February 28, 2014

Ch. 17: Electrochemistry Remember: LEO the lion goes GER. Review Redox reactions from Ch 4. Especially oxidation numbers. Oxidation Rduction

the loss of e- by a substance

--e- are a product

gain of e-s by an element --e-s are a reactant

Reducing Agent --substance that supplies the e- to the substance that gains e- and is oxidized Oxidizing Agent --substance that accepts e-; this is the substance that is reduced

Oxidation number --number assigned to each element in a compound in order to keep track of the e- during a chemical rxn

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Half-reactionReview Balancing of redox reactions using half- reactions ---each half-rxn is balanced for mass and for charge Steps in balancing: 1. Recognize the rxn as redox 2. separate into half rxns 3. balance each half rxn for mass--balance atoms --add H+ and H2O or OH- and H2O 4. balance each half rxn for charge-----add electrons 5. multiply each half rxn by an appropriate factor to balance e- lost and gained in each half rxn. 6. Add half rxn together to produce an overall balanced equation (e- should drop out) 7. check overall rxn.

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Cr2+ +

I2

Cr3+

I1-

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Co(s) +

NO31-

Co3+

NO2(g)

(in acid)

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Al(s) +

S(s)

Al(OH)3(s) + HS1- (in base)

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Problems 14 and 15:

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17.1 Galvanic Cells A battery is an electrochemical cell or a collection of such cells that produces a current, or flow of electrons, at a constant voltage as result of an electron transfer. Many metals are purified or prepared by electrolysis. Use electrical energy to produce a chemical change. Electrodeconducts e-s into an out of a soln Anodeterminal at which oxidation occurs (negative terminal) Cathode- terminal at which reduction occurs (positive terminal) Salt bridgeallows for the movement of ions (maintains a balance of ion charges)

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--Look at diagram on page 793/794Label diagram using this rxn:

Zn(s) + Cu2+(aq)
eee-

Cu(s)

Zn2+(aq)
ee-

Anode

Cathode
Reducing agent

Oxidizing agent
Salt bridge
Zn2+ SO42-

Cu2+
SO42-

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Example: Sketch the galvanic cell for the following redox reaction and label: anode, cathode, reducing agent, oxidizing agent, identify solution in each side and direction of the electron flow
Ni(s) + 2 Ag+ (aq)
ee-

Ni2+(aq) +
e
-

2 Ag(s)
ee-

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Standard conditions--when reactants and products are present in pure solids or in soln (1M) or gases at 1 barr

Standard electrode potential, E

**product-favored electrochemical rxns have positive values for E

Ecell = Ecathode -

Eanode

A cell will run spontaneously in a direction that produces a positive cell potential

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Dependence of Cell Potentials on Concentration Just as acid-base reactions always move in the direction of the weaker acid-base pair, redox reactions move toward the direction the weaker oxidizing agent/ reducing agent pair. When using Table 17.1(pg 796), the table of standard reduction potentials (E), the half-reactions are always written in the following form: Oxidized form + n eCu2+ (aq) + 2 eCu(s) Reduced form E = +0.34 V

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Calculating the potential E of an electrochemical cell Example: Page 797 Anode, oxidation: 3 (Mg Mg 2+ + 2e-) -E (anode) = -(-2.37V) = 2.37 V Cathode, reduction: 2 (Al3+ + 3 eNet process: 2 Al3+ + 3 Mg Al ) E (cathode) = -1.66 V

3 Mg 2+ + Al

Ecell = -1.66 V + 2.37 V = 0.71 V --chart page796 --potentials for isolated half-rxns cannot be measured directly because the potential measures the potential nrg difference for e-s in 2 different chemical environments

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Important points concerning cell potentials 1. All reactions are written: Oxidized form + n e All potentials are for reduction reactions 2. When writing the reaction: Reduced form E is reversed. 3. All half reactions are reversible
-

Reduced form Oxidized form + n e , the sign of

-

4. The more positive value for E, the better the oxidizing ability of the substance on the left side of the reaction. 5. The more negative value of E, the less likely the reaction will occur as a reduction and the more likely that the reverse reaction (oxidation) occurs. 6. The reaction between anything substance on the left side of table (oxidizing agent) with any substance lower than it on the right side (reducing agent) is product favored under standard conditions. 7. The algebraic sign of the half-reaction potential is the sign of the electrode when it is attached to the H /H O standard cell.
2 3 +

8. Electrochemical potentials depend on the nature of the reactants and products and their conc, not on the quantities of materials used. Changing the coefficients for a half reaction does not change the value of E.

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Line Notation: Way of representing the reaction of a galvanic cell

indicates phase change

Mg(s)

Mg2+(aq)

Al3+(aq)

Al(s)

Anode (oxidation rxn)

Cathode (reduction rxn)

written left side

salt bridge

written right side

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Balance this redox rxn; calculate cell potential;and write line notation

Fe2+(aq) + MnO41-(aq) + H+(aq)

Mn2+(aq) + Fe(s) + H2O(l)

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Electrochemical cells and potentials

Electrons generated at the site of oxidation are driven toward the cathode by an electromotive force or emf

--emf is due to differences in electric potential nrg of the e- at the 2 electrodes

--quantity of electric work done is proportional to the # of ethat go from higher to lower potential nrg and to the size of the potential nrg difference

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electric work = charge x potential nrg difference

charge is measured in coulombs (C)

Coulombs (C) = quantity of charge that passes a point in an electrical circuit when a current of 1 amp flows for 1 sec

volt = 1 joule / 1 coulomb

Work (J) = 1 volt x 1 coulomb

1 e- has an electric charge of 1.6022 x 10-19 C

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--maximum work that can be accomplished by an electrochemical cell and the charge passing thru the circuit
--cell potential depends in turn on the substances that make up the cell, whether they are gases or solutes in sol'n, and on their con'c

--quantity of charge depends on the quantity of reactants consumed

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E and

Grxn = -nFE F = Faraday constant = 9.6485 x 104 J/V mole Zn + Cu2+ Zn2+ + Cu E = +1.10 V Grxn)

--product-favored rxn have a negative free nrg change (