My Notes
My Notes
My Notes
Statement:
The entropy of a system approaches a constant value as the temperature approaches absolute
zero. At absolute zero, the system must be in a state with minimum thermal energy. This
statement holds true if the perfect crystal has only one state with minimum energy. Entropy is
related to the number of possible microstates according to:
S=kB ln Ω
Explanation:
In simple terms, the third law states that the entropy of a perfect crystal of a pure substance
approaches zero as the temperature approaches zero. The alignment of a perfect crystal leaves no
ambiguity as to (concerning, wrt) the location and orientation of each part of the crystal. As the
energy of the crystal is reduced, the vibrations of the individual atoms are reduced to nothing,
and the crystal becomes the same everywhere.
a) Single possible configuration for a system at absolute zero, i.e., only one microstate is
accessible. Thus S = k ln W = 0. b) At temperatures greater than absolute zero, multiple
microstates are accessible due to atomic vibration (exaggerated in the figure). Since the number
of accessible microstates is greater than 1, S = k ln W > 0.
The third law provides an absolute reference point for the determination of entropy at any other
temperature. The entropy of a closed system, determined relative to this zero point, is then
the absolute entropy of that system. Mathematically, the absolute entropy of any system at zero
temperature is the natural log of the number of ground states times Boltzmann's
constant kB = 1.38×10−23 J K−1.
The entropy of a perfect crystal lattice as defined by Nernst's theorem is zero provided that its
ground state is unique, because ln(1) = 0. If the system is composed of one-billion atoms, all
alike, and lie within the matrix of a perfect crystal, the number of combinations of one-billion
identical things taken one-billion at a time is Ω = 1. Hence:
S-So=kBlnΩ=0
The difference is zero, hence the initial entropy S0 can be any selected value so long as all
other such calculations include that as the initial entropy. As a result, the initial entropy value
of zero is selected S0 = 0 is used for convenience.
S-S0=S-0=0
S=0
The experimental observations about the behavior of gases discussed so far can be
explained with a simple theoretical model known as the kinetic molecular theory.
This theory is based on the following postulates, or assumptions.
1. Gases are composed of a large number of particles that behave like hard,
spherical objects in a state of constant, random motion.
2. These particles move in a straight line until they collide with another particle or
the walls of the container.
3. These particles are much smaller than the distance between particles. Most of
the volume of a gas is therefore empty space.
4. There is no force of attraction between gas particles or between the particles
and the walls of the container.
5. Collisions between gas particles or collisions with the walls of the container are
perfectly elastic. None of the energy of a gas particle is lost when it collides
with another particle or with the walls of the container.
6. The average kinetic energy of a collection of gas particles depends on the
temperature of the gas and nothing else.
2009
State and explain Second Law of Thermodynamics. Prove that Clausius and
Kelvin-Plank
(b) A Carnot engine operates between the temperatures 850 K and 300 K.
The engine performs
1200 J of work each cycle, which takes 0.25 s. Calculate its efficiency and its
average power.
What are the rates of heat input and heat exhaust per cycle?
2010
Define Internal energy. State and explain First and Third laws of thermodynamics.
(14)
(b) What is a heat engine? Determine the efficiency of the engine if it takes
10,000 J of heat and
2011
Why does the boiling temperature of a liquid increase with pressure? A bubble of
5.0 mol of helium is submerged at a certain depth in liquid water when the water
bubble expands. How much heat Q is added to the helium during the expansion
and
temperature increase?
(3,7)
(b) Two blocks of copper, the mass m of each being 850 g, are put into thermal
contact
in an insulated box. The initial temperatures of the two blocks are 325 K and 285 K
and the constant heat c of capacity of copper is 0.386 J/g.K. What is the
final
2012
2013
Laws of thermodynamics. 10
2014
(b) Show that the entropy remains constant in a reversible process but increases in
an irreversible one.
2015
Discuss the applications of First Law of Thermodynamics. 6
2016
(8)
(6)
(6)
2017
statistical mechanics?
statistics.
(d) A 0.5m
1800 rpm. A force of 5.0N acts on the rim of the shaft. What would be the
(6)
(6)
(5)
(3) (20)
2018
Show that the entropy remains constant in a reversible process but increases in
an irreversible one. 6
When 20.9 J of heat was added as heat to a particular ideal gas, the volume of the
gas changed from 50 to 100 cubic centimeters while the pressure remained at 1
atm.
2019
Laws of thermodynamics 10
2020
No question