ࡱ>  ynRoot Entry FAData WordDocument_jObjectPoolT/,b  !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~g89Root Entry F𩡗@Data WordDocumentlObjectPoolT/,Equation Native 1Tablee+SummaryInformation(DocumentSummaryInformation8L]vj^}EF      !"#$%&'()*+,-./0123456789:;<=>?@ABCDGIHKJLMNOPQSRTUVWXZ[u]\^_a`bcdefghijkmlmoqrtkvwxM{~lmnopqrstuvwxyz{|}~4.3, each repeat unit has eight carbons and eight hydrogens. Thus, m = 8(AC) + 8(AH) = (8)(12.01 g/mol) + (8)(1.008 g/mol) = 104.14 g/mol (b) We are now asked to compute the number-average molecular weight. Since the degree of polymerization is 25,000, using Equation 14.6  EMBED Equation.3  14.5 Below, molecular weight data for a polypropylene material are tabulated. Compute (a) the number-average molecular weight, (b) the weight-average molecular weight, and (c) the degree of polymerization. Molecular Weight Range (g/mol)xiwi8,00016,0000.050.0216,00024,0000.160.1024,00032,0000.240.2032,00040,0000.280.3040,00048,0000.200.2748,00056,0000.070.11 Solution (a) From the tabulated data, we are asked to compute  EMBED Equation.3 , the number-average molecular weight. This is carried out below. Molecular wt Range Mean Mi xi xiMi 8,000-16,000 12,000 0.05 600 16,000-24,000 20,000 0.16 3200 24,000-32,000 28,000 0.24 6720 32,000-40,000 36,000 0.28 10,080 40,000-48,000 44,000 0.20 8800 48,000-56,000 52,000 0.07 3640 ____________________________  EMBED Equation.3  (b) From the tabulated data, we are asked to compute  EMBED Equation.3 , the weight-average molecular weight. Molecular wt. Range Mean Mi wi wiMi 8,000-16,000 12,000 0.02 240 16,000-24,000 20,000 0.10 2000 24,000-32,000 28,000 0.20 5600 32,000-40,000 36,000 0.30 10,800 40,000-48,000 44,000 0.27 11,880 48,000-56,000 52,000 0.11 5720 ___________________________  EMBED Equation.3  (c) Now we are asked to compute the degree of polymerization, which is possible using Equation 14.6. For polypropylene, the repeat unit molecular weight is just m = 3(AC) + 6(AH) = (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol And  EMBED Equation.3  14.6 Molecular weight data for some polymer are tabulated here. Compute (a) the number-average molecular weight, and (b) the weight-average molecular weight. (c) If it is known that this material's degree of polymerization is 710, which one of the polymers listed in Table 14.3 is this polymer? Why? Molecular Weight Range g/molxiwi15,00030,0000.040.0130,00045,0000.070.0445,00060,0000.160.1160,00075,0000.260.2475,00090,0000.240.2790,000105,0000.120.16105,000120,0000.080.12120,000135,0000.030.05 Solution (a) From the tabulated data, we are asked to compute  EMBED Equation.3 , the number-average molecular weight. This is carried out below. Molecular wt. Range Mean Mi xi xiMi 15,000-30,000 22,500 0.04 900 30,000-45,000 37,500 0.07 2625 45,000-60,000 52,500 0.16 8400 60,000-75,000 67,500 0.26 17,550 75,000-90,000 82,500 0.24 19,800 90,000-105,000 97,500 0.12 11,700 105,000-120,000 112,500 0.08 9000 120,000-135,000 127,500 0.03 3825 _________________________  EMBED Equation.3  (b) From the tabulated data, we are asked to compute  EMBED Equation.3 , the weight-average molecular weight. This determination is performed as follows: Molecular wt. Range Mean Mi wi wiMi 15,000-30,000 22,500 0.01 225 30,000-45,000 37,500 0.04 1500 45,000-60,000 52,500 0.11 5775 60,000-75,000 67,500 0.24 16,200 75,000-90,000 82,500 0.27 22,275 90,000-105,000 97,500 0.16 15,600 105,000-120,000 112,500 0.12 13,500 120,000-135,000 127,500 0.05 6375 _________________________  EMBED Equation.3  (c) We are now asked if the degree of polymerization is 710, which of the polymers in Table 14.3 is this material? It is necessary to compute m in Equation 14.6 as  EMBED Equation.3  The repeat unit molecular weights of the polymers listed in Table 14.3 are as follows: Polyethylene--28.05 g/mol Poly(vinyl chloride)--62.49 g/mol Polytetrafluoroethylene--100.02 g/mol Polypropylene--42.08 g/mol Polystyrene--104.14 g/mol Poly(methyl methacrylate)--100.11 g/mol Phenol-formaldehyde--133.16 g/mol Nylon 6,6--226.32 g/mol PET--192.16 g/mol Polycarbonate--254.27 g/mol Therefore, polystyrene is the material since its repeat unit molecular weight is closest to that calculated above. 14.7 Is it possible to have a poly(methyl methacrylate) homopolymer with the following molecular weight data and a of polymerization of 527? Why or why not? Molecular Weight Range (g/mol)wixi8,00020,0000.020.0520,00032,0000.080.1532,00044,0000.170.2144,00056,0000.290.2856,00068,0000.230.1868,00080,0000.160.1080,00092,0000.050.03 Solution This problem asks if it is possible to have a poly(methyl methacrylate) homopolymer with the given molecular weight data and a degree of polymerization of 527. The appropriate data are given below along with a computation of the number-average molecular weight. Molecular wt. Range Mean Mi xi xiMi 8,000-20,000 14,000 0.04 560 20,000-32,000 26,000 0.10 2600 32,000-44,000 38,000 0.16 6080 44,000-56,000 50,000 0.26 13,000 56,000-68,000 62,000 0.23 14,260 68,000-80,000 74,000 0.15 11,100 80,000-92,000 86,000 0.06 5160 _________________________  EMBED Equation.3  For PMMA, from Table 14.3, each repeat unit has five carbons, eight hydrogens, and two oxygens. Thus, m = 5(AC) + 8(AH) + 2(AO) = (5)(12.01 g/mol) + (8)(1.008 g/mol) + (2)(16.00 g/mol) = 100.11 g/mol Now, we will compute the degree of polymerization using Equation 14.6 as  EMBED Equation.3  Thus, such a homopolymer is possible since the calculated degree of polymerization is 527. 