ENGRD 221 Prof. N.

Zabaras Problem 1

Solutions to Homework 12

11/28/2007

1 Known: The reaction is: CO2 CO + O2 2 Find: Determine log10 K at (a) 500 K (b) 1800 oR

Assumption: Ideal gas principles apply Analysis: We use the equilibrium condition o (1) ln K = G RT 1 o o o (2) where G o = g CO + gO g CO 2 2 2 with g = h Ts (3)

h = h fo + h (4),
where h fo is the enthalpy of formation from Table A-25 and h is the difference between the enthalpy at the given temperature minus the enthalpy at 298 K (from Table A-23) Combing the equations (2)-(4) gives: 1 1 o o o G o = h fo + h CO + h fo + h O h fo + h CO T sCO + sO sCO (5) 2 2 2 2 2 2 where the o symbol means that the property is evaluated at the given temperature and 1 atm of pressure.

] [

(a) T = 500 K, plugging in values from tables A-23 and A-25 into Eq. (5): 1 [ 110,530 + (14,600 8,669 )] + 2 [0 + (14,770 8,682 )] [ 393,520 + (17,678 9,364 )] G o = 500 212.719 + 1 (220.589 ) 254.814 2 o G = 239,551 kJ kmol Using this in Eq. (1) results in: kJ 239,551 o G kmol = ln K = log10 K = 25.027 , which matches closely kJ RT 8.314 500 K kmol K with the value presented in Table A-27 of log10 K = 25.025

(b) T = 1800 oR = 1000K. This analysis is the same as in part (a), except now the h will be evaluated from 500 K to 1000 K:

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ENGRD 221 Prof. N. Zabaras

Solutions to Homework 12

11/28/2007

1 [ 110,530 + (30,355 8,669)] + 2 [0 + (31,389 8,682)] [ 393,520 + (42,769 9,364)] G o = 1 1000 234.421 + (243.471) 269.215 2

G o = 195,683 kJ

kmol

Using this in Eq. (1) results in: kJ 195,683 G o kmol = ln K = log10 K = 10.222 , which matches closely kJ RT 8.314 1000 K kmol K with the value presented in Table A-27 of log10 K = 10.221

Problem 2

Let y be the mole fraction of P4, therefore (1-y) is the mole fraction of P2. The equilibrium constant is then given as:

(1 y ) 2 Ptotal 2 1 ( ) = K eq (T ) y Pref
Therefore,

(1 y ) 2 K eq (T ) = Ptotal y Pref
As stated, the mole fractions of P4 and P2 are equal, so y = at Ptotal = Pref = 1 atm implies that Keq = at 1430K. Note: If the initial mole fractions are equal (and they sum to one), yP4 = yP2 = 1/2. If Ptotal = 3/8 atm, then

(1 y ) 2 1/ 2 = , or y 3/8

y2

10 1 y + 1 = ( y )( y 3) 3 3

Thus y = 1/3 is the only solution that makes sense for a mole fraction as you cannot have a mole fraction greater than unity.

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ENGRD 221 Prof. N. Zabaras Problem 3

Solutions to Homework 12

11/28/2007

(a) Only the chemical potential of He must be equal across the membrane because the amount of He is the only exchangeable extensive quantity:
left , final right , final He = He or

0 He

left , final right , final PHe PHe 0 + RT ln = He + RT ln Pref Pref

or

left , final right , final PHe = PHe

(b) Write equations expressing any constraints on the system. The total number of He atoms in the system are fixed:

Multiply both sides by RT/Vchamber where Vchamber is half of the total volume (we can do this because the volumes on both sides are equal). We can then write the following:

Therefore:
left , final right , final PHe = PHe =

1 left ,init 1 1 3 right , init + PHe ( PHe ) = ( + 1) = 2 2 2 4

Partial pressure should increase in the left chamber because it is initially lower there. Partial pressures of Xe in both the chambers remain same as their initial values.

Problem 4 Known: The reactions are specified as: 1. CO + H 2 O H 2 + CO2 (1) 2. 2CO2 2CO + O2 (2) 3. 2 H 2 O 2 H 2 + O2 (3)

K3 Find: Show that the equilibrium constants are related by the expression K 1 = K 2 Assumptions: (1) Ideal gas principles apply. (2) The temperature is T.

