QUESTIONS AND PROBLEMS 2.4 (a) What is an isotope? (b) Why are the atomic weights of the ele- ments not integers? Cite two reasons. 2.2 Cite the difference between atomic mass and atomic weight. (a) How many grams are there in 1 amu of a material? 23 (b) Mole, in the context of this book, is taken in units of gram-mole. On this basis, how ‘many atoms are there in a pound-mole of a substance? (a) Cite two important quantum-mechanical concepts associated with the Bohr model of the atom, (b) Cite two important additional refine ‘ments that resulted from the wave-mechanical atomic model. 24 Relative to electrons and electron states, what does each of the four quantum numbers specify? Allowed values for the quantum numbers of electrons are as follows: 1.2.3. = 0,1,2,3,. my = 0, +1, 52, 43,... 41 26 n snd The relationships between 1 and the shell des- ignations are noted in Table 2.1. Relative to the subshells, = O corresponds to an ssubshell I corresponds to a psubshell I= 2 corresponds to a dsubshell I= 3 corresponds to an fsubshell For the K shell, the four quantum numbers for each of the two electrons in the Isstate, in the order of rimym,, are 100(3) and 100(3) 2a 28 29 242 ‘Write the four quantum numbers for all ofthe clectronsin the L and Mshells, and note which correspond to the s, p, and d subshells. Give the electron configurations for the fol- lowing ions: Fe’, Fe, Cut, Ba’, Br-, and se. Cesium bromide (CsBr) exhibits predomi- nantly ionic bonding. The Cs* and Br- ions have electron structures that are identical to which two inert gases? With regard to electron configuration, what do all the elements in Group VIIA of the periodic table have in common? Without consulting Figure 2.6 or Table 2.2, determine whether each of the electron con- figurations given below ts an inert gas, a halo- gen, an alkali metal, an alkaline earth metal, or a transition metal. Justify your choices, (a) 15%28*2p'3s'3p"sa"As? (by Ls22st2p9s%3p% (© 192s%2p%, (@) 1s2s2p3s2 (©) 1tastep'astap'sd%4s? (8) 15°25%2p'3s%3 ps! (a) What electron subshell is being filled for the rare earth series of elements on the peri- odie table? (b) What electron subshell is being filled for the actinide series? Calculate the force of attraction between a K* and an 0% ion the centers of which are separated by a distance of 1.5 nm, The net potential energy between two adj cent ions, Ey, may be represented by the of Equations 2.8 and 2.9, that is, m (2.11)Calculate the bonding energy Ey in terms of the parameters A, B, and n using the follow- ing procedure: 1, Differentiate Ex with respect to r,and then set the resulting expression equal to zero, since the curve of Ey versus ris a minim at Ey 2. Solve for rin terms of A, B, and n, which yields 1, the equilibrium interionic spacing. 3. Determine the expression for Ey by substi- tution of ry into Equation 2.11 2.14 Fora K*-CI" ion pair, attractive and repulsive energies Es and Ex, respectively, depend on the distance between the ions 1, according to 1.436 Es For these expressions, energies are expressed in electron volts per K*=CI- pair, and ris the distance in nanometers. The net energy Evvis just the sum of the two expressions above. (a) Supetimpose on asingle plot Ey. Ex. and Eq versus cup to 1.0 nm. (b) On the basis of this plot, determine (1) the equilibrium spacing 1 between the K* and CF ions, and (ii) the magnitude of the bonding energy E, between the two ions. (©) Mathematically determine the s and Ep values using the solutions to Problem 2.13 and compare these with the graphical results from part b. 2.15. Consider some hypothetical X* — Y~ ion pair for which the equilibrium interionic spacing and bonding energy values ate 0.35 nim and 6.13 eV, respectively. If it is known that 2 in Equation 2.11 has a value of 10, using the results of Problem 2.15, determine explicit ex- pressions for attractive and repulsive energ- ies, Eq and Ex of Equations 2.8 and 2.9. 2.16 The net potential energy Eybetween twoad- Jacent ions is sometimes represented by the expression Ew (2.12) in which ris the interionie separation and C, D, and p are constants whose values depend on the specific material (a) Derive an expression for the bonding en- ergy E, in terms of the equilibrium interionie separation i and the constants D and p using the following procedure: 1. Differentiate Ey with respect to rand set the resulting expression equal to zero, 2. Solve for C in terms of D, p, and 1. 3. Determine the expression for Ey by substitution for C in Equation 2.12 (b) Derive another expression for Bp in terms of 1, C, and p using a procedure analogous to the one outlined in part a 2.17 (a) Briefly cite the main differences between ionic, covalent, and metallic bonding, (b) State the Pauli exclusion principle. 