Refrigeration (Kylteknik) : 1. Introduction, Historic Overview, Brief Re-Wrap of Thermodynamics

Refrigeration (Kylteknik)
course # 424519.0 E v. 2017
1. Introduction, historic overview,

brief re-wrap of thermodynamics
Ron Zevenhoven
Åbo Akademi University
Thermal and Flow Engineering Laboratory / Värme- och strömningsteknik
tel. 3223 ; ron.zevenhoven@abo.fi
Åbo Akademi Univ - Thermal and Flow Engineering Piispankatu 8, 20500 Turku 9.1.2017 1/66
ÅA 424519 Refrigeration / Kylteknik
1.1 Refrigeration and this course
Some course details
 Course code 424519 E (5 study points ECTS, as of 2017)
 Course is given every second year (2017, 2019,....., period 3)
 Lectures & exercises by R. Zevenhoven, ~12 x 2-3h
 Written exam: 24.3.2017, 5.5.2017, ......... Minplan!!!
 Assumed background:
– Värmeteknik + Processteknik (earlier: Processteknikens grunder)
+ Teknisk termodynamik / Engineering thermodynamics
or: Principles of process engineering (MPCE / Vaasa E-technology)
 Course material:
– can be downloaded from http://users.abo.fi/rzevenho/kursRZ.html
– 2 books ÅA course library: 1) Refrigeration and air conditioning,
R. Arora (2010) https://abo.finna.fi/Record/alma.1231208
2) Handbook of liquefied natural gas, S. Moktahab et al., 2014,
https://abo.finna.fi/Record/alma.1238231 incl. E-book
– also ”Kylteknik” by G. Öhman (ÅA 1996) (57 p.) can be consulted
for further reading : http://users.abo.fi/rzevenho/Kylteknik%20_Ohman%2019962000.pdf
9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering 3/66
Piispankatu 8, 20500 Turku
Contents of course
 Introduction, historic overview, thermodynamics
 Vapor-compression refrigeration processes
 Absorption refrigeration processes, expansion refrigeration
systems
picture: http://www.sgisland.org/pages/zone/download.htm
 Thermo-electric processes, process comparison, process

equipment and control
 Very low temperatures; Gas processing (O , H , CO , LPG, LNG...) 2 2 2
 Air conditioning, cooling towers

 Food cooling and freezing
 Heat pumps, heat pipes, cold thermal
energy storage (cold TES)
 Solar cooling
 Exercises
Refrigeration: what and why /1
Picture: http://www.happynews.com/living/kitchen/refrigerator-feature-reviews.htm
 ”Refrigeration is the process of removing heat from
matter which may be solid, a liquid or a gas. Removing
heat from the matter cools it, or lowers the
temperature.” (D03)
 ”In a refigeration process, energy is converted into heat
transfer.” (S90)
 ”Refrigeration is the transfer of heat from a lower
temperature region to a higher temperature region.”
(ÇB98)
 “Med kylteknik avser man tekniken att
alstra och upprätthålla temperaturer som är
lägre än omgivningens temperatur” (Ö96)


 In principle, the temperature range covered by
refrigeration is from ambient temperature down to Picture: http://www.pchemlabs.com/images/17literdewar62104b.JPG
absolute zero: +15°C → -273.15°C (0 K)

 In practice the ranges are
– down to ~ -30°C ( ~ 240 K) for household and food
applications
– down to -200°C ( ~ 70 K) for industrial gas processing
(natural gas, O2, N2, CO2, ......)
 The ”cryogenic” (Gr: κρυος = ”cold”)
region below 70 K is the region of
low-temperature physics, but also
important for H2.
Picture: http://www.danisco.com/cms/resources/image/4682c2c0fd85cb33/meat.gif
Picture: http://www.tektondesign.com.mv/images/lpg1.png
 The aim of refigeration is
– To provide human comfort
– Generating low temperatures for
applications such as food storage, gas
liquefaction and other industrial
applications, storage and transport
 Natural sources for cooling:
– Ice, snow (0°C), + salt ( → -21°C with
23 %-wt NaCl in water)
– Air (-60°C → + 60°C), + windchill !
– Groundwater ~ +10°C
– Surface water 0°C → +30°C
 Not to be mixed up with cooling
applications, such as cast iron cooling
at ~1800 K: → ”simple” heat transfer
processing !

