Chapter 1

Introduction

1.1 Basic Definitions

Thermodynamics is the science that seeks to predict the amount of energy needed to
bring about a change of state of a system from one equilibrium state to another. While
thermodynamics tells us nothing about the mechanisms of energy transfer, rates of change,
and time associated with a system changing from one equilibrium state to another, it is still
the lynch-pin that allow us to answer these questions.

• Definition of 'heat': Heat is energy in transit solely as a result of a temperature

difference.

• Definition of 'work': Work is energy exchange between system and surroundings due
to any phenomenon except a temperature difference.

• Definition of 'temperature': Temperature is a measure of the mean kinetic energy of

molecules. Absolute zero (0oK) is a state of complete motionless of molecules.

• 'Rate': 'Rate' implies an element of speed, how fast an event happens, and time.

• 'System': In thermodynamics, the universe can be divided into two parts. One part is
the system, the other part is the rest of the universe called the surroundings. System
can be classified as (1) isolated system where no mass or energy is transferred across
the system boundaries, (2) closed system (system) where only energy is transferred
across the system boundaries, or (3) open system (control volume) where mass and
energy can be transferred across the system boundaries. A system is any designated
region of a continuum of fixed mass. The boundaries of a system may be deformable
but they always enclose the same mass.

Surroundings

Boundary
System

Figure 1.1 Schematic diagram of the "universe", showing a system and the
surroundings.

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 • 'Control volume': A 'control volume' is also any designated region of a continuum
except that it may permit matter to cross its boundaries. If the boundaries of a control
volume are such that matter may not enter or leave the control volume, the control
volume is identical to a system. In these respects, a 'system' is a subset of a 'control
volume'.

• 'Equilibrium': 'Equilibrium' means that there are no spatial differences in the variables
that describe the condition of the system, also called the 'state' of a system, such as its
pressure, temperature, volume, and mass (P, T, V, m), and that any changes which
occur do so infinitesimally slowly.

The laws of thermodynamics are applicable only to equilibrium states which means that the
state does not really change significantly with time, differences in variables between the state
of a system and its surroundings are of infinitesimal magnitude and that within the system
itself there are no spatial variations of the variables that determine its state. Using
thermodynamics, we can predict the amount of energy needed to change a system from an
equilibrium state to another. For example it will take about 75 kJ to change 1 kg of air at
25oC and 1 atm to 100oC and 1 atm. It will take much more energy, about 2257 kJ, to change
1 kg of water at 100oC and 1 atm to water vapor (steam) at the same temperature and
pressure.

State 1 75 kJ Air, 1 atm State 2

Air, 1 atm 100oC
25oC
required
1 kg
1 kg

Water
1 atm Steam
100oC 1 atm
1 kg 2257 kJ 100oC
State 1 1 kg State 2
required

Figure 1.1 Energy required changing air or water from state 1 to state 2.

1.2 Property

A property is a macroscopic characteristic of a system such as pressure, temperature, volume,

and mass. At a given state each property has a definite value independent of how the system
arrived at that state. The properties of air in state 1 shown in Figure 1.1 are: pressure at 1 atm,
temperature at 25oC, and mass of 1 kg.

A property can be classified as extensive or intensive. An extensive property depends on the

size of the system while an intensive property is independent on the size of the system.
Consider systems (1) and (2) shown in Figure 1.2 both at 100oC and 1 atm containing 2 and 5
kg of steam, respectively.

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 System (2)
System (1)
100oC
100oC
1 atm
1 atm
5 kg
2 kg

Figure 1.2 Example of intensive and extensive properties.

Temperature, pressure, and specific volume of both systems are intensive properties. Total
mass and total volume of each system are extensive property. At 100oC and 1 atm, the
specific volume v of each system is 1.674 m3/kg. The mass of system (1) is m1 = 2 kg and
that of system (2) is m2 = 5 kg. The total volume of system (1) is V1 = m1v = (2 kg)(1.674
m3/kg) = 3.348 m3. The total volume of system (2) is V2 = m2v = (5 kg)(1.674 m3/kg) = 8.37
m3. An intensive property might be obtained from an extensive propery by dividing the
extensive property by the mass of the system.