2.18 Offer an explanation as to why covalently bonded materials are generally less dense than ionically or metallically bonded ones. 2.19 Compute the percents ionic character of the interatomic bonds for the following com pounds: TiO,, ZnTe, CsCl, InSb, and MgCl. 2.20 Make a plot of bonding energy versus melting temperature for the metals listed in Table 23. Using this plot, approximate the bonding en- ergy for copper, which has a melting temperé ture of 1084°C. 221 Using Table 2.2, determine the number of covalent bonds that are possible for atoms of the following elements: germanium, phos- phorus, selenium, and chlorine. 2.22 What type(s) of bonding would be expected for each of the following materials: brass (a copper-zine alloy), rubber, barium sulfide (BaS), solid xenon, bronze, nylon, and alumi- num phosphide (AIP)? 2.23 Explain why hydrogen fluoride (HF) has a higher boiling temperature than hydrogen chloride (HCI) (19.4 vs. 85°C), even though HF has a lower molecular weight 2.24 On the basis of the hydrogen bond, explain the anomalous behavior of water when it freezes. That Is, why is there volume expan. sion upon solidification?QUESTIONS AND PROBLEMS Note: To solve those problems having an asterisk (*) by their numbers, consultation of supplementary topics [appearing only on the CD-ROM (and not in print)] will probably be necessary. 31 32 33 34 35 36 37 38 What isthe difference between atomicstrue- 3.9 Calculate the radius of aniridiumatom given ture and crystal structure? that Irhas an FCC crystal structure, a density What is the difference between a erystal of 224 g/cm’, and an atomic weight of 192.2 structure and a crystal system? g/mol If the atomic radius of aluminum is 0.143 3410 Caleutate the radius of a vanadium atom, nm, calculate the volume of its unit cell in given that V has a BCC crystal structure, a cubic meters. density of 5.96 glem?, and an atomic weight Show for the body-centered cubic crystal of 50.9 g/mol. structure that the unit cell edge length a and 3.41 Some hypothetical metal has the simple cu- the atomic radius Rare related through a bic erystal structure shown in Figure 3.40. If ARV] its atomic weight is 70-4 g/mol and the atomic For the HCP crystal structure, show that the radius ts 0.126 nm, compute tts density deal cla ratio is 1.633. $12 Zirconinm hasan HCP crystal structure and Show that the atomic packing factor for BCC a density of 6.51 g/em’. is 0.68. (a) What Is the volume of its unit cell in ‘Show that the atomic packing factor for HCP cubic meters? is 0.74 (b) If the c/a ratio is 1.598, compute the Tron has a BCC crystal structure, an atomic values of ¢ and 3. radius of 0.124 nm, and an atomic weight 3.13 Using atomic weight, erystal structure, and of 55.85 g/mol. Compute and compare its atomic radius data tabulated inside the front density with the experimental value found cover, compute the theoretical densities of inside the front cover. lead, chromium, capper, and cobalt, anc then Ficune 3.40 Hard-sphere unit cell representation of the simple cuble crystal structure,314 315 3.16 3.7 3.18 319 3.20 compare these values with the measured densities listed in this same table. The cla ratio for cobalt is 1.623. Rhodium has an atomic radius of 0.1345 nm (1.345 A) and a density of 12.41 g/cm’, De- termine whether it has an FOC or BCC erys- tal structure. Below are listed the atomic weight, den and atomic radius for three hypothetical alloys. For each determine whether its crystal structure is FCC, BCC, or simple then justify your determination. A si cubic unit cell is shown in Figure 3.40. Atomic Atomic Weight Density Radius Alley (g/mol) (g/cm) (am) A TTA 8.22 0.125 B 1076 13.42 0.133 c 4273 9.23 0.142 The unit cell for tin has tetragonal symmetry, with a and b lattice parameters of 0.583 and 0.318 nm, respectively. If its density, atomic weight, and atomic radius are 7.30 g/cm’, 118.69 g/mol, and 0.151 nm, respectively. compute the atomic packing factor. Todine has an orthorhombic unit cell for which the a, 6, and c lattice parameters are 0.479, 0.725, and 0.978 nm, respectively. (a) If the atomic packing factor and atomic radius are 0.547 and 0.177 nm, respectively, determine the number of atoms in each unit cell. (b) The atomic weight of iodine is 126.91 g/ mol; compute its density. ‘Titanium has an HCP unit cell for which the ratio of the lattice parameters c/a is 1.58. If the radius of the Ti atom is 0.1445 nm, (a) determine the unit cell volume, and (b) cal- culate the density of Ti and compare it with the literature value. Zine has an HCP crystal structure, a c/a ratio of 1.856, and a density