|
5. Survey
of Period
3: Na across to Ar (8 elements, Z = 11 to 18)
5.3 Period 3 trends in bonding, structure, oxidation
state, formulae & reactions
M+
X- ionic bond, Mδ+-Xδ+
polar bond and M-X a relatively
non-polar bond (no partial charges shown)
(0) DATA TABLE on
period 3 elements - structure of elements and compounds, oxidation
states and formulae
|
Element |
Sodium |
Magnesium |
Aluminium |
Silicon |
Phosphorus |
Sulfur |
Chlorine |
Argon |
|
old/latest Group |
1 |
2 |
3/13 |
4/14 |
5/15 |
6/16 |
7/17 |
0/18 |
|
ZSymbol
|
11Na |
12Mg |
13Al |
14Si |
15P |
16S |
17Cl |
18Ar |
|
Structure of element |
solid metallic
lattice of Na+ and free e- |
solid metallic
lattice of Mg2+ and free e-s |
solid metallic
lattice of Al3+ and free e-s |
solid giant
covalent lattice Sin |
solid small
covalent molecules P4 |
solid small
covalent molecules S8 |
gaseous small
covalent molecules Cl2 |
gaseous single atoms Ar |
|
electron configuration |
[Ne]3s1 |
[Ne]3s2 |
[Ne]3s23p1 |
[Ne]3s23p2 |
[Ne]3s23p3 |
[Ne]3s23p4 |
[Ne]3s23p5 |
[Ne]3s23p6 |
|
common oxidation states
e.g. in oxides,
chlorides, hydrides |
+1
max +1 |
+2
max +2 |
+3
max +3 |
+4
max +4 |
+3, +5
max +5 |
-2, -2, +4, +6
max +6 |
-1, +1, +3,
+5, +7
max +7 |
at Xe can get max of +8 in some compounds,
but not for Ar! |
|
electronegativity of element |
0.93 |
1.31 |
1.61 |
1.90 |
2.19 |
2.58 |
3.16 |
3.20 |
|
formula of oxides
(oxidation states of the period 3 element) |
Na2O,
Na2O2
(+1) |
MgO
(+2) |
Al2O3
(+3) |
SiO2
(+4) |
P4O6 and
P4O10
(+3,
+6) |
SO2,
SO3
(+4, +6) |
Cl2O, ClO2,
Cl2O7
(+1,+4,+7) |
- |
|
Ratio of
period 3 element to oxygen (formulae in bold) |
1 : 0.5 |
1 : 1 |
1 : 1.5 |
1 : 2 |
1 : 2.5 |
1 : 2.5 |
- |
- |
|
bonding
and structure of oxides |
ionic lattice |
ionic lattice |
ionic lattice |
solid covalent giant
structure |
solid covalent small
molecules |
covalent small
gaseous
molecules |
covalent small
gas/liquid
molecules |
- |
|
Melting
point of oxide in highest oxidation state |
1275oC |
2852oC |
2072oC |
1723oC |
580oC |
17/62oC |
-91oC |
- |
|
electronegativity difference X-O (O
is 3.44) nature of bond |
2.51
ionic
Na+ O2-or
O22- |
2.13
ionic
Mg2+ O2- |
1.83
ionic with
some covalent character
Al3+ O2- |
1.54
covalent
Siδ+-Oδ- |
1.25
covalent
Pδ+-Oδ- |
0.86
covalent
Sδ+-Oδ- |
0.28
covalent
Clδ+-Oδ- |
- |
|
formula of chlorides |
NaCl |
MgCl2 |
AlCl3 |
SiCl4 |
PCl3,
PCl5 |
S2Cl2,
SCl2, SCl4 |
Cl2 |
- |
|
bonding in chlorides |
ionic lattice |
ionic lattice |
ionic lattice, readily vaporises to covalent dimer molecules Al2Cl6 |
covalent small
liquid
molecules |
liquid covalent small
molecules |
covalent small
liquid
molecules |
small
diatomic gaseous molecule |
- |
|
electronegativity difference X-Cl
(Cl is 3.16) nature of bond |
2.23
Na+ H- |
1.85
Mg2+ Cl- |
1.55
Al3+ Cl- |
1.26
Siδ+-Clδ- |
1.25
Pδ+-Clδ- |
0.58
Sδ+-Clδ- |
0.00
Cl-Cl |
- |
|
Formula of hydride |
NaH |
MgH2 |
AlH3 |
SiH4 |
PH3 |
H2S |
HCl |
- |
|
bonding and structure of hydride |
ionic lattice |
'polymer-like' structure of
