CHEMICAL ENGINEERING

THERMODYNAMICS-I
Tuba Siraj Ansari
Lecturer
Chemical Engineering

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 Course Overview (CH-107)
1. Introduction to Thermodynamics:
 Basic concepts and terminologies
 Zeroth law of thermodynamics

2. First Law of Thermodynamics:

 Thermodynamic process
 Specific heat
 Enthalpy calculations,
 Energy balance to open and closed system and its applications.

3. Volumetric Properties of Pure Fluids:

 PVT relations of pure substances ideal and real gases
 Compressibility factor, law of corresponding states and eccentric factor
 equations of state and its applications

4. Second Law of thermodynamics:

 Entropy, isentropic process, entropy changes ideal gas, entropy balance to open and closed system and its applications
 Ideal work, lost work and its applications.
 Gas Power Cycles, Basic assumptions and analysis of gas power cycles, Carnot cycle
 Introduction to gas turbine, Rankine cycle & Brayton cycle.

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 Text and Reference Books:

Smith J.M., Van H.C. Ness Yunus A. Cengel Milo D Koretsky

“Introduction To Chemical “Thermodynamics: An “Engineering & Chemical
Engineering Engineering Approach”, 7th Thermodynamics”, 2nd
Thermodynamics”, 7th Edition, McGrawhill , 2008 Edition, Wiley, August ,
Edition, McGraw Hill, 2005 2013

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LECTURE # 1

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• The science of energy, that concerned with the ways in which energy is stored within a
body.

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Thermodynamics in daily life

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 It deals with equilibrium and
feasibility of a process.
 Energy transformations – mostly
involve heat and work
movements.
 The Fundamental law is the
conservation of energy principle:
energy cannot be created or
destroyed, but can only be
transformed from one form to
another.
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 History of Thermodynamics

Thermodynamics did not emerge as a

science until the construction of the
first successful atmospheric steam
engines in England by Thomas Savery
in 1697 and Thomas Newcomen in
1712.
These engines were very slow and
inefficient, but they opened the way
for the development of a new
science.

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 Why thermodynamics in Chemical Engineering

Unit operation:
• Physical transformation. (gas absorption, heat transfer, filtration)
• Chemical and physical change. (oxidation, nitration, etc)
A chemical engineer whether he/she is concerned with unit operation or unit process has to;
• Evaluate energy requirement for initiating transformation in both process.
• Study energy changes involved in above two process.
• Enables him/her to calculate maximum amount of work a fuel can provide in engine.
• Enables him/her to calculate maximum efficiency of a turbine or refrigerator and
maximum yield of a chemical reaction.
• Also helps in establishing optimum range of temperature and pressure that are to be
use in chemical or physical process.
• Calculate useful work & minimize work lost by system.

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 Introduction

• Energy: Capacity to do work.

• Conservation of energy: Conversion of energy from one form to another.

• Power: Rate of doing work.

• Thermodynamics: Is the science of energy interaction and its effect on physical properties of matter

• Physical properties: The properties which we can observe by our senses i.e. touch, smell, sight, taste
and hearing.

• Like by sense of sight we can observe that which object is small or large.

• By sense of touch we can feel the temperature, hardness etc.

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 Definitions

Thermodynamics also define as: the study of three E’s

1. Energy
2. Entropy (measure of randomness)
3. Equilibrium
I. Thermal Equilibrium : Equality of Temperature

I. Mechanical Equilibrium : Equality of Force and Pressure

II. Chemical Equilibrium : Equality of Chemical potential

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APPROACH OF THERMODYNAMICS:

1. Microscopic (Statistical Thermodynamics):

 It Is The Study Of Avg. Behavior Of Molecules Constituting Of
Matter.
 A Knowledge Of The Structure Of Matter Is Essential.
 A Large No Of Variables Are Needed To Describe The State
Of Matter.
 The Values Of These Variables Can Not Be Measure

2. Macroscopic (Classical Thermodynamics):

 The structure of matter is not considered.
 Only a few variables are used to describe the state of matter
such as temperature, pressure and volume.
 The values of these variables can be measured.
 Studies the average behavior of large groups of Molecules

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Application Areas of Thermodynamics

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 Definitions

Thermodynamics system:

• In a thermodynamic analysis, the system is the subject of the investigation.

• Quantity of matter or a region of space on which our study is focused.

CONTROL MASS CONTROL VOLUME

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 Types of Systems
Closed System:
In a closed system no mass can transfer across the system boundary but energy can transfer through it.

Open System:
In an open system both the mass and energy transfer across the system boundary. Boundary for an open
system is usually drawn with dotted or broken line
Isolated System:
In case of an isolated system, no mass or energy can transfer across the boundary.

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 Everything external to the system is the surroundings.

• A boundary is a closed surface surrounding a system through which energy and mass may
enter or leave the system.
• May be fixed or movable.
• Volume of boundary is zero.

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 Description of Systems

1. Extensive properties: Dependent on the mass of the system, e.g. Vol. & mass
2. Intensive properties: Independent on the mass of the system, e.g. Pres.,
temp., etc
Properties Symbols
Volume V V/2 Extensive Specific Volume
Mass m m/2 Properties V
V=
Temperature T T 𝑛
Intensive Ex In
Pressure P P Properties
Density ρ ρ

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 Properties of Systems
• The condition of a system at any instant of time is called its state.

• The state at a given instant of time is described by the properties of the system.

• A property of a system is an observable (macroscopic) characteristic of the system.

• Macroscopic properties: Temperature ‘T’, Pressure ‘P’, Volume ‘V’, etc.

• Process: Continuous change of state. Or large no of states between initial and final
point.

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 Thermodynamic Process and Paths
Reversible Process:
The process which can be reversed in the direction following the same path is called a
reversible process.
Irreversible Process:
The process which cannot be reversed in the direction following the same path is called a
irreversible process.

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Processes that are usually idealized as reversible include:
• Frictionless movement
• Electric current flow through a zero resistance
• Steady chemical reaction

Processes that are irreversible include:

• Movement with friction
• Unrestrained expansion
• Electric current flow through a non zero resistance
• Spontaneous chemical reaction
• Mixing of matter of different composition or state.

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 Phase

Quantity of matter homogeneous throughout in chemical composition and physical

structure is called phase.

Homogenous and Heterogenous System:

 A system consists of single phase (either liq. solid or gas) is called a homogenous
system.
 While a system consists of more than one phase is called a heterogenous system.

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Quasi-Static Equilibrium

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LECTURE # 2

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 Laws of thermodynamics
 Zeroth Law → Defines Temperature (T)
 Thermal equilibrium
 First Law → Defines Energy (U)
 Law of conservation of energy
 Work and heat transfer
 Enthalpy H=U+PV
 Concept of internal energy
 Second Law → Defines Entropy (S)
 Direction of heat flow (high to low)
 Concept of entropy
 Third Law → Gives numerical value of Entropy
 Concept of absolute zero.

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 Zeroth Law of thermodynamics

If A and B are in Thermal Equilibrium

and B and C are in Thermal Equilibrium
then A and C are in Thermal Equilibrium
As a result,
 B acts like a thermometer
 A, B and C all are at the same temperature
 From the Zeroth law ,the concept
of temperature and
measurement of temperature
can be easily define.

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 Temperature

• We are familiar with temperature as a measure of “hotness” or “coldness,” it is not easy to give an
exact definition for it.
• Based on our physiological sensations, we express the level of temperature qualitatively with words
like freezing cold, cold, warm, hot, and red-hot.

• For Celsius:
• Ice point (the freezing point of water at standard pressure) is ZERO.
• The Steam point (boiling point of pure water at standard pressure) is 100.
• This distance is divided into 100 equal spaces called “degree”.
°F = 1.8 °C + 32 ΔT(K) = ΔT(oC)
°C = (°F-32)/ 1.8 ΔT(R) = ΔT(oF)
K = °C + 273.15
R = 1.8 K
°F = R – 459.67

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Temperature

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 Temperature

Avg. K.E of the molecules is directly proportional to absolute temperature.

1 3
̅
mV = 2 𝐾𝑇
2 2
1
𝑚𝑉2̅ 𝛼𝑇
2
Basic:
Heat is produce by the K.E of the molecules and the Temperature is the degree of hotness

K.E of
Heat content Temperature
molecules

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 Heat and Work Transfer

• Energy can cross the boundary of a closed system in two distinct forms: heat and work.
• It is important to distinguish between these two forms of energy.

• 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.

• That is, an energy interaction is heat only if it takes place because of a temperature difference. Then it follows
that there cannot be any heat transfer between two systems that are at the same temperature.

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 Heat and Work Transfer

• Work, like heat, is an energy interaction between a system and its surroundings.
• Work is the energy transfer associated with a force acting through a distance.
• A rising piston, a rotating shaft, and an electric wire crossing the system boundaries are all associated with work
interactions.
• As mentioned earlier, energy can cross the boundary of a closed system in the form of heat or work. Therefore,
if the energy crossing the boundary of a closed system is not heat, it must be work.

Similarity of heat and work transfer:

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).

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 Work
 Work W is performed whenever a force acts through a distance. The quantity of
work is given by: Work = Force x length
Here compression work will be discussed:

F = Pext x A
W = Pext x A x l
W = Pext x ΔV

W = Pext x ΔV
Negative sign

 Having a “-” sign here implies W > 0 if ΔV < 0 , that is, positive work
means that the surroundings do work to the system.
 If the system does work on the surroundings (ΔV >0) then W < 0.

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 Work
If Pext is not constant the we see the system by small changes (so that
equilibrium of the system do not disturb going from one point to another
)
đW = Pext dV
đ = not exact differential
Integral; 2
P = Path dependent
𝑾 = − ∫ 𝑷𝐞𝐱𝐭 d𝑽
1
Example: assume a reversible process i.e Pext = P
Ar (g, P1, V1) = Ar (g, P2, V2)
Compression; V1 > V2 and P1 < P2

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 Work
Two paths: Ar (g, P1, V1) = Ar (g, P2, V2)
First Path Second Path
(1) First V1 → V2 at P = constant = P1 (1) First P1 → P2 at V = constant = V1
(2) then P1 → P2 at V = constant = V2 (2) then V1 → V2 at P = constant = P2
P2 x P2 x
2
𝑾 = − ∫ 𝑷𝐞𝐱𝐭 d𝑽 W2
P1 x 1 P1 x
W1
V1 > V2 and P1 < P 2
V2 V1 V2 V1
0 0
𝑉2 𝑉2
𝑉1 𝑉2
𝑾𝟏 = − ∫ 𝑷𝐞𝐱𝐭 d𝑽 − ∫ 𝑷𝐞𝐱𝐭d𝑽
𝑉1 𝑉2
𝑾𝟐 = − ∫ 𝑷𝐞𝐱𝐭 d𝑽 − ∫ 𝑷𝐞𝐱𝐭d𝑽
𝑉1 𝑉1
𝑉2
𝑉2
𝑾𝟏 = − ∫ 𝑷𝟏 d𝑽 = − 𝑷𝟏 𝑽𝟐 − 𝑽𝟏
𝑉1 𝑾𝟐 = − ∫ 𝑷𝟐 d𝑽 = − 𝑷𝟐 𝑽𝟐 − 𝑽𝟏
𝑉1
𝑾𝟏 = 𝑷𝟏 𝑽𝟏 − 𝑽𝟐 > 𝟎 𝑾𝟐 > 𝑾𝟏 𝑾𝟐 = 𝑷𝟐 𝑽𝟏 − 𝑽𝟐 > 𝟎
W > 0 = Work is done to the system to compress

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 Heat
That quantity flowing between the system and the surroundings that can be used
to change the temperature of the system and/or the surroundings.
Heat = q
q
 If heat flows in to the system then q is positive T1 T2 T2 > T1 q > 0
q
 If heat exit from a system then q is negative T1 T2 T2 < T1 q < 0

Heat (q), same as W is a function of path. Not state function

It is possible to change a state (P1, V1, T1) = (P2, V2, T2)