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ENGRD 221 Prof. N. Zabaras Solutions to Homework 12 11/28/2007 Analysis: Rearranging Eq. 14.31, the equilibrium constants corresponding to the three reactions have the forms: G o (1) G o (3) G o (2 ) ln K1 = ln K 2 = ln K 3 = , , RT RT RT where o o o o (G o )(1) = g H + g CO g CO gH 2 2 2O

(G ) (G )
o o

( 2) (1)

o o o = 2 g CO + gO g CO 2 2 o o o = 2g H + gO 2g H 2 2 2O

From inspection it is evident that (G o )(1) = 1 ( G o )( 3) (G o )( 2 ) 2 Dividing through by R T gives: (G o )(1) = 1 (G o )(3) (G o )(2) RT R T R T 2 Using Eq. 14.31 this becomes: 1 ln K 1 = [ln K 3 ln K 2 ] 2 Which can then be reduced to:

K3 K1 = K 2

ps. The whole problem can also be seen as follows: Reaction 1 can be written as a combination of reactions 2 and 3: (1) = (2) + (3) (try it!). Thus

(G )
o

(1)

1 (G o )(3) (G o )(2) and since RTlnK=- Go , we conclude: 2

1 2

1 2

ln K1 =

K 1 1 K [ln K3 ln K 2 ] = 2 ln K 3 = ln( K 3 )1/ 2 2 2 2

Problem 5 Known: (a) One kmol of N2O4 dissociates to form an equilibrium mixture of N2O4 and NO2 at 25 oC. (b) One kmol of CH4 dissociates to form an equilibrium mixture at 1000 K, 5 atm. For C + 2 H 2 CH 4 , log10 K = 1.011 at 1000 K. Find: In each case determine the equilibrium composition. Assumption: Ideal gas mixture principles apply. Analysis:

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ENGRD 221 Prof. N. Zabaras Solutions to Homework 12 11/28/2007 (a) Applying conservation of mass: N 2 O4 N 2 O4 + NO2 1 (1-x) + y N: 2(1-x) + y = 2, or y = 2x, where (1-x) is the amount of N2O4 present in the final mixture. The total number of moles of mixture is n = (1-x) + 2x = 1 + x. At equilibrium N 2 O4 2 NO2 , so the equilibrium constant takes the form
2x 2 2 1 1 + x 2 [ 2 x] 8x2 p = K= = 1 x pref (1 x )(1 + x ) 1 x 2 1+ x
2

(1)

Using the equilibrium condition with the given G o value: kJ 5400 o G kmol = ln K = K = 0.11322 (2) kJ RT 8.314 (298.15 K ) kmol K Combining Eqs. (1) and (2) gives: 8x 2 = 0.11322 8.11322 x 2 = 0.11322 x = 0.118 1 x2 Therefore 1-x = 0.882 and y = 2x = 0.236, so there are 0.882 kmol of N2O4 and 0.236 kmol of NO2. (b) From mass balance: 1CH 4 (1 x )CH 4 + 2 xH 2 + xC , where the total number of moles in the mixture, n, is 1-x + 2x + x = 1+2x. The equilibrium constant reads for C + 2 H 2 CH 4 :
1 x 1 2 1 1+ 2x (1 x ) (1 + 2 x)2 2 (1 x ) 1 + 2 x 2 1 p K= = ( 5) = 2 2 pref ( x) 2 x 25 x 2 x ( x )( 2 x ) 1 + 2 x 1 + 2 x

Given log 10 K = 1.011 K = 101.011 = 10.257 :

2 ( 1 x) 1 + 2x 256.413 = (x ) 2 x

Using the solver function in Excel, on a programmable calculator, or by another favorite method of yours, we compute x = 0.1088, so there are 1-x = 0.8912 kmol of CH4, 2x = 0.2176 kmol of H2, and x = 0.1088 kmol of C.

