REVIEW of Electrochemistry Lecture 04

I. Introduction A. Terms
Electrochemistry - deals with the relationship of chemical reactions and electricity.

Redox Reactions - Chemical reactions which involve a transfer of electrons.

Electrochemical Cell - a system consisting of electrodes that dip into an electrolyte in which a reaction either generates or uses an electric current. Cell 1: Voltaic Cell - An electrochemical cell in which a spontaneous reaction generates an electric current. Cell 2: Electrolytic Cell - An electrochemical cell in which an electric current forces a reaction to occur.

I. Introduction

B. review - Redox Reactions

- Two General Classes of Chemical Reactions: Redox & Non-Redox - Redox reactions = ones in which electrons are transferred & two processes are associated with redox reactions: 1) Electrolysis: Electricity forces a chemical reaction to occur. Example: 2 H2O + electricity 2 H2(g) + O2(g)

2) A Voltaic Cell (battery): spontaneous redox reaction generates electrical potential. Example (1 M Cu+2 and Zn+2) Zno + Cu+2 Zn+2 + Cuo + electricity
(1.1 volts)

B. Review - Redox Reactions - Oxidation = loss of electrons. Know - Reduction = gain of electrons. Know - Both must occur together, but we frequently break them up into two half reactions. Example: Zno + Cu+2 -----) Zn+2 + Cuo

Oxidn: Zno -----) Zn+2 + 2 eRedn: Cu+2 + 2 e- -----) Cuo

a) Oxidizing Agent causes oxidn. & is reduced b) Reducing Agent causes redn. & is oxidized - Classes of Redox Reactions: Displacement, Combustion (Cu2+) (Zno)

Combination, Decomposition,

B. Review - Oxidation Numbers (ON)

Definition: The charge that an atom (or group of atoms) would have if it were ionic Usefulness: 1) Naming variably charged compounds. Example: FeCl3 = Iron(III)chloride 2) Determining if a reaction is redox. 3) Balancing a redox reaction.

Rules for Determining ON: Note - priority of rules are important; lowest # rule takes precedent when a conflict occurs. Know Rules

B. Review - Oxidation Numbers (ON). Rules

1) The sum of ONs must add up to give the charge

2) The ON of a neutral element by itself is 0

3) Group I, II, III elements in ionic form are +1, +2 & +3 respectively (H -1 when combined with Ia, IIa, IIIa) 4) F is -1 5) O is -2 (O is -1 when found as a peroxide, O2-2)

6) Cl, Br, I are -1 (when together, most electronegative rules)

B. Review of ON Examples: Determine the ON of single N in each: (Treat as a Quiz & Complete in < 5 minutes) N2 N3-1 NH3 0 -1/3 -3 N2O NO +1 +2 NF3 N2O4 NO3-1 +3 +4 +5

- 1) Which one would be most reactive and why?

- 2) Ethanol/Nitric Acid experience in the lab.

- 3) HClO4 - What is ON of Cl? Comments on perchloric acid.

B. Review ON Examples
- The top two are redox: 1) 2) 3) Mg + Cl2 CH4 + 2 O2 HCl + NaOH MgCl2 CO2 + 2 H2O H2O + NaCl

In any redox reaction you should be able to determine: The ON for each element Which reagent has been oxidized Which reagent has been reduced Which reagent is the oxidizing agent Which reagent is the reducing agent What are the two half reactions for each How many moles of e- are transferred in each half rxn

II. Balancing Redox Rxns A. acidic media

Many are difficult and require a systematic method: Note that you must first determine if the reaction occurs in acid or base.

Steps: 1-3 for acidic media & Steps 1-6 for basic media 1. Assign ONs & split into two half reactions 2. Complete & balance each half reaction: a. balance atom undergoing redox b. balance O by adding H2Os c. balance H by adding H+s d. balance ionic charge by adding e-s 3. Combine half reactions and finish (if in acidic media): a. multiply each half reaction by integer to cancel e-s. b. add & simplify by canceling same species on both sides.

II. Balancing Redox Rxns B. Basic media

4. If in basic media add OH- equal to # H+ to both sides.

5. Convert H+ & OH- on same side to H2O & simplify by canceling H2O if needed. 6. Check result by noting if following are both balanced: elements & charge.

II. Balancing Redox Rxns

C. Example 1 in acid

Zn + NO3- + H+ -----) Zn+2 + NH4+ + H2O

1)

Zn -----) Zn2+ NO3- -----) NH4+

0 ---) +2 on Zn (Oxidn.) +5 ---) -3 on N (Redn.)

