Chapter 4:
The Second Law of
Thermodynamics
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Chapter 4:
The Second Law of
Thermodynamics
The first law reflects the observation that energy is conserved, but it imposes no
restriction on the process direction.
The existence of restrictions, leads to constitutes the second law.
The difference between the two forms of energy, heat and work, provide insight
into the second law.
Work is transformed into other forms of energy: For example: EP by elevation of a
weight and EK by acceleration of mass of an object.
On the other hand, all efforts to devise a process for the continuous conversion of
heat completely into work or into mechanical or electrical energy have failed.
The fact is the flow of heat between two bodies always takes place from the hotter
to the cooler body, and never in the reverse direction.
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Chapter 4:
The Second Law of
Thermodynamics
Non-chemical reversibility and entropy
Non-chemical reversibility refers to processes in which heat or work
is transferred. For “reversibility” is focus on heat transfer. This is
because heat energy is always dissipated to the surroundings and
the universe at large, unlike the mechanical work. The term entropy
is described as “disorder” of a system, therefore it is defined as the
amount of heat transferred per temperature
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Chapter 4:
The Second Law of
Thermodynamics
The second law of thermodynamics
This law consider the entropy change for the system, the surroundings
in contact with the system, and the universe on the whole.
For a completely reversible process, qsystem = qsurroundings. Then, the change
in entropy of the universe is equal to zero. However, real process are
not irreversible, since it is impossible to completely manage where all
heat energy goes, so in general
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Chapter 4:
The Second Law of
Thermodynamics
The above inequality is a mathematical statement of the second
law of thermodynamics. For a truly reversible process, the
entropy change of the universe, due to that process, would be
zero. However, for real heat exchange is not completely
reversible, and the entropy of the universe always increases due
to the action of real processes.
The second law is expressed in two statements that describe
this restriction:
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Chapter 4:
The Second Law of
Thermodynamics
Statements of the second law
Statement 1: No apparatus can operate in such a way that its only effect (in system
and surroundings) is to convert heat absorbed by a system completely into work
done by the system.
Statement 2: No process is possible which consists solely in the transfer of heat
from one temperature level to a higher one.
NB: statement 1 does not mean that heat cannot be converted into work; only that
the process cannot leave both the system and its surroundings unchanged.
Statement 1a: It is impossible by a cyclic process to convert the heat absorbed by a
system completely into work done by the system.
The second law does not prohibit the production of work from heat, but it does
place a limit on how much of the heat directed into a cyclic process can be
converted into work done by the process. 6
Chapter 4:
The Second Law of
Thermodynamics
Entropy and Gibbs free energy (ΔG)
Let’s consider to included Gibbs free energy. The surroundings is
giving off or absorbing heat, and, now, related to the enthalpy change
of the system
; ΔH is the heat of reaction
Combine the entropy change of the universe in terms of the entropy
change of the system and surroundings
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Chapter 4:
The Second Law of
Thermodynamics
Gibbs free energy is defined as G = H – TS, therefore the change is
ΔG = ΔH – TΔS
Whether or not a reaction is spontaneous depends on the change in
the Gibbs free energy of the reaction. For a reaction in general, the
heat of reaction ΔH, and the entropy change associated with the
reaction ΔS are related to the spontaneity of the reaction. For ΔG < 0,
the reaction is spontaneous, while for ΔG > 0, the reaction will be non-
spontaneous.
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Chapter 4:
The Second Law of
Thermodynamics
The second law and heat engines
In practical the use of the second law of thermodynamics is in
the analysis of heat engines. A heat engine is essentially a device
which produces work, W, as a result of heat transferred Q
between an energy reservoir at a high temperature T H and an
energy reservoir at a lower temperature TC or produce work from
heat in a cyclic process.
For example: a steam power plant in which the working fluid
(H2O) periodically returns to its original state. This cycle consist of
the following steps:
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Chapter 4:
The Second Law of
Thermodynamics
1) Liquid water from a condenser is pumped into a boiler at elevated pressure.
