Lecture 3

3. The First Law of Thermodynamics:

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Objectives:

ü Introduce the concept of energy

ü Forms of Energy
ü Representations of the First Law of Thermodynamics
ü The First Law of Thermodynamics for a Cycle
ü The First Law of Thermodynamics for a Closed System:
ü Energy Balance for Closed Systems:
ü Definition of enthalpy (H):
ü Define the specific heats, cv and cp
ü Internal energy, Enthalpy and Specific heats of Ideal gases
ü Mass and Energy analysis of a control volumes
ü Energy balance for a control volume:
ü Energy analysis of steady-flow systems (SSSF)
ü Energy analysis of unsteady-flow systems (USUF)

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 ü Introduce the concept of energy:

Energy can be viewed as the ability to cause changes. Energy is the capacity to do
work or to produce heat.

ü Forms of Energy

Energy: thermal, mechanical, kinetic, potential, electric, magnetic, chemical, and

nuclear, and their sum constitute the total energy E of a system. The total energy of a
system on a unit mass basis is denoted by e and is defined as:

𝐸 𝑘𝐽
𝑒= ( )
𝑚 𝑘𝑔

Thermodynamics only deals with the change of the total energy. Thus the total
energy of a system can be assigned a value of zero (E = 0) at some convenient
reference point.

The change in total energy of a system is independent of the reference point selected.

For example, the decrease in the potential energy of a falling rock depends on only
the elevation difference and not the reference level chosen.

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.

• 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.

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 § 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:
𝑚𝑉 !
𝐾𝐸 = (𝑘𝐽)
2

Where V is the velocity of the system relative to some fixed reference frame.

§ 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:
𝑃𝐸 = 𝑚𝑔𝑧 (𝑘𝐽)

Where g is the gravitational acceleration and z is the elevation of the center of

gravity of a system relative to some arbitrarily selected reference plane.

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.

Internal energy, U, is a extensive property and can be explained per unit mass,
specific internal energy, as:

𝑈 𝑘𝐽
𝑢= ( )
𝑚 𝑘𝑔

The internal energy of a substance in a saturation state and with a given quality is
found in the same way as the specific volume and can be calculated by one of the
following relations:

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 𝑢 = 𝑢! + 𝑢!"

𝑢 = 1 − 𝑥 𝑢! + 𝑥𝑢!

Thomas Young coined the term energy in 1807, and Lord Kelvin proposed its use in
thermodynamics in 1852. The term internal energy and its symbol U first appeared in
the works of Rudolph Clausius and William Rankine in the second half of the
nineteenth century.

• The magnetic, electric, and surface tension effects are significant in some
specialized cases only and are not considered in this course. In the absence of these
effects, the total energy of a system consists of the kinetic, potential, and internal
energies and is expressed as:

𝐸!"! = 𝑈 + 𝐾𝐸 + 𝑃𝐸

𝑒!"! = 𝑢 + 𝑘𝑒 + 𝑝𝑒

The above forms of energy can be contained or stored in a system, and thus can
viewed as the static forms of energy.

• The forms of energy that are not stored in a system can be viewed as the
dynamic forms of energy, or as energy interactions.
• The dynamic forms of energy are recognized at the system boundary as they
cross it, and they represent the energy gained or lost by a system during a
process.
• The only two forms of energy interactions associated with a closed system are
heat transfer and work.

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 An energy interaction is heat transfer if its driving force is a temperature
difference.

Otherwise it is work.
• The open systems can also exchange energy via mass transfer, since any time
mass is transferred into or out of a system, the energy contained in the mass is
also transferred with it.

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 ü Representations of the First Law of Thermodynamics

There are a variety of ways to represent the first law of thermodynamics, also known
as the principle of conservation of energy. Perhaps the simplest, but also the most
obtuse, is the following.

ü The First Law of Thermodynamics for a Cycle

During any cycle, the cyclic integral of heat added to a system is proportional to
the cyclic integral of work done by the system.

