Single Surface Area Measurements

(FlowSorb II---BET)
Louis Scudiero
Washington State University
Instrument description
The FlowSorb II instrument shown below in figure 1 permits measurements of (1)
single point surface area and (2) multipoint surface area measurements, (3) total pore
volume, and (4) distribution of pore wall area and pore volume as a function of pore size.

(3)

(1)

(4)

(5)
(6)
(2)
(7)
(8)

Figure 1 FlowSorb II

The instrument consists of a flowmeter (1), a heating mantle (2), a surface area display
with zero adjustment knobs (3), 2 U shape tube (mounted at degas and test) (4), a cold
trap with Dewar (5), a toggle switch for gas selection (6) and a Dewar for cooling (gas
adsorption) (7) and a beaker containing room temperature water (8) for heating (gas
desorption) experiments.

Theory taken from Appendix 1 [Micromeritics instruction manual for Flowsorb II

2300 (1986)]
One form of BET equation that describes the adsorption of a gas upon a solid surface is
P

P0

P
V 1
P0

(Vm C ) + (C 1)V C P
m P0

(1)

Where V is the volume of gas adsorbed at pressure P (under std temperature and
pressure, STP), P0 the saturation pressure which is the vapor pressure of liquefied gas at
the adsorbing temperature, Vm the volume of gas (STP) required to form an adsorbed
monomolecular layer, and C a constant related to the energy of adsorption.
The surface area S of the sample giving the monolayer adsorbed gas volume Vm is then
calculated from

S=

Vm AN
M

(2)

where A is Avogadros number (in number of gas molecules in a mole of gas at STP), M
the molar volume of the gas, and N the area of each adsorbed gas molecule.
In this experiment the single point surface area measurement will be used. Therefore the
constant C in equation 1 is typically a large number (C >> 1). The equation 1 reduces to
P

P0

P
V 1
P0

1
Vm

1 P
+
C P0

(3)

Now if P/P0 >> 1/C Eq. 3 can be further simplified

P

P0

P
V 1
P0

Finally Eq. 4 can be rearranged to give

1 P
Vm P0

P
Vm = V 1
P0

Substituting Eq. 5 into Eq. 2 we get to the final expression

(4)

(5)


P
S = VAN 1 M
P0

(6)

The expression gives the sample surface area once the volume V of gas adsorbed (or
desorbed) is measured.

Procedure for Single Point Surface Area Measurements

Power on the instrument and allow gas mixture to flow in the selected path (short
for this experiment) for at least 30 minutes before measurements. The power switch is
located on the right side of the instrument. Lift up the gas switch that is below the power
switch to allow gas in (see figure 2).

Power

Gas

Figure 2: Power and gas switches

1. Start-up
Remove the U-shape tube from the DEDAS and weigh it accurately. Add a small
amount of Alumina powder using the provided funnel and weigh the U-shape tube again.
The difference will give the amount of alumina in the sample holder. This amount should
be about 50 -200 mg. Place the tube containing the Alumina at the DEGAS position,
slide on the heating mantle and plug the power cord and connect the thermocouple jack
(see figure 3). The temperature dial is set to 150 C which is an adequate temperature for

degassing alumina. This will take between 15 to 30 min. In the meantime you need to
calibrate the FlowSorb II following the procedure outlined below.

Sample glass tubes

Mantle and
Thermocouple outlets
2 position hinged tray
Dewar support
Figure 3: U-shape tube with sample in the DEGAS position

2. Calibration
This is done by injecting 1 mL of a gas mixture into the instrument through the
septum. The resulting volume measured should be equal to the calibration value which is
calculated using the following expression.

273.15 AtmP N A N % N 2 atmP

1
S = v

RmT 760 Vm 100 SatP

(7)

Where v is the volume of gas injected (1 mL), NA = 6.023x1023 molecule/gram mole is

the Avogadro number, N = 16.2x10-20 m2 is the accepted value for area of a solid surface
occupied by an adsorbed N2 molecule and Vm = 22.414 L/gram mole is the molar volume
of a gas at standard conditions.

The saturated pressure of liquid nitrogen is typically 15 mmHg greater than the
atmospheric pressure.
Example: For Patm = 702 mmHg, RmT = 23 C and %N2 = 20 the value of S will be equal
to (8)

20

P
P
N

100 atm
273.15 atm A
S := v

296.15 760 Vm
Psat

S = 2.982m

This calculated value of S will be used to calibrate the surface area as described below.
a) Fill the 1 mL syringe with 1mL of gas (N2 from cylinder or from LN2). If LN2 is
used allow 2 to 3 min for the gas temperature to reach room temperature.
b) Set on SHORT PATH unless a large volume of gas will be adsorbed.
c) Dewar tray (TEST) is in the down position.
d) Adjust the gas flow in the flowmeter to have the ball at the orange mark or slightly
lower. (A gas flow around 35 40 will allow easy adjustment of the calibration value for
the surface area)
e) Depress DET and X1 pushbuttons.
f) After equilibrium, zero the Digital DISPLAY using COARSE/FINE ZERO.
g) Depress SURFACE AREA pushbutton.
h) CLEAR SA DISPLAY.
i) Inject slowly the 1 mL of gas.
j) THRESHOLD light will begin to flash after 1 2 minutes (counting).

When

counting ceases, use the CALIBRATION knob to adjust the SA value to the S value as
calculated above (20% N2, S = 2.982 m2) if needed.

Figure 4: Clear SA display and Threshold

pushbuttons

Figure 5: Display meter and the different

reading functions.

k) Repeat from step (e) to confirm calibration. The surface area value should read 2.98
m2 for 20% gas mixture after the three injection or DET should read 0.00 0.02.

Figure 7: Inject port for calibration of

the Flowsorb

Figure 6: Calibration and coarse and fine

adjustment knobs

Note that the calculated S value of 2.98 is only for the 20% mixture if a different gas
mixture is used the value of S needs to be recalculated for that mixture using Eq. 8.

3. Surface area measurements

At this point you have to switch sample holder from DEGAS to TEST as fast as possible
to avoid air to accumulate in the column.
a) Adjust the gas flow rate if necessary.
b) Adjust the level of liquid nitrogen about the cold trap if needed.
c) Depress DET, pushbutton.
d) After air pulse passes, depress SURFACE AREA pushbutton. (X1 is fine for
this experiment)
e) Place the Dewar containing the liquid nitrogen (LN2) about the sample and
adjust its level.
f) Depress CLEAR SA DISPLAY pushbutton to clear display of adsorption
result when counting ceases.
g) Counting will starts after a couple of minutes and could last for several
minutes (up to 15 min). The THRESHOLD light will indicate when the counting
starts and when it ceases (no flashing for 15 20 seconds). Record the value of
the sample surface area that is displayed. This is the adsorbed surface area of the
sample.

h) Remove LN2 Dewar and promptly warm up the sample using a beaker
containing water at room temperature. For this measurement the Dewar support
has to be in the low position as shown in figures 1 and 3
i) Assure that the gas flow rate has returned to normal before counting begins.
j) After counting ceases (THRESHOLD light stops flashing for 15 20
seconds), record value displayed as the sample surface area.
You should repeat the measurements at least twice and if time permits use a different
gas mixture (30%) and repeat the measurements.

Calculations and Discussions

1. Record adsorbed (using LN2) and desorbed (water beaker at RT) surface area of
alumina. Compare these values (in m2/gram) with the surface area value given on
the bottle. Perform an error analysis.
2. Discuss some of the approximations that are made in order to determine this
value.
3. Describe what the isotherm would look like if the partial pressures of N2 used
approached one atmosphere pressure?
4. Would the experimental surface area be higher or lower if the conditions for BET
theory were not met? Explain.