( ) ( ) ВЛИЯНИЕ ЭЛЕКТРОЛИТОВ НА ЧУВСТВИТЕЛЬНОСТЬ

ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
257
ɍȾɄ 535.8:543.420.62;543.422.5;543.432
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f.s. x¶ÆÒÀĸ, b.b. h¾ÆÀĸ, n.b. qÆÄÇÀÉÆþÃ
(À¶Ê»ºÆ¶ ¶Ã¶Á¾È¾Í»ÇÀÄ¿ ˾¾¾; e-mail: Michael@analyt.chem.msu.ru)
jÇÇÁ»ºÄ¸¶ÃÑ È»ÆÂÄÄÅȾͻÇÀ¾» ǸĿÇȸ¶ ¸ÄºÃÑË Æ¶ÇȸÄÆĸ ǾÁÒÃÑË ÓÁ»ÀÈÆÄÁ¾Èĸ (H2SO4,
HCl, NaCl, Na2SO4, NaOH). uÇȶÃĸÁ»ÃÄ, ÍÈÄ ÅƾÆĺ¶ ÓÁ»ÀÈÆÄÁ¾È¶ ÄÀ¶½Ñ¸¶»È ¸Á¾µÃ¾» ö
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ÄȺ»ÁÒÃÑË ¾ÄÃĸ. o¶¾·ÄÁÒλ» ɸ»Á¾Í»Ã¾» ÀÄÓÊʾ̾»Ãȶ ÍɸÇȸ¾È»ÁÒÃÄÇȾ È»ÆÂÄÁ¾Ã½Ä¸ÑË ¾½Â»Æ»Ã¾¿ ö·ÁÔº¶»Èǵ ¸ ƶÇȸÄÆ¶Ë Ç»ÆÃÄ¿ À¾ÇÁÄÈÑ (¸ 2 ƶ½¶ Åƾ ÀÄÃÌ»ÃÈƶ̾¾ 0,6 n)
¾ ¸ ƶÇȸÄÆ¶Ë ËÁÄƾº¶ öÈƾµ (¸ 1,5 ƶ½¶ Åƾ ÀÄÃÌ»ÃÈƶ̾¾ 3 n), ¶ ¸ ƶÇȸÄÆ» ÇÄÁµÃÄ¿ À¾ÇÁÄÈÑ ½Ã¶Í¾ÂÄ¹Ä ÓÊÊ»Àȶ û ö·ÁÔº¶»Èǵ.
Ɍɟɪɦɨɥɢɧɡɨɜɚɹ ɫɩɟɤɬɪɨɦɟɬɪɢɹ (ɌɅɋ) ɹɜɥɹɟɬɫɹ ɫɨɜɪɟɦɟɧɧɵɦ ɦɟɬɨɞɨɦ ɦɨɥɟɤɭɥɹɪɧɨɣ ɚɛɫɨɪɛɰɢɨɧɧɨɣ
ɫɩɟɤɬɪɨɫɤɨɩɢɢ [1]. ȼ ɟɟ ɨɫɧɨɜɟ ɥɟɠɢɬ ɢɡɦɟɧɟɧɢɟ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɫɪɟɞɵ ɩɪɢ ɩɨɝɥɨɳɟɧɢɢ ɥɚɡɟɪɧɨɝɨ ɢɡɥɭɱɟɧɢɹ, ɩɪɨɩɨɪɰɢɨɧɚɥɶɧɨɟ ɤɨɧɰɟɧɬɪɚɰɢɢ ɩɨɝɥɨɳɚɸɳɟɝɨ ɜɟɳɟɫɬɜɚ. Ɇɟɬɨɞ ɨɛɥɚɞɚɟɬ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɶɸ, ɩɪɟɜɵɲɚɸɳɟɣ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɶ ɫɩɟɤɬɪɨɮɨɬɨɦɟɬɪɢɢ ɧɚ ɞɜɚ-ɬɪɢ ɩɨɪɹɞɤɚ, ɱɬɨ ɩɨɡɜɨɥɹɟɬ ɢɫɩɨɥɶɡɨɜɚɬɶ ɟɝɨ ɞɥɹ ɨɩɪɟɞɟɥɟɧɢɹ ɫɥɟɞɨɜɵɯ ɤɨɧɰɟɧɬɪɚɰɢɣ ɪɚɡɥɢɱɧɵɯ ɫɨɟɞɢɧɟɧɢɣ. ɇɚ ɚɧɚɥɢɬɢɱɟɫɤɢɣ ɫɢɝɧɚɥ ɞɚɧɧɨɝɨ
ɦɟɬɨɞɚ ɨɱɟɧɶ ɫɢɥɶɧɨ ɜɥɢɹɸɬ ɫɜɨɣɫɬɜɚ ɫɪɟɞɵ, ɩɪɟɠɞɟ ɜɫɟɝɨ ɬɟɩɥɨɩɪɨɜɨɞɧɨɫɬɶ ɢ ɬɟɩɥɨɟɦɤɨɫɬɶ. ȼ ɥɢɬɟɪɚɬɭɪɟ ɯɨɪɨɲɨ ɨɩɢɫɚɧɵ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɜɨɞɵ ɢ ɧɟɤɨɬɨɪɵɯ ɪɚɫɩɪɨɫɬɪɚɧɟɧɧɵɯ ɨɪɝɚɧɢɱɟɫɤɢɯ ɪɚɫɬɜɨɪɢɬɟɥɟɣ [1, 2], ɨɞɧɚɤɨ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɟ
ɫɜɨɣɫɬɜɚ ɪɚɫɬɜɨɪɨɜ ɷɥɟɤɬɪɨɥɢɬɨɜ ɞɨ ɫɢɯ ɩɨɪ ɦɚɥɨ
ɢɡɭɱɟɧɵ, ɯɨɬɹ ɩɪɟɞɫɬɚɜɥɹɸɬ ɡɧɚɱɢɬɟɥɶɧɵɣ ɢɧɬɟɪɟɫ
ɜɜɢɞɭ ɨɱɟɧɶ ɲɢɪɨɤɨɝɨ ɢɯ ɢɫɩɨɥɶɡɨɜɚɧɢɹ ɜ ɚɧɚɥɢɬɢɱɟɫɤɨɣ ɩɪɚɤɬɢɤɟ.
ɇɚɫɬɨɹɳɚɹ ɪɚɛɨɬɚ ɩɨɫɜɹɳɟɧɚ ɢɫɫɥɟɞɨɜɚɧɢɸ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɨɜ ɧɟɤɨɬɨɪɵɯ
ɲɢɪɨɤɨ ɪɚɫɩɪɨɫɬɪɚɧɟɧɧɵɯ ɷɥɟɤɬɪɨɥɢɬɨɜ ɫ ɰɟɥɶɸ ɩɨɜɵɲɟɧɢɹ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɬɟɪɦɨɥɢɧɡɨɜɵɯ ɨɩɪɟɞɟɥɟɧɢɣ ɧɚ ɨɫɧɨɜɟ ɬɟɨɪɟɬɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɚ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɯ ɩɚɪɚɦɟɬɪɨɜ ɫɪɟɞ ɢ ɢɯ ɩɪɨɜɟɪɤɢ ɧɚ ɩɪɢɦɟɪɚɯ ɦɨɞɟɥɶɧɵɯ ɫɢɫɬɟɦ.
r¶ÇÍ»Èöµ ͶÇÈÒ
ȼɫɥɟɞɫɬɜɢɟ ɛɟɡɵɡɥɭɱɚɬɟɥɶɧɨɣ ɪɟɥɚɤɫɚɰɢɢ ɷɥɟɤɬɪɨɧɧɨ-ɜɨɡɛɭɠɞɟɧɧɵɯ ɫɨɫɬɨɹɧɢɣ ɦɨɥɟɤɭɥ ɜ ɩɨɥɟ ɢɡɥɭɱɟɧɢɹ ɥɚɡɟɪɚ ɩɪɨɢɫɯɨɞɢɬ ɥɨɤɚɥɶɧɵɣ ɧɚɝɪɟɜ ɜɟɳɟɫɬɜɚ.
ɋɨɡɞɚɜɚɟɦɵɣ ɩɪɨɮɢɥɶ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɨɩɪɟɞɟɥɹɟɬɫɹ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɵɦ ɪɚɫɩɪɟɞɟɥɟɧɢɟɦ ɷɧɟɪɝɢɢ
ɜ ɩɚɞɚɸɳɟɦ ɫɜɟɬɨɜɨɦ ɥɭɱɟ ɢ ɞɟɣɫɬɜɭɟɬ ɤɚɤ ɨɩɬɢɱɟɫɤɢɣ ɷɥɟɦɟɧɬ [1]. ɉɨɥɨɠɟɧɢɹ, ɩɪɢɧɢɦɚɟɦɵɟ ɞɥɹ
ɪɚɫɱɟɬɚ ɫɜɨɣɫɬɜ ɬɚɤɨɝɨ ɨɩɬɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ, ɢ ɜɵɜɨɞ ɭɪɚɜɧɟɧɢɹ, ɨɩɢɫɵɜɚɸɳɟɝɨ ɪɚɫɩɪɟɞɟɥɟɧɢɟ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɜ ɫɪɟɞɟ, ɫɨɡɞɚɜɚɟɦɨɝɨ ɬɟɦɩɟɪɚɬɭɪɧɵɦ ɩɨɥɟɦ, ɩɪɢɜɟɞɟɧɵ ɜ ɥɢɬɟɪɚɬɭɪɟ:
n (r , t ) = n 0 +
dn
ΔT ( r , t ) ,
dT
(1)
ɝɞɟ n0 – ɩɨɤɚɡɚɬɟɥɶ ɩɪɟɥɨɦɥɟɧɢɹ ɨɛɪɚɡɰɚ ɞɨ ɨɛɥɭɱɟɧɢɹ.
Ɏɚɡɨɜɵɣ ɫɞɜɢɝ, ɜɧɨɫɢɦɵɣ ɞɚɧɧɵɦ ɨɩɬɢɱɟɫɤɢɦ ɷɥɟɦɟɧɬɨɦ ɜ ɡɨɧɞɢɪɭɸɳɢɣ ɥɭɱ, ɜɵɪɚɠɚɟɬɫɹ ɜ ɜɢɞɟ:
Φ=
θ t
1
∫
t c 0 1 + 2 t′ / t c
⎡
⎛ −2r 2 / ω 2 ⎞ ⎤
e ⎟⎥
⎢1 − exp ⎜
dt′,
⎜ 1 + 2 t '/ t c ⎟ ⎥
⎢
⎝
⎠
⎣
⎦
(2)
ɝɞɟ tÇ – ɯɚɪɚɤɬɟɪɢɫɬɢɱɟɫɤɨɟ ɜɪɟɦɹ ɪɚɡɜɢɬɢɹ ɬɟɪɦɨɥɢɧɡɵ, ωe – ɪɚɞɢɭɫ ɥɭɱɚ ɜ ɩɟɪɟɬɹɠɤɟ, ɚ
θ = 2, 303
Pe Adn / dT
kλ
,
(3)
p
ɝɞɟ A – ɨɩɬɢɱɟɫɤɚɹ ɩɥɨɬɧɨɫɬɶ ɨɛɪɚɡɰɚ, k – ɬɟɩɥɨɩɪɨɜɨɞɧɨɫɬɶ, λp – ɞɥɢɧɚ ɜɨɥɧɵ ɢɡɥɭɱɟɧɢɹ, ɡɨɧɞɢɪɭɸɳɟɝɨ ɬɟɪɦɨɥɢɧɡɭ, Pe – ɦɨɳɧɨɫɬɶ ɢɧɞɭɰɢɪɭɸɳɟɝɨ
ɢɡɥɭɱɟɧɢɹ [1].
Ⱦɟɣɫɬɜɢɟ ɨɩɬɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ ɚɧɚɥɨɝɢɱɧɨ ɞɟɣɫɬɜɢɸ ɪɚɫɫɟɢɜɚɸɳɟɣ ɥɢɧɡɵ, ɬɚɤ ɤɚɤ ɩɨɤɚɡɚɬɟɥɶ
ɩɪɟɥɨɦɥɟɧɢɹ ɛɨɥɶɲɢɧɫɬɜɚ ɜɟɳɟɫɬɜ ɜɞɚɥɢ ɨɬ ɫɢɥɶɧɵɯ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ ɭɦɟɧɶɲɚɟɬɫɹ ɫ ɪɨɫɬɨɦ ɬɟɦɩɟɪɚɬɭɪɵ (ɡɚ ɢɫɤɥɸɱɟɧɢɟɦ ɫɢɥɶɧɨ ɚɝɪɟɝɢɪɨɜɚɧɧɵɯ
ɠɢɞɤɨɫɬɟɣ ɜɛɥɢɡɢ ɮɚɡɨɜɨɝɨ ɩɟɪɟɯɨɞɚ) [1]. ȼɵɪɚɠɟɧɢɟ (3) ɩɪɟɞɫɬɚɜɥɹɟɬ ɫɨɛɨɣ ɚɧɚɥɢɬɢɱɟɫɤɢɣ ɫɢɝɧɚɥ
ɦɟɬɨɞɚ ɬɟɪɦɨɥɢɧɡɨɜɨɣ ɫɩɟɤɬɪɨɦɟɬɪɢɢ. ȿɝɨ ɦɨɠɧɨ
ɩɪɟɨɛɪɚɡɨɜɚɬɶ ɤ ɜɢɞɭ:
θ = 2,303 ⋅ AE0 Pe ,
(4)
ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
258
ɝɞɟ ɮɚɤɬɨɪ ɭɜɟɥɢɱɟɧɢɹ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ g0
dn / dT
E0 = −
kλ p
∂n(T , ρ) = (
(5)
ɨɩɪɟɞɟɥɹɟɬɫɹ ɬɨɥɶɤɨ ɫɜɨɣɫɬɜɚɦɢ ɫɪɟɞɵ.
ɉɪɢɱɢɧɨɣ ɜɨɡɧɢɤɧɨɜɟɧɢɹ ɨɩɬɢɱɟɫɤɨɣ ɧɟɨɞɧɨɪɨɞɧɨɫɬɢ ɜ ɫɪɟɞɟ ɜ ɩɨɥɟ ɢɡɥɭɱɟɧɢɹ ɥɚɡɟɪɚ ɹɜɥɹɟɬɫɹ ɥɨɤɚɥɶɧɵɣ ɧɚɝɪɟɜ ɜɫɥɟɞɫɬɜɢɟ ɛɟɡɵɡɥɭɱɚɬɟɥɶɧɨɣ ɪɟɥɚɤɫɚɰɢɢ
ɷɥɟɤɬɪɨɧɧɨ-ɜɨɡɛɭɠɞɟɧɧɵɯ ɫɨɫɬɨɹɧɢɣ ɦɨɥɟɤɭɥ ɢ ɜɵɡɜɚɧɧɨɟ ɷɬɢɦ ɢɡɦɟɧɟɧɢɟ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ. ɉɨɤɚɡɚɬɟɥɶ ɩɪɟɥɨɦɥɟɧɢɹ ɹɜɥɹɟɬɫɹ ɨɞɧɨɣ ɢɡ ɮɭɧɞɚɦɟɧɬɚɥɶɧɵɯ ɯɚɪɚɤɬɟɪɢɫɬɢɤ ɜɟɳɟɫɬɜɚ. Ʉɚɤ ɢɡɜɟɫɬɧɨ, ɜ
ɫɨɨɬɜɟɬɫɬɜɢɢ ɫ ɭɪɚɜɧɟɧɢɹɦɢ Ɇɚɤɫɜɟɥɥɚ, ɜɞɚɥɢ ɨɬ
ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ ɨɧ ɨɩɪɟɞɟɥɹɟɬɫɹ ɞɢɷɥɟɤɬɪɢɱɟɫɤɨɣ ɢ
ɦɚɝɧɢɬɧɨɣ ɩɪɨɧɢɰɚɟɦɨɫɬɹɦɢ ɜɟɳɟɫɬɜɚ ( n = εμ ) .
Cɜɹɡɶ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɜɟɳɟɫɬɜɚ ɫ ɟɝɨ
ɷɥɟɤɬɪɨɦɚɝɧɢɬɧɨɣ ɩɨɥɹɪɢɡɭɟɦɨɫɬɶɸ ɨɩɢɫɵɜɚɟɬɫɹ
ɭɪɚɜɧɟɧɢɟɦ Ʌɨɪɟɧɬɰɚ–Ʌɨɪɟɧɰɚ:
Rm =
n 2 −1 M
,
n2 +2 ρ
(6)
ɝɞɟ Rm – ɦɨɥɹɪɧɚɹ ɪɟɮɪɚɤɰɢɹ.
ȼ ɩɪɚɤɬɢɤɟ ɨɛɵɱɧɨ ɢɫɩɨɥɶɡɭɸɬɫɹ ɡɧɚɱɟɧɢɹ ɩɨɤɚɡɚɬɟɥɟɣ ɩɪɟɥɨɦɥɟɧɢɹ, ɨɩɪɟɞɟɥɟɧɧɵɟ ɜ ɧɨɪɦɚɥɶɧɵɯ ɭɫɥɨɜɢɹɯ (20°ɋ). ɉɨɤɚɡɚɬɟɥɶ ɩɪɟɥɨɦɥɟɧɢɹ ɫɥɨɠɧɵɦ ɨɛɪɚɡɨɦ ɡɚɜɢɫɢɬ ɨɬ ɡɧɚɱɢɬɟɥɶɧɨɝɨ ɱɢɫɥɚ ɩɚɪɚɦɟɬɪɨɜ ɢ ɧɟ
ɜɵɪɚɠɚɟɬɫɹ ɧɚɩɪɹɦɭɸ ɱɟɪɟɡ ɮɭɧɤɰɢɢ ɫɨɫɬɨɹɧɢɹ ɫɢɫɬɟɦɵ. ȼ ɬɟɪɦɨɥɢɧɡɨɜɨɣ ɫɩɟɤɬɪɨɦɟɬɪɢɢ ɩɪɢɧɰɢɩɢɚɥɶɧɨ
ɜɚɠɟɧ ɯɚɪɚɤɬɟɪ ɡɚɜɢɫɢɦɨɫɬɢ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ
ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ, ɩɨɫɤɨɥɶɤɭ ɷɬɚ ɡɚɜɢɫɢɦɨɫɬɶ ɧɚɪɹɞɭ ɫ
ɜɟɥɢɱɢɧɨɣ ɬɟɩɥɨɩɪɨɜɨɞɧɨɫɬɢ ɨɩɪɟɞɟɥɹɟɬ ɭɜɟɥɢɱɟɧɢɟ
ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɦɟɬɨɞɚ.
ɉɪɢ ɦɚɥɵɯ ɢɡɦɟɧɟɧɢɹɯ ɬɟɦɩɟɪɚɬɭɪɵ ɞɨɩɭɫɬɢɦɨ
ɪɚɫɫɦɚɬɪɢɜɚɬɶ ɜɤɥɚɞ ɬɟɦɩɟɪɚɬɭɪɵ ɢ ɩɥɨɬɧɨɫɬɢ ɜ ɢɡɦɟɧɟɧɢɟ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɜ (1) ɩɨ ɨɬɞɟɥɶɧɨɫɬɢ:
∂n(T , ρ) = (
∂n
∂n
) P ∂T + ( )T ∂ρ .
∂T
∂ρ
(7)
ɉɟɪɜɵɣ ɱɥɟɧ ɩɪɚɜɨɣ ɱɚɫɬɢ ɞɚɧɧɨɝɨ ɭɪɚɜɧɟɧɢɹ –
ɜɤɥɚɞ ɡɚɜɢɫɢɦɨɫɬɢ ɦɨɥɹɪɧɨɣ ɪɟɮɪɚɤɰɢɢ ɦɨɥɟɤɭɥ ɨɛɪɚɡɰɚ ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ. Ɉɛɵɱɧɨ ɷɬɨɬ ɜɤɥɚɞ ɨɬɧɨɫɢɬɟɥɶɧɨ ɦɚɥ ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɜɤɥɚɞɨɦ ɡɚɜɢɫɢɦɨɫɬɢ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɨɬ ɩɥɨɬɧɨɫɬɢ, ɨɩɪɟɞɟɥɹɟɦɵɦ ɭɪɚɜɧɟɧɢɟɦ Ʌɨɪɟɧɬɰɚ–Ʌɨɪɟɧɰɚ ɢ ɜɵɪɚɠɟɧɧɵɦ ɜɬɨɪɵɦ ɱɥɟɧɨɦ ɩɪɚɜɨɣ ɱɚɫɬɢ ɭɪɚɜɧɟɧɢɹ (7). Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɞɚɧɧɵɣ ɱɥɟɧ ɜɵɪɚɠɚɟɬɫɹ ɱɟɪɟɡ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɢɣ ɤɨɷɮɮɢɰɢɟɧɬ ɨɛɴɟɦɧɨɝɨ ɪɚɫɲɢɪɟɧɢɹ β. Ɂɚɜɢɫɢɦɨɫɬɶ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɨɬ ɬɟɦɩɟɪɚɬɭɪɵ (1), ɬɚɤɢɦ ɨɛɪɚɡɨɦ, ɦɨɠɟɬ ɛɵɬɶ ɜɵɪɚɠɟɧɚ ɫɭɦɦɨɣ ɞɜɭɯ ɱɥɟɧɨɜ:
∂n
∂n
) P ∂T + ( )T ∂ρ .
∂T
∂ρ
(8)
ɂɫɩɨɥɶɡɭɹ ɭɪɚɜɧɟɧɢɟ Ʌɨɪɟɧɬɰɚ–Ʌɨɪɟɧɰɚ (6), ɩɨɥɭɱɚɟɦ:
(n 02 + 2)2 R m (n 2 + 2)(n 2 − 1)
⎛ ∂n ⎞
0
,
= 0
⎜ ⎟ =
6n 0
6n 0 ρ0
M
⎝ ∂ρ ⎠T
(9)
ɝɞɟ n0 ɢ ρ0 – ɡɧɚɱɟɧɢɹ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɢ
ɩɥɨɬɧɨɫɬɢ ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ ɩɪɢ ɩɪɨɦɟɠɭɬɨɱɧɨɦ ɡɧɚɱɟɧɢɢ ɬɟɦɩɟɪɚɬɭɪɵ. ɉɥɨɬɧɨɫɬɶ ɥɢɧɟɣɧɨ ɫɜɹɡɚɧɚ ɫ ɬɟɦɩɟɪɚɬɭɪɨɣ ɱɟɪɟɡ ɪɚɜɧɨɜɟɫɧɵɟ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɢɟ
ɮɭɧɤɰɢɢ. ȼɬɨɪɨɣ ɱɥɟɧ ɬɟɦɩɟɪɚɬɭɪɧɨɣ ɡɚɜɢɫɢɦɨɫɬɢ
ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɦɨɠɟɬ ɛɵɬɶ ɩɪɟɞɫɬɚɜɥɟɧ ɜ
ɫɥɟɞɭɸɳɟɦ ɜɢɞɟ:
⎛ ∂n ⎞
⎜ ⎟
⎝ ∂ρ ⎠ T
(
)(
)
n 02 + 2 n 02 − 1
⎛ ∂n ⎞
⎛ ∂ρ ⎞
. (10)
=
−ρ
β
=
−β
⎜
⎟
0 ⎜ ∂ρ ⎟
6n 0
⎝ ∂T ⎠ P
⎝ ⎠T
Ⱦɥɹ ɝɚɡɚ ɩɪɢ ɞɚɜɥɟɧɢɢ ɩɨɪɹɞɤɚ ɧɟɫɤɨɥɶɤɢɯ ɚɬɦɨɫɮɟɪ ɩɨɤɚɡɚɬɟɥɶ ɩɪɟɥɨɦɥɟɧɢɹ ɦɨɠɟɬ ɛɵɬɶ ɩɪɹɦɨ ɜɵɪɚɠɟɧ ɱɟɪɟɡ ɩɨɤɚɡɚɬɟɥɶ ɩɪɟɥɨɦɥɟɧɢɹ ɜɧɟ ɨɩɬɢɱɟɫɤɨɝɨ
ɷɥɟɦɟɧɬɚ (ɬ.ɟ. ɜɧɟ ɧɚɝɪɟɬɨɣ ɨɛɥɚɫɬɢ) ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ ɝɚɡɨɜɵɯ ɡɚɤɨɧɨɜ. ɗɬɨ ɫɜɹɡɚɧɨ ɫ ɬɟɦ, ɱɬɨ ɝɚɡ ɩɪɢ
ɧɢɡɤɨɦ ɞɚɜɥɟɧɢɢ ɢɦɟɟɬ ɩɨɤɚɡɚɬɟɥɶ ɩɪɟɥɨɦɥɟɧɢɹ,
ɨɱɟɧɶ ɛɥɢɡɤɢɣ ɤ 1. ɋɥɟɞɨɜɚɬɟɥɶɧɨ, ɞɥɹ ɞɢɚɩɚɡɨɧɚ ɧɨɪɦɚɥɶɧɵɯ ɞɚɜɥɟɧɢɣ ɜ ɨɛɪɚɡɰɟ ɝɚɡɚ ɦɨɠɧɨ ɡɚɩɢɫɚɬɶ:
n 02 − 1
1
⎛ ∂n ⎞
2
≈
−
β
n
−
=
−
(
1)
,
⎜
⎟
0
2
2T 0
⎝ ∂T ⎠ T 0
(11)
ɝɞɟ T0 – ɪɚɜɧɨɜɟɫɧɚɹ ɬɟɦɩɟɪɚɬɭɪɚ ɨɛɪɚɡɰɚ. ɉɪɢ ɩɨɫɬɨɹɧɧɨɣ ɩɥɨɬɧɨɫɬɢ ɬɟɦɩɟɪɚɬɭɪɧɚɹ ɡɚɜɢɫɢɦɨɫɬɶ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɨɩɪɟɞɟɥɹɟɬɫɹ ɬɟɦɩɟɪɚɬɭɪɧɨɣ ɡɚɜɢɫɢɦɨɫɬɶɸ ɦɨɥɹɪɧɨɣ ɪɟɮɪɚɤɰɢɢ:
2
2
ρ (n 0 + 2) ⎛ ∂R m ⎞
⎛ ∂n ⎞
⎜
⎟.
⎜
⎟ =
6n 0 ⎝ ∂T ⎠
⎝ ∂T ⎠ ρ M
(12)
Ɉɫɧɨɜɧɵɦ ɩɚɪɚɦɟɬɪɨɦ, ɨɩɪɟɞɟɥɹɸɳɢɦ ɮɚɤɬɨɪ ɭɜɟɥɢɱɟɧɢɹ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ (5), ɹɜɥɹɟɬɫɹ ɬɟɦɩɟɪɚɬɭɪɧɚɹ ɡɚɜɢɫɢɦɨɫɬɶ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɜɟɳɟɫɬɜɚ –
dn/dT. Ⱦɥɹ ɩɨɞɚɜɥɹɸɳɟɝɨ ɛɨɥɶɲɢɧɫɬɜɚ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɨɜ, ɜ ɬɨɦ ɱɢɫɥɟ ɪɚɫɬɜɨɪɨɜ ɷɥɟɤɬɪɨɥɢɬɨɜ, ɩɪɹɦɵɯ
ɞɚɧɧɵɯ ɨ ɩɨɤɚɡɚɬɟɥɟ ɩɪɟɥɨɦɥɟɧɢɹ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ,
ɨɬɥɢɱɧɨɣ ɨɬ ɤɨɦɧɚɬɧɨɣ, ɜ ɥɢɬɟɪɚɬɭɪɟ ɧɟɬ. ȿɞɢɧɫɬɜɟɧɧɨɣ ɜɨɡɦɨɠɧɨɫɬɶɸ ɨɰɟɧɤɢ ɢ ɪɚɫɱɟɬɚ ɬɟɦɩɟɪɚɬɭɪɧɨɣ
ɡɚɜɢɫɢɦɨɫɬɢ ɩɨɤɚɡɚɬɟɥɹ ɩɪɟɥɨɦɥɟɧɢɹ ɜ ɬɚɤɢɯ ɫɥɭɱɚɹɯ ɹɜɥɹɟɬɫɹ ɢɫɩɨɥɶɡɨɜɚɧɢɟ ɭɪɚɜɧɟɧɢɹ Ʌɨɪɟɧɬɰɚ–Ʌɨɪɟɧɰɚ ɢ ɬɚɛɥɢɰ ɩɥɨɬɧɨɫɬɢ, ɨɛɵɱɧɨ ɞɨɫɬɭɩɧɵɯ ɜ
ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
259
Ɍɚɛɥɢɰɚ1
r¶ÇÍ»È È»ÆÂÄÄÅȾͻÇÀ¾Ë ǸĿÇȸ ƶÇȸÄÆĸ ÓÁ»ÀÈÆÄÁ¾Èĸ [3–5]
Ɇɨɞɢɮɢɤɚɬɨɪ,
ɫ, ɦɨɥɶ/ɥ
ρ, ɤɝ/ɞɦ3
–dρ/dT, ɤɝ/ɦ3
nD
–dn/dT⋅104, K−1
k, ȼɬ/ɦ.Ʉ
E0/E0, ɜɨɞ
0
0,9982
3,58
1,33319
0,91
0,5994
1
0,204
1,0131
6,31
1,33572
2,31
0,5969
1,76
0,408
1,0252
6,80
1,33801
2,47
0,5916
1,90
0,612
1,0372
7,28
1,34023
2,64
0,5864
2,04
0,816
1,0492
7,76
1,34245
2,79
0,5813
2,19
1,020
1,0612
8,24
1,34465
2,96
0,5762
2,34
1,531
1,0912
9,45
1,34999
3,36
0,5641
2,71
2,041
1,1212
10,07
1,35513
3,74
0,5526
3,08
0
0,9986
3,58
1,33319
0,91
0,5988
1
0,548
1,0092
4,49
1,33779
1,66
0,5774
1,89
1,096
1,0183
4,78
1,34227
1,78
0,5558
2,10
1,644
1,0273
5,07
1,34669
1,90
0,5345
2,33
2,192
1,0364
5,36
1,35102
2,01
0,5137
2,58
2,740
1,0455
5,65
1,35528
2,13
0,4932
2,85
0
0,9982
3,58
1,33299
0,91
0,5988
1
0,342
1,0134
4,10
1,33667
1,5
0,5784
1,66
0,684
1,0262
4,61
1,34002
1,69
0,5579
1,86
1,025
1,0390
5,12
1,34332
1,87
0,5375
2,07
1,368
1,0518
5,63
1,34651
2,05
0,5170
2,28
1,709
1,0646
6,13
1,34963
2,23
0,4966
2,49
2,564
1,0966
7,41
1,35721
2,68
0,4455
3,02
3,418
1,1286
8,68
1,36446
3,13
0,3944
3,54
ɋɟɪɧɚɹ ɤɢɫɥɨɬɚ*
ɋɨɥɹɧɚɹ ɤɢɫɥɨɬɚ**
ɏɥɨɪɢɞ ɧɚɬɪɢɹ**
qƾ»Ͷþµ. Ɂɧɚɱɟɧɢɹ ɩɪɢɜɟɞɟɧɵ ɞɥɹ ɬɟɦɩɟɪɚɬɭɪɵ: *17,5°ɋ ɢ ** 20°ɋ.
ɫɩɪɚɜɨɱɧɨɣ ɢɥɢ ɫɩɟɰɢɚɥɶɧɨɣ ɥɢɬɟɪɚɬɭɪɟ ɞɥɹ ɛɨɥɶɲɢɧɫɬɜɚ ɪɚɫɩɪɨɫɬɪɚɧɟɧɧɵɯ ɪɚɫɬɜɨɪɨɜ. Ɉɞɧɚɤɨ ɤ
ɞɚɧɧɵɦ, ɩɨɥɭɱɟɧɧɵɦ ɜ ɪɟɡɭɥɶɬɚɬɟ ɬɚɤɨɝɨ ɪɚɫɱɟɬɚ,
ɫɥɟɞɭɟɬ ɨɬɧɨɫɢɬɶɫɹ ɫ ɨɫɬɨɪɨɠɧɨɫɬɶɸ ɜɫɥɟɞɫɬɜɢɟ
ɨɝɪɚɧɢɱɟɧɧɨɣ ɩɪɢɦɟɧɢɦɨɫɬɢ ɞɚɧɧɨɝɨ ɭɪɚɜɧɟɧɢɹ ɜ
ɤɨɧɞɟɧɫɢɪɨɜɚɧɧɵɯ ɮɚɡɚɯ. ȼ ɱɚɫɬɧɨɫɬɢ, ɪɚɫɱɟɬ dn/dT
ɞɥɹ ɜɨɞɵ ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ ɷɬɨɝɨ ɦɟɬɨɞɚ ɧɟɜɨɡɦɨɠɟɧ – ɨɧ ɩɪɢɜɨɞɢɬ ɤ ɩɨɥɨɠɢɬɟɥɶɧɨɣ ɨɲɢɛɤɟ, ɩɪɟɜɵɲɚɸɳɟɣ 50%. ɉɨ ɫɪɚɜɧɟɧɢɸ ɫ ɜɨɞɨɣ, ɜɫɟ ɞɪɭɝɢɟ
ɫɪɟɞɵ ɦɟɧɟɟ ɩɨɥɹɪɧɵ, ɱɬɨ ɩɨɡɜɨɥɹɟɬ ɨɠɢɞɚɬɶ ɛɨɥɶɲɟɝɨ ɫɨɨɬɜɟɬɫɬɜɢɹ ɪɚɫɱɟɬɨɜ ɞɟɣɫɬɜɢɬɟɥɶɧɨɫɬɢ. Ⱦɥɹ
ɩɪɨɜɟɞɟɧɢɹ ɪɚɫɱɟɬɚ ɢɫɩɨɥɶɡɭɟɬɫɹ ɭɪɚɜɧɟɧɢɟ, ɜɵɜɟɞɟɧɧɨɟ ɢɡ (11) ɢ (12):
(
)(
)
n 2 −1 n 2 + 2
dn ⎛ dn ⎞
⎛ dρ ⎞
.
≅⎜
⎟ =⎜
⎟ ⋅
6n 0ρ0
dT ⎝ dT ⎠ P ⎝ dT ⎠ P
(13)
Ʉɨɪɪɟɥɹɰɢɨɧɧɵɟ ɭɪɚɜɧɟɧɢɹ ɞɥɹ ɬɟɩɥɨɩɪɨɜɨɞɧɨɫɬɢ,
ɩɪɢɝɨɞɧɵɟ ɞɥɹ ɬɚɤɢɯ ɪɚɫɬɜɨɪɨɜ, ɜ ɥɢɬɟɪɚɬɭɪɟ ɧɟ ɨɩɢɫɚɧɵ. Ɉɞɧɚɤɨ ɬɟɩɥɨɩɪɨɜɨɞɧɨɫɬɶ ɦɧɨɝɢɯ ɩɪɨɦɵɲɥɟɧɧɨ
ɜɚɠɧɵɯ ɪɚɫɬɜɨɪɨɜ ɬɨɱɧɨ ɨɩɪɟɞɟɥɟɧɚ ɩɪɢ ɧɟɫɤɨɥɶɤɢɯ
ɡɧɚɱɟɧɢɹɯ ɬɟɦɩɟɪɚɬɭɪɵ ɢ ɩɪɟɞɫɬɚɜɥɟɧɚ ɜ ɫɩɪɚɜɨɱɧɨɣ
ɥɢɬɟɪɚɬɭɪɟ [3–5], ɱɬɨ ɩɨɡɜɨɥɹɟɬ ɜɵɩɨɥɧɢɬɶ ɪɚɫɱɟɬ
ɮɚɤɬɨɪɚ ɭɜɟɥɢɱɟɧɢɹ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɬɟɪɦɨɥɢɧɡɨɜɵɯ
ɢɡɦɟɪɟɧɢɣ ɞɥɹ ɪɹɞɚ ɫɢɫɬɟɦ. ȼ ɬɚɛɥ. 1 ɩɪɢɜɟɞɟɧɵ
ɪɚɫɱɟɬɵ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜ ɪɚɫɬɜɨɪɨɜ ɫɟɪɧɨɣ
260
ɢ ɫɨɥɹɧɨɣ ɤɢɫɥɨɬ, ɚ ɬɚɤɠɟ ɪɚɫɬɜɨɪɚ ɯɥɨɪɢɞɚ ɧɚɬɪɢɹ
ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ.
