HORIBA Scientific

Particle Analysis

Carl Lundstedt

BET Theory and how its used to

calculate surface area

June 25, 2019

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 BET Theory seeks to explain the physical
adsorption of gas molecules onto solid surfaces

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 Particles of similar size can vary drastically in
surface area

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 Physical adsorption occurs due to Van der Waals forces
when at low temperatures and without chemical reactions

Adsorbate

Adsorbent

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 BET Theory extends the Langmuir theory from
monolayer adsorption to multilayer adsorption

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 We use the BET equation to determine the
monolayer absorbed gas volume (vm)

1 𝑐𝑐 − 1 𝑝𝑝 1
= +
𝑣𝑣[(𝑝𝑝0 /𝑝𝑝) – 1] 𝑣𝑣𝑚𝑚 𝑐𝑐 𝑝𝑝0 𝑣𝑣𝑚𝑚 𝑐𝑐

𝑣𝑣 = adsorbed gas quantity

𝑝𝑝0 = saturation pressure of adsorbate
𝑝𝑝 = equilibrium pressure of adsorbate
𝐸𝐸 −𝐸𝐸
𝑐𝑐 = BET constant = exp 1 𝐿𝐿
𝑅𝑅𝑅𝑅
𝐸𝐸1 = heat of adsorption for the first layer
𝐸𝐸𝐿𝐿 = heat of vaporization

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 BET equation can be plotted to determine monolayer
adsorbed gas quantity and the BET constant

1 𝑐𝑐 − 1 𝑝𝑝 1
= +
𝑣𝑣[(𝑝𝑝0 /𝑝𝑝) – 1] 𝑣𝑣𝑚𝑚 𝑐𝑐 𝑝𝑝0 𝑣𝑣𝑚𝑚 𝑐𝑐

𝑦𝑦 = 𝑚𝑚𝑥𝑥 + 𝑏𝑏

1
𝑣𝑣[(𝑝𝑝0 /𝑝𝑝) – 1]

𝑐𝑐 − 1
𝑣𝑣𝑚𝑚 𝑐𝑐

1
𝑣𝑣𝑚𝑚 𝑐𝑐
𝑝𝑝
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𝑝𝑝0 7
 Take numerical values for slope and intercept to
solve for vm and c

𝑐𝑐 − 1
𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 =
𝑣𝑣𝑚𝑚 𝑐𝑐
1
intercept =
𝑣𝑣𝑚𝑚 𝑐𝑐
1
𝑣𝑣𝑚𝑚 =
𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 + 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
𝑐𝑐 = 1 +
𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖

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 From the monolayer absorbed gas volume (vm),
we can determine total and specific surface area

𝑣𝑣𝑚𝑚 𝑁𝑁𝑁𝑁
𝑆𝑆𝑡𝑡 =
𝑉𝑉
𝑆𝑆𝑡𝑡 = total surface area of sample material
𝑣𝑣𝑚𝑚 = monolayer absorbed gas volume
𝑁𝑁 = Avogadro’s number = 6.02 x 1023 molecules/mol
𝑠𝑠 = cross-sectional area of adsorbed gas molecule
𝑉𝑉 = molar volume of adsorbed gas
𝑆𝑆𝑡𝑡
𝑆𝑆𝐵𝐵𝐵𝐵𝐵𝐵 = [=] m2/g
𝑎𝑎

𝑆𝑆𝐵𝐵𝐵𝐵𝐵𝐵 = specific surface area

𝑎𝑎 = mass of sample

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 Can only assume linear relationship for adsorption
isotherms in the range of 0.05 < 𝑝𝑝/𝑝𝑝0 < 0.30

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 Pore width can make a big difference on shape of
isotherm

Micropores Mesopores Macropores

Zeolite, Mesoporous silica, Sintered metals

Activated Activated carbon and ceramics
carbon,
Metal organic
framework
2 nm 50 nm

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 Usually apply BET theory to Type 2 and Type 4
isotherms, apply to Type 1 with caution

Macroporous/
Microporous non-porous
(C > 150) (C > 80) (C < 2)

Mesoporous Step-wise
(C > 80) (C < 2) multilayer
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 Have to insert sample into cell and degas sample to
remove excess moisture on surface

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 BET measurement includes calibration of 1 cm3 of
nitrogen, adsorption, and desorption

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 Large surface area samples will adsorb and desorb
more nitrogen

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 BET multipoint measurement example

1st point 2nd point 3rd point

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 Plot at least 3 points to obtain multi-point plot, solve
for BET constant (c) and Vm (monolayer volume)

BET constant = 145.84

Surface area = 11.36 m2/g

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 19
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