Research 2

MAPUA INSTITUTE OF TECHNOLOGY
Muralla St. Intramuros, Manila

School of Mechanical Engineering and Manufacturing Engineering
Research 2
OXYGEN BOMB CALORIMETER AND
ORSAT APPARATUS
8 JEREMIAS, John Karlo B.
Date of Submission: September 17, 2015
ME139L / A3
Group 1
GRADE
Engr. Teodulo A. Valle

Instructor
TABLE OF CONTENTS
PART 1
OXYGEN BOMB CALORIMETER
PAGE
OBJECTIVES
INTRODUCTION
HISTORY OF CALORIMETRY
CONCEPTS AND THEORIES INVOLVED
HEAT
HEAT OF COMBUSTION
HEAT TRANSFER
THERMAL ENERGY
HEAT CAPACITY
INTERNAL ENERGY
ENTHALPY
FIRST LAW OF THERMODYNAMICS
SPECIFIC HEAT
TEMPERATURE
PRESSURE
GENERAL TYPES OF CALORIMETER
CALORIMETER SELECTION
BOMB CALORIMETER (IN DEPTH)
CHARACTERISTICS
10
PARTS AND FUNCTIONS
11
DESIGN
15
GENERAL PROCEDURE
16
CALIBRATION
20
SAFETY CONSIDERATIONS
21
TABLE OF CONTENTS
PART 2
ORSAT APPARATUS
PAGE
OBJECTIVES
23
INTRODUCTION
23
ORSAT APPARATUS
25
GAS ANALYSIS
26
ORSAT APPARATUS CONSTRUCTION
27
METHODS OF ANALYSIS
28
FLUE GAS ANALYSIS BY ORSAT APPARATUS
29
MODERN ANALYZERS DERIVED FROM ORSAT APPARATUS
30
SETTING-UP THE ORSAT APPARATUS
31
GOVERNING CHEMICAL ABSORPTION IN ORSAT APPARATUS
32
LEAK-CHECK PROCEDURE FOR ORSAT ANALYZER
33
REFERENCES
34
RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2
Part 1
OXYGEN BOMB CALORIMETER
OBJECTIVES
1. To be able to learn the operation of a bomb calorimeter
2. To be familiar with the parts of a bomb calorimeter.
3. To be able to learn the determination of the heat of combustion of different
compounds.
INTRODUCTION
Calorimetry
(klrmtr)
is
the
measurement of heat and the determination of heat

capacity. Heat is evolved in exothermic processes
and absorbed in endothermic processes; such
processes include chemical reactions, transitions
between the states of matter, and the mixing of two
substances to form a solution. A number of different
Simple Calorimeter
units are used in heat measurement, e.g., the calorie, the British thermal unit (Btu), and
the joule. The apparatus used in heat measurement is called a calorimeter. The
measurement given by the most common type of calorimeter depends upon the
temperature change in a fixed quantity of water (or some other liquid whose heat capacity
is known) when heat is transferred between the water and an exothermic or endothermic
process. If the temperature change is not too large, then the heat transferred is equal to
the heat capacity of the water times the mass of the water times the change in
temperature. The accuracy of this method of heat measurement depends on the
assumption that all the heat transferred in the process passes into or out of the water in
which the temperature change is measured, no heat being lost to the environment and
none being absorbed by the walls of the container. The amount of heat given off by the
combustion of a fuel can be determined very accurately in the so-called bomb calorimeter,
which consists of a combustion chamber (the "bomb") set in another chamber filled with
water. Heat generated by combustion of the fuel is transmitted to the water, raising its

temperature. The calorie content of food is tested
this way. Calorimeters are also employed to
measure the energies of elementary particles.
HISTORY OF CALORIMETRY
Little productive work on the measurement of
heat changes was accomplished prior to the midnineteenth century for two reasons. First, the exact
nature of heat itself was not well understood. Until
the work of the Scottish chemist Joseph Black in the
late eighteenth century, the distinction between
Ice Calorimeter
The world's first ice-calorimeter, used in the winter of
1782-83, by Antoine Lavoisier and Pierre-Simon
Laplace, to determine the heat evolved in
variouschemical changes; calculations which were
based on Joseph Black's prior discovery of latent
heat. These experiments mark the foundation of
thermochemistry.
temperature and heat was not at all clear. It then

took until about 1845 before the nature of heat as a
form of energy and not of matter was made clear in
the experiments of James Joule and others.

Secondly, given such uncertainties, it is hardly surprising that appropriate
equipment for the measurement of heat changes was not available until after the 1850s.
Lavoisier and Laplace had made use of a primitive ice calorimeter to measure the heats
of formations of compounds in 1780, but their work was largely ignored by their colleagues
in chemistry.
In fact, credit for the development of modern techniques of calorimetry should
probably be given to the French chemist Pierre Eugne Berthelot (1827-1907). In the
1860s, Berthelot became interested in the problems of heat measurement. He
constructed what was probably the first modern calorimeter and invented the terms

endothermic and exothermic to describe reactions in which heat is taken up or given off,
respectively.
CONCEPTS AND THEORIES INVOLVED
Heat
Heat may be defined as energy
in
transit
from
high temperature object to a

lower temperature object. Heat
released in a chemical reaction
can
be
experimentally
determined
by
using
an
adiabatic calorimeter. The reaction must proceed without any side reactions and
sufficiently fast that the heat exchange with the surroundings is negligible. The
heat of combustion can be most conveniently measured using an adiabatic bomb
calorimeter. In such calorimeter, the combustion reaction occurs in a closed
container under constant volume (bomb). The bomb is immersed in a weighted
quantity of water and surrounded by an adiabatic shield that serves as a heat
insulator. Continuous stirring ensures that heat is distributed evenly in the
calorimeter. The bomb and the water bath,
which are in direct thermal contact,
constitute an adiabatic bomb calorimeter.
Heat of Combustion
The
heat
of
combustion
(Hc0)
is
the energy released by the substance

as
heat
when
Heat of Combustion
compound
undergoes
complete combustion with oxygen under standard conditions. The chemical

reaction is typically a hydro carbon reacting with oxygen to form carbon

dioxide, water and heat. The heat of combustion is conventionally measured with
a bomb calorimeter. It may also be calculated as the difference between the heat
of formation (fH0) of the products and reactants.
Heat Transfer
Heat transfer is a path function

