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Chapter 15 CHEMICAL REACTIONS

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Chapter 15 CHEMICAL REACTIONS Powered By Docstoc
					                    Chapter 15

                 Chemical Reactions

             Study Guide in PowerPoint

                    to accompany


Thermodynamics: An Engineering Approach, 7th edition
      by Yunus A. Çengel and Michael A. Boles
   The combustion process is a chemical reaction whereby fuel is oxidized and energy
   is released.




Fuels are usually composed of some compound or mixture containing carbon, C, and
hydrogen, H2.
                                      CH4         Methane
Examples of hydrocarbon fuels are:   C8H18        Octane
                                     Coal         Mixture of C, H2, S,
                                                  O2, N2 and non-combustibles

Initially, we shall consider only those reactions that go to completion. The
components prior to the reaction are called reactants and the components after the
reaction are called products.

For more information and animations illustrating this topic visit the Animation Library
developed by Professor S. Bhattacharjee, San Diego State University, at this link.
                                                                                      2
test.sdsu.edu/testhome/vtAnimations/index.html
                                 Reactants  Products
For complete or stoichiometric combustion, all carbon is burned to carbon dioxide
(CO2) and all hydrogen is converted into water (H2O). These two complete
combustion reactions are as follows:
                                    C  O2  CO2
                                        1
                                    H2  O2  H2 O
                                        2
Example 15-1

A complete combustion of octane in oxygen is represented by the balanced combustion
equation. The balanced combustion equation is obtained by making sure we have the
same number of atoms of each element on both sides of the equation. That is, we
make sure the mass is conserved.
                          C8 H18  A O2  B CO2  D H2 O
Note we often can balance the C and H for complete combustion by inspection.

                            C8 H18  A O2  8 CO2  9 H2 O


                                                                                    3
 The amount of oxygen is found from the oxygen balance. It is better to conserve
 species on a monatomic basis as shown for the oxygen balance.

                         O: A(2)  8(2)  9(1)
                                    A  12.5

              C8 H18  12.5 O2  8 CO2  9 H2 O
Note: Mole numbers are not conserved, but we have conserved the mass on a total
basis as well as a specie basis. Also, 12.5 kmol of O2 are used to form the CO2 and
H2O. If 15 kmol of O2 were supplied to the process, 2.5 kmol of O2 would be excess
oxygen in the products.


The complete combustion process is also called the stoichiometric combustion, and
all coefficients are called the stoichiometric coefficients.



                                                                                   4
In most combustion processes, oxygen is supplied in the form of air rather
than pure oxygen.

Air is assumed to be 21 percent oxygen and 79 percent nitrogen on a
volume basis. For ideal gas mixtures, percent by volume is equal to
percent by moles. Thus, for each mole of oxygen in air, there exists 79/21
= 3.76 moles of nitrogen. Therefore, complete or theoretical combustion of
octane with air can be written as


                 C8 H18  12 .5 ( O2  3. 76 N 2 ) 
                            8 CO2  9 H2 O  47 N 2



                                                                             5
Air-Fuel Ratio

Since the total moles of a mixture are equal to the sum of moles of each component,
there are 12.5(1 + 3.76) = 59.5 moles of air required for each mole of fuel for the
complete combustion process.

Often complete combustion of the fuel will not occur unless there is an excess of air
present greater than just the theoretical air required for complete combustion.

To determine the amount of excess air supplied for a combustion process, let us define
the air-fuel ratio AF as
                                           kmol air
                                     AF 
                                          kmol fuel
Thus, for the above example, the theoretical air-fuel ratio is

                    12.5(1  3.76)         kmol air
             AFth                  59.5
                          1               kmol fuel

                                                                                    6
On a mass basis, the theoretical air-fuel ratio is
                                                  kg air
                                                28.97
                            kmol air             kmol air
               AFth  59.5
                           kmol fuel [8(12)  18(1)] kg fuel
                                                    kmol fuel
                             kg air
                     1512
                        .
                            kg fuel
Percent Theoretical and Percent Excess Air