 The main interests of refrigeration
industry (D03):
Picture: http://www.lawrencepumps.com/products/cryogenic.htm
– Technical information on systems

and system components
– Energy and exergy analysis for
efficiency optimisation
– Application of optimum methods
and techniques
– Techniques for measurement and
evaluation of performance
– Methodologies for using data for
improved (future) designs

Refrigeration methods
 Reverse Rankine cycles can ”pump” heat to higher
temperatures
 Rapid expansion of a compressed gas gives a cooling effect
(Joule-Thomson effect)
 Adding salts to water has a cooling effect (Tmelt ↓ plus a
ΔHsolution effect); Phase transition heat effects, especially
condensing and vaporising (ΔHvaporise = ΔHcondense )
 The most important refrigeration technologies are
based on
– Vapor compression / evaporation: the main industrial and small-scale
application (due to superior efficiency)
– Absorption: used more for air conditioning, and for refrigeration at
locations where cheap heat is available
– Expansion of a gas: mainly used for very low temperatures (liquefaction)
1.2 Historic overview
Natural refrigeration processes /1
Picture: http://www.concordiastation.org/DOMEC/GIF/ice-core_storage.jpg
 Air conditioning by forced flow
of air around ice blocks
 Storage of ice, snow in cellars

(ancient China, ancient Europe)
 Pot-in-pot cooling systems (Nigeria):

A small earthenware pot is placed inside a larger
one, and the space between the two is filled with
moist sand. The inner pot is filled with fruit,
vegetables or soft drinks; a wet cloth covers the
whole thing. As water in the sand evaporates
through the surface of the outer pot, it carries heat,
drawing it away from the inner core.
source: http://lordramki.blogspot.com/2004/05/pot-in-pot-cooling-
system.html
Natural refrigeration processes /2

 Egyptians have wind from the north most of the year, and
”windcatchers” are put on roofs for in-door ventilation.
Picture: http://web-owls.com/2006/05/23/daily-life-ancient-egypt/
 Wet cloth can give a further cooling effect. During night-

time temperature drops near 0°C (and humidity is low !).
 Ice can be produced in a shallow
pan of water: the vaporisation of
some of the water gives a cooling
effect that produces some ice.
This method has been in use in India
for ages.
source: http://www.answers.com/topic/refrigerator

Technical refrigeration processes /1
 Energy is converted into heat that is transferred using a
medium referred to as refrigerant (sv: köldmediet)
 At a low temperature Tcold, the refrigerant takes up heat
Qin and at a higher temperature Thot the refrigerant gives
off heat Qout to another substance (for example to air at
Thot = Tsurroundings)
 The Second Law of Thermodynamics
shows that an energy input W is needed
to transfer heat from low to high
temperature
 The First Law of Thermodynamics shows
that Qhot = Qcold + W
note that also input heat can be used!
Picture: SEHB06

 Most of the early developments: during 1755-1850
 1755: Cullen (Scotland): cooling by evaporation of
water at very low pressures
Picture: http://www.prsrefrigeration.com/technical/cycle.php
 1834: Perkins (USA) vapor-compression refrigeration

process (making ice) using di-ethyl ether (R-610), based
on a compressor, a condenser, an evaporator and a
valve between the condenser and the evaporator.
 1827 – 1844: Stirling

(England), Gorrie (USA):
expansion refrigeration
process using air as
refrigerant (R-729) (”cold-
air machine”)
 1850: Carré (France):
refrigerator/ref_images/ref-overview_drawing03.gif
Picture: http://www.polarpowerinc.com/products/
absorption refrigeration
process using SO2 (R-764) +
Picture: http://www.answers.com/topic/thermoelectric-effect
water and later ammonia
(R-717) + water
 1834: Peltier (France) noted
a refrigeration effect when
applying a voltage difference
in a system made of two
wires of different metals
(reversing the thermo-
electric effect noted by
Seebeck (Estonia/Germany)
Two metals A and B,
in 1821) electric current I → T1 ≠ T2

 By ~ 1850, today’s three main refrigeration methods were
known.
 1853: vapor-compression machine by Twining (USA)
 1874: Linde’s large-scale, reliable refrigerator.
Picture: http://www.fsb.hr/r-conference/Gif/rlogotr.gif
 During 1877 – 1908 liquefaction of gases is developed, at

lower and lower temperatures, starting with O2, ending
with He. (Low-temperature physics is born!)
 During 1850-1930 the vapor-compression process is further
refined, with better compressors, better valves etc. using
NH3, SO2, CH3Cl (R-40), CO2 (R-744), CH2Cl2 (R-30),
iso-butane (R-600a), ethyl chloride (R-160)
 CO2 was primarily used as refrigerant on ships; large
industry was satisfied with (toxic) gases, mainly NH3,
and smaller users used mainly MeCl, EtCl and SO2
Boiling point data
As As
Gas T boil °C Gas T boil °C
refrigerant refrigerant
CO2 R-744 -78 CH3Cl R-40 -24
NH3 R-717 -34 (C2H5)2O R-610 +35
O2 R-732 -183 i-C4H10 R-600a -12
N2 R-728 -196 CH2Cl2 R-30 +40
H2 R-702 -253 CF3CH2F R-134a -26
CH4 R-50 -162 CCl3F R-11 +24
SO2 R-764 -10 CCl2F2 R-12 -30
He R-704 -269
For pressure = 1 bar