14.8 High-density polyethylene may be chlorinated by inducing the random substitution of chlorine atoms for hydrogen. (a) Determine the concentration of Cl (in wt%) that must be added if this substitution occurs for 5% of all the original hydrogen atoms. (b) In what ways does this chlorinated polyethylene differ from poly(vinyl chloride)? Solution (a) For chlorinated polyethylene, we are asked to determine the weight percent of chlorine added for 5% Cl substitution of all original hydrogen atoms. Consider 50 carbon atoms; there are 100 possible side-bonding sites. Ninety-five are occupied by hydrogen and five are occupied by Cl. Thus, the mass of these 50 carbon atoms, mC, is just mC = 50(AC) = (50)(12.01 g/mol) = 600.5 g Likewise, for hydrogen and chlorine, mH = 95(AH) = (95)(1.008 g/mol) = 95.76 g mCl = 5(ACl) = (5)(35.45 g/mol) = 177.25 g Thus, the concentration of chlorine, CCl, is determined using a modified form of Equation 4.3 as  EMBED Equation.3   EMBED Equation.3  (b) Chlorinated polyethylene differs from poly(vinyl chloride), in that, for PVC, (1) 25% of the side-bonding sites are substituted with Cl, and (2) the substitution is probably much less random. Molecular Shape 14.9 For a linear polymer molecule, the total chain length L depends on the bond length between chain atoms d, the total number of bonds in the molecule N, and the angle between adjacent backbone chain atoms , as follows:  EMBED Equation.3  (14.11) Furthermore, the average end-to-end distance for a series of polymer molecules r in Figure 14.6 is equal to  EMBED Equation.3  (14.12) A linear polytetrafluoroethylene has a number-average molecular weight of 500,000 g/mol; compute average values of L and r for this material. Solution This problem first of all asks for us to calculate, using Equation 14.11, the average total chain length, L, for a linear polytetrafluoroethylene polymer having a number-average molecular weight of 500,000 g/mol. It is necessary to calculate the number-average degree of polymerization, DP, using Equation 14.6. For polytetrafluoroethylene, from Table 14.3, each repeat unit has two carbons and four flourines. Thus, m = 2(AC) + 4(AF) = (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol and  EMBED Equation.3  which is the number of repeat units along an average chain. Since there are two carbon atoms per repeat unit, there are two CC chain bonds per repeat unit, which means that the total number of chain bonds in the molecule, N, is just (2)(5000) = 10,000 bonds. Furthermore, assume that for single carbon-carbon bonds, d = 0.154 nm and q = 109 (Section 14.4); therefore, from Equation 14.11  EMBED Equation.3   EMBED Equation.3  It is now possible to calculate the average chain end-to-end distance, r, using Equation 14.12 as  EMBED Equation.3  14.10 Using the definitions for total chain molecule length, L (Equation 14.11) and average chain end-to-end distance r (Equation 14.12), for a linear polyethylene determine: (a) the number-average molecular weight for L = 2500 nm; (b) the number-average molecular weight for r = 20 nm. Solution (a) This portion of the problem asks for us to calculate the number-average molecular weight for a linear polyethylene for which L in Equation 14.11 is 2500 nm. It is first necessary to compute the value of N using this equation, where, for the C C chain bond, d = 0.154 nm, and q = 109. Thus  EMBED Equation.3   EMBED Equation.3  Since there are two C C bonds per polyethylene repeat unit, there is an average of N/2 or 19,940/2 = 9970 repeat units per chain, which is also the degree of polymerization, DP. In order to compute the value of  EMBED Equation.3  using Equation 14.6, we must first determine m for polyethylene. Each polyethylene repeat unit consists of two carbon and four hydrogen atoms, thus m = 2(AC) + 4(AH) = (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol Therefore  EMBED Equation.3  (b) Next, we are to determine the number-average molecular weight for r = 15 nm. Solving for N from Equation 14.12 leads to  EMBED Equation.3  which is the total number of bonds per average molecule. Since there are two CC bonds per repeat unit, then DP = N/2 = 16,900/2 = 8450. Now, from Equation 14.6  EMBED Equation.3  Molecular Configurations 14.11 Sketch portions of a linear polystyrene molecule that are (a) syndiotactic, (b) atactic, and (c) isotactic. Use two-dimensional schematics per footnote 8 of this chapter. Solution We are asked to sketch portions of a linear polystyrene molecule for different configurations (using two-dimensional schematic sketches). (a) Syndiotactic polystyrene  (b) Atactic polystyrene  (c) Isotactic polystyrene  14.12 Sketch cis and trans structures for (a) butadiene, and (b) chloroprene. Use two-dimensional schematics per footnote 11 of this chapter. Solution This problem asks for us to sketch cis and trans structures for butadiene and chloroprene. (a) The structure for cis polybutadiene (Table 14.5) is  The structure of trans butadiene is  (b) The structure of cis chloroprene (Table 14.5) is  The structure of trans chloroprene is  Thermoplastic and Thermosetting Polymers 14.13 Make comparisons of thermoplastic and thermosetting polymers (a) on the basis of mechanical characteristics upon heating, and (b) according to possible molecular structures. Solution (a) Thermoplastic polymers soften when heated and harden when cooled, whereas thermosetting polymers, harden upon heating, while further heating will not lead to softening. (b) Thermoplastic polymers have linear and branched structures, while for thermosetting polymers, the structures will normally be network or crosslinked. 14.14 (a) Is it possible to grind up and reuse phenol-formaldehyde? Why or why not? (b) Is it possible to grind up and reuse polypropylene? Why or why not? Solution (a) It is not possible to grind up and reuse phenol-formaldehyde because it is a network thermoset polymer and, therefore, is not amenable to remolding. (b) Yes, it is possible to grind up and reuse polypropylene since it is a thermoplastic polymer, will soften when reheated, and, thus, may be remolded. Copolymers 14.15 Sketch the repeat structure for each of the following alternating copolymers: (a) poly(butadiene-chloroprene), (b) poly(styrene-methyl methacrylate), and (c) poly(acrylonitrile-vinyl chloride). Solution This problem asks for sketches of the repeat unit structures for several alternating copolymers. (a) For poly(butadiene-chloroprene)  (b) For poly(styrene-methyl methacrylate)  (c) For poly(acrylonitrile-vinyl chloride)  14.16 The number-average molecular weight of a poly(styrene-butadiene) alternating copolymer is 1,350,000 g/mol; determine the average number of styrene and butadiene repeat units per molecule. Solution Since it is an alternating copolymer, the number of both types of repeat units will be the same. Therefore, consider them as a single repeat unit, and determine the number-average degree of polymerization. For the styrene repeat unit, there are eight carbon atoms and eight hydrogen atoms, while the butadiene repeat consists of four carbon atoms and six hydrogen atoms. Therefore, the styrene-butadiene combined repeat unit weight is just m = 12(AC) + 14(AH) = (12)(12.01 g/mol) + (14)(1.008 g/mol) = 158.23 g/mol From Equation 14.6, the degree of polymerization is just  EMBED Equation.3  Thus, there is an average of 8530 of both repeat unit types per molecule. 