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Advanced Thermodynamics
The Laws of Thermodynamics
Lecture 2, 26
th
February 2014
Advanced Thermodynamics
Centre for Energy
2
Outline
1. The First Law: Closed & Open Systems
2. Enthalpy, Heat Capacities & Entropy
3. The Second Law
4. The Fundamental Equation
Text References:
Kyle, Chapters 1.1 1.3, 2 and 4.1, 4.4 & 4.5
Prausnitz, Chapters 1 and 2
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What is Thermodynamics
An experimentally-based science that, without reference to
the microscopic nature of matter, establishes the
relationships among the variables describing systems at
equilibrium.
Laws of Thermodynamics are observed facts, not theories
based on models. The science of Thermodynamics is the
logical framework based on the application of these laws.
According to Einstein, Thermodynamics is:
the only physical theorythat will never be overthrown
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First Law for Closed System
Conservation of Energy
systems energy change =net energy exchange with surroundings
For CLOSED systems
Heat + Work Kinetic +Potential +Internal =
(speed) (height) (volume or
temperature)
W Q E U E E
pot kin
+ = A = A + A + A
(Work done
ON system)
W Q U + ~ A
(Only CHANGES
in U are knowable)
dW dQ dU + =
State variable Path variables
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Enthalpy
It is useful to define a state variable H
called the enthalpy.
PV U H +
Such a definition leads to
P
Q H = A
Heat transferred at
constant pressure
However, this doesnt restrict the use of H
to constant pressure processes it is much
more general and powerful!
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Heat Capacity
Heat required to produce a temperature change
path
path
dT
dQ
C
|
.
|

\
|

Constant volume: Constant pressure:

V
dQ dU =
P
dQ dH = dW=0
V
V
T
U
C
|
.
|

\
|
c
c
=
}
=
= A
const V
V
dT c u
}
=
= A
const P
P
dT c h
def
n
of H
P
P
T
H
C
|
.
|

\
|
c
c
=
extensive state
variable
V
V
T
u
c
|
.
|

\
|
c
c
=
V
P
T
h
c
|
.
|

\
|
c
c
=
intensive state
variable
molar heat
capacities
Divide by #
of moles
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First Law for Open Systems
Conservation of energy now must include energy
carried by mass entering or leaving system
Energy carried by each unit mass:
kin pot
e e u e + + =

}
+ + = A
out
j j
in
i i
dm e dm e W Q E

}
+ =
out
j j j
in
i i i S
dm v P dm v P W W
Fluid work, W
f
Shaft work
Ignoring e
pot
& e
kin
:

}
+ + + + = A
out
j j j j
in
i i i i S
dm v P u dm v P u W Q E ) ( ) (
i
h
j
h
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First Law for Open Systems
Steady State: AE = 0 & integrands constant
S
in
i i
out
j j
W Q H m h m h + = A =

W
S
is NOT the total work, but it is the net work
exchanged with the surroundings
}
= PdV W
}
= VdP W
S
Exercise: Show this
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The Second Law: Statements
Many statements of the 2
nd
Law, usually
associated with heat engines or refrigerators.
It is impossible for a device operating in a cyclic
manner to completely convert heat into work.
The 2
nd
Law recognises the QUALITY of energy
forms heat is a lower quality than work.
Absolute temperatures, the existence of
Entropy & the 2
nd
Law are inseparable.
Forbids perpetual motion!!
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Entropy
The 2
nd
Law implies the existence of an
extensive property called Entropy, S, with
T
dQ
dS
rev
0 =
}
dS
S is a state function
Absolute temperature
REVERSIBLE process
Often the subscript rev is dropped but it should
not be forgotten!
TdS dQ =
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The Second Law
For any process changing the state of an
isolated system:
0 > AS
If the process is not reversible then:
0 > AS
This is useful because a non-isolated system can
be considered together with its surroundings:
0 > A + A
surr
S S
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The Fundamental Equation
CLOSED system, surrounded by reservoir at
(T
res
, P
res
). Combine 1
st
& 2
nd
Laws:
Restrict to
PAV work
S T Q
res
A s W Q U + = A
V P S T U
res res
A A s A
For system undergoing infinitesimal change:
PdV TdS dU s
For system undergoing reversible process:
PdV TdS dU =
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Lecture 2: Core Ideas
1. First Law for Closed & Open Systems
W Q U + = A
S
W Q H + = A
2. Enthalpy, Heat Capacity and Entropy
PV U H + =
( )
path path
dT dQ C / = TdS dQ =
3. The Second Law
0 > AS
Valid for open systems?
4. The Fundamental Equation
Combine 1
st
& 2
nd
laws: PdV TdS dU =