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Thermodynamics Chemistry Chapter 6

June 9, 2022 by Bhagya

Thermodynamics Chemistry Chapter 6

• 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.

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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.

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Homogeneous System: A system is said to be homogeneous when all the constituents present is in the
same phase and is uniform throughout the system.

For example: A- mixture of two miscible liquids.

Heterogeneous system: A mixture is said to be heterogeneous when it consists of two or more phases
and the composition is not uniform.

For example: A mixture of insoluble solid in water. ’

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.

They are also known as state functions.

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.

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• Work Done in Isothermal and Reversible Expansion of Ideal Gas

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• Isothermal and Free Expansion of an Ideal Gas

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

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• 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.

Thermodynamics Chemistry Chapter 6 img-6

• 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.

Thermodynamics Chemistry Chapter 6 img-7

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.

Thermodynamics Chemistry Chapter 6 img-8

• 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.

Thermodynamics Chemistry Chapter 6 img-9

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.

Thermodynamics Chemistry Chapter 6 img-10

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.

Thermodynamics Chemistry Chapter 6 img-11

• 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.

Thermodynamics Chemistry Chapter 6 img-12

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.

Thermodynamics Chemistry Chapter 6 img-13

• 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.

Thermodynamics Chemistry Chapter 6 img-14

Conventions regarding thermochemical equations

1. The coefficients in a balanced thermochemical equation refer to the number of moles of

reactants and products involved in the reaction.

Thermodynamics Chemistry Chapter 6 img-15

• Hess’s Law of Constant Heat Summation

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.

Thermodynamics Chemistry Chapter 6 img-16

• 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.

Thermodynamics Chemistry Chapter 6 img-17

• 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

Thermodynamics Chemistry Chapter 6 img-18

• 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.

(iii) If ΔG is positive (> 0) the process is non-spontaneous.

• Free Energy Change in Reversible Reaction

Thermodynamics Chemistry Chapter 6 img-19

Thermodynamics Chemistry Chapter 6 img-20

Thermodynamics Chemistry Chapter 6 img-21

Heat of Combustion

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