UV Spectrometric Indirect Analysis of Brominated MWCNTs with UV Active Thiols and an Alkene—Reaction Kinetics, Quantification and Differentiation of Adsorbed Bromine and Oxygen
Abstract
:1. Introduction
2. Results and Discussion
2.1. Results of the Analyses of Brominated MWCNTs
R No. | Reagent | CNT sample with weight mC and Vj and f | β (μmol/g) | k (L∙mol−1∙h−1), single param. + temperature | τ (h), above: from k below: from a, b, c | Iteration parameters a, b, c multiparameter fitting | |
---|---|---|---|---|---|---|---|
R4 | 4-(2,2,2-Trifluoro-ethoxy-methyl)-1-naph-tha-linemethanthiol (11) + 1.00 mL tri-ethylamine | 0.0127 g CNT1 f = 40, Vj = 0.000250 L | 5601 ± 87 P = (RFS)2 ≅ 1* Br2 | 275 ± 16 P T = 297 K 138 ± 12 A T = 297 K | 1.328 ± 0.077 P | a (L∙mol−1∙h−3) | −8.834 A |
1.709 A | b (L∙mol−1∙h−2) | 117.7 A | |||||
c (L∙mol−1∙h−1) | −72.48 A | ||||||
R5 | 1-Naphthaline-methan-thiol (16) + 1.0 mL tri-ethylamine | 0.0589 g CNT3 f = 37, Vj = 0.000270 L | 3388 ± 165 P = (RS)2 ≅ 1* Br2 | 1535 ± 154 P T = 295 K | 0.232 ± 0.023 P | a (L∙mol−1∙h−3) | 8883 P |
0.250 P | b (L∙mol−1∙h−2) | −6854 P | |||||
c (L∙mol−1∙h−1) | 2582 P | ||||||
R6 | 1-Naphthaline-methan-thiol (16) + 1.0 mL tri-ethylamine | 0.0940 g CNT0 f = 5, Vj = 0.00100 L | 207 ± 20 P = (RS)2 ≅ 2* O2 | 2041 ± 117 P T = 296 K | 1.531 ± 0.088 P | a (L∙mol−1∙h−3) | 0 P |
1.682 P | b (L∙mol−1∙h−2) | 795.6 P | |||||
c (L∙mol−1∙h−1) | 518.6 P |
R No. | Reagent | CNT sample with weight mC and Vj and f | β (μmol/g) | k (L∙mol−1∙h−1) single param. + temperature | τ (h) | Iteration parameters a, b, c multiparameter fitting | |
---|---|---|---|---|---|---|---|
R1 | 3-Vinyl-N,N-diethylbenzamide (13) | 0.1216 g CNT1 f = 200, Vj = 0.00100 L | 0 | 0 T = 295 K | ∞ | a (L∙mol−1∙h−3) | 0 |
∞ | b (L∙mol−1∙h−2) | 0 | |||||
c (L∙mol−1∙h−1) | 0 | ||||||
R2 | 3-Vinyl-N,N-diethylbenzamide (13) | 0.1585 g CNT2 f = 200, Vj = 0.00100 L | 0 | 0 T = 295 K | ∞ | a (L∙mol−1∙h−3) | 0 |
∞ | b (L∙mol−1∙h−2) | 0 | |||||
c (L∙mol−1∙h−1) | 0 | ||||||
R3 | 3-Vinyl-N,N-diethylbenzamide (13) | 0.1249 g CNT3 f = 10, Vj = 0.00100 L | 0 | 0 T = 296 K | ∞ | a (L∙mol−1∙h−3) | 0 |
∞ | b (L∙mol−1∙h−2) | 0 | |||||
c (L∙mol−1∙h−1) | 0 |
Reaction | Corrected and uncorrected concentration profiles c(t) | Corrected concentration profile and iterated curves |
---|---|---|
R4 | Figure 2 | Figure 3 |
R5 | Figure 4 | Figure 5 |
R6 | Figure 6 | Figure 7 |
2.2. Discussion of the Chosen Discontinuous Off-Line Sampling Procedure
3. Experimental
3.1. Materials
Material | at % C | at % O | at % Br |
---|---|---|---|
CNT0 | 99.4 | 0.6 | – |
CNT1 | 75.6 | 6.5 | 17.9 |
CNT2 | 74.1 | 4.3 | 21.7 |
CNT3 | 97.4 | 1.0 | 1.6 |
3.2. Instruments
3.3. Initial Material Analyses of the CNT Samples
3.4. Syntheses of Reagents and Measurement of UV-Extinction Coefficients
Reagent | Solvent | λ (nm) | ελ (L∙mol−1∙cm−1) | Concentration detection limit (98% confidence) (μmol/L) |
---|---|---|---|---|
1-Naphthalenemethan-thiol (16) + triethylamine | CH3CN | 284.5 | 7672 ± 36 | 2.13 |
1-Naphthalenemethan-thiol (16) + triethylamine | CH3CN | 287.5 | 6822 ± 11 | 0.83 |
