Thermodynamics of processes

Wei Yan

Center for Energy Resources Engineering (CERE)

Department of Chemistry
Technical University of Denmark
Content

 Flow processes
 Introduction
 Duct flow of compressible fluids
 Turbines (expanders)
 Compressors and pumps
 Power generation
 Introduction
 Steam power plan
 Internal combustion engine
 Jet engines
 Refrigeration and liquefaction
 Introduction
 Carnot refrigerator
 Adsorption refrigeration
 Heat pump
 Liquefaction processes (Linde, Claude…)

2
Introduction: Application of thermodynamics
to flow processes

 The thermodynamics of flow is based on the mass, energy, and entropy balances.
The discipline underlying the study of flow is fluid mechanics, which encompasses
not only the balances of thermodynamics but also a momentum balance that arises
from the laws of classical mechanics (Newton’s laws). This makes fluid mechanics a
broader field of study. The distinction between thermodynamics problems and fluid-
mechanics problems depends on whether this momentum balance is required for
solution. Those problems whose solutions depend only on mass conservation and on
the laws of thermodynamics are commonly set apart from the study of fluid
mechanics and are treated in courses on thermodynamics. Fluid mechanics then deals
with the broad spectrum of problems which require application of the momentum
balance.

 Thermodynamic analysis of flow processes is most often applied to processes

involving gases or supercritical fluids. In these compressible flow processes the fluid
properties change as a result of changes in pressure, and thermodynamic analysis
provides relationships between these changes.

3
Duct flow of compressible fluids

 Sizing of pipes and shaping of nozzles require application of the momentum balance
of fluid mechanics, and therefore are not part of thermodynamics.
 Thermodynamics does provide equations that interrelate the changes in pressure,
velocity, cross sectional area, enthalpy, entropy, and specific volume of a flowing
stream.
 We consider here the adiabatic, steady-state, one-dimensional flow of a
compressible fluid in the absence of shaft work and of changes in potential energy.
u 2
Energy balance H  0
2
dH  udu (differential form) (7.3)

Continuity equation d (uA / V )  0

dV du dA
  0 (7.4)
V u A

4
Duct flow of compressible fluids

Fundamental property relation dH  TdS  VdP (6.9)

Specific volume as a function of its entropy and pressure
V  V ( S , P)

 V   V 
dV    dS    dP
 S  P  P  S
 V   V   T  VT
1st term on RHS:       
 S  P  T  P  S  P CP

 V   V  V2
2nd term on RHS: c  V 
2 2
     2
 P S  P  S c
dV  T V
 dS  2 dP (7.5)
V CP c

5
Duct flow of compressible fluids

With the above 4 equations, we treat dS and dA as independent and develop equations
that express the remaining differentials as functions of these two.

Combine (7.3) and (6.9): udu  TdS  VdP (7.6)

Eliminate dV and du from (7.4) by Eqs. (7.5) and (7.6):

  u2  u 2 dA
(1  M )VdP  1 
2
 TdS  0 (7.7)
 C P  A
where M is the Mach number, defined as the ratio of the speed of the fluid in the duct
to the speed of sound in the fluid, u/c. Equation (7.7) relates dP to dS and dA.
Combine Eqs. (7.6) and (7.7) to eliminate VdP:

  u2 2 
 C  M 
 
2
1 u
udu   P  TdS  
2 
dA  0
 1 M  2
 1  M  A (7.8)
 
 
Equation (7.8) relates du to dS and dA. Combined with Eq. (7.3) it relates dH to dS
and dA, and combined with Eq. (7.4) it relates dV to these independent variables. 6
Duct flow of compressible fluids

For fluid traversing a differential length dx of its path, Eqs. (7.7) and (7.8) become
dP   u 2  dS u 2 dA
(1  M )V
2
 1  T  0 (7.9)
dx  CP  dx A dx

  u2 2 

du  CP  dS
M
 
2
T 1 u dA
u    2 
0 (7.10)
dx  1 M 2
 dx  1  M  A dx
 
 
According to the second law, we have for adiabatic flow

dS irreversible
0
dx reversible

7
Duct flow: Pipe flow

 For the case of steady-state adiabatic flow of compressible fluids in a horizontal pipe
of constant cross-sectional area, dA/dx=0, and Eqs. (7.9) and (7.10) reduce to
  u2    u2 2 
1  C   dS
T  CP  dS
M
dP du
 u T  P 
dx V  1  M  dx
2
dx  1  M  dx
2

