Thermodynamics Revision Short Notes Self Study Material Chemistry Class 11

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Thermodynamics Revision Short Notes Self Study Material Chemistry Class 11

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Thermodynamics is the branch of science that deals with the relationships between heat, work, temperature, and energy. It is concerned with how energy is converted from one form to another and how it is transferred between systems.

Thermodynamics Revision Short Notes Self Study Material Chemistry Class 11

Macroscopic and Microscopic Properties

A thermodynamic system is a part of the universe that we are interested in studying. The surroundings are everything outside of the system. Systems can be classified as follows:

• Closed system: No exchange of matter or energy between the system and the surroundings.
• Open system: Exchange of matter and energy between the system and the surroundings is allowed.
• Isolated system: No exchange of matter or energy between the system and the surroundings.

The macroscopic properties of a system are those that can be measured directly, such as pressure, volume, temperature, and amount of substance. The microscopic properties of a system are those that describe the behavior of the individual particles in the system, such as kinetic energy and potential energy.

State Functions

A state function is a property of a system that depends only on the current state of the system and not on how the system reached that state. Examples of state functions include pressure, volume, temperature, and internal energy.

Internal Energy

The internal energy of a system is the total energy of all the particles in the system. It includes the kinetic energy and potential energy of the particles. Internal energy is a state function.

Work

Work is the transfer of energy between a system and its surroundings by the application of a force. Work is done when the force causes the system to move. Work can be positive or negative. Positive work is done when the system does work on the surroundings. Negative work is done when the surroundings does work on the system.

Heat

Heat is the transfer of energy between a system and its surroundings due to a temperature difference. Heat is always transferred from a region of higher temperature to a region of lower temperature. Heat is a state function.

The First Law of Thermodynamics

The first law of thermodynamics states that the total energy of an isolated system is constant. This means that energy can neither be created nor destroyed, but only converted from one form to another. The first law of thermodynamics can be expressed mathematically as follows:

ΔU = q + w

where:

• ΔU is the change in internal energy of the system
• q is the heat absorbed by the system
• w is the work done on the system

Reversible and Irreversible Processes

A reversible process is a process that can be exactly reversed. An irreversible process is a process that cannot be exactly reversed. All real processes are irreversible.

Types of Thermodynamic Processes

There are four main types of thermodynamic processes:

• Isothermal process: A process in which the temperature of the system remains constant.
• Adiabatic process: A process in which no heat is transferred between the system and the surroundings.
• Isochoric process: A process in which the volume of the system remains constant.
• Isobaric process: A process in which the pressure of the system remains constant.

Applications of Thermodynamics

Thermodynamics has many applications in chemistry, including:

• Predicting the spontaneity of chemical reactions
• Calculating the enthalpy change of chemical reactions
• Designing heat engines and refrigerators
• Understanding the behavior of gases and liquids

Conclusion

Thermodynamics is a fundamental branch of chemistry that deals with the relationships between heat, work, temperature, and energy. It has many applications in chemistry and other fields.

Additional Details

Here are some additional details about some of the important concepts in thermodynamics:

• Enthalpy: Enthalpy is a state function that is defined as the sum of the internal energy of a system and the product of the system’s pressure and volume. It is denoted by the symbol H. The change in enthalpy of a system during a process can be calculated using the following equation:

ΔH = ΔU + PΔV

• Spontaneity: A spontaneous process is a process that occurs naturally without any outside intervention. The second law of thermodynamics states that the entropy of an isolated system always increases over time. This means that spontaneous processes are always accompanied by an increase in entropy.
• Chemical reactions: Thermodynamics can be used to predict the spontaneity of chemical reactions. A chemical reaction will be spontaneous if the total change in entropy of the system and the surroundings is positive.
• Heat engines: A heat engine is a device that converts heat energy into mechanical energy. The efficiency of a heat engine is limited by the Carnot cycle. The Carnot cycle is a theoretical cycle that is the most efficient possible cycle for a heat engine.
• Mayer’s formula: Mayer’s formula is a relationship between the molar specific heats of gases. It states that the difference between the molar specific heat at constant pressure (Cp) and the molar specific heat at constant volume (Cv) is equal to the gas constant (R).
• Cp – Cv = R
• Carnot engine: The Carnot engine is a theoretical heat engine that is the most efficient possible cycle for a heat engine. The Carnot cycle consists of four reversible processes:
  1. Isothermal expansion
  2. Adiabatic expansion
  3. Isothermal compression
  4. Adiabatic compression

• Carnot theorem: The Carnot theorem states that all reversible heat engines operating between the same two temperatures have the same efficiency.
• Entropy: Entropy is a state function that is a measure of the disorder of a system. The second law of thermodynamics states that the entropy of an isolated system always increases over time.
• Gibbs free energy: Gibbs free energy is a state function that is used to predict the spontaneity of chemical reactions at constant temperature and pressure. It is denoted by the symbol G. The change in Gibbs free energy of a system during a process can be calculated using the following equation:
• ΔG = ΔH – TΔS

where T is the temperature of the system.

• Bond energy: Bond energy is the amount of energy required to break a chemical bond. It is a measure of the strength of a chemical bond. Bond energies can be used to calculate the enthalpy change of chemical reactions.

