Chapter 9

Refrigeration and Liquefaction

The word refrigeration implies the maintenance of a temperature below that of the surround-
ings. It is best known for its use in the air conditioning of buildings and in the preservation
of foods and chilling of beverages. Examples of large-scale commercial processes requiring
refrigeration are the manufacture of ice and solid CO2, the dehydration and liquefaction of
gases, and the separation of air into oxygen and nitrogen.
It is not our purpose here to deal with details of equipment design, which are left to spe-
cialized books.1 Rather, we consider:

∙ The model refrigerator, operating on a reverse Carnot cycle

∙ Refrigeration via the vapor-compression cycle, as in the common household refrigerator
and air conditioner
∙ The choice of refrigerants as influenced by their properties
∙ Refrigeration based on vapor absorption, an alternative to vapor compression
∙ Heating or cooling by heat pumps with heat extracted from or rejected to the surroundings
∙ The liquefaction of gases by refrigeration

9.1  THE CARNOT REFRIGERATOR

As indicated in Sec. 5.2, a refrigerator is a heat pump that absorbs heat from a region at a
temperature below that of the surroundings and rejects heat to the surroundings. It operates
with the highest possible efficiency on a Carnot refrigeration cycle, the reverse of the Carnot
engine cycle, as shown by Fig. 5.1(b). The two isothermal steps provide heat absorption QC
at the lower temperature TC and heat rejection QH at the higher temperature TH. The cycle
is completed by two adiabatic steps between these two temperatures. The cycle requires the

1ASHRAE Handbook: Refrigeration, 2014; Fundamentals, 2013; HVAC Systems and Equipment, 2016; HVAC

Applications, 2015; American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc., Atlanta;
Shan K. Wang, Handbook of Air Conditioning and Refrigeration, 2nd Ed., McGraw-Hill, New York, 2000.

327
328 CHAPTER 9.  Refrigeration and Liquefaction

addition of net work W to the system. Because all steps of the cycle are reversible, it gives the
minimum possible work required for a given refrigeration effect.
The working fluid operates in a cycle for which ΔU is zero. The first law for the cycle
is therefore:
W = − (QC + QH) (9.1)
where we note that QC is a positive number and QH (larger in absolute value) is negative. The
measure of the effectiveness of a refrigerator is its coefficient of performance ω, defined as:
heat absorbed at the lower temperature ___ ​Q​ C​
ω ≡ ​_________________________________
​           ​ = ​   ​ ​ (9.2)
net work W

Equation (9.1) may be divided by QC and then combined with Eq. (5.4):

W ​QH​  ​​ − W ​T​ H​​ ​T​ C​​ − ​T​ H​​

− ___
​ ​    ​  = 1 + ​ ___ ​​   ​​ 
  ____  ​   = 1 − ​ ___ ​  = ​ _______  ​​ 
 
​Q​ C​​ ​Q​ C​​ ​Q​ C​​ ​T​ C​​ ​T​ C​​

​T​ C​​
Equation (9.2) becomes: ​​​ω = ​ _______    ​​​​   (9.3)
​T​ H​​ − ​T​ C​​

For example, refrigeration at a temperature level of 5°C in surroundings at 30°C, gives:

5 + 273.15
________________________
​
ω = ​   
    ​  = 11.13​
​(​30 + 273.15​)​ − ​​(​5 + 273.15​)​
Equation (9.3) applies only to a refrigerator operating on a Carnot cycle,
which yields the maximum possible value of ω for a refrigerator operat-
ing between given values of TH and TC.
It shows clearly that the refrigeration effect per unit of work decreases as the temper-
ature of heat absorption TC decreases and as the temperature of heat rejection TH increases.

9.2  THE VAPOR-COMPRESSION CYCLE

The vapor-compression refrigeration cycle is represented in Fig. 9.1, along with a TS dia-
gram showing the four steps of the process. A liquid refrigerant evaporating at constant T
and P absorbs heat (line 1 → 2), producing the refrigeration effect. The vapor produced is
compressed via dashed line 2 → 3′ for isentropic compression (Fig. 7.6), and via line 2 → 3,
sloping in the direction of increasing entropy, for an actual compression process, reflecting
inherent irreversibilities. At this higher T and P, it is cooled and condensed (line 3 → 4) with
rejection of heat to the surroundings. Liquid from the condenser expands (line 4 → 1) to its
original pressure. In principle, this can be carried out in a turbine from which work is obtained.
However, for practical reasons it is usually accomplished by throttling through a partly open
control valve. The pressure drop in this irreversible process results from fluid friction in the
valve. As shown in Sec. 7.1, the throttling process occurs at constant enthalpy.
9.2.  The Vapor-Compression Cycle 329

3 4 3
Condenser
3

T Throttle
Compressor
valve
2
1
1 2
Evaporator
S

Figure 9.1: Vapor-compression refrigeration cycle.

On the basis of a unit mass of fluid, the equations for the heat absorbed in the evaporator
and the heat rejected in the condenser are:
QC = H2 − H1    and    QH = H4 − H3
These equations follow from Eq. (2.31) when the small changes in potential and kinetic energy
are neglected. The work of compression is simply: W
​  = ​H​ 3​ − ​H​ 2​, and by Eq. (9.2), the coeffi-
cient of performance is:
​H​ 2​ − ​H​ 1​
ω = ​______
​     
​​ (9.4)
​H​ 3​ − ​H​ 2​
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 absorp-
∙

tion in the evaporator2 by the equation:

∙
​​Q ​​  C​​
​​m  ​ = ​ _______
∙
   ​​   (9.5)
​H​ 2​​ − ​H​ 1​​
The vapor-compression cycle of Fig. 9.1 is shown on a PH diagram in Fig. 9.2, a diagram
commonly used in the description of refrigeration processes, because it shows the required
enthalpies directly. Although the evaporation and condensation processes are represented by
constant-pressure paths, small pressure drops do occur because of fluid friction.
For given TC and TH, vapor-compression refrigeration results in lower values of ω than
the Carnot cycle because of irreversibilities in expansion and compression. The following
example provides an indication of typical values for coefficients of performance.

2In the United States refrigeration equipment is commonly rated in tons of refrigeration; a ton of refrigeration is

defined as heat absorption at the rate of 12,000(Btu)(hr)−1 or 12,660 kJ per hour. This corresponds approximately to
the rate of heat removal required to freeze 1(ton) of water, initially at 32(°F), per day.
330 CHAPTER 9.  Refrigeration and Liquefaction

Const S

4 3

Figure 9.2: Vapor-compression

refrigeration cycle on a PH In P
diagram.
1 2

Example 9.1
A refrigerated space is maintained at −20°C, and cooling water is available at 21°C.
Refrigeration capacity is 120,000 kJ⋅h−1. The evaporator and condenser are of suffi-
cient size that a 5°C minimum-temperature difference for heat transfer can be realized
in each. The refrigerant is 1,1,1,2-tetrafluoroethane (HFC-134a), for which data are
given in Table 9.1 and Fig. F.2 (App. F).
(a) What is the value of ω for a Carnot refrigerator?
∙
(b) Calculate ω and m ​​  ​​  for a vapor-compression cycle (Fig. 9.2) if the compressor
efficiency is 0.80.

Solution 9.1
(a) Allowing 5°C temperature differences, the evaporator temperature is −25°C =
248.15 K, and the condenser temperature is 26°C = 299.15 K. Thus, by Eq. (9.3) for
a Carnot refrigerator,
248.15
ω = ​_____________
​        ​ = 4.87​
299.15 − 248.15
(b) With HFC-134a as the refrigerant, enthalpies for states 2 and 4 of Fig. 9.2 are read
directly from Table 9.1. The entry at −25°C indicates that HFC-134a vaporizes in
the evaporator at a pressure of 1.064 bar. Its properties as a saturated vapor at these
conditions are:
​H​ 2​ = 383.45 kJ​⋅kg​​ −1​        ​S​ 2​ = 1.746​kJ​⋅kg​​ −1​ ​⋅K​​ −1​​
​
9.3.  The Choice of Refrigerant 331

The entry at 26°C in Table 9.1 shows that HFC-134a condenses at 6.854 bar; its
enthalpy as a saturated liquid at these conditions is:
​H​ 4​ = 235.97 kJ ​⋅kg​​ −1​​
​
If the compression step is reversible and adiabatic (isentropic) from saturated
vapor at state 2 to superheated vapor at state 3′,
​​S​ 3′ ​ ​  = ​S​ 2​ = 1.746 kJ​⋅kg​​ −1​ ​⋅K​​ −1​​
This entropy value and the condenser pressure of 6.854 bar are sufficient to spec-
ify the thermodynamic state at point 3′. One could find the other properties at
this state using Fig. F.2, following a curve of constant entropy from the saturation
curve to the condenser pressure. However, more precise results can be obtained
using an electronic resource such as the NIST WebBook. Varying the temperature
at a fixed pressure of 6.854 bar shows that the entropy is 1.746 kJ⋅kg−1⋅K−1 at
T = 308.1 K. The corresponding enthalpy is:
​​H​ 3′ ​ ​  = 421.97 kJ​⋅kg​​ −1​​
and the enthalpy change is:
​(​ΔH​)​ S​ = ​H3​ ′ ​ ​  − ​H​ 2​ = 421.97 − 383.45 = 38.52 kJ​⋅kg​​ −1​​
​
By Eq. (7.17) for a compressor efficiency of 0.80, the actual enthalpy change for
step 2 → 3 is:
​(​ΔH​)​ S​ _____
38.52
​H​ 3​ − ​H​ 2​ = ​_____
​       ​  = ​   = 48.15 kJ​⋅kg​​ −1​​
 ​ 
η 0.80

Because the throttling process of step 1 → 4 is isenthalpic, H1 = H4. The ­coefficient

of performance as given by Eq. (9.4) therefore becomes:
​H​ 2​ − ​H​ 4​ _____________
383.45 − 235.97
ω = ​______
​     
​ = ​      ​  
= 3.06​
​H​ 3​ − ​H​ 2​ 48.15

and the HFC-134a circulation rate as given by Eq. (9.5) is:

∙
​​Q ​​  C​​ 120,000
​​m  ​ = ​ _______ = ​______________
  ​ = 814 kg​·h​​ −1​​
∙
   ​      
​H​ 2​​ − ​H​ 4​​ 383.45 − 235.97

9.3  THE CHOICE OF REFRIGERANT

As shown in Sec. 5.2, the efficiency of a Carnot heat engine is independent of the ­working
medium of the engine. Similarly, the coefficient of performance of a Carnot refrigerator is
independent of the refrigerant. The irreversibilities inherent in vapor-compression cycles
cause the coefficient of performance of practical refrigerators to depend to a limited extent
on the refrigerant. Nevertheless, such characteristics as toxicity, flammability, cost, corrosion
332 CHAPTER 9.  Refrigeration and Liquefaction

properties, and vapor pressure are of greater importance in the choice of refrigerant. Moreover,
environmental concerns strongly constrain the range of compounds that can be considered for
use as refrigerants. 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 many
requirements limit the choice of refrigerants to relatively few fluids.
Ammonia, methyl chloride, carbon dioxide, propane, and other hydrocarbons can serve
as refrigerants, particularly in industrial applications. Halogenated hydrocarbons came into
common use as refrigerants in the 1930s. Fully halogenated chlorofluorocarbons were the
most common refrigerants for several decades. However, these stable molecules were found
to persist in the atmosphere for many years, allowing them to reach the stratosphere before
finally decomposing by reactions that severely deplete stratospheric ozone. As a result, their
production and use is now banned. Certain less-than-fully halogenated hydrocarbons, which
cause relatively little ozone depletion, and hydrofluorocarbons that cause no ozone depletion
now serve as replacements in many applications. A primary example is 1,1,1,2-tetrafluoroethane
(HFC-134a).3 Unfortunately, these refrigerants have extremely high global warming potentials,
hundreds to thousands of times greater than CO2, and for that reason are now being banned
in many countries. New hydrofluorocarbon refrigerants with lower global warming potential,
such as 2,3,3,3-tetrafluoropropene (HFO-1234yf), are beginning to replace first-generation
hydrofluorocarbon refrigerants such as R134a.
A pressure/enthalpy diagram for 1,1,1,2-tetrafluoroethane (HFC-134a) is shown in
Fig. F.2 of App. F; Table 9.1 provides saturation data for the same refrigerant. Tables and
­diagrams for a variety of other refrigerants are readily available.4

Cascade Cycles
Limits placed on the operating pressures of the evaporator and condenser of a refrigeration
system also limit the temperature difference TH − TC over which a simple vapor-compression
cycle can operate. With TH fixed by the temperature of the surroundings, a lower limit is
placed on the temperature level of refrigeration. This can be overcome by the operation of
two or more refrigeration cycles employing different refrigerants in a cascade. A two-stage
cascade is shown in Fig. 9.3.
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 chosen such that each cycle operates at a reasonable pressure.
For example, assume the following operating temperatures (Fig. 9.3):
T​ C′ ​​ ​  = − 16° C  ​​
TH = 30° C  ​​ ′ ​​ ​  = − 10° C    TC = − 50° C
T​ H
If tetrafluoroethane (HFC-134a) is the refrigerant in cycle 2, then the intake and
discharge pressures for the compressor are about 1.6 bar and 7.7 bar, and the pressure ratio is

