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Chemical Thermodynamics: Scope / Importance of Thermodynamics
Chemical Thermodynamics: Scope / Importance of Thermodynamics
Chemical Thermodynamics: Scope / Importance of Thermodynamics
INTRODUCTION
Thermodynamics is a science that deals with the relationship of heat and energy and their
inter conversion of one form into the other as heat energy, electrical energy, chemical
energy, mechanical energy etc.
Greek roots
therme meaning heat and
dynamics meaning power or strength or motion
A more elegant definition the power of heat. Or Flow of heat
It helps to determine the extent to which a process can proceed before attainment
of equilibrium
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4-10-2014
Types of System
Open system: A system which can exchange both matter and energy with its
surroundings is called open system.
Closed system: A system which can exchange energy but not matter with its
surroundings is called a closed system.
Isolated system: A system which cannot exchange both energy and matter with its
surroundings is called an isolated system.
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4-10-2014
Homogeneous system: A system which consists of only one phase and uniform
throughout.
Example: Mixture of gases
Heterogeneous system: A system which consists of two or more phases and not
uniform throughout.
Example: A system consisting of two or more immiscible liquids, ice in water
Macroscopic properties
The properties of a system in bulk which are easily measurable and can be
Extensive or Intensive in nature.
Intensive Property
The properties which are independent of the quantity of matter present in the
system are called intensive property.
Extensive Property
The properties which depend on the amount or mass of matter in the system are
called Extensive property.
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4-10-2014
Intensive Property
Extensive property
Temperature,
Volume
Boiling point
Mass
Density
Internal energy
Viscosity
Heat capacity
Refractive index
Free energy
Freezing point
Enthalpy
Thermal conductivity
Entropy
Specific heat
Number of moles
Surface tension
Process
A thermodynamic process is an operation carried out on the system to bring about a
desired change in the system. During a process the state of the system changes.
Different types of Process
Adiabatic Process During this process no heat enters or leaves the system. q=0
The process s carried out only in isolated system.
Cyclic process- Cyclic process is an operation when the system returns to its
original state after undergoing series of changes. For a cyclic process dE=0 :
dH=0
Spontaneous Process A process which occurs on its own without any driving
force.
Non Spontaneous Process A process which occurs with the aid of driving force
Reversible Process The process is reversible if it is carried out slowly so that all
the steps is reversible and at equilibrium.
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4-10-2014
Irreversible Process The process does not go back to its initial state. The driving
force and opposing force differ by large amount. The process is carried out
abruptly in non equilibrium conditions.
Reversible process
Reaction occurs in many steps
Irreversible process
It has only two steps, initial and
final step
It is a slow process
It is a rapid process
It is an imaginary process
It is a real process
It cannot be reversed
thermodynamic variables
Endothermic reactions If heat is taken by the system from surrounding (q > 0 or +ve)
Examples: Melting, evaporation, sublimation.
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4-10-2014
A system in which the macroscopic properties do not undergo any change with
time is said to be in thermodynamic equilibrium. During this state three types of
equilibrium exists within the system. They are
Mechanical equilibrium
No mechanical work is done by one part of the system on other part. At this state
the pressure is constant throughout the system.
Chemical equilibrium
No chemical change occurs at any part of the system. At this stage the
composition is same throughout the system.
Thermal equilibrium
No heat flow from one part of the system to other part. The temperature remains
same throughout the system.
STATE of the SYSTEM: The state of the system is the conditions of existence of
system and is described by macroscopic properties.
State Function or State Variables
The macroscopic properties of the system ( Temperature, pressure, surface tension,
viscosity, internal energy, enthalpy ) which changes with the change in the state of the
system is called state variables or state function. Change in the value of state function
depends only on the initial and final state of a system and not on the path through which
the system attains the final state. Ex. U, H, G, S
Path function or path variables
The property which depends on the path through which a system attains the final state is
called path function.
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4-10-2014
- Extensive property
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Energy Energy is ability to do work. All forms of energy can be divided into the two
following categories:
Kinetic Energy or Energy in action or The energy of motion
Potential Energy or Stored energy or The energy of position
Many systems we encounter will contain both kinetic and potential energy
Energy is a state function.
Internal Energy - ( E) or (U) The total amount of energy associated with the given
substance.
Internal energy = kinetic + potential energy of the molecules or atoms of a body
Kinetic energy = translation, rotation, vibration of the molecules or atoms
E = Ev + Er + Ee + Et
Change in internal energy can be easily measured by applying first law of
thermodynamics.
E = q w
Enthalpy (H) It is the heat content of a system.
H= E + PV
Amount of heat that passes between the system and the surroundings is given by
qp = E +PV
-state function
LAWS OF THERMODYNAMICS
The Zeroth law of thermodynamics : If a system A is in thermal equilibrium with system
B , and system B is in thermal equilibrium with system C , then systems A and C are in
equilibrium with each other.
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4-10-2014
Energy can neither be created nor destroyed, but it can be converted from one
form to another form.
Compression: I law: E = q + w
Expansion : I law: E = q + (- w)
If the process has undergone infinitesimal change, the I Law expression becomes
dE = dq dw
or
dE = dq PdV
Limitations of I Law
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4-10-2014