14.17 Calculate the number-average molecular weight of a random nitrile rubber [poly(acrylonitrile-butadiene) copolymer] in which the fraction of butadiene repeat units is 0.30; assume that this concentration corresponds to a degree of polymerization of 2000. Solution This problem asks for us to calculate the number-average molecular weight of a random nitrile rubber copolymer. For the acrylonitrile repeat unit there are three carbon, one nitrogen, and three hydrogen atoms. Thus, its repeat unit molecular weight is mAc = 3(AC) + (AN) + 3(AH) = (3)(12.01 g/mol) + 14.01 g/mol + (3)(1.008 g/mol) = 53.06 g/mol The butadiene repeat unit is composed of four carbon and six hydrogen atoms. Thus, its repeat unit molecular weight is mBu = 4(AC) + 6(AH) = (4)(12.01 g/mol) + (6)(1.008 g/mol) = 54.09 g/mol From Equation 14.7, the average repeat unit molecular weight is just  EMBED Equation.3  = (0.70)(53.06 g/mol) + (0.30)(54.09 g/mol) = 53.37 g/mol Since DP = 2000 (as stated in the problem),  EMBED Equation.3  may be computed using Equation 14.6 as  EMBED Equation.3  14.18 An alternating copolymer is known to have a number-average molecular weight of 250,000 g/mol and a degree of polymerization of 3420. If one of the repeat units is styrene, which of ethylene, propylene, tetrafluoroethylene, and vinyl chloride is the other repeat unit? Why? Solution For an alternating copolymer which has a number-average molecular weight of 250,000 g/mol and a degree of polymerization of 3420, we are to determine one of the repeat unit types if the other is styrene. It is first necessary to calculate  EMBED Equation.3  using Equation 14.6 as  EMBED Equation.3  Since this is an alternating copolymer we know that chain fraction of each repeat unit type is 0.5; that is fs = fx = 0.5, fs and fx being, respectively, the chain fractions of the styrene and unknown repeat units. Also, the repeat unit molecular weight for styrene is ms = 8(AC) + 8(AH) = 8(12.01 g/mol) + 8(1.008 g/mol) = 104.14 g/mol Now, using Equation 14.7, it is possible to calculate the repeat unit weight of the unknown repeat unit type, mx. Thus  EMBED Equation.3   EMBED Equation.3  Finally, it is necessary to calculate the repeat unit molecular weights for each of the possible other repeat unit types. These are calculated below: methylene = 2(AC) + 4(AH) = 2(12.01 g/mol) + 4(1.008 g/mol) = 28.05 g/mol mpropylene = 3(AC) + 6(AH) = 3(12.01 g/mol) + 6(1.008 g/mol) = 42.08 g/mol mTFE = 2(AC) + 4(AF) = 2(12.01 g/mol) + 4(19.00 g/mol) = 100.02 g/mol mVC = 2(AC) + 3(AH) + (ACl) = 2(12.01 g/mol) + 3(1.008 g/mol) + 35.45 g/mol = 62.49 g/mol Therefore, propylene is the other repeat unit type since its m value is almost the same as the calculated mx. 14.19 (a) Determine the ratio of butadiene to styrene repeat units in a copolymer having a number-average molecular weight of 350,000 g/mol and degree of polymerization of 4425. (b) Which type(s) of copolymer(s) will this copolymer be, considering the following possibilities: random, alternating, graft, and block? Why? Solution (a) This portion of the problem asks us to determine the ratio of butadiene to styrene repeat units in a copolymer having a weight-average molecular weight of 350,000 g/mol and a degree of polymerization of 4425. It first becomes necessary to calculate the average repeat unit molecular weight of the copolymer,  EMBED Equation.3 , using Equation 14.6 as  EMBED Equation.3  If we designate fb as the chain fraction of butadiene repeat units, since the copolymer consists of only two repeat unit types, the chain fraction of styrene repeat units fs is just 1 fb. Now, Equation 14.7 for this copolymer may be written in the form  EMBED Equation.3  in which mb and ms are the repeat unit molecular weights for butadiene and styrene, respectively. These values are calculated as follows: mb = 4(AC) + 6(AH) = 4(12.01 g/mol) + 6(1.008 g/mol) = 54.09 g/mol ms = 8(AC) + 8(AH) = 8(12.01 g/mol) + 8(1.008 g/mol) = 104.14 g/mol Solving for fb in the above expression yields  EMBED Equation.3  Furthermore, fs = 1 fb = 1 0.50 = 0.50; or the ratio is just  EMBED Equation.3  (b) Of the possible copolymers, the only one for which there is a restriction on the ratio of repeat unit types is alternating; the ratio must be 1:1. Therefore, on the basis of the result in part (a), the possibilities for this copolymer are not only alternating, but also random, graft, and block. 