Palladium and gold extraction from hydrochloric solutions by calixarenes. Torgov V. 1, Kostin G. 1, Mashukov V. 1, Korda T. 1, Kalchenko V. 2, Drapailo. - презентация

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2 Palladium and gold extraction from hydrochloric solutions by calixarenes. Torgov V. 1, Kostin G. 1, Mashukov V. 1, Korda T. 1, Kalchenko V. 2, Drapailo A. 2, Kasyan O. 2 1 Institute of Inorganic Chemistry SB RAS, pr. Lavrenteva, 3, Novosibirsk, Russia 2 Institute of Organic Chemistry NAS Ukraine, Murmanskaya str., 5, Kyiv, Ukraine

3 Applications: 1)Smart chemical sensing system 2)Molecular scaffolds for construction of supramolecular systems 3)Catalysts for sterioselective reaction in biological system 4)Selective receptors for cations, anions and neutral molecules Calix[4]arenes-are new class of extractants. narrow rim wide rim The volume of cavity is about 10 cubic nanometers 3

4 Different classes of calixarenes used in our investigation 4

5 Gold (III) extraction from hydrochloric solution. LR1R1 XnD Au 2t-BuS4<0,01 3aCH 2 SC 6 H 4 CH 3 CH bCH 2 SMeCH cCH 2 SBuCH aCH 2 SC 6 H 4 CH 3 CH bCH 2 SMeCH CH 2 SC 6 H 4 CH 3 S40,85 Influence of HCl concentration and diluent's properties Screening investigations CCl 4 >Toluene

6 Step-by-step coordination of gold (n=1-4) to calixarenes. P-1, Z=4 a= Å b= Å c= Å α=85.15° β=85.15° γ=89.97° nAuCl L = (AuCl 3 ) n L + nCl - 6 For 3c max Au/L=2

7 nAuCl L = (AuCl 3 ) n L + nCl - LlgK 11 lgK 12 lgK 13 lgK 14 (n) 3a5,4510,8416,2118,930,07 (24) 3b5,6811,3216,7120,280,06 (20) 3a3,937,82--0,07 (22) LlgK 1 add lgK 2 add lgK 3 add lgK 4 add 3a5,455,345,372,72 3b5,685,645,393,57 3c3,933,89-- AuCl (AuCl 3 ) n-1 L = (AuCl 3 ) n L + Cl - K 1 add K 2 add K 3 add >> K 4 add C 4 H 9 > CH 3 > C 6 H 4 CH 3 Efficient constants of gold extraction and constants of stepwise addition. 7

8 Side reaction of gold extraction Lk1k1 EaEa k2k2 EaEa 3a(0,64±0,06)*10 –3 490,38±0,0139 3b(1,8±0,1)*10 –3 420,11±0,0231 3c(0,71±0,06)*10 – Intramolecular (k 1 ): 3b (Me) > 3c (Bu) >> 3a (p-Tol) Intermolecular (k 2 ): 3c > 3a > 3b Diluent : DCE > CCl 4 toluene

9 The equilibrium and kinetic of the extraction of palladium (II) from hydrochloric solution. Tolyl3,6- 3cCH 2 SBuCH 2 40,85>3,6- 4bCH 2 SMeCH 2 6>3,6 - 4cCH 2 SBuCH 2 60,27>3,6- 5CH 2 SC 6 H 4 CH 3 S4-0,210,49- Screening investigation

10 Kinetic of the extraction of palladium (II) from hydrochloric solution 10 Influence of polarity of diluents. Pd CCl 4 >>Toluene=DCE kinetic LAuPd Calix[4]arene0%5% Thiacalix[4]arene0%5% Calix[4,6]arene[4]>[6][6]=[4] Au DCE>CCl 4 >toluene thermodynamic

11 Kinetic of the extraction of palladium (II) from hydrochloric solution 11 Influence of HCl concentration

12 Efficient constants of Pd extraction and constants of stepwise addition. PdCl 4 2- (в) + L (oрг) = PdCl 2 L (орг) + 2Cl - (в) K 1 2PdCl 4 2- (в) + L (oрг) = (PdCl 2 ) 2 L (орг) + 4Cl - (в) K 2 PdCl 4 2- (в) + 2QCl (oрг) = Q 2 PdCl 4(орг) + 2Cl - (в) К ан Q 2 PdCl 4(орг) + L (орг) = PdCl 2 L (орг) + 2QCl (орг) 1 2Q 2 PdCl 4(орг) + L (орг) = (PdCl 2 ) 2 L (орг) + 4QCl (орг) 2 12 Constants of complex formation and extraction were defined for PdCl 2 L and (PdCl 2 ) 2 L by conjugate equilibrium method.

13 NMR specters ( 13 C). 13

14 LРастворительLgK 1 lgK 2 lgK 1 /K 2 (n) 3aТолуол7,3414,787,440,057 (18) 3b7,0814,307,220,046 (17) 3c6,1712,466,290,035 (13) 3b3bCCl 4 7,0914,076,980,056 (16) 14 Concentration constants of Pd complexation Pd K 1 =K 2 K 1 (3a)>K 1 (3b)>K 1 (3c) CCl 4 =toluene Au 1.K 1 add K 2 add K 3 add >> K 4 add 2.K 1 (3b)>K 1 (3a)>K 1 (3c) 3.DCE>toluene>CCl 4

15 Summary PdAu control property kineticthermodynamic substitutions 3a>3b>>3c3a>3b>3c3b>3a>3c size [6] = [4]-[6] > [4] diluentCCl 4 >>toluene >DCE CCl 4 =tolueneDCE>toluene>CCl 4 HClmin. at 1-3 M-C HCl D Au empty calix and thiocalix Works «cone» > 1,3 alternate no extraction Bridging SIncrease 5>3cDecrease 5<3c

16 Congratulations 16 1.Kalchenko V.I. 2.Korda T.M 3.Tkachev S.V 4.Torgov 5.Kostin

17 Laboratory of Chemistry of extraction processes INCh, Novosibirsk

18 Contents Gold (III) extraction from hydrochloric solution and side reaction. Step-by-step coordination of gold (n=1-4) to calixarenes Step-by-step coordination of gold (n=1-4) to calixarenes Constants of gold extraction and constants of stepwise addition Constants of gold extraction and constants of stepwise addition Side reaction of gold extraction Side reaction of gold extraction The equilibrium and kinetic of the extraction of palladium (II) from hydrochloric solution. Concentration Pd extraction Concentration Pd extraction NMR specters ( 13 C) NMR specters ( 13 C) Concentration Pd extraction and constants of stepwise addition Concentration Pd extraction and constants of stepwise additionConclusions Screening investigation Screening investigation Influence of HCl concentration and polarity of diluents Influence of HCl concentration and polarity of diluents Calix[4,6]arenes Screening investigation Screening investigation Influence of HCl concentration Influence of HCl concentration Influence of polarity of diluents Influence of polarity of diluents