3The abbreviated designation is nomenclature of the American Society of Heating, Refrigerating, and Air-

Conditioning Engineers.
4ASHRAE Handbook: Fundamentals, Chap. 30, 2013; R. H. Perry and D. Green, Perry’s Chemical Engineers’

Handbook, 8th ed., Sec. 2.20, 2008. “Thermophysical Properties of Fluid Systems” in NIST Chemistry WebBook,
http://webbook.nist.gov.
9.3.  The Choice of Refrigerant 333

Table 9.1: Properties of Saturated 1,1,1,2-Tetrafluoroethane (R134A)†

Volume Enthalpy Entropy
m3⋅kg−1 kJ⋅kg−1 kJ⋅kg−1⋅K−1
T(°C)  P (bar) Vl Vv Hl Hv Sl Sv
−40 0.512 0.000705 0.361080 148.14 374.00 0.796 1.764
−35 0.661 0.000713 0.284020 154.44 377.17 0.822 1.758
−30 0.844 0.000720 0.225940 160.79 380.32 0.849 1.752
−25 1.064 0.000728 0.181620 167.19 383.45 0.875 1.746
−20 1.327 0.000736 0.147390 173.64 386.55 0.900 1.741
−18 1.446 0.000740 0.135920 176.23 387.79 0.910 1.740
−16 1.573 0.000743 0.125510 178.83 389.02 0.921 1.738
−14 1.708 0.000746 0.116050 181.44 390.24 0.931 1.736
−12 1.852 0.000750 0.107440 184.07 391.46 0.941 1.735
−10 2.006 0.000754 0.099590 186.70 392.66 0.951 1.733
−8 2.169 0.000757 0.092422 189.34 393.87 0.961 1.732
−6 2.343 0.000761 0.085867 191.99 395.06 0.971 1.731
−4 2.527 0.000765 0.079866 194.65 396.25 0.980 1.729
−2 2.722 0.000768 0.074362 197.32 397.43 0.990 1.728
0 2.928 0.000772 0.069309 200.00 398.60 1.000 1.727
2 3.146 0.000776 0.064663 202.69 399.77 1.010 1.726
4 3.377 0.000780 0.060385 205.40 400.92 1.020 1.725
6 3.620 0.000785 0.056443 208.11 402.06 1.029 1.724
8 3.876 0.000789 0.052804 210.84 403.20 1.039 1.723
10 4.146 0.000793 0.049442 213.58 404.32 1.049 1.722
12 4.430 0.000797 0.046332 216.33 405.43 1.058 1.721
14 4.729 0.000802 0.043451 219.09 406.53 1.068 1.720
16 5.043 0.000807 0.040780 221.87 407.61 1.077 1.720
18 5.372 0.000811 0.038301 224.66 408.69 1.087 1.719
20 5.717 0.000816 0.035997 227.47 409.75 1.096 1.718
22 6.079 0.000821 0.033854 230.29 410.79 1.106 1.717
24 6.458 0.000826 0.031858 233.12 411.82 1.115 1.717
26 6.854 0.000831 0.029998 235.97 412.84 1.125 1.716
28 7.269 0.000837 0.028263 238.84 413.84 1.134 1.715
30 7.702 0.000842 0.026642 241.72 414.82 1.144 1.715
35 8.870 0.000857 0.023033 249.01 417.19 1.167 1.713
40 10.166 0.000872 0.019966 256.41 419.43 1.191 1.711
45 11.599 0.000889 0.017344 263.94 421.52 1.214 1.709
50 13.179 0.000907 0.015089 271.62 423.44 1.238 1.70
55 14.915 0.000927 0.013140 279.47 425.15 1.261 1.705
60 16.818 0.000950 0.011444 287.50 426.63 1.285 1.702
65 18.898 0.000975 0.009960 295.76 427.82 1.309 1.699
70 21.168 0.001004 0.008653 304.28 428.65 1.333 1.696
75 23.641 0.001037 0.007491 313.13 429.03 1.358 1.691
80 26.332 0.001077 0.006448 322.39 428.81 1.384 1.685
† Data in this table are from E. W. Lemmon, M. O. McLinden and D. G. Friend, “Thermophysical Properties of Fluid Systems” in
NIST Chemistry WebBook, NIST Standard Reference Database Number 69, Eds. P. J. Linstrom and W. G. Mallard, National Institute
of Standards and Technology, Gaithersburg MD, 20899, http://webbook.nist.gov.
334 CHAPTER 9.  Refrigeration and Liquefaction

QH

Condenser at TH

Cycle 2 Ws(2)

Interchanger
TC
Figure 9.3: A two-stage
­cascade refrigeration system.
TH

Cycle 1 Ws(1)

Evaporator at TC

QC

about 4.9. If difluoromethane (R32) is the refrigerant in cycle 1, these pressures are about 1.1
and 5.8 bar, and the pressure ratio is about 5.3. These are all reasonable values. On the other
hand, for a single cycle operating between −50°C and 30°C with HFC-134a as refrigerant, the
intake pressure to the condenser is about 0.29 bar, well below atmospheric pressure. Moreover,
for a discharge pressure of about 7.7 bar the pressure ratio is 26, too high to achieve with a
single-stage compressor.

9.4  ABSORPTION REFRIGERATION

In vapor-compression refrigeration the work of compression is usually supplied by an electric

motor. But the source of the electric energy is most likely a heat engine (central power plant) used
to drive a generator. Thus the work for refrigeration comes ultimately from a heat engine. This
suggests a combination of cycles wherein work produced by an engine cycle is used internally by a
coupled refrigeration cycle in a device that takes in heat both at elevated temperature TH and at cold
temperature TC and rejects heat to the surroundings at TS. Before considering practical absorption-
refrigeration processes, we first treat a combination of Carnot cycles that produce this effect.
The work required by a Carnot refrigerator absorbing heat at temperature TC and reject-
ing heat at the temperature of the surroundings TS follows from Eqs. (9.2) and (9.3):
9.4.  Absorption Refrigeration 335