2) Heat from a fuel is transferred in the boiler to the water, converting it to high
temperature steam at the boiler pressure.
3) Energy is transferred as shaft work from the steam to the surroundings by a
device like a turbine, in which the steam expands to reduce pressure and
temperature.
4) Exhaust steam from the turbine is condensed by transfer of heat to the
surroundings, producing liquid water for return to the condenser,
Therefore step 1 to 4 is the complete cycle process.
All heat engine cycles are absorption of heat into the system at a high T, rejection
of heat to the surroundings at lower T and production of work (W).
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Chapter 4:
The Second Law of
Thermodynamics
Heat engines, the two temperatures levels which characterize their operations are
maintained by heat reservoirs.
In operation, the working fluid of a heat engine absorbs heat from a hot reservoir
produces a net amount of work discards heat heat to a cold reservoir, and
returns to its initial state.
The thermal efficiency of the engine is defined as net work output/heat absorbed
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Chapter 4:
The Second Law of
Thermodynamics
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Chapter 4:
The Second Law of
Thermodynamics
Heat Engine
An operating in a completely reversible manner which is called a Carnot engine.
This device is called a Carnot engine. It was discovered by Nicolas Leonard Sadi
Carnot in 1824, in order to functions, this device operates in a cyclic manner
between several thermodynamics states
Reversible isothermal heat absorption QH and TH
Isentropic work output
Reversible isothermal heat rejection QC at TC
Isentropic work input
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Chapter 4:
The Second Law of
Thermodynamics
Step 1: A system at an initial T of a cold reservoir at TC undergoes a reversible
adiabatic process that causes its T to rise to that of a hot reservoir at TH.
Step 2: The system maintains contacts with the hot reservoir at TH and undergoes
a reversible isothermal process during which heat is absorbed from the hot
reservoir.
Step 3: The system undergoes a reversible adiabatic process in the opposite
direction of step 1 that brings its temperature back to the of the cold reservoir at
TC.
Step 4: The system maintains contact with the reservoir at TC and undergoes a
reversible isothermal process in the opposite direction of step 2 that returns it to
its initial state with rejection of heat to the cold reservoir.
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|𝑄 𝐻| 𝑇 𝐻
=
|𝑄 𝐶| 𝑇 𝐶
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Chapter 4:
The Second Law of
Thermodynamics
In reality, the heat transfer processes would have an associated entropy change,
which would result in the net entropy change of the universe being positive.
Therefore, an idealized heat engine model useful to analyze the limits of the real
heat engines, since no real engine can be more efficient that the Carnot engine
operating between the same reservoirs. The Carnot efficiency is defined as follow
in the equation.
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Chapter 4:
The Second Law of
Thermodynamics
As a result of this analysis is the statement that all reversible heat
engines operating between the same reservoirs have the same
efficiency. If the temperature is known for the reservoirs being
used for a heat engine, then, the maximum efficiency can be
determined for any heat engine operating those reservoirs. For
real heat engine, the efficiency will be less than the Carnot
efficiency.
Example 5.1
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Chapter 4:
The Second Law of
Thermodynamics
Entropy
Carnot engine can be written
If the heat quantities of the working fluid (rather than to the
heat reservoirs) the numerical value of QH is positive and that
QC is negative, therefore
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Chapter 4:
The Second Law of
Thermodynamics
For a complete cycle of a Carnot engine, the two quantities Q/T
associated with the absorption and rejection of heat by the
working fluid of the engine sum to zero. The working fluid of a
cyclic engine periodically returns to its initial state and its
properties such as temperature, pressure and internal energy
are return to their initial values. The characteristic of a Carnot
engine is that the sum of its changes is zero for complete cycle.
