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Debabrata Goswami
Jan 2017
IITK
COURSE CONTENT
Zeroth Law of Thermodynamics: Equilibrium, State Functions, Temperature, Equations of State.
First Law of Thermodynamics: Work, Heat, Internal Energy, Heat Capacity, Concept of Enthalpy.
Second Law of Thermodynamics: Reversible and Irreversible Process, Heat Engines, Carnot
Cycle, Different statements of the Second Law, Spontaneous Change, Entropy.
Third Law of Thermodynamics: Concept of the absolute zero temperature.
Free Energy and Standard States: Free energies and Thermodynamic potentials, Legendre
Transforms, Equilibrium and Non Equilibrium, Chemical Potentials, Free Energy, Standard States,
Reaction Thermodynamics, Equilibrium Constant.
Equilibrium Thermodynamics: Chemical Potential of Mixtures, Phase Equilibrium, Phase Rule,
Clapeyron Equation, Phase Diagram.
Real Gases: Equations of State, Phase Transitions.
Solutions: Molarity, Partial Molar Quantities, Mixing, Ideal Solutions, Non Ideal Solutions,
Electrolytes, Ionic activity and the Debye Hueckel Theory, the Nernst Equation, Colligative
properties, Multi component phase diagrams.
Kinetic Theory of Gases and Transport Processes.
Reaction Kinetics: Reaction Rates, Rate Laws, Reaction Mechanisms, Applications
COURSE EVALUATION
Attendance + Homework Assignments
10%
Quizzes
10%
30%
50%
THERMODYNAMICS
Study of Systems at equilibrium describing their macroscopic properties
Self Contained
Built on four Laws, observations and mathematics
Zeroth Law
1st Law
2nd Law
3rd Law
DEFINITIONS
System : That part of the Universe, which we choose to study (Certain quantity of matter
within a boundary)
Surroundings : The rest of the Universe
Boundary : The surface dividing the System from the Surroundings
Systems can be
Open : Mass and Energy can transfer between the System and the Surroundings
Closed : Energy can transfer between the System and the Surroundings, but NOT mass
Isolated : Neither Mass nor Energy can transfer between the System and the Surroundings
System description requires
A few macroscopic properties: p, T, V, n, m,
Knowledge if System is Homogeneous or Heterogeneous
Knowledge if System is in Equilibrium State
Knowledge of the number of components
THERMODYNAMIC PROPERTIES
(n, m, V,)
(T, P, r,)
gas
p =1 bar
T = 100C
THERMODYNAMIC TRANSFORMATIONS
Change of State:
Notation :
3 H2 (g, 5 bar, 100 C) = 3 H2 (g, 1 bar, 50 C)
initial state
final state
When a hot object is placed in thermal contact with a cold object, heat flows from the
warmer to the cooler object. This continues until they are in thermal equilibrium (the heat
flow stops). At this point, both bodies are said to have the same temperature.
This intuitively straightforward idea is formalized in the zeroth Law of thermodynamics
and is made practical through the development of thermometers and temperature scales.
ZEROTH LAW
TEMPERATURE
Operational definition of temperature (T)
Need : (1) substance
(2) property that depends on T
(3) reference points
(4) interpolation scheme between reference points
Example : Ideal Gas Thermometer with the Celsius scale.
Units of pressure
Units of temperature
1 Pa 1 N m 2
1 atm 1.01325 105 Pa
1 bar = 105 Pa
1
1 torr =
atm
760
PV
RT
T=300K
compressibility factor
Ideal gas: z = 1
z < 1:
z > 1:
V b RT
2
V
The set of parameters Pc, Vc, Tc for which the number of solutions changes
from one to three, is called the critical point. The van der Waals equation has
an inflection point at Tc.
ISOTHERMS
(P VS. V AT CONSTANT T)
P
T Tc :
0
T
P
0 : unstable region
V T
(V b) 2 V 3
V T
2a (V b) 2
0 for V
RT
3
(3 or 1 real roots)
2P
2 RT
6a
2
3
4
V T (V b) V
3a (V b)3
0 for V
RT
4
Vc 3b
8a
Tc
27 Rb
a
Pc
27b 2
3
1 8
P
V TR
R
2 R
VR
3 3
PR
P
V
T
, VR , TR
"reduced" variables
Pc
Vc
Tc
VIRIAL COEFFICIENTS
Z
PV
B
B
1 2V 3V2 Virial expansion
RT
V
V
B2V (T ) 2 N A
e u ( r ) / kBT 1 r 2 dr
c12 c6
u ( r ) 4 12 6
r
r
THERMODYNAMICS
Thermodynamics is the study of the effects of work, heat, and energy on a
system
Thermodynamics is only concerned with macroscopic (large-scale) changes and
observations
GETTING STARTED
All of thermodynamics can be expressed in terms of four
quantities
Temperature (T)
Internal Energy (U)
Entropy (S)
Heat (Q)
CLASSICAL VS STATISTICAL
Classical thermodynamics concerns the relationships
between bulk properties of matter. Nothing is examined
at the atomic or molecular level.
