Two Types of Chemical Rxns

1. Exchange of Ions no change in charge/oxidation numbers

Oxidation/Reduction
Chapter 20

Acid/Base Rxns NaOH + HCl

Two Types of Chemical Rxns

Precipitation Rxns Pb(NO3)2(aq) + KI(aq)

Two Types of Chemical Rxns

2. Exchange of Electrons changes in oxidation numbers/charges Fe(s) + CuSO4(aq) FeSO4(aq) + Cu(s) Remove spectator ions Fe + Cu2+ Fe2+ + Cu Protons Electrons

Dissolving Rxns CaCl2(s)

Review of Oxidation Numbers

Oxidation numbers the charge on an ion or an assigned charge on an atom. Al Cl2 P4 Mg2+ Cl-

Review of Oxidation Numbers

Calculate the oxidation numbers for:

HClO S8 Mn2O3 KMnO4 HSO4-

Cr3+ Fe2(SO4)3 SO32NO3-

Oxidation
1. Classical Definition addition of oxygen 2. Modern Definition an increase in oxidation number Fe + O2 Fe2O3 CO + O2 CO2 CH3CH2OH CH3CHO CH3COOH

Oxidation

Fe + O2

(limited oxygen)

Fe + O2

(excess oxygen)

Oxidation

Reduction
1. Classical addition of hydrogen 2. Modern decrease (reduction) in oxidation number N2 + 3H2 2NH3 (Haber process) R-C=C-R + H2 | | H H (unsaturated fat)

C + O2

(limited oxygen)

C + O2

(excess oxygen)

(saturated fat)

Oxidizing/Reducing Agents
Oxidation and Reduction always occur together. Oxidizing Agents
Get reduced Gain electrons

Oxidizing/Reducing Agents
0 Got oxidized, reducing agent Cu + O2 0 +2 CuO -2

Got reduced, oxidizing agent

Reducing Agents
Get oxidized Lose electrons

Identify the Oxidizing/Reducing Agents in the following (Calculate the ox. numbers also). Cu + S8 Cu2S H2 + O2 H2O Cu + AgNO3 Cu(NO3)2 + Ag H2O + Al + MnO4- Al(OH)4- + MnO2

Balancing Redox Reactions

Half-Reaction Method Break eqn into oxidation half and reduction half Easy Examples:
Al + Fe2+ Fe + Al3+ Cu + Zn2+ Cu2+ + Zn Mg + Na+ Mg2+ + Na

Balancing Redox Reactions

Whats really happening: Cu2+ + Zn Cu + Zn2+

Balancing Redox Reactions

Steps for more complicated examples 1. Balance all atoms except H and O 2. Balance charge with electrons 3. Balance O with water 4. Balance H with H+ =================================== 5. (Add OH- to make water in basic solutions)

Balancing Redox Reactions

Example 1: MnO4- + C2O42- Mn2+ + CO2 1. Separate into half reactions MnO4- Mn2+ C2O42- CO2

Balancing Redox Reactions

MnO4- Mn2+ +7 +2 5e- + MnO4- Mn2+ 5e- + MnO4- Mn2+ + 4H2O 8H+ + 5e- + MnO4- Mn2+ + 4H2O

Balancing Redox Reactions

C2O42- CO2 C2O42- 2CO2 +3 +4 (1 e- per carbon) C2O42- 2CO2 + 2e-

Balancing Redox Reactions

C2O42- 2CO2 + 2e+ MnO4- Mn2+ + 4H2O (X 5) (X 2)

Balancing Redox Reactions (Acidic Solutions)

Cr2O72- + Cl- Cr3+ + Cl2 14 H+ + Cr2O72- + 6Cl- 2Cr3+ + 3Cl2 + 7H2O Cu + NO3- Cu2+ + NO2 + 2NO3- Cu2+ + 2NO2 + 2H2O

8H+

5e-

5C2O42- 10CO2 + 10e16H+ + 10e- + 2MnO4- 2Mn2+ + 8H2O 16H++5C2O42-+2MnO4- 2Mn2+ + 10CO2 + 8H2O