14.20 Crosslinked copolymers consisting of 60 wt% ethylene and 40 wt% propylene may have elastic properties similar to those for natural rubber. For a copolymer of this composition, determine the fraction of both repeat unit types. Solution For a copolymer consisting of 60 wt% ethylene and 40 wt% propylene, we are asked to determine the fraction of both repeat unit types. In 100 g of this material, there are 60 g of ethylene and 40 g of propylene. The ethylene (C2H4) molecular weight is m(ethylene) = 2(AC) + 4(AH) = (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol The propylene (C3H6) molecular weight is m(propylene) = 3(AC) + 6(AH) = (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol Therefore, in 100 g of this material, there are  EMBED Equation.3  and  EMBED Equation.3  Thus, the fraction of the ethylene repeat unit, f(ethylene), is just  EMBED Equation.3  Likewise,  EMBED Equation.3  14.21 A random poly(isobutylene-isoprene) copolymer has a number-average molecular weight of 200,000 g/mol and a degree of polymerization of 3000. Compute the fraction of isobutylene and isoprene repeat units in this copolymer. Solution For a random poly(isobutylene-isoprene) copolymer in which  EMBED Equation.3  = 200,000 g/mol and DP = 3000, we are asked to compute the fractions of isobutylene and isoprene repeat units. From Table 14.5, the isobutylene repeat unit has four carbon and eight hydrogen atoms. Thus, mib = (4)(12.01 g/mol) + (8)(1.008 g/mol) = 56.10 g/mol Also, from Table 14.5, the isoprene repeat unit has five carbon and eight hydrogen atoms, and mip = (5)(12.01 g/mol) + (8)(1.008 g/mol) = 68.11 g/mol From Equation 14.7  EMBED Equation.3  Now, let x = fib, such that  EMBED Equation.3  since fib + fip = 1. Also, from Equation 14.6  EMBED Equation.3  Or  EMBED Equation.3  Solving for x leads to x = fib = f(isobutylene) = 0.12. Also, f(isoprene) = 1 x = 1 0.12 = 0.88 Polymer Crystallinity 14.22 Explain briefly why the tendency of a polymer to crystallize decreases with increasing molecular weight. Solution The tendency of a polymer to crystallize decreases with increasing molecular weight because as the chains become longer it is more difficult for all regions along adjacent chains to align so as to produce the ordered atomic array. 14.23 For each of the following pairs of polymers, do the following: (1) state whether or not it is possible to determine whether one polymer is more likely to crystallize than the other; (2) if it is possible, note which is the more likely and then cite reason(s) for your choice; and (3) if it is not possible to decide, then state why. (a) Linear and syndiotactic poly(vinyl chloride); linear and isotactic polystyrene. (b) Network phenol-formaldehyde; linear and heavily crosslinked cis-isoprene. (c) Linear polyethylene; lightly branched isotactic polypropylene. (d) Alternating poly(styrene-ethylene) copolymer; random poly(vinyl chloride-tetrafluoroethylene) copolymer. Solution (a) Yes, for these two polymers it is possible to decide. The linear and syndiotactic poly(vinyl chloride) is more likely to crystallize; the phenyl side-group for polystyrene is bulkier than the Cl side-group for poly(vinyl chloride). Syndiotactic and isotactic isomers are equally likely to crystallize. (b) No, it is not possible to decide for these two polymers. Both heavily crosslinked and network polymers are not likely to crystallize. (c) Yes, it is possible to decide for these two polymers. The linear polyethylene is more likely to crystallize. The repeat unit structure for polypropylene is chemically more complicated than is the repeat unit structure for polyethylene. Furthermore, branched structures are less likely to crystallize than are linear structures. (d) Yes, it is possible to decide for these two copolymers. The alternating poly(styrene-ethylene) copolymer is more likely to crystallize. Alternating copolymers crystallize more easily than do random copolymers. 14.24 The density of totally crystalline polypropylene at room temperature is 0.946 g/cm3. Also, at room temperature the unit cell for this material is monoclinic with lattice parameters a = 0.666 nm  = 90( b = 2.078 nm  = 99.62( c = 0.650 nm  = 90( If the volume of a monoclinic unit cell, Vmono, is a function of these lattice parameters as Vmono = abc sin b determine the number of repeat units per unit cell. Solution For this problem we are given the density of polypropylene (0.946 g/cm3), an expression for the volume of its unit cell, and the lattice parameters, and are asked to determine the number of repeat units per unit cell. This computation necessitates the use of Equation 3.5, in which we solve for n. Before this can be carried out we must first calculate VC, the unit cell volume, and A the repeat unit molecular weight. For VC VC = abc sin b = (0.666 nm)(2.078 nm)(0.650 nm) sin (99.62) = 0.8869 nm3 = 8.869 ( 10-22 cm3 The repeat unit for polypropylene is shown in Table 14.3, from which the value of A may be determined as follows: A = 3(AC) + 6(AH) = 3(12.01 g/mol) + 6(1.008 g/mol) = 42.08 g/mol Finally, solving for n from Equation 3.5 leads to  EMBED Equation.3   EMBED Equation.3  = 12.0 repeat unit/unit cell 14.25 The density and associated percent crystallinity for two polytetrafluoroethylene materials are as follows:  (g/cm3)crystallinity (%)2.14451.32.21574.2 (a) Compute the densities of totally crystalline and totally amorphous polytetrafluoroethylene. (b) Determine the percent crystallinity of a specimen having a density of 2.26 g/cm3. Solution (a) We are asked to compute the densities of totally crystalline and totally amorphous polytetrafluoroethylene (rc and ra from Equation 14.8). From Equation 14.8 let  EMBED Equation.3 , such that  EMBED Equation.3  Rearrangement of this expression leads to  EMBED Equation.3  in which rc and ra are the variables for which solutions are to be found. Since two values of rs and C are specified in the problem statement, two equations may be constructed as follows:  EMBED Equation.3   EMBED Equation.3  In which rs1 = 2.144 g/cm3, rs2 = 2.215 g/cm3, C1 = 0.513, and C2 = 0.742. Solving the above two equations for ra and rc leads to  EMBED Equation.3   EMBED Equation.3  And  EMBED Equation.3   EMBED Equation.3  (b) Now we are to determine the % crystallinity for rs = 2.26 g/cm3. Again, using Equation 14.8  EMBED Equation.3   EMBED Equation.3  = 87.9% 14.26 The density and associated percent crystallinity for two nylon 6,6 materials are as follows:  (g/cm3)crystallinity (%)1.18867.31.15243.7 (a) Compute the densities of totally crystalline and totally amorphous nylon 6,6. (b) Determine the density of a specimen having 55.4% crystallinity. Solution (a) We are asked to compute the densities of totally crystalline and totally amorphous nylon 6,6 (rc and ra from Equation 14.8). From Equation 14.8 let  EMBED Equation.3 , such that  EMBED