CH6503 CHEMICAL ENGINEERING THERMODYNAMICS-II

UNIT-V
REFRIGERATION

Principle of refrigeration (or) Refrigeration process:

❖ Refrigeration is the process of producing & maintaining a temperature below that of the
surrounding atmosphere.
❖ It implies production of low temperature by continually absorbing heat at a low level and
rejecting it at a high level.

Applications:

1. Chemical process industries – manufacture of rubber, textiles, chlorine, plastics, HF etc.

2. It is used to remove heat of chemical reactions and to liquefy process gases for gas separation
by distillation and condensation.
3. Separation of volatile hydrocarbons in petroleum industries, separation of gasoline from natural
gas, solvent recovery, crystallization of salts from solutions, manufacture of ice, transport and
preservation of food and beverages
4. Refrigeration is also used in manufacture of rayon, photographic film, gelatin etc.

Refrigeration cycle:

❖ A typical refrigeration cycle includes evaporation of the liquid, compression of the refrigerant
vapor, condensation of the vapor into liquid and finally expansion of the liquid.
i. Vapour Compression cycle
ii. Vapour Absorption cycle
iii. Air refrigeration cycle

Refrigeration capacity (or)‘Ton of refrigeration’

❖ Refrigeration Capacity is measured in ton of refrigeration. One ton is defined as the heat
absorption at the rate of 12000 BTU per hour. This rate corresponds to the rate of heat removal
that is required to freeze 1 ton of water in a day at 273 K.
❖ One ton of refrigeration is equivalent to a refrigeration rate of 12660 kJ/h.
❖ It determines the rate of circulation of the refrigerant, which decides the design and size of the
various units such as condenser, compressor, evaporator and the expansion devices.

Coefficient of performance(COP):

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 Let Q2 be the heat that is absorbed at a low temperature T2
& Q1 be the heat rejected at high temperature T1.
By first law of thermodynamics,
External work required to bring this transfer is

❖ The efficiency or Coefficient of performance (COP) of a refrigerator is defined as the quantity of

heat absorbed at the low temperature per unit of work.

Refrigerant:
❖ A refrigerant is a compound that can readily absorb heat at one temperature, then compressed by
a heat pump to a higher temperature and pressure where it changes phaseand discharges the
absorbed heat.
(E.g) Propane and ammonia, Methyl chloride, carbondioxide, sulphur dioxide propane and
ammonia

Carnot refrigeration cycle:

● Carnot Cycle working under the principle of ideal refrigeration cycle operating between the same two
thermal reservoirs. It consists of the following steps:
1. Reversible adiabatic compression (AB),
2. isothermal heat rejection (BC),
3. reversible adiabatic expansion (CD),
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 4. isothermal heat absorption (DA).
● 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 represents the heat absorbed. It 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 against a
temperature gradient is given by W = Q1-Q2, which is the enclosed area ABCD in fig.

● COP of carnot cycle depends only on temperature levels between which the machine operates and is
independent of the working fluid.
Eqn. (1) on rearrangement gives

which is the minimum work required for transferring heat Q2 from a low temperature T2 to
a higher temperature T1.
● It is impossible to construct a refrigeration machine that will pump heat with less expenditure of
work less than eqn.(2).
● Because of inherent irreversibilities in any practical processes, COP of actual machine will be less
than eqn.(1) & work required for transfer of a given quantity of heat will be more than that given
by eqn.(2).
● However, these equations can be used as a standard for comparison of the actual processes and
suggest possible improvement in such processes.

Problem: A refrigeration machine operating at a condenser temperature of 290K needs 1 KW of

power per ton of refrigeration. Determine the following:

i. The coefficient of performance.

ii. The heat rejected to the condenser.
iii.The lowest temperature that can be maintained.

Solution:

(i) 1Ton of refrigeration = 12660 kJ/h = 3516.67 W

Q2 = 3516.67 W; W=1000.

