Chapter 19 – Electrochemistry

19.1 How to Assign Oxidation Numbers (i.e. Oxidation States)

Oxidation – loss of electrons LEO OIL
Reduction – gain of electrons GER RIG

RULES FOR ASSIGNING OXIDATION NUMBERS

1. Elements in their elemental form are in the zero oxidation state.
2. Group 1 metals are +1 and Group 2 metals are +2.
3. Hydrogen is +1 except when bonded to a metal only (when it’s –1).
4. Transition elements must be determined from anion’s charge
(except Al = +3, Zn = +2, Cd = +2, Ag = +1)
5. The most electronegative elements get their typical oxidation state.
6. The last element not assigned balances the charge of the compound/ion.

Determine the oxidation numbers of all elements in the following:

Cl2 O2 O3

MgCl2 H2O2

N2 O 4 KO2

NaHCO3 NaN3

CuSO4

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19.2 How to Balance Oxidation-Reduction Reactions
Oxidizing Agent (Oxidant) – species that is reduced
Reducing Agent (Reductant) – species that is oxidized

HOW TO BALANCE REDOX REACTIONS (HALF-REACTION METHOD)

1. Split into half reactions.
2. Balance all elements except oxygen and hydrogen.
3. Balance oxygen by adding H2O.
4. Balance hydrogen by adding H+.
5. Balance the charge by adding electrons.
6. Mulitply half reactions by factors to make the number of electrons the same.
7. Combine half reactions canceling anything that shows up on both sides of the reaction.
8. Conditional: If balancing in base add the same number of OH- to both sides as H+ present.
On the side with the H+ the H+/OH- combine to form H2O.
9. Cancel any excess H2O that now shows up on both sides of the reaction (if necessary).

Balance the following redox reactions:

H2O2(aq) + PbS(s) → PbSO4(s) + H2O(l)

MnO4-(aq) + I-(aq) → Mn2+(aq) + I2(s)

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19.3 Galvanic Cells
CHARACTERISITICS OF ELECTROCHEMICAL CELLS
1. The anode is ALWAYS the site of oxidation. (an ox)
2. The cathode is ALWAYS the site of reduction. (red cat)
3. Electrons ALWAYS flow from anode to cathode.
4. Anions flow to the anode and cations to the cathode through the salt bridge (in galvanic cells).
5. In galvanic/voltaic cells (spontaneous), the cathode is + and the anode is –.
In electrolytic cells (nonspontaneous), the cathode is – and the anode is +.
6. Often, the cathode gains mass, while the anode loses mass (for metal/metal salt galvanic cells).

Galvanic vs Electrolytic Cells

GALVANIC (VOLTAIC) CELLS
Spontaneous (G < 0, Ecell > 0)
Produce Energy (Electricity)

Function as Batteries

ELECTROLYTIC CELLS
Nonspontaneous (G > 0, Ecell < 0)
Consume Energy (Electricity)

Often Used to Produce Elements

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19.3b Cell Notation & Cathodic Protection
Cell Notation
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) Zn(s) + 2Fe3+(aq) → Zn2+(aq) + 2Fe2+(aq)

Cathodic Protection
Fe is made an inert cathode in a spontaneous reaction between O2 and a more active metal (such as Zn).

Fe is readily corroded by oxidation in a reaction with O2.

2Fe + O2 + 4H+ → 2Fe2+ + 2H2O Fe2+ → Fe3+ → Fe2O3 (rust)

Having a more active metal around means it will be oxidized instead of iron (act as a sacrificial anode). Zinc is
commonly used for this purpose.
2Zn + O2 + 4H+ → 2 Zn 2+ + 2H2O

Ultimately, iron will simply act as an inert electrode and pass the electrons lost by the zinc to O2.

