Chapter 1 CET Student

COURSE:
Chemical Engineering
Thermodynamics (BNQ20104)
BY:
Dr. Nadirul Hasraf Bin Mat Nayan
Department of Chemical Engineering
Faculty of Engineering Technology
Universiti Tun Hussein Onn Malaysia
CHAPTER 1: INTRODUCTION & BASIC

CONCEPTS OF
THERMODYNAMICS
CHAPTER 1.1 : Thermodynamics and Energy
CHAPTER 1.2 : Dimensions and Units
CHAPTER 1.3 : Closed and Open Systems
CHAPTER 1.4 : Properties of a Systems
CHAPTER 1.5 : State and Equilibrium
CHAPTER 1.6 : Processes and Cycles
CHAPTER 1.7 : Forms of Energy
CHAPTER 1.8 : Energy and Environment
CHAPTER 1: INTRODUCTION & BASIC

CONCEPTS OF
THERMODYNAMICS
CHAPTER 1.9 : Temperature and Zeroth Law of
Thermodynamics
CHAPTER 1.10 : Pressure
CHAPTER 1.11 : The Manometer
CHAPTER 1.12 : Barometer and the Atmospheric Pressure
CHAPTER 1.13 : Thermodynamic Aspects of Biological
Systems
CHAPTER 1.1: Thermodynamics and

Energy
- Thermodynamics can be defined as the science of energy.
- Energy can be viewed as the ability to cause changes.
- The name thermodynamics stems from the Greek words:
+
HEA
T
POWE
R
- To describe the early efforts of the Greek to convert heat into

power

Energy
There are three principal laws of thermodynamics:
1st
Law
Energy is
conserved, its
formed can be
converted
0th
Law
2nd
Law
Law of
Thermodynamics
Thermal
equilibrium is
transitive
Energies can
flow

Energy
Laws of Thermodynamics
- The
first
and
second
law
of
thermodynamics emerged simultaneously
in the 1850s, primarily out of the work of
William Rankine, Rudolph Clausius and
Lord Kelvin.
- It is well-known that a substance consists
of a large number of particles called
molecules.
- For example, the pressure of a gas in a
container is the result of momentum

Energy
- However, one does not need to know the behaviour of the gas
particles to determine the pressure in the container. It would be
sufficient to attach a pressure gauge to the container.
- This macroscopic approach to the study of thermodynamics that does
not require a knowledge of the behaviour of individual particles is
called classical thermodynamics.
- A more elaborate approach (microscopic), based on the average
behaviour of large groups of individual particles, is called statistical
thermodynamics.

Energy
i. Macroscopic (or classical thermodynamics)
- In this approach, a certain quantity of matter is considered, without taking into
account the events occurring at the molecular level.
- This macroscopic approach to the study of thermodynamics that does not
require knowledge of the behaviour of individual particles.
- Macroscopic thermodynamics is only concerned with the effects of the action
of many molecules, and these effects can be perceived by human
senses.
- The macroscopic observations are completely
assumptions regarding the nature of matter.
independent
of
the

Energy
ii. Microscopic (or statistical thermodynamics)
- From the microscopic viewpoint, matter is composed of a large number of
small molecules and atoms.
- This microscopic approach to the study of thermodynamics that require
knowledge of the behaviour of individual particles.
- Microscopic thermodynamics is concerned with the effects of the action of
many molecules, and these effects cannot be perceived by human
senses.
- The microscopic observations are completely dependent on the assumptions
regarding the nature of matter.

Energy
First Law of Thermodynamics
- Is simply an expression of the conservation of energy

principle, and it asserts (stress) that energy is a
thermodynamics property.
- It simply states that during an interaction, energy
can change from one form to another but total
amount of energy remains constant.
- That is, energy cannot be created or destroyed.

Energy

Energy
- Example 1 of the 1st Law:

PE =
10
KE =
0
Energy cannot be
destroyed, it can
only change form
PE =
7
KE =
3

Energy
- Example 2 of the 1st Law:

- The conversion of energy principle
has forms the backbone of the diet
industry.
- A person who has greater energy
input (food) than energy output
(exercise) will gain weight (store
energy in form of fat), vice versa
-
Conservation of energy
principle for the human
body
Ein Eout = Ebalance

Energy
Second Law of Thermodynamics
- Asserts that energy has quality as well as quantity,

and actual processes occurring the direction of
decreasing quality of energy.
- Example of the 2nd Law:
Heat flows in the direction

of decreasing temperature
CHAPTER 1.2: Dimensions and Units

- Any physical quantity can be characterized by dimensions.
-
The arbitrary magnitude assigned to the dimensions are called units.
- Basic dimensions such as mass m, length L, time t, and temperature T

are selected as primary or fundamental dimensions.
- Other dimensions such as velocity , energy E, and volume V are
expressed in terms of the primary dimensions and are called
secondary dimensions, or derived dimensions.

- Two sets of units commonly used in thermodynamics are the English
system, which is also known as the United States Customary System
(USCS) and the metric SI, the International Systems.
- The SI is a simple and logical system based on a decimal relationship
between the various units, and it is being used for scientific and
engineering work.
- The English system, however, has no numerical base, and various units in
this system are related to each other rather arbitrarily (12 in. in 1 ft., 16
oz. in lb) which make it confusing and difficult to learn.
- The United States is the only industrialized country that has not fully
converted to the metric system.

Some SI and English Units
- In SI, the units of mass, length, and time are the kilogram (kg), meter
(m), and second (s), respectively.
- The respective units in the English system are the pound-mass (lbm),
foot (ft), and second (s).
- The mass and length units in the two systems are related to each other
by:
1 lbm = 0.45359 kg
1 ft = 0.3048 m

Some SI and English Units
- In SI, the force unit is the newton
(N), and it is defined as the force
required to accelerate a mass
of 1 kg at a rate of 1 m/s2.
- In the English system, the force
unit is the pound-force (lbf) and
is defined as the force required
to accelerate a mass of 32.174
lbm (1 slug) at a rate of 1
ft/s2.
The
definition
of the
force units

- Units can give terrible headaches if they are not used
carefully in solving problems.
- However, with some attention and skill, units can be
used to our advantages.
- They can be used to check formulas and they can
even be used to derived formula, as shown in the
following exercise.

