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    Bonding

    AtomPeriodic TableElectron ConfigurationsBonding
    Metals (particularly those in groups 1 and 2) tend to lose the number of electrons that would leave them with the same number of electrons as in the preceding noble gas in the periodic table. By this means, a positively charged ion is formed. Similarly, nonmetals (especially those in groups 16 and 17, and, to a lesser extent, those in Group 15) can gain the number of electrons needed to provide atoms with the same number of electrons as in the next noble gas in the periodic table. Thus, nonmetals tend to form negative ions. Positively charged ions are called cations, and negatively charged ions are called anions. Ions can be either monatomic (containing only one atom) or polyatomic (containing more than one atom). Compounds that contain ions are called ionic compounds. Ionic compounds generally form from metals and nonmetals. Compounds that do not contain ions, but instead consist of atoms bonded tightly together in molecules (uncharged groups of atoms that behave as a single unit), are called covalent compounds. Covalent compounds usually form from two nonmetals. Atoms gain or lose electrons to form ions with particularly stable electron configurations. The charges of cations formed by the representative metals may be determined readily because, with few exceptions, the electronic structures of these ions have either a noble gas configuration or a completely filled electron shell. The charges of anions formed by the nonmetals may also be readily determined because these ions form when nonmetal atoms gain enough electrons to fill their valence shells. Covalent bonds form when electrons are shared between atoms and are attracted by the nuclei of both atoms. In pure covalent bonds, the electrons are shared equally. In polar covalent bonds, the electrons are shared unequally, as one atom exerts a stronger force of attraction on the electrons than the other. The ability of an atom to attract a pair of electrons in a chemical bond is called its electronegativity. The difference in electronegativity between two atoms determines how polar a bond will be. In a diatomic molecule with two identical atoms, there is no difference in electronegativity, so the bond is nonpolar or pure covalent. When the electronegativity difference is very large, as is the case between metals and nonmetals, the bonding is characterized as ionic.

    13.1 Ionic and Molecular Compounds

    Learning Objectives

    By the end of this section, you will be able to:

    • Define ionic and molecular (covalent) compounds
    • Predict the type of compound formed from elements based on their location within the periodic table
    • Determine formulas for simple ionic compounds

    In ordinary chemical reactions, the nucleus of each atom (and thus the identity of the element) remains unchanged. Electrons, however, can be added to atoms by transfer from other atoms, lost by transfer to other atoms, or shared with other atoms. The transfer and sharing of electrons among atoms govern the chemistry of the elements. During the formation of some compounds, atoms gain or lose electrons, and form electrically charged particles called ions (Figure 13.1).

    Figure 13.1

    (a) A sodium atom (Na) has equal numbers of protons and electrons (11) and is uncharged. (b) A sodium cation (Na+) has lost an electron, so it has one more proton (11) than electrons (10), giving it an overall positive charge, signified by a superscripted plus sign.

    Figure A shows a sodium atom, N a, which has a nucleus containing 11 protons and 12 neutrons. The atom’s surrounding electron cloud contains 11 electrons. Figure B shows a sodium ion, N a superscript plus sign. Its nucleus contains 11 protons and 12 neutrons. The ion’s electron cloud contains 10 electrons and is smaller than that of the sodium atom in figure A.

    You can use the periodic table to predict whether an atom will form an anion or a cation, and you can often predict the charge of the resulting ion. Atoms of many main-group metals lose enough electrons to leave them with the same number of electrons as an atom of the preceding noble gas. To illustrate, an atom of an alkali metal (group 1) loses one electron and forms a cation with a 1+ charge; an alkaline earth metal (group 2) loses two electrons and forms a cation with a 2+ charge, and so on. For example, a neutral calcium atom, with 20 protons and 20 electrons, readily loses two electrons. This results in a cation with 20 protons, 18 electrons, and a 2+ charge. It has the same number of electrons as atoms of the preceding noble gas, argon, and is symbolized Ca2+. The name of a metal ion is the same as the name of the metal atom from which it forms, so Ca2+ is called a calcium ion.

    When atoms of nonmetal elements form ions, they generally gain enough electrons to give them the same number of electrons as an atom of the next noble gas in the periodic table. Atoms of group 17 gain one electron and form anions with a 1− charge; atoms of group 16 gain two electrons and form ions with a 2− charge, and so on. For example, the neutral bromine atom, with 35 protons and 35 electrons, can gain one electron to provide it with 36 electrons. This results in an anion with 35 protons, 36 electrons, and a 1− charge. It has the same number of electrons as atoms of the next noble gas, krypton, and is symbolized Br. (A discussion of the theory supporting the favored status of noble gas electron numbers reflected in these predictive rules for ion formation is provided in a later chapter of this text.)

    Note the usefulness of the periodic table in predicting likely ion formation and charge (Figure 13.2). Moving from the far left to the right on the periodic table, main-group elements tend to form cations with a charge equal to the group number. That is, group 1 elements form 1+ ions; group 2 elements form 2+ ions, and so on. Moving from the far right to the left on the periodic table, elements often form anions with a negative charge equal to the number of groups moved left from the noble gases. For example, group 17 elements (one group left of the noble gases) form 1− ions; group 16 elements (two groups left) form 2− ions, and so on. This trend can be used as a guide in many cases, but its predictive value decreases when moving toward the center of the periodic table. In fact, transition metals and some other metals often exhibit variable charges that are not predictable by their location in the table. For example, copper can form ions with a 1+ or 2+ charge, and iron can form ions with a 2+ or 3+ charge.

    Figure 13.2

    Some elements exhibit a regular pattern of ionic charge when they form ions.

