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20.

Metals and Their Compounds


The two categories of elements, metals and non- Pure Metals and Alloys
metals, are so different that most elements can be easi-
ly distinguished as either a metal or a nonmetal. A metal atom has at least one loosely held electron
Compounds can also be classified, although there are in a large outer orbital. The atom also has room for
three categories rather than two: combinations of metal another electron. These facts account for the properties
with metal, metal with nonmetal, and nonmetal with of metals in the following way. In a solid metal the
nonmetal. Each class has a distinctive set of character- atoms are close enough together that the orbitals of the
istics. The combination of two metals produces an alloy loosely held valence electrons try to spread out into the
that is difficult to distinguish from a pure metal because whole piece of metal and overlap significantly (Fig.
its characteristics are also metallic. A metal combined 20.1). To some degree the orbitals of the valence elec-
with a nonmetal yields a salt. The majority of such trons of the large number of atoms in the piece of metal
combinations are difficult to distinguish visually from are trying to occupy the same space inside the piece of
table salt, but some are colored and nearly all are toxic. metal at the same time. If they could do so completely,
The combination of two nonmetals produces a materi- the valence electrons would be in identical orbitals and
al—usually a transparent gas—that is difficult to distin- have identical energies. However, the Exclusion
guish from a pure nonmetallic element. Principle forbids more than two electrons occupying
These categories show regularities yet to be identical orbitals at the same time. Hence, the orbitals
explained: Why are salts so different from pure ele- find a compromise and the energy levels of the electrons
ments? Why can most metals be melted together in any split into very many levels that are very close together
proportion and then be solidified into a homogeneous (Fig. 20.2).
alloy such that none of either starting metal is left as The orbitals of these valence electrons spread sig-
excess? Why does a compound composed of a metal nificantly beyond the locale of a particular atom so that
and a nonmetal or of a nonmetal and another nonmetal a given electron does not “belong” to a particular atom.
nearly always leave some of one reactant in excess, The valence electrons can be thought of as a very
unchanged at the end of the reaction? This chapter will mobile kind of “glue” that exists between the atoms to
begin to answer these questions. hold them together. The valence electrons can easily

Figure 20.1. Lithium metal orbitals that overlap permit electrons to move freely throughout the entire lump of metal.

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Figure 20.2. Lithium orbital energies split and form many energy levels that are very close together as more and more
atoms are added.

Figure 20.3. Malleability of a metal. (a) Forces applied to a group of metal atoms. (b) The solid deforms, but will
spring back to its original shape if the force is removed. (c) The solid is deformed permanently by layers sliding to new
positions.

drift from one orbital to another through the overlap- hit with a hammer, but most metals simply
ping regions to any part of the lump of metal. bend or flatten, particularly if they are hot. For
The drifting electrons give metals their unique example, gold can be pounded thinner than
properties, the most common of which are discussed paper (to about a millionth of a centimeter
below. thickness). This characteristic response to
force is termed malleability. On the micro-
1. Electrical conductivity. If electrons are scopic level, the metal nuclei must slide past
forced into one end of a piece of metal, they each other into new positions without ever
push other mobile electrons out the other end. substantially weakening the metallic bond.
This is the mechanism by which wires carry The sea of mobile electrons flows wherever it
electricity and is called electrical conductivity. is needed to keep the bonds strong during
bending and flattening operations (Fig. 20.3).
2. Metallic luster. The closely spaced energy
levels shown in Figure 20.2 permit metals to 4. Thermal conductivity. If thermal energy is
absorb virtually every visible wavelength of added to a piece of metal, the kinetic energy of
light and many invisible wavelengths. A pho- the electrons is increased. The electrons move
ton of almost any energy can find an energy rapidly through the metal distributing this
gap that just fits. However, the atoms do not kinetic energy throughout by collisions. Thus,
keep the photons, but immediately radiate the whole piece of metal becomes hot much
them back (reflection). If all of the visible sooner than an equivalent piece of nonmetal.
light is reflected, the metal appears silver, or if This transport of thermal energy is termed
it is roughened, it appears white. If some of thermal conductivity.
the violet and blue light is permanently
absorbed, the metal appears gold or copper 5. Chemical reactivity. The mobile electrons
colored. High reflectivity in at least a part of are easy prey for electron-hungry atoms such
the visible spectrum confers metallic luster. as oxygen, so most metals react easily to form
oxides or other compounds with nonmetals. In
3. Malleability. Things like glass shatter when fact, only a few metals (such as gold, silver,