   
   
For subsonic flow, M2<1 and we have
dP du
 0 and 0
dx dx
The pressure decreases and the velocity increases in the direction of flow.
The velocity cannot exceed the sonic value. Otherwise the above inequalities would
reverse.
The equations for pipe flow indicate that when flow is supersonic the pressure
increases and the velocity decreases in the direction of flow. However, such a flow
regime is unstable. When a supersonic stream enters a pipe of constant cross section,
a compression shock occurs, the result of which is an abrupt and finite increase in
pressure and decrease in velocity to a subsonic value 8
Duct flow: Nozzles

 Nozzles have changing cross-sectional area available for flow that results in the
interchange of internal and kinetic energy of a fluid.
 The design of effective nozzles is a problem in fluid mechanics, but the flow through
a well-designed nozzle is susceptible to thermodynamic analysis
In the limit of reversible flow, dS/dx=0 and Eqs. (7.9) and (7.10) become:

dP u 2  1  dA du  1  u dA
   2 
  dx  1  M  A dx
dx VA  1  M 2  dx

The characteristics of flow depend on whether the flow is subsonic (M<1) or

supersonic (M>1).

Subsonic: M<1 Supersonic: M>1

Converging Diverging Converging Diverging
dA/dx - + - +
dP/dx - + + -
du/dx + - - +
9
Duct flow: Nozzles

 For subsonic flow in a converging nozzle, the velocity increases and the pressure
decreases as the cross-sectional area diminishes. The maximum obtainable fluid
velocity is the speed of sound, reached at the exit.
 Supersonic velocities are readily attained in the diverging section of a properly
designed converging/diverging nozzle. With sonic velocity reached at the throat, a
further increase in velocity and decrease in pressure requires an increase in cross-
sectional area, a diverging section to accommodate increasing volume of flow.

P2
P1

The speed of sound is attained at the throat of a converging/diverging nozzle only when
the pressure at the throat is low enough that the critical value of P2/P1 is reached. If
insufficient pressure drop is available in the nozzle for the velocity to become sonic,
the diverging section of the nozzle acts as a diffuser (i.e., the pressure rises and the
velocity decreases)
10
Duct flow: Nozzles

 The relation of velocity to pressure in an isentropic nozzle for ideal gas with
constant heat capacities.
Combine Eqs. (6.9) and (7.3): udu  VdP
Integration, with nozzle entrance and exit conditions denoted by 1 and 2, yields:
( 1)/ 
2 PV  P  
u2  u1  2 VdP 
P2
2 2 1 1
1   2   (7.11)
P1   1   P1  
Here we have used PV γ = const. for adiabatic process.
Equation (7.11) may be solved for the pressure ratio P2/P1 for which u2 reaches the
speed of sound, i.e. where
 P  2 P2 
u22  c 2  V22    V2      PV
 V S ,V V2
2 2
 V2 

If we set u1=0, solution for the pressure ratio at the throat gives
 /( 1)
P2  2 

P1    1  11
Duct flow: Throttling process

 When a fluid flows through a restriction, such as an orifice, a partly closed valve, or
a porous plug, without any appreciable change in kinetic or potential energy, the
primary result of the process is a pressure drop in the fluid.
 Such a throttling process produces no shaft work, and in the absence of heat transfer,
the energy balance becomes
H  0 or H 2  H1

 The enthalpy of an ideal gas depends on temperature only, a throttling process does
not change the temperature of an ideal gas.
 For most real gases at moderate conditions of temperature and pressure a reduction
in pressure at constant enthalpy results in a decrease in temperature.
 The system can be in a two-phase state after throttling.