 The need for less toxic refrigerants especially for small-scale Picture: http://ozonewatch.gsfc.nasa.gov/monthly/index.html
and household users resulted in the development of so-called
freons in 1930, with freon R-12 (CCl2F2), R-11 (CCl3F) and
later many others
 After World War II: mass production of small scale
refrigeration and air-conditioning units for house-holds and
vehicles; improved system components, energy efficiency,
better insulation, control systems
 In the mid-1970s it was shown that freons
destroy the earth’s protective ozone layer; its
use and production is now banned under treaties
like the 1987 Montreal Protocol.
 Current emphasis lies still with freon substitution
and energy efficiency
The antarctic
ozone hole
Refrigerants: time line
Source: HTW08
Åbo Akademi Univ - Thermal and Flow Engineering Piispankatu 8, 20500 Turku 9.1.2017 19
Refrigerators and heat pumps

The objective of a
refrigerator (a) is to
remove heat from a cold
medium;
the objective of a heat
pump (b) is to supply
heat to a warm medium
Coefficient of performance COP
Desired output Cooling effect QL 
Refrigerator : COPR     (Carnot)
Required output Work input Wnet,in TH  
TL
Desired output Heating effect QH 
Heat pump : COPHP     (Carnot)
Required output Work input Wnet,in   TL
TH
with QH  QL  Wnet,input  COPHP  COPR  1 Picture: ÇB98
Other issues to be considered
Picture: http://techalive.mtu.edu/meec/module13/AirConditioning.htm Picture: ÇB98
 Air conditioning ↑  Food refrigeration ↑

 Cooling towers →  Hydrogen ↓
Picture: http://www.ohiocitizen.org/campaigns/ Picture: http://www.corrosion-doctors.org/

electric/2005/toledo%2005%20003b.jpg Hydrogen/Hindenburg.htm
Other issues to be considered
 Liquefied natural gas (LNG)  Solar cooling

floating storage and regasification unit transporting medicine
(FSRU), built for Lithuania’s liquefied through the desert
natural gas (LNG) terminal at Klaipéda.
(1.12.2009)
(27.10.2014)
Picture: http://en.delfi.lt/lithuania/energy/ Picture: http://inhabitat.com/
floating-lng-terminal-independence-sails-into-klaipeda.d?id=66226156 solar-powered-camel-clinics-carry-medicine-across-the-desert/
1.3 Brief re-wrap of thermodynamics

taken from Processteknikens grunder (PTG) #3 and #4: see Z13
First Law of Thermodynamics

Also known as the ”conservation of energy” principle
 ”The energy of an isolated system is constant” (A83)
 Energy can be converted from one form into another, and
vice versa
for example heat Q can be converted into work W and vice
versa - but there are limitations !
Closed system ΔE = W + Q (or: dE = δW + δQ)

. .
Open system ΔE = W + Q + min· ein - mout· eout
 Energy cannot be produced and speaking about ”energy

production” is wrong and silly (but it allows for distinguishing
amateurs from specialists)
Types of energy
 In a closed system, energy is  These energies are relative to a
present (”stored”) as potential reference frame reference state:
energy* Ep and kinetic – potential energy relative to a
energy** Ek (mechanical position z = 0 in a gravity field
energy) and internal – kinetic energy relative to a
energy*** U (thermal energy) non-moving reference frame with
velocity v = 0
 For a mass m, with vertical
position z in a gravity field and – internal energy relative to zero
temperature T = 0, or
velocity v defined as
surroundings temperature T =
Ep = m· g· z T°.
Ek = ½· m· v2
= ½· m· v2
U = m· u
* sv: lägesenergi; ** sv: rörelseenergi; *** sv: inre energi Pictures: SEHB06
Total energy of a system

 Total energy of a system
E = Ek + Ep + U (J)
= m· ek + m· ep + m· u (J)
with specific energies ek, ep and u (J/kg)
.
 A mass stream m (kg/s) corresponds to an
energy stream Ė
. .
Ė = Ėk + Ėp + U = m· (ek + ep + u) (W = J/s)
Energy transfer
 For a closed system ENERGY can be transferred across
the boundary by WORK or by HEAT transfer
 For an open system, MASS may cross the bounday and

the ENERGY associated with that can enter the system, in
addition to WORK or by HEAT transfer (as for a closed
system)
 Generally, for solid matter and
objects, work changes kinetic energy
and potential energy of a system, while
heat changes internal energy. For gases
and liquids it is more complicated:
friction in fluid flow gives viscous heat,
compression of a gas at constant
volume increases its temperature, etc.
Picture: KJ05
p,V,T surface for a pure component
For a substance that

expands on melting
Source:http://newark.rutgers.edu/~huskey/images/PVT_phase_diagram.jpg

Processes in p,V and T,V diagrams
T = constant for ideal gas
(isothermal)
 For n moles of an ideal gas, pV = nRT

