Periodic Table: Anomalies of first member of group

Number 68
1
C
hem
F
actsheet
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Before working through this Factsheet you should:
Be familiar with the general trends across periods and down groups in
the periodic table;
Be familiar with general properties of Groups 1, 2 and 7.
After working through this Factsheet you will:
Understand why period 2 elements generally display noticeably
different properties to the other elements in the same group;
Be familiar with examples of the atypical properties of lithium,
beryllium and fluorine;
Understand what is meant by the "diagonal relationship" in the Periodic
Table.
Anomalies of lithium
Thermal decomposition of carbonates, nitrates and hydroxides to
give the oxide.
This is due to the high charge density of the lithium ion - combination
with the high charge density oxide ion is favoured.
Does not form peroxides and superoxides readily due to small size
of the ion.
Some compounds show a degree of covalent character due to
polarising power of the small Li
+
ion.
Relatively low solubility of carbonate, fluoride, hydroxide and
phosphate due to the high lattice enthalpy.
Anomalies of beryllium
Compounds show appreciable covalent character - eg dissolving
in organic solvents, low melting points, hydrolysed by water. This
is due to its much larger ionisation energy and the much smaller
size of its ions.
Amphoteric hydroxide.
Does not form oxide in air at room temperature.
Will not react with water and dilute acids.
Anomalies of fluorine
Hydrofluoric acid is a weak acid (due to the high H-F bond strength).
Hydrogen fluoride has a high boiling point (hydrogen bonding).
The F-F bond strength is very low, because the small size of the
atom brings the lone pairs close together.
Forms compounds with all elements except helium, neon and argon.
Does not form oxy-acids as it is more electronegative than oxygen.
Only exhibits oxidation state of -1, as it is the most electronegative
element.
Is such a strong oxidising agent that it must be prepared by
electrolysis, rather than chemically.
Because of its small size, more fluorine atoms can be packed
around a central atom - eg AlF
6
3
is formed, but only AlCl
4

.
Why are period 2 elements different?
The atoms are very small in size;
The elements are very electronegative;
They have no d-orbitals.
Consequences of small size
Lower than expected electron affinity.
We might have expected high electron affinity for these elements - the
new electron will be very close to the nucleus. However, because of
their small size, the extra electron is being put into a region that is
already crowded with electrons - producing a significant amount of
repulsion.
For example, although the general trend is for electron affinity to
decrease down a group, fluorine has a lower electron affinity than
chlorine, and oxygen has a lower electron affinity than sulphur.
Increased covalent character for small cations.
This is due to high charge density on the cations - bonds are polarised.
For example lithium chloride dissolves in alcohols, unlike the remainder
of group 1 chlorides; beryllium chloride dissolves in diethyl ether,
unlike the remainder of group 2 chlorides.
Consequences of high electronegativity
Coupled with small size, high electronegativity accentuates nonmetallic
behaviour.
This means that the metallic elements form compounds with appreciable
covalent character, as described above. Some oxides - eg beryllium - are
amphoteric.
Nitrogen, oxygen and fluorine can be involved in hydrogen bonds.
As a consequence, the boiling points of NH
3
, H
2
O and HF are higher
than those of PH
3
, H
2
S and HCl, although the general group trend is for
boiling points of hydrides to increase down the group.
Consequences of lack of d-orbitals
Form a maximum of four bonds.
For example, nitrogen exhibits a maximum valency of 3 (eg ammonia
NH
3
) but phosphorus can form PCl
5
. Similarly, sulphur forms SF
6
, but
no equivalent compound is formed by oxygen.
Some reactions which occur for other members of the group cannot
occur for the first member.
This is because some reactions progress via a transition state involving
an additional bond; the lack of availability of d-orbitals in the second
energy level means that a mechanism that works for the rest of the
group will not work for the first member.
For example, carbon tetrachloride (CCl
4
) is resistant to hydrolysis, but
the other tetravalent group 4 chlorides will hydrolyse.
Cl

Li
+
C C Si Si
-bonds are more efficient between 2p orbitals than 3p (or higher).
This is due to the strong overlap because of the small size of the atoms.
For example carbon forms very many compounds with double or triple
carbon-carbon bonds, whilst silicon does not. Nitrogen and oxygen
exist as diatomic molecules (involving multiple bonds), whilst
phosphorus and sulphur exist as P
4
and S
8
respectively, with no multiple
bonds.
Remember: ionic compounds generally dissolve in polar solvents and
covalent compounds in non-polar solvents.
Chem Factsheet
2
68. Periodic Table: Anomalies of first member of group
So, for example, atomic radius decreases from lithium to beryllium, but
increases from beryllium to magnesium. The result is that the atomic radii
of lithium and magnesium are similar (1.5510
-10
m

