Rates of chemical reaction

▪Give examples of
chemical
reactions.

▪Why do chemical
reactions
happen?
▪ Give the chemical reactions observed in the
laboratory experiment.
▪ What factors were considered that affected the
chemical reactions?
▪ What theory was used to explain such observed
effects?
Basic principle:
Molecules must
collide to react.
▪ Describes how fast
reactants are used up and
how fast products are
formed
▪ Chemical kinetics is the
study of the rates of
chemical reactions, its
factors and mechanisms.
The rate at which reactants disappears and products appear
aA + bB ―> cC + dD

1Δ 𝐴 1Δ 𝐵 1 Δ[𝐶] 1 Δ[𝐷]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = − =− = =
𝑎 Δ𝑡 𝑏 Δ𝑡 𝑐 Δ𝑡 𝑑 Δ𝑡

Mg(s) + 2 HCl (aq) ―> MgCl2(aq) + H2(g)

At some time, we observe that the reaction
2 N2O5(g) ―> 4NO2(g) + O2(g)
mol
is forming NO2 at the rate of 0.0072 .
𝐿𝑠
Δ 𝑂2 mol
1. What is the rate of change of 𝑂2 , , in , at this time?
Δ𝑡 𝐿𝑠
Δ 𝑁2𝑂5 mol
2. What is the rate of change of 𝑁2𝑂5 , , in , at this
Δ𝑡 𝐿𝑠
time?
3. What is the rate of reaction at this time?
Plot the data for all
reactants and
products on a graph
of concentration (y)
against time (x).
▪ Describe the resulting
graph.
▪ Which substance decreased
in concentration?
▪ Which substance increased
in concentration?
▪ Given the definition of reaction rate, calculate the rate of
consumption of NO2 and rates of formation of NO and O2 from 0
to 50 seconds
▪ Calculate these rates using a time range of 150 to 300 seconds
▪ These are called average rates, which are rates under a given
time range
▪ What if you want to determine the rate of a reaction in a
specific time? For example, determine the rate of consumption
of NO2 at 175 seconds.
▪ To do this, draw a line tangent to the point at t = 175 s.
▪ The slope of this tangent line is called the instantaneous rate.
▪ Do the same for O2 and NO at 175 seconds.
▪ What do you observe with the values computed?
▪ How rate depends on
concentrations
▪ Rate law is experimentally
deduced for each reaction from a
study of how it varies with
concentration
▪ 𝑟𝑎𝑡𝑒 ∝ [𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡] or
1
𝑟𝑎𝑡𝑒 ∝
𝑝𝑟𝑜𝑑𝑢𝑐𝑡
▪ 𝑟𝑎𝑡𝑒 = 𝑘[𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡] or
𝑘
𝑟𝑎𝑡𝑒 =
𝑝𝑟𝑜𝑑𝑢𝑐𝑡
▪ 𝑟𝑎𝑡𝑒 = 𝑘 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 z

where k = rate constant

z = determined experimentally

+ 𝑥 − 𝑦
▪ 𝑟𝑎𝑡𝑒 = 𝑘 𝑁𝐻4 𝑁𝑂2
where x/y gives the order of reaction
Determining rate law from experimentally measured rate data
▪ Determining the rate law

+ 𝑥 − 𝑦
𝑟𝑎𝑡𝑒 = 𝑘 𝑁𝐻4 𝑁𝑂2
Solve for
(a) the reaction orders with respect to A and B,
(b) the rate constant,
(c) the reaction rate when [A] = 0.050 M and [B] = 0.100 M.
▪ 3NO(g) ―> N2O(g) + NO2(g) ▪ Rate = k 𝑁𝑂 2

(2nd order in NO)

▪ 2NO2(g) + F2(g) ―> 2N2OF(g) ▪ Rate = k 𝑁𝑂2 𝐹2
(1st order in NO2; 1st order in F2)

▪ 2NO2(g) ―> 2NO(g) + O2(g) ▪ Rate = k 𝑁𝑂2 2

▪ 2nd order in NO2

▪ H2O2(g) + 3I-(aq) + 2H+ ―> ▪ Rate = k H2O2 I− H+ 0

2H2O(l) + I3(g)- 1st order in H2O2

1st order in I−
0th order in H+
▪ One
▪ Rate is directly proportional to the concentration of that reactant

▪ Two
▪ Rate is directly proportional to the square of that concentration

▪ Zero
▪ Rate does not depend on the concentration of that reactant, as long
as there is some of the reactant present
- Provides insights on how reactions proceed and will describe,
in detail, the order to which bonds are broken and reformed
and how the rearrangement of the position of atoms take place
▪ Consider the reaction below:
𝑁𝑂2 (𝑔) + 𝐶𝑂 𝑔 → 𝑁𝑂 𝑔 + 𝐶𝑂2 (𝑔)

The experimentally determined rate law is:

𝑟𝑎𝑡𝑒 = 𝑘[𝑁𝑂2 ]2 [𝐶𝑂]0

THINK: Propose a series of reaction that will describe the

formation of products.
Step 1: 𝑁𝑂2 (𝑔) + 𝑁𝑂2 (𝑔) → 𝑁𝑂3 (𝑔) + 𝑁𝑂 (𝑔)
Step 2: 𝑁𝑂3 (𝑔) + 𝐶𝑂 (𝑔) → 𝑁𝑂2 (𝑔) + 𝐶𝑂2 (𝑔)

➢ ANALYZE THIS!
A. For the proposed mechanism, which step is slow and which step
is fast? Why?
B. Is there any intermediate for this mechanism? Which is it?
▪ Overall, a reaction mechanism is a series of elementary steps which
satisfy these requirements:
▪ Sum of elementary steps must give the overall balanced equation
for the reaction. (See Hess’s Law)
▪ Proposed mechanism must be in agreement with the
experimentally determined rate law.

