Calculations

Combustion
• Fuel is a combustible substance containing carbon as the main
constituent which on proper burning gives a large amount of heat
that can be used economically for domestic and industrial purpose.
• The various fuels used economically are wood, coal, kerosene, petrol,
diesel, gasoline, coal gas, producer gas, water gas, natural gas etc.
•A fuel is a combustible substance containing carbon as the main constituent
which on proper burning gives large amount of heat that can be used
economically for domestic and industrial purposes. During the process of
combustion of a fuel, the atoms of carbon, hydrogen, etc. combine with oxygen
with simultaneous liberation of heat (Exothermic reaction). The calorific value
of a fuel depends mainly on the two elements.

C + O2 CO2 + 94 kcals.
2H2 + O2 2H2O + 68.5 kcals.

•So, carbon compounds have been used for many centuries as the source of heat
and energy.
•The main source of fuel is coal and petroleum. These are stored fuels available
in earth's crust and are generally called fossil fuels because they were formed
from the fossilised remains of plants and animals.
• It is given to us that formation of water from hydrogen and oxygen gas is
exothermic, which means the energy of the reactant is higher than that of
the products.
• To initiate combustion, energy is required to force dioxygen into a spin-
paired state, or Singlet oxygen. This intermediate is extremely reactive. The
energy is supplied as heat, and the reaction then produces additional heat,
which allows it to continue.
• Combustion in oxygen is a chain reaction in which many distinct
radical intermediates participate. The high energy required for initiation is
explained by the unusual structure of the dioxygen molecule. The lowest-
energy configuration of the dioxygen molecule is a stable, relatively
unreactive diradical in a triplet spin state.
 Classification of Fuels
1. Primary fuels which occur in nature as such, e.g. coal, petroleum and natural gas.
2. Secondary fuels which are derived from the primary fuels, e.g. coke, gasoline, coal gas, etc.
Both primary and secondary fuels may be further classified based upon their physical state as
(i) solid fuels (ii) liquid fuels and (iii) gaseous fuels.
CALORIFIC VALUE
• Calorific value of a fuel is "the total quantity of heat liberated, when a unit mass (or
volume) of the fuel is burnt completely.“
Units of heat :
(1) 'Calorie' is the amount of heat required to raise the temperature of one gram of water through
one degree Centigrade (15-16°C).
(2) "Kilocalorie" is equal to 1,000 calories. It may be defined as 'the quantity of heat required to
raise the temperature of one kilogram of water through one degree Centigrade. Thus: 1 kcal =
1,000 cal
(3) "British Thermal unit" (B.T.U.) is defined as "the quantity of heat required to raise the
temperature of one pound of water through one degree Fahrenheit (60-61°F). This is the English
system unit.
1 B.T.U. = 252 cal = 0.252 kcal 1 kcal = 3.968 B.T.U.
(4) The centigrade heat unit (CHU) is the amount of heat required to raise the temperature of one
pound of water by one Celsius degree. It is equal to 1.8 BTU or 1,899 joules.
• Calorific values are expressed in Kcal/Kg. of fuel at N.T.P.
• in S.I. system J/Kg or KJ/Kg (or) MJ/Kg.
 HCV and LCV (HHV or LHV) GCV or NCV
Higher or gross calorific value:
 Usually, all fuels contain some hydrogen and when the calorific value of
hydrogen-containing fuel is determined experimentally, the hydrogen is
converted into steam. If the products of combustion are condensed to the
room temperature (15°C or 60°F), the latent heat of condensation of steam
also gets included in the measured heat, which is then called "higher or
gross calorific value". So, gross or higher calorific value (HCV) is "the
total amount of heat produced, when unit mass/volume of the fuel has been
burnt completely and the products of combustion have been cooled to room
temperature"(i.e., 15°C or 60°F ).
Lower or net calorific value (LCV)
• In actual use of any fuel, the water vapour and moisture, etc., are not
condensed and escape as such along-with hot combustion gases. Hence,
a lesser amount of heat is available. So, net or lower calorific value (LCV)
is "the net heat produced, when unit mass /volume of the fuel is burnt
completely and the products are permitted to escape".
• Net calorific value= Gross calorific value - Latent heat of condensation
of water vapour produced
= GCV - Mass of hydrogen per unit weight of the fuel burnt x 9 x Latent
heat of condensation of water vapour
Dulong's formula for calorific value from the chemical composition of fuel is :

