1

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:
gas-cylinder 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 doesnt 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 (cont)
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., o-Zr 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
single-component (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 1-component 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, |

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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 constant-p process
- for an open (flow) system, H replaces U in
the 1
st
Law
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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 one-component 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

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Derivative Properties
Specific heats (heat capacities):
C
P
= (ch/cT)
P
- constant-pressure

C
V
= (cu/cT)
V
- constant-volume

Coefficients of expansion:
o = (1/v)(cv/cT)
P
- thermal expansion
o(Hg) used for mercury thermometer

| = -(1/v)(cv/cp)
T
- compressibility

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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 = mv
2
kg-m
2
/s
2
; but from F = ma, N = kg-m/s
2

kg-m
2
/s
2
= N-m = J

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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)
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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
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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

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Thermodynamic Processes
-Process - change in p-V-T
state of system due to
exchange of heat and/or
work with the surroundings.
- Plot process path on a
pressure-volume 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



-
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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
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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
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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)
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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 A)




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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)

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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
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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 path-dependent, AU is not


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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 path-independent.


Any quantity whose change is independent of the
path must be a thermodynamic property as in the
1
st
Law, where Q W is path-independent
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
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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
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
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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
>

=
|
|
.
|

\
|
+
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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 (ATPmuscle)
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
= (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 non-pv 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