If we denote a cyclic integral, also known as a closed contour integral, by , the

mathematical representation of this law is

𝛿𝑄 = 𝛿𝑊 (𝑄 𝑖𝑛 𝐽, 𝑊𝑖𝑛 𝐽)

ü The First Law of Thermodynamics for a Closed System:

The first law of thermodynamics deals with macroscopic properties, work, energy,
enthalpy, etc.

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.

The first law of thermodynamics is simply an expression of the conservation of

energy principle, and it asserts that energy is a thermodynamic property.

For a closed system undergoing a process, the change in energy is equal to the heat
added to the system minus the work done by the system.

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 ∆𝐸!"! = 𝑄 − 𝑊 (1)

• This is the law of conservation of energy, written in a form useful to a systems

involving heat transfer.

Ø Q → heat flow into the system

Ø W → work done on the system (work done by the system)

Q & W are not state functions → i.e. they depend on the path of a process.

For an infinitesimal process the first law of thermodynamics for a closed system can
be written as:
𝑑𝐸!"! = 𝛿𝑄 − 𝛿𝑊

! ! !
If we integrate from 1 to 2, we get, ! 𝑑𝐸 = ! 𝛿𝑄 − ! 𝛿𝑊

yielding, 𝐸! − 𝐸! = 𝑄!!! − 𝑊!!!

ü Energy Balance for Closed Systems:

Energy balance for closed system undergoing any kind of process was expressed as:

𝐸!" − 𝐸!"# = ∆𝐸!"!#$% = 𝐸!"#$% − 𝐸!"!#!$% (𝑘𝐽)

!!" !"!#$% !"#$%&'" !!!"#$ !"
!" !!"#,!"#$ !"!#$% !"!#$%!&

or, in the rate form, as:

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 𝑑𝐸!"!#$%
𝐸!" − 𝐸!"# = (𝑘𝑊)
!"#! !" !"# !"!#$% !"#$%&'"
𝑑𝑡
!"#$ !"#!!"#$ !"
!" !!"#,!"#$
!"!#$% !"!#$%!&

ü Definition of enthalpy (H):

Enthalpy is a new extensive property as:

𝐻 = 𝑈 + 𝑃𝑉

or per unit mass,

ℎ = 𝑢 + 𝑃𝑣

The enthalpy like internal energy, is a extensive property and can be explained per
unit mass, specific enthalpy, as:

𝐻 𝑘𝐽
ℎ= ( )
𝑚 𝑘𝑔

The enthalpy of a substance in a saturation state and with a given quality is found in
the same way as the specific volume and specific internal energy. For saturation state,
the enthalpy can be calculated by one of the following relations:

ℎ = ℎ! + ℎ!"

ℎ = 1 − 𝑥 ℎ! + 𝑥ℎ!

ü Specific Heats:
The specific heat is defined, as the energy required raising the temperature of a
unit mass of a substance by one degree. In general, this energy depends on how the

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process is executed. In thermodynamics, we are interested in two kinds of specific
heats:

Specific heat at constant volume (𝑐! ):

1 𝛿𝑄 1 𝛿𝑈 𝜕𝑢 𝑘𝐽
𝑐! = = = ( )
𝑚 𝛿𝑇 ! 𝑚 𝛿𝑇 ! 𝜕𝑇 ! 𝑘𝑔. 𝐾

• It is the slope of the plot of internal energy with temperature.

Specific heat at constant pressure (𝑐! ):

1 𝛿𝑄 1 𝛿𝐻 𝜕ℎ 𝑘𝐽
𝑐! = = = ( )
𝑚 𝛿𝑇 ! 𝑚 𝛿𝑇 ! 𝜕𝑇 ! 𝑘𝑔. 𝐾

• It is the slope of the plot of enthalpy with temperature.