Exercise 1:
A tank is filled with oil whose density is
3
= 850 kg/m3. if the volume of the
tank is V = 2 m , determine the amount
of mass m in the tank.
CHAPTER 1.3: Closed and Open

Systems
- A thermodynamics system, or simply a system, is defined
as a quantity of matter or a region in space chosen for study.
- The mass or region outside the system is called the
surroundings.
- The real or imaginary surface that separates the system from
its surroundings is called boundary.
- The boundary of a system can be fixed or movable.

Systems
-Thermodynamics system,
surroundings, and boundary-
- The boundary of a
system can be fixed or
movable.
- Boundary is the contact
surface shared by both
the system and the
surroundings.
- Mathematically, the
boundary has zero
thickness, thus it
neither contain any
mass nor occupy any
volume in space.

Systems
- A thermodynamics system, may be considered to be closed or
open, depending on whether a fixed mass or a fixed volume in
space is chosen for study.
i. Closed System
- A closed system, or a control mass,
consists of a fixed amount of mass, and no
mass can across its boundary.
- That is, no mass can enter or leave a
closed system.
- But energy, in the form of heat or work,
can across the boundary, and the volume
of a closed system does not have to be
fixed.
- If, as a special case, even energy is not
allowed to cross the boundary, that system
is called an isolated system.
Thermodynamics
Isolated System

Systems
i. Closed System
- Examples of closed
system:
i. Pressure cooker
ii. A rubber balloon filled with
air and tightly closed
iii. The gas confined between
a piston and cylinder
(energy)
YES
m=
constant
Mass
(energy)
YES
NO

Systems
i. Closed System
Moving
boundary
GAS
2 kg
1 m3
Fixed
boundary
-A Closed System With A Moving
boundary-

Systems
ii. Open System
Open System
Mass In
Energy Out
Energy In
- An open system, or a control

volume, as it is often called, is
a properly selected region in
space.
- It usually encloses a device that
involves mass flow such as a
compressor, turbine, or nozzle.
- Flow through these devices is
best studied by selecting the
region within the device as the
control volume.
- Both mass and energy can
cross the boundary of a control
Mass Out

Systems
ii. Open System
- A large number of engineering
problems involve mass flow in and
out of
a system and, therefore, are
modeled as control volumes.
- A water heater, a car radiator, a

turbine, and a compressor all
involve mass flow and should be
analyzed as control volumes
(open systems) instead of as
control masses
Mass
Energy
- Water Heater (Open

System)

Systems
ii. Open System
- In general, any region in space can be selected as a control
volume.
- There are no concrete rules for the selection of control volumes,
but the proper choice certainly makes the analysis much easier.
- If we were to analyze the flow of air through a nozzle, for example,
a good choice for the control
volume would be the region within
Nozzle
the nozzle.
Air In
Air Out

Systems
ii. Open System
- The boundaries of a control volume are called a control surface,
and they can be real or imaginary.
- In the case of a nozzle, the inner surface of the nozzle forms the
real part of the boundary, and the entrance and exit areas form
the imaginary part, since there are no physical surfaces there.
Control
surface
Control
surface
- A control volume with real and

Systems
ii. Open System
- A control volume with fixed and moving

boundaries -

Systems
ii. Open System
- Most control volumes,

however, have fixed
boundaries and thus do
not involve any moving
boundaries.
- A control volume can
also involve heat and
work interactions just as
a closed system, in
addition to mass
An open system (a
control volume)
with one inlet and
one exit

Systems
Types of
System
Closed
Energy
Yes
Mass
Transfer
No
Examples
Open
Yes
Yes
Turbines,
pumps,
valves
Isolated
No
No
Thermos
flask
Gas in sealed
container
CHAPTER 1.4: Properties of a

Systems
Any characteristic of a system is called a property.
Some
familiar
properties
are
pressure
temperature T, volume V, and mass m.
P,
The list can be extended to include less familiar ones

such as viscosity, thermal conductivity, modulus of
elasticity, thermal expansion coefficient, electric
resistivity, and even velocity and elevation.

Systems
Properties are considered to be either intensive or
extensive.
i. Intensive Properties
-. Intensive properties are those that are independent
of the mass of a system, such as temperature,
pressure, and density.
-. An intensive property doesn't change when you take
away some of the sample (size of the sample
changes).

Systems
extensive.
i. Intensive Properties
-. Density is defines as the mass per volume.
-. Density is written as :
= m / V (the mass of an object divided by its volume)
-. So the density seems to depend on the volume.
-. However, say you take 2 L of water, which weighs 2 kg.
-. Its density will then be:
2 kg / 2L = 1 kg/L
-. So if you take half of the amount of water, its mass will be: 1 L of water
weigh 1 kg.
-. Its density will still be:

Systems
extensive.
ii. Extensive Properties
-. Extensive properties are those whose values
depend on the size of the system.
-. An extensive property changes when the size of the
sample changes.
-. Examples are total mass, total volume, and total
momentum.
CHAPTER 1.5: State and Equilibrium

- Consider a system not undergoing
any change. At this point, all the
properties can be measured or
calculated throughout the entire
system, which gives us a set of
properties
that
completely
describes the condition, or the
state, of the system.
- At a given state, all the properties
of a system have fixed values. If
the value of even one property
State 1
State 2
A system at two
different states

- Thermodynamics deals with equilibrium states.
- The word equilibrium implies a state of balance.
- In an equilibrium state there are no unbalanced
potentials (or driving forces) within the system.
- A system in equilibrium experiences no changes when
it is isolated from its surroundings.

