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To answer (a), write what the rate law would be if each step were rate limiting:
For step 1, rate=k1 [Cl2], so clearly this step is not rate-determining.
For step 2, rate = k2 [Cl][CO] , but Cl is an intermediate and cannot show up
in the rate law. But we know from step 1 that k-1[Cl]2=k1[Cl2] (assuming a fast
equilibrium step), thus
[Cl]2 = k1[Cl2]/k-1 and [Cl]= (k1[Cl2]/k-1)1/2
substituting back into the rate expression gives:
rate = k2 [Cl][CO] = k2 (k1[Cl2]/k-1)1/2 [CO] = k [Cl2]1/2 [CO], so this step is not
rate-determining.
For step 3, rate= k3 [COCl][Cl2] but COCl is an intermediate.
We know that k-2[COCl] = k2 [Cl][CO]; [COCl] =k2[Cl][CO]/k-2 ] (assuming
a fast equilibrium step
Thus rate = k3 [COCl][Cl2] = k3(k2[Cl][CO]/k-2)[Cl2] =k [Cl][CO][Cl2]
We know that [Cl]= (k1[Cl2]/k-1)1/2 from above,
2. The rate constant for a reaction at 40°C is exactly 3.00 times the rate constant
at 20°C. Calculate the Arrhenius energy of activation for the reaction
assuming a temperature-independent pre-exponential factor A.
since k=Ae-Ea/RT , k40°C/k20°C=3= Ae-Ea/RT2/ Ae-Ea/RT1 (the A’s cancel)
T2=273+40 = 313K
T1=273+20 = 293K
ln 3 = -Ea/R(1/T2-1/T1)= 1.09 = -Ea/R (1/313K – 1/293K)
Ea=41.5 kJ/mol (activation energies are always positive)
3. The reaction
A ==> B + C
Is second order in A. When [A]o=0.100M, the reaction is 20% complete in 40
minutes
(a) Calculate the value of the rate constant (in L/min mol)
(b) Calculate the half-life of the reaction
(a) For a second-order reaction:
1/[A]t = kt + 1/[A]o
[A]t=0.8 [A]o=.08M
Thus, (1/0.08M)- (1/0.10M) = k (40 minutes)
k=0.0625M-1m-1
-1 -1
(c) t1/2 = 1/k[A]o; 1/(0.0625M m )(0.1M) = 160 minutes = t1/2
Mechanism 1
NO + H2 <=> NOH2 fast
NOH2 + NO ==> N2O + H2O slow
Mechanism 2
2NO <=> N2O2 slow
N2O2 + H2 ==> N2O + H2O fast