Selected ATcT [1, 2] enthalpy of formation based on version 1.176 of the Thermochemical Network [3]

This version of ATcT results[3] was generated by additional expansion of version 1.172 to include species related to Criegee intermediates that are involved in several ongoing studies[4].

Chlorine dioxide

Formula: OClO (g)

CAS RN: 10049-04-4

ATcT ID: 10049-04-4*0

SMILES: O=Cl=O

InChI: InChI=1S/ClO2/c2-1-3

InChIKey: OSVXSBDYLRYLIG-UHFFFAOYSA-N

Hills Formula: Cl1O2

2D Image:

Aliases: OClO; Chlorine dioxide; Dioxido-lambda5-chloranyl; Chlorosyloxidanyl; Chlorine peroxide; Chlorine (IV) oxide; Chloroperoxyl; Chlorosyloxy; Chloryl radical; Chlorine oxide; Alcide; Oxine

Relative Molecular Mass: 67.4515 ± 0.0011

Δ_fH°(0 K)	Δ_fH°(298.15 K)	Uncertainty	Units
101.42	98.95	± 0.29	kJ/mol

3D Image of OClO (g)

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Top contributors to the provenance of Δ_fH° of OClO (g)

The 20 contributors listed below account only for 84.6% of the provenance of Δ_fH° of OClO (g).
A total of 35 contributors would be needed to account for 90% of the provenance.

Please note: The list is limited to 20 most important contributors or, if less, a number sufficient to account for 90% of the provenance. The Reference acts as a further link to the relevant references and notes for the measurement. The Measured Quantity is normaly given in the original units; in cases where we have reinterpreted the original measurement, the listed value may differ from that given by the authors. The quoted uncertainty is the a priori uncertainty used as input when constructing the initial Thermochemical Network, and corresponds either to the value proposed by the original authors or to our estimate; if an additional multiplier is given in parentheses immediately after the prior uncertainty, it corresponds to the factor by which the prior uncertainty needed to be multiplied during the ATcT analysis in order to make that particular measurement consistent with the prevailing knowledge contained in the Thermochemical Network.

Contribution (%)	TN ID	Reaction	Measured Quantity	Reference
14.0	951.1	OClO (g) → ClO (g) + O (g)	Δ_rH°(0 K) = 247.3 ± 0.5 (×1.509) kJ/mol	Delmdahl 2001
11.6	946.12	OClO (g) → 2 O (g) + Cl (g)	Δ_rH°(0 K) = 122.47 ± 0.20 kcal/mol	Karton 2009c
11.4	951.2	OClO (g) → ClO (g) + O (g)	Δ_rH°(0 K) = 59.0 ± 0.2 kcal/mol	Davis 1996
8.7	953.1	OClO (g) + Br (g) → BrO (g) + ClO (g)	Δ_rG°(298.15 K) = 6.80 ± 0.86 kJ/mol	Clyne 1977, 3rd Law
5.2	967.7	OCl(O)O (g) → Cl (g) + 3 O (g)	Δ_rH°(0 K) = 160.08 ± 0.40 kcal/mol	Karton 2009c, Karton 2017
5.1	946.11	OClO (g) → 2 O (g) + Cl (g)	Δ_rH°(0 K) = 122.33 ± 0.30 kcal/mol	Karton 2006, Karton 2009c, Karton 2011
5.0	951.10	OClO (g) → ClO (g) + O (g)	Δ_rH°(0 K) = 59.03 ± 0.30 kcal/mol	Karton 2009c
5.0	972.7	OCl(O)O (g) + ClO (g) → 2 OClO (g)	Δ_rH°(0 K) = -21.42 ± 0.20 kcal/mol	Karton 2009c
2.9	946.10	OClO (g) → 2 O (g) + Cl (g)	Δ_rH°(0 K) = 122.31 ± 0.40 kcal/mol	Karton 2009c, Martin 2008, Karton 2011
2.8	951.9	OClO (g) → ClO (g) + O (g)	Δ_rH°(0 K) = 59.19 ± 0.40 kcal/mol	Karton 2009c
2.3	967.6	OCl(O)O (g) → Cl (g) + 3 O (g)	Δ_rH°(0 K) = 159.68 ± 0.60 kcal/mol	Karton 2009c
2.2	972.6	OCl(O)O (g) + ClO (g) → 2 OClO (g)	Δ_rH°(0 K) = -21.50 ± 0.3 kcal/mol	Karton 2009c
1.4	946.9	OClO (g) → 2 O (g) + Cl (g)	Δ_rH°(0 K) = 122.14 ± 0.56 kcal/mol	Karton 2009c, Martin 2008, Karton 2011
1.4	951.8	OClO (g) → ClO (g) + O (g)	Δ_rH°(0 K) = 59.04 ± 0.56 kcal/mol	Karton 2009c
1.2	1072.7	HOClO (g) → H (g) + 2 O (g) + Cl (g)	Δ_rH°(0 K) = 192.11 ± 0.35 kcal/mol	Karton 2009c, Karton 2017
0.9	1072.6	HOClO (g) → H (g) + 2 O (g) + Cl (g)	Δ_rH°(0 K) = 192.05 ± 0.40 kcal/mol	Karton 2009c
0.8	1075.7	HOClO (g) + ClO (g) → HOCl (g) + OClO (g)	Δ_rH°(0 K) = -23.75 ± 0.30 kcal/mol	Karton 2009c
0.7	951.11	OClO (g) → ClO (g) + O (g)	Δ_rH°(0 K) = 59.30 ± 0.8 kcal/mol	Grant 2010, Matus 2008a
0.6	934.1	ClO (g) → Cl (g) + O (g)	Δ_rH°(0 K) = 22182.3 ± 3 cm-1	Coxon 1976, note ClO, note ClOa
0.4	1075.6	HOClO (g) + ClO (g) → HOCl (g) + OClO (g)	Δ_rH°(0 K) = -23.68 ± 0.40 kcal/mol	Karton 2009c

