In general, emf values in gas phase versus a solution vary because of the stability asscoiated with the hydrated cation product when it forms in solution. It is probably that because Li+ intereacts better with water than Cs+, it is more favorable for Li to lose and electron than Cs in water.
However, in the gas phase, reduction potential correlates to the ionization energy (energy to lose of an electron in the gas phase). Because the Cs valence electron is farther from the nucleus than the Li valence electron, Cs can lose an electron more easily than Li, which gives it a higher gas phase reduction potential.
so going down a period 1A, in liquid phase, Li is a stronger reducing agent because Li+ forms a more stable interaction with water. This also explains why going down 1A and reacting with water, we get more exothermic reactions. ...because further down the period, the reactions are more unstable.
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