Department of Materials Science & Engineering

Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 1: Introduction

1 11-08-2025
MLL262: Course structure and timing

➢ L-T-P: 3-1-0
➢ Slot C Lecture: Tue, Wed, Fri (8:00 – 8:50 AM)
➢ Tutorial Sessions: Mon 1:00 – 2:00 PM
➢ Lecture and tutorial sessions can be interchanged if needed be

2 11-08-2025
MLL262: Course policy

➢ 40%: End-sem ➢ 15%: Something more interactive (after mid-sem)

➢ 30%: Mid-sem “Pitch your start-up idea”
➢ 10%: 3 quizzes (best of 2) (must be related to MLL262: metal/metalloids
➢ 5%: Assignments and tutorial performances extraction/processing/refining, waste recycling, battery
recycling, sustainable metal productions, etc.)

3 11-08-2025
MLL262: Official Attendance Criteria

Students with attendance below 75% will receive a one-grade

reduction in their final course grade.
Exception: If a student scores an A or A– with attendance
below 75%, they may retain their grade.

4 11-08-2025
MLL262: Principles of Metal Extraction

5 11-08-2025
“Memories”: Happy/Sad/Boring?

Let’s have a fresh start!

+2 chemistry *NCERT

6 11-08-2025
A more recent connection: MLL452

Metal (e.g., Fe/Steel)

Energy? Energy?

Extraction Processes

Ore (Naturally Occurring) Metal-oxides/compounds (Fe3+)

7 11-08-2025
Sources of metallic elements
Primary extraction routes: From naturally occurring primary sources Secondary extraction routes:
➢ Majority of metals, expect for a few noble ones, are found in form of minerals
From scraps or waste recycling
➢ Minerals are naturally occurring compounds of one or more metals with non-
metals, like oxygen, sulphur, etc.

➢ Ores are (sub-sets of minerals) naturally occurring aggregates of minerals from

which one or metals can be extracted economically

8 11-08-2025 https://economictimes.indiatimes.com/news/international/new-zealand/worlds-largest-iron-ore-mine-
Web Sources
discovered-6-trillion-find-could-make-australia-unstoppable/articleshow/121688130.cms?from=mdr
Sources of elements: What is the most abundant element on earth’s crust other than oxygen?

9 11-08-2025
MLL262: Principles of Metal Extraction (“Extractive Metallurgy”) → Objectives

1. Why MLL262? ..Its vast industrial opportunities and relevance in today’s context
2. What are the different metal/metalloid extraction routes?
3. What are the (thermodynamic and kinetic) fundamentals underpinning these routes?
4. How some of the metals/metalloids are extracted and refined for practical use?
5. What are the future prospects of this topic, which areas require attention and how to approach those?

10 11-08-2025
MLL262: Principles of Metal Extraction → Contents
Module 1: Motivation and Introduction
Module 2: Mineral Beneficiation,
➢ Why MLL262?
metallurgical fuels and furnaces
➢ Sources of metals
➢ Separation & concentration of minerals
➢ Types of metal bearing minerals
➢ Fuels and furnaces, ore agglomeration
➢ Overview of extraction routes

Module 3: Pyrometallurgy
Module 4: Hydrometallurgy
➢ Related thermodynamics and kinetics
➢ Related thermodynamics and kinetics
➢ Iron and steel making
➢ Unit steps
➢ Alternate routes of iron and steel making
➢ Au and U extraction
➢ Extraction of Cu and Si

Module 5: Electrometallurgy
Module 6: Summary & New Developments
➢ Related thermodynamics and kinetics
➢ Alternatives and sustainable extraction
➢ Unit steps
➢ Urban Mining
➢ Mg, Na and Al extraction/refining

11 11-08-2025 Please note that often combination of extraction processes (pyro+electro, hydro+electro, etc.) are used for extracting of a particular metal
MLL262: Principles of Metal Extraction → Textbooks

1. Principles of Extractive Metallurgy, T. Rosenqvist

2. Principles of Extractive Metallurgy, H. S. Ray and A. Ghosh
3. Ironmaking and Steelmaking: Theory and Practice, A. Ghosh and A. Chatterjee
4. Extraction Of Nonferrous Metals, H. S. Ray
5. Introduction to the Thermodynamics of Materials, D. Gaskell

Recent Review article:

The Materials Science behind Sustainable Metals and Alloys, Chemical Reviews, 123, 5, 2436-2608, 2023, D. Raabe

12 11-08-2025
Leisure Reading

Courtesy: Prof. R. Prasad

13 11-08-2025
 Department of Materials Science & Engineering
Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 2

1 11-08-2025
 Why MLL262?

2 11-08-2025
Some important definitions
➢ Minerals → Naturally occurring compounds of one or more metals with non-metals, like oxygen, sulphur, etc.

➢ Ores → Naturally occurring aggregates of minerals (sub-sets of minerals) from which one or metals can be extracted
economically, e.g., Fe2O3 (haematite) is an ore of Fe while FeS2 (pyrite) is not an ore of Fe

➢ Grade → Wt. % metal in an ore → should be above certain limit for viable extraction

➢ Reserves → Ore deposit with average metal content above the minimum exploitable grade

➢ Resources → Ore deposit with average metal content below exploitable grade but expected to be profitable for
future extraction

➢ Gangue → Waste part of the ore, which is not suitable for metal extraction

➢ Slag (pyrometallurgy) → Flux + Gangue (flux is added to remove gangue by lowering the melting point and
increasing slag fluidity)

3 11-08-2025
Human civilizations into ages according to the materials dominating in the society

??

4 11-08-2025 https://wootznano.medium.com/advanced-materials-explained-48dc6e9acb56
History of Extractive Metallurgy

5 11-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Sources of Metals: Earth’s Crust

The terms “Metals” will be used in general representing metals as well as metalloids

6 11-08-2025 Principles of Extractive Metallurgy, H. S. Ray and A. Ghosh

Sources of Metals: Ocean/Sea

Although ocean floors are rich in nodules, which continue to grow,

but only those present above 300 meters are economical to mine

7 11-08-2025 Principles of Extractive Metallurgy, H. S. Ray and A. Ghosh

Concentration factor needed for economic extractions

Extraction Of Nonferrous Metals, H. S. Ray

8 11-08-2025
History of Extractive Metallurgy and Sources of Metals

How come Au, Cu, Ag, Sn, Fe, Pb, etc. became the first
metals to be extracted and used (in metallic form)?

