Bomb Calorimeter Principle

The amount of heat released or absorbed by any chemical process can be measured using an
insulated container called a "calorimeter." If the reaction in question occurs in an aqueous
solution, an effective calorimeter can be as simple as a Styrofoam coffee cup and a
thermometer.In this case, because the Styrofoam cup is an open container, the pressure is
constant, and measuring the heat is the same as measuring the change in enthalpy of a chemical
reaction (ΔH).

When the reaction occurs, the change in temperature will be proportional to the enthalpy released
by the reaction. For example, let's say that one mole of a substance can react inside 100 g of
water inside the calorimeter so that the water absorbs all the heat, and the temperature of the
water increases by 5 degrees. Using the mass of the water (m), the specific heat of the water (c),
and the change in temperature (ΔT), we can calculate the heat released by the reaction:

q = mcΔT = 100g • 4.18 J/g °C • 5°C = 2090 J = 2.09 kJ

Because one mole of the substance dissolved, the value of ΔH is -2.09 kJ/mol. Note that this
value is negative because the reaction gave off the enthalpy that the water absorbed.
 However, many chemical reactions, such as combustion reactions, do not take place in
a solution. To more efficiently measure the heat released by combustion reactions,
chemists use a bomb calorimeter, which is a sealed vessel that contains a smaller
container called a "bomb." The bomb (not related to a military weapon) is a container
designed to withstand high pressure, and is equipped with valves for adding gases and
electrical contacts for initiating combustion reactions. (Figure 7-11)
The basic principle is the same: A chemical reaction heats a quantity of water in an
insulated container. In this case, however, the reaction takes place inside a sealed
container, or bomb. The bomb contains the chemical to be analyzed and enough
oxygen to make sure the sample burns completely. The bomb sits submerged in a
container of water, and ignition wires start the combustion. Because the reaction takes
place in a rigid, sealed container, no pressure-volume work is done by the reaction; all
the energy will be released as heat, and none as work. In other words, a bomb
calorimeter always measures the heat that is released by a reaction, but in this case the
heat represents not the change in enthalpy (ΔH), but the change in internal energy
(ΔU). Conveniently, there are simple calculations that can be done to convert the
internal energy change into the enthalpy change chemists need.

Chemists have measured the change in enthalpy for thousands of different reactions
and have collected them into tables that can be found in almost any chemistry book. So,
there is no need for a chemist to perform calorimetry on a particular reaction, as that
value can be found in a table of enthalpies of reactions. (Section 8 will explain how an
enthalpy change for a reaction that is not in the table can be determined without doing a
new calorimetry experiment.)

Formula

A bomb calorimeter is a constant volume calorimeter (constant volume is isochoric). So the heat
measured by such an instrument is equivalent to the change in internal energy or ΔUΔU. The
heat can be determined from the temperature change, ΔTΔT, and the heat capacity of the
calorimeter, CcalCcal. For a bomb calorimeter, the heat capacity is usually quite large due to all
the water and the hardware (stirring paddles, blades, the stainless steel "bomb" holding the
reactants, the wiring, the walls of the calorimeter, etc...). This value is Ccal. It is used to
find qvqv of the system:
qcal=CcalΔT=−qv,systemqcal=CcalΔT=−qv,system
Sometimes, it is more convenient to split the overall heat capacity of the calorimeter into its
component parts: (1) the water, and (2) the hardware.

Ccal=Chardware+mwaterCs,waterCcal=Chardware+mwaterCs,water
The hardware heat capacity will be in units of J/K or kJ/K while the water heat capacity has to be
calculated from the mass of the water and the specific heat of water (4.184 J g-1 K-1). So the
water part is slightly variable due to the fact that you can fill the calorimeter up with slightly
different masses of water each time you use it. If you put all that into one formula for a bomb
calorimeter, you get:
qcal=ChardwareΔT+mwaterCs,waterΔTqcal=ChardwareΔT+mwaterCs,waterΔT
One last thing to note. Many tables will list heat capacities using °C instead of K. Realize that
these two units are equivalent in this context because we are using ΔTΔT and not plain TT. A
change in Kelvin of 10 is exactly a change of 10 in °C as well. So don't try to change Celsius to
Kelvin and vice versa here. This will be true throughout all your science courses.

Converting ΔUΔU to ΔHΔH

Chemists are almost always interested in the enthalpy change to know what would have
happened at constant pressure. It is possible to get ΔHΔH from a bomb calorimeter experiment.
It just takes an additional step to do a conversion from ΔUΔU to ΔHΔH.
To convert from ΔUΔU to ΔHΔH requires knowing the amount of work done (ww) during the
reaction. In the case of a chemical reaction, work can be easily calculated by simply counting
the number of moles of gas products and gas reactants.

