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EQUILIBRIUM ANDEQUILIBRIUM AND
EXTERNAL EFFECTSEXTERNAL EFFECTS• Temperature, catalysts, and can!es "nTemperature, catalysts, and can!es "nc#ncentrat"#n a$$ect e%u"l"&r"a'c#ncentrat"#n a$$ect e%u"l"&r"a'
• Te #utc#me "s !#(erned &yTe #utc#me "s !#(erned &y LELEC)ATELIER*S +RINCI+LEC)ATELIER*S +RINCI+LE
• '''"$ a system at e%u"l"&r"um "s'''"$ a system at e%u"l"&r"um "s
d"stur&ed, te system tends t# s"$t "tsd"stur&ed, te system tends t# s"$t "tse%u"l"&r"um p#s"t"#n t# c#unter tee%u"l"&r"um p#s"t"#n t# c#unter tee$$ect #$ te d"stur&ance'-e$$ect #$ te d"stur&ance'-
Copyright © 1999 by Harcourt Brace & Company
All rights reserved.
Requests or permission to ma!e copies o any part
o the "or! should be mailed to# $ermissions
%epartment Harcourt Brace & Company '())
*ea Harbor %rive +rlando ,lorida
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EQUILIBRIUM ANDEQUILIBRIUM AND
EXTERNAL EFFECTSEXTERNAL EFFECTS
)enr" Le Catel"er )enr" Le Catel"er
./012.345./012.345
Stud"ed m"n"n!Stud"ed m"n"n!en!"neer"n!'en!"neer"n!'
Interested "n !lassInterested "n !lassand ceram"cs'and ceram"cs'
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EQUILIBRIUM AND EXTERNAL EFFECTSEQUILIBRIUM AND EXTERNAL EFFECTS
• Temperature can!eTemperature can!e 2226 can!e "n 72226 can!e "n 7• C#ns"der te $"88 "n a s#$t dr"n9C#ns"der te $"88 "n a s#$t dr"n9 C:C:;;<!= ><!= >
));;:<l"%=:<l"%= C:C:;;<a%= > eat<a%= > eat
• Decrease T' ?at appens t# e%u"l"&r"umDecrease T' ?at appens t# e%u"l"&r"ump#s"t"#n@ T# (alue #$ 7@p#s"t"#n@ T# (alue #$ 7@
• 7 C:7 C:;; + <C: + <C:;;== 7 "ncreases as T !#es7 "ncreases as T !#es
d#n &ecaused#n &ecause C:C:;; "ncreases and "ncreases and
+<C:+<C:;;= decreases'= decreases'
• Increase T' N# at@Increase T' N# at@
• E%u"l"&r"um s"$ts le$t and 7 decreases'E%u"l"&r"um s"$ts le$t and 7 decreases'
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Temperature E$$ectsTemperature E$$ects
#n E%u"l"&r"um#n E%u"l"&r"umNN;;:: <c#l#rless= > eat<c#l#rless= > eat
; N:; N:;; <&r#n=<&r#n=
))## > 0G'; 9H > 0G'; 9H
77c 1'111GG at ;G4 7 1'111GG at ;G4 7
77c 1'1103 at ;3/ 7 1'1103 at ;3/ 7
Kc [NO2]
2
[N2O4]
Kc [NO2]
2
[N2O4]
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EQUILIBRIUM AND EXTERNAL EFFECTSEQUILIBRIUM AND EXTERNAL EFFECTS
• Add catalystAdd catalyst 2226 n# can!e "n 72226 n# can!e "n 7• A catalyst #nly a$$ects te RATE #$A catalyst #nly a$$ects te RATE #$
appr#ac t# e%u"l"&r"um'appr#ac t# e%u"l"&r"um'
Catalytic exhaust systemCatalytic exhaust system
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• NN;;<!= > 4 )<!= > 4 );;<!=<!= ; N); N)44<!=<!=
• 7 4'0 .17 4'0 .1// at ;3/ 7at ;3/ 7
N)N)44
+r#duct"#n+r#duct"#n
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EQUILIBRIUM AND EXTERNAL EFFECTSEQUILIBRIUM AND EXTERNAL EFFECTS
• C#ncentrat"#n can!esC#ncentrat"#n can!es 2226 n# can!e2226 n# can!e"n 7 J #nly te p#s"t"#n #$"n 7 J #nly te p#s"t"#n #$e%u"l"&r"um can!es'e%u"l"&r"um can!es'
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Le Catel"er*s +r"nc"pleLe Catel"er*s +r"nc"ple
Add"n! a reactant- t# a cem"calAdd"n! a reactant- t# a cem"calsystem'system'
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Le Catel"er*s +r"nc"pleLe Catel"er*s +r"nc"ple