184
and copper) are found uncombined in nature. Oxidation States
The others have reacted with oxygen or other
nonmetals and are found as ores. According to Figure 17.7, metals have one or more
electrons that are easily removed because they are near
6. Alloy formation. In metals, the sea of elec- the top of the energy well. These elements are general-
trons accommodates one type of metal atom ly to the left in the Periodic Table. In contrast, non-
about as well as another, particularly if their metals have vacancies for electrons deep in the well.
sizes and orbital energy levels are similar. This Metals often give one or more electrons to a nonmetal,
means that metals near one another (especially thus forming a positive metal ion and a negative non-
vertically) in the Periodic Table should be able metal ion. In forming the ions, the orbitals of the
to substitute for one another in solid metals. valence electrons transfer from the metal atom to center
Many pairs of metals permit substitution for on the nonmetal atom. These oppositely charged ions
one another in all proportions to form alloys are then electrically attracted and become attached to
simply by melting the two together. Some one another through what is known as an ionic bond.
properties of the resulting alloy, such as densi- The oxidation state of an atom in a compound is a
ty, are intermediate between those of the two quantitative indication of the number of electrons that
components. Other properties can turn out the atom has lost or gained in forming the ion or chem-
quite different than one might expect from the ical bond. An atom that has lost an electron is said to be
original components. Some metals, that are far in the +1 oxidation state; an example is Li1+. An atom
apart in the Periodic Table, will permit only that has lost two electrons is in the +2 oxidation state;
limited substitution. an example is Be2+. Similarly, there can be negative
oxidation states for atoms that acquire extra electrons;
Science attempts to explain these characteristics
examples are –1 for Cl1– and –2 for O2–.
with one simple concept: Mobile electrons are the basis
of a metal’s electrical conductivity, metallic luster, mal- The important thing to note is that stable chemical
leability, thermal conductivity, and chemical reactivity. bonds will form if doing so lowers the overall energies

Figure 20.4. Common oxidation states of the elements.