Top 10 species with enthalpies of formation correlated to the Δ_fH° of OClO (g)

Please note: The correlation coefficients are obtained by renormalizing the off-diagonal elements of the covariance matrix by the corresponding variances.
The correlation coefficient is a number from -1 to 1, with 1 representing perfectly correlated species, -1 representing perfectly anti-correlated species, and 0 representing perfectly uncorrelated species.

Correlation Coefficent (%)	Species Name	Formula	Δ_fH°(0 K)	Δ_fH°(298.15 K)	Uncertainty	Units	Relative Molecular Mass	ATcT ID
78.1	Chlorite	[OClO]- (g)	-105.51	-107.68	± 0.37	kJ/mol	67.4520 ± 0.0011	14998-27-7*0
61.9	Perchloryl	OCl(O)O (g)	191.77	186.10	± 0.62	kJ/mol	83.4509 ± 0.0013	13932-10-0*0
53.4	Chloryl ion	[OClO]+ (g)	1100.26	1097.60	± 0.53	kJ/mol	67.4510 ± 0.0011	25052-55-5*0
26.4	Chlorous acid	HOClO (g)	25.76	20.71	± 0.63	kJ/mol	68.4594 ± 0.0011	13898-47-0*0
18.3	Perchloryloxy	OCl(O)(O)O (g)	248.4	240.8	± 1.8	kJ/mol	99.4503 ± 0.0015	12133-63-0*0
10.2	Bromooxidanyl	BrO (g)	131.22	123.68	± 0.28	kJ/mol	95.9034 ± 0.0010	15656-19-6*0
9.7	Perchloryl cation	[OCl(O)O]+ (g)	1252.1	1246.4	± 2.5	kJ/mol	83.4504 ± 0.0013	23594-88-9*0
9.0	Chlorate	[OCl(O)O]- (g)	-208.2	-213.7	± 1.4	kJ/mol	83.4514 ± 0.0013	14866-68-3*0
8.5	Chloryl hydride	HCl(O)O (g)	197.7	191.2	± 1.6	kJ/mol	68.4594 ± 0.0011	174365-32-3*0
8.2	Chlorooxidanyl	ClO (g)	101.124	101.716	± 0.035	kJ/mol	51.45210 ± 0.00095	14989-30-1*0

Most Influential reactions involving OClO (g)

Please note: The list, which is based on a hat (projection) matrix analysis, is limited to no more than 20 largest influences.

