Thermodynamics of Steady Flow Combustion

Steady Flow Combus2on

Combus2on stoichiometry Applica2on of the 1st law and 2nd law to combus2on processes Combined 1st and 2nd law 2nd law eciency

Combus2on Stoichiometry
Combus'on burning or rapid oxida2on of HC fuels Generic form of HC fuels CaHb Common Oxidant Atmospheric air 0.21 O2 + 0.79 N2 (for 1 mole of air) O2 + 3.76 N2 (for 1 mole of O2) Complete Combus,on CaHb + Air CO2 + H2O Incomplete Combus,on CaHb + Air CO + CO2 + H2O
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Combus2on Stoichiometry
Stoichiometric Rela2on C H + (O2 + 3.76 N 2 ) CO2 + H 2O + N 2

where the unknown stoichiometric coefficients are " % = = 2 = + 4 = 3.76 $ + 4 ' # & Where the + is the minimum no. of moles of O2 per 4 mole of CaHb eec2ng the complete combus2on of CaHb

Dening =

Actual air flow rate >1 Theorectical air flow rate

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Combus2on Stoichiometry
C H + + ( O2 + 3.76 N 2 ) 4

Where 1 ) is dened as the excess air (

CO2 + H 2O + 3.76 + N 2 + ( 1) + O2 2 4 4

The reac2on is said to be with 400% theore2cal air or with 300% excess air If < Incomplete combus,on 1 If pure O2 is used:

1st Law Analysis

Open, Steady ow system m n 0 = Q W + nri hri n pi h pi i=1 i=1
W
Reactants Hr Control Volume Combus2on Chamber Products HP

Q Let n r1 = n fuel , the molal ow rate of fuel m n Q W 0= + ri hri pi h pi

Q W Hr Hp

n fuel n fuel i=1 i=1 0 = Q W + H r H p

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1st Law Analysis

Case: W = 0 and temp of products and reactants are T0,P0
Q = H p Hr

quan22es evaluated at reference To and Po.

Q < 0 i.e. exothermic |Q|= Hp Hr is a nite and a measurable quan2ty

H r = 1 hr1 To , Po + r 2 hr1 To , Po +
Hp p1 p1 o o p2 p2 o o component enthalpies are evaluated at To and Po.

() ( ) ( ) = h (T , P ) + h (T , P ) +

1st Law Analysis

Enthalpy of forma'on

h (To , Po ) = 0 Elementary substances h fo = 0 h (To , Po ) = h fo For Compounds

Combus2on of CH with (-1) excess air

Hr = h
o f C H

+0+0
O2

H p = h

N2

o f CO2

o + hf H O + 0 + 0 2 2

Q : Enthalpy of combus2on of CH.

Heat transfer per mole of fuel Q = h

o f CO2

o + h f H O h foC H 2 2

1st Law Analysis

Hea2ng value of fuel =|Q| =Hr Hp

If Hydrogen appears as H2O (vapor) LHV If Hydrogen appears as H2O (liquid) HHV
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1st Law Analysis

Case: Reactants & Products are at dierent To and Po 0 = Q W + Hr H p but hri and hpi are not at To and Po Let T and P represent the temperature and pressure of the one par,cular cons,tuent in the stream of reactants or products and let h ( T P ) be its enthalpy: , h (T , P ) = h (T , P ) + h (T , P ) h (T , P )
o o o o h

h T , P = h fo + h

where h is the enthalpy change

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1st Law Analysis

At low pressures, cons2tuents obey the ideal gas model: h = h (T ) only h (To ) = 0 In conclusion, the per mole of fuel enthalpy is:

H r = ri ( h fo + h )
i =1

ri

H p = pi ( h fo + h )
i =1

pi

Fig 7.7 in the textbook shows that h ( ) is T prac2cally linear in temp.