(process quantity), as opposed to a point
function (state quantity). Heat flows between
systems that are not in thermal equilibrium
with each other; it spontaneously flows from
the areas of high temperature to areas of low
Modes Of Heat Transfer
temperature. Heat may be transferred by

conduction, convection or radiation. Conduction or diffusion is the transfer of
energy between objects that are in physical contact. This is most evident in metals.
In conduction, Fouriers Law is applied to obtain the heat transfer.
=
where k is thermal conductivity constant, A is the area perpendicular to the

direction of heat transfer T is temperature change and x is thickness.
Meanwhile, convection is the transfer of energy between an object and its
environment, due to fluid motion. Convection may be classified as natural or
forced convection. Forced convection employs the use of work to abruptly drive
fluids, whereas natural convection allows transfer of heat without working
mechanisms. Heat transfer by convection is obtained by using Newtons Law of
Cooling:
=
where h is the convective heat transfer constant, A is the Area and T is
temperature change. Finally, radiation is the transfer of energy to or from a body
by means of the emission or absorption of electromagnetic radiation. Heat transfer
by radiation is obtained by using Stefan-Boltzmann Equation:

= 4
Where A is the area, is emissivity, is Boltzmann Constant (5.67x108 W/m2K4),
and T4 is the fourth power or the change in temperature.
Thermal Energy
Thermal energy is the part of the total internal energy of a thermodynamic
system or sample of matter that results in the system's temperature. The internal
energy, also often called the thermodynamic energy, includes other forms of
energy in a thermodynamic system in addition to thermal energy, namely forms
of potential energy, such as the chemical energy stored in its molecular structure
and electronic configuration, intermolecular interactions, and the nuclear
energy that binds the sub-atomic particles of matter.
Heat Capacity
Heat capacity (usually denoted by a capital C, often with subscripts),
or thermal capacity, is the measurable physical quantity that characterizes the
amount of heat required to change a substance's temperature by a given amount.
In the International System of Units (SI), heat capacity is expressed in units
of joule(s) (J) per kelvin (K).
Internal Energy
Internal energy (U) is the total amount
of energy contained by a thermodynamic system.
It is the energy needed to create the system, but
excludes the energy to displace the system's
surroundings, any energy associated with a move
as a whole, or due to external force fields. Internal
Internal energy is the energy from

the inside of the material.
energy has two major components, kinetic

energy and potential energy. The kinetic energy is due to the motion of the
system's particles (translations, rotations, vibrations), and the potential energy is
associated with the static constituents of matter, static electric energy

of atoms within molecules or crystals, and the static energy of chemical bonds.
The internal energy of a system can be changed by heating the system or by
doing work on it.
Enthalpy
Enthalpy is a measure of the total energy of a thermodynamic system. It
includes the internal energy, which is the energy required to create a system, and
the amount
of
energy required
to make room for it
by displacing
its environment and establishing its volume and pressure. Enthalpy is

a thermodynamic potential. It is a state function and an extensive quantity. The
unit of measurement for enthalpy in the International System of Units (SI) is
the joule, but other historical, conventional units are still in use, such as the British
thermal unit and the calorie. It is obtained by using the expression:
= +
where U is the change in the internal energy and pV as the change is flow work.
First Law Of Thermodynamics
The first law of thermodynamics states that the energy of a closed system
is conserved. Therefore, to change the energy of a system, energy must be
transferred to or from the system. Heat and work are the only two mechanisms by
which energy can be transferred to or from a control mass. Heat is the transfer of
energy
caused
by
the
temperature
difference.
The
first
law
of
thermodynamics states that the increase in internal energy is equal to the total
heat added and work done. If the system is isolated, its internal energy cannot
change.
=
Specific Heat
Specific heat is defined as the amount of energy that has to be transferred
to or from one unit of mass or mole of a substance to change its temperature by

one degree. Specific heat is a property, which means that it depends on the
substance under consideration and its state as specified by its properties.
Temperature
Temperature is a physical property of a system that underlies the common
notions of hot and cold; something that is hotter generally has the greater
temperature. Temperature is one of the principal parameters of thermodynamics.
The basic unit of temperature (symbol: T) in the International System of Units (SI)
is the kelvin (K).
Pressure
Pressure is the force per unit area applied in a direction perpendicular to
the surface of an object. Gauge pressure (also spelled gage pressure) is the
pressure relative to the local atmospheric or ambient pressure. Atmospheric
pressure is the pressure at the atmosphere. Absolute pressure is the sum of
absolute and gage pressure.
GENERAL TYPES OF CALORIMETER
1. Bomb Calorimeter
A bomb calorimeter is a type of constant-volume
calorimeter used in measuring the heat of
combustion of a particular reaction
2. Calvet Type Raction

The detection is based on a three-dimensional
flux meter sensor. The flux meter element consist
a ring of several thermo couple in series. The
corresponding thermopile of high thermal
conductivity surrounds the experimental space
within the calorimetric block. The radial
arrangement of the thermopile guarantees an
almost complete integration of the heat. This is
verified by the calculation of the efficiency ratio
that indicates that an average value of 94% +/- 1%
of heat is transmitted through the sensor on the
Bomb Calorimeter
Calvet Type

full range of temperature of the Calvet-type calorimeter. In this setup, the sensitivity
of the calorimeter is not affected by the crucible, the type of purge gas or the flow
rate. The main advantages of the setup is the increase of the experimental vessel's
size and consequently the size of the sample without affecting the accuracy of the
calorimetric measurement.
3. Constant Pressure Calorimeter
A constant-pressure calorimeter measures the change in enthalpy of a reaction
occurring in solution during which the atmospheric
pressure remains constant
4. Differential Scanning Calorimeter
In a differential scanning calorimeter (DSC), heat flow into
a sample usually contained on the small aluminium
capsule or 'pan' is measure differentially. By comparing it
into an empty reference pan.
5. Isothermal Titration Calorimeter
In an isothermal titration calorimeter, the heat of reaction
is used to follow a titration experiment
.
Isothermal Titration
Calorimeter
Differential Scanning
Calorimeter
Constant Pressure
Type

