Chemical Thermodynamics and its Application

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Dr. Suchismita Acharya

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Core Courses

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Course Name : Chemical Thermodynamics and its Application

 

Code(Credit) : CUTM 1472(3-2-1)

 

Course Objectives

  • The Course covers the fundamentals laws of Thermodynamics and its related Phenomena
  • To understand the applicability of chemical thermodynamics in various industrial processes  as well as day to day life incidents.
  • To understand the conceptual basis of thermodynamic scale of temperature as standard scale
  • To understand the concept of chemical equilibrium in attaining high products by controlling various factors.
  • To understand the concept of ideal and non-ideal solution along with  various colligative properties.
  • To practice various thermochemical experiments

Course Outcomes

COs Course outcomes Mapping COs with POs (High-3, Medium-2, Low-1)
CO1 Able to gain entire Knowledge on Thermodynamics, Chemical Equilibria and Colligative properties. PO1 (3)
CO2 To know different thermodynamic equations, chemical equilibriums and their relationship among each other. PO2 (3). PO4 (2)
CO3 Able to interpret and analyse the data for publication PO4 (3)

Course Syllabus

   Module I : Introduction to Thermodynamics 

  • Intensive and extensive variables; state and path functions; isolated, closed and open systems  Zeroth law of thermodynamics
  • First law: Concept of heat (q), work (w), internal energy (U), and statement of first law
  •  Enthalpy (H), relation between heat capacities,Calculations of q, w, U and H for reversible condition.
  • Calculations of q, w, U and H for irreversible and free expansion of gases (ideal and van der Waals) under isothermal and adiabatic conditions
  • Asignment 1 (Flip Class : Types of Systems and First law) (1 h)
  • Asignment 2 (Flip Class : Calculation of Work done for various systems) (1 h)

Module II : Thermochemistry 

  • Heats of reactions: standard states; Enthalpy of formation of molecules and ions and enthalpy of combustion and its applications
  •  Effect of temperature (Kirchhoff’s equations) and pressure on enthalpy of reactions, Adiabatic flame temperature, explosion temperature
  • Assignment 3 (Flip Class: Calculation of bond energy, bond dissociation energy and resonance energy from thermochemical data) (2h)
  • Practice 1: Determination of heat capacity of a calorimeter for different volumes using change of enthalpy data of a known system (method of back calculation of heat capacity of calorimeter from known enthalpy of solution or enthalpy of neutralization).
  • Practice 2: Determination of heat capacity of the calorimeter and enthalpy of neutralization of hydrochloric acid with sodium hydroxide.
  • Practice 3: Determination of heat capacity of the calorimeter and integral enthalpy (endothermic and exothermic) solution of salts.
  • Practice 4: Determination of enthalpy of hydration of copper sulphate

Module III : Chemical Thermodynamics I

  • Thermodynamic scale of temperature
  • Statement of  the second law of thermodynamics; molecular and statistical interpretation of entropy.
  • Calculation of entropy change for reversible and irreversible processes
  • Third Law: Statement of third law, concept of residual entropy , calculation of absolute entropy of molecules
  •  Free Energy Functions: Gibbs and Helmholtz energy; variation of S, G, A with T, V, P; Free energy change and spontaneity
  • Relation between Joule-Thomson coefficient and other thermodynamic parameters; inversion temperature
  • Thermodynamic equation of state
  • Assignment 4 : (Flip Class) Gibbs-Helmholtz equation (1h)
  • Assignment 5 : (Flip Class) Maxwell relations (1h)

Module IV : Chemical Thermodynamics and Open System

  • Partial molar quantities, dependence of thermodynamic parameters on composition
  • Gibbs Duhem equation, chemical potential of ideal mixtures, change in thermodynamic functions in mixing of ideal gases
  • Assignment 6 (Flip class) (Problem Solving approach) (2h)
  • Assignment 7  (Flip class) (Partial molar quantities) (1h)

Module V : Chemical Equilibrium: I

  • Criteria of thermodynamic equilibrium
  • Degree of advancement of reaction, chemical equilibria in ideal gases
  • Thermodynamic derivation of relation between Gibbs free energy of  reaction and  reaction quotient.
  • Concept of fugacity
  •  Equilibrium constants and their quantitative dependence on temperature, pressure and concentration
  • Coupling of exoergic and endoergic reactions
  • Free energy of mixing and spontaneity
  • Assignment 8 (Flip Class) (Concept of fugacity and equilibrium) (1h)
  • Practice 5: To study the shift of equilibrium between ferric ions and thiocyanate ions by increasing the concentration of either of them

Module VI : Chemical Equilibrium: II

  • Thermodynamic derivation of relations between the various equilibrium constants Kp, Kc and Kx. Le Chatelier principle (quantitative treatment)
  • Equilibrium between ideal gases and a pure condensed phase.
  • Introduction to dilute  Solutions
  • Introduction to Colligative Properties
  • Practice 6 : Le Chatelier principle in Contact Process (Demonstration)
  • Practice 7 : Le Chatelier principle in Haber Process (Demonstration)

Module VII: Colligative Properties

  • Excess thermodynamic functions. Thermodynamic derivation using chemical potential to derive relations between the relative lowering of vapour pressure and amount of solute
  • Thermodynamic derivation using chemical potential to derive relations between the elevation of boiling point and amount of solute
  •  Thermodynamic derivation using chemical potential to derive relations between Depression of freezing point and amount of solute
  • Thermodynamic derivation using chemical potential to derive relations between the osmotic pressure and amount of solute.
  • Assignment 9  (Flip class) ( Raoult’s and Henry’s Laws and their
    applications) (1h)
  • Assignment 10  (Flip class) (Applications in calculating molar masses of normal, dissociated and associated solutes in solution) (1h)
  • Practice 8: To find the freezing point depression of a solution
  • Practice 9: To find the molar mass through freezing point depression of a solution
  • Practice 10: Determining the Vant Hoff's factor
  • Practice 11: To find the elevation of boiling point of a solution
  • Practice 12: To find the molar mass through elevation of boiling point of a solution

 

 

Books for Reference

 

Text Books:

  1. Atkins P. and De Paula, J. Physical Chemistry Tenth Ed., OUP, 2014.
  2. Castellan, G. W. Physical Chemistry 4th Ed., Narosa, 2004.

Reference Books:

  1. Engel, T. and Reid, P. Physical Chemistry 3rd Ed., Prentice Hall, 2012
  2. .McQuarrie, D. A. and Simon, J. D. Molecular Thermodynamics Viva Books, 2004.
  3. Roy, B. N. Fundamentals of Classical and Statistical Thermodynamics Wiley, 2001
  4. Levine, I .N. Physical Chemistry 6th Ed. Tata Mc Graw Hill, 2010.

 

 

Session Plan

Session 1

Systems and Surroundings, intensive and extensive variables , state and  path functions, isolated, closed and open systems, Zeroth law of thermodynamics

https://www.youtube.com/watch?v=oXxX1NmE7Ho

https://www.youtube.com/watch?v=dWwZIOSi_Vw

https://www.youtube.com/watch?v=FdXxJuRw7Ck

https://www.youtube.com/watch?v=JK9sENnK_Bk

https://www.youtube.com/watch?v=S2hsaTO0bO8

Session 2

First law: Concept of heat (q), work (w), internal energy (U), and statement of first law

https://www.youtube.com/watch?v=O7HwhkYt6YU

Session 3

Enthalpy (H), relation between heat capacities, calculations of q, w, U and H for reversible condition.

https://www.youtube.com/watch?v=x_pbr5RFhVc

https://www.youtube.com/watch?v=yhNHJ7WdT8A

https://www.youtube.com/watch?v=sYe0ulf428w

Session 4

Calculations of q, w, U and H for irreversible , and free expansion of gases (ideal and van der Waals) under isothermal and adiabatic conditions ,

https://www.youtube.com/watch?v=guP4wKNBtM4

https://www.youtube.com/watch?v=8zJrjEV9n8o

https://www.youtube.com/watch?v=x8cGJBMT8Yo

https://www.youtube.com/watch?v=Cx9vo4Ovo3c

Session 5 (Assignment 1) (1h)

Asignment 1 (Flip Class : Types of Systems and First law) 

Session 6 (Assignment 2) (1h)

Asignment 2 (Flip Class : Calculation of Work done for various systems) 

Session 7

Heats of reactions: standard states; Enthalpy of formation of molecules and ions and enthalpy of combustion and its applications

https://www.youtube.com/watch?v=nASUmuqu7so

https://www.youtube.com/watch?v=9N5ppQrnrYY

https://www.youtube.com/watch?v=I3G9yFvoTkI

Session 8

Effect of temperature (Kirchhoff’s equations) and pressure on enthalpy of reactions, adiabatic flame temperature ,  explosion  temperature

https://www.youtube.com/watch?v=mFRvwerRRag

https://www.youtube.com/watch?v=OHZQd6hp3Iw

https://www.youtube.com/watch?v=HnSBzkTqDFE

Session 9 (Assignment 3) (1h)

Assignment 3 (Flip Class: Calculation of bond energy, bond dissociation energy and resonance energy from thermochemical data

https://www.youtube.com/watch?v=QFzZdcMnlK4

https://www.youtube.com/watch?v=Bau0Myl0mko

https://www.youtube.com/watch?v=MTpqLnALKcU

Session 10 (Practice 1) (2h)

Practice 1: Determination of heat capacity of a calorimeter for different volumes using change of enthalpy data of a known system (method of back calculation of heat capacity of calorimeter from known enthalpy of solution or enthalpy of neutralization)

https://vlab.amrita.edu/?sub=2&brch=190&sim=1352&cnt=1

Session 11 (Practice 2) (2h)

Practice 2: Determination of heat capacity of the calorimeter and enthalpy of neutralization of hydrochloric acid with sodium hydroxide

https://vlab.amrita.edu/?sub=2&brch=190&sim=1546&cnt=1

Session 12 (Practice 3) (2h)

Practice 3: Determination of heat capacity of the calorimeter and integral enthalpy (endothermic and exothermic) solution of salts.

https://www.youtube.com/watch?v=75_d9qBW-og

Session 13 (Practice 4) (2h)

Session 14

Thermodynamic scale of temperature

https://www.youtube.com/watch?v=elAn6-CNv-w

Session 15

Statement of  the second  law of thermodynamics; molecular and statistical interpretation of entropy

https://www.youtube.com/watch?v=NrQDGgRiQfU

Session 16

Calculation of entropy change for reversible and irreversible processes

https://www.youtube.com/watch?v=Cc2Qq3WFjQc

https://www.youtube.com/watch?v=OiiapmxzccE

Session 17

Third Law: Statement of third law, concept of residual entropy , calculation of absolute entropy of molecules

https://www.youtube.com/watch?v=kuGmsnzjbpE

Session 18

Free Energy Functions: Gibbs and Helmholtz energy; variation of S, G, A with T, V, P; Free energy change and spontaneity

https://www.youtube.com/watch?v=8N1BxHgsoOw

Session 19

Relation between Joule-Thomson coefficient and other thermodynamic parameters; inversion temperature

https://www.youtube.com/watch?v=nptVYDXaTok

Session 20

Thermodynamic equation of state

https://www.youtube.com/watch?v=p0IzTNyOXoE

Session 21 (Assignment 4) (1h)

Assignment 4 : (Flip Class) Gibbs-Helmholtz equation  

https://www.youtube.com/watch?v=zCKF0DCmyos

Session 22 (Assignment 5) (1h)

Assignment 5 : (Flip Class)

Session 23

Partial molar quantities, dependence of thermodynamic parameters on composition

https://www.youtube.com/watch?v=ZlyD1qi3aL0

Session 24

Gibbs Duhem equation, chemical potential of ideal mixtures, change in thermodynamic functions in mixing of ideal gases

https://www.youtube.com/watch?v=y41yI-RCyvg&t=25s

https://www.youtube.com/watch?v=WCFDWoN_9UI

Session 25 (Assignment 6) (2h)

Assignment 6 (Flip class) (Problem Solving approach) 

Session 26 (Assignment 7) (1h)

Assignment 7 (Flip class) (Partial molar quantities) 

