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1.
Environ Pollut ; 268(Pt A): 115329, 2021 Jan 01.
Article in English | MEDLINE | ID: mdl-33137681

ABSTRACT

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) emission is one of main concerns for the secondary pollution of municipal solid waste incinerators (MSWI). For timely response to emission, 1,2,4-trichlorobenzene (1,2,4-TrClBz) as dioxin indicator can be monitored via online measurement techniques. In this study, multi-walled carbon nanotubes (MWCNTs) were investigated for their suitability as a 1,2,4-TrClBz sorbent for MSWI stack gas analysis. The tests include, batch adsorption, continuous adsorption-desorption of 1,2,4-TrClBz via thermal desorption coupled with gas chromatography (TD-GC-ECD), temperature and concentration stability of MWCNTs, and adsorption performance of the system. Thermogravimetric/derivative thermogravimetric (TGA/DTG) analysis reveals that MWCNTs has higher capacity in terms of weight loss (14.34%) to adsorb 1,2,4-TrClBz compared to Tenax TA (9.46%) and also shows fast desorption of adsorbate at temperature of 87 °C compared to Tenax TA (130 °C). Interestingly, carbon nanotubes and Tenax TA gave almost similar adsorption-desorption response, and from TD-GC-ECD analysis it was found that with increasing mass flow of 1,2,4-TrClBz (7.42 × 10-6 - 44.52 × 10-6 mg ml-1) through sorbent traps, average peak areas increased from 2.86 ± 0.02 to 13.54 ± 0.26 for MWCNTs and 2.89 ± 0.02 to 13.38 ± 0.12 for Tenax TA, respectively. The stability of MWCNTs for temperature was 400 °C and for concentration of 1,2,4-TrClBz was 50 ppbv. However, regeneration of sorbent at 100 ppbv (1,2,4-TrClBz) was not possible. TD-GC-ECD system showed high adsorption performance with 3.86% and 3.59% relative standard deviation at 250 °C and 300 °C, respectively. Further Fourier Transform Infrared Spectroscopy (FTIR) analysis confirmed that adsorbate can be fully desorbed at 300 °C.


Subject(s)
Dioxins , Nanotubes, Carbon , Polychlorinated Dibenzodioxins , Adsorption , Chlorobenzenes , Incineration
2.
Environ Pollut ; 244: 202-208, 2019 Jan.
Article in English | MEDLINE | ID: mdl-30340166

ABSTRACT

A home-made analytical instrument based on thermal desorption gas chromatography coupled to resonance enhanced multiphoton ionization time-of-flight mass spectrometry (TD-GC-REMPI-TOFMS) was applied for atline measurement of 1,2,4-trichlorobenzene for the prediction of polychlorinated dibenzodioxin and dibenzofuran (PCDD/F) concentrations in the stack gas of a municipal solid waste incinerator (400 ton/day). Conventional high resolution gas chromatography/high resolution mass spectroscopy (HRGC/HRMS) measurements for the determination of PCDD/F concentrations were performed to compare with TD-GC-REMPI-TOFMS measurements. 1,2,4-Trichlorobenzene correlated with I-TEQ at r = 0.867, 0.953 and 0.944 in unstable, stable and integrated conditions. The correlation was independent of the facility operating conditions observed in this study. Using a linear model to predict I-TEQ by 1,2,4-trichlorobenzene over the test, the average of the relative difference between predicted and measured I-TEQ was 18.9%. 1,2,4-Trichlorobenzene measured by TD-GC-REMPI-TOFMS can be used as a robust indicator of I-TEQ in stack gas.


