SUB: CHEMICAL ENGINEERING THERMODYNAMICS
Unit-1 Basic Concepts and definition:
1.What is Thermodynamics: Thermodynamics is the branch of
physics that deals with the relationship between heat and other forms of
energy.
In particular, it describes how thermal energy is converted to and from
other forms of energy and how it affects matter.
The branch of Physics that deals with heat and temperature, and their
relation to energy, work, radiation, and properties of matter
To be specific, it explains
how thermal energy is converted to
or from other forms of energy and
how matter is affected by this
process. Thermal energy is the
energy that comes from heat. This
heat is generated by the movement
of tiny particles within an object.
The faster these particles move; the
more heat is generated.
2. Scope of Thermodynamics:
Energy stored in chemical substances is called chemical energy.
Thermodynamics deals with all types of energies & conversion of
one form of energy into other forms.
Chemical thermodynamics is the study of the interrelation of heat
and work with chemical reactions.
3.Limitation of Thermodynamics
Properties such as pressure, temperature, volume and composition are the
properties of matter in bulk.
Thermodynamics deals with macroscopic properties.
It helps to predict whether the chemical reaction can occur under a given set of
conditions but it does not tell anything about the rate of reaction.
It is more concerned with the initial and final states of the system.
It does not deal with the internal structure of molecules or atoms.
System: In thermodynamics, a substance or group of substances in which we
have special interest is called a system. Example= Reaction vessel.
Surrounding: The part of the universe outside the system and separated
from the system by boundaries is called surroundings.
Process: The changes taking place within the system is referred to as a
process. Thus hydrocarbon fuel and oxygen in a combustion chamber constitute the
system and the combustion of fuel to form water and carbon dioxide constitutes a
process.
Types of System-Homogeneous and Heterogeneous
Homogeneous System : A homogeneous thermodynamic
system is defined as the one whose chemical composition and
physical properties are the same in all parts of the system, or
change Continuously From one point to another.(a single phase
solution).
Example: liquid water in a beaker, column of dust-free air above the
earth’s surface.
Heterogeneous System: A heterogeneous system is
denned as one consisting of two or more homogeneous
bodies.( have more than one phase )
Example: A liquid mixture of benzene and water forms a
heterogeneous system made up of two immiscible liquid phases.
Water and water vapour taken in a closed container.
Closed and Open, state of system
Systems may be considered to be
• Closed or open.
Closed System (control mass):
• Fixed amount of mass
• No mass can cross its boundary or energy can exchange
• Example: Batch Reactor.
• No mass + No energy = isolated system
• Example: A fluid enclosed in a perfectly insulated in a closed
vessel. (Thermoflask)
Open System (control volume):
Encloses a device that involves mass flow such as compressor,
turbine, or nozzle.
Both mass and energy can cross the boundary of a control volume.
PROPERTIES:
Property: Any characteristic of a system, such as pressure P, temperature T,
volume V, and mass m, etc
Properties are considered to be either intensive or extensive.
Intensive properties: do not change as the amount or size of a
substance changes.
Examples: Colour, Hardness, Density, Freezing/boiling point, Thermal conductivity
Extensive properties: Extensive properties scale with the amount or
size of a substance. They must exhibit and additive property when changing the
amount of a substance.
Examples: Mass, Volume, Energy,Entropy .
FUNCTIONS: STATE AND PATH FUNCTIONS
STATE FUNCTION: The thermodynamic state of a system refers to the
temperature, pressure and quantity of substance present. State functions only
depend on these parameters and not on how they were reached.
Examples of state functions include density, internal energy, enthalpy, entropy.
PATH FUNCTION: In contrast, functions that depend on the path from two
values are call path functions.
Path functions depend on the route taken between two states. Two Examples of path
functions are heat and work.
Example: Isothermal Process (Constant Temperature)
Isobaric Process (Constant Process)
Isochoric Process(Constant Volume)
PROCESS: REVERSIBLE AND IRREVERSIBLE PROCESS
Reversible Process:
In thermodynamics, a reversible process is a process whose direction can be returned to
its original position by inducing infinitesimal changes to some property of the system via
its surroundings. Throughout the entire reversible process, the system is in
thermodynamic equilibrium with its surroundings.
