Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

CHAPTER 2

CHEMICAL THERMODYNAMICS AND EQUILIBRIUM

Chemical thermodynamics is application of general thermodynamic laws to a chemical reacting
system. It studies how chemical reactions affect the properties of the system and more importantly,
the interaction between the system and the surroundings (via work and heat).

1. Review of the First Law of Thermodynamics

SURROUNDINGS
BOUNDARY
SYSTEM

Ein
E Eout

E system = E in - Eout

Energy transfer between the system and surroundings can only occur in the form of work and
heat. Work and heat depend on the process during which the energy transfer takes place (path
function), and can not be determined by the initial and final states of the system undergoing energy
transfer (not state function). Therefore unlike internal energy or enthalpy, work and heat are not
system properties and can not be used to define the state of a system.

The energy of a system consists of internal energy, kinetic energy, potential energy, electric energy,
magnetic energy, etc. For a simple compressible system in which the effects of electric, magnetic, and
surface tension are absent, the change the system energy can be written as
E = U + KE + PE

For closed (fixed mass) systems with neglecting changes of kinetic and potential energy, the first law
can be written from a change from state 1 to state 2 as
Q12 W12 =U2 U1
Note the sign of heat and work is defined differently: heat is positive when heat is transferred to
(energy added to) the system, while work is positive when work is done (energy lost) by the system.

For open system (control volume) under steady-state, steady-flow condition, the first law can be
written as
Q cv W cv= m
(uo ui ) + m
(Povo Pv
i i)

where u and v are mass-specific internal energy and volume, and Povo and Pivi are the flow work at
the outlet and inlet of the control volume. Flow work is the work associated with pressure forces which
push fluids into and out of the control volume.

Given H U + PV , it can be written as

Q cv W cv = m
(ho hi )

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 Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

Or in the mass-specific form,

qcv wcv =ho hi

2. Enthalpy of Combustion
Considering a closed system changing from state 1 to state 2, doing only boundary work (PdV) and at
constant pressure, the first law becomes
Q12 =U + PV =U + (PV + V
P) =H
=0
If a chemical reaction at a given temperature causes such change of state, the resulted energy
change is called enthalpy of reaction,
Q=
HR =
Hprod Hreac
Enthalpy of a chemical compound consists of two parts, enthalpy of formation and sensible enthalpy.
hi (T ) h0f ,i (Tref ) + hs ,i (T ,Tref )
=
Sensible enthalpy is the enthalpy difference between a reference state and a state of interest and can
be calculated with the knowledge of specific heat.
T
hs ,i (T ,Tref ) =hi (T ) hi (Tref ) = cp ,i dT
Tref

Standard enthalpy of formation, h , is a special type of enthalpy of reaction, which is the change of
0
f ,i

enthalpy that accompanies the formation of 1 mole of the compound from its elements, with all
substances in their standard states. The standard state is usually defined as 1 atm and 25C (298.15
K).

Note that for ideal gases, the enthalpies are only a function of temperature and not a function of
pressure.

The standard enthalpy of reaction for a stoichiometric combustion reaction

C x Hy Oz + a(O2 + 3.76N2 ) xCO2 + (y / 2)H2O + 3.76aN2
where a=
(x + y / 4 z / 2) , can be calculated as
o
H=
R xhfo,CO2 + (y / 2)hfo,H2O hfo, fuel
Note: 1. h is molar-based enthalpy.
2. Standard enthalpies of formation of elements, e.g. O2, N2, are zero.

The heat of combustion, HCo , (also called heating value of the fuel) is numerically equal to the
enthalpy of reaction, HRo , but with opposite sign. The higher heating value (HHV) is the heat of
combustion calculated assuming that all of the water in the products has condensed to liquid; the
lower heating value (LHV) corresponds to the case where no water is condensed, thus a smaller
value than the corresponding HHV. For most combustion applications, the temperatures of
combustion products are higher than 100C, so LHVs are more commonly used.

It is important to note that HRo is the enthalpy of a reaction where both the reactant and product are
at the standard state. In other words, HCo , LHV and HHV all refer to combustion reactions where the
fuel/oxidizer and combustion products are at 25C and 1 atm. Different heating values will be resulted
if the reaction conditions are different.

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 Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

LHV of Common Fuels

Fuel LHV (MJ/kg) Note
Hydrogen 121.0
Methane 50.0 Major component for natural gas
Propane
n-Butane
46.4
45.8
} Major components for liquefied petroleum gas

Gasoline 44
Kerosene 43
Diesel fuel 43

}
Methanol 19.9
Ethanol 28.9 Lower than hydrocarbons due to containing oxygen
Biodiesel 37

3. Adiabatic Flame Temperature

Adiabatic flame temperature is the highest flame temperature one can obtain in a process for a given
fuel/air mixture, due to the zero heat transfer between the combusting gas and the surroundings.

