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SolutionsManual CH 02

SolutionsManual Ch 02

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904 views92 pages

SolutionsManual CH 02

SolutionsManual Ch 02

Uploaded by

King Aragorn
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© © All Rights Reserved
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PROBLEM 2-1

Determine the mass fraction of O2 and N2 in air, assuming the molar composition is 21 percent O2
and 79 percent N2.

GIVEN: Air with a molar composition of 79% N2 and 21% O2

FIND: The mass fraction of O2 and N2 in the air

APPROACH: This is a simple conversion problem using:


MWi
MWmix = ∑ χi MWi and Yi = χi
MWmix
0.79 and χO2 =
Given the molar composition: χ N2 = 0.29
mixture molecular weight:
MWmix = Σχi MWi = χ N2 MWN2 + χO2 MWO2
= 0.79 ( 28.013) + ( 0.21) ( 32 )= 28.85 kg/kmol
mass fraction of O2 and N2
 MWO2   32 
YO2 = χ O2  =0.21 =0.233
 MWmix   28.85 
 MWN2   28.013 
YN2 =
χ N2  =0.79  =0.767
 MWmix   28.85 

COMMENT: Note that YO2 > χO2 since MWO2 > MWmix and that ∑ Yi =
1 as would be expected.

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written consent of McGraw-Hill Education. 2-30
PROBLEM 2-2

A mixture is composed of the following number of moles of various species:


Species No. of moles
CO 0.095
CO2 6
H2O 7
N2 34
NO 0.005
A. Determine the mole fraction of nitric oxide (NO) in the mixture. Also, express your result as
mole percent, and as parts-per-million.
B. Determine the molecular weight of the mixture.
C. Determine the mass fraction of each constituent.

GIVEN: The following mixture:

Species # Moles χi Yi MWi


CO 0.095 0.002 0.002 28.010
CO2 6 0.127 0.195 44.011
H2O 7 0.149 0.094 18.016
N2 34 0.722 0.707 28.013
NO 0.005 106 × 10−6 111 × 10−6 30.006
TOTAL 47.1 1.0 1.0

FIND:

a) The mole fraction, mole %, and ppm of NO in the mixture


b) Determine the MW of the mixture
c) Determine the mass fraction of each constituent

Ni N NO 0.005
a)=
χi = =
∑ N i N CO + N CO2 + N H2O + N N2 + N NO 0.095 + 6 + 7 + 34 + 0.005

χ NO = 106 ×10−6 kmol/kmol-mix


MOLE % =χi ⋅100 =0.0106 %
# NO N NO ⋅ A
PPM = (1×106 ) = (1×106 ) =
χ NO (1×106 ) =
106 ppm
TOT # ∑ Ni ⋅ A
where A ≡ Avogadro’s Number

b) MWmix = ∑ χi MWi = χCO MWCO + χCO2 MWCO2 + χ H2O MWH2O + χ N2 MWN2 + χ NO MWNO

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where χCO , χCO2 , χ H2O , and χ N2 are found in the same manner as χ NO was found

MWmix
= ( 0.002 )( 28.010 ) + ( 0.127 )( 44.011) + ( 0.149 )(18.016 ) + 0.722 ( 28.013) + (106 ×10−6 ) ( 33.006 )
MWmix = 28.6 kg/kmol-mix
c)
Yi = χi
MWi =CO: Y (=
0.002 )( 28.01/28.6 ) 0.002
MWmix =CO 2 : Y (=
0.127 )( 44.011/28.6 ) 0.195
( kgi /kg mix ) =H 2 O: Y (=
0.149 )(18.016/28.6 ) 0.094
=N 2 : Y (=0.722 )( 28.013/28.6 ) 0.707
NO: Y = (106 ×10−6 ) ( 30.006/28.6 ) =
111×10−6

χi (1×106 ) and that ∑ χi =1 and ∑ Yi =


COMMENT: Note that ppmi = 1 can often be used to

check your calculations

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PROBLEM 2-3

Consider a gaseous mixture consisting of 5 kmol of H2 and 3 kmol of O2. Determine the H2 and
O2 mole fractions, the molecular weight of the mixture, and the H2 and O2 mass fractions.

GIVEN: Mixture with 5 kmole H2 and 3 kmole O2

FIND: χ H2 , χ O2 , MWmix , YH2 , YO2

SOLUTION:
Ni 5
a) =
χi ; χ=
H2 = 0.625
N tot 5+3
χO2 = 1 − χ H2 = 1 − 0.625 = 0.375
b) MWmix = ∑ χi MWi = χ H2 MWH2 + χO2 MWO2
= 0.625 ( 2.016 ) + .375 ( 31.999 )
MWmix = 13.260
MWi 2.016
c) Yi =
χi ; YH2 =
0.625 0.095
=
MWmix 13.260
YO2 =
1 − YH2 =
1 − 0.095 =0.905

COMMENT: Even though the mole fraction of H2 is large, its low molecular weight results in its
having a small mass fraction.

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written consent of McGraw-Hill Education. 2-33
PROBLEM 2-4

Consider a binary mixture of oxygen and methane. The methane mole fraction is 0.2. The mixture
is at 300 K and 100 kPa. Determine the methane mass fraction in the mixture and the methane
molar concentration in kmol of methane per m3 of mixture.

0.2
GIVEN: O2−CH4 mixture @ 300 K & 100 kPa; χO2 =

FIND: YCH4 , N CH4 / ∀

ASSUMPTIONS: ideal gas mixture

SOLUTION:

MWCH4
a) YCH4 = χCH4
MWmix
MWCH4
= χCH4
( )
χCH4 MWCH4 + 1 − χCH4 MWO2
16.043 0.2 (16.043)
0.2
=
0.2 (16.043) + 0.8 ( 31.999 ) 28.808
YCH4 = 0.111

b) PCH4 ∀ = N CH4 R u T; PCH4 = χCH4 P


χCH4 P
N CH4 /∀ =
R uT

=
(=
0.2 )100.103
8.018.10−3
kmol
8315 ( 300 ) m3

COMMENT: Careful treatment of units is required in part b.

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written consent of McGraw-Hill Education. 2-34
PROBLEM 2-5

Consider a mixture of N2 and Ar in which there are three times as many moles of N2 as there are
moles of Ar. Determine the mole fractions of N2 and Ar, the molecular weight of the mixture, the
mass fractions of N2 and Ar, and the molar concentration of N2 in kmol/m3 for a temperature of
500 K and a pressure of 250 kPa.

GIVEN: N2-Ar mixture with N N2 = 3 N Ar ;


T = 500 K; P = 250 kPa

FIND: χ i , MWmix , Yi , N N2 /∀

ASSUMPTION: ideal gas mixture

SOLUTION:
N N2 3N Ar 3
a) χ N2 = = = = 0.75
N mix 3N Ar + N Ar 4
χ Ar =1 − 0.75 = 0.25
b) MWmix = ∑ χi MWi
= 0.75 ( 28.014 ) + 0.25 ( 39.948 )
MWmix = 30.998
MWN2 28.014
c) YN2 χ=
= N2 0.75
= 0.678
MWmix 30.998
YAr =
1 − YN2 =
0.322

d) PN2 ∀ N=
= N 2 R u T; PN 2 χ N2 Ptot
χ N2 Ptot ( 0.75) 250 ⋅ 103
N=
N2 / ∀ = = 0.0451 kmol N2 /m3
RuT 8315 ( 500 )

COMMENT: Careful treatment of units is required in part d.

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PROBLEM 2-6

Determine the standardized enthalpy in J/ kmolmix of a mixture of CO2 and O2 where χCO2 =
0.10
and χCO2 =
0.90 at a temperature of 400 K.

GIVEN: CO2-O2 mixture with


= χ CO2 0.1;
= χ O2 0.9 ; T = 400 K

FIND: Standardized enthalpy of mixture

ASSUMPTION: Ideal-gas behavior

SOLUTION: This is a straightforward application of Eqn. 2.15a combined with the definition of
standardized enthalpy (Eqn. 2.34).
h CO2 = h fo,CO2 + ∆h S,CO2 = −393,546 + 4003 ( Table A.2 )
= −389,543kJ kmol
h O2 = h fo,O2 + ∆h S,O2 = 0 + 3031= 3031 kJ/kmole ( Table A.11)
h mix = ∑ χi h i = χCO2 h CO2 + χO2 h O2 ( Eqn. 2.15a )
0.1( 389,543) + 0.9 ( 3031)
=−
h mix = −36, 226 kJ/kmolmix

COMMENTS: The use of Appendix A tables made this problem simple. Note that the same
information is available as curvefit equations in Table A-13.

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PROBLEM 2-7

Determine the molecular weight of a stoichiometric (Φ = 1.0) methane–air mixture.

GIVEN: A stoichiometric mixture of methane and air

FIND: The mixture molecular weight

ASSUMPTIONS: Air consists of N2 and O2 and has the following composition: 21% O2 and
79% N2 by volume

APPROACH: Determine the stoichiometric ratio of air and fuel and then find the constituent
mole fractions and MWmix
Stoichiometric relation: C x H y + aO 2 + 3.76aN 2 → xCO 2 + y/2 H 2 O + 3.76 aN 2
methane: x = 1, y = 4 → a = x + y/4 = 2
so the air-fuel stoichiometric mixture is
1CH 4 + 2O 2 + 7.52N 2
N CH4 N CH4 1
=N CH4 1 =χ CH4 = = = 0.095
N TOT N CH4 + N O2 + N N2 10.52
N O2 2
N O2 2
= χ O2
= = = 0.190
N TOT 10.52
N N2 7.52
N N2 7.52
= χ N2
= = = 0.715
N TOT 10.52
MWmix =
∑ χ i MWi =
χ CH4 MWCH4 + χ O2 MWO2 + χ N2 MWN2
= ( 0.095)(16.043) + ( 0.190 )( 32 ) + ( 0.715)( 28.013)
MWmix = 27.6 kg/kmole

COMMENT: If this was a fuel-rich or fuel-lean mixture,


x + y/4
=a = where φ equivalence ratio
φ

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written consent of McGraw-Hill Education. 2-37
PROBLEM 2-8

Determine the stoichiometric air–fuel ratio (mass) for propane (C3H8).

GIVEN: A stoichiometric air-propane (C3 H8) mixture

FIND: The stoichiometric A/F ratio (mass)

ASSUMPTIONS: Air is comprised of 79% N2 and 21% O2 by volume

APPROACH: Determine the molar A/F ratio and convert to mass A/F ratio
Stoichiometric relation: C3 H8 + aO 2 + 3.76aN 2 → 3CO 2 + 4H 2 O + 3.76aN 2
x + y/4
=a = x 3,= y 8,= φ 1
φ
a =5
a + 3.76a 4.76a
Molar A/F ratio:
= A/F =
1 1
 MWair   MWair 
= Mass A/F ratio (= A/F )molar   4.76a  
 MWfuel   MWfuel 
A  28.85 
  = 4.76 ( 5 )  
 F  MASS  44.096 
( A/F )MASS = 15.6

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written consent of McGraw-Hill Education. 2-38
PROBLEM 2-9

Propane burns in a premixed flame at an air–fuel ratio (mass) of 18:1. Determine the equivalence
ratio Φ.

GIVEN: Propane (C3H8) burning at an air-fuel ratio (mass) of 18:1

FIND: The equivalence ratio, φ

ASSUMPTIONS: Air is comprised of 79% N2 and 21% O2 by volume

APPROACH: Determine the stoichiometric A/F ratio and then the equivalence ratio
Stoichiometric relation: C3 H8 + aO 2 + 3.76aN 2 → 3CO 2 + 4H 2 O + 3.76aN 2
x + y/4
=a = x 3,=y 8,= φ 1 = a 5
φ
 MWair  28.85 
= A/F )STOICH 4.76a
=   4.76
= ( 5)   15.6
 MWfuel   44.096 
Equivalence ratio:
( A/F )STOICH 15.6
= φ = = 0.87
( A/F )ACTUAL 18.0
φ = 0.87

COMMENTS: Since φ < 1 this combustion process is fuel-lean. Also note that φ does not depend
on whether the A/F ratios are expressed in terms of moles or mass since φ is also a ratio.

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written consent of McGraw-Hill Education. 2-39
PROBLEM 2-10

For an equivalence ratio of Φ = 0.6, determine the associated air–fuel ratios (mass) for methane,
propane, and decane (C10H22).

GIVEN: An equivalence ratio of 0.6

FIND: The corresponding A/F ratios (mass) for methane (CH4), propane (C3H8) and decane
(C10H22)

ASSUMPTIONS: Air is comprised of 79% N2 and 21% O2 by volume

APPROACH: Use the relationships:


x + y/4 MWair
a = and A/F )mass 4.76a
φ MWfuel
methane (CH4) x = 1, y = 4, MW = 16.043 kg/kmole
1 + 4/4  28.85 
a= 3.33 → A/F )mass =
= 4.76 ( 3.33)  
0.6  16.043 
A/F )mass = 28.50 kg-air/kg-fuel
propane (C3H8) x = 3, y = 8, MW = 44.096 kg/kmole
3 + 8/4  28.85 
a= 8.33 → A/F )mass =
= 4.76 ( 8.33)  
0.6  44.096 
A/F )mass = 25.94 kg-air/kg-fuel
decane (C10H22)
10 + 22/4  28.85 
a= =25.83 → A/F )mass =4.76 ( 25.83)  
0.6  142.284 
A/F )mass = 24.93 kg-air/kg-fuel

COMMENTS: Note how the A/F ratio (mass) changes only slightly from one hydrocarbon fuel
to another, while the A/F ratio (molar) varies from 15.9 (methane) to 123 (decane).
The difference in behavior is due to the MWfuel increasing as the molar A/F ratio increases.

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written consent of McGraw-Hill Education. 2-40
PROBLEM 2-11

In a propane-fueled truck, 3 percent (by volume) oxygen is measured in the exhaust stream of the
running engine. Assuming complete combustion without dissociation, determine the air–fuel ratio
(mass) supplied to the engine.

GIVEN: 3% (by volume) O2 measured in the exhaust of a propane (C3H8)-fueled truck

FIND: The air-fuel ratio (mass) supplied to the engine

ASSUMPTIONS: Complete combustion with no dissociation

APPROACH: Use conservation of O atoms to determine the A/F ratio from the exhaust oxygen
mole fraction
assumed combustion reaction: C3 H8 + aO 2 + 3.76 aN 2 → 3CO 2 + 4H 2 O + bO 2 + 3.76 aN 2
conservation of O atoms: 2a= 3(2) + 4 + b(2)
a= 5 + b
b= a − 5
exhaust O2 mole fraction:
N O2 b
= χ O2 =
N CO2 + N H2O + N O2 + N N2 3 + 4 + b + 3.76a
using b = a − 5
a −5 5 + 2χ O 2
= χ O2 = →a
4.76a + 2 1 − 4.76χO2
exhaust O 2 3% (by volume) → χO2 =0.03
5 + 2 ( 0.03)
=a = 5.90
1 − 4.76 ( 0.03)
 MWair   28.85 
A/F )mass 4.76a
= =   4.76 ( 5.90 )  
 MWfuel   44.096 
A/F )mass = 18.37

COMMENT: This engine is running at a fuel-lean condition


x + y/4 x + y/4 5
a= → φ= = = 0.85
φ a 5.9

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PROBLEM 2-12

Assuming complete combustion, write out a stoichiometric balance equation, like Eqn. 2.30,
for 1 mol of an arbitrary alcohol CxHyOz. Determine the number of moles of air required to burn 1
mol of fuel.

GIVEN: 1 mole of alcohol (CxHyOz) undergoing complete combustion.

FIND: Stoichiometric balance equation and number of moles of air to burn 1 mole of alcohol

ASSUMPTIONS: no dissociation and air that is 79% N2 and 21% O2 (vol)

APPROACH: Use conservation of elements for the combustion of one mole of alcohol
Stoichiometric balance:
C x H y O z + aO 2 + 3.76aN 2 → bCO 2 + cH 2 O + 3.76aN 2
conservation of carbon: x =b → b =x
conservation of H: y = 2c → c = y/2
conservation of O: z + 2a = 2b + C = 2x + y/2
a=x + y/4 − z/2
numbers of moles of air to burn 1 mole of alcohol:
N air a + 3.76a
= = 4.76a
N fuel 1
N air
= 4.76  x + y 4 − z 2 
N fuel

COMMENT: Note that stoichiometric combustion of an alcohol (CxHyOz) requires less oxygen
than the combustion of a comparable hydrocarbon fuel (CxHy) due to the presence of oxygen in
the fuel.

