Äīźóģåķņ āē’ņ čē źżųą ļīčńźīāīé ģąųčķū. Ąäšåń īščćčķąėüķīćī äīźóģåķņą : http://www.chem.msu.ru/rus/vmgu/131/22.pdf Äąņą čēģåķåķč’: Wed Nov 28 19:28:06 2012 Äąņą čķäåźńčšīāąķč’: Sun Apr 10 04:59:03 2016 Źīäčšīāźą:

ā °

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22

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543.544.054.9:547.234.1/.22


.. , .. , .. , .. ( ; e-mail: smolenkov@analyt.chem.msu.ru)
(), (), 2- () () () () ­ . pH 3,5 20 25 40°C . 275­305 . - - . Zorbax SB-C18 (150ā4,6 ) 20 (pH 3,5) 2­5% . 0,25­0,5 0,4­0,7 / .

: , , , 2-, , , , .

[1] , , , , , . ( ) . [2, 3] - . [4]. 10-6% [5]. () , , .

[6, 7] , 4-5,7- [8, 9]. ( [10, 11], 2-- [12­14] 4-- [15­ 17] , 4- [18] 2,3 [19]) . , . , - , . (, ) ( , ) .


. . -. . 2. . 2013. . 54. 1

23

, , . ­ () . 1,1-, , 2-, 40%- , 50%- , -1,1- ( 97­98%, «Sigma-Aldrich», ); ( ), 85%- H3PO4, CH3COONH4, NaH2PO42H2O («...», «Panreac», ); H2SO4 («..», «», ), («Milli-Q», «Millipore», ). «Agilent 1200» («Agilent technologies», ), , , , , «U-2900» («Hitachi», ). 200­500 . . 1 3 . Zorbax SB-C18 (150ā4,6 , 5 , «Agilent technologies», ) 1 /. : 20 (pH 3,5) 5 2%

. 100 . 305 289 . 190­400 . 1 «Eppendorf» ( 1,5­2,0 ) 20 1 (pH 3,5) 10 : 40%- ( 0,4%) 5%- ( 0,05%). 20 25 40°C . 100 0,5 250 . , : - / - . -. . - - . , 223 209 , 250­350 230­330 . 0,05 -1,1- () , -


24

. . -. . 2. . 2013. . 54. 1

- . ( ):
(1,89±0,01)ā10 [291] (1,61±0,01)ā104 [294] (2,64±0,01)ā104 [305]
4

(1,57±0,01)ā104 [275] (1,09±0,01)ā104 [279] (1,91±0,01)ā104 [289]

. , pH . , , 100%. pH ( ) : , , , pH. pH 2 7 pH 3­4. , pH 3,5. , . , (20­25°C) 90 20 () 0,01 0,4% (0,5%). (0,4%)

, . , . 0,05% , 20 40°C. , 2­3 , , . 98%. . - ( ), , , . 2 5% . pH 3,5, . , pH 3,5 (pKa = 3,33) , , pH . . 1, 2 , , . , . (k“) :
1,6 0,9 2,2 1,5 4,8 4,3


. . -. . 2. . 2013. . 54. 1

25

. 1. , 0,5 / , ( 0,4%) 20 25°C ( Zorbax SB-C18 (150ā4,6 ); : 20 (pH 3,5), 5% ; 305 )

. 2. , 1,0 / , ( 0,05%) 20 40°C ( Zorbax SB-C18 (150ā4.6 ); : 20 (pH 3,5); 2% . 289 )

() , (4 )

, ( ). , , [20],


26

(n = 3, = 0,-95) R Si=aāci c 0,01 / ­ 0,999 0,999 0,999 0,999 1,000 0,25 0,20 0,50 0,50 0,999 0,999 1 ­ 0,999 0,999 0,999
** 2



Si = aāci c 10 /

R , /

2

C*, /

c, /

sr, %

Si = (7,6±0,3)ā102āci Si = (2,5±0,1)ā103āci Si = (2,6±0,1)ā103āci

Si = (7,0±0,3)ā102āci

Si = (6,7±0,3)ā102āci

1,0 1,0 0,5 0,5

0,0010­10 0,0010­10 0,0005­10 0,0005­10

17 15 10 7



Si = (8,0±0,3)ā102āci



Si = (2,6±0,1)ā103āci



**

Si = (2,6±0,1)ā103āci

Si = (1,3±0,1)ā103āci Si = (1,8±0,1)ā103āci

Si = (9,7±0,3)ā102āci

Si = (9,6±0,3)ā102āci

0,999 0,999 0,999

0,7 0,5 0,4

1,4 1,0 0,8

0,0014­10 0,0010­10 0,0008­10

17 14 12



Si = (1,4±0,1)ā103āci



Si = (1,8±0,1)ā103āci

. . -. . 2. . 2013. . 54. 1

*

/ ;

.


