9.6
Celdas de concentración
Una celda de concentración es una celda electroquímica en la que la fem surge de una diferencia en la concentración de una especie entre dos semicelda…
En una celda de concentración, la fem surge de la diferencia de concentraciones entre dos medias celdas, lo que crea potenciales electrodos desiguales que impulsan un flujo espontáneo de electrones e iones.
Las celdas de concentración se dividen en celdas de concentración de electrodos y celdas de concentración de electrolitos.
En una celda de concentración de electrodos, los electrodos son idénticos, pero la concentración de la especie electroactiva varía en cada electrodo.
Un ejemplo estándar es el electrodo de hidrógeno, donde electrodos de platino idénticos están expuestos a gas de hidrógeno a diferentes presiones en la misma solución de iones de hidrógeno. Según la ecuación de Nernst, la célula opera espontáneamente y produce un emf positivo cuando p₂ es menor que p₁.
Por otro lado, las celdas de concentración de electrolitos consisten en electrodos idénticos sumergidos en el mismo electrolito a diferentes concentraciones. Estas células funcionan sin transferencia ni con transferencia.
Por ejemplo, una celda de concentración de zinc utiliza electrodos de zinc en soluciones con diferentes concentraciones de iones Zn²⁺. Según la ecuación de Nernst, la fem es positiva y el proceso es espontáneo cuando a₂ supera a a₁.
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Q1: What is the source of emf in a concentration cell?
In a concentration cell, emf arises from concentration differences between two half-cells, creating unequal electrode potentials that drive spontaneous electron and ion flow. Unlike galvanic cells powered by chemical reactions, the driving force here is the transfer of matter from higher to lower concentration, making the overall process physical in nature.
Q2: How do electrode concentration cells differ from electrolyte concentration cells?
Electrode concentration cells have identical electrodes with different concentrations of electroactive species, such as hydrogen gas at different pressures. Electrolyte concentration cells have identical electrodes immersed in the same electrolyte at different concentrations. Both types generate emf through concentration gradients, but the location of the difference distinguishes them.
Q3: What does the Nernst equation predict for hydrogen electrode concentration cells?
According to the Nernst equation, a hydrogen electrode concentration cell with identical platinum electrodes exposed to hydrogen gas at different pressures operates spontaneously with positive emf when the lower pressure (p₂) is less than the higher pressure (p₁). This spontaneous flow is analogous to gas expansion from high to low pressure regions.
Q4: How does a zinc concentration cell generate emf?
A zinc concentration cell consists of zinc electrodes immersed in solutions with different Zn²⁺ ion concentrations. The Nernst equation shows that emf is positive and the process is spontaneous when the ion activity at one electrode (a₂) exceeds that at the other (a₁), driving zinc transfer from higher to lower concentration regions.
Q5: What is the difference between concentration cells with and without transference?
Electrolyte concentration cells without transference use a salt bridge to separate solutions, allowing indirect ion transfer via the bridge. Cells with transference employ a porous membrane keeping solutions in direct contact, enabling ions to migrate across the junction. Both configurations generate emf from concentration differences but differ in ion transport pathways.
Q6: What is an example of an electrode concentration cell using amalgams?
A lead amalgam cell exemplifies electrode concentration cells with different metal concentrations. The cell notation Hg–Pb(c₁) | Pb²⁺(aq) | Hg–Pb(c₂) shows two mercury-lead amalgam electrodes at different lead concentrations. Positive emf corresponds to spontaneous lead transfer from the more concentrated amalgam to the less concentrated one.
Q7: Why is the overall process in a concentration cell considered physical rather than chemical?
Concentration cells operate through the transfer of matter from regions of higher to lower concentration, driven by concentration gradients rather than chemical reactions. This physical process of matter redistribution, similar to gas expansion or diffusion, distinguishes concentration cells from galvanic cells where electrical energy originates from chemical transformations.