ÀÇŻƾ»ÃȶÁÒöµ ͶÇÈÒ
bÅŶƶÈÉƶ. ȼɫɟ ɩɪɟɞɜɚɪɢɬɟɥɶɧɵɟ ɢɡɦɟɪɟɧɢɹ ɧɚ
ɷɬɚɩɟ ɫɩɟɤɬɪɨɮɨɬɨɦɟɬɪɢɱɟɫɤɢɯ ɢɫɫɥɟɞɨɜɚɧɢɣ ɩɪɨɜɨɞɢɥɢ ɧɚ ɫɩɟɤɬɪɨɮɨɬɨɦɟɬɪɟ “Shimadzu UVmini
1240CE” (əɩɨɧɢɹ) ɩɪɢ ɢɧɬɟɪɜɚɥɟ ɞɥɢɧ ɜɨɥɧ 400–
700 ɧɦ. Ⱦɥɹ ɬɟɪɦɨɥɢɧɡɨɜɵɯ ɢɡɦɟɪɟɧɢɣ ɢɫɩɨɥɶɡɨɜɚɧ
ɥɚɡɟɪɧɵɣ ɬɟɪɦɨɥɢɧɡɨɜɵɣ ɫɩɟɤɬɪɨɦɟɬɪ, ɩɚɪɚɦɟɬɪɵ ɤɨɬɨɪɨɝɨ ɨɩɢɫɚɧɵ ɜ [6]. Ɍɟɪɦɨɥɢɧɡɚ ɢɧɞɭɰɢɪɭɟɬɫɹ ɜ
ɤɜɚɪɰɟɜɨɣ ɤɸɜɟɬɟ (l = 1 ɫɦ) ɢɡɥɭɱɟɧɢɟɦ ɚɪɝɨɧɨɜɨɝɨ
ɢɨɧɧɨɝɨ ɥɚɡɟɪɚ “Innova 90-6” (“Coherent”, ɋɒȺ) ɫ
λ = 488,0 ɢ λ = 514,5 ɧɦ (TEM00-ɦɨɞɚ, ɦɨɳɧɨɫɬɶ ɜ
ɤɸɜɟɬɟ ɫ ɨɛɪɚɡɰɨɦ 100 ɦȼɬ). ȼ ɤɚɱɟɫɬɜɟ ɡɨɧɞɢɪɭɸɳɟɝɨ ɥɚɡɟɪɚ ɢɫɩɨɥɶɡɨɜɚɧ He–Ne-ɥɚɡɟɪ “SP-106-1”
( “Spectra Physics”, ɋɒȺ), 632,8 ɧɦ (TEM00-ɦɨɞɚ,
10 ɦȼɬ). ɋɢɝɧɚɥ (ɢɧɬɟɧɫɢɜɧɨɫɬɶ ɜ ɰɟɧɬɪɟ ɡɨɧɞɢɪɭɸɳɟɝɨ ɥɭɱɚ) ɫ ɮɨɬɨɞɢɨɞɚ ɩɨɞɚɟɬɫɹ ɧɚ ɛɥɨɤ Ⱥɐɉ–
ɐȺɉ, ɫɜɹɡɚɧɧɵɣ ɫ PC-ɫɨɜɦɟɫɬɢɦɵɦ ɤɨɦɩɶɸɬɟɪɨɦ.
ɋɢɧɯɪɨɧɢɡɚɰɢɹ ɩɪɨɰɟɫɫɚ ɢɡɦɟɪɟɧɢɣ ɨɫɭɳɟɫɬɜɥɹɟɬɫɹ
ɤɨɦɩɶɸɬɟɪɨɦ ɩɪɢ ɩɨɦɨɳɢ ɫɩɟɰɢɚɥɶɧɨɣ ɩɪɨɝɪɚɦɦɵ.
Ɉɬɧɨɫɢɬɟɥɶɧɨɟ ɫɬɚɧɞɚɪɬɧɨɟ ɨɬɤɥɨɧɟɧɢɟ ɢɡɦɟɪɟɧɢɣ ɧɚ
ɫɩɟɤɬɪɨɦɟɬɪɟ cɨɫɬɚɜɥɹɟɬ 0,01–0,02. ɉɟɪɟɞ ɩɪɨɜɟɞɟɧɢɟɦ ɬɟɪɦɨɥɢɧɡɨɜɨɝɨ ɷɤɫɩɟɪɢɦɟɧɬɚ ɞɥɹ ɩɨɞɬɜɟɪɠɞɟɧɢɹ
ɧɟɢɡɦɟɧɧɨɫɬɢ ε488 ɢɡɦɟɪɹɥɢ ɨɩɬɢɱɟɫɤɭɸ ɩɥɨɬɧɨɫɬɶ
ɜɫɟɯ ɨɛɪɚɡɰɨɜ ɨɤɪɚɲɟɧɧɵɯ ɜɟɳɟɫɬɜ ɜ ɪɚɡɥɢɱɧɵɯ ɫɪɟɞɚɯ ɧɚ ɫɤɚɧɢɪɭɸɳɟɦ ɫɩɟɤɬɪɨɮɨɬɨɦɟɬɪɟ “Shimadzu
UVmini 1240CE” ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ ɬɨɣ ɠɟ ɤɜɚɪɰɟɜɨɣ
ɤɸɜɟɬɵ (l = 1 ɫɦ), ɜ ɤɨɬɨɪɨɣ ɩɪɨɜɨɞɢɥɢ ɬɟɪɦɨɥɢɧɡɨɜɵɟ ɢɡɦɟɪɟɧɢɹ.
r¶ÇȸÄƾȻÁ¾ ¾ Æ»¶¹»ÃÈÑ. ȼ ɪɚɛɨɬɟ ɢɫɩɨɥɶɡɨɜɚɥɢ ɫɥɟɞɭɸɳɢɟ ɪɚɫɬɜɨɪɢɬɟɥɢ: ɞɢɫɬɢɥɥɢɪɨɜɚɧɧɭɸ
ɜɨɞɭ (pH 5,8; ɞɥɹ ɫɩɟɤɬɪɨɮɨɬɨɦɟɬɪɢɢ); ɛɢɞɢɫɬɢɥɥɢɪɨɜɚɧɧɭɸ ɞɟɢɨɧɢɡɢɪɨɜɚɧɧɭɸ ɜɨɞɭ (ɭɞɟɥɶɧɨɟ ɫɨɩɪɨɬɢɜɥɟɧɢɟ 18 ɆɈɦ×ɫɦ, ɪɇ 6,5; ɨɱɢɫɬɤɭ ɩɪɨɜɨɞɢɥɢ ɧɚ ɭɫɬɚɧɨɜɤɟ “Milli-Q”, “Millipore”, Ɏɪɚɧɰɢɹ). ɂɫɩɨɥɶɡɨɜɚɥɢ
ɫɥɟɞɭɸɳɢɟ ɪɟɚɝɟɧɬɵ: ɮɟɪɪɨɢɧ ɫɭɥɶɮɚɬ (ɜɨɞɧɵɣ ɪɚɫɬɜɨɪ, 0,1 ɦɚɫ.%, “ɱ.ɞ.ɚ”); ɛɢɯɪɨɦɚɬ ɚɦɦɨɧɢɹ
(“ɱ.ɞ.ɚ”); ɯɥɨɪɢɞ ɧɚɬɪɢɹ (“ɯ.ɱ.”); ɫɭɥɶɮɚɬ ɧɚɬɪɢɹ
(“ɯ.ɱ.”); ɫɟɪɧɭɸ ɤɢɫɥɨɬɭ (“ɯ.ɱ.”); ɫɨɥɹɧɭɸ ɤɢɫɥɨɬɭ
(“ɯ.ɱ.”); ɝɢɞɪɨɤɫɢɞ ɧɚɬɪɢɹ (“ɱ.ɞ.ɚ”). ȼɫɟ ɪɚɫɬɜɨɪɵ
ɝɨɬɨɜɢɥɢ ɧɟɩɨɫɪɟɞɫɬɜɟɧɧɨ ɩɟɪɟɞ ɩɪɨɜɟɞɟɧɢɟɦ ɷɤɫɩɟɪɢɦɟɧɬɚ. Ȼɚɡɨɜɵɟ ɪɚɫɬɜɨɪɵ ɨɤɪɚɲɟɧɧɵɯ ɜɟɳɟɫɬɜ
(ɮɟɪɪɨɢɧɚ ɢ ɛɢɯɪɨɦɚɬɚ ɚɦɦɨɧɢɹ) ɝɨɬɨɜɢɥɢ ɪɚɫɬɜɨɪɟɧɢɟɦ ɬɨɱɧɵɯ ɧɚɜɟɫɨɤ ɜ ɜɨɞɟ. Ɋɚɫɬɜɨɪɵ ɯɪɚɧɢɥɢ ɜ
ɩɪɨɛɢɪɤɚɯ ɢ ɤɨɥɛɚɯ ɫ ɩɪɢɬɟɪɬɵɦɢ ɩɪɨɛɤɚɦɢ. Ʌɚɛɨɪɚɬɨɪɧɭɸ ɩɨɫɭɞɭ ɜɵɦɚɱɢɜɚɥɢ ɜ ɯɪɨɦɨɜɨɣ ɫɦɟɫɢ, ɡɚɬɟɦ
ɜ ɚɡɨɬɧɨɣ ɤɢɫɥɨɬɟ ɢ ɬɳɚɬɟɥɶɧɨ ɩɪɨɦɵɜɚɥɢ ɞɢɫɬɢɥɥɢɪɨɜɚɧɧɨɣ ɜɨɞɨɣ. ȼɫɟ ɜɡɜɟɲɢɜɚɧɢɹ ɩɪɨɜɨɞɢɥɢ ɧɚ ɚɧɚɥɢɬɢɱɟɫɤɢɯ ɜɟɫɚɯ ɫ ɬɨɱɧɨɫɬɶɸ 0,1 ɦɝ, ɚ ɢɡɦɟɪɟɧɢɹ
ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
ɨɛɴɟɦɨɜ — ɝɪɚɞɭɢɪɨɜɚɧɧɵɦɢ ɩɢɩɟɬɤɚɦɢ ɫ ɬɨɱɧɨɫɬɶɸ ±0,01 ɦɥ. Ɋɚɫɬɜɨɪɟɧɢɟ ɫɭɥɶɮɚɬɚ ɧɚɬɪɢɹ ɩɪɨɜɨɞɢɥɢ ɜ ɭɥɶɬɪɚɡɜɭɤɨɜɨɣ ɜɚɧɧɟ “Branson” ɜ ɬɟɱɟɧɢɟ 30–
60 ɦɢɧ.
