Dr.

Farhan Altaee Thermodynamics/Chapter One

THERMODYNAMICS (I)
References
1. B.G., Kyle,” Chemical and Process Thermodynamics”,3 rd
edition, Prentice-Hall Inc., New Jersey (1984).

2. K.V. Narayanan,” A Text book of Chemical Engineering

Thermodynamics”, Prentice Hall of India, New Delhi (2011).

3. G.N. Pandey and J.C. Chaudhri,” Chemical Eng.

Thermodynamics”, Prentice Hall of India, New Delhi (2008).

4. J.M. Smith, H.C. Van Ness,” Introduction to Chemical

Engineering Thermodynamics, 6th edition Mc-Hill, New York.

5.J.M. Smith and H.C. Van Ness, Introduction to Chemical

Engineering Thermodynamics”, 4th edition, Mc-Hill, New York
(1987).

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Dr. Farhan Altaee Thermodynamics/Chapter One

Chapter One

Definitions

Thermodynamics: is a branch of physical science that treat with various

phenomena of energy and related properties of matters, especially the law of
transformation of heat into other forms of energy.

Pure substance: It is a homogeneous substance and its molecular structure

does not vary.

State: the thermodynamic state of a system is defined completely by the

knowledge of two independent and intensive properties (e.g. pressure,
specific volume, temperature…etc.).

Cycle: If processes are carried out on a working substance so that, at the

end, the substance is returned to its original state, then the substance is said
have been taken through a cycle. This is required in many engines.

System: all physical things in nature have some form of boundary whose
shape in general identities it. Inside its boundary, there are certain things
with particular functions to carry out. This arrangement is called system.

Types of Systems:

1. Closed system: inside this system, the mass of a substance remains

constant[ i.e. no mass transfer through the system boundary]. For
example: a piston of a cylinder.
2. Opened system: if the mass of a substance in a system changes or is
continuously changing [ i.e. a mass is crossing the system boundary].
For example: air compressor.

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Dr. Farhan Altaee Thermodynamics/Chapter One

3. Isolated system: In this type of a system mass and energy cannot be

transferred to or from the surrounding.

Non-Flow Process: A fixed mass of fluid undergoes a change of state with

no mass transfer across the boundaries, for example, the compression of the
mixture in an internal combustion engine.

Steady-Flow Process: A uniform mass flow rate from one state to another
where the mass must cross the control surface ( boundary) at inlet and exit.

Energy: It is defined as the capacity of a body or working substance to do

work in a process [e.g. a force moving through a distance].

Types of Energy:

1. Potential Energy: Is the energy of position.

∆𝑃𝐸 = 𝑚𝑔∆𝑍
∆𝑍 = 𝑒𝑙𝑒𝑣𝑎𝑡𝑖𝑜𝑛 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑐𝑒.
𝑚 = 𝑚𝑎𝑠𝑠
𝑔 = 𝑔𝑟𝑎𝑣𝑖𝑡𝑎𝑡𝑖𝑜𝑛𝑎𝑙 𝑎𝑐𝑐𝑒𝑙𝑒𝑟𝑎𝑡𝑖𝑜𝑛.

2. Kinetic Energy: Is the energy of motion.

1
∆𝐾𝐸 = 𝑚(𝐶22 − 𝐶12 )
2

𝑚
𝐶 = 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 ( )
𝑠

3. Internal Energy(∆𝑼): It is the result of the atoms motion and

molecules which make up the body. If the particle is in motion, then it
will possess kinetic energy, and greater the kinetic energy, the higher

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Dr. Farhan Altaee Thermodynamics/Chapter One

the temperature of the body will become. The change in temperature

will result a change in internal energy.
The internal energy of a body is denoted by the symbol (U) and has a
unit (N.m). the specific internal energy is the internal energy per unit
mass and denoted (u) in J/kg.
Work: The normal force acting on the piston is given by the product
of the pressure and the surface area:
𝐹 = 𝑃𝐴
For a small displacement (𝛿𝑥) of the piston and from work definition
with constant pressure:
𝛿𝑊 = 𝑃𝐴𝛿𝑥
𝛿𝑊 = 𝑃𝛿𝑉
Integrating yields:
𝑊𝐷𝑖𝑠𝑝 = 𝑃(𝑉2 − 𝑉1 )
Where 𝑊𝐷𝑖𝑠𝑝 is the displacement work introduced by releasing a
piston by the applied force.
Flow work: In processes involving fluid flow, it is useful to consider
the work done by an imaging piston acting on a fluid element about to
enter the system.
Power: This is defined as the rate of doing work and is measured in
(N.m/s) or (J/s) which is the Watt.
Other units of power:
1 metric hp=735.5 Watt
1 British hp=745.7 Watt
𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒
Mechanical Power: It is the rate of doing work= (J/s)
𝑇𝑖𝑚𝑒 𝑡𝑎𝑘𝑒𝑛

𝑃𝑜𝑤𝑒𝑟 = 𝑇𝜔

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Dr. Farhan Altaee Thermodynamics/Chapter One

Where T is the torque (N.m) , and 𝜔 is the rotational speed (1/s).

