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THERMODYNAMICS

The document provides a comprehensive overview of thermodynamics, covering basic concepts, thermodynamic processes, and the laws governing energy transformations. It details the first, second, and third laws of thermodynamics, along with key concepts such as enthalpy, Gibbs free energy, and entropy. Additionally, it includes short answer questions, numerical problems, and application-based questions to reinforce understanding of the subject.

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hhoneysugar2002
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11 views

THERMODYNAMICS

The document provides a comprehensive overview of thermodynamics, covering basic concepts, thermodynamic processes, and the laws governing energy transformations. It details the first, second, and third laws of thermodynamics, along with key concepts such as enthalpy, Gibbs free energy, and entropy. Additionally, it includes short answer questions, numerical problems, and application-based questions to reinforce understanding of the subject.

Uploaded by

hhoneysugar2002
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as DOCX, PDF, TXT or read online on Scribd
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THERMODYNAMICS

1. Basic Concepts of Thermodynamics

 System and surroundings


 Types of systems (open, closed, isolated)
 State functions and path functions
 Extensive and intensive properties

2. Thermodynamic Processes

 Isothermal process (constant temperature, ΔT = 0)


 Adiabatic process (no heat exchange, q = 0)
 Isochoric process (constant volume, ΔV = 0)
 Isobaric process (constant pressure, ΔP = 0)
 Cyclic and reversible vs. irreversible processes

3. First Law of Thermodynamics

 Internal energy (ΔU)


 Work done on/by the system (W = -PΔV)
 Heat transfer (q)
 Mathematical form: ΔU = q + W
 Sign conventions of heat and work

4. Enthalpy and Its Types

 Enthalpy (H) and enthalpy change (ΔH)


 Relation between ΔH and ΔU: ΔH = ΔU + PΔV
 Enthalpy of formation (ΔHf°)
 Enthalpy of combustion (ΔHc°)
 Enthalpy of neutralization
 Enthalpy of fusion and vaporization

5. Work Done in Different Processes

 Work done in an isothermal process: W = -nRT ln(V₂/V₁)


 Work done in an adiabatic process: W = (Cv/R) (T₂ - T₁)
 Work done in an isochoric process: W = 0
 Work done in an isobaric process: W = PΔV

6. Second Law of Thermodynamics

 Concept of entropy (S)


 Entropy change (ΔS) in different processes
 ΔS = q_rev / T (for reversible process)
 Spontaneity and Gibbs free energy (ΔG)

7. Gibbs Free Energy (ΔG) and Spontaneity

 Gibbs equation: ΔG = ΔH - TΔS


 Criteria for spontaneity:
o If ΔG < 0 → Spontaneous
o If ΔG > 0 → Non-spontaneous
o If ΔG = 0 → Equilibrium

8. Third Law of Thermodynamics

 Definition: Entropy of a pure crystalline substance is zero at absolute zero (0 K)


 Importance in calculating absolute entropy

9. Specific and Molar Heat Capacities

 Heat capacity (C)


 Molar heat capacity at constant volume (Cv)
 Molar heat capacity at constant pressure (Cp)
 Relation: Cp - Cv = R

10. Hess's Law of Constant Heat Summation

 Definition and applications


 Calculation of enthalpy change using Hess’s law

11. Bond Enthalpy & Lattice Energy


Adiabatic (q = Isochoric (V = Isobaric (P =
Property Isothermal (ΔT= 0)
0) constant) constant)
q = 0 (No heat
Heat Change (q) q = nRT ln(V₂/V₁)
exchange)
q = nCvΔT q = nCpΔT

Internal Energy Change (ΔU) ΔU = 0 ΔU = nCvΔT ΔU = nCvΔT ΔU = nCvΔT


Enthalpy Change (ΔH) ΔH = 0 ΔH = nCpΔT ΔH = nCvΔT ΔH = nCpΔT
ΔS = 0 (For
Entropy Change (ΔS) ΔS = nR ln(V₂/V₁)
reversible)
ΔS = nCv ln(T₂/T₁) ΔS = nCp ln(T₂/T₁)

