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Sect. 1 Basics of Thermodynamics
The language of thermodynamics
• System: the material in the portion of space
to be analyzed
• Surroundings: exterior environment
• Boundary: A separator, real or imaginary,
between system and surroundings
2
Thermodynamic Systems
• Closed : fixed mass (solid or fluid) within the
• Open (flow) : A volume with partly solid boundaries and
imaginary boundary sections through which fluid passes
2
surroundings
surroundings
3
Example of a more complex system:
gascylinder blowdown
4
Boundary
• the boundary encloses the system
•Adiabatic (insulated) does not allow heat to pass
• Rigid cannot expand or contract (no work done)
• Isolated exchanges neither heat nor work with the
surroundings (rigid and adiabatic)
Surroundings
• space outside the system boundary
• exchanges heat and work with system through boundary
• examples:
thermal reservoir – exchanges heat with system
work devices: spring, piston, weight, atmosphere
5
What does a system consist of?
• Components: distinct chemical species
1. single component: pure substance
2. two components – binary system
• a pure substance can become a binary system:
steam is a single component; but at very high T, it
dissociates into H
2
, OH, and O
2
and becomes a two
component system: (H and O)
• a binary system treated as a single component:
air is O
2
+ N
2
, but at low T, is effectively a single
component because composition doesn’t change
At very high temperatures, reaction produces NO
x
“air” is now a binary, with components N and O
6
• Multicomponent system: three or more components
Steel is an alloy of Fe, Ni, and Cr – this is a
nonreacting ternary. The concentrations of the
species are independent (but their atom fractions
must add to unity)
At low temperature, a mixture of H
2
, CO
2
and O
2
is a nonreacting ternary; at high temperature, it is
a reactive ternary (H, C, and O) with many
chemical reactions
7
Phases: regions of a system with
uniform properties
• phases are solid, liquid, or gas
• solids and liquids are collectively called condensed
phases
• liquids and gases are collectively called fluid
phases
• a gas phase can be called a vapor if it is
condensible (e.g., H
2
O)
• a phase can contain one or more components
8
Phases (con’t)
• a homogeneous system consists of a single phase
• a heterogeneous system consists of two or more phases
separated by sharp interfaces
• a system may contain more than one liquid or solid phases,
but only one gas (vapor) phase; examples:
solid + liquid (e.g., ice and water)
two solids (e.g., oZr and Zr)
two solids and a gas (e.g., Fe, FeO, and O
2
)
gas + liquid (e.g., liquid water and steam)
two immiscible liquids (e.g., oil and water)
9
10
Thermodynamic properties
singlecomponent (pure substance),
• characteristics that fix the condition of a system
• microscopic properties: average of the quantum
numbers of all atoms or molecules in a system –
statistical thermodynamics
• macroscopic properties (also called state variables)
a few characteristics that determine the measurable
gross condition of the system –
classical thermodynamics
11
Classification of thermodynamic properties
(for a pure or 1component substance)
• Fundamental: p,T, V, U, S
• Auxiliary: (derived from fundamental) H, F, G
• Absolute: p, T, v, s, C
P
, C
V
• Relative (to a reference state): U, H, F, G
• Extensive (· amount): V, S, U, H, F, G
• Intensive: p, T (v, u, s, h, f, g)
• Derivative: C
P
, C
V
, o, 
12
fundamental macroscopic properties
• pressure (p) – momentum transferred to walls
by molecular impacts
• temperature (T) – molecular speeds (gas) or
amplitudes of atomic vibrations (solids)
• volume (V)
• internal energy (U) – kinetic and potential
energy contained in molecules or atoms
• entropy (S) – measure of the degree of order
of a system (disorder ~ high S)
13
Auxiliary properties
• enthalpy: H ÷ U +pV
 like internal energy, but automatically
accounts for pV work
 AH (change in enthalpy) is the heat added in
a constantp process
 for an open (flow) system, H replaces U in
the 1
st
Law
14
Auxiliary properties: Free Energies
• Helmholz free energy: F ÷ U – TS
 F is the link between statistical and
classical thermodynamics (F is rarely
used in purely classical approach)
• Gibbs free energy: G ÷ H – TS
 G is the criterion of equilibrium in chemical
reactions
 AG is the maximum work done (or needed)
in a flow process.
15
Absolute and relative properties:
• p, T, V, and S are absolute: zero values are unique;
 absolute zero temperature: 0 K
 The absolute zeros of p and V are obvious
 C
P
and C
V
are derivatives of relative properties
 The absolute value of S comes from the 3
rd
Law:
The entropy of a solid is zero at 0 K.
(all substances are solid at this temperature)
• U, H, F, G are relative: i.e., they must be assigned a
zero value at an arbitrary “reference state” (the
same state for all four)
16
Extensive and Intensive properties
• Extensive: value proportional to amount in
system: V, U, S, H, F, G
• Intensive: value independent of the amount of
material: p, T
• For a onecomponent system (pure substance)
extensive properties can be made intensive by
dividing by the amount (n = moles of substance)
 v = V/n; v = molar volume, or reciprocal
of the molar density
 u = U/n; s = S/n; h = H/n; g = G/n
17
Derivative Properties
• Specific heats (heat capacities):
C
P
= (ch/cT)
P
 constantpressure
C
V
= (cu/cT)
V
 constantvolume
• Coefficients of expansion:
o = (1/v)(cv/cT)
P
 thermal expansion
o(Hg) used for mercury thermometer
 = (1/v)(cv/cp)
T
 compressibility
18
Units of thermodynamic properties
(SI, or metric)
• pressure: Pascal(Pa) = Newton(N)/m
2
; = 10
5
atm
temperature: Kelvins (K) or degrees Celsius:
o
C = K
– 273 (strictly, not SI)
• volume: cubic meters (m
3
) – length in meters (m)
• U, H, F, G: Joules(J or kJ), calorie or kcal also used
 1 cal = 4.184 J 1 kcal = 4.184 kJ
• KE = ½mv
2
kgm
2
/s
2
; but from F = ma, N = kgm/s
2
kgm
2
/s
2
= Nm = J
19
Thermodynamic State of a pure substance
• all properties fixed if any two are specified.
(why 2? see later)
• To know all properties, two Equations of State
(EOS) are needed :
 v(p,T) “volumetric” EOS
 C
P
(T,p) or C
V
(T,v) = “thermal” (EOS)  fixes s,
u, h, g (with specification of a ref. state)
20
Heat: (Q)
• Energy exchanged between system and
surroundings (reservoirs) due to a AT
• Mechanisms (not thermodynamic)
 conduction: molecular motion
 convection: bulk fluid movement
 radiation : electromagnetic fields
• Heat is not a thermodynamic property: it
causes changes in them
21
Work: (W)
• Expansion (“pV” ): W = FAx = (F/A)(AAx) = pAV
• Shaft: rotation of a shaft by a moving fluid
• Electrical: flow of electrons down a potential
gradient
• External: all FAx except pAV;
why? pAV is often not “useful” work: just pushing
back or being pushed by the surrounding
atmosphere
• Work is not a thermodynamic property, but can
change them
• All forms of work are theoretically interconvertible
22
Thermodynamic Processes
Process  change in pVT
state of system due to
exchange of heat and/or
work with the surroundings.
 Plot process path on a
pressurevolume graph
 state of system at 2 is
independent of path (A or B)
 but, Q and W are different
for each path
• Cannot infer Q from this
diagram
• Path depends on how T
varies with V.
}
=
2
1
V
V
dV ) V ( p W
23
“ISO” processes
• In most processes, one property is constant:
Process
Restraint
Property
constant
Example
isothermal T Melting ice
isobaric p Heat gas in
cylinder/piston
isochoric V Heat gas in
closed vessel
isentropic S Gas cylinder
blowdown
cyclic  Returns to
Initial state
24
Reversible Processes
• Internal: in the system
• External: in the surroundings
• Work done by the system is the same as the work
done on the surroundings
• For the same initial and final states, work done
reversibly is always > work done irreversibly
• Requirements of reversibility:
 very slow; moves through equilibrium states
 in fluids, no turbulence
 no friction
 infinitesimal T – T
surr
for heat; p – p
surr
for work

