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Basic concepts:
Before attempting to describe the operations that comprise a chemical process, it is necessary to introduce
several basic concepts and basic laws that must be understood before a description is meaningful.
1. Equilibrium – a state where there is zero net interchange of properties (usually mass or energy in
chemical processing) for all combinations of phases
– a state of balance or quality between opposing forces
– equilibrium state gives the limit of an operation. It represents end points of any naturally occurring
processes which cannot be changed without making some change in the conditions governing the
system.
– For equilibrium to exist within any closed system where two phases co-exist, it is necessary that:
i. the two phases have the same temperature
ii. they have the same pressure, and
iii. any substance which is able to pass freely between the two phases have the same chemical
potential in each of the phases
2. Driving Force – the difference between the existing condition and the equilibrium condition.
3. Flow Patterns. In many of the operations for transferring energy or material from one phase to
another, it is necessary to bring two streams into contact to permit a change toward equilibrium of
energy or material, or both.
a. Co-current Flow – both streams flow in the same direction. The limit in amount of transfer that
can occur is firmly set by equilibrium conditions that will be reached between the two streams.
b. Counter-current Flow – the two streams being contacted are made to flow in opposite directions.
BASIC LAWS
Much of the background needed for an understanding of unit operations is based on the
fundamental laws of physical sciences. Some of these relationships are as follows:
1. Law of Conservation of Mass – Matter can neither be created, nor destroyed. Thus the material
entering any system must either leave or accumulate within it. There can be no loss or gain during a
process taking place within the system. Under steady-state conditions, the law of conservation of mass
requires that the input must be equal to the output from the system.
2. Momentum Balances – In a system, through which a gas or liquid, momentum may enter or leave the
system by virtue of the overall fluid motion as well as the shear forces acting on the fluid elements.
3. Energy Balances – (Law of Conservation of Energy) Energy can neither be created nor destroyed, but
can be transformed from one form to another. The total energy of any closed system remains constant.
4. Ideal Gas Law – Although the ideal-gas law does not apply precisely to any actual gas, where the
intermolecular attraction and the volume of the molecules themselves are not negligible, a great
majority of gases and vapors at ordinary temperatures and pressures obey the law sufficiently.
5. Avogadro’s Hypothesis – Equimolal quantities of all gases occupy the same volume at the same
conditions of temperature and pressure.
6. Perfect Gas Mixture – In a mixture of ideal gases, the molecules of each component gas behave
independently as though they alone are present in the container. The partial pressure of the component
gas present in a mixture of gases is the pressure that would be exerted by the component gas if it alone
were present in the same volume and the same temperature as the mixture.
𝑛𝐴 𝑅𝑇
𝜌𝐴 = where nA – number of moles of component A in mixture
𝑉
7. Dalton’s Law – The total pressure exerted by a gaseous mixture is equal to the sum of the partial
pressures of its components.
𝜌𝑇 = 𝜌𝐴 + 𝜌𝐵 + 𝜌𝐶 + ….
8. Amagat’s Law – The total volume occupied by a gaseous mixture is equal to the sum of the partial
volumes of its components.
𝑉𝑇 = 𝑉𝐴 + 𝑉𝐵 + 𝑉𝐶 + ….
9. Ideal Solution – Volume is conserved when components that form an ideal solution are mixed. That
is, the volume of an ideal solution at a given temperature and pressure is equal to the sum of the
volumes of its pure constituents at the same temperature and pressure. Ideal solutions, in general,
assume no chemical interactions, similar molecular sizes and equal attractive forces between like and
unlike molecules.
𝑉 = ∑ 𝑛𝑖 𝑣𝑖 where vi – molal volume of pure component I at the temperature and pressure of
solution
10. Average Molecular Weight of a Gas Mixture – A mole of any pure substance is defined as that
quantity whose weight is numerically equal to its molecular weight. The average molecular weight of
a mixture of substances is given by
𝑀𝑚 = ∑ 𝑦𝑖 𝑀𝑖 where Mi – molecular weight of each component i
Mm – molecular weight of mixture
Examples: mass transfer through a gas: water in an open pail evaporates into still air
mass transfer through a liquid: a piece of sugar added to a cup of coffee diffuses to the
surrounding solution
mass transfer through a solid: A freshly cut green timer when exposed to the atmosphere
will dry partially when the water in the timber diffuses
through the wood, to the surface, and then to the
atmosphere
The three fundamental transport processes of momentum, heat, and mass are characterized by
the same general type of equation:
𝑑𝑟𝑖𝑣𝑖𝑛𝑔 𝑓𝑜𝑟𝑐𝑒
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 =
𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒
Mass transfer can be treated in a manner somewhat similar to that used in heat transfer with
Fourier’s Law of conduction. However, an important difference is that in molecular mass transfer, one or
more of the components of the medium is moving while in heat transfer by conduction, the medium is
usually stationary.
PRINCIPLES OF DIFFUSION
Diffusion is the movement of the chemical species occurring in one phase, across the interface and
into another phase. The diffusional transfer of mass is a result of a concentration gradient.
