Comparative Study of Solvation Behaviour of Oxidising Agents Like Kclo3, Kbro3 and KIO3 in Aqueous Solvent Systems at Different Temperatures

Introduction

Generally, an oxidizing agent donates oxygen atoms to a reactant or substrate and hence the oxidizing agent is also called as an oxygenation reagent or oxygen-atom transfer agent [1] or it also serve as electron acceptors. Apart from oxidising agent, KBrO₃ has been used as a food additive, mainly in the bread-making process, flour treatment, as a component of cold-wave hair lotions.Though potassium bromate (KBrO₃) is banned for food use, it is used as a flour improver and high riser in bakery industries. It is known as a renal carcinogen and toxic effects of potassium bromate on endocrine glands was studied [2].KClO₃ is used as safe animal husbandry tool[3]for economically important food animals like sheep, cattle, swine and poultry animals. Potassium chlorate is also measured in dietary supplements and flavour enhancing ingredients [4]and also in bottled drinking water or mineral water. [5].

Potassium iodate also has been used as a food additive, to prevent iodine deficiency. It may be used to protect against the health risks caused by accumulation of radioactive iodine in the thyroid by administrating and saturating the body with a stable source of iodine in the form of KIO₃ prior to exposure [6].KIO₃is the best alternative to potassium iodide KI, as KI has poor shelf life in humid and hot climates [7].The importance of oxidizing agents towards the medical science lead us to undertake the present study.

The extensive information on the transport, thermodynamic and physicochemicalproperties of oxidizing agents  are needed and plays a vital role in multiple industries, biochemical processes, in designing and development of drugs, medicines, vaccines, dyes, marine productsand also for thermal treatment and storage of foods. For this perspective, the comparative study of solvation behaviour of oxidizing agents in aqueous solutions of 0.5 % KCl, play crucial rolenot only in generation but systematization of physicochemical information of the studied solute and solvents. The major intent of this study was to assess the effect of molar concentration of solute and temperature on the apparent molar volume, various interaction parameters and solvolysis of oxidizing agent in different solvent systems. [8-9].

Experimental

Materials

The water used for the preparation of solutions was deionised and purified by successive distillation. The specific conductance of distilled water was found <5x 10^-6 S.cm^-1.The KClO_3, KBrO₃ and KIO_3, of high purity was obtained from Sigma Aldrich, while KCl from  S.D. Fine Lab were vacuum dried and used without further purification.The solutions of molarity range (6.5×10^-3 to 3.65×10^-2) mol.L^-1 were prepared and the measurements of phytochemical properties were carried out at four different temperatures. The precision of balance used was ± 1×10^-5g.

Density Measurements

Calibration of the bicapillary pycnometer was done by measuring the densities of triple distilled water. The densities of KClO₃, KBrO₃ and KIO₃solutions in aqueous 0.5 % KCl, were measured by the same calibrated pycnometer at 298.15, 303.15, 308.15, and 313.15K temperatures. The density was measured with an accuracy of ±1.48 ×10^-4 g.cm^-3.

Viscosity measurements

The six different concentrations (0.0065M to 0.0365M) of solutions of KClO₃, KBrO₃ and KIO₃were prepared in aqueous 0.5 % KCl, solvent systems. To determine the influence of temperature on viscosity, the time outflow were measured at 298.15, 303.15, 308.15, and 313.15K for all six different concentrations.by using Ubbelohde viscometer. The solution viscosities were measured with an uncertainty of ± 2.4×10^-4 mPa.s and the flow time will be measured at the accuracy of± 0.01 s. Demerstat with an accuracy of ± 0.1 K is used to maintain the required temperature of thermostat.

Data Evaluation

The measured density data is used to evaluate the apparent molar volumes , using the following equation [10-13].

where ,M₂, is the molar mass of the  KClO₃,KBrO₃ and KIO_{3 ,}C is the concentration (mol.L^-1) and P and P_o the densities of the solution and the solvent, respectively.

The apparent molar volumes ( ∅_v ) of all the three oxidising agents were plotted against the square root of selected concentration range (C^½) in accord with the Masson’s equation [14]

Values of  empirical parameters ∅⁰_v and S_v which depends on temperature and also on the nature of solute, solvent have been obtained from the linear graphs plotted between  ∅_v and C^½The viscosity data for the KClO₃,KBrO₃ and KIO₃ in aqueous 0.5 % KCl, were plotted in accordance with Jones-Dole equation [15]

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 [16-17] and the B-coefficient reflect the solute-solvent interactions. Since in general, A/B <<1, the Jones –Dole equation reduces to,    

The relation between molar concentration and relative viscosity data of these solutions have also been fitted in Moulik equation,

The density data of these solutions have also been used to deduce the values of R and S constants using Root’s equation,

The viscosity data have been also employed to determine the diffusion controlled reaction rate constant k_d[18].

Results and Discussion

The densities ( P )and viscosities (η) values of KClO₃, KBrO₃ and KIO₃ in aqueous 0.5 % KCl, at different temperatures are reported Table-1.  It is observed that densities and even viscosities increase with increase in molar concentration while it decrease with increase in temperature for all selected oxidising agents.Similar observations were previously made by [19-22] for other solutions.

Table 1: Densities and Viscosities of KClO₃, KBrO₃ and KIO₃solution in 0.5% KCl, at different temperatures.

Solute System	Molar Conc. of Solute (C) mol/dm3	Temperatures				Temperatures
		298.15K	303.15K	308.15K	313.15K	298.15K	303.15K	308.15K	313.15K
		Density, (P ) / (g.cm-3)				Viscosity, (η) / (mPa.s)
KClO3	0.0065	1.00362	1.00198	1.00032	0.99920	0.9143	0.8311	0.7491	0.6757
	0.0105	1.00450	1.00284	1.00120	1.00009	0.9174	0.8351	0.7539	0.6812
	0.0155	1.00560	1.00391	1.00229	1.00117	0.9213	0.8400	0.7598	0.6882
	0.0215	1.00690	1.00519	1.00358	1.00249	0.9259	0.8459	0.7670	0.6966
	0.0285	1.00845	1.00668	1.00513	1.00402	0.9314	0.8528	0.7754	0.7063
	0.0365	1.01010	1.00854	1.00713	1.00572	0.9376	0.8607	0.7850	0.7175
KBrO3	0.0065	1.00431	1.00299	1.00143	0.99946	0.9180	0.8397	0.7615	0.6834
	0.0105	1.00538	1.00407	1.00263	1.00068	0.9231	0.8457	0.7685	0.6902
	0.0155	1.00676	1.00541	1.00398	1.00219	0.9294	0.8532	0.7771	0.7011
	0.0215	1.00839	1.00705	1.00569	1.00402	0.9370	0.8622	0.7875	0.7128
	0.0285	1.01036	1.00898	1.00764	1.00617	0.9460	0.8728	0.7996	0.7263
	0.0365	1.01236	1.01107	1.00991	1.00861	0.9561	0.8848	0.8134	0.7419
KIO3	0.0065	1.00518	1.00391	1.00264	1.00099	0.9296	0.8461	0.7672	0.6834
	0.0105	1.00666	1.00531	1.00401	1.00238	0.9349	0.8516	0.7742	0.6902
	0.0155	1.00851	1.00711	1.00572	1.00407	0.9417	0.8586	0.7824	0.7011
	0.0215	1.01073	1.00925	1.00775	1.00615	0.9497	0.8669	0.7924	0.7128
	0.0285	1.01333	1.01176	1.01018	1.00855	0.9592	0.8767	0.8042	0.7263
	0.0365	1.01649	1.01476	1.01293	1.01101	0.9699	0.8879	0.8177	0.7419

The values of apparent Molar Volumes ( ∅_v ) and Relative Viscosities ( n_r ) of KClO₃, KBrO₃ and KIO₃ in selected solvent systems and at four different temperatures are reported in table-2. The positive values of for all three solute systems decrease with increase of concentration in KCl. Derived relative viscosities from the viscosity data are found to increase with increase in concentrations.

Table 2: Apparent molar volumes and Relative viscosities of KClO₃, KBrO₃ and KIO₃ solution in 0.5% KCl, atdifferent temperatures.

Solute System	Molar Conc. of Solute (C) mol/dm3	Temperatures				Temperatures
		298.15K	303.15K	308.15K	313.15K	298.15K	303.15K	308.15K	313.15K
		Apparent molar volumes, ( ∅v) /cm3.mol-1				Relative viscosities, ( nr)
KClO3	0.0065	121.43	121.61	121.76	121.91	1.0188	1.0095	1.0099	1.0177
	0.0105	121.34	121.54	121.70	121.84	1.0223	1.0131	1.0163	1.0261
	0.0155	121.25	121.45	121.62	121.74	1.0266	1.0179	1.0244	1.0366
	0.0215	121.16	121.37	121.52	121.67	1.0318	1.0239	1.0341	1.0492
	0.0285	121.06	121.28	121.41	121.57	1.0379	1.0312	1.0454	1.0639
	0.0365	120.94	121.14	121.30	121.47	1.0448	1.0396	1.0583	1.0807
KBrO3	0.0065	165.59	165.81	166.06	166.40	1.0231	1.0236	1.0267	1.0293
	0.0105	165.39	165.62	165.89	166.20	1.0286	1.0309	1.0360	1.0396
	0.0155	165.23	165.44	165.71	165.98	1.0356	1.0401	1.0477	1.056
	0.0215	165.03	165.25	165.48	165.74	1.0441	1.0510	1.0617	1.0735
	0.0285	164.85	165.08	165.29	165.53	1.0541	1.0639	1.0782	1.0939
	0.0365	164.62	164.88	165.09	165.29	1.0655	1.0785	1.0966	1.1175
KIO3	0.0065	212.39	212.67	213.00	213.32	1.0358	1.0312	1.0344	1.0293
	0.0105	212.14	212.43	212.74	213.07	1.0418	1.0381	1.0434	1.0396
	0.0155	211.89	212.17	212.48	212.82	1.0494	1.0466	1.0548	1.0560
	0.0215	211.60	211.88	212.20	212.52	1.0583	1.0567	1.0683	1.0735
	0.0285	211.27	211.60	211.89	212.24	1.0688	1.0687	1.0843	1.0939
	0.0365	210.99	211.26	211.54	211.96	1.0808	1.0824	1.1024	1.1175

