C 4 l ha cht (A, B, C, D) b mt nhn, mi l cha c th l dung dch ca mt trong

cc cht: HCl, H3AsO4, NaH2AsO4, cng c th l dung dch hn hp ca chng. xc nh cc

l ha cht trn, ngi ta tin hnh chun 10,00 ml mi dung dch bng dung dch NaOH
0,120 M, ln lt vi tng cht ch th metyl da cam (pH = 4,40), phenolphtalein (pH = 9,00)
ring r.
Kt qu chun thu c nh sau:
Dung dch VNaOH = V1 (ml) VNaOH = V2 (ml)
chun Dng ch th metyl da cam Dng ch th phenolphtalein
A 12,50 18,20
B 11,82 23,60
C 10,75 30,00
D 0,00 13,15
1. Hy bin lun xc nh thnh phn nh tnh ca tng dung dch A, B, C, D.
2. a) Tnh nng ban u ca cht tan trong dung dch C.
b) Tnh s mol Na3AsO4 cn cho vo 10,00 ml dung dch C thu c hn hp c pH = 6,50
(coi th tch ca dung dch khng thay i khi thm Na3AsO4 v b qua s phn li ca nc).
I3- /I-.
3. Cho hai cp oxi ha kh: H3AsO4/H3AsO3 v
a) Bng tnh ton, hy cho bit chiu phn ng xy ra pH = 0 v pH =14.
I3-
b) T gi tr pH no th c kh nng oxi ha c As(III)?
c) Vit phng trnh ion xy ra trong dung dch : pH = 0, pH = 14 v pH tnh c t b).
pK ai(H3AsO 4 ) pK a(H3AsO3 )
Cho: = 2,13; 6,94; 11,50; = 9,29 (pKa = -lgKa, vi Ka l hng s
0 RT
E 0H AsO /H AsO = 0,56 V; E I-3/3I- = 0,5355 V; 2,303 = 0,0592;
3 4 3 3 F
phn li axit); 25 oC:
[H3AsO4] = [H3AsO3] = 1M.

Hng dn gii:
1. Bin lun h: H3AsO4 l axit 3 chc, nhng ch c kh nng chun ring c nc 1 v nc
2 v Ka3 = 1011,50 rt nh.
pK a1 + pK a2
pH H AsO-
2 4 2
= 4,535 4,40 nu dng ch th metyl da cam (pH = 4,40)
th chun ht nc 1 ca H3AsO4.
pK a2 + pK a3
pH HAsO2-
4 2
Tng t, = 9,22 9,00 nu dng ch th phenolphtalein
2
HAsO 4
(pH = 9,00) th chun n , do :

- Nu dung dch chun l dung dch HCl th V2 V1

- Nu dung dch chun l H3AsO4 th V2 2V1
H 2 AsO 4
- Nu dung dch chun l th V1 = 0 < V2
- Nu dung dch chun l hn hp ca H3AsO4 v HCl th nc 1 chun ng thi
HCl v 1 nc ca H3AsO4, nc 2 ch chun 1 nc ca H3AsO4, do V1 < V2 < 2V1.
H 2 AsO 4
- Nu dung dch chun l hn hp ca H 3AsO4 v th V2 > 2V1. Nh vy cn
c vo kt qu chun , suy ra: Dung dch A gm H 3AsO4 v HCl; Dung dch B ch gm
H 2 AsO 4 H 2 AsO 4
H3AsO4; Dung dch C gm H3AsO4 v v dung dch D l dung dch .

H 2 AsO4
2. a) Gi nng ban u ca H3AsO4 v trong dung dch C ln lt l C1 v C2, ta c:
H 2 AsO 4
Ti thi im metyl da cam chuyn mu, thnh phn chnh ca h l , c th coi
chun ht nc 1 ca H3AsO4:
H 2 AsO 4
H3AsO4 + OH H2O +

10,00. C1 10,75 . 0,120 (1)
Tng t, ti thi im chuyn mu ca phenolphtalein, sn phm chnh ca dung dch l
HAsO24
, c th chp nhn lng NaOH cho vo trung ha ht 2 nc ca H 3AsO4 v 1 nc ca

H 2 AsO4
:
HAsO24
H3AsO4 + 2OH 2H2O +
H 2 AsO4 HAsO24
+ OH- H2O +

10,00 . (2C1 + C2) 30,00 . 0,120
(2)

T (1) v (2) C1 0,129 (M) v C2 0,102 (M)
CAsO3-
4
b) Gi s mol Na3AsO4 cn cho vo 10,00 ml dung dch C l x = 100x (M)
Ti pH = 6,50:
[H 3AsO 4 ] [H + ] 106,50