A system is said to be in thermodynamic equilibrium
if it maintains:
a.Thermal Equilibrium (Equality of Temperature)
b. Mechanical Equilibrium (Equality of Forces / Pressure)

c. Chemical Equilibrium (Equality of Chemical Potential)
- Is defined as the state in

which two objects connected
by a permeable barrier don't
have any heat transfer
between them.
- This happens when the two
objects have the
sametemperature.
- Illustration of thermal
equilibrium -
a. Thermal Equilibrium (Equality of Temperature):

A
0
A
50
B
100
B
50

Mechanism of Thermal Equilibrium:
A
A
B
B
COLD
HOT
- Energy is transferred at a faster rate from the hotter

object to the colder object.
- Energy is also transferred from the colder object to the
hotter one, but at a slower rate.
- There is a net flow of energy from the hotter object to the
colder object.

Mechanism of Thermal Equilibrium:
A
A
B
B
Energy transfer at the same rate

between A and B
No net heat
transfer
- The hotter object cools down while the colder object

warm up.
- After some time, energy is transferred at the same rate
between the two objects.
- There is no net heat transfer between the objects.
- The two objects are said to be in thermal equilibrium.

Example of Thermal Equilibrium:
- Wet towel is placed on the
forehead of a person who has high
fever.
- Initially the temperature of the
cloth is lower that the body
temperature of the person.
- Heat energy is transferred from the
forehead to the towel until
thermal equilibrium is reached.
- In this way, heat energy is
- 2nd Law of
Thermodynamics -

b. Mechanical Equilibrium (Equality of Forces /
Pressure):
- When the net (total) force acting on a object is zero,
the object is said to be in mechanical equilibrium.
- This does not mean that no forces are acting on an
object in mechanical equilibrium; all the forces
must add up to zero (cancel out).
- This is known as equilibrium rule.

b. Mechanical Equilibrium:
- The equilibrium rule:
- The
symbol stand for the sum of
- F stands for force.

- The sum of upward forces acting on the scaffold

equals the sum of the downward forces acting on
it.

There are two types of mechanical equilibrium:
i. Static equilibrium
ii. Dynamic equilibrium.
- Static
- Dynamic

i. Static equilibrium
-. Any object which is instatic
equilibriumhas zero net force
acting on it and is at rest.
-. In other words, any object in
static
equilibrium
is
not
moving and will not start
moving unless an external force
The upward
force
- The upward
and downward
forces cancel out
each other, so
the net force is
0.
The downward
force
- No net force
means no
acceleration!
- Static
Equilibrium -

ii. Dynamic equilibrium
-. Any object which is indynamic equilibriumhas
zero net force acting on it and is moving at a
constant velocity.
-. In other words, any object in dynamic equilibrium
is moving at a constant speed in a straight line
and will not change speed or direction unless

ii. Dynamic equilibrium
-. When the push on the box is the same as the

force of friction between the box and the floor,
the net force is zero and the box slides at an

c. Chemical Equilibrium (Equality of Chemical
Potential):
- Is the state in which both reactants and products are
present inconcentrationswhich
tendency to change with time.
have
no
further
- Any chemical system in a closed system will always

reach a state of equilibrium.
- In an open system, some reactions can go to completion
if it is arranged such that the product leaves the system
as it is produced (example: a liquid reaction mixture).

c. Chemical Equilibrium :
- Reactant = substance that is consumed in

the course of a chemical reaction
- Products = substance that is formed in the
course of a chemical reaction

c. Chemical Equilibrium :
Pressurized
- Consider the gas phase chemical system represent by the
following chemical equation:

2 NO2(g)
2 NO2(g)
N2O4(g)
- Reactants are reddish brown, products are colourless.

Temperatu
re Outlet
N2O4(g)
- Both temperature and pressure affect this equilibrium.

- Higher pressures (by compressing the container containing
the reaction mixture) will favour the production of product
(colourless) at the expense of the amount of reactant
Temperature Inlet (coloured) hence, the equilibrium can be observed to change
as the reaction vessel is compressed.
Reaction vessel

Graph of Chemical Equilibrium :
The amount of reactant is diminished from the initial
reaction (used up in the forward reaction) the forward
rate will drop.
The amount of product is increased due to the forward

reaction, then the backward rate will increase from
zero.
At this
point,
reactant is
being
produced
and used
up at equal
rates and
so is the
product.
Shows the measurable physical parameters for a system as it approaches

equilibrium, starting from a conditions of only reactants and no products.

Mechanism of Chemical Equilibrium :
Reaction begins
No products yet
formed
High rate of
collisions
between
reactant and
product
Products formed
Collisions
between
reactants
decrease
Rate of forward
reaction
decreases
Rate of forward
reaction equal to
rate of reverse
reaction
Dynamic
equilibrium
established
Concentrations

The State Postulate:
- The state of a system is described by its properties.
- Do not need to specify all the properties in order
to fix a state.
- Once a sufficient number of properties are specified,
the rest of the properties will assume certain values
automatically.
- In other words, specifying a certain number of
properties is sufficient to fix a state.
- The number of properties required to fix the state of
a system is given by the state postulate.

The state of a simple compressible system is
completely specified by two independent,
properties
simple compressibleintensive
system = no electrical,
magnetic, kinetic, gravity, or
surface tension effects. If any of these must be considered, then one additional
property must be known for each added effect.
Example: for motion (kinetic) effects, velocity must be known.
Compressible = volume not fixed.
-1 a pair can be changed without affecting the other.
Independent = one property of
Example: a. temperature and specific volume (density ) are always independent.
Intensive = the value of the property is not dependent on that amount of material

-The state of nitrogen is fixed by two

independent, intensive properties-
CHAPTER 1.6: Processes and Cycles

State
A process
between states 1
and 2 and the
process path
State
Process
path
Any change that a system undergoes from one

equilibrium state to another is called a process.
The series of states through which a system passes
during a process is called the path of the process.
- The P-V diagram of a compression

process -

QUASI-EQUILIBRIUM PROCESS
(a) Slow compression

(quasi-equilibrium)
(b) Very fast

compression
(nonquasi-equilibrium)
Can be viewed as a sufficiently slow process that allows

the system to adjust itself internally so that properties in
one part of the system do not change any faster than
those at other parts.

