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MAE 501 course notes Spring 2013 Copyrighted by R. D.

Gould

ADVANCED ENGR THERMODYNAMICS

II. THERMODYNAMICS DEFINITIONS

1. System:

A collection of matter in a three-dimensional region of space bounded by an


arbitrary surface. You MUST define this BEFORE working your problem!

a.) Closed System:


No mass crosses a closed system boundary, however, energy may
Constraint: impermeable to mass

i.) Closed System with Rigid Boundary (internal constraint):


Rigid boundary: Constant volume (d = 0)
Example: Steel tank

ii.) Closed System with Moving Boundary:


Boundary moves: (Volume of the system is not constant)
Examples: Balloon with tied knot, piston-cylinder device

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS

b.) Open System (or Control Volume, C.V.):

Mass is permitted to cross system boundaries

i.) Open System with Rigid Boundary:


Constant volume (rigid) control volume
Examples: Water nozzle, rigid tank with valve opened,
turbines, compressors, heat exchangers,

ii.) Open System with Moving Boundary:


Volume of the C.V. is not constant
Example: Untie knot of balloon W

2. Surroundings (or environment):

Everything external to the system. Q


Tsurr system

bdry

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


3. Boundary:

A zero volume (no mass, not wall) surface, usually located at the interface
between two materials (or commonly between the system and surroundings)
The properties on a boundary are shared by both the system and the
surroundings (i.e continuous function).

Consider the boundaries of the control volumes and systems below

(a) (b)

(c) (d) (e)

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


Distinction between wall and boundary (Bejan, pp. 1-3):
T T T T

x x x x

Bejan Fig. 1.1 Bejan Fig. 1.2


(incorrect use of bdry) (correct use of boundary)

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


4. Isolated system:

A system not influenced by its surroundings.


No heat or work (ENERGY) crosses an isolated system boundary!

5. Property :
Any measurable characteristic of a system.
Properties are point functions and thus do not depend on how the system
arrived at its condition.
a.) Extensive Property: (Depends upon the size of the system): add
1. Volume partition
2. Mass
3. Total energy, total enthalpy, total entropy,
4. All mass dependent properties
5. 1st and 2nd laws use extensive properties! (1) (2)
b.) Intensive Property: (Independent of system size):
1. Temperature
2. Pressure
3. Specific volume (v V/m)
4. Any specific extensive property (per unit mass or mole)

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


6. Walls and constraints:

Permit or prevent redistribution of extensive properties.


In an closed composite system the internal constraints are impermeable walls

Extensive Non-permitted Permitted or Observation if


property or restrictive nonrestrictive permitted

V, volume Rigid wall Moving wall Boundary work


N, moles Impermeable Permeable wall Mass transfer
E, energy Adiabatic Diathermal Heat transfer

Adiabatic: Zero heat transfer regardless of magnitude of temperature gradient


normal to the boundary.

Diathermal: Temperature gradient normal to the boundary is zero even in the


presence of heat transfer.

Recall Fouriers law for heat conduction: qn = -kAn T/ n

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


7. State:
A description of the condition of the substance defined by specifying its
properties (p, T, v, u, h, s, ).
8. State Postulate: (n = #WM +1)
The number of independent intensive thermodynamic properties required to
fully describe a specified pure substance is equal to the number of reversible
work modes plus one (n = #WM +1). For simple systems (i.e. 1 work mode)
only 2 properties are needed to fully describe the state of a pure substance.

Derivation of the State Postulate Wbdry

1st law (closed system): Qnet,in,1-2 - Wnet,out,1-2 = E = E2 E1


Q
The 1st law says that we can change the energy of a system by transferring
energy as work and/or heat.
If we have a compressible substance we can increase its energy through PdV
work. Volume is the independently variable property of the work mode (i.e.
Wbdry,out = PdV)

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


In addition, we can hold the volume fixed and change the system energy by
heat transfer, for which temperature may be the most appropriate
independently variable property. This gives us one more free variable.

Therefore, for each of the independent ways of varying the energy of a


substance there is one independently variable thermodynamic property.

