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Synergic Extraction of Rare Earth Elements Using Picrolonic Acid and Other Neutral Oxo-Donors

Thesis Info

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Author

Rehman, Habib-Ur-

Program

PhD

Institute

University of the Punjab

City

Lahore

Province

Punjab

Country

Pakistan

Thesis Completing Year

2009

Thesis Completion Status

Completed

Subject

Chemistry

Language

English

Link

http://prr.hec.gov.pk/jspui/handle/123456789/1110

Added

2021-02-17 19:49:13

Modified

2024-03-24 20:25:49

ARI ID

1676727426402

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Extensive work is being carried on the extraction of rare earth elements due to their special chemical, metallurgical, optical, magnetic and nuclear properties and their use in advanced technologies as well as in nuclear industry. Different chemical processes are being applied for the extraction of rare earth elements from their ores and their mutual separation on laboratory scale as well as on commercial basis. However, these processes are facing problems such as large number of stages due to low separation factor, low efficiency and waste management. Keeping in view of these problems, in the present research work, a synergic extraction system comprising of picrolonic acid as an acidic chelating agent and oxygen based neutral donors, for the extraction / separation of rare earth elements has been studied. Synergic extraction of Ce(III), Nd(III), Eu(III), Tb(III), Tm(III) and Lu(III) as representative of trivalent lanthanides, using picrlonic acid (1-p-nitrophenyl-3-methyl-4- nitro-5-pyrazolone, HPA, pKa = 2.52) as acidic chelating agent with crown ether such as 18- crown-6 (18C6), Benzo-15crown-5 (B15C5), 12crown4 (12C4) as neutral oxo-donors in chloroform from aqueous buffer solution of pH 1-2 having ionic strength 0.1 mol L -1 (K + /H + , Cl - ) has been studied. Radiotracer technique using their appropriate radio-isotopes prepared in the research reactor of PINSTECH such as Ce 141 , Nd 147 , Sm 151 , Eu 152/154 , Tb 160 , Tm 170 , Lu 177 , Hg 203 , Fe 59 etc., were used for the quantification of metal ions in the aqueous and organic phases. Quantitative extraction (>98%) of these metal ions was observed only using HPA and B15C5 synergic mixture at pH 2 within five minutes and the extraction was increased with the increase in ionic radii of lanthanide ions. Composition of the extracted species was determined by slope analysis method and found to be Ln(PA)3.nS, where Ln represent lanthanide ion, PA conjugate base of HPA molecule and S as neutral oxo-donor. The value of n is 1 and 2. Among the various cations and anions tested for their influence on iiithe extraction these lanthanides only Fluoride, oxalate, Cu(II) , Fe(II) and Zn(II) had some deleterious effect. The proposed synergic system presented clean separation of lanthanide ions from mono, and various divalent metal ions especially alkali and alkaline earth metal ions. The effect of other neutral donors such as trioctylphosphineoxide (TOPO), triphenylphosphineoxide (TPPO), tributylphosphate (TBP) and triphenylphosphate (TPP) was also studied on the extraction of Eu(III). Quantitative extraction of Eu(III) was observed with TOPO, TPPO and TBP from aqueous phase of pH2. Synergic adduct composition was found to be Eu(PA) 3 TBP, Eu(PA) 3 .2TOPO and Eu(PA) 3 .2TPPO by slope analysis method. On the basis of the estimated values of the synergic coefficient, and extraction constants (log K ex ), the oxo-donor effect was found in the order of TOPO>TPPO>TBP. The effect of various diluents such as 1-octanol (ONL), 1-hexanol (HNL), 1-butanol (nBNL), 2-butanol (2-BNL), n-butylether (BE), dichloroethylether (DCEE), acetylacetone (ACAC), diisobutylketone (DIBK), cyclohexanone (CHN), benzene, toluene on the extraction of Eu(III) from aqueous solution of pH 1-2 using HPA as extractant has been studied. The extraction of Eu(III) using benzene and toluene was found to be negligible, with 1 & 2-butanol it was low (< 50%), where as with the other diluents studied, the extraction was quantitative at pH 2. On the basis of log K ex , the solvents can be arranged with respect to their extractability in the order ACAC > DIBK > BE > DCEE > ONL > HNL > CHN. To find the trend of lanthanide extraction within the series, three solvents CHN, ONL and DCEE as representative of ketones, alcohols and ethers, respectively, were selected for the extraction of Ce(III), Tb(III) and Lu(III) using HPA as chelating agent from aqueous solutions of pH 1-2, quantitative extraction was observed at pH2 and their extraction order was found to be Ce(III)>Tb(III) >Lu(III).The composition of the extracted adduct was found to be M(PA) 3 in CHN, ONL and M(PA) 3 .HPA in DCEE by slope analysis method. ivThe synergic mixture comprising HPA and B15C5 in benzene and toluene separately were studied for the extraction of Eu(III) from aqueous solution of pH 1-2 and quantitative extraction was observed at pH 1 with both the solvents. On the basis of their estimated values of synergic coefficient and log K ex , benzene was found to be better solvent than toluene. The composition of the synergic adduct was found to be Eu(PA) 3 .2B15C5 and proposed to be a sandwich type complex having one crown ether molecule on either side of the metal chelate bound to the central metal only through three oxygen atoms.
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37. Al-Saffat/The Rows

37. Al-Saffat/The Rows

I/We begin by the Blessed Name of Allah

The Immensely Merciful to all, The Infinitely Compassionate to everyone.