9 11-08-2025
Factors affecting commercial production of metals

➢ Accessibility of ore deposits

➢ Richness of ore deposits
➢ Nature of extraction and refining processes
➢ Properties of the metal
➢ Production cost vs. economic gain (end-use of the metal)

10 11-08-2025
Relevance of Metal Industries: Iron and Steel

11 11-08-2025
Some niche applications of ferrous alloys: Structural materials

12 11-08-2025
Relevance of Iron and Steel

“Per capita steel consumption”

reflects nations development

World average ~200 kg/capita

13 11-08-2025
Comparison of Iron and Steel Producers

14 11-08-2025
Indispensable futuristic need for non-ferrous metals → Elemental state, alloys or compounds!!

15 11-08-2025
Commercial classification table of non-ferrous metals
Group Metals Remarks
Primary Al, Cu, Pb, Zn, Sn, Ni Extensively used; second in importance to iron
Mainly by-products of primary metals but also form their own deposits. Used in almost
Secondary As, Sb, Bi, Cd, Hg, Co
equal amounts (10-20 thousand tons annually)
Light Be, Mg, Al, Ti Low specific gravity (below 4.5), used construction materials for automotive/aerospace
Precious Au, Ag, Pt, Os, Ir, Ru, Rh, Pd Do not corrode; highly priced
W, Mo, Nb, Ta, Ti, Zr, Hf, V, Melting points above 1650°C. Mainly used as alloying elements in steel but also used in
Refractory
Re, Cr the elemental form, some resist high temperature without oxidation
Sc, Ge, Ga, In, Tl, Hf, Re, Se, Do not form minerals of their own, distributed in extremely minute amounts in the
Scattered
Te earth's crust
Undergo radioactive decay, some of them (U, Pu, and Th) undergo fission, Po prepared
Radioactive Po, Ra, Ac, Th, Pa, U, Pu
artificially in nuclear reactors
Y, La, Ce, Pr, Nd, Sm, Eu, Gd,
Rare earths Always occur together! Not rare as the name implies, important components of magnets
Tb, Dy, Ho, Er, Tm, Yb, Lu
Ferroalloy metals Cr, Mn, Si, B Once mainly used as alloying elements to steel, but now also used in elemental form
Alkali Li, Na, K, Rb, Cs Soft and highly reactive (Li and Na are important battery materials)
Alkaline earths Be, Mg, Ca, Sr, Ba Higher melting point and less reactive than the alkali metals

16 11-08-2025
What about other metals production? Where do India stand?

Old data but still the ranking is quite similar

17 11-08-2025
Indian industries in non-ferrous sector
Al Company Capacity (MT) Location
NALCO 0.46 Angul, Odisha
Renukoot, UP ➢ Production in 2021 in India → 2nd largest Al
HINDALCO 1.354 producer, after China (37 MT)
Hirakud, Odisha
BALCO 0.575 Korba, MP ➢ 3rd largest consumer, demand expected to
Vedanta Ltd. 1.74 Jharsuguda, Odisha double in the next decade
TOTAL 4.129

➢ Installed capacity of Cu production in India is 1.08 MT/yr (7th rank, 50% self-sufficiency), mainly by Vedanta & HINDALCO
➢ India's overall installed Zn capacity is 0.92 MT/yr (3rd rank, 100% self-sufficiency), mainly by Hindustan Zinc Limited
➢ The installed capacity of Pb in India is 0.21 MT/yr (3rd rank, 75%).

18 11-08-2025
Towards the future

19 11-08-2025
Critical Minerals for India

Urban Mining and Recycling

20 11-08-2025 Ministry of Mines (India): https://mines.gov.in/admin/download/649d4212cceb01688027666.pdf

MLL262 is a basic requirement for metal and metallurgy based
industries, which caters numerous other industries!!

21 11-08-2025
 Towards Sustainability and Environment

22 11-08-2025
CO2 Emission

23 11-08-2025
CO2 Problem in Steel Industry
1T of Steel → 2.3 – 2.5T of CO2

India aims to produce 300 mT of steel (million tons) by 2030 What about the global scenario considering
steel + other metal industries?
➢ Need to think about 700 mT of CO2 annually
➢ 2 million km2 of rain forest* needed to absorb this much CO2
➢ India is 3.3 million km2, so need to forest 2/3 India??!!

Quest for Alternative and

Sustainable Metal Extraction!!

*by the way, not all trees are equally effective

24 11-08-2025
Other Common Environmental Issues
➢ Air pollution and greenhouse gas emissions

➢ High energy consumption (increased carbon footprints)

➢ Land degradation and habitat Loss

• Mining (especially open-pit) destroys natural landscapes, forests, and ecosystems
• Leads to soil erosion and long-term damage to biodiversity

➢ Water Pollution
• Highly acidic/alkaline and heavy metal contamination in rivers, groundwater
• Toxic chemicals (e.g., cyanide, arsenic) used in processing can enter water systems

➢ Toxic Waste and Tailings Disposal

• Large amounts of waste often contain toxic materials
• Poorly managed tailings

25 11-08-2025
Typical objectives of Extractive Metallurgy

➢ Increase refined metals production rates (continuous/semi-continuous processing)

➢ Reduce energy and cost (optimal land, capital, fuel and raw material utilization)
➢ Minimize waste → Valuable by-product recovery
➢ Recycling wastes → Secondary extraction (using sustainable techniques)
➢ Lowering environmental impacts and ensuring safety

26 11-08-2025
 Department of Materials Science & Engineering
Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 3

1 11-08-2025
Overview of Cu extraction Ore (0.5 – 2 % Cu)

Grinding

Froth Flotation Gangue and other sulphides

Chalcopyrite, CuFeS2

High purity Cu for electrical connections

2 11-08-2025
Different types of ores for some common metals
Symbol Main Ores (Formula)
Al Bauxite (Mixture of Al(OH)₃, AlO(OH)); Gibbsite (Al(OH)₃)
Bauxite
Fe Hematite (Fe₂O₃), Magnetite (Fe₃O₄), Goethite (FeO(OH)), Limonite (FeO(OH)·nH₂O)
Chalcopyrite (CuFeS₂), Chalcocite (Cu₂S), Bornite (Cu₅FeS₄), Malachite (Cu₂CO₃(OH)₂),
Cu
Cuprite (Cu₂O), Azurite (Cu₃(CO₃)₂(OH)₂)
Si Quartz (SiO₂) (source for metallurgical-grade Si)
Mg Magnesite (MgCO₃), Dolomite (CaMg(CO₃)₂), Brucite (Mg(OH)₂) Quartz

