Theoretical predictions of thermodynamic parameters of adsorption of nitrogen containing environmental contaminants on kaolinite

Supporting Information

Andrea Michalkova Scott,a,*Elizabeth A. Burns,b Brandon Lafferty,a Frances C. Hill,a

aU. S. Army Engineer Research and Development Center (ERDC), 3909 Halls Ferry Rd., Vicksburg, MS 39180, USA

bBadger Technical Services, LLC, 3909 Halls Ferry Rd., Vicksburg, MS 39180, USA

This document includes description of the BLYP-D2 optimized structures of the adsorption systems of nitrogen containing compounds (NCCs, 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dinitroanisole (DNAN), and 3-nitro-1,2,4-triazol-5-one (NTO)) in a parallel and perpendicular orientation toward the octahedral and tetrahedral kaolinite surface. We will use the following notations in the text, Tables, and Figures for presented kaolinite systems: K(o)-TNT(=), K(o)-DNAN(=), K(o)-NTO(=), K(o)-DNT(=), K(t)-TNT(=), K(t)-DNAN(=), K(t)-NTO(=), and K(t)-DNT(=) for the systems with the adsorbate in a parallel orientation toward the kaolinite surface and K(o)-TNT(), K(o)-DNAN(), K(o)-NTO(), K(o)-DNT(), K(t)-TNT(), K(t)-DNAN(), K(t)-NTO(), and K(t)-DNT() for the systems with the adsorbate in a perpendicular orientation toward the kaolinite surface. First experimental T∆Sads [kcal/mol] values for various adsorption systems are presented in Table S1 with the list of references on the bottom of this file. Tables S2-S5 present low vibrational frequencies [cm-1] and T∆Sads [kcal/mol] values calculated at the BLYP-D2 and M06-2X-D3(Cluster) levels for adsorption of nitrogen containing compounds (NCCs) in a parallel orientation toward the tetrahedral (K(t)) and octahedral (K(o)) kaolinite surfaces from the gas phase (K-NCCs(=)). Figures S1-S6 illustrate the optimized structures of TNT, DNT, and DNAN adsorbed in a perpendicular orientation on the octahedral and tetrahedral surface of kaolinite (K-NCCs()).

Table S1: Experimental T∆Sads [kcal/mol] values for various adsorption systems

System / T∆Sads
HC_ZSM-22 (zeolites) (gas phase) / -10.6- -2.9 (473 K) [1]
HC_Na-Y (zeolites) (gas phase) / -8.7- -7.1 (443 K) [2]
HC_H-ZSM-5 (zeolites) (gas phase) / -9.9 - -7.7 (341 K), -10.7 - -8.3 (370 K), -11.6 - -9.0 (400 K) [3]
Hexane_zeolite (gas) / -13.3 - -12.1 (474 K) [4]
CO/CO2/N2_Mg-MOF-74 (gas phase) / -9.5, -13.2 (CO,CO2 at 298 K), -3.1 (N2 at 100 K) [5]
Stearic acid_kaolinite (gas phase) / -4.9 (298 K) [6]

Table S2: Low vibrational frequencies [cm-1] for adsorption of nitrogen containing compounds (NCCs) on the octahedral (K(o)) kaolinite surface from gas phase

