CHY1009 ; Module 2

-States of mater and adsorption isotherms

Dr. K. Selvakumar
VITAP University
[email protected]
Sates of mater
The Physical States of Matter - Particulate
theory of matter
Greek philosopher Democritus described matter as made up of tiny
microscopic particles.

the particulate theory of matter was first presented by Democritus

in 400 BC
Traditionally there are three states of matter
The Physical States of Matter - Particulate
theory of matter

John Dalton who is credited with first developing the modern

atomic theory of matter in the early 1800s.

The theory presented by Democritus was predominately a

philosophical statement and therefore not widely accepted.

In contrast, Dalton’s theory was based on careful experimental

observations and measurements and so became the first atomic
theory of matter founded on scientific concepts and principles.

According to the modern atomic theory, matter can be classified

according to both its physical and chemical state
The Physical States of Matter - Particulate
theory of matter
Physical States of Mater- Properties

Gas Liquid Solid

These characteristics affect the physical properties of matter,

such as volume occupancy, density, light scattering, etc.,
Density (mass/cm3) of Gas, Liquid, Solids

ρ = mass/unit volume = M/V

For a given mass of substance, density increases while going

from gas-to-liquid and liquid-to-solid.

Interparticle distance decreases, this decreases volume.

Density (ρ ) ∝ 1/Volume (V)

Density (mass/cm3) of Gas, Liquid, Solids - Examples

Solid Gas
Liquid (g/cm3)
(g/cm3) (g/cm3)
Ar 1.65 1.40 0.001784
N2 1.026 0.8081 0.001251
O2 1.426 1.149 0.001429

-the density of a typical solid is about 20% larger than the

corresponding liquid,

-while the liquid is roughly 800 times as dense as the gas.

Plasma – 4th states
of Matter
• Plasma is a “superheated matter”
comprised of ions formed from atoms or
molecules by striping of at least one electron.

• It comprises over 99% of the visible universe.

• In the night sky, plasma glows in the form of

stars, nebulas, and even the auroras that
sometimes ripple above the north and south
poles.

• Plasma is often called “the fourth state of

matter,” along with solid, liquid and gas.
https://www.nasa.gov/sites/default/files/thumbnails/image/147515main_phases_large.jpg
 Adsorption isotherms
Surface chemistry is the study of processes that occur
at the interface of two bulk phases.

Bulk phase may be a solid or liquid or gas

Liquid - liquid
 Phenomena
Interaction Open of Adsorption
Surfaces
solid
The with ofGases
phenomena interaction of a gas or liquid, or ionic species
with a solid surface is referred as adsorption.

Adsorptive

Adsorbate

Adsorbent
Except in special cases, adsorption is an exothermic process,
releases heat to the surrounding.
Enthalpy change is negative ∆Had = -Ve
 Examples of Adsorption
 (i) Adsorption of O2, H2, CO, Cl2, NH3 or SO2 on surface of charcoal,

 (ii) In a solution of an organic dye, say methylene blue on the

surface of charcoal, i.e., are adsorbed.

 (iii) Aqueous solution of raw sugar, when passed over beds of

animal charcoal, becomes colourless as the colouring substances
are adsorbed by the charcoal.

 (iv) The air becomes dry in the presence of silica gel because the
water molecules get adsorbed on the surface of the gel.

 The process of removing an adsorbed substance from a

surface on which it is adsorbed is called desorption.
 What kind of bonding interaction occurs
between adsorbent and adsorbate?

The attractive interaction can be either long range or short

range

1. Long range interaction: Physical contact, due to Van der

Waals force.

2. Short range interaction: Chemical bonding, such as covalent,

ionic, metallic bonding
Accordingly, the first one is called physisorption (Physical adsorption)
and the second one is called chemisorption (Chemical adsorption).
 Example of Physisorption

Surface of gold atoms

Coronene

Sticking of benzene-like molecules, for example coronene,

on the surface of gold (111) is an example of physisorption.
Example of Chemisorption
Metal hydride is formed through
chemical bonding, hence,
chemisorption.