Cu +

4H+

14H+ +

Mn2+ + BiO3- Bi3+ + MnO42Mn2+ + 5BiO3- 5Bi3+ + 2MnO4- + 7H2O

Balancing Redox Reactions (Basic Solutions)

Just add enough OH- to each side to make all of the H+ to water. NO2- + Al NH3 + Al(OH)45H2O + OH- + NO2- + 2Al NH3 + 2Al(OH)4Cr(OH)3 + ClO- CrO42- + Cl2 2Cr(OH)3 + 6ClO- 2CrO42- + 3Cl2 + 2OH- + 2H2O Balance in Both Acidic and Basic Solutions F- + MnO4- MnO2 + F2

HNO2 + H2O2 O2 + NO H is +1

Voltaic (Galvanic) Cells

F- + MnO4- MnO2 + F2 + 8H + 6F + 2MnO4- 2MnO2 + 3F2 + 4H2O 4H2O + 6F- + 2MnO4- 2MnO2 + 3F2 + 8OHHNO2 + H2O2 O2 + NO 2HNO2 + H2O2 O2 + 2NO + 2H2O Voltaic(Galvanic) Cells redox reactions that produce a voltage
Spontaneous reactions ( G<0) Voltage of the cell (Eocell) is positive Batteries

Electrolytic cells redox reactions that must have a current run through them.
G>0 and Eocell is negative. Often used to plate metals

Voltaic (Galvanic) Cells

History Galvani (died 1798) uses static electricity to move the muscles of dead frogs Volta (1800) Created the first battery

Voltaic (Galvanic) Cells

Voltaic cell 1. Anode Oxidation site 2. Cathode Reduction site (RC cola) 3. Salt bridge completes the circuit

Voltaic (Galvanic) Cells

Cell Notation Zn | Zn2+(aq) ||Cu2+(aq) | Cu Anode Zn Zn2+ + 2e2+ Cathode Cu + 2e Cu Cell Cu2+ + Zn Cu + Zn2+

Voltaic (Galvanic) Cells

Hydrogen Electrode
1. Standard Electrode 2. Voltage(potential) = 0 Volts 2H+(aq) + 2e- H2(g) H2(g) 2H+(aq) + 2e0 volts 0 volts

3. Often used in electrodes (like pH)

Standard Reduction Potentials

Always written as a reduction If cell is positive, produces a voltage Rules
Flipping an equation changes the sign of E Multiplying an equation does not change the magnitude of E

Calculating Cell Potential

A cell is composed of copper metal and Cu2+(aq) on one side, and zinc metal and Zn2+(aq) on the other. Calculate the cell potential. Zn2+ + 2e- Zn -0.76 V Cu2+ + 2e- Cu +0.34 V flip the zinc equation Zn Zn2+ + 2e+0.76 V 2+ Cu + 2e Cu +0.34 V Zn + Cu2+ Zn2+ + Cu +1.10 V

Example 1
What is the cell emf of a cell made using Cu and Cu2+ in one side and Al and Al3+ in the other? Write the complete cell reaction.

Example 2
Calculate the standard emf for the following reaction. Hint: break into half-reactions.

2Al(s) + 3I2(s) 2Al3+(aq) + 6I-(aq)

ANS: 2.2 V

Example 3
A voltaic cell is based on the following half reactions. In+(aq) In3+(aq) + 2eBr2(l) + 2e- 2Br-(aq)

Example 4
Calculate the standard emf for the following reaction. Cr2O72- + 14H+ + 6I- 2Cr3+ + 3I2 + 7H2O

+1.06 V

If the overall cell voltage is 1.46 V, what is the reduction potential for In3+?

Two half reactions in a voltaic cell are: Zn2+(aq) + 2e- Zn(s) Li+(aq) + e- Li(s) a) Calculate the cell emf. b) Which is the anode? Which is the cathode? c) Which electrode is consumed? d) Which electrode is positive? e) Sketch the cell, indicating electron flow.

Given the following half-reactions: Pb2+ + 2e- Pb Ni2+ + 2e- Ni a. Calculate the cell potential (Eo). b. c. d. e. f. Label the cathode and anode. Identify the oxidizing and reducing agents. Which electrode is consumed? Which electrode is plated? Sketch the cell, indicating the direction of electron flow.

