Ombustion: P - R T Cellphone

COMBUSTION
PPROF
ROF ..SSEUNG
EUNGW OOKBBAEK
WOOK AEK

DDEPARTMENT OFAAEROSPACE
EPARTMENTOF EROSPACEEENGINEERING
NGINEERING, ,KAIST, INKOREA
KAIST,IN KOREA
RROOM
OOM::Building
BuildingN7-2
N7-2 #3304
#3304
TTELEPHONE
ELEPHONE::3714
3714
Cellphone
Cellphone ::010
0105302
5302--5934
5934
swbaek@kaist.ac.kr
swbaek@kaist.ac.kr
http://procom.kaist.ac.kr
http://procom.kaist.ac.kr
TTAA :: Bonchan
BonchanGu
Gu
RROOM
OOM::Building
BuildingN7-2
N7-2 ##3315
3315
TTELEPHONE
ELEPHONE::3754
3754
Cellphone
Cellphone ::010
0103823
3823--7775
7775
ryan.bonchan@kaist.ac.kr
ryan.bonchan@kaist.ac.kr
SYLLABUS (1/4)
COURSE CODE : MAE 415
COURSE NAME : COMBUSTION ENGINEERING
PROFESSOR : SEUNG WOOK BAEK (Rm #3304, Ext. 3714)
GRADING SYSTEM
1 Final Exam ( June 11th, 2015 )
Homework
ISSUES IN COMBUSTION SCIENCE
How to efficiently mix fuel and oxidizer
Convection and diffusion
How to efficiently burn fuel and oxidizer: energy saving

How to reduce pollutant emission such as CO,CO2 and NOx
How to improve safety and reduce impact on environment
To develop green, sustainable and alternative energy
SYLLABUS (2/4)
REFERENCES
F.A.Williams, Combustion Theory, Addison Wesley, 2nd Ed.
D.B.Spalding, Combustion and Mass Transfer, Pergamon
Press
I.Glassman, Combustion, Academic Press, 2nd Ed.
M.Kanury, Introduction to Combustion Phenomena, Gordon
and Breach Science Publishers
P.A.Libby and F.A.Williams (Editors), Turbulent Reacting
Flows, Springer Verlag
L.A.Kennedy (Editor), Turbulent Combustion, Progress in
Astronautics and Aeronautics, Vol.58
SYLLABUS (3/4)
K.K.Kuo, Principles of Combustion, Wiley
V.R.Kuznetsoz and V.A.Sabelnikov, Turbulence and
Combustion, Hemisphere Publishing Corporation
JOURNALS
Combustion and Flame
Combustion Science and Technology
Symposium (International) on Combustion
Combustion Theory and Modeling
AIAA Journal
Progress in Energy and Combustion Science
SYLLABUS (4/4)
Combustion, Explosion and Shock Waves
Progress in Astronautics and Aeronautics
Fire Safety Journal
International Journal of Heat and Mass Transfer
Journal of Heat Transfer
Journal of Thermophysics and Heat Transfer
Journal of Propulsion and Power
Thermochemistry
Combustion- high temperature, moderate or high pressure,

perfect gas, real gas effects for high pressure environment
Thermodynamic properties of a single perfect gas
R
Equation of p T CR T
state : W
energy
R : Universal gas constant mole K

mass
W : Molecular weight mole

C : Concentration mole
unit volume
PROPULSION AND COMBUSTION LABORATORY Combustion Engineering

Internal Energy
u : per unit mass
u u 0 cV T dT
T
T0
u 0 : Internal energy of formation

energy
cV : Specific heat
mass K

Enthalpy
p RT T RT
hu u u 0 cV dT
W T0 W
or
RT T R R T R T0
h u0 0 T cP dT
W
0
W W W
c P T dT
T
= h0 T0
h0 : Enthalpy of formation

