Renewable Energy

Lecture 2
First and Second Laws of Thermodynamics

MECH 4390, Instructor: Dr. Evgeny Shafirovich

Forms of Energy

• Energy can exist in numerous forms.

• Their sum constitutes the total energy, E, of a system.
• Macroscopic forms of energy:
 Kinetic energy, KE: The energy that a system possesses as a result of its motion relative
to some reference frame.
 Potential energy, PE: The energy that a system possesses as a result of its elevation in a
gravitational field.
• Microscopic forms of energy: Related to the molecular structure of a system
and the degree of the molecular activity.
 Internal energy, U: The sum of all the microscopic forms of energy.

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Forms of Internal Energy

• Sensible energy: associated with the kinetic energies

of the molecules.
• Latent energy: associated with the phase of a system.
• Chemical energy: associated with the atomic bonds in
a molecule.
• Nuclear energy: associated with the strong bonds
within the nucleus of the atom.

Thermal = Sensible + Latent

Internal = Sensible + Latent + Chemical + Nuclear

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Energy Transfer by Heat and Work

• Heat: The form of energy that is transferred between two systems

(or a system and its surroundings) by virtue of a temperature
difference.
• Work: The energy transfer associated with a force acting through a
distance (a rising piston, a rotating shaft, an electric wire crossing
the system boundaries… )
• The difference between heat transfer and work: An energy
interaction is heat transfer if its driving force is a temperature
difference. Otherwise it is work.

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The First Law of Thermodynamics

• Conservation of energy: Energy can be neither created nor destroyed

during a process; it can only change forms.
• The net change in the total energy of the system during a process is equal
to the difference between the total energy entering and the total energy
leaving the system during that process.

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Energy Change of a System, ∆Esystem

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Mechanisms of Energy Transfer, Ein and Eout

• Closed system:
 Heat, Q
 Work, W

• Control volume:
 Heat, Q
 Work, W
 Mass flow, m

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Energy Balance for a Closed System

Sign convention:

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Flow Work

Flow work: required to push the mass into or out of the control volume;
is necessary to maintain a continuous flow through a control volume.

Enthalpy: h = u + Pv

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Energy of a Flowing Fluid

Enthalpy: h = u + Pv

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Energy Transport by Mass

When KE and PE are negligible:

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Energy Balance for a Steady-flow System

With sign convention:

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The Second Law of Thermodynamics

Processes occur in a certain direction,

and not in the reverse direction.

• The 2nd law deals with

 Direction of processes
Coffee does not get hotter
 Allows us to assign quality to energy in a cooler room.
 Useful for determining theoretical limits for
performance of engineering systems

• All processes satisfy both the 1st and 2nd laws.

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Thermal Energy Reservoirs

• Thermal energy reservoir is a body that can

absorb or reject a finite amount of thermal
energy without any change in temperature.
• Examples: oceans, lakes, rivers,
atmospheric air (large thermal energy
capacity)
• Another example: a two-phase system
• Source vs sink

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Heat Engines

The devices that convert heat to work.

1. They receive heat from a high-temperature source (e.g.,

furnace, solar energy).
2. They convert part of this heat to work (e.g., a rotating shaft).
3. They reject the remaining waste heat to a low-temperature
sink (e.g., atmosphere).
4. They operate on a cycle.

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Thermal Efficiency

• Net work output of engine is always less than the amount of heat input.
• Only part of heat transferred to heat engine is converted to work.

Desired output
Performance =
Required input

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The Second Law of Thermodynamics:
Kelvin–Planck Statement

It is impossible for any device that operates

on a cycle to receive heat from a single
reservoir and produce a net amount of work.

• No heat engine can have a thermal efficiency of 100%.

• Heat engine must reject heat.
• The impossibility of having a 100% efficient heat engine
is NOT due to friction or other dissipative effects.

Impossible!!!

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Refrigerators and Heat Pumps

• The transfer of heat from a low-temperature medium to a high-

temperature medium requires a special device called a refrigerator
or a heat pump.

• Refrigerators and heat pumps, like heat engines, are cyclic devices.

• Working fluid called refrigerant.

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Objective of a Refrigerator

• The objective of a refrigerator is to remove heat (QL)

from the refrigerated space.
• To accomplish this, it requires work input.
• The efficiency of a refrigerator is expressed in terms of
the coefficient of performance (COP).

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Objective of Heat Pump

• The objective of a heat pump is to add heat (QH)

to a heated space.
• To accomplish this, it requires work input.
• The same cycle as for a refrigerator

for fixed values of QL and QH

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The Second Law of Thermodynamics:
Clausius Statement

It is impossible to construct a device

that operates in a cycle and produces
no effect other than the transfer of heat
from a lower-temperature body to a
higher-temperature body.