1. Adiabatically 2. Non adiabatically
Historically measured in calories
[1 cal = heat needed to raise 1 g H2O 1°C, from 14.5°C to 15.5°C]
The modern unit of heat (and work) is the Joule.
1 cal = 4.184 J

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 Joules Experiment

• Joules (1840): Observe that there is a relation between work and heat which result in temperature increase

• Schematic diagram for Joule´s experiment. Insulating walls are necessary to prevent heat transfer from the enclosed
water to the surroundings.
• As the weights fall at constant speed, they turn a paddle wheel, which does work on water.
• If friction in mechanism is negligible, the work done by the paddle wheel on the water equals the change of potential
energy of the weights.

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 Relationship between WORK and HEAT
 Work is done on water. The energy is transferred to the water – i. e. the
system- . The energy transferred appears as an increase in temperature.
 We can replace the insulating walls by conducting walls. We can transfer heat
through the walls to the system to produce the same increase in temperature.
 The increase in temperature of the system is a consequence of an increase in
Internal Energy. Internal energy is a state function of the system

Experimentally it was found that;

∆Ein = Qin + Wout

“The sum of the heat transferred into the system and the work done
on the system equals the change in the internal energy of the system”

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 Forms of Energy

TOTAL ENERGY

MACROSCOPIC MICROSCOPIC

SPIN, TRANSLATIONAL,
ROTATIONAL,
K.E and P.E
VIBRATIONAL
(INTERNAL ENERGY)

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 Forms of Energy

• Energy can exist in numerous forms such as thermal, mechanical, kinetic, potential, electric, magnetic, chemical,
and nuclear, and their sum constitutes the total energy E of a system.
• Thermodynamics provides no information about the absolute value of the total energy. It deals only with the
change of the total energy.
• The various 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 energy that a system possesses as a result of its motion relative to some reference frame is called
𝟏
kinetic energy (KE). 𝑲𝑬 = 𝟐 𝒎𝑽𝟐 (𝒌𝑱)
• 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)
• 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.
• Total energy: 𝑬 = 𝑼 + 𝑲𝑬 + 𝑷𝑬 (𝒌𝑱)

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 Internal Energy
• Internal energy is defined earlier as the sum of all the microscopic forms of energy of a
system.
• The molecules of a gas move through space with some velocity, and thus possess
some kinetic energy. This is known as the translational energy.
• The atoms of polyatomic molecules rotate about an axis, and the energy associated
with this rotation is the rotational kinetic energy.
• The atoms of a polyatomic molecule may also vibrate about their common center of
mass, and the energy associated with this back-and-forth motion is the vibrational
kinetic energy.
• The electrons in an atom rotate about the nucleus, and thus possess rotational kinetic
energy.
• Electrons also spin about their axes, and the energy associated with this motion is the
spin energy.
• The internal energy associated with the atomic bonds in a molecule is called chemical
energy.
• The internal energy associated with the phase of a system is called the latent energy.
• The average velocity and the degree of activity of the molecules are proportional to the
temperature of the gas. Therefore, at higher temperatures, the molecules possess higher
kinetic energies, and as a result the system has a higher internal energy.

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 First Law of Thermodynamics

∆𝑈𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑞 + 𝑊 ∆𝑈𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 = −𝑞 − 𝑊
∆𝑈𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝑈𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑈𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 = 0

Law of energy conservation

“Although energy assumes many forms, The total quantity of
energy is constant and when energy disappears in one form it
appears simultaneously in other form”

Mathematically;

ΔU = Q - W
Change in
Heat added Work done
internal energy = to the system −
by the system
of the
system

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 Specific heat capacity

1 kg (Unit
Mass)
ΔT= 1 oC

Amount of
Heat (KJ)

“Specific heat is the amount of heat required to cause a unit change in temperature for a unit
quantity of mass”

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 Specific heat capacity

Specific heat capacity

At constant At constant
Pressure Volume

• Cp = Cv for Incompressible fluids.

• Cp > Cv for Compressible fluids.
• Cp – Cv = R for Compressible fluids.

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