▪ There is no such thing as a 100% accurate reaction mechanism, just a

“possibly correct” one.
𝑪𝒍𝟐 (𝒂𝒒) + 𝑯𝟐𝑺 (𝒂𝒒) → 𝑺 𝒔 + 𝟐𝑯𝑪𝒍 (𝒂𝒒) Rate = k [𝐶𝑙2 ][𝐻2𝑆]
Proposal A:
Cl2 → Cl+ + Cl- (slow)
Cl- + H2S → HCl + HS- (fast)
Cl- + HS- → HCl + S (fast)
Cl2 + H2S → 2HCl + S (overall)
𝑪𝒍𝟐 (𝒂𝒒) + 𝑯𝟐𝑺 (𝒂𝒒) → 𝑺 𝒔 + 𝟐𝑯𝑪𝒍 (𝒂𝒒) Rate = k [𝐶𝑙2 ][𝐻2𝑆]

Proposal B:
Cl2 + H2S → HCl + Cl+ + HS- (slow)
Cl + + HS- → HCl + S (fast)
Cl2 + H2S → 2HCl + S (overall)
𝑪𝒍𝟐 (𝒂𝒒) + 𝑯𝟐𝑺 (𝒂𝒒) → 𝑺 𝒔 + 𝟐𝑯𝑪𝒍 (𝒂𝒒)
Proposal C:
Cl2 ↔ Cl + Cl
Cl + H2S ↔ HCl + HS
HS + Cl → HCl + S
Cl2 + H2S → 2HCl + S
Rate = k [𝐶𝑙2 ][𝐻2𝑆]
(fast, equilibrium)
(fast, equilibrium)
(slow)
(overall)
- The equation that relates concentration and time
- Calculating half-life (t½)
First Order:
ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0

Second Order:
1 1
= 𝑘𝑡 +
[𝐴]𝑡 [𝐴]0

Zero Order:
[𝐴]𝑡 = −𝑘𝑡 + [𝐴]0
Integration rate
equation:
𝐴0
𝑙𝑛 = 𝑎𝑘𝑡
𝐴

Half-life equation:
𝑙𝑛 ∙ 2
𝑡1 =
2 𝑎∙𝑘
Integration rate
equation:
1 1
− = 𝑎𝑘𝑡
𝐴 𝐴0

Half-life equation:
1
𝑡1 =
2 𝑎𝑘 𝐴 0
Integration rate
equation:
𝐴 = 𝐴 0 − 𝑎𝑘𝑡

Half-life equation:
𝐴0
𝑡1 =
2 2 ∙ 𝑎𝑘
 Zero First Second

Rate-law expression rate = k rate = k 𝐴 rate = k 𝐴 2

𝑚𝑜𝑙 1 1
Unit of k or 𝑀 ∙ 𝑠 −1
or 𝑠 −1
or 𝑀−1 ∙ 𝑠 −1
𝐿∙𝑠 𝑠 𝑀∙𝑠

Integrated 𝐴0 1 1
𝐴 = 𝐴 0 − 𝑎𝑘𝑡 𝑙𝑛 = 𝑎𝑘𝑡 − = 𝑎𝑘𝑡
rate equation 𝐴 𝐴 𝐴0

Half-life, 𝑡1 𝐴0 𝑙𝑛 ∙ 2 1
𝑡1 = 𝑡1 = 𝑡1 =
2
2 2 ∙ 𝑎𝑘 2 𝑎∙𝑘 2 𝑎𝑘 𝐴 0

Plot that gives 1

𝐴 vs. 𝑡 𝑙𝑛 𝐴 vs. 𝑡 vs. 𝑡
straight line 𝐴
Direction of straight
Down with time Down with time Up with time
line slope
The gas-phase decomposition of NOBr is second order in
𝑁𝑂𝐵𝑟 , with k=0.810M-1s-1 at 100C. We start with 4.00x10-3M
NOBr in a flask at 100C. How many seconds does it take to
use up 1.50x10-3M of this NOBr?
2 NOBr(g) → 2 NO(g) + Br2(g)
rate = k 𝑁𝑂𝐵𝑟 2

Answer: 92.6 seconds

Compound A decomposes to form B and C in a reaction that
is first order with respect to A and first order overall. At 250C,
the specific rate constant for the reaction is 0.0450s-1. What is
the half-life of A 250C?
A→B + C

Answer: 15.4 seconds

▪ Activated complex (transition state): arrangement of atoms found
at the top of a potential energy diagram as a reaction proceeds
from reactants to products.
 𝑘 = 𝐴𝑒 −𝐸𝐴 Τ𝑅𝑇
wherein:
k = rate constant
A = frequency factor
(accounting for collision frequency, z and steric factor, p)
EA = activation energy
R = gas constant (8.3145 J mol−1 K −1)
T = temperature in Kelvin