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cycle
conserv non
ds F 0
Work is path-dependent for non-conservative forces
friction & other dissipative forces can still do work
m
m
Process Variable: Heat
What is Heat?
(as opposed to Temperature)
Rigid, impermeable box
Can system ever change?
Temperature measures the
state RIGHT NOW
Heat changes the system
Heat content of the
system is meaningless
State Functions vs. Process Variables
Can we describe these mathematically?
Classification of Thermodynamic Variables
System in
State A
T
A
, P
A
, V
A
Process
System in
State B
T
B
, P
B
, V
B
Mathematical Descriptions of Relationships
... + + = NdY MdX dZ
Infinitesimal steps in functions X, Y, result in
infinitesimal change in state function Z:
Where the coefficients M & N are
the partial derivatives:
,... Y
X
Z
M
|
.
|
\
|
c
c
=
,... X
Y
Z
N
|
.
|
\
|
c
c
=
Maxwells relations tell us how
those coefficients are related
,... ,... Y X
X
N
Y
M
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c
What is Equilibrium?
A system in balance
Conditions for Equilibrium
Equilibrium
A system is in thermodynamic
equilibrium if it is not capable of a finite
spontaneous change to another state
without a finite change in the state of
the environment
A system not in equilibrium with its
environment will change
spontaneously until it has
exhausted its capacity for change
Types of Equilibrium
Thermal: equality of T across the system boundary
Mechanical: equality of P across the system boundary
Phase Equilibrium: no tendency for net transfer of one
or more species from one phase to another
Chemical: no tendency for chemical reaction
Ice & Water in a closed
system at 1 atm.
Whats the condition
for equilibrium?
Conditions for Equilibrium
Equilibrium
A system is in thermodynamic
equilibrium if it is not capable of a ___,
_________ change to another state
without a _____ _____ in the state of
_________________
A system not in equilibrium with its
environment will change
__________ until it has exhausted
its ______________
Types of Equilibrium
Thermal: equality of T across the system boundary
Mechanical: equality of P across the system boundary
Phase Equilibrium: no tendency for net transfer of one
or more species from one phase to another
Chemical: no tendency for chemical reaction
Ice & Water in a closed
system at 25C. Whats
the condition for
equilibrium?
Discussion
Ice & Water in a closed, thermally
isolated system.
True/False & why?
Ice and water can never be in phase
equilibrium because they are different states
of aggregation (1 Liquid, 1 Solid)
If we removed the thermally isolated
constraint, the system would absorb heat
from the environment and melt the ice.
The system will never be in phase
equilibrium because molecules are
constantly transferring from ice to water and
back again
Aside: Equilibrium vs. Stead-State
Whats the difference?
Equilibrium: all state variables are
constant and net reaction rate = 0
Example: Pour 80 L of water into a empty tub and let it
settle, the state variables (volume, pressure,
temperature, composition) are constant.
Steady-state: all state variables may
be constant but net reaction rate
may be nonzero
Example: Start with empty tub, pull out the drain plug &
turn on the faucet. After some time, the flow in will
equal the flow out so again the volume will stabilize.
Net reaction rate (in this case, mass flow), is nonzero.
Laws of Thermodynamics
E
x
A
B
C
1st Law: Conservation of Mass & Energy
Mass Conservation:
the ancient Greeks, really
1774: Lavoisier conclusively demonstrated conservation
of mass in chemical reactions
1st Law: Conservation of Mass & Energy
What do we mean by energy?
The capacity to do work ?
vs.
The capacity to induce a change
in that which inherently resists
change
Capacity = Effort & Change
= Driving Force x Displacement
If DF + displacement contained in system, this
results in a change in internal energy, which is as
important to thermodynamics as changes in
position or motion of entire system.
1st Law: Conservation of Mass & Energy
Energy Conservation:
1797: Count Rumford at the cannon factory showed
caloric cannot be depleted
1799: Humphrey Davy melts ice in a vacuum, end of
caloric gas theory of thermal conduction
Equivalence of Work & Heat:
1843-1848: Joule & Kelvin
demonstrated indisputably
the precise equivalence of
mechanical work & total
thermal energy obtainable
from it
E, m treated separately:
What about E = mc
2
?
