In: Chemistry
Chemical kinetics
For the reaction 2A + B → C + D + 2E, data for a run with [A]0 = 800 mmol/L and [B]0 = 2.00 mmol/L are
t/ks |
8 |
14 |
20 |
30 |
50 |
90 |
[B]/[B]0 |
0.836 |
.745 |
.680 |
.582 |
.452 |
.318 |
and data for a run with [A]0 = 600 mmol/L and [B]0 = 2.00 mmol/L are
t/ks |
8 |
20 |
50 |
90 |
[B]/[B]0 |
0.901 |
0.787 |
0.598 |
0.453 |
Find the order with respect to each reactant (A and B) and
the rate
constant.
Reaction rate
d[A]/2dt = - d[B]/dt = k[A]x[B]y
t/ks |
0 |
8 |
14 |
20 |
30 |
50 |
90 |
|
Exp. 1 |
[B]/[B]0 |
1 |
0.836 |
.745 |
.680 |
.582 |
.452 |
.318 |
[B] used |
0 |
0.328 |
0.51 |
0.64 |
0.836 |
1.096 |
1.364 |
|
Exp.2 |
[B]/[B]0 |
1 |
0.901 |
0.787 |
0.598 |
0.453 |
||
[B] used |
0 |
0.198 |
0.426 |
0.804 |
1.094 |
|||
Ratio exp1/exp2 |
1.656566 |
1.502347 |
1.363184 |
1.246801 |
OBSERVE THAT AT t=14ks [B] used is 0.51 mol/L .It means for A 2x0.51 mol A /L consumed that is MORE than available.
I will continue for a model solution.
Observe that :
[B]0 = 2.00 mmol/L is the same in both experiments.
Verify and observe that:
x is not 0 (the reaction rate depends on [A])
Observe that the ratio of [B] consumed in first and second experiments during the first time interval (8 ks) is 1.65 that aprox. Let’s assume that the concentrantions of [B] consumed during this interval are close to the initial reaction rates.
1.66 is close to (8 mmol/L / 6 mmol/L)2 = 1.332 = 1.77
It means that x=2
t/ks |
0 |
8 |
14 |
20 |
30 |
50 |
90 |
|
Exp. 1 |
[B]/[B]0 |
1 |
0.836 |
.745 |
.680 |
.582 |
.452 |
.318 |
[B] used |
0 |
0.328 |
0.51 |
0.64 |
0.836 |
1.096 |
1.364 |
|
d[B]/dt[A]2 |
0.5125 |
0.796875 |
1 |
1.30625 |
1.7125 |
2.13125 |
||
1/[ d[B]/dt[A]2 ] |
1.95122 |
1.254902 |
1 |
0.76555 |
0.583942 |
0.469208 |
Observe in this table that 1/[ d[B]/dt[A]2 ] is in a liner relation to t. Then y=0
Reaction rate is now
d[A]/2dt = - d[B]/dt = k[A]2
For the first time interval:
[A] consumed is 2x0.328 = 0.656 mol/L
1/[A] = kt + 1/[Ao] as for a second reaction rate
1/0.656 = 8000 k + 1/0.800
1.524 = 8000 k + 1.25
0.274 M-1 = 8000 k
k = 0.000034 M-1 s-1
This is a provisional solution. I will revise it in the next 24 h.
Observe that :
[B]0 = 2.00 mmol/L is the same in both experiments.
Verify and observe that:
x is not 0 (the reaction rate depends on [A])
Observe that the ratio of [B] consumed in first and second experiments during the first time interval (8 ks) is 1.65 that aprox. Let’s assume that the concentrantions of [B] consumed during this interval are close to the initial reaction rates.
1.66 is close to (8 mmol/L / 6 mmol/L)2 = 1.332 = 1.77
It means that x=2
t/ks |
0 |
8 |
14 |
20 |
30 |
50 |
90 |
|
Exp. 1 |
[B]/[B]0 |
1 |
0.836 |
.745 |
.680 |
.582 |
.452 |
.318 |
[B] used |
0 |
0.328 |
0.51 |
0.64 |
0.836 |
1.096 |
1.364 |
|
d[B]/dt[A]2 |
0.5125 |
0.796875 |
1 |
1.30625 |
1.7125 |
2.13125 |
||
1/[ d[B]/dt[A]2 ] |
1.95122 |
1.254902 |
1 |
0.76555 |
0.583942 |
0.469208 |
Observe in this table that 1/[ d[B]/dt[A]2 ] is in a liner relation to t. Then y=0
Reaction rate is now
d[A]/2dt = - d[B]/dt = k[A]2
For the first time interval:
[A] consumed is 2x0.328 = 0.656 mol/L
1/[A] = kt + 1/[Ao] as for a second reaction rate
1/0.656 = 8000 k + 1/0.800
1.524 = 8000 k + 1.25
0.274 M-1 = 8000 k
k = 0.000034 M-1 s-1
This is a provisional solution. I will revise it in the next 24 h.