нитратсодержащие ионные жидкости как активные компоненты

ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
245
ɍȾɄ 543.257.1:543.852
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(À¶Ê»ºÆ¶ ¶Ã¶Á¾È¾Í»ÇÀÄ¿ ˾¾¾; e-mail: [email protected])
d À¶Í»Çȸ» ¶ÀȾ¸ÃÄ¹Ä ÀÄÂÅÄûÃȶ qdw-ÅÁ¶ÇȾʾ̾Æĸ¶ÃÃÑË Â»Â·Æ¶Ã Ã¾ÈƶÈ-Ç»Á»ÀȾ¸ÃĹÄ
ÓÁ»ÀÈÆĺ¶ ¾ÇÇÁ»ºÄ¸¶ÃÑ º¸» þÈƶÈÇĺ»Æ¼¶Ï¾» ¾ÄÃÃÑ» ¼¾ºÀÄÇȾ (jh) ö ÄÇÃĸ» À¶È¾Äö
½¶Â»Ï»ÃÃÄ¹Ä ¾Â¾º¶½ÄÁ¾µ. j½ÉÍ»ÃÑ ÅÄÈ»Ã̾Ä»ÈƾͻÇÀ¶µ ķƶȾÂÄÇÈÒ ¾ ÄÇÃĸÃÑ» ÓÁ»ÀÈÆÄ˾¾ͻÇÀ¾» ˶ƶÀȻƾÇȾÀ¾ ¾ÄÃ-Ç»Á»ÀȾ¸ÃÑË ÓÁ»ÀÈÆĺĸ ¸ ƶÇȸÄÆ¶Ë KNO3. jÇÇÁ»ºÉ»ÂÑ»
»·ƶÃÑ, Çĺ»Æ¼¶Ï¾» 5% ¶ÀȾ¸ÃÄ¹Ä ÀÄÂÅÄûÃȶ, º»ÂÄÃÇÈƾÆÉÔÈ ·Á¾½À¾¿ À È»ÄƻȾͻÇÀÄ–
ÂÉ ÄÈÀÁ¾À ÅÄ ÄÈÃÄÎ»Ã¾Ô À NO3 . jÇÅÄÁҽĸ¶Ã¾» ·ÄÁ»» ¹¾ºÆÄÊÄ·ÃÄ¿ jh ö ÄÇÃĸ» º¾ÄÀȶº»Ì¾Á¾Â¾º¶½ÄÁ¾µ ÅĸÑζ»È ÍɸÇȸ¾È»ÁÒÃÄÇÈÒ ÄÅÆ»º»Á»Ã¾µ ¾ Çþ¼¶»È ÅÆ»º»Á ķöÆɼ»Ã¾µ:
–6
ÀÆÉȾ½Ã¶ ÓÁ»ÀÈÆĺÃÄ¿ ÊÉÃÀ̾¾ 57 Âd/º»À, Cmin=3,7·10 n. j½Éͻà ¾ÃȻƸ¶Á Æo ÊÉÃÀ̾Äþ–
Æĸ¶Ã¾µ »·ƶÃÑ ¾ ÄÅÆ»º»Á»Ã¶ ÅÄÈ»Ã̾Ä»ÈƾͻÇÀ¶µ Ç»Á»ÀȾ¸ÃÄÇÈÒ À NO3 ¸ ÅƾÇÉÈÇȸ¾¾
Ƶº¶ ÅÄÇÈÄÆÄÃÃ¾Ë ¶Ã¾ÄÃĸ. qÄ ÄÇÃĸÃÑ ÓÁ»ÀÈÆÄ˾¾ͻÇÀ¾Â ˶ƶÀȻƾÇȾÀ¶Â – ÅÆ»º»ÁÉ
ķöÆɼ»Ã¾µ ¾ ¸Æ»Â»Ã¾ ÄÈÀÁ¾À¶ – ƶ½Æ¶·ÄȶÃÃÑ¿ ÓÁ»ÀÈÆĺ ÅÆ»¸ÄÇËĺ¾È ÀÄ»ÆÍ»ÇÀ¾ ºÄÇÈÉÅÃÑ¿ ¶Ã¶ÁĹ. qÄÀ¶½¶Ã¶ ¸Ä½ÂļÃÄÇÈÒ ¾ÇÅÄÁҽĸ¶Ã¾µ ƶ½Æ¶·ÄȶÃÃÑË ÓÁ»ÀÈÆĺĸ ºÁµ ÅƵÂÄ–
¹Ä ÅÄÈ»Ã̾Ä»ÈƾͻÇÀÄ¹Ä ÄÅÆ»º»Á»Ã¾µ jh, Çĺ»Æ¼¶Ï¾Ë NO3 ¸ ¸ÄºÃÑË Æ¶ÇȸÄƶË.
