Thermodynamics: An Engineering Approach
Thermodynamics: An Engineering Approach
9th Edition
ISBN: 9781259822674
Author: Yunus A. Cengel Dr., Michael A. Boles
Publisher: McGraw-Hill Education
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Chapter 16.6, Problem 15P

(a)

To determine

The logarithm equilibrium constant for the reaction at 1440 R.

Compare the results for the values of KP obtained from the equilibrium constants of Table A-28.

(a)

Expert Solution
Check Mark

Answer to Problem 15P

The logarithm equilibrium constant for the reaction at 1440 R is 4.93×1014_.

The equilibrium constant obtained from the equilibrium constants of Table A-28 at 1440Ris 6.4712×1016_.

Explanation of Solution

Express the standard-state Gibbs function change.

ΔG*(T)=vH2g¯*H2(T)+vO2g¯*O2(T)vH2Og¯*H2O(T)=vH2(h¯Ts¯)H2+vO2(h¯Ts¯)O2vH2O(h¯Ts¯)H2O=[vH2(h¯f,H2o+(h¯H2h¯oH2)Ts¯H2)+vO2(h¯fo,O2+(h¯O2h¯oO2)Ts¯O2)vH2O(h¯fo,H2O+(h¯H2Oh¯oH2O)Ts¯H2O)] (I)

Here, the Gibbs function of components H2,O2,andH2O at 1 atm pressure and temperature T are g¯*H2(T),g¯*O2(T),andg¯*H2O(T) respectively, enthalpy on the unit mole basis of H2,O2,andH2O are h¯H2,h¯O2,andh¯H2O respectively, absolute entropy of H2,O2,andH2O are s¯H2,s¯O2,ands¯H2O, temperature of H2,O2,andH2O are TH2O,TCO,TH2,andTCO2, sensible enthalpy at the specified state of H2,O2,andH2O are h¯H2,h¯O2,andh¯H2O, the sensible enthalpy at the standard reference state of 25°C and 1 atm of H2,O2,andH2O are h¯H2o,h¯O2o,andh¯H2Oo, the enthalpy of formation at a specified states of 25°C and 1 atm for the components H2,O2,andH2O are h¯f,H2o,h¯f,O2o,andh¯f,H2Oo, stoichiometric coefficients of components H2,O2,andH2O are vH2,vO2,andvH2O respectively.

Write the equation to calculate the natural logarithms of equilibrium constant for the chemical equilibrium of ideal-gas mixtures.

lnKP=ΔG*(T)RuT (II)

Here, universal gas constant is Ru and temperature of Gibbs function of formation is T.

Write the equation to calculate the equilibrium constant for the chemical equilibrium of ideal-gas mixtures.

KP=e(ΔG*(T)RuT) (III)

Conclusion:

From the equilibrium reaction, the values of vH2O,vCO,vH2,andvCO2 are 1, 1, 1, and 1 respectively.

Refer Table A-26, obtain the values of h¯f,H2o,h¯f,O2o,andh¯f,H2Oo as below:

h¯f,H2o=0h¯f,O2o=0 h¯f,H2Oo=104,040 Btu/lbmol

Refer Table A-22, obtain the value of h¯H2o at temperature of 537 R.

h¯H2o=3640.3Btu/lbmol

Refer Table A-22, obtain the value of h¯H2 and s¯H2 at temperature of 1440R.

h¯H2=9956.9Btu/lbmols¯H2=38.079Btu/lbmolR

Refer Table A-19E, obtain the value of h¯O2o at temperature of 537 R.

h¯O2o=3725.1 Btu/lbmol

Refer Table A-19E, obtain the value of h¯O2 and s¯O2 at temperature of 1440 R.

h¯O2=10532.0Btu/lbmols¯O2=56.326Btu/lbmolR

Refer Table A-23, obtain the value of h¯H2Oo at temperature of 537 R.

h¯H2Oo=4258.0Btu/lbmol

Refer Table A-23, obtain the value of h¯H2O and s¯H2O at temperature of 2500 K.

h¯H2Oo=11993.4Btu/lbmols¯H2O=53.428Btu/lbmolR

Substitute 1 for vH2, 0 for h¯foH2, 9956.9Btu/lbm for h¯H2 , 3640.3 Btu/lbm for h¯oH2, 1440 R for T, 38.079Btu/lbmR for s¯H2, 0.5 for vO2, 0 for h¯fo,O2, 10532.0Btu/lbm for h¯O2, 3725.1 Btu/lbm for h¯oO2, 56.325Btu/lbmR for s¯O2, 1 for vH2O, 104,040 Btu/lbm for h¯fo,H2O, 11,933.4Btu/lbm for h¯H2O, 4258Btu/lbm for h¯oH2O, and 53.428Btu/lbmR for s¯H2O in Equation (I).