intermediate ionic/covalent nature |
'polymer-like' structure of an
intermediate ionic/covalent nature |
small covalent gaseous molecule |
small covalent gaseous molecule |
small covalent gaseous molecule |
small covalent gaseous molecule |
- |
|
electronegativity difference X-H (H is 2.20) nature of bond |
1.27
Na+ H- |
0.89
Mgδ+-Hδ- |
0.59
Alδ+-Hδ- |
0.30
Si-H |
0.01
P-H |
0.38
Hδ+-Sδ- |
0.96
Hδ+-Clδ- |
- |
TOP OF PAGE
and sub-index
(1) The
structure and physical properties of the period 3 elements
(see also section 5.1)
-
The trend is metal
lattice ==> giant covalent structure ==> small covalent
molecules
-
Sodium Na, magnesium Mg and
aluminium Al
are silvery solids, with a metal lattice structure, high boiling
points and are good
conductors of heat/electricity due to the delocalised free
electrons moving between the immobile metal ions.
-
Si has a
non-metallic giant covalent structure based on a tetrahedral
arrangement of S-Si bonds and is a poor conductor of
heat/electricity.
-
Phosphorus P4,
sulfur S8 and chlorine Cl2 are simple-small covalent
molecules and Ar consists of single atoms. The molecules are
only held together by the weakest of the intermolecular forces,
namely the instantaneous dipole - induced dipole forces, and
consequently have very low melting/boiling points.
TOP OF PAGE
and sub-index
(2) Electron
configuration and oxidation states of period 3 elements
-
Electron configurations
of 2,8,1 or 1s22s22p63s1
to 2,8,8 or 1s22s22p63s23p6
-
Filling
the s orbital (max 2 e-'s) gives the metallic s-block
elements of Groups 1-2,
-
filling the p orbitals gives the
predominantly non-metallic p block elements of Group 3-7, 0
(Gps 13-18) bar aluminium for Period 3.
-
Oxidation states
in compounds (numerically = valency) are: sodium Na (+1 only),
magnesium Mg (+2
only), aluminium Al (+3 only), Si (+4, -4 with electropositive metals), P (usually -3, +3 or +5), S
(-2, +4 and +4), Cl (-1, +1, +3, +5 and +7), Ar has no stable
compounds due to the full outer quantum level (shell) being
full, conferring extra electronic stability on the atom.
TOP OF PAGE
and sub-index
(3) Reaction of
element with oxygen and the structure of the oxides of period 3 (see
also section 5.1)
|
(Gp 1) 4Na(s)
+ O2(g) ==> 2Na2O(s)
and Na2O2
on heating the metal in air |
(Gp 2) 2Mg(s)
+ O2(g) ==> 2MgO(s)
on strongly heating metal in air |
|
(Gp 3)
4Al(s)
+ 3O2(g) ==> 2Al2O3(s)
needs high temperature |
(Gp 4)
Si(s) + O2(g)
==> SiO2(g)
needs high temperature |
|
(Gp 5)
P4(s)
+ 5O2(g) ==> P4O10(s)
on heating in air |
(Gp 6)
S(s)
+ O2(g) ==> SO2(g)
and a little SO3
on heating in air |
|
(Gp 7) Chlorine -
no reaction |
(Gp 0) Argon - no
reaction |
TOP OF PAGE
and sub-index
(4) Reaction of
period 3 oxides
with water, acids and alkalis
(see also section 5.1)
|
(Gp 1) Na2O(s)
+ H2O(l) ==> 2NaOH(aq)
pH 13-14
strong base from ionic oxide
ionic equation:
(Na+)2O(s)
+ H2O(l) ==> 2Na+(aq) + 2OH-(aq)
and for sodium peroxide
Na2O2(s)
+ 2H2O(l) ==> 2NaOH(aq)
+ H2O2(aq) |
(Gp 2) MgO(s)
+ H2O(l) ==>
