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Chemical Kinetics
Joshua Micole Felizarta, LPT
Overview • Rate of Reaction • Factors Affecting Reaction • Rate Law for a Reaction Chemical Kinetics • Study of the rate of chemical reactions, including the mechanism by which the reaction occurs and the different factors that affect it.
• Molecules or atoms of reactants must collide with each other in
chemical reactions. • Molecules must have enough energy to initiate a reaction Chemical reactions can be either: • Fast: • Combustion of gasoline and oxygen • Vinegar and baking soda (bubble formation) • Slow: • Rusting of iron • Green patina (film) on copper Rate of reaction • The change in the concentration of a reactant or product per change in time.
Example: aA + bB → cC + dD (hypothetical chem eq)
Expression of chemical reaction
1 Δ[𝐴] 1 Δ[𝐵] 1 Δ[𝐶] 1 Δ[𝐷]
Rate = − ( ) = − ( ) = ( ) = ( ) 𝑎 Δ𝑡 𝑏 Δ𝑡 𝑐 Δ𝑡 𝑑 Δ𝑡 Reaction Rate Defined Reaction rate: changes in a concentration of a product or a reactant per unit time. [] [ ] concentration Reaction rate = —— t
change [ ]
t
t Expressing reaction rates For a chemical reaction, there are many ways to express the reaction rate. The relationships among expressions depend on the equation. Note the expression and reasons for their relations for the reaction 2 NO + O2 (g) = 2 NO2 (g) [O2] 1 [NO] 1 [NO2] Reaction rate = – ——— = – — ———— = — ——— t 2 t 2 t Make sure you can write expressions for any reaction and figure out the relationships. For example, give the reaction rate expressions for 2 N2O5 = 4 NO2 + O2
7 Practice Exercise 1. 2 H₂O₂ → 2 H₂O + O₂ 2. 2 N₂O → 2 N₂ + O₂ 3. 2 C₄H₁₀ + 13 O₂ → 8 CO₂ + 10 H₂O 4. N₂ + 3 H₂ → 2 NH₃ 5. 2 N₂O₅ → 4 NO₂ + O₂ Calculating reaction rate The concentrations of N2O5 are 1.24e-2 and 0.93e-2 M at 600 and 1200 s after the reactants are mixed at the appropriate temperature. Evaluate the reaction rates for 2 N2O5 = 4 NO2 + O2 Solution:
(0.93 – 1.24)e-2 – 0.31e-2 M
Decomposition rate of N2O5 = – ———————— = – —————— 1200 – 600 600 s = 5.2e-6 M s-1. Note however, The reaction rates rate of formation of NO2 = 1.02e-5 M s-1. are expressed in 3 rate of formation of O2 = 2.6e-6 M s-1. forms Factors Influencing Reaction Rates • Concentrations • Surface Area • Temperature • Catalyst Factors Concentration • As the concentration of the reactant increases, the reaction rate increases.
• More concentration, more collisions. More collisions, more reactions.
Factors Surface area • As the surface of the reactants increases, the reaction rate increases.
• High surface area, more reaction rates.
Factors Temperature • As the temperature of a system increase, the reaction rate increases.
• Temperature = measure of average kinetic energy of a particles
Factors Catalyst • The presence of a catalyst increases the reaction rate. • It lowers the activation energy.
• Ways to lower AE:
• Increase the frequency of collisions • Reduce intermolecular bonding within reactant molecules Rate Law • Mathematical expression that shows how the rate of reaction depends on the concentration of reactants.
In A → product
Expression rate = k [A]ˣ
where k = rate constant rate = M/s (molar per second) Order of a Reaction • Zero-order reaction (x = 0) • First-order reaction (x = 1) • Second-order reaction (x =2) Zero-order reaction (x=0) • Has a constant rate that is equal to its rate constant k regardless of the change in the concentration of reactant
rate = k [A]⁰ = k First-order reaction (x=1) • The rate k doubles when the concentration of a reactant is doubled.
rate = k [A]¹ = k[A]
Second-order reaction (x=2) • The rate k quadruples when the concentration of the reactant is doubled.
rate = k [A]² Rate Laws for Different Reaction Reaction Order Rate Law Units of k Zero rate = k [A]⁰ = k M·s-¹ First rate = k [A]¹ = k[A] s-¹ Second rate = k [A]² M-¹·s-¹ Third rate = k [A]³ M-²·s-¹ Example 1 • 2 O₃ → 3 O₂ Experiment Initial [O₃] Initial Rate (M) (M/s) I 2.00 0.500
II 4.00 1.000
III 6.00 1.500
Example 2 • N₂O₄ → 2 NO₂ Experiment Initial [N₂O₄] Initial Rate (M) (M/s) I 0.50 0.050
II 1.00 0.200
III 1.50 0.450
Example 3 Hypothetical equation A+B→C
Experiment Initial [A] Initial [B] Initial Rate of
(M) (M) Reaction (M/s) I 0.012 0.0034 1.4 x 10-³ II 0.024 0.0034 2.8 x 10-³ III 0.012 0.0068 5.6 x 10-³ Practice Problem 1 • CHCl₃ + Cl₂ → CCl₄ + HCl Experiment Initial [CHCl₃] Initial [Cl₂] Initial Rate (M) (M) (M/s) I 0.0011 0.014 2.60 x 10 -⁴
II 0.0011 0.028 5.20 x 10 -⁴
III 0.0022 0.028 2.08 x 10 -³
IV 0.0022 0.014 1.04 x 10 -³
Assignment 1 • BrO₃- + 5 Br- + 6H → 3 Br₂ + 3 H₂O Experiment Initial [BrO₃-] Initial [Br-] Initial [H] Initial Rate (M) (M) (M) (M/s) I 0.0050 0.0017 0.0042 3.80 x 10 -⁴ II 0.0050 0.0034 0.0042 7.60 x 10 -⁴ III 0.0100 0.0034 0.0042 1.52 x 10 -³
