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TABELU

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lk 2+ Be 2+
Alcrl '+ (l)
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Forza

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0,950 o,

0,9?5 0, 964

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l)

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0,000s 0,001 0,0025 0,

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(l) relorl oc-d!

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0.880 0,

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i',,,,]
e2s 0.899 0,850

0,

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E60 n, 830
8,05

0, ?55

u, /55 I o,6eol 0, s95 0,520

0, {50

ll
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i0,673l 0,53 0,

0, 805 0,142

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c,632 0,540 rc,++sl 0.3 2s

1,8{l

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l tt'

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7-;

F-r)
J essa ..^,Ud^Jt ; HB. B-

y*wk llg e- ()-o,L ,,**,k B- ; (- L-*,


,-.r1, k', su",vn

"

@* I*gg*se^k vv\.o- */'au* ,qk.o ,W

lovo-

,r(.t-,^k a>v\ A c-'*A'z&r<. -L. ,."(/". ,rn(,iz,\,* s.L ,*u-L o ,ntJll*


na*irr" j&
o*Hi :e Tr,,kv<- ( * %, u*|)w6a v?.?so
"4rl*) o un'rlk "p..;voo"
t pr,,l-* (*ro',,,n ve*o t,urb*) ) .,",[L - Jak:
-L L;
..,vvc,,")x

t{ {l k++ q-

0t+ ltr + kq
Hrr+ 63.$ BJ + /fBJ
b.

&1

(, -r)

Lz

ofg.,tie

pn

B, r.k'*

HB,

6, +n$

bz
Q"*k

nz.,c=,r\cx,t

-q

,4S

o{

{r* *uk

l',8"

t 6rf

e")

\\
o

b*z', -l*

co,,gr.lv-o

{" {*+;,,^k J^ g;b,a

j*

sy.<tY

!h.L

Q*"L a

,J,*;.*

,J.r-(. t"l-

"2['

rlt

?'zx>Ytu tt-t c-rt


.L-e.n.>V c-EA,?io t
kno,* es*^a- u gv,-,d- L ac<tfi-u o l /-t^-',t-

bo

,r/*^t.

.<,,,.i...@

,{- ,l,n e t" uLrro / & ,rG^k /ix<- of-+<- 1r.1.-tYfoi, *L'/'k o 6-si-tt '
Prcl-''cob5"e :
&bL].
y,ruL;
?,*th,,
"'"^,
,1,- u*({ro-o z /-r.*ol*, 1r--k,-' (Ur") ;
o.ryrcsEal
l- s&n^u @
*a; o 6& - "ln ,L' e2k*zo o.a-l$^o r,*k; (nn, q.) )
2^ sr8-,w1 f
(XU
3^5.r{"-l t*.*1*, o @ - oL'"' L' p*/'*^z,.' J-nn+'' .wk*i
''r') )
.\.or1 ,zcr--lto''u' *- ln-,'*
iwe,-t-i F''ot"ni (Ut^"t'*) "ln{ .5"(.*l "@o
*'7* , ck (ro- ootv^f1-'$.-s i c'evz- w*L l* , t -* (-'(u
Escnolo'. - 'e.
iore rbaossotta ("*ozL -'-u6*k'l
c*g-u L occz'lln*< rva p*kn l'r*r/-r,*,*Lsi ,'\^
c

,l*k

Q-'*k' vw o-".1,sb
HB+
o4

D"

N'L

51

,{30+ P'a)
Hto + H+
=
He (u{ ,,*r*Lsl.-rz t, su's 'o'nku"h\o
tbo + B- + t$o+ (rd

a-o{'a'

brqez
,aL^t*

coh

,*'{-'/*

5 k

ke+s

=
Hs+ (f-U,* t&*t*t-)

/^"'* s'{c"e^lt L'-si'a

B- +HS+ F-n)

, a^a-llt^,-s,1- r\4 f,4 s,r(*te / ; /-tk


iure a*r a ', *9 c-st-so /",t(.' o1u* <-- *pp *b Hto* ) f Ut*L uu-H 'n

/o"< 0,

,\ar.r-

5a,,; ctti coeuf ) "u / 'o7*


fo- ,+*ort*si
prkro i.

urh/.'

-l- Lrtr

(u4 *tib , /
,i^' .,,\o t\"r
"/k /orn*ar,,-e
HLO tt* + oH- b-=J

v^ "o^1."Lo g

e*J*

e 'h E*t

/'' "[o'*'- 't^


os*i 4ln'Q " Lr-r- *^.gok"
[
)

*r-k*u 'ht[u- L"+i,,lv' ,


+ Hro
= Hs+ + oH- (r-e)
caw-r

\ooe.-L,

D^/;rn^L av1 H S k

t"-o-?,e.

,*L&

b+lls

L * L iony 5- sr sso

b-L J". ( ' * 1*o e *t

sctziv<,tt A'
"A' t,^ ,o(u.nk *al* , ai fvo'

ke*

rS-

(=_u)

oAo,.+"q.G iovs li*l'a

g*k

gb>*a-t* zr.r.,,rr"-rt-

v-o-ziou.t

'

(; -r";
Z ilP .+ otr + Hto+
oL
e.1L,
' Lr
l-r* %* r v{.o. cow o.^L
ao,asov..o ,*FY
(*cJ-r-(," l; *1*
"t,*
Vv\e@uL br*. Ut* ar,a>b'< l; y,*th k'f" si "br-, *u\oP"aoso ui;6r
e
-

Aa.t"" epcr.aciU

.fu,*f, tVli*

in *T"o

,.

,L st(rzvu

o[.r

, de b 1*k
;

sov,-o

HU + HrO + Aet

at+e<b*

{'*L

<",r$"Jrou.*h

c.,.-r\,,5ok

("-) d &u

J*

&czrtto '.

.\^.

Sr&)?rVrn

t^,,yl vi

trro)

pr-*L q,u"f\rk*rrk t9rso d*th*' U^


h ",oiL
s,ri (*6; *J v,.,.- k

o7^

6o,,r/r,

I
La =

JX

c{,1"&

s,z fr^. \

oinJ
-l

v.*,^

'p,skb d

oLrc,cf +frto'+

,Jrl

o*\@ott

(vc,-clz ,-r"h6r*k

Qvnw,fi

,,,-t,0h J-

ii,o- t"+"

c-*;vgo,La-

uQ,rs-

".Lt--

,U

trnl

Lsk,

u?;

esh-y"*t'.r^^h

;s"{,k' k ('7*Ahu

a-iclo

("'hk

oLL-"s{.>&

A=c-flo-B}ss

/rrb

(, >oL-e^k <*,lro (ob-a- *-*(-,* 5; okr *


'ynnL*
g"(*'L
*9
'(
t ok
'"f*
^'to LL

,1r,o-?o;

"L

v^ *iJ* ; $th , k
/tLt" o x vn o"l-o *l-t- /rU'L,

sp- rh vh.d- nt-L-tuv.1

l* 5.4 L*t'' c.,vs'6 E


Q*&- **z.bwi. " ^;
l" Wj
*.o*vi ,U -"

luok

:\ust* - Q,,uL' ('kroa 5 ..\*k

v?4o

*,k

"(,- Lr,.o
eGivt

tb"-, ;

aiLr\&"
^14?1..r{

oo'lo

,4fl , ",^Ll'o.+,

CkrboK + Kzo qi

y*SL

,ur,3fi,*

Lou
,4t

Hro+

LL

o^lulto"-l".

io,.^,

^4
+

(.=,,, fl ,

nr^c.?rbnr

"^'k
h'ot-'' L

i-

-r$n1b,^. , {

bssi ,h sc{rzrvt* (uo


*ryo.Lb*^le W ,l; e
sluenfe
ovr k ,^ofu^ A
D, cvt946tuva?* b &,rn
VDt^\4r. *[e"rL*k
vr(,*rk Af"b
L uh L^J- o /; u^.- Lt** rh un It;ak
"K&
(t*
o & h<a- e (. f{oenl'e
lnU'Ii,bn" ol* 5i ,lrt.r., lr*

^dn

'2*k

/.'*

fe ,^o(,*

voa-

L.e

f,oL,Lrri'*n

(t'ra"x ) , s f uo-

TABELLA

6tl

oI

.:
=*
+

Hro

'il'
'
I.'*0.

.11:.I-9i-

coon + llao

re
;il:

. i;

oII

Po^- '
HPol' +

H"

0'

( J.l

H:

o'

H:

o'

(4)
(5t

;o:-' *

(5)
(7)
(e)

+ H3 PO.
+ H2P0:
+ ttpoi

OHoHoH-

=:

9l{-r-c-o-o--+

=+

xpol-

H'

1 Pol'
cxs

proolltlc lD tcc"l -

fff,J --' Alctffire..zio;t

r!

oH- +NHl
H' o
II:

:'

(l't)

(it)

rL. p,,rl,)^ / e so4)sivor,*.-k , /*l/n


J,'* oL 0'"^h(+' /d1". 1za-2.btl- ryb
so(uc'le
* lr,rlon o ^. t@ l,';/o L *Jr^, p,'-k; c G su'e
&'* (U f'ol-

* i*1A.- tn*rqe /;

avr<LL< *- /.-SS" svl,lo ,h vh snl'*'lz

ft'''t4P

f,"UL "1,*
*. sc^vry^Vu*

l'o.. rrn*r,0.r> (n o"o) , ('o. - L,-,; J"^>'


- /eL"U L/*t6
(rU) ,t nof^ , aaprt(o,'e /A- o-*Li /"k ,
'o.'*
,2,
0
(WUr\
_
"
kro c- pi; /""1t /"1&
a.vonl,o yr*hr^-ru^,L 0* "h"ro f.rx , .z*.,li t* L-s'
- b-ri ezo; gr- . uL /"''* /*" {" ouL'4^'
tiveutnt
,h

d*b
t
/ "J.
[aw<- st';o/'i'c't*'

"

"J"sl' "''th'

'h

u*s 6o-:r- "bL'l'ts'@ t @A


Pocff
fao*o1,vo J*

olo t* v{1 'n"*k'* d;

( 'uob o-o*h ( nr"..*i

'

,oL' /tL,l,; e s,r'(,|,a- ,k l'o, . p-.Ln'* c- L


{ "Q*^fe t'* g"'k;?'to
tlc(, .
c
x/.*
kLr
f'*'Ji
vrkz^t
?i; ]rrte / for
fn^l( / e^h h- /r!/" nl^o-?b*t- "l"k
g,ahas in- ,tI*. .u&,,"1- /^' 5o(.r-!^^u', e rrvL;
e6s

i s o*prrt

c-ot*\-L

('* (/"-tla
/o*n',t (* pt-?t,,r-u a*p'\'}*
L ( *(*^Q - Vn,,..ro * fl sstw,.la f ,..*,b* &rk,*k fE@ (L'*

0" b*s.c c\resox {*pp LL'L P

P..,ih-,

prrr) Giso e- o*tt- ,nla /^

yk; e

no;t(i t rt;"
,- rV or1,u , si *^pr(-* k
(" cl-ssi/\ -?iol.& ,n ooln

:Q"-1,

"L

$16 {

ook 1

Stw

/-'k k

l"b'L'

W ,\, &rk / /"LrL o ,r*% &-Lt

noa,o\- cot^

(,*

kL

b,.trr*

l-"*

ssL*^,k'

U^ *crl. f'f *ve*rV w* b.*c 5c "i .-l-tt\ 'Q' sv(ue*L - AI cy t"f tb ;(


Lwv* un *dilo 'h Hro "
C\coo6 I kro CnrLof + firo*
b<rl

&trCooV

L
k* M hrfuq ,n**^hob I tor.-"t
fnrl- -r;.Jn
o- a)n,- p-A** .tnl("' urr*on r y',vL,
CtN{-ooH + K$o4 Cnr".rLr* n hsoT G-t=)
h"{- e

ov.4-

"

un t'{"nuk *Pbib @ , ,,i soLro lisl lL{- t-vgLr,*lo L esso v^


\/vtz
-n2a "k
ftsobo "*t*
-"i1, ^alev.*- cot? vy{- 4
f*h
"L d ,t\c
lo.Uf eal'o b./p' V,elo'a Lo>rol<-Lttl 0" * **
o-e-,\orc {rL ilur*k. }r. ffh
Ad ascv.ple tL \" uvr *(,,*^b opwHa "&i a"o :
cl3a*{ + M\ + On3coc + "r4r F-.f4)
LL
bz
b<
re1
[n

t\^ *7*
lu'o' avnvv<' M 6b-f(i7'v'*s["rs- ,'vn";,n o'w-rV.^t o'-tL
/
D-"1* i s"3"'h "1-t;b"gi
r-,,>io*- )'; "t('t-; co'* 'Y "o&'^f' '
",,t^fu*(,

L1^&

on>c-ool4

KzO

J,ve s ,"*k M ev.lqnea. tKeC@-

lu*

3i u,*&e

i>r

AW.

Lt*(t';l-t

t l-L

,*(-r-1.
K"

+ c?tr@o- + Hro* lr-rr)

(,*

nL-L>;

ry' ey*LLn' r.L\^^L ot*y'.t


/b K* J-L

co sL.-'lL

arl*

Larr,*o- '

--

ltt1*-

aplto

&nro*

,\^ oa* -

eok@oK

t' * Q unnL' a''sil'wuuu

(,unt)

/*

l|@^k

' &oN-

cK3Coo'

(,-,

L*ia*
ay.\itlt*
,\^ *7"*. l2
-slr^k

kL

Lir^ ;r(-o^t,

LH.o

&P*ttr"

Hlo*

si f'o-

,Sl4dr-

"l

p.,*L,6r'

,{rga

K".Vb = *\*' Lox- (3-{4


PolE ('o.7*

u'.r'l<-

&a\caoH

kL=
Loaan-

J"k*

ob.

o-orl"*

Lk

&,4' oo. o*lri* ; e


cnrcoo. + ok- (r-r4

,e.-ohsi

Hro

evt lunza.

0*

g- ,o"r(. rc.a.uvvi

-t

cc^

st

titrt

* o,{- (r-04

tl

l,<

c.os(aanh'

kw= Ko-

Kb

a,q' s; mt,,-u,,-t^o: ko= Kq,r

/*

Klo

kb=L*-

lda-

(Zun)
L

" uv,A r*glo, &a.roo -AsE (* .-sl.r. [e *r;J^ Snar,es1,'rr-k pt-g".>"wlz


"/L
('z.,k*cr*
(r;Je
[t]/*
iulr',-
ieLra;2o
e
R
,ln'
sn-rr<v1'.
a*r^k
-lbt
1--,,e. IL wr &,.to o *W' o,lt* , L ,,wtk e-lo L /-"* ltfut o.),1". . lolU*- Lse.
- Yerrro oi /etrr. - y,^ gr{" vv*L yJ"leJ s,s(*z* ol<-' o-"*(l+- *,f(V A e/-W tM
t/t^ *n,.,,r{o J'; aT l'^n'?iov*- L

- /rrn*o
o,(/.'

,,o'L, s; ["/^st*

ba-se

s,,sha2a

'1"

L'-o 7L'
'1'U;

'

(" (r- b,,4 *,,,*L gr,,n "t J 6,ot,* p-. oln L*" i s"-'J- L"'''s ,
*^* l^' &';^skJ ' 7'/-t'-'
u"'*('" ais'J^a .,b'sh\"i,'*n t'* *tL l"' /n't"\ e
,

uvr

+,

o^ln li

L,or\

7v;

ttvt ocL

"ol,^(*^t"

H+fb-Hg+

Jt;

ulun{

Sc*o i

ou

r Hro

HEo+

=:
Sol t Hro + l.trsoo
C"'* + 6czo

i-

,:

uva

ou-b l;

l'trsot

/+^-;, .; <,r
/"r14 /*

: l*$rp* lrlrL** ,l
o[* e- o^ a-"iL d Arrol./-

/)/

rr1ro

c-e;o

L-d tn'

- cr(rri

5or+Hro +
x

-*r*

"zx
14+

(Q*uA

aL' t3'o'sbl , qb4 i

tt o,6o y,*hhl",

o*'sg.*lnnk

f bk

*,**

rnorcC^*o,$

,,,v1

<APi>,orp

e-Q'auiyu.

- f,*""F"

"tt qry, tN

&Cgva

I"rl-

A.?t

DErr

catw -p''f

- *c,1

E.gyst

Nrl so(w^l< n.f,-, {'.1,i?;Lnv kl u,&e^b pvyo ; , tzcon,.L L rcou*<


* a<-rrope-ror<sr >eral;/lr^-L* :
zhzo ; Hro+ t oN- (r-r4
L ngp*onLa l- //;sso-ban\rq- Je.&' or(,o. D*[ yol.,ll\o o*ro /,-tl'y,.*1
Kw =

*rr*.

or- = fqu [trr*J-Er-

t""-3 (116)
l* \,,,\ ,,"1-," J; @Ir;'o) , e>ff'r*^L &. ana^l,.-o,*'
oo5 - ,(ot4

oL o @
i. ft"(r,;,{ . D*1, l^
Lfir*=En- = 4 "
nu.Le-

rJJ'

G*i:

6*ssissih.e- Jssouv e-bxu

, y;*L A

u#'ntr, L H*+

,10r" n'sp.k-r< ,o^ce^{>o?r\-'^

Kw =

fn orJ l*

lnlt' *f*
e-

"i p,i

oN- si

6*5i/l.,t-o.tt

y-rs,,,o

'*ih,

@"

U-I)

Jo*<-: |rronJ "*J= (t,)- Au)

le *l-,L L' W*\ vo&.\a- * (- b^p*b^ , ,vl*fu'o 4- Fml ;c. *1"..


b*,- 4-l) - C^ t, v.s,4\h.L J"lh k,*r*-k* vte-/1.'b'1^a &
b otvoo W
" (wL'
L'L*
'
ovlA^
Hlo*
o
a'
rV,
[eXeL'
o^r,^('*e,v-;J
oi* lu.' (
"*0'o7-o
1''
.TABELL

Iy,1- Prooocto ronrco delll':cqur a diverse tenperacurc


oC

(o

o
ro

I o'113s' 1o'"
I o,z'zo'lo'r'
I o.saos' lo-"
| ,.oot 'ro'"'-"
I l.{69 ' lo

:o

,t
30
-l-k
{O

so
60

I 2,s19 ' l0

I s'*zl
| s,crr

to'l'
1o-''

N'rlL ,Qruoi '?* /; aciLi,b*ri o '&, L*


+* k ,./.,-2i'vh{, (t ,r"") ,
l*

sstat *ry t< ,tf"#'.*

t4-,

uvvt

oflrp*'-,-,1;ta
oy(

ow-

l.'(o-14
a.
*r{.
o+
5

(o-o)

v\

'e"

q *rr,,+ + L$ oo,- = &g


<,o,-ti,rl,.,

"k

.\

nd*

Lve-(o, - Lt &tiro* _ eT

Qr,"l, oi ?{ s.,n\/e/e; gll + f

,"1^*
Q

I e

on
l.l = t44+- gon
e

lefr

*th gun [1n,,.- t

OH =

(a

s' &a,u^i

\wo,r'-

cwzuabt

\$eLul 4-2.

co

"(.si

n
- bt

Krot

l<rxt

= L4

-pK
-1

-s)

G-')

aOll

ttc{la
d

L (*,ut'.* l't'

J^Lit<

*
v. 4!"r^2",n tll
M si .,l(**

e , [.-h [t\l*

[<-*)

o,r - aa (4
lfpott{ = 4l-(

k" oi4 urr* A *sk le ,

(K* = L4

&on- =

a,elr-* v\D- s,t.(*

*N),-LY, *Ll-^k E
5z u (*h'o*

(q-r)

Kvs = -4-4

lC

,Y

4%d
t*U

lrl!*

PsJu;e ?,bY-g

e/'

,(,

P'a"x-o' 4-L,

fig /

C.p ru--

,fr=a
log

o.

tos

log

lrro*

oor-

io

o
t-

E.

6
t-

-7
o

a5
t

Q
J

L]

U
I

- .t0

-'l

LJ
C)

l1

.t

-12

(o-t

13

I
I

_14

01234

10 1l

fs. aPll=t7 ,

h*.n'' 4o-z e

onru,

't3

12

PH

= 4o'lz

Prodollo ionico dett'acqua a 25 oC ( X*= 1,oo.1o-to)


Tlntl.l.A lY,2 - o1"or . oort- , pll o

hol

l?tot
dl

qil-

Solt r ion i

Solrrrioni . ocirlc

Ii

rg-t ro-3 io-, I o.3t q.rl o-a


-l -2 -t -t -6 -c

P
pt?l

'

16'!! 1o-r',to't' 1-tl lo'ro1g-! to''


-tt -tt -12 -lt -r0 -0 -0

?q

rl
f{ .13'12

nall

Itc

0-'

lf

,t

t09!

&iluir'oni olcoliac

l0-t lo't lo'ro lo-rr t0-lt 1g-rr ro-rr

-'l
,|

f0
I

'?,'rt-

polt

1-'

-7
7

l0

-r I

-12

-13

lt

t2

fq

lo- to-t lo't lo'o lo-t


-3

lo-r

-rl

14

t'

('o11";ln- /rru'",*c1vr- ,; v1,"!-.tf


"Lt* so.,(an?< ,
e 1^V"ln L Kw lto*- s't ()u; , * t;Xaz., Grs',ieu,r*,.-tknl'e. Co*.ny*,*t0^
'*ttr* 1uf" l.i ,,.-si L prga,\?\,u t; Krry n.,vt i ,,'*k,&- " fta,- sc s; sawt4-,,n
iu,,.:a, e- yr,\rLi \,/4r-!^o; ,-t#"c.r.E.h L'
t^t-L(, o"f* eflr&;h , v*b' t'' h"*

5- e; t,xLy*"n

t*-!-|-'aclv

bi fuo' F; Coyr s i li*,^- Kw = (r*). . G*"-y* PL


p,({-*(; , rl*^L
""
Lr-tot< t * Si
S"L,ot"; ei- tr.,tLvu ,.rica r'L S oroo 1t*D^ si t>ot*+-ek t*
&
fl'* Kw = (n*). L f -vl i c.,nci f,sa,a *ltro* = |trlo'J e- o* -= [*7 , ^*
t?-so

/rtt'-'y^

eue Es pot-Sup(a,..,.ua cl<- ,Pno/Lrl r bw,*l/*-

4 Lso.
uu"lu-

frr,*)

),

D.,nJ =

s&*,V'.

&c?era.

9lt1 "L' N{of

(d-,

W*)"= 4d1\'8."

*qr< ""1"{n:

<

*lrr*

@ox- = fr,o- Dnr*J fon- D*] = kq, = 4d11'"o

fi=,|ffi,

e po*L.

: fr' ['r"-3 t*J

'

oq* -

,-ou-

dse :

Kw =

r| (v-*)-

si

l'a'

( o-r4

b-r"J
[7,oo
) lffi'"

%9

psol.,

(u:

,(3,8o 7

q orrrr (-g f* f,torJ


q flTo*J. - b2 Ft -PIt
=

a n&"* rb

,oto:

p * i,*

."*i

i"e:

fr=

Lrrol =
J^'

(r ri

%b"f = Ll#

Jo*, qfox-]=- 01 ft
",t,^-sLo

l,n

o,

LSft

-a"o * 6,3o = -

o/LO

(a-t)
,,)

to -

pH

/-&

&-...-

(arc)

oN-= L1
I

ft t"*'J A ,4

: -0.i & -pk* * /

-i4,oo

*ftl

Q'ru)

ez-so; Ltrt"n-) = ot'!-o' lq,oo n pl4

-4\,3o

+ pl4 [r-r.)

l^

,1U.
,br.,

L''rr-

zir*. ry
\ow,<

co

ll

T.4,ESLLA

-rr)

esti>rr;ts a; li*"ti
Lr"Z / \aE Lta 1-3 .

o-

IY,3 - Uot krotJ c to3 forJ lo ,uD!toac rrct


Crl fi t 35 oc.
oct |t
t

9H

l.

00

2,

OO

3, 00
00
5, 00

{,

f .00
?. 00

8,00
9.00
10.00
11.00

t2.00
13.00

1'

fvawL

pH

. t2.90
- 11. 90
- :0,90
- 9.90
- 8,90
- ?.90
- 4.90
- 5.90
- {.90
- 3,90
- 2.90
. 1,90
- 0,90

HEurR.o

?,90
8,90
9,90

- :0. 90
- 11.90

(- Jb,*-

toc [orJ

oc [flro-J

- 0,90
- 1. 90
- 2,90
' 3.90
- {,90
- 5,90
- 6.90

la *^"un*nn-

po>souo

ionngS."rrb

7u; qt

e-

(A-nd e-

e-^va-?rb;

On

fr-:oi YPo kr.B


l{^b
\

l^

zrilo ,k

vq

*a*"'

,^.o^

k a4"k

b* =4

y"*Lo

w"=Z

AUO,rr-O

V'a

(trciL

e-

t'-oo*(*(',*

('o-.[-

)l

z &r*fu

\0.e-;-v4- G -n s)
rzE*LE

);

/rfu "ru'/n . REveJ

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J; 4n "' oi aasisat'
n* U g"rr, b,{^ |.o- J;
VT
l- 6l"ss.s

rq
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e'G

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l*r*'*

L/^ '* illo+ , 'b s i


af,sfoc,-eonr bfi'' *ub t (e^k ,g '"-2' k

u-rr)

hg*h'o / o((\rl< rh yr*'("

-,4;D:\&'

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Qro^/o

/^

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qr-'biep?rr,r'*

,\t sJuznr c x6u;lo lel!0*


&r"\'ha- R.wLE a a}ru'or{ uf('n4

lorrrto

/; /,,,r. ,q;k'

"r,

t4

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loltl *r;L @ {<abi lt- >o\^<:.


L ht' Uo^r A' uv\ e-r;b QA u'\^- .,'tz a L' *(^E 1'*'k

c-

d,,,,*0^h,o

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rt

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o Wn}';,nVz

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i' :

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c-t

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tn

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o ,*"^-'rl * ,r.-b l* f.k* e-b>vd,1l-'

{ ,[-z: Luro[t"r) = k,4


o

(fR ,

*-r-av<.t"a
&r4

lu*t*-a

c,;*d

iil(.

n,(),"ro

_-(4.oo

/n t

e<

co,PC-altoA

;; (z

(^).

= (r-)

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Zlor"

6w<'rra4!1hsg

",(r-L.

k (r= o,oerl

@'o)

dz ?roL

c.sh^k e p-o/t-c'

rbw,'a^o

/'ru-

'.-Ssa^^f i

Pan

1o

{,oo

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njiss " .

no,e'-H

zr,t t *'v*e aot'/..-','$ fillotJ ,.,."tn


q* si k ^ c,-,-,7& k,.,^r-k
l'ur^*{,o tlg / , .oL*io"- su//l'uv-k*""k J't''k, "'
a,fvol,- santt Fn*th'
';bv,
/rs',.vto : y,bk *l[^ u,b>pu
t* ,*cQ*tl'o*b* 'k/' &10' ou>L rh &ft :
n s't ,\';,\s ev\ 6

N,E"@

(3lL/l.r

r{,

1,4- n*SSE

,,".-{*

(= frl

) ,,, flh

q^un(>o-?ty'*

C* = fBJ

/^'@

(l-r

e ,j"& & Y'u^

yrc*,*Y-l< /",k

1*

(=

po

ne,-vk

t^^0(,' oo''lo

f"'f ) 1 f'hk:

.>gi,* ,-*,k b conl) v\* { '-('{*''o"l'--Uk ovw'A'o fl


,glliu*ro
1t*k
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r*

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fr,*L
0r

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,l- L,ra:

,,*-sl-oI

fn "*l M /*a"u
L*
--G * In*3
(!-r*)

l"t

i,a.@,s-

Fr*J= G+r[ffi*
L

sans G-rq

L s/r*rrr^r ewp. "'L;t-L ru ,*ll*%-* L !rr.1 e y^L

tt W iil!- or(ror* a*ss, l; r./vr acrbo rbltr?b\1zo


Si (o5s",*n tr {0** &-** k?9tto*'r'*>ic,,t .

l Pa

(a-zr)

7-,VL

?H=

oln

k G-rr) t,i,*

Dul >7 Don-_

Q""^J

q^\,&hvo a.pf-sl-,^*L"

sln*,v,-; ,({"ik t;
M /^'
bn{ e1;0;b*v l'(/' u1'* .

,L

,^bl* f*b

j,*ile a^lzr,i

e,a

f*

uo* *rf"

6 >'t'" ["'f

"r,(-*(,"-,, fnrorJ e y-vk


w--.,^,- p-ho 5,b?o- h,u-,o *^k

fnro+f = $

L"l!*

.{o-8 n

C- + tt 4-L* ak'r

I "*lg

i^* G=
i:,"

(eu

{T;,,

r) .

G-rs\ *LLi,,^.*

(o + 2-'lo'
u-1

?_

lo y*tl. s *L

'6->rr,

f o\4 (r*b

tfu^ Gz / 4eo Kq, z 4oz -,(;rt > l;iz


c "i ,"^^.1;r- 1u*ln C" > i; 11
<qy,,* t ;L oL<. t" sl.ts, *L
fut"! v66
f
Gs

[el

Q-zs)

Q*.[.-

[nr*]=

f ,r"nJ = (o-

-Qa

e- L /**k

Poc-se.

@-r"\

oln'.

z--t{1 n

, frr

S--r.Atfr-11

il:prt+- q @

ffi

/-

c*to
auiwA)
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t'
I

fn r"'-J

-t

4o

i fl

W!

(l)*ssur-r"oo - ,resi r-sg,eLt* 4-4 - ?U. '>


--G >,(fb
> ,@'61 >i ,.rss. b :"&au,r *(prosstt--o-[t

LnrorJ = e

-W

lm
-)
(.t

> 4o*3

tr'

_a
{'to ''

TA1FILA

0.,o&z'*.

vtsL

-S+lr.t-4

Q-zs);
(a

-za; ;

?U *W* .d-!- o- ?.

di solluzlooe acquoar d1 acldo


force a divarsr cooceatrszlooe

gH calcolrto

,I'

3i.;;;'f.o
(rv.

con

rr

lv' rol

trv. :sl

|
{,o>; {;-*., I| ar. <;r.vlrr-,
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r.oo . roJ
1.oo .
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1.oo .

ro4
to't
io-3

N.E. I'vrlorl

2A)

5. 00
5, 00

6, ?9

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,.nt;tflr6?t-sonodr scsrtarG

ig-1 r,v w**ou-$L Pil t.


- b)

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r lypsgtLo -r,l-.*,(^r- , &- ancp,'l>p-z'!.e

(bv, c.w{>v:.;c^Pd- /rU'

t fr$:*

*oL

43'-{

'

sb

, ,roz't i,l,t-.<,t ,'f W


oil, ,, h L' ur' *l'Lo s- o'L e lr' '
f'U* yoft t\,-ra-o- g (*nott" ..t"e'
Yt

sso -

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e*

hreL.

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t^/^^ /;

h <oL,>&* ( "v; ('ey 'N^' bnb /nll.'*?* e f*lb


fi
u{ ") ,t *- l" /.* ?'6 otlra-vvt-Q- It yDlt.'- gr,b"< h l-k" 6 tg.u'e
(rcsr^h ( *ro* oN- e,b-) (h a/-vuw* ldl
lruk

ey[Q^bn

*&e'u-

NdlL* 7iryae
i(, puru+o l4

4-L

;,t

r*'p*[*L f,. gtr^ l*

k-t*roL)L

f^^r,-k

r\^-,.|,,a

b a)rve- J*t-

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"

Lwro*)

= 4d?fr

?Et-

cnno,-l.,a-"bx*

-U-

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tva

sac.r?+r

o H. ,t;l t! i,

A @^

t.or'oP':oYt'a

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roq

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-8

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J
ln
t,

r,
c:

-10

11

g,,i"f,+ %[nro*J.4tu'J
Lr fr"J = 4,'tl
(t **.

-12

ffi

-13
-14

Hce

ovna--

fls 2

(etio<:

llzO * ,r'a

,(:

log

o Drf , 4o-Poil .

+( ,Ltr'
(P*

t"x7 - 4o-11 .k

1"4

1.t; /L.6r.* te,,o-u- r-.*b /rlV*

?"*

s-L>"t* 'b \11 L

p,,G inv< bp[n"-J = Lt [4-J , tuJ,tut- h*y l*

{-r*il.**X s

tl,,t^

vv.a.

.t 7

e,b1

9 10 11

b6 Loo+J.
PH= 3

1?

pH

Ac. ctoridr ico 10-3 M in acqua a 250 C

&; [u7,o

-*,

&-O,
Pa-

!1o.w fr*Yr

<a ltaZL'

'p*unli '\'t s&2,v4-

*P

,;t-<,[.la Hg

u1^

LT

,r

z;oJ t"/ft1-v-lc""t"k lt";l<'


Lnt8 [u7 LK-)' k*
=

c,b'4- ?u

(.

e5z

b!-

ll,-

'(. y",^'Lh't rbr*'- '(tk!o-c1-a


[nr{D,of = (x*1.= Kuv

*nctnfo--z,b'+

ttlL

ewtl4-

W,@,

E-4. ec-

U-+)

o5ry

ry

(t-r)

u--eL ,i l'o:

frr*J=fu:*t"r]
(*

4- sg..ae

sr Lc-;

r(,

['sJ

,-s

6L?u-Dio

G-r,)

t r -rLoP u :v?,6<,1:r4'

+'k!" LA/'o-u"L L @, nsk .s-,-,-- q-& "A*


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/r,l/' n'i/o LL ss., ^wL'

t'

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6=frErte-l
A >Jn*,v,-' L /.."2*

rb,^

c-nc.

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& ,-"1*H'

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> oroo

s'uu".*t e ut'*o-o ) ftlt! n,e.uu


furfi c,l'- 5;o,.^-o @, E "

t^!!^ Ar4:

f,,dJ = te

e l,t!*

fs-3 = furor3 - [oNa

(-rt) =

G-rr)

/ fl

.. nesc E

LvWhvq

|iQ-1Jz-

i l*uY "Q, evtie^o,,.lo ci

(d-*) (rUt'f

k-'

-".

lr.rL

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lt-'

sz*w1

Lq

(l-,W'.r" t; "L k"r"h."I^L)

. J.,l!^,Q-tr), fuuJ = G- te1 Q'o) (i,U'uy. ["lL ,,^o")


(o''4
e p- Lo (i,tl , 4= G- fu*\* D*7
L fi sosituist,- U U-r e 6 0-,,) ,*//* @-")
k
f uriJ = k*

.Lo

b*b
It .o*] =

C_

Ltt

",

fourJ

(t-t e)

ta6j[on;J
,*LrAr r\^ funz,o.t ltllt un*^(*,* L @
G

V,,u

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tnfl'-'' (^^*x*)

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J; r1^^- snL z,o* L oa$ y.-.9,-Fr.olrL ,t"lrr(- rh a-ct,a
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si

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Lo-rn\ fr,,,,*k:

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ltt

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f,NJ = 4;+

<+

4on'

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r'1,

;* > 4oo [u7

g-u,--L

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J=

&rt

ls:

G-r

4'-3

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gvnwL' ?t'{=? A-^.) .
U ('ruL JL,k y*sl- r ve.nfi'^."* pv,- G-z,p)n . l^
oi L

b*o

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cor*ln1.,"->)or-{

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f-"b m
te7 <<

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L -

Lr^b r*e,b J^/t^ B

mrL tr

''(

1*rk

c,^ b

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4/l

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Wa
b.7

Lurr+J,

*"

N'e!,b Q- tu) ,

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D"n-J

P;

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fJ,L'

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;rk ,hfn,,*)e &Lnr&J

fir.,oJ = lG
(a-a',)

L.
Ikrrn)

pil=-*eAk - 4LaG = *ro" - p.sc (lrr\


+
ti k-'*tu
si *lo|* Ji)*^k
y,rrsL c- t s!-ro.r<. -yp*ts,^,--lt' 'l'*
Jy
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Q
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il u^ Q *^ e',--ssiv\

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t Otzt<-crt'Otf'rrr|
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,a

L]ro,J

[^rorJ,

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r
C, > aoo (fnrrnl r

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lurl!* Q. -r.)
af*- @ @, t*a. *)l^ G-rt) ai (* {-*,*',*.o @
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h'c-

([n," *J u fr*-])

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L ,;

.tnrL'

G"q(ka
ru|rs)
Urr*)=-k'*'l

iaot.,,o;

Il',5 - Conctatrrzion. IdroEcniolicl di roluzloni


rli rcidt deboli

TABELLA

l! t.
dl dlslt

r. ?{.

l0

lEo?

s, 9.

{2) | rIv,ul
tt

(IY,

Jta
,.*. ro{ l0'
I rtal
.,oJ lr0 '
.

to

o-]

sEo,rdo

El/t

ti,oa?

olec@H

[x,

c-

co3

tctdo

ro't

.,0{

l0
t0
I

l0'

t,r-,.l
10

5e

-5,

16

(rY.

{?)

I\'. iE)

4-ea

_,ll

.r

rol"'t"l

.ro{
.

lr

l(Iv.{3)

ro{

t{.!. : r.lorl lBttrtlt

at

Eo dl tlrlrrt'

c f'B] ;x F'" oo'n o'" F7/in g,-,:k (p-Eo s; fffirrn I E (.^,

t) feJ

&'sur^q-

;ltu,r E, @"@Lg7 e Dr s'i

Tersova

@-,rJ e- (r-,1 :

rnt'ouo-tz ui :,Vth t'a-at*t<'

I G-3i)
Dtl: c-: finror) - Lyl A-")

[e-] =pro+J-LouJ

5z fG "

ye<."\o

E ^.bu p*q *t

hl. @

"L -1"0k

fL

"8-1..-

o!i.,

l<a-Norr,)

;rl

l't'on

a*Ubnw

L,^ a-oL,

l",k

(nn)

p,k

-k

A^-,

Hb + llrO
sg,skk

Ay'*

+L- A'*)

r v{/t5o

sir"",lLo.

Y"/.|i Lf"

(',*,,.*,t-

cW fnrd] , * ro',,,,, El si ,lr,-,'o .o- t,u-"e- c-o. @ g- "r*r- @


coarzsa
[ot,u- 'u**-L'
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e %*

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a-cottYa-lLz?'a' eg/L :

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I

si

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plt ,

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ln funzion del pH la soluzlonl " acquose di ac.
acetlco 1 25 oC e a P'0,1 Jr..

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a.

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Coppia ac.acellco

- ione acet-aho in acqua a 25 "C e

p=91

4,65; n(x*;.=13,80 i pK,

[e(K.),"=

14

pH

14]

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'() A pfi=o,f 4 &kro+= j,4 1o-1 +D 7o,o31 to,oooa!+(tr.\o-lotL3 '[o-27:
Verl^

..

Z) "

?W

= E,o

-r

orror = ,{,o..(o-,'

-1,0

t -.(o-"n

-t-,f

-.t;tt

o,o)z-no

i f uo- at|-'.rc ,t &,v6 ro-t^** Lf l'-.o


svoi ,'o-'. Nel[& e,<o'u @,-e) ,eu'<
!!. SJ*&-\ acy,ms' J; nuln /"tt.r^- e !-r)
o ?ro e [/"=q4n1 (; ^^' 'ol*; "
Ur*r dl" f L sluz"n" tr;'-q
?

Cr" 4- tlrr*;

FsJ4-\

&r/rl; ,-,

0* *'rl,*h h,k

!ns> r.esq

'

rsdtu

?b4*= z,o) &",4*= 95 1,r0ro,')*='t1ft


5,,* n^p-[oh *l/- I'462'l] La.-'tl)'

bJL* qu,,* (!- ) i '{ou' 'k

7o- t(.

{,

6. 00

6,9

?,ss
cc-

9,0c
"!s. tt '

-'Llo'n *J

4,-U-

{"

.- e .d

trrl
- r*'3

,I'r ltr.tr.

fro

.{.}
r * ""'*'t
:;
l
I

lral'I
- ts,6

lHrrl-; ros
8.3
"?,t
3"

- r6.
- r{,

{,

- :2,6
- t 8. fi

3,3

.o
.-

:.1

ri*pq,:

r"0

'r.[S
:1.*

.* 0

I -

'

d.!
Y.

[*ff;,$.*.

e- "^ J*' '-onk-*(o '\A-v4-'w^4tu l

spte w*LJt

3"0

lt*?
rt, $

,J,^^ pl'l" i^- ".^o^f'aa't^' 'L' /' lJ< &

* 3,0
* ,,"3
- t",
- ?.f

t,o*

2.3

. LI
:i*f.

rtr.

"L'

s6

, S0

'

(*nk

g*

:
.-

3,00,

ct"- i(. /"b-6r*,^*'* c.^sisk L' k ^Fffe


n';!'L;
l; orv<' -n"'Y*'l'^Li oi ht
W',o{n hil^6*'
'o-*'vb'{
2" - L 4yvt L*- P&-"
tl
"{t-L ,

1., 00

t* s [N, rc, ]

otl8rru..l

pH

::kf**I
u-o'l'll

? 6 e

dl rc"'ronioilio'o'rot r

2. 0s

:n-r-*[.*

'r'I

':

,1

--

*6'

x,^

5.8-

. 1.0

1..
, -,*

:" * -?;0.'

-,.

I
I

-tt

- 1.8

'L:3"
aa

M uy,()b-v <L f*-!- fn-

tr , Ln I','tJ=Lnr"rf (qc=-Lrts) L- 'Q' pH l'!t^


lnlsoo?,o-a

s,tnlo

6Lht
sr&z,v*t {,' "*";Lo (u*', , zsx*L l,,osrn,obt&- Drr""J r'(-(t

A h!,

p14

z,ru\ 0*

(=

UzPqJ

o'Y<'v

a"t;z yYe 'J

ctvua 3 - l." XYe '' ('' f "*

d; Kr?oU oL, z
f^^^*65q Nrpe[' ,lh-

, ("

soL,eb.<-

l-'t-a1'*t

kt*

[-o lUte"; )

o*{-" "ss"l' " F"i7;


)'a,-ce 'lu i9"tVl ti

,.'o..

e-

JuU''

*":{o t*Llu

tr|

)r11^ .o0u*"r* /rl

J''usnoo

wtr.'vu- 'L'
f"'!lL

cnVca

L< .Q

pL/

cc( t 4- l"/' Ptr' J'L

**W '*
U /^sso^\q-?b*e a aYr-a- ,{ fYzt 1""* e<ur<a G-A) ; ^'t ["'Ptl
(
,il
*6t1 ,
U rtr;] , , **'nl vv, {-'-'*'t{' ' I l1Dre"{' e

eshc.

&"""
"5o-

*n,,r-k bo.s-o- (nno''3 t^u/e) O 0t sn!n*'* ia <!-.,v'- Wfr

b^^eq-

l-[*

I p,,A m,E "E

1a;4 = [0rct1
co,*

&soisss

@,W

h{..t

T*/^'

-1

Lrori J=

e @

rr"erh.ur^*-le.

"!(-

6"-I poa.' A,A e E oki t .-ik^6o*


{ flk-. r- pn/t^r* fr , J,tL,,- { 6*/,* ,,
s

giv,^o g*l-v.+

*,-^J-*

,,e91^o

@t

@iilb

".bn1,-

*k. o ?tn,/"^e* P
(l* si;rh^- & t""t*) t^"ltL

%A-

**,

W
,*z* Wr'A ,'-lt"

{,"*k

Ttq u.

E{P0'.']

F,toJ

/St

xx--_ - 7.*,

,ln 6

los,[o

ejl

ros

pH

1
\

tr.r/
../

\r

t1\

ffi

,I
I

21 3
I

lrlt

s 6 7I

or.rtryr.

Ac. fosforico 10-eM

(x"r)r=Z,o,

ojg

r0 rr !1' 13
I

rr,!l

14

pH

il acqua a 25 oC e rr = Orl M

(K.,r)r=6,9; p (K",r),n 41,7 (K-]=1g,eo


;p.

, p K..=

14.ool

A,

fl. pK tt

*-U.^,

l* 6""tt'!"

os*tratv

ef, *- 6rtL"rL dru,*lo /'!'4!-' b'*- "l

/'-,1-.,e-,u^r ,lolt'

,lo

P*/-u'no''le

e-Eto aowi"y'ok,'

[". pu^ H tr , Frnc'^'e,* L *{" & f^"G^zo A c @'


-ail'Jrr,n ' p,,k E (
) @),

- l;

- , i^-cco"zJ.r* -l{ror*, ts L wk< /'(/*


Pryo

d^-

4f

h!

L^^e *L;co-*N,<-

sste,* ,\^ "1'N;b^v

A'so sfu<' ^'*L*6'* t i"^t*

!,'' & 7%.t ' -')

g';"Ln'

te 'lL'il*hi {- h*a si "'d; t\ *6*k'


(-o
lo
p'*
i
-lnssr,*
,,in
obeot^'.,1ui,lf"rk-k
yr^V
J'- s'o X"'L'k 'Jk
\ t; ?*[" E '-I;"1" f"^'l'L" a*"-h svzu-ssiw
,","*[* (.L
r 7G'4)

g'- l'y(^r*

lrl

/in6,<*,-*-

s,o,r.o

stfi,u**,hu.*-,k- J,)*,se,

r r*

Q",i.r(r o"l

Lt l'" L* - y^/-#' ,

Q=

Lnr*l

pq-

e3e^\f

rt f,o<-s+'^J"

, fu

t''|vt

";{'

t [n,e]+ fa*] * [*=J


pft = plta, t

'-o

firreJ = frre-J

s& &
[orrJ
fl {
,r&
trt
(. Lru-J . LB'J so,* $*n**t" Q"'tl- '' f'; ,"-"* \e4o "0" *'
bla,*o. /r-0!r 6-a-ts,( ^. C-=zpru]=.

h^

e g,,t^Ji % l*.-- L*oaual"vt 5-,^a v-&k L.rsa tgk ,W* f*?' , .i fwt- eszX<
,{rL
A-,*0"6,o-""-k ["
,
funlo
M'*f;/a
".rt,r?.vv.c
(* y^L

(b^ L-r.- op7*asir*3rr^r- f^L

A**.

l"

-,sro^Fi

sve {rss, t

soan ,'/f'oou

hr-*k

Esez-r.: :

tln-*

5 rt b,lo

uv.o-

a; *sl--h

so-".o :

't,oo

Ko,4

- 1t__Y1.

= ),oo

L u^ o^'lo {-fr"grhL @ i k

ffu,"=

j'ro

Ej s : 'l,oo

u[iGc{A;

k!!" /,n,sr- ifGn rh 1-t{bno "i L^^o


c"l.J.* ,*-Lv-(e L oLrwL *(rhw ur*k e si olln^f* ; ,^1"", "-(k
I^ hL *r" &-

un,r,.r,.;?"-"n

gaota

A+),

4'14 e-

l *h-

,,e.,t

; o$S*-wa .

Jrllr.

n,,.^it

fELLt

!.

6l-

il

WU* w

|
|

rrt*scua$LE

[."Ls^-J= -y'o,Ba
u
------ ._\

.-r.

Do,

r'3'50
{,oo
,i, to
6-00

." r-rpl *c,os *


>{;..9,0O- lo.00 1I,00 *
r:. oc rt, 00 II i

|
|
I

vt/ . ?il=Pk,t

Urs''J

,'0*
,04
d

r{

( tt

I n(r,3-1t;00

aasge+alc

iltr"]

* 3.0
- 1.0{
* *.f,?
- , g
{"s}

1,oo
oo

: rr

t cs Is"J

:.
Jpx--,'i.oo

er L*ruJ= eT"1

[r*tsl

fua.zloac rlat pa d"tte cooc:_


trel,{oBl dcllt rprctr !s csrlllhrlo
axlle
roi!rlanr.cquotr, i,oO.tg"? # *t un *ej,da
tl(" pir tl {tlr !{c.r'. 3,00 , }(o. , l, S.
I
rtr(o,, ' , o0 * dn. * - 9, .'

qLrr4-

hR^r\=

IY, 14 - yrrrtrln ln

'5*

::i

-l

tt.3ll
t{*t{ &e
tt,lal * rt 80
:l.lr i -. l{ 5{lI
:.t0 * l?, r0
:r,rs I - t*, 0 II
rr,ro I -. 33, 5l
I

ill

6{T1

lwneJ =

Fl

Uu'-L s*{1

Frynr

7--

l-

r.s

roe[Fr,J toe

F:,]

IlgJl

ros[#J

-2
-3

/:\

,i

-5

la

:.ti
.j:
.t

t:

t::
t::

-b

'.:

-8

10

11

1? 13
PH]

Soluzione acquosa 0,0100 M di un acido HoB con


plql= qOO pK.,z= q50 pK.= 5,OO p(ro= gr00

16.; o

* I't, {
{.? - lq,8?
- 1, ?- I- r;E?
i:
-" ql?'
- :,16 | - s. ts '* r,16
* 2"1 I * .S "- ?, 1u
l"; ri.lr * "t

3"4

3.t{

t. {

{, r
- t-t * . 1.!r
.* *, O+, ;*. !"fi: * - 5,{
; e.lo *:'- 23A "- ?.J0l
* E.0.r * 3"0{
2. O,1
* ro.oo : {. ' --- 3,ool
- 13.00 * ,00 - :,0
- l{.oo * .0s - :.goi
l

I
I

tu
a,R

ggailzaB ilE

wma
Ta.eauzalgtw

-1

-7

-*'

\e*sc.qraB|tE

-4

"-;*?3 I -" t0;50


* {,{ l* 1, j1

l-+scurursioe-

2134

bsEBl

h:]

tn*(x8'-i t*ei*-l

wt
Cop.TT-

log c

or F.,-)

W*eaa+tlrl

ra*'suueaaits

WEE

'ur-tl.;.

b-.

. J-;

/r,(!'nc,.\b l-th*ut

wgp*s^hlo (o^ &

utYvc

L' Lul^b"*'\'-(

su-i

o,.1*

\r^. ih

5!&4- *"h

(;

'

J.,W elvo-ar, ^ (a -no / tar t 4a1 ,1o4 e4t I r 1,,,\,o,v.,o L /''*"1"'"


"I
wJt^; , +ir\k- ,ll,t- .o^.t,.lro-2.\-o kh&, /:ulL' o.ru"d, i L' h t+" {, 3 K-c^e rh
srLruv,q ^ 6pnzrv* tt, b^'*; '-'A e fu[
- e t*vLub,.- /r,ll ul*ti

?q,,lo^-L

/{

I:teot) := L
F
L-

,t^s* df I sii"

Q-r-")

.t rort

0-r"r)

f,lrP"ol

C"

Kql

= okror'F

'

i,*

s,s

,s

,3

;, 00
t,fl*
t, ss

$,t
{, 0l

T, &s

*:.

11oL

q.I
0,
Sr

,'{t'

q' q1
0r1

oi'r
$r!

'" {.{.

0-
0, *

, 6

..0:F**

10:04
l!" 0*

"

E'

oror'

0,,

,i.

0,4'

&lt3ot -

k,n-h'

'k,t

s, r

, '

_ Lrr;J ^ ys,, .V^,t. Kq,l

**i *
o, -

x3,i

Ko,t 'lQ,t
oro* 'F

* oa?

1.8

3" fi

Q-,",\

xroi- ] et]'
.. -L-

[, Sr

, fr$

dxro+ 'AGrt

v.-po:
1

*-F0'?' iI

pH

drll ... f""t,lc dcl *r's!


i;;i t" asqut. !t ! r s ' ,J trf' ls'fra'

U{"-?"rbu"fnoo

rALLA TY,T5

G-r"t\

(!-,'E\

'ke,t

.n Jo^L "l*-'-

,(,.
'[tPo4+ d kr,oa- t Lur,i- t lrrr- : 4
,

llo(,H?b,"*L n

N'dL^

F08E

f A

u* (4-tr)

sovt'o

a o&,v".o
*

*fu^

lt "'l'";
A-rl
";il@

Atrw

/; "C\t;tuzrvxt

sv\-o

ac"/^o

<,o*Q,"t"A--2'rro"^

,J-,

) ""1*- ,rL,-(-.; L 29'<

p"*loA'

iwp*y*L Z" *sL-o-,| "r''*sl" " /nk


,(o!-'!-'

A-2o')

- 1r-l-d'

#tfr-'-

/ai

"

*h ,
*o i

rbt",.'

'ld^r^
.

1,4@5cud,tt.

Tu",

Ffi4,

Jo c-sl

,co P.

r- Fis.8

1r0

ct

qe

\l
\

0rg

or7

0,6 (

gs

r/
t,

,\

->5uroi ----'

l-o('
I

Hfol

Hfor

or4

I :l

or3

0r1

po-

n
;:t

:.r

l:t

i:\
!ir

o12

\
\
\

/:\
/:\

2 1s 14

pH+O 1
lrO
0c

0rg
0r8

ru

O'7

0r6

qs
q4

Lpor*

*rr-

.l-\\

HPO;

\\

013

0,2

orl
0

Curve di distribuzione dell'ac. fosforico in ac'Qua


25 oC e p= oJ M
.."........!-

11

,4cr1 fottQaoya

6^ ,t,
h,/J"

5s

D'/4.

J; '!/-(. gnv'_- ,talo s ,aossu^'a 'rn-t+vv<'- & bnuzr[^*v^. L'


,*"(rr-( e brl-{. /r' u/v\ y*-!-ssi aa-{n LL"&- , cko so,*

len-o-

U 5f

co.kr1r"r-oa-u*h-

g^*'":2

DEBoLT

rh .y."(;L*v L i fo$so,o lt,Vl; *'Lo

K,-,,=ffi5

f r,*l=+= +

rcLhr,'

/e=Ir^oJt[n^-.,rJ+ *b,-J,

fl.ELE "l-

B<.ioi

- kt iOo pee.

E /futo

De'Bot-E Vrprno?tat1 cr *

l'oo:l* kk "C,2/4 *yr,* ,.'tl* /soc*var',* J,!.t(.'raL "bL/z 9*^.


Lb . upgry*\o-r'o "t; a^/r^& ,@ sot z"v,< o-4Fusso, l; Jr< *uli @ a

'{ x,"L a J"L"L


a
e
{
g*
h,k
T,",{^'

@ ,h
tl-E

co^,s*l>*'ei\o"^a

LkL

/n'U\'oc^d'a

@ e G| Ytl* k @

u Kurn 0*- *rhk J; d,iluln: l"fl' au*o "Gb'L tl*av; f * 6o-sst /"2*
Dcro''- estl'aL to't;'/u ?* A*-ht
e-

'

Ko,*

Kw =
furo+\=

Cr=

0,4 [r;1

-rrl

@a')

tr+J

Lnr"l b"l @-t)

&;l *f.;l . [*J


fn;]

(a+zt

Q-z,t)

Cv= [nr"J*

b'Zl,o"

^">*) I

["oJ

(a-zrz)

si ico,vt i

(!-rrl)
o;L l-,,k l^- vvq- c-.,,'(2-,^l"o-=.v*"
ln*rar*.* e f"VL J"l!* Q-zzt)
'l')

{,'

4 ), 4o-6 t1 fox-J

'.

[.nr"n}=

fn;J

t+]

@_rrd

c,iee

./

vi[-

Cv k art
[r,lo*] l

lz

ky

-zze)

c^^;;

fnyc+J"

(k.,l. Cr) fur,,J - Ka,E (.,* G) -_o

@-zzt)

>l

DoD
I

5" k &",*

io^'t"r-

J;.*,/tcl.'s3\rr.r"

ur!-.z

l..*

vol;^

d.-

{-,*r.-,^

vst-r-a'-

(* ,-,bk-k

ional.o-.

f "".(!* JL""*

ao(',z.v*

Vv,.0-

voLi$ si

,l,oo

1;\ f1 /; t{c( (rg)

4,oo"z 11 J; w3c@n (l^q;\ Ko,T = 4,?4'105'


l{a,a
(An Luo'nJyoilv+z'w*
,U^-l"g A ar orool Yl e, TurVl', fo*siot^.- vt'.ll-

L *rn

ft*nl''* (^,-o'4;' - apo.t;t) Lnr*) -

L ;
C'r =

Drr*J--

4t'(5

[e;J

.{,}4-'t"-'(,(,oo..(it + t,oo-r;')

"{;) s-'"* --

La-] =

4, oo

' 4'3

- 2,34

ptt

E;"/c

(y f u**\
fcwjcoot)=

[urol I

=o

Cr

kot

Ka,

l,4s.roa

t',re"l * K*,r

8""ru

- ,(Co o51g'1- tUr'e?apYot v,'lzvv"su, (*

M' "r('no"o J'e *-c;Jn' LL"0'


6 ro'p.(f*e a,.o..tn[-ovnb^ hk-a; e- @ e @

Supgou*

&

&,vvq-

ko,o

[*= [r,'r] F,J (^'t


',,{;*- (t

= ['qJ n [r;]

e
Q-.1o

@c@

Ca

lob'{n's'

- [n,al tG]

iuu'4

lrt]

[*J

-- Drt"l +Is;]

Q-zs,)
(+

-rtr)

1-.Lr

k,,r

'/[ox-d1=[qnJ

(t

lqJ=
!
u

k".'t

D""rl+ko,r

(+or)
(t

Lr;J

=
Dtl

ko,*.

orJ t Ka,le

c't"o

tnA"

4- .-"to^H l^' o(-'u'Lt--

3e) . [ui],[u;J
e

uA' si

:i

[t

Cx

r"f =

CE Kort

K.,x

firr"'tJ + k,r

[rr*J

Kw
I npn)

4--

+ x",E

@-z.,)

k;
CE l(a.rr

fittc;lL =

t4-

l(",r fi'e'J

Lxrr] * K-*,"

[nro+J >>

fnro+Jz

K* k

(L'zt

q\ ,L,,e*

AaD-

g-zs)

+ Kw

,*o*^t{'

r!' y*

si

t^

: f',*l D:-] : fh.,rJ'


Lr,
G

( D

r*J'=

Irr*l:

d, f\otJr. 6

v.ll'W',x svitL

C-y

ton-l

cAczqlr-.2,u^.

vn Wrn

[ilrr,J t k",r

v^

<-f.*ziv,'r- L

;,/,

, L

t\o1
lo

Qeeoo

1tt4

L @

62t"<t-l>*zlv,w,

(D b,

frrro+l =

[,

,b-l!t-

.*ll.- (a-rt

ka,t

tt*

trr"rl|

drx ,Lt 'i{ y"rJ,*L- "(rLl*-

*- s\ (u; #os*^^r

@!(r*,;1i*-L

l,/if. X

ujs^utrG''lL-kvna-cLyoL*us''t*ot(t'oo'nk'"lnL'"b*v*'

-r k e- u5"olo Jk sorn,-*_ /- q^rol-i


s. *qaLbo-,o t*!L tr(-z,n^ ,Lk "r^h L
^ol
t

ft

oo s i

l4-zz*) W_qar"

"l.h

S4F4

/l

C, K"r + C=

<- y i,.G Kw

Ka

Lxg) + Kc,t

si P"; szu$/^a'

sFzsso

Sz

.1.)

frr*]

@-n*)

/,1,/"

t,Lxo*
.lrl-

Irrro*] @^ k

Q-r,

f;

.'5 A't'' 5.o

i{

't
."sf
svcesivc afTr-<..iw. +,u , ,-l.r
[rl"r3 p
e
t
Q-rrl\
L co*c,.a},oz,,* /rlb *Lt* sf t c a ,-t*0"* Llla- s"l^lz (1va-z:,v'J / ,* -,LL
,- k ,{ "*{'n L' Llr"! '

\,o-0r*

*tl*

'"ht- o*"1. Lz * ,yu'L rh u;"rr-(* s-l-o Fi h f,* , ,l koo*


e?'L?1,,M , I
slr.ss, st'
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Iy,t6, - vartrzlooa dl lo8 [xnf] . loc [!iH.] 1o fuozlooc dcl pH u 25 oc.a .' o,l l{ pr una soIuzlooc lcquosr r. 0,0100 l, df asloailct-

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a 25 oC (nK{r= q38; pKqz= 1Q32; pK*=p0)

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tl<- ,

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uw-

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t

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= Kq =

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> K51
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b"fu,

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= Lur.J u [uJ &-r"s)


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ur 4

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io -

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u^4- t.'s< l"L!* gI *4 v^ qiL
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+ Klor
= &r
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su,Lc

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l* so".,i?io/E pe'sowr'ra

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oni 2rb..r- rD ,t,-

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t, = [s;J '
s

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k*' Ko,, ' lf t,. * |ern*J) r k* 'kr,, l kn,r k "- ft, lJ
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=
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fu, t

k,,, G-, J I L 'L^ti**re

f^ k*tL z eno ct; ccl e i,(1o : r*J r frToa) = tro'J * .|rr|


s= Ur*,)* furo;l + [ufl Qarc) i ?r.^t*L
( fK r
, ff
l,t

[t"J = Lrrr- J + L"r-) - ,*4


lou, Ln*l =

/s f,^,"')
fu,ot

s, fi--. tnr.l'= k* - Kn,n * Yo,, "Kg z Lrql ld-sr


k"r, + [nc.;J

Ka,t

)t ', tr r".j

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Kq,

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l',,*'"' e"
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fx3"*J'=

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,t[;

fornuJ =

eri.,r-L,-,, LrrotlT>Kw z
r,*^

c.,r.

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fr'J

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?N=
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pfr=

f^b

t(*o,, !rLo,n ?-ttt


tr'"

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po,t"r"t,*a o, o-( t1 r 2f'<-

&bbuL v! 4-

(*"r* =

lZttrcoorlnnl

,/

h^

J',^x.,,

fn,,, = fo,-

*V&

- y^

gkw +

f*o}'

r, L :

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br'l - ltlg
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p, =
2t

gr,^t *ho

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r{'a.

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(-*+ As)

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I
f ';* J

32 = !,o4.

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f*ro1 = ,(;z 1 l.ur*,-) ,oo-t

'

"-.n

ot-='(,o?'1'-a

"

-lo-7

gk= t,oo + ztsj -

-r_b

oreo) ,

/or**

! g(u"),* ! e kr,,)^ @-tt)n

(a*3,o

li,,r^Lo ,.J'=
{Uf^b,4^
la

pit=

t=orn,1

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"' p k"F).= 4 ttr p*

@-tr f

<fr+' 51 *nt

4,;

t"^rl= 4,4"ti'; [,n,.ot<)24,4' ,.'

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s

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s "[e.,.a-

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frl!,, L Q*.) e 0?t d


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= [nr,J * b'J @*2rc)

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/"

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s"L ( rh ,L pt*l Cu) " 7*-LL l; c R\(oo- ,k s,4,
e, h (11- l; fo p^f
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( rn ,l ."nb );
c-.ih,o l^y

- t"o t<-sh ?H , EVo) 6i (oo [r*t'-''n'u rispet+' 4-

fcesc.,ox) t

tclx? n'a,iJ.

L U4q4 s dlua e:
L's)
f"r3roonJ= l,'x) Q-tt,o
k k (+-tqn,Lis) ;
cL,*
5isk'-*
k
,(
"<-'' !-'*
&L
p,.
E
a- [*,]

(" %. 'r,r) ;

T-'L"-I

I t,,^ln
t*

ocehpL
P, o*t eu..11,..*k {- pl'l 7io/ , ok t ,t gH J*11- .',y'-*o* "C
L qp.t^-or^av *-tL <-* tre.'u*: u*'(.k;
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"
(t r,r) < f"n*l e <-hq fca,co"J : Dt"no:J ,

Cop.N-Tig.il
log

ros

's[tol

[cx3coo:l

i,o* [.

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{,,,

[--r]

-t
-2
-3
- 4, 36 .:.1

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:$
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iB

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12

pH

Sotuzione acquosa 1,00'10-2M di c H3c 00 ht H4


a25 oC0 -0,1 M

'-/*Z

U*l gr(^:e,o* o-T,osq ,il

a,t\qrtura

! /nv-*,,.^o

E Br. cN-; p[*.,r)*


g b<u,T). = 4, E3 - e [Ko,T)" , g 2J

[-q-r-=NU4

oro 'fo

-4163 o

o t'( 2',t'

L i&efrt

f(u,E)*=s,s;J

I"' L""* '!l^ (q-.rr) ai ,,rn!.;


lo o)t

o6ro* : 4,7 - 4;"

5,33

&o*- = 2,4 '1;

5t o!-uL,*.
Ll,tror) . stil -no4

(fi=?,oo+4,6r-z/32 a

-i';/g

; [.x)

-- 2,] -.to

-t"Y(

: f.*c_t l-"^/(
[rl-J' ,'rr - 4o-? ! ,.4;\ d)"*ft
&rr]= 4,4'(;' = r-4;t b"lk
funorJ= rtz\ -,(.o-t

[urpJ= Atxf

5i

<>tttztw.

-4o4

v f, -4o-) bJk

oll L lo<. rcoo-^ f,-khtf,k

srr^.o

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Q*h/t r (u; vrvl4 k

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l** laxz-}tsr* c,,^ a^' ; .G-k k .-rL * HCtt.
TA- &o,1*rnt^* Lprl^^^r- "t
f*rL a)sleuq ; nr-'.,J ,*tk Fy- <-{2.
L u,,Ji.z.* /-I'*>q r ytLw/- J.L u^ (;rrrlU ,,*?-t-t, LL L ar-,
NH4r

t Hzo e-r [nrnJ + [Hro*) = [rnrJ + [axJ (E-ro 7-LL,.

_ (" ayv?.
"[q

L;rc#ov--k

,\r.{&r{- 6s",^o

f. *!-r*(- E{- t t

; !-6^,,;l; J; E.uJ e k NrtJ (*


eL [u,o[ AF*:) 2fz
" ,/.r/t H ;
,-Ll+*

Jt!-

Arturu.J

y\-?1 6'^4

viy-rl-l<

cca p,,.t-lt L!- LTLN.J

(*t l;

trll" hr^ f-b

<,..'*t. ', po; o ,1"t*r<)

&- atrv!
Jsa^o

l"L

%Eu-J .

F* ut,u.!,r,*,k

sphua*h;

% trq
,L^-,I.,o (-v, b r,,ko t
1,1"

!4^-

(K ,o.- f,*k

cotuv,,,,1u< rcvuo

Ls-[k*I (r"^b A. )

Con

+tLo

(- rcfr* A %L"4 (r*t- Au);


{ l"n

assa"-a.

c-.,ry,-eso

4 FruJ , [*rJ )
- L,*.uJ c- vo2yvu J; F,r)

t,,a f*.lL- cpmV^/"-h .^l A^ (n*

t\^ 4r\fa a-L;Jo L

g.t

fi*e

Lr.,{-)

pH *nV" J"'k

P; J& Ao o- P , [on7 lr*tu,^L& ay,l{- a- F"rJ


b%t=2,\ "L 7"lo P)' r*,t*k L k-s+4b) /.',)r,^.:
[n.uJ = [rq| U''nn U)
/- t'o)
o -l
c-"';?-/*"k
{'
P
.t
t!cpu*lo
,.JL''klt*
?l(
lb)
-e" (a-roo
a- zrc
" v'ln'l
A 'r4 /,( Jrlk ",%oo* Zz.f trot\ d- o, o-r oo H !) ,**,n /tu*o.-L
+@*,iL tl [trc^t) = Lrnrl 2 [ru'J =[,tnqrJ = -(i2'3'
z.
tl-

1u^L

Cop.IT -Fis. t 2

L)<r

logc

E
o

[Hc

trs[HHr] ros[o

=
,o

GI

-t

-ot
o
o-

I u,r,

rr

- 2,i'?'

:1

-t

ft
l,l
o

-et

=
trr (J
L'

'46"-

' -7

o,

-5

c,
N

23L567

10 1r

@pH

12

o,

2o

rn
f0

-EAte

Vr* s.b*v,q
han n -nlog

3-lNrfleo-J

5-l.b cro1ootl s- 22 e 7u*ttrt

J; Llo,-L-,.nL l;

eclvosc-

cot/t (non;o

- ?uo e4.*.\z

c.,-r.ztr-+^

t+

c,,lr,a-

"'-4u

*o'* /'' ,"'n.']*

t A un "d. z J,*- kw /LL,2,.' : H*; {:',^


e .GLL@-"":'
?t- 0 @llo 1-:srn-t* v\rzur &-,os[,*l,i ilrk fu

u*hh*"

bb"!, el

lrrl,J;

tt ) i uleLk ,
e J"!k (f -a rr) ,i ta
yt fW , fucor- J - S, r
(a-urr

5t

f,n1*r-

oL

*t'.Lz[.u<

pK=

ry

= B,?

ca-. <tt^[,o*
-

c!

'(

3i""/(

-,- l"

Cor- \n**k

,\^. ,-?-zn

,*

.a

4" Poz,.,"j 5-'o ?-,b y.Lk

(-V,-

zz .{: Ho; f*"^yk)

*!!* Q-rro) ((*)" ' (r,,r), =!,r'4;2n (*,o no'o.e -16') e ,*s"". ,*Lt& ,yk o
c.o^l-a ,!,fi'rp1^r.*-u . {l!" -.h*{'. dsJe.
ko, ), (r-,,). fnrc.r-J , ,i;13 {",^rL o,n,L.
$ F*- o^.[" t*trn,*,- (W,4, , ('l,* i>p1, & trrq] e r 1,o- ,'sc',r k [<-lr* hj.
C" ,!- *l* A pl'l ""2.*LL = gtz s', of co.Jov
.-e
*UrS=6,)-70t; Luil-=111"(;6 ) frro*J= 7/3't;r ; L"n1'=2,o'f;6
P.ifu

Cq.N-Fie'13

('*r)

f'4o-7

^=
PU*I* = 6t3

tog

(f",^=B-4{1r

r(k,4u= '(s't

.l'r[Sol

' r oe

[xrc

oe

od

[xc
ros

oil

[c

o!-]

ro e

[o

-l
-2

{ur*-otBc)

,"'Bl

-3

(ron). = 6.to-7
-

fu,4.

3r3--C

= 4'1'dlo

-5
_

,"i

s.Z-

-7
2.

i0

Eqt T

8i

rt

r dq'
pH

tz

Sotuzione acquosa lrOO'10'M di NaHCO, a


I.0.1

25 oC

I*a. l'!!"
olk

1,.n

[t,*;J

'
'(4
(4 -rra
-aa

"o/-,^ *S*r
EB

4;t

^r

Jz (a-r,+

h , .k

E-W.

Lrt)

soll;,

Q-t.r;L.'

r/"r* h

c-e,, *tr,o,

fuc?:tu^*

" & 04^

5t

d-h:

[rri)=o,z-{;d
iihr^-o-

,irilo\gon

e paolo^+ rq

litrl[

vt,

Ur*r\+ lnol = kIJ

rt

3.,,aal

,J-k l^

["xJ 1a-za")

@; o Hro

y,vL'

e'

lt!" Ar[uro;l , uk& p" h^-". k ,-,oun]r.nu- *


L[teri
f"l!.
b*i
he ,n0.'u7,,1^L* /; fL
- [ t { bll" *'sr* ir,n e'teu'Q'
o,Sl;k co.,Lr*l-c- gol 11 (Or^,
l-,t,",01- J; fil ,
,o,
*r)
c
(f,,u
N.i(@z
qolH il
ifH=
&
nLi.*
[oc"r7 (o or. , r-) e 60-t+ s', -,q$a
['-\,*'
e
Ur{
'\Pk'
trlsr.<-

c2,^

r\^

ri g,s- {.,^r.-ur,* /,\rrk. & p<to;) , e, h'*"b ci-ll-o 6-slfl "L'nv''n k


,"&o.-."*r*rri,".,.k" G-tsr) e ,'' (* Y;U\'*'L |-*zL*) f t(' *0''L il f'

3) gg.^&,^L ,u

zse-l<

& ,"k f.a.",V

,h1, ,-h,^* e Jrl'oa^b^,t ,oa


yv6 e-w,v*-(lul-

e-

@-lrrt,,J

.Ln

'll'uy,,;(;Lnv

, u &

=ro,L'k

uel-^h L

a4'. 1,oo - ,(;1

(; i
"(-

&rgx

a- zroz " /-

H - &^

t;s)
^

i*e-e'h-" , (Dt'<-

c.q@*:n;ffirr. -

(X*).- 4,il - 1;14

[++s

Torsov-o fu "ll* Yf*"si


[+*a:1 " P-lt] A)
&t
r,,L I KL,. < Cs e Ko,o < 't , i -.1;[

N'llt-

(ov,

l" (+-*")

^u*.^yo'' :

La,l'=ffitu-u{.
&

Pl"hhk
s*LEt), ti

rc.r-?<sr'rr

(^* ,"!. s.0ue.1 c


[+orJ= IGJ r Cs, f,^ f"( *-t^te

sot^-o

dk

gLk+B;

t,-r 11

/
*
f

l"\f; 'L
"((*i,h4eu".c.

4,oo -

V,,r).=

-
4O

- Q-vl,

srOuu* "*pp*s,n)*'t G-

& @-rt / Q-4) e (g-ttt


Ln* -- z, s s . .ro3 J/e
[ra1 - s,ao- 4o-? N/e

sento

hs)

"

,i Lo,

"4

rt yrtta'vL

'

[*-J. 2,81 ' /os e '"/e


ItJt* , [oxf = trc -,r;at S'Y(
{rs6 lvo-L F*.h ,ol *,(/" <-*aCau^+ ,r,-L,^^r^ ,
i,aL.,t.4 + 2,38 -{o-3

fl'r"*JrrgJ

[g'J

r['rJ

= qsg-fio-e +91o-.u-r| -Z 7,7c-3 /

1prosri,."n-a,u^^

-fh;k ,r",*lo 6 Q-lir)

f*rb

(aso

s)h;

2.st-ln;7-

ef r$"*,

ot* (- **-*'^ f*&kJ. .U tlg- str-Lne-J * Cs - }-- **t .r-so J^ltL (a -.1+ 3 t

{-r*hhu- J&* ,., 1*uC, p.uiot*o

[lrdJ=W

1,8 -'rrt) r (l,oo'tia

'7,oo 'to$-4too {o1)

,(-oo.,(dz + 4,e.ts1

,tLk.k Kqn 'ko,t L Ko,'r = Kur' '


Gr"<. i v..Q ,.e p;* L;u, /tL n,*l-*

h.ov\

s frt

u^7('/;,o*

t^d U
l( a,

F"r|ts;l-cs
t4,,

<Ql e ,k-

1z

(a-lrrtt:s)

r - krw.
Koo +

.l t *AX- "&

?il.o sgr,tk
i wr.LL

{r- l*

C5

,*

,t .Qp 6j,*Loa

t_

sr ("o *(*t ir"e.ez*

o-

@- sd a)

(3

r.e-.ea\a^a

d'oo.rr^A&

y*L|;{-J* ,or,a sofituvn kw^l. f*

offlr<

e .L
Kn,n

sptnl<

tt,h

; l*"or*L{, nsf"k r 4

{".^*f- ; ,-.LJ; L;or'- /"ll*

(a-la

) "l*

'.

(t-*r)

,-

5; ,-1"-L.* y^v,h' t
[ure) .

?,a4 -4o\

co-so k
f*lL

t*(k ,' fre). lqz-t,4 l-";/( ; [s'],t,tt-'t;!/% ;

*^I^'t,t''t prck^.\^c

t"'LCt/*tJ-

t"'J,

r,2

ritt

t^[- ont,' 4'; L' , ori

l'W,

.,o r"^e

Qr;".h' q- e-pf,r,se;b,,.*; /-k


sisJ'uc'
/'L
u'okt
e1'-z+i
J'h'
s.llrfnk ,&
t fuo- ,"lr-!'* "(olh g - *a) ;
5or"o
vrb^t!. e "tq , ,!. y*it .n-t , t"t
St4? "L fW ,*if- (+-.f l )
t;
,n/o,th t tushiur^L n,o,=
Lnr-J
^lo..
f o.-o

h'}t -'k i 6t'yloh


, o{<wL4 LttrorJ>3,o('ai| 7-iY( J' pr'oli*rr-t<
, ("n,1. (a^ i{ *l*a J; }roa t-i"/C ,

Cg= {,oo

,t^k

a *o-[er..rlq

tfii L

- 't;t H

; vecJ,u,k

h,r-- '-''*' A

vd

oly..Hrr,.o

"!"*r'bk

,uLfrz

ort H -

p. (4-str) i &ilu,+ ,,wf,z [uEo+J ' 3t1 - l;4 t ''';/e .,l- *n


"
*te;b ,.l,- b ,-*La"'. &k"-"euh'/l,. ^- f"'ll!" ,.'L*-o 'n- .
$^t**,^l-e td- sr&a,'..<- ".so!*', (4-sf 31 e y,,r,r,as1;o cL* -L t* rc.oa.iv; ,.-,keh4b

r[1. s,&r+*q

,tf

l-u.o+J =
L-

U<",4. &n'). fue-J

@ql.+[ueJ

(o,*',b DsJ=c, o.ll,* {./a


d-

*1*l- . [uro+). m

s,r.t*t

c-;

[r.eJ=gu-t; 4e ; [r*7= lo .61

(a - sa a) 5

l";* i [s,7-t4.r{') [* J- 4$.{;1' tj* )

9-L.*^. fnro! + [ilrq ? [ur-J * foxJ a,q.tit = s,d --ro-r


h,"r i s.lL{-k r."" prsl' t;4.
<-*kav^+

y"!*k; Lnr) e- oqLoo (,; Cq,so t* (s *\gzk ,l ooso lc**/n"J<' , ' &' l<'
/t+&+L
leozr\nn^'
f*khl;.t* sorno f;, s7)^11 & aa^rs,.- Jr//- /;{niav*. Qrl'l) '''^'

,L

aprt

^* {,rl-.L fr

egwssito*b*i
.2

svccz ss"t

*JW @-rrr] gd, lA;

Lr'-

d,r^'

t' [n J.

(i'

?r*t- "s1., L it'L[n-.k .


- r!-. frr^L b,E = Kb pH (=o) e
D.o-

Lovr-<,t

L*ztr'"* {'!-

- s i 1"t

-r*"p(r:/,^.ra

"frr-hue-,"'^l<

,Vl\pr-,t

*k I^!!&

t"'('

L *!rl.

sVr"r&r^.rr^h

7'o,,-,Io

/e1..(.'0.L soqo ""{f,-*-kv'o-[t 'L''t'r'c l**nL


prr/-l,^t"^^l g>*sota {''rsi elLL o lrc

/" ,*tb^H

frcxak "k 0-

sv cc'sri r<

,<-o-z'bJ

tbw- @"r)r.l,'' ,u a,*r (ru- + ha + 82- + la.o+ (r"'x ' K*'t)


d,,e rco*-,v-^ Esr^-.o: ll
ll nr'- + H.o = l("ts- + di' (ro" = Ko,z)
f-.*. &
L- t-.o* aa-o-2t'u-<- ilrB- * lQo +- Hr& + tl- ,t" fr*h ks{ d
fr"r**Lr{*. t\a

b** "!k

s'!.-a-

eil=

Kr,

qu,t''L

7w

esrz,L

*2;e, q G-rre lX)

t(k,, r tf*o,, (,v .ss)

P"-

b-6r .*L..4-v F; *"fl--tsi


S

u>ot"o

ti

+Lr,

,o*),

5-

, Ao1t*t^.-) &prr\;1)

Hgr:

H L 25-L e /L=94 t( ) Gq L "'[*"t]"';sl"'


lr.0,(*;L, (fo,|*= 4,oo-,to-1 / (V*rr)*=4,oo'4ia e- (nqr) ^=3,41'16'z )
(frrr)*= ,,oo
e ?(E"rl^ : ,{.{, fo .
/ .p(k",.)*= ],oo
7*vL', ,
- L co,nl)3.r\or 1rcku>a f, qA ,,(;,nlb er-tn, /rk l^ HBr' H7O J:
"
z[u5eJt [n.r-J + [rr"! - [u') * PnJ G-tar)
.,o-

>.:{re;u* --f,-ro

oroloo

A"5''* ,.un"6* ,\. c*'sidu,,qo,<t ,*(tJ"


6,*/.* ("q 4<l)
(" ** l"!- L6 7rrrJ , et[6'7 L1tur'3 ) Lf brJ el !^^^- u,tr.,a y,* ("
t
o,otooft,
spoe HrB (f*Wr*t*) ck hr*a f*e/^ ,", s,.ler,o a. c-nu.^h.,zbv* 2*
7,w/,' f2u

c-rEi

-',(

"{-

eg*;z i, a,"--L

a,w.fo J^

a>Yr

0^

<-"'z('?,r'u'a

y*k;t*

?t'( Lw { *or*\p 7 <*\l-,-o- J'lk 4d Fu{ esr&z W&

"tlt ,oh^r.-e- [g''Jr br-J "- l-* 0,t e 40


l^ f"*"L a-che z [k$3+ p.) {>os,,*b& dy,l h . [An1 fd; U
A-r+ 4".r.r- , [rrs / [*,J r bn)
(q- t^' L'')
- 1*\"( r\^ ,*ob \"k*,*/L ,h' pt(
k'J e rJ s.,,o *o([o tzr'z+h<
f
e Ls'1 ,.-J) ,"^k e ,tte
.

^%.=o,4o

1,",Ls"J

J-ute*
f,-'v e* Q-larA;'J
[nrel= ,tf + 44o tt"J

- t/ brl., o/eo

IJ ( -. o, f*)
essur. u,ri {-^'h &' *nhz,.|""*- /j "frh l"!. crh',^e. , ofu sQ
y;
l*k
k /ot"t A ctrv' /,L 0,60,"J (p a,c,,,,"-)f&* ; s-JLsl-(Le ih vh f*
&'J o 'h c-'lt- U cuvv. ld q [6tJ f
N.c.l,* 0o- L.,ft' t'!. %
''no

4,4o

/r4- <,er*.n,.4^ Loz.b* ( = ,{, 40 Y o ,o'too fl


- fr"U" . p.rrk s"L

f/o;

( q'

I f *$ l',h".,,k P J^' y"ul<- d'* <orw '- tr pll /'g- sl*u"'t


,-0* $,.rltT ,^ll" .-,.I'au^ ' y'"e e! c' "ry ""lt & 3t lg ,
o,o4oo H lrl *.L
,-sste,,- o*J4 ,.eJo,,l -k ,! H lil
- (,'h (,/ o vl /-l f*
f
fu^b P t ["tgJ
I
i ln*,,-r"f& ,
, t;'6t^v^l-o ^ *f* { t"'Lo- o ','qyt^L ?'ufihb' ,

-i(.

pH ,n.,;sp^!*nk

I^d

ry,^atM*,. p>elr,,'-',^o*A

,-*l-

lle2* r ho +
ll ,u'- . wro 4

g3' + ft, o4

(K*,taKo't)

on-

(,t*,o= W.)

t(r6- +

p! , pr use-c- L

i*r{,k [!a'-J =C, =4@-r;2 Y7 / p^vL {k ^!eA


b,s) , $lrr/u.,y,L.

,J'-t.

fe

,rrlo^L; J; ^^*[*t"a-.(,r*'( t') , ' '-A.

o,p"-k)t^ -J'.-. lrl!-

U.,4. -'(,r,,"(K-,414 e @*,.,) <'

(,

1"v,.Q

$lall;t)

Cao.E-Fig.l4
Crp.E-Fig.l4
r rn

o [trshotJ

['ogff,t]

t"glpl

tl.-u'l

l'o!l

@ryJ)bs[?']

I
bsE

'

P'-

Q(Ptoss;brr-1

@,s,4
@t^"

oakl* pH
,lUi.,o ,tn orQ"a *''"k
(, klr'$W,a^' (to'/-t." tl

}*f1, .04t)

-l

4,4.'lo-t+
4,31,1

d.

x, -

t /lxKf

-4

-el- /
_T

\./i

: l\

16r i-4,t2

ls-a-t l-4,t

io,'t- l,-z,oi)
-4EE 4r,
1, o, 1(.t
k{,2'c;l
l--}E
eLs, 1tu.
, ?r*.- ri et, ltir!*hs't c-

.i

Ll

.^-l

P"..,p,^k-(={{1)

-8

f^

frrrn = o,e

o ' Lt

-t0
-11

1 Z 3_ 1. 5 6 7 8 T9: 10 11 12 Il
Uq,r" =4,2F- 40-'.
pH___:itr
?Y*=\,.y\.-t-,f4tzl't,5-o-' ri'r@
=J$r. ,o-'L
r_LLq{,
rl
It
Soluzione BCQUosa, di NEHB 1,oo'10:t M a 25'o C*{ / '
l,:0I M.
L

skle e-Wl
[s*,s, 6c,\o ct o\re.Sr U;V; )
l/"^ -l-Tr-* of *r* ,2U L.,..Lo,t^6-o-e,rr^{, / s = 4oo o "l'''z f{ J^ f"""L "*-to k
u()rnlln *,,na l*t',- l^q
, Nx4r e tlto :
".&*ir,< fy-L,-\.o- P vvt
"

u[HreJ* fn,e)

*RroJ = [s*J

+ f^rx,J +

'{gt-

[ov)

Q-'q=)

L akw
- )e /,t 3*-.., e"S-^^|,*L co4*olu.*', "LL- ,!!, *1* 7o' -llt Pi* , *"1u.
lr! 0%t rrl ,1"!. % L*o! * t*,A- **u,^I*a.\e*s 'k{. " f* o fr!!"- L '"1" fu +r4" g,, '{, s;s}cr..o. Nltat*Nt\ h!. a,v M lnertx @at)
f.i]r.4.'

L csre

,fr,{

* [il,eJ + FPrJ =

u.,"k T'qL M{4'- .l^,r- 7.rr


..(. plt loill slrs.',o,." bz H i 6,1.r-1lxal{B >.4n l/r^r^gr.<
teo-ywr*, lrr.yun:
1^r^&.
os*'Lvo' dL t &- Pfl -' S,z0 , 'io [g'7 (tWc"l&)
d,.' 3,lg l^L
t4* s''
(OO, 1= 21- *r,r) sov.@ l,os.^r^ti ,rf"k & f^rl r *lo^k A Q*4
sr.
cnna;s1o^[u'k

t;

xlvr[Ib

yr-sr-,l"

fortJ

turl

U-u',u)
de ; s dod'.- ,J'l- tr.tltr] , [nre) ; .-k si vt'*a- f '^ fV *tto*'[' 8,2 i
*frr'oj]) ,- or,^^!,t
- f^ pk * 8,2 u ft(- lrtl "is,0[e J^.L t4* .l*- {,&reJ
*rs,[.t,o & [UruJ ; 7e, *ll'ry,,(^6,, U (+-t+br) ,""- eseue. a.u,e.s's a,.'lofir
5\ gv{ c-6rrssii^vre &

pro[co-r'<-le

o:

F,*J = IrnJ (t-sa*{*)

,asy^lo^k */- O*1" ,t rLo,,o


NIE HB
f,r"l-{"
fX ,{rl!- s.&e.v*t J^ NL
bA[rrBJ = tZ Lrul e, y'tiatt,*
An
["1
*fttJ
c
LS'Luro)
/,L
t
? &ru c,jrvt
g,ts
I
topl*.*^k k siko*"r^r 'L*k ,t"tt* ("-w*h) ; l-!' fk ry o

-{

y** arl,l. oh , "A" /4 *,,*1.^b,k e{*"-r^-b,& w.S" - fral , o- i,t*J "/ * C^*rJ
- t"!-

p*L;o*.l i

so^n,

Il

,U

H{ + ltrO

ll l;e' + tLe
in.'{,!x r"r"reh. oh*,

p,wlo
.

P,fe'). trtJ

7*ot-

*,(.

tn .l* 6

NX: + KrO{

(Ko,,

= K o,*)

t1g' + oil-

(K"ro

" K*,')

[n6{ * NnlJ - Cs

E'.,e
zr,loerb*^

-p-.{-*t *. il &r{* 1; prot possuh-e ur*.44- Q-nzL;s) csu ; *4..'


J^ t*nc,lul>t-"'+,,'e (@o, *r).= *o'^") i, t*oh l.",,o ri
"gp"-,.frr* lrtt, -sh,^h

nsp"ko c (b,r), (*,"). tu'-I e (q").r^\a,k *


Fur h,qs.*,* G*[ (r.,=).
aQ) 6 Q-nz) s fr- {f,serr"o.ri o-: [rprJ" =@qrt (r",o). Jo ";,

. : ,(r",r),

[rt']

(il= 7@,*)^" tf @,,1^.


l't7.;?'.o
esse,^l^o ko*J* = s,3? e ((K",.)*= 1& >2 Ph =
=
?

?fr, tf(,,",il,- pL

. Dr I.o{" 'oL* Jrl. pt{ e p,,*,L l,*=f r- = g8o , si o&1,-I *{r"i , M o-,Lu-. ,^-r,o*k (,U ktAu u 6orr.) ; ,& J Oy,u /"L bsto

?W=0,'ft,

t'rlb -; ,o0'J }yo'r! t,th/,*


vel$o

(,

,{l*rsv"oa+,i

eora

l-k

U
1*?o*'\ "-[q

{'*k &

"'"ht'

rlsle.^o

</ f^&'

'

Cap&Flg.l5
-log

ue[rqeJ

-t
-2

bek l(zpz
c &lt
ItB Q,o -.trs
.-2rcl
H bL-f o-s
'-ir2l (x- 4,3t"1c-6
g^ 4,6'{o-r

-!-'

,:zEir..

.3

* -1
-5

Itzo-

-6
-7
-8
-9

-lo
-tt

2*3

Soluzlone acquosa
e
0,1 M,

,r.

579:9tOll12t3

(DPH

di

NaNHTHB 1,00.10-i

M a 25 oc

,',r *[ff]ridrllilfib]it*,i:,

{ t -'to-A

-9,&o

-0 os
'9,v4
-5t
),21

'-13a Nvt 6t1-4;q


'-5171

-0,t't

l.{e-

3,4-4rl

-'Lro3

Nrr'

3,4 .

ta\

-L,ol

SqLE

urla

ssZrz"u'<-

-L

LJ'.,t a-

?-

Hfl:

Hsz-

<-.^,..c,t"r.uab,^r,

"!1*.

= 4,*

6L n serfc- 2rz u 7,9'n'

"q;,,rlL *-to' /&1.., ,1, tr*"j


,rr-t^l.o p^ ln
z[rb| * ,sJ* fir,o{ = [e*J . [*'J * &r J (+-ras)

#ffi*

Nrt4r

e ttro ;

,-*1r4.

J; il* , r J*
zC,

[r,.

Cr,r--a) ,

- 0* f *s.e,t"..*
1,.^,*ar

d,L

{r- c^tvt.

lnfri

tttll-

M - UUt eu v^^' c-r,,e.,,Lr,.-t"u^. Lt*

p^,t-<. @|.{,rnle

D,;-L

[r! fll l; (rc

rnpp\a

M[an

.->

L c-.nL:-l,h{

p^

s"Lvwn d,; (Uuo)rre

*&a>.,. "{) NarHB (f n= |,lg

o- f t4 < 3,,tg (Lr'-J r [nJ\

g*h*

a_

z NW+r + H82- a.uc (*r=2.,e'<i'tl,

h si -k { ?tl t"ll.

c-v?.1)\?v,Jt^k

OAta
I

r&4

"l'v

ria

o*t;^*}*

a {'*r.-^t(, dr.'lA' r Nq , sx*ro,d.o

l.^.- fuo' csr? Yfr-sriuok

c"

?"k
M eso-L,- ' '(''r'n'pre f-II' ,-r*ty^/t^k
k
.
h^,,L P lill" c^trvl .W l* [u's) c l''l' %t*'J , /"u<- "**'")'"
o,oz
Q-:au-lu) ; h/. { is,tk Ue*:-*
o,ozfl) *?N
-,o(h"^[ o- 7l( r-.76^\^r U f* f;o A It L,"r] (*C*,

:Y;ffi

(f^ Crr" = ?,rtl ) (,,e'L s'('kn' 6Aq l'"!k [+-taeU') , tz^. plt I e 3si
,,"L .hio-a.qr^.-,k .l.. ('p,*l + [nrol) ." [t"rJ ) 7 1,,v'L U
st
Q=ror\) f\

d;

rr-3

L(yrosS

lti'/t4

o- l

[^,4 = [tr G-rrt

. +--

*)

{o i4t^c2*1**o-- 'J'll'"
- JrL g*h- s "l^o^,o^,c ;fr,,{r'*h , l-,w,_ d!- u"4 t- ,
,th" rp,ao.Y ^ '1''46'J " nL Pn aull-'lk '
F.,xo f*r',' '"Lt ;rp"F" e- &B'J , . [urr] eJ n
- p..,-L[ /l{,gJ
("

"[7

rcc.aror,.

f L*,o^L

[rn,J

5.fuo

llt,f
{[

*Hf

# N[,

[s" + flro *

+ Hror

ilr9- t Ott'

(t*''*Ka,4

(^,, = & 4

,*A 6"- ,( ?rt /-ssql*o ,-^"'vct J"lk


Cr% = C5 ,
[ore)
*

-f
e

,ror

LKu,)n

i vuteT'tz&a, { Lo toL

.-i

*trror -

,rrt (*,*r)^ - z (^,r)* (u,*)*'-

.f f^ (^,r)^= 4,,o-4,-7 e

[r",

fu

z(t [r**,1*
'rd

&firrt

crrst cs

"L<

Fn,l=

orron(or')^([",r)^

i "(f+'*
o

Q-rqgt^), n'r-t"[qr&

* (k,*)n

*l-, it:] -to-to L-

uk

or

s,46-aJs

- Jo F*,tL ,rr,P* J^ q kp, e tu frrn , f"o- e 98o / s; ulla^5.'* ; tJr; *,0* W


-; .rfu lrl[ l-*Ulk oJJ^{tn- e,l>o i 4,,',rl A,^h !-- e1vu2<haar es-ke /"1'
f,sJ"r-o t lu ci & apy*sr"o-*uJ /-lt so'r.o
"t!;[o.
Cap.M-Fig,16

-0i

{-

1t3? - 4o-{

^ r,ga

0)-

3tof ''ri6

'452

f$-

b,c4-'ti4

\o(

ry

8,64'6<

\,o

Hsc*

be[H.pJ

tog F

?rJ

toe[B

-l
'-1,72

-2

'-

-3

'-5,0G Fg2'

-4

fl1r

-5

2,04

\..
.\.

-7
-8

.-?.s2
._eloe

-9

-10

-ll I

z 3 4 5
2
E 6 t

Soluzione. acquose
e F = 0r1 M.

lo lt 12
It_s9 lo
It_

E9

t3

pH

di (NH4)eHg l,o0.lo-t Ma25oC

Qc

0,t'lo-9
'(,'(g -dg

th,

log c

,'/.k

4(

''ti'

4,34-fo-L

oS

-7r 32

'2,o

4,

-772

c-,,so , bPo 1*"li tre*g , e 6r'rp4ds-t' l; ,."*.il+^o ,L r'&au*<


&
L',g*J^gu,
i/y\ L.r* I"L,U 8e ., yn *;&^ JtL,& H\o , oulxve h.on.o pio I'L, n
ttl.olr,&"
&lt'aoil-, l{L e CL 4o a^*"ln*tqe.fvrrrlr^l; ) sru- L k c/t(&{,rlre ,*.
^b^
1,,,,,,,,,,,,,,,,r0".lila'

o[of,.(,

kfu" L-*. gt - .Ir. "o(,gzin,- sl


[un+J to*J (n,,,).Q-us)
=

-vnLh,

,'f
g
;

ht

.(k*\.(qr*);

[ua)

rd)f*1,&d.G-rJ;

d. "!r*_,^,^rL.0J1...__, fr**J r EirUI= f6J rb Q_lrr) ;


IL = tu,3 r [r,o! (q-u i
b= tt,%J . [r;J p-rz) .

arJlz"^.

D"L @-zez) e (1-nt,s)

[nrdJ

rk

.i l-(;.u

(rt,r).

t*f r(tEl.

Jn

(u*),

r'rJ r @*),

s-^o

,i* 0r ,.*k Pq LlC6) ,

r o&*\,

W G-''4

Frd)

sfa.-ti"o
4o 4o iw furr3 - f"{g t*el"*
"; (r
o,bhoss".t t; E,i,l. t *n nl-**- *$;rh.,n Zlr,^,t . Vu&a^-o .{* .o<i t
- fl S,;'yL,'- i* .-f,o d!\&- b"* &JL"&. g" (fr,r=.tpo o') ,k,.o*{o

vaQ yua-\o-r

l;

uns sr&a',o^q oroof se 11 Crt) <- uvt Lrt- t"g"(,

r^.orb

t-

ok

,*4

svr-

tt,.,

W*o.* o,^f&r.k:

t\., cc.-rs,o,

errfe; G-rrtr

H *l t& qnr gl , c.a+t.,t-....,*r1 *


oloof,ll ,h c.^1,. lfi&u AiLr"^ ,!. <u-so: fs., ..,v'0r,,rl(o,;' Bnj_

Jiso.,ufi ,

B; z

, h

ilO

sr&au* gofu. tl (r^) )l /-.;k

Br * IfBo =:

v r"' a^/e/It' vvto' &ao*

HB,- (rcr,o = {t*'l"-t)

.o./.naio*

gooyoo

7*k,^ ,-,oLkt

fu3dj+BU)=fcrJ*

[*J+

qno-.tii

u^ qL4U oil*sg;&.a,k Gnirlrr@^L b


44w.t-QaAoa,u* &A s"8 p*; 0- Oroalaa
r
u,
, 'L6;J: o,-,ros f'* e [nu"j: ?o.,r'o '*"0k t '; e.r / ossuu.q.do

qe

fW'

,t o,F''; k aV*

aelf awh

U'd) fr;l

''".

L*

'

ft{'o+\^o'ooroo

Korrr

oloooa

4,oo..(o- :)

[urol - q*Hru'

tnk J

{ ?n lrlh ,&n*u 5",..-' I'"'.' a- '


Q,vL *!!^ Q-re) tor) r .(is F* el

cbe

s,o

rrrpho

a- @o,r) =fdt

,p*tr

I'rnb^r

d*.*rL&

abp"fo e'

[rrn*J:

ti'fZ

t3ra )

y,l-*LL< f,,un d>ur*,n<

4r4 e I -Std
t
'[.e
e
[urrrJ= r,*.rJ s;y(
t"e-k ,,.1!"

l.'1,

(a-*4,) <. @'ur)


G [uro*)
z

rr' l.* t

[ut$ iy-#' o- ,L)

,^,**k*{- &*)r.

tr;efioo.r;t |,\u

kw = f,oo -to-r\

1v*,f' I"W.

si /*;

Luu"J

frro!

+ Ko,E

au 6 tc,o?&A

e+rt)

- Z) Sugp;wt* l;
k L-* gt

,[0.
aw,

r^"[ler& .

F,n

esseit-

h^L

[on ;

*yLfu *'4, (* /*"*W l"'

,^,(!" okrs" c-,.I,),b^; Ll

,,*tk p lrt,&

,41r.ssi"*2io' r-

6il't+g;

-----==_

sio.-

arrrrLk anust&- &ro*J


Qv,w/,' ,,rfu*

pro:h,ai,*^k

{,oo",(o-5

po[r--k \r*
c-on v^er- Kr,, = ,{,o-t;3. L AZ

-oz

( 'J* tie- ^tY!'k U


S-;*

(Lr.'

4.Lo?;,,,,..

@-*r) , ri

U-rr4 [roJ: tos d*% d

tr-"t*,*&(- ip.k"

ca-s,o

,{,oo-4o7

rl"s*^5 rk, e- Lh,orJ


,

i *o-t

l" G-rd JivN,*;

[q""J

cL k,,

G-.tx)

f"-J t KL,,e Rrd) + Ko,,-

(o,.uv.

gttg

f"" 1".- ,",t'l*

opy*ts),tuozn\<

t p f*bt

[n*L g,.r.,k l*
e "k k

s.

Set,,^L^u-l*o

,L

lfu-*'su^t^Y
a

@*sr)pl" 4,

&-au<

Prc^|c:t* i,^ eso-[.r

&

ota,
o.Irb<

t-o'{4

lL(,

Lon

lB

L6*hb,,.- l^'

f+ CL-= fir,o -4o-2 n ("u* r.o'-rr;1el'J


lg;J pu Co = (,oo .<r-'n Qu'c*e t*)
fgrnrJ

Lrrr*J

&rJ

fu,dJ + Lu,rrJ
?"Wl

&;J

[u;) Qty t;) -- A- 3ryJ

IBIHI ; f* ,; 0t ,'&zt* ,.&n


}- Truln
l"/r^^v* s
?,,r% a>vm>(o*/".,1" J p'^h P.
"' 2,L e o f n *ttrvn AL;' el;nun'< z,a

,\.o,^ (uo- ess,a- ,^^*L..,-t

f; oy*,+< yh {
p*Lo %8,r3 - %Dnrot
Q",\^{ (-w buo'^q
@-lrt

e{f*"sir.*-er\,.q

l;r) s\ 1uo- *.g1*rri,^n^- o ,

pe-t*U

,t

pV

, n! s pc'

,Ixrseane

Yfr- a- kt I e L

&rrJ = [e;J Q_ln l-)

J; hlL s"&:+ux- e

frril*
,ff,<

Qt+ul=qt,i;J =,IW;
f*^L J.!l& 6-,", b) . tL KL,r

b',{J * Kb,n

<y'14A tp.n

eyto

(,

dn.k

"l p,^k P

Jov<

i ({

rc,'t^wtt J"L

*!,J-

kss

b,!*ho

Q-rrr)

l'q vvJefvo"r\"* "Q 2' Erbo

ilrO{ -? : Zroo'4;t t-'0-/

'

[nr*J. s olynt t

l'"4

Ld

<-

.. -4,7o h "i,

lr;tT a,7"\

a\sf i,a luuh (zso k

r-+-oe&,^t

(<*tl

.84e
bn-

5- (o-t o

1/ 6.1.

(_'

*3,)o

{dl - zft?.

o*t 1

),3'1o-l

"-

6D

1,1.<"'l

-41&

tt%

,t'&-l

2A8

\,tg'

a ca$rte w$o /*,r*?.(b^\

v.u.

B; , ,.t0'eyrrCbnv i\,0\ d,\ ta *f L caVt* N 6" i( /" g


) *e-, L-c"r' s-lLsJni* *; t"'h" &l';R & ,.,.,st-"h "l ; 6;%* /'k' '"^"J+
, lnllL ,u.o-r( "rofri, ,"^ln^L usT o.r*l(*,L;Q A- a.ypt-ssiaa-a-: hk
C, ,c,tu"o v^r,*h * 6l; si f*c.^o &^L* .ek s-(rabi dn' o*rd^' e
oL' Lrs t h.Ls(; t^ yvo.-l'i t ^ol^ "f ^ 'o!.,k '
,t"

Szltr

cap.U,-rig.tz
lo9

to 9

ros[a,x'l

-l

lrt r]

to g

to 9,

[a;]

I|.e

[t,l
ros[oH]

[tt.o'

- 2,00(log c" I

-zl{..2..

- 2.4s" '' '


- z,z gt'j ' '

-2,3o(log cs )

'fr',;

-4
-5
-6
-7
-B
-9 .'

- 9.30'

_10

-f7

910

67

11

12

pH

Soluzione ecquosa
HBu

1,OO' 10-z

.1 O'5; Krr=

diBl

5,00.10 M +

(Ko,r= 1,OO' Og K.,n= 1,OO'

t00'1O-14

30 Ltj?;losvt \

AnPr"rlJe

l.;tq- A;b,--,,[ * un B-ttfp


- laua*ti r*' - oto s-0r2.,u,.1. J"' ,Ler- tk
b*Lt f,.J. A vo,to-?:lar{ /t-0- pH o{/*'b J
:; 'ti""l" "e 1''*'lilo'

t'o^

aace-

vvL Lo+'e' , ewth 5c

55ivo J,; Jr\ oe.b

OL'H

/ a t"t" k 'U eti{-

tik- J; .'n oppo*(v'< stsleno 'uL-kt"'


A,J r"W& , ,."7rLt ^k ,\^ u.f* r,\A *L )-b!, Hg e 6- ,,o L*n ,-^^U6*k
g' ( U co,.^"e^h,oi'o''* irl,tyei^r"r")^r r fa Lnr* *"*" io'.r,-o. , si ,J*q L'.

p.co^k u* c**lo

7-o"

fxyol = ko

ryfej

Jr* (6 . C5

s:svo

;(t"UJ L

:2 Lfuron) -- (s+ -tw""J -[:')- (4-ztr)


\'
* Lnr8- &rJ

bae.tt

a,-* L( L;%^-*v /.1!. h,{-9" L

at, Z

[r-r""; t*(r;'

W' ouL . /"il*

cow(Lslra*,t^t

'-

S. *.11(nO) '\^

MJ ,

b,-,sz

odrtr-

,-{-

.-erU

ot'^t-t-*a

^rfI-rlo

fnro*J =
su"{l^,--[r--

a-) , L**

k* L

wG*

0UB'l

nn

e$*^L dr1'"ft-'tc

1,,:1!'J .Ko Q-zal

a4

C5

s,Cre'"* l

coxct,^lto*;.or^s

"[/1* L

gi
@'*
e

ft g

+ B* #tu lnx-k o^"L !^ o.id.o JL"k


(* t,(r*"* s*VLr* 1nn,h' , l-7*r, a4-/ H8, gt
!. nr*h .-,;[, at ^i :
furor)

["r)= kn, Q-r)

[*" Cr; t 4* [r7


=

ab'.. 1"0 t"l,

e-zzz)

[*"t*[ur*3 = [uJ + k-) * ["nJ


(s

,L\soa'k

kkl" lrfu^ * p1r. H& -g- -

S. lo r> Wd' - L,.f) e- zs >> (pr,"*J - f""f)


nJ""

5,,,c

lrr"J G-r(4)

A-)h\

(".) U4u) ;

{*u ? [cu7 G-,rr) ,


)o

q",J
',

G+ cro [t,ot.PxJ[ur"!=k* cs - ru *
@+te).
\
_["rf
fk,eJ
{"

or,<-ss

b,o

ur^.e-

p[= 7(4^

".{uu

o*

4,

@' lo-2

H A *o+L --- A\- e lroo -tol H

* = 4,6; r &t #

.b

= i.

1*0h Qt'4
ft<r--h ,^rln ,{,*- 4d' '^*e/ J^" o;L 6filu"a ,
S) oqV* , un @-4. e f,rn f
,/'-orzll e t*s*rr-.L ["rJ , * fl(
s L'^ l" l*L s--a ,;*
,,*le .o- qo , f nsl- f"k

Sc /.ro-,-

(n-Xe)
0ril"/1

{.'o.:L

!,

e9,L

7w

olA'e1*t;Lnv

,L

"n

fipt

a':

*
Q
J(s.
[o,rrJ=

4-

l-,k ?J-k

s.''"L L u*zto*:
vwl

oyr-ss,r"s<-

nntL.

n,trL

B^ t'

Hg +

r-'^<a.L'oab'<

u&t-u^q^k *^

?u
(rce

bos,z

g-

H2o Q-tc*)

l*Lr. Jr,l.l'oub LLr& LL'ssoc.vfa

= Q r Cru e f*/k /r/l- L"4" -,^.,Vg-k t,,*LL" E)"Cs -Cnr")


A- au"t^[,aart'c l-/-,& Jr]tla .-6\s ile -B- it*,u
e.- & C= (-+(5 =

X^pbLz BeJ

= [oE*16-J,

Vr.l.

o hV, 6

frc*,n?-a.

l;

z,L4.t;6 t7 (fA= Et1y' cressl*

4,oo

.,r;t *(/t J^'

t-tce

L &g-

vna^vtt ,(

uylw^k .rF,^b 4,oo ' *a >'(fu Ji "/{*

l{Q-,

h-

l"tJ. f,-ofi'auVo
r-*e-[r*au^. ilr*yi.,u,,nIo swb
"l-ol* "Je & oow4*rL.-*'o*"
'/,r1"" el { pk so.n$,. ,\,rl,l.iln ,J*1, o- Z,oo (Ol = 116,) -. 'vJ; k

_
- sl*"^. l; a.;l- *r-kv + ,,r-Lrf, d; *Jr'o L /r^ur*ol- L
L,^*(.t

- <

a*-r:,

lr*

u)^{. Sr?^rerV.^.

ok*L suiy{rYr^/n {"

,,vnr,&re,, t
Sz

lvvnh

2,oo

la--

-<;' r.!ft ,J; o"i'l*

|urra^1"

(e *c,

le-J"g*

"6ur1'-

,l4o'0ci -2- n)

0.

fK= 4,(r

; ,;
f

C te *rk

fo

3,o

3,o -4o-z

qe

d .-l*k

ln'

s,iv

,(. pH so,r&'

\io'0o-L
2,O'1o'?

%f;*X*sr^< "{,oo.to''

?K= 4,$r bt

u"r-h\p

= gt<t

rl "U 'uL'

r'/u';J*'^

a'va<bb

,UL A-tt-

--liL - 4, ,o . t;7. _
g
lrz
'

Z,Oo.

io-Z + ,Qoo-to-l

[rl- ftt ."oW 4; otoz ''b, e f,ttv,"k, 0"g!r-uv-+ Lo, +d-hf',^&L o,btz'tt'L ('o6X:"^6 fTU h; iJ*2'''"t t"2l"v "; uL ato
u^.6- sl'au'^r L''l*'J;N
p.e.J,,4^te- Qr,nt Totitclh^, p.Jv*< ull- |'i/.ac.rn"U
-il
(cUPQ-J'e' sL l"tLt *-k*
/o.)a-zrro,^
*L
lc-l.p.,*.*
fril
-ado-L-n
obb'''"* u'>b "Ah"tt ' 'b 6rc Jrl!^ co,'ce^I,.gr*^a J-f^ eltV$tf sbss\ tl'
c4";l*;; P*bta
,'t r'N* -)A'' - o'nJb so- ,"'l!t A c';f'
s',a- e* *'&ou*.
tto*n7't't"
/t!' ?K '
s'l'a;
/*
!u^y*
-r!! tr l-/g s Lor- i aup\ &i ***[u*.a+r't, ^r^ (""h u^4 /-le t"hzo'*

esc,.,** k 'uq a?r\T''t {an7"-.' (en


Ci'M:pig'ls ,*rlrc ,.-t .L^ bt u .,-o,)j.o "-gV"nn)1 *
n 1*^t .so

0-

voz,"h-e"t,.e

5\h-Jvu otu. k

13
lH

l,*L **"Fffi-)

12

}-^to.

l1

gl^'

4-"\{{roa^r

-.!--B=

Y-Z

10

t6't'

I
I

'

7
6

-o

5
/'l*

--J-.--''

..-

--.:':

()

o
=

2A,

o
:tr
o

acg-f9rte

_j

,.1

100

150
'titotato

2@ o,ak {- s*,

,&

Gi,h&

&r\

c,\,a- lar1a,*.

ttrs<.e tA!.rPo

''<4*o
^/E

lotp*

Ah^.,s\rh[ &fl'a**

A'

untou (a*l-^i'

ur.-g-

srl.renb*r

lrffi

aog*t-

*y2,*t* "t vv,,L "l-t u"* f,+"le {

t^,e

F.^r,"A*-

Cg

L*-

i"&t-e- c,t. F , "l e.0^L; f Lub,

/-/k B / ^ l,o-r*1;,
-rrt r^*Fi

J;

vvg

,,r^"'o.-,

(4 -s rs1

/=

A hL*u" u"L-L*se
[an^U /s 6,**& ; /3 , bk
(; #^*r A fl' l+,'y*.

el

Marzr-r,rt
l^s

JrU" p*b*

T'ln--*rlo

Gvr%ue

*6J*

& A

oA

'k

/r11" akw

U (* JCL),;*,'^

'[/^a- t)w'rn't>$t-

A f'( (-t\fi)

e- -hf 6"aihv" -

Aabo b Beae ) *"* ho'\,o ff2oto


60r*(fu* o,n B p ,./1,\o- srLt>io* ,-c-r,t/os$ J ,n e,c,,:*a /./k t,'o..,.of,'pl'1-o l1&,
- (u^s,t,rob ,-w,yLt-**,.b 4\."oU-k) . (nr,tcz^L*-at^r- Cy 4l / u,gL r& t *
f
.

uvw-b"iz

n*^.p*k

/-k

f*ln t-kl" q7iv"k , ,*bAt

,k ;

e ?,1-e4

k a\. CL t*r/t . &ssur".'o,r-o tal-t ,oLo* lrl{. sv(ttztu* w^ *^+ y*e^Ltk*'t"


pL ('ry,*L Jill^ L*te.. L o*1n2'1"^* L' Zg.'*,6 Ah- "*,

fh"! t fear) -_ [qJ


P'lJ^'t

?'il;

l"^k ('oat* 7,*k b

{* G-t*) r'"t"s

J"')

cL

(u +f"xl

b,J

Lv;,,-

Q_ru)

s?zh.o

ft r*J + cL - ce

- f'ro*) -)

l"/H B{J = (t

t,n)

cL=

atr

L-,

Kw=

f)r* "k*).

CL=

olr- :oslihe-L

G.+
' frr,,'*,ro,

^lk

ok'ot

c.sh.*k e Bfi!=cL,

,'*J (+ -nz)

-rn)

*W

f"L- fu= *rrn* %, ^ =r* Lnr*J6n-br) e

o_ssu

,^r^L

l,*,

1Q-t+z) cll,v
,
(+-:+r)

'

frn_

,4t,*-

ylk

NaL /:

"H*,u\
P",,

a),"l.*t*-\

JCb

k,x

J onror

t@?8"
'Hrot \d

'frld

z(t-:

Pt=
Jn c,

-Lt

lril

_4

=-#

Q-nn)

A o\rr

. _t

oI nnr*

d4
-\to tqa

onr"r

.-zr \o o\*

e6*L

Ovt,-

Q-t*)

Jeh

frro

J?tt

fr,*

fi"
n"

&=z3ol
J

rk

f q*

(+- rru)

'r 3'"

'k,,,

uY\e

Lr* /""t. ["

\'(-nsJ

f ,ror I

Q-

r*s

ri,-)

)Z

f - 4eo (n'-: + Ln;*J


^ ,J*L L ,"!-,J.* k

L il,\ ";L kk

,,' t,o:

4\

/ =,,to (#,#

-tr)

(4

Kw

,B=

Cz(,roSs

Q-t*r)

k(t 4 -"?) *l!^ Q-r*q)

,.*;'

Sir*

5r

rrcf

e ,".h l"<,'-L

"(-

Lnro+

2,go

;:

e 7*l-Il

"

opP/A& u /-ru rst..'q- .-slo-k ,


f^ cr.l frr* = r-s*lk n r!^
u-!*,-[- uu"l*' 'h Cy e Kq selio c-s1.,rli , t^fr" U-*)

,'*v*ph^
'it "*-sc )r

^p""k
O._

IbA.lno

kf* ell". s'&z."^^


B-

t.{r"o

ov'L

TtrT**

4 fi^

l,l'opyu^Lu JrJt!*

*r*l'^?,.\x.r. yA*

t'""-

/.,k ui L

sJ.z^ t"Lt*^L .;,k

,\,.

.1

CX

4 W*N. U L.*. /*L rrn h/.(4- (4.. C; , si ,l,va I^ *,6au'r ,,^a


?t [,.\" ^u, l'r,n" *('- Cr -Cf ) "
r,*i,r*/o li c-,".L l-1, hon *r
.Le- tuD t l, f" c-,-^(e,,A.-au.. wL,uCL) J* s ,A!* f e{&"r\^,. cotr 0.
i,,o.0.'=

M;

L"r*

, ,fu'nf; '&r* t l.,o*Jo I = Cl , , ,.x 0" s,,/,rar^r l"L s{, t,,A


f" <-r^r,[u.s-zro^r .*!r* C) i lrL k *L,.* 4 ,b^: [''! sJ.- ,t Ptl

e'

f', T\

of "tt.W L L"* /nk t

4 *^f *,0,-l-

oq\* {o(/Z$^L *

s,

IA "J" f"

- 4 1.l++o sL (.^Lu\- .t,L f- L'4^ d; yLu

g.c,"*

".,'s.lu

(on(tz,(o.eh^.

q),

*rA', e- f/(, (, frrr!

?*E*-v,*A TA ,!k u*r*l.ao^^g lofr' ",L e+tt*+ ,1rr |vvkaA\ze.L l*0["


Lro, <-s c.ol.^r. L pltrg b*-J cao,'sp* ,lL y'"^^tih- dn' Lve %Xi^k [,
(;,czsso .r;l1k &L'o-c;L
.

fl - uu

_
uv{-

"t{r-,-*-o-

Ktr, =

*o1*** L tlT-

4,* -rrro
;

- L ,&r.*

W
d; p

cov\ o6Xi'^L+

fnr* =Er^ c

l;

ore{oo

deor(

X,

vtuano[

Ztu

e tr7,( n (k*,f"

""rlo-lc ^.r/"b&h),

; kr). = 4,r8 - br'


A ,-L o-;.G 4roo - t;L 11 Lo_
o,8o

^Lt'%,{ = 'Ly fa"- [.n,otJ = -b

[,.[!* ft-lr* [i.) e

o,Bo.,loo.46?

=-Lf Eo-tot =@
ro6yu^li ")

n7.,to-k

,",JU+

TDt-

L**.-

,rtl.A

4-at e ,*.4- t4*

l^ ^ff;6 le-r{r"-q J";^-rcr- u. fl /,.-^L'e


tttb. r*.e,vth.oer\^x lelU'o^t- (" t!!ll* L*) lA " *fi'V ( ,^{"rc *L!p
o p{--l ; ^\ee' *L p"'1" U 1"i*'4at2s '
rudlca ttagorr-dl unr' soluzlo!c'gcquosr"dlua
Iy,J7 - -icldor'!Etl-.onotrrot1co.-&
'''
*l-.-q F & fil=* coz+|Vn"
?s-..9c".' p' o, I- ' L')'L
, M fe

(rr,.* si r"e&

c^{'4

TABELLA

^a

tn'(q[zloEa. dcl. 9Il'-.-."[r"o*J- ';':

-'HcLto't lr: -. HCI I NrCl

'{

..:- 31.0O

{.

001

i'n
-- :'

1-26.- 1o -r

.- -?-0G:

+ HrOII

2;9-10:-

?;9-10-a'

'2.9'10-'

3;8.10:'

to"

1..26.10-''

2. d-

2..9.10-E'

0. 00:

I. 26.- tO--.''
1,26-10-ro

lr'.00-

1,26. 1o'11

2, g -lo'.'
2,9-lO-t

1,26-

2,9- lO-lt

8, 00-

9:ooNaCl

1',28-10:'l'= ."--

I , 2{i' l0

6; oo-

HsC! 10.:1 tti

.-----*...
rlzs:ro:*. 4i2;9-lo:-'':
'''
l,'26rlo-''

' 5,00:'

..'-.

l2-3- lo-t'

I*00-lG:t

2-10.'

Jt-

F-

2, 00,

lo'r2

".(-

,o25

t ,Lra.ro^. a-?nso-

A - ft=g4 oJ 2roz ,
P"t-t v** q sa..a ,<a-?.il ftDUlfLc
M a.['" , lrlu ""!-," c-n V',,J* o,*"k
/t &frt*1r- Lr',,,o, I^ ["4 -*/'tao'{
",0-

,L

1""'-lv'^*
^\-r- e $ 1.,'
I
Cap, N-Fig. ,g
I ,nl"l" {zer"e uLl_

hr*

b,

7.,L(. r\ vte s!,rh.*\ _


&z?S.\ r^r,0,L r,,*J2.-r'

!
I

&k

6'r.7,)r.le

'

J* n

s\

c,^ril,aza. t/v4 sll"irlxL*

)p20

'tE^r"tr*
NaOH + NAC

+ NaCl

t(

,\ "lt l"rl.

gr,-r"*^L

"\"eLh

),o15

,Lrs
),o10

IrOO5

ct
0ro00

e-

!
I
I

_t

Z,l to

"u

Non s/(

t,o3o

J"!-02.

1 s 6 7 I s 10 11 r1rr.

hdice tanpone deLta sotuzione acquosa di un cido f orte


in funione det pH,variato per aggiunta

fortr a 25 'C e

/.=0,1

* (pK"r:ldoo;

11

di una baqe
p[K,).-f3,Bo).

sr,.-.

c)

/.i

/1.-o, [o
o

Base
BASe

S16

r.&roh< uofuos,.-

h.p

Lefp+^q

r8ots.

Y1o,-6P,2^rh eC

Hgrp+B

,i *t"y

e.,\

fua g

-r**lrl2,tL{. J"q

a,-

,-or,.Lte<

C6.

fnrrJ+ fen"j I [ua)* fon)

d.nro- oi t3*:/.c,'t6Y.

?,irLo Du-)=cL
[rx-J=.

In;l

irc*to^k

ri

9
=?bl
I p4

(k*,o)^

&ilro,

r (Kr,r)n

roS;ov,-o-u.<.-l*

d/o-

/-k

,"r!-

,h><,

r"

l!r,,+

z z,3o p,,

t+)

R.a

"U,r**L L

f04

[uu"J . [*;J

k" -- n"I

ci

rr) n (k,v)"

C+-: r" J

c=

(!*). , n*
fnroJ hy *r,o,
G (x",o).

er4- L""-

&npi

fr,u

(on,ott

Cs (Ko,r l,

fu,otJ

tu,,!

@ l
r(.rrL)'

Q-wL;s)

- @r*Afr*h t^ uh-'. ,'LtannL urra L.* /"L& .,^' s, ntF*j, .* nof,-. rbk.)
NillL. owue. k i" l.r&.2,r,'< t; vrr uuyn l.a& (Drr vho- L".- k/" (''8 a-re) s'i *lo;iJro 2o\4. Lr** ' v,^q /; ofe li S,-*a. V^ra- lrl f*b L; e7V"["^*"
*.0!* s,%o.v* 6onp gnx-^l', ('a;to J.L/" ul ,{ "ro to.lo (rbu+t),
1*b
"{
*!!- t&,
Lp
L
.(o
ui
k
se"-.
- ua*t-,<
f.-k Jn' ,7;t.lan*,

fr^L

( /.'r.rro
.
ar;t
(
/rA"
W
*;"yi-)
iL
,*4l".lL'
h
?to,{. sh, pns.^
"
A*J. Dn f*uh u!.li**- zsv*-- s t^ !'"^dtokt tzrbvE
r
e;
(Stl*
Lr4,
/."k

6-&e
Iorw},re ou-o

-Wp^*

Fo^E.

?o'.,-

to-v,^go^.

(n*+@rf {"

7"o,,,,1n

'*l!-

",%,.ou-

o-T\,ersr-

l>"r*,obiT on,k (r"h" 6L Cs = torv + (srv, "/r. +4;i3) *hA 6 (q-nz),

e L* Q-w-Lo)

t f '

l^t Yt<-

F=

@.-:

(a-s ez)

?,tc

(A+e"bi)
p'i"l^e-

frr*J e &"J

spr,,.a

,J'!.t" G -t un -L,)" Q*.u b s)


.r,;L l"L& e & Jn 5\'D t"0*

,o* 4rtp\* & gfi

Dzq,;r*^^L

"; ".g.Lunl* Blo

k Q-tye) t si ,l*.,*,t n^*sl i r^o htr^v d.h^'o

"b A l,^.ossii^"o f-',^L [arr*J= (la" ,o). I .rd


p4 uha- l*k c--a(i*lr-n-e,t- l- k&r- N sisfr,h^&- g.,6 *bo-,l,/- ",' l*
?l(= p $^

(,*,*Lo
-r

( ,n ,^*).p ,"(.,...* J; (*,,tc2inn L? .


1"r"J.

,,!!- Q-*r) t

Ur

'&b;,a"

vo

cc-1o.*t*'

dtqr-* ,i;

^ (1"r. **"d*k
t"
)

lrl.

o";l*-Lvse

Z
/7

/5

"i.{"u*r,e:"t"r^i lill' ou-do e


"l*,llo,-

6UA-

r1

5.

r:p"r-

t*-[

rdJ -- 0r",o),
(
or?r

G,o=fr,=.

Ct

"ruu^l-.
t*

or. LLQ +Lox -"yJ_


=

lrn &U-orrr_

(+ -tesJ

u-,w,k /*' ,,. er;te ,tLL"& e lrL


,6f..uu--[. h!U* a^cn-t -a7-., " 1o l,,.0-" (o
uv,e

e o-.J* 1!u^z-r,,n bL ^P(t /',!!" c*,ncQoy


l"* ^^iudo(u , *1g,-b -[* Lb^'^^s'" l- pH '
s L ,k F*, ? o/or4,

oroof."
e c-5 I (/'Q .
(E=o,o'(H ti k
ft*,
=
,.o,^d,
I
b*L lr* pe*J e [e;] &tn 4o .ff"* %o , ,i wuLL" fr,

*,nJn

?il =

(u),-

-t

(X -- p (a)^ -

I"--^1. ,"!k 6u-.*") ,o\,zfrw*-,l^ [\"tJ= Qn)r,b

bl, a-,*r)

fentr

--

ffi

off,R

cv = o, / cs (+-tw)

[,\")=%,

:i L,

k ..f,-d[- h,f* ai e- **,4\ L u,r& L t* fk- ,1" *l* r',*,a',t^"o5i g; J^U 'l^r f y,Lz*; i^,oy1 laf J"L;k , b qr.un'- JrL fouF.rn t L,.-,,.on ll' l"lu,,"!l. J;
pll au\pt<.,p l* p (rc.)^ -t
. g Ul^ h* -t A
cnq,-

fu^ J; T*U 0""''*h .ste- uo* p;; ui.Q f


Wl "*d- Lb,k K%: + ,oln ",li*

c-

I*g* "tek

TABELLA

r*-1"*rk' k "p* n^csil'{d- i,rlL ,olu*t'u oTuZ


a3)
tlEpone ln fuoztone dcl pH dellc so- se- f,il(,'oo{* L{& (.8*,, tre-= *

'L"ok

FY

["4!*

It',18 - lndlce
uo ac ido dahola o,o1oo
luzlone
(K)n' "cqui'al
l,oo. lo-" I 25 oc e lr.' 0,1 lr.

,l
^r

3', 00

2,9- lO-'
3,1. 10-'

3,56

l,6. Lo-'

2, 00
(

xErr

4, 00

{,50

HB
II

Nr:8;,
r_

. 5, 00

5,50
6; 00

7, 00.
__

xe+81,

_8..-00

8,

{5

ll-con

. p ((o),

J,(l'*r* f,t ,( u'n,,,*o


,"U* & A r,'l.,- 7r*dn hYhi*<
i fnu^k ,& {- ,tlo ,,-n-k ,r4- "**
l,.cn,,o /* *^"'^',
&Uf *,tn
"QL& r
NeL a-1o

pH

r,-yi g*h'u.

a1n.

.2,2.lO-"
{, s,.to - 3'
u,,-"
5, ?a'lo-t na:.
{ . 2.' 10,

1,9-10

2,3- 10-'

z.e .

r'"

t n.tn-6 uln-.

3,1-10-"
2 -,

2-

9.-

10.:'

9' t0 -'

- --2;9-10:2: - --

,q,l,L. srLao*

'"Lk *!!*

s,!, *o,u &a

P&'*tL hh , p

srL

Nr{.

GR"

3rrll

,& ,.(gx -- a,+r) -

a.ut^ta-l-t

k ,J

ar*r^)<,

(- f,.n- o* nnl^AV ,wq tV


, ?ntl.,
,,
Lso Aaozl- ItL"Q1 pol;

c-wctv,l>ttbnc

To*L

A-

"fol-(u Z'r,tu,*"two *U*

,l L fq

?K=?@^r;r

vsu+^.,-t,-*; ; fi$o . B; [** AL< L* A'h-*) soro

k *r0 (rO.2,@
ns. 4^{\ c pt{<\,re frq. 4-D r ,,*rc k{.pS^e) * .tf*tr,,"(2"--1. /-/k;
^ao
fi!!*t* {"L1, (h,,"*^b '*f't- ,L' } J- fW=),4o L*b ur*+-*\r*uh ol)'*rt*^'r[
ttfu" -*r*-t^,^"2,*..r- to!!,' ,r'L {-rl< . SLrro .ose f* e,v<*< s*& i.; 7tv- l-st.kL ,L+n* JrL J- ,rt" LL-& [^ ui^- l"L.""h ^f,,- ky"^ A=1!"@)
4"*";

P.uri,q-,^- o^,e,!q

fN

oo,/o- h

(*

t-Lre'no*lo

,,,Q-

r^^.rrha

#k

/7 zlg'

*"*"

,,n

u.,Lo

,; rfi

,\"

l*" *.ooL

JtL tl+ l- t"!- t"{- vl ,Vl,J- lo.1r"{ *r(}-'h-.L^..r


Cap.

IV-Fig,2O

o,o3o
d
H

^ 1&

lrl ptl r,!- ,,(-

o,02o

i.-/

Bi+ 0H-

BdHro+

t".dz

__

HBo+

uor,*l,- -

,!;;n,-k

ffi'uov-

B!

q;

'J/
\.

z s4,*1 $.6 z alg


to'r
e$
P(*",n)'

lndice tartrpone detta so[uzione acquosa

bote HB, in funzione

del

12 13

t4

pH

di un acido de-

variato per aggiunta di uha base forte (o di un acido forte), a 25 "C e A= q1 M

(f(xJ"=

e- t^rh.o ck

lr!!". ,n(uoou
('";,t;t ,*L*;a
i ,?o

o,0oo;-

l\

t+r. L yrfu.-

v@vr

_1

pir-

0rolo

-t

/""_ *,r&,n

(J lo'
or005

,&

le"ua

t/
|/'

o,o15

t,L io

le.-;'-o,

,"u*k [,n ,*\-ta-

o,o25

Sroo

pH,

i P K",= 14,oo ; p(Kr).= 13,80 ' C=Loo'lorM).

t(

,'.-

u_

(-

C-,

.k L*o E *,4"-. L: p ,!!-. f<e^24


NvA

cps-e

L *o|

*uo.n h*Qu"*k t,n?S1txss,b'\


*r&t',* .l f i; *((Y rz.\b*["*

ir+rro'{l'r^'z-L s' f 't'


0,

,k".,

ih

n.o*-o7^ A,.-

,.

Lo,) *

c4tt").'fk"l

([rr"! * tr.L)

[,,or]
,(*

e" ^rlo*,1 ac,k ,GrU" l)rcr*z o/fr- acL 1'*

cot'ge,io,.-o

hd[a- s!..*rt,* ,h

f t<*^h'

<pa Ltvl,-rrzs^r

r!,.L.i
,Glh s-l,t>'u,<
G-zw) i\^.L.* "t* Mi
a U .!or^a,"s. ; b"l; lerru^V i uV*qaa .b, f-&' "J */*'rr* ".( q.o
Lu" t-owf.,w.nk Jilk s"&tuw"
P".""r-.G

oro

fr no = 2,)c

(ry)r_[r,d]

@,"!

i^L'
[o
"l

t"d)

(fud+

2,3o

= r.o * fixer

[^").)'

@-rcr\ h,.^ ; .,0,1r- J* Ate.srzzsp*


e
G o*4
f oo.

/rr.*

, (*

> 2,)o [nr"!

G-rrl

Q.rd

r+ * oa+ ...

p"k

Q -see)

/; p f

(4gg)

Lh&. ,.,(,r*,.^

l;

ou2k

f ,*_ = z,)o ["^J k-rs")

o(rn

e f^\A L Q-lee) i suv<:


/3--.Brronr

@u

/,r-

+ Aas,

* An% r

fr**

@-'xl

9 - S.&-=** a-eft,ola- &' 3 -Ff,\ a-,>.G --b*te


("t;l; f* ki)
^.ou*1*[rLk
(a,-).
(r,,,*)"
,oc
=
e h,). =1* ; I
o ?f"C e
= $"o
p

P* lrfl. e $- 6 capty ]\-

lzgtt'l;

o/ o.(

oo

ll"Lrr^k U (+-, ee 1 4-isa e +-ew) ,il"*-* ; v.l'd J" f3 M T.L {4d /


l,11,rt *n^I*""l"*i il*yn,b^&. \^,J
p*so,*k -Q fnr.r = fon- = or8o
yt- c^sr p (.*)-:'t),b ) eU",4^ = ),,(o ; I k*l*: f,,b ; ?(ry*)* = 3,i" NrlL t L*,* ta,* [ g*n*L -;J;/L *-Li* t;s^neh .

t *b, J"!k 'taL 4-{s 5dh, ^\r'^.kh r!. t4- "//" }

4-"1

,&

f'^l*

l" c^,yv< kllzSpk


wgpv.'^l-,^n # i.A; Lhp,r* 4"-lr\v0t . 1- t\ p*t- l^ pfl= z,.to e- <,,t^e.
o ,nl-l- ',&*o,t &to y.-^h *k vh *i, &rk "Lk o- A. a-c.'J.l (t I
fi y,q- 5z ot,.( 17 J; tk Hor e coVza. 2, li f",wl ,-ll, t"(,,*r,< ,*6$4t.
y\^ o,i.. frrlc / ,\ a* /,' ,,*-Lu /**
( no ^,nrt ) , ah ood "6A<
frcx.-R
(r,."^'6') el /^' "*Ll' /'LL (u-'"'t),
k

s,2yve.

o-

t*k

penp *p1"r--nk

I e( onny^lui
^eH fi f^&'

F =f [,lr) ) *-k

vi uv r.--ssit"^o o vn

ikU"no^r. t lL. ,^^.r",.(


fr" fl'( ut*,?*dr^U ; h. c. i-i;
?r,\;i i

lL

u)rva. il

u,^,,Vi"'o

nLt"t*

*JllL'

g''&'4

tl ."li; ,-!L tl.t* o*l*i


J; F

r-'rrt)-^daa^o,ru*o

J;
"A- fu*$

crt.,3p,*"G*k curvt' l) likL++"* JtlU


Wr* lr; ,,,U; Ji pt( f^h *.0!Jd, t,< *o{r' iL 7*tAu'^q '
,^;,,rnb. J; a-c;{{-rk c
osv*r,Mv,,--o -k
,g ,^*-.s r.,p /r,(!,' ' ";{o t B' ; u+sclv*h J*IA' "L'q
[or?.o* Jnfi',e-ctee- o^ ""!; pv A*rr J; fft t /.k- {-r,(- oo,L l.a . o c-sh^lt
t; z6lsor-\o*\,^r hin ,uflfruu^k^e^k fZ*U e / y''t^'Li , 0' ,\J^l* h'-f< /'!l^

L'^ct^ko2ilt-i

Sirr- s'(.;.zbo< e-?u\rla- P

!r e t!? coep,.c "*too-ii"" ;;;?r;i"

ilj:l1t;tll:;:31
z;to

| :. oo
I r, to
:..rs. ro'' I r,co
r-oo: ro-' I r-10..
':-rs-{o'"-l
r, r s- ro.'t
r,oo.

ro'"

r.so

r. oo. ro-"'
r s- ro-o-

:,

r,oo. ro-"

I
|

s. to
s. oo

I o, io
r.oo'ro-'!r,ro
-r. co. ro'' i a. ro
r,oo. ro'o I g. ro
t; oo-to-rof ro;ro

r.oo-ro't'ltr.
. ^^-.^-r:1,.

r*Lt'b

k" otL' c /^ bayz

--ifi:-:::ilHi:":Hfiii: ::1.{.11.::',::: <.-,^v.pok l-h


i)

TABEILA-IV;te

r.oo'ro'2'l

@Xvt

ro

,^

:1:'9t
'"

;q;l?;"':91;]3i:

2.3-lo:z I r. s-t o-t'. ?-,r-to-c f-::to:" i-s'10'''


1;2'10'e t,r3'1o'2
r. l- to'' I r. :' to''-

:-:' ro -' I s. l' ro''

z,2'ro-'|+.:'ro'"

:-:' ,0."'ir-s'ro-"--

:' ro-o o. s' to


z.:'ro-tl2-3'lo'''
z.:'rol?]i-:-ro-"o
:-r' lo'",i I z,:- ro5.9-ro-'|:.:'to -

r.

J,6'to''lz.:'ro-'
r, o. ro-ti ?.:' to-"
-'
r; o' ro j z- :' ro-!
-'o
:- c-

ro

'' I l- 3' Lo
ro'rl

n- lo''1-2- 3-

8.2'lo''
:.3' r0
T:2't0 - 3. 6' -'
"0''
't
{. c' to
1. 9' io
.: 5 10 -!tC7:2t0
{.:'
-0-'
5,i. l0'' 2.3' 10 " 6. o' t
-3 :.
l'
r.3'.10-"
to
:'
1-2- 1o
1.3- 10-'
l. g. to't
.l. o ".o
2.3'to-'' :.;l-10
:.3'to - !,9'to-' l, ?'l0''
''
5.',. l0 ' 5-?. l0
?. I' l0
-' l, 3. lo -a 2.1'to-'
-:-3--lo
1.3' ,0 -l
2,:' to-' :.3'l0
3, G'l0-'
'?.1'10''
3. 8'

.L,i2ao eer+e-

*;

ao,*v* /'tl&
(q-lu L;t) ( o,Ye' Lr*rJ \,ow\ ; l-'o,t.,.tr.LtQ **il, p
/<au,i,*.
1,..r1.,
furorl

,tot- re**o

<-

10

.lk

%y"T:sl r.,- ,!A:' A,,e- oo4.t


,^-.\.i/*d ; pU4^ ["i gu.C

1""* ,f"*L, "^ 7K avresSr..-ln*K .i


ngr\,
fr,,i. & ur;,., p ,g,LL (*r* "

,!rt*rt ( O,*';J,
Z u,k *k .k r,/.' t,, -'n.n^. [a"tkLb.* e2*t - f"!,-'*ll
,1"","^)* r--9 L'ULw (-o.ry,* lrll- sr(n i',r^* J vh A\,r/!" .(* si gvo-uht^,tA ^f{;-Ul.",t^,1" *rl.^*k o cot^v^yu- ,ht- *+ /t f*bi *,ll'l,Lteao

@wf l; 1lt .
iu y-r+y, g*V.<,i.pro {, pnp*^. ,
oG C=or4h

, ,-^J;,

byt -s1,. .l;.(J:roc-klio,4

W ptt' z

g,L*.wu l.,''.i-'* Jt,

M. t"-

" Aor+po,r,t ,'u*r,&'!

{o'', l{',

'/v.'L

<o-1 ,'t^J3

;14/- '{;

?'(;On /;

u4-a-

g- 3+''ti J"a'-:
o,o(?(,'*1

@ig.d

a, o41

0,o30

Pt

o,o25f I

7,...t

(;")

,-,;""&"rLk

'o.t!,**l.^,.'"(

a;t'
t"A"t. f4n

l),^

s"?-

(a\resc.nl'a

pK. + or48 "


0,o20

0,o15

0,o10

.I

0rooo

24
P(lt

il'

p(rqiln

10

11

P(k",r)t

13

1?
pH

acquosa
lndhc tampone in funzione det PH di una eoluzione
4S119 o baEe f orte e tre coPPie acido-base
contenente

p[K.), rispettivamente

11

eti

l,to-s,to-frc14

(pKr.l4,ooi P[Kwt'$,so i C=
i-i,rH
'r

+rl

25.' c

1,00'lo'r M)'

i i i i + , ' ' '

Curve di distribuzione delta coppia ac.acetico - ione


acetato in acqua a 25 oC e.p = 011 M

5'Jna,,- k*y,* h"-k d'l!- Lven< \xtv J; u^ a.;J@ g!-p*Ll* fsto.^o ecst1-e,
r-,,,+["-ak (pbt (o. u.--ar--!- J;" "-;*i vwv.oyt, ,!l-" t* ss k ,z-rl-r^,.J-, tb
Wffib ,!,,ar* du' At.n\o FrrsFo , b -^i 'osA,r*[., .lvccc-rsN(
fzgr,to J; vc-o- nO' , pu; g55..r. "'*s,Vo,.r-hr 4w* U ,rrLau.-- J;
G*

1.,o,^.og',-liri

<-w

.c-,^f,,o

?ro.^r kl-,L tdrr"!* e Q

fu" s*1t- a,Q--Utn (e\A Aro,^,n

F--)urot A*rr.^+ )nr*i


=

,,r.

[[nrd)

O,r"c-,^*^h () e-V*s.:b

h0l--

c-.^/.'e.\^.

,^,;

b^

CL =

!4^o-

L*
/-

, A-J

uUgr-^.rt ^,C tt

L.

. kn,e. [r."J

l-

llar"*l K",A,)
.-

@-to
a5

l;

. v\

L/\^

C. k..-;: ftrr4

(trya, ko,) @+t)

i'. 7$y*h'u i, i,,^^.

o'r,.l

d/* /^'*t;z-.

a-

[neJ +zfe,)

L*r- /r.*- rt*a^ , ,w- ksL, z

C' Ko.,t'Cn"*J
[!-,8)' * [uro+1.Ka,4

roLu?eFt Es.{&..ll

')--

Kt,t-Kt,z

oor*

[u"-1)

l\^l'l

J*uu'

/3 =,ln o +fxre

',^n:

b*L n&'*

[,rrd]t

- K",1 ' Kn,L

t furo!"Kq + k,r -Kt t

,e<"{--

= L,lo (["r1+!.rr&)* z,to

t ?* Lt^^'t A

5. (taof,o

J; A J

'/A = +J rta

f(pu)

*Pueo|

(trr"'J t r.,tr)l

6,s.o.o-

A=

f"n) [ur*) t [nu| . , Br) :

r#, - B"')

,.nLf.i A

t*

f7s L";l;

cau-r5S+w&,^k curw.t

.-p1rr*:iu,n-4a^.t

. k"i [t\"i

t cg r)"

lZ.',1

,l-

d^'

[,rJ ,

,ho '"r1.,

,c"Kti I Hzot

[rr'-*Jt

, 4lo(rd) ko,L t:.,,t

8:r"

'' )- ) ([,,r"!t 1[\)La/ td\4.orr)'


I

^ .Buru n-h< r{ yr*^.* (st

-A

nro ,

G4e+)

@-r-<.or-fMf,^h*)os

*Je

(- c,svtrsp*r{"*k co^Jiavr." dl

(./v\ r*V\v,o:t*A
olok'r*,,*r+r",1;U-.,

O-r!r;n,

zssz*
1fo*\\,-')-> &--rSr\ (vr

Mw.e, ,-r^b L "-eio,,rfi tu.rzss;w

I
+^,g,.a{- IL(t

AA Lse-\)w
A

cnbo

\Ans4,r-,

&ao 5rr..ui

r.c

/'\>.

*o\ei

ea

A{Aao

a\,t

<.c

r\,\ L^.^o-

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agTns>t-z.,.*

("* ('A,n 14o*!i t",'

tnu h

orrn--G.

p*

c-,t.^!-

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4.

7o
4,,t

*1r,r-rLi

f k,,

o-o;L;

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4,lT

18

4,

4z

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2,3

4,4

l gZ

S(EL\A

E;

'-AlJ<:^r

U^ "Lt* l-U. J* .--.s[,v,*tz p L, ,r".(,L d"A- "rra--< , ,J- L ?"


l( k -fr* yosszte *'-A'\< &^ (t e,Lfr- sf-k
rVnltk e ,^,-Q",-?s.i J^" ku*r*
\ ,Lz) "* . b yn"b ab!t,"'o \a c*t'-po ,f- ?P (ruPtu tl''i
f*l
*ffr*k, si 'rvq- ,- ku7*
io,F."wi ,1 . arier-Fiarl ltfrlor,,eh*; r,rhLt.*r. L* ,
or,.,.v,'.Jr-en-ltfuJ

;d*tal, lt

w. "!!"

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ff-?t, tt c<-sr't;t
e445eo d; '\^;

X"#* rl
frnr-^.

M l*

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k,**

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cl,* 5\

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rh s"{o.;a* f

e" ,o-

h.,a

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<-

t^-'"-)

ff*; - hv;
qvwwce-a(4 ?- c'-,,

fott<

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"ulk h-0!*. 6on
.,,v, 0l "u,u.*l* fit0" .o,-ren(,o2-{o'{' /'P' l"'^{t^ )
{ trr,f"* L' plf 1,.orl 17 e dL
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",P-lo.

4; l-r*."* {; f"*

5i f,otlove P>ufry "^'L


t*L
,b;z-e r'ot n- c-sL"'-k f

cu^+r*"rr.,\

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fA ^ o.'^hu'k
grco\}r.kL[""P , rbr* ln*id,i'

L^r",""'

fi""*

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c.ot@ o.t

,*Lrn.u

k-p- , a

,u1r",r,*h

14

rw /r","*^ ts

,,k

sb"* hrrp

[,r^

l/vl;*

('n*r,^,ornJp-ro ^

lb*f- utm*auV ,

rb"-)-c -

s'L'a.; [**r.* ,*,(!- 7'"8^' A,


)

l(- nil"rb W

ve-14u

c,,Y,

Jtlt' o-";{o e /'lU" b-.'- f v%.rLa, ;( pl( Cv- ,l


," stl-h,* b^[<*,1 adL (t*) w.,,^ny,-k'l a,s d"L'c

f*-s*,*r L e"*

o ,tU*.

khg
A-l us.^(b P4 f. thlc,^^o. oln si "l{+"^. "(o '*' *a{o LL&
v.^rh-pr- {-',-a
r (un n,"U b grcsr,r)\,^t ,U.,/.i,--l-,0- *^0k GnS 4-z-)
r^;t\

TABELLA

co*6,^ 6,

/*-

(y,20 - Preparaztone dl tsogonl e (orza lonlca


s ian t

E-. Sls !eoa

ll9-B-

Fo

rzr

lon I

cE-

Ma8'l
-il..It/

-1,

_0..05,'
o, ro..

0,t5.
-0.2

0*

0,25

Soluzlone d1 acldo
forle d&888luotera

60luztoo dl psrtenza

0.05

os-

'

KCl
*-0,

05._

0,05.

o,to.

0,05

0-, 15

0 ,.0 5_

0.20

'ilcl
,N

--

xcr
,r

0.2

0,05

0.2-

0, 10

0,2:

- 0.2:
: 0;2

..

0, l5
0, r0o,.25

lu,-.\.c-

tlC,a+t*re &r4* I.prt6 rhr Soq"r'

(-ar\;sy^

l""h L

lu.*,, o

L
)<nv

"rJ^V*6

lr*,*

fg 6p62alra<0 svr-'

('r,,ln,,**Lo
"r[rr^*

es

LL

g p*

LVe

d;

50rq

Pr-rn*ln
/
<:-ol*L vOlyc\* ,t^

.s.,,..io

wl,x*l.

/r/h

o *-\Ll "lt*

(t1rn>;r"u-

=#

bt;vt

4e-@?b^L.

1l,.

C*

egsl*-.

k,^1*l,,,ra , a- pte*h,<

/; l/o.-'f lt"fr

G-u',)

\ n* *Y*l*h 6 <u>l'o-,ti / L\s' av*ia"< t k


,'^)*k o- hU",tL l.,r^trrr^f"v< f
o-"d| t'p. {nB
"!^r;

G*
t

ar-o-oxt

lrlle. "dilk L; lvrVi^v L

(tf#)
*tI*

vrtu{l-

Q",* u' ["f^l--k

t-6ts.r rV. v^

^k / 6't es(tuw

lrh!!*

ev'ulenl

J.JL fu.,ry*-t* (- u**h J; 7&L,v /o- r"rfi /*

yp-r,\a,u^q

*5L,,

i\^; ",c -

L efhL*o uei

,n),. l,-L

t*,nlvla- lr.0l'

r*Uo {--r-

Dr-LLA

^slu"^h

+-e,,^f,"^'{""*

4-,4)

L'r-+,,^

\r,.q *-1" e

O ,*l"rw ,t" l*
r"jy*r,-l-V l* gyaz

q,&

y[*-

rL*\- [rlt'*y,u.

,J[, .L4-hh kL,0 L /"'*uu


c4r\a-

c,y\

o-

?Ke,rs

=f6)

dnu"<A okn *i ,,,-"h,^r,*h


y*"J^lrV -

q^ u ,,;r,-r(. f^rA

w- tr-oa>lva

L ^s 4-r 4) ,oo6b.lrfrl"-* o*-l.-o (,1* c

c[w-,

&- 6o' 4tf4L'


lr; Lroa t

1o -f

sElwkT viavertL t e

b ,,,r

o- 2rZ

U* O" q {o'a .
,- s l..*L & .Is o c"h-e'w'r.
'(,2r4 ,o-t, w**l-.

t,-oxrt-,1 a. 22r( "c ) ;


I
urt^<r^k

lovc(
4'['l,.

*L 0^ h,rr"***,- ,!' 'L' sofli^r'

dtp.' ooda o-.,hlo Gyt ('r-7<

f*b

L<roe,o^r

&' .,^A)

(- c-si//zg.s- ",Yr'h\i " f,rl6

.n"'t'rf,Qyro1o

o"e

?.L

ttu4-to

b^e .t-(o,k.I

-Ks-*S

,-t!",-h

",tho,^,- J.

c- 2l'1?

kL

1,oo8.'(o-f4

"(;tr1.to",

= fr?r-'(o-lo

:,

kL=

.5,,(14'(o*44 :- 6,2! -b-9


4r r4L' 4o*9

a\; , *t,,*kn/.^ k
rub,,,LybLo
flf"a

e)^!t^ ,ol^.{o

(e,^^fr-*lr^
c-

,,"0*2.

nurn

(yL

out.,c F,L ,n^

(molellt'
TABELU 1V,21 I Cosls'nr1 d1 dl'ssoc!ezlone
ln

l{u

(o,

1,65?

l,?00

10

l,

.11.
20
25
3.0

0,

35

''1:',

{0

2,919

'{5

1, ?53

809

I .008

?{5

l,
.

1';St,L

,,t o'

o;?5-

I o;rl
I

e pL L"i!*,Lt" &./2(o

1,3?{

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1,5?0

5, 55
?.516

{0

6,,056

5-.

6,226

e. t8

6.5 31.,

'6; {30.;

5. {9S

6, {?l
6. {?5'
6. {39

.1,92._

k l.trt^-(tt* ,,*(l- tyf /^' 7"*^ b


6_ lc"_ . t{ KLry
r^,oh
"r.r^.,-/Liuo,,l- o {r/?!, a-s i d.&' , ('L(x,
led^ J,v...' conv6a.h au)Sp"^ l",/rH
a*r**Lt ,n,

5. 8z

0, 56
I

r-lo'

5, ?0

6,'3{9

'

Ko,

8,39{

1: ?03

Ko,
I

8,968

?50

t,6?0
l. 634
5,{7{
50'
'-:
:- I . 589i
5t.
9;6 t{=

l.0l

t,128

-*-A;fu .

,b,,^r-

acqus

Q0.

5.9r

-*1:3t-.

1,7{.

rr1o.'

1, 80

1,729

0,29?0

l'o^,*^,.taa.q

/rlt

come

scala d1 concencrzlone) olsurate


o e 60 oc'

0, l l3s

Atrl,^.&li

T" ffr*^"!L/ eAl K*

^k

t,?101. ?74

1. 820

{, 6?I
1.852
4;4L
{;os--1

(,

t<-r^yr-,++vvv-

1,-nt; &

ll" *n Jn$; ,h^ s"h "


"

8*r",-L _
('*rnyr^"o*^ls o,.Lx-{-q
, ,L(n o0- ce,^,

|.rfr, lrM^

t"Y"

A'*r-*.^Lu*

i*,r,r ,

[tlL

'*Jn

c.n

Y% pr*l'vr.c.

.892

FtNE

itil-i
t I
i

-i l-ao't^q'o';
-i
-lertpeart,o',
I
'l-':'Yr
i tL ,^/os.4.o

$on1l-ess' s-euatul

1><<:l?o 6'
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'-

I
O,l
o,l

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.lollrecirlo

n'l;osrto

,+1

'.'i-r::;l

,;."*n,,-

li.\t',:,t)Ut l!1lil.'iil#t!U{i,!r lil({tjUrCU"rutl

.j-i-.-!I{llgj.ole" cli trn o.cirLo .Ia rapp::or;o;rtazl-one g::nftcs

cto11o, so1,-12::ione

in iu:rzioire cI

luzior.rc /-roqlrotj& clol1 ro.c:Lo.

clel

i ioni or:sic:'i1e:ILl1}n1! a]1e

so

lLt "ouYa clj. tii:olazl-onc" d.i una

ba

nLln8r-'o

l^na1o,g,'rrrro:tto

e1

eo Ia ra.,p1.osentu.?,iouo 6rafica rtol pH clell.a eoluzi-ono l.tr fr:nz:Lono do1 nulls-'


I'O

'

ir.i-1.,:.o:boiri*g.r,grn-r;:! c.l1ir.

" ro

c1i

soluztono aoquosa tlo}la l:aso' Uoualrnente iI

nuElo-

ioni or:r:i<rj.Lc o d.i- j.oui ir1ro6;ono (protoni ic-:'ri'ta.ti) viene ospresoo at-

. .brar.arso 1r,r} (ii soluzio:ro cl id.rosgid.o o cli aciclo nonopl'oiici foltt gggi*Ii
aIla aoluziono. Una cr.trr"e i
, y'il tt)'lcY4 tx:-/
L^f
^ --'
,[Orag

zfoll'a=

a) Sia n iI

1;j-Lola"zj.ono pu anchc

-f f
,f
o ai f.nrO'4'gr..*fl por :nole

nurnero

rli protoni agglr,rnti

esprimatri

d.j. aciri.o

come

pil iu fun-

o di base..

o unn base pel nrolo d.i baeo

BUU,il&ly;lt

UtiflJl tota-l.e noI oors: d'e11a' bi'bolazlone'


upponierno rlj-

to

{'orma cLl

ateta ula b."g tipo POI- (n'-) prescnto in soluzions sot-

(llaf)rI"- o oonci.:ntro.zrono totalo C^ 'o eupponiEuno d.i agglungoro


--a
J__

alla soluziono u3 acio fortc H-.p--, 1a oul cottcon'traziclno','ari& lungo 1'arco


_*

+-

II n

nol1 prov.rohl una

el ha.tro i

nog.,1511ti

eensibil-o variazlono cl:t volune. Durat:to la titolazlopo

bilanci r1i carlohe e d.i ua.r:ee J-n acscltza di a1trI olo;t'='


/,,

/-u,,-'
//'

!'
t

t
r.

,,.11'L

i i-nd.Iff r:ron {;l.:

[n*''] -' [,,,n']

)
I

g, ., [n,n] + [,,,, ]
.o - [u,,'-j

r --l
l
L I,|

r ^---l
4-2 Lifil'
J

- [n-] .{ [un ]
.F

+J[,,']i -lcit-l

(")

[n']

ftr:r'-1 +.

(r]

-] [rr.t ,, J [r.r] ,. : [u.r.] + 3 [rn.{ * :

rra::i-a nol- crlrno d.oIIa tito.i-azlono o co::rlspont.o a Ii.0

[a"]/

(p)

.1"

a6,3iun to a1lo

.{-

so.l-uz:lono co'bto forlna di. 1l A.Qr-tirrtl.i-

la.llculvar cl.i tj.Lol.E.zicne" do1In base nr-'

zronc :\. fr.,.-J

claLla (o)

- 3 [u,r] * ', [u.l]


. Ilvlclondo

-'r-a

s:n..

d.ata d.al pII 1n fr.u -

t
/'1
L,r.:
tlli1
L

Ln]-[,,*n] fu.n]-z
t.

I
l

-l + f -F-l r- ---l
Lt. J llr,o'l - Lnol
T

-I

"

-L

* Ittlt I+ Lir,o'l

fcu

(a) po:: 0r, si, o'ttieno iI nunelo di

(dali"

(4)

(a)
1;ro'borri aggiu-lrtl psr.

no

1e d.i b&o 'botaler

[n-]

ot +d-

..u

- "lclIIJB 1' -lctHr3-

Da cpranto

visto & pngi 6 <Ieg1i eppuntl:


nn.u

'drr";":

*
iln"^-

+-1 r -l
,
UI'o J - Loti l
C

(u)

'r$r"- 'i

pex cut"t
!-!=r-J

In,o'.J

nl-n.f

(..7
-r

_r..,o

(r)

,.t.{:',,},'j- ,r. r. .l a*;1'

^.i ^1..

l_on

i1 nrrrlero
al

ugualo

d"ei-

protoni aggir.nti (r:he

mZ,l,c

numoro\'.,J.'rl

cianno 1a crl-rra

d.l titoJ.aziono)

proLoni loga'bi (che el iegr"no a n3- por forrnare 1e spe/,,

i\"
I

3
r)

li'

,r,o*or:a'Le cr ch,: din:ro

",ro

ll

l..tu cltr.''sa

rli. {icrlnc.aiorto) p11

-i-]a-lull)1'o

doi pro'bonl
""

""4'

ore d.errouo ciisero J.n cq.tr1.1:li.'riD cou Le formo plo"botrato ai varl pnntt
l. I:.Lorl
dp j- pt'o toul ;rrc'rtnlr:tr Li da.L solvetrte
ti,.r-l.l.c. L.i-Ioi-iulo::.i.r-ljnr-irr..r L bi__p.'
__-".--_:-

;tcqrla o t:Lrc aoltrr r;r..1:i- -(l lrff l.


--.-2,
--.

t c /b tt

11!
qu.an-bo

r t3r.1rr

.?

/ r)

i!

c s ./, t /,,'c rtt


r,,4, <
-

llJI/l

".
!--,lIL.-,,;.t;-i;\,0 cs,r..,ne u:.i[L e
,!o 4,1, 7o z/t

,/,,ji
,::.r'r ril,,lcc,l, I'irc j.ti1-o3.o:

montre
'lt.i'att
l;.^J

i tanto mirtoro

ti-.J++ il..r 'r iu"o


.15[U.ri o"tro s:. :L<r'o]-izza (reaziono vorso slnj.stra)

Bx- *- J

!.)

Suppor:j.a.nro

cli

+{

a.'u3,re ull a.cicio

H.3 a cotrosnLrglione Lotalo

suppoulamo

/1*oH-

d.i ag4iiun6ore

a1la

r.ro.lyziouo r.rn ilrossirlo

forto

B,(lii|lJfi

con

1o

steege pr.omos..

so 1'stto ;'or i1 1:rcco(enbo caso a) '


Dura.nte 1a li1;olazionol

t,,''] ., 1,,.r'*] ', t,t,,


cu - [t.u] + Fr", I

] + a [m'-] n : t '-] 'r' [0,, ]

(g)

. Lrr"-] + [r'-.]

(t, )

corllopond.e .1 0II u.g8iunto a1l'a soL,fJ -r"ia ne1 coxso dolla titoLazlone o

\-*,

luztona eotto forma. ai. fn+oi


euind.i IE',cuxva d.i titola..riona'1 d.elltacld.o E.ts sar. clate cla1 pII ln funalouo

di

D.f'J,

alIa

(,g),

'tfl - [u,r] + z [rrs'-]'r 3 Lr'-] + Lor-] ", J

co. (:

Lr,r-l r' e [rr"n-]

L,t.o'] = (rica'raid: 13d.aI1a (u) )

{ [nn'-]; ..' [orr ] -

[*,0*]

(r)
i/{t,

si o'i; [:tr:rte i,l nunoro <LJ, :loni


Itl.rid.et:t1c In. (i) 1:cr' 0<1'
|
I
: -..
a.s5g
pr'oboni
nottrS-t!!
. r'ror nr;Ie c'l-i. n.ci.il.oi i!,t::rritlu r;ort'inp,:trd i:.rrch" o.]. nuli)ur',o i3 'ii
f;:,,!i,.i :i":t:it,tx'"1!:.i!;;,:+;7 ;',Li::t{:,f:',;1,
. lf31i;1.fr|J;iLr'.;/cLrrl, tre.L cu.Er) :Ln old,::rc, irc h.e. J iu. "p61;;;i1;:3;"-'.1'J.'Ilrn1;-u;1f'Uifin1],P'-:{ti;I

'

*tLL,;At

qiilr,,i",t"aririuli**:L
cher

conto cL. quanlo si riot'cr: uo1 oaso -o) pr'4oorlon'bc, la (i) d.ivione:.;;:;ji'j'.'
.

tu (t) e l.a (t)

, oio tram-f(pu)

(Li f or:nnzi.onerr

t"t

ur,r.r1o

C,:nno 1a rel.aziotto

ui-f(pil)^

conto {,l-La ta.b. Vr6 a p. 1l do6li app".mtit Ia

soluzj.oni 0,-l o.0rCI

l'1 d.i- ac.

fosf orico col l,t+olt-

0lr- e-6;giuntl
n

PII

tla

cB-0,1

],1

per

,ii,.:

molo

Ca=0r 01

1i

1, oo:

219

2 roo

L'

,3roo
a,9.0,

'5roo

,'

-0r g
ar4

-9 ,0

-o r5
0rB

tL

o,

Zto,

Q19o

O19o

7'r9

lrot

1,0r,

Bo

5, oo

10
*, /

1r1

frl

7r@'

1
Lr+

lr6

Lr6

Br oo

l19,

lo
1r/z

9 r-oo

1, O.

1,9

I,9u

019

ztvz.

2, o.

0rB

na
.-, -

al
c, )

0,

zr ll
L,U

10,

00.

,0"

11, 0o

L2,00

311

11,00

or o5

Jr9,

l?-,9

zi.ons

.LoI1a

noutrali zazlone
rrrPo;)

o l tluo-pr.'otoni (formazlone dJ.

riolla maggloro utlllti'


_.__-.i*---;..
clcllu. crrv& dl formaziono per vode-

dl

1lsP0. e

irT1.-Lglfgzio"o__lii_Ul_:"rU" (ta curva d.l tltolazlone


.".-/--fi-,rti!
-- --.-_____--_*-j_-_.-

farrrbbo

p'coiuaro oho I,"".irl;',;i'lolato fosso d.i1:rotico). In of.Fobti per valori estremi


d.i pil si. ont::a nol1a coslid.ott a.. zona tampone cloll'B.oqua. i. I : .,.

.1..

9
=

o
.!
f

12

10

-2

,'lr*-rr,.r,i

itl{

-l

Diagrarnrni

di

log

pH

a",ou, irr funzionc dcl p]l pcr alcuni

rrr

bsrNH'l

di

l,;g 4.vrr.;H:)

irr fu'rzionc di log INtl') pcr

alt

rrni rnctalli

&r4

Y
lr

3
J

P
IJ

1'

8'

.,10

12

Pll

tnelallici
- Costanti di rrabilir corrdizionali di alcrrrri corrrplc:si

,;db

co'

F
tl+
llFl

s\
-0rL

-or[t

5"Q,,t

6t*

lJ

lei

A, ?io'ar dt/

Fori

CniL,rnnJ,^, e ""2furo
nsJ + n2+ + S2'
5. ;e plt di, ",, nvi s<4.
Ks- e KzS >

nS
lf

", = [nzlfsz-1

2- /-.^L A

*'

s'-nH+ +

HS^

Hrs

uT"ieLn' .L, Jissoc-".s...a,^q L.

l{rs =

Hs-

ki

r H+

[n s-]
fn, sJ

Hs-:fl*+sz[s') [nI' = 10, 'Zo

[,,,tJ
s r{^t,t f',r: dil5=

f^ /+""

7Q'6-' nu i *

Hs- +H+
5rt?;via-1.^.o

76

ytfl

[tr*J Ds,J
--

[n t-J

'.

H,S

1o-a'-Kat

= 4o

-'3
=

k*,

= kr,,

nS

+,(-Fu*

sr-a

Lk /*,

fn,! = [sr-J + [rs-J * [r,s]

s = fitr*J = ftr-J

{ [t'J[u*J + tt'J [rr]


7o-13

s = [nrr) =[sz-]

S'=fn'-lLr,-J

(,r

[n.]
4o-t\

lr#.

5'=

kro (" +

s=

[*

5; , ,(i",^. (,*

[k+J +
4,i1t

4O-t\

vv

['-J' \
,

nr" /

4o-.o

"L' =r(n,t t- i,

cr,,yv

fu^zo,*

[.a!

pH

.{

AW

r pt**,, l*

s =rtr-

dr*.y,'*L{^'
Eseaau

"g

IC

b$,b f,.rnlu

k^;;

ptf

so*o 'ru"L;rs

Fi'^Q-

Soov^o

W =,W U_
v

W
s=rfi-W

a ,Jk
.

1o'r

=*,; {oB

, G tohh("k

puo-

.or(*

Ey^r,,,

4o'"'L
4o^lo
v

(o-1o
C

L*

e-

Eserreio,

urvl

srL Lt)

. .[r o-']
'(

U tt(.'*
>

U^ to(.{u,-

@- gLl= o

dlo

o- p\=o

F",r

= 1o-2r.lono

=a9

k t*r,r,,*tiQ

Kso =4{21,t

5=

S=

at

Kro=4r?

FK=z

-2 [ul = y'o-2

,l*r los =@

+[tJ=1

.,L
4o'1"

t.
d4 ?tnc^t

?
/*w

,*(.(-

f;u "J-,Lte

Zsspz*

(-ont;ln rok

euv?4

K* z

4o-t1.

srLLrQ

(r'n)

i';'.:1.:;',

mltc. .

''.'i.-,-)r.,

'acrdt ,

".

0'10 ntolc/litro
). E<LVPlo x.9. Calcolarc il pl{ di una soluzione contcncntc
cianidrico'
acido
di
molc/litro
di acido acclico e 0'15
1- ,6111i1rni di oquilibrio s()no lc scgucntt:
lHr l[Ac-] - l,'ti x l0-$[HAc]'

til+ I tcN-)

4,8 . v' l0-)o IHCN I'

tH+ltOH-l- 1,0 x lo-t('


I hilanci di

nrassa:

.!uo.l

* tAc-l: o,to

tilcNI

1- [CN-)

0'7s'

messa si conFgurrno nolla if,FIrcscn'


pq6
il problcma ncccsslria unf, ssL'l
li5qlvcrc
tazionc grafica di fig- 7-6'

L'cquilibrio dcl sistcma c ibilanci di

iH+l: tAc-l*

tCN-l

+ totl-L
di

IH+l'
Scgucndo sul diagra-mma l'andemonto dolla "ur-'" r-'ppr*onta(iva'
di pH pcr cui [ol{-i
si vcdc cho cssa intcrscc..r la curva di [Ar] ad un valorc
bilancio
c [CN-] sono cntrambi tra-tcurlbili: con buoneilpprossi.mi'zione' il
si pu scrivcro pcrci nolla forml scmplrhcrL3:
di

II+ ] - tAc-l: '' -P.{-

dj acido
['.ii-'-" tn9:lg-4:]-gi "

pratica.-1d.!nLsoluziono

-gl:.-{o :o:{sg9gd-o--in
tic o : i.
-c-u{" -si1iiG.,:*

!Ip.H
ac

2'qs'

,@9!.1-".,---:s.o

log[CN-]

i"

1.ilt f'

6.!

0'l

molaro

x l0r"
-1,0't' tCN-l:.8'5

IlpuntorrpprcsnLativodi[oH-l(minorcdito.:')addiritturafuorid:rlla
ss.la dcl diagramma0.10M HAc'
p. - {.7

o!-

iHc.Nl

'

:l

O,2J

I HCN,

p'.

9.32

:ffilH

ry

I
I

...- 3

I
I

(J-{

-t

xo

'l
I

-G

-!
-8

ll{Acl
:'

1-r-r-.,-\ '
$ G 7. 8 .9

r--a

ro ll

t \!

72

13

.'.i

i.: :.:.:, :'-ii:,


d,"
1,, r i:ir,,l;.;f
i'i:.:":' ii :i,;1..i '

*l.i:f i;:,i f .i,f ,ffi l*, irft1


'i.
.j:1., :.1.- :'.;,.',::i'.'.i, .t.,.,,.
,.

.',u..:

1,;'i;,;,

;;.

. ,'

fl
I.

'.; (a

':

:'

ffi

,',,,''' - :

i
;l ii f iig
.;#ti r{i {:,
:'I.o-',,rtL1,.:iji:,;';:;:'..::ii.;.r''

:--.,:[u*ttr-r-;

HJ fi

i .r''''i'i};-,HTrl5t;ii tt

':,.

'

ii

;i

:i'

- ','-','!"''r-.'.tY'.t'..;.".'

Scsucndo sui'grefico'l'andemcntd della

linea'*r;;;*.i,i,ir. i 1"*t'.i;"0.
tl" ,*:.intcrscca.la linea di [Ar] ad un ialord'4i pg p"r cui
lc concenrraztont dt In- c OH-. sono dcl tutto trascurabili..bcvc ciscio pcrci
'

[H-J_1ar],

l,

'.

pH:2,88...

Anchc in qu6(o c-so. il pH orienuto


soluziono ai ,.;.io
"dtr'n.
acrtico puro 0, I molarc. Il rupporro di"orrirpond
(ra le duo lormo
concrntraziono
dclI'indicatorc si ricava dalla:
...
.

[Hrn] [H+]:_.-.-:n,
l,l2 x,if
[tn_] ,(r" 1,6...
x l0_.
di tOH-] minoro di l0-r:. vi

L-a conccn(rlzionc
dil-uori del diagramma.

corrispondo un punto al
.

.a'.

O,l

M HAc, pX.:

C,|S

mc(ilar:rcio
-'M HIn, pX.
-

I,0 x
I

(J

':

J,g

-{

c
I

-c
I

.-'t

-;
7 8.9 lo.rrlz-rr
pH

Frc. 7-7. Diagramrna logaritrru"co pcr


una soiuziono con(cncnte I,0 x
molc/litro di mctilarancio c O,t
IO_{
-JI"ifi"Ja;
dalta sovrapposizione a.i ai.gr";i'i"ir""'".,a;. acido acctico. l-a fiEura risulra

,.

. Esrvpto N. l l. Ca.lcolarc il pH di una soluzrbnc -con(cncn(c


litro di acido acctico c
molc/l;t . ai ..;jl formico (HCOOH)- 0,10 molc/
.0,0.5

>

, - [H+][.A.r-]- l,7j x lg-jtne.l,


lH+llHcoo- j- 1,77 x.ro-jIscou],
:' [H+J[OH-J: 1,g x tg-r. .::
'

c dai bilanci di mzs"a

..',

. ': :

;'

. [HAc]* to.-rl:.i;

,\
I

(r;
(2)
(3)

!
I
I

t
I

I
I
I

({)

t_
I
I

st rrcava il diagramma raPnrcscnato in fig- 7-8.


inoluc nrccssario un biIancio di carica:
.: ..,

[]r+l: tHcoo-l+ tac-li

iori-].

'- :
':
.-.r,.1...1,.:,': ..' :-

i.
!

I
t

II
I

(6)

:i,,:l;::.fi|
' , ' '' ;l:.ii'i:lfil
.',
.
''!!i:.'.','i:ij-t
+!'.' +',:-'- ' -.------- --'*.

'i

scgucndo sul diagramma.la tinca rappre<ntariva


lcrrtca anzitutto ta tinea- lHcoo-1.'irarcu-r_endo di Jllr J, s[ vctlc chc cssa innolle (6) 3li altrl due lcrmini
di conccntraziono, si otricnc a"tt, i.riura dcl grafrco:

lH+J: tHcoo-l
.

qucsro pH

2,g2

- _3,22,

log[Ac-J

Il

pH

2,S4.

[Ac_J

6,0

t0_r.

rappr.rrto formiato/accuto ha

il valoro
IHCOo-l

2,rl2. to-3
-J"-J:: 4'e' = =iffq-

*fit##;*;3 ;U#*}r
l-;;;;;;

ffi

x rg.-s;

:**r
-..
i;H_J,.

ryn

tncrica, rrascurando nolla


el ,ora

,ffi

Dalla (4) o daila


1t;, cspt;c;tando [Ac-J, si orrieno,

;.

;: .'; "::

lH+l_ lHcoo_l* tArl.

ry

r^--r
t'nl r -

ffi
{. ld

1,75

(6a)

lcr-c

fnrl +-i u;fp

(1)

Dallc (5) e (2), risohcndo pcr


[HCOO-J:

us

[HCoo-J' *

Ir

Sostitucndo

;;.lg_i*,0lH+j+r,fi-xJF.'

in (6a) i valori cosl otrcnuti si ha


g,gJ x tO-.
Irr+r_
rr.
J +)+t,tlxloF{-lF
1s+1{-1,r; ,o= +

ffi

1.75

I+

(8)

x If
r,7il-ii=s'

Poich' dar proccdinrento gra6coi


IH+ ] risurtato dc*ordinc di ,o.., s possono
ragionevolmcntc trascurare al r{cnominetorc
le cos[anti addirivc (minori

ffi

5% di lH+. Nc

ry

tT*l':

#ffi

del

vicnc

t0,60

x tor;

= 3.25,x l0;

[r]+.J

pt,l

Il valorc di pH non m.olto divcrso da qucllo


ricavato_pcr via
st-anic Ic approssimazioni piuttosto *zz.j"tc.-

ihq
qry

tffi

0,050

ffi

3.75

I-

rifr

grli.

- {.?5

l^c-l

llluoo-l

-J

(J-l

--5
-6
-8
-9

graFrca, nono-

0,10M HAc,

_,

CH

2,49.

HCOOH,

t Pr(. 0l- '

'.1'

I.'\c]

torrl

approssimez

Escmpio

ll

lll+

678

0l0llt213

pH

FtG' 7-8' Diagramma togaritmico pcr una


soruzionc corltcnehro 0,r moro/ritro
acido- accrico c 0,05 mote/tirro
'acido r;;;".
k nr." risurta dara sovrapposizionc dci diagrammi dci
duo acidi.

di

u;Jd.-,-..dt*lr^ifil-,*._!lrilrarig*^..

_,

'.).1-

.l

__

"rtgroEo

reo

seu-ffi

rt rq
SA'c[s,' ac'NFa
.l

j.r,.

I,q studio_-_speitrofotometrlco dei complessl l_n


ii,l ,'
--oluzlone gomtncl ad &\rere u:1 rlsore matematj-co
,.1'. con 1f,-g1eto do de1le varlazloril. contlnue , attrlbui-

rr-*-

-.

't

tri

,I

i,

r*.*" urn
'..''t' ' appilcato precedentemente.
rn segulto, a.che per 1a mancata applj-cazlone dl
altri metodl , quall 1 'analis1 rogarltm.Lca e ra ti*
\o7-azlone spettrofotometrica, 1I metodo di Job fu
largamente adottato notosta-.r te 1_Il.mfl;!_S-bS__-eSsq
-gglpgrlgj -Lnfa'btl per ur-r "orraruiio *umpJ-ice in so*
luzione r de1 tlpo:

';.

"

rl

mA+nB

AB
mn cofi,e:t-S5o

e L.u"grscono per dar luogo acl un unlco

ouando

,A.

compl

so,

es

:'

11 J[glgg-pJgl,l*?**ugr$-q*,*.Q"p*-xpr,Llnus

varido e perrnette crt identlfrcare ir rapport, **


g:li indlcl m ed n del- romplesso dal.ra postztone del
massimo delle partlcolarl curve assorbanza in fun------*- ----.---zlone del- rapporto molare del conponentl

1ar.

miscer-a:

secondo 1o schema generale rlportato nella tabelra A;


se Ho utJ

r'::','

{rgQRo g1,o

1=r)*.
L'.2 =1 \

\ ft-&v

?q^jo
d'i,o5tnt""-o'-u-

Cou.rg-ge4o
c{e_ 'lo
'poQn

r.r-r.,.-

fu.lqpo

k/c-

*r<&:c.trg

t\

.i

lr.r c-r:,

.,=

t
U

I
I

C* n Cc-

^tI,

'.1
,,.Y,

l'

- )L:

I
l
l
l
I

TAB.
Tormula generale secondo Job (14)
.A.

oNJ J tr rr,
.q-4riQ:''
i'

-t
J

v
I

_!

-t
;!

I*l
*l

tl,

SS foNflrrso PrrJ

c-orf

PuS--

el
-\
- \o

Se lnve ce si ha la f omrazlone

su c ce s slva

dl pll
complessi,
che avvlene nel1a magglor parto del
t\r\""
-"osa'
1,._
\L rtrx
easl , ]-a poslzione de1 masslmo, rrcavabrle dalle
;ft#:,,S
curve dl Job, lnfluenzata da varl fattorl, quall
11 pH e 1a lungrez2.
d'!onda ol-tre che cralla Jailro:lti:]:,-,.*
---. +
"-y-l-vYrorrcgftLrrrr;1

r--J-'

"]

ll
*i

I
*

|
'lslzlone
delIa soluzlone. fnoltra I compor.ientl che i,-,o ^
l.:.-rrvr|UIglUUl.ilpUI1eIlU].Cne-got-'.,l.to'.jt
,' reaglscono non devono sublre Ll"r., tipo dl i.eaz-rone
se condarra o col]a berar-e sra tra
-r-oro I che con 1-1
solvdnte o con eventuaLl. legandl pre sentl ln cornpe _
tlzlone come r per esempb, 1'1dro11sl dello ione meta111co, de1 complesso, 1a dlssoclazlone o lrasso*

_l

"l
i

j
;

:i'i
.l...
1.,':.'r

'
()
:l, /

l,
I

t-

l'

_.{}

clazlone del legando e Ia formazlone d1 complessl


ml stl
-+ Huttl i casl menzlonati lnfluenzano notevolmonte
1a poslzione de1 masslmo e qulndl comp-1_l cBno 1a soluzlone del sistema. Generailzzando sl pu dlre che
.11 metodo dl Job permette 1o studlo d1 slsteml seml1cl anche se non consente Ia dlstinzlone tra com-

parte del slstemr compressl sl possono gtte--peqq solo.


stsi-Drt\ Eft&fc^
. informazionl Ou*it*u*tr".lN'FonAAcllTA-m=rr-iTlE11Vtr-t-x

QtAu\rxnve i,x-sffit( cofteesli


' -------------<Ilaetodo deIIe so1uzlon1 corrlspondentl (15) successivamente lntrodotto, non presenta sqstanzlarl
vantaggi rispetto aI rnetodo _Lqg*b*.
-;ir;"centementS)rr*us(16 ) ha lntrodotto
un me_

l co che perme tte 1 re satta lndlvl cjuazl one


deg11 indicl de1le specie complessate ed 11 calcolo
de1le costantl dl formazione, anche ile1 caso dl comle ssl
]1ng9f9etl*rg con Ia limltazione del conl:_

to do

p1ess1

mistl

r^k:x"xrx,7'
t;

l
I

/ ct"ryl /rtfiortltg We
c-"

,-r.};o*,rs3=e>

^r--*4\ - 15 - 16
rfi,q

-t ry

t
?

I
I

=t

'

_v

o,

5r"t

'*

l,'

IJ
:r1J,.,.
r'\,
;

-l

(.

lnilne

prma x'udeslnskJ (17)


.,, .u)romme{
pol
v"a
scuol-a
B4s,
cecoso'o^^^1r)
cecoslovac"*(r)
if;;l':,,i.aua
;il:i,":t
,^*_: lntrodotto
":-.
.nanno
i:,*::\. i..

iiitr r,

-l

"

iffix
ll

fi,U;

)
-j

ah r

. ^,

**su**;

compone"*r
id91l
titi:=-r------ ,;;; ll-II-rJ-^jli

-l

l i'r"

rli::

1a

un nuo_

ne- v'lr.r.a
"^'ll
qL
a"i
t-qLl.-rgrlgpr11
"inl

"u :1 pH, rlsolte

pro po st

funzl onl
r.A3.

rneur"n_

da

rlpor-

1o studio

de1

I;.-T\,'i.,hA

R=L

'3.'.:l^'; \.

ffi#r'*.*
dlftfiiilil
ffi=

..i

ii

:+[+t$nli7t i .

I,lndaglno qr_ron*-:l; l-ro f o t ome t

.. ={"Lo31o.o
k (_A D
QurL\gtu
ro steti tol'-^*l'
agstr=u"l

.,.*

r1 c a d
,,on. cr-omotronJ o,Cc-f-n-\

i,,.;l;TfT1-,--:!3tt

gt

6q.

;l
cos6i

!h, *f6.

rt
,l

\L/

fusfuffi.'?*''
;ilt
j..

'

..

*qtx= 3 YNiJlT*coH1-o*
"''a o
iir.
i:ii::.' o 1-

\-f-

t'
l
I

l,

i:

r:t:,,-ii-

I
!

_ ZL-

t
I

i
.T

j
I

t\
...

f,a re ezi one deJ. cromo (f f f ) c on acl do cromotropi


co cjiventa significativa a tog
[rJrf per formare
un conposto solub1le verde-pa111do neIIe c
ondi zi oni
sperimentall in cul abbiamo operato.
la reazione p::ocede molto lentamente a temperatu_
ra ambiente e ragS-iunge la comple tezza dopo
alcuni

giorni; 'ra velocit. delra reazione aumenta


alr-raumen_
ta.re del1a temperatura.
soluzl0nl ottenute da acido cromotropico e
cromo(rrr)
hanno identiche caratterlstlche e sono
stabili per
diverse settima-ne sia tenendole a 25 oC
sia facendo_
1e bollire e riportandole poi alla tempera.t.ura
di 25 0c;
anche r-e caratterlstiche spettrofotometriche
rimangono
invariate.
Per cui 1e mlsure spettrofotometriche
sono state
fatte dopo aver mescolato i componentl,
averr_i fatti
bollire per 2 ore ed averlj- successivamente
riportati
c

1
L)

Oar

U.

Gli spettri- di assorblmento sono statl


reglstra.ti
1n funzione delll_?@:j"11
recces"" ,.-f*"" ai
uno dei due costltuentl il sistema.

te

le curve di assorblmento che sono sta.te


registra_
in._eccesso_di_
iglt 119t.4llri r rnostrano massimi a

tr
'::o

I'

-LL

:r

I lu(

, 340, 325 )-4) llm.

.*)

ff*f

Gl-i spettrl ln eccesso di agente com lessante so'r


no sr-nili ai precedenti fatta eccezione per un
nuovo
massimo che com.pare a llO

-nm.

Per ellmlnare f interferenza dovuta all'agente coraplessant per il forte essorblmento a basse lunghe zze
c1 roncla, le misure sono state eseguite a 37 5 nm.
DI
EAUIL]BRI
ffi

-:itekffi

COKfPLBSSAZIOKE
aa
ttF*r.sa!--.dE

I risultati dellrappllcazlone de1 metodo de1le soluzioni e gu immo lecolarl eed e111a t,1 i a ret
mettono
A1
in eviden z^1 pre s enza L1I
co:
om pre S si c on conpo sl- zl- one
I ro o Z
( fi g. 2)
.nd o - 1r1, 1
met allo/l egan
La pre SCTLZ.za di dlfferren ti qui l- ib ri di c omp lessazLone rl- s ulta lnoltre daall- ECcu rve AC id it /assorbanza
,+ -r.l
o

.[ = f (-1o sul 'lJ )n n eonnC J)


o stan te (ng.
"M
"f.r"Ni
e da1le c urve'o as s orbanzaa-c oncce.ntr a oi on ed el co mponentl
A- = f (CI)
A =J_ r.
e
1( c)
n
n
1o
!
l',I
1o gLH
s
"1,1

t,

.:-^ il
\J.t
,

h6

IL1

[H.j

\= costa nte

L_

3)

flg. 4).
Una co mpleet a analisi de 11e
1 o cur 1/ e SE con do i-1 .fit'd6
di Somner (18 ) mette ip eevi den ai SE gu ent t o,u illbFI-

2:\
I

l:L

in soluzlone:
2Ir + .L2*
1^

II + H^L"-::*
2'4
I'IHI, + E2L'- :
..

M^T,
'2.

+ 2

.+

r -Il
(-rog[H]

H'
-l.

[Hl E
.rt1
tYI(Ht)2 + H*l t-roelI J
I"[HL

H'

,:

-ros

L's

.'\

). 'r.,
/ + ,3i'5)
')
ir ..a \
4';' t :5r.3)
i

.i
I

'

l,t

l:

tl

. ..:.,
j, i;, ''|-14
art
i.:.
,'ir:I, t

I
I
I
l
I
I

- 24 -

La formazlone de1la specle pollnucJ.eata ha luogo


con rllascio di d.ue protonl 1n soJ-uzloni con largo
u"sso dl metallo (cM/cL = 10 t 20), mentre per un
rapporto metalJ.o/Iegand.o m-lnorer si ha 1a formazi-one
di una specle mononucleare secondo ltequilibrio riportato. ,A.1-lrsumentare deI- pH si ha 1a coordinazione
di una second.a molecola di legando e ancora rilascio
d.i un protone secondo. 1 f e quilibrlo riportato.
L'idrolisi del complessl .rnlzta a pH >z 2r5 per sol
luzioni 1n eccesso di metallo e pH >.5r3 per soluzio-

t'
I
I

t,

)\

ni in eceesso di legando .
. -_-f val-ori de11 tassorbivita molare calcol-ata "(llS)rl^
e i va]-ori delle costanti di equilibrlo ottenuti-at'
raccolti ne1l.a tabella:
1'analisi grafi"r(18)
"oro

lv
i
I
I

6-

_A't

ro

specie

Ln.lo-t s r,- t
(,{ = a 7tr,,,")

MzL
liiHL

o,64to,o?
or62!o,02

l{(Hr)2

qui

libri

log costan-te

,zot

O, O6

[orr] L*1'/
[uHr] [r.]

ZM

[nr nrlrJ Lyl ,

Frrrj

/Tq' Jl

frurru-l

/ b' hrL

.[,i

1ni, ) zl

[uriJ
L*,r]

LnrJ.2

t*r] lnrri

/ [-] [nr] '

1r 58!C, 02 ,
a , 65t

o, 02l'
1,1

-lr75tO,OZj'
,,
19,5910, 04

6,ol-to,o4i,
9r621O,06

l.

Per 1 teccesso dl metallo 1 valorl del-le costanti


di eguilibrlo sono stati correttl tenendo conto del1 tidroli-si clel metallo assumendo 1a presenza(19 )
\\1,
j*
crr(oH)
cr(ou)2*,Wrr=101o)
e
delre specie
Wzz=1o?')('0,

ir
.l

,l

fz'

1
I

-LG-

?
-I

-ACIDO

CROi{OTROPICO

,],Ifi-u ilrga .cg-r P{

-{
{

'i
i,,

1IT
Lz :'eazione tra i1 cr'^ e I'acido cromotropico.
lniluenzata cial pH; in pratica pir alta lracidita
e:ag;icre la. vel-ocit cle11a reazione come risiurta
da' r a fig. 5 , rlove .riene ripor.tato 1 randamento de1la
Teeztone (C/Cl,l = costi.:.nte; aciclit costante ) se{Tuen_
do 1 ,andanento 'de1r-ra.ssorba,nza.
^@nm in funzione
oc.
de1 tenpo ed a ?5ro ! o,2
si ''red-e che 1a reazione
richiede circa 3o ore per rac.qiungere l-a compl etezza,
zentre Ia reazione molto pir) rapida (ro*r! minuti
se si eleva la tempe::atura lntorno ai SO oC.
-'---

I
I

o"},911.,

II

]"-"p"Lggg*., g

s*b] lq,

"i-gseEig:]e

c o1o

rai o

E' noto che 1"r1cido ,cromctropico non assorbe nel


visibile ma nerrru.1/. come si vede darra fig. 1; i1
cr'- in a.'nbiente aci do ha uno spettro con un ,,plateaLl,r
ner f into::no di 42, nm ed un massimo a
3 50 run come si
',zede da1la fig, 6,.
!o spettro di una solu zLone di acido cronotropico
e Cr'* in aribiente acido (Cr/C* = costante
I a.cidrta
-u-ariabile) prusenta un massimo
ne1 vislbi-le.intorno
a 535 nm (ffg. 7), mentre neI,U.v. (fiS. B) presenta
una spalla intorno e 2IO nm.
' ', i ., \i

ri'/ r."
I

ll'''

','''' ( [lt

No
' .'- i ..

\3Bo

nax

\)

il

't,

vl

tr. i'i
?]

t.

-2t-

l
-t
I

-I

I prodotto cli ossidazione deII 'acid.o crornotropico con lIrO, un composto colorato in arancione
con uno speitro de1 tipo riportato in fig. 9 per 1a
regione del- visibil-e ed in fig. tO per Ia regione
o-l I tTl

',f

Si nota che 1'effetto .deIl'ossidazione nettamente diverso nei due casi. fnfatti il massimo nel
'
.t,
vlsrbil-e cade a 425 nm e non e 535 nrr,. 1ffi$i1
I{e11 ' U. \I. si ha uno spettro del tipo di c7ue11o
di fig. 10 con un "plaioau" a 310 nm ed un massirno
accennato a 22O nm

lJ

Effetto della concentrazione del- CrW


TTT

La rcazione tra 1 raciclo cromotropi co e d i1 Cr "


ad acidit fissa influenzata dalla concentrazione dj- crornato. Infatti come si pu vedere dalla fiS.
11 1'assor-bauza a 5l-O: nm :::_":" per utY rapl;orto m/t
fino a 2- e quindj- decresce fino a valori minini per
un certo rapporto ltt/L 6,5 . Que sto lascie pensare che
inizialmente tra iI cromato e l-'aciclo cromotropico
si ha una reazione redox con formazione di una specie colorata (interrredio ) che v-iene invece degr"adata acl elevati ::ap1,orti di '![/L.
r prodotti di degradazione evi-denziati sono CrIlI
( racco]-ta
(reazione violet'ia con EI['A e caldo ) , CO.
z
su Ba(' oll )^t ) ed So,2- (precipitato con lar, ) .
,+--_

74

II
I

-28*

-_l

-l)

E[c$,g-."eJe

*sg*gg!!ragls]g

/t condizioni fisse di cromato ed aciclit, un eccesso di acido cromotropico non infruenza la reazio_

ne

rapporti LfM >, lo"

come si ve de a"f-*""ij-co
gral l_ co rlel
I a f i'i cg. 12 ,
del-l-a
il- rnassinro a (525 Inm rimane prssocch costante Der
.t

-.J

I
lI
-

; inf atti

-l

Effetto del]a concentrazione di acido cromotropico

+-%wY!ffiffiffiffiE@

^\rI
eur
.%.-

La conce,trazione dei due reagenii influe,za ra


reazi-o.e o1t'e che . nei mocli gi riportati anche su1l-o stato r'isico dei procotti; infat-ui- per concentrazlorri rnaggiori di 5. fO-i M (CN/CL = I ) si separa un
composto sol-ido col-orato.

ggw&flQ AL]g- r Ar o sol,r po

i
t

lv

-i-l

-t
-l
.-l
-t
I

-r*

I1 ccntposto aIl-o stato solido che si seDara da


sol-uzr-onr- ci crw ed aciclo cronotropi co stato
allaTtzzato rnediante ane_f isi el_ementare, termogravirne_
trica, Tralisi spettroscopica I.R. e di riflettaanzz
di ff u sa.

J
_ 29

l
,J

.[nallsl elementare
@

fic

iletermin azl.onL

-i

lx

Lr

27

,65

3r93

26

r1,2

3i16

24 r25

2 r1o

/"s
12 r7.4

/" cr
10, 25

re si duo
14r 10

8,BB

-l
I

I risultati delle tre ana11si, eseguite 1n diversi laboratori, non sono in accordo.
Tuttaviar ssumendo i valori delltanalisi ilGir , che
l- 'uniea completa, ed in particolare considerando il
rapporto C/S/Cr, si trova un rapporto lO/Z/t, che sa*
rebbe consistente con un composto ln cui iI rapporto
\1/L di 1:1.
gssume, quindi 'la pre senza. dl un composto dl for-S_1-_

f\

rnulalIItr,
\Z xII^On \

li
li:
li

'it

rl
Ir

!i

ll
t,r

Bl9#33{-P,-EJ*-l*AI4.I-gEBr,log84yII$gBIg

tlpo sono rlportatl neIle figg. 1l


14. si nota cha la decomposlzlon termi-ca awiene
Termogramml

I
I

-l

l-n

Ji.

I
I
I
I
i

J
-'i
j

- 3o -

tre stadis un pri-mo stadlo flno a lBO oC; un seconrlo stadio, costituit Oa plr processi sovrapposti e
d.a 1BO B 52O oC ed un terzo stadio
non risolviblll,
da 57O a 72O oC. Ne1 prluo stadio si ha perdita dl
come confemr f* presenz dt un picco endoter.acqua
mico ne11 'analisi lgrmodiff erenz:-al.e. (ff S. f 5 ) ; ne1
s_econdo Ia decomposizione flno a s1fato di cromo (III

e ne1 terzo stadio i1 passaggio da solfato ad ossido


di cromo (rrl) .
f,e perdite percentuali in peso sono riassunte ne1- G
fri, f. \ ill
1a s eguent e tabella: ) \i. ,\r,,
10 staclio ( lo + 1Bo oc)
Zo stad.io (1BO + jZO oC )
oC
J o stadio (SlO + 72O

9,4

/"

55,5 /'

5,6

I risultati dellranalisi termogravimetrica non ci


consentono quindi di qssegnare con esattezza Ie perdite ponderali a ciaseun processo; ad elevata temperatura infatti i valori sperimental-i non sono in accoroo per l-a decomposizione del solfato ad ossido:
il fatto potrebbe essere giustificato da una interazione delIo-_S che rimane parzialmente legato a1 platino de1 crogiolo.
(.
t' i ^

Ir t-t - lr,0
it t-

\
I

r.n\
co. I\.',-d/1.
.

t{,'

5to

"t

1t

.J..

Y/0

\-..

(1,o3

,l
!,

- 31'

]r
i

I
I

\\.
..

I risultati derr'\f sf termogpT,.t,,etri;a ro,.

de1le perdite ponci condentono 11 calcolo\esatto


.\
lnfattl 1 valoij- spederall; ad elevata temperd,tura
.
rimentali non sono in accor(o per 1a decomposlzione
de1 solfato ad ossldo.

:l
i

:l,

..

AN^lill

SI

SPET

TROSCOPI-q{-I -.Rt

t,

a
!

t1

(.

ranalisi spettroscopica I.R. soI risults.ti


no riportati in fie. 15 e vengono discussi ll-:lt:
con fo spettro dellracido cromotroplco da sof'ronto
,+
l_o (rie. ]7) e con 1o spettro de1 composto solido
Croriro (II1 ) - /rcido cromotropi co, ottenuto come riparte sperimentale -(fre. 18).
poritriri"
G1i spettri I.R. dei due composti del cromo sono
abbastarza siniili tra di loro e mos-trano entram-trl
una banrle larga intorno a 3 4oo J-I- ao:rrrt" tr gruppo ossidrilico legato, banda che nello spettro f.R.
del solo e.cido cromotropico te4 evidenzlabile e
stretta.
de11

4U4lIJ*3IgE99zu4

u Er rr,pgr Atg

j{..

!II3gg4,

I,o spettro di riflettanza dif'fusa Cromo (1II)


Acido cromotropico riportato ne1la fig. 19 mentre guelJ.o deJ.lracido cromotroplco da soJ-o riportato ne11a fig. 20.
I1 composto risulta completamente opaco.
-

Li
it

-37-,

''v

,t.|

CONCTUSIONI
r-',{aa-F-

1uc d'ei rleuJ.tatl espostl che debtrono ritenersi pressoch completl per ouanto concerne i1 sistena Crrrr-te1do cromoiroplcor ltr& preliminari ed
j-1 sistema cru-acido
lndica.tivl per. quanto concern
cromotropico, si possono {rarie aleune considerazio.4.11a

ni ed i presupposti per 11 lavoro conclusivo'


a1ItaUna risposta precisa s1 avuta in merito
zione ossidante de1 C'W nel rl8ualdi de11.]acido
crontotropico: ossia si tratta dl una ossi daz:-one
distruttiva con liberazione dl CO2t HZO ed HSO; e
formazio4e di c"rrr. la reazlone procede per stadi
i =i""tta aiiendenza di elcuni f,attori dei quali
suff--n"iu", del prodotto finale di reazione determinante la concentrazlone de1 cromato come pu rilevarsi dalla f1g' 11'
Di fatto 11 primo" stadio clella reaziorte consiste
in una ossidazione przlale dellracldo cromotropico
colorato
che porta alla formazione dl un compostoTTT
nel guaIe presente ,L::tl-p'n:*=: 9"' Cr"' (ottenutoperriduzione)conilsubstratoparz:-a1,menteossi_
dato (prodotto intermedio ). Questo si ev-i.nce da1 fatto che in soluzionl di acido cromotropico1rTa concentrazlone fissa, 1'aggiunta progressiva di Cr'* determina
un aumento dl tale complesso flno a raggiungere un
cuemassimo (prino tratto deJ-la curva di fig'11)' In
sta soluzione non si trova c'rrr libero n iI c'rrr
pu legarsi alJ.'acido cromotroplco non ossidato 1n

.7

t
I

)
:I

I
l
l
,

;:.i
t.

, ,.r,ii

quanto 1e caratterl-etj-"o"otlln"*tra1r de1 composto ottenuto sono dlverse da qubile del complesso c=llf_
acldo cromotroplco non os1dato.
.
Pertanto in manler sciiBlhatlca guesto primo sta-

dlo si pu cosl ihdici"gl

crt

crw

st.,

H+

--------------) cr,q.bcrrrl
(intermedlo colorato)

= acrdo cromoiropico
cr/-o = acido cromotropico ossldato parziarmente
nml

uJ_A

i.nche 1r HZOZ ln grado di ossldare 1rr:cldo cro_


motropico, ma 11 prodotto intermedio che si ottiene
non 1o stesso che sl ottlene da1 crw, come dirno-

strano le caratteristiche spettrall di tali composti


(confronta fig. g con fig.l ). In que-sto caso si ot_
.
tiene:
CTA + H^Otz

CTAO

---)

HeO

11 composto si isola a1lo stato solido e si presenta di colore rosso-violetto scuro; si pir ipoti z
zare una formula de1 tlpo

crr o({ryr

:r

tj

.r

,(
I

I
t

Prove di eomplessazlone
tra urrIr e CTAO non danno alcun effetto; ci algitrlflca
che 1]. CTAO non com_
_
rrr
Piessa il Crt
I r*j:-". *t condlloirr 1 ,lnterme dr-o crAocrrrr
o

sij
_

I
i

"1io fiiliIlH- compG%*;;;:


;enar"
to
stadio flnaie a"ri" r"rrioir"
po"i'-:"ir"

comple_
ta ossidazlone
ne con llberazlone
l-1bera:
di ,o2, Hro, nsol e
n_frr
ur ; in forma esemplificati.va
.
4
,

I
/
I

\ crr,ocrrrt +'

r-.r.w
va

H+

flzo + ,oz + eltsoO +

r1 meceanlsmo che--sl potrebbe


ipoti ,r*r"(rr)
Ia reazione il seguente:
r
ot- zo

crrlr
per

i\

(/ \

/_)"

+ HcYo;

/-r-_-

()

so;

r;$?

tr-

-l- {+> \
So;

l\
HeO

"oz

HSO
4

crrrr

r''

lnterme di o C- r ,.\.
C

o&\ 0

!
!

.l

-i

't

,!

.r
.t
1l

Ir

:I

,,:.1,i4,!i,,.:

t.

t,,:

.,.*.

t:

ir*posto da Menta"tt(22) per


]-a reazlone r"ITf-c"tecoIo. I,tautore propone una
reazione a pl +dii 684 lnlzlale formazione di un
Meccanlsmo analgo

l
l

complesso secondo 1 {.tiA{one:


i'

2+

Fer* + Hrcat

fre(cat )]. +

2H'

e successiva ossidzlona del catecolo e chinone secondo le reazioni.:.

-t
I

F"J* + Hrcat :

I,"2* + Hcat' *

a.

I,'eJ-+Hcat

'F"2* + qno +

H*
H+

in corso ulterlorl studi per deflnire la cinetica chimica, Ia composlzione de1 composto in soluzione ed ogni altro parametro utlle alla definizione
del probema.
Per quanto concerne 1a reazlone tra i1 crTrr e
I tacido cromotropico, essa av';iene attraverso l1berazione del protonl e chelazlone de1 metallo attraverso
i gruppi ossidrilici:
Sono

ry(H

-0
L
/-.),

OZ"\O

ol \0

r)

._

l.r
t,
t:
:

:,
al
.'i

-36,
i
I

lor,'(

o'\

Me;
/\
00-

ri

Me-0

i H"L
i

/
-oug

o"\

La reazione molto J-enta a temirera{ura embiente


ed avviene rapidamente sol.o eI.evando I.a temperatura.
f complessi che si ottengono aono d{. medj.a forza:
essi non trovano alcun impiego utile per iI- dosaggio
spettrofotometrico de1 CTTII, sia per Ia sensibilit
scarsa si a per 1e cotrdizioni operative in modo De.riicolare di.J.ungh ezza cl t onda.

"conpLgss

l-

(LLO Sf,xf,o Scx-llol

t1

ii

rl

it

rl

ii

-1

il

ccKeue ssI

-l

NEL

ti

C,*^

ll
lr

TNTRODUZ ]ONE
I
I

I composti di cbirdinTzione de1 .name


con 1e fosfine e le ansine tenzianie sono noti
da tempo (1-B ): I in essi i1
espl.ica

.metal1o

sm

pne

i1

i1

numeno

nLlmeno

(n,"r)
=

,'
J

,i
I

id.ogenobonato di sodio si ottiene i1 composto


te t naid

..:

di coordlnazione quattro.

E' noto che pen tn.ttamento de1ltal.geno Lnis(trifenilfosfina)


ranre(I) coh tetra-

t1

lilo, H.
t:

dt ossidazione (I) e quasl. scrnpn

nogJ

enobonato b i s ( t n if

{'

en

i 1f osf ina )

ranre ( r

"t

in cui i1 gnuppo BH,

legato aI nretalLo attna


'-+ ..-,,.*--.-*
,,.... ,,

.,l

,t,

,!:

=.

venso due idrogni a ponte con legaml .Lricontrici

,:

,.1,

''1.
',1

*,
l{'

.:

h.P

:;t
'.:i

hro,,,,,,

-:,

:i

.,.ntNI-{
t5

''

:
-i

Ph,P4

-I

,il

w-l

i's
-
i,l

l
I

il

i,,t1

,,1

rl
'II

.t

I
I

l
I

\,

5-

Di questo composto stata studlata

1a neattivitr con acid i aventi poco canattene


I
I

legante: in tale occasione. stata messa in


evidenza 1a stabilit de11'acido di Lewis

I
..,]

+
(Ph^P)^ cue la tendenza del rame aIla te.rz_

tr'i-co, pcrc.l.ot J.co e 'Letnal'luonobonico sono

.;

statj. isolati e descritti

-i.

con gIi acldi n1-

tnacoondi.nazione" Infatti

i composti:

ftnrr.n

l,

cur'loJ

_i

i1 primo

rnonomel^o

coI gruppo nitrato

cltelan'be

ed i1 seconclo dimero con due gnuPPi Penclorato


)

tI

a ponte, ocl in'l'1ne, in pr.:senza d1. f osf ilat

com post"

I
I
I

[,Ph3l'

cr-rerf

non

elettrollta

monomero.
t
t

I
I

La tendenza quincli aIIa tetracoorcl inazione pen questi derivabi fosfj.nici di rarno(I)

cos esaspera.ta da legane io1i.-.:,_,"


)

No,

-1

a"

,.J

-1
-

-l
-l

-l
J-

rairt

lessi
''';

'

1';

''i

'

-l
-l

'venti gia' di per

saiicilico, ac. antranilico, amminoacidir'Phi


';

Ilii,t"r'l

r.1t

se

azione antiinfiammatoria, sono spsso iiffi,

iu' attivi dei

leee.lti_Lbsr(U.
it"rr{i
,1

stato inoltre dimostrato che questi stei;i


r ..,...l.!{
--._

'

plessi pron'uovollo

.;:..,1,1fi-',:

processi di ricostruzione dei tessuti prevenetido,ll,ulce.a e promuovencio


1a

c\catrtzzazione.

In queste azioni si possono suggerire alcdrrl

quali l'ac.

fra

i quali due

sembrano piu' verosin-rili:

I complessi di rame possono


il _:-_
seivii aejt
*_*"-_1_-_.a.a,.1;:
metallo stesso e quindi rifornire ed ttiv5iA etrj

I
I
J

I
l
I
-ia

b) I complessi di rame possono avere


3 --.

ilnai;
,,
.

.:

ha portato allo

stato

di malattia, quali ad esempio I mr


i "i, ,i

,ssociate

processi

infiammatori, dove

1a

iiberazione o il acctiitii

un ruoio etiologico (cio da causa inir

plossidi puo' avere


io etiologico stato

"..;:r,.,

;- --: :,

I
I
-
I

"(-,

di artrite (3), di

provato in modelli anirnali Pi


epilessia (4), di cancro (5-7).

co dovuta a1l'

Nei casi in cui ia causa dell'


t

-l

.";i.&,iail&.98iiil&&j

.,. ., t.,-. :. _.;;..-. : -;:

)'

o-distnUtante dei

accumulo del sttperossiio, ailgl{r,


I

r,;:

r"til

complessi di rame opprlt il iorO fi


'

l1a

alilvazione di

; iii

questo enzima puo'raPpreSehtafei ' tl'''


.

'.t..

1ibile.

.I.:l

ntineoplastici in

che hanno hotevole

tUne. Cosi

il

tassolo

I
I

estratto

dal

tasso barbasso, cosi' 1 p

[tau" da una spllgna


ci-Platino(B).

l
l
I
J

I
I

I
:

-q

ri

r3

J-'
.LJ

LJ

rj
.L'
,L'
I

I_l
l_I

ii

.'lt
,1i,i&l

t',

AJla luce deile prenr

quih.di. pensato

possibilita'dl lo

,!t1

tl_"_,,'-'
!r

alcuni funghl oiig

sostanze iossiche

I.

,rit,ilii
I

,"sp,in;ii

,fliiofre tossica di questo fungo nel

..-.,'1]r:.,

caso che dopo la sua intlohd

quantifa' elevate di bevande

--.--..-

alcooliciie.
11

Disutfiram ha

f,

fofnriiiX

l_l
l_l

'i

A tale fine abbiamo scelto tra le


lcii ,i
trova nel funpo
(-or'i-,,.
- (f -vrrrIuJ

il Diilliif{

SoSittze tossiche presenti in

selie di tiansizione che sono

spesso coinvolti in re

akamentarius ed

di studiare la

Uil

hte:
ii

(CzHs)2NJ'--

'r.ii

g
lt

'- -'

---. '*

. g-- N(czHs)z
rSr

-l

di
I

l:*l
-l

ffi.i

doppierti solirari e fra questi,

pi esposri sono quelli present

ne gruppo

hochetonico:

(et\.ti-1",

*l
-J
I

.n

&

t',i,,lr',r;.;;;;;,i-o.,-,-;,.,;,ii,;1;:;.*:,:iat;r:::.I*a.riiirH;;:;;tir;it:iau;";:.*)dtf.lgi'=**viti!i''4'"1-:'"

""

'-''

4,,

t'

-gia

nel grrrppo

disoli(l

adatto perci

Disulfiram

forma
\rt

h.a

Abbi
Rame

cu(c1oi;e

MeOH

-.(/
trfrO

A
T ambiente

::;Ii
,,iti,t"li
ll'ii

'
,

'
q!-CdffiJittde
scuro da essa si separano dei
assltme Subitd
assltme
ia soiuzione -""-"'- -,, tI t$,cdifiL-litde
;='i,iimf,if,;
'

"i;

:'--'-Yj*:lY:"

cristalli

,.rriche

''

dopo tuti l Uppil,lHilt indaginisono risul-tati essere:

i,ri,'ffiiii:",

, ,;' ,
,,'

llliii$ii.

,,j,rill::
i

*".i
I

..d

ri' i:ri:

:r

._J

5l

i..

l
I

GH.

A=

-N
CHs

-l

I
I
I
I

Per verifica abbiamo


D

i" i,l.g ili

g.ca

1b

m m a ro

CzHs

ptF

so

coinposto

partire dal

+*

co ( D i. i'Uiilifl.,:i,

\
2

il

c-s

Na.3, iird..{'iiicu

( c1o4 )2

urrro

QHs
CzHs

C.H.

b*m

crg{

*l

+2NaClOo +lZHrO
CzHs

-l
I
I

:i

-l
I

-l
I

ottenuto ha
na le
te stSg'l
t*lii ,li3llf;lifrl'.S$,.e-S
ll11 composto
'":Tfo:'o obtenuto
,,.S[*f-g!r*o di fusione, spetro
.
I.R., anatisi

cHN

ciel

i'ii r;:.:,

composto,,;'

,J:,
', .',
.

I
I

*l
I
I

,;
-t
I

I
-l
I

l-

i.

,'ijl:.iff],.,
'.;ii:friil;,,
..:i-",,'n4i.i,^,'

I-a struttura ai raggi-x hii cohielti{l"lilibgart.zza eha formutazione


' lir:: ; ';
.i;i
risultando il complesso avl UHa d{
quagi plairare quadrata
. . {;{r (i;.,{j
r';
'!i

-l

'rl'[

'j;'

.T
.i

',

.:
,/Jrrl

;, ",

:iIl

.t_..]
' ') tt1

I,'

t,
,j

,l
-l

t'

...t1!-

i
I

bontatti

ed

'1:.i.r1'

con

pitl{ ignificativi

dngsli,

il metallo al cenko

de
't.

kovano i quattro

atomi di due gruppi

La carica 2+ del

metallo viene quindi

ditiocarbammati

risultando qr-iindi un
Dobbiamo quindi dedurre

chU

;:{$ii"',
nelld fdaione tra Disulfiram
.

:t::fif,!&ilii.,
. l' !ir: : .

Cu (ClOq)2. 6H2O si ha idtog nazili,{I:


. . r .,iril:t
.
:.

ii'

^,',.1.t1

i,'i'
:

..'..,''

!:,I
i, :'.,,,
"' ,.;;i...
g

s 'ii:S(
\
/
.,
1 ri;;i'.,['i.,'
i.e1,iliri'

C
l\
t'

':

:i; lt;;1
. ' :), ,ir:i;-1
" :'_i\{"

11,,,, : .,

, :,"i,:i-j't
.r,.1.+,
r.

:,j:,.1i
,

'

'
.

, ' ! .li

,.1i

: |.t:..'i

.,:'r,1;.l:il.
.,:il 1 i"rl'l
' i':t,'ri t
'

'.r

)rl
..'r: i rl.r

,.ij,,lrar !.
'_.- .t '. I
: ".1 t ..,

'. ,

:1,,,,i

i;
. ,: liiri.
;r:,'

''.' ., r".''lj,r'
.'
)' l -9,,i t,

C--

ll,,r'I
S

l:

rj
ll'

l?
'i'i,i

t..

i
1,t,.

.,i

cohsegllAnte io

btiie diSolfuro a spese della


)i,',

t-

!ie si ossida ad
(conferiiiato ai

aicleidica

ilivela l presenza di aldeide

[_

l__
cH2o

!I

t-

I_

.;

,;.;i."

,ill

iijl

e successiva chelaziotie

t_
I

L_
I

L-

)s
t.

I',
\

:''
::..:r,.

r\
I
I

C--

. l,/

S,

-e.i

J"
J
J
J
J

JJ
J

J
J
J
J'*

J
J
J

c tr( E T i rNA.
AIcuni oligonretalli sono essenziali per la vita, e, sotLo
fornra di corlplessi in particolare, sono risultati agenti farnracologici

rnarcatarnente attivi.

attivita' tton e' tnostrata dagli ioni degli


oligontetalli quando si presCItnno allo stato "ittorganico" lle'dai
leganti liberi i quali talvolta presentiuro un'aItivita' piu' genericl
QuesLa

neno circoscritta colr etfetti collaterali indesiderati

Alla luce cli queste


sintesi

L-D d-(@gal.

,,
HH ,,

)-(^s^v/*lf
(,*)-",-,.

ranre perslg-.[-4!g.e.Jil"."c-Uli9!"islinA,.

.-..4-.-*..*--|

(l

cohoscenze abbiamo realizzato la

di un Iruovo cotnlrlesso tra il

tl *-"u'
N-c-N

crtET r siJ

l,
l-t

(1)

clte e' da tempo conosciuta corne un potente anLagonista dei


receLtori H2 ed e' sta[a largarnente usata per trattamenli nei casi di
ulce.ra peptica; essa inoitre presenta nella sua fonnula diversi atorni

cor doppietl,i elcttronici non conclivisi e atti a [urtziottare conle

[rasi

cli Lewis e quincli un buon legrite policentato.

Il

cornplesso isolato

di cui abbianio

determinato la

strut.tura (2)

J
J

'.<-

J
q

:lLI li:

Q - Pca^: - ?- (o.,

t L-(

.f

1(

Aoo\

VER.

(2)

e le alrre propieta' clrirqtrq:lSl_e1_

rl:rr::!Lj:"'

i:l:"-llillti"t e

r-_s_B!g_s_ojlg

risigg"iloJggl-?l:-.

q_!_o_

a{ afl]j"qi

r (n ;

Nell'indagine farrnacologica sono stati effettuati test di


screening relativi alla tossicita', sistema nervoso centrale,
cardiovascolari, nretabolici, in[iarnmatori, allergici, rnicrobiologici. Da

rilevare in particolare che rnentre la cimetidina cla sola inibisce


sect'ezione gastrica,

il

la

cornplesso det ralne e' inattivo su tale

fettornetto, merLre presenta una forte azione antagonista sull'ulcera


cla stress ed e'scarsamenle attivo su quella da etanolo.
Questo cotnportatnento
rneccanisrno

di

azione e

J
J
J
i
I

per]sare ad

url

cliverso

in pullig"glll" ii

azione sui recettori H2. Dalle

_J

fa quindi

:.91:tr1:.r:?_,,o,1 rnostra
analisi cardiovascolari si deduce una

clebole attivita' anLagonista sui B recettori.

.
cottrplesso

L'atralisi istochirnica

e fisiopatologica contlotta sul

(2) e'consistita nel ,saggiare I'effetto che tale sostanza ha

su alcuni pararnetri funzionali cli cellule coltivatc "in vitro".


I3sperienze prelirninari rilevano una maggior inibizione

della sintesi del DNA nei fibroblasti norrnali e nelle cel.luie

neoplastiche.

I
.J

r-'ql

#
*1

Abbianro ora indirizzato

il

nostro interesse sulla

interazione della cime[iclina con I'oro, eiernento d'interesse

/ t<

slaLtC^'Jia & .t'("'{., :rL^


O"n{qb(oqe fit t *.f, :

PLre- Av- q
farnraco

1e

c c-r

!i

tygi Jf

y11*{=5:'_" I i,:*11? !l i"

Dalla reaziorte tra clorotrifenil[os[inaoro (I) e


cirnetidina in presetr za di LgJl si e' isolato e caratlerizzato il
cornplesso

tiolato

cli

(3) che

all'inclagine strutturale

^"

_l1li

:{ '. *

OilrLt r,

e'risultato essere un

[ormula:

-P*Au"
(CoH s ): -P-Au

5-

lt

-S - CH2-CH2-N H-

il

C-NH-CH3

(3)

-,i!i

s
J

con I'oro (I) in coordittazione 2lineare.

Lo gg"ualll-ryqllg.g--p-gltfl-Lg

l-1.--r-911ura

del legarne C-S

J
_g

JJ
J

J
Jt_
J
.l
[r_,
J

in (4) ecl il tiolato che si libera si le[a all'atorno di


oro (I).Non ci sent-iarno di attribuire que--s-!A .to!!urA alla presenza
conre

della KOH, perchc' clurante gti^.11[cf] ,,tgi ""l-"flr1ti def. ratne noi
abbianro spesso operato in queste conclizioni e non abbialno rnai

rilevato situazioni del genere; sianro quin<li piu'propensi

ad

attribuire Ia causa ad unA azione catalitica <lell'oro..

-'.

'

' ' rr:'ou ur,l i

L+]

resziouwua'zi,rr gitE!rr';.''a!-qF?r.*T*{er.r

Il tiolaro (3)

all;r prelitnirrare inclagilrc [arrnacologica

prcsenta aLtivil"a' antibaItcrica rispetto

ai ceppi Metlr Res S.Aurcus,

E.Coli, f'.F'oetus.

,it

3
3
3
3

l
l
l
l
l

A' M' l-Jiarrrrcci, Ir. I)cirrlrtirr, 4. L.'Garacru, M. 4.rrr.sser.o,


N.
Mirsciocchi, I_. Nalclirri, A. panzancili.
A4c(;rl cotrPlcxcs oI cirrrcti<line. Sl,rrtlresis
arrcl X_r ay structurc oI tlrc
IcirrrctidintrecopPcr(r I)J'r- cnriorr. i,,or.g. r,i,.,.,. Acra,
00, 000(1990)
l. I)crnartirr, M. L.

Garurrltr, itrl. ,1^,r1ssero,


N. 41sciocclri, I_. NalrJirri,
-----' ^"
A. I,arrzanelli.
Syrrthcsis anrl X-ray str ucturc oI guanirlirre,
N_c1,11y1e_N,_(2_

nlctcaptocthyl)-N"_rr)etlryl_rjcrivative
clrlorotrilrlrcnylPhrisIrrine gorcr(r). Irrorg.witlr
t,i,,.,, Acr.a (su[:rrittecr).

l'. Pippia, L. Sciol^, A4. A. 4elo,i, G..I.ilocca,


S. IJ;rrrri.
cor,,prcxcs ancr prorircrntivc flcrivity
.::,i,,1:J,,;:,"j:1ii:
Ccll biology intcrnational relror.ts ) 4, 175(1990).

in rreoprflsric

l
3
-1

4&

L HI*'G oc.ur,&-

Ia,uza

]k:b\n6"a'Sc.
\>.- Q

,*. r- c,+

jffi:"ll
re

23)

Ossidanti e riducenti

rcazione risultante (2-33) dc-

-globalc

gli ioni Cut in soluzione


con fornrazione

di

rame

(2-30)

"$r;.t

di ossi-

-.0"

cli ossido-riduzione

esSere rappre.sentatl convenlen-

Queste rappresentazioni gracorLsentono la risoluzionc

di immediata
in Iunzione di alcuni Paradi esistenza di alcune sPecie,

rcbbero

,f,,*-"
'. +0,77

3:'*;
3o,,,.n.

3i,::',

Nei sisterni ossidoriduttivi, ia r


possibili stati di ossidazionr.'. det
elettrodo inerte imme*o .i iisicmal
Consicleriamo

possibiti

standard del sistema

un elcmento fra i divcrsi


potenzialc assunto da ltn
Fco, Fc'+ e

*trilibri

Feti in

e
(3- 1)

+2 ! i
Fe'+ +e C
Fe,n

ut,

Cu

joni

si

(2-33\

SeEilpotcnziale
Fe'+
il rapporto

frl

solu-

potenziali

3-2)

sistern a,

in base alla (3-2):


(3-3)

cio, a 25 "C

I [FC'*]
isos

ffi

(3-4)

Se si varia il rapporto [Ftt*]/[f'.'* ].Vuti" naturalmente il potenziale


dell'eiettrodo. D'altra Parte, sc -si impgl rdl ltl'elettrodo un potenziale diverso

J8t

Capitolo lV

soddisfare

la

(3-4).

rdo'espiicitamente l'attine,di Nernst, si ha:


(3-s)

h deposizione
ol -re-'.
rapporti ira le atti-

Sc

Fe

vit di Fe', Fe'+ e Fe't

Il sistema pu e
dei piri semplici
si prende come i
caso stato preso
funzione di Z.

1o

Cor

predor
potenz

si ha
log([

ptr

1(

Pcr

iog.o**u in cliversi modi. Uno


,,,1'ln-diagrammi di questo tipo
[i
itato di ossidazione, in questo
:.
piirta in ordinata il log(atf a,) in

di IF
fcrro
via vi

in

dis

clato
zioni

Da.

ol6

in

CD

cqr

infatt:

I{,,

{'

trascu

signifi

o che
sali f
SUSSiSI

gram:

non

la pr
poten
rri-1.1::-

'1,0

1,5

al
E

'dcl-Ferro iri funzionc de1 potenziale.

ier

retta

Ur
riduz
delle

Si hanno, pertanto, dellc


(pendenza: - 1/0,0295
fi.qqante per -0,440; 0)

comt

Ossiclani "

log([Fe.f.
i,0)

,,.1,:ff , : i'.' ;i.

T+,

ti t*,i+}?#$],ffi t ;

it?,
r:,;. J1 =j{ii:
- f ^-ii;.i
;::.;;i;.;;,;;;;;5;; J,' iL.'..:.
pOtcnzlaie SLallLldru !.3,1, Jr "t

la prevalenza della.fornvi F1l+i


, ..
r LlL
,i l,o rrrinu...
5l rr4

iog(tr.'.1/tt':]) -

-rt

P, 1{,,<,: t+.. ,'


:-..

10, cio, all'equiti6rio,;i.i;',iise1

enorl a U,//
v,
:l -,1'r
tone I e',

': ,, 'r :'r',n";'. .


''lttg9pil$1".
pcr l0'o ioni Fe'+"
per -E=
tr/ esiste un equilibrio fra ferro,'riiel^lliq.d;ftq,a soluzione
-0,+4
rmente, il
IF.".] : 1. Se il potenziale dell'elettrodtl ;i+^s
.ad
attivit.
;;'tare in .t.riti|{glit!''9
re*o metattico (ar.":i)
sistema
nel
il,.lt$g'T:t
D'altra
Fe'*.
di
via via decrescente
Parte,
di E",,
non p,rl-u*,-rr.r.." ptt"'iuti::frilii'
cliscussione, rlv'r
rrr uDLuNrullL'
i.
. r. l. r.,.11,,
solucon
equi#ttti
vieube
attivita,
sua
la
dato che, essendo costante
'
itreali"iiiii'fiii,{rq[l'
zioni co,ccnenti Fe'* l-.""..",t^rio.,i
:
esistere
,irii[tuitit
Dal cliagrarnma si vede anche che il ferro'.nt"1119;ff.,1,pu
condizioni'
a
pH=.0.,(I=9)::L*iiilii
in ;qriliu;i; con una soluzione acida
t.tii, Ia specie predominante Fe?+. Quildi:1.{Ef""liii9li:
ht.,ii,
Quindi il fe["..$iiii:"qlie liberando
del tutto
H., iormanc.lo in enonne prevalenza ioni r.'l-9. 11a'{*#il 'i!:'i"l:
non
1 o,li1,"
( [ Fe'n ]/ [ Fe'. t
l"r
";,.,,,ili.
E3'1,
"ii,r1.$"qitimente,
- -..,.i_,,,..,.,i
rrvrr posano esistere soluzioni
che non
----:----stsllrllL.r
sigrifica LlrL
:_t+i,l.,t
ioSi
^.i9i.;,3""i;tfil'ff'te-di
rapfr--fii,arbitrari di
contgni,lti
soluzioni
possano
preparare
o1h. no., si
sali ferrici e ierrosi ; il diagramma clice chc'tali,soluziorii'-/non Possono
dal diasussistere in presenza di fer mctailico. Appare ingltre'g,"yifl9.1te,
:
riferipite,{lilllmireazione
Eor,n,
gramma, .f,. it potenziale stanclard
intliiii,,
Fc.* *3 e r= Fe .,:'l:'

;;

t;ri;'

I :;f..:rL r .'l'l,,,lif'liti'l'

accessibile per via..diretll ::::4i,ii.r-rcomnatibiie


- , sperimentalmenle
la presenza contemporanea cli ferro metalligg.e..Ft'*''-,lafrtil ttu'ia' tale

rclativa
porenriale ricarabile dal cliagr.amma stesso,'piolung^andgllaailta
la
al ferro rnetallico, oltre il ,uo- .u*po di esistenza, f,"" ,l$i",*lqrsccare

' ,,l'i').. ' .,:.'. il''l


retta relativa al Fct*.
g]i tqa.ililti
in
diagram,*
Un altro modo per rapPresentare
si
ripoll.il'g.*'l*,r:
riduZione illutraio i., figura n'-3,.in cui

di

ossido-

itli::::t al
dele diverse sp..ie in-.rrion" del potenzi^f.'lilLi'E*,i;i,i riferisce
cio:
comportamen,o di ,no soluzione a conienut :l:'llf,,,i,in{,;,,$r1 .lotu"'
Mitr:,,'li l;1,],I#r,
f Fe3+l +
IFe,+-l:0.1
-r [Fe'*]
IFe'*]
-0,t I{,i1,,,,;,,'1
,
..,,r,,,rf

i i. .)

'

(3-6)

S-r:sfvNA
Capitolo IV

1,0

1,5

Fcrro in funzione del potcnzialc.

preservar

il sistema

da Processl

semplice ed del turto analoga


dei sistemi aciclo-base. Il burtto_

'coordinate

corri

tte Fe2l e Fe.+ ad uguale attivit

lr

il

ll

M. II potenziale clel sisterna a


'potenziale verso
valc
o per
.j.;;"X,.11'.1'"j..XIJ
^;;",;si ossida
a Fe.+. Se invece ci .si
osserva la graduale diminuzione
di
1 solito, le attivit con le concentra_
essere definita dall,equazione cl

I
I

I
I

i
i
I

\J-/)

I
I

(3-B)

;
I

'K",

t
I
I

iJ

FL1-* 1

-t n .t

t.'

,.

;1,
i:\,

i:

i
-i

'r.i:I

I ct.l'L'r
't/.:,,:.t:l

".1
'r

ii{i':.,.':.

'.,.t'2)7

Ossidanti e

oDDUre:
/

:'i

q-q\

..contrasseg-nate

oer lFet+l =

ler E( *

I/ si ha la

allo stato mencio di-asi-i,

1al!ig-o, Pa q!-lcstq pgnto in


i. gg.uezip,li non sono pi
Nel diagramma rapor
rneta.llico iF.";. Erro crrispionde
negativi di E a partire da E= -0,
attivitr ao:1.
' Nelle figure rv-4 e tv-5 sono
al sister44 dei rame. caratterizzato d
ril
-0,155 V. Per Ia costruzione del
itato ci riferimento Cu+.,
Si vede dai diagrammi come la
concentrazioni e le specic p

ltubilitl del ferro


'

esi verso valori


"..:-0,+7 z.
:i

La

sua

(--.

l'

ri:;

'.J:,!

i relativi

:;,0,337 v1 E,o2,,;1':

" .

kl,

scelto come
.

a basse
r'
slano sempre Cuo
slstere solo

e Cu'+.
,16
0,

10

-5
-

0,5

Fig. 4 - Rapporti dcllc attivita

n.l sistcmi

'"1

:r3

r..,".i

s.:r

;,;,,i1',.:ij{t

:i: ,::;f

iiiji;

"

t,-t'r'

;r,r

f,l
-r,i.

.'l, :..!

2)8
Capitolo IV

jl

&Jlu !gut1

il ramc metarico non


a pH=0,^1f:Oi;-,;,,^f" in onrU;.nti or.i_
danti (.E1 4,") il rame passa in soluzione
come ione Cu.*.
Il processo pu esscrc rea,rizzato per via elettroritica.
appri.^nao
-i"ro al rame
metallico un potenziale I)
8., si ha l,ossidazione Cr;i.
se si raggiunge il potenziale.,,, ir meta,o pu
passare in^ soluzione come cu+.
ou.tlcglaj9r appare crre

1v-a,
ossidabile da soluzioni
acide

ci

succede in pratica se, subentran.lo


unu certa polari zzazione di concentrazione, ad elevata den.sit di corrente,
ir metar ,i.r.. .uggiungerc
potenziali sufficientemente positivi.
^

Anche l'esame delra figura rv-5 interessante.


Il diagramma mostra
che, per il rame, il punto der sistema,
s, cade in una zoia di potenziari
pi negativi di quero sufficiente u p.oiurr.
riduzione .gri ,oni a cuo.
si pu dire che in questo.si.t.*u ii punto ravirtuare.
Le cu*e rerative a
Cu'* e Cu*, nell,interno cli q.ucsla ,onu (f
<.gru) sono tratteggiare. Si pu
riassumere quanto .espo.sto n diug.ama-clicenclo
c,e in ambicnti suffi_
cientemente ossidanti (,2>fr) it
,u*. prescnte in enorme prevaenza
come Cu'*. Diminuendo E, aumenta
gradualment. Iu for_u Cu+, che
resta tuttavia sempre presente in quuntlt
trascurabire comc terminc ad_

clitivo.

Per .E:,,,0,

il rapporto ICu*]/[Cur+]

diventa

il

massimo possibile

CC

el:

dr
se.

e,

o)

cu'

r-

le,,

Crt*

4
I

*l\.

-5

In
val

-10

o(

rid,
ces

/t,

or

sidi
I

15

/
I

dia

0,3

0,6
n. a.t

0,9

deF

po,.,iri""t..

di

x86

3
I

Ossidanti e riducenti

come

El

l
l
l
l
j
j

3v
lt

l
:

239

si ricava dal diagramma,

assume

il

valore

lCi l0-r,5-0,00316. A

valori pi negativi di E,.n si ha Ia deposizione di rame rnetallico.


Dinrinuendo graduairnente ir potcnziale, Ia fasel lolicla si rnerte

...

in

cqui-

librio con soluzioni sernprc pi.diluite di ioni Cu=* i Cu*. per.E


compreso
fra E".o . Et;.,; i; soluzion in equilibrio con cuiion,i*. i.,
p.. varenza
ancora Cu'+, per E1Er., la specic piri abbondant in soluzione
Cu+.
da tenere presente, tuttavia, .tr.
di per E-_p2,r=0, 153 la soluzionc
molto diiuita:
ICr*] - [Cu'*J ^, 10-'.

b)

liaslussi {(pu)

di ossido-ricruzionc sono legati alla produzionc o ar


di ioni H+ o OHIn questi casi le specie H+ e oH-, comparendo nelle semireazioni,
entrano anche nelle cspressioni di .8, per cui il potere ossidante
o riducente
dele coppie i* gioco diventa funzione der pH. pcr esempio, una
generica
Numerosi processi

consumo

semireazione

,,,,..

O*+-H*+n e i= fud
stabilir un potenziale, funzione di a11,, secondo l,equazione

E:Eo*
cio,

a 25"C:

af

#," gr#{,

g" + -Q!59 tos aot


E:Fo
'
'^In altri casi, le variazioni di pH possono

ff

o,oss

(3-10)

(3-l

pH

1)

(3-r2)

influenzare indirettamente il
y"t::t, dti P-oI1'g.l-.- di gx,d..:rid-caqrre. ci succedc quando gti ioni H+
o oH-, pur non essendo implicati dirgtg.+sg.gg nel ^processo" di ossidoriduzione, con-dizionano la connti";ii"'i.gli oni pa.tecipanti
ar proJ!, lrovCand -associzioii ; -.iisoCimlqUf ; a -l; rR..;Cii"ti
o riduce'ti abbino carauere acido o' b;;i;, o a precipiiariori" di i;;;r'idi o la formazione di.complessi, ecc. " ''
sisimi o.rido-ii.lrttivi di questo tipo possono essere rappresenrati da
diagrammi come quelli gi irlustrati purch si rifecano'ra ,r, varore
definito e costante di pH.
Di uso assai generale sono i diagrammi r, (pH) detti anche diagrammi
di predomina',za o diagrammi di pourbaix.-Esi sono particorarmente

,l

il

dl

*:
{1

-( o=
/Ll

'.,11

,iri_,F,

ffi/,

240

Capitolo IV

efficaci Per raPPresentare le conszioni di stabilit


dclle specie costituenti i
sistemi redor

Consideriamo in primo luogo:


pir, diagramma Iog

lL , (q

riferito

ad

ioni H.. u; l**p;o' non troppo


:,'Tl:H :.i::",i
fl i.1: ^1,,1"**_^rc
O^,,: dal.vanadio,
ch pu assumere t ;;j;;;.;r,::.

:"Tpli.i,o.U
0,2,3,4
e 5 e d origine alle specie Vo, Vr*, V.l,
Vgri . i._.
Le coppie coniugate e i nspettivi poi.nrioii standard
ai.ralrio.,. ,o,ro,
V'"+2 e r= Vo
Eoru: -1,43
(3_12)
Vt*+, +=r Vr* ,,.,..
Eo*: _0,255
(3_13)
VO'+ + 2 H* + a r=r Vr-+ +-HiO

8o,,1: +

0,361

nppucancro r equazlone clr


di Nernst
Nernst .,alle
singole semireazioni
.alle singole
lr,];j

.iii:i'r

i
I
I

I
I
I
i

(3-I4)

VO=+*2H++er+Vor++HrO ro.,r:+1,00
lt:i:::1".1'equazione .'
spettivamente:
[vt*]
rro , ^ /lQ^ '^- !5J
E-8"*+0,0301og

(3_15)

si

ortiene

,,'ill
l"s
'
f,+ = ffi
.,,ii,,,
.tvT'
E-Eo*+0,0se,"*
: ir#
,"*
f##, ,l',1
f#C
i':
l

(3-12')

(3-13,)

rffif1,r ## = "-t;il,t,r'

.E: Eo,, + 0,059 1on -[VO'*l [H*]'

r,:E'.r+0,0ss r"s

,".*

IYffifft;

intermedio,
ottiene:

vt+,

ros

f+e+

Lfr#&A

di riferimento il vanadio nelo stato di

,"*f

(pendenza=

ossidazione

i:%#

(pendcnza=

-310,'059:

,"*fH}:o

1/0,059

(pendcnza=0) (-r

si

N^_.
-- O't'l;

-50) ( t "
tO,Z)(*

.. * :

.l

vallc
note'
tacca

':1.'r:
rl a t:

.".'

rtl
..t 'l

Si
che

'"'##:efiffi#,,;,!P.ta."r"=l/0,059 - 16,7) (,

:..

i. )

reaz
men
siste

: -

. t;..

.!

.r

15')

combinando opportunamente.re equazioni


precedenti,

,"'#*:et#f=s

:.

(3_I+')

(3_

Se si assu.me comc specie

Di
nella

.rl,j

Ossidanti e riducenti

241

: .':

_E?

,^, IVOr*] ."s


Iv.*]
in

il

Fissando determinati valori di pH,


diagramm a log aif ar,(E) rappresenta

2/0,059 = 33,4)

i)

riportate

diagramma riportato

(1.

PH:0 si ottiene

in figura rv-6,:iLa,leti
iruovi.

diagramma non prescntano elementi

I'interpretazione

de I

\i,g;t;

'rRlt
:tr

\\
Er,o\N

iiflir

\\

tt\

.,iiil+t:l",
,Tir,:" i i'

.r1qi:il,:.

10

. ':.i.:'

vo/
/r/
//
lco
lt r,.

trtp

-'10

-1,0

Fis. 6 - Rapporti dcllc auivitr

Ir\
O
:'
.", ,:,;,ii:t:, t"""Ot:.ll
t *-.j-L;:

'l,0iE /
funzione dct potenziale

.,',

, i.r
L'intcrsezione delle varic rette forniscono i potenziali stancla4c.l di semireazioni non sempre direttamente realizzabili ("-;'l E"4, E"o,), analogamente a quanto gi stato illustrato nci preccdenti esempi relativi ai
sistemi del ferro e del rame.
:,,:,' ,
si pu notare, tuttavia, che il diagramma si estende per un ampio intervallo luori dal campo di stabilit. dell'acqua. Solo fattori cinetici consentono
chc i' pratica le soluzioni di v'+ abbiano uira ca stabilit e solo per
notevoli fenomeni di passivazionc e sowaieru;oneilili.iranadio risulta inattl'$i
taccabile dall'acqua c dagli acidi diluiti. . r
Diagra,mmi analoghi, rifcriti al sistema dd maiiganese, sono riportati
rrella figura rv-7.
,iir.,i,
..,,. : .i.{y.\,;:,
'

1...ri't+li.

-'"

( /'

'r-' -J't]

iffi1;
ir:'':ii

tr,

:'u,;i',

:j

tuiirl
.i!

't,

iriiii

242

Capitolo IV

vr

In talunr der
:.".

;:,,i

',:ri'.i
i;i.

l'J,t

allc specic
l'ambiente alcalino nuila

MPor.

i,ono implicati anche altri solidi, oltrc


iriconoscono, inlatti, le curve relative
Or. P., il campo aciclo srato scelto
iilvln'*, oppure il biossido, MnO=; per
lipreso per riferimento lvln(Oll),, oppure

'o

pH lO

-rct

Fig.

-12o

-liro

12o

Rapponi dclle artivit


:

di pH.

in lunzionc

40

dcl potcnziale

243

si costruiscono facilment..
(3-10). Dalla (3-12),

1;io, it generico sistema


'si ottiene : .-.

Si:C

llx

i.l,,r.

[l{ i ,rt l,

r- u+

(3-16)

). Ricordiamo che nella


numero di protoni e di

dircttamente

(3-16) nz e n rappresentano ' nslittlvame


elettroni in gioco'nel processo .oriid.ito,i
\

Esenp iq-..-;Costruire

' Fr'-

i,
il dlagramma

alla coppia VO.*,

vo.+.

Discussiottc
La

semire azione

di riduzione :

"'

';::l
Eo

= 1,00

da cui:

E:

1,00

1 0,059 log

(3- 1 7)

posto [VO*

II diagramma quindi rapprcsentato da unaiietta passante per .E: 1,00 V


pH=0, e con pendcnza dEf dpH= -Q,1?,,
-0,120" In qucsto e.scmpio si ha
liji:]t:,:
un intervcnto diretto degli ioni ,1=. i,
' ;;.
i:;;..1i;
a

'

Esempio

'

7.1I

Calcolare

il

i( S"+2,

''''t: per
diagramma E(pH)
E(pH),
t

il

sistema:

'

Sr:r . EuEo-.''i'0,50
V
=l::0150
..i....r
''i'iir":'

(3- 1 B)

Discussione
:

In questo caso la variazione di acidit ha un. effetto indiretto per azione


degli ioni H+ sulla specie S'-. Dalla (3-18), considerando unitaria l'attivit dello zolfo solido, arrotondando il terminei,2,303 RTlnF, si ha:

E:
In

-soluzion_e

valgono

-0,50-0,03

i"s,f.i-l

gli equilibri acidorbasici

ii;t,;,

-TtrFf-- = = lo-'
IH*] [S--]
ffi:Kr=lo-1'
/(r

;\

(3-1s)

(3-20)

, r,: r l:;

(3-2

r)

.,h;
.. le'!

'f 4,1

Capitolo

Iv

ti

&
v

1= lQ-zo

(3-22)
.

poich, dala

(3-23)

H*l [s,-]

lti

c dalla (3-22):

[H.s]:1
I

1..'l

(3-2+)

irl.:(

, :;,,'i.
j,
., !,-i'
': :;-ll

si ottiene:

i.j!l

(3-25)

:i"':
l:.t
t:,,:

',I

i [H*]'\
'

c quindi si

,t'..,E?",l='

(3-26)

-J

,,c1[u.i

'

.lH+l=
' K,K,

(3-2i)

in soluzione H,S; nella


come tcrmini additivi .esi
(3-2 B)

da cui:
(3-2s)

rna retta, di pendenza dEldpH:


; (v. figura rv-8, retta a).
e in soluzionc HS - e nella
tiascurabili rispeuo a L}J*f I K,(3-30)

']9IHII
oclle (3-19)

il rdorc di [S,-]

dato dd-

!'L

22)

23)

l+)

la
si

))

a
1.

;.ld.

246
Capitolo IV

(3-34)

Le (3-33)

alle semireazioni

HS-

(3_33')

:,

(3_34)

ls,

completo delle tre rette

sp_ecie

stabili e prcsenti quindi in

RH e potenziale. Lungo le linee


ri di p,f, le specie che formano le

concentrazione.

attraversare una retta r.erticale


.versare una orizzontale implica

:o

rette inclinate comporra pro_


protoni ed elettroni.

3
PH) rclativo al sistema CI:,

Cl-

E"

Cl-

assai scmplicc:

=1,36 v

J-J J.)

d.ovrebbe dipendcre rJl pH.


,,ton
,no tn(tlrettamentc in quarrru

in_

lii
* Cl- a 11*
.,

[,
;

(J-J

.CI" viene progressivamente


l;la. formazione

,ffii

di acido

E"

= 1,63 V

E":1,50

duzione;

Pu

sor_

ipocloroso
ossido-riduttivi e precisamente :

i.2fi,o

Lo ione CIO-

O.r

K:7

(3_3s)

,5

all'equilibrio

(3-37)
(3-38)

di

ossido-ri-

Capitolo

Iy

l'azione di ioni H+ ed
rap_
: per E:1,36 (retra a).

fl;+eg#rr:

(3-41)

(3-42)

T
__ --^qrrzrvrrs c,rcl

pn con I,,ietta
Iql?f
h:
1 '
:'x'"r'"-'---:,.

= [Cl,] = 1) quindi rappresen- _rrr


rJLrr.

{r.=,J,o,a_o,ospu

La.rerta
!a rclra a inter:eca
rnterceca iu
la retta
.Litu'ii;i;,-^
atintrno a
., o
" ^Lr
4,.8,.e
quindi a pH
1H
;''"'ilpl,,"

:ii:"'ff 9;,""I;"l;;,"i

I
I

"i ,r,,.*"'id,d,

l,*..i,i

(3_+3)

>

4,8,

",.

0..

*2H+ +2e

l
i

l
l
I

(3-4s)

Aumentando
con

il pH ;tjiilil

CIO- e quindi al disiiiijafi

I^ :if"

(retta c)
{.r.erra
d)

(3-46)

a 7,5, si sostituisce la
rn9 a sostituirsi

il

,;, tcto-l

specie HCIO
(3_40) p.*"rr,o,

"

(3-+7)

e quindi:
cio

toE-l

r;')ftra:

(rctta

d)

(3-48)

:l
.t

ffiw,l

3
tv

lllEr X

i
Si voglia, per
di vanadilc.'iracciarido
relative alle due coppie intr

il

d.co..o di reazioni

iv-10) lc curve lt(pH)

I,+2e d 2IVOr**2H++e +r
cvidente chc in ambiente

l-

si rende
quella del vanadio, per cui ia i

VO,**2I-a!11+
e cio

3i
)

i vanadati

(3-4s)

ossidano gli

E
1,0

3
)

3
3

3
I

3
T

14 P l'l
l, vo,+ e I-, I,.
iir, .

Fig. 10 - Diagramma ,E(pH)

*"

Gi. si avuto odo di r


,. r'
comDa-nvano soecre allo stato solido.iA
, . ,r _i*r{.. .

'

s'
ss

)"

{t
!g

-,

r;i!'hiil
,,ilr.

i.'i;ii-ir

.#

.'l

li

,-": ii4

i,ri',,!li
:,-:i.,:,:..

;-'t,.'

:.

ioiianzc solide

diagrammi in cui
;Appartengono r suitemr
:'

12

lV

Capirolo

Fe; Cu2+, Cu; S, Sr-; ecc.) che


ierie pi6 o meno numerosa di
usrur o ol torau poco. solublli, ,llCijirislstenza
condizionata da opportuni. va.lori
pH
..hf||ili,1*i.,p*b,flffip*e
specie
atrive nei proessi cti
.di

ossido-riduzione.

Il

;,1:lli:l:''t',11i-^il.q1l.ii',,

ferro, oltre agli ioni,Fc,u. ei4;lli;ia i rispettivi idrossidi


Fe(oI{), e
Fe(OH)3 e FerO.. Il
del
manianese,
olrre
al
metallo
Mno,
com_
_sistema
prende i solidi Mn(OH).,'MnOrH,
{nO,. euerte sostanze devono com_
parire nei diagrammi E(pH).
i',
Bench allo studio degli equilibri,terogenci
siano cledicati successivi capitoli, tuttavia si ritiene utile compici""is qresro
paragrafo ir tratramento
delle rappresentazioni
qatgi,qhg fa io.t.rriorr.-di diagrammi rela_
fl^n:h:,
t

ivi

ai'i't.-i

r.,r1;narl;;;t.;:

"*ido-,id;;;ii'
studentc non abbia
gia ricev,uto aai;gorsi.ai chimica

:.ffi;:ilH"i;

g.n..il..

plr T:Tt.l1,jl::"-+dj.4g.j:re. c1i1q,q!.i


. !ito 93ryide'!
:,,
sist ma

de
-Fe

sono

,*

i izu Hiii{)1_l:g.gg[ii,'

impricari in

+ 2e i=r Fe

(3-50)
(3-5

(3-52)

Fe(OH). i+ Fer+ +3O:r

:Cl ,+

(3-5 3)

.na conlentrazionc totale IFe:ts] +


- 1 l. In esso Ie linee assumono i
:;',i!; "

pH, si

riferisce

all'e quilbrio

si estcnde 6no ad irrcipiente


;
"t'.t,

J1s-",'

per [Fe'+] = 1, si

(3_5+)

6,6.
Rife r

li1ea
Fe +

2H,o

r-Jr)

A pI.

''i,-,

-'(

252
Capitolo IV
1f

e&sendo

[H+] [OH:

diventa

(pH

6,6)

(3-58)

(3-se)

una linea vertical", pH .ortai


incipiente precipitazionc di una i

{ineq

ii pH di

d.
(3_60)

Termina al

'(PH:

M di

1,5).

I inea

e.

Indica

il limitc di

E.'i t lr.
Iog ,(r, -37,4
a.t

Fe(OH). r=r Fe!+ 4

*!,\ea

l.

Fe'+

(3-6 1 )

Si riferisce al processo

I
l

(3-62)

L'equazione dclla
della rctta A, :

unaiogo

quello

s.

r
s:

(J-oJJ

valida nell'intervallo

tr

i
(3-64)

Dall'equazione:

f(
c/
S

(3-6s)

rt

ponendo

IFc'*]

il

d.

aoo

itf '."rl'::l;, la: i.,1.::,rllrl:i

;::; i'

tt

i,"
i'.-:
l,'-,.

;n+irr

t.

2i2 .1v
E ,Biii2?'a
.i..

.-.) Lt'
2.4'n?".

1..i'=
-';'i';.

;ii

OI
dl

9..?

4.4

.24;!i..Z.Z=-=
Za
'=i a:i:ii1=;*
=.

;a

'=='r'ld6?

Z*'e'z?;o1n=

fi,: i !;??iEi:

'2'22e';
zlr:27 2.''?'u e?

I A?,1
I.f
i+'u=zZ ; 1\ Z i1 ;e?'z'rlX;
EE: E.c :

.:l
':l

e!;2;7A

a
ta

2=?.*u1,*;

;;a i'^21 E ii3;airi:e

i!
i'i.?'*e

A
,s=9r

"_,.=.?a.2 z-o
3 E:.Ei -1",

;=r:rr,;Ei?:;l
C 12
().- ,i?'=22,?ou:

i.7:S;-i[?"?
zZ'=';',t3=

="r?
14
?2 iZirszi
.=o irr'zei
i..=*
==.==iZ
=7c=*..=-n =*
; iie:t2 112 o.i '-';13iei
-:\

-:r!.!.:'t
i i
t^::
-,9

'=t':!-

:r* il l*
i',1a
:-

.
.r
-

:'-.9;
":'=
--r

qr

i;:'l

i-J1!'!

'1l 'J .:a a-

--1r:a1 :!,4'.)
- -U=i

-'=

^i;:2t;
1:
all
v ;.:
2 .i
i:= =

2ei'7.?=
*,4.*al

,t_
'?;
2

*4")(4 -; ': :
.':r
' ,t .C'.
1
-'i'-:.11
e'{:;! $
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,::':.,
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.:J\'36:::::

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E
{ ;''.!"
ri."1
7

i
t:a

a
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:ir*";'z
it7l.i?u'7
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rE;iz3
s 2#2,

l.aai-zi

t= .Z = j

c...Y -

i3

i=i

i;i'Liu?Z
it

?rii ili= |i i; l;* i:F; i'i

l :zZe;z: 1- ?! E i;
ii
itzi= :?**z=;ig'!.E;;;: a?rvYq'i3=;
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; :s=B-?
::
Eii;:;a;
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:r = Ei=;=
Ii Ei;
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ii:iqir;
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i E,:-jnz E;i. :*;E 3: s: zil!ii:rIi s
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3;
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Lt
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;
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l 1t! ?I,;:,iii
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:i

; 13,;;3ir:
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=i

L=*-'

:iir,i;i;:
;:5
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:?Zi E; g 3 i*ri:A Z=.i:; 1"i l'


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t=?;i
i
u:
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i'-x

Z.:-

r=,-.-*r=3.-

o-c-c!l

=-..3=;6-,

..,

(J

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a,

r
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r*;I;;F;
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gt
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r ;.;.-e-u
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!,
+ Z
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:I:l?c1;, 3:;:i5*
;'a

I iI!IEls;;
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7i,:' rin:I
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i;i
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:=
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t:

iZ-t?,=:-e",; ?
?1u=;r;:i:ah

:;:itii;
;i+3:;AE.:.4;:

1,?

ii:

iE';r=!-e a; ;; i i:i !; i I
s

??-.= ?Ei ;
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t
t*,
;:a;
;
il:ti'
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;?:il
i
1
=:
d.u
AA., 6 Z
)i a4- a.=2.--;
_ \'i ili_ ; )lI
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;
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:..t

r-l

ol

5 l:;
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;-l
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a
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u
c-

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ei i ;i

il

j;.:

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=
g

o
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o
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co

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r*6al
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H.,f
i,

.9 t;.

lo

ir^
i:.
:. ^

+.g
d
N

li"=.3I .!
., a ^,.

Ittill
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._
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a_

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go

a_HL!-l:.

- :.a

eq

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9'"lo

1 1.. + r
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eo

": ?

t)

..i,

l)=u

s
4..

' ;.. er
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O
'u1 9-

"o:a
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'i-'t:
3es:

.a o o !-\c d
+ 'r5;ef!
ffinF -E

g-::

f:

Iii'
t;z

-+

5
1ir!i",
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ii*s?H
3:IA.

.:

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I:

+=!Ei ; i *fi'3
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s
iit,t,
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1.n2"1: j fr : j_=
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z
:"
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izia
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r.a 5L
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.-

i ! il

-r.

'

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sE
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r
Es:E;ilr=iii
El
i--6
z'z,?iiif i =
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o
o
r
I
U

; 6
'a.r-.-.,
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,.,

;iiliii

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i'{
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iX[;
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r
+

;i!;
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?
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=
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a ='. :E; i f ! E si
s:i:g*
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.+ ;sa.=
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I
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E:=E

.;3

i
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E
2

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,,
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'i'=';i'=
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i.=z?a^i

-i, 3i
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o.:
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t.g
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dl

I
tL

oj:

i<

lt

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l*9=-='eEe

5a*
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EZ.=
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i i:z ;:lilEE;: E: !==!=:
; E;;;EeTzz, *-o; 5;; :T
:- g:
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;:E.i?;
I
Esiii=spEx" r5"

IIa
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Zi'i=-'287
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E:
a li=u;,E ?
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