Galvanic Cell Explorer

Wire a redox couple to the standard hydrogen electrode, read its reduction potential on the meter, and follow the electrons.

1Left cell: reference
  • H+1.00 M (pH 0)
  • H2 gas1 atm
  • Electrodeplatinum
  • E0.000 V

The standard hydrogen electrode is the zero of the scale by definition. Nothing here is adjustable.

2Right cell: experimental
3E°′ table

The cell

Speed

Readings

Against the hydrogen reference, ΔE°′ is simply E°′ of the right cell, and the reference H+ is at pH 0. For the ΔG°′ of a biochemical reaction, put its second couple in the left cell so that both sides are at pH 7.

Nernst equation, live

25 °C, so 2.303 RT/F = 0.0592 V

Try this
  1. Leave the hydrogen electrode on the left and NAD+/NADH on the right at standard conditions. The meter reads the table value. Which way are the electrons pushed, and which cell is the anode?
  2. Make [NADH] ten times [NAD+]. Before you look: by how many millivolts should a two-electron couple move for a tenfold change in the ratio, and in which direction?
  3. Put H+/H2 in the right cell and slide its pH from 7 down to 0. Why does the meter stop at exactly zero?
  4. Choose O2/H2O and move the pH. Then compare NAD+/NADH over the same pH range. Why is one slope twice the other?
  5. Set the left cell to another couple: NAD+/NADH on the left, O2/H2O on the right. Read ΔE°′ and ΔG°′. Then swap the two cells. What changes on the meter, and what does not change?
  6. Step down the electron transport group one carrier at a time, each carrier against the one before it. Which steps release the most free energy per pair of electrons?
  7. Pyruvate/lactate against NAD+/NADH: which way does the reaction run at standard conditions? Now change the concentrations until the electrons reverse. ΔG°′ did not change. What did?
  8. Glutathione: cut [GSSG] and [GSH] by the same factor of ten. The ratio is unchanged but E moves. Use the half-reaction to explain why.
  9. Put the same couple in both cells with different ratios. There is still a voltage. What is ΔE°′ for this cell, and where does the driving force come from?
  10. Zn2+/Zn on the left and Cu2+/Cu on the right, then press Run to equilibrium. Why does the voltage hold nearly steady for most of the run and then collapse?
  11. Switch the E°′ table. Which couples change, and by how much would that change a calculated ΔG°′?
How to read this cell

The reference. The left cell starts as the standard hydrogen electrode: platinum in 1 M H+ with H2 bubbling over it at 1 atm. Its potential is defined as 0.000 V, so every reading against it is the reduction potential of the right cell.

The meter. It reads E = E(right) − E(left). A positive reading means the right cell takes electrons (it is the cathode). A negative reading means the right cell gives them up (it is the anode). The meter draws almost no current, so nothing is used up while you measure; at each electrode the couple is turning over in both directions at the same rate.

E°′. Biochemistry tables list the potential with every solute at 1 M, gases at 1 atm and pH 7. Set the right cell to those conditions and the meter shows the table value. Because the reference stays at pH 0, the hydrogen couple itself reads −0.414 V when it is moved to pH 7.

Away from standard conditions. The Nernst equation corrects E°′ for the actual concentrations and pH. A tenfold change in the ratio of oxidized to reduced form moves E by 59 mV divided by the number of electrons.

Two couples. Electrons go from the couple with the lower E to the couple with the higher E. ΔE = E(acceptor) − E(donor) and ΔG = −nFΔE, so a positive ΔE is a negative ΔG.

Under each beaker. The half-reaction is written the way it is running, and E is given for that direction: the reduction potential in the cathode cell, and the same number with its sign reversed in the anode cell, where the couple is being oxidized. Those two values add up to ΔE. The meter and the tiles always use reduction potentials.

Running the cell. Run to equilibrium closes the circuit through a resistor. Reactant is used up, Q climbs, and E falls until Q equals K′eq and E is zero. The Speed switch moves in tenfold steps. It sets how fast the run plays and how fast the dots move; the time on the plot is the same at every setting.

What the model assumes
  • 25 °C. Activities are taken as concentrations (and as pressures in atm for gases). Solids and water have activity 1.
  • The number of H+ in each half-reaction is fixed as written at pH 7. Real couples change slope where a species gains or loses a proton, so readings far from pH 7 are a guide only.
  • Every cell except the hydrogen reference is buffered, so its pH stays where the slider puts it. The reference is 1 M strong acid with no buffer.
  • Standard state is a reference point, not a recipe. Nobody makes 1 M cytochrome c.
  • Most of these couples do not exchange electrons with bare platinum at a useful rate. In the laboratory an enzyme or a mediator dye carries the electrons. The potentials are the same.
  • When the cell runs: 100 mL in each half-cell, a 10 Ω load, no internal resistance. Gases are supplied at constant pressure and metal electrodes do not run out.
  • The dots are a picture, not a count. Their number follows the logarithm of concentration. A tenfold step on the Speed switch plays the run exactly ten times faster, but moves the dots only about three times faster so they stay visible.
cochranlearning.com · Galvanic Cell Explorer v1.0