Engineering

Therrmodynamics

CHAPTER FOUR
4. First Law of Thermodynamics
1. Introduction to First Law of Thermodynamics
2. Definition of Heat
3. Mechanisms of Heat Transfer
4. Specific Heats
5. Internal Energy, Enthalpy and Specific Heats of
Gases, Liquids, and Solids
6. The First Law of Thermodynamics for Control
Volume
THE FIRST LAW OF THERMODYNAMICS
• The first law of thermodynamics states that energy can be neither
created nor destroyed during a process; it can only change forms.
• 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.
• This principle is called the first law of thermodynamics or just the first
law.
• It simply states that the change in the total energy during an
adiabatic process must be equal to the net work done.
• The value of the net work must depend on the end states of the
system only.

FIGURE 2–42 The work (electrical) done on an adiabatic system FIGURE 2–44 The work (boundary) done on an adiabatic system is
is equal to the increase in the energy of the system. equal to the increase in the energy of the system.
• Energy Balance by the conservation of energy principle can be
expressed as follows:

• Energy Change of a System, ΔEsystem

• Note that energy is a property, and the value of a property does not
change unless the state of the system changes.
• 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:
Where

FIGURE 2–46 For stationary systems, ΔKE = ΔPE = 0; thus

ΔE = ΔU.
• 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.
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.
 – Car engines and hydraulic, steam, or gas turbines produce work,
while compressors, pumps, and mixers consume work.
3. Mass Flow, m Mass flow in and out of the system serves as an
additional mechanism of energy transfer.
• For example, when some hot water is taken out of a water heater and is
replaced by the same amount of cold water, the energy content of the hot-
water tank (the control volume) decreases as a result of this mass
interaction.

FIGURE 2–47 The energy content of a control volume can be changed by mass flow as well
as by heat and work interactions.

• Energy balance for energy transfer in the forms of heat, work, and
mass can be:
 – The heat transfer Q is zero for adiabatic systems,
– The work transfer W is zero for systems that involve no
work interactions,
– The energy transport with mass Emass is zero for systems
that involve no mass flow across their boundaries (i.e.,
closed systems).
• Energy balance for any system undergoing any kind of process can be
expressed more compactly as:

• or, in the rate form, as

• For constant rates, the total quantities during a time interval Δt are
related to the quantities per unit time as
• The energy balance can be expressed on a per unit mass basis as

• Energy balance can also be expressed in the differential form as

• For a closed system undergoing a cycle, the initial and final states are
identical, and thus ΔEsystem = E2 − 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

FIGURE 2–48 For a cycle ΔE = 0, thus Q = W

FIGURE 2–49 Schematic for
Example 2–10.
FIGURE 2–50 Schematic for Example 2–
11. ©Design Pics/PunchStock RF
FIGURE 2–51 Schematic for Example 2–
12.
FIGURE 2–52 Fluorescent lamps lighting a classroom
as discussed in Example 2–13. ©PhotoLink/Getty
Images RF
Definition of Heat
• Heat is a form of energy that can be transferred from one object or
system to another as a result of a difference in temperature.
• It is associated with the motion of particles, such as atoms and
molecules, within a substance.
• The greater the temperature difference between two objects in
contact, the greater the heat flow between them.
• Heat can be measured in units such as joules or calories, and it is
typically represented by the symbol "Q".
• Heat is involved in many natural phenomena, including
thermodynamics, weather systems, and chemical reactions.
Mechanisms of Heat Transfer
• Heat can be transferred in three different ways: conduction,
convection, and radiation.
• All modes of heat transfer require the existence of a temperature
difference,
• All modes of heat transfer are from the high-temperature medium to
a lower temperature one.
• Conduction is the transfer of energy from the more energetic
particles of a substance to the adjacent less energetic ones as a result
of interactions between the particles.
• Conduction can take place in solids, liquids, or gases.

✓ Δx is a layer of constant thickness proportional to ΔT

✓ ΔT the temperature difference across the layer
✓ A the area normal to the direction of heat transfer
✓ k is the thermal conductivity of the material
 FIGURE 2–69 Heat conduction from warm air to a cold canned drink through the wall of the aluminum can

• Materials such as copper and silver, which are good electric

conductors, are also good heat conductors, and have high k values.
• Materials such as rubber, wood, and styrofoam are poor conductors
of heat and therefore have low k values.
• In the limiting case of Δx → 0, the preceding equation reduces to the
differential form

• which is known as Fourier’s law of heat conduction.

