Rates of Chemical Reaction
Rates of Chemical Reaction
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
+ 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
▪ 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)
➢ 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.
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) Rate = k [𝐶𝑙2 ][𝐻2𝑆]
Proposal C:
Cl2 ↔ Cl + Cl (fast, equilibrium)
Cl + H2S ↔ HCl + HS (fast, equilibrium)
HS + Cl → HCl + S (slow)
Cl2 + H2S → 2HCl + S (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
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