The apparent molar volumes at infinite dilution

and slopes S_v , calculated using Masson equation (2) are reported in table-3. The ∅_V⁰  values of KClO₃, KBrO₃ and KIO₃ under investigation in KCl, are large and positive suggests presence of strong solute-solvent interactions promotes structure making effect [23].

Table 3: Masson,Moulik, Jone-Dole and Roots parameters of KClO₃, KBrO₃ and KIO₃solution in 0.5% KCl  at different temperatures.

Parameters	Temperature (K)	KClO3	KBrO3	KIO3
Masson’s Parameters
∅V0	298.15	121.7	166.2	213.4
	303.15	121.9	166.4	213.7
	308.15	122.1	166.8	214.1
	313.15	122.2	167.2	214.3
Sv	298.15	-4.05	-8.62	-12.8
	303.15	-4.03	-8.34	-12.64
	308.15	-3.89	-8.93	-13.06
	313.15	-3.16	-10.07	-12.42
Moulik Parameters
K	298.15	57.27	66.49	71.27
	303.15	68.16	86.46	80.91
	308.15	64.00	112.20	108.80
	313.15	86.68	142.70	142.70
M	298.15	1.03	1.05	1.08
	303.15	1.02	1.06	1.07
	308.15	1.03	1.06	1.08
	313.15	1.03	1.07	1.07
Jone-Dole Parameters
A	298.15	0.03	0.21	0.28
	303.15	0.05	0.19	0.30
	308.15	-0.03	0.19	0.28
	313.15	0.03	0.17	0.29
B	298.15	0.35	0.71	0.54
	303.15	0.93	1.15	0.47
	308.15	1.58	1.60	1.14
	313.15	1.79	2.28	1.16
Roots Parameters
R	298.15	1.45	0.75	0.74
	303.15	1.46	0.73	0.73
	308.15	1.50	0.73	0.73
	313.15	1.39	0.59	0.59
S	298.15	-5.17	-2.36	-2.36
	303.15	-5.21	-2.31	-2.31
	308.15	-5.50	-2.21	-2.21
	313.15	-4.86	-1.41	-2.36

The Diffusion reaction rate constant (kd) evaluated by equation (7) and are reported in table-4.The apparent molar volumes of transfer Δ ∅(tr) of KClO₃, KBrO₃ and KIO₃ and are obtained from the following  relation and are included in table-5

Table 4:  Diffusion reaction rate constant k_d (L mol^-1 s^-1) values of KClO₃, KBrO₃ and KIO₃ solution in 0.5% KCl solution .            

Solvent System	Molar Conc. of (C) mol/dm3	Temperatures
		298.15K	303.15K	308.15K	313.15K
		Diffusion reaction rate constant kd (L mol-1 s-1 ) x 1010
KClO3	0.0065	7.23	8.09	9.12	10.28
	0.0105	7.21	8.05	9.06	10.19
	0.0155	7.18	8.00	8.99	10.09
	0.0215	7.14	7.95	8.91	9.97
	0.0285	7.10	7.88	8.81	9.83
	0.0365	7.05	7.81	8.70	9.68
KBrO3	0.0065	7.20	8.00	8.97	10.16
	0.0105	7.16	7.95	8.89	10.06
	0.0155	7.11	7.88	8.79	9.90
	0.0215	7.05	7.79	8.68	9.74
	0.0285	6.99	7.70	8.54	9.56
	0.0365	6.91	7.60	8.40	9.36
KIO3	0.0065	7.11	7.94	8.90	10.16
	0.0105	7.07	7.89	8.83	10.06
	0.0155	7.02	7.83	8.73	9.90
	0.0215	6.96	7.75	8.62	9.74
	0.0285	6.89	7.67	8.49	9.56
	0.0365	6.82	7.57	8.36	9.36

Table 5: The apparent molar volumes of transfer Δ (tr) of KClO₃, KBrO₃ and KIO₃ solution in 0.5% KCl solution .  