Δngases=Σngasproducts−ΣngasreactantsΔngases=Σngasproducts−Σngasreactants
Now the work can be calculated with the formula:
work:w=−ΔngasesRTwork:w=−ΔngasesRT
So this leads to the final formula for the conversion:
ΔU=ΔH−ΔngasesRTΔU=ΔH−ΔngasesRT
or with a little algebraic rearranging...
ΔH=ΔU+ΔngasesRT

Principle and formula

What Is a Bomb Calorimeter?
A bomb calorimeter is a device that is designed to measure the amount of heat that is given off
or taken in by a reaction. It's designed to be isolated from the surroundings, meaning that no heat
can leave or enter the device. In order to accomplish this, the outside wall of the calorimeter is a
vacuum-sealed wall similar to an insulated mug you might carry coffee in. Inside the calorimeter
is a vessel in which the reaction occurs surrounded by a water bath. The temperature of the water
bath can be monitored via thermometer.
When a reaction takes place in the calorimeter, the temperature of the water bath changes. If an
exothermic reaction occurs, the water bath temperature goes up. If an endothermic reaction
occurs, the water bath temperature goes down.
In an ideal calorimeter, all the heat exchange would take place with the water. However, in real
life, the materials from the calorimeter itself, the stainless steel, thermometer, etc., exchange heat
with the system as well. We can correct for this by using a heat capacity for the calorimeter in
our calculations.
Because all the heat is exchanged inside the calorimeter, we can set the total heat to zero. We
have three terms for the three parts of our calorimeter: the calorimeter itself, the water bath, and
the chemical reaction, which you can see labeled in the equation below:

Substituting the equations for the heat of the water and the heat of the calorimeter, we get this
much more detailed equation:

Looking at this equation, you should note that the term for qcal has no mass. This is because it is assumed that
the mass of the calorimeter is constant and therefore can be included in Ccal .
Also note that ΔT should always be calculated as Tf (final temp) - Ti (initial temp). This means that if the
temperature of that object goes down, ΔT will be negative. Cp is the specific heat capacity for water and is 1
cal/g°C.
Looking at the equation below, you can see how we solve for qrxn :
 Procedure and operations of bomb calorimeter

In short, the process of a calorimeter involves measuring the heat of a fuel sample when burned
under stable temperature conditions to evaluate the heating energy of the fuel sample. The fuel
sample can be a solid or liquid, but not a gas.

Our calorimeters require approximately 0.5g of sample matter (i.e. food) weighed in a crucible. We
need to have the weight entered with four decimal places (i.e. 0.4972g) . Place crucible inside the
stainless steel container ("the bomb vessel") and fill bomb vessel with 30 bar (435psi or 30 atm) of
pure oxygen.
Place the filled bomb vessel inside the calorimeter and close the lid. The bomb vessel is now sealed
and isolated from outside temperature influences. Once the bomb vessel temperature has stabilized in
the bomb well, the sample is then ignited.

An electrical ignition charge instantly heats the ignition wire, which in turn burns the attached firing
cotton. The burning cotton thread falls into the fuel sample below causing the sample to ignite.
During the burning of the fuel sample, the crucible can momentarily rise to above 1000 Deg C with
the pressure spiking to 3 x the initial pressure. With in seconds, the heat of the reaction starts to
dissipate into the bomb vessel and the pressure starts to subside.

To accurately measure the temperature of the vessel, sensitive high resolution temperature sensors
are used, measuring every 6 seconds for the duration of the determination.

Once the determination is complete, typically within 4 minutes ( depending on which model you
have), the calorimeter calculates the Calorific Value ( CV ) of the fuel sample. At this point in time,
the bomb vessel is removed from the bomb well to be cooled. Typically the bomb vessel is now
between 8 to 14 Deg C higher in temperature.

Once the bomb vessel is sufficiently cooled in a cooler, it can be reused again.
 Reference
https://ch301.cm.utexas.edu/section2.php?target=thermo%2Fthermochemistry%2Fbomb-calorim.html

https://www.learner.org/courses/chemistry/text/text.html?dis=U&num=Ym5WdElUQS9PQ289&sec=YzJ
WaklUQS9OeW89

https://study.com/academy/lesson/bomb-calorimeter-definition-equation-example.html

https://www.ddscalorimeters.com/bomb-calorimeter-work/