Ch 1

Introductory
Concepts and
Definitions
Using thermodynamics
Defining Systems

The system is whatever we want to study.

It may be as simple as a free body or as complex as an entire

chemical refinery.

Quantity of matter contained within a closed, rigid-walled tank, or a

pipeline through which natural gas flows.

The composition of the matter inside the system may be fixed or may
be changing through chemical or nuclear reactions.
The shape or volume of the system being analyzed is not
necessarily constant, as when a gas in a cylinder is compressed by a
piston or a balloon is inflated.

Everything external to the system is considered to be part of the

system’s surroundings.

The system is distinguished from its surroundings by a specified

boundary, which may be at rest or in motion.
1. Closed Systems

A closed system always contains the same matter. There can be no

transfer of mass across its boundary. A closed system refers to a fixed
quantity of matter.

The term control mass is sometimes

used in place of closed system.

A special type of closed system that does

not interact in any way with its
surroundings is called an isolated system.
2. Control Volumes
is a region of space through which mass may flow.

the term open system is used interchangeably with control volume.

Selecting the System Boundary
The choice of system boundary is governed by two considerations:
(1) what is known about a possible system, particularly at its
boundaries.
(2) The objective of the analysis.

The system boundary encloses the

compressor, tank, and all of the
piping. This boundary might be
selected if the electrical power
input is known, and the objective
of the analysis is to determine how long the compressor must operate
for the pressure in the tank to rise to a specified value.
A control volume enclosing only the compressor might be chosen if the
condition of the air entering and exiting the compressor is known, and the
objective is to determine the electric power input.

Macroscopic and Microscopic Views of Thermodynamics

The macroscopic approach to thermodynamics (classical
thermodynamics) is concerned with the gross or overall behavior.
No model of the structure of matter at the molecular, atomic, and
subatomic levels is directly used in classical thermodynamics. Although
the behavior of systems is affected by molecular structure, classical
thermodynamics allows important aspects of system behavior to be
evaluated from observations of the overall system.
The microscopic approach to thermodynamics (statistical
thermodynamics) is concerned directly with the structure of matter. The
objective of statistical thermodynamics is to characterize by statistical
means the average behavior of the particles making up a system of
interest and relate this information to the observed macroscopic
behavior of the system.

For applications involving lasers, plasmas, high speed gas flows,

chemical kinetics, very low temperatures (cryogenics), and others, the
methods of statistical thermodynamics are essential.

The microscopic approach is used in this text to interpret internal

energy and entropy .
Property, State, and Process

A property is a macroscopic characteristic of a system such as mass,

volume, energy, pressure, and temperature to which a numerical value
can be assigned at a given time without knowledge of the previous
behavior (history) of the system.

The state refers to the condition of a system as described by its

properties.

A process is a transformation from one state to another.

A system is said to be at steady state if none of its properties changes

with time.
A quantity is a property if, and only if, its change in value between two
states is independent of the process such as mass flow rates and
energy transfers by work and heat.

Thermodynamic properties can be placed in two general classes:

1) Extensive property: if its value for an overall system is the sum of
its values for the parts into which the system is divided. Mass,
volume, energy, and several other properties introduced later are
extensive. Extensive properties depend on the size or extent of a
system. The extensive properties of a system can change with time.
2) Intensive properties are not additive in the sense previously
considered. Their values are independent of the size or extent of a
system and may vary from place to place within the system at any
moment.

Intensive properties may be functions of both position and time,

whereas extensive properties can vary only with time.

Specific volume, pressure, and temperature.

Equilibrium
In mechanics, equilibrium means a condition of balance maintained by
an equality of opposing forces.

In thermodynamics, including not only a balance of forces but also a

balance of other influences. several types of equilibrium must exist
individually to fulfill the condition of complete equilibrium; among these
are mechanical, thermal, phase, and chemical equilibrium.

Test: Isolate the system from its surroundings and watch for changes in
its observable properties. If there are no changes, we conclude that the
system was in equilibrium at the moment it was isolated. The system
can be said to be at an equilibrium state.
Measuring Mass, Length, Time, and Force

SI Units:
SI is the abbreviation for Système International d'Unités (International
System of Units), which is the legally accepted system in most countries.
The conventions of the SI are published and controlled by an
international treaty organization.
Newton’s second law of motion:
the net force acting on a body is proportional to the product of the mass
and the acceleration,

The newton, N, is the force required to

accelerate a mass of 1 kilogram at the
rate of 1 meter per second per second.
Example: determine the weight in newtons of an object whose mass is 1000
kg, at a place on Earth’s surface where the acceleration due to gravity =
9.80665 m/s2.
2) English Engineering Units

The English unit of force, the pound force, lbf, is the force required to
accelerate one pound mass at 32.1740 ft/s2, which is the standard
acceleration of gravity.
Example: determine the weight of an object whose mass is 1000 lb at a
location where the local acceleration of gravity is 32.0 ft/s2.
Specific Volume
At any instant the density at (ρ) point is defined as

The density, or local mass per unit volume, is an intensive property that
may vary from point to point within a system.

The mass associated with a particular volume V is determined in

principle by integration
The specific volume is defined as the reciprocal of the density. It is
the volume per unit mass.

Specific volume is an intensive property and may vary from point to

point.

SI units for density and specific volume are kg/m3 or g/cm3 and
m3/kg or cm3/g respectively.

English units used for density and specific volume are lb/ft3 and
ft3/lb, respectively.
A mole (n) is an amount of a given substance numerically equal to its
molecular weight and its unit is kilomole (kmol) or the pound mole
(lbmol),

Where (m) is the mass in kilograms and (M) the molecular weight in
kg/kmol.