of 7.13 g/cm’, Caleu- late the atomic radius for Zn. Rhenium has an HCP crystal structure, an atomic radius of 0.137 nm, and a c/a ratio of 1.615, Compute the volume of the unit cell for Re. B22 3.23 326 (a) To which crystal system does this unit cell belong? (b) What would this crystal structure be called? (© Calculate the density of the material, given that its atomic weight is 141 g/mol Using the Molecule Definition File (MDP) on the CD-ROM that accompanies this book, generate a three-dimensional unit cell for the intermetallic compound AuCu, given. the following: 1) the unit cell is cubic with an edge length of 0.374 nm, 2) gold atoms are situated at all cube corners, and 3) copper atoms are positioned at the centers of all unit cell faces, Using the Molecule Definition File (MDF) on the CD-ROM that accompanies this book, generate a three-dimensional unit cell for the intermetallic compound AuCu given. the following: 1) the unit cell is tetragonal with 2 = 0.289 nm and ¢ = 0.367 nm (see Table 3.6), 2) gold atoms are situated at all unit cell corners, and 3) a copper atom is positioned at the center of the unit call. Sketch a unit cell for the bady-centered or- thorhombic crystal structure. For a ceramic compound, what are the two. characteristics of the component ions that determine the crystal structure? Show that the minimum cation-to-anion ra- dius ratio for a coordination number of 4 is 0.225.327 3.28 3.29 3.30 331 3.32 3.33 Show that the minimum cation-to-anion ra- dius ratio for a coordination number of 6 is 0.414. Hint: Use the NaCl crystal structure (Figure 3.5), and assume that anions and cat~ ions are just touching along cube edges and across face diagonals. Demonstrate that the minimum cation-to- adius ratio for a coordination number On the basis of ionic charge and ionic radii, predict the crystal structures for the follow- ing materials: (a) CsI, (b) NiO, ©) KT, and (@) NIS. Justify your selections Which of the cations in Table 3.4 would you predict to form iodides having the cesium chloride crystal structure? Justify your choices. Compute the atomic packing factor for the cesium chloride crystal structure in which telty = 0.732 Table 3.4 gives the ionic radif for K+ and 0% as 0.138 and 0.140 nm, respectively. What would be the coordination number for each O* ton? Briefly describe the resulting crystal structure for K,O. Explain why this is called the antifluorite structure. Using the Molecule Definition File (MDF) on the CD-ROM that accompanies this book, generate a three-cimensional unit coll for lead oxide, PbO, given the following: (1) the unit cell is tetragonal with 2 = 0.307 nm and c= 0.502 nm, (2) oxygen ions are situated at all cube corners, and, in addition. at the centers of the two square faces, (3) ‘one oxygen ion is positioned on each of two of the other opposing faces (rectangular) at the 0.520.287c coordinate, and (4) for the other two rectangular and opposing faces. oxygen ionsare located at the 0.52-0.763cco- ordinate. Calculate the density of FeO, given that it hay the rock salt crystal structure. Magnesium oxide has the rock salt crystal structure and a density of 3.58 p/cm’ (a) Determine the unit cell edge length (b) How does this result compare with the edge length as determined from the radi Table 3.4, assuming that the Mg’ and O {ons just touch each other along the edges? 3.36 3.37 3.38 3.39 3.40 341 3.2 3.43 344 are 0.154 nm and 109.5°, respectively. How does this value compare with the mea- sured density? Compute the theoretical density of ZnS given that the Zn—S distance and bond angle are 0.234 nm and 109.5°, respectively How does this value compare with the mea- sured density? Cadmium sulfide (CaS) has a cubic unit cell, and from x-ray diffraction data it 1s known that the cell edge length is 0.582 nm. If the measured density is 4.82 g/cm?, how many Ca? and S* ions are there per unit cell? (@) Using the ionic radii in Table 3.4, com- pute the density of CsCl. Hint: Use a modifi- cation of the result of Problem 3.4. (b) The measured density is 3.99 g/cm}, How do you explain the slight discrepancy be- tween your calculated value and the mea- sured one? From the data in Table 3.4, compute the density of CaF2, which has the fluorite structure, A hypothetical AX type of ceramic material is known to have a density of 2.65 gicm! and a unit cell of cubic symmetry with a cell edge length of 0.43 nm. The atomie weights of the A and X elements are 866 and 40.3 g/mol, respectively. On the basis of this informa- tion, which of the following crystal structures Is (are) possible for this material: rock salt, cesium chloride, or zine blende? Justify your choice(s) The unit cell for