Periodic Trends 2
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For on-line help on
this topic, please see the two following Chemcal modules:
Atomic
Properties .
Electronic
Structures of Atoms and Ions
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Shortcut to Questions
Q: 1 2 3
4 5
6 7 8 9
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1
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(a) Does metallic character increase
or decrease across a row in the periodic table from left to right?
(b)
Does metallic character increase or decrease down a group in the
periodic table.
(c)
Therefore the best metals tend to be found in what region of the
Periodic Table?
(d) The
most non-metallic elements tend to be found in what region of the
Table?
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2 |
Give three characteristic properties of strongly
metallic elements.
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3 |
Give three characteristic
properties of strongly non-metallic elements.
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4 |
List some typical characteristics of basic
oxides.
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5 |
List some typical characteristics of acidic
oxides.
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6 |
Give an example of an amphoteric oxide and
give two typical reactions.
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7 |
Define the term "first ionisation enthalpy".
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8 |
Define the term
"electron affinity".
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9 |
What are the general trends of the above
within the periodic table?
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10 |
What is meant by the term "electronegativity"?
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Periodic
Trends 2 (Answers) |
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1
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The metallic character
of an element refers to the extent to which that element displays
the characteristics of a metal. Chemical characteristics of metals
include the following:
* form cations in ionic compounds with non-metals
* have ionic halides
* have ionic hydrides containing the H- ion
* have basic oxides
The underlying reason
why metals have these properties is the relative ease with which
electrons can be removed from metal atoms, allowing them to form
cations. This is expressed quantitatively via the ionization energy
of any given element, defined as the energy required to remove an
electron from a gas phase atom of that element. Contrary to the
statement that is sometimes encountered, atoms are not "keen
to lose electrons" - just the opposite as the ionization
energy is always energy that must be supplied in order to remove
electrons from the attraction of the positively charged nucleus.
However, for metals this energy requirement is much less than for
non-metals in the same Period of the Table. For example, the first
ionization energy of the metal sodium is 502 kJ/mol while that of
the non-metal chlorine from the same Period is 1257 kJ/mol. The
energy needed to remove a second electron from any atom is higher
than that for the first as there is a greater attraction between
the remaining electrons and the excess +1 charge the nucleus bears
after the loss of the first electron. Even more energy is required
to remove a third electron and so on.
Metallic character can
be related to Periodic Table position in the same way as the first
ionization energies of the elements. Thus the following generalizations
are valid:
Across a Period: Metallic character decreases from left to
right across each Period of the Table as the outer electrons experience
increasing effective nuclear charge and thus require more energy
for their removal.
Down a Group. Metallic character increases down each Group
of the Table as the outer electrons are further from the nucleus
and require less energy for their removal.
(a)
metallic character decreases from left to right in each Period.
(b)
Metallic character increases down a Group.
(c) The
most metallic elements are in the bottom left hand corner of the
Table.
(d) The
most non-metallic elements are in the top right hand corner of the
Table.
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2 |
Strongly
metallic elements would have:
*low ionization energy for the valence electrons
*basic oxides containing the O2- ion.
* ionic halides
* strongly basic hydrides because they contain the H- ion
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3 |
Strongly non-metallic
elements would have:
*very high ionization energies, even for the first ionization energy.
* acidic oxides
* covalent halides
* covalent hydrides which may be acidic, neutral or weakly basic
but not strongly basic as they lack the H- ion.
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4
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Basic oxides are those
that react with H+ ions to form a salt and water. They
can do this because basic oxides contain the O2- ion
which reacts with the H+. Such compounds containing the
O2- anion must also contain a cation. It is a defining
property of metals that they form cations in compounds because their
outer electrons are relatively easy to remove in reactions. Thus
basic oxides are usually the oxides of metals.
e.g. sodium is a Group
1 element, all of which are metals. Hence Na2O is a basic
oxide and it reacts with H+ as follows:
Na2O + 2H+
→2Na+ + H2O
The salt would be sodium
chloride if the acid used were hydrochloric acid.
Another property of basic
oxides is that if they are soluble in water, they form a basic solution.
Most oxides are not soluble, but Group 1 oxides dissolve.
e.g. Na2O
+ H2O → 2Na+ + 2OH-
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5 |
Acidic oxides are those
that react with OH- ions to form a salt and water. They
can do this because the central atom is a non-metal and it can form
covalent bonds to the O atom of the OH- ion. It is a
defining property of non-metals that they can form covalent compounds
with other non-metals. Thus acidic oxides are generally the oxides
of non-metals.
e.g.. CO2
+ 2OH- → CO32- + H2O
The salt would be sodium
carbonate if the hydroxide used were sodium hydroxide.
Another property of acidic
oxides is that if they are soluble in water, they form an acidic
solution.
e.g. CO2 +
H2O → H2CO3
H+ + HCO3-
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6 |
Amphoteric oxides are able to react with both H+ and OH- and such compounds are usually found as oxides of elements located near the middle of the Periodic Table. These elements typically exhibit some properties of metals as well as some of non-metals. Thus they have sufficient ionic character for their oxides to react with H+ but also the ability to form covalent bonds to the O atoms of OH- ions.
e.g. PbO + 2H+ →
Pb2+ + H2O
The salt would be lead(II) chloride if the acid used were hydrochloric acid.
PbO + H2O + 2OH- →
[Pb(OH)4]2-
The salt formed would be sodium tetrahydroxoplumbate(II) if excess sodium hydroxide were used.
Other commonly encountered amphoteric oxides are Al2O3 and ZnO.
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7 |
The first ionization
enthalpy (energy) of an element is defined as the energy required
to remove the first electron from a gas phase atom of an element,
and can be represented by the equation:
X(g) → X+(g)
+ e-
Ionization enthalpy is
listed as kJ/mole of electrons removed.
Note that even for the
most metallic elements, the sign of this enthalpy is +ve, indicating
that energy must be supplied and that the often seen statement that
"metals are keen to lose electrons" is incorrect.
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8 |
The electron affinity
of an atom is the energy change for the reaction
X(g) + e-
→ X-(g) in which one mole of electrons is added
to a mole of isolated, gas phase atoms.
Usually this reaction
is exothermic, so the sign of ΔH would be negative. Consequently
compilations of electron affinity are usually listed as -ΔH.
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9 |
(i)
First Ionisation Enthalpy
The following generalizations apply to trends in atom's first ionization
energy with Periodic Table position.
Down a Group: As the outer electrons are progressively occupying orbits
further from the nucleus and screened by increasing numbers of inner
electrons, the attraction they experience to the nucleus decreases
and therefore the energy needed to remove an electron (i.e. to ionize
the atom) also decreases.
Across a Period: Recall that the reason that atomic radius decreases
from left to right across any Period is the increasing effective nuclear
charge experienced by the outer electrons as more protons are added
to the nucleus while the accompanying additional electrons are placed
in the same outer orbitals. The increased attraction to the nucleus
that results not only decreases the atomic radius, but also leads
to an increase in the amount of energy needed to remove an electron
- i.e. to ionize the atom.
(ii)
Electron Affinity
The following generalizations apply to trends in atom's electron
affinity with Periodic Table position.
Down a Group: Electron affinity usually decreases down a Group due
to the increasing distance between the nucleus and the added electron
in the atom's outer shell, an effect enhanced through screening
by the inner electrons. This reduced attraction between the added
electron and the nucleus results in less energy being released when
the electron is captured by the atom.
Across a Period: Electron affinity generally increases from left
to right across any given Period of the Table. This arises for the
same reasons as atomic radius decreases and first ionization energy
increases - namely the increasing effective nuclear charge experienced
by the outer electrons as progressively more protons are added to
the nucleus.
However, note that these trends are not as consistent as other trends
in properties with Periodic Table position examined. For example,
the electron affinity of F = 339 kJ/mol while the value for Cl =
355 kJ/mol is larger.
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10 |
The electronegativity
of an atom is the power of that atom to attract electrons to itself.
Electronegativity is not a directly measurable quantity like ionization
energy or electron affinity but instead is calculated from measured
bond energies. A number calculated from the bond energy is assigned
as the electronegativity of the element. The larger the number,
the greater is the electronegativity. The most electronegative atom
is F with an electronegativity value of 3.99 while the least electronegative
is Fr with a value of 0.7. It is useful to know the order of electronegativities
for the three most electronegative elements is F > O > Cl.
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