The Kinetics of the Redox Reaction of Platinum(IV) Ions with Ascorbic Acid in the Presence of Oxygen
Abstract
:1. Introduction
2. Materials and Methods
2.1. Reagents
2.2. Methods of Analysis
3. Results and Discussion
3.1. Experimental Conditions
3.2. Spectra of Reagents
3.3. Kinetic Curves Determination and Proposed Mechanism
3.4. Stoichiometry
3.5. The Dependency of kobs vs. Initial Concentration of the Reductant
3.6. The Influence of Temperature on Second-Order Rate Constant
3.7. The Influence of pH
3.8. The Influence of Ionic Strength
3.9. The Influence of Chloride Concentration
3.10. The Role of Oxygen Dissolved in Aqueous Solution in the Reduction Process
3.11. Mechanism Description
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Initial Concentration of Reagents | Ionic Strength | T | pH | |
---|---|---|---|---|
C0,Pt(IV), mM | C0,H2Asc, M | I, M | K | |
The stoichiometry | ||||
C0,H2Asc:C0,Pt(IV) 0.25 0.33 0.5 0.75 1 2 4 6 | 0.10 | 313 | 2.50 | |
Dependency of kobs vs. initial reductant concentration | ||||
1.00 | 0.04 | 0.40 | 313 | 2.50 |
0.05 | ||||
0.06 | ||||
0.07 | ||||
0.08 | ||||
0.10 | ||||
The influence of temperature | ||||
1.00 | 0.06 | 0.06 | 287 | 2.50 |
298 | ||||
303 | ||||
308 | ||||
313 | ||||
The influence of pH | ||||
1.00 | 0.06 | 0.06 | 313 | 2.15 2.50 |
3.65 | ||||
4.17 | ||||
5.04 | ||||
The influence of ionic strength (addition of NaClO4) on the rate constants | ||||
1.00 | 0.06 | 0.00 0.05 0.10 0.20 0.30 0.40 | 313 | 2.50 |
The influence of chloride ions on the rate constants (at constant value of [Na+] = 0.4 M) | ||||
1.00 | 0.06 | 0.4 | 313 | NaCl addition 0.00 0.05 0.10 0.20 0.30 0.40 |
, mM | s−1 | k1 M−1s−1 | s−1 | M−1s−1 |
---|---|---|---|---|
40 | 23.49 ± 0.79 | 3.91 ± 0.13 | 4.25 ± 0.19 | 7.08 ± 0.32 |
50 | 26.32 ± 0.40 | 4.38 ± 0.07 | 4.22 ± 0.04 | 7.04 ± 0.37 |
60 | 30.49 ± 0.40 | 5.08 ± 0.07 | 3.89 ± 0.22 | 6.48 ± 0.40 |
70 | 39.06 ± 0.32 | 5.51 ± 0.05 | 3.51 ± 0.24 | 5.85 ± 0.40 |
80 | 42.37 ± 0.30 | 7.06 ± 0.05 | 3.61 ± 0.23 | 6.02 ± 0.38 |
100 | 50.00 ± 0.20 | 8.33 ± 0.03 | 3.97 ± 0.16 | 6.61 ± 0.27 |
ln A | [M−1s−1] | EA/R |
EA |
---|---|---|---|
21.7 | 26 | 6587 | 54 |
ΔH/(R) | ΔH± [kJ × mol−1] | (23.77 + Δs/R) | ∆S± [J × K−1 × mol−1] |
---|---|---|---|
6279 | 52 | 15 | −73 |
pH | s−1 | s−1 |
---|---|---|
2.15 ± 0.05 | 10.86 ± 0.06 | 1.20 ± 0.06 |
2.50 ± 0.05 | 16.76 ± 0.22 | 0.66 ± 0.18 |
3.65 ± 0.05 | 62.89 ± 1.02 | 62.89± 0.18 |
4.17 ± 0.05 | 89.28 ± 0.03 | - |
5.04 ± 0.05 | 105.2 ± 0.10 | - |
I M | s−1 | s−1 |
---|---|---|
0.00 | 17.45 ± 0.06 | 3.30 ± 0.02 |
0.05 | 25.00 ± 0.02 | 2.11 ± 0.05 |
0.10 | 27.78 ± 0.02 | 2.36 ± 0.03 |
0.20 | 29.76 ± 0.02 | 3.44 ± 0.05 |
0.30 | 29.82 ± 1.31 | 3.52 ± 0.19 |
0.40 | 30.49 ± 0.40 | 3.89 ± 0.22 |
[Cl−] M | s−1 | k1 M−1s−1 | s−1 | M−1s−1 |
---|---|---|---|---|
0.00 | 30.48 ± 0.40 | 5.08 | 3.89 ± 0.05 | 6.48 |
0.05 | 39.06 ± 0.30 | 6.51 | 4.41 ± 0.03 | 7.34 |
0.10 | 35.84 ± 0.39 | 5.97 | 4.52 ± 0.05 | 7.54 |
0.20 | 37.45 ± 0.10 | 6.24 | 5.21 ± 0.06 | 8.68 |
0.30 | 40.32 ± 0.20 | 6.72 | 5.57 ± 0.06 | 9.41 |
0.40 | 40.65 ± 0.20 | 6.77 | 5.41 ± 0.10 | 9.01 |
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Luty-Błocho, M.; Szot, A.; Hessel, V.; Fitzner, K. The Kinetics of the Redox Reaction of Platinum(IV) Ions with Ascorbic Acid in the Presence of Oxygen. Materials 2023, 16, 4630. https://doi.org/10.3390/ma16134630
Luty-Błocho M, Szot A, Hessel V, Fitzner K. The Kinetics of the Redox Reaction of Platinum(IV) Ions with Ascorbic Acid in the Presence of Oxygen. Materials. 2023; 16(13):4630. https://doi.org/10.3390/ma16134630
Chicago/Turabian StyleLuty-Błocho, Magdalena, Aleksandra Szot, Volker Hessel, and Krzysztof Fitzner. 2023. "The Kinetics of the Redox Reaction of Platinum(IV) Ions with Ascorbic Acid in the Presence of Oxygen" Materials 16, no. 13: 4630. https://doi.org/10.3390/ma16134630