Solvent System	Molar Conc. of KBrO3 (C) mol/dm3	Temperatures
		298.15K	303.15K	308.15K	313.15K
		Δ (tr) /cm3.mol-1
KClO3	0.0065	-0.06	-0.10	-0.12	-0.03
	0.0105	-0.11	-0.13	-0.16	-0.07
	0.0155	-0.12	-0.13	-0.19	-0.12
	0.0215	-0.15	-0.17	-0.22	-0.18
	0.0285	-0.24	-0.15	-0.27	-0.19
	0.0365	-0.20	-0.20	-0.29	-0.28
KBrO3	0.0065	-0.65	-0.76	-0.82	-0.93
	0.0105	-0.66	-0.65	-0.68	-0.77
	0.0155	-0.68	-0.64	-0.6	-0.67
	0.0215	-0.75	-0.6	-0.51	-0.49
	0.0285	-0.80	-0.6	-0.42	-0.37
	0.0365	-0.83	-0.57	-0.37	-0.21
KIO3	0.0065	-0.17	-0.23	-0.08	-0.13
	0.0105	-0.23	-0.24	-0.13	-0.17
	0.0155	-0.24	-0.24	-0.17	-0.26
	0.0215	-0.29	-0.27	-0.22	-0.29
	0.0285	-0.36	-0.27	-0.25	-0.36
	0.0365	-0.40	-0.3	-0.39	-0.42

 

Figure-1 is the plot of ∅_v (cm³.mol^-1)Versus C^½ (mol^1/2.dm^-3/2) for KClO₃ solution in 0.5% KCl at T=298.15 to 313.15K. KBrO₃ and KIO₃ solution in 0.5% KCl also gave the similar linear plots. It is clear that for all the three solutes i.e. KClO₃, KBrO₃ and KIO₃ in 0.5 % KCl solution, the values of ∅_v (cm³.mol^-1) are positive while the listed slope S_v is negative. Since extent of solute-solute interactions are interpreted from the slope S_v,here Sv is negative [24-25], which indicate the strong interaction amongst solute-solute. Secondly there is no specific trend with S_v values either with temperature or concentration, it proposes that the solute-solute interactions are unaffected to change in temperature.

Figure 1: Plots of (cm3.mol-1) versus C½ (mol1/2.dm-3/2) for KClO3, KBrO3, KIO3 in 0.5 % KCl at T=298.15 to 313.15K. Click here to View figure

Plots of (η_r – l)/C^1/2 vs C^1/2 for  KClO₃,KBrO₃ and KIO₃solution in 0.5% KCl at different temperatures are shown in figure 2. The linear plots of (η_r – l)/C^1/2 vs C^1/2 are obtained at all temperatures with regression coefficients higher than 0.99. The slopes of the plots are positive.

Figure 2: Plots of (ηr-1)/C½ vs C½ for KClO3, KBrO3, KIO3 in 0.5 % KCl at T=298.15 to 313.15K. Click here to View figure

Sharma, Rani, R., Kumar, A., & Bamezai,[26]observed that during ionic-ionic interactions, co-sphere of two ionic species overlaps and it adds to increase the  volume  of solution while decrease in volume is noted due to overlapping of  co-sphereof hydrophilic-hydrophobic groups or  ion hydrophobic groups The negative values of  Δ∅_v (tr) have been reported  in terms of weaker ion-ion and ion-hydrophilic group interactions than the ion-hydrophobic interaction. It results in an decrease in volume. Co-sphere overlap model developed by Gurney [27]is utilised for the better understanding of various inter ionic attractions. It is also interpreted that the properties of solvent molecule in the hydration co-sphere depend on the nature of solute species [28-29].

Conclusions

In the present research article, solvolysis and transport properties of KClO₃, KBrO₃ and KIO₃solutions in 0.5% salt solutions at different temperatures and concentrations are methodically reported. he effect of temperature on the ∅⁰_v has been reported in terms of ion-solvent interactions. It has been concluded that in all the three solute systems, there exist strong solute– solvent interactions in these systems. The ∅⁰_v values reported in present study are found to be positive suggest presence of ion-solvent interactions. Thelarge and positive ∅⁰_v  values for all the three solute systems has been employed to predict the  presence of strong solute-solvent interactions promotes structure making effect . The Moulik, Roots and Jones-Dole reduced equation are verified for KClO_3, KBrO₃, and KIO₃ solutions in these solvent systems. The positive K_d value interprets that solvolysis ofKClO_3, KBrO₃, and KIO₃in 0.5% salt solutions at different temperatures and concentrations is diffusion controlled process rather than activated controlled process.

Acknowledgement

I would like to sincerely acknowledge the guidance and help provided by Dr. Arun B. Nikumbh for compilation of this research report.

Conflict of Interest

There is no conflick of interest.

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