Picture: SEHB06

Polytropic processes of ideal gases /1

 A general expression for a gas
process can be written as
pVn = constant
with polytropic exponent n
 n = 0: p = constant (isobar)
n=1: pV = constant = nRT (isotherm)
n = γ = cp/cv: pVγ = constant (isentrope) *, **
n = ∞: V = constant (isochore, isometric)
* isentropic = with constant entropy S :

** This requires that
ΔS = ΔQ/T = 0, i.e. an adiabatic reversible
process cp and cv ≈ constant !
! A process without heat transfer is called
adiabatic, this is not the same as isothermal ! Picture: T06
Polytropic processes of ideal gases /2
calculating p,V work for ideal gases
n
 Pressure-volume work W is calculated as p  W V 

   =
p  V 
W12 = - V1∫V2 pdV, and for any polytropic n
T  V 
process pVn = constant = C, i.e. p1V1n = p2V2n  
T  V 
n
p   T  n
 
 This means p = C / Vn and for n≠1: p  T 
V2 V2
dV C p V  p 2 V2

W12  W   pdV  - C
V1
V
V1
n
-
1- n
( V21n  V11n )   1 1
n 1
and for an isothermal process (n = 1, p1V1 = p2V2 = nmolRT):
V2 V2
dV V2 V
W12  W    pdV  - nmolRT V  - nmolRT(lnV2  lnV1 )  nmolRT ln   p1V1 ln 2
V1 V1
V1 V1
Note: work done ON (=into) system = -∫pdV, work done BY (=out of) system = ∫pdV
Example: calculating p,V work /1

 Oxygen at 300 K expands slowly and out
isothermally from 100 kPa to 45 kPa.
The mass of the O2 is 0.052 kg;
calculate the work Wout done by the
gas.
 Answer: (the cooling effect that arises from the expansion is

compensated for by a heat flow Q ≈ Wout)
m = 0.052 kg  nmol = m/M = 0.052 kg/0.032 kg/mol = 1.625 mol
W = - nmol· RT· ln(V2/V1) = - Wout
Source and
ideal gas law gives p1V1 = nmolRT = p2V2 V2/V1 = p1/p2 picture: KJ05
 This gives Wout = nmol· RT· ln(p1/p2) =
=1.625 mol * 8.314 J/(molK) * 300 K * ln(100/45) = 3236 J = 3.24 kJ
System energy increases by Q + W = Q - Wout
Example: calculating p,V work /2
 A well insulated piston-cylinder set-up
contains 0.031 m3 air at 40°C and 102
kPa; calculate the work needed to
compress this air slowly to 350 kPa.
Consider the process adiabatic. For air,
γ = cp/cv = 1.4
 Answer: the process can be described as isentropic

V2 V2 V2
 pV n 1n 
dV p1V1  p 2 V2
 
n
W   pdV  - pV  -  V   
Vn 1 - n  V1 n 1
V1 V1
Source and
 V2 follows from p1V1γ = p2V2γ  V2 = V1(p1/p2)1/γ picture: KJ05
= 0.031m * (102 kPa/350 kPa)
3 1/1.4 = 0.0128 m 3
 Thus, Win = -(102 kPa * 0.031 m3 – 350 kPa * 0.0128 m3) /(1.4 - 1)
= 3290 J = 3.29 kJ = W System energy increases by W = W in
Enthalpy /1
 Consider the addition of heat to a gas (assume an ideal
gas for the moment) in two different situations
(a) a rigid tank, i.e. a constant volume process
(b) a cylinder-piston assembly, i.e. a constant
pressure process
picture: KJ05
Enthalpy /2
(a) constant volume
The energy balance (no potential energy or
kinetic energy effects):
ΔU = Q + W, and since no work is done:
ΔU = Q
This implies that all heat is used to increase
the temperature of the gas at constant volume.
With specific heat at constant volume,
cv (J kg-1K-1), gas mass m and temperature T:
ΔU = m· cv· ΔT, or Δu = cv· ΔT
which can be written as
cv = Δu / ΔT or cv = du / dT
IF u is a function of T only !
picture: KJ05
Enthalpy /3
(b) constant pressure
The energy balance (no potential energy or
kinetic energy effects):
ΔU = Q + W, and some work is done to
increase the volume as to keep pressure
constant: W = - V∫ p dV,
with p = external pressure = internal pressure
(at equilibrium: assume a slow or ”quasi-
equilbrium” process !)
As p is constant, W = - p· ΔV, and thus
ΔU = Q - p· ΔV, or Q = ΔU + p· ΔV
= (at constant pressure) Q = Δ (U + p· V)
Part of the heat Q is used to increase volume V !
picture: KJ05