COP = Q2/W = 3516.67/1000 =3.52

(ii) The heat rejected, Q1=Q2+W =3516.67 + 1000 = 4516.67 W =4.52 Kw

(iii) Let T2 is the lowest possible temperature in the refrigerator

Vapour- Compression Cycle:

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❖ The actual refrigeration cycle are less efficient than ideal carnot cycle because of presence of the
inevitable irreversible effects, such as friction, imperfect heat insulation and because of the finite
temperature difference that is maintained for a good heat transfer rate in the refrigerator and the
condenser.
❖ In this cycle, the refrigerant vapour is compressed (AB) to such a pressure that the available
cooling water can condense the vapor in a condenser (BC) operated at this pressure is maintained
constant.
❖ The vapour, during condensation rejects heat to the cooling medium. By passing through a throttle
valve, the pressure of the liquid leaving the condenser is reduced (CD) to the pressure maintained
in the evaporator. The liquid then evaporates (DA), absorbing heat at constant temperature T2.

❖ The vapour thus produced enters the compressor, and the cycle is repeated. The process is
represented on the T-S diagram as shown in fig. The liquid portion of refrigerant leaving the
throttling valve is vapourised at constant pressure P2 and constant temperature T2 in the refrigerator.
❖ The vapour leaving the refrigerator is saturated (A). It is possible that the vapour leaving the
refrigerator may get slightly superheated or may be slightly unsaturated.
❖ On adiabatic compression, the vapour gets superheated (B) and this vapour enters the condenser at
adiabatic compression, the vapour gets superheated (B) and this vapour enters the condenser at
pressure P1.
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❖ The reversible adiabatic compression is an isentrophic process, represented by the vertical line
AB. In the condenser, the vapour is first cooled and the superheat is removed from the vapour, as
shown by the line BE, and then it is condensed at constant temperature T2. The saturated liquid
(C) leaving the condenser is expanded by throttling.
❖ The throttling is a constant enthalpy process and is represented by the curve CD. Throttling results
in the partial vaporization of the liquid, and the point (D) representing the mixture leaving the
valve lies in the two-phase region.
❖ Fig. (c) shows the vapour-compression cycle on a pressure enthalpy system. As the heat
absorption in the refrigerator occurs at constant –pressure, the heat absorbed during vaporization
is equal to the change in the enthalpy of the refrigerant.

The heat rejected is

Since the work required, W = Q1-Q2, & HD = HC (the process CD is isenthalpic),

❖ If the rate of heat absorption is specified, the rate of circulation of the refrigerant (m) can be easily
evaluated.

❖ For a refrigerator rated at 1ton (Q2 = 12660 kJ/h), the rate of circulation in kg/h may be evaluated by

❖ The vapour leaving the compressor is superheated at condenser pressure P1. Its temperature is
greater than the saturation temperature T1. The Throttling process is highly reversible.
❖ Because of these two reasons, the ordinary cycle is less efficient than the carnot cycle. By
allowing the evaporation to proceed upto point A in Fig (b), and compressing the resultant vapour
liquid mixture adiabatically to saturation at pressure P1, (process A` E) the first difficulty can
overcome.
❖ If the expansion process (CD) were carried out in an expansion engine instead of throttling, the
irreversibilities can be minimized to a great extent.
❖ This is done in an expansion engine vapour- compression cycle. Here the expansion is isentropic
and hence CD is a vertical line on the T-S diagram.

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 The heat absorbed and heat rejected during this cycle are

&

The work input, W = Q1-Q2,

❖ As the expansion engine operating on a two-phase mixture is expensive, this cycle is preferred
only for large installations. Because of their simplicity and low cost, the throttle valves are
preferred over turbines in small installations.

Problem:A Vapour-compression cycle using ammonia as refrigerant is employed in an ice manufacturing

plant. Cooling water at 288K enters the condenser at a rate of 0.25 kg/s and leaves at 300K. Ammonia at
294K condenses at a rate of 0.50kg/minute. Enthalpy of liquid ammonia at 294K is 281.5 kJ/kg. The
compressor efficiency is 90%. Saturated ammonia vapour at 258K and enthalpy of 1426 kJ/kg enters the
compressor. What is the power requirement of the compressor and refrigeration capacity in tons?

