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Electrochemistrystudy of interchange of chemical and electrical energy

Generating electric current from spontaneous chemical reactions and use of current to produce chemical change Labs #31 The Thermodynamics of the Dissolution of Borax #33 Electrolytic Cells; Avogadros Number Chemical Equations Chapter 12

Oxidation-Reduction Reactions (Redox Reactions)


Oxidation: (LEO)
Loss of electrons-atoms or ions undergo increase in oxidation state (is oxidized) Electrons given to another atom which is being reduced (reducing agent or reductant) Reduction: (goes GER) Gain of electrons-atoms/ions undergo decrease in oxidation state (is reduced) Takes electrons away from another atom which is being oxidized (oxidizing agent or oxidant)
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Redox reaction can be written as two half-reactions (one reduction, one oxidation) To generate current Separate oxidizing agent from reducing agent Electron transfer occurs through wire Electron transfer directed through device to provide useful work Reactants separated by salt bridge/porous partition Each half-reaction has a potential, or voltage, associated with it Given as reduction half-reactions Read in reverse and change sign on voltage to get oxidation potentials
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Electrochemical cells device associated with redox reaction (galvanic cells, electrolytic cells)

Electrochemical process involves electron transfer at interface between electrode and solution
Species undergoing reduction receive electrons from cathode
Species in solution act as oxidizing agent

Species undergoing oxidation donate electrons to anode

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Species in solution act as reducing agent


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http://college.hmco.com/chemistry/shared/media/animations/anodereaction.html

http://college.hmco.com/chemistry/shared/media/animations/cathodereaction.html

Galvanic Cell (voltaic cell)



Chemical energy electrical energy Harnesses energy of spontaneous redox reactions Physically separate chemicals in 2 half-reactions
Electrons generated by oxidation half-reaction flow through electrical conductor before being used in reduction half-reaction Flow diverted through meters, motors, light bulbs to perform useful work before reaching destination Current (defined by physicists as flow of positive charge) always in opposite direction from flow of electrons (always from anode to cathode)
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Electrodes are metal strips


Sign of electrodes determined by
Since electrons flow out of anode and into external circuit, anode is negative Since electrons flow from external circuit into cathode, cathode is positive Opposite is true for electrolytic cells

Where reactions occur (The Red Cat ate An Ox)


Oxidation occurs at anode (AN OX)-on left Reduction occurs at cathode (RED CAT)-on right 4/7/2014 6

Porous barrier separate two compartments


Allows for migration of positive/negative ions between half-cells, completing electric circuit Problem with porous barriers
Inside barriers, ionic solutions mix Has effect on operation of cell
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http://college.hmco.com/chemistry/shared/media/animations/electrochemicalhalf.html

Galvanic cells with salt bridges


Inverted tube contains electrolyte Gel (agar) added to provides firmness but permits ion flow Prevents two reacting solutions from mixing Ions dont react with other ions in cell or with electrode material Maintains electrical neutrality in system Provides - ions to equal + ions created at anode (during oxidation) and + ions to replace - ions being used up at cathode (during reduction)
Anions always migrate toward anode Cations toward cathode

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Electron Flow

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The ANODE...

The CATHODE...

Supplies electrons to external circuit (wire) Is negative pole of battery Is site of OXIDATION Is written on left- hand side if convention is followed Is half-cell with lowest electrode potential

Accepts electrons from external circuit (wire) Is positive pole of battery Is site of REDUCTION Is written on right-hand side if convention is followed Is half-cell with highest electrode potential

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Cell Potential (Ecell) or Electromotive force (emf)


Force with which electrons flow from - electrode (anode on left) to + electrode (cathode on right) through external wire
Due to PE difference of electrons before/after transfer In electrochemical cell, electric potential created between two dissimilar metals Greater tendency or potential of two half-reactions to occur spontaneously, greater emf of cell 1 V = 1 J/coulomb (of charge transferred) Measured with voltmeter which draws current through known resistance (heat is produced)
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Measured in volts (V-why called cell voltage)