Subject(s)
Chlorobenzenes/analysis , Dibenzofurans, Polychlorinated/analysis , Gas Chromatography-Mass Spectrometry , Polychlorinated Dibenzodioxins/analysis , Air Pollutants/analysis , Incineration
3.
R Soc Open Sci ; 5(7): 172056, 2018 Jul.
Article in English | MEDLINE | ID: mdl-30109050

ABSTRACT

Comprehensive diagnosis of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) emissions was systematically conducted on three hazardous waste incinerators (HWIs). Results indicated that PCDD/F mainly existed in the solid phase before the bag filter. This was especially true for higher chlorinated dioxin and furan congeners (hexa-, hepta- and octa-). The aged bag filters tended to increase the gas-phase PCDD/F. Emissions also increased due to PCDD/F desorption from circulated scrubbing solution and plastic packing media used in the wet scrubber. The PCDD/F concentrations were elevated during the start-up process, reaching up to 5.4 times higher than those measured during the normal operating period. The ratios of PCDFs/PCDDs revealed that the surface-catalysed de novo synthesis was the dominant pathway of PCDD/F formation. Installation of more efficient fabric filters, intermittent replacement of circulated scrubbing solution will result in reduced PCDD/F emission. Additionally, 2,3,4,7,8-PeCDF correlated well with the international toxic equivalent quantity (I-TEQ) value, which suggests that 2,3,4,7,8-PeCDF could act as an I-TEQ indicator.

4.
J Phys Chem A ; 115(5): 726-34, 2011 Feb 10.
Article in English | MEDLINE | ID: mdl-21210701

ABSTRACT

The dissociative photoionization of 1,1-C(2)H(2)Cl(2), (E)-1,2-C(2)H(2)Cl(2), and (Z)-1,2-C(2)H(2)Cl(2) has been investigated at high energy and mass resolution using the imaging photoelectron photoion coincidence instrument at the Swiss Light Source. The asymmetric Cl-atom loss ion time-of-flight distributions were fitted to obtain the dissociation rates in the 10(3) s(-1) < k < 10(7) s(-1) range as a function of the ion internal energy. The results, supported by ab initio calculations, show that all three ions dissociate to the same C(2v) symmetry ClC═CH(2)(+) product ion. The 0 K onset energies thus establish the relative heats of formation of the neutral isomers, that is, the isomerization energies. The experimental rate constants, k(E), as well as ab initio calculations indicate an early isomerization transition state and no overall reverse barrier to dissociation. The major high energy channels are the parallel HCl loss and the sequential ClC═CH(2)(+) → HCCH(+) + Cl process, the latter in competition with a ClC═CH(2)(+) → ClCCH(+) + H reaction. A parallel C(2)H(2)Cl(2)(+) → C(2)HCl(2)(+) + H channel also weakly asserts itself. The 0 K onset energy for the sequential Cl loss reaction suggests no barrier to the production of the most stable acetylene ion product; thus the sequential Cl-atom loss is preceded by a ClC═CH(2)(+) → HC(Cl)CH(+) reorganization step with a barrier lower than that of the second Cl-atom loss. The breakdown diagram corresponding to this sequential dissociation reveals the internal energy distribution of the first C(2)H(2)Cl(+) daughter ion, which is determined by the kinetic energy release in the first, Cl loss reaction at high excess energies. At low kinetic energy release, this distribution corresponds to the predicted two translational degrees of freedom, whereas at higher energies, the excess energy partitioning is characteristic of only one translational degree of freedom. New Δ(f)H(o)(298K) of 3.7, 2.5, and 0.2 ± 1.75 kJ mol(-1) are proposed for 1,1-C(2)H(2)Cl(2), (E)-1,2-C(2)H(2)Cl(2), and (Z)-1,2-C(2)H(2)Cl(2), respectively, and the proton affinity of ClCCH is found to be 708.6 ± 2.5 kJ mol(-1).

