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.,/1.0</* 2 /!,"1"&"(()* 2%0$/(%*, < /./9"((/.0$ 2 $/(%* H+,

%1./,9$,5?@$6.- (% /0,$#%0"&'(/ +%,-:"(()6 #"(0,%6.

> ,"+5&'0%0" .!"#$B$3".2/4 %1./,9#$$ 8+ </+($2%"0 ,%+1"&"($" +%,-1/< $ *":B%+()4 .2%3/2 !/0"(#$%&% (% 2%:1/4 $+ !/<",6(/.0"4 *"*9,%(). C"6%($+* /02&$2% .0"2&-((/7/ D&"20,/1% /!$.)<%"0.- */1"&'? *"*9,%() . B$2.$,/<%(()* +%,-1/*. E+*"("($" ,8 ,%.0</,% (% "1$($#5 < $1"%&'(/* .&53%" <)+)<%"0 $+*"("($" !/0"(#$%&% -3"42$ (% 59,16 *> !,$

25û .

 

 

 

 

F/0"(#$%& .0"2&-((/7/ D&"20,/1% /!$.)<%"0.- 5,%<("($"*G

 

E # const ! 0,059lg a

H

! .

(2.3)

 

 

 

 

> .&%7%"*/" const <6/1-0 <"&$3$() !/0"(#$%&/<

<(";("7/

$

<(50,"(("7/ D&"20,/1/< .,%<("($- $ !/0"(#$%& %.$**"0,$$. F,$3$() "7/

!/-<&"($- /95.&/<&"() ,%+&$3$"* .0,5205,)

$ ./.0%<%

<(";("4

$

<(50,"(("4 !/<",6(/.0"4 *"*9,%(), </+($2%?@"7/ +% .3"0 5&"053$<%($- ("2/0/,)6 2/*!/("(0/< !,$ $+7/0/<&"($$ ;%,$2%. F/0"(#$%& %.$**"0,$$ */:"0 1/.0$7%0' <"&$3$(), .//0<"0.0<5?@"4 /1(/4 "1$($#" ,8.

H&- $+*","($- ,8 .0"2&-(()4 D&"20,/1 !,$7/1"( < /7,%($3"((/* $(0",<%&" ,8, 2/0/,)4 +%<$.$0 /0 ./.0%<% .0"2&%. I( !,$7/1"( 1&- /!,"1"&"($- ,8 < /9&%.0$ /0 0 1/ 12. > .$&'(/2$.&)6 ,%.0</,%6 !,"1!/&%7%"0.-, 30/ ("!,%<$&'()" ,"+5&'0%0) /95.&/<&"() ,%+,5;"($"*

.0"2&%. > @"&/3()6 ,%.0</,%6 D&"20,/1 ,"%7$,5"0 (" 0/&'2/ (% $/() 8+ (/ $ $/() Na+ $ 1,57$6 @"&/3()6 *"0%&&/<. C"(-- ./.0%< .0"2&%, */:(/ !/&53$0' E J 1&- /!,"1"&"($- $/(/< Na+ $ K+. F,$ +%*"(" Na2O (% Li2O «(%0,$"<5?» !/7,";(/.0' */:(/ 5*"(';$0' $ $+*",-0' ,8 <!&/0' 1/ ,8

13, 1%:" !,$ <)./2/4 2/(#"(0,%#$$ (%0,$-.

0"2&-(()4 D&"20,/1 (" 35<.0<$0"&"( 2 /2$.&$0"&-* $ </..0%(/<$0"&-*, (" /0,%<&-"0.-. I( */:"0 ,%9/0%0' < .,"1%6, ./1",:%@$6 2%0$/() ,%+&$3()6 *"0%&&/<.

28

> +%<$.$*/.0$ /0 (%+(%3"($- .0"2&-(()" D&"20,/1) $*"?0 ,%+(5? B/,*5 $ ,%+*", (/0 2,/;"3()6 .0",:"('2/<, 1&- <<"1"($- < /01"&'(5? 2&"025, 1/ !,/3()6 ;%,$2/< ,%+*",/* 10-15 ** !,$ $+*","($$ < !/0/2").

8% ,$.. 2.2 !,"1.0%<&"(% .6"*% /9)3(/7/ $ 2/*9$($,/<%((/7/ ,8-

D&"20,/1%. K%2 !,%<$&/, < 2/*9$($,/<%((/* ,8-D&"20,/1" $.!/&'+5?0.- 1<% 6&/,$1.","9,-()6 D&"20,/1%.

E*"?0.- .0"2&-(()" $/(/."&"20$<()" D&"20,/1) 1&- $+*","($- 2/(#"(0,%#$4 Na+, Li+, K+ $ Ag+.

