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TUTORIAL 2
1. At 25 C, the half-life period for the decomposition of N205 is 5.7 hours and
is independent of the initial pressure of N205, calculate:
a- The time for the reaction.
b- The specific rate constant for the reaction.
Answer:
a. The t1/2 is independent on the initial conc. So, it is
1st order reaction, hence the reaction never goes to
an end and the life time is infinity.
b. t1/2 =
k=
0.693
k
0.693 0.693
=
= 0.1215 hr-1
t half
5 .7
Answer:
-log Ct = log Co (kt / 2.303)
log 40 = log 50 (k.20 / 2.303)
20k/2.303 = log 50 -log 40 = log50/40
k= log50/40 . 2.303/20 = 0.01116 m-1
-log Ct = log Co (kt / 2.303)
log (50*70/100) = log 50 (0.01116t / 2.303)
log (35) = log 50 (0.01116t / 2.303)
tshelf = log 50/35 . 2.303/0.01116
tshelf =31.97 month
0.693
0.693
=
= 62.1 month
K
0.01116
3. An ophthalmic solution dispensed at 5 mg/ml conc. exhibits a first order reaction, with
a rate constant of 0.0005 day-1. How much drug is remaining after 120 days? & how long
will it take for the drug to degrade to 90% of its initial concentration?
Answer:
- thalf =
Answer:
When a = b
x
= kt
a (a x)
K=
x
0.00566
=
=
at (a x) 0.01 * 20(0.01 0.00566)
t1/2 =
1
1
=
=
ak
0.01 * 6.52
6.52
L.mole-1min-1
15.34 min
5. Answer:
=
=
Beq
Aeq
68%
32%
0.68
= 2.125
0.32
Kf = 2.125 Kr
slope = (Kf + Kr)/2.303
Slope * 2.303 = Kf + Kr
0.01 * 2.303 = Kf + Kr
Kf = 0.02303 - Kr
2.125 Kr = 0.02303 - Kr
3.125 Kr = 0.02303
Kr = 0.0073696 min-1
Kf = 2.125 Kr
Kf = 2.125 * 0.0073696 = 0.01566 min -1
0.5
12
5.52
5.42
5.32
5.02
4.80
4.52
4.10
What is the order of glucose decomposition and the specific reaction rate constant?
Determine the half-life period. Does the available data allow an accurate calculation
of the kinetic parameters?
Answer:
We cannot determine the order or t1/2 because the readings are incomplete.
To determine the order of a reaction, you must be given data until
Ct = 1/2Co.( i.e the initial concentration reaches half.)
Using the graphical method:
No.6
time
(h)
0.5
2
3
4
6
8
12
glucose remaining
mole
5.52
5.42
5.32
5.02
4.8
4.52
4.1
No.6 Tut 2
6
y = -0.1307x + 5.6197
R2 = 0.9839
5
4
Series1
Linear (Series1)
2
1
0
0
10
15
time (h)
No.6 Tut. 2
y = -0.0118x + 0.7531
R2 = 0.9881
0.8
0.7
0.6
0.5
Series1
0.4
Linear (Series1)
0.3
0.2
0.1
0
0
10
time (h)
15
By equation:
zero order
t (h)
0.5
2
3
4
6
8
12
C0 or a
5.6
5.6
5.6
5.6
5.6
5.6
5.6
ct
5.52
5.42
5.32
5.02
4.8
4.52
4.1
C0-ct
0.08
0.18
0.28
0.58
0.8
1.08
1.5
0.16
0.09
0.093333
0.145
0.133333
0.135
0.125
First order
t
0.5
2
3
4
6
8
12
C0 or a ct
c0/c
log c0/c 2.303/t
k
5.6
5.52 1.014493 0.006249
4.606 0.028783
5.6
5.42 1.03321 0.014189
1.1515 0.016338
5.6
5.32 1.052632 0.022276 0.767667 0.017101
5.6
5.02 1.115538 0.047484 0.57575 0.027339
5.6
4.8 1.166667 0.066947 0.383833 0.025696
5.6
4.52 1.238938 0.09305 0.287875 0.026787
5.6
4.1 1.365854 0.135404 0.191917 0.025986
average
k=
0.024004
7.
