Study of Protonation Behaviour and Distribution Ratios of Hydroxamic Acids in Hydrochloric and Perchloric Acid Solutions Through Hammett Acidity Function, Bunnett-Olsen and Excess Acidity Method

Manisha Agarwal; Priyanka Singh; Rama Pande

Korean Chemical Engineering Research, Vol.57, No.2, 164-171, April, 2019

DOI10.9713/kcer.2019.57.2.164 Export Citation

Study of Protonation Behaviour and Distribution Ratios of Hydroxamic Acids in Hydrochloric and Perchloric Acid Solutions Through Hammett Acidity Function, Bunnett-Olsen and Excess Acidity Method

Manisha Agarwal, Priyanka Singh¹, and Rama Pande^{2, †}

School of Studies in Chemistry, Pt. Ravishankar Shukla University, Raipur-492010, Chhattisgarh, India
¹Rungta College of Engineering & Technology, Bhilai-490024, Chhattisgarh, India
²Department of Chemistry, Govt. Digvijay PG Autonomous College, Rajnandgaon-491441 Chhattisgarh, India

E-mail:

The protonation parameters, dissociation constants (pKBH+) of conjugate acid, slope values (m, φ and m*) and correlation coefficients (r) of hydroxamic acids were determined by Hammett acidity function method, Bunnett- Olsen method and excess acidity method in hydrochloric and perchloric acid solutions. Effect of acid concentration on partition and percentage protonation was also studied. pKBH+ values show that hydroxamic acids do not behave as Hammett bases, but hydroxamic acids behave as weak bases in strong acidic solutions. The values of pKBH+ obtained through Bunnett-Olsen method and excess acidity method were compared with the Hammett acidity function. ChemAxon's MarvinSketch 6.1.5 software was also used for determining pKa, pI and microspecies distribution (%) of hydroxamic acids with pH. Hydrogen donor and acceptor values and logD were also obtained. The results show that N-p-chlorophenyl-4- bromobenzohydroxamic acid has the highest pKa and lowest logD values. On the contrary, N-phenyl-3,5-dinitrobenzohydroxamic acid has lowest the pKa and highest logD values.

Keywords:Dissociation constant;hydroxamic acid;logD and protonation parameters

[References]

Garcia VS, Gonzalez VDG, Vega JR, Marcipar IS, Gugliotta LM, Latin Am. Appl. Res., 42, 405 (2012)
Kostiainen R, Kotiaho T, Kuuranne TS, J. Mass Spec., 38, 357 (2003)
Yadav SS, Pande R, Khare D, Tripathi M, J. Chem. Thermodyn., 54, 76 (2012)
Singh P, Pande R, J. Fluoresc., 26, 67 (2016)
Singh P, Khare D, Pande R, Chem. Pap., 68(10), 1298 (2014)
Vernon F, Eccles H, The Theory and Practice Ion Exchange, London SCI 39.1 (1976).
Sharma P, Obrai S, Kumar R, Chem. Bio. Phy. Sci. Sec. A, 3, 91 (2013)
Hassan KF, Kandil SA, Abdel-Aziz HM, Siyam T, Chromatogr. Res. Int., 2011, 1 (2011)
Gidwani MS, Kaur H, Pal U, Menon SK, J. Anal. Chem., 64, 104 (2009)
Farkas E, Enyedy EA, Zekany L, Deak G, J. Inorg. Biochem., 83, 107 (2001)
Jiao C, Zhang Z, Tao J, Zhang D, Chen Y, Lin H, RSC Adv., 7, 27787 (2017)
Tondon SG, Bhattacharya SC, J. Chem. Eng. Data, 7, 553 (1962)
Gupta VK, Tondon SG, J. Chem. Eng. Data, 17, 257 (1972)
Marziano NC, Cimino GM, Passerini RC, J. Chem. Soc.-Perkin Trans. 2, 64, 1253 (1977)
Csizmadia A, Tsantili-Kakoulidou I, Pander F, Darvas, J. Pharm. Sci., 86, 865 (1997)
Cox RA, Yates K, Can. J. Chem., 61, 2225 (1983)
Cox RA, Stewart R, J. Am. Chem. Soc., 98, 488 (1976)
Cox RA, Yates K, J. Am. Chem. Soc., 100, 3861 (1978)
Cox RA, Yates K, Can. J. Chem., 59, 2116 (1981)
Buglass AJ, Hudson K, Tillet J, J. Chem. Soc. Sec. B, 42, 123 (1971)
Zhang S, Zhang T, Tang SW, J. Chem. Eng. Data, 61(6), 2088 (2016)
Bunnett JF, Olsen FP, Can. J. Chem., 44, 1899 (1966)
Arnett EM, Prog. Phys. Org. Chem., 1, 223 (1963)
Vernon F, Khorassani IH, Talanta, 25, 410 (1978)
Pande R, Tandon SG, Talanta, 38, 1015 (1991)
Monzyk BF, United States Patent: 5174917(1992).
Zhang W, Pranolo Y, Urbani M, Cheng CY, Hydrometallurgy, 119-120, 67 (2012)
Ghosh KK, Indian J. Chemistry, 40A, 2683 (2003)
Garcia B, Ibeas S, Hoyuelos FJ, Leal JM, Secco F, Venturini M, J. Org. Chem., 66, 7986 (2001)
Beccia MR, Coordination chemistry. Universita degli studi di Pisa, pp. 7-9(2012).

