CHAPTER 2

FORMS OF ENERGY
AND THE FIRST LAW OF
THERMODYNAMICS

INTRODUCTION

Energy exists in numerous forms such as thermal, mechanical,

electric, chemical, and nuclear. Even mass can be considered a
form of energy. Energy can be transferred to or from a closed
system (a fixed mass) in two distinct forms: heat and work. For
control volumes, energy can also be transferred by mass flow.
An energy transfer to or from a closed system is heat if it is
caused by a temperature difference. Otherwise it is work, and it
is caused by force acting through a distance.
If we think of a macroscopic system as consisting of many
interacting particles, we know that it has a well-defined total
energy which satisfies a conservation principle.

The macroscopic forms of energy are those a system possesses

as a whole with respect to some outside reference frame. The
microscopic forms of energy, on the other hand, are those
related to the molecular structure of a system and the degree
of the molecular activity, and 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 sum of all forms of the energy a system possesses is called

total energy. In the absence of magnetic, electrical and surface
tension effects, the total energy of a system consists of the
kinetic, potential, and internal energies.
The total energy of a system on a unit mass basis is denoted by
e and is expressed as
e =

E
m

kJ/kg

The mechanical energy is the form of energy that can be

converted to mechanical work completely and directly by a
mechanical device such as a propeller. It differs from thermal
energy in that thermal energy cannot be converted to work
directly and completely. The forms of mechanical energy of a
fluid stream are kinetic, potential, and flow energies.

The internal energy of a system is made up of sensible,

latent, chemical and nuclear energies. The sensible
internal energy is due to translational, rotational, and
vibrational effects.

Thermal energy is the sensible and latent forms of internal

energy, and it is referred to as heat in daily life.
Energy can be transferred to or from a system in three forms:
heat, work, and mass flow.
Energy can cross the boundaries of a closed system in two
forms: heat and work.

FORMS OF ENERGY
In thermodynamic analysis, it is often helpful to consider the
various forms of energy that make up the total energy of a
system in two groups: macroscopic and microscopic. 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 (Fig. 2.1). 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.

Figure 2.1: The macroscopic energy of an object changes with

velocity and elevation.

Kinetic Energy
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). When all parts of
a system move with the same velocity, the kinetic energy is
expressed as
KE = mv2
(kJ)
On a unit mass:
ke = v2

kJ/kg

where V denotes the velocity of the system relative to some

fixed reference frame. The kinetic energy of a rotating solid
body is given by I2 where I is the moment of inertia of the
body and is the angular velocity.

Potential Energy
From the fundamentals of Mechanics, the energy possessed by
a body by virtue of its position or configuration is termed
potential energy (PE). The potential energy of a body of mass
m which is at an elevation z from the earths surface (or any
particular datum) is given by:
PE = mgz

(kJ)

On a unit mass:
pe = gz

kJ/kg

where, g is the acceleration due to gravity (= 9.81 m/s 2), and z

is the elevation of the center of gravity of a system relative to
some arbitrarily selected reference level.

Internal Energy
Energy is also associated with the motion of the electrons, spin
of the electrons, intra-atomic (nucleus-electron, nucleusnucleus) interactions, etc. Molecules are also subject to intermolecular interactions which are electromagnetic in nature,
especially at short intermolecular separation distances. All
these forms of energy are microscopic in form and they cannot
be readily estimated in terms of macroscopically measurable
properties of matter.
Thus the energy possessed by matter due to the microscopic
modes of motion is referred to as the internal energy of the
matter.
The concept of internal energy was first demonstrated by the
British scientist James P. Joule during 1840s by a series of
carefully executed experiments.
On a sub-molecular scale energy is associated with the
electrons and nuclei of atoms, and with bond energy resulting
from the forces holding atoms together as molecules. With

The molecules of a gas move through space with some

velocity, and thus possess some kinetic energy. This is known
as the translational energy.

The atoms of polyatomic molecules rotate about an axis, and

the energy associated with this rotation is the rotational
kinetic energy.

The electrons in an atom rotate about the nucleus, and thus

possess rotational kinetic energy.

The atoms of a polyatomic molecule may also vibrate about

their common center of mass, and the energy associated with
this back-and-forth motion is the vibrational kinetic energy.

Electrons also spin about their axes, and the energy associated
with this motion is the spin energy. Other particles in the
nucleus of an atom also possess spin energy.