Session 27

Criteria of thermodynamic equilibrium

https://www.youtube.com/watch?v=CmaTnV4m93E

Session 28

Degree of advancement of reaction, chemical equilibria in ideal gases

https://www.youtube.com/watch?v=1GiZzCzmO5Q

Session 29

Thermodynamic derivation of relation between Gibbs free energy of  reaction and  reaction quotient

https://www.youtube.com/watch?v=DyK7cR0k3ds

Session 30

Session 31

Equilibrium constants and their quantitative dependence on temperature, pressure and concentration

https://www.youtube.com/watch?v=6caqV49o1-M

https://www.youtube.com/watch?v=24pmSqoupJg

Session 32

Coupling of exoergic and endoergic reactions

https://www.youtube.com/watch?v=Pa9bgjp81EM

Session 33

Free energy of mixing and spontaneity

https://www.youtube.com/watch?v=Z2kzBdpB64o

Session 34 (Assignment 8) (1h)

Assignment 8 (Flip Class) (Concept of fugacity and equilibrium) 

Session 35 (Practice 5) (2h)

Practice 5: To study the shift of equilibrium between ferric ions and thiocyanate ions by increasing the concentration of either of them

https://www.youtube.com/watch?v=3_QgX1z_wLM

Session 36

Thermodynamic derivation of relations between the various equilibrium constants Kp, Kc and Kx. Le Chatelier principle (quantitative treatment)

https://www.youtube.com/watch?v=XmgRRmxS3is

Session 37

Equilibrium between ideal gases and a pure condensed phase.

https://www.youtube.com/watch?v=ss2ZC3gpeA8

Session 39

Introduction to Colligative Properties

https://www.youtube.com/watch?v=hOhgXRukRDg

Session 41 (Practice 7) (2h)

Practice 7: Le Chatelier principle in Haber Process (Demonstration)

https://www.chemguide.co.uk/physical/equilibria/haber.html

Session 42

Thermodynamic derivation using chemical potential to derive relations between the relative lowering of vapour pressure and amount of solute

https://www.youtube.com/watch?v=AmJUhVrO50E

Session 43

Thermodynamic derivation using chemical potential to derive relations between the elevation of boiling point and amount of solute

https://www.youtube.com/watch?v=WA-UbQdd5UQ

Session 44

Thermodynamic derivation using chemical potential to derive relations between Depression of freezing point and amount of solute

https://www.youtube.com/watch?v=xQul_6N4Tac

Session 45

Thermodynamic derivation using chemical potential to derive relations between the osmotic pressure and amount of solute

https://www.youtube.com/watch?v=NIwHkecDgNQ

Session 46 (Assignment 9) (1h)

Assignment 9 (Flip class) ( Raoult’s and Henry’s Laws and their applications) 

https://www.youtube.com/watch?v=QRYT-QfPBK4

https://www.youtube.com/watch?v=9JtTpPEesOk)

Session 47 (Assignment 10) (1h)

Assignment 10 (Flip class) (Applications in calculating molar masses of normal, dissociated and associated solutes in solution (1h)

https://www.youtube.com/watch?v=sIIZ-onZLKw

Session 48 (Practice 8) (2h)

Practice 8:To find the freezing point depression of a solution

https://vlab.amrita.edu/?sub=2&brch=190&sim=337&cnt=1

Session 49 (Practice 9) (2h)

Practice 9:To find the molar mass through freezing point depression of a solution

https://vlab.amrita.edu/?sub=2&brch=190&sim=337&cnt=1

Session 50 (Practice 10) (2h)

Practice 10: Determining the Vant Hoff's factor

https://vlab.amrita.edu/?sub=2&brch=190&sim=337&cnt=1

Session 51 (Practice 11) (2h)

Practice 11: To find the elevation of boiling point of a solution

https://vlab.amrita.edu/?sub=2&brch=190&sim=1545&cnt=1

Session 52 (Practice 12) (2h)

Practice 12: To find the m find the molar mass through boiling point elevation of a solution

https://vlab.amrita.edu/?sub=2&brch=190&sim=1545&cnt=1

Our Main Teachers

Currently working as an Assistant Professor in the department of Chemistry, Centurion University of Technology and Management, Bhubaneswar campus.