Chemical Engineering

Thermodynamics
Yang, Yanhui

Content

Introduction and necessary calculus

Polytropic process for ideal gas
Throttling process (isenthalpic process)
Joule-Thomson effect
Turbine (expanders and isentropic process)
Compressors and pumps
Refrigeration processes
Reverse Carnot and vapor compression cycle
Liquefaction processes
General methods of liquefaction
Industrial liquefaction processes
Linde liquefaction and Claude Liquefaction process
Analysis of the liquefaction processes
2

Introduction

Fridge and AC

Calculus

1 kmol of a pure substance with no phase change involved:

Calculus

To derive based on basic laws and definition of thermodynamics

property:
From H=H(T, P)

Substitute Eq. (iv) into (iii) and then Eqs. (iii) and (ii) into (i)

Example: What is the change of enthalpy of 1 kmol of a system

changes from T1, P1 to T2 and P2?
5

Calculus

Derive:

dU=TdS-PdV

s P

?
v T T v
u
P

P
v T
T v

A=U-TS
dA=-PdV-SdT
6

Polytropic process for ideal gas

Polytropic process is a thermodynamics process that obeys the

relation:
where p is the pressure, V is the volume, n is the
polytropic index (any real number), and C is the constant. This
equation can be used to accurately characterize processes of
certain systems (closed system), notably the compression or
expansion of a gas in some cases liquids and solids.

An ideal gas is changed from state 1

to state 2 by the following process:
1. Isothermal process from state 1
to state 2
2. Isobaric step to 2 followed by
isometric step
3. Adiabatic process to 2 followed
by isomeric step.
Determine and compare the
changes in U, H, Q and W for
7
individual process

Polytropic process for ideal gas

System: 1 kmol of an ideas gas in a closed system at P1 & V1

Process: as indicated below, assume all mechanical reversible.

Isothermal process (Step 1-2): the change in U:

Isothermal process (Step 1-2): the change in H:

Q and W:
From 1st law:

Polytropic process for ideal gas

Isobaric (const-P) followed by isomeric (const-V) process (step 12=2)

Isobaric process (step 1-2), from 1st law
U and H

Heat and Work

Polytropic process for ideal gas

Isometric (isochoric) process (step 2-2)

W
Q, U and H

Combine isobaric and isometric process (step 1-2-2)

10

Polytropic process for ideal gas

Adiabatic followed by isometric process (step 1-2-2)

Adiabatic process (step 1-2)

Define heat capacity ratio as:

For ideal gas:

Integration at constant heat capacities:

By combining with ideal gas law, PV=RT

11

Polytropic process for ideal gas

For an ideal gas with constant heat capacities undergoing an

adiabatic process, PVT relationships may generally be expresses as
(for mechanical reversible process only):

Compression work or expansion work: , this work may be applied to

either reversible or irreversible process because it is determined
from 1st law.
As the temperature at the end of an adiabatic process is usually not
known, adiabatic work cannot be readily calculated. They may be
replaced by the initial temperature and volume using the above PTV
relationships. As the PVT relations are developed based on
adiabatic reversible process, this equation applies only to reversible
process.
12

Polytropic process for ideal gas

Derive work for adiabatic process of ideal gas

For adiabatic process: Q=0, W=U=Cv(T2-T1)

For ideal gas:

If reversible process:

13

Polytropic process for ideal gas

The P-V relationship for an ideal gas under going mechanical

reversible process may be expressed as
Where the constant depends on type of process

PVT relationships may generally be expressed as:

14

Polytropic process for ideal gas

Work and heat of a polytropic process

From 1st law:

Substitute Cv and integrate to give Q

15

Polytropic process for ideal gas

Derive heat for polytropic process

16

Polytropic process for ideal gas

Example: An ideal gas undergoes the following sequence of
mechanically reversible processes in a closed system:

a. From an initial state of 343.15K and

1 bar, it is compressed adiabatically
to 423.15K.
b. it is then cooled from 423.15K to
343.15K at constant pressure.
c. Finally, it is expanded isothermally
to its original state.
Calculate W, Q, U, and H for each
of the three processes and for the
entire cycle. Take Cv=3R/2 and
Cp=5R/2.

