# A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals

^{1}

^{2}

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## Abstract

**:**

**Dataset:**doi: 10.5281/zenodo.4467868

**Dataset License:**Dataset is made available under the Creative Commons license CC BY (SA).

## 1. Summary

## 2. Data Description

#### 2.1. Summary of Data

- Original literature data (Excel Sheets “Data” and “References”);
- Functional group definitions (Excel Sheet “Groups List”);
- Derived kinetic constants (Excel Sheets “Concentration Lookup”, “Group defaults” and “Group Rates Matrix”).

#### Chemical Structure Format (the SMILES Convention)

#### 2.2. Summary Statistics

#### 2.3. Data Schema

## 3. Methods

#### 3.1. Literature Search for Data

_{10}, m and c values from Equation (2) below. This is not ideal, as these are semi-anecdotal reports gathered up to a century ago under a wide range of conditions and illustrates the need for more systematic measurement of some literature values.

#### 3.2. Data Checking and Validation

#### 3.3. Rate Units

^{−1}. This is true of almost all reactions studied; for those where second-order kinetics applies at higher concentrations (e.g., [17,18]), first-order kinetics are approximated at low concentrations. If rate constants or raw data were reported in units other than second

^{−1}, the rate was converted according to Equation (1) reported in time units other than seconds where:

^{−1}, rate(units) is the rate in some other time unit, and (seconds/unit) is the number of seconds in that time unit.

_{3}and H

_{2}S

_{2}O

_{7,}become significant players in reaction chemistry [21], Hammett acidity becomes highly nonlinear with concentration [1], and this simple formalism is less reliable.

#### 3.4. Calculation of Q_{10} Values

_{10}value—the multiple by which a reaction rate increases for a 10 °C increase in temperature. A wide range of temperature data was converted to a uniform Q

_{10}parameter for the 83 reports that included data on rates at different temperatures.

_{10}was calculated from the reports of the rate at a different temperature as follows: For a table of rate values and temperatures, starting with the lowest temperature, the gradient of a plot of (log(rate/rate

_{o}) vs. (T − T

_{o})/10 gave as gradient log(Q

_{10}), where the rate is the rate at temperature T, and rate

_{o}is the rate at temperature To.

_{10}for a single concentration of sulfuric acid (measurements designated SINGLE_Q10). This was reported in the database, together with the concentration at which it was measured. Others allowed calculations of Q

_{10}for several acid concentrations (measurements, which were designated MULTIPLE_Q10). For these, the value of Q

_{10}was plotted as a function of acid concentration, and the data set records the gradient and intercept of a straight line least-squares match through those data to form Equation (3):

_{10}= n ∗ (conc.) + d

_{10}data, as shown in Table 1 (By contrast, all entries, by definition, had kinetic rate data).

#### 3.5. Inference of Unmeasured Kinetic Parameters for Solvolysis Reactions

_{3}group to a molecule). Solvolysis reactions have kinetics that depends on the nature of the group being affected, and there is a wide range of possible groups. Sulfonations, by contrast, happens almost exclusively on phenyl rings (for reasons discussed below) and hence have more uniform chemistry.

- A mean gradient m from all the Equation (2). If no gradient was available for a functional group, i.e., there are no MULTIPLE values for that functional group, then the mean of the gradient m for the entire dataset is used instead. The result is designated GROUP_RATE_DEFAULT_GRADIENT;
- A mean gradient for Q
_{10}as a function of acid concentration for each functional group. If a functional group has no MULTIPLE_Q10 values, then the mean of the gradient of Q_{10}with acid concentration for the entire dataset is used instead. The result is designated GROUP_Q10_DEFAULT_GRADIENT.

- Fill in a complete set of parameters for Equations (1) and (2) as follows:
- For MULTIPLE data:
- Rate gradients m and constants c for Equation (2) were taken from the experimental data

- For SINGLE data:
- Rate gradients m for Equation (2) were looked up in the table of GROUP_RATE_DEFAULT_GRADIENT values
- Rate constants c for Equation (2) were calculated according to:c = LOG(rate) − GROUP_RATE_DEFAULT_GRADIENT ∗ concentration,

- For MULTIPLE_Q10 data
- Gradient n and constant d in Equation (3) relating Q10 to acid concentration were taken from experimental data

- For SINGLE_Q10 data
- Gradient n in Equation (3) relating Q10 to acid concentration were looked up in the table GROUP_Q10_DEFAULT_GRADIENT
- The constant d in Equation (3) was calculated according to Equation (5):d = Measured_Q10 − GROUP_Q10_DEFAULT_GRADIENT ∗ concentration,

- For No_Q10 values (i.e., measurements where no data on the dependence on rate with temperature was published)
- Gradient n in Equation (3) relating Q10 to acid concentration were looked up in the table of GROUP_Q10_DEFAULT_GRADIENT
- The constant d in Equation (3) was assumed to be the global average value of d = 3.41612

- Calculate rates for all molecules based on the interpolated constant data. With the “filled in” table of values for m, c, n and d, we calculate the predicted rate constant k for each reaction in the original dataset according to Equation (6):$$k={10}^{\left(m.acid+c\right)}\xb7{\left(n.acid+d\right)}^{\frac{\left(T-To\right)}{10}}$$
^{−1}.The selection of T and acid is arbitrary, but to build a systematic table in which values can easily be looked up, a matrix of temperatures from −20 °C to 100 °C and 60% acid to 100% acid was used. - Average rates for all reactions in each functional group, to make an average rate for that functional group

_{10}(rate constant)

#### 3.6. Inference of Unmeasured Kinetic Parameters for Sulfonation Reactions

_{3}in pure sulfuric acid) [22,23].