Molar Specific Heat (Cv, Cp) Cv = Cp (since ΔT = 0) Cp - Cv = R Cv = (R/γ-1) Cp = (γR/γ-1)


c = q/mΔT (not defined c = 0 (no heat
Specific Heat (per gram) here) exchange)
c = Cv/M c = Cp/M

1. Short Answer Questions

1. Define the following terms:


o System
o Surroundings
o State functions
o Path functions
2. Differentiate between open, closed, and isolated systems with examples.
3. State the First Law of Thermodynamics. How does it relate to the law of
conservation of energy?
4. Explain the concept of enthalpy (H). How is it different from internal energy (U)?
5. What is Hess's Law of Constant Heat Summation? Illustrate with an example.
6. Define standard enthalpy of formation. How is it different from standard enthalpy
of combustion?
7. What are intensive and extensive properties? Provide two examples of each.
8. Explain the significance of Gibbs free energy (G) in predicting the spontaneity of a
process.
9. Describe the Third Law of Thermodynamics and its importance.
10. What is the relationship between Cp and Cv for an ideal gas? Derive the expression.

2. Numerical Problems
1. Calculate the work done when 2 moles of an ideal gas expand isothermally and
reversibly from a volume of 5 L to 10 L at 300 K.
Hint: Use the formula W=−nRTln⁡(VfVi)W = -nRT \ln\left(\frac{V_f}{V_i}\
right)W=−nRTln(ViVf).
2. Determine the change in internal energy (ΔU) when 1 mole of an ideal gas is heated
from 300 K to 400 K at constant volume. (Given: Cv = 12.5 J/mol·K)
Hint: Use ΔU=nCvΔTΔU = nC_vΔTΔU=nCvΔT.
3. For the reaction: N₂(g) + 3H₂(g) → 2NH₃(g), the standard enthalpy change (ΔH°) is
-92.4 kJ/mol. Calculate the standard enthalpy change when 34 grams of NH₃ are
formed.
Hint: Molar mass of NH₃ = 17 g/mol.
4. Calculate the entropy change (ΔS) when 1 mole of water vapor condenses at 100°C
and 1 atm. (Given: ΔHvap = 40.79 kJ/mol)
Hint: Use ΔS=ΔHTΔS = \frac{ΔH}{T}ΔS=TΔH, with T in Kelvin.
5. A gas expands adiabatically, and its temperature drops from 500 K to 400 K. If the
molar heat capacity at constant volume (Cv) is 20 J/mol·K, calculate the work done
during the expansion for 1 mole of the gas.
Hint: For adiabatic processes, ΔU=WΔU = WΔU=W and ΔU=nCvΔTΔU =
nC_vΔTΔU=nCvΔT.

3. Conceptual Questions

1. Why is the enthalpy of neutralization of strong acids and bases nearly constant (~57
kJ/mol)?
2. Explain why the entropy of the universe always increases for a spontaneous process.
3. Discuss the significance of the Helmholtz free energy and its applications.
4. Why is it impossible to convert all the heat extracted from a hot reservoir into work
without any loss? Relate this to the Second Law of Thermodynamics.
5. How does the concept of free energy help in understanding the equilibrium position
of a chemical reaction?

4. Application-Based Questions

1. Describe how a bomb calorimeter is used to measure the enthalpy change of a


combustion reaction.
2. Explain the working principle of a refrigerator in terms of thermodynamic
processes.
3. How does Le Chatelier's principle relate to the changes in enthalpy and entropy
during a chemical reaction?
4. Discuss the environmental implications of the entropy changes associated with the
melting of polar ice caps.
5. Explain how the concept of Gibbs free energy is applied in biological systems,
particularly in ATP hydrolysis.

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