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YOUR STUDY SPACE · CBSE

Thermodynamics — Class 11 Chemistry

Chemistry Part I · Chapter 5

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Chapter summary

Thermodynamics studies the energy changes accompanying physical and chemical processes in macroscopic systems, considering only initial and final equilibrium states, not the rate or mechanism of change. The system, surroundings and boundary are defined, and systems are classified as open, closed or isolated by their exchange of matter and energy. The internal energy is a state function whose change in an adiabatic process equals the work done; combined with heat it gives the first law of thermodynamics, , an expression of energy conservation. Pressure-volume work is examined for reversible, irreversible and free expansions. Enthalpy is defined as , with the heat absorbed at constant pressure equal to , related to by , and with for an ideal gas. Calorimetry (bomb and constant-pressure) measures these quantities. Standard reaction, formation, combustion, atomisation, bond, lattice (via the Born-Haber cycle) and solution enthalpies are introduced, together with Hess's law of constant heat summation. Spontaneity requires more than a fall in enthalpy: the entropy , a measure of disorder, and the second and third laws are introduced, and Gibbs energy provides the criterion for a spontaneous change. Finally, links Gibbs energy to chemical equilibrium.
System, surroundings and types of systemsInternal energy and the first lawPressure-volume workEnthalpy and heat capacityCalorimetryReaction, formation and bond enthalpiesHess's law and Born-Haber cycleEntropy, spontaneity and Gibbs energyGibbs energy and equilibrium

Key ideas & terms

Internal energy
The total energy of a system, a state function whose change equals the adiabatic work done on the system.
Enthalpy
A state function defined as ; its change equals the heat absorbed at constant pressure.
State function
A property such as , , , or whose value depends only on the state of the system, not on the path taken.
Entropy
A state function measuring the degree of randomness or disorder; for a reversible process .
Gibbs energy
The function ; a negative change indicates a spontaneous process.
Hess's law
The total enthalpy change of a reaction is the same whether it occurs in one step or several steps.

Extra questions & answers

State the first law of thermodynamics.

The energy of an isolated system is constant: ; energy can be neither created nor destroyed.

Distinguish open, closed and isolated systems.

An open system exchanges both matter and energy, a closed system exchanges only energy, and an isolated system exchanges neither.

What is the sign convention for and ?

Both are positive when heat is absorbed by the system and when work is done on the system.

How are and related for a gaseous reaction?

, where is moles of gaseous products minus gaseous reactants.

State the relation between and for an ideal gas.

.

State Hess's law of constant heat summation.

If a reaction occurs in steps, its standard reaction enthalpy is the sum of the standard enthalpies of the individual steps.

What is the standard enthalpy of formation of an element in its reference state?

It is taken to be zero by convention.

Define a reversible process.

A change carried out so slowly through a series of near-equilibrium states that it could be reversed by an infinitesimal change.

Why can an endothermic reaction be spontaneous?

Because the total entropy change of system plus surroundings can still be positive, making negative.

How is Gibbs energy related to the equilibrium constant?

By .