K/*$..$- ELFMK ,"2/*"(15"0 $.!/&'+/<%0' !/(-0$" /9 /9,%+#%6

.,%<("($- (.0%(1%,0()6 /9,%+#%6) $ 95B",()6 ,%.0</,%6 $+ $(1$<$15%&'()6 2/*!/("(0/< $ $6 .*"."4 1&- ./+1%($- /!,"1"&"((/4 2$.&/0(/.0$ $ (%.0,/42$ ,8-*"0,/<.

 

 

 

 

>(";($4

 

 

 

 

 

 

 

 

 

 

 

>(50,"(($4

 

 

 

 

 

 

 

D&"20,/1

 

 

 

D&"20,/1

 

 

 

 

.,%<"("($-

 

 

.,%<("($-

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

>(";($4

 

 

 

 

 

 

 

0,1 C HCl

 

,%.0</,

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

>(50,"(($4

 

0"2&-((%-

 

 

 

 

 

 

 

 

 

 

 

F/,$.0)4

 

 

,%.0</,

 

*"*9,%(%

 

 

 

 

 

 

 

 

 

 

!,$!/4

 

 

 

 

 

 

 

Ag/AgCl

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

0"2&-((%-

 

 

 

 

 

 

 

 

 

*"*9,%(%

 

 

 

 

 

 

 

 

 

 

 

 

 

 

0"2&-(()4 D&"20,/1

K/*9$($,/<%(()4 .0"2&-(()4 D&"20,/1

 

=$.. 2.2. ,8-35<.0<$0"&'()4 D&"20,/1

F",<$3()4 .0%(1%,0()4 /9,%+"# ,8 (primary pH standard). J0/ <"@".0</ 1/&:(/ /0<"3%0' .&"15?@$* 2,$0",$-*: </.!,/$+</1$*/.0' !,$7/0/<&"($- < <)./2/3$.0/* ./.0/-($$; 1/.05!(/.0' < 2%3".0<"

.",0$B$#$,/<%((/7/ /9,%+#% .,%<("($- (certified reference material, CRM);

29


!,$7/0/<&"(()" $+ ("7/ ,%.0</,) 1/&:() 9)0' 5.0/43$<)*$ 1&$0"&'(/"

<,"*- $ $*"0' ($+2$4 /.0%0/3()4 !/0"(#$%& :$12/.0(/7/ ./"1$("($-; $*"0' ,8 < $(0",<%&" 3 - 11. =%.0</,) /!,"1"&"((/4 2/(#"(0,%#$$,

!,$7/0/<&"(()" $+ !",<$3(/7/ .0%(1%,0(/7/ /9,%+#% < </1",

,"2/*"(1/<%(/ (%+)<%0' !",<$3()*$ /9,%+#%*$ .,%<("($- (primary reference standards, PS), % $+*","((5? < ($6 <"&$3$(5 ,8 ,"2/*"(1/<%(/ /9/+(%3%0' ,8PS. K/(#"(0,%#$$ 2/*!/("(0/< < ,%.0</,%6 <),%:%?0 < */&-&'(/.0-6 (*/&'·27, m).

> 2%3".0<" !",<$3(/7/ .0%(1%,0(/7/ /9,%+#% 3%.0/ $.!/&'+5?0

7$1,/B0%&%0 2%&$-, % < 2%3".0<" !",<$3(/7/ /9,%+#% .,%<("($- – "7/ 0,05 C ,%.0</,, ,8 D0/7/ ,%.0</,% (reference value pH standard, RVS) /9/+(%3%?0 ,8RVS, % $+*",-?0 < -3"42" 9"+ :$12/.0(/7/ ./"1$("($-. J0$ <"&$3$() ,8 !,$ ,%+&$3(/4 0"*!",%05," (!/ ;2%&" N"&'.$-) < </1" !,$<"1"() < 0%9&.2.1.

&"15"0 !/13",2(50', 30/ < .0%(1%,0(/* </1/,/1(/* D&"20,/1" 1%<&"($" </1/,/1% ./.0%<$&/ 1 %0*. (101325 F%), % (" 1 9%, (105 F%), 2%2 D0/

9)&/ ,"2/*"(1/<%(/ 2/*$..$"4 ELFMK < 1981 7.

 

 

O%9&$#%

2.1.

!"#$#%&

'(RVS 0,05 )

*+,%+-+

'./0*+'.

