Master 2 « Énergie et matériaux avancés - Énergie

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Physical quantities
- Enthalpy
- Entropy
- Exergy

Frédéric Siros
Enthalpy
 Open Thermodynamic System

Courtesy Olivier Cleynen

Steady-state operation:
• Same masse flow entering
and exiting the system

Sign convention: from the fluid’s

standpoint
• W, Q >0 if supplied to the
fluid, <0 if removed from it
• Example on figure: Q>0
(heating), W>0 (compressor)
Let us neglect, regarding the fluid
entering and exiting the control
volume:
• Kinetic energy (1/2 V2)
• Potential energy: g . altitude
 U (Internal Energy)

• Wtotal and Q depend on

the path from 1 to 2, T
but W + Q does not
1

• Wtotal + Q can therefore

be seen as the variation
of a state function

• This state function is the

Internal Energy: U 2
S

• ΔU = U2 – U1 = Wtotal + Q
 Useful Work, Insertion & Extraction Work

• The fluid mass unit entering the system is “pushed” by the following fluid;
therefore, it receives work: p1.V1 = insertion work

• Symmetrically, the fluid mass unit exiting the system “pushes” the previous
fluid; it provides p2.V2 to the outside world: - p2.V2 = extraction work

• Therefore, the work received by the fluid is Wuseful + p1.V1 - p2.V2

(e.g. Wuseful = compressor work on previous slide)

• We are interested in Wuseful only,

not in p1.V1 - p2.V2

Courtesy Olivier Cleynen

 Why H (Enthalpy) is more popular among
Process Engineers than U (Internal Energy)

• Wuseful = Wtotal – ( p1.V1 – p2.V2 ) = Wtotal + p2.V2 – p1.V1

• ΔU = U2 – U1 = Wtotal + Q

• I am interested in Wuseful + Q only

• Wuseful + Q = [ Wtotal + p2.V2 – p1.V1 ] + Q = [U2 + p2.V2] – [U1 + p1.V1]

• Wuseful + Q = H2 – H1 with H = U + P.V ΔH = Wuseful + Q

H of fluid going through some components

Heat Turbine Valve (pressure drop)

Exchanger

Wuseful = 0 Q=0 Wuseful = Q = 0

ΔH = Q ΔH = Wuseful ΔH = 0l
 Total Enthalpy = Enthalpy + Kinetic Energy
Example: turbine stage – Adiabatic (Q = 0)

One stage Next stage

Question: Stator Rotor

Absolute
speeds
What about the following
quantities before/after the
stator and the rotor of a
given turbine stage?

• Enthalpy

• Total Enthalpy

• Speed:
V2 = VAxial2 + Vtangential2

Courtesy NASA
 Total Enthalpy = Enthalpy + Kinetic Energy
Example: turbine stage – Adiabatic (Q = 0)  ΔHtotal = Wuseful

Through the stator: One stage Next stage

• The fluid’s total enthalpy Stator Rotor
remains unchanged, Absolute
therefore: speeds
• ΔHtotal = 0  ΔH = -½.V2
• The stator converts
enthalpy into
tangential speed

Through the rotor:

• The rotor “captures” the
tangential speed and
converts the corresponding
kinetic energy into work on
the shaft
Courtesy NASA
Entropy
 First & Second Principles of Thermodynamics

• Thermodynamics is the science of energy conversion

• The First Principle can be formulated as follows:

“Energy can’t be lost, neither it can be obtained from nothingness”
The First Principle is about Energy Accounting, regardless of its quality

• Clausius, Thomson and Planck had formulations of the Second Principle that
can be summarized as follows:
“Work is a kind of energy that can be converted completely into heat by
any arbitrarily process; however it is impossible to design a process that is
able to convert the produced heat completely into work in order to restore
the initial state entirely”
 Intensive versus Extensive Quantities

B
• An intensive physical quantity does
not depend on the on the amount of A
the substance for which it is measured.
Examples: Pressure
Temperature TA = TB  TA+B = TA = TB

• An extensive physical quantity is additive for subsystems

Example: Volume VA = VB  VA+B = VA + VB

• Two quantities are conjugate if:

o One is extensive and the other is intensive;
o Their product is an energy
o Example: P and V
 Entropy and Thermodynamic Temperature

Pressure / Volume conjugate pair:

• Let us consider a system at a pressure P whose volume changes by dV

• -P . dV = δW = Work = Energy gained by the system

Can we define an extensive function X so that temperature and X constitute a

conjugate pair (in a similar manner as V and P)?
• Let us consider a system at a temperature T whose X changes by dX

