Thermodynamics I

WOLDIA UNIVERSITY

WOLDIA INSTITUTE OF TECHNOLOGY

SCHOOL OF MECHANICAL AND CHEMICAL ENGINEERING
PROCESS ENGINEERING CHAIR

CHEMICAL ENGINEERING THERMODYNAMICS I MODULE

By: Molla z. (Msc)

Woldia, Ethiopia
March, 2023

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 Thermodynamics I

CHAPTER ONE
1. INTRODUCTION AND BASIC CONCEPTS
1.1. Definition and scope of thermodynamics
The name thermodynamics originated from the Greek words therme (heat) and dynamis
(power), which is most descriptive of the early efforts to convert heat into power.
Thermodynamics is a branch of science which deals with the study of heat and work and their
relation to other forms of energy. Thermodynamics is a branch of science which deals with the
study of heat and work and their relation to other forms of energy.
One of the most fundamental laws of nature is the conservation of energy principle. It simply
states that during an interaction, energy can change from one form to another but the total
amount of energy remains constant. That is, energy cannot be created or destroyed. A rock
falling off a cliff, for example, picks up speed as a result of its potential energy being converted
to kinetic energy.
Classical versus Statistical Thermodynamics
Substances consist of large number of particles called molecules. The properties of the substance
naturally depend on the behavior of these particles. But one does not need to know the behavior
of the gas particles to determine the pressure in the container. It would be sufficient to attach a
pressure gage to the container. This macroscopic approach to the study of thermodynamics
which does not require knowledge of the behavior of individual particles is called classical
thermodynamics. It provides a direct and easy way to the solution of engineering problems. A
more elaborate approach, based on the average behavior of large groups of individual particles, is
called statistical thermodynamics (Microscopic Approach).

1.2. Systems and their behaviors

A system is defined as a quantity of matter or a region in space chosen for study. The mass or
region outside the system is called the surroundings. The real or imaginary surface that
separates the system from its surroundings is called the boundary. The boundary of a system can
be fixed or movable. Note that the boundary is the contact surface shared by both the system and
the surroundings. Mathematically speaking, the boundary has zero thickness, and thus it can
neither contain any mass nor occupy any volume in space.

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 Thermodynamics I

Types of Thermodynamics System

Systems may be considered to be closed or open, depending on whether a fixed mass or a fixed
volume in space is chosen for study.
Open system (control volume)
• Both mass and energy can cross the boundary of a system. (eg. Compressor, turbine and
nozzle).
Closed system (control mass)
• Consists of a fixed amount of mass, and no mass can cross its boundary.
• That is, no mass can enter or leave a closed system, but energy can transfer in the form of
heat and work
Isolated system
• Neither mass nor energy is not allowed to cross the boundary, that system is called an
isolated system
Properties of a system
Any characteristic of a system is called a property. Some familiar properties are pressure P,
temperature T, volume V, and mass m.
Properties are considered to be either intensive or extensive.
Intensive properties are those that are independent of the mass of a system, such as
temperature, pressure, and density.
Extensive properties are those whose values depend on the size or extent of the system. Total
mass, total volume and total momentum are some examples of extensive properties.
An easy way to determine whether a property is intensive or extensive is to divide the system
into two equal parts with an imaginary partition, as shown in Fig. below. Each part will have the
same value of intensive properties as the original system, but half the value of the extensive
properties.

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 Thermodynamics I

Fig: Criterion to differentiate intensive and extensive properties.

Extensive properties per unit mass are called specific properties. Some examples of specific
properties are specific volume (v=V/m) and specific total energy (e=E/m).
Thermodynamic Processes
The prefix iso is often used to designate a process for which a particular property remains
constant.
• Isothermal process is a process during which the temperature T remains constant;
• Isobaric process is a process during which the pressure P remains constant;
• Isochoric (or isometric) process is a process during which the volume v remains
constant.
• Isentropic process is a thermodynamic process in which the entropy of gas or any fluid
remains constant
1.3. Measurement of amount or size
Three measures of amount or size of a homogeneous material are in common use:
 Mass (m), number of moles (n) and total volume Vt.
These measures for a specific system are in direct proportion to one another. Mass may be
divided by the molar mass ℳ (formerly called molecular weight) to yield number of moles:

Total volume, representing the size of a system, is a defined quantity given as the product of
three lengths. It may be divided by the mass or number of moles of the system to yield specific
or molar volume:

 Specific volume:

 Molar volume:
Density is defined as mass per unit volume
ρ= (kg/m3)

The reciprocal of density is the specific volume v, which is defined as volume per unit mass.
v= =

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 Thermodynamics I

The density of most gases is proportional to pressure and inversely proportional to temperature.
Fluids are divided into liquids, or incompressible fluids, and gases, or compressible fluids.
Specific gravity or relative density is defined as the ratio of the density of a substance to the
density of some standard substance at a specified temperature (usually water at 4°C, for which
ρH2O=1000 kg/m3). That is,

Specific gravity (SG) =

NB: The specific gravity of a substance is a dimensionless quantity.
1.4. Temperature
First it is vital to discuss the difference between heat and temperature as follows.
Temperature
• Temperature is a measurement of the average kinetic energy of the molecules in any
object.
• Temperature can also be defined as a degree of hotness or coldness of an object.
Heat
• Heat is defined as a flow of thermal energy due to differences in temperatures.
• Heat is simply thermal energy in transit
The Zeroth law of thermodynamics states that if two bodies are in thermal equilibrium with a
third body, they are also in thermal equilibrium with each other. Generally speaking, zeroth law
of thermodynamics deals with temperature and temperature scale.
What is most important is that the zeroth law establishes that temperature is a fundamental and
measurable property of matter.
Temperature Scales
Temperature scales enable us to use a common basis for temperature measurements, and several
have been introduced throughout history. All temperature scales are based on some easily
reproducible states such as the freezing and boiling points of water, which are also called the ice
point and the steam point, respectively. The temperature scales most commonly used includes
the Celsius scale, Fahrenheit scale, Kelvin scale and Rankile scale. The thermodynamic
temperature scale used in SI units is the Kelvin scale (K) and in the English unit the Rankile
scale (R).
To convert from one temperature scale to others we use the following conversion factors.

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 Thermodynamics I

( ) ( ) ( ) ( )
When we are dealing with temperature differences ∆T, the temperature interval on both scales is
the same. Raising the temperature of a substance by 10°C is the same as raising it by 10 K.
( ) ( ) ( ) ( )
1.5. PRESSURE
Pressure is defined as a normal force exerted by a fluid per unit area. We speak of pressure only
when we deal with a gas or a liquid. The counterpart of pressure in solids is normal stress. Since
pressure is defined as force per unit area, it has the unit of newton per square meter (N/m2),
which is called a pascal (Pa).
Three other pressure units commonly used in practice, especially in Europe, are bar, standard
atmosphere, and kilogram-force per square centimeter.
The actual pressure at a given position is called the absolute pressure, and it is measured
relative to absolute vacuum (i.e., absolute zero pressure). Most pressure-measuring devices,
however, are calibrated to read zero in the atmosphere. The difference between the absolute
pressure and the local atmospheric pressure is gauge pressure. Pressures below atmospheric
pressure are called vacuum pressures.

