Chemical Thermodynamics and its Application

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Dr. Niladri Sarkar

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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

Learning Outcomes

  • After completion of the course student should able to understand different thermodynamic activities happening in everyday life in nature.
  • They should know different chemical equilibriums and relationship between them.
  • They should have a general idea about elevation in boiling point and depression in freezing point, their conditions of occurrence and effects.
  • They should able to know why there is lowering in vapour pressure , Rault’s law , Henry’s law and their applications
  • They should have practical experiences on how to calculate heat capacity of calorimeter from known enthalpy of solution or enthalpy of neutralization
  • They will know how to determination of basicity/proticity of a polyprotic acid by the thermochemical method

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

 

 

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

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