Determination of Heating Value of a Gaseous Fuel

Calorimetry & Calorimeters

 Calorimetry is the measurement of the quantity of
heat exchanged in chemical reactions or through
physical changes.
 A calorimeter is a device used to measure the heat
exchanged through these processes
 A calorimeter used to measure the heat of chemical
reactions may be operated under constant
(atmosphere) pressure, or constant volume
Gas Calorimeter
A device used to measure the
heating value of a gaseous fuel
The combustion process takes
place at constant pressure
(atmospheric), and the role of the
calorimeter is that of a steady state
heat exchanger
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)
Principle of Using a Calorimeter to
Measure the Heating Value
 A known amount of fuel is burned
 The heat is transferred to water
 The temperature change of water is measured
 The heat gained by the water is measured using the
following equation:
Q = mwater•Cwater•ΔTwater
 Corrections are applied to drive the heating value
Heating Value
 The amount of energy released by the complete
combustion of a unit mass or volume of a fuel at
standard condition
 When the fuel contains hydrogen, water would appear
in the products of combustion
 Depend on the state of water in products, the heating
value would be referred to as either lower or higher
heating value
Higher & Lower Heating Values
 The higher heating value (HHV) aka the gross heat
of combustion is that when all products of
combustion are cooled to the pre-combustion
temperature, and water vapor formed during
combustion is condensed
 The lower heating value (LHV) is defined as the net
calorific value and is determined by subtracting the
heat of vaporization of water vapor (generated during
combustion of fuel) from the higher heating value
(Meriçboyu et al., 1998).Dec 18, 2014
How the two values are related?
The lower heating value is equal to the
higher heating value minus the latent
heat of evaporation of water formed by
the combustion reaction at the standard
temperature (hfg).

LHV = HHV – mass of condensate × hfg, water at Ts

Exp#1 –Gas Calorimeter
Objective
To determine the higher and lower
heating value of a gas by the
continuous flow calorimeter
method and to become familiar
with the calculations and
corrections used in precision
calorific work.
Higher & Lower Heating Values of a gas
 The HHV (total calorific value, or gross heat of
combustion) of a gas is the number of Btu evolved by the
complete combustion at constant pressure of one
standard cubic foot of gas with air, if the temperature of
the gas, air, and products of combustion are all 60 F and if
all the water formed by the combustion reaction is
condensed.
 Lower Heating value (net calorific value) of a gas is the
number of Btu evolved by the complete combustion at
constant pressure of one standard cubic foot of gas with
air, if the temperature of the gas, air, and products of
combustion are all 60 F and the water formed by the
combustion reaction would remain in the vapor state
Note: The latent heat of water (hfg) at 60 oF is 1059.9 Btu/lbm
How does it work?
 The gas is fed to a burner, which is placed inside the
calorimeter, at a steady rate and the volume of flow is
metered so that the total quantity used can be determined
 The gaseous fuel is burned with air at constant pressure
 The heat of combustion is transferred to a stream of water
flowing through the calorimeter
 This water is collected during the test and weighed
afterwards
 The temperature rise of the water in the apparatus is
recorded, so that the total amount of heat transferred to
the water can be calculated.
Higher Heating Value of Gas
 The heat absorbed by the water equals to :

WCp(Tout- Tin)
 Ignoring the corrections, the higher heating value of
the fuel is given by:
Where:
 HHV= Higher heating value of the gaseous fuel
(Btu/Standard 𝑓𝑡 3 )
 W= Weight of the heated water collected (lbs)
 Cp= Specific heat of water at constant pressure
(Btu/lb 𝑚𝑜𝐹)
 Tout= Water outlet Temperature (oF)
 Tin = Water inlet Temperature(oF)
 Vs = Standard volume of the gaseous fuel used(𝑓𝑡 3 )
Why Standard Volume?
 A gas has different volume at different pressure and
temperature
 In order to compare the heating values of different
gases measured at various pressures and temperatures,
it is necessary to use standard conditions
ASTM vs. ASME
 Two sets of standards:
o ASTM (American Society of Testing and
Materials) recommends 60 oF and 30 inch
Hg
o ASME (American Society of Mechanical
Engineers) recommends 68 oF and 29.921
inch Hg
 ASTM is used in our calculations
How to determine the Standard Volume?
 Applying the ideal gas law:
𝑃𝑠 𝑉𝑠 𝑃𝑚 𝑉𝑚
=
𝑇𝑠 𝑇𝑚
Note: subscript m stands for measured and subscript s stands for
standard

