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Bomb Calorimeter
ChE 124- Thermodynamics Laboratory
Under Prof. Dennis C. Ong

Barade. Esmaya. Mayagma. Rivera | September 2017


Introduction

Calorimetry is a technique used to measure the amount of


heat evolved in a chemical or physical process. It is used to measure
amounts of heat transferred from a given sample. To do so, the heat
is exchanged within a controlled and calibrated equipment.
Introduction

Calorimeter is a device used to measure

the amount of heat evolved in a combustion


process.

Bomb Calorimeter the temperature change is acquired after the


combustion reaction where heat flows to the water,
increasing its temperature. (Helmenstine, A. M., 2015)
Introduction
Introduction

Combustion is a type of oxidation reaction where one of


the reactants is oxygen and the other is the fuel either in its
gaseous, liquid or solid phase.
Introduction

Standard enthalpy of combustion is the

enthalpy change which occurs when one mole of the compound is


burned completely in oxygen under standard conditions. The heat of
combustion is utilized to quantify the performance of a fuel in a
combustion system such as furnaces, power generation turbines and
motors. (Heat of Combustion. (N.D.)
Introduction

d nU = 𝑑𝑄 + 𝑑𝑊
𝑑𝑊 = −𝑃 𝑑𝑉
Since the bomb calorimeter used maintains the volume at a constant
value, the change in work or the work produced will be equal to zero.

𝑑 𝑛𝑈 = 𝑑𝑄
The bomb calorimeter also assumes an adiabatic system so that heat
released or absorbed by the system will be equal to the heat absorbed or
released by the surroundings. (Smith, Van Ness, & Abbott, 2005) The heat Q
can then be calculated as follows:
−𝑞𝑠𝑦𝑠 = 𝑞𝑠𝑢𝑟𝑟 = 𝐶𝑐𝑎𝑙 Δ𝑇𝑠𝑢𝑟𝑟
Introduction

Heating value, also known as the calorific value is


defined as the heat produced after the complete combustion of a
unit of fuel.
Introduction

Presence of soot in the capsule after the combustion means


incomplete combustion of sample. The heat released by combustion
of fuse is accounted for by recognizing that:

∆U = ∆Usample·msample + ∆Uburnedfuse·mburned fuse = -Cv∆T


Introduction

Taking the sample as the system, the gross heat of combustion is


given by

And the enthalpy of combustion can then be calculated by


Introduction

Higher heating value (HHV) is the heat released when the


water produced is in its gaseous state while

the lower heating value (LHV) is equal to HHV minus the


latent heat of vaporization of the water molecules produced in the
reaction. (Laurito, 1994)
Introduction

Standardization- calibration of an oxygen bomb calorimeter


Introduction

Benzoic acid- a standard sample with known ΔU


Introduction

Naphthalene is a white, volatile, solid polycyclic

hydrocarbon with a strong mothball odor. It is obtained from either


coal tar or petroleum distillation and is primarily used to
manufacture phthalic anhydride, but is also used in moth
repellents. (U.S. National Library of Medicine. (N. D.)
Introduction

Butanol or butyl alcohol ( C H OH), a colorless


4 9

liquid, has been found as a minor product in the fermentation of

BUTANOL
sugars. It is considered as a potential biofuel and can be used in
cars designed for gasoline. It can also be added to diesel fuel to
reduce soot emissions.
Introduction

Based on Perry et al. (2008), the molar heat of combustion or the


higher heating value(kJ/mol) at 25°C of 1-Butanol ((CH3(CH2)3OH))
is -2454 kJ/mol. The reaction is given by

CH3(CH2)3OH + 6O2(g) → 4CO2(g) + 5H2O(l).


Objective

To calibrate the bomb calorimeter by


determining its heat capacity.
Objective

To determine the heating value of naphthalene.


Objective

To determine the heating value of butanol.