Fig: Absolute, gage, and vacuum pressures.

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 Thermodynamics I

Variation of Pressure with Depth

Pressure in a fluid at rest does not change in the horizontal direction. This can be shown easily
by considering a thin horizontal layer of fluid and doing a force balance in any horizontal
direction. However, this is not the case in the vertical direction in a gravity field. Pressure in a
fluid increase with depth because, more fluid rests on deeper layers and the effect of this “extra
weight” on a deeper layer is balanced by an increase in pressure.
To obtain a relation for the variation of pressure with depth, consider a rectangular fluid element
of height ∆z, length ∆x, and unit depth (into the page) in equilibrium, as shown in Fig. below.
Assuming the density of the Fluid r to be constant, a force balance in the vertical z-direction
gives:

Manometer is used to measure small to moderate pressure difference. Atmospheric pressure is

measured by a device called a barometer; thus, the atmospheric pressure is often referred to as
the barometric pressure. The Italian Evangelista Torricelli (1608–1647) was the first to
conclusively prove that the atmospheric pressure can be measured by inverting a mercury-filled
tube into a mercury container that is open to the atmosphere.

1.6. Work
Work, W, is performed whenever a force acts through a distance. By its definition, the quantity
of work is given by the equation:

The SI unit of work is the newton meter or joule, symbol J. By convention, work is regarded as
positive when the displacement is in the same direction as the applied force and negative when
they are in opposite directions.
Work is done when pressure acts on a surface and displaces a volume of fluid. An example is the
movement of a piston in a cylinder so as to cause compression or expansion of a fluid contained

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 Thermodynamics I

in the cylinder. The force exerted by the piston on the fluid is equal to the product of the piston
area and the pressure of the fluid. The displacement of the piston is equal to the total volume
change of the fluid divided by the area of the piston.

The minus signs in these equations are made necessary by the sign convention adopted for work.
When the piston moves into the cylinder so as to compress the fluid, the applied force and its
displacement are in the same direction; the work is therefore positive. The minus sign is required
because the volume change is negative. For an expansion process, the applied force and its
displacement are in opposite directions. The volume change in this case is positive, and the
minus sign is again required to make the work negative.
1.7. Energy
In thermodynamics, we deal with change of the total energy only. Total energy of a system has
two groups: macroscopic and microscopic.
Macroscopic forms of energy: forms of energy that a system possesses as a whole with respect
to some outside reference frame, such as kinetic and potential energy.
 Kinetic energy: energy that a system possesses as a result of its relative motion relative to
some reference frame, KE

( )

 Potential energy: is the energy that a system possesses as a result of its elevation in a
gravitational field, PE
( )
Microscopic forms of energy: are those related to molecular structure of a system. They are
independent of outside reference frames. The sum of microscopic energy is called the internal
energy, U.
The total energy of a system consists of the kinetic, potential, and internal energies:

( )

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 Thermodynamics I

Mechanisms of Energy Transfer

Energy can be transferred to or from a system in three forms: heat, work, and mass flow. Energy
interactions are recognized at the system boundary as they cross it, and they represent the energy
gained or lost by a system during a process.
1. Heat Transfer, Q Heat transfer to a system (heat gain) increases the energy of the
molecules and thus the internal energy of the system, and heat transfer from a system
(heat loss) decreases it since the energy transferred out as heat comes from the energy of
the molecules of the system.
2. Work Transfer, W An energy interaction that is not caused by a temperature difference
between a system and its surroundings is work. A rising piston, a rotating shaft, and an
electrical wire crossing the system boundaries are all associated with work interactions.
3. Mass Flow, m Mass flow in and out of the system serves as an additional mechanism of
energy transfer. When mass enters a system, the energy of the system increases because
mass carries energy with it (in fact, mass is energy). Likewise, when some mass leaves
the system, the energy contained within the system decreases because the leaving mass
takes out some energy with it.

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 Thermodynamics I

CHAPTER TWO
2. PROPERTIES OF PURE SUBSTANCES
2.1. Pure substance
• A substance that has a fixed chemical composition throughout is called a pure
substance.
Example: Water, nitrogen, helium, and carbon dioxide
• A pure substance does not have to be of a single chemical element or compound.
• A mixture of various chemical elements or compounds also qualifies as a pure substance
as long as the mixture is homogeneous.
Example: Air (N2, O2, CO2, water vapour…)
• A mixture of oil and water is not a pure substance. Since oil is not soluble in water, it
will collect on top of the water, forming two chemically dissimilar regions.
• A mixture of ice and liquid water, for example, is a pure substance because both phases
have the same chemical composition.
2.2. Phases of a pure substance
Phase – is identified as having a distinct molecular arrangement that is homogeneous throughout
and separated from the others by easily identifiable boundary surfaces.
There are three principal phases – solid, liquid and gas, but a substance can have several other
phases within the principal phase. Examples include solid carbon (diamond and graphite) and
iron (three solid phases). Nevertheless, thermodynamics deals with the primary phases only.
Solid
• At fixed position
• Cannot move relative to each other but they oscillate about their equilibrium position
• Solids are closely packed in a three-dimensional crystal lattice
• Solids have strongest molecular bonds

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 Thermodynamics I

Liquid
• No longer at fixed position
• They can rotate and translate freely
• Weakest molecular bond strength relative to solids but stronger than gases

Fig. Groups of molecules move about each other in the liquid phase
Gas
• The molecules move randomly and collide with each other.
• Molecules in the gas phases are far apart, they have no ordered structure
• The intermolecular forces are very small
• Molecules in the gas phase are at a considerably higher energy level than they are in
liquids or solid phases.

Fig. molecules move about at random in the gas phase

Phase-change processes of pure substances
As a familiar substance, water is used to demonstrate the basic principles involved. Remember,
however, that all pure substances exhibit the same general behavior.
Compressed Liquid and Saturated Liquid
In order to introduce the rather complex phase change interactions that occur in pure substances
we consider an experiment in which we have liquid water in a piston-cylinder device at 20°C and

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 Thermodynamics I

100kPa pressure. Heat is added to the cylinder while the pressure is maintained constant until the
temperature reaches 300°C, as shown in the following T-v diagram (temperature vs specific
volume):

From State (1) to State (2) the water maintains its liquid phase and the specific volume increases
very slightly until the temperature reaches close to 100°C (State (2) - Saturated Liquid). As
more heat is added the water progressively changes phase from liquid to water vapor (steam)
while maintaining the temperature at 100°C, until there is no liquid remaining in the cylinder
(State (4) - Saturated Vapor). If heating continues then the water vapor temperature increases
(T > Tsat) and is said to be in the Superheated region (State (5)).
The Quality Region
The Quality Region (also referred to as the Saturated Liquid-Vapor Mixture Region) is
enclosed between the saturated liquid line and the saturated vapor line, and at any point within
this region the quality of the mixture (also referred to as the dryness factor) is defined as the
mass of vapor divided by the total mass of the fluid, as shown in the following diagram:

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 Thermodynamics I

Notice that properties relating to the saturated liquid have the subscript f, and those relating to
the saturated vapor have the subscript g. In order to evaluate the quality, consider a volume V
containing a mass m of a saturated liquid-vapor mixture.