Influence Coefficient	TN ID	Reaction	Measured Quantity	Reference
0.890	948.1	[OClO]- (g) → OClO (g)	Δ_rH°(0 K) = 2.1451 ± 0.0025 eV	Distelrath 2000
0.860	947.1	OClO (g) → [OClO]+ (g)	Δ_rH°(0 K) = 10.350 ± 0.005 eV	Flesch 1993
0.384	972.7	OCl(O)O (g) + ClO (g) → 2 OClO (g)	Δ_rH°(0 K) = -21.42 ± 0.20 kcal/mol	Karton 2009c
0.240	1075.7	HOClO (g) + ClO (g) → HOCl (g) + OClO (g)	Δ_rH°(0 K) = -23.75 ± 0.30 kcal/mol	Karton 2009c
0.208	1001.4	OCl(O)(O)O (g) + OClO (g) → 2 OCl(O)O (g)	Δ_rH°(0 K) = 7.78 ± 0.85 kcal/mol	Ruscic W1RO
0.198	1081.4	HCl(O)O (g) + ClO (g) → HClO (g) + OClO (g)	Δ_rH°(0 K) = -12.86 ± 0.85 kcal/mol	Ruscic W1RO
0.188	953.1	OClO (g) + Br (g) → BrO (g) + ClO (g)	Δ_rG°(298.15 K) = 6.80 ± 0.86 kJ/mol	Clyne 1977, 3rd Law
0.186	1001.1	OCl(O)(O)O (g) + OClO (g) → 2 OCl(O)O (g)	Δ_rH°(0 K) = 8.78 ± 0.90 kcal/mol	Ruscic G3X
0.177	1081.1	HCl(O)O (g) + ClO (g) → HClO (g) + OClO (g)	Δ_rH°(0 K) = -13.20 ± 0.90 kcal/mol	Ruscic G3X
0.177	1081.2	HCl(O)O (g) + ClO (g) → HClO (g) + OClO (g)	Δ_rH°(0 K) = -13.09 ± 0.90 kcal/mol	Ruscic G4
0.171	972.6	OCl(O)O (g) + ClO (g) → 2 OClO (g)	Δ_rH°(0 K) = -21.50 ± 0.3 kcal/mol	Karton 2009c
0.156	1001.2	OCl(O)(O)O (g) + OClO (g) → 2 OCl(O)O (g)	Δ_rH°(0 K) = 9.03 ± 0.90 (×1.091) kcal/mol	Ruscic G4
0.150	1001.3	OCl(O)(O)O (g) + OClO (g) → 2 OCl(O)O (g)	Δ_rH°(0 K) = 8.19 ± 1.0 kcal/mol	Ruscic CBS-n
0.143	1081.3	HCl(O)O (g) + ClO (g) → HClO (g) + OClO (g)	Δ_rH°(0 K) = -14.11 ± 1.0 kcal/mol	Ruscic CBS-n
0.142	951.1	OClO (g) → ClO (g) + O (g)	Δ_rH°(0 K) = 247.3 ± 0.5 (×1.509) kJ/mol	Delmdahl 2001
0.135	1075.6	HOClO (g) + ClO (g) → HOCl (g) + OClO (g)	Δ_rH°(0 K) = -23.68 ± 0.40 kcal/mol	Karton 2009c
0.116	946.12	OClO (g) → 2 O (g) + Cl (g)	Δ_rH°(0 K) = 122.47 ± 0.20 kcal/mol	Karton 2009c
0.116	951.2	OClO (g) → ClO (g) + O (g)	Δ_rH°(0 K) = 59.0 ± 0.2 kcal/mol	Davis 1996
0.087	973.8	OCl(O)O (g) → OClO (g) + O (g)	Δ_rH°(0 K) = 37.77 ± 0.40 kcal/mol	Karton 2009c
0.087	948.2	[OClO]- (g) → OClO (g)	Δ_rH°(0 K) = 2.140 ± 0.008 eV	Gilles 1992

References

1		B. Ruscic, R. E. Pinzon, M. L. Morton, G. von Laszewski, S. Bittner, S. G. Nijsure, K. A. Amin, M. Minkoff, and A. F. Wagner, Introduction to Active Thermochemical Tables: Several "Key" Enthalpies of Formation Revisited. J. Phys. Chem. A 108, 9979-9997 (2004) [DOI: 10.1021/jp047912y]
2		B. Ruscic, R. E. Pinzon, G. von Laszewski, D. Kodeboyina, A. Burcat, D. Leahy, D. Montoya, and A. F. Wagner, Active Thermochemical Tables: Thermochemistry for the 21^st Century. J. Phys. Conf. Ser. 16, 561-570 (2005) [DOI: 10.1088/1742-6596/16/1/078]
3		B. Ruscic and D. H. Bross, Active Thermochemical Tables (ATcT) values based on ver. 1.176 of the Thermochemical Network (2024); available at ATcT.anl.gov
4		T. L. Nguyen et al, ongoing studies (2024)
5		B. Ruscic, Uncertainty Quantification in Thermochemistry, Benchmarking Electronic Structure Computations, and Active Thermochemical Tables. Int. J. Quantum Chem. 114, 1097-1101 (2014) [DOI: 10.1002/qua.24605]
6		B. Ruscic and D. H. Bross, Thermochemistry Computer Aided Chem. Eng. 45, 3-114 (2019) [DOI: 10.1016/B978-0-444-64087-1.00001-2]

Formula

The aggregate state is given in parentheses following the formula, such as: g - gas-phase, cr - crystal, l - liquid, etc.

Uncertainties

The listed uncertainties correspond to estimated 95% confidence limits, as customary in thermochemistry (see, for example, Ruscic [5] and Ruscic and Bross[6]).
Note that an uncertainty of ± 0.000 kJ/mol indicates that the estimated uncertainty is < ± 0.000₅ kJ/mol.

Website Functionality Credits

The reorganization of the website was developed and implemented by David H. Bross (ANL).
The find function is based on the complete Species Dictionary entries for the appropriate version of the ATcT TN.
The molecule images are rendered by Indigo-depict.
The XYZ renderings are based on Jmol: an open-source Java viewer for chemical structures in 3D. http://www.jmol.org/.

Acknowledgement

This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Contract No. DE-AC02-06CH11357.