Revealing the Toxicity of Chlorate Through the Analysis of Molecular Interaction using Viscosity Measurements and Apparent Molar Volumes

While chlorate has the ability to induce flowering in longan, it also has adverse impacts on the crop. Revealing the toxicity of chlorate in the environment is more than just about the environment and about human health, as well. Because of the large introduction of this chemical into the environment from the paper processing industry, there is indeed a lot of concern about its toxicity. Chlorate toxicology in the longan plant has been thoroughly investigated in solutions using viscosities and apparent molar volumes. The hydration of molecules and volume changes are involved in various chemical and biological processes in plant tissues, and their complete understanding demands a good idea for volumetric and viscometric study. It offers good data acquisition techniques for solute, solvent and solvent-solvent interactions. Multi-component systems containing KClO3+ water + ionic solid (ionic solids = KCl, KNO3, NH4NO3 and KH2PO4, are currently being worked out to study the dependence of transport properties of potassium chlorate in aqueous electrolyte solutions, with concentrations and temperature of solutions. The assessed kd values are used to predict whether the solvolysis of KClO3 in the presence of other electrolytes is a quick or slow process. keywords: Toxicity, KClO3, Volumetric and Viscometric properties, Diffusion controlled Reaction Rate Constant kd.


INTRODUCTION
Lychees and longans are close family members. longans and lychees are comparable in nutritional composition. Both are minimal in calories and carbohydrates and are nil in fat. The antioxidants and fibres are abundant in longan and lychee similarly are great source of vitamin C. of fireworks and matching bands also involves extensively utilised potassium chlorate. In smoke compositions such as smoke grenades it is utilised as a component. In laboratories and educational facilities, potassium chlorate is used to generate oxygen, other than explosives. It is also utilised for the destruction of pests as a pesticide in agriculture. (https://www.businesswire.com/portal/site/home/ my-business-wire/, 2020).
A significant amount of information is needed on the properties of transport, thermodynamic and solution to comprehend how the co-solvent or co-solute can change the nature and structure of the water. (Bahadur, 2019).
This work examines the interaction like ion-solvent, ion-ion and solvent-solvent of potassium chlorate with aqueous ionic salts, as both the solute and solvents are utilised for agricultural operations. In this study the chemical and the electrostatic effect due to dielectric constant of the co-solute which are already present in soil like KCl, KNO 3 and NH 4 NO 3 , KH 2 PO 4 would play vital role in influencing solutesolvent interaction. (Ganjare, 2020). Viscosity data can be used to determine the diffusion controlled reaction rate constant k d .
The current study used multi-component systems containing an ionic solid, water, and KClO 3 (ionic solids = KCl, KNO 3 , and NH 4 NO 3 , KH 2 PO 4 )) to evaluate the relationship between the transport properties of KClO 3 solutions in aqueous electrolyte solutions and solution concentrations and temperature.
The densities of aqueous solutions were measured using 15 cm 3 double arm pycnometer in a transparent glass walled water bath. (Kharat, 2007) Triple distilled water was used to calibrate the pycnometer. At desired temperatures, the densities of KClO 3 solutions in aqueous 1% KCl, KNO 3 and NHNO 3 , KH 2 PO 4 , and pure water were determined using a bi-capillary pycnometer. An average of triplicate measurements was the final result and the density was calculated with an accuracy of ±1.25 ×10 -4 g.cm -3 . The thermostat temperature is maintained at the appropriate temperatures using a demerstat with an accuracy of ±0.1 K.
Viscosities of all salt solutions of ten different concentrations in water were measured using Ubbelohde viscometer at temperatures of 298.15,

Fig. 2. Longan Fruit
Longan (Dimocarpus longan), a subtropical fruit plant belonging to the Sapindaceae family, is ideally suited to tropical regions with distinct wet/ dry seasons as well as subtropical locales with a cool, nonfreezing fall/winter period. In India, it is one of the minor fruits. There is currently insufficient documentation on longan production in India to analyze the real scenario. The longan is an important crop in Southeast Asia economically. Although leaves and flowers are sold in markets, they are not used in traditional medicine. The dried flowers are shipped to Malaysia to be used as medicine.
Though chlorate is able to precisely induce flowering in longan, it also causes toxic effects on the crop. KClO 3 serves as a herbicide or a defoliant on many other plants. (Nahar, 2010) (Manochai P. J., August 2008) While chlorate is able to specifically induce flowering in longan, it also causes toxic effects on the crop. (Sritontip C. Y., 2003). Great concern is paid upon the toxicity of chlorate (Daniel, 1990) because of heavy introduction of this chemical into the environment from paper making industry. (Moore & Calabrese, 1982). An increasing demand from end user industries, such as farming, explosives, laboratories and disinfectants is predicted to contribute significantly to the growth of the potassium chlorate market in the forecast time frame. The explosives based on potassium chlorate are more effective than ordinary powder. The production 303.15, 308.15, and 313.15K. Measurements to monitor reproductibility of results have been repeated at least three times The overall precision of viscosity measurements was ± 2.0×10 -4 mPa.s. At 0.01 second intervals the flow time is accurately recorded.
All chemicals were taken from Sigma Aldrich, Germany, with more than 99% purity and was further desiccated over anhydrous CaCl 2 before use. (Nanda, Nanda, & Mohanty, 2012), The sample specification is given in Table 1a,b. It is known the properties like density, viscosity, etc., are influenced by the presence of oxygen atom in a molecule. The presence of such groups increases the hydrophilicity and electrostriction between water and solute particles. (Nanda, Nanda, & Dalai, 2021).

