Why is mercury a liquid at STP?

Vocabulary

Mercury is puzzling in several ways. It's a liquid at room temperature and inert pair
pressure, but all of its neighbors on the periodic table are solids. Mercury is lattice
much less reactive than cadmium or zinc. It's difficult to oxidize, and it
metal
doesn't conduct heat or electricity as well as other members of its group.
oxidize
Why are most metals solids? Most metals share their valence electrons valence electron
with surrounding metal atoms. Picture the metal as a lattice of positive ions
glued together by "sea" of shared valence electrons. This electron sea model explains many
properties of metals. For example, metals conduct electricity because the shared electrons are
free to move about; taking an electron from one part of the metal will cause electrons from
surrounding areas to rush in and fill the hole. Metals can be drawn into wire or pounded into
sheets because the metal ions can slide past each other but still be bound together by the shared
valence electrons.

The electron sea model explains some trends in metal hardness and melting point. Harder, high-
melting-point metals tend to share more valence electrons than softer, more easily melted metals.
For example, magnesium has a higher melting point than sodium because Mg2+ centers are glued
together by an electron sea with 2 electrons for every atom, while each atom in sodium metal
contributes only one electron.

Mercury hangs on to its valence 6s electrons very tightly. Mercury-mercury bonding is very
weak because its valence electrons are not shared readily. (In fact mercury is the only metal that
doesn't form diatomic molecules in the gas phase).

Heat easily overcomes the weak binding between mercury atoms, and mercury boils and melts at
lower temperatures than any other metal. The thin valence electron sea makes mercury's ability
to conduct electricity and heat much poorer than expected for a metal at that position in the
periodic table.

Why is the pair of 6s electrons so inert? The s electrons are able to come very close to the
nucleus. They swing around very massive nuclei at speeds comparable to that of light. When
objects move at such high speeds, relativistic effects occur. The s electrons behave as though
they were more massive than electrons moving at slower speeds. The increased mass causes
them to spend more time close to the nucleus. This relativistic contraction of the 6s orbital lowers
its energy and makes its electrons much less likely to participate in chemistry- they're buried deep
in the atomic core.

Why doesn't this effect make gold and thallium liquid too? Let's compare the electronic
configurations for gold, mercury, and thallium:

Atom Average atomic mass Ground state configuration

Au 196.9665 [Kr] 4d10 4f14 5s2 5p6 5d10 6s1
Hg 200.59 [Kr] 4d10 4f14 5s2 5p6 5d10 6s2
Tl 204.383 [Kr] 4d10 4f14 5s2 5p6 5d10 6s2 6p1
All three atoms have very low energy 6s orbitals. But the gold 6s orbital is only half filled.
Accepting an electron into that low energy orbital will lower energy overall, and metal-metal
bonding is expected to be strong as a result. Still, the 6s electron is held tightly and gold's
reputation as a 'noble metal' comes from its inertness.

Thallium is more massive, so the 6s pair is even more inert than in Hg. But thallium has a 6p
electron. Remember that p electrons can't approach the nucleus as closely as s electrons; the p
orbital has a nodal plane that passes through the nucleus. So that 6p electron is fairly reactive
compared to the 6s electrons. That explains why the most common ion of thallium is Tl+, and not
the +3 ion like B and Al and other members of its family.

Reference

1. L.J. Norrby, "Why is mercury liquid? Or, why do relativistic effects not get into
chemistry textbooks?" Journal of Chemical Education, 68, 110-113 (1991).
2. D. S. Rustad, "How soft is mercury? (Letter to the Editor)", Journal of Chemical
Education, 64, 470 (1987).