Mg(OH)2(aq/s)
~pH 11-12 weak base from ionic oxide
ionic equation:
Mg2+(s) + H2O(l)
==> Mg2+(aq) + 2OH-(aq) |
|
(Gp 3/13)
Al2O3,
insoluble, no reaction with water (pH remains at 7), but amphoteric with
respect to strong acids and strong bases (alkalis) |
(Gp 4/14) SiO2,
insoluble, no reaction with water (pH remains at 7), but weakly acidic and
will dissolve a little in strong bases (alkalis) e.g. conc. NaOH(aq) |
|
(Gp 5/15)
P4O6(s) +
6H2O(l) ==> 4H3PO3(aq)
~pH 2 weak
acid from covalent oxide
P4O10(s) +
6H2O(l) ==> 4H3PO4(aq)
pH
0-1
strong acid from covalent oxide
Because phosphoric(V) acid is tribasic,
there are three possible 'phosphate' anions
H2PO4-,
HPO42- and PO43- |
(Gp 6/16) SO2(aq)
+ H2O(l) ===> H2SO3(aq)
sulfurous acid, theoretically dibasic, but the main ionic
reaction is
SO2(aq)
+ H2O(l)
H+(aq) + HSO3-(aq)
pH 2-3
weak acid from covalent oxide
There are two possible anions
HSO3-
hydrogensulfite or hydrogensulfate(IV) ion
and SO32-
sulfite or sulfate(IV) ion
SO3(g)
+ H2O(l) ==> H2SO4(aq)
pH 0-1
strong acid from covalent oxide
Sulfuric(VI) is dibasic so there are two
possible anions
HSO4-
hydrogensulfate or hydrogensulfate(VI) ion
SO42- sulfate or
sulfate(VI) ion |
|
(Gp 7/17)
Cl2O(g)
+ H2O(l) ==> 2HClO(aq)
~pH 3?
weak acid from covalent oxide
Cl2O7(l)
+ H2O(l) ==> 2HClO4(aq)
pH 1
strong acid from covalent oxide |
(Gp 0/18) argon has no
oxide |
TOP OF PAGE
and sub-index
(5) Reaction of
period 3 element
with chlorine and the structure of the chloride
(see also section 5.1)
|
(Gp 1)
2Na(s)
+ Cl2(g) ==> 2NaCl(s) |
(Gp 2)
Mg(s)
+ Cl2(g) ==> MgCl2(s) |
|
(Gp 3/13)
2Al(s) + 3Cl2(g) ==> 2AlCl3(s)
|
(Gp 4/14)
Si(s)
+ 2Cl2(g) ==> SiCl4(l) |
|
(Gp 5/15)
P4(s)
+ 3Cl2(g) ==> 4PCl3(l)
P4(s)
+ 5Cl2(g) ==> 4PCl5(s) |
(Gp 6/16)
2S(s)
+ Cl2(g) ==> S2Cl2(l) also
unstable SiCl2, SiCl4 |
|
(Gp 7/17)
chlorine itself |
(Gp 0/18) no reaction with argon |
TOP OF PAGE
and sub-index
(6) Reaction of the
period 3 chlorides with water (see also
section 5.1)
|
(Gp 1)
NaCl(s)
+ aq ==> Na+(aq) + Cl-(aq)
just
dissolves, ~pH 7 |
(Gp 2)
MgCl2(s)
+ aq ==> Mg2+(aq) + 2Cl-(aq)
just
dissolves, ~pH 7 |
|
(Gp 3/13)
AlCl3(s)
+ 3H2O(l) ==> Al(OH)3(s)
+ 3HCl(g)
with limited
water you get hydrolysis to give acid fumes
AlCl3(s)
+ aq ==> Al3+(aq) + 3Cl-(aq)
excess
water, weakly acidic solution due to the acidity of [Al(H2O)6]3+ |
(Gp 4/14)
SiCl4(l)
+ 2H2O(l) ==> SiO2(s) + 4HCl(aq)
hydrolysis
to give strongly acid solution |
|
(Gp 5/15)
PCl3(l)
+ 3H2O(l) ==> H3PO3(aq)
+ 3HCl(aq)
hydrolysis
to give weakly acid solution
PCl5(s)
+ 4H2O(l) ==> H3PO4(aq)
+ 5HCl(aq)
hydrolysis to give strongly acid solution |
(Gp 6/16) S2Cl2(g)
+ H2O(l) ==> HCl(aq), S(s),
SO2(aq), H2SO3(aq), H2SO4(aq),
H2S(aq)
complex
redox - hydrolysis reaction but final solution is quite acidic
|
|
(Gp 7/17)
chlorine itself |
Gp 0/18
argon has no chloride |
Reaction of the
period 3 chloride with water
-
The ionic sodium
chloride NaCl
and magnesium chloride MgCl2 dissolve in water to form a nearly neutral
solution of hydrated ions.
