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REDOX 1

REDOX & Electrochemistry

REDOX 2

There are two types of chemical reactions: 1) acid-base reactions (Lewis) 2) electron-transfer reactions Oxidation/oxidize: when you remove electrons from a material Reduction/reduce: when you add electrons to a material You cannot have oxidation without reduction; you cannot generally reduce a molecule without oxidizing another molecule (and the other way around). Oxidizing agent: a chemical that causes another material to be oxidized (the oxidizing agent is reduced!) Reducing agent: a chemical that causes another material to be reduced (the reducing agent is oxidized!)

REDOX

REDOX 3

Oxidation States In order to understand redox reactions, we first need to be able to figure out what the oxidation state of an element is. The oxidation state is a method to indicate how many electrons are "assigned" to a particular element. For this we use a +/- system:

+n n
0

indicates that an atom has lost electrons and now has a positive charge indicates that an atom has gained electrons and now has a negative charge indicates that an atom has its elemental number of electrons assigned to it and, therefore, has no charge

Oxidation state is a formalism, that is, is may or may not reflect the actual charge on an atom. Common reference atoms & their oxidations states: Alkali metals = +1, alkaline earths = +2 O = 2 (exception, peroxides, H2O2, 1) Halides = 1 (exception, oxyhalides)

REDOX 4

The key to being able to figure out the oxidation state of an element in a molecule is to note its electronegativity:

The higher the electronegativity the more the element likes to add electrons to its valence shell. The lower the electronegativity the more likely an element will lose electrons.

Let's dissect an example reaction:

Reaction: PH 3 + O 2
Electronegativities: H = 2.1

P2 O5 + H2 O
P = 2.1 O = 3.5

PH 3 + O 2 -3 +1 0

P2O5 + H2O

+5 -2 +1 -2 Atoms that gain electrons usually gain enough to fill their valence shell (octet rule). Atoms that lose electrons only lose enough to get them down to the next lowest filled valence shell (but not always all the way!).

REDOX 5

When two elements have the same electronegativity (as with phosphorus and hydrogen) the element that is furthest to the upper right hand side of the periodic table is the one that gets the electrons.
1
1

Periodic Table of the Elements


2
4
Berylium

18
2

H
Hydrogen

13
5

14
6

15 16
7 8

17
9

He
Helium

3
Lithium

10

Li Be
11
Sodium

Group 8

B
Boron

C
Carbon

N
Nitrogen

O
Oxygen

F
Fluorine

Ne
Neon

12
Magnesium

13

14

15

16

17

18

Na Mg
19 20
Calcium

3
21
Scandium

4
22

5
23

6
24
Chromium

7
25
Manganese

8
26
Iron

9
27
Cobalt

10
28
Nickel

11
29
Copper

12 Al
30
Zinc

Si
Silicon

P
Phosphorus

S
Sulfur

Cl
Chlorine

Ar
Argon

Aluminum

31
Galium

32
Germanium

33
Arsenic

34
Selenium

35
Bromine

36

K
Potassium

Ca Sc
38
Strontium

Ti
Titanium

V
Vanadium

Cr Mn Fe Co Ni
42
Molybdenum

Cu Zn
47
Silver

Ge As Se
49
Indium

Kr
Krypton

37
Rubidium

39

40
Zirconium

41
Niobium

43
Technetium

44
Ruthenium

45
Rhodium

46
Palladium

48
Cadmium

50
Tin

51
Antimony

52
Tellurium

53

54

Rb Sr
55
Cesium

Y
Yttrium

Zr Nb Mo Tc Ru Rh Pd Ag Cd In
72
Hafnium

Sn Sb Te
82
Lead

I
Iodine

Xe
Xenon

56
Barium

57
Lanthanum

73
Tantalum

74
Tungsten

75
Rhenium

76
Osmium

77

78
Platinum

79
Gold

80
Mercury

81

83
Bismuth

84
Polonium

85
Astatine

86
Radon

Cs Ba La

Hf Ta

W Re Os

Ir
Iridium

Pt Au

Tl
Thallium

Pb Bi Po At Rn

It is important to remember that the bond between phosphorus and hydrogen is, in reality, pretty much neutral and covalent in character (although the hydrogen atoms actually do have a small amount of positive charge on them). Only when there is a considerable difference in the electronegativities of two atoms does one see formal charge separations and polar bonds occurring.

