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Predicting the direction of redox reactions Know that standard electrode potentials can be listed as an electrochemical series. Use E values to predict the direction of simple redox reactions and to calculate the e.m.f. of a cell.
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GOLDEN RULE The more +ve electrode gains electrons (+ charge attracts electrons)
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Electrodes with negative emf are better at releasing electrons (better reducing agents).
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–+0 – 0.76 V –ve electrode Zn 2+ + 2 e - Zn + 0.34 V +ve electrode Cu 2+ + 2 e - Cu + 1.10 V e–e– Cu 2+ + Zn → Cu + Zn 2+
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USE OF Eo VALUES - WILL IT WORK? E° values Can be used to predict the feasibility of redox and cell reactions In theory ANY REDOX REACTION WITH A POSITIVE E° VALUE WILL WORK An equation with a more positive E° value reverse a less positive one
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USE OF Eo VALUES - WILL IT WORK? What happens if an Sn(s) / Sn2+(aq) and a Cu(s) / Cu2+(aq) cell are connected? Write out the equationsCu2+(aq) + 2e¯ Cu(s) ; E° = +0.34V Sn2+(aq) + 2e¯ Sn(s) ; E° = -0.14V the half reaction with the more positive E° value is more likely to work it gets the electrons by reversing the half reaction with the lower E° value therefore Cu2+(aq) ——> Cu(s) and Sn(s) ——> Sn2+(aq) the overall reaction isCu2+(aq) + Sn(s) ——> Sn2+(aq) + Cu(s) the cell voltage is the difference in E° values... (+0.34) - (-0.14) = + 0.48V An equation with a more positive E° value reverse a less positive one
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USE OF Eo VALUES - WILL IT WORK? An equation with a more positive E° value reverse a less positive one Will this reaction be spontaneous? Sn(s) + Cu2+(aq) ——> Sn2+(aq) + Cu(s) Write out the appropriate equations Cu2+(aq) + 2e¯ Cu(s) ; E° = +0.34V as reductions with their E° values Sn2+(aq) + 2e¯ Sn(s) ; E° = - 0.14V The reaction which takes place will involve the more positive one reversing the other i.e.Cu2+(aq) ——> Cu(s) and Sn(s) ——> Sn2+(aq) The cell voltage will be the difference in E° values and will be positive... (+0.34) - (- 0.14) = + 0.48V If this is the equation you want then it will be spontaneous If it is the opposite equation (going the other way) it will not be spontaneous
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USE OF Eo VALUES - WILL IT WORK? An equation with a more positive E° value reverse a less positive one Will this reaction be spontaneous? Sn(s) + Cu2+(aq) ——> Sn2+(aq) + Cu(s) Split equation into two half equationsCu2+(aq) + 2e¯ ——> Cu(s) Sn(s) ——> Sn2+(aq) + 2e¯ Find the electrode potentialsCu2+(aq) + 2e¯ Cu(s); E° = +0.34V and the usual equationsSn2+(aq) + 2e¯ Sn(s); E° = - 0.14V Reverse one equation and its signSn(s) ——> Sn2+(aq) + 2e¯ ; E° = +0.14V Combine the two half equationsSn(s) + Cu2+(aq) ——> Sn2+(aq) + Cu(s) Add the two numerical values(+0.34V) + (+ 0.14V) = +0.48V If the value is positive the reaction will be spontaneous
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Predicting redox reactions 5.3 exercise 2
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–+0 – 0.76 V –ve electrode Zn 2+ + 2 e - Zn – 0.25 V +ve electrode Ni 2+ + 2 e - Ni + 0.51 V e–e– Ni 2+ + Zn → Ni + Zn 2+ PREDICTING REDOX REACTIONS – Q1