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Voltage of voltaic cells


All based on spontaneous chemical reactions G must always be negative Voltage of voltaic cell is always positive (+EMF) Subtract smaller reduction potential from larger one
Same as EMF = cathode anode

Under standard conditions, voltage of cell is same as total voltage of redox reaction
Standard emf of standard cell potential (E0cell)

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Under nonstandard conditions, cell voltage computed by using Nernst equation As galvanic cell operates
Redox reaction of cell approaches equilibrium Capacity to deliver useful electrical energy decreases At equilibrium, cell ceases to function (dead battery)

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Standard Reduction Potentials


Cell potentials can be measured Half-cell potential cannot
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Measuring Potential
Galvanic cell under standard conditions made using arbitrary standard hydrogen electrode (SHE) and test half-cell w/different half reaction
Assigned standard electrode potential of exactly 0.00 V
Under ideal conditions where ideal behavior is assumed

Half reaction always written as reduction


Eo values corresponding to reduction half-reactions with all solutes standard reduction potentials-Eocell
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Standard Reduction Potentials


All solutions are 1M, gases at 1 atm, T 25oC Write oxidation/reduction half-reactions for cell Look of reduction potential (Eoreduction) for reduction halfreaction in table Half reaction w/higher reduction potential Look of reduction potential for reverse of oxidation halfreaction and reverse sign (Eooxidation = -Eoreduction) Half reaction w/lower reduction potential/sign reversed Add potentials to get overall standard cell potential Two half reactions are balanced for # electrons exchanged but value of each Eo remains unchanged (intensive property-does not depend on how many times reaction occurs) If sum positive, reaction is spontaneous/runs on own (always positive for electrochemical cells) If sum negative, energy supplied to make reaction go
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Each half-reaction associated w/signed numerical value More positive it is, greater oxidizing power of redox half-reaction More negative it is, greater reducing power of reverse redox halfreaction Larger difference between Ered values, larger Ecell
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(1 atm)

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Line Notation

Anode written first on left/cathode on right


Reactants written 1st on each side

Vertical bar is boundary between two phases If both substances in same phase, separated by comma, not vertical bar Double line represents salt bridge or porous disk When platinum electrode present, placed at left and/or right end of cell diagram

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Using the table of standard reductions provided write the equation for the reaction between the following two half cells, and determine its voltage Au (s) | Au 3+ (aq) ||Cu 2+ (aq) | Cu (s) Gold is higher on table and written as found on table Au 3+ (aq) + 3 e - Au (s) Eo = + 1.50 V Copper is lower so it's written as oxidation (sign reversed) Cu (s) Cu 2+ (aq) + 2 eEo = -0.34 V Equation balanced for exchange of electrons (each needs 6) 2 Au 3+ (aq) + 6e - 2 Au (s) E = + 1.50 V 3 Cu (s) 3 Cu 2+ (aq) + 6e E = -0.34 V
*** Size of values for Eo of reactions not changed ***

Add two half reactions and E0 values 2 Au 3+ (aq) + 3 Cu (s) 2 Au (s) + 3 Cu 2+ (aq) E = + 1.50 V + ( - 0.34 V ) = 1.16 V
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Place the following in order of increasing strength as oxidizing agents:

-0.44

0.954

2.87

0.22

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Describe a galvanic cell based on the two half-reactions below:

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Homework:
Read 17.1-17.2, pp.827-837 Q pp. 867-869, #14 a/b/c/f/i/k, 16 a/b/d/f, 26a, 28 (a only), 30b, 32 (b only), 34a, 36b

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Cell Potential, Electrical Work, and Free Energy

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Complete Description of a Galvanic Cell

Electrical energy delivered by galvanic cell equal to quantity of useful work obtained as result of cell operation
Work, w, measured in relation to amount of charge, q, transferred between anode/cathode of cell This quantity, potential difference, E, is defined as E = w/q. SI unit is joule per coulomb or volt (V) Cell potential (always positive for galvanic cell)

