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Rutgers University Department of Ceramic & Materials Engineering

Laboratory 254: M2

BET Surface Area Measurement

Glenn K. Lockwood Lab date: February 7, 2005 Professor Richard E. Riman TAs: David Babson, Milca Aponte

trabecular bone. . and cortical bone was affirmed. and these figures were then compared to the specific surface areas of previously measured samples of titania and cortical bone. a BET analyzer was used to measure the specific surface areas of hydroxyapatite and trabecular bone using nitrogen gas. and it was from this information that the specific surface areas were calculated. titania. the applicability of the BET equation to measuring the specific surface areas of hydroxyapatite. Thus. The data collected from the analysis was highly consistent and fit the BET equation remarkably well.Abstract In this experiment.

Introduction In the field of material processing. various biotechnology applications. meaning they occur in multiphase systems. being able to identify and characterize high surface area materials is of great interest in material science and engineering. Other areas in which high surface area materials are being used and studied in are petroleum processing. However. are currently being researched in hopes that they may lead the way to the largescale production of hydrogen gas from biomass for use as a clean energy source[1]. One of the more popular methods of making such measurements involves coating such high surface area materials in a single layer of nitrogen atoms at the freezing point of nitrogen. In these cases. Thus. making such measurements becomes relatively difficult when dealing with nanoparticles that have high specific surface areas. the majority of chemical reactions that are of great significance are heterogeneous. it only makes sense that maximizing the surface area of a solid reactant to maximize the rate of reaction would be of paramount importance. the more product can be formed at once and the more economical the process is. these reactions can only take place where the two reactants meet at the phase boundaries. knowing the exposed surface area per gram of material can help determine if a certain reaction is economically feasible before ever ha ving to expend the money. and many of the more important processes in material science involve solid reactants in some way or another. and advanced chemical sensing technology[2]. and labor required to physically test it. time. A perfect example of this are the nanostructured catalysts that. as the larger the phase interface. As such. the sample can then be removed from the . after this monolayer of nitrogen is formed. due to their extremely high active surface area. chemical separation applications.

an equation was developed by Stephen Brunauer. Knowing this volume. and C is a constant. In this experiment. and Edward Teller which included correctional factors that made this method incredibly useful[3]. causing the adsorbed nitrogen to “jump off” of the material and be measured. Vm is the volume of gas required to cover a unit mass of the material with a complete monolayer of gas atoms. This BET equation can also be plotted as a linear equation from which value for the volume of gas required to form a complete monolayer can be extracted. However. The area covered by the adsorbed nitrogen is then the surface area of the material. the specific surface area of the material tested can then be derived using other more basic formulas. leaving some spots covered by only a single atom while others may have multiple nitrogen atoms stacked onto each other. Paul Emmett. Unfortunately. V is the volume of gas adsorbed per unit mass of material at pressure P. this process is carried out for several different materials to compare specific surface area values using a BET instrument which operates using nitrogen as the adsorbate. . This creates an uneven covering over the surface of the material.nitrogen atmosphere and heated. such a process is not feasible in reality because the nitrogen does not only adsorb to the material’s surface. but to other nitrogen atoms that have already been adsorbed as well. Taking this volume of nitrogen to be equivalent to the amount required to coat the material being tested entirely would give erroneously large results since more nitrogen was adsorbed than it would take to create a single monolayer. The equation is described as P 1 ( C − 1) P = + V ( P0 − P) Vm C Vm C P0 y = b + m x where P0 is the saturation pressure of the gas (atmospheric pressure if the process is carried out at the boiling point of nitrogen at atmospheric pressure).

Figure 1 displays a superposition of all of the data measured by the BET machine and the linear best fit lines for them. after the sample was finished. and massed again and the BET analyzer configured and its dewar flask filled with liquid nitrogen and set into place. These tubes were then massed. and the machine set to make five measurement points. Results and Discussion Of the two samples tested in the laboratory (the trabecular bone and hydroxyapatite). cortical bone. all of the results were remarkably precise and conformed to the mathematical relationships described by the BET equation. as can be seen from the plots. mass. The machine was then activated and. The cortical bone sample was not analyzed due to time constraints. the sample ID. Thus. each set of data obtained is highly linear when plotted in the form of the BET equation. degassed. .Procedure Before entering the lab. the tube containing it was loaded into the analyzer. The functions that describe these best fit lines are based on multiple points and are determined statistically based on the empirical data. it was removed from the machine and the resulting data saved to disk. all that had to be done in the laboratory was load each degassed sample and collect the results of the analysis. The first sample to be tested was the trabecular bone. the titania sample tested beforehand. or trabecular bone. The sample of degassed hydroxyapatite was then massed and the analysis procedure repeated. three sample tubes had been cleaned and each filled with a sample of either hydroxyapatite. and density entered into the software. and the results obtained from a previous testing of cortical bone.