_{p}is the rate of sulfonation of benzene, S

_{i}is the multiplicative factor for substituent i, and z is the number of i substituents on the ring. Multiplicative factors for the addition of substituents to the ring were then estimated using a simulated annealing algorithm [9] to minimize the difference between predicted values and experimental values for the range of substituted phenyls present in the original experimental dataset under the same matrix of conditions described in Section 3.5, algorithm step 2 above.

## 4. User Notes

- Lookup of reaction rates for specific functional groups, using tables in the sheets “group defaults” (for sulfonation) and “group rates matrix” (for solvolysis) for a specific set of conditions;
- Lookup interpolated kinetic data from the sheet “data” to build a customized database of rates, either for a customized set of conditions or using a different averaging schema;
- Use the primary data from the datasheet to build a new algorithm for “filling in” missing data and/or trace original data from the references listed.

## Author Contributions

## Funding

## Data Availability Statement

## Conflicts of Interest

## References

- Liler, M. Reaction Mechanisms in Sulphuric Acid and Other Strong Acid Solutions; Academic Press: London, UK, 1971. [Google Scholar]
- Cerfontain, H. Mechanistic Aspects in Aromatic Sulfonation and Desulfonation; Interscience Publishers: New York, NY, USA, 1968. [Google Scholar]
- Cox, R.A.; Yates, K. Kinetic equations for reactions in concentrated aqueous acids based on the concept of “excess acidity”. Can. J. Chem.
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**1988**, 28, 31–36. [Google Scholar] [CrossRef] - Van Drie, J.H.; Weininger, D.; Martin, Y.C. ALADDIN: An integrated tool for computer-assisted molecular design and pharmacophore recognition from geometric, steric, and substructure searching of three-dimensional molecular structures. J. Comput. Aided Mol. Des.
**1989**, 3, 225–251. [Google Scholar] [CrossRef] - Edward, J.T.; Meacock, S.C.R. 383. Hydrolysis of amides and related compounds. Part I. Some benzamides in strong aqueous acid. J. Chem. Soc.
**1957**, 2000–2007. [Google Scholar] [CrossRef] - Smith, C.R.; Yates, K. Structure, medium, and temperature dependence of acid-catalyzed amide hydrolysis. J. Am. Chem. Soc.
**1971**, 93, 6578–6583. [Google Scholar] [CrossRef] - Greaves, J.S.; Richards, A.M.; Bains, W.; Rimmer, P.B.; Sagawa, H.; Clements, D.L.; Seager, S.; Petkowski, J.J.; Sousa-Silva, C.; Ranjan, S. Phosphine gas in the cloud decks of Venus. Nat. Astron.
**2020**. [Google Scholar] [CrossRef] - Xiao-yong, Z. Process for purification of crude acetylene gas by using concentrated sulphuric acid. Polyvinyl Chloride.
**2009**, 7. [Google Scholar] - Sheldrick, G.M. Nuclear Magneic Resonace Studies of Inorganic Hydrides; University of Cambridge: Cambridge, UK, 1966. [Google Scholar]
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- Dorfman, Y.; Yukht, I.; Levina, L.; Polimbetova, G.; Petrova, T.; Emelyanova, V. Oxidation of Ph3 and Ash3 through metal-complexes, free and connected oxygen. Uspekhi Khimii
**1991**, 60, 1190–1228. [Google Scholar] - Miller, S.A. Acetylene: Its Properties, Manufacture and Uses; Ernest Bern Ltd.: London, UK, 1965; Volume I. [Google Scholar]
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**2007**, 41, 6212–6224. [Google Scholar] [CrossRef] - Hammett, L.P. The Determination of the Proton-Attracting Properties of Liquids. J. Chem. Phys.
**1940**, 8, 644. [Google Scholar] [CrossRef] - Jorgenson, M.J.; Hartter, D.R. A Critical Re-evaluation of the Hammett Acidity Function at Moderate and High Acid Concentrations of Sulfuric Acid. New H0 Values Based Solely on a Set of Primary Aniline Indicators. J. Am. Chem. Soc.
**1963**, 85, 878–883. [Google Scholar] [CrossRef] - Cox, R.A. Mechanistic studies in strong acids. I. General considerations. Catalysis by individual acid species in sulfuric acid. J. Am. Chem. Soc.
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**1943**, 65, 2233–2236. [Google Scholar] [CrossRef] - Den Hertog, H.J.; van der Plas, H.C.; Buurman, D.J. The reactivity of pyridine towards sulphuric acid at elevated temperatures. Recl. Des Trav. Chim. Des Pays Bas
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**Figure 1.**Data types and their relationships are presented in this paper. Top row—the data sets presented here. Central row—the relationship between the data sets and their interconversion. Bottom row—types of data and applications that can be taken from the current data set for uses as a literature resource, a resource for modeling or a lookup table for chemical stability.