2)

Zn -----) Zn2+ + 2 e(balance redox atom) NO3- -----) NH4+ + 3 H2O (balance O with H2O) 10 H+ + NO3- -----) NH4+ + 3 H2O (balance H with H+ ) 10 H+ + NO3- + 8 e------) NH4+ + 3 H2O (bal. Charge w e-)

3) 4 [Zn -----) Zn2+ + 2 e-] (8e- lost) 1 [10 H+ + NO3- + 8 e------) NH4+ + 3 H2O] (8e- gained) 4 Zn + 10 H+ + NO3- + 8 e----) 4 Zn2+ + 8 e- + NH4+ + 3 H2O 4 Zn + 10 H+ + NO3- -----) 4 Zn2+ + NH4+ + 3 H2O

II. Balancing Redox Rxns C. Example 2 (basic) Pb(OH)3- + ClO- -----) PbO2 + Cl1) ClO- -----) ClPb(OH)3- -----) PbO2 +1 ---) -1 on Cl +2 ---) +4 on Pb (oxn) (rdn)

2)

2 H+ + ClO- + 2 e- -----) Cl- + H2O Pb(OH)3- -----) PbO2 + H2O + H+ + 2e-

3) 2H+ + ClO- + Pb(OH)3- + 2e- -----) Cl- + 2H2O + H+ + PbO2 + 2eH+ + ClO- + Pb(OH)3- -----) Cl- + 2H2O + PbO2 4) OH- + H+ + ClO- + Pb(OH)3- ---) Cl- + 2H2O + PbO2 + OH5) H2O + ClO- + Pb(OH)3- ---) Cl- + 2 H2O + PbO2 + OH6) ClO- + Pb(OH)3-

Cl- + H2O + PbO2 + OH-

II. Balancing Redox Rxns C. Example 3 MnO4- + S2O32- -----) Mn2+ + SO42- (acidic)

1)

a) MnO4- ----) Mn2+ b) S2O32- ----) SO42-

[+7 ---) +2 Redn] [+4 ---) +6 per S Oxn] (x 8)

2) a) 5e- + 8H+ + MnO4- ----) Mn2+ + 4H2O

b) 1S2O32- -----) 2SO425H2O + S2O32- -----) 2SO42- + 10H+ 5H2O + S2O32- -----) 2SO42- + 10H+ + 8e3)

(x 5)

40e- + 64H+ + 8MnO4- + 25H2O + 5S2O32- ---) 8Mn2+ + 32H2O + 10SO42- + 50H+ + 40e-

14 H+ + 8 MnO4- + 5 S2O32- ----) 8 Mn2+ + 7 H2O + 10 SO42-

II. Balancing Redox Rxns C. Example 4 MnO4- + I- -----) MnO2 + IO3- (basic)

1) MnO4- -----) MnO2 +7 ---) +4 Mn I- -----) IO3-1 ----) +5 I 2) 4H+ + MnO4- + 3e- -----) MnO2 + 2H2O 3H2O + I- -----) IO3- + 6H+ + 6e3) 2 [4H+ + MnO4- + 3e- -----) MnO2 + 2H2O] 1 [3H2O + I- -----) IO3- + 6H+ + 6e-]
8H+ + 2MnO4- + 6e- + 3H2O + I- ----) 2MnO2 + 4H2O + IO3- + 6H+ + 6e2H+ + 2MnO4- + I- ----) 2MnO2 + H2O + IO3-

4) 2OH- + 2H+ + 2MnO4- + I- ----) 2MnO2 + H2O + IO3- + 2OH5) 2H2O + 2MnO4- + I- ----) 2MnO2 + H2O + IO3- + 2OHH2O + 2MnO4- + I- ----) 2MnO2 + IO3- + 2OH6) Double check balancing of atoms & charge.

III. Voltaic Cells

A. Introduction - A voltaic cell (battery) is an electrochemical cell in which a spontaneous redox reaction generates an electric current. - It consists of two half cells which are connected: Oxidation half cell consists of electrode (anode = - ) & electrolyte. Reduction half cell consists of electrode (cathode = + ) & electrolyte. Internal connection of a salt bridge that allows the flow of ions but prevents mixing of electrolytes from two half cells. External connection of anode to the cathode. Electrons travel from anode to cathode.

