11/24/2023

HARAMAYA UNIVERSITY
HARAMAYA INSTITUTE OF TECHNOLOGY
DEPARTMENT OF CHEMICAL ENGINEERING
CHEMICAL ENGINEERING THERMODYNAMICS I
BY
Melkiyas Diriba (MSc. In Chemical Process and Product Design)
2023/24 1
 Chapter Three: Energy and First law of thermodynamics

Learning Outcomes

At the end of this chapter the students will be able to:

 Know the concept of first law of thermodynamics

 Examine and understand the mechanisms of energy transfer

 Design the energy balances for closed and open systems and

 Compute the problems related to the applications of first law.

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 Forms of Energy
◦ Energy can exist in numerous forms such as thermal, mechanical, kinetic, potential,
electric, magnetic, chemical, and nuclear (Fig. 1), and their sum constitutes the total
energy E of a system. The total energy of a system on a unit mass basis is denoted by e and
is expressed as

E
ⅇ=m (kJ/kg)

 At least six different forms of energy are encountered

in bringing power from a nuclear plant to your home:
 Nuclear,
 Thermal,
 Mechanical,
 Kinetic,
 Magnetic, and Fig. 1. Nuclear plant
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 Electrical. 3
 The macroscopic forms of energy are those a system possesses as a whole with respect to
some outside reference frame, such as kinetic and potential energies.

 The microscopic forms of energy are those related to the molecular structure of a system
and the degree of the molecular activity, and they are independent of outside reference
frames.

 The sum of all the microscopic forms of energy is called the internal energy of a system and
is denoted by U.

 The macroscopic energy of a system is related to motion and the influence of some
external effects such as gravity, magnetism, electricity, and surface tension.

 The energy that a system possesses as a result of its motion relative to some reference
frame is called kinetic energy (KE).

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When all parts of a system move with the same velocity, the kinetic energy is expressed as

where V denotes the velocity of the system relative to some fixed reference frame.

𝟏
 The kinetic energy of a rotating solid body is given by 𝑰𝝎𝟐 where I is the moment of inertia
𝟐

of the body and 𝛚 is the angular velocity.

 The energy that a system possesses as a result of its elevation in a gravitational field is called potential
energy (PE) and is expressed as  where g is the gravitational acceleration and
z is the elevation of the center of gravity of a
system relative to some arbitrarily selected
11/24/2023 reference level. 5
 The magnetic, electric, and surface tension effects are significant in some specialized cases
only and are usually ignored.

 In the absence of such effects, the total energy of a system consists of the kinetic, potential,
and internal energies and is expressed as

Mechanical Energy: The mechanical energy can be defined as the form of energy that can be
converted to mechanical work completely and directly by an ideal mechanical device such as an
ideal turbine.
 Kinetic and potential energies are the familiar forms of mechanical energy.
 Thermal energy is not mechanical energy, however, since it cannot be converted to work directly
and completely (the second law of thermodynamics).
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Flow work is expressed in terms of fluid properties, and it is convenient to view it as part of
the energy of a flowing fluid and call it flow energy.

Therefore, the mechanical energy of a flowing fluid can be expressed on a unit mass basis
as

where P/𝛒 is the flow energy, 𝒗𝟐 /2 is the kinetic energy, and gz is the potential energy of the
fluid, all per unit mass. It can also be expressed in rate form as

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 Therefore, the mechanical energy of a fluid does not change during flow if its pressure,

density, velocity, and elevation remain constant.

 In the absence of any irreversible losses, the mechanical energy change represents the

mechanical work supplied to the fluid (if ∆𝒆𝒎 > 𝟎) or extracted from the fluid (if ∆𝒆𝒎 < 𝟎).

 The maximum (ideal) power generated by a turbine, for example, is

Example 3.1. A site evaluated for a wind farm is observed to have steady winds at a speed of

8.5 m/s. Determine the wind energy (a) per unit mass, (b) for a mass of 10 kg, and (c) for a

flow rate of 1154 kg/s for air.

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 Energy Transfer by Heat
 Energy can cross the boundary of a closed system in two distinct forms: heat and work as shown in Fig.
below.

 It is important to distinguish between these two forms of energy.

