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The First Law of Thermodynamics:: Objectives
The First Law of Thermodynamics:: Objectives
The First Law of Thermodynamics:: Objectives
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Objectives:
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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
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.
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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 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.
During any cycle, the cyclic integral of heat added to a system is proportional to
the cyclic integral of work done by the system.
𝛿𝑄 = 𝛿𝑊 (𝑄 𝑖𝑛 𝐽, 𝑊𝑖𝑛 𝐽)
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.
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)
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
Energy balance for closed system undergoing any kind of process was expressed as:
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𝑑𝐸!"!#$%
𝐸!" − 𝐸!"# = (𝑘𝑊)
!"#! !" !"# !"!#$% !"#$%&'"
𝑑𝑡
!"#$ !"#!!"#$ !"
!" !!"#,!"#$
!"!#$% !"!#$%!&
𝐻 = 𝑈 + 𝑃𝑉
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:
1 𝛿𝑄 1 𝛿𝑈 𝜕𝑢 𝑘𝐽
𝑐! = = = ( )
𝑚 𝛿𝑇 ! 𝑚 𝛿𝑇 ! 𝜕𝑇 ! 𝑘𝑔. 𝐾
1 𝛿𝑄 1 𝛿𝐻 𝜕ℎ 𝑘𝐽
𝑐! = = = ( )
𝑚 𝛿𝑇 ! 𝑚 𝛿𝑇 ! 𝜕𝑇 ! 𝑘𝑔. 𝐾
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
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
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
The specific heat values for some common gases are listed as a function of
temperature in Table A–2b
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)
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:
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.
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
!"#$ !! !"!#$% !"#$%&'" !"#$ !" !!!"#$ !"
!" !!"#,!"#$ !"# !"## !"#$%"& !"#$%& !"!#$%
The first law of thermodynamics for a control volume can be written as:
𝑉! 𝑉! 𝑑𝐸!.!.
𝑄!.!. + 𝑚(ℎ + + 𝑔𝑧) = 𝑊!.!. + 𝑚(ℎ + + 𝑔𝑧) +
2 2 𝑑𝑡
!" !"#
!"# !"#! !"#$% !"# !"#! !"#$
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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 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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