​T​ S​ − ​T​ C​
W = ​______
​      ​  
​Q​ C​​
​T​ C​

where TS replaces TH and QC is the heat absorbed. If a source of heat is available at a temper-
ature TH > TS, then this work may be obtained from a Carnot engine operating between TH
and TS. The heat required QH for the production of work is found from Eq. (5.5), where we
have substituted TS for TC and changed the sign of W, because W in Eq. (5.5) refers to a Carnot
engine, but here it refers to the refrigerator:
− W ​T​ S​
___ ​T​ H​
​   ​  = ​___
​ ​  ​ = W ​______
   ​  − 1​      or​    ​QH      ​​  
​QH
​  ​ ​T​ H​ ​T​ H​ − ​T​ S​
​QH​  ​​ ​T​ H​​ _______​T​ S​​ − ​T​ C​​
​Elimination of W gives: ​ ___ ​  = ​ _______    ​ ​   ​​    (9.6)
​Q​ C​​ ​T​ H​​ − ​T​ S​​ ​T​ C​​
The value of QH/QC given by this equation is of course a minimum because Carnot cycles
cannot be achieved in practice. It provides a limiting value for absorption refrigeration.
A schematic diagram for a typical absorption refrigerator is shown in Fig. 9.4. Note that
just as in the preceding derivation, W​ ​is eliminated, and both QH and QC enter the system, with
heat discarded only to the surroundings. The essential difference between a vapor-compression
and an absorption refrigerator is in the different means employed for compression. The section
of the absorption unit to the right of the dashed line in Fig. 9.4 is the same as in a vapor-
compression refrigerator, but the section to the left accomplishes compression by what amounts
to a heat engine. Refrigerant as vapor from the evaporator is absorbed in a relatively nonvolatile
liquid solvent at the pressure of the evaporator and at relatively low temperature. The heat given
off in the process is discarded to the surroundings at TS. The liquid solution from the absorber,

QH
Heat discarded to
Heat added from
surroundings at TS
source at TH
3 4
Condenser

Regenerator

Heat
exchanger

2
1
Evaporator
Absorber

Heat absorbed for

Pump refrigeration at TC
Heat discarded to
QC
surroundings at TS

Figure 9.4: Schematic diagram of an absorption-refrigeration unit.

336 CHAPTER 9.  Refrigeration and Liquefaction

which contains a relatively high concentration of refrigerant, passes to a pump, which raises
the pressure of the liquid to that of the condenser. Heat from the higher temperature source at
TH is transferred to the compressed liquid solution, raising its temperature and evaporating the
refrigerant from the solvent. Vapor passes from the regenerator to the condenser, and solvent,
which now contains a relatively low concentration of refrigerant, returns to the absorber by way
of a heat exchanger, which serves to conserve energy and adjust stream temperatures toward
optimum values. Low-pressure steam is the usual source of heat for the regenerator.
The most commonly used absorption-refrigeration system operates with water as the
refrigerant and a lithium bromide solution as the absorbent. This system is obviously limited
to refrigeration temperatures above the freezing point of water. It is treated in detail by Perry
and Green.5 For lower temperatures, ammonia can serve as refrigerant with water as the sol-
vent. An alternative system uses methanol as refrigerant and polyglycolethers as absorbent.
Consider refrigeration at a temperature level of −10°C (TC = 263.15 K) with a heat source
of condensing steam at atmospheric pressure (TH = 373.15 K). For a surroundings temperature
of 30°C (TS = 303.15 K), the minimum possible value of QH/QC is found from Eq. (9.6):

( ) ( )
​QH
___ ​  ​ 373.15 303.15 − 263.15
​    ​ = ​​ _____________
​ ​       ​ ​   _____________
​    ​ ​ = 0.81​
​Q​ C​ 373.15 − 303.15 263.15

For an actual absorption refrigerator, the value would be on the order of three times this result.

9.5  THE HEAT PUMP

The heat pump, a reversed heat engine, is a device for heating houses and commercial build-
ings 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 ​​Q​ C​ / W = 4,​
the heat available to heat the house QH is equal to five times the energy input to the compres-
sor. 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 refrig-
erant is simply reversed, and heat is absorbed from the building and rejected through under-
ground coils or to the outside air.

Example 9.2
A house has a winter heating requirement of 30 kJ⋅s−1 and a summer cooling
requirement of 60 kJ⋅s−1. Consider a heat-pump installation to maintain the house

5R. H. Perry and D. Green, op. cit., pp. 11–90 to 11–94.

 Rev. Confirming Pages

9.6.  Liquefaction Processes 337

temperature at 20°C  in winter and 25°C  in summer. This requires circulation of the
refrigerant through interior exchanger coils at 30°C  in winter and 5°C  in summer.
Underground coils provide the heat source in winter and the heat sink in summer. For
a year-round ground temperature of 15°C, the heat-transfer characteristics of the coils
necessitate refrigerant temperatures of 10°C in winter and 25°C in summer. What are
the minimum power requirements for winter heating and summer cooling?

Solution 9.2
The minimum power requirements are provided by a Carnot heat pump. For win-
ter heating, the house coils are at the higher-temperature level TH, and the heat
requirement is QH = 30 kJ⋅s−1. Application of Eq. (5.4) gives:

( 30 + 273.15 )
​T​ C​ 10 + 273.15
​ ​  ​ ___
​Q​ C​ = − ​QH ​    ​ = 30​​ _
​  ​ ​ = 28.02 kJ​⋅s​​ −1​​
  
​T​ H​
This is the heat absorbed in the ground coils. By Eq. (9.1),
​ ​  ​ − ​Q​ C​ = 30 − 28.02 = 1.98 kJ​⋅s​​ −1​​
W = − ​QH
Thus the power requirement is 1.98 kW.
For summer cooling, QC = 60 kJ⋅s−1, and the house coils are at the lower-
temperature level TC. Combining Eqs. (9.2) and (9.3) and solving for W:

( 5 + 273.15 )
​T​ H​ − ​T​ C​ 25 − 5
W = ​Q​ C​ ______
​ ​      = 60​​ _
​   ​    ​ ​ = 4.31 kJ​⋅s​​ −1​​
​T​ C​
The power requirement here is therefore 4.31 kW. Actual power requirements for
practical heat pumps are likely to be more than twice this lower limit.

9.6  LIQUEFACTION PROCESSES

Liquefied gases are used for a variety of purposes. For example, liquid propane in cylinders
serves as a domestic fuel, liquid oxygen is carried in rockets, natural gas is liquefied for ocean
transport, and liquid nitrogen provides low-temperature refrigeration. Gas mixtures (e.g., air)
are liquefied for separation into their component species by distillation.
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.

The first method requires a heat sink at a temperature lower than that to which the gas is
cooled, and is most commonly used to precool a gas prior to its liquefaction by the other two
methods. An external refrigerator is required for a gas temperature below that of the surroundings.

smi96529_ch09_327-347.indd 337 06/19/17 12:36 PM

338 CHAPTER 9.  Refrigeration and Liquefaction

The three methods are illustrated in Fig. 9.5. The constant-pressure process (1)
approaches the two-phase region (and liquefaction) most closely for a given drop in tempera-
ture. The throttling process (3) does not result in liquefaction unless the initial state is at a low
enough temperature and high enough pressure for the constant-enthalpy process to cut into
the two-phase region. This is indeed the situation for an initial state at A′, but not at A, where
the temperature is the same but the pressure is lower than at A. The change of state from A to
A′ may be accomplished by compression of the gas to the pressure at B and constant-pressure
cooling to A′. Reference to a PH diagram for air6 shows that at a temperature of 160 K, the
pressure must be greater than about 80 bar for any liquefaction to occur along a path of con-
stant enthalpy. Thus, if air is compressed to at least 80 bar and cooled below 160 K, it can be
partially liquefied by throttling. An efficient process for cooling the gas is by countercurrent
heat exchange with that portion of the gas which does not liquefy in the throttling process.

A A
1
Figure 9.5: Cooling processes on a TS diagram. T
3 2 3

Liquefaction by isentropic expansion along process (2) occurs from lower pressures (for
given temperature) than by throttling. For example, continuation of process (2) from initial
state A ultimately results in liquefaction.
The throttling process (3) is commonly employed in small-scale commercial
liquefaction plants. The temperature of the gas must decrease during expansion, and
this indeed occurs with most gases at usual conditions of temperature and pressure. The
exceptions are hydrogen and helium, which increase in temperature upon throttling unless
the initial temperature is below about 100 K for hydrogen and 20 K for helium. Liquefaction
of these gases by throttling requires initial cooling to temperatures lower than obtained by
method 1 or 2.
The Linde liquefaction process, which depends solely on throttling expansion, is shown
in Fig. 9.6. After compression, the gas is precooled to ambient temperature. It may be even
further cooled by refrigeration. The lower the temperature of the gas entering the throttle
valve, the greater the fraction of gas that is liquefied. For example, a refrigerant evaporating
in the cooler at −40°C provides a lower temperature at the valve than if water at 20°C is the
cooling medium.

6R. H. Perry and D. Green, op. cit., Fig. 2–5, p. 2–215.

9.6.  Liquefaction Processes 339

Cooler
3 4 7
Exchanger

Throttle
8
15
Win 10

2
9

1 Liquid
Gas feed

Figure 9.6: Linde liquefaction process.

A more efficient liquefaction process would replace the throttle valve with an expander,
but operating such a device into the two-phase region is impractical. The Claude process,
shown in Fig. 9.7, is based in part on this idea. Gas at an intermediate temperature is extracted
from the heat-exchange system and passed through an expander from which it exhausts as
a saturated or slightly superheated vapor. The remaining gas is further cooled and throttled
through a valve to produce liquefaction as in the Linde process. The unliquefied portion,
which is saturated vapor, mixes with the expander exhaust and returns for recycle through the
heat-exchanger system.
An energy balance, Eq. (2.30), applied to that part of the process lying to the right of the
dashed vertical line yields:
∙
​​​m  ​​  9​​​H​ 9​ + ​​m ​​  15​​​H​ 15​ − ​​m ​​  4​​​H​ 4​ = ​​W ​​  out​​​
∙ ∙ ∙

∙
If the expander operates adiabatically, ​​​W  ​​  out​​​as given by Eq. (7.13) is:
∙
​​​W  ​​  out​​  = ​​m ​​  12​​​(​H​ 12​ − ​H​ 5​)​​
∙

Moreover, by a mass balance, ​​​m  ​​  15​​  = ​​m ​​  4​​ − ​​m ​​  9​​​. The energy balance, after division by ​​​m  ​​  4​​​, there-
∙ ∙ ∙ ∙

fore becomes:
​​m ​​  9​​ ​​m ​​  4​​ −​​m ​​  9​​ ​​m ​​  12​​
∙ ∙ ∙ ∙

​ ​ ___ ∙  ​​  H​  ​​ + _______

​  ∙  ​​H​   15​​ − ​H​ 4​​  = ​ ____
  ∙  ​(​  H​  ​​ − ​H​ 5​​)
​​m ​​  4​​ 9 ​​m ​​  4​​ ​​m ​​  4​​ 12
​With the definitions, z​  ≡ ​​m ​​  9​​ / ​​m ​​  4​​​ and x​  ≡ ​​m ​​  12​​ /​ m ​​  4​​​, solution of this equation for z yields:
∙ ∙ ∙ ∙

x​​(​H​ 12​ − ​H​ 5​)​ + ​H​ 4​ − ​H​ 15​
z = ​_______________
​   
       ​​ (9.7)
​H​ 9​ − ​H​ 15​

In this equation z is the fraction of the stream entering the heat-exchanger system that is
liquefied, and x is the fraction of this stream that is drawn off between the heat exchangers and
340 CHAPTER 9.  Refrigeration and Liquefaction

Cooler Exchangers

4 5 6
I II
14 7

11
3 15

Win Wout
13

8
2
12 10

1
Gas feed

Liquid

Figure 9.7: Claude liquefaction process.

passed through the expander. This latter quantity (x) is a design variable and must be specified
before Eq. (9.7) can be solved for z. Note that the Linde process results when x = 0, and in this
event Eq. (9.7) reduces to:
​H​ 4​ − ​H​ 15​
z = ​_______
​     
​​ (9.8)
​H​ 9​ − ​H​ 15​
Thus the Linde process is a limiting case of the Claude process, obtained when none of
the high-pressure gas stream is sent to an expander.
Equations (9.7) and (9.8) suppose that no heat flows into the system from the surround-
ings. This can never be exactly true, and heat leakage may be significant when temperatures
are very low, even with well-insulated equipment.

Example 9.3
Natural gas, assumed here to be pure methane, is liquefied in a Claude process. Com-
pression is to 60 bar and precooling is to 300 K. The expander and throttle exhaust
to a pressure of 1 bar. Recycle methane at this pressure leaves the exchanger sys-
tem (point 15, Fig. 9.7) at 295 K. Assume no heat leaks into the system from the
9.6.  Liquefaction Processes 341

surroundings, an expander efficiency of 75%, and an expander exhaust of saturated

vapor. For a draw-off to the expander of 25% of the methane entering the exchanger
system (x = 0.25), what fraction z of the methane is liquefied, and what is the tempera-
ture of the high-pressure stream entering the throttle valve?