Solution:
Since heat is rejected at constant pressure in the condenser,

- is the cooling water circulation rate

- is the temperature rise of water

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 Heat absorbed and work required are evaluated as

Power requirement of the compressor:

= 3.0625/0.9 = 3.4028 kW = 4.56hp

Refrigerator capacity = 9.5375 x3600 kJ/h = 9.5375 x3600/12660 = 2.71 ton

Choice of refrigerant (or) Properties of refrigerant:

1. Boiling temperature: It is necessary thatthe operating pressure be maintained above atmospheric

to avoid air and moisture leaks into the system. The normal boiling point of the refrigerant should
therefore be lower than the desired temperature levels in the refrigerator.
2. Freezing point: The freezing point of the refrigerant should be well below the minimum
temperature at which the system is operated.
3. Critical temperature and pressure: The critical temperature and pressure of the refrigerant
should be above the operating system temperature and pressure. If the operating temperature is
above the critical temperature, it is impossible to condense the gas by compressing it to high
pressures.
4. Condenser and evaporator pressures: The condenser pressure should not be very high. If
pressure is very high, the cost of equipment & the cost of operation would be excessive. If the
evaporator pressure is excessively low, the compression ratio would be abnormally high. If the
refrigerant has sub-atmospheric vapour pressures at the temperature in the refrigerator coils, the
possibility of contamination by leaks cannot be overruled.
5. Specific volume: Specific volume of vapour determines the size of the compressor. Low suction
volumes are desirable for reciprocating compressors and high suction volumes for centrifugal
compressors.
6. Latent heat: A high latent heat of vaporization of the refrigerant is desired, because it results in
high refrigerating effect per unit weight of the refrigerant and low rate of circulation of the
refrigerant.
7. Specific heat of liquid: If the specific heat of the refrigerant liquid is unduly high, large quantity
of heat would have to be removed to cool the hot liquid entering the evaporator to bring its
temperature down to the saturation value. Therefore low specific heat of liquid refrigerant is
preferred.
8. Molecular weight: It affects the compressor size because the specific volume of the vapour
directly related to it. A high molecular weight refrigerant gives high specific volumes of vapour,
which is preferred for centrifugal compressors, whereas for reciprocating compressors a low
molecular weight for the refrigerant is advantageous.
9. Safety aspects: Refrigerants are grouped according to toxicity and flammability.
Group1: Halogenated hydrocarbons are relatively non-flammable, non-toxic and non-explosive
Group2: These are either toxic or flammable. e.g. methyl chloride and sulphur dioxide

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 Group3: Highly flammable and explosive refrigerants like propane, propylene, ethane, ethylene,
methane etc.,
10. Other desirable properties: Normally a refrigerant would be in use for a very long period.
Consequently, the chemical stability of the refrigerant is another important criterion in choice of a
proper refrigerant. They should be non-corrosive, low viscosity and high thermal conductivity. It
is necessary that they should have a vapour pressure above atmospheric pressure at the evaporator
temperature and the vapour pressure should not be excessively high at the condenser temperature.

Air-Refrigeration Cycle:
❖ The refrigeration cycle is shown in diagram. Here, the working fluid is air, which undergoes no
phase change in the unit.
❖ The air is compressed adiabatically to a pressure P1 and temperature T1 in the compressor (AB) . In
the cooler, it is then cooled at constant pressure P1 (BC).
❖ The air at pressure P1 is expanded in an engine or a turbine to a pressure P2 which is an ideal case is
equal to the pressure of air at the compressor intake (CD). The work output of the expander
contributes a part of the work requirement of the compressor.
❖ The gas leaving the expander is passed through the refrigerator, where it absorbs heat at constant
pressure P2(DA). The gas leaving the refrigerator enters the compressor, and the cycle is repeated.
❖ In the T-S diagram, T1 is the temperature of the cooling water and T2 is the temperature to be
maintained in the refrigerator.

