5. Chemical Equilibria

7/26/2019 5. Chemical Equilibria

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TKM 406 Termodinamika TeknikKimia 2

Chemical Equilibria


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Reaction Coordinate

......AA......AA 33332211 ++++

3111

H3COOHCH

224 HCOOHCH

224

+=+===

++

=

==

=

=

=

ddn

.....dndndndn

i

i

4

4

3

3

2

2

1

1

=

====

=

ddn

.....3

dn

1

dn

1

dn

1

dn

i

iHCOOHCH 224


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Reaction Coordinate

===+=

++==

+=

i0i0i

0

0

i0iii

i0ii

nnnn

nn

nn

nny

nn

If, initially there are 2 mol CH4, 1 mol H2O, 1 mol CO, and 4 mol H2:

++=

++=

+=

+=

+=+++=

=+++=+++=

+=+===

=+++=+++=

====

2834y

281y

281y

282y

28nnnnn

23111

34n1n1n2n

84112nnnnn

4n1n1n2n

224

224

224

224

224

224

HCOOHCH

HCOOHCH

HCOOHCH

HCOOHCH

0,H0,CO0,OH0,CH0

0,H0,CO0,OH0,CH


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Reaction Coordinate


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Reaction Coordinate: Mlti!leReaction"

.......................................................................

......AA......AA 2,3232,3232,2222,121 ++++

......AA......AA j,3j3j,3j3j,2j2j,1j1 ++++

......AA......AA 1,3131,3131,2121,111 ++++

2224

224

H4COOH2CH

H3COOHCH

++++


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Reaction Coordinate: Mlti!leReaction"

22,i

2,i

2,4

2,4

2,3

2,3

2,2

2,2

2,1

2,1d

dn.....

dndndndn=

==

=

=

=

11,i

1,i

1,4

1,4

1,3

1,3

1,2

1,2

1,1

1,1

d

dn

.....

dndndndn

======

2

2,i

2,i2,H2,CO2,OH2,CH

11,i

1,i1,H1,CO1,OH1,CH

ddn

.....4

dn

1

dn

2

dn

1

dn

ddn.....3

dn1

dn1

dn1

dn

2224

224

=

====

=

=

====

=

jj,i

j,i

j,4

j,4

j,3

j,3

j,2

j,2

j,1

j,1d

dn.....

dndndndn=

==

=

=

=


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Reaction Coordinate

===

+=

+

+

==

+=

i

j,ij0i0i

j

jj,10

j

jj,10

j

jj,i0i

ii

j

jj,i0ii

nnnn

nn

n

n

n

ny

nn

If, initially there are 2 mol CH4, 1 mol H2O, 1 mol CO, and 4 mol H2:

21

21H

21

2CO

21

1CO

21

21OH

21

21CH

228

434y

228

y

228

1y

228

21y

228

2y

22

24

++

++=

++

=

++

+=

++

=

++

=


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Reaction Coordinate


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Reaction Coordinate #$%ili&rim Condition

( ) 0dG P,Tt =


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Reaction Coordinate #$%ili&rim Condition 'Cont()


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Method of $%ili&rim Con"tant

( ) ( ) ( ) ( ) ffffK 3H1

CO

1

OH

1

CH 224=

= TR

Gexp)aK

0ii

ii

i)fK i*or +a"e":

224 H3COOHCH ++

*or ideal +a"e":

PKKK y

=

PKKy

=


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Method of$%ili&ri

mCon"tant


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ro&lem"


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ro&lem Hint: -i.erent /ayead" to The ame Re"lt"


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ro&lem"

C l l ti f $ ili& i


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Calclation of $%ili&rimCon"tant

( )

=!

K2"8,fi!

K2"8 GG

( ) = ! K2"8,fi! K2"8 HH

2T

TR

H

dT

K#nd

=

2"8!

K2"8 K#n2"8RG =

dTCHH

T

2"8

!p

!2"8

T

+=

( ) = !pi!p CC

dT

TR

HK#nd

2

T

K#n

K#n

T

K2"8

=


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)K2"8!

fG


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)K2"8!

fG


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)K2"8!

fG


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)K2"8!

fG


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)K2"8!

fH


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)K2"8!

fH


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)K2"8!

fH


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)K2"8!

fH

ea a!ac y a a


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ea a!ac y a a 3a"e"

ea a!ac y a a


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ea a!ac y a a 3a"e"


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HeatCa!acity

-ata olid

H t C it D t Li id


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Heat Capacity Data - Liquid


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ro&lem"

ro&lem"


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ro&lem"


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ro&lem"


32/44

ro&lem"

ro&lem"


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ro&lem"


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ro&lem"


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ro&lem"


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ro&lem"


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ro&lem"


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Mlti!le Reaction"

&ed of coal 'a""me !re car&on) in a coal+a"i5er i" fed ith "team and air and !rodce a+a" "tream containin+ H2, CO, O2, H2O, CO2, and

728 If the feed to the +a"i5er con"i"t" of 1 mol of

"team and 289 mol of air, calclate thee%ili&rim com!o"ition of the +a" "tream at ; 20 &ar and T ; 1


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Mlti!le Reaction"


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ro&lem"


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ro&lem"


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ro&lem"


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a+ran+e Mlti!lier forCom!le= Reaction

0aPnn#nTRG

$

i$$ii!

fi =+ +

=i

$i$i Aan*ir"t te!: tomic >alance"

?2 te!:

7o8 of e%n ; no8 ofin@ol@ed atom

7o8 of e%n ; no8 of

"!ecie" in@ol@ed

A"e Com!ter to ol@e ll The $%ation imltaneo"ly8


44/44

ro&lem

Calclate the e%ili&rim com!o"ition at 1000 Kand 1 &ar of a +a"!ha"e "y"tem containin+ the"!ecie" CH4, H2O, CO, CO2, and H28 In the initial

nreacted "tate ther are !re"ent 2 mol of CH4

and 9 mol of H2O8 ""me ideal +a"e"8

t 1000 K:

1%!COf

1%!COf

1%! OHf

%1!CHf

&!#'3"("0G

&!#'200240G

&!#'1"2420G

&!#'1"20G

2

4

=

=

=

=

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5. Chemical Equilibria