17

Polytropic process for ideal gas

Solutions:
System: an ideal gas (1 mol) initially at 343.15K and 1 bar
Process: adiabatic compression, cooling at constant pressure and
isothermal expansion to original state
For R=8.314 J/molK, Cv=12.471 and Cp=20.785 J/molK
Step a: Q=0,

Pressure
Step b:

is found

.
.

18

Polytropic process for ideal gas

Solutions: (contd)
Step c: for ideal gases undergoing an isothermal process,
are zero.
.

For the entire cycle: Q=0-1663+1495=-168J

W=998+665-1495=168J
U=998-998+0=0
H=1663-1663+0=0

19

Polytropic process for ideal gas

Example: if the previous processes are carried out irreversibly but

so as to accomplish exactly the same changes of state (the same
changes in P, T U, and H), then different values of Q and W result.
Calculate Q and W if each step is carried out with and efficiency of
80%.
Solutions: same system and processes but irreversible.
For step a compression, W=998/0.80=1248J. This step cannot be
adiabatic by the 1st law: Q=U-W=998-1248=-250J
Step b cooling: W=665/0.80=831J, and Q= U-W=-998-831=-1829J
Step c expansion: work is done by the system, W=(1495)(0.80)=1196J. Q= U-W=0+1196=1196J.
For the entire cycle, U and H are zero. Q=-250-1829+1196=883J. W=1248+831-1196=883J
The total work and heat required for irreversible steps are more than
five times the total work required for reversible steps for efficiency of
20
80%

Throttling process (isenthalpic

process)

When a fluid flows through a restriction (orifice, partially closed

valve, etc.), a reduction of pressure occurs

From a steady state energy balance:

Isenthalpic process:
21

Joule-Thomson effect

During the throttling process, a reduction in pressure may

accompany by a change in T if there is no phase change involved.

At constant enthalpy, dH=0

For an ideal gas, there is no change in T

22

Joule-Thomson effect

23

Turbine (expanders and

isentropic process)

Turbine is a device that converts internal energy of a high pressure

steam to shaft work under adiabatic reversible condition.
Shaft work production from steady state energy balance:

Also, since the process is reversible and Q=0, from entropy balance:
Isentropic process:

Turbine efficiency:

24

Turbine (expanders and

isentropic process)

25

Turbine (expanders and

isentropic process)

Example: A steam turbine with rated capacity of 56400 kW (56400

kJ/S) operates with steam at inlet conditions of 8600 kPa and
773.15K), and discharges into a condenser at a pressure of 10 kPa.
Assuming a turbine efficiency of 0.75, determine the state of the
steam at discharge and the mass rate of flow of the steam.
Solutions:
System: working fluid at 8600 kPa and 773.15 K.
Process: a steam turbine, efficiency 0.75.
At the inlet conditions of 8600 kPa and 773.15K, the steam tables
provides: H1=3391.6kJ/kg and S1=6.6858kJ/kg/K.
If the expansion to 10 kPa is isentropic, then, S2=S1=6.6858.
Steam with this entropy at 10 kPa is wet.
,
(fraction of vapor) at
discharge point 2.

26

Turbine (expanders and

isentropic process)
Solutions (contd)
The enthalpy H2 is also given as

Thus the steam in its actual final state is also wet, with its quality
given by:
Then

27

28

Compressors

29

Compressors

They are basically operating like turbines in reverse way.

Work is done on the system (working fluid) as it is compressed and
system energy increases.

They are also operating under adiabatic and reversible conditions

(isentropic process).

Compressor efficiency:
30

Compressors
Example: Saturated-vapor steam at 100 kPa (Tsat=372.78K) is
compressed adiabatically to 300 kPa. If the compressor efficiency is
0.75, what is the work required and what are the properties of the
discharge steam?.
Solutions:
System: saturated vapor steam at 100 kPa
Process: compress adiabatically to 300 kPa
For saturated steam at 100 kPa, S1=7.3598 kJ/kg/K and
H1=2675.4kJ/kg.
For isentropic compression to 300 kPa, S2=S1=7.3598 kJ/kg/K.
Interpolating in the steam tables for superheated steam at 300 kPa
shows that steam with this entropy has the enthalpy:
H2=2888.8kJ/kg.
Thurs the work H=2888.8-2675.4=213.4kJ/kg

31

Compressors
Solutions (contd):
Efficiency: H= 213.4/0.75=284.5 kJ/kg
Thus H2=H1+H=2675.4+284.5=2959.9 kJ/kg
For superheated steam with this enthalpy: T=519.25K and
S2=7.5015kJ/kg/K
Work=284.5kJ/kg

32

33

Pumps

Liquids are moved by pumps (work required).

