KIMIA BAHAN BAKAR

Combustion or burning is a complex sequence of

exothermic chemical reactions between a fuel and an
oxidant accompanied by the production of heat or both
heat and light in the form of either a glow or flames.
Chemical reaction equation of combustion:


Example: Fuel: Hydrocarbons (C and H)
Oxidant: air (oxygen and nitrogen)
Combustion product gases: CO
2
or CO and H
2
O
Fuel
Combustion
product
gases
Heat
Oxidant
+
+
Combustion of wood (cellulose) that
produce flame, heat and ash/carbon
In a complete combustion reaction, a compound reacts with
an oxidizing element, such as oxygen or fluorine, and the
products are compounds of each element in the fuel with the
oxidizing element. For example:
CH
4
+ 2O
2
CO
2
+ 2H
2
O
CH
2
S + 6F
2
CF
4
+ 2HF + SF
6

A simpler example can be seen in the combustion of
hydrogen and oxygen, which is a commonly used reaction
in rocket engines:
2H
2
+ O
2
2H
2
O(g) + heat
The result is water vapor
In the large majority of the real world uses of combustion,
the oxygen (O
2
) oxidant is obtained from the ambient air
and the resultant flue gas from the combustion will contain
nitrogen:
CH
4
+ 2O
2
+ 7.52N
2
CO
2
+ 2H
2
O + 7.52N
2
+ heat

When air is the source of the oxygen, nitrogen is by far the
largest part of the resultant flue gas.
In reality, combustion processes are never perfect or
complete. In flue gases from combustion of carbon (as in
coal combustion) or carbon compounds (as in combustion of
hydrocarbons, wood etc.) both unburned carbon (as soot)
and carbon compounds (CO and others) will be present.
Also, when air is the oxidant, some nitrogen will be oxidized
to various nitrogen oxides (NOx).
In reality, combustion processes are never perfect or
complete. In flue gases from combustion of carbon (as in
coal combustion) or carbon compounds (as in combustion of
hydrocarbons, wood etc.) both unburned carbon (as soot)
and carbon compounds (CO and others) will be present.
Also, when air is the oxidant, some nitrogen will be oxidized
to various nitrogen oxides (NOx).
Types of
combustion
Rapid combustion
Slow combustion
Complete combustion
Incomplete combustion
Turbulent combustion
Complete combustion:
In complete combustion, the reactant will burn in oxygen,
producing a limited number of products. When a hydrocarbon
burns in oxygen, the reaction will only yield carbon dioxide
and water. When a hydrocarbon or any fuel burns in air, the
combustion products will also include nitrogen. When
elements such as carbon, nitrogen, sulfur, and iron are
burned, they will yield the most common oxides. Carbon will
yield carbon dioxide. Nitrogen will yield nitrogen dioxide.
Sulfur will yield sulfur dioxide. Iron will yield iron(III) oxide. It
should be noted that complete combustion is almost
impossible to achieve. In reality, as actual combustion
reactions come to equilibrium, a wide variety of major and
minor species will be present. For example, the combustion of
methane in air will yield, in addition to the major products of
carbon dioxide and water, the minor product carbon monoxide
and nitrogen oxides, which are products of a side reaction
(oxidation of nitrogen)
Incomplete combustion:
Incomplete combustion occurs when there isn't enough
oxygen to allow the fuel (usually a hydrocarbon) to react
completely with the oxygen to produce carbon dioxide and
water, also when the combustion is quenched by a heat sink
such as a solid surface or flame trap. When a hydrocarbon
burns in air, the reaction will yield carbon dioxide, water,
carbon monoxide, pure carbon (soot or ash) and various
other compounds such as nitrogen oxides.
Chemical equation of Combustion
The complete chemical equation for stoichiometric burning
of hydrocarbon in oxygen is as follows:
(g)
O
2
H
2
y
(g) 2
CO x
(g) 2
O
4
y 4x
(g)
y
H
x
C +
+
+
|
.
|

\
|
Example for propane combustion:
Propane: C
3
H
8
(x=3; y=8)

