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CHAPTER
Subshells
1s
2s
2p
3s
3p
3d
4s
4p
4d
4f
The electron configuration of an atom or monatomic ion describes the number of electrons at each energy level.
When writing electron configurations for atoms or monatomic ions the following principles apply:
in the most stable state (the ground state) of any atom or ion the electrons occupy subshells with the
lowest available energy levels. They are allocated to subshells in order of increasing energy as shown
in the following energy sequence:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s
lower energy
higher energy
each subshell can accommodate a maximum number of electrons as shown in Table 1.2.
Subshell
10
14
CHAPTER 1
Elemental and
environmental chemistry
CHAPTER 1
10
Cr (24 electrons)
1s 2s 2p 3s 3p 4s 3d
Cu (29 electrons)
1s 2s 2p 3s 3p 4s 3d
For positive ions of the transition elements (for example Fe2+ and Fe3+)
1. Write the electron configuration for the atom of the element.
1s2 2s2 2p6 3s2 3p6 4s2 3d6
2. Decrease the number of electrons equal to the numerical value of the charge on the ion by deleting the 4s
electrons first, with any subsequent deletions required being made from the 3d subshell.
The Fe2+ ion
the electron configuration for the Fe2+ ion is 1s2 2s2 2p6 3s2 3p6 3d6
The Fe3+ ion
the electron configuration for the Fe3+ ion is 1s2 2s2 2p6 3s2 3p6 3d5.
Q1.1
Using subshell notation, write the electron configurations for the following atoms and ions (use a copy of the
periodic table to find atomic number values):
a. Argon atom:
...............................................................................................................................................................
...............................................................................................................................................................
c. Manganese atom:
...............................................................................................................................................................
...............................................................................................................................................................
10
4p .
Its outer shell is the 4th shell which is occupied by 7 electrons in total. Bromine is in period 4, group VII.
CHAPTER 1
Fe (26 electrons)
CHAPTER 1
I
II
VIII
III
IV
VI
VII
PERIOD NUMBER
2
3
TRANSITION ELEMENTS
4
5
**
LANTHANIDES
**
ACTINIDES
For all elements in group I, there is one electron in the highest energy s subshell.
For example:
lithium (Li)
rubidium (Rb)
1s22s1
1s22s22p63s23p64s23d104p65s1
For all elements in group II, there are two highest energy electrons in an s subshell.
For example:
magnesium (Mg)
calcium (Ca)
1s22s22p63s2
1s22s22p63s23p64s2
For all elements in group III, there is one electron in the highest energy p subshell.
For example:
boron (B)
gallium (Ga)
1s22s22p1
1s22s22p63s23p64s23d104p1
For all elements in group IV, there are two electrons in the highest energy p subshell.
For example:
silicon (Si)
germanium (Ge)
1s22s22p63s23p2
1s22s22p63s23p64s23d104p2
For elements in groups V to VIII there are in turn 3 to 6 electrons in the highest energy p subshell
(helium being an exception at the top of group VIII).
Groups III to VIII form the p block of the periodic table.
For the transition elements, the highest energy electrons are in a d subshell.
1s22s22p63s23p64s23d2
1s22s22p63s23p64s23d7
titanium (Ti)
cobalt (Co)
For the lanthanides and actinides, the highest energy electrons are in an f subshell.
The following is an example of an electron configuration of an element from the lanthanides:
1s22s22p63s23p64s23d104p65s24d105p66s24f 6
The lanthanides and actinides form the f block of the periodic table.
The s, p, d and f blocks of the periodic table are summarised in Figure 1.2.
s-block
p-block
s1
p6
s2
p1
p2
p3
p4
p5
d-block
d1 10
*
**
f-block
f 1 14
*
**
Q1.3
Using subshell notation, write the electron configurations for the following atoms for which the atomic number is
given in brackets. From the electron configuration, determine the block of the periodic table to which the element
belongs.
Electron configuration
Periodic table block
a. Arsenic, As (33):
........................................................
........................................................
b. Rubidium, Rb (37):
........................................................
........................................................
c. Krypton, Kr (36):
........................................................
........................................................
d. Cobalt, Co (27):
........................................................
........................................................
By inspection of a copy of the periodic table, determine the main group and block for each of the following elements.
Main group number
a. Francium:
........................................................
........................................................
b. Thorium:
n/a
........................................................
........................................................
c. Tungsten:
n/a
........................................................
........................................................
d. Thallium:
........................................................
........................................................
CHAPTER 1
The following are examples of electron configurations of elements from the first row (period 4) of the
transition elements:
CHAPTER 1
Electron configurations of the atoms of the s and p block elements can be used as a basis for explaining and
predicting their chemical properties. The connection between the electron configuration of an element and its
position on the periodic table can be used to make predictions about the properties of an element, including its
metal/metalloid/non-metal nature, the charge(s) of its monatomic ion(s) and its likely oxidation state(s) in its
compounds.