    Group one of the periodic table contains L i superscript plus sign in period 2, N a superscript plus sign in period 3, K superscript plus sign in period 4, R b superscript plus sign in period 5, C s superscript plus sign in period 6, and F r superscript plus sign in period 7. Group two contains B e superscript 2 plus sign in period 2, M g superscript 2 plus sign in period 3, C a superscript 2 plus sign in period 4, S r superscript 2 plus sign in period 5, B a superscript 2 plus sign in period 6, and R a superscript 2 plus sign in period 7. Group six contains C r superscript 3 plus sign and C r superscript 6 plus sign in period 4. Group seven contains M n superscript 2 plus sign in period 4. Group eight contains F e superscript 2 plus sign and F e superscript 3 plus sign in period 4. Group nine contains C o superscript 2 plus sign in period 4. Group ten contains N i superscript 2 plus sign in period 4, and P t superscript 2 plus sign in period 6. Group 11 contains C U superscript plus sign and C U superscript 2 plus sign in period 4, A g superscript plus sign in period 5, and A u superscript plus sign and A u superscript 3 plus sign in period 6. Group 12 contains Z n superscript 2 plus sign in period 4, C d superscript 2 plus sign in period 5, and H g subscript 2 superscript 2 plus sign and H g superscript 2 plus sign in period 6. Group 13 contains A l superscript 3 plus sign in period 3. Group 14 contains C superscript 4 negative sign in period 2. Group 15 contains N superscript 3 negative sign in period 2, P superscript 3 negative sign in period 3, and A s superscript 3 negative sign in period 4. Group 16 contains O superscript 2 negative sign in period 2, S superscript 2 negative sign in period 3, S e superscript 2 negative sign in period 4 and T e superscript 2 negative sign in period 5. Group 17 contains F superscript negative sign in period 2, C l superscript negative sign in period 3, B r superscript negative sign in period 4, I superscript negative sign in period 5, and A t superscript negative sign in period 6. Group 18 contains H e in period 1, N e in period 2, A r in period 3, K r in period 4, X e in period 5 and R n in period 6.

    Example 13.1

    Composition of Ions

    An ion found in some compounds used as antiperspirants contains 13 protons and 10 electrons. What is its symbol?

    Solution

    Because the number of protons remains unchanged when an atom forms an ion, the atomic number of the element must be 13. Knowing this lets us use the periodic table to identify the element as Al (aluminum). The Al atom has lost three electrons and thus has three more positive charges (13) than it has electrons (10). This is the aluminum cation, Al3+.

    Check Your Learning

    Give the symbol and name for the ion with 34 protons and 36 electrons.

    Se2−, the selenide ion

    Example 13.2

    Formation of Ions

    Magnesium and nitrogen react to form an ionic compound. Predict which forms an anion, which forms a cation, and the charges of each ion. Write the symbol for each ion and name them.

    Solution

    Magnesium’s position in the periodic table (group 2) tells us that it is a metal. Metals form positive ions (cations). A magnesium atom must lose two electrons to have the same number electrons as an atom of the previous noble gas, neon. Thus, a magnesium atom will form a cation with two fewer electrons than protons and a charge of 2+. The symbol for the ion is Mg2+, and it is called a magnesium ion.

    Nitrogen’s position in the periodic table (group 15) reveals that it is a nonmetal. Nonmetals form negative ions (anions). A nitrogen atom must gain three electrons to have the same number of electrons as an atom of the following noble gas, neon. Thus, a nitrogen atom will form an anion with three more electrons than protons and a charge of 3−. The symbol for the ion is N3−, and it is called a nitride ion.

    Check Your Learning

    Aluminum and carbon react to form an ionic compound. Predict which forms an anion, which forms a cation, and the charges of each ion. Write the symbol for each ion and name them.

    Al will form a cation with a charge of 3+: Al3+, an aluminum ion. Carbon will form an anion with a charge of 4−: C4−, a carbide ion.

    The ions that we have discussed so far are called monatomic ions, that is, they are ions formed from only one atom. We also find many polyatomic ions. These ions, which act as discrete units, are electrically charged molecules (a group of bonded atoms with an overall charge). Some of the more important polyatomic ions are listed in Table 13.1. Oxyanions are polyatomic ions that contain one or more oxygen atoms. At this point in your study of chemistry, you should memorize the names, formulas, and charges of the most common polyatomic ions. Because you will use them repeatedly, they will soon become familiar.

    Table 13.1

    Common Polyatomic Ions

    NameFormulaRelated AcidFormula
    ammoniumNH4+NH4+  
    hydroniumH3O+H3O+  
    peroxideO22-O22-  
    hydroxideOH-OH-  
    acetateCH3COOCH3COOacetic acidCH3COOH
    cyanideCNhydrocyanic acidHCN
    azideN3-N3-hydrazoic acidHN3
    carbonateCO32-CO32-carbonic acidH2CO3
    bicarbonateHCO3-HCO3-  
    nitrateNO3NO3nitric acidHNO3
    nitriteNO2NO2nitrous acidHNO2
    sulfateSO42−SO42−sulfuric acidH2SO4
    hydrogen sulfateHSO4HSO4  
    sulfiteSO32−SO32−sulfurous acidH2SO3
    hydrogen sulfiteHSO3HSO3  
    phosphatePO43−PO43−phosphoric acidH3PO4
    hydrogen phosphateHPO42−HPO42−  
    dihydrogen phosphateH2PO4H2PO4  
    perchlorateClO4ClO4perchloric acidHClO4
    chlorateClO3ClO3chloric acidHClO3
    chloriteClO2ClO2chlorous acidHClO2
    hypochloriteClOhypochlorous acidHClO
    chromateCrO42−CrO42−chromic acidH2CrO4
    dichromateCr2O72−Cr2O72−dichromic acidH2Cr2O7
    permanganateMnO4MnO4permanganic acidHMnO4

