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Home  > 68025-25-2 > FAQ > Why transition metal chloride complex have lower reduction potential than metal aqua ions?

Why transition metal chloride complex have lower reduction potential than metal aqua ions?

Temple
Temple Answered Aug 28 2021

Why transition metal chloride complex have lower reduction potential than metal aqua ions? For example:

AuX3+(aq)+3eX??Au(s)E°=+1.52 V[AuClX4]X?(aq)+3eX??Au(s)+4ClX?E°=+0.93 V

Au3+(aq)+3e?[AuCl4]?(aq)+3e??Au(s)?Au(s)+4Cl?E°E°=+1.52 V=+0.93 V(1)(2)

Is it because the chloride complex formation constant is very high (higher than aqua ions) so the reduction of AuX3+Au3+ is less favored?

Isaac
Isaac Answered Aug 28 2021

The anion AuClX4X?AuCl4? is the most known complex of gold(III). It is very stable complex and have very high formation constant (KfKf). That is the reason the metal chloride complex have a lower reduction potential than metal aqua ion. As pointed out in the other answer, this is a consequence of Nernst's law. Let's look at the two redox equations we are dealing with:

AuX3+(aq)+3eX?????Au(s)E°cathode[AuClX4]X?(aq)+3eX?????Au(s)+4ClX?(aq)E°anode

Au3+(aq)+3e?[AuCl4]?(aq)+3e?????Au(s)????Au(s)+4Cl?(aq)E°cathodeE°anode(1)(2)

If we substract the equation (2)(2) from the equation (1)(1), we get:

AuX3+(aq)+4ClX?(aq)????[AuClX4]X?(aq)E°cell=E°cathode?E°anode

Au3+(aq)+4Cl?(aq)????[AuCl4]?(aq)E°cell=E°cathode?E°anode(3)

The equation (3)(3) is the reaction for the formation of AuClX4X?AuCl4? with formation constant KfKf. If you applied the Nernst equation for the equation (3), then at 25 °C:

E°cell=RTnFlnQ=RTnFlnKf=0.0592nlogKf

This last solution of the equation (4) (where n=3) is because, when at equilibrium Q=K. If we know the Kf, we could have find the E°cell, and hence E°anode (which is for AuClX4X?). Unfortunately, I couldn't find Kf for AuClX4X? ion formation. Thus, I'd show how big Kf for AuClX4X? by applying the given values of E°cathode=+1.52 V and E°anode=+0.93 V on the equation (4):

E°cell=0.0592nlogKf ?logKf=n0.0592E°cell=30.0592(1.52?0.93)=29.9

 Kf=1029.9=7.91×1029

It is also in similar way you can find the E° for redox half-reaction of PtClX4X2? since we know its formation constant (Kf=1.0×1016):

PtX2+(aq)+2eX?????Pt(s)E°cathode=1.18 V[PtClX4]X2?(aq)+2eX?????Pt(s)+4ClX?(aq)E°anode=?

If we substract the equation (6) from the equation (5), we get:

PtX2+(aq)+4ClX?(aq)????[PtClX4]X2?(aq)E°cell=E°cathode?E°anode

From equation (4) where n=2:

E°cell=0.0592nlogKf=0.05922log(1.0×1016)=0.474

Since, E°cell=E°cathode?E°anode=0.474 V, and E°cathode=1.18 V,

E°anode=11.18 V?0.474 V=0.706 V

 [PtClX4]X2?(aq)+2eX?????Pt(s)+4ClX?(aq)E°=0.706 V (calculated)

This value is in good agreement with the experimental value, which is given as 0.755 V in electrpchemical series of CRC Handbook of Chemistry and Physics.

Source of formation constant of platinum complex ion

Garner
Garner Answered Aug 28 2021

This difference of redox potentials is a consequence of Nernst's law. The second equation is nothing else as the first one, where the concentration of the AuX3+ in a solution of AuClX4X? is extremely low. This sort of comparison could be used to calculate the equilibrium constant of the equilibrium AuX3++4ClX??AuClX4X?

Here, Nernst's law can be written : Au?AuX3++3eX?
E=0.93V=1.52V+0.059V3?log [AuX3+]
so that the concentration [AuX3+] in AuClX4X? is given by log[AuX3+]=30.059V(0.93V?1.52V)=?30
This means that in a 1 molar solution of AuClX4X?, the concentration of the ion AuX3+ is only 1×10?30 M. But the redox reaction happening in AuClX4X? is the same redox reaction that occurs between Au and AuX3+. Just the concentration of AuX3+ is extremely low in AuClX4X? solutions.

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