5.
J Phys Chem A ; 114(50): 13134-45, 2010 Dec 23.
Article in English | MEDLINE | ID: mdl-21128587

ABSTRACT

Threshold photoelectron photoion coincidence has been used to prepare selected internal energy distributions of nitrosobenzene ions [C(6)H(5)NO(+)]. Dissociation to C(6)H(5)(+) + NO products was measured over a range of internal energies and rate constants from 10(3) to 10(7) s(-1) and fitted with the statistical theory of unimolecular decay. A 0 K dissociative photoionization onset energy of 10.607 ± 0.020 eV was derived by using the simplified statistical adiabatic channel model. The thermochemical network of Active Thermochemical Tables (ATcT) was expanded to include phenyl and phenylium, as well as nitrosobenzene. The current ATcT heats of formation of these three species at 0 K (298.15 K) are 350.6 (337.3) ± 0.6, 1148.7 (1136.8) ± 1.0, and 215.6 (198.6) ± 1.5 kJ mol(-1), respectively. The resulting adiabatic ionization energy of phenyl is 8.272 ± 0.010 eV. The new ATcT thermochemistry for phenyl entails a 0 K (298.15 K) C-H bond dissociation enthalpy of benzene of 465.9 (472.1) ± 0.6 kJ mol(-1). Several related thermochemical quantities from ATcT, including the current enthalpies of formation of benzene, monohalobenzenes, and their ions, as well as interim ATcT values for the constituent atoms, are also given.

6.
J Phys Chem A ; 114(37): 10016-23, 2010 Sep 23.
Article in English | MEDLINE | ID: mdl-20738134

ABSTRACT

The dissociation dynamics of gas phase formic acid ions (HCOOH(+), DCOOD(+), HCOOD(+), DCOOH(+)) are investigated by threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy and high level ab initio calculations. The slow rate constants for this seemingly simple H loss reaction and the large onset energy shifts due to isotopic substitution point to a substantial exit barrier through which the H or D atoms tunnel. Modeling of the HCOOH(+) experimental data using RRKM theory with tunneling through an Eckart potential are best fitted with a barrier of about 17 kJ mol(-1). High level ab initio calculations support the experimental findings with a computed barrier of 15.9 kJ mol(-1), which is associated with the substantial geometry change between the product HOCO(+) cation and the corresponding HCOOH(+) molecular ion. Because of this exit channel barrier, the formic acid ion dissociation does not provide a route for determination of the HOCO(+) heat of formation. Rather, the most accurate value comes from the calculations employing the high accuracy extrapolated ab initio thermochemistry (HEAT) scheme, which yields a Δ(f)H(o)(0K)[HOCO(+)] = 600.3 ± 1.0 kJ mol(-1) (Δ(f)H(o)(298K)[HOCO(+)] = 597.3 ± 1.0 kJ mol(-1)). The calculated proton affinity of CO(2) is thus 534.7 ± 1.0 kJ mol(-1) at 0 K and 539.3 ± 1.0 kJ mol(-1) at 298.15 K.

7.
J Phys Chem A ; 114(42): 11285-91, 2010 Oct 28.
Article in English | MEDLINE | ID: mdl-20617794

ABSTRACT

The dissociation dynamics of energy selected i-C(3)H(7)X (X = H, Cl, Br, and I) ions have been investigated by imaging photoelectron-photoion coincidence (iPEPICO) spectroscopy using synchrotron radiation from the X04DB VUV beamline in the Swiss Light Source of the Paul Scherrer Institut. The 0 K dissociation energy (E(0)) for i-C(3)H(8) was determined to be 11.624 ± 0.002 eV. This leads to a 298 K isopropyl ion heat of formation of 805.9 ± 0.5 kJ mol(-1). The Δ(f)H(298K)°(i-C(3)H(7)(+)) combined with the measured 0 K onsets for i-C(3)H(7)(+) formation from isopropyl chloride (11.065 ± 0.004 eV), isopropyl bromide (10.454 ± 0.008 eV), and isopropyl iodide (9.812 ± 0.008 eV) yields the 298 K isopropyl chloride, bromide, and iodide heats of formation of -145.7 ± 0.7, -95.6 ± 0.9, and -38.5 ± 0.9 kJ mol(-1), respectively. These values provide a significant correction to literature values and reduce the error limits. Finally, the new i-C(3)H(7)(+) heat of formation leads to a predicted adiabatic ionization energy for the isopropyl radical of 7.430 ± 0.012 eV and a 298 K proton affinity for propene of 744.1 ± 0.8 kJ mol(-1).