The portion of the internal energy of a system associated with

the kinetic energies of the molecules is called the sensible
energy. At higher temperatures, the molecules possess higher
kinetic energies, and as a result the system has a higher
internal energy.

The internal energy is also associated with various binding

forces between the molecules of a substance, between the
atoms within a molecule, and between the particles within an
atom and its nucleus. The forces that bind the molecules to
each other are strongest in solids and weakest in gases. If
sufficient energy is added to the molecules of a solid or liquid,
the molecules overcome these molecular forces and break
away, turning the substance into a gas. This is a phase-change
process. The internal energy associated with the phase of a
system is called the latent energy.

The internal energy associated with the atomic bonds in a

molecule is called chemical energy.

During a chemical reaction, such as a combustion process,

some chemical bonds are destroyed while others are formed.
As a result, the internal energy changes. The nuclear forces are
much larger than the forces that bind the electrons to the
nucleus. The tremendous amount of energy associated with the
strong bonds within the nucleus of the atom itself is called
nuclear energy.

The best known fission reaction involves the split of the

uranium atom (the U-235 isotope) into other elements and is
commonly used to generate electricity in nuclear power plants
to power nuclear submarines and aircraft carriers, and even to
power spacecraft as well as building nuclear bombs.
The complete fission of 1 kg of uranium-235 releases 6.73 X
1010 kJ of heat, which is more than the heat released when
3000 tons of coal are burned.

Example 1. An average car consumes about 5 L of gasoline a

day, and the capacity of the fuel tank of a car is about 50 L.
Therefore, a car needs to be refueled once every 10 days. Also,
the density of gasoline ranges from 0.68 to 0.78 kg/L, and its
lower heating value is about 44,000 kJ/kg (that is, 44,000 kJ of
heat is released when 1 kg of gasoline is completely burned).
Suppose all the problems associated with the radioactivity and
waste disposal of nuclear fuels are resolved, and a car is to be
powered by U-235. If a new car comes equipped with 0.1-kg of
the nuclear fuel U-235, determine if this car will ever need
Assumptions:
refueling under average driving conditions.
Gasoline is an incompressible substance with an average
density of 0.75 kg/L.
Nuclear
Solution:fuel is completely converted to thermal energy.
The mass of gasoline used per day by the car is
mgasoline = (V)gasoline = (0.75 kg/L) (5 L/day) = 3.75 kg/day

Note that the heating value of gasoline is 44,000 kJ/kg, the

energy supplied to the car per day is
E = (mgasoline) (Heating value)
= (3.75 kg/day) (44,000 kJ/kg) = 165,000 kJ/day
The complete fission of 0.1 kg of uranium-235 releases
(6.73 x 1010 kJ/kg) *0.1 kg) = 6.73 x 109 kJ
of heat, which is sufficient to meet the energy needs of the car
for
Energy content of
6.73 x 109 kJ
No. of days =
=
fuel use
Daily energy
165,000
= 40,790 days
kJ/day

= 112 yrs
which is equivalent to about 112 years. Considering that no car
will last more than 100 years, this car will never need refueling.
It appears that nuclear fuel of the size of a cherry is sufficient
to power a car during its lifetime.

Like other intensive, macroscopic variables such as pressure,

temperature, mass or volume, internal energy is a state
variable as it is wholly dependent on the energy states that its
atoms / molecules. Thus any change in the (say, specific)
internal energy due to a process would only depend on the
initial and final states, and not on the path followed during the
change. Thus as Ufor changes in P, V or T, one may write:
dU = U = U2 U1
kJ

U1

On a unit mass:
u = u2 u1

kJ/kg

U is not a directly measurable property since no absolute

values of internal energy are possible, but U is.
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
E = U + KE + PE = U + m v2 + mgz
or, on a unit mass basis:

kJ

Most closed systems remain stationary during a process and

thus experience no change in their kinetic and potential
energies. Closed systems whose velocity and elevation of the
center of gravity remain constant during a process are
frequently referred to as stationary systems. The change in the
total energy E of a stationary system is identical to the change
in its internal energy U.