QUASI-EQUILIBRIUM PROCESS
- Compression of gas in piston

cylinder -
Uniform distribution of molecules

Minimizes resistance to compression force
Minimizes work required for compression
Work-producing devices operating in a quasiequilibrium manner deliver the most work

NONQUASI-EQUILIBRIUM PROCESS
- Compression of gas in piston

cylinder -
Results in non-homogeneous distribution of

molecules with higher density and greater
resistance to compression at piston surface
Thus, increasing work required for same
compression.

THE STEADY-FLOW PROCESS
The terms steady and uniform are used frequently in
thermodynamics engineering, and thus it is important to
have a clear understanding of their meanings.
The term steady implies no change with time.
The opposite of steady is unsteady, or transient.
The term uniform, however, implies no change with
location over a specified region.
These meanings are consistent with their everyday use such
as steady girlfriend, uniform properties, etc.

A large number of engineering devices such as turbines,
pumps, compressors, heat exchangers and boilers operate
for long periods of time under the same conditions, and they
are classified as steady-flow devices.
Processes involving such devices can be represented
reasonably well by a somewhat idealized process, called the
steady-flow process.
A process during which a fluid flows through a control

An example of steady-flow process:
Pressure
measurements
taken along the pipe at two
different times of a day,
shown in the figure, remain
the same since the flow is
steady.
(a) measurements taken at

10.00 am
But, observe that the

values of pressure vary
along the pipe illustrating
the nonuniform nature of
the steady flow.
(b) measurements taken at

2.00 pm
-Steady-flow of water through a pipe-

Characteristics of a Steady-Flow Process:
A steady flow is one that remains unchanged with time, and therefore
a steady flow has the following characteristics:
i. Characteristic 1:
. No property at any given location within the system boundary
changes with time.
. That also means, during an entire steady flow process, the total
volume Vs of the system remains a constant, the total mass ms of
the system remains a constant, and that the total energy content Es

ii. Characteristic 2:
. Since the system remains unchanged with time during a steady flow
process, the system boundary also remains the same.
iii.Characteristic 3:
. Rates at which heat and work are transferred across the boundary of
the system remain unchanged.

iv. Characteristic 4:
. No property at an inlet or at an exit to the open system changes
with time.
. That means that during a steady flow process, the mass flow rate,
the energy flow rate, pressure, temperature, specific (or molar)
volume, specific (or molar) internal energy, specific (or molar)
enthalpy, and the velocity of flow at an inlet or at an exit remain
constant.
CHAPTER 1.7: 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.
The total energy of a system on a unit mass basis is denoted by e

and is defined as:
e = E / m (kJ / kg)
Thermodynamics provides no information about the absolute value

of the total energy, because it only deals with the change of the
total energy, which is what matters in engineering problems.
CHAPTER 1.8: Energy and

Environment
Our contemporary society requires the constant expenditure
of huge amounts of energy to heat our homes, provide
telephone and cable service, transport us from one location
to another, provide light when it is dark outside, and run the
machinery that manufactures material goods.
Malaysia alone consumes almost 105kJ per person per day.
In contrast, the average energy consumption in the US is
about 106kJ per person per day, although actual values vary
widely depending on a countrys level of industrialization.
In this section, we describe various sources of energy and
their impact on the environment.

Environment
i.FUELS
According to the law of conservation of energy, energy can never
actually be consumed
It can only be changed from one form to another.
Whatisconsumed on a huge scale, however, are resources that can
be readily converted to a form of energy that is useful for doing
work.
As you will see, energy that is not used to perform work is either
stored as potential energy for future use or transferred to the
surroundings as heat.
A major reason for the huge consumption of energy by our society is
the lowefficiencyof most machines in transforming stored energy
into work.

Environment
i.FUELS
Automobiles, for example, are only
about 20% efficient in converting the
energy
stored
in
gasoline
to
mechanical work; the rest of the
energy is released as heat, either
emitted in the exhaust or produced by
friction in bearings and tires.
The production of electricity by coalor oil-powered steam turbines is
significantly more efficient (adjacent
figure): about 38% of the energy
released from combustion is converted
to electricity.
Electricity from Coal. A coal-powered

electric power plant uses the
combustion of coal to produce
steam, which drives a turbine to

Environment
i.FUELS
In general, it is more efficient to use primary sources of energy
directly (such as natural gas or oil) than to transform them to a
secondary source such as electricity prior to their use.
For example, if a furnace is well maintained, heating a house with
natural gas is about 70% efficient.
In contrast, burning the natural gas in a remote power plant,
converting it to electricity, transmitting it long distances through
wires, and heating the house by electric baseboard heaters have an
overall efficiency of less than 35%.

Environment
ii. COAL
Coal is a complex solid material derived
primarily from plants that died and were
buried hundreds of millions of years ago and
were
subsequently
subjected
to
high
temperatures and pressures.
Because plants contain large amounts
ofcellulose, derived from linked glucose units,
the structure of coal is more complex than
that of petroleum.
In particular, coal contains a large number of
oxygen atoms that link parts of the structure
together, in addition to the basic framework of

Environment
ii. COAL
The combustion of coal releases the sulphur in FeS 2as SO2, which is a
major contributor to acid rain.
Oil and natural gas resources are limited.
Current estimates suggest that the known reserves of petroleum will
be exhausted in about 60 years, and supplies of natural gas are
estimated to run out in about 120 years.
Coal, on the other hand, is relatively abundant, making up more than
90% of the worlds fossil fuel reserves.
As a solid, coal is much more difficult to mine and ship than
petroleum (a liquid) or natural gas.

