Chapter 14 Chemical Reactions

14-16 Ethane is burned with an unknown amount of air during a combustion process. The AF ratio and the
percentage of theoretical air used are to be determined.

Assumptions 1 Combustion is complete. 2 The combustion products contain C02, H2O, O2, and N2 only.

Properties The molar masses of C, H2, and air are 12 kg/kmol, 2 kg/kmol, and 29 kg/kmol, respectively
(Table A-I).

Analysis (a) The combustion equation in this case can be written as

~H6"+c{O2+3.76'1J ~ 2CO2+3H2O+202+3.76cN2

O2 balance: a = 2 + 15 + 2 ~ a =55

Substituting, C2H6 +55[02 +3.76N2] ~ 2C02 +3H2O+202 +20.68N2

The air-fuel ratio is determined by taking the ratio of the mass of the air to the mass of the fuel,

AF = ~ = (~:5 x 4. 76kmolX29kg/kmol ) = 25.3 kgair/kgfuel

mfuel (2kmoIX12kg/kmol)+ (3kmoIX2kg/kmol)

(b) To find the percent theoretical air used, we need to know the theoretical amount of air. which is
determined from the theoretical combustion equation of ClH6,

~H6 + Oth[O2 + 3.7Et'J2] --+ 2CO2 + 3H2O + 3. ~N 2

O2 balance: Clth= 2+ 15 --+ Cith= 35

Then,

Percent theoretical air = -~ = 157 %

-35

14-4
 Chapter 14 Chemical Reactions

14-22 Butane is burned with air. The masses of butane and air are given. The percentage of theoretical air
used and the dew-point temperature of the products are to be determined.

Assumptions 1 Combustion is complete. 2 The combustion products contain COz, HzO, and Nz only. 3
Combustion gases are ideal gases.

Properties The molar masses of C, Hz, and air are 12 kg/kmol, 2 kg/kmol, and 29 kg/kmol, respectively
(Table A-l ).

Analysis (a) The theoretical combustion equation in this case can be written as

C4H1O+ 0t!1[O2 + 3.7EX'\12] r 4CO2 + 5H2O + 3. 7~N 2

where Qlhis the stoichiometric coefficient for air. It is determined from

O2 balance: Clth= 4+ 25 --4

Oth=65

The air-fuel ratio for the theoretical reaction is determined by laking lhe ratio of the mass of lhe air lo the
mass of lhe fuel for .

mair,lh = , (~;5 x 4.76k~oIX29kg/kmol) .

AFth = (4kmoIX12kg/kmol)+ (5kmoIX2kg/kmol) = 15.5kgalr/kgfuel
mfuel

The actual air-fuel ratio used is

25 kg
AF act =~- - = 25 kg air I kg fuel
mfuel I kg

(b) The combustion is complete, and thus products will contain only C02, H2O, O2 and N2° The air-fuel
ratio for this combustion process on a mole basis is

-AF Nair mair /M air -= (25 kgy(29 kg/kmol)

= -= 50 k mo 1air /k mo If ue 1
°

NfueJ mfuel/Mfuel .(1 kg)/(58 kg/kmol)

Thus the combustion equation in this case can be written as

C4H1O +(50/4.76XO2 +3.76N2]~4CO2 +5H2O+4.002 +39.5N2

The dew-point temperature of a gas-vapor mixture is the saturation temperature of the water vapor in the
product gases corresponding to its partial pressure. That is,

Thus,
T dp = Tsar @8571 kPa = 42.7°C

14-9
,
j
 Chapter 14 Chemical Reactions

14-42 The enthalpy of combustion of liquid octane at a 25°C and 1 atm is to be determined using the data
from Table A-26 and to be compared to the value listed in Table A-27.

Assumptions The water in the products is in the liquid phase.

Analysis The stoichiometric equation for this reaction is

C8Hl8 +12.5[02 +3.76N2]~8C02 +9H2O(f.)+47N2

Both the reactants and the products are at the standard reference state of 25°C and 1 atm. Also, N2 and O2
are stable ele.ments, and thus their enthalpy of formation is zero. Then the enthalpy of combustion of C8HI8
becomes

Using 11; values from Table A-26.

hc = (8kmoIX- 393.520kJ/kmol)+ (9kmoIX- 285.830kJ/kmol)

-(lkmolX- 249.950kJlkmol)
= -5,470,680 kJ

The listed value in Table A-27 is -5,512,200 kJ/kmol for gaseous octane. The hc value for liquid octane is
obtained by adding ~ = 41 ,460 kJ/kmol to it, which yields -5,470, 740 kJ .Thus the two values are

practically identical. Since the water in the products is assumed to be in the liquid phase, this h, value
corresponds to the higher heating value of CsH!s.