Solution 9.3
Data for methane are available in the NIST WebBook,7 from which the following
values were obtained:
​H​  ​​ = 855.3 kJ·​kg​​  −1​  (at 300 K and 60 bar)
​​  4​  ​ 
     ​   ​​ ​
​H​ 15​​ = 903.0 kJ·​kg​​  −1​  (at 295 K and 1 bar)

For saturated liquid and vapor, at a pressure of 1 bar:

​ ​ sat​= 111.5 K
T ​
​H​ 9​ = − 0.6  ​kJ·kg​​ −1​ ​(​saturated liquid​)​
​
  
​  
   ​ ​ ​  ​  ​ ​​ ​    
​  ​​
​H​ 12​= 510.6  ​kJ·kg​​ −1​ (​ ​saturated vapor​)​
​S​ 12​ = 4.579  ​kJ·kg​​ −1​ ​·K​​ −1​ (​ ​saturated vapor​)​

The enthalpy at the draw-off point between exchangers I and II, H5, is required
for solution of Eq. (9.7). The expander efficiency η is known, as is H12, the
enthalpy of the expander exhaust. The calculation of H5 (=H11), the expander
inlet enthalpy, is less straightforward than the usual calculation of the exhaust
enthalpy from the entrance enthalpy. The equation defining expander efficiency
can be written:

​ ′​    ​ ​  − ​H​ 5​​)​

ΔH = ​H​ 12​ − ​H​ 5​ = η ​​(​ΔH​)​ S​ = η(​H12

Solution for H12 yields:

​ ​ ′  ​ ​  − ​H​ 5​​)​

​H​ 12​ = ​H​ 5​ + η(​H12 (A)

′​   ​​​  is the enthalpy at 1 bar as the result of isentropic expansion from point
where ​​H12
5. This enthalpy is readily found once the conditions at point 5 are known. Thus
a trial calculation is indicated, wherein the first step is to assume temperature T5.
This leads to values for H5 and S5, from which H​  ′ ​​​  can be found. All quantities
​​ 12
in Eq. (A) are then known, and their substitution into this equation shows whether
or not it is satisfied. If not, a new value is chosen for T5, and the process contin-
ues until Eq. (A) is satisfied. For example, at 60 bar and 260 K, the enthalpy and
entropy are 745.27 kJ⋅kg−1 and 4.033 kJ⋅kg−1⋅K−1, respectively. The saturated liq-
uid and vapor at 1 bar have Sl = −0.005 and Sv = 4.579, respectively. Using these
values, isentropic expansion from 260 K and 60 bar to 1 bar would give a vapor
fraction of 0.8808. This would give:

′  ​ ​  = ​H​ 9​ + 0.8808​​(​ ​H​ 12​ − ​H​ 9​)​ = 449.6​ kJ·kg​​ −1​​
​​H​ 12

7E. W. Lemmon, M. O. McLinden and D. G. Friend, op. cit., http://webbook.nist.gov.

342 CHAPTER 9.  Refrigeration and Liquefaction

Using this value in Eq. (A) yields H12 = 508.8 kJ⋅kg−1, which is below the known
value of H12 = 510.6 kJ⋅kg−1. Thus, T5 must be higher than the assumed value of
260 K. Repeating this process (in an automated fashion using a spreadsheet) for
other values of T5 shows that Eq. (A) is satisfied for:

​T​ 5​ = 261.2 K   ​H​ 5​ = 748.8​ kJ⋅kg​​ −1​  ​​(​at 60 bar​)​​
​

Substitution of values into Eq. (9.7) now yields:

0.25​​(​510.6 − 748.8​)​ + 855.3 − 903.0
z = ​ ___________________________
​  
      ​  
= 0.1187​
− 0.6 − 903.0

Thus 11.9% of the methane entering the exchanger system is liquefied.

The temperature at point 7 depends on its enthalpy, which is found from energy
balances on the exchanger system. Thus, for exchanger I,

​​​m  ​​  4​​​(​H​ 5​ − ​H​ 4​)​ + ​​m ​​  15​​​(​H​ 15​ − ​H​ 14​)​ = 0​
∙ ∙

With ​​​m ​​  15​​ = ​​m ​​  4​​ − ​​m ​​  9​​​ and m

​​​  ​​  9​​/​​m ​​  4​​  = z​, this equation may be rearranged to give:
∙ ∙ ∙ ∙ ∙

​H​ 5​ − ​H​ 4​ 748.8 − 855.3
​H​ 14​ = ​______
​       + ​H​ 15​ = ​___________
​         ​  
+ 903.0​
1 − z 1 − 0.1187

Then,

​H​ 14​ = 782.2 ​ kJ⋅kg​​ −1​  ​T​ 14​ = 239.4 K​​(​at 1 bar​)​​
​

where T14 is found by evaluating H for methane at 1 bar and varying the tempera-
ture to match the known H14.
For exchanger II,

​​​m  ​​  7​​​(​H​ 7​ − ​H​ 5​)​ + ​​m ​​  14​​​(​H​ 14​ − ​H​ 12​)​ = 0​
∙ ∙

With ​​​m ​​  7​​ = ​​m ​​  4​​ − ​​m ​​  12​​​ and m

​​​  ​​  14​​ =​ ​m ​​  4​​  − ​​m ​​  9​​​and with the definitions of z and x, this
∙ ∙ ∙ ∙ ∙ ∙

equation upon rearrangement becomes:

1 − z 1 − 0.1187
​H​ 7​ = ​H​ 5​ − ​___
​     ​(​H​  ​ − ​H​ 12​)​ = 748.8 − ​_______
  ​( 
   ​782.2 − 510.6​)​​
1 − x 14 1 − 0.25

Then

​H​ 7​ = 429.7  ​kJ·kg​​ −1​  ​T​ 7​ = 199.1 K​​(​at 60 bar​)​​
​

As the value of x increases, T7 decreases, eventually approaching the saturation

temperature in the separator, and requiring an exchanger II of infinite area. Thus x
is limited on the high side by the cost of the exchanger system.
The other limit is for x = 0, the Linde system, for which by Eq. (9.8),
855.3 − 903.0
z = ​___________
​    
   ​ = 0.0528​
− 0.6 − 903.0
9.8. Problems 343

In this case only 5.3% of the gas entering the throttle valve emerges as liquid. The
temperature of the gas at point 7 is again found from its enthalpy, calculated by
the energy balance:
​H​ 7​ = ​H​ 4​ − ​​(​1 − z​)​(​H​ 15​ − ​H​ 10​)​​
​
Substitution of known values yields:
​H​ 7​ = 855.3 − ​​(​1 − 0.0528​)​(​903.0 − 510.6​)​ = 483.6 ​ kJ⋅kg​​ −1​​
​
The corresponding temperature of the methane entering the throttle valve is
T7 = 202.1 K.

