Thomas G. Lestina and Kevin J. Farrell, Heat Transfer Research Inc.

(HTRI), USA,
examine how using a second-law approach can help to improve the efficiency and
environmental impact of process heat exchangers.

P
rocess heat exchangers have traditionally been
designed using methods based on the zeroth and
first law of thermodynamics. First-law efficiencies
deviate from unity only as a result of thermal
leakages to or from the environment and thus are deficient
discriminators among designs. A second-law approach
requires quantification of thermodynamic irreversibilities in
the design – mainly from heat transfer over a finite
temperature difference and frictional pressure drop of the
stream(s). The resulting second-law efficiency is a better
comparator and informs calculations of environmental
impact and sustainability. This article defines and discusses
the value of the approach with an example case study.
Energy intensive industries, such as refining, petrochemical,
and chemical processors, seek to improve energy efficiency
to reduce costs. The current emphasis on sustainability
increases the incentive to do so. Energy efficiency studies
most often address an entire system, where the interrelated
performance of a network of unit operations can be
assessed. Heat exchanger performance can be an important
part of these studies. HTRI has recently been using some
overlooked thermodynamic principles to inform design

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decisions for efficient process heat exchanger operation. The
insights from this recent research can be used as an
additional tool to improve heat exchanger design.
The subject of thermodynamics was developed in the
nineteenth century in order to improve the performance of
heat engines. The great early thermodynamicists including
Carnot, Clausius, and Joule were most interested in conserving
fuel and not particularly concerned about pollution or
climate change. Now, the growing awareness of environmental
impact has stimulated a closer look at the thermodynamic
performance of all processes. Although important, the
thermodynamic performance is not the sole consideration; an
acceptable design solution must address criteria developed
from concerns about safety, material selection and availability,
geography, radiated noise, sustainability, size, maintenance,
and economics, among others.
The laws of thermodynamics
Taken together, four fundamental laws of thermodynamics
form the basis for the rest of the subject. Current control
volume or open system analyses with heat exchanger design
tools, such as HTRI’s Xchanger Suite®, rely on the zeroth and
first laws of thermodynamics along with conservation of
mass. The heat exchanger efficiency that HTRI advocates is
based on the second law as well. This requires the tracking of
the entropy of the fluids that are exchanging heat and
recording the dead state temperature and pressure.
Availability, a measure of the maximum work that the stream
can do, can then be calculated. The four laws of
thermodynamics are stated below, using simple declaratives.
Zeroth law
There is a useful quantity called temperature that reflects
thermal equilibrium.
First law
There is a useful quantity called enthalpy in an open system
that satisfies . In a heat exchanger, no
shaft work is performed, and no heat is exchanged with the
environment – only among the streams. Changes in kinetic
and potential energy are usually negligible. Therefore, the
first law simplifies to an enthalpy balance.
Second law
There is a useful quantity called entropy which satisfies
for any real process.
Third law*
There is not a thermodynamic process by which one can
attain absolute zero temperature.
Second-law considerations for process
heat exchangers
The log mean temperature difference (F-LMTD) method and
the effectiveness-NTU ( -NTU) method underlie most
thermal rating methods. Either method can solve the
exchanger rating or sizing problem and will yield an identical
solution. These methods utilise the same assumptions, none
of which are ever completely true in an actual design.
Nonidealities, such as bypass streams and flow maldistribution,
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further diminish the accuracy of these design solutions in
actual exchangers with their as-built imperfections. While
these thermal performance analysis techniques are based on
the zeroth and first law of thermodynamics with the
conservation of mass, they do not acknowledge or quantify
the irreversibilities due to nonideal performance.
Entropy increases in any real process according to the
second law, which decreases the quality of the energy.
When a system operates irreversibly, it destroys work at a
rate that is proportional to the system’s rate of entropy
generation – a principle called the Gouy-Stodola theorem.
Formally, the irreversibility is:
(1)
It is possible to monetise the destroyed work in terms of
the equivalent carbon dioxide (CO2) produced using an
emissions factor for the energy source and locale. This
presents an opportunity to reduce the carbon footprint – a
ceiling value, as according to the second law, it can never be
taken to zero. Heat transfer over a finite temperature
difference and pressure drop are the two principal sources of
irreversibility in a heat exchanger. Other sources may be
unrestrained expansion, mixing, turbulence, chemical
reaction, resistive loss in electrical circuits, and interactions
with the environment (e.g., heat loss or heat ingress in the
case of cryogenic heat exchangers). Unfortunately, design
approaches to minimise one irreversibility source typically
exacerbate others.
Availability is a thermodynamic function that depends
on the state of both the environment and the system, and
reflects the quality of the energy: **
(2)
Availability represents the maximum useful work that can
be obtained from a system by a reversible heat engine
operating between the energy source and the environment.
The environment is usually the dead state, noted with the
0 subscript, because no useful work can be extracted from
the environment. The atmosphere contains a tremendous
amount of energy, but it cannot be used for doing work
unless there is a lot of wind (kinetic energy). The dead state
is typically 25 °C and 1 bar pressure. The quality of energy
decreases in every thermodynamic process, including heat
transfer. In the open system of a two-stream heat exchanger,
availability (but not all of it) moves from the hot fluid to the
cold fluid; availability always decreases in the process. This
observation allows a simple efficiency law to be formed for
a two-stream heat exchanger.
(3)
2nd, two–stream =
Where:
Streams possess availability by virtue of temperature
and/or pressure that exceeds that of the dead state.
Fuel streams have added chemical availability, which is often
taken simply as the gross calorific value, as this is the
maximum work that could be extracted.
A heat exchanger has its own boundary or envelope
around it. Material and energy streams cross this boundary.
Obviously, the scope and accuracy of any performance
estimate of the unit operation is limited to the streams and
utilities captured in the control volume and boundaries and
the fidelity of the modelling. Clearly, all unit operations that
make up the complete process must be analysed, but in
considering a single heat exchanger, our knowledge is limited
to the control volume boundary and what is inside.
The flow of availability through a process can be viewed
in a Grassman diagram, as in Figure 1. The streams entering
the heat exchanger are to the left of the vertical bar in the
middle, and the streams departing the heat exchanger are to
the right of the vertical bar. The irreversibility is the portion
of the availability entering the exchanger that is destroyed in
the heat exchange process.
For multi-stream heat exchangers and those with
turbomachinery (shaft work) or chemical reactions in the
control volume, HTRI suggests an
alternative second-law efficiency:
drop for the gas side to ensure that compressor power
requirements are not exceeded. Because the gas side has the
highest thermal resistance, the design of an intercooler
requires a careful balance between heat exchange and
pressure drop. A rule of thumb for these applications is to
ensure that all allowable pressure drop is used for the gas
side. This example shows how fouling and applying this rule
of thumb can affect the second-law efficiency, cost of
construction, and carbon footprint.
Consider a skid-mounted moist air intercooler with an
air/water mixture on the shell side and cooling water on the
tube side. Table 1 lists design process conditions. The
thermal design is performed using HTRI’s shell-and-tube
software Xist®, and fabrication costs and associated carbon
emissions were determined using Exchanger Optimizer with
a 5 times (x) cost factor for the continuous-finned tube vs a
plaintube. The operational irreversibilities, – ,
were
monetised to a CO2e emission (reduction opportunity). It is
understood that the operational carbon footprint
calculated in this way is more properly understood as an
upper bound on the CO2e reduction opportunity; it can