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Chapter 4:
The Second Law of
Thermodynamics
Each Carnot cycle has its own isotherm TH and TC and associated
heat quantities QH and QC as shown in above Figure. When the
adiabatic curves are so closely spaced that the isothermal steps
are infinitesimal, then the heat quantities become: dQH and dQC
TH and TC are absolute temperatures of the working fluid of the
Carnot engines and the traversed by the working fluid of the
cycle. Therefore, the summation of quantities dQ/T for the
Carnot engines leads to integral
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Chapter 4:
The Second Law of
Thermodynamics
“rev” indicates that the cycle is reversible. The quantities dQrev/T sum to
zero for the arbitrary cycle, exhibiting the characteristic of a property.
The existence of a property whose differential changes for the arbitrary
cycle are given by these quantities is called entropy and its differential
changes, then
Where St is the total molar entropy of the system, alternatively
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Chapter 4:
The Second Law of
Thermodynamics
Entropy changes of an ideal gas
For one mole or a unit mass of fluid undergoing a mechanically reversible
process in a closed system, the first law becomes
dU = dQrev – PdV
Differentiation of the defining equation for enthalpy, H = U + PV, yield to
dH = dU + PdV + VdP
Eliminating dU: dH = dQrev – PdV + PdV + VdP
dH = dQrev – VdP
Then, dQrev = dH – VdP
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Chapter 4:
The Second Law of
Thermodynamics
dQrev = dH – VdP
For an ideal gas, and , then substitutions
dQrev = – dP
divide by T
As a results
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Chapter 4:
The Second Law of
Thermodynamics
Or divide by R
Integrate from an initial state at conditions T0 and P0 to a final
conditions T and P gives. This is a derivation of molar entropy, (S)
of an ideal gas
𝑇 𝑖𝑔
Δ𝑆 𝐶 𝑑𝑇 𝑃
=∫
𝑃
−𝑙𝑛
𝑅 𝑇 𝑅 𝑇0
𝑃0
Example 5.2 26
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Chapter 4:
The Second Law of
Thermodynamics
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Chapter 4:
The Second Law of
Thermodynamics
Mathematical statement of the second law
Consider two heat reservoirs, one at temperature TH and a second at
the lower TC. Let a quantity of heat |Q| be transferred from hotter to
the cooler reservoir. The entropy changes of the reservoirs at TH and at
TC are
These two entropy changes are added to give
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Chapter 4:
The Second Law of
Thermodynamics
Because TH > TC, the total entropy change as a result of this irreversible
process is positive. Also, ΔStotal becomes smaller as the difference TH – TC
gets smaller. When TH is only infinitesimally higher than TC, the heat
transfer is reversible and ΔStotal approaches zero. Therefore, for the
process of irreversible heat transfer, ΔStotal is always positive, approaching
zero as the process becomes reversible.
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Chapter 4:
The Second Law of
Thermodynamics
Consider now an irreversible process in a closed system wherein no
heat transfer occurs as presented on the PV diagram, which shows an
irreversible, adiabatic expansion of 1 mol of fluid from an initial
equilibrium state at point A to final equilibrium state at point B.
The original irreversible process and the reversible restoration process
constitute a cycle for which ΔU = 0 and for which the work is
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Chapter 4:
The Second Law of
Thermodynamics
According to the statement 1 of the second law, Qrev cannot be directed into the system for
the cycle would then be a process for the complete conversion into work of the heat
absorbed. Therefore, is negative and it follows that S A – SB is also negative, hence SB > SA.
Because the original irreversible process is adiabatic (ΔS surr = 0), the total entropy change of
the system and surroundings as a result of the process is ΔS total = SB – SA > 0.
Therefore, the same result were found for adiabatic process for direct heat transfer: ΔS total
is always positive as approaching zero a limit when the process becomes reversible. The
can conclude that for any process is leading to the general equation
ΔStotal > 0
NB: This is the mathematical statement of the second law affirms that every process
proceeds in such a direction that the total entropy change associated with it is positive, the
limiting value of zero being attained only by a reversible process. No process is possible for
which the total entropy decreases
Example 5.4
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Chapter 4:
The Second Law of
Thermodynamics
Entropy balance for open systems
Entropy is not conserved, the second law states that the total entropy change
associated with any process must be positive, with a limiting value of zero a
reversible process. This requirement is taken into account by writing the entropy
balance both the system and its surrounding and including an entropy generation
term to account for the irreversibility of the process, thus
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Chapter 4:
The Second Law of
Thermodynamics
The third is the time rate of change of the entropy of the surroundings,
resulting from heat transfer between system and surroundings.