9.7 SYNOPSIS

After thorough study of this chapter, including working through example and end-of-chapter
problems, one should be able to:

∙ Compute the coefficient of performance for a Carnot refrigeration cycle and recognize
that this represents an upper limit for any real refrigeration process.
∙ Carry out a thermodynamic analysis of a vapor compression refrigeration cycle like that
illustrated in Fig. 9.1.
∙ Describe a practical absorption refrigeration process and explain why its use might be
advantageous.
∙ Sketch a cascade refrigeration system, explain why one might use such a system, and
understand how to approach the selection of refrigerants for such a system.
∙ Carry out a thermodynamic analysis of a Linde or Claude liquefaction process, such as
that presented in Ex. 9.3.

9.8 PROBLEMS

An easy way to rationalize definitions of cycle performance is to think of them as:

9.1.
What you get
Measure of performance = ​______________
​    
   ​​
What you pay for
Thus, for an engine, thermal efficiency is ​η = ​​|​W​|​ / ​|​QH ​  ​|​; for a refrigerator, the coeffi-
cient of performance is ​ω = ​​|​Q​ C​|​ / ​|​W​|​. Define a coefficient of performance ϕ for a heat
pump. What is ϕ for a Carnot heat pump?

The contents of the freezer in a home refrigerator are maintained at −20°C. The
9.2.
kitchen temperature is 20°C. If heat leaks amount to 125,000 kJ per day, and if elec-
tricity costs $0.08/kWh, estimate the yearly cost of running the refrigerator. Assume a
coefficient of performance equal to 60% of the Carnot value.
344 CHAPTER 9.  Refrigeration and Liquefaction

Consider the startup of a refrigerator. Initially, the contents are at the same
9.3.
­temperature as the surroundings: ​T​ ​C​ 0​ ​ = ​T​ H​,​ where TH is the (constant) surroundings
­temperature. With the passage of time, owing to work input, the contents’ ­temperature
is reduced from ​​T​ ​C​ 0​​​ to its design value TC. Modeling the process as a Carnot
­refrigerator ­operating between an infinite hot reservoir and a finite cold reservoir of
total heat capacity Ct, determine an expression for the minimum work required to
decrease the contents ­temperature from ​T​ ​C​ 0​​​ to TC.

A Carnot refrigerator has tetrafluoroethane as the working fluid. The cycle is the same
9.4.
as that shown by Fig. 8.2, except the directions are reversed. For TC = −12°C  and
TH = 40°C, determine:

(a) The pressures at states 1, 2, 3, and 4.

(b) The quality xv at states 3 and 4.
(c) The heat addition per kg of fluid.
(d) The heat rejection per kg of fluid.
(e) The mechanical power per kg of fluid for each of the four steps.
(f) The coefficient of performance ω for the cycle.

Which is the more effective way to increase the coefficient of performance of a Carnot
9.5.
refrigerator: to increase TC with TH constant, or to decrease TH with TC constant? For
a real refrigerator, does either of these strategies make sense?

In comparing the performance of a real cycle with that of a Carnot cycle, one has
9.6.
in principle a choice of temperatures to use for the Carnot calculation. Consider a
vapor-compression refrigeration cycle in which the average fluid temperatures in
the condenser and evaporator are TH and TC, respectively. Corresponding to TH and
TC, the heat transfer occurs with respect to surroundings at temperature ​T​σ​  ​ H​​ and ​T​σ​  ​ C​​.​
Which provides the more conservative estimate of ωCarnot: a calculation based on TH
and TC, or one based on ​T​σ​  ​ H​​ and ​T​σ​  ​ C​​?​

A Carnot engine is coupled to a Carnot refrigerator so that all of the work produced by
9.7.
the engine is used by the refrigerator in extraction of heat from a heat reservoir at 0°C
at the rate of 35 kJ⋅s−1. The source of energy for the Carnot engine is a heat reservoir
at 250°C. If both devices discard heat to the surroundings at 25°C, how much heat
does the engine absorb from its heat-source reservoir?
  If the actual coefficient of performance of the refrigerator is ω = 0.6 ωCarnot and if
the thermal efficiency of the engine is η = 0.6ηCarnot, how much heat does the engine
absorb from its heat-source reservoir?

A refrigeration system requires 1.5 kW of power for a refrigeration rate of 4 kJ⋅s−1.

9.8.

(a) What is the coefficient of performance?

(b) How much heat is rejected in the condenser?
(c) If heat rejection is at 40°C, what is the lowest temperature the system can possibly
maintain?
9.8. Problems 345

A vapor-compression refrigeration system operates on the cycle of Fig. 9.1. The

9.9.
refrigerant is tetrafluoroethane (Table 9.1, Fig. F.2). For one of the following sets of
operating conditions, determine the circulation rate of the refrigerant, the heat-transfer
rate in the condenser, the power requirement, the coefficient of performance of the
cycle, and the coefficient of performance of a Carnot refrigeration cycle operating
between the same temperature levels.

(a) Evaporation T = 0°C; condensation T = 26°C; η(compressor) = 0.79; refrigeration

rate = 600 kJ·s−1.
(b) Evaporation T = 6°C; condensation T = 26°C; η(compressor) = 0.78; refrigeration
rate = 500 kJ·s−1.
(c) Evaporation T = −12°C; condensation T = 26°C; η(compressor) = 0.77; refrigera-
tion rate = 400 kJ·s−1.
(d) Evaporation T = −18°C; condensation T = 26°C; η(compressor) = 0.76; refrigera-
tion rate = 300 kJ·s−1.
(e) Evaporation T = −25°C; condensation T = 26°C; η(compressor) = 0.75; refrigera-
tion rate = 200 kJ·s−1.

9.10. A vapor-compression refrigeration system operates on the cycle of Fig. 9.1. The
refrigerant is water. Given that the evaporation T = 4°C, the condensation T = 34°C,
η(compressor) = 0.76, and the refrigeration rate = 1200 kJ⋅s−1, determine the circula-
tion rate of the refrigerant, the heat-transfer rate in the condenser, the power require-
ment, the coefficient of performance of the cycle, and the coefficient of performance
of a Carnot refrigeration cycle operating between the same temperature levels.

9.11. A refrigerator with tetrafluoroethane (Table 9.1, Fig. F.2) as refrigerant operates with
an evaporation temperature of −25°C and a condensation temperature of 26°C. Satu-
rated liquid refrigerant from the condenser flows through an expansion valve into the
evaporator, from which it emerges as saturated vapor.

(a) For a cooling rate of 5 kJ·s−1, what is the circulation rate of the refrigerant?
(b) By how much would the circulation rate be reduced if the throttle valve were
replaced by a turbine in which the refrigerant expands isentropically?
(c) Suppose the cycle of (a) is modified by the inclusion of a countercurrent heat
exchanger between the condenser and the throttle valve in which heat is trans-
ferred to vapor returning from the evaporator. If liquid from the condenser enters
the exchanger at 26°C and if vapor from the evaporator enters the exchanger at
−25°C and leaves at 20°C, what is the circulation rate of the refrigerant?
(d) For each of (a), (b), and (c), determine the coefficient of performance for isen-
tropic compression of the vapor.