Materials

Graduated
Thermometer Cylinder
Ice packs

Fuse (Platinum Wire)

Sample (Benzoic acid,


Watch Glass naphthalene, butanol)
Materials

For the determination of heating value of a liquid fuel, Fume hood,


syringe, Butanol(sample), Gelatin Capsule were the additional
materials needed.
Methodology

Preparation of
Preparation of Preparation of Experiment
the Calorimeter
sample and fuse the bomb Proper
water
Preparation of sample

Weighing of Sample Molding of sample


in an Analytical into pellets using a
balance pelletizer

Pelletized sample
stored in a desiccator
Preparation of fuse

The material used as fuse to facilitate ignition of the benzoic acid

was 7-cm-long platinum wires. The wires were also


weighed then set aside until use.
Preparation of the bomb

Weighing of Pressurizing of
Cleaning of the Attachment of
Steel capsule the bomb
bomb head and fuse to the
(empty and (Pressure < 590
cylinder electrodes
with pellet) psig)
Preparation of the bomb

• NOTE!
Make sure that the fuse is in contact with the
sample to ensure occurrence of combustion
Preparation of the Calorimeter water

3 liters of calorimeter water with temperature of approximately


25ºC was prepared. The temperature was adjusted with the help of
ice packs that were made prior to the day of the experiment. After
attaining the desired temperature, the water was then transferred
to the Dewar of the calorimeter.
Experiment Proper

The sealed bomb was placed inside the dewar filled with
3 L of distilled water

then the two ignition wires were attached to the


terminal sockets of the bomb head and the
thermometer was placed into position in the
calorimeter cover.
Experiment Proper

After the cover was secured in place, the stirrer was turned on and
temperature was recorded for 6 minutes every 30 seconds interval.
In order to initiate combustion, the firing button was pressed for 1-2
seconds.
Experiment Proper

Temperature was then recorded for another 12 minutes also every


30 seconds interval. After a total of 18 minutes, the stirrer was
turned off then the set-up was allowed to settle for about 20
seconds before taking it out and cleaning the bomb.
Experiment Proper

The experimenters then observed if any deterioration occurred in


the bomb. Since none were observed, the bomb was taken out to an
open area and the gas was slowly released to depressurized it
before opening the screw cap.
Experiment Proper

Using tweezers, the unburnt fuse was then removed, inside the
steel capsule and on the electrodes, and weighed. The steel capsule
was also weighed after combustion. After the experiment, the bomb
was cleaned with distilled water and dried with a clean cloth. The
experiment was done for two trials.
CALIBRATION OF BOMB CALORIMETER

EXPERIMENT 1
Results & Discussion
Table 1. Change in temperature (corrected), internal energy, enthalpy and
the heat capacity of the calorimeter.

Trial 1 Trial 2
ΔT (oC) 1.168 1.166

ΔU (J/mol) -3095092.422 -3095092.511

ΔH (J/mol) -3.100E+06 -3.100E+06

Ccal(J/K) 𝟏𝟒𝟏𝟐𝟔. 𝟎𝟗𝟑 𝟏𝟒𝟑𝟗𝟏. 𝟒𝟒𝟗


Conclusion and Recommendation

After the calibration procedure, the heat capacity of the


calorimeter is 14,258.771 J/K which is an average for 2 trials. It is
recommended to conduct more than two trials in calibrating the
bomb calorimeter to get a more accurate result. Also, temperature
reading must be exact to obtain accurate and precise data and
results.
DETERMINATION OF HEATING VALUE OF A
SOLID PURE SUBSTANCE
USING A BOMB CALORIMETER
EXPERIMENT 2
Methodology

Preparation of
Preparation of Preparation of Experiment
the Calorimeter
sample and fuse the bomb Proper
water
Results & Discussion
Parameters Trial 1 Trial 2
Mass of sample (g) 0.8156 0.8082
Table 2.1 Recorded
Mass of wire (g) 0.0122 0.0119
weights before and after
Mass of steel capsule 12.8018 12.6667
combustion
(g)

Mass of capsule and 13.6063 13.4670


pelletized
Naphthalene (g)
Mass of capsule and 12.9407 12.8274
soot (g)
Mass of unburned fuse 0.0091 0.0093
(g)
Mass of burned fuse 0.0031 0.0026
(g)
Mass of combusted 0.6656 0.6396
naphthalene (g)
Results & Discussion
Table 2.2 Summary of calculated values
Ccal (from exp 1) 5213.967505 5138.649791 Mean:
(J/K) 5176.308648
Trial 1 Trial 2 Mean values
∆T (°C) 1.839 1.781 1.810
Qwire (J/mol) 48.230 𝟒𝟔. 𝟕𝟏𝟒 47.472
HHV (kJ/mol) 5707.177 𝟓𝟕𝟓𝟐. 𝟒𝟑𝟕 5729.807
LHV (kJ/ mol) 5528.245 𝟓𝟓𝟕𝟑. 𝟓𝟎𝟓 5550.875
∆H of combustion naphthalene -5732.933 −𝟓𝟕𝟕𝟕. 𝟏𝟕𝟖 5755.056
(kJ/mol)
∆H of combustion naphthalene from −4981 −4981 −4981
Literature(kJ/mol)