◦ A process during which there is no heat transfer is called an adiabatic process.

◦ There are two ways a process can be adiabatic:

i. Either the system is well insulated so that only a negligible amount of heat can pass
through the boundary, or

ii. Both the system and the surroundings are at the same temperature and therefore there is
no driving force (temperature difference) for heat transfer.
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◦ The amount of heat transferred during the process between two states (states 1 and 2) is
denoted by Q12, or just Q.

◦ Heat transfer per unit mass of a system is denoted q and is determined from

 When 𝑸ሶ varies with time, the amount of heat transfer during a process is determined by

integrating 𝑸ሶ over the time interval of the process:

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Heat is transferred by three mechanisms: conduction, convection, and radiation.

i. Conduction: is the transfer of energy from the more energetic particles of a substance

to the adjacent less energetic ones as a result of interaction between particles.

ii. Convection: is the transfer of energy between a solid surface and the adjacent fluid

that is in motion, and it involves the combined effects of conduction and fluid motion.

iii. Radiation: is the transfer of energy due to the emission of electromagnetic waves (or

photons).

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 Energy Transfer by Work
 Work, like heat, is an energy interaction between a system and its surroundings.

 If the energy crossing the boundary of a closed system is not heat, it must be work.

 Work is the energy transfer associated with a force acting through a distance.

 A rising piston, a rotating shaft, and an electric wire crossing the system boundaries are all
associated with work interactions.

 Work is also a form of energy transferred like heat and, therefore, has energy units such as
kJ.

 The work done during a process between states 1 and 2 is denoted by W12, or simply W. The
work done per unit time is called power and is denoted 𝒘.
ሶ

 Heat and work are directional quantities, and thus the complete description of a heat or work
interaction requires the specification of both the magnitude and direction
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Heat and work are energy transfer mechanisms between a system and its surroundings, and
there are many similarities between them:

i. Both are recognized at the boundaries of a system as they cross the boundaries. That is,

both heat and work are boundary phenomena.

ii. Systems possess energy, but not heat or work.

iii. Both are associated with a process, not a state. Unlike properties, heat or work has no

meaning at a state.

iv. Both are path functions (i.e., their magnitudes depend on the path followed during a

process as well as the end states).

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Mechanical Forms of Work
There are several different ways of doing work, each in some way related to a force acting through a
distance (Fig. 3).

In elementary mechanics, the work done by a constant force F on a body displaced a
distance s in the direction of the force is given by
There are two requirements for a work
interaction between a system and its
surroundings to exist:
i. There must be a force acting on the
boundary, and
ii. The boundary must move.
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 Shaft Work
 Energy transmission with a rotating shaft is very common in engineering practice.

 Often the torque T applied to the shaft is constant, which means that the force F applied is also
constant.

 For a specified constant torque, the work done during n revolutions is determined as follows: A force F
acting through a moment arm r generates a torque T of (Fig. 4).

The power transmitted through the shaft is the shaft work done per unit time, which can be expressed
as

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 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.

 Therefore, every bit of energy should be accounted for during a process.

 Consider a system undergoing a series of adiabatic processes from a specified state 1 to another specified
state 2.

 Being adiabatic, these processes obviously cannot involve any heat transfer, but they may involve
several kinds of work interactions.

 Careful measurements during these experiments indicate the following:

 For all adiabatic processes between two specified states of a closed system, the net work done is the same
regardless of the nature of the closed system and the details of the process.
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 Energy Balance
 The net change (increase or decrease) in the total energy of the system during a process is
equal to the difference between the total energy entering and the total energy leaving the
system during that process. That is,

(Total energy entering the system) - (Total energy leaving the system) = (Change in the total
energy of the system)

or

Ein - Eout = 𝜟Esystem

Energy Change of a System, 𝚫Esystem

Energy change = Energy at final state - Energy at initial state
or

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∆Esystem = Efinal - Einitial = 𝐄ሶ 𝟐 − 𝐄ሶ 𝟏 17
 Also, energy can exist in numerous forms such as internal (sensible, latent, chemical, and
nuclear), kinetic, potential, electric, and magnetic, and their sum constitutes the total
energy E of a system.