14-20
 Chapter 14 Chemical Reactions

wnere ath IS the stoichiometric coefficient and is Q

determined from the O2 balance. CJH8

2~=3+2+1.~ ~ ~=5
25°C Products

Air 1200K
--.
12°C
C3Hg(f.)+12.5(O2 +3.76N2)~3CO2 +4H2O+7.502 +47N2
(a) The air-fuel ratio for this combustion process is

mair {12.5 x 4. 76kmol X 29kg/kmol )

AF=
-
= 39.2kgair/kgfuel
mfuel

-QOU! = IN p(h; + h-ho)p -IN R(h; + h -ho)R

Assuming the air and the combustion products to be ideal gases, we have h = h(T). From the tables,

II; h285 K h298 K h1200 K

Substance
-r"' TT / n, ~~~~! k.J/kmol k.J/kmol k.J/kmol-
C3Hs (e) -I 18,91D
O2 0 8296.5 8682 38,447
N2 0 8286.5 8669 36, 777
H2O (g) -241,820 9904 44,380
C02 -393,520 9364 53,848
The hi of liquid propane is obtained by adding ~ of propane at 25°C to hi of gas propane.

Substituting,

-QOUI
= (3X- 393,520+ 53,848- 9364)+ (4X- 241,820 + 44,380- 9904)+ (7.5Xo + 38,447 -8682)
+ (47Xo + 36,777- 8669)- (lX-118,910 + h298 -h298 ) -(12.5Xo + 8296.5- 8682)
-(47Xo + 8286.5- 8669 )
= -190,464kJ/kmoIC3H8
or
9o1i = 100.464 kJ /krrol C3HB
Then the rate of heat transfer for a mass flow rate of 0.1 kg/min for the propane becomes

QOUI =NQou, =(~)QOUI =(~}190,464kJ/kmol)=S194 kJ/min

~
 Chapter 14 Chemical Reactions

C2H2 +1.3athl02 +3.76N2)~2C02 +H2O+0.3ath02 +(1.3)(3.76)athN2 75.000kJ/kmol

where ath is the stoichiometric coefficient and is determined
from the O2 balance, ~

1..'X:ltt1= 2+ 0.5+ 0..'X:ltt1 ~ Clth= 2.5 .

25°C Products

Thus, -+-AIr Tp

30% excessair
C2H2 +3.25(02 +3.76N2)~2C02 +H2O+0.7502 +12.22N2 27°C
Under steady-flow conditions the energy balance Ein -Eout = Msystem applied on the combustion chamber
with W = O reduces to
I
-QOUI =LNp(h; +h-ho)p -LNR(h; +h-ho)R

Assuming the air and the combustion products to be ideal gases, we have h = h(7). From the tables.
--
h; h298 K h300 K
Substance kJ/kmol kJ/kmol kJ/kmol

C2H2 226, 730

O2 0 8682 8736
N2 0 8669 8723
H2O (g) -241,820 9904
C02 -393,520 9364
Thus;

-75,000 = (2)(- 393,520 + hco2 -9364)+ (1)(- 241,820 + hH2O -9904)

+ (0.75)(0 + hO2 -8682)+ (12.22)(0 + hN2 -8669 )- (1)(226,730)

-(3.25)(0 + 8736- 8682) + (12.22)(0 + 8723- 8669)

It yields 2~2+ ~20 + Q 75~2 + 12Z2.~2 = 1.':r2;1184 kJ

The temperature of the product gases is obtained from a trial and error solution. A first guess is obtained
by dividing the right-hand side of the equation by the total number of moles, which yields 1,321 , 184/(2 + I
+ 0.75 + 12.22) = 82,729 kJlkmol. This enthalpy value corresponds to about 2500 K for N2. Noting that
the majority of the moles are N2, Tp will be close to 2500 K, but somewhat under it because of the higher
specific heats of CO2 and H2O.
At 2350 K:

2hco2 +hH2O +0.75ho2 +12.22hN2 =(2)(122,091)+(1)(100,846)+(0.75)(81,243)+(12.22)(77,496)

= 1,352,961kJ ( Higher than 1,321 ,184 kJ )

At 2300 K:

= 1,320,517kJ (Lowerthanl,321,184kJ)

By interpolation, T p = 2301 K

14-40

~
 Chapter 14 Chemical Reactions

CsH1s(f.)+1.5ath(02 +3.76N2~8CO2 +9H2O+O.5atnO2 + (1.5X3.76~thN2

where arb is the stoichiometric coefficient and is determined from the To= 298 K
O2 balance, 0
CBH1B (e)
l.~ = 8+ 4.5+ O.~ ~ Dth= 12.5
~ Products

