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12.5 Correlation in between Bonding and also the properties of Solids

Learning Objective

To know the correlation in between bonding and the nature of solids.

Based top top the nature that the pressures that organize the component atoms, molecules, or ions together, solids may be officially classified together ionic, molecular, covalent (network), or metallic. The sports in the family member strengths of this four varieties of interaction correlates nicely through their large variation in properties.

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Ionic Solids

You learned in thing 8 "Ionic matches Covalent Bonding" that an ionic solidA solid that consists of positively and negatively charged ions held together by electrostatic forces. Consists of positively and negatively fee ions organized together by electrostatic forces. (For an ext information around ionic solids, watch Chapter 8 "Ionic versus Covalent Bonding", section 8.2 "Ionic Bonding".) The stamin of the attractive pressures depends ~ above the charge and also size that the ions that compose the lattice and also determines countless of the physical properties that the crystal.

The lattice energy, the energy required to different 1 mol the a crystalline ionic solid right into its component ions in the gas phase, is directly proportional come the product that the ionic charges and inversely proportional to the sum of the radii of the ions. Because that example, NaF and also CaO both crystallize in the face-centered cubic (fcc) sodium chloride structure, and also the size of their component ions are around the same: Na+ (102 pm) matches Ca2+ (100 pm), and F− (133 pm) versus O2− (140 pm). Due to the fact that of the higher charge on the ions in CaO, however, the lattice energy of CaO is practically four times better than that of NaF (3401 kJ/mol versus 923 kJ/mol). The pressures that organize Ca and O together in CaO are lot stronger than those that hold Na and also F with each other in NaF, for this reason the warmth of blend of CaO is nearly twice that of NaF (59 kJ/mol matches 33.4 kJ/mol), and also the melting point of CaO is 2927°C versus 996°C because that NaF. In both cases, however, the values are large; the is, straightforward ionic compounds have actually high melt points and are fairly hard (and brittle) solids.

Molecular Solids

Molecular solidsA heavy that consists of molecules held together by relatively weak forces, such together dipole-dipole interactions, hydrogen bonds, and also London dispersion forces. Consist of of atoms or molecules organized to each other by dipole–dipole interactions, London dispersion forces, or hydrogen bonds, or any mix of these, i beg your pardon were questioned in thing 11 "Liquids". The setup of the molecule in hard benzene is as follows:


The framework of heavy benzene. In heavy benzene, the molecules room not arranged with their plane parallel come one another but in ~ 90° angles.

Because the intermolecular interaction in a molecule solid are reasonably weak compared with ionic and covalent bonds, molecular solids often tend to it is in soft, short melting, and also easily vaporized (ΔHfus and ΔHvap are low). For comparable substances, the stamin of the London dispersion pressures increases smoothly with boosting molecular mass. Because that example, the melting points the benzene (C6H6), naphthalene (C10H8), and anthracene (C14H10), with one, two, and also three fused aromatic rings, are 5.5°C, 80.2°C, and also 215°C, respectively. The enthalpies of fusion also boost smoothly within the series: benzene (9.95 kJ/mol) 6H5CH3) and also m-xylene <m-C6H4(CH3)2> have actually melting clues of −95°C and −48°C, respectively, i m sorry are substantially lower 보다 the melting point of the lighter but more symmetrical analog, benzene.

Self-healing rubber is an example of a molecule solid through the potential for significant commercial applications. The material deserve to stretch, yet when snapped right into pieces it can bond ago together again through reestablishment of its hydrogen-bonding network there is no showing any kind of sign that weakness. Amongst other applications, that is gift studied because that its use in adhesives and bicycle tires that will certainly self-heal.


Toluene and also m-xylene. The methyl groups attached to the phenyl ring in toluene and m-xylene prevent the ring from packing together as in hard benzene.

Covalent Solids

Covalent solidsA hard that is composed of two- or three-dimensional networks of atoms hosted together by covalent bonds. Are developed by networks or chains of atom or molecules organized together by covalent bonds. A perfect single crystal that a covalent hard is therefore a solitary giant molecule. Because that example, the structure of diamond, displayed in part (a) in number 12.19 "The frameworks of Diamond and also Graphite", consists of sp3 hybridized carbon atoms, every bonded to four other carbon atoms in a tetrahedral variety to develop a large network. The carbon atoms form six-membered rings.