a) Metal surface (adsorbent)

b) Physisorption of H2 through van der Waals interaction
c) Chemisorptions of H2 through M-H bond (metal hydrides)
d) Chemisorbed H atom may slid into the bulk metal through diffusion
“Chemisorption always accompanied by physisorption”
http://cdn.intechopen.com/pdfs-wm/40231.pdf
 Thermodynamic Considerations
• Adsorption (or any) spontaneous process
requires ∆G < 0. Because the translational freedom
of the adsorbate is reduced when it is adsorbed, ∆S
is negative.
• Therefore, in order for ∆G = ∆ H − T∆S to be
negative, ∆H must be negative (that is, the process is
exothermic).
• Exceptions may occur if the adsorbate dissociates
and has high translational mobility on the surface.
Enthalpies of Physi- and Chemisorption

Exothermic reactions, enthalpy change is negative

Enthalpies of chemisorption are greater than enthalpies of
physisorption. These enthalpies are close to covalent bond enthalpies.
Vs
 Quantitative Models on
Adsorption
Amount of gas adsorbed on a solid depends on T and P (or
concentration of solution species) of the gas in contact with the
solid surface.

The amount of gas adsorbed on the solid surface is studied at

constant temperature.
The plot of amount of gas adsorbed as a function of pressure is
known as adsorption isotherm.

This behavior can be explained by empirical or theoretical models.

 Langmuir Adsorption Isotherm
A
Adsorptive, A(g)

S (Surface of adsorbent)

1. Surface of the adsorbent is homogeneous

2. It has N active sites

number of adsorption sites occupied
3. The fraction of sites adsorbed θ = Na/N 𝑜𝑟 𝜃 =
number of adsorption sites available
4. Surface only allows the formation of monolayer

5. There is no intermolecular interaction between adsorbate

Adsorption isotherms-Solid-Gas interaction
Deriving the Langmuir isotherm

You need to consider the dynamic equilibrium between the molecules

(A) in the gas phase and those on the surface (denoted AM):

rate of adsorption
p partial pressure
N is the total number of sites

rate of desorption

at equilibrium
At equilibrium there is no net change in θ, implying that the sum of these two rates must be
zero:
Adsorption isotherms-Solid-Gas interaction
Deriving the Langmuir isotherm
at equilibrium
At equilibrium there is no net change in θ, implying that the sum of these two rates must be
zero:

solving for θ gives the Langmuir isotherm

Langmuir isotherm

( Some text books use α instead of K)

Adsorption isotherms-Solid-Gas interaction
Langmuir isotherm

Langmuir isotherm
where,
x = mass of adsorbate
m = mass of adsorbent
 Point of saturation

This model is inadequate to explain some cases of adsorption.

In certain cases the adsorption continues even
after the point of Freundlich saturation limit. (for example liquid
condensation).
Adsorption isotherms-Effect of T
Lower the T more the surface coverage (adsorption)
 1
Continued…. 𝑥
𝑚
=𝑘𝑝 𝑛

kf approximately indicates adsorption capacity

1/n is a function of the strength of adsorption

n varies with the nature of the adsorbent and

range for favorable adsorption is of 1-10.

1/n = 0, x/m = constant, the adsorption is

independent of pressure.

1/n = 1, x/m = k P, i.e. x/m ∝ P, the adsorption

varies directly with pressure.

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Limitations of Freundlich Isotherm

Freundlich equation is purely empirical and

has no theoretical basis.

The equation is valid only upto a

certain pressure and invalid at higher
pressure.

Frendilich’s adsorption isotherm fails at

high concentration of the adsorbate.

31
Differences between Freundlich and
Langmuir adsorption isotherms

FRENDLICH ADSORPTION LANGMUIR ADSORPTION

ISOTHERM ISOTHERM
• Tells about the quantity of • Tells about the number
gas adsorbed by unit mass of active site undergoing
of solid adsorbent with adsorption and pressure.
pressure. • Represented by formula
• Represented by formula θ = 𝐾𝑃ൗ1+ KP
x/m = KP1/n

32
Adsorption isotherms-Solid-liquid interaction

mass balance equation

for adsorption

where
qe = mass of material adsorbed (at equilibrium) per mass of adsorbent, mg adsorbate/g
adsorbent
C0 = initial concentration of adsorbate, mg/L
Ce = equilibrium concentration in solution when amount adsorbed equals qe, mg/L
V = volume of liquid in the reactor, L
m = mass of adsorbent, g
Adsorption isotherms-Solid-liquid interaction

Adsorption isotherms: Freundlich isotherm

For the special case that the surface energies are heterogeneous
(particularly good for mixed adsorbates) in which the energy term,
“kF”, varies as a function of surface coverage, the Freundlich
model is appropriate.
The model equation is:

1
𝑛
𝑞𝑒 = 𝑘𝑓 𝐶𝑒

kf and n are system specific constants.

