THERMODYNAMICS

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THERMODYNAMICS

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of the examples of chemical reaction are (1) Photosynthesis, (2) Metabolism, (3)

Combustion, (4) Petroleum refining, and (5) Plastics manufacturing. Energy

cannot be extracted from a system that is constrained unless the thermodynamic

constraint is removed. Fossil fuels such as coal, oil and natural gas are stored

below the earth’s surface and are in thermal, mechanical and chemical

equilibrium. If the chemical constraint is removed (allow the fuel to come in

physical contact with air), it is possible to release the chemical energy.

For example, consider the reaction

CH 4 + aO2 → bCO2 + cH 2O (5.1)

involving one kmole of fuel and “a” kmoles of molecular oxygen. Species on the

left hand side of the reaction equation (Eq. (5.1)) are usually called the reactants

as they react and are consumed during the overall chemical reaction. Species on

the right hand side of Eq. (5.1), produced as a result of chemical reaction are

called products. In case of a steady flow reactor, the input and output streams

contain the following quantity in kmole of the elements.

Input Output

C 1 = b

H 4 = 2c

O 2a = 2b+c

We deduce from the carbon atom balance that b=1, from the H atom balance that

c=2, and from O balance that a=(2b+c)/2. Consequently, Eq. (5.1) can be written

in the form of the stoichiometric reaction

CH 4 + 2O2 → CO2 + 2 H 2O (5.2)

The coefficients (1, 2, 1 and 2) in Eq. (5.2) are called the stoichiometric

coefficients.

The minimum amount of air which provides sufficient oxygen for the complete

combustion of all the element like carbon, hydrogen, etc., which may oxidize is

called the theoretical or stoichiometric air. There is no oxygen in the products

when complete combustion (oxidation) is achieved with this theoretical air.

86

Let us consider again the combustion of 10 kmole of CH4, 25 kmoles of O2, 5

kmoles of CO2 and 3 kmole of H2O during which the fuel completely burns. Thus

only 10 kmole of CH4 are consumed in the reactor. Applying Eq. (5.2) we readily

determine that 20 kmole of O2 are utilized during the process, and hence 5 kmole

of O2, 15 (=10+5) kmole of CO2 and 23 (=20+3) kmole of H2O leave the

combustor. The stoichiometric coefficients do not necessarily represent the

amounts of species entering and leaving a reactor. From Eq. (5.2), the

stoichiometric air fuel ratio is

On mass basis, the A:F ratio is

Atmospheric air contains 21% oxygen, 78% nitrogen, and 1% argon by volume.

In combustion calculations, however, the argon is usually neglected, and air is

assumed to consist of 21% oxygen and 79% nitrogen by volume (or molar basis).

On a mass basis, air contains 23% oxygen and 77% nitrogen. If we desire more

accuracy, air is a mixture of 78% N 2 , 1% Ar and 21% O2 . In this case,

Fuel and air are often introduced separately (without premixing) into a

combustor, e.g., boiler, CI engine etc. Due to the large flow rates and short

residence time there is no assurance that each molecule of fuel is surrounded by

the appropriate number of oxygen molecules required for the stoichiometric

combustion. Therefore, it is customary to supply excess air in order to facilitate

better mixing and thereby ensure complete combustion. The excess oxygen

remains unburned and appears in the product.

Incomplete combustion occurs when the air supplied is less than the

stoichiometric amount required. For this condition, the products of incomplete

oxidation may contain a mixture of CO, CO2 , H 2 and H 2 O .

The equivalent ratio is defined as the actual fuel-air ratio to stoichimetric fuel-air

ratio.

87

F : Aactual A : Fstoichiometric ( O2 : F ) stoichiometric (5.3)

φ= = =

F : Astoichiometric A : Factual ( O2 : F )actual

The stoichiometric ratio is given by

1 (5.4)

SR =

φ

For example, if φ = 0.5 , for methane-air combustion, this implies that the

excess air is supplied for every kmole of fuel that is burned. In such case SR=2.

In otherwords, air supplied is two times as large as the stoichiometric or

theoretical air demand of the fuel. Eq. (5.2) can be written under such condition

as

⎛ 2⎞ ⎛1 ⎞ ⎛ 2⎞ (5.5)

CH 4 + ⎜ ⎟ ( O2 + 3.76 N 2 ) → CO2 + 2 H 2O + 2 ⎜ − 1⎟ O2 + ⎜ ⎟ × 3.76 N 2

⎝φ ⎠ ⎝φ ⎠ ⎝φ ⎠

5.2 DEGREE OF REACTION

Let us suppose that we have a mixture of four substances, A1, A2, A3 and

A4 capable of undergoing a reaction of the type

ZZX v3 A3 + v4 A4

v1 A1 + v2 A2 YZZ (5.6)

where the v ' are the stoichimetric coefficients.

Starting with arbitrary amounts of both initial and final constituents, let us imagine

that the reaction proceeds completely to the right with the disappearance of at

least one of the initial constituents, say, A1 . Then the original number of moles of

the initial constituents is given in the form

n1 (original) = n0v1 (5.7)

where n0 is an arbitrary positive number, and N 2 is the residue(or excess) of

A2 , i.e., the number of moles of A2 which cannot combine. If the reaction is

assumed to proceed complete it to the left with the disappearance of the final

constituent A3 then

n3 (original) = n0′v3 (5.9)

88

where n0′ is an arbitrary positive number and N 4 is the excess number of moles

of A4 left after the reaction is complete from right to left. For a reaction that

occurred completely to the left, there is a maximum possible amount of each

initial constituent, and a minimum possible amount of each final constituent, so

that

n1 (max) = n0v1 + n0′v1 = (n0 + n0′ )v1 (5.11)

where n0v1 = Original number of moles of A1

n0′v1 = Number of moles of A1 formed by chemical reaction

(n0′v3 A3 + n0′v4 A4 → n0′v1 A1 + n0′v2 A2 )

where ( n0v2 + N 2 ) = Original number of moles of A2

n0′v2 = Number of moles of A2 formed by chemical reaction

The constituent A3 completely disappears by reaction, hence

n3 (min)= 0 (5.13)

The excess number of moles of A4 that are left after the reaction is complete to

left

n4 (min)= 0 (5.14)

Similarly, if the reaction is imagined to proceed completely to the right, there is a

minimum amount of each initial constituent, and a maximum amount of each final

constituent, so that

n1 (min) = 0 (5.15)

n2 (min) = N 2 (5.16)

n0v3 = amount formed by chemical reaction

(n0v1 A1 + n0v2 A2 → n0v3 A3 + n0v4 A4 )

n4 (max) = (n0 + n0′ )v4 + N 4 (5.18)

Let us suppose that the reaction proceeds partially either to the right or to the left

to the extent that there are n1 moles of A1 , n2 moles of A2, n3 moles of A3 and

n4 moles of A4 . The degree (or advancement) of reaction ε is defined in terms

of any one of the initial constituents, say, A1 as the fraction

89

n1 (max) − n1 (5.19)

ε=

n1 (max) − n1 (min)

It is seen that when n1 = n1 (max), ε = 0 , the reaction will start from left to right.