❖ The area under the curve DA down to the S-axis is the heat absorbed in the refrigerator and the
enclosed area ABCD is the work required for the removal of heat. It can be easily shown that, an
ideal Carnot refrigerator operating between temperature levels T1 and T2 removes greater amount of
heat with less work than an air-refrigeration machine.
❖ Let the rate of air circulation be . Assume that the heat capacity of air remains constant during the
cycle. The heat absorbed is

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 and the heat rejected is

❖ The initial and final temperatures of the fluid undergoing adiabatic process are related to the initial
and final pressures

Using the above eqn, we can write

Substitute (3) in (1)

Advantage of the air-refrigeration cycle:

❖ The air is available at no cost. Majority of the commonly used refrigerants possess undesirable
properties like corrosiveness, explosiveness, toxicity, and flammability. Compared to these, air is
harmless.
Disadvantages:
❖ The disadvantages of the air cycles are their low efficiencies, large heat transfer surfaces required,
and large quantity of air to be circulated through the unit.
❖ The heat transfer in the refrigerator and the cooler occurs through air-films, which offer very high
resistance to heat transfer, large temperature difference would be necessary between the air and the
refrigerator as well as between the air and the cooler.
❖ For any specified refrigeration requirement, this would lead to an increase in the difference between
the temperature of air in the cooler and that in the refrigerator, which, in turn, leads to low
efficiencies.
❖ Also, since the specific heat of air is low, relatively large quantity of air is circulated through the
unit in order to achieve inappreciable amount of refrigeration.

Problem:Anair-refrigeration machine rated at 10 ton is used to maintain the temperature of a cold room
at 261 K when the cooling water is available at 293 K. The machine operates between pressures of 1.013
bar and 4.052 bar. Assume a 5-K approach in the cooler and the refrigerator. The specific heat of air may
be taken as 1.008kJ/kg K and γ = 1.4. Calculate the COP and air-circulation rate.

Solution:

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 The temperature of the air leaving the refrigerator is TA= (T2) = 261-5 = 256 K
The temperature of the air leaving the cooler is TC = (T1) = 293+5 = 298 K

To determine temperature TB;

Similarly, TD = 200.5 K.

(1)

COP = 256/(380.4-256)
= 2.06

(2) To find the air-circulation rate, consider the energy balance in the refrigerator.

Vapour- Absorption refrigeration system: (additional topic)

❖ In a vapour-compression cycle, external work is required to run the compressor. The ultimate
source of this work is normally a heat engine, which absorbs heat from a high temperature source
and rejects part of it to a heat sink; the difference is transformed to work.
❖ The net effect is, a part of the heat that is absorbed from a high temperature source by a heat engine
is utilized in a vapour-compression refrigeration system for pumping heat from a low temperature
region to a high temperature region.
❖ An absorption refrigeration unit uses the heat absorbed from a high temperature source directly for
achieving the necessary refrigeration.
❖ The principle behind absorption refrigeration is shown in fig. For a refrigeration rate of Q2 kJ/h, the
minimum work required when the refrigerator and the condenser are at temperatures T2 and T1
respectively is given by

❖ In order to deliver a work equal to W, a heat engine operating between a high temperature source
at T3 and the surroundings at T1 should absorb a quantity of heat Q3, where

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 Substitute (1) into (2) gives

Eqn.(3) gives the amount of heat from a high temperature source required to obtain a refrigeration
capacity of Q2. The ratio (Q2/Q3), which is the refrigeration obtained per unit quantity of high
temperature heat, is known as the efficiency of an absorption refrigeration cycle.

Eqn.(4) represents the ideal case, because both heat engine and the refrigerator were assumed to
operate on the carnot cycle.
❖ Actual efficiency will be less than the value given by this equation. For e.g. consider a heat source
of saturated steam at 1 bar (T3 = 373K), surroundings at 300K (T1) and a refrigerator space at
263K (T2). Using Eqn.(4), we get the efficiency of 1.27. For the actual absorption refrigerator, the
efficiency would be roughly only one third of this value.

