CAGAYAN STATE UNIVERSITY

Carig Campus
College of Engineering

CHEMISTRY FOR ENGINEERS

CHEM111

UNIT II
ENERGY: FUELS
Learning Objectives:
At the end of this unit, the students will be able to:
1. Distinguish different types of fuels.
2. Calculate the amount of energy that can be derived from fuels.
CONTENTS:
I. Fuels
II. Classification of Fuels
III. Units of Heat and of the Calorific Value
IV. Calorimetry and the Calorific Value

INTRODUCTION
The International Energy Agency (IEA) reported that the world’s fuel utilization has been
increasing over the years. As shown on Fig. 7.1 the world’s consumption of fuel increased from 81,911
ktoe (kiloton of oil equivalent, with 1 toe=10 Gcal) in 1990 to 817,603 ktoe in 2017, where oil was
attributed to be the largest division of the fuel consumed. Fuels are mainly used for transportation,
industrial and domestic purposes (Fig. 7.2). Because of the wide utilization of fuels in our daily lives,
the need to study fuel and its calorific values are important.

*Source: International Energy Agency – Data and Statistics

Figure 2b.1.1 World’s Total Final Energy Consumption by Source (1990-2017)

Module 9_Fuels (Part 1): Page 1 of 12

 *Source: International Energy Agency – Data and Statistics

Figure 2b.1.2 World’s Total Final Energy Consumption by Sector (1990-2017)

I. FUELS
A fuel is a combustible substance that reacts with air resulting to a release in heat or light.
This heat can be converted to other forms of energy which can then be used for transportation,
domestic, and industrial purposes. Generally, fuels are composed of carbon and hydrogen.
The combustion reaction occurs when the fuel (be it in solid, liquid, or gaseous form) reacts
with the oxygen (𝑂2 ) present in air. This unit process produces carbon dioxide (𝐶𝑂2 ) and water
(𝐻2 𝑂). A complete combustion is observed when all the combustible components of the fuel are
converted: all carbon is converted to carbon dioxide, all hydrogen is converted to water, all sulfur
is converted to sulfur dioxide.

Figure 2b.1.3 The combustion reaction (Google images)

Module 9_Fuels (Part 1): Page 2 of 12

 The reactions that occur during complete combustion are:
𝐶 + 𝑂2 → 𝐶𝑂2 All carbon atoms converted to carbon dioxide
1
𝐻2 + 𝑂2 → 𝐻2 𝑂 All hydrogen is converted to water
2
𝑆 + 𝑂2 → 𝑆𝑂2 All sulfur is converted to sulfur dioxide

An organic fuel’s complete combustion is represented by the equation below:

𝟏 𝒙 𝒙
𝑪𝒘 𝑯𝒙 𝑶𝒚 𝑺𝒛 + [𝟐𝒘 + + 𝟐𝒛 − 𝒚] 𝑶𝟐 → 𝒘𝑪𝑶𝟐 + 𝑯𝟐 𝑶 + 𝒛𝑺𝑶𝟐 𝑬𝒒. (𝟐𝒃. 𝟏. 𝟏)
𝟐 𝟐 𝟐

Energy is released in the form of heat during combustion. Thus, the energy of product is
lower compared to the energy of the reactants, which is a result of the fuel’s elemental
components (carbon, hydrogen, oxygen) rearrangement of valence electrons.
The following conditions must be satisfied for combustion to proceed:
(a) Presence of a combustible material.
(b) Presence of a supporter to combustion.
(c) Attainment of ignition temperature.

II. CLASSIFICATION OF FUELS

Fuels are classified based on occurrence and on their physical state/state of aggregation.

Fuels based on occurrence have two types:

i. Natural fuels. They are also known as primary fuels since they occur in nature.
e.g. Wood, peat, coal, petroleum, natural gas, crude oil
ii. Derived fuels. Also known as secondary fuels since they are derived from natural fuels.
e.g. Charcoal, coke, kerosene oil, diesel

Fuels can also be classified based on their physical state: solid, liquid, and gaseous fuels.