When n1 = n1 (min), ε = 1, reaction is complete from left to right.

(n0 + n0′ )v1 − n1 (5.20)

ε=

(n0 + n0′ )v1

Therefore

n1 = (n0 + n0′ )v1 − (n0 + n0′ )v0ε = n (at start) − n (consumed) (5.21)

or,

consumed in the reaction = ( n0 + n0′ )v1 (1 − ε )

= (n0 + n0′ )v2 + N 2 − (n0 + n0′ )v2ε

= (n0 + n0′ )v2 (1 − ε ) + N 2

= 0 + (n0 + n0′ )v3ε

= (n0 + n0′ )v3ε

= N 4 + (n0 + n0′ )v4ε

= (n0 + n0′ )v4ε + N 4

The number of moles of the constituents change during a chemical reaction, not

independently but restricted by the above relations (Eqs. (5.22-5.25)). These

equations are the equations of constraint. The n ' s are functions of ε only. In a

homogeneous system, in a given reaction, the mole fraction x ' s is also function

of ε only, as illustrated below.

(5.26)

ZZX 1 N 2 + 1 O2

NO YZZ

2 2

90

n0 n

in which n0 moles of NO dissociates to produce moles of N 2 and 0

2 2

moles of O2 . The n ' s and x ' s as function of ε are shown in the Table-5.1

given below

A v n x

n1 1 − ε

A1 = NO v1 = 1 n1 = n0 (1 − ε ) x1 = =

∑n 1+ ε

1 n0 ε

A3 = N 2 v3 = n3 = ε x3 =

2 2 1+ ε

1 n ε

A4 = O2 v4 = n4 = 0 ε x4 =

2 2 1+ ε

∑ n = n0 (1 + ε )

of reaction changes from ε to ε + d ε , and the various n ' s will change by the

amounts (Upon differentiation of Eqs. (5.22-5.24) w.r.t. ε )

dn2 = −(n0 + n0′ )v2 d ε

dn3 = (n0 + n0′ )v3d ε

dn4 = (n0 + n0′ )v4 d ε

or,

= = = = (n0 + n0′ )d ε

−v1 −v2 v3 v4

which shows that the dn ' s are proportional to the v ' s.

Let us consider a homogeneous phase having arbitrary amounts of the

constituents, A1, A2, A3 and A4 , capable of undergoing the reaction

ZZX v3 A3 + v4 A4

v1 A1 + v2 A2 YZZ (5.28)

91

The phase is at uniform temperature T and pressure p . The Gibbs function of

the mixture is

G=µn +µ n +µn +µ n

1 1 2 2 3 3 4 4

(5.29)

where the n ' s are the number of moles of the constituents at ant moment, and

the µ ' s are the chemical potentials. Let us imagine that the reaction is allowed to

take place at constant T and p . The degree of reaction changes by an

infinitesimal amount from ε to ε + d ε . The change in the Gibbs function is

dGT , p = ∑ µk dnk = µ1dn1 + µ 2 dn2 + µ3dn3 + µ 4 dn4 (5.30)

The equations of constraint in differential form are

(1) When the reaction proceeds spontaneously to the right, d ε is positive, and

since dGT , p < 0

(v1µ1 + v2 µ 2 ) > (v3 µ3 + v4 µ 4 ) (5.36)

(v1µ1 + v2 µ 2 ) < (v3 µ3 + v4 µ 4 ) (5.37)

i.e., ∑ vk µ k is positive.

(3) At equilibrium, the Gibbs function will be minimum, hence

v1µ1 + v2 µ2 = v3 µ3 + v4 µ 4 (5.38)

which is called the equation of reaction equilibrium. Therefore, it is the value of

∑ vk µk which causes or forces the spontaneous reaction and is called the

“chemical affinity”.

92

5.4 LAW OF MASS ACTION

pressure, when the constituents are ideal gases, the chemical potential are given

by the expressions of the type

µ = RT (φ + ln p + ln x )

k k

(5.39)

k

Substituting in the equation of reaction equilibrium (Eq. (5.38))

v1 (φ1 + ln p + ln x1 ) + v2 (φ2 + ln p + ln x2 ) (5.40)

= v3 (φ3 + ln p + ln x3 ) + v4 (φ4 + ln p + ln x4 )

On rearranging

v3 ln x3 + v4 ln x4 − v1 ln x1 − v2 ln x2 + (v3 + v4 − v1 − v2 )ln p (5.41)

= −(v3φ3 + v4φ4 − v1φ1 − v2φ2 )

∴

x3v .x4v v + v −v −v

3 4 (5.42)

ln v v p 3

= −(v3φ3 + v4φ4 − v1φ1 − v2φ2 )

4 1 2

x1 .x2

1 2

Denoting

ln K = −(v3φ3 + v4φ4 − v1φ1 − v2φ2 ) (5.43)

where K , is known as the equilibrium constant, is a function of temperature only

⎡ x v3 x v4 ⎤ (5.44)

⎢ x v .x v ⎥ p

3 4 v + v −v −v

=K 3 4 1 2

⎣ 1 2 ⎦ ε =ε

1 2

This equation is called the law of mass action. K has the dimension of pressure

raised to the (v3 + v4 − v1 − v2 ) th power. Here the x ' s is the values of mole

fractions at equilibrium when the degree of reaction is ε e .

