Fuel & combustion Learning outcomes

Fuel Classification of fuels Solid fuel Liquid fuel Gaeous fuel Crieteria of fuel selection Enthalpy of formation & combustion Heating values or calorific values Adiabatic flame tempertaure

Heating 0r calorific value The calorific value of a fuel is the quantity of heat produced by its combustion - at constant pressure and o under "normal" conditions (i.e. to 0 C and under a pressure of 1,013 mbar). The combustion process generates water vapor and certain techniques may be used to recover the quantity of heat contained in this water vapor by condensing it. The Higher Calorific Value (or Gross Calorific Value - GCV) suppose that the water of combustion is entirely condensed and that the heat contained in the water vapor is recovered. The Lower Calorific Value (or Net Calorific Value - NCV) suppose that the products of combustion contains the water vapor and that the heat in the water vapor is not recovered.

Higher Calorific Value (Gross Calorific Value - GCV) Fuel kJ/kg Acetone Alcohol, 96% Anthracite Bituminous coal Butane 29,000 30,000 32,500 - 34,000 17,000 - 23,250 49,510 14,000 - 14,500 7,300 - 10,000 20,900 Btu/lb

Carbon Charcoal Coal Coke Diesel Ethanol Ether Gasoline Glycerin Hydrogen Lignite Methane Oils, vegetable Peat Petrol Petroleum Propane Semi anthracite

34,080 29,600 15,000 - 27,000 28,000 - 31,000 44,800 29,700 43,000 47,300 19,000 141,790 16,300 55,530 39,000 - 48,000 13,800 - 20,500 48,000 43,000 50,350 26,700 - 32,500 11,500 - 14,000 5,500 - 8,800 61,000 7,000 20,400 12,800 8,000 - 14,000 12,000 - 13,500 19,300 12,800

Sulfur Tar Turpentine Wood (dry)

9,200 36,000 44,000 14,400 - 17,400 kJ/m3 6,200 - 7,500 Btu/ft3

Acetylene Butane C4H10 Hydrogen Natural gas Methane CH4 Propane C3H8 Town gas

56,000 133,000 13,000 43,000 39,820 101,000 18,000 kJ/l Btu/Imp gal 164,000 177,000 154,000 2550 950 - 1150 3200

Gas oil Heavy fuel oil Kerosene

38,000 41,200 35,000

1 kJ/kg = 1 J/g = 0.4299 Btu/ lbm = 0.23884 kcal/kg 1 Btu/lbm = 2.326 kJ/kg = 0.55 kcal/kg 1 kcal/kg = 4.1868 kJ/kg = 1.8 Btu/lbm

1 dm3 (Liter) = 10-3 m3 = 0.03532 ft3 = 1.308x10-3 yd3 = 0.220 Imp gal (UK) = 0.2642 Gallons (US)

Adiabatic flame temperature

In the study of combustion, there are two types of adiabatic flame temperature depending on how the process is completed, constant volume and constant pressure, describing the temperature the combustion products theoretically reach if no energy is lost to the outside environment. The constant volume adiabatic flame temperature is the temperature that results from a complete combustion process that occurs without any work, heat transfer or changes in kinetic or potential energy. The constant pressure adiabatic flame temperature is the temperature that results from a complete combustion process that occurs without any heat transfer or changes in kinetic or potential energy. Its temperature is lower than the constant volume process because some of the energy is utilized to change the volume of the system (i.e., generate work). It is a commonly misunderstood that the adiabatic flame temperature is the maximum temperature that can be achieved for given reactants because any heat transfer from the reacting substances and/or any incomplete combustion would tend to lower the temperature of the products. However, since the assumptions inherent in the adiabatic flame temperature assume chemical equilibrium, states in thermal equilibrium but not chemical equilibrium are not constrained by this limit. In fact, several fuel rich acetylene and methane flames have been found to exceed their adiabatic flame temperatures by hundreds of degrees.