HCV = 1/100 [8,080 C + 34,500 (H – O/8)+ 2,240 S] kcal/kg

or
H.C.V.= (33800 C +144000 (H2 - O2/8) + 9270 S) KJ/Kg. Where C, H2 O2 & S repents the mass
of carbon, hydrogen, oxygen and sulfur in kJ/Kg

where C, H, O, and S are the percentages of carbon, hydrogen, oxygen and sulphur in the fuel respectively.
In this formula, oxygen is assumed to be present in combination with hydrogen as water, and
LCV = [ HCV - 9H/100 x 587] kcal/kg = [HCV - 0.09 H x 587] kcal/kg
This is based on the fact that 1 part of H by mass gives 9 parts of H2O, and latent heat of steam is 587 kcal/kgIf

.
 H.C.V. is known then L.C.V. is obtained by
L.C.V. = H.C.V. – Heat of steam formed during combustion
let mS= Mass of steam formed in KJ/Kg. of fuel = 9 H2
Since amount of heat per Kg. of steam is the latent heat of vaporization of water
corresponding to a standard temperature of 25 oC is 2466 KJ/Kg.
L.C.V. = H.C.V. – ms x 2466
L.C.V. = H.C.V. – 9 H2 x 2466 KJ/Kg.
 Solid fuel
COAL
•Coal is regarded as a fossil fuel produced from large accumulations of vegetable
debris due to partial decay and alteration by the action of heat and pressure over
millions of years. Coal is a highly carbonaceous matter that has been formed as a
result of alteration of vegetable matter (e.g., plants) under certain favourable
conditions. It is chiefly composed of C, H, N, and O, besides non-combustible
inorganic matter.

Classification of Coal
•Coals are classified on the basis of their rank. Rank is defined as the degree or
extent of maturation and is therefore a qualitative measure of carbon contents. Peat,
lignite and sub-bituminous coals are referred as low rank coals while bitu-
minous coals and anthracites are classed as high rank. In European terminology,
the lignite and sub-bituminous coals are called soft coals while bituminous coals
and anthracite coals are termed as hard coals. In North American terminology, the
coal series is written as
•Wood peat lignite bituminous anthracite.
Analysis of biomass/coal
In order to assess the quality of material the following two types of analysis
are made.

1. Proximate Analysis It includes the determination of moisture, volatile

matter, ash and fixed carbon. This gives quick and valuable information
regarding commercial classification and determination of suitability for a
particular industrial use.

2. Ultimate Analysis It includes the determination of carbon, hydrogen, nitro-

gen, sulphur and oxygen in coal. Since it is used for the determination of
elements present in the coal, it is also called elemental analysis. This analysis
gives exact results and are useful in calculating the calorific value of coal
using Dulong's formula.
 Proximate analysis
(1) Moisture: About 1 g of finely powered air-dried coal sample is weighed in a
crucible. The crucible is placed inside an electric hot air-oven, maintained at 105° -
110°C. The crucible is allowed to remain in oven for 1 hour and then taken out,
cooled in a desiccator and weighed. Loss in weight is reported as moisture (on
percentage-basis).

Percentage of moisture = Loss in weight x 100

Wt. of coal taken

(2) Volatile matter: The dried sample of coal left in the crucible in (1) is then
covered with a lid and placed in an electric furnace (muffle furnace), maintained at
925°± 20°C. The crucible is taken out of the oven after 7 minutes of heating. The
crucible is cooled first in air, then inside a desiccator and weighed again. Loss in
weight is reported as volatile matter on percentage-basis.
Percentage of volatile matter=
Loss in weight due to removal of volatile matter x 100
Wt. of coal sample taken
(3) Ash: The residual coal in the crucible in (2) is then heated without lid in a
muffle furnace at 700 ± 50° C for 1/2 hour. The crucible is then taken out, cooled
first in air, then in desiccator and weighed.

Heating, cooling and weighing is repeated, till a constant weight is obtained. The
residue is reported as ash on percentage-basis.

Percentage of ash = Wt. of ash left x 100

Wt. of coal taken

(4) Fixed carbon:

Percentage of fixed carbon = 100 - % of (moisture + volatile matter + ash)

 high percentage of fixed carbon is desirable.

 Importance of proximate analysis

Proximate analysis provides following valuable information in assessing the

quality of coal:

 (1) Moisture: Moisture lowers the effective calorific value of coal. Moreover,
it quenches the fire in the furnace. Hence, lesser the moisture content, better
the quality of coal as a fuel. However, presence of moisture, up to 10%,
produces a more uniform fuel-bed and less of "fly-ash".