[1] Garcia VS, Gonzalez VDG, Vega JR, Marcipar IS, Gugliotta LM, Latin Am. Appl. Res., 42, 405 (2012)

[2] Kostiainen R, Kotiaho T, Kuuranne TS, J. Mass Spec., 38, 357 (2003)

[3] Yadav SS, Pande R, Khare D, Tripathi M, J. Chem. Thermodyn., 54, 76 (2012)

[4] Singh P, Pande R, J. Fluoresc., 26, 67 (2016)

[5] Singh P, Khare D, Pande R, Chem. Pap., 68(10), 1298 (2014)

[6] Vernon F, Eccles H, The Theory and Practice Ion Exchange, London SCI 39.1 (1976).

[7] Sharma P, Obrai S, Kumar R, Chem. Bio. Phy. Sci. Sec. A, 3, 91 (2013)

[8] Hassan KF, Kandil SA, Abdel-Aziz HM, Siyam T, Chromatogr. Res. Int., 2011, 1 (2011)

[9] Gidwani MS, Kaur H, Pal U, Menon SK, J. Anal. Chem., 64, 104 (2009)

[10] Farkas E, Enyedy EA, Zekany L, Deak G, J. Inorg. Biochem., 83, 107 (2001)

[11] Jiao C, Zhang Z, Tao J, Zhang D, Chen Y, Lin H, RSC Adv., 7, 27787 (2017)

[12] Tondon SG, Bhattacharya SC, J. Chem. Eng. Data, 7, 553 (1962)

[13] Gupta VK, Tondon SG, J. Chem. Eng. Data, 17, 257 (1972)

[14] Marziano NC, Cimino GM, Passerini RC, J. Chem. Soc.-Perkin Trans. 2, 64, 1253 (1977)

[15] Csizmadia A, Tsantili-Kakoulidou I, Pander F, Darvas, J. Pharm. Sci., 86, 865 (1997)

[16] Cox RA, Yates K, Can. J. Chem., 61, 2225 (1983)

[17] Cox RA, Stewart R, J. Am. Chem. Soc., 98, 488 (1976)

[18] Cox RA, Yates K, J. Am. Chem. Soc., 100, 3861 (1978)

[19] Cox RA, Yates K, Can. J. Chem., 59, 2116 (1981)

[20] Buglass AJ, Hudson K, Tillet J, J. Chem. Soc. Sec. B, 42, 123 (1971)

[21] Zhang S, Zhang T, Tang SW, J. Chem. Eng. Data, 61(6), 2088 (2016)

[22] Bunnett JF, Olsen FP, Can. J. Chem., 44, 1899 (1966)

[23] Arnett EM, Prog. Phys. Org. Chem., 1, 223 (1963)

[24] Vernon F, Khorassani IH, Talanta, 25, 410 (1978)

[25] Pande R, Tandon SG, Talanta, 38, 1015 (1991)

[26] Monzyk BF, United States Patent: 5174917(1992).

[27] Zhang W, Pranolo Y, Urbani M, Cheng CY, Hydrometallurgy, 119-120, 67 (2012)

[28] Ghosh KK, Indian J. Chemistry, 40A, 2683 (2003)

[29] Garcia B, Ibeas S, Hoyuelos FJ, Leal JM, Secco F, Venturini M, J. Org. Chem., 66, 7986 (2001)

[30] Beccia MR, Coordination chemistry. Universita degli studi di Pisa, pp. 7-9(2012).