The law of mass action can also be written in this form

p3v . p4v

3 4 (5.45)

=K

p1v . p2v

1 2

The equilibrium constant K is defined by the expression

ln K = −(v3φ3 + v4φ4 − v1φ1 − v2φ2 ) (5.46)

93

d dφ dφ dφ dφ (5.47)

ln K = −(v3 3 + v4 4 − v1 1 − v2 2 )

dT dT dT dT dT

Let,

φ = 0 − ∫ ∫ p2 − 0

h 1 c dT s (5.48)

RT R T R

Therefore,

= − 02 − ∫ p 2

dφ h c dT (5.49)

dT RT RT

1 h

=

RT 2

( h0

+ ∫ c p

dT ) = −

RT 2

Therefore,

d 1 (5.50)

ln K = ( v h

3 3

+ v h

4 4

− v h

1 1

− v h

2 2

)

dT RT 2

where the h ' s refer to the same temperature T and the same pressure p . If v1

moles of A1 and v2 moles of A2 combine to form v3 moles of A3 and v4 moles of

A4 at constant temperature and pressure, the heat transferred would be, as

shown in Fig.5.1, equal to the final enthalpy (v3h3 + v4 h4 ) minus the initial

enthalpy (v1h1 + v2 h2 ). This is known as the heat of reaction, and is denoted by

∆H .

H

A1

V1 A3

V3

V2 A2 T,P V4 A4

∆H = v3h3 + v4 h4 − v1h1 − v2 h2 (5.51)

94

Therefore,

d ∆H (5.52)

ln K =

dT RT 2

This is known as the van’t Hoff equation. This equation can be used to calculate

the heat reaction at any desired temperature or within a certain temperature

range. By rearranging Eq. (5.52)

d ln K ∆H (5.53)

=

dT R

T2

or,

d ln K ∆H (5.54)

=−

d (1/ T ) R

Therefore,

d log K d log K (5.55)

∆H = −2.303R = −19.148 kJ / kgmol

1 1

d( ) d( )

T T

If K1 and K 2 are the equilibrium constants evaluated at temperatures T1 and T2

respectively

log K1 − log K 2 (5.56)

∆H = −19.148

1 1

−

T1 T2

or,

TT K (5.57)

∆H = −19.148 1 2

log 1

T1 − T2 K2

If ∆H is positive, the reaction is said to be endothermic. If ∆H is negative, the

reaction is exothermic.

h = h0 + ∫ c p dT (5.59)

Therefore,

∆H = v3h03 + v4 h04 − v1h01 − v2 h02 + ∫ (v3c p 3 + v4c p 4 − v1c p1 − v2c p 2 )dT (5.60)

∆H = ∆H 0 + ∫ (v3c3 + v4c4 − v1c1 − v2c2 )dT (5.61)

95

If c p is known as a function of temperature and if at any temperature ∆H is

known, then at any other temperature, ∆H can be determined for a certain

chemical reaction from the above relation.

Some chemical reactions may be expressed as the result of two or more

reactions. If ∆H 0 is known for each of the separate reactions, then ∆H 0 of the

resultant reaction may be calculated.

For example,

ZZX H 2 + 1 O2

H 2O YZZ ∆H 0 = 239,250 J / gmol

2

ZZX CO + 1 O2

CO2 YZZ ∆H 0 = 279,890 J / gmol

2

ZZX CO2 + H 2

CO + H 2O YZZ ∆H 0 = −40640 J / gmol

where

φ = 0 − ∫ ∫ p 2 dT − 0

h 1 c dT s (5.63)

RT R T R

On substitution

1 (5.64)

ln K = (v3h03 + v4 h04 − v1h01 − v2 h02 )

RT

+ ∫ ∫ 3 p 3 4 p 4 2 1 p1 2 p 2

1 (v c + v c − v c − v c )dT

.dT

R T

1

+ (v3 s03 + v4 s04 − v1s01 − v2 s02 )

R

If

∆H 0 = v3h03 + v4 h04 − v1h01 − v2 h02 (5.65)

∆S0 = v3 s03 + v4 s04 − v1s01 − v2 s02

Then,

ln K = −

∆H 0 1

+ ∫ ∫ (v c

3 p3

+ v4c p 4 − v1c p1 − v2c p 2 )dT

dT +

∆S 0 (5.66)

RT R T2 R

This equation is sometimes called as the Nernst’s equation.

96

5.8 THERMAL IONIZATION OF A MONATOMIC GAS

One interesting application of Nernst’s equation was made by Dr. M.N. Saha to

the thermal ionization of a monatomic gas. If a monatomic gas is heated to a high

enough temperature (5000 K and above), some ionization occurs, with the

electrons in the outermost orbit being shed off, and the atoms, ions, and

electrons may be regarded as a mixture of three ideal monatomic gases,

undergoing the reaction

ZZX A+ + e

A YZZ (5.67)

Starting with n0 moles of atoms,

A v n x

1− εe

A1 = A v1 = 1 n1 = n0 (1 − ε e ) x1 =

1+ εe

εe

A3 = A+ v3 = 1 n3 = n0ε e x3 =

1+ εe

ε

A4 = e v4 = 1 n4 = n0ε 0 x4 = e

1 + εe

∑ n = n (1 + ε 0 e

)

⎧ x3v .x4v ⎫

3 4 (5.68)

ln K = ln ⎨ v v ⎬ . p v + v −v −v 3 4 1 2

⎩ x1 .x2 ⎭ε

1 2

or,

εe ε (5.69)

. e

1 + ε e 1 + ε e v + v −v ε e2

ln K = .p 3

= ln

4 1

.p

1− εe 1 − ε e2

1+ εe

5

Since the three gases are monatomic, c p = R which, on being substituted in the

2

Nernst’s equation, gives

ε e2 ∆H 0 5 (5.70)

ln . p = − + ln T + ln B

1 − ε e2 RT 2

∆S 0

where = ln B

R

97

Now,

ε e2 p ∆H 0 (5.71)

ln . 5/ 2 = −

1 − ε e T .B

2

RT

ε e2 T 5/ 2 (5.72)

∴ = Be −∆H 0 / RT

.