Direction of electron flow (direction that yields + potential) Designation of anode/cathode Nature of each electrode/ions present in compartments
Chemically inert conductor (such as Pt) required if only ions are present (no substance in reaction is conducting solid)
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Electric work and cell potential


Free energy change occurring during chemical reaction is measure of maximum work that system can perform Potential (E) = -Work (w) / Charge (q)
So w = -qE Work leaving system has negative charge

Faraday (F) = charge in coulombs per mole of electrons (96,485 C/mol e-)
Then q = nF and w = -nFE n = number of moles of electrons
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G (Gibbs free energy) is measure of spontaneity of process occurring at constant T/P emf, E, of redox reaction also indicates whether reaction is spontaneous From thermodynamics we know that
G = U TS + (PV) and U = heat + w Therefore, at constant T/P: G = w Therefore: G = -nFE and at standard state: G0 = -nFE0 (relationship between emf/free energy changes )
Go = Standard Gibbs free energy change (kJ/mol or Joules) n = moles of electrons exchanged in reaction (mol) F = Faradays constant, 96,485 coulombs/mole (1 mole of electrons has a charge of 96,485 coulombs) Eo = Standard reaction potential (V or Joules/Coulomb)
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Since both n/F are +


+ value of E leads to value of G, which indicates spontaneous reaction

If G and E have opposite signs, E predicts direction of reaction


If Eo is positive, Go is negative (< 0)reaction spontaneous (has positive cell potentials) If Eo is negative, Go is positive (> 0)reaction is nonspontaneous (but is spontaneous in reverse direction)

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Relationship between thermodynamics (push behind electrons) and electrochemistry

Relationship between reaction potential and free energy for a redox reaction is given by
Emf = potential difference (V) = work (J) charge (C) Driving force (emf) is defined in terms of potential difference (in V) between two points in circuit One coulomb is amount of charge that moves past any given point in circuit when current of 1 ampere (amp) is supplied for one second (1 ampere = 1 coulomb/sec) Faradays law states that during electrolysis, passage of 1 faraday through circuit brings about oxidation of one equivalent weight of substance at one electrode (anode) and reduction of one equivalent weight at other electrode (cathode)
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emf is not converted to work with 100% efficiency


Energy always lost as heat, but wmax useful for calculating efficiency of conversion
wmax = -qEmax

Relationship to free energy (energy driving reaction due to movement of charged particles giving rise to potential difference)
wmax = EG EG = -qEmax = -nFEmax EG = -qEmax EG0 = -nFE0
When Ecell positive (spontaneous), EG will be negative (spontaneous), so there is agreement

Standard cell potential, Eocell, measured and standard electrode potential of test half-cell determined by using Eocell = Eocathode - Eoanode
Eocathode-standard reduction potential for reaction occurring at cathode, represents tendency to remove es from electrode surface Eoanode-standard reduction potential for reaction occurring at anode and represents its tendency to remove es from anode

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Dependence of Cell Potential on Concentration


Cell voltages at nonstandard concentrations (not 1 M)

Nernst Equationway to relate E0 at standard conditions and E, potential at any real condition

Standard state impossible to achieve in reality As soon as wire hooked to two half-cells, reaction proceeds and changes concentrations of all reactants and products Heating or cooling makes reaction deviate from standard temperature
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Calculating Nernst Equation


From thermodynamics, recall G = Go + RTlnQ If we divide everything by nF
since G = nFE, or E = G/(nF) Ecell = cell potential at non-standard conditions E0cell = standard reduction potential R = 8.314 J/molK (the gas constant) F = 96485 coul/mol (Faraday's constant) T = absolute temperature n = number of moles of electrons transferred in balanced equation Q = reaction quotient for reaction aA + bB cC + dD

Expressed in terms of base 10 rather than ln (standard conditions of 298K) Can be used to find cell potential at any set of conditions Cells spontaneously discharge until they achieve 37 equilibrium (at equilibrium, cell is dead) 4/7/2014

Consider the Daniell Cell at 25 C Zn(s) + Cu2+(aq) Cu(s) + Zn2+(aq)