Enthalpy /4 Enthalpy takes into
consideration that a constant
(b) constant pressure (continued) pressure process may give
The quantity U + p·V is referred to as a volume change which
enthalpy, H (unit: J) implies exchange of work
with the environment
→ the energy balance gives
Q = ΔH = m· Δh with specific enthalphy h
With specific heat at constant pressure,
cp (J kg-1K-1), gas mass m and temperature T:
Q = ΔH = m· cp· ΔT, or Δh = cp· ΔT
which can be written as
cp = Δh / ΔT or cp = dh / dT
IF h is a function of T only !
Simular to u, h must be fixed to a reference
value h = h° at T = T°
picture: KJ05
Like U, p, T and V, enthalpy is a thermodynamic state property
Specific heat of gases /1

 Specific heat is also referred to as heat capacity
 For an ideal gas u = u(T) and cv = du/dT, and
h = h(T) and cp = dh/dT
 Specific heat ratio cp/cv = γ
 According to the so-called State Principle ”any two

independent thermodynamic properties are sufficient to describe
the state of a system containing a single pure substance”
(a simplification of the so-called phase rule by J.W. Gibbs
for multi-phase, multi-component systems)
 Thus, u= u(p,T) or u= u(v,T) and h= h(p,T) or h= h(v,T)

Specific heat of gases /2
 Thus, u= u(p,T) or u= u(v,T) and h= h(p,T) or h= h(v,T)
 This leads to partial differential expressions:
 u   u   u 
du    dT    dV  c v dT    dV
  T V   V T   V T
 h   h   h  =0
dh    dT    dp  c p dT    dp
 T  p  p  T  p  T for an
ideal gas
 Another important parameter is the Joule-Thomson
coefficient µJT, that quantifies how the temperature of a
substance will increase or decrease when pressure is
changed at constant enthalphy: VERY
IMPORTANT
 T   h 
μJT    and    c p  μJT FOR THIS
 p  h  p T COURSE
The total energy balance

 The total energy of a system equals
E = mgz + ½mv2 + U + pV = mgz + ½mv2 + H,
or as energy concentration (and using m = ρ·V)
e = gz + ½v2 + u + p/ρ = gz + ½v2 + h
 For a process that involves energy transfer to the system as

heat and/or work:
ΔE = Q + W
Δ(mgz + ½mv2)+ ΔU + Δ(pV) = Δ(mgz + ½mv2) + ΔH = Q + W
Δe = q + w
Δ(gz + ½v2)+ Δu + Δ(p/ρ) = Δ(gz + ½v2)+ Δh = q + w

Throttling valves
 A throttling device is used to
reduce the pressure of a
flowing fluid, producing a large
reduction in pressure over a
short distance.
 Mass and energy balances
show
– One inlet and one outlet Throttling devices
– No work is done  Note that (partial) vaporisation
– Steady state (usually) or condensation is possible,
– No significant heat transfer giving a temperature effect!
 → A constant enthalpy, (↔ Joule-Thomson coefficient)
”isenthalpic” process,
hin = hout Source and picture: KJ05
Entropy /1
 A spontaneous process occurs (fast or slow) without
outside intervention
 Earlier it was thought that processes are spontaneous if
exothermic (= producing heat, ΔH < 0), but, for example,
ice melting at > 0°C is endothermic (= consuming heat,
ΔH > 0) and spontaneous!
 The driving force for a spontaneous process
is an increase of the ENTROPY of the universe
 Nature spontaneously proceeds towards the states that
have the highest probability
http://wps.prenhall.com/wps/media/objects/602/616516/Media_Assets/Chapter17/Text_Images/FG17_01.JPG
Entropy /2
 The entropy of the universe must increase:
ΔSuniverse = ΔSsystem + ΔSsurroundings
ΔSuniv > 0 : spontaneous process
ΔSuniv < 0: spontaneous process in reverse direction
ΔSuniv = 0: equilibrium
http://wps.prenhall.com/wps/media/objects/602/616516/Media_Assets/Chapter17/Text_Images/FG17_03.JPG
Entropy /3
 ΔSuniv = ΔSsys + ΔSsurr , > 0 if ΔSsys > -ΔSsurr
ΔSsurr is primarily determined by the flow of energy in or
out the system as heat
 Exothermic processes: Q to surroundings, ΔSsurr > 0
Endothermic processes: Q into system, ΔSsurr < 0
 If ΔSsurr or ΔSsys < 0, temperature determines what will
happen, for example: water → ice if T < 0°C (at 1 bar)
 ΔSsurr depends on temperature:
quantity of heat from system to surroundings Q
ΔSsurr  
temperature T
ΔHsystem
 (if no work is done, - Q  - ΔH)  
T
ΔHsys Note: Q =
ΔSsys   ΔGsys  0
T heat into the system !