1 − εe 2

p

where ε e is the equilibrium value of the degree of ionization. This is known as

the Saha’s equation. For a particular gas the degree of ionization increases with

an increase in temperature and a decrease in pressure. It can be shown that

∆H 0 is the amount of energy necessary to ionize 1 gmole of atoms. If we denote

the ionization potential ∆H 0 of the atom in volts by E , then

Coulomb electron (5.73)

∆H 0 = E (volt ) ×1.59 × 10−19 × 6.06 × 1023

electron gmol

= 9.6354 × 10 E J / gmol

4

εe 96354 E 5 (5.74)

ln p = − + ln T + ln B

1 − ε e2 RT 2

Expressing p in atmospheres, changing to common logarithms and introducing

the values of B from statistical mechanics, Saha finally obtained the equation

ε2 96,354 E 5 ωω (5.75)

log e

p (atm) = − + log T + log i e − 6.491

1− ε 2

e

19.148T 2 ωa

where ωi , ωe and ωa are constants that refer to the ion, electron and atom

respectively. The value ωe for an electron is 2 . The value of E , ωi andωa for a

few elements are given below

Element E , volts ωa ωi

5.12 2 1

Na

3.87 2 1

Ca

6.09 1 2

Cd

8.96 1 2

Zn

9.36 1 2

98

For alkali metals like Cs, Na, K etc., the ionization potential is less. It means less

energy is required to ionize one gmole of atoms. So these are used as seed for

magnetohydrodynamic power generation. Saha applied Eq. (5.70) to the

determination of temperature of stellar atmosphere. The spectrum of a star

contains lines which originate from atoms (arc lines) and those which originate

from ions (spark lines). A comparison of the intensities of an arc line and a spark

line from the same element gives a measure of ε e . Considering a star as a

sphere of ideal gas, the pressure of a star can be estimated. Thus, knowing

ε e , p, E and the ω ' s, temperature of star can be calculated.

by

g = RT (φ + ln p ) (5.76)

For the reaction of the type

ZZX v3 A3 + v4 A4

v1 A1 + v2 A2 YZZ (5.77)

The Gibbs function change of the reaction ∆G is defined by the expression

∆G = v3 g 3 + v4 g 4 − v1 g1 − v2 g 2 (5.78)

where the g ' s refer to the gases completely separated at T , p, ∆G is also

known as the free energy change. Substituting the values of the g ' s

∆ G = RT (v φ + v φ − v φ − v φ ) + RT ln p v3 + v4 −v1 −v2

3 3 4 4 1 1 2 2

(5.79)

But

ln K = −(v3φ3 + v4φ4 − v1φ1 − v2φ2 ) (5.80)

∴ ∆G = − RT ln K + RT ln p v + v −v −v

3 4 1 2 (5.81)

If p is expressed in atmospheres and ∆G is calculated from each gas is at a

pressure of 1 atm, the second term on the right drops out. Under these

conditions ∆G is known as the standard Gibbs function change and denoted by

∆G 0

(5.82)

∆G 0 = RT ln K

This is an important equation which relates the standard Gibbs function change

with temperature and the equilibrium constant. From this the equilibrium constant

can be calculated from changes in the changes in the standard Gibbs function, or

vice versa. For dissociation of water vapour,

1 (5.83)

ZZX H 2 + O2

H 2O YZZ

2

ln K 298 = −93.7.

99

Therefore,

∆G298

0

= −8.3143 × 298 × (−93.7) = 232,157 J / gmol (5.84)

(v3c p 3 + v4c p 4 − v1c p1 − v2 c p 2 ) (5.85)

∆G 0 = ∆H 0 − T dT − T ∆S0

T2

from which also ∆G may be calculated directly. Values of ∆H 0 , ∆S0 and ∆G298

0 0

+

Table 5.3 Fundamental ideal gas reactions

0

J / gmol

ZZX 2 H

H 2 YZZ 427,380 4.90 404,335

HCL YZZ −22.25 95,110

2 2

ZZX 1 H 2 + 1 Br2 50,280

HBr YZZ −24.05 54,050

2 2

1

ZZX H 2 + I 21

HI YZZ 5, 320 −21.00 8, 380

2 2

ZZX 1 N 2 + 1 O2

NO YZZ −90,500 −10.48 −87,570

2 2

ZZX H 2 + 1 O2

H 2O YZZ 239,250 14.70 232,545

2

ZZX H 2 + 1 S 2

H 2 S YZZ 80,450 6.90 71,230

2

ZZX CO + 1 O2

CO2 YZZ 279,890 18.69 258,940

2

ZZX NO + 1 O2

NO2 YZZ 59,500 11.44 37,290

2

ZZX 1 S 2 + O2

SO2 YZZ 349,025 3.77 329,330

2

ZZX 1 N 2 + 3 H 2

NH 3 YZZ 39,800 40.27 16,380

2 2

ZZX SO2 + 1 O2

SO3 YZZ 94,690 89.50 67,880

2

ZZX 2 NO2

N 2O4 YZZ 56,980 174.30 5, 030

100

Both ∆S0 and ∆G298 may be added and subtracted in the same manner as ∆H 0 .

0

For example,

ZZX H 2 + 1 O2

H 2O YZZ ∆G298

0

= 232,545 J / gmol

2

ZZX CO + 1 O2

CO2 YZZ ∆G0 = 258,940 J / gmol

2

ZZX CO2 + H 2

CO + H 2O YZZ ∆G298

0

= −26,395 J / gmol

∆G298

0

26,395

ln K 298 = = = 10.653

RT 8.3143 × 298

K 298 = 42,330

calculated. From Eq.(5.35), if n0 = 1 and n0′ = 0

⎛ ∂G ⎞

⎜ ⎟ = (v3 µ3 + v4 µ4 − v1µ1 − v2 µ2 )

⎝ ∂ε ⎠T , p

Since µ k = RT (φk + ln p + ln xk )

And g k = RT (φk + ln p )

So µ k = g k + RT ln xk

Therefore

⎛ ∂G ⎞ x3v .x4v

3 4

⎜ ⎟ = v3 g 3 + v4 g 4 − v1 g1 − v2 g 2 + RT ln v v

⎝ ∂ε ⎠T , p x1 .x2

1 2

x3v .x4v

3 4

= ∆G + RT ln

x1v .x2v

1 2

At ε = 0, x3 = 0, x4 = 0

⎛ ∂G ⎞

⎜ ⎟ = −∞

⎝ ∂ε ⎠T , p

and at ε = 1, x1 = 0, x2 = 0

101

⎛ ∂G ⎞

⎜ ⎟ = +∞

⎝ ∂ε ⎠T , p

1 v v

At ε = , x1 = 1 , x2 = 2

2 ∑v ∑v

v v

x3 = 3 , x4 = 4

∑v ∑v

where ∑ v = v3 + v4 + v1 + v2

v3 v4

⎛ v3 ⎞ ⎛ v4 ⎞

⎜ ⎟ ⎜ ⎟

⎛ ∂G ⎞ ⎝ ∑ v⎠ ⎝ ∑v ⎠

⎜ ⎟ = ∆G + RT ln

⎝ ∂ε ⎠Tε =, p1

v v

⎛ v1 ⎞ ⎛ v2 ⎞

1 2

⎜ ⎟ ⎜ ⎟

⎝ ∑v ⎠ ⎝ ∑v ⎠

2

If p = 1 atm, T = 298 K

⎛ ∂G ⎞

⎟ p =1atm = ∆G298

0

⎜

⎝ ∂ε ⎠T = 298 K

1

ε=

2

⎛ ∂G ⎞ 1

The slope ⎜ ⎟ at ε = is called the “affinity” of the reaction, and it is equal

⎝ ∂ε ⎠T , p 2

to ∆G

0

at the standard reference state. The magnitude of the slope at

1

ε = (Fig.5.2) indicates the direction in which the reaction will proceed.

