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The rows or periods of different length in the table represent the filling of
different orbitals: s in Row 1; s + p in Rows 2 and 3; s + d + p in Rows 4 and 5;
and s + f + d + p in Rows 6 and 7. The fully developed table from Chapter 8 is
shown in the right margin, with the representative elements (filling of s and p
orbitals), transition metals (d orbitals), and inner transition metals (f orbitals)
differentiated by color. Each period begins with the occupancy of a new s
orbital and (after Row 1) ends with a noble gas with a closed s + p electron
shell. The representative elements are divided vertically into eight groups,
labeled IA through VIIA, and 0 for the noble gases. The Roman numeral in the
group number indicates the number of s and p electrons in the outer shell. Representative elements reflect the filling of s and p
orbitals, transition metals of f orbitals. The extra-long form
of the periodic table at the top shows the filling of the
orbitals in their proper order, but is large and clumsy. The
standard long form of the table below it removes the inner
transition metals to as separate block, and the short form
shown on the previous page also separates out the
transition metals
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In Chapters 3 and 6 we introduced several measures of atomic The transition metals add little to the trend and need not be shown,
size: metallic and covalent radii, ionic radii, and van der Waals but their absence can be detected by the extra decrease in radii
radii. Metallic and covalent radii form a smooth, continuous between Groups IIA and IIIA: Ca and Ga, Sr and In, Ba and Tl.
series across the periodic table because they both describe
atoms held together by shared electrons. In metals the electrons
are shared between many atoms, and it is natural to think of the
metal ions and the bonding metallic electrons separately. In
contrast, one seldom regards an molecule as consisting of
two ions held together by four bonding electrons, but the
distinction is more conventional than real.
Ionic radii are larger than covalent or metallic radii for negative
ions, which have picked up more electrons, and smaller for
positive ions, which have lost them. Van der Waals radii are
important mainly for nonmetals, and are large because they
represent packing of atoms without electron sharing.
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The metals all are packed spheres of positive ions held together by mobile
electrons. In close packing (cp), the densest way of packing marbles or other
spherical objects, each atom has twelve nearest neighbors touching it, and
74% of the volume of the metal is occupied by atoms. (There are two main
kinds of close packing, cubic and hexagonal, which differ only in the way that
the individual close-packed layers of atoms are stacked.) In a slightly less Close packing (cp)
dense form, bodycentered packing (bcp), each atom has eight neighbors in
contact with it in the directions of the corners of a cube, and the atoms occupy
only 68% of the total volume.
(a) Cubic
Close packing is favored in metals with small atoms and many electrons to hold
them; body-centered packing is found in metals with larger atoms and fewer
electrons to bind them together. It is not uncommon for a metal to show a
close-packed structure at low temperatures, and change to a body-centered
structure at higher temperatures when the atoms are vibrating more freely. The
alkali metals in Group IA all have the bcp structure at room temperature; but
the smallest two, Li and Na, change to close packing below -200°C. Among the (b) Hexagonal
alkaline earths (Group IIA), which are held together by two electrons per atom,
the smallest two, Be and Mg, always use the dense cp structure.
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The first nonmetal in Row 2, boron, is encountered at the top of Group IIIA. It
has a complex three-dimensional covalent cage structure. The no-man's-land
between metals and nonmetals is especially dramatic in Groups IVA, VA, and Close packing (cp)
VIA, with the lighter elements being nonmetals, the heavier elements at the
bottom of the table metals, and a transition zone separating them. In this zone,
one element often has two different crystal forms, or allotropes, one metallic
and the other nonmetallic. The nonmetallic allotrope is held together by (a) Cubic
covalent bonds with all electrons localized, whereas the metallic form usually
will show the dark color and metallic luster that indicate the presence of mobile
electrons.
(b) Hexagonal
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diamond graphite
The diamond and graphite structures (above), which we first saw in chapter 4, now can be understood in terms of orbitals and bonding. Each carbon atom in diamond
uses sp3 hybridization to form four bonds to neighbors, and all bonding electrons are localized. In graphite, three electrons per carbon atom are localized in sp2-
derived bonds within one sheet, and the fourth electron is delocalized over the entire sheet as though in a "two dimensional metal."
