QUIZ 2 CHE 171 (Reaction Mechanism)
1. The gas-phase reaction of chlorine with chloroform is described by the equation:
Cl2(g) + CHCl3(g) HCl(g) + CCl4(g)
The rate law determined from experiment has a noninteger order:
rate=k[Cl2]1/2[CHCl3]
A proposed mechanism for this reaction follows:
Ist step: fast equilibrium
2nd step: slow (RDS)
3rd step (fast not needed)
Is this an acceptable mechanism for this reaction?
Solution: If the problem states the relative rates of elementary steps (ie: fast equilibrium, slow..), consider only
the fast equilibrium step in getting the concentration of the intermediate.
𝑟𝑎𝑡𝑒𝑓 = 𝑟𝑎𝑡𝑒𝑟
𝑘1 [𝐶𝑙2 ] = 𝑘−1 [𝐶𝑙]2 (eqn 1)
𝑘1 [𝐶𝑙2 ] 1/2
[𝐶𝑙] = ( 𝑘−1
) (eqn 2)
Proof of eq 1:
Rewrite the first step as:
Cl2 2Cl (k1)
2Cl Cl2 (k-1)
𝑑[𝐶𝑙] 𝑑[𝐶𝑙]
𝑟𝑎𝑡𝑒 = → = 2𝑟𝑎𝑡𝑒 = 2𝑘1 [𝐶𝑙2 ]
2𝑑𝑡 𝑑𝑡
𝑑[𝐶𝑙] 𝑑[𝐶𝑙]
𝑟𝑎𝑡𝑒 = − → = −2𝑟𝑎𝑡𝑒 = −2𝑘2 [𝐶𝑙]2
2𝑑𝑡 𝑑𝑡
𝑟𝑎𝑡𝑒𝑓 = 𝑟𝑎𝑡𝑒𝑟
2𝑘1 [𝐶𝑙2 ] = 2𝑘2 [𝐶𝑙]2
𝑘1 [𝐶𝑙2 ] = 𝑘2 [𝐶𝑙]2
Get the overall rate law based from RDS:
𝑟𝑎𝑡𝑒 = 𝑘2 [𝐶𝑙][𝐶𝐻𝐶𝑙3 ] (eq3)
Substitute (2) to (3)
1/2
𝑘1 [𝐶𝑙2 ]
𝑟𝑎𝑡𝑒 = ( ) 𝑘2 [𝐶𝐻𝐶𝑙3 ]
𝑘−1
𝑘1 1/2
𝑙𝑒𝑡 𝑘 = 𝑘2 ( )
𝑘−1
𝑟𝑎𝑡𝑒 = 𝑘[𝐶𝑙2 ]1/2 [𝐶𝐻𝐶𝑙3 ]
Valid Mechanism
2. The compound NO2Cl is thought to decompose to NO2 and Cl2 by the following mechanism:
Derive the rate law for the production of Cl2 using the steady-state approximation.
Solution: If in case that the relative rates of reaction are not stated, account all the intermediates appearing
as a product and reactant in the elementary steps. Then perform SS approximation.
Intermediate: Cl
𝑑[𝐶𝑙]
= 𝑘1 [𝑁𝑂2 𝐶𝑙] − 𝑘−1 [𝑁𝑂2 ][𝐶𝑙] − 2[𝑁𝑂2 𝐶𝑙][𝐶𝑙] = 0
𝑑𝑡
𝑘1 [𝑁𝑂2 𝐶𝑙]
[𝐶𝑙] = (eq1)
[𝑁𝑂 ]+𝑘
𝑘−1 2 2 [𝑁𝑂2 𝐶𝑙]
𝑑[𝐶𝑙2 ]
𝑑𝑡
= 𝑘2 [𝑁𝑂2 𝐶𝑙][𝐶𝑙] (rate of Cl2 production) (eq2)
Subs (1) to (2),
𝒅[𝑪𝒍𝟐 ] 𝒌𝟏 𝒌𝟐 [𝑵𝑶𝟐 𝑪𝒍]𝟐
=𝒌 [𝑵𝑶
𝒅𝒕 −𝟏 𝟐 ]+𝒌𝟐 [𝑵𝑶𝟐 𝑪𝒍]
3. The kinetics of the reaction between H2 and Br2 were determined experimentally by Bodenstein around 100 years
ago. The overall reaction has the equation
𝑑[𝐻𝐵𝑟]
H2 + Br2 2HBr = 𝑘[𝐻2 ][𝐵𝑟2 ]1/2
𝑑𝑡
The following mechanism has been proposed:
Br2 2Br (k1 is forward and k5 is reverse rate constant)
𝑘2
Br + H2 → HBr+H
𝑘3
H + Br2 → HBr + Br
𝑘4
H + HBr → H2 + Br
𝑘 [𝐻𝐵𝑟]
If ( 4) ( [𝐵𝑟 ] ) ≪ 1, show that the proposed mechanism is consistent with the experimentally determined rate law.