2

( δ G /δ ε ) = +α

T ,p

G ( δ G /δ ε ) = −α

T ,p

T,p

ε = 0 ε = εe ε = 1 /2 ε =1

102

For water vapour reaction, ∆G298 is a large positive number, which indicates the

0

1

equilibrium point is far to the left of ε = , and therefore, ε e is very small. Again

2

ZZX 1 1

for the reaction, NO YZZ N 2 + O2 , ∆G298 0

is a large negative value, which

2 2

1

shows that the equilibrium point is far to the right of ε = , and so ε e is close to

2

unity.

process is

nRT (5.86)

dG = Vdp = dp = nRTd (ln p )

p

dG = nRTd (ln f ) (5.87)

where f is called the fugacity, first used by Lewis. The value of fugacity

approaches the value of pressure, as the letter tends to zero, i.e., when ideal gas

conditions apply. Therefore,

f (5.88)

lim

p →0

=1

p

For an ideal gas f = p. Fugacity has the same dimension as pressure.

Integrating Eq. (5.87)

f (5.89)

G − G 0 = nRT ln

f0

0 0

where G and f

f / f 0 is called the activity.

Therefore,

(5.90)

G − G 0 = nRT ln a

For ideal gases, the equilibrium constant is given by

P3v .P4v 3 4 (5.91)

K= v v

P1 .P2 1 2

103

3 4

f 3v . f 4v (5.92)

K real = v v 1 2

f1 . f 2

∆G 0 = −nRT ln K real (5.93)

and

d ln K real ∆H 0 (5.94)

=

dT RT 2

5. 11 ENTHALPY OF FORMATION

Let us consider the steady state steady flow combustion of carbon and oxygen to

from CO2 (Fig.5.3). Let the carbon and oxygen each enter the control volume at

250 C and 1 atm. Pressure, and the heat transfer be such that the product CO2

0

leaves at 25 C ,1 atm Pressure. The measured value of heat transfer is

−393,522 kJ / kgmol of CO2 formed. If H R and H P refer to the total enthalpy

of the reactants and products respectively, then the first law applied to the

reaction C + O2 → CO2 gives

C .V .

C

25 C ,

1 a tm 2 5 C , 1 a tm

C O 2

O 2

Q C .V . = -3 9 3 ,5 2 2 k j/k g m o l o f C O 2

For all the reactants and products in a reaction, the equation may be written as

∑

n h + Q = n he

R

i C .V ∑

P

e

(5.95)

i

104

where R and P refer to the reactants and products respectively. The enthalpy of

0

all the elements at the standard reference state of 25 C , 1 atm is assigned the

value of zero. In the carbon-oxygen reaction, H R = 0. Hence, the energy

equation gives

Q = H = −393,522kJ / kg mol

C .V P

(5.96)

0

This is known as the enthalpy of formation of CO2 at 25 C , 1atm., and

CO2

= −393,522 kJ / kgmol . In most cases,

0

however, the reactants and products are not at 25 C , 1atm , therefore, the

change of enthalpy (in case of constant pressure or S.S.S.F. process) between

250 C , 1atm. and the given state must be known. Thus the enthalpy at any

temperature and pressure, hT , p is

( )

h T , p = h 0f

298 K ,1atm

( )

+ ∆h

298 K ,1atm →T , p

(5.97)

hT , p = h 0f + ∆ h (5.98)

where ∆ h represents the difference in enthalpy between any given state and the

enthalpy at 298.15 K , 1atm . Table 5.4 gives the values of the enthalpy of

formation of a number of substances in kJ / kgmol .

105

Table 5.4 Enthalpy of Formation, Gibbs Function of Formation, and Absolute

0

Entropy of Various Substance at 25 C , 1atm pressure

Molecular h 0f g 0f s0

Substance

Weight , M kJ / kgmol kJ / kgmol kJ / kgmolK

CO( g ) 28.011 −110529 −137150 197.653

CO2 ( g ) 44.001 −393522 −394374 213.795

H 2O ( g ) 18.015 −241827 −228583 188.833

H 2O(l ) 18.015 −285838 −237178 70.049

CH 4 ( g ) 16.043 −74873 −50751 186.256

C2 H 2 ( g ) 26.038 +226731 +209234 200.956

C2 H 4 ( g ) 28.054 +52283 +68207 219.548

C2 H 6 ( g ) 30.070 −84667 −32777 229.602

C3 H 8 ( g ) 44.097 −103847 −23316 270.019

C4 H10 ( g ) 58.124 −126148 −16914 310.227

C8 H18 ( g ) 114.23 −208447 +16859 466.835

C8 H18 (l ) 114.23 −249952 +6940 360.896

Table 5.5 give the values of ∆ h = h − h298 kJ / kg mol for various substances at

0 0

different temperature.

