RADIATION PROPERTIES OF GASES AND VAPORS

• O2, N2, H2 and dry air neither emit nor absorb radiation
• H2O, CO2, CO, SO2, NH3 and hydrocarbons
• During molecular collisions, rotation and vibrations of individual atoms in a
molecule can be excited so that atoms that possess free electrical charges can
emit electromagnetic waves.
• We shall restrict our consideration here to the evaluation of the radiation
properties of H2O and CO2.
RADIATION PROPERTIES OF GASES AND VAPORS

• Typical changes in energy level due to changes in vibrational frequency or

rotation manifest themselves in a strong peak at the wavelength.
• This process results in absorption or emission bands.
• The shape and width of these bands depend on the temperature and pressure of
the gas.
• While monochromatic absorptivity is primarily a function of the thickness of the
gas layer.
RADIATION PROPERTIES OF GASES AND VAPORS

• Experimental measurements generally yield the absorptivity of a gas layer over a band
width corresponding to the width of the spectrometer used.
• The quantity of primary interest is the effective total absorptivity or emissivity.
• This quantity assumes that the gas is gray and its value depends not only on the pressure,
temperature, and composition, but also on the geometry of the radiating gas.
• Whereas the emission and absorption of radiation are surface phenomena for opaque
solids, its thickness, pressure, and shape as well as its surface area must be taken into
account.
MONOCHROMATIC ABSORPTIVITY OF WATER
VAPOR
MONOCHROMATIC ABSORPTIVITY OF WATER
VAPOR
INTENSITY OF RADIATION

• Iλ0 passes through a gas layer of thickness L, the radiant-energy absorption in a

differential distance dx is governed by the relation

𝑑𝐼λ𝑥 = −𝑘λ′ 𝐼λ𝑥 𝑑𝑥

where Iλx = intensity at distance x

𝑘λ′ = monochromatic absorption coefficient
INTENSITY OF RADIATION

• Integration between the limits x = 0 and x = L yields

′
𝐼λ𝐿 = 𝐼λ0 𝑒 𝐿
−𝑘λ

where IλL = intensity of radiation at L

• The difference between the intensity of radiation entering the gas at x = 0 and
the intensity of radiation leaving the gas layer at x = L is the amount of energy
absorbed by the gas
′
𝐼λ0 − 𝐼λ𝐿 = 𝐼λ0 1 − 𝑒 λ𝐿
−𝑘 = 𝛼𝐺λ 𝐼λ0
GAS BODIES OF FINITE DIMENSIONS

• The effective absorptivity or emissivity depends on the shape and size of the gas
body.
• An approximate method was developed by Hottel and Egbert for engineering
calculations.
• Hottel evaluated the effective total emissivities of a number of gases at various
temperatures and pressures, and presented his results in graphs.
EMISSIVITY OF WATER VAPOR AT A TOTAL
PRESSURE OF 1 ATM
EMISSIVITY OF CARBON DIOXIDE AT A TOTAL
PRESSURE OF 1 ATM
GAS BODIES OF FINITE DIMENSIONS

• The emissivities of H2O and CO2 at a total pressure PT other than 1are given by
the expression.

𝜀𝐻2𝑜 𝑃𝑇 = 𝐶𝐻2 𝑜 𝜀𝐻2𝑜 𝑃𝑇 = 1

𝜀𝐶𝑂2 𝑃𝑇 = 𝐶𝐶𝑂2 𝜀𝐶𝑂2 𝑃𝑇 = 1
• The correction factors are plotted in a graph.
CORRECTION FACTOR FOR WATER VAPOR
CORRECTION FACTOR FOR CARBON DIOXIDE
GAS BODIES OF FINITE DIMENSIONS

• When both H2O and CO2 exists in a mixture, the emissivity of the mixture can be
calculated by adding the emissivity of the gases determined by assuming that
each gas exists alone and then subtracting a factor Δε, which accounts for
emission in overlapping wavelength bands.
• The emissivity of a mixture of H2O and CO2 is:
𝜀𝑚𝑖𝑥 = 𝐶𝐻2 𝑜 𝜀𝐻2𝑜 𝑃𝑇 + 𝐶𝐶𝑂2 𝜀𝐶𝑂2 𝑃𝑇 − ∆𝜀
FACTOR Δε TO CORRECT THE EMISSIVITY OF A
MIXTURE OF VAPOR AND CO2
GAS BODIES OF FINITE DIMENSIONS