Gaseous fuels include natural gas composed of hydrocarbon gases, gases manufactured as fuel,
and gases obtained as by-products of some industrial operations; can be natural or derived.

(a) Natural gas – associated with petroleum oil deposits, with coal seams, or with the decay of
organic matter.
(b) Derived gases
Table 2B.1. Examples of Derived Gases
Gas Fuel Source Reaction
Wood gas Wood Distillation or carbonization
Peat gas Peat Distillation or carbonization
Coal gas Coal Carbonization
Producer gas Coal Gasification in air
Water gas Coal Gasification in air and steam
Lurgi gas Coal Gasification in 𝑂2 and steam
Blast furnace gas Coal Hydrogenation in the reduction of ores

Module 9_Fuels (Part 1): Page 3 of 12

 Petroleum
Refinery gas Cracking
and oil shale
Petroleum Hydrogenation, Water gas reaction,
Oil gas
and oil shale Partial oxidation
Acetylene Carbides Hydrolysis
Hydrogen gas Water Electrolysis
*Source: Laurito (1994)

As with all other gaseous systems, the fuel gas volume varies with the temperature and
pressure of the system. Table 7.2 shows common conditions of the system:
Table 2B.2. Common System Conditions
Condition Temperature and Pressure
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑎𝑛𝑑 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑠𝑡𝑝 0°𝐶 𝑎𝑛𝑑 760 𝑚𝑚 𝐻𝑔 (1 𝑎𝑡𝑚)
32°𝐹 𝑎𝑛𝑑 30 𝑖𝑛 𝐻𝑔 𝑜𝑟
𝑁𝑜𝑟𝑚𝑎𝑙 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑎𝑛𝑑 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒
𝑁𝑇𝑃 20°𝐶 𝑎𝑛𝑑 760 𝑚𝑚 𝐻𝑔 (1 𝑎𝑡𝑚)
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑎𝑛𝑑 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 60°𝐹 𝑎𝑛𝑑 30 𝑖𝑛 𝐻𝑔 𝑜𝑟
(for natural gases and similar fluids) 𝑆𝑇𝑃 15.56°𝐶 𝑎𝑛𝑑 760 𝑚𝑚 𝐻𝑔 (1𝑎𝑡𝑚)

Other system conditions of gaseous fuels are:

• Dry condition – no water vapor is present in the gas
• Wet condition – the gas is saturated with water vapor at STP
At saturation:
Partial Pressure of water in gas = Vapor pressure at partial saturation
%𝑅𝐻 (𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 ℎ𝑢𝑚𝑖𝑑𝑖𝑡𝑦)
= 𝑉𝑎𝑝𝑜𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑥
100
We can calculate the vapor pressure using Antoine’s equation:
𝑩
𝐥𝐨𝐠 𝑽𝑷 = 𝑨 − 𝑬𝒒. (𝟐𝒃. 𝟐. 𝟏)
𝑪+𝑻
Where: 𝑉𝑃 − 𝑣𝑎𝑝𝑜𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑖𝑛 𝑚𝑚 𝐻𝑔
𝑇 − 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑖𝑛 °𝐶
𝐴 = 7.96681, 𝐵 = 1668.21, 𝐶 = 228 (these are constants for water)

Liquid fuels are classified based on their chemical nature and usage.
Petroleum or crude oil is a deep brown oil derived from the organic matter originally present
in marine sediments. It mainly consists of hydrocarbons, paraffins, naphthenes and aromatics in
varying proportions. Petroleum is produced when dead organic matter that has settled is attacked
by anaerobic bacteria (bacteria that do not require oxygen to survive) wherein the organic
compounds are destroyed and the remaining unsaturated fatty oils and fatty acids undergo
polymerization. In addition, sulfur, nitrogen, and oxygen are present in the form of derivatives
of hydrocarbons in the oil. The average ultimate analysis of petroleum shows its contents to be
𝐶 = 84 − 87%, 𝐻 = 11 − 14%, 𝑆 = 0.5 − 3%, 𝑁 = 0 − 0.6%, 𝑂 = 2 − 3%.