Environment
ii. COAL
Consequently, more than 75% of the coal produced each year is
simply burned in power plants to produce electricity.
A great deal of current research focuses on developing methods to
convert coal to gaseous fuels (coal gasification) or liquid fuels (coal
liquefaction).
In the most common approach to coal gasification, coal reacts with
steam to produce a mixture of CO and H2known assynthesis gas, or
syngas, Because coal is 70%90% carbon by mass, it is approximated
as C in the below equation:
Converting coal to syngas removes any sulphur present and produces

Environment
The Carbon Cycle and the
Greenhouse
Even if carbon-basedEffect:
fuels could be burned with 100%
efficiency, producing only CO (g) and H O(g), doing so could still
2
potentially damage the environment when carried out on the

vast scale required by an industrial society.
The amount of CO2released is so large and is increasing so
rapidly that it is apparently overwhelming the natural ability of
the planet to remove CO2from the atmosphere.
In turn, the elevated levels of CO2are thought to be affecting

Environment
The Carbon Cycle and the
As you will see, there

is little doubt that
Greenhouse
Effect:
atmospheric
CO2levels are increasing, and the major reason for this
increase is the combustion of fossil fuels.
There is substantially less agreement, however, on whether

the increased CO2levels are responsible for a significant
increase in temperature.
CHAPTER 1.9: Temperature and

Zeroth Law of Thermodynamics
Although 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.
However, we cannot assign numerical values to temperatures based on
our sensations alone.
Furthermore, our senses may be misleading.
A metal chair, for example, will feel much colder than a wooden one
Why??
even when both are at the same temperature.

IN-CLASS EXERCISE:
Scenario 1:
You have just come in your room after a long day of
class. The bright sun has been beating down on you all
day. You go inside and collapse into a nearby chair
resting your tired arms on the wooden rests and
grasping the metal supports with your hands. Suddenly
you notice that your hands feel cooler than your arms,
in fact all of the metal in the room feels cooler than the
wooden or fabric objects.
In a group of five (5), discuss why this

scenario happen?

IN-CLASS EXERCISE:
Scenario 2:
A cup of hot coffee left on the table became cold.
It is a common experience that a cup of hot coffee

left on the table eventually cools off and a cold
drink eventually warms up.
That is, when a body is brought into contact with
another body that is at a different temperature,
heat is transferred from the body at higher
temperature to the one at lower temperature until
both bodies attain the same temperature.
At that point, the heat transfer stops, and the two

-Two bodies reaching thermal

equilibrium after being brought into
contact-

For a system to achieve thermal
equilibrium, the equality of temperature is
the only requirement required.
Essentially, two systems that are in
thermodynamic equilibrium will not
exchange any heat.

Temperature Scales.
Temperature scales enable us to use a common basis for
temperature measurements.
The temperature scales used in the SI and in the English
system today are the Celsius scale and the Fahrenheit
scale.
In thermodynamics, it is very desirable to have a temperature
scale that is independent of the properties of any substance.
Such
temperature
scale
is
called
thermodynamic

Temperature Scales.
Celsius scale:
0 and 100C
Fahrenheit scale:
32 and 212F
Kelvin scale:
273.15K and
373.15K

Zeroth Law of Thermodynamic:
As the name suggests, its value as a fundamental physical
principle was recognized more than half a century after the
formulation of the first and the second laws of
thermodynamics.
It was named the zeroth law since it should have preceded
the first and the second laws of thermodynamics.
The zeroth law was first formulated and labeled by R. H.
Fowler in 1931.

The zeroth law of thermodynamics states that if two
bodies are in thermal equilibrium with a third body, they
are also in thermal equilibrium with each other.
Therefore A and C are in thermal
equilibrium.
If they were brought into contact,
there would be no net heat transfer

We leave two cups of coffee (where one is
observably hotter than the other) on the kitchen
table and we just leave them there.
After 30 minute what will we notice about the two
cups of coffee?
HOT
COLD

They will both cool down and

will seemingly both have the
same temperature.

Environme
nt
HOT
COLD

= =
Environme
nt
HOT
COLD

= =
Environme
nt
HOT
COLD

C
A
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

Pressure is defined as a normal
(employed) by a fluid per unit area.
force
exerted
The term pressure is used only when we deal with a gas or

a liquid.
Since pressure is defined as force per unit area, it has the
unit of newton's per square meter (N/m2), which is called a
pascal (Pa).
2
That is:
1 Pa = 1 N / m

Three other pressure units commonly used in
practice are:
i. Bar
ii. Standard atmosphere
iii. Kilogram-force per square centimetre:
-Pressure units conversion-

Type of pressure: Definitions
i. Absolute Pressure
The actual pressure at a given position is called the absolute
pressure, and it is measured relative to absolute vacuum.
Pabs=Patm+Pgauge
ii. Gauge Pressure
Pressure greater than atmospheric pressure that are measured
relative to atmospheric pressure.
Gauge pressure is the difference between the absolute pressure
and atmospheric pressure:
= P
- P

Type of pressure: Definitions
iii.Vacuum Pressure
Pressures below atmospheric pressure.
Measured by vacuum gauges that indicate the difference
between the atmospheric pressure and the absolute pressure.
Pvac= Patm- Pabs

IN-CLASS EXERCISE:
Problem 1: Absolute Pressure of a Vacuum
Chamber
A vacuum gage connected to a chamber reads 5.8 psi at
a location where the atmospheric pressure is 14.5 psi.
Determine the absolute pressure in the chamber.

IN-CLASS EXERCISE:
Problem : Absolute Pressure of a Vacuum
Chamber
A vacuum gage connected to a chamber reads 35 kPa
at a location where the atmospheric pressure is 92 kPa.
Determine the absolute pressure in the chamber.