Ƚɨɬɨɜɢɥɢ ɧɟɫɤɨɥɶɤɨ ɫɟɪɢɣ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɨɜ, ɫɨɞɟɪɠɚɳɢɯ ɭɤɚɡɚɧɧɨɟ ɤɨɥɢɱɟɫɬɜɨ ɨɤɪɚɲɟɧɧɨɝɨ ɜɟɳɟɫɬɜɚ. ȼ ɪɚɫɬɜɨɪɵ ɤɚɠɞɨɣ ɫɟɪɢɢ ɞɨɛɚɜɥɹɥɢ ɧɭɠɧɨɟ
ɤɨɥɢɱɟɫɬɜɨ ɦɨɞɢɮɢɤɚɬɨɪɚ ɢ ɪɚɡɛɚɜɥɹɥɢ ɞɟɢɨɧɢɡɢɪɨɜɚɧɧɨɣ ɜɨɞɨɣ ɞɨ 50 ɦɥ. Ɍɟɪɦɨɥɢɧɡɨɜɵɟ ɢɡɦɟɪɟɧɢɹ
ɩɪɨɜɨɞɢɥɢ ɩɪɢ λ = 488,0 ɢ λ = 514,5 ɧɦ ɜ ɬɟɱɟɧɢɟ
3-5 ɦɢɧ. Ⱦɥɹ ɩɨɜɵɲɟɧɢɹ ɩɪɚɜɢɥɶɧɨɫɬɢ ɪɟɡɭɥɶɬɚɬɨɜ
ɚɧɚɥɢɡɚ ɢ ɭɜɟɥɢɱɟɧɢɹ ɬɨɱɧɨɫɬɢ ɨɩɪɟɞɟɥɟɧɢɹ ɮɚɤɬɨɪɚ
ɭɜɟɥɢɱɟɧɢɹ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɩɨ ɨɬɧɨɲɟɧɢɸ ɤ ɜɨɞɟ
ɝɪɚɞɭɢɪɨɜɨɱɧɵɟ ɡɚɜɢɫɢɦɨɫɬɢ ɜ ɪɚɫɬɜɨɪɚɯ ɦɨɞɢɮɢɤɚɬɨɪɨɜ ɛɵɥɢ ɨɬɫɧɹɬɵ ɜ ɬɨɬ ɠɟ ɞɟɧɶ ɢ ɩɪɢ ɬɟɯ ɠɟ ɭɫɥɨɜɢɹɯ, ɱɬɨ ɢ ɜ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɚɯ.
dÑ·ÄÆ ¾Ãº¾À¶ÈÄÆÃÑË ÇÄ»º¾Ã»Ã¾¿
Ⱦɥɹ ɢɡɭɱɟɧɢɹ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜ ɪɚɫɬɜɨɪɨɜ
ɫɨɥɟɣ ɜ ɤɚɱɟɫɬɜɟ ɢɧɞɢɤɚɬɨɪɧɨɝɨ ɨɤɪɚɲɟɧɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ ɜɵɛɪɚɧ ÈƾÇ-(1,10-ɮɟɧɚɧɬɪɨɥɢɧɚɬ) ɠɟɥɟɡɚ(II),
ɩɨɫɤɨɥɶɤɭ ɨɧ ɨɛɥɚɞɚɟɬ ɛɨɥɶɲɢɦ ɡɧɚɱɟɧɢɟɦ (ɛɨɥɟɟ
11000) ɦɨɥɹɪɧɨɝɨ ɤɨɷɮɮɢɰɢɟɧɬɚ ɩɨɝɥɨɳɟɧɢɹ ɧɚ ɪɚɛɨɱɟɣ ɞɥɢɧɟ ɜɨɥɧɵ ɚɪɝɨɧɨɜɨɝɨ ɢɨɧɧɨɝɨ ɥɚɡɟɪɚ. ɇɟɢɡɦɟɧɧɨɫɬɶ ɫɜɟɬɨɩɨɝɥɨɳɟɧɢɹ ɮɟɪɪɨɢɧɚ ɜ ɪɚɫɬɜɨɪɚɯ ɩɪɢ
ɪɚɡɥɢɱɧɵɯ ɡɧɚɱɟɧɢɹɯ ɢɨɧɧɨɣ ɫɢɥɵ ɩɨɞɬɜɟɪɠɞɟɧɚ
ɫɩɟɤɬɪɨɮɨɬɨɦɟɬɪɢɱɟɫɤɢɦɢ ɢɡɦɟɪɟɧɢɹɦɢ.
tƾÇ-(1,10-ɮɟɧɚɧɬɪɨɥɢɧɚɬ) ɠɟɥɟɡɚ(II) ɧɟɭɫɬɨɣɱɢɜ ɜ
ɚɝɪɟɫɫɢɜɧɵɯ ɫɪɟɞɚɯ, ɢ ɩɨɷɬɨɦɭ ɜ ɤɚɱɟɫɬɜɟ ɢɧɞɢɤɚɬɨɪɧɨɝɨ ɨɤɪɚɲɟɧɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ ɞɥɹ ɢɡɭɱɟɧɢɹ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜ ɪɚɫɬɜɨɪɨɜ ɫɢɥɶɧɵɯ ɤɢɫɥɨɬ ɢ ɨɫɧɨɜɚɧɢɣ ɜɵɛɪɚɧɵ ɛɢɯɪɨɦɚɬ-ɢɨɧɵ. ɂɯ ɫɜɟɬɨɩɨɝɥɨɳɟɧɢɟ ɜ
ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɚɯ ɡɚɜɢɫɢɬ ɬɨɥɶɤɨ ɨɬ pH, ɢ ɩɪɟɞɜɚɪɢɬɟɥɶɧɵɟ ɫɩɟɤɬɪɨɮɨɬɨɦɟɬɪɢɱɟɫɤɢɟ ɢɡɦɟɪɟɧɢɹ ɩɨɤɚɡɚɥɢ, ɱɬɨ ɜ ɢɧɬɟɪɜɚɥɟ pH ɨɬ 6 ɞɨ 0,2 ɡɧɚɱɢɦɵɯ ɢɡɦɟɧɟɧɢɣ ɫɩɟɤɬɪɚ ɩɨɝɥɨɳɟɧɢɹ ɜ ɞɢɚɩɚɡɨɧɟ ɞɥɢɧ ɜɨɥɧ ɨɬ
480 ɞɨ 520 ɧɦ ɧɟ ɩɪɨɢɫɯɨɞɢɬ.
ȼ ɫɢɥɶɧɨɳɟɥɨɱɧɵɯ ɫɪɟɞɚɯ ɪɚɜɧɨɜɟɫɢɟ ɛɢɯɪɨɦɚɬ–
ɯɪɨɦɚɬ ɫɦɟɳɟɧɨ ɜ ɫɬɨɪɨɧɭ ɩɨɫɥɟɞɧɟɝɨ, ɱɬɨ ɫɨɩɪɨɜɨɠɞɚɟɬɫɹ ɢɡɦɟɧɟɧɢɟɦ ɫɩɟɤɬɪɚ ɩɨɝɥɨɳɟɧɢɹ. Ⱦɥɹ ɬɨɝɨ
ɱɬɨɛɵ ɭɱɟɫɬɶ ɷɬɨ ɹɜɥɟɧɢɟ, ɧɨɪɦɢɪɨɜɚɥɢ ɨɬɧɨɲɟɧɢɟ
ɤɨɷɮɮɢɰɢɟɧɬɨɜ ɧɚɤɥɨɧɚ ɝɪɚɞɭɢɪɨɜɨɱɧɵɯ ɝɪɚɮɢɤɨɜ ɧɚ
ɜɟɥɢɱɢɧɭ ɨɬɧɨɲɟɧɢɹ ɨɩɬɢɱɟɫɤɢɯ ɩɥɨɬɧɨɫɬɟɣ ɜɨɞɧɨɝɨ ɢ
ɳɟɥɨɱɧɨɝɨ ɪɚɫɬɜɨɪɚ ɩɪɢ ɞɥɢɧɟ ɜɨɥɧɵ ɬɟɪɦɨɥɢɧɡɨɜɵɯ
ɢɡɦɟɪɟɧɢɣ.
p·Æ¶·ÄÈÀ¶ Æ»½ÉÁÒȶÈĸ È»ÆÂÄÁ¾Ã½Ä¸ÑË
¾½Â»Æ»Ã¾¿
Ɍɟɪɦɨɥɢɧɡɨɜɵɣ ɫɢɝɧɚɥ θ ɨɩɪɟɞɟɥɹɟɬɫɹ ɨɬɧɨɫɢɬɟɥɶɧɵɦ ɢɡɦɟɧɟɧɢɟɦ ɢɧɬɟɧɫɢɜɧɨɫɬɢ ɥɚɡɟɪɧɨɝɨ ɢɡɥɭɱɟɧɢɹ ɜ ɰɟɧɬɪɚɥɶɧɨɣ ɱɚɫɬɢ ɩɭɱɤɚ, ɩɪɨɲɟɞɲɟɝɨ ɨɛ-
ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
261
ɪɚɡɟɰ, ɩɪɢ ɞɨɫɬɢɠɟɧɢɢ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɨɝɨ ɪɚɜɧɨɜɟɫɢɹ [1]:
θ=
1⎛
⎜1 +
B⎜
⎝
I ɜɵɤɥ − I ɜɤɥ ⎞
⎟,
⎟
I ɜɤɥ
⎠
(14)
ɝɞɟ Iɜɤɥ ɢ Iɜɵɤɥ – ɡɧɚɱɟɧɢɹ ɢɧɬɟɧɫɢɜɧɨɫɬɢ ɜ ɰɟɧɬɪɟ
ɡɨɧɞɢɪɭɸɳɟɝɨ ɥɭɱɚ ɛɟɡ ɬɟɪɦɨɥɢɧɡɵ (ɜɵɤɥɸɱɟɧɧɵɣ
ɢɧɞɭɰɢɪɭɸɳɢɣ ɥɚɡɟɪ) ɢ ɩɪɢ ɧɚɥɢɱɢɢ ɪɚɡɜɢɜɲɟɣɫɹ ɬɟɪɦɨɥɢɧɡɵ (ɜɤɥɸɱɟɧɧɵɣ ɥɚɡɟɪ), ɚ ɝɟɨɦɟɬɪɢɱɟɫɤɢɣ ɮɚɤɬɨɪ B ɨɩɪɟɞɟɥɟɧ ɤɚɤ
⎛
2mV
⎞
,
B = 0,5arctg ⎜
2⎟
⎝ 1 + 2m + V ⎠
(15)
ɝɞɟ V – ɪɚɫɫɬɨɹɧɢɟ ɦɟɠɞɭ ɩɟɪɟɬɹɠɤɨɣ ɡɨɧɞɢɪɭɸɳɟɝɨ
ɥɭɱɚ ɢ ɨɛɪɚɡɰɨɦ, m – ɫɨɨɬɧɨɲɟɧɢɟ ɩɥɨɳɚɞɟɣ ɩɨɩɟɪɟɱɧɨɝɨ ɫɟɱɟɧɢɹ ɡɨɧɞɢɪɭɸɳɟɝɨ ɢ ɢɧɞɢɰɢɪɭɸɳɟɝɨ ɥɭɱɟɣ ɜ ɨɛɪɚɡɰɟ. ɉɟɪɟɫɱɟɬ ɚɧɚɥɢɬɢɱɟɫɤɨɝɨ ɬɟɪɦɨɥɢɧɡɨɜɨɝɨ ɫɢɝɧɚɥɚ θ ɜ ɨɩɬɢɱɟɫɤɭɸ ɩɥɨɬɧɨɫɬɶ ɩɪɨɜɨɞɹɬ ɫ
ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ ɭɪɚɜɧɟɧɢɹ (4).
r»½ÉÁÒȶÈÑ ¾ ¾Ë Ä·Çɼº»Ã¾»
sƶ¸Ã»Ã¾» Âĺ¾Ê¾Ì¾ÆÉÔÏ¾Ë Ç¸Ä¿Çȸ ƶÇȸÄÆĸ
ÓÁ»ÀÈÆÄÁ¾Èĸ
ȼ ɪɚɫɬɜɨɪɚɯ ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ ɧɚɛɥɸɞɚɟɬɫɹ (ɪɢɫ. 1)
ɯɨɪɨɲɟɟ ɫɨɝɥɚɫɨɜɚɧɢɟ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɨɩɪɟɞɟɥɟɧɧɨɝɨ ɮɚɤɬɨɪɚ ɭɜɟɥɢɱɟɧɢɹ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɫ ɪɚɫɫɱɢɬɚɧɧɵɦ ɩɨ ɭɪɚɜɧɟɧɢɸ (13). Ɉɬɤɥɨɧɟɧɢɹ ɧɟ ɩɪɟɜɵɲɚɸɬ 5%, ɱɬɨ ɨɛɵɱɧɨ ɩɪɨɢɫɯɨɞɢɬ ɬɨɥɶɤɨ ɜ ɪɚɫɬɜɨɪɚɯ
ɦɚɥɨɩɨɥɹɪɧɵɯ ɧɟɚɫɫɨɰɢɢɪɨɜɚɧɧɵɯ ɠɢɞɤɨɫɬɟɣ [7].
Ɇɨɠɧɨ ɩɪɟɞɩɨɥɨɠɢɬɶ, ɱɬɨ ɜ ɭɦɟɪɟɧɨ ɤɨɧɰɟɧɬɪɢɪɨɜɚɧɧɵɯ (0,01–1,0 Ɇ) ɪɚɫɬɜɨɪɚɯ ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ ɚɫɫɨɰɢɚ-
ɰɢɹ ɦɨɥɟɤɭɥ, ɩɪɨɢɫɯɨɞɹɳɚɹ ɜɫɥɟɞɫɬɜɢɟ ɞɢɩɨɥɶ-ɞɢɩɨɥɶɧɵɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ, ɩɨɞɚɜɥɟɧɚ ɡɚ ɫɱɟɬ ɜɨɡɧɢɤɧɨɜɟɧɢɹ ɢɨɧ-ɞɢɩɨɥɶɧɵɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ ɦɨɥɟɤɭɥ ɜɨɞɵ ɫ
ɢɨɧɚɦɢ ɝɢɞɪɨɤɫɨɧɢɹ ɢ ɫɭɥɶɮɚɬɚ. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɫɟɪɧɭɸ ɤɢɫɥɨɬɭ ɦɨɠɧɨ ɪɚɫɫɦɚɬɪɢɜɚɬɶ ɤɚɤ ɢɞɟɚɥɶɧɵɣ
ɫɬɪɭɤɬɭɪɨɪɚɡɪɭɲɚɸɳɢɣ ɦɨɞɢɮɢɤɚɬɨɪ. Ʉɚɤ ɩɨɤɚɡɚɧɨ ɜ
ɬɚɛɥ. 2, ɩɨ ɦɟɪɟ ɩɨɜɵɲɟɧɢɹ ɤɨɧɰɟɧɬɪɚɰɢɢ ɫɟɪɧɨɣ
ɤɢɫɥɨɬɵ ɜ ɪɚɫɬɜɨɪɟ ɨɬɤɥɨɧɟɧɢɹ ɨɬ ɭɪɚɜɧɟɧɢɹ Ʌɨɪɟɧɬɰɚ–Ʌɨɪɟɧɰɚ ɭɦɟɧɶɲɚɸɬɫɹ, ɢ ɩɪɢ ɤɨɧɰɟɧɬɪɚɰɢɢ 0,6 Ɇ
ɩɪɚɤɬɢɱɟɫɤɢ ɨɬɫɭɬɫɬɜɭɸɬ. ȼɢɞɢɦɨ, ɬɚɤɚɹ ɬɟɧɞɟɧɰɢɹ
ɫɜɹɡɚɧɚ ɫ ɬɟɦ, ɱɬɨ ɩɨ ɦɟɪɟ ɭɜɟɥɢɱɟɧɢɹ ɤɨɧɰɟɧɬɪɚɰɢɢ
ɢɨɧɨɜ ɝɢɞɪɨɤɫɨɧɢɹ ɢ ɫɭɥɶɮɚɬ-ɢɨɧɨɜ ɜ ɪɚɫɬɜɨɪɟ ɜɨɡɪɚɫɬɚɟɬ ɞɨɥɹ ɢɨɧ-ɞɢɩɨɥɶɧɵɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ ɢ ɫɨɤɪɚɳɚɟɬɫɹ ɞɨɥɹ ɞɢɩɨɥɶ-ɞɢɩɨɥɶɧɵɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ, ɚ
ɫɥɟɞɨɜɚɬɟɥɶɧɨ, ɭɦɟɧɶɲɚɟɬɫɹ ɚɫɫɨɰɢɚɰɢɹ.
ɗɬɨ ɦɨɠɧɨ ɨɛɴɹɫɧɢɬɶ ɬɟɦ, ɱɬɨ ɢɨɧ, ɧɚɯɨɞɹɳɢɣɫɹ ɜ
ɪɚɫɬɜɨɪɟ, ɫɜɹɡɵɜɚɟɬ ɧɟɫɤɨɥɶɤɨ ɦɨɥɟɤɭɥ ɜɨɞɵ ɢɨɧ-ɞɢɩɨɥɶɧɵɦɢ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹɦɢ ɜ ɫɨɥɶɜɚɬɧɭɸ ɨɛɨɥɨɱɤɭ.
ɉɪɢ ɷɬɨɦ ɪɚɡɪɭɲɚɟɬɫɹ ɧɟɤɨɬɨɪɚɹ ɱɚɫɬɶ ɚɫɫɨɰɢɚɬɨɜ,
ɨɛɪɚɡɨɜɚɧɧɵɯ ɦɨɥɟɤɭɥɚɦɢ ɜɨɞɵ ɡɚ ɫɱɟɬ ɞɢɩɨɥɶ–ɞɢɩɨɥɶɧɵɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ. ȿɫɥɢ ɱɢɫɥɨ ɦɨɥɟɤɭɥ ɜɨɞɵ,
ɜɯɨɞɹɳɢɯ ɜ ɫɨɥɶɜɚɬɧɭɸ ɨɛɨɥɨɱɤɭ, ɩɪɟɜɨɫɯɨɞɢɬ ɱɢɫɥɨ
ɦɨɥɟɤɭɥ ɜ ɚɫɫɨɰɢɚɬɟ, ɪɚɡɪɭɲɟɧɧɨɦ ɩɪɢ ɫɨɥɶɜɚɬɚɰɢɢ,
ɬɨ ɧɚɛɥɸɞɚɟɬɫɹ ɞɨɩɨɥɧɢɬɟɥɶɧɨɟ ɫɬɪɭɤɬɭɪɨɨɛɪɚɡɨɜɚɧɢɟ
ɜ ɜɨɞɟ. ȿɫɥɢ ɠɟ ɤɨɥɢɱɟɫɬɜɨ ɦɨɥɟɤɭɥ ɜ ɨɛɪɚɡɭɸɳɟɣɫɹ
ɫɨɥɶɜɚɬɧɨɣ ɨɛɨɥɨɱɤɟ ɦɟɧɶɲɟ, ɱɟɦ ɜ ɪɚɡɪɭɲɟɧɧɨɦ ɚɫɫɨɰɢɚɬɟ, ɬɨ ɫɬɟɩɟɧɶ ɚɫɫɨɰɢɚɰɢɢ ɦɨɥɟɤɭɥ ɫɧɢɠɚɟɬɫɹ.
Ɉɞɧɚɤɨ ɪɚɫɫɦɨɬɪɟɬɶ ɜɥɢɹɧɢɟ ɨɬɞɟɥɶɧɵɯ ɢɨɧɨɜ ɧɚ
ɚɫɫɨɰɢɚɰɢɸ ɜɨɞɵ ɡɚɬɪɭɞɧɢɬɟɥɶɧɨ, ɩɨɫɤɨɥɶɤɭ ɜ ɪɚɫɬɜɨɪɟ ɜɫɟɝɞɚ ɩɪɢɫɭɬɫɬɜɭɸɬ ɢɨɧɵ ɤɚɤ ɦɢɧɢɦɭɦ ɞɜɭɯ ɪɚɡɧɵɯ ɬɢɩɨɜ. ȼ ɫɜɹɡɢ ɫ ɷɬɢɦ ɩɪɨɜɟɞɟɧɵ ɷɤɫɩɟɪɢɦɟɧɬɵ
ɜ ɪɚɫɬɜɨɪɚɯ ɫɭɥɶɮɚɬɚ ɧɚɬɪɢɹ.
E 0/E 0, ɜɨɞɵ
2.2
2
1.8
1.6
1.4
1.2
1
0
0.056 0.104
0.306 0.423
0.612
ɬɟɨɪɢɹ
ɷɤɫɩɟɪɢɦɟɧɬ
Ʉɨɧɰɟɧɬɪɚɰɢɹ H2SO4, M
Ɋɢɫ. 1. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɨɩɪɟɞɟɥɟɧɧɵɣ ɢ ɪɚɫɱɟɬɧɵɣ ɮɚɤɬɨɪɵ ɭɜɟɥɢɱɟɧɢɹ
ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɬɟɪɦɨɥɢɧɡɨɜɵɯ ɢɡɦɟɪɟɧɢɣ ɜ ɪɚɫɬɜɨɪɚɯ ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ
ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
262
Ɍɚɛɥɢɰɚ 2
ÀÇŻƾ»ÃȶÁÒÃÑ» ¾ ƶÇÍ»ÈÃÑ» ʶÀÈÄÆÑ É¸»Á¾Í»Ã¾µ ÍɸÇȸ¾È»ÁÒÃÄÇȾ, ÅÆ»º»ÁÑ Ä·Ã¶Æɼ»Ã¾µ ·¾ËÆĶÈ-¾ÄÃĸ (*) ¾
Ê»ÆÆľö(**) ¸ ƶÇȸÄÆ¶Ë ÓÁ»ÀÈÆÄÁ¾Èĸ (n = 10, P = 0,95) Åƾ ºÁ¾Ã» ¸ÄÁÃÑ ¾ÃºÉ̾ÆÉÔÏ»¹Ä ¾½ÁÉͻþµ 488,0 (*) ¾ 514,5 ÃÂ
(**), ÂÄÏÃÄÇȾ ¾ÃºÉ̾ÆÉÔÏ»¹Ä ¾½ÁÉͻþµ 100 ÂdÈ
ȿ0/ȿ0, ɜɨɞɵ
(ɷɤɫɩɟɪɢɦɟɧɬ)
ȿ0/ȿ0, ɜɨɞɵ
(ɪɚɫɱɟɬ)
Ɉɬɤɥɨɧɟɧɢɟ ɨɬ
ɪɚɫɱɟɬɚ ɩɨ
ɭɪɚɜɧɟɧɢɸ (13), %
ɉɪɟɞɟɥ
ɨɛɧɚɪɭɠɟɧɢɹ,
ɦɨɥɶ/ɥ×108
sr ɜ ɫɟɪɟɞɢɧɟ
ɝɪɚɞɭɢɪɨɜɨɱɧɨɣ
ɡɚɜɢɫɢɦɨɫɬɢ
0
1
1
−
50
0,03
0,056
1,147
1,21
–5,1
15
ɬɨ ɠɟ
0,104
1,320
1,39
–4,9
20
ɬɨ ɠɟ
0,306
1,483
1,83
–5,2
25
ɬɨ ɠɟ
0,423
1,835
1,91
–3,9
25
ɬɨ ɠɟ
0,612
2,034
2,05
–0,6
50
ɬɨ ɠɟ
0
1
1
–
50
0,03
0,548
1,017
1,873
–48,3
20
ɬɨ ɠɟ
1,096
1,092
2,112
–45,7
20
ɬɨ ɠɟ
0
1
1
–
2
0,03
0,3
–
1,75
–41,7
1,5
ɬɨ ɠɟ
1,0
1,204
2,06
–41,5
3
ɬɨ ɠɟ
3,0
1,534
3,30
–53,3
3
ɬɨ ɠɟ
0
1
1
–
50
0,03
0,5
1,149
1.841
–37,6
20
ɬɨ ɠɟ
1,0
1,587
1.807
–12,2
20
ɬɨ ɠɟ
0
1
ɪɚɫɱɟɬ ɧɟ ɩɪɨɜɨɞɢɥɢ
5,0
0,03
0,423
1,110
1,0
0,05
Ɇɨɞɢɮɢɤɚɬɨɪ
ɫ, ɦɨɥɶ/ɥ
ɋɟɪɧɚɹ ɤɢɫɥɨɬɚ*
ɋɨɥɹɧɚɹ ɤɢɫɥɨɬɚ*
ɏɥɨɪɢɞ ɧɚɬɪɢɹ**
Ƚɢɞɪɨɤɫɢɞ ɧɚɬɪɢɹ*
ɋɭɥɶɮɚɬ ɧɚɬɪɢɹ**
ɇɚɛɥɸɞɚɟɦɵɣ ɜ ɪɚɫɬɜɨɪɚɯ ɫɭɥɶɮɚɬɚ ɧɚɬɪɢɹ ɮɚɤɬɨɪ
ɭɜɟɥɢɱɟɧɢɹ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɬɟɪɦɨɥɢɧɡɨɜɵɯ ɢɡɦɟɪɟɧɢɣ ɡɧɚɱɢɬɟɥɶɧɨ ɦɟɧɶɲɟ ɧɚɛɥɸɞɚɟɦɨɝɨ ɜ ɪɚɫɬɜɨɪɚɯ
ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ ɬɚɤɨɣ ɠɟ ɦɨɥɹɪɧɨɫɬɢ (ɬɚɛɥ. 2).