Statistical thermodynamics seeks to explain those bulk
properties in terms of constituent atoms. The statistical
part treats the aggregation of atoms, not the behavior
of any individual atom
FIRST LAW
The first law of thermodynamics is an extension of the law
of conservation of energy
The change in internal energy of a system is equal to the
heat added to the system minus the work done by the
system
U = Q - W
PROCESS TERMINOLOGY
Adiabatic no heat transferred
Isothermal constant temperature
Isobaric constant pressure
Isochoric constant volume
ADIABATIC PROCESS
An adiabatic process transfers no heat
therefore Q = 0
U = Q W
When a system expands adiabatically, W is positive (the system does
work) so U is negative.
When a system compresses adiabatically, W is negative (work is done
on the system) so U is positive.
ISOTHERMAL PROCESS
An isothermal process is a constant temperature process. Any heat
flow into or out of the system must be slow enough to maintain
thermal equilibrium
For ideal gases, if T is zero, U = 0
Therefore, Q = W
Any energy entering the system (Q) must leave as work (W)
Thermal Processes
We will assume that all processes we discuss are quasi-static they
are slow enough that the system is always in equilibrium.
We also assume they are reversible:
For a process to be reversible, it must be possible to return both the
system and its surroundings to exactly the same states they were in
before the process began.
Thermal Processes
This is an idealized reversible process. The gas is compressed; the
temperature is constant, so heat leaves the gas. As the gas expands,
it draws heat from the reservoir, returning the gas and the reservoir
to their initial states. The piston is assumed frictionless.
Thermal Processes
Work done by an expanding gas, constant pressure:
Thermal Processes
If the volume stays constant, nothing moves and no work is done.
Thermal Processes
If the temperature is constant, the pressure varies inversely
with the volume.
Thermal Processes
The work done is the area under the curve:
Thermal Processes
An adiabatic process is one in which no heat flows into or out of the system.
The adiabatic P-V curve is similar to the isothermal one, but is steeper. One
way to ensure that a process is adiabatic is to insulate the system.
Thermal Processes
Another way to ensure that a process
is effectively adiabatic is to have the
volume change occur very quickly. In
this case, heat has no time to flow in
or out of the system.
Thermal Processes
Here is a summary of the different types of thermal processes:
where
The efficiency is the fraction of the heat supplied to the engine that appears
as work.
If the two reservoirs are at the same temperature, the efficiency is zero; the
smaller the ratio of the cold temperature to the hot temperature, the closer
the efficiency will be to 1.
Note that
- more heat is exhausted to the kitchen than is removed from the refrigerator.
Entropy
A reversible engine has the following relation between the heat transferred and
the reservoir temperatures:
Rewriting,
This quantity, Q/T, is the same for both reservoirs, and is defined as the change in
entropy.
Entropy
Entropy
A real engine will operate at a lower efficiency than a reversible engine; this
means that less heat is converted to work. Therefore,
Entropy
To generalize:
The total entropy of the universe increases whenever an irreversible process
occurs.
The total entropy of the universe is unchanged whenever a reversible process
occurs.
Since all real processes are irreversible, the entropy of the universe continually
increases. If entropy decreases in a system due to work being done on it, a
greater increase in entropy occurs outside the system.
Entropy
As the total entropy of the universe increases, its ability to do work
decreases. The excess heat exhausted during an irreversible process
cannot be recovered; doing that would require a decrease in entropy,
which is not possible.
Summary: Thermodynamic
Laws
0
Temperature
Energy Conservation
Entropic Increase
Absolute Entropy
)0
0]
Summary
When two objects have the same temperature, they are in thermal
equilibrium.
The first law of thermodynamics is a statement of energy
conservation that includes heat.
Summary
In a reversible process it is possible to return the system and its
surroundings to their initial states.
Irreversible processes cannot be undone.
The work done during a process is equal to the area under the
curve in the PV plot.
The work done at constant pressure is
The work done at constant volume is zero.
The work done in an isothermal expansion is
Summary
An adiabatic process is one where no heat transfer occurs.
The value of the specific heat depends on whether it is at constant
pressure or at constant volume.
Molar specific heat is defined by:
For a monatomic gas at constant volume:
Summary
In a PV plot,
is constant, where
Summary
A reversible engine has the maximum possible efficiency,
Summary
Coefficient of performance of a refrigerator:
Summary
Change of entropy during a reversible heat
exchange:
Summary
It is impossible to lower the temperature of an object to
absolute zero in a finite number of steps.