EEZG614, Air Pollution Control Technologies

Lecture 1: Introduction, Stoichiometry and Applications of Ideal

Gas Law and Pollutants of Global Concern
Dr. Somak Chatterjee
BITS Pilani
Pilani Campus
Assistant Professor, Department of Chemical Engineering
Contents

• Stoichiometry: Mole fraction and mass fraction

• Air Pollution: classification, sources and effects

• Pollutants of global concern

• The Ideal Gas Law

• Concentration Measurements in Gases

• Gas Flow Measurement

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Basic Calculations
The ideal gas law & concentration measurements
For gases, percentages are usually expressed as percent by volume.
For an ideal gas (ambient air approximates an ideal gas), volume percent is the same as
mole percent.
Ideal gas is always satisfying the ideal gas law.

where P= absolute pressure (atm); V=Volume (liters) ; n= number of gmol; R = ideal gas law
constant ( 0.08206 L-atm/gmol-K) ; T = absolute temperature (K).
Ideal gas law can also be written as:

where M=mass of the sample; : Molecular weight of the gas

Equation 2 can rearrange to give the mass density of an ideal gas as:

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Basic Calculations
Definition and Scales of Concentration:
Mass concentration, p, defined as the ratio of the mass of pollutant
to the mass of air plus mass of pollutant:

𝒎𝒑
𝝎𝒑 =
𝒎𝒂 +𝒎 𝒑

Where mp is the mass of the pollutant and ma is the mass of pure air in
a given volume of air-pollutant mixture.

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Basic Calculations
Volume concentration, yp, defined as the ratio of the volume of
pollutant (vp ) to the volume of air (va) plus volume of pollutant:

𝒗𝒑
𝒚𝒑=
𝒗 𝒂 +𝒗 𝒑

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Basic Calculations
Volume concentration in parts per million (ppm), yppm:

𝒚 𝒑𝒑𝒎 = 𝒚 𝒑 × 𝟏𝟎𝟔

()---(4)

𝟏 𝒑𝒑𝒎=𝟎 . 𝟎𝟎𝟎𝟏 %  𝒃𝒚 𝒗𝒐𝒍𝒖𝒎𝒆

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 Basic Calculations
Mass- Volume concentration, p, defined as the ratio of the mass of
the pollutant to the volume of air plus volume of pollutant:

𝒎𝒑
𝝆 𝒑=
𝒗 𝒂+ 𝒗𝒑

The relation between p in g/m3 and yppm :

𝒑𝒑𝒎 (𝒎𝒘 ) ( 𝟏 𝟎 )
𝟑
𝝆 𝒑= 𝒂𝒕 𝟏 𝒂𝒕𝒎 𝟐𝟓 ° 𝑪
𝟐𝟒 .𝟒𝟓

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Basic Calculations
The relation between p in g/m3 and yppm :
• It is necessary to specify a temperature and a pressure because a fixed amount
of gas may occupy different volumes depending on these parameters.
• In air pollution work, the reference conditions are usually chosen as 25 ⁰C and
1.0 atm
• Solving the ideal gas law for the volume of the pollutant gas, and dividing by the
volume of the total gas, the pollutant volume fraction in the gas can be written
as:
Where the subscripts p and t indicate pollutant gas and total gas, respectively.

𝑽 𝒑 𝒏𝒑 𝑹𝑻 / 𝑷
= − −−− −(𝟓)
𝑽𝒕 𝑽𝒕
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Basic Calculations
The relation between p in g/m3 and yppm
𝑽𝒑 𝒏 𝒑 𝑹𝑻 / 𝑷
= − − − − −(𝟓)
𝑽𝒕 𝑽𝒕
Consider the left side of above equation and recall the following equation:

Therefore, multiply both sides of equation by . Also, in the right-hand side of this
equation, substitute for np , which is the mass of the pollutant gas divided by the
MW. Thus equation 6 becomes