Applications of Thermodynamics in Chemistry

Thermodynamics has many applications in chemistry, including:

• Predicting the spontaneity of chemical reactions: Thermodynamics can be used to predict whether a chemical reaction will occur spontaneously under a given set of conditions. This is important for designing chemical processes and for understanding the behavior of chemical systems.
• Calculating the enthalpy change of chemical reactions: The enthalpy change of a chemical reaction is the amount of heat that is absorbed or released during the reaction. Thermodynamics can be used to calculate the enthalpy change of a reaction from the bond energies of the reactants and products.
• Designing heat engines and refrigerators: Thermodynamics can be used to design heat engines and refrigerators that are more efficient.
• Understanding the behavior of gases and liquids: Thermodynamics can be used to understand the behavior of gases and liquids, such as their compressibility and their tendency to expand. This is important for designing chemical engineering equipment and for understanding the behavior of chemical systems.

Conclusion

Thermodynamics is a powerful tool that can be used to understand and predict the behavior of chemical systems. It has many applications in chemistry and other fields.

1. Introduction to Thermodynamics:

• Thermodynamics is the branch of science that deals with energy and its transformations.
• Key concepts: System, Surroundings, Universe, State of a System.

2. Thermodynamic Terms:

• Internal Energy (U): The sum of all microscopic forms of energy in a system.
• Enthalpy (H): H = U + PV (Pressure-Volume work).
• Heat (q) and Work (w): Transfer of energy between the system and surroundings.
• Heat transfer conventions: Endothermic and Exothermic processes.

3. First Law of Thermodynamics:

• The law of conservation of energy.
• ΔU = q – w, where ΔU is the change in internal energy, q is heat, and w is work.
• The first law explains energy transfer but doesn’t provide information about the direction of a process.

4. Enthalpy:

• Enthalpy change (ΔH) is used in constant pressure processes.
• ΔH = q_p (heat at constant pressure).
• ΔH = ΔU + PΔV.

5. Measurement of ΔU and ΔH:

• Calorimetry: Determining heat transfer through temperature changes.
• Bomb calorimeter and coffee cup calorimeter.

6. Enthalpy Changes for Chemical Reactions:

• Standard Enthalpy of Formation (ΔH°f): The enthalpy change when one mole of a compound is formed from its elements in their standard states.
• Hess’s Law: The enthalpy change of a reaction is the same whether it occurs in one step or several steps.
• Standard Enthalpy of Combustion (ΔH°c): Enthalpy change when one mole of a substance undergoes complete combustion.

7. Second Law of Thermodynamics:

• Entropy (S) and the concept of disorder.
• The law states that energy spontaneously tends to disperse or become more chaotic.
• Processes occur in a direction that increases the overall entropy of the universe.

8. Gibbs Free Energy (G):

• ΔG = ΔH – TΔS, where ΔG is the change in free energy.
• Predicts the spontaneity and feasibility of a reaction at constant temperature and pressure.
• Negative ΔG: Spontaneous and exergonic.
• Positive ΔG: Non-spontaneous and endergonic.

9. Third Law of Thermodynamics:

• Entropy approaches zero as the temperature approaches absolute zero.

10. Entropy Changes in Chemical Reactions:

• Entropy change for a reaction is calculated using the standard molar entropy values.
• ΔS° = ΣS°(products) – ΣS°(reactants).

11. Gibbs-Helmholtz Equation:

• ΔG = ΔH – TΔS and the equilibrium constant (K).

12. Spontaneity and Equilibrium:

• Relates ΔG to the equilibrium constant (K).
• If Q (reaction quotient) = K, the system is at equilibrium.
• If Q < K, the reaction proceeds forward.
• If Q > K, the reaction proceeds backward.

13. Factors Affecting Spontaneity:

• Temperature, pressure, and concentration effects on ΔG.
• Le Chatelier’s principle and its application to equilibrium.

14. Spontaneity and Reversible Processes:

• Reversible processes are idealized and can be reversed by an infinitesimal change in external conditions. They are used to understand the thermodynamic behavior of real processes.
• Irreversible processes are spontaneous and lead to an increase in the entropy of the universe.

15. Carnot Cycle:

• An idealized reversible cycle used to understand the maximum efficiency of a heat engine.
• Consists of four reversible processes: isothermal expansion, adiabatic expansion, isothermal compression, and adiabatic compression.
• The efficiency of a Carnot engine depends only on the temperatures of the hot and cold reservoirs.

16. Refrigerators and Heat Pumps:

• These devices operate in a manner opposite to heat engines. They use work to transfer heat from a cold reservoir to a hot one.
• The coefficient of performance (COP) is a measure of their efficiency.

17. Thermodynamic Equations:

• Maxwell’s Relations: A set of equations that relate thermodynamic variables, including temperature, pressure, volume, and entropy.
• Clausius-Clapeyron Equation: Describes the variation of vapor pressure with temperature for a phase transition.

18. Phase Transitions:

• Solid to liquid, liquid to gas, and other phase transitions involve changes in enthalpy and entropy.
• The phase diagram represents the regions where different phases are stable under different conditions of temperature and pressure.

19. Chemical Equilibrium and Thermodynamics:

• The relationship between ΔG and the equilibrium constant K for chemical reactions.
• Predicting the direction of a chemical reaction based on ΔG and K.

20. Standard Conditions and Standard State:

• Standard temperature and pressure (STP).
• The concept of the standard state for gases (1 atm and 298 K).

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