ΔG*(T)=[1(0+(9956.9Btu/lbm3640.3 Btu/lbm)1440R×38.079Btu/lbmR)H2+0.5(0+(10532.0Btu/lbm3725.1 Btu/lbm)1440R×56.325Btu/lbmR)O21(104,040 Btu/lbm+(11,933.4Btu/lbm4258Btu/lbm)1440R×53.428Btu/lbmR)O2]=87,632 Btu/lbmol

Substitute 87,632Btu/lbmol for ΔG*(T), 1440 R for T, and 1.986Btu/lbmolR for Ru in Equation (II).

KP=87,632Btu/lbmol(1.986Btu/lbmolR)×1440R=30.64

Substitute 30.64 for KP in Equation (III).

KP=e(30.64)=4.93×1014

Thus, the equilibrium constant obtained from the equilibrium reaction at 1440R is 4.93×1014_.

Convert the temperature from Rankine to Kelvin.

T=1440R×1 K1.8 R=800 K

Refer Table A-28, “Natural logarithms of the equilibrium constant” obtain the equilibrium constant for the reaction by interpolating for the temperature of 800 K as 34.974_.

Substitute 34.974 for KP in Equation (III).

KP=e(34.974)=6.4712×1016

Thus, the equilibrium constant obtained from the table A-28  at 1440 R is 6.4712×1016_.

Refer Table A-28 “Natural logarithms of the equilibrium constant”, obtain the equilibrium constant for the dissociation reaction N22N  at 3000 k is lnKP=22.359

The value obtained for equilibrium constant at 1440R from the definition of the equilibrium constant is 30.64 which is smaller than the value obtained for equilibrium constant at 34.974 from the Table A-28.

(b)

To determine

The logarithm equilibrium constant for the reaction at 3960 R.

Compare the results for the values of KP obtained from the equilibrium constants of Table A-28.

(b)

Expert Solution
Check Mark

Answer to Problem 15P

The logarithm equilibrium constant for the reaction at 3960 R is 1.125×103_.

The equilibrium constant obtained from the equilibrium constants of Table A-28 at 3960 R is.

1.150×103_

Explanation of Solution

Express the standard-state Gibbs function change.

ΔG*(T)=vH2g¯*H2(T)+vO2g¯*O2(T)vH2Og¯*H2O(T)=vH2(h¯Ts¯)H2+vO2(h¯Ts¯)O2vH2O(h¯Ts¯)H2O=[vH2(h¯f,H2o+(h¯H2h¯oH2)Ts¯H2)+vO2(h¯fo,O2+(h¯O2h¯oO2)Ts¯O2)vH2O(h¯fo,H2O+(h¯H2Oh¯oH2O)Ts¯H2O)]                                      (IV)

Here, the Gibbs function of components H2,O2,andH2O at 1 atm pressure and temperature T are g¯*H2(T),g¯*O2(T),andg¯*H2O(T) respectively, enthalpy on the unit mole basis of H2,O2,andH2O are h¯H2,h¯O2,andh¯H2O respectively, absolute entropy of H2,O2,andH2O are s¯H2,s¯O2,ands¯H2O, temperature of H2,O2,andH2O are TH2O,TCO,TH2,andTCO2, sensible enthalpy at the specified state of H2,O2,andH2O are h¯H2,h¯O2,andh¯H2O, the sensible enthalpy at the standard reference state of 25°C and 1 atm of H2,O2,andH2O are h¯H2o,h¯O2o,andh¯H2Oo, the enthalpy of formation at a specified states of 25°C and 1 atm for the components H2,O2,andH2O are h¯f,H2o,h¯f,O2o,andh¯f,H2Oo, stoichiometric coefficients of components H2,O2,andH2O are vH2,vO2,andvH2O respectively.