Only change in u or h is important (not the absolute level)
Need a convention for h0 and u 0
1) Prescribe a standard state, i.e., T0 and p 0
2) The formation enthalpy of the chemical elements in their
T0 p0
natural phase at and will be zero.
p
3) 0 1 atm T
, 0 298 . 16 K
h0 for, H 2 g : h0 0 H 2 O g : h0 0 C s : h0 0
N 2 g : h0 0 H 2 l : h0 0

dh vdp
Tds dh vdp ds
T T
Entropy
dh R dp cP RT p
ds s s0
dT ln
T W p T0 T W p0
Let s 0 = Entropy at p 0 and any temperature T .
R p
s s0 ln
W p0
Gibbs Free Energy
f h Ts per unit mass basis
R p RT p
f h T ( s 0 ln ) f 0 ln
W p0 W p0
f 0 h 0 Ts 0 h Ts 0
RT p
f f0 ln
W p0
On a molar basis
p
Wf F F 0 R T ln
p0
F : Molar basis
Helmholtz Free Energy

a u Ts

Mixture of perfect gases ;
aH 2 bO2 cN 2
CT : Total number of moles per unit volume

C K : Total number of moles of species K per unit volume
X K : Mole fraction of species K
CK
CT C K XK XK 1
K CT K

: Density of the mixture
K : Partial density of species K
YK : Mass fraction of species K
WK : Molecular weight of species K
K WK C K
K K
K
YK
,
K
YK 1

CK K YK
WK WK

K
K WK CK W j C j CK YK
K K j WK WK
K YK Yj
CT CK
K WK K WK j Wj
CK Y / WK K W C W X
XK K , YK K K K K
CT Y j / W j W j C j W j X j
j j j
W : Mean molecular weight of the mixture

YK
K WK W 1
W WK X K K

K Y j /W j Y j /W j
j j

1 YK YK 1
, W ( ) X KWK
W K WK K W
K
K
EQUATION OF STATE
pK CK R T
Partial pressure exerted by species K if it occupies

the whole volume at temperature T.
PROPULSION AND COMBUSTION LABORATORY

Daltons Law
p pK RT CK CT RT CTWRT RT
K K
but Y
CT K ,
W K WK
Y R
p R T K T
K WK W
Internal Energy
u u
K
K YK

u K u K 0 cVK T dT
T
T0
T
u YK u K YK uK0 YK cVK T dT
T0
K K
T
u u 0 cV dT where u 0 YK u K 0
T0
K
T T T
Y
K
K
T0
cVK dT Y
T0
K
K cVK dT
T0
cV dT
cV YK cVK
K

Enthalpy
h Y
K
K hK
T
h h0 c P dT when YK is fixed
T0
h0 YK hK 0 c P YK c PK
K K
Entropy
s YK s K
K

cP
T R p
s s0 dT ln
T0 T W p0
T c PK R pK
s K s K0 dT ln
T0 T WK p 0
Y c
T
K PK
YK pK
s YK sK YK sK0 K
dT R ln
K K T
T0
K WK p0
TcP YK pK p
s0 dT R ln ln
T0 T
K WK p p0

cP
T YK pK p WK X K W X
s s0 dT R ln
ln YK K K
T0 T
K WK p p0 W j X j W
j
T cP R p Y
s s0 dT ln R K ln X K
T0 T W p0 K WK R
cP
T R p YK

W
X K ln X K
s s0 dT ln R ln X K K
T0 T W p0 K WK
1 4 4 44 2 4 4 4 43 1 44 2 4 43
Entropy that a perfect gas of W and cP Entropy increases due to mixing
would have for p and T XK 1 so that positive term
RT p
YK f K
0
f fK fK ln K
K WK p0
YK p
f f 0
RT ln K
K WK p0

YK XK

WK W
Y p Y p p
f f 0 RT K ln K f 0 RT K (ln ln K )
K WK p0 K WK p0 p
RT p Y RT
f f0 ln R T K ln X K X K ln X K
W p0 K W
K W K
hK
Caution ; c PK T
p
h
When there is reaction c P
T p
h hK YK
h YK h K YK hK
K T p K T p K T p
h Y
cP hK K
T p K T p