-
The ionic AlCl3
and the covalent all hydrolyse to form acid solutions.
-
aluminium chloride Al2Cl6
==> hydrochloric acid or weakly acidic aluminium ion
-
silicon(IV) chloride SiCl4,
(silicon tetrachloride) ==> hydrated silicon dioxide +
hydrochloric acid
-
phosphorus(III) chloride PCl3
(phosphorus trichloride) ==> phosphoric(III) acid +
hydrochloric acid
-
with phosphorus(V) PCl5
(phosphorus pentachloride) ==> phosphoric(V) acid +
hydrochloric acid
-
and disulfur dichloride
S2Cl2 ==> a variety products including acidic
sulfur dioxide and hydrochloric acid.
-
The
general trend is for ionic metal chloride salts to give
nearly neutral solutions => metal/non-metal covalent
chlorides that hydrolyse to give acidic solutions.
TOP OF PAGE
and sub-index
(7) Reaction of
period 3
elements with water
|
(Gp 1)
2Na(s) + 2H2O(l) ==>
2NaOH(aq) + H2(g) |
(Gp 2)
Mg(s)
+ 2H2O(l) ==> Mg(OH)2(aq)
+ H2(g) |
|
(Gp 3/13)
aluminium has no reaction with water |
(Gp 4/14)
silicon has no reaction with water |
|
(Gp 5/15)
phosphorus has no reaction with water |
(Gp 6/16)
sulfur has no reaction with water |
|
(Gp 7/17)
Cl2(g) + H2O(l)
HClO(aq) + HCl(aq) |
(Gp 0/18) argon has no reaction with water |
TOP OF PAGE
and sub-index
(8) The period
3 hydrides
MHx
-
A hydride is formed by combining
an element with hydrogen.
-
For hydrides the difference
in electronegativity works both ways!
-
From left to right across
the period you change from an
-
ionic sodium hydride crystal lattice Na+H-
-
to small non-polar molecule covalent
hydrides (silane SiH4 and phosphine PH3)
-
and then
a weakly acidic polar covalent hydride molecule (hydrogen sulfide H2S)
-
and finally a strongly acidic polar covalent molecule (hydrogen chloride
HCl).
-
The formulae follow a simple
period pattern of rising and falling valency for the Period 3 elements.
-
On reaction with water, the
ionic metal hydrides at the start of the period give an alkaline
solution
-
In the middle are neutral
hydrides like phosphine which in contact with water do not change the
pH.
-
Then you get weakly acidic
==> strongly acidic hydrides when they dissolve in water e.g.
-
So things are a bit
complicated with hydrides on period 3 due to the left and right sided
differences in electronegativity!
X = metal or non-metal
TOP OF PAGE
and sub-index
(9) Radii of isoelectronic
ions, cations and anions overlapping periods 2 and 3
-
Isoelectronic means species having the same total
number of electrons.