Equation.3  Rearrangement of this expression leads to  EMBED Equation.3  in which rc and ra are the variables for which solutions are to be found. Since two values of rs and C are specified in the problem, two equations may be constructed as follows:  EMBED Equation.3   EMBED Equation.3  In which rs1 = 1.188 g/cm3, rs2 = 1.152 g/cm3, C1 = 0.673, and C2 = 0.437. Solving the above two equations for ra and rc leads to  EMBED Equation.3   EMBED Equation.3  And  EMBED Equation.3   EMBED Equation.3  (b) Now we are asked to determine the density of a specimen having 55.4% crystallinity. Solving for rs from Equation 14.8 and substitution for ra and rc which were computed in part (a) yields  EMBED Equation.3   EMBED Equation.3  = 1.170 g/cm3 Diffusion in Polymeric Materials 14.27 Consider the diffusion of water vapor through a polypropylene (PP) sheet 2 mm thick. The pressures of H2O at the two faces are 1 kPa and 10 kPa, which are maintained constant. Assuming conditions of steady state, what is the diffusion flux [in [(cm3 STP)/cm2-s] at 298 K? Solution This is a permeability problem in which we are asked to compute the diffusion flux of water vapor through a 2-mm thick sheet of polypropylene. In order to solve this problem it is necessary to employ Equation 14.9. The permeability coefficient of H2O through PP is given in Table 14.6 as 38 ( 10-13 (cm3 STP)-cm/cm2-s-Pa. Thus, from Equation 14.9  EMBED Equation.3  and taking P1 = 1 kPa (1,000 Pa) and P2 = 10 kPa (10,000 Pa) we get  EMBED Equation.3   EMBED Equation.3  14.28 Argon diffuses through a high density polyethylene (HDPE) sheet 40 mm thick at a rate of 4.0 107 (cm3 STP)/cm2-s at 325 K. The pressures of argon at the two faces are 5000 kPa and 1500 kPa, which are maintained constant. Assuming conditions of steady state, what is the permeability coefficient at 325 K? Solution This problem asks us to compute the permeability coefficient for argon through high density polyethylene at 325 K given a steady-state permeability situation. It is necessary for us to Equation 14.9 in order to solve this problem. Rearranging this expression and solving for the permeability coefficient gives  EMBED Equation.3  Taking P1 = 1500 kPa (1,500,000 Pa) and P2 = 5000 kPa (5,000,000 Pa), the permeability coefficient of Ar through HDPE is equal to  EMBED Equation.3   EMBED Equation.3  14.29 The permeability coefficient of a type of small gas molecule in a polymer is dependent on absolute temperature according to the following equation:  EMBED Equation.3  where  EMBED Equation.3 and Qp are constants for a given gas-polymer pair. Consider the diffusion of hydrogen through a poly(dimethyl siloxane) (PDMSO) sheet 20 mm thick. The hydrogen pressures at the two faces are 10 kPa and 1 kPa, which are maintained constant. Compute the diffusion flux [in (cm3 STP)/cm2 s] at 350 K. For this diffusion system  EMBED Equation.3  Qp = 13.7 kJ/mol Also, assume a condition of steady state diffusion Solution This problem asks that we compute the diffusion flux at 350 K for hydrogen in poly(dimethyl siloxane) (PDMSO). It is first necessary to compute the value of the permeability coefficient at 350 K. The temperature dependence of PM is given in the problem statement, as follows:  EMBED Equation.3  And, incorporating values provided for the constants PM0 and Qp, we get  EMBED Equation.3   EMBED Equation.3  And, using Equation 14.9, the diffusion flux is equal to  EMBED Equation.3   EMBED Equation.3   EMBED Equation.3  PAGE  Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. 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Style2$a$:Oa: , SuperscriptCJEH:Oa: Style3  ROR kPNEquation$ 8^a$OJQJ_HaJHOH mnoindent$da$OJQJ_HaJ<Z@< m Plain Text OJQJaJ>Oa> m Superscript_1CJEH6Oa6 m SubscriptCJEH:O: mh2 $d5OJQJ_H8O8 mlist_1 0^`0\O\ m Equation_1)!$ 8xd^a$gdJkaJ0O"0 mlist_2 "^8O28 tJequation # H$0oB0 tJindent $`i{X1X( z_1043838479F//Ole CompObjRObjInfo  !$'*-.14569<?BCFILOPSVWX[^_befgjmnoruvwz}FMicrosoft Equation 3.0DNQE Equation.3 FMicrosoft EquationDNQE Equation.3Equation Native #_1177419820D' F//Ole CompObj RObjInfo Equation Native  _1177420190F//Ole    Times New RomanwDTimes{P="wM wn wm=1,000,000 g/mol42.08 g/mol= 23,700FMicrosoft EquationDNQE Equation.3CompObjRObjInfoEquation Native _1072953062F//  Times New Roman"wM wn = (wDwP)wm=(25,000)(104.14 g/mol) = 2.60  10 6  g/molFMicrosoft EquationDNQE Equation.3Ole CompObjRObjInfoEquation Native J.  Times New Roman"uM unFMicrosoft EquationDNQE Equation.3  Times New Roman"wM_1177420694"F//Ole CompObjRObjInfoEquation Native _1072953573F//Ole "CompObj #R wn  =wx wi wM wi  =33,040 g/molFMicrosoft EquationDNQE Equation.3.  Times New Roman"uM uwObjInfo!%Equation Native &J_1177420989$F//Ole (FMicrosoft EquationDNQE Equation.3  Times New Roman"wM ww  =ww wi wM wi  =36,240 g/molCompObj#%)RObjInfo&+Equation Native ,_1177421093;)F//Ole /CompObj(*0RObjInfo+2Equation Native 3FMicrosoft EquationDNQE Equation.3  Times New RomanwDwP="wM wn wm=33,040 g/mol42.08 g/mol=785_1072954217O.F//Ole 7CompObj-/8RObjInfo0:FMicrosoft EquationDNQE Equation.3.  Times New Roman"uM unFMicrosoft EquationDNQE Equation.3Equation Native ;J_11774388573F//Ole =CompObj24>RObjInfo5@Equation Native A_10729542768F//Ole D  Times New Roman"wM wn =wx wi wM wi  =73,800 g/molFMicrosoft EquationDNQE Equation.3CompObj79ERObjInfo:GEquation Native HJ_11774391381@=F//.  