• Convection is the mode of energy transfer
between a solid surface and the adjacent
liquid or gas that is in motion, and it
involves the combined effects of
conduction and fluid motion.
• The faster the fluid motion, the greater
the convection heat transfer.
• In the absence of any bulk fluid motion,
FIGURE 2–70 Heat transfer from a hot surface to
heat transfer between a solid surface and air by convection.

the adjacent fluid is by pure conduction.

• 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
FIGURE 2–71 The cooling of a boiled egg by forced and
density differences due to the variation of natural convection.
temperature in the fluid .
• The rate of heat transfer by convection Q · conv is determined from
Newton’s law of cooling, expressed as

• where
– h is the convection heat transfer coefficient,
– A is the surface area through which heat transfer takes place,
– Ts is the surface temperature, and
– Tf is bulk fluid temperature away from the surface.
• Radiation is the energy emitted by matter in the form of
electromagnetic waves (or photons) as a result of the changes in the
electronic configurations of the atoms or molecules.
• Thermal radiation is the form of radiation emitted by bodies because
of their temperature.
• It differs from other forms of electromagnetic radiation such as X-
rays, gamma rays, microwaves, radio waves, and television waves that
are not related to temperature.
 FIGURE 2–72 Unlike conduction and convection, heat transfer by radiation can occur
between two bodies even when they are separated by a medium colder than both of them.

• The maximum rate of radiation that can be emitted from a surface at

an absolute temperature Ts is given by the Stefan–Boltzmann law as

• where A is the surface area and σ = 5.67 × 10−8 W/m2 ·K4 is the
Stefan– Boltzmann constant.
• The idealized surface that emits radiation at this maximum rate is
called a blackbody, and the radiation emitted by a blackbody is called
blackbody radiation.
• The radiation emitted by all real surfaces is less than the radiation
emitted by a blackbody at the same temperatures and is expressed as

• where ɛ is the emissivity of the surface. The property emissivity,

whose value is in the range 0 ≤ ɛ ≤ 1, is a measure of how closely a
surface approximates a blackbody for which ɛ = 1.
✓ absorptivity, α, is the fraction of the radiation energy incident on a
surface that is absorbed by the surface.
✓ Like emissivity, its value is in the range 0 ≤ α ≤ 1. A blackbody absorbs
the entire radiation incident on it.
✓ That is, a blackbody is a perfect absorber (α = 1) as well as a perfect
emitter.
✓ In general, both ɛ and α of a surface depend on the temperature and
the wavelength of the radiation. Kirchhoff’s law of radiation states
that the emissivity and the absorptivity of a surface are equal at the
same temperature and wavelength.
 The rate at which a surface absorbs radiation
is determined from

FIGURE 2–73 The absorption of radiation incident on an

opaque surface of absorptivity α.

• where Q · incident is the rate at which radiation is incident on the

surface and α is the absorptivity of the surface.
• For opaque (nontransparent) surfaces, the portion of incident
radiation that is not absorbed by the surface is reflected back.
• The difference between the rates of radiation emitted by the surface
and the radiation absorbed is the net radiation heat transfer.
• If the rate of radiation absorption is greater than the rate of radiation
emission, the surface is said to be gaining energy by radiation.
• Otherwise, the surface is said to be losing energy by radiation.
• The net rate of radiation heat transfer between these two surfaces is
determined from

Where
➢ ɛ is surface emissivity
➢ A surface area at absolute temperature
Ts that is completely enclosed by a
much larger surface at absolute
temperature Tsurr

FIGURE 2–74 Radiation heat transfer between a body and the inner surfaces of a
much larger enclosure that completely surrounds it.
FIGURE 2–75 Heat transfer from the
person described in Example 2–18.
ENERGY BALANCE FOR CLOSED SYSTEMS
• Energy balance for any system undergoing any kind of process was
expressed as

• or, in the rate form, as

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

• The energy balance can be expressed on a per unit mass basis as

• Energy balance can also be expressed in the differential form as

• For a closed system undergoing a cycle, the initial and final states are
identical, and thus ΔEsystem = E2 − 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

• The energy balance relation in that case for a closed system becomes

• where Q = Qnet,in = Qin − Qout is the net heat input and W =

Wnet,out = Wout − Win is the net work output.
 FIGURE 4–11 For a cycle ΔE = 0, thus Q = W.
FIGURE 4–12 Various forms of the first-law relation for closed
systems.
• SPECIFIC HEATS
• The specific heat is defined as the energy required to raise the
temperature of a unit mass of a substance by one degree.
• There are two kinds of specific heats: specific heat at constant
volume cv and specific heat at constant pressure cp.
• The specific heat at constant volume cv can be viewed as the energy
required to raise the temperature of the unit mass of a substance by
one degree as the volume is maintained constant.
• The energy required to do the same as the pressure is maintained
constant is the specific heat at constant pressure cp.
• The conservation of energy principle ein − eout = Δesystem for this
process can be expressed in the differential form as

• Where
 FIGURE 4–19 Constant-volume and constant- pressure specific heats cv and cp ( values given are for
helium gas).