B. Example
Zn + Cu2+ -----) Zn2+ + Cu Anode Zn ---) Zn2+ + 2eCathode + Cu2+ + 2e- ---) Cu

Zn | Zn2+ (1.0 M) || Cu2+(1.0 M) | Cu

C. Voltaic Cell Shorthand Notation same example: Zn+2 & Cu2+ at 1.0 M
Zn + Cu2+ -----) Zn2+ + Cu

Zn | Zn2+ (1.0 M) || Cu2+(1.0 M) | Cu

Anode (-) (oxidation) Cathode (+) (reduction) Know the following Conventions: Anode written on left Cathode written on right | = phase boundary || = salt bridge Zn = anode electrode Cu = cathode electrode , = separates different ions in the same half cell M = Molar concentration of ions Zn ---) Zn2+ + 2eCu2+ + 2e- ---) Cu

This battery develops 1.1 volts at 25 oC

C. Voltaic Cell Notation (ions at 0.1 M)

Cd + 2Ag+ -----) Cd2+ + 2Ag Anode Cd ---) Cd2+ + 2eCathode + 2Ag+ + 2e- ---) 2Ag Cd | Cd2+ (0.1 M) || Ag+ (0.1M) | Ag (this cell develops 1.2v)

C. Voltaic Cell Notation Additional Examples

Pt | H2 | H+|| (Half Cell) Hydrogen electrode as anode (electrode on left) H2 -----) 2H+ + 2 eThree phases: Pt solid, H2 gas, H+ solution Cathode Reaction Fe3+ + e- -----) Fe2+ (electrode on right)

||Fe3+, Fe2+ | Pt

||Cd2+ | Cd

Cathode Reaction Cd2+ + 2e- ------) Cd

(electrode on right)

Tl | Tl+ || Sn2+ | Sn

2 Tl + Sn2+ -----) 2 Tl+ + Sn 2 Tl ----) 2 Tl+ + 2 e(anode) Sn2+ + 2e- ---) Sn (cathode)

D. Work & Voltage of a Cell

Much of the early work on cell physics & chemistry came from Michael Faraday - 1791 to 1867 He was responsible for uncovering ONs, terminology (anode, cathode, etc), benzene, electromagnetism, Faradays Laws & Faradays constant. 1 Faraday = Charge on 1 mole of electrons = 96,500 c.

D. Work & Voltage of a Cell Work done in a redox rxn = G = - n x F x Ecell

n= moles of e- transferred Ecell = voltage of the cell F = Charge of 1 mole of e- = 1 Faraday = 96,485 coulombs

Notes:
o Units: Joules = moles x (coul/mole) x volts = coul x volt = J o 1 coulomb x 1 volt = 1 joule o Since batteries are spontaneous redox rxns the sign is -: G = - nFEcell

Free Energy, G = maximum useful work done

G = - nFEcell At 1M concentrations, 1 atm pressure & 25 oC: G = Go Go = - nFEocell

E. Standard Cell Voltages - some notes

- Can measure the [cell voltage or potential or electromotive force (EMF)] using a voltmeter; and can calculate theoretical voltages from equations & tables. - The voltage (E) developed by a cell is the sum of the oxidation and reduction potentials: Ecell = Eoxidation + Ereduction (note: you supply signs) - Note: cant separate the two half reactions in the lab; so, how calculate E r & O? By setting an arbitrary standard and comparing all other half cell reactions to this standard. - Arbitrary Standard is the hydrogen half cell reduction under standard conditions (1 M, 1 atm, 25oC) ; a voltage of 0.000 was assigned.

E. Standard Cell Voltages || H+ (1.0 M) | H2 (1.0 atm) | Pt 2H+ + 2eH2

H2 Electrode

Eo = 0.0000 volts at 25 oC (1 M HCl & 1 atm H2)

E. Standard Cell Voltages

- If we couple the hydrogen electrode under standard conditions with another half reaction and measure the Ecell , then we can determine the E for the unknown half reaction.

Eocell = Eohalf reaction + Eohydrogen electrode = Eohalf reaction + 0.000

Eocell = Eohalf reaction under standard conditions

- Example:

Zn | Zn2+ (1.00M) || H+ (1.00M) | H2 (1.00atm) | Pt

Zn + 2H+ Zn2+ + H2 Eocell measured as 0.76 volts

Eocell = EoZn + EoH2 = EoZn + 0.000;

EoZn = Eocell = 0.76 v 19.1,

Notes: 1) Convention: Half reactions are written as reductions. See Table pg 786; if need half reaction as oxidn, then reverse the sign. 2) Eo1/2 value is the same regardless of #e- transferred = constant.

