Chemistry - Why does increasing number of salt bridges increase voltage of electrochemical battery?

The voltage you measure between the terminals of a voltaic cell will depend on two factors:

  1. The intrinsic maximum voltage $(V_\mathrm{max} = E_\mathrm{cell})$ that the cell could produce, depending on the $E^o_{red}$ of each half cell, the ion concentrations and the temperature. This is calculated from the Nernst equation:

    $$E_\mathrm{cell} = E^⦵_\mathrm{cell} - \frac{RT}{zF}\ln{Q_r}$$

  2. Resistive terms that come from within the cell, including overpotentials at the electrodes and other factors that influence the internal resistance of the cell.

Overall, the observed voltage $(V_L)$ measured at the terminals of the cell will be lower than the theoretical $V_\mathrm{max}$ because the internal resistance of the cell involves a voltage drop, in the same way that you would see an external voltage drop across a resistor in series in the circuit.

$V_L$ can be calculated in the following way:

$$V_L = V_\mathrm{max} - V_I$$

where $V_I$ is the internal voltage drop from the internal resistance of the cell. This drop in voltage depends on the internal resistance of the cell ($R_I$) and the total current $(I)$ running through the cell (and the circuit, see

$$V_I = I \cdot R_I$$

Your question seems to revolve around how the salt bridge affects the internal resistance of the cell. It would make sense that the more salt bridges you add, the less internal resistance would result, so the smaller the voltage drop and the larger the measured voltage from the cell.

It is possible to think of the salt bridge, which involves the flow of ions, as being analogous to a wire, which involves the flow of electrons. The resistance of a wire $(R)$ is dependent on it cross-sectional area (see

$$R = \frac{ρL}{A}$$

where $ρ$ is resistivity; $L$ is length; $A$ is cross sectional area.

So it follows that the same may be true for a salt bridge. By adding more salt bridges, you are increasing the cross-sectional area, decreasing the internal resistance and increasing the observed voltage, which would approach the theoretical maximum voltage as the internal resistance approaches zero.