25
Example: Reversible Isothermal
compression of an ideal gas
add small weights (total mass m) so that descent of
piston is gentle; remove heat with very small T  T
surr
This is also W
surr
, the work done by the surroundings
( )
f o
V
V
V
V
rev
V / V ln nRT V / dV nRT pdV W
f
0
f
0
÷ = = =
} }
26
Irreversible version
add single block of mass m; rapid descent;
violent bouncing of piston until final state reached
• Cannot integrate pdV
27
Work to compress irreversibly
( )
55 . 0
1 3
3 ln
1 V / V
V / V ln
W
W
f o
f o
irr
rev
=
÷
=
÷
=
• the work done by the surroundings can be calculated:
W
surr
= p
surr
(V
o
V
f
) + mg (V
o
V
f
)/A
• Force balance on final state: p
f
– p
surr
= mg/A
• Combine:
W
surr
=  p
f
(V
o
V
f
) =  p
f
V
f
(V
o
/V
f
 1) = nRT (V
o
/V
f
 1)
• For V
o
/V
f
= 3
• The surroundings do less work in the reversible
than in the irreversible process
28
Internal equilibrium (system)
• Single phase
 no change of pressure, temperature or composition
with time (mechanical, thermal & chem. equilibrium)
 no gradients of any properties, except at interfaces
between phases
• Multiphase  each phase must have:
 same temperature (thermal equilibrium)
 same pressure (mechanical equilibrium)
 same chemical potential (chemical equilibrium)
29
External Equilibrium
(between system and surroundings)
• Both have the same pressure (unless the
boundary is rigid)
• Both have the same temperature (unless the
boundary is adiabatic)
• No work can be performed by or on the
system (no Ap, AT or Aµ)
30
Constraints and equilibrium
• Constraining a system means fixing two of its
properties
• If U and V are fixed (isolated system), equilibrium
occurs when the entropy is a maximum (mainly of
theoretical importance)
• If p and T are fixed, equilibrium occurs when the
Gibbs free energy is a minimum (useful for phase
equilibrium and chemical equilibrium)
31
The First Law of Thermodynamics
• Cannot be derived from any fundamental principle
(it is one)
• Has never failed an experimental test in 150 years
• Comes in two versions:
 within a system: the “1
st
law”
 between system and surroundings or two
systems: “Law of Conservation of Energy”
32
1
st
Law
• relates changes in system energy to heat and work:
AU + A(PE) + A(KE) = Q – W – W
S
– W
el
U = internal energy
PE = potential energy
KE = kinetic energy
Q = heat (positive if added to the system)
W = expansion (pV) work; + if done by the system
W
S
= shaft work (rotation of a shaft)
W
el
= electrical work (charging a battery)
• Heat and work are equivalent in the 1
st
law
• Even though Q and W are pathdependent, AU is not
33
Conservation of Energy
• Heat and work are exchanged between the
system and the surroundings:
AU
sys
= (Q – W)
sys
AU
surr
= (Q – W)
surr
• Add the 1
st
Laws for system & surroundings:
AU
sys
+ AU
surr
= 0
• This is the Law of Conservation of Energy
34
Where the 1
st
Law is inadequate
• Consider an isolated system consisting of two
rigid subsystems of different temperatures that
communicate thermally:
• Energy conservation and the 1
st
Law yield:
AU
1
+ AU
2
= Q
1
+ Q
2
= 0 or Q
1
=  Q
2
• Either Q
1
or Q
2
must be negative (i.e., one of the
two arrows must be reversed) – the 1
st
Law
cannot tell which one, but the 2
nd
Law can.
35
The Second Law of Thermodynamics
• The 2
nd
Law was “discovered” by Clausius from
numerous observations showing that if a process is
reversible, is pathindependent.
• Any quantity whose change is independent of the
path must be a thermodynamic property – as in the
1
st
Law, where Q – W is pathindependent
• Clausius called the property entropy, with the
symbol S:

.

\

2
1
rev
T
Q
d

.

\

= ÷
2
1
rev
1 2
T
Q
d S S
36
Irreversible processes
• For irreversible processes, the equality no
longer holds. Instead:
• In irreversible processes, entropy is created!
• Other forms of the 2
nd
Law:
dS >

.

\

> ÷
2
1
1 2
T
Q
d S S
} }
= =
2
1
rev
rev
0
T
Q
and TdS Q
;
T
Q δ
37
“law of entropy production”
• Entropy production is to the 2
nd
Law as
energy conservation is to the 1
st
Law
• add 2
nd
Law for system and surroundings (T
surr
>T
sys
)
entropy can be produced but never destroyed
}


.

\

o > A
2
1
sys
sys
T
Q
S
}


.

\

o ÷ > A
2
1
surr
surr
T
Q
S
0 S S
surr sys
38
The direction of heat flow revisited
• begin with: AS
1
+ AS
2
> 0
• but AS
1
= Q
1
/T
1
and AS
2
= Q
2
/T
2
(heat flow to and from
reservoirs is reversible)
• T
1
= T
2
, is the source of irreversiblity
Q
1
/T
1
+ Q
2
/T
2
> 0; from 1
st
Law: Q
1
= Q
2
If T
1
>T
2
, then Q
2
>0
and Q
1
<0
0
T T
T T
Q
T
1
T
1
Q
2 1
2 1
2
2 1
2
>
÷
=


.