 (2) Volatile matter: A high volatile matter containing coal burns with a long
flame, high smoke and has low calorific value. Hence, lesser the volatile
matter, better the rank of the coal. Higher volatile content in coal is
undesirable.
 A high volatile matter content means that high-proportion of fuel will be distilled
and burned as a gas or vapour. The volatile matter present in the coal may be
combustible gases (such as methane, hydrogen, carbon monoxide and other
hydrocarbons) or non-combustible gases (like CO2 and N2). Volatile matter
content is of special significance in coal gas manufacture and in carbonization
plants, particularly when by-product recovery is the main object. Thus, high-
volatile matter containing coals do not cake well; whereas medium-volatile matter
content coals are capable of yielding hard and strong coke on carbonization.
 (3) Ash is a useless, non-combustible matter, which reduces the calorific value of
coal. Moreover, ash causes the hindrance to the flow of air and heat, thereby
lowering the temperature. Also, it often causes. trouble during firing by forming
clinker), which block the inters paces of the grate. This in-turn causes obstruction
to air supply; thereby the burning of coal becomes irregular. Hence, lower the ash
content, better the quality of coal. The presence of ash also increases transporting,
handling and storage costs. The presence of ash also causes early wear of furnace
walls, burning of apparatus and feeding mechanism.
 (4) Fixed carbon: Higher the percentage of fixed carbon, greater is its calorific
and better the quality coal. Greater the percentage of fixed carbon, smaller is the
percentage of volatile matter. This also represents the quantity of carbon (in coal)
that can be burnt by a primary current of air drawn through the hot bed of a fuel.
Significance of ultimate analysis
(1) Carbon and hydrogen: Greater the percentage of carbon and hydrogen
better is the coal in quality and calorific value. However, hydrogen is mostly
associated with the volatile matter and hence, it affects the use to which the
coal is put. Also higher percentage of carbon in coal reduces the size of
combustion chamber required. The amount of carbon, the major combustible
constituent of coal, depends on the type of coal and its percentage increases
with rank from lignite to anthracite. Thus, percentage of carbon forms the
basis of classification of coal.

(2) Nitrogen has no calorific value and hence, its presence in coal is
undesirable; thus, a good quality coal should have very little nitrogen
content.
Nitrogen:

• About 1 g of accurately weighed powdered 'coal is heated with concentrated H2SO4

along-with K2SO4(catalyst) in a long-necked flask(called Kjeldahl's flask). After the
solution becomes clear, it is treated with excess of KOH and the liberated ammonia is
distilled over and absorbed in a known volume of standard acid solution. The unused
acid is then determined by back titration with standard NaOH solution. From the volume
of acid used by ammonia liberated, the percentage of N in coal is calculated as follows:

Volume of acid used x Normality x 1.4

Percentage of N = Weight of coal taken
(3) Sulphur, although contributes to the heating value of coal, yet on
combustion produces acids (SO2 and SO3), which have harmful effects of
corroding the equipment's and also cause atmospheric pollution. Sulphur is,
usually, present to the extent of 0.5 to 3.0% and derived from ores like iron
pyrites, gypsum, etc., mines along-with the coal.
• Presence of sulphur is highly undesirable in coal to be, used for making coke
for iron industry, since it is transferred to the iron metal and badly affects the
quality and properties of steel. Moreover, oxides of sulphur (formed as
combustion products) pollute the atmosphere and leads to corrosion.

(4) Oxygen content decreases the calorific value of coal. High oxygen-content
coals are characterized by high inherent moisture, low calorific value, and low
coking power. Moreover, oxygen is in combined form with hydrogen in coal
and thus, hydrogen available for combustion is lesser than actual one. An
increase in 1% oxygen content decreases the calorific value by about 1. 7% and
hence, oxygen is undesirable. Thus, a good quality coal should have low
percentage of oxygen
Ultimate analysis
Carbon and hydrogen: About 1-2 g of accurately weighed coal sample is
burnt in a current of oxygen in a combustion apparatus. C and H of the
coal are converted into CO2 and H2O respectively. The gaseous products
of combustion are absorbed respectively in KOH and CaCl2 tubes of
known weights. The increase in weights of these are then determined.

Increase in weight of KOH tube x 12 x 100

Percentage of C = Weight of coal sample taken x 44

Increase in weight of CaCl2 tube x 2 x 100

Percentage of H = Weight of coal sample taken x 18
Sulphur is determined from the washings obtained from the known mass of
coal, used in a bomb calorimeter for determination of a calorific value.
During this determination, S is converted into sulphate. The washings are
treated with barium chloride solution, when barium sulphate is precipitated.
This precipitate is filtered, washed and heated to constant weight.

