Professional Documents
Culture Documents
NIM : 101314015
Kelas : KIMIA B
Outer-sphere reactions (hal.93-95)
Consequently the bond length of Fe-C in the newly formed [Fe (CN)6]3- ion will be
longer than the equilibrium value and the length of the Fe-C bond in the product [
Fe(CN)6]4- ion will be shorter than the equilibrium value. In the words two
vibrationally- excited ions will have been produced. Violation of the principle of
conservation of energy isimplied unless aprior rearrangement of the coordination
shells of each ion takes place in the formation of the activated complex activation
energy must be supplied to equalize the length of Fe-C bonds in the two ions. Since the
bond length are not very dissimiliar, little free energy of activation is required and exchange
takes place rapidly. The slowness of the exchange between [Co(NH3)6]2+ and [Co(NH3)6]3+
(k10-8M-1s-1at 64o) can hardly arise from the slight difference in Co-N bond lights.
to occur without hindrance but small enoughto be neglected in calculating the free energy
of activation, than a simple relationship applies between the rate constants of related
outer-sphere processes. From the treatment of Marcus , 3 if k12 and K12 are the rate and the
equilibrium constant, respectively, for the electron transfer process then an interralionship
exist with the rate constans (k12 and k22) for the exchange reactions of the reactans. For
example, if k12 and K12 refer to the reaction
[Fe(CN)6]4- + [Mo(CN)8]3-
[Fe(CN)6]3- + [Mo(CN)8]4-
And
[Mo(CN)8]3- + [Mo(CN)8]4-
[Mo(CN)8]4- + [Mo(CN)8]3-
then
k12=(k11k22K12f)1/2
(3.1)
where
Log f =
(log K22)2
4 log (k11k22/Z2)
And Z is a measure of the number of collisions occurring between two neutral species in unit
time at the mean separation distance in the activated complex.
Table 3.1 shows a compararison between the rate constan observed and those
calculated on the basis of eq. (3,1). Whith the exception of the systems Co3+ + Fe2+ and
[Co(NH3)6] + [Ru(NH3)6]2+ , there is a remarkable agreement between the experimental
results and the Marcus theory.
Tabel 3.1
Comparison of observed and calculated rate constans fos some outer-sphere electron
transfer reactions at 25o*.
-1 -1
k11M s
-1 -1
k22M s
K12
Fe3+ -Cr2+
4.0
210-5
21019
Ce(IV)-[W(CN)8]4-
4.4
7104
1.61015
-1 -1
k12 obs., M s
-1 -1
k12 calt., M s
2.3103
6 105
108
6.1 108
Ce(IV)-[Fe(CN)6]4-
4.4
3102
6.31012
1.9106
6.0 106
Ce(IV)-[Mo(CN)8]4-
4.4
3104
6.31010
1.4107
1.3 107
[IrCl6]2[W(CN)6] 4-
2105
7104
3.9106
6.1107
8.1107
[IrCl6]2[6] 4- -[Fe(CN)6]4-
2105
3102
1.7104
3.8105
5.7105
[IrCl6]2[6] 4- -[Mo(CN)8]4-
2105
3104
1.6102
1.9106
1.0106
[Mo(CN)8]3--[W(CN)8]4-
3104
7104
2.5104
5.0106
1.7107
[Mo(CN)8]3--[Fe(CN)6]4-
3104
3102
1.1102
3.0104
2.7104
[Fe(CN)6]3- -[W(CN)8]4-
3102
7104
2.4102
4.3104
5.1104
[Co(NH3)6]3+-V2+
3.310-12
110-2
1.3106
3.310-3
1.510-4
1.410-2
310-2
310-7
4.2101
6 106
[Co(NH3)6]3+-[Ru(NH3)6]2+
Co2+-Fe2+
3.310-12
5.0
3
4.0
1020
terjadi sebelum elektron berpindah tempat. Pendapat dapat diperluas untuk sistem dimana
terjadi perubahan kimia . Dan standar terhadap Pelepasan energi terhadap reaksi negatif.