VARIATION OF PRESSURE WITH DEPTH:
It will come as no surprise to you that pressure in a
fluid at rest does not change in the horizontal direction.
This can be shown easily by considering a thin
horizontal layer of fluid and doing a force balance in
any horizontal direction.
However, this is not the case in the vertical direction in
a gravity field.
Pressure in a fluid increases with depth because more
fluid rests on deeper layers, and the effect of this
extra weight on a deeper layer is balanced by an

The pressure of a fluid at rest increases with depth (as a

result of added weight).

If we take point 1 to be at the
free surface of a liquid open to
the atmosphere (adjacent
figure), where the pressure is
the atmospheric pressure
Patm, then the pressure at a
depth h from the free surface
becomes:
P = Patm + gh or Pgauge
Pressure in a liquid at rest

increases linearly with distance
from the free surface.

Pressure in a fluid at rest is independent of the shape
or cross section of the container.
It changes with the vertical distance, but remains
constant in other directions.
A consequence of the pressure in a fluid remaining
constant in the horizontal direction is that the
pressure applied to a confined fluid increases
the pressure throughout by the same amount.

PASCALS LAW:
Pascal realized that two hydraulic cylinders of different
areas could be connected, and the larger could be used
to exert a proportionally greater force than that applied
to the smaller.
Pascals machine has been the source of many
inventions that are a part of our daily lives such as
hydraulic brakes and lifts.

PASCALS LAW:
This is what enables us to lift a car easily by one arm,
as shown in figure below.
-Lifting of a large weight by a small force by the

IN-CLASS EXERCISE:
In a group of five, discuss the mechanism how a
hydraulic jack can lift a car according to Pascals Law .
C
R
E
EX E
IS
-Lifting of a large weight by a small force by the

A manometer, is a device commonly used to
measure small and moderate pressure differences.
A manometer mainly consists of a glass or plastic Utube containing one or more fluids such as mercury,
water, alcohol, or oil.
To keep the size of the manometer to a manageable
level, heavy fluids such as mercury are used if large
pressure differences are anticipated.

Consider the manometer shown in
adjacent figure that is used to
measure the pressure in the tank.
Since the gravitational effects of
gases are negligible, the pressure
anywhere in the tank and at position
1 has the same value.
Furthermore, since pressure in a
fluid does not vary in the horizontal
direction within a fluid, the pressure
-The basic
manometer-

The differential fluid column of
height h is in static equilibrium, and
it is open to the atmosphere.
Then the pressure at point 2 is
determined directly to be:
P2 = Patm + gh
where is the density of the fluid in
the tube.
-The basic
manometer-

IN-CLASS EXERCISE:
Measuring Pressure with a
Manometer.
A manometer is used to measure the
pressure in a tank. The fluid used has a
specific gravity of 0.85, and the
manometer column height is 55 cm, as
shown in adjacent figure. If the local
atmospheric pressure is 96 kPa,
-Schematic for
in-class

Many engineering problems and some manometers involve
multiple immiscible fluids of different densities stacked on
top of each other.
Such systems can be analyzed easily by remembering that:
(1)the pressure change across a fluid column of height h is
P = gh
(2)pressure increases downward in a given fluid and decreases
upward (Pbottom > Ptop), and
In stacked-up fluid
layers, the pressure
change across a fluid
layer of density and
height h is gh.

The last principle, which is a result of Pascals law, allows us
to jump from one fluid column to the next in manometers
without worrying about pressure change as long as we dont
jump over a different fluid, and the fluid is at rest.
Then the pressure at any point can be determined by
starting with a point of known pressure and adding or
subtracting gh terms as we advance toward the point of
interest.

For example, the pressure at the
bottom of the tank in adjacent figure
can be determined by starting at the
free surface where the pressure is Patm,
moving downward until we reach point
1 at the bottom, and setting the result
equal to P1.
It gives:
Patm + 1gh1 + 2gh2 + 3gh3 = P1

Manometers are particularly wellsuited to measure pressure drops
across a horizontal flow section
between two specified points due to
the presence of a device such as a
valve or heat exchanger or any
resistance to flow.
This is done by connecting the two
legs of the manometer to these two
points, as shown in figure.
-Measuring the pressure

drop across a flow section
or a flow device by a
Th
eith e work
er a
in
gas g fluid
o
c
den r a liqu an be
sity
i
is d whos
1
Di
h.
ight,
e
h
d
ui
tial fl
fferen
The density of the manometer

fluid is 2
-Measuring the pressure drop across a flow section or a flow

device by a differential manometer-
Relation for the pressure difference P1 - P2

can be obtained by starting at point 1
with P1, moving along the tube by adding
or subtracting the gh terms until we
reach point 2, and setting the result equal
to P2:
Note that we jumped from point A

horizontally to point B and ignored the part
underneath since the pressure at both
points is the same.
Simplifying,
-Measuring the pressure

drop across a flow section
or a flow device by a

IN-CLASS EXERCISE:
Measuring Pressure with a Multifluid
Manometer.
Problem:
The water in a tank is pressurized by air, and the pressure is

measured by a multifluid manometer as shown in figure. The tank is
located on a mountain at an altitude of 1400 m where the
atmospheric pressure is 85.6 kPa. Determine the air pressure in the
tank if h1 = 0.1 m, h2 = 0.2 m, and h3 = 0.35 m. Take the densities
of water, oil, and mercury to be 1000 kg/m3, 850 kg/m3, and
13,600 kg/m3, respectively.

IN-CLASS EXERCISE:
Measuring Pressure with a Multifluid
Manometer.
Schematic for in-class exercise:
CHAPTER 1.12 : Barometer and the

Atmospheric Pressure
Atmospheric pressure is measured by

a device called a barometer
Thus, the atmospheric pressure is

often referred to as the barometric
pressure.
The Italian Evangelista Torricelli

(16081647)
was
the
first
to
conclusively
prove
that
the
atmospheric
pressure
can
be
measured by inverting a mercuryfilled tube into a mercury container
-The basic
barometer-

From the figure, the pressure at point
B is equal to the atmospheric
pressure, and the pressure at C can
be taken to be zero since there is only
mercury vapour above point C and the
pressure is very low relative to Patm
and can be neglected.
Thus, writing a force balance in the
vertical direction gives:
-The basic
barometer-

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 0C (Hg = 13,595 kg/m3) under standard
gravitational acceleration (g = 9.807 m/s2).
If water instead of mercury were used to measure the standard

atmospheric pressure, a water column of about 10.3 m would be
needed.
The standard atmospheric pressure, is 760 mmHg (29.92 inHg) at 0C.
The unit mmHg is also called the torr in honor of Torricelli.

