6.

Bab 15 : Reaksi Kimia

15-1 Bahan Bakar & Pembakaran
15-2 Proses Pembakaran Teoritik & Aktual
15-3 Entalpi Pembentukan & Entalpi Pembakaran
Nilai Kalor (Heating Value)
a. HHV (High Heating Value)
b. LHV (Low Heating Value)
Suhu Nyala Adiabatik

Bahan Bakar & Pembakaran

FIGURE 151
Kebanyakan bahan bakar hidrokarbon cair dihasilkan dari
destilasi minyak bumi

Pembakaran (Combustion)
Pembakaran adalah reaksi kimia dimana bahan bakar
dioksidasi & sebagian besar energi dihasilkan.
FIGURE 153
O2 21% mol
N2 79% mol
Sehingga :
1 kmol O2 di udara terdapat
3,76 kmol N2

FIGURE 154
Pada proses pembakaran tunak, komponen-komponen yang masuk ruang
bakar disebut sebagai REAKTAN & komponen yg keluar disebut
sebagai PRODUK.

Rasio udara bahan bakar (airfuel ratio, AF)

biasanya dinyatakan berdasarkan basis massa & didefinisikan
sebagai :

FIGURE 156
Rasio udara - bahan bakar (airfuel ratio, AF) menunjukkan jumlah
massa udara yg digunakan per satuan massa bahan bakar selama
proses pembakaran.

EXAMPLE 151
Balancing the Combustion Equation
1 kmol oktana (C8H18) dibakar dengan udara yg mengandung 20
kmol O2. Asumsikan produk hanya mengandung CO2, H2O, O2,
dan N2, tentukan :
a. Jumlah mol setiap gas dalam produk dan
b. Rasio AF pada proses pembakaran ini.

Solution : Jumlah bahan bakar & oksigen di udara diberikan.

Jumlah produk dan rasio AF ditanyakan.
Asumsi : Produk pembakaran hanya mengandung CO2, H2O, O2, dan N2 .
Properties : Massa molar udara Mair = 28.97 kg/kmol = 29.0 kg/kmol
(Table A1).
Analysis :
Massa Molar dari Udara dapat ditentukan dari :

Persamaan kimia untuk proses pembakaran ini dapat ditulis sbb :

Jumlah massa atau jumlah mol setiap komponen dari reaktan &
produk harus sama, sehingga :

Dengan mensubstitusikan koefisien di atas, persamaan pembakaran

menjadi :

Rasio Udara Bahan Bakar (AF) :

Kesimpulan : 24,2 kg udara digunakan untuk membakar 1 kg

bahan bakar selama proses pembakaran ini.

Pembakaran Teoritik & Aktual

Proses pembakaran dikatakan lengkap / sempurna
jika semua komponen yg dapat terbakar dari bahan
bakar terbakar sempurna (tak ada sisa bahan bakar pada produk)
Pembakaran
Teoritik

Pembakaran
Aktual

Proses pembakaran ideal dimana bahan bakar terbakar secara

sempurna dengan udara teoritik disebut pembakaran teoritik /
stoikiometri.
Sebagai contoh, pembakaran teoritik metana sbb :

FIGURE 159
Proses pembakaran lengkap tanpa
oksigen berlebih pada produk
pembakaran disebut :
pembakaran teoritik.

EXAMPLE 152
Pembakaran Dengan Udara Berlebih
Etana (C2H6) dibakar dengan 20% udara berlebih selama proses
pembakaran. Asumsikan pembakaran sempurna / lengkap yang
berlangsung pada tekanan 100 kPa. Tentukan :
a. Rasio AF

Persamaan Reaksi Pembakaran :

Koefisien ath
ditentukan dari kesetimbangan O2 antara reaktan & produk sbb :

Sehingga Persamaan Reaksi Pembakaran menjadi :

(a) Rasio AF dapat dihitung sbb :

Energi Sensibel, Energi Laten,

Energi Kimia & Energi Nuklir

FIGURE 1514
Bentuk energi mikroskopik dari
suatu zat terdiri dari :
1.
2.
3.
4.