In most cases, more than theoretical air is supplied to ensure complete combustion and
to reduce or eliminate carbon monoxide (CO) from the products of combustion. The
amount of excess air is usually expressed as percent theoretical air and percent excess
air.
                                                AFactual
                        Percent theoreticalair          100%
                                                  AFth
                                           AFactual  AFth
                        Percentexcessair                  100%
                                               AFth                             7
Show that these results may be expressed in terms of the moles of oxygen only as
                                                  N O2 actual
                      Percent theoretical air                  100%
                                                    N O2 th

                                             N O2 actual  N O2 th
                      Percent excess air                            100%
                                                    N O2 th
Example 15-2

Write the combustion equation for complete combustion of octane with 120 percent
theoretical air (20 percent excess air).
                    C8 H18  12(12.5) (O2  3.76 N 2 ) 
                              .
                            8 CO2  9 H2 O  (0.2)(12.5) O2  12(47) N 2
                                                               .
Note that (1)(12.5)O2 is required for complete combustion to produce 8 kmol of
carbon dioxide and 9 kmol of water; therefore, (0.2)(12.5)O2 is found as excess
oxygen in the products.
                        C8 H18  12(12.5) (O2  3.76 N 2 ) 
                                  .
                                8 CO2  9 H2 O  2.5 O2  12(47) N 2
                                                            .
                                                                                  8
Second method to balance the equation for excess air (see the explanation of this
technique in the text) is:


            C8 H18  12 Ath (O2  3.76 N 2 ) 
                      .
               8 CO2  9 H2 O  0.2 Ath O2  12 Ath (3.76) N 2
                                               .


            O:     12 Ath (2)  8(2)  9(1)  0.2 Ath (2)
                    .
                           Ath  12.5
NOTE: THIS METHOD WORKS ONLY FOR COMPLETE COMBUSTION!!!

WHEN PERCENT OR EXCESS THEROETICAL AIR IS SUPPLIED TO AN
INCOMPLETE COMBUSTION PROCESS, THE AMOUNT OF SUPPLIED O2
(1.2ATH IN THIS EXAMPLE) NOT USED FOR FORMING CO2 MUST BE
ACCOUNTED FOR IN THE EXCESS O2 IN THE PODUCTS.


                                                                                9
Incomplete Combustion with Known Percent Theoretical Air

Example 15-3

Consider combustion of C8H18 with 120 % theoretical air where 80 % C in the fuel goes
into CO2.


Theoretical        C8 H18  Ath O2  8 CO2  9 H 2O
Combustion
                   theoretical O :         Ath (2)  8(2)  9(1)
                                     Ath  12.5
   The chemical reaction equation for incomplete Combustion with excess
   theoretical air and X amount of O2 in products is

    C8 H18  12(12.5) (O2  3.76 N 2 ) 
              .
       0.8(8) CO2  0.2(8) CO  9 H2 O  X O2  12(47) N 2
                                                 .
                                                                              10
O balance gives
               O:   12(12.5)(2)  0.8(8)(2)  0.2(8)(1)  9(1)  X (2)
                     .
                             X  3.3
Why is X > 2.5, the amount of O2 in the previous complete combustion example?

Then the balanced equation is
                    C8 H18  12(12.5) (O2  3.76 N 2 ) 
                              .
                       6.4 CO2  16 CO  9 H2 O  3.3 O2  12(47) N 2
                                  .                         .
Combustion Equation When Product Gas Analysis Is Known

Example 15-4

Propane gas C3H8 is reacted with air such that the dry product gases are 11.5 percent
CO2, 2.7 percent O2, and 0.7 percent CO by volume. What percent theoretical air was
supplied? What is the dew point temperature of the products if the product pressure is
100 kPa?