The Zeroth Law of Thermodynamics: It was first formulated by
R.H. Flower in 1931. It was named the zeroth law because it was
recognized after the 1st and 2nd Laws of thermodynamics.
The Zeroth Law of Thermodynamics states that if two bodies are in
equilibrium with a third body they also in thermal equilibrium with
each other. By replacing the third body with a thermometer, the law
can be restarted as two bodies are in thermal equilibrium if both have
the same temperature reaching even if they are not in contact.
Temperature: Is that property which determine the ability of a
system to transfer heat.
Temperature scales are:
I. Celsius Scale: based on two points i.e. freezing point and
boiling point.
0℃ − 𝑓𝑟𝑒𝑒𝑧𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 for pure substance
100℃ − 𝑏𝑜𝑖𝑙𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 for pure substance
II. Kelvin Scale: Also based on the freezing and boiling points of
water.
0𝐾 = −273.15℃
𝑇(𝐾) = 𝑡(℃) + 273.15
III. Fahrenheit Scale: Also based on the freezing and boiling
points of water.

32℉ 𝑖𝑠 𝑡ℎ𝑒 𝑓𝑟𝑒𝑒𝑧𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

212℉ 𝑖𝑠 𝑡ℎ𝑒 𝑏𝑜𝑖𝑙𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

𝑡(℉) = 1.8℃ + 32

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Dr. Farhan Altaee Thermodynamics/Chapter One

Enthalpy: Is a property of a substance and is a form of energy.

Perfect Gas: A gas is made of molecules that move around
with random motion. In a perfect gas, the molecules may
collide but they have no tendency to stick together.
Equation of State:
For a process from 1 to A (t=c)

𝑃1 𝑉1 = 𝑃𝐴 𝑉𝐴 (Boyl’s Law)

Boyl’s Law state that during a change of any gas in which the
mass and temperature remain constant, the volume varies inversely
with pressure i.e.:

𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 , 𝑃1 𝑉1 = 𝑃2 𝑉2 = 𝑃𝑛 𝑉𝑛

Charles’s Law states: During the change of the state of any gas in
which the mass and pressure remain constant. The volume varies in
proportional with the absolute temperature:

𝑉
=𝐶
𝑇

𝑉1 𝑉2 𝑉𝑛
= =
𝑇1 𝑇2 𝑇𝑛

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Dr. Farhan Altaee Thermodynamics/Chapter One

1st Law of Thermodynamics and Other Basic Concepts

The first law of thermodynamics in general deals with law of

conservation of energy and may be stated as when energy disappears in one
form it appears simultaneously in other forms.

So “first law” for a process applied both to system and surrounding in

general as:

∆(Energy of system) + ∆(Energy of surrounding) = 0

Where: Energy in the system in the form of:

“U, EK, EP”

Energy in the surrounding in the form of:

“Q, W”

W1 is (+ve) when done by system

(-ve) when done on system.

Q is (+ve) when transferred from surrounding to system

(-ve) when transferred from system to surrounding

Mathematical equations for first law :

∆U2
1. ∆U + m. + m. g∆Z = Q − W "open system"
2

2. ∆U = Q − W "closed system"

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Dr. Farhan Altaee Thermodynamics/Chapter One

W; work is “shaft work”, Ws and work when “fluid flow changes its
value” from initial to final volume as:

W = P. (V2 − V1 ) constant pressure

The heat supplied at constant pressure can be measured as the change

in another thermodynamics property of the system which call the
“enthalpy”. Is denoted by “H” and is perhaps the most widely used of
all thermodynamics functions. It is defined as:

H = U + P. V

And

∆H = ∆U + ∆(PV)

U: the internal energy of the system

P: the absolute pressure
V: the volume of the system

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Dr. Farhan Altaee Thermodynamics/Chapter One

The Steady-State Flow Process

For more important industrially are processes which involve the

steady-state flow of a fluid through equipment. For such processes the
more general first law expression must be used:

∆U2
∆U + + g. ∆Z = Q − W
2

W = Ws + P2 . V2 − P1 . V1

∆U2
∆U + + g. ∆Z = Q − Ws − P2 V2 + P1 V1
2

∆H = ∆U + ∆(PV)

∆U2
∆H + + g. ∆Z = Q − Ws
2

For many of applications considered in thermodynamics, the kinetics

and potential energy terms are very small compared with the others
and may be neglected. In this case:
∆H = Q − Ws

When no shaft work is accomplished, it reduce to:

∆H = Q

H2 − H1 = Q

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Dr. Farhan Altaee Thermodynamics/Chapter One

Example(1)

In a steady-state flow system, a substance flows at the rate of (4

kg). it enters at a pressure of 620 kN/m2 , a velocity of 300m/s,
internal energy 2100 kJ/kg and specific volume 0.37 m3/kg. it leaves
the system at a pressure of 130 kN/m2, a velocity of 150m/s, internal
energy 1500kJ/kg and specific volume 1.2 m3/kg. during its passage
through the system the substance has a loss by heat transfer of 30kJ/kg
to the surrounding. Determine the work of the system, stating whether
it is from or to the system. Neglect any change in potential energy.
Solution

∆U2
∆U + + g. ∆Z = Q − Ws − ∆(PV)
2

∆U2
Ws = Q − [∆U + ] − (P2 V2 − P1 V1 )
2

1502 −3002
= 30 − [1500 − 2100] + [ ] − (130x1.2 − 620x0.37)
2x1000

kJ
= 676.75
kg

kJ
= 676.75 x4kg
kg

= 2707 kJ is positive

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Dr. Farhan Altaee Thermodynamics/Chapter One

Example (2) : A steam turbine using steam at (1368 kpa) and (645K)
and discharge saturated steam at (137kpa) is used to generate work for
certain chemical plant. The turbine acts adiabatically and the feed and
discharge velocities may be considered equal. Determine the
theoretical work developed by the turbine if it uses (1650kg) steam.
From the steam tables, enthalpy of superheated steam at (1368 kpa
and 645 K) is 3200 kJ/kg and enthalpy of saturated steam at (137 kpa
is 2690 kJ/kg).
Solution

∆U2
∆H + + g. ∆Z = Q − Ws
2

Q=0 “the process is adiabatic”

∆Z = 0 “the same level”
∆U = 0 “the velocities are equal”
∆H = −Ws

∆H = −(H2 − H1 )
= −(2690 − 3200)
= 510 kJ/kg
kJ
= 510 x1650 kg
kg
= 841500 kJ

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Dr. Farhan Altaee Thermodynamics/Chapter One

The Heat Capacity:

It is customary to define a heat capacity (C) in terms of the heat
required to produce a temperature change when the system is
constrained to specified path:
∂Q
C=( )
∂T path
Path of constant volume: p. dv = 0
Therefore dW = 0
dU = dQ v

The constant volume heat capacity “Cv” is now expressed as:

∂U
Cv = ( )
∂T v
For constant pressure: dU = Q − W , W=p.dv

dH = dQ p
And the constant pressure heat capacity “Cp” becomes:

∂H
Cp = ( )
∂T p
The internal energy and enthalpy changes can be expressed as:

[∆U = ∫ Cv . dT]
v

[∆H = ∫ Cp . dT]
p

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Dr. Farhan Altaee Thermodynamics/Chapter One

Example(3):
Water at (368K) is pumped from storage tank at the rate of
(0.25m3). The motor for the pump supplies work at the rate of (0.214
kJ/kg), the water passes through a heat exchanger, where it gives up
heat at the rate of (100.8kJ/kg) and is delivered to a second stage tank
at an elevation of (0.2m) above the first tank. What is the temperature
of the water delivered to the second storage tank? Assume that the
enthalpy of water is zero at (273K) and the specific heat of water is
constant at (4.2kJ/kg.K).
Solution
1000kg
mass of water = ρ. V = 3
. 0.25m3 = 250kg
m

∆Ep = m. g. ∆Z = 250x9.8x0.2 = 0.490kJ/kg

Q = −100.8kJ/kg
Ws = −0.214kJ/kg
∆Ek = 0 “no change in the kinetic energy of water”
∆H + ∆Ep + ∆Ek = Q − Ws
100.78kJ
∆H = Q − Ws − ∆Ep = −100.8 + 0.214 − 0.490 = −
kg
H2 − H1 = −100.78kJ/kg

H1 = Cp (T1 − To )
= 4.2(368 − 273)
= 399 kJ/kg

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Dr. Farhan Altaee Thermodynamics/Chapter One

H2 = H1 − 100.78kJ/kg

= 399 − 100.78

= 298.22kJ/kg

H2 = Cp (T2 − To )

T2 : temperature of water at the second tank

298.22 = 4.2(T2 − 273)

T2 = 344 K

Joule’s Experiments:
To understanding of heat and its relation to work, by James
Joule (1818-1891).

