𝑯𝟗 𝑪𝒍
Va =
Instantaneous rate (vận tốc tức thời)
Va V
Example:
C4H9Cl(aq) + H2O(l) ↔ C4H9OH(aq) + HCl(aq)
Va= = = =
Instantaneous Rate:
V= = = =
Example: C4H9Cl(aq) + H2O(l) ↔ C4H9OH(aq) + HCl(aq)
-[C4H9Cl] [C4H9OH]
Va = =
t t
Rate Law
For a general reaction:
aA + bB cC + dD
V= = = =
Rate law: Each reaction has its own equation that gives its rate
as a function of reactant concentrations
V = k [A]m [B]n
Where, For a reaction k has a specific value; k is rate constant;
k changes with temperature.
Note: m need not equal a; n need not equal b. Values m and n can
be obtained from experiment
Reaction Order (Bậc phản ứng)
The reaction order can be found by adding the exponents on the
reactants in the rate law
V= k [A]m [B]n
Order of the reaction = m + n
Questions:
a) Determine the order of the reaction and write the rate expression
b) Calculate the rate constant, and determine its units
c) Calculate the reaction rate for a concentration of HI = 0.0020M
Example
Solution
We have, V = k [HI]n
a) V1 = k ([HI]1)n V2 = k ([HI]2)n
V2 /V1 = ([HI]2)n/([HI]1)n 3.0 x 10-3 / 7.5 x 10-4 = (0.010/0.0050)n
4 = 2n
n=2 V = k [HI]2
b) Calculate the rate constant, and determine its units
We have, V1 = k [HI]12
7.5 x 10-4 mol L-1 s-1 = k (0.0050 mol L-1)2
k = 30 L mol-1 s-1
c) Calculate the reaction rate for a concentration of HI = 0.0020M
V = k [HI]2 = 1.2 x 10-4 mol L-1 s-1
Examples
2 NO(g) + O2(g) ↔ 2 NO2(g)
Determine the rate expression and the value of the rate constant
from the data below.
[NO] (mol L-1) [O2](mol L-1) rate (mol L-1 s-1)
1.0 x 10-4 1.0 x 10-4 2.8 x 10-6
1.0 x 10-4 3.0 x 10-4 8.4 x 10-6
2.0 x 10-4 3.0 x 10-4 3.4 x 10-5
Solution
We have, V = k [O2]m [NO]n
To determine the rate law from the data, first determine the
dependence of the rate on each reactant separately.
V2/V1 = k [O2]2m [NO]2n / k [O2]1m [NO]1n
8.4 x 10-6 / 2.8 x 10-6 = (3.0 x 10-4)m/ (1.0 x 10-4)m
3= 3m => m = 1; 1st order in O2
Example
We have, V3/V2 = k [O2]3m [NO]3n / k [O2]2m [NO]2n
3.4 x 10-5 / 8.4 x 10-6 = (2.0 x 10-4)n/ (1.0 x 10-4)n
4= 2n => n = 2; 2nd order in NO
V = k [O2][NO]2 Order of reaction = 3
2.8 x 10-6 mol L-1s-1 = k [1.0 x 10-4 mol L-1] [1.0 x 10-4 mol L-1]2
time
First Order Reactions
For the general reaction: A → Products
We have, V = - d[A]/ dt
On the other hand, the experimental rate law for 1st order reaction is:
V = k [A]
V = - d[A]/ dt = k [A]
d[A]/ dt = - k [A]
ln [A] = - kt
[A]o
[A]o where is the initial concentration of A at time t = 0
Units of k:
Example
ln[A] = ln [A]o - kt
V= k [N2O5]
Half life (bán hủy) of 1st order reaction
Half life : time it takes for the concentration of the reactant A to fall
to half its initial value. t1/2 when [A] = [A]o/2
0.693
t1/2 =
k
Examples
What is the rate constant k for the first order decomposition of
N2O5(g) at 25oC if the half life at this temperature is 4.03 x 104 s?
Under these conditions, what percent of the N2O5 molecules have
not reacted after one day?
N2O5(g) → N2O4(g) + 1/2 O2(g)
Solution
a) For 1st order reaction, t1/2 = 0.6931 / k
k = 1.72 x 10-5 s-1
[N2O5]
b) ln = - kt [N2O5]/[N2O5]o = e-kt
[N2O5 ]o
[N2O5]/[N2O5]o = 0.226
22.6% N2O5 molecules have not reacted after one day
Second order reactions
A+B Products
Or 2A Products
Rate Law, V = k [A] [B] or V = k [A]2
1 1
kt
[A] [A]o
1
Half life: t1/2
k[A]o
Units of k:
Examples
2C2F4 → C4F8
1 1
ln[C2F4] vs time is not linear kt
[A] [A]o
V = k [C2F4]2 slope = k
Summary
[A] 1 1
Integrated
- ln = - kt kt
Rate Laws
[A]o [A] [A]o
0.693 1
Half-life - t1/2 = t1/2
k k[A]o
Unit of rate
constant mol.L-1.time-1 time-1 L.mol-1.time-1
(k)
Relationship between temperature (T) and k
In general, as temperature increases, so
does the increasing reaction rate because k
depends on temperature.
Arrhenius Equation:
Where,
k: Rate constant
A: frequency factor, with each reaction.
Ea: Activation Energy
R = 8.314 J.mol-1.K-1 = 1.987 cal.mol-1.K-1
For a general reaction, we have, V = k[A]m.[B]n
When [A] = [B] = 1 → V = k
k is the private rate of reaction
Catalysts
Catalyst: A compound which takes part in a chemical reaction,
speeds up the rate, but does not itself undergo a chemical
change.
Catalyst lowers Ea
Ea ↓ → k ↑
P AV n A RT
nA RT nB RT
PA [ A]RT PB [ B]RT
V V
P b [ B ]RT b [ B ]b RT b
K B K RT
b a
p c
P a [ A]RT a [ A]a RT a
A
Or Kp = Kc (RT) ∆n
Le Châtelier’s Principle
when factors that influence an equilibrium are altered,
the equilibrium will shift to a new position that tends to
minimize those changes.
[NH 3 ]2
Kc
[N 2 ][H 2 ]3
o
ΔG = Δ G + RT In Q
Where, G = free energy at any moment
Go = standard-state free energy
R = ideal gas constant = 8.314 J/mol-K
T = temperature (Kelvin)
lnQ = natural log of the reaction quotient
𝒄 𝒅
o
Δ G = - RT In Kc = -RTln 𝒂 𝒃
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