The same equations for compressors apply to pumps.
For energy balance:
As liquid is incompressible under normal conditions:

34

Pumps
Example: water at 318.15K and 10 kPa enters an adiabatic pump
and is discharged at a pressure of 8600kPa. Assume the pump
efficiency to be 0.75. Calculate the work of the pump, the
temperature change of the water, and the entropy change of the
water. V=1010 cm3/kg, =0.00425/K and Cp=4.178 kJ/kg/K
Solutions:
System: water at 318.15 K and 10 kPa
Process: pump to 8600 kPa with efficiency 0.75
Work(isentropic)=H=1010(8600-10)=8.676kJ/kg
Efficiency: work required=8.676/0.75=11.57kJ/kg
The temperature change: 11.57=4.178T+1010[1(0.00425)(318.15)](8600-10)/10e6
T=0.97K
Entropy change S=4.178ln(319.12/318.15)-(0.00425)(1010)(860010)/10e6=0.0090kJ/kg/K

35

Refrigeration
Clausius statement of second law: It is impossible to construct a
cyclic process whose only effect is to transfer heat from a lower
temperature body to a higher one (without external work)
Heat transfer between two reservoirs at TH and Tc insulated from
other parts of the universe:
System: cold reservoir
Process: heat transfer
Entropy change of cold reservoir:

Entropy change of hot reservoir:

36

Refrigeration

Normal Carnot cycle

37

Refrigeration
Carnot gas refrigeration cycle

38

Refrigeration
Carnot vapor refrigeration cycle
Reverse Carnot cycle
Ideal refrigeration cycle in four steps

39

Refrigeration

Carnot vapor refrigeration cycle

Step 1-2: isothermal absorption of heat at TC in the evaporator (lowT reservoir)

Step 2-3: Isentropic compression in a compressor

Step 3-4: Isothermal rejection of heat at TH in the condenser (high-T

reservoir)

Step 4-1: Isentropic expansion through a turbine

40

Refrigeration

Performance of a Carnot vapor refrigeration cycle

Define coefficient of performance (COP) =cooling capacity/work
supplied:

Refrigerator is to keep a space cold

(cold reservoir) by removing heat from
it and discard it to hot reservoir.
Heat pump is to keep a space warm
(hot reservoir) by pumping energy
from cold reservoir into the space to
be heated.
The COP of heat pump:

41

Refrigeration

Vapor compression refrigeration cycle

Evaporation at constant pressure provides for the absorption of heat
at a constant low temperature reservoir.
Condensation of a vapor after compression to a high pressure
provides for the rejection of heat at a high temperature.
Working fluids is refrigerants.

42

Refrigeration

Vapor compression refrigeration cycle

turbine

Throttling

turbine

Throttling

43

Refrigeration

Vapor compression refrigeration cycle

4 steps cycle:
Step 1-2: Absorption of heat at a constant pressure and temperature
in evaporator.

Step 2-3: isentropic compression.

Step 3-4: Rejection of heat at a constant pressure in a condenser.

Step 4-1: Isentropic expansion in a turbine or throttling through an

orifice.
throttling

44

Refrigeration

Vapor compression refrigeration cycle

Coefficient of performance (COP):
Expansion using turbine:

Expansion using throttle valve (isenthalpic):

Rate of circulation of refrigerant:

45

Refrigeration

Example: A refrigerated space is maintained at 261.15K, and

cooling water is available at 294.15K. Refrigeration capacity is
35.2kW. The evaporator and condenser are of sufficient size that a
5.6K minimum temperature difference for heat transfer can be
realized in each. The refrigerant is Tetrafluorethane (HFC-134a), for
which data are given below.
A. what is the value of for a Carnot vapor refrigerator?
B. Calculate and refrigerant flow rate for the vapor compression
refrigeration cycle if the compressor efficiency is 0.80

46

Refrigeration
Heat flow

Water, 294.15K
Condenser,
(294.15+5.6)K

Evaporator,
(261.65-5.6)K
Heat flow

Room, 261.65K
47

Refrigeration

420.33

428.41

48

Refrigeration

For a Carnot vapor refrigerator,

. )
.