Find cell potential at following conditions when [Cu2+] = 1.00 M, [Zn2+] = 1.0109 M and when [Cu2+] = 0.10 M, [Zn2+] = 0.90 M. Recall that standard potential for Daniell cell is Eo = +1.10 V Nernst equation used to find potentials at nonstandard conditions:
When [Cu2+] = 1.00 M, [Zn2+] = 1.0109 M

When [Cu2+] = 0.10 M, [Zn2+] = 0.90 M


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Depiction of concentration cell

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0.0592 E E logQ n

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Cell in which current flows due only to difference in concentration of ion in 2 different compartments of cell Le Chteliers principle used to determine effect on potential
Shift to left reduces potential Shift to right increases potential

If concentrations are different, stress is put on system that will be equalized by electron flow to allow reduction and oxidation to occur
Voltages typically small

When concentrations in half-cells become equal, E0cell = 0 and system is at equilibrium


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Calculate the EMF of the cell Zn(s) | Zn2+ (0.024 M) || Zn2+ (2.4 M) | Zn(s)
Zn2+ (2.4 M) + 2 e = Zn Reduction Zn = Zn2+ (0.024 M) + 2 e Oxidation Zn2+ (2.4 M) = Zn2+ (0.024 M), DE = 0.00 Using Nernst equation:
(0.024) DE = 0.00 - 0.0592/2 log (0.024/(2.4) = (-0.296)(-2.0) = 0.0592 V
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Show that voltage of electric cell is unaffected by multiplying reaction equation by positive number Mg | Mg2+ || Ag+ | Ag Mg + 2 Ag+ = Mg2+ + 2 Ag
DE = DEo 0.0592/2 log [Mg2+]/[Ag+]2

2 Mg + 4 Ag+ = 2 Mg2+ + 4 Ag
DE = DEo 0.0592/4 log [Mg2+]2/[Ag+]4 Simplified to the 1st equation, showing cell potential DE not affected

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The standard reaction potential is related to the equilibrium constant At equilibrium, Ecell = 0 and Q = K

Calculation of Equilibrium Constants for Redox Reactions


As cells discharge, concentration changes, Ecell changes.

For a cell at concentrations and conditions other than standard, a potential can be calculated using the Nernst equation
If Eo is positive, then K > 1 and forward reaction favored If Eo is negative, then K < 1 and reverse reaction is favored

nE log( K ) at 25 C 0.0592

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The standard cell potential dE for the reaction Fe + Zn2+ = Zn + Fe2+ is -0.353 V. If a piece of iron is placed in a 1 M Zn2+ solution, what is the equilibrium concentration of Fe2+?

Equilibrium constant K may be calculated using K = 10(n DE)/0.0592 = 10-11.93 = 1.2x10-12 = [Fe2+]/[Zn2+]. Since [Zn2+] = 1 M, it is evident that [Fe2+] = 1.2-12 M
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Homework:
Read 17.3-17.4, pp. 837-846 Q pp. 869-871, #38, 40, 46, 48, 54, 60, 66, 70

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Batteries

Portable, self-contained electrochemical power source (DC) consisting of one or more voltaic cells, connected in series Greater voltages achieved by using multiple voltaic cells in single battery (12V) When connected in series, battery produces voltage that is sum of emfs of individual cells Higher emfs achieved by using multiple batteries in series Electrodes marked + (cathode) and (anode)

Lead-acid storage battery


As battery discharged, uses up sulfate ions/electrodes become coated w/lead sulfate Reverse reactions regenerate sulfate ion in solution/reduce amount of lead sulfate contaminating electrode surfaces Each pair produces ~2 volts (6 pairs of electrodes used in 12-volt car battery) When jump starting car, connect ground cable on dead car to metallic contact away from battery. Otherwise, could explode Causes electrolysis of water/production of H2/O2 which could ignite
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Common Dry Cell Battery (acid version)

Zinc-anode Carbon rod in contact with moist paste-cathode

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Alkaline dry cell


NH4Cl replaced w/KOH or NaOH Last longer than acid cells because zinc (anode) corrodes more slowly in basic environment Cathode (graphite rod) inserted into paste made of manganese dioxide, water and potassium hydroxide Zn(s) + 2OH-(aq) ZnO(s) + H2O + 2e- (anode) 2MnO2(s) + H2O + 2e- Mn2O3(s) + 2OH-(aq) (cathode) Total voltage is 1.54 volts Not rechargeable

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Mercury Battery

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Fuel Cells

Galvanic cells where reactants continuously supplied Energy normally lost as heat is captured and used to produce an electric current Redox reaction
Hydrogen oxidized at anode and oxygen reduced at cathode to form water and electricity 2x as effective as gas, oil or coal-powered generators in converting chemical energy into electricity
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Type of Battery
Lead acid

Advantages
Rechargeable Long life 12 V Inexpensive No toxic metals used Lots of power (1.5 V down to 1.2 V) Lightweight Higher capacity (3.6-3.9 V) Rechargeable Longer lasting Less likely to leak/explode

Disadvantages
Heavy Contain acid Weather issues Heavier

Alkaline/Dry cell

Lithium (solid state)

Expensive

Fuel cells

No recharging No harmful pollutants


Fast/simple charge (rechargeable) High # charges 1.2 V continuously

high initial cost Fuel not readily available Toxic metals Expensive

Nickel-Cadmium (Ni-Cd)

Mercury
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More constant voltage (1.35 V) Longer life Lighter

More expensive
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Corrosion oxidation of metal


Oxidation of most metals by oxygen is spontaneous redox reactions Many metals develop thin coating of metal oxide on outside that prevents further oxidation Some metals, such as copper, gold, silver and platinum (noble metals), are relatively difficult to oxidize

Corrosion of Iron
Anodic regions Regions of steel alloy where iron is more easily oxidized Fe Fe2+ + 2eCathodic regions Areas resistant to oxidation Electrons flow from anodic regions & react w/oxygen O2 + 2H2O + 4e- 4OHPresence of water essential to iron corrosion Presence of salt accelerates corrosion by increasing electron conduction from anodic to cathodic regions
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Prevention of Corrosion

Coating w/metal that forms oxide coat to protect metal that would not develop protective coat Galvanizing
Place sacrificial of more easily oxidized metal on top of metal to protect
Zinc over iron

Alloying
Addition of metals that change steels reduction potential.
Nickel and chromium alloyed to iron

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Cathodic Protection
Connection of easily oxidized metals (an anode) to less easily oxidized metals keeps less from experiencing corrosion Anode corrodes-must be replaced periodically
Magnesium as anode to iron pipe Titanium as anode to steel ships hull

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Electrolysis
Decomposition of substance by electric current
Galvanic Cell Electrolytic Cell

Cathode + (reduction) - (reduction) Anode - (oxidation) + (oxidation)

http://www.infoplease.com/chemistry/simlab/electrolpt3.html

Electrolytic cells

Nonspontaneous reactions Electrical energy required to induce reaction


Two electrodes immersed in electrically conductive sample Electrical voltage (>1.10 V) applied to them Voltage increased until electrons flow in opposite direction (electrolytic) At cathode-reduction occurs (RED CAT) At anode-oxidation occurs (AN OX)

Electrical energy is converted into chemical energy Electrolytic cells are used for electroplating
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(a) Standard galvanic cell based on spontaneous reaction Zn + Cu2+ Zn2+ + Cu (b) Standard electrolytic cell: Power source forces opposite reaction Cu + Zn2+ Cu2+ + Zn

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What voltage is necessary to force the following electrolysis reaction to occur?


2I-(aq) + Cu2+(aq) I2(s) + Cu(s)
Which process would occur at the anode? Cathode? Assuming the iodine oxidation takes place at a platinum electrode, what is the direction of electron flow in this cell?

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Calculating Quantity of Substance Produced or Consumed


To determine quantity of substance either produced or consumed during electrolysis given time known current flowed
Write balanced half-reactions involved Calculate number of moles of electrons that were transferred Calculate number of moles of substance that was produced/consumed at electrode Convert moles of substance to desired units of measure 70

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A 40.0 amp current flowed through molten iron(III) chloride for 10.0 hours (36,000 s). Determine the mass of iron and the volume of chlorine gas (measured at 25oC and 1 atm) that is produced during this time.

Write half-reactions that take place at anode/cathode


anode (oxidation): 2 Cl- Cl2(g) + 2 e cathode (reduction) Fe3+ + 3 e- Fe(s)

Calculate number of moles of electrons Calculate moles of iron/chlorine produced using number of moles of electrons calculated and stoichiometries from balanced half-reactions. (3 moles electrons produce 1 mole of Fe/2 moles of electrons produce 1 mole of chlorine gas)

Calculate mass of iron using molar mass and calculate volume of chlorine gas using ideal gas law (PV = nRT).
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Calculating Time Required


To determine quantity of time required to produce known quantity of substance given amount of current that flowed
Find quantity of substance produced/consumed in moles Write balanced half-reaction involved Calculate number of moles of electrons required Convert moles of electrons into coulombs Calculate time required
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How long must a 20.0 amp current flow through a solution of ZnSO4 in order to produce 25.00 g of Zn metal
Convert mass of Zn produced into moles using molar mass of Zn Write the half-reaction for the production of Zn at the cathode Zn2+(aq) + 2 e- Zn(s) Calculate moles of e- required to produce moles of Zn using stoichiometry of the balanced half-reaction (2 moles of electrons produce 1 mole of zinc) Convert moles of electrons into coulombs of charge using Faraday's constant Calculate time using current and coulombs of charge
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Calculating Current Required


To determine amount of current necessary to produce known quantity of substance in given amount of time
Find quantity of substance produced/or consumed in moles Write equation for half-reaction taking place Calculate number of moles of electrons required Convert moles of electrons into coulombs of charge Calculate current required 74 4/7/2014

What current is required to produce 400.0 L of hydrogen gas, measured at STP, from the electrolysis of water in 1 hour (3600 s)? Calculate number of moles of H2 Write equation for half-reaction that takes place. Hydrogen produced during reduction of water at cathode. Equation for this half-reaction is 4 e- + 4 H2O(l) 2 H2(g) + 4 OH-(aq) Calculate number of moles of electrons (4 mole of erequired to produce 2 moles of hydrogen gas, or 2 moles of e-'s for every one mole of hydrogen gas) Convert moles of electrons into coulombs of charge Calculate current required
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How many grams of copper can be reduced by applying a 3.00 A current for 16.2 min to a solution containing Cu2+ ions?

Time current Coulombs moles e- moles Cu g Cu


16.2 min 60 sec 3 C 1 mol e- 1 mol Cu 63.54 g Cu = 1 min 1 sec 96,486 C 2 mol e- 1 mol Cu 0.96 g Cu

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Electrolysis can be used to separate mixture of ions, if reduction potentials are fairly far apart

Remember, metal ion with highest reduction potential is easiest to reduce Predict order of reduction and which of following ions will reduce first at cathode of electrolytic cell: Ag+, Zn2+, IO3-

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Electroplating
Deposit neutral metal atoms on electrode by reducing metal ions in solution
One metal coated with another

Presence of active electrode that takes part in electrolysis reaction


Anode-piece of plating metal Cathode-object to be plated Plating solution is NiSO4 because SO42- ion does not participate in plating reaction
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How long must a current of 5.00 A be applied to a solution of Ag+ to produce 10.5 g silver metal?

10.5 g Ag 1 mol Ag 1 mol e- 96,485 C 1 sec 1 min = 107.868 g Ag 1 mol Ag 1 mol e- 5 C 60 sec 31.3 min

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http://college.hmco.com/chemistry/shared/media/animations/electrolysisofwater.html

Electrolysis of Water
Requires soluble salt/dilute acid to serve as electrolyte

Anode
2H2O(l) O2(g) + 4H+(aq) + 4eEoox = -1.23 V

Cathode
2H2O(l) H2(g) + 2OH-(aq) Eored = -0.83 V


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Overall reaction
6H2O(l) 2 H2(g) + O2(g) + 4H+(aq) + 4e- Eocell = -2.06 V If in single container, H+/OHcombine to yield 4 additional water molecules

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What volume of H2(g) and O2(g) is produced by electrolyzing water at a current of 4.00 A for 12.0 minutes (assuming ideal conditions)?