Metals:
Non-metals:
Metalloids:
The similarity in chemical properties of the elements within each particular group is explained in terms of
the similarity of their electron configurations. When elements react, their atoms either lose or gain electrons
(to form positive or negative ions respectively) or they share electrons with those of other atoms (to form
covalent bonds). The electron configurations of the resultant ions are more stable than the configurations of the
atoms from which they have been formed. Similarly, when atoms share electrons they acquire more stable
electron configurations.
Valence electrons
For s block elements, the valence shell electrons are the highest energy s subshell electrons.
For p block elements, the valence shell electrons are the outer s and p subshell electrons.
The charge on the monatomic ions of the group I elements is always 1+.
Consequently the oxidation state of the group I elements in their compounds is always +1.
The group I elements are classified as metals because their atoms lose electrons in
chemical reactions.
2NaCl(s)
K2S(s)
Note that hydrogen is not included as a member of group I. Although its electron configuration
1
is 1s , its properties are quite different to those of other members of group I. Sometimes it is
not shown at the top of group I but is given a separate box of its own.
In compounds with non-metals, hydrogen atoms share their one valence electron with valence
electrons of the other non-metal atoms.
CHAPTER 1
Electrons lost or shared by atoms are those from the valence (outer) shells. Electrons gained are accepted into
valence shells. Outer shell electrons are called valence electrons.
CHAPTER 1
Group II elements
These elements also readily form compounds by reacting with non-metal elements such as the halogens, oxygen
and sulfur and with oxidising agents such as water and the hydronium ion. In these reactions, the atoms of the
group II elements lose their valence electrons to form an M2+ ion. The electrons lost are gained by the other
reactant. The product compounds are ionic with formulae such as MCl2, MS, MO and M(OH)2.
The configuration of the M2+ ion is more stable than that of the M atom.
The charge on the monatomic ions of the group II elements is always 2+.
Consequently the oxidation state of the group II elements in their compounds is always +2.
Except for beryllium, the group II elements are classified as metals because their atoms
lose electrons in chemical reactions. Beryllium is classified as a metalloid.
2CaO(s)
MgS(s)
Covalence
The covalence of an element is equal to the number of electrons that its atoms share when
forming covalent bonds with other atoms. When boron shares its 3 outer shell electrons with,
for example, electrons from three chlorine atoms, then boron is exhibiting a covalence of 3.
or
they exist as triple positive ions, such as Al3+, in compounds with non-metals. These ions are formed
when atoms of the group III elements lose the s2p1 outer shell electrons in electron transfer reactions.
The charge on the monatomic ions of the group III elements is usually 3+.
The oxidation state of the group III elements in their compounds is usually +3. In some
compounds their oxidation state is 3.
The elements range from a non-metal, boron, at the top of the group, to metalloids,
aluminium and gallium, in the middle and metals at the bottom of the group.
Group IV elements
In their compounds
or
they exist as 2+ or 4+ ions, such as Pb2+, Sn2+ or Pb4+, in compounds with non-metals.
4+ ions are formed when the atoms of group IV elements lose the s2p2 outer shell electrons in electron
transfer reactions.
2+ ions are formed when the atoms of group IV elements lose only the p2 electrons of the s2p2 outer
shell electrons in electron transfer reactions.
The charge on the monatomic ions of the group IV elements is usually 2+ or 4+.
The oxidation state of the group IV elements in their compounds is either +4, +2 or 4.
The elements range from the non-metals, carbon and silicon, at the top of the group, to
metalloids for the rest of the group.
Group V elements
In their compounds
either they exhibit a covalence of 3, as in the case of nitrogen in all of its compounds such as NH3, and of
phosphorus and arsenic in some of their compounds, for example AsCl3. In these compounds, the
nitrogen, phosphorus and arsenic atoms share only the p3 electrons from the s2p3 outer shell
configuration to form covalent bonds with other non-metal atoms. In sharing in this way they are
conforming to the octet rule.
or
they exhibit a covalence of 5, as in the case of phosphorus and arsenic in some of their compounds, for
example, AsCl5 and P4O10. In these compounds, the phosphorus and arsenic atoms share all of the s2p3
electrons from the s2p3 outer shell configuration to form covalent bonds with other non-metal atoms.
In sharing in this way they are expanding the octet.
or
they exist as 3 ions, such as N3 or P3 in compounds with metals. 3 ions are formed when atoms of
the group V elements gain three electrons into the p subshell thereby changing the outer shell
configuration from s2p3 to s2p6. The resultant ions conform to the octet rule.