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ENGRD 221 Prof. N. Zabaras Problem 6

Solutions to Homework 12

11/28/2007

Known: A gaseous mixture with a specified molar analysis is heated at a pressure of 1.5 bar and forms an equilibrium mixture of CO2, CO, and O2 at 3000 K (Please note that in the problem by mistake we gave 2000K so the results here maybe a bit different from the ones you submitted to us!). Find: Determine the molar analysis of the equilibrium mixture. Assumptions: (1) The analysis is based on 1 kmol of initial mixture. (2) The equilibrium mixture is modeled as an ideal gas mixture. Analysis: On the basis of 1 kmol of initial mixture, the reaction is 0.2CO2 + 0.4CO + 0.4O2 CO2 + CO + O2 Writing equations for the quantities of each element present reduces the coefficients as follows: C: 0.2 + 0.4 = + = 0.6 1 O: 2(0.2) + 0.4 + 2(0.4) = 2 + + 2 1.6 = 2 + (0.6 ) + 2 = 2 So 1 0.2CO2 + 0.4CO + 0.4O2 CO2 + (0.6 )CO + O2 2 1 2 .2 The amount of the mixture is n = + (0.6 ) + = 2 2 At equilibrium, this is just the dissociation reaction for carbon dioxide: 1 CO2 CO + O2 2 So the equilibrium constant takes the form:
0.6 2.2 ) ( 2 1 2 2.2 ( ) 2
1 2

K=

( 2.2 )
2

p pref

1 1+ 1 2

p 1 .5 (0.6 ) 1 = K= p ref 1.01325 2 .2

[1.21671]

From Table A-27 at 3000 K, log10 K = 0.485 K = 0.32734

0.32734 0.6 1 = Thus 1.21671 2.2

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ENGRD 221 Prof. N. Zabaras Solutions to Homework 12 11/28/2007 Using an equation solver or iteration with a hand calculator, = 0.408 2.2 0.408 n= = 0.896 2 So the analysis of the equilibrium mixture in terms of mole fractions is 0.408 y CO2 = = = 0.4554 n 0.896 0.6 0.192 y CO = = = = 0.2143 n n 0.896 1 2 = 0.296 = 0.3304 y O2 = = n n 0.896 But by the assumption that n = 1 kmol, the analysis can be expressed as 45.54% CO2, 21.43% CO, and 33.04% O2.
Problem 7 Known: CO2 gas at 25 oC, 5.1 atm enters a heat exchanger operating at steady state. An equilibrium mixture of CO2, CO, and O2 exits at 2800 K, 5 atm. Find: Determine the composition of the exiting mixture and the heat transfer per kmol of CO2 entering.

Schematic & Given Data:

Assumptions: (1) The control volume shown in the accompanying figure is at steady state with  Wcv = 0 and negligible effects of kinetic and potential energy. (2) The ideal gas model applies to the incoming CO2 and the exiting equilibrium mixture. Analysis:
1 At equilibrium CO2 CO + O2 and the reaction has the form 2 x 1CO2 (1 x )CO2 + xCO + O2 2

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ENGRD 221 Prof. N. Zabaras

Solutions to Homework 12 x 2+ x . The amount of mixture is n = (1 x ) + x + =

2 2
x x 2 ( x + 2) ( x + 2) 2 2 K= 1 x x + 2) ( 2
1 2

11/28/2007

The equilibrium constant takes the form

p pref

x 5x = 1 x x + 2

x 5x 2 From Table A-27 at 2800 K, log10 K = 0.825 K = 0.14962 = 1 x x + 2 Using a solver function or an iteration method, x = 0.1867, so the equilibrium has the following composition in kmol per kmol of CO2 entering the heat exchanger: CO2: 1-x = 0.8133 CO: x = 0.1867 O2: x/2 = 0.09335 The energy rate balance for a control volume at steady state neglecting kinetic and potential energy effects can be written as:   Q W 0 = cv cv + ni hi (Ti ) ne he (Te ) i i n n i e  Q = cv + 1 hCO2 (T1 ) 0.8133 h fo + h CO + 0.1867 h fo + h CO + 0.09335 h fo + h O 2 2  CO2 n

+ 0.09335 h fo + h (T2 ) h (298) O h fo

2

 Q cv = 0.8133 h fo + h (T2 ) h (298) CO + 0.1867 h fo + h (T2 ) h (298) CO 2  CO2 n

[ ]

CO2

Using values from the ideal gas tables, A-23 and A-25:  Q cv = 0.8133[ 393,520 + 149,808 9,364] + 0.1867[ 110.530 + 94,784 8,669]  CO2 n
+ 0.09335[0 + 98,826 8,682] [ 393,520] = 191,550 kJ kmol (CO2 )

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