IRREVERSIBLE PROCESS: An irreversible process is a process that
cannot return both the system and the surroundings to their original conditions. That is,
the system and the surroundings would not return to their original conditions if
the process was reversed .
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.
F=cma, Where F= force, m= mass of the body, a= acceleration and c is proportionality
constant.
Pressure: Pressure is defined as the normal component of the force per unit
area exerted by the fluid on a real or imaginary boundary.
Work : Energy is expended in the form of work when a force acts through a
distance. dW=F dZ
Where W = work, F= acting force & Z = displacement.
The unit of work in SI system is N m or joule.
Energy :
It is a quantity that can be stored within the system & can be exchange between the
systems and surroundings.
Energy possessed by the system, due to its position above some arbitrary reference
plane is referred to as its potential energy.
PE= mgz
The energy possessed by the body by virtue of its motion is called its kinetic energy.
KE= ½ mu2
Steady state, Equalibrium state and phase rule
Steady state :
A system, which is interacting with the surroundings, is said to have attained a
steady-state condition when the properties at a specified location in the system do
not vary with time.Consider the walls of a furnace, the inside surface of which is
exposed to hot combustion gases and the outside surface to the atmospheric
air.Heat transfer occurs from the inside of the furnace to the outside and the
temperature at a specified location in the wall varies with time. When the wall has
attained steady state with respect to heat transfer, the temperature at any given point
remains constant and does not vary with time.
Equalibrium state:
A system, is said to be in a state of equilibrium if the properties are uniform
throughout and they do not vary with time.A System is in thermal equalibrium, when
no heat exchange occurs between various points within the system and the
temperature is uniform throughout.In a system which is in mechanical equalibrium,
the pressure is uniform.Even under the conditions of uniform temperature and
pressure, transfer of mass may occur between the various phases constituting the
system, or chemical reaction may occurs between the various components present
in the system.
In a System,which is in a state of thermodynamic equalibrium ,in addition to the
absence of heat and work exchange,there would be no mass transfer between the
phases,no diffusion of mass within the phase,and no chemical reaction between the
constituents.
ZEROTH LAW OF THERMODYNAMICS?
When a body ‘A’ is in thermal equilibrium with another body ‘b’, and
also separately in thermal equilibrium with a body ‘C’, then body ‘B’
and ‘C’ will also be in thermal equilibrium with each other. This
statement defines the zeroth law of thermodynamics. The law is
based on temperature measurement.
There are also various ways to state the zeroth law of
thermodynamics. However, in simple terms, it can be said,
“Systems that are in thermal equilibrium exist at the same
temperature”.
Zeroth law of thermodynamics takes into account that
temperature is something worth measuring because it predicts
whether the heat will transfer between objects or not. This is true
regardless of how the objects interact. Even if two objects are not
in physical contact, heat still can flow between them, by means of
radiation mode of heat transfer. Whereas, zeroth law of
thermodynamics states that, if the systems are in thermal
equilibrium, no heat flow will take place.
TEMPERATURE:
The temperature measures the degree of hotness or coldness of a
body.
Since the physiological sensation of hotness or coldness does not
give a quantitative measure of the temperature, we should device
some methods for defining and measuring it.
The zeroth law of thermodynamics forms the basis for the
measurement of temperature. When two bodies are in thermal
equilibrium, we say that the temperature of both the bodies are
equal.
IDEAL GAS TEMPERATURE SCALE:
A Low pressure gas is confined in a constant –volume gas
thermometer as shown in figure
It is brought into contact with the system whose temperature Is to
be measured.
By raising or lowering the tube containing mercury,the volume of
the gas in the bulb can be maintained constant at the level M
indicated in the figure.
In this experiment a constant volume gas thermometer is used to
measure temperature using the Ideal Gas scale. On this scale
temperature has been defined as proportional to the product of PV
for a fixed mass of gas. If the volume of the gas is kept constant,
then the temperature is proportional to the pressure of the gas.
T∞P And
If T1 and P1 are assigned the values of the temperature and
pressure of the gas at the triple point of water (where T = 273.16
K), then the formula becomes.
where P is the pressure of the gas at temperature T, and Ptp is the
pressure of the gas at the triple point of water.