Strengths of Oxidizing and Reducing Agents

larger the reduction potential, stronger the oxidizing agent
Wants to be reduced, can oxidize something else.

Stronger Oxidizing Agents

F2 + 2eCl2 + 2e. . . . . Li+ + e-

2F 2Cl-

+2.87 V +1.36 V

lower the reduction potential, stronger the reducing agent

Would rather be oxidized

Li

-3.05V

Example 1
Which of the following is the strongest oxidzing agent? Which is the strongest reducing agent? NO3Cr2O72Ag+

Example 2
Which of the following is the strongest reducing agent? Which is the strongest oxidizing agent? I2(s) Fe(s) Mn(s)

Example 3
Can copper metal (Cu(s)) act as an oxidizing agent?

Spontaneity
Voltaic Cells Positive emf Spontaneous Can produce electric current Batteries Electrolytic Cells Negative emf Not spontaneous Must pump electricity in Electrolysis

Example 1
Are the following cells spontaneous as written? a) Cu + 2H+ Cu2+ + H2 b) Cl2 + 2I- 2Cl- + I2 c) I2 + 5Cu2+ + 6H2O 2IO3- + 5Cu + 12H+ d) Hg2+ + 2I- Hg + I2

EMF and Go
G = -nFE
n = number of electrons transferred E = Cell emf F = 96,500 J/V-mol (Faradays Constant) Positive Voltage gives a negative G (spont)

Ex 1
Calculate the cell potential and free energy change for the following reaction: 4Ag + O2 + 4H+ 4Ag+ + 2H2O

Ex 2
Calculate G and the EMF for the following reaction. Also, calculate the K.
3Ni2+ + 2Cr(OH)3 + 10OH- 3Ni + 2CrO42- + 8H2O

ANS: +0.43 V, -170 kJ/mol

ANS: +87 kJ/mol, -0.15 V, 6 X 10-16

EMF and K
Go = -RTlnK -nFEo = -RTlnK
lnK = nFEo

Example 1
Calculate G, cell voltage and the equilibrium constant for the following cell: O2 + 4H+ + 4Fe2+ 4Fe3+ + 2H2O

( Go = -nFEo)
(assume 298 K)

RT log K = nEo 0.0592

ANS: -177 kJ/mol, 0.459 V, 1 X 1031

Example 2
If the equilibrium constant for a particular reaction is 1.2 X 10-10, calculate the cell potential. Assume n = 2.

Concentration Cells: Nernst Equation

G = Go + RT lnQ -nFE = -nFEo + RT lnQ E = Eo RT lnQ (assume 298 K) nF E = Eo 0.0592 log Q n Can adjust the voltage of any cell by changing concentrations

Using the Nernst Eqn

Suppose in the following cell, the concentration of Cu2+ is 5.0 M and the concentration of Zn2+ is 0.050 M. Calculate the cell voltage. Zn(s) + Cu2+(aq)Zn2+(aq) + Cu(s) +1.10 V
E = Eo 0.0592 V log Q n E = 1.10V - 0.0592 V log [Cu][Zn2+] 2 [Cu2+][Zn] E = 1.10V - 0.0592 V log [Zn2+] 2 [Cu2+] E = 1.10V - 0.0592 V log [0.050] 2 [5.0] E = +1.16 V

Example 1
Calculate the emf at 298 K generated by the following cell (Eo= 0.79 V) where: [Cr2O72-]= 2.0 M, [H+ ]=1.0 M, [I-]=1.0 M and [Cr3+ ]= 1.0 X 10-5M. Cr2O7
2-

Example 2
Calculate the emf at 298 K generated by the following cell (Eo= 2.20 V) where: [Al3+]= 0.004 M and [I- ]=0.010 M. 2Al(s) + 3I2(s) 2Al3+(aq) + 6I-(aq)

