MPEN 227: THERMODYNAMICS 1 By H.

Tarus

Basic Concepts of Thermodynamics

Thermal Sciences
The thermal sciences involve the storage, transfer and conversion of energy.

IMPORTANT QUESTIONS ABOUT ENERGY:

• how is energy stored in matter?

– kinetic energy (flywheels, windmills) and gravitational potential (hydroelectric
dams)
• how is energy exchanged between a system and its surroundings?
– work, heat transfer
• how is energy transformed or converted?
– chemical → electrical or mechanical (fuel cells and automotive engines)
– phonons → electric (photovoltaics) or thermal (solar panels)
– nuclear → electric (fission reactors)

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 windmills
hydroelectric
(kinetic energy)
(gravitational potential)

automotive engine
(chemical conversion)
solar energy
(photo-thermal conversion)

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We will study the basic laws and principles that govern the three disciplines of thermal sciences,
namely, thermodynamics, heat transfer and fluid mechanics.

Thermodynamics Heat Transfer

Conservation of mass Conduction
Conservation of energy Convection

ics
Second law of thermodynamics Radiation

am
Properties Conjugate

He
n

at
dy

Tr
mo

an
er Thermal

sfe
Th
Systems

r
Engineering

Fluids Mechanics

Fluid Mechanics
Fluid statics
Conservation of momentum
Mechanical energy equation
Modeling

Thermodynamics: the study of energy, energy transformations and its relation to matter. The anal-
ysis of thermal systems is achieved through the application of the governing conservation
equations, namely Conservation of Mass, Conservation of Energy (1st law of thermodynam-
ics), the 2nd law of thermodynamics and the property relations.

Heat Transfer: the study of energy in transit including the relationship between energy, matter,
space and time. The three principal modes of heat transfer examined are conduction, con-
vection and radiation, where all three modes are affected by the thermophysical properties,
geometrical constraints and the temperatures associated with the heat sources and sinks used
to drive heat transfer.

Fluid Mechanics: the study of fluids at rest or in motion. While this course will not deal exten-
sively with fluid mechanics we will be influenced by the governing equations for fluid flow,
namely Conservation of Momentum and Conservation of Mass.

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Thermodynamics

Whenever there is an interaction between energy and matter, thermodynamics is involved.

The following common thermodynamic systems are just a few examples of forms of energy con-
version in everyday life.

Given Energy −→ Thermodynamic −→ Desired Energy

Form System Form

Chemical, Solar,
N uclear, Kinetic (W ind), −→ P owerP lant −→ Electricity
P otential (Hydroelectric)

Chemical (gas) −→ V ehicle −→ M otion

Chemical (f ood) −→ Human −→ M otion

Instead of tracking the movement of matter and energy on a particle by particle basis (microscopic
approach), classical thermodynamics uses a macroscopic approach where we use the conservation
equations (energy and mass) to track movement on an average over a fixed domain.

Matter

• consists of small fundamental particles (protons, neutrons and electrons)

fundamental particles → ≈ 103 different atoms → millions of molecules

• to get a physical sense about the size and number of molecules in matter, consider the fol-
lowing:

– number molecules in 1 cm3 of liquid water is 3.37 × 1022

– number molecules in 1 cm3 of air is 2.67 × 1019
– during evaporation, if 1 million (106 ) molecules were released each second, it would
take 3.36 × 1013 seconds (5.6 × 1011 minutes, 9.4 × 109 hours, 5.6 × 107 weeks,
1.1 × 106 years) to evaporate 1 mm3 of water.
– realistically, 1 mm3 of water will evaporate in about 1 minute (5.6×1017 molecules/second)

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 • using the classical approach, what we see as the behavior of materials is actually the behavior
of a large molecular population

Energy

• energy can be either random or non-random (directed)

Principal Forms Formulation

Potential non-random mgz

Kinetic non-random mV 2 /2
Elastic Strain Energy non-random
Electrical non-random
Thermal Energy random U
Chemical Energy random
Radiant Energy non-random or random
Nuclear Energy random

• most of the available energy resources are of the random type

• the total energy of the system per unit mass is denoted as e and is given as


E kJ
e=
m kg

• thermodynamics deals almost exclusively with the change in energy between states, ∆e