12
Duct flow: Throttling process

 Example: Throttling a real gas from conditions of moderate temperature and

pressure usually results in a temperature decrease. Under what conditions would an
increase in temperature be expected?
 Solution:
The sign of temperature change is determined by the sign of the derivative (∂T/∂P)H,
called the Joule-Thomson coefficient μ:
 T 
  
 P  H

A positive μ corresponds to a temperature decrease and a negative μ corresponds to a

temperature increase.
Since H = f(T, P),
1
 T   T   H   H   H  1  H 
                  
 P  H  H  P  P T  T  P  P T CP  P T

13
Duct flow: Throttling process

From dH = TdS + VdP,

 H   S   V 
   V  T    V  T  
 P T  P T  T  P

Here we have used the Maxwell relation (∂S/∂P)T = - (∂V/∂T)P . Substituting V=ZRT/P
allows this equation to be rewritten in terms of Z as
 H  RT 2  Z 
    
 P T P  T  P

Substitution into the earlier expression for μ gives

RT 2  Z 
  
CP P  T  P

Thus, (∂Z/∂T)P and μ have the same sign.

14
Duct flow: Throttling process

The condition (∂Z/∂T)P = 0 defines the Joule-Thomson inversion curve, which

separates the region of positive μ from that of negative μ. The following figure shows
reduced inversion curves (between Tr and Pr for which μ = 0).

The solid line correlates data for Ar, CH4,

N2, CO, C2H4, C3H8, CO2 and NH3.

The dashed line is calculated from

(∂Zr/∂Tr)Pr = 0 using the Redlich-Kwong EoS

15
Duct flow: Turbines (Expanders)

 Internal energy  expansion  high-velocity stream/kinetic energy  strikes on

blades attached to a rotating shaft  shaft work
 A turbine (or expander) consists of alternate sets of nozzles and rotating blades
through which vapor or gas flows in a steady-state expansion process. The overall
result is the conversion of the internal energy of a high-pressure stream into shaft
work.
 When steam provides the motive forces
as in most power plants, the device is called
a turbine; when it is a high-pressure gas,
such as ammonia or ethylene in a chemical
plant, the device is usually called an expander.

16
Duct flow: Turbines (Expanders)

 Energy balance
WS  H  H 2  H1 WS  mH  m( H 2  H1 )
 Usually, the inlet conditions T1 and P1 and the discharge pressure P2 are fixed.
Therefore, only H1 is known; both H2 and WS are unknown.
 If the fluid in the turbine expands reversibly and adiabatically, the process is
isentropic, and
S2  S1

This second equation fixes the final state of the fluid and determines H2.
WS (isentropic)  (H ) S

 The shaft work 𝑊𝑆 (isentropic) is the maximum that can be obtained from an
adiabatic turbine with given inlet conditions and given discharge pressure.
 Actual turbines produce less work due to irreversibility. The turbine efficiency is
defined by WS

WS (isentropic)
17
Duct flow: Turbines (Expanders)

Apparently,
H

(H ) S

 Values of η often fall in the range from 0.7 to 0.8. The following HS diagram
illustrates an actual expansion in a turbine and a reversible expansion for the same
intake conditions and the same discharge pressure.

18
Duct flow: Compressor

 Compression processes bring about pressure increases. Compressors, pumps, fans,

blowers, and vacuum pumps are all devices designed for this purpose. We are
concerned here not with the design of such devices, but with specification of energy
requirements for steady-state compression causing an increase in fluid pressure.
 The compression of gases may be accomplished in equipment with rotating blades
(like a turbine operating in reverse) or in cylinders with reciprocating pistons.
 The energy balance equation is essentially the same as for turbines or expanders.
Here potential and kinetic-energy changes are presumed negligible.

WS  H  H 2  H1

WS  mH  m( H 2  H1 )

19
Duct flow: Compressor

 In a compression process, the isentropic work is the minimum shaft work required
for compression of a gas from a given initial state to a given discharge pressure.
 The compressor efficiency

WS (isentropic)

WS
It can also be given by

(H ) S

H

The efficiency is usually in the range of 0.7 to 0.8.

20
Duct flow: Pumps

 Liquids are usually moved by pumps, which are generally rotating equipment.
 The same energy balance equation Ws = ΔH applies. Since the values of the enthalpy
of compressed (subcooled) liquids are seldom available, some further derivations
may be made:
dH  VdP (const S )

WS (isentropic)  (H ) S   VdP  V ( P2  P1 )

P2

P1
Also we can utilize the following equations
dT
dH  CP dT  V (1   T )dP dS  CP  VdP
T
Considering temperature changes in the pumped fluid are very small and the properties
of liquids are insensitive to pressure, we have
T
H  CP T  V (1   T )P S  CP ln 2  V P
T1

21
Introduction: Production of power from heat

 Energy is conserved. What do we mean by “using energy”?

