Engineering Chemistry
Chapter 1. Fuels and Energy Storage Systems
Introduction: The prosperity of any Country can be decided by its fuel
consumption. India’s per capita fuel consumption is 595 kg. (reference) The
booming economy should demand much elevated level of energy consumption.
Hence their stock is limited and diminishing very fast due to Asymmetric effect
of industrialization. We could fast reach an energy crisis in the next few decades;
when demand outstrips supply ( John Pickrell 4 September 2006. The quality
of fuel depends upon the quantity and intensity of heat generated on burning of a
definite quantity of a fuel.
Fuels –
It is a naturally occurring or artificially prepared combustible carbonaceous
material which is used as a source of energy.
Definition- It can be defined as- “Any combustible substance which when
burnt in presence of oxygen gives heat and light.”
Examples: Wood, Coal, Charcoal, Petrol, Diesel, Kerosene, etc.
Carbon and Hydrogen are the main constituents of a fuel. Fuel also
contains sulfur, oxygen and nitrogen in minute quantities in addition to
carbon and hydrogen. Carbon, hydrogen and sulfur are combustible
elements in a fuel.
During combustion of a fuel , the carbon and hydrogen atoms combine with
oxygen with simultaneous liberation of heat and results in the formation of
new compounds like CO2 and H2O. These new compounds have less
energy in them, hence the energy released during combustion is the
difference in the energy of the reactants and that of products formed.
Fuel + energy Products + heat
Classification:
Fuels are mainly classified in two types-
1. Primary Fuel (Natural) – Those are found naturally. e.g. wood, coal,
natural gas, petroleum, etc.
2. Secondary Fuel (Artificial) – Those which are prepared from primary
fuels. e.g. coke, charcoal, producer gas, blast furnace gas. etc.
Characteristics of good fuel-
While selecting the fuel for a particular purpose , following characteristics are
considered.
It should be easily available and cheap.
Storage, handling and transportation of the fuel should be easy.
The ignition temperature of the fuel should not be too low or too high. High
ignition temperature indicate more time required to reach higher
temperature whereas low temperature may lead to fire which is dangerous
for storage and transport.
A fuel should have less percentage of moisture as it reduces calorific value.
A good fuel should contain less amount of combustible matter so that on
combustion, it forms less smoke, clinker and ash or the level of emission
of smoke should be low.
There should be minimum of waste after the combustion of a fuel. Solid
fuel leave behind ash as an undesirable waste which restrict further
combustion.
The fuel should have high calorific value, so that upon burning smaller
quantity fuel, greater heat can be obtained.
The fuel upon combustion should produce less pollution of environment.
Particularly, it should not generate the harmful gases like CO, NOx, SO2
etc.
A fuel should have better thermal efficiency and it should burn with
uniform combustion rate.
Calorific value:
The Calorific value of a fuel is measured in terms of the heating
efficiency or the performance during its ignition in the presence of
oxygen.
It is defined as “The total quantity of heat liberated, when a unit mass of
the fuel is burnt completely.”
The unit of calorific value of a solid or liquid is kcal/kg or J/kg or cal/gm.
For gaseous fuels, it is important to refer the temperature and pressure of
the gas along with heat quantity per unit volume because volume of gas
varies with temperature and pressure. Hence unit of calorific value for a
gaseous fuel is kJ/m3 at the given temperature and pressure.
Generally calorific value of fuels is expressed in two ways-
1. Gross / higher calorific value represented as GCV or HCV
2. Net / lower calorific value represented as NCV or LCV
Gross / Higher Calorific Value: (HCV/GCV)
It is defined as “The total amount of heat produced, when unit mass/
volume of the fuel has been burnt completely in air or oxygen and the
products of combustion have been cooled to room temperature.”
Explanation – Most of the fuels used by us are hydrocarbon fuels. And
usually, all fuels contain some hydrogen and when the calorific value of
hydrogen containing fuel is determined, the hydrogen is converted into
steam. If the products of combustion are condensed to the room
temperature, the latent heat of condensation of steam also gets included in
the measured heat, which is then called higher or gross calorific value.