Petroleum/crude oil can be classified according to its chemical nature:

(a) Paraffin-base crude oils. These are composed of saturated hydrocarbons up to 𝐶35 𝐻72 which
are semi-solids (waxes) at room temperature, and very little to no asphaltic (bituminous)

Module 9_Fuels (Part 1): Page 4 of 12

 matter. The C atoms in the hydrocarbons (HCs) of the paraffin series are all connected by a
single bond.
(b) Asphalt-base crude oils. These contain mainly naphthenes (or cycloparaffins) with smaller
amounts of paraffins and aromatics. These also contain large proportions of asphaltic matter.
(c) Mixed-base crude contains combinations of the above types of compounds but is generally
rich in waxes. They can be considered the ‘gray area’ between the two other classifications.
About 90% of all crude produced at present fall in this last category.

Classification of petroleum/crude oils according to its use:

(a) Light oils or spirits are fuels suitable for use with internal combustion engines and jet engines.

Table 2B.2.1 Light oils and how they are synthesized

Fraction Synthesis
Distillation or cracking natural petroleum oils
and related natural deposits
Light fractions Hydrogenation of coal, coal tar, or heavy oil
residues
Fischer-Tropsch process
Alcohols
(Methyl and Ethyl Fermentation process
alcohol)
Distillation of coal tar or by extraction from
Benzole
coal gas
Blendinf of methyl alcohol and gasoline/
Alcogas
diesel

(b) Furnace oils (or fuel oils) are the heaviest grades of natural petroleum oils and lubricating oils.
They are made up mostly of residues from which the more valuable lubricating oils and fractions
have been removed thru distillation. Commercial types of fuel oils usually are mixed with other
petroleum fractions to regulate its viscosity and to help it reach its ideal flash point.

Figure 2b.3.1 Fractions of crude oil and their uses

(Source: http://science-resources.co.uk/)
Module 9_Fuels (Part 1): Page 5 of 12
 Solid fuels are classified into natural and artificial fuels.

(a) Natural solid fuels

Coal – a primary fuel that is highly carbonaceous matter that has been formed from the fossilized
remains of plants, 100 to 300M years ago, under suitable conditions. It is mainly composed of C,
H, N, O and other non-combustible inorganic matter. It is also known are as fossil fuel.
The combined action of high temperatures, pressures, anaerobic conditions, and the
presence of bacteria over long periods of time has converted the cellulosic material of wood into
coal. This process involves the evolution of 𝐶𝑂2 and methane, loss of water, increase in calorific
value and hardness of the transition from wood to anthracite. The continuity of transformation
can be proved graphically by plotting oxygen and C percentages of coal at different stages of
formation. The transition also results in the decrease in H, N, and S contents.
𝑊𝑜𝑜𝑑 ⟶ 𝑃𝑒𝑎𝑡 ⟶ 𝐿𝑖𝑔𝑛𝑖𝑡𝑒 ⟶ 𝐵𝑖𝑡𝑢𝑚𝑖𝑛𝑜𝑢𝑠 𝑐𝑜𝑎𝑙 ⟶ 𝐴𝑛𝑡ℎ𝑟𝑎𝑐𝑖𝑡𝑒

