CHEMICAL ENGINEERING

THERMODYNAMICS – I
(CHE 2151)
Basic concepts and definition: Classical and Statistical thermodynamics, system,
boundary, surroundings, internal energy, work, heat, equilibrium, reversible process,
intensive and extensive function, ideal gas temperature scale.
First law of thermodynamics for non-flow process, flow process, State and path
function, Enthalpy, Heat capacity
PVT behavior of gases: Ideal gas, definition, ideal gas law, equation of state for real
gases, graphical representation of P-V-T behavior, V-T diagram, P-V diagram and P-T
diagram, Thermodynamic analysis of processes. Generalized correlations for
thermodynamic property of gases, reduced equation of state, two parameter and
three parameter correlations
Second law of thermodynamics: Spontaneous process, qualitative difference between
heat and work, heat reservoir, heat pump, heat engine, Kelvin Plank statement, Clausius
statement, irreversibility, entropy, Carnot principle, postulates, thermodynamic
temperature scale, third law of thermodynamics.
Thermodynamic relations: Classification of thermodynamic processes, Helmholtz and
Gibbs free energy, fundamental property relations, Maxwell’s relations and their
applications, Clausius-clapeyron equation, modified equations for U, H and S,
relationship between Cp and Cv, ratio of heat capacity, effect of pressure and volume
on Cp and Cv, Gibbs Helmholtz equations.
Applications of laws of thermodynamics:
Refrigeration, choice of refrigerant, Carnot cycle, vapour compression cycle, air
refrigeration, Heat pumps, Liquefaction processes, free expansion, isotropic
expansion, Steam power plant, Rankine cycle, Reheat and regenerative cycles. Internal
combustion engines.
 TEXT/ REFERENCES
❑ K.V. Narayanan, A Text Book of Chemical Engineering
Thermodynamics, Prentice Hall of India, 2006
❑ J.M Smith, H. C. VanNess and M.M.Abbot,
Introduction to Chemical Engineering
Thermodynamics, (7e), McGraw Hill, 2004
❑ T.E. Daubert, Chemical Engineering Thermodynamics,
McGraw –Hill , 1985
❑ Y.V.C.Rao, Chemical Engineering Thermodynamics,
Universities Press, 2004
 Thermodynamics Definition

❖ The word “thermo-dynamic,” used first by

Thomson (later Lord Kelvin)
(from the Greek therme, meaning "heat“ and
dynamis, meaning " power")
- is the science of energy conversion
involving heat and other forms of energy, most
notably work.
- It is also a study of macroscopic variables
such as temperature, volume and pressure
 Introduction
Initially, thermodynamics is the study of the flow of
heat to produce mechanical energy that could be used
for locomotive;
- used for steam engines, turbines, pumps, air
conditioners etc.

❑ Because such equipment also used in chemical plant, it is

also important for those engineers to learn the
fundamental of such equipment.
CHEMICAL
PROCESS
PLANT
 Introduction
The production of chemicals, polymers, pharmaceuticals
and other biological materials, and oil and gas
processing, all involve chemical or biochemical reaction
that produce a mixture of reaction product.
(e.g: Production of acetic acid from ethanol using Acetobacter
aceti bacteria)
C2 H 5OH + O2 → CH 3CO2 H + H 2O

1. These must be separated from the mixture and

Purified to result in product of commercial value.
2. These is the area where thermodynamics plays a
central role in bioprocess eng.
3. Separation processes, e.g. distillation are designed
based on information from thermodynamics
 Application of Thermodynamics
• The field of chemical engineering is commonly divided into
two: unit operations and unit processes.
• The former involves only physical transformation such as
gas absorption, distillation, heat transfer, and filtration,
whereas the latter consists of the combination of the
physical changes with chemical processes such as oxidation,
nitration, and catalysis.
• In chemical processes, like the synthesis of ammonia from
a mixture of nitrogen and hydrogen, thermodynamics
enables us to determine the maximum yield of ammonia
obtained under given conditions of temperature and
pressure.
• In a unit operation like distillation, it predicts the minimum
reflux ratio provided in the fractionation column to achieve
a specified separation.
 Application of Thermodynamics
• The fundamental problems that a chemical engineer
encounters, whether they are related to unit
operations or to unit processes, involve two basic
aspects of a change—the equilibrium and the rate of
change.
• The strength and limitations of thermodynamics will
become obvious when we try to find answers to these
problems.
 Chemical thermodynamics