Bis-(1-Naphthylmethyl)-disulfide (17) + triethylamine | CH3CN | 284.5 | 15740 ± 157 | 1.79 |
Bis-(1-Naphthylmethyl)-disulfide (17) + triethylamine | CH3CN | 287.5 | 16868 ± 161 | 1.84 |
4-(2,2,2-Trifluoroethoxymethyl)-1-naphthalenemethan-thiol (11) + triethylamine | CH3CN | 289.7 | 8876 ± 65 | 2.54 |
4-(2,2,2-Trifluoroethoxymethyl)-1-naphthalenemethan-thiol (11) + triethylamine | CH3CN | 292.7 | 8196 ± 58 | 2.41 |
Bis-[4-(2,2,2-Trifluoroethoxymethyl)-1-Naphthylmethyl]-disulfide (12) + triethylamine | CH3CN | 289.7 | 18974 ± 58 | 0.45 |
Bis-(4-(2,2,2-Trifluoroethoxymethyl)-1-Naphthylmethyl)-disulfide (12) + triethylamine | CH3CN | 292.7 | 19826 ± 55 | 0.43 |
N,N-Diethyl-3-vinylbenzamide (13) | CHCl3 | 241.5 | 13011 ± 188 | 2.97 |
N,N-Diethyl-3-vinylbenzamide (13) | CHCl3 | 243.5 | 13681 ± 164 | 2.46 |
(±)-N,N-Diethyl-3-(1,2-Dibromoethyl)-benzamide (14) | CHCl3 | 241.5 | 6862 ± 61 | 3.54 |
(±)-N,N-Diethyl-3-(1,2-Dibromoethyl)-benzamide (14) | CHCl3 | 243.5 | 6586 ± 50 | 3.00 |
3.5. General Procedure
Reaction | Reagent | CNT sample | mas (g) | Vrs (L) | Vprs (L) | Vs (L) | Vt (L) | mar (g) |
---|---|---|---|---|---|---|---|---|
R1 | 3-Vinyl-N,N-diethyl-benzamide (13) | CNT1 | 0.6845 | 0.1000 | 0.02500 | 0.05000 | 0.07500 | 0.1711 |
R2 | 3-Vinyl-N,N-diethyl-benzamide (13) | CNT2 | 0.6845 | 0.1000 | 0.02500 | 0.05000 | 0.07500 | 0.1711 |
R3 | 3-Vinyl-N,N-diethyl-benzamide (13) | CNT3 | 0.1836 | 0.1000 | 0.00050 | 0.06500 | 0.07000 | 0.0092 |
R4 | 4-(2,2,2-Trifluoro-ethoxy-methyl)-1-naphthalene-methanthiol (11) | CNT1 | 0.0572 | 0.0200 | 0.01500 | 0.01500 | 0.03000 | 0.0429 |
R5 | 1-Naphthalene-methan-thiol (16) + 1.0 mL tri-ethylamine | CNT3 | 0.2583 | 0.0500 | 0.01500 | 0.07500 | 0.09000 | 0.0775 |
R6 | 1-Naphthalene-methan-thiol (16) + 1.0 mL tri-ethyl-amine | CNT0 | 0.1951 | 0.1000 | 0.00500 | 0.07000 | 0.07500 | 0.0098 |
Reaction | λ1 (nm) | λ2 (nm) |
---|---|---|
R1 | 241.5 | 243.5 |
R2 | 241.5 | 243.5 |
R3 | 241.5 | 243.5 |
R4 | 289.7 | 292.7 |
R5 | 284.5 | 287.5 |
R6 | 284.5 | 287.5 |
3.6. Theory and Calculation
3.6.1. Quantification
3.6.2. Reaction Kinetics and Modeled Mechanism
4. Conclusions
Acknowledgements
Conflict of Interest
References
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Hanelt, S.; Friedrich, J.F.; Meyer-Plath, A. UV Spectrometric Indirect Analysis of Brominated MWCNTs with UV Active Thiols and an Alkene—Reaction Kinetics, Quantification and Differentiation of Adsorbed Bromine and Oxygen. Materials 2013, 6, 3035-3063. https://doi.org/10.3390/ma6083035
Hanelt S, Friedrich JF, Meyer-Plath A. UV Spectrometric Indirect Analysis of Brominated MWCNTs with UV Active Thiols and an Alkene—Reaction Kinetics, Quantification and Differentiation of Adsorbed Bromine and Oxygen. Materials. 2013; 6(8):3035-3063. https://doi.org/10.3390/ma6083035
Chicago/Turabian StyleHanelt, Sven, Jörg F. Friedrich, and Asmus Meyer-Plath. 2013. "UV Spectrometric Indirect Analysis of Brominated MWCNTs with UV Active Thiols and an Alkene—Reaction Kinetics, Quantification and Differentiation of Adsorbed Bromine and Oxygen" Materials 6, no. 8: 3035-3063. https://doi.org/10.3390/ma6083035