Net / Lower Calorific Value: (LCV/NCV)
It is defined as “The net heat produced, when unit mass/ volume of the
fuel is burnt completely, and the products are permitted to escape”.
When a fuel is in use, the water vapour and moisture are not condensed
and escape as such along with hot combustion gases hence less heat is
available so termed as lower calorific value.
Net calorific value = (GCV – latent heat of condensation of steam)
Units of calorific value:
For solid or liquid fuel, the calorific value is expressed in calorie/gram or
kilocalorie/kg or British thermal unit/lb i.e B.Th.U.
In case of gaseous fuel, the unit of calorific value is kilocalorie/cubic
meter. i.e. kcal/m3 or B.Th.U./cubic feet i.e. B.Th.U/ft3.
1 kcal/kg = 1.8 x B.Th.U/ lb
1 kcal/m3 = 0.1077 x B.Th.U/ ft3
1 B.Th.U/ ft3 = 9.3 x kcal/m3
Solid fuel-
Main solid fuels are wood and various varieties of coal and secondary fuels
like charcoal and coke can be prepared from wood and coal..
Solid fuels are cheap and easily available, easy to transport, storage and
use.
They do not undergo spontaneous consumption hence safe for use.
Calorific value of solid fuels is low in comparison with that of liquid or
gaseous fuels.
Coal:
Coal is the most important highly carbonaceous solid fuel.
As calorific value depends on carbon content it has high calorific value.
The major constituents of coal are carbon, hydrogen, oxygen, nitrogen
and small amount of some non-combustible matter.
Coal is formed from the parent material wood by progressive
transformation which is called coalification.
The classification of coal is based upon the degree of alteration from
parent material wood, which is shown as follows –
Wood Peat Lignite Bituminous coal Anthracite coal
During formation of Anthracite, there occurs decrease in moisture
content, hydrogen, oxygen, nitrogen and sulphur, volatile matter and
increase in carbon content and so the calorific value. Increase in hardness.
Peat –
It is brown fibrous jelly like mass and contains high amount of
water.
The average composition of peat is C= 57%, H = 6%, O = 35%,
Ash = 2.5 to 6%.
Its calorific value is 5,400 kcal/kg.
It is useful as domestic fuel.
Lignite –
It is soft, brown coloured intermediate stage between peat and
bituminous coal.
Dried lignite contains Carbon = 60 – 70 %, Oxygen – 20%, ash =
4-6 %.
The average calorific value is 6000 to 7000 kcal/kg.
It burns with long smoky flame.
It is used as domestic fuel, for thermal power plants, for boilers.
It is also used in the manufacture of producer gas.
Bituminous Coal –
It is black or dark grey coal.
It covers wide variety of common coals which contain bitumen,
coal and tar. This coal is further subdivided into following-
1. Sub-bituminous-
Black, homogeneous and smooth.
High moisture and volatile content
Calorific value is 7,000 kcal/kg
Carbon = 75- 83 % Oxygen = 10-20 %
2. Bituminous-
Black in colour with laminated structure.
Carbon = 78 -90%, volatile matter = 20 – 45%.
The calorific value is 8000 to 8500 kcal/kg
Used for industrial purpose for manufacturing metallurgical
coke, coal gas and steame generation.
3. Semi-bituminous-
Rich in carbon i.e 90-95 % and have low volatile matter i.e
9- 20%, low ash content.
The calorific value is 8500 to 8600 kcal/kg.
Anthracite Coal –
Highest ranking coal
Carbon = 92-93%, volatile matter = 8 % and ash = 2-3%,
Very hard and brittle
The calorific value is 8600 to 8700 kcal/kg
Useful in steam generation, metallurgy and house hold use.
Analysis of Coal:
To decide the quality of coal, the coal is analysed by the following two steps.
1. Proximate Analysis: It involves determination of Moisture, Volatile
matter, Ash content and Fixed carbon.
i) Determination of Moisture in coal-
About 1 gm of finely powdered air-dried coal sample is weighed in a
crucible
The crucible is placed inside an electric hot oven, maintained at 105
degree Celsius to 110 degree Celsius
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
Formula:
% of moisture = Loss in weight/Wt. of coal taken x 100
ii)Determination of Volatile matter in coal-
• The dried sample coal sample left in step one is then covered with a lid
and placed in an electric furnace maintained at 925 degree Celsius
• The crucible is taken out of the electric 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
Formula :
% of volatile matter = Loss in weight due to removal of volatile matter/Wt.
of coal taken x 100
iii) Determination of Ash content in coal-
• The residual coal in the crucible from last step is then heated without lid
in a muffle furnace at 700 degree Celsius for half an hour.