0

Table 5.5 Enthalpy of formation at 25 C , ideal gas enthalpy, and Absolute

Entropy at 0.1 MPa (1bar) Pressure

(h )

0

f 298

= 0kJ / kmol (h )

0

f 298

= 0kJ / kmol

M = 28.013 M = 31.999

Temperature ( 0

h − h 298

0

) s

0

( 0 0

h − h 298 ) s

0

0 -8669 0 -8682 0

100 -5770 159.813 -5778 173.306

200 -2858 179.988 -2866 193.486

106

298 0 191.611 0 205.142

300 54 191.791 54 205.322

400 2971 200.180 3029 213.874

500 5912 206.740 6088 220.698

600 8891 212.175 9247 226.455

700 11937 216.866 12502 231.272

800 15046 221.016 15841 235.924

900 18221 224.757 19246 239.936

1000 21406 288.167 22707 243.585

1100 24757 231.309 26217 246.928

1200 28108 234.225 29765 250.016

1300 31501 236.941 33351 252.886

1400 34936 239.484 36966 255.564

1500 38405 241.878 40610 258.078

1600 41903 244.137 44279 260.446

1700 45430 246.275 47970 262.685

1800 48982 248.304 51689 264.810

1900 52551 250.237 55434 266.835

2000 56141 252.078 59199 268.764

Carbon Dioxide ( CO ) 2

Carbon Monoxide ( CO )

(h ) 0

f 298

= −393522kJ / kmol (h )

0

f 298

= −110529kJ / kmol

M = 44.01 M = 28.01

Temperature ( 0

h − h 298

0

) s

0

( 0

h − h 298

0

) s

0

0 -9364 0 -8669 0

100 -6456 179.109 -5770 165.850

200 -3414 199.975 -2858 186.025

298 0 213.795 0 197.653

300 67 214.025 54 197.833

400 4008 225.334 2975 206.234

500 8314 234.924 5929 212.828

600 12916 243.309 8941 218.313

700 17765 250.773 12021 223.062

800 22815 257.517 15175 227.271

900 28041 263.668 18397 231.006

1000 33405 269.325 21686 234.531

1100 38894 274.555 25033 237.719

1200 44484 279.417 28426 240.673

1300 50158 283.956 31865 243.426

107

1400 55907 288.216 35338 245.999

1500 61714 292.224 38848 248.421

1600 67580 296.010 42384 250.702

1700 73492 299.592 45940 252.861

1800 79442 302.993 49522 254.907

1900 85429 306.232 53124 256.852

2000 91450 309.320 56739 258.710

Water ( H O)

2

Hydrogen,Diatomic (H ) 2

(h )

0

f

298

= −241827 kJ / kmol (h )

0

f

298

= 0kJ / kmol

M = 18.015 M = 2.016

Temperature (h − h )

0 0

298 s

0

(h − h )

0 0

298 s

0

0 -9904 0 -8468 0

100 -6615 152.390 -5293 102.145

200 -3280 175.486 -2770 119.437

298 0 188.833 0 130.684

300 63 189.038 54 130.864

400 3452 198.783 2958 139.215

500 6920 206.523 5883 145.738

600 10498 213.037 8812 151.077

700 14184 218.719 11749 155.608

800 17991 223.803 14703 159.549

900 21924 228.430 17628 163.060

1000 25978 232.706 20686 166.223

1100 30167 236.694 23723 169.118

1200 34476 240.443 26794 171.792

1300 38903 243.986 29907 174.281

1400 43447 247.350 33062 176.620

1500 48095 250.560 36267 178.833

1600 52844 253.622 39522 180.929

1700 57685 256.559 42815 182.929

1800 62609 259.372 46150 184.833

1900 67613 262.078 49522 186.657

2000 72689 264.681 52932 188.406

For the S.S.S.F. process as shown in Fig.5.4 the first law gives

108

H R + QC .V . = H P + WC .V . (5.99)

or,

∑n h + Q

R

i i C .V .

= ∑ ne he + WC .V .

p

(5.100)

or,

∑ n ⎡⎣ h

R

i

0

f

+ ∆ h ⎤⎦ + QC .V . = ∑ ne ⎡⎣ h 0f + ∆ h ⎤⎦ + WC .V .

p e

(5.101)

i

C .V

n1 n3

Reactants

Products

n2 n4

Q c.v W c.v

When the states of reactants and products are not in the standard reference

state (298 K , 1atm), then, as shown in Fig.5.5,

109

R

R0

h0 P

RP

H

P0

298 K T

QC .V . = H P − H R = ( H P − H P ) + ( H P − H R ) + ( H R − H R )

0 0 0 0

(5.102)

= ∑ ne (h p − h p ) + ∆ h RP − ∑ ni (h R − h R ) (5.103)

0

0 0

P R

0

where ∆ h PR is the enthalpy of reaction at the standard temperature (298 K ) . The

variation of enthalpy with pressure is not significant.

QC .V . = U P − U R = (U P − U P ) + (U P − U R ) + (U R − U R )

0 0

(5.104)

0 0

= ∑ ne (u p − u p ) + ∆u − ∑ ni (u R − u R )

0

0 RP 0

p R

0

where ∆u RP is the internal energy of reaction at 298 K .

changes in K.E. and P.E., then the energy equation becomes

H =H R P

(5.105)

or,

∑n h = ∑n h

R

i i

p

e e

(5.106)

or,

∑n h = ∑n h

R

i i

p

e e

(5.107)

or,

110

∑ n ⎡⎣ h + ∆ h ⎤ = ∑ ne ⎡ h f + ∆ h ⎤

0 0 (5.108)

⎦i P ⎣ ⎦e

i f

R

For such a process, the temperature of the products is called the adiabatic flame

temperature which is the maximum temperature achieved for the given reactants.

The adiabatic flame temperature can be controlled by the amount of excess air

supplied; it is the maximum with a stoichiometric mixture. Since the maximum

permissible temperature in a gas turbine is fixed from metallurgical

considerations, close control of the temperature of the products is achieved by

controlling the excess air. For a given reaction the adiabatic flame temperature is

computed by trial and error. The energy of the reactants H R being known, a

suitable temperature is chosen for the products so that the energy of products at

that temperature becomes equal to the energy of the reactants.

VALUE

the product and the enthalpy of the reactants when complete combustion occurs

at a given temperature and pressure. Therefore,

h RP = H P − H R (5.109)

or,

h RP = ∑ ne ⎡ h f + ∆ h ⎤ − ∑ ni ⎡ h f + ∆ h ⎤

0 0 (5.110)

P ⎣ ⎦e R ⎣ ⎦i

where h RP is the enthalpy of combustion ( kJ / kg or kJ / kgmol ) of fuel. The

value of the enthalpy of combustion of different hydrocarbon fuels at

250 C , 1atm are given in Table 5.6.The internal energy of combustion, µ RP , is

defined similar way.

µ RP = U P − U R (5.111)

= ∑ ne ⎡ h f + ∆ h − pv ⎤ − ∑ ni ⎡ h f + ∆ h − pv ⎤

0 0 (5.112)

p ⎣ ⎦e R ⎣ ⎦i

If all the gaseous constituents are considered ideal gases and the volume of

liquid and solid considered is assumed to be negligible compared to gaseous

volume.

u RP = u RP − RT (n −n

gaseous products

) (5.113)

gaseous reac tan ts

111

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 constant pressure. Similarly, the negative of the internal energy of

combustion is sometimes designated as the heating value at constant volume in

the case of combustion, because it represents the amount of heat transfer in the

constant volume process. The higher heating value (HHV) or higher calorific

value (HCV) is the heat transferred when H 2O in the products is in the liquid

state. The lower heating value (LHV) or lower calorific value (LCV) is the heat

transferred in the reaction when H 2O in the products is in the vapour state.

