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 stru tures alle! "or are s#et he! $elo%. &a' Pol( hlorotri"luoroeth(lene

&$' Pol(&)in(l al ohol'

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

Molecular Wei ht
14.. 'ompute repeat unit molecular weights for the following: (a) poly(vinyl chloride), (b) poly(ethylene terephthalate), (c) polycarbonate, and (d) polydimethylsilo(ane. Solution &a' /or pol(&)in(l hlori!e'0 ea h repeat unit onsists o" t%o ar$ons0 three h(!ro-ens0 an! one hlorine &Ta$le 14.1'. I" AC0 AH an! ACl represent the ato+i %ei-hts o" ar$on0 h(!ro-en0 an! hlorine0 respe ti)el(0 then m 2 .&AC' 3 1&AH' 3 &ACl' 2 &.'&1..41 -5+ol' 3 &1'&1.446 -5+ol' 3 17.47 -5+ol 2 8..49 -5+ol &$' /or pol(&eth(lene terephthalate'0 "ro+ Ta$le 14.10 ea h repeat unit has ten ar$ons0 ei-ht h(!ro-ens0 an! "our o*(-ens. Thus0 m 2 14&AC' 3 6&AH' 3 4&AO' 2 &14'&1..41 -5+ol' 3 &6'&1.446 -5+ol' 3 &4'&18.44 -5+ol' 2 19..18 -5+ol & ' /or pol( ar$onate0 "ro+ Ta$le 14.10 ea h repeat unit has si*teen ar$ons0 "ourteen h(!ro-ens0 an! three o*(-ens. Thus0 m 2 18&AC' 3 14&AH' 3 1&AO' 2 &18'&1..41 -5+ol' 3 &14'&1.446 -5+ol' 3 &1'&18.44 -5+ol' 2 .74..: -5+ol &!' /or pol(!i+eth(lsilo*ane0 "ro+ Ta$le 14.70 ea h repeat unit has t%o ar$ons0 si* h(!ro-ens0 one sili on an! one o*(-en. Thus0 m 2 .&AC' 3 8&AH' 3 &ASi' 3 &AO'

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

2 &.'&1..41 -5+ol' 3 &8'&1.446 -5+ol' 3 &.6.49 -5+ol' 3 &18.44 -5+ol' 2 :4.18 -5+ol

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.1 )he number*average molecular weight of a polypropylene is ,!!!,!!! g+mol. 'ompute the degree of polymeri,ation. Solution ;e are as#e! to o+pute the !e-ree o" pol(+eri<ation "or pol(prop(lene0 -i)en that the nu+$er,a)era-e +ole ular %ei-ht is 104440444 -5+ol. The repeat unit +ole ular %ei-ht o" pol(prop(lene is =ust m 2 1&AC' 3 8&AH' 2 &1'&1..41 -5+ol' 3 &8'&1.446 -5+ol' 2 4..46 -5+ol No% it is possi$le to o+pute the !e-ree o" pol(+eri<ation usin- E>uation 14.8 as

P =

M n 1, 000, 000 g/mol = = 23, 760 m 42.08 g/mol

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.4 (a) 'ompute the repeat unit molecular weight of polystyrene. (b) 'ompute the number*average molecular weight for a polystyrene for which the degree of polymeri,ation is -.,!!!. Solution &a' The repeat unit +ole ular %ei-ht o" pol(st(rene is alle! "or in this portion o" the pro$le+. /or pol(st(rene0 "ro+ Ta$le 14.10 ea h repeat unit has ei-ht ar$ons an! ei-ht h(!ro-ens. Thus0 m 2 6&AC' 3 6&AH' 2 &6'&1..41 -5+ol' 3 &6'&1.446 -5+ol' 2 144.14 -5+ol &$' ;e are no% as#e! to o+pute the nu+$er,a)era-e +ole ular %ei-ht. Sin e the !e-ree o"

pol(+eri<ation is .704440 usin- E>uation 14.8

= (DP) m = (25,000)(104.14 g/mol) = 2.60 10 6 g/mol

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.7 /elow, molecular weight data for a polypropylene material are tabulated.

'ompute (a) the

number*average molecular weight, (b) the weight*average molecular weight, and (c) the degree of polymeri,ation. Molecular Weight Range (g/mol) #,!!!0 %,!!! %,!!!0-1,!!! -1,!!!02-,!!! 2-,!!!01!,!!! 1!,!!!01#,!!! 1#,!!!0.%,!!! Solution &a' /ro+ the ta$ulate! !ata0 %e are as#e! to o+pute 0 the nu+$er,a)era-e +ole ular %ei-ht. This is arrie! out $elo%. Mole ular %t Ran-e 60444,180444 180444,.40444 .40444,1.0444 1.0444,440444 440444,460444 460444,780444

xi !.!. !. % !.-1 !.-# !.-! !.!"

wi !.!!. ! !.-! !.2! !.-" !.

Mean 3i 1.0444 .40444 .60444 180444 440444 7.0444

(i 4.47 4.18 4..4 4..6 4..4 4.4:

( i 3i 844 1.44 8:.4 140464 6644 1844

???????????????????????????? = xi M i = 33, 040 g/mol

&$' /ro+ the ta$ulate! !ata0 %e are as#e! to o+pute 0 the %ei-ht,a)era-e +ole ular %ei-ht. Mole ular %t. Ran-e 60444,180444 180444,.40444 .40444,1.0444

Mean 3i 1.0444 .40444 .60444

wi 4.4. 4.14 4..4

wi3i .44 .444 7844

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

1.0444,440444 440444,460444 460444,780444

180444 440444 7.0444

4.14 4..: 4.11

140644 110664 7:.4

??????????????????????????? = wi M i = 36, 240 g/mol

& ' No% %e are as#e! to o+pute the !e-ree o" pol(+eri<ation0 %hi h is possi$le usin- E>uation 14.8. /or pol(prop(lene0 the repeat unit +ole ular %ei-ht is =ust m 2 1&AC' 3 8&AH'

2 &1'&1..41 -5+ol' 3 &8'&1.446 -5+ol' 2 4..46 -5+ol An!

