ESCUELA POLITCNICA NACIONALFACULTAD DE INGENIERA QUMICAY AGROINDUSTRIACARRERA DE INGENIERA QUMICAINGENIERA DE LA REACCIN IDeber No. 4EJERCICIOS DE LEYES DEVELOCIDAD YESTEQUIOMETRACAPTULO 3Profesor:Ing. Marcelo Alb!aAlumo!":Sr"a. Gabr#ela R#$#e$%" &e e're(":M#%rcole&' () *e abr#l *e )+(()Semes're: Mar$o , Ago&"o )+((-Le)es &e *elo$+&"& )es'e,u+ome'r-" E.er$+$+o P37B"/ L" re(l" 0r1$'+$" &e ,ue l" *elo$+&"& &e re"$$+2 se &u0l+$"$o u +$reme'o &e345 / e l" 'em0er"'ur"s2lo o$urre " u" 'em0er"'ur" es0e$-6$" 0"r" u" eer(-"&e "$'+*"$+2 &"&"7 De&u8$" u" rel"$+2 e're l"'em0er"'ur")l"eer(-"&e"$'+*"$+20"r"l"$u"l se$um0l"l"re(l"0r1$'+$"7 9"("$"soom+so&e$u"l,u+er*"r+"$+2 &e l" $o$e'r"$+2 $o l" 'em0er"'ur"7k=A eEaRTln( k)=ln( A)EaR ( 1T )ln(k1)=ln ( A) EaR ( 1T1) ln(k2)=ln ( A) EaR ( 1T2)ln(k1)ln(k2)=(ln ( A) EaR ( 1T1))(ln ( A) EaR ( 1T2))ln(k1k2)= EaR ( 1T2)EaR ( 1T1)ln(k1k2)= EaR ( 1T2 1T1)4ln(k1k2)= EaR (T1T2T1T2 )k2=2k1T2=T1+10[ K ]ln( k12k1)=EaR (T1(T1+10)T1(T1+10) )ln(2)=EaR (10T1 (T1+10))ln(2)= EaR (10T1(T1+10))Ea=R ln(2)T1(T1+10)10T1=[ K ]:/ De'erm+e l" eer(-" &e "$'+*"$+2 ) el f"$'or &efre$ue$+" " 0"r'+r &e los s+(u+e'es &"'os:k(m1)+'++( +'+.+T ( )+'+ (++'+k=A eEaRTln( k)=ln( A)EaR ( 1T ).ln(k1)=ln ( A) EaR ( 1T1) ln(k2)=ln ( A) EaR ( 1T2)ln(k1)ln(k2)=(ln ( A) EaR ( 1T1))(ln ( A) EaR ( 1T2))ln(k1k2)= EaR ( 1T2)EaR ( 1T1)ln(k1k2)= EaR ( 1T2 1T1)ln(0,0010,050 )=Ea1,987kcalkgmol K (1( 100+273) K 1( 0+273) K )Ea=7915,36 kcalkgmolk=A eEaRTA=k eEaRTA=0,001m1 e7915,36 kcalkgmol(1,987kcalkgmol K )(0+273) KA=2,1735103m1/ E.er$+$+o P310A"/ Es$r+:"l"le)&e*elo$+&"&&el"ss+(u+e'esre"$$+oes"sum+e&o ,ue $"&" u" &e ell"s es eleme'"l res0e$'o "l" *elo$+&"& &e re"$$+274/C2 H6C2H4+H2rC2H6=k CC2 H6;/C2 H4+1/ 2O2C H2OC H3rC2H4=k CC2H4CO21/ 23/(C H3)3COOC(C H3)3C2H6+2C H3COC H3r(C H3 )3COOC(C H3 )3=k1C(C H3 )3COOC(C H3)3k2CC2H6CC H3COC H32kEq=k1k2k2= k1kEqr(C H3 )3COOC(C H3 )3=k1C(C H3)3COOC(C H3)3( k1kEq)CC2H6CC H3COC H32r(C H3 )3COOC(C H3 )3=k1(C(CH3 )3COOC(CH3 )3CC2H6CC H3COCH32kEq)0 e*"lu"&o'o&"s l"s $os'"'es7 E'o$es> "sum+e&o ,ue l"s re"$$+oes,uesemues'r"soeleme'"lese$u"'o"l"le)&el"*elo$+&"& &e re"$$+2> eA0rese l" *elo$+&"& &e re"$$+2 $omou" fu$+2 &e l" $o*ers+27 Por e.em0lo:rA=f ( x)"/ L" re"$$+2 e f"se l-,u+&":O3H2OH2SO4OHOHL"s$o$e'r"$+oes++$+"les&el 2A+&o&ee'+leo)&el"(u" so 4 lbmol / f t3 ) 3>B< lbmol / f t3> res0e$'+*"me'e7D"'os:oCA0=1lbmol / f t3oCB0=3,74lbmol / f t3Co4o la reacc#5n e& en 6a&e l78#*a' &e 9a a con*erar al 9ol4encon&"an"e. E&"o #4:l#ca 8e la "abla e&"e8#o4%"r#ca &er; la 4#&4a(+can*o la reacc#5n &e lle9a a cabo en n reac"or ba"c< 8e can*ola reacc#5n &e *e&arrolla en n reac"or con"#no. A*e4;&' co4o larelac#5n e&"e8#o4%"r#ca e& *e (' e9#*en"e4en"e la e&:ec#e A e& elreac"#9o l#4#"an"e.