Write the equation to calculate the natural logarithms of equilibrium constant for the chemical equilibrium of ideal-gas mixtures.

lnKP=ΔG*(T)RuT (V)

Here, universal gas constant is Ru and temperature of Gibbs function of formation is T.

Write the equation to calculate the equilibrium constant for the chemical equilibrium of ideal-gas mixtures.

KP=e(ΔG*(T)RuT) (VI)

Conclusion:

From the equilibrium reaction, the values of vH2O,vCO,vH2,andvCO2 are 1, 1, 1, and 1 respectively.

Refer to Table A-26; obtain the values of h¯f,H2o,h¯f,O2o,andh¯f,H2Oo as below:

h¯f,H2o=0h¯f,O2o=0 h¯f,H2Oo=104,040 Btu/lbmol

Refer to Table A-22, obtain the value of h¯H2o at temperature of 537 R.

h¯H2o=3640.3Btu/lbmol

Refer to Table A-22, obtain the value of h¯H2 and s¯H2 at temperature of 3960 R.

h¯H2=29,370.5Btu/lbmols¯H2=45.765Btu/lbmolR

Refer to Table A-19E, obtain the value of h¯O2o at temperature of 537 R.

h¯O2o=3725.1 Btu/lbmol

Refer to Table A-19E, obtain the value of h¯O2 and s¯O2 at temperature of 1440 R.

h¯O2=32,441.0Btu/lbmols¯O2=65.032Btu/lbmolR

Refer to Table A-23, obtain the value of h¯H2Oo at temperature of 537 R.

h¯H2Oo=4258.0Btu/lbmol

Refer to Table A-23, obtain the value of h¯H2O and s¯H2O at temperature of 2500 K.

h¯H2Oo=39,989Btu/lbmols¯H2O=64.402Btu/lbmolR

Substitute 1 for vH2, 0 for h¯foH2, 29370.5Btu/lbm for h¯H2 , 3640.3 Btu/lbm for h¯oH2, 3960 R for T, 45.765Btu/lbmR for s¯H2, 0.5 for vO2, 0 for h¯fo,O2, 32,441Btu/lbm for h¯O2, 3725.1 Btu/lbm for h¯oO2, 39650Btu/lbmR for s¯O2, 1 for vH2O, 104,040 Btu/lbm for h¯fo,H2O, 39,989Btu/lbm for h¯H2O, 4258Btu/lbm for h¯oH2O, and 64.402Btu/lbmR for s¯H2O in equation (IV).

ΔG*(T)=[1(0+(29370.5Btu/lbm3640.3 Btu/lbm)3960R×45.765Btu/lbmR)H2+0.5(0+(32,441Btu/lbm3725.1 Btu/lbm)3960R×65.032Btu/lbmR)O21(104,040 Btu/lbm+(39,989Btu/lbm4258Btu/lbm)3960R×64.402Btu/lbmR)O2]=53,436 Btu/lbmol

Substitute 53,436Btu/lbmol for ΔG*(T), 3960 R for T, and 1.986Btu/lbmolR for Ru in Equation (V).

lnKP=53,436Btu/lbmol(1.986Btu/lbmolR)×3960R=6.79

Substitute 6.79 for KP in Equation (VI).

KP=e(6.79)=888.91

Thus, the equilibrium constant obtained from the equilibrium reaction at 3960 R is 1.120×103_.

Convert the temperature from Rankine to Kelvin.

T=3960R×1 K1.8 R=2200 K

Refer Table A-28, “Natural logarithms of the equilibrium constant” obtain the equilibrium constant for the reaction by interpolating for the temperature of 2200 K as 6.768.

Substitute 6.768 for KP in equation (VI).

KP=e(6.768)=1.150×103

Thus, the equilibrium constant obtained from the table A-28 at3960 R is 1.150×103_.

The value obtained for equilibrium constant at 3960R from the definition of the equilibrium constant is 6.79 which is almost equal to the value obtained for equilibrium constant as 6.768 from the Table A-28.

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Chapter 16 Solutions

Thermodynamics: An Engineering Approach

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