CALORIMETER SELECTION
The principal factors affecting selection of a calorimeter for a specific application
deal with the precision required and the anticipated workload, and not with the type of
sample to be tested. The same calorimeters are used for all oxygen combustible samples;
solids and liquids alike. Special sample holders and specific techniques may be required
for holding volatile liquid samples to prevent evaporation loss during weighing operations,
and certain additives may be required to obtain complete combustion of slow-burning
samples, but with only a few exceptions, all can be burned in the same oxygen bomb
using the same calorimeter system. Specially constructed, extra high strength bombs are
available for burning explosives and similar hazardous materials, and bombs with a
platinum lining or made of special corrosion resistant materials are available for use with
samples which liberate unusual amounts of fluorine, chlorine or other corrosive
combustion products.
Until recently, adiabatic calorimeters were the preferred choice in most industrial
laboratories. Modern adiabatic jackets with microprocessor controls can approach the
theoretical goal of eliminating all heat leaks, providing excellent precision in calorimetric
tests, but specialized jackets and control systems are required. Tests may be slower and
may require more externally supplied heating and cooling medium than an isoperibol
system.
Isoperibol calorimeters with their controlled constant temperature jackets are an
excellent choice for all calorific tests provided they are equipped with microprocessor
controls to monitor the test and to compensate for heat flow within the calorimeter.
BOMB CALORIMETER (In-Depth)
A bomb calorimeter is used for measuring energy released in a combustion
reaction. This reaction takes place in a water bath, so that the water absorbs the
energy released and we can measure how much its temperature rises accordingly.
A bomb calorimeters are used, they're instruments used in Chemistry and
they're used for measuring energy released in a combustion reaction. So we know that
combustion reactions are extremely exothermic meaning they release a lot of heat

when they go forward. So how do we know how much heat they actually do release?
Well we have this thing a bomb calorimeter and this is a very simple drawing of what
one looks like and essentially what happens is we have inside the bomb calorimeter
we have a reaction that's contained within a water bath. And so the reaction is going
to take place, the combustion reaction is going to release a lot of energy notice the
red around it saying energy, energy, energy and what that energy is going to do
according to the law of conservation of energy is going to, the same amount of energy
that's released is going to be absorbed by the water surrounding it. So we can actually
determine the amount of energy that this reaction is actually releasing by looking at
the temperature change of the water. Indirect calorimetry calculates heat that living
organisms produce from their production of carbon dioxide and nitrogen waste (frequently
ammonia in aquatic organisms, or urea in terrestrial ones), or from their consumption
of oxygen. Lavoisier noted in 1780 that heat production can be predicted from oxygen
consumption this way, using multiple regression.
CHARACTERISTICS OF BOMB CALORIMETERS:
Heats of combustion as determined in an oxygen bomb calorimeter are
measured by a substitution procedure in which the heat obtained from the sample
is compared with the heat obtained from combustion of a similar amount of benzoic
acid or other standardizing material whose calorific value is known. These
measurements are obtained by burning a representative sample in a highpressure
oxygen atmosphere within a metal pressure vessel or bomb. The energy
released by this combustion is absorbed within the calorimeter and the resulting
temperature change within the absorbing medium is noted. The heat of combustion
of the sample is then calculated by multiplying the temperature rise in the
calorimeter by a previously determined energy equivalent or heat capacity
determined from previous tests with a standardizing material. Corrections must be
applied to adjust these values for any heat transfer occurring in the calorimeter, as
well as for any side reactions which are unique to the bomb combustion process.
Four essential parts are required in any bomb calorimeter: (1) a bomb or
vessel in which the combustible charges can be burned, (2) a bucket or container
10

for holding the bomb in a measured quantity of water, together with a stirring
mechanism, (3) an insulating jacket to protect the bucket from transient thermal
stresses during the combustion process, and (4) a thermometer or other sensor
for measuring temperature changes within the bucket.
The bomb must be a strong, thick-walled metal vessel which can be opened
for inserting the sample, for removing the products of combustion and for cleaning.
Valves must be provided for filling the bomb with oxygen under pressure and for
releasing residual gases at the conclusion of a test. Electrodes to carry an ignition
current to a fuse wire are also required. Since an internal pressure up to 1500 psig
can be developed during combustion, most oxygen bombs are constructed to
withstand pressures of at least 3000 psig.
In the moist, high-pressure oxygen environment within a bomb, nitrogen
present will be oxidized to nitric acid, sulfur present will be oxidized to sulfuric acid,
and chlorine present will be released as a mixture of chlorine and hydrochloric
acid. These acids combine with the residual high temperature oxygen to form a
corrosive vapor which will etch ordinary metals. Therefore the bomb must be made
of materials which will not be attacked by these combustion products. Parr oxygen
bombs are made of complex high-chromium-nickel alloys which have proven to be
particularly well suited for this purpose, as demonstrated by the many thousands
of these bombs which are still in service after having been used for many years.
The calorimeter bucket must be carefully designed with sufficient capacity
to hold the bomb completely submerged in water, with a probe to read temperature
and a stirrer included to promote rapid thermal equilibrium without introducing
excessive heat in the form of mechanical energy. Buckets are commonly made
with a highly polished outer finish to minimize the absorption and emission of
radiant heat.
Parts and Functions
11

In the oxygen bomb calorimeter there are three main parts: a.) A bomb,
which houses the sample and oxygen for the combustion reaction; b.) The steel
bucket, which holds a measured amount of water, thermometer and the bomb;
and c.) The outer jacket, which thermally insulates the entire apparatus. Specific
Oxygen Bomb Calorimeter Parts and