Figure 2.2: For stationary systems, KE = PE = 0, thus E =

U

Control volumes typically involve fluid flow for long periods of

time, and it is convenient to express the energy flow associated
with a fluid stream in the rate form. This is done by
incorporating the mass flow rate , which is the amount of
mass flowing through a cross section per unit time. It is related
to the volume flow rate , which is the volume of a fluid flowing
through a cross section per unit time, by
Mass flow rate:
= = A Vave kg/s
where: is the fluid density, A is the cross-sectional area of
flow, and Vavg is the average flow velocity normal to A.

Figure 2.3: Mass and energy flow rates associated with the flow
of steam in a pipe of inner diameter D with an average velocity
of Vavg.

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.
A pump transfers mechanical energy to a fluid by raising its
pressure, and a turbine extracts mechanical energy from a
fluid by dropping its pressure. Therefore, the pressure of a
flowing fluid is also associated with its mechanical energy.
But a pressure force acting on a fluid through a distance
produces work, called flow work.

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
v
emech =
+
+ gz
p

2
2
where p/ is the flow energy,
It can also be expressed in rate form
mech = emech = (

v
+2
2

+ gz)

Then the mechanical energy change of a fluid during

incompressible ( = constant) flow becomes
p2 p1
v2 2
emech =
+
+ g (z2 z1)
kJ/kg
2

v1 2
mech = [

p2 p1

v2

v12 2

+ g (z 2 z1)] kW

Example 2. A site evaluated for a wind farm is observed to

have steady winds at a speed of 8.5 m/s with a 12-m diameter
flow section and the air density is 1.2 kg/m3. 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.
Solution:
Wind energy per unit mass of air is
e = ke =

v2
( 8.5
= (
2
m/s)22

J/kg
) (2 2
m /s

) = 36.J/kg

Wind energy for an air mass of 10 kg is

E = me = 10 kg (36.1 J/kg) = 361 J
Wind energy for a mass flow rate of 1154 kg/s is
= e = (1154 kg/s) (36.1 J/kg) x ( 1
1000
kW
J/s

) = 41.7 kW

WORK

During a process the surroundings can do work on the system

of interest or the system can do work on its surroundings.

Our definition of work includes the work done by expanding

exhaust gases after combustion occurs in the cylinder of an
automobile engine, as shown in Fig. 2.4. The energy released
during the combustion process is transferred to the crankshaft
by means of the connecting rod, in the form of work. Thus, in
thermodynamics, work can be thought of as energy being
transferred across the boundary of a system, where, in this
Connectin
example, the system
is the gas in the cylinder.
g rod

W
Velocit
y
Piston

Gase
s

Cylinde
r

Figure 2.4: Work done by expansion of gases in a cylinder

Work, designated W, is often defined as the product of a force

and the distance moved in the direction of the force: the
mechanical definition of work. It is the energy transferred to the
system by force in a mechanical interaction.
Thermodynamic definition: Work is done by a system if the sole
external effect on the surroundings could be the raising of a
weight. The magnitude of the work is the product of that weight
Consider
the piston-cylinder
arrangement shown in Fig. 2.5. In
and the distance
it could be lifted.
state 1, a material at pressure P is confined in a cylinder of
cross-sectional area A. The height of the piston in the cylinder
is x. The pressure force of the material on the piston is just
balanced by weights on top of the piston.

Figure 2.5: Sketch of piston-cylinder arrangement as work is

done and as the material expands when weights are removed

As one of the weights is removed, the piston rises to a new

height x + dx. Let a long time elapse so the system comes to
rest at its new equilibrium. There is a new pressure in the
chamber, p + dp sufficient to balance the new weight force.
Obviously work was done as a force acted through a distance.
How much work was done? The differential work is given as
W = Fdx
F varies during the process.
state 1: F = pA
state 2: F = (p + dp)A.
approximation of F by its average value:
F (pA + (p + dp)A) = pA + (dp /2)A

W = (pA + (dp /2)A)dx

0
W = pA dx + (A/2) dp dx
W = pA dx
A.dx = dV
W = p dV
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:
W1 - 2 =

2
1

p dV

W1 - 2 emphasize that the work depends on the path from state

1 to state 2.
The path-dependence of W1 - 2 can be seen by realizing that2 W1 1

= p dV represents the area under a curve in a pV diagram.

Typical pressure-volume diagrams are shown in Fig. 2.6. The
work W1-2 is the area under the pV curve.
2

The states 1 and 2 in Fig. 2.6 (a) and (b) are identical, yet the
areas under the pV curves are very different; work depends on
the actual path that connects the two states. Thus, work is a
path function, as contrasted to a point function (that is
dependent only on the end points). The differential of a path
function is called an inexact differential, whereas the
differential of a point function is an exact differential. An
inexact differential will be denoted with the symbol .