❖ Calculation of heat and work requirements

for physical and chemical processes

❖ Determination of equilibrium conditions for

chemical reactions

❖ Determination of equilibrium for the

transfer of chemical species between
phases.
 Scope of Thermodynamics
❖ The heat and work effects accompanying a physical
or chemical process can be accurately predicted
using thermodynamic calculations.

❑ What is the maximum work obtained from a specified

change in the state of the system? Or, what is the
minimum work required to effect a certain change in
the system? What is the efficiency with which work
is produced when a certain fuel is burned in a steam
engine?
✓ The answers to these questions are readily
provided by thermodynamics.
 Scope of Thermodynamics
❖ It also helps us to determine a priori whether a
proposed process is possible or not.

❖ Since it deals with the direction of change and

equilibrium, it enables one to calculate the equilibrium
conditions for both physical and chemical changes.

❑ For example, thermodynamics can predict the equilibrium

yield in a chemical reaction and also gives insight into the
driving force for the change under the given conditions of
temperature and pressure.
❑ The equilibrium yield gives the engineer an ultimate value
that he strives to attain by trying improvements in the
process.
 Blast furnaces - equilibrium
❖ In the blast furnaces, iron is produced by reduction of
iron oxide by carbon monoxide.
Fe2O3 + 3CO → 2Fe + 3CO2
❖ In the early years of the development of blast
furnace technology, the presence of carbon monoxide
in the effluent gases was thought to be due to
insufficient contact time in the furnace.
❖ To improve the time of contact of coal with the ore,
furnaces as tall as 30 to 40 m were built, but the
conversion could not be improved.
❖ The concept of equilibrium conversion was not
recognised at that time.
 Blast furnaces - equilibrium
❖ Later, with the application of thermodynamics to
chemical reaction equilibrium, it became clear that in a
chemical reaction conversions above the equilibrium
value could never be attained in practice.

❖ Apart from predicting the equilibrium yield,

thermodynamics also helps us to derive information on
the possible side reactions and methods of eliminating
undesired products.
 Limitations of Thermodynamics
❑ Thermodynamic considerations do not establish the
rates of chemical or physical processes. Rates depend
on driving force and resistance.
❑ Although driving forces are thermodynamic variables,
resistances are not.
❑ Thermodynamics, do not reveal the microscopic
mechanisms of physical or chemical processes. On the
other hand, knowledge of the microscopic behavior of
matter can be useful in the calculation of
thermodynamic properties.
❑ The chemical engineer deals with many chemical
species, and experimental data are often lacking. This
has led to development of "generalized correlations“
that provide property estimates in the absence of
data.
Classical and Statistical thermodynamics

❖Classical thermodynamics formulate the

macroscopic state.
❑ Studies the average behavior of large groups of
molecules
❑ Defines macroscopic properties such as
temperature and pressure

❖Statistical thermodynamics formulate the

microscopic state.
❑ Defines the properties of a system based on the
behavior of molecules/atoms
 Thermodynamic system

❖The application of thermodynamics to

any real problem starts with the
identification of a particular body of
matter as the focus of attention. This
body of matter is called the system
 SYSTEM AND ITS SURROUNDINGS:
❖ A system in thermodynamics refers to that part of
universe in which observations or study are made and
remaining universe constitutes the surroundings.
❖ System and the surroundings together constitute the
universe:

THE SYSTEM

THE UNIVERSE

THE
SURROUNDINGS
Boundary: The surroundings
real or imaginary (environment)
surface that
separates the SYSTEM
system from its
surroundings. boundary (surface)

❖ The boundary
of a system can
be fixed or
movable.
 PHYSICAL STATES OF THE SYSTEM

HOMOGENEOUS HETEROGENEOUS
SYSTEM SYSTEM

Is a system without Is a system, within which

surfaces separating the there is a surface
different properties of separating the different
the system (phase) properties of the system

PHASE is a set of homogeneous parts of a

heterogeneous system, with identical physical and
chemical properties, and separated from other parts
through visible surfaces
By the nature of the interaction with the
surroundings thermodynamic systems are
divided into 3 types:

❑ Open : Mass and Energy can transfer

between the System and the Surroundings

❑ Closed : Energy can transfer between the

System and the Surroundings, but not Mass

❑ Isolated : Neither Mass nor Energy can

transfer between the System and the
Surroundings
water in an open beaker Hot water in contact Water in contact with
is an open system as it with its vapour in a its vapour in a closed
can exchange both closed container insulated vessel is an
energy and matter with isolated system
the surrounding
 Open system (control volume): A properly
selected region in space.
 It usually encloses a device that involves
mass flow such as a compressor, turbine,
or nozzle.
 Both mass and energy can cross the
boundary of a control volume.
Control surface: The boundaries of a
control volume. It can be real or imaginary.

An open system (a
control volume) with
one inlet and one exit.
24
 PROPERTIES OF A SYSTEM
Any characteristic of a system.
▪ Some familiar properties are pressure P, temperature
T, volume V, and mass m.
▪ Properties are considered to be either intensive or
extensive.

Intensive properties: Those that are independent of the

mass of a system, such as temperature, pressure, and
density.
Extensive properties: Those whose values depend on the
size—or extent—of the system.

25
 • Chemical potential
INTENSIVE PROPERTIES • Concentration
• Density (or specific
EXTENSIVE PROPERTY gravity)
• Ductility
• Elasticity
• Hardness
• Energy
• Melting point and
• Entropy
boiling point
• Gibbs energy • Pressure
• Length • Specific energy
• Mass • Specific heat
• particle number capacity
• number of moles • Specific volume
• Volume • Spectral absorption
• electrical charge maxima (in solution)
• Weight • Temperature
• Viscosity
Criterion to differentiate intensive
and extensive properties.

27
 State
❑ At a given state, all the properties of the system
have fixed values.
❑ If the value of one property changes, the state
changes.
❑ If no properties are changing, then it is at equilibrium

A system at two different states.

 Equilibrium
A state where in there is no tendency for a
change
Rate = Driving force / Resistance

❑ True equilibrium – driving force becomes zero.

❑ False equilibrium – resistance being infinitely
large.
 Equilibrium
❑ Thermal equilibrium
Temperature is same
throughout system

❑ Phase equilibrium
No change in the amounts
of different phases
A closed system reaching
❑ Chemical equilibrium thermal equilibrium.
Chemical composition
does not change with
time.
 Thermodynamic Process
❑ Process: Any change that a system undergoes from one
equilibrium state to another.
❑ Path: The series of states through which a system
passes during a process.
To describe a process completely, one should specify the
initial and final states, as well as the path it follows, and the
interactions with the surroundings.

❑ Quasistatic or quasi-equilibrium
process: When a process
proceeds in such a manner that
the system remains practically in
equilibrium at all times.
 Types of processes
❑ Processes in which both the system and its
surroundings can be simultaneously returned to their
initial states after the process has been completed
are called a reversible process.
– frictionless
– never more than differentially removed from equilibrium
– traverses a succession of equilibrium states
– driven by forces whose imbalance is differential in magnitude
– can be reversed at any point by a differential change in
external conditions
– when reversed, retraces its forward path, and restores the
initial state of system and surroundings
• The reversible process is ideal; it represents a limits
to the performance of actual process.
 Types of processes
• Processes in which the system and its
surroundings cannot be simultaneously
returned to their initial states after the
process has been completed are called a
irreversible.