For constant pressure system, we have

Q Hprod Hreac
=
Hprod = Hreac
If combustion starts from a standard state, we have
Hreac = H 0f ,reac
But due to the adiabatic process, the product wont be at the standard state, so
Hprod H 0f ,prod + Hs ,prod (T 0 ,Tad )
=
So
H=
0
f ,reac H 0f ,prod + Hs ,prod (T 0 ,Tad )
Tad
nprod 0 cp ,prod dT
HC0 =
T
In other words, all the energy (enthalpy) released from combustion is used to raise the
temperature of the product.

For constant volume system, both Q and PdV are zero, the first law becomes
Uprod Ureac =
0
Replace U with H and plug in ideal gas law,
(Hprod Hreac ) V (Pf P 0 ) =
0 eq. 1

(Hprod Hreac ) Ru (nprodTad nreacT 0 ) =

0
For combustion starts from a standard state,
Hprod Hreac = H 0f ,prod + Hs ,prod (T 0 ,Tad ) H 0f ,reac
Tad
= HC0 + nprod 0 cp ,prod dT
T
After rearrangement,
Tad
=HC0 nprod 0 cp ,prod dT Ru (nprodTad nreacT 0 )
T

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 Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

Since Tad is the only unknown, it can be solved through iterations.

Sometimes, an average cp, such as the one at Tavg

= (Tad + T 0 ) / 2 , can be used as an approximation,
which greatly simplifies the problem. For example, for the constant-pressure case, it becomes
=HC0 nprod cp ,prod (Tavg )(Tad T o )
Or
HC0
=Tad +To
nprod cp ,prod (Tavg )

For combustion does not start from the standard state, the energy that is required to bring the
reactant to the standard state needs to be considered. With this being taken into account, the rest
steps are the same.

Note that compared to the constant-pressure case, there is no boundary work being done in the
constant volume case. The saved energy is used to further increase flame temperature. This is why
adiabatic flame temperature is always higher at constant volume conditions.

Adiabatic flame temperature is affected by

i) Fuel type: hydrogen and acetylene have exceptionally high Tad; olefins typically have higher Tad
than paraffins with the same carbon number; paraffins have similar Tad regardless of carbon
number (chain length).
ii) Equivalence ratio: maximum Tad around = 1 (slightly on the rich side for most fuels)
iii) Dilution level: Tad in oxygen is much higher than in air, typically > 3000 K, because of no N2
dilution.
Adiabatic Flame Temperature of Fuels
(Constant-Pressure, in Air, reactants at 25C, 1 atm.)
Fuel Formula Tad (K)
Hydrogen H2 2483
Methane CH4 2226
Acetylene CHCH 2539
Ethylene CH2=CH2 2369
Ethane CH3-CH3 2259
Propane CH3-CH2-CH3 2267
n-Butane CH3-(CH2)2-CH3 2270
n-Octane CH3-(CH2)6-CH3 2275
n-Dodecane CH3-(CH2)10-CH3 2277

4. Chemical Equilibrium

Experimentally measured adiabatic flame temperatures are lower than those calculated using the
above method. This is caused by the dissociation of the combustion products, such as
CO2 CO + (1 / 2)O2
We can use chemical equilibrium to determine the extent of dissociation and how much dissociation
affects adiabatic flame temperature.

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 Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

4.1 Criterion for Chemical Equilibrium

Chemical equilibrium is the state in which the concentrations of both reactants and products have no
further tendency to change with time.

Consider a reaction occurring in a simple compressible, closed system with only boundary work being
done. At a given temperature and pressure, applying both the first and second laws of
thermodynamics to a system in which chemical reactions are occurring,
Q PdV =
dU

Q dU + PdV TdS T 0
dS
T
Also, we know that the Gibbs function is defined as G= H TS , and its differential at constant
temperature and pressure is
(dG)T ,P =dH TdS SdT
=(dU + PdV + VdP ) TdS SdT
=dU + PdV TdS
Compare the above two equations, we find
(dG)T ,P T 0
which means that the state of a reacting system can only change from a higher Gibbs function to a
lower Gibbs function. In other words, a chemical reaction at a specified temperature and pressure
only proceeds in the direction that Gibbs function decreases. The chemical equilibrium is reached
when the Gibbs function does not decrease any more and attains a minimum value. The criterion for
chemical equilibrium can be expressed as
(dG)T ,P = 0

To obtain a relation for chemical equilibrium in terms of the properties of the individual reacting
compounds, assume the following reaction
A A + BB C C + D D
At chemical equilibrium
(dG)T ,P
= =
(dG )
i
=
(g dN )
i T ,P
i
i i T ,P 0

or gAdNA + gBdNB + gC dNC + gD dND =

0
Note that gi is molar-based Gibbon function.
From the reaction stoichiometry among the four compounds, the following relationship can be
obtained
( A ): ( B ): C : D
dNA : dNB : dNC : dND =
Substitute this relation into the last equation gives another expression of the criterion for chemical
equilibrium, we obtain
C gC + D gD AgA BgB =
0 eq. 2
Note that dG = 0 is a function of temperature and pressure at which the reaction takes place. In other
words, chemical equilibrium occurs at different states when reaction temperature and pressure
change.

