Surface Analysis

Summer 2016

Dr. Oswald Prucker

prucker@imtek.de

Part 2: Sorption of liquids and gases on surfaces

Definitions

• Adsorption is a process at surfaces.

Molecules settle down on surfaces and

get attached through relatively weak

forces. They may over time be

released again (= desorption). The

entire process is dynamic.

• Adsorption is the temporary

attachment of particles on surfaces.

• Absorption is the incorporation of a

material (e.g. or liquid) in a body (such

as a sponge). The absorbed material

disappears inside the body.

Absorption vs. Adsorption ... =)

Taken from: Carsten Schmuck, Bernd Engels,

Tanja Schirrmeister, Reinhold Fink, Chemie für Mediziner,

Pearson Studium, 2008, S. 124

… even more definitions

Substrate – often used to describe surfaces of solid state bodies, on

which adsorbtion occurs (also: adsorbent) the orange bar

Adsorbate – general name of molecular species which is adsorbed

onto a substrate the red balls

Adsorption – is a process in which a molecule will be adsorbed at a

surface the „down arrow“

Desorption – the opposite of adsorption

the „up arrow“

How do we describe sorption phenomena

Adsorption isotherms

• coverage - measure for the part of the surface to which an adsorbate (species) is

adsorbed. Usually denoted using the ‘theta’ symbol,

• =1 indicates complete coverage of the solid surface with a monolayer.

Chemistry is better ;-)

Two major types of adsorption:

• Physisorption

• Chemisorption

Physisorption

Physical adsorption (Physisorption) – attachment through vdW forces. There is no

significant change in charge distribution, neither within the molecule nor at the surface.

no chemistry involved.

Chemisorption

Chemical adsorption (chemisorption) – attachment through chemical reactions;

significant charge redistribution.

Chemical bonds may be anything from ionic to covalent.

Chemisorption vs. Physisorption

Chemisorption Physisorption

Variable depending on Depends of molar

Enthalpy of

type of attachment: mass and polarity:

Adsorption

40 - 800 kJ mol-1 5-40 kJ mol-1

Nature of adsorption irreversible reversible

Max. coverage only monolayers multilayers possible

fast, no activation

Kinetic aspects activation barrier

barrier

Influence on isotherms

physisorption

chemisorption/

physisorption

Example one: chemisorption of O2 on charcoal monolayer

Example two: physisorption of N2 on silica gel multilayer

Understanding isotherms

Important factors describing the amount of gas molecules which adsorb to solid

surfaces at constant temperature and constant pressure [discret point on

isotherm].

Interaction energy between adsorbent and adsorbate (adsorption energy)

Interaction between adsorbate molecules (apparent in heat of condensation)

Mobility of the adsorbed molecules

Surface heterogenities

Existence of pores and

pore size distribution

Understanding isotherms

Type I: relatively strong

adsorption, resulting in

monolayer formation

Typ II: polylayer formation

with strong interaction

Typ III:polylayer formation

with low interaction

Typ IV und V: adsorption

at porous surfaces

Quantitative description of adsorption

How to we quantitatively describe isotherms?

[Engineers like math]

Literature survey brings about around 50 different mathematical equations, which

are based on different models and which are making different assumptions to

describe an adsorption process.

At the moment no standard theory of adsorption

Henry isotherm

1903/07 Henry, Dalton Henry

Monolayer adsorption at solid surfaces

Adsorption layer is mobile

No interactions between adsorbed

molecules in the adsorbate

Dalton

bc

: coverage

b : Adsorption coefficient

c: concentration of the volume

Langmuir isotherms

Langmuir 1918

Accounts for footprint of molecules Kc k ads

, K

Initially coverage increases 1 Kc k des

linearily, then levels of to reach a

plateau

Equilibrium:

Adsorption: c + * c* (kads)

Desorption: c* c + * (kdes)

[with c: molecule, *: site, and

k: rate constants]

Irving Langmuir (1881 – 1957)

Born in Brooklyn, New York

Nobel price in Chemistry: 1932

Langmuir isotherms

Kc k ads

, K

1 Kc k des

Maximum coverage: 1

No adsorption beyond monolayer

Langmuir isotherms

Kc k ads

, K

1 Kc k des

High K or c 1

Low K or c Kc (Henry)

Langmuir isotherms

Kc G / RT

K e

1 Kc

Adsorption at a fixed concentration is governed by

thermodynamics enthalpy and temperature are key

Langmuir isotherms

Kc k ads

, K

Shortcomings of the theory: 1 Kc k des

Chemists understand it.

Large molecules may occupy more than one adsorption site

Does not account for multilayer builtup.

Coverage does not influence the probability of adsorption to a site.

All sites are equal, i.e. not influenced by the neighbor. No site-

dependent rate constants.

Langmuir isotherms

Example: Adsorption of colloids or nanoparticles

Currently heavily pursued field of research.

Description is difficult because ... reality bites:

Substrates are rough

Bunch of interactions between particles and particle/substrate:

electrostatic, vdW or steric arguments (entropic)

Transport mechanisms

Desorption processes? (often: irreversible adsorption)

Langmuir model yields only crude approximation

Random Sequential Adsorption (RSA model)

Sequential adsorption at free sites

No diffusion at the surface, no displacement

= 86.5%

Monolayers only

New particle is admitted to a large enough site

“Random Car Parking” problem

Random Sequential Adsorption (RSA model)

squares 0.56

spheres 0.56

At t=0: empty substrate

Monotonic increase in coverage with t

Jammed state: remaining sites are too small

Coverage lower than in close-packed state

Random Sequential Adsorption (RSA model)

(a) = 0.56,

(b) = 0.5 (aspect ratio 4),

(c) = 0.45

(d) = 0.38

RSA – an example

Practical use of isotherms: BET method

A method to determine surface areas of powders

1 1

N amount of gas adsorbed in

equilibrium

Nmono monolayer capacity

C constant including heat of adsorption

and condensation

P equilibrium pressure

P0 saturation vapor

Assumptions:

• gas molecules physically adsorb on a solid in layers infinitely

• there is no interaction between each adsorption layer

• the Langmuir theory can be applied to each layer

1. Your company „CoolCoats“ produces coatings for

electrochemical sensors. A batch of these sensors was
accidentally exposed to a gas during the production
process and eventually these sensors did not pass quality
control. You believe that the problems are caused by a
chemical reaction between the gas and the surface, but
you cannot completely rule out that physisorption took
place. How can you distinguish between these two
sorption phenomena?
1. Your company „CoolCoats“ produces coatings for electrochemical sensors. A batch of these
sensors was accidentally exposed to a gas during the production process and eventually these
sensors did not pass quality control. You believe that the problems are caused by a chemical
reaction between the gas and the surface, but you cannot completely rule out that physisorption took
place. How can you distinguish between these two sorption phenomena?
2. Briefly discuss the differences between the Henry and the Langmuir model for the
description of adsorption processes! Which circumstances lead to similar results for both
models?

Henry doesn’t account for the footprint of

the adsorbed molecules on the surface,
therefore adsorption is assumed not to be
influenced by the availability of adsorption
sites/interaction between adsorbed
molecules -> adsorption continues
infinitely…
Langmuir accounts for that -> initially
linear adsorption behavior, with reduced
adsorption rates when more adsorption
sites are already occupied/interaction
occurs
Small Concentrations or small K values
lead to similar results of Langmuir and
Henry equation
2. Briefly discuss the differences between the Henry and the Langmuir model for the
description of adsorption processes! Which circumstances lead to similar results for both
models?