Method
Model/
System / BLYP-D2
Cluster / M06-2X-D3
Cluster
K(o)-TNT(=) / 38, 46, 49, 54, 58, 67, 72, 85, 87, 90, 100, 103, 105, 115, 118, 119, 128, 130, 136, 138, 140, 140, 142, 145, 150, 150, 153, 154, 164, 169, 171, 176, 179, 182, 184, 187, 189, 191, 194, 195, 196, 199 / 14, 28, 42, 49, 54, 55, 64, 68, 76, 86, 91, 93, 98, 104, 111, 113, 120, 126, 129, 132, 135, 139, 143, 147, 150, 151, 155, 157, 163, 164, 170, 173, 175, 181, 183, 185, 190, 192, 194, 195, 197
K(o)-DNAN(=) / 36, 42, 44, 51, 60, 65, 70, 82, 89, 92, 93, 102, 107, 111, 114, 122, 127, 130, 133, 136, 141, 143, 147, 149, 150, 152, 159, 165, 166, 168, 170, 175, 176, 180, 180, 183, 185, 189, 191, 195, 197, 198 / 23, 41, 44, 50, 51, 61, 63, 73, 80, 88, 94, 96, 108, 109, 111, 115, 122, 128, 131, 133, 136, 141, 145, 150, 154, 158, 160, 163, 167, 172, 174, 175, 178, 180, 185, 188, 188, 193, 197, 199
K(o)-DNT(=) / 40, 45, 53, 65, 67, 73, 78, 88, 89, 92, 101, 105, 112, 117, 125, 129, 133, 134, 137, 138, 142, 146, 147, 149, 151, 159, 162, 166, 169, 175, 177, 178, 180, 182, 183, 186, 190, 193, 196, 199 / 24, 31, 45, 48, 57, 63, 66, 74, 81, 89, 91, 94, 108, 111, 117, 123, 134, 136, 138, 141, 143, 147, 150, 154, 156, 159, 163, 167, 172, 176, 177, 179, 182, 187, 189, 190, 193, 197
K(o)-NTO(=) / 36, 42, 53, 60, 65, 68, 85, 87, 95, 102, 107, 110, 113, 119, 124, 125, 129, 133, 137, 139, 140, 147, 149, 149, 150, 158, 161, 165, 166, 169, 171, 174, 176, 180, 183, 184, 188, 194, 196, 199 / 21, 35, 46, 47, 57, 60, 70, 81, 89, 98, 105, 106, 108, 117, 121, 127, 132, 135, 140, 141, 142, 146, 147, 150, 155, 160, 161, 166, 171, 174, 178, 181, 185, 186, 188, 193, 195, 196

Table S3: Low vibrational frequencies [cm-1] for adsorption of nitrogen containing compounds (NCCs) on the tetrahedral (K(t)) kaolinite surface from gas phase

Method
Model/
System / BLYP-D2
Cluster / M06-2X-D3
Cluster
K(t)-TNT(=) / 36, 43, 51, 53, 63, 67, 72, 77, 81, 85, 88, 89, 94, 96, 105, 111, 119, 121, 127, 131, 133, 135, 139, 145, 147, 150, 152, 153, 156, 159, 164, 167, 168, 171, 176, 184, 185, 187, 190, 193, 197, 197 / 23, 38, 43, 48, 57, 61, 66, 71, 74, 85, 87, 91, 105, 109, 111, 113, 113, 115, 122, 129, 131, 135, 137, 144, 147, 147, 149, 151, 155, 159, 160, 164, 167, 173, 175, 176, 177, 183, 185, 193, 196
K(t)-DNAN(=) / 56, 62, 63, 67, 72, 77, 79, 85, 87, 90, 97, 102, 106, 109, 111, 121, 123, 130, 132, 136, 142, 147, 148, 152, 153, 156, 159, 159, 154, 170, 170, 172, 173, 177, 182, 188, 190, 191, 196, 198 / 34, 35, 39, 42, 57, 65, 71, 81, 83, 85, 94, 97, 106, 111, 114, 116, 120, 123, 130, 135, 136, 139, 144, 150, 152, 153, 155, 161, 162, 169, 173, 177, 177, 179, 181, 185, 188, 191, 198
K(t)-DNT(=) / 46, 54, 64, 69, 72, 77, 84, 86, 88, 90, 98, 108, 111, 113, 116, 124, 126, 129, 135, 138, 143, 143, 147, 149, 153, 157, 160, 163, 165, 168, 171, 173, 180, 181, 184, 187, 191, 193, 198 / 23, 27, 40, 52, 59, 65, 70, 75, 82, 89, 91, 99, 100, 107, 112, 116, 117, 124, 126, 128, 133, 134, 142, 146, 149, 152, 155, 158, 160, 164, 165, 169, 172, 174, 176, 183, 185, 186, 193, 195, 197
K(t)-NTO(=) / 35, 43, 53, 61, 64, 69, 72, 76, 82, 86, 94, 105, 111, 115, 117, 126, 131, 136, 138, 139, 144, 145, 147, 150, 153, 156, 161, 167, 169, 172, 176, 179, 182, 184, 188, 191, 196, 199 / 38, 40, 44, 51, 53, 65, 67, 70, 83, 84, 89, 103, 107, 113, 116, 119, 128, 132, 136, 141, 143, 145, 149, 153, 156, 159, 162, 164, 171, 174, 177, 180, 185, 190, 191, 195, 195

