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SOAL LATIHAN MEKANISME REAKSI

Nama : Tiara Ria Eva Veronika

NIM : 160332605810

Offering :H

1. The condensation reaction of acetone, (CH3)2CO (propanon), in aqueous solution is catalyzed


by bases, B, which react reversibly with acetone to form the carbanion C3H5O-. The carbanion
then reacts with a molecule of acetone to give the product . a simplified version of the
mechanism is
(1) AH + B → BH+ + A-
(2) A- + BH+ → AH + B
(3) A- + HA → product
Where AH stands for acetone and A- its carbanion. Use the steady-state approximation to find
the concentration of the carbanion and derive the rate equation for the formation of the product
Jawab :
(1) AH + B → BH+ + A-
(2) A- + BH+ → AH + B
(3) A- + HA → product
𝑑 [𝑃] …………………………
r= = 𝑘3 [𝐴− ][𝐻𝐴] (1)
𝑑𝑡

𝑑 [𝐴− ]
= 𝑘1 [𝐴𝐻][𝐵] − 𝑘2 [𝐴− ][𝐵𝐻 + ] − 𝑘3 [𝐴− ][𝐻𝐴] = 0
𝑑𝑡
Catatan : tanda (-) apabila A- berada pada reaktan, sedangkan tanda (+) apabila A- berada pada
produk
Mencari [A-]
𝑘1 [𝐴𝐻][𝐵] − 𝑘2 [𝐴− ][𝐵𝐻 + ] − 𝑘3 [𝐴− ][𝐻𝐴] = 0
𝑘1 [𝐴𝐻][𝐵] ………………………………. (2)
[A-] = 𝑘 [𝐵𝐻 + ]+ 𝑘 [𝐻𝐴]
2 3

Mencari turunan persamaan laju pembentukan produk


Persamaan 2 disubstitusi kedalam persamaan 1
𝑑 [𝑃]
= 𝑘3 [𝐴− ][𝐻𝐴]
𝑑𝑡
𝑑 [𝑃] 𝑘1 [𝐴𝐻][𝐵]
= 𝑘3 ( ) [𝐻𝐴]
𝑑𝑡 𝑘2 [𝐵𝐻 + ] + 𝑘3 [𝐻𝐴]
Sehingga turunan persamaan laju pembentukan produk adalah :
𝑑 [𝑃] 𝑘3 𝑘1 [𝐴𝐻]2 [𝐵]
=
𝑑𝑡 𝑘2 [𝐵𝐻 + ] + 𝑘3 [𝐻𝐴]

2. Consider the following chain mechanism :


(1) AH → A. + H.
(2) A. → B. + C
(3) AH + B. →A. + D
(4) A. + B. → P
Identify the initiation, propagation, and termination steps, and use the steady-state
approximation to deduce that the decomposition of AH is first order in AH.
Jawab :
Yang termasuk inisiasi, propagasi, dan terminasi adalah:
(1) AH → A. + H. inisiasi
(2) A. → B. + C propagasi
(3) AH + B. →A. + D
(4) A. + B. → P terminasi
𝑑[𝐴𝐻]
= −𝑘1 [𝐴𝐻] − 𝑘3 [𝐴𝐻][B. ] ……………………………………………………(1)
𝑑𝑡

𝑑[B. ]
= 0 = 𝑘2 [A. ] − 𝑘3 [𝐴𝐻][𝐵. ] − 𝑘4 [A. ][B. ]
𝑑𝑡
𝑘3 [𝐴𝐻][𝐵. ] + 𝑘4 [A. ][B. ] = 𝑘2 [A. ]
[B. ](𝑘3 [𝐴𝐻] + 𝑘4 [A. ]) = 𝑘2 [A. ]
𝑘2 [A.] ……………………………………………………(2)
[B. ] =
𝑘3 [𝐴𝐻]+ 𝑘4 [A.]

𝑑[A. ]
= 0 = 𝑘1 [𝐴𝐻] − 𝑘2 [A. ] + 𝑘3 [𝐴𝐻][𝐵. ] − 𝑘4 [A. ][B. ]
𝑑𝑡
𝑘2 [A. ] + 𝑘4 [A. ][B. ] = 𝑘1 [𝐴𝐻] + 𝑘3 [𝐴𝐻][𝐵. ]
[A. ] = (𝑘2 + 𝑘4 [B. ]) = 𝑘1 [𝐴𝐻] + 𝑘3 [𝐴𝐻][𝐵. ]
𝑘1 [𝐴𝐻]+ 𝑘3 [𝐴𝐻][𝐵.] ……………………………………………………(3)
[A. ] =
𝑘2 +𝑘4 [B.]
Disubstitusi persamaan 3 ke persamaan 2
𝑘2 [A. ]
[B. ] =
𝑘3 [𝐴𝐻] + 𝑘4 [A. ]

𝑘1 [𝐴𝐻]+ 𝑘3 [𝐴𝐻][𝐵.]
𝑘2 +𝑘4 [B.]
[B. ] = 𝑘2 𝑘 [𝐴𝐻]+ 𝑘 [𝐴𝐻][𝐵.]
𝑘3 [𝐴𝐻]+ 𝑘4 [ 1 𝑘 +𝑘 3[B.] ]
2 4

𝑘2 𝑘1 [𝐴𝐻] + 𝑘2 𝑘3 [𝐴𝐻][𝐵. ]
𝑘2 + 𝑘4 [B. ]
[B. ] =
𝑘 [𝐴𝐻] + 𝑘3 [𝐴𝐻][𝐵. ]
𝑘3 [𝐴𝐻] + 𝑘4 [ 1 ]
𝑘2 + 𝑘4 [B. ]
𝑘2 𝑘1 [𝐴𝐻] + 𝑘3 𝑘2 [𝐴𝐻][𝐵. ]
( )
𝑘2 + 𝑘4 [B. ]
[B. ] =
𝑘 𝑘 [𝐴𝐻] + 𝑘2 𝑘4 [𝐴𝐻][𝐵. ] + 𝑘1 𝑘4 [𝐴𝐻] + 𝑘4 𝑘3 [𝐴𝐻][𝐵. ]
( 3 2 )
𝑘2 + 𝑘4 [B. ]
𝑘1 𝑘2 [𝐴𝐻]+𝑘2 𝑘3 [𝐴𝐻][𝐵.] 𝑘2 +𝑘4 [B.]
[B. ] = x𝑘
𝑘2 +𝑘4 [B.] 2 𝑘3 [𝐴𝐻]+𝑘3 𝑘4 [𝐴𝐻][𝐵.]+𝑘1 𝑘4 [𝐴𝐻]+𝑘4 𝑘3 [𝐴𝐻][𝐵.]

𝑘1 𝑘2 [𝐴𝐻] + 𝑘2 𝑘3 [𝐴𝐻][𝐵. ]
[B. ] =
𝑘2 𝑘3 [𝐴𝐻] + 𝑘3 𝑘4 [𝐴𝐻][𝐵. ] + 𝑘1 𝑘4 [𝐴𝐻] + 𝑘4 𝑘3 [𝐴𝐻][𝐵. ]

𝑘2 𝑘3 [𝐵. ][𝐴𝐻] + 𝑘3 𝑘4 [𝐴𝐻][𝐵. ]2 + 𝑘1 𝑘4 [𝐴𝐻][𝐵. ] + 𝑘3 𝑘4 [𝐴𝐻][𝐵. ]2 = 𝑘1 𝑘2 [𝐴𝐻] + 𝑘2 𝑘3 [𝐴𝐻][𝐵. ]