Energi Sensibel
Energi Laten
Energi Kimia
Energi Nuklir

Entalpi Reaksi (Enthalpy of Reaction, hR)

FIGURE 1515
Saat ikatan kimia yg ada rusak
& terbentuk ikatan baru yg lain
selama proses pembakaran
sejumlah besar energi
sensibel diserap atau
dilepaskan.

Sifat ini disebut Entalpi Reaksi (Enthalpy of Reaction, hR) yang

didefinisikan sebagai perbedaan antara entalpi Produk pada suatu
kondisi tertentu dengan entalpi Reaktan untuk suatu rekasi sempurna.

Entalpi Pembakaran
(Enthalpy of Combustion, hC)
Untuk Proses Pembakaran Entalpi Reaksi biasanya dikenal sebagai
Entalpi Pembakaran (Enthalpy of Combustion, hC) yang menunjukkan
sejumlah kalor yang dilepaskan selama proses pembakaran tunak
saat 1 kmol (atau 1 kg) bahan bakar secara sempurna terbakar pada
suhu & tekanan tertentu.

Entalpi Reaksi (hR) atau Entalpi Pembakaran (hC) dapat dituliskan sbb :

Entalpi Reaksi = Entalpi Pembakaran

(hR = hC)

FIGURE 1517
Entalpi Pembakaran menunjukkan
sejumlah energi yang dilepaskan saat
bahan bakar terbakar selama proses
pembakaran tunak pada kondisi tertentu.

Entalpi Pembentukan
(Enthalpy of Formation, hC)
Entalpi Pembakaran disebut juga sebagai Entalpi Pembentukan
(Enthalpy of Formation, h f) saat dipandang sebagai entalpi dari
suatu zat pada kondisi tertentu karena komposisi kimia
pembentuknya.

FIGURE 1518
Entalpi Pembentukan dari suatu senyawa
atau molekul menunjukkan energi
yang diserap atau dilepaskan saat
komponen terbentuk dari elemenelemennya selama proses pembakaran
tunak pada kondisi tertentu.

( Tabel A-26 )

Nilai Kalor
(Heating Value, HHV & LHV)
Nilai Kalor (Heating value) suatu bahan bakar didefinisikan sebagai
jumlah kalor yang dilepaskan saat bahan bakar terbakar sempurna.
Dengan kata lain, Nilai Kalor bahan bakar sama dengan Harga
Mutlak Entalpi Pembakaran dari bahan bakar, & dapat dituliskan sbb :

Nilai Kalor tergantung pada fasa H2O pada Produk.

Nilai Kalor disebut HHV (Higher Heating Value) jika H2O pada
produk berada pada fasa cair.
Nilai Kalor disebut LHV (Lower Heating Value) jika H2O pada
produk berada pada fasa uap.

Hubungan antara HHV dan LHV sbb :

FIGURE 1519
HHV suatu bahan bakar
sama dengan jumlah dari LHV
dan Kalor Laten Penguapan
H2O pada produk.

EXAMPLE 155
Evaluation of the Enthalpy of Combustion
Tentukan Entalpi Pembakaran dari Oktana cair (C8H18) pada kondisi
25C dan 1 atm, menggunakan data Entalpi Pembentukan (Tabel A-26).
Asumsikan H2O pada produk berfasa cair.

Tabel A-26 Entalpi Pembentukan pada 25C dan 1 atm sbb :

- CO2 (g)
= - 393,520 kJ/kmol
- H2O (l)
= - 285,830 kJ/kmol
- C8H18 (l)
= - 249,950 kJ/kmol
Persamaan stoikiometri pembakaran C 8H18 sbb :

Reaktan & Produk pada kondisi referensi standar (25C dan 1 atm).
N2 dan O2 adalah elemen yang stabil
sehingga entalpi pembentukannya sama dengan NOL.

Sehingga Entalpi Pembakaran C8H18 menjadi :

Sehingga :

TEMPERATUR NYALA ADIABATIK

(ADIABATIC FLAME TEMPERATURE)

FIGURE 1525
Suhu dari ruang bakar akan
mencapai nilai maksimum, jika
pembakaran sempurna & tidak ada
energi hilang ke lingkungan.

Suhu nyala adiabatik suatu proses pembakaran aliran tunak dapat ditentukan dari :

FIGURE 1526
The maximum temperature
encountered in a combustion chamber
is lower than the theoretical adiabatic
flame temperature.

EXAMPLE 158
Adiabatic Flame Temperature in Steady Combustion
Liquid octane (C8H18) enters the combustion chamber of a gas turbine steadily at
1 atm and 25C, and it is burned with air that enters the combustion chamber at
the same state, as shown in Fig. 1527. Determine the adiabatic flame temperature
for (a) complete combustion with 100 percent theoretical air, (b) complete
combustion with 400 percent theoretical air, and (c) incomplete combustion (some
CO in the products) with 90 percent theoretical air.

Solution Liquid octane is burned steadily. The adiabatic flame temperature is to be

determined for different cases.
Assumptions 1 This is a steady-flow combustion process. 2 The combustion
chamber is adiabatic. 3 There are no work interactions. 4 Air and the combustion
gases are ideal gases. 5 Changes in kinetic and potential energies
are negligible.
Analysis
(a) The balanced equation for the combustion process with the theoretical amount of
air is

The adiabatic flame temperature relation Hprod Hreact in this case reduces to

since all the reactants are at the standard reference state and h f 0 for O2 and N2.
The h f and h values of various components at 298 K are

Substituting, we have

which yields

It appears that we have one equation with three unknowns. Actually we have
only one unknownthe temperature of the products Tprodsince h h(T )
for ideal gases. Therefore, we have to use an equation solver such as EES or
a trial-and-error approach to determine the temperature of the products.

A first guess is obtained by dividing the right-hand side of the equation by the total
number of moles, which yields 5,646,081/(8 + 9 + 47) 88,220 kJ/kmol. This
enthalpy value corresponds to about 2650 K for N2, 2100 K for H2O, and 1800 K
for CO2. Noting that the majority of the moles are N2, we see that Tprod should be
close to 2650 K, but somewhat under it. Therefore, a good first guess is 2400 K. At
this temperature,

This value is higher than 5,646,081 kJ. Therefore, the actual temperature is
slightly under 2400 K. Next we choose 2350 K. It yields

which is lower than 5,646,081 kJ. Therefore, the actual temperature of the products
is between 2350 and 2400 K. By interpolation, it is found to be

(b) The balanced equation for the complete combustion process with 400
percent theoretical air is

By following the procedure used in (a), the adiabatic flame temperature in this case
is determined to be

Notice that the temperature of the products decreases significantly as a result of

using excess air.

(c) The balanced equation for the incomplete combustion process with 90 percent
theoretical air is

Following the procedure used in (a), we find the adiabatic flame temperature in
this case to be

Discussion Notice that the adiabatic flame temperature decreases as a

result of incomplete combustion or using excess air. Also, the maximum
adiabatic flame temperature is achieved when complete combustion occurs
with the theoretical amount of air.

FIRST-LAW ANALYSIS
OF REACTING SYSTEMS

Steady-Flow Systems
the enthalpy of a component on a unit mole basis as (Fig. 1521)

FIGURE 1521
The enthalpy of a chemical component
at a specified state is the sum of the
enthalpy of the component at 25C, 1
atm (hf), and the sensible enthalpy of
the component relative to 25C, 1 atm.

The steady-flow energy balance relation can be expressed for a chemically reacting
steady-flow system more explicitly as

Rate of net energy transfer in by heat,

work, and mass

Rate of net energy transfer out by heat,

work, and mass

In combustion analysis, it is more convenient to work with quantities expressed per

mole of fuel. Such a relation is obtained by dividing each term of the equation above
by the molal flow rate of the fuel, yielding

Energy transfer in per mole of fuel by

heat, work, and mass

Energy transfer out per mole of fuel by

heat, work, and mass

Taking heat transfer to the system and work done by the system to be positive
quantities, the energy balance relation just discussed can be expressed more compactly
as

or as

where

If the enthalpy of combustion h C for a particular reaction is available, the

steady-flow energy equation per mole of fuel can be expressed as

A combustion chamber normally involves heat output but no heat input. Then the
energy balance for a typical steady-flow combustion process becomes

Energy in by mass per

mole of fuel

Energy out by mass per

mole of fuel

Closed Systems
The general closed-system energy balance relation can be expressed for a stationary
chemically reacting closed system as

To avoid using another property the internal energy of formation ufwe utilize
the definition of enthalpy (u h Pv or u f u u h Pv) and express the
above equation as (Fig. 1522)

FIGURE 1522
An expression for the internal energy
of a chemical component in terms of
the enthalpy.

