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Module 4

The document discusses the following topics in thermodynamics and chemistry: 1. Thermodynamic functions including energy, entropy, enthalpy, Helmholtz free energy, and Gibbs free energy. 2. Estimations of entropy and free energies for chemical reactions. 3. Free energy and cell potential, including the Nernst equation and its applications. 4. Acid-base, oxidation-reduction, and solubility equilibria. 5. Use of free energy considerations in metallurgy through Ellingham diagrams.

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Sanjeeb Sutradhar
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115 views

Module 4

The document discusses the following topics in thermodynamics and chemistry: 1. Thermodynamic functions including energy, entropy, enthalpy, Helmholtz free energy, and Gibbs free energy. 2. Estimations of entropy and free energies for chemical reactions. 3. Free energy and cell potential, including the Nernst equation and its applications. 4. Acid-base, oxidation-reduction, and solubility equilibria. 5. Use of free energy considerations in metallurgy through Ellingham diagrams.

Uploaded by

Sanjeeb Sutradhar
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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B.

Tech First Year Course


Course Title- Chemistry-I (Concepts in Chemistry for Engineering)
Course Code- BTCH101-18
Scheme& Credit – L-3, T-1, P-0, C-4

-Dr. Sanjeeb Sutradhar


Use of Free Energy in Chemical Equilibria (L-6)

Thermodynamic functions: Energy, entropy, and free energy. Estimations of entropy and
free energies.
Free energy and emf. Cell potential, the Nernst equation and applications.

Acid base, oxidation reduction, and solubility equilibria. Water chemistry. Corrosion.

Use of free energy considerations in metallurgy through Ellingham diagrams.


References
Thermodynamics functions: Energy, entropy, and free energy

Internal energy-(E/U)
Total amount of energy associated with a system at constant V and constant T

Enthalpy(H)
sum of internal energy and product of pressure and volume
H= E+PV

Relation between H and E (Under gaseous condition)


=>
=>
=>
=>
=>
Thermodynamics functions: Energy, entropy, and free energy

Entropy (S) (S= state function and q= path function)


Property of a system which measures the randomness or the amount of disorder of a system

Entropy Change Accompanying Change of Phase


Entropy of fusion: Solid to liquid at its melting point

Entropy of vaporization: Liquid to vapour at its boiling point

Entropy of sublimation: Solid to vapor at a particular temperature

Entropy of Transition: Solid changes one crystalline state to other at transition temperature
Thermodynamics functions: Energy, entropy, and free energy

Entropy change for a reversible process:

Entropy change for a irreversible process:


Thermodynamics functions: Energy, entropy, and free energy

Helmholtz free energy (Free energy, F/A/Y)

In an isothermal process the decrease of the work function is a measure of the


maximum work obtainable from that change in state

Gibbs Free Energy (Gibbs energy/Gibbs function, G)


Part of the energy of the system which is available for conversion to useful work

For a change with constant pressure and temperature


Thermodynamics functions: Energy, entropy, and free energy

Spontaneity of a reaction
DG=0 (Equilibrium)
DG= -ve (spontaneous)
DG= +ve (forward direction)
Estimations of entropy and free energies
Entropy for a chemical reaction:

Gibbs free energies for a chemical reaction:

Gibbs free energies for a isothermal process: (dG=VdP –SdT)


Free energy and emf/Cell Potential
Cell potential or emf: Potential difference causes current from electrode at higher
potential to electrode at lower potential (open circuit)

In an electrochemical cell, the system does work by transferring electrical charge through
an external circuit.

Work done for a reaction in the electrochemical cell

In general, for comparing cell voltage, standard condition is used


Nernst Equation and Its Applications
 Calculation of the emf of a cell
 Calculation of the single electrode potential
 Calculation of the equilibrium constant

Ans=0.4581

Ans=0.1182 v
Acid base

Arrhenius Concept of Acids And Bases


Acids: Substances dissociate in aqueous solution gives H+

Base: Substances dissociate in aqueous solution gives OH-

It can’t predict for NH3, CaO etc.

Bronsted-Lowry Concept of Acids And Bases


Acids: Substances has a tendency to donate a proton

Base: Substances has a tendency to accept a proton

Amphoteric: Substance exhibit both acidic or basic behavior


e.g. H2O, HS-, HCO3-, HSO3-
Acid base
Conjugate acid-base pairs

Acid is strong its conjugate base is weak and vice versa


Base is strong its conjugate acid is weak and vice versa
Limitation: acid-base reactions where there is no proton transfer

Lewis Concept of Acids And Bases


Acid: Substances accept a pair of electrons to form a co-ordinate or dative bond
Base: Substances donate a pair of electrons to form a co-ordinate or dative bond
Oxidation Reduction
Oxidation: Loss of one or more electrons
Reduction: Gain of one or more electrons

Oxidizing agents (Oxidant): Substance oxidizes the other substance


e.g. KMnO4, K2Cr2O7, HNO3

Reducing agents (Reductant): Substance reduces the other substance


e.g. Ferrous salt, oxalic acid, HBr, HI, H2S

Oxidizing and Reducing agents: e.g. H2O2, HNO2


Mg + CuSO4 MgSO4 + Cu
Cu + 2AgNO3 Cu(NO3)2 + 2Ag
Solubility Equilibria

Strong electrolyte: Dissociate completely into ions


e.g. NaCl, KCl
Week electrolyte: e.g. CH3COOH
 Dissociate slowly into ions
 Ionic equilibrium
Degree of ionization or dissociation

Case-I: Ionic equilibrium involving soluble ionic compounds (weak acids and weak bases)

Degree of ionization increase with dilution and would approach unity in very dilute solutions
Solubility Equilibria
Case-II: Ionic equilibrium involving sparingly soluble ionic compounds

Product of the concentrations of its ions, in a saturated solution, each concentration raised
to a power equal to the number of times each ion occurs in the equation for the
dissociation of the salt

Ans: 1.4 x 10-11

Application Ksp:
Kion=Ksp ---- Saturated Kion>Ksp --Precipitate Kion<Ksp ---- Unsaturated
Water Chemistry

Characteristics
Physical states Solvent Property Density Viscosity

Hardness of water (milli equivalent/litre) : Property of water to form an insoluble


curd with soap instead of lather
Two types -
 Temporary – Ca(HCO3)2, Mg(HCO3)2, Fe(HCO3)2
Remove- Boiling and addition of lime
 Permanent – CaCl2, CaSO4, Ca(NO3)2
Remove- Boiling and addition of Ca(OH)2, CaCO3
Advantages Disadvantages
Reduced prevalence of hypertension Discoloration of foods
Reduced prevalence of tetany Decrease life time of pipes
Corrosion
Pitting Corrosion- Crevice (Joint) Corrosion-
Aluminum, Mg alloys, Cu alloy gaskets, flanges, fasteners, lap joints

Corrosion prevention method-


 Pre-treatment of metal
 Sacrificial protection
 Coating
Use of free energy considerations in metallurgy through Ellingham
diagrams
Ellingham Diagrams:
Plots of ∆G0 values for 1 mole of a
common reactant like O2 , sulfur or
halogen versus temperature for a number
of metal & non metal to their oxide,
sulphide or chloride reactions

Use for selecting suitable reducing agent


in metallurgy process
Characteristics:
 Curves are straight lines with +ve
slopes
 Lower the position greater is the
stability
Use of free energy considerations in metallurgy through Ellingham
diagrams
 Stability of metal oxides are decreases with increase of temperature
 At high temperature, C becomes reducing agent
 Lower Gibbs free energy of metal reduce the higher Gibbs free energy of metal oxide
 Higher the gap, better is the reducing agent
 Intersection of two lines indicates an oxidation-reduction in equilibrium

Limitations of Ellingham Diagram:


 Does not tell anything about the kinetics of the reduction process.
 Concept is based on ∆Gᶿ whose value is calculated from ‘K’ from the relation: ∆Gᶿ =
-RTlnK. It has presumed that all reactants & products are in equilibrium. But this
is not always true.
 Reactants/products may be solid. So at room temperature activation energy of
reaction is high & reaction may not occur even if ∆Gᶿ is negative.

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