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UBC Materials Engineering


MTRL 252: Thermodynamics of Materials

7. System Equilibria

Leili Tafaghodi

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Simultaneous Equilibria

Within gas reformer both the reforming and


shift reaction proceed
Final composition involves simultaneous
equilibria
CH 4  H 2 O( g )  CO  3H 2 (1)
CO  H 2 O  H 2  CO 2 (2)
Define extents for both reactions; 1 and 2

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Simultaneous Equilibria
CH 4  H 2 O(g )  CO  3H 2 (1)
CO  H 2O  H 2  CO 2 (2)

Stoichiometry
n CH4  n oCH4   1 n H 2O  n oH 2O   1   2

n CO  n oCO   1   2 n CO2  n oCO2   2

n H 2  n oH 2  3 1   2 n  n o  2 1

Partial Pressures 4

 n oCH   1 
p CH4  4  P
 n 
 
 n oH2O  1   2 
p H 2O   P
 n 
 
 no  1   2 
p CO   CO  P

 n 
 n oCO2   2 
p CO2   P
 n 
 
 n oH2  31   2 
p H2   P
 n 
 

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Substitute into K’s


p CO p 3H 2 X CO X 3H 2 P 2
K1  
p CH4 p H 2O X CH X H 2O
4

p H 2 p CO2 X H 2 X CO2
K2    fn( P )
p CO p H 2O X CO X H 2O

Two variables; 1 and 2; use Solver

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Example
1 mole of CH4, 2 moles of H2O and 0.1 mole of CO at total
pressure of 1 atm, react according to the following
reactions. Calculate the final equilibrium composition for
the above gas mixture. Calculate the overall Gibbs free
energy of the reaction and the Gibbs free energy of mixing.
CH 4  H 2O(g )  CO  3H 2 (1)
CO  H 2O  H 2  CO 2 (2)
Reaction 1 Reaction 2
∆G° ∆G°
Temp (K) (J/mol) K (J/mol) K
900 -1820 ? -7191 ?

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Example (continued)

Reaction 1 Reaction 2
∆G° ∆G°
Temp (K) (J/mol) K (J/mol) K
900 -1820 1.28 -7191 2.61

Initial Composition
CH4 H2O CO CO2 H2 total
mole 1 2 0.1 0 0 3.1
X 0.32 0.65 0.03 0.00 0.00 1.00

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Example (continued)

Final Comosition
CH4 H2O CO CO2 H2 total
mole 0.29 0.90 0.42 0.39 2.52 4.52
X 0.06 0.20 0.09 0.09 0.56 1.00

ε error Target
Reaction 1 0.71 0.00 0.00
Reaction 2 0.39 0.00 Target = error1 2+error2 2

Error=K from Gibbs-K from eq. composition

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Example (continued)
∆ =∆ −∆

= (1 − ) + 2− − + 0.1 + − +
(3 + ) +

─ -2 -0.1

=− + − − + − + (3 + ) +

= ∆ + ∆ = -4105 J

G M  n A RT ln p A  n B RT ln p B  n C RT ln p C ∆ =−

 RT  n A ln X A P  n B ln X B P  n A ln X B P 

Gas Phase Equilibria


Gaseous equilibria within C-O-H system
CO  H 2O  H 2  CO 2

CH 4  CO 2  2CO  2H 2

CH 4  H 2 O( g )  CO  3H 2

Equilibrium calculations performed with


specific end-use for
 Combustion; chemical energy → sensible heat
 Reduction of oxides by CO and/or H2
 Atmospheres for heat treating

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Combustion
Predict oxidation level for H2 and C
Equilibrium for methane combustion
Simultaneous Equilibria
CH 4  2O 2  CO 2  2H 2O
CO  0.5O 2  CO 2
H 2  0.5O 2  H 2 O

At elevated temperatures dissociation of CO2


and H2O occurs
Overall Reaction
CH 4  2O 2  aCO 2  bH 2 O  cCO  dH 2  eO 2
a < 1; b < 2 and c, d, e not trivial

Incomplete oxidation to CO2 and H2O →


H R less negative (exothermic)

Equilibrium Products Of Methane


Combustion 12
70

60
H2O

H2
50 CO2
CO
Mole Percent

40 O2

30

20

10

0
1500 1700 1900 2100 2300 2500
Combustion Temperature (C)

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Atmospheres for Heat


Treating
Neutral or reducing to prevent oxidation
Ti  O 2  TiO 2

Heat treating metal components requires


non-oxidizing atmosphere
1
Process atmosphere p O2  Ti/TiO2 equilibrium
K
C-O system is capable of low pO2

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The C-O System


 Considered select reactions in gaseous C-H-O
systems
 Will now examine C-O system more closely
 Case 1: n oO insufficient to consume n oC ; i.e.
2

with solid C present; 2-phase system

 Case 2: n oO > than required to consume n oC ;


2

single phase CO-CO2-O2 system

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C-O System with Solid


Carbon
C has two oxidation states; CO and CO2

Two Independent reactions


C  O 2  CO 2 (1)

2C  O 2  2CO (2)

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Other Reactions
Derived from (1) and (2)
2C  O 2  2CO (2)
C  O 2  CO 2 (1)
C  CO 2  2CO (3)

C  O 2  CO 2 (1)
C  CO 2  2CO (3)
2CO  O 2  2CO 2 (4)