; or
( )
(g)
O
2
H
2
8
(g) 2
CO 3
(g) 2
O
4
12
(g) 8
H
3
C +
+
+
8
(g)
O
2
H 4
(g) 2
CO 3
(g) 2
O
(g) 8
H
3
C + + 5
The complete chemical equation for stoichiometric burning
of hydrocarbon in air as oxidant agent (oxidizer) by
simplification is as follows:



where: a = x + y/4

In that combustion chemical equation, air assumed consist
of 21%v of oxigen (O
2
) and 79%v of nitrogen (N
2
), i.e.,
that for each mole of O
2
in air, there are 3.76 mole of N
2
.
2
N 3.76a O
2
H 2 y
2
CO x
2
3.76N
2
O a
y
H
x
C + + + +
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\
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.
|

\
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Example for propane combustion:
Propane: C
3
H
8
(x=3; y=8)
2
N 18.8 O
2
H 4
2
CO 3
2
3.76N
2
O 5
8
H
3
C + + + +
|
|
.
|

\
|
Term and its formula in complete combustion by
oxidizer of air:
Stoichiometric air-fuel ratio, (A/F)
stoic

fuel
MW
air
MW
1
4.76a
stoic
fuel
m
air
m
stoic
F A = =
|
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.
|

\
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|
.
|

\
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Equivalence ratio, u
( )
( )
( )
( )
stoic
A F
A F
F A
stoic
F A
= = u
Equivalence ratio, u, is commonly used to to indicate
quantitively wheter a fuel-oxidizer mixture is rich, lean, or
stoichiometric. u > 1 for fuel-rich mixtures, u < 1 for
fuel-lean mixtures, and u = 1 for stoic mixtures

Percent stoichiometric air
% 100
1

u
u
=
|
.
|

\
|
air excess %

Percent excess air
u
=
% 100
air tric stoichiome %
Example:
A small, low-emission, stationary gas-turbine engine
operates at full load (3950 kW) at an equivalence ratio of
0.286 with an air flowrate of 15.9 kg s
-1
. The equivalent
composition of the fuel (natural gas) is C
1.16
H
4.32
.
Determine the fuel mass flowrate and the operating air-
fuel ratio for engine!
Data:
Ar C=12.011; Ar H=1.008; Ar O=15.999; Ar N=14.007
Thermochemistry of Combustion
Panas
Panas sebagai bentuk energi yang mengiringi reaksi pembakaran
merupakan bentuk energi yang bersifat tidak permanen eksistensinya
dalam suatu benda. Oleh karena itu, panas dikatakan sebagai energi
dalam transit dari satu benda ke benda yang lain, atau antara sistem
dengan lingkungannya. Dalam pengertian termodinamika , panas
tidak pernah dianggap tersimpan di dalam suatu benda.
Kapasitas panas
Kapasitas panas dari suatu bahan didefinisikan sebagai jumlah panas
yang diperlukan untuk menaikkan temperatur bahan tersebut sebesar
satu derajat. Tiap-tiap bahan karena memiliki sifat-sifat yang spesifik,
maka kapasitas panas setiap bahan juga akan berbeda-beda
Rumusan dasar dari kapasitas panas adalah sebagai berikut:
dT
Q
C
o
=
Karena pemanasan dapat dilakukan dengan dua cara
kemungkinan, maka dikenal dua jenis kapasitas panas, yaitu:
1. Kapasitas panas pada volum konstan, atau
V
V
dT
Q
C
|
.
|

\
|
=
o
2. Kapasitas panas pada tekanan konstan, atau
dT
dU
C
V
=
P
P
dT
Q
C
|
.
|

\
|
=
o
dT
dH
C
P
=
Kapasitas panas bahan dalam bentuk lain dapat dinyatakan
untuk tiap massa atau tiap mole bahan, dikenal: kapasitas
panas jenis (specific heat capacity), c, dan kapasitas panas
jenis molar (molar specific heat capacity),
c
c
Data-data tentang kapasitas panas dari gas, cair dan padatan
dapat ditemui di banyak literatur, umumnya dinyatakan sebagai
fungsi temperatur. Untuk gas, kapasitas panas dirujukkan untuk
gas ideal.
|
|
.
|

