Calculating E°cell
Calculating the standard cell potential is the most common quantitative task in MCAT electrochemistry. The formula is straightforward, and every calculation follows the same pattern.
The Master Equation
Important: Both E°cathode and E°anode are the standard reduction potentials from the table. You do not need to reverse any signs before plugging in. The subtraction does the work.
Step-by-Step Process
- Identify the cathode and anode. The species with the higher (more positive) E° is reduced at the cathode. The species with the lower E° is oxidized at the anode.
- Look up both reduction potentials from the table.
- Subtract: E°cell = E°cathode - E°anode.
- Interpret the sign. Positive = spontaneous (galvanic). Negative = nonspontaneous (requires external energy).
Worked Example 1: Daniell Cell
Half-reactions from the table:
- Cu2+ + 2e- -> Cu E° = +0.34 V
- Zn2+ + 2e- -> Zn E° = -0.76 V
Copper has the higher E°, so it is the cathode (reduction). Zinc has the lower E°, so it is the anode (oxidation).
E°cell = E°cathode - E°anode = (+0.34) - (-0.76) = +1.10 V
The positive value confirms this is a spontaneous reaction.
Worked Example 2: Iron-Silver Cell
Half-reactions:
- Ag+ + e- -> Ag E° = +0.80 V
- Fe2+ + 2e- -> Fe E° = -0.44 V
E°cell = (+0.80) - (-0.44) = +1.24 V
Silver is reduced, iron is oxidized. Spontaneous.
Worked Example 3: Testing a Nonspontaneous Direction
What if someone proposes: Cu + Zn2+ -> Cu2+ + Zn?
That would make zinc the cathode and copper the anode:
E°cell = E°cathode - E°anode = (-0.76) - (+0.34) = -1.10 V
Negative E°cell means this direction is nonspontaneous. You would need to supply at least 1.10 V of external energy to force this reaction (making it an electrolytic cell).
Critical Rule: Do NOT Multiply E° by Coefficients
When balancing a cell reaction, you may need to multiply one half-reaction to equalize electrons. Never multiply the E° value.
Example: Building a cell from Al and Cu:
- Cu2+ + 2e- -> Cu E° = +0.34 V
- Al3+ + 3e- -> Al E° = -1.66 V
To balance electrons, you multiply the copper half-reaction by 3 and the aluminum half-reaction by 2:
- 3Cu2+ + 6e- -> 3Cu E° is still +0.34 V (not 3 x 0.34)
- 2Al3+ + 6e- -> 2Al E° is still -1.66 V (not 2 x -1.66)
E°cell = (+0.34) - (-1.66) = +2.00 V