Conversion of energy from a form capable of producing mechanical work into heat
and/or transfer of heat from a source at higher temperature to a lower temperature.
 Various energy conversions from solar power: Except for nuclear power, solar
power is the ultimate source of almost all power used by humankind
Solar powerfossil fuelspower plants (thermal efficiencies < 35%)
Solar powerwindswind power
Solar powerphotovoltaic cellselectricity
 Our topics here:
 Steam power plants in relation to the Carnot, Rankine, and regenerative Rankine
cycles
 Internal-combustion engines in relation to the Otto, Diesel, and Brayton cycles
 Jet and rocket engines

22
Steam power plant

 A simple steam power plant: a steady-state cyclic process consisting of two

isothermal steps connected by two adiabatic steps.

Step 12: isothermal vaporization at TH

Step 23: adiabatic expansion of saturated
vapor in a turbine producing a
two-phase mixture of saturated
liquid and vapor at TC
Step 34: isothermal partial-condensation
at TC
Step 41: adiabatic compression in a pump

If all the above steps are reversible (23

and 41 are isentropic), they constitute a
Carnot cycle. The power generated by the turbine WS is much
greater than the power required by the pump Wpump

23
Steam power plant: Carnot cycle

 Representation of the process on a TS diagram

Step 12: isothermal vaporization at TH

Step 23: adiabatic expansion of saturated
vapor in a turbine producing a
two-phase mixture of saturated
liquid and vapor at TC
Step 34: isothermal partial-condensation
at TC
Step 41: adiabatic compression in a pump

Point 1: Saturated liquid

Point 2: Saturated vapor
Point 3: Two-phase mixture of saturated
liquid and vapor
Point 4: Two-phase mixture of saturated The thermal efficiency of this cycle:
liquid and vapor
TC
Carnot  1 
TH
24
Steam power plant: Rankine cycle

 The Carnot cycle has severe practical difficulties in steps 23 and 41. Step 2-3
requires a turbine to take in saturated steam and produce an exhaust with high liquid
content (severe erosion problems). Step 41 needs a pump that takes in a mixture of
liquid and vapor (cavitation problems) and discharge a saturated liquid.
 An alternative cycle is taken as the standard, at least for fossil-fuel-burning power
plants.
Step 12: A constant-pressure heating
process in a boiler.
Step 23: Reversible, adiabatic (isentropic)
expansion of vapor in a turbine to
the pressure of condenser.
Step 34: A constant-pressure, constant-
temperature process in a condenser.
Step 41: Reversible, adiabatic (isentropic)
pumping to the pressure of the boiler.
Point 1: Subcooled liquid
Point 2: Superheated vapor
Point 3: Two-phase mixture with a modest moisture content
25
Point 4: Saturated liquid
Steam power plant: Rankine cycle

 Power plants actually operate on a cycle that departs from the Rankine cycle due to
irreversibilities of the expansion and compression steps. Steps 23 and 41 are
affected by these irreversibilities. The lines on the TS diagram are no longer vertical
but tend in the direction of increasing entropy.
 The turbine exhaust is normally still wet, but with sufficiently low moisture content.
 Slight subcooling in the condenser may occur, but the effect is inconsequential.

 For the boiler and the condenser, the energy balance neglecting kinetic- and
potential-energy changes is Q  H Q  mH
26
Steam power plant: Rankine modifications

 The thermal efficiency of a steam power cycle is increased when

 the pressure and hence the vaporization temperature in the boiler is raised
(limitation due to costs/corrosion, usually lower than 100 bar/600 oC).
 the pressure and hence the condensation temperature in the condenser is reduced.
 Two modifications of the Rankine cycle are in common use to improve its efficiency
 Rankine cycle with reheat
 Regenerative Rankine cycle

27
Steam power plant: Regenerative cycles

 A common modification of the Rankine cycle is a regenerative cycle using

feedwater preheaters (Fig 5.5）. It is also common to withdraw some steam from
turbine outlets for process use and heating （Fig 5.6). Often in actual processes open
feedwater preheaters are used (Fig 5.7).