Problem for notes
Binary mixture of H 2 2 He 4
Y
W
K
2YH 2 1 Y
X X H2 K
, X H2
Y YH 2 1 1 Y
K He
j W j
H2
1 YH 2 YHe , c Y c 1 Y c
P H2 PH 2 H2 PHe
Specification of Composition
p KV nK R T , pV nT R T For same V , T

p K n K m K / WK W
YK
p n m /W WK
For same P and T, partial volume of species K
R R
pVK m K T, pV m T
WK W
VK m K W n K WK W n K

V m WK nT W WK nT
mK
Here, V is not V K so that YK .
m

Material Balance for Chemical Reactions
Ex) Combustion of Octane with Air
Air: 0.21O 0.79 N 3.76 moles of N per 1 mole of O
2 2 2 2
Molecular Weight: 0.21 32 0.79 28 28.8 29

For complete combustion (stoichiometric)
25 25 79 25 79
C8 H 18 O2 N 2 8CO2 9 H 2 O N 2
2 2 21 2 21
C8 H 18 1
Stoichiometric Coefficients:
25 79
O 25 / 2, N2
2
2 21

On a mass basis,
25 25 79 25 79
C8 H 18 O2 N 2 8CO2 9 H 2 O N2
2 2 21 2 21
114 8 44 918
25 25 79 25 79
32 28 28
2 2 21 2 21

1831 lbs ( or gms )
or 15.1 kg of air/ 1 kg of octane

For reactants
1 1
X C8 H18 0.0165
25 25 79 60.52
1
2 2 21
25 / 2 25 / 2 79 / 21
X O2 0.2065, X N 2 0.7769
60.52 60.52

25 25 79 25 79
C8 H 18 O2 N 2 8CO2 9 H 2 O N2

114 2 2 21 8 44 918 2 21
25 25 79 25 79
32 28 28
2 2 21 2 21

1831 lbs ( or gms )
114
YC8 H18 0.0623
1831
1831
W 30.3
60.52
: MEAN MOLECULAR WEIGHT OF REACTANTS
MASS OF PRODUCTS = 1831

8
X 0.125 nP nR
CO2
25 79
89
2 21

EQUIVALENCE RATIO :
mass of fuel
mass of oxidizer

mass of fuel

mass of oxidizer stoichiometric
FOR 1
CH 4 2O2 2 3.76 N 2 CO2 2 H 2O 2 3.76 N 2
1 : STOICHIOMETRIC
1 : FUEL LEAN
1 : FUEL RICH
FOR 0.9 0.9CH 4 2O2 2 3.76 N 2
FOR 1 CH 4 different
ENERGY Eq. FOR CHEMICAL REACTION

CONSTANT VOLUME SYSTEM NO MOTION

1st LAW : Q dE W
Q : HEAT TRANSFER
(POSITIVE WHEN ADDED TO THE SYSTEM)
dE : INTERNAL ENERGY
W : WORK DONE BY THE SYSTEM
1: REACTANT STATE
1 Q2 E 2 E1
2: PRODUCT STATE

ONLY IMPORTANCE IS E, NOT THE ABSOLUTE VALUES.
TB
: REFERENCE OR
BASIC TEMPERATURE 25C
E B
: INTERNAL ENERGY OF REACTION,
DETERMINED IN A BOMB CALORIMETER

Q E 2 E1 E 2 E 2 B E 2 B E1B E1B E1
E2 E2 B E E E
B 1
1 B
fixed composition tabulated fixed composition
FOR CONSTANT PRESSURE PROCESS;

Q dE W dE pdV dH Vdp
Q2 H 2 H1 H 2 H 2 B H 2 B H1B H1 H1B
1
14243
H B

H B H 2 B H1B
H B : ENTHALPY OF REACTION
H B E B p 2 BV2 B p1BV1B
E B :INTERNAL ENERGY OF
REACTION AT TB
FOR PERFECT GASES;
E B V const E B p const

Q H 2 H1 H 2 H 2 B 1H42 B2 4H13B H1 H1 B
H B EB p2 BV2 B p1 BV1 B
p 2 BV2 B p1BV1B n2 R TB n1 R TB nR TB
n n 2 n1 H B E B nR TB
ENTHALPY OF FORMATION AND ENTHALPY OF COMBUSTION
ENTHALPY OF FORMATION -THAT CHANGE OF ENTHALPY
WHICH OCCURS WHEN A COMPOUND IS FORMED FROM THE
ELEMENTS, WHICH ARE IN THEIR STABLE STATE, AT SAME
STANDARD TEMPERATURE AND PRESSURE.