𝑘3 2
Solution: Approach is similar to problem 2 but this requires tedious algebra to simplify everything. Please
take note of the relationship of rate with stoichiometry.
Intermediates: Br and H
SS approx.:
𝑑[𝐵𝑟]
𝑑𝑡
= 2𝑘1 [𝐵𝑟2 ] − 2𝑘5 [𝐵𝑟]2 − 𝑘2 [𝐵𝑟][𝐻2 ] + 𝑘3 [𝐻][𝐵𝑟2 ] + 𝑘4 [𝐻][𝐻𝐵𝑟] = 0 (eq1)
Check this out: Dito kayo malimit magkamali
Proof:
Rewrite the first step as:
Br2 2Br (k1)
2Br Br2 (k5)
𝑑[𝐵𝑟] 𝑑[𝐵𝑟]
𝑟𝑎𝑡𝑒 = → = 2𝑟𝑎𝑡𝑒 = 2𝑘1 [𝐵𝑟2 ]
2𝑑𝑡 𝑑𝑡
𝑑[𝐶𝑙] 𝑑[𝐶𝑙]
𝑟𝑎𝑡𝑒 = − → = −2𝑟𝑎𝑡𝑒 = −2𝑘2 [𝐵𝑟]2
2𝑑𝑡 𝑑𝑡
𝑑[𝐻]
= 𝑘2 [𝐵𝑟][𝐻2 ] − 𝑘3 [𝐻][𝐵𝑟2 ] − 𝑘4 [𝐻][𝐻𝐵𝑟] = 0 (eq2)
𝑑𝑡
𝑑[𝐻𝐵𝑟]
𝑑𝑡
= 𝑘2 [𝐵𝑟][𝐻2 ] + 𝑘3 [𝐻][𝐵𝑟2 ] − 𝑘4 [𝐻][𝐻𝐵𝑟] = 0 (eq3)
Solving (1) and (2)
1 1
𝑘
[𝐵𝑟] = ( 1 )2 [𝐵𝑟2 ]2 (eq4)
𝑘 5
𝑘2 [𝐻2 ][𝐵𝑟]
[𝐻] = (eq 5)
𝑘3 [𝐵𝑟2 ]+𝑘4 [𝐻𝐵𝑟]
Subs (4) and (5) to (3), and after performing some math acrobatics:
𝑘1 1/2 1/2
𝑑[𝐻𝐵𝑟] 2𝑘2 (𝑘5 ) [𝐻2 ][𝐵𝑟2 ]
=
𝑑𝑡 𝑘 [𝐻𝐵𝑟]
1 + (𝑘4 ) ( )
3 [𝐵𝑟2 ]
𝑘 [𝐻𝐵𝑟]
If ( 4) ( [𝐵𝑟 ] ) ≪ 1 then
𝑘3 2
𝑑[𝐻𝐵𝑟] 𝑘1
= 2𝑘2 ( )1/2 [𝐻2 ][𝐵𝑟2 ]1/2
𝑑𝑡 𝑘5
𝑘
Let 𝑘 = 2𝑘2 (𝑘1 )1/2
5
𝒅[𝑯𝑩𝒓]
= 𝒌[𝑯𝟐 ][𝑩𝒓𝟐 ]𝟏/𝟐
𝒅𝒕
Mechanism is valid.