8.
J Phys Chem A ; 114(2): 804-10, 2010 Jan 21.
Article in English | MEDLINE | ID: mdl-19839625

ABSTRACT

The dissociation dynamics of energy selected neopentane, t-butyl iodide, and t-butyl hydroperoxide ions have been investigated by threshold photoelectron-photoion coincidence (TPEPICO) spectrometry. Although the methyl loss reaction from neopentane ions producing the t-butyl ion is in competition with a lower energy methane loss channel, modeling these two channels with the statistical theory of unimolecular decay provides a 0 K dissociation onset for methyl loss of 10.564 +/- 0.025 eV. This leads to a 298 K t-butyl ion heat of formation of 714.3 +/- 2.5 kJ x mol(-1), which is some 3 kJ x mol(-1) higher than the previously accepted value. The Delta(f)H degrees (298K)(t-C(4)H(9)(+)) combined with the measured 0 K onsets for t-C(4)H(9)(+) formation from t-butyl iodide (9.170 +/- 0.007 eV) and from t-butyl hydroperoxide (9.904 +/- 0.012 eV), yields 298 K t-butyl iodide and t-butyl hydroperoxide heats of formation of -68.5 +/- 2.6 kJ x mol(-1) and -233.2 +/- 2.8 kJ x mol(-1), respectively. Finally, the new t-C(4)H(9)(+) heat of formation leads to a predicted adiabatic ionization energy for the t-butyl radical of 6.86 +/- 0.20 eV, and a 298 K proton affinity for isobutene of 798.8 +/- 2.5 kJ x mol(-1). The predicted ionization energy exceeds all measured values by 0.10 eV.

9.
J Phys Chem A ; 113(40): 10710-6, 2009 Oct 08.
Article in English | MEDLINE | ID: mdl-19746895

ABSTRACT

The 0 K onset of C(3)H(6) --> C(3)H(5)(+) + H(*) is measured by threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy. From the onset (11.898 +/- 0.025 eV) the heat of formation of the allyl ion (CH(2)CHCH(2)(+)) is determined to be DeltaH degrees (f,0K) = 967.2; DeltaH degrees (f,298K) = 955.4 +/- 2.5 kJ mol(-1). The value is significantly more positive than prior determinations, and resolves a discrepancy between measurements of the allyl radical and allyl ion heats of formation and recent highly precise measurements of the allyl radical adiabatic ionization energy. The new allyl ion heat of formation leads to a new proton affinity for propadiene (allene) of 765.0 +/- 2.6 kJ mol(-1). An attempt is made to determine the CH(3)CCH(2)(+) heat of formation by measuring the 0 K onset of 2-ClC(3)H(5) --> C(3)H(5)(+) + Cl(*). However, C(3)H(5)(+) appears at too low an energy to be the higher energy CH(3)CCH(2)(+) structure. Rather, 2-ClC(3)H(5)(+) undergoes a concerted hydrogen transfer and Cl-loss via an intramolecular S(N)2 like mechanism to produce the allyl ion. The 0 K onset of 3-ClC(3)H(5) --> C(3)H(5)(+) + Cl(*) (11.108 +/- 0.010 eV) is measured to determine the 3-ClC(3)H(5) heat of formation (DeltaH degrees (f,0K) = 14.9; DeltaH degrees (f,298K) = 1.1 +/- 2.7 kJ mol(-1)). 3-ClC(3)H(5)(+) is suggested to readily isomerize to trans 1-ClC(3)H(5)(+) prior to dissociation.

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