• The crucible is taken out of the electric oven, cooled first in air, then
inside a desiccator and weighed again
• Heating, cooling and weighing is repeated, till a constant weight is
obtained. The residue is reported as ash on percentage basis.
• Formula :
% of Ash = Weight of ash left /Wt. of coal taken x 100
iv) Determination of fixed carbon in coal-
• Percentage of fixed carbon
• Formula :
% of fixed carbon = 100 - % of (moisture + volatile matter + ash)
Significance of proximate analysis: Proximate analysis provides some
information in assessing the quality of coal.
Moisture: Moisture lowers the calorific value of coal so lesser the moisture
content, better is the quality of coal.
Volatile Matter: Higher volatile content is undesirable which reduces calorific
value. Hence lesser the volatile matter, better is the quality of coal
Ash content: It is useless, non combustible matter, which reduces the calorific
value of coal. So lower the percentage of ash, better is the quality of coal.
Fixed carbon: Higher the percentage of fixed carbon, greater is its calorific value
and better is the quality of coal.
Lithium-ion battery- Class notes.
Electrochemical sensors-
Sensor is a device which is able to detect a change in physical / chemical
quantity and produce an electrical signal suitable for a computer.
Ex- colour sensor, Temperature Sensor, Gas Sensor… etc.
These sensors work to make our lives easier.
Functions–
Electrochemical sensor is one of the broadest and oldest types of sensors.
They are used in quantitative analysis-
For the analysis of inorganics in complex aqueous matrices.
For the detection of metal ions i.e. Cu2+, Pb2+, Zn2+ etc.
For measurements of non-metals such as CN-, Cl-, Br-.
pH can also be determined
For detection of oxygen and toxic gases.
Construction-
The electrochemical sensor cell consists of a casing containing an
electrolyte gel and three electrodes.
The side of a casing has a gas permeable membrane and a gas capillary.
These sensors are composed of noble metal electrodes i.e. silver, gold or
platinum.
The electrolyte is normally an aqueous solution of strong inorganic acids.
In its simplest form electrochemical sensors consist of –
1. A Diffusion barrier
2. Anode- sensing / working/ measuring electrode
3. Cathode- Counter electrode
4. An electrolyte
5. Reference electrode
The electrochemical sensor may be considered to be comprised of two
main sections namely the electrochemical sensor cell and the supporting
electronics i.e amplifier, register, thermistor and microchip.
The rest of the instrument provides for the electrical supply requirements
of the sensor, amplifies the signal and display it in a meaningful way.
Working principle-
Electrochemical sensors are used primarily to detect oxygen and toxic
gases.
Each sensor is designed to be specific to the gas, it is intended to detect.
Electrochemical sensors use a chemical reaction to measure the
concentration of specific gas in an environment.
In an environment free of chemically reactive gases, oxygen diffuses into
the cell and adsorbs on both electrodes.
The result is a stable potential between the two electrodes in which little or
theoretically no current flows.
When a chemically reactive gas passes through the diffusion barrier, it is
either oxidized or reduced depending upon the gas, thereby resulting
potential difference between the two electrodes causes a current to flow.
For ex. – When carbon monoxide a reducing gas diffuses to the anode, it is
oxidized thereby causing the potential of the anode to shift in negative
direction.
This cell utilizes a third electrode called reference electrode which has the
following functions-
1. It has a stable potential from which no current is drawn.
2. It eliminates interference from side reactions with the counter electrode.
Applications-
To detect oxygen and toxic gases ( CO, H2S, SO2, NO,NO2,etc)
To monitor waste stream discharges (BOD,COD)
Environmental monitoring of air quality.
Detection of explosive gases and toxic vapours.
Oxygen monitoring in the medical sector.
Food quality control.