Figure 2.6: Work depends on the path between two states

The sign of the work done depends on the direction in which
the piston is moved. The work done on the system will be
positive if the displacement is in the same direction as that of
the applied force F, and it will be negative if the displacement is
in the opposite direction.
A positive amount of work is done by the gas if V is increasing;

Other forms of work

Mechanical Form:
We note that there are other forces besides pressure forces,
and those forces can also do work. Consider
a stretching wire stretched by tension force F through length
change dL. The differential work is
W = dL
Work transferred by a rotating shaft is a common occurrence
in mechanical systems. The work results from the shearing
forces due to the shearing stress , which varies linearly with
the radius over the cross-sectional area. The differential
shearing force due to the shearing stress is
dF = dA = (2rdr)

Figure 2.7: Work due to a rotating shaft transmitting a torque.

The linear velocity with which this force moves is r. Hence,

the rate of doing work (force times velocity) is
=

r AdF =

r
2rdr = 2
r2 dr
0
0

where R is the radius of the shaft. The torque T is found from

the shearing stresses by integrating over the area:
R

T = A r dF = 2 0 r2 dr
Therefore,
= T
To find the work transferred in a given time t, we simply
multiply the above equation by the number of seconds:
W = Tt
The angular velocity must be expressed in rad/s. If it is
expressed in rev/min (rpm), multiply by 2 /60.

Example 3. The drive shaft in an automobile delivers 100 N m

of torque as it rotates at 3000 rpm. Calculate the horsepower
transmitted.
Solution:
The power is found by using = T. This requires to be
2
expressed in rad/s:
60
= 3000 x

= 314.2 rad/s

Hence
= T = 100 314.2 = 31 420 W
hp

31
746
420
or

= 42.1

Example 4. Determine the power transmitted through the

shaft of a car when the torque applied is 200 N m and the
shaft rotates at a rate of 4000 revolutions per minute (rpm).
Solution:
The shaft power is determined directly from:
= (200 N.m) (4000 rev/min) (

2
60
sec/min
rad/rev

= T
) = 83, 800 W

The work necessary to stretch a linear spring (Fig. 2.8) with

spring constant k from a length x1 to x2 can be found by using
the relation for the force:
F = kx

where x is the distance the spring is stretched from the

unstretched position. Note that the force is dependent on the
variable x. Hence,
W=

x2

F xdx =
1

x2
x1

k xdx = k (x22 x12 )

Figure 2.8: Work needed to stretch a spring.

Example 5. The air in a 10-cm-diameter cylinder shown is
heated until the spring is compressed 50 mm. Find the work
done by the air on the frictionless piston. The spring is initially
unstretched, as shown. Consider patm = 100 kPa.

Figure 2.9: Schematic for Example 5

Solution:
The pressure in the cylinder is initially found from a force
balance as shown on the free-body diagram:
p1 A = patm A + W
p1 x 0.052 m2 = 100 000 N/m2 x x 0.052 m2 + 50kg x 9.81
m/s2
p1 = 162 500 Pa
To raise the piston a distance of 50 mm, without the spring, the
pressure would be constant and the work required would be
force times distance:
W1 = pA d = 162 500 N/m2 x ( x 0.052) m2 x 0.05m = 63.81 J
the work required to compress the spring is calculated to be
W2 = k (x22 x12) = (10 000 N/m) (0.052) m2 = 12.5 J

 a surface with surface tension S. The differential work is

W = dA
Work Done to Raise or to Accelerate a Body
When a body is raised in a gravitational field, its potential
energy increases. Likewise, when a body is accelerated, its
kinetic energy increases.

Example 6. Consider a 1200-kg car cruising steadily on a level

road at 90 km/h. Now the car starts climbing a hill that is
sloped 30 from the horizontal (Fig. 2.10). If the velocity of the
car is to remain constant during climbing, determine the
additional power that must be delivered by the engine.

Figure 2.10: Schematic for Example 6.

Solution:
The additional power required is simply the work that needs to
be done per unit time to raise the elevation of the car, which is
equal to the change in the potential energy of the car per unit
time:

g = mgz/t = mgVvertical

= 1200 kg (9.81 m/s2)(90 km/hr) sin 30o x(1000m/km)

(1hr/3600 sec)
= 147 kJ/sec = 147 kW (197 hp)
The car must produce almost 200 hp of additional power while
climbing the hill to maintain its velocity.

