CHEMICAL

KINETICS
Meeting 2
 Rate Laws
• Rate laws are always determined experimentally.
• The order of a reactant is not related to the stoichiometric coefficient of the
reactant in the balanced chemical equation.
• Reaction order is always defined in terms of reactant (not product)
concentrations.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

1
rate = k [F2][ClO2]
 Variation of Reaction rates and Order
2nd order, rate = k [A]2

rate

1st order, rate = k [A]

k = rate, 0th order

[A]
[A] = ___?

The variation of reaction rates as functions of concentration for various order is interesting.
Mathematical analysis is an important scientific tool, worth noticing.
 Determining Rate Laws
Rate laws have to be determined experimentally.

(A) Isolation Method:

This technique simplifies the rate law by making all the reactants
except one, in large excess.
Therefore,
The dependence of the rate on each reactant can be found by isolating each
reactant in turn and keeping all other substances (reactants) in large excess.
Using as example: r = k[A]tm [B]tn Make B in excess, so [B]>>[A].
Hence, by the end of the reaction [B] would not have changed that much,
although all of A has been used up And we can say, [B]  [B]0
Since A is the reactant that changes, then the rate becomes dependent
on A, and we can say

r = k’[A]tm , where k’ = k[B]0n

where k’ is the pseudo-first-order rate constant

Logging both sides gives: log r = log k’ + m log [A]t

y = c +m x
A plot of log r vs log [A]t gives a straight line with slope = m,
and intercept log k’ If m = 1, the reaction is said to be pseudo-first-order

With the roles of A and B reversed, n can be found in a similar manner

k can then be evaluated using any data set along with the known values of m and n
(B) Initial Rate Method:
- often used in conjunction with the isolation method,
-The rate is measured at the beginning of the reaction
for several different initial concentrations of reactants.

Initial rate

Follow reaction to ~ 10%

[A]t completion

t/s
 Recall
A+B P, Rate0 = k[A]0a[B]0b

Taking ‘logs’

log Rate0 = log k + a log [A]0 + b log[B]0

y c m x
** Keep [A]0 constant for varying values of [B]0 ** Keep [B]0 constant for varying
to find b values of [A]0 to find a from the slope
of the graph, log R0 vs log [A]0
** Substitute values of a, b, [A]0,
slope = b
Log Ro [B]0 to find k.

Intercept = log k + a log[A]0

log[B]0
However, in some cases, there may be no need to use the plots as shown previously.
EXAMPLE
R1 = k[A]a[B]b For these experiments, B is kept constant
R2 = k[nA]a[B]b while A is varied and R1 and R2 are known.
Dividing R2 by R1

(a) If R2 = 2R1, and n=2, then a = 1, so 1st

order with respect to A
(b) If R2 = 4R1, and n=2, then a = 2, so 2nd
order with respect to A
Concluding:
if n=2, and Rate doubles 1st order
Rate increases by a factor of 4 2nd order
Rate increases by a factor of 9 3rd order
Differential Rate Laws
Dependence of reaction rate on the concentrations of reactants is called the rate law, which is
unique for each reaction.
For a general reaction, a A + b B + c C  products
the rate law has the general form
order wrt A, B, and C, determined experimentally
reaction rate = k [A]X [B]Y [C]Z
the rate constant
For example, the rate law is
Use differentials to express rates
rate = k [Br-] [BrO3-] [H+] for 5 Br- + BrO3- + 6 H+  3Br2 + 3 H2O
The reaction is 1st order wrt all three reactants, total order 3.
 Differential Rate Law determination
Estimate the orders from the results observed for the reaction
H2O2 + 3 I- + 2 H+  I3- + 2 H2O
Exprmt [H2O2] [I-] [H+] Initial rate M s-1
1 0.010 0.010 0.0050 1.15e-6
2 0.020 0.010 0.0050 2.30e-6 1 for H2O2
3 0.010 0.020 0.0050 2.30e-6 1 for I-
4 0.010 0.010 0.0100 1.15e-6 0 for H+
Differential Rate Law determination - continue
Now, lets find k and the rate law
Thus, rate = 1.15e-6 = k (0.010)(0.010) from experiment 1 (or any experiment)
k = 1.15e-6 M s-1 / (0.010)(0.010) M3 = 0.0115 M-1 s-1
And the rate law is therefore,
– d [H2O2] k
rate = ————— = 0.0115 [H2O2] [I-] a differential rate law
dt total order 2
The rate when [H2O2] = [I-] = [H+] = 1.0 M:
The rate is the same as the rate constant k, when concentrations of reactants are all unity (exactly
1), doesn’t matter what the orders are.
Differential Rate Law determination – continue

The reaction rate –d[H2O2]/dt = 0.0115 [H2O2] [I–], for H2O2 + 3 I- + 2 H+  I3- + 2 H2O
What is – d[I–]/dt when [H2O2] = [I–] = 0.5 M?
Solution: Please note the stoichiometry of equation and how the rate changes.
– d[I–]/dt = – 3 d[H2O2]/dt = 3* 0.0115 [H2O2] [I–]
= 0.0345 * 0.5 * 0.5
= 0.0086 M s-1
In order to get a unique rate constant k, we evaluate k for the reaction
a A + b B  product
this way
rate = -1/a d[A]/dt = -1/b d[B]/dt = k [A]x [B]y
Differential Rate Law determination - continue

From the following reaction rates observed in 4 experiments, derive the rate law for the reaction
A + B + C  products
where reaction rates are measured as soon as the reactants are mixed.
Expt 1 2 3 4
[A]o 0.100 0.200 0.200 0.100
[B]o 0.100 0.100 0.300 0.100
[C]o 0.100 0.100 0.100 0.400
rate 0.100 0.800 7.200 0.400

This example illustrates the strategy to determine, and a reliable method to

solve rate-law experimentally.

Solution next
Differential Rate Law determination - continue

From the following reaction rates, derive the rate law for the reaction
A + B + C  products
where reaction rates are measured as soon as the reactants are mixed.
Expt 1 2 3 4 order
[A]o 0.100 0.200 0.200 0.100 3 from expt 1 & 2
[B]o 0.100 0.100 0.300 0.100 2 expt 1, 2 & 3
[C]o 0.100 0.100 0.100 0.400 1 expt 1 & 4
rate 0.100 0.800 7.200 0.400

Assume rate = k [A]x[B]y[C]z

Integrated Rate Laws
concentrations as functions of time
One reactant A decomposes in 1st or 2nd order rate law.
Differential rate law Integrated rate law
– d[A] / dt = k [A] = [A]o – k t
d[A]
– —— = k [A] [A] = [A]o e – k t or ln [A] = ln [A]o – k t
dt
d[A] 1 1 [A] conc at t
– —— = k [A]2 —— – —— = k t
dt [A] [A]o [A]o conc at t = 0

Describe, derive and apply the integrated rate laws

Learn the strategy to determine rate-law
Concentration and time of 1st order reaction
Describe the features of plot of [A] vs. t and ln[A] vs. t for 1st order
reactions. Apply the technique to evaluate k or [A] at various times.

[A ln[A
] ]
ln [A] = ln [A]o – k t
[A] = [A]o e – k t

t½

t t
 First-order reaction
A product

# of
half-lives [A] = [A]0/n
1 2

2 4

3 8

4 16
Half life & k of First Order Decomposition
The time required for half of A to decompose is called half life t1/2.
Since [A] = [A]o e – k t or ln [A] = ln [A]o – k t
When t = t1/2, [A] = ½ [A]o
Thus ln ½ [A]o = ln [A]o – k t1/2
– ln 2 = – k t1/2
k t1/2 = ln 2 = 0.693  relationship between k and t1/2

Radioactive decay usually follow 1st order kinetics, and half life of an isotope is used to indicate
its stability.
Evaluate t½ from k or k from t½
1st order reaction calculation
N2O5 decomposes according to 1st order kinetics, and 10% of it decomposed in 30 s. Estimate k,
t½ and percent decomposed in 500 s. Apply integrated rate law
to solve problems

Solution: Assume [A]o = [N2O5]o = 1.0, then [A] = 0.9 at t = 30 s or

0.9 = 1.0 e – k t apply [A]o = [A] e– k t
ln 0.9 = ln 1.0 – k 30 s
– 0.1054 = 0 – k * 30
k = 0.00351 s – 1
t½ = 0.693 / k = 197 s apply k t ½ = ln 2
[A] = 1.0 e – 0.00351*500 = 0.173
Percent decomposed: 1.0 – 0.173 = 0.827 or 82.7 %
After 2 t½ (2*197=394 s), [A] = (½)2 =¼, 75% decomposed.
After 3 t½ (3*197=591 s), [A] = (½)3 =1/8, 87.5% decomposed.
Typical Problem wrt 1st Order Reaction
The decomposition of A is first order, and [A] is monitored. The following data are recorded:
t / min 0 2 4 8
[A]/[M] 0.100 0.0905 0.0819 0.0670
Calculate k (What is the rate constant? k = 0.0499)
Calculate the half life (What is the half life? Half life = 13.89)
Calculate [A] when t = 5 min. (What is the concentration when t = 5 min?)
Calculate t when [A] = 0.0100. (Estimate the time required for 90% of A to decompose.)

Work out all the answers

 Second-Order Reactions
D[A]
rate = - = k [A]2
Dt
Half life for second order [A] is the concentration of A at
1 1 any time t
- = kt t½ = t when [A] = [A]0/2
[A] [A]0 [A]0 is the concentration of A at
1
t½ = time t=0
k[A]0
 A 2nd Order Example
Dimerization of butadiene is second order:
2 C4H6(g) = C8H12(g).
The rate constant k at some temperature is 0.100 /min. The initial concentration of butadiene [B] is
2.0 M.
Calculate the time required for [B] = 1.0 and 0.5 M
Calculate concentration of butadiene when t = 1, 5, 10, and 30.

Apply the right model and work out all the parameters.

t= 1 5 10 15 30 35
[B] = 1.67 1.0 0.67 0.50 0.29 0.25
 Zero-Order Reactions

D[A]
rate = - = k [A]0 = k
Dt
[A] - [A]0 = -kt
Half life for zero order
t½ = t when [A] = [A]0/2
[A] is the concentration of A at any time t
[A]0 [A]0 is the concentration of A at time t=0
t½ =
2k
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] - [A]0 = - kt t½ =
2k
ln 2
1 rate = k [A] ln[A] - ln[A]0 = - kt t½ =
k
1 1 1
2 rate = k [A]2 - = kt t½ =
[A] [A]0 k[A]0
Contoh soal
Concentration of
The table below shows the Time (s)
experimental data for the reaction Phenolphthalein (M)
between phenolphthalein and 0.0050 0.0
excess base. Determine the rate law 0.0045 10.5
including k and the t½ (half-life of
0.0040 22.3
the reaction).
0.0035 35.7

0.0030 51.1

0.0025 69.3

0.0020 91.6

0.0015 120.4

0.0010 160.9

0.00050 230.3
 nk Y
T ha ou