• Spontaneous process is a process, which

under particular conditions occurs by itself
without extraneous source of energy.
In most of the processes that we will
study, one thermodynamic property is held
constant. Some of these processes are
❑ Adiabatic/Isentropic process - a process
with no heat transfer into or out of the
system.
❑ Isochoric process - a process with no
change in volume, in which case the system
does no work.
❑ Isobaric process - a process with no change
in pressure.
❑ Isothermal process - a process with no
change in temperature.
 THERMODYNAMIC PROCESS

ISOTHERMAL ADIABATIC PROCESS

(T=const) (Q = 0)
No heat exchange between
the system and
ISOBARIC the surroundings
(Р=const)

Processes in which the system

ISOCHORIC returns to its original state
(V=const) after a series of successive
transformations, called
cyclic process
or thermodynamic cycle
Process diagrams:
❑ Thermodynamic
properties as
coordinates —
visualizing the
processes.
❑ Some common
properties are
temperature T,
pressure P, and volume
V (or specific volume v). The P-V diagram of a compression
process.

37
The Steady-Flow Process
 The term steady During a steady-
implies no change flow process,
with time. The fluid properties
within the
opposite of steady control volume
is unsteady, or may change with
transient. position but not
with time.
 A large number of
engineering devices
operate for long
periods of time
under the same
conditions, and they
are classified as
steady-flow
devices. Under steady-flow conditions, the mass
and energy contents of a control volume
39
remain constant.
 Dimensions and Units

Measures of amount or
size
Temperature
Force
Thermodynamics
Pressure

Work

Energy

Heat
 Dimensions and Units
❑ Dimension is recognize through our sensory
perceptions and not definable without the definition
of arbitrary scales of measure, divided into specific
units of size.
❑ The units have been set by international agreement,
and are codified as the International System of Units.

Note: See Table 1.1 for

Prefixes (eg: deca,
hecto, kilo, etc.) of SI
units. (eg: 1 cm = 10-2
m, 1 kg = 103 g)
 Measures of amount or size
• Three measures of amount or size are in common use:
Mass, m ; Number of moles, n ; Total volume, Vt

• Mass, m divided by the molar mass M (molecular weight) to yield

number of moles;
m
n= or m = Mn
M
Total volume, divided by the mass or number of moles of the system
to yield specific or molar volume.
t
• Specific volume: V = V or V t = mV
m
Vt
• Molar volume: V= or V t = nV
n
 Temperature
❑ Although we are familiar with temperature as
a measure of “hotness” or “coldness,” it is not
easy to give an exact definition of it.

❑Definition : Temperature is a measure of the

mean kinetic energy of molecules. Absolute
zero (0 K) is a state of complete motionless of
molecules.

❑ Temperature is commonly measured with liquid-in-

glass thermometers, herein the liquid expands when
heated.
 Temperature Scales
❑ All temperature scales are based on some easily
reproducible states such as the freezing and boiling
points of water: the ice point and the steam point.
Ice point: A mixture of ice and water that is in
equilibrium with air saturated with vapor at 1 atm
pressure (0°C or 32°F).
Steam point: A mixture of liquid water and water
vapor (with no air) in equilibrium at 1 atm pressure
(100°C or 212°F).
Celsius scale: in SI unit system
Fahrenheit scale: in English unit system
Thermodynamic temperature scale: A temperature
scale that is independent of the properties of any
substance.
Kelvin scale (SI) Rankine scale (E)
Relations among temperature scales
 Temperature Scales

❑The reference temperature in the original

Kelvin scale was the ice point, 273.15 K, which
is the temperature at which water freezes (or
ice melts).