Figure 12.19 The frameworks of Diamond and also Graphite


(a) Diamond consists of sp3 hybridized carbon atoms, every bonded to 4 other carbon atoms. The tetrahedral variety forms a gigantic network in i m sorry carbon atoms form six-membered rings. (b) These next (left) and also top (right) views of the graphite structure display the layers of unify six-membered rings and the plan of atoms in alternative layers of graphite. The ring in alternative layers space staggered, such the every various other carbon atom in one great lies directly under (and above) the center of a six-membered ring in an surrounding layer.

The unit cabinet of diamond can be explained as an fcc variety of carbon atoms v four additional carbon atoms inserted into four of the tetrahedral holes. The thus has actually the zinc blende structure explained in section 12.3 "Structures of an easy Binary Compounds", other than that in zinc blende the atom that compose the fcc variety are sulfur and the atoms in the tetrahedral holes are zinc. Elemental silicon has actually the exact same structure, together does silicon carbide (SiC), i m sorry has alternate C and also Si atoms. The structure of crystalline quartz (SiO2), presented in ar 12.1 "Crystalline and also Amorphous Solids", have the right to be viewed as being derived from the framework of silicon by inserting one oxygen atom between each pair the silicon atoms.

All compounds with the diamond and also related structures space hard, high-melting-point solids that space not conveniently deformed. Instead, they have tendency to shatter when subjected to big stresses, and also they usually do not conduct electricity really well. In fact, diamond (melting point = 3500°C in ~ 63.5 atm) is one of the hardest substances known, and also silicon carbide (melting point = 2986°C) is provided commercially as an abrasive in sandpaper and also grinding wheels. That is complicated to deform or melt these and also related compound because solid covalent (C–C or Si–Si) or polar covalent (Si–C or Si–O) bonds should be broken, which needs a large input that energy.

Other covalent solids have an extremely different structures. Because that example, graphite, the other typical allotrope of carbon, has actually the structure displayed in part (b) in number 12.19 "The frameworks of Diamond and also Graphite". It has planar networks that six-membered ring of sp2 hybridized carbon atoms in which every carbon is external inspection to 3 others. This leaves a solitary electron in one unhybridized 2pz orbital that can be supplied to type C=C twin bonds, resulting in a ring v alternating double and single bonds. Since of the resonance structures, the bonding in graphite is ideal viewed together consisting the a network that C–C solitary bonds v one-third the a π bond holding the carbons together, comparable to the bonding in benzene.

To fully describe the bonding in graphite, we need a molecular orbital approach similar to the one used for benzene in chapter 9 "Molecular Geometry and also Covalent Bonding Models". In fact, the C–C distance in graphite (141.5 pm) is slightly longer than the distance in benzene (139.5 pm), continual with a net carbon–carbon shortcut order of 1.33. In graphite, the two-dimensional airplane of carbon atoms space stacked to type a three-dimensional solid; just London dispersion pressures hold the class together. Together a result, graphite exhibits properties typical of both covalent and also molecular solids. early out to strong covalent bonding within the layers, graphite has a very high melt point, as intended for a covalent solid (it in reality sublimes at about 3915°C). The is also very soft; the great can quickly slide previous one an additional because the the weak interlayer interactions. Consequently, graphite is supplied as a lubricant and as the “lead” in pencils; the friction in between graphite and a item of paper is enough to leave a thin layer that carbon ~ above the paper. Graphite is unusual amongst covalent solids in that its electrical conductivity is an extremely high parallel to the plane of carbon atoms since of delocalized C–C π bonding. Finally, graphite is black because it contains an immense variety of alternating dual bonds, which outcomes in a very small energy difference in between the individual molecule orbitals. Thus light of practically all wavelength is absorbed. Diamond, top top the other hand, is colorless as soon as pure since it has no delocalized electrons.

Table 12.5 "A compare of Intermolecular (Δ" compare the strengths of the intermolecular and also intramolecular interactions for three covalent solids, reflecting the comparative weak of the interlayer interactions.

Table 12.5 A to compare of Intermolecular (ΔHsub) and Intramolecular Interactions

problem ΔHsub (kJ/mol) typical Bond power (kJ/mol)
phosphorus (s) 58.98 201
sulfur (s) 64.22 226
iodine (s) 62.42 149

Metallic Solids

Metals are identified by their capability to reflect light, dubbed lusterThe ability to reflect light. Metals, because that instance, have actually a shiny surface ar that reflects light (metals space lustrous), conversely, nonmetals perform not., your high electrical and thermal conductivity, their high warmth capacity, and also their malleability and also ductility. Every lattice allude in a pure metallic aspect is occupied by an atom of the same metal. The packing performance in metallic crystals has tendency to it is in high, therefore the result metallic solidsA heavy that consists of steel atoms organized together by metallic bonds. Are dense, with each atom having as numerous as 12 nearest neighbors.

