بسم هللا الرحمن الرحيم
REVISION
By
Omnia Elsabouny
Example
1- The reaction A B + C is known to follow zero
order and have half – life of 7.5 min
a-What is the value of the rate constant if [Co] = 2.5 M
b-How long it takes the reaction to reach [C] = 0.25 M
c- What would be the concentration of [C] be after 45
second if we started with [Ao]=2.5M
A drug product is known to be ineffective after it decompose
to 75%. The original concentration of the drug in the product
was 40 mg/ml, when assayed after 18 months, the
concentration was found to be 32 mg/ml. Assuming that the
decomposition is first-order, what expiration date (in years)
should be assigned on the label? What is the half life of this
product ?
Answer:
1st order:
K = 2.303/t log C0/C
K=2.303/18 log 40/32
K= 0.0124 month-1
t = 2.303/K log C0/C
t = 2.303/0.0124 log 100/75
t = 23.21 month = 1.93 years
t1\2= 0.693\ k
= 0.693\ 0.0124 = 55.89 months
Drug x is available as pediatric oral suspension containing
80 mg/ml. Assuming that the rate constant of drug
decomposition is 4.73x10-4 (mg/ml)-1. month-1. Calculate
the half-life of this product (in years)? What would be the
remaining drug concentration after 1-year storage at room
temperature?
Answer:
K = 4.73x10-4 (mg/ml)-1. month-1 ======> Second-order
decomposition
t1/2 = 1 / a K
= 1/ 80 x 4.73x10-4
= 26.43 month = 2.2 years
1 / a-x = 1 / a + Kt
= 1 / 80 + ( 4.73x10-4 x 12)
a-x (remaining concentration) = 55.02 mg/ml
Example :-
In the saponification of methyl acetate at
25°C, the concentration of sodium
hydroxide remaining after 75 minutes
was 0.00552. The initial concentration
of ester and of the base was each 0.01M
Calculate the second order rate constant
and the half life of the reaction?.
PROBLEM :
The reaction of butadiene gas (C4H6) with itself produces C8H12 gas as
follows:
2C4H6(g)→C8H12(g)
The reaction is second order with a rate constant equal to 5.76×10−2 L
/mol⋅min under certain conditions. If the initial concentration of
butadiene is 0.200 M, what is the concentration remaining after 10.0
min?
ANSWER :
We know three variables in this equation: [A]0 = 0.200 mol/L, k=5.76×10−2 M -1
min -1 , and t = 10.0 min. Therefore, we can solve for the remaining variable, [A]t:
Problem :
If the reactant concentration changes from 0.08M to
0.04M in 10 minutes for the second-order reaction.
Calculate the time it takes for the reactant concentration
to reach 0.01M ?
Answer:
By substituting values given in data in the below equation:
𝟏 𝟏
= +kt
[𝑨] [𝑨]𝟎
We can find the rate constant k.
1/0.08 − 1/0.04 = k.10
K = 1.25 M−1⋅ min−1
Using the same equation, we can calculate the time when the
concentration of the reactant reaches 0.01M,
1/0.08 − 1/0.01 = 1.25t
t = 70 mins
Example:- Time, Glucose
hours remaining
(moles / l
The rate of decomposition of 0.056 M x10-2)
glucose at 140°C in an aqueous
solution containing 0.35 N HCl was 0.5 5.52
found to be: 2 5.31
3 5.18
-What is the order?
4 5.02
-The half life ? 6 4.78
-The specific rate of this decomposition ?- 8 4.52
10 4.31
12 4.09
Answer:-
(1) Determination of reaction order by graphical method:-
A logC
Intercept = Ao Intercept = log Co
Slope = - K Slope = - K ∕ 2.303
t t
Zero - order First - order
l / a -x
Slope = K
Intercept = l / a
t
Second - order
(2) Determination of reaction order by substitution method:-
Time At x10-2 Log At 1/At Kzero K1st K2nd
0.5 5.52
2 5.31
3 5.18
4 5.02
6 4.78
8 4.52
10 4.31
12 4.09
Example:-
Decomposition of hydrogen peroxide (a-x) Time
(min)
at 25 in aqueous solution containing
57.50 0
0.02 M KI. 50.40 5
43.5 10
-Determine order of reaction and rate 29.10 25
constant from graphical method. 16.7 45
9.6 65
-After that compute t0.5 of reaction. 0 100
Example:- (I-)(mole/l) t ( min)
0.015 3.83
Determine the reaction order
and the rate constant. 0.026 7.75
0.035 12
Answer:-
0.052 24
Determination of the order by
substitution method 0.059 32
then determine the rate constant
0.064 39.5