Example 7. Determine the power required to accelerate a 900kg car shown in Fig. 2.11 from rest to a velocity of 80 km/h in
20 s on a level road.

Figure 2.11: Schematic for Example 7.

Solution: The work needed to accelerate a body is simply the
change in the kinetic energy of the body,
W = m (v2
= 222 kJ

80kg)
000
v1 2) = (900
[(
3600
m
sec

The average power

= W/t =

1 kJ/kg
) 2 02] x
1000 m2/s2

222
= 11.1 kW (14.9 hp)
kJ 20
sec
This is in addition to the power
required to overcome friction,
rolling resistance, and other imperfections.

Non mechanical work

a system with electrical work where E is the electrical field
strength, q is the particle charge, and x is the distance:
W = qEdx.
The potential difference V across the battery terminals is the
force that drives the charge through the resistor during the
time increment t. The current i is related to the charge. The
work is given by the expression
W = Vi t
The power would be the rate of doing work, or
W = Vi

Figure 2.12: Work due to a current fl owing through a resistor.

In total, for materials which are more than simple compressible

substances, we have
W = PdV dL $dA qEdx . . .
It can be shown that the more work modes we include, the
more independent thermodynamic variables are necessary to
specify the state of the system.
Lastly we note that a gas expanding into a vacuum has W1 - 2 1 p dV
because it is inherently a non-equilibrium process.
2

Non equilibrium work

It must be emphasized that the area on a PV diagram
represents the work for a quasiequilibrium process only. For
nonequilibrium processes the work cannot be calculated using
the integral of PdV. Either it must be given for the particular
process or it must be determined by some other means. The
paddle wheel provides us with a nonequilibrium work mode.

Example 8. A 100-kg mass drops 3 m, resulting in an

increased volume in the cylinder shown of 0.002 m3. The
weight and the piston maintain a constant gage pressure of
100 kPa. Determine the net work done by the gas on the
surroundings. Neglect all friction.

Figure 2.13: The paddle wheel provides a non-equilibrium

work mode.
Solution:
The paddle wheel does work on the system, the gas, due to the 100-kg mass
dropping 3 m. That work is negative and is
W = F d = (100 9.81) 3 = 2940 Nm
The work done by the system on this frictionless piston is positive since the
system is doing the work. It is
W = PA h = PV = 200 000 0.002 = 400 Nm
where absolute pressure has been used. The net work done is thus
Wnet = W paddle wheel + W boundary = 2940 + 400 = 2540 J

HEAT
Energy transfer takes place between two bodies of different
temperatures until thermal equilibrium is established. The
direction of energy transfer is always from the higher
temperature body to the lower temperature one. Once the
temperature equality is established, energy transfer stops.
Energy is said to be transferred in the form of heat. Transfer of
energy that we cannot account for by any of the work modes is
called heat transfer.
Heat is transferred by
convection, and radiation.

three

mechanisms:

conduction,

Conduction, also called heat diffusion, 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. This is characterized by Fouriers law:
where q is the heat flux vector with units J/s/m 2 = W/m2, k is the
q = kT,
thermal conductivity with units
J/s/m/K = W/m/K, and T is the
vector representing the gradient of temperature.

In one dimension,
d
q = k
dx
t
If multiplied by the local cross-sectional area, = qA, and
d
= kA
dx
t

(Thot
~ kA
TcoldL
)

Figure 2.14: Heat conduction from warm air to a cold canned

drink through the wall of the aluminum can.

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. For some
systems, convective effects are well modeled by Newtons law
of cooling:
q = h(Thot Tcold),
= qA = hA (Thot Tcold)
where h is a constant with units W/m2/K
Convection is called forced convection if the fluid is forced to
flow in a tube or over a surface by external means such as a
fan, pump, or the wind. In contrast, convection is called free (or
natural) convection if the fluid motion is caused by buoyancy
forces induced by density differences due to the variation of
temperature in the fluid.