9.12. A vapor-compression refrigeration system is conventional except that a counter-

current heat exchanger is installed to subcool the liquid from the condenser by heat
exchange with the vapor stream from the evaporator. The minimum temperature dif-
ference for heat transfer is 5°C. Tetrafluoroethane is the refrigerant (Table 9.1, Fig.
F.2), evaporating at −6°C and condensing at 26°C. The heat load on the evaporator is
346 CHAPTER 9.  Refrigeration and Liquefaction

2000 kJ·s−1. If the compressor efficiency is 75%, what is the power requirement? How
does this result compare with the power required by the compressor if the system
operates without the heat exchanger? How do the refrigerant circulation rates compare
for the two cases?

9.13. Consider the vapor-compression refrigeration cycle of Fig. 9.1 with tetrafluoroethane
as refrigerant (Table 9.1, Fig. F.2). If the evaporation temperature is −12°C, show the
effect of condensation temperature on the coefficient of performance by making cal-
culations for condensation temperatures of 16, 28, and 40°C.

(a) Assume isentropic compression of the vapor.

(b) Assume a compressor efficiency of 75%.

9.14. A heat pump is used to heat a house in the winter and to cool it in the summer. During
the winter, the outside air serves as a low-temperature heat source; during the summer,
it acts as a high-temperature heat sink. The heat-transfer rate through the walls and
roof of the house is 0.75 kJ⋅s−1 for each °C of temperature difference between the
inside and outside of the house, summer and winter. The heat-pump motor is rated
at 1.5 kW. Determine the minimum outside temperature for which the house can be
maintained at 20°C during the winter and the maximum outside temperature for which
the house can be maintained at 25°C during the summer.

9.15. Dry methane is supplied by a compressor and precooling system to the cooler of a
Linde liquid-methane system (Fig. 9.6) at 180 bar and 300 K. The low-pressure meth-
ane leaves the cooler at a temperature 6°C lower than the temperature of the incoming
high-pressure methane. The separator operates at 1 bar, and the product is saturated
liquid at this pressure. What is the maximum fraction of the methane entering the
cooler that can be liquefied? The NIST Chemistry WebBook (http://webbook.nist.
gov/chemistry/fluid/) is a source of data for methane.

9.16. Rework the preceding problem for methane entering at 200 bar  and precooled to
240 K by external refrigeration.

9.17. An advertisement is noted in a rural newspaper for a dairy-barn unit that combines a
milk cooler with a water heater. Milk must, of course, be refrigerated, and hot water
is required for washing purposes. The usual barn is equipped with a conventional air-
cooled electric refrigerator and an electric-resistance water heater. The new unit is
said to provide both the necessary refrigeration and the required hot water at a cost
for electricity about the same as the cost of running just the refrigerator in the usual
installation. To assess this claim, compare two refrigeration units: The advertised unit
takes 15 kJ·s−1 from a milk cooler at −2°C, and discards heat through a condenser at
65°C to raise the temperature of water from 13 to 63°C. The conventional unit takes
the same amount of heat from the same milk cooler at −2°C and discards heat through
an air-cooled condenser at 50°C; in addition, the same amount of water is heated elec-
trically from 13 to 63°C. Estimate the total electric power requirements for the two
cases, assuming that the actual work in both is 50% greater than required by Carnot
refrigerators operating between the given temperatures.
9.8. Problems 347

9.18. A two-stage cascade refrigeration system (see Fig. 9.3) operates between TC = 210 K
and TH = 305 K. Intermediate temperatures are ​​T​ C′ ​ ​  = 255 K​ and ​​TH
′​   ​ ​  = 260 K​. Coef-
ficients of performance ω of each stage are 65% of the corresponding values for a
Carnot refrigerator. Determine ω for the real cascade, and compare it with that for a
Carnot refrigerator operating between TC and TH.
9.19. Do a parametric study for the Claude liquefaction process treated in Sec. 9.6 and
Ex. 9.3. In particular, show numerically the effect of changing the draw-off ratio x
on other process variables. The NIST Chemistry WebBook (http://webbook.nist.gov/
chemistry/fluid/) is a source of data for methane.
9.20. The condenser of a home refrigerator is commonly underneath the appliance; thus,
the condensing refrigerant exchanges heat with household air, which has an average
temperature of about 21°C. It is proposed to reconfigure a refrigerator so that the
condenser is outside the home, where the average yearly temperature is about 10°C.
Discuss the pros and cons of this proposal. Assume a freezer temperature of −18°C,
and an actual coefficient of performance 60% that of a Carnot refrigerator.
9.21. A common misconception is that the coefficient of performance of a refrigerator must
be less than unity. In fact, this is rarely the case. To see why, consider a real refriger-
ator for which ω = 0.6 ω Carnot. What condition must be satisfied in order for ω < 1?
Assume that TH is fixed.
9.22. A furnace fails in a home in the winter. Mercifully, the electric power remains on. The
resident engineer tells her spouse not to worry; they’ll move into the kitchen, where
the heat discarded from the refrigerator may provide for a temporarily comfortable
living space. However (the engineer is reminded), the kitchen loses heat to the out-
doors. Use the following data to determine the allowable rate of heat loss (kW) from
the kitchen for the engineer’s proposal to make sense.
Data:  Desired kitchen temperature = 290 K.
Refrigerator freezer temperature = 250 K.
Average mechanical power input to refrigerator = 0.40 kW.
Performance: Actual ω = 65% of Carnot ω.
9.23. Fifty (50) kmol·h−1 of liquid toluene at 1.2 bar is cooled from 100 to 20°C. A
vapor-compression refrigeration cycle is used for the purpose. Ammonia is the work-
ing fluid. Condensation in the cycle is effected by an air-cooled fin/fan heat exchanger
for which the air temperature may be assumed essentially constant at 20°C. Determine:
(a) The low and high pressure levels (bar) in the refrigeration cycle.
(b) The circulation rate of ammonia (mol·s−1).

Assume 10°C minimum approach temperature differences for heat exchange. Data for
ammonia:
​ H​nlv​  ​ = 23.34 kJ ​mol​​  −1​
Δ
​​    ​  ​  4104.67​ ​P​​  sat​​​
ln  ​P​​  sat​ = 45.327 − ​ ________
 ​  − 5.146 ln T + 615.0 ____
  ​  2 ​ 
T ​T​​  ​
where Psat is in bars and T is in kelvins.