Weight of BaSO4 obtained x 32 x 100

Percentage of S = Weight of coal sample taken in bomb x233

Ash determination is carried out as in proximate analysis.

Oxygen: It is obtained by difference.

Percentage of O = 100 - Percentage of (C + H + S + N + ash)

Bomb Calorimeter
• This apparatus is used to find the calorific value of solid and liquid fuels.
• Construction of Bomb calorimeter: a bomb calorimeter consists of the
following:
• A stainless steel bomb in which a combustion of fuel is made to take place
• Two Electrodes and an oxygen inlet valve
• Nickel or stainless steel crucible
• The bomb is placed in copper calorimeter, which is surrounded by air and
water jacket to prevent heat losses due to radiation
• The calorimeter is provided with electrically operated stirrer and Beckmann’s
thermometer which can accurately read temperature difference upto 1/100th
of a degree
Working of Bomb calorimeter:
• A known mass of the given fuel is taken in nickel crucible supported
over a ring inside the steel bomb which is connected with two
electrodes. The bomb lid is tightly screwed and filled with O2 upto 25
atm. Pressure. The bomb is then lowered into the copper calorimeter
containing known mass of water. The water is stirred with the help of
mechanical stirrer and the initial temp is recorded. The electrodes are
then connected to 6 volt battery and the circuit is completed. The
sample burns and the heat is liberated. Uniform stirring of water is
continued and the maximum temp. attained is recorded.
IMPORTANT FORMULAES :
1. Theoretical C.V. of the fuel =33800 C +144000 (H2 – O2/8) +9270 S KJ/Kg.

2. L.C.V. = H.C.V. – 9 H2 x 2466 KJ/Kg.

3. Mass of air required for complete combustion of 1 Kg. of fuel.

= 100/23 (2.67 C + 8 H2 +S – O2) Kg.

4. Mass of excess air supplied = 100/23 x Mass of excess Oxygen in flue gas.
Example
A sample of coal has following composition on mass basis Carbon
82%, Hydrogen 8%, Sulphur 2%, Oxygen 4% and Ash 4%.
Calculate using Dulong’s formula higher and lower calorific value of
fuel.
Answer: HCV: 38701.4 KJ/Kg.
LCV: 36925.88 KJ/Kg.
Example: 2
A sample of coal has the following composition by mass, carbon
76%, Hydrogen 5%, Oxygen 8.5%, Nitrogen 2%, Sulphur 1.5% and
Ash 7% calculate higher and lower calorific value of fuel per Kg.
Answer: HCV: 31497.05 KJ/Kg. L.C.V. = 30387.35 KJ/Kg.
Example 3
A coal has the following composition by mass Carbon 80%,
Hydrogen 5%, Oxygen 6%, Nitrogen 2.5%, Sulphur 1.5% and Ash 5%.
Calculate HCV and LCV per kg of coal.
HCV: 33299.05 KJ / Kg
LCV: 32189.35 KJ / Kg
Example 4:
The following is the percentage composition of a sample of coal on
mass basis. C = 85, H2 = 4, O2 = 10 and remaining is ash
find minimum mass of air required for complete combustion of 1 Kg. of
coal.
Answer: 40.82 Kg. per Kg. of Coal burnt.
Example:
The following is the percentage composition of coal on mass basis.
C = 80, H2 = 3.3, O2 = 4 and S = 0.9 and remaining is ash.
Calculated theoretical air required to 1 Kg. of coal completely.
Answer: 10.456 Kg. per Kg. of Coal burnt.
Example:
During a boiler trial the coal analysis on mass basis was reported as
C = 62.4%, H2 = 4.2%, O2 = 4.5%, Moisture = 15% and Ash
13.9%. Calculate
(a) minimum air required to burn 1 Kg. of coal also
(b) calculate H.C.V. & L.C.V.

Answer: 8.613 Kg. per Kg. of Coal burnt.

H.C.V. = 26329.2 KJ/Kg.
LCV = 25397.052 KJ/Kg
Example
• A steam boiler uses coal in the furnace. The ultimate analysis of coal
by mass received is:
C = 78%, H2 = 3%, O2 = 3%, S = 1%, ash = 10%, moisture = 5%
Excess air supplied is 30%.
Calculate the (a) mass of air to be supplied and
(b) Mass of gaseous products formed per Kg of coal burnt?
• Answer: 13.13 kg
• CO2 =2.86 Kg, H2O = 0.27 Kg, SO2 = 0.02 Kg, Excess O2 =/Kg of coal =
• Mass of N2 = 10.1 Kg