Diamond and graphite illustrate this behavior for carbon; diamond In graphite the electrons are delocalized and free to wander within
is the nonmetallic allotrope, and graphite has some of the the layers of carbon atoms. The black color and metallic sheen of
properties of a metal (see above). The lack of color in diamond graphite result from the absorption and reemission of many
tells us that it has no closely spaced electronic energy levels to wavelengths of light by these mobile electrons.
absorb visible light; all of its electrons are tied down in covalent
bonds.
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The maximum wavelength absorbed and the color seen in this series of
molecules are given in the table for molecules with chain lengths from n = 1 to
8. As the length of the delocalized chain increases, the absorption of radiation
shifts from the ultraviolet into the visible, the complement of the absorbed color
is seen, and at n = 7 or 8 a metallic luster begins to appear. Compounds of
longer molecules in this series are a shiny black, like graphite, because the
region of absorption is so broad that it encompasses virtually the entire visible
spectrum. Graphite, with its endless hexagonal-mesh sheets, can be
considered as the infinite extension of aromatic molecules like benzene and
naphthalene.
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As we have seen before, the melting point, or the temperature needed to break
a solid apart into fluid atoms or molecules, is a convenient measure of the
forces between these atoms or molecules. Melting points for the representative
elements are plotted on the three-dimensional graph, with the periodic table as
the base and temperature along the vertical axis. Along the left edge, the alkali
metals in Group IA, having one electron per atom and an open bcp structure,
are soft and low-melting. The hardness of the metal and its melting point
increase in Group IIA, in which twice as many electrons are available. Al, Ga,
and In are lower melting because of the imperfections and openness of their
metal structures. Within one group, the heavier metals are softer and lower
melting because their atoms are farther apart.
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Melting points provide information about the forces between atoms in a solid.
Melting points of metals increase with the number of bonding electrons per atom
(Li to Be; K to Ca), and decrease with atomic size for atoms with the same
number of bonding electrons (Li to Cs). Hardness and melting point increase
with greater covalent bonding between atoms (Li to C; Pb to C). The change
from infinite three-dimensional frameworks of covalent bonds to indisvidual,
covalently bonded molecules causes a drastic drop in melting points (C to N; Si
to P).
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Cathode:
Anode:
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Magnesium and calcium usually are obtained by electrolysis of fused salts such
as molten , although these +2 salts also can be reduced by metallic Na or
K:
Here the chloride ions play a passive role in the reaction, which involves only a
transfer of electrons from sodium to magnesium ion.
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The four series of transition metals, and the electron-filling process for the first
of these, are shown below. Generally, each new transition metal along one row
has two electrons in the outer s orbital, and an increasing number of electrons
in the buried d orbital belonging to the preceding principal quantum number. In
Row 4 chromium (Cr) and copper (Cu) are exceptions to this rule, stealing one
of the two s electrons to half-fill or fill the d orbitals. These are minor
exceptions, and it is the filling principle that is important.
In chemical reactions of the transition metals, the s electrons are lost most
easily, and +1 and +2 oxidation states are common. Higher oxidation states
also are possible for atoms that have d electrons and, in principle, the highest
possible state would correspond to the loss of all of the outer s and d electrons:
+3 for scandium, +4 for titanium, and +7 for manganese. Electron pairing
Electron-shell diagram for transition metals. The s orbital
complicates matters from iron onward, as we shall see.
is the outer shell, and the d orbitals from the preceeding
principle quantum number are buried more deeply.
The A-group representative elements in the periodic table
are interrupted to accommodate the transition metals (B
group).
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Above: The four series of tranistion metals, occuring in Rows 4 through 7 of the table. Immediately below are electron shell diagrams for
the first transition metal series. The common argon core for these elements is represented by the solid color in the center.
Because of the way in which the elements were synthesized (see Chapter 8), elements in the first series of transition metals are much
more common than those in later series, and hence are more familiar. All of these elements are metallic solids at room temperature
except mercury, which is a liquid with a freezing point of -39°C.
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Transition metals exhibit many different oxidation states, more Each d electron can go into a separate orbital in these elements,
than for any other class of elements. For reasons that we shall so pairing of two electrons with opposite spin in the same orbital is
see in the next section, ions in many of these states are brightly not necessary. Pairing to fill an orbital must begin with iron (Fe),
colored, which indicates the electronic absorption of energy in the and this pairing effectively removes both electrons from bonding
visible spectrum. The name "chromium" came from "chroma" for activity. The maximum oxidation number decreases in the
color. In principle, the maximum oxidation number for a transition progression from iron to zinc (Zn) at the end of the first transition-
metal would be the total number of outer s and d electrons, and metal series. The +2 and +3 states are most common for these
this maximum indeed is found from scandium (Sc) to manganese latter transition metals.
