Combustion and Fuels

Usu. Hydrocarbons or Hydrogen in Air are used

Other fuels include: CO, NH3, CS2, H2S, If you use an oxidizer other than air, there is a host of new fuels that can be used (rocket fuels)

Why hydrocarbons?
Many are liquids - high density, easy to transport Lots of it although in the wrong places, e.g., Middle East, Saudi Arabia, Iran, Iraq Relatively non-toxic fuel & combustion products Relatively low explosion hazard

Why Air? (Air = 0.21O2 + 0.79N2)

Its there and FREE! (although much $$ spent to reduce air pollution)

MEM 380, Spring 2003

Types of Hydrocarbons
Alkanes - CnH2n+2
H | H-C-H | H Methane H H | | H - C - C| - H | H H Ethane H H H | | | H - C - C| - C - H | | H H H Propane

Napthenes - Alkanes w/ Rings

H C H-C-C-H H H H Cyclopropane (not very stable -lots of strain in C-C bonds)

MEM 380, Spring 2003

Types of Hydrocarbons
Olefins- Contains one or more C=C
H C=C H Ethylene H H H H H H | C=C-C H H Propene H H H H | | | | C| = C - C = C | H H Butadiene

Acetylenes - Contains one or more C|C bond

H - C | C - H Acetylene (very reactive)!

MEM 380, Spring 2003

Types of Hydrocarbons
Aromatics - contains one or more six-sided ring structures
C C C C|

H |
C C

Benzene

Alcohols - contains one or more -OH groups

H | H - C -O H Methanol | H H H | | H - C - C| - O H Ethanol | H H
MEM 380, Spring 2003

More Fuels
Hydrogen H-H

Carbon Monoxide C = O H Ammonia H-N H

MEM 380, Spring 2003

Stoichiometry
Balancing chemical reactions when products are known (assumed) Example: 1 CH4 + ? (O2 + 3.76 N2) --> ? CO2 + ? H2O + ? N2
from Dr. Pearlmans crystal ball

Balance to get: 1 CH4 + 2 (O2 + 3.76 N2) --> 1 CO2 + 2 H2O + 2 (3.76) N2 Fuel - Air Ratio (FAR) is defined as
Mass Mass
nM uel ! uels i i ir n M air i i

where

ni: moles o i Mi: molecular weight o species i

MEM 380, Spring 2003

FAR
In our example, FAR = FAR = 0.058 AFR = Air to fuel ratio = 1/ FAR = 17.2 Also, Xf = mass fuel/ mass total = mass fuel/ (mass air + mass fuel)
X ! f m f el m air f el m
 m  f el    m  air  !  m 1   f el  m   air

1 mole CH4 x 16g/mol CH4 (2 mole O2 x 32g/mol O2 + 2 x 3.76 mol N2 x 28g/mol N2)

! FAR  1  FAR
    

MEM 380, Spring 2003

Equivalence Ratio
FAR (mixt re) J! FAR (stoic iometric)


J< 1 Excess air (lean mixt re) J> 1 Excess f el (ric mixt re)

If 1 mol CH4 burns with 1 mol air, then: Reactants: 1 CH4 + 1 (O2 + 3.76 N2)
  1     1  J !   ! 2 1      2 

MEM 380, Spring 2003

Equivalence Ratio
What is J for methane-air where the mole fraction of air and products is unknown? 1 CH4 + ? (O2 + 3.76 N2) --> ? CO+ ? CO2 + ? H2O + ? N2 Cant Solve! - too many unknowns 5 unknowns 4 equations (1 for each atom)

Need to consider chemical equilibrium to solve!

MEM 380, Spring 2003

Thermodynamic Calculations of Combustion Processes Motivation: Cannot always determine the amount of various products based on stoich. Considerations - many possible products to choose from. Chemical Thermodynamics to the rescue: Lets us determine which products are obtained if we wait long enough (as short as 1ms to forever). Quiz: What chemical reaction yields the highest known flame temperature? H2 -O2 at J = 1 (T=3079 K at 1atm) NO!!
MEM 380, Spring 2003

Thermodynamic calculations of combustion processes The HIGHEST KNOWN temperature is associated with: C4N2 - O3 at J = 1 (T=5516 K at 1atm) Carbon Sub-Nitride Ozone

C4N2 + O3 -> 4 CO + N2

WHY ?
MEM 380, Spring 2003

Why?
H2-O2 has more heat release per unit mass and per mole of reactants, but the Products are NOT just H2O H2 + O2 -> H2O Rather, H2 + O2 -> 0.58H2O + 0.05O2 + 0.15H2 + 0.08H + 0.11OH + 0.33O Water dissociates into smaller molecules and: 1. Produces more mol of products to soak up more heat, lowering the flame temp. 2. Energy is partly used to break the water into these other things, thus reducing the flame temp.
MEM 380, Spring 2003

Why?
If we prevent water from dissociating, flame temp increases to 4998K. Still lower. Why? Water is triatomic molecule w/ many degrees of freedom (vibrate & rotate). Energy is stored in these d.o.f. How does carbon sub-nitride do it? CO and N2 have fewer d.o.f., so each one soaks up less energy CO and N2 are very stable even at 5500K (dont dissociate)

MEM 380, Spring 2003

Goal of Combustion Thermodynamics

Given Initial State (P, T, Yi) and an assumed Process (Constant P, Constant V, Constant S, ), find the final state of the mixture. Three common processes in engine apps: 1. Compression from low P/ high Vol. To high P/ low Vol. (usu. Pressure or volume is known and the composition is frozen (doesnt change). This process is usually assumed Isentropic (constant entropy)
MEM 380, Spring 2003

Goal of Combustion Thermodynamics

2. Combustion - Usu. assumed constant pressure or constant volume. Composition must change to provide heat release. 3. E pansion - from high P/low V to low P/ high V. The volume ratio or the final pressure ratio is usu. given. Again, assumed isentropic. These analyses are needed to determine the work input/ output, efficiency, heat release, etc.

MEM 380, Spring 2003

Assumptions
Assumptions that we will use: Ideal Gases Adiabatic Kinetic and Potential Energy Negligible Combustion Process is Constant P or Constant V Compression/ Expansion processes reversible -> isentropic (constant entropy)

Lets first consider the combustion process, then the compression and expansion processes
MEM 380, Spring 2003

1st Law of Thermodynamics

For a control mass, dE = HQ + HW where E: energy of system, Q: heat transfer to system, W: work transferred to the system E = U + PE + KE, so dE = dU + d(PE) + d(KE) = HQ + HW For d(PE) = d(KE) = 0, HQ = 0 (adiabatic) & HW = - PdV for simple compressible substance Get, dU + PdV = 0 -> dH = 0 for constant pressure process (recall, H = U+PV) --> Hreactants = H products
MEM 380, Spring 2003

1st Law of Thermodynamics

Also, recall h=H/M (M: mass = constant for a fixed control mass) Since, Hreactants = Hproducts @Hreactants/Mreactants = Hproducts /Mproducts Thus, hreactants = hproducts or constant volume process (dV=0): dU = 0 or U = H - VP = constant or h - vP = constant (v=V/M, h = H/M) Thus, (h - vP)reactants = (h - vP)products for constant V process

MEM 380, Spring 2003

Total Enthalpy
n H! n h i i i!1

Enthalpy/mole of species i

Total enthalpy  of a mixture

Moles of species i

  h ! h  h  (ho   i  298 i f,i

Thermal contribution  = cp,i (T-298) if cp is constant a f(T) only for ideal gases Chemical contribution ~: per mol o: standard state f: formation i: species i
MEM 380, Spring 2003

For Constant Pressure Process

n n   o   h  h H! n h ! n  (h   i i i!1 i 298 i i!1 f,i   


hreactants = hproducts

n and recall h=H/M and M! niMi i!1

      

(h o n hh i 298 i i!1, f,i reactants n niMi i!1,

     

= same sum for products

reactants

(Energy Equation)

MEM 380, Spring 2003

For Constant Volume Process

Know PV=nRT
n ni i Pv=nRT=(n/M)RT = RT n!1 niMi i!1

Recall, h-vP = constant

~ ~ ~o  (h  RT n hh i 298 i i!1, f, i reactants = same sum for products n niMi i!1,

reactants

MEM 380, Spring 2003

For Constant Volume Process

In constant volume process, usu. we want to know the final pressure
nf R Tf nf R Tf nf R Tf f f f Pf ! ! !P V i niR iTi n R T i i

P i

Recall, R=Ro/M, therefore Rf = Ro/Mf and Ri = Ro/Mi where Mf=Mi=total mass of reactants (products) doesnt change @ Rf = Ri
nf Tf Pf ! P ! niTi i
T P f i T i n i prod. n i reacts.