Entropy /4 The Definition
 For a cycle with irreversible step 1→2 and
reversible return 2→1 T, s diagram
  
δQ δQ δQ
 T   T   ; 

T
 (S  S  )  
 
δQ δQ
S   S   ; S   S    S generated

T 
T
 For a real process:

δQ Q
Sgenerated > 0 dS   ΔS   Q  T ΔS
T T
 For a reversible process: 
 : S  Q
entropy of a heat stream Q
Sgenerated = 0
T
 For an impossible process: 
 : Sm
entropy of a mass stream m  s
Sgenerated < 0
dS c p

dT T picture: KJ05
Second Law of Thermodynamics /1

 ”The entropy of an isolated system will
always increase until it reaches a state of
equilibrium* at which the entropy is
maximised” (SEHB06)
http://www.theonion.com/content/node/28308/print/
 Clausius: ”Heat cannot move

spontaneously from cold to hot bodies”
(KJ05); ”The entropy of the universe
tends toward a maximum” (T06) Conservative Christians
protest the second law of
thermodynamics on the
 Kelvin-Planck: ”Although all work can steps of the Kansas Capitol
(September, 2000)
always be converted completely to heat,
heat cannot be completely and
continuously converted into work” (T06)

Second Law of Thermodynamics /2
 RZ: ”Producing work by extracting
http://www.oup.com/uk/orc/bin/0198792859/resources/images/fig04.06.jpg
heat from 1 kg of hot substance will
result in 1 kg of cold substance”
 vS91: ”Endast sådana processer och

förändringar är möjliga som ökar den
totala oordningen”
 Some implications:
1) Every process has losses;
2) We cannot build a perpetuum
mobile machine;
3) Heat cannot be converted into
work with 100% efficiency.

Heat → work: power cycles /1

”A thermodynamic cycle consists of
a sequence of processes in which
the working fluid returns to it’s
original thermodynamic state” (T06)
 An air power cycle and its p-V diagram pictures: KJ05

1→2: Heat-up at constant volume: pressure ↑
2→3: Heat-up at constant pressure: volume ↑, work is done
3→4: Cooling at constant volume: pressure ↓
4→1: Compression (volume ↓) and cooling at constant pressure
 The cycle generates

.
work .Wnet = Wout – Win, pictures: KJ05
.
or power Wnet = Wout – Win,
 The First Law of Thermodynamics gives energy we want to use
. . . ηthermal 
Qin = Wnet + Qout, or Qin = Wnet + Qout energy we must put in
 Assuming that the goal is to produce work W Q  Qout Q
 net  in    out
Qin Qin Qin
(i.e. generate power) using the incoming heat
  Q  
streams, the thermal efficiency or Carnot  Wnet Q
 in out Q
   out
Q 
Q Q
efficiency of the cycle, ηcycle, can be defined. in in in

Example of a refrigeration cycle
Example of a power cycle

pictures: KJ05
 A power cycle is typically operated between two thermal
reservoirs, with thermal efficiency η = 1- QL/QH
A power cycle A refrigeration cycle
 Is it possible to construct a cycle

with QL = 0 ?
 The energy balance for that case:
Wnet = QH pictures: KJ05

 Let’s assume that the work Wnet is
used to drive a refrigeration cycle
 The energy balance for
that: Wnet = QL+ QH’
which with Wnet = QH
gives QL+ QH = QH’
or QL = QH’ - QH
 No work enters the system indicated

by which would mean that
heat QL moves spontaneously from
low-temperature TL to high-temperature reservoir TH
 This contradicts the Second Law of Thermodynamics →
not possible.
pictures: KJ05
Energy conversion heat ↔ work
100% conversion
p,V work Non - p,V work
100% conversion
100% conversion
100% conversion
Conversion partly
Conversion partly
Environment
Fraction Fraction
T°/T1 T°/T2
is lost is lost
at T = T°
Only if T1 < T2
Heat Heat
at T=T1 Only if T1 > T2 at T=T2
Conversion of heat (to work) is limited

Process thermodynamics modelling
 The starting point:

equations for the First and Second law of
Thermodynamics:
Energy Balance: Total Energy = constant
Entropy Balance: Entropy Generation ≥ 0
 P Q  dE
Pin  Q in out out  E  H  ½mv 2  mg(z - z0 )
dt
Q Q
m  sin     S gen  m  sout     dS
     
 T in  T  out dt
See also ÅA VST course 424300 Teknisk termodynamik
9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering
A refrigeration process /1 (vS91)
Ambient
Power P (W)
surroundings
T = T0
. . .
Heat Q1 (W) Heat Q1 (W) Heat Q2 at T2 (W)
Cold rum, T = T1 Refrigerator
 A cold room must be maintained at a low temperature

T1 < T0
.
 A heat stream Q1 from the surrounding must be
(continuously) removed to achieve this, using an cooling
device, refrigerator (sv: kylmaskin), driven by electric
power P
A refrigeration process /2 (vS91)

Ambient
Power P (W)
Energy balance : surroundings

 P  Q T = T0
Q1 2 . . .
Entropy balance :
  Cold rum, T = T1 Refrigerator
Q Q
1
 S gen  2
T1 T2
.
 The heat stream Q2 at T2 
Q 
Q Q P Q