Shape of the Freundlich isotherm changes upon changing the
qe
values of n and k

Ce
Adsorption isotherms-Solid-liquid interaction
Adsorption isotherms: Langmuir model
This model assumes monolayer coverage and constant binding
energy between surface and adsorbate.
The model equation is:

K  Q0a  Ce
qe  ⇒ 𝐶𝑒 1 𝐶𝑒
1  K  Ce = +
𝑞𝑒 𝐾𝑄𝑎 0 𝑄𝑎 0

Q 0a represents the maximum adsorption capacity

(monolayer coverage) (g solute/g adsorbent).

Ce has units of mg/L

K Langmuir equilibrium constant has units of
L/mg
Adsorption isotherms-Solid-liquid interaction
Adsorption isotherms: Langmuir model
𝐶𝑒 1 𝐶𝑒
= +
𝑞𝑒 𝐾𝑄𝑎 0 𝑄𝑎 0

1
Slope =
𝑄𝑎 0

Intercept
1
=
𝐾𝑄𝑎 0
 Application of Adsorbents
• Organic contaminants such as pharmaceuticals, cosmetics,
pesticides can be removed from water using the method of
adsorption.

• To speed up chemical reactions (catalysis)

• To remove bad odor and color in water

• Used as a solid support purify proteins and chemical

compounds

• Used to remove unwanted impurities from gas

38
 Uses of activated carbon as a adsorbent

• Uses
Remove man-made organic chemicals
Remove miscellaneous tastes and
odor from water assuming no bacterial
problems
Remove radon gas from water

• Maintenance
Carbon must be replaced routinely
 Porous Nature of Activated Carbon
Generally activated carbon is porous. They provide large surface area
(m2/g). Pore size depends on the carbon source.
 Problems
Example 1
Adsorption of benzene onto activated carbon has been reported
to obey the following Freundlich isotherm equation, where c is in
mg/L and q is in mg/g:

qbenz  50.1 cbenz

0.533

A solution at 25oC containing 0.50 mg/L benzene is to be treated

in a batch process to reduce the concentration to less than
0.01 mg/L. The adsorbent is activated carbon with a specific
surface area of 650 m2/g.
Compute the required activated carbon dose.
Example 1
Solution:

𝐶0 = 0.5 𝑚𝑔/𝐿 1/𝑛

𝑞𝑒 = 𝑘 𝐶𝑒
qbenz  50.1 cbenz
0.533
𝐶𝑒 = 0.01 mg/L

𝑞𝑒 = ? 𝑞𝑒 = 50.1 (0.01)0.533
𝑚 𝑞𝑒 = 4.30 𝑚𝑔/𝑔
=?
𝑉
Example 1
Solution:

𝐶0 = 0.5 𝑚𝑔/𝐿 𝑚 𝐶0 − 𝐶𝑒
=
𝑣 𝑞𝑒
𝐶𝑒 = 0.01 mg/L
𝑚 0.5 − 0.01 mg/L
𝑞𝑒 = 4.30 mg/g =
𝑣 4.3 mg/g
𝑚
=? 𝑚
𝑉 = 0.114 g/L
𝑣
Example 2
The data given below are for the adsorption of CO on charcoal at 273
K. Confirm that they fit the Langmuir isotherm, and find the constant
K and the volume corresponding to complete coverage.

Solution:
a plot of p/V against p should give a straight
line of slope 1/V∞ and intercept
1/KV∞.

1/Vm = 1/V∞
Example 2
Solution:

y = mx + c 1
Slope = = 0.00900 (from graph)
𝑉∞

𝑉∞ = 111 𝑐𝑚3

1
Intercept = = 1.20 (from graph)
𝐾𝑉∞
Example 3

Determine the maximum P adsorption capacity of this clay

(mg P / g clay).
Example 3 Solution: 𝐶𝑒 1 𝐶𝑒
= +
𝑞𝑒 𝐾𝑄𝑎 0 𝑄𝑎 0