-#,'+10.".0. 2."#3 4'# '.5"#$%&6 0!74!'.08'.6

 

 

 

 

 

 

 

 

 

 

 

 

t, ûC

 

pH

 

t, ûC

 

pH

 

t, ûC

pH

 

 

 

 

 

 

 

 

 

 

0

 

4,000

 

35

 

4,018

 

65

4,097

 

 

 

 

 

 

 

 

 

 

5

 

3,998

 

37

 

4,022

 

70

4,116

 

 

 

 

 

 

 

 

 

 

10

 

3,997

 

40

 

4,027

 

75

4,137

 

 

 

 

 

 

 

 

 

 

15

 

3,998

 

45

 

4,038

 

80

4,159

 

 

 

 

 

 

 

 

 

 

20

 

4,001

 

50

 

4,050

 

85

4,183

 

 

 

 

 

 

 

 

 

 

25

 

4,005

 

55

 

4,064

 

90

4,21

 

 

 

 

 

 

 

 

 

 

30

 

4,011

 

60

 

4,060

 

95

4,24

 

 

 

 

 

 

 

 

 

 

8%,-15 . 52%+%(()*$ 0",*$(%*$ ELFMK ,"2/*"(15"0.- 0",*$(

"&$#'() #$"&*+, "&-.+.(/ "0 (operational pH standard, pHOS). P7/ 7/0/<-0

30



$+ <"@".0<, 2/0/,)" 1/&:() /0<"3%0' 2,$0",$-*: </.!,/$+</1$*/.0' !,$7/0/<&"($- < <)./2/3$.0/* ./.0/-($$, 5.0/43$</.0' ,%.0</,/< /!,"1"&"((/" <,"*-.

1+2#%+.3&,(( 45678 9# #$"&*,&% "&-.+.(/ 9"( (*%+"+.(( "0.//:;".. &.&<(!. =(%((. – 2005. – >.60, ?11. – @. 1220 – 1225.

2.2. 9"!20'+,& / 0*!',&7# 7!7:'.%.7#

8"2/0/,)" !&/6/ ,%.0</,$*)" ./&$ !,$ 2/*(%0(/4 0"*!",%05," /9&%1%?0 $/((/4 !,/</1$*/.0'? $ .!/./9() <.05!%0' < $/(//9*"(()" <+%$*/1"4.0<$- (% *":B%+(/4 7,%($#" 0<",1/" <"@".0<//</1%. J0/ !,$</1$0 2 /9,%+/<%($? *":B%+(/7/ !/0"(#$%&%, 2%2 $ < .&53%"

.0"2&-((/4 *"*9,%(). F,$*",%*$ 0%2$6 <"@".0< -<&-?0.- LaF3, Ag2S.

E+<".0() 0,$ 0$!% *"*9,%(, /.(/<%(()6 (% $.!/&'+/<%($$ !&/6/ ,%.0</,$*)6 ("/,7%($3".2$6 ./&"4:

Q*/(/2,$.0%&&$3".2$" *"*9,%();

Q*"*9,%() $+ .!,"../<%((/7/ !/,/;2%;

Q!/,/;2//9,%+(%- ./&' <2&?3"(% < $(",0(5? *%0,$#5 (/9)3(/ !/&$*",(5?).

!"!#$%&'())%*+%+ ,+,-$(".

R0/,$1()4 D&"20,/1 – /1$( $+ <%:()6 D&"20,/1/<. C"*9,%(%

./.0/$0 $+ !&%.0$(2$ */(/2,$.0%&&% LaF3 . 1/9%<2%*$ Eu (II) 1&- !/<);"($- D&"20,/!,/</1(/.0$ *"*9,%(). "&"20$<(/.0' 0%2/4 *"*9,%() /9".!"3$<%"0.- .0,/"($"* 2,$.0%&&$3".2/4 ,";"02$. > *"*9,%(" $+ */(/2,$.0%&&% LaF3 $/() F /9&%1%?0 <)./2/4 !/1<$:(/.0'?,

!","1<$7%-.' < 2,$.0%&&$3".2/4 ,";"02" ./7&%.(/ .6"*": LaF3 + <%2%(.$- (1),2%) S LaF2+ + F .

31

H/9%<&"($" EuF2 5<"&$3$<%"0 2/&$3".0</ <%2%(.$4 $, .&"1/<%0"&'(/,

!,/</1$*/.0'.

F/0"(#$%& D&"20,/1% &$("4(/ +%<$.$0 /0 lgaF < $(0",<%&" 2/(#"(0,%#$4 100 – 106 */&'/1*3. T/&"" 3"* 1000-2,%0()" $+9)02$ 7%&/7"($1- $ 1,57$6 $/(/< (" *";%?0 /!,"1"&"($?. I!,"1"&"($? *";%?0 $/() 8+, 2/0/,)" . F--$/(%*$ /9,%+5?0 ("1$../#$$,5"*)" ./"1$("($-, (% 2/0/,)" D&"20,/1 (" 1%"0 /02&$2%.

H+ + 3F- U HF + 2F- U HF 2 + F- U HF32

F/D0/*5 %20$<(/.0' .</9/1()6 F -$/(/< . 5*"(';"($"* ,8 !/($:%"0.-.

M($/() I8- *";%?0 /!,"1"&"($?, 0%2 2%2 (% !/<",6(/.0$ D&"20,/1% /9,%+5"0.- La(OH)3, ,%.0</,$*/.0' 2/0/,/7/ ./$+*",$*% . ,%.0</,$*/.0'? */(/2,$.0%&&% LaF3.

> ,"+5&'0%0" ,"%2#$$:

LaF3 + 3OH- U La(OH)3 + 3F-

/.</9/:1%"0.- /!,"1"&"((/" 2/&$3".0</ F-- $/(/<. F/D0/*5 0%2/4 D&"20,/1 */:"0 ,%9/0%0' < /7,%($3"((/4 /9&%.0$ ,8. =%9/3$4 1$%!%+/( ,8 E J-F-

&":$0 < $(0",<%&" ,8 5,5 – 6,5, ./+1%<%"*)4 %#"0%0()* $&$ #$0,%0()* 95B",/*.

E/() Al3+, Fe3+ *";%?0 /!,"1"&"($? <.&"1.0<$" /9,%+/<%($-

!,/3()6 B0/,$1()6 2/*!&"2./< %($/((/7/ 0$!% [AlF6]3-, [FeF6]3- $ 1,. H&- 5.0,%("($- *";%?@"7/ <&$-($- 2%0$/(/< *"0%&&/< 2 %(%&$+$,5"*/*5 ,%.0</,5 1/9%<&-?0 .$&'()4 2/*!&"2.//9,%+/<%0"&', (%!,$*", JHOM.

32


/$+&&!0("".+ %1 2!$!3#( ,+,-$(".

> 2%3".0<" D&"20,/1(/%20$<(/7/ <"@".0<% (JM>) !,$*"(-?0 ("/,7%($3".25? ./&', $*"?@5? $/((5? !,/</1$*/.0' !,$ 2/*(%0(/4 0"*!",%05," Ag2S. F/,/;2//9,%+()4 Ag2S &"72/ .!,"../<%0' < *"6%($3".2$ .0%9$&'()" *"*9,%() < B/,*" 0/(2$6 1$.2/<. C"*9,%(% $+

Ag2S $.!/&'+5?0.- 1&- /9(%,5:"($- 2%2 Ag+, 0%2 $ S2-.

F/1<$:()* $/(/* < D0/4 *"*9,%(" -<&-"0.- $/( Ag+.

V5<.0<$0"&'(/.0' 2 S2--$/(5 /!,"1"&-"0.- !,/$+<"1"($"* ,%.0</,$*/.0$

Ag2S. C"6%($+* $/(()6 <%2%(.$4 0/0 :", 30/ $ 1&- F--$/(/<. W,%<("($" 8",(.0% 1&- Ag2S $*""0 <$1:

E # const ! 0,059lgaAg! ,

 

 

E # const

$

0,059

lg aS2

,

 

 

 

2

 

 

 

 

 

 

71"

const$ # const ! 0,059lg K61Ag S .

 

 

 

 

 

 

2

 

 

 

 

C"*9,%(), $+7/0/<&"(()"

!,"../<%($"* .*"."4

,%+&$3()6 ./&"4, !,"1.0%<&"() < 0%9&. 2.2.

 

 

 

O%9&$#% 2.2. )!7:'.%& %. +/%+*! /7!/!; 4+'+<2+*

 

 

 

 

 

 

 

I!,"1"&-"*)4 $/(

 

/.0%< *"*9,%()

 

 

 

 

 

 

 

 

 

Cl (Br , I )

 

 

Ag2 S

AgCl

 

 

 

 

 

 

 

 

 

CN

 

 

Ag2 S

AgI

 

 

 

 

 

 

 

 

Cd 2!

 

 

Ag2 S CdS

 

 

Pb2!

 

 

Ag2 S PbS

 

 

 

 

 

 

 

 

Cu2!

 

 

Ag2 S CuS

 

 

 

 

 

 

 

(2.4)

(2.5)

!/,/;2/<

>/ <."6 D0$6 .&53%-6 !",<$3()* -<&-"0.- /02&$2 *"*9,%() (% $/(

Ag+. V5<.0<$0"&'(/.0' !/ /0(/;"($? 2 1,57$* $/(%* /!,"1"&-"0.-

33