The standard atmospheric pressure Patm changes from 101.325 kPa at sea
level to 89.88, 79.50, 54.05, 26.5, and 5.53 kPa at altitudes of 1000, 2000,
5000, 10,000, and 20,000 meters, respectively.
This show the decline of atmospheric pressure with elevation.
The decline of atmospheric

ramifications in daily life.
For example, cooking takes longer at high altitudes since water boils at a
lower temperature at lower atmospheric pressures.
Nose bleeding is a common experience at high altitudes since the difference

between the blood pressure and the atmospheric pressure is larger in this
case, and the delicate walls of veins in the nose are often unable to withstand
pressure
with
elevation
has
far-reaching

Measuring Atmospheric Pressure with a
Barometer:
Example:
Determine the atmospheric pressure at a location
where the barometric reading is 740 mm Hg and the
gravitational acceleration is g = 9.81 m/s2. Assume
the temperature of mercury to be 10C, at which its
density is 13,570 kg/m3.

Measuring Atmospheric Pressure with a
Barometer:
Example:
The barometer of a mountain hiker
reads 930 mbars at the beginning of
a hiking trip and 780 mbars at the
end. Neglecting the effect of altitude
on local gravitational acceleration,
determine the vertical distance
climbed. Assume an average air
density of 1.20 kg/m3.

Effect of Piston Weight on Pressure in a
Cylinder:
Example:
The piston of a vertical pistoncylinder
device containing a gas has a mass of 60
kg and a cross-sectional area of 0.04 m2,
as shown in adjacent figure. The local
atmospheric pressure is 0.97 bar, and the
gravitational acceleration is 9.81 m/s2.
(a) Determine the pressure inside the
cylinder.
(b) If some heat is transferred to the gas
and its volume is doubled, do you
-Schematic for the pistoncylinder device, and the

free-body diagram of the
CHAPTER 1.13 : Thermodynamic

Aspects of Biological Systems
Urea, NH2CONH2, is an important industrial chemical.
It is used to make synthetic resins for adhesives and
melamine plastics
Its major use, however, is an nitrogen fertilizer for plants
Urea is produced by reacting ammonia with carbon dioxide:
2NH3(g) + CO2
NH2CONH2 (aq) + H2O (l)
Suppose you wasnt to determine whether this or some
other reactions could be useful for the industrial preparation
of urea,
some
of your
immediate
question
Does the
reaction
naturally
go in the direction
it ismight
written?be the
following:
Will
the reaction mixture contain a sufficient amount of product
at equilibrium?

Thermodynamics is the study of the relationship
between heat and other forms of energy involved in
a chemical or physical process.
With only heat measurements of substance, you
can answer the questions just posed.
You can predict the natural direction of a chemical
reaction, and you can also determine the
composition of a reaction mixture at equilibrium

First Law of Thermodynamics:
The total amount of energy in an isolated
system is conserved, though the form of the
energy may change.
Second Law of Thermodynamics:
In all natural processes, the entropy of the
universe increases.

Thermodynamic Concepts:
The system is the portion of the universe we are concerned with;
everything else is the surroundings.
The system + surroundings = universe
Closed system: No exchange of energy or matter

Isolated system: Energy exchange occurs
Open system: Energy or matter exchange

at
r
occurs
ve
Ne ibriu
il
equ !!
m

First Law Of Thermodynamics:
The first law of thermodynamics is simply a conservation of energy statement.
The internal energy changes if work and/or heat are exchanged.

In biological systems, we are usually dealing with constant-pressure processes and in
this case the term enthalpy, H, is used.
Enthalpy, H, is the heat exchanged at constant pressure.
When a chemical reaction releases heat, it is exothermic and has a negative H.
Since enthalpy is heat, it is readily measured using a calorimeter or from a plot of
R(lnKeq) versus 1/T, a van't Hoff plot. (To get ahead of the story, the point is that if G
and H are known, S can be calculated.)

H and Spontaneity:
Many chemical events occur spontaneously, meaning on their own,
without the input of additional energy.
Example:
Water spontaneously freezes at -5oC ad 1 atm. It spontaneously melts at 80oC and 1 atm.
Some spontaneous changes need a little input of energy initially, but once they get rolling, it
continues without the need for this extra energy.
In contrast, a nonspontaneous change requires the constant input of

some form of energy in order to maintain the chemical, physical, or
change in location that they system is undergoing.
Example:
A book falls off the table spontaneously (if left balancing precariously on the edge), but what
are the chances that the book will spontaneously put itself back on top of the table?

H and Spontaneity:
It was believed, that if a reaction was exothermic or endothermic, that
the sign of H would predict whether or not a reaction was
spontaneous.
It was also believed that exothermic reactions were spontaneous while
endothermic reactions were nonspontaneous.
While many exothermic reactions are spontaneous, there are several
real world simple examples of spontaneous endothermic reactions.
o Ice placed in your hand removes the heat from your hand and uses that heat energy to
Example:
change from a solid to a liquid.
o Water vaporizing is also an endothermic reaction.

H and Spontaneity:
Think about the order and disorder associated with solids, liquids,
gases and ions in solution.
As we proceed from the solid state to the liquid state to the gas state
disorder increases (or order decreases).
It appears that order, or lack thereof might be important for
determining if a reactions is spontaneous or not.
Therefore, there must be other factors that we must consider when
determining if a reaction is spontaneous or not.

