Oxidation- Reduction Reactions Oxidation and Reduction - Oxidation loss of electrons - Reduction gain of electrons - Oxidizing agent causes

oxidation and is reduced - Reducing agent causes reduction and is oxidized - OIL RIG Assigning Oxidation Numbers - Oxidation numbers are assigned to atoms to keep track of the redistribution of electrons during chemical reactions - Rules o Oxidation free elements (not in compound) is 0 o Oxidation number of monoatomic ion equal to its charge o Oxidation number Group IA = 1 o Oxidation number Group 2A = 2 o Oxidation number Group 7A = -1 unless combined with more electronegative element, then = +1 o Oxidation number hydrogen = -1 with less electronegative o Oxidation number oxygen -2, except with more electronegative atom (e.g F), then +2 o Oxidation number of all in compound = to neutral or charge Balancing Redox Reactions - Method is half reaction method o Separate the 2 half reactions o Balance all except for H and O o Add H2O to balance O o Add H+ to blance H o Balance charges with eo Add half reactions, confirm all balanced Electrochemical Cells - 3 Types of Electrochemical Cells o Galvanic/ Voltaic Cel o Electrolytic o Concentration Cells - Oxidation occurs at anode, reduction occurs at cathode - Movement of electrons: Anode to Cathode, Current: Cathode to Anode - Galvanic/ Voltaic Cells o Redox reaction gives off energy, and reaction is spontaneous (-deltaG) o Made of half-cells connected by a conductive material Separation of oxidation and reduction reactions o If it was only connected by a wire, charge would accumulate and provide counter voltage large enough to prevent redox reaction from taking place Hence, salt bridge dissipates counter charge gradient

o Cell Diagram Zn | Zn2+ (xM SO42-) || CU2+ (yM SO42-)| Cu Single line = phase boundary, Double line =barrier (Salt bridge) Electrolytic Cells o Opposite of galvanic cells in almost all characteristic and behavior o Nonspotaneous reactions, positive Gibbs, driven by external voltage o Drives oxidation at the anode, reduction at the cathode Michael Faraday o Number of moles exchanged can be determined from balanced half reaction o Faraday charge = 96487 C/mol eConcentration Cells o Similar to galvanic cell properties, except electrodes are chemically identical (e.g both are copper) o Current generated as function of a concentration gradient of solutions that results in a potential difference driving movement of electrons o Current ceases when concentrations of ion species in half cells are equal Electrode Charge Designation o Galvanic Cell Anode: Negative Electrode (Source of electrons) Cathode: Positive Electrodes Therefore electrons flow from negative to positive (low to high potential) and current flows positive to negative (high to low potential) o Electrolytic Cell Anode: Positive (Because it is attached to positive pole of external voltage source) Cathode: Negative (attached to negative pole external voltage) o Both types of cells Oxidation takes place at anode, attracts anions Reduction at cathode, attracts cation

Reduction Potentials and the Electromotive Force Reduction Potential - Measured in Volts (V) and defined relative to standard hydrogen electrode (SHE) - Standard Reduction Potential (Ered0) o Measure of tendency of species to be reduced o Higher Ered means greater relative tendency for reduction to occur o Lower Ered means greater relative tendency for oxidation to occur o Tie it to Ered = oxidation/ reduction, which = cathode/ anode Electromotive Force - Used to calculate the standard electromotive force (emf/ E0cell) - emf = Ecath Eanode = Ered + Eox o Do not multiply by number of moles oxidized or reduced

Standard emf galvanic cell positive, standard emf electrolytic cell negative

Thermodynamics of Redox Reactions emf and Gibbs Free Energy - G = -nFEcell o n= number moles electrons exchanged, F= Faradays, Ecell = emf cell - If reaction under standard conditions (298 K, 1 atm pressure, 1 M) o G0 = -nFE0cell - Negative sign helps eliminate answers Effect of concentration on emf - Determined using the Nerst Equation o Ecell = E0cell (RT/nF)(ln Q) o Whereby Q is reaction quotient of reaction at given time Given aA + bB cC + dD Q = {[C]c[D]d}/{[A]a[B]b} Emf and the Equilibrium Constant (Keq) G0 = - RT lnKeq (R = 8.314 J/(K*mol)) - Therefore nFE0cell = RTlnKeq o Keq less than 1, then ln is negative and therefore Ecell negative o Keq mor than 1, then ln positive and therefore Ecell positive

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