\

+ ÷
39
How to calculate system entropy
change for an irreversible process
• Example: doubling the volume of an ideal gas
in an isolated system (AU = 0):
Irreversible version:
initial state (T
o
) final state(T
o
)
Boltzmann eqn: S=nN
Av
klnW; AS=nRln(W
f
/W
o
) = nRln2
40
• Reversible version:
41
AU = 0 for the reversible process as well
• from the 1
st
Law, Q = W
• work can be calculated for the reversible
process only
• From the 2
nd
Law:
AS = Q/T = nRln(V
f
/V
o
) = nRln2
• Since entropy is a thermodynamic property,
the path used to compute it is immaterial
• AS computed for the reversible process is the
same as the AS for the irreversible process
(but, work was done in reversible process)
( ) Q V / V ln nRT pdV W
0 f
V
V
f
0
= = =
42
Entropy, Free Energy and Equilibrium
du = Tds – pdv  ow
ext
•isolated system, dv = du = 0
•Equilibrium: system cannot perform external work, or dw
ext
= 0
 Electrical (battery)
 Chemical (ATP÷muscle)
For reversible process: Tds pdv
• for a closed system: du = oq  ow
(PV)
ow
ext
ds
u,v
= 0 s
State of
system
equilibriu
m state
At equilibrium with u & v constant
the entropy is a maximum
o = small increment of heat or work
d = small increment of a thermodynamic property
43
Thermal equilibration of identical solids
T
1
Q
T
2
T
f
T
f
energy conservation:
AU
Tot
=AU
1
+AU
2
= 0
C
V
(T
f
– T
1
) + C
V
(T
f
– T
2
) = 0 T
f
= ½(T
1
+ T
2
)
AS
Tot
= AS
1
+ AS
2
=


.

\

=


.

\

+


.

\

2 1
2
f
V
2
f
V
1
f
V
T T
T
ln C
T
T
ln C
T
T
ln C
Eliminate T
f
:
(
(
¸
(
¸
+
= A
2 1
2
2
1
V tot
T T 4
) T T (
ln C S
T
2
/T
1
AS
Tot
/C
V
0.9 0.0028
1.0 0
1.1 0.0023
Thermal equilibration results in an increase in
the entropy of the isolated system
44
h ÷ u + pv ÷ dh = du + pdv + vdp ÷ use du equation:
dh = Tds + vdp  oW
ext
Enthalpy
Helmholz free energy
f ÷ u – Ts ÷ df = du – Tds – sdT ÷ use du equation:
df =  pdv – sdT  oW
ext
Gibbs free energy
g ÷ h – Ts ÷ dg = dh – Tds – sdT ÷ use dh equation:
dg = vdp – sdT  oW
ext
45
du = Tds – pdv
dh = Tds + vdp
df =  pdv – sdT
dg = vdp – sdT
• These were derived assuming
reversible oq and oW
(pv)
• However, since they involve
only state functions (properties),
they are valid for any process
Neglecting external work:
Collectively, they are called:
1. Fundamental differentials, or
2. Tds equations (first two), or
3. Gibbs equations
46
Equilibrium at constant T and p
with dT = dp = 0:
dw
ext
= dg
• Reversible nonpv work at constant p and T
• System is at equilibrium when dw
ext
= 0
dg
T,p
= 0
At equilibrium with p & T constant
the Gibbs free energy is a minimum
dg = vdp – sdT  oW
ext
equilibrium
state
State of
system
g
47
The Phase Rule
• Fixes how many properties can be varied for a
given number of components (C) and phases (P)
• The allowable variable properties are called
degrees of freedom (f):
• Single component (C = 1) 1 phase (P = 1); f = 2
• Single component (C = 1) 2 phases (P = 2); f = 1
e.g. the vapor pressure of a condensed phase = F(T)
• Single component (C = 1) 3 phases (P = 3) f = 0
e.g. the triple point where gas, liquid & solid coexist
• Two components (C = 2); 3 phases (P = 3) ] = 1
e.g. a metal, its oxide and O
2
gas: at each T, there is a
unique at which M and MO
x
coexist
2
O
p
f = C + 2 – P  N
rxn
48
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