Untuk kasus seperti reorientasi koordinasi kulit memberi reaksi kurang ketat karena energy
eksitasi getaran dari produk dibebaskan sebagai bagian dari standar reaksi pelepasan energi.
Pernyataan berbeda , sebagai reaksi menjadi lebih exotermik (misalnya Go lebih negatif)
struktur terhadap transisi akan lebih menyerupai reaktan tersebut. Energy aktivasi akan
menurun dan laju reaksi akan meningkat. Tentunya reaksi oxsidasi-reduksi antara ion-ion
logam yang berbeda (dimana Go 0) lebih cepat secara keseluruhan , maka reaksi
pertukaran isotop terhadap reaktan baik. Jika intraksi orbital mencakup proses perpindahan
elektron cukup besar untuk memungkinkan terjadinya transfer electron tanpa hambatan
namun kecil untuk diabaikan dalam menghitung energy bebas aktivasi, sehingga aplikasi
hubungan sederhana berlaku antara laju konstan terhadap proses bola luar. Dari perlakuan
Marcus ,3 jika k12 dan K12 kecepatan dan keseimbangan konstan, secara berturut-turut ,
untuk proses transfer elektron maka
kecepatan konstan (k11 dan k22) untuk perubahan reaksi terhadap reaktan. Contoh, jika k12
dan K12 bereaksi
[Fe(CN)6]4- + [Mo(CN)8]3-
[Fe(CN)6]3- + [Mo(CN)8]4-
[Fe(CN)6]3- + [Fe(CN)6]4-
[Mo(CN)8]3- + [Mo(CN)8]4-
[Mo(CN)8]4- + [Mo(CN)8]3-
Dan
Kemudian
k12=(k11k22K12f)1/2
(3.1)
Dimana
(log K12)2
4 log (k11k22/Z2)
Dan Z merupakan jumlah tumbukan yang terjadi antara dua jenis netral pada satuan volume
Log f =
terhadap solusi pada satuan waktu yang berarti pemisahan jarak pada pengaktifan
kompleks.
Table 3.1 menunjukkan perbandingan antara laju konstan yang diamati dan
perhitungan terhadap dasar kesetimbangan . (3,1). Dengan pengecualian system Co3+ + Fe2+
dan
k11M s
-1 -1
k22M s
K12
-1 -1
k12 obs., M s
Fe3+ -Cr2+
4.0
210-5
21019
Ce(IV)-[W(CN)8]4-
4.4
7104
Ce(IV)-[Fe(CN)6]4-
4.4
Ce(IV)-[Mo(CN)8]4-
-1 -1
k12 calt., M s
2.3103
6 105
1.61015
108
6.1 108
3102
6.31012
1.9106
6.0 106
4.4
3104
6.31010
1.4107
1.3 107
[IrCl6]2[W(CN)6] 4-
2105
7104
3.9106
6.1107
8.1107
[IrCl6]2[6] 4- -[Fe(CN)6]4-
2105
3102
1.7104
3.8105
5.7105
[IrCl6]2[6] 4- -[Mo(CN)8]4-
2105
3104
1.6102
1.9106
1.0106
[Mo(CN)8]3--[W(CN)8]4-
3104
7104
2.5104
5.0106
1.7107
[Mo(CN)8]3--[Fe(CN)6]4-
3104
3102
1.1102
3.0104
2.7104
[Fe(CN)6]3- -[W(CN)8]4-
3102
7104
2.4102
4.3104
5.1104
[Co(NH3)6]3+-V2+
3.310-12
110-2
1.3106
3.310-3
1.510-4
1.410-2
310-2
310-7
4.2101
6 106
[Co(NH3)6]3+-[Ru(NH3)6]2+
Co2+-Fe2+
3.310-12
5.0
3
4.0
1020