 (3) and (4) obtained by manipulation of (1) and


(2)  not thermodynamically independent

 If (1) and (2) at equilibrium; (3) and (4) also at


equilibrium

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Simultaneous Equilibria
p CO2
C  O 2  CO 2 K1  (1)
a Cp O2
2
p CO
2C  O 2  2CO K2  (2)
a C2 p O2

p CO2  p CO  p O2  P (3)

3 Equations; 4 Unknowns;
a C ; p CO 2 ; p CO ; p O 2

Specify aC

Algebraic Manipulation
Specified aC
3 Equations; 3 Unknowns; p CO2 ; p CO ; p O2

 C  O 2  CO 2 p CO2  K 1a C p O2 (1)

 2C  O 2  2CO p CO  a C K 2p O 2 (2)

 Substitute into p CO2  p CO  p O2  P (3)

 Simplify  p O  1  K 1a C   a C K 2p O  P
2 2

Explicit expression for p O 2

With p O 2 ; (1) → p CO 2 ; (2) → p CO

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C-O system with Solid C 19

C-O System Equilibium (C at unit activity)


100 0
90 -5
80 -10
70 % CO -15
Percent CO

60 Log PO2 -20

Log PO2
50 -25
40 -30
30 -35
20 -40
10 -45
0 -50
200 400 600 800 1000 1200 1400
Temperature (C)

T > 1000oC; equilibrium  ‘pure’ CO

O2 always present; Oxidizing for Ti, Al, etc

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Example
950oC; P = 1; aC = 1
C  O 2  CO 2 K 1  7.96x1016

2C  O 2  2CO K 2  4.75x1018

Solver or Goal seek to find partial pressure of oxygen


Solution
p CO  0.984 p CO2  0.016 p O 2  2.04x10 19

p CO
Per mole of gas  n CO  X CO 
P

For P  1

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Molar O : C Ratio
950oC; P = 1; aC = 1
O n p CO  2p CO 2  2p O 2
 O   1.016
C nC p CO  p CO 2

Each C gasified consumes 1.016 O

For n oO  1.016n oC 22

 System is 2-phase; C and CO-CO2-O2


 Gas composition independent of O/C
 What changes is % C gasified  linear
function of initial O/C ratio

1.0
% C Gasified

n oO n oC 1.016

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C-O System; No Solid C


950oC and n oO  1.016 n oC

 All C is gasified
 Gas composition is function of O/C ratio

Without solid C need consider only


CO-CO2-O2 equilibrium
p CO2
CO  0.5O 2  CO 2 K
p CO p O0.52

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Apply Extent of Reaction
Stoichiometry
CO + 0.5O2 = CO2
n CO  n oCO   n O 2  n oO2  0.5 

n CO2  n oCO2   n  n o  0.5 

n oCO  
X CO  ; p CO  X CO P
n
n oCO  0.5 
XO2  ; pO2  XO2 P
n
n oCO 2  
X CO 2  ; p CO 2  X CO 2 P
n

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Thermodynamics
CO + 0.5O2 = CO2
X CO2
K
X CO X O0.52 P 0.5

 In theory can use Goal Seek


 At 950oC, K  3.7 x10 7 (reaction shifted far
to right)

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Direct Method
p CO2
CO  0.5O 2  CO 2 K (1)
p CO p O0.52

p CO 2  p CO  p O 2  P (2)

Get 3rd equation by specifying O/C ratio


O p CO  2 p CO2  2 p O2
 (3)
C p CO  p CO2

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Solution
p CO2
K (1)
p CO p 0O.52

From (2)  p CO  P  p CO2  p O 2 (2-b)

O p CO  2 p CO2  2 p O2
 (3)
C p CO  p CO2 Substitute into (3)
O
p CO2  ( P  p O 2 )  ( P  p O2 ) (4)
C

Therefore
O
p CO  P  ( P  p O2 )  ( P  p O2 )  p O 2 (5)
C

Substitute (4) and (5) into (1)

(1) now explicit expression for p O 2

Gas Composition Versus O/C ratio at 950C


0

-2
CO
-4 CO2

-6

-8
Log (p)

-10

-12 O2

-14

-16 O2
CO2
-18 CO
-20
0.0 0.5 1.0 1.5 2.0 2.5
O/C Ratio

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C Activity in Gas Phase


 Solid carbon not present in the gas
 However can still calculate aC
2
 p CO 
C  CO 2  2CO log a C  log  

 K p CO 2 

Gas Phase aC
Gas of aC in contact with steel [aC]
CO; CO 2 ; a C

[ aC ]

aC
[C]  C G  RT ln
[a C ]

Component will escape from higher activity


to lower activity (G < 0)

 If [aC] > aC gas is decarburizing


 If [aC] = aC gas is neutral
 If [aC] < aC gas is re-carburizing

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CO-CO2 Mixtures 31

Soot Formation
CO-CO2 can form C ‘soot’
2CO  C  CO 2

G o  169,008  172.19T

 Exothermic  shifts to right as T 


 moles of gas  shifts to right as P 
 If C formed → aC = 1
p CO2
 Equilibrium is 2
 K
p CO

2CO=C + CO2 32
The Equilibrium for Soot Formation
4

2 No Soot
Log(PCO2/PCO)

-1

-2 5 atm

-3 1 atm
0.5 atm
-4 0.1 atm

-5
400 600 800 1000 1200 1400
Temperature (C)

 Below equilibrium → CO2 lean → soot


formation
 Inhibited by T  and P 

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