1. 生物电分析化学 Electroanalytical Chemsitry and Its Biological Applications 刘宏 2015年秋

2. 课程目标
掌握核心概念和原理
具备在该领域的继续学习的能力

3. Syllabus 双语教学 不点名，作业不计分 开卷考试 教师邮箱: liuh@seu.edu.cn 答疑与讨论：河海院121室
课程网页:

4. 课程大纲 Overview of electrochemistry（电化学概论） Equilibrium (平衡)
Electrochemical Kinetics (电化学动力学)
Mass-transfer（传质）
Potential step/sweep techniques (电势阶跃/扫描技术)
Ultra-microelectrode (超微电极，UME)
Scanning electrochemical Microscope (扫描电化学显微镜，SECM)
Finite-element simulation of electrochemical processes (电化学过程的有限元模拟)
Applications：biomedical diagnostics， sensors, biofuel cell， brain research and single-cell studies（实际应用: 生物医学诊断、传感器、生物燃料电池、脑科学、单细胞研究）

5. Textbook Allen Bard 教授 2013美国国家科学奖章
巴德（Bard A.J.），福克纳（Faulkner L.R.）著，邵元华 等译
化学工业出版社

6. Electrochemistry
Electrochemistry is the study of chemical reactions which take place at the interface of an electrode, usually a solid metal or a semiconductor, and an ionic conductor, the electrolyte.
These reactions involve electric charges moving between the electrodes and the electrolyte (or ionic species in a solution). Thus electrochemistry deals with the interaction between electrical energy and chemical change.

7. Overview of electrochemistry
Electrochemical cell (electrolytic, galvanic)
Half cell and standard reduction potential
Nernst equation
Three-electrode cell
Potential step techniques (chronoamperometry, chronocoulometry)
Potential sweep techniques (LSV, CV)

8. Electrochemical parameters
Charge (q)
Potential (E)
Current (i)
Capacitance (C)
Resistance (R)
Conductance (G)

9. Electrochemical cell Spontaneous Non-spontaneous Generate power
Cell voltage > 0
Non-spontaneous
Consume power
Cell voltage < 0

10. Electrochemical cell Battery discharge: galvanic cell
Battery charge: electrolytic cell

11. Half Cell 1. E = 0.340 V 2. E = -0.763 V Cell voltage:
0.340 V - ( V) = V
thermodynamic, at standard conditions

12. Nernst Equation E0’ – standard reduction potential
R – gas constant R= (J/mol/K)
T- absolute temperature T= t (K)
n – electron transferred
F – Faraday constant F= (C/mol)
Co(x=0) – concentration of oxidized species
CR(x=0) – concentration of reduced species
X=0 means “on the electrode surface”

13. Electrochemical Cells
Two-electrode cell:
Three-electrode cell:
iR drop: EiRs= iRs
If Rs=100 Ω, i=1mA, EiRs= 0.1V

14. Reference Electrode
E0’= V vs. NHE

15. Faraday’s Law Faraday’s law: Nonfaradaic processes
charging/discharging
Faradaic processes
redox (reducing/oxidizing) events
n is number of moles (n = m/M)
t is the total time the constant current was applied.
z is the no. of electrons transferred.

16. Non-Faradaic Processes

17. Faradaic Processes

18. Electrochemical Kinetics

19. Mass Transfer Nernst-Plank Equation: Diffusion: Migration: Convection:
If the solution is kept still and excess supporting electrolyte (KCl or KNO3) is added to the solution, the contribution of convection and migration can be negligible .

20. Potential Step Techniques
CO* O R
Chronoamperometry：
CO(x=0)
O + ne R
Cottrell equation for a planar electrode:
DO： diffusion coefficient of O
CO： concentration of O

21. Potential Sweep Techniques

22. Non-Faradaic Processes
Potential Sweep：

23. Faradaic Processes

24. Assignment
Select two half cells listed in the table on Page 13 to construct (a) an electrolytic cell and (b) a galvanic cell. Write down the anodic, cathodic and overall reactions. Calculate the cell voltages at (a) standard conditions and (b) if the concentration of every solute is 1.00 mM.
Explain why we want to use a three electrode system in a potential-step experiment.
A 0.1 cm2 electrode with Cd=20 mF/cm2 is subjected to a potential step under conditions where Rs is 1, 10, 100 Ω. In each case, what is the time constant, and what is the time required for the double-layer charging to be 95% complete?
Consider the nernstian half-reaction:
the i-E curve for a solution at 25 0C containing 2.00 mM A3+ and 1.00 mM A+ in excess electrolyte shows il,c = 4.00 mA and il,a = mA. Sketch the i-E curve for this system.

25. Assignment