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Thermodynamics

Thermodynamics pdf

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26 views7 pages

Thermodynamics

Thermodynamics pdf

Uploaded by

skmohan13456
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Thermodynamics

Important Terms and Definitions


System: Refers to the portion of universe which is under observation.
Surroundings: Everything else in the universe except system is called surroundings. The Universe = The
System + The Surroundings.

Open System: In a system, when there is exchange of energy and matter taking place with
the surroundings, then it is called an open system.
For Example: Presence of reactants in an open beaker is an example of an open system. Closed System: A
system is said to be a closed system when there is no exchange of matter ‘ but exchange of energy is possible.
For example: The presence of reactants in a closed vessel made of conducting material.
Isolated System: In a system, when no exchange of energy or matter takes place with the surroundings, is
called isolated system.
For example: The presence of reactants in a thermoflask, or substance in an insulated closed vessel is an
example of isolated system.
Isothermal process: When the operation is carried out at constant temperature, the process is said to be
isothermal. For isothermal process, dT = 0 Where dT is the change in temperature.
Adiabatic process: It is a process in which no transfer of heat between system and surroundings, takes place.
Isobaric process: When the process is carried out at constant pressure, it is said to be isobaric. i.e. dP = 0
Isochoric process: A process when carried out at constant volume, it is known as isochoric in nature.
Cyclic process: If a system undergoes a series of changes and finally returns to its initial state, it is said to be
cyclic process.
Reversible Process: When in a process, a change is brought in such a way that the process could, at any
moment, be reversed by an infinitesimal change. The change r is called reversible.
Internal Energy
It is the sum of all the forms of energies that a system can possess.
In thermodynamics, it is denoted by AM which may change, when
— Heat passes into or out of the system
— Work is done on or by the system
— Matter enters or leaves the system.
Change in Internal Energy by Doing Work
Let us bring the change in the internal energy by doing work.
Let the initial state of the system is state A and Temp. TA Internal energy = UA
On doing’some mechanical work the new state is called state B and the temp. TB. It is found to be
TB > TA
uB is the internal energy after change.
∴ ΔU = UB – UA
Change in Internal Energy by Transfer of Heat
Internal energy of a system can be changed by the transfer of heat from the surroundings to the system
without doing work.
ΔU = q
Where q is the heat absorbed by the system. It can be measured in terms of temperature difference.
q is +ve when heat is transferred from the surroundings to the system. q is -ve when heat is transferred from
system to surroundings.
When change of state is done both by doing work and transfer of heat.
ΔU = q + w
First law of thermodynamics (Law of Conservation of Energy). It states that, energy can neither be created nor
be destroyed. The energy of an isolated system is constant.
ΔU = q + w.
Work (Pressure-volume Work)
Let us consider a cylinder which contains one mole of an ideal gas in which a frictionless piston is fitted
Work Done in Isothermal and Reversible Expansion of Ideal Gas

Isothermal and Free Expansion of an Ideal Gas


For isothermal expansion of an ideal gas into vacuum W = 0
Enthalpy (H)
It is defined as total heat content of the system. It is equal to the sum of internal energy and pressure-volume
work.
Mathematically, H = U + PV
Change in enthalpy: Change in enthalpy is the heat absorbed or evolved by the system at constant pressure.
ΔH = qp
For exothermic reaction (System loses energy to Surroundings),
ΔH and qp both are -Ve.
For endothermic reaction (System absorbs energy from the Surroundings).
ΔH and qp both are +Ve.
Relation between ΔH and ΔU.
Extensive property
An extensive property is a property whose value depends on the quantity or size of matter present in the
system.
For example: Mass, volume, enthalpy etc. are known as extensive property.
• Intensive property
Intensive properties do not depend upon the size of the matter or quantity of the matter present in the system.
For example: temperature, density, pressure etc. are called intensive properties.
Heat capacity
The increase in temperature is proportional to the heat transferred.
q = coeff. x ΔT
q = CΔT
Where, coefficient C is called the heat capacity.
C is directly proportional to the amount of substance.
Cm = C/n
It is the heat capacity for 1 mole of the substance.
• Molar heat capacity
It is defined as the quantity of heat required to raise the temperature of a substance by 1° (kelvin or Celsius).
• Specific Heat Capacity
It is defined as the heat required to raise the temperature of one unit mass of a substance by 1° (kelvin or
Celsius).
q = C x m x ΔT
where m = mass of the substance
ΔT = rise in temperature.
Relation Between Cp and Cv for an Ideal Gas
At constant volume heat capacity = Cv
At constant pressure heat capacity = Cp
At constant volume qv= CvΔT = ΔU
At constant pressure qp = Cp ΔT = ΔH
For one mole of an ideal gas
ΔH = ΔU + Δ (PV) = ΔU + Δ (RT)
ΔH = ΔU + RΔT
On substituting the values of ΔH and Δu, the equation is modified as
Cp ΔT = CvΔT + RΔT
or Cp-Cv = R
Measurement of ΔU and ΔH—Calorimetry
Determination of ΔU: ΔU is measured in a special type of calorimeter, called bomb calorimeter.
Working with calorimeter. The calorimeter consists of a strong vessel called (bomb) which can withstand very
high pressure. It is surrounded by a water bath to ensure that no heat is lost to the surroundings.
Procedure: A known mass of the combustible substance is burnt in the pressure of pure dioxygen in the steel
bomb. Heat evolved during the reaction is transferred to the water and its temperature is monitored.
Enthalpy Changes During Phase Transformation
Enthalpy of fusion: Enthalpy of fusion is the heat energy or change in enthalpy when one mole of a solid at its
melting point is converted into liquid state.
Enthalpy of vaporisation: It is defined as the heat energy or change in enthalpy when one mole of a liquid at
its boiling point changes to gaseous state.
Enthalpy of Sublimation: Enthalpy of sublimation is defined as the change in heat energy or change in
enthalpy when one mole of solid directly changes into gaseous state at a temperature below its melting point
Standard Enthalpy of Formation
Enthalpy of formation is defined as the change in enthalpy in the formation of 1 mole of a substance from its
constituting elements under standard conditions of temperature at 298K and 1 atm pressure.
Enthalpy of Combustion: It is defined as the heat energy or change in enthalpy that accompanies the
combustion of 1 mole of a substance in excess of air or oxygen.

Thermochemical Equation
A balanced chemical equation together with the value of ΔrH and the physical state of reactants and products
is known as thermochemical equation.

Spontaneity
Spontaneous Process: A process which can take place by itself or has a tendency to take place is called
spontaneous process.
Spontaneous process need not be instantaneous. Its actual speed can vary from very slow to quite fast.
A few examples of spontaneous process are:
(i) Common salt dissolves in water of its own.
(ii) Carbon monoxide is oxidised to carbon dioxide of its own.
• Entropy (S)
The entropy is a measure of degree of randomness or disorder of a system. Entropy of a substance is
minimum in solid state while it is maximum in gaseous state.
The change in entropy in a spontaneous process is expressed as ΔS
Gibbs Energy and Spontaneity
A new thermodynamic function, the Gibbs energy or Gibbs function G, can be defined as
G = H-TS
ΔG = ΔH – TΔS
Gibbs energy change = enthalpy change – temperature x entropy change ΔG gives a criteria for spontaneity at
constant pressure and temperature, (i) If ΔG is negative (< 0) the process is spontaneous.
(ii) If ΔG is positive (> 0) the process is non-spontaneous.
• Free Energy Change in Reversible Reaction

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