> T1 must be such that S gen  2  1  1  1 0
·
T2 T1 T2 T1
Sgen > 0
. .  (T2  T1 )  T S
P  Q1 2 gen
 Q2 > Q1: the refrigerator T1
”pumps out” more heat  (T2  T1 )  Q
 ( T2  1)
Pmin imum  Q1 1
than it receives T1 T1

A refrigeration process /3 (vS91) COP
Ambient
Power P (W)
Energy balance : surroundings
 P  Q T = T0
Q 1 2 . . .
Entropy balance :
  Cold rum, T = T1 Refrigerator
Q 1  Q
 S gen  2
T1 T2

Q 1 T1 Q
1 1
 A device that   
P T 
T2  T1 Q 2  Q 
transports heat from a
2
1 1
T1
lower temperature to energy we want to get out
  COP
a higher temperature energy we must put in
is called a ”heat " coefficient of performance" ,
pump” note : COP  1 or  100%

A refrigeration process /4
”HOT”
The heat carrier

is called ”refrigerant” ”COLD”
picture: KJ05
 Schematic of vapor-compression refrigeration cycle.

Properties of pure substances /1
Condensation of a gas at constant pressure
saturation
temperature
for this pressure
p = constant
pictures: after KJ05
When cooled to low enough temperatures, gases condense into liquids.

In the cooling process above, liquid droplets start to form at point C
where a saturated (sv: mättad) vapour exists. Further cooling along
CDE gives a two-phase mixture (droplets in gas) until at point E a
saturated liquid is obtained.

Condensation of a gas at constant pressure
picture: KJ05
Connecting, for different pressures, the saturation points for the gas (C,
C’, C”,....) gives the saturated vapour line; similarly the saturation
points for the liquid (E, E’, E”, ...) gives the saturated liquid line.
These lines come together at the critical point, on what is called the
liquid-vapour dome (sv: kupol)
Condensation of a gas : mixture quality
Under the liquid-vapour
dome, a two-phase (liquid-
vapour) mixture exists; the
quality, x, of this mixture
is defined as the mass
fraction vapor in the
mixture: x=0 x=1
mgas picture: KJ05

mV
x 
mgas  mliquid m V  mL
mg
 (with " f" from german " flüssig" )
mg  mf
Note that x is a thermodynamic property, like p,T,v, u, h, s


Condensation of a gas : mixture quality
m gas mV
x 
m gas  m liquid m V  mL
http://smirnov.mae.wvu.edu/courses/mae320/figs/F3-8.jpg
mg
x (with " f" from german " flüssig" )
mg  mf
With specific volume v = V/m (m3/kg)

(= 1/density !) this gives for x:
v = (1-x)·vL + x·vv or v = (1-x)·vf + x·vg
DATA FOR
u = (1-x)·uL + x·uv or u = (1-x)·uf + x·ug
hf, hg, vf, vg,
h = (1-x)·hL + x·hv or h = (1-x)·hf + x·hg etc. etc.
s = (1-x)·sL + x·sv or s = (1-x)·sf + x·sg from Tables

Water/steam h,p diagram
critical
point
Source: http://www.ent.ohiou.edu/~thermo/me328/chapter.info/Chapter10_1.html
Example: Isothermal compression of steam

 Thirty-one (31) kg of (supersaturated)
steam in a piston-cylinder assembly are
compressed slowly (i.e. reversibly) and
isothermally at 500°C from 100 kPa to
300 kPa. Making use of entropy data,
calculate the heat transfer ΔQ. picture: KJ05
ΔT=0 → pΔV+VΔp=0
Answer: energy balance ΔU = ΔW + ΔQ = (ΔpV=0) = ΔH ≈ 0 (T=cst)
 For a reversible process: S2–S1 = 1∫2 δQ/T = (1/T) 1∫2 δQ = ΔQ/T
 With ΔQ = T·ΔS = T· m· Δs + table data for entropy : ΔQ < 0 since cooling
is needed to keep
s1 = 8.8342 kJ/kgK, s2 = 8.3251 kJ/kgK gives temperature constant
ΔQ = 31 kg· 773 K· (8.3251 – 8.8342) kJ/kgK = -12200 kJ