ɗɬɨ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɨ ɬɨɦ, ɱɬɨ ɢɨɧ ɧɚɬɪɢɹ ɹɜɥɹɟɬɫɹ ɡɧɚɱɢɬɟɥɶɧɨ ɛɨɥɟɟ ɫɥɚɛɵɦ ɫɬɪɭɤɬɭɪɨɪɚɡɪɭɲɚɸɳɢɦ ɦɨɞɢɮɢɤɚɬɨɪɨɦ, ɱɟɦ ɢɨɧ ɝɢɞɪɨɤɫɨɧɢɹ. ȼɢɞɢɦɨ,
ɭ ɩɨɫɥɟɞɧɟɝɨ ɛɨɥɟɟ ɜɵɫɨɤɨɟ ɨɬɧɨɲɟɧɢɟ ɡɚɪɹɞɚ ɤ
ɩɥɨɳɚɞɢ ɩɨɜɟɪɯɧɨɫɬɢ. ɋɥɟɞɨɜɚɬɟɥɶɧɨ, ɫɨɥɶɜɚɬɧɚɹ
ɨɛɨɥɨɱɤɚ ɢɨɧɚ ɝɢɞɪɨɤɫɨɧɢɹ ɦɟɧɶɲɟ, ɱɟɦ ɨɛɨɥɨɱɤɚ
ɢɨɧɚ ɧɚɬɪɢɹ, ɢ ɩɨɷɬɨɦɭ ɚɫɫɨɰɢɚɰɢɹ ɡɚ ɫɱɟɬ ɞɟɣɫɬɜɢɹ
ɢɨɧ-ɞɢɩɨɥɶɧɵɯ ɜɡɚɢɦɨɞɟɣɫɬɜɢɣ ɜ ɫɥɭɱɚɟ ɢɨɧɚ ɝɢɞɪɨɤɫɨɧɢɹ ɫɥɚɛɟɟ. ɉɨɞɬɜɟɪɠɞɟɧɢɟɦ ɜɵɲɟɫɤɚɡɚɧɧɨɦɭ
ɫɥɭɠɢɬ ɬɨ, ɱɬɨ ɜ ɪɹɞɭ ɤɚɥɢɣ–ɧɚɬɪɢɣ–ɥɢɬɢɣ ɫɩɨɫɨɛ-
ɧɨɫɬɶ ɢɨɧɨɜ ɤ ɫɧɢɠɟɧɢɸ ɫɬɟɩɟɧɢ ɚɫɫɨɰɢɚɰɢɢ ɜɨɞɵ
ɩɚɞɚɟɬ, ɩɪɢɱɟɦ ɢɨɧ ɥɢɬɢɹ ɜɨɨɛɳɟ ɹɜɥɹɟɬɫɹ ɫɬɪɭɤɬɭɪɨɨɛɪɚɡɭɸɳɢɦ ɦɨɞɢɮɢɤɚɬɨɪɨɦ [8]. Ⱦɚɧɧɚɹ ɤɨɧɰɟɩɰɢɹ ɩɨɡɜɨɥɹɟɬ ɨɛɴɹɫɧɢɬɶ ɫɢɥɶɧɨɟ ɪɚɡɥɢɱɢɟ ɜ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜɚɯ ɪɚɫɬɜɨɪɨɜ ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ ɢ
ɫɭɥɶɮɚɬɚ ɧɚɬɪɢɹ.
ɇɚɛɥɸɞɚɟɦɨɟ ɜ ɪɚɫɬɜɨɪɚɯ ɫɨɥɹɧɨɣ ɤɢɫɥɨɬɵ ɭɜɟɥɢɱɟɧɢɟ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɬɟɪɦɨɥɢɧɡɨɜɨɝɨ ɨɩɪɟɞɟɥɟɧɢɹ
(ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɜɨɞɨɣ) ɡɧɚɱɢɬɟɥɶɧɨ ɦɟɧɶɲɟ, ɱɟɦ ɜ
ɪɚɫɬɜɨɪɚɯ ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ ɢ ɯɥɨɪɢɞɚ ɧɚɬɪɢɹ (ɬɚɛɥ. 2).
ɂɡ ɷɬɨɝɨ ɦɨɠɧɨ ɫɞɟɥɚɬɶ ɜɵɜɨɞ, ɱɬɨ ɯɥɨɪɢɞ-ɢɨɧɵ ɹɜɥɹɸɬɫɹ ɫɬɪɭɤɬɭɪɨɨɛɪɚɡɭɸɳɢɦ ɦɨɞɢɮɢɤɚɬɨɪɨɦ, ɱɚɫɬɢɱɧɨ ɭɪɚɜɧɨɜɟɲɢɜɚɸɳɢɦ ɫɬɪɭɤɬɭɪɨɪɚɡɪɭɲɚɸɳɟɟ
ɞɟɣɫɬɜɢɟ ɢɨɧɚ ɝɢɞɪɨɤɫɨɧɢɹ. Ɉɞɧɚɤɨ ɜ ɪɚɫɬɜɨɪɚɯ ɯɥɨ-
ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
263
Ɋɢɫ. 2. Ɂɚɜɢɫɢɦɨɫɬɢ ɜɟɥɢɱɢɧɵ ɬɟɪɦɨɥɢɧɡɨɜɨɝɨ ɫɢɝɧɚɥɚ (θ) ɨɬ ɤɨɧɰɟɧɬɪɚɰɢɢ ɛɢɯɪɨɦɚɬɚ
ɩɪɢ ɜɚɪɶɢɪɨɜɚɧɧɨɣ ɤɨɧɰɟɧɬɪɚɰɢɢ ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ: 1 – ɜɨɞɚ (r = 0,997), 2 – 30 ɝ/ɥ H2SO4
( r = 0,997), 3 – 60 ɝ/ɥ H2SO4 (r = 0,999); T = 298 K, λ = 488,0 ɧɦ
ɪɢɞɚ ɧɚɬɪɢɹ ɧɚɛɥɸɞɚɟɬɫɹ ɡɧɚɱɢɦɨɟ ɭɜɟɥɢɱɟɧɢɟ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ. ɗɬɨ ɩɪɨɬɢɜɨɪɟɱɢɬ ɩɪɟɞɫɬɚɜɥɟɧɢɹɦ ɨ
ɬɨɦ, ɱɬɨ ɢɨɧ ɝɢɞɪɨɤɫɨɧɢɹ ɛɨɥɟɟ ɫɢɥɶɧɵɣ ɫɬɪɭɤɬɭɪɨɪɚɡɪɭɲɚɸɳɢɣ ɦɨɞɢɮɢɤɚɬɨɪ, ɱɟɦ ɢɨɧ ɧɚɬɪɢɹ. ȿɫɥɢ
ɫɪɚɜɧɢɜɚɬɶ ɮɚɤɬɨɪɵ ɭɜɟɥɢɱɟɧɢɹ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɜ
ɪɚɫɬɜɨɪɚɯ ɫɭɥɶɮɚɬɚ ɢ ɯɥɨɪɢɞɚ ɧɚɬɪɢɹ ɫ ɪɚɜɧɨɣ ɦɨɥɹɪɧɨɣ ɤɨɧɰɟɧɬɪɚɰɢɟɣ ɢɨɧɨɜ ɧɚɬɪɢɹ, ɬɨ ɜ ɪɚɫɬɜɨɪɟ
ɯɥɨɪɢɞɚ ɮɚɤɬɨɪ ɭɜɟɥɢɱɟɧɢɹ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɜɵɲɟ
ɧɚ 8% (ɬɚɛɥ. 2).
ɂɡ ɫɤɚɡɚɧɧɨɝɨ ɜɢɞɧɨ, ɱɬɨ ɩɪɟɞɫɤɚɡɚɬɶ ɜɥɢɹɧɢɟ
ɜɟɳɟɫɬɜɚ ɧɚ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɶ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɯ
ɢɡɦɟɪɟɧɢɣ ɜ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɚɯ ɧɟ ɩɪɨɜɨɞɹ ɷɤɫɩɟɪɢɦɟɧɬɚ ɧɟɜɨɡɦɨɠɧɨ, ɩɨɫɤɨɥɶɤɭ ɧɟɥɶɡɹ ɬɨɱɧɨ ɨɩɪɟɞɟɥɢɬɶ ɜɥɢɹɧɢɟ ɢɨɧɨɜ ɧɚ ɫɬɪɭɤɬɭɪɭ ɜɨɞɵ ɩɨ ɨɬɞɟɥɶɧɨɫɬɢ. ɇɟɥɶɡɹ ɬɚɤɠɟ ɧɟ ɭɱɢɬɵɜɚɬɶ ɜɥɢɹɧɢɟ ɷɥɟɤɬɪɨɥɢɬɚ ɧɚ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɟ ɫɜɨɣɫɬɜɚ ɫɪɟɞɵ. ȼ ɪɚɫɬɜɨɪɚɯ ɫɟɪɧɨɣ ɢ ɫɨɥɹɧɨɣ ɤɢɫɥɨɬ ɩɪɢ ɪɚɜɧɵɯ pH
ɧɚɛɥɸɞɚɸɬɫɹ ɫɨɜɟɪɲɟɧɧɨ ɪɚɡɥɢɱɧɵɟ ɡɧɚɱɟɧɢɹ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɯ ɩɚɪɚɦɟɬɪɨɜ. ȿɫɥɢ ɜɥɢɹɧɢɟ ɫɨɥɹɧɨɣ
ɤɢɫɥɨɬɵ ɧɚ ɬɟɪɦɨɥɢɧɡɨɜɵɣ ɫɢɝɧɚɥ ɩɪɟɧɟɛɪɟɠɢɦɨ
ɦɚɥɨ, ɬɨ ɜɥɢɹɧɢɟ ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ ɨɱɟɧɶ ɡɧɚɱɢɬɟɥɶɧɨ. ɋɥɟɞɨɜɚɬɟɥɶɧɨ, ɞɥɹ ɩɪɟɰɢɡɢɨɧɧɵɯ ɨɩɪɟɞɟɥɟɧɢɣ
(ɧɚɩɪɢɦɟɪ, ɨɩɪɟɞɟɥɟɧɢɟ ɤɨɧɫɬɚɧɬ ɭɫɬɨɣɱɢɜɨɫɬɢ) ɩɪɢ
ɫɨɡɞɚɧɢɢ ɤɢɫɥɨɣ ɫɪɟɞɵ ɥɭɱɲɟ ɢɫɩɨɥɶɡɨɜɚɬɶ ɫɨɥɹɧɭɸ ɤɢɫɥɨɬɭ, ɚ ɟɫɥɢ ɧɟɨɛɯɨɞɢɦɨ ɩɨɜɵɫɢɬɶ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɶ ɨɩɪɟɞɟɥɟɧɢɹ (ɧɚɩɪɢɦɟɪ, ɩɪɢ ɪɚɛɨɬɟ ɫ
ɧɢɡɤɢɦɢ ɚɧɚɥɢɬɢɱɟɫɤɢɦɢ ɫɢɝɧɚɥɚɦɢ) ɥɭɱɲɟ ɢɫɩɨɥɶɡɨɜɚɬɶ ɫɟɪɧɭɸ ɤɢɫɥɨɬɭ.
