Introduction to Gas Sorption

Introduction to Gas Sorption

2000 Quantachrome Corporation

PHYSISORPTION
Introduction
The Mechanisms of Adsorption
Interpretation of the Multi-point BET Plot
The Single-Point Method
Pore Size Measurement
Micropore Estimation
Introduction
Adsorption of a gas allows the probing of a solid
surface hence the determination of its area.
This includes surface irregularities and pore interiors.
To some extent, adsorption will always occur on
a solid surface exposed to a gas or vapor

The amount adsorbed is a function of
temperature,
gas pressure
interaction potential between gas and solid.
Introduction (continued)
Mathematical expression of gas adsorption will be
introduced.
Subsequent surface area calculation detailed.
Experimental conditions and theoretical considerations for
real-life applications.
Adsorption Process
Adsorbent
Adsorbate Adsorptive
Langmuir behavior
At equilibrium, the rate of arrival of adsorptive and the
rate of evaporation of adsorbate are equal, i.e.
Adsorption = Desorption
Confining adsorption to a monolayer,
the Langmuir equation can be written


KP
KP
V
V
m
+
=
1
Langmuir Equation
V
P
KV V
P
m
+ =
1
Or linearized as:
where V is the volume of gas adsorbed at
pressure P, Vm is the monolayer capacity and K
is a constant for any given gas-solid pair.
BET Equation
Extending the mechanism to multiple layers,
Brunauer, Emmett and Teller derived the little-
more complicated expression
( )( ) ) P P ( C P P ) P P (
) P P ( C
V
V
o o o
o
m
+
=
1 1
Which, when linearized gives...
BET Equation
the familiar form
|
|
.
|

\
|

+ =

0 0
1 1
1 /
1
P
P
C V
C
C V P P V
m m
where Po is the saturated vapor pressure of the gas over the
solid, P/Po is the relative pressure and C is the so-called BET
C-constant which is related to the net heat of adsorption.
Langmuir vs. BET
Langmuir vs. BET
Principles of BET Surface Area
Measurement and Calculation
Determine the monolayer capacity Vm from which the
surface area of the solid can be computed.
Adsorbate most commonly used is nitrogen...
Readily available in high purity
Appropriate coolant, liquid nitrogen, also plentiful.
Gas-solid interaction relatively strong.
Widely accepted cross sectional area.
Measurement
Obtain at least three data points in the relative pressure range
0.025 to 0.30
Plot 1/[V
STP
(Po/P)-1] versus P/Po. It should yield a straight
line if the BET model holds true.
On all surfaces the BET model fails to accurately predict the
multilayer adsorption behavior above P/Po = 0.5 (the onset of
capillary condensation which fills pores with liquid adsorbate)
Calculation
Fit best straight line through BET data set using
least squares regression to find:
C V
C
s slope
m
1
=
C V
i
m
1
= intercept
Calculation (continued)
i s
V
m
+
=
1
v
m av m
t
M
A L V
S =
Solving for V
m

Total surface area, S
t
, is calculated thus
L
AV
= 6.023 x 10
23
A
m
= 0.162 nm
2
M
v
= 22 414 mL nm
2
to m
2
, x 10
18

