Chapter - 3

The first law of thermodynamics

1
Learning objectives
• By the end of this chapter you will be able to:
• Classify types of energy in thermodynamic analysis.
• State the first law of thermodynamics.
• Do energy balance analysis for a closed system.
• Write moving boundary work for different processes.
• Develop a relation between internal energy (u), enthalpy (h) and specific
heats (cp and cv) for ideal gases and for liquids and solids.
• Do energy balance analysis for open systems (control volume system).
• Define flow work and energy of flowing fluid.
• Energy analysis of steady flow process.
• Energy analysis of unsteady flow process.
2
Introduction
static dynamic

They are the only forms in which energy

can cross the boundaries of a closed
system
Forms of energy
• Energy exist in numerous forms such as : Thermal, Mechanical,
kinetic, potential, electric, magnetic, nuclear and the summation of all
is called the total energy.
• In the study of thermodynamics energy is grouped as macroscopic
and microscopic.
• Macroscopic : An energy a system posses as a whole with respect to
some outside reference frame. E.g. kinetic and potential energy
• Microscopic : Energy of a system related to molecular structure of a
system and degree of molecular activities. E.g. molecular kinetic
energy, chemical energy, latent energy. The summation of all
microscopic energy is called internal energy (U).
Forms of energy
• Magnetic, electric, surface tension and gravitational effects are
significant in some specialized cases only and are often neglected.
• Therefore the total energy of a simple compressible system is given by
• 𝐸 = 𝐾. 𝐸 + 𝑃. 𝐸 + 𝑈 𝑘𝐽
1
•𝐸= 𝑚𝑉 2 + 𝑚𝑔ℎ + 𝑈 𝑘𝐽
2
• In most cases closed systems are considered stationary i.e ∆𝐾. 𝐸 =
∆𝑃. 𝐸 = 0, and the change in total energy is reduced to change in
internal energy
• ∆𝐸 = ∆𝑈
Forms of energy
• 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.
𝐸ሶ = 𝑚𝑒
ሶ (𝑘𝑊)

Mass flow rate

𝑚ሶ = 𝜌𝑉ሶ = 𝜌𝐴𝑐 𝑉𝑎𝑣𝑔 (Kg/s)
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.
• 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.
• pressure force acting on a fluid through a distance produces work,
called flow work, in the amount of P/ρ per unit mass.
• mechanical energy of a flowing fluid

𝑃 𝑉2
𝑒𝑚𝑒𝑐 = + + 𝑔𝑧 (kJ/kg)
𝜌 2
Mechanical energy
• It can also be expressed in rate form as
𝑃 𝑉2
𝐸ሶ 𝑚𝑒𝑐 = 𝑚ሶ + + 𝑔𝑧 (kW)
𝜌 2
• Then the mechanical energy change of a fluid during incompressible
(ρ = constant) flow becomes
𝑃2 −𝑃1 𝑉22 −𝑉12
∆𝑒𝑚𝑒𝑐 = + + 𝑔(𝑧2 − 𝑧1 ) (kJ/kg)
𝜌 2

𝑃2 − 𝑃1 𝑉22 − 𝑉12
∆𝐸ሶ 𝑚𝑒𝑐 = 𝑚ሶ + + 𝑔 𝑧2 − 𝑧1 (kW)
𝜌 2
Energy transfer by heat
• 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.
• Heat is energy in transition. It is recognized only as it crosses the
boundary of a system.

• A process during which there is no

heat transfer is called an adiabatic
process.
• Thermal equilibrium
• Insulation
Energy transfer by heat
• 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
𝑄
𝑞= kJ/kg
𝑚

• The heat transfer rate is denoted by 𝑄ሶ

𝑡2
𝑄= ሶ
‫𝑡𝑑𝑄 𝑡׬‬ kJ
1
Energy transfer by work
• Energy interaction that is not caused by a temperature difference
between a system and its surroundings is work.
• More specifically, work is the energy transfer associated with a
force acting through a distance.
• The work done during a process between states 1 and 2 is denoted
by W12, or simply W. The work done per unit mass of a system is
denoted by w and is expressed as
𝑊
𝑤= kJ/kg
𝑚
• The work done per unit time is called power.
𝑊
ሶ
𝑊= kW
𝑡
• 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.