B=CB0CA0=3,74lbmol / f t31lbmol / f t3B=3,74

C=CC0CA0=0lbmol / f t31lbmol / f t3 C=0CA=CA0 ( 1x) CA=1x[lbmolf t3 ]CB=CA0(

Bba x)CB=3,74x[lbmolf t3 ]CC=CA0(

C+ca x)CC=x[lbmolf t3 ]rA=kCACBrA=k (1x) ( 3,74x)[lbmolf t3! ]S+ k=0,1"m3/ mol ! " $o u" eer(-" &e "$'+*"$+2 3/ &e 4;=55> $"l$ule el es0"$+o C '+em0o 3 / )((el *olume 0"r" lo(r"r el D5E &e $o*ers+2 ") "7oT=300 K k=0,1" m3/ mol !rA=k (1x) ( 3,74x)rA=(0,1 " m3mol !)(( 10,90) lbmolf t3 )(( 3,740,90) lbmolf t3 ) 453,6 gmol1lbmol (10cm)31" m3 1f t3(30,48cm)3rA=0,4549 lbmolf t3!#C$TR=( %A0rA )x %A0=CA0&0#C$TR=(CA0&0rA )x#C$TR=( (1lbmolf t3 )&00,4549 lbmolf t3! )( 0,90)#C$TR=1,9782&0 [ f t3] &0=[ f t3! ]()' =#&0 '=1,9782&0 [ f t3]&0[ f t3! ]ok=A eEaRTk1=A eEaR T10,1 " m3mol !=A e12500 calmol1,987calmol K (300 K)A=1,2794108 " m3mol !k2=A eEaRT2k2=(1,2794108 " m3mol !)e12500 calmol1,987calmol K ( 350 K)k2=2 "m3mol !(-rA=k (1x) ( 3,74x)rA=(2 " m3mol !)(( 10,90) lbmolf t3 )(( 3,740,90) lbmolf t3 ) 453,6 gmol1lbmol (10cm)31" m3 1f t3(30,48cm)3rA=9,0986 lbmolf t3!#C$TR=( %A0rA )x %A0=CA0&0#C$TR=(CA0&0rA )x#C$TR=( (1lbmolf t3 )&09,0986 lbmolf t3! )( 0,90)#C$TR=0,0989&0 [ f t3] &0=[ f t3! ]' =#&0 '=0,0989&0 [ f t3]&0[f t3! ]:/ A l" 0+rol+s+s +so'@rm+$" +so:1r+$" e f"se ("seos":C2 H6C2H4+H2(4E'r" e'"o 0uro e el re"$'or " F "'m ) 4455 7 GC2mo$"m:+"r-" su e$u"$+2 0"r" l" $o$e'r"$+2 s+ el re"$'orse efe$'H" e u re"$'or 0or lo'es &e *olume $os'"'eIA B+C1(2# (cteD"'os:ooo)A0=1oCB0=0 kgmol/ m3B=0oCC0=0kgmol / m3C=0La "abla e&"e8#o4%"r#ca *e e&"a reacc#5n en 6a&e ga&eo&a' = :arala cal el 9ol4en no e& con&"an"e' e& la g#en"e>%A=%A0 ( 1x)%B=%A0(