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Chapter 4:
The Second Law of
Thermodynamics
For a steady state flow process the mass and entropy of the fluid in
the control volume are constant, and is zero
In addition, if one entrance and one exit with for both streams is the
same then,
Example 5.5
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Chapter 4:
The Second Law of
Thermodynamics
Calculation of ideal work
In any steady state flow process requiring work, then
there is an absolute minimum amount which must be
expended and maximum amount which may be
accomplished as the result of a given change of state of
the fluid flowing through the control volume. The limiting
value obtains when the change of state associated with
the process is accomplished completely reversibly. Then,
for such process, the entropy generation is zero
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Chapter 4:
The Second Law of
Thermodynamics
The energy balance for steady state flow process (Chapter 2), the
only work in the process is shaft work and the general energy
balance, becomes
The shaft work, , is a work for completely reversible process. Then, is
called ideal work,
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Chapter 4:
The Second Law of
Thermodynamics
In most application to chemical process, the kinetic and potential
terms are negligible
For the special case of a single stream flowing through the control
volume, the terms may be expressed as rates or upon division by on
the basis of unit amount of fluid flowing through the control volume.
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Chapter 4:
The Second Law of
Thermodynamics
For thermodynamic efficiency for work required
For thermodynamic efficiency for work produced
Example 5.7
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Chapter 4:
The Second Law of
Thermodynamics
Lost work
Work that is wasted as the result of irreversibilities in a process is called
lost work, Wlost, and defined as the difference between the actual work
of a process and ideal work for the process.
From energy balance equation,
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Chapter 4:
The Second Law of
Thermodynamics
Therefore, substituting for and
For the case of a single surroundings temperature,
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Chapter 4:
The Second Law of
Thermodynamics
Multiple by
Therefore
As a consequence of the second law, . When a process is completely
reversible, the equality holds and . For irreversible process the
inequality holds, and , the energy that becomes unavailable for work, is
positive.
Example 5.9
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Chapter 4:
The Second Law of
Thermodynamics
The third law of thermodynamics
Measurements of heat capacities at very low temperatures provide data for the calculation
from the equation below of entropy change down to 0K.
When these calculations are made for different crystalline forms of the same
chemical species, the entropy at 0K appears to be the same for all forms. When
the form is non-crystalline, e.g., amorphous or glassy, calculation show that the
entropy of the more random form is greater than that of the crystalline form,
that’s leads to defined the third law of thermodynamics, which it stated that the
absolute entropy is zero for all perfect crystalline substances at absolute zero
temperature. When T = 0 as the lower limit of integration, the absolute entropy
of a gas at temperature T is based on calorimetric data
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Chapter 4:
The Second Law of
Thermodynamics
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Chapter 4:
The Second Law of
Thermodynamics
Tutorial Section
Tuesday 11h00 to 12h00
Contact: Dr Mbuyu Ntunka
Email: mbuyun@[Link]
NB: Attempt All tutorials and problems in the text book first before
meet the Tutor
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Aim and Objectives
Evaluate the photocatalytic activity of a locally produced TiO2
pigment on the degradation of bacteria in river water for potable
water purposes and hence optimize the process. The specific
objectives are as follows:
Evaluate the photocatalytic activity of the mTiO2 on degradation of
organics in river water to produce clean water.
Optimize process parameters of temperature, starting pH of the
solution and mTiO2 loading on the degradation of bacteria in river
water.
Investigate the percentage removal of mTiO2 and bacteria in treated
water using a Polyester Woven Microfiltration Membrane (PEWMM).
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