• T . dX = δQ = Heat = Energy gained by the system

The answer is Yes! This function is the Entropy. Its symbol is S: δQ = T . dS

• It is most commonly described as measuring the magnitude of disorder of a
system
Entropy – Irreversibility of real transformations
Lets us consider an open system
T = its Thermodynamic Temperature (in °K)
S = its Entropy

This system exchanges Q (heat) with the outside world

• For a perfect, reversible transformation: dS = δQ / T

• For a real, non-reversible transformation: dS = δQ / T + dSirrev

• dSirrev is the Entropy generated by the irreversibility of the transformation

 Exercise: example of a perfect gas

Can we express the Entropy of a Perfect Gas as a function of its usual

state variable? If yes, How?

Reminder:
• The state of a gas can be expressed as a function of two state variables, e.g.
among P, T and V

• P, V and T of a Perfect Gas are linked by the following law: P . V = r . T

(r = e.g. 287 J/kg for air)

Corresponding hypotheses: kinetic theory, no interaction between molecules

• The Internal Energy of a Perfect Gas can be expressed as: dU = CV.dT

CV constant
 Exercise: example of a Perfect Gas

The elementary amount of Work exchanged by the gas with the outside world is:

δQ = dU – δW = dU + P.dV with: dU = CV . dT
and P = r . T / V (perfect gas)

δQ = CV . dT + r . T . dV/V

dS = δQ/T = = CV . dT/T + r . dV/V

S = CV . Ln(T) + r . Ln(V) + Constant

As a proxy for disorder, the Entropy of a perfect gas increases when:

• Its temperature increases (more molecular agitation),
• Its volume increases (less spatial constraint)
Exergy
(Without spelling mistake!)
 Carnot efficiency – Exergy of heat

• The Exergy (“Ex”) of a amount of heat Q at temperature T is its “Work

equivalent”

• This “Work equivalent” is calculated as the highest achievable amount of work

that can be obtained until reaching the equilibrium with the environment (sink
temperature To)

• This highest possible conversion efficiency is that of a Carnot cycle:

W / Q = 1 – To/T

• Let us call this efficiency “Carnot factor”: Θ = 1 – To/T

 All kinds of Energy are not equal

• Work, like electric energy, is pure Exergy: 1 kJWork = 1 kJElectricity = 1 kJEx

• Heat is less valuable than Work

• Heat at low temperature is less valuable than heat at high temperature

• Examples, supposing an ambient temperature of 300 K (~27°C):

o Heat at 600 K is 50% Exergy

o The chemical Exergy of common fuels is roughly equal to their Lower

Heating Value
due to the very high combustion temperature at stoichiometric conditions

o The external temperature of the sun is ~6000 K; therefore, the energy of

the solar irradiation is ~95% Exergy
 Question : general expression of Exergy of heat
System
The fluid enters the boundary
system at 1 and exits
2
it at 2.
Wuseful
The system provides
Work (W) and Heat
(Q at temperature T)
to the outside word.

Note: W<0 and Q<0.

Supposing that the

ambient temp. is To, 1
how can I express
the Exergy
variation of the
fluid?
 Answer: general expression of Exergy of heat
System
boundary
Wuseful is pure Exergy
2
The Exergy value of Q is Wuseful
the work provided by a
Carnot Engine:
ExQ = Q . (1-To/T)

Therefore, the fluid’s

Exergy variation is:

Wuseful + Q . (1-To/T)
1
= Wuseful + Q - To . Q/T

Ex = H - To . S
Carnot
Ambient
Ex = H – To . S sink at To
WCarnot Engine
 Heat = Exergy + Anergy

Let us consider the heat exchanged = Q. The Exergy it contains is:

Ex = Q . (1 – To/T) Q can therefore be written as:

Q = Exergy + Anergy with Anergy = Q . To/T

• The Exergy is the heat content that can be converted into Work

• The Anergy is the remaining heat content that cannot be converted

into Work
 Exergy and Anergy content of Energy

High temperature Heat

Work

Exergy Exergy Anergy

Electric Energy Low temperature Heat

Exergy Exergy Anergy

 Exergy loss incurred by some components

Heat Turbine Valve (pressure drop)

Exchanger

Some Exergy is lost, A lot of Exergy is

Some Exergy is lost,
because of the aero- lost: it is a highly
because of the T
dynamic imperfection irreversible
between both fluids
(friction) of the expansion transformation
EARTH PLANET
References

 Also Volumes 2 & 3

 THANK YOU FOR YOUR ATTENTION

frederic.siros@edf.fr