185
of the valence electrons by putting them lower in ener- the constituent elements.
gy wells. The filled shells of the noble gases (helium, Why do the regularities exist among the elements?
neon, argon, etc.) are particularly low energy arrange- They are based on ionization energies whose precise val-
ments of the electrons. These elements do not react ues can be traced back to the Wave Model and the
with other elements because the reaction does not pro- Exclusion Principle. If only one electron in an atom has
vide a means to an overall lowering of the electron ener- a low ionization energy, the oxidation state will be +1. If
gies. The effective oxidation state of the noble gases is two electrons have low ionization energies, the oxidation
identically zero. Many ions achieve this “noble gas state will be +2, and so on. If there are no electrons with
electron configuration,” but of course no change has low ionization energies, but there is a vacancy in an
been made to the nucleus. orbital deep in the well, the atom will try to fill the vacan-
In general, metallic elements near the left of the cy with an electron. This results in a –1 oxidation state.
Periodic Table assume positive oxidation states in
chemical reactions. Nonmetallic elements near the right Compounds Between Metals and Nonmetals
side of the Periodic Table assume negative oxidation
states. Near the middle of the Periodic Table things are Imagine a metallic sodium ion, Na+, and a nonmetal-
somewhat ambiguous. Will an element like carbon lic chloride ion, Cl–, that could form an ionic bond. But
(which has four valence electrons) lose its four valence why should the pairing stop there? Could the Na+ attract
electrons (like a metal), or gain four to fill its shell (like another negative ion and the Cl– attract another positive
a nonmetal)? The answer depends on the specific com- ion? Yes. Long chains of alternating Na+ and Cl– ions
pound that is being formed. An element in the middle, form a sheet like a checkerboard (Fig. 20.5), and finally
such as carbon, will do whichever best lowers its elec- the checkerboards stack so that positive ions are always
tron energy. Thus, for elements near the middle of the above negative ions and vice versa. The result is a crys-
chart there is a tendency for atoms to assume different tal of salt based on the electrical attraction of the ions.
oxidation states in different chemical reactions, depend-
ing on the particular compound which is being formed.
Although many elements can have more than one
oxidation state (depending on the compound), the prim-
ary (likely) oxidation state is related to the atom’s posi-
tion in the Periodic Table. All of the elements in column
1 (labeled IA in the Periodic Table) will have an oxida-
tion state of +1 in ionic compounds. Elements in IIA
have +2 oxidation states. What would you predict for
column IIIA? Check your answer in Figure 20.4.
Elements in columns VIA and VIIA of the Periodic
Table tend to gain electrons to fill their valence shells
and can be predicted with confidence to have primary
oxidation states of –2 and –1, respectively. Elements in
these columns sometimes have additional possible oxi-
dation states in compounds. See sulfur and chlorine in Figure 20.5. Drawing of a small part of a single layer
Figure 20.4, for example. of a NaCl (sodium chloride) crystal.
Elements in the B columns of the Periodic Table are
also prone to having more than one possible oxidation A salt is much different than a metal. Ionic bond-
state. However, we can use the additional information ing accounts for the characteristics of salts discussed
that these elements are all metals (and, therefore, tend to below.
be electron donors) to predict that at least in some com-
pounds these elements will have positive oxidation 1. Electrically nonconducting. The electrons in
states that correspond directly to the number of valence both ions of a salt are all in stable, closed
electrons indicated by their column number. For exam- shells, and are difficult to remove from their
ple, chromium (24Cr) in column VIB will in at least respective ions. Because there are no mobile
some cases have an oxidation state of +6. The rule is electrons, solid salts have no way to conduct
even less precise for the elements in the centermost electricity. However, if the salt is melted,
columns of the Periodic Table (labeled VIII [neither A whole ions may move about and conduct elec-
nor B]). Here we can only predict that, as metals, the tricity, but they are so big and awkward they
elements will have positive oxidation states, but we are not nearly as conductive as the electrons in
must rely on experimental analysis of the individual a metal. Also, if the salt is dissolved in a liq-
compounds to determine the precise oxidation states of uid like water, the ions separate and are able to

186
conduct electricity, but in an inefficient man-
ner. Materials that conduct electricity when
dissolved in water are called electrolytes.

2. Transparent. The energy levels of most salts


are spaced widely apart, so most salts will
absorbs only photons with high energies. Such
high-energy photons are in the invisible, ultra-
violet part of the spectrum. Visible light is not
absorbed by most salts—it passes through and
the salts appear transparent. However, most of
the salts of metals in columns IIIB through IIB
absorb some visible light weakly; this gives
them pale colors. There are also a few highly
colored salts like potassium dichromate; most
of them are composed of more than two ele-
ments (e.g., K2Cr2O7). If a transparent salt
crystal is ground to powder, the small crystals
bend a light ray many times before it emerges
from the powder. This means light will no
longer pass straight through as it did in a single
crystal, so light coming in from the side may
bend and come out the front. The net result is
that the powder appears white, even though it Figure 20.6. Force applied to layers of ions in a salt
is basically transparent or slightly colored. A crystal will slide ions with the same charge over one
block of salt with many cracks or bubbles in it another and split the crystal.
will also appear white. Many otherwise trans-
parent minerals in nature appear opaque and
white for this reason. small excess charge would cause a spark to jump from
the crystal. This implies that there are nearly the same
3. Brittle. Salt crystals break and shatter when number of Na+ as Cl– ions in a crystal of table salt. We
hit with a hammer—they do not bend or flat- can use subscripts to indicate how many ions there are
ten. Imagine sliding one layer of a NaCl crys- in each crystal. For example, a small crystal containing
tal over the underlying layer (Fig. 20.6). When 70 of each type of ion would be designated Na70Cl70.
one sliding layer moves a short distance, all of Because the proportion is always one-to-one, it is cus-
the positive ions will be directly over other tomary to write the simplest formula, NaCl. Other one-
positive ions, and likewise for the negative to-one compounds are LiF and CaO. Note that the
ions. The repulsion is more than enough to metal is written first, the nonmetal last.
force the two layers apart, which breaks Now consider Mg2+ ions coming together with Cl–
(cleaves) the crystal. Brittleness, however, ions to form a crystal. Two Cl– ions are required to neu-
does not always dominate. Glass, most rocks, tralize the +2 charge on the magnesium ion. The pro-
and objects made of fired clay can be con- portion is now one magnesium to two chlorides, and the
sidered super-cooled liquids, because under formula is MgCl2. By knowing the oxidation numbers,
mild stress, only a few atoms at a time move we can determine the proper proportions and the proper
and no breakage occurs. Over a long time subscripts in the formulas of compounds composed of a
many atoms will have moved, and the object metal and a nonmetal. The pivotal concept is the can-
will have a different shape. Thick rock layers cellation of charges.
bend, fold, and take on some surprisingly con- You should be cautioned that this system works
torted shapes if they are not pushed too rapid- best for the combination of a metal with a nonmetal. It
ly. If they cannot adapt quickly enough, they predicts just one compound—there may be others. If
snap and cause earthquakes. the oxidation states are known, the rule works for non-
metals also. For example, nitrogen in the unusual oxi-
Formulas and Names of Salts dation state of +4 can combine with oxygen in its –2
oxidation state. The resulting compound of two non-
The charge in a crystal must be balanced (same metals has the formula NO2. However, it is technically
total positive as negative charge). Even a relatively incorrect to discuss such compounds in terms of oxida-