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19.4 Standard Cell Potentials

 = cat - an OR  = red + ox STANDARD HYDROGEN

ELECTRODE (SHE)
Zn2+ + Co → Zn + Co2+  =
2H+ + 2e- → H2 0.00v

REDUCTION POTENTIALS
Al3+ + 3e- → Al -1.66V
Mn2+ + 2e- → Mn -1.18V
Zn2+ + 2e- → Zn -0.76V
2Cr3+ + 3Cu → 2Cr + 3Cu2+  = Cr3+ + 3e- → Cr -0.74V
Fe2+ + 2e- → Fe -0.44V
Co2+ + 2e- → Co -0.28V
Ni2+ + 2e- → Ni -0.25V
2H++2e- → H2 0V
Cu2+ + 2e- → Cu +0.34V
Ag+ 1e- → Ag +0.80V
What is the balanced reaction for the galvanic cell composed of Mn2+/Mn
Br2 + 2e- → 2Br- +1.07V
and Fe2+/Fe half cells and calculate its standard cell potential?

Reduction Potentials
a) What is the strongest oxidizing agent?

b) What is the strongest reducing agent?

c) Which pairs will react spontaneously under standard conditions?

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19.5 How to Calculate Nonstandard Cell Potential (Nernst Equation)
Nernst Equation for Non-Standard Potentials
RT 0.0257 0.0592
E = E° − ln Q E = E° − ln Q E = E° − log Q 𝐍𝐄𝐑𝐍𝐒𝐓 𝐄𝐐𝐔𝐀𝐓𝐈𝐎𝐍
nF n n
QUALITATIVE EFFECTS
Shift to the right results in a higher potential
Shift to the left results in a lower potential

Calculate the cell potential for the following reaction at 298K when [Zn2+] = 0.0010M and [Co2+] = 0.10M.
Zn2+(aq) + Co(s) → Zn(s) + Co2+(aq)

19.5b Concentration Cells

Concentration cells have the same components at the anode and cathode, but with different concentrations.
As such the standard cell potential (E֯cell) is zero, and they are run under nonstandard conditions. The Nernst
equation is used to solve for Ecell.

RT 0.0257 0.0592
E = E° − ln Q E = E° − ln Q E = E° − log Q 𝐍𝐄𝐑𝐍𝐒𝐓 𝐄𝐐𝐔𝐀𝐓𝐈𝐎𝐍
nF n n

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19.6 Cell Potential (Ecell), G, and the Equilibrium Constant (Keq)

G, Ecell, & Keq Spontaneous

G = -nFE Relates G and Ecell Reactions
G = -nFE Relates G and Ecell G < 0
Ecell > 0
G = -RT lnKeq Relates G and Keq
Q<K
RT
E° = ln K eq Relates E and Keq
nF

Calculate G and Kc for the following redox reaction at 298K.

REDUCTION POTENTIALS
Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)
Al3+ + 3e- → Al -1.66V
Mn2+ + 2e- → Mn -1.18V
Zn2+ + 2e- → Zn -0.76V
Cr3+ + 3e- → Cr -0.74V
Fe2+ + 2e- → Fe -0.44V
Co2+ + 2e- → Co -0.28V
Ni2+ + 2e- → Ni -0.25V
2H+ + 2e-→H2 0V
Cu2+ + 2e- → Cu +0.34V
Ag+ 1e- → Ag +0.80V
Br2 + 2e- → 2Br- +1.07V

COMMON BATTERIES
PbO2(s) + Pb(s) + 2HSO4-(aq) + 2H+ → 2PbSO4(s) + 2H2O(l)
Lead Storage Battery
Anode = Pb Cathode = PbO2
2H2(g) + O2(g) → 2H2O
Hydrogen Fuel Cell
Anode = H2 Cathode = O2

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19.7 Electrolytic Cells
a) What are the products of electrolysis of NaBr(l)?

b) What are the products of electrolysis of a solution of NaBr? Na+ + 1e- → Na Ered = -2.71V
2H2O + 2e- → H2 + 2OH- Ered = -0.83V
2Br- → Br2 + 2e- Eox = -1.07V
2H2O → O2 + 4H+ 4e- Eox = -1.23V

19.8 Electrolysis Calculations

(IAmps )(t s )(MWproduct ) (IAmps )(t s )
= mass of product = moles of product
(n)(F) (n)(F)

How many moles of Mn will be formed if MnCl2 is electrolyzed for 2 hours using 10 Amps?

How long will it take to plate out 1.0kg of Al from molten AlCl3 with a current of 100.0 A?

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