(Mn), with 3 to 7 outer electrons (see above).
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All of the s and d orbitals are filled in Zn, Cd, and Hg, thereby reducing the
mobility of electrons from one atom to the next, and lowering the electrical and
thermal conductivity of the metals. With all outer electrons paired, interactions
between atoms are lessened, which makes the solids soft and low-melting.
Mercury, the transition metal of largest atomic size, is a liquid above -390°C,
but this is not a fundamental chemical difference because on a warm summer
day cesium and gallium are liquids also.
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There are two mirror-related ways of doing this, which leads to left-handed and
right-handed complexes. Only two molecules of diethylenetriamine are needed
to enclose a transition-metal ion completely, and one ethylenedi-
aminetetraacetate ion (EDTA) provides all six bonding electron pairs. EDTA
completely encloses a metal ion in a molecular cocoon, and its attraction for
metal ions is so strong that it will tear them away from many enzyme
molecules. EDTA is used as a means of removing the last traces of metals
from solutions in analytical and biochemical experiments where their presence
would be confusing or harmful.
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This list varies somewhat from one transition metal to another, but generally a
more intense, concentrated packet of negative charge on a ligand causes a
larger crystal-field splitting than does a large, diffuse cloud of negative density.
For example, a localized lone electron pair on a nitrogen atom in
ethylenediamine or ammonia is more effective than the diffuse negative charge
on a bromide ion.
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Boron makes very strong covalent bonds to C and N in crystals. Boron carbide,
, and boron nitride, BN, are nearly as hard and as good abrasives as
diamond. Boron nitride has the diamond structure (bottom left) and is
isoelectronic with diamond. Every boron atom has one less electron than
carbon, but every nitrogen atom has one more, so there are just enough
electrons to hold the diamondlike structure together. Boric oxide, , is
obtained from natural borax, , which was made famous by the
Death Valley twentymule teams that hauled it out of desert deposits.
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The melting point of indium also is depressed, but not as much as gallium.
Because gallium expands when it freezes (another indication of weak
association of atoms in the solid) it finds a minor use in dental alloys and type
metal. Both fillings and type must expand as they solidify to take a sharp
impression of their moulds.
Indium is used in some alloys, and thallium salts find their main use in
odorless, tasteless rat poisons.
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About 21% of the atoms in the crust of the Earth are silicon; carbon accounts
for 0.03%; and less than one atom per million is germanium, tin, or lead. The
relative proportions for C and Si are reversed in a living organism: 11% of the
body weight typically is C, and Si and Sn are needed in trace amounts; Ge and
Ph are of no use. Lead, like most of the other heavy metals, is toxic.
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-N-C-C-N-C-C-N-C-C-N-C-C-
Ammonia is a base because the nitrogen atom has a lone electron pair that can
bind a proton:
: :
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If we think of how much oxygen is in the atmosphere and its importance to us,
the turnover of the atmosphere from reducing to oxidizing seems like an
immense change. If we regard it only as a freeing of less than two parts per
million of mineral oxygen, then the turnover seems less revolutionary. But such
a two-parts-per-million change is the basis for all -breathing life.
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The halogens all achieve a -1 oxidation state by gaining one electron per atom
to complete their outer electron shell. Cl, Br, and I also occur in positive
oxidation states as in perchloric acid, , but fluorine is too electronegative
for this to occur. The most common halogen compounds are salts with metal
cations, and the name halogen itself means "salt-former." The hydroacids HF,
HCI, HBr, and III increase in acid strength as the halogen atom becomes larger
and its proton becomes more weakly held. All but HIP are completely
dissociated in water.
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We have tended to focus on the elements that are important to us and to our
environment and to avoid the chemistry of the unusual elements. This is why
we neglected many heavier elements, and all the inner transition metals. These
first ten chapters are a study of matter and an introduction to the chemical
elements. The next seven chapters are a study of energy and reactivity. These
chapters will add quantitative and time dimensions to what so far has been only
a descriptive science. They also will provide the necessary background for the
last part of the book, the carbon compounds and the chemistry of living
organisms.
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