    Note that there is a system for naming some polyatomic ions; -ate and -ite are suffixes designating polyatomic ions containing more or fewer oxygen atoms. Per- (short for “hyper”) and hypo- (meaning “under”) are prefixes meaning more oxygen atoms than -ate and fewer oxygen atoms than -ite, respectively. For example, perchlorate is ClO4,ClO4, chlorate is ClO3,ClO3, chlorite is ClO2ClO2 and hypochlorite is ClO. Unfortunately, the number of oxygen atoms corresponding to a given suffix or prefix is not consistent; for example, nitrate is NO3NO3 while sulfate is SO42−.SO42−. This will be covered in more detail later in the module on nomenclature.

    The nature of the attractive forces that hold atoms or ions together within a compound is the basis for classifying chemical bonding. When electrons are transferred and ions form, ionic bonds result. Ionic bonds are electrostatic forces of attraction, that is, the attractive forces experienced between objects of opposite electrical charge (in this case, cations and anions). When electrons are “shared” and molecules form, covalent bonds result. Covalent bonds are the attractive forces between the positively charged nuclei of the bonded atoms and one or more pairs of electrons that are located between the atoms. Compounds are classified as ionic or molecular (covalent) on the basis of the bonds present in them.

    Ionic Compounds

    When an element composed of atoms that readily lose electrons (a metal) reacts with an element composed of atoms that readily gain electrons (a nonmetal), a transfer of electrons usually occurs, producing ions. The compound formed by this transfer is stabilized by the electrostatic attractions (ionic bonds) between the ions of opposite charge present in the compound. For example, when each sodium atom in a sample of sodium metal (group 1) gives up one electron to form a sodium cation, Na+, and each chlorine atom in a sample of chlorine gas (group 17) accepts one electron to form a chloride anion, Cl, the resulting compound, NaCl, is composed of sodium ions and chloride ions in the ratio of one Na+ ion for each Cl ion. Similarly, each calcium atom (group 2) can give up two electrons and transfer one to each of two chlorine atoms to form CaCl2, which is composed of Ca2+ and Cl ions in the ratio of one Ca2+ ion to two Cl ions.

    A compound that contains ions and is held together by ionic bonds is called an ionic compound. The periodic table can help us recognize many of the compounds that are ionic: When a metal is combined with one or more nonmetals, the compound is usually ionic. This guideline works well for predicting ionic compound formation for most of the compounds typically encountered in an introductory chemistry course. However, it is not always true (for example, aluminum chloride, AlCl3, is not ionic).

    You can often recognize ionic compounds because of their properties. Ionic compounds are solids that typically melt at high temperatures and boil at even higher temperatures. For example, sodium chloride melts at 801 °C and boils at 1413 °C. (As a comparison, the molecular compound water melts at 0 °C and boils at 100 °C.) In solid form, an ionic compound is not electrically conductive because its ions are unable to flow (“electricity” is the flow of charged particles). When molten, however, it can conduct electricity because its ions are able to move freely through the liquid (Figure 13.3).

    Figure 13.3

    Sodium chloride melts at 801 °C and conducts electricity when molten. (credit: modification of work by Mark Blaser and Matt Evans)

    This figure shows three photos connected by right-facing arrows. The first shows a light bulb as part of a complex lab equipment setup. The light bulb is not lit. The second photo shows a substances being heated or set on fire. The third shows the light bulb again which is lit.

    In every ionic compound, the total number of positive charges of the cations equals the total number of negative charges of the anions. Thus, ionic compounds are electrically neutral overall, even though they contain positive and negative ions. We can use this observation to help us write the formula of an ionic compound. The formula of an ionic compound must have a ratio of ions such that the numbers of positive and negative charges are equal.

    Example 13.3

    Predicting the Formula of an Ionic Compound

    The gemstone sapphire (Figure 13.4) is mostly a compound of aluminum and oxygen that contains aluminum cations, Al3+, and oxygen anions, O2−. What is the formula of this compound?

    Figure 13.4

    Although pure aluminum oxide is colorless, trace amounts of iron and titanium give blue sapphire its characteristic color. (credit: modification of work by Stanislav Doronenko)

    This is a photograph of a ring with a sapphire set in it.

    Solution

    Because the ionic compound must be electrically neutral, it must have the same number of positive and negative charges. Two aluminum ions, each with a charge of 3+, would give us six positive charges, and three oxide ions, each with a charge of 2−, would give us six negative charges. The formula would be Al2O3.

    Check Your Learning

    Predict the formula of the ionic compound formed between the sodium cation, Na+, and the sulfide anion, S2−.

    Na2S

    Many ionic compounds contain polyatomic ions (Table 13.1) as the cation, the anion, or both. As with simple ionic compounds, these compounds must also be electrically neutral, so their formulas can be predicted by treating the polyatomic ions as discrete units. We use parentheses in a formula to indicate a group of atoms that behave as a unit. For example, the formula for calcium phosphate, one of the minerals in our bones, is Ca3(PO4)2. This formula indicates that there are three calcium ions (Ca2+) for every two phosphate (PO43−)(PO43−) groups. The PO43−PO43− groups are discrete units, each consisting of one phosphorus atom and four oxygen atoms, and having an overall charge of 3−. The compound is electrically neutral, and its formula shows a total count of three Ca, two P, and eight O atoms.