Saturation Temperature and Saturation Pressure

The temperature at which water starts boiling depends on the pressure; therefore, if the pressure
0
is fixed, so is the boiling temperature Water boils at 100 C at 1 atm pressure. .
 Saturation temperature T : The temperature at which a pure substance changes phase
sat

at a given pressure.
 Saturation pressure P : The pressure at which a pure substance changes phase at a
sat

given temperature.
 The amount of energy absorbed or released during a phase-change process is called
Latent heat.
 The amount of energy absorbed or released without phase change process is called
Sensible heat.
 Latent heat of fusion: The amount of energy absorbed during melting. It is equivalent to
the amount of energy released during freezing.
 Latent heat of vaporization: The amount of energy absorbed during vaporization and it
is equivalent to the energy released during condensation.

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 Thermodynamics I

2.3. Property diagrams for phase-change processes

The variations of properties during phase-change processes are best studied and understood with
the help of property diagrams. Next, we develop and discuss the T-v, P-v, and P-T diagrams for
pure substances.

1. The T-v Diagram

Consider water at a pressure of 1 MPa inside a cylinder. At this pressure, water has a somewhat
smaller specific volume than it does at 1 atm pressure. At 1Mpa pressure:
 First, water starts boiling at a much higher temperature (179.98°C) at this pressure, but
at 1atm it boils at 100°C.
 Second, the specific volume of the saturated liquid is larger and the specific volume of
the saturated vapor is smaller than the corresponding values at 1 atm pressure. That is, the
horizontal line that connects the saturated liquid and saturated vapor states is much
shorter as shown in fig.

Fig: T-v diagram of constant-pressure phase-change processes of a pure substance at various

pressures (numerical values are for water).
The critical point is defined as the point at which the saturated liquid and saturated vapor states
are identical. The temperature, pressure, and specific volume of a substance at the critical point

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 Thermodynamics I

are called, respectively, the critical temperature Tcr, critical pressure Pcr, and critical specific
volume Vcr.
Above the critical state, there is no line that separates the compressed liquid region and the
superheated vapor region. However, it is customary to refer to the substance as superheated
vapor at temperatures above the critical temperature and as compressed liquid at temperatures
below the critical temperature.

Fig: T-v diagram of a pure substance.

2. The P-v Diagram
The general shape of the P-v diagram of a pure substance is very much like the T-v diagram, but
the T = constant lines on this diagram have a downward trend, as shown on the Fig.

Fig: P-v diagram of a pure substance.

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 Thermodynamics I

3. The P-T Diagram

This is called phase diagram since all three phases are separated from each other by three lines.
 The sublimation line separates the solid and vapor regions,
 The vaporization line separates the liquid and vapor regions, and
 The melting (or fusion) line separates the solid and liquid regions.
These three lines meet at the triple point, where all three phases coexist in equilibrium. The
vaporization line ends at the critical point because no distinction can be made between liquid and
vapor phases above the critical point.

Fig: P-T diagram of pure substances.

2.4. The ideal-gas equation of state
Property tables provide very accurate information about the properties, but they are bulky and
vulnerable to typographical errors.
Any equation that relates the pressure, temperature, and specific volume of a substance is called
an equation of state. There are several equations of state, some simple and others very complex.
The simplest and best-known equation of state for substances in the gas phase is the ideal-gas
equation of state. This equation predicts the P-v-T behavior of a gas quite accurately within some
properly selected region.
The equation PV = RT is now understood to define an ideal gas and to represent a model of
behavior more or less approximating the behavior of real gases. It is called the ideal gas law, but
is in fact valid only for pressures approaching zero and temperatures approaching infinity. Thus,
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 Thermodynamics I

it is a law only at limiting conditions. As these limits are approached, the molecules making up a
gas become more and more widely separated, and the volume of the molecules themselves
becomes a smaller and smaller fraction of the total volume occupied by the gas.
Furthermore, the forces of attraction between molecules become ever smaller because of the
increasing distances between them. In the zero-pressure limit, molecules are separated by infinite
distances. Their volumes become negligible compared with the total volume of the gas, and the
intermolecular forces approach zero.
The ideal gas law is comprising of three different laws as Boyles, Charles and Avogadro’s law.

Boyles law = V at constant T

Charles law = VT at constant P

Avogadro's law= VN at constant T&P
By combining the above three laws ideal gas law was formulated.

The gas constant R is different for each gas and is determined from
( )
Where Ru is the universal gas constant and M is the molar mass (also called molecular weight)
of the gas. The constant Ru is the same for all substances, and its value is

Ideal gas and non-ideal gas

Ideal gas
• Obeys ideal gas equation of state (PV= RT)
• Obeys the postulates of kinetic molecular theory
 No force of attraction between gas molecules
 Actual volume of the gas molecules is negligible compared to the container volume
 The gas particles have perfect elastic collisions with no energy loss.
Non ideal /real gas

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 Thermodynamics I

• Do not obey the ideal gas equation of state

• Do not obey the postulate of kinetic molecular theory
Compressibility factor
Compressibility factor (Z) is a factor that accounts for the deviation of real gases from ideal-gas
behavior at a given temperature and pressure.

It can also be expressed as

Where Obviously, Z=1 for ideal gases.

Z is bigger than unity, the more the gas deviates from ideal-gas behavior. Gases behave as an
ideal gas at low densities (i.e., low pressure, high temperature). The pressure or temperature of a
substance is high or low relative to its critical temperature or pressure.
Gases behave differently at a given temperature and pressure, but they behave very much the
same at temperatures and pressures normalized with respect to their critical temperatures and
pressures. The normalization is done as:

Here PR is called the reduced pressure and TR the reduced temperature. The Z factor for all
gases is approximately the same at the same reduced pressure and temperature. This is called the
principle of corresponding states. When either P or T is unknown, it can be determined from
the compressibility chart with the help of the pseudo reduced specific volume, defined as:

Other equations of state

The ideal-gas equation of state is very simple, but its range of applicability is limited. It is
desirable to have equations of state that represent the P-v-T behavior of substances accurately
over a larger region with no limitations. Such equations are naturally more complicated.
Van der-Waals equation of state
The first practical cubic equation of state is the Van der Waals equation of state was proposed in
1873, and it has two constants that are determined from the behavior of a substance at the critical
point.