B+ba x)%B=%A0x%C=%A0(

C+ca x)%C=%A0x(.S# la reacc#5n &e e6ec"?a en n reac"or :or lo"e& a 9ol4encon&"an"e'=&e4an"#enencon&"an"e& "a4b#%na la :ren=la"e4:era"ra *el &"e4a' la "abla e&"e8#o4%"r#ca *e la reacc#5ne& la g#en"e>CA0= )A0 PRT =(1) (6atm)0,0821m3atmkgmol K ( 1100 K ) CA0=0,06643 kgmolm3*=ba+ ca1=1+11*=1+=)A0*=( 1) ( 1) +=1CA=CA0( 1x1++x )( PP0 )(T0T )CA=0,06643(1x1+x )[ kgmolm3]CB=CA0(

B+ba x1++x )( PP0)(T0T )CB=0,06643(x1+x)[ kgmolm3]CC=CA0(

C+ca x1++x )( PP0)(T0T )CC=0,06643(x1+x)[kgmolm3]rA=kCArA=k(0,06643(1x1+x ))[ kgmolm3! ](/rA=0,06643k(1x1+x )[ kgmolm3! ]$/ L" oA+&"$+2 +so'@rm+$"> +so:1r+$"> $"'"l-'+$"> e f"se("seos":O3 O2C2H4()A+12BC3/ 2(1# (cteL" "l+me'"$+2 e'r" e u re"$'or P?R " F "'m ) ;F5JC> )es u" me8$l" es'e,u+om@'r+$" &e oA-(eo ) e'+leo7D"'os:oooCB0=1/ 2CA0B=1/ 2oCC0=0kgmol / m3C=0Co4o la al#4en"ac#5n e& e&"e8#o4%"r#ca' &e :e*e "o4ar acal8#era *e lo& reac"#9o& co4o reac"#9o ba&e. @or e&o' &e lo 9a a*egnar co4o "al al e"#leno AC2 H4B. En"once&' :ara n reac"or*e C!o con"#no' la "abla e&"e8#o4%"r#ca e&>(0%A=%A0 ( 1x)%B=%A0(

Bba x)%B=%A0(1212 x)%C=%A0(

C+ca x)%C=%A0xCon*eran*o 8e la reacc#5n e& en 6a&e ga&eo&a' = *e :ren ="e4:era"ra con&"an"e&' la "abla e&"e8#o4%"r#ca e&>)A0=CA0CT 0=CA0CA0+CB0 )A0=CA0CA0+12 CA0)A0=23CA0= )A0 PRT =(23)( 6 atm)0,0821m3atmkgmol K ( 260+273) K CA0=0,0914 kgmolm3*=caba1=1121*=12+=)A0*=(23)(12 )+=13(1CA=CA0( 1x1++x )( PP0 )(T0T )CA=0,0914( 1x113 x)[kgmolm3]CB=CA0(

Bba x1++x )( PP0)(T0T )CB=0,0914( 1212 x113 x )[kgmolm3]CC=CA0(

C+ca x1++x )( PP0)(T0T )CC=0,0914(x113 x)[kgmolm3]rA=kCACB1/ 2rA=k(0,0914( 1x113 x))(0,0914( 1212 x113 x ))1/ 2[kgmolm3! ]rA=0,0276k((1x)(1212 x)(113 x)3/2)[ kgmolm3! ]&/ L" re"$$+2 +so'@rm+$"> +so:1r+$"> $"'"l-'+$"> e f"se("seos" se lle*" " $":o e u re"$'or P?R7(232H2A+2BC3(1# (cteL" "l+me'"$+2 e'r" "l re"$'or P?R " F "'m ) 4B5JC $omou" me8$l" es'e,u+om@'r+$"7 GQu@ m"s" &e $"'"l+8"&or ese$es"r+" 0"r" "l$"8"r el K5E &e $o*ers+2 e u re"$'orCSTR Lu+&+8"&o " 4B5JC ) ;B5JCI L" $os'"'e &e*elo$+&"& es'1 &e6+&" 0"r" el :e$eo ) u" *elo$+&"& &eLu.o *olum@'r+$o ++$+"l 3&0/ &e 50" m3/ min7kB=53molkgcat min at m3 a300 K con Ea=80 k,molD"'os:ooo&0=50"m3/ minoCB0=2CA0B=2oCC0=0kgmol / m3C=0Igal 8e en el ca&o an"er#or' co4o la al#4en"ac#5n e&e&"e8#o4%"r#ca' &e:e*e"o4ar acal8#era*elo&reac"#9o&)+co4o ba&e. En e&"e ca&o' &e "o4ar; co4o reac"#9o ba&e albenceno AAB' *e 4o*o 8e en can"o a la "abla e&"e8#o4%"r#ca'&e "#ene lo g#en"e>%A=%A0 ( 1x)%B=%A0(