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1st Law Analysis

Case: W = 0 and Q = 0 (Adiaba2c). Adiaba2c Flame Temperature Hr = H p
here the products reach extremely high temperatures. Adiaba2c and zero work control surface Products Reactants T , P Taf, Po Products, To, Po o o Combus2on

Hea2ng Value System external to combus2on chamber receives joules per mole of fuel LHV System is insulated Cannot dispose LHV
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1st Law Analysis

LHV heats the mixture of products to the Adiaba,c Flame Temperature (Taf) Taf is obtained from Hr(To,Po) = Hp(Taf,Po) Taf is theore2cally highest value because:
E.g. CO2 CO + O2

no combus2on chamber is perfectly insulated at Taf one of the products can undergo chemical dissocia2on

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1st Law Analysis

Dissocia2on ends Tnew products = Toriginal products Remaining products being cooled Products Taf , Po Heat transfer Products of Dissocia2on Dissocia2ng frac2on Tafd < Taf E.g. H 2 2 H ; O2 2O ; N 2 2 N
1 1 H 2O H 2 + O2 ; H 2O OH + H 2 2 2
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Adiaba2c and zero work control surface

New Products Tafd, Po

cooler and dierent than original mixture

2nd Law Analysis

Represents entropy interac2ons
Reactants Sr Control Volume ( C.C) Ti Qi/Ti Products SP

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2nd Law Analysis

The per mole of fuel statement
= Qi S + S 0 S gen r p Ti i

C.C. acts as producer of entropy Adiaba2c combus2on: S gen = S p Sr 0

lim In the T 0 s = 0 s = s(T )

In combus2on processes s = s(T , P)

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2nd Law Analysis

At P = Po (atm)
s (T , Po ) = s o (T )
s T , P = s o T + s T , P s T , Po

( ) (

) (
s

is due to pressure change at constant temperature

In many cases temperatures are very high and par2al pressure Ps are low to jus2fy the ideal gas model

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2nd Law Analysis

Assuming all cons2tuents are ideal gases:
P S r = ri so R ln Po ri i =1 P S p = pi so R ln Po pi i =1
n m

If the cons2tuents appear in liquid form, IC substance model is used

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Maximum Power Output

How chemical reac2ons are used to produce mechanical power? Steady ow apparatus Reactants Products Hp, Sp, Bp Hr, Sr, Br Combus2on chamber and power plant W To Temperature reservoir To Q
o

1st Law 0 = Qo W + H r H p 2nd Law S

gen

Qo = Sr + S p 0 To
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Maximum Power Output

Combined 1st and 2nd law
W = H r H p To Sr S p To S gen
m n

W = ri h To s pi h To s To S gen ri i=1 pi i=1

bri bpi m n

W = ri bri pi bpi To S gen i=1 i=1

Br Bp

where

Br = H r To Sr and

B p = H p To S p

Work output per mole of fuel <= Br Bp Sepng Sgen = 0 Wrev = Br Bp W

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Maximum Power Output

Special Case: inlet and outlet mixtures are at To, Po
Wrev = ri ( h To s )
i =1 m m o ,ri

pi ( h To s )
i =1 n

o , pi

i =1 i =1 where ( h T o s ) o is the par2al molal Gibbs free energy

Wrev = ri o ,ri pi o , pi

Wrev = Gr G p Wrev W

Work lost (ToSgen) is due to:

combus2on processes power plant between combus2on chamber and ambient

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Maximum Power Output

Case: Power plant replaced by Carnot engine
(To, Po) Reactants Hr , Br Reservoir To
Combus2on Chamber (To, Po) Products Hp , Bp

Tf

QH=Hr Hp W Carnot cycle Power plant QL Same as -Qo

Irreversibility (Wrev W) is due to C.C. alone

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Maximum Power Output

Eec2ve ame temperature of the C.C.
" T % W = H r H p $1 o ' $ T f ' # exergy &

heat transfer

2nd law eciency

H r H p To W II = = 1 Wrev Br Bp T f

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