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written consent of McGraw-Hill Education. 2-42
PROBLEM 2-13

Using the results of problem 2.12, determine the stoichiometric air–fuel ratio (mass) for methanol
(CH3OH). Compare your result with the stoichiometric ratio for methane (CH4). What implications
does this comparison have?

GIVEN: Methanol (CH3OH) and the results of the problem 2-8

FIND: The stoichiometric A/F ratio (mass) and compare with that of methane.

APPROACH: Use the relationship developed in problem 2-8 for both methanol and methane
Methanol (CH3OH): CxHyOz x = 1, y = 4, z = 1
MW = 32 kg/kmole
 MWair 
A/F )mass= 4.76 [ x + y/4 − z/2]  
 MWfuel 
 28.85 
= 4.76 [1 + 4/4 − 1/2]   6.4
=
 32 
A/F )mass = 6.4
methane ( CH 4 ) : C x H y O z =
x 1,=
y 4,=
z 0
MW = 16 kg/kmole
 MWair 
= 4.76 [ x + y/4 − z/2] 
A/F )mass 
 MWfuel 
 28.85 
= 4.76 [1 + 4/4 − 0]  
 16 
A/F )mass = 17.2

COMMENTS: The large difference in the A/F ratios for the methanol and methane is primarily
due to the differences in fuel MW. On a molar basis the A/F ratio for methanol is 7.14 and 9.52
for methane.

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written consent of McGraw-Hill Education. 2-43
PROBLEM 2-14

Consider a stoichiometric mixture of isooctane and air. Calculate the enthalpy of the mixture
at the standard-state temperature (298.15 K) on a per-kmol-offuel basis (kJ/kmolfuel), on a
per-kmol-of-mixture basis (kJ/kmolmix), and on a per-mass-of-mixture basis (kJ/kgmix).

GIVEN: Stoichiometric mixture of isooctane & air

FIND: H per kmol of C8H18; h mix ; h mix .

ASSUMPTIONS: Air is 79% N2 & 21% O2: ideal gas

APPROACH: We start by finding the stoichiometric proportions of each component:


C8 H18 + a ( O 2 + 3.76N 2 ) → products ( Eqn.2.30 )
a =+
x y/4 =+ 12.5 ( Eqn.2.31)
8 18/4 =
So (1) C8 H18 + 12.5O 2 + 47 N 2 → Products
As the above is written for 1 kmol of C8H18,
a) H = (1) h C H
8 18
+ 12.5 h O2 + 47h N2 [= ] J/kmol-C8 H18

At 298 K, h isooc tan e = −224,109 kJ/kmol (Evaluated from curvefit coefficients in Table B.2)

o
h O2 h=
= f ,O 2 0
h N2 h=
= f ,O 2 0
H ( kJ/kmol − C8 H18 ) =
(1)( −224,109 ) + 12.5 ( 0 ) + 47 ( 0 )
= −224,109

b) h mix = ∑ χi h i ; χi = N i /N tot
χC8H18 = 1/ (1 + 12.5 + 47 ) = 1/60.5 = 0.0165
χ=
O2 12.5 (1 + 12.5 + 47
= ) 0.2066
χ N2 = 1 − χC8H18 − χO2 = 0.7769
h mix =0.0165 ( −224,109 ) + 0.2066 ( 0 ) + 0.7769 ( 0 )
h mix = −3700 kJ/kmol-mix

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written consent of McGraw-Hill Education. 2-44
c) h mix =
∑ Yi h i =
h mix /MWmix
MWmix = ∑ χi MWi
= 0.0165 (114.230 ) + 0.2066 ( 31.999 ) +
0.7769 ( 28.014 ) = 30.260
−3698
h mix = = −122.2 kJ/kg-mix
30.260

COMMENTS: We note that although both n-octane and isooctane are represented as C8H18, they
have different molecular structures as discussed in the Chapter 2 Appendix. Because of these
structural differences, the enthalpy-of-formations of the two compounds have different values.
Table B.2 was used to calculate h fo for isooctane as the value given in Table B.1 is for n-octane.
Spreadsheet software simplifies calculating properties from the Table B.2 curvefit coefficients.

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written consent of McGraw-Hill Education. 2-45
PROBLEM 2-15

Repeat problem 2.14 for a temperature of 500 K.

GIVEN: Isooctane-air, Ф = 1, T = 500 K

FIND: H (per kmol C3H8), h mix , h mix

ASSUMPTIONS: Air is 79% N2 & 21% O2; ideal gas.

APPROACH: We need only evaluate the enthalpies of the constituents at 500K and then follow
the solution to problem 2-14.
hf ∆h s @ 500K h ( 500K )

Isooctane – – − 175,807 Table B.2*

O2 0 6097 6097 Table A.11

N2 0 5920 5920 Table A.7

* Evaluated using spreadsheet software

( )
(1)( −175,807 ) + 12.5 ( 6097 ) + 47 ( 5920 )
a) H kJ/kmolC8H18 =

H = +178, 646 kJ ( for1mole C8 H18 )

H 178, 646
b) =
h mix = = 2953 kJ/kmol-mix
N mix 1 + 12.5 + 47

2953
c)
= h mix h mix /MW
= mix = 97.59 kJ/kg-mix
30.260

COMMENT: Note the use of Table B.2 in combination with Tables A.7 & A.11.

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written consent of McGraw-Hill Education. 2-46
PROBLEM 2-16

Repeat problem 2.15, but now let the equivalence ratio Φ = 0.7. How do these results compare
with those of problem 2.15?

GIVEN: Isooctane-air, Ф = 0.7, T = 500 K

FIND: H ( per kmol C3 H8 ) , h mix , h mix

ASSUMPTIONS: See problem 2-14

APPROACH: After calculating the proportions of the constituents for Ф = 0.7, we follow the

same solution as for problem 2-17.

12.5
(1) C8 H18 + ( O2 + 3.76 N 2 ) → Products
Φ

N h ( 500K ) 
χ

C8 H18 1 0.0116 −175,807 

O2 17.86 0.2077 6097  see problem 2-15
N2 67.14 0.7807 5920 
∑ Ni = 86.00 

1( −175,807 ) + 17.86 ( 6097 ) + 67.14 ( 5920 )


a) H =
H = +330,554 kJ ( for 1 kmol C8 H18 )

H 330,554
b) =
h mix = = 3844 kJ/kmol-mix
N mix 86

c) MWmix = ∑ χi MWi = 0.0116 (114.230 ) + 0.2077 ( 31.999 ) + 0.7807 ( 28.014 ) = 29.842

h mix 3844
h mix
= = = 128.8 kJ/kg-mix
MWmix 29.842

COMMENT: Note how for non-stoichiometric combustion “ a/Φ ” is substituted for “a” in
Eqn. 2.30. As expected, the mixture enthalpy increases with the addition of excess air.

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written consent of McGraw-Hill Education. 2-47
PROBLEM 2-17

Consider a fuel which is an equimolar mixture of propane (C3H8) and natural gas (CH4). Write out
the complete stoichiometric combustion reaction for this fuel burning with air and determine the
stoichiometric fuel–air ratio on a molar basis. Also, determine the molar air–fuel ratio for
combustion at an equivalence ratio, Φ, of 0.8.

GIVEN: Equimolar mixture of C3H8 & CH4 burning with air

FIND: N F /N A for Φ =1 and Φ =0.8

ASSUMPTIONS: Air is 79% N2 & 21% O2

APPROACH: C, H, & O element balances are required to determine the coefficient “a”.

C3 H8 + CH 4 + a ( O 2 + 3.76N 2 ) →
b CO 2 + c H 2 O + 3.76aN 2

C : 3= ( b 4)
+1 b =
H : 8= ( C 6)
+ 4 2C =
O : 2a = 2b + c = 2 ( 4 ) + 6 = 14
a=7

a) For Φ =1 ,

NF 1+1 kmolfuel
= = 0.0600
N A 7 ( 4.76 ) kmolair

b) For Φ =0.8

NF kmolF
Φ ( N F /N A )Φ=1 ==
= 0.8 ( 0.060 ) 0.048
NA kmolair

COMMENT: An alternative approach would be to define a composite fuel (C3H8 + CH4 ≡


C4H12) and calculate “a” from Eqn. 2.31 ( a =+
x y/4 =+
4 12/4 =7) .

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written consent of McGraw-Hill Education. 2-48
PROBLEM 2-18

Determine the enthalpy of the products of “ideal” combustion, i.e., no dissociation, resulting from
the combustion of an isooctane–air mixture for an equivalence ratio of 0.7. The products are at
1000 K and 1 atm. Express your result using the following three bases: per kmol-of-fuel, per kg-
of-fuel, and per kg-of-mixture. Hint: You may find Eqns. 2.68 and 2.69 useful; however, you
should be able to derive these from atom-conservation considerations.

GIVEN: Ideal (no dissociation) combustion products of C8H18-air for

Φ 0.7,
= = T 1000 K,
= P 1 atm

FIND : H prod ( per kmole C8 H18 )


H prod ( per kg C3 H18 )
h prod

ASSUMPTIONS: No dissociation (given), ideal gas mixture

APPROACH: We first find the mixture composition & then calculate the mixture enthalpy.

( x + y/4 ) Φ ,
Employing Eqn. 2.68, a =

8 + 18/4 12.5
=a = ⋅ Thus,
0.7 0.7

12.5
C8 H18 + ( O2 + 3.76N 2 ) →
0.7
12.5
b CO 2 + d H 2 O + f O 2 + 3.76 N 2
0.7

C= ( b 8)
: 8 b=
H :=
18 2d
= ( d 9)
 12.5 
O:   2 = 2b + d + 2f
 0.7 
= 16 + 9 + 2f
1  12.5 
=f  2 − 16=
− 9  5.357
2  0.7 
N tot = b + d + f + 3.76a
12.5
= 8 + 9 + 5.357 + 3.76
0.7
= 89.50
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Mole fractions, χi =N i /N tot :

χ
= CO 2 8/89.5= 0.0894
χ
= H2O 9/89.5= 0.1006
χ
= O2 5.357/89.5
= 0.0599
χ
= N2 67.14/89.5
= 0.7502
∑ =1.000

Species i Ni h fo,i o
∆h s,i (1000K ) N i h i (1000K )

CO2 8 − 393,546 33,425 −2,880,968

H2O 9 − 241,845 25,993 −1,942,668

O2 5.357 0 22,721 121,716

N2 67.14 0 21,468 1,441,362

∑ Ni =
89, 497 ∑ Ni h i =
−3, 260,558

H ( per kmole ) =
∑ Ni h i =
−3, 260,558kJ
C8 H18

∑ Ni h i −3, 260,558
H ( per kg ) = = = −28,544 kJ
C8 H18 MWC8 H18 114, 230

∑ Ni h i / ∑ Ni
h prod =
MWprod
MWprod = ∑ χi MWi
= 0.0894 ( 44.011) + 0.1006 (18.016 )
+ 0.0599 ( 31.999 ) + 0.7502 ( 28.014 )
= 28.68
−3, 260,558
h prod = = −1270 kJ/kg-prod
89.497 ( 28.68 )

COMMENT: This problem illustrates calculation of product properties on a “fuel basis”, i.e., per
mole of fuel or mass of fuel.

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written consent of McGraw-Hill Education. 2-50
PROBLEM 2-19

Butane (C4H10) burns with air at an equivalence ratio of 0.75. Determine the number of moles of
air required per mole of fuel.

GIVEN: C4 H10 -air, Φ =0.75

FIND: N A /N F

SOLUTION:
C4 H10 + a ( O 2 + 3.76N 2 ) → products
For Φ = 1, a = x + y/4 = 4 + 10/4 = 6.5
N A 4.76a 4.76 ( 6.5 )
= = = 41.25
NF Φ 0.75

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PROBLEM 2-20

A glass melting furnace is burning ethene (C2H4) in pure oxygen (not air). The furnace operates at
an equivalence ratio of 0.9 and consumes 30 kmol/hr of ethene.
A. Determine the energy input rate based on the LHV of the fuel. Express your result in both
kW and Btu/ hr.
B. Determine the O2 consumption rate in kmol/ hr and kg/s.

GIVEN: C2 H= 
4 -O 2 , Φ 0.9,
= N C2 H 4 30 kmol/hr
FIND: a) E ( = m C2 H 4LHV )
 ,m
b) N  O2
O2

SOLUTION:
=a) E m
=C2 H 4 LHV

N C2 H 4 MWC2 H 4 LHV

kmol 1hr kg kJ
= 30 28,054 47,161 Table B.1
hr 3600s kmol kg
kJ
= 11025
s
E = 11025kW
1000W 3.412 BTU/hr
E = 11025kW
kW W
BTU
E = 37.62 ⋅ 106 =37.62 mm BTU/hr
hr
b) For stoichiometric conditions,
C2 H 4 + aO 2 → 2CO 2 + 2H 2 O
O-balance:2a = 4 + 2; a = 3
N O2 a
= N =
N N
O2 C2 H 4 C2 H 4
N C2 H 4 Φ

 kmol 3 kmol
=N O2 30
= 100
hr 0.9 hr

= kmol 1hr kg kg
m
= O2 N O 2 MWO 2 100 31.999
= 0.889
hr 3600s kmol s

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PROBLEM 2-21

Methyl alcohol (CH3OH) burns with excess air at an air–fuel ratio (mass) of 8.0. Determine the
equivalence ratio, Φ, and the mole fraction of CO2 in the product mixture assuming complete
combustion, i.e., no dissociation.

GIVEN: CH3OH-air (Φ < 1); A/F = 8 kgf/kgair

FIND: Φ, χCO2

ASSUMPTIONS: no dissociation; air is 79% N2, 21% O2.

SOLUTION: For Φ = 1

a) CH 3OH + a ( O 2 + 3.76 ) N 2 → CO 2 + 32 H 2 O + 3.76aN 2

O-balance: 1 + 2a = 2 + 1.5; a = 2.5/2 = 1.25

4.76a MWair
( A F )Φ=1 = (Eqn. 2.32)
MWCH3OH

4.76 (1.25 ) 28.85


= = 5.358
32.040

( A/F )φ =1 5.358
=
Φ = = 0.670 Eqn. 2.33a
( A/F ) 8

a 3 a
b) CH 3OH + ( O2 + 3.76N 2 ) → CO2 + H 2O + bO2 + 3.76 N 2
Φ 2 Φ

O-balance: 1 + 2a =2 + 1.5 + 2b
Φ
1  2a  a 1.25
b =  − 2.5  = − 1.25 = − 1.25
2 Φ  Φ 0.67
b = 0.6157

N CO2 1 1
χCO2= = =
N tot 1 + 1.5 + 0.6157 + 3.76(1.25) 0.67 10.131

0.0987
χCO2 =

COMMENT: O-element balances must account for oxygen content in the fuel.

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PROBLEM 2-22

The lower heating value of vapor n-decane is 44,597 kJ/ kg at T = 298 K. The enthalpy of
vaporization of n-decane is 276.8 kJ/ kg of n-decane. The enthalpy of vaporization of water at 298
K is 2442.2 kJ/ kg of water.
A. Determine the lower heating value of liquid n-decane. Use units of kJ/ kg n-decane to
express your result.
B. Determine the higher heating value of vapor n-decane at 298 K.

GIVEN: n-decane LHV = 44,597 kJ/kg (vapor)

n-decane hfg = 276.8 kJ/kg

water hfg = 2442.2 kJ/kg

FIND: a) LHV n-decane (liq.)

b) HHV n-decane (vap.)