Mn 33,040 g/mol = = 785 m 42.08 g/mol

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.8 3olecular weight data for some polymer are tabulated here. 'ompute (a) the number*average molecular weight, and (b) the weight*average molecular weight. (c) 4f it is known that this material5s degree of polymeri,ation is " !, which one of the polymers listed in )able 1.2 is this polymer6 7hy6 Molecular Weight Range g/mol .,!!!02!,!!! 2!,!!!01.,!!! 1.,!!!0%!,!!! %!,!!!0".,!!! ".,!!!0$!,!!! $!,!!!0 !.,!!! !.,!!!0 -!,!!! -!,!!!0 2.,!!!

(i !.!1 !.!" !. % !.-% !.-1 !. !.!# !.!2

wi !.! !.!1 !. !.-1 !.-" !. % !. !.!.

Solution &a' /ro+ the ta$ulate! !ata0 %e are as#e! to o+pute 0 the nu+$er,a)era-e +ole ular %ei-ht. This is arrie! out $elo%. Mole ular %t. Ran-e 170444,140444 140444,470444 470444,840444 840444,:70444 :70444,940444 940444,1470444 1470444,1.40444 1.40444,1170444

Mean 3i ..0744 1:0744 7.0744 8:0744 6.0744 9:0744 11.0744 1.:0744

(i 4.44 4.4: 4.18 4..8 4..4 4.1. 4.46 4.41

( i 3i 944 .8.7 6444 1:0774 190644 110:44 9444 16.7 ?????????????????????????

xi M i

= 73,800 g/mol

&$' /ro+ the ta$ulate! !ata0 %e are as#e! to o+pute 0 the %ei-ht,a)era-e +ole ular %ei-ht. This !eter+ination is per"or+e! as "ollo%s@ Mole ular %t.
E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

Ran-e 170444,140444 140444,470444 470444,840444 840444,:70444 :70444,940444 940444,1470444 1470444,1.40444 1.40444,1170444

Mean 3i ..0744 1:0744 7.0744 8:0744 6.0744 9:0744 11.0744 1.:0744

wi 4.41 4.44 4.11 4..4 4..: 4.18 4.1. 4.47

wi3i ..7 1744 7::7 180.44 ..0.:7 170844 110744 81:7 ?????????????????????????

wi M i

= 81, 450 g/mol

& ' ;e are no% as#e! i" the !e-ree o" pol(+eri<ation is :140 %hi h o" the pol(+ers in Ta$le 14.1 is this +aterialA It is ne essar( to o+pute m in E>uation 14.8 as

M n 73,800 g/mol = = 103.94 g/mol DP 710

The repeat unit +ole ular %ei-hts o" the pol(+ers liste! in Ta$le 14.1 are as "ollo%s@ Pol(eth(lene,,.6.47 -5+ol Pol(&)in(l hlori!e',,8..49 -5+ol Pol(tetra"luoroeth(lene,,144.4. -5+ol Pol(prop(lene,,4..46 -5+ol Pol(st(rene,,144.14 -5+ol Pol(&+eth(l +etha r(late',,144.11 -5+ol Phenol,"or+al!eh(!e,,111.18 -5+ol N(lon 808,,..8.1. -5+ol PET,,19..18 -5+ol Pol( ar$onate,,.74..: -5+ol There"ore0 pol(st(rene is the +aterial sin e its repeat unit +ole ular %ei-ht is losest to that al ulate! a$o)e.

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.: 4s it possible to have a poly(methyl methacrylate) homopolymer with the following molecular weight data and a of polymeri,ation of .-"6 7hy or why not6 Molecular Weight Range (g/mol) #,!!!0-!,!!! -!,!!!02-,!!! 2-,!!!011,!!! 11,!!!0.%,!!! .%,!!!0%#,!!! %#,!!!0#!,!!! #!,!!!0$-,!!!

wi !.!!.!# !. " !.-$ !.-2 !. % !.!.

xi !.!. !. . !.!.-# !. # !. ! !.!2

Solution This pro$le+ as#s i" it is possi$le to ha)e a pol(&+eth(l +etha r(late' ho+opol(+er %ith the -i)en +ole ular %ei-ht !ata an! a !e-ree o" pol(+eri<ation o" 7.:. The appropriate !ata are -i)en $elo% alon- %ith a o+putation o" the nu+$er,a)era-e +ole ular %ei-ht.

Mole ular %t. Ran-e 60444,.40444 .40444,1.0444 1.0444,440444 440444,780444 780444,860444 860444,640444 640444,9.0444

Mean 3i 140444 .80444 160444 740444 8.0444 :40444 680444

(i 4.47 4.17 4..1 4..6 4.16 4.14 4.41

( i 3i :44 1944 :964 140444 110184 :444 .764 ?????????????????????????

xi M i

= 47, 720 g/mol

/or PMMA0 "ro+ Ta$le 14.10 ea h repeat unit has "i)e ar$ons0 ei-ht h(!ro-ens0 an! t%o o*(-ens. Thus0 m 2 7&AC' 3 6&AH' 3 .&AO'

2 &7'&1..41 -5+ol' 3 &6'&1.446 -5+ol' 3 &.'&18.44 -5+ol' 2 144.11 -5+ol No%0 %e %ill o+pute the !e-ree o" pol(+eri<ation usin- E>uation 14.8 as

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

Mn 47, 720 g/mol = = 477 m 100.11 g/mol

Thus0 su h a ho+opol(+er is not possible sin e the al ulate! !e-ree o" pol(+eri<ation is 4:: &an! not 7.:'.