Ⱦɚɧɧɵɟ ɩɪɢɦɟɪɵ ɩɨɤɚɡɵɜɚɸɬ, ɱɬɨ ɧɚ ɬɟɪɦɨɥɢɧɡɨɜɵɣ ɫɢɝɧɚɥ ɜɥɢɹɟɬ ɧɟ ɬɨɥɶɤɨ ɡɧɚɱɟɧɢɹ pH ɢ ɢɨɧɧɨɣ
ɫɢɥɵ, ɧɨ ɢ ɩɪɢɪɨɞɚ ɢɨɧɨɜ. ɉɪɨɜɟɞɟɧɧɵɟ ɢɫɫɥɟɞɨɜɚɧɢɹ
ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜ ɪɚɫɬɜɨɪɨɜ ɫɨɥɟɣ ɩɨɤɚɡɵɜɚɸɬ, ɱɬɨ ɧɟɥɶɡɹ ɧɟ ɭɱɢɬɵɜɚɬɶ ɩɪɢɪɨɞɭ ɢ ɤɨɧɰɟɧɬɪɚ-
ɰɢɸ ɦɨɞɢɮɢɤɚɬɨɪɚ ɢɨɧɧɨɣ ɫɢɥɵ, ɩɨɫɤɨɥɶɤɭ ɷɬɨ ɦɨɠɟɬ
ɩɪɢɜɟɫɬɢ ɤ ɡɧɚɱɢɬɟɥɶɧɵɦ ɩɨɝɪɟɲɧɨɫɬɹɦ ɨɩɪɟɞɟɥɟɧɢɹ.
dѸĺÑ
ɂɡ ɜɵɲɟɫɤɚɡɚɧɧɨɝɨ ɦɨɠɧɨ ɫɞɟɥɚɬɶ ɜɵɜɨɞ, ɱɬɨ ɧɚ
ɦɟɬɪɨɥɨɝɢɱɟɫɤɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɬɟɪɦɨɥɢɧɡɨɜɵɯ ɨɩɪɟɞɟɥɟɧɢɣ ɜ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɚɯ ɫɢɥɶɧɨ ɜɥɢɹɟɬ ɫɨɫɬɚɜ
ɫɪɟɞɵ. ɉɪɢɦɟɧɹɹ ɪɚɡɥɢɱɧɵɟ ɦɨɞɢɮɢɤɚɬɨɪɵ, ɦɨɠɧɨ
ɞɨɛɢɬɶɫɹ ɡɚɦɟɬɧɨɝɨ ɪɨɫɬɚ ɤɨɷɮɮɢɰɢɟɧɬɚ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɢ ɩɪɟɞɟɥɨɜ ɨɛɧɚɪɭɠɟɧɢɹ ɬɟɪɦɨɥɢɧɡɨɜɵɯ ɢɡɦɟɪɟɧɢɣ. Ɍɚɤ, ɜ ɪɚɫɬɜɨɪɚɯ ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ (0,5 Ɇ) ɧɚɛɥɸɞɚɟɬɫɹ ɩɨɱɬɢ ɞɜɭɤɪɚɬɧɨɟ ɭɜɟɥɢɱɟɧɢɟ ɤɨɷɮɮɢɰɢɟɧɬɚ
ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɬɟɪɦɨɥɢɧɡɨɜɵɯ ɢɡɦɟɪɟɧɢɣ (ɪɢɫ. 2)
ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɜɨɞɨɣ ɛɟɡ ɡɧɚɱɢɦɵɯ ɤɨɧɰɟɧɬɪɚɰɢɣ
ɷɥɟɤɬɪɨɥɢɬɨɜ, ɱɬɨ ɩɪɢɜɨɞɢɬ ɤ ɥɭɱɲɢɦ ɦɟɬɪɨɥɨɝɢɱɟɫɤɢɦ ɯɚɪɚɤɬɟɪɢɫɬɢɤɚɦ ɨɩɪɟɞɟɥɟɧɢɹ. Ɍɨ ɠɟ ɦɨɠɧɨ
ɫɤɚɡɚɬɶ ɢ ɩɪɨ ɪɚɫɬɜɨɪɵ ɯɥɨɪɢɞɚ ɧɚɬɪɢɹ (ɤɨɧɰɟɧɬɪɚɰɢɢ ɫɜɵɲɟ 1 Ɇ) ɢ ɝɢɞɪɨɤɫɢɞɚ ɧɚɬɪɢɹ (ɤɨɧɰɟɧɬɪɚɰɢɢ
ɫɜɵɲɟ 1 Ɇ), ɤɚɤ ɩɨɤɚɡɚɧɨ ɜ ɬɚɛɥ. 2. ɉɨɫɤɨɥɶɤɭ
ɞɚɧɧɵɟ ɫɪɟɞɵ ɲɢɪɨɤɨ ɩɪɟɞɫɬɚɜɥɟɧɵ ɜ ɦɟɬɨɞɢɤɚɯ
ɮɨɬɨɦɟɬɪɢɱɟɫɤɨɝɨ ɨɩɪɟɞɟɥɟɧɢɹ ɷɥɟɦɟɧɬɨɜ ɢ ɨɪɝɚɧɢɱɟɫɤɢɯ ɫɨɟɞɢɧɟɧɢɣ, ɩɨɥɭɱɟɧɧɵɟ ɪɟɡɭɥɶɬɚɬɵ ɢɦɟɸɬ
ɞɨɫɬɚɬɨɱɧɨ ɛɨɥɶɲɨɟ ɡɧɚɱɟɧɢɟ ɞɥɹ ɩɨɜɵɲɟɧɢɹ ɱɭɜɫɬɜɢɬɟɥɶɧɨɫɬɢ ɚɧɚɥɢɡɚ. ɇɚ ɧɚɲ ɜɡɝɥɹɞ, ɨɩɬɢɦɢɡɚɰɢɹ
ɫɭɳɟɫɬɜɭɸɳɢɯ ɭɫɥɨɜɢɣ ɨɩɪɟɞɟɥɟɧɢɹ ɪɚɡɥɢɱɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɜ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɚɯ ɤɢɫɥɨɬ ɢ ɨɫɧɨɜɚɧɢɣ
ɦɨɠɟɬ ɨɤɚɡɚɬɶɫɹ ɩɟɪɫɩɟɤɬɢɜɧɵɦ ɩɭɬɟɦ ɪɚɡɪɚɛɨɬɤɢ
ɱɭɜɫɬɜɢɬɟɥɶɧɵɯ ɦɟɬɨɞɢɤ ɬɟɪɦɨɥɢɧɡɨɜɨɝɨ ɨɩɪɟɞɟɥɟɧɢɹ.
ȼ ɰɟɥɨɦ ɩɪɨɜɟɞɟɧɧɵɟ ɢɫɫɥɟɞɨɜɚɧɢɹ ɩɨɤɚɡɚɥɢ ɩɟɪɫɩɟɤɬɢɜɧɨɫɬɶ ɢɫɩɨɥɶɡɨɜɚɧɢɹ ɬɟɪɦɨɥɢɧɡɨɜɨɣ ɫɩɟɤɬɪɨɦɟɬɪɢɢ ɞɥɹ ɢɫɫɥɟɞɨɜɚɧɢɹ ɬɟɪɦɨɨɩɬɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜ
ɪɚɫɬɜɨɪɨɜ ɷɥɟɤɬɪɨɥɢɬɨɜ. ȼɚɠɧɵɦ ɦɟɲɚɸɳɢɦ ɮɚɤɬɨ-
ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 4
264
ɪɨɦ ɜ ɩɨɞɨɛɧɵɯ ɢɫɫɥɟɞɨɜɚɧɢɹɯ ɦɨɠɟɬ ɛɵɬɶ ɬɟɪɦɨɞɢɮɮɭɡɢɹ ɢ ɷɮɮɟɤɬ ɋɨɪɷ (ɨɛɪɚɡɨɜɚɧɢɟ ɝɪɚɞɢɟɧɬɚ
ɤɨɧɰɟɧɬɪɚɰɢɣ) ɡɚ ɫɱɟɬ ɥɨɤɚɥɶɧɨɝɨ ɧɚɝɪɟɜɚ ɫɪɟɞɵ ɥɚɡɟɪɧɵɦ ɢɡɥɭɱɟɧɢɟɦ, ɨɫɨɛɟɧɧɨ ɜ ɜɵɫɨɤɨɜɹɡɤɢɯ ɫɪɟɞɚɯ, ɬɚɤɢɯ ɤɚɤ ɪɚɫɬɜɨɪɵ ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ. ȼ ɞɚɧɧɨɣ
ɋɉɂɋɈɄ ɅɂɌȿɊȺɌɍɊɕ
1. Bialkowski S.E. Phototermal spectroscopy methods for
chemical analysis. N.Y., 1996.
2. Bolshov M., Kuritsyn Yu. Laser Analytical Spectroscopy.
Ullmann’s Encyclopedia of industrial chemistry. 6th ed.
2001. P. 57.
3. ɋɩɪɚɜɨɱɧɢɤ ɯɢɦɢɤɚ. Ɍ. 3. Ɇ., 1964.
4. ɇɨɜɵɣ ɫɩɪɚɜɨɱɧɢɤ ɯɢɦɢɤɚ ɢ ɬɟɯɧɨɥɨɝɚ. Ɍ. 2. ɋɉɛ.,
2002. C. 1213.
ɪɚɛɨɬɟ ɜɥɢɹɧɢɟ ɷɬɢɯ ɮɚɤɬɨɪɨɜ ɩɪɚɤɬɢɱɟɫɤɢ ɧɟ ɢɡɭɱɚɥɨɫɶ, ɧɨ ɷɬɢ ɹɜɥɟɧɢɹ ɡɚɫɥɭɠɢɜɚɸɬ ɫɚɦɨɝɨ ɩɪɢɫɬɚɥɶɧɨɝɨ ɜɧɢɦɚɧɢɹ ɧɟ ɬɨɥɶɤɨ ɤɚɤ ɦɟɲɚɸɳɢɟ ɮɚɤɬɨɪɵ,
ɧɨ ɢ ɫ ɮɢɡɢɱɟɫɤɨɣ ɬɨɱɤɢ ɡɪɟɧɢɹ, ɚ ɬɚɤɠɟ ɤɚɤ ɮɚɤɬɨɪɵ ɨɩɬɢɦɢɡɚɰɢɢ ɩɪɢ ɪɚɡɪɚɛɨɬɤɟ ɦɟɬɨɞɢɤ ɬɟɪɦɨɥɢɧɡɨɜɨɝɨ ɨɩɪɟɞɟɥɟɧɢɹ.
5. CRC Handbook of Chemistry and Physics (3rd Electronic
Edition): Section 6: Fluid Properties.
6. qÆÄÇÀÉÆþà n.b., b·ÆÄÇÀ¾Ã b.e., r¶ºÉÎÀ»¸¾Í f.€. //
ɀȺɏ. 1999. 54. ɋ. 101.
7. Beysens D., Galmettes P. // J. Chem. Phys. 1977. 66. P.
1642.
8. Franko M., Tran C.D. // J. Phys. Chem. 1991. 95. P. 6688.
ɉɨɫɬɭɩɢɥɚ ɜ ɪɟɞɚɤɰɢɸ 23.11.06
THE EFFECT OF ELECTROLYTES ON THE SENSITIVITY OF
THERMAL-LENS MEASUREMENTS IN AQUEOUS SOLUTIONS
D.S. Tsar’kov, A.A. Zhirkov, M.A. Proskurnin
(Division of Analytical Chemistry)
Thermooptical properties of aqueous solutions of strong electrolytes (H 2SO 4, HCl, NaCl,
Na2SO4, and NaOH) were investigated, and it was found that the nature of the electrolyte affects
the thermal lens signal. This effect cannot be considered as a sum of effects from ions comprising
the electrolyte in question. The maximum increase in the sensitivity of thermal-lens
measurements is observed in solutions of sulfuric acid (twofold increase compared to water for
the concentration of 0.6M) and sodium chloride (1.5-fold increase at 2M), while the effect in
hydrochloric acid is negligible.