28
Steam power plant with feedwater heating

29
Internal-combustion engines

 In a steam power plant, the steam is an inert medium to which heat is transferred
from an external source. It is therefore characterized by large heat-transfer surfaces
(both for the absorption of heat and for the rejection of heat). The ability of the walls
to withstand high temperatures and pressures imposes a limit on the temperature of
heat absorption.
 In an internal-combustion engine, a fuel is burned within the engine itself, and the
combustion products serve as the working medium. No heat-transfer surfaces are
needed.
 The analysis for internal-combustion engine is however more complicated. There is
no working medium undergoes a cyclic process. Usually, one imagines cyclic
engines with air as the working fluid. The combustion step is replaced by the addition
to the air of an equivalent amount of heat. By assuming ideal-gas state for the air, a
quantitative analysis of an ideal cycle for each internal-combustion engine is possible.

30
The Otto engine

 Four strokes:
 01: an intake stroke
 123: All valves closed; Fuel/air mixture
compressed approximately adiabatically (12);
Ignition, combustion, rapid pressure increase at
nearly constant volume (23)
 341: Approximately adiabatic expansion (34);
The exhaust value opens and the pressure falls
rapidly at nearly constant volume (34)
 10: The piston pushes the remaining combustion
gases from the cylinder.

 The effect of increasing the compression ratio—the ratio of the volumes at the
beginning and the end of compression from point 1 to point 2—is to increase the
efficiency of the engine, i.e., to increase the work produced per unit quantity of fuel.

31
Internal-combustion engines

 Air-standard Otto cycle

The analysis can be done for idealized cycle
consisting of two adiabatic and two constant-
volume steps.

W (net ) QDA  QBC T T

   1 B C
QDA QDA TA  TD
 1
1
  1  
r
r  VCig / VDig is the compression ratio

 The thermal efficiency increases with r: more rapidly at low values of r but more
slowly at high values of r.
 Compression ratios in automobile engines are usually not much above 10.

32
The Diesel Engine

 The fundamental difference between the Otto

cycle and the Diesel cycle is that in the Diesel
cycle the temperature at the end of compression
is sufficiently high that combustion is initiated
spontaneously.
 This higher temperature results because of a
higher compression ratio that carries the
compression step to a higher pressure. The fuel is
not injected until the end of the compression step,
and then is added slowly enough that the
1  (1/ r ) 
 (1/ r ) 

combustion process occurs approximately   1  e

constant pressure   1/ re  1/ r 
re  VBig / VAig is the expansion ratio

 For the same compression ratio, the Otto engine has a higher efficiency than the Diesel
engine. But the Diesel engine operates at a higher compression ratios, and consequently
at higher efficiencies. Compression ratios can exceed 20 in Diesel engines employing
indirect fuel injection.
33
The gas turbine engine

 Turbines are more efficient than reciprocating engines. This is utilized in the gas-
turbine engine.

 The higher temperature of the combustion gases entering the turbine, the higher the
efficiency of the unit. The limiting temperature is determined by the strength of the
metal turbine blades and is generally much lower than the theoretical flame
temperature of the fuel. Sufficient excess air must be supplied to keep the
combustion temperature at a safe level.
34
The gas turbine engine

 The Brayton cycle is the idealization of the gas-turbine engine.

( 1)/ 
T T P 
  1 D A  1  A 
TC  TB  PB 

35
Introduction: Refrigeration and liquefaction

 The word refrigeration implies the maintenance of a temperature below that of the
surroundings.
 Best known for its use in the air conditioning of buildings and in the
preservation of foods and chilling of beverages
 Large-scale commercial processes requiring refrigeration: the manufacture of ice
and solid CO2, the dehydration and liquefaction of gases, and the separation of
air into oxygen and nitrogen

 Our focus is not the details of equipment design, but

 the model refrigerator, operating on a reverse Carnot cycle
 refrigeration via the vapor-compression cycle
 refrigeration based on vapor absorption
 heating or cooling by heat pumps
 the liquefaction of gases by refrigeration.