REDOX 6

Problem: What are the oxidation state assignments for the following compounds: a) CH4 b) CO2

c) KMnO4

d) FeS

e) H2SO4

f) HCN

g) Na2CrO4

h) N2

i) MnO2

j) H2C2O4

REDOX 7

Balancing Redox Equations


The best way of balancing redox reactions is the half cell method. Break up the overall rxn into 2 half-cell rxns: one for the reduction and one for the oxidation. We then want to multiply each half cell reaction to make the overall # of electrons the same so they cancel out.

Note that this fairly simple rxn (and many redox rxns) could have been balanced the normal way. But if it is a redox rxn and looks hard, use the half cell method.

REDOX 8

Let's do another balancing act:

Note that in the last two examples, one of the products or reactants (O2, P2O5, and Al2O3) had two redox active atoms present (O, P, and Al) and that had to be accounted for when writing out the half cell reaction. Also note that when balancing half cell rxns, we mainly worry about the redox active atoms and not the H and O atoms (assuming they are not changing oxidation states). These will be balanced at a later point (see next example).

REDOX 9

Another EXAMPLE:

This is the core redox balanced reaction. Now, you have to check the oxygen, and then hydrogen atom balance:

REDOX 10

To balance the rxn in basic solution you need to balance the rxn first as if it was in acidic solution (as shown above). Then you get rid of the H+ by adding as many OH to each side as there are protons and reacting the H+ and OH together to make waters:

REDOX 11

Problem: Balance the following (in water): Cr3+ + Cl (g) (acidic) a) Cr O 2- + Cl2 7 2

b) MnO4- + CN-

MnO2(s) + CNO- (basic)

REDOX 12

c) Na2S2O3(aq) + NaOCl(s)

NaCl(aq) + Na2S4O6(aq) (acidic)

d) Au(s) + CN(aq) + O2(g)

Au(CN)4(aq) + OH(aq) (basic)

REDOX 13

Electrochemical/Voltaic/Galvanic Cell Consider the reaction of Zn(s) and Cu2+(aq): Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) This reaction involves the transfer of 2 e- between the Zn(s) and Cu2+. The Cu2+ oxidizes the Zn, and is in turn reduced to form metallic Cu, while the Zn metal dissolves into solution as Zn2+. This reaction is spontaneous with a G = 212 kJ/mol. Mixing Zn(s) and Cu2+ together in a beaker causes a spontaneous reaction that gives off all the energy as heat, warming the solution. The transferring of the electrons between the Zn and Cu2+, however, can accomplish much more useful work if we can figure out a way to get the eto flow through a wire as electricity, where the work represented by G (free energy) can now be used as electrical work.

REDOX 14

To harness the intrinsic chemical energy stored in these oxidizing and reducing agents, we must separate them to force the electrons to flow though an external circuit and do some work.
flow of electrons

salt bridge or semi-permeable membrane

Zn

Zn

2+

Zn

2+ Cl

Cl Cu Cl 2+

Cu

2+

Cu

Cu

Cl Zn

2+ Cl -

Cl -

Cl 2+

Cu Cu Cu Cu Cu Cu

Cu

Cl Cl Zn

Cl -

2+

Zn

2+

Cl -

Cl - Cu

2+

Cl - Cl Cu
2+

ANODE oxidation

Anion flow

CATHODE reduction

Red Cat = Reduction occurs at Cathode

REDOX 15

There are different configurations of liquid galvanic cells that one can setup:
flow of electrons salt bridge or semi-permeable membrane