Second Law Of Thermodynamics:
A spontaneous change has a natural tendency to occur
without outside intervention.
The driving force for a spontaneous process is an increase in
the entropy (and disorder) of the universe.
There is a natural tendency for nature to become more
disordered.
Think about all the work you have to do to keep your room
clean, to keep the kitchen clean.
It would and is so much easier to just throw the dirty clothes
on the floor, to leave the dishes in the sink.

Second Law Of Thermodynamics:
It is so hard and takes so much work to actually put
the clothes away or in the dirty clothes hamper and
to wash the dirty dishes and then put them away.
Too much work
These are two classic easy examples to illustrate that
disorder or more disorder is favored.
Nature constantly moves towards more disorder.

All spontaneous changes are accompanied by
an increase in the entropy of the
system/surroundings.
This increase in entropy of the
system/surroundings means that the final
entropy is greater than the initial entropy
which means that the entropy of the universe
also increases!

The greater the degree if disorder, the greater

its entropy.

Entropy:
Ssystem = Sfinal Sinitial
=/
Where =
T is temperature in Kelvin

The magnitude of S is dependent upon the amount of substance

present.
More/less moles of reactants and products will mean more or less
disorder for the chemical reaction.
As we are examining a change in entropy for a chemical reaction, there
are many similarities between the reactions that are used to calculate
the entropy state function values and the reactions used to calculate
n p S productreactions:
- n r S reactant
the enthalpy values forchemical
S =

Third Law of Thermodynamics:

the entropy of a pure, perfect
crystal at 0 K will be 0.

Gibbs Free Energy:
By making two different independent measurements for two different S
variables the system and the surroundings we are making life very
difficult for ourselves.
Isnt there an easier way?
Wouldnt it be nice if spontaneity could be defined by ONE variable
instead of taking into consideration Ssystem and Ssurroundings and H??
There IS such a variable and it mathematically takes into
consideration both H and S at the same time for a given temperature
which means we do not have to think so hard
This variable is called Gibbs free energy or simply free energy and is
given the symbol G.

Gibbs Free Energy:
And the change in the free energy of the system is related to the
enthalpy component and the entropy component at a temperature of
the system:

Gibbs Free Energy:
The free energy change G for the system =
The sign of G is going to tell us if the reaction is spontaneous or not.

And now we do not have to worry about Ssurroundings anymore!
Gibbs free energy is just another way of examining the S of the universe under some
temperature condition and determining if the reaction is spontaneous.
In fact, Gsystem = -TSuniverse So that if Suniverse is a positive #, G will be negative (all
temperatures are given in K, so the temperature value is always a positive
component).
And if Suniverse is negative, then G will be positive.
We know that spontaneous processes occur when Suniverse is positive, therefore

Problem:
An
enzymatic hydrolysis of fructose-1-P

Fructose -1-P +H2O fructose +Pi
was allowed to proceed to equilibrium at 25C. The original

concentration of fructose-1-P was 0.2 M, but when the system
had reached equilibrium the concentration of fructose 1-P was
only 6.52 x 10-5 M. Calculate the equilibrium constant for this
reaction and the standard free energy of hydrolysis of
fructose 1-P.

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CHAPTER 1: INTRODUCTION & BASIC

CHAPTER 1: INTRODUCTION & BASIC

CHAPTER 1.1: Thermodynamics and

- To describe the early efforts of the Greek to convert heat into

CHAPTER 1.1: Thermodynamics and

CHAPTER 1.1: Thermodynamics and

CHAPTER 1.1: Thermodynamics and

CHAPTER 1.1: Thermodynamics and

CHAPTER 1.1: Thermodynamics and

CHAPTER 1.1: Thermodynamics and

- Is simply an expression of the conservation of energy

CHAPTER 1.1: Thermodynamics and

CHAPTER 1.1: Thermodynamics and

- Example 1 of the 1st Law:

CHAPTER 1.1: Thermodynamics and

- Example 2 of the 1st Law:

Ein Eout = Ebalance

CHAPTER 1.1: Thermodynamics and

- Asserts that energy has quality as well as quantity,

Heat flows in the direction

CHAPTER 1.2: Dimensions and Units

The arbitrary magnitude assigned to the dimensions are called units.

- Basic dimensions such as mass m, length L, time t, and temperature T

CHAPTER 1.2: Dimensions and Units

CHAPTER 1.2: Dimensions and Units

CHAPTER 1.2: Dimensions and Units

CHAPTER 1.2: Dimensions and Units

CHAPTER 1.2: Dimensions and Units

CHAPTER 1.2: Dimensions and Units

CHAPTER 1.3: Closed and Open

CHAPTER 1.3: Closed and Open

CHAPTER 1.3: Closed and Open

CHAPTER 1.3: Closed and Open

CHAPTER 1.3: Closed and Open

CHAPTER 1.3: Closed and Open

- An open system, or a control

CHAPTER 1.3: Closed and Open

- A water heater, a car radiator, a

- Water Heater (Open

CHAPTER 1.3: Closed and Open

CHAPTER 1.3: Closed and Open

- A control volume with real and

CHAPTER 1.3: Closed and Open

- A control volume with fixed and moving

CHAPTER 1.3: Closed and Open

- Most control volumes,

CHAPTER 1.3: Closed and Open

CHAPTER 1.4: Properties of a

The list can be extended to include less familiar ones

CHAPTER 1.4: Properties of a

CHAPTER 1.4: Properties of a

CHAPTER 1.4: Properties of a

CHAPTER 1.5: State and Equilibrium

CHAPTER 1.5: State and Equilibrium

CHAPTER 1.5: State and Equilibrium

b. Mechanical Equilibrium (Equality of Forces / Pressure)

CHAPTER 1.5: State and Equilibrium

- Is defined as the state in

a. Thermal Equilibrium (Equality of Temperature):

CHAPTER 1.5: State and Equilibrium

- Energy is transferred at a faster rate from the hotter

CHAPTER 1.5: State and Equilibrium