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Determination of Heating Value of Diesel Fuel

Objective
To determine the higher heating
value (total calorific value, or gross
heat of combustion) and the lower
heating value of a sample of liquid
diesel fuel using a non-adiabatic
bomb calorimeter
What is a Bomb Calorimeter?
 A device used to measure the heating value of a liquid
or solid fuel
 Uses the same principle of a gas calorimeter, but
operates at constant volume
 Uses pure oxygen instead of air
 Two distinct types:
 Adiabatic (No heat transfer with the surrounding)
 Non-adiabatic (Some heat can be transferred between
the calorimeter and the surrounding environment)
Figure 1- A Parr plain Bomb calorimeter
How Does it Work?
 Sample fuel is burned with pure oxygen in a
pressurized constant volume combustion chamber
(bomb)
 Heat of combustion is transferred to the water in the
inner jacket (bucket)
 Temperature change of water is measured
 Knowing the mass and specific heat of water and
bomb, the amount of transferred heat is measured
 Appropriate corrections are applied to find the higher
heating value
Figure 2-Cross section of a plain calorimeter

Main components:
A. Thermometer
B. Inner jacket (Bucket)
C. Bomb
D. Stirrer
E. Stirrer motor
F. Wire to firing
mechanism
Higher Heating Value
The heat absorbed by the bomb and water
equals to :
Q=W∆𝑻
Where:
W=(𝒎𝑪)𝒃𝒐𝒎𝒃 +(𝒎𝒄)𝒘𝒂𝒕𝒆𝒓
W is called the bomb calorimeter water equivalent

∆𝑻 = (𝑻𝒇𝒊𝒏𝒂𝒍 − 𝑻𝒊𝒏𝒊𝒕𝒊𝒂𝒍 )
Major Corrections Applied:
 Radiation Correction (only for non-adiabatic
calorimeter)
 Acid Corrections (𝑒1 & 𝑒2 )
 Fuse wire correction (𝑒3 )
 Correction to account for combustion happening at
constant volume instead of constant pressure (𝑒4 )
 Correction to account for the combustion products not
being at the same temperature as the reactants (𝑒5 )
Radiation Correction
 In a non-adiabatic bomb calorimeter some heat is
exchanged between the water in the bucket and the main
jacket, therefore ,∆𝑇 must be corrected
 To find the corrected temperature change, from collected
data:
 Temperature vs. time is plotted
 𝑇𝑖 (initial Temperature), 𝑇𝑎 (ignition Temperature),
𝑇𝑐 (maximumTemperature), and 𝑇𝑓 (final Temperature) are
marked on the graph
 𝑇𝑏 (the temperature at which 60% of temperature change
occurs),𝑟1 𝑎𝑛𝑑 𝑟2 (rate of heat transfer prior to ignition and
after maximum T is reached) are calculated
FIG. 3: An example of (temperature, time) data plot showing the
positions for reading Ti, Ta, Tb, Tc, and Tf
Corrected Temperature change
𝑇𝑏 = 𝑇𝑎 + 0.6(𝑇𝑐 − 𝑇𝑎 )
𝑇𝑎 − 𝑇𝑖
𝑟1 =
𝑡𝑎 − 𝑡𝑖
𝑇𝑐 − 𝑇𝑓
𝑟2 =
𝑡𝑓 − 𝑡𝑐
Where: T stands for temperature and t stands for time

∆Tcorrected = 𝑻𝒄,𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒆𝒅 − 𝑻𝒂,𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒆𝒅


∆Tcorrected =(𝑻𝒄 + 𝒓𝟐 (𝒕𝒄 − 𝒕𝒃 )) − (𝑻𝒂 + 𝒓𝟏 (𝒕𝒃 − 𝒕𝒂 ))
Acid Corrections (𝑒1 &𝑒2 )
 Diesel fuel contains impurities such as sulfur and
nitrogen.
 At high pressure, sulfur and nitrogen are oxidized and
form 𝑆𝑂𝑥 & 𝑁𝑂𝑥 , which react with water in the product
and form nitric acid (HNO3) and sulfuric acid
(H2SO4)
 These reactions are exotermic and produce heat,
which is added to the heat of combustion
 Since these acids are not formed during combustion in
a power plant, the heat generated cannot be credited
to the sample
Acid Corrections
 𝑒1 accounts for the heat produced by nitric acid and a
portion of heat produced by the sulfuric acid and is
determined using a standard anhydrous solution
5
𝑒1 (𝑐𝑎𝑙) = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑚𝑙 ×
9
Note: 1 ml of standard anhydrous solution has an
5
equivalent heat of cal
9