MEM 380, Spring 2003

Heating Value of a Fuel

For a const. P process we said:

~ ~ ~ n hh  (h o i 298 i i!1, f, i reactants n niMi i!1,

reactants

! Constant

i!1, reactants

~ ~  n hh i 298 i

i!1, reactants

n n ~ ~ ~o ~o  n (h  n ( h n hh i f,i i i f,i 298 i i!1, i!1, i!1, products products ! reactants n nM niMi i i i!1, n

reactants

(Chemical enthalpy change per unit mass)

MEM 380, Spring 2003

LHS
i!1, reactants

~ ~  n hh i 298 i

i!1, reactants

i!1, ro cts

~ ~ n hh i 298 i

nM i i

n ~ ~ n hh i 298 i i!1,

is total thermal enthalpy of mixture =

p T  298M

Avg Cp per unit mass

Cp, reactants T T  298 - C  298 p, products products reactants

MEM 380, Spring 2003

RHS
n n ~o ~ n (h  n (ho  i f, i i f, i i ! 1, i ! 1, reactants pro cts n M f el f el
M n f el f el n nM i i i ! 1, reactants

-QR Heating Value of the Fuel (per unit mass of fuel)

Fuel Mass Total Mass = fuel mass/(fuel+air mass) = FAR/(1+FAR)

MEM 380, Spring 2003

Example of QR Calculation
Combustion of iso-octane-air 1C8H18 + 25/2(O2+3.76N2) -> 8CO2 (g) + 9H2O (g) + 25/2(3.76)N2
n n ~o ~ n (h  n (h o i f, i i f, i i ! 1, i ! 1, reactants pro ucts ! n M fuel fuel

Q R

[1mol(-59.74kcal/mol)+25/2(0+0)] [8(-94.1)+9(-57.8)+25/2(0)] = [1mol (0.114 kg/mol)]

Table 4.4

= 10640 kcal/kg fuel = 4.5 x 107 J/kg fuel (most HCs ~4-5x107)
MEM 380, Spring 2003

LHS = RHS
FAR Cp, reactants T T  298 - C  298 ! Q p, products products reactants 1 FAR
R

If we assume p, reactants } p, products

FAR T -T ! Q p products reactants 1 FAR
R

Not bad if mostly N2

Good approximation to energy equation to get Tproducts =Tflame

Note:

For constant volume combustion everything else same except replace p by

MEM 380, Spring 2003

Example
3H2 + O2 -> 2H2O + 1H2 Pi = 1atm, Treactants=400K Question: What is Tproducts if Pf=1atm (constant pressure process)? Reactants: H2: cp=6.9 cal/mol/K at 298K O2: cp=7.0 cal/mol/K at 298K Products: H2O: cp=8.03 cal/mol/K at 298K hreactants =
~ (ho f ~o (h f
!0 !0 ~ (ho ! 57.8 kcal/mol f

[3mol(6.9cal/mol/K)(400-298)K+0)+1mol(7.0)(400-298)+0] [3mol(0.002kg/mol)+1mol(0.032kg/mol)]

= 7.4 x 104 cal/kg [2mol(8.03cal/mol/K)(T-298)-52800)+1mol(6.9)(T-298)+0] hproducts = [2mol(0.018kg/mol)+1mol(0.002kg/mol)] = 7.4 x 104 cal/kg

MEM 380, Spring 2003

Example (cont.)
Set hreactants = hproducts & Solve for T (=5459K) Too high!! Why? Because cp{const. Alternative, use cp{const, look up (h-h298) in tables A.5 & A.12 [3mol(707cal/mol+0)+1mol(723cal/mol+0)] hreactants = [3mol(0.002kg/mol)+1mol(0.032kg/mol)] =7.4 x 104 cal/kg hproducts = [2mol(h-h298)H2O-57800cal/mol]+1mol((h-h298)H2+0)] [2mol(0.018kg/mol)+1mol(0.002kg/mol)]

Need to find T such that hreactants = hproducts: Guess, then reinterate. At T=4014K, (h-h298)H2O=44064 cal/mol; (h-h298)H2=30455 cal/mol Evaluate hproducts = 7.8x104 cal/kg, getting close, reiterate!
MEM 380, Spring 2003