Mn Pyrolusite (MnO₂), Braunite (Mn₂⁺Mn₆³⁺SiO₁₂), Manganite (MnO(OH))

Zn Sphalerite ((Zn,Fe)S), Smithsonite (ZnCO₃) Hematite
Co Cobaltite (CoAsS), Smaltite (CoAs₂), Carrollite (CuCo₂S₄), Linnaeite (Co₃S₄)
Li Spodumene (LiAlSi₂O₆), Lithium-rich brines
V Patronite (VS₄), Roscoelite (K(V,Al,Mg)₂AlSi₃O₁₀(OH)₂)
Ilmenite
Zr Zircon (ZrSiO₄)
REEs Bastnäsite (REECO₃F), Monazite (REEPO₄), Xenotime (YPO₄), Allanite
Mo Molybdenite (MoS₂), Powellite (CaMoO₄) Pitchblende

Pb Galena (PbS), Cerussite (PbCO₃)

Ti Ilmenite (FeTiO₃), Rutile (TiO₂)
W Wolframite ((Fe,Mn)WO₄), Scheelite (CaWO₄)
U Pitchblende (UO₂), Carnotite (K₂(UO₂)₂(VO₄)₂·3H₂O)

3 11-08-2025
Typical ores of metals based on their position in the electrochemical series

4 11-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Ore sensing and sorting techniques
➢ Appearance and Physical properties (magnetic, electronic, radioactivity) Hyperspectral data from Cuprite, Nevada

➢ X-ray Fluorescence (XRF): Detecting the characteristic X-rays emitted

(fluorescence) by elements when excited by a primary X-ray source. Used for
identifying minerals with Fe, Cu, Zn, Mn, Pb, etc.

➢ Hyperspectral Remote Sensing: Optical techniques by satellite/airborne

sensors measuring reflectance spectra of surface minerals. Effective in early-
stage exploration over large areas.

➢ Magnetic Sensing: Detects variations in magnetic susceptibility (magnetic

field maps) of ores, especially for magnetic minerals such as magnetite.

➢ Radiometric (Gamma-ray) Sensing: Measures natural gamma radiation

emitted by minerals with isotopes of U, Th, etc.

➢ X-ray Transmission (XRT): Via density and atomic number contrast→ how X-
rays pass through minerals → used for dense ores of W, Pb, Zn, etc.

5 11-08-2025
Mineral Beneficiation Overview: Physical separation and Concentration

Ore: Value Mineral + Gangue

Mineral Beneficiation → Economical Exploitation

➢ Reducing the gangue: Reduces transport cost

➢ Reduces the cost of further processes (less size of ore to deal with)

➢ Energy cost is reduced

6 11-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Extraction Processes Overview: Chemical separation (Pyro/Electro/Hydro- Metallurgy)

Depends on..

➢ Stability of the ore (reactivity of the metal)

➢ Degree of purity required

➢ Local facilities available

➢ Ore grade

7 11-08-2025
General Comparison: Chemical separation (Pyro/Electro/Hydro- Metallurgy)

Parameters Pyrometallurgy Hydrometallurgy Electrometallurgy

Temperature High Room Room/high*
Initial Capital High Low High
Energy Required High Low High
Handling low grade ores No Well-suited Yes (if combined with hydro)
Environmental Issues CO, SO2, CO2, NOx Toxic Chemicals Gas evolution
Rate of reaction High Low Intermediate
Production Cost Low (w.r.t. productivity) Intermediate High
Purity Lower (for bulk) High/Intermediate High

8 11-08-2025
MLL262: Principles of Metal Extraction → Contents
Module 1: Motivation and Introduction
Module 2: Mineral Beneficiation,
➢ Why MLL262?
metallurgical fuels and furnaces
➢ Sources of metals
➢ Separation & concentration of minerals
➢ Types of metal bearing minerals
➢ Fuels and furnaces, ore agglomeration
➢ Overview of extraction routes

Module 3: Pyrometallurgy
Module 4: Hydrometallurgy
➢ Related thermodynamics and kinetics
➢ Related thermodynamics and kinetics
➢ Iron and steel making
➢ Unit steps
➢ Alternate routes of iron and steel making
➢ Au and U extraction
➢ Extraction of Cu and Si

Module 5: Electrometallurgy
Module 6: Summary & New Developments
➢ Related thermodynamics and kinetics
➢ Alternatives and sustainable extraction
➢ Unit steps
➢ Urban Mining
➢ Mg, Na and Al extraction/refining

9 11-08-2025 Please note that often combination of extraction processes (pyro+electro, hydro+electro, etc.) are used for extracting of a particular metal
 Department of Materials Science & Engineering
Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 4

1 11-08-2025
MLL262: Principles of Metal Extraction

Module 2: Mineral Beneficiation,

metallurgical fuels and furnaces
➢ Separation & concentration of minerals
➢ Fuels and furnaces, ore agglomeration

2 11-08-2025
Ores

Explosives are used in mining to remove ores from

their natural beds

3 11-08-2025
Mineral Beneficiation Overview: Physical separation and Concentration

Ore (“run-of-mines” lump size 0.1 – 1 m): Value Mineral + Gangue

Mineral Beneficiation (“Ore-dressing”) → Economical Exploitation

➢ Reducing the gangue: Reduces transport cost (it can be so that cost
of transportation of mined ores to smelting units/plants can be
higher than ore itself!)

➢ Reduces the cost of further processes (less size of ore to deal with)

➢ Energy/chemical reagent cost is reduced

4 11-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Comminution
➢ Particle size reduction (crushing and grinding → utilizing materials brittleness)
➢ Separation of dissimilar mineral particles “ore-liberation” via size reduction: Ideal is release of the valuable minerals
from the associated gangue minerals at the coarsest possible particle size

Ease of comminution depends on:

→ How the minerals have originally grown
→ Bond strength between minerals at phase boundaries

5 11-08-2025 Wills’ Mineral Processing Technology: An Introduction to the Practical Aspects of

Ore Treatment and Mineral Recovery, by Barry A. Wills, Tim Napier-Munn
Crushing and Grinding

➢ Comminution down to particle size 6 mm (maximum) → Crushing

➢ Comminution below 6 mm particle size → Grinding

Crushing → Accomplished by compression of the ore against rigid surfaces, or by impact against surfaces in a rigidly
constrained motion path. Done in machines like jaw crushers, gyratory crushers, cone crushers, etc.