CHAPTER 1
either they exhibit a covalence of 4, as in the case for carbon and silicon in their compounds, for example,
CCl4 and SiH4. When carbon and silicon form compounds, their atoms share the s2p2 outer shell
electrons to form covalent bonds with other non-metal atoms.
10
Group VI elements
CHAPTER 1
In their compounds
either they exhibit a covalence of 2, as in the case of oxygen in all of its compounds such as H2O, and of sulfur
and selenium in some of their compounds, for example SF2. In these compounds the oxygen, sulfur and
selenium atoms share only two of the p4 electrons from the s2p4 outer shell configuration to form
covalent bonds with other non-metal atoms. In sharing in this way they are conforming to the octet rule.
or
they exhibit a covalence of 4, as in the case of sulfur and selenium in some of their compounds, for
example SO2 and SeF4. In these compounds, the sulfur and selenium atoms share all of the p4 electrons
from the s2p4 outer shell configuration to form covalent bonds with other non-metal atoms. In sharing in
this way they are expanding the octet. It must be noted that oxygen does not exhibit a covalence of 4.
or
they exhibit a covalence of 6, as in the case of sulfur and selenium in some of their compounds, for
example SF6 and SeO3. In these compounds, the sulfur and selenium atoms share all of the s2p4 electrons
from the outer shell configuration to form covalent bonds with other non-metal atoms.
In sharing in this way they are expanding the octet. It must be noted that oxygen does not exhibit a
covalence of 6.
or
they exist as 2- ions, such as O2 or S2 in compounds with metals. 2 ions are formed when the atoms
of group VI elements gain two electrons into the p subshell thereby changing the outer shell
configuration from s2p4 to s2p6. The resultant ions conform to the octet rule.
they exhibit a covalence of 3, 5 or 7 and in sharing in this way they are expanding the octet. It must be
noted that fluorine does not exhibit a covalence of 3, 5 or 7.
In such compounds, the atoms of the group VII elements share electrons in the following ways:
covalence of 3: three of the p5 electrons shared
covalence of 5: all five of the p5 electrons shared
covalence of 7: all seven of the s2p5 electrons shared
or
they exist as 1 ions, in compounds with metals. 1 ions are formed when the atoms of group VII
elements gain one electron into the p subshell, thereby changing the outer shell configuration from s2p5
to s2p6. The resultant ions conform to the octet rule.
11
Element
Oxidation state
Example
Nitrogen
+4
NO2
Nitrogen
+2
NO
Chlorine
+4
ClO2
Table 1.3 Some anomalous oxidation states for nitrogen and chlorine.
These oxidation states cannot be explained in terms of electron configurations and shared pairs of electrons.
Other bonding models that are beyond the scope of this course must be used.
VIII
H
non-metal
ox state
+1
II
III
IV
VI
VII
Li
metal
ox state
+1
Be
metalloid
ox state
+2
B
non-metal
ox states
+3, 3
C
non-metal
ox states
+4, 4
N
non-metal
ox states
+5, +3, 3
O
non-metal
ox state
2
F
non-metal
ox state
1
Na
metal
ox state
+1
Mg
metal
ox state
+2
Al
metalloid
ox state
+3
Si
non-metal
ox states
+4, 4
P
non-metal
ox states
+5, +3, 3
S
non-metal
ox states
+6, +4, +2,
2
C1
non-metal
ox states
+7, +5, +3,
+1, 1
K
metal
ox state
+1
Ca
metal
ox state
+2
Ga
metalloid
ox state
+3
Ge
metalloid
ox states
+4, +2
As
metalloid
ox states
+5, +3
Se
non-metal
ox states
+4, +2
Br
non-metal
ox states
+7, +5, +3,
+1, 1
Rb
metal
ox state
+1
Sr
metal
ox state
+2
TRANSITION
METALS
CHAPTER 1
There are some examples of the s and p block elements exhibiting oxidation states (and covalences) that are
different from those given in the summaries above. Some of the more common of these are given in Table 1.3.
12
CHAPTER 1
Group VII
Period 1
Period 4
The periodic table can then be divided into regions of high, intermediate and low electronegativities as shown
on part of the periodic table in Figure 1.4.
The numerical values beneath the symbols of the elements are Pauling electronegativity values. (Linus Pauling,
an American chemist, developed a scale of electronegativity values last century.)
II
III
IV
VI
VII
Li
0.98
Be
1.57
B
2.04
C
2.55
N
3.04
O
3.44
F
3.98
Na
0.93
Mg
1.31
Al
1.61
Si
1.90
P
2.19
S
2.58
Cl
3.16
K
0.82
Ca
1.00
Ga
1.81
Ge
2.01
As
2.18
Se
2.55
Br
2.96
Rb
0.82
Sr
0.95
Low electronegativity
(metals)
Intermediate
electronegativity
(metalloids)
High electronegativity
(non-metals)
Acidic oxides
Acidic oxides react with hydroxide ions to produce oxyanions (negatively charged ions of the element and
oxygen) and water molecules. Examples of oxyanions are carbonate, CO32, sulfate, SO42 and aluminate, AlO2.