If a substance has higher specific heat, then more heat has to be added to raise its
!"
temperature. Water with a high specific heat (of 𝑐! = 4186 !"#$.! ) heats up slowly as
!"
compared to air (with a specific heat, 𝑐! = 29.07 !"#$.! ) ⇒ this implies that oceans

will heat up slowly as compared to the atmosphere.

As T→0K, the heat capacity tends to zero, i.e. near 0 Kelvin very little heat is
required to raise the temperature of a sample. (This automatically implies that very
little heat has to add to raise the temperature of a material close to 0K.
This is of course bad news for cooling to very low temperatures − small leakages of
heat will lead to drastic increase in temperature).

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 ü Internal energy, Enthalpy and Specific heats of Ideal gases:

We defined an ideal gas as a gas whose temperature, pressure, and specific volume
are related by:

𝑃𝑣 = 𝑅𝑇

It has been demonstrated mathematically and experimentally, that for an ideal gas the
internal energy is a function of the temperature only. That is,

𝑢 = 𝑢(𝑇)

Using the definition of enthalpy and the equation of state of an ideal gas, we have
ℎ = 𝑢 + 𝑃𝑣
ℎ = 𝑢 + 𝑅𝑇
𝑃𝑣 = 𝑅𝑇

Since R is constant and 𝑢 = 𝑢 𝑇 , it follows that the enthalpy of an ideal gas is also a
function of temperature only:

ℎ = ℎ(𝑇)

Since u and h depend only on temperature for an ideal gas, so the specific heats cv

and cp also are 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.

Thus, for ideal gases, the partial derivatives in equations cv and cp, can be replaced

by ordinary derivatives. Then the differential changes in the internal energy and
enthalpy of an ideal gas can be expressed as:

𝑑𝑢 = 𝑐! 𝑇 . 𝑑𝑇

𝑑ℎ = 𝑐! 𝑇 . 𝑑𝑇

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The change in internal energy or enthalpy for an ideal gas during a process from state
1 to state 2 is determined by integrating these equations:

Δ𝑢 = 𝑢! − 𝑢! = 𝑐! 𝑇 . 𝑑𝑇 (𝑘𝐽 𝑘𝑔)
!

Δℎ = ℎ! − ℎ! = 𝑐! 𝑇 . 𝑑𝑇 (𝑘𝐽 𝑘𝑔)
!

To carry out these integrations, we need to have relations for cv and cp as functions

of temperature, which available at thermodynamics tables.

The specific heat values for some common gases are listed as a function of
temperature in Table A–2b

A special relationship between cp and cv for ideal gases can be obtained by

differentiating the relation h = u + RT, which yields:

𝑑ℎ = 𝑑𝑢 + 𝑅 𝑑𝑇

Replacing dh by (𝑐𝑝𝑑𝑇) and du by (𝑐𝑣 𝑑𝑇) and dividing the resulting expression by
dT, we obtain:

𝑐𝑝 = 𝑐𝑣 + 𝑅 (𝑘𝐽/𝑘𝑔. 𝐾)

This is an important relationship for ideal gases since it enables us to determine cv

from knowledge of cp and the gas constant R.

At this point, we introduce another ideal-gas property called the specific heat
ratio, k, defined as:

𝑐!
𝑘=
𝑐!

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The specific ratio also varies with temperature, but this variation is very mild.

ü Constant cv and cp

The ideal-gas specific heats of monatomic gases such as argon, neon, and helium
remain constant over the entire temperature range. Thus, ︎∆𝑢 and ∆ℎ of monatomic
gases can easily be evaluated from:

Δ𝑢 = 𝑢! − 𝑢! = 𝑐! (𝑇! − 𝑇! ) (𝑘𝐽 𝑘𝑔)

Δℎ = ℎ! − ℎ! = 𝑐! (𝑇! − 𝑇! ) (𝑘𝐽 𝑘𝑔)

ü Mass and Energy analysis of a control volumes

The conservation of mass principle for a control volume: The net mass transfer to or
from a control volume during a time interval Δt is equal to the net change (increase or
decrease) in the total mass within the control volume during Δt.

𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑙𝑒𝑎𝑣𝑖𝑛𝑔 𝑁𝑒𝑡 𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝑚𝑎𝑠𝑠

− =
𝑡ℎ𝑒 𝐶𝑉 𝑑𝑢𝑟𝑖𝑛𝑔 Δ𝑡 𝑡ℎ𝑒 𝐶𝑉 𝑑𝑢𝑟𝑖𝑛𝑔 Δ𝑡 𝑤𝑖𝑡ℎ𝑖𝑛 𝑡ℎ𝑒 𝐶𝑉 𝑑𝑢𝑟𝑖𝑛𝑔 Δ𝑡

𝑚!" − 𝑚!"# = ∆𝑚!.!. = 𝑚!"#$% − 𝑚!"!#!$% (𝑘𝑔)

It can also be expressed in rate form as:

𝑑𝑚!.!. 𝑘𝑔
𝑚!" − 𝑚!"# = ( )
𝑑𝑡 𝑠

Where 𝑚!" and 𝑚!"# are the total rates of mass flow into and out of the control

!!!.!.
volume, and is the time rate of change of mass within the control volume
!"

boundaries.

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 ü Energy balance for a control volume:

The rate form of the general energy balance for a control volume can be written as:
𝐸!" − 𝐸!"# = 𝑑𝐸!.!. 𝑑𝑡
!"#$ !! !"!#$% !"#$%&'" !"#$ !" !!!"#$ !"
!" !!"#,!"#$ !"# !"## !"#$%"& !"#$%& !"!#$%

The first law of thermodynamics for a control volume can be written as:

𝑉! 𝑉! 𝑑𝐸!.!.
𝑄!.!. + 𝑚(ℎ + + 𝑔𝑧) = 𝑊!.!. + 𝑚(ℎ + + 𝑔𝑧) +
2 2 𝑑𝑡
!" !"#
!"# !"#! !"#$% !"# !"#! !"#$

ü Energy analysis of steady-flow systems (SSSF)

A large number of engineering devices such as turbines, compressors, and nozzles

operate for long periods of time under the same conditions once the transient start-up
period is completed and steady operation is established, and they are classified as
steady-flow devices. Processes involving such devices can be represented reasonably
well by a somewhat idealized process, called the steady-flow process, which is
defined as a process during which a fluid flows through a control volume steadily.
That is, the fluid properties can change from point to point within the control volume,
but at any point, they remain constant during the entire process. (Remember, steady
means no change with time.)

During a steady-flow process, no intensive or extensive properties within the control

volume change with time. Thus, the volume V, the mass m, and the total energy
content E of the control volume remains constant.

𝑚!.!. = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ⟹ 𝑑𝑚!.!. 𝑑𝑡 = 0

𝐸!.!. = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ⟹ 𝑑𝐸!.!. 𝑑𝑡 = 0

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 ü Energy analysis of unsteady-flow systems (USUF)

Many processes of interest, however, involve changes within the control volume with
time. Such processes are called unsteady-flow, or transient- flow, processes.

The general unsteady-flow process, in general, is difficult to analyze because the

properties of the mass at the inlets and exits may change during a process. Most
unsteady-flow processes, however, can be represented reason- ably well by the
uniform-flow process, which involves the following idealization: The fluid flow
at any inlet or exit is uniform and steady, and thus the fluid properties do not change
with time or position over the cross section of an inlet or exit. If they do, they are
averaged and treated as constants for the entire process.

The general energy balance was given earlier as:

𝑚!" − 𝑚!"! = ∆𝑚!.!.

The energy balance for a uniform-flow system can be expressed explicitly as:

!! !!
𝑄!.!. + !" 𝑚(ℎ + !
+ 𝑔𝑧) = 𝑊!.!. + !"# 𝑚(ℎ + !
+ 𝑔𝑧) + (𝑚! 𝑒! − 𝑚! 𝑒! )!.!.
!"# !"#! !"#$% !"# !"#! !"#$

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