Mass Transfer Fundamentals

(ChE-206)
Saqib Javed

Thermodynamics of Separation Process

+
Distillation (Intro)

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 Outline
• Background
• Why study Thermodynamics for Separation??
• Laws of thermodynamics
• Application of energy/entropy balance
• Phase equilibria
• VLE diagram
• Distillation

Separation Process Principles, Seader, 2nd/3rd ed.

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 Background
• Separations are achieved by enhancing the rate of mass
transfer by diffusion of certain species relative to mass
transfer of all species by bulk movement within a particular
phase.
• The driving force and direction of mass transfer by
diffusion is governed by thermodynamics, with the usual
limitations of equilibrium.
• Both transport and thermodynamic considerations are
crucial in separation operations. The rate of separation is
governed by mass transfer, while the extent of separation is
limited by thermodynamic equilibrium.

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 Why study Thermodynamics for Separation??

• Thermodynamic properties and equations

play a major role in separation operations,
particularly with respect to energy
requirements, phase equilibria, and sizing
equipment.
• Most industrial separation operations utilize
large quantities of energy in the form of heat
and/or shaft work.

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 General Separation Process

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• Energy estimates can be made by applying;

1 Law of
st

Thermodynamics

2 Law of
nd

Thermodynamics
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 1st Law of Thermodynamics

• It
  states that “change in the Internal energy of
a closed system is equal to the amount
of heat supplied to the system, minus the
amount of work done by the system on its
surroundings”.

• Internal energy is a state function.

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 Important Note
• All separation processes must satisfy the
energy balance.
• Inefficient separation processes require large
transfers of heat and/or shaft work both into
and out of the process.
• Efficient processes require smaller levels of
heat transfer and/or shaft work.

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• It referred as ‘the conservation of energy or
the energy balance’.
• The sum of all forms of energy flowing into the
system equals the sum of the energy flows
leaving the system.

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 Drawbacks of 1st Law

• It provides no information on energy

efficiency.
• It places no restriction on the direction of a
process.
• Satisfying the first law does not guarantee that
the process will occur.

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 2nd Law of Thermodynamics

• It states that “It is impossible to construct a

device, operating in a cycle, producing as its
sole effect net positive work while exchanging
heat with only one reservoir”.
• It referred as ‘the entropy balance’.

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It describes that;
• processes occur in a certain direction.
• Energy Efficiency of the system
• A process can occur when and only when it
satisfies both the first and the second laws of
thermodynamics.

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 Phase equilibria
• Phase/phase equilibrium
• Binary system
• Gibb’s Phase rule
• Raoult’s Law
• Henry’s Law
• Dew/bubble point
• Understanding of VLE diagram.

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 Phase
• A homogenous portion of a system that has
uniform physical and chemical
characteristics.
• Example: pure material, solid solution, liquid
solution, and gaseous solution, syrup and
sugar.
 Several phases may be present simultaneously
 phases are recognizable and separable

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• Homogeneous system = Single phase system
• Heterogeneous system = Multi phase system

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 Phase equilibrium 
• It is the state of balance between
two phases of a molecule.
• Thermodynamic definition: a system is at
equilibrium; if its free energy is at a minimum
• At equilibrium >>> system is stable
• If you change the temperature, pressure, or
composition, the free energy will change

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 Intensive Extensive
variable variable
Independent Depend on
of quantity quantity

mass or
T, P, x, y molar flow
rates

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• Binary System >> >2 components.
• Question>> When we combine two elements,
what “equilibrium state/phase” would we
expect to get?
• Answer is given by Phase rule

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 Gibb’s Phase Rule
• DOF: The no of independent variables is called
the number of degrees of freedom (F).
• Gibbs Phase Rule >>> a tool to define the
number of phases and/or degrees of phase
changes that can be found in a system at
equilibrium.
• Doesn’t applicable to non-equilibrium systems.

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• The DOF for Gibbs phase rule is,
>>>“ the number of intensive variables, V,
less (minus) the number of independent
equations, E.”
• For derivation of Phase Rule, see topic 4.1
(Seader)

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 Limitation of Gibb’s Phase Rule

• The Gibbs phase rule is limited because;

>>> it does not deal with the extensive
variables of feed, product, and energy streams,
whether for a batch or continuous process.
• However, the rule can be extended for
process applications by adding material and
energy streams, with their extensive variables
and additional independent equations.

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 Understanding of vapor pressure

• Vapor Pressure >> Pressure exerted by vapors

in a vessel.
• http://www.chemguide.co.uk/physical/phas
eeqia/vapourpress.html#

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 Raoult’s Law
It states that, “the vapor pressure of an ideal
solution is proportional to the mole fraction of
solvent”.

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 Henry's Law

• Useful for dilute solutions.

• It states that “at very low concentrations, the
partial pressure of the dilute component over
a liquid mixture is proportional to the
concentration”.

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 Point to remember

• If Henry's Law applies to one component of a

binary system, the other component is often
concentrated enough for Raoult's Law to
apply.

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Bubble point
• It is the temperature (at a given pressure)
where the first bubble of vapor is formed
when heating a liquid consisting of two or
more components.
Dew point
• It is the temperature at which the first drops
of a vapor mixture begin to condense.

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 VLE diagram
• Liquid and vapor are in equilibrium
• Rate of condensation = rate of evaporation

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 Tie-line

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• Tie line >>> a line connecting the phases in
equilibrium with each other – at a fixed
temperature (Isotherm)

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 Distillation

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 Distillation

• A method of separating mixtures based on differences

in volatility of components in a boiling liquid mixture.
• A unit operation, or a physical separation process, and
not a chemical reaction.
Applications:
 Use to separate liquid mixtures into various components
 Widely used in oil refinery
 Used to obtain pure products with greater efficiency

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 Importance of VLE data
• Distillation columns are designed based on the
boiling point properties of the components in
the mixtures being separated.
• Thus the sizes, particularly the height, of
distillation columns are determined by the (VLE)
data for the mixtures.

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• For vapor-liquid equilibrium, the separation
factor is the relative volatility.
 Light key (more volatile)
 Heavy key (less volatile)

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• If the ratio of partial pressure to the mole
fraction in liquid is defined as the volatility,
then,

• The ratio of these two volatilities is known as

the relative volatility given as,

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• Relative volatility is a measure of the difference between the vapor pressure of
the more volatile components of a liquid mixture and the vapor pressure of the
less volatile components of the mixture.

• This measure is widely used in designing large industrial distillation processes. In

effect, it indicates the ease or difficulty of using distillation to separate the more
volatile components from the less volatile components in a mixture.

• The higher is the relative volatility of a liquid mixture, the easier it is to separate
the mixture components by distillation.

• By convention, relative volatility is typically denoted as the Greek letter alpha, α.

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 Design Factors

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