14H+

6I-

2Cr3+

+ 3I2 + 7H2O ANS: +2.36 V

ANS: 0.89 V

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Example 3
If the voltage of a Zn-H+ cell is 0.45 V at 298 K when [Zn2+]=1.0 M and PH2=1.0 atm, what is the concentration of H+? Note that atm can be used just like molarity. Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)

Example 4
What pH is required if we want a voltage of 0.542 V and [Zn2+]=0.10 M and PH2=1.0 atm? Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)

ANS: 5.2 X 10-6M

ANS: 5.84 X 10-5M, pH = 4.22

Batteries
Lead Acid Battery 12 Volt DC Discharges when starting the car, recharges as you drive (generator). Running reaction backward.
PbO2(s) + Pb(s) +2HSO4
-(aq)

Alkaline Batteries
Basic Zinc can acts as the anode
2MnO2(s)+2H2O(l)+2e-2MnO(OH)(s) + 2OH-(aq) Zn(s) + 2OH-(aq) Zn(OH)2(s) + 2e2PbSO4(s) +2H2O(l)

2H+(aq)

Rechargable uses Ni-Cd

Corrosion
Iron rusts in acidic solns (not above pH=9) Water needs to be present Salts accelerate the process O2 + 4H+ + 4e- 2H2O Fe Fe2+ + 2e(The Fe2+ eventually goes to Fe3+, Fe2O3)

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Preventing Corrosion
Paint Sometimes oxide layer(Al2O3) Galvanizing (coating Fe with Zn) Fe2+ + 2e- Fe E = -0.44 V Zn2+ + 2e- Zn E = -0.76 V Zinc is more easily oxidized (Zn Zn2+ + 2eE = +0.76 V)

Example 1
Cathodic protection (sacrificial anode) Magnesium used in water pipes Magnesium rods used in hot water heaters An iron gutter is nailed using aluminum nails. Will the nail or the iron gutter corrode first? Fe2+ + 2e- Fe Al3+ + 3e- Al E = -0.44 V E = -1.66 V

Al will corrode first (Al Al3+ + 3e- ,E = +1.66 V)

Ex 2
Which of the following metals could provide cathodic protection to iron: Al Cu Ni Zn

Electrolysis and Electroplating

Plating of silver on silverware

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Electrolytic cells
Must run electricity through them Running a voltaic cell backwards Used to produce sodium metal Na+(aq) + e- Na (s) Cl2(g) + 2e- 2Cl-(aq) -2.71 V +1.36 V As a voltaic cell 2Na(s) 2Na+(aq) + 2e- +2.71 V Cl2(g) + 2e 2Cl-(aq) +1.36 V 2Na(s) + Cl2 (s)2NaCl(aq) +4.07 V As an electrolytic cell 2Na+(aq) + 2e- 2Na (s) -2.71 V 2Cl-(aq) Cl2(g) + 2e-1.36 V 2NaCl(aq) 2Na(s) + Cl2 (s) -4.07 V

Quantitative Electrolysis
Electric current = Amperes 1 ampere = 1Coloumb 1 second 1 F = 96,500 C/mol

Example 1
What mass of aluminum can be produced in 1.00 hour by a current of 10.0 A? Al3+ + 3e- Al Q= I t Q = (10.0 A)(3600 s) = 36,000 C

I = Q t

One mole of electrons has a charge of 96,500 C One electron has a charge of 1.602 X 10-19 C

Example 2
Moles of e- = (36,000C)(1 mol e-) = 0.373 mol e(96,500 C) Al3+ + 3e- Al 0.373 mol Al3+ + 3e- 0.373 mol Al 0.124 mol Al 3.36 g Al
What mass of magnesium can be produced in 4000 s by a current of 60.0 A? Mg2+ + 2e- Mg

ANS: 30.2 g Mg

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Example 3
What current is required to plate 6.10 grams of gold in 30.0 min? Au3+ + 3e- Au (6.10 grams Au)(1mol Au) = 0.0310 mol Au (196.97g Au) How long would it take to plate 50.0 g of magnesium from magnesium chloride if the current is 100.0 A?

Q=It I = Q/t (Actually I = dQ/dt) I = 8966 C = 5.0 amps 1800 s

Au3+ + 3e-

Au 0.0310 mol Au Au 0.0310 mol Au

Au3+ + 3e- 0.0929 mol e

(0.0929 mol e)(96,500 C) = 8966 C (1 mol e)

Given the following: Ag+(aq) + e- Ag(s) +0.799V Fe3+(aq) + e- Fe2+(aq) +0.771 V a. Write the reaction that occurs. b. Calculate the standard cell potential. c. Calculate Grxn for the reaction from the cell potential. d. Calculate for the reaction. e. Predict the sign of Srxn. f. Sketch the cell, labeling anode, cathode, and the direction of electron flow.

Do SO3 and SO32- have the same molecular shape? How about SO2?

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16. a) Not redox b) I oxidized (-1 to +5) , Cl reduced (+1 to -1) c) S oxidized (+4 to +6), N reduced (+5 to +2) d) Br oxidized (-1 to 0), S reduced (+6 to +4) 20 a. Mo3+ + 3e- Mo b. H2O + H2SO3 SO42- + 2e- + 4H+ c. 4H+ + 3e- + NO3- NO + 2H2O d. 4H+ + 4e- + O2 2H2O e. 4OH- + Mn2+ MnO2 + 2e- + 2H2O f. 5OH- + Cr(OH)3 CrO42- + 3e- + 4H2O g. 2H2O + 4e- + O2 4OH-

22. a. 3NO2- + Cr2O72- +8H+ 3NO3- + 2Cr3+ + 4H2O b. 2HNO3 + 2S +H2O 2H2SO3 + N2O c. 2Cr2O72- + 3CH3OH + 16H+ 4Cr3+ 3HCO2H + 11H2O d. 2MnO4- + 10Cl- + 16H+ 2Mn2+ + 5Cl2 + 8H2O e. NO2- + 2Al + 2H2O NH4+ + 2AlO2f. H2O2 + 2ClO2 + 2OH- O2 + 2ClO2- + 2H2O

26. a) Al oxidzed, Ni2+ reduced b) Al Al3+ + 3e- Ni2+ + 2e- Ni c) Al anode, Ni cathode d) Al negative, Ni positive e) Electrons flow towards the Ni electrode f) Cations migrate towards Ni electrode

34 a) Cd is anode, Pd is cathod b) Ered = 0.63 V

36 a) 2.87 V b) 3.21 V c) -1.211 V d) 0.636V 38 a) 1.35 V b) 0.29 V

41 a) Mg b) Ca c) H2 d) H2C2O4 2+ 42 a) Cl2 b) Cd c) BrO3- d) O3 3+ 44. a) Ce (weak reductant) b) Ca (strong reductant) c) ClO3- (strong oxidant) d) N2O5 ( oxidant) 46 a) H2O2 strongest oxidizing agent b) Zn strongest reducing agent 50.a) 3.6 X 108 b) 1041 c) 10103 52. 0.292 V 54 a) 4 X 1015 b) 2 X1065 c) 7.3 X1049

62a) 2.35 V b) 2.48 V c) 2.27 V 64. a) 0.771 V b) 1.266 V 88. a) 173 g b) 378 min 90.E = 1.10 V Wmax = -212 kJ/mol Cu W = -1.67 X 105 J

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1a) 14H+ + Cr2O72- + 3Fe 2Cr3+ + 3Fe2+ + 7H2O b) 2Br- + F2 2F- + Br2 c) 4OH- + 2Cr(OH)3 + ClO3- 2CrO42- + Cl- + 5H2O 2b) 0.463 V c) -89.4 kJ/mol d) 4.4 X 1015 e) 0.442 V 3) F2 is str. oxidizing agent, Li, str. reducing agent 4) b) 78 minutes c) 1.19 g d) 0.695 g

In a measuring cup: 5 mL of oil 5 mL of ethanol 5 mL of 50% NaOH solution (approximately 30 drops). Place in beaker Heat the mixture, stirring with popsicle stick. Remove from heat. After ~5 minutes, add 10 mL of saturated salt solution. Collect some of the solid and test the pH of your soap. Compare the pH to that of commercial bar soap and liquid detergent solution. See if it lathers.

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