ɉɪɚɤɬɢɱɟɫɤɢ ɜɨ ɜɫɟɯ ɩɪɟɞɥɨɠɟɧɧɵɯ ɤ ɧɚɫɬɨɹɳɟɦɭ
ɜɪɟɦɟɧɢ ɩɥɚɫɬɢɮɢɰɢɪɨɜɚɧɧɵɯ ɦɟɦɛɪɚɧɧɵɯ ɢɨɧ-ɫɟɥɟɤɬɢɜɧɵɯ ɷɥɟɤɬɪɨɞɚɯ (ɂɋɗ) ɧɚ ɧɢɬɪɚɬ-ɢɨɧ ɢɫɩɨɥɶɡɭɸɬ
ɚɫɫɨɰɢɚɬɵ ɝɢɞɪɨɮɨɛɧɵɯ ɨɪɝɚɧɢɱɟɫɤɢɯ ɤɚɬɢɨɧɨɜ ɫ
ɢɨɧɚɦɢ NO3– [1]. ȼ ɩɨɞɚɜɥɹɸɳɟɦ ɛɨɥɶɲɢɧɫɬɜɟ ɫɥɭɱɚɟɜ ɚɧɢɨɧɨɨɛɦɟɧɧɢɤɨɦ ɫɥɭɠɚɬ ɫɨɥɢ ɚɥɤɢɥɚɦɦɨɧɢɹ
ɥɢɛɨ ɚɥɤɢɥɮɨɫɮɨɧɢɹ. ɉɪɢ ɷɬɨɦ ɜɨ ɜɪɟɦɹ ɤɨɧɞɢɰɢɨɧɢɪɨɜɚɧɢɹ ɜ ɪɚɫɬɜɨɪɟ ɩɨɬɟɧɰɢɚɥɨɩɪɟɞɟɥɹɸɳɟɝɨ ɢɨɧɚ
NO3– ɷɤɫɬɪɚɝɢɪɭɟɬɫɹ ɜ ɥɢɩɨɮɢɥɶɧɭɸ ɦɟɦɛɪɚɧɭ, ɢɡɛɢɪɚɬɟɥɶɧɨɫɬɶ ɢ, ɫɥɟɞɨɜɚɬɟɥɶɧɨ, ɩɨɬɟɧɰɢɨɦɟɬɪɢɱɟɫɤɚɹ
ɫɟɥɟɤɬɢɜɧɨɫɬɶ ɤɨɬɨɪɨɣ ɫɨɨɬɜɟɬɫɬɜɭɟɬ ɪɹɞɭ ɥɢɩɨɮɢɥɶɧɨɫɬɢ Ƚɨɮɦɟɣɫɬɟɪɚ [2]. Ɇɟɦɛɪɚɧɧɵɟ ɷɥɟɤɬɪɨɞɵ ɧɚ
ɨɫɧɨɜɟ ɚɧɢɨɧɨɨɛɦɟɧɧɢɤɨɜ ɩɪɟɞɥɨɠɟɧɵ ɞɥɹ ɢɨɧɨɦɟɬɪɢɱɟɫɤɨɝɨ ɨɩɪɟɞɟɥɟɧɢɹ ɬɚɤɢɯ ɨɬɧɨɫɢɬɟɥɶɧɨ ɝɢɞɪɨɮɨɛɧɵɯ ɨɪɝɚɧɢɱɟɫɤɢɯ ɚɧɢɨɧɨɜ, ɤɚɤ ɋIO4–, BF4–, SCN –,
–
NO3 [3,4]. ɗɥɟɤɬɪɨɞɧɨɚɤɬɢɜɧɵɣ ɤɨɦɩɨɧɟɧɬ ɮɨɪɦɢɪɭɟɬɫɹ ɧɚ ɩɨɜɟɪɯɧɨɫɬɢ ɦɟɦɛɪɚɧɵ ɜ ɪɟɡɭɥɶɬɚɬɟ ɩɪɨɞɨɥɠɢɬɟɥɶɧɨɝɨ ɤɨɧɞɢɰɢɨɧɢɪɨɜɚɧɢɹ ɦɟɦɛɪɚɧɵ ɜ ɪɚɫɬɜɨɪɟ ɩɨɬɟɧɰɢɚɥɨɩɪɟɞɟɥɹɸɳɟɝɨ ɢɨɧɚ ɡɚ ɫɱɟɬ ɨɛɪɚɡɨɜɚɧɢɹ ɫɨɨɬɜɟɬɫɬɜɭɸɳɟɝɨ ɚɫɫɨɰɢɚɬɚ. Ȼɨɥɟɟ ɩɟɪɫɩɟɤɬɢɜɧɵ, ɧɚ ɧɚɲ ɜɡɝɥɹɞ, ɂɋɗ, ɜ ɦɟɦɛɪɚɧɭ ɤɨɬɨɪɵɯ
ɝɢɞɪɨɮɨɛɧɵɣ ɚɫɫɨɰɢɚɬ, ɫɨɞɟɪɠɚɳɢɣ ɰɟɥɟɜɨɣ ɢɨɧ, ɜɜɟɞɟɧ ɧɟɩɨɫɪɟɞɫɬɜɟɧɧɨ [5, 6].
