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Outher-sphere reactions

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.

However , these Co(III) complexes display widely different electronic configurations


[Co(NH3)6]2+ is t2g5eg2 whereas [Co(NH3)6]3+ is t2g6, inferring that changes in the electronic
arrangement , in addition to coordination rearragements, must needs occur before electron
transfer can take place. The argument can be extended to systems in which there is a net
chemical change and the standard free energy of reaction is negative. For such cases
reorientation of the coordination shells of the reactans is less stringent since the vibrational
excitation energy of the products is liberated as part of the standard free energy of reaction.
Stated differently, as the reaction becomes more exothermic (i.e., Go becomes more
negative) the structure of the transition state will more closely resemble that of reactans,
the free energy activation will decrease and the rate of reaction will increase. Certainly,
oxidation-reduction reactions between ions of different metals (for which Go0) are
faster, on the whole, then isotopic exchange reactions of either reactant. If the interaction
of the orbitals involved in the electron transfer processis large enough for electron transfer
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
6/5/2012example, 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 k11 and k22 refer to exchange reactions

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

Ce(IV)-[Fe(CN)6]4-

4.4

Ce(IV)-[Mo(CN)8]4[IrCl6]2[W(CN)6] 4-

-1 -1

k12 obs., M s

-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

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

*From N.Sutin, Proceedings of Symposium on Exchange Reactions, Brookhaven


National Laboratory, International Atomic Energy Agency, Vienna, 1965, and references
cited therein.
Calculated from k12=(k11k22K12f)1/2

Terjemahan:

Reaksi bola luar


Akibatnya panjang ikatan Fe-C dalam bentuk ion baru [Fe(CN)6]3 menjadi lebih panjang dari
nilai kesetimbangan dan panjang ikatan Fe-C dan produk ion [Fe(CN)6]4- akan lebih pendek
dari nilai kesetimbangan . Dengan kata lain dua peningkatan getaran ion akan terproduksi.
Pelanggaran prinsip kekekalan energi kecuali penataan ulang kordinasi kulit pada setiap
tepat ion sebelumnya. Pada informasi terhadap pengaktifan secara kompleks , pengaktifan
energi harus disamakan panjang ikatan Fe-C pada 2 ion. Sehingga panjang ikatannya
tersebut tidak terlalu berbeda , sedikit energi lepas pada pengaktifan yang dibutuhkan dan
penukaran tempat secara cepat. Kelambanan pertukaran antara [Co(NH3)6]2+ dan
[Co(NH3)6]3+ (k 10-8 M-1 s-1 pada 64o), sangat dapat timbul dari sedikit perbedaan panjang
ikatan Co-N. akan tetapi Co(III) ini secara kompleks memperlihatkan luas konfigurasi
elektron yang berbeda yaitu [Co(NH3)6]2+ dengan t2g5eg2 dimana [Co(NH3)6]3+ dengan t2g6,
disimpulkan bahwa perubahan terhadap penataan eletronik , pada penataan ulang , harus
terjadi sebelum elektron berpindah tempat. Pendapat dapat disampaikan ke sistem yang
terdapat pengubahan suatu kimia . Dan standar terhadap Pelepasan energi terhadap reaksi

negatif. Beberapa contoh kasus reorientasi koordinasi kulit memberi reaksi sedikit keras
karena getaran pembangkit energi terhadap 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. Pembebasan energy aktivasi akan berkurang dan kecepatan reaksi akan
meningkat. Tentunya reaksi oxsidasi-reduksi antara ion-ion logam yang berbeda (dimana
Go0) lebih cepat secara keseluruhan , daripada reaksi perubahan isotopik terhadap
reaktan yang lain. Jika intraksi orbital mencakup proses perpindahan elektron cukup besar
untuk memungkinkan terjadinya perpindahan electron tanpa hambatan cukup kecil untuk
diabaikan pada perhitungan terhadap pengaktifan pelepasan energi, sehingga aplikasi
hubungan sederhana antara kecepatan 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

suatu hubungan timbal balik yang ada dengan

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-

dan k11 dan k22 mengubah reaksi


[Fe(CN)6]4- + [Mo(CN)6]3-

[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

Maka
k12=(k11k22K12f)1/2

(3.1)

Dimana
Log f =

(log K12)2
4 log (k11k22/Z2)

Dan Z merupakan ukuran bilangan tubrukan yang terjadi antara dua jenis netral pada satuan
volume terhadap solusi pada satuan waktu yang berarti pemisahan jarak pada pengaktifan
kompleks.

Table 3.1 menunjukkan perbandingan antara kecepatan konstan yang diamati dan
perhitungan terhadap dasar kesetimbangan . (3,1). Dengan pengecualian system Co3+ + Fe2+
dan

[Co(NH3)6] + [Ru(NH3)6]2+ , terdapat persetujuan yang luar biasa antara hasil

eksperimen dan teori Marcus.


Tabel 3.1
Perbandingan pengamatan dan perhitungan laju konstan untuk beberapa reaksi transfer
electron bola luar pada suhu 25o.
-1 -1

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

*From N.Sutin, Proceedings of Symposium on Exchange Reactions, Brookhaven


National Laboratory, International Atomic Energy Agency, Vienna, 1965, and references
cited therein.
Calculated from k12=(k11k22K12f)1/2

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