. )

For Vapor compression refrigeration cycle, the enthalpies for state 2 and 4
are read directly from Table. The enthalpy at 261.15-5.6=255.55K indicates
that HFC-134a vaporizes in the evaporator at a pressure of 0.1471MPa. Its
properties as a saturated vapor at these conditions are H2=388.03KJ/kg and
S2=1.7392KJ/kgK. The entry at 294.15+5.6=299.75K in Table shows that
HFC-134a condenses at 0.6977MPa, its enthalpy as a saturated liquid is
H4=236.83KJ/kg. If the compression step is reversible and adiabatic
(isentropic) from saturated vapor at state 2 to superheated vapor at state 3,
S3=S2=1.7392KJ/kgK. The enthalpy from Figure at this entropy and at a
pressure 0.6977MPa is about H3=420.33KJ/kg. The enthalpy change is
420.33-388.03=32.3KJ/kg. Consider the efficiency of 0.80, the actual
enthalpy change is 32.3/0.80=40.38KJ/kg. Because the throttling process of
step 4-1 is isenthalpic, H1=H4. The coefficient of performance is therefore
becomes (388.03-236.83)/40.38=3.74
The HFC-134a circulating rate is 35.2/(388.05-236.83)=0.2328kg/s

49

Refrigeration

Absorption refrigerator
The essential difference between a vapor-compression and an
absorption refrigerator is the different means employed for
compression.
In vapor-compression refrigeration, the work of compression is
usually supplied by an electric motor, from a heat engine (central
power plant). Thus, the work for refrigeration comes ultimately from
heat at a high temperature level.
The absorption-refrigeration machine is that directly use heat as the
energy source for refrigeration. Usually low-pressure steam is the
source of heat.
The most commonly used absorption-refrigeration system operates
with water as the refrigerant and lithium bromide solution as the
absorbent. Ammonia can also serves as refrigerant with water as
the solvent. Alternatively, methanol as refrigerant and
50
polyglycolethers as absorbent.

Refrigeration

51

Refrigeration

The work required by a Carnot refrigerator absorbing heat at

temperature TC and rejecting heat at the temperature of the
surroundings, here designated TS:

If a source of heat is available at a temperature that of the

surroundings, say at TH, then work can be obtained from a Carnot
engine operating between this temperature and the surroundings
temperature TS. The heat required for the production of work is
found:
and
Elimination of W gives:

Of course, the value calculated is a minimum because Carnot cycles

cannot be achieved in practice. For an actual absorption refrigerator,
the value would be on the order of three times this results.
52

Refrigeration
Example: A house has a winter heating requirement of 30 kJ/s and
a summer cooling requirement of 60 kJ/s. Consider a heat pump
installation to maintain the house temperature at 293.15K in winter
and 298.15K in summer. This requires circulation of the refrigerant
through interior exchanger coils at 303.15K in winter and 278.15K in
summer. Underground coils provide the heat source in winter and
the heat sink in summer. For a year-round ground temperature of
288.15K, the heat-transfer characteristics of the coils necessitate
refrigerant temperatures of 283.15K in winter and 298.15K in
summer. What are the minimum power requirement for winter
heating and summer cooling?
Solutions:
System: working fluid in the coils for heating and cooling
Process: heat pump

53

Refrigeration
Winter

QH

Qc

Summer

Room, 293.15K

Underground,
288.15K

Coil, 303.15K

Coil, 298.15K

Coil, 283.15K

Coil, 278.15K

Underground,
288.15K

Room, 298.15K

QH

Qc

54

Refrigeration

Solutions (contd)
The minimum power requirements are provided by a Carnot heat
pump and refrigeration cycle. For winter heating, the house coils are
at the higher temperature level TH, and the heat requirement is
QH=30 kJ/s.
TC
283.15
QC QH

30
28.02kJ / s
TH
303.15

This is the heat absorbed from the ground coils.

Thus the power requirement is 1.98kW.

For summer cooling, Qc=60kJ/s, and the house coils are at the
lower temperature level Tc.

w QH QC 30 28.02 1.98kJ / s

W QC

TH TC
298.15 278.15
60
4.31kJ / s
TC
278
.
15

The power requirement here is therefore 4.31kW

55

Quiz

Oct. 7th, Wednesday

9:30-11:30
LT 2A
Close book/lecture notes/tutorials
Content: up to refrigeration
Liquefaction is not included

56

Liquefaction

Liquefied gases are used for a variety of purposes: 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 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.