Equivalence of Work & Heat
Energy conservation: The change in internal energy (U)
of a system is equal to the heat (Q) added to the system
plus the mechanical work (W) and non-mechanical work
(W) done on the system.
dU = oQ + oW + oW
Path independent Path dependent!
P
V
Initial State
Final State
For a cycle, AU=0
But Q, W, W = 0
Mass conservation: material neither created nor destroyed
AU = Q + W + W
Heat in: Q +ve
Heat out: Q ve
Work done on: W +ve
Work done by: W -ve
oW = - P dV
dU = oQ - PdV + oW
Equivalence of Work & Heat
True or False?
Why?
Work and Heat are equivalent because they are both forms of energy.
Work and Heat are equivalent because The Prof just said so.
Work and Heat are equivalent because Joule & Kelvin said so, and theyre
names I recognize from the Nobel Prize list.
If Joule & Kelvin say so
Do you believe Heat & Work are equivalent?
Think, Pair, Share
Do you expect that:
Stones, cooling themselves, could convert their heat
contents into work: roll uphill unaided?
Hot water could spontaneously convert its heat into
kinetic or potential energy?
Not in our experience. So dU = oQ + oW + oW cannot be
the full story on thermodynamics!
Nature does not allow heat to be spontaneously converted
into work without the accompaniment of other changes.
(Kelvins formulation of 2nd law!)
2
nd
Law: Directionality of Processes
Times arrow in classical thermodynamics: Entropy (S)
Changes occur in the direction that increases entropy for the
universe ( system + surroundings)
For any given process, entropy of the system may increase or
decrease: but the total entropy of universe must increase
heat
engine
Hot reservoir Cold reservoir
oW s oQ
h
- oQ
c
Entropy as waste or unavailable energy
Entropy as Disorder
Ordered structures (crystals) vs.
ice, H
2
O
water, H
2
O
graphite, C
amorphous C
quartz, SiO
2
silica, SiO
2
Atomic example:
Molecular examples: let = molecule
As more became known about the nature of matter, the
statistical thermodynamics concept of entropy as disorder
(mixedupness) arose
disordered structures (gasses,
most liquids, amorphous solids)
Configurational Entropy
As more became known about the nature of matter, the
statistical thermodynamics idea of entropy as disorder
(mixedupness) arose
Configurational entropy
A
B
Case 1
Case 3
Case 2
Which has the greatest (configurational) entropy? Which has the least?
Configurational Entropy
Configurational entropy
A
B
Case 1
Case 3
Case 2
Which has the greatest (configurational) entropy? Which has the least?
They all have the same entropy because all microstates are equivalent.
Case 1 has the most entropy because it is the least likely to occur.
Cause 2 has the most entropy because it is the most mixed up.
True/False? Discuss your evidence.
Configurational Entropy vs. Microstates
Each microstate is unique but there are many more essentially random ones
Consider what can be swapped for what
A
B
Case 1
Case 3
Case 2
1 2 3 4 5 6 7 8 9 10
1
2
3
4
5 6
7 8
9
10
1 2 3
4 5 6 7
8 9 10
Neighbor Tally
38 A-B nearest neighbors
9 B-B nearest neighbors
x A-A nearest neighbors
74 A-B nearest neighbors
0 B-B nearest neighbors
y A-A nearest neighbors
22 A-B nearest neighbors
37 B-B nearest neighbors
z A-A nearest neighbors
Try to make an equivalent state with
the same number of interactions
Configurational Entropy vs. Microstates
1 2 3 4 5 6 7 8 9 10
Neighbor Tally
38 A-B nearest neighbors
9 B-B nearest neighbors
x A-A nearest neighbors
42 A-B nearest neighbors
7 B-B nearest neighbors
x-2 A-A nearest neighbors
38 A-B nearest neighbors
9 B-B nearest neighbors
x A-A nearest neighbors
1 2 3 4
5
6 7 8 9 10
1 2 3 4 5 6 7 8 9 10
Can only swap for if I swap the entire row
Case 1 (lowest entropy): limited # of equivalent states
Case 1
Configurational Entropy vs. Microstates
Case 2 (highest entropy): nearly infinite # of equivalent states
Case 2
1
2
3
4
5 6
7 8
9
10
Neighbor Tally
74 A-B nearest neighbors
0 B-B nearest neighbors
y A-A nearest neighbors
