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Handout14A-Oxi-RedTitra

# Handout14A-Oxi-RedTitra - CEM 834 OXIDATION–REDUCTION...

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CEM 834 OXIDATION–REDUCTION TITRATIONS FALL 2005 In an oxidation–reduction titration, a spontaneous electron transfer reaction occurs in homogeneous solution as the titrant is added. The potential is measured with an indicator electrode as a function of the volume of titrant. The overall cell potential (E cell ) is given by E cell = E ind – E ref + E J where E ind is the potential of the indicator electrode, E ref is the potential of the reference electrode, and E J is the junction potential. As E ref and E J are constant during the titration, the overall cell potential follows the potential of the indicator electrode. To calculate the titration curve, we will use the fraction titrated (Φ). For an oxidation–reduction reaction T 0 0 A CV n C V n      (1) where C 0 and V 0 are the concentration and volume of the analyte, C and V are the concentration and volume of the titrant, and n A and n T are the number of electrons transferred by the analyte and titrant, respectively. We will calculate the indicator electrode potential as a function of the fraction titrated throughout the oxidation–reduction titration. Consider the case where 100.0 mL of 0.100 M Fe 2+ is titrated with 0.100 M Ce 4+ in 0.1 M H 2 SO 4 at 25 ºC, as shown in the figure below.

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2 The overall reaction is Fe 2+ + Ce 4+ Fe 3+ + Ce 3+ (2) and the individual half reactions are Fe 3+ + e Fe 2+ / 3+ 2+ o Fe , Fe E = 0.68 V (3) Ce 4+ + e Ce
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Handout14A-Oxi-RedTitra - CEM 834 OXIDATION–REDUCTION...

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