MgFe,O, (MgO-Fe,O;) has cubic symmetry with a unit call edge length of 0.836 nm, If the density of this material is 4.52 g/em?, compute its atomic packing factor. For this computation, you will need to use ionic radii listed in Table 3.4. ‘The unit cell for ALO; has hexagonal sym- metry with lattice parameters a = 0.4759 nm and ¢ = 1.2989 nm. If the density of this material is 3.99 glem’, caleulate its atomic packing factor. For this computation use ionic radii listed in Table 3.4 Compute the atomic packing factor for the diamond cubiecrystal structure (Figure3.16)846 3.47 38 349 3.50 Assume that bonding atoms touch one an. other, that the angle between adjacent bonds is 109.5%, and that each atom internal to the nit cell is positioned ald of the distance away from the two nearest cell faces (a is the unit cell edge length). Compute the atomic packing factor for ce. sium chloride using the ionic radi in Table 3.4 and assuming that the ions touch along the cube diagonals. Tn terms of bonding. explain why silicate ma- terials have relatively low densities. Determine the angle between covalent bonds in an SiO} tetrahedron, Draw an orthorhombic unit cell, and within that cell a [121] direction and a (210) plane. ‘Sketch a monoclinic unit cell, and within that cell a [OT1] direction and a (002) plane. Here are unit cells for two hypothetical metals: (a) What are the indices for the directions indicated by the two vectors in sketch (a)? feces (b) What are the indices for the two planes drawn in sketch (1)? Yam o 351 3.52 Within a cubic unit call, sketch the follow. ing directions: (@ (To; @) (TT: (o) (zn: fee (©) Te () (123); (@ (133); a) (703) Determine the indices for the directions Ey shown in the following cubic unit cell: 3 Determine the indices for the directions ge in the following cubic unit cell 354 For tetragonal crystals, cite the indices of directions that are equivalent to each of the following directions (@) (101); (b) [110}; (© (010)3.55 (a) Convert the [100] and [111] directions into the four-index Miller-Pravais scheme for hexagonal unit cells (b) Make the same conversion for the (010) and (101) planes. 3.56 Determine the Miller indices for the planes $3 shown in the following unit cell I 3.87 Determine the Miller indices for the planes shown in the following unit cell: 3.58 Determine the Miller indices for the planes $3 shown in the following unit cell: ee 3.59 Sketch the (1101) and (1120) planes ina hex- agonal unit cell, 3.60 Determine the indices for the planes shown Gg in the hexagonal unit cells shown below.3.61 3.62 3.63 3.64 3.65 3.66 3.67 Sketch within a cubic unit cell the follow. ing planes: (@) (WT): (9 a: @) (12); © (12) © (102), (@) (123), @ (31); ) (73). Sketch the atomic packing of (a) the (100) plane for the FCC crystal structure, and (b) the (111) plane for the BCC crystal structure (similar to Figures 3.240 and 3.255). For each of the following crystal structures, represent the indicated plane in the manner of Figures 3.24 and 3.25, showing both anions and cations: (a) (100) plane for the rock salt crystal structure, (b) (110) plane for the cesium chloride crystal structure, (© (11) plane for the zinc blende crystal structure, and ()_ (110) plane for the perov- skite crystal structure, Consider the reduced-sphere unit cell shown in Problem 3.21, having an origin of the coor- dinate system positioned at the atom labeled with an O. For the following sets of planes, determine which are equivalent: (@) (100), (070), and (001) (b) (110), (101), (011), and (110). (© (11), (111), (114), and (117) Cite the indices of the direction that results from the intersection of each of the following par of planes within a cubie crystal: (a) (110) and (111) planes; (b) (110) and (170) planes: and (©). (L0T) and (001) planes. The zinc blende crystal structure is one that may be generated from close-packed planes of anions. (@) Will the stacking sequence for this strue- ture be FCC or HCP? Why? (b)_ Will cations fill tetrahedral or octahedral positions? Why? (©) What fraction of the positions will be oc- cupied? The corundum crystal structure, found for AbO:, consists of an HCP arrangement of 3.68 3.69 3.70" 3.71" 3.72" 3.73" 3m" 35 © tons; the Al** fons occupy octahedral po- sitions, (@) What fraction of the available octahe- dral positions are filled with AL* ions? (b) Sketch two close-packed O*- planes stacked inan AB sequence, and note octahe- dral_ positions that will be filled with the AP* ions. Tron sulfide (FeS) may form a crystal struc- ture that consists of an HCP arrangement of S* ions. (@), Which type of interstidal site will the Fee ions occupy? (b), What fraction of these available intersti- tial sites will be occupied by Fe® ions? ‘Magnesium silicate, MgoSiOx, forms in the olivine crystal structure which consists of an HCP arrangement of O* ions, (@) Which type of interstitial site will the Mg** ions occupy? Why? () Which type of interstitial site will the Si** ions occupy? Why? (© What fraction of the total tetrahedral sites will be occupied? (@) What fraction of the total octahedral sites will be occupied? Compute and compare the linear densities of the [100], [110], and [111] directions for FCC. Compute and compare the linear densities of the [110] and [111] directions for BCC. Calculate and compare the planar densities of the (100) and (111) planes for FCC. Calculate and compare the planar densities of the (100) and (110) planes for BCC. Calculate the planar density of the (0001) plane for HCP. Here are shown the atomic packing schemes for several different crystallographic diree- tions for some hypothetical metal. For each direction the circles represent only those atoms contained within a unit cell, which cir- cles are reduced from their actual size.[J 0.30 1 (cor) e040 nm —v} (00), (O10) f——0.0 nn —>} (oo 0 64 rm» ——o} O—O—O (ony toy [e056 nm ——+} ina) (a) To what crystal system does the unit cell belong? (b) What would this crystal structure be called? Below are shown three different crystallo- graphic planes for a unit cell of some hypo- thetical metal; the circles represent atoms: " O Fe-c.40.om-af on) 036 n>] a9) (a) To what crystal system does the unit cell belong? (b) What would this crystal st called? (c) If the density of this metal is 8.95 g/cm’, determine lts atomle weight icture be Explain why the properties of polycrystalline materials are most often isotropic 3.18" 3.79" 2.80" 3.81" 3.82" 3.83" 3.84" 3.85" Using the data for molybdenum in Table 3.1, compute the interplanar spacing for the (111) set of planes. Determine the expected diffraction angle for the first-order reflection from the (113) set of planes for FCC platinum when monochro- matic radiation of wavelength 0.1542 nm is used Using the data for al in Table 3.1 compute the interplanar spacings for the (110) and (221) sets of planes. ‘The metal iridium has an FCC crystal struc- ture. If the angle of diffraction for the (220) set of planes occurs at 69.22° (first-orcler re~ flection) when monochromatic x-radiation having a wavelength of 0.1542 nm is used compute (a) the interplanar spacing for this set of planes, and (b) the atomic radius for an iridium atom, ‘The metal rubidium hasa BCC crystal struc- ture. If the angle of diffraction for the (321) set of planes occurs at 27.00" (first-orde: flection) when monochromat having a wavelength of 0.0711 compute (a) the interplanar spacing for this set of planes, and (b) the atomic radius for the rubidium atom, m Is used, For which set of crystallographic planes will a first-order diffraction peak occur at ad fraction angle of 46.21° for BCC iron when monochromatic radiation having a wave. Iength of 0.0711 nm is used? Figure 3.37 shows an x-ray diffraction pat- tem for a-iron taken using a diffractometer and_ monochromatic n having a wavelength of 0.1542 nm; each diffraction peak on the pattern has been indexed. Com- pute the interplanar spacing for each set of planes indexed; also determine the lattice parameter of Fe for each of the peaks. xral The diffraction peaks shown in Figure 3.37 are indexed according to the reflection rules for BCC (ie., the sum lr + & + I must be even). Cite the A, k, and / indices for the first four diffraction peaks for FCC crystals consistent with A, k, and / all being elther odd or even.—) “66 70 FicuRe 3.41 Diffraction pattern Ditton angle 20 3.86" Figure 3.41 shows the first four peaks of the x-ray diffraction pattern for copper. which has an FCC crystal structure; monochro- matic x-radiation having a wavelength of 0.1542 nm was used. a) Index (ie, give fh, k, and J each of these peaks. (b) Determine the each of the peaks (© For each peak, determine the atomic ra- dis for Curand compare these with the value presented in Table 3. \'lices for) nterplanar spacing for 3.87. Would you expect a material in which the atomic bonding is predominantly tonic in na- ture to be more or less likely to form a non- crystalline solid upon solidification than a covalent material? Why? (See Section 2.6.) Design Problem 3.DL* Gallium arsenide (GaAs) and gallium phos- phide (GaP) both have the zinc blende crys- tal structure and are soluble in one anather at all concentrations. Determine the con- centration in weight percent of GaP that must be added to GaAs to yield a unit cell edge length of 0.5570 nm. The densities of GaAs and GaP are 5.307 and 4.130 g/cm’, respectively,