• it does not provide any information regarding the absolute value of energy

• if we neglect the contributions of magnetic, electric, nuclear energy, we can write the total
energy as

mV 2
E = U + KE + P E = U + + mgz
2
V2
e = u+ + gz (per unit mass)
2

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Dimensions and Units
Dimensions
• all physical quantities have dimensions (and a physical quantity is described by its dimen-
sions)

• dimensions can be primary (fundamental) or secondary (derived)

Primary Dimensions:
mass, m
length, L
time, t,
temperature, T
Secondary Dimensions:
velocity, L/t
acceleration, L/t2
force, m · L2 /t2
energy, m · L2 /t2 .
we will also examine u, h, s, Cp, Cv

Units

• units are used to quantify and measure the dimensions

• while there are currently two main systems in use, we will use SI units exclusively

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SI: International System
– SI is the prefered because it is logical (base 10) and needs no correction factors
– unit convention:

Parameter Units Symbol

length, L meters m
mass, m kilograms kg
time, t seconds s
temperature, T kelvin K
velocity, V meter per second, ≡ L/t m/s
acceleration, a meter per second squared ≡ L/t2 m/s2
force, F newton, ≡ m · L/t2 N
energy, E joule ≡ m · L2 /t2 J

Note: 1 N = 1 kg · m/s2
1J = 1N · m = 1 kg · m2 /s2
gc = 1 kg · m/N · s2

IP (USCS): Inch-pound or US Customary System

– USCS needs correction factors and conversions are arbitrary
– unit convention:

Parameter Units Symbol

length, L feet ft
mass, m pounds mass lbm
time, t seconds s
temperature, T Rankine R
velocity, V feet per second, ≡ L/t f t/s
acceleration, a feet per second squared ≡ L/t2 f t/s2
force, F pounds force, ≡ m · L/t2 lbf
energy, E British thermal units ≡ m · L2 /t2 Btu

Note: 1 Btu = 778.2 lbf · f t

1 ton = 12000 Btu/hr
gc = 32.174 lbm · f t/lbf · s2

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Thermodynamic Systems

Isolated Boundary

Surroundings

W ork

at Surroundings
He
System - everything that interacts
with the system

System Boundary System

(real or imaginary - may be as simple
fixed or deformable) as a melting ice cube
- or as complex as a
nuclear power plant

SYSTEM:

• any specified collection of matter under study.

• all systems possess properties like mass, energy, entropy, volume, pressure, tempera-
ture, etc.
• systems may be fixed in space or moving
• the system boundary may be real or imaginary, fixed or deformable
• thermodynamic systems are classified as either open or closed
Closed System: composed of a control (or fixed) mass where heat and work can cross
the boundary but no mass crosses the boundary.
Open System: composed of a control volume (or region in space) where heat, work,
and mass can cross the boundary or the control surface

WORK & HEAT TRANSFER:

• thermodynamics deals with the properties of matter as a system interacts with its sur-
roundings through work and heat transfer
• work and heat transfer are NOT properties → they are the forms that energy takes to
cross the system boundary

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Types of Systems

Surroundings (environment, ambient): Everything that interacts with the system under consider-
ation

Control Mass: The specified matter under consideration

Control Volume: The specified space under consideration

Closed System: A control mass that does not transfer mass to the surroundings

Open System: A control volume that can transfer both energy and mass with the surroundings

General System: A closed or open system that communicates with the surroundings by heat or
work

Isolated System: A closed system that does not communicate with the surroundings by any means

Rigid System: A closed system that communicates with the surroundings by heat only

Adiabatic System: A closed or open system that does not transfer energy with the surroundings
by heat

weights
by-pass flow
g fan
piston

gas
system engine core
boundary

Closed System Open System

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Choosing an Appropriate System Boundary
Isolated system (one that does not interact with its surroundings)

• assume to be perfectly insulated −→ adiabatic

• select the outer boundary as the surface of the control volume

• the piston is held in place with a pin in state 1

• when the pin is released the spring expands and the gas is compressed

a 1st law balance gives:

E1 + W1−2 − Q1−2 = E2

Since no work or heat transfer crosses the system boundary, W1−2 = Q1−2 = 0, therefore

E1 = E2

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Non-isolated system (choose the gas as our system)