SOLUTION:

a) =
LHV(liq.) LHV(vap.) − h fgC10 H22

(see graph)

LHV(l) = 44597 − 276.8 = 44,320 kJ/kg

 N H2 O MWH2 O 
b) HHV(vap)
= LHV(vap) +   h fg,H2 O
 N C H MWC H 
 10 22 10 22 

where the term in brackets is mass of H2O per mass of C10H22. To find N H2O N C10 H22 , we
write:

C10 H 22 + 15.5 ( O 2 + 3.76N 2 ) → 10CO 2 + 11H 2 O + 15.5(3.76)N 2

11 18.016
HHV(vap) =
44,597 + 2442.2 =
47,999 kJ/kg
1 142.284

COMMENTS: Visualizing LHV, HHV graphically greatly aids in performing these


computations. Note how the conversion from LHV ↔ HHV involves the mass ratio of water
formed to fuel burned. The HHV-value of 47,999 kJ/kg is for practical purposes the same as the
value given in Table B.1 (HHV = 48,002 kJ/kg).

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written consent of McGraw-Hill Education. 2-54
PROBLEM 2-23

Determine the enthalpy of formation in kJ/kmol for methane, given the lower heating value of
50,016 kJ/kg at 298 K.

GIVEN: The lower heating value for methane, LHV = 50,016 kJ/kg @ 298 K
FIND: The enthalpy of formation of methane at 298 K
ASSUMPTIONS: Complete combustion of methane to form CO2, H2O and N2
APPROACH: Use the stoichiometric relation to determine the proper A/F ratio and combustion
products for 1 kmole of methane. Then use the first law of thermodynamics to evaluate the
reactant enthalpy.
Stoichiometric relation
CH 4 + aO 2 + 3.76aN 2 → CO 2 + 2H 2 O + 3.76aN 2
x+ y/4=
a= 2

BASED ON FIRST LAW ANALYSIS OF CONTROL VOLUME (CV) at steady-state


H=
R, 298 H P, 298 + LHV298

H P,=
298 1  h f,298
o
+ ( h − h f,298
o
) CO2 + 2  h fo + ( h − h f,298
o
) H2O + 7.52  h fo298 + ( h − h f,298
o
) N2
using Appendix A − T = 298 Κ
H P,298 =−
1[ 393546 + 0] + 2[−241847 + 0] + 7.52[0 + 0] =−877240 kJ
H R, =
298 1  h f,298

o
( o
+ h − h f,298  )
 CH4 
o
(
+ 2  h fo + h − h f,298
 O2 )
 + 7.52  h f,298

o o
+ h − h f,298 
 N2( )
again using Appendix A − T = 298 Κ
H R, 298= 1  h f,298
o
+ O  + 2 [ 0 + 0]O + 7.52 [ 0 + 0]N= 1  h f,298
o

CH 4 2 2 CH 4

 16 kg 
1  h f,298
HR = o
 H P, 298 + LHV298 =
= −877240 kJ + (50,016 kJ/kg)   (1kmole)
CH 4
 kmole 

 h f,o 298  = −76984 kJ/kmole


CH 4

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PROBLEM 2-24

Determine the standardized enthalpy of the mixture given in problem 2.2 for a temperature of 1000
K. Express your result in kJ/kmol of mixture.

GIVEN: The mixture composition in problem 2-2 at T = 1000 K


FIND: The absolute enthalpy of the mixture (kJ/kmol-mix)
APPROACH: Determine the absolute enthalpy of each species in the mixture using Appendix A
and then calculate the mixture absolute enthalpy from:
h mix = Σχi h i

mixture composition (from problem 2-2) and species enthalpies (Appendix A)

Species # Moles χ
o
h f,298 (kJ/kmol) (h 1000 − h f,o 298 ) (kJ/kmol)

CO 0.095 0.002 −110541 21697


CO2 6 0.127 −393546 33425
H2O 7 0.149 −241847 25993
N2 34 0.722 0 21468
NO 0.005 106 × 10−6 90297 22241

h mix = Σχi h i where h i =  h f,o 298 + ( h1060 − h f,o 298 ) 


i

h mix = ( χh i ) + ( χh i ) + ( χh i ) + ( χh i ) + ( χh i )
CO CO 2 H2O N2 NO

h mix =0.002[−110541 + 21697] + 0.127[−393546 + 33425] + 0.149[−241847 + 25993]


+ 0.722[0 + 21468] + 106 ×10−6 [90297 + 22241]
h mix = −62563kJ/kmole

COMMENTS: Note how much the N2 contributes to the mixture specific enthalpy (15500
kJ/kmole-mix) despite having a relatively small absolute enthalpy itself (21468 kJ/kmole-N2).
This is due to the large mole fraction of N2 present in the mixture.

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written consent of McGraw-Hill Education. 2-56
PROBLEM 2-25

The lower heating value of methane is 50,016 kJ/kg (of methane). Determine the heating value:
A. per mass of mixture.
B. per mole of air–fuel mixture.
C. per cubic meter of air–fuel mixture.

GIVEN: Methane lower heating value, LHV = 50,016 kJ/kg-fuel at 298 K

FIND: The lower heating value per: a) mass of fuel-air mixture


b) kmole of fuel-air mixture
c) cubic meter of fuel-air mixture

ASSUMPTIONS: fuel-air mixture behaves as an ideal gas and P = 1 atm

APPROACH: Determine the stoichiometric A/F ratio for methane and using this mixture ratio
perform a units conversion

Stoichiometric relation: CH4 + aO2 + 3.76aN2 → CO2 + 2H2O + 3.76aN2


for ϕ = 1 a = x + y/4 x=1 y=4
a=2
MWair 28.85 kg-air
a) A F )MASS 4.76a
= = 4.76(2)
= 17.12
MWfuel 16.043 kg-fuel
 1   kg-fuel 
LHV [ kJ kg-mix ] = LHV [ kJ kg-fuel]   
 1 + A F   kg-mix 
 1 kg-fuel 
LHV [ kJ kg-mix ] = ( 50016 kJ kg-f )  
 1 + 17.12 kg-mix 
LHV = 2760 kJ/kg-mix
kmol-air
b) A F )MOLAR
= 4.76a
= 4.76(2)
= 9.52
kmol-fuel
 kg-fuel  1  kmol-fuel 
LHV [ kJ kmol-mix ] =LHV [ kJ kg-fuel] ⋅ MWf  ⋅
 kmole-fuel  1 + A F  kmol-mix 

 1 
LHV [ kJ kmol-mix ] (=
= 50016 )(16.043)   76274 kJ kmole-mix
 1 + 9.52 
LHV [ kJ kmol-mix ] = 76274 kJ kmole-mix

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N  kmol-mix 
LHV  kJ m3 -mix  LHV [ kJ kmol-mix ] ⋅
c) =  
V m3 
N P 101.325 kmols
Assuming ideal gas= = = 0.0409
V R u T (8.315)(298) m3
LHV  kJ m3 -mix 
= 76274 kJ kmol ) ( 0.0409 kmols m3 )
(= 3119 kJ m3 -mix

LHV  kJ m3 -mix  = 3119 kJ m3 -mix

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written consent of McGraw-Hill Education. 2-58
PROBLEM 2-26

The higher heating value for liquid octane (C8H18) at 298 K is 47,893 kJ/kg and the heat of
vaporization is 363 kJ/kg. Determine the enthalpy of formation at 298 K for octane vapor.

GIVEN: The higher heating value of liquid octane (C8H18) at 298 K is 47893 kJ/kg-f and the
enthalpy of vaporization is 363 kJ/kg-fuel

FIND: The enthalpy of formation of octane vapor at 298 K

ASSUMPTIONS: Complete combustion, all H2O exists in liquid form, and no dissociation

APPROACH: Determine the product composition for stoichiometric combustion of octane. Then
use a first-law analysis to calculate the enthalpy of formation for liquid octane, from which the
vapor enthalpy can be found.
Stoichiometric relation:
C8 H18 + aO 2 + 3.76aN 2 → 8 CO 2 + 9 H 2 O(l ) + 3.76aN 2
Since the reactants and products are at 298 K, the sensible
enthalpies of all species are zero and the O2 and N2 heats of
formation are zero. Consequently O2 and N2 can be neglected
in this calculation.
First-law analysis: HR,298 = HP + HHV at steady-state
o o
H P,298 = 8 [h f ]CO2 + 9 [h fH2O(v) − h fg,H2O ]H2O(l ) = 8 [−393546]CO2 + 9 [−241847 − 44011]H2O(l )
−5.7211 × 106 kJ (enthalpies from Appendix A)
H P,298 =
H R ,298 = (1) [h fo ]C8H18 (l )
 kg.f 
HHV[kJ/kmol-fuel]
= HHV [kJ/kg-f ] MWfuel  =  = 5.471×106 kJ / kmol-f
47893 (114.23)
 kmol-f 
o
H R ,298 =
H P,298 + HHV(1 kmol-fuel) → h fC8 H18 ( l )
−5.7211 × 106 + 5.471 × 106 kJ/kmol
=
= −250273 kJ/kmol-fuel
o o  kgf 
h fC h fC
= + h fgC8H18 =
−250273 kJ/kmol-f + 363 kJ/kg-f 114.23
8 H18 (v) 8 H18 (l)
 kmol 
o
h fC8 H18 (v)
= −208807 kJ/kmol

COMMENTS: The absolute enthalpy of a species in the vapor-phase can be found from the
liquid-phase enthalpy:
h=
(v) h (l) + h fg
Results agree well with Appendix B.1

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written consent of McGraw-Hill Education. 2-59
PROBLEM 2-27

Verify the information in Table 2.1 under the headings ∆hR (kJ/kg of fuel), ∆hR (kJ/kg of mix), and
(O/F)stoic for the following:
A. CH4–air
B. H2–O2.
C. C(s)–air.
Note that any H2O in the product is assumed to be in the liquid state.

GIVEN: The following reactions: CH4-air, H2-O2, and C(s)-air


FIND: the heat of reaction ∆hr in kJ/kg-fuel, kJ/kg-mix and the A/F (mass) ratio. Compare the
results with Table 2.1.
ASSUMPTIONS: complete combustion, no species dissociation
APPROACH: Calculate the A/F ratio using conservation of elements and then determine ∆hr
from the first law of thermodynamics.
= N
∆H  h −N
 h −N h
r P P f f a a

a) methane-air: CH 4 + aO 2 + 3.76aN 2 → CO 2 + 2H 2 O(l) + 3.76aN 2


x+y 4
a
= = 2 for =
x 1,= φ 1
y 4,=
φ
 MWa   28.85 
A/F=
: 4.76a   4.76(2)
=   17.12
 MWf   16.043 

∆H  
N
first law: ∆h=
r 
Nf
=
r
∑ N i
h i,p − h f − ah O2 − 3.76ah N 2
f

∆h r = 1[ −393546]CO + 2 [ −285856]H O(l) − [ −74831] − 2 [ 0]O − 7.52 [ 0]O


2 2 2 2

for products and reactants at 298 K (i.e., h = h fo )

1  kmole-f 
∆h r = −890427 kJ kmol-f → ∆h r [ kJ kg-f ] = ∆h r [ kJ kmole-f ] ⋅  
MWf  kg-f 
 1 
∆h r =−890427  =−55503 kJ kg-f
 16.043 

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1  kg-f 
∆h r [ kJ kg-mix ] =
∆h r [ kJ kg-f ] ⋅
1 + A F  kg-mix 
1
∆h r [ kJ kg-mix ] =
−55503 ⋅
1 + 17.12
∆h r =−3063 kJ kg-mix

b) H2-O2: H 2 + aO 2 → H 2 O(l)
x+y 4 1
=a = for x = 0, y = 2, φ = 1
φ 2
MWO2 1  32 
A/F a =
= =   8= A/F 8
MWH2 2  2 

N
h r ∑ i h P,i − ah O2 −=
∆= h f 1h H2 O(l) − 2h O2 − h H2
N
f

1[ 285856] − 2 [ 0] − 1[ 0]
=−
∆h r =−285856 kJ/kmole-f
1 −285856
∆h r =∆h r ⋅ = → ∆h r =−142928 kJ/kg-f
MWf 2
1  1 
∆h r [ kJ/kg-mix ] =
∆h r [ kJ/kg-f ] ⋅ −142928 
= 
1 + A/F  1+ 8 
∆h r [ kJ/kg-mix ] =
−15880 kJ/kg-mix

c) C(s) + aO 2 + 3.76aN 2 → CO 2 + 3.76aN 2


x + y/4  MWa   28.85 
a
= = 1 for=
x 1,= φ 1 A/F
y 0,= = 4.76a  =  4.76(1)  
φ  MWf   12 
A/F = 11.44

N
∆h r = ∑ i h p,i − ah O2 − 3.76ah N2 − h f =1[ −393546]CO − 1[ 0]O − 3.76 [ 0]N − 1[ 0]C(s)

N 2 2 2
f

∆h r =−393546 kJ/kmole-f
1 1
∆h r [ kJ/kg-f ] =∆h r ⋅ =−393546 ⋅ = −32796 kJ/kg-f ∆h r = −32796 kJ/kg-f
MWf 12
1  1 
∆h r [ kJ/kg-mix ] =
∆h r [ kJ/kg-f ] −32796 
= =−2636 kJ/kg-mix ∆h r =−2636 kJ/kg-mix
1 + A/F  1 + 11.44 

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written consent of McGraw-Hill Education. 2-61
PROBLEM 2-28

Generate the same information requested in problem 2.27 for a stoichiometric mixture of C3H8
(propane) and air.

GIVEN: A stoichiometric mixture of propane (C3H8) and air


FIND: ∆h r (kJ/kg-f ), ∆h r (kJ/kg-mix) , and A/F (mass) ratio
ASSUMPTIONS: Complete combustion with no dissociation, water in combustion products
exists in liquid-phase since T = 298 K
APPROACH: Calculate the A/F ratio using elemental conservation and then determine ∆h r
from the first law of thermodynamics
Combustion equation: C3 H8 + aO 2 + 3.76 aN 2 → 3CO 2 + 4 H 2 O + 3.76 aN 2
x + y/4 3 + 2 MWair
a= = = 5 → A/F =
4.76a
φ 1 MWfuel

 28.85 
=A/F 4.76(5)
=   15.57
 44 
First-law analysis:

o
∆h r =
3 h fCO 2
+ 4 h fo,H2O(l) − h fo,f =
3 [−393546] + 4 [−285856] − [−103847]
∆h r =−2.2202 ×106 kJ/kmole-f
1  kmole   1 
∆h[kJ/kg-fuel] =
∆h r [kJ/kmole].   −2.2202 ×106 
=
MWf  kg-f   44.096 
∆h r =−50349 kJ/kg-f
1  kg-f   1 
∆h r [kJ/kg-mix] =
∆h r [kJ/kg-f ].   −50459 
=
1 + A/F  kg-mix  1 + 15.57 
∆h r =−3039 kJ/kg-mix

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COMMENTS: Note that this ∆h r is based on condensed H2O in the product mixture. Also,
−HHV from Appendix B.1 as would be expected.
∆h r (kJ/kg-f ) =

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written consent of McGraw-Hill Education. 2-63
PROBLEM 2-29

Consider a liquid fuel. Draw a sketch on h–T coordinates illustrating the following quantities: hl(T);
hv(T); heat of vaporization, hfg; heat of formation for fuel vapor; enthalpy of formation for fuel
liquid; lower heating value; higher heating value.

GIVEN: A liquid fuel undergoing combustion


FIND: On an h-T sketch illustrate the following quantities; hl(T), hv(T), enthalpy of vaporization,
hfg, enthalpy of formation for fuel vapor, enthalpy of formation for fuel liquid, lower heating
value, and higher heating value

COMMENTS: Note that the greatest enthalpy change at T = const (or greatest temperature
change for h = const) occurs when fuel vapor is burned and the products contain liquid H2O.
Also, the lower and higher heating values for fuel vapor can be found by adding the enthalpy of
vaporization to the fuel liquid lower and higher heating values.

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written consent of McGraw-Hill Education. 2-64
PROBLEM 2-30

Determine the adiabatic flame temperature for constant-pressure combustion of a stoichiometric


propane–air mixture assuming reactants at 298 K, no dissociation of the products, and constant
specific heats evaluated at 298 K.