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.6 8igh*density polyethylene may be chlorinated by inducing the random substitution of chlorine atoms for hydrogen. (a) 9etermine the concentration of 'l (in wt:) that must be added if this substitution occurs for .: of all the original hydrogen atoms. (b) 4n what ways does this chlorinated polyethylene differ from poly(vinyl chloride)6 Solution &a' /or hlorinate! pol(eth(lene0 %e are as#e! to !eter+ine the %ei-ht per ent o" hlorine a!!e! "or 7B Cl su$stitution o" all ori-inal h(!ro-en ato+s. Consi!er 74 ar$on ato+sC there are 144 possi$le si!e,$on!insites. Ninet(,"i)e are o upie! $( h(!ro-en an! "i)e are o upie! $( Cl. Thus0 the +ass o" these 74 ar$on ato+s0 mC0 is =ust mC 2 74&AC' 2 &74'&1..41 -5+ol' 2 844.7 -

Li#e%ise0 "or h(!ro-en an! hlorine0 mH 2 97&AH' 2 &97'&1.446 -5+ol' 2 97.:8 mCl 2 7&ACl' 2 &7'&17.47 -5+ol' 2 1::..7 Thus0 the on entration o" hlorine0 'Cl0 is !eter+ine! usin- a +o!i"ie! "or+ o" E>uation 4.1 as

+ +

100

177.25 g 100 = 20.3 wt% 600.5 g + 95.76 g + 177.25 g

hlori!e'0 in that0 "or PDC0 &1' .7B o" the

&$'

Chlorinate! pol(eth(lene !i""ers "ro+ pol(&)in(l

si!e,$on!in- sites are su$stitute! %ith Cl0 an! &.' the su$stitution is pro$a$l( +u h less ran!o+.

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

Molecular Sha!e
14.9 ;or a linear polymer molecule, the total chain length < depends on the bond length between chain atoms d, the total number of bonds in the molecule =, and the angle between ad>acent backbone chain atoms ?, as follows:

= 2

( 1.

;urthermore, the average end*to*end distance for a series of polymer molecules r in ;igure 1.% is e@ual to
= d
N

&14.1.'

A linear polytetrafluoroethylene has a number*average molecular weight of .!!,!!! g+molA compute average values of < and r for this material. Solution This pro$le+ "irst o" all as#s "or us to al ulate0 usin- E>uation 14.110 the a)era-e total hain len-th0 <0 "or a linear pol(tetra"luoroeth(lene pol(+er ha)in- a nu+$er,a)era-e +ole ular %ei-ht o" 7440444 -5+ol. Ta$le 14.10 ea h repeat unit has t%o ar$ons an! "our "lourines. Thus0 m 2 .&AC' 3 4&A/' It is ne essar( to al ulate the !e-ree o" pol(+eri<ation0 9B0 usin- E>uation 14.8. /or pol(tetra"luoroeth(lene0 "ro+

2 &.'&1..41 -5+ol' 3 &4'&19.44 -5+ol' 2 144.4. -5+ol an!

Mn 500, 000 g/mol = = 5000 m 100.02 g/mol

%hi h is the nu+$er o" repeat units alon- an a)era-e hain. Sin e there are t%o ar$on ato+s per repeat unit0 there are t%o CEC hain $on!s per repeat unit0 %hi h +eans that the total nu+$er o" hain $on!s in the +ole ule0 =0 is =ust &.'&7444' 2 140444 $on!s. /urther+ore0 assu+e that "or sin-le ar$on, ar$on $on!s0 d 2 4.174 n+ an! 2 149 &Se tion 14.4'C there"ore0 "ro+ E>uation 14.11

= 2
E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

 109 = (10, 000)(0.154 nm) sin = 1254 nm 2

It is no% possi$le to al ulate the a)era-e hain en!,to,en! !istan e0 r0 usin- E>uation 14.1. as

= d

N = (0.154 nm) 10, 000 = 15.4 nm

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.14 &sing the definitions for total chain molecule length, < (C@uation 1. end*to*end distance r (C@uation 1. -), for a linear polyethylene determine: (a) the number*average molecular weight for < D -.!! nmA (b) the number*average molecular weight for r D -! nm. Solution

) and average chain

&a' This portion o" the pro$le+ as#s "or us to al ulate the nu+$er,a)era-e +ole ular %ei-ht "or a linear pol(eth(lene "or %hi h < in E>uation 14.11 is .744 n+. It is "irst ne essar( to o+pute the )alue o" = usin- this e>uation0 %here0 "or the CEC hain $on!0 d 2 4.174 n+0 an! 2 149. Thus

2500 nm = 19, 940 109 (0.154 nm) sin 2

Sin e there are t%o CEC $on!s per pol(eth(lene repeat unit0 there is an a)era-e o" =5. or 1909445. 2 99:4 repeat units per hain0 %hi h is also the !e-ree o" pol(+eri<ation0 9B. In or!er to o+pute the )alue o" usinE>uation 14.80 %e +ust "irst !eter+ine m "or pol(eth(lene. Ea h pol(eth(lene repeat unit onsists o" t%o ar$on an! "our h(!ro-en ato+s0 thus m 2 .&AC' 3 4&AH'

2 &.'&1..41 -5+ol' 3 &4'&1.446 -5+ol' 2 .6.47 -5+ol There"ore

= (DP) m = (9970)(28.05 g/mol) = 280, 000 g/mol

&$' Ne*t0 %e are to !eter+ine the nu+$er,a)era-e +ole ular %ei-ht "or r 2 .4 n+. Sol)in- "or = "ro+ E>uation 14.1. lea!s to

r2 (20 nm) 2 = = 16,900 d2 (0.154 nm) 2

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

%hi h is the total nu+$er o" $on!s per a)era-e +ole ule. Sin e there are t%o CEC $on!s per repeat unit0 then 9B 2 =5. 2 1809445. 2 6474. No%0 "ro+ E>uation 14.8

= (DP) m = (8450)(28.05 g/mol) = 237,000 g/mol

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

Molecular Confi urations

14.11 Sketch portions of a linear polystyrene molecule that are (a) syndiotactic, (b) atactic, and (c) isotactic. &se two*dimensional schematics per footnote # of this chapter. Solution ;e are as#e! to s#et h portions o" a linear pol(st(rene +ole ule "or !i""erent on"i-urations &usint%o,!i+ensional s he+ati s#et hes'. &a' S(n!iota ti pol(st(rene

&$' Ata ti pol(st(rene

& ' Isota ti pol(st(rene

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.1. Sketch cis and trans structures for (a) butadiene, and (b) chloroprene. &se two*dimensional schematics per footnote Solution This pro$le+ as#s "or us to s#et h is an! trans stru tures "or $uta!iene an! hloroprene. &a' The stru ture "or cis pol($uta!iene &Ta$le 14.7' is of this chapter.

The stru ture o" trans $uta!iene is

&$' The stru ture o" cis hloroprene &Ta$le 14.7' is

The stru ture o" trans hloroprene is

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Thermo!lastic and Thermosettin Polymers

14.11 3ake comparisons of thermoplastic and thermosetting polymers (a) on the basis of mechanical characteristics upon heating, and (b) according to possible molecular structures. Solution &a' Ther+oplasti pol(+ers so"ten %hen heate! an! har!en %hen oole!0 %hereas ther+osettin-

pol(+ers0 har!en upon heatin-0 %hile "urther heatin- %ill not lea! to so"tenin-. &$' Ther+oplasti pol(+ers ha)e linear an! $ran he! stru tures0 %hile "or ther+osettin- pol(+ers0 the stru tures %ill nor+all( $e net%or# or rosslin#e!.

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.14 (a) 4s it possible to grind up and reuse phenol*formaldehyde6 7hy or why not6 (b) 4s it possible to grind up and reuse polypropylene6 7hy or why not6 Solution &a' It is not possible to -rin! up an! reuse phenol,"or+al!eh(!e $e ause it is a net%or# ther+oset pol(+er an!0 there"ore0 is not a+ena$le to re+ol!in-. &$' Fes0 it is possible to -rin! up an! reuse pol(prop(lene sin e it is a ther+oplasti pol(+er0 %ill so"ten %hen reheate!0 an!0 thus0 +a( $e re+ol!e!.

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

Co!olymers
14.17 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 pro$le+ as#s "or s#et hes o" the repeat unit stru tures "or se)eral alternatin- opol(+ers. &a' /or pol(&$uta!iene, hloroprene'

&$' /or pol(&st(rene,+eth(l +etha r(late'

& ' /or pol(&a r(lonitrile,)in(l hlori!e'

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.18

)he number*average molecular weight of a poly(styrene*butadiene) alternating copolymer is

,2.!,!!! g+molA determine the average number of styrene and butadiene repeat units per molecule. Solution Sin e it is an alternatin- opol(+er0 the nu+$er o" $oth t(pes o" repeat units %ill $e the sa+e. There"ore0 onsi!er the+ as a sin-le repeat unit0 an! !eter+ine the nu+$er,a)era-e !e-ree o" pol(+eri<ation. /or the st(rene repeat unit0 there are ei-ht ar$on ato+s an! ei-ht h(!ro-en ato+s0 %hile the $uta!iene repeat onsists o" "our ar$on ato+s an! si* h(!ro-en ato+s. There"ore0 the st(rene,$uta!iene o+$ine! repeat unit %ei-ht is =ust m 2 1.&AC' 3 14&AH'

2 &1.'&1..41 -5+ol' 3 &14'&1.446 -5+ol' 2 176..1 -5+ol /ro+ E>uation 14.80 the !e-ree o" pol(+eri<ation is =ust

Mn 1, 350, 000 g/mol = = 8530 m 158.23 g/mol

Thus0 there is an a)era-e o" 6714 o" $oth repeat unit t(pes per +ole ule.

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.1:

'alculate

the

number*average

molecular

weight

of

random

nitrile

rubber

Epoly(acrylonitrile*butadiene) copolymerF in which the fraction of butadiene repeat units is !.2!A assume that this concentration corresponds to a degree of polymeri,ation of -!!!. Solution This pro$le+ as#s "or us to al ulate the nu+$er,a)era-e +ole ular %ei-ht o" a ran!o+ nitrile ru$$er opol(+er. /or the a r(lonitrile repeat unit there are three ar$on0 one nitro-en0 an! three h(!ro-en ato+s. Thus0 its repeat unit +ole ular %ei-ht is mA 2 1&AC' 3 &AN' 3 1&AH'

2 &1'&1..41 -5+ol' 3 14.41 -5+ol 3 &1'&1.446 -5+ol' 2 71.48 -5+ol The $uta!iene repeat unit is o+pose! o" "our ar$on an! si* h(!ro-en ato+s. Thus0 its repeat unit +ole ular %ei-ht is mBu 2 4&AC' 3 8&AH'

2 &4'&1..41 -5+ol' 3 &8'&1.446 -5+ol' 2 74.49 -5+ol /ro+ E>uation 14.:0 the a)era-e repeat unit +ole ular %ei-ht is =ust

= f Ac mAc + f Bu mBu
2 &4.:4'&71.48 -5+ol' 3 &4.14'&74.49 -5+ol' 2 71.1: -5+ol Sin e 9B 2 .444 &as state! in the pro$le+'0 +a( $e o+pute! usin- E>uation 14.8 as

= m (DP) = (53.37 g/mol)(2000) = 106, 740 g/mol

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.16 An alternating copolymer is known to have a number*average molecular weight of -.!,!!! g+mol and a degree of polymeri,ation of 21-!. 4f one of the repeat units is styrene, which of ethylene, propylene, tetrafluoroethylene, and vinyl chloride is the other repeat unit6 7hy6 Solution /or an alternatin- opol(+er %hi h has a nu+$er,a)era-e +ole ular %ei-ht o" .740444 -5+ol an! a !e-ree o" pol(+eri<ation o" 14.40 %e are to !eter+ine one o" the repeat unit t(pes i" the other is st(rene. It is "irst ne essar( to al ulate

usin- E>uation 14.8 as

Mn 250,000 g/mol = = 73.10 g/mol DP 3420

Sin e this is an alternatin- opol(+er %e #no% that hain "ra tion o" ea h repeat unit t(pe is 4.7C that is fs 2 f( 2 4.70 fs an! f( $ein-0 respe ti)el(0 the hain "ra tions o" the st(rene an! un#no%n repeat units. Also0 the repeat unit +ole ular %ei-ht "or st(rene is ms 2 6&AC' 3 6&AH'

2 6&1..41 -5+ol' 3 6&1.446 -5+ol' 2 144.14 -5+ol No%0 usin- E>uation 14.:0 it is possi$le to al ulate the repeat unit %ei-ht o" the un#no%n repeat unit t(pe0 m(. Thus

m f s ms fx

73.10 g/mol - (0.5)(104.14 g/mol) = 42.06 g/mol 0.5

/inall(0 it is ne essar( to al ulate the repeat unit +ole ular %ei-hts "or ea h o" the possi$le other repeat unit t(pes. These are al ulate! $elo%@ meth(lene 2 .&AC' 3 4&AH' 2 .&1..41 -5+ol' 3 4&1.446 -5+ol' 2 .6.47 -5+ol mprop(lene 2 1&AC' 3 8&AH' 2 1&1..41 -5+ol' 3 8&1.446 -5+ol' 2 4..46 -5+ol mT/E 2 .&AC' 3 4&A/' 2 .&1..41 -5+ol' 3 4&19.44 -5+ol' 2 144.4. -5+ol mDC 2 .&AC' 3 1&AH' 3 &ACl' 2 .&1..41 -5+ol' 3 1&1.446 -5+ol' 3 17.47 -5+ol 2 8..49 -5+ol

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

There"ore0 prop(lene is the other repeat unit t(pe sin e its m )alue is al+ost the sa+e as the al ulate! m(.

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14.19

(a) 9etermine the ratio of butadiene to styrene repeat units in a copolymer having a

number*average molecular weight of 2.!,!!! g+mol and degree of polymeri,ation of 11-.. (b) 7hich type(s) of copolymer(s) will this copolymer be, considering the following possibilities: random, alternating, graft, and block6 7hy6 Solution &a' This portion o" the pro$le+ as#s us to !eter+ine the ratio o" $uta!iene to st(rene repeat units in a opol(+er ha)in- a %ei-ht,a)era-e +ole ular %ei-ht o" 1740444 -5+ol an! a !e-ree o" pol(+eri<ation o" 44.7. It "irst $e o+es ne essar( to al ulate the a)era-e repeat unit +ole ular %ei-ht o" the opol(+er0 E>uation 14.8 as

0 usin-

Mn 350,000 g/mol = = 79.10 g/mol DP 4425

I" %e !esi-nate fb as the hain "ra tion o" $uta!iene repeat units0 sin e the opol(+er onsists o" onl( t%o repeat unit t(pes0 the hain "ra tion o" st(rene repeat units fs is =ust 1 G fb. No%0 E>uation 14.: "or this opol(+er +a( $e %ritten in the "or+

= f b mb + f s ms = f b mb + (1 f b ) ms
in %hi h mb an! ms are the repeat unit +ole ular %ei-hts "or $uta!iene an! st(rene0 respe ti)el(. These )alues are al ulate! as "ollo%s@ mb 2 4&AC' 3 8&AH' 2 4&1..41 -5+ol' 3 8&1.446 -5+ol' 2 74.49 -5+ol ms 2 6&AC' 3 6&AH' 2 6&1..41 -5+ol' 3 6&1.446 -5+ol' 2 144.14 -5+ol

Sol)in- "or fb in the a$o)e e*pression (iel!s

m ms 79.10 g/mol 104.14 g/mol = = 0.50 mb ms 54.09 g/mol 104.14 g/mol

/urther+ore0 fs 2 1 G fb 2 1 G 4.74 2 4.74C or the ratio is =ust

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

 0.50 = = 1.0 0.50

&$' O" the possi$le opol(+ers0 the onl( one "or %hi h there is a restri tion on the ratio o" repeat unit t(pes is alternatin-C the ratio +ust $e 1@1. There"ore0 on the $asis o" the result in part &a'0 the possi$ilities "or this opol(+er are not onl( alternatin-0 $ut also ran!o+0 -ra"t0 an! $lo #.

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14..4 'rosslinked copolymers consisting of %! wt: ethylene and 1! wt: propylene may have elastic properties similar to those for natural rubber. ;or a copolymer of this composition, determine the fraction of both repeat unit types. Solution /or a opol(+er onsistin- o" 84 %tB eth(lene an! 44 %tB prop(lene0 %e are as#e! to !eter+ine the "ra tion o" $oth repeat unit t(pes. In 144 - o" this +aterial0 there are 84 - o" eth(lene an! 44 - o" prop(lene. The eth(lene &C .H4' +ole ular %ei-ht is m&eth(lene' 2 .&AC' 3 4&AH'

2 &.'&1..41 -5+ol' 3 &4'&1.446 -5+ol' 2 .6.47 -5+ol The prop(lene &C1H8' +ole ular %ei-ht is m&prop(lene' 2 1&AC' 3 8&AH'

2 &1'&1..41 -5+ol' 3 &8'&1.446 -5+ol' 2 4..46 -5+ol There"ore0 in 144 - o" this +aterial0 there are

60 g = 2.14 mol of ethylene 28.05 g/mol

an!

40 g = 0.95 mol of propylene 42.08 g/mol

Thus0 the "ra tion o" the eth(lene repeat unit0 f&eth(lene'0 is =ust

(ethylene) =

2.14 mol = 0.69 2.14 mol + 0.95 mol

Li#e%ise0

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

 (propylene) =

0.95 mol = 0.31 2.14 mol + 0.95 mol

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14..1

A random poly(isobutylene*isoprene) copolymer has a number*average molecular weight of

-!!,!!! g+mol and a degree of polymeri,ation of 2!!!. 'ompute the fraction of isobutylene and isoprene repeat units in this copolymer. Solution /or a ran!o+ pol(&iso$ut(lene,isoprene' opol(+er in %hi h 2 .440444 -5+ol an! 9B 2 14440 %e are as#e! to o+pute the "ra tions o" iso$ut(lene an! isoprene repeat units. /ro+ Ta$le 14.70 the iso$ut(lene repeat unit has "our ar$on an! ei-ht h(!ro-en ato+s. Thus0 mib 2 &4'&1..41 -5+ol' 3 &6'&1.446 -5+ol' 2 78.14 -5+ol

Also0 "ro+ Ta$le 14.70 the isoprene repeat unit has "i)e ar$on an! ei-ht h(!ro-en ato+s0 an! mip 2 &7'&1..41 -5+ol' 3 &6'&1.446 -5+ol' 2 86.11 -5+ol

/ro+ E>uation 14.:

= f ib mib + f ip mip
No%0 let ( 2 fib0 su h that

= 56.10 x + (68.11)(1 x)
sin e fib 3 fip 2 1. Also0 "ro+ E>uation 14.8

=
Or

3000 =

200,000 g/mol [56.10 x + 68.11(1 x)] g/mol

Sol)in- "or ( lea!s to ( 2 fib 2 f&iso$ut(lene' 2 4.1.. Also0 f&isoprene' 2 1 G ( 2 1 G 4.1. 2 4.66
E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

Polymer Crystallinity
14... C(plain briefly why the tendency of a polymer to crystalli,e decreases with increasing molecular weight. Solution The ten!en ( o" a pol(+er to r(stalli<e !e reases %ith in reasin- +ole ular %ei-ht $e ause as the hains $e o+e lon-er it is +ore !i""i ult "or all re-ions alon- a!=a ent hains to ali-n so as to pro!u e the or!ere! ato+i arra(.

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14..1 ;or each of the following pairs of polymers, do the following: ( ) state whether or not it is possible to determine whether one polymer is more likely to crystalli,e than the otherA (-) if it is possible, note which is the more likely and then cite reason(s) for your choiceA and (2) if it is not possible to decide, then state why. (a) <inear and syndiotactic poly(vinyl chloride)A linear and isotactic polystyrene. (b) =etwork phenol*formaldehydeA linear and heavily crosslinked cis*isoprene. (c) <inear polyethyleneA lightly branched isotactic polypropylene. (d) Alternating poly(styrene*ethylene) copolymerA random poly(vinyl chloride*tetrafluoroethylene) copolymer. Solution &a' Fes0 "or these t%o pol(+ers it is possi$le to !e i!e. The linear an! s(n!iota ti pol(&)in(l hlori!e' is +ore li#el( to r(stalli<eC the phen(l si!e,-roup "or pol(st(rene is $ul#ier than the Cl si!e,-roup "or pol(&)in(l hlori!e'. S(n!iota ti an! isota ti iso+ers are e>uall( li#el( to r(stalli<e. &$' No0 it is not possi$le to !e i!e "or these t%o pol(+ers. Both hea)il( rosslin#e! an! net%or# pol(+ers are not li#el( to r(stalli<e. & ' Fes0 it is possi$le to !e i!e "or these t%o pol(+ers. The linear pol(eth(lene is +ore li#el( to r(stalli<e. The repeat unit stru ture "or pol(prop(lene is he+i all( +ore o+pli ate! than is the repeat unit stru ture "or pol(eth(lene. /urther+ore0 $ran he! stru tures are less li#el( to r(stalli<e than are linear stru tures. &!' Fes0 it is possi$le to !e i!e "or these t%o opol(+ers. opol(+er is +ore li#el( to opol(+ers. r(stalli<e. Alternatinopol(+ers The alternatin- pol(&st(rene,eth(lene' r(stalli<e +ore easil( than !o ran!o+

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14..4 )he density of totally crystalline polypropylene at room temperature is !.$1% g+cm 2. Also, at room temperature the unit cell for this material is monoclinic with lattice parameters a D !.%%% nm b D -.!"# nm c D !.%.! nm G D $! H D $$.%- I D $!