Components
Parts and Functions:
1. Oxygen Supply delivers/provides oxygen to the oxygen chamber/crucible.
2. Ignition Wires facilitates the detonation or blast off of the sample specimen.
3. Stirrer hasten the rate of diffusion of heat through the water.
4. Insulating Jackets prevents major heat losses in the system. This is made
from highly insulating material.
5. Bucket holds the bomb, water and the sample together.
6. Heater maintains the heat of the steel bomb at constant temperature before
and after the explosion.
7. Water absorbs the heat released by the ignition of the specimen.
8. Ignition Coils directly heats up and ignite the sample to blast.
9. Steel Bomb seals the oxygen and the crucible containing the sample together.
It also transmits heat of the ignited/combusted substance to water.
12

10. Crucible holds or contains the sample specimen/substance to be tested
11. Air Space provides additional insulation to the system
12. Magnifying piece facilitates easier temperature reading.
13. Thermometer displays the temperature of the sample (before and after
combustion).
Four essential parts are required in any bomb calorimeter: (1) a bomb or
vessel in which the combustible charges can be burned, (2) a bucket or container
for holding the bomb in a measured quantity of water, together with a stirring
mechanism, (3) an insulating jacket to protect the bucket from transient thermal
stresses during the combustion process, and (4) a thermometer or other sensor
for measuring temperature changes within the bucket.
The bomb must be a strong, thick-walled metal vessel which can be opened
for inserting the sample, for removing the products of combustion and for cleaning.
Valves must be provided for filling the bomb with oxygen under pressure and for
releasing residual gases at the conclusion of a test. Electrodes to carry an ignition
current to a fuse wire are also required. Since an internal pressure up to 1500 psig
can be developed during combustion, most oxygen bombs are constructed to
withstand pressures of at least 3000 psig.
In the moist, high-pressure oxygen environment within a bomb, nitrogen
present will be oxidized to nitric acid, sulfur present will be oxidized to sulfuric acid,
and chlorine present will be released as a mixture of chlorine and hydrochloric
acid. These acids combine with the residual high temperature oxygen to form a
corrosive vapor which will etch ordinary metals. Therefore the bomb must be made
of materials which will not be attacked by these combustion products. Some
oxygen bombs are made of complex high-chromium-nickel alloys which have
proven to be particularly well suited for this purpose, as demonstrated by the many
thousands of these bombs which are still in service after having been used for
many years.
The calorimeter bucket must be carefully designed with sufficient capacity
to hold the bomb completely submerged in water, with a probe to read temperature
13

and a stirrer included to promote rapid thermal equilibrium without introducing
excessive heat in the form of mechanical energy. Buckets are commonly made
with a highly polished outer finish to minimize the absorption and emission of
radiant heat.
The bomb and bucket are held in a calorimeter jacket which serves as a
thermal shield, controlling any heat transfer between the bucket and the
surroundings. The jacket will minimize the effects of drafts, radiant energy and
changes in room temperature during a test, but it may not completely eliminate all
heat leak. Therefore it is necessary to have a means for establishing precisely the
amount of heat transferred during a test, or controlling the transfer so that it is
uniform from one test to another.
Several types of jacketing systems are used in oxygen bomb calorimeters.
The simplest of these is the uncontrolled or plain insulating jacket. With this type
of jacket it is assumed that the jacket temperature will remain constant throughout
the test without employing an auxiliary temperature control system. Because of
their simplicity, plain jacket calorimeters are recommended mainly as a low cost
instrument for users who make only occasional calorific tests, or whose workload
does not justify the purchase of a temperature controlled model. A plain jacket
calorimeter requires no permanent connections. It can be set up and ready to
operate in a few minutes, and when not in use it is easily disassembled for storage.
For best precision, the temperature of the calorimeter jacket must be closely
controlled. This usually requires a water filled jacket equipped with a means for
adjusting the jacket temperature, either by an immersion heater or by hot and cold
water injections. With a temperature controlled jacket the calorimeter can be
operated either in an adiabatic or isoperibol mode. In an adiabatic system the
jacket temperature is adjusted continuously during a test to keep it equal at all
times to the temperature in the bucket. Thus, by maintaining a zero differential
between the jacket and bucket, there will be no heat transfer between the jacket
and bucket, there will be no heat transfer between these components and the
calculations and corrections required for an uncontrolled or isoperibol system can
be eliminated.
14

BOMB CALORIMETER DESIGN
The design of a typical bomb calorimeter is shown in the Figure. The
material to be analyzed is deposited inside a steel reaction vessel called a bomb.
The steel bomb is placed
inside a bucket filled with
water, which is kept at a
constant temperature relative
to the entire calorimeter by use
of a heater and a stirrer. The
temperature of the water is
monitored with a thermometer
fitted
with
eyepiece,
accurate
taken.
magnifying
which
readings
Heat
allows
to
losses
Bomb Calorimeter Design
be
are
minimized by inserting an air

space between the bucket and an exterior insulating jacket. Slots at the top of the
steel bomb allow ignition wires and an oxygen supply to enter the vessel, both of
which are critical in starting the chemical reaction. When an electric current passes
through the ignition coil, a combustion reaction occurs. The heat released from the
sample is largely absorbed by the water, which results in an increase in
temperature.
Operations
A bomb calorimeter works by the ignition of a sample in an excess of
oxygen. This is achieved by pressurizing a number of times up to 25 atmospheres.
These pressurizations are needed to ensure that the bomb has had all the air (and
moisture) removed from the bomb and be replaced by an excess of oxygen. The
oxygen is required to ensure complete combustion of a sample. The ignition is
initiated by passing a large voltage across a bare fuse wire which has been suitably
fixed into the sample.
15