FIGURE 4–20 Formal definitions of cv and cp. FIGURE 4–21 The specific heat of a substance changes
with temperature.
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

• Using the definition of enthalpy and the equation of state of an ideal

gas, we have

The differential changes in the internal

energy and enthalpy of an ideal gas can be
expressed as

FIGURE 4–23 For ideal gases, u, h, cv, and cp vary with

temperature only.
• The specific heat functions can be replaced by the constant average
specific heat values as:

For small temperature intervals, the specific heats may be assumed to

vary linearly with temperature.

Three ways of calculating Δu.

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

obtained by differentiating the relation h = u + RT, which yields

• Which gives
• The specific heat ratio k of ideal-gas property is
Schematic and P-V
diagram for Example 4–8.
Schematic and P-V diagram
for Example 4–9.
Schematic and P-V diagram for
Example 4–10.
• INTERNAL ENERGY, ENTHALPY, AND SPECIFIC HEATS
OF SOLIDS AND LIQUIDS
• A substance whose specific volume (or density) is constant is called
an incompressible substance.
• The specific volumes of solids and liquids essentially remain constant
during a process.
• The constant-volume and constant-pressure specific heats are
identical for incompressible substances.

• Internal Energy Changes

• Enthalpy Changes
• Using the definition of enthalpy h = u + Pv and noting that v =
constant,
Schematic for Example
4–12.
Schematic for Example 4–13
The First Law of Thermodynamics for Control Volume
CONSERVATION OF MASS
• Technically, mass is not exactly conserved. It turns out that mass m
and energy E can be converted to each other according to the well-
known formula proposed by Albert Einstein (1879–1955):

• where c is the speed of light in a vacuum, which is c = 2.9979×108

m/s.
• All physical and chemical systems exhibit energy interactions with
their surroundings, but the amount of energy involved is equivalent
to an extremely small mass compared to the system’s total mass.
• For example, when 1 kg of liquid water is formed from oxygen and
hydrogen at normal atmospheric conditions, the amount of energy
released is 15.8 MJ, which corresponds to a mass of only 1.76 × 10–
10 kg.
• Even in nuclear reactions, the mass equivalence of the amount of
energy interacted is a very small fraction of the total mass involved.
• Therefore, in most engineering analyses, we consider both mass and
energy as conserved quantities.
• For closed systems, the conservation of mass principle is implicitly
used by requiring that the mass of the system remain constant during
a process.
• For control volumes, however, mass can cross the boundaries, and so
we must keep track of the amount of mass entering and leaving the
control volume.
• The amount of mass flowing through a cross section per unit time is
called the mass flow rate and is denoted by 𝑚.ሶ

Note that both δ and d are used to indicate differential quantities,

but δ is typically used for quantities (such as heat, work, and mass
transfer) that are path functions and have inexact differentials,
while d is used for quantities (such as properties) that are point
The normal velocity Vn for a surface is the
functions and have exact differentials component of velocity perpendicular to the surface.
• The mass flow rate through the entire cross-sectional area of a pipe
or duct is obtained by integration:

• For incompressible flow or even for compressible flow where ρ is

approximated as uniform across Ac,

• Where average velocity is

The average velocity Vavg is defined as the average speed through a

cross section.