1.3 Units
The SI units (Système International d'Unitès, translated Internal System of Units) are used in
this text. It happens that seven primary quantities are needed to completely describe all
natural phenomena1. The decision as to which quantities are primary is arbitrary. The units of
the primary quantities and their symbols are listed in Table 1.3-1 and are defined arbitrarily
as follows:

Meter: the length of the trajectory traveled by light in a vacuum per 1/299,792,458 s,

Kilogram: the mass of the platinum cylinder deposited at the International Office for
Weights and Measures, Sèvres, France,

Second: 9,192,631,770 times the period of radiation in energy level transitions in the fine
spectral structure of 133Cs,

Kelvin: 1/273.16 of the triple point temperature of water with naturally occurring amounts of
H and O isotopes,

Amperes: the current which, on passing through two parallel infinite conducting wires of
negligible cross section, separated by 1 m and in vacuum, induces a force (per unit length) of
2×10-7 N/m,

Mole: the amount of a matter containing the number of particles equal to the number of
atoms in 0.012 kg of the pure isotope 12C,

Candela: the amount of perpendicular light (luminosity) of 1/60×10-6 m2 of the surface of an

absolute black body at the melting temperature of platinum and a pressure of 101,325 Pa.

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 Table 1.3-1 The seven primary quantities and their units in SI

Primary quantity Unit

Length Meter (m)
Mass Kilogram (kg)
Time Second (s)
Temperature Kelvin (K)
Electric current Ampere (A)
Amount of matter Mole (mol)
Amount of light Candela (cd)

Several of the derived quantities with units are listed in Table 1.3-2. A derived unit is a
quantity expressed in terms of a product and/or quotient of two or more primary units.

Table 1.3-2 The derived quantities and their units in SI

Derived quantity Unit

Cp, specific heat capacity J/kg·K
E, energy J = N·m, joule
F, force N = kg·m/s2, newton
k, thermal conductivity W/m·K
p, pressure Pa = N/m2, pascal
q, heat transfer rate W = J/s = kg·m2/s3, watt
q", heat flux W/m2 = J/s·m2
q ′′′ , heat generation rate per unit volume W/m3
µ, viscosity N/m2=kg/s·m
ρ, density kg/m3

1.4 Pressure
Any force acting on a surface consists of a component perpendicular to the surface and a
component parallel to the surface. These two components are called normal force and shear
force as shown in Figure 1.4-1. Pressure is defined as a normal force per unit area on which
the force acts. The SI pressure unit, N/m2, is called a pascal (Pa). Pressure at any point is a
fluid is the same in any direction.
Normal force
Normal stress = Normal force/A Fn

Shear force
Fs
Area (A)

Figure 1.4-1 Normal and parallel components of a force on a surface.

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Consider a hole in the wall of a tank or a pipe as shown in Figure 1.4-2. The fluid pressure p
may be defined as the ratio F/A, where F is the minimum force that would have to exerted on
a frictionless plug in the hole to keep the fluid from emerging1

F(N)
2
A(m2)
A(m )

Fluid
F(N) P(N/m2)

P(N/m2) Fluid flowing through a pipe

Figure 1.4-2 Fluid pressure in a tank and a pipe.

The pressure at a given position measured relative to absolute zero pressure or absolute
vacuum is called the absolute pressure. Most pressure-measuring devices are calibrated to
read zero in the atmosphere as shown in Figure 1.4-3. These pressure gages indicate the
difference between the absolute pressure and the local atmospheric pressure. Pressures below
atmospheric pressure are called vacuum pressures and are measured by vacuum gages that
indicate the difference between the atmospheric pressure and the absolute pressure. Absolute,
gage, and vacuum pressures are all positive quantities and are related to each other by

Pgage = Pabs − Patm

Pvac = Patm − Pabs

Pgage
7
5 6 89 Pabs
4 10
Patm 3 Patm
Pvac 2 kPa
1
0
Patm
Pabs Patm

Pabs = 0 Pabs = 0

Figure 1.4-3 Absolute, gage, and vacuum pressures.

Two common pressure units are the bar and standard atmosphere:

1 bar = 105 Pa = 0.1 Mpa = 100 kPa

1 atm = 101,325 Pa = 101.325 kPa = 1.01325 bar = 14.696 psi

1
R. M. Felder and R. W. Rousseau, Elementary Principles of Chemical Processes, Wiley, 2000, p.54.
1-5
1.5 Variation of pressure with elevation
Fluid at rest cannot support shearing stress. It can only support normal stress or pressure that
can result from gravity or various other forces acting on the fluid. Pressure is an isotropic
stress since the force acts uniformly in all directions normal to any local surface at a given
point in the fluid. An isotropic stress is then a scalar since it has magnitude only and no
direction. By convention, pressure is considered a negative stress because it is compressive,
whereas tensile stresses are positive. The direction of pressure force is always pointing
inward the control volume. We now investigate how the pressure in a stationary fluid varies
with elevation z as shown in Figure 1.5-1.

P|z+∆z

∆z

z
P|z

Figure 1.5-1 Forces acting on control volume A∆z

Applying a momentum or force balance in the z-direction on the control volume A∆z we
obtain

ΣFz = maz = 0

AP|z − AP|z+∆z − ρg A∆z = 0

Dividing the equation by the control volume A∆z and letting ∆z approach zero we obtain

lim P |z + ∆z − P |z dP
= = − ρg (1.51)
∆z → 0 ∆z dz

Equation (1.5-1) is the basic equation of fluid statics. It can be integrated if the density and
the acceleration of gravity are known functions of elevation. We will assume g a constant
since the change in elevation is usually not significant enough for g to vary. The integration
will depend on the variation of density. If the density is not a constant, a relation between ρ
and z or P must be obtained. For constant density fluids, equation (1.5-1) can be easily
integrated

P2 z2
dP = − ρg dz P2 − P1 = − ρg(z2 − z1)
P1 z1

This equation can also be written as

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 P2 + ρgz2 = P1 + ρgz1 = Φ = constant

The sum of the local pressure P and static head ρgz is called the potential Φ that is constant
at all points within a given incompressible fluid.

Example 1.5-1. 2 ----------------------------------------------------------------------------------

The manometer system shown in Figure 1.5-2 contains oil and water, between which there is
a long trapped air bubble. For the indicated heights of the liquids, find the specific gravity of
the oil. The two sides of the U-tube are open to the atmosphere.

h1 = 2.5 ft
Oil

h2 = 0.5 ft Air
P2 h4 = 3.0 ft
P1

h3 = 1.0 ft Water

Figure 1.5-2 A manometer system with oil, air, and water

Solution ------------------------------------------------------------------------------------------

The pressure P1 at the water air interface on the left side of the U-tube has the same value as
the pressure P2 in the water at the same elevation on the right side of the U-tube.

P1 = Patm + ρogh1 + ρagh2

P2 = Patm + ρwg (h4 − h3)

If the pressure due to the weight of air is neglected compared to that of oil and water, we can
determine the specific weight so of oil as follow

ρo h − h3 3 .0 − 1 .0
ρogh1 = ρwg (h4 − h3) so = = 4 = = 0.80
ρw h1 2 .5

2
Wilkes, J., Fluid Mechanics for Chemical Engineers, Prentice Hall, 1999, p. 28

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1.6 Temperature
When two objects are brought into contact and isolated from the surrounding, energy tends to
move spontaneously from one to the other. The object that gives up energy is at a higher
temperature, and the object that receives energy is at a lower temperature. We would be able
to observe that the electrical resistance of the warmer object decreases with time, and that of
the colder block increases with time; eventually there would be no change in the electrical
resistances of these objects. The two objects are then in thermal equilibiurm. They are at the
same Temperature. We could then define temperature as a measure of the tendency of an
object to spontaneously give up energy to its surroundings.

Any object with at least one measurable property that changes as its temperature changes can
be used as a thermometer. Most thermometers operate on the principle of thermal expansion:
Materials tend to occupy more volume at a given pressure when they are at a higher
temperature. A mercury thermometer is just a convenient device for measuring the volume of
a fixed amount of mercury. To define actual units for temperature we arbitrary assign 0 to the
freezing point and 100 to the boiling or steam point of water. We then mark these two points
on our mercury thermometer, measure off a hundred equally spaced intervals in between, and
declare that this thermometer now measures temperature on the Celsius (or centigrade) scale,
by definition.

The Kelvin scale is an absolute temperature scale that measures temperature from absolute
zero instead of from the freezing point of water. The relationship between these two
temperature scales is given by

T(oC) = T(K) − 273.15 (1.6-1)

By definition, the Rankin scale, is related to the Kelvin scale by a factor of 1.8:

T(oR) = 1.8T(K) (1.6-2)

A degree of the same size as that on the Rankine scale is used in the Fahrenheit scale but the
zero point is shifted according to the relation

T(oF) = T(oR) − 459.67 (1.6-3)

From equations (1.6-1), (1.6-2), and (1.6-3) the Fahrenheit scale can be related to the Celsius
scale by

T(oF) = 1.8T(oC) + 32

Many of the equations of thermodynamics are correct only when you measure temperature
on the absolute scale, Kelvin or Rankine. There will be no problem in using the Celcius and
Fahrenheit scales when the difference between two temperatures is needed.

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