In the most famous series of measurement, he placed known

amount of water, oil, and mercury in an insulated container and
agitated the fluid with a rotating stirrer:

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Dr. Farhan Altaee Thermodynamics/Chapter One

The amount of work done on the fluid were accurately measured, and
the temperature changes of the fluid were carefully noted. He found for each
fluid that a mixed amount of work was required per unit mass for energy
degree of temperature rise caused by stirring and the original temperature of
the fluid.

W=Q
Thus Joule was able to show conclusively that quantitative
relationship exists between work and heat, therefore, heat is form of
energy.

State and Path Functions:

Any quantity whose value depends only on the initial and final state
(i.e. initial and final temperature, pressure, composition,….etc.) and not on
the path that is followed to reach the final state is called “the state function”
such as change in internal energy, enthalpy, and entropy (∆U, ∆H and ∆S)
so that:

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Dr. Farhan Altaee Thermodynamics/Chapter One

∆U = U2 − U1

∆H = H2 − H1

∆S = S2 − S1

Regardless of the path.

On the other hand, quantities such as heat (Q) and work (W) depended
on how the process takes place, i.e. depend on the initial and final states of
the system and on the path, hence they are known as” path functions”.

Another difference between state and path functions is that a state

function represents a property of a system and always has a value, whereas
work and heat appear only when changes are carried out in a system by a
process which requires time.

The Reversible Process:

Imagine a cylinder, with a perfectly smooth piston, which contains gas.

If you push with a force only just large enough to overcome the internal
pressure, the volume will start to decrease slowly. Then if you decrease the
force only slightly, the volume will start to increase. This is the hallmark of
a reversible process: an infinitesimal change in the external conditions
reverses the direction of the change. Heat flow is only reversible if the
temperature difference between the bodies is infinitesimally small.

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Dr. Farhan Altaee Thermodynamics/Chapter One

Reversible processes require the absence of friction or other hysteresis

effects. They must also be carried out infinitesimally slowly. Otherwise
pressure waves and finite temperature gradients will be set up in the system,
and irreversible dissipation and heat flow will occur.

Because reversible processes are very slow, the system is always very
nearly in equilibrium at all times. In that case all its state variables are well
defined and uniform, and the state of the system can be represented on a plot
of, for instance, pressure versus volume. A finite reversible process passes
through an infinite set of such states, and so can be drawn as a solid line on
the plot. During an irreversible process the system is not in an equilibrium
state, and so cannot be represented on the plot; an irreversible process is
often drawn as a straight dotted line joining the initial and final equilibrium
states. The work done during the process is not then equal to the area under
the line, but will be greater than that for the corresponding reversible
process.

Irreversible Process is the process accompanied by dissipative effect.

All real process are practically irreversible and the reversible one is the ideal
case and cannot be realized but it can be established mathematically.

The actual work input or output for the process can be estimated from
that of the reversible one by using the efficiency (η) according to the
following equations:

actual work output from the process

η=
work output from reversible process

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Dr. Farhan Altaee Thermodynamics/Chapter One

Wact.
= x100
Wrev.

This equation when the work done by the system (W is +ve).

And

work input for reversible process

η=
actual work input for the process

Wrev.
= x100
Wact.

When the work done on the system (W is –ve)

Process: it is the operation or a series of operations done on the system to

change it from state to another. The most common thermodynamics process
are:

a) Isothermal: the process carried out under constant pressure.

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Dr. Farhan Altaee Thermodynamics/Chapter One

b) Isobaric: the process carried out under constant pressure.

c) Isometric or Isochoric: the process carried out under constant volume.
d) Adiabatic or Isentropic: the process in which no heat is transferred
between the system and its surrounding. It is achieved under one of
the following circumstances:
1. The system is perfectly insulated.
2. Heat is very small compared to other terms in energy equation and
may be neglected.
3. The process takes place so fast that there is no time for heat to be
transferred.
Polytropic: it is the general case without specific conditions.

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Dr. Farhan Altaee Thermodynamics/Chapter One

Equations for PVT Relationship of an Ideal Gas Under the

Following Changes:

i) Reversible Isometric (constant volume) change:

V1 = V2

dW = p. dV = 0

P1 T1
=
P2 T2

dU = dQ = n. CV . dT

dH = n. CP . dT

ii) Reversible Isobaric (constant pressure) change:

P1 = P2
V1 T1
=
V2 T2

dU = n. CV . dT

dH = dQ = n. CP . dT
W = Q − ∆U
Or
W = P. ∆V
∆U = Q − W
∆H = ∆U + P. dV

iii) Isothermal (constant temperature) change:

T1 = T2
P1 V1 = P2 V2
∆U = 0

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Dr. Farhan Altaee Thermodynamics/Chapter One

∆H = 0

V2
Q = W = n. R. T. ln
V1

P1
= n. R. T. ln
P2

iv) Reversible adiabatic change:

Q=0

∆U = −W

T2 V1 γ−1
=( )
T1 V2

γ−1
T2 P2 γ
=( )
T1 P1

P2 V1 γ
=( )
P1 V2

∆H = ∆U + P. ∆V

n. (P1 V1 − P2 V2 )
W=
(γ − 1)

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Dr. Farhan Altaee Thermodynamics/Chapter One

γ−1
P γ
n. R. T1 [1 − ( 2 ) ]
P1
W=
(γ − 1)

Example :
One kilogram mole of nitrogen undergoes a process in
which it is heated, from initial state of (2.026bar) and (277.4K)
at constant volume to a pressure such that when it is
compressed reversibly at constant temperature, its final pressure
and temperature are (8.104 bar) and (388.5K). calculate Q, W,
∆U, and ∆H for the processes assuming N2 to be an ideal gas.
Solution

Since 1 2 is a constant

Volume step

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Dr. Farhan Altaee Thermodynamics/Chapter One

P1 V1 P2 V1
=
T1 T2

P 1 T2 2.026x388.5
P2 = = = 2.8bar
T1 277.4

Q1 = ∆U1 = n. Cv (T2 − T1 )
1x20934J
= (115.5 − 4.4)
kmole. ℃
= 2325767.4J

∆H1 = n. CP (T2 − T1 )

∆H1 = 1x29307.6(115.5 − 4.4) = 3256074.3J

W=0

Since 2 3 is isothermal step

T2 = T3
∆U3 = 0

∆H3 = 0
P2
Q 3 = W3 = n. R. T. ln
P3
2.8
= 1x8314x388.5ln = −3415680.9 J
8.104
W = W1 + W3 = −3415680.9 J

Q = Q1 + Q 3

∆U = ∆U1 + ∆U3 = 2325767.4 J

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Dr. Farhan Altaee Thermodynamics/Chapter One

∆H = ∆H1 + ∆H3 = 3256074.3 J

Q = 2325767.4 − 3415680.9 = −1089913.5 J

Solved Problems:

1. A cylinder contains fluid under pressure 700KN/m2. The process is

done under constant pressure from volume 0.25m3 to a volume of
1.68m3. calculate the work done.
Solution

W = P(𝑉2 − 𝑉1 )

= 700(1.68 − 0.28)

= 980 kJ

2. Steady flow of 10kg and temperature of 200℃. If the heat dissipation

477J
from the alloy is 715.5kJ. what is the final temperature. Use C𝑓 = .
kg.K

solution
Q = m. C𝑓 (𝑡2 − 𝑡1 )
715.5x103 = 10x477(𝑡2 − 200)

𝑡2 = 350℃

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Dr. Farhan Altaee Thermodynamics/Chapter One

3. 2kg of gas occupying (0.7m3) has an original temperature of (15℃). It

was then heated at constant volume until its temperature becomes
(135℃). How much heat was transferred to the gas and what is its
0.72kj 0.29kJ
final pressure? Use CV = and R = .
kg.K kg.K

Solution
Heat transferred at constant volume Q12
Constant volume means W12 = 0
𝑄12 = ∆𝑈12 = 𝑚𝐶𝑉 (𝑇2 − 𝑇1 )
= 2x0.72(135 − 15) = 172.3kJ
From equation of state:
𝑃1 𝑉1 = 𝑚𝑅𝑇1

𝑚𝑅𝑇1 2𝑥0.29𝑥288
P1 = = = 238.6𝑘𝑝𝑎
𝑉1 0.7

P1 P2
=
𝑇1 𝑇2

408
P2 = 238.6𝑥 = 338.1𝑘𝑝𝑎
288

25