EXAMPLE 156
First-Law Analysis of Steady-Flow Combustion
Liquid propane (C3H8) enters a combustion chamber at 25C at a rate of
0.05 kg/min where it is mixed and burned with 50 percent excess air that
enters the combustion chamber at 7C, as shown in Fig. 1523. An analysis
of the combustion gases reveals that all the hydrogen in the fuel burns
to H2O but only 90 percent of the carbon burns to CO2, with the remaining
10 percent forming CO. If the exit temperature of the combustion gases is 1500
K, determine (a) the mass flow rate of air and (b) the rate of heat
transfer from the combustion chamber.

Solution Liquid propane is burned steadily with excess air. The mass flow
rate of air and the rate of heat transfer are to be determined.
Assumptions 1 Steady operating conditions exist. 2 Air and the combustion
gases are ideal gases. 3 Kinetic and potential energies are negligible.
Analysis We note that all the hydrogen in the fuel burns to H2O but 10
percent of the carbon burns incompletely and forms CO. Also, the fuel is
burned with excess air and thus there is some free O2 in the product gases.
The theoretical amount of air is determined from the stoichiometric reaction to be

O2 balance:

Then the balanced equation for the actual combustion process with 50 percent
excess air and some CO in the products becomes

(a) The airfuel ratio for this combustion process is

Thus,

(b) The heat transfer for this steady-flow combustion process is determined from
the steady-flow energy balance Eout Ein applied on the combustion chamber per
unit mole of the fuel,

or

Assuming the air and the combustion products to be ideal gases, we have h
h(T ), and we form the following minitable using data from the property tables:

The hf of liquid propane is obtained by subtracting the hfg of propane at 25C

from the hf of gas propane. Substituting gives

Thus 363,880 kJ of heat is transferred from the combustion chamber for each kmol
(44 kg) of propane. This corresponds to 363,880/44 8270 kJ of heat loss per
kilogram of propane. Then the rate of heat transfer for a mass flow rate of 0.05
kg/min for the propane becomes

EXAMPLE 157
First-Law Analysis of Combustion in a Bomb
The constant-volume tank shown in Fig. 1524 contains 1 lbmol of methane (CH4)
gas and 3 lbmol of O2 at 77F and 1 atm. The contents of the tank are ignited, and
the methane gas burns completely. If the final temperature is 1800 R, determine (a)
the final pressure in the tank and (b) the heat transfer during this process.

Solution Methane is burned in a rigid tank. The final pressure in the tank and the
heat transfer are to be determined.
Assumptions 1 The fuel is burned completely and thus all the carbon in the fuel
burns to CO2 and all the hydrogen to H2O. 2 The fuel, the air, and the combustion
gases are ideal gases. 3 Kinetic and potential energies are negligible. 4 There are
no work interactions involved.
Analysis
The balanced combustion equation is

(a) At 1800 R, water exists in the gas phase. Using the ideal-gas relation for both the
reactants and the products, the final pressure in the tank is determined to be

Substituting, we get

(b) Noting that the process involves no work interactions, the heat transfer during
this constant-volume combustion process can be determined from the energy
balance Ein Eout Esystem applied to the tank,

Since both the reactants and the products are assumed to be ideal gases, all the
internal energy and enthalpies depend on temperature only, and the Pv terms in
this equation can be replaced by RuT. It yields

since the reactants are at the standard reference temperature of 537 R.

From h f and ideal-gas tables in the Appendix,

Substituting, we have

Discussion On a mass basis, the heat transfer from the tank would be 308,730/16
19,300 Btu/lbm of methane.