❖ The compressor in the vapour compression unit is replaced by an absorber-regenerator

combination as shown in fig.
❖ Heat is liberated when the refrigerant vapour is absorbed in a non-volatile solvent. A typical
absorption refrigeration cycle for moderate temperature applications uses water as the refrigerant
and lithium bromide solution as the absorbent.
❖ For lower temperatures, ammonia is used as the absorbent and water as the solvent. The heat
liberated during absorption is discarded to the surroundings at temp.T1.
❖ The liquid leaving the absorber is a solution of the refrigerant in a relatively non-volatile solvent.
It is pumped through a heat exchanger as shown in fig.
❖ The temperature and pressure of solution increases when the liquid reaches the regenerator.
Regeneration of the refrigerant is achieved by evaporating it from the solution and the heat

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 required for this is absorbed from the source at T3. Low pressure steam is usually used as the
source.
❖ The regenerated absorbent liquid, which is almost free of the refrigerant, is cooled by passing
through the heat exchanger.
❖ The heat given off by the solvent utilized to raise the temperature of the solution leaving the
absorber. The solvent is recycled to the absorber.

Liquefaction processes:

❖ It is widely used for the separation of gaseous mixture into their component parts. It is used for
the production of pure gases such as oxygen and nitrogen from air which is used in missile and
rocket development. Liquid hydrogen finds application in nuclear weapons development and
rocket propulsion.
❖ It makes the task of storage space and transportation of gases simple. Reduction of storage space
and transportation costs achieved.

❖ Three methods of Liquefaction:

1. Vaporization of a liquid
2. Joule-Thomson expansion
3. Expansion of gas in an engine delivering external work

1. Vaporization of a liquid:

1. This method can be used to reach liquid-air temperatures by employing series of liquids of
different boiling points.
2. The liquid of lowest boiling point absorbs heat from the system to be refrigerated and
delivers this heat to next higher boiling liquid in a condenser-boiling combination.
3. Then the fluid of highest boiling point is condensed by cooling (air or water) thus
discharging the heat to the atmosphere.
4. This method has been used for liquefaction of air and natural gas. The lowest temperature
can be attained by this method is 63K, the triple point of nitrogen.

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2. Free Expansion:
1. For liquefaction of the gas by this method, the initial pressure of gas should be raised to a
high value that on Joule-Thomson expansion, which is an isenthalpic operation, the constant
enthalpy lines cut into the two-phase region as shown in fig. Otherwise, no liquefaction is
possible by Joule-Thomson expansion. For e.g., the gas at an initial state such as one
represented by a point A in fig., cannot be liquefied by throttling.
2. The Linde process for gas liquefaction works on the principle of Joule-Thomson expansion. It
can be used for liquefaction of gases that cool on Joule-Thomson expansion, that is for gases
that posses a positive Joule-Thomson Coefficient.
3. Most gases have a positive Joule-Thomson coefficient at ordinary conditions, hydrogen and
helium bring exceptions. Even hydrogen and helium have positive coefficients below 100K
and 20K respectively. The Linde process for liquefaction of air is shown in fig.
4. The temperature of air at the upstream side of the throttle valve is reduced to a sufficiently
low value (e.g.170K at 100 bar) so that the constant enthalpy lines cut into the two-phase
region.
5. The cooling of air is achieved by passing it counter-currently to the unliquefied part of the air
leaving the throtling valve.
6. The fresh air and the unliquefied air form the input to the compressor.

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7. Air leaving the compressor is cooled by ambient air or by cooling water and subsequently by
counter-current heat exchange with the recycled air. In the throttling valve, a fraction of the
gas is liquefied.
8. By applying the first law, it can be shown that the fraction x of the liquefied air is given by

3. Isentropic Expansion:

1. The Claude process for gas liquefaction utilizes isentropic expansion of a compressed gas.
The throttle valve in Fig. will be replaced by an expansion turbine. The process can be
followed on the T-S diagram as shown in fig.
2. The vertical line DE represents the isentropic expansion. The fraction of gas liquefied can be
determined as follows.
3. The energy balance around the heat exchanger, turbine and the separator gives

where Ws –work delivered by the turbine

4. If the turbine operates adiabatically, the shaft work Ws is equal to the decrease in enthalpy of
the gas during expansion.

