Chem 353

Physical Chemistry II
Part III. Change
Chapter 22 – Processes on Solid Surfaces
22A An introduction to solid surfaces
22B Adsorption and desorption
22C Heterogeneous catalysis

2019 Fall Semester

22B.1 Adsorption isotherms
Isotherm: an eqn relating one property to another at constant T.
Adsorption isotherm: an eqn relating amount of adsorbate on the absorbent to the
concentration of adsorbing molecules in gas or liquid phase (moving phase) at a fixed
temperature.
(An equation that relates the amount of a substance to a surface to its concentration in the gas phase or in solution, at a
fixed temperature, is known as an adsorption isotherm.)
SIX TYPES OF SORPTION-ISOTHERMS by IUPAC 1985

Adsorbate

Surface (Adsorbent)
(a)Langmuir Isotherm Adsorbate
22B.1 Adsorption isotherms
Surface (Adsorbent)

• Simplest isotherm developed by Irving Langmuir

Assumptions:
1) All parts of the surface are equal and behave exactly the same (no preference of
adsorption on sites)
2) Monolayer coverage
3) Adsorption of a molecule to a site is independent of neighbors
(no interaction btw adsorbed molecules)
TYPE I:
Pores are typically microporus with the exposed surface residing
almost exclusively inside the microspores, which once filled with
adsorbate, leave little or no external surface for further adsorption.

~1015 molecules cover 1 cm2 of the surface

(a)Langmuir Isotherm
22B.1 Adsorption isotherms

Adsorption:
• Suppose that a dynamic equilibrium is established Assumptions:
1) All parts of the surface are equal and
A behave exactly the same
| | 2) Monolayer coverage
𝑘𝑎 3) Adsorption of a molecule to a site is
𝐴 + −𝑆 − ֞ − 𝑆 − independent of neighbors
𝑘𝑑

 a fraction 𝜽 of the surface is covered and

 a fraction 𝟏 − 𝜽 will not be covered. Adsorbate
𝜽 = extend of coverage
Surface (Adsorbent)
# 𝒐𝒇 𝒂𝒅𝒔𝒐𝒓𝒑𝒕𝒊𝒐𝒏 𝒔𝒊𝒕𝒆𝒔 𝒐𝒄𝒄𝒖𝒑𝒊𝒆𝒅
𝜽=
# 𝒐𝒇 𝒂𝒅𝒔𝒐𝒓𝒑𝒕𝒊𝒐𝒏 𝒔𝒊𝒕𝒆𝒔 𝒂𝒗𝒂𝒍𝒊𝒂𝒃𝒍𝒆
(a)Langmuir Isotherm Assumptions:
1) All parts of the surface are equal and
22B.1 Adsorption isotherms behave exactly the same
2) Monolayer coverage
3) Adsorption of a molecule to a site is
independent of neighbors
Adsorption:
𝒅𝜽
Rate of change of surface coverage due to adsorption: = 𝒌𝒂 𝒑 𝑵 𝟏 − 𝜽
𝒅𝒕
𝒅𝜽
And rate of change of 𝜽 due to desoprtion : = − 𝒌𝒅 𝑵𝜽
𝒅𝒕
At eq no net change thus sum is zero, thus
𝜽 𝒌𝒂
𝒌𝒂 𝒑 𝑵 𝟏 − 𝜽 = 𝒌𝒅 𝑵𝜽 ⇒ = 𝒑=𝜶𝒑
𝟏 − 𝜽 𝒌𝒅

𝜶𝒑 Langmuir
𝜽= Isotherm
𝟏 + 𝜶𝒑

Rem 𝜽 = 𝑽/𝑽∞
Volume correspond to complete coverage
(a)Langmuir Isotherm
22B.1 Adsorption isotherms Assumptions:
1) All parts of the surface are equal and
behave exactly the same
2) Monolayer coverage
3) Adsorption of a molecule to a site is
independent of neighbors
Adsorption:
Rate of adsorption: 𝝊𝒂 = 𝒌𝒂 𝑨 𝑵 𝟏 − 𝜽
and rate of desorption: 𝝊𝒅 = 𝒌𝒅 𝑵𝜽
At eq: 𝝊𝒂 = 𝝊𝒅 thus
𝜽 𝒌𝒂
𝒌𝒂 𝑨 𝑵 𝟏 − 𝜽 = 𝒌𝒅 𝑵𝜽 ⇒ = 𝑨 =𝑲𝑨
𝟏 − 𝜽 𝒌𝒅

