1. What is Combustion Process and Explain enthalpy of Formation.

Combustion process:

Combustion is an exothermic chemical reaction between a fuel and oxygen which proceeds at a fast
rate with the release of energy in the form of heat.

The main combustion elements in a fuel are carbon (c) and hydrogen (h2) with other elements
appearing in small quantities.

Combustion of carbon with oxygen to form carbon dioxide.

C + o2 Co2

The amount of heat liberated when one Kmol of carbon is burnt/oxidized at 25® C equal to 393,522kJ

The enthalpy equation for the reaction is

C(s) + o2(g) Co2(g) + 393,522 KJ/Kmol carbon

The enthalpy equation for the combustion of hydrogen to form liquid water.

H2 (g) + 1/2o2(g) H2O(l) +285 830KJ/Kmol Hz

The standard heat / enthalpy in a combustion reaction is called the standard heat / enthalpy of
combustion. This is always based on 1 mole of the substances burnt/oxidized.

Atmospheric air contains 21% oxygen, 78% nitrogen and 1% argon by volume. In combustion
calculation, the argon is usually neglected and air is assumed to consist of 21% oxygen and 79% nitrogen by
volume. On mass basis, air contains 23% oxygen and 77% nitrogen.

Enthalpy of formation:

Let us consider the steady state steady flow combustion of carbon and oxygen to form Co 2 as shown
in figure.
C.V

C 25°c, 1atm

25°c 1atm CO2

O2

Q C.V = -393,522 KJ/Kg of mol of CO2

 Let the carbon and oxygen enter the control volume at 25°c and 1 atm, pressure and the heat
transfer be such that the product CO2 leaves at 25°c, 1atm pressure
 The measure value of heat transfer is -393,522 KJ per kg of CO2 formed
 If HR and HP refer to the total enthalpy of the reactants and products respectively.

Then the first law applied to the reaction

C + o2 Co2 gives

HR + Qc.v = Hp
 Generally all the reactants and products in a reaction , the equation may be written as

+ Qc.v =

Where R and P refer to the reactants and products respectively.

 The enthalpy of all the elements at the standard reference state of 25°c ,1 atm is assigned the
value of zero
 In carbon- oxygen reaction, HR = 0

i.e. HP = Qc.v = -393522 KJ/Kgmol

It is also denoted by f°

 f° = -393522 KJ/Kgmol

But in most cases, the reactants and products are not at 25°c, 1 atm. Therefore, the change in
enthalpy between 25°c, 1 atm and the given state must be known.

Thus the enthalpy at any temperature and pressure, T,p is

T,p = f° + Δ

Where Δ referents the difference in enthalpy between any given state and the enthalpy at 298.15K,
1atm.

2. Explain Steady Flow analysis of reacting mixtures.

Steady Flow analysis of reacting mixtures:

C.V

n1 n3

Reactants Products

n2 n4

QC.V W C.V

The significance of the enthalpy of formation is that it is most convenient in performing a first-law
analysis, of a reaction system, for the enthalpies of different substances can be added or subtracted.

The first law for a steady-state, steady flow process in the form (SSSF)

Qc.v + HR = Wc.v+ Hp
OR
Qc.v + = Wc.v +
 Where R and P refer to the reactants and products respectively.

Where = [ f° + Δ ]i

=[ f° + Δ ]e

 When the states of reactants and products are not in the standard reference state (298k,1atm)
Then

Qc.v = HR- Hp

= p - p0 ) +Δ Rp - R - R0 )

Where Δ Rp is the enthalpy of reaction at the standard temperature (298 k)

For constant volume reaction,

Qc.v = Up- UR

= p- p0) +Δ Rp - R - R0)

Where Δ Rp is the internal energy of reaction at 298 k

R
R0
H
P

Δh Rp

P0

298k T

Enthalpy of reactants and products varying temperature.

3. Explain Adiabatic Combustion temperature

Adiabatic Combustion temperature:

Consider a given combustion process that takes place adiabatically and with no work or changes in
K.E or potential energy involved. The temperature of the products is referred to as the adiabatic Flame
temperature.

With the assumption of no work and no changes in kinetic or potential energy, this is the maximum
temperature that can be achieved for the given reactants because any heat transfer from the reacting
substances and any incomplete combustion would tend to lower the temperature of the products.
 For a given fuel and given pressure and temp of reactants, the maximum adiabatic flame temperature
that can be achieved is with a stoichiometric mixture. The Adiabatic flame temperature can be controlled by
the amount of excess air that is used.

The energy equation is

HR=Hp

Or

[ f° + Δ ]i = [ f° + Δ ]e

For example:

In gas turbine, where the maximum permissible temperature is determined by metallurgical

consideration in the turbine is determine by metallurgical consideration in the turbine and close control of
the temp. Of the products is essential.

4. Explain Enthalpy of reaction and heating value.

Enthalpy of reaction and heating value.