i. Wood: can be burned directly as fuel and may be converted into charcoal or producer gas.
It contains lignocellulose, resins and proteins. The average composition of wood on a
moisture-free basis is 𝐶 = 55%, 𝐻 = 6%, 𝑂 = 43%, ash = 1%. Wood’s calorific value varies
from 4000 to 6400 BTU/lb.
ii. Peat or Turf: a brown fibrous mass of partially decayed plant material that has
accumulated. It’s a soft coal-like substance that contains 80 to 90% moisture and about 57%
C with a calorific value of ~5,400 kcal/kg. It is used as a domestic fuel in steam boilers,
power stations, gas producers, etc. Low temperature carbonization of peat is used for
getting peat coke and its by-products. Peat is easy to ignite and burns freely giving a long
pleasant flame.
iii. Lignites or Brown coals: a soft and brown-colored coal. It usually contains 20 to 60%
moisture. Airdried lignite contains 𝐶 = 60 − 70%, 𝑂 = 20% with calorific values of 6500 to
7100 kcal/kg. It burns with a smoky flame. It is usually powdered, dried and presses into
briquettes and used for domestic purposes, for boilers and for production of producer gas.
iv. Bituminous coals: further classified based on carbon content:
(a) Sub-bituminous coal. It contains 𝐶 = 70 − 78%, 𝐻 = 4 − 5%, 𝑂 = 20% at 10 − 20%
moisture with a calorific value of 6800 – 7600 kcal/kg. It ignites easily and if it is low in
S content, it is used for gaseous fuel production.
(b) Bituminous coal. It contains 𝐶 = 78 − 90% with calorific value 8000 – 8500 kcal/kg. Its
chief use is for combustion in household and industrial furnaces and boilers, railway
locomotives and thermal power stations. By carbonization or gasification it is converted
to coke, gaseous fuels like producer gas, water gas, coal gas, and liquid fuels like coal
tar fuels.
(c) Semi-anthracite. This is intermediate form between bituminous coals and anthracite.
When air-dried, moisture content is 1-2%, volatile matter is 10-15% and the calorific
value is 8500-8800 kcal/kg.
v. Anthracite: the most C-heavy coal having percentages of C at around 92-98%. It also has
the lowest volatile matter and moisture contents and calorific values ranging from 8400-
8600 kcal/kg. It burns without smoke but ignites with difficulty, and possesses no coking
power. Its chief uses are in boilers, domestic ovens and metallurgical furnaces.

(b) Artificial solid fuels

i. Wood charcoal – solid residue from the carbonization of wood which involves heating wood
strongly in the absence of oxygen.

Module 9_Fuels (Part 1): Page 6 of 12

 ii. Peat charcoal – made by carbonizing peat at low temperatures.
iii. Lignite briquettes – air dried lignite.
iv. Coke – carbonized coal.

Table 2B.2.2. Comparisons between solid, liquid, and gaseous fuels

Properties Solid Fuels Liquid Fuels Gaseous Fuels
Costlier than solid
Price and Cheap and easily They are also costly
fuels, but cheaper in
availability available. except natural gas.
the countries of origin.
Can easily be They should be stored
Transportation and
transported through in leak proof tanks and
Transport storage are easy.
pipes and must be can be transported/
and storage Chance of spontaneous
stored in closed distributed through
explosion is rare.
containers carefully. pipelines.
Combustion Slow Quick Very fast
Even riskier than liquid
Fire hazards Less risk Greater risk
fuels
Always produced in
Smoke and combustion (presence Ash is not produced but Neither ash nor smoke
ash of ash in a substance smoke is produced. is produced.
reduces calorific value)
Calorific
Least Higher Highest
value (W/W)
Thermal
Least Higher Highest
efficiency
*Source: Goel & Kumar (2006)

III. UNITS OF HEAT & OF THE CALORIFIC VALUE

Units of Heat
(a) Calorie (cal): The amount of heat required to raise the temperature of one gram (1 g) of water
by one degree centigrade (1°C). e.g. 14.5 to 15.5°C
1 𝑐𝑎𝑙 = 4.18 𝐽𝑜𝑢𝑙𝑒 = 4.18 𝑥 107 𝑒𝑟𝑔𝑠
(b) Kilocalorie (kcal): The amount of heat required to raise the temperature of one kilogram (1 kg)
of water by one degree centigrade (1°C). e.g. 14.5 to 15.5°C
1 𝑘𝑐𝑎𝑙 = 1000 𝑐𝑎𝑙
(c) British thermal unit (BTU): The amount of heat required to raise the temperature of one pound
(1 lb.) of water by 1 degree Fahrenheit (1°F). e.g. 60 to 61°F
1 𝐵𝑇𝑈 = 252 𝑐𝑎𝑙 = 0.252 𝑘𝑐𝑎𝑙
1 𝑘𝑐𝑎𝑙 = 3.968 𝐵𝑇𝑈
(d) Centigrade heat unit (CHU): The amount of heat required to raise the temperature of one pound
(1 lb.) of water by one degree centigrade (1°C). e.g. 14.5 to 15.5°C

𝟏 𝒌𝒄𝒂𝒍 = 𝟏𝟎𝟎𝟎 𝒄𝒂𝒍 = 𝟑. 𝟗𝟔𝟖 𝑩𝑻𝑼 = 𝟐. 𝟐 𝑪𝑯𝑼

Units of Calorific Value

(a) For solid and liquid fuels: calorie per gram (𝑐𝑎𝑙/𝑔) or kilocalorie per kilogram (𝑘𝑐𝑎𝑙/𝑘𝑔) or British
thermal unit per pound (𝐵𝑇𝑈/𝑙𝑏).