4f the volume of a monoclinic unit cell, Jmono, is a function of these lattice parameters as Jmono D abc sin determine the number of repeat units per unit cell. Solution /or this pro$le+ %e are -i)en the !ensit( o" pol(prop(lene &4.948 -5 + 1'0 an e*pression "or the )olu+e o" its unit ell0 an! the latti e para+eters0 an! are as#e! to !eter+ine the nu+$er o" repeat units per unit ell. This o+putation ne essitates the use o" E>uation 1.70 in %hi h %e sol)e "or n. Be"ore this an $e arrie! out %e +ust "irst al ulate J'0 the unit ell )olu+e0 an! A the repeat unit +ole ular %ei-ht. /or J' J' D abc sin 2 &4.888 n+'&..4:6 n+'&4.874 n+' sin &99.8. ' 2 4.6689 n+ 1 2 6.689 14,.. +1 The repeat unit "or pol(prop(lene is sho%n in Ta$le 14.10 "ro+ %hi h the )alue o" A +a( $e !eter+ine! as "ollo%s@ A 2 1&AC' 3 8&AH'

2 1&1..41 -5+ol' 3 8&1.446 -5+ol' 2 4..46 -5+ol /inall(0 sol)in- "or n "ro+ E>uation 1.7 lea!s to

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

(0.946 g/cm 3 )( 8.869

10 -22 cm 3/unit cell)( 6.022 10 23 repeat units/mol ) 42.08 g/mol

2 1..4 repeat unit5unit ell

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14..7 )he density and associated percent crystallinity for two polytetrafluoroethylene materials are as follows: "g/cm 3# -. 11 -.- . crystallinity "% # . .2 "1.-

(a) 'ompute the densities of totally crystalline and totally amorphous polytetrafluoroethylene. (b) 9etermine the percent crystallinity of a specimen having a density of -.-% g+cm 2. Solution &a' ;e are as#e! to o+pute the !ensities o" totall( r(stalline an! totall( a+orphous

pol(tetra"luoroeth(lene &c an! a "ro+ E>uation 14.6'. /ro+ E>uation 14.6 let that

% 0 su h 100

(H s H a ) H s (H c H a )

Rearran-e+ent o" this e*pression lea!s to

( ) + = 0
in %hi h c an! a are the )aria$les "or %hi h solutions are to $e "oun!. Sin e t%o )alues o" s an! ' are spe i"ie! in the pro$le+ state+ent0 t%o e>uations +a( $e onstru te! as "ollo%s@

(1 1 1 ) + 1 1 = 0 (2 2 2 ) + 2 2 = 0
In %hi h s1 2 ..144 -5 + 10 s. 2 ...17 -5 + 10 '1 2 4.7110 an! '. 2 4.:4.. Sol)in- the a$o)e t%o e>uations "or a an! c lea!s to

1 2 (C1 C 2 ) C1 H s1 C2 H s2

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

(2.144 g/cm 3)( 2.215 g/cm 3)(0.513 0.742 ) = 2.000 g/cm 3 3 3 (0.513) (2.144 g/cm ) (0.742) ( 2.215 g/cm )

An!

1 2 (C 2 C1) H s2 (C2 1) H s1 (C1 1)

(2.144 g/cm3)( 2.215 g/cm3)(0.742 0.513) = 2.301 g/cm 3 (2.215 g/cm3)(0.742 1) (2.144 g/cm 3 )(0.513 1)

&$' No% %e are to !eter+ine the B r(stallinit( "or s 2 ...8 -5 + 1. A-ain0 usin- E>uation 14.6

% crystallinity =

H c (H s H a ) 100 H s (H c H a )
2.000 g/cm 3 ) 100 2.000 g/cm 3)

(2.301 g/cm 3 )( 2.260 g/cm 3 (2.260 g/cm 3)( 2.301 g/cm 3

2 6:.9B

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14..8 )he density and associated percent crystallinity for two nylon %,% materials are as follows: "g/cm 3# . ## . .crystallinity "% # %".2 12."

(a) 'ompute the densities of totally crystalline and totally amorphous nylon %,%. (b) 9etermine the density of a specimen having ...1: crystallinity. Solution &a' ;e are as#e! to o+pute the !ensities o" totall( r(stalline an! totall( a+orphous n(lon 808 & c an! a "ro+ E>uation 14.6'. /ro+ E>uation 14.6 let

% crystallinity 0 su h that 100

(H s H a ) H s (H c H a )

Rearran-e+ent o" this e*pression lea!s to

( ) + = 0
in %hi h c an! a are the )aria$les "or %hi h solutions are to $e "oun!. Sin e t%o )alues o" s an! ' are spe i"ie! in the pro$le+0 t%o e>uations +a( $e onstru te! as "ollo%s@

(C1 H s1 H s1) + H cH a C1H s1H a = 0

(C2 H s2 H s2 ) + H cH a C2H s2H a = 0
In %hi h s1 2 1.166 -5 +10 s. 2 1.17. -5 + 10 '1 2 4.8:10 an! '. 2 4.41:. Sol)in- the a$o)e t%o e>uations "or a an! c lea!s to

H s1 H s2 (C1 C2 ) C1 H s1 C2 H s 2

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

g/cm 3)(1.152 g/cm 3) (0.673 0.437) = 1.091 g/cm 3 3 3 (0.673) (1.188 g/cm ) (0.437) (1.152 g/cm )

(1.188

An!