❑The reference point was changed to a much

more precisely reproducible point, the triple
point of water (the state at which all three
phases of water coexist in equilibrium), which
is assigned the value 273.16 K.
 Magnitudes of Temperature
❑ The magnitudes of each division of 1 K and 1C are
identical, and so are the magnitudes of each division of
1 R and 1F. That is,
 
T K = (T2 C + 273.15) - (T1 C + 273.15)
 
= T2 C - T1 C = T  C
T R = T  F
 Ideal-gas temperature scale
❑ A temperature scale nearly identical to the Kelvin scale is
the ideal-gas temperature scale. The temperatures on
this scale are measured using a constant-volume gas
thermometer.

A constant-volume gas thermometer would

read 273.15°C at absolute zero pressure.
 THERMAL EQUILIBRIUM
Two bodies reaching thermal equilibrium after
being brought into contact in an isolated
enclosure.
 ZEROTH LAW OF THERMODYNAMICS
The zeroth law of thermodynamics: If two bodies are
in thermal equilibrium with a third body, they are also in
thermal equilibrium with each other.

❑ By replacing the third body with a thermometer, the

zeroth law can be restated as two bodies are in
thermal equilibrium if both have the same
temperature reading even if they are not in contact.
 Force
❑ According to Newton’s second law of motion, the
force acting on a body is directly proportional to the
time rate of change of momentum.
❑ For a body of constant mass, Newton’s law reduces to
𝐹 = 𝑐𝑚𝑎
where F is the force, m is the mass of the body, a is the
acceleration, and c is a proportionality constant.
❑ In the SI system, the constant c is unity and we have
𝐹 = 𝑚𝑎
❑ When a body of mass 1 kg is accelerated by 1 m/s2,
the force acting on the body is 1 kg m/s2, which is
designated as 1 newton or (1 N).
 Force
Metric engineering
SI unit
system units
Newton (N) Kilogram force (kgf)

1
F = ma F = ma
gc

 In the metric engineering system of units, force is treated as an

additional independent dimension along with length, time, and
mass.
1
1 kgf = x 1 kg x 9.80665 ms −2
gc
gc = 9 .80665 kg m kgf −1 s −2

* Note : The kilogram force is equivalent to 9.80665 N

Weight & Mass
[Example] An astronaut weighs 730 N in Houston, Texas,
where the local acceleration of gravity is g = 9.792 m s-2.
What are the astronaut’s mass and weight on the moon where
g = 1.67m s-2.
A body
weighing 60
kgf on earth
will weigh
only 10 kgf
on the moon.
[Example] A man circling the earth in a spaceship weighed
300 N at a location where the local gravitational acceleration
was 4.5 m/s2. Calculate the mass of the man and his weight on
the earth where the gravitational acceleration is 9.81 m/s2.
 Pressure
❑ Any force acting on a surface consists of a component
perpendicular to the surface and a component parallel
to the surface. These two components are called
normal force and shear force.

❑ Pressure is defined as a normal force per unit area on

which the force acts. The SI pressure unit, N/m2, is
called a pascal (Pa).
 Pressure
SI unit Metric engineering system units
Pascal psi(lbf/in2)
❑ The primary standard for pressure measurement is
the dead-weight gauge in which a known force is
balanced by a fluid pressure acting on a known area.
 Pressure
❑ A normal force exerted by a fluid per unit area.

