PE8491 Chemical Engineering

Thermodynamics
Unit –IV
December 2019-April 2020

Dr. R.Malini,
Scientist,
Electro-inorganic chemicals Division
CSIR-CECRI
Unit IV
Refrigeration and liquefaction process,
Thermodynamic Potentials,
thermodynamic correlation,
Maxwell relations,
criteria for Equilibria and stability.
Clapeyron equation
REFRIGERATION
Refrigeration is the process of producing and maintaining a temperature below that of the
surrounding atmosphere.
Examples:
air conditioning of buildings, transportation, and preservation of foods and beverages, the
manufacture of ice and the dehydration of gases, lubricating-oil purification, low-temperature
reactions, and separation of volatile hydrocarbons.
Since heat cannot flow from a body at low temperature to one at a higher temperature
spontaneously, external work is required to achieve refrigeration. Thus, refrigeration is
essentially an operation involving the pumping of heat from one temperature to a higher
temperature.
In mechanical refrigeration, which is the most commonly used method for commercial
applications, the low temperature is produced by the evaporation of a liquid whose properties
are, such that, at the pressure of evaporation, the saturation temperature is low. The evaporated
liquid is then returned to its original state for continuous operation.
 The complete series of processes that the working fluid— the refrigerant—undergoes,
constitute a refrigeration cycle.
A typical refrigeration cycle includes evaporation of the liquid refrigerant, compression of the
refrigerant vapour, condensation of the vapour into liquid, and finally expansion of the liquid.
 THE CARNOT
REFRIGERATOR
 The refrigeration cycle is a reversed heat-engine cycle.
 It consists of two isothermal steps in which heat |Qc| is absorbed at the lower
temperature Tc and heat |QH | is rejected at the higher temperature TH, and two
adiabatic steps.
 The cycle requires the addition of net work W to the system. Since ΔU of the
working fluid is zero for the cycle, the first law is written as

The measure of the effectiveness of a refrigerator is its coefficient of performance

ω, defined as:

Equation may be divided by |Qc|:

This equation applies only to a refrigerator operating on a Carnot cycle, and it gives the
maximum possible value of ω for any refrigerator operating between given values of
TH and Tc. It shows clearly that the refrigeration effect per unit of work decreases as
the temperature of heat absorption Tc decreases and as the temperature of heat
rejection TH increases.
For refrigeration at a temperature level of 278.15 K (5°C) in a surroundings at 303.15
K (30°C), the value of ω for a Carnot refrigerator is:
 Carnot Refrigeration Cycle
AB - Reversible adiabatic
compression
BC - Isothermal heat rejection
CD - Reversible adiabatic
expansion
DA - Isothermal heat absorption
•During the isothermal heat absorption (DA),
an amount of heat Q2 is absorbed at low
temperature level T2. The area ADXY on the T-S
diagram [Fig. 5.8(b)] represents the heat
absorbed which is equal to T2 ∆S, where ∆S is
the change in entropy of the fluid due to the
heat absorption. Heat rejected at higher
temperature T1 is equal to Q1 and is
represented by the area BCXY. It is equal to T1
∆S.
The external work done for this transfer of heat
 Vapor-compression refrigeration cycle

A liquid evaporating at constant pressure (line 1 →2) provides a means for heat
absorption at a low constant temperature.
The vapor produced is compressed to a higher pressure, and is then cooled and
condensed with rejection of heat at a higher temperature level.
Liquid from the condenser returns to its original pressure by an expansion process.
The pressure drop in this irreversible process results from fluid friction in the valve.
line 4 → 1 represents this throttling process.
The dashed line 2 → 3' is the path of isentropic compression
Line 2 → 3, representing the actual compression process, slopes in the direction of
increasing entropy, reflecting inherent irreversibilities.
To design the evaporator, compressor, condenser, and auxiliary equipment one must
know
the rate of circulation of refrigerant m. This is determined from the rate of heat
absorption in
the evaporator by the equation:

