ANILIDES TO CLEAN INDUSTRIAL WASTE WATERS Tsagana Sumyanova, - - PowerPoint PPT Presentation

STUDY OF PROSPECTIVE COMPLEXES OF F-ELEMENTS WITH ANILIDES TO CLEAN INDUSTRIAL WASTE WATERS

Tsagana Sumyanova, Natalya Borisova, Alexey Ivanov Radiochemistry Division, Chemistry Department, M.V. Lomonosov Moscow State University

The use of f-elements from wastes separated during the purification of industrial waste water

13 July, 2017, Kaliningrad 3rd Student Workshop on Ecology and Optics of Coastal Zones 2

A selective extraction

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Prospective 2,2’-bipyridyl-6,6’-dicarboxamides

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R = o,p-diMe (1) o,m-diMe (2); o,m,m-triMe (3); p-tret-Bu (4); o-F (5); m-F (6); p-F (7); o-Br (8); H (9[1])

[1] European Journal of Inorganic Chemistry, 2014, 2219–2229

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The absorption spectra of the o-fluoride anilide substituent and the complex with neodymium nitrate in dry acetonitrile

260 280 300 320 340 360 0.0 0.2 0.4 0.6 0.8 1.0

A wavelengthnm

• -fluoride anilide

the complex with Nd

3+

Job’s plot for o-fluoride anilide with ion Tb3+ (in solution)

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0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.2 0.4 0.6 0.8 1.0

A cL/(cL+cM)

                   

 M L L L M L L n m

C C C f A A A A m n n C C C X L M nL mM

The structure of the ligand complex of unsubstituted anilide with gadolinium according to X-ray diffraction analysis (in solid state)

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The dependence of the molar absorption coefficient on titre volume of metal for the o- fluoride anilide with Nd3+ system

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0.0 0.2 0.4 0.6 0.8 5000 10000 15000 20000

 titre volume, ml

     

                     

  3 титр M 3 L L ML L L

LM V V C LM C C A ) ( ) (

1

   

The lanthanide ion dependence of the stability constants values for anilides 1-9

13 July, 2017, Kaliningrad 3rd Student Workshop on Ecology and Optics of Coastal Zones 9 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 4.8 5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8 7.0

lg ions f-elements

• ,p-diMe
• ,m-diMe
• ,m,m-tri-Me

p-tret-Bu p-F

• -F

m-F

• -Br

H

1

The lgβ1 complexes of investigated anilides with lanthanide ions fall into 5,5-6,2 region

3rd Student Workshop on Ecology and Optics of Coastal Zones 10 13 July, 2017, Kaliningrad La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 4.8 5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8 7.0

lg ions f-elements

• ,p-diMe
• ,m-diMe
• ,m,m-tri-Me

p-tret-Bu p-F

• -F

m-F

• -Br

H

1

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The fluorine in the o-position of the anilide stabilizes the complex due to conjugation of halogen long pairs with the phenyl ring

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 4.8 5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8 7.0

lg ions f-elements

• ,p-diMe
• ,m-diMe
• ,m,m-tri-Me

p-tret-Bu p-F

• -F

m-F

• -Br

H

1

The long-chain substituent (t-Butyl) decrease the stability of the complexes irrespectively the position of the alkyl-group

13 July, 2017, Kaliningrad 3rd Student Workshop on Ecology and Optics of Coastal Zones 12 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 4.8 5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8 7.0

lg ions f-elements

• ,p-diMe
• ,m-diMe
• ,m,m-tri-Me

p-tret-Bu p-F

• -F

m-F

• -Br

H

1 N N O N N O

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The o-fluorine-phenyl-amide could be serving as the most suitable candidate to clean industrial waste waters

Acknowledgements

We thank the RNF grant №16-13-10451 for financial support

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• Dr. N. Borisova, Radiochemistry Division, Faculty
• f Chemistry, Lomonosov Moscow State University
• Dr. A. Ivanov, Radiochemistry Division, Faculty of

Chemistry, Lomonosov Moscow State University

15 13 July, 2017, Kaliningrad

Thank you for your attention! And to the Organizing Committee