%error 15.096 15.984 15.54


Results & Discussion

Temperature vs. Time data


plot showing Ti, Ta, Tb, Tc,
and Tf
Conclusion

The value of heat of combustion of naphthalene in literature


is equal to −4981 kJ/mol. Our results showed approx. 15% error
from the theoretical value. The difference is most likely due to the
multiple sources of error described in the discussion part. In spite of
the error, we can still conclude that heating value of naphthalene
can be determined using bomb calorimetry. Since the end product
of naphthalene is a gas, it is preferable to use its LHV than its HHV.
Recommendation

It is recommended to accurately read and record the


temperature of calorimeter water for only minute changes may
contribute to larger errors. It is also highly suggested to ensure the
contact of the fuse to the sample for it may not ignite if not
properly attached. Good points should be continued and improved if
possible.
Determination of Heating
Value of Liquid Fuels
EXPERIMENT 3
Methodology

Preparation of
Preparation of Preparation of Experiment
the Calorimeter
sample and fuse the bomb Proper
water
Preparation of sample and fuse

Weighing of wire, gel Attachment of 10-


capsule and steel cm wire to the gel
capsule capsule

Injection of butanol into


the gel capsule with the
use of a syringe.
Preparation of the bomb

Attachment of the wire and gel capsule


to the electrodes of the bomb
Results & Discussion

Temperature vs Time graph for the combustion of butanol


Combustion of Butanol
27.5

i a b c f
27

26.5
TEMPERATURE IN 0C

26

25.5

25

24.5
0 2 4 6 8 10 12 14 16 18 20
TIME (MIN)
Results & Discussion

Table 3.1 Summary of calculated values


Parameter Values
Mass of Combusted Butanol (g) 0.47836
Mole of Combusted Butanol (mol) 0.00645368
Mass of Gelatin Capsule (g) 0.0173
Mass of Combusted Wire (g) 0.002
Moles of Combusted Wire ( mol) 1.0252E-05
Corrected ΔT (oC) 1.378603
HHV (kJ/mol) 2994.29
LHV (kJ/mol) 𝟐𝟕𝟕𝟎. 𝟔𝟐
Enthalpy of Combustion (kJ/mol) -3026.29
Results & Discussion

The results show that the enthalpy of combustion is -3026.29


kJ/mol. However, from Perry's Table 2-179, the net enthalpy of
combustion of 1-butanol is -2454 kJ/mol and -2446 kJ/mol for 2-
butanol. This entails a difference of about 23%, too large an error.
Conclusion & Recommendation

This could be attributed to the assumption that the gel capsule was
completely combusted therefore neglecting the fact that maybe
some of the remaining mass uncombusted was actually that of the
gel capsule and therefore affecting the exact calculation of the HHV
and eventually the experimental enthalpy of combustion.
Results & Discussion

This could have been prevented or minimized if there was a concrete way
in determining the actual constituents of the combustion residue,
preferably laboratory tests, to obtain more accurate values. However,
errors can also come from human error like experimenter readings of
measuring devices since the experiment required several methods
requiring accurate measurement of materials (e.g. volume measurement
of sample, weighing of sample, pre-combustion set-up, post-combustion
residue).
Results & Discussion

Still, the gross errors can be due to the bomb calorimeter itself, but
it is highly unlikely since the Ccal obtained from the previous
experiments should have accounted for these discrepancies, which
leads to the possible faulty calibration from past experiments.
Possible causes of errors

• Human Error- reading of thermometer at inaccurate time


intervals

• Equipment error- the heat may escape through the walls of


the calorimeter, thus adding uncertainty on the calculated values
of temperature and heats of combustion.
Possible causes of errors

Inaccuracy of the measurement of water inside the


calorimeter may also be a cause of error since additional volume
may require more energy to increase the temperature of water by
1°C.
Conclusion and Recommendation