𝑲𝑨 Simple
𝜽= Langmuir
𝟏 + 𝑲[𝑨]
Isotherm
(a)Langmuir Isotherm
22B.1 Adsorption isotherms
𝜶𝒑 𝟏 𝟏
𝜽= 𝑶𝑹 =𝟏+
𝟏+𝜶𝒑 𝜽 𝜶𝒑
𝑲𝑨 𝟏 𝟏
𝜽= 𝑶𝑹 =𝟏+
𝟏 + 𝑲[𝑨] 𝜽 𝑲[𝑨]
𝑨𝒕 𝑨 = 𝟎 ⇒ 𝜽 = 𝟎
𝑨𝒕 𝑨 = ∞ ⇒ 𝜽 = 𝟏

𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒

𝐾 𝐴 ≫1

𝑣𝑒𝑟𝑦 𝑙𝑜𝑤 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒

𝐾[𝐴] ≪ 1
 Adsorption with Dissociation
• Chemisorption w/dissociation of a molecule
(Adsorption of a single molecule occupy more sites)
A A
| | 𝑘𝑎 | |
𝐴2 + −𝑆 − 𝑆 − ֞ −𝑆 − 𝑆 −
𝑘𝑑
𝐴𝑑𝑗𝑎𝑐𝑒𝑛𝑡 𝑠𝑖𝑡𝑒𝑠
A. Hussain et al.,
𝜐𝑎 = 𝑘𝑎 𝐴 [𝑁 1 − 𝜃 ]2 𝑎𝑛𝑑 𝜐𝑑 = 𝑘𝑑 𝑁2𝜃2 Topics in Catalysis, 54, 415-423, 2011.

At eq. 𝜐𝑎 = 𝜐𝑑 thus

𝜃 𝑘𝑎
1/2
𝑲𝟏/𝟐 𝑨 𝟏/𝟐 (𝜶𝒑)𝟏/𝟐
1−𝜃
=
𝑘𝑑
𝐴 𝑜𝑟 𝜽 =
𝟏 + 𝑲𝟏/𝟐 𝑨 𝟏/𝟐
𝒐𝒓 𝜽=
𝟏 + (𝜶𝒑)𝟏/𝟐
 Adsorption with Dissociation
(𝜶𝒑)𝟏/𝟐 𝟏 𝟏
𝜽= 𝒐𝒓 =𝟏+
𝟏 + (𝜶𝒑)𝟏/𝟐 𝜽 (𝜶𝒑)𝟏/𝟐
𝑲𝟏/𝟐 𝑨 𝟏/𝟐 𝟏 𝟏
𝜽= 𝒐𝒓 = 𝟏 + 𝟏/𝟐
𝟏 + 𝑲𝟏/𝟐 𝑨 𝟏/𝟐 𝜽 𝑲 𝑨 𝟏/𝟐

𝑨𝒕 𝑨 = 𝟎 ⇒ 𝜽 = 𝟎
𝑨𝒕 𝑨 = ∞ ⇒ 𝜽 = 𝟏

𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒

𝐾 1/2 𝐴 1/2 ≫ 1

Similar to nondissociative coverage

𝑣𝑒𝑟𝑦 𝑙𝑜𝑤 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒
𝐾 1/2 𝐴 1/2 ≪ 1
Example

Benzene adsorbed on graphite is found to obey the Langmuir isotherm to a good approximation. At a pressure of 1.00 Torr
the volume of benzene adsorbed on a sample of graphite was found to be 4.2 mm3 at STP (0 C and 1 atm pressure); at
3.00 Torr it was 8.5 mm3. Assume a benzene molecule to occupy 30 Å2 , estimate the surface area of the graphite.
Solution
𝑽 𝜶𝒑
Remember: 𝜽 = 𝑽 𝒂𝒏𝒅 𝜽 = 𝟏+𝜶𝒑 ; Let the saturated surface coverage is 𝑽∞ = X mm3;
∞

𝟒.𝟐 𝟏.𝟎𝜶 𝟖.𝟓 𝟑.𝟎 𝜶

at 1 torr 𝜽 = = 𝟏+𝟏.𝟎𝜶 and at 3 torr 𝜽 = = 𝟏+𝟑.𝟎𝜶
𝑿 𝑿

𝟒. 𝟐 𝟏. 𝟎𝜶/(𝟏 + 𝟏. 𝟎𝜶)
= ⇒ 𝜶 = 𝟎. 𝟑 𝒂𝒏𝒅 𝑽∞ = 𝟏𝟕. 𝟒 𝒎𝒎𝟑
𝟖. 𝟓 𝟑. 𝟎𝜶/(𝟏 + 𝟑. 𝟎𝜶)

The maximum amount of benzene adsorbed is thus 17.4 mm3.

