EXAMPLE1: The gas phase reaction 2NO + O2 = 2NO2 has the observed rate law

r=k[NO]2[O2]. Devise some mechanisms for this reaction that have a rate-determining step
and that lead to this rate law.

r=k[NO]2[O2] kelangan 2n at 4o

n2o2 + o2
no3 + no

first possible mech By steady state approximation:

NO + NO <> N2O2 Rate=k[N2O2][O2]
N2O2 + O2 > 2NO2 k1[NO]2 = k-1[N2O2] = = = [N2O2]= (k1/k-1)
Overall: 2NO + O2 > 2NO2 [NO]2
Rate= k2 (k1/k-1) [NO]2[O2]

Second possible mech: By steady state approximation:

NO + O2 <> NO3 Rate=k[NO3][NO]
NO3 + NO > 2NO2 k-1[NO3] = k1[NO][O2]/k-1
Overall: 2NO + O2 > 2NO2 Rate= k2 (k1/k-1) [NO]2[O2]

EXAMPLE2: The reaction Hg22+ + Tl3+ > 2Hg2+ + Tl+ in aqueous solution has the rate law
R=k([Hg22+][Tl3+]/[Hg2+]).
Devise a mechanism consistent with the rate law.

Hg22+ <> Hg + Hg2+

Hg + Tl3+ > Tl+ + Hg2+

By steady-state:

EXAMPLE3: The reaction I2 + H2 > 2HI has the rate law r=k[I 2]1/2[H2]. Devise a mechanism
consistent with the rate law.

I2 <> 2I
I + H2 > HI + H (slow)
H + I > HI (fast)
Overall reaction: H2 + I2 > 2HI

By steady stae
k1[I2] = k-1[I]2
[I]= (k1/k-1)1/2 [I2]1/2
EXAMPLE4: The formation of phosgene CO + Cl 2 = COCl2 has the rate law r=k[CO][Cl 2]3/2.
Devise mechanism(s) consistent with the rate law. (see picture as well)

Cl2 <> 2Cl

CO + Cl <> COCl
Cl2 + COCl > COCl2 + Cl (slow)
Cl + Cl > Cl2 (fast)

By steady-state
K3[COCl][Cl2]
K2[CO][Cl] = k-2[COCl]

Cl2 > Cl
Cl2 + Cl > Cl3
CO + Cl3 > COCl2 + Cl

Cl2 <> 2Cl

CO + Cl <> COCl
CO + Cl2 > COCl2 + Cl