Bomb calorimetry is used to determine the enthalpy of combustion, DcombH, for
hydrocarbons:
CxHYOz (s) + (2X+Y/2-Z)/2 O2 (g) X CO2 (g) + Y H2O (l)
Since combustion reactions are usually exothermic (give off
heat), DcombH is typically negative. (However, be aware that older literature
defines the "heat of combustion" as -DcombH, so as to avoid compiling tables of
negative numbers!)
It can be clearly seen that the system is prone to errors by either fuse wire
breaking or the cotton coming adrift with the increase of gas pressure on
pressurization. The actual heat of formation is the change in heat content when
one mole of compound is formed from its constituent elements in their standard
physical states at 298.15K and 1 atmosphere pressure.
General Procedures
1) Prepare the sample
For best results and for safety purposes it
is desirable to use sufficient amount of sample to
produce a temperature rise of about 2.0 C starting
from
temperature
somewhat
below
room
Sample Preparation
temperature.
16

Warning: DO NOT USE MORE THAN ONE GRAM
2) Attach the wires to the electrodes.
All manipulations prior to closing the bomb can be performed by
holding the bomb head in the support. Cut a single length of the nickel-alloy
wire, 10 cm long, from the provided card. Attach the wire to the electrodes of the
calorimeter. The wire must be tightly wrapped to reduce resistance. Attach one
end of the wire to the loop electrode; then attach the other end to the straight
electrode. Bend the wire up as in step 1 and insert the capsule into the loop
holder.
Warning: AVOID SHORTING WIRE TO CAPSULE
3) Place water in the bomb.
Place 1.0 ml of distilled water in the bomb from a pipette. This amount
of water serve to saturate the oxygen as an aid in combustion and to assure
that water resulting from combustion is in the liquid state and also to dissolve any
acid formed. Place the bomb head with the fuse wire attached to the firing leads
and capsule containing the sample in position in the bomb and close the bomb.
Then, place on the screw ring with great care until you are sure the threads are
properly meshed; only then should an attempt be made to screw it all the way
on. The bomb is self-sealing and is closed simply by screwing the cap down firmly
by hand.
4) Fill the bomb with oxygen.
17

Attach the filling connection to the
bomb inlet valve in the following manner:
With the bomb placed in the bench
clamp remove the inlet thumb nut and
attach the filling tube, drawing the union
nut down moderately tight. Close the
control valve on the filling connection,
Pressurize the bomb with oxygen
and open or "crack" the oxygen tank valve not more than one quarter turn.
Open the filling connection control valve slowly. Observe the gauge and allow the
pressure to rise slowly until a pressure of 25 atmospheres is reached, then close
the control valve. If by accident, the oxygen pressure, introduced into the
bomb,
should
ever
exceed
30
atmospheres,
DO
NOT
under
any
circumstances, ignite the charge. The dangerously high pressures which can
be developed under such conditions might cause the bomb to explode.
5) Place the bomb on the bucket and then fill the bucket with water.
Grasp the bomb valve between
the thumb and forefinger and lower the
bomb into the bucket; taking care to avoid
jarring or disturbing the contents. Set the
bomb with its feet spanning the location
and turned so that the electrode terminal is
near the insulated ignition wire. Attach
the thrust terminal to the bomb electrode.
18
The bomb is placed on the

bucket and was filled with water.

Add 2000 ml of water to the bucket (use the provided volumetric flask).Place
the cover on the jacket with the thermocouple toward the operator. Lower
the cover into position, using care to avoid striking the thermocouple against
anything. The location pin at the rear of the cover should fall into the hole
on the top rim of the jacket. Put on the rubber drive belt and start the motor.
6. Read and record the initial temperature
Read and record the temperature to the nearest 0.005 F (0.002 C).
7. Run the motor for 5 minutes to attain thermal equilibrium.
Be prepared to take temperature readings as soon as equilibrium is
indicated by a slow uniform rise.
8. Fire the charge (by switching the ignition switch on) at the start of the sixth
minute.
Record the exact time and temperature at the firing point. After firing,
approximately 20 seconds will elapse before the mercury starts to rise. The rate
of rise will be rapid during the first few minutes and decrease as the calorimeter
approaches maximum temperature. Temperature readings should be recorded at
15-second intervals during the first two minutes and at one minute intervals
thereafter until successive readings is constant.
9. Open the calorimeter and examine the interior of the bomb.
At the completion of a test, stop the motor, remove the belt, and lift
the cover from the jacket. Wipe the thermocouple with a clean dry cloth and set
the cover on the support stand. Disconnect the firing connection from the bomb
terminal and lift the bucket and bomb out of the jacket. Replace the cover and
19

thermocouple on the empty jacket. Lift the bomb out of the bucket and relieve
all residual pressure. This should be done slowly and at a uniform rate. After all
pressure has been relieved, remove the screw cap, lift out the bomb head and
place it on the support stand.
Examine the interior of the bomb for soot or other evidence of incomplete
combustion. Discard the test if any is found.
10. Calculate the heat of reaction of the substance.
Calibration Procedures
a. Estimating Cv
The heat capacity of the bomb calorimeter can be estimated by considering
the calorimeter to be composed of 450 g water and 750 g stainless steel. Knowing
the specific heat capacity of water to be 1 cal/gK and estimating the specific heat
capacity of steel to be 0.1 cal/gK yields
b. Measuring Cv
For accurate work, the heat capacity of the calorimeter must be
measured.
This is done by depositing a known amount of energy into the
calorimeter and observing the temperature increase.
The two most common
methods for measuring Cv are

1. Burning a standard with known DU, e.g., benzoic acid.
mbenzoic acid DUbenzoic acid = mbenzoic acid -6318 cal/gK = -Cv DT
20