1 mol at STP occupies 22.4 L = 2.24107 mm3
17.4 mm3 is thus 17.4/(2.24107) mol = 7.7710-7 mol
=7.7710-7  6.0221023 = 4.681017 molecules.

The estimated area of the surface is thus

4.68101730 Å2 = 1.401019Å2 = 0.140 m2
Example
A surface is half-covered by a gas when the pressure is 1 bar. If the simple Langmuir isotherm applies:
a. What is K?
b. What pressures give 75%, 90%, 99%, 99.9% coverage?
c. What coverage is given by pressures of 0.1 bar, 0.5 bar, 1000 bar?

Solution
a. K  1 bar
K [A] K  1 bar 1
θ 0.5 
1  K [A] 1  K  1 bar

b.
P  1 bar 1 θ
θ P θ  0.75  P  3 bar
1  P  1 bar 1 1 θ
θ  0.90  P  9 bar
θ  0.99  P  99 bar
θ  0.999  P  999 bar
c.
P  1 bar 1
θ P  0.1 bar  θ  0.091
1  P  1 bar 1
P  0.5 bar  θ  0.33
P  1000 bar  θ  0.999
Example
The following results were reported by Langmuir for the adsorption of nitrogen on mica at 20 C:

Pressure/atm 2.8 4.0 6.0 9.4 17.1 33.5

Amount of gas
adsorbed/mm3 12.0 15.1 19.0 23.9 28.2 33.0
at 20 C and 1 atm
a. Make a linear plot of these values in order to test the Langmuir isotherm. If it applies, evaluate the
constant K.
b. Suppose that 1015 molecules cover 1 cm2 of the surface. Make an estimate of the effective area in
Langmuir’s experiment.
Solution
The amount x adsorbed is proportional to  and therefore,
aK [A]
x  aθ 
1  K [A]
To convert atmospheres to concentrations:
n P P /atm
  mol dm  3
V RT 0.08205  293.15
To convert amount of gas adsorbed to moles:

PV 1(atm)V V /mm 3
n  1
 mol
RT 0.08205  293.15 atm dm mol
3
10  0.08205  293.15
6

Concentration/mol dm-3 0.116 0.166 0.249 0.391 0.711 1.39

Amount adsorbed/10-7 mol 4.99 6.28 7.90 9.94 11.7 13.7

a. A linear plot may be obtained by plotting 1/x against 1/[A]:

aK [A] 1 1 1
x  
1  K [A] x aK [A] a

[A]-1/mol dm-3 8.62 6.02 4.02 2.56 1.41 0.719

x-1/106 mol 2.00 1.59 1.27 1.01 0.85 0.73
2.5

1.5 1
 0.615  10 6 a  1.63  10 6 mol
a
1 1 K  3.82 dm 3 mol 1
 0.161 10 6
aK
0.5
y = 0.1611x + 0.6147
R² = 0.9996
0
0 5 10

b.
Complete coverage, a, corresponds to
1.6310-6 mol = 9.821017 molecules
Using the knowledge that 1015 molecules covers 1 cm2 of the surface, the surface
area was thus about
9.82 1017/1015 = 103 cm2=10-1 m2
(b)The isosteric enthalpy of adsorption
22B.1 Adsorption isotherms
𝝏𝒍𝒏 𝜶𝒑𝒐 𝚫𝐚𝐝𝐬 𝐇 𝐨
=
𝝏𝑻 𝜽
𝑹 𝑻𝟐

Rem: 𝜶𝒑 = 𝜽/(𝟏 − 𝜽) when 𝜽 is const. 𝜶𝒑 is constant.

𝒑 𝒑 𝒑
Thus 𝜶𝒑𝒐 = const. And 𝐥𝐧 𝜶𝒑𝒐 = 𝐥𝐧 𝜶𝒑𝒐 + 𝐥𝐧 = 𝒄𝒐𝒏𝒔𝒕.
𝒑𝒐 𝒑𝒐 𝒑𝒐
𝒑
𝝏 𝐥𝐧 𝒑𝒐
𝒑 𝝏 𝒄𝒐𝒏𝒔𝒕. 𝝏 𝐥𝐧 𝜶𝒑𝒐 𝚫𝐚𝐝𝐬 𝐇𝐨
𝐥𝐧 = 𝒄𝒐𝒏𝒔𝒕. −𝐥𝐧 𝜶𝒑𝒐 => = − = −
𝒑𝒐 𝝏𝑻 𝜽 𝝏𝑻 𝝏𝑻 𝐑𝐓 𝟐