H s1 H s2 (C 2 C1 ) H s2 (C2 1) H s1(C1 1)

g/cm 3)(1.152 g/cm 3) (0.437 0.673) = 1.242 g/cm 3 (1.152 g/cm3 ) (0.437 1) (1.188 g/cm 3) (0.673 1)

(1.188

&$' No% %e are as#e! to !eter+ine the !ensit( o" a spe i+en ha)in- 77.4B r(stallinit(. Sol)in- "or s "ro+ E>uation 14.6 an! su$stitution "or a an! c %hi h %ere o+pute! in part &a' (iel!s

(H c H a ) H c

(1.242 g/cm 3)(1.091 g/cm 3 ) (0.554 ) (1.242 g/cm 3 1.091 g/cm3 ) 1.242 g/cm3
2 1.1:4 -5 +1

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$iffusion in Polymeric Materials

14..: 'onsider the diffusion of water vapor through a polypropylene (BB) sheet - mm thick. )he pressures of 8-O at the two faces are kBa and ! kBa, which are maintained constant. Assuming conditions of steady state, what is the diffusion flu( Ein E(cm 2 S)B)+cm-*sF at -$# K6 Solution This is a per+ea$ilit( pro$le+ in %hi h %e are as#e! to o+pute the !i""usion "lu* o" %ater )apor throu-h a .,++ thi # sheet o" pol(prop(lene. In or!er to sol)e this pro$le+ it is ne essar( to e+plo( E>uation 14.9. The per+ea$ilit( oe""i ient o" H.O throu-h PP is -i)en in Ta$le 14.8 as 16 14,11 & +1 STP', +5 +.,s,Pa. Thus0 "ro+ E>uation 14.9

2 1 =

an! ta#in- B1 2 1 #Pa &10444 Pa' an! B. 2 14 #Pa &140444 Pa' %e -et

(cm3 STP)(cm) 10, 000 Pa 1, 000 Pa = 38 10 -13 0.2 cm cm 2 - s - Pa

= 1.71 10 -7

(cm3 STP) cm 2 - s

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

14..6 Argon diffuses through a high density polyethylene (89BC) sheet 1! mm thick at a rate of 1.! L !0" (cm2 S)B)+cm-*s at 2-. K. )he pressures of argon at the two faces are .!!! kBa and .!! kBa, which are maintained constant. Assuming conditions of steady state, what is the permeability coefficient at 2-. K6 Solution This pro$le+ as#s us to o+pute the per+ea$ilit( oe""i ient "or ar-on throu-h hi-h !ensit( pol(eth(lene at 1.7 I -i)en a stea!(,state per+ea$ilit( situation. It is ne essar( "or us to E>uation 14.9 in or!er to sol)e this pro$le+. Rearran-in- this e*pression an! sol)in- "or the per+ea$ilit( oe""i ient -i)es

= 2 1

Ta#in- B1 2 1744 #Pa &107440444 Pa' an! B. 2 7444 #Pa &704440444 Pa'0 the per+ea$ilit( oe""i ient o" Ar throu-h HJPE is e>ual to

(cm3 STP) 4.0 10 -7 (4 cm) cm2 - s = (5, 000, 000 Pa - 1, 500, 000 Pa)

= 4.57 10 -13

(cm 3 STP)(cm) cm2 - s - Pa

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14..9 )he permeability coefficient of a type of small gas molecule in a polymer is dependent on absolute temperature according to the following e@uation:

Qp = PM 0 exp RT
where

PM 0 and Mp are constants for a given gas*polymer pair. 'onsider the diffusion of hydrogen through a

poly(dimethyl silo(ane) (B93SO) sheet -! mm thick. )he hydrogen pressures at the two faces are ! kBa and kBa, which are maintained constant. 'ompute the diffusion flu( Ein (cm 2 S)B)+cm- 0sF at 2.! K. ;or this diffusion system

PM 0 = 1.45 10 8 (cm 3 STP)(cm)/cm 2 - s - Pa

Mp D 2." kN+mol Also, assume a condition of steady state diffusion Solution This pro$le+ as#s that %e o+pute the !i""usion "lu* at 174 I "or h(!ro-en in pol(&!i+eth(l silo*ane' &PJMSO'. It is "irst ne essar( to o+pute the )alue o" the per+ea$ilit( oe""i ient at 174 I. The te+perature !epen!en e o" B3 is -i)en in the pro$le+ state+ent0 as "ollo%s@
= 0

An!0 in orporatin- )alues pro)i!e! "or the onstants B3 an! Mp0 %e -et 4
3 13, 700 J/mol -8 (cm STP)(cm) exp = 1.45 10 cm 2 - s - Pa (8.31 J/mol- K)(350 K)

= 1.31 1010
An!0 usin- E>uation 14.90 the !i""usion "lu* is e>ual to

(cm3 STP)(cm) cm2 - s - Pa

2 1 =

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.

= 1.31 10 -10

(cm 3 STP)(cm) cm2 - s - Pa

10,000 Pa - 1, 000 Pa 2.0 cm

= 5.90 10 -7

(cm3 STP) cm2 - s

E* erpts "ro+ this %or# +a( $e repro!u e! $( instru tors "or !istri$ution on a not,"or,pro"it $asis "or testin- or instru tional purposes onl( to stu!ents enrolle! in ourses "or %hi h the te*t$oo# has $een a!opte!. Any other reproduction or translation of this work beyond that permitted by Sections !" or !# of the $"% &nited States 'opyright Act without the permission of the copyright owner is unlawful.