 𝑒2 is the excess heat produced by the sulfuric acid, but


it’s negligble due to the low sulfur content
Fuse Wire Correction (𝑒3 )
 No wire is used to initiate the combustion process in a
power plant, so a correction must be made for the heat
of combustion of the fuse wire consumed in the
experiment
 No. 34 B&S gage Nickel-Chromium alloy wire used in
this experiment has a heat of combustion of 1600
cal/gram or 2.3 cal/cm of wire consumed

𝒆𝟑 (𝒄𝒂𝒍) = 𝒍𝒃𝒖𝒓𝒏𝒕 𝒘𝒊𝒓𝒆 ×2.3


Constant volume vs constant pressure
 The heat of combustion is defined as the heat released
from complete combustion at 25𝑜 C and constant
pressure of one atm
 Heating value is the heat of combustion per unit mass
of the fuel
 The combustion in bomb calorimeter occurs at
constant volume Q= ∆𝑈 = 𝑈𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑈𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
 Higher heating value is defined as
HHV= ∆𝐻 = 𝐻𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 −𝐻𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
Correction 𝑒4
Since:
H=U + PV
Then:
∆H = (U + PV)Products – (U + PV)Reactants
∆H = 𝑈𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 – 𝑈𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 + V(𝑃𝑓 –𝑃𝑖 )
Or
HHV=Q+V(𝑃𝑓 –𝑃𝑖 )
Therefore:
𝒆𝟒 = V(𝑷𝒇 –𝑷𝒊 )
Correction to account for products to be at
higher temperature (𝒆𝟓 )
Diesel fuel has the chemical formula of 𝐶16 𝐻34 or the
simplified formula of 𝐶𝐻2.1

CH2.1 + 1.525 O2 → CO2 + 1.05 H2O

HHV is the heat of combustion when products are


returned to the temperature of reactants
𝑒5 is the extra heat released when the products are
cooled from final T to initial T
𝒆𝟓 = (𝑴𝑪𝒗 )𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 ∆T
Higher Heating Value
𝑾∆𝑻𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒆𝒅 −𝒆𝟏 −𝒆𝟐 −𝒆𝟑
HHV= + 𝒆𝟒 + 𝒆𝟓
𝒎𝒇𝒖𝒆𝒍

Where:
W=1346 cal/ 𝑜𝐹 = 2423 𝑐𝑎𝑙/ 𝑜𝐶
𝑚𝑓𝑢𝑒𝑙 = 1 gram
𝑒4 = - 23 Cal/gram of fuel
𝑒5 = 3.94 cal/ 𝑜𝐶 × (𝑇𝑓 − 𝑇𝑖 )
(𝑇𝑓 − 𝑇𝑖 ) must be in 𝑜𝐶
Lower Heating Value
LHV = HHV -𝒎𝒘𝒂𝒕𝒆𝒓 𝒉𝒇𝒈,𝒘𝒂𝒕𝒆𝒓 𝒂𝒕 𝟐𝟓 𝒐𝑪

𝟏×𝟏.𝟎𝟓×𝟏𝟖 𝒈𝒘𝒂𝒕𝒆𝒓
𝒎𝒘𝒂𝒕𝒆𝒓 = = 1.34
𝟏𝟒.𝟏 𝒈𝒇𝒖𝒆𝒍
𝑘𝐽 𝑐𝑎𝑙
𝒉𝒇𝒈,𝒘𝒂𝒕𝒆𝒓 𝒂𝒕 𝟐𝟓 𝒐𝑪 =2441.7 = 583.19
𝑘𝑔 𝑔