Module 9_Fuels (Part 1): Page 7 of 12

(b) For gaseous fuels: kilocalorie per cubic meter (𝑘𝑐𝑎𝑙/𝑚3 ) or British thermal unit per cubic feet
(𝐵𝑇𝑈/𝑓𝑡 3 )
** for solids and liquids, the calorific value is expressed in heat/mass. For gaseous fuels, it is in
heat/volume.

Relation between the different units of calorific value:

1 𝑐𝑎𝑙/𝑔 = 1 𝑘𝑐𝑎𝑙/𝑘𝑔 = 1.8 𝐵𝑇𝑈/𝑙𝑏
1 𝑘𝑐𝑎𝑙/𝑚3 = 0.1077 𝐵𝑇𝑈/𝑓𝑡 3
1 𝐵𝑇𝑈/𝑓𝑡 3 = 9.3 𝑘𝑐𝑎𝑙/𝑚3

Generally, the calorific value of carbon from a combustion reaction is illustrated below:
𝑪 + 𝑶𝟐 → 𝑪𝑶𝟐 + 𝟑𝟗𝟒 𝒌𝑱/𝒎𝒐𝒍𝒆
Considering that there are 12 g/mol of carbon and 44 g/mol of CO2, and because 12 g of carbon
produces 394 kJ of energy, the calorific value of 1 g C is 𝟑𝟐. 𝟖𝟑 𝒌𝑱 or 𝟑𝟗𝟒 𝒌𝑱⁄𝟏𝟐𝒈.

IV. CALORIMETRY AND THE CALORIFIC VALUE

The calorific value or heating value of a fuel is defined as the total amount of heat evolved (or
produced) by the combustion of a unit quantity (in mass or in volume) of fuel at a reference
temperature. The ambient temperature (25 °C) may be used as reference temperature.

(a) Higher calorific value (HCV): It is also known as gross calorific value (GCV) or higher heating
value (HHV). It is the amount of heat evolved when a unit quantity of fuel undergoes complete
combustion and the water formed is in liquid state.
The hydrogen present in the fuel is converted into steam (water in gaseous form, 𝐻2 𝑂(𝑣)). When
the products of combustion are allowed to cool at room temperature, this causes the water to
change its state from vapor to liquid (𝐻2 𝑂(ℓ)). Due to this change in the state of water, the
latent heat is included on the computation of higher calorific value.
𝐻2 𝑂(𝑣) → 𝐻2 𝑂(ℓ)
Thus,
𝑸 = 𝒎𝑳 𝑬𝒒. (𝟐𝒃. 𝟒. 𝟏)
Where: 𝑄 = 𝐻𝑒𝑎𝑡
𝑚 = 𝑀𝑎𝑠𝑠
𝐿 = 𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡
Latent heat is defined as the energy which is released/absorbed by a body or a system during
phase transitions (evaporation, condensation, etc.).
(b) Lower calorific value (LCV): It is also known as net calorific value (NCV) or lower heating value
(LHV). It is the amount of heat evolved when a unit quantity of fuel undergoes combustion and
the water formed is in its gaseous state.
The steam or 𝐻2 𝑂(𝑣) formed by combustion escapes along with the hot combustion products.
The latent heat is not included in the computation. Thus, the LCV is always less than the HCV
value by the amount corresponding to the heat of condensation of water vapour, 𝐿𝐻2𝑂 =
587 𝑐𝑎𝑙/𝑔.
𝑳𝑪𝑽 = 𝑯𝑪𝑽 − 𝑳 𝑬𝒒. (𝟐𝒃. 𝟒. 𝟐)