𝑽𝒑𝟔 𝟔 𝑴 𝒑 / 𝑴 𝑾𝑷 𝑹𝑻
𝑪𝒑𝒑𝒎=𝟏 𝟎 =𝟏 𝟎 ( )( )−−− −−−(𝟔)
𝑽𝒕 𝑽𝒕 𝑷

Mp = mass of pollutant gas

MWP = molecular weight of pollutant gas, g/gmol

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Basic Calculations
The relation between p in g/m3 and yppm :
Equation (6) can be rearranged algebraically to isolate the
concentration in units of mass per volume (in units of g/l):
𝑴𝒑 𝑪 𝒑𝒑𝒎 × 𝐌𝐖 𝒑 × 𝟏 𝟎− 𝟔
= − − − − (𝟕)
𝑽𝒕 𝑹𝑻
𝑷

From the ideal gas law RT/P is identically equal to V/n, the volume
occupied by one mole of an ideal gas. Making the replacement,
Equation (7) becomes
𝑴 𝒑 𝑪 𝒑𝒑𝒎 ×𝐌𝐖 𝒑 ×𝟏 𝟎−𝟔
= ¿ − −−− −−(𝟖)
𝑽𝒕 𝑽 /𝒏
The units of the left side of the Eq. (8) are in grams/liter, which are not the most convenient
for reporting pollutant concentration in air. To convert to units of µg/m 3­ (the more usual
units) the left side of Eq. (8) must be multiplied by a factor of 10 ­9 (the product of 10-6 µg/g
and 10-3 L/m3). Of course, to maintain the quality of Eq. (8) the right side of the equation
must be multiplied by 10­9 also.
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Basic Calculations
The relation between p in g/m3 and yppm
• Recall from high school chemistry that the volume per mole of an ideal gas (the
V/n term) has the value 22.4 L/gmol at T=0 oC (273 K) and P=1 atm.
• In air pollution work, it is typical to define standard temperature as 25 oC (298
k).
• At this temperature the value of V/n is 24.45 L/gmol. After multiplying both
sides of Eq. (1.8) by 10­9 and after substituting for V/n the final conversion
equation is:

Cmass = mass concentration µg/m3

Cppm = volume or molar concentration, ppm

𝟏𝟎𝟎𝟎× 𝑪 𝒑𝒑𝒎 ×𝐌𝐖 𝒑

𝑪𝒎𝒂𝒔𝒔 = −−− −−−(𝟗)
𝟐𝟒.𝟒𝟓
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Basic Calculations
The relation between p in g/m3 and yppm
• Note that Eq. (9) applies only at 25 oC and 1 atm.
• For any other temperature and pressure an equation like equation
(9) can be obtained by simply calculating an appropriate value of
V/n (=RT/P) for the denominator (but remember that unit must be
in L/gmol).

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Problem 1

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Problem 2

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Problem 3

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Problem 4

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Gas Flow Measurement
• A fixed number of moles of gas at a certain temperature and pressure
occupies a certain volume.
• If the pressure and temperature of this fixed number of moles of gas are
changed, then the volume can be easily calculated. Equation (1) can be
written as follows:

• Since n is constant in this case, applying Eq. (10) to the two sets of
conditions yields:

𝑷 𝒐𝒍𝒅 𝑽 𝒐𝒍𝒅 𝑷 𝒏𝒆𝒘 𝑽 𝒏𝒆𝒘

= − −−−− −(𝟏𝟏)
𝑻 𝒐𝒍𝒅 𝑻 𝒏𝒆𝒘
𝑷 𝒐𝒍𝒅 𝑻 𝒏𝒆𝒘
𝑽 𝒏𝒆𝒘 =𝑽 𝒐𝒍𝒅 − −−− −−(𝟏𝟐)
𝑷 𝒏𝒆𝒘 𝑻 𝒐𝒍𝒅
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Gas Flow Measurement
𝑷 𝒐𝒍𝒅 𝑻 𝒏𝒆𝒘
𝑽 𝒏𝒆𝒘 =𝑽 𝒐𝒍𝒅 − −−− −−(𝟏𝟐)
𝑷 𝒏𝒆𝒘 𝑻 𝒐𝒍𝒅

Eq. (12) can be applied to a static system or to a flow system as long as the
number of moles under consideration remains constant.