Table S4: T∆Sads [kcal/mol] values for adsorption of nitrogen containing compounds (NCCs) on the tetrahedral (K(t)) and octahedral (K(o)) kaolinite surfaces from the gas phase obtained at the BLYP-D2(Cluster) level

System / T∆Svib / T∆Srot / T∆Strans / T∆Stot
K(o)-TNT(=) / 0.9 / -8.8 / -12.4 / -20.2
K(o)-DNAN(=) / 3.3 / -8.5 / -12.3 / -17.5
K(o)-DNT(=) / 1.8 / -8.4 / -12.2 / -18.8
K(o)-NTO(=) / 4.2 / -7.7 / -12.0 / -15.4
K(t)-TNT(=) / 2.0 / -8.8 / -12.4 / -19.2
K(t)-DNAN(=) / 0.6 / -8.5 / -12.3 / -20.2
K(t)-DNT(=) / 0.9 / -8.4 / -12.2 / -19.7
K(t)-NTO(=) / 3.7 / -7.7 / -12.0 / -16.0

Table S5: T∆Sads [kcal/mol] values for adsorption of nitrogen containing compounds (NCCs) on the tetrahedral (K(t)) and octahedral (K(o)) kaolinite surfaces from the gas phase obtained at the M06-2X-D3(Cluster) level

System / T∆Svib / T∆Srot / T∆Strans / T∆Stot
K(o)-TNT(=) / 3.8 / -9.4 / -12.4 / -18.0
K(o)-DNAN(=) / 4.9 / -9.2 / -12.3 / -16.5
K(o)-DNT(=) / 4.5 / -9.0 / -12.2 / -16.7
K(o)-NTO(=) / 5.7 / -8.3 / -12.0 / -14.5
K(t)-TNT(=) / 5.6 / -9.4 / -12.4 / -16.1
K(t)-DNAN(=) / 5.4 / -9.2 / -12.3 / -16.1
K(t)-DNT(=) / 7.0 / -9.0 / -12.2 / -14.2
K(t)-NTO(=) / 6.4 / -8.3 / -12.0 / -13.8

References:

(1) Tielens F, Denayer JFM, Daems I, Baron GV, Mortier WJ, Geerlings P (2003) J Phys Chem B 107 :11065-11071

(2) De Moor BA, Reyniers M-F, Gobin OC, Lercher JA, Marin GB (2010) J Phys Chem C 115 :1204-1219

(3) Boulard S, Gilot P, Brosius R, Habermacher D, Martens JA (2004) Top Catal 30:49-53

(4) Valenzano L, Civalleri B, Chavan S, Palomino GT, Arean CO, Bordiga S (2010) J Phys Chem C 114:11185-11191

(5) Sari A, Ipyldak O (2006) Bull Chem Soc Ethiop 20:259−267

Figure captions

Figure S1. The optimized structure of TNT adsorbed in a perpendicular orientation towards the octahedral kaolinite surface (K(o)-TNT()) obtained at the BLYP-D2(PBC) level of theory.

Figure S2. The optimized structures of DNT adsorbed in a perpendicular orientation towards the octahedral kaolinite surface (K(o)-DNT()) obtained at the BLYP-D2(PBC) level of theory.

Figure S3. The optimized structures of DNAN adsorbed in a perpendicular orientation towards the octahedral kaolinite surface (K(o)-DNAN()) obtained at the BLYP-D2(PBC) level of theory.

Figure S4. The optimized structure of TNT adsorbed in a perpendicular orientation towards the tetrahedral kaolinite surface (K(t)-TNT()) obtained at the BLYP-D2(PBC) level of theory.

Figure S5. The optimized structures of DNT adsorbed in a perpendicular orientation towards the tetrahedral kaolinite surface (K(t)-DNT()) obtained at the BLYP-D2(PBC) level of theory.

Figure S6. The optimized structures of DNAN adsorbed in a perpendicular orientation towards the tetrahedral kaolinite surface (K(t)-DNAN()) obtained at the BLYP-D2(PBC) level of theory.

Figure S1.

Figure S2.

Figure S3.

Figure S4.

Figure S5.

Figure S6.