11.

0 REACTION KINETICS
Objectives: 1. 2. Define reaction rate, average rate, instantaneous rate and initial rate. Determine the reaction rate based on a differential equation.

REACTION KINETICS
Chemical kinetics is the study of the rates of chemical reactions, the factors that affect these rates, and the reaction mechanisms by which reactions occur.
Important

industrial process -Time -Optimum yield -Optimum conditions control over reaction, obtain products economically, using optimum conditions

Rate of reaction

• Reaction rate is the change in the concentration
of a reactant or a product with time. • Unit of rate (mol L-1 s-1 )

1 • rate ∝ Time
Example;

A

 B →

- d[A] rate = dt d[B] rate = dt

d[A] = change in concentration of A dt = period of time d[B] = change in concentration of B

Because [A] decreases with time, d[A] is negative.

A

B

time d[A] rate = dt rate = d[B] dt [B] ↑

[A] ↓

Rate of reaction
• The average rate is the rate over a period of time. • The rate of reaction at a given time is called an instantaneous rate of reaction. • The instantaneous rate at the beginning of a reaction is called the initial rate of reaction. • Instantaneous rate is determined from a graph of concentration vs time by drawing a line tangent to the curve at that particular time.

Rate of reaction
Reaction: H2O2(aq) → H2O(l) + ½ O2(g) Reaction rates are obtained from the slopes of the straight lines;
purple

An average rate from the purple line. The instantaneous rate at t =300 s from the red line.

blue

red

The initial rate from the blue line.

Br2 (aq) + HCOOH (aq)

2Br- (aq) + 2H+ (aq) + CO2 (g)

instantaneous rate = rate at a specific time [Br2]final – [Br2]initial d[Br2] average rate = =dt tfinal - tinitial

The differential rate equation
A differential rate equation enables the relationship between the rate of disappearance of reactants and the formation of products. Consider the reaction, aA + bB  → cC + dD

Rate =

1 d[A] 1 d[B] 1 d[C] 1 d[D] − =− = = a dt b dt c dt d dt

a,b,c and d are the stoichiometric coefficients

The differential rate equation
Example: The formation of NH3,

N2(g) + 3H2(g)  2NH3(g) → The differential rate equation is;

d[N 2 ] 1 d[H 2 ] 1 d[NH 3 ] =− = Rate = − dt 3 dt 2 dt
The equation means that the rate of disappearance of N2 is 1/3 the rate of disappearance of H2 and 1/2 the rate of formation of NH3.

Example 1:
Consider the reaction, 2HI  H2 + I2, → determine the rate of disappearance of HI when the rate of I2 formation is 1.8 x 10-6 M s-1 .

Solution:

1 d[HI] d[H 2 ] d[I 2 ] = = Rate = − 2 dt dt dt
d[I 2 ] = 1.8 × 10-6 dt 1 d[HI] d[I 2 ] = Rate = − 2 dt dt

d[HI] = 2 × 1.8 × 10-6 = 3.6 × 10-6 M s-1 dt

EXERCISE 1: Hydrogen gas produced nonpolluting product is water vapour when react in O2 due to this reaction has been used for fuel aboard the space shuttle, and may be used by Earth-bound engines in the near future. 2H2(g) + O2(g) 2H2O(g) • Express the rate in terms of changes in [H2], [O2] and [H2O] with time. • When [O2] is decreasing at 0.23 mol L-1 s-1 , at what rate is [H2O] increasing? (0.46 mol L-1 s-1 )

Exercise 2:
Consider the reaction, NO(g) + O2(g)  →2NO2(g). Suppose that at a particular time during the reaction nitric oxide (NO) is reacting at the rate of 0.066 M s-1 a) At what rate is NO2 being formed? b) At what rate is molecular oxygen reacting?

Exercise 3: Consider the reaction, N2(g) + 3H2(g)  2NH3(g) → Suppose that at a particular moment during the reaction molecular hydrogen is reacting at the rate of 0.074 M s-1 a) At what rate is ammonia being formed? b) At what rate is molecular nitrogen reacting?

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