 In the absence of electric, magnetic, and surface tension effects (i.e., for simple
compressible systems), the change in the total energy of a system during a process is the
sum of the changes in its internal, kinetic, and potential energies and can be expressed as

 Thus, for stationary systems, the changes in kinetic and potential energies are zero (that is,
𝚫KE = 𝚫PE = 0), thus the above equation reduce to

𝚫E = 𝚫U
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 Mechanisms of Energy Transfer, Ein and Eout
 Energy can be transferred to or from a system in three forms: heat, work, and mass flow.

 The only two forms of energy interactions associated with a fixed mass or closed system are heat transfer
and work.

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.

Work Transfer, W: Work transfer to a system (i.e., work done on a system) increases the energy of the
system, and work transfer from a system (i.e., work done by the system) decreases it since the energy
transferred out as work comes from the energy contained in the system.

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).
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 Noting that energy can be transferred in the forms of heat, work, and mass, and that the net
transfer of a quantity is equal to the difference between the amounts transferred in and out,
the energy balance can be written more explicitly as

 Energy balance for any system undergoing any kind of process can be expressed more
compactly as

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 Joule's Experiments

 In the most famous series of measurements, he placed known amounts of water, oil, and

mercury in an insulated container and agitated the fluid with a rotating stirrer.

 The amounts of work done on the fluid by the stirrer were accurately measured, and the

temperature changes of the fluid were carefully noted.

 He found for each fluid that a fixed amount of work was required per unit mass for every

degree of temperature rise caused by the stirring, and that the original temperature of the

fluid could be restored by the transfer of heat through simple contact with a cooler object.

 Thus Joule was able to show conclusively that a quantitative relationship exists between

work and heat and, therefore, that heat is a form of energy.

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 The same proportionality was obtained by the following different methods of transforming
work into heat:

i. The mechanical work was converted to electricity and the electric current was passed
through coils immersed in water.

ii. A gas confined in a cylinder immersed in water was compressed mechanically.

iii. Two metal pieces immersed in water were rubbed against each other by mechanical
work.

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 Conservation of energy
 In the early part of nineteenth century the scientists developed the concept of energy and
hypothesis that it can be neither created nor destroyed;
this came to be known as the law of the conservation of energy.

 The first law of thermodynamics is merely one statement of this general law/principle with
particular reference to heat energy and mechanical energy i.e., work.
 For example, when a pendulum swings, potential energy is converted to kinetic energy and back again.

 It is a fundamental principle of physics that states that the total energy in a closed system
remains constant overtime.
◦ The law of conservation of energy has many applications in physics and chemistry.
o It can be used to solve problems involving isolated systems, conservative forces, and non-
conservative forces.
o It also important in environmental science, where it is used to study the impact of human
activities on the environment.
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 Energy analysis of Closed System

Moving Boundary Work

 One form of mechanical work frequently encountered in practice is associated with the
expansion or compression of a gas in a piston–cylinder device.

 During this process, part of the boundary (the inner face of the piston) moves back and
forth.

 Therefore, the expansion and compression work is often called moving boundary work, or
simply boundary work (Fig.6).

Fig.6. The work associated with a moving boundary is called boundary work.
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 Moving boundary work is the primary form of work involved in automobile engines.

 During their expansion, the combustion gases force the piston to move, which in turn forces
the crankshaft to rotate.

 The moving boundary work associated with real engines or compressors cannot be
determined exactly from a thermodynamic analysis alone because the piston usually
moves at very high speeds, making it difficult for the gas inside to maintain equilibrium.

 Then the states through which the system passes during the process cannot be specified,
and no process path can be drawn.

 Work, being a path function, cannot be determined analytically without a knowledge of the
path.

 Therefore, the boundary work in real engines or compressors is determined by direct

measurements.
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Consider the gas enclosed in the piston–cylinder device shown in Fig. 7.

 The initial pressure of the gas is P, the total volume is V, and the cross-
sectional area of the piston is A.
 If the piston is allowed to move a distance ds in a quasi-equilibrium
manner, the differential work done during this process is

 That is, the boundary work in the differential form is equal to the product of the absolute

pressure P and the differential change in the volume dV of the system.