Therefore, for a chemical reaction to occur, the sum of the reactants Gibbs function must be larger
than the products Gibbs function, so that the reaction can proceed in the direction of decreasing
Gibbs function until (dG)T ,P = 0 . In this regard, chemical potential, or the potential to drive the
reaction down the Gibbs function gradient, can be defined as, for the ith species

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 Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

G
i =
ni P ,T ,n j i

And the criterion for chemical equilibrium can be expressed as

dn
i
i i =0

4.2 Equilibrium Constants for Ideal Gases

For individual components, the Gibbs function can be expressed as
g=i gi0 + gi
where gi is the Gibbs function difference between the standard state and a specified state for the ith
component. At constant temperature, g can be obtained as follows,
=0 =0
(g )T =h s T T s =T (s )T
Note enthalpy of ideal gases depends only on temperature.

Given simple compressible system with only quasi-equilibrium boundary work mode (i.e. reversible
process, so Q = TdS ), the first law can be written as (in the molar-based form)
du dv
Tds Pdv = du ds = + Ru
T v
At constant temperature, du = 0 , therefore
v2 dv
(s )T =
( s2 s1 )T =Ru = Ru ln(P2 / P1 )
v1 v

and
(g )T =
RuT ln(P2 / P1 )
Substitute into gi above
gi (T=
, Pi ) gi0 (T ) + RuT ln(Pi / P 0 )
where Pi is the partial pressure for the ith component.

Apply this expression to each component and substitute them into Eqn. 2,
C [gC0 (T ) + RuT ln(PC / P 0 )] + D [gD0 (T ) + RuT ln(PD / P 0 )]
A [gA0 (T ) + RuT ln(PA / P 0 )] B [gB0 (T ) + RuT ln(PB / P 0 )] =
0

Defining the standard-state Gibbs function change as

GT0 C gC0 (T ) + D gD0 (T ) AgA0 (T ) BgB0 (T )
G=

And after rearrangement we have

RuT [ C ln(PC / P 0 ) + D ln(PD / P 0 ) A ln(PA / P 0 ) B ln(PB / P 0 )]
GGT0 =
(P / P 0 ) C (PD / P 0 ) D
= RuT ln C 0 A 0 B
(PA / P ) (PB / P )
Now we define the equilibrium constant Kp for a chemical reaction of ideal gas mixtures as
(PC / P 0 ) C (PD / P 0 ) D
Kp =
(PA / P 0 ) A (PB / P 0 ) B
We then have

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 Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

GGT0 =
RuT ln K p
Or K p exp(GGT0 / RuT )
=
Therefore, by knowing the standard-state Gibbs function change at a specified temperature, the
equilibrium constant Kp of an ideal-gas mixture can be determined for that temperature.

Note that for ideal gas mixtures, the partial pressure Pi is related to the total pressure P by the molar
fraction, xi.
Pi = xi P
So the equilibrium constant in terms of molar fraction, xi, can be expressed as
xC C xD D
KP = (P / P 0 )
x A A xB B
Or K x = K P (P / P 0 )
where = C + D A B .
3
Similarly, in terms of molar concentration, [Xi] (in the unit of mol/m ),
[ X i ] = Pi / RuT
the equilibrium constant can be written as
[C ] C [D] D (PC / RuT ) C (PD / RuT ) D
=KC = = K P (P 0 / RuT )
[ A] A [B] B (PA / RuT ) A (PB / RuT ) B

Remarks about the equilibrium constant of ideal gas mixtures:

1) The Kp of a reaction of ideal gases depends only on temperature and partial pressure of each
species but does not depends on the total pressure, because Kp is determined by GGT0 which is
only a function of temperature for ideal gases.
2) The larger the Kp, the more complete the reaction.
3) If the equilibrium constant of the forward reaction is Kp, the equilibrium constant of the reverse
reaction is 1/Kp.

EXAMPLE Chemical equilibrium of CO2 dissociation

EXAMPLE Chemical equilibrium of water-gas shift reaction

4.3 Principle of Le Chatelier

As discussed, chemical equilibrium, (dG)T ,P = 0 , is a function of reaction temperature and pressure.
An empirical rule, called Principle of Le Chatelier, can be used to predict the effect of a change in
conditions on a chemical equilibrium. The Principle of Le Chatelier states: A system initially in a state
of equilibrium when subjected to a change will shift in such a way to minimize the change.