**Figure 2.**Pipeline for calculation of interpolated kinetic values for the reactions in the database. See Section 3.5 text for details. Yellow boxes show data types as listed in Table 2.

No_Q10 | SINGLE_Q10 | MULTIPLE_Q10 | |
---|---|---|---|

SINGLE | 182 | 14 | 0 |

MULTIPLE | 326 | 38 | 31 |

Field Name | Field Description |
---|---|

Sheet “Data”(in columns) | |

NAME | Compound name |

InChI | IUPAC InChI code for the compound |

SMILES | SMILES string for compound |

REACTION | Type of chemical reaction undergone |

SINGLE_CONC | For SINGLE type, the concentration of acid used |

SINGLE_CONC_UNITS | For SINGLE type, units for concentration reported |

REF_TEMP | Temperature at which reaction was reported |

SINGLE_RATE | For SINGLE type, rate of reaction |

MUTLIPLE_GRADIENT | For MULTIPLE type, gradient (m) in Equation (2) |

MULTIPLE_INTERCEPT | For MULTIPLE type, intercept (c) in Equation (2) |

TIME_UNITS | Units of time in which rates are reported (seconds, minutes, etc.) |

MULTIPLE_CONC_UNITS | For MULTIPLE type, units of concentration for Equation (2) |

SINGLE_Q10 | For SINGLE_Q10 type, value of Q10 |

SINGLE_Q10_CONC | For SINGLE_Q10 type, concentration at which Q10 was calculated |

MULTIPLE_Q10_GRADIENT | For MULTIPLE_Q10 type, gradient (n) in Equation (3) |

MULTIPLE_Q10_INTERCEPT | For MULTIPLE Q10 type, intercept (d) in Equation (3) |

REFERENCE | Literature reference (see “Sheet reference”’ below) |

MULTIPLE_STANDARD_GRADIENT | For MULTIPLE type, gradient (m) in Equation (2) normalized to % concentration units and seconds^{−1} rate units |

MULTIPLE_STANDARD_INTERCEPT | For MULTIPLE type, intercept (d) in Equation (2) normalized to % concentration units and seconds^{−1} rate units |

SINGLE_STANDARD_CONC | For SINGLE type, concentration converted to % acid |

SINGLE_STANDARD_RATE | For SINGLE type, rate converted to seconds^{−1} |

GROUP | Functional group number (see “Sheet, groups list” below) |

EXTRAPOLATED_EQUATION_GRADIENT | Filled in gradient in Equation (2) as described in Section 3.5 below |

EXTRAPOLATED_EQUATION_INTERCEPT | Filled in intercept in Equation (2) as described in Section 3.5 below |

EXTRAPOLATED_Q10_GRADIENT | Filled in gradient in Equation (3) as described in Section 3.5 below |

EXTRAPOLATED_Q10_INTERCEPT | Filled in intercept in Equation (3) as described in Section 3.5 below |

Sheet “Concentration lookup” | |

MOLAR and %_MOLAR | Values of concentration of sulfuric acid in molar, and corresponding values of % acid |

Ho and %_Ho | Values are Hammett acidity of sulfuric acid and corresponding values of % acid |

Sheet “Groups list”(in columns) | |

NUMBER | Number code used in GROUP column in data and group defaults sheets |

NAME | Internal name for this functional group |

SMARTS | SMARTS string description of this functional group |

STRUCTURE | Pictorial representation of structure |

Sheet “Group defaults” (in rows) | |

GROUP | Group number |

NAME | Internal name for this functional group |

GROUP_RATE_DEFAULT GRADIENT | Default gradient for use in extrapolating SINGLE measurement types for this functional group |

GROUP_Q10_DEFAULT | Default Q10 value for this group |

Sheet “Group rates matrix” (in columns) | |

GROUP | Functional group number |

NAME | Functional group name |

Columns 3 (C) thru 119 (DO): | |

Row 1: | Temperature |

Row 2: | Acid concentration |

Rows 3 thru 132: | Log of reaction rate constant in seconds^{−1} of that functional group (column 1) at the temperature and acid concentration specified at the head of the column |

Sheet “References” (in columns) | |

References as cited in sheet “Data” |

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## Share and Cite

**MDPI and ACS Style**

Bains, W.; Petkowski, J.J.; Seager, S. A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals. *Data* **2021**, *6*, 24.
https://doi.org/10.3390/data6030024

**AMA Style**

Bains W, Petkowski JJ, Seager S. A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals. *Data*. 2021; 6(3):24.
https://doi.org/10.3390/data6030024

**Chicago/Turabian Style**

Bains, William, Janusz Jurand Petkowski, and Sara Seager. 2021. "A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals" *Data* 6, no. 3: 24.
https://doi.org/10.3390/data6030024