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+ 0 + 0.34 V –ve electrode Cu 2+ + 2 e - Cu + 0.80 V +ve electrode Ag + + e - Ag + 0.46 V e–e– 2 Ag + + Cu → 2 Ag + Cu 2+ PREDICTING REDOX REACTIONS – Q2
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0 – 2.36 V –ve electrode Mg 2+ + 2 e - Mg – 0.26 V +ve electrode V 3+ + e - V 2+ + 2.10 V e–e– Mg(s)|Mg 2+ (aq)||V 3+ (aq),V 2+ (aq)|Pt(s) PREDICTING REDOX REACTIONS – Q3 a – YES: Mg reduces V 3+ to V 2+
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0 + 0.77 V –ve electrode Fe 3+ + e - Fe 2+ + 1.36 V +ve electrode Cl 2 + 2 e - 2 Cl - + 0.59 V e–e– PREDICTING REDOX REACTIONS – Q3 b + NO: Cl - won’t reduce Fe 3+ to Fe 2+
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0 + 1.09 V –ve electrode + 1.36 V +ve electrode Cl 2 + 2 e - 2 Cl - + 0.27 V e–e– PREDICTING REDOX REACTIONS – Q3 c + YES: Cl 2 oxidises Br - to Br 2 Br 2 + 2 e - 2 Br - Pt(s)|Br - (aq),Br 2 (aq)||Cl 2 (g)|Cl - (aq)|Pt(s)
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0 – 0.14 V –ve electrode Sn 2+ + 2 e - Sn + 0.77 V +ve electrode Fe 3+ + e - Fe 2+ + 0.91 V e–e– PREDICTING REDOX REACTIONS – Q3 d – YES: Sn reduces Fe 3+ to Fe 2+ + Sn(s)|Sn 2+ (aq)||Fe 3+ (aq),Fe 2+ (aq)|Pt(s)
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0 + 1.33 V –ve electrode Cr 2 O 7 2- + 14 H + + 6 e - 2 Cr 3+ + 7 H 2 O + 1.36 V +ve electrode Cl 2 + 2 e - 2 Cl - + 0.03 V e–e– PREDICTING REDOX REACTIONS – Q3 e + NO: H + /Cr 2 O 7 2- won’t oxidise Cl - to Cl 2
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0 + 1.36 V –ve electrode MnO 4 - + 8 H + + 5 e - Mn 2+ + 4 H 2 O + 1.51 V +ve electrode Cl 2 + 2 e - 2 Cl - + 0.03 V e–e– PREDICTING REDOX REACTIONS – Q3 f + YES: H + /MnO 4 - oxidises Cl - to Cl 2 Pt(s)|Cl - (aq)|Cl 2 (g)||MnO 4 - (aq),H + (aq),Mn 2+ (aq)|Pt(s)
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0 – 0.44 V –ve electrode Fe 2+ + 2 e - Fe 0.00 V +ve electrode 2 H + + 2 e - H 2 + 0.44 V e–e– PREDICTING REDOX REACTIONS – Q3 g – YES: H + oxidises Fe to Fe 2+ Fe(s)|Fe 2+ (aq)||H + (aq)|H 2 (g)|Pt(s)
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0 0.00 V –ve electrode Cu 2+ + 2 e - Cu + 0.34 V +ve electrode 2 H + + 2 e - H 2 + 0.34 V e–e– PREDICTING REDOX REACTIONS – Q3 h + NO: H + won’t oxidise Cu to Cu 2+
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0 + 1.36 V MnO 4 - + 8 H + + 5 e - Mn 2+ + 4 H 2 O + 1.51 V Cl 2 + 2 e - 2 Cl - PREDICTING REDOX REACTIONS – Q4 + + 1.33 V Cr 2 O 7 2- + 14 H + + 6 e - 2 Cr 3+ + 7 H 2 O + 0.77 V Fe 3+ + e - Fe 2+ YES NO
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+ 0 ? V –ve electrode Be 2+ + 2 e - Be + 0.34 V +ve electrode Cu 2+ + 2 e - Cu + 2.19 V e–e– Be 2+ + Cu → Be + Cu 2+ PREDICTING REDOX REACTIONS – Q5a 2.19 = 0.34 - E left E left = 0.34 – 2.19 = – 1.85 V
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– 0 ? V –ve electrode Th 4+ + 4 e - Th + 0.00 V +ve electrode 1.90 V e–e– 4 H + + Th → 2 H 2 + Th 4+ PREDICTING REDOX REACTIONS – Q5b When using SHE E = cell emf = – 1.90 V 2 H + + 2 e - H 2
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0 0.00 V –ve electrode + 1.09 V +ve electrode + 1.09 V e–e– PREDICTING REDOX REACTIONS – Q6a + Br 2 + 2 e - 2 Br - Pt(s)|H 2 (g)|H + (aq)||Br 2 (aq),Br - (aq)|Pt(s) 2 H + + 2 e - H 2 H 2 + Br 2 → 2 H + + 2 Br -
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0 + 0.34 V –ve electrode + 0.77 V +ve electrode + 0.43 V e–e– PREDICTING REDOX REACTIONS – Q6b + Fe 3+ + e - Fe 2+ Cu(s)|Cu 2+ (aq)||Fe 3+ (aq),Fe 2+ (aq)|Pt(s) Cu 2+ + 2 e - Cu 2 Fe 3+ + Cu → 2 Fe 2+ + Cu 2+
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