• Generally accepted sign convention:

• 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.
• Heat and work are energy transfer
mechanisms between a system and its
surroundings, and there are many similarities
between them:
1. Both are recognized at the boundaries of a system as they cross
the boundaries. That is, both heat and work are boundary
phenomena.
2. Systems possess energy, but not heat or work.
3. Both are associated with a process, not a state. Unlike properties,
heat or work has no meaning at a state.
4. Both are path functions (i.e., their magnitudes depend on the path
followed during a process as well as the end states).
• Path functions have inexact differentials designated by the symbol δ
• Exact differentials designated by the symbol d
Boundary work

• The work associated with a moving

boundary is called boundary work.
• Moving boundary work is the primary form
of work involved in automobile engines.
• The boundary work in real engines or
compressors is determined by direct
measurements.
• A quasi-equilibrium process, also called a quasistatic process, is
closely approximated by real engines, especially when the
piston moves at low velocities.
• If the piston is allowed to move a distance ds
in a quasi-equilibrium manner, the
differential work done during this process is

𝛿𝑊𝑏 = 𝐹𝑑𝑠 = 𝑃𝐴𝑑𝑠 = 𝑃𝑑𝑉

• P is always positive
• dV is positive for expansion (work done
by system; Wout)
• dV is negative for compression (work A gas does a differential
done on the system; Win) amount of work δWb as
it forces the piston to
• The moving boundary work is also called the move by a differential
PdV work. amount ds.
• 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
2
𝑊𝑏 = න 𝑃 𝑑𝑉 kJ
1

The area under P-V graph

indicates the boundary work
2 2
𝐴 = න 𝑑𝐴 = න 𝑃 𝑑𝑉
1 1
• This integral can be evaluated only if we know the functional
relationship between P and V during the process. That is, P = f(V)
should be available.
2
𝑊𝑏 = න 𝑃 𝑑𝑉 kJ
1
Isobaric process
2
𝑊1−2 = න 𝑃𝑑𝑉
1

2
𝑊1−2 = 𝑃 න 𝑑𝑉 = 𝑃 𝑉2 − 𝑉1
1
Isometric / Isochoric process
2
𝑊1−2 = න 𝑃𝑑𝑉
1

2
𝑊1−2 = න 𝑃𝑑𝑉 = 0
1

Isothermal process 𝑃1 𝑉1
𝑃1 𝑉1 = 𝑃2 𝑉2 𝑃=
𝑉
2 2 2
𝑃1 𝑉1
𝑊1−2 = න 𝑃𝑑𝑉 = න 𝑑𝑉 = 𝑃1 𝑉1 න 𝑑𝑉
1 1 𝑉 1

𝑉2
𝑊1−2 = 𝑃1 𝑉1 ln
𝑉1
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
𝑃 = 𝐶𝑉 −𝑛
2 2
𝑊1−2 = න 𝑃𝑑𝑉 = න 𝐶𝑉 −𝑛 𝑑𝑉
1 1

𝑉2−𝑛+1 − 𝑉1−𝑛+1 𝑃2 𝑉2 − 𝑃1 𝑉1
𝑊1−2 =𝐶 =
−𝑛 + 1 1−𝑛
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.
• Experimentally its observed that during an adiabatic process
between two specified states 1 and 2, 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.
• Considering that the net work is the same for all the value of the
net work must depend on the end states of the system only, and
thus it must correspond to a change in a property of the system.
• This property is the total energy.
The first law of thermodynamics
• 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.

𝐸𝑖𝑛 − 𝐸𝑜𝑢𝑡 = ∆𝐸𝑠𝑦𝑠𝑡

 The first law of thermodynamics

LHS RHS
𝐸𝑖𝑛 − 𝐸𝑜𝑢𝑡
= 𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡 + 𝑊𝑖𝑛 − 𝑊𝑜𝑢𝑡
+ 𝐸𝑚𝑎𝑠𝑠,𝑖𝑛 − 𝐸𝑚𝑎𝑠𝑠,𝑜𝑢𝑡
 Energy analysis of closed system

For a cycle ΔE = 0, thus Q = W

Energy balance for closed system
• The energy balance relation in that case for a closed system
becomes
𝑄𝑛𝑒𝑡,𝑖𝑛 − 𝑊𝑛𝑒𝑡,𝑜𝑢𝑡 = ∆𝐸𝑠𝑦𝑠

or 𝑄 − 𝑊 = ∆𝐸𝑠𝑦𝑠

• For a closed system undergoing a cycle

𝑄𝑛𝑒𝑡,𝑖𝑛 = 𝑊𝑛𝑒𝑡,𝑜𝑢𝑡 𝑄ሶ 𝑛𝑒𝑡,𝑖𝑛 = 𝑊ሶ 𝑛𝑒𝑡,𝑜𝑢𝑡
Example:

A piston–cylinder device contains 25 g of saturated water vapor that is

maintained at a constant pressure of 300 kPa. A resistance heater within
the cylinder is turned on and passes a current of 0.2 A for 5 min from a
120-V source. At the same time, a heat loss of 3.7 kJ occurs.
(a) Show that for a closed system the boundary work Wb and the change
in internal energy ΔU in the first-law relation can be combined into
one term, ΔH, for a constant-pressure process.
(b) Determine the final temperature of the steam.
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.
• In general, this energy depends on how the process is executed
(at constant volume or at constant pressure).

• The specific heat at constant

pressure cp is always greater than cv
because at constant pressure the
system is allowed to expand, and
the energy for this expansion work
must also be supplied to the system.
Specific heats
• Now we try to express the specific heats in terms of other
thermodynamic properties.
• Consider a fixed mass stationary closed system undergoing a
constant volume heating process; the differential energy
balance will be given by;
𝛿𝑞 − 𝛿𝑤 = 𝑑𝑢
From the definition of cv heat added 𝛿𝑞 = 𝑐𝑣 𝑑𝑇
Therefore cv can be defined in terms of u and T as
𝑐𝑣 𝑑𝑇 = 𝑑𝑢 𝜕𝑢
𝑐𝑣 =
𝜕𝑇 𝑣
Specific heats
• Similarly for a constant pressure heating of a stationary closed
system the differential energy balance will be;
𝛿𝑞 − 𝛿𝑤 = 𝑑𝑢
𝛿𝑞 − 𝑃𝑑𝑣 = 𝑑𝑢
𝛿𝑞 = 𝑑𝑢 + 𝑃𝑑𝑣 ℎ = 𝑢 + 𝑃𝑣
𝑑ℎ = 𝑑𝑢 + 𝑃𝑑𝑣 + 𝑣𝑑𝑃
𝛿𝑞 = 𝑑ℎ
From the definition of cp, 𝛿𝑞 = 𝑐𝑝 𝑑𝑇
𝑐𝑝 𝑑𝑇 = 𝑑ℎ
𝜕ℎ
𝑐𝑝 =
𝜕𝑇 𝑃
Internal energy, entropy and specific heats of
ideal gas
• Ideal gases obey the ideal gas equation of state ;
𝑃𝑣 = 𝑅𝑇
• for an ideal gas the internal energy is a functions 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

Therefore;
ℎ = ℎ(𝑇)
Internal energy, entropy and specific heats of
ideal gas
• Since u and h depend only on temperature for an ideal gas, the
specific heats cv and cp also depend, at most, on temperature
only.
𝑑𝑢 = 𝑐𝑣 𝑇 𝑑𝑇
𝑑ℎ = 𝑐𝑃 𝑇 𝑑𝑇
• 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:
2 2
∆𝑢 = න 𝑐𝑣 𝑇 𝑑𝑇 ∆ℎ = න 𝑐𝑃 𝑇 𝑑𝑇
1 1
Internal energy, entropy and specific heats of
ideal gas
• Having the functional relation of the specific heats with
temperature, performing the integration provides accurate values
of ∆𝑢 and ∆ℎ , but its tedious and inconvenient for hand
calculation.
• The other alternatives are;
1. Using tabulated data: This is the easiest and most accurate
way when tables are readily available.

∆𝑢 = 𝑢2 − 𝑢1

∆ℎ = ℎ2 − ℎ1
Internal energy, entropy and specific heats of
ideal gas
2. By using average specific heats: This is very simple and
certainly very convenient when property tables are not
available. The results obtained are reasonably accurate if the
temperature interval is not very large.
∆𝑢 = 𝑐𝑣 𝑎𝑣 𝑇2 − 𝑇1
∆ℎ = 𝑐𝑃 𝑎𝑣 𝑇2 − 𝑇1
Where 𝑇2 + 𝑇1
𝑇𝑎𝑣 =
𝑐𝑣,𝑎𝑣 = 𝑐𝑣@𝑇𝑎𝑣 2

𝑐𝑃,𝑎𝑣 = 𝑐𝑃@𝑇𝑎𝑣
Specific Heat Relations of Ideal Gases
A special relationship between cp and cv for ideal gases can be
obtained by differentiating the relation ℎ = 𝑢 + 𝑅𝑇
𝑑ℎ = 𝑑𝑢 + 𝑅𝑑𝑇
𝑑ℎ = 𝑐𝑃 𝑑𝑇
𝑑𝑢 = 𝑐𝑣 𝑑𝑇
𝑐𝑃 = 𝑐𝑣 + 𝑅 𝑘𝐽/𝑘𝑔𝐾