C s O2 g CO2 g GIVES OFF 94052 cal :exothermic reaction
H 0
f CO
2
94052 cal / gmole of CO2
HEAT OF FORMATION = H 0f 94052 cal / gmole of CO2

ALSO A COMBUSTION PROCESS
ENTHALPY OF COMBUSTION H 0
c H f 94052 cal / gmole o
0
HEAT OF COMBUSTION 94052 cal / gmole of CO2

HEAT OF COMBUSTION OF 94052
C (s) cal / g of C ( s)
12

H B E B nR TB
ENDOTHERMIC REACTION
1
Ex) N 2 g O2 g NO2 g
2
H
0
f NO
2
8091 cal / gmole of NO2
HEATING VALUES; FOR C+O2 REACTION,

H B E B ,BECAUSE THERE IS NO pdV WORKS.
IN GENERAL, H B E B
HIGHER HEATING VALUES AND LOWER HEATING VALUES
DEPEND ON STATE OF PRODUCTS.

IMPORTANT CASE IS H 2 O g vs. H 2 O l
1
H 2 O2 H 2 O
2
IF H 2 O IS LIQUID, HHV H 2 O 34.32 kcal / g of H 2

LHV DIFFERS FROM HHV BY HEAT OF VAPORIZATION.
9 g of H 2 O
LHV HHV 0.602 kcal / g of H 2 O 28.9 kcal / g of H 2
g of H 2

REFERENCES FOR THERMOCHEMICAL DATA
1. NBS, Tables of Selected Values of Chemical Thermal
Properties, Circular Letter 500
2. JANAF Thermo-Chemical Tables (1993)
3. Penners Book
4. Van Wylen & Sonntag (SI units)
5. CHEMKIN: Software package for the analysis of gas-
phase chemical and plasma kinetics (2000)
EXAMPLE
10g OF H2 (g) BURN IN AIR (=1) AT CONSTANT
PRESSURE. INITIAL TEMPERATURE IS 298K AND FINAL
TEMPERATURE IS 2000K SO THAT H2O IS GASEOUS.
CALCULATE THE HEAT LIBERATED ;
Q H 2 H1
10 g of H 5moles 2
5 5
5H 2 ( g ) O2 ( g ) (3.76) N 2 ( g ) 5H 2 O( g ) 9.4 N 2 ( g )
2 2
H 2 5H H 2O ( g ), 2000 K 9.4 H N 2 ( g ), 2000 K
5
H1 5H H 2 ( g ), 298 K H O2 ( g ),298 K 9.4 H N 2 ( g ),298 K
2
H H 2O ( g ), 2000 K H 2000 K H 298 K H f , H 2O ( g ), 298 K
19630 2367.7 57798 40535.7 cal
mole
H N 2 ( g ), 2000K 15494.8 2072.3 H f , N 2 ( g ), 298K
H H 2 ( g ), 298 K H O2 ( g ), 298 K H N 2 ( g ), 298 K 0
Q 76512cal MINUS INDICATES THAT HEAT WAS
TRANSFERRED OUT OF THE SYSTEM. IN OTHER
WORDS, THE FLAME TEMPERATURE, IF ADIABATIC,
WOULD BE HIGHER THAN 2000 K.
IF THE PROBLEM WERE AT CONSTANT VOLUME,
Q E 2 E1
E H pV H n RT
5E H 2O ( g ), 2000 K
5H H 2O ( g ), 2000 K
n RT
5 (40535.7)cal 5 1.9807 2000cal, etc.
CALCULATION OF ENTHALPY OF REACTION FROM
THE ENTHALPY OF FORMATION
R
H