12
16
20
24
Conc.
(mg/5ml)
100
81.4
68.8
56.4
44.6
36.2
31.2
0
4
8
12
16
20
24
Co or a
100
100
100
100
100
100
100
ct
100
81.4
68.8
56.4
44.6
36.2
31.2
No.7 Tut 2
Log ct
2
1.910624
1.837588
1.751279
1.649335
1.558709
1.494155
y = -2.8661x + 94.193
R2 = 0.9733
120
100
conc mg/5ml
80
Series1
60
Linear (Series1)
40
20
0
0
10
15
time months
20
25
30
No.7 Tut 2
y = -0.0215x + 2.0013
R2 = 0.9978
2.5
2
1.5
Series1
Linear (Series1)
1
0.5
0
0
10
15
20
25
30
time months
By equation:
zero order
t
0
4
8
12
16
20
24
Co or a
100
100
100
100
100
100
100
ct
100
81.4
68.8
56.4
44.6
36.2
31.2
Co-Ct
k=Coct/t
c0/c
log c0/c
0
18.6
4.65
31.2
3.9
43.6 3.633333
55.4
3.4625
63.8
3.19
68.8 2.866667
first order
t
0
4
8
12
16
Co or a
20
24
t1/2 method:
100
100
100
100
100
100
100
ct
2.303/t
100
1
0
81.4 1.228501 0.089376 0.57575 0.051458
68.8 1.453488 0.162412 0.287875 0.046754
56.4 1.77305 0.248721 0.191917 0.047734
44.6 2.242152 0.350665 0.143938 0.050474
36.2 2.762431 0.441291 0.11515 0.050815
31.2 3.205128 0.505845 0.095958 0.04854
8. A fast reaction in solution between compounds A and B was followed over a period of
60 s at 3I0 K by assaying the concentrations of A and B that remained at various time
intervals. The following results were obtained:
Time (s)
0.2
0.1
10
0.166
0.066
20
0.146
0.046
30
0.134
0.034
60
0.114
0.014
Answer:
No.8
A)
Graphical method:
time (s)
0
10
20
30
60
remaining conc of A
0.2
0.166
0.146
0.134
0.114
Try second order plot when the initial concentrations are not equal.
remaining
remaining
time (s)
conc of A
conc of B
b
a
0
0.2
0.1
0.1
10
0.166
0.066
0.1
20
0.146
0.046
0.1
30
0.134
0.034
0.1
60
0.114
0.014
0.1
x=aab-x(
remaining x(remaining) remaining)
b(a-x)
0
0.2
0.1
0.034
0.166
0.066
0.054
0.146
0.046
0.066
0.134
0.034
0.086
0.114
0.014
0.02
0.0166
0.0146
0.0134
0.0114
0.2
0.2
0.2
0.2
0.2
x= b remaining
0
0.034
0.054
0.066
0.086
b(aa(b-x) x)/a(b-x)
0.02
1
0.0132 1.257576
0.0092 1.586957
0.0068 1.970588
0.0028 4.071429
Log
0
0.099534157
0.200565028
0.294595886
0.60974682
No.8 tut 2
0.7
y = 0.0101x
2
R = 0.9996
Log b(a-x)/a(b-x)
0.6
0.5
0.4
Series1
0.3
Linear (Series1)
0.2
Linear (Series1)
0.1
0
-0.1 0
20
40
60
80
time (s)
B) k= slope * 2.303/(a-b)
k=0.0101*2.303/(0.2-0.1)
k=
0.232603 dm3/mol.s
C) Half life: The half-life or shelf life of a secondorder reaction can
Only be calculated when the initial concentration of both
Reactants are equal (a = b).
T1/2= 1/ak