Bonding in metallic solids is quite different from the bonding in the other kinds of solids we have discussed. Due to the fact that all the atoms space the same, there deserve to be no ionic bonding, yet metals constantly contain too couple of electrons or valence orbitals to type covalent bonds with each of your neighbors. Instead, the valence electrons room delocalized throughout the crystal, providing a strong cohesive force that holds the metal atoms together.

Note the Pattern

Valence electrons in a metallic solid room delocalized, providing a solid cohesive force that stop the atom together.

The stamin of metallic bonds different dramatically. Because that example, cesium melts in ~ 28.4°C, and mercury is a liquid at room temperature, conversely, tungsten melts at 3680°C. Metallic bonds tend to be weakest for elements that have practically empty (as in Cs) or nearly full (Hg) valence subshells, and also strongest for aspects with about half-filled valence shells (as in W). As a result, the melt points of the metals increase to a maximum around group 6 and also then diminish again indigenous left to right across the d block. Various other properties concerned the stamin of metallic bonds, such as enthalpies that fusion, boil points, and hardness, have similar periodic trends.

A somewhat oversimplified means to explain the bonding in a metallic crystal is come depict the crystal as consisting of positively fee nuclei in one electron seaValence electrons that are delocalized transparent a metallic solid. (Figure 12.20 "The Electron-Sea design of Bonding in Metals"). In this model, the valence electrons room not tightly tied to any one atom yet are dispersed uniformly transparent the structure. Very tiny energy is essential to remove electrons native a hard metal because they room not bound to a single nucleus. When an electric potential is applied, the electrons have the right to migrate through the solid toward the optimistic electrode, thus developing high electric conductivity. The ease through which metals have the right to be deformed under pressure is attributed come the ability of the steel ions to adjust positions within the electron sea there is no breaking any specific bonds. The transfer of power through the heavy by succeeding collisions between the metal ions likewise explains the high thermal conductivity of metals. This version does not, however, explain countless of the other properties the metals, such together their metallic luster and also the observed trends in bond strength as reflected in melt points or enthalpies of fusion. A more complete summary of metallic bonding is presented in ar 12.6 "Bonding in Metals and also Semiconductors".

Figure 12.20 The Electron-Sea version of Bonding in Metals


Fixed, positively charged steel nuclei from group 1 (a) or group 2 (b) room surrounded by a “sea” of cell phone valence electrons. Because a group 2 metal has actually twice the variety of valence electrons as a team 1 metal, it should have a greater melting point.

Substitutional Alloys

An alloyA solid equipment of 2 or an ext metals whose properties differ from those the the ingredient elements. Is a mixture of steels with metallic properties the differ native those of its ingredient elements. Brass (Cu and Zn in a 2:1 ratio) and also bronze (Cu and Sn in a 4:1 ratio) are instances of substitutional alloysAn alloy created by the substitution the one metal atom for an additional of similar size in the lattice., which room metallic solids with huge numbers of substitutional impurities. In contrast, tiny numbers the interstitial impurities, such together carbon in the stole lattice that steel, provide an interstitial alloyAn alloy developed by inserting smaller sized atoms into holes in the steel lattice.. Because scientists can integrate two or much more metals in differing proportions to tailor the properties of a product for specific applications, many of the metallic substances us encounter are actually alloys. Examples include the low-melting-point alloys used in solder (Pb and also Sn in a 2:1 ratio) and also in fuses and fire sprinklers (Bi, Pb, Sn, and also Cd in a 4:2:1:1 ratio).

The compositions of most alloys can vary over large ranges. In contrast, intermetallic compoundsAn alloy that is composed of particular metals that combine in only particular proportions and also whose properties are typically quite various from those of your constituent elements. Consist of of certain metals that incorporate in only specific proportions. Your compositions space largely established by the family member sizes of your component atoms and also the proportion of the total variety of valence electron to the variety of atoms present (the valence electron density). The structures and also physical nature of intermetallic link are commonly quite different from those of your constituent elements, but they might be comparable to facets with a comparable valence electron density. Because that example, Cr3Pt is one intermetallic compound supplied to cloak razor blades advertised as “platinum coated”; that is an extremely hard and also dramatically lengthens the valuable life the the razor blade. With similar valence electron densities, Cu and also PdZn have been uncovered to it is in virtually identical in their catalytic properties.

Some general properties of the four major classes of solids room summarized in Table 12.6 "Properties the the major Classes the Solids".

