bet theory and how its used to calculate surface area
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BET Theory and how its used to calculate surface area
HORIBA ScientificParticle Analysis
Carl Lundstedt
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)
1𝑣𝑣[(𝑝𝑝0/𝑝𝑝) – 1]
=𝑐𝑐 − 1𝑣𝑣𝑚𝑚𝑐𝑐
𝑝𝑝𝑝𝑝0
+1𝑣𝑣𝑚𝑚𝑐𝑐
𝑣𝑣 = adsorbed gas quantity𝑝𝑝0 = saturation pressure of adsorbate𝑝𝑝 = equilibrium pressure of adsorbate𝑐𝑐 = BET constant = exp 𝐸𝐸1−𝐸𝐸𝐿𝐿
𝑅𝑅𝑅𝑅𝐸𝐸1 = 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
1𝑣𝑣[(𝑝𝑝0/𝑝𝑝) – 1]
=𝑐𝑐 − 1𝑣𝑣𝑚𝑚𝑐𝑐
𝑝𝑝𝑝𝑝0
+1𝑣𝑣𝑚𝑚𝑐𝑐
𝑦𝑦 = 𝑚𝑚𝑥𝑥 + 𝑏𝑏
1𝑣𝑣[(𝑝𝑝0/𝑝𝑝) – 1]
𝑝𝑝𝑝𝑝0
1𝑣𝑣𝑚𝑚𝑐𝑐
𝑐𝑐 − 1𝑣𝑣𝑚𝑚𝑐𝑐
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Take numerical values for slope and intercept to solve for vm and c
𝑠𝑠𝑠𝑠𝑠𝑠𝑝𝑝𝑠𝑠 =𝑐𝑐 − 1𝑣𝑣𝑚𝑚𝑐𝑐
intercept = 1𝑣𝑣𝑚𝑚𝑐𝑐
𝑣𝑣𝑚𝑚 =1
𝑠𝑠𝑠𝑠𝑠𝑠𝑝𝑝𝑠𝑠 + 𝑖𝑖𝑖𝑖𝑖𝑖𝑠𝑠𝑖𝑖𝑐𝑐𝑠𝑠𝑝𝑝𝑖𝑖
𝑐𝑐 = 1 +𝑠𝑠𝑠𝑠𝑠𝑠𝑝𝑝𝑠𝑠
𝑖𝑖𝑖𝑖𝑖𝑖𝑠𝑠𝑖𝑖𝑐𝑐𝑠𝑠𝑝𝑝𝑖𝑖
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From the monolayer absorbed gas volume (vm), we can determine total and specific surface area
𝑆𝑆𝑡𝑡 =𝑣𝑣𝑚𝑚𝑁𝑁𝑠𝑠𝑉𝑉
𝑆𝑆𝑡𝑡 = total surface area of sample material𝑣𝑣𝑚𝑚= monolayer absorbed gas volume𝑁𝑁 = Avogadro’s number = 6.02 x 1023 molecules/mol𝑠𝑠 = cross-sectional area of adsorbed gas molecule𝑉𝑉 = molar volume of adsorbed gas
𝑆𝑆𝐵𝐵𝐸𝐸𝑅𝑅 = 𝑆𝑆𝑡𝑡𝑎𝑎
[=] m2/g
𝑆𝑆𝐵𝐵𝐸𝐸𝑅𝑅 = specific surface area𝑎𝑎 = 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
2 nm 50 nm
Micropores Mesopores Macropores
Zeolite,Activated carbon,Metal organicframework
Mesoporous silica, Activated carbon
Sintered metals and ceramics
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Usually apply BET theory to Type 2 and Type 4 isotherms, apply to Type 1 with caution
Microporous(C > 150)
Macroporous/non-porous(C > 80)
Mesoporous(C > 80) (C < 2)
(C < 2)
Step-wisemultilayer
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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
3rd point2nd point1st 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 = 145.84Surface area = 11.36 m2/g