187
tion “states” that imply that one of the atoms has entire- Electrically charged ions with opposite charges are then
ly lost one or more electrons and the other atom has attracted to one another and become attached to one
taken full possession of one or more electrons. Ions will another in an ionic bond. Atoms that have lost elec-
not be formed completely by elements near one another trons in ionic bonds are said to be in positive oxidation
in the Periodic Table. The smaller nonmetal atom will states. Atoms that have gained electrons in ionic bonds
pull harder on the electrons than the larger metal atom are said to be in negative oxidation states. The oxida-
does, but the electrons will not leave entirely. tion states are further characterized by the number of
Nevertheless, the pretense that they leave helps us write electrons gained or lost: –1 (for atoms that have gained
down the correct formula, so we keep the concept but one electron), +2 (for atoms that have lost two elec-
change the name to oxidation number to remind our- trons), etc.
selves that we may not be dealing with completely Ionic compounds of a metal and a nonmetal are
formed ions. called salts. Salts are generally crystalline solids, trans-
In naming these salts, the metal is named first fol- parent, brittle, white in color (although occasionally
lowed by the nonmetal with its last syllable changed to colored), electrically nonconducting as a solid, but con-
-ide: NaCl is sodium chloride, Li2O is lithium oxide, ducting in water solutions or in melted form. These
and Al2S3 is aluminum sulfide. characteristics can be easily understood in terms of the
The elements chosen for the preceding examples nature of the ionic bond.
usually can have only one oxidation number. Many Bonding between nonmetals (covalent bond) will
other elements have at least two common oxidation be described in the next chapter.
numbers; the name must indicate which is the oxidation
number of interest. One way to do this is to use Roman STUDY GUIDE
numerals in parentheses to indicate the oxidation state Chapter 20: Metals and Their Compounds
of the metal. For example, FeO would be named
iron(II) oxide, and Fe2O3 would be named iron(III) A. FUNDAMENTAL PRINCIPLES: No new funda-
oxide. mental principles.
When two nonmetals are combined, it is not always
clear from the oxidation numbers how many atoms are B MODELS, IDEAS, QUESTIONS, OR APPLICA-
in the molecule, so the number of atoms of each element TIONS
in the molecule is mentioned using the following pre- 1. What useful groups are compounds often divided
fixes: mono- for one, di- for two, tri- for three, and into?
tetra- for four. (Other prefixes are used for higher num- 2. Under what conditions do atoms form metallic
bers.) Some examples are CO, carbon monoxide; CO2, bonds?
carbon dioxide; and N2O3, dinitrogen trioxide. 3. What are the properties of compounds held in
metallic bonds and why do these compounds have
Summary such properties?
4. Under what conditions do atoms form ionic bonds?
Elements can be divided into two categories: met- 5. What are the simplest rules needed to determine the
als and nonmetals. In turn we can divide the types of primary oxidation states of different atoms?
chemical bonds into three categories: metals with met- 6. What are the properties of compounds held in ionic
als (metallic bond), metals with nonmetals (ionic bond), bonds, and why do these compounds have such
and nonmetals with nonmetals (covalent bond). A dis- properties?
tinctive class of physical characteristics is associated 7. What procedure leads to the correct chemical for-
with each type of bond. mula for reactants formed in reactions involving
In a solid metal the atoms are so close together that compounds held together in ionic bonds?
the orbits of the valence electrons overlap. Because the
outer electrons are so loosely held, they can easily drift C. GLOSSARY
from one orbital to another through the overlapping 1. Alloys: Alloys are mixtures of metals. Metals
regions to any part of the lump of metal. The freedom readily form alloys within certain limits.
of the valence electrons to drift results in the following 2. Brittleness: A characteristic of ionic substances,
properties for metals bound by the metallic bond: good such as salts, that readily shatter when struck a
electrical conductivity, metallic luster, malleability, sharp blow.
good thermal conductivity, high chemical reactivity, 3. Electrical Conductivity: A measure of the degree
and readiness to form alloys. to which a substance conducts an electrical current.
It is energetically favorable in metal-nonmetal Metals have a high electrical conductivity.
reactions for the metal to give up valence electrons to 4. Electrical Nonconductivity: A characterization of
the nonmetal, thus forming electrically charged ions. ionic substances, such as salts, that do not readily

