Diagonal

relationship

Pictorial representation of examples of diagonal

relationship.
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A diagonal relationship is said to exist

between certain pairs of diagonally
adjacent elements in the second and third
periods (first 20 elements) of the periodic
table. These pairs (lithium (Li) and
magnesium (Mg), beryllium (Be) and
aluminium (Al), boron (B) and silicon (Si),
etc.) exhibit similar properties; for
example, boron and silicon are both
semiconductors, forming halides that are
hydrolysed in water and have acidic
oxides.

The organization of elements on the

periodic table in to horizontal rows and
vertical columns makes certain
relationships more apparent (periodic law).
Moving rightward and descending the
periodic table have opposite effects on
atomic radii of isolated atoms. Moving
rightward across the period decreases the
atomic radii of atoms, while moving down
the group will increase the atomic radii.[1]
Similarly, on moving rightward a period, the
elements become progressively more
covalent, less basic and more
electronegative, whereas on moving down
a group the elements become more ionic,
more basic and less electronegative. Thus,
on both descending a period and crossing
a group by one element, the changes
"cancel" each other out, and elements with
similar properties which have similar
chemistry are often found – the atomic
size, electronegativity, properties of
compounds (and so forth) of the diagonal
members are similar.
It is found that the chemistry of a first-
group (second period) element often has
similarities to the chemistry of the second-
group (third period) element one column to
the right of it in the periodic table. Thus,
the chemistry of Li has similarities to that
of Mg, the chemistry of Be has similarities
to that of Al, and the chemistry of B has
similarities to that of Si. These are called
diagonal relationships. (It is not as
noticeable after B and Si.) The reasons for
the existence of diagonal relationships are
not fully understood, but charge density is
a factor. For example, Li+ is a small cation
with a +1 charge and Mg2+ is somewhat
larger with a +2 charge, so the ionic
potential of each of the two ions is roughly
the same. Using the Li–Mg pair (under
room temperature and pressure):

1. When combined with oxygen under

standard conditions, Li and Mg form
only normal oxides whereas Na
forms peroxide and metals below Na,
in addition, form superoxides.
2. Li is the only Group 1 element which
forms a stable nitride, Li3N.[2] Mg, as
 well as other Group 2 elements, also
form nitrides.[2]
3. Lithium carbonate, phosphate and
fluoride are sparingly soluble in water.
The corresponding Group 2 salts are
insoluble. (Think lattice and solvation
energies).
4. Both Li and Mg form covalent
organometallic compounds. LiMe
and MgMe2 (cf. Grignard reagents)
are both valuable synthetic reagents.
The other Group 1 and Group 2
analogues are ionic and extremely
 reactive (and hence difficult to
manipulate).[3]
5. Chlorides of both Li and Mg are
deliquescent (absorb moisture from
surroundings) and soluble in alcohol
and pyridine. Lithium chloride, like
magnesium chloride (MgCl2·6H2O)
separates out from hydrated crystal
LiCl·2H2O.

References
1. Ebbing, Darrell and Gammon, Steven
D. "Atomic Radius". General Chemistry
(PDF) (9th ed.). Houghton Mifflin.
 pp. 312–314. ISBN 978-0-618-93469-
0.
2. Clark, Jim (2005). "Reactions of the
Group 2 Elements with Air or Oxygen" .
chemguide. Retrieved January 30,
2012.
3. Shriver, Duward (2006). Inorganic
Chemistry (4th ed.). Oxford University
Press. ISBN 978-0199264636. Li/Mg
p. 259; Be/Al p. 274; B/Si p. 288.

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