Data Evaluation
The apparent molar volumes ∅ V , were obtained from the density results using the following equation (Cui, et  (1) Where M is the molar mass of the KClO 3 in g mol -1 , C is the concentration (mol.L -1 ), ρ and ρ 0 and the densities of the solution and the solvent, respectively in g cm -3 The apparent molar volumes (∅ V ) were plotted against the square root of concentration (C ½ ) in accordance with the Masson's equation. Partial molar volumes at infinite dilution were obtained by least-squares fitting to the equation: (Caro, 2020).
Where ∅ V 0 is the limiting apparent molar volume and S v a semi-empirical parameter which depends on the nature of solute, solvent as well as temperature. The apparent molar volumes of transfer at infinite dilutions ∆ f v ⁰ (tr) of KClO 3 obtained from the relation.
The positive ∆∅ V 0 (tr) studied in the present investigation suggest that the ion-ion and ionhydrophilic group interactions are stronger than the ion hydrophobic interaction that results in an increase in volume.  Where η r = (η/η o ) and η, η o are viscosities of the solution and solvent respectively, C is the molar concentration. The B-coefficients were obtained from the linear plots using the least-square fitting method. The A-coefficient reflects solute-solute interaction (Pérez-Durán, 2019) and the B-coefficient reflect the solute-solvent interactions. Since in general, A/B <<1, the Jones -Dole equation reduces to, The relative viscosity data of these solutions have also been fitted in Moulik equation, The density data of these solutions have also been fitted in Root's equation, where R and S are constants.
The diffusion controlled reaction rate constant k d can be evaluated by using the viscosity data as (Rathi & Nikumbh, 2019).
The evaluated values are used to predict whether the solvolysis is fast or slow process.

RESULT AND DISCUSSION
The values of densities and viscosities of KClO 3 solutions decrease with increase in temperature and increases with increase in concentration. The apparent molar volume values of ∅ V decrease with concentration while the relative viscosities are found to increase with concentrations.

CONCLUSION
The increase in densities and viscosities with concentration may be due to strengthening of solute-solvent interactions. (Gupta, 2019). All the investigated parameters has been revealed that there exist strong solute-solvent interaction.
This molecular interaction data help to reveal the toxicity of chlorate. When chlorate is added in the soil or injected in the stem of Longan plants, it creates a strong solute-solvent interaction with the other aqueous ionic solids which are already present in the soil or plant tissues. Chlorate acts as a structure maker and form a tight solvation layer as well as high compactness around the solute. Over-application of flower-inducing chlorate failed to induce flower but caused toxic effects such as leaf chlorosis and drop in longan. The solvolysis of KClO 3 in water and KNO 3 or other nitrate and phosphate solutions at different temperatures is diffusion controlled process. The co-sphere of solvent significantly suppressed nitrate reducing activity in the leaves. This suggested that chlorate not only inhibited photosynthesis due to stomata closure but also due to breakdown of photosynthetic apparatus in chloroplasts. (Sritontip C. Y., 1999) The higher values of densities of KClO 3 in KCl, KNO 3 , NH 4 NO 3 and KH 2 PO 4 are due to the relative salvation, corresponding relative volumes of system and molar mass of the salts. Strong molecular interactions induces chlorate stress (LU Jiemei, 2017) due to occurrence of osmotic adjustment which results in massive accumulation of soluble amino acids and sugars. Excessive use of chlorate as a bleaching agent toxifies the water (Lubbers, Chauhan, & Bianchine, 1981), soil and disturbs the environment's equilibrium. (Kanitz, 1996). Reducing the usage of chlorate, used in the production of colours, safety matches, and explosives for tanning and finishing leather, is important in order to conserve and save the environment.