Note: The work W done by the system = - n· R·T· ln(V2/V1) = n· R·T· ln(p1/p2)
= 1722 mol· 8.314 J/molK·773K· ln(3 bar/1 bar) = -12158 kJ; there is a small
enthalpy change of the steam (→ table) = Δh = 31 kg *-2 kJ/kg = -62 kJ ;
here we see a deviation from ideal gas behaviour!
h,p diagram for CO2, for R134a
https://www.ohio.edu/mechanical/thermo/property_tables//
See also diagrams at
http://joho.p.free.fr/EC/ENERGIE/_Ressources/FLUIDES%20Frigorig%C3%A8nes/Dupont%20de
%20Nemours/www.dupont.com/suva/emea/products/technical/molier_pe.html
And: http://professor.iaut.ac.ir/Book_Dl.aspx?FDDILKJ=216 (english/american units....)
Note: this last slide is not from course PTG
Sources #1
 A83: P.W. Atkins ”Physical chemistry”, 2nd ed., Oxford Univ. Press (1983)
 A11: R. C. Arora ”Refrigeration and air conditioning”, 2nd. Ed. PHI Learning Private
Limited, New Delhi (2011) Chapters 1-2
 ÇB98: Y.A. Çengel, M.A. Boles “Thermodynamics. An Engineering Approach”, McGraw-Hill (1998)
 D03: İ. Dinçer “Refrigeration systems and applications” Wiley (2003)
 HTW08: G.F. Hundy, A.R. Trott, T.C. Welsh “Refrigeration and air conditioning 4th ed. Butterworth-
Heinemann (2008)
 KJ05: D. Kaminski, M. Jensen ”Introduction to Thermal and Fluids Engineering”, Wiley (2005)
 SEHB06: P.S. Schmidt, O. Ezekoye, J. R Howell, D. Baker “Thermodynamics: An Integrated Learning
System” (Text + Web) Wiley (2006)
 S90: A.L. Stolk ”Koudetechniek A1”, Delft Univ. of Technol. (1990)
 T06: S.R. Turns ”Thermal – Fluid Sciences”, Cambridge Univ. Press (2006)
 vS91: R. von Schalien ”Teknisk termodynamik och modellering”, 6. ed, Åbo Akademi University (1991)
 Z13: R. Zevenhoven, Processteknikens grunder / Principles of process engineering, course
compendium (2013) download: http://users.abo.fi/rzevenho/PTG%20Aug2013.pdf
 Ö96: G. Öhman ”Kylteknik”, Åbo Akademi Univ. (1996)
 See also: Martinez, I. ”Lectures on Thermodynamics” – lecture 18 (English or Spanish)
http://webserver.dmt.upm.es/~isidoro/bk3/index.html updated and based on “Termodinámica básica y
aplicada", Ed. Dossat, Madrid (1992) ISBN 84-237-0810-1


Refrigeration (Kylteknik) : 1. Introduction, Historic Overview, Brief Re-Wrap of Thermodynamics

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Refrigeration (Kylteknik)

course # 424519.0 E v. 2017

1. Introduction, historic overview,

ÅA 424519 Refrigeration / Kylteknik

1.1 Refrigeration and this course

 Thermo-electric processes, process comparison, process

 Air conditioning, cooling towers

9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering 5/66

Refrigeration: what and why /2

absolute zero: +15°C → -273.15°C (0 K)

Refrigeration: what and why /4

– Technical information on systems

9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering 8/66

ÅA 424519 Refrigeration / Kylteknik

1.2 Historic overview

 Storage of ice, snow in cellars

 Pot-in-pot cooling systems (Nigeria):

Natural refrigeration processes /2

 Wet cloth can give a further cooling effect. During night-

9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering 12/66

Technical refrigeration processes /2

 1834: Perkins (USA) vapor-compression refrigeration

 1827 – 1844: Stirling

Technical refrigeration processes /4

 During 1877 – 1908 liquefaction of gases is developed, at

For pressure = 1 bar

Technical refrigeration processes /5

Refrigerators and heat pumps

Picture: http://techalive.mtu.edu/meec/module13/AirConditioning.htm Picture: ÇB98

 Air conditioning ↑  Food refrigeration ↑

Picture: http://www.ohiocitizen.org/campaigns/ Picture: http://www.corrosion-doctors.org/

Other issues to be considered

 Liquefied natural gas (LNG)  Solar cooling

1.3 Brief re-wrap of thermodynamics

First Law of Thermodynamics

Closed system ΔE = W + Q (or: dE = δW + δQ)

 Energy cannot be produced and speaking about ”energy

Total energy of a system

 For an open system, MASS may cross the bounday and

p,V,T surface for a pure component

For a substance that

9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering 28/66

 For n moles of an ideal gas, pV = nRT

9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering 29/66

Polytropic processes of ideal gases /1

* isentropic = with constant entropy S :

 Pressure-volume work W is calculated as p  W V 

Example: calculating p,V work /1

 Answer: (the cooling effect that arises from the expansion is

System energy increases by Q + W = Q - Wout

 Answer: the process can be described as isentropic

9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering 36/66

Specific heat of gases /1

 Specific heat ratio cp/cv = γ

 According to the so-called State Principle ”any two

9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering 38/66

The total energy balance

 For a process that involves energy transfer to the system as

9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering 40/66

9.1.2017 Åbo Akademi Univ - Thermal and Flow Engineering 44/66

 For a real process:

Second Law of Thermodynamics /1