;--liJ,. - KMUTT · I • 4 . I tl I 11 '1 al &J '1 < L ~au ivl""l 3 ~1u ~ ~ 11111 -J
15
2 • sol id-state l J.JJ.J l u 'll.J '"' 1u"1u 1 "Jl '11lJ'VI 1Lfl'j1 ?Jv ..J 1 , l ;--liJ,. 1u I ' 6 O: 4 O lL« ::: 5 5 : 4 5 I ii La fl 111 ',j 51 '1 J.J ll1 Yltivu n 1 'l i L fl 'j 1 ri 11lJ L ri ' . I slope pH l1'l I • respon se time interfering ions .., .J .J 'lJ\J. VI 4 I ' ' • ·- --- -- -- - ---- - ---- -- -- -- - -- - ·- ·· -·-· -· · --- - - ··· -· --· •
Transcript of ;--liJ,. - KMUTT · I • 4 . I tl I 11 '1 al &J '1 < L ~au ivl""l 3 ~1u ~ ~ 11111 -J
2 •
sol id-state l J.JJ.J l u 'll.J
'"' 1u"1u 1 ~uu1 ~Vl ~ln 1'jc:f~1'1lL~::'Vl~~t:iumttuiJ~n1 "Jl ~ '11lJ'VI 1~n1') 1Lfl'j1 ~l1 ?Jv ..J 1 , l
;--liJ,. ~nau ~ 1u I '
6 O: 4 O lL« ::: 5 5 : 4 5
I
ii L a fl 111 ',j 11~ ~ 51 '1 J.J ll1 Yltivu flru'1"11~1un1'l1~'31\J'VI1-:i n 1 'l i L fl 'j 1 ~..r 1~LLn~1-l ri 11lJ L filJ~u ~i~ ri ' .
I
slope ~1'1 pH l1'l ~'11UL ~~ I
•
response time interfering ions ~u11flEtiLu~{aaau~tafl~~al~fl1~~~~~~1~ ~ .., .J .J 'lJ\J. VI 1~!11151ct11.fVI 4
I
1~~an15'Vl~avuflrualJu~n15Lti'11U'Vl1'1n151Lfl51~'Vl1~~~~~ ~~~~~n15 ' '
•
· - -------- ----- ---- ----- - -- - - · - ··- ·-· -· ·--- - - ··· - · - - · · ·- -- -~---------
•
3
• 1 • U'VIU 1 '1 I I I
1mf~qu"uun11 L ;1Jun11sau'lusa1u"'ucn1 ~ 9 \12~11~~ lUULU~~ ruivt111a"u \1~ v ~
IV I I V V IV I • IV
J.M1ll1u1a"1:1n'11)J ~ LLU"l 1 UlJLU011 ~a~ L fl;tl ~il11U f1Yl1..J ci w'liinu la -3il1ntru ~ ~~ i'l'M L tlu •
' I tJ rV t.t
n11u 1 :;\11:1'"'1, ~tJ4J ::>J 1Cll111J~1tJ L~ :=uanq 1nii11"~L \Jun11 am1"ni;·~ Ll£1 ~U'i ~ ali01 ')Cllll\flUU""n finH1 fl1U I I IVIV V V SI . I I
L fli'a ~tl12Ufl~1 ~ -1 ~L rWU~SflW'1iL ;q L~ ~'l-a '31U1 YIL ifuua ~ L 'i.iU L fl; f.) -31"fltl'l111 L ifun1 tlL ilu ... I I t.1 t.1 V I
Lu~ • 1 fl; a-31..,?ln 11 flflnaufl~u LLa" L ~ucnu uan~1nil Lta 1ilavu~ L '1 mi\1a L afl 1~1 t-.01 if uL fl; v ~a - '\J
lit.I V IV VV IV I IV
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Lia11avau~1am1~aLaflL'fi1fl L~U homogeneous L""L1J1~(i ) n1'ia11~~alWflaa~u~l~fMW-
BLafllY11~1 LLUU solid-state L)l11L1J'iU lflUL~~~11at«1HB1-la"11l1ill'U( 2 )
" fliltl L tJ fl1 E ilil'U; L arm~a L ~fl l fl1 fl LllJlJ sol id-state L l.111L'U1U L if ua La f1 l '1, '1 I I ._, : ._, ..-v t' I
~nLL~U l lJ11l 1J1ln'l ift1tJ L naiJ'i1a ~a1HU1l 11Utl1JlJ10tJa ~flmJ L tla1tru inert material L tl\J V I ... I VV
Ag ?s 1 Vl1JD1 'j)'l ~L'M L ifu USJU LL~ ~tJa -Jl lllJ L 'U 'lU fl1Ufl11il ~·~ ~ ., l "" Lu,ul11 m1~:: l flfm1'5 l~n -l I' I I It:
1uaau1QM1~flmJ1~a,8vaui1~a~1ua1,a~a1uLl11uu 'II
a"'nl«U~~v~flm.Jl~tl;aaaui1ami~a1aT11~~~L~U solid-state LlJ11l1J1U Lflf.I I t; V I I I
vt'"111J1~1tJ,~nt1uri111~1m1aitl'ru 3 '11u ~a "' t' I It! I I'
2. 1 fl ilU L l1 i1 'i a aau~ l ~ rmli L iJ>J LU 1U l ~Ut·11t.'l~L\1 n1'j lLa n L U;lJUTlmJ L tl u5 E tlv\J " ,.. t ...
iiia11«tft1tJ tl,::nm.i~1f.I cus nu Ag2S ~al11ifu~UtJl~U1rlU tl ... fllt1ULUIU~1flfl11iltN!~ -1 'Ill I I
2.2 ~Lafl1~~~~1~~-vl1tilU (Internal ref erence electrode ) fl1UL~m .. •
•
'1~ L ~11 .Ag/AgCl I f
2.3 811a~a1un1a\u (Internal filling solution) lUua11a~a1tMCW . " " I ..- .
nia'lui1i1afl1~1ft tl'i~na11fl1ua1,a~&1u~a~ cuso~ -
rUJ KCl ~ ~'l~t1~nit11wuna\J Jfu
Ag/AgCl
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•
I •
4
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L ~au ivl""l 3 ~1u ~ ~ 11111 -J<iluiJ111 'l ~ ntn.1nu L it1~~ 1 ftflatJ L tla'javilu~ La T"Mlti-•
finri11 ~;, <E rsE > ~ 1"'t11 ;L ~a~2Jflatl 1 tla;aaau~L amiwa 1aft19l1t1u" •
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MJftcu~YJa '3t1nu1 ~'W1t1a ..J Ag/Ager iJ f1'nt111 ww1~~1'l l!lta~~1uanila-l1""1u~u I I •
ll1\LUfl~1n
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~nfl1 '1 'W'W1 tJtl '3 Ag/AgCl L~~ t1n~11 w'W1vt U1 lUtltl ~L)JU L U'j\!~Tl1Yl ~11 ~-..11 ~n111"'~;-l11JlflU I t1 \JI tJ t.I_, I
. 111'Ufll constant rl..JUUfl1)fl11ww1~1'"'tllfl (EISE) ~~L~'jf.J...,UYl1Ufl11lJLmJ!JU11il'3tlmlLUil'l I I ·I ( tJ <
~aau'lu~1'J~ ~~1m1L")J1 u~u-diJei"'aaf.I ~ ..Ja11111 r1 LLfifl~r1113.1/i11~ fiL flrl-la110141 tJa .JL u;umit
3.
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-- const. + 2.303RT l 2 2F og aCu +
2.303RT 2F
--,__ ~ cJ ...
slope Y.lfl '3tlmJ l UtJ'j tltluU'IJ L rl frllilB l Clfl L ~1 fl " ' ' LLtlfl~i~t18..JflmJLt.}v'l~LltlU (tl.l'Cl15) aCu2+ --
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R = f11fl ~ tltl -:)LLflil
.. ' T = vl'IMnlJ~"1.11ru
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F : fl 1 fl '3'VI tlil ..J'W 1 'j 1 L ff.I
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11 ~LLafl ~'l un.111 1 f\ • ll 'l ~ nBU f\1t1B La fl 1·11"Jfli}1 -la '31l 1f.llU L tlU Ag I Ag Cl L 91; HJ.Ji f\ 1tltln1nt1 \j
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B La fl l '11 'la ia~ 1 f\ Ag i. u HCl 0 • 1 1>.Ja 1 ~ L~ 1 c;} a L ~ aaJ fl1tl(i1111•ll'!11tl11"..J~aa11sl'lii L 1'i), I I .. ~1'\M 2
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\if un1'JL91; BlJ solid-state L JJJJ L 1J 1U ~ ..JL'\:l 01 "iYlrnJ aua ~flilf\tlU L 1.J a1aaau~1n I I I I 'IJ .
Ag~s ~~ eus 1 flHLUJ -:iaanL tfua"~,1a1u911-:1 ~ 4 v"V111~11u · 91'-il~a
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Ag2s : CuS
Ag2s : eus
Ag2
S : CUS
Ag2s : CUS
25 : 75
30 : 70
40 : 60
45 : 55
tJ I I V tJ I I
Lta1uia1u"a~Uf\Laa1utJ1~lJ1Cll 1 . 3 - 1 • 4 TI"JJJ 1'1.JaU~OOJ\11lU 11 o0 c LtlUL 161 12 {11>.J~ , v ii tJ I I.I tJ I I I I.I
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hardness BUI~~ L l11 ~ nu Yl-.llLafl~ LU'ltM 1 'H. I I I I I " ~· . .
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l lJilU 1"'1U\-1 1 L~ ~~1\M 2 L !11U ~ ~ Ot>lJ "
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n"u1flu11111'lua1iM 21J11~L1tl1lJ'1411a~a11:1 cuso4
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~ ~ 1 ~flat! L tJfl WlltlU~ L afli1~ii L Stl 1Yl1tl911>.tfia "1011 fl-3 Ll~fl~l u 'itl~ 1 fl ,,
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LlJlJLlJ'iU l1a11'111USJW1flfl11U1:111 13.00 L1IU9'L>.19l'i Lt1\!il1AUl:Jfm1~Jl1t1Uan 1.5 0 L1.IU-!I
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state L JJ>.I L 1J 1U l1a'1 ~W •
'... .... ... .; ... •" flmJ L 1.Ja1aaau~ L fiiM.ltil L.ttfllf11Xll':I111 solid-state . L JJJJL 1J "S\Jl1 t1"S1 -3!JU
" V I V V I
L 1m.1~au Lta1 L;;v~:;u 1"1Vl tl~illltJOlflWfln11 L!J ~1Uc;tt1~1\li.J~JJ'lt~'i11a ~~1u cuso 4 o. c1
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l>m11 nauL~ai~1lJJJLu1uvuiun11~L~JJ1~~~~~11~n1,Lflnluaau1~~11~flmJ1uv15aau • \j
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solid-state L lJlJ L lJ "lUVlfl.11 '3t1n1110!}~Jafl-N • • I · I V_,I I f''ll
4.2.1 TI11ftOH1LOH1TIUft1 slope l\a~fti1~Lt1JtJU~it!tM&1lJ110iLtl11:l'Lfl I ""' I j'tl "
011'M1fl1 slope ua:tl11U L mJTJUfl°iUft;t11lJ1,a1-L f\11~, ft l1 il fl l ftti , II' IW t1 t I I'
uiflmJ1ua1aaauiLa~~aLafl1ft1R1a11~iruu1itltl1fl11JJ~1~iinu~a~~11a~a1aiJ1"1~1u .: " " -1 1 " ~ -8 "'\" " ... " " "\ " " cuso
4 l1fl11JJlmJW i .o >< 10 im11 n~ 1.0 x 10 LJJa11 Ll1fJUfnJflLftflL9l1flll1~tt'3
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'lra~n11lfMlftt1a~n111flfl1UBLaflL~1JMR,1'3Wu~1lJuufl,1a1lM 1 n~ ·4 l~ULSU~1.Di slope I I I
., ... 0 • .... .... .., L"t11m.J +26.8, +25.8, +25.8 ua:: +28.0 l1 25 C V11ita1ru (1112.mqlt!J slope L\'11ntJ
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+29.6 ~ 2s0 c>< 4> L1l1fl'3L~l~u11a1afl1Y11m1a11~iru911ua9'~1a11M 4 i~u~~iMfin1~~a'1 I I I VVI I .. ,, I II
n111"fla ~ctflL~:: L~a~~ 11cv1n ..m1 ~11JJ t mltru91 iam'1 ~1lJ11a7 L fl11::M1 ft iw::tt1 ~n11-lt1a '1n11 ., , . 111 at I I " '1 I I 111 t.1 11 U " I
i! ..:J1uua1 l1l.l11il 1 afll11-, .Ma11-iirufl1>Ja~11a11iM 4 0Lll'J1 '3TI11 '7tJil '1n11itt ~u1flO'l1-ln11 _ .. 'II .. .. " ""'''. I "
ua::a1u1,ni~iun11i1fl11~w..11.l;iJ1wflmJLUa1eaaua~1u1fln~fl11~1~tn.mr1in11 ~'1u.ftfl'1i~
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ua: Na OH tla 1u1itJWfl1f\11lJ~1 '1t'l01Jf1'lfJflmJ l Utl1BtlilU~larr:i•la lafl Lfl1mR'J1 ~w 111lJB'll,1 I f ~ t
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+210 r .... I I I
+200 ~ ; I !
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slope 26 .8
slope 25.8
slope 25.8
+160
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~1~i~11~1iiM 4 Mf111ulmi1U11a~flm.ILua,aaau 1.0 x 10-2 lua1' M 2s0 c
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uaft~Jm~a~ pH ~afl11~~1~t1ha~a~flm.ILua1aa~uiLatm~alaftl~1.Ma11~?ru . I I I ""' t' t'I
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-c • ~ ~ .... aa1utt1"3 pH 1.5 tl-3 s.o ua:: J.O n~ 8.0 L~ilfl112JLmJmltlil~aUlUil1ilililULl11m.J ..,
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2 1Jm1, luiflfl1fl11"~1~fin1:Jfl1HfttlULUil1EilBU~lSfl-J\I" I I 11
~wa L afl 1fl"J ma11-:1Wf11JJtlt.lfl'j 1'41uM 4 L ~au rru~ LSfl Lil43 ~1 ~ ~ Li! l ffi 90-02. TJi) '3 Orion . " Ill I 4' 111 \I
Research Inc. ~1a~rruqu11a1ti~flU'MSV~q1n~iJflm.l1tJa1naau~LatM~~LaflLf1,rM811~iru • I J I "'"' t'
a'1LULua11a~a1a"1~1~1u cuso4
a1uft1fl11~~1~YinaL;"~~~L1a1 o iu1~ l~~a1uft1fl11i.i I f' I I f' SI I f' I I t' • '-.
~1 ~t1nt.m n 91 2 1uil1 quft1fl11JJf11 'ltina L YJ1Silll11 ~t1>Jml:J u ifl1fl111!9l1 '1tfntm1 fllU l rau '\ ,, .
I I 11
n11l'll~tn.JtruL 1a1 · it11nuuai'1Ll11f1-:11.uvJ~ 6 0"3 7 q1nn~1rSi'1.fl · ~t111ti1 response
~ ,~ ... J t ~ ~ ~ I ~ ~ ~ ~ . time Vll11 ~ ,1i.in1'111a1t1ui11n uan~1nULL'11tl'1'WU11LiJBS11a:s1aJJfl11u l nlJ11UYJa~flmJ _
• response time I
Lti"~u~a~flatJL"a{uau ~-:iuaft~Luf1111~ 1 •
.. 4.2.4 n1,~nH1Ra~a~ interfering
•
" flaULUB1BD0U~Latm~altttllf11~ •
t I I " '
01,~~lt1Ra~a~ interfer~ng ion.~Bfl1fl11~fl1~tfna~a~flmJL"il1 •
I 11 ., ' I ~ V t.I " '- < aaatJiLatm~a 1afilfl1 rMft11 ~W911illlft11~1W 4 'lun$cti\n1ii9ll ~Hll1fl11iJL mlmJ!JD 'lflm.I L tltl"i
interfering ions lu . .
•
•
..
...
f c,I
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• 411
'llM 7 "
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L 1a1 ( 1U1VI)
12
•
~.... .... ""' .... ..: time profile ml~ftaULUa1aaau1LafM~aLafll~1tl'I Lmfl~ potential .
' A ... SI ' ...., 0 .... .... 4 l1 25 C ll.18fl'l1~ L ml!IU Tm '1flaU L \Ja1aaau
., SI I I II( " q
a,1~~u~1~a~11a1im
' 1.0 x 10-4 1~a11
-> E
E ...... +180 - - - • (1)
: E95 tjl tO
.&-> I r-1 +170 I 0 > I (l) I >
: t95 ·rf +160 ., ' IO t-i • Q) '
6 .... ...
i.ol 0 2 8 10 12 L~a1 (1U1l1)
LL'Cffl-3 potential time profile 1Ja-3ftmJL11a;aaau~Latm)jalatt19'1,d-" "' f • • !. v ., '
a11 ~irufl1>Jatt11a1w 4 ~ 25° c L iiatl1'l>J t.mJtrutta '1flml L t1111aaau
•
•
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-
+30
I
I . • .
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1.Ox10-? 1 .Ox1 o-6 1. ox10-5 1.0><10-.4 1.Ox10-3 1.ox10-z 1 .. Ox10-1
•
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c. J
•
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4 l mJ'lJU 1 .0 x ~ o- 3 l~~1'l lJ1fl'ii.;,~~ 100 ~~a~Yl'l ~1L~'-1
el V " I f' '
interfering ion a~LUll1~fl1111LmJtJUvf-3LL11 1 .o .x 10-? l11~1CS o~ 1 .o x 1 o-1
lJJa1'
I I I ' ' '"" I I
L~au11u1flfl1fl11~111'3¥\na~a~flm.IL~a1aaau~L~rm~aL~fl1~1~a,1~~u~111a~11a1lM 4 v • v .. ... . ~ .. ~
Ll11f1Jl]1Jilltifl l1l"lfli11'3il'3 LJ.il m 90-02 till~ Orion Reserch Inc. '
ui~a~1~1UL~UU051~ '&I V I I I
L ~U1JflUfl11lJ L m!W'l.ltl -3 interfering ion ~ L 1.l~uu Lu.la '3Lll ll11n!Jua i~LLafl~LU'itl~ B \I
I I ' Ill &I I I " ~ '"' • <Oil '"' "i .. ~ " cJ 2+ "D.J'Wl..111flal.JLUil'lDtlllU'ilLafMlit1LaflLflljfMa11~wvi12.1avi11~1ui1 4 un interfere ~11:1 Hg ,
'lJ
" " Ag-+, r-, Br - , Fe
3+, ·s_2- L~~ c1- L ;a ~1iia '1vrul,1nua11i-N fia Hg2+ > Ag+ > 1-
- 3+ 2- -> Fe > S > Cl • > Br I . ... I I t.1
~inn1n11 ~ ... ""' et
cl-, Br- I- L~~ s; ln~n11 interfere LUn~~1naaauLl1a1u I V 'lllV I I
~1lJ1'ltl L n~LifUL n~a;1~~a1Huii.11uau (AgCl I AgBr J AgI Lt~~ Ag2S) L flS:tJU8tM~1tJll-l I I
t1111Lu1u ~~ill Hg2+ , L~~ Ag+ a1~11uLnft.IDn~a1rru s= Ltlua1"ltJ1:nmi~~H1n11a:a1u I I 'Ill I
111in11fl1":ia::;a1U'lliJ '1 CuS ~ '3L if u~f~'.VI lll1Lnfln11a~a1U~tl -J~'l'iJtl-.lllJ)J L tl 'SUt\tlnlJ1 ( 6 ) a1\l 11 I I
n'jru'lfa~ Fe3
+ t11JJ110Lnfl11:nau~v'1 Fe 2o3 .nH2o1111.u~1~ pH s ~..:Jltlua1-rlJ"r:::ntJ1..1tJLl-l I I I 'Ill
Fe3+ inUU)Jl;UULtlU Fe(OH)3 ;~L~m.Ja~u~1~a~L""L1J1~LuaihJ1lJ1llD.f1n ~~11~ft11>.J
a1lJ11U l Uni "l L~n L uiHUBiltlU1~l1~1 ~m.J L tJa;aaallLUa1'iti~a1urrud~1 tltl .:Jl lJlJ l lJ 1U L a1:11t.J ( 6 )
s. "' " ' ' ~ 1nn11a11 'll~ ::vt flam.i flcuairu~n11'l tJ -:1i.rv11 "n1 'j1 L fl'71:l1 YJtl '1fltlU l U a 'j a a au ,
U I I V
~La~~aLaftL~'J~L~lJ solid-state LlJ~lU'JU ~aanli.~ ~~Lui~"lu~1,1.M 1 11n11a'1~ , I t; I "' tJ I
YJ1i.lv~ 'J 1t11UV1v ~ 4 v"'1111a1u t41J.J 11 on1 ~ i'1 fl '3111 t1u1 flfl'l~1"'vi'i"'Ylil11fl1 'lun1"ra11 ~lJJ LL'W "~u tJ 'Ill 'Ill " I f'
Lnu1uun a1)J110~11~iru1.~LB~LfllUtlLU;tru-L~111Jfla~LUtl1BiltlU~Laf°M~aLaflL~1ftl~tl solid-t' I 11 I II I I t1
state L>.J>J L 1J 1\m -l 4 a"'9111a'l'U Lia 1WU 1:l0'11a11 ~1>JtlVl'S1a1lM 4 ll1 Rafl1n'I flclm.Jflntt1JJ1..I~ 'I
4' t.1 I I V I ,. V I
~1'1n1"Jilfl11:~1flfln11 ~"L~lJ1::;a1.M~:u11u1~111~1u~U\'11~n111l~11:~~1~ ~ ~,~~1ua~ V I V 'Ill ., " II
LL1 maJJ t TJu u~ ~~1n 11 -3-31\J L if'lmu uan-.,1nu11 ... 'la1"11n\Ji'ltl'l?1iun1' L .;uun1'laauT1v ~ ., I
UOL;UU unfln~1 ~,~1~u1a~Hua:i1~11~u1atJLftL~uau1~~
. .. .... • •
• I I • • I
. • l I
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l • •
!
i I
i I
I •• I ' ' ' • •
I
15
. ' " . .. ~1UB~11S1\m i O~ 4
I
•
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---------- ------ -- -- -·· ----~--. I I
I " • i i)fl11t11tm 1 ---------·~- ------·-· - - ------___________ __,_ ___ ._.,. ___ ·~
- --- · • • ..
. 1. slope ~1nn'1~
2. °/o actual slopE
I . Wiit"
4. ~1~fl113.ll!IUmM'~ " . ..
'11UL flft ( 1Mtt11}
I I I.I ._,
5. 1'1~ ~H ~ttJ-31U1tl I II "
ftL ~8 C:u 2+ l TWYJU
1 • O>< 1 0 - 4 1i.ia 1;
6. response time
... .... J 2+ (1U1l1} Lllil CU
L tJJJtn.1
1 • o~ 1 o - 4 1lla 1;
·7. interfering ions
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I I
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I I
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+26.8
-
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8. W1ftfl113.IS1'l(1f.M·.) I 13.00 ' •
'Ill I 4' I •
Lauu1ftu11na1~(1J.iJ.} 1.50 " . . !
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... " 9. 11~ia1wtJt1 '3a11111e111 ~
.,J " vtr•1J.111 n11Utll" . 5.00
•
•
+25.8
-
-1 A1 1.ox10 · n~
2.5x10-S
--
-
-•
-
13.00
l .50
s.oo
rl~ii1tr'-:i1wtil~2!t 1'us11ti~t1111 G "
1 c. 01'1 l mJ10lt1 ·• ,:
+25.8 -
-
•
-1 .. 1 .ox1 o tl~
-4 2 .ox1 O
--
-
-
-
13.00 -1. 50
5. 00.
+28.0
-•
, • ox 1 o _, n ~ .. · 4 .ox1 o-6
J.0-8.0
1 • s-s. er
2.9±0.1
2.1±o.1
Ag2 +>Ag +>I-
- 3+ >Br >Fe
=>Cl >S
-
13 .oo
5.00 •
-·
··-
I
1 • 11\1 v
2525 ~U1 938-94$.
2. 'II
" m111tUJ 2526 ~U1 2-16.
•
16
I
" 4'
36' Ulrul'l . 1
•
I
" ~ 6, \11.Jlm 2
3. Jiri Koryta, "Ion-selective electrode", 15 t published,
Willium Clowes and Sons Limited, London, 1975.
4. Buckingham, ~ •• D., and West, T.S., 11 MTP International Review ~
of Science", Physical Chemistry series one, vol.12,
Butterworths, 1973, pp.124-150.
5. M. Mascimi . and A. Liberti , "Anal. Chem. Ac ta. 11 , 53 ( 1 971 )
202-206.
6. G.J. Moody, R. Boke and J.D.R. Thomas, "Analyst", 95(1970)
910-918 .
•
-
•
•
•
•