Grinding → Accomplished by abrasion and impact of the ore by the free motion of unconnected media such as rods,
balls, or pebbles. Done in machines like ball mills, rod mills, pebble mills, etc.

6 11-08-2025 Wills’ Mineral Processing Technology: An Introduction to the Practical Aspects of

Ore Treatment and Mineral Recovery, by Barry A. Wills, Tim Napier-Munn
Crushers

➢ Primary: jaw crushers, gyratory crushers, etc. → down to 100 mm particle size

➢ Secondary: cone crushers, roll crushers, etc. → down to 6 mm particle size

7 11-08-2025 Wills’ Mineral Processing Technology: An Introduction to the Practical Aspects of

Ore Treatment and Mineral Recovery, by Barry A. Wills, Tim Napier-Munn
Jaw Crusher
Jaw crusher → Economical for crushing rates below 545 tons/h

https://youtu.be/yTIePG1E-kY?si=YMZitVXpZwpEkbLz
8 11-08-2025
Gyratory crusher

Gyratory crusher → High throughput → For crushing rates above 900 tons/h, gyratory crushers are always selected

https://www.youtube.com/shorts/qKmKE1YiYnY
9 11-08-2025
https://youtu.be/yrWzS_oqNGU?si=FFE_GRZLrqrMomlo
Grinding

➢ Grinding is the last stage in the process of comminution

➢ Particles are reduced in size by a combination of impact and abrasion, either dry or in suspension in water (ball mill,
rod mill, pebble mill)
➢ Extremely fine grinding → jet mills or micronizers

Comminution via griding:

• Cataracting (impact with balls, rods, pebbles)
• Cascading (attrition among rolling balls)
• Interparticle collisions and rubbing
• Frictional forces at the lining of the mill

10 11-08-2025
Ball mills

What is the critical speed of a ball/rod mill?

11 11-08-2025
Energy Requirement in crushing and grinding
Typical Energy Consumption for Crushing and Grinding
➢ Coarse Crushing: 0.2–0.5 kWh per ton of ore
➢ Fine Crushing: 0.5–2 kWh per ton of ore
➢ Coarse Grinding: 1–10 kWh per ton of ore
➢ Micronizing: >100 kWh per ton of ore

Why is crushing/griding energetically expensive?

Increase in surface area does not account for the energy → Actual energy often 100
or 1000 times larger than expected from size reduction!!!
*Beneficiation/ore-dressing cost only
Energy loss → heat, friction, vibrations, and lattice defect!!

Mineral processing operations are often a compromise between

improvements in metallurgical efficiency and milling costs

12 11-08-2025
Mineral Beneficiation Overview: Physical separation and Concentration

13 11-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Sieve screening: Separation based on size

Entire setup is vibrated

14 11-08-2025
Sieve screening: Basics
Sieve Screening → Sizing/separation (wet/dry conditions)
➢ Typically, particles > 38 µm
➢ Mesh size: number of wires per unit length,
➢ ↑mesh size, ↓opening
➢ E.g., -100/+200 mesh powder passes through 100 mesh size but not
200 (150 µm > particle > 75 µm)

General Issues:
➢ Overloading of smaller size opening
➢ Particle shape
➢ 1 – 8 % error (1 % with correct procedure)
➢ Time of sieving is crucial:
o too long → operando particle breaking
o too short → insufficient time for fine particles to pass

Important to follow a standardized test methodologies

15 11-08-2025
Sieve screening: Plots
➢ Screening analysis results are often presented cumulatively, showing the total
percentage of material passing or retained on each screen
➢ Results are typically plotted as cumulative % passing vs. the log(particle size)
➢ Also plotted evenly spaced standard screen sizes on the x-axis, help visualize the
distribution of particle size

16 11-08-2025
Efficient closed loop process

17 11-08-2025
 Department of Materials Science & Engineering
Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 5

1 11-08-2025
MLL262: Principles of Metal Extraction

Module 2: Mineral Beneficiation,

metallurgical fuels and furnaces
➢ Separation & concentration of minerals
➢ Fuels and furnaces, ore agglomeration

2 11-08-2025
Mineral Beneficiation Overview: Physical separation and Concentration

3 11-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Classification
➢ Sieve screening for particles sizes > 38 μm
➢ Classification effective for finer particles

➢ Classification separating method on basis of the velocity with which the particles fall through a fluid medium (water/air)
➢ Mineral beneficiation → hydraulic classification → water as medium
➢ Terminal velocity (vT) of particles in a fluid → size (diameter: d), shape and density (Ds) of the particle

Stokes’ law → Laminar flow

Newton’s law → Turbulent flow

Stokes’ law → Valid for particles below 100 μm (most grinded materials falls in laminar regime)

4 11-08-2025 Wills’ Mineral Processing Technology: An Introduction to the Practical Aspects of

Ore Treatment and Mineral Recovery, by Barry A. Wills, Tim Napier-Munn
Classification: Settling ratio
vT of a particle in a particular fluid → function only of the particle size (shape) and density
➢ If two particles have the same density, then the particle with the larger diameter has the higher vT
➢ If two particles have the same diameter, then the heavier particle has the higher vT

Settling ratio: Ratio of the sizes (diameters) of two particles of different densities that settle at the same vT

Free Settling Hindered Settling

Laminar flow

FSR =

Turbulent

System behaves as a heavy liquid whose density is that of

the pulp rather than that of the carrier liquid

5 11-08-2025 Free Settling Ratio (FSR)

Hydraulic Classifier
➢ Series of sorting columns → higher water velocity (↑) in the first column and relatively low velocity in the last one
➢ Coarser denser particles in the first spigot and fines in the latter

Classification can also be carried out with air under dry conditions
Hydrocyclone (water based)→ Very efficient at fine separation sizes

6 11-08-2025
Efficient closed loop process

7 11-08-2025 Wills’ Mineral Processing Technology: An Introduction to the Practical Aspects of

Ore Treatment and Mineral Recovery, by Barry A. Wills, Tim Napier-Munn
Mineral Beneficiation: Concentration

8 11-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Mineral Beneficiation: Gravity Separation

Gravity Separation (mostly for pre-concentration)→ Based on density differences

➢ Concentration of very heavy/light minerals within a wide range of grain sizes

➢ Utilizes hindered settling → separation almost purely based n density with negligible effect of size

➢ Efficiencies drops with grain sizes finer than 100 μm

9 11-08-2025 Wills’ Mineral Processing Technology: An Introduction to the Practical Aspects of

Ore Treatment and Mineral Recovery, by Barry A. Wills, Tim Napier-Munn
Gravity Separation: Heavy Media Seperation

Heavy Media Separation → Fluids with intermediate gangue and ore densities are made

10 11-08-2025 Wills’ Mineral Processing Technology: An Introduction to the Practical Aspects of

Ore Treatment and Mineral Recovery, by Barry A. Wills, Tim Napier-Munn
 Department of Materials Science & Engineering
Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 6

1 18-08-2025
MLL262: Principles of Metal Extraction

Module 2: Mineral Beneficiation,

metallurgical fuels and furnaces
➢ Separation & concentration of minerals
➢ Fuels and furnaces, ore agglomeration

2 18-08-2025
Mineral Beneficiation Overview: Physical separation and Concentration

3 18-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Gravity Separation: Jigging
Jigging → Separate particles of different densities in a fluid (usually water) by using pulsating motion

→ Coarse, closely sized feed (e.g., 3–10 mm) with narrow specific gravity differences (e.g., fluorite 3.2 from quartz 2.7)
effectively concentrated
→ Larger density differences allow effective concentration over a wider size range.

https://www.youtube.com/watch?v=dauNWfbEBkM
4 18-08-2025 https://millops.community.uaf.edu/amit-145/amit-145-lesson-4/
Mineral Beneficiation Overview: Physical separation and Concentration

5 18-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Froth Flotation: Surface Properties
Froth Flotation → Most versatile mineral processing method → handle greater tonnage of ores (highly effective for low
grade and complex ores) → Widely used for sulfide ores (easily made hydrophobic), certain oxides, and silicates.

Best for very fine particles not concentrated by gravity methods

6 18-08-2025 Wills’ Mineral Processing Technology: An Introduction to the Practical Aspects of

Ore Treatment and Mineral Recovery, by Barry A. Wills, Tim Napier-Munn
Froth Flotation: Hydrophobic Minerals

7 18-08-2025 Wills’ Mineral Processing Technology: An Introduction to the Practical Aspects of

Ore Treatment and Mineral Recovery, by Barry A. Wills, Tim Napier-Munn
Froth Flotation: Reagents
➢ Frothers ➢ Depressants
❑ Prevent bubble collapse; reduce particle sinking ❑ Opposite of activators; prevent flotation
❑ Form stable froth (preventing bursting) to carry of certain minerals
hydrophobic minerals ❑ E.g.: Sodium cyanide, sodium silicate
❑ E.g.: Pine oil, higher alcohol

➢ Collectors ➢ Conditioners
❑ Make mineral surface hydrophobic ❑ Adjust pulp pH for optimum flotation
❑ Organic compounds (e.g., xanthates for metal ❑ Often alkaline for sulfide flotation
sulfides, fatty acids for metal oxides)
❑ Adsorb on mineral surface; selectivity based on
mineral type.
Combinations of reagents make process highly selective
(even for complex ores, which are fine and off similar
➢ Activators density)
❑ Enhance collector action (↑ hydrophobicity) → Bulk Flotation: All valuable sulfides recovered
❑ E.g.: Cu(SO4) 2 activates sphalerite (ZnS) by forming together
CuS layer → ZnS does not reach satisfactory → Selective Flotation: Individual minerals recovered
hydrophobicity only with xanthate collector separately (e.g., PbS, CuFeS2, ZnS, FeS2)

8 18-08-2025
Froth Flotation

Advantages Disadvantages
High separation efficiency High reagent cost
Low grades ores can be used Strict grinding sizes (too coarse
particles can be problematic)
Wide applicability (doesn’t depend Environmental issues
on ore)

9 18-08-2025
Mineral Beneficiation Overview: Physical separation and Concentration

10 18-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Magnetic Separation
Ferromagnetic materials effectively separated → Dry as well as wet

No magnetic ordering Magnetic ordering

Diamagnetic Paramagnetic Antiferromagnetic Ferromagnetic Ferrimagnetic

11 18-08-2025
Magnetic Separation

12 18-08-2025
Electrostatic Separation
Only for dry feed (size range 1 – 0.1 mm) → limited application

13 18-08-2025
 Department of Materials Science & Engineering
Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 7

1 18-08-2025
MLL262: Principles of Metal Extraction

Module 2: Mineral Beneficiation,

metallurgical fuels and furnaces
➢ Separation & concentration of minerals
➢ Fuels and furnaces, ore agglomeration

2 18-08-2025
Mineral Beneficiation Overview: Physical separation and Concentration

Dewatering
➢ Common in mineral beneficiation & hydrometallurgy
➢ Objective: Remove water from pulp (high water content) to
concentrate valuable element

3 18-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Mineral Beneficiation Overview: Physical separation and Concentration

➢ Dewatering groups:
❑ Sedimentation (Thickening)
❑ Filtration
❑ Thermal drying

Stage 1 – Sedimentation/Thickening: Removes ~80% water → thickened pulp (55–65% solids)

Stage 2 – Filtration: Produces moist filter cake (80–90% solids)
Stage 3 – Thermal Drying: Final product (~95% solids)

4 18-08-2025
1. Sedimentation thickening
Settling layers: Settling rates of particles → Stokes’/Newton's laws
➢ A: Clear water (laminar/turbulent)→ Lec 5
➢ B: Diluted suspension → Free settling
➢ C: Concentrated suspension → Hindered settling
➢ D: Almost solid cake → Exudation of water

Mechanisms:
➢ Free Settling (Zone B)
➢ Hindered Settling (Zone C)
➢ Exudation of Water (Zone D)

Flocculation: Speeds settling for fine particles

➢ Particles adhere to form larger flocs
➢ Adherence promoted by London-Van der Waals' forces,
effective only at very close range
➢ Opposed by electrostatic repulsion (particle with
electrically charged atmosphere)
➢ Promoted by: lime, alum, starch, polymers

5 18-08-2025 Principles of Extractive Metallurgy by Rosenqvist

Continuous Thickener – Working Principle
➢ Cylindrical tank
➢ Pulp fed to centre via feed-well (up to 1 m below surface) → minimal disturbance
➢ Overflow: Clarified liquid to peripheral launder
➢ Underflow: Settled solids to central outlet as thickened pulp
➢ Rotating radial arms with blades rake solids to outlet.