• The graphs for emissivity of vapor and carbon dioxide apply strictly only to a
system in which a hemispherical gas mass of radius L radiates to an element of
surface located at the center of the base of the hemisphere.
• However for shapes other than hemispheres, an effective beam length can be
calculated using a table.
MEAN BEAM LENGTH OF VARIOUS GAS SHAPES
EXAMPLE 1
Determine the emissivity of a gas mixture consisting of N2, H2O and CO2 at a
temperature of 800 K. The gas mixture is in sphere with diameter of 0.4 m, and the
partial pressures of the gases are 𝑃𝑁2 = 1 atm, 𝑃𝐻2𝑂 = 0.4 atm, 𝑃𝐶𝑂2 = 0.6 atm.
𝐿 = 2/3 𝐷 = 0.27 𝑚

𝑇 = 800 𝐾
𝑃𝐻2𝑂 𝐿 = 0.107 𝑎𝑡𝑚 𝑚
𝑃𝐶𝑂2 𝐿 = 0.160 𝑎𝑡𝑚 𝑚
EMISSIVITY OF WATER VAPOR AT A TOTAL
PRESSURE OF 1 ATM
EMISSIVITY OF CARBON DIOXIDE AT A TOTAL
PRESSURE OF 1 ATM
EXAMPLE 1
The emissivity of water vapor and carbon dioxide at 1 atm total pressure is
𝜀𝐻2𝑂 𝑃𝑇=1 = 0.15
𝜀𝐶𝑂2 𝑃𝑇=1 = 0.125
Since the total gas pressure is 2 atm, we must correct the 1-atm values for ε.
𝐶𝐻2𝑂 = 1.62
𝐶𝐶𝑂2 = 1.12
We add PcL + PwL to get Δε.
∆𝜀 = 0.014
CORRECTION FACTOR FOR WATER VAPOR
CORRECTION FACTOR FOR CARBON DIOXIDE
FACTOR Δε TO CORRECT THE EMISSIVITY OF A
MIXTURE OF VAPOR AND CO2
EXAMPLE 1
The emissivity of the mixture will be
𝜀𝑚𝑖𝑥 = 𝐶𝐻2 𝑜 𝜀𝐻2𝑜 𝑃𝑇 + 𝐶𝐶𝑂2 𝜀𝐶𝑂2 𝑃𝑇 − ∆𝜀

𝜀𝑚𝑖𝑥 = 1.62 0.15 + 1.12 0.125 − 0.014

𝜀𝑚𝑖𝑥 = 0.369
EXAMPLE 2
Determine the absorptivity of a mixture of H2O vapor and N2 gas at a total
pressure of 2.0 atm and a temperature of 500 K if the mean beam length is
0.75m. Assume that the radiation passing through the gas is emitted by a source at
1000 K and the partial pressure of the water vapor is 0.4 atm.
EXAMPLE 2
• The absorptivity of H2O vapor is approximately given by the relation
0.45
𝑇𝐻2𝑂
𝛼𝐻2𝑂 = 𝐶𝐻2 𝑂 𝜀𝐻′ 2𝑂
𝑇𝑠
• Pressure-mean beam length product equal to
𝑇𝑠
𝑃𝐻2𝑂 𝐿
𝑇𝐻2𝑂
EXAMPLE 2
• The absorptivity of CO2 is approximately given by the relation
0.65
′
𝑇𝐶𝑂2
𝛼𝐶𝑂2 = 𝐶𝐶𝑂2 𝜀𝐶𝑂2 𝑇𝑠
• Pressure-mean beam length product equal to
𝑇𝑠
𝑃𝐶𝑂2 𝐿
𝑇𝐶𝑂2
EXAMPLE 2
• Since nitrogen is transparent, the absorption in the mixture is due to the water
vapor alone. The absorptivity of H2O is
0.45
𝑇𝐻2𝑂
𝛼𝐻2𝑂 = 𝐶𝐻2 𝑂 𝜀𝐻′ 2𝑂
𝑇𝑠

𝑃𝐻2𝑂 𝐿 = 0.4 𝑥 0.75 = 0.3 𝑎𝑡𝑚 𝑚

1 1
𝑃𝑇 + 𝑃𝐻2𝑂 = 2 + 0.4 = 1.2 𝑎𝑡𝑚
2 2
EXAMPLE 2
• Using the values we get, the emissivity and correction factor of water vapor will
be
𝜀𝐻2𝑂 = 0.29
𝐶𝐻2𝑂 = 1.40
Substitute to the absorptivity equation, we get
0.45
500
𝛼 = 1.4 𝑥 0.29
1000
𝛼 = 0.30