We assume 100 kmol of dry product gases; then the percent by volume can be
interpreted to be mole numbers. But we do not know how much fuel and air were
supplied or water formed to get the 100 kmol of dry product gases.          11
                 X C3 H8  A (O2  3.76 N 2 ) 
                   115 CO2  0.7 CO  2.7 O2  B H2 O  A(3.76) N 2
                     .
  The unknown coefficients A, B, and X are found by conservation of mass for each
  species.                 C: X (3)  115(1)  0.7(1)
                                           .                  X  4.07
                            H: X (8)  B (2)                  B  16.28
                            O: A(2)  115(2)  0.7(1)
                                           .
                                           2.7(2)  B (1)     A  22.69
                            N 2 : A(3.76)  85.31
The balanced equation is
           4.07 C3 H8  22.69 (O2  3.76 N 2 ) 
             115 CO2  0.7 CO  2.7 O2  16.28 H2 O  85.31 N 2
                .
  Second method to find the coefficient A:

  Assume the remainder of the 100 kmol of dry product gases is N2.

                           kmol N 2  100  (115  0.7  2.7)  851
                                               .                  .
                                                                              12
Then A is
                                  851.
                               A       22.65 ( fairly good check )
                                  3.76
These two methods don’t give the same results for A, but they are close.

What would be the units on the coefficients in the balanced combustion equation?

Later in the chapter we will determine the energy released by the combustion process
in the form of heat transfer to the surroundings. To simplify this calculation it is
generally better to write the combustion equation per kmol of fuel. To write the
combustion equation per unit kmol of fuel, divide by 4.07:
                    C3 H8  557 (O2  3.76 N 2 ) 
                             .
                       2.83 CO2  017 CO  0.66 O2  4.0 H2 O  20.96 N 2
                                   .
The actual air-fuel ratio is
                                                                 kg air
                                  (5.57)(1  3.76) kmol air 28.97
                                                                kmol air
                     AFactual   
                                                              kg fuel
                                    1kmol fuel[3(12)  8(1)]
                                                             kmol fuel
                                         kg air
                                 17.45                                        13
                                        kg fuel
The theoretical combustion equation is
                            C3 H8  5 (O2  3.76 N 2 ) 
                                        3 CO2  4.0 H2 O  18.80 N 2
The theoretical air-fuel ratio is
                                                             kg air
                               (5)(1  3.76) kmol air 28.97
                                                            kmol air
                        AFth 
                                                           kg fuel
                                1kmol fuel[3(12)  8(1)]
                                                          kmol fuel
                                      kg air
                              15.66
                                     kg fuel
The percent theoretical air is
                                                   AFactual
                         Percent theoretical air           100%
                                                    AFth
                                                   17.45
                                                        100  111%
                                                   15.66
                                                                       14
or
                                                N O2 actual
                    Percent theoretical air                  100%
                                                 N O2 th
                                                 .
                                                557
                                                   100  111%
                                                  5
The percent excess air is
                                         AFactual  AFth
                    Percent excess air                  100%
                                              AFth
                                         17.45  15.66
                                                      100  11%
                                             15.66
Dew Point Temperature

The dew point temperature for the product gases is the temperature at which the
water in the product gases would begin to condense when the products are cooled at
constant pressure. The dew point temperature is equal to the saturation temperature
of the water at its partial pressure in the products.


                                                                              15
                         Tdp  Tsat at Pv  yv Pproducts
                               N water
                          yv 
                                Ne
                                 products
Example 15-5

Determine dew point temperature of the products for Example 15-4.
                                            4
                     yv                                   0.1398
                          2.83  0.17  0.66  4  20.96
                     Pv  yv Pproducts  0.1398(100 kPa )
                         13.98 kPa
                    Tdp  Tsat at13.98 kPa
                        =52.31oC
What would happen if the product gases are cooled to 100oC or to 30oC?

                                                                         16
Example 15-6

An unknown hydrocarbon fuel, CXHY is reacted with air such that the dry product
gases are 12.1 percent CO2, 3.8 percent O2, and 0.9 percent CO by volume. What is
the average makeup of the fuel?

We assume 100 kmol (do you have to always assume 100 kmol?) of dry product
gases; then the percent by volume can be interpreted to be mole numbers. We do
not know how much air was supplied or water formed to get the 100 kmol of dry
product gases, but we assume 1 kmol of unknown fuel.

                     C X HY  A (O2  3.76 N 2 ) 
                        12.1 CO2  0.9 CO  38 O2  B H2 O  D N 2
                                              .
 The five unknown coefficients A, B, D, X, and Y are found by conservation of mass
 for each species, C, H, O, and N plus one other equation. Here we use the
 subtraction method for the nitrogen to generate the fifth independent equation for the
 unknowns.
                     C X HY  A (O2  3.76 N 2 ) 
                        12.1 CO2  0.9 CO  38 O2  B H2 O  D N 2
                                              .
                                                                                 17
The unknown coefficients A, B, D, X, and Y are found by conservation of mass for
each species. Here we assume the remainder of the dry product gases is nitrogen.

                 N 2 : D  100  (12.1  0.9  38)  83.2
                                                .
                                  D     83.2
                           O2 : A           22.13
                                3.76 3.76
                      O: A(2)  (12.1)(2)  (0.9)(1)  (38)(2)  B(1)
                                                         .
                           B  1154
                                  .
                       C: 1( X )  12.1(1)  (0.9)(1)
                              X  13.0
                       H: 1(Y )  B(2)
                               Y  23.08
The balanced equation is

      C13 H23.08  22.13 (O2  3.76 N 2 ) 
        12.1 CO2  0.9 CO  38 O2  1154 H2 O  83.2 N 2
                                .          .
                                                                             18
Enthalpy of Formation

Consider the chemical reaction that occurs during the
decomposition process in the compost pile shown below. On the
day this photo was taken, the ambient temperature was 69°F. At
two feet inside the pile, the temperature was 135°F. This process
is an exothermic reaction and heat energy is given off during the
decomposition.




                                                                    19
When a compound is formed from its elements (e.g., methane, CH4, from C and H2),
heat transfer occurs. When heat is given off, the reaction is called exothermic.
When heat is required, the reaction is called endothermic. Consider the following.




The reaction equation is
                                C  2 H2  CH4
The conservation of energy for a steady-flow combustion process is
                                     Ein  Eout
                              Qnet  HReactants  HProducts


                              Qnet  HProducts  HReactants                   20
                        Qnet      N h
                                 Products
                                                e e        Nh
                                                          Reactants
                                                                      i i


                        Qnet  1hCH4  (1hC  2hH2 )
 A common reference state for the enthalpies of all reacting components is
 established as
    The enthalpy of the elements or their stable compounds is defined to
    be ZERO at 25oC (298 K) and 1 atm (or 0.1 MPa).

                                Qnet  1hCH4  (1(0)  2(0))
                                       hCH4
                                                                        o
This heat transfer is called the enthalpy of formation for methane, h f . The
superscript (o) implies the 1 atm pressure value and the subscript (f) implies 25°C
         o
data, h f is given in Table A-26.

During the formation of methane from the elements at 298 K, 0.1 MPa, heat is given
off (an exothermic reaction) such that
                                                            kJ
                           Qnet  h    o
                                      f CH       74,850
                                            4             kmolCH4                 21
                         o
The enthalpy of formation h f is tabulated for typical compounds. The enthalpy of
formation of the elements in their stable form is taken as zero. The enthalpy of
formation of the elements found naturally as diatomic elements, such as nitrogen,
oxygen, and hydrogen, is defined to be zero. The enthalpies of formation for several
combustion components are given in the following table.
                     Substance            Formula M       h fo kJ/kmol
                               Air                 28.97        0

                             Oxygen         O2      32          0
                             Nitrogen       N2      28          0
                        Carbon dioxide     CO2      44       -393,520
                       Carbon monoxide     CO       28       -110,530
                        Water (vapor)    H2Ovap     18       -241,820
                        Water (liquid)    H2Oliq    18       -285,830
                             Methane       CH4      16        -74,850
                          Acetylene        C2H2     26       +226,730
                             Ethane        C2H6     30        -84,680
                             Propane       C3H8     44       -103,850
                             Butane       C4H10     58       -126,150
                        Octane (vapor)    C8H18     114      -208,450
                                                                                    22
                          Dodecane        C12H26    170      -291,010
The enthalpies are calculated relative to a common base or reference called the
enthalpy of formation. The enthalpy of formation is the heat transfer required to form
the compound from its elements at 25oC (77 F) or 298 K (537 R), 1 atm. The
enthalpy at any other temperature is given as

                                      h  hfo  (hT  h o )
Here the term h o is the enthalpy of any component at 298 K. The enthalpies at the
temperatures T and 298 K can be found in Tables A-18 through A-25. If tables are
not available, the enthalpy difference due to the temperature difference can be
calculated from



Based on the classical sign convention, the net heat transfer to the reacting system is
                  Qnet  H P  H R
                            N e [h fo  (hT  h o )]e 
                           Products
                                                               N i [h fo  (hT  h o )]i
                                                            Reactants


 In an actual combustion process, is the value of Qnet positive or negative?


                                                                                            23
Example 15-7

Butane gas C4H10 is burned in theoretical air as shown below. Find the net heat
transfer per kmol of fuel.




Balanced combustion equation:
                              C4 H10  6.5 (O2  3.76 N 2 ) 
                                        4 CO2  5 H2 O  24.44 N 2
The steady-flow heat transfer is
         Qnet  H P  H R
                    N e [h fo  (hT  h o )]e 
                   Products
                                                       N i [h fo  (hT  h o )]i
                                                    Reactants

                                                                                    24
Reactants: TR = 298 K
         Comp       Ni            h fo                    hT              ho       Ni [hfo  (hT  h o )]i
                 kmol/kmol       kJ/kmol          kJ/kmol             kJ/kmol         kJ/kmol fuel
                   fuel
         C4H10   1           -126,150           --                   --           -126,150
         O2      6.5         0                  8,682                8,682        0
         N2      24.44       0                  8,669                8,669        0

                                  HR        N [h
                                          Reactants
                                                      i    f
                                                            o
                                                                 (hT  h o )]i

                                                                  kJ
                                          126,150
Products: TP = 1000 K                                          kmol C4 H10

         Comp       Ne            h fo                    hT              ho      Ne [hfo  (hT  h o )]e
                 kmol/kmol       kJ/kmol          kJ/kmol             kJ/kmol         kJ/kmol fuel
                   fuel
         CO2     4           -393,520           42,769               9,364        -1,440,460
         H2O     5           -241,820           35,882               9,904        -1,079,210
         N2      24.44       0                  30,129               8,669        +524,482


                                                                                                             25
 HP      N [h
        Products
                   e   f
                        o
                             (hT  h o )]e   Qnet  H P  H R
                                                                    kJ
                     kJ                            1,869,038
      1,995,188                                                kmol C4 H10
                  kmol C4 H10

Adiabatic Flame Temperature


The temperature of the products of
combustion when the process takes
place adiabatically is called the
adiabatic flame temperature.

Shown here is the view of the riser
tubes during the combustion process
inside a steam power plant boiler.



Photo courtesy of Progress Energy
Carolinas, Inc.                                                           26
Example 15-8

Liquid octane C8H18(liq) is burned with 400 percent theoretical air. Find the adiabatic
flame temperature when the reactants enter at 298 K, 0.1 MPa, and the products
leave at 0.1MPa.




The combustion equation is


            C8 H18  4(12.5) (O2  3.76 N 2 ) 
                      8 CO2  37.5 O2  9 H2 O  188 N 2
                                                                                 27
   The steady-flow heat transfer is

          Qnet  H P  H R
                     N e [h fo  (hT  h o )]e 
                    Products
                                                                 N i [h fo  (hT  h o )]i
                                                              Reactants

                 0 ( Adiabatic Combustion)

Thus, HP = HR for adiabatic combustion. We need to solve this equation for TP.


Since the temperature of the reactants is 298 K, (            hT  h o )i = 0,

                 HR           Nh
                          Reactants
                                      i
                                           o
                                          f i


                        1( 249,950)  4(12.5)(0)  4(12.5)(3.76)(0)
                                                   kJ
                        249,950
                                                kmol C4 H10                                   28
   Since the products are at the adiabatic flame temperature, TP > 298 K

               HP         
                         Products
                                    N e [h fo  (hTP  h o )]e

                       8(393,520  hTP  9364)CO2
                         9(241,820  hTP  9904) H 2O
                         37.5(0  hTP  8682)O2
                         188(0  hTP  8669) N2
                       (7, 443,845  8hTP , CO2  9hTP , H 2O
                                                                    kJ
                            37.5hTP , O2  188hTP , N2 )
                                                                 kmol C4 H10
Thus, setting HP = HR yields


          N h
        Pr oducts
                    e TP , e    8hTP , CO2  9hTP , H2O  37.5hTP , O2  188hTP , N 2

                                7,193,895                                               29
To estimate TP, assume all products behave like N2 and estimate the adiabatic flame
temperature from the nitrogen data, Table A-18.

                       242.5hTP , N 2  7,193,895
                                                      kJ
                              hTP , N 2    29,6655
                                                  .
                                                    kmol N 2
                                   Tp  985 K
Because CO2 and H2O are triatomic gases and have specific heats greater than
diatomic gases, the actual temperature will be somewhat less than 985 K. Try TP =
960 K and 970K.
                                                       Ne

                                          CO2    8
                                                h960 K                40,607
                                                                      h970 K      41,145
                                          H2O   9                     34,274      34,653
                                          O2    37.5                  29,991      30,345
                                          N2    188                   28,826      29,151
Interpolation gives: TP = 962 K.
                                                  N h
                                                 Produts
                                                           e TP , e
                                                                      7,177,572   7,259,362
                                                                                              30
Example 15-9

Liquid octane C8H18(liq) is burned with excess air. The adiabatic flame temperature is
960 K when the reactants enter at 298 K, 0.1 MPa, and the products leave at
0.1MPa. What percent excess air is supplied?




Let A be the excess air; then combustion equation is
    C8 H18  (1  A)(12.5) ( O2  3.76 N 2 ) 
         8 CO2  12.5 A O2  9 H2 O  (1  A)(12.5)(3.76) N 2



                                                                                 31
The steady-flow heat transfer is
                 Qnet  H P  H R
                           N [h
                          Products
                                     e   f
                                          o
                                               (hT  h o )]e       N [h
                                                                  Reactants
                                                                              i   f
                                                                                   o
                                                                                        (hT  h o )]i

                       0 ( Adiabatic combustion)
Here, since the temperatures are known, the values of hT are known. The product
                                                        P
gas mole numbers are unknown but are functions of the amount of excess air, A.
The energy balance can be solved for A.
                                                    A3
Thus, 300 percent excess, or 400 percent theoretical, air is supplied.

Example 15-10

Tabulate the adiabatic flame temperature as a function of excess air for the complete
combustion of C3H8 when the fuel enters the steady-flow reaction chamber at 298 K
and the air enters at 400 K.

The combustion equation is
          C3 H8  (1  A)(5) (O2  3.76 N 2 ) 
               3 CO2  5 A O2  4 H2 O  (1  A)(5)(3.76) N 2
                                                                                                         32
where A is the value of excess air in decimal form.

The steady-flow heat transfer is

          Qnet  H P  H R
                    N [h
                   Products
                              e   f
                                   o
                                        (hT  h o )]e       N [h
                                                           Reactants
                                                                       i     f
                                                                              o
                                                                                   (hT  h o )]i

                0 ( Adiabatic combustion)
                              Percent Excess Air       Adiabatic Flame Temp. K



                                         0                             2459.3

                                        20                             2191.9

                                        50                             1902.5

                                        100                            1587.1

                                        217                                1200

                                                                                                    33
Enthalpy of Reaction and Enthalpy of Combustion

When the products and reactants are at the same temperature, the enthalpy of
reaction hR, is the difference in their enthalpies. When the combustion is assumed
to be complete with theoretical air supplied the enthalpy of reaction is called the
enthalpy of combustion hC. The enthalpy of combustion can be calculated at any
value of the temperature, but it is usually determined at 25oC or 298 K.

                      hC  H P  H R when TP  TR  25o C  298 K
                               N e h fo e       N i h fo i
Heating Value                 Products          Reactants

The heating value, HV, of a fuel is the absolute value of the enthalpy of combustion
or just the negative of the enthalpy of combustion.

                                         HV  hC
The lower heating value, LHV, is the heating value when water appears as a gas in
the products.

                  LHV  hC  hC with H2 Ogas in products
                                                                                34
 The lower heating value is often used as the amount of energy per kmol of fuel
 supplied to the gas turbine engine.

 The higher heating value, HHV, is the heating value when water appears as a liquid
 in the products.

              HHV  hC  hC with H2 Oliquid in products

The higher heating value is often used as the amount of energy per kmol of fuel
supplied to the steam power cycle.

See Table A-27 for the heating values of fuels at 25oC. Note that the heating values
are listed with units of kJ/kg of fuel. We multiply the listed heating value by the molar
mass of the fuel to determine the heating value in units of kJ/kmol of fuel.

The higher and lower heating values are related by the amount of water formed
during the combustion process and the enthalpy of vaporization of water at the
temperature.

                          HHV  LHV  N H2Ohfg H2O
                                                                                      35
Example 15-11

The enthalpy of combustion of gaseous octane C8H18 at 25oC with liquid water in the
products is -5,500,842 kJ/kmol. Find the lower heating value of liquid octane.

             LHVC8 H18 gas  HHVC8 H18 gas  N H 2O h fg H 2O
                                 kJ          kmol H 2O               kJ
             5,500,842                  9             (44, 010)
                             kmol C8 H18    kmol C8 H18           kmol H 2O
                                 kJ
             5,104, 752
                             kmol C8 H18
                          LHVC8 H18 liq  LHVC8 H18 gas  h fg C8 H18
                                                    kJ
                           (5,104752  41,382)
                                                kmol C8 H18
                                            kJ
                           5, 063,370
                                       kmol C8 H18 liq
Can you explain why LHVliq< LHVgas?
                                                                               36
Closed System Analysis

Example 15-12

A mixture of 1 kmol C8H18 gas and 200 percent excess air at 25oC, 1 atm, is burned
completely in a closed system (a bomb) and is cooled to 1200 K. Find the heat
transfer from the system and the system final pressure.




Apply the first law closed system:




                                                                               37
 Assume that the reactants and products are ideal gases; then
                                    PV  NRu T




The balanced combustion equation for 200 percent excess (300 percent theoretical)
air is


               C8 H18  (3)(12.5) (O2  3.76 N 2 ) 
                    8 CO2  25 O2  9 H2 O  141 N 2

                                                                               38
                 Qnet  8( 393,520  53,848  9364  8.314(1200)) CO2
                         9( 241,820  44,380  9904  8.314(1200)) H2 O
                         25(0  38,447  8682  8.314(1200)) O2
                         141(0  36,777  8669  8.314(1200)) N 2
                         1( 208,450  h298 K  h o  8.314(298)) C8 H18
                         37.5(0  8682  8682  8.314( 298)) O2
                         141(0  8669  8669  8.314(298)) N 2
                                      kJ
                       112  10
                          .       6

                                  kmol C8 H18

To find the final pressure, we assume that the reactants and the products are ideal-
gas mixtures.
                                PV1  N 1 Ru T1
                                 1

                                PV2  N 2 Ru T2
                                 2

                                                                                   39
where state 1 is the state of the mixture of the reactants before the combustion
process and state 2 is the state of the mixture of the products after the combustion
process takes place. Note that the total moles of reactants are not equal to the total
moles of products.
                                   PV2 N 2 Ru T2
                                    2
                                       
                                   PV1
                                    1    N 1 Ru T1
but V2 = V1.