We can apply this principle to the above two examples. CO2 dissociation is an endothermic
(absorbing heat) reaction, and the moles of reactant are less than the moles of the product. In this
case, increasing temperature will favor CO2 dissociation, and reducing temperature will favor CO
oxidation, as such will minimize the temperature change of the system. Similarly, increasing pressure
will favor CO oxidation, and reducing pressure will favor CO2 dissociation. For water-gas shift reaction,
it is a mild exothermic (releasing heat) reaction (from CO to CO2), and the product and reactant have
equal moles. In this case, increasing temperature will moderately inhibit the conversion of CO + H2O
to CO2 + H2, but changes in pressure will have no effect on the equilibrium. For both reactions,

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 Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

increasing concentration of any species will shift the equilibrium to the direction to consume more of
this species. For example, increasing CO2 concentration will favor CO2 dissociation.

5. Equilibriums for Combustion Calculations

The chemical equilibrium of CO2 dissociation and water-gas shift reaction can be used to balancing
more practical combustion reaction equations, so that combustion-product compositions and adiabatic
flame temperatures can be more accurately calculated.

Now instead of writing an equation for stoichiometric ( = 1) and complete (producing only CO2 and
H2O) combustion, we can write a more general equation:
C x Hy Oz + a(O2 + 3.76N2 ) bCO2 + cCO + dH2O + eH2 + fO2 + 3.76aN2 eq. 3
Since equivalence ratio is usually given information, so is the fuel composition (x, y, z), the
coefficient for air, a, can then be considered as a known, via
x +y /4z /2
a=

For lean conditions ( < 1) where CO and H2 can be neglected, the eq. 3 becomes
C x Hy Oz + a(O2 + 3.76N2 ) bCO2 + dH2O + fO2 + 3.76aN2
where c = e = 0. This reaction can be easily balanced using conservation of C, H, and O atoms.
b=x
d = y /2
1
f = 1 (x + y / 4 z / 2)

This is a familiar case for adiabatic flame temperature calculation, except for the excess air.

For stoichiometric conditions ( = 1) where H2 can be neglected but CO2 dissociation can not, the
eq. 3 becomes
C x Hy Oz + a(O2 + 3.76N2 ) bCO2 + cCO + dH2O + fO2 + 3.76aN2
where e = 0. Using C, H, O atom balance,
b+c = x
d = y /2
2b + c + d + 2 f = z + 2(x + y / 4 z / 2)
There are four unknowns and three equations. To solve the problem, we add CO2 dissociation
reaction,
CO2 CO + 1 / 2O2
and assume chemical equilibrium,
1/2
xCO xO1/2 c f 1/2 1 o 1/2 0 (T ) o 1/2
=Kx = 2
= K p (P / P
= ) exp (P / P )
xCO2 b ntot RuT
where ntot is the total number of moles of the combustion product and ntot = b + c + d + f + 3.76a.

Kx and Kp can be calculated from the knowledge of combustion temperature and pressure and
standard Gibbs function of species. Iterations are required for cases where combustion temperature
and pressure are unknown and to be solved, like calculating the adiabatic flame temperature.

For rich conditions ( > 1) where O2 can be neglected but not for CO or H2, the eq. 3 becomes

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 Advanced Thermodynamics - Semester 2 2017 - Lecture Notes

C x Hy Oz + a(O2 + 3.76N2 ) bCO2 + cCO + dH2O + eH2 + 3.76aN2

where f = 0. Using C, H, O atom balance,
b+c =x
d +e=y /2
2(x + y / 4 z / 2)
2b + c + d = z +

There are also four unknowns and three equations. To solve the problem, we add water-gas shift
reaction,
CO + H2O CO2 + H2
and assume chemical equilibrium,
be o 0 0 (T )
Kx
= = K p (P / P=) exp
c d RuT
Kx and Kp can be calculated from the knowledge of combustion temperature (no need for pressure)
and standard Gibbs functions. Estimation and iteration are again required for cases that combustion
temperature is to be solved, like calculating adiabatic flame temperature.

Note that
1) We considered CO2 dissociation for stoichiometric case but did not consider it for lean or rich
cases. This is reasonable treatment because the flame temperature is highest for ~ 1, and CO2
dissociation is highly dependant on temperature (as shown in Example #2). In general for
combustion temperature < 2000 K, CO2 dissociation can be safely neglected.
2) Equilibrium of water-gas shift (WGS) reaction should be restricted to 1.2 cases. Lower than
that, CO2 dissociation becomes important and assuming WGS equilibrium can result in significant
errors.

EXAMPLE Chemical equilibrium of NO formation