(4)

Where – is the total availability

destruction in the control volume of
all sources – flow availability, shaft
work, and chemical availability (e.g.,
combustion). Calculating the net rate
of change in availability of all the
streams in a heat exchanger allows
the calculation of the rate of
availability destruction or lost work, Figure 1. Grassman diagram for (a) generic two-stream heat exchanger
and thus the rate of irreversibility. and (b) air cooler.
The second-law efficiency values
depend on the dead state
temperature. For high temperature cold streams and a dead Table 1. Design process conditions for moist air
intercooler
state temperature of 25 °C, higher efficiencies are expected.
Similarly, for low dead state temperatures, high efficiencies Parameter Value
are also expected to increase to 100% at absolute zero Shell side – moist air (1.86 % H2O by weight)
temperature. Second-law efficiencies can most effectively Flow rate (kg/s) 7.0
help compare different designs and operating conditions for Temperature, in/out (K) 431.15 / 311.91
a particular application. For waste heat recovery applications
Weight fraction vapour, in/out 1.000 / 0.9995
(feed-effluent exchangers, recuperators, and flue gas
economisers), differences in efficiencies can be directly Inlet pressure (kPa) 243.80
related to energy costs and emissions. For other applications, Allowable pressure drop (kPa) 5.4
differences in efficiency can indicate other issues. Fouling, 2
Fouling (m K/W) 0.0001
flow bypassing, and other degradation mechanisms reduce Tube side – cooling water
the second-law efficiency. Variations in exchanger
Flow rate (kg/s) 37.8
geometries have a more subtle impact, as the following
example case demonstrates. Temperature, in/out (K) 305.15 / 310.69
Inlet pressure (kPa) 451.32
Example case Allowable pressure drop (kPa) 70
Intercoolers remove the heat of compression with the
Fouling (m2 K/W) 0.0004
purpose of reducing the work input to reach the specified
Duty (MW) 0.875
pressure. Intercoolers typically have low allowable pressure