ȼ ɩɨɫɥɟɞɧɢɟ ɝɨɞɵ ɜ ɚɧɚɥɢɬɢɱɟɫɤɨɣ ɯɢɦɢɢ ɜɫɟ ɛɨɥɟɟ ɲɢɪɨɤɨ ɢɫɩɨɥɶɡɭɸɬ ɢɨɧɧɵɟ ɠɢɞɤɨɫɬɢ (ɂɀ) – ɢɨɧɧɵɟ ɨɪɝɚɧɢɱɟɫɤɢɟ ɫɨɟɞɢɧɟɧɢɹ, ɧɚɯɨɞɹɳɢɟɫɹ ɜ ɪɚɫɩɥɚɜɥɟɧɧɨɦ ɫɨɫɬɨɹɧɢɢ [7, 8]. ɑɚɳɟ ɜɫɟɝɨ ɤ ɂɀ ɨɬɧɨ-
16 ȼɆɍ, ɯɢɦɢɹ, ʋ 4
ɫɹɬ ɫɨɟɞɢɧɟɧɢɹ, ɬɟɦɩɟɪɚɬɭɪɚ ɩɥɚɜɥɟɧɢɹ ɤɨɬɨɪɵɯ ɧɟ
ɩɪɟɜɵɲɚɟɬ 100°ɋ. ɂɨɧɧɵɟ ɠɢɞɤɨɫɬɢ ɢɫɩɨɥɶɡɭɸɬ ɜ
ɤɚɱɟɫɬɜɟ ɪɚɫɬɜɨɪɢɬɟɥɟɣ, ɪɚɡɛɚɜɢɬɟɥɟɣ ɢ ɷɤɫɬɪɚɝɟɧɬɨɜ
ɜ ɠɢɞɤɨɫɬɧɨɣ ɷɤɫɬɪɚɤɰɢɢ [9–11], ɜɨɥɶɬɚɦɩɟɪɨɦɟɬɪɢɢ
[12], ɜ ɤɚɩɢɥɥɹɪɧɨɦ ɷɥɟɤɬɪɨɮɨɪɟɡɟ ɢ ɯɪɨɦɚɬɨɝɪɚɮɢɢ
[13–15]. ɉɨɹɜɢɥɚɫɶ ɢɧɮɨɪɦɚɰɢɹ ɨ ɜɨɡɦɨɠɧɨɫɬɢ ɢɫɩɨɥɶɡɨɜɚɧɢɹ ɂɀ ɢ ɜ ɤɚɱɟɫɬɜɟ ɷɥɟɤɬɪɨɞɧɨɚɤɬɢɜɧɵɯ
ɤɨɦɩɨɧɟɧɬɨɜ (ɗȺɄ) ɢ ɩɥɚɫɬɢɮɢɤɚɬɨɪɨɜ ɩɨɥɢɦɟɪɧɨɝɨ
ɫɜɹɡɭɸɳɟɝɨ ɦɟɦɛɪɚɧ ɂɋɗ [16].
ȼ ɧɚɫɬɨɹɳɟɣ ɪɚɛɨɬɟ ɜ ɤɚɱɟɫɬɜɟ ɚɤɬɢɜɧɨɝɨ ɤɨɦɩɨɧɟɧɬɚ ɉȼɏ-ɦɟɦɛɪɚɧɵ ɂɋɗ, ɨɛɪɚɬɢɦɨɝɨ ɤ NO3–, ɦɵ
ɢɫɫɥɟɞɨɜɚɥɢ ɞɜɟ ɂɀ ɧɚ ɨɫɧɨɜɟ ɤɚɬɢɨɧɨɜ 1,3-ɞɢɚɥɤɢɥɢɦɢɞɚɡɨɥɢɹ — C8C 12Im NO3 ɢ (C16) 2Im NO3.
ÀÇŻƾ»ÃȶÁÒöµ ͶÇÈÒ
r¶ÇȸÄÆÑ ¾ Æ»¶¹»ÃÈÑ. ɂɨɧɧɵɟ ɠɢɞɤɨɫɬɢ ɧɢɬɪɚɬ 1-ɨɤɬɢɥ-3-ɞɨɞɟɰɢɥɢɦɢɞɚɡɨɥɢɹ ɋ8ɋ12Im NO3 (ɠɢɞɤɨɫɬɶ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ) ɢ ɧɢɬɪɚɬ 1,3-ɞɢɝɟɤɫɚɞɟɰɢɥɢɦɢɞɚɡɨɥɢɹ (C16) 2Im NO3 (ɬɜɟɪɞɨɟ ɫɨɟɞɢɧɟɧɢɟ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ, tɩɥ = 68,5°ɋ) ɫɢɧɬɟɡɢɪɨɜɚɧɵ ɫɨɝɥɚɫɧɨ [17] (ɬɚɛɥ. 1). ɉɪɢ ɢɡɝɨɬɨɜɥɟɧɢɢ
ɩɥɚɫɬɢɮɢɰɢɪɨɜɚɧɧɵɯ ɦɟɦɛɪɚɧ ɜ ɤɚɱɟɫɬɜɟ ɪɚɫɬɜɨɪɢɬɟɥɹ-ɩɥɚɫɬɢɮɢɤɚɬɨɪɚ ɢɫɩɨɥɶɡɨɜɚɥɢ Ä-ɧɢɬɪɨɮɟɧɢɥɨɤɬɢɥɨɜɵɣ ɷɮɢɪ (Ä-ɇɎɈɗ, ε = 24,5, Sigma). ɉɨɥɢɦɟɪɧɨɣ
ɦɚɬɪɢɰɟɣ ɫɥɭɠɢɥ ɩɨɥɢɜɢɧɢɥɯɥɨɪɢɞ ɦɚɪɤɢ “C-70 “.
ɂɫɯɨɞɧɵɟ ɪɚɫɬɜɨɪɵ KNO3, ɚ ɬɚɤɠɟ ɪɚɫɬɜɨɪɵ ɂɀ
ɝɨɬɨɜɢɥɢ ɪɚɫɬɜɨɪɟɧɢɟɦ ɜ ɞɢɫɬɢɥɥɢɪɨɜɚɧɧɨɣ ɜɨɞɟ ɬɨɱ-
ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
246
Ɍɚɛɥɢɰɚ 1
jh – ÓÁ»ÀÈÆĺÃĶÀȾ¸ÃÑ» ÇÄ»º¾Ã»Ã¾µ
ɇɚɡɜɚɧɢɟ ɫɨɟɞɢɧɟɧɢɹ
1-Ⱦɨɞɟɰɢɥ-3ɨɤɬɢɥɢɦɢɞɚɡɨɥɢɹ ɧɢɬɪɚɬ
C8C12Im+ NO3-
H17C8
1,3-Ⱦɢɝɟɤɫɚɞɟɰɢɥɢɦɢɞɚɡɨɥɢɹ
ɧɢɬɪɚɬ
(C16)2Im+ NO3-
H33C16
N
N
+
+
ɧɨɣ ɧɚɜɟɫɤɢ ɜɟɳɟɫɬɜɚ; ɪɚɫɬɜɨɪɵ ɫ ɦɟɧɶɲɟɣ ɤɨɧɰɟɧɬɪɚɰɢɟɣ ɩɨɥɭɱɚɥɢ ɩɨɫɥɟɞɨɜɚɬɟɥɶɧɵɦ ɪɚɡɛɚɜɥɟɧɢɟɦ.