5. The fraction of gas liquefied is an isentropic expansion is clearly greater than that in a free
expansion. However, since the turbine is to be operated with a two phase-mixture, the
isentropic expansion process has certain practical difficulties.
6. To overcome these, only a portion of gas leaving the compressor may be expanded
isentropically. The remaining portion is cooled in a heat exchanger before it is expanded in a
throttle valve.
7. The saturated gas leaving the turbine is used to cool the portion of the gas that is throttled. In
this way, the inlet stream to the valve can be cooled to a very low temperature, which will
result in greater liquefaction.
8. The cost of power is an important consideration in the commercialization of liquefaction
process, it is essential that the thermodynamic efficiency of the process is known. It is
defined as the ratio of the minimum reversible work for the given process to the actual work.
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 9. It can be evaluated by the product of two efficiencies, (i.e) the cycle efficiency and practical
efficiency.

10. The reversible work is the least possible amount of work that is necessary to effect a given
change in the state of the system. It is given by second law of thermodynamics as

where T0 is the temperatureof the heat sink to which heat may be rejected in large
quantities.
11. The reversible work depends only on initial and final states of the system and is independent
of the cycle.
12. The theoretical work for ideal operation is evaluated as the work required by the given cycle
if it is operated after eliminating all irreversible effects. The practical efficiency takes into
account the imperfections of the equipment used in the cycle.

Comparison between Joule-Thomson and Isentrophic cooling:

❖ Joule-Thomson cooling occurs when a non-ideal gas expands from high to low pressure at
constant enthalpy (Isoenthalphic) condition. The effect can be amplified by using the cooled
gas to pre-cool the incoming gas in a heat exchanger.
❖ Isenthalpic expansion is through control valve where entropy changes. Whereas expansion
through a steam turbine is isentropic one and enthalpy drops. Isentropic expansion is more
efficient process as compared to isenthalphic one.

Solution:

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 Comparison between vapour compression and vapour absorption system:

S.No. Vapour compression system Vapour absorption system

Uses electricity - a high grade energy as Uses heat – a low grade energy-as the
1 the energy source for refrigeration energy source for refrigeration
Uses a compressor for vapour Uses an absorber-generator assembly for
2 compression vapour compression
Moving parts are in the compressor, more Moving parts are in the pump,little wear
3 wear and tear, high maintenance cost and and tear, very low cost of maintenance
noisy operation and quiet operation.
COP decreases considerably with COP is not affected if the system works
4 decrease in evaporator temperature at lower evaporator temperature
The capacity-tons of refrigeration of the The capacity of the system remains
5 system decreases rapidly with decrease in almost same with decrease in evaporator
evaporator temperature. temperature.
The COP of this system decreases with The COP of this system does not vary
decrease in loads. Poor performance at with variation in load. The system at
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reduced loads- the COP varies with load. reduced load is almost efficient as at full
load- the COP does not vary with load.
7 Charging of refrigerant is difficult Charging of refrigerant is simple
More chances of leakage of refrigerant No chance of leakage of refrigerant as
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there is no compressor to cause leakage
Liquid traces of refrigerant in the suction Liquid traces of refrigerant in the piping
9 line may damage the compressor at the exit of evaporator create no danger.

Cogeneration

❖ Cogeneration or Combined Heat and Power (CHP) is defined as the sequential generation of two
different forms of useful energy from a single primary energy source, typically mechanical
energy and thermal energy (simultaneously generate both electricity and useful heat).
❖ Mechanical energy may be used to drive an alternator for producing electricity, or rotating
equipment such as motor, compressor, pump or fan for delivering various services.
❖ Thermal energy can be used either for direct process applications or for indirectly producing
steam, hot water, hot air for dryer or chilled water for process cooling.

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❖ Cogeneration provides a wide range of technologies for application in various domains of
economic activities. The overall efficiency of energy use in cogeneration mode can be up to
85% & above.

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