    Example 13.4

    Predicting the Formula of a Compound with a Polyatomic Anion

    Baking powder contains calcium dihydrogen phosphate, an ionic compound composed of the ions Ca2+ and H2PO4.H2PO4. What is the formula of this compound?

    Solution

    The positive and negative charges must balance, and this ionic compound must be electrically neutral. Thus, we must have two negative charges to balance the 2+ charge of the calcium ion. This requires a ratio of one Ca2+ ion to two H2PO4H2PO4 ions. We designate this by enclosing the formula for the dihydrogen phosphate ion in parentheses and adding a subscript 2. The formula is Ca(H2PO4)2.

    Check Your Learning

    Predict the formula of the ionic compound formed between the lithium ion and the peroxide ion, O22−O22− (Hint: Use the periodic table to predict the sign and the charge on the lithium ion.)

    Li2O2

    Because an ionic compound is not made up of single, discrete molecules, it may not be properly symbolized using a molecular formula. Instead, ionic compounds must be symbolized by a formula indicating the relative numbers of its constituent ions. For compounds containing only monatomic ions (such as NaCl) and for many compounds containing polyatomic ions (such as CaSO4), these formulas are just the empirical formulas introduced earlier. However, the formulas for some ionic compounds containing polyatomic ions are not empirical formulas. For example, the ionic compound sodium oxalate is comprised of Na+ and C2O42−C2O42− ions combined in a 2:1 ratio, and its formula is written as Na2C2O4. The subscripts in this formula are not the smallest-possible whole numbers, as each can be divided by 2 to yield the empirical formula, NaCO2. This is not the accepted formula for sodium oxalate, however, as it does not accurately represent the compound’s polyatomic anion, C2O42−.C2O42−.

    Molecular Compounds

    Many compounds do not contain ions but instead consist solely of discrete, neutral molecules. These molecular compounds (covalent compounds) result when atoms share, rather than transfer (gain or lose), electrons. Covalent bonding is an important and extensive concept in chemistry, and it will be treated in considerable detail in a later chapter of this text. We can often identify molecular compounds on the basis of their physical properties. Under normal conditions, molecular compounds often exist as gases, low-boiling liquids, and low-melting solids, although many important exceptions exist.

    Whereas ionic compounds are usually formed when a metal and a nonmetal combine, covalent compounds are usually formed by a combination of nonmetals. Thus, the periodic table can help us recognize many of the compounds that are covalent. While we can use the positions of a compound’s elements in the periodic table to predict whether it is ionic or covalent at this point in our study of chemistry, you should be aware that this is a very simplistic approach that does not account for a number of interesting exceptions. Shades of gray exist between ionic and molecular compounds, and you’ll learn more about those later.

    Example 13.5

    Predicting the Type of Bonding in Compounds

    Predict whether the following compounds are ionic or molecular:

    (a) KI, the compound used as a source of iodine in table salt

    (b) H2O2, the bleach and disinfectant hydrogen peroxide

    (c) CHCl3, the anesthetic chloroform

    (d) Li2CO3, a source of lithium in antidepressants

    Solution

    (a) Potassium (group 1) is a metal, and iodine (group 17) is a nonmetal; KI is predicted to be ionic.

    (b) Hydrogen (group 1) is a nonmetal, and oxygen (group 16) is a nonmetal; H2O2 is predicted to be molecular.

    (c) Carbon (group 14) is a nonmetal, hydrogen (group 1) is a nonmetal, and chlorine (group 17) is a nonmetal; CHCl3 is predicted to be molecular.

    (d) Lithium (group 1) is a metal, and carbonate is a polyatomic ion; Li2CO3 is predicted to be ionic.

    Check Your Learning

    Using the periodic table, predict whether the following compounds are ionic or covalent:

    (a) SO2

    (b) CaF2

    (c) N2H4

    (d) Al2(SO4)3

    (a) molecular; (b) ionic; (c) molecular; (d) ionic

    Link to Supplemental Exercises

    Supplemental exercises are available if you would like more practice with these concepts.

    13.2 Ionic Bonding

    Learning Objectives

    By the end of this section, you will be able to:

    • Explain the formation of cations, anions, and ionic compounds
    • Predict the charge of common metallic and nonmetallic elements, and write their electron configurations

    As you have learned, ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell.

    Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions. The properties of ionic compounds shed some light on the nature of ionic bonds. Ionic solids exhibit a crystalline structure and tend to be rigid and brittle; they also tend to have high melting and boiling points, which suggests that ionic bonds are very strong. Ionic solids are also poor conductors of electricity for the same reason—the strength of ionic bonds prevents ions from moving freely in the solid state. Most ionic solids, however, dissolve readily in water. Once dissolved or melted, ionic compounds are excellent conductors of electricity and heat because the ions can move about freely.

    Neutral atoms and their associated ions have very different physical and chemical properties. Sodium atoms form sodium metal, a soft, silvery-white metal that burns vigorously in air and reacts explosively with water. Chlorine atoms form chlorine gas, Cl2, a yellow-green gas that is extremely corrosive to most metals and very poisonous to animals and plants. The vigorous reaction between the elements sodium and chlorine forms the white, crystalline compound sodium chloride, common table salt, which contains sodium cations and chloride anions (Figure 13.5). The compound composed of these ions exhibits properties entirely different from the properties of the elements sodium and chlorine. Chlorine is poisonous, but sodium chloride is essential to life; sodium atoms react vigorously with water, but sodium chloride simply dissolves in water.

    Figure 13.5

    (a) Sodium is a soft metal that must be stored in mineral oil to prevent reaction with air or water. (b) Chlorine is a pale yellow-green gas. (c) When combined, they form white crystals of sodium chloride (table salt). (credit a: modification of work by “Jurii”/Wikimedia Commons)

    Three pictures are shown and labeled “a,” “b,” and “c,” from left to right. Image a shows a glass jar with a lid that is full of a clear, colorless liquid in which a silver solid is suspended. Image b depicts a glass bottle with a blue lid that is full of a yellow-green gas. Image c shows a black dish that is full of a white, crystalline solid.

    The Formation of Ionic Compounds

    Binary ionic compounds are composed of just two elements: a metal (which forms the cations) and a nonmetal (which forms the anions). For example, NaCl is a binary ionic compound. We can think about the formation of such compounds in terms of the periodic properties of the elements. Many metallic elements have relatively low ionization potentials and lose electrons easily. These elements lie to the left in a period or near the bottom of a group on the periodic table. Nonmetal atoms have relatively high electron affinities and thus readily gain electrons lost by metal atoms, thereby filling their valence shells. Nonmetallic elements are found in the upper-right corner of the periodic table.

    As all substances must be electrically neutral, the total number of positive charges on the cations of an ionic compound must equal the total number of negative charges on its anions. The formula of an ionic compound represents the simplest ratio of the numbers of ions necessary to give identical numbers of positive and negative charges. For example, the formula for aluminum oxide, Al2O3, indicates that this ionic compound contains two aluminum cations, Al3+, for every three oxide anions, O2− [thus, (2 ×× +3) + (3 ×× –2) = 0].

    It is important to note, however, that the formula for an ionic compound does not represent the physical arrangement of its ions. It is incorrect to refer to a sodium chloride (NaCl) “molecule” because there is not a single ionic bond, per se, between any specific pair of sodium and chloride ions. The attractive forces between ions are isotropic—the same in all directions—meaning that any particular ion is equally attracted to all of the nearby ions of opposite charge. This results in the ions arranging themselves into a tightly bound, three-dimensional lattice structure. Sodium chloride, for example, consists of a regular arrangement of equal numbers of Na+ cations and Cl anions (Figure 13.6).

    Figure 13.6

    The atoms in sodium chloride (common table salt) are arranged to (a) maximize opposite charges interacting. The smaller spheres represent sodium ions, the larger ones represent chloride ions. In the expanded view (b), the geometry can be seen more clearly. Note that each ion is “bonded” to all of the surrounding ions—six in this case.

    Two diagrams are shown and labeled “a” and “b.” Diagram a shows a cube made up of twenty-seven alternating purple and green spheres. The purple spheres are smaller than the green spheres. Diagram b shows the same spheres, but this time, they are spread out and connected in three dimensions by white rods. The purple spheres are labeled “N superscript postive sign” while the green are labeled “C l superscript negative sign.”

    The strong electrostatic attraction between Na+ and Cl ions holds them tightly together in solid NaCl. It requires 769 kJ of energy to dissociate one mole of solid NaCl into separate gaseous Na+ and Cl ions:

    NaCl(s)Na+(g)+Cl(g)ΔH=769kJNaCl(s)Na+(g)+Cl(g)ΔH=769kJ

    Electronic Structures of Cations

    When forming a cation, an atom of a main group element tends to lose all of its valence electrons, thus assuming the electronic structure of the noble gas that precedes it in the periodic table. For groups 1 (the alkali metals) and 2 (the alkaline earth metals), the group numbers are equal to the numbers of valence shell electrons and, consequently, to the charges of the cations formed from atoms of these elements when all valence shell electrons are removed. For example, calcium is a group 2 element whose neutral atoms have 20 electrons and a ground state electron configuration of 1s22s22p63s23p64s2. When a Ca atom loses both of its valence electrons, the result is a cation with 18 electrons, a 2+ charge, and an electron configuration of 1s22s22p63s23p6. The Ca2+ ion is therefore isoelectronic with the noble gas Ar.

    For groups 13–17, the group numbers exceed the number of valence electrons by 10 (accounting for the possibility of full d subshells in atoms of elements in the fourth and greater periods). Thus, the charge of a cation formed by the loss of all valence electrons is equal to the group number minus 10. For example, aluminum (in group 13) forms 3+ ions (Al3+).

    Exceptions to the expected behavior involve elements toward the bottom of the groups. In addition to the expected ions Tl3+, Sn4+, Pb4+, and Bi5+, a partial loss of these atoms’ valence shell electrons can also lead to the formation of Tl+, Sn2+, Pb2+, and Bi3+ ions. The formation of these 1+, 2+, and 3+ cations is ascribed to the inert pair effect, which reflects the relatively low energy of the valence s-electron pair for atoms of the heavy elements of groups 13, 14, and 15. Mercury (group 12) also exhibits an unexpected behavior: it forms a diatomic ion, Hg22+Hg22+ (an ion formed from two mercury atoms, with an Hg-Hg bond), in addition to the expected monatomic ion Hg2+ (formed from only one mercury atom).

    Transition and inner transition metal elements behave differently than main group elements. Most transition metal cations have 2+ or 3+ charges that result from the loss of their outermost s electron(s) first, sometimes followed by the loss of one or two d electrons from the next-to-outermost shell. For example, iron (1s22s22p63s23p63d64s2) forms the ion Fe2+ (1s22s22p63s23p63d6) by the loss of the 4s electrons and the ion Fe3+ (1s22s22p63s23p63d5) by the loss of the 4s electron and one of the 3d electrons. Although the d orbitals of the transition elements are—according to the Aufbau principle—the last to fill when building up electron configurations, the outermost s electrons are the first to be lost when these atoms ionize. When the inner transition metals form ions, they usually have a 3+ charge, resulting from the loss of their outermost s electrons and a d or f electron.

    Example 13.6

    Determining the Electronic Structures of Cations

    There are at least 14 elements categorized as “essential trace elements” for the human body. They are called “essential” because they are required for healthy bodily functions, “trace” because they are required only in small amounts, and “elements” in spite of the fact that they are really ions. Two of these essential trace elements, chromium and zinc, are required as Cr3+ and Zn2+. Write the electron configurations of these cations.

    Solution

    First, write the electron configuration for the neutral atoms:

    Zn: [Ar]3d104s2

    Cr: [Ar]3d54s1

    Next, remove electrons from the highest energy orbital. For the transition metals, electrons are removed from the s orbital first and then from the d orbital. For the p-block elements, electrons are removed from the p orbitals and then from the s orbital. Zinc is a member of group 12, so it should have a charge of 2+, and thus loses only the two electrons in its s orbital. Chromium is a transition element and should lose its s electrons and then its d electrons when forming a cation. Thus, we find the following electron configurations of the ions:

    Zn2+: [Ar]3d10

    Cr3+: [Ar]3d3

    Check Your Learning

    Potassium and magnesium are required in our diet. Write the electron configurations of the ions expected from these elements.

    K+: [Ar], Mg2+: [Ne]

    Electronic Structures of Anions

    Most monatomic anions form when a neutral nonmetal atom gains enough electrons to completely fill its outer s and p orbitals, thereby reaching the electron configuration of the next noble gas. Thus, it is simple to determine the charge on such a negative ion: The charge is equal to the number of electrons that must be gained to fill the s and p orbitals of the parent atom. Oxygen, for example, has the electron configuration 1s22s22p4, whereas the oxygen anion has the electron configuration of the noble gas neon (Ne), 1s22s22p6. The two additional electrons required to fill the valence orbitals give the oxide ion the charge of 2– (O2–).

    Example 13.7

    Determining the Electronic Structure of Anions

    Selenium and iodine are two essential trace elements that form anions. Write the electron configurations of the anions.

    Solution

    Se2–: [Ar]3d104s24p6

    I: [Kr]4d105s25p6

    Check Your Learning

    Write the electron configurations of a phosphorus atom and its negative ion. Give the charge on the anion.

    P: [Ne]3s23p3; P3–: [Ne]3s23p6

    Link to Supplemental Exercises

    Supplemental exercises are available if you would like more practice with these concepts.

    13.3 Covalent Bonding

    Learning Objectives

    By the end of this section, you will be able to:

    • Describe the formation of covalent bonds
    • Define electronegativity and assess the polarity of covalent bonds

    Ionic bonding results from the electrostatic attraction of oppositely charged ions that are typically produced by the transfer of electrons between metallic and nonmetallic atoms. A different type of bonding results from the mutual attraction of atoms for a “shared” pair of electrons. Such bonds are called covalent bonds. Covalent bonds are formed between two atoms when both have similar tendencies to attract electrons to themselves (i.e., when both atoms have identical or fairly similar ionization energies and electron affinities). For example, two hydrogen atoms bond covalently to form an H2 molecule; each hydrogen atom in the H2 molecule has two electrons stabilizing it, giving each atom the same number of valence electrons as the noble gas He.

    Compounds that contain covalent bonds exhibit different physical properties than ionic compounds. Because the attraction between molecules, which are electrically neutral, is weaker than that between electrically charged ions, covalent compounds generally have much lower melting and boiling points than ionic compounds. In fact, many covalent compounds are liquids or gases at room temperature, and, in their solid states, they are typically much softer than ionic solids. Furthermore, whereas ionic compounds are good conductors of electricity when dissolved in water, most covalent compounds are insoluble in water; since they are electrically neutral, they are poor conductors of electricity in any state.

    Formation of Covalent Bonds

    Nonmetal atoms frequently form covalent bonds with other nonmetal atoms. For example, the hydrogen molecule, H2, contains a covalent bond between its two hydrogen atoms. Figure 13.7 illustrates why this bond is formed. Starting on the far right, we have two separate hydrogen atoms with a particular potential energy, indicated by the red line. Along the x-axis is the distance between the two atoms. As the two atoms approach each other (moving left along the x-axis), their valence orbitals (1s) begin to overlap. The single electrons on each hydrogen atom then interact with both atomic nuclei, occupying the space around both atoms. The strong attraction of each shared electron to both nuclei stabilizes the system, and the potential energy decreases as the bond distance decreases. If the atoms continue to approach each other, the positive charges in the two nuclei begin to repel each other, and the potential energy increases. The bond length is determined by the distance at which the lowest potential energy is achieved.

    Figure 13.7

    The potential energy of two separate hydrogen atoms (right) decreases as they approach each other, and the single electrons on each atom are shared to form a covalent bond. The bond length is the internuclear distance at which the lowest potential energy is achieved.

    A graph is shown with the x-axis labeled, “Internuclear distance ( p m )” while the y-axis is labeled, “Energy ( J ).” One value, “0,” is labeled midway up the y-axis and two values: “0” at the far left and “0.74” to the left, are labeled on the x-axis. The point “74” is labeled, “H bond H distance.” A line is graphed that begins near the top of the y-axis and to the far left on the x-axis and drops steeply to a point labeled, “negative 7.24 times 10 superscript negative 19 J” on the y-axis and 74 on the x-axis. This low point on the graph corresponds to a drawing of two spheres that overlap considerably. The line then rises to zero on the y-axis and levels out. The point where it almost reaches zero corresponds to two spheres that overlap slightly. The line at zero on the y-axis corresponds to two spheres that are far from one another.