H

f P

H

f R

Reaction Products Reactants
REACTION ; aA bB mM nN
b m n
or A B M N
a a a
H

R mole of A
m
a

H f M

n
a
H f N

b
a
H f H
B

f A

EX) GASEOUS CH4 + O2 REACT TO YIELD H2O(l)+CO2(g).
CALCULATE H
R
PER MOLE OF CH4
CH ( g ) 2O ( g ) CO ( g ) 2 H O(l )
4 2 2 2
H

R CH 4
H f CO2 (g)

2 H
f H O (l )
2

H
f CH 4 (g)

2 H
f O2 ( g )
94.05 2 68.32 17.9 212.8kcal

EXOTHERMIC PER MOLE OF CH4

CONSIDER A CHEMICAL SYSTEM OF CONSTANT MASS
EITHER HOMOGENEOUS OR HETEROGENEOUS IN
MECHANICAL AND THERMAL EQUILIBRIUM BUT NOT IN
CHEMICAL EQUILIBRIUM. THE SYSTEM IS IN CONTACT
WITH A RESERVOIR AT TEMPERATURE T AND
UNDERGOES AN INFINITESIMAL IRREVERSIBLE
EXCHANGE OF HEAT, Q, TO THE RESERVOIR. PROCESS
MAY INVOLVE CHEMICAL REACTION AND TRANSPORT
BETWEEN PHASES.

dS: ENTROPY CHANGE OF THE SYSTEM
dSO: ENTROPY CHANGE OF THE RESERVOIR
dS+dSo: ENTROPY CHANGE OF THE UNIVERSE
dS dS 0
O
Q Q
dS dS 0
T
O
T
Q Q s
FROM SYSTEM Qs
dS 0
T

1ST LAW Qs dE pdV
Qs
FROM SYSTEM dS 0
T
dE pdV TdS 0
VARIOUS CONSTRAINTS
CASE A ; HOLD E AND V CONSTANT
dS 0 ISOLATED SYSTEM
CASE B ; HOLD p AND T CONSTANT
d [ E pV TS ] d [ H TS ] dF 0
GIBBS FREE ENERGY DECREASES
-
WHEN FP ,T 0 ; HAVE CHEMICAL EQUILIBRIUM
CASE C ; HOLD V AND T CONSTANT

d [ E TS ] dA 0
AT EQUILIBRIUM ; AV ,T 0
RT pK
fK fK 0 ln
WK p0
pK pK
WK f K FK WK f K 0
RT ln FK RT ln
0
p0 p0
EQUILBRIUM OF A MIXTURE OF PERFECT GASES

UNDERGOING CHEMICAL REACTION
CONSIDER THE REACTION,
aA bB
cC dD
FOR P0 1atm

WE KNOW GIBBS FREE ENERGY FA
AND ANY TEMPERATURE T PER MOLE.
FA AT ANY T AND P ;
FA FA RT ln p A p0
FB FB RT ln pB p0
, ETC
pK
FK FK 0
RT ln
p0
F cFC dFD aFA bFB

o pC o pD o pA o pB
c
FC RT ln d
FD RT ln a
FA RT ln b
FB RT ln
p0 p0 p0 p0
LET F
cF C

dFD

aF
A bF B

C 0 D 0
c d
p p p p
F F RT ln
o
b
p A p0 pB p0
a
P0 1 atm
pCc pDd
F F RT ln a b
o
p A pB
pCc pDd
DEFINE K P a b equilibrium constant based on pressure
p A pB
AT EQUILIBRIUM F 0
F RT ln K P
F RT
KP e
F f (T )
K P g (T )
pA
NOTE THAT X A mole fraction
p
pB pX B pC pX C pD pX D
X Cc X Dd c d ( a b ) X Cc X Dd n
KP a b p a b p
XAXB XAXB
WHERE n (c d ) ( a b)
EFFECT OF T ON EQUILIBRIUM COMPOSITION IS GIVEN IN
Kp
n
EFFECTS OF p ON THE p TERM.
FOR THE CASE OF n 0 , IE. C + D = A + B
NO PRESSURE EFFECT
EQUILIBRIUM CONSTANT BASED ON CONCENTRATION ; K C
mole
C Concentration
unit volume
CCc C Dd
KC a b pC CC RT , ETC
C AC B
pCc pDd

n n
K C a b RT K p RT
p A pB
VALUES OF KP ARE TABULATED FOR SPECIFIC
CHEMICAL REACTION.
EX) DISSOCIATION OF CO2
1 pCO pO1 22
CO2
CO O2 K P1 (1)
2 pCO2