𝝏 𝐥𝐧 𝒑/𝒑𝒐 𝜟𝒂𝒅𝒔 𝑯𝒐
= A plot of ln (p/po) against 1/T is a straight line
𝝏(𝟏/𝑻) 𝜽
𝑹 with a slope of 𝜟𝒂𝒅𝒔 𝑯𝒐 /R
(c)BET Isotherm
22B.1 Adsorption isotherms

• Allows physisorption of additional layers above

the monolayer
• A multilayer model http://www.jhu.edu/~chem/fairbr/OLDS/derive.html

• Assumes Langmuir model applies to each layer. Applications:

• Pharmaceuticals
• Catalysts
𝑉: 𝑣𝑜𝑙. 𝑜𝑓 𝑔𝑎𝑠 𝑎𝑑𝑠𝑜𝑟𝑏𝑒𝑑 • Projectile propellants
𝑉 𝑐𝑧 𝑉𝑚𝑜𝑛 : 𝑉𝑜𝑙. 𝑜𝑓 𝑚𝑜𝑛𝑜𝑙𝑎𝑦𝑒𝑟 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒 • Medical implants
= 𝑐: 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 • Filters
𝑉𝑚𝑜𝑛 1 − 𝑧 {1 − 1 − 𝑐 𝑧} 𝑧: 𝑝/𝑝∗ • Cements

(Δ𝑑𝑒𝑠 𝐻 𝑜 −Δ𝑣𝑎𝑝 𝐻 𝑜 )/𝑅𝑇

𝑐=𝑒
• It is better to use to estimate the surface area
𝑉 1 • BET method can be used to measure TYPE II
= 𝑤ℎ𝑒𝑛 𝑐 ≫ 1 (nonporous), IV(weak substrate) and VI(layering)
𝑉𝑚𝑜𝑛 1−𝑧 isoterms.
(c)BET Isotherm
22B.1 Adsorption isotherms

OR

𝑧 1 𝑐−1 𝑧 http://www.jhu.edu/~chem/fairbr/OLDS/derive.html

= +
1 − 𝑧 𝑉 𝑐𝑉𝑚𝑜𝑛 𝑐𝑉𝑚𝑜𝑛

OR

𝑝 1 𝑐−1 𝑝
∗
= +
𝑉 𝑝 −𝑝 𝑐𝑉𝑚𝑜𝑛 𝑐𝑉𝑚𝑜𝑛 𝑝∗
Other Isoterms
Adsorption Isotherms
Deviation from ideality:
• Surfaces are not uniform or homogeneous
• Adsorption of one species may favor or inhibit the adsorption of the others.
• the enthalpy of adsorption often becomes less negative as θ increases,
which suggests that the energetically most favourable sites are occupied
first.

Temkin Isoterm
• Considers no saturation!!!
• Fit of a system behavior to an empirical 𝜽 = 𝒄𝟏 𝐥𝐧 (𝐜𝟐 𝐩)
formula
• Consider that adsorption enthalpy c1 and c2 are constants
changes linearly with pressure.
 Other Isoterms Deviation from ideality:
Adsorption Isotherms
• Surfaces are not uniform or homogeneous
• Adsorption of one species may favor or inhibit the adsorption of the others.
• the enthalpy of adsorption often becomes less negative as θ increases, which
suggests that the energetically most favourable sites are occupied first.

Freundlich Isoterm
• Considers no saturation!!!
• Fit of a system behavior to an empirical formula
• Attemps to incorporate the role of substrate-substrate interactions on the surface
• Good for heterogeneous surface energies.

𝒙 = 𝒌 𝒄𝒏 (𝐧 < 𝟏 𝐢𝐧 𝐠𝐞𝐧𝐞𝐫𝐚𝐥)
𝜽 = 𝒄𝟏 𝑷𝟏/𝒄𝟐
Amount of
substance Empirical
c1 and c2 are constants
absorbed constants
22B.2 The rates of adsorption and desorption
22B.2 The rates of adsorption and desorption
22B.2 The rates of adsorption and desorption
22B.2 The rates of adsorption and desorption
22B.2 The rates of adsorption and desorption
Temperature programmed desorption (TPD)
or thermal desorption spectroscopy (TDS).
Temperature programmed desorption
22B.2 The rates of adsorption and desorption

𝐷: Diffusion coefficient
𝐷0 : Diffusion coefficient in the limit of infinite temperature