So:
𝑃𝑚 𝑉𝑚 𝑇𝑠
𝑉𝑠 =
𝑃𝑠 𝑇𝑚
Where:
 Vm = The volume of gas used during the run and measured
by the gas meter in 𝑓𝑡 3
 Ps and Pm are partial pressures of gas at standard and
experimental conditions
Note: The gas is saturated with water vapor, so the pressure of
dry gas must be used:
 Ps = Standard pressure – water saturation pressure at 60F
 Ps = 30in Hg – 0.52 in Hg = 29.48 in Hg
 Pm = Gas absolute pressure – water saturation pressure at gas
temperature
 Ts = Standard Temperature = 60 F = 519.7 R
 Tm= Gas absolute temperature (R)
Major Corrections Applied
Cs: Corrected Specific Heat of water
Cs is the correction to account for the change of specific
heat of water with temperature
Note: Cp of water is not always exactly
1 Btu/lboF
∆𝑯 = 𝑪𝒑 ∆𝑻
Since the change in temperature of water is small,
Cp can be considered constant. So:
𝒉𝒇,𝒘𝒂𝒕𝒆𝒓 𝒂𝒕 𝑻𝒐𝒖𝒕 −𝒉𝒇,𝒘𝒂𝒕𝒆𝒓 𝒂𝒕 𝑻𝒊𝒏
𝑪𝑷𝒘𝒂𝒕𝒆𝒓 =
𝑻𝒐𝒖𝒕 −𝑻𝒊𝒏
Ce: Heat loss to the Surrounding
Ce is the correction for the heat loss from the calorimeter to
the surrounding environment when the inlet water is at
combustion air temperature

Where:
o hc is the convective heat transfer coefficient of the
calorimeter: ℎ𝑐 = 5 Btu/hr. 𝑓𝑡 2
o A is the surface area of the calorimeter shell= 2.1 𝑓𝑡 2
o t is the time of run in hour (5 minute =0.0833 hr )
𝑜
o ∆T= 𝑇𝑠ℎ𝑒𝑙𝑙 - 𝑇𝑟𝑜𝑜𝑚 (in 𝐹)
(The temperature difference between the shell and the
surrounding air in 𝑜𝐹)
Ct : Correction to refer the results of
the test to the standard temperature
of 60 oF

Ct is the correction to account for the fact that

neither the reactant nor the products are at the
standard temperature of 60 oF, therefore, the
results must be corrected
How to Calculate Ct?
 The HHV of the gas refers to the heat evolved when all
reactants and products are at standard temperature of
60oF:
HHV=Enthalpy of products at 60 oF-Enthalpy of reactants at 60 oF
 The heat evolved (Q)is measured with the gaseous fuel
entering at 𝑇𝑓𝑢𝑒𝑙 , air entering at 𝑇𝑎𝑖𝑟 , exhaust gases
leaving at 𝑇𝐸𝑥ℎ𝑎𝑢𝑠𝑡 , and the condensate leaving at
𝑇𝐶𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑒 :
Q =Enthalpy of products -Enthalpy of reactants
Considering the following combustion reaction with
50% excess air to assure complete combustion:
𝟕𝟗
CH4 + 3(O2 + N2) → CO2 +2 H2O(L) + O2 + 11.285 N2
𝟐𝟏
Ct is calculated using the following equation:

Ct = [(CpCO2 + CpO2 + 11.285 CpN2)(Texh - 60) + 2CpH2O (Tcond -60)]-

[(3CpO2 + 11.285 CpN2)(Tair - 60) + CpCH4 (Tgas -60)]

Proof is in the handout and will be demonstrated in

class
Higher Heating Value
Applying the corrections:

𝑊 𝐶𝑝𝐻2𝑂 ∆𝑇𝐻2 𝑂 + 𝐶𝑒
𝐻𝐻𝑉 = − 𝐶𝑡
𝑉𝑠
Where:
 W= weight of the heated water collected during run (lbs)
Cp= corrected specific heat of water (Btu/lb oF)
 ∆𝑇𝐻2𝑂 =Tout – Tin
Note: Use average temperature of water in and out
 Tout=Water outlet Temperature (oF)
 Tin = Water inlet Temperature (oF)
 Vs = Standard volume of gaseous fuel (ft3)
 Ce = Correction for heat loss from the calorimeter (Btu)
 Ct = Correction to refer the results of the test to the
standard temperature of 60 𝒐𝑭 in Btu/SCF
Lower Heating Value
𝑚𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑒 × ℎ𝑓𝑔,𝑤𝑎𝑡𝑒𝑟 𝑎𝑡 60𝐹
𝐿𝐻𝑉 = 𝐻𝐻𝑉 −
𝑉𝑠

Note:
Heat of vaporization of water (ℎ𝑓𝑔 ) 𝑎𝑡 60 oF = 1059 Btu/lbm