Table 12.6 nature of the significant Classes the Solids

Ionic Solids molecular Solids Covalent Solids Metallic Solids *Many exception exist. Because that example, graphite has actually a fairly high electrical conductivity in ~ the carbon planes, and also diamond has the highest thermal conductivity of any kind of known substance.
poor conductors that heat and also electricity poor conductors of heat and electricity poor conductors that heat and also electricity* good conductors that heat and also electricity
relatively high melting point low melting point high melting point melting points depend strongly ~ above electron configuration
hard however brittle; break under stress soft very hard and brittle easily deformed under stress; ductile and malleable
relatively dense low density low density usually high density
dull surface dull surface dull surface lustrous

Note the Pattern

The general order of increasing strength of interaction in a hard is molecular solids 6(CH3)6, and also Zn as ionic, molecular, covalent, or metallic solids and arrange lock in order of raising melting points.

Given: compounds

Asked for: classification and also order of melt points


A situate the ingredient element(s) in the routine table. Based on their positions, predict whether each solid is ionic, molecular, covalent, or metallic.

B kinds the solids in bespeak of raising melting points based upon your classification, beginning with molecule solids.


A Germanium lies in the p block simply under Si, along the diagonal heat of semimetallic elements, which says that element Ge is most likely to have the exact same structure as Si (the diamond structure). Therefore Ge is more than likely a covalent solid. RbI has a steel from team 1 and a nonmetal from group 17, so the is one ionic hard containing Rb+ and I− ions. The compound C6(CH3)6 is a hydrocarbon (hexamethylbenzene), which consists of diverted molecules the stack to type a molecular solid v no covalent bonds in between them. Zn is a d-block element, so it is a metallic solid.

B Arranging this substances in order of boosting melting clues is straightforward, through one exception. We suppose C6(CH3)6 to have actually the lowest melting allude and Ge to have actually the highest melting point, through RbI what in between. The melt points that metals, however, are daunting to predict based upon the models presented for this reason far. Since Zn has a filled valence shell, it should not have actually a specifically high melt point, therefore a reasonable guess: v is C6(CH3)6 6(CH3)6, 166°C; Zn, 419°C; RbI, 642°C; and Ge, 938°C. This agrees through our prediction.


Classify C60, BaBr2, GaAs, and also AgZn as ionic, covalent, molecular, or metallic solids and then arrange them in stimulate of boosting melting points.

Answer: C60 (molecular) 2 (ionic) 60, around 300°C; AgZn, around 700°C; BaBr2, 856°C; and also GaAs, 1238°C.


The significant types that solids room ionic, molecular, covalent, and metallic. Ionic solids consists positively and negatively charged ions organized together by electrostatic forces; the toughness of the bonding is reflected in the lattice energy. Ionic solids have tendency to have high melting points and also are rather hard. Molecular solids are held together by reasonably weak forces, such together dipole–dipole interactions, hydrogen bonds, and London dispersion forces. Together a result, they often tend to be quite soft and have low melt points, which rely on their molecular structure. Covalent solids consist of two- or three-dimensional networks of atoms held together by covalent bonds; they often tend to be very hard and have high melting points. Metallic solids have unusual properties: in addition to having high thermal and also electrical conductivity and also being malleable and ductile, they exhibit luster, a shiny surface that reflects light. An alloy is a mixture of steels that has bulk metallic properties various from those that its constituent elements. Alloys can be formed by substituting one steel atom for an additional of comparable size in the lattice (substitutional alloys), by inserting smaller sized atoms right into holes in the metal lattice (interstitial alloys), or through a mix of both. Return the elemental composition of most alloys deserve to vary over large ranges, certain metals incorporate in just fixed proportions to form intermetallic compounds with distinct properties.

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Key Takeaway

Solids deserve to be classified together ionic, molecular, covalent (network), or metallic, whereby the general order of boosting strength of interaction is molecular 

Conceptual Problems

Match every vial through its contents.

The toughness of London dispersion forces in molecule solids tends to rise with molecular mass, causing a smooth rise in melt points. Some molecular solids, however, have significantly lower melting points 보다 predicted by their molecular masses. Why?

Suppose you want to synthesize a solid the is both warmth resistant and also a great electrical conductor. What specific types of bonding and molecular interactions would you want in your beginning materials?

Explain the differences between an interstitial alloy and a substitutional alloy. Given an alloy in which the identity of one metallic aspect is known, how can you recognize whether the is a substitutional alloy or an interstitial alloy?

How are intermetallic compounds different from interstitial alloys or substitutional alloys?