( )( )
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 Thermodynamics I

Includes two of the effects not considered in the ideal-gas model: the intermolecular attraction
forces and the volume occupied by the gas molecules themselves.

And
Where Tcr =critical temperature and Pcr =critical pressure
The accuracy of the Van der Waals equation of state is often inadequate, but it can be improved
by using values of a, & b that are based on the actual behavior of the gas over a wider range
instead of a single point. Despite its limitations, the van der Waals equation of state has a
historical value in that it was one of the first attempts to model the behavior of real gases.
Beattie-bridgeman equation of state
The Beattie-Bridgeman equation, proposed in 1928, is an equation of state based on five
experimentally determined constants. It is expressed as

The properties with a bar on top are molar basis. The five constants can be found in the table

below where P is in kPa, is in m3/kmol, T is in K and Ru is equal to 8.314 (kPa-m3) / (Kmol-

K). The Beattie-Bridgeman equation is known to be reasonably accurate for densities up to about
0.8ρcr, where ρcr is the density of the substance at the critical point.
Benedict-Webb-Rubin Equation of State
Benedict, Webb, and Rubin raised the number of experimentally determined constants in the
Beattie-Bridgeman Equation of State to eight in 1940.

This equation of state is accurate when ρ < 2.5 ρcr.

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 Thermodynamics I

2.5. Generalized correlations for gases

Generalized correlations find widespread use. Most popular are correlations of the kind
developed by Pitzer and coworkers for the compressibility factor Z and for the second virial
coefficient B.
Pitzer Correlations for the Compressibility Factor: The correlation for Z takes the form:

Where Z0 and Z' are functions of both Tr and Pr

( )
( )
And is the centric factor depend on of (Tc, Pc and Vc).

Equation of state that represents “Z” above is said to be generalized because of their general
applicability to all gases. A disadvantage of the generalized compressibility factor correlation is
its graphical nature; thus, figures may be used for quick estimates of Z0 and Z' verses Pr and Tr.
2.6. Generalized correlations for liquids
Although the molar volumes of liquids can be calculated by means of generalized cubic
equations of state, the results are often not of high accuracy. In addition, generalized equations
are available for the estimation of molar volumes of saturated liquids. The simplest equation,
proposed by Rackett,
( )

The only data required are the critical constants, given in App. B. from Smith thermodynamics
book. Lydersen, and Hougen developed a two-parameter corresponding-states correlation for
estimation of liquid volumes. It provides a correlation of reduced density p, as a function of
reduced temperature and pressure. By definition,

Where: ρc is the density at the critical point.

A better procedure is to make use of a single known liquid volume (state 1) by the identity,
Where V2 = required volume VI = known volume and ρr1, ρr2 = reduced

densities read from the graph.

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 Thermodynamics I

CHAPTER THREE
3. ENERGY AND THE FIRST LAW OF THERMODYNAMICS
3.1. Joule's Experiments
In his classical experiment, Joule submerged two tanks connected with a pipe and a valve in a
water bath, as shown in Fig. below. Initially, one tank contained air at a high pressure and the
other tank was evacuated. When thermal equilibrium was attained, he opened the valve to let air
pass from one tank to the other until the pressures equalized. Joule observed no change in the
temperature of the water bath and assumed that no heat was transferred to or from the air. Since
there was also no work done, he concluded that the internal energy of the air did not change even
though the volume and the pressure changed. Therefore, he reasoned, the internal energy is a
function of temperature only and not a function of pressure or specific volume.

Fig Schematic of the experimental apparatus used by Joule

Using the definition of enthalpy and the equation of state of an ideal gas, we have

Since R is constant and u=u (T), it follows that the enthalpy of an ideal gas is also a function of
temperature only: ( )
Since u and h depend only on temperature for an ideal gas, the specific heats cv and cp also
depend, at most, on temperature only.
Therefore, at a given temperature, u, h, cv, and cp of an ideal gas have fixed values regardless of
the specific volume or pressure.
Internal energy has no concise thermodynamic definition. It is a thermodynamic primitive. It
cannot be directly measured; there are no internal-energy meters. As a result, absolute values are
unknown. However, this is not a disadvantage in thermodynamic analysis, because only changes
in internal energy are required.

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 Thermodynamics I

3.2. The First Law of Thermodynamics

The first law of thermodynamics, also known as the conservation of energy principle, provides a
sound basis for studying the relationships among the various forms of energy and energy
interactions. Based on experimental observations, the first law of thermodynamics states that
energy can be neither created nor destroyed during a process; it can only change forms.
One formal statement is:
Although energy assumes many forms, the total quantity of energy is constant, and when
energy disappears in one form it appears simultaneously in other forms.
A major consequence of the first law is the existence and the definition of the property total
energy E. The first law applies to the system and surroundings, and not to the system alone. In its
most basic form, the first law requires:
( ) ( )
The system may change in its internal energy, in its potential or kinetic energy, and in the
potential or kinetic energy of its finite parts.

( )

( )

( )
Most systems encountered in practice are stationary, that is, they do not involve any changes in
their velocity or elevation during a process. Thus, for stationary systems, the changes in kinetic
and potential energies are zero (that is, ∆KE= ∆PE=0), and the total energy change relation in the
above equation reduces to ∆E =∆U for such systems.
The first law cannot be proven mathematically, but no process in nature is known to have
violated the first law, and this should be taken as sufficient proof. Note that if it were possible to
prove the first law on the basis of other physical principles, the first law then would be a
consequence of those principles instead of being a fundamental physical law itself. From the
first-law point of view, heat and work are not different at all. From the second-law point of view,
however, heat and work are very different, as is discussed in later chapters.

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 Thermodynamics I

3.3. Energy balance for closed systems

If the boundary of a system does not permit the transfer of matter between the system and its
surroundings, the system is said to be closed, and its mass is necessarily constant. Since no
streams enter or leave a closed system, no internal energy is transported across the boundary of
the system. All energy exchange between a closed system and its surroundings then appears as
heat and work, and the total energy change of the surroundings equals the net energy transferred
to or from it as heat and work.
( ) ( )
( )
Where
This equation means that the total energy change of a closed system equals the net energy
transferred into it as heat and work.