Zn

Cl -

2+ - Cl Cu 2+ 2+ Cu Zn Cl Cl Cl - Cl Zn2+ Cl - Cl 2+ 2+ 2+ Zn Cl Cl Cu Cu

Zn

2+

Zn

2+ Cl

Cl -

Cu

2+

Cu

Cu

Cl -

Cl -

Cu Cu Cu Cu Cu Cu

semipermeable membrane

ANODE oxidation

Anion flow

CATHODE reduction

flow of electrons

flow of electrons

ANODE oxidation
Zn

Zn

Cu ANODE oxidation CATHODE reduction CATHODE reduction

Anion flow

salt bridge

Daniell Cell

REDOX 16

Measuring Cell Potentials (Voltages)

M H2
X H+ H+ X X H+ salt bridge or semi-permeable membrane H+
+ X M X M+ + X H X X X X X M+ M+ X + H X X + M+ X H + X M + + X H X M

X M+

Pt

M+

On a platinum electrode, H2(g) and H+(aq) are in redox equilibrium with one another (1 atm H2, 1M H+). This is called a hydrogen electrode.
H2 2H + + 2e-

By setting this electrochemical potential to 0.0 V, we have a reference electrode to which we can measure the innate ability of a material in the other electrode compartment of the electrochemical cell to either accept (be reduced/cathode) or give up (be oxidized/anode) electrons from/to H2/H+.

REDOX 17

Standard Reduction Potentials at 25C


Half Cell Rxn F (g) + 2eO3(g) + 2H+(aq) + 2eCo3+(aq) + eCl2(g) + 2eO2(g) + 4H+(aq) + 4eAg+(aq) + eCu+(aq) + eCu2+(aq) + 2eAgCl(s) + eCu2+(aq) + e2H+(aq) + 2ePb2+(aq) + 2eV3+(aq) + eZn2+(aq) + 2eAl3+(aq) + 3eH2(g) + 2eMg2+(aq) + 2eNa+(aq) + eLi+(aq) + e2

2F-(aq) O2(g) + H2O Co2+(aq) 2Cl-(aq) 2H2O Ag(s) Cu(s) Cu(s) Ag(s) + Cl-(aq) Cu+(aq) H2(g) Pb(s) V2+(aq) Zn(s) Al(s) 2H-(aq) Mg(s) Na(s) Li(s)

Ered (V) +2.87 +2.07 +1.81 +1.36 +1.23 +0.80 +0.52 +0.34 +0.22 +0.15 0.00 -0.13 -0.24 -0.76 -1.66 -2.25 -2.36 -2.71 -3.05

It is critically important that you learn how to read, interpret, understand, and properly use this table.

REDOX 18

Voltage (or potential) represents the driving force for pushing the electrons from one location to another (for example, from a reducing agent to an oxidizing agent). The higher the voltage the more strongly the electrons will be pushed through the wire (or solution). A positive cell potential (voltage) indicates a spontaneous electrochemical reaction. A negative cell potential (voltage) indicates a non-spontaneous reaction (the opposite reaction will, therefore, be spontaneous!). Note that the sign notation here is opposite that we learned for G!
Problems: Which of the following substances is the

best reducing agent? a) Cu b) Zn c) Pb d) Ag e) H2

Which of the following substances is the best oxidizing agent? a) Cu+ b) O3 c) O2 d) Na+ e) Li+

REDOX 19

To calculate the voltage of an electrochemical cell one can simply add together the two half-cell reactions that make up the overall galvanic (electrochemical) cell. Lets calculate the spontaneous cell potential (voltage) for our Cu/Zn cell. First look up the two half cell reactions from the table of Standard Reduction Potentials:
Cu2+(aq) + 2eZn2+(aq) + 2eCu(s) Zn(s) +0.34 -0.76

The more positive potential (relative to the hydrogen electrode) for the Cu2+ reduction compared to the Zn2+ reduction means that Cu2+ is a stronger oxidizing agent (wants to be reduced more) than Zn2+.