Figure 2.15: The cooling of a boiled egg by forced and

natural convection.
Radiation is the transfer of energy due to the emission of

electromagnetic
waves (or photons). For some systems, the
radiative heat transfer rate is well modeled by
q = (Thot 4 Tcold4)
= qA = A (Thot 4 Tcold4)
where is the Stefan-Boltzmann constant, = 5.67 10 8
W/m2/K4

Figure 2.16: heat transfer by radiation can occur between

two bodies, even when they are separated by a medium
colder than both of them.
Heat is defined as the form of energy that is transferred
between two systems (or a system and its surroundings) by
virtue of a temperature difference. Energy is transferred to the
system via atomic level collisions where there is a thermal
interaction. That is, an energy interaction is heat only if it takes
place because of a temperature difference. Then it follows that
there cannot be any heat transfer between two systems that
are at the same temperature. The transfer of heat into a
system is frequently referred to as heat addition and the
transfer of heat out of a system as heat rejection.

Figure 2.17: Temperature difference is the driving force for heat

transfer. The larger the temperature difference, the higher is
the rate of heat transfer.
Heat is energy in transition. It is recognized only as it crosses
the boundary of a system.
Consider the hot baked potato one more time. The potato
contains energy, but this energy is heat transfer only as it
passes through the skin of the potato (the system boundary)
to reach the air, as shown in Fig. 2.18. Once in the
surroundings, the transferred heat becomes part of the internal
energy of the surroundings. Thus, in thermodynamics, the term
heat simply means heat transfer.

Figure 2.18: Energy is recognized as heat transfer only as it

crosses the system boundary.
A process during which there is no heat transfer is called an
adiabatic process.
There are two ways a process can be adiabatic: Either the
system is well insulated so that only a negligible amount of
heat can pass through the boundary, or both the system and
the surroundings are at the same temperature and therefore
there is no driving force (temperature difference) for heat
transfer.

It should be noted that the energy contained in a system might

be transferred to the surroundings either by work done by the
system or by heat transferred from the system. In either case,
heat and work are qualitatively equivalent and are expressed in
units of energy. An equivalent reduction in energy is
accomplished if 100 J of heat is transferred from a system or if
100 J of work is performed by a system. In Fig. 2.19 the burner
illustrates heat being added to the system and the rotating
shaft illustrates work being done on the system. In either case,
energy is being added to the system.

Figure 2.19: Energy added to a system.

Because a system does not contain heat, heat is not a property.

Thus, its differential is inexact and is written as Q, where Q is
the heat transfer. For a particular process between state 1 and
state 2 the heat transfer could be written as Q 1-2 but it will
generally be denoted simply as Q. It is sometimes convenient
to refer to the heat transfer per unit mass, or q, defined as
q = Q (kJ/kg)
m
The heat transfer rate is denoted , and has the unit kJ/s, which
is equivalent to kW. The amount of heat transfer during a
process is determined by integrating over the time interval of
the process:
t

Q = t 2dt
1

Notes of comparison:
Q and W as well as q and w are affiliated with transient
phenomena; both cross boundaries when the system changes
state.
Q and W as well as q and w only exist at system boundaries.
Q and W as well as q and w are both path-dependent, have
inexact differentials, and are not properties of the system.
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. The
generally accepted formal sign convention for heat and work
interactions is as follows: heat transfer to a system and work
done by a system are positive; heat transfer from a system and
work done on a system are negative. Another way is to use the
subscripts in and out to indicate direction (Fig. 2.20).

Figure 2.20: Accepted formal sign convention for heat and

work interactions
Example 9. A paddle wheel adds work to a rigid container by
rotations caused by dropping a 50-kg weight a distance of 2 m
from a pulley. How much heat must be transferred to result in
an equivalent effect?
Solution
For this non-quasiequilibrium process the work is given by
W = mg d = 50 9.8 2 = 980 J
The heat Q that must be transferred equals the work, 980 J.

THE FIRST LAW OF THERMODYNAMICS

The First Law of Thermodynamics states that work and heat are
mutually convertible. The present tendency is to include all
forms of energy. The First Law can be stated in many ways:
1. Energy can neither be created nor destroyed; it is always
conserved. However, it can change from one form to
another.

Figure 2.21: Energy cannot be created or destroyed; it can only

change forms.

2. All energy that goes into a system comes out in some form
or the other. Energy does not vanish and has the ability to
be converted into any other form of energy.

Figure 2.22: Conversion of heat into useful work.

3. If the system is carried through a cycle, the summation of

work delivered to the surroundings is equal to summation of
heat taken from the surroundings.