For stationary system the above equation becomes:

For a cyclic process ( ) the above equation becomes:

3.4. Thermodynamic state and state function

State is condition of a system identified by properties (e.g., T, P, v). In a given state each
property has one value.
If a gas is heated or cooled, compressed or expanded, and then returned to its initial temperature
and pressure, its intensive properties are restored to their initial values. Such properties do not
depend on the past history of the substance or on the means by which it reaches a given state.
They depend only on present conditions, however reached. Such quantities are known as state
functions.
The differential of a state function represents an infinitesimal change in its value. Integration of
such a differential result in a finite difference between two of its values, e.g.:

∫ ∫

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 Thermodynamics I

Heat and work are not properties; they account for the energy changes that occur in the
surroundings and appear only when changes occur in a system. They depend on the nature of the
process causing the change,
The differentials of heat and work are not changing, but are infinitesimal amounts. When
integrated, these differentials give not finite changes, but finite amounts. Thus,

∫ ∫

Any change that a system undergoes from one equilibrium state to another is called a process,
and the series of states through which a system passes during a process is called the path of the
process.
3.5. Equilibrium
Equilibrium is a word denoting a static condition, the absence of change. Thermodynamics deals
with equilibrium states. The word equilibrium implies a state of balance. In an equilibrium
system there are no unbalanced potentials (driving force) within the system.
• Thermal equilibrium: if the temperature is the same throughout the entire system
• Mechanical equilibrium: if there is no change in pressure at any point of the system with
time
• Chemical equilibrium: if the chemical composition of a system does not change with
time, that is no chemical reactions occur
Note that two systems are said to be in thermodynamic equilibrium when they are in thermal,
mechanical and chemical equilibrium with each other.

3.6. The reversible process

A reversible process is defined as a process that can be reversed without leaving any trace on the
surroundings. It means both system and surroundings are returned to their initial states at the end
of the reverse process. Processes that are not reversible are called irreversible.
Reversible processes do not occur and they are only idealizations of actual processes. We use
reversible process concept because, a) they are easy to analyze (since system passes through a
series of equilibrium states); b) they serve as limits (idealized models) to which the actual
processes can be compared.

24
 Thermodynamics I

The factors that cause a process to be irreversible are called irreversibility. They include
friction, unrestrained expansion and compression, mixing of two fluids, and heat transfer across a
finite temperature difference, electric resistance, inelastic deformation of solids, and chemical
reactions.
3.7. Constant-V and Constant-P Processes
The energy balance for a homogeneous closed system of n moles is:
( )
Where Q and W always represent total heat and work, whatever the value of n.
The work of a mechanically reversible, closed-system process is given by
( )
By combining the above two equation yields:
( ) ( )
This is the general first-law equation for a mechanically reversible, closed-system process, and
this equation can be simplified as follows for constant volume and pressure process as follows:
Constant-Volume Process
If the process occurs at constant total volume, the work is zero (Pd(nV)=0).
( )
Thus, for a mechanically reversible, constant-volume, closed-system process, the heat transferred
is equal to the internal-energy change of the system.
Constant-Pressure Process
( ) ( ) ( ) ( )
For a constant-pressure change of state:
( ) ( ) ( )
The appearance of the group U+ P V, both here and in other applications, suggests the
designation for convenience of a new thermodynamic property called enthalpy (H).

Where H, U, and V are molar or unit mass values. The preceding equation may now be written:
( )

25
 Thermodynamics I

Thus, for a mechanically reversible, constant-pressure, closed-system process, the heat

transferred equals the enthalpy change of the system. The enthalpy plays a role in constant-
pressure processes analogous to the internal energy in constant-volume processes.
3.8. Enthalpy
In the analysis of certain types of processes, particularly in power generation and refrigeration
we frequently encounter the combination of properties . For the sake of simplicity and
convenience, this combination is defined as a new property, enthalpy, and given the symbol h:

( ) Or ( )

It also appears in energy balances for flow processes as applied to heat exchangers, evaporators,
distillation columns, pumps, compressors, turbines, engines, etc., for calculation of heat and
work.
The tabulation of values of Q and W for the infinite array of possible processes is impossible.
The intensive state functions, however, such as specific volume, specific internal energy, and
specific enthalpy, are intrinsic properties of matter. Once determined, their values can be
tabulated as functions of temperature and pressure for each phase of a particular substance for
future use in the calculation of Q and W for any process involving that substance.
Since U, P, and V are all state functions, H is also a state function. Like U and V, H is an
intensive property of the system. The differential form of enthalpy given as:
( )
This equation applies whenever a differential change occurs in the system. Upon integration, it
becomes an equation for a finite change in the system:
( )
3.9. Heat capacity
We know from experience that it takes different amounts of energy to raise the temperature of
identical masses of different substances by one degree. For example, we need about 4.5 kJ of
energy to raise the temperature of 1 kg of iron from 20 to 30°C, whereas it takes about 9 times
this energy (41.8 kJ to be exact) to raise the temperature of 1 kg of liquid water by the same
amount. Therefore, it is desirable to have a property that will enable us to compare the energy
storage capabilities of various substances. This property is the specific heat.

26
 Thermodynamics I

The specific heat is defined as the energy required to raise the temperature of a unit mass of a
substance by one degree.
In thermodynamics, we are interested in two kinds of specific heats: specific heat at constant
volume cv and specific heat at constant pressure cp.
Specific heat at constant pressure, cp: The energy required to raise the temperature of the unit
mass of a substance by one degree as the pressure is maintained constant.

( )

(Constant P)

∫
Specific heat at constant volume, cv: The energy required to raise the temperature of the unit
mass of a substance by one degree as the volume is maintained constant.

( )

(Constant V)

∫
The Cp  Cv because at constant pressure the system is allowed to expand and the energy for this
expansion work must also be supplied to the system. When a gas is heated at constant volume the
work is done only to increase U of the system. When gas is heated at constant pressure work is
done to overcome this pressure and expand in volume as a result it increases the internal energy
of the system. Specific heats (both cv and cp) are properties; therefore, depend on the state
and/or independent of the type of processes.
3.10. Mass and Energy Balances for Open Systems
Control volumes (open system): Mass can cross the boundaries, and so we must keep track of
the amount of mass entering and leaving the control volume.
Conservation of mass: Mass, like energy, is a conserved property, and it cannot be created or
destroyed during a process. The laws of mass and energy conservation apply to all processes, to
open as well as to closed systems.
Measures of Flow
Open systems are characterized by flowing streams, for which there are four common measures
of flow:

27
 Thermodynamics I

• Mass flow rate (m), molar flow rate (n), volumetric flow rate (q) and velocity (u).
The measure of flow can be interrelated as:

Where M is molar mass. Importantly, mass and molar flow rates relate to velocity:

Flow rates m, n, and q represent measures of quantity per unit of time. Velocity u is quite
different in nature, as it does not suggest the magnitude of flow. Nevertheless, it is an important
design parameter.
Mass Balance for Open Systems
The region of space identified for analysis of open systems is called a control volume; it is
separated from its surroundings by a control surface. The fluid within the control volume is the
thermodynamic system for which mass and energy balances are written.

The convention is that flow is positive when directed into the control volume and negative when
directed out. The mass balance is expressed mathematically by:

In this form the mass-balance equation is often called the continuity equation.