 This expression also explains why the moving boundary work is sometimes called the P

dV work.

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 The total boundary work done during the entire process as the piston moves is obtained by
adding all the differential works from the initial state to the final state:

(*)

 This integral can be evaluated only if we know the functional relationship between P and V during the
process.

 The quasi-equilibrium expansion process described is shown on a P-V diagram in Fig. 8.

 On this diagram, the differential area dA is equal to P dV, which is the differential work.
 The total area A under the process curve 1–2 is obtained by adding these differential areas:

11/24/2023 Fig.8. The area under the process curve on a P-V diagram represents the boundary work. 27
 Polytropic Process
 During actual expansion and compression processes of gases, pressure and volume are often related
by PVn = C, where n and C are constants.

 A process of this kind is called a polytropic process (Fig. 9). Below we develop a general expression
for the work done during a polytropic process.

 The pressure for a polytropic process can be expressed as

Substituting this relation into Eq. (*), we obtain

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 Energy Balance for Closed Systems
Energy balance for any system undergoing any kind of process was expressed as

For constant rates, the total quantities during a time interval Dt are related to the quantities per unit time
as

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 Mass and Energy balances for open system
 The laws of mass and energy conservation apply to all processes, to open as well as to closed
systems.

 Indeed, the open system includes the closed system as a special case.

Measures of Flow
Open systems are characterized by flowing streams, for which there are four common measures of flow:
 Mass flowrate, m
 Molar flowrate, n
 Volumetric flowrate, q
 Velocity, u

The measures of flow are interrelated: 𝒎ሶ = M𝒏ሶ and q = uA

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 The area for flow A is the cross-sectional area of a conduit, and 𝛒 is specific or molar
density.

 Although velocity is a vector quantity, its scalar magnitude u is used here as the average
speed of a stream in the direction normal to A.

 Flowrates 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.

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◦ Two streams with flow rates ml and m2 are shown directed into the control volume, and one stream
with flow rate m3 is directed out.

◦ Since mass is conserved, the rate of change of mass within the control volume, dmcv/dt, equals the
net rate of flow of mass into the control volume.

◦ 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:

◦ where the second term for the control volume shown in Fig. is:

11/24/2023 Fig. Schematic representing of a control volume 32

 The difference operator "𝚫" here signifies the difference between exit and entrance flows
and the subscript "fs" indicates that the term applies to all flowing streams.

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

equation.

 The flow process characterized as steady state is an important special case for which conditions
within the control volume do not change with time. Then,

 The term "steady state" does not necessarily imply that flowrates are constant, merely that the inflow
of mass is exactly matched by the outflow of mass.

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 When there is but a single entrance and a single exit stream, the mass flowrate riz is the
same for both streams; then,

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 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 U + ½ u2 + zg, where u is the average velocity

of the stream, z is its elevation above a datum level, and g is the local acceleration of gravity.

 Thus, each stream transports energy at the rate (U + 1/2u2 + zg)𝒎.

ሶ

 The net energy transported into the system by the flowing streams is therefore -A [(u + 1/2u2 + zg)𝒎]
ሶ fs,

where the effect of the minus sign with "𝚫" is to make the term read in - out.
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◦ The rate of energy accumulation within the control volume includes this quantity in addition to the
heat transfer rate Q and work rate:

◦ Another form of work is the shaft work indicated in Fig. 11 by rate Ws,.

◦ In addition work may be associated with expansion or contraction of the control volume and there
may be stirring work.

◦ These forms of work are all included in a rate term represented by W .

◦ The preceding equation may now be written

(i)

11/24/2023 Fig.11. Control volume with one entrance and one exit 36
◦ For many (but not all) applications, kinetic- and potential-energy changes in the flowing
streams are also negligible, and above equation, then simplifies to:

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 Energy Balances for Steady-State Flow Processes
 Flow processes for which the accumulation term of Eq. (i), d(mU)cv/dt, is zero are said to occur at
steady state.

 The only work of the process is shaft work, and the general energy balance, Eq. (i), becomes:

(ii)

 A further specialization results when the control volume has but one entrance and one exit.

 The same mass flowrate m then applies to both streams, and Eq. (ii) then reduces to:

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