Air I 25°C

50% excess air

CgH]g(t')+18.75(O2 +3.76N2) --+ 8CO2 +9H2O+6.2502 +70.5N2
25°C

Under steady-flow conditions the energy balance E;, -E,", = ~E,y",m applied on the combustion chamber
with W = O reduces to

-QO"' = l:::Np(h; +h -ho )p -LNR(h; +h -ho )R QO"' = l:::Nph;p -LNRh;J1

since all of the reactants are at 25°C Assuming the air and the combustion products to be ideal gases, we
have h = h(7) From the tables,

Substance kJ /kho r
-mol
CHRIs (I.) -249,950
O2 0
N2 0
R2O (I) -285,830
C02 -393,520

Substituting,
i
,
,
-Qout = (8X-393.520)+ (9X-285,830)+0+0-(IX-249,950)-0-0 = -5,470,680 kJ /krnol of C8HI8
j

or Qott = 5.470.~kJ/knDI of CSH1S

The CsHJs is burned at a rate of 0.4 kg/min or

.I.U~,

The heat transfer for this process is also equivalent to the enthalpy of combustion of liquid C8H18, which
could easily be de determined from Table A-27 to be ft, = 5,470,740 kJ/kmol C8H18.

14-47
 Chapter 14 Chemical Reactions

(b) The entropy generation during this process is determined from

The CgH1g is at 25°C and I atm, and thus its absolute entropy is ~ H = 360.79 kJ/kmol.K (Table A-26).
"\.;8 18

The entropy values listed in the ideal gas tables are for I atm pressure. Both the air and the product gases
are at a total pressure of I atm, but the entropies are to be calculated at the partial pressure of the
components which is equal to P i = yj P total,where yj is the mole fraction of component i. Also,

Si =Nisi(T,p;)=Ni~i.(T,Po)-Ru In(y,Pm))

The entropy calculations can be presented in tabular form as

Sp = 17,538 kJ/K
Thus,

and

Sgen =Nsgen =~.51xlO-3 krnol/min}17,799 kJlkmol.K)=62.47 kj/min.K

(c) The exergy destruction rate associated with this process is determined from

X destroyed
=ToSgen =(298 KX62.47 kJ/min.K)=18,617 kJ/min=310.3 kW

14-48
 Chapter 14 Chemical Reactions

14-91 The highest possible temperatures that can be obtained when liquid gasoline is burned steadily with
air and with pure oxygen are to be determined.

Assumptions 1 Steady operating conditions exist. 2 Air and combustion gases are ideal gases. 3 Kinetic and
potential energies are negligible. 4 There are no work interactions. 5 The combustion chamber is adiabatic.
,
l
Analysis The highest possible temperature that can be achieved during a combustion process is the c
temperature which occurs when a fuel is burned completely with stoichiometric amount of air in an i
i
adiabatic combustion chamber. It is determined from ,
;
L N p (h i + h -h o )p = L N R (h i + h -h o )R ~ L N p (hi + hr -h o )p = (Nh i )C8H18

since all the reactants are at the standard reference temperature of 25°C, and for O2 and N2. The theoretical
combustion equation of CsHIs air is

CgHIg +12.5(02 +3.76N2)~8C02 +9H2O+47N2

From the tables.

ii; h29S K
Substance
kJ/k mo I kJ/kmol

CsHIs (l) -249,950

O2 0 8682
N2 0 8669
H2O (g) -241,820 9904
C02 -393,520 9364

Thus,

It yiel~s

The adiabatic flame temperature is obtained from a trial and error solution. A first guess is obtained by
dividing the right-hand side of the equation by the total number of moles, which yields 5,646,081/(8 + 9 +
47) = 88,220 kJ/kmol. This enthalpy value corresponds to about 2650 K for N2. Noting that the majority
of the moles are N2, T p will be close to 2650 K, but somewhat under it because of the higher specific heat
ofH2O.

At 2400 K: 8hco2 + 9hH20 + 47hN2 = (8Xl25,l52)+ (9 XlO3,508)+ (47X79,320)

= 5,660,828k1 (Higherthan5,646,O8lkJ )

At 2350 K: 8hco.. +9hH..o +47hN.. =(8Xl22,O9l)+(9XlOO,846)+(47X77,496)

..-= 5,526,654k1 (Lowerthan5,646,O8lkJ)

By interpolation, Tp = 2395 K

If the fuel is burned with stoichiometric amount of pure O2, the combustion equation would be

CsHIS + 12502 8CO2 + 9H2O

Thus,

14-66
 It yields

Byextrapolation, Tp = 3597 K

14-67
 Chapter 14 Chemical Reactions

14-93 Liquid octane is burned with 200 percent excess air during a steady-flow combustion process. The
heat transfer rate from the combustion chamber, the power output of the turbine, and the reversible work
and exergy destruction are to be determined.

