Instructor: Eyerus Mulugeta
Thermodynamics I Outline FMSE
Chapter Subjects
1 Introduction
2 Fundamental concepts
3 Internal Energy and Entropy
4 Auxiliary Functions and
Thermodynamic Potentials.
Enthalpy Change(∆H)
• For a substance of fixed composition ,the enthalpy change with
change in temperature at constant pressure P can be calculated as
follows: From that definition;
On integration from Tl to T2,
• The enthalpy change associated with a chemical reaction or phase
change at constant pressure and temperature can be calculated from
the enthalpy of each species involved in the process.
• When species A under goes the phase transformation from α to β,
• The enthalpy change due to chemical reaction (∆H) is the difference
between the sum of enthalpies of the products and the sum of
enthalpies of the reactants :
The additive properties of enthalpy is known as Hess's Law. According to this law;
• The enthalpy change associated with a given chemical reaction is the same
whether it takes place in one or several states.
• Enthalpy is a state function, meaning it depends only on the initial and final
states, not on the path taken.
• Enthalpies or enthalpy changes may be added or subtracted in parallel with the
same manipulations performed on their respective components or reactions.
Second Law of Thermodynamics
• In any natural (spontaneous) process, the total entropy of an isolated
system always increases.
• Common Statements of the Second Law
– Heat always flows spontaneously from higher to lower temperature
systems, and never the reverse.
– It is impossible to convert all heat from a heat source completely into
work without losses.
– Wood will burn spontaneously in air if ignited, but the reverse process,
i.e., the spontaneous recombination of the combustion products to
wood and oxygen in air, has never been observed in nature.
Reversible and Irreversible Processes
• A process, which involves the spontaneous change of a system
from a state to some other state, is called spontaneous or natural
process. As such a process cannot be reversed without help of an
external agency, the process is called an irreversible process.
• The equilibrium state is a state of rest. Once at equilibrium, a
system will not move away from equilibrium unless some
external agency (the surroundings) acts on it. A process
during which the system is never away from equilibrium is
called a reversible process.
• A reversible process proceeds with an infinitesimally small
driving force in such a way that the system is never more
than an infinitesimal distance from equilibrium, a condition
which is virtually indistinguishable from equilibrium, then the
process can be regarded as a reversible process. Thus a
reversible process is infinitely slow.
Entropy (s )
What is entropy?
To answer this question, we need to consider the degradation of a system.
There are two distinct types of spontaneous process:
• Conversion of work or mechanical energy in to heat, and
• Flow of heat from higher to lower temperature systems.
First consider the degradation of mechanical energy of the following system : Now
the system is at equilibrium and the piston does not move in either direction
• If the external pressure is suddenly decreased by dP, the piston
moves out due to the pressure imbalance.
• The volume inside the cylinder expands and the internal pressure
decreases.
• Water vaporises and heat flows from the reservoir because the
vaporisation is endothermic.
• After one mole of water has vaporised, the external pressure is
restored to its original value, PO and thus equilibrium is restored.
• In the process described above, the system (cylinder) pressure of
PO- dP. The amount of work done is
where V = molar volume of water vapour
In the irreversible process, however, the amount of work the system does, w, is
less than its maximum capacity. Where has the rest of the capacity gone?
The mechanical energy of (wmax- w) has been degraded to thermal energy
(heat)in the system (cylinder).
• In summary,
• The fact that less heat enters from the surroundings in the irreversible process than in
the reversible process is due to the heat produced by the degradation of work in the
irreversible process.
• Therefore an irreversible process is one in which the system is degraded during the
process. The extent of degradation, however, differs from process to process. This
suggests that there exists a quantitative measure of the extent of degradation, or degree
of irreversibility, of a process.
The degree of irreversibility is related to temperature(T) and the
amount of heat (q).
– The more the heat flow, the higher the degree of
irreversibility.
– The lower the temperature of the body to which heat flows,
the higher the degree of irreversibility.
Therefore,
Example:
Each of these processes is spontaneous and hence irreversible. Therefore
degradation occurs in each process.
Path1 = path2 + path3
Degradation in Path 1> Degradation in Path 2,
Degradation in Path 1> Degradation in Path 3.
Path 1 is more irreversible than either Path 2 or Path 3.
• Now we define a new thermodynamic function, S ,called
entropy, as
• The entropy change(∆S) is the measure of the degree of
irreversibility of a process. The total entropy change
associated with the process consists of two terms :
– Entropy change of the system : ∆s sys
– Entropy change of the surroundings : ∆S , sur
• Recall that the total heat appearing in the system is the sum of
heat entering from the surroundings(q) and heat produced by
degradation due to irreversibility(qr - q) :
The total heat leaving the surroundings is q :Negative sign is due to heat loss
of the surroundings.
What is entropy?
• Change in entropy measures the degree of irreversibility of a
process, or the capacity for spontaneous change of a process.
• Entropy is not directly measurable. But entropy changes are
calculated from measurable quantities such as temperature,
pressure, volume and heat capacity.
• Entropy increases in all irreversible, spontaneous or natural
processes.
• Entropy is ameasure of “mixed-up-ness” or “ disorderness ” of
a system
• Unlike internal energy (U) or enthalpy (H), entropy has its
absolute value.
Example 1
If one mole of a perfect gas undergoes an isothermal process, is ∆S
independent of pressure?
The entropy change depends on the pressure change. This equation
tells us that as the pressure is raised the entropy of a gas decreases:
i.e., molecules in the gas become more ordered.
Example 2
When a system undergoes a process at a constant pressure, does
the entropy change depend on the temperature?
This equation tells us that the entropy of a substance held at
constant pressure increases when the temperature increases.
Example 3
Example 4
Prove the following statement : An isothermal change in phase (phase
transformation) of a substance produced by input of energy as heat
always leads to an increase in the entropy of the substance.
Criterion of Equilibrium
When a system is left to itself, it would either
Move spontaneously to some
Remain unchanged in its
other state
initial state If this is the case, the system
is initially
If this is the case,the
in a non-equilibrium state.
initial state is the The system will
equilibrium state. spontaneously move
to the equilibrium state .
Note
• All real processes involve some degree of
irreversibility and thus all real processes lead to an
increase in the total entropy.
• The total entropy can never decrease. It can only
increase.
• A process will cease to proceed further, if the total
entropy has reached its maximum.
Heat Engines
• A heat engine is a device for converting heat into work. (e.g., steam
engine, internal combustion engine) The following figure is the
schematic representation of a heat engine.
• Each cycle takes heat from the high
temperature reservoir :q2,
• use some of it to generate work :w,
• and rejects unused heat to the cold
reservoir : q1.
What is the maximum amount of work that can be obtained per cycle
from the heat engine?
• The maximum work we can obtain from the operation of a heat
engine is that generated when all the processes are reversible, since
there is no degradation of work in a reversible process.
The Carnot cycle is the operation of an idealised (reversible) engine
in which heat transferred from a hot reservoir, is partly converted into
work, and partly discarded to a cold reservoir.
This is remarkable result tells the efficiency depends only on the
temperatures of the reservoirs.
Example 5
A Carnot engine can be run in reverse and used to transfer energy
as heat from a low temperature reservoir to a high temperature
reservoir. The device is called a heat pump, if it is used as a heat
source, or a refrigerator, if it is used to remove heat. Prove that in
the latter case work must be done on the engine.
Quiz
1. State second law of thermodynamics.(2)
2. What is entropy?(2)
3. Change in entropy measures the degree of
irreversibility. T/F(1)