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PHN NG TO KT TA

TS Vi Anh Tun
Khoa ha hc Trng i hc KHTN - HQG H Ni

Phn ng to kt ta l phn ng to thnh cht rn t cc cht tan trong dung dch.


Th d:
Ag+ + Cl- AgCl (r)
Ca2+ + C2O42- CaC2O4 (r)
Trong ho phn tch, phn ng to kt ta c s dng :

Tch cht cn xc nh khi cc cht cn tr.

Phn tch khi lng.

Phn tch gin tip.

Chun kt ta.

1. Tch s tan v tan


1.1

Tch s tan
Qu trnh ho tan l qu trnh thun nghch, do cng tun theo nh lut tc dng

khi lng. Xt cn bng ha tan (Mn+ l ion kim loi, Xm- l gc axit hoc OH-):
MmXn

mMn+ + nXm-

T = [M]m[X]n

(*)
T c gi l tch s tan (solubility product).
Tch s tan c s dng :
So snh tan ca cc cht t tan "ng dng".
Xem mt dung dch bo ho hay cha:
m n
Q = CM C X > T: dung dch qu bo ho => xut hin kt ta.
m n
Q = CM C X = T: dung dch bo ho.
m n
Q = CM C X < T: dung dch cha bo ho => khng xut hin kt ta.

Tnh tan ca cc cht t tan (mui, hidroxit).


Cu 1.1.
13

So snh tan ca AgCl v AgBr trong nc ct. Bit T AgCl = 10-10, TAgBr = 10-

.
1

Hng dn gii

(AgCl > AgBr)

*Ch : Mc d TAgCl= 10-10 > TMg(OH)2= 1,2.10-11, nhng trong nc ct, tan ca
Mg(OH)2 li ln hn tan ca AgCl.
Cu 1.2.

(a) Trn 1 ml dung dch K2CrO4 0,12M vi 2 ml dung dch Ba(OH)2 0,009M.

C kt ta BaCrO4 to thnh khng? Bit TBaCrO4= 1,2. 10-10.


(b) Tnh nng cn bng ca cc cu t sau khi trn.
Hng dn gii
(a. Q= 0,04 0,006 = 2,4.10-4 > T => c kt ta to thnh;
(b) TPGH: CrO42-: 0,034 M
BaCrO4

Ba2+ + CrO42-

Cb

0,034 + x

T = x (0,034 + x) = 1,2.10-10

x = 3,53. 10-9 M.

[CrO42-] = 0,034 M;
[Ba2+] = 3,53.10-9 M)

Cu 1.3. Metylamin, CH3NH2, l mt baz yu phn li trong dung dch nh sau:


CH3NH2 + H2O

CH3NH3+ + OH-

(a) 25C, phn trm ion ho ca dung dch CH3NH2 0,160M l 4,7%. Hy tnh [OH-],
[CH3NH3+], [CH3NH2], [H3O+] v pH ca dung dch.
(b) Hy tnh Kb ca metylamin.
(c) Nu thm 0,05 mol La(NO3)3 vo 1,00 L dung dch cha 0,20 mol CH3NH2 v 0,20
mol CH3NH3Cl. C kt ta La(OH)3 xut hin khng? Cho tch s tan ca La(OH)3 l 1.1019

Hng dn gii
(a) [CH3NH2]= 0,152 M; [CH3NH3+]=[OH-]= 7,5.10-3; pH= 11,9
(b) 3,7.10-4
(c) Q = 2,56.10-12 > T, c kt ta)
Cu 1.4.

MgF2(r)

Mg2+(aq) + 2 F-(aq)

Trong dung dch bo ho MgF2 18 C, nng ca Mg2+ l 1,21.10-3 M.


(a) Hy vit biu thc tch s tan, T, v tnh gi tr ny 18 C.
2

(b) Hy tnh nng cn bng ca Mg2+ trong 1,000 L dung dch MgF2 bo ho 18C
cha 0,100 mol KF.
(c) Hy d on kt ta MgF2 c to thnh khng khi trn 100,0 mL dung dch Mg(NO3)2
3.10-3 M vi 200,0 mL dung dch NaF 2,00.10-3 M 18C.
(d) 27C nng ca Mg2+ trong dung dch bo ho MgF2 l 1,17.10-3 M. Hy cho bit
qu trnh ho tan MgF2 l to nhit hay thu nhit? Gii thch.
Hng dn gii
(a) 7,09.10-9
(b) 7,09.10-7M
(c) Q < T, khng c kt ta
(d) To nhit)
Cu 1.5. Dung dch bo ha H2S c nng 0,100 M.
Hng s axit ca H2S: K1 = 1,0 10-7 v K2 = 1,3 10-13.
(a) Tnh nng ion sunfua trong dung dch H2S 0,100 M khi iu chnh pH = 2,0.
(b) Mt dung dch A cha cc cation Mn2+, Co2+, v Ag+ vi nng ban u ca mi ion
u bng 0,010 M. Ho tan H2S vo A n bo ho v iu chnh pH = 2,0 th ion no to
kt ta?
Cho: TMnS = 2,5 10-10 ; TCoS = 4,0 10-21 ; TAg2S = 6,3 10-50.
(c) Hy cho bit c bao nhiu gam kt ta ch(II) sunfua c tch ra t 1,00 lit dung dch
bo ha ch(II) sunfat? bit nng sunfua c iu chnh n 1,00 .10-17 M? Cho cc
gi tr tch s tan: TPbSO4 = 1,6 10-8 v TPbS = 2,5 10-27.
Hng dn gii
[S 2 ] =

a)

K a1K a 2
CH S = 1,3.1017
[ H + ]2 + [ H + ]K a1 + K a1K a 2 2

[Mn2+] [S2-] = 10-2 1,3 .10-17 = 1,3 .10-19 < TMnS = 2,5 .10-10

b) C:

khng c kt ta
[Co2+] [ S2-] = 10-2 1,3 .10-17 = 1,3 .10-19 > TCoS = 4,0 .10-21

; c kt ta

[Ag+]2[S2-] = (10-2)2 1,3 .10-17 = 1,3 .1021 > TAg2S = 6,3 .10-50

; c kt ta

CoS
Ag2S
c) C:

[Pb2+][SO42-] = 1,6.10-8.
3

[Pb2+] = [SO42-] = 1,265.10-4.

Khi nng sunfua t 1,00.10-17 M th nng Pb2+ cn li trong dung dch l:


[Pb2+] = 2,5.10-27/ 1,00.10-17 = 2,5.10-10.

1.2

mPbS = (1,265.104 2,5.1010 ) 239,2 1 = 3,03.102 gam = 30,3mg )

Quan h gia tan v tch s tan


tan (S, solubility) ca mt cht l nng ca cht trong dung dch bo ho.

tan thng c biu din theo nng mol/l.


tan v tch s tan l nhng i lng c trng cho dung dch bo ho ca cht t
tan. Do , tch s tan v tan c mi quan h vi nhau, iu c ngha l ta c th tnh
c tan ca mt cht t tan t tch s tan ca n v ngc li.
MmXn

m Mn+ + n XmmS

nS
1

C:

T = [M] [X] = [mS] [nS]

T m+n
S = m n
m n

*Nhn xt: Cng thc trn ch ng nu Mn+ v Xm- khng tham phn ng no khc.
Cu 1.6.

Cho tch s tan ca Ag2CrO4 25oC l 2,6.10-12.

(a) Hy vit biu thc tch s tan ca Ag2CrO4.


(b) Hy tnh [Ag+] trong dung dch bo ha Ag2CrO4.
(c) Hy tnh khi lng Ag2CrO4 c th tan ti a trong 100 ml nc 25oC.
(d) Thm 0,1 mol AgNO3 vo 1,0 lit dung dch bo ha Ag2CrO4. Gi thit th tch dung
dch khng thay i. Hy cho bit [CrO42-] tng, gim hay khng i? Gii thch.
Trong dung dch bo ha Ag3PO4 25oC, nng Ag+ l 5,3.10-5 M.
(e) Hy tnh tch s tan ca Ag3PO4 25oC.
(g) Lm bay hi 1,00 lit dung dch bo ha Ag3PO4 25oC n cn 500 ml. Hy tnh
[Ag+] trong dung dch thu c.
p s
b. 8,66.10-5 M.
c. 2,88.10-3 gam;
d. gim;
e. 2,63.10-18.
g. khng i, 5,3.10-5 M)
4

2. Kt ta phn on
Nu trong dung dch c cha hai hay nhiu ion c kh nng to kt ta vi cng mt
ion khc, nhng cc kt ta hnh thnh c tan khc nhau nhiu th khi thm cht to kt
ta vo dung dch, cc kt ta s ln lt c to thnh. Hin tng to thnh ln lt
cc kt ta trong dung dch c gi l kt ta phn on.
*iu kin kt ta hon ton:

[X] < 10-6M, hoc

%X cn li trong dung dch < 0,1%

Cu 2.1.

Thm AgNO3 rn vo dung dch NaCl 0,10 M v Na 2CrO4 0,0010 M. Cho tch

s tan ca AgCl l 1,8.10-10 v ca Ag2CrO4 l 2,4.10-12.


(a) Hy tnh nng Ag+ cn thit bt u xut hin kt ta AgCl.
(b) Hy tnh nng Ag+ cn thit bt u xut hin kt ta Ag2CrO4.
(c) Kt ta no c to thnh trc khi cho AgNO3 vo dung dch trn?
(d) Hy tnh phn trm ion Cl- cn li trong dung dch khi Ag2CrO4 bt u kt ta?
p s
(a) 1,8.10-9M
(b) 4,9.10-5M
(c) AgCl
(d) 3,7.10-3%)
Cu 2.2. tan l mt yu t quan trng dng nh gi mc gy nhim mi
trng ca mui. tan ca mui ph thuc nhiu vo bn cht ca mui, dung mi v
cc iu kin th nghim nh nhit , pH v s to phc.
Mt dung dch cha BaCl2 v SrCl2 c cng nng l 0,01 M. Cu hi t ra l liu
c th tch hon ton hai mui ny ra khi nhau bng cch thm dung dch bo ha natri
sunfat hay khng. Bit iu kin tch hon ton l t nht 99,9% Ba2+ b kt ta
dng BaSO4 v SrSO4 chim khng qu 0,1 % khi lng kt ta. Bit cc gi tr tch s
tan nh sau: TBaSO4 = 1 10-10 v TSrSO4 = 3 10-7.
(a) Hy tnh nng ca Ba2+ cn li trong dung dch khi 99,9% Ba2+ b kt ta v cho
bit phng php ny c dng c tch hon ton hai mui ra khi nhau hay khng?
5

S to phc c th lm tng ng k tan. Bit tch s tan ca AgCl l 1,7 10-10,


hng s bn tng cng ca phc Ag(NH3)2+ l 1,5 107.
(b) Hy chng minh (bng php tnh c th) tan ca AgCl trong dung dch amoniac 1,0
M cao hn so vi tan trong nc ct.
Hng dn gii
[ Ba 2 + ] =

a.

100 99,9
0,01 = 1,0.10 5 M
100

Sau khi 99,9% Ba2+ b kt ta th nng SO42- trong dung dch l:


1.10 10
[ SO ] =
=
= 10 5 M
2+
5
[ Ba ] 1,0.10
TBaSO4

2
4

3.107
[ Sr ] =
=
= 3.10 2 M > 0,01 M
2
5
[ SO4 ] 1,0.10
TSrSO4

2+

Sr2+ cha kt ta. Vy c th s dng phng php ny tch hon ton hai mui ra
khi nhau.
b. tan ca AgCl trong nc ct:

S1 = [ Ag + ] = TAgCl = 1,30.10 5 M
Tnh tan ca AgCl trong dung dch amoniac 1,0 M.
AgCl + 2 NH3
b
cb

Ag(NH3)2+ + Cl

K = 1,5.107 1,7.1010 = 2,55.103

1,0
1,0 - 2x

x2
= 2,55.10 3
2
(1,0 2 x )

K=

S2 = x = 4,59.10-2 M;

x = 4,59.10-2 M

S2
= 4,6.103 lan )
S1

3. Cc yu t nh hng n tan
Trong thc t, ion kim loi ca kt ta c th to phc vi OH - v anion ca kt ta
c th phn ng vi H+ trong dung dch. Ngoi ra, nhng cu t khc c trong dung dch
cng c th tham gia phn ng vi cc ion ca kt ta hoc t nht cng lm bin i h s
hot ca chng. Nhng yu t u nh hng n tan ca kt ta.
3.1 nh hng ca pH
6

Cu 3.1.

(a) Hy cho bit dung dch ca cc mui sau c tnh axit, baz hay trung tnh?

Gii thch. Natri photphat, ng (II) nitrat v xesi clorua.


(b) Hy tnh khi lng bc photphat cn dng pha 10 lit dung dch bo ha. Khi tnh
b qua s thy phn ca ion photphat.
Bit bc photphat c T = 1,3 .1020.
(c) Hy cho bit trong thc t nu ha tan lng bc photphat tnh c phn (b) vo 10
lit nc th dung dch thu c bo ha hay cha? Gii thch.
Hng dn gii
a.

Na3PO4: baz; Cu(NO3)2: axit; CsCl: trung tnh;

b.