                                                                                   40
Second Law Analysis of Reacting Systems

Second law for the open system




The entropy balance relations developed in Chapter 7 are equally applica-ble to both
reacting and nonreacting systems provided that the entropies of individual
constituents are evaluated properly using a common basis.

Taking the positive direction of heat transfer to be to the system, the entropy balance
relation can be expressed for a steady-flow combustion chamber as

                   Qk
                  T  SReact  SProd  S gen  SCV             ( kJ / k )
                    k

                                                                                  41
For an adiabatic, steady-flow process, the entropy balance relation reduces to
                                S gen , adiabatic  SProd  SReact  0

The third law of thermodynamics states that the entropy of a pure crys-talline
substance at absolute zero temperature is zero. The third law provides a common
base for the entropy of all substances, and the entropy values relative to this base
are called the absolute entropy.

The ideal-gas tables list the absolute entropy values over a wide range of
temperatures but at a fixed pressure of Po = 1 atm. Absolute entropy values at other
pressures P for any temperature T are determined from
                                                            P
                      s (T , P)  s o (T , Po )  Ru ln             [ kJ / ( kmol  K )]
                                                            Po
For component i of an ideal-gas mixture, the absolute entropy can be written as
                                                            yi Pm
                     si (T , Pi )  sio (T , Po )  Ru ln              [ kJ / ( kmol  K )]
                                                             Po
where Pi is the partial pressure, yi is the mole fraction of the component, and Pm is
the total pressure of the mixture in atmospheres.


                                                                                              42
Example 15-13

A mixture of ethane gas C2H6 and oxygen enters a combustion chamber at 1 atm,
25oC. The products leave at 1 atm, 900 K. Assuming complete combustion, does the
process violate the second law?




The balanced combustion equation is
                            C2 H6  35 O2  2 CO2  3 H2 O
                                     .


                                                                           43
The mole fractions for the reactants and the products are
                                                    1       1
                                       yC2 H6           
                                                 1  35 4.5
                                                      .
                                                    .
                                                   35       .
                                                           35
                                         yO2            
                                                 1  35 4.5
                                                      .
                                                   2      2
                                        yCO2           
                                                 23 5
                                                   3      3
                                        y H2 O         
                                                 23 5
Now calculate the individual component entropies.

For the reactant gases:




                                                                44
SReact      N s
           Reactants
                       i i


       1(242.0)  35(207.1)
                    .
                   kJ
       966.9
              kmolC2 H6  K


                               45
For the product gases:




                         46
                                   SProd     N s
                                             Products
                                                        e e


                                          2(2712)  3(232.6)
                                                .
                                                      kJ
                                          1240.2
                                                  kmolC2 H6  K
The entropy change for the combustion process is
                                                                        kJ
                           S Prod  S React  (1240.2  966.9)
                                                                    kmolC2 H6  K
                                                     kJ
                                          273.3
                                                 kmolC2 H6  K
Now to find the entropy change due to heat transfer with the surroundings. The
steady-flow conservation of energy for the control volume is
     Qnet sys  H P  H R
                 N e [h fo  (hT  h o )]e 
                Products
                                                           N i [h fo  (hT  h o )]i
                                                        Reactants



                                                                                        47
Qnet sys  2( 393,520  37,405  9364) CO2
         3( 241,820  31,828  9904) H2O
         1( 214,820  h298 K  h o ) C2 H6
         35(0  8682  8682) O2
           .
                      kJ
       1306  10
          .          6

                   kmol C2 H6
       Qk Qnet sys
      T  T
        k    o

                              kJ
              1306  106
                .
                          kmol C2 H6
            
                   (25  273) K
                           kJ
             4,383
                     kmol C2 H6  K
                                               48
The entropy generated by this combustion process is




Since Sgen, or Snet , is ≥ 0, the second law is not violated.




                                                                 49

				
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