The molar volume ( )

Its unit is m3/kmol and ft3/lbmol

Pressure
The pressure (p) at the specified point is defined as the limit

It is the force applied perpendicular to the surface of an object per unit

area over which that force is distributed.

This term is used for fluids (liquids and gases) where in the case of
solid the term stress is used.

Absolute pressure: pressure with respect to the zero pressure of a

complete vacuum.
Pressure Measurement
Manometers and barometers measure pressure in terms of the length
of a column of liquid such as mercury, water, or oil.
If the pressures at points a and b of Fig. 1.7 are equal. Applying an
elementary force balance, the gas pressure (p) is

where patm is the local atmospheric pressure, ρ is the density of the

manometer liquid, g is the acceleration of gravity, and L is the
difference in the liquid levels.

The barometer shown in Fig. 1.8, Since the pressures at points a and
b are equal, a force balance gives the atmospheric pressure (patm)
as
Because the pressure of the mercury vapor is much less than that of
the atmosphere, Eq. 1.12 can be approximated closely as

Pressures measured with manometers and barometers are frequently

expressed in terms of the length (L) in millimeters of mercury (mmHg),
inches of mercury (inHg), inches of water (inH2O), and so on.
A Bourdon tube gage is shown in Fig. 1.9. The figure shows a curved tube
having an elliptical cross section with one end attached to the pressure to be
measured and the other end connected to a pointer by a mechanism. When
fluid under pressure fills the tube, the elliptical section tends to become
circular, and the tube straightens. This motion is transmitted by the
mechanism to the pointer. By calibrating the deflection of the pointer for
known pressures, a graduated scale can be determined from which any applied
pressure can be read in suitable units.
An important class of sensors utilizes the piezoelectric effect: A charge is
generated within certain solid materials when they are deformed. This
mechanical input/electrical output provides the basis for pressure
measurement as well as displacement and force measurements. Another
important type of sensor employs a diaphragm that deflects when a force is
applied, altering an inductance, resistance, or capacitance. Figure 1.10
shows a piezoelectric pressure sensor together with an automatic data
acquisition system.
Buoyancy
When a body is completely or partially submerged in a liquid, the
resultant pressure force acting on the body is called the buoyant force.
Pressure Units
The SI unit of pressure and stress is the pascal:

English units for pressure and stress are pounds force per square foot,
lbf/ft2, and pounds force per square inch, lbf/in.2
The term gage pressure is applied when the pressure of the system is
greater than the atmospheric pressure, patm.

When the local atmospheric pressure is greater than the pressure of the
system, the term vacuum pressure is used.
FIg. 1.12 Relationships among the absolute, atmospheric, gage, and
vacuum pressures.
Temperature
Consider two copper blocks, one is hot and the other is cold. If the
blocks were brought into contact and isolated from their surroundings,
they would interact in a way that can be described as a thermal (heat)
interaction:

Volume of the warmer block decreases while the volume of the

colder block increases and finally the blocks would feel equally warm.

The electrical resistance of the warmer block decreases and that of

the colder block increases until they would become constant.

When all changes in such observable properties cease, the

interaction is at an end. The two blocks are then in thermal
These considerations lead that the blocks have a physical property
called temperature that determines whether they will be in thermal
equilibrium.

It postulates that when the two blocks are in thermal equilibrium, their
temperatures are equal.

When two objects are in thermal equilibrium with a third object, they
are in thermal equilibrium with one another (The zeroth law of
thermodynamics).

If we want to know if two objects are at the same temperature, It is

necessary only to see if they are individually in thermal equilibrium with
a third object. The third object is usually a thermometer.
Thermometers
Thermometric property: is a property that changes as temperature
changes.

Thermometric substance : is the particular substance that exhibits

changes in the thermometric property.

Any object with at least one measurable property that changes as its
temperature changes can be used as a thermometer.(Fig 1.13a)

Thermocouples : when two dissimilar metals (platinum & alloy) are

joined, an electromotive force (emf) that is primarily a function of
temperature will exist in a circuit.
Electrical resistance sensors: based on the fact that the electrical
resistance of various materials (platinum, nickel, or copper or
semiconductors) changes in a predictable manner with temperature.

Devices using conductors are known as resistance temperature

detectors. Semiconductor types are called thermistors (Fig. 1.13b).

Infrared-sensing ear thermometer: (Fig. 1.13c) They are known as

radiation thermometers and optical pyrometers.

They are not required to come in contact with an object to determine

its temperature, an advantage when dealing with moving objects or
objects at extremely high temperatures.
Kelvin and Rankine Temperature Scales
The Kelvin scale is an absolute thermodynamic temperature scale
that provides a continuous definition of temperature, valid over all ranges
of temperature.
The SI unit of temperature on the Kelvin scale is the kelvin (K).
The lowest possible value of temperature is zero and lower
temperatures than this are not defined.
The Rankine scale, the unit of which is the degree rankine (oR), is
proportional to the Kelvin temperature according to

The Rankine scale is also an absolute thermodynamic scale with an

absolute zero that coincides with the absolute zero of the Kelvin scale.
Celsius and Fahrenheit Scales
Triple point of water: the state of equilibrium among steam, ice, and
liquid water.
The Celsius temperature scale uses the unit degree Celsius (oC),
which has the same magnitude as the kelvin.

A degree of the same size as that on the Rankine scale is used in the
Fahrenheit scale, but the zero point is shifted as: