CHBE_221_Lecture_2_-_Intro_to_Adsorption

Page 1: Introduction to Adsorption

  • Lecture 2 - Adsorption (Detour)

  • Notable Quote: "It is a scientific fact that your body will not absorb fat if you take it from another person’s plate" - Dave Barry

Page 2: Topics to Cover

  • Key Topics:

    • Adsorption and related applications

    • Adsorption mechanisms

    • Langmuir, BET, and Freundlich isotherms for gas-solid and liquid-solid adsorption

    • Graphical representation of isotherms to determine model parameters

Page 3: Understanding Adsorption

  • Definition:

    • Adsorption involves the adhesion of liquid or gas molecules (adsorbate) to the surface of a solid (adsorbent).

  • Absorption:

    • Distinct from absorption, where the absorbate penetrates the absorbent's volume.

Page 4: Importance of Adsorption

  • Natural Phenomenon:

    • Found in many chemical and biological processes.

  • Applications:

    • Purification processes (e.g., pharmaceutical separation)

    • Analytical processes (e.g., ion exchange chromatography)

    • Pollution control (e.g., CO2 capture, water treatment)

    • Heterogeneous catalysis systems

  • Desorption:

    • Opposite of adsorption; involves detachment of molecules from the surface.

  • Kinetics Factors:

    • Influence includes system state (pressure, temperature, pH, concentration, surface area).

Page 5: Adsorption Process Flow

  • Process Steps:

      1. Feed/sample

      1. Adsorption

      1. Wash

      1. Elute

  • Time Depiction: Timeline visualizing the adsorption process.

Page 6: CO₂ Capture Example

  • Process Description: CO₂ capture for sequestration involves:

    • Absorbing CO₂ from a process stream.

    • Removing other gases followed by desorption via decreased pressure/increased temperature.

    • Collecting CO₂-rich gas in various applications (e.g., pipelines, power plants).

Page 7: Adsorbent Structure

  • Adsorption Column:

    • Contains a porous resin bead (with or without ligand) designed for optimal adsorption.

    • Open pore structure with sizes ranging from 10 to 150 μm.

Page 8: Antibody Screening and Purification

  • Mechanism:

    • Antibodies selectively bind to specific molecules (antigens).

    • Used to screen for/purify antibodies against target antigens through adsorption.

    • Allows for purification of desired proteins using antibodies as adsorbents.

Page 9: Adsorption Mechanisms

  • Binding Types:

    • Physisorption: Physical binding via weak intermolecular forces (e.g., van der Waals).

    • Chemisorption: Stronger binding via covalent or ionic bonds from chemical reactions.

  • Thermodynamics: Inquiry if adsorption is typically exothermic or endothermic and the implications for engineers.

Page 10: Requirements for Adsorption

  • Necessary Conditions:

    • Availability of free adsorption sites.

    • Contact of adsorbate with the adsorption site.

    • Energy level for binding (activation energy).

    • Energy dissipation upon binding is essential.

  • Dynamic Equilibrium:

    • Occurs when the rate of adsorption equals the rate of desorption.

Page 11: Surface Coverage

  • Extent of Surface Coverage (θ):

    • Defined as the ratio between occupied and available adsorption sites.

    • Can be measured or estimated through various methods.

Page 12: Adsorption Isotherms

  • Basic Representation:

    • Adsorption of substance A on adsorbent M can be modeled as:

      • A + M(surface) ⇌ AM

    • Rates depend on concentration or partial pressure.

  • Isotherm Models:

    • Graphically represent adsorbate quantity at equilibrium as a function of concentration or pressure at constant temperature.

Page 13: Langmuir Isotherm Assumptions

  • Key Assumptions:

    • Monolayer coverage is the maximum limit for adsorption.

    • Adsorbate occupies vacant sites only.

    • All adsorption sites are equivalent.

    • No interactions between adsorbed molecules.

Page 14: Adsorption Kinetics (Langmuir)

  • Kinetic Modeling:

    • Rate of adsorption is proportional to adsorbate collisions and vacant sites.

    • Expressed as: ( \frac{d\theta}{dt} = k_a p N (1 - \theta) )

Page 15: Desorption Dynamics

  • Desorption Equation:

    • Rate of change in θ due to desorption: ( \frac{d\theta}{dt} = -k_d N \theta )

  • Equilibrium Condition:

    • ( k_a p N (1 - \theta) - k_d N \theta = 0 )

Page 16: Langmuir Isotherm Equation

  • Final Form:

    • Rearranging yields: ( \theta = \frac{\alpha p}{1 + \alpha p} )

    • Where p is the adsorbate's partial pressure.

Page 17: Gas Langmuir Representation

  • Substitution:

    • Use of volume ratios to express θ as ( \theta = \frac{V}{V_\infty} )

    • Rearranges to define behavior & represent within a linear framework.

Page 18: Plot Interpretation

  • Graph Analysis:

    • Producing a linear graph of p/V vs p helps determine suitability of Langmuir model for data evaluation.

Page 19: Langmuir Isotherm Example

  • Data: Collected p(kPa) and corresponding p/V values analyzed.

  • Confirmed linear trend, indicating Langmuir as an appropriate model with calculated values: ( V_\infty = 111 ; cm^3 ) and ( \alpha = 7.51 \times 10^{-3} ; kPa^{-1} )

Page 20: Trends in Langmuir Isotherm

  • Graphical Results: Adsorption isotherms for varying α values; trends indicative of model behaviors.

Page 21: Langmuir Isotherm for Liquids

  • Same principles apply but focus shifts to concentration (C) instead of partial pressure.

  • Rearrangement enables plotting to determine suitable model parameters.

Page 22: BET Isotherm Introduction

  • Need for BET: Developed for systems beyond monolayer limits, allowing multiple adsorption layers.

  • Gas Adsorption Equation:( \frac{V}{V_{mon}} = \frac{cz}{1 - z} [1 - \frac{1 - c}{c}] )

Page 23: BET Behavior Analysis

  • Observation of Trends: Theoretical understanding of BET behaviors with increasing adsorption concentrations.

  • Constants defined for both layers in BET model.

Page 24: BET Isotherm Rearrangement

  • Rearranging leads to linear expression: ( y = mx + b )

    • System modeled based on straight-line criteria demonstrating adherence to BET.

Page 25: Example - BET Isotherm

  • Data Evaluation: Analyzed nitrogen adsorption data at specified conditions; determined that c = 298 & Vmon = 816 mm3.

Page 26: Temkin and Freundlich Isotherms

  • Addressing Limitations:

    • Temkin and Freundlich consider variability in energy during adsorption.

  • Formulations provided for gas and liquid systems.

Page 27: Model Assessment with Freundlich

  • Linear Transformations:

    • Organizing Freundlich equations into a linear form facilitates assessment of model suitability.

Page 28: Practical Application in Labs

  • Upcoming Lab: Investigating adsorption of methylene blue on activated carbon; measuring dye concentration over time, determining kinetics and isotherm suitability.

  • Importance: Accurate modeling critical for catalysis and designing separation processes.

Page 29: Design Considerations

  • Design Query: Essential factors for designing an adsorption column to treat organic pollutants.

Page 30: Future Studies

  • Course Continuation: Next lectures will pivot to cell biology basics and evolutionary considerations in bioengineering.