• assume to be perfectly insulated −→ adiabatic

• select the region containing the gas as the surface of the control volume

• the piston is held in place with a pin in state 1

• when the pin is released the spring expands and the gas is compressed

a 1st law balance gives:

E1 + W1−2 − Q1−2 = E2

but only Q1−2 = 0, and

E1 + W1−2 = E2

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Thermodynamic Properties of Systems

Basic Definitions

Thermodynamic Property: Any observable or measurable characteristic of a system. Any math-

ematical combination of the measurable characteristics of a system

Intensive Properties: Properties which are independent of the size (or mass) of the system

• they are not additive ⇒ XA+B = XA + XB

• examples include: pressure, temperature, and density

Extensive Properties: Properties which are dependent of the size (or mass) of the system

• they are additive ⇒ XA+B = XA + XB

• examples include: volume, energy, entropy and surface area

Intensive Properties

Pressure P N/m2 or P a
Temperature T K
Extensive Properties

Volume V m3
Mass m kg
Other Properties (Intensive and Extensive)

Specific VolumeA V /m = v m3 /kg

Density ρ = 1/v = m/V kg/m3
Total EnergyB E/m = e J/kg
Internal EnergyB U/m = u J/kg
EnthalpyB H/m = h = u + P v J/kg
EntropyB S/m = s J/kg · K
Specific Heat Cp, Cv J/kg · K
Ideal Gas Constant R = Cp − Cv J/kg · K

A
Notes: The term “specific” denotes that the property is independent of mass.

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 There are two exceptions:

1) specific gravity (or relative density) is given where:

ρs = ρ/ρH2 O and ρH2 O is 1000 kg/m3 .
2) specific weight is weight per unit volume
(i.e. W/V = mg/V = ρg = γ)

B
The given internal energy, enthalpy and entropy are specific properties.
The term “specific” is dropped.

Internal Properties: Properties which are related to the internal structure of a system

External Properties: Properties which are measured with respect to an external reference, i.e.
ambient conditions such as T0 and P0

Specific Properties: Extensive properties expressed per unit mass to make them intensive prop-
erties
extensive property
• specific property (intensive) −→
mass
Example: Specific volume, v:

V
v=
m

Vtotal = m
 A
v + mB
 A
v
 B
=VA =VB

• Entropy is an extensive property with the dimensions of energy/temperature

J
S:
K

S = SA + SB

= m A sA + m B sB

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Measurable Properties

• P, V, T, and m are important because they are measurable quantities. Many other thermo-
dynamic quantities can only be calculated and used in calculations when they are related to
P, V, T, and m

– Pressure (P ) and Temperature (T ) are easily measured intensive properties.

Note: They are not always independent of one another.
– Volume (V ) and mass (m) are easily measured extensive properties

Pressure

F orce N
• P ressure = ; → ≡ Pa
Area m2
– in fluids, this is pressure (normal component of force per unit area)
– in solids, this is stress

1 kP a = 103 P a : 1 M P a = 106 P a

1 bar = 105 P a : 1 atm = 101, 325 P a

Pressure

gauge
pressure
Patm absolute
vacuum
pressure
pressure ABSOLUTE
ATMOSPHERIC
absolute PRESSURE
vacuum pressure

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• gauge pressure = absolute pressure - atmospheric pressure

Pgauge = Pabs = Patm when Pabs > Patm

• vacuum pressure

Pvac = Patm = Pabs when Pabs < Patm

• in thermodynamics calculations, always absolute pressure

• most pressure measuring devices are calibrated to read zero in the atmosphere (they measure
Pgauge or Pvac ). Be aware of what you are reading!

• Manometer a device that measures pressure using a column of liquid

– the cross sectional area of the tube is not important

– the manometer measures gauge pressure
– ρg (kg/m2 s2 ) and is called the specific gravity

– the fluid pressure at any point, 1 in a manometer is given as

P1 = Patm + ρgh

• Bourdon Tube a device that measures pressure using mechanical deformation

• Pressure Transducers devices that use piezoelectrics to measure pressure

– very accurate and robust

– can measure from 10−6 to 105 atm
– can measure Pgauge or Pabs

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• Barometer device that measures atmospheric pressure

– it is (basically) a manometer with a near vacuum on one end

– atmospheric pressure = barometric pressure
– Patm = ρgh, changes with elevation and weather

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Temperature

• temperature is a pointer for the direction of energy transfer as heat

TA > TB TA < TB
Q Q
TB TB
TA TA

It follows that temperature is a property two systems have in common when they are in
thermal equilbrium with each other

Thermal Equilibrium: TA = TB and Q=0

0th Law of Thermodynamics: if system C is in thermal equilibrium with system A,

and also with system B, then TA = TB = TC

• two bodies are in thermal equilibrium if they have the same temperaure, even if they are not
in contact with one another
• the 0th law makes a thermometer possible

C
TA = TC C TB = TC

A
B

TA = TB

• in accordance with the zeroth law, any system that possesses an equation of state that relates
T to other accurately measurable properties can be used as a thermometer
e.g. an ideal gas obeys the equation of state
PV
T =
mR

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• experimentally obtained Temperature Scales The Celsius and Fahrenheit Scales are based
on the melting and boiling points of water

• conventional thermometry depends on material properties (e.g. mercury expands with T in

a repeatable and predictable way)

• thermodynamic Temperature Scales (independent of the material) The Kelvin and Rankine
scales are determined using a constant volume gas thermometer

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State and Equilibrium
• the state of a system is its condition as described by a set of relevant energy related properties.

• thermodynamic equilibrium referes to a condition of equilibrium with respect to all possible

changes in a given system.

Definitions

Thermodynamic State: The condition of a thermodynamic system (as determined by its proper-
ties)

Equilibrium State: The state of balance. It implies:

1. Thermal Equilibrium: no temperature differences between parts of the system or be-

tween the system and its surroundings
2. Mechanical Equilibrium: no unbalanced forces acting on any part of the system
3. Phase Equilibrium: no tendancy for the phase transformation i.e. no vaporization or
soldification
4. Chemical Equilibrium: no chemical reaction, i.e. not composition change
5. Electrostatic equilibrium: no tendancy for charge transfer

Thermodynamics deals with systems in a state of thermodynamics equilibrium because prop-

erties are only meaningful when the system is in equilibrium such that it can be measured
uniquely.

Simple Material: One open to only one reversible work mode

Simple Compressible Material: One only open to the compression-expansion reversible work
mode. A system is called simple compressible in the absence of electric, magnetic, grav-
itational, motion, and surface tension effects.

State Postulate

• when the intensive properties of a system are specified, the thermodynamic state of the sys-
tem is known intensively

• how long does the list of intensive properties have to be in order to describe the intensive
state of the system?

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 same
substance

A B

mA = 10 kg mB = 0.1 kg

T = 500 K
P = 0.1 MPa
3
v = 0.5 m /kg
u = 3.0 kJ/kg
.
.
.

• System A and B have the same intensive state, but totally different extensive states.

State Postulate (for a simple compressible system): The state of a simple

compressible system is completely specified by 2 independent and intensive properties.

• note: a simple compressible system experiences negligible electrical, magnetic, gravita-

tional, motion, and surface tension effects, and only P dV work is done

• in a single phase system, T, v, and P are independent and intensive (in a multiphase system
however, T and P are not independent)

• if the system is not simple, for each additional effect, one extra property has to be known to
fix the state. (i.e. if gravitational effects are important, the elevation must be specified and
two independent and intensive properties)

• it is important to be able to:

– find two appropriate properties to fix the state

– find other properties when the state is fixed (we will discuss this later)

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Thermodynamic Processes
Process: Any change that a system undergoes from one equilibrium state (initial state) to another
(end state)

Quasi-Equilibrium Process: System remains infinitesimally close to an equilibrium state at all

times

Cyclic Process: A process for which the end state is the same as the initial state

Isothermal Process: A process in which the temperature remains constant

Isobaric Process: A process in which the pressure remains constant

Isochoric (Isometric) Process: A process in which the volume remains constant

Isentropic Process: A process in which the entropy remains constant

Isenthalpic Process: A process in which the enthalpy remains constant

Adiabatic Process: A process in which no heat transfer occurs

Reversible Process: An imaginary process in which the system and surroundings can be returned
to its original condition after the process has been executed

Irreversible Process: A process for which it’s impossible to retain the initial state of the system
without having a net effect on the surroundings

• Here we concentrate on the meaning of different terms as we need to know in practice.

• the initial and end states are equilibrium states (i.e. no changes occur when they are isolated
from the surroundings)

– this implies thermal equilibrium (no ∆T ), mechanical equilibrium (dP/dt = 0),

phase equilibrium (no phase change), and chemical equilibrium (no chemical reactions)

• the process is any change from one equilibrium state to another. (If the end state = initial
state, then the process is a cycle)

• the process path is a series intermediate states through which a system passes during the
process (we very seldom care what the process path is)

• if the process is rapid (non-quasi-equilibrium), we cannot specify the path exactly

• a quasi-equilibrium (quasi-static) process is one that is sufficiently slow so that all the inter-
mediate states are close to equilibrium states

– quasi-equilibrium processes serve as standards to which actual processes can be com-

pared

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 – the quasi-equilibrium process is used as the standard model in engineering thermody-
namic analysis

• processes are categorized based on how the properties behave:

– isobaric (P = constant)
– isothermal (T = constant)
– isochoric or isometric (V = constant)
– isentropic (s = constant)
– isenthalpic (h = constant)
– adiabatic (no heat transfer)

Energy
Process: Stored (static) Energy: Energy forms which can be stored in the matter

Transit (dynamic) Energy: Energy forms which are defined at the system boundary

Internal Energy: All the microscopic forms of energy

Sensible Energy (heat): Part of the internal energy due to the motion of molecules

Latent Energy (heat): Part of the internal energy due to molecular binding forces

Kinetic Energy: All the macroscopic forms of the stored energy which are related to the motion
of the matter

Potential Energy: All the macroscopic forms of the stored energy which are related to the posi-
tion of the matter

Total Energy: Sum of all forms of stored energy

Heat (transfer): All transit energy forms that appear because of a temperature difference

Work (transfer): All transit energy forms that appear because of driving forces other than a tem-
perature difference

Stored Energy
• how is energy stored in matter?

• stored energy = energy in storage = static energy

• energy has different forms (matter may keep the energy in different forms)

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 • an appropriate physical model for stored energy is:

Stored Energy = E = Emac + Emic

• Emac is macroscopic forms of energy

– forms of the energy in the system (matter) as a whole with respect to some outside
reference frame

Emac = KEmac + P Emac

– KEmac = Kinetic Energy: Energy due to motion of the matter with respect to an
external reference frame (KE = mV 2 /2 or Iw2 /2)
– P Emac = Potential Energy: Energy due to the position of the matter in a force field
(gravitational, magnetic, electric). It also includes energy stored due to elastic forces
and surface tension (P E = mgz or kx2 /2)

• Emic = microscopic forms of energy (commonly called internal energy, U )

– forms of the energy in the matter due to its internal structure (independent of external
reference frames)

Emic = KEmic + P Emic

– KEmic = Kinetic Energy of molecules and P Emac = Potential Energy of molecules:

Latent phase energy (molecular binding forces), chemical energy (atomic bond forces),
nuclear energy (subatomic binding forces)

Note:
∗ part of the internal energy that is related to KEmic depends on the temperature of
the material. It is common to refer to this energy as “sensible energy”
∗ sensible energy is due to molecular motion (cooling water is sensible heat transfer)
∗ latent energy is due to molecular binding forces (freezing water is latent heat trans-
fer)

• Therefore:

Stored Energy = E = KE + P E + U

Transit Energy

• a system (matter) can exchange energy

• all forms of the stored energy can be exchanged with mass exchange

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 • energy can be exchanged in other (transit) forms

– heat transfer (radiative and conductive, but not convective)

– work transfer (mechanical, electrical)

Heat

• transit form of energy that occurs when there is ∆T (a temperature gradient)

• heat flow can be slowed (but not stopped) using insulation

• notation - Q (kJ ), q (kJ/kg), Q̇ (kW ), q̇ (kW/kg)

• thermodynamics does not specify how q is calculated when ∆T is known (this will be
discussed when you take “Heat Transfer”)

Work

• transit form of energy that occur due to all other driving forces

• notation - W (kJ ), w (kJ/kg), Ẇ (kW ), ẇ (kW/kg)

• we will consider different work transfer modes and the method of calculating W

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