Therefore,

LHV = HHV − mH O .h fg 2

(5.114)

where mH O is the mass of water formed in the reaction.

2

So far only first law aspects of chemical reactions have been discussed. The

second law analysis of chemical reactions needs a base for the entropy of

various substances. The entropy of substances at the absolute zero of

temperature, called absolute entropy, is dealt with by the third law of

thermodynamics formulated in the early twentieth century primarily by Nernst

(1864-1941) and Max Planck (1858-1947). The third law states that the entropy

of a perfect crystal is zero at the absolute zero of temperature ant it represents

the maximum degree of order. A substance not having a perfect crystalline

structure and processing a degree of randomness such as a solid solution or a

glassy solid has a finite value of entropy at absolute zero. The third law provides

an absolute base from which the entropy of each substance can be measured.

The entropy relative to this base is referred to as the absolute entropy. Table 5.5

gives the absolute entropy of various substances at the standard state

250 C , 1atm. For any other state,

( ) (5.115)

0

sT , p = sT + ∆ s

T ,1atm ,→T , p

0

where s T refers to the absolute entropy at 1 atm, and temperature T, and

(s)T ,1atm ,→T , p

refers to the change of entropy for an isothermal change of pressure

from 1atm to pressure p (Fig.5.6).

112

A b s o lu te e n tro p y is

tm

k n o w a lo n g th is

1a

is o b a r, a s s u m in g id e a l g a s b e h a v io u r a t

1 a tm

T

( s ) T ,1 a tm T ,p

T .p

s

Fig. 5.6 Absolute entropy

0

Table 5.5 give the value of s for various substances at 1 atm. and at different

temperatures. Assuming ideal gas behaviour ( ∆s ) T ,1atm ,→T , p

can be determined

(Fig 5.6).

p2 (5.116)

s 2 − s1 = − R ln

p1

or,

( ∆s ) T ,1atm , →T , p

= − R ln p (5.117)

where p is in atm.

0

Table 5.6 Enthalpy of Combustion of Some Hydrocarbons at 25 C

Liquid H 2O in Vapour H 2O in

Pr oducts Pr oducts

( Negative of ( Negative of

Higher Heating Lower Heating

Value) Value

Liquid Liquid

Gaseous Gaseous

Hydro − Hydro −

Hydro − Hydro −

Hydrocarbon carbon carbon

Formula carbon carbon

kJ / kg kJ / kg

kJ / kg kJ / kg

fuel fuel

fuel fuel

113

(1) (2) (3) (4) (5) (6)

Paraffin Family

−55496

CH 4 −50010

Methane −51875

C2 H 6 −47484

Ethane −49975 −50345

C3 H 8 −45983 −46353

Propane −49130 −49500

C4 H10 −45344 −45714

Butane −48643 −49011

C5 H12 −44983 −45951

Pentane −48308 −48676

C6 H14 −44733 −45101

Hexane −48071 −48436

C7 H16 −44557 −44922

Hexane −47893 −48256

C8 H18 −44425 −44788

Octane −47641 −48000

C10 H 22 −44239 −44598

Decane −47470 −47828

C12 H 26 −44100 −44467

Olefin Family

Ethene C2 H 4 −50296 −47158

Propene C3 H 6 −48917 −45780

Butene C4 H 8 −48453 −45316

Pentene C5 H10 −48134 −44996

Hexene C6 H12 −47937 −44800

Heptene −47800 −44662

C7 H14

Octene −47693 −44556

C8 H16

Nonene −47612

C9 H18 −44475

Decene −47547

C16 H 20 −44410

Alkylbenzene Family

Benzene C6 H 6 −41831 −42266 −40141 −40576

Methylbenezene C7 H 8 −42473 −42847 −40527 −40937

Ethylbenzene C8 H10 −42997 −43395 −40924 −41322

Propylbenzene C9 H12 −43416 −43800 −41219 −41603

Butylbenzene C10 H14 −43748 −44123 −41453 −41828

114

5.16 SECOND LAW ANALYSIS OF REACTIVE SYSTEMS

The reversible work for a steady state flow process, in the absence of changes in

K.E. and P.E., is given by

Wrev = ∑ ni ⎡ h f + ∆ h − T0 s ⎤

0 (5.119)

R ⎣ ⎦i

−∑ ne ⎡ h f + ∆ h − T0 s ⎤

0

P ⎣ ⎦e

I = ∑ neT0 s e − ∑ niT0 s i − QC .V . (5.120)

P R

The availability,ψ , in the absence of K.E. and P.E. changes, for an S.S.S.F.

process is

ψ = (h − T s ) − (h − T s )

0 0 0 0

(5.121)

When an S.S.S.F. chemical reaction takes place in such a way that both the

reactants and products are in temperature equilibrium with the surroundings, the

reversible work is given by

W = ng − ng

rev ∑R

i i ∑ P

e e

(5.122)

where the g ′ s refer to the Gibbs function. The Gibbs function for formation, g f , is

0

0

defined similar to the enthalpy of formation, h f . The Gibbs function of each of the

0

elements at 25 C and 1atm. is assumed to be zero, and the Gibbs function of

0

each substance is found relative to this base. Table 5.4 gives g f for some

0

substance at 25 C , 1atm.

For a fuel at T0, p0, the chemical exergy is the maximum theoretical work that

could be obtained through reaction with environmental substances. However,

due to various irreversibilities like friction and heat loss, the actual work obtained

is only a fraction of this maximum theoretical work. The second law efficiency

may thus be defined as the ratio of

115

Actual work done (5.143)

η II =

Maximum theoretical work

WcV (5.144)

η II =

m fuel xach

The associated irreversibility and the consequent exergy loses require to be

reduced to enhance the second law efficiency, which in turn, reduce the fuel

consumption and also increases the cost. The trade off between the fuel savings

and the additional costs must be carefully weighed.

the system attains the dead state. Under such conditions, exergy of the system is

zero. However, the contents of a system even at the dead state may undergo

chemical reaction with environmental components and produce additional work.

certain amount of fuel at T0 , p0 . Work is obtainable by allowing the fuel to react

with oxygen from the environment to produce the components of CO2 and H 2O .

The chemical exergy is thus defined as the maximum theoretical work that could

be developed by the combined system. Thus for a given system at a specific

state

the environment (Fig.5.7) which is assumed to be consisting of an ideal gas

mixture at T0, p0.

116

Work

p0, T0

Ca H b

CO 2 at T0

O2 at T0 XCO2, p0

XO2 p0

H2O at T0,XH20 p 0

T0

The oxygen that reacts with the fuel is at a partial pressure of x02 p0, where x02 is

the mole fraction of oxygen in the environment. The fuel and oxygen react

completely to produce CO2 and H 2O, which exit in separate steams at τ o and

respective partial pressures of χ co ρo and χ H ρo . The reaction is given by

2

.

2O

⎛ b⎞ b (5.123)

Ca H b + ⎜ a + ⎟ O2 → aCO2 + H 2O

⎝ 4⎠ 2

At steady state, the energy balance gives

⋅ (5.124)

Q cV

R = WcV + nH

+ nH P

or,

WcV Q cV Q 0 ⎛ b⎞ b (5.125)

= + H R − H P = cV + (h f + ∆ h)Ca H b + ⎜ a + ⎟ h 0 − ahCO − h H O

n n ⎝ 4⎠

2 2 2

n 2

where n is the rate of fuel flow in moles, and K.E. and P.E. effects are neglected.

An entropy balance for the control volume gives

Q cV / n ⎛ b⎞ (5.126)

0= + sC H + ⎜ a + ⎟ so

⎝ 4⎠

a b 2

T0

b s

− as CO − s H O + gen

n

2 2

2

Eliminating Q cV between Eq. (5.125) and Eq. (5.126)

117

WcV ⎡ ⎛ b⎞ b ⎤ (5.127)

= ⎢ hC H + ⎜ a + ⎟ h o − ahCO − h H O ⎥

n ⎝ 4⎠

a b 2 2 2

⎣ 2 ⎦

⎡ ⎛ b⎞ b ⎤ T s

−T0 ⎢ s C H + ⎜ a + ⎟ s o − as CO − s H O ⎥ − 0 gen

⎝ 4⎠ n

a b 2 2 2

⎣ 2 ⎦

The specific enthalpies in Eq. (5.127) can be determined knowing only the

temperature T0 and the specific entropies can be determined knowing T0 , p0 and

the composition of the environment. For maximum work,

(5.128)

T s

I = 0 gen = 0

n

⎡ ⎛ b⎞ b ⎤ (5.129)

a ch = ⎢ hC H + ⎜ a + ⎟ hO − ahCO − h H O ⎥

⎝ 4⎠

a b 2 2 2

⎣ 2 ⎦

⎡ ⎛ b⎞ b ⎤

−T0 ⎢ s C H + ⎜ a + ⎟ s O − as CO − s H O ⎥

⎝ 4⎠

a b 2 2 2

⎣ 2 ⎦

The specific entropies for O2 , CO2 and H 2O are written from Eq. (5.104),

s i (T0, xi p0 ) = s i (T0, p0 ) − R ln xi (5.130)

where the first term on the right is the absolute entropy at T0 and p0, and xi is the

mole fraction of component in the environment .Therefore ,Eq.(5.129) becomes,

(5.131)

⎡ ⎛ b⎞ b ⎤

a ch = ⎢ hC H + ⎜ a + ⎟ h o − ahCO − h H O ⎥ (at T0, p0 )

⎝ 4⎠

a b 2 2 2

⎣ 2 ⎦

⎡ ⎛ b⎞ ⎤

−T0 ⎢ s C H + ⎜ a + ⎟ s O − as CO − s H O ⎥ ( at T0, p0 )

b

⎝ 4⎠

a b 2 2 2

⎣ 2 ⎦

(x )

a +b / 4

+ RT ln

O2

(x ) (x )

0 a b/2

CO2 H 2O

⎡ ⎛ b⎞ b ⎤ (5.132)

a ch = ⎢ g C H + ⎜ a + ⎟ g O − ag CO − g H O ⎥ (at T0, p0 )

⎣ ⎝ 4⎠ 2 ⎦

a b 2 2 2

118

(x )

a +b / 4

O2

+ RT ln

(x ) (x )

0 a b/2

CO2 H 2O

where

g (T0, p0 ) = g f + ∆ g T (5.133)

0

0 , p0→Tref , pref

For the special case when T0 and p0 are the same as Tref and pref , ∆ g will be

zero. The chemical exergy of pure CO at T0 , p0 where the reaction is given by

1 (5.134)

CO + O2 → CO2

2

⎡ ⎤

(a )

(5.135)

= ⎢ g CO + g O − g CO ⎥ ( at T0, p0 )

1

ch

⎣ 2 ⎦

CO 2 2

(x )

1/ 2

+ RT ln

O2

0

xCO 2

T0, p0. The chemical exergy of liquid water is,

(a ) ch

H 2O ( l )

= ⎡⎣ g H O ( l ) − g H O ( g ) ⎤⎦ ( atT0, p0 )

2 2

(5.137)

V2

= (u − u0 ) + p0 (v − v0 ) − T0 ( s − s0 ) + + gz + ach

2

and the specific flow exergy is given by

V2 (5.139)

a = (h − h0 ) − T0 ( s − s0 ) +

+ gz + ach

2

Between two states of system a constant composition, ach cancels, leaving just

the thermo-mechanical contribution. For example, to find the chemical exergy of

liquid octane, the reaction is

C H (l ) + 12.5O → 8CO + 9 H O( g )

8 18 2

(5.140)

2 2

N 2 75.67%, O2 20.35%, H 2O3.12%, CO2 0.03%, others 0.83%. Then,

a ch = ⎡⎣ g C H8 18 ( l )

+ 12.5 g O − 8 g CO − 9 g H O ⎤⎦ ( atT0, p0 )

2 2 2

(5.141)

119

(x )

12.5

+ RT ln

O2

(x ) (x )

0 8 9

CO2 H 2O

(a )C H

ch 8 18

(l ) = 6940 + 12.45(0) − 8(−394,374) − 9(−228,583) (5.142)

( 0.2035)

12.5

+8.3143(298.15)ln

( 0.003) ( 0.0312 )

8 9

= 5,408,068.72kJ / kgmol

= 47,346kJ / kg

120

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