Ɋɚɫɬɜɨɪɵ ɫɨɥɟɣ “ɩɨɫɬɨɪɨɧɧɢɯ” ɚɧɢɨɧɨɜ ɞɥɹ ɢɡɭɱɟɧɢɹ
ɩɨɬɟɧɰɢɨɦɟɬɪɢɱɟɫɤɨɣ ɫɟɥɟɤɬɢɜɧɨɫɬɢ (1.10 –3 Ɇ):SO42,
Cl–, Br–, I–, CH3COO–, ClO4– ɝɨɬɨɜɢɥɢ ɪɚɫɬɜɨɪɟɧɢɟɦ
ɬɨɱɧɨɣ ɧɚɜɟɫɤɢ ɫɨɨɬɜɟɬɫɬɜɭɸɳɟɣ ɫɨɥɢ ɳɟɥɨɱɧɨɝɨ
ɦɟɬɚɥɥɚ (Na, K ɢɥɢ Li) ɦɚɪɤɢ “ɯ.ɱ.” ɢɥɢ “ɱ.ɞ.ɚ.” ɜ
ɞɢɫɬɢɥɥɢɪɨɜɚɧɧɨɣ ɜɨɞɟ.
j½¹ÄÈĸÁ»Ã¾» ÅÁ¶ÇȾʾ̾Æĸ¶ÃÃÑË Â»Â·Æ¶Ã
js
ɉɥɟɧɨɱɧɵɟ ɦɟɦɛɪɚɧɵ ɂɋɗ ɝɨɬɨɜɢɥɢ ɩɨ ɢɡɜɟɫɬɧɨɣ
ɦɟɬɨɞɢɤɟ [18] ɪɚɫɬɜɨɪɟɧɢɟɦ ɉȼɏ, ɩɥɚɫɬɢɮɢɤɚɬɨɪɚ ɢ
ɗȺɄ ɜ ɫɜɟɠɟɩɟɪɟɝɧɚɧɧɨɦ ɬɟɬɪɚɝɢɞɪɨɮɭɪɚɧɟ ɩɪɢ ɩɟɪɟɦɟɲɢɜɚɧɢɢ. ɋɨɞɟɪɠɚɧɢɟ ɗȺɄ, ɩɥɚɫɬɢɮɢɤɚɬɨɪɚ ɢ
ɉȼɏ ɫɨɫɬɚɜɢɥɨ 5,0; 63,5 ɢ 31,5 ɦɚɫ.% ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ.
ȼ ɤɚɱɟɫɬɜɟ ɷɥɟɤɬɪɨɞɧɨɚɤɬɢɜɧɨɝɨ ɤɨɦɩɨɧɟɧɬɚ – ɢɨɧɨɨɛɦɟɧɧɢɤɚ ɜ ɦɟɦɛɪɚɧɧɭɸ ɤɨɦɩɨɡɢɰɢɸ ɜɜɨɞɢɥɢ ɧɟɩɨɫɪɟɞɫɬɜɟɧɧɨ ɂɀ.
ɗɥɟɤɬɪɨɯɢɦɢɱɟɫɤɢɟ ɫɜɨɣɫɬɜɚ ɩɪɢɝɨɬɨɜɥɟɧɧɵɯ ɦɟɦɛɪɚɧ ɢɡɭɱɚɥɢ ɩɭɬɟɦ ɢɡɦɟɪɟɧɢɹ ɗȾɋ ɝɚɥɶɜɚɧɢɱɟɫɤɨɣ
ɰɟɩɢ ɫ ɩɟɪɟɧɨɫɨɦ:
Ag/AgCl
ȼɧɭɬɪɟɧɧɢɣ
ɫɬɚɧɞɚɪɬɧɵɣ
ɪɚɫɬɜɨɪ
ɉɥɚɫɬɢɮɢɰɢɪɨɜɚɧɧɚɹ
ɦɟɦɛɪɚɧɚ
ɂɫɫɥɟɞɭɟɦɵɣ
ɪɚɫɬɜɨɪ
AgCl/Ag
Ⱦɥɹ ɢɡɦɟɪɟɧɢɹ ɗȾɋ ɩɪɢɦɟɧɹɥɢ ɢɨɧɨɦɟɪ “ÀÇÅ»ÆÈ-001”. ȼ ɤɚɱɟɫɬɜɟ ɜɧɟɲɧɟɝɨ ɷɥɟɤɬɪɨɞɚ ɫɪɚɜɧɟɧɢɹ ɢɫɩɨɥɶɡɨɜɚɥɢ ɯɥɨɪɢɞɫɟɪɟɛɪɹɧɵɣ ɷɥɟɤɬɪɨɞ ɦɚɪɤɢ
“dm-1 n3”. Ɂɧɚɱɟɧɢɟ ɤɨɷɮɮɢɰɢɟɧɬɨɜ ɩɨɬɟɧɰɢɨɦɟɬɪɢɱɟɫɤɨɣ ɫɟɥɟɤɬɢɜɧɨɫɬɢ (lg K pot − ) ɨɰɟɧɢɜɚɥɢ ɦɟɬɨX , NO3
Ɉɛɨɡɧɚɱɟɧɢɟ
ɦɟɦɛɪɚɧ
ɋɬɪɭɤɬɭɪɧɚɹ ɮɨɪɦɭɥɚ
N
N
C12H25
C16H33
-
I
-
II
NO3
NO3
ɞɨɦ ɛɢɢɨɧɧɵɯ ɩɨɬɟɧɰɢɚɥɨɜ ɩɪɢ ɤɨɧɰɟɧɬɪɚɰɢɢ ɨɫɧɨɜɧɨɝɨ ɢ ɦɟɲɚɸɳɟɝɨ ɢɨɧɨɜ 1·10–3 Ɇ. Ɉɫɧɨɜɧɵɟ ɩɚɪɚɦɟɬɪɵ ɮɭɧɤɰɢɨɧɢɪɨɜɚɧɢɹ ɢɫɫɥɟɞɭɟɦɨɝɨ ɷɥɟɤɬɪɨɞɚ ɫɪɚɜɧɢɜɚɥɢ ɫ ɯɚɪɚɤɬɟɪɢɫɬɢɤɚɦɢ ɧɢɬɪɚɬ-ɫɟɥɟɤɬɢɜɧɨɝɨ ɷɥɟɤɬɪɨɞɚ “mjt 021”, ɜɵɩɭɫɤɚɟɦɨɝɨ ɧɚɭɱɧɨ-ɩɪɨɢɡɜɨɞɫɬɜɟɧɧɨɣ ɤɨɦɩɚɧɢɟɣ “o¾ÀÄ-böÁ¾È”.
