Yesica Narvez

102113011313

Cintica formal
3

Problem 1.18 A second order reaction with initial concentration of each reactant as 0.5 mol dm was
carried out in presence of acid as catalyst. At pH 4.0 the half-life of reaction was found to be 60 min.
Calculate the observed and true rate constant for the reaction.
Solution
+

Rate = ktrue [H ][A][B] = kobs [A][B], when kobs = ktrue [H+]

3

[A]0 = [B]0 = 0.5 mol dm

+

pH

[H ] = 10

= 10

mol dm

For a second order reaction

1
k obs [initial conc .]

t1/2 =

k =

mol dm min

obs

= 0.0333

60 0.5
= 3.33 10

k
k

true

mol dm min

3.33 102

obs

[H ]
=

=
10

mol dm
2

mol 1 dm 3min 1

3.33 10 mol dm min

(i)

Mtodo
estacionario

HBr + H

(ii)

HBr + Br

(iii)

Consider the following

reactions:

Br2 ki Br + Br
Br + H 2

kp

H + Br2

kp2

H + HBr
H2
Br + Br

Rate of formation of
product

kt

kinh

Br2

+ Br

(iv)

d [ HBr ]
=k v [ Br ] [ H 2 ]+ k v [ H ][ Br ] k inh [ H ][ Br ]
dt
For determination of rate of reaction, [Br] and [H] must be known and can be determined by applying
steady state approximation with respect to [H] and [Br], respectively.
On applying the steady state approximation with respect to [H], we get
k p1 [Br][H 2 ] = k p 2 [H][Br2 ] + kinh [H][HBr]

k
or

[H] =

p2

p1

(b)

[Br][H 2 ]

(c)

[Br2 ] + kinh [HBr]

Applying the steady state with respect to [Br], we get

k [Br ] +k
i

[H][Br ] + k
p2

inh [H][HBr]

= k t[Br]

+ k p1 [Br][H

] (d)

From equations (b) and (c), we get

k [Br ] = k [Br]
2

[Br] =

k i 1 /2
1 /2
B r2 ]
[
kl

(e)

Substituting the value of [Br] in equation (c), the value of [H] becomes

[ H ]=

k
k pl i
kt

1 /2

()

1 /2

[ B r2 ] [ H 2 ]

(f)

k p2 [ B r 2 ] +k inh [ HBr ]

Again, from equations (a) and (b), we get

d [HBr] = 2kp 2 [H][Br2 ]

(g)

dt
Substituting the value of [H] from equation (f), the rate of reaction becomes

2k k

p1 p2 (

d [HBr]
=

dt

or

p 2 [Br2

2k k

d [HBr]

p1 p2

1/2

k i / kt )

3/2

[Br2 ] [H 2 ]

] + kinh [HBr]
1/2

1/2

( k i / kt ) [Br2 ] [H 2 ]

=
1 + k inh [HBr]/ kp 2 [Br2 ]

dt

Fotoqumica
Solved problem 3. When irradiated with light of 5000 wavelength, 1 x 10 -4
mole of a substance is decomposed. How many photons are absorbed during
the reaction if its quantum efficiency is 10.00 (Avogadro number N = 6.02 x
1023)
Solution
Quantum efficiency of the reaction = 10,00
N. Of moles decomposed = 1 x 10.4
N. of molecules decomposed = 1 x 10-4 x

6,02 x 1023 = 6,02 x 1019

We know that,

N . of molecules descomposed
N . of photonsabsorbed

6,02 x 1019
N . of photons absorbed

N. of photons absorbed

6,02 x 1019

=6,02 x 1018
10