Since 1 part of hydrogen (by mass) produces "𝑎" parts of water (by mass). Combining Eq. (2b.4.1)
and (2b.4.2) gives us:

𝑳𝑪𝑽 = 𝑯𝑪𝑽 − (𝒎𝑯𝟐 × 𝒂 × 𝑳) 𝑬𝒒. (𝟐𝒃. 𝟒. 𝟑)

Module 9_Fuels (Part 1): Page 8 of 12
 1
If we consider the following reaction: 𝐻2 + 𝑂2 → 𝐻2 𝑂, we see that 2 g of hydrogen gives 18 g
2
water upon combustion (since H2=2 g/mol, H2O=18 g/mol). This means that 1 g of hydrogen gas
gives 9 g water upon combustion, giving us:
𝒎𝑯𝟐
𝑳𝑪𝑽 = 𝑯𝑪𝑽 − 𝒙 𝟗 𝒙 𝑳𝒔𝒕𝒆𝒂𝒎 𝑬𝒒. (𝟐𝒃. 𝟒. 𝟒)
𝒎𝒇𝒖𝒆𝒍
Where : 𝐿𝐶𝑉 = 𝐿𝑜𝑤𝑒𝑟 𝑐𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑣𝑎𝑙𝑢𝑒, 𝐻𝐶𝑉 = 𝐻𝑖𝑔ℎ𝑒𝑟 𝑐𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑣𝑎𝑙𝑢𝑒
𝐿𝑠𝑡𝑒𝑎𝑚 = 𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑠𝑡𝑒𝑎𝑚 = 587 𝑐𝑎𝑙/𝑔
𝑚𝐻2 = 𝑀𝑎𝑠𝑠 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛, 𝑚𝑓𝑢𝑒𝑙 = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑓𝑢𝑒𝑙

Empirical relations between coal analysis and calorific values:

Dulong’s formula:
𝟏 𝑶
𝑯𝑪𝑽 = [𝟖𝟎𝟖𝟎 𝑪 + 𝟑𝟒𝟓𝟎𝟎 (𝑯 − ) + 𝟐𝟐𝟒𝟎 𝑺] 𝒌𝒄𝒂𝒍/𝒌𝒈 𝑬𝒒. (𝟐𝒃. 𝟒. 𝟓)
𝟏𝟎𝟎 𝟖
Where : 𝐻𝐶𝑉 = 𝐺𝑟𝑜𝑠𝑠 𝑐𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑣𝑎𝑙𝑢𝑒
𝐶, 𝐻, 𝑂, 𝑆 = % 𝑏𝑦 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑎𝑟𝑏𝑜𝑛, ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛, 𝑜𝑥𝑦𝑔𝑒𝑛, 𝑎𝑛𝑑 𝑠𝑢𝑙𝑓𝑢𝑟 𝑖𝑛 𝑡ℎ𝑒 𝑓𝑢𝑒𝑙

Assumptions in Dulong’s formula:

• The calorific value (CV) of the fuel is the algebraic sum of the individual heating values of
its elemental components.
• Oxygen is combined with hydrogen as in combined water and moisture, so that the surplus
𝑂
moisture available for combustion (Net H) is 𝐻 −
8
• The heat of formation of coal is zero.
Thus,
𝑳𝑪𝑽 = [𝑯𝑪𝑽 − (𝟎. 𝟎𝟗 𝑯 × 𝟓𝟖𝟕)] 𝑬𝒒. (𝟐𝒃. 𝟒. 𝟔)

Considering the combustion reaction we have been discussing previously (refer to page 3 of this
module), we can see that 32g of oxygen is needed for the combustion of 12g carbon to produce 44g
𝐶𝑂2 . Similarly, 4g of hydrogen requires 32g oxygen to form 36g 𝐶𝑂2 . Thus, 1 part of H gives 9 parts
of water (4/36 = 9).
2𝐻2 (𝑔) + 𝑂2 (𝑔) ⟶ 2𝐻2 𝑂 (𝑔)
Mass proportions 4 32 36