𝐹 𝑚𝑔 𝐴ℎ𝜌𝑔
𝑃= = = = ℎρ𝑔
𝐴 𝐴 𝐴
 Pressure
❑ The pressure used in all calculations of state
is the absolute pressure measured relative to
absolute zero pressure.
❑ However, pressures are often measured
relative to atmospheric pressure, called gauge
or vacuum pressures.
❑ In the English system the absolute pressure
and gauge pressures are distinguished by
their units, psia (pounds force per square inch
absolute) and psig (pounds force per square
inch gauge), respectively; however, the SI
system makes no distinction between absolute
and gauge pressures.
 Pressure
❑Absolute pressure: The actual pressure at a
given position. It is measured relative to
absolute vacuum (i.e., absolute zero pressure).
❑Gauge pressure: The difference between the
absolute pressure and the local atmospheric
pressure.
▪ Most pressure-measuring devices are calibrated to
read zero in the atmosphere, and so they indicate
gauge pressure.
❑Vacuum pressures: Pressures below
atmospheric pressure.
 Pressure
These pressures are related by 𝑃𝑔𝑢𝑎𝑔𝑒 = 𝑃𝑎𝑏𝑠 − 𝑃𝑎𝑡𝑚
𝑃𝑣𝑎𝑐 = 𝑃𝑎𝑡𝑚 − 𝑃𝑎𝑏𝑠
Or these last two results may be written as
𝑃𝑎𝑏𝑠 = 𝑃𝑎𝑡𝑚 ± 𝑃𝑔𝑢𝑎𝑔𝑒
Where the +Pgauge is used when Pabs > Patm and –Pgauge is used for a vacuum gauge.

The relation among atmospheric, gauge, and vacuum pressures is shown below.
The Manometer
It is commonly used to measure small and
moderate pressure differences. A manometer
contains one or more fluids such as mercury,
water, alcohol, or oil.
Measuring the
pressure drop across
a flow section or a
flow device by a
differential
manometer.

The basic
manometer.

In stacked-up fluid layers, the

pressure change across a fluid layer of
density  and height h is gh. 63
 THE BAROMETER AND ATMOSPHERIC PRESSURE
• Atmospheric pressure is measured by a device called a barometer; thus, the
atmospheric pressure is often referred to as the barometric pressure.
• A frequently used pressure unit is the standard atmosphere, which is
defined as the pressure produced by a column of mercury 760 mm in height
at 0°C (Hg = 13,595 kg/m3) under standard gravitational acceleration (g =
9.807 m/s2).

The length or the

cross-sectional area
of the tube has no
effect on the height
of the fluid column
of a barometer,
provided that the
tube diameter is
large enough to
avoid surface
tension (capillary)
The basic barometer. effects.
[Example] A vacuum guage connected to a tank reads 30 kPa
at a location where the atmospheric pressure is 98 kPa.
What is the absolute pressure in the tank?
[Example] A pressure guage connected to a valve stem of a
truck tire reads 240 kPa at a location where the atmospheric
pressure is 100 kPa. What is the absolute pressure in the
tire, in kPa?
[Example] A dead weight with a 1-cm diameter piston is used to
measure pressures very accurately. In a particular instance a mass
of 6.14 kg (including piston, pan and weight) brings it into balance.
If the local acceleration of gravity is 9.82 ms-2
(i) what is the gauge pressure being measured?
(ii) If the barometric pressure is 748 torr, what is the absolute
pressure?
[Example] At 27℃ the reading on a manometer filled with mercury
is 60.5 cm. The local acceleration of gravity is g = 9.784 m s-2. To
what pressure does this height of mercury correspond?
Variation of Pressure with Depth
When the variation of density
with elevation is known

The pressure of a fluid at rest

increases with depth (as a Free-body diagram of a rectangular
result of added weight). fluid element in equilibrium.
 In a room filled with
a gas, the variation of
pressure with height
is negligible.

Pressure in a liquid
at rest increases
linearly with
distance from the
free surface.

The pressure is the

same at all points on
a horizontal plane in
a given fluid
regardless of
geometry, provided
that the points are
interconnected by
the same fluid.
[Example] A special manometer fluid has a specific gravity of
2.95 and is used to measure a pressure of 1.15 bar at a
location where the barometric pressure is 760 mm Hg. What
height will the manometer fluid indicate?
 WORK
Product of force acting on a body and the distance travelled
by the body

𝑊 =𝐹×𝑙 _ 𝑑𝑊 = 𝐹 ×dl

𝑉
_ 𝑑𝑊 = −𝑃 𝐴 𝑑 𝐴

For Constant cross section area

_ 𝑑𝑊 = −𝑃 𝑑𝑉
dl

𝑉2
F
_ 𝑊 = − න 𝑃 𝑑𝑉
𝑉1
72
 POWER
❑ Rate of work done. Unit: J/s or W (watts)
❑ 1 hp = 746 W
[Example] A man whose weight is 600 N takes 2 min for
claimbing up a staircase. What is the power developed in him,
if the staircase is made up of 20 stairs each 0.18 m in height?

Solution:
Total vertical displacement = 20 × 0.18 = 3.6 m

Work done = Force × Displacement = 600 × 3.6 = 2160 N m(=2160 J)

Work done 2160 𝐽

Power developed = = = 18 (=18 W)
𝑇𝑖𝑚𝑒 2×60 𝑠
 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 deals only with the change of the total energy.
❑ Macroscopic forms of energy: Those a system possesses as a
whole with respect to some outside reference frame, such as
kinetic and potential energies.
❑ Microscopic forms of energy: Those related to the molecular
structure of a system and the degree of the molecular activity.
❑ Internal energy, U: The sum of all the
microscopic forms of energy.
❑ Kinetic energy, KE: The energy that a
system possesses as a result of its
motion relative to some reference
frame.
❑ Potential energy, PE: The energy that a The macroscopic energy of
system possesses as a result of its an object changes with
elevation in a gravitational field. velocity and elevation.
 ENERGY
❑ Quantity that can be stored within the system and can be
exchanged between the system and surroundings
❑ The exchange of energy occurs either as heat or work
(Energy in transit); they cannot be stored within the system
Kinetic Energy:
➢ The energy possessed by the body by virtue of its motion.
𝑑𝑢
𝑑𝑊 = 𝐹 𝑑𝑙 _ 𝑑𝑊 = 𝑚𝑎 𝑑𝑙 _ 𝑑𝑊 = 𝑚 𝑑𝑡 𝑑𝑙

𝑑𝑙
_ 𝑑𝑊 = 𝑚 𝑑𝑡 𝑑𝑢 _ 𝑑𝑊 = 𝑚𝑢 𝑑𝑢
𝑢2
𝑢22 𝑢12 𝑚𝑢2 1 2
_ 𝑊 = 𝑚න 𝑢 𝑑𝑢 = 𝑚 − =∆ _ 𝐾𝐸 = 2 𝑚𝑢
𝑢1 2 2 2
75
Potential Energy:
➢ The energy possessed by the system due to its
position above some arbitrary reference plane.

𝑑𝑊 = 𝐹 𝑑𝑙 _ 𝑑𝑊 = 𝑚𝑎 𝑑𝑙 _ 𝑊 = 𝑚𝑔 𝑧2 − 𝑧1

_ 𝑊 = 𝑚𝑔 𝑧2 − 𝑧1 _ 𝑊 = ∆(𝑚𝑔𝑧)

_ 𝑃𝐸 = 𝑚gz

76
[Example] The potential energy of a body of mass 10 kg is 1.5
kJ. What is the height of the body from the ground? If a
body of 10 kg is moving at a velocity of 50 m/s, what is its
kinetic energy?
[Example] Nitrogen gas is confined in a cylinder and the pressure
of the gas is maintained by a weight placed on the piston. The mass
of the piston and the weight together is 50 kg. The acceleration
due to gravity is 9.81 m/s2 and the atmospheric pressure is 1.01325
bar. Assume frictionless piston. Determine:
(i) The force exerted by the atmosphere, the piston, and the
weight on the gas if the piston is 100 mm in diameter.
(ii) The pressure of the gas.
(iii) If the gas is allowed to expand pushing up the piston and the
weight by 400 mm, What is the work done by the gas in kJ.
(iv) What is the change in the potential energy of the piston and
the weight after the expansion in part (iii)?
[Example] A spherical ballon of diameter 0.5 m contains a gas
at 1 bar and 300K. The gas is heated and the balloon is
allowed to expand. The pressure inside the balloon is found to
vary linearly with the diameter. What is the work done by the
gas when pressure inside reaches 5 bar?
Historical Background on Heat
• Kinetic theory: Treats molecules as
tiny balls that are in motion and thus
possess kinetic energy.
• Heat: The energy associated with
the random motion of atoms and
molecules.
Heat transfer mechanisms:
• Conduction: The transfer of energy
from the more energetic particles of
a substance to the adjacent less
energetic ones as a result of
interaction between particles.
• Convection: The transfer of energy
between a solid surface and the In the early nineteenth century,
adjacent fluid that is in motion, and heat was thought to be an
it involves the combined effects of invisible fluid called the caloric
conduction and fluid motion. that flowed from warmer bodies
• Radiation: The transfer of energy to the cooler ones.
due to the emission of
electromagnetic waves (or photons).
 Energy Transfer by Heat
❖Heat always flows
from a higher
temperature to a
lower one.
– Temperature as the
driving force for the
transfer of energy as
heat.
– Heat is never regarded
as being stored within
a body.
– It exists only as energy The larger the temperature
difference, the higher is the rate of
in transit from one heat transfer.
body to another.
 Heat and work
❑ Unit: calorie is defined as the
quantity of heat which when
transferred to one gram of
water raised its temperature
one degree Celsius, or, British
thermal unit (BTU) is defined as
the quantity of heat which when
transferred to one pound mass
of water raised its temperature
one degree Fahrenheit or, Joule
In SI system.
❖ Work is energy exchange Energy can cross the
between system and boundaries of a closed
system in the form of heat
surroundings due to any
and work.
phenomenon except a
temperature difference.
Thermodynamics and Heat Transfer

• Thermodynamics is concerned with the

amount of heat transfer as a system
undergoes a process from one
equilibrium state to another.
• Heat Transfer deals with the
determination of the rates of such
energy transfers as well as variation of
temperature.
83
Juole’s Experiment
❑ Energy is added to a fluid as
work, but is transferred from
the fluid as heat.
❑ What happens to this energy
between its addition to and
transfer from the fluid?
❑A rational concept is that it is
contained in the fluid in
another form, called internal
energy.
 Internal Energy (U)
❑ Energy of the
molecules making up
the system.
❑ It is the translational,
rotational and
vibrational energy due
to motion, rotation
and vibration of the
molecules.
❑ It cannot be directly
measured
Classification

86
 Thermodynamic Functions
Derivative quantities, dependent on the parameters of
the system state and immeasurable by direct methods
are called thermodynamic functions:

THERMODYNAMIC FUNCTIONS

STATE FUNCTIONS:
U – Internal energy,
PATH FUNCTIONS: H – Enthalpy,
Q – HEAT, S – Entropy,
W – WORK
G – Gibbs free energy,
 STATE and PATH Function
❑ In thermodynamics, state function is
a property of a system that depends only on
the current state of the system, not on the
way in which the system acquired that state.
A state function describes the equilibrium
state of a system.
❑ In contrast, path function – mechanical
work and heat are not properties of the
system, they characterize the process of
energy exchange between the system and
the surroundings, therefore they depend on
the path (specific transition) of the process.
 Thermodynamics of State & Path Functions

❑ The differential of a state function represents an

infinitesimal change in its value
𝑈2
න 𝑑𝑈 = 𝑈2 − 𝑈1 = ∆𝑈
𝑈1

❑ The differential of heat and work are not changes,

but are infinitesimal amounts.

න 𝑑𝑄 = 𝑄

and
න 𝑑𝑊 = 𝑊