36
The Carnot refrigerator

 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 (see (b))

 The measure of the effectiveness of a

refrigerator is its coefficient of performance ω,
defined as

heat absorbed at the temperature QC

 
net work W
For refrigerator operating on a Carnot cycle:
W Q T T T
W  (QC  QH )    1 H  1 H  C H
QC QC TC TC
TC
 
TH  TC

37
The Carnot refrigerator

 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 (see (b))

 The measure of the effectiveness of a

refrigerator is its coefficient of performance ω,
defined as

heat absorbed at the temperature QC

 
net work W
For refrigerator operating on a Carnot cycle:
W Q T T T
W  (QC  QH )    1 H  1 H  C H
QC QC TC TC
TC
 
TH  TC

38
The Carnot refrigerator

 Coefficient of performance (COP)

heat absorbed at the temperature QC
 
net work W
TC
 for a refrigerator operating on a Carnot cycle
TH  TC

Example: COP for refrigeration at a temperature level of 5 oC in surroundings at 30 oC

5  273.15
  11.13
(30  273.15)  (5  273.15)
 The calculation is valid only for a refrigerator operating on a Carnot cycle
 It corresponds to the maximum possible COP
 COP is often greater than 1

39
The vapor-compression cycle

Step 12: Evaporation of liquid refrigerant at constant T and P absorbs heat .

Step 23′: Isentropic compression of the vapor to a higher P and T.
(Step 23: actual compression process with inherent irreversibilities)
Step 34: Cooling and condensation of the vapor to saturated liquid.
Step 41: Isenthalpic expansion to a lower P (the original pressure).

40
The vapor-compression cycle

 Energy balance:
QC  H 2  H1 QH  H 4  H 3 W  H3  H 2 H 4  H1

 COP H 2  H1

H3  H 2

 Rate of circulation of refrigerant

QC
m
H 2  H1
41
The vapor-compression cycle

 Vapor-compression refrigeration cycle on a PH diagram

42
 The choice of refrigerant

 The COP of a Carnot refrigerator does not depend on the working medium
(refrigerant). The irreversibilities have somewhat dependence on the refrigerant.
 The choice of refrigerant is based on the characteristics such as toxicity,
flammability, cost, corrosion properties, and vapor pressure. Environmental concerns
strongly constrain the choice of refrigerant.
 Industrial refrigerants: ammonia, methyl chloride, carbon dioxide, propane, and
other hydrocarbons
 Halogenated hydrocarbons: came into common in 1930s; too stable and destroy
stratospheric ozone; replaced by less-than-fully halogenated hydrocarbons or
hydroflurocarbons.

Dichloro(difluoro)methane 1,1,1,2-Tetrafluoroethane 2,3,3,3-Tetrafluoropropene

R-12 / CFC-12 / Freon 12 R-134a / HFC-134a / Freon 134a R-1234yf / HFO-1234yf / Opteon YF
GWP 10900 GWP 1430 GWP <1 43
Absorption refrigeration

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

an electric motor. But the source of electric energy is most likely a heat engine. Thus
the work for refrigeration comes ultimately from a heat engine.
 This suggests a combination of cycles where
 work produced by an engine cycle is used internally
 heat taken both at elevated temperature TH and at cold temperature Tc
 heat rejected to the surroundings at Ts

 Analysis of such a combination of Carnot cycles:

TS  TC
A Carnot refrigerator W  QC 
TC  QH TH TS  TC
 
A Carnot engine QH  W
TH  QC TH  TS TC

TH  TS

The value of QH/QC given by the above equation is a minimum limiting value for
absorption refrigeration 44
Absorption refrigeration

 The essential difference between a vapor-

compression and an absorption refrigerator
is in the different means employed for
compression
 The section to the right of the dashed line is
the same as in a vapor-compression
refrigerator.
 A nonvolatile liquid solvent is used to
absorb refrigerant from the evaporator. The
liquid solution is pumped to the regenerator
where the refrigerant is desorbed.

 Example refrigerant-absorbent: water-lithium bromide, ammonia-water, methanol-

polyglycolethers
 For refrigeration at a temperature level of -10 oC with a heat source of condensing
steam at atmospheric pressure (TH =373.15 K) and a surroundings temperature of 30
oC (T =303.15 K), the minimum Q /Q is found to be 0.81 (the actual value around
S H C
3× larger)
45
Heat pump

 The heat pump, a reversed heat engine, is a device for heating houses and
commercial buildings during the winter and cooling them during the summer. In the
winter it operates so as to absorb heat from the surroundings and reject heat into the
building. In the summer the flow of refrigerant is simply reversed, and heat is
absorbed from the building and rejected through underground coils or to the outside
air.

Vapor-compression refrigeration cycle: A typical refrigeration cycle on a PV

(1) condenser, (2) expansion valve, (3) diagram
evaporator, (4) compressor
46
Heat pump—Example

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

47
Heat pump

 Solution:
The minimum power requirements are provided by a Carnot heat pump. For winter
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:
T  10  273.15  1
QC  QH C  30    28.02 kJ  s
TH  30  273.15 
This is the heat absorbed in the ground coils. By Eq. (9.1),

W  QH  QC  30  28.02  1.98 kJ  s1

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:

TH  TC  25  5  1
W  QC  60    4.31 kJ  s
TH  5  273.15 
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. 48
Liquefaction processes

 Widely used liquefied gases : liquid propane, liquid oxygen, LNG, liquid nitrogen
 Three ways to liquefy gases:
1. Heat exchange at const. P
2. Isentropic expansion
3. Throttling

Method 1 is usually used to precool the gas

before applying 2 or 3 although for the same
temperature drop, method 1 approaches the
liquid region most closely.

The change from state A to A′ may be accomplished by compression of the gas to the
pressure at B and constant-pressure cooling to A′. For air at 160 K, the pressure must
be greater than around 80 bar for any liquefaction to occur along the path of constant
enthalpy.

An efficient process of cooling is by countercurrent heat exchange with that portion of

gas which does not liquefy in the throttling process.
49
Linde liquefaction process

 The Linde liquefaction depends solely on throttling expansion

 After compression, the gas is precooled to ambient temperature, and maybe further
cooled by refrigeration. The lower the temperature of gas entering the throttle valve,
the greater the faction of gas that is liquefied.

 A more efficient process liquefaction process would replace the throttle valve with
an expander, but operating such a device into the two-phase region is impractical. 50
Claude liquefaction process

 In the Claude process, 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.

51
Claude liquefaction process

 Energy balance analysis

For the part of the process lying to the right of
the dashed vertical line:
m9 H 9  m15 H15  m4 H 4  Wout

For the expander: Wout  m12 ( H12  H 5 )

By a mass balance m15  m4  m9
Rewrite the energy balance
m9 m  m9 m
H9  4 H15  H 4  12 ( H12  H 5 )
m4 m4 m4
With the definitions, z  m9 / m4 and x  m12 / m4
x( H12  H 5 )  H 4  H15
z
H 9  H15
z is the fraction of 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 passed through the
expander H  H15
z 4
The Linde process is a limiting case (x=0) of the Claude process H 9  H15 52
Example: Methane liquefaction through
throttling

 Methane is compressed to 60 bar, and then cooled and throttled to 1 bar. It is known
that 10 % methane has been liquefied after throttle. Calculate the temperature before
the throttle using the PR EoS. Draw schematically the process in a PH diagram
Use the following ideal gas Cp coefficients.

CP  A  BT  CT 2  DT 3 where T is in K and C p is in J/(mol  K)

A=19.25, B=5.213×10-2, C=1.197×10-5, D=-1.132×10-8

53
Example: Methane liquefaction through
throttling

Methane

54
Exercise: Linde process

 Methane is liquefied through a Linde process shown in the figure. We know that P1,
P5-P8 are 1 bar, P2-P4 are 60 bar, T3 is 25 oC , T1 and T8 are 20 oC. We further
assume that the compressor has an isentropic efficiency of 0.8 and a mechanic
efficiency of 1.0. Use the PR EoS to calculate
 H3 and H8 in J/mol
 Equilibrium temperature T5
 H6, H7
 The fraction of liquefaction z
 H4, T4
 Compression work (J/mol) and COP

55