3 Ag+ + PO43-

Ag3PO4

3S

T = (3S )3 S

T
1,3.10 20
4
S=
=
= 4,68.10 6 M
27
27

mAg3PO4 = 4,68.10-6 10 419 = 1,96.10-2 gam

c. Cha, v PO43- b thy phn lm tng tan ca mui)


Cu 3.2. Tnh tan ca AgOCN trong dung dch HNO3 0,001M.
Cho TAgOCN= 2,3.10-7; HOCN c Ka=3,3.10-4.
Hng dn gii
AgOCN
-

OCN + H

Ag+ + OCN

HOCN

T = [Ag+][OCN-]
Ka =

(1)

[ H + ][OCN ]
[ HOCN ]

(2)

Lp phng trnh
[Ag+] = [OCN-] + [HOCN]
[H+] + [HOCN] = 10-3

(3)
(4)

Gii h:
(2, 4)

3,3.10

(103 [ HOCN ])[OCN ]


=
[ HOCN ]

10 3.[OCN ]
[ HOCN ] =
3,3.104 + [OCN ]

(5)
7

(3, 5)

[ Ag + ] = [OCN ] +

103[OCN ]
3,3.104 + [OCN ]

(6)

t [OCN-]= x
(1,6)

103 x
(x +
) x = 2,3.10 7
4
3,3.10 + x

x3 + 1,33.10-3 x2 - 2,3.10-7 x - 7,59.10-11 = 0

x= 2,98.10-4 = [OCN-]

(5)

[HOCN]= 4,75.10-4

(4)

[H+]= 5,25.10-4
[Ag+]= 7,72.10-4 = S.

(1) =>

*Nhn xt: v nng ca ion cc ion v phn t gn bng nhau nn khng th gii gn
ng c)
Cu 3.3.

(a) 100 ml nc 25oC ha tan c ti a 440 ml kh H2S ( ktc). Hy tnh

nng mol ca H2S trong dung dch bo ha. Gi thit rng qu trnh ha tan H2S khng
lm thay i th tch ca dung dch.
(b) Dung dch FeCl2 0,010 M c bo ha H2S bng cch xc lin tc dng kh H2S vo
dung dch. Cho TFeS = 8,0 .10-19. H2S c Ka1 = 9,5 .10-8 v Ka2 = 1,3 .10-14. Hng s ion ca
nc Kw = 1 .10-14. Hy cho bit thu c nhiu kt ta FeS hn th cn phi tng hay
gim pH ca dung dch?
(c) Hy tnh pH cn thit lp nng Fe2+ gim t 0,010 M xung cn 1,0 .10-8 M.
(d) Ngi ta thm axit axetic vo dung dch phn (b) nng u ca axit axetic t
0,10 M. Hy tnh nng u ca natri axetat cn thit lp nng Fe 2+ trong dung
dch thu c l 1,0.10-8 M. Khi tnh ch s to thnh H+ do phn ng: Fe2+ + H2S
FeS (r) + 2H+. Bit axit axetic c Ka = 1,8 .10-5. Gi s vic thm axit axetic v natri
axetat khng lm thay i th tch ca dung dch.
(e) Hy tnh pH ca dung dch m trc khi xc kh H2S.
Hng dn gii
(a.

[H 2 S ] = CH 2S

0,44
22,4
=
= 0,196 M
0,1

(H2S phn li khng ng k)

b. Tng pH.
c. C:

TFeS
8,0.10 19
[S ] =
=
= 8,0.10 11
2+
8
[ Fe ] 1,0.10

Mt khc:

[S 2 ] =

[ H 2 S ]K a1 K a 2
[ H + ]2

[ H 2 S ]K a1K a 2
0,196 9,5.108 1,3.1014
[H ] =
=
= 1,77.10 6 M
2
11
[S ]
8.10
+

pH = 5,75;

d.

Fe2+ + H2S FeS (r) + 2 H+


0,01

0,02

CH3COO- + H+
b

cb

a-0,02

CH3COOH

0,02

0,1

0,1 + 0,02

C:

[CH 3COO ]
pH = pK a + log
[CH 3COOH ]

5,75 = 4,74 + log

a = 1,25 M

e.

[CH 3COO ]
1,25
pH = pK a + log
= 4,74 + log
= 5,84 )
[CH 3COOH ]
0,1

Cu 3.4.

(QG 2007) Mt dung dch c ba cht HCl, BaCl2, FeCl3 cng nng

a 0,02
0,12

0,0150M. Sc kh CO2 vo dung dch ny cho n bo ho. Sau thm t t NaOH vo


dung dch n nng 0,120M. Cho bit: nng CO2 trong dung dch bo ho l 3.102

M; th tch ca dung dch khng thay i khi cho CO2 v NaOH vo; cc hng s: pKa

ca H2CO3 l 6,35 v 10,33; pKs ca Fe(OH)3 l 37,5 v ca BaCO3 l 8,