E. Standard Cell Voltages Calculate Eocell Eo cell = Eo reduction + Eo oxidation Use Table 19.1 & must change sign for oxidation. Example: I2 + 2Li -----) 2Li+ + 2ITable values: 2Li+ + 2e- ---) 2Li Eo = -3.04 v
I2 + 2e- -----) 2IEo = 0.54 v

What is Eocell?

Eocell = 3.58 v (reverse Li1/2 rxn)

Li Iodine battery can reverse the rxn by adding electricity to recharge battery

E. Standard Cell Voltages Use of Standard Cell Voltages (table 19.1, pg 786) 1) Can tell strength of reducing/oxidizing agents: Reaction with largest + volts wants to go most 2) Can determine the Eocell from Standard Cell Voltages: Eocell = Eo reduction + Eo oxidation 3) Can tell which way a redox rxn wants to go: Will spontaneously go such that Ecell is largest 4) Can be used to calculate G: 5) Can be used to calculate Keq:
Go = - nFEocell Eo = (2.30 RT / nF) Log K

6) Used to calculate Ecell not under std conditions.

F. Calculations Involving Eo
1) Can tell strength of reducing/oxidizing agents: Reaction with largest + Eo1/2 value wants to go most Mg2+ + 2e- ---) Mg Eo1/2 = -2.4 F2 + 2e- ---) 2FEo1/2 = 2.9 F2 wants to be reduced more than Mg+2 2) Can determine the Eocell from Standard Cell Voltages: Given: Al | Al3+ || Cr3+ | Cr (Direction mandated by convention) Al ---) Al3+ + 3e- Eo = 1.66 v Cr3+ + 3e- ----) Cr Eo = - 0.74 V Eocell = Eoox + Eored = 1.66 + (-0.74) = 0.92 V 3) Can tell which way a redox reaction will spontaneously go. Goes such that Eocell is the largest positive value. Zn2+ + Cu ---) Zn + Cu2+ Zn + Cu2+ ---) Zn2+ + Cu Eo = - 1.10 v Eo = + 1.10 v = Not Spontaneous = Spontaneous

F. Calculations Involving Eo
4) Free Energy from Eo Go = - nFEocell & Eo from Go Eo cell = -Go/nF
Zn | Zn2+ (1.0M) || Ag+(1.0M) | Ag

Example: Calculate the Go in J for: Zn + 2Ag+ ----) 2Ag + Zn2+ Zno -----) Zn+2 + 2e2Ag+1 + 2e- -----) 2Ago Eo = 0.76 + 0.80 = 1.56 v

Eo1/2 = +0.76 v Eo1/2 = +0.80 v

Note: 2 m of e- transferred, but Eo1/2 = 0.80v for Ag (Eocell is a constant)

Go = - nFEocell = - 2.00m x 9.65x104c/m x 1.56v = - 3.01x105 J

Example: Calculate Eo for a rxn in which Go = -409 kJ & n=2 Eo = -Go/nF = - (-409x103J) / (2m x 9.65x104c/m) = 2.12 J/c = 2.12 v
(1 coulomb x 1 volt = 1 joule; 1 volt = 1 joule/coulomb)

F. Calculations Involving Eo

5) Get Keq from Eo

Go = - nFEo

&

Go = - RTLn K (from last chapter)

-nFEo = - 2.30 RT Log K

- nFEo = - RT Ln K

Eo = (2.30 RT / nF) Log K

@ 298 K (25 oC) 2.30RT/F = 0.0592 V

Eo = (0.0592) Log Keq n

Example: Calc K at 25oC for Zn + Cu2+

(true at 25 oC)

Zn2+ + Cu

Eo = 1.10 V

Eo = (0.0592) Log K n
Log K = 37.2

1.10 = (0.0592) Log K 2

K = 1037.2 K = 1.58 x 1037

F. Calculations Involving Eo
6) Cell EMF for Nonstandard Conditions From: Get: (not 1 M or not 25 0C) G = - nFE & G = Go + RT Ln Q (last chapter) E = Eo - RT/nF Ln Q = Eo - 2.30RT/nF Log Q

E = Eo - 0.0592/n Log Q

at 25 oC = Nerst Equation

(know)

- Can now calculate E at various temperatures & concentrations. - n = # moles of electrons in the balanced redox reaction - Q = same form as Keq except initial M used - not equilibrium concentrations. Example: Calculate E at 25 oC for

Zn | Zn2+(1.00x10-5) || Cu2+(0.100) | Cu Eo = 1.10 V

Zn (s) + Cu2+ (------) Zn2+ + Cu (s)

Q = [Zn2+]/[Cu2+] =

1.00x10-5 M / 0.100 M

1.00x10-4

E = Eo - 0.0592/n Log Q = 1.10 - 0.0592/2 Log (1.00x10-4) E = 1.10 - (-0.12) = 1.22 V

IV. Electrolytic Cells, Examples

- Place inert electrodes in a solution and force a non-spontaneous redox rxn to occur by running electricity through the solution with a battery = electrolysis.