Example 2b.2.1
Calculate the gross and net calorific values of coal having the following compositions: 85%
carbon, 8% hydrogen, 4% ash, 2% nitrogen, 1% sulfur. Latent heat of combustion of steam is
587 cal/g.
Solution:
1 𝑂
𝐻𝐶𝑉 = [8,080𝐶 + 34,500 (𝐻 − ) + 2,240𝑆]
100 8
1 0
= [(8,080 × 85) + 34,500 (8 − ) + (2,240 × 1)]
100 8
1
= [686,800 + 276,000 + 2,240]
100

Module 9_Fuels (Part 1): Page 9 of 12

 1
= [965,040]
100

𝐻𝐶𝑉 = 9,650.4 𝑐𝑎𝑙/𝑔𝑚

Example 2b.2.2 A coal has the following composition by weight: 𝐶 = 90%, 𝑂 = 3.0%, 𝑆 =
0.5%, 𝑁 = 0.5%, 𝑎𝑛𝑑 𝑎𝑠ℎ = 2.5%. The net calorific value of this coal was found to be
8,490.5 𝑘𝑐𝑎𝑙/𝑘𝑔. Calculate the percentage of hydrogen and the higher calorific value of coal.

Solution:
𝐻𝐶𝑉 = 𝐿𝐶𝑉 + (0.09𝐻 × 587)
= 8,490.5 + (0.09𝐻 × 587)
𝐻𝐶𝑉 = 8,490.5 + 52.8𝐻 𝑘𝑐𝑎𝑙/𝑘𝑔

According to Dulong’s formula

1 3.0
𝐻𝐶𝑉 = [(8,080 × 90) + 34,500 (𝐻 − ) + (2,240 × 0.5)]
100 8
= [7,272 + 345𝐻 − 129.4 + 11.2]
𝐻𝐶𝑉 = [7,153.8 + 345𝐻] 𝑘𝑐𝑎𝑙/𝑘𝑐𝑎𝑙

Considering both equations for HCV:

𝐻𝐶𝑉 = 𝐻𝐶𝑉
7,153.8 + 345𝐻 = 8,490.5 + 52.8𝐻
(345 − 52.8) 𝐻 = 8,490.5 − 7,153.8
1,336.7
%𝐻 =
292.2
%𝐻 = 4.575%
Thus,
𝐻𝐶𝑉 = 𝐿𝐶𝑉 + (0.09𝐻 × 587)
= 8,490.5 + [(0.09 × 4.575) × 587]
= 8,490.5 + 241.3
𝐻𝐶𝑉 = 8,732.20 𝑘𝑐𝑎𝑙/𝑘𝑔

Example 2b.2.3 A sample of coal was found to have the following % composition by weight:
𝐶 = 75%, 𝐻 = 5.2%, 𝑂 = 12.1%, 𝑁 = 3.2%, 𝑎𝑛𝑑 𝑎𝑠ℎ = 4.5%. Calculate (i) The minimum amount
of 𝑂2 and air by weight necessary for complete combustion of 1 kg of coal; (ii) Gross and net
calorific values of the coal sample using Dulong’s formula.
Solution: (i) Given that weight of coal = 1 kg
% 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐶𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑
1 32
𝐶 = 750 𝑔 𝐶𝑂 + 𝑂2 ⟶ 𝐶𝑂2 750 × = 2000 𝑔
2 12
1 16
𝐻 = 52 𝑔 𝐻2 + 𝑂2 ⟶ 𝐻2 𝑂 52 × = 416 𝑔
2 2

Module 9_Fuels (Part 1): Page 10 of 12

 𝑇𝑜𝑡𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 2000 + 416
= 2416 𝑔 𝑂2 or
2.416 𝑘𝑔 𝑂2

𝑁𝑒𝑡 𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑓𝑜𝑟 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = 2416 − 121

= 2295 𝑔 𝑂2 𝑜𝑟
2.295 𝑘𝑔 𝑂2
𝑀𝑖𝑛𝑖𝑚𝑢𝑚 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑖𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 100
2.295 ×
𝑓𝑜𝑟 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 23
= 9.978 𝑘𝑔