    It is essential to remember that energy must be added to break chemical bonds (an endothermic process), whereas forming chemical bonds releases energy (an exothermic process). In the case of H2, the covalent bond is very strong; a large amount of energy, 436 kJ, must be added to break the bonds in one mole of hydrogen molecules and cause the atoms to separate:

    H2(g)2H(g)ΔH=436kJH2(g)2H(g)ΔH=436kJ

    Conversely, the same amount of energy is released when one mole of H2 molecules forms from two moles of H atoms:

    2H(g)H2(g)ΔH=−436kJ2H(g)H2(g)ΔH=−436kJ

    Pure vs. Polar Covalent Bonds

    If the atoms that form a covalent bond are identical, as in H2, Cl2, and other diatomic molecules, then the electrons in the bond must be shared equally. We refer to this as a pure covalent bond. Electrons shared in pure covalent bonds have an equal probability of being near each nucleus.

    In the case of Cl2, each atom starts off with seven valence electrons, and each Cl shares one electron with the other, forming one covalent bond:

    Cl+ClCl2Cl+ClCl2

    The total number of electrons around each individual atom consists of six nonbonding electrons and two shared (i.e., bonding) electrons for eight total electrons, matching the number of valence electrons in the noble gas argon. Since the bonding atoms are identical, Cl2 also features a pure covalent bond.

    When the atoms linked by a covalent bond are different, the bonding electrons are shared, but no longer equally. Instead, the bonding electrons are more attracted to one atom than the other, giving rise to a shift of electron density toward that atom. This unequal distribution of electrons is known as a polar covalent bond, characterized by a partial positive charge on one atom and a partial negative charge on the other. The atom that attracts the electrons more strongly acquires the partial negative charge and vice versa. For example, the electrons in the H–Cl bond of a hydrogen chloride molecule spend more time near the chlorine atom than near the hydrogen atom. Thus, in an HCl molecule, the chlorine atom carries a partial negative charge and the hydrogen atom has a partial positive charge. Figure 13.8 shows the distribution of electrons in the H–Cl bond. Note that the shaded area around Cl is much larger than it is around H. Compare this to Figure 13.7, which shows the even distribution of electrons in the H2 nonpolar bond.

    We sometimes designate the positive and negative atoms in a polar covalent bond using a lowercase Greek letter “delta,” δ, with a plus sign or minus sign to indicate whether the atom has a partial positive charge (δ+) or a partial negative charge (δ–). This symbolism is shown for the H–Cl molecule in Figure 13.8.

    Figure 13.8

    (a) The distribution of electron density in the HCl molecule is uneven. The electron density is greater around the chlorine nucleus. The small, black dots indicate the location of the hydrogen and chlorine nuclei in the molecule. (b) Symbols δ+ and δ– indicate the polarity of the H–Cl bond.

    Two diagrams are shown and labeled “a” and “b.” Diagram a shows a small sphere labeled, “H” and a larger sphere labeled, “C l” that overlap slightly. Both spheres have a small dot in the center. Diagram b shows an H bonded to a C l with a single bond. A dipole and a positive sign are written above the H and a dipole and negative sign are written above the C l. An arrow points toward the C l with a plus sign on the end furthest from the arrow’s head near the H.

    Electronegativity

    Whether a bond is nonpolar or polar covalent is determined by a property of the bonding atoms called electronegativity. Electronegativity is a measure of the tendency of an atom to attract electrons (or electron density) towards itself. It determines how the shared electrons are distributed between the two atoms in a bond. The more strongly an atom attracts the electrons in its bonds, the larger its electronegativity. Electrons in a polar covalent bond are shifted toward the more electronegative atom; thus, the more electronegative atom is the one with the partial negative charge. The greater the difference in electronegativity, the more polarized the electron distribution and the larger the partial charges of the atoms.

    Figure 13.9 shows the electronegativity values of the elements as proposed by one of the most famous chemists of the twentieth century: Linus Pauling (Figure 13.10). In general, electronegativity increases from left to right across a period in the periodic table and decreases down a group. Thus, the nonmetals, which lie in the upper right, tend to have the highest electronegativities, with fluorine the most electronegative element of all (EN = 4.0). Metals tend to be less electronegative elements, and the group 1 metals have the lowest electronegativities. Note that noble gases are excluded from this figure because these atoms usually do not share electrons with others atoms since they have a full valence shell. (While noble gas compounds such as XeO2 do exist, they can only be formed under extreme conditions, and thus they do not fit neatly into the general model of electronegativity.)

    Figure 13.9

    The electronegativity values derived by Pauling follow predictable periodic trends, with the higher electronegativities toward the upper right of the periodic table.

    Part of the periodic table is shown. A downward-facing arrow is drawn to the left of the table and labeled, “Decreasing electronegativity,” while a right-facing arrow is drawn above the table and labeled “Increasing electronegativity.” The electronegativity for almost all the elements is given.

    Electronegativity versus Electron Affinity

    We must be careful not to confuse electronegativity and electron affinity. The electron affinity of an element is a measurable physical quantity, namely, the energy released or absorbed when an isolated gas-phase atom acquires an electron, measured in kJ/mol. Electronegativity, on the other hand, describes how tightly an atom attracts electrons in a bond. It is a dimensionless quantity that is calculated, not measured. Pauling derived the first electronegativity values by comparing the amounts of energy required to break different types of bonds. He chose an arbitrary relative scale ranging from 0 to 4.