2. Doing electrical work by passing current though a resistor.
DU = w + q = VIt + 0 = Cv DT
Safety Considerations
Combustion reactions in an oxygen bomb calorimeter need not be considered
unusually hazardous as they are carried out routinely in thousands of laboratories.
Nevertheless, since they do involve nearly explosive reactions at high pressures, constant
vigilance is required to ensure safe operation. Care must be taken when charging the
bomb to be sure that the amount of sample placed in the bomb and the charging pressure
do not exceed the limits prescribed for the bomb being used.
It is extremely important that the bomb be maintained in good repair at all times.
Any bomb that is leaking oxygen from a valve, from an electrode or from any other seal
should never be fired. The combined flame front and high pressure oxygen released
under such conditions can ignite the bomb itself in the area of the leak. Each bomb should
also be subjected to hydrostatic and proof tests on a regular basis to confirm that it has
not been weakened by corrosion or wear, and that it is suitable for continued service.
Summarizing these basic safety rules, laboratory supervisors should insist upon
strict compliance with the following instructions:
A. Do not use too much sample. The standard 1108 bomb cannot be expected to
withstand the effects of combustible charges which liberate more than 8000 calories
frequently. This generally limits the total weight of combustible material (sample plus firing
oil, gelatin or any other combustion aid) to not more than 1.10 gram.
B. Do not charge the bomb with more oxygen than is necessary to obtain complete
combustion. As a rule, it is best to use the lowest gas pressure that will give complete
combustion. Lower pressures permit higher gas temperatures and greater turbulence,
both of which help to secure better combustion. The range of charging pressures for the
1108 bomb falls between 20 and 35 atmospheres, and should never exceed 40
atmospheres.
C. Keep all parts of the bomb especially the o-rings, insulated electrode assemblies and
valves in good repair at all times. Do not fire the bomb if gas bubbles are leaking from
the bomb when it is submerged in water.
21

D. Stand back from the calorimeter for at least 15 seconds after firing and, above all, keep
clear of the top of the calorimeter. If the bomb should explode it is most likely that the
force of the explosion will be directly upward.
E. Proceed with caution and use only a fraction of the allowable maximum sample when
testing new materials that may burn rapidly, or that may have explosive characteristics.
22

Part 2
ORSAT APPARATUS
OBJECTIVES:
1. To be able to learn the operation of the Orsat Apparatus
2. To be familiar with the parts and functions
3. To determine the flue gas or products of combustion parameters
INTRODUCTION
Flue gases are the outlet gases
obtained when a fuel is burned with air in
combustion equipment like engines and
boilers. Based on the fuel composition flue
gases are formed, a fuel having carbon and
hydrogen compounds generates flue gas
containing oxides of carbon and hydrogen
because the oxygen in air burns with
components that release heat energy and
resulting the combusted materials. In
construction
of
fire
heater,
boilers,
combustion engines and combuster the outlet
is given out with a cylinder shape chimney so
FLUE GAS REMOVAL
that the hot flue gases are eject into the
atmosphere. In design and calculating the performance of the above equipments the flue
gas is used for analysis which help to determine the composition of the carbon dioxide,
oxygen, nitrogen and carbon monoxide.
23

COMBUSTION ENGINE
Knowledge of composition of flue gases is important to mechanical engineers especially
those engaging in automotives. Cars have internal combustion engine which burns fuel
in presence of oxygen to provide power to the engine. It requires various elements
oxygen and nitrogen from air and carbon, hydrogen, sulfur and other trace elements from
fuel. The result of the combustion of fuel and oxygen are water and various gaseous
materials. Identification of the composition of the combustion by-products is important
since it will help in designing the parameters of cars, troubleshooting defects.
Normally, when a fossil fuel is combusted in the atmospheric air, the flue gas will mainly
consist of: Nitrogen (from air, also from the fuel), Carbon dioxide (product of carbon
oxidation), Water vapour (product of hydrogen oxidation) and Carbon monoxide (product
of incomplete carbon oxidation).
Knowing composition of the flue gas from an industrial process is quite important from
several points of view:
o Combustion process quality. Detection of certain flue gas components can prove
that the combustion process is carried out inefficiently. High carbon monoxide
content proves that there is not enough air (oxidiser) supplied or that it is not getting
properly mixed with the fuel. On the other hand excessive oxygen content proves
that the mixture is too lean, and therefore considerable masses of air might be
heated unnecessarily decreasing process efficiency.
o Environmental aspects. Excessive emissions of various harmful substances,
mainly nitrogen oxides and sulphur oxides are normally prohibited by legal
regulations.
o Possible influence on other processes if the flue gas is directly used in any kind of
equipment.
In industrial facilities the combustion process optimisation is mainly done with economy
in mind. This is important, as usually maximising combustion efficiency will also lead to
increased emission of pollutants (particularly nitrogen oxides). Generally therefore the
combustion optimisation is done in a way ensuring maximum possible efficiency which
enables meeting the emission limits (and thus avoiding high penalties).
24

ORSAT APPARATUS
The Orsat apparatus is used to measure volumes of carbon dioxide, oxygen and
carbon monoxide within a fixed volume
of a sample gas (100cc). However it is
not particularly accurate at detecting
very low concentrations.
The Orsat apparatus works using
a very simple method. To find the
volume of a particular gas within the
sample a fixed volume of the sampled
gas is passed through a specific solution
which absorbs only the required gas.
The remaining volume of the gas can
then be re- measured and compared
with the original volume to find the
proportion of a specific gas within the sample.
The sampled gas is passed through a sequence of solutions each removing one
of the gases and the remaining volume calculated afterwards. A solution of caustic potash
is used to absorb the carbon dioxide, a mixture of pyrogallic acid, caustic potash and
water is used to absorb the oxygen, and to remove the carbon monoxide a solution of
cuprous chloride is used. The orsat apparatus contains three cylinders, each filled with a
specific solution that will absorb either oxygen, carbon dioxide, or carbon monoxide. As
the gas sample is bubbled through each cylinder and the respective gas is absorbed, the
25

volume difference is recorded and a calculation gives % by volume of oxygen, CO2, and
CO.
GAS ANALYSIS
The general principles involved in the various processes of gas analysis are best
exemplified by a consideration of the quantitative estimation of the constituents of fuel
gases, such analytical tests being the chief task of gas examiners. Gasometric methods
are, strictly speaking, branches of volumetric analysis, one of the main divisions of
quantitative work.
The composition of a gas is usually expressed in
percentages by volume, as it is easier to measure a gas
than to weigh it. As, however, the volume of a gas
depends upon its temperature, pressure and moisture
content, all volumes must be compared at the same
temperature and pressure and further must be either dry
or fully saturated with moisture ; if the conditions under
which they are compared are not the same, the volumes
in each case must be referred to a standard condition. The standard usually em ployed
is the International Standard, in which all volumes are referred to the dry volume which
the gases would occupy at o C and 76omm. of mercury pressure. If V is the volume of a
gas saturated with moisture measured at t C and hmm. of mercury, and a is the vapour
pressure of water at t C (obtained from tables), then the volume V. at the standard
conditions is given by the equation:
26