Vapor-compression refrigeration cycle on a

P H diagram
Refrigerator Capacity
 The refrigerator capacity determines the rate of circulation of the
refrigerant, which in turn, decides the design and size of the various
units such as condenser, compressor, evaporator, and the expansion
devices.
 The capacity is sometimes measured in ton of refrigeration.
 One ton is defined as the heat absorption at the rate of 12000 BTU per
hour (One BTU is the amount of heat required to raise the temperature
of one pound, i.e. 0.4536 kg of water by one degree Fahrenheit, or
(1/1.8) K. Thus, 1 BTU = 1.055 kJ).
 This rate corresponds to the rate of heat removal that is required to
freeze 1 ton of water in a day originally at 273 K.
 One ton of refrigeration is equivalent to a refrigeration rate of 12660
kJ/h in SI units.
 THE CHOICE OF
REFRIGERANT
 The efficiency of a Carnot heat
engine is independent of the
working medium of the engine.
 The coefficient of performance of a
Carnot refrigerator is independent
of the refrigerant.
 The irreversibilities inherent in the
vapor-compression cycle cause the
coefficient of performance of
practical refrigerators to depend to
some extent on the refrigerant.
Ammonia, methyl chloride, carbon dioxide,
propane and other hydrocarbons
What is the commonly used refrigerant in refrigerator and air conditioner in India???
 The characteristics such as its toxicity,
flammability, cost, corrosion properties, and
vapor pressure in relation to temperature are of
greater importance in the choice of refrigerant,
so that air cannot leak into the refrigeration
system, the vapor pressure of the refrigerant at
the evaporator temperature should be greater
than atmospheric pressure.
 On the other hand, the vapor pressure at the
condenser temperature should not be unduly
high, because of the initial cost and operating
expense of high-pressure equipment.
 These two requirements limit the choice of
refrigerant to relatively few fluids
fully halogenated chlorofluorocarbons are
replaced by hydrogenated fluorocarbons,
A two-stage cascade refrigeration system

•The two cycles operate so that the heat

absorbed in the interchanger by the refrigerant
of the higher-temperature cycle 2 serves to
condense the refrigerant in the lower-
temperature cycle 1.
• The two refrigerants are so chosen that at the
required temperature levels each cycle operates
at reasonable pressures

Here, the two cycles operate so that the heat

absorbed in the interchanger by the refrigerant
of the higher-temperature cycle 2 serves to
condense the refrigerant in the lower-
temperature
cycle 1. The two refrigerants are so chosen that
at the required temperature levels each cycle
operates at reasonable pressures.
A two-stage cascade refrigeration system
For example, assume the following operating
temperatures

If tetrafluoroethane (HFC-134a) is the

refrigerant in cycle 2, then the intake and
discharge
pressures for the compressor are about 1.45 bar
and 7.72 bar, and the pressure ratio is about
5.32. If propylene is the refrigerant in cycle 1,
these pressures are about 1.1 bar and 4 bar,
and the pressure ratio is about 3.64. These are
all reasonable values.

On the other hand, for a single cycle operating

between 227 K and 303 K with HFC-134a as
refrigerant, the intake pressure to the condenser
is about 0.4 bar, well below atmospheric
pressure. Moreover, for a discharge pressure of
about 7.72 bar the pressure ratio is 19.3, too
high a value for a single-stage compressor.
Absorption-Refridgeration
 The most commonly used
absorption-refrigeration system
operates with water as the
refrigerant and a lithium bromide
solution as the absorbent.
Heat Pump
The heat pump, a reversed heat engine, is a device for heating houses and commercial
buildings during the winter and cooling them during the summer.
In the winter it operates so as to absorb heat from the surroundings and reject heat into the
building.
Refrigerant evaporates in coils placed underground or in the outside air; vapor compression
is followed by condensation, heat being transferred to air or water, which is used to heat the
building.
Compression must be to a pressure such that the condensation temperature of the refrigerant
is higher than the required temperature level of the building.
The operating cost of the installation is the cost of electric power to run the compressor.
If the unit has a coefficient of performance, | Qc | /W = 4, the heat available to heat the house
|QH| is equal to five times the energy input to the compressor.
Any economic advantage of the heat pump as a heating device depends on the cost of
electricity in comparison with the cost of fuels such as oil and natural gas.
The heat pump also serves for air conditioning during the summer.
The flow of refrigerant is simply reversed, and heat is absorbed from the building and
rejected through underground coils or to the outside air
LIQUEFACTION PROCESSES
 Liquefied gases are in common use for a variety of purposes.
 Examples:
 liquid propane in cylinders as a domestic fuel,
 liquid oxygen is carried in rockets,
 natural gas is liquefied for ocean transport
 liquid nitrogen is used for low-temperature refrigeration
 gas mixtures (e.g., air) are liquefied for separation into their component
species by fractionation.
 Liquefaction results when a gas is cooled to a temperature in the two-
phase region. This may be accomplished in several ways:
1. By heat exchange at constant pressure.
2. By an expansion process from which work is obtained.
3. By a throttling process.