REDOX 20

To add these half-cell rxns together to give us our overall spontaneous net rxn and cell potential, we must switch one of the two half-cell rxns around so that it is written as an oxidation rxn (a compound giving up electrons on the product side of the rxn). The half-cell rxn with the smaller positive, or more negative potential gets flipped around (reversed). This would be the Zn rxn:
Cu2+(aq) + 2eCu(s) Zn(s) Zn2+(aq) + 2e+0.34 +0.76

When one flips one of the half-cell rxns around, one also flips (reverses) the sign of the cell potential!! The next step is to multiply each of the half cell rxns by the appropriate # to balance the # of electrons involved so that they cancel out. For the Cu/Zn cell, there are 2e- on each side of the two half-cell rxns, so everything is already balanced:
Cu2+(aq) + 2eCu(s) Zn2+(aq) + 2e+ Zn(s) Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s) +0.34 V +0.76 V +1.1 V

REDOX 21

So the net reaction has a voltage of +1.1 V, the positive potential indicates that the rxn is spontaneous. Note that the voltage calculated for the cell is for standard conditions (1 atm, 1 M). Changing the concentrations away from 1M will change the cell potential! Similarly, changing the temperature will also affect the voltage. The Nernst Equation allows one to calculate the voltage (potential) of a electrochemical reaction when one is not working under standard conditions! Also note that for galvanic cells (batteries) we always want to use a spontaneous reaction that gives off energy that we can use to perform work. But on homeworks or tests I may give you an overall balanced reaction that is non-spontaneous. In this case you need to write down the half-cell rxns in the right order to give the overall balanced rxn and calculate the cell potentials from the way that these half-cell reactions are written.

REDOX 22

Example: What is the potential for the following

reaction? 2Na+(aq) + 2Cl(aq)


Reduction half cell: Oxidation half cell: Na+(aq) + 1e2Cl(aq)

Cl2(g) + 2Na(s)
Na(s) Cl2(g) + 2e2.71 V 1.36 V

sum = 4.07 V
This half-cell was the one that was flipped around (reversed)

Non-spontaneous

The reverse reaction is very spontaneous with a cell potential of +4.07 V.

REDOX 23

Example: What is the potential for the

electrochemical cell composed of the following 2 phrased like this, we are looking for a spontaneous half cell rxns? When reaction that gives a positive cell potential!
Cr+3(aq) + 3eMnO2 + 4H+ + 2eCr(s) Mn2+(aq) + 2H2O -0.74 +1.28

The Cr+3(aq) + 3e- Cr(s) rxn has the more negative potential, so it gets flipped around:
Cr(s) Cr+3(aq) + 3eMn2+(aq) + 2H2O MnO2 + 4H+ + 2e+0.74 +1.28

Now we have to balance the # of electrons in each rxn so we can add them together. 6 e- is the common factor, so we need to multiply the Cr rxn by 2 and the MnO2 rxn by 3: 2[Cr(s) Cr+3(aq) + 3e- ]
Mn2+(aq) + 2H2O] 3[MnO2 + 4H+ + 2e2Cr(s) + 3MnO2 + 12H+ 2Cr+3(aq) + 3Mn2+(aq) + 6H2O

+0.74 +1.28 +2.02V

Note that you do NOT multiply the cell potentials by the numerical factors (2 or 3) used to balance the # of electrons in each half-cell rxn!!

DANGER!! Common mistake!!

REDOX 24

Example: Zn metal reacts with HCl, but Cu metal

doesnt. Calculate the cell potentials for these rxns to see if they fit the experimental data. Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)

Splitting this rxn into the two half cell rxns, we have:
Zn(s) Zn2+(aq) + 2eH2(g) 2H+(aq) + 2eZn(s) + 2H+(aq) Zn2+(aq) + H2(g) +0.76 0.00 +0.76V

Note that the Zn half-cell rxn is flipped around from how it is written in the Standard Reduction Table, since it is acting as a reducing agent here. The calculated positive cell potential indicates a spontaneous rxn.

REDOX 25

For the copper rxn, we have: Cu(s) + 2H+(aq)


Cu2+(aq) + 2eH (g ) 2H+(aq) + 2eCu(s)
2

Cu2+(aq) + H2(g)
0.34 0.00 0.34V

Cu(s) + 2H+(aq)

Cu2+(aq) + H2(g)

Once again, note that the copper half-cell rxn is flipped around from how it is written in the Standard Reduction Table, since it is acting as a reducing agent here. So here we calculate that the cell potential is negative, indicating a nonspontaneous rxn or one that should not occur normally, which fits the experimental data. This is because copper metal is a more inert material relative to zinc metal. One could also note the position of copper above the hydrogen half cell rxn, which indicates that the reverse rxn of Cu+2 with H2 gas would be spontaneous:
Cu2+(aq) + H2(g) Cu(s) + 2H+(aq)

+0.34V

REDOX 26

Example: What about the reaction of Cu with

nitric acid? Will this be a spontaneous rxn? Nitric acid is not like the other strong acids (HCl, HBr, HI, H2SO4) in that it is a good oxidizing acid due to the presence of the NO3 anion, which is not just a simple inert counter-anion for H+. The combination of NO3 and H+ makes for a rather strong oxidizing mixture.
3[Cu(s) Cu2+(aq) + 2e-] 2[NO3(aq) + 4H+(aq) + 3eNO(g) + 2H2O] 0.34 +0.96 +0.62V

3Cu(s) + 8H+(aq) + 2NO3(aq) 3Cu2+(aq) + 2NO(g) + 4H2O

If you get nitric acid on your skin, you will not only feel the burning of the acid (H+), but your skin will be oxidized to a yellow-brown color! So concentrated nitric acid is doubly dangerous!

REDOX 27

Although one can add half-cell rxns to yield overall redox equations, one can not simply add two halfcell rxns to yield another half-cell rxn. For example, consider the addition of the following two half cell rxns to generate a third half cell rxn:
Cu2+(aq) + 1eCu+(aq) + 1eCu2+(aq) + 2eCu+(aq) Cu(s) Cu(s) +0.16 V +0.52 V +0.68 V

The correct half-cell potential for this rxn is 0.34 V, which is exactly half of what we incorrectly attempted to calculate above. This factor of comes from the fact that all the half-cell potential values are normalized to a single e- value even if multiple e- are used in the half cell rxn. As you might expect, the electrochemical potential for a rxn is directly related to the G for a reaction (only with an opposite sign relationship!):

G = nFE
n = # of electrons being transferred, F = Faradays constant (96.5 kJ/Vmol), E = standard potential.

REDOX 28

Problems: Calculate the cell potentials for the

following reactions. Are they spontaneous or not? a) F2(g) + 2Na(s) b) Cu(s) + Zn2+(aq) c) 2Al3+(aq) + 3Pb(s) d) 2Co3+(aq) + 2Cl-(aq) e) 2Mg(s) + O2(aq) + 4H+(aq) f) 2Al(s) + 6H+(aq) g) 2Cu(s) + Cl2(g) 2Na+(aq) + 2F(aq) Cu2+(aq) + Zn(s) 2Al(s) + 3Pb2+(aq) 2Co2+(aq) + Cl2(g)
2Mg2+(aq) + 2H2O(aq)

2Al3+(aq) + 3H2(g) 2Cu+(aq) + 2Cl(aq)

REDOX 29

Non-Standard Conditions: Nernst Equation E values are for standard conditions (1 M or 1 atm). If the reactant/product concentrations are different the cell potential, E, will differ from E. One can calculate non-standard potentials using the Nernst equation:

2.303 RT E= E log Q nF
R = gas constant, 8.314 J/molK T = absolute temperature, K n = # of moles of electrons transferred F = faraday, 96,485 C/moleQ = reaction quotient

2.303 RT At room temp, 25 C , = 0.0592 V imol F substituting this into the Nernst eq gives : 0.0592 E= E log Q n

REDOX 30

Example: Calculate the potential for the Fe3+/Fe2+ electrode when the concentration of Fe2+ is five times greater than that of Fe3+. Look up potential in a half cell table: Fe3+ + eFe2+ E = +0.771 V The Fe2+ concentration is five times greater than that of Fe3+, so the Q expression is:

[products] p [Fe2+ ] Q= =5 r = 3+ [reactants] [Fe ]


Assume room temp (25C = 298K) and solve using the Nernst equation:

0.0592 E= E log Q n 0.0592 E = 0.771 log(5) 1 E = 0.771 (0.0592)(0.7) = 0.730 V


Problem: The potential for this is lower than E

where both concentrations are 1 M. This should make sense based on Le Chateliers principle. Why?

REDOX 31

half-cell consists of Cu2+/Cu, [Cu2+] = 0.4 M. The other half-cell involves Zn2+/Zn with [Zn2+] = 0.4 M. Apply the Nernst equation to the overall cell reaction to determine the cell potential.

Problem: A cell is constructed at 25C as follows. One

Problem: Consider the following half-cell rxn:


Pb(s) + SO42(aq) PbSO4(s) + 2eE = +0.13 V

Can the Nernst equation help us figure out how to change concentrations to increase the cell potential? Why?

REDOX 32

Lead-Acid Storage Battery

Anode Rxn:
Pb(s) + SO42(aq) PbSO4(s) + 2eE = +0.13 V

Cathode Rxn:
PbO2(s) + 4H+(aq) + SO42(aq) + 2ePbSO4(s) + 2H2O E = +1.69 V

Overall Rxn:
Pb(s) + PbO2(s) + 4H2SO4(aq) 2PbSO4(s) + 2H2O E = +1.82 V

REDOX 33

Dry Cell (regular battery)


Graphite Cathode Moist Paste of NH4Cl, MnO2 & carbon Porous separator Zinc anode
Note that the production of NH3(g) in this regular cell produces an insulating layer between the cathode and the MnO2/NH4+. This causes these batteries to fade relatively quickly after steady use. Letting them sit for a while, allows the NH3(g) to diffuse away & allow fresh reagents to come in contact with the cathode, thus the battery becomes rejuvenated.

Anode Rxn:
Zn Zn2+ + 2eE = 0.76 V

Cathode Rxn:
2MnO2 + 8NH4+ 2Mn3+ + 4H2O + 8NH3 E = 1.21 V

Overall Rxn:
Zn + 2MnO2 + 8NH4+ 2Mn3+ + Zn2+ + 4H2O + 8NH3
Real batteries only produce 1.5 V because the real chemistry is far more complicated and less efficient.

E = 1.97 V

REDOX 34

Alkaline Cells
Graphite Cathode Moist Paste of KOH, MnO2 & graphite Porous separator Zinc anode
The simple replacement of NH4Cl electrolyte with a KOH gel eliminates the production of the problematic NH3 gas that occurs in the regular dry cell. This battery has much improved stability for delivering electrical current until all the reagents are used up.

Anode Rxn: Zn + 2OH Cathode Rxn: 2MnO2 + 2H2O Overall Rxn:


Zn + 2MnO2 + H2O 2MnO(OH) + Zn(OH)2

Zn(OH)2 + 2e2MnO(OH) + 2OH

E = 1.5 V

REDOX 35

Corrosion of Steel/Iron

Cathode O2
Fe
2+

O2

Fe 2+

Water

Steel

Anode
2OH Fe(OH)2

Cathode: O2 + H2O + 2eAnode: Sum: Fe Fe2+ + 2eO2 + Fe + H2O

Subsequent Redox rxn: 4Fe(OH)2 + O2 + 4OH

RUST
2Fe2O3 4H2O

The presence of NaCl (salt) in the water makes it more conductive to e- flow, making it easier for the O2 to oxidize the iron without having to come directly in contact with it. Instead it can react anywhere at the surface of the water drop.

REDOX 36

Standard Reduction Potentials - 25C

REDOX 37

REDOX 38

Tables from Chemistry, 8th Ed, Whitten, Davis, Peck & Stanley (Thomson-Brooks/Cole)