1. Molten NaCl

- at cathode: 2Na+ + 2e- ---) 2Na - at anode: 2Cl- ---) Cl2 + 2e2NaCl(s) + elec. -----) 2Na(s) + Cl2 (g)

2. Aqueous NaCl - at cathode: 2H2O + 2e- ---) H2 + 2OH- at anode: 2Cl- ---) Cl2 + 2e2H2O + 2Cl- + elec. -----) H2 + 2OH- + Cl2 3. Water + non reacting Electrolyte (like Na2SO4) - at cathode: 4H2O + 4e- -----) 2H2(g) + 4OH- at anode: 2H2O -----) 4e- + 4H+ + 1O2(g) 2H2O + elec. ----) 2H2(g) + 1O2(g)

IV. Electrolytic Cells

Electroplating - process of depositing a metal on an electrode. Can be used for analysis, beauty, or for protective coating. - Can be used for quantitative analysis:

Example: Analysis of Cu in brass (mix of Sn, Pb, Cu)

Dissolve brass in HNO3; add two Pt electrodes to the HNO3 solution; apply > +0.34 volts. Cu forms at the cathode: Cu2+ + 2e ----) Cuo Sn+2 Eo = -0.14 v Pb+2 Eo = -0.13 v Cu+2 Eo = +0.34 v

Weigh the cathode before and after the process to quantitatively determine the amount of Cu in the brass.

- Note: 1. Can predict what will form at electrodes from knowing the ions in the solution & from a table of Eo values; the metal ion with the largest + reduction potential will plate out on the cathode first. 2. Can also determine amount of Cu by measuring current (amps) and time necessary to plate out all of the Cu (see next section).

IV. Electrolytic Cells - Stoichiometry

- Note that electrolysis can be used for stoichiometric calculations. - Equations and values to know: c = a x sec a= c/sec coulombs = amperes x seconds

1F = Charge on 1 mole of e- = 96500 c

Example: How many g of Cu are present in the previous example if a current of 0.852 amp is needed for 600 seconds in order to remove all of the blue color? 1Cu+2 + 2e- ------) 1Cu(s) c = a x s = 0.852 a x 600 s = 511 coulombs 511 c x 1 mole e- x 96500 c 1 mole Cu x 63.5 g Cu = 0.168 g Cu 2 mole e1 mole Cu

- Note: Can also weigh a Pt cathode before & after; would gain 0.168 g.

V. More Applications of Electrochemistry

pH Electrode: Ecell = Ereference electrode + Eindicator electrode

V. Few More Applications of Electrochemistry

pH electrode:
AgCl(s) + H+Inside (---) Ag(s) + H+outside + Cl-

[Cl-] = 1 M n = 1 [H+Inside ] = constant Ecell = Eo - (0.0592/n) Log Q = Eo - 0.0592 Log {[H+out ]x[Cl-] / [H+Ins ]} Ecell = K - 0.0592 Log [H+out ] = K + 0.0592 pH Ecell = 0.0592 pH + K [1) Eqn a pH meter uses; 2) a plot of voltage vs pH will be a straight line with a slope of 0.0592; 3) when calibrating a pH meter, you are setting the slope = 0.0592 and the Y intercept = K ] Other Ion Specific Electrodes - Example: Fluoride Specific Electrode typical F- ISE (ion-selective electrode) LaF3 Crystal - Potential developed across membrane Et = Constant - 0.0592 Log F(at 25oC) F F F F Note the potential interferences from the F lab.
F- F-

V. Few More Applications of Electrochemistry

Electrochemical Detectors for Liquid Chromatography - Control the voltage of an electrode system in an LC mobile phase. If compound of interest goes past the cell & can be oxidized at the selected voltage, then will get a current which is proportional to the concentration of the compound. Can detect pg amounts of chemicals.

V. More Applications of Electrochemistry

Batteries Example: Car Battery Pb + HSO4- -----) PbSO4 + H+ + 2ePbO2 + 3H+ + HSO4- + 2e- -----) PbSO4 + 2H2O

PbO2 + Pb + 2H+ + 2HSO4- (-----) 2 PbSO4 + 2H2O

One cell develops 2 V; so, a six cell battery connected in series will develop 12 Volts