Bba x)%B=%A0( 22x)%C=%A0(

C+ca x)%C=%A0xCon*eran*o 8e la reacc#5n e& en 6a&e ga&eo&a' = *e :ren ="e4:era"ra con&"an"e&' la "abla e&"e8#o4%"r#ca e&>)A0=CA0CT 0=CA0CA0+CB0 )A0=CA0CA0+2CA0)A0=13CA0= )A0 PRT =(13)( 6 atm)0,0821m3atmkgmol K ( 170+273) KCA0=0,055 kgmolm3*=caba1=121*=2)(+=)A0*=(13)(2) +=23CA=CA0( 1x1++x )( PP0 )(T0T )CA=0,055( 1x123 x)[ kgmolm3]CB=CA0(

Bba x1++x )( PP0)(T0T )CB=0,055( 22x123 x)[ kgmolm3]CC=CA0(

C+ca x1++x )( PP0)(T0T )CC=0,055(x123 x)[ kgmolm3]rA-=kB PA PB2Ci= PiRT Pi=CiRTrA-=kB (CART) (CBRT )2rA-=kB ( RT)3CACB2))rA-=kB (RT)3(0,055( 1x123 x))(0,055( 22x123 x))2[molmin kgcat ]rA-=1,6628104kB ( RT)3((1x) (22x)2(123 x)3)[molmin kgcat ].=%A00x"xrA- =CA0&00x"xrA-.=( )A0 PRTmol"m3)(50 " m3min )00,8"x1,6628104kB ( RT )3((1x) ( 22x)2(123 x)3)[molmin kg cat ].=3,007105)A0PkB( RT )200,8 (123 x)3"x( 1x) ( 22 x)2 [ kgcat ].=3,007105(13)(6[ atm])kB ( RT)2(53)[ kgcat ].=1,0023106kB ( RT)2[ kgcat ]o)-T=300 K kB=53molkgcat min at m3k=A eEaRT53molkgcat min at m3=A e80 k,mol 1000,1k,1cal4,186,(1,987calmol K)( 300 K)A=4,44651015molkgcat min at m3kB2=A eEaR T2kB2=(4,44651015molkgcat min at m3)e80 k,mol1000 ,1k,1cal4,186,(1,987calmol K)(300 K)kB2=1,6552106molkgcat min at m3.=1,0023106kB ( RT)2[ kgcat ].=1,00231061,6552106 molkgcat min at m3 ((0,0821 " m3atmmol K )( 443 K))2 [ kgcat ])4okB3=A eEaR T3kB3=(4,44651015molkgcat min at m3)e80 k,mol 1000,1k,1cal4,186,(1,987calmol K)( 543 K)kB3=9,0228107molkgcat min at m3.=1,00231069,0228107molkgcat min at m3((0,0821 "m3atmmol K )( 443 K ))2 [ kg cat ] E.er$+$+o P313BL" form"$+2 &e +'ro"+l+" 3ll"m"&" '"m:+@ fast orange> u+'erme&+"r+o +m0or'"'e e el 'eM+&o/ se efe$'H" " 0"r'+r &el" re"$$+2 &e or'o+'ro$loro:e$eo 3ONC?/ ) "mo-"$o"$uoso732NH3NO2ClNO2NH23NH4Cl).L"re"$$+2ef"sel-,u+&"es&e0r+meror&eres0e$'o"lONC?) "l "mo-"$o> $ou" $os'"'e&e *elo$+&"&&ek=0,0017m3/ kgmol min" >0"r"l"$u"ll"eer(-"&e"$'+*"$+2 es7 L"s $o$e'r"$+oes ++$+"les&e ONC? ) "mo-"$o so1,8kgmol /m3)6,6kgmol / m3>res0e$'+*"me'e7D"'os:ok=0,0017m3/ kgmol min a (11oCA0=1,8kgmol / m3oCB0=6,6 kgmol/ m3oCC0=0kgmol / m3C=0oC/0=0kgmol /m3/=0(CB0)0ece!aria=1,8 kgmol Am3 2kgmol B1kgmol A(CB0)0ece!aria=3,6 kgmol Bm3

) I C"l$ulel"s $o$e'r"$+oes &e"mo-"$oe%+&r2(eo $u"&o l" $o*ers+2 &el %+&r2(eo es F5E7CA0= )A0 PRT =(0,5) (16,4 atm)0,0821m3atmkgmol K ( 227+273) K CA0=0,2kgmolm3*=caba1=23131*=23-4+=)A0*=(12)(23 )+=13CA=CA0( 1x1++x )( PP0 )(T0T )CA=0,2( 1x113 x)[ kgmolm3]CA=0,2(10,60113 ( 0,60))[ kgmolm3]CA=0,1 kgmolm3CB=CA0(