1 pCO2
K P1
1
CO O2
CO2 KP2 (2)
2 pCO pO1/22
2
pCO
2CO O2
2CO2 K P1
2
K P3 2
2
(3)
p pO2
CO
EQUILIBRIUM COMPOSITION
EX) 100% WATER VAPOR, INITIALLY AT 1 atm AND 2200

K DISSOCIATES INTO H2 (g) AND O2 (g). ASSUMING
PERFECT GASES THROUGHOUT, DETERMINE THE
EQUILIBRIUM COMPOSITION
1
CHEMICAL REACTION H 2O( g ) H 2 ( g ) O2 ( g )
2
pH 2 pO1 22 12
X H 2 X O2 1 2
KP p
p H 2O X H 2O
H 2 O aH 2 O bH 2 cO2 EQUILIBRIUM COMPOSITION
H : 2 2a 2b b 1 a
O : 1 a 2c c (1 a ) 2
(1 a)
H 2 O aH 2 O 1 a H 2 O2
2
(1 a) 3 a
nT a (1 a)
2 2
1 a
1 a a
X H2
3 a X 2 X H 2O
O2
3 a 3 a
2 2 2
12
1 a
1 a 2
3 a 3 a
1 a P
32 12
KP 2 2 p12
, KP 1.145 10 3
a 3 a
12
a
3 a
2
0.0137 EQUILIBRIUM
H 2 O 0.9863H 2 O 0.0137H 2 O2
2 COMPOSITION
H 2 O aH 2 O bH 2 cO2
1 a p
32 12
KP (1 a)
a 3 a
12 H 2O aH 2 O 1 a H 2 O2
2
EXAMINE LIMITING CONDITIONS

CASE I - LOW TEMPERATURES
; VERY LITTLE DISSOCIATION
LET a 1 1
13
3 2 P1 2 2
KP 12
OR K P2 3
2 P
A) HIGHER PRESSURE ; LOWER ; GREATER a
LESS DISSOCIATION
B) HIGHER TEMPERATURE ; HIGHER KP GREATER ;
SMALLER a
MORE DISSOCIATION
1 a
32
p1 2 (1 a)
KP H 2 O aH 2 O 1 a H 2 O2
a 3 a
12
2
CASE II - HIGH TEMPERATURES ; HIGH DISSOCIATION

a 1
12 12
P P 1
KP 1 2 OR
3 3 KP
A) HIGHER PRESSURE ; HIGHER ; HIGHER a
LESS DISSOCIATION
B) HIGHER TEMPERATURE ; HIGHER KP ; LOWER = a
MORE DISSOCIATION

EQUILIBRIUM WHEN SIMULTANEOUS REACTIONS
OCCURRING
THE NUMBER OF INDEPENDENT REACTIONS, WHICH MUST
BE CONSIDERED IN EQUILIBRIUM CALCULATIONS, IS
EQUAL TO THE LEAST NUMBER OF EQUATIONS WHICH
INCLUDE ANY REACTANT AND PRODUCT WHICH ARE
PRESENT TO AN APPRECIABLE DEGREE IN THE
EQUILIBRIUM MIXTURE.
EX) CALCULATE THE COMPOSITION OF THE EQUILIBRIUM
MIXTURE OBTAINED WHEN 5 MOLES OF STEAM, H2O
(g) REACT WITH 1 MOLE OF CH4 AT ELEVATED
TEMPERATURE AND SOME ARBITRARY PRESSURE
CH 4 5H 2O aCH 4 bH 2O cCO dH 2 eCO2
C: 1 =a+c+e
H : 14 = 4a + 2b + 2d
O : 5 = b + c + 2e
CH 4 5 H 2O
aCH 4 bH 2O 3 2a b CO 7 2a b H 2 4 a b CO2
MECHANISM FOR REACTION ;