and 1.610
-10
m
respectively).
Diagonal Relationships
This refers to the similarities exhibited between the first element of some
groups and the second element of the next group to the right.
Note: this relationship does not hold for all the groups; the only significant
relationships are the ones illustrated above.
Why is there a relationship?
Diagonal relationships occur because of the trends in properties down
groups and across periods.The trend in properties across a period is usually
opposite to the trend down a group - for example, ionisation energy increases
across a period but decreases down a group, while atomic radius decreases
across a period but increases down a group (Fig 1).
In particular, the polarising power of the corresponding ions is similar.
This is because the increase in size from one period to the next is offset by
the increased charge.
Similarities between lithium and magnesium include:
on reaction with air, forms oxide, not peroxide or superoxide
carbonates thermally decompose, giving the oxide and carbon dioxide
nitrates thermally decompose, giving the oxide, nitrogen dioxide and
oxygen
Similarities between beryllium and aluminium include
appreciable covalent character of compounds (eg the chlorides are largely
covalent)
formation of electron-deficient covalent chlorides, which tend to
dimerize or polymerize
amphoteric oxides
hydrolysis of salts
Note that lithium and beryllium differ from the remainder of the elements
in their groups with regard to these properties, as discussed above.
Increase in:
atomic radius
metallic character
Decrease in:
ionisation energy
electronegativity
acidity of oxides
Increase in:
ionisation energy
electronegativity
acidity of oxides
Decrease in:
atomic radius
metallic character
Fig 1. Trends in the periodic table
Li Be B C
Na Mg Al Si
Acknowledgements: This Factsheet was researched and written by Cath Brown.
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
1NU. ChemistryFactsheets may be copied free of charge by teaching staff or
students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in
any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136
Practice Questions
1. (a) Explain why the boiling points of hydrogen fluoride and hydrogen
bromide are both higher than that of hydrogen choride
(b) Explain why hydrofluoric acid is a weak acid
2. Lithium chloride dissolves in alcohols; sodium chloride does not.
(a) Explain the significance of these observations
(b) Account for these observations
3. (a) Explain why some chemical similarities between beryllium and
aluminium are to be expected
(b) State two such similarites
4. Explain why alkenes are common, but the corresponding silicon
compounds, silenes, are very rare.
5. Suggest why lithium fluoride is insoluble
6. Explain why PCl
5
exists, but not NCl
5
A n s w e r s
1 . ( a ) T h e b o i l i n g p o i n t o f h y d r o g e n f l u o r i d e i s h i g h e r t h a n t h a t o f
h y d r o g e n c h l o r i d e b e c a u s e o f t h e s t r o n g h y d r o g e n b o n d i n g p r e s e n t
i n H F , w h i c h i s n o t p r e s e n t i n H C l . T h e b o i l i n g p o i n t o f h y d r o g e n
b r o m i d e i s h i g h e r t h a n t h a t o f h y d r o g e n b r o m i d e b e c a u s e o f t h e
i n c r e a s i n g s t r e n g t h o f t h e V a n d e r W a a l s f o r c e s , d u e t o i n c r e a s i n g
m o l e c u l a r s i z e
( b ) T h e g r e a t e r t h e d e g r e e o f i o n i s a t i o n i n w a t e r , t h e s t r o n g e r t h e a c i d .
S i n c e t h e H - F b o n d i s v e r y s t r o n g , h y d r o g e n f l u o r i d e d o e s n o t
i o n i z e f u l l y i n w a t e r
2 . ( a ) A l c o h o l i s a n o r g a n i c s o l v e n t . C o v a l e n t s u b s t a n c e s w o u l d b e
e x p e c t e d t o d i s s o l v e i n i t , b u t n o t i o n i c o n e s . T h i s s u g g e s t s t h a t
l i t h i u m c h l o r i d e h a s a p p r e c i a b l e c o v a l e n t c h a r a c t e r .
( b ) T h e l i t h i u m c a t i o n i s v e r y s m a l l w i t h a v e r y h i g h c h a r g e d e n s i t y .
T h e i o n i c b o n d b e c o m e s p o l a r i s e d , g i v i n g r i s e t o s o m e c o v a l e n t
c h a r a c t e r .
3 . ( a ) T h i s i s a n e x a m p l e o f t h e d i a g o n a l r e l a t i o n s h i p . T r e n d s a c r o s s t h e
p e r i o d a r e i n t h e o p p o s i t e d i r e c t i o n t o t r e n d s d o w n t h e g r o u p ,
l e a d i n g t o s i m i l a r i t e s b e t w e e n a n e l e m e n t a n d t h e e l e m e n t d i a g o n a l l y
b e l o w i t t o t h e r i g h t . T h e s e s i m i l a r i t e s i n c l u d e i o n i s a t i o n e n e r g y ,
e l e c t r o n e g a t i v i t y , a t o m i c r a d i u s a n d p o l a r i s i n g p o w e r o f c a t i o n s .
( b ) A n y t w o o f : a p p r e c i a b l e c o v a l e n t c h a r a c t e r o f c o m p o u n d s ;
a m p h o t e r i c o x i d e s ; h y d r o l y s i s o f s a l t s ; e l e c t r o n - d e f i c i e n t c h l o r i d e s
w h i c h d i m e r i z e / p o l y m e r i z e ( o t h e r a c c e p t a b l e a n s w e r s a r e p o s s i b l e -
t h e y s h o u l d r e f e r t o p r o p e r t i e s s h a r e d b y b e r y l l i u m a n d a l u m i n i u m ,
b u t n o t s h a r e d w i t h t h e r e m a i n d e r o f g r o u p 2 )
4 . T h e s m a l l s i z e o f c a r b o n a t o m s a l l o w s a h i g h d e g r e e o f o v e r l a p b e t w e e n
n e i g h b o u r i n g 2 p - o r b i t a l s . T h e l a r g e r s i z e o f s i l i c o n a t o m s m e a n s t h e r e
i s v e r y l i t t l e o v e r l a p b e t w e e n t h e 3 p - o r b i t a l s
5 . E x t r e m e l y h i g h l a t t i c e e n t h a l p d u e t o b o t h a n i o n a n d c a t i o n b e i n g s m a l l .
6 . N i t r o g e n h a s n o d - o r b i t a l s a v a i l a b l e , a n d s o c a n n o t f o r m m o r e t h a n f o u r
b o n d s .