• The volume of the fluid flowing through a cross section per unit time
is called the volume flow rate 𝑉ሶ

The volume flow rate is the volume of fluid flowing through a cross section per
unit time.
• The mass and volume flow rates are related by

• Conservation of Mass Principle:

– The conservation of mass principle for a control volume can be expressed as:

– Or in the rate form

– The mass of a differential volume dV within the control volume is
dm = ρ dV.
Total mass within the CV:
Rate of change of mass within the CV:

For no mass crossing the control

surface (i.e., the control volume is a
closed system),
The differential control volume dV and the differential
control surface dA used in the derivation of the
conservation of mass relation.
• Now consider mass flow into or out of the control volume through a
differential area dA on the control surface of a fixed control volume.
Let n → be the outward unit vector of dA normal to dA and V → be
the flow velocity at dA relative to a fixed coordinate system, as shown
in Fig. 5–6. In general, the velocity may cross dA at an angle θ off the
normal of dA, and the mass flow rate is proportional to the normal
component of velocity V → n = V → cos θ ranging from a maximum
outflow of V → for θ = 0 (flow is normal to dA) to a minimum of zero
for θ = 90° (flow is tangent to dA) to a maximum inflow of V → for θ =
180° (flow is normal to dA but in the opposite direction). Making use
of the concept of dot product of two vectors, the magnitude of the
normal component of velocity is
• Normal component of velocity:

• Differential mass flow rate:

• The net flow rate into or out of the control volume through the entire
control surface is obtained by integrating δm ˙ over the entire control
surface,
• Net mass flow rate:

A control surface should always be selected normal to the flow

at all locations where it crosses the fluid flow to avoid
complications, even though the result is the same.

• Note that Vn = V → · n → = V cos θ is positive for θ < 90° (outflow)

and negative for θ > 90° (inflow).
• Using 𝑑𝑚𝑐𝑣 Τ𝑑𝑡 + 𝑚𝑜𝑢𝑡 ሶ − 𝑚𝑖𝑛 ሶ= 0, the conservation of mass
relation for a fixed control volume is
• General conservation of mass:

• It states that the time rate of change of mass within the control
volume plus the net mass flow rate through the control surface is
equal to zero.
• Therefore, the general conservation of mass relation can be

• Or all the inlets and outlets are:

• The above equations are also valid for moving or deforming control
volumes provided that the absolute velocity 𝑉 is replaced by the
relative velocity 𝑉𝑟 , which is the fluid velocity relative to the control
surface.
• The conservation of mass principle for a general steady-flow system
with multiple inlets and outlets is expressed in rate form as

• It states that the total rate of mass entering a control volume is equal
to the total rate of mass leaving it.
• Many engineering devices such as nozzles, diffusers, turbines,
compressors, and pumps involve a single stream (only one inlet and
one outlet).
• For single-stream steady-flow systems,
• The conservation of mass relations for steady, incompressible flow:

Schematic for Example 5–1. ©John M.

Cimbala
Schematic for Example 5–2.
FLOW WORK AND THE ENERGY OF A FLOWING FLUID
• Unlike closed systems, control volumes involve mass flow across their
boundaries, work is required to push the mass into or out of the
control volume.
• This work is known as the flow work, or flow energy.

In the absence of acceleration, the

force applied on a fluid by a piston is
Schematic for flow work equal to the force applied on the
piston by the fluid.

Flow work is the energy needed to push a fluid into or out of a control volume, and it is
equal to Pv
Total Energy of a Flowing Fluid
• The total energy of a simple compressible system consists of three
parts: internal, kinetic, and potential energies .
• On a unit-mass basis, it is expressed as:

• where V is the velocity and z is the elevation of the system relative to

some external reference point.
• The fluid entering or leaving a control volume possesses an additional
form of energy—the flow energy Pv.
• Then the total energy of a flowing fluid on a unit-mass basis (denoted
by θ) becomes

• Pv + u = h (or enthalpy )
• So
 The total energy consists of three parts for a
nonflowing fluid and four parts for a flowing fluid.

• Energy Transport by Mass

The product 𝑚ሶ 𝑖 𝜃𝑖 is the

energy transported into
control volume by mass per
unit time.
ENERGY ANALYSIS OF STEADY-FLOW SYSTEMS
• Turbines, compressors, and nozzles, which operate under the same
conditions for long periods of time once the transient start-up period
is completed and steady operation is established, are classified as
steady-flow devices.
• Processes involving such devices are somewhat idealized process,
called the steady-flow process.
• The boundary work is zero for steady-flow systems (since VCV =
constant).
• And mCV = constant and ECV = constant
• Then the rate form of the general energy balance reduces for a
steady-flow process to

• The energy balance for a general steady-flow system is

• When performing a general analytical study or solving a problem that
involves an unknown heat or work interaction, it is common practice
to assume heat to be transferred into the system (heat input) at a
rate of 𝑄ሶ , and work produced by the system (work output) at a rate
of W˙ , and then solve the problem.
• The first-law or energy balance relation in that case for a general
steady-flow system becomes

• For single-stream devices,