(ii) 𝐺𝐶𝑉 = 1 𝑂
[8,080 𝐶 + 34,500 (𝐻 − )]
100 8

= 1 12.1
[(8,080 × 75) + 34,500 (5.2 − )]
100 8
𝐺𝐶𝑉 = 7,332 𝑘𝑐𝑎𝑙/𝑘𝑔

𝑁𝐶𝑉 = 𝐻𝐶𝑉 − (0.09𝐻 × 587)

= 7,332 − [(0.09 × 5.2) × 587]
𝑁𝐶𝑉 = 7,057 𝑘𝑐𝑎𝑙/𝑘𝑔

Self-Learning Assessment 2.10

1. Calculate the gross and net calorific values of a coal sample having the following
compositions: 𝐶𝑎𝑟𝑏𝑜𝑛 = 80%, 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 = 12%, 𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 = 3%, 𝐴𝑠ℎ = 3%, 𝑆𝑢𝑙𝑓𝑢𝑟 = 2%,
𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑠𝑡𝑒𝑎𝑚 = 587 𝑐𝑎𝑙/𝑔
2. A sample of coal has the following compositions 𝐶 = 90%, 𝐻 = 6%, 𝑆 = 2%, 𝑂 = 1.5% 𝑎𝑛𝑑 𝐴𝑠ℎ =
0.5%. Calculate the gross and net calorific values if the latent heat of condensation of steam =
580 cal/g.

SUMMARY

Module 9_Fuels (Part 1): Page 11 of 12

 1. Empirical correlations and calorific values – Dulong’s formula

1 𝑂
𝐻𝐶𝑉 = [8080 𝐶 + 34500 (𝐻 − ) + 2240 𝑆] 𝑘𝑐𝑎𝑙/𝑘𝑔
100 8

𝐿𝐶𝑉 = [𝐻𝐶𝑉 − (0.09 𝐻 × 587)]

Table 2B.S.1. Differences Between Gross and Net Calorific Value

Gross calorific value
1. The amount of heat released when a unit
quantity of fuel is burned completely and
the products of combustion are allowed
to cool at room temperature.
2. Latent heat of condensation of steam is
included.
3. It is also known as higher calorific value
(HCV).
4. Higher than net calorific value.
Net calorific value
1. The amount of heat released when a unit
quantity of fuel is burned completely and
the products of combustion are allowed
to escape.
2. Latent heat of condensation of steam is
not included.
3. It is also known as lower calorific value
(LCV).
4. Lesser than gross calorific value.
*Source: Goel & Kumar (2006)

2. Units
𝑐𝑎𝑙 𝑘𝑐𝑎𝑙 𝐵𝑇𝑈
(a) Solid fuel or liquid fuel: 𝑜𝑟 𝑜𝑟
𝑔𝑚 𝑘𝑔 𝑙𝑏
(b) Gaseous fuel: 𝑘𝑐𝑎𝑙/𝑚3 𝑜𝑟 𝐵𝑇𝑈/𝑓𝑡 3
(c) Unit conversion
i. 1 𝑘𝑐𝑎𝑙/𝑘𝑔 = 1.8 𝐵𝑇𝑈/𝑙𝑏
ii. 1 𝑘𝑐𝑎𝑙/𝑚3 = 0.1077 𝐵𝑇𝑈/𝑓𝑡 3
iii. 1 𝐵𝑇𝑈/𝑓𝑡 3 = 9.3 𝑘𝑐𝑎𝑙/𝑚3

References:
1. Goel, N. & Kumar, S. (2006). Concise Engineering Chemistry (2nd Ed). AITBS
Publishers and Distributors, India. ISBN 81-7473-233-2
2. Laurito, E. (1994). Stoichiometry of Fuel Combustion and Related Process Industries.
National Book Store, Inc., Philippines. ISBN 971-08-5782-7
3. Mukhopadhyay, R. & Datta, S. (2007). Engineering Chemistry. New Age International
Limited Publishers, India. ISBN 978-81-224-2872-8

Module 9_Fuels (Part 1): Page 12 of 12