both of which can be solved. . Once Vm is calculated.From these linear regression lines. P is the known pressure the machine lets into the sample tube during each run. and b = . m= . P0 is the vapor pressure of the nitrogen at the temperature of the material (which is at the boiling temperature of nitrogen. After a point is plotted for each testing run made on a sample. For example. x= . the unknown factors in the BET equation (namely. the line of best fit’s slope then is equal to m = (C-1)/VmC and its y-intercept is equal to b = 1 /VmC. Thus. This is possible because all of the terms in the se x. applying it to the equation Total Surface Area = a0 N AVm 2240 where a0 is the cross-sectional area of a nitrogen atom and NA is Avogadro’s number will give the surface area of the entire sample being tested. m and b are a system of two equations and two unknowns (C and Vm).and y-equivalencies are known. C and Vm) can be equated to the terms in the linear regression function and solved as a simple system of equations. by knowing the BET equation P 1 (C − 1) P = + V ( P0 − P) Vm C Vm C P0 and its counterparts in linear form (y = mx + b) y= P ( C − 1) P 1 . so the vapor pressure simply is equal to atmospheric pressure). V ( P0 − P) Vm C P0 Vm C a data plot can be made simply by plotting the measured values for P /Po on the x-axis and P /V(Po-P ) on the y-axis. Dividing this surface area by the mass of the sample then yields the specific sur face area of the material. and V is the measured volume of the nitrogen multilayer that was adsorbed to the surface of the material.

One final observation that is reflected in the data and proven in the math of the BET equation was that materials with higher surface areas also had the largest volume of nitrogen adsorbed to a multilayer on their surfaces. Of particular interest in Figure 2. are the error bars. which had a specific surface area of 76. it is obvious that the materials with the lowest relative data sets and thus the highest volumes of nitrogen adsorbed (such as hydroxyapatite and titania) would have generally higher specific surface areas than the materials with the higher data sets. Titania powder also was found to have a fairly large specific surface area. Barely visible (with the largest percent standard error being in the hydroxyapatite measurement. because the y axis in Figure 1 is proportional to the inverse of the volume adsorbed. this principle could be used to compare the relative specific surface areas of different materials without having to actually calculate them. no material tended to irregularly attract more nitrogen atoms than any other.6471 ± 0. it is clear that hydroxyapatite has a specific surface area that far surpasses the other three materials that data was obtained for. such as the trabecular and cortical bones. these very small error margins also indicate that the data obtained by the BET analysis machine was highly consistent. though. Thus.5099 m2 /g).Considering the BET surface area calculations that resulted from this experiment as shown in Figure 2. while the two natural bone samples had the lowest specific surface areas. and a definite proportionality exists between specific surface area and amount of nitrogen adsorbed to the surface in a multilayer. For example. While not entirely useful when examining just one material. .

Titania also has a relatively high specific surface area. the data collected from the BET machine. Furthermore. while trabecular bone and cortical bone have the lowest specific surface areas of the four. . displays a highly linear trend from which the volume of a nitrogen monolayer can be extracted. The standard deviation displayed by the data points from this trendline is incredibly small as well.Conclusion Based on the data collected before and during this experiment. when plotted in the form of the BET equation. it is clear that hydroxyapatite has the most specific surface area of all of the materials tested. reaffirming the validity of using the BET equation to obtain specific surface area measurements as well as exemplifying the high degree of precision in using a BET analysis machine.

As roughly indicated by the graphs. trabecular bone.120000 0.007 0.100000 0.25000 0.080000 y = 0.20000 0.000000 0. the plotted points are all very close to being linear. .5144x + 0.020000 y = 0.160000 0.0567x + 0.060000 y = 0. and hydroxyapatite) and the results obtained from a previous testing of cortical bone.05000 0.30000 0.15000 0.00000 0.Appendix Figure 1 : Results of BET Analysis for Tested Materials 0.35000 0 0 0 0 0 0 0 0 P/Po Titania Cortical Bone Linear (Cortical Bone) Trabecular Bone Linear (Hydroxyapatite) Linear (Trabecular Bone) Hydroxyapatite Linear (Titania) This is a plot of the five steps made in the analysis of the three materials tested (titania.0007 0.040000 0.1804x + 0.10000 0.0997x + 0.0153 0.180000 y = 0.140000 P/V(Po-P) 0.0001 0.

. Also plotted are error bars indicating the specific error of the five passes made for each materials. these error margins are so narrow that they are hard to see.Figure 2 : Specific Surface Areas as Calculated by the BET Method 90 80 70 BET Surface Area (m^2/g) 60 50 40 30 20 10 0 Titania Trabecular Bone Hydroxyapatite Cortical Bone This is a comparison of the specific surface areas obtained by using the BET analysis machine on four materials. however.

2.htm> Copyright 1998 Galen D.. Stucky.html> Copyright 2005 Dictionary and Atlas of Nanoscience and Nanotechnology.ifs. “High Surface Area Materials.” p. Laboratory II Handbook. Galen D.” <http://nanoatlas.11 .org/loyola/nano/US. “Catalysis.Review/07_03.wtec. Stucky. Referenced 1. “BET Surface Area Measurement.” <http://www.