FIRST LAW APPLIED TO COMBUSTION

Steady Flow Calorimetry The aim is to extract the maximum energy (heat) from the products of combustion and to reduce the product's temperature to the reactant's temperature. ie as per the Gas Calorimeter

2 Products Adiabatic chamber Cooling water . Q

1 Reactants Applying the SFEE:-

& +W & =m & {(h 2 - h1 ) + DKE + DPE} Q

& = m & fuel + m & air = m & fuel ( 1 + AFR ) NB : m

. The change in KE & PE is negligible, & W=0, therefore:

& = m &P - H &R & ( h 2 - h1 ) = H Q

. NB: Q . is negative since it flows out of the system. |Q| is a maximum when exit temperature is a minimum
Combust2a.ppp 1

HP<HR therefore the products of combustion contain less stored energy than the reactants (as we would expect). In order to obtain a standard measure of the heat released by combustion it is necessary to standardise the temperature of the reactants and products. This temperature is 25C (see your tables). 15C is also used. This standard measure is known as the Enthalpy of Combustion and is usually expressed in kJ or MJ per kmol. In practice the temperatures of the reactants and products will not be standard, so we may write :-

& = (H & -H & )+H & - (H & -H & )-H & Q P P0 P0 R R0 R0

where subscript '0' denotes standard conditions. ie.

& = (H & -H & ) - (H & -H & ) + DH & Q P P0 R R0 0

The first two terms are the sensible heat differences and relate to the specific heat capacity Cp. The last term is the standard chemical energy release. thus and

&P - H & P0 = m & P (Cp ) P (TP - T0 ) H &R - H & R0 = m & R (Cp ) R (TR - T0 ) H

Because Cp varies with temperature it is necessary to use a mean value. The Cp value at the mean temperature is often sufficiently accurate. If more precise values are required actual molar enthalpies may be used.
Combust2a.ppp 2

If we do not extract heat from the combustion reaction the products leave with the heat from the reaction. This is known as Adiabatic Combustion, and allows the maximum temperature of the products to be found. This maximum temperature is often called the 'adiabatic flame temperature'. . Putting Q=0 in the above equation gives a method for determining the adiabatic flame temperature for a particular fuel, oxidant and fuel/oxidant ratio. Example: Octane (C8H18) vapour burns with air at an AFR of 60 by mass. Determine the adiabatic flame temperature given that the Enthalpy of Combustion of Octane is -5116.2 MJ/kmol. Assume the reactants enter the combustion chamber at standard temperature. First write the combustion equation:

C8 H18 + y(0. 21O2 + 0. 79N2 ) aCO2 + bH2O + cO2 + dN2

The molar mass of C8H18 is 114 kg/kmol, & air is 29 kg/kmol. 29y = 60 114 y = 235.86 We may solve for a to d in the normal way to obtain:a=8 b=9 c = 37.03 d =186.33
Combust2a.ppp 3

From the First Law equation:

&0 & R ( C p ) R ( TR - T0 ) = m & P ( C p ) P ( TP - T0 ) + D H m

This term is zero

\ also &0 & P ( C p ) P ( TP - T0 ) = - D H m &R = m & fuel + m & air = m & fuel (1 + AFR ) m

D h0 & =m & and D H 0 fuel M fuel

enthalpy/kmol molar mass of fuel

so or

( C p ) P ( TP - T0 ) = -

1 D h0 1 5116 . 2 = = 0. 73572 MJ / kg (1 + AFR ) M fuel 61 114

( C p ) P ( TP - T0 ) = 735 . 72 kJ / kg

Before we can find TP we need Cp, but before we can find Cp (at the average temp {TP+T0}) we need TP! We estimate TP, find Cp, then recalculate TP etc. A good first estimate for TP can be found by putting Cp=1kJ/kg whence TP 760C (1033K) & Tav 386C (660K) For the exhaust gas mixture which we found from the combustion equation we can now determine a mean Cp and use it to refine the value for TP, etc. An alternative method is to use the molar enthalpies directly.

Combust2a.ppp

&P - H & P0 = n & A (hAT - hA0 ) + n &B (hBT - hB0 ) + etc H

'h' is the molar enthalpy of each of the gas mixture constituents A, B etc. Using the listed molar enthalpies (Haywood Table 3) we can easily set up a table to determine HP-HP0 at different temperatures. We need set up the table only for temperatures around our previous estimate.

target SUM = -5116.2 MJ By linear interpolation:Tp= 972K (699C)

Combust2a.ppp

Diagrammatic Representation of Combustion Processes Calorimeter Processes (Const. Temperature) Flow H

a Re n cta ts Re a

Non-flow
(Bomb Calorimeter)

U
n cta ts

HRT-HRO D Ho

u rod

p.) a (v cts

(liq
HPT-HPO

.)
D Uo

ts uc d o Pr

p.) a (v

(liq

.)

To T

Temp.

To

Temp.

H
R nts a t c ea

Pro

cts u d

(va

p.)

HR1=HP2 (Q=0)

D Ho Adiabatic Flame temp.

To T1
Combust2a.ppp

T2

Temp.
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