37:01
a. By those lining up in rows,

37:02
a. and those drivers, driving away,

37:03
a. and those reciting the Reminder – The Divine Qur’an.

37:04
a. Indeed, your Allah is the One and Only Allah of everyone.
b. HE has no parents, no partners, no siblings, no sons, and no daughters.

37:05
a. Allah is Rabb - The Lord of the celestial realm and the terrestrial world and whatever is
within and between them, and,
b. Allah is also Rabb - The Lord of the vast expanse of the East and the West.

37:06
a. Indeed, WE adorned the sky of the terrestrial world with splendor of the glittering stars.

37:07
a. And secured them with meteors against every defiant Satan.

37:08
a. So that they, who seek to know the unknowable, may not be able to eavesdrop on the Exalted Assembly of angels,
b. for they will be pelted with meteors from every side -

37:09
a. – and driven off,
b. for them will be a constant and perpetual punishment.

37:10
a. Except for the one, who is able to eavesdrop and snatch a word of such knowledge,
b. he is instantaneously pursued by flaming fireballs.

37:11
a. So ask them:
b. ‘Are they more difficult to be created, or those WE created others than them?
c. In fact, WE created them – the human species - out of mere sticky clay!

Defending Prophet’s Integrity in the Light of Shariah & Contemporary Work

Defending Prophet’s honor is religious and social duty of every Muslim, The Holy Prophet (r) being more valuable than our own lives and souls. The theme of love rests in its high correlation with obedience. That the one whom someone loves, his obedience and submission to him becomes easier, even to the extent of contentment and pleasure. Love of Allah and Holy Prophet (r) has been stressed upon in the article so that obedience of Allah and his Prophet and submission to them is expressed as easy and doable, and an instigation to avoid disobedience is generated. Success of a man lies in obedience of Allah and that of Holy Prophet (r). In this article, the facet of “Love” with Holy Prophet (r) has been comprehensively narrated. The prophet was deputed to be obeyed and followed to the dooms day unchecked of followers’ class, color or ethnicity. Such unconditioned following required his person to be of an extensively inclusive character, which it did, and that every single instant of his esteemed life is preserved. The most divinely of the services is moral building of nations on practical patterns. One way is of preaching, while even cultured is to assemble written material to be followed for long or elsewise forcefully bind people to follow ethical doctrines and avoid vice.

On Variants of Hermite-Hadamard Type Inequalities With Applications.

In the proposed study, we present several significant results annexed to the wellknown Hermite-Hadamard inequality. Also, we focus on various newly established classes of convex functions and their corresponding variants of Hadamard type inequalities. This PhD dissertation is devoted to sift out certain inequalities of Hadamard type from the class of convex functions to their recently established versions, namely MT-convex functions, co-ordinated convex functions etc. In addition, we are mainly concerned with various updated versions and analogues of the well-known Hermite-Hadamard inequalities in terms of integrations such as, classical integrals, Riemann-Liouville’s fractional integrals and α-fractional conformable integrals. Eventually, as applications, the proposed results are further utilized to achieve some novel bounds for special means of positive real numbers. Also, some explicit bounds are also being derived to the versatile composite quadrature rules in terms of distinct functions belonging to different classes of convex functions. At the end, different inequalities have been obtained pertaining to F-divergence measures. In the first chapter, we present some basic concepts, certain necessary terminologies and recall a few important results from the theory of convex analysis in general, and convex sets and convex functions in particular, where many of them will be encountered through out the thesis. Also, these core and elementary notions will provide comparatively a better foundation to the readers in the understanding of the proposed study. In the second chapter, we present several integral identities for differentiable, twice differentiable and three times differentiable functions connected with both left and right hand parts of the classical Hermite-Hadamard inequality. Then, we obtain various Hadamard type inequalities based on these identities via classical integrals. These results have some natural applications to special means of real numbers and trapezoidal as well as midpoint formulas. In the third chapter, we discover two novel integral identities for twice differentiable functions. Then, we employ these identities to establish some general inequalities for the functions whose second derivatives absolute values are MTconvex. These inequalities provide us some new estimates for the right hand side of the Hermite-Hadamard type inequalities for classical integrals and Riemann- Liouville’s fractional integrals. Next, by making use of these results, we point out applications to some means of real numbers and several error estimations for the trapezoidal formula. In the fourth chapter, we obtain some new Hermite-Hadamard type inequalities for convex functions on the co-ordinates. These results refine the earlier work done by Dragomir and Chen . In the fifth chapter, we establish two integral identities for conformable fractional integrals. Then, under the utility these results, we design several integral inequalities connected with the left and right hand side of the Hermite-Hadamard type inequalities for conformable fractional integrals. These results extends the earlier known results from classical integrals to conformable fractional integrals. In the sixth chapter, we give applications of our main results established in the Chapters 2, 3, 4 and 6 respectively. In addition to that, in Section 6.1 applications to special means of real number are provided. Then, in the next Section 6.2, some new error estimates for trapezoidal formula are given. Furthermore, in the next Section 6.3, error estimates for midpoint formula are addressed. In the last Section 6.4, some applications to F-Divergence measures are provided.