GIVEN: A stoichiometric propane (C3H8)-air mixture at 298 K


FIND: The adiabatic flame temperature, Tad
ASSUMPTIONS: no dissociation, constant specific heats evaluated at 298 K
APPROACH: Use element conservation to determine the correct fuel-air mix and product
composition. Then use a first-law analysis to evaluate Tad
Stoichiometric relation:
C3 H8 + aO 2 + 3.76aN 2 → 3CO 2 + 4H 2 O + 3.76aN 2
at φ =1 a =+ x y/4 = 5
C3 H8 + 5O 2 + 18.8N 2 → 3CO 2 + 4H 2 O + 18.8N 2
(Since the reactants are at T = 298 K the O2 and N2
contributions to the reactant enthalpy are zero)
First law for adiabatic conditions: H R 298 = H PT
ad

(1)[−103847 + 0]C3 H8 =
3[−393546 + 37.198(Tad − 298)]CO2 + 4[−241847 + 33.448(Tad − 298)]H2 O
+ 18.8[0 + 29.071(Tad − 298)]N2
Solving for Tad : Tad = 2879 K

COMMENTS: Note that this flame temperature is much greater than the adiabatic flame
temperature in Appendix B.1. This is due to the assumption of no species dissociation and the
assumption of constant specific heats evaluated at 298 K. An examination of Appendix A shows
that the specific heats can vary significantly from 298 K to 2879 K.

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PROBLEM 2-31

Repeat problem 2.30, but using constant specific heats evaluated at 2000 K. Compare your result
with that of problem 2.30 and discuss.

GIVEN: A stoichiometric propane (C3H8)-air mixture at 298 K


FIND: The adiabatic flame temperature, Tad
ASSUMPTIONS: no dissociation, constant specific heats evaluated at 2000 K
APPROACH: Use element conservation to determine the correct fuel-air mixture and product
composition. Then use a first-law analysis to evaluate Tad
Stoichiometric relation:
C3 H8 + aO 2 + 3.76aN 2 → 3CO 2 + 4H 2 O + 3.76aN 2
at φ = 1 a= x + y/4 =5
C3 H8 + 5O 2 + 18.8N 2 → 3CO 2 + 4H 2 O + 18.8N 2
(Since the reactants are at T = 298 K the O2 and
N2 contributions to the reactant enthalpy are zero)
First law for adiabatic conditions: H R 298 = H PT
ad

(1)[−103847 + 0]C3 H8 =
3[−393546 + 60.433(Tad − 298)]CO2 + 4[−241847 + 51.143(Tad − 298)]H2 O
+18.8[0 + 35.988(Tad − 298)]N2
Solving for Tad : Tad = 2222 K

COMMENTS: Note that this flame temperature is much closer to the value listed in
Appendix B.1 than the temperature calculated in problem 2-17. This is due to a more appropriate
estimate of the constant specific heats. The effects of dissociation on the flame temperature are
still unaccounted for.

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PROBLEM 2-32

Repeat problem 2.30, but now use property tables (Appendix A) to evaluate the sensible enthalpies.

GIVEN: A stoichiometric propane (C3H8)-air mixture

FIND: The adiabatic flame temperature, Tad


ASSUMPTIONS: no dissociation, species thermophysical properties equal to those in
Appendix A
APPROACH: Use element conservation to determine the correct fuel-air mixture and product
composition. Then use Appendix A to evaluate the species thermophysical properties and a first-
law analysis to determine the flame temperature. This is an iterative process in which a flame
temperature is guessed, the first law is checked, and if necessary a new flame temperature is
chosen.
See problems 2-17 and 2-18 for correct fuel-air mixture and product composition. A control
volume sketch for the energy conservation is also shown first law for adiabatic conditions:
H R,298 = H P,Tad → HP  HR = 0

(1)[−103847 = 3[−393546 + ∆h s ]CO2 + 4[−241847 + ∆h s ]H2 O + 18.8[0 + ∆h s ]N2


Rearranging in form H p − H R= 0 : 3∆h s,CO2 + 4∆h s,H2 O + 18.8∆h sN2 − 2.0442 × 106= 0
T(K) ∆h s,CO2 ( kJ/kmol ) ∆h s,H2O ( kJ/kmole ) ∆h s,N2 ( kJ/kmole ) HP − HR

2000 91420 72805 56130 −423476


2100 97477 77952 59738 −316887
2200 103562 83160 63360 −209706
2300 109670 88426 66997 −101942 ΛΙΝΕΑΡ
ΙΝΤΕΡΠΟΛΑΤΙΟΝ
2400 115798 93744 70645 6296 ΥΣΙΝΓ
Η Π − ΗΡ = 0

Tad = 2394 K

COMMENTS: Note that this flame temperature is slightly greater than that listed in Appendix B.1
despite using accurate thermophysical properties from Appendix A. This is due to neglecting
species dissociation.

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PROBLEM 2-33

Once more, repeat problem 2.30, but eliminate the unrealistic assumptions, i.e., allow for
dissociation of the products and variable specific heats. Use HPFLAME (Appendix F), or other
appropriate software. Compare and contrast the results of problems 2.30–2.33. Explain why
they differ.
GIVEN: A stoichiometric propane (C3H8)-mixture at 298 K
FIND: The adiabatic flame temperature using the computer code HPFLAME or other software.
Compare and contrast the results of problems 2-17 to 2-20
Using HPFLAME: Tad = 2267K which matches Appendix B.1

The adiabatic flame temperatures calculated in problems 2-17 through 2-20 differ for two
main reasons; the method of evaluating the thermophysical properties and whether dissociation
of the product species is considered. In problem 2-17 the species sensible enthalpies were
Tad

estimated using constant specific heats at 298 K. Thus, ∆h sens


= ∫ C dt → ∆h
298
P =
sens

CP,298 (Tad − 298).

Since specific heat increases with temperature, we were effectively using too low of a specific
heat, resulting in too high of an adiabatic flame temperature for a given ∆hsens.
In problem 2-18 the adiabatic flame temperature was calculated using constant specific heats
evaluated at 2000 K. While using these specific heats yields an adiabatic flame temperature close
to that listed in Appendix B.1, the thermophysical properties are wrong. This can be seen by
comparing the adiabatic flame temperature calculated in problem 2-18 (above) with that
calculated in problem 2-19. In problem 2-19, tabulated values of sensible enthalpies
(Appendix A) were used but the calculated flame temperature is much greater than that
calculated using HPFLAME or listed in Appendix B.1. This difference cannot be attributed to
incorrect thermophysical properties and must therefore be due to dissociation of the product
species.
From the results of problems 2-17 through 2-20 it becomes apparent that accurate evaluation
of mixture thermophysical properties and product dissociation are required to obtain a close
calculation of adiabatic flame temperature.

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written consent of McGraw-Hill Education. 2-68
PROBLEM 2-34

Using the data in Appendix A, calculate the adiabatic constant-pressure flame temperature for a
boiler operating with the fuel blend and equivalence ratio given in problem 2.17. Assume complete
combustion to CO2 and H2O and neglect any dissociation. Also, assume the heat capacity of the
combustion products is constant evaluated at 1200 K. The boiler operates
at 1 atm, and both the air and fuel enter at 298 K.

GIVEN: Equimolar fuel blend of C3H8 & CH4 burns in air (Φ = 0.8)
Tair = TF = 298 K
P = 1 atm = constant
FIND: Tad

ASSUMPTIONS: No dissociation (given)


Constant CP @ 1200 K (given)
Air ≡ 79% N 2 , 21% O 2
SOLUTION: Apply first law, Eqn. 2.40a:
HR (Ti, P) = HPr (Tad, P)
To evaluate the above, we need to determine the composition of the reactants and products:
7
C3 H8 + CH 4 + (O 2 + 3.76 N 2 ) →
Φ
 1− Φ  7
4CO 2 + 6H 2 O + 7   O 2 + 3.76 N 2
 Φ  Φ
Reactants:
N h (= h fo ) Nh Table
C3H8 1 −103,847 −103,847 B.1
CH4 1 −74,831 −74,831 B.1
O2 8.75 0 0 −
N2 32.90 0 0 −
HR = Σ Ni h i =−178, 678 [=] kJ

Products:
N h fo CP @ 1200 K Nh fo NCP Table
CO2 4 −393,546 54.360 −1,574,184 217.440 A.2
H2O 6 −241,845 43.874 −1,451,070 263.244 A.6
O2 1.75 0 34.936 0 61.138 A.11
N2 32.90 0 32.762 0 1077.870 A.7
−3,025,254 1619.692

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H Pr = ΣN i h i = Σ N i  h fio + CPi (Tad − 298.15) 
= ΣN i h fi + Σ N i CPi (Tad − 298.15)
H Pr =
−3, 025, 254 + 1619.692 (Tad − 298.15)[=
]kJ
HR = HP (Eqn.2.40a)

−178, 678 =
−3, 025, 254 + 1619.692 (Tad − 298.15)

−178, 678 + 3, 025, 254


Tad − 298.15
= = 1978.1
1619.692

Tad =1978.1 + 298.15 = 2276 K

COMMENTS: Tabulating needed information for reactants & products helps to organize
calculations of this type.

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PROBLEM 2-35

Repeat problem 2.30, but for constant-volume combustion. Also, determine the final pressure.

GIVEN: C3H8-air
Ф = 1, Ti = 298, Pi = 1 atm
Constant-volume combustion
FIND: Tad, Pfinal
ASSUMPTIONS: No dissociation (given)
Constant CP,i @ 298 K
Air ≡ 79% N 2 , 21% O 2
SOLUTION: Apply first law, Eqn. 2.41:
U R (Ti , Pi ) = U Pr (Tad , Pf )
or

HR − Hpr − Ru(NRTi − NprTad) = 0 Eqn. 2.43

To evaluate Eqn. 2.43, we need the composition of both the reactants & products:

C3 H8 + 5 ( O 2 + 3.76N 2 ) → 3CO 2 + 4H 2 O + 5 ( 3.76 ) N 2

Reactants:
N h ( = h fo ) Nh Table
C3H8 1 −103,847 −103,847 B.1
O2 5 0 0 _
N2 18.8 0 0 _

R
24.8 kmol −103,847 kJ

HR = ∑N h
R
i i = −103,847 kJ

Products:
N h fo CP @ 298 K Nh fo NCP Table
CO2 3 −393,546 37.198 −1,180,638 111.594 A.2
H2O 4 −241,845 33.448 −967,380 133.792 A.6
N2 18.8 0 29.071 0 546.535 A.7

Pr
25.8 −2,148,018 791.921

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H Pr = ∑ N i h i = ∑ N i  h fi + CP,i ( Tad − Tref ) 
Pr

∑ Ni h fi + ∑ Ni CPi ( Tad − Tref )


=
−2,148, 018 + 791.921( Tad − Tref )
H Pr =

Substituting into Eqn. 2.43 with Tref = Ti,

HR − HPr − RuNRTi + RuNPrTad = 0

−103.847 − [−2,148,018 + 791.921 (Tad − Ti)]

−8.3145 (24.8) 298.15 + 8.3145(25.8)Tad = 0

Simplifying:

2,218,804 − 577.407 Tad = 0

Tad = 3843 K

N R R u Ti N pr R u Tad N T
=∀ = = ⇒ Pf Pi Pr ad
Pi Pf N r Ti
25.8 3843
=Pf 1=
atm 13.4 atm
24.8 298.15

COMMENT: As expected, the constant-vol. adia.flame temperature is significantly greater than


the const.-P value of 2879 K from problem 2.30.

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written consent of McGraw-Hill Education. 2-72
PROBLEM 2-36

Use the condition given in problem 2.33, but calculate the constant-volume adiabatic flame
temperature using UVFLAME (Appendix F), or other appropriate software. Also, determine the
final pressure. Compare your results with those of problem 2.35 and discuss.

GIVEN: C3H8-air;  = 1; Ti = 298 K; Pi = 1 atm.

FIND: Tad @ constant volume, Pfinal

ASSUMPTIONS: Ideal gas; product dissociation.

SOLUTION: To use UVFLAME, we need to determine HR(per kmol of fuel), NR, and MWR:

C3H8 + 5(O2 + 3.76 N2) → Products

H R = −103,848 kJ/kmolC3H8 ( Table B.1)

NR = 1 + 5(4.76) = 24.8 kmole

(1)44.096 + 23.8(28.85)
MWR = 29.465
24.8

OUTPUT FROM UVFLAME:

Constant-Volume Adiabatic Flame Calculation for Specified Fuel, Phi−, & Reactant Properties
Using Olikara & Borman Equilibrium Routines

Problem Title: PROBLEM 2.36 (2nd Ed.)

Data below are as read from the input file. Compare with INPUT.UV. If they do not agree, your
input data have not been entered correctly.

CARBON ATOMS 3.0


HYDROGEN ATOMS 8.0
OXYGEN ATOMS 0.0
NITROGEN ATOMS 0.0
EQUIVALENCE RATIO 1.000
FINAL TEMPERATURE (K) guess 2500.0
REACTANT TEMPERATURE (K) 298.1
REACTANT PRESSURE (Pa) 101325.0
ENTHALPY OF REACTANTS (kJ/kmol of fuel) −103848.0
MOLES OF REACTANTS (kmol/kmol of fuel) 24.800
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written consent of McGraw-Hill Education. 2-73
MOLEC WT OF REACTANTS (kg/kmol) 29.465
FLAME TEMP. & COMBUSTION PRODUCTS PROPERTIES
Const-vol Flame Temperature [K] = 2631.53
Pressure [Pa] = 0.946107E+06
Mixture Enthalpy [J/kg] = 0.5593E+06
Mixture Specific Heat, Cp [J/kg-K] = 0.255109E+04
Specific Heat Ratio, Cp/Cv = 1.1531
Mixture Molecular Weight [kg/kmol] = 27.8520
Moles of Fuel per Mole of Products = 0.03809654

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written consent of McGraw-Hill Education. 2-74
The mole fractions of the product species are:

H: 0.00104322 O: 0.00083162 N:
0.00000026
H2: 0.00538231 OH: 0.00664940 CO:
0.02220778
NO: 0.00594248 O2: 0.00910174 H2O
0.14315753
CO2: 0.09208184 N2: 0.71360183

From above:
Tad = 2631.5 K
5
=Pfinal 9.46107.10
= Pa 9.337 atm

Compared with results using Cp’s evaluated at 298 K and ignoring dissociation (problem 2-35),
these values are much lower (Tad = 2632 K vs. 3843 K). This is as expected, since Cp’s @ 298 K
are much too low and dissociation is important.

COMMENT: Note the minimal computation required to use UVFLAME to calculate constant-
volume adiabatic flame temperatures.

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written consent of McGraw-Hill Education. 2-75
PROBLEM 2-37

Derive the equivalent system (fixed mass) form of the first law corresponding to Eqn. 2.35, which
is used to define the heat of reaction. Treat the system as constant pressure with initial and final
temperatures equal.

GIVEN: A system of fixed mass at constant pressure and temperature

FIND: Equivalent system form of Eqn. 2.35 (First Law) which is used to define the heat of
reaction.

ASSUMPTIONS: expansion/contraction of the system boundary is a reversible process, only


work done by system is boundary expansion/contraction

APPROACH: Write the first law for the system. Substitute the appropriate expression for
constant pressure work and solve for the specific heat transfer.

sketch of system:

First law for a system:

1Q2 − 1W2 = m(u2 − u1)

For a system at constant pressure the reversible work can be expressed as


2

1 W2 = ∫ Pdv =
1
P(V2 − V1 ) = mP(v 2 − v1 ) v ≡ specific volume

substituting into the first law

1 Q 2 − mP(v 2 − v1 )= m(u 2 − u1 )
1 Q 2= m[(u 2 + Pv2 ) − (u1 + Pv1 )]= m(h 2 − h1 )
1 q=
2 Q 2 /m
1 = h 2 − h1

if state 1 is the reactants and state 2 is the products then

q =h P − h R ← same form as Eqn. 2.35

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COMMENTS: Note that the first law for a constant pressure system has the same form as for a
control volume. This is only true for constant pressure. Also, the internal energies u1 and u2 are
mixture internal energies. Even assuming ideal gas behavior, u1 ≠ u2 at constant temperature if
the composition changes. (See Joule’s experiment with gases and internal energy)

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written consent of McGraw-Hill Education. 2-77
PROBLEM 2-38

A furnace, operating at 1 atm, uses preheated air to improve its fuel efficiency. Determine
the adiabatic flame temperature when the furnace is run at a mass air–fuel ratio of 18 for air
preheated to 800 K. The fuel enters at 450 K. Assume the following simplified thermodynamic
properties:
Tref = 300 K,
MW
=fuel MW
= air MW
=prpd 29 kg/kmol,
c=
p ,fuel 3500 J/kg-K; =
c p ,air c=
p ,prod 1200 J/kg-K,
h fo,air h=
= o
f ,prod 0,
h fo=
,fuel 1.16 ⋅ 109 J/kmol.

GIVEN: A/F m
= =A mF
 18 CP,F = 3500 J/kg-K
TA = 800 K (preheated) CP,A = 1200 J/kg-K
TF = 450 K CP,Pr = 1200 J/kg-K
P = 1 atm
hf,A = hf,Pr = 0 h f ,F = 1.16 · 109 J/kmol

FIND: Tad for P = 1 atm

ASSUMPTIONS: Air ≡ 79% N2/21% O2; properties as given.

SOLUTION: Write first law (mass basis) recognizing that

m
=Pr m
A+ m
F

 W
Q,  =0

m
 AhA + m
 F h F =(m
 A +m
 F )h Pr

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Divide by m
 F & substitute properties (hi = hfi + cpi (Ti − Tref)):

mA  hF 
  ( 0 + CP,A (TA − Tref ) ) + (1)  + CP,F (TF − Tref ) 
mF  MWF 
m
 
=  A + 1 0 + CP,Pr (Tad − Tref 
m
F 
 1.16 ⋅ 109 
18 (1200(800 − 300) ) +  + 3500(450 − 300) 
 29 
= (18 + 1) (1200(Tad − 300) )

Solve for Tad

1.080 ⋅107 + 4.0525 ⋅107 = 2.28 ⋅104 (Tad − 300)


Tad 2251 + 300
=
Tad = 2551 K

COMMENTS: i) Use of simplified properties focuses attention on energy conservation. ii) The
use of a mass-based first law simplifies the solution (HR = HPr).

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written consent of McGraw-Hill Education. 2-79
PROBLEM 2-39

Consider the constant-pressure, adiabatic combustion of a stoichiometric (Φ = 1) fuel–air mixture


where (A/F)stoic = 15. Assume the following simplified properties for the fuel, air,
and products, with Tref = 300 K:
Fuel Air Products
cp(J/kg-K) 3500 1200 1500
h f ,300 ( J/kg )
o
2 ⋅ 10 7
0 −1.25 ⋅ 106

A. Determine the adiabatic flame temperature for a mixture initially at 600 K.


B. Determine the heating value of the fuel at 600 K. Give units.

GIVEN: Adiabatic, const.-P combustion: (A/F)φ =1 = 15, Φ = 1, Tref = 300, TF = TA = 600 K,


simplified properties

FIND: a) Tad b) HV @ 600 K

ASSUMPTIONS: Air is 79% N2, 21% O2

SOLUTION: a) HR = HPr or hR = hPr

Stoichiometry:

1 kgF + 15 kgA → 16 kgPr

H R = m A h A + m F h F = m A ( h fo,A + c P,A (TA − Tref ) ) + m F ( h fo,F + c P,F (TF − Tref ) )


H Pr = (m A + m F ) ( h fo,Pr + CP,Pr (Tad − Tref ) )
(m A + m F )h Pr =
Substitute property values & let=
m F 1,=
m A 15 :
H R = 15 ( 0 + 1200(600 − 300) ) + 1( 2 ⋅ 107 + 3500(600 − 300) )
H R = 5.4 ⋅ 106 + 2.105 ⋅ 107= 2.645 ⋅ 107 J
H Pr = 16 ( −1.25 ⋅ 106 + 1500(Tad − 300) )
H Pr =−2 ⋅ 107 + 2.4 ⋅ 104 (Tad − 300)
Set H R = H Pr & solve for Tad :
2.645 ⋅ 107 =−2 ⋅ 107 + 2.4 ⋅ 104 (Tad − 300)

a) Tad = 2235 K

b) HV = HR – HPr for 1 kg Fuel @ 600 K


From part a), HR(600) = 2.645·107 J (per kgF).

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H Pr (600) = 16 ( h of ,Pr + CP,Pr (T − Tref ) )
T = 600

= 16 ( −1.25 ⋅10 + 1500(600 − 300) )


6

−1.28 ⋅107 J (per kg F )


H Pr =
HV= H R − H Pr= 2.645 ⋅107 − (−1.28 ⋅107 )
HV
=600 3.925 ⋅107 J (per kg F )

COMMENT: This ficticious fuel with simplified properties has a low HV (240,000 kJ/kg)
compared to most real fuels (HV ∼ 45,000 kJ/kg, cf. Table B.1).

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written consent of McGraw-Hill Education. 2-81
PROBLEM 2-40

Consider the combustion of hydrogen (H2) with oxygen (O2) in a steadyflow reactor as shown in
the sketch. The heat loss through the reactor walls per unit mass flow ( Q /m ) is 187 kJ/kg. The
equivalence ratio is 0.5 and the pressure is 5 atm.

For a zero-Kelvin reference state, approximate enthalpies-of-formation are

f ,H 2 (0)
o
f ,O2 (0)
o
h= h= 0 KJ/mol,
h fo,H2 O (0) = −238,000 KJ/mol,
h fo,OH (0) = −38,600 KJ/mol,

A. Determine the mean molecular weight of the combustion product gases in the outlet stream,
assuming no dissociation.
B. For the same assumption as in part A, determine the mass fractions of the species in the
outlet stream.
C. Determine the temperature in the product stream at the reactor outlet, again assuming no
dissociation. Furthermore, assume that all species have the same constant molar specific
heats, c p ,i , equal to 40 kJ/kmol-K. The H2 enters at 300 K and the O2 at 800 K.
D. Now assume that dissociation occurs, but that the only minor product is OH. Write out all of
the equations necessary to calculate the outlet temperature. List the unknowns in your
equation set.

GIVEN: Steady-flow reactor with H2 − O2 @ Φ = 0.5, P = 5 atm,

 m
Q  = 187 kJ/kg; zero-K reference state

h fo,is : h=
o
f ,O 2
o
h=
f ,H 0 2

o
h f ,H 2 O = −238, 000 kJ/kmol
h fo,OH = −38, 600 kJ/kmol

FIND: a) MWPr (w/o dissociation)

b) Yi,Pr (w/o dissociation)

c) Tout (w/o dissoc.)


= for Tin,H2 300
= K, Tin,O2 800 K, all CPi = 40 kJ/kmol-K

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d) Add OH to products & write equations needed to find Tad.

SOLUTION:

1
a) 2H 2 + O 2 → 2H 2 O + xO 2
Φ
2 1 1
O-balance : = 2 + 2x; x = − 1 = −1 = 1
Φ Φ 0.5
MWPr = ∑ Ni MWi /∑ Ni
2(18.016) +1(31.999)
= = 22,68 kg/kmol
3
MWO2 N O2 MWO2 1 31.999
b) YO2 =χ O2 = =
MWPr N Pr MWPr 3 22.68
= 0.470
YH2 O =
1 − YO2 =
0.530

c) First law: Q −W  o= m
 (h Pr − h R )
Q /m + hR = h Pr
hR χ H 2 h H 2 + χ O2 h O2
hR =
YH2 h H2 + YO2 h O2 or h R = =
MWR χ H2 MWH2 + χO2 MWO2

Reactants

N χ h kJ/kmol
H2 2 0 + 40 (300 − 0) =
0.5 12, 000
O2 2 0.5
0 + 40 (800 − 0) =32, 000
MWR =0.5 (2.016) + 0.5 (31.999) =17.008

h R = 0.5(12000) + 0.5(32000) = 22,000 kJ/kmol


22,000
=hR = 1294 kJ/kg
17.0

Products
N χ h (=h f +CP (T-0)) kJ/kmol
H 2O 2 0.666 (−238,000 + 40 TPr )
O2 1 0.333 (0 + 40 TPr )

h Pr
= ∑
=
χh i i 0.666(−238,000 + 40 TPr ) + 0.333 (40 TPr )
MWPr 22.68
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hPr = −6995.88 + 1.7637 TPr ([=] kJ/kg)
  +h =
Returning to first law: Q/m h Pr
R

−187 + 1294 = −6995.88 + 1.7637 TPr

Solving for TPr:

TPr = 4594 K

1
d) 2H 2 + O2 → a H 2O + b O 2 + c OH
Φ

Element conservation: ratio of H-to-Q atoms in reactants equals H-to-O ratio in products,
i.e.,

# H atoms 4 2χ H2 O + χOH
i) = = 1=
#O atoms 4 χ H2 O + 2χO2 + χOH

ii) χOH + χO2 + χ H2O =1


1 kP
Equilibrium: H 2 O + O 2 
 
 2OH
2
2
χOH (p/p O ) 2 χOH
iii) = O 1/ 2 O 1/ 2
= (p/p O )1/ 2 K P
χ H2 O (p/p ) χO2 (p/p ) χ H2 O χ1/O22

where K
= P exp(−∆G T / R u T)
 −(2gOH (T) − g H2 O − 0.5 gO2 (T)) 
= exp  
 R uT 

Eqns. i–iii define the product mixture composition, χ H2O , χO2 , & χOH . Knowing these,
the first law is formulated as in part C:

iv)  /m
Q  + hR =
h Pr

The LHS of Eqn. iv is unchanged from part c. The RHS becomes

h Pr χ H2O h H2O (T) + χO2 h O2 (T) + χOH h OH (T)


hR
= =
MWPr χ H2O MWH2O + χO2 MWO2 + χOH MWOH

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where

h H2O (T) = h fo,H2O + cP (T − Tref )


h O2 (T) = h fo,O2 + cP (T − Tref )
h OH (T) = h fo,OH + cP (T − Tref ).

with the above substitutions into Eqn. iv, our equation set is complete: Eqns. i–iv
with unknowns χ H2O , χO2 , χOH , & T.

COMMENTS: Part d shows, in a simple manner, how dissociation of products is coupled to a


first-law analysis.

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PROBLEM 2-41

Verify that the results given in Table 2.2 satisfy Eqns. 2.64 and 2.65 for the following conditions:
A. T = 2000 K, P = 0.1 atm.
B. T = 2500 K, P = 100 atm.
C. T = 3000 K, P = l atm.

1
GIVEN: The equilibrium reaction CO 2 ↔ CO + O 2
2

FIND: Verify that the results of Table 2.2 satisfy Eqns. 2.64 and 2.65 for the following
conditions:

a) T = 2000 K, P = 0.1 atm


b) T = 2500 K, P = 100 atm
c) T = 3000 K, P = 1 atm

ASSUMPTIONS: ideal gas behavior (χi =Pi P)

APPROACH: Calculate ∆G oT using Appendix A and compare with Table 2.2. Using ∆G oT ,
calculate KP. Compare with the value of KP calculated using the mole fractions listed in
Table 2.2.

a) T = 2000 K, P = 0.1 atm


∆G oT  ∑ N i gfo,i  −  ∑ N i gfo,i 
=
P R

where Ni represents the stoichiometric coefficients of the equilibrium reaction


1
∆G oT =  Ngfo  +  Ngfo  −  Ngfo  = 1gfoCO + gfoO2 − 1gfoCO2
CO O2 CO 2 2

∆G oT = 1(−285948) + 12 (0) − 1(−396410) = 110462 kJ agrees with Table 2.2

 ∆G oT   −110462  −3
K P =exp  −  =exp   =1.304 ×10
 R u T   (8.315)(2000) 
1/2
χCO χO2 1/2  P  (0.0315)(0.0158)1/2  0.1 atm 
1/2

KP
=  =   = 1.314 ×10−3
χCO2  PO  (0.9527)  1 atm 
2 methods of determining KP match so the data in Table 2.2 satisfy Eqn. 2.65

b) T = 2500 K, P = 1 atm

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∆G oT = 1gfoCO + 12 gfoO − 1gfoCO = 1(−327245) + 12 (0) − 1(−396152) = 68907 kJ
2 2

 −∆G oT   −68907 
=K P exp
=   exp  =  0.03634
 R uT   (8.315)(2500) 
1/2
χCO χO2 1/2  P  (0.0289)(0.0145)1/2
=KP =   = (100)1/2 0.03638
χCO2  PO  (0.9566)

The value of ∆G oT calculated here matches ∆G oT in Table 2.2 so Eqn. 2.64 is satisfied
and the KP calculated from ∆G oT matches the KP determined from the mole fractions in
Table 2.2 so Eqn. 2.65 is satisfied

c) T = 3000 K, P = 1 atm

∆G oT = 1gfoCO + 12 gfoO − 1gfOCO = 1(−367684) + 12 (0) − 1(−395562) = 27878 kJ


2 2

 ∆G  o
 27878 
K P =exp  −  =exp  −
T
 =0.32707
 R uT   (8.315)(3000) 
1/2 1/2
χCOχO2 1/2  P  (0.3581)(0.1790)1/2  1 atm 
=KP =   =   0.32730
χCO2  PO  (0.4629)  1 atm 

Again, these calculations show that the results in Table 2.2 satisfy Eqns. 2.64 and 2.65

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PROBLEM 2-42

Consider the equilibrium reaction O2 ⇔ 2O in a closed vessel. Assume the vessel contains
1 mol of O2 when there is no dissociation. Calculate the mole fractions of O2 and O for the
following conditions:
A. T = 2500 K, P = l atm.
B. T = 2500 K, P = 3 atm.
GIVEN: A closed vessel containing 1 kmole of O2 when there is no dissociation

FIND: The mole fractions χO and χO2 at the following conditions:


a) T = 2500 K, P = 1 atm
b) T = 2500 K, P = 3 atm
ASSUMPTIONS: Ideal gas, system is in chemical equilibrium
APPROACH: There are two unknowns (χO and χO2 ) so 2 equations must be used. The first is the
definition of KP and the second is ∑ χi =1

a) T = 2500 K O 2 ↔ 2O

∆G oT  Ngfo,T  −  Ng=
= o

F,T  O 2(88203)
= − 0 176406 kJ/kmole
O 2

 −∆G   (176406) 
KP =
exp  =exp  −  206.3 ×10−6
=
 R uT   (8.315)(2500) 
χO2
KP = ( P/PO ) = 206.3 ×10−6 ← FIRST EQUATION
χ O2
From ∑ χi = 1 = χ O + χO2
χ O2 = 1 − χ O ← SECOND EQUATION

substituting the second equation into the first and rearranging yields

(P PO ) χO2 + K P χO − K P =0 quadratic equation

−K P ± K P2 + 4 ( P/PO ) (K P ) Note: Only + yields physically


solving for χo χo =
2 ( P/PO ) realistic result

T=
2500 K, P =
1 atm: K P = 1 → χO = 0.0143, χO2 = 1 − χO = 0.9857
206.3 × 10−6 , P/PO =
T=
2500 K, P =
3 atm: K P = 3 → χO = 0.00826, χO2 = 1 − χO = 0.9917
206.3 × 10−6 , P/PO =

COMMENTS: Note how this system follows the principle of Le Châtelier. Increasing the system
pressure causes the system to shift towards more O2, thereby reducing the number of moles in the
system ( N O + N O2 )
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PROBLEM 2-43

Repeat problem 2.42A, but add 1 mol of an inert diluent to the mixture, e.g., argon. What is the
influence of the diluent? Discuss.

GIVEN: The equilibrium reaction O2 ↔ 2O in a closed vessel containing 1 kmole of inert


diluent and 1 kmole of O2 with no dissociation
FIND: The mole fractions χ O and χ O2. Compare these results with those found in problem 2.22.
Discuss.
ASSUMPTIONS: ideal gas behavior, system is in chemical equilibrium, inert diluent (Ar) does
not play a role in the equilibrium reaction
APPROACH: Calculate ∆G oT and K P . Using the definition of K P and conservation of elements,
solve for the two unknowns χ O and χ O2
O 2 O Ar
conservation of elements:
1 0 1
Initial equilibrium shift − Z +2Z 0
final state 1 − Z 2 Z 1 ← # of moles
N O2 1− Z NO 2Z
mole fractions:=
χ O2 = , χO
= =
N TOT 2 + Z N TOT 2 + Z
at T = 2500 K: Note: Ar is not part of the equilibrium reaction
G oT  Ngfo  −  Ngfo =
∆=  2[88203]O − 1[0]
= 176406 kJ/kmole
O O2

 ∆G oT   176406 
K P =exp  −  =exp  −  =206.3 × 10−6
 R uT   (8.315)(2500) 
χ o2  P  −6
KP
= =  206.3 × 10
χ o2  Po 

substituting f χ O and χ O2 in terms of Z

[2Z/(2 + Z)]2
KP = 206.6 × 10−6 for P =
= Po =
1 atm
[(1 − Z)/2+Z]

−K P ± K 2P − 4(4 + K P )(−2K P )
(4 + K P )Z2 + K P Z − 2K P = 0 → Z =
2(4 + K P )
for physically realistic results
−K P ⊕
Z=
2(4 + K P )
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Solving for Z: Z = 0.0101
1 − Z 1 − 0.0101
χO= = = 0.492 0.492
χ O2 =
2
2 + Z 2 + 0.0101
2Z 2(0.0101)
χO= = = 0.01 χo =0.01
2 + Z 2 + 0.0101
1 1
χ=
Ar = = 0.4974 0.4794
χ Ar =
2 + Z 2 + 0.0101
To compare the results of problem 2-22 with the above results, we must look at number of
moles instead of mole fractions since there is argon present in this problem (i.e., even with no
dissociation of O2 to form O, the mole fractions would be different despite the fact that there
would be 1 kmole of O2 present in both problems)
Problem 2-22 Problem 2-23
O: N o = χo N TOT =
0.014 No =
χo N TOT =
χo (2 + Z) =
0.01(2.01) =
0.02
O: N o 2 =
χo2 N TOT =
0.9926 N o2 =
χo2 (2 + Z) =
0.492(2.01) =
0.989
o
COMMENTS: Note that the diluent does not affect ∆G T or the formulation of KP in terms of
mole fractions since it does not participate in the equilibrium reaction. The diluent does,
however, affect the system by altering how the mole fractions are defined. For example, the
total number of moles in problem 2-22 could be written as 1 + Z while in this problem
NTOT = 2 + Z due to the diluent. This result is consistent with Le Châtelier’s principle in that
reducing the partial pressures (with the diluent) results in more dissociation.

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PROBLEM 2-44

Consider the equilibrium reaction CO 2 ⇔ CO + 12 O 2 . At 10 atm and 3000 K, the equilibrium mole
fractions of a particular mixture of CO2, CO, and O2 are 0.6783, 0.2144, and 0.1072, respectively.
Determine the equilibrium constant Kp for this situation.

GIVEN: At P = 10 atm, T = 300 K:


χ=
CO 2 0.6783,=
χCO 0.2144,= χO2 0.1072

FIND: KP for CO 2  CO + 1/2 O 2


ASSUMPTIONS: ideal gas mixture
SOLUTION: This is a straightforward application of the definition of KP (Eqn. 2.65):
(Pco /P O )(PO2 /P O )1/2 χ CO χO2 1/2
KP = O
(P/P O )1/2
(PCO2 /P ) χ CO2
1/ 2
0.2144 (0.1072)1/ 2  10 
KP =   0.1035 (3.1623)
0.6783  1
K P = 0.3273

COMMENT: Note the influence of the total pressure on the result. Note also that, since the
temperature is given, we could have calculated Kp from exp ( −∆G T /R u T ), a more complicated
approach. From Appendix A Tables 1, 2, & 11: ∆G 3000 =−367, 685 + 12 (0) − (−395,562) =27,877
kJ/kmol; Kp = exp(−27877/8.315(3000)) = 0.327, the same result as above.

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PROBLEM 2-45

Consider the equilibrium reaction H 2O ⇔ H 2 + 12 O 2 . At 0.8 atm, the mole fractions are
χ H2 O= 0.9, χ H2= 0.03, and χO2 =
0.07. Determine the equilibrium constant Kp for this situation.

GIVEN: At P = 0.8 atm, H2O, H2, O2 mixture has the composition:


χ H2O = 0.9, χ H2 = 0.03, and χO2 = 0.07.

FIND: K P for H 2 O  H 2 + 瞌 2

ASSUMPTIONS: ideal gas mixture


SOLUTION: This is a straightforward application of the definition of KP (Eqn. 2.65):
1/ 2
(PH2 /P o )(Po2 /P o )1/ 2 χ H2 χ O2
=Kp = (P/P o )1/ 2
(PH2O /P o ) χ H2O
1/ 2
0.03(0.07)1/ 2  0.8 
=   0.008819 (0.8944)
0.9  1 
K P = 0.00789

COMMENT: Note how the total pressure enters into this calculation.

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PROBLEM 2-46

Consider the equilibrium reaction H 2O + CO ⇔ CO 2 + H 2 at a particular temperature T. At T, the


enthalpies-of-formation of each species are as follows:
−251,7000 kJ/kmol, h fo,CO2 =
hHo2 O = −396,000 kJ/kmol,
−118,700 kJ/kmol, h fo,H2 =
h fo,CO = 0.
A. What is the effect of pressure on the equilibrium? Explain.
B. What is the effect of temperature on the equilibrium? Explain (calculation required).

GIVEN: Water-gas shift reaction @ T & enthalpies-of-formation at T:


h f0,H2O = −251, 700 

h f0,CO = −118, 700 
 kJ/kmol
h f0,CO2 = −396, 600 

h f0,H2 = 0 
FIND: a) Effect of P on equilibrium?
b) Effect of T on equilibrium?
ASSUMPTIONS: ideal gas behavior
χCO2 χ H2
SOLUTION: a) KP (T) = (P/P O )1+1−1−1
χ H2O χCO

The net exponent of P/PO is zero. There is no effect of P.


b) ∆H R= h fo,CO2 + h fo,H2 − h fo,H2O − h fo,CO
=−396, 600 + 0 − (−251, 700) − (−118, 700)
∆H R =
−26, 200 ⇒ exothermic@ T
Le Châtelier’s law thus indicates that the reaction will shift to the reactants side with increasing
T: H 2 O + CO ← CO 2 + H 2
COMMENT: This problem demonstrates the application of Le Châtelier’s principle.

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PROBLEM 2-47

Calculate the equilibrium composition for the reaction H 2 + 12 O 2 ⇔ H 2O when the ratio of
the number of moles of elemental hydrogen to elemental oxygen is unity. The temperature is 2000
K, and the pressure is 1 atm.

GIVEN: The reaction H 2 + 12 O 2 ↔ H 2 O and a ratio of moles of elemental H to elemental O equal


to one
FIND: The equilibrium composition at T = 2000 K and P = 1 atm
ASSUMPTIONS: The above reaction is the only reaction involving H & O
APPROACH: Evaluate ∆G oT , determine KP, and using the definition of KP and conservation of
elements, determine χ H2 χO2 & χ H2O

1
Evaluation of ∆G oT :=
∆G To 1 (g fo,T ) H2O − 1 (g fo,T ) H2 − (g of ,T )O2
2
1
Using Appendix A ∆G o2000 =
1 (−135643) − 1 (0) − (0) =
−135643 kJ/kmol
2
 ∆G oT   135643 
K P =exp  −  =exp   =3.486 ×103
 RT  (8.315)(2000) 
In terms of χi :
1

χ H2O  P  2
KP =  o (1)
P 
1
χ H 2 χ O2 2

Conservation of elements:
#H 2χ H2O + 2χ H2
= 1= (2)
#O χ H2O + 2χO2

and by definition:
∑ χi = 1 = χ H 2 o + χ H 2 + χ O2 (3)

Solving (2) and (3) for χ H2 & χ H2O in terms of χO2 and substituting into (1):
−1/2
χ H2 =3χO2 − 1  2 − 4χ O2  P 
 KP =  
χ H2 O = 2 − 4χ O2  (3χ O2 − 1)(χ O2 )1/2  PO 

Solving for χO2 by trial & error:

with =
P P=
o 1 atm

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0.3334
χ O2 =
χ H2 = 3χO2 − 1 = 0.0003
χ H2O = 2 − 4χO2 = 0.6662

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PROBLEM 2-48

Calculate the equilibrium composition for the reaction H 2O ⇔ H 2 + 12 O 2 when the ratio of
the number of moles of elemental hydrogen to elemental oxygen, Z, is varied. Let Z = 0.5, 1.0, and
2.0. The temperature is 2000 K, and the pressure is 1 atm. Plot your results and discuss. Hint: Use
spreadsheet software to perform your calculations.

GIVEN: Equilibrium: H 2 O  H 2 + 12 O 2 @ 2000 K, 1 atm

# H-atoms
FIND: χ H2 , χO2 , χ H2O when is 0.5, 1 & 2
# O-atoms

ASSUMPTIONS: ideal gas behavior

SOLUTION: Apply element conservation:


# H-atoms 2χ H O + 2χ H2
(≡ Z) = 2
# O-atoms 2χO2 + χ H2O

Rearranging,

Z ( 2χO2 + χ H2O ) − 2χ H2O − 2χ H2 , or

i) ( Z − 2 ) χH O + 2ZχO
2 2
− 2χ H2 =0

ii) χ H 2 O + χ O2 + χ H 2 − 1 = 0

Apply equilibrium:
12 12
χ H 2 χ O2  P   −∆G oT 
iii)  O = K
= P exp  
χ H2O P   R uT 

use i) & ii) to eliminate χ H2 & express χ H O =f ( χO ) .


2 2

2 2(Z + 1)
iv) χ H2O = − χ O2
Z Z

Similarly, use i) & ii) to express χ H2 as function of χO2 :

Z−2 Z+2
v) χ H= + χ O2
2
Z Z

Now substitute iv) & v) into iii):


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1/2 1/2
 Z − 2  P  1/2  Z + 2  P  3/2 2(Z + 1)
  O  χO2 +   O  χO2 + K P χ O2
 Z  P   Z  P  Z

2K P
− 0 ≡ f (O 2 )
= vi)
Z

To solve the above transcendental equation for χ O2 , we apply the Newton-Raphson iteration
method:

f (χold
O2 )
vii) χOnew =χOold2 −
2
f ′(χold
O2 )

f ′ ( df/dχO2 ) is
where the derivative =

1/2 1/2
1  Z − 2  P  3  Z + 2   P  1/2
f ′ ( χ O2 )
−1/2
viii)
=    O  χ O2 +    χ O2
2  Z  P  2  Z   PO 
2(Z + 1)
+ KP
Z

We evaluate ∆G T=  gf ,H2 + 12 gf ,O2 − gf ,H2O  T = 2000


o o o o

=0 + 12 (0) − (−135,643) =+135,643 kJ/kmol


 −∆G OT   −135,643 
=K P exp
=   exp  
 R uT   8.315(2000) 
=K P 2.86857 ⋅ 10−4

Eqn. vii) was applied iteratively in a spreadsheet to obtain the following results:

Z χ O2 χ H2 χ H2O

0.5 0.6000 0.000148 0.39982

1.0 0.3334 0.00033 0.6662

2.0 0.00273 0.00545 0.99182

COMMENT: As the #H-atoms to #O-atoms increases, both χ H2 and χ H2O increase. For Z = 2,
χ H2O is nearly unity, i.e., nearly all of the H and O atoms, in a 2:1 ratio, are contained in the
water.

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written consent of McGraw-Hill Education. 2-97
PROBLEM 2-49

Calculate the equilibrium composition for the reaction H 2O ⇔ H 2 + 12 O 2 when the ratio of the
number of moles of elemental hydrogen to elemental oxygen, Z, is fixed at Z = 2.0, while the
pressure is varied. Let P = 0.5, 1.0, and 2.0 atm. The temperature is 2000 K. Plot your results and
discuss. Hint: Use spreadsheet software to perform your calculations.

1
GIVEN: Equilibrium reaction H 2 O  H 2 + O 2 @ T = 2000 K
2
# mol H
= 2 (≡ Z)
# mol O

FIND: χ H2 , χO2 , χ H2O for a) P = 0.5 atm, b) P = 1 atm, c) P = 2 atm


ASSUMPTIONS: ideal gas behavior
SOLUTION: The spreadsheet developed in problem 2-48 is used here w/o any changes other than,
now, P is varied, while Z is fixed.
Patm χ O2 χ H2 χ H2O
0.5 0.00343 0.00686 0.98971
1.0 0.00273 0.00545 0.99182
2.0 0.00217 0.00433 0.99350

COMMENTS: As expected, the dissociation of H2O decreases as the pressure increases. At


2000 K, we expect that other dissociation species should be included in the analysis, in particular,
OH, O, and H.

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written consent of McGraw-Hill Education. 2-98
PROBLEM 2-50

Reformulate problem 2.47 to include the species OH, O, and H. Identify the number of equations
and the number of unknowns. They should, of course, be equal. Do not solve your system.

GIVEN: The species H2, O2, OH, O, H and H2O


FIND: The solution formulation, indicating the number of unknowns and the equations that will
be used to find the unknowns.
ASSUMPTIONS: ideal gas behavior, system in chemical equilibrium
APPROACH: There are 6 species and consequently 6 unknowns. Therefore there must be 6
equations to find a solution. One equation comes from conservation of elements, one from
∑ χi =1 , and the other four from the definition of equilibrium constants KP
# H atoms 2 χ H2 + χOH + χ H + 2 χ H2O
Conservation
= of elements: = Z (1)
# Oatoms 2 χO2 + χOH + χO + χ H2O

Summation of χi : ∑ χi = χ H2 + χO2 + χOH + χO + χ H2O = 1 (2)

Equilibrium reactions:
−1/2
 ∆G OT  χ H2O  P 
H 2 + O2 ↔ H 2O
1
2 K PH2O exp  −
=  = 1/2   (3)
 R u T  H 2 O χ H 2 χ O2  PO 
2
 ∆G OT  χH  P 
H 2 ↔ 2H (K P ) H =
exp  −  =   (4)
 R u T  H χ H2  PO 

 ∆G OT  χO 2  P 
O 2 ↔ 2O (K P )O =
exp  −  =   (5)
 R u T  O χO2  PO 
−1
 ∆G OT  χOH  P 
H + O ↔ OH (K P )OH exp  −
=  =   (6)
 R u T  OH χ H χO  PO 
Equations 1–6 can be solved to find the six unknowns:
χ H2 , χO2 , χOH , χO , χ H , χ H2O

COMMENTS: Note that other equilibrium reactions involving the species of interest could have
been chosen for equations 3–6. For example, the equilibrium reactions OH + H ↔ H 2 O or
1
H 2 + OH ↔ H 2 O would have been equally valid choices.
2

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written consent of McGraw-Hill Education. 2-99
PROBLEM 2-51

Use STANJAN or other appropriate software to calculate the complete equilibrium for the H–O
system using the conditions and atom constraints given in problem 2.47.

GIVEN: An H-O system containing one mole each of elemental hydrogen and oxygen at a
temperature of 2000 K and pressure of 1 atm
FIND: The complete equilibrium of the system
APPROACH: Using STANJAN with the appropriate inputs

Computed properties

Independent atom population element potential

H 1.00000000E+00 -13.7382

O 1.00000000E+00 -14.9286
Products at T = 2000.00 K P = 1.000E+00 atmospheres

species mol fraction mol fraction mass fraction mols*


in the phase in mixture in mixture

phase 1: molal mass = 22.635 kg/kmol

H .29482E-04 .29482E-04 .13129E-05 2.21525E-05


HO .58544E-02 .58544E-02 .43988E-02 4.39892E-03
H2 .33139E-03 .33139E-03 .29515E-04 2.48999E-04
H2O .66217E+00 .66217E+00 .52704E+00 4.97540E-01
O .38202E-03 .38202E-03 .27003E-03 2.87042E-04
O2 .33124E+00 .33124E+00 .46826E+00 2.48887E-01

* Species mols for the atom populations in mols.

Mixture properties: molal mass = 22.635 kg/kmol

T = 2000.00 K P = 1.0133E+05 Pa V = 7.2503E+00 m**3/kg


U =-4.7862E+06 J/kg H =-4.0516E+06 J/kg S = 1.1988E+04 J/kg-K

Made 0 (T,P) iterations; 4 equilibrium iterations; v 3.95 IBM-PC

COMMENTS: Compare these results with those obtained in problem 2-24 to see the effects of
incorporating the additional species H, O, and OH.

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written consent of McGraw-Hill Education. 2-100
PROBLEM 2-52

For the conditions given below, list from highest to lowest the mole fractions of CO2, CO, H2O,
H2, OH, H, O2, O, N2, NO, and N. Also, give approximate values.
A. Propane–air constant-pressure combustion products at their adiabatic flame temperature for
Φ = 0.8.
B. As in part A, but for Φ = 1.2.
C. Indicate which species may be considered major and which minor in parts A and B.

GIVEN: Propane-air combustion products at 1 atm


FIND: The approximate mole fractions of CO 2 , CO, H 2O, H 2 , H, OH, O 2 , O, N 2 , NO and N
for the following conditions. List the species from highest to lowest mole fraction.
a) φ = 0.8, T = Tad
b) φ = 1.2, T = Tad
ASSUMPTIONS: The products are in chemical equilibrium
APPROACH: Use HPFLAME code with HReactants = −103,847 kJ/kmole-fuel
SOLUTION: φ = 0.8 Tad = K φ = 1.2, Tad = K
Species χ Species χ
N2 0.737 N2 0.69
H2O 0.125 H2O 0.155
CO2 0.094 CO2 0.079
O2 0.038 CO 0.054
H2 0.020
 NO 3500 ppm
OH 1800 ppm OH 860 ppm

CO 890 ppm H 800 ppm
minor 
H 2 250 ppm NO 240 ppm
species 
O 176 ppm O2 77 ppm

H
 34 ppm O 20 ppm
N
0.14 ppb N 1 ppb
COMMENT: Note the relatively large concentration of CO for φ = 1.2 and NO for φ = 0.8.

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Problem Title: PROBLEM 2-52 PART A
Data below are as read from the input file. Compare with INPUT.HP. If they do
not agree, your input data have not been entered correctly.

CARBON ATOMS 3.0


HYDROGEN ATOMS 8.0
OXYGEN ATOMS 0.0
NITROGEN ATOMS 0.0
EQUIVALENCE RATIO 0.800
TEMPERATURE (K) guess 2000.0
PRESSURE (Pa) 101325.0
ENTHALPY OF REACTANTS (kJ/kmol fuel) -103847.0
FLAME TEMP. & COMBUSTION PRODUCTS PROPERTIES
Flame Temperature [K] = 2042.03
Mixture Enthalpy [J/kg] = -0.1151E+06
Mixture Specific Heat, Cp [J/kg-K] = 0.160011E+04
Specific Heat Ratio, Cp/Cv = 1.2282
Mixture Molecular Weight [kg/kmol] = 28.3900
Moles of Fuel per Mole of Products = 0.03146029
The mole fractions of the product species are:
H: 0.00003419 O: 0.00017639 N: 0.00000000
H2: 0.00025351 OH: 0.00180270 CO: 0.00088887
NO: 0.00372180 O2: 0.03750533 H2O: 0.12466922
CO2: 0.09349201 N2: 0.73745598

Problem Title: PROBLEM 2-52 PART B


Data below are as read from the input file. Compare with INPUT.HP. If they do
not agree, your input data have not been entered correctly.
CARBON ATOMS 3.0
HYDROGEN ATOMS 8.0
OXYGEN ATOMS 0.0
NITROGEN ATOMS 0.0
EQUIVALENCE RATIO 1.200
TEMPERATURE (K) guess 2000.0
PRESSURE (Pa) 101325.0
ENTHALPY OF REACTANTS (kJ/kmol fuel) -103847.0
FLAME TEMP. & COMBUSTION PRODUCTS PROPERTIES
Flame Temperature [K] = 2201.09
Mixture Enthalpy [J/kg] = -0.1685E+06
Mixture Specific Heat, Cp [J/kg-K] = 0.166262E+04
Specific Heat Ratio, Cp/Cv = 1.2304
Mixture Molecular Weight [kg/kmol] = 27.1613
Moles of Fuel per Mole of Products = 0.04407123
The mole fractions of the product species are:
H: 0.00080465 O: 0.00002376 N: 0.00000001
H2: 0.02031565 OH: 0.00085746 CO: 0.05358114
NO: 0.00024014 O2: 0.00007722 H2O: 0.15513821
CO2: 0.07863255 N2: 0.69032921

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written consent of McGraw-Hill Education. 2-102
PROBLEM 2-53

Consider the adiabatic, constant-pressure combustion of n-decane (C10H22) with air for reactants
at 298.15 K. Use HPFLAME (Appendix F) to calculate Tad and species mole fractions for O2, H2O,
CO2, N2, CO, H2, OH, and NO. Use equivalence ratios of 0.75, 1.00, and 1.25 and evaluate each
condition for three pressure levels: 1, 10, and 100 atm. Construct a table showing your results and
discuss the effects of equivalence ratio and pressure on Tad and the product mixture composition.

PROBLEM 2.53
PHI = 0.75 PHI = 0.75 PHI = 0.75 PHI = 1.0 PHI = 1.0 PHI = 1.0
Cl0H22 P = 1 atm P = 10 atm P = 100 atm P = 1 atm P = 10 atm P = 100 atm

Tad(K) 1973.2 1978.5 1980.8 2276.6 2330.1 2365.6


h(J/kg) -8.38E+04 -8.38E+04 -8.38E+04 -1.10E+05 -1.10E+05 -1.10E+05
Cp(J/kg-K) 1514 1462 1441 2287 1941 1728
Cp/Cv 1.239 1.248 1.252 1.163 1.188 1.210
MWmix 28.67 28.68 28.69 28.37 28.48 28.55
NF/Nprod mix 0.00962 0.00962 0.00963 0.01248 0.01253 0.01257
X H 1.43E-05 2.70E-06 4.93E-07 4.69E-04 1.49E-04 4.14E-05
X O 1.18E-04 3.89E-05 1.25E-05 3.42E-04 1.11E-04 3.08E-05
X N 5.25E-10 1.80E-10 5.87E-11 2.57E-08 1.46E-08 6.70E-09
X H2 1.13E-04 3.73E-05 1.20E-05 3.02E-03 1.75E-03 9.52E-04
X OH 1.26E-03 7.28E-04 4.15E-04 0.00320 0.00193 0.00105
X CO 4.55E-04 1.51E-04 4.88E-05 0.01380 0.00850 0.00481
X NO 3.51E-03 3.56E-03 3.59E-03 0.00263 0.00222 0.00171
X O2 0.04787 0.04784 0.04786 0.00634 0.00361 0.00186
X H2O 0.1051 0.1055 0.1057 0.1325 0.1351 0.1367
X CO2 0.0958 0.0961 0.0962 0.1111 0.1168 0.1209
X N2 0.7458 0.7461 0.7462 0.7267 0.7298 0.7319

PHI = 1.25 PHI = 1.25 PHI = 1.25


Cl0H22 P = 1 atm P = 10 atm P = 100 atm

Tad(K) 2179.0 2186.2 2188.5


h(J/kg) -1.35E+05 -1.35E+05 -1.35E+05
Cp(J/kg-K) 1604 1525 1500
Cp/Cv 1.238 1.251 1.255
MWmix 27.26 27.28 27.28
NF/Nprod mix 0.0148 0.0148 0.0148
X H 7.60E-04 2.50E-04 8.02E-05
X O 1.40E-05 1.54E-06 1.59E-07
X N 8.01E-09 2.77E-09 9.00E-10
X H2 0.02331 0.02326 0.02325
X OH 6.09E-04 2.04E-04 6.57E-05
X CO 0.06847 0.06844 0.06844
X NO 1.54E-04 5.23E-05 1.69E-05
X O2 3.54E-05 3.93E-06 4.06E-07
X H2O 0.1385 0.1391 0.1393
X CO2 0.0793 0.0794 0.0794
X N2 0.6888 0.6893 0.6894

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COMMENTS:

1. At lean, stoichiometric, & rich conditions, the effect of increasing P is to suppress


dissociation and, as a result, flame temperatures increase slightly. This effect on
Tad is greatest at phi = 1, where temperatures are highest. We note that pressure has
a negligible influence on the major species [CO2, H2O, N2, O2 (lean), and H2
(rich)], while the minor species mole fractions decrease greatly with pressure.

2. The most significant effect of equivalence ratio is the lower flame temperatures at
rich & lean conditions. The CO2 mole fraction exhibits the same behavior as Tad,
while the H2O mole fraction falls at lean conditions only, & shows a small increase
at the rich condition. For the lean condition, H2 & CO are minor species & O2 a
major species; at the rich condition, O2 is a minor species & H2 & CO are major
species.

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PROBLEM 2-54

Consider the combustion products of decane (C10H22) with air at an equivalence ratio of 1.25,
pressure of 1 atm, and temperature of 2200 K. Estimate the mixture composition assuming no
dissociation except for the water-gas shift equilibrium. Compare with results of TPEQUIL.

GIVEN: The products of decane (C10H22)-air combustion at an equivalence ratio


of 1.25

FIND: The mixture composition

ASSUMPTIONS: ideal gas behavior, only dissociation is the water-gas equilibrium shift, Kp is
not a strong function of temperature in temperature range of interest

APPROACH: write the overall combustion equation, determine the A/F ratio, and solve for the
species concentrations using conservation of elements and the equilibrium water-gas shift
CO + H2O ↔ CO2 + H2

combustion equation: Cx Hy + aO2 + 3.76aN2 → bCO2 + cCO + dH2O + eH2 + fO2 + 3.76aN2

x + y/4 10 + 22/4
=a = = 12.4
φ 1.25

Conservation of: b = will solve for using water-gas shift KP


C c=x−b
O d = 2a − 2b − c = 2a − b − x
H e = y/2 − d = y/2 − 2a + b + x
f = 0 since combustion is fuel-rich

looking at water-gas equilibrium: CO + H2O ↔ CO2 + H2


2
χCO2 χ H 2 b ⋅ e  1/ N TOT  b ⋅ e
KP = = ⋅  =
χCO χ H2O c ⋅ d  1/ N TOT  c ⋅ d

b(y / 2 − a + b + x)
KP =
(x − b)(2a − b − x)

rearranging: (1 − KP)b2 + (y/2 − 2a + 2aKP + x)b + (x2Kp − 2axKP) = 0

solving this quadratic equation for b:

(2a (K P − 1) + x + y/2) ± [2a (K P − 1) + x + y/2]2 − 4(K P − 1) K P (2ax − x 2 )


b=
2 (K P − 1)

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where only the negative root yields a physically realistic value of b (i.e. b must be positive)
the preceding equation can be solved by substituting for a, x, y and KP (which must still be
determined)

 ∆G OT 
K P exp  −
= 
 R uT 

guessing an approximate flame temperature of 2200 K and assuming that KP doesn’t vary much
over a few hundred degrees K
O
∆G
= T (1)gfo CO2 + (1)gfo H2 − (1)gfo CO − (1)gfo H2O

at 2200 K:

∆G OT = (−396346) + 0 − (−302576) − (−124030) = 30260

 ∆G   30260 
K P =exp  −  =exp  −  =0.19125
 R uT   (8.315)(2200) 

solving for b: a = 12.4, x = 10, y = 22, KP = 0.19125

b = 5.361

c = x − b = 10 − 5.361 = 4.638

d = 2a − b − x = 2(12.4) − 5.361 − 10 = 9.439

e = y/2 − 2a + b + x = 11 − 2(12.4) + 5.361 + 10 = 1.561

# χ χCO2 χ H2 (0.0793)(0.0231)
Species Moles Check: =KP =
χCO χ H2O (0.0686)(0.1396)
CO2 5.36 0.079
K P = 0.191
CO 4.64 0.069
H2O 9.44 0.140
H2 1.56 0.023
N2 46.62 0.690
67.62 1.0

COMMENTS: From this problem we see that dissociation plays an important role in
determining the combustion products, and therefore, adiabatic flame temperature in a fuel-rich
process. Compare these results to problems 2-19 and 2-20 where only slight dissociation
decreased the adiabatic flame temperature by approximately 130 K.

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written consent of McGraw-Hill Education. 2-106
PROBLEM 2.55

A natural gas–fired industrial boiler operates with excess air such that the O2 concentration in the
flue gases is 2 percent (vol.), measured after removal of the moisture in the combustion products.
The flue gas temperature is 700 K without air preheat.
A. Determine the equivalence ratio for the system assuming that the properties of natural gas are
the same as methane.
B. Determine the thermal efficiency of the boiler, assuming that both the air and fuel enter at 298
K.
C. With air preheat, the flue gases are at 433 K (320°F) after passing through the air preheater.
Again, determine the thermal efficiency of the boiler for both air and fuel entering at the
preheater and burner, respectively, at 298 K.
D. Assuming premixed operation of the burners, estimate the maximum temperature in the
combustion space (P = 1 atm) with air preheat.

GIVEN: A natural gas-fired industrial boiler operates with excess air such that the O2
concentration in the flue gases is 2% (vol) after removal of the moisture in the combustion products.
The flue gas temperature without air preheat is 700 K.

FIND: a) equivalence ratio of system assuming natural gas is CH4

b) thermal efficiency of the boiler if air and fuel enter at 298 K (no air preheat)

c) with air preheat, the flue gases exit the preheater at 433 K. Determine the thermal
efficiency if fuel enters at 298 K and air enters the preheater at 298 K

d) assuming premixed burner operation, estimate the maximum temperature in the


combustion space with air preheat (P = 1 atm)

ASSUMPTIONS: no product dissociation, all energy lost by flue gases in preheater is transferred
to air entering boiler, ∆KE & ∆PE are negligible, steady-state

APPROACH: Determine the A/F ratio from element conservation then use conservation of energy
to determine the boiler efficiency

a) combustion equation: CH4 + aO2 + 3.76aN2 → CO2 + 2H2O + bO2 + 3.76aN2

in products:

O atom conservation: b =a − 1 − 1 =a − 2
↑ ↑
CO 2 H 2O

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Note that the water is still included in the O-atom conservation even though it is not included in
the measured O2 mole fraction

Substituting b = a – 2 into the definition of the O2 mole fraction

a−2 a−2
=
χ O2 = = 0.02
1 + (a − 2) + 3.76a 4.76a − 1

x+y 4
a 2.19 → =
= a x = 1, y = 4
φ
b = a − 2 = 0.19
A/F)molar = 4.76a = 10.42 φ = 0.914


Q
b) defining the boiler thermal efficiency: η = BOILER
Q
MAX

where Q  
BOILER is the heat transferred by the boiler and Q max represents the maximum possible

heat transfer (products at 298 K)

schematic for first-law analysis:

first law for control volume:

Q 1
q= =  h  −h − A
∑ N h air
   i i  prod fuel 
N fuel N fuel F MOLAR
 N   A
=q  ∑ i h i  − h fuel −  h air

 N fuel  prod F MOLAR

for q max ( Tprod = 298 k ) : h = h fo + ( h − h fo ) = h fo


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N
∑ N i
h i = 1h foCO + 2h foH O + bh fO
2 2
o
2
o
+ 3.76ah fN 2
← from combustion equation
fuel

=1[ −393546] + 2 [ −241847 ] + 0 + 0 =−877240 kJ/(kmole-fuel)

so, q max =−877240 − [ −74831]fuel − 10.42(0)air =−802409 kJ/(kmole-fuel)

for no preheat ( Tprod =700 K ) =h =h fo + h − h fo ( )



N
∑ N i hi =1[ −393546 + 17749]CO2 + 2[ −241847 + 14209] + 0.19[0 + 12503]O2 + 8.23[0 + 11942]N2
fuel

= −730415 kJ/(kmole-fuel)

q BOILER =−730415 − [ −74831] − 10.42(0) =−655584 kJ/kmole-fuel



Q q BOILER −655584
= η =BOILER

= = 0.82
Q q max −802409 max

η = 0.82 without preheat

c) with air preheat (Tprod = 433 K): h = h fo + (h − h fo )


N
q=
BOILER ∑ N i hi − h fo − A/F)MOLAR h air
fuel


N
∑ N i =1[ −393546 + 5421]CO2 + 2[ −241847 + 4609]H2 O + 0.19[0 + 4043]O2 + 8.23[0 + 3946]N2
fuel

= −829357 kJ/(kmole-fuel)
q BOILER =−829357 − [ −74831]fuel − 10.42 ( 0 )air =−754526 kJ/kmole-fuel
−754526
=η = 0.94 =η 0.94 with preheat
−802409

d) Estimate the maximum gas temperature in the combustion space with air preheat.

Assume that this temperature is the adiabatic flame temperature and that the flue gas
temperature before entering the preheater is 700 K (i.e., the temperature of the flue gas
exiting the boiler remains constant, regardless of whether air preheat is used)

first law for the preheater:

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per kmole of fuel burned:

ah O2 + 3.76ah N2 =−730415 − [ −829357 ] =98942 kJ/(kmole-fuel)



H air (kJ/kmole-fuel)

determine adiabatic flame temperature:

HP = HR = Hfuel + Hair

HP = [−74831 + 0] + 98942 kJ/kmole-fuel = 24111 kJ/kmol-fuel

H P =1h CO2 + 2h H2 O + 0.19h O2 + 8.23h N2


= 1[ −393546 + ∆h sens ]CO + 2 [ −241847 + ∆h sens ]H O + 0.19 [ 0 + ∆h sens ]O + 8.23[ 0 + ∆h sens ]N
2 2 2 2

∆h sens,CO2 + 2∆h sens,H2 O + 0.19∆h sens,O2 + 8.23∆h sens, N2 − 901351 kJ/kmol-fuel =R


where ∆h sens =h − h fo and R = 0 for correct solution

using Appendix A:

T (K) R (kJ/kmole-fuel)

2200 −97329

2300 −50028

2400

2500
−2508

45233 } Linear interpolation


for R = 0 yields
T = 2405 k

COMMENTS: Measured combustion product mole fractions are typically based on a “dry”
mixture since H2O is usually condensed out of the mixture before the mixture enters the
measuring instruments. This prevents H2O from condensing in the instruments and damaging
them. Also note that the temperature in part d is the upper limit since dissociation is neglected
and the combustion process is assumed to be adiabatic.
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written consent of McGraw-Hill Education. 2-110
PROBLEM 2-56

The equivalence ratio of a combustion process is often determined by extracting a sample of the
exhaust gas and measuring the concentrations of major species. In a combustion experiment using
isooctane (C8H18), continuous gas analyzers monitor the exhaust gas and measure a CO2
concentration of 6 percent by volume and a CO concentration of 1 percent by volume. The sample
gas is not dried before the measurements are made.
A. What is the equivalence ratio associated with this combustion process? Assume the process is
overall lean.
B. If an O2 analyzer was monitoring the exhaust gas, what would it be reading?

GIVEN: C8 H18 products:


= χCO2 0.06 (wet);
= χCO 0.01(wet)

FIND: a) Φ b) χO2

ASSUMPTIONS: All of the carbon in the fuel is converted to CO & CO2 and all of the hydrogen
to H 2O. Φ < 1.
SOLUTION: a =+
x y/4 =+
8 18/4 =
12.5
 12.5 12.5 
z C8 H18 + ( O2 + 3.76 N 2 )  → 6CO2 + 1CO + dH 2O + fO2 + (z)3.76   N2
 Φ   Φ 
C-balance: 8Z = 6 + 1 (RHS ≡ 100 kmoles)
Z = 7/8
7 63
H-balance: / 8 = 2d ⇒ d = = 7.875
8 8
7 12.5 63
O-balance: 2 = 12 + 1 + = 2f
8 φ 8
10.9375
i) = +10.4375 + f
φ
63 7 12.5
Overall: ΣN pr= 100 ⇒ 6 + 1 ++ f + 3.76 = 100
8 8 φ
41.125
or =f 85.125 − ii)
Φ
Substitute i) → ii)
10.9375 41.125 52.0625
a) − 10.4375 =85.125 − ;φ = =0.5448
φ φ 95.5625
41.125
b)=
f 85.125 − = 9.6386 χ=
O2 f /100
= 0.0964 or 9.64%
0.5448

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COMMENT: What is the source of CO in a lean product mixture? Perhaps incomplete mixing or
insufficient residence time to convert CO → CO2 (see Chapter 5)

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PROBLEM 2-57

An inventor has devised an atmospheric-pressure process to manufacture methanol. The inventor


claims he has developed a catalyst that promotes the economical reaction of CO and H2 to yield
methanol; however, a cheap supply of CO and H2 is needed. The inventor proposes burning natural
gas (CH4) in oxygen under fuel-rich conditions to yield a gas mixture of CO, CO2, H2O, and H2.
A. If methane burns in oxygen at an equivalence ratio Φ = 1.5, and the combustion reactions go
to equilibrium, what will be the resulting gas composition? Assume the combustion
temperature is controlled to 1500 K.
B. What would be the composition if the temperature were controlled to 2500 K?

GIVEN: CH4/O2 burned to yield CO, CO2, H2O, H2; Φ = 1.5

FIND: a) mixture composition for T = 1500 K

b) mixture composition for T = 2500 K

ASSUMPTIONS: ideal gas mixture

APPROACH: “Water-gas shift” equilibrium will control the composition together with the
relative proportions of C, H, & O in the reactant stream.

2
CH 4 + O 2 → b CO 2 + c CO + d H 2 O + e H 2
Φ

Arbitrarily reference to # H atoms:

#C atoms 1 χCO + χCO2


i) = =
# H atoms 4 2χ H2 O + 2χ H2
#O atoms 4/Φ 1 2 χCO + 2χCO2 + χ H2 O
ii) = = = =
# H atoms 4 Φ 3 2χ H 2 O + 2 χ H 2
iii) 1 = χCO + χCO2 + χ H2 O + χ H2
Equilibrium: CO + H 2O  CO 2 + H 2
χCO2 χ H2
iv) K p (T) =
χCO χ H2 O

a) Simultaneously solve Eqns. i–iv for Kp(T) evaluated at T = 1500 K. From Table 2.3,
Kp(1500) = 0.3887.

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Alternatively, Eqns. 2.72, 2.73, 2.74, 2.75, 2.76 can be employed to solve this problem.
( χ N ≡ 0 ) using spreadsheet software, we obtain the following results:
2

T (K) Kp % CO2 % CO %H2O % H2

1500 0.3887 13.4 20.0 42.2 24.5

2500 0.1622 9.1 24.3 46.5 20.2

COMMENTS: Relatively large amounts of CO and H2 are produced at these conditions. The
effect of temperature is not particularly strong.

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PROBLEMS 2-58 to 2-62

Consider the combustion of 1 kmol of propane with air at 1 atm. Construct a single graph using
H–T coordinates that shows the following:
A. Reactants’ enthalpy, H, in kJ versus temperature, over the range of 298–800 K for Φ = 1.0.
B. Repeat part A for Φ = 0.75.
C. Repeat part A for Φ = 1.25.
D. Products’ enthalpy, H, for ideal combustion (no dissociation) versus temperature, over the
range of 298–3500 K for Φ = 1.0.
E. Repeat part D for Φ = 0.75.
F. Repeat part D for Φ = 1.25, using the water-gas equilibrium to account for incomplete
combustion.
Using the graph constructed in problem 2.58, estimate the constant-pressure adiabatic flame
temperatures for the following conditions:
A. For reactants at 298 K with Φ = 0.75, 1.0, and 1.25.
B. For Φ = 1.0 with reactants’ temperatures of 298 K, 600 K, and 800 K.
C. Discuss your results from parts A and B.

Repeat problem 2.58, but use the code TPEQUIL (Appendix F) to calculate the products’ H versus
T curves. Use the same scales as you did in problem 2.58 so that the results can be overlaid for
comparison. Discuss the differences associated with the product enthalpy curves for the ideal
combustion case compared with the equilibrium case. Hint: Make sure the basis for all the
enthalpies is per mole of methane. You will have to convert the results from TPEQUIL to this
basis.

Repeat parts A and B of problem 2.59 using the graph obtained in problem 2.60. Compare your
results with those of problem 2.59 and discuss.

Use the code HPFLAME (Appendix F) to determine the adiabatic flame temperature for the
conditions given in parts A and B of problem 2.59. Compare your results with those of
problems 2.59 and 2.61. Discuss.

THIS SERIES OF PROBLEMS CAN BE USED AS A SINGLE PROJECT.

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PROBLEM 2-63

A furnace uses preheated air to improve its fuel efficiency. Determine the adiabatic flame
temperature when the furnace is operating at a mass air–fuel ratio of 16 for air preheated to
600 K. The fuel enters at 300 K. Assume the following simplified thermodynamic properties:

Tref = 300 K,
MW
=fuel MW
= air MW
=prod 29 kg/kmol,
c p=
,fuel c=
p ,air c p=
,prod 1200 J/kg-K,
o
h=
f ,fuel
o
h=
f ,prod 0,
h of ,fuel = 4 ⋅107 J/kg.

GIVEN: A furnace utilizing preheated air and operating at a mass air-fuel ratio of 16. The air is
preheated to 600 K and the fuel enters at 300 K.

FIND: the adiabatic flame temperature

ASSUMPTIONS: The following simplified thermodynamic properties apply

Tref = 300 K
MWf MW
= = air MW
=prod 29 kg/kmole
Cp,f C=
= p,air Cp,prod
= 1200 J/kg ⋅ K
h of ,air h=
= o
f ,prod 0
h of ,f = 4 × 107 J/kg

APPROACH: This a first law analysis

o o
 −W
Q  =H
 −H →H
 =H
P R P R

for A/F )mass =


m prod
 F (1 + A/F )
m
 F ( A/F )
 air = m
m
 f (1)
f =m
m

 =H
H 
p R

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m
 ph p = m
 f hf + m  f (1 + A/F ) 0 + CP ( Tad − Tref )  = m
 air h air → m  f ( A/F ) 0 + CP ( Tair − Tref ) 
P air

 f  h of + Cp ( Tf − Tref ) 
+m
f

(1 + 16)[0 + 1200(Tad − 300)] = (16)[0 + 1200(600 − 300)] + (1) [4 × 107 + 1200(300 − 300)]

solving for Tad: Tad = 2543 K

COMMENTS: Because of the simplified thermodynamic properties and the fact that implicitly
there is no dissociation, preheating the air (∆T = 300) results in Tad being nearly 300 K higher
(∆Tad = 283 K). If the fuel were preheated too, then ∆Tad = 300 K, exactly.

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PROBLEM 2-64

In one strategy to decrease the amount of oxides of nitrogen (NOx) formed and emitted from boilers,
a portion of the flue gases is recirculated and introduced with the air and fuel. The effect of the
recirculated gases is to decrease the maximum temperatures in the flame zone. Decreased flame
temperatures result in less NOx being formed. To increase the effectiveness of a given amount of
recycled gases, the gases may be cooled. Your job is to determine what combinations of percent
FGR and TFGR result in maximum (adiabatic) flame temperatures of approximately 1950 K.
Your design should be based on the following constraints and assumptions: the fuel enters
the burner at 298 K and 1 atm; the air enters the burner at 325 K and 1 atm; the oxygen (O2) mole
fraction in the cold, i.e., undissociated, flue gases is χ O2 = 0.02; the flue gas composition can be
approximated as complete combustion products for all conditions, with the equivalence ratio
determined from the flue-gas O2 content; the percent FGR is defined as the molar percentage of
fuel and air supplied; the natural gas can be treated as methane; and the maximum flue-gas
temperature is 1200 K.
Use graphs and tables as appropriate to present your results. Also, discuss the practical
ramifications of adding FGR (pumping requirements, capital equipment costs, etc.). How might
these considerations affect the choice of operating conditions (%FGR, TEGR)?

NOTE: This problem can be used as a small project.

GIVEN: T=
CH 4 298 K; =
Tair 325 K; =
χO2 0.02

FIND: Combinations of % FGR & TFGR that result in Tad = 1950 K.

ASSUMPTIONS: FGR composition based on no dissociation; natural gas NCH4;


TFGR, max = 1200 K.

APPROACH: i) Use χO2 to determine stoichiometry


ii) Apply 1st law (Eqn. 2.40) to determine required enthalpy of FGR
iii) Relate HFGR to % FGR & TFGR

SOLUTION:

For no dissociation, flue gas composition can be obtained:

2 2
CH 4 + ( O2 + 3.76N 2 ) → CO2 + 2H 2O + aO2 + 3.76N 2
φ φ

2 2
O-balance: 2   = 2 + 2 + 2a; a = − 2 (I)
φ  φ

 2 
= a/ 1 + 2 + a + ( 3.76 )  (II)
Given % O2: 0.02
 φ 
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Simultaneous solution of I & II yields:

a = 0.2325

φ = 0.8958

2 ( 3.76 )
N tot = N CO2 + N H2O + N O2 + N N2 = 1 + 2 + 0.2325 +
0.8958

N tot 11.627 ⇒ FGR composition:


=
1 0.2325
χ=
CO 2 = 0.0860 =
χ O2 = 0.0200
11.627 11.627
2 8.395
χ=
H2O = 0.1720 χ
= N2 = 0.7220
11.627 11.627

First law: HR = Hpr(1950 K)

or

1h CH4 + N A h A + N FGR h FGR ( TFGR ) =


N pr h pr (1950 K ) (III)

Now Npr depends on both the combustion of the fuel and NFGR, i.e.,

 N pr   N pr 
N pr =
NF   + N FGR   ; F ≡ CH 4 (IV)
 NF   N FGR 

We use TPEQUIL to determine Npr/NF:

Output from TPEQUIL

Equil. Calc. for Specified Fuel, Phi, T, & P Using


Olikara/Borman Code

Data below are as read from the input file.


Compare with INPUT.TP. If they do not agree, your
input data have not been entered correctly.

CARBON ATOMS 1.0


HYDROGEN ATOMS 4.0
OXYGEN ATOMS 0.0
NITROGEN ATOMS 0.0
EQUIVALENCE RATIO 0.8958
TEMPERATURE (K) 1950.0
PRESSURE (Pa) 101325.0

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CALCULATED COMBUSTION PRODUCTS PROPERTIES
Mixture Enthalpy [J/kg] = −0.5328E+06
Mixture Specific Heat, Cp [J/kg-K] = 0.158621E+04
Specific Heat Ratio, Cp/Cv = 1.2360
Mixture Molecular Weight [kg/kmol] = 27.7295
Moles of Fuel per Mole of Products = 0.08594273 = NF/Npr

or Npr/NF = 11.6357

11.6357
and Npr/NFGR = = 1.0007 ~ 1
11.627

Substitute IV into III & solve for NFGR/NF:

N FGR ( N pr /N F ) h pr − h F ( 298 K ) − ( N A /N F ) h air ( 325 K )


= (V)
NF h FGR − ( N pr /N FGR ) h pr

where See TPEQUIL


Output

(N pr /N F ) h pr (1950 K ) = ( N pr /N F ) h pr MWpr
 kJ  kg
= 11.6357  −532.8  27.7295
 kg  kmol
=−1.71909 ⋅ 105 kJ/kmol,

h F = h CH4 (298) = −74,831 kJ/kmol (Table B.1),


kJ
h air = 0.21( 789 ) + 0.79 ( 783) = 784.3 ,
kmol
(Tables A.11 & A.7)
(N pr /N FGR ) h pr =
(1) ( −532.8 ) 27.7295 =
−14, 774 kJ/kmol
2(4.76) 2 ( 4.76 )
N A /N F
= = = 10.627
φ 0.8958

Substituting numerical values from above into V:

N FGR −1.71909 ⋅ 105 − ( −74,831) − 10.627 ( 784.3) −105, 413


= (VI)
NF h FGR − ( −14,774 ) h FGR + 14,774

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To complete our solution, we calculate h FGR for a range of temperatures (330–1200 K); solve
Eqn. VI for NFGR/NF; and apply the definition of % FGR:

N FGR ⋅ 100% N FGR /N F


% FGR
= = ⋅ 100%
NA + NF N A /N F + 1

100
= (N
= FGR /N F ) 8.6(N FGR /N F )
11.627

h FGR (TFGR=
) ∑χ
FGR
i h i (TFGR )

For Example, at 1200 K,

h FGR (1200 K) = 0.0860 (−393,546 + 44, 488)


+ 0.1720 ( −241,845 + 34,518 )
+ 0.020 ( 0 + 29, 775 )
+ 0.7220 ( 0 + 28,118 )
= −44, 782 kJ/kmol

TFGR (K) h FGR (TFGR ) kJ/kmol NFGR/NF % FGR

330 −74,409 1.768 15.2


600 −65,858 2.064 17.7
900 −55,669 2.578 22.2
1200 −44,782 3.513 30.2

COMMENT: As expected, less % FGR is required for cooler recycled gases.

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