Rem#("n! a reactant- $r#m a cem"calRem#("n! a reactant- $r#m a cem"calsystem'system'
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Le Catel"er*s +r"nc"pleLe Catel"er*s +r"nc"ple
Add"n! a pr#duct- t# a cem"calAdd"n! a pr#duct- t# a cem"calsystem'system'
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Le Catel"er*s +r"nc"pleLe Catel"er*s +r"nc"ple
Rem#("n! a pr#duct- $r#m a cem"calRem#("n! a pr#duct- $r#m a cem"calsystem'system'
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Butane2Butane2
Is#&utaneIs#&utaneE%u"l"&r"umE%u"l"&r"um
K =[isobutane][butane]
2.5K =[isobutane][butane]
2.5
butanebutane
isobutaneisobutane
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ButaneButane Is#&utaneIs#&utane
butanebutane
isobutanisobutan
Assume y#u are at e%u"l"&r"um "t "s# .';0Assume y#u are at e%u"l"&r"um "t "s# .';0M and &utane 1'01 M' N# add .'01 MM and &utane 1'01 M' N# add .'01 M&utane' ?en te system c#mes t#&utane' ?en te system c#mes t#e%u"l"&r"um a!a"n, at are "s# ande%u"l"&r"um a!a"n, at are "s# and
&utane@&utane@ 7 ;'07 ;'0
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ButaneButane Is#&utaneIs#&utaneAssume y#u are at e%u"l"&r"um "t "s# .';0Assume y#u are at e%u"l"&r"um "t "s# .';0
M and &utane 1'01 M' N# add .'01 MM and &utane 1'01 M' N# add .'01 M&utane' ?en te system c#mes t#&utane' ?en te system c#mes t#e%u"l"&r"um a!a"n, at are "s# ande%u"l"&r"um a!a"n, at are "s# and
&utane@&utane@ 7 ;'07 ;'0
S#lut"#nS#lut"#n
Calculate Q "mmed"ately a$ter add"n! m#reCalculate Q "mmed"ately a$ter add"n! m#re&utane and c#mpare "t 7'&utane and c#mpare "t 7'
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ButaneButane Is#&utaneIs#&utaneAssume y#u are at e%u"l"&r"um "t "s# .';0Assume y#u are at e%u"l"&r"um "t "s# .';0
M and &utane 1'01 M' N# add .'01 MM and &utane 1'01 M' N# add .'01 M&utane' ?en te system c#mes t#&utane' ?en te system c#mes t#e%u"l"&r"um a!a"n, at are "s# ande%u"l"&r"um a!a"n, at are "s# and
&utane@&utane@ 7 ;'07 ;'0
S#lut"#nS#lut"#n
Calculate Q "mmed"ately a$ter add"n! m#reCalculate Q "mmed"ately a$ter add"n! m#re&utane and c#mpare "t 7'&utane and c#mpare "t 7'
Q =[isobutane][butane]
1.250.50 + 1.50
= 0.63Q =[isobutane][butane]
1.250.50 + 1.50
= 0.63
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ButaneButane Is#&utaneIs#&utaneAssume y#u are at e%u"l"&r"um "t "s# .';0Assume y#u are at e%u"l"&r"um "t "s# .';0
M and &utane 1'01 M' N# add .'01 MM and &utane 1'01 M' N# add .'01 M&utane' ?en te system c#mes t# e%u"l"&r"um&utane' ?en te system c#mes t# e%u"l"&r"um
a!a"n, at are "s# and &utane@a!a"n, at are "s# and &utane@ 7 ;'07 ;'0
S#lut"#nS#lut"#n
Calculate Q "mmed"ately a$ter add"n! m#reCalculate Q "mmed"ately a$ter add"n! m#re&utane and c#mpare "t 7'&utane and c#mpare "t 7'
Q "s LESS T)AN 7' Tere$#re, te react"#n "llQ "s LESS T)AN 7' Tere$#re, te react"#n "lls"$t t# te KKKKKKKKKKKK's"$t t# te KKKKKKKKKKKK'
Q =[isobutane][butane]
1.250.50 + 1.50
= 0.63Q =[isobutane][butane]
1.250.50 + 1.50
= 0.63
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ButaneButane Is#&utaneIs#&utane #u are at e%u"l"&r"um "t "s# .';0 M and #u are at e%u"l"&r"um "t "s# .';0 M and
&utane 1'01 M' N# add .'01 M &utane'&utane 1'01 M' N# add .'01 M &utane'
S#lut"#nS#lut"#n