In contrast to discrete equilibrium stage processes, continuous contact processes do not attain
equilibrium at any point within the system.
The exploitation of the concentration difference in the form of the rate of mass transfer equations
before the attainment of equilibrium between phases is central to the design calculation of mass transfer
separation process.
Additional Problems
1. A mixture of helium and nitrogen gas is contained in a pipe at 298 K and 1 atm total pressure which is
constant throughout. At one end of the pipe at point 1 the partial pressure P A1 of He is 0.60 atm and at
the other end 0.2 m, PA2 = 0.20 atm. Calculate the flux of He at steady state is DAB of the He-N2 mixtures
is 0.687 x 10-4 m2.
2. Ammonia gas (A) and nitrogen gas (B) are diffusing in counter-diffusion through a straight glass tube
2.0 ft long with an inside diameter of 0.080 ft at 298 K and 101.32 KPa. Both ends of the tube are
connected to large mixed chambers at 101.32 KPa. The partial pressure of NH 3 in one chamber is
constant at 20.0 KPa and 6.666 KPa in the other chamer. The diffusivity at 298 K and 101.32 KPa is
2.30 x 10-5 m2/s.
a. Calculate the diffusion of NH3 in lbmol/hr and kg/s
b. Calculate the diffusion flux of N2
c. Calculate the partial pressure at point 1.0 ft in the tube
3. Calculate the rate of diffusion of sugar through a stagnant film of coffee 0.10 cm thick when the
concentrations at 15% and 5%, respectively, on either side of the film. Assume the diffusivity of sugar
through coffee under the given conditions to be 0.70 x 10 -5 cm2/s and the density of a 10% solution is
1.0139 g/cc.
4. Calculate the time it will take to evaporate a 10-mm unknown liquid at 25 °C (density = 40 lb/ft3, MW=60)
in a 5-m diameter circular tank. The vapor pressure at 25 °C is 180 mmHg, pressure is atmospheric and
Dv = 0.0329 ft2/hr. Stagnant air film is 3mm.
5. A drop of liquid toluene is kept at uniform temperature of 25.9 °C and is suspended in air by a fine wire.
The initial radius is 2.0 mm. the vapor pressure of toluene at 25..9 v is 3.84 KPa and the density of liquid
toluene is 866 kg/m3.
a. Derive an equation to calculate the time for the drop to evaporate completely in a large volume of
still air
b. Calculate the time, in seconds, for complete evaporation
6. In an O2 – N2 gas mixture at 1.01325 bar and 20 °C, the concentration of O2 at two planes 0.002 m apart
are 20% and 10% volume respectively. (a) Calculate the rate of diffusion of O 2 expressed as kg moles
of Oxygen/m2 s for the case where N2 is non-diffusing. DO2-N2 = 0.181 x 10-4 m2/s assuming equimolal
counter diffusion.
7. A vertical glass tube of diameter 0.3 cm is filled with benzene at 20 °C to a depth of 2 cm from top end.
After 24 hours, the liquid level in the tube had fallen to 2.5 cm from the top end. Estimate the diffusivity
of benzene into air if the air above the liquid surface in the tube is stagnant. The vapour pressure and
density of benzene at 30 °C are 60 mmHg and 800 kg/m3 respectively.
8. A vertical glass tube 1 cm in diameter is filled with liquid acetone to a depth of 5 cm from the top open
end. After 4 hours of operation at 303 K and at a total pressure of 1 atm, the level dropped by 2 mm. the
density of the liquid is 790 kg/m 3 and its vapour pressure is at 288 mmHg under the given operating
conditions. Neglecting the counter diffusion of air to replace the liquid, calculate the diffusivity of acetone
in air.
9. A gas mixture containing 1/5 hydrogen and 4/5 methane by volume is prepared through which oxygen
is allowed to diffuse. The total pressure is 1 x 10 5 N/m2 and temperature is 2 °C. estimate the rate of
diffusion of O2 through the gas film of thickness 3 mm when concentration change across the film is 12%
to 7% by volume. Diffusivity data at 1 atm, 0 °C is
a. DO2-N2 = 7.1 x 10-5 m2/s
b. DO2-N2 = 1.88 x 10-5 m2/s
10. A vertical glass tube 3 mm in diameter is filled with toluene to a depth of 2 cm from the top open end.
After 275 hours of operation at 303 K and at a total pressure of 1 atm, the level dropped to 7.75 cm
from the top. The density of the liquid is 820 kg/m 3 and its vapour pressure is at 57 mmHg under the
given operating conditions. Neglecting the counter diffusion of air to replace the liquid, calculate the
diffusivity of toluene in air.
11. The diffusivity of CCl4 is determined by Winklemann method in which the level of liquid contained in a
narrow tube maintained at a constant temperature of 321 K is continuously measured. At the top of the
tube air is flowing and the partial pressure of the vapour at the top of the tube may be taken as zero at
any instant. Assuming molecular mass transport, estimate the diffusivity of CCl4 in air. Vapor pressure
of CCl4 is 282 mmHg ad density of CCl4 is 1540 kg/m3. The variation in liquid level with respect to time
is given below: