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)
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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.