. . -. . 2. . 2013. . 54. 1

27

(c) 1, 2 4 / ( 500 ) , , (0,5 /) . , , , ( ). , , , . , , , . 5 , ­ 7 . , , ,

( ) . «-» . . 3. 0,5 5,0 / , , . (n = 6, = 0,95):
, / 0,5 5,0 , / 0,49±0,06 5,1±0,5 sr, % 12 10

, , , . , , , .

. 3. () 0,5 / ( . . 1)


28 1. Schirmann J-P., Bourdauducq P. Hydrazine. // Ullmann's Encyclope d i a o f I n d u s t r i a l C h e m i s t r y. We i n h e i m . 2 0 0 7 . V. H. P. 615. 2. .. // . 2000. 1. C. 25. 3. Ghoudhary G., Hansen H. // Chemosphere. 1998. 37. P. 801. 4. .. // . . . 2012. 2. 4. . 14 ( ). 5. Smolenkov A.D., Shpigun O.A. Direct liquid chromatographic determination of hydrazines: A review. // Talanta. 2012. ( ). http://dx.doi.org/10.1016/j.talanta. 2012.07.005 6. Newsome W.H., Collins P. //Intern. J. Anal. Chem. 1988. 34. P. 155. 7. Rutschmann M.A., Buser H.R. // J. Agric. Food Chem. 1991. 39. P. 176. 8. .., .., .. // . . . 2000. 7. . 14. 9. () .. . ... . . . ., 2009. 10. Conditt M.K., Baumgardner J.R., Hellmann L.M. // J. Assoc. Off. Anal. Chem. 1988. 71. P. 735. 11. Kester P.E., Danielson N.D. // Chromatographia. 1984. 18. N 3. P. 125.

. . -. . 2. . 2013. . 54. 1

12. Wright D. // J. Assoc. Off. Anal. Chem. 1987. 70. P. 718. 13. Majumdar T.K., Geno P.W., Yau A. // J. Agric. Food. Chem. 1995. 43. P. 1421. 14. Brinkman J.H.W., Dijk A.G., Wagenaar R. // J. Chromatogr. A. 1996. 723. P. 355. 15. .., .. // . 2006. 61. . 139. [Sotnikov E.E., Moskovkin A.S. J. Anal. Chem. 2006. 61. P. 129] 16. .., .., .. // . 2004. 59. C. 511. [Denisov A.A., Smolenkov A.D., Shpigun O.A. J. Anal. Chem. 2004. 59. P. 452.] 17. .., .., .. // . . . 2006. 6. . 787. 18. .. // . 2002. 24. . 384. 19. .., .., .., .. // . 2012. 67. . 404. 20. .1.31.2008.04405. 1,1-, , . 57-05 30.05.2005 . ., 2005.
17.09.12

appliCation of glyoxal and glyoxyliC aCid for determination of n- and n,n- alkylSuBStituted HydraZineS By liquid CHromatograpHy
r.S. Smirnov, a.d. Smolenkov, t.a. Bolotnik, o.a. Shpigun
u sing chr omatography and spectr ophotometry for investigation of r eaction of 1,1dimethylhydrazine (udmH), methylhydrazine (mH) and 2-hydroxyethylhydrazine (HeH) with excess of glyoxal (gl) and glyoxylic acid (gla) in aqueous solutions it was shown that corresponding monohydrazone was produced as the single derivatization product. the derivatization reaction is quantitative within 20 min at pH 3.5 and at 25 or 40 °C temperature for gl and gla respectively. electronic absorption spectra of derivatives have maxima in the range of 275­305 nm. the conditions for simultaneous determination of hydrazines in water samples by rp­HplC with uV-detection with preliminary derivatization were proposed. the derivatives were separated on a Zorbax SB-C18 (150ā4.6 mm) column with a mobile phase of 20 mm phosphate buffer solution (pH 3.5) ­ (2­5)% acetonitrile. the limits of detection were 0.25­0.5 or 0.4­0.7 µg/l for derivative of gl and gla respectively.

key words: alkylhydrazines, 1,1-dimethylhydrazine, methylhydrazine, 2-hydroxyethylhydrazine, glyoxal, glyoxylic acid, HPLC, water analysis.
: ­ (gmfta@yandex.ru); ­ . . . , . . . ( smolenkov@analyt.chem.msu.ru ); ­ ; ­ , . . , .-. .