If soluble in water, acidic oxides react with water to form oxyacids (acids consisting of the element combined
with hydrogen and oxygen). Examples of oxyacids are carbonic acid, H2CO3, sulfuric acid, H2SO4 and
orthophosphoric acid, H3PO4.
These oxyacids consist of molecules with covalent hydroxyl groups (O H) as part of their structure.
For example, the structure of H2CO3 is:
O
H
C
O
H
O
Oxyacids undergo complete or partial ionisation with water to produce hydronium ions.
For example:
H2CO3 + H2O
H3O+ + HCO3
13
Acidic oxides are the oxides of non-metals. They are the oxides of the elements with high electronegativity and
are covalent molecular (such as CO2 and SO3) or continuous covalent compounds (such as SiO2).
Oxide
P4O10
(phosphate)
SO2
(orthophosphoric acid)
(sulfite)
SO3
(sulfurous acid)
(sulfate)
CO2
(sulfuric acid)
(carbonate)
SiO2
(carbonic acid)
NO REACTION
(silicate)
* Note: The oxidation numbers of the elements are unchanged in these reactions.
One of the oxides of chlorine is Cl2O. It is an acidic oxide with a corresponding oxyanion, CIO (hypochlorite), and a
corresponding oxyacid, HCl0 (hypochlorous acid).
a. Write an equation for the reaction of Cl2O with hydroxide ions.
...................................................................................................................................................................................................
Basic oxides
Basic oxides react with acids (or hydrogen ions) to produce positively charged metal ions and water molecules.
When reacting in this way, the solid oxides appear to dissolve in the acid.
If soluble in water, basic oxides react with water to form metal ions and hydroxide ions in solution.
Basic oxides are the oxides of metals. They are the oxides of elements with low electronegativity and are ionic
compounds consisting of metal ions and oxide, O2, ions.
Table 1.5 summarises the reactions of some basic oxides with hydrogen ions and with water (where reactions
occur).
Oxide
Na2O
MgO
CuO
NO REACTION
Fe2O3
NO REACTION
* Note: The oxidation numbers of the elements are unchanged in these reactions.
CHAPTER 1
Table 1.4 below summarises the reactions of some acidic oxides with hydroxide ions and with water (where
reactions occur).
14
Barium oxide, BaO, and lithium oxide, Li2O, are both basic oxides.
CHAPTER 1
Amphoteric oxides
Amphoteric oxides display basic character by reacting with acids (or hydrogen ions) to produce positively
charged monatomic ions and water molecules. When reacting in this way, the solid oxides appear to dissolve
in the acid.
Amphoteric oxides also display acidic character by reacting with hydroxide ions to produce oxyanions and
water molecules. When reacting in this way, the solid oxides appear to dissolve in the hydroxide solution.
Amphoteric oxides do not react with water.
Table 1.6 summarises the reactions of two amphoteric oxides with hydrogen ions and with hydroxide ions.
Oxide
ZnO
Al2O3
3+
Q1.6
b. Write an equation for the reaction of PbO with hydroxide ions, given that it forms the plumbate ion, PbO22.
...................................................................................................................................................................................................
Q1.7
When rubidium oxide is mixed with water the resulting solution has a pH greater than 7.
Explain, with the aid of an equation, why the solution has a pH greater than 7.
..........................................................................................................................................................................................................
..........................................................................................................................................................................................................
..........................................................................................................................................................................................................
..........................................................................................................................................................................................................
15
Molecular substances
Small molecules are formed when atoms of non-metal elements covalently bond to each other. These non-metal
elements are located in the top right-hand section of the periodic table:
III
IV
VI
VII
Si
Cl
As
Se
Br
Hydrogen atoms can also form small molecules with atoms of the elements shown above.
There is a small number of non-metal elements and non-metal non-metal compounds that
are not molecular.
For example, silicon dioxide, SiO2, diamond, C, and silicon carbide, SiC, are not molecular.
These substances consist of continuous lattices of atoms bonded to each other by covalent
bonds. They are commonly referred to as continuous covalent substances.
Element 2
Compound 1
Compound 2
Formula Cl20
Compound 3
Compound 4
Silver chloride
CHAPTER 1
Compounds and elements consisting of molecules are described as molecular substances. Molecules consisting
of 10 or less atoms per molecule may be considered as small molecules. Some common examples are CO2,
SO2, H2S, Cl2, NH3, O3, CFCl3 and H2SO4.