[H 2 AsO-4 ] K a1 10 2,13 = = H 2 AsO4
1 [H3AsO4] [ ] H3AsO4 tham gia phn ng ht.
+ 6,50
[H 2 AsO 4 ] [H ] 10
6,94 100,44 1
2
[HAsO 4 ] K a2 10 H 2 AsO4 HAsO 24
[ ] [ ]
2 + 6,50
[HAsO 4 ] [H ] 10
? 1
[AsO34 ] K a3 1011,50
Na3AsO4 cng tham gia phn ng ht.
H 2 AsO 4 HAsO24
Vy thnh phn chnh ca h l v . Cc qu trnh xy ra:
3
AsO 4 H 2 AsO4 HAsO24
H3AsO4 + + K1 = 109,37
(3)
0,129 100x 0,102
0,129 - 100x 0 0,102 + 100x 100x
2
HAsO4 H 2 AsO4
H3AsO4 + 2 K2 = 104,81 (4)
0,129 - 100x 100x 0,102 + 100x
0 200x - 0,129 0,36 - 100x
-
[H 2 AsO 4 ] CH AsO-
0,44
2-
= 10 2 4
100,44
[HAsO4 ] CHAsO 2-
4
V 0,36 - 100x = 100,44(200x - 0,129)
3
x = 1,099.10 (mol).
Kim tra:
AsO34
100x = 0,1099 < 0,129 trong phn ng (3), ht trc l hp l.
CH AsO- CHAsO2-
2 4 ? 4 ?
= 0,36 - 100x = 0,2501 [H+] v = 200x - 0,129 = 0,0908 [H+]
CH AsO- H AsO C HAsO2- HAsO2
2 4 2 4 4 4
[ ] v [ ] l ph hp.
Vy s mol Na3AsO4 cn cho vo 10,00 ml dung dch C pH = 6,50 l 1,099.103 mol.
 E 0H3AsO4 /H3AsO3 0,56 E 0I- /3I- 0,5355
3
3. a) pH = 0: V> V, nn phn ng s xy ra theo chiu
I3-
H3AsO4 oxi ha I thnh H3AsO3 v .
Theo bi ra H3AsO3 c coi nh l axit n chc, nn pH =14:
[H3 AsO3 ] [H + ] 10-14
= = = 1
[H 2 AsO3- ] Ka 10-9,29 H 2 AsO3
dng tn ti ca As(III) l .
2- + -14
[HAsO4 ] [H ] 10
= = -11,50 = 1
3-
[AsO 4 ] K a3 10 AsO34
Tng t: dng tn ti ca As(IV) l . Vy
3
AsO 4 H 2 AsO3
cp oxi ha kh l / .
3
AsO 4
+
+ 3H H3AsO4 (Ka1Ka2Ka3) 1 = 1020,57
K1 102 . 0,56/0,0592
H3AsO4 + 2H+ + 2e H3AsO3 + H2O
H 2 AsO3
H3AsO3 + H+ Ka = 109,29

4 H2O OH + H+ Kw = 1014
2(E0 - )/0,0592
AsO34 H 2 AsO3
AsO3-
K 2 10 4 /H 2AsO3

+ 3H2O + 2e + 4 OH
E 0AsO3- /H AsO-
E 0I- /3I- 0,5355
4 2 3 3
1 4
K2 = (Ka1Ka2Ka3) K1Ka (Kw) - 0,76 (V) < (V), nn phn ng
3
I3- H 2 AsO3 AsO 4
s xy ra theo chiu ngc li: oxi ha thnh v I.
I3- /I- I3-
b) V s chnh lch th ca 2 cp H3AsO4/ H3AsO3 v nh, nn c kh nng oxi ha
c As(III) ngay trong mi trng axit. Khi :
0,0592 [H3AsO 4 ][H + ]2
E H3AsO4 /H3AsO3 0,56 + lg E 0I- /3I- 0,5355
2 [H 3AsO3 ] 3
<

= 0,56 0,0592pH < 0,5355 pH > 0,41.
-
I3
Vy t gi tr pH > 0,41 th c kh nng oxi ha c As(III).
I3-
c) H3AsO4 + 3I + 2H+ H3AsO3 + + H2O (pH = 0)
H 2 AsO3 I3- AsO34
+ + 4OH + 3I + 3H2O (pH = 14)
I3-
H3AsO3 + + H2O H3AsO4 + 3I + 2H+ (pH > 0,41)