Vo=V (ha) 273/760(273+t)
In Great Britain the gas industry is bound by statute to use a different standard,
namely the volume saturated with moisture at 6o F and 3oin. of mercury pressure.
Thus if V is the volume at t F and hin., the vapour pressure of water at t F being a,
then the volume under standard conditions is:
Vo=V (ha) r 7.64/(460+t)
Tables to facilitate these calculations are given in text-books of gas analysis.
The volumetric analysis of a gas is usually carried out on a small quantity,
ranging from 5 to Ioo cu.cm., and if this small sample is to be representative of a large
bulk of gas, special pre cautions must be taken to ensure that the sample is properly
taken. The methods employed in the volumetric analysis of gases are based on: (I)
Successive absorption of the constituents by suit able reagents each of which absorbs
one only; (2) burning the gas with air or oxygen and measuring the change in volume
and the amount of carbon dioxide produced; (3) selective oxidation by passing the gas
over suitable reagents; e.g., heated copper oxide.
ORSAT APPARATUS CONSTRUCTION
The apparatus consists essentially of a calibrated water-jacketed gas burette

connected by glass capillary tubing to two or three absorption pipettes containing
chemical solutions that absorb the gasses it is required to measure. For safety and
portability, the apparatus is usually encased in a wooden box. a device used to determine
the composition of a mixture of gases by passing the mixture through a series of solvents,
each of which absorbs only one of the gases. Also, Orsat analyzer.
27
The absorbents are:
Potassium Hydroxide (Caustic Potash)
Alkaline pyrogallol
Ammoniacal Cuprous chloride
The base of the gas burette is connected to a levelling bottle to enable readings to
be taken at constant pressure and to transfer the gas to and from the absorption media.
The burette contains slightly acidulated water with a trace of chemical indicator (typically
methyl orange) for colouration.
In construction of fire heater, boilers, combustion engines and combuster the outlet
is given out with a cylinder shape chimney so that the hot flue gases are eject into the
atmosphere. In design and calculating the performance of the above equipments the flue
gas is used for analysis which help to determine the composition of the carbon dioxide,
oxygen, nitrogen and carbon monoxide. Based on this analysis results the fuel inlet flow
rate, air flow rate and burner are controlled to get the efficiency of the fired heaters. By
the following presentation the flue gas analysis can be demonstrated by using Orsat
apparatus, of course this is a standard piece of equipment. Many high accurate digital
and portable devices are available to determine the composition of flue gas.
METHODS OF ANALYSIS:
By means of a rubber tubing arrangement, the gas to be analyzed is drawn into
the burette and flushed through several times. Typically, 100mls is withdrawn for ease of
calculation. Using the stopcocks that isolate the absorption burettes, the level of gas in
the leveling bottle and the burette is adjusted to the zero point of the burette.
28

The gas is then passed into the caustic potash burette, left to stand for about two
minutes and then withdrawn, isolating the remaining gas via the stopcock arrangements.
The process is repeated to ensure full absorption. After leveling the liquid in the bottle
and burette, the remaining volume of gas in the burette indicates the percentage of carbon
dioxide absorbed.
FLUE GAS ANALYSIS BY ORSAT APPARATUS

Flue gases are the outlet gases obtained when a fuel is burned with air in
combustion equipments like engines and boilers. Based on the fuel composition flue
gases are formed, a fuel having carbon and hydrogen compounds generates flue gas
containing oxides of carbon and
hydrogen because the oxygen in air
burns with components that release
heat energy and resulting the
combusted
materials.
In
construction of fire heater, boilers,

combustion engines and combuster
the outlet is given out with a cylinder
shape chimney so that the hot flue
gases are eject into the atmosphere. In design and calculating the performance of the
above equipments the flue gas is used for analysis which help to determine the
composition of the carbon dioxide, oxygen, nitrogen and carbon monoxide. Based on this
analysis results the fuel inlet flow rate, air flow rate and burner are controlled to get the
29

efficiency of the fired heaters. By the following presentation the flue gas analysis can be
demonstrated by using Orsat apparatus, of course this is a standard piece of equipment.
Many high accurate digital and portable devices are available to determine the
composition of flue gas.
Modern analyzers derived from Orsat apparatus
Based on the Orsat analyzing technique not only flue gases but process gas like
methane, propane and natural gas can be analyzed continuously in a process flow
streams. Many new models are reengineered and modified by electronic and automation
technology so that they do multi task in a process industry. They measure, control and
disengage the process systems. The demand for composition measurement in
continuous flow pipeline even at high temperature and pressures fulfilled by latest
engineered models that are nitrogen analyzer, oxygen analyzer, carbon dioxide analyzer,
methane analyzer.
These modules contain a measuring probe, a signal transmitter and receiver,
instrument air sockets, display and controls box. Measuring probes are developed based
on the membrane technology, a thin film membrane allow specified molecules to pass
through it and these molecules will affect the conductivity of the thermocouple type
system which give out signal proportional to the chemical molecules.
30

SETTING-UP THE ORSAT APPARATUS
A.
Secure apparatus on a steady platform, at a height that will place the instrument
at eye level (about 1 m above the floor level).
B.
Charge the reagents into appropriate pipettes; about 150 ml of each reagent will
be required.
C.
Place the levelling bottle on the Orsat shelf and add the confining liquid. Carefully
add or remove liquid to get the liquid level in the burette exactly on zero. (If the
bottle seems likely to overflow, glue a 25 mm wooden block onto the shelf to raise
the bottle.)
D.
Connect the sampling tube from the storage room to the inlet of the apparatus with
a clear, flexible plastic tube (6 mm internal diameter).
31