The value of enthalpy of combustion of butanol in literature is equal


to -2454 kJ/mol. Our results showed approx. 23% error from the
theoretical value. The difference is most likely due to the multiple
sources of error described in the discussion part. In spite of the
error, we can still conclude that it is possible to determine the
heating value of butanol using bomb calorimetry given that the
calibration of the bomb calorimeter is accurate.
Conclusion and Recommendation

It is recommended to minimize the errors in volume measurement of


sample, weighing of sample, pre-combustion set-up, post-combustion
residue in order to attain more accurate data that will lead to more
accurate results thus less error. It is also recommended to conduct an
experiment that will determine the extent of combustion of the gel
capsule alone. The value may then be used in calculating the heat of
combustion of butanol or any other liquid fuel.
References

• Atkins and de Paula. (2002). Physical Chemistry (7th ed.). Oxford, UK: Oxford University Press.
• Bomb Calorimetry. (N. D.). Retrieved from
• http://www.chem.hope.edu/~polik/Chem345-1997/calorimetry/bombcalorimetry1.html
• Calibration of Oxygen Bomb Calorimeters. (2008, October 31). Retrieved from
http://www.siamzim.com/pdf/calorimeters/TN_101.pdf
• Calorimetry. (N. D.). Retrieved from
• https://courses.lumenlearning.com/chemistryformajors/chapter/calorimetry/
• Helmenstine, A. M. Coffee Cup Calorimetry and Bomb Calorimetry. (2015). Retrieved from
http://chemistry.about.com/od/thermodynamics/a/coffee-cup-bomb-calorimetry.htm
• Lower, S. (N. D.). Constant Volume Calorimetry. Retrieved from
• http://chemwiki.ucdavis.edu/Physical_Chemistry/Thermodynamics/Calorimetry/Constant_Volume_Calorimetry
• Smith, J., Van Ness, H., & Abbott, M. (2005). Introduction to
Chemical Engineering
• Thermodynamics 7th Edition. New York: McGraw-Hill.
• U.S. National Library of Medicine. (N. D.). Naphthalene.
Retrieved from:
• https://pubchem.ncbi.nlm.nih.gov/compound/naphthalene#sectio
n
References

• Atkins and de Paula. (2002). Physical Chemistry (7th ed.). Oxford, UK: Oxford University Press.
• Bomb Calorimetry. (N. D.). Retrieved from
• http://www.chem.hope.edu/~polik/Chem345-1997/calorimetry/bombcalorimetry1.html
• Calibration of Oxygen Bomb Calorimeters. (2008, October 31). Retrieved from
http://www.siamzim.com/pdf/calorimeters/TN_101.pdf
• Clarke Energy. (2013, January 25). Heating Value. Retrieved from Clarke Energy:
• https://www.clarke-energy.com/2013/heating-value/
• Calorimetry. (N. D.). Retrieved from
https://courses.lumenlearning.com/chemistryformajors/chapter/calorimetry/
• Helmenstine, A. M. Coffee Cup Calorimetry and Bomb Calorimetry. (2015). Retrieved from
• http://chemistry.about.com/od/thermodynamics/a/coffee-cup-bomb-calorimetry.htm
• Heat of Combustion. (N.D.) Retrieved from: https://neutrium.net/heat_transfer/heat-of-
• combustion/)
References

• Laurito, E. R. (1994). Stoichiometry of Fuel Combustion and Related Process Industries.


Quezon City: New Galaxic Lithographic Arts & Printing Press.

• Lower, S. (N. D.). Constant Volume Calorimetry. Retrieved from


http://chemwiki.ucdavis.edu/Physical_Chemistry/Thermodynamics/Calorime
try/Constant _Volume_Calorimetry
• Perry, R. H., & Green, D. W. (2008). Perry's chemical engineers' handbook. New York:
McGraw-Hill. Retrieved on 01 September 2017
• Smith, J., Van Ness, H., & Abbott, M. (2005). Introduction to Chemical Engineering
Thermodynamics 7th Edition. New York: McGraw-Hill.
• U.S. National Library of Medicine. (N. D.). Naphthalene. Retrieved from:
https://pubchem.ncbi.nlm.nih.gov/compound/naphthalene#section