6 18-08-2025
2. Filtration
➢ Separate solids from liquids in diluted suspensions as well as thickened pulp
➢ Principle: Liquid flows through a porous filter medium (cloth, screen, or membrane → different pore sized filter cloths)
➢ Solids form a cake on the surface
➢ Driving force: Suction (vacuum), applied pressure, or gravity
➢ Flow rate (largely laminar): 𝑄 = 𝑘∆𝑝. 𝐴/(𝐿. 𝜇)
k = Permeability (depends on particle size & cake porosity), A = area, L = Cake thickness, μ = Viscosity of liquid

Factors affecting performance:

❑ Smaller particles → lower permeability → slower filtration rate
❑ Higher pressure → reduced void space in cake → slower filtration
❑ Cake thickness increases over time → declining rate

7 18-08-2025 Principles of Extractive Metallurgy by Rosenqvist

Rotary drum filter

8 18-08-2025
3. Thermal Drying
➢ Getting rid of the left over water/moisture

9 18-08-2025
Mineral Beneficiation Overview: Physical separation and Concentration

10 18-08-2025 Extraction Of Nonferrous Metals, H. S. Ray

Agglomeration

What is the driving force for agglomeration techniques, like

sintering?

11 18-08-2025
Sintering/Pelletizing Fundamentals
➢ Reduction in surface energy is the driving force for sintering
➢ Surface energy (per unit volume) inversely proportional to particle size (smaller particles sinter faster)
➢ But not entire surface energy is available for sintering (also it is not enough) → high temperatures are needed

Initial stage Intermediate stage Final stage

Rapid formation/growth of Continuous (open) pore structure Open pore structure to closed pores
interparticle neck latter part: grain growth pore removal (towards full density)
density: 60 – 65 % density: 65 – 92 % density beyond 92 %

Initial point of Short time:

Late stage
contact neck growth

2 sphere sintering steps schematic

12 18-08-2025 Randall M. German, Powder Metallurgy Science, 2nd Edition, 1994

Initial sintering stage: Neck formation and growth

Diffusion mechanism → mass flow in response of driving force

➢ Surface diffusion → initial stages (low temperatures), neck formation/ growth without much shrinkage/densification
➢ Bulk diffusion → grain boundary diffusion, volume diffusion, viscous flow, plastic flow → controls densification

13 18-08-2025 Randall M. German, Powder Metallurgy Science, 2nd Edition, 1994

 Sintering: Pore structure evolution
Pores needs to be eliminated for full density → bulk diffusion!

Final sintering stage:

Intermediate stage: Connected Final stage: Spherical closed ➢ Closed pores are difficult to remove (trapped
open pore network at edges of grain pores at grain corners gases) → Vacuum sintering need to close
➢ Pore Ostwald Ripening: Small pores → Large
one (so number of pores reduced)

14 18-08-2025 Randall M. German, Powder Metallurgy Science, 2nd Edition, 1994

Sintering: Microstructure from beginning to end

Initial Intermediate

Final Fracture surface from

final → just to show that
spherical pores are
distributed at the grain
boundaries

15 18-08-2025 Randall M. German, Powder Metallurgy Science, 2nd Edition, 1994

Sintering vs. Palletization (for Fe ores → Iron making)

Sintered Ore Pelletized Ore

Size: 10 – 40 mm Size: 9.5 – 12.5 mm

Shape: Irregular, porous Shape: Spherical, uniform

Lower mechanical strength, Higer mechanical strength,

Higher reactivity (porosity) Lower dust generation

Fe content: 55 – 62 % Fe content: 64 – 68 %

16 18-08-2025
 Department of Materials Science & Engineering
Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 8

1 18-08-2025
Mineral Beneficiation Overview: Physical separation and Concentration

2 18-08-2025
Fuels and Furnaces → Pyrometallurgical Routes

Module 3: Pyrometallurgy
Module 2: Mineral Beneficiation, ➢ Related thermodynamics and kinetics
metallurgical fuels and furnaces ➢ Iron and steel making
➢ Separation & concentration of minerals ➢ Alternate routes of iron and steel making
➢ Fuels and furnaces, ore agglomeration ➢ Extraction of Cu and Si

3 18-08-2025
Different Metallurgical Fuels

➢ Coal
➢ Coke
Used as fuel (heat of combustion and calorific value)+ reducing agent
➢ Oil
➢ Gas

Calorific value→ Fuel selection, and cost calculations all depend on how much heat a fuel can deliver per kilogram
NCP: Net Calorific Value (kcal/kg) …..(MJ/kg = 0.004186 kcal/kg)
NCP= 81C + 340 (H − O/8) + 22S − 5.84 (9H + M)

➢ C, H, O, S: Weight percentages of carbon, hydrogen, oxygen, and sulfur in the fuel

➢ M: Moisture content (wt %)

4 18-08-2025
Different Types of Coal: Precursor to Coke

Coal production world-wide

India → Average 0.8 million tons per day!

5 18-08-2025
Coke: Crucial Metallurgical Fuel Especially for Blast Frunace Iron Making

Coke → Destructive distillation of bituminous coal Coke by carbonization/ destructive distillation of coal
(not peat, lignite, sub-bituminous, or anthracite)

6 18-08-2025
Coke vs. Coal

Coke is used in blast furnace instead of coal:

➢ Higher mechanical strength (especially at high temperatures)
➢ Burden support
➢ Permeability (gas flow)
➢ Lower impurity level (lower slag amount and unwanted
elements in hot metal)

Coke accounts for 60% of hot metal (Fe) cost in iron making!!

