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Thermodynamics Chemistry Chapter 6

June 9, 2022 by Bhagya

Thermodynamics Chemistry Chapter 6

• Import ant Terms and Definit ions
Syst em: 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.

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Open Syst em: In a system, when there is exchange of energy and matter taking place with
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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 TOP Universit ies in India
system is said to be a closed system when there is no exchange of matter ‘ but exchange of energy is
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possible.
For example: The presence of reactants in a closed vessel made of conducting material. TOP Pharmacy Colleges in India
Isolat ed Syst em: In a system, when no exchange of energy or matter takes place with the surroundings, is
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called isolated system.
For example: The presence of reactants in a thermoflask, or substance in an insulated closed vessel is an Mat h Riddles for Kids wit h Answers
example of isolated system.
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Homogeneous Syst em: A system is said to be homogeneous when all the constituents present is in the
same phase and is uniform throughout the system. NCERT Solut ions for Class 11 Physics
For example: A- mixture of two miscible liquids.
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Het erogeneous syst em: A mixture is said to be heterogeneous when it consists of two or more phases and
the composition is not uniform. NCERT Solut ions for Class 12 Physics
For example: A mixture of insoluble solid in water. ’
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The state of the system: The state of a thermodynamic system means its macroscopic or bulk properties
which can be described by state variables:
Pressure (P), volume (V), temperature (T) and amount (n) etc. NCERT Solut ions for Class 10 Science Chapt er 1
They are also known as state functions.
Isot hermal process: When the operation is carried out at constant temperature, the process is said to be NCERT Solut ions for Class 10 Science Chapt er 2
isothermal. For isothermal process, dT = 0 Where dT is the change in temperature. Met als and Nonmet als Class 10
Adiabat ic process: It is a process in which no transfer of heat between system and surroundings, takes
place. carbon and it s compounds class 10
Isobaric process: When the process is carried out at constant pressure, it is said to be isobaric. i.e. dP = 0 Periodic Classificat ion of Element s Class 10
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 Life Process Class 10
be cyclic process. NCERT Solut ions for Class 10 Science Chapt er 7
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. NCERT Solut ions for Class 10 Science Chapt er 8

• Int ernal Energy NCERT Solut ions for Class 10 Science Chapt er 9

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 NCERT Solut ions for Class 10 Science Chapt er 10
— Heat passes into or out of the system NCERT Solut ions for Class 10 Science Chapt er 11
— Work is done on or by the system
— Matter enters or leaves the system. NCERT Solut ions for Class 10 Science Chapt er 12
Change in Int ernal Energy by Doing Work NCERT Solut ions for Class 10 Science Chapt er 13
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 NCERT Solut ions for Class 10 Science Chapt er 14
On doing’some mechanical work the new state is called state B and the temp. TB . It is found to be NCERT Solut ions for Class 10 Science Chapt er 15
TB > TA
uB is the internal energy after change. NCERT Solut ions for Class 10 Science Chapt er 16
∴ Δu = uB – uA
Change in Int ernal 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.
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• Work SOLUTIONS Work)
(Pressure-volume RD SHARMA CLASS 12 CLASS 11 CLASS 10 CLASS 9 CBSE SAMPLE PAPERS
Let us consider a cylinder which contains one mole of an ideal gas in which a frictionless piston is fitted.
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• Work Done in Isot hermal and Reversible Expansion of Ideal Gas

• Isot hermal and Free Expansion of an Ideal Gas

For isothermal expansion of an ideal gas into vacuum W = 0

• Ent halpy (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 ent halpy: 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.
Relat ion bet ween ΔH and Δu.
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• Ext ensive propert y

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.
• Int ensive propert y
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 capacit y
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 capacit y
It is defined as the quantity of heat required to raise the temperature of a substance by 1° (kelvin or
Celsius).
• Specific Heat Capacit y
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.
• Relat ion Bet ween 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—Calorimet ry
Determination of ΔU: ΔU is measured in a special type of calorimeter, called bomb calorimeter.
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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.

• Ent halpy Changes During Phase Transformat ion

Ent halpy 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.
Ent halpy of vaporisat ion: It is defined as the heat energy or change in enthalpy when one mole of a liquid at
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Ent halpy of Sublimat ion: 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.

• St andard Ent halpy of Format ion

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.

Ent halpy of Combust ion: 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 Equat ion

A balanced chemical equation together with the value of ΔrH and the physical state of reactants and
products is known as thermochemical equation.
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Convent ions regarding t hermochemical equat ions

1. The coefficients in a balanced thermochemical equation refer to the number of moles of reactants and
products involved in the reaction.

• Hess’s Law of Const ant Heat Summat ion

The total amount of heat evolved or absorbed in a reaction is same whether the reaction takes place in
one step or in number of steps.

• Born-Haber Cycle
It is not possible to determine the Lattice enthalpy of ionic compound by direct experiment. Thus, it can be
calculated by following steps. The diagrams which show these steps is known as Born-Haber Cycle.
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• Spont aneit y
Spont aneous 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 spont aneous process are:
(i) Common salt dissolves in water of its own.
(ii) Carbon monoxide is oxidised to carbon dioxide of its own.
• Ent ropy (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 Spont aneit y

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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Heat of Combust ion

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