物理化学研究方法30.pptVIP

Cyclic voltammetry Nernstian (reversible) systems Peak current is linear with square root of scan rate No effects of scan rate on peak potential Reductive peak current is equal to oxidative peak current Value of peak potential difference is 58 mV/n Peak current and scan rate At 25℃, ip is Totally irreversible systems Scan rate In LSV, the potential is scanned from a lower limit to an upper limit Unit of scan rate(υ): V/s or mV/s Effects of scan rate on charging current: Differential Pulse Voltammetry/Polarography Differential Pulse Voltammetry/Polarography Sampled Current Polarography Sampled Current Polarography Sampled Current Polarography Potential step Concentration profiles for various times into the experiment Potential step under diffusion control Cottrell equation: Instrumental and experimental limitations: (1) Potentiostatic limitations, (2) limitations in the recording device, (3) limitations imposed by Ru and Cd, (4) limitations due to convection: the available “time window” for Cottrell measurements lies approximately between 20 μsec and 200 sec. Chronocoulometry At t=0, the potential is shifted to E2, which is sufficiently negative to enforce a diffusion-limited current. The following equation describes the chronocoulometric response: Effects of the additional components on chronocoulometric response Where Qdl is the capacitive charge and nFAΓquantifies the faradaic component given to the reduction of Γof adsorbed species: Bulk electrolysis methods The bulk electrolytic methods are characterized by large A/V conditions and as effective mass transfer conditions as possible. Current efficiency: Current Step When the RsCd circuit is charged by a constant current i, for a current step, assuming a constant Cd, the potential increases linearly with time. Sand equation The measured value of τat known i can be used to determine C* or D. A lack of constancy of the transition time constant, iτ1/2/C*, with i or C* indicates complications