r»½ÉÁÒȶÈÑ ¾ Ä·Çɼº»Ã¾»
j½Éͻþ» ÓÁ»ÀÈÆÄ˾¾ͻÇÀ¾Ë ˶ƶÀȻƾÇȾÀ
js ö ÄÇÃĸ» jh
ɂɫɫɥɟɞɨɜɚɧ ɩɨɬɟɧɰɢɨɦɟɬɪɢɱɟɫɤɢɣ ɨɬɤɥɢɤ ɦɟɦɛɪɚɧ,
ɫɨɞɟɪɠɚɳɢɯ ɜ ɤɚɱɟɫɬɜɟ ɷɥɟɤɬɪɨɞɧɨɚɤɬɢɜɧɨɝɨ ɤɨɦɩɨɧɟɧɬɚ ɂɀ ɧɚ ɨɫɧɨɜɟ ɤɚɬɢɨɧɨɜ ɞɢɚɥɤɢɥɢɦɢɞɚɡɨɥɢɹ ɢ
–
ɢɨɧɚ NO3 (ɬɚɛɥ. 1). ɍɫɬɚɧɨɜɥɟɧɨ, ɱɬɨ ɜ ɪɚɫɬɜɨɪɚɯ
KNO3 ɜɫɟ ɢɫɫɥɟɞɭɟɦɵɟ ɂɋɗ ɩɪɨɹɜɥɹɸɬ ɨɬɤɥɢɤ ɤ
NO3–, ɤɪɭɬɢɡɧɚ ɷɥɟɤɬɪɨɞɧɨɣ ɮɭɧɤɰɢɢ ɛɥɢɡɤɚ ɤ ɬɟɨɪɟɬɢɱɟɫɤɨɣ ɜɟɥɢɱɢɧɟ (ɪɢɫ. 1). ȼɪɟɦɹ ɨɬɤɥɢɤɚ ɷɥɟɤɬɪɨɞɨɜ ɧɟ ɩɪɟɜɵɲɚɟɬ ɞɜɭɯ ɦɢɧɭɬ. ɉɨɬɟɧɰɢɚɥ ɦɟɦɛɪɚɧɵ
ɧɟ ɡɚɜɢɫɢɬ ɨɬ ɤɢɫɥɨɬɧɨɫɬɢ ɢɫɫɥɟɞɭɟɦɨɝɨ ɪɚɫɬɜɨɪɚ ɜ
ɢɧɬɟɪɜɚɥɟ ɪɇ 3,0–10,0. ɂɫɩɨɥɶɡɨɜɚɧɢɟ ɜ ɤɚɱɟɫɬɜɟ ɚɤɬɢɜɧɨɝɨ ɤɨɦɩɨɧɟɧɬɚ ɦɟɦɛɪɚɧɵ (ɋ16) 2Im NO3 (ɛɨɥɟɟ
ɝɢɞɪɨɮɨɛɧɨɣ ɂɀ) ɩɨɡɜɨɥɹɟɬ ɩɨɜɵɫɢɬɶ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɶ ɨɩɪɟɞɟɥɟɧɢɹ ɢ ɫɧɢɡɢɬɶ ɩɪɟɞɟɥ ɨɛɧɚɪɭɠɟɧɢɹ NO3– (ɬɚɛɥ. 2).
ɗɥɟɤɬɪɨɯɢɦɢɱɟɫɤɢɟ ɫɜɨɣɫɬɜɚ ɦɟɦɛɪɚɧ ɧɚ ɨɫɧɨɜɟ
ɂɀ ɫɨɩɨɫɬɚɜɢɥɢ ɫ ɯɚɪɚɤɬɟɪɢɫɬɢɤɚɦɢ ɧɢɬɪɚɬ-ɫɟɥɟɤɬɢɜɧɨɝɨ ɷɥɟɤɬɪɨɞɚ “mjt 021”. ɍɫɬɚɧɨɜɥɟɧɨ, ɱɬɨ ɩɨ
ɜɫɟɦ ɯɚɪɚɤɬɟɪɢɫɬɢɤɚɦ ɂɋɗ ɧɚ ɨɫɧɨɜɟ ɂɀ ɧɟ ɭɫɬɭɩɚɸɬ ɤɨɦɦɟɪɱɟɫɤɨɦɭ ɚɧɚɥɨɝɭ, ɚ ɩɨ ɩɪɟɞɟɥɭ ɨɛɧɚɪɭɠɟɧɢɹ (Cɦɢɧ) ɢ ɜɪɟɦɟɧɢ ɨɬɤɥɢɤɚ ɩɪɟɜɨɫɯɨɞɹɬ ɟɝɨ
(ɬɚɛɥ. 2).
ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
247
Ɍɚɛɥɢɰɚ 2
Á»ÀÈÆÄ˾¾ͻÇÀ¾» ǸĿÇȸ¶ »·ƶÃ
ɏɚɪɚɤɬɟɪɢɫɬɢɤɚ ɂɋɗ
ɗɥɟɤɬɪɨɞ
ɤɪɭɬɢɡɧɚ,
ɦȼ
ɢɧɬɟɪɜɚɥ
ɥɢɧɟɣɧɨɫɬɢ,
Ɇ
ɋɦɢɧ·106,
M
ɜɪɟɦɹ ɨɬɤɥɢɤɚ
(10–1 Ɇ), ɦɢɧ
ɪɚɛɨɱɢɣ
ɢɧɬɟɪɜɚɥ pH
I
–51±5
1·10–1–1·10–5
5,0
2,5
3–10
II
–57,1±0,8
1·10–1–1·10–5
3,7
2,5
3–10
“ɗɅɂɌ 021”
–58±1
1·10–1–1·10–5
5,9
4,0
2–9
pÅÆ»º»Á»Ã¾» Ç»Á»ÀȾ¸ÃÄÇȾ »·ƶÃÑ
À þÈÆ¶È ¾ÄÃÉ
Ⱦɥɹ ɢɡɭɱɟɧɢɹ ɩɨɬɟɧɰɢɨɦɟɬɪɢɱɟɫɤɨɣ ɫɟɥɟɤɬɢɜɧɨɫɬɢ
ɦɟɦɛɪɚɧɵ ɧɚ ɨɫɧɨɜɟ ɂɀ ɢɡɦɟɪɟɧɵ ɤɨɷɮɮɢɰɢɟɧɬɵ
ɩɨɬɟɧɰɢɨɦɟɬɪɢɱɟɫɤɨɣ ɫɟɥɟɤɬɢɜɧɨɫɬɢ ɜ ɪɚɫɬɜɨɪɚɯ ɫɨ–3
ɥɟɣ (1·10 Ɇ) ɩɨɫɬɨɪɨɧɧɢɯ ɚɧɢɨɧɨɜ: ɫɭɥɶɮɚɬɚ, ɯɥɨɪɢɞɚ,
ɛɪɨɦɢɞɚ, ɢɨɞɢɞɚ, ɚɰɟɬɚɬɚ, ɩɟɪɯɥɨɪɚɬɚ. ɉɨɥɭɱɟɧɧɵɟ
ɤɨɷɮɮɢɰɢɟɧɬɵ ɫɟɥɟɤɬɢɜɧɨɫɬɢ ɩɪɢɜɟɞɟɧɵ ɜ ɬɚɛɥ. 3.
ɍɫɬɚɧɨɜɥɟɧɨ, ɱɬɨ ɜɥɢɹɧɢɟ ɩɨɫɬɨɪɨɧɧɢɯ ɢɨɧɨɜ ɧɚ
ɨɬɤɥɢɤ ɤ NO3– ɪɚɫɬɟɬ ɜ ɪɹɞɭ:
2–
–
–
–
–
–
–
SO4 < Ac < CI < Br < Sal < I < CIO4 .
ɇɚɢɛɨɥɶɲɚɹ ɫɟɥɟɤɬɢɜɧɨɫɬɶ ɧɚɛɥɸɞɚɟɬɫɹ ɜ ɩɪɢɫɭɬ2–
ɫɬɜɢɢ SO4 , ɫɢɥɶɧɟɟ ɜɫɟɝɨ ɢɨɧɨɦɟɬɪɢɱɟɫɤɨɦɭ ɨɩɪɟɞɟɥɟɧɢɸ NO3– ɦɟɲɚɟɬ ɩɪɢɫɭɬɫɬɜɢɟ ɜ ɢɫɫɥɟɞɭɟɦɨɦ
ɪɚɫɬɜɨɪɟ CIO4–.
j½Éͻþ» ÄÈÀÁ¾À¶ þÈƶÈ-Ç»Á»ÀȾ¸ÃÑË ÓÁ»ÀÈÆĺĸ ¸ ƶÇȸÄÆ¶Ë jh
ɗɥɟɤɬɪɨɞɵ, ɫɨɞɟɪɠɚɳɢɟ ɜ ɤɚɱɟɫɬɜɟ ɚɤɬɢɜɧɨɝɨ ɤɨɦɩɨɧɟɧɬɚ ɂɀ, ɢɫɩɨɥɶɡɨɜɚɧɵ ɞɥɹ ɢɨɧɨɦɟɬɪɢɱɟɫɤɨɝɨ
ɨɩɪɟɞɟɥɟɧɢɹ NO3– ɜ ɪɚɫɬɜɨɪɟ ɂɀ ɋ8ɋ 12Im NO 3.