𝑐𝑃ҧ = 𝑐𝑣ҧ + 𝑅𝑢 𝑘𝐽/𝑘𝑚𝑜𝑙𝐾

At this point, we introduce another ideal-gas property called the

specific heat ratio k, defined as
𝑐𝑃
𝑘=
𝑐𝑣
Internal energy, enthalpy, and specific
heats of solids and liquids
• Solids and liquids are incompressible substances, i.e. during a
process their density remains constant.
• For incompressible substance the 𝑐𝑃 and 𝑐𝑣 are identical, i.e.
𝑐𝑃 = 𝑐𝑣 = 𝑐

Internal Energy Changes

The specific heat of incompressible substance is dependent on
temperature only.
𝑑𝑢 = 𝑐𝑣 𝑑𝑇 = 𝑐 𝑇 𝑑𝑇
Internal energy, enthalpy, and specific
heats of solids and liquids
Internal Energy Changes
The change in internal energy between states 1 and 2 is then
obtained by integration:
2
∆𝑢 = 𝑢2 − 𝑢1 = න 𝑐 𝑇 𝑑𝑇
1
For small temperature intervals, a c value at the average
temperature can be used and treated as a constant, yielding
∆𝑢 = 𝑐𝑎𝑣 (𝑇2 − 𝑇1 )
Internal energy, enthalpy, and specific
heats of solids and liquids
Enthalpy Changes
From the definition of ℎ = 𝑢 + 𝑃𝑣
𝑑ℎ = 𝑑𝑢 + 𝑃𝑑𝑣 + 𝑣𝑑𝑃
For incompressible substance 𝑑𝑣 = 0
𝑑ℎ = 𝑑𝑢 + 𝑣𝑑𝑃
Integrating
∆ℎ = ∆𝑢 + 𝑣∆𝑃 = 𝑐𝑎𝑣 ∆𝑇 + 𝑣∆𝑃
For solids the 𝑣∆𝑃 is not significant therefore
∆ℎ = ∆𝑢 = 𝑐𝑎𝑣 ∆𝑇
Internal energy, enthalpy, and specific
heats of solids and liquids
Enthalpy Changes
There are two cases for liquids
1. Constant-pressure processes, as in heaters ∆𝑃 = 0
∆ℎ = ∆𝑢 = 𝑐𝑎𝑣 ∆𝑇
2. Constant-temperature processes, as in pumps ∆𝑇 = 0
∆ℎ = ∆𝑢 + 𝑣∆𝑃 = 𝑐𝑎𝑣 ∆𝑇 + 𝑣∆𝑃 = 𝑣𝑑𝑃
Review exercise

Nitrogen at an initial state of 300 K, 150 kPa,

and 0.2 m3 is compressed slowly in an
isothermal process to a final pressure of 800
kPa. Determine the work done during this
process.
Review exercise

The volume of 1 kg of helium in a piston-cylinder device is initially 5 m3 . Now

helium is compressed to 2 m3 while its pressure is maintained constant at 180 kPa.
Determine the initial and final temperatures of helium as well as the work
required to compress it, in kJ. Take R = 2.0769 kJ/kg.K
Review exercise

A piston–cylinder device initially contains 0.4 kg of nitrogen gas at 160 kPa and
140℃. The nitrogen is now expanded isothermally to a pressure of 100 kPa.
Determine the boundary work done during this process. Take R = 0.2968 kJ/kg.K
Review exercise

A piston–cylinder device contains 0.15 kg of air initially at 2 MPa and 350℃. The
air is first expanded isothermally to 500 kPa, then compressed polytropically with
a polytropic exponent of 1.2 to the initial pressure, and finally compressed at the
constant pressure to the initial state. Determine the boundary work for each
process and the net work of the cycle.
Review exercise

A piston–cylinder device contains 2.2 kg of nitrogen initially at 100 kPa and 25℃.
The nitrogen is now compressed slowly in a polytropic process during which PV 1.3
= constant until the volume is reduced by one-half. Determine the work done and
the heat transfer for this process. (take R = 0.2968 kPa.m3 /kg.K; 𝑐𝑣,𝑎𝑣 = 0.744
kJ/kg.K)