188
conduct electricity. a. Determine the positive or negative oxidation
5. Ionic Bond: The chemical bond that binds a states of the different atoms.
metallic ion to a nonmetallic ion by electrical b. Write the chemical formula for the compound.
attraction. c. Write and balance the chemical equation for
6. Ions: A charged object formed when an atom or the reaction.
molecule loses or gains electrons. d. Sketch an energy well for each kind of atom in
7. Malleability: The characteristic of substances that the compound. Draw a circle around each electron
allows them to be worked into desirable shapes or soon to be lost in one atom, and an empty circle at
drawn out into wires. Metals are malleable. the location soon to be filled in the other atom.
8. Metal: See Chapter 18. e. List the main parts of the Wave Model of the
9. Metallic Bond: The chemical bond that binds atom.
metal atoms to other metal atoms in forming metal f. State the fundamental principle of wave-parti-
substances. cle duality that the Wave Model is based on.
10. Metallic Luster: The shiny appearance of metals. 3. Sketch a diagram showing a possible arrangement
11. Negative Oxidation State: The state of an atom of the ions in a salt. Explain what would happen to
which has gained one or more electrons to form an this arrangement if shear forces were exerted on the
ionic bond. The precise oxidation state is repre- salt. Why is the salt brittle? Also, using your under-
sented by a – sign followed by the number of elec- standing of ionic bonds, explain why table salt dis-
trons gained. solved in water is an ionic conductor. Name and
12. Nonmetal: See Chapter 18. state the fundamental principle that explains the
13. Oxidation Number: A signed number that indi- forces that are involved.
cates how many electrons an atom loses (positive
number) or gains (negative number) by forming a E. EXERCISES
compound. In ionic bonding the transfer is com- 20.1. When gold and silver are mixed, the appear-
plete and distinct ions are formed. In covalent ance is still that of pure gold. How could you distin-
bonding the transfer is only partial and distinct ions guish the alloy from pure gold?
are not formed.
14. Positive Oxidation State: The state of an atom 20.2 Which of the following pairs of metals is most
which has lost one or more electrons to form an likely to form alloys of all compositions?
ionic bond. The precise oxidation state is repre- (a) 56Ba and 31Ga
sented by a + sign followed by the number of elec- (b) 50Sn and 82Pb
trons lost. (c) 3Li and 83Bi?
15. Salt: An substance formed from the ionic bond of
a metal with a nonmetal. NaCl is a salt. 20.3. Define the following terms: (a) electrical
16. Thermal Conductivity: A measure of the degree conductivity, (b) metallic luster, (c) malleability, (d)
to which a substance conducts heat. Metals have a thermal conductivity.
high thermal conductivity.
17. Transparency: A characteristic of ionic sub- 20.4. Which of the following pairs of metals is
stances, such as salts, that readily transmit light. most likely to form alloys of all proportions?
Opposite to opaqueness. (a) 55Cs and 49In
(b) 78Pt and 79Au
D. FOCUS QUESTIONS
(c) 82Pb and 19K
1. Consider atoms held together in metallic bonds:
a. What happens to the valence electrons when
20.5. In the left half of Figure 20.4 notice the
the bonds are formed?
prominent diagonal lines of oxidation states. How far is
b. What happens to the energy of the system
it vertically from one line to the next? How far hori-
when the bonds are formed?
zontally?
c. What happens to the orbitals when the bonds
are formed?
20.6. How many of the 23 elements listed in the
d. How does this account for the luster of metals?
left half of Figure 20.4 have only a single oxidation
e. What is the Wave Model of the atom?
state?
f. State the fundamental principle of wave-parti-
cle duality that the Wave Model is based on.
20.7. Write down the primary oxidation state of the
2. Consider the following elements held together in
following elements on the basis of their positions in the
ionic bonds: (a) sodium, chlorine; (b) magnesium,
Periodic Table:
chlorine. In each case:

189
(a) 19K (a) K+ and F–
(b) 10Ne (b) Na+ and S2–
(c) 29Cu (c) Mg2+ and N3–
(d) 35Br
(e) 15P 20.16. Determine the principal oxidation states of
the following elements and then write the correct chem-
20.8. Write down the primary oxidation states of ical formulas for the combinations:
the following elements and check your answers in (a) 4Be and 35Br
Figure 20.4: (b) 31Ga and 8O
(a) 5B
(b) 20Ca 20.17. Write the names of the following com-
(c) 17Cl pounds:
(d) 1H (a) BeO
(e) 18Ar (b) CaCl2
(f) 28Ni (c) LiF
(g) 24Cr (d) Na2S

20.9. Referring to Figure 18.3, select two atoms 20.18. Write the names of the following com-
that are likely to have negative oxidation states because pounds:
they have very high ionization energies. Avoid the (a) CrO
noble gases 2He, 10Ne, and 18Ar. Now look these ele- (b) CrO3
ments up in Figure 17.7 to see if there is a vacancy for (c) Cr2O3
an electron in a low-lying orbital. (d) NO2
(e) SO3
20.10. Referring to Figure 18.3, select two atoms
that are likely to have positive oxidation states because 20.19. Complete Table 20.1.
they have low ionization energies. Now look these ele-
ments up in Figure 17.7 to see if the top electrons are 20.20. Which of the following is an ionic com-
near the top of the well. pound?
(a) O2
20.11. Use Figure 20.4 to write the common oxi- (b) NH3
dation states of the following elements (e.g., He: 0; and (c) CO2
C: –2,0,2, and 4): (d) CH4
(a) N
(e) MgF2
(b) P
(c) O
(d) S 20.21. The correct formula for potassium sulfide
(e) Ne is:
(f) Ar (a) KS
(b) K2S
20.12. From Figure 17.6, state which electron Li is (c) KS2
likely to lose to become Li1+. Do the same for Be going (d) K3S
(e) KS3
to Be2+ (two electrons).
20.22. Determine the primary oxidation state for
20.13. How many I– ions will be required to neu-
Rb. If two Rb atoms combine with one S atom, what is
tralize the charge on an Al3+ ion? the oxidation state of S?
(a) +2
20.14 How many Al3+ and O2– ions must be com- (b) +1
bined to achieve charge neutralization? (Hint: It will (c) 0
require more than one of each type of ion.) (d) –1
(e) –2
20.15. Write the chemical formulas for the follow-
ing combinations:

190
Table 20.1.

LUSTER OR
NAME FORMULA COLOR FORM CONDUCTIVITY

Sodium fluoride solid salt

Iron-cobalt alloy metallic luster

CuCl2

Calcium oxide

Calcium chloride CaCl2

Silver-gold alloy indefinite

Chromium (III) oxide

FeO

Magnesium bromide

Na

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