𝑘2 𝑘3 [𝐵. ][𝐴𝐻] − 𝑘2 𝑘3 [𝐴𝐻][𝐵. ] + 𝑘3 𝑘4 [𝐵. ]2 [𝐴𝐻] + 𝑘1 𝑘4 [𝐴𝐻][𝐵. ] + 𝑘3 𝑘4 [𝐴𝐻][𝐵. ]2 = 𝑘1 𝑘2 [𝐴𝐻]

2𝑘3 𝑘4 [𝐵. ]2 [𝐴𝐻] + 𝑘1 𝑘4 [𝐴𝐻][𝐵. ] = 𝑘1 𝑘2 [𝐴𝐻]

Diasumsikan nilai k3 <<< k1 , k2 , k4 maka :

k1k4[AH][ B.] = k1k2[AH]

𝑘 𝑘 [𝐴𝐻]
[ B.] = 𝑘1 𝑘2 [𝐴𝐻]
1 4

𝑘2
[ B.] =
𝑘4

Substitusi nilai [ B.] ke persamaan 1 :

𝑑[𝐴𝐻]
= −𝑘1 [𝐴𝐻] − 𝑘3 [𝐴𝐻][B. ]
𝑑𝑡
𝑘
= −𝑘1 [𝐴𝐻] − 𝑘3 [𝐴𝐻][𝑘2 ]
4

𝑘2 𝑘3 [𝐴𝐻]
= −𝑘1 [𝐴𝐻] −
𝑘4

−𝑘1 − 𝑘2 𝑘3
=( ) [𝐴𝐻]1
𝑘4

𝑑 [𝐴𝐻]
= 𝑘 [𝐴𝐻]1 (terbukti bahwa reaksi dekomposisi AH adalah reaksi orde 1)
𝑑𝑡

3. Devise the rate law for the decomposition of N2O5,


2 N2O5(g) → 4 NO2(g) + O2(g)
On the basis of the following mechanism :
N2O5 → NO2 + NO3 ka
NO2 + NO3 → N2O5 k’a
NO2 + NO3 → NO2 + O2 + NO kb
NO + N2O5 → NO2 + NO2 + NO2 kc
Jawab :
N2O5 → NO2 + NO3
k1 = [N2O5]
NO2 + NO3 → N2O5
k-1 = [NO2][NO3]

NO2 + NO3 →NO2 + O2 + NO


k2 = [NO2][NO3]
NO + N2O5 → NO2 + NO2 + NO2
k3 = [NO][N2O5]
𝑑 [𝑁𝑂3 ]
= k1[N2O5]- k-1[NO2][NO2]- k2[NO2][NO3]
𝑑𝑡

= k1[N2O5] – (k1+k2) [NO2][NO3] ...............................................(1)

= 0 → pada steady state

𝑑 [𝑁𝑂]
= k2 [NO2][NO3] – k3[NO][N2O5] ...............................................(2)
𝑑𝑡
= 0 → pada steady state
𝑑 [𝑁2 𝑂5 ]
= k1[N2O5]+ k-1 [NO2][NO3] – k3[NO][N2O5] ...............................................(3)
𝑑𝑡

[NO3] pada steady state pada persamaan 1


0 = k1[N2O5] – (k1+k2) [NO2][NO3]
𝑘1 [𝑁2 𝑂5 ] ...............................................(4)
Maka, [NO3] = (𝑘
1 +𝑘2 )[𝑁𝑂2 ]

[NO] pada steady state pada persamaan 2


0 = k2[NO2][NO3] – k3 [NO][N2O5]
𝑘2 [𝑁𝑂2 ][𝑁𝑂3 ] ...............................................(5)
Maka, [NO] = 𝑘3 [NO][𝑁2 𝑂5 ]

Subtitusi persamaan 4 dan 5


𝑘2 [𝑁𝑂2 ][𝑁𝑂3 ]
[NO] = 𝑘3 [NO][𝑁2 𝑂5 ]
𝑘2 [𝑁𝑂2 ] 𝑘1 [𝑁2 𝑂5 ]
= +
𝑘3 [𝑁2 𝑂5 ] (𝑘 1 +𝑘2 )[𝑁𝑂2 ]