28
 Thermodynamics I

The flow process characterized as steady state is an important special case for which conditions
within the control volume do not change with time. The control volume then contains a constant
mass of fluid, and the first or accumulation term is zero,

When there is but a single entrance and a single exit stream, the mass flow rate is the same for
both streams; then,

Since specific volume is the reciprocal of density,

The General Energy Balance

Since energy, like mass, is conserved, the rate of change of energy within the control volume
equals the net rate of energy transfer into the control volume. Streams flowing into and out of the
control volume have associated with them energy in its internal, potential, and kinetic forms, and
all contribute to the energy change of the system.
Each unit mass of a stream carries with it a total energy ( )

Each stream transports energy at the rate

The net energy transported into the system by the flowing streams is therefore

The rate of energy accumulation within the control volume includes this quantity in addition to
the heat transfer rate Q ˙ and work rate:

The work done by this piston in moving the unit mass through the entrance is PV, and the work
rate is (PV) m ˙. Because Δ denotes the difference between exit and entrance quantities, the net

29
 Thermodynamics I

work done on the system when all entrance and exit sections are taken into account is

Another form of work is the shaft work indicted by rate In addition; work may be associated
with expansion or contraction of the entire control volume. These forms of work are all included

in a rate term represented by the preceding equation may now be written:

Combination of terms in accord with the definition of enthalpy, , leads to:

For many (but not all) applications, kinetic- and potential-energy changes in the flowing streams
are also negligible, and the above equation simplifies to:

Flow processes for which the accumulation term in the above equation, (d(mU)cv/dt), is zero are
said to occur at steady state.
No expansion of the control volume is possible under these circumstances. The only work of the
process is shaft work, and the general energy balance becomes:

30
 Thermodynamics I

3.11. Limitations of first law of thermodynamics

There are some important limitations of First Law of Thermodynamics.
1. When a closed system undergoes a thermodynamic cycle, the net heat transfer is equal to
the net-work transfer. The law does not specify the direction of flow of heat and work nor
gives any condition under which energy transfer can take place.
2. The heat energy and mechanical work are mutually convertible. The mechanical energy
can be fully converted into heat energy but only a part of heat energy can be converted
into mechanical work. Therefore, there is a limitation on the amount of conversion of one
form of energy into another form.

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 Thermodynamics I

CHAPTER FOUR
4. THE SECOND LAW OF THERMODYNAMICS
INTRODUCTION TO THE SECOND LAW
The second law of thermodynamics asserts that processes occur in a certain direction and that the
energy has quality as well as quantity. The first law places no restriction on the direction of a
process, and satisfying the first law does not guarantee that the process will occur. Thus, we need
another general principle (second law) to identify whether a process can occur or not.
Heat transfer from a hot container to the cold surroundings is possible; however, the reveres
process (although satisfying the first law) is impossible.
A process can occur when and only when it satisfies both the first and the second laws of
thermodynamics.
The second law also asserts that energy has a quality. Preserving the quality of energy is a major
concern of engineers. In the above example, the energy stored in a hot container (higher
temperature) has higher quality (ability to work) in comparison with the energy contained (at
lower temperature) in the surroundings.
The second law is also used in determining the theoretical limits for the performance of
commonly used engineering systems, such as heat engines and refrigerators etc.
4.1. Thermal energy reservoirs
Thermal energy reservoirs are hypothetical bodies with a relatively large thermal energy capacity
(mass x specific heat) that can supply or absorb finite amounts of heat without undergoing any
change in temperature. Lakes, rivers, atmosphere, oceans are example of thermal reservoirs.
A body does not actually have to be very large to be considered a reservoir.
A reservoir that supplies energy in the form of heat is called a source, and one that absorbs
energy in the form of heat is called a sink. Thermal energy reservoirs are often referred to as
heat reservoirs since they supply or absorb energy in the form of heat.
4.2. Heat engines
We have seen that work always converts directly and completely to heat, but converting heat to
work requires the use of some special devices. These devices are called Heat Engines.
Heat engines differ considerably from one another, but all can be characterized by the following:
1. They receive heat from a high-temperature source (Oil furnace, nuclear reactor, etc.).

32
 Thermodynamics I

2. They convert part of this heat to work (usually in the form of a rotating shaft).
3. They reject the remaining waste heat to a low-temperature sink (the atmosphere, rivers,
etc.).
4. They operate on a cycle.

Fig: Part of the heat received by a heat engine is converted to work, while the rest is rejected to a
sink.
Heat engines and other cyclic devices usually involve a fluid to and from which heat is
transferred while undergoing a cycle. This fluid is called the working fluid.
Thermal Efficiency
The fraction of the heat input that is converted to net-work output is a measure of the
performance of a heat engine and is called the thermal efficiency (ƞth).

For heat engines, the desired output (benefit) is the net-work output, and the required input (cost)
is the amount of heat supplied to the working fluid.

Or

Is it possible to save the rejected heat Qout in a power cycle? The answer is NO, because
without the cooling in condenser the cycle cannot be completed. Every heat engine must waste

33
 Thermodynamics I

some energy by transferring it to a low‐temperature reservoir in order to complete the cycle,

even in idealized cycle.
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.
The Kelvin–Planck statement can also be expressed as no heat engine can have a thermal
efficiency of 100 percent, or as for a power plant to operate, the working fluid must exchange
heat with the environment as well as the furnace.
Note that the impossibility of having a 100% efficient heat engine is not due to friction or other
dissipative effects. It is a limitation that applies to both idealized and the actual heat engines.
4.3. Thermodynamic temperature scales
A temperature scale that is independent of the properties of the substances that are used to
measure temperature is called a thermodynamic temperature scale. Such a temperature scale
offers great conveniences in thermodynamic calculations, and its derivation is given below using
some reversible heat engines.
The efficiency of a reversible engine is independent of the working fluid employed and its
properties, the way the cycle is executed, or the type of reversible engine used. Since energy
reservoirs are characterized by their temperatures, the thermal efficiency of reversible heat
engines is a function of the reservoir temperatures only. That is,

Since: . In these relations TH and TL are the temperatures of the high- and low-

temperature reservoirs, respectively.

The functional form of f (TH, TL) can be developed with the help of the three reversible heat
engines shown in Fig. below. Engines A and C are supplied with the same amount of heat Q1
from the high-temperature reservoir at T1. Engine C rejects Q3 to the low-temperature reservoir

34
 Thermodynamics I

at T3. Engine B receives the heat Q2 rejected by engine A at temperature T2 and rejects heat in
the amount of Q3 to a reservoir at T3.
The amounts of heat rejected by engines B and C must be the same since engines A and B can be
combined into one reversible engine operating between the same reservoirs as engine C and thus
the combined engine will have the same efficiency as engine C. Since the heat input to engine C
is the same as the heat input to the combined engines A and B, both systems must reject the same
amount of heat.