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never be zeroed unless all energy sources are ‘green’ or theIn Figure 2, the relative scale of the three design configurations
second law is violated.
Table 2 presents geometry and performance attributes
of three designs of a TEMA X-shell-and-tube heat
exchanger: a plain tube version, a continuous-finned
version, and a compact, continuous-finned version.
Figure 2. TEMA X-shell-and-tube heat exchanger designs for an intercooler,
illustrating relative sizes and tube bundle configurations.
is compared. Also included are performance parameters of a
simulation of the continuous-finned configuration, with no
fouling factors on either side in the fourth column of Table 2,
in order to quantify the effect of fouling.
This simple comparison yields many interesting
observations. The plain tube
configuration has the highest
second-law efficiency by either
definition, but it costs approximately
30% more than the others to build and
emits nearly three times as much
carbon during fabrication. This
configuration also carries over 88% of
the thermal resistance on the shell side,
so enhancements there dramatically
reduce the tubecount, the cost to build,
and carbon emissions associated with
fabrication.
The potential to reduce the
operational carbon emission varies over
8% among the three design
configurations. Application of the
long-time rule of thumb to fully utilise
available pressure drop motivates the
compact, continuous-finned design,
which actually exacerbates the

Table 2. Comparison of intercooler designs

Design Plain tube Continuous fin Continuous fin, no Compact continuous fin
fouling factors
Shell inner diameter (mm) 778 762 610
Tube length (m) 4.267 2.591 2.286
Tube outer diameter 15.875
(mm)
Tube pitch ratio 1.26 2.05 1.50
Tubepass 4 2 2
Tubecount 1040 151 U-tubes 201 U-tubes
Fin density (1/m) No fins 433.1 433.1
Heat transfer area (m2) 190 500 264
Calculated P/ allowable 0.28 0.47 1.00
P P, shell side
0.158 0.154 0.168 0.150

0.161 0.166 0.156 0.174

0.839 0.834 0.844 0.826

Fabrication price, 133 101 105

(US$1000)
CO2e emissions from 14 5 4
fabrication (t)
Operational CO2e 556 573 523 604
emission reduction
potential (tpy)***
Effectiveness (first law), 0.944 0.944 0.974 0.944

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second-law efficiency and has the greatest irreversibility
among the three.
Interestingly, the three designs have identical
effectiveness, , which is a first-law quantity. The column
with the label, ‘Continuous fin, no fouling factor’, represents a
simulation Xist run of the exchanger, with continuous fins,
but with no fouling factors. The result is a 1.0% improvement
in and a 9% reduction in the operational carbon,
which underscores the clear payback in fouling mitigation.
With the fouling factors considered, performance, cost, and
overall emissions drive one to the continuous-fin
arrangement. The compact continuous-fin arrangement has
about the same impact initially, but it is more expensive to
operate with the slightly lower second-law efficiency. Clearly,
the consideration of irreversibilities is a much better
comparator for design options and further motivates the
development of accurate models of the complex
thermal-hydraulic behaviour within the heat exchanger.
Nomenclature
af = specific flow availability (J/kg)
h = specific enthalpy (J/kg)
h0 = specific enthalpy at dead state (J/kg)
Sl = irreversibility rate (W)
Sl = mass flow rate of cold stream (kg/s)
Sl = mass flow rate of hot stream (kg/s)
Sl = heat duty (W)
T0 = dead state temperature (K)
s = specific entropy (J/kg K)
s0 = specific entropy at dead state (J/kg K)
S l= shaft work rate (W)
S l = actual work rate (W)
S l = reversible work rate (W)
S l = rate of change of flow availability for cold stream (W)
S l = change in specific flow availability of cold stream (J)
S l = rate of change of flow availability for hot stream (W)
S l = change in specific flow availability of hot stream (J)
S l = rate of net availability destruction (a positive
quantity) (W)
S l = rate of kinetic energy change (W)
S = rate of potential energy change (W)
S = rate of enthalpy energy change (W)
S = pressure drop (Pa)
S = change in entropy, of both system and
surroundings (J/K)
Sl = effectiveness
S l = second-law efficiency of heat exchanger
S l S l = second-law efficiency of two-stream heat
exchanger
Reference
1. HINDERINK, A. P., VAN DER KOOI, H. J., and DE SWAAN ARONS, J., ‘On the
efficiency and sustainability of the process industry’, Green Chemistry,
pp. 176 – 180, (1999).
Notes
*Interest in the third law is resurging because quantum computers operate
near absolute zero temperature.
**Some texts use the newer term exergy instead of availability. While
defined carefully from Greek and Latin roots, exergy sounds too much like
energy and entropy so availability is used here.
*** An emissions factor of 0.454 kg CO2e /kWhr was assumed.
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