-
The table below considers
the isoelectronic cations and anions associated with Periods 2, 3 and 4.
|
isoelectronic system |
Group 4/14 |
Group 5/15 |
Group 6/16 |
Group 7/17 |
(Group 0/18) |
Group 1 |
Group 2 |
Group 3/13 |
|
Period |
Period 2 |
Period 3 |
|
[Ne]
10e 1s22s22p6 |
C4- |
N3- |
O2- |
F- |
(Ne) |
Na+ |
Mg2+ |
Al3+ |
|
total nuclear charge |
+6 |
+7 |
+8 |
+9 |
(+10) |
+11 |
+12 |
+13 |
|
radius
in
picometre (pm) |
260 |
171 |
140 |
136 |
(38-112*) |
95 |
65 |
50 |
|
name of ion |
carbide |
nitride |
oxide |
fluoride |
(neon) |
sodium |
magnesium |
aluminium |
|
Period |
Period 3 |
Period 4 |
|
[Ar]
18e 1s22s22p63s23p6 |
Si4- |
P3- |
S2- |
Cl- |
(Ar) |
K+ |
Ca2+ |
Sc3+ |
|
nuclear charge |
+14 |
+15 |
+16 |
+17 |
(+18) |
+19 |
+20 |
+21 |
|
radius
in
picometre (pm) |
271 |
212 |
184 |
181 |
(71-154*) |
133 |
99 |
81 |
|
name of ion |
silicide |
phosphide |
sulfide |
chloride |
(argon) |
potassium |
calcium |
scandium |
Excluding the noble gases
themselves where this is frankly, something of a data problem!,
there is a clear pattern of decreasing ionic radius with
increase in total nuclear charge (+ atomic/proton number) for the two
isoelectronic series tabulated above,
based on the electron
configurations of neon and argon.
From left to right the
proton/electron ratio is steadily increasing so that the electrons are
experiencing an increasingly greater attractive force of the nucleus,
hence the steady decrease in radii for an isoelectronic series.
* all sorts of values
are quoted for noble gas radii e.g. atomic or covalent and ionic, the
higher values fit into the pattern above which is quite clear for all the cations and
anions listed.
|
WHAT NEXT?
PLEASE NOTE
GCSE Level periodic table notes are on separate webpages
Period 2-4 survey
sub-index: 4.1 Period 2 Survey of the
individual elements, 4.2 Period
2 element trends and explanations of physical properties * 4.3 Period 2 element trends in bonding,
structure, oxidation state, formulae & reactions,
5.1
Period 3 survey of elements,
5.2 Period 3 element trends
& explanations of physical properties, 5.3
Period 3 element trends in bonding, structure, oxidation
state, formulae & reactions, 6.1
Survey of
Period 4 elements, 6.2 Period 4 trends in physical properties, 6.3
Period 4 trends in bonding, formulae and
oxidation state, 6.4 Important element trends down a Group
Advanced
Level Inorganic Chemistry Periodic Table Index:
Part 1
Periodic Table history
Part 2
Electron configurations, spectroscopy,
hydrogen spectrum,
ionisation energies *
Part 3
Period 1 survey H to He *
Part 4
Period 2 survey Li to Ne * Part
5 Period 3 survey Na to Ar *
Part 6
Period 4 survey K to Kr AND important
trends down a group *
Part 7
s–block Groups 1/2 Alkali Metals/Alkaline Earth Metals *
Part 8
p–block Groups 3/13 to 0/18 *
Part 9
Group 7/17 The Halogens *
Part 10
3d block elements & Transition Metal Series
*
Part 11
Group & Series data & periodicity plots All
11 Parts have
their own sub-indexes near the top of the pages
Group numbering and the modern periodic
table
The original group numbers of
the periodic table ran from group 1 alkali metals to group 0
noble gases. To account for the d block elements and their
'vertical' similarities, in the modern periodic table, groups 3
to group 0 are numbered 13 to 18. So, the p block elements are
referred to as groups 13 to group 18 at a higher academic level,
though the group 3 to 0 notation is still
used, but usually at a lower academic level. The 3d block
elements (Sc to Zn) are now considered the head (top) elements
of groups 3 to 12.
|
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