The enthalpy of combustion is defined as the difference between the enthalpy of the products and the
enthalpy of reactants when complete combustion occurs at a given temperature and pressure

RP = Hp - HR

Or

RP = [ f° + Δ ]e - [ f° + Δ ]i

Where is the enthalpy of combustion (KJ/Kg or KJ/mol) of the fuel

The internal energy of combustion, is defined in

RP= Up - UR

= [ f° + Δ ]e - [ f° + Δ ]i

If all the gaseous constituent are considered ideal gases and the volume of liquid and solid
considered is assume to be negligible compared to gaseous volume.
RP = RP - T ( η gaseous products - η gaseous Reactants)

 In the case of a constant pressure or steady flow process, the negative of the enthalpy of
combustion is frequently called the heating value at constant pressure, which represents the heat
transferred from the chamber during combustion at const. pressure.
  Similarly, the negative of the internal energy of combustion is called as the heating value at
constant volume in the case of combustion, because it represents the amount of heat transfer in
the const volume process.
 The higher heating value (HHV) or higher calorific value (HCV) is the heat transferred when
H2O in the products is in the liquid phase.
 The lower heating value (LHV) or lower calorific value (LCV) is the heat transferred when H2O
in the products is in the vapour phase.

~ LHV =HHV – m H2O. hfg

Where mH2O is the mass of water formed in the reaction.

5. Explain Second law Analysis of reactive system (Chemical Reaction).

Second law Analysis of reactive system (Chemical Reaction)

The concepts of first and second laws of thermodynamics are involved in reversible work
irreversibility and availability (energy)

To determining the maximum work (Availability) that can be done through a combustion process and
with examining the irreversibility’s associate with such process.
The reversible work for a steady-state process in which there is no heat transfer with reservoirs other
than the surroundings, and also absence of changes in kinetic and potential energy is

Wrev = (hi Tosi ) - (he Tose ) (1)

To apply the equation to a steady state process. That involves a chemical reaction
Eq (1) becomes
Wrev = [ f°+Δ -To ]i - [ f°+Δ -To ]e (2)

Irreversibility for such a process can be written as

I = Wrev – W

= To e - To i - QC.V (3)

The availability , Ψ for a steady- flow process in the absence of kinetic and poteneial energy changes
is given by

Ψ = (h - ToS) –( ho – ToSo) (4)

If a steady- state chemical reaction takes places in such a manner that both the reactants and products
are in temperature equilibrium with the surroundings the Gibbs function (g= h- Ts )
 The reversible work is given be Eq (2) becomes

Wrev = i- e
= -ΔG (5)

In which ΔG = ΔH - TΔs

6. Explain Availability Analysis of chemical reaction:

Availability Analysis of chemical reaction:

Where a system is at the dead state, it is in thermal and mechanical equilibrium with the
environment, and the value of its energy is zero is thermo mechanical contribution to energy is zero.
However, the content of contents of a system at the dead state may undergo chemical reaction with
environmental components and produce additional work.
Here a combined system formed by an environment and a system having a certain amount of fuel at
To,Po The cork obtainable by allowing the fuel to react with oxygen from the environment to produce the
environment components of CO2 and H2O is evaluated.
The chemical energy is thus defined as the maximum theoretical work that could be developed by the
combined system.

Total Energy = Thermo mechanical energy + Chemical energy

Work

Po,To
Ca Hb

CO2 at To

XCO2 Po

O2 at To

XO2/ Po

H2O at To , XH2O Po

Heat transfer environment at Po To

 Let us consider a hydrocarbon fuel (CaHb) at To,Po reacting with oxygen from the environment
which is assumed to be consisting of an ideal gas mixture at To , Po.
 The oxygen that reacts with the fuel is at a partial pressure of Xo2,Po , Where xo2 is the mole
fraction n of oxygen in the environment
 The fuel and oxygen react completely to produce CO+2+ and H2O, Po
 The reaction is given by

CaHb + (a + ) O2 a Co2 + H2O (1)

At steady state, the energy balance gives

+ = +

= + H R - HP

= + ( f° + Δ ) Ca Hb + (a + ) o2 –a Co2 - Ho2 (2)

Where is the rate of fuel flow in moles, and KE and PE are neglected.

An enthalpy balance for the control volume

O= / To + aHb+ (a + ) o2 – a co2 - Ho2 + (3)

Eliminating from eq (2) and (3) wer get

=[ aHb+(a + ) o2 –a Co2 - Ho2]

– To[ aHb+ (a + ) o2 – a co2 - Ho2] - To (4)

For maximum Work ,To =0

(4) => Chemical energy ch

=> ch = [ aHb+(a + ) o2 –a Co2 - Ho2]

– To[ aHb+ (a + ) o2 – a co2 - Ho2] (5)

The specific entropies of O2 ,CO2 and H2O are written as

1 (To, x1Po) = si ( To, po) - lnxi (6)

Where T0 ,po is the absolute entropy and xi is the mole fraction of component i in the environment .

ch = [ aHb+(a + ) o2 –a Co2 - Ho2]at(To,Po)

– To[ aHb+ (a + ) o2 – a co2 - Ho2]at(To,Po) +

R To ln (7)
In terms of Gibbs functions

ch = [ aHb+(a + ) o2 –a Co2 - Ho2]at(To,Po) + To ln (8)

The specific energy of system is

a = a thermo – mech + a chem

= (u-uo)+po(v-vo)-To(s-so) + + gz +ach

=> a = (h-ho)- To(s-so) + + gz +ach (9)