Thus: The number of independent intensive thermodynamic properties


required to fully describe a specified pure substance is equal to the
number of reversible work modes plus one.

The state of a pure simple compressible substance is completely defined by


two independent, intensive properties (i.e. u = u(T,v)).

If, in addition, potential energy is active in your problem, you have one
additional work mode and will need to specify an additional variable, i.e.
E(T,v,z).

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


Callens Postulate I: Equilibrium states of simple systems are completely characterized
by internal energy U, volume V and the number of moles N1, N2,
.., Nr of each chemical component. (Callen, p. 13)

9. Simple Compressible Substance (SCS) or Simple System:


Any substance for which the only important reversible work mode is volume
change (i.e. boundary or PdV work).
Not subject to the influence of gravitational, electrical, and magnetic fields and
inertial forces.
Sufficiently large that surface effects can be neglected.
Homogeneous and isotropic definite chemical composition.
The state of a single component, simple compressible substance is completely
defined by two independent, intensive properties (i.e. u = u(T,v)).

10. Phase of a Substance:


Defined as a quantity of matter which is homogeneous in chemical
composition and in physical structure.
All substances can exist in solid, liquid and gaseous phases.

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


11. Equilibrium:

A system is in a state of equilibrium if a change of state cannot occur while the


system is not subject to interactions with the surroundings.
Thermodynamic properties are defined only when a system is in equilibrium!

a.) Thermal Equilibrium:


Temperature is uniform throughout the system (no temperature
gradient).
b.) Mechanical Equilibrium:
There are no unbalanced forces within the system.
Pressure is uniform throughout the system (no pressure gradient).
c.) Chemical Equilibrium:
There is no tendency for a net chemical reaction to take place when
chemical species are allowed to interact.
Chemical composition is uniform throughout the system.
d.) Phase Equilibrium:
There is no tendency for phase transformation (i.e. melting) when the
two phases are brought in contact

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS

e.) Thermodynamic Equilibrium:


There is no net flow of macroscopic energy or matter within a system
in thermodynamic equilibrium, though the molecules are free to flow.
The atoms/molecules have relaxed to a stable state.
If all the conditions for mechanical, thermal, chemical and phase
equilibrium are satisfied, this system is in a state of thermodynamic
equilibrium.
12. Process:
The change of a system from one equilibrium state to another.
A complete description of a process requires specification of end states and its
path.
a.) Isothermal Process (constant temperature) Wout P
b.) Isobaric Process (constant pressure)
c.) Isochoric Process (constant volume)
d.) Isentropic Process (constant entropy)

Qin

system boundary V

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


13. Quasistatic (Quasiequilibrium) Process:

A series of state changes where the substance within the system is


infinitesimally close to a state of equilibrium at all times.
A quasistatic process may be considered practically as a series of equilibrium
states and its path can be represented graphically as a continuous line on a state
diagram.
The expressions for boundary work (i.e. W = PdV) and heat transfer (i.e. Q
= TdS) are valid only for quasistatic processes.
From an atomic/molecular point of view, how quickly one can undergo a
process, while meeting the quasistatic requirement, is a matter of how quickly
the atom/molecules communicate the change amongst one another and relax to
an equilibrium state.

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


14. Reversible Process:

If at the conclusion of the process, the initial states of the system and
surroundings can be restored without leaving any net change at all elsewhere,
the process is reversible.
A reversible process must be a quasistatic process.
Reversible processes cannot involve such phenomena as solid or fluid friction,
electric resistance, inelastic deformation, and hysteresis in magnetization or
polarization.
Some debate on definitions
Old interpretation: quasistatic implies reversible
New interpretation: reversible process is more restrictive
If complete equilibrium is reached at each step along the path, then quasistatic
is also reversible.
If for example, the thermal diffusion time scale is different from the viscous
mixing time scale, this process may be quasistatic in terms of mixing, but may
not reversible.

15. Cycle:
A process whose initial and final states are identical

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MAE 501 course notes Spring 2013 Copyrighted by R. D. Gould

ADVANCED ENGR THERMODYNAMICS


Solution Flowchart

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