Times New Roman"uM uwFMicrosoft EquationDNQE Equation.3  Times New Roman"wM ww =ww wi wM wi Ole JCompObj<>KRObjInfo?MEquation Native N =81,450 g/molFMicrosoft EquationDNQE Equation.3  Times New Romanwm ="wM wn wDwP=73,800 g/mol710=_1177439731BF//Ole QCompObjACRRObjInfoDTEquation Native U_1155800330vGF//Ole YCompObjFHZR103.94 g/mol FMicrosoft EquationDNQE Equation.3  Times New Roman"uM un  = ux ui uM ui   = 52,760 g/molObjInfoI\Equation Native ]_1155800563LF//Ole `FMicrosoft EquationDNQE Equation.3  Times New RomanuDuP = uM   un   um = 52,760 g/mol100.11 g/mol = 527CompObjKMaRObjInfoNcEquation Native d_10729550006YQF//Ole hCompObjPRiNObjInfoSkEquation Native lFMicrosoft EquationDNQE Equation.3  Times New RomanuC Cl  = um Cl um C  + um H  + um Cl  x 100_1177440494VF//Ole pCompObjUWqRObjInfoXsFMicrosoft EquationDNQE Equation.3 = 177.25 g600.5 g + 95.76 g + 177.25 g  100 = 20.3 wt%Equation Native t_1072955289[F//Ole xCompObjZ\yRFMicrosoft EquationDNQE Equation.3Y  Times New RomanuL = uNud sin q2()FMicrosoft EquationDNQE EObjInfo]{Equation Native |u_1177440831`F//Ole ~CompObj_aNObjInfobEquation Native V_1177441086^heF//quation.3:  Times New Romanwr = wd wN FMicrosoft EquationDNQE Equation.3Ole CompObjdfRObjInfogEquation Native   Times New RomanwDwP = "wM wn wm = 500,000 g/mol100.02 g/mol = 5000FMicrosoft EquationDNQE Equation.3_1177441175jF//Ole CompObjikRObjInfolEquation Native _1177441226coF//Ole CompObjnpR = (10,000)(0.154 nm) sin 1092()[] = 1254 nmFMicrosoft EquationDNQE Equation.3  Times New Romanwr =ObjInfoqEquation Native _1072966517,tF//Ole  wd wN   = (0.154 nm) 10,000   = 15.4 nmFMicrosoft EquationDNQE Equation.3b  Times New RomanuN = uLud sin q2()CompObjsuRObjInfovEquation Native ~_1177441413yF//Ole CompObjxzRObjInfo{Equation Native FMicrosoft EquationDNQE Equation.3 = 2500 nm(0.154 nm) sin 1092() = 19,940_1072966583~F//Ole CompObj}RObjInfoFMicrosoft EquationDNQE Equation.3.  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B4Hq1/@4ҳ T4Hq1/@4ҳKxTMo@;mmM(B|  z Aȵ׉{nTwʉW8AGLì$.Bڻ3o޼5Э[e6av`>{֦1n} WoR?O/NvDLk6"r8TbXae6ߛyޝD"6gqua#@5˱[9,w$X\Y0yӘ*dلQ'w>jEp\U5GIfh7 \lk0ar| Ȳ4Xۦ^eSw:J.CG1[{x|DD7^WK^@2Bz (Q,7J o/); xɭ;"bcLi؄ F#[]$_1pjE1]sRni֐Ŵ1ΧilHJ">)ЖpcEbIV/2\*$#.&) ʳJx"wg"X>'B̷?h瑙 Xl6S9$jPu9s ODFKho\zo=C^//&1͗ilҸ)(Q!ww^|guBXz7e|>x$b<0D\' N"` *vN E7qtya [BMx9T:4ұQ(󯶕TNշeuW`W]e@Д>Q >}x'Rjh ƒcԬ^Ff6M+h4;un8ѝhQ"N񄏽֣00| < ڵ,rnjX~aJwb|~1GaR6RVe8t&QWύC'MXLrRuJv$&DhR4h/Ea kԳψ0 &<9?4jGitbV{X*0;_1072976685F//Ole CompObjRObjInfoEquation Native >_1177489912F//Ole CompObjRFMicrosoft EquationDNQE Equation.3  Times New Roman"wm = "wM wn wDwP = 250,000 g/mol3420 = 73.10 g/molObjInfoEquation Native _1177489732F//Ole CompObjRObjInfoEquation Native _1177489933F//FMicrosoft EquationDNQE Equation.3  Times New Romanwm wx  = "wm- wf ws wm ws  wf wxFMicrosoft EquationDNQE EOle CompObjRObjInfoEquation Native quation.3 = 73.10 g/mol - (0.5)(104.14 g/mol)0.5 = 42.06 g/molFMicrosoft EquationDNQE E_1072977049F//Ole CompObjRObjInfo   "#&)*-014789<?@ADGJMNQTUX[^abcfilopqrsvyz}quation.3"  Times New Roman"umFMicrosoft EquationDNQE Equation.3  Times New Roman"wm Equation Native >_1177490270F//Ole CompObjRObjInfoEquation Native _1177490345F//Ole  = "wM wn wDwP = 350,000 g/mol4425 = 79.10 g/molFMicrosoft EquationDNQE Equation.3  Times New Roman"wm CompObj RObjInfoEquation Native _1177490510F//= wf wb wm wb  + wf ws wm ws  =w wf wb wm wb  + (1 - wf wb )wm wsFMicrosoft EquationDNQE Equation.3I  Times New Romanwf Ole CompObjRObjInfoEquation Native ewb  = "wm - wm ws  wm wb - wm ws  = 79.10 g/mol - 104.14 g/mol54.09 g/mol - 104.14 g/mol = 0.50FMicrosoft EquationDNQE Equation.3_1177490592F//Ole CompObjRObjInfo   Times New Romanwf wb wf ws  = 0.500.50 = 1.0FMicrosoft EquationDNQE Equation.3Equation Native !_1177490878F//Ole $CompObj%RObjInfo'Equation Native (_1177490917F//Ole + 60 g28.05 g/mol=2.14 mol of ethyleneFMicrosoft EquationDNQE Equation.3 40 g42.CompObj,RObjInfo.Equation Native /_1177490959F//08 g/mol=0.95 mol of propyleneFMicrosoft EquationDNQE Equation.3  Times New Romanwf(ethylene) =2.14 molOle 2CompObj3RObjInfo5Equation Native 62.14 mol+0.95 mol= 0.69FMicrosoft EquationDNQE Equation.3  Times New Romanwf(propylene) =0.95 mo_1177490999F//Ole :CompObj;RObjInfo=Equation Native >_1072977953F//Ole BCompObjCRl2.14 mol+0.95 mol= 0.31FMicrosoft EquationDNQE Equation.3.  Times New Roman"uM unObjInfoEEquation Native FJ_1177491520F//Ole HFMicrosoft EquationDNQE Equation.3  Times New Roman"wm = wf wiwb wm wiwb  + wf wiwp wm wiwpCompObjIRObjInfoKEquation Native L_1177491577]F//Ole OCompObjPRObjInfoREquation Native SFMicrosoft EquationDNQE Equation.3p  Times New Roman"wm = 56.10wx + (68.11)(1 - wx)FMicrosoft EquationDNQE E_1072978647F//Ole VCompObjWRObjInfoYquation.3M  Times New RomanuDuP = "uM un "umFMicrosoft EquationDNQE Equation.3Equation Native Zi_1177491641F//Ole \CompObj]RObjInfo_Equation Native `_1072979079F//Ole d 3000=200,000 g/mol[56.10 Times New Romanwx+68.11(1-wx)] g/molFMicrosoft EquationDNQE Equation.3CompObjeRObjInfogEquation Native hs_1177493077&F//W  Times New Romanun = ruV uC uN A uAFMicrosoft EquationDNQE Equation.3X =  e( 0.946 g/cm 3 e)( 8.869 Ole jCompObjkRObjInfomEquation Native nt 10 -22  cm 3 /unit cell e)( 6.022  10 23  repeat units/mol e) 42.08 g/molFMicrosoft EquationDNQE Equation.3_1072979329r F//Ole tCompObj  uRObjInfo wEquation Native x_1072979335F//Ole {CompObj|Rm  Times New RomanuC=% crystallinity100FMicrosoft EquationDNQE Equation.3  Times New RomanuC =ObjInfo~Equation Native _1072979346 F//Ole  r uc  e( r us  - r ua e) r us  e( r uc  - r ua e)FMicrosoft EquationDNQE Equation.3 r  Times New RomanCompObjRObjInfoEquation Native _1072979358F//uc  e( uCr us  - r us e)  + r uc r ua  - uCr us r ua  = 0FMicrosoft EquationDNQE Equation.3 r  Times New RomanOle CompObjRObjInfoEquation Native uc  e( uC 1 r us1  - r us1 e)  + r uc r ua  - uC 1 r us1 r ua  = 0FMicrosoft EquationDNQE Equation.3_1072979367+F,,Ole CompObjRObjInfo Equation Native _1072979397#F,,Ole CompObj"$R r  Times New Romanuc  e( uC 2 r us2  - r us2 e)  + r uc r ua  - uC 2 r us2 r ua  = 0FMicrosoft EquationDNQE Equation.3ObjInfo%Equation Native _1177493573(F,,Ole zzzzzzz z z z z zzzzzzzzzzzzzzzzzzz z!z" r  Times New Romanua  = r us1 r us2  e( uC 1  - uC 2 e) uC 1 r us1  - uC 2 r us2FMicrosoft EquationDNQE ECompObj')RObjInfo*Equation Native _1072979418!?-F,,quation.3 =  e( 2.144 g/cm 3 e)( 2.215 g/cm 3 e)  e( 0.513 - 0.742 e) (0.513) e( 2.144 g/cm 3 e)  - (0.742) e( 2.215 g/cm 3 e)  = 2.000 g/cm 3FMicrosoft EquationDNQE Equation.3+ r  Times New Romanuc  = r us1 r us2 e( uC 2  - uC 1 e) r(qt~®cV>k:4G#^8 1ݴeVUhrROy<j`-*}s;˜,f!Q)&(4Aշҋʣ5z*&Ks _J`vf$n)UD[=|q/ r]q$niC5;=P4ޖH7ɩ: ntVDBC˒^I&ϗ\c^i_ׯY;u:4E|X?~P@C*ięDvoN'RdX;1H_F[(\g*ytʿ}v@:3;KY[2d>wfό͎LcŲ+c5X,b2]L5_vez[_aDdH + c $A"? 