\
|
+ + A = +
2
2
1
v
C C
g
z
g
g
U W Q
|
|
.
|

\
|
+ + = +
2
2
1
v o o
C C
g
z
g
g
U d W Q
Hukum I Termodinamika untuk sistem tertutup:
Hukum I Termodinamika untuk sistem terbuka:
|
|
.
|

\
|
+ + A = +
2
2
1
v
C C
g
z
g
g
H W Q
|
|
.
|

\
|
+ + = +
2
2
1
v o o
C C
g
z
g
g
H d W Q
Untuk kasus reaksi pembakaran, Ep dan Ek dapat diabaikan
Termokimia Panas Reaksi Kimia (contoh: reaksi pembakaran)
Panas reaksi secara umum didefinisikan sebagai panas yang
menyertai keberlangsungan suatu sistem reaksi kimia.
Berdasarkan Hukum I Termodinamika untuk proses alir dengan
mengabaikan perubahan energi kinetik dan energi potensial dan
tidak ada kerja mekanik eksternal, dan untuk proses non-alir yang
dioperasikan pada tekanan konstan, diperoleh bahwa Q = AH.
Analisa ini yang menjadi dasar umum bahwa kuantitas panas yang
meyertai reaksi kimia (panas reaksi) sama dengan perubahan
entalpi dari reaksi tersebut.
Panas reaksi standar (AH
R
o
) adalah panas reaksi kimia yang
nilainya merupakan selisih antara total panas pembentukan dari
komponen produk reaksi terhadap total panas pembentukan dari
komponen reaktan pada tekanan 1 atm dan temperatur 25
o
C.
Oleh karena itu panas reaksi standar dirumuskan sebagai berikut:
( ) ( )
tan
, ,
reak
o
i f i
produk
o
j f j
o
R
H n H n H

A A = A
AH
f
o
adalah panas pembentukan standar dan ni
,j
adalah jumlah mol
stokiometri dari tiap komponen yang terlibat dalam reaksi
Pada reaksi-reaksi aktual/nyata, sering reaksi kimia tidak hanya
dilangsungkan pada temperatur 25
o
C. Untuk menghitung panas
reaksi (AH
R
) pada kasus reaksi seperti ini, dikembalikan pada konsep
bahwa perubahan entalpi merupakan fungsi keadaan, sehingga
antara temperatur aktual reaktan dan temperatur aktual produk dapat
dihubungkan dengan temperatur standar.
Reaktan, 25
o
C Produk, 25
o
C
Produk, T
2
Reaktan, T
1

(1)
(2) (3)
(4)
AH
1, 2

AH
R
o

AH
3, 4

AH
R

Rumusan perhitungan: AH
R
= AH
1, 2
+ AH
R
o
+ AH
3, 4

( )dT reaktan C H
T
P
}
= A
298
2 , 1
1
( )dT produk C H
T
P
}
= A
2
298
4 , 3
Contoh soal:
1. How much heat is required when 10,000 kg of CaCO
3
is
heated at atmospheric pressure from 50oC to 880
o
C?
C
P
of CaCO
3
:

with R = 8.314 kJ kmol
-1
K
-1
.
(Ar Ca=40.08; Ar C=12.01; Ar O=16)


2. What is the standard heat combustion of n-pentane gas at
25
o
C if the combustion product are H
2
O
(l)
and CO
2(g)
?
AH
f
o
n-pentane
(g)
: -146,760 J mol
-1

AH
f
o
H
2
O
(l)
: -285,830 J mol
-1

AH
f
o
CO
2
O
(g)
: -393,509 J mol
-1

3. What is the maximum temperature that can be reached by
the adiabatic complete combustion of methane with
20%mole exess air? Both the methane and the air enter
the burner at 25
o
C.
2
T
5
10 3.12 T
3
2.637x10 15.572
R
P
C

+ =
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Soal Kuis
Sejumlah gas C
3
H
8
telah dibakar habis
dengan udara (pada STP). Jumlah gas
CO
2
dan H
2
O yang terbentuk 7,5 liter.
Bila kadar O
2
dalam udara 18,5%
(%volum), hitunglah volum gas C
3
H
8

yang telah dibakar dan volum udara
yang diperlukan!