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Problem 5

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Problem 5

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Gas Flow Measurement
• The measurement of gas flow rates is important in air pollution
work.
• Many different types of devices exist for measuring gas flow rates.
• Some commonly used devices are venturi meters, orifice meters,
rotameters, wet test meters, and dry gas meters.
• The Bernoulli equation governs the operation of the first three of
these widely used flow meters.
• However, since density of gas varies with pressure and temperature,
the ideal gas law also must be considered in deriving and using
calibration equations for these meters. The Bernoulli equation can
be written
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Bernoulli's Equation
• The Bernoulli equation can be written as:
--------(14)

where, P = absolute pressure, ρ = density, g = gravitational

acceleration, z = elevation, u = velocity
• When dealing with the flow of gases, if the pressure drop is small
compared to the upstream static pressure, the gas behave
essentially as if it is incompressible.
• Thus, equation for incompressible fluids gives good results. For an
incompressible fluids, Eq. (14) applied to two definite locations
becomes: 𝑷𝟏 𝒖 𝟐𝟏 𝑷 𝟐 𝒖𝟐𝟐
+ 𝒈 𝒁𝟏+ = +𝒈 𝒁 𝟐 + −−− −−(𝟏𝟓)
𝝆𝟏 𝟐 𝝆𝟐 𝟐
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Gas Flow Measurement
For a horizontal venture meter (and a constant density fluid), Eq. (15)
becomes
𝟐 𝟐( 𝑷 𝟏 − 𝑷 𝟐 )
𝟐
𝒖𝟐 −𝒖 = 𝟏 −−− −−(𝟏𝟔)
𝝆𝟏

with the assumption of constant density, and through the use of the
continuity equation, u2 can be related to u1 as follows:

u1 = B2 u2 --------------------------- (17)

where B= D2/D1, the ratio of diameters at points 2 and 1; that is, B is

the ratio of the smaller throat diameter to the larger upstream
diameter
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Gas Flow Measurement
Substituting for in Eq. (16) result in:

------------------------(18)

In practice, venturis are not perfectly frictionless, so an empirical

venture coefficient is introduced into Eq. (18) – that is,

-------------------(19)
for well designed venturis, Cv is on the order of 0.98 or 0.99.
Also, when D2 is less than D1/4, the term 1 - B4 is approximately equal
to 1.0.
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Gas Flow Measurement
• The linear velocity through the throat is not most convenient from
of flow measurement.
• For liquid or for gases with “small” pressure drops, and for fully
turbulent flows, the volumetric flow rate, Q, is obtained by
multiplying the linear velocity by the throat area, A:

----------------------(20)

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Gas Flow Measurement
• For gases, the pressure drop can be considered “small” if (P1 - P2) is
less than 10% of P1. If it is larger, compressibility is significant, and Eq.
(20) should not be used. Thus, for ambient air monitoring, the
pressure drop must be less than about 1.5 psi.
• If a constant K is defined as the venturi coefficient, Cv, over the
denominator of Eq. (20) and if ideal gas behavior is assumed, then Eq.
(20) can be written as:

-----------------------(21)

MW = gas molecular weight; R = ideal gas law constant; T 1 = absolute

temperature at point 1; K = a constant (

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Classification Air Pollutants

• Primary Pollutants: Emitted from the sources ex particulate matter,

such as ash, smoke, dust, fumes. Mist, spray, inorganic gases, and
radioactive pollutants.

• Secondary Pollutants: These are formed in the atmosphere by

chemical interactions among primary pollutants and normal
atmospheric constituents.