2 ACTUAL REACTIONS ARE ;

CH 4 5 H 2O
aCH 4 bH 2O 3 2a b CO 7 2a b H 2 4 a b CO2
CH 4 H 2O
CO 3H 2 H R 0 (1)
CO H 2O CO 2 H 2 H R 0 (2)
pCO pH3 2 pCO2 pH 2
K P1 KP2
pCH 4 pH 2O pCO pH 2O
nT a b c d e 8 2a
3 2a b
3 2a b 7 2a b
3
p 2 pCO X CO p p
K P1 8 2a
ab 8 2a
2
etc.
K P2
4 a b 7 2a b
3 2a b b
PRODUCT RULE FOR KPs
aA
cC eE (1)
eE bB
dD (2)
ADD aA bB
cC dD (3)
pCc pEe pDd pCc pDd

K P1 KP2 e b K P3 a b K P1 K P 2
p Aa pE pB p A pB

ADIABATIC FLAME TEMPERATURE Q 0
POINT (2) FINAL TEMPERATURE AND H AFTER

A NON-ADIABATIC REACTION
POINT (2i) ISOTHERMAL REACTION
POINT (c) ADIABATIC FLAME TEMPERATURE ; H2=H1
CONSTANT PRESSURE REACTION GENERAL CASE
m n
a A b B i i i i
i i
R P
DETERMINE TC FROM H2=H1 Q 0
H2 DEPENDS ON THE bi WHICH DEPENDS ON Tc WHICH
DEPENDS ON THE bi.
n m
b
i
i ,TC H Bi ,TC ai ,Ti H Ai ,T1
i

FOR PERFECT GASES
i bi,TC H C P dT ai ,T1 H f A C P dT
n m

TC

T1
f B
i TB i i TB

n m
WHERE i ,T
b
i

C
H f B
i ,T

a i
i
H
f A

1
Hi

r
TO CALCULATE Tc
1. ASSUME TC FOR GIVEN PRESSURE
2. CALCULATE THE bi FROM THE KPs
3. SUBSTITUTE INTO H2=H1
4. ITERATE UNTIL H2=H1

CALCULATE THE ADIABATIC FLAME TEMPERATURE
OF A = 0.8 METHANE O2 MIXTURE AT p = 10 atm,
TAKING INTO ACCOUNT THE DISSOCIATION OF CO2
AND H2O
1.0 CH 2O
4
CO 2 H O
2 2 2
0.8 0.8CH 4 2O2

aCO2 bH 2O cCO dH 2 eO2
0.8CH 4 2O2

aCO2 bH 2O 0.8 a CO 1.6 b H 2 1.6 0.5a 0.5b O2
2 UNKNOWNS
nT a b c d e 4 0.5a 0.5b
a e
X CO2 X O2 etc.
nT nT
Dissociation Reactions
1 1
1 pCO pO2 2
X CO X O22 1
CO2 CO O2 K P1 p 2
2 pCO2 X CO2
1 1
1 pH 2 pO2 2
X H 2 X O22 1
H 2 O H 2 O2 KP2 p 2
2 pH 2O X H 2O
H 2 H1

a H CO2 TC

b H H 2O TC

c H CO TC d H H 2 TC

e H O2 TC

0.8 H CH 4 T1

2 H O2 T1

Procedure ; assume Tc; Calculate a,b,c,d,e
Substitute into H2=H1 (from Energy Equation)
If Tc=3000K
Hco 2
HH 0 2
a[-94.05 kcal/mole + 38.94-2.24]+b[-57.8+32.16-2.37]

Hco HH 2
+c[-26.42+24.43-2.07]+d[0+23.19-2.02]
Ho 2 HCH 4 Ho 2
+e[0+25.52-2.07] = 0.8[-17.89]+2[0]

Tables of Thermodynamic Properties


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