ɉɨ ɫɪɚɜɧɟɧɢɸ ɫ ɪɚɫɬɜɨɪɚɦɢ KNO3 ɩɨɜɟɞɟɧɢɟ ɂɋɗ
ɫɢɥɶɧɨ ɦɟɧɹɟɬɫɹ. Ɉɛɧɚɪɭɠɟɧɨ ɫɭɳɟɫɬɜɟɧɧɨɟ ɜɥɢɹɧɢɟ
ɧɚ ɨɬɤɥɢɤ ɤ NO3– ɩɪɢɫɭɬɫɬɜɢɹ ɜ ɢɫɫɥɟɞɭɟɦɨɦ ɪɚɫɬɜɨɪɟ ɤɪɭɩɧɨɝɨ ɝɢɞɪɨɮɨɛɧɨɝɨ ɤɚɬɢɨɧɚ
ɞɢɚɥɤɢɥ-ɢɦɢɞɚɡɨɥɢɹ (ɋ8ɋ 12Im+ ). ɍɫɬɚɧɨɜɥɟɧɨ, ɱɬɨ
ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɶɸ ɤ NO3– ɜ ɭɡɤɨɦ ɢɧɬɟɪɜɚɥɟ ɤɨɧɰɟɧɬɪɚɰɢɣ ɨɛɥɚɞɚɟɬ ɬɨɥɶɤɨ ɦɟɦɛɪɚɧɚ II, ɫɨɞɟɪɠɚɳɚɹ
ɜ ɤɚɱɟɫɬɜɟ ɚɧɢɨɧɨɨɛɦɟɧɧɢɤɚ (ɋ16) 2Im+ (ɛɨɥɟɟ ɝɢɞɪɨɮɨɛɧɵɣ ɤɚɬɢɨɧ ɢɦɢɞɚɡɨɥɢɹ). ȼ ɨɛɥɚɫɬɢ ɦɚɥɵɯ ɤɨɧɰɟɧɬɪɚɰɢɣ ɂɀ (ɧɢɠɟ 1–10–4 Ɇ) ɧɚɛɥɸɞɚɟɬɫɹ ɧɟɩɨɥɧɚɹ ɚɧɢɨɧɧɚɹ ɮɭɧɤɰɢɹ ɫ ɤɪɭɬɢɡɧɨɣ (43±3) ɦȼ/ɞɟɤ,
Ɋɢɫ. 1. Ɉɬɤɥɢɤ ɷɥɟɤɬɪɨɞɨɜ I, II ɢ “mjt 021” ɧɚ KNO3, ɝɞɟ 1 – ɷɥɟɤɬɪɨɞ I, 2 –
ɷɥɟɤɬɪɨɞ II, 3 – “mjt 021” (ɩɭɧɤɬɢɪɨɦ ɨɛɨɡɧɚɱɟɧɚ ɬɟɨɪɟɬɢɱɟɫɤɚɹ ɮɭɧɤɰɢɹ)
17 ȼɆɍ, ɯɢɦɢɹ, ʋ 4
ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
248
Ɋɢɫ. 2. Ɉɬɤɥɢɤ ɂɋɗ ɫ ɦɟɦɛɪɚɧɨɣ II ɜ ɜɨɞɧɨɦ ɪɚɫɬɜɨɪɟ C8C 12Im NO3
(ɩɭɧɤɬɢɪɨɦ ɨɛɨɡɧɚɱɟɧɚ ɬɟɨɪɟɬɢɱɟɫɤɚɹ ɮɭɧɤɰɢɹ)
Ɍɚɛɥɢɰɚ 3
qÄÈ»Ã̾Ä»ÈƾͻÇÀ¶µ Ç»Á»ÀȾ¸ÃÄÇÈÒ ÓÁ»ÀÈÆĺĸ
ɗɥɟɤɬɪɨɞ
lg K pot
X ,NO3−
II
ɗɅɂɌ 021
SO42–
–3,41
–3,39
Ac–
–2,04
–1,97
Cl–
–1,45
–1,36
Br–
–0,94
–0,69
Sal–
0,99
1,38
I–
1,01
1,06
ClO4–
2,55
2,81
sɦɢɧ ɫɨɫɬɚɜɥɹɟɬ 6,3×10–6 Ɇ (ɪɢɫ. 2). ɉɨɞɨɛɧɚɹ ɫɭɛɧɟɪɧɫɬɨɜɫɤɚɹ ɷɥɟɤɬɪɨɞɧɚɹ ɮɭɧɤɰɢɹ, ɜɟɪɨɹɬɧɨ, ɨɛɴɹɫɧɹɟɬɫɹ ɩɪɢɫɭɬɫɬɜɢɟɦ ɜ ɪɚɫɬɜɨɪɟ ɝɢɞɪɨɮɨɛɧɵɯ ɤɚɬɢɨɧɨɜ ɢɦɢɞɚɡɨɥɢɹ, ɤɨɬɨɪɵɟ, ɩɪɨɧɢɤɚɹ ɜ ɦɟɦɛɪɚɧɭ, ɫɧɢɠɚɸɬ ɟɟ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɶ ɤ ɧɢɬɪɚɬɭ. ɉɪɢ ɛɨɥɟɟ ɜɵ-
ɫɨɤɢɯ ɤɨɧɰɟɧɬɪɚɰɢɹɯ ɂɀ (ɜɵɲɟ 2×10–4 Ɇ), ɦɟɦɛɪɚɧɚ ɭɬɪɚɱɢɜɚɟɬ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɶ ɤ ɚɧɢɨɧɭ, ɧɚɛɥɸɞɚɟɬɫɹ ɨɛɪɚɳɟɧɢɟ ɷɥɟɤɬɪɨɞɧɨɣ ɮɭɧɤɰɢɢ ɧɚ ɤɚɬɢɨɧɧɧɭɸ,
ɱɬɨ, ɩɨ-ɜɢɞɢɦɨɦɭ, ɬɚɤɠɟ ɨɛɭɫɥɨɜɥɟɧɨ ɜɥɢɹɧɢɟɦ ɝɢɞɪɨɮɨɛɧɨɝɨ ɤɚɬɢɨɧɚ. Ɉɬɦɟɬɢɦ, ɨɞɧɚɤɨ, ɱɬɨ ɜ ɭɡɤɨɦ
ɢɧɬɟɪɜɚɥɟ ɤɨɧɰɟɧɬɪɚɰɢɣ ɂɀ (1×10–4–1×10–5 Ɇ) ɩɨɬɟɧɰɢɚɥ ɷɥɟɤɬɪɨɞɚ ɯɨɪɨɲɨ ɜɨɫɩɪɨɢɡɜɨɞɢɦ, ɱɬɨ ɩɨɡɜɨɥɹɟɬ ɪɟɤɨɦɟɧɞɨɜɚɬɶ ɪɚɡɪɚɛɨɬɚɧɧɵɣ ɂɋɗ ɞɥɹ ɫɟɥɟɤɬɢɜɧɨɝɨ ɨɩɪɟɞɟɥɟɧɢɢɹ ɂɀ, ɫɨɞɟɪɠɚɳɢɯ NO3–, ɜ ɬɨɦ
ɱɢɫɥɟ ɞɥɹ ɨɰɟɧɤɢ ɪɚɫɬɜɨɪɢɦɨɫɬɢ ɩɨɞɨɛɧɵɯ ɂɀ ɜ
ɜɨɞɟ.