Figure 2.23: A schematic for a power plant Q = W.

4. No machine can produce energy without corresponding

expenditure of energy.
5. Total energy of an isolated system in all its form, remain
constant.
The energy change is the difference
between the final and initial states

E = Eout Ein
The system is the mixture of reactants, and
the surroundings are the flask, the solvent,
the room and the rest of the universe.

Energy flowing out of the system to

the surroundings has a negative sign
because Eout < Ein
Energy flowing into the system
from the surroundings has a
positive sign because Eout > Ein

Figure 2.24: The total energy E of an isolated system is

constant

For any thermodynamic process, in general one needs to

account for changes occurring both within a system as well as
its surroundings. Since the two together forms the universe
in thermodynamic terms, the application of the first law to a
process leads to the following mathematical form:
(Total energy of the universe) = 0
(Total energy of the system) + (Total energy of the
surroundings) = 0
Where finite change occurring during the thermodynamic
process
Energy Change of a System, esystem
The determination of the energy change of a system during a
process involves the evaluation of the energy of the system at
the beginning and at the end of the process, and taking their
difference.
Energy change = Energy at final state Energy at initial state
Or

=E

=E

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
E = U + KE + PE - total energy equation
where:
U = m(u2 u1)
KE = m(v22 v12)
KE = mg (z2 z1)

Mechanisms of Energy Transfer, Ein and Eout

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. 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). Likewise, when
some mass leaves the system, the energy contained within the
system decreases because the leaving mass takes out some
energy with it.

The net transfer of a quantity is equal to the difference

between the amounts transferred in and out,

Ein Eout = (Qin Qout) + (Win Wout) + (Emass,in Emass,out) =

Esystem

Application of the First Law to Closed Systems

Recall that closed systems do not allow transfer of mass across
its boundary. As already pointed out work and heat may enter
or leave such a system across its boundary (to and fro with
respect to the surrounding) and also be stored in the common
form of internal energy. Since in a system may also possess
potential and kinetic energies, one may reframe the first law as
follows.
E = U + KE + PE - total energy equation
If the energy transfer across the system boundary takes place
only the form of work and heat:
U + KE + PE = Q + W
The above equation may also be written in a differential form:
dU + dKE + dPE = Q + W
If there is no change in potential and kinetic energies for the
system or it is negligible as is usually true for most
thermodynamic systems of practical interest the above
equation reduces to:

In many situations of practical interest the thermodynamic

work for closed systems is typically the pdV work, hence
2

dU = Q + W = Q 1 p
dV
U = Q W - Energy equation for a closed system
The statement, that the internal energy of a thermodynamic
system can be increased either by doing work or adding heat,
is the physical content of the first law of thermodynamics.
Various forms of the first-law relation for closed systems.
General:
Stationary systems:
Per unit mass:
Differential form:

Q W = E
Q W = U
q w = e
q w = de

Example 10. An insulated container is filled with a mixture of

water and ice at zero C. An electric heating element inside the
container is used to add 1680 J of heat to the system while a
paddle does 450 J of work by stirring. What is the increase in
the internal energy of the ice-water system?
Solution:
Stirring is work done ON the gas (W is negative)
U = Q W; W = 450 J
= (1680 + 450) J
=2130 J

The First Law Applied to a Cycle

For a closed system undergoing a cycle, the initial and final
states are identical, and thus Esystem = E 2 E1 = 0. Then the
energy balance for a cycle simplifies to Ein Eout = 0 or Ein = Eout.
Noting that a closed system does not involve any mass flow
across its boundaries, the energy balance for a cycle can be
expressed in terms of heat and work interactions as
Wnet out = Qnet in or

net out = net in

Figure 2.25: For a cycle, E = 0,

thus Q = W

Example 11. A rigid tank contains a hot fluid that is cooled

while being stirred by a paddle wheel. Initially, the internal
energy of the fluid is 800 kJ. During the cooling process, the
fluid loses 500 kJ of heat, and the paddle wheel does 100 kJ of
work on the fluid. Determine the final internal energy of the
fluid. Neglect the energy stored in the paddle wheel.

Figure 2.26: Schematic for Example 11.

Assumptions: The tank is stationary and thus the kinetic and
potential energy changes are zero, KE = PE = 0. Therefore,
E = U and internal energy is the only form of the systems
energy that may change during this process. Energy stored in
the paddle wheel is negligible.

