Which of the following processes is endothermic? Explain with reason?

A) #\text{S} -> \text{S}^-#
B) #\text{S}^(-) -> \text{S}^(2-)#
C) #\text{Na} -> \text{Na}^-#
D) #\text{P} -> \text{P}^-#

1 Answer
Jun 22, 2018

Well, likely #(B)#... we try to shove an electron onto an anion, and it should not be immediately happy... One would see the same occurrence with oxygen anion.

Note that I am using the convention that an atom that becomes more stable due to gaining an electron has a negative electron affinity. My reference page lists these values as the opposite sign, and I am aware of that.


But as physical chemists, we ought to examine the data...

#A)# #"S"(g) + e^(-) -> "S"^(-)(g)#

The first electron affinity of sulfur atom is #bb(-"2.0771043 eV")#, i.e. the atom becomes more stabilized by adding the electron in.

Although we are adding electrons into a #3p^4# valence shell, which adds repulsion, it seems to balance out to be negative due to the increase in atomic radius.

#B)# #"S"^(-)(g) + e^(-) -> "S"^(2-)(g)#

The second electron affinity of sulfur atom is #bb"4.726 eV"#, i.e. the atom gets more destabilized by adding the electron in.

This makes sense, because one would be shoving an electron into an electron-dense region before forming the noble gas configuration.

#C)# #"Na"(g) + e^(-) -> "Na"^(-)(g)#

The first electron affinity of sodium atom is #bb(-"0.5479263 eV")#.

There is some electron repulsion because it would go into the half-filled #3s# orbital, but apparently it is sufficiently counterbalanced by the increase in atomic radius that results, because it is actually a little negative, not positive value.

[This is not obvious. And well, alright, this value is not that small, but it looks small.]

#D)# #"P"(g) + e^(-) -> "P"^(-)(g)#

The first electron affinity of phosphorus atom is #bb(-"0.7466071 eV")#.

There is some electron repulsion because it would go into one of the orbitals in the half-filled #3p# subshell, but apparently it is sufficiently counterbalanced by the increase in atomic radius that results, because it is actually a little negative, not positive value.

[This is not obvious. And well, alright, this value is not that small, but it looks small.]