A combustion process without heat loss or gain is adiabatic. The adiabatic flame temperature of some common fuel gases like hydrogen, methane, propane and octane with oxygen or air as oxidizers are indicated in the table below:

Adiabatic Flame Temperature (K) Fuel Oxygen as Oxidizer Butane - C4H10 Hydrogen - H2 Methane - CH4 3373 3473 Air as Oxidizer

2243 2483 2223

Natural gas Propane - C3H8

2799

2223 2268

reactants enter the combustion process at 25oC (77oF) and 1 atm pressure products leaves the process at 1 atm pressure combustion is stoichiometric without any excess air

Excess air will reduce the adiabatic flame temperature and is often introduced to avoid flame temperatures exceeding limits sets by the materials in the combustion system

Thermodynamics of Adiabatic flame temperature

First law of thermodynamics for a closed reacting system From the first law of thermodynamics for a closed reacting system we have,
RQP

RWP = UP UR

where, RQP and RWP are the heat and work transferred during the process respectively, and UR and UP are the internal energy of the reactants and products respectively. In the constant volume adiabatic flame temperature case, the volume of the system is held constant hence there is no work occurring,

and there is no heat transfer because the process is defined to be adiabatic: RQP = 0. As a result, the internal energy of the products is equal to the internal energy of the

reactants: UP = UR. Because this is a closed system, the mass of the products and reactants is constant and the first law can be written on a mass basis, .

Internal energy versus temperature diagram illustrating closed system calculation

Enthalpy versus temperature diagram illustrating closed system calculation In the constant pressure adiabatic flame temperature case, the pressure of the system is held constant which results in the following equation for the work,

Again there is no heat transfer occurring because the process is defined to be adiabatic: RQP = 0. From the first law, we find that,

Recalling the definition of enthalpy we recover: HP = HR. Because this is a closed system, the mass of the products and reactants is constant and the first law can be written on a mass basis,

. We see that the adiabatic flame temperature of the constant pressure process is lower than that of the constant volume process. This is because some of the energy released during combustion goes into changing the volume of the control system. One analogy that is commonly made between the two processes is through combustion in an internal combustion engine. For the constant volume adiabatic process, combustion is thought to occur instantaneously when the piston reaches the top of its apex (Otto cycle or constant volume cycle). For the constant pressure adiabatic process, while combustion is occurring the piston is moving in order to keep the pressure constant (Diesel cycle or constant pressure cycle).

Adiabatic flame temperatures and pressures as a function of stoichiometry (relative ratio of fuel and air)

Constant volume flame temperature of a number of fuels If we make the assumption that combustion goes to completion (i.e. CO2 and H2O), we can calculate the adiabatic flame temperature by hand either at stoichiometric conditions or lean of stoichiometry (excess air). This is because there are enough variables and molar equations to balance the left and right hand sides,

Rich of stoichiometry there are not enough variables because combustion cannot go to completion with at least CO and H2 needed for the molar balance (these are the most common incomplete products of combustion),

However, if we include the Water gas shift reaction,

and use the equilibrium constant for this reaction, we will have enough variables to complete the calculation. Different fuels with different levels of energy and molar constituents will have different adiabatic flame temperatures.

Constant pressure flame temperature of a number of fuels

Nitromethane versus isooctane flame temperature and pressure

We can see by the following figure why nitromethane (CH3NO2) is often used as a power boost for cars. Since it contains two moles of oxygen in its molecular makeup, it can burn much hotter because it provides its own oxidant along with fuel. This in turn allows it to build-up more pressure during a constant volume process. The higher the pressure, the more force upon the piston creating more work and more power in the engine. It is interesting to note that it stays relatively hot rich of stoichiometry because it contains its own oxidant. However, continual running of an engine on nitromethane will eventually melt the piston and/or cylinder because of this higher temperature.

Effects of dissociation on adiabatic flame temperature In real world applications, complete combustion does not typically occur. Chemistry dictates that dissociation and kinetics will change the relative constituents of the products. There are a number of programs available that can calculate the adiabatic flame temperature taking into account dissociation through equilibrium constants (Stanjan, NASA CEA, AFTP). The following figure illustrates that the effects of dissociation tend to lower the adiabatic flame temperature. This result can be explained through Le Chatelier's principle