Applying the above equation to all three engines separately, we obtain

( ) ( ) ( )

This corresponds to:

( ) ( ) ( )

A careful examination of this equation reveals that the left-hand side is a function of T1 and T3,
and therefore the right-hand side must also be a function of T1 and T3 only, and not T2. That is,
the value of the product on the right-hand side of this equation is independent of the value of T2.
This condition will be satisfied only if the function f has the following form:

( ) ( )
( ) ( )
( ) ( )

So that (T2) will cancel from the product of f (T1, T2) and f (T2, T3), yielding

( )
( )
( )

35
 Thermodynamics I

For a reversible heat engine operating between two reservoirs at temperatures TH and TL, the
above equation can be written as:

( )
( )

This is the only requirement that the second law places on the ratio of heat transfers to and from
the reversible heat engines. Several functions (T) satisfy this equation, and the choice is
completely arbitrary. Lord Kelvin first proposed taking (T) = T to define a thermodynamic
temperature scale as:

This temperature scale is called the Kelvin scale, and the temperatures on this scale are called
absolute temperatures. On the Kelvin scale, the temperature ratios depend on the ratios of heat
transfer between a reversible heat engine and the reservoirs and are independent of the physical
properties of any substance. On this scale, temperatures vary between zero and infinity.

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:

Differentiation of the defining equation for enthalpy, H = U + PV, yields:

Eliminating dU gives:

For the ideal-gas state, d H ig = C P ig dT and V ig = RT / P . With these substitutions and

36
 Thermodynamics I

division by T,

Although derived for a mechanically reversible process, this equation relates properties
only, independent of the process causing the change of state, and is therefore a general
equation for the calculation of entropy changes in the ideal-gas state.

37
 Thermodynamics I

CHAPTER FIVE

5. THERMODYNAMIC CYCLES

Refrigerators and Heat Pumps

In nature, heat flows from high‐temperature regions to low‐temperature ones. The reverse
process, however, cannot occur by itself. The transfer of heat from a low temperature region to a
high‐temperature one requires special devices called refrigerators and or heat pump.
Refrigerators are cyclic devices, and the working fluids used in the cycles are called refrigerant.

Heat pumps transfer heat from a low‐temperature medium to a high‐temperature one.

Refrigerators and heat pumps are essentially the same devices; they differ in their objectives
only. Refrigerator is to maintain the refrigerated space at a low temperature. On the other hand, a
heat pump absorbs heat from a low‐temperature source and supplies the heat to a warmer
medium.

Fig.: Objectives of refrigerator and heat pump.

Coefficient of Performance (COP)
The performance of refrigerators and heat pumps is expressed in terms of the coefficient of
performance (COP) which is defined as:

It can be seen that

38
 Thermodynamics I

Air conditioners are basically refrigerators whose refrigerated space is a room or a building.
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 higher‐temperature body. In other words, a
refrigerator will not operate unless its compressor is driven by an external power source.
Kelvin‐Planck and Clausius statements of the second law are negative statements, and a negative
statement cannot be proved. So, the second law, like the first law, is based on experimental
observations.
The two statements of the second law are equivalent. In other words, any device violates the
Kelvin‐Planck statement also violates the Clausius statement and vice versa.
Any device that violates the first law of thermodynamics (by creating energy) is called a
perpetual‐motion machine of the first kind (PMM1), and the device that violates the second law
is called a perpetual‐motion machine of the second kind (PMM2).
Example
An inventor claims to have developed a refrigerator that maintains the refrigerated space at 35°F
while operating in a room where the temperature is 75°F and that has a COP of 13.5. Is this
claim reasonable?
Solution An extraordinary claim made for the performance of a refrigerator is to be evaluated.
Assumptions Steady operating conditions exist.

39
 Thermodynamics I

Discussion This is the highest COP a refrigerator can have when absorbing heat from a cool
medium at 35°F and rejecting it to a warmer medium at 75°F. Since the COP claimed by the
inventor is above this maximum value, the claim is false.

5.2. The Vapor-Compression Cycle

Vapor compression refrigeration systems are the most commonly used among all refrigeration
systems. As the name implies, these systems belong to the general class of vapor cycles, wherein
the working fluid (refrigerant) undergoes phase change at least during one process. In a vapor
compression refrigeration system, refrigeration is obtained as the refrigerant evaporates at low
temperatures. The input to the system is in the form of mechanical energy required to run the
compressor. Hence these systems are also called as mechanical refrigeration systems. Vapor
compression refrigeration systems are available to suit almost all applications with the
refrigeration capacities ranging from few Watts to few megawatts. A wide variety of refrigerants
can be used in these systems to suit different applications, capacities etc.
A simple vapor compression refrigeration system consists of the following components:
 A compressor which compresses the vaporous working fluid and providing required
mechanical energy, W, to the system
 The condenser that absorbs heat (at constant pressure) from the working medium and
transfer it to the high temperature source
 An expansion (throttling) valve that expands the liquid working medium during a
constant enthalpy process
 An evaporator facilitates the evaporation of the working medium while it absorbs heat
from the low temperature reservoir
Process of vapor compression cycle
1. Process 1-2:
Isentropic compression of saturated vapor in compressor (P increases, T increases @ constant

40
 Thermodynamics I

S (entropy), v (specific volume) decreases

2. Process 2-3:
Constant (P) heat rejection in condenser
3. Process 3-4:
Isenthalpic expansion of saturated liquid in expansion device, (P decreases, T decreases @
Constant h (enthalpy), v (specific volume) increases
4. Process 4-1:
Constant (P) heat extraction in the evaporator

5.3. ABSORPTION REFRIGERATION SYSTEMS

Another form of refrigeration that becomes economically attractive when there is a source of
inexpensive thermal energy at a temperature of 100 to 200°C is absorption refrigeration. Some
examples of inexpensive thermal energy sources include geothermal energy, solar energy, and
waste heat from cogeneration or process steam plants, and even natural gas when it is available
at a relatively low price.

As the name implies, absorption refrigeration systems involve the absorption of a refrigerant by
a transport medium. The most widely used absorption refrigeration system is the ammonia–water
system, where ammonia (NH3) serves as the refrigerant and water (H2O) as the transport
medium. Other absorption refrigeration systems include water–lithium bromide and water–
lithium chloride systems, where water serves as the refrigerant.

41
 Thermodynamics I

5.4. THE CHOICE OF REFRIGERANT

When designing a refrigeration system, there are several refrigerants from which to choose, such
as chlorofluorocarbons (CFCs), ammonia, hydrocarbons (propane, ethane, ethylene, etc.), carbon
dioxide, air (in the air-conditioning of aircraft), and even water (in applications above the
freezing point). The right choice of refrigerant depends on the situation at hand. Of these,
refrigerants such as R-11, R-12, R-22, R-134a, and R-502 account for over 90 percent of the
market in the United States.

Two important parameters that need to be considered in the selection of a refrigerant are the
temperatures of the two media (the refrigerated space and the environment) with which the
refrigerant exchanges heat.