Assumptions 1 Combustion is complete. 2 Steady operating conditions exist. 3 Air and the combustion
gases are ideal gases. 4 Changes in kinetic and potential energies are negligible.

Properties The molar mass ofCgH1g is 114 kg/kmol (Table A-1).

Analysis (a) The fuel is burned completely with the excess air, and thus the products will contain only C02,
H2O, N2, and some free O2. Considering 1 kmol of CgH1g, the combustion equation can be written as
,
CgH1g +3a1h(02 +3.76N2~8CO2 +9H2O+2athO2 +(3X3.76ath)N2
where ath is the stoichiometric coefficient and is determined from the O2
Q
balance,
C8H18 :

.?i:fttI = 8+ 4.5+ ~ ~ Clth= 12.5 25°C.

-.
8 aIm

Substituting, Air I

200%excess
CsHIS +37.5(02 +3.76N2~8C02 +9H20+2502 +14lN2 air 1300 K

8 aIm
The heat transfer for this combustion process is determined from the
energy balance Ein -Eoul ::::l1Esystem applied

chamber with W:::: 0,

on the combustion
I
:::J
Combustion
~ w

gases

~\ -

Assuming the air and the combustion products to be ideal gases, we 950 K
have h = h(7). From the tables, 2atm

ii; ii5oo K ii298K iiI300 K ii950 K

Substance
~~~~ k.J/kmol k.J/kmol k.J/kmol k.J/kmol
C8HI8 (t) -249,950
O2 0 14,770 8682 42,033 26,652
N2 0 14,581 8669 40,170 28,501
H2O (g) -241,820 9904 48,807 33,841
C02 -393,520 9364 59,552 40,070
Substituting,
-QOUI = (8X- 393.520+ 59,522 -9364 )+ (9 X- 241,820+ 48,807 -9904 )

+(25Xo+42,033-8682)+ (141Xo+40,170- 8669 )

-(lX- 249,950+ hz98 -h298)- (37.5Xo+ 14.770-8682)- (141Xo+ 14,581- 8669 )
= -109,675kJ/kmo1C8HI8

The C8HI8 is burned at a rate of 0.8 kg/min or

.m 0.8 kg/min -3 .
,
N=- -=
(()( ) ( )()) =7.018xlO kmoVmm
M 8 12 + 18 1 kg/kmol
Thus,
QOUI= NQou, = (7.018 x 10-3 kmollminXl09,675 kJ/kmol) =770 kJ/min

14-70
 Chapter 14 Chemical Reactions

Substituting,
Wout =: (8X59,522 -40,070)+ (9 X48,807 -33,841)+ (25X42,033- 29,652)+ (141X40,1 70- 28,501)
=: 2,320,164 kJlkmol CSH18

Thus the power output of the turbine is

WOU!
= Nwou! = ~.018x 10-3 kmollmin}2,320,164 kJ/kmo1)= 16,283 kJ/min = 271.4 kW

(c) The entropy generation during this process is determined from

Sgen

where the entropy of the products are to be evaluated at the turbine exit state. The CsHIs is at 25°C and 1
atm, and thus its absolute entropy is 5.. H =360.79 kJ/krnol. K (Table A-26). The entropy values listed in
~ 18
the ideal gas tables are for 1 atrn pressure. The entropies are to be calculated at the partial pressure of the
components which is equal to Pi = YiP IOlaJ,where Yi is the mole fraction of component i. Also.

Si = Nisi (T.P; )= Ni~.(T.Po)- Ruln(y;p m))

The entropy calculations can be presented in tabular form as

Nj Yj
s;(T,1 atm) Ruln(y;P m ) N .s.
I I
C8HI8 1 1.00 360.79 17.288 343.50
O2 37.5 0.21 220.589 4.313 8,110.34
-B2- 141 0.79 206.630 15~329 26,~

-CO2 8 ()()L1~7 '"\££ AAA --SB= 35,427.28 kJ~~

CO2 8 0.0437 266.444 -20.260 2,293.63

H2O 9 0.0490 230.499 -19.281 2,248.02

O2 25 0.1366 241.689 -10.787 6,311.90
-B2- 141 0.7~226.389 3.~95 31,~~

Sp = 42,267.48 kJ/K
Thus,

Sgen =42,267.48-35,427.28+!Q9,67~ = 7208.2 kJ/K (per kIno])

298 K
Then the rate of entropy generation becomes

Sgen ==Nsgen ==~ .018 X 10-3kmol/min }7208.2 kJ/kmol. K) ==50.59 kJ/min .K

and

x destruction
=ToSgen =(298 K)(50.59 kJ/min .K)=15,075 kJ/min =251.2kW

Wrev
= W + X destruction
= 271.4 + 251.2 = 522.6 k W

14- 71