Energy balance – Part 2

Energy balance of chemical process: Combustion of methane

Solve: 100 moles of methane is burnt to full combustion in a furnace isothermally. Air supply is in
25% excess. Assume, both air and methane enter the furnace at 25 degc and exhaust gases leave
furnace at 700 degc. Find out what is Q in and Q out for this combustion reaction.

General: Combustion reactions are high temperature redox exothermic reactions. The heat
produced in a combustion reaction can make it self-sustaining

Basic concepts

Qin

Mass in Mass out

Q out

[1] Energy accumulated within the system: [Energy- in through system boundaries] – [Energy- out
from system boundaries] = [Energy accumulated within the system].

[2] System: Certain quantity of matter or space which is under thermodynamic study or analysis is
called system. The space beyond the boundary of a system is called as universe or surroundings.

[3] Energy equation: Δ Ecv + (ΔEk + ΔEp + ΔH) = Q + Ws [Ws is work done]. ΔEk is kinetic energy
differential between in and out, ΔEp is potential energy differential and ΔH stands for in-out
enthalpy change, ΔH = ΔU + P*ΔV. P*ΔV is work done by system or on system with appropriate sign.
ΔU is change in internal energy. Internal energy U stands for molecule’s internal stored energy like
bond energies, molecular, atomic, and subatomic motions and interactions. It is not kinetic or
potential energy. Three forms of energies [1] kinetic energy [2] potential energy and [3] internal
energy are considered in energy balance. Kinetic Energy is associated with directed motion,
Potential energy of a system is due to the position of the system in a potential field. We will
consider only gravitational potential energy. The gravitational potential energy of an object of mass
m at an elevation z in a gravitational field is mg*height difference. U has already been explained
above. The energy flows represented by Q and Ws can be either into or out of the system;
appropriate signs must be used to indicate the direction of flow. Heat Q is positive if heat is added
to the system and negative if heat is removed

[4] Adiabatic process: No energy goes out or comes into system, delta Q = 0. For any work done in a
system, energy is supplied internally,

[5] Isothermal process: For any work done in a system, energy is supplied by surrounding. Both
system and surrounding stay at same temperature, delta T = 0. Energy is supplied by surrounding.

Important points when energy transfer takes place in a chemical process

Enthalpy of formation: There is an important concept in thermodynamics called enthalpy of

formation. Enthalpy of formation in a molecule is the change in enthalpy when 1 mole of a molecule
is formed under standard state conditions, at 25 degc (298.15 K) and 1 atm pressure. Enthalpy of
formation for a molecule with identical atoms like, O2, N2 or H2 gas is taken as zero. These are
natural stable molecules. Two identical atoms of same element cannot exchange energy under
identical condition. So for such cases no change in enthalpy is considered in thermodynamics. Note:
Enthalpy of formation remains stored in the bonds of molecules. These are bond energies. Every
time a reactant molecule converts to a new molecule, bond energy changes because new bonds
form.

Endothermic and exothermic reactions: In a chemical reaction when reactants react, the first thing
that happens is their bonds break. This bond breaking requires energy. When product molecules are
formed from broken reactant atoms new bonds are formed. Bond making releases heat. When bond
making energy [ at product stage] > bond breaking energy [at reactant stage] , overall there is
release of energy. Such processes are called exothermic. Q has negative sign in exothermic process.
When bond making energy [at product stage] < bond breaking energy at reactant stage], overall
there is a gain in energy. Such processes are called endothermic process. Q in endothermic reactions
has positive sign.
Process

Chemical reaction

100 moles methane is burnt to full combustion with 25% excess air.

CH4 + 2O2= CO2 + 2H2O

25% excess air is = [200/0.21]1.25 =1190 moles of air [O2 in air = 21%]

Mass in – 100 mole methane + 1190 moles air = 1290 moles.

The reaction produces, 100 mole CO2 and 200 moles H2O.Exhaust gases carry in addition, excess
O2 and N2. Out of 1190 moles of air, O2 = 1190*0.21= 250 moles and N2= 940 moles, Excess O2 =
[250-200] = 50 moles , N2 = 940 moles , N2 does not react. Exhaust gas composition is as follows:
CO2=100, H2O=200, O2=50, N2= 940 all in moles. Total exhaust gas = 100+200+50+940= 1290
moles.

Mass out – 1290 moles

Heat transfer

It is a high temperature exothermic reaction. Once the combustion reaction sets in it generates own
heat to make the process self-sustaining.

Enthalpy in

Enthalpy enters furnace with CH4 and O2 in the form of their enthalpy of formation [bond
energies]

Enthalpy of formation of methane, ΔHfCH4 = -74.87 kj/mol

Enthalpy of formation of oxygen , ΔHfO2 = 0 kj/mol

Total enthalpy carried by reactants = - 100*74.87 kj = -7487 kj

Heat-in is -7487 kj for 100 moles methane.

Enthalpy out

Chemical reaction between CH4 and O2 generates heat

CH4 + 2O2= CO2 + 2H2O

Enthalpy of formation of products

Enthalpy of formation of CO2 , ΔHfCO2 = - 393.522 kJ/mol, Enthalpy of formation of H2O, ΔHfH20
= -286.0 kJ/mol

This equals to total = 100*(- 393.522) + 200* (-286.0) = -96552.2kj

ΔH = [-96552.2(enthalpy of formation of product) - [-7487](enthalpy of formation of reactants) =-

89065.2kj.

This is the heat of reaction generated by combustion of 100 moles of methane. This is enthalpy out
from furnace.

Energy equation: ΔEcv + (ΔEk + ΔEp + ΔH) = Q+Ws

There is no mechanical work in combustion reaction, W =0. Process is isothermal, ΔT = 0. Height
difference between inlet and out let of furnace is not given, differential potential energy therefore
cannot be calculated, Ep = 0. Pipe dia of inlet / outlet are not available to calculate inlet and outlet
velocity therefore, Ek = 0. It’s a steady flow process, there is no accumulation of energy in the
furnace therefore, ΔEcv = 0. Energy equation reduces to ΔH = Q . ΔH in this case is change in
enthalpies of formation when reactants are converted to products. Please note enthalpy of
formation is the energy which gets stored in chemical bonds. These are bond energies. Every
molecule has its own bond energy. When new molecules form, bond energy or bond enthalpies
change.

ΔH = [-96552.2(enthalpy of formation of product) - [-7487](enthalpy of formation brought by

reactants) =-89065.2kj [this is for 100 moles of methane]. So, the heat of reaction, is – 890.652 kJ
per mole of methane. This is the text book figure for heat of combustion of methane.

Heat out from furnace /100 moles methane is 89065.2kj