    Portrait of a Chemist

    Linus Pauling

    Linus Pauling, shown in Figure 13.10, is the only person to have received two unshared (individual) Nobel Prizes: one for chemistry in 1954 for his work on the nature of chemical bonds and one for peace in 1962 for his opposition to weapons of mass destruction. He developed many of the theories and concepts that are foundational to our current understanding of chemistry, including electronegativity and resonance structures.

    Figure 13.10

    Linus Pauling (1901–1994) made many important contributions to the field of chemistry. He was also a prominent activist, publicizing issues related to health and nuclear weapons.

    A photograph of Linus Pauling is shown.

    Pauling also contributed to many other fields besides chemistry. His research on sickle cell anemia revealed the cause of the disease—the presence of a genetically inherited abnormal protein in the blood—and paved the way for the field of molecular genetics. His work was also pivotal in curbing the testing of nuclear weapons; he proved that radioactive fallout from nuclear testing posed a public health risk.

    Electronegativity and Bond Type

    The absolute value of the difference in electronegativity (ΔEN) of two bonded atoms provides a rough measure of the polarity to be expected in the bond and, thus, the bond type. When the difference is very small or zero, the bond is covalent and nonpolar. When it is large, the bond is polar covalent or ionic. The absolute values of the electronegativity differences between the atoms in the bonds H–H, H–Cl, and Na–Cl are 0 (nonpolar), 0.9 (polar covalent), and 2.1 (ionic), respectively. The degree to which electrons are shared between atoms varies from completely equal (pure covalent bonding) to not at all (ionic bonding). Figure 13.11 shows the relationship between electronegativity difference and bond type.

    Figure 13.11

    As the electronegativity difference increases between two atoms, the bond becomes more ionic.

    Two flow charts and table are shown. The first flow chart is labeled, “Electronegativity difference between bonding atoms.” Below this label are three rounded text bubbles, connected by a downward-facing arrow, labeled, “Zero,” “Intermediate,” and “Large,” respectively. The second flow chart is labeled, “Bond type.” Below this label are three rounded text bubbles, connected by a downward-facing arrow, labeled, “Pure covalent,” “Polar covalent,” and “Ionic,” respectively. A double ended arrow is written vertically to the right of the flow charts and labeled, “Covalent character decreases; ionic character increases.” The table is made up of two columns and four rows. The header line is labeled “Bond type” and “Electronegativity difference.” The left column contains the phrases “Pure covalent,” “Polar covalent,” and “Ionic,” while the right column contains the values “less than 0.4,” “between 0.4 and 1.8,” and “greater than 1.8.”

    A rough approximation of the electronegativity differences associated with covalent, polar covalent, and ionic bonds is shown in Figure 13.11. This table is just a general guide, however, with many exceptions. For example, the H and F atoms in HF have an electronegativity difference of 1.9, and the N and H atoms in NH3 a difference of 0.9, yet both of these compounds form bonds that are considered polar covalent. Likewise, the Na and Cl atoms in NaCl have an electronegativity difference of 2.1, and the Mn and I atoms in MnI2 have a difference of 1.0, yet both of these substances form ionic compounds.

    The best guide to the covalent or ionic character of a bond is to consider the types of atoms involved and their relative positions in the periodic table. Bonds between two nonmetals are generally covalent; bonding between a metal and a nonmetal is often ionic.

    Some compounds contain both covalent and ionic bonds. The atoms in polyatomic ions, such as OH, NO3,NO3, and NH4+,NH4+, are held together by polar covalent bonds. However, these polyatomic ions form ionic compounds by combining with ions of opposite charge. For example, potassium nitrate, KNO3, contains the K+ cation and the polyatomic NO3NO3 anion. Thus, bonding in potassium nitrate is ionic, resulting from the electrostatic attraction between the ions K+ and NO3,NO3, as well as covalent between the nitrogen and oxygen atoms in NO3.NO3.

    Example 13.8

    Electronegativity and Bond Polarity

    Bond polarities play an important role in determining the structure of proteins. Using the electronegativity values in Figure 13.9, arrange the following covalent bonds—all commonly found in amino acids—in order of increasing polarity. Then designate the positive and negative atoms using the symbols δ+ and δ–:

    C–H, C–N, C–O, N–H, O–H, S–H

    Solution

    The polarity of these bonds increases as the absolute value of the electronegativity difference increases. The atom with the δ– designation is the more electronegative of the two. Table 13.5 shows these bonds in order of increasing polarity.

    Table 13.5

    Bond Polarity and Electronegativity Difference

    BondΔENPolarity
    C–H0.4CδHδ+CδHδ+
    S–H0.4SδHδ+SδHδ+
    C–N0.5Cδ+NδCδ+Nδ
    N–H0.9NδHδ+NδHδ+
    C–O1.0Cδ+OδCδ+Oδ
    O–H1.4OδHδ+OδHδ+

    Check Your Learning

    Silicones are polymeric compounds containing, among others, the following types of covalent bonds: Si–O, Si–C, C–H, and C–C. Using the electronegativity values in Figure 13.9, arrange the bonds in order of increasing polarity and designate the positive and negative atoms using the symbols δ+ and δ–.
    BondElectronegativity DifferencePolarity
    C–C0.0nonpolar
    C–H0.4CδHδ+CδHδ+
    Si–C0.7Siδ+CδSiδ+Cδ
    Si–O1.7Siδ+OδSiδ+Oδ

    Link to Supplemental Exercises

    Supplemental exercises are available if you would like more practice with these concepts.

    Files

    Previous Citation(s)
    Flowers, P., Neth, E. J., Robinson, W. R., Theopold, K., & Langley, R. (2019). Chemistry in Context. In Chemistry: Atoms First 2e. OpenStax. https://openstax.org/details/books/chemistry-atoms-first-2e

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