2H2O(l) 2H2(g) + O2(g) Actual ratio is not exactly 2:1 for a variety of reasons including oxygen solubility.
12 min 60 sec 4 C 1 mol e- 1 mol H2 22.4 L = 1 min 1 sec 96,486 C 2 mol e- 1 mol H2 0.334 L H2 0.167 L O2

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Electrolysis of molten salts

NaCl
Good conductor as liquid Melting salt frees ions Makes it electrically conductive

Ions of opposite charge migrate to these electrodes and react


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Electrolysis of aqueous solutions


Aqueous solutions of salts are electrically conductive and can be electrolyzed For solutions, two possible reactions occur (water can be both oxidized and reduced)
At cathode

If metal ion is very active metal, water will be reduced (2H2O + 2e- H2 + 2OH-) If metal ion is inactive or active metal, metal ion will be reduced
Oxidation of salts anion or () Oxidation of water (2H2O O2 + 4H+ + 4e-)

At anode

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To determine which will occur at anode


If anion is polyatomic ion, it generally will not be oxidized
SO42-/NO3-/ClO4- not oxidized in aqueous solution Cl-/Br-/l- will be oxidized in aqueous solution

If anion in one salt is oxidized in aqueous electrolysis, that same anion in any other salt will also be oxidized
If solution of NaBr results in Br- being oxidized to Br2, predict that solutions of KBr, CaBr2, NH4Br and AlBr3 will all produce Br2 at anode

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Commercial Electrolytic Processes


Abundance of elements on earth: 1st Oxygen 2nd Silicon 3rd Aluminum (very active metal so difficult and expensive originally to purify)

Since metals are easily oxidized, most found as ores, mixtures of ionic compounds. Au, Ag, and Pt are more difficult to oxidize, so often found as pure metals.

Production of aluminum from molten-salt electrolysis


(purification of aluminum from bauxite ore)

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Hall-Heroult process

Electrorefining (purifying) metals


Copper ore is refined by roasting Impure copper is anode Small strip pure copper is cathode During electrolysis, copper is oxidized to Cu2+ at anode and then reduced to copper metal again at cathode Impurities such as silver and gold drop to bottom as sludge which is then salvaged

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Metal Plating
Electroplating thin layers of decorative metal on less expensive metal (silver and gold onto iron, chromium on to car parts for decoration and resistance to corrosion)

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Electrolysis of concentrated aqueous sodium chloride solutions (brine) produces hydrogen and hydroxide ions at cathode and chlorine gas at anode If electrodes separated by porous membrane, H2, NaOH, and Cl2 produced If solution stirred, chlorine gas reacts with sodium hydroxide to form sodium hypochlorite (NaOCl) solution (bleach) Electrolysis of molten NaCl produces sodium metal and chlorine gas (Downs cell)
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Homework:
Read 17.5-17.8, pp. 846-866 Q pp. 871-872, #74, 76, 78, 80, 84, 88 a (dont forget water) Do 1 additional exercise and 1 challenge problem Submit quizzes by email to me: http://www.cengage.com/chemistry/book_content/05471253 21_zumdahl/ace/launch_ace.html?folder_path=/chemistry /book_content/0547125321_zumdahl/ace&layer=act&src= ch17_ace1.xml http://www.cengage.com/chemistry/book_content/05471253 21_zumdahl/ace/launch_ace.html?folder_path=/chemistry /book_content/0547125321_zumdahl/ace&layer=act&src= ch17_ace2.xml http://www.cengage.com/chemistry/book_content/05471253 21_zumdahl/ace/launch_ace.html?folder_path=/chemistry /book_content/0547125321_zumdahl/ace&layer=act&src= 4/7/2014 90 ch17_ace3.xml