Impossible!!! 21
 Equivalence of the Two Statements

Violation of Kelvin–Planck statement leads to violation of Clausius statement.

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 Perpetual-motion Machines

A perpetual-motion machine that

violates the second law (PMM2)
A perpetual-motion machine that violates the first law (PMM1)

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Reversible and Irreversible Processes

• Reversible process: A process that can be

reversed without leaving any trace on the
surroundings.
• Irreversible process: A process that is not
reversible.
• All the processes occurring in nature are
irreversible.
• But reversible processes:
 Easier to analyze
 Serve as idealized models to which actual
processes can be compared Two familiar reversible
 Deliver most work; require least work processes

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Irreversibilities

• The factors that cause a process to be irreversible

are called irreversibilities:
 friction
 unrestrained expansion
 mixing of two fluids
 electric resistance
 inelastic deformation of solids
 chemical reactions
 heat transfer across a finite temperature difference

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Friction renders a Irreversible compression Irreversible heat transfer across
process irreversible. and expansion processes a finite temperature difference

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Internally and Externally Reversible Processes

• Internally reversible process: If no

irreversibilities occur within the boundaries
of the system during the process (e.g.,
quasi-equilibrium).
• Externally reversible: If no irreversibilities
occur outside the system boundaries (e.g.,
heat transfer through infinitesimal dT).
• Totally reversible process: It involves no Totally reversible process
irreversibilities within the system or its
surroundings.

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• Heat transfer through a differential temperature difference dT can be
considered to be reversible.

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The Carnot Cycle

Nicolas Léonard Sadi

Carnot
1796 – 1832

• Reversible Isothermal Expansion (process 1-2, TH = constant)

• Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TL)
• Reversible Isothermal Compression (process 3-4, TL = constant)
• Reversible Adiabatic Compression (process 4-1, temperature rises from TL to TH) 29
P-V diagram of the Carnot cycle

• Area under process curve on P-V diagram

represents boundary work for quasi-equilibrium
(internally reversible) processes.
• Area under 1-2-3 is work done by expanding gas.
• Area under 3-4-1 is work done to compress gas.
• Area enclosed by cycle path (1-2-3-4-1) is the net
work.

Carnot cycle
(Carnot heat engine cycle)

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The Reversed Carnot Cycle

Carnot cycle Reversed Carnot cycle

(Carnot heat engine cycle) (Carnot refrigerator cycle)
• Reverse directions of heat and work
interactions
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The Carnot Principles

1. The efficiency of an irreversible

heat engine is always less than the
efficiency of a reversible one
operating between the same two
reservoirs.

2. The efficiencies of all reversible

heat engines operating between the
same two reservoirs are the same.

The violation of either statement leads to the violation of the second law.
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The Thermodynamic Temperature Scale

• Independent of properties of substances that are used to measure

temperature.
• Recall 2nd Carnot principle says all reversible heat engines (RHEs)
have same efficiency operating between same two reservoirs.
• So efficiency of RHEs is independent of working fluid, its properties,
details of cycle and engine.
• Since energy reservoirs are characterized by their temperature,
thermal efficiency of RHE is only function of reservoir temperatures.

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ηth ,rev = g (TH , TL )
QH φ (TH )
= f (TH , TL )
QH
or =
QL QL φ (TL )
φ (T ) = T
 QH  TH
  = William Thomson
 QL  rev TL (Lord Kelvin)
1824 − 1907

• For reversible cycles, the heat transfer ratio QH /QL can

be replaced by the absolute temperature ratio TH /TL.

• This temperature scale is called the Kelvin scale, and

the temperatures on this scale are called absolute
temperatures.

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• The magnitude of a Kelvin is defined
as 1/273.16 of the temperature
interval between absolute zero and
the triple point temperature of water.

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The Carnot Heat Engine

The Carnot heat engine is the most efficient

of all heat engines operating between the
same high- and low-temperature reservoirs.

Any heat engine:

Carnot heat engine:

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No heat engine can have a
higher efficiency than a
reversible heat engine operating
between the same high- and
low-temperature reservoirs.

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The Quality of Energy
• Effect of source temperature on efficiency:
More of the high-temperature thermal
energy can be converted into work.
• The higher the temperature, the higher the
quality of the energy.

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The Carnot Refrigerator and Heat Pump

Any refrigerator or heat pump:

Carnot refrigerator or heat pump:

No refrigerator can have a higher COP

than a reversible refrigerator operating
between the same temperature limits. 39