74 A-B nearest neighbors
0 B-B nearest neighbors
y A-A nearest neighbors
74 A-B nearest neighbors
0 B-B nearest neighbors
y A-A nearest neighbors
1
2
3
4
5 6
7 8
9
10
1
2
3
4
5 6
7
8
9
10
In fact I can swap any for any
Configurational Entropy vs. Microstates
Case 3 (moderate entropy): Moderate # of equivalent arrangements
Case 3
1 2 3
4 5 6 7
8 9 10
Neighbor Tally
22 A-B nearest neighbors
37 B-B nearest neighbors
z A-A nearest neighbors
22 A-B nearest neighbors
37 B-B nearest neighbors
z A-A nearest neighbors
22 A-B nearest neighbors
37 B-B nearest neighbors
z A-A nearest neighbors
1 2 3
4 5 6 7
8 9 10
1 2 3
4 5 6
7 8 9 10
Have to swap several for
Can have many microstates with same S
Entropy
A measure of disorder or
randomness
C
o
n
f
i
g
u
r
a
t
i
o
n
a
l
e
n
t
r
o
p
y
6 equivalent microstates
Nearly equivalent microstates
~45 equivalent microstates
8
A
B
Case 1
Case 3
Case 2
Entropy and Randomness
Consider it atomistically: in any conglomeration of atoms, each atom has
thermal kinetic energy & an associated velocity which continually change both
in magnitude and direction by chance collisions with other atoms
From a strictly statistical point of view, an essentially random positional
arrangement (Case 2, on previous slides) has by far the highest probability of
occurring at any given moment.
BUT it doesnt win because it is opposed by (and at least partially
counterbalanced by) the forces derived from the potential energy of the atoms.
HOWEVER:
The tendency towards randomness is always present and is stronger when
atomic kinetic energies are higher (i.e., at higher temperatures)
Described mathematically as:
T
Q
dS
rev
o
=
change in heat, applied reversibly
(i.e. without losses) to achieve the event
temperature at which the event occurs
incremental change in entropy
for a particular event
The 2nd Law, Mathematically
The entropy of an isolated system not at equilibrium will tend
to increase over time, approaching a maximum value.
For a process taking place for a system at equilibrium
(reversible), the entropy of a system + surroundings, the
entropy of system + surroundings is constant:
In a spontaneous (irreversible) process:
0 = +
rev
surr
rev
sys
dS dS
0 > +
irrev
surr
irrev
sys
dS dS
Combined Statement of 1
st
& 2
nd
Laws
dU = oQ - P dV + oW
1
st
Law:
2
nd
Law:
T
Q
dS
rev
o
=
dU = T dS - P dV + oW
A centerpiece of the mathematical
framework of thermodynamics!
3
rd
Law: Absolute Zero
As a system approaches absolute zero of temperature all
processes cease and the entropy of the system approaches
a minimum value which is the same for all substances.
For conveniences sake, choose this minimum value to be 0
Handy for calculating the change in entropy for chemical
reactions without having to actually measure every case
experimentally.
AS (Reaction) = Products - Reactants
To simplify the calculations of AS for chemical reactions, the
values of S are tabulated for elements & many compounds at
a standard state, taken to be 298K and 1 atm pressure:
o
S
298
Substance S
298
(J/mol K)
C (graphite) 5.69
O
2
205.03
CO 197.9
CO
2
213.64
First write a stoichiometrically
balanced equation for the reaction
C + O
2
= CO
(
+ = A ) (
2
1
) ( ) ( ) (
2 298 298 298 298
O S C S CO S rxn S
o o o o
(
+ = A ) 3 . 205 (
2
1
69 . 5 9 . 197 ) (
298
rxn S
o
56 . 89 ) (
298
= A rxn S
o
J/mol K
Summary
Thermodynamics describes the quest for equilibrium
Classification of Systems
Classification of Variables
State Functions
Process Variables
Classification of Relationships
Equilibrium & the Laws of Thermodynamics
0: You have to play the game.
1: You cannot win.
2: You cannot break even, except at absolute zero.
3: You cannot reach absolute zero.
The Minute Paper (Anonymous!)
Take an index card
On the front of the card
What do you think was the most important point of todays
lecture?
On the back of the card
What was the muddiest point in this lecture? That is, what
was least clear to you?
Turn in the index card when you leave, please!