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1 e)  - r us1 e( uC 1  - 1 e)FMicrosoft EquationDNQE Equation.3 =  e( 2.1_1177493902:2F,,Ole CompObj13RObjInfo4Equation Native _11774939687F,,Ole CompObj68R44 g/cm 3 e)( 2.215 g/cm 3 e)  e( 0.742 - 0.513 e)  e( 2.215 g/cm 3 e)  e( 0.742 - 1 e)  - e( 2.144 g/cm 3 e)  e( 0.513 - 1 e)  = 2.301 g/cm 3FMicrosoft EquationDNQE Equation.3 % crystallinity = r  Times New Romanwc  e( r ws  - r wa e) r ws  e( r wc  - r wa e)   100ObjInfo9Equation Native _11774939745N<F,,Ole FMicrosoft EquationDNQE Equation.3v =  e( 2.301 g/cm 3 e)( 2.260 g/cm 3  - 2.000 g/cm 3 e)  e( 2.260 g/cmCompObj;=RObjInfo>Equation Native _1072979531AF,, 3 e)( 2.301 g/cm 3  - 2.000 g/cm 3 e)   100FMicrosoft EquationDNQE Equation.3p  Times New RomanuCOle CompObj@BRObjInfoCEquation Native =%crystallinity100FMicrosoft EquationDNQE Equation.3  Times New RomanuC = r uc  e( r us  - r_1072979540bFF,,Ole CompObjEGRObjInfoHEquation Native _1072979548KF,,Ole CompObjJLR ua e) r us  e( r uc  - r ua e)FMicrosoft EquationDNQE Equation.3 r  Times New Romanuc  e( uCr us -r us ObjInfoMEquation Native _1177494326PF,,Ole e)  + r uc r ua  - uCr us r ua  = 0FMicrosoft EquationDNQE Equation.3 r  Times New Romanwc  e( wC 1 r ws1  - CompObjOQRObjInfoREquation Native  _1072979562IXUF,,r ws1 e)  + r wc r wa  - wC 1 r ws1 r wa  = 0FMicrosoft EquationDNQE Equation.3 r  Times New RomanOle CompObjTVRObjInfoWEquation Native       !$'()*+,-03458;<=>?BEFILMNORUVY\]`cdefilmpstwz}uc  e( uC 2 r us2  - r us2 e)  + r uc r ua  - uC 2 r us Times New Romanw2 r ua  = 0FMicrosoft EquationDNQE Equation.3_1072979588ZF,,Ole CompObjY[RObjInfo\Equation Native _11774944250_F,,Ole  CompObj^`R r  Times New Romanua  = r us1 r us2  e( uC 1  - uC 2 e) uC 1 r us1  - uC 2 r us2FMicrosoft EquationDNQE Equation.3ObjInfoaEquation Native _1072979609SEdF,,Ole  =  e( 1.188 g/cm 3 e)( 1.152 g/cm 3 e)  e( 0.673-0.437 e) (0.673) e( 1.188 g/cm 3 e) -(0.437) e( 1.152 g/cm 3 e) = 1.091 g/cm 3FMicrosoft EquationDNQE Equation.30 r  Times New Romanuc  = r us1 r us2  e( uC 2  - uC 1 e) r us2  e( uC 2  - 1 e)  CompObjceRObjInfofEquation Native L_1177494626iF,,- r us1 e( uC 1  -1 e)FMicrosoft EquationDNQE Equation.3 =  e( 1.188 g/cm 3 e)( 1.152 Ole "CompObjhj#RObjInfok%Equation Native &g/cm 3 e)  e( 0.437-0.673 e)  e( 1.152 g/cm 3 e)  e( 0.437-1 e) - e( 1.188 g/cm 3 e)  e( 0.673-1 e) = 1.242 g/cm 3FMicrosoft EquationDNQE E_1072979693nF,,Ole .CompObjmo/RObjInfop1quation.3 r  Times New Romanus  = -r uc r ua uC e( r uc -r ua e) -r ucFMicrosoft EquationDNQE EEquation Native 2_1177494877g{sF,,Ole 6CompObjrt7Rquation.3M = - e( 1.242 g/cm 3 e)( 1.091 g/cm 3 e)  e( 0.554 e)  e( 1.242 g/cm 3 - 1.091 g/cm 3 e) - 1.242 g/cm 3ObjInfou9Equation Native :i_1072980258lxF,,Ole @FMicrosoft EquationDNQE Equation.3ation.39q  Times New RomanuJ= uP uM DuPDux=uP uM uP 2 -uP 1 DuxCompObjwyAfObjInfozCEquation Native D_1177495597}F,,Ole GCompObj|~HfObjInfoJEquation Native K FMicrosoft EquationDNQE Equation.3ation.39q = 38  10 -13 (cm 3  STP)(cm)cm 2 -s-Pa[] 10,000 Pa -1,000 Pa0.2 cm()i      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`fgnjlu~opqrstuwxyz{|}RFMicrosoft EquationDNQE Equation.3ation.39q = 1.71  10 -7 (cm 3  STP)cm 2 -sEquation Native T_1072980634F,,Ole WCompObjXfFMicrosoft EquationDNQE Equation.3ation.39q  Times New RomanuP uM =uJ DuxDuP=uJ DuxuP 2 -uP 1FMicrosoft EquationDNQE EObjInfoZEquation Native [_1177495984F,,Ole ^%@@@ NormalCJOJQJmH sH tH DA@D Default Paragraph FontZi@Z  Table Normal :V 4 l4a _H(k(No List 4 @4 Footer  !TOT Solns,$ lHdh^`Ha$CJdOd Solutions,$ <quation.3ation.39q  Times New RomanwP wM =4.0  10 -7 (cm 3  STP)cm 2 -s[](4 cm)(5,000,000 Pa - 1,500,000 Pa)Ole gCompObjhfObjInfojEquation Native kFMicrosoft EquationDNQE Equation.3ation.39q =4.57  10 -13 (cm 3  STP)(cm)cm 2 -s-PaFMicrosoft EquationDNQE E_1177496206F,,Ole nCompObjoNObjInfoqquation.3  Times New RomanwP wM  = wP wM 0   exp - wQ wp wRwT()FMicrosoft EquationDNQE Equation.3}EF      !"#$%&'()*+,-./0123456789:;<=>?@ABCDGIHKJLMNOPQSRTUVWXZ[]_a`bcdefghijkmloqrtkvwx{~scriptCJEH:Oa: Style3  ROR kPNEquation$ 8^a$OJQJ_HaJHOH mnoindent$da$OJQJ_HaJ<Z@< m Plain Text OJQJaJ>Oa> m Superscript_1CJEH6Oa6 m SubscriptCJEH:O: mh2 $d5OJQJ_H8O8 ml. 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Bgʰ}oXFK Tgʰ}oXF^ exTMF-vb[ 6>"0{Fja!c|1d9҈I3;9&!`$? {tUz|݅W [ހ{eug1c>)i| g c}E19% &<>,K[zz!UY7I33%Df6/´MaG{0+xEBKwZ)w܀Fm251Microsoft Word 11.5.3@b @@\N@@(bd ՜.+,D՜.+,< hp  'Self3F{ Chap 15 Solns Title 8@ _PID_HLINKS'ALH41144114 a><  Soln_Prob 14 a\<  Soln_Prob 14 a|<  Soln_Prob 1441= 1441= 1441>1441>>14 aC Soln_Prob 14JDCSoln_Probe 14 a(D Soln_Prob 14 FMicrosoft Word DocumentNB6WWord.Document.8 = 5.90  10 -7 (cm 3  STP)cm 2 -s Oh+'0  4 @ L Xdlt|'Chap 15 SolnsBill CallisterNormalBill Callister b Qjbjbjhhy d0DDD8|T\;'`XIII# % % % % % % ,(R+|Q I'"IIIQ A_&AAAI@# Ad I# AA:,7T VD# 7&0'- +A+7A\;\;d@]\;\;@CHAPTER 14 POLYMER STRUCTURES PROBLEM SOLUTIONS Hydrocarbon Molecules Polymer Molecules The Chemistry of Polymer Molecules 14.1 On the basis of the structures presented in this chapter, sketch repeat unit structures for the following polymers: (a) polychlorotrifluoroethylene, and (b) poly(vinyl alcohol). Solution The repeat unit structures called for are sketched below. (a) Polychlorotrifluoroethylene  (b) Poly(vinyl alcohol)  Molecular Weight 14.2 Compute repeat unit molecular weights for the following: (a) poly(vinyl chloride), (b) poly(ethylene terephthalate), (c) polycarbonate, and (d) polydimethylsiloxane. Solution (a) For poly(vinyl chloride), each repeat unit consists of two carbons, three hydrogens, and one chlorine (Table 14.3). If AC, AH and ACl represent the atomic weights of carbon, hydrogen, and chlorine, respectively, then m = 2(AC) + 3(AH) + (ACl) = (2)(12.01 g/mol) + (3)(1.008 g/mol) + 35.45 g/mole = 62.49 g/mol (b) For poly(ethylene terephthalate), from Table 14.3, each repeat unit has ten carbons, eight hydrogens, and four oxygens. Thus, m = 10(AC) + 8(AH) + 4(AO) = (10)(12.01 g/mol) + (8)(1.008 g/mol) + (4)(16.00 g/mol) = 192.16 g/mol (c) For