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Classification Air Pollutants
Categories of Air Pollutants:
• Particulate Matter

Not gases, can be suspended droplets or solid particles (size

range 200 µm to 0.1 µm and less
• Gaseous Pollutants

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Classification Particulate Matter
• Particulate matter : Any material, except uncombined water, that
exists in the solid or liquid state in the atmosphere or gas stream at
standard condition:
• Classification of various particulates may be made as follows:
• Dust – solid particles larger than colloidal size capable of
temporary suspension in air (size ranging from 1 to 200 m)

• Smoke – Small gas borne particles of the size ranging from 0.01 to
1 m resulting from combustion

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Classification Particulate Matter
• Fumes – Particles formed by condensation, sublimation, or
chemical reaction (size ranging from 0.1 to 1 m ) , tobacco smoke
• Mist – It is made up of liquid droplets generally smaller than 10
m which are formed by condensation in the atmosphere or are
released from industrial operations.
• Fog – It is the mist in which the liquid is water and is sufficiently
dense to obscure vision.
• Aerosol – Under this category are included all air-borne
suspensions either solid or liquid; these are generally smaller than
1 m . Dispersion of microscopic solid or liquid particles in
gaseous media.

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Behavior and Fate of Air Pollutants
Natural Pathways of exchange of pollutants from atmosphere to
earth surface
Particulates:
• Wet removal by precipitation.
• Dry removal by sedimentation, impaction and diffusion.
Gases:
• Wet removal by precipitation.
• Chemical reaction in the atmosphere to produce aerosols and / or
absorption on aerosols with subsequent removal.
• Absorption or reaction at land and ocean surfaces.
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Wet Precipitation
• Wet precipitation has two distinct mechanisms – “rainout” and
“washout”
• The rainout includes various processes taking place inside clouds,
where the contaminants serve as condensation nuclei on which
droplets condense.
• The washout mechanism refers to the removal of pollutants below
the cloud level by falling rain.
• The rainout mechanism is particularly effective for particles whose
size is less than 0.1 m .
• Washout is most effective in removing particles larger than 2 m .

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Dry Deposition
Atmospheric turbulence is particularly effective for coagulating larger
particles whose Brownian motion is less pronounced. The rate of
settling of the particles depends on their settling velocities according
to the Stokes’ law:
gd 2
 2C 
vt   p   a 1  
p

18 a  dp p 

Where:
vt = terminal settling velocity; dp = particle diameter;
p and a = density of particle and air, respectively;
a = viscosity of air; P = air pressure; C = constant
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Photochemical Smog
• The conditions for the formation of photochemical smog are air
stagnation, abundant sunlight, and high concentrations of
hydrocarbon and nitrogen oxides in the atmosphere.
• Smog arises from photochemical reactions in the lower atmosphere
by the interaction of hydrocarbons and nitrogen oxide released by
exhausts of automobiles and some stationary sources.
• This interaction results in a series of complex reactions producing
secondary pollutants such as ozone, aldehydes, ketones, and
peroxyacyl nitrates.

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Photochemical Smog
The starting mechanism is the absorption of ultraviolet light from the
Sun by NO2. This causes the nitrogen dioxide to decompose into nitric
oxide and highly reactive atomic oxygen
NO2  hv  NO  O
The atomic oxygen initiates oxidizing processes or quickly combines
with molecular oxygen to form ozone, which itself is reactive and acts
as an oxidant:

O  O2  M  O3  M
O3  NO  NO2  O2
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Photochemical Smog
M is an energy-absorbing molecule or particle is required to stabilize
O3 or else it will rapidly decompose.
Under normal conditions, the ozone formed will be quickly removed by
reaction with NO to provide NO2 and O2.
However, when hydrocarbons are present in the atmosphere this
mechanism is partially eliminated as NO reacts with the hydrocarbon
radical peroxyacyl (RCO.3) and as a result ozone concentration builds
up to dangerous levels.
Hydrocarbons compete for free oxygen released by NO2 decomposition
to form oxygen-bearing free radicals such as the acyl radical.
HC  O  RCO  (acyl radical )
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Photochemical Smog
This radical takes part in a series of reactions involving the formation
of still more reactive species, which in turn react with O2,
hydrocarbons and nitric oxide.

RCO  O2  RCO 3 peroxyacyl radical 

RCO 3  HC  RCHO aldehydes 
R2CO (ketones )
RCO3   NO  RCO2   NO2
RCO 3 O2  RCO2  O3
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 Thank you

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