Jharkhand → Coking coal (80 % of Indian coking coal)

7 18-08-2025
Metallurgical Furnaces

8 18-08-2025
Different Types Furnaces

9 18-08-2025
Muffle Furnace: Common Lab Furnace

➢ Box type furnace

➢ High-temperature heating in an enclosed chamber
➢ It is widely used for sintering, and heat treatment under
controlled conditions

10 18-08-2025
Shaft Furnace
Vertical, less floor space, solid feed (also called charge/burden) from top, gas blown from bottom,
counter-current reactor

11 18-08-2025
Rotary Kiln Furnace
Horizontally laid rotary shaft (mechanical rotation), inclined at the discharge end
(sponge Fe production, calcination, etc.)

Good for those materials (poor strength, low gas permeability) which cannot be fed
in vertical shaft

12 18-08-2025 https://www.youtube.com/shorts/Ktl7T6UWExw
Retort (Coke Oven)
Closed end sealed chambers, often present in batches, indirect heating (from coil surrounding the reactor)

13 18-08-2025 https://www.youtube.com/watch?v=PYEEn0fERK0
Electric Arc Furnace (Hearth Type)
Hearth type of furnace is where materials are heated on a shallow, dish-shaped hearth
EAF is hearth type furnace → Used for secondary steel making

14 18-08-2025 https://www.youtube.com/watch?v=eKRWF4ei1NU
Multiple Hearth Furnace
Large working capacity counter-current gas flow surface area exposure is enhanced (each layer), e.g.,
roasting of sulfide ore

15 18-08-2025 https://www.youtube.com/watch?v=PYEEn0fERK0
Fluidized Bed Furnace
Increased surface area, greater mass/heat transfer, fine feed particles in “suspended” form by passing gas from
bottom (thus “fluidized bed”)
→ Excellent mixing and uniform temperature throughout the bed
→ Sulfide ore roasting, Direct reduced iron (DRI) from FINMET

16 18-08-2025 https://www.youtube.com/watch?v=pd9zCb-exkU
Fuels and Furnaces → Pyrometallurgical Routes

Module 3: Pyrometallurgy
Module 2: Mineral Beneficiation, ➢ Related thermodynamics and kinetics
metallurgical fuels and furnaces ➢ Iron and steel making
➢ Separation & concentration of minerals ➢ Alternate routes of iron and steel making
➢ Fuels and furnaces, ore agglomeration ➢ Extraction of Cu and Si

Related thermodynamics and kinetics fundamentals

17 18-08-2025
 Department of Materials Science & Engineering
Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 9, 10, 11, 12, 13

1 01-09-2025
Fuels and Furnaces → Pyrometallurgical Routes

Module 3: Pyrometallurgy
Module 2: Mineral Beneficiation, ➢ Related thermodynamics and kinetics
metallurgical fuels and furnaces ➢ Iron and steel making
➢ Separation & concentration of minerals ➢ Alternate routes of iron and steel making
➢ Fuels and furnaces, ore agglomeration ➢ Extraction of Cu and Si

Related thermodynamics and kinetics fundamentals

2 01-09-2025
CP Table

3 01-09-2025 Introduction to the Thermodynamics of Materials, Gaskell

Standard heat of formation (ΔHf0)

Substance Formula Phase −ΔHf∘ (kJ·mol⁻¹)

Water H₂O (l) 285.8

Water H₂O (g) 241.8
Alumina Al₂O₃ (s) 1675.7
Graphite C (s, graphite) 0
Diamond C (s, diamond) -1.9
Hydrogen H₂ (g) 0
Oxygen O₂ (g) 0
Quartz SiO₂ (s) 910.7
Carbon monoxide CO (g) 110
Carbon dioxide CO₂ (g) 395

4 01-09-2025
Temperature dependency

5 01-09-2025
Entropy and microstates

6 01-09-2025
Entropy and microstates

Sthermal

Sthermal + Sconfigurational

7 01-09-2025 Introduction to the Thermodynamics of Materials, Gaskell

Entropy and microstates
Conventional materials High entropy materials
Terminal compositions Multiple elements (≥ 5) Center of phase space
Equal or near-equal amount

High entropy approach

Murty et al., High Entropy Alloys (2014)

8 01-09-2025 https://tuprints.ulb.tu-darmstadt.de/14345/1/Doctoral_thesis_Abhishek_Sarkar.pdf
Phase Transformation

9 01-09-2025 Phase Transformations in Metals and Alloys, Porter and Easterling

Phase Transformation: Pressure – Temperature Interdependency

10 01-09-2025
Ideal and Regular Solution Model Uphill diffusion: Chemical potential
gradient vs. Conc. gradient

11 01-09-2025
 Department of Materials Science & Engineering
Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 15, 16

1 09-09-2025
Ellingham Diagram

Ellingham diagram:
➢ Relative stability of oxides
➢ Reducing ability of reductants, like C, CO, H2

Why is slope for 2C + O2 = 2CO negative, while for others it is positive?

2 09-09-2025 Introduction to the Thermodynamics of Materials, Gaskell

Ellingham Diagram: Change in State

3 09-09-2025 Introduction to the Thermodynamics of Materials, Gaskell

Ellingham Diagram: Metallothermic Reductions

4 09-09-2025
Ellingham Diagram for Metal Sulfides

2Zn + S2 = 2ZnS

2Ca + S2 = 2CaS

5 09-09-2025
Ellingham Diagram (Richardson scale): Effect of pO2

6 09-09-2025 Introduction to the Thermodynamics of Materials, Gaskell

Ellingham Diagram: Effect of pCO/pCO2

7 09-09-2025 Introduction to the Thermodynamics of Materials, Gaskell

Ellingham Diagram: Boudouard Reaction (Solution Loss reaction)
CO is more stable oxide of C at higher temperatures

To be discussed in detail in Tutorial 3

8 09-09-2025 Introduction to the Thermodynamics of Materials, Gaskell

Ellingham Diagram and Blast Furnace Iron Making

500 - 800 K

> 900 K

9 09-09-2025 To be discussed in detail in during blast furnace iron making

Ellingham Diagram: Effect of pH2/pH2O
Towards green iron and steel making

10 09-09-2025
 Department of Materials Science & Engineering
Indian Institute of Technology Delhi (IITD)

MLL262: Principles of Metal Extraction

Lecture 17, 18

1 10-09-2025
Kinetics
Thermodynamics gives the idea about the final equilibrium state but no idea about the rate/feasibility of the reaction

Collision Theory
• Chemical reaction occurs if reactants collide with one another with
sufficient energy, and with the proper orientation
• The rate of the reaction depends on the frequency of collisions

Fraction of effective collisions = e-Ea​/RT

Collision frequency → A

Rate constant (k) = Ae-Ea​/RT

2 10-09-2025
Kinetics

3 10-09-2025
Ostwald Step Rule: When Ea is too high for direct transition

4 10-09-2025
Diffusion
➢ Atomic jumps are thermally assisted (to overcome the Ed of diffusion)

➢ All the atoms have the same G: equal probability of jumps from A to C or C to A

➢ What happens chemical potential is different from case A to C?

Ed

𝒅҆𝝁𝒊
Potential (chemical) gradient : Jump in certain directions
𝒅҆𝒙
more favorable

5 10-09-2025
Chemical Potential vs. Concentration Gradient in Diffusion

6 10-09-2025 Porter and Easterling, Phase transformations in metals and alloys, 2009
Fick’s first law
➢ Diffusion: Mass transfer driven by chemical potential/concentration gradient
𝝏𝑪 𝑎𝑡𝑜𝑚𝑠
𝑱 = −𝑫 𝐽=
𝝏𝒙 𝑚2 . 𝑠
1 1
𝐽1→2 = Г𝑛1→2 𝐽2→1 = Г𝑛2→1
6 6
1 1 𝜕𝐶
𝐽𝑛𝑒𝑡 = 𝐽1→2 − 𝐽2→1 = 6 Г(𝑛1→2 − 𝑛2→1 ) 𝐽𝑛𝑒𝑡 = − Гα2
6 𝜕𝑥

𝜕𝐶 1 ∆C
𝐽 = −𝐷 𝐷 = Гα2
𝜕𝑥 6

∆x
Г temperature dependent; 𝑧𝑣𝑒𝑥𝑝(−𝛥𝐺𝑑 /𝑅𝑇)
𝑑𝐶
→ constant, steady state
𝐷 = 𝐷0 𝑒𝑥𝑝(−𝛥𝐻𝑑 /𝑅𝑇) = 𝐷0 𝑒𝑥𝑝(−𝐸𝑑 /𝑅𝑇) 𝑑𝑥
Г = number of jumps per unit time
n = number of atoms unit area
𝛥𝐺𝑑 = free energy of atomic migration
7 10-09-2025 Porter and Easterling, Phase transformations in metals and alloys, 2009
Fick’s second law

𝑑𝐶 𝑉 = 𝐴δ𝑥
→ is not constant, unsteady state: realistic scenario
𝑑𝑥

𝜕𝐶 𝜕𝐶 𝜕𝐽
𝐽 = −𝐷 =−
𝜕𝑥 𝜕𝑡 𝜕𝑥

𝝏𝑪 𝝏𝟐 𝑪
=𝑫 𝟐 Fick’s second law
𝝏𝒕 𝝏𝒙
𝑚1 = 𝐽1 𝐴δ𝑡
𝑚2 = 𝐽2 𝐴δ𝑡
(𝑚1 −𝑚2 ) δ𝐽𝐴δ𝑡
δ𝐶 = =−
𝑉 𝐴δ𝑥
δ𝐶 δ𝐽
=−
δ𝑡 δ𝑥

8 10-09-2025
Reactions in Extractive Metallurgy: Heterogenous

1. Supply of the reactant in the direction of fluid flow

2. Diffusion of reactant to the interface
3. Interface reaction (intrinsic rate)
• Adsorption of reactants
• Actual reaction (bond breaking/formation)
• Desorption of products
4. Diffusion of products from the interface
5. Removal of products in the direction of fluid flow

9 10-09-2025
Reactions in Extractive Metallurgy: Heterogenous

1. Supply of the reactant in the direction of fluid flow

2. Diffusion of reactant to the interface
3. Interface reaction (intrinsic rate) 1, 2, 4, 5: Involves Mass Transfer → Diffusion/Convection
• Adsorption of reactants
• Actual reaction (bond breaking/formation)
• Desorption of products
4. Diffusion of products from the interface
5. Removal of products in the direction of fluid flow

10 10-09-2025
Mass-Transfer at Solid-Fluid Interface

11 10-09-2025
Mass-Transfer between Two Fluids

Differences between solid-fluid and fluid-fluid interface:

1. Fluid layer is stagnant at solid-fluid interface but not at fluid-fluid one, where flow and consequent renewal of
interfacial layer is to be considered
2. Fluid-fluid interface can also be under turbulence

𝐷𝑖 2 𝑘𝑚,𝑖 = (𝐷𝑖 𝑆)1/2

𝑘𝑚,𝑖 = 2( )
𝜋𝑡𝑒

Higbie’s theory Danckwert’s theory

te = time of exposure of fluid element on surface S = surface renewal factor
(20/sec for mild turbulence, as high as 300 per/sec for high)

12 10-09-2025
Reactions in Extractive Metallurgy: Heterogenous

1. Supply of the reactant in the direction of fluid flow

2. Diffusion of reactant to the interface
3. Interface reaction (intrinsic rate)
• Adsorption of reactants
• Actual reaction (bond breaking/formation)
• Desorption of products
4. Diffusion of products from the interface
5. Removal of products in the direction of fluid flow

13 10-09-2025
Adsorption/desorption of reactants
➢ Central to gas-solid reactions
➢ Surface effect → Adsorbate gets distributed through the surface
of the adsorbent

Adsorption → Exothermic process → Surfaces have high energies (broken bonds)

Surface properties → Area/Porosity, chemistry crucial for adsorption

14 10-09-2025
Physisorption and Chemisorption
Feature Physisorption Chemisorption
Weak van der Waals
Forces involved Strong chemical bonds
forces
Heat of
Low (~10–40 kJ/mol) High (~80–200+ kJ/mol)
adsorption (-ve)
Reversibility Easily reversible* Usually irreversible
Non-specific (easily
liquifiable gases with
Highly specific (depends
Specificity higher van der Waals
on adsorbate & surface)
forces easy to
physisorbed)
Initially favored at higher
Temperature Decreases with rise in
T (like a reaction) but
effect T
then decreases
Surface coverage Multilayer possible Monolayer only
Significant activation
Activation energy Negligible or very low
energy required
Nature Physical process Chemical process
15 10-09-2025
BET theory (Brunauer–Emmett–Teller theory) used for
surface area measurements is based on physisorption