Other desirable characteristics of a refrigerant include being nontoxic, noncorrosive,

nonflammable, and chemically stable; having a high enthalpy of vaporization (minimizes the
mass flow rate); and, of course, being available at low cost.

5.5. HEAT PUMP SYSTEMS

A heat pump transports heat from a low temperature level to a higher temperature level. To do
this, the heat pump requires drive power. This can be mechanical, electrical or thermal. Usually
heat pumps which operate according to the principle of a compression refrigeration system are
used. Less often, heat pumps running on the absorption process are used.

The COP is an important indicator for the operation of heat pumps. COP stands for “Coefficient
of Performance”. The COP indicates how efficiently a heat pump works. The COP indicates the
ratio of heat capacity and the required drive power. This value allows an easy comparison
between different heat pumps. The COP is directly dependent on the temperature of the heat
source and the heating temperature in the building. Therefore, the COP changes at each operating
point of the heat pump. The larger the COP, the more effective the heat pump.

The most common energy source for heat pumps is atmospheric air (air-to-air systems), although
water and soil are also used. The major problem with air-source systems is frosting, which
occurs in humid climates when the temperature falls below 2 to 5°C.

42
 Thermodynamics I

Review Questions

1. Heating of water under atmospheric pressure is __________ process.

A. Isochoric B. Isobaric C. Adiabatic D. Isothermal

2. Internal energy change of a system over one complete cycle in a cyclic process is

A. zero B. +ve C. -ve D. dependent on the path

3. High __________ is an undesirable property for a good refrigerant.

A. specific heat B. latent heat of vaporization

C. viscosity D. specific vapor volume

4. Entropy is a measure of the __________ of a system.

A. disorder B. orderly behavior

C. temperature changes only D. none of these

5. Fundamental principle of refrigeration is based on the __________ law of

thermodynamics.

A. Zeroth B. First C. Second D. Third

6. In a working refrigerator, the value of COP is always

A. 0 B. < 0 C. < 1 D. > 1

7. A refrigerator may be termed as a

A. Heat pump B. Heat engine C. Carnot engine D. None

8. Measurement of thermodynamic property of temperature is facilitated by __________

law of thermodynamics.

A. 1st B. Zeroth C. 3rd D. none of these

43
 Thermodynamics I

9. Isobaric process means a constant process.

A. Temperature B. Pressure C. volume D. entropy

10. No work is done by the system, when a reaction occurs at constant

A. volume B. temperature C. pressure D. none of these

11. "At the absolute zero temperature, the entropy of every perfectly crystalline substance
becomes zero". This follows from the

A. Third law of thermodynamics

B. Second law of thermodynamics

C. Nernst heat theorem

D. Maxwell's relations

12. During Joule-Thomson expansion of gases

A. enthalpy remains constant.

B. entropy remains constant.

C. temperature remains constant.

D. None of these.

13. 1st law of thermodynamics is nothing but the law of conservation of

A. momentum B. mass C. energy D. none of these

14. Out of the following refrigeration cycles, which one has maximum COP?

A. Air cycle B. Carnot cycle

C. Ordinary vapor compression cycle

44
 Thermodynamics I

D. Vapor compression with a reversible expansion engine

15. Heat pump

A. Accomplishes only space heating in winter. B. Accomplishes only space cooling in summer.

C. Accomplishes both (a) and (b). D. Works on Carnot cycle.

16. The temperature at which both liquid and gas phases are identical, is called the
__________ point.

A. Critical B. Triple C. Freezing D. Boiling

17. Isentropic process means a constant __________ process.

A. Enthalpy B. Pressure C. Entropy D. None

18. A liquid under pressure greater than its vapour pressure for the temperature involved
is called a __________ liquid.

A. Sub-cooled B. Saturated C. Non-solidifiable D. None

19. In polytropic process (PVn = constant), if n = 1; it means a/an __________ process.

A. Adiabatic B. Reversible C. Isothermal D. None

20. Co-efficient of Performance (COP) of a refrigerator is the ratio of the

A. Work required to refrigeration obtained. B. Refrigeration obtained to the work required.

C. Lower to higher temperature. D. Higher to lower temperature.

21. At __________ point, all the three phases (i.e. Solid, liquid and gas) co-exist.

A. Eutectic B. Triple C. Plait D. Critical

22. Which of the following is not a reversible process?

A. Expansion of an ideal gas against constant pressure.

B. Atmospheric pressure vaporization of water at 100°C.

45
 Thermodynamics I

C. Solution of sodium chloride in water at 50°C. D. None of these.

23. Entropy, which is a measure of the disorder of a system is:

A. Independent of pressure. B. Independent of temperature.

C. Zero at absolute zero temperature for a perfect crystalline substance. D. All

24. Compressibility factor of a gas is

A. Not a function of its pressure. B. Not a function of its nature.

C. Not a function of its temperature. D. Unity, if it follows PV = nRT

25. Chemical engineering thermodynamics is concerned with the __________ in/of chemical
processes.

A. Reaction mechanism B. Calculation of rates

C. Energy transformation from one form to another D. None

26. An isolated system can exchange __________ with its surroundings.

A. Matter B. Energy C. Neither matter nor energy D. Both matter and energy

27. The internal energy of an ideal gas is a function of its __________ only.

A. Molecular size B. Volume C. Pressure D. Temperature

28. Work done is a

A. Property of the system B. Path function C. Point function D. State description of a

system

29. Extensive properties of a thermodynamic system depend upon the __________ of the system.

A. Specific volume B. Temperature C. Mass D. Pressure

30. Equation which relates pressure, volume and temperature of a gas is called the

A. Equation of state B. Gibbs Duhem equation

46
 Thermodynamics I

C. Ideal gas equation D. None

31. __________ law of thermodynamics ascertains the direction of a particular spontaneous

process.

A. Zeroth B. First C. Second D. Third

32. __________ functions are exemplified by heat and work.

A. Path B. Point C. State D. None

33. The equation, PV = nRT, is best obeyed by gases at

A. Low pressure & high temperature. B. High pressure & low temperature.

C. Low pressure & low temperature. D. None.

34. The extensive properties are

A. Volume, mass and number of moles. B. Free energy, entropy and enthalpy.

C. Both (a) and (b). D. None

35. Cp - Cv = R is valid for __________ gases.

A. Ideal B. All C. Very high-pressure D. Very low temperature

36. Reduced pressure of a gas is the ratio of its

A. Pressure to critical pressure. B. Critical pressure to pressure.

C. Pressure to pseudo-critical pressure. D. Pseudo-critical pressure to pressure.

37. Which of the following is not the limitation of first law of thermodynamics?

A. Does not take in to account the law of conservation of energy

B. Does not indicate the direction in which change takes place

C. Gives no information about the extent of change

47
 Thermodynamics I

D. Gives no information about the heat source

48