57

Liquefaction

1. Cooling at constant pressure:

requires an external refrigerator to
cool a gas prior to liquefaction by
methods below.
2. Isentropic expansion process:
may be accomplished from a lower
pressure (for a given temperature)
than by throttling process.
3. Isenthalpic throttling process:
requires a high pressure and low
temperature for the constant
enthalpy process to cut into the 2phase region.
58

59

Liquefaction

Linde liquefaction process by throttling expansion

60

Liquefaction

The gas/vapor (1) is firstly compressed (3) and precooled to ambient

temperature (4). Multi-stage compression is usually used in the
Linde liquefaction process to achieve the required high pressures.
The stream (4) is further cooled in heat exchanger (7) before
isenthalpic throttling to produce a vapor/liquid mixture.
The lower the temperature of the entering the throttle valve, the
greater the fraction of gas that is liquefied.
The Joule-Thomson coefficient must be such that the gas cools on
expansion, and the temperature must be low enough and the
pressure high enough to assure that the expansion will end in the
two-phase region.
In the vapor-liquid separator, the vapor phase is recycled (10) and
after heat exchanger (15) is returned to the compressor, and liquid is
withdrawn.

61

Liquefaction

Claude process - modified using an expander

62

Liquefaction

Same as Linde process, feed (1) is compressed (3) and precooled

(4).
Part of the gas (11) after compression, precooling and cooling (5) is
extracted from the heat-exchange system (11) and passed through
an expander from which it emerges as a saturated or slightly
superheated vapor (12).
The remaining gas (6) is further cooled (7) and throttled through a
valve to produce a liquid-vapor (8) as in the Linde process.
The unliquefied portion (10) which is saturated vapor mixes with the
expander exhaust (12) and returns for recycle (13) through the heatexchanger system.

63

Liquefaction

Analysis of the liquefaction processes (both Linde and Claude)

Define z as the fraction of stream
entering exchanger system
that is liquefied, and x as the fraction of
that is drawn off to the
expander in Claude process.

Note: the quantity x is a design variable and is usually specified. (for

Linde process, x=0)
Energy and mass balance, system is on the right hand side of the
vertical dashed line.

If the expander is operated adiabatically, from 1st law:

64

Liquefaction

Fraction of

liquefied:

Note: the quantity x is a design variable and must be specified

before the above equation used to solve for z.
For Linde process: x=0
65

Liquefaction
Example: natural gas (assume pure methane) is to be liquefied in a
Linde process as follows: initial compression to 60 bar and
precooling to 300K, the throttle exhaust is at a pressure of 1 bar,
and recycle methane leaves the exchanger system at 295K.
Determine the fraction of methane liquefied and the temperature of
the high-pressure stream entering the throttle valve and the Joule
Thomson coefficient.
Solutions:
System: 1 kg/s of methane gas after compressed and precooled to
60 bar and 300K (stream 4).
Process: liquefaction by Linde process.
Fraction of methane liquefied (from P-H diagram: H4=565 kJ/kg;
H9=-285 kJ/kg; H15=630 kJ/kg)
66

Liquefaction

Linde liquefaction process by throttling expansion

300K, 60 bar

? K, 60 bar

295K, 1 bar
1 bar, saturated vapor

112 K, 1 bar ,
two phase
region

1 bar, saturated liquid

67

Liquefaction

T7 and the Joule-Thomson coefficient

Apply energy balance to the heat exchange:
From P-H diagram:

At 60 bar and H7=184.1 kJ/kg, T7=203K

Throttling process is represented by the constant enthalpy line,
which is the vertical line drawn from 7 and intercepting the 1 bar line
at 8.
Joule-Thomson coefficient:
68

Liquefaction

69

Summary

Introduction and necessary calculus

Polytropic process for ideal gas
Throttling process (isenthalpic process)
Joule-Thomson effect
Turbine (expanders and isentropic process)
Compressors and pumps
Refrigeration processes
Reverse Carnot and vapor compression cycle
Liquefaction processes
General methods of liquefaction
Industrial liquefaction processes
Linde liquefaction and Claude Liquefaction process
Analysis of the liquefaction processes
70