𝑘1 𝑘2 ...............................................(6)
=𝑘 (𝑘−1 +𝑘2 )
3

Subtitusi persamaan 4 dan 6 ke persamaan 3


𝑑 [𝑁2 𝑂5 ]
= k1[N2O5]+ k-1 [NO2][NO3] – k3[NO][N2O5]
𝑑𝑡
𝑘1 [𝑁2 𝑂5 ] 𝑘 𝑘
= k1[N2O5]+ k-1 [NO2] (𝑘 )[𝑁𝑂 ]
- 𝑘 (𝑘1 2+𝑘 ) [N2O5]
1 +𝑘 2 2 3 −1 2

𝑘 𝑘 𝑘1 𝑘2
= [N2O5] (𝑘1 − (𝑘 −1+𝑘1 ) + (𝑘−1 +𝑘2 )
)
−1 2

𝑑 [𝑁2 𝑂5 ] 2 𝑘1 𝑘2 [𝑁2 𝑂5 ] 𝑘1
=− (𝑘−1 +𝑘2 )
atau −2 k2 [𝑁2 𝑂5 ]
𝑑𝑡 𝑘−1

4. An oversimplified version of the CH3CHO decomposition mechanism is


(The CHO reacts to form minor amounts of various species)
(a) Identify the initiation, propagation, and termination steps.
(b) What is the overall reaction, neglecting minor product formed in initiation and termination
steps?
(c) Show that r = k[CH3CHO]3/2, where k = k2(k1/2k4)1/2
Jawab :
(a)
Inisiasi
Propagasi
Propagasi

Terminasi

𝑑[𝐶𝐻4 ]
(b) = k2 [CH3] [CH3CHO] .....................................(persamaan 1)
𝑑𝑡

Pendekatan steacly-state → CH3 dan CH3CO maka harus dihilangkan

𝑑[𝐶𝐻3 ]
= k1 [CH3CHO] – k2 [CH3] [CH3CHO] + k3 [CH3CO] – 2k4 [CH3]2...(persamaan 2)
𝑑𝑡

𝑑[𝐶𝐻3 𝐶𝑂]
= k2 [CH3] [CH3CHO] – k3 [CH3CO] ........(persamaan 3)
𝑑𝑡

Eliminasi persamaan 2 dan 3

𝑑[𝐶𝐻3 ]
= k1 [CH3CHO] – k2 [CH3] [CH3CHO] + k3 [CH3CO] – 2k4 [CH3]2
𝑑𝑡

𝑑[𝐶𝐻3 𝐶𝑂]
= k2 [CH3] [CH3CHO] – k3 [CH3CO]
𝑑𝑡
+
0 = k1 [CH3CHO] – 2k4[CH3]2
2k4[CH3]2 = k1[CH3CHO]

𝑘1 [𝐶𝐻3 𝐶𝐻𝑂]
[CH3]2 = 2𝑘4

𝑘1 [𝐶𝐻3 𝐶𝐻𝑂]
[CH3] = √ 2𝑘4

𝑘
= (2𝑘1 )½ [CH3CHO] ½..............(persamaan 4)
4

Disubstitusikan persamaan 4 ke persamaan 1

𝑑[𝐶𝐻4 ]
= k2 [CH3] [CH3CHO]
𝑑𝑡

𝑘
= k2 (2𝑘1 )½ [CH3CHO] ½ [CH3CHO]
4

𝑘
= k2 (2𝑘1 )½ [CH3CHO]3/2
4

𝑑[𝐶𝐻4 ] 𝑘
(c) r = = k2 (2𝑘1 )½ [CH3CHO]3/2
𝑑𝑡 4

k
3/2
r = k [CH3CHO]