电化学原理简介及其於材料腐蚀之应用(2005-11-04).ppt

電化學原理簡介及 其於材料腐蝕之應用 研一課 鄭勝元 2005/11/09 * * Introduction to Electrochemical Theory and Its Application to the Corrosion of Materials Content Theory: Electrode Potential Thermodynamics Electrochemical Kinetics of Corrosion Mixed Potential Theory Electrochemical Instrument and Experimental Setup Application: DC (potentiodynamic, potentiostitic, C-V curve,...) AC Impedance Conclusions (○) Fe → Fe 2+ + 2e- 2H+ + 2e- → H2 Overall reaction: Fe(s) + 2H+(aq) → Fe2+(aq) + H2(g) ….△G, △E (×) Fe2+ + 3(OH)- → Fe(OH)3……..Ksp What is electrochemical reaction ? Zn Cu V, A Electrode - - - - - - First row (Water Dipole) IHP Second row Solved Ion OHP Double layer Capacity - - - - + + + + Potential Distance Second row Solved Ion OHP IHP: Inner Helmholty plane OHP: Outer Helmholty plane Electrode potential Standard Electromotive Force Potentials (Reduction Potentials) Reaction Standard potential, e0 (volts vs. SHE) Noble Active Au3+ + 3e- = Au + 1.498 Cl2 + 2e- = 2Cl- + 1.358 ………………… ………………… Fe3+ + e- = Fe2+ + 0.771 ………………… Cu2+ + 2e- = Cu + 0.342 2H+ + 2e- = H2 0 Pb2+ + 2e- = Pb - 0.126 ………………… Fe2+ + 2e- = Fe - 0.447 Cr3+ + 3e- = Cr - 0.744 Zn2+ + 2e- = Zn - 0.762 ………………… ………………… Al3+ + 3e- = Al - 1.662 K+ + e- = K - 2.931 Activity: K＞ Na＞ Ca ＞ Mg ＞ Al ＞ Zn ＞ Fe ＞ Sn ＞ Pb ＞ H2 ＞ Cu ＞ Hg ＞ Ag ＞ Pt ＞ Au aA + mH+ + ne- → bB +dH2O △G = G0 + RTln( ) …..(1), △G = -nEF …..(2) (Nernst equation) pH E H2O H2 O2 H+ OH- 4OH- → 2H2O + O2 + 4 e- E = E0 O2/H2O - 0.059 pH 2H2O + 2e- → H2 + 2OH- E = E0 H+/H2 - 0.059 pH Thermodynamics Pourbaix diagram pH E Al (Immunity) Al2O3 Passivity Al3+ Corro