pÅÆ»º»Á»Ã¾» ƶÇȸÄƾÂÄÇȾ s8s12ImNO3
¸ ¸Äº»
Ⱦɥɹ ɨɩɪɟɞɟɥɟɧɢɹ ɫɨɞɟɪɠɚɧɢɹ ɂɀ (C8C 12ImNO3)
ɜ ɜɨɞɟ ɢɫɩɨɥɶɡɨɜɚɥɢ ɷɥɟɤɬɪɨɞ II ɫ ɦɟɦɛɪɚɧɨɣ ɧɚ ɨɫɧɨɜɟ (ɋ16) 2ImNO3. Ƚɪɚɞɭɢɪɨɜɚɧɢɟ ɂɋɗ ɩɪɨɜɨɞɢɥɢ ɜ
ɪɚɫɬɜɨɪɟ C8C 12ImNO3. Ⱦɥɹ ɩɪɢɝɨɬɨɜɥɟɧɢɹ ɧɚɫɵɳɟɧɧɨɝɨ ɪɚɫɬɜɨɪɚ ɢɫɩɨɥɶɡɨɜɚɥɢ ɨɩɢɫɚɧɧɭɸ ɪɚɧɟɟ
ɦɟɬɨɞɢɤɭ [19]. Ɋɚɜɧɵɟ ɨɛɴɟɦɵ ɂɀ ɢ ɞɢɫɬɢɥɥɢɪɨɜɚɧɧɨɣ ɜɨɞɵ ɜɫɬɪɹɯɢɜɚɥɢ 10 ɦɢɧ. ɉɨɫɥɟ ɪɚɫɫɥɨɟɧɢɹ ɠɢɞɤɨɫɬɟɣ ɨɬɛɢɪɚɥɢ 1 ɦɥ ɜɨɞɧɨɣ ɮɚɡɵ, ɪɚɡɛɚɜɥɹɥɢ ɞɢɫɬɢɥɥɢɪɨɜɚɧɧɨɣ ɜɨɞɨɣ (1:10) ɢ ɩɪɨɜɨɞɢɥɢ
ɢɡɦɟɪɟɧɢɹ. ɋɨɞɟɪɠɚɧɢɟ ɂɀ ɧɚɯɨɞɢɥɢ ɦɟɬɨɞɨɦ ɩɪɹɦɨɣ ɩɨɬɟɧɰɢɨɦɟɬɪɢɢ. ɍɫɬɚɧɨɜɥɟɧɨ, ɱɬɨ ɪɚɫɬɜɨɪɢɦɨɫɬɶ ɋ8ɋ 12Im NO3 ɫɨɫɬɚɜɥɹɟɬ 5,6×10–4 Ɇ.
Ɋɚɛɨɬɚ ɜɵɩɨɥɧɟɧɚ ɩɪɢ ɮɢɧɚɧɫɨɜɨɣ ɩɨɞɞɟɪɠɤɟ ɊɎɎɂ (ɝɪɚɧɬ ʋ 05–03–32976).
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ɉɨɫɬɭɩɢɥɚ ɜ ɪɟɞɚɤɰɢɸ 10.10.06
NITRATE-CONTAINING IONIC LIQUIDS AS ACTIVE MEMBRANE
COMPONENTS OF NITRATE-SELECTIVE ELECTRODES
V.V. Sviridov, O.A. Avramenko, A.A. Rayeva, I.V. Pletniov, V.E. Baulin, N.V. Shvedene
(Division of Analytical Chemistry)
Two dialkylimidazolium-based ionic liquids were investigated as active components in the PVC
membranes of nitrate ion-selective electrodes (ISE). The main potentiometric characteristics
including selectivity to nitrate ion and pH-function were studied. The membranes involved
contain 5% of active component and display close to theoretical response for nitrate ion. Using of
more hydrophobic ionic liquid increases the sensitivity up to 57 mV/pC and decreases the low
–6
detection limit (smin=3.7·10 n). In comparison to commercial nitrate-selective electrode ELIT
021 advantages of ISE developed were found: the lower Cmin and the lower time of response. It was
shown that ISE developed is applicable for direct potentiometric detection of ionic liquids
containing nitrate ion in aqueous solutions.
18 ȼɆɍ, ɯɢɦɢɹ, ʋ 4