Q "s less tan 7, s# e%u"l"&r"um s"$ts r"!t JQ "s less tan 7, s# e%u"l"&r"um s"$ts r"!t J
aay $r#m &utane and t#ard "s#&utane'aay $r#m &utane and t#ard "s#&utane'Set up c#ncentrat"#n ta&leSet up c#ncentrat"#n ta&le
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ButaneButane Is#&utaneIs#&utane #u are at e%u"l"&r"um "t "s# .';0 M and #u are at e%u"l"&r"um "t "s# .';0 M and
&utane 1'01 M' N# add .'01 M &utane'&utane 1'01 M' N# add .'01 M &utane'
S#lut"#nS#lut"#n
Q "s less tan 7, s# e%u"l"&r"um s"$ts r"!t JQ "s less tan 7, s# e%u"l"&r"um s"$ts r"!t J
aay $r#m &utane and t#ard "s#&utane'aay $r#m &utane and t#ard "s#&utane'Set up c#ncentrat"#n ta&leSet up c#ncentrat"#n ta&le
&utane&utane "s#&utane"s#&utane
In"t"alIn"t"alCan!eCan!e
E%u"l"&r"umE%u"l"&r"um
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ButaneButane Is#&utaneIs#&utane #u are at e%u"l"&r"um "t "s# .';0 M and #u are at e%u"l"&r"um "t "s# .';0 M and
&utane 1'01 M' N# add .'01 M &utane'&utane 1'01 M' N# add .'01 M &utane'
S#lut"#nS#lut"#n
Q "s less tan 7, s# e%u"l"&r"um s"$ts r"!t JQ "s less tan 7, s# e%u"l"&r"um s"$ts r"!t J
aay $r#m &utane and t#ard "s#&utane'aay $r#m &utane and t#ard "s#&utane'Set up c#ncentrat"#n ta&leSet up c#ncentrat"#n ta&le
&utane&utane "s#&utane"s#&utane
In"t"alIn"t"al 1'01 > .'011'01 > .'01 .';0.';0Can!eCan!e 2 2 > >
E%u"l"&r"umE%u"l"&r"um ;'11 2 ;'11 2 .';0 > .';0 >
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ButaneButane Is#&utaneIs#&utane #u are at e%u"l"&r"um "t "s# .';0 M and #u are at e%u"l"&r"um "t "s# .';0 M and
&utane 1'01 M' N# add .'01 M &utane'&utane 1'01 M' N# add .'01 M &utane'
S#lut"#nS#lut"#n
K = 2.50 =[isobutane]
[butane]
1.25 + x
2.00 - xK = 2.50 =
[isobutane]
[butane]
1.25 + x
2.00 - x
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ButaneButane Is#&utaneIs#&utane #u are at e%u"l"&r"um "t "s# .';0 M and #u are at e%u"l"&r"um "t "s# .';0 M and
&utane 1'01 M' N# add .'01 M &utane'&utane 1'01 M' N# add .'01 M &utane'S#lut"#nS#lut"#n
.'1G M .'1G M
At te ne e%u"l"&r"um p#s"t"#n,At te ne e%u"l"&r"um p#s"t"#n,
&utane 1'34 M and "s#&utane ;'4; M'&utane 1'34 M and "s#&utane ;'4; M'
E%u"l"&r"um as s"$ted t#ard "s#&utane'E%u"l"&r"um as s"$ted t#ard "s#&utane'
K = 2.50 =[isobutane]
[butane]
1.25 + x
2.00 - xK = 2.50 =
[isobutane]
[butane]
1.25 + x
2.00 - x
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N"tr#!en D"#"de E%u"l"&r"umN"tr#!en D"#"de E%u"l"&r"umNN;;::<!=<!= ; N:; N:;;<!=<!=
Increase + "n te systemIncrease + "n te system&y reduc"n! te (#lume'&y reduc"n! te (#lume'
Kc =[NO2]
2
[N2O4] = 0.0059 at 298 KKc =
[NO2]2
[N2O4]
= 0.0059 at 298 K
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N"tr#!en D"#"de E%u"l"&r"umN"tr#!en D"#"de E%u"l"&r"um
NN;;::<!=<!= ; N:; N:;;<!=<!=
Increase + "n te system &y reduc"n! teIncrease + "n te system &y reduc"n! te(#lume'(#lume'
In !ase#us system te e%u"l"&r"um "ll s"$t t#In !ase#us system te e%u"l"&r"um "ll s"$t t#
te s"de "t $eer m#lecules <"n #rder t#te s"de "t $eer m#lecules <"n #rder t#reduce te +='reduce te +='
Tere$#re, react"#n s"$tsTere$#re, react"#n s"$ts LEFTLEFT and + #$ N:and + #$ N:;; decreases and + #$ Ndecreases and + #$ N;;::FF "ncreases'"ncreases'
Kc =[NO2]
2
[N2O4] = 0.0059 at 298 KKc =
[NO2]2
[N2O4] = 0.0059 at 298 K
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