Bba x1++x )( PP0)(T0T )CB=0,2(113 x113 x )CB=0,2[kgmolm3]CB=0,2[kgmolm3]CC=CA0(

C+ca x1++x )( PP0)(T0T )CC=0,2(23 x113 x )[ kgmolm3]-.CC=0,2(23( 0,60)113( 0,60) )[kgmolm3]CC=0,1kgmolm3$/ Su0o+e&o ,ue l" re"$$+2 es eleme'"l $ok02=40" m3/ mol !> es$r+:"l"*elo$+&"&&ere"$$+2$omofu$+2 &e l" $o*ers+2 H+$"me'e> 0"r": 34/ u s+s'em"&e Lu.o $o'+uo ) 3;/ u s+s'em" :"'$% &e *olume$os'"'e7rA=kCACBo S#&"e4a *e C!o con"#norA=kCACBrA=(40m3kgmol !)(0,2( 1x113 x)kgmolm3)(0,2 kgmolm3)rA=1,6( 1x113 x)[ kgmolm3! ]o S#&"e4a ba"c< *e 9ol4en con&"an"eCo4o la "e4:era"ra &e 4an"#ene con&"an"e' = &e con*era lo4#&4o :ara la :ren' la "abla e&"e8#o4%"r#ca *e la reacc#5ne& la 4#&4a :ara n &"e4a #n"er4#"en"e 8e :ara n &"e4acon"#no. @or lo "an"o>-/rA=kCACBrA=(40m3kgmol !)(0,2( 1x113 x)kgmolm3)(0,2 kgmolm3)rA=1,6( 1x113 x)[ kgmolm3! ] E.er$+$+o P316BC"l$ulel"$o*ers+2)l"s$o$e'r"$+oeseel e,u+l+:r+o0"r" $"&" u" &e l"s re"$$+oes s+(u+e'es:"/ L" re"$$+2 e f"se l-,u+&":Co CA0=CB0=2mol / " m3) kC=10"m3/ mol:/ L" re"$$+2 e f"se ("seos":Efe$'u"&" e u re"$'or &e Lu.o s+ $"-&" &e 0res+27 Se"l+me'" A 0uro " u" 'em0er"'ur" &e ) 45 "'m7 Aes'" 'em0er"'ur":kC=0,25"m3/ mo l2La reacc#5n ocrre a87-0$/ L" re"$$+2 e f"se ("seos" &e l" 0"r'e 3:/ efe$'u"&" eu re"$'or 0or lo'es &e *olume $os'"'e7&/ L" re"$$+2 e f"se ("seos" &e l" 0"r'e 3:/ efe$'u"&" eu" re"$'or 0or lo'es &e 0res+2 $os'"'e7 E.er$+$+o P317BCos+&ere u re"$'or 0or lo'es $+l-&r+$o e $u)o eA'remo se%"+s'"l"&ou0+s'2s+fr+$$+2$oe$'"&o"uresor'e>$omo lo mues'r" l" #+(ur" 47 L" re"$$+2:Cu)" eA0res+2 &e *elo$+&"& es:rA=k1CA2CBSe efe$'u"r1 e es'e '+0o &e re"$'or:#+(ur" 47 Reac"or :or lo"e& c#l7n*r#co con :#&"5nIform"$+2 "&+$+o"l:o E es'1 0rese'es Hmeros +(u"les &e moles &eA ) ?7o Volume ++$+"l: 0,5f t3-1o V"lor &e k1: 1,0( f t3/lbmol )2!1o L"rel"$+2e'reel *olume&el re"$'or)l"0res+2&e'ro &el re"$'or es: s+ #=[f t3] ) P=[ atm]o Tem0er"'ur" &el s+s'em" 3se $os+&er" $os'"'e/:o Cos'"'e &e los ("ses: 0,73f t3atm/lbmol R"/ Es$r+:" l" le) &e *elo$+&"& eA$lus+*"me'e e fu$+2 &e l"$o*ers+2>e*"lu"&oum@r+$"me'e 'o&osloss-m:olos,ue se" 0os+:le7rA=5,03109((1x)3( 1+3 x)3/ 2)[lbmolf t3! ]:/ C"l$ulel"$o*ers+2)l"*elo$+&"&&ere"$$+2$u"&o#=0,2 f t37rA=8,631010 lbmolf t3!