E.
Make sure there are no leaks in the connections of the apparatus and in the
sampling line
GOVERNING CHEMICAL ABSORPTION REACTIONS IN ORSAT APPARATUS

Typical flue gas analyzers measure the quantity of carbon dioxide, carbon
monoxide and oxygen by a chemical absorption principle. Based on the absorption factor
of these three components their respective absorbing solutions are selected in three
different bulb compartments. When the gas is passed into these bulbs consecutively,
where each component is separated in sequence that helps to know the volume drop
from initial flue gas volume.
Water vapor in flue gas removed by adsorption on solid calcium chloride and then
passed into three pipettes. The sequence of absorption should always be started from
CO2, O2 and CO if the absorption solutions are ammoniacal cuprous chloride; alkaline
pyrogalic acid and KOH were selected as reagent in the analyser.
Gas then passed into KOH (potassium hydroxide) solution pipette to absorb
CO2 to form potassium carbonate by the reaction 2KOH + CO2 K2CO3+ H2O at
ambient conditions.
After confirming no change in the volume of reservoir than gas led to alkaline
pyrogallic acid containing pipette to absorb oxygen by the reaction:
2C6H3(OH)3(pyrogallol) + 2KOH(saturated alkaline)+ O2 4H2O

+ 2C5H3OCOOK and a physical color change is observed.
Finally carbon monoxide is absorbed by ammoniacal cuprous chloride pipette by

the reaction,
32
2CuCl + 2CO (in NH3 solution) [CuCl(CO)]2
LEAK-CHECK PROCEDURE FOR ORSAT ANALYZER

Moving an Orsat analyzer frequently causes it to leak. Therefore, an Orsat analyzer
should be thoroughly leak checked on site before the flue gas sample is introduced into
it. The procedure for leak checking an Orsat analyzer is as follows:
o Bring the liquid level in each pipette up to the reference mark on the capillary tubing,
and then close the pipette stopcock.
o Raise the leveling bulb sufficiently to bring the confining liquid meniscus onto the
graduated portion of the burette and then close the manifold stopcock.
o Record the meniscus position.
o Observe the meniscus in the burette and the liquid level in the pipette for movement
over the next 4 minutes.
o For the Orsat analyzer to pass the leak check, two conditions must be met:
o The liquid level in each pipette must not fall below the bottom of the capillary tubing
during this 4-minute interval.
o The meniscus in the burette must not change by more than 0.2 ml during this 4minute interval.
o If the analyzer fails the leak-check procedure, check all rubber connections and
stopcocks to determine whether they might be the cause of the leak. Disassemble,
clean and regrease leaking stopcocks. Replace leaking rubber connections. After
the analyzer is reassembled, repeat the leak-check procedure.
33

REFERENCES
http://www.scimed.co.uk/wp-content/uploads/2013/03/Introduction-to-bombcalorimetry.pdf
http://www.jhu.edu/chem/fairbr/teach/Exp%203.pdf
http://www.siamzim.com/pdf/calorimeters/TN_101.pdf
http://chemistry.bd.psu.edu/jircitano/Bomb.pdf
http://www.infralabindia.com/product.php?pid=513
http://en.wikipedia.org/wiki/Orsat_gas_analyser
http://www.gutenberg.org/files/22657/22657-h/chapters/fluegas.html
http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm
http://www.brightstorm.com/science/chemistry/thermochemistry/bombcalorimeters/
http://www.acornusers.org/education/Thesis/BombCalorimetry.html
http://chemistry.bd.psu.edu/jircitano/Bomb.pdf
http://www.inclusive-science-engineering.com/flue-gas-analysis-by-orsatapparatus/
http://en.wikipedia.org/wiki/Orsat_gas_analyser
http://gluedideas.com/Encyclopedia-Britannica-Volume-5-Part-1-Cast-IronCole/Gas-Analysis.html
http://www.merriam-webster.com/dictionary/orsat%20apparatus
http://www.jstor.org/stable/20021663
34

Research 2

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MAPUA INSTITUTE OF TECHNOLOGY

Muralla St. Intramuros, Manila

8 JEREMIAS, John Karlo B.

Date of Submission: September 17, 2015

Engr. Teodulo A. Valle

CONCEPTS AND THEORIES INVOLVED

FIRST LAW OF THERMODYNAMICS

GENERAL TYPES OF CALORIMETER

BOMB CALORIMETER (IN DEPTH)

PARTS AND FUNCTIONS

ORSAT APPARATUS CONSTRUCTION

FLUE GAS ANALYSIS BY ORSAT APPARATUS

MODERN ANALYZERS DERIVED FROM ORSAT APPARATUS

SETTING-UP THE ORSAT APPARATUS

GOVERNING CHEMICAL ABSORPTION IN ORSAT APPARATUS

LEAK-CHECK PROCEDURE FOR ORSAT ANALYZER

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

measurement of heat and the determination of heat

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

temperature and heat was not at all clear. It then

the experiments of James Joule and others.

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

high temperature object to a

the energy released by the substance

complete combustion with oxygen under standard conditions. The chemical

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

Heat transfer is a path function

Modes Of Heat Transfer

temperature. Heat may be transferred by

where k is thermal conductivity constant, A is the area perpendicular to the

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

Internal energy is the energy from

energy has two major components, kinetic

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

to make room for it

its environment and establishing its volume and pressure. Enthalpy is

First Law Of Thermodynamics

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

2. Calvet Type Raction

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

Oxygen Bomb Calorimeter Parts and

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

Bomb Calorimeter Design

minimized by inserting an air

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

Pressurize the bomb with oxygen

The bomb is placed on the

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

This is done by depositing a known amount of energy into the

calorimeter and observing the temperature increase.

The two most common

methods for measuring Cv are

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS

RESEARCH 2: OXYGEN BOMB CALORIMETER AND ORSAT APPARATUS