Interpretation of the Multi-point BET Plot
Never use data points too low in relative pressure.
Never use points too high in relative pressure.
Non-linear BET Behavior
Interpretation of the Multi-point BET Plot
Never use data points too low in relative pressure.
Never use points too high in relative pressure.
Discard those points at low relative pressure which represent
under-equilibrated data...
Under-equilibrated Data
B
Under-equilibrated Data
C
Interpretation of the Multi-point BET Plot
Never use data points too low in relative pressure.
Never use points too high in relative pressure.
Discard those points at low relative pressure which represent
under-equilibrated data.
Never use less than three, preferably five, data points in the
final calculation.
Always use equally, or near equally, spaced data points
whenever possible.
Confirm known or suspected sample characteristics with the
behavior of the BET plot at higher relative pressures.
The Single-point Method
By reducing the experimental requirement to
only one datum point, the single-point method
offers the advantage of simplicity and speed,
often with little loss in accuracy.
0
1 P P V V
m
=
i.e. V
m
= 1/slope
Multi-point/single point/corrected
single point comparison
Sample
No.
Multipoint
BET
(m2/g)
Uncorrected
Single-point
(m2/g)
Uncorrected
Difference
(%)
Corrected
Single-
point
(m
2
/g)
Corrected
Difference
(%)
1 4.923 4.241 -13.9 4.948 +0.51
2 4.286 3.664 -14.5 4.275 -0.26
3 8.056 6.867 -14.8 8.011 -0.56
4 5.957 5.194 -12.8 6.060 +1.73
Pharm. Processing 9-10 (Jan. 1993)
Multi-point/single point/corrected
single point comparison
Sample
No.
Multipoint
BET
(m2/g)
Uncorrected
Single-point
(m2/g)
Uncorrected
Difference
(%)
Corrected
Single-
point
(m
2
/g)
Corrected
Difference
(%)
1 4.923 4.241 -13.9 4.948 +0.51
2 4.286 3.664 -14.5 4.275 -0.26
3 8.056 6.867 -14.8 8.011 -0.56
4 5.957 5.194 -12.8 6.060 +1.73
Corrected by multiplier C/C-2
The Single-point Method
A relative pressure of 0.3 gives good general agreement with
the multi-point method.
A simple first-order empirical correction can be made for the
so-called single point error at P/P0 = 0.3 by multiplying the
single point BET value by C/C-2.
Variation in Single-point BET Surface Area
as a Function of Chosen Relative Pressure
Surface Area Test Methods
ASTM: Carbon C819
Carbon black D3037, D4820
Aluminum oxide C1069
Silica D1993
Ceramics C1251
Catalysts D4780, D4567, D4365, D3663
Pharmaceutical Industry: <846>
Inconvenient Single-point BET Behavior
In certain cases, the single -point value never goes
through a maximum, but continues to increase with
increasing relative pressure.
If there is truly no linear region, then the BET
equation is invalid for that particular sample.
Isotherms of such samples appear to have some
type III character at very low pressure, indicative of
very weak adsorption yet demonstrate enhanced
adsorption within the normal BET range.
Enhanced Adsorption
Can be attributed to cooperative adsorption process.
Described for slit-shaped pores of critical dimensions.
Water on carbon (hydrophobic surface) is a typical example.
Types of Isotherms
S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
Chapman & Hall, NY, NY 1991
Types of Hysteresis
Cylindrical Slit
Tapered/wedge
Tapered/wedge Bottle-neck
Mesopore (Greek meso = middle): 2nm - 50 nm diameter
Macropore (Greek macro = large): >50 nm diameter
Pore Size Distribution
Hysteresis is indicative of the presence of mesopores
and the pore size distribution can be calculated from
the sorption isotherm.

Whilst it is possible to do so from the adsorption
branch, it is more normal to do so from the desorption
branch...
Micropore (Greek micro = small): 0 nm - 2 nm diameter
Pore Size Distribution
AG
ads
= RT(lnP
ads
- lnP
0
)
AG
des
= RT(lnP
des
- lnP
0
)
AG
des
< AG
ads

Adsorption / Desorption
Adsorption =
multilayer formation
Desorption =
meniscus development

Kelvin* Equation
u

cos
rRT
V 2
P
P
ln
0

) P / P log(
.
) A ( r
k
0
15 4
* Lord Kelvin a.k.a. W.T. Thomson
Pore Size
t r r
k p
r
p
= actual radius of the pore
r
k
= Kelvin radius of the pore
t = thickness of the adsorbed film
Statistical Thickness, t
Halsey equation
Generalized Halsey
deBoer equation
Carbon Black STSA
BJH Method
(Barrett-Joyner-Halenda)
Kelvin
2
pore
2
Kelvin pore
r
r
V V
t
t
=
t r r
Kelvin pore
Estimation of Micropores...
the t-plot method
This method uses a mathematical representation of multi-
layer adsorption. The thickness, t, of an adsorbate layer
increases with increasing pressure. The t-curve so
produced is very similar in appearance to a type II
isotherm. For every value of P/Po, the volume adsorbed
is plotted against the corresponding value of t.
If the model describes the experimental data a straight line
is produced on the t-plot...
t-plot Method
(mesoporous only)
1 2 3 4 5 6 7
t ()
Slope = V/t = A
t-plot Method
(in the presence of micropores)
1 2 3 4 5 6 7
t ()
Intercept = micropore volume
t-plot Method
showing a knee
1 2 3 4 5 6 7
t ()
X
X
X
X
X
X
X
C
A
B
A
C
B
Slope A - slope B = area contribution by micropores size C
Micropore (MP) Plot
t (A

)
Gas volume
is converted
to liquid
volume
Differences in tangents yields
pore area distribution assuming
cylindrical geometry
Estimation of Micropores
Dubinin-Radushkevich (DR) Theory
(
(

|
.
|

\
|
|
|
.
|

\
|
=
P
P
log
T
B exp W W
0
2
2
0
|
W = volume of the liquid adsorbate
W
0
= total volume of the micropores
B = adsorbent constant
| = adsorbate constant
A linear relationship should be found between log(W) and log
2
(Po/P)...
Log
2
(Po/P)
L
o
g

(
W
)

Extrapolation
yields Wo
Estimation of Micropores
Dubinin-Radushkevich (DR) Plot
0
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