Solution:
Let U2 be the final internal energy of the system
Ein Eout

Wsh,in

Esystem

Net
energy
transfer
by
heat, work and
mass

Qout = U = U2 U1

100 kJ 500 kJ = U2 800 kJ

U2 = 400 kJ

Change
in
potential,
kinetic, internal,
etc., energies

Example 12. A room is initially at the outdoor temperature of

25C. Now a large fan that consumes 200 W of electricity when
running is turned on (Fig. 2.27). The heat transfer rate between
the room and the outdoor air is given as = UA (T i To) where
U = 6 W/m2 C is the overall heat transfer coefficient, A = 30
m2 is the exposed surface area of the room, and T i and To are
the indoor and outdoor air temperatures, respectively.
Determine the indoor air temperature when steady operating
conditions are established.

Figure 2.27: Schematic for Example 12.

Solution:
Ein Eout
Rate of net
energy transfer
by heat, work
and mass

elect in = out

Esystem
Rate of change in
potential, kinetic,
internal, etc.,
energies

= UA (Ti To)

200 W = 6 W/m2 C (30 m2) (Ti

25oC)
Ti
= 26.1 oC

Example 13. The lighting needs of a classroom are met by 30

fluorescent lamps, each consuming 80 W of electricity. The
lights in the classroom are kept on for 12 hours a day and 250
days a year. For a unit electricity cost of P3.15 per kWh,
determine annual energy cost of lighting for this classroom.
Also, discuss the effect of lighting on the heating and airconditioning requirements of the room.
Assumptions: The effect of voltage fluctuations is negligible so
that each fluorescent lamp consumes its rated power.
Lighting power = (Power consumed per lamp) x (No. of lamps)
= 80 W/lamp x 30 lamps = 2400 W = 2.4 Kw
Operating hours = (12 h/day) x (250 days/year) = 3000 h/year

Then the amount and cost of electricity used per year become
Lighting energy = (Lighting power) x (Operating hours)
= 2.4 kW x 3000 h/year = 7200 kW-h /year
Lighting cost

= (Lighting energy) x (Unit cost)

= (7200 kWh/year) x (3.15/kWh) = P22, 680/year

Light is absorbed by the surfaces it strikes and is converted to

thermal energy. Disregarding the light that escapes through the
windows, the entire 2.4 kW of electric power consumed by the
lamps eventually becomes part of thermal energy of the
classroom. Therefore, the lighting system in this room reduces
the heating requirements by 2.4 kW, but increases the airconditioning load by 2.4 kW.

The First Law Applied to a Process

The process of change in a thermodynamic system may occur
under various types of constraints, which are enlisted below:
Work done by a gas on the surroundings
Constant pressure (isobaric) (P = 0); W = pV
Constant volume (isochoric) (V = 0); W = PV = 0
For an Ideal Gas only
V
Constant temperature (isothermal) (T = 0); W 2= nRT ln
V1
3
Without heat transfer (adiabatic) (Q = 0); W =
nR (T f
2
Ti)

Many processes in thermodynamics are well modeled as a

polytropic process.
POLYTROPIC PROCESS: a process which is described well by an
equation of the form
PVn = constant = C.

W1 - 2 =

12p dV

Figure 2.28: p V diagram for various polytropic processes.

Example 14. Energy is added to a piston-cylinder

arrangement, and the piston is withdrawn in such a way that
the temperature (i.e., the quantity pV) remains constant. The
initial pressure and volume are 200 kPa and 2 m3, respectively.
If the final pressure is 100 kPa, calculate the work done by the
ideal gas on the piston.
Solution:
2

W1 - 2 =1 p dV
W1 - 2 =
W1 - 2

; pV = C, then p =

2d
C
(
) dV = C

1
1
V
V
V
2

V2
= C ln
V1

Since

pV = C,

p1V1 = p2V2

C
V

(the work for a gas undergoing a polytropic process with n = 1)

W1 - 2 = p1 V1 ln

V2
V1

V
= p2 V2 ln 2
V1

solving for V2:

V2 = p1V1 / p2

= (200 x 103 N/m2) (2 m3) / 100 N/m2

V 2 = 4 m3
3
4m
3
W1 - 2 = (200 x 10 3 N/m2) (2 m2m
) ln
3 (
277 kJ

) = 277 x 103 N.m =