polycarbonate, from Table 14.3, each repeat unit has sixteen carbons, fourteen hydrogens, and three oxygens. Thus, m = 16(AC) + 14(AH) + 3(AO) = (16)(12.01 g/mol) + (14)(1.008 g/mol) + (3)(16.00 g/mol) = 254.27 g/mol (d) For polydimethylsiloxane, from Table 14.5, each repeat unit has two carbons, six hydrogens, one silicon and one oxygen. Thus, m = 2(AC) + 6(AH) + (ASi) + (AO) = (2)(12.01 g/mol) + (6)(1.008 g/mol) + (28.09 g/mol) + (16.00 g/mol) = 74.16 g/mol 14.3 The number-average molecular weight of a polypropylene is 1,000,000 g/mol. Compute the degree of polymerization. Solution We are asked to compute the degree of polymerization for polypropylene, given that the number-average molecular weight is 1,000,000 g/mol. The repeat unit molecular weight of polypropylene is just m = 3(AC) + 6(AH) = (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol Now it is possible to compute the degree of polymerization using Equation 14.6 as  EMBED Equation.3   EMBED Equation.3  14.4 (a) Compute the repeat unit molecular weight of polystyrene. (b) Compute the number-average molecular weight for a polystyrene for which the degree of polymerization is 25,000. Solution (a) The repeat unit molecular weight of polystyrene is called for in this portion of the problem. For polystyrene, from Table 1#5hit YZrsgdvOgdvO l d^` gdvOgdvOgdvOڎێ܎ݎZ[nopqst|qdjrhkPNhvOEHUjZf? hvOUV h>N~hvOjh>N~hvOUj~h_ghvOEHUjV%E hvOUVjehtJhvOEHUj1/F hvOUV hkPNhvOhvOCJEHhvO6CJEH hvO6jbhkPNhvOEHUjZd? hvOUVhvOjhvOU#LMNQXZ>\@\B\D\^߼۲ۛ}odWLjUF hvOUVjhvOhvOEHUj UF hvOUVhhvO6CJOJQJhhvOOJQJ$hhvO6B*CJOJQJph!hhvOB*CJOJQJph hvO0JjhvO0JU hY]hvOj)h_ghvOEHUjW%E hvOUVhvOjhvOUj@h_ghvOEHUjV%E hvOUVMNOPQXZD\^c df hgd#yugdvO $h]ha$gdvO$a$gdvOh]h&`#$/ 000P:pvO/ =!"#$%|HH(EG(HH(d'` (3)(1.008 g/mol) + 35.45 g/mol  ^^^ccccccc dfhhhh h˾jfh#yuh#yuEHUjVF h#yuOJQJUVjh#yuh#yuEHUjğVF h#yuUVh#yu hvO6jhvOhvOEHUjXUF hvOUVjrhvOhvOEHUjUF hvOUVhvOjhvOhvOEHU 8,000-20,000 14,000 0.05 7000-32,000 26,000 0.15 39 32,000-44,000 38,000 0.21 79 44,000-56,000 50,000 0.28 14 56,000-68,000 62,000 0.18 11,1 68,000-80,000 74,000 0.10 74 80,000-92,000 86,000 0.03 258not d degree of polymerization is 47 (and not 527) = 20 Ole CompObjRObjInfoEquation Native Ole CompObjRObjInfoEquation Native f propyleneFMicrosoft EquationDNQE Equation.3 60 g28.05 g/mol=2.14 mol of ethylene wn  = wx wi wM wi   = 47,720 g/molFMicrosoft EquationDNQE Equation.3 40 g42.08 g/mol=0.95 mol oFMicrosoft EquationDNQE Equation.3M????_O_MMM@@????vXM3?A????@vXMM:JS,??S8 W5FvS Se_0_S cMcSM?ssd]ss CHAPTER 14 POLYMER STRUCTURES PROBLEM SOLUTIONS Hydrocarbon Molecules Polymer Molecules The Chemistry of Polymer Molecules 14.1 On the basis of the structures presented in this chapter, sketch repeat unit structures for the following polymers: (a) polychlorotrifluoroethylene, and (b) poly(vinyl alcohol). Solution The repeat unit structures called for are sketched below. (a) Polychlorotrifluoroethylene  (b) Poly(vinyl alcohol)  Molecular Weight 14.2 Compute repeat unit molecular weights for the following: (a) poly(vinyl chloride), (b) poly(ethylene terephthalate), (c) polycarbonate, and (d) polydimethylsiloxane. Solution (a) For poly(vinyl chloride), each repeat unit consists of two carbons, three hydrogens, and one chlorine (Table 14.3). If AC, AH and ACl represent the atomic weights of carbon, hydrogen, and chlorine, respectively, then m = 2(AC) + 3(AH) + (ACl) = (2)(12.01 g/mol) + (3)(1.008 g/mol) + 35.45 g/mole = 62.49 g/mol (b) For poly(ethylene terephthalate), from Table 14.3, each repeat unit has ten carbons, eight hydrogens, and four oxygens. Thus, m = 10(AC) + 8(AH) + 4(AO) = (10)(12.01 g/mol) + (8)(1.008 g/mol) + (4)(16.00 g/mol) = 192.16 g/mol (c) For polycarbonate, from Table 14.3, each repeat unit has sixteen carbons, fourteen hydrogens, and three oxygens. Thus, m = 16(AC) + 14(AH) + 3(AO) = (16)(12.01 g/mol) + (14)(1.008 g/mol) + (3)(16.00 g/mol) = 254.27 g/mol (d) For polydimethylsiloxane, from Table 14.5, each repeat unit has two carbons, six hydrogens, one silicon and one oxygen. Thus, m = 2(AC) + 6(AH) + (ASi) + (AO) = (2)(12.01 g/mol) + (6)(1.008 g/mol) + (28.09 g/mol) + (16.00 g/mol) = 74.16 g/mol 14.3 The number-average molecular weight of a polypropylene is 1,000,000 g/mol. Compute the degree of polymerization. Solution We are asked to compute the degree of polymerization for polypropylene, given that the number-average molecular weight is 1,000,000 g/mol. The repeat unit molecular weight of polypropylene is just m = 3(AC) + 6(AH) = (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol Now it is possible to compute the degree of polymerization using Equation 14.6 as  EMBED Equation.3   EMBED Equation.3  14.4 (a) Compute the repeat unit molecular weight of polystyrene. (b) Compute the number-average molecular weight for a polystyrene for which the degree of polymerization is 25,000. Solution (a) The repeat unit molecular weight of polystyrene is called for in this portion of the problem. For polystyrene, from Table 1#5hit YZrsgdvOgdvO l d^` gdvOgdvOgdvOڎێ܎ݎZ[nopqst|qdjrhkPNhvOEHUjZf? hvOUV h>N~hvOjh>N~hvOUj~h_ghvOEHUjV%E hvOUVjehtJhvOEHUj1/F hvOUV hkPNhvOhvOCJEHhvO6CJEH hvO6jbhkPNhvOEHUjZd? hvOUVhvOjhvOU#LMNQXZ>\@\B\D\^߼۲ۛ}odWLjUF hvOUVjhvOhvOEHUj UF hvOUVhhvO6CJOJQJhhvOOJQJ$hhvO6B*CJOJQJph!hhvOB*CJOJQJph hvO0JjhvO0JU hY]hvOj)h_ghvOEHUjW%E hvOUVhvOjhvOUj@h_ghvOEHUjV%E hvOUVMNOPQXZD\^c df hjgdr$gd#yugdvO $h]ha$gdvO$a$gdvOh]h&`#$/ 000P:pvO/ =!"#$%|HH(EG(HH(d'` (3)(1.008 g/mol) + 35.45 g/mol  ^^^ccccccc dfhhhh hjjj˾viehr$jhr$hr$EHUjLVF hr$UVjfh#yuh#yuEHUjVF h#yuOJQJUVjh#yuh#yuEHUjğVF h#yuUVh#yu hvO6jhvOhvOEHUjXUF hvOUVjrhvOhvOEHUjUF hvOUVhvOjhvOhvOEHU 8,000-20,000 14,000 0.05 7000-32,000 26,000 0.15 39 32,000-44,000 38,000 0.21 79 44,000-56,000 50,000 0.28 14 56,000-68,000 62,000 0.18 11,1 68,000-80,000 74,000 0.10 74 80,000-92,000 86,000 0.03 258not d degree of polymerization is 47 (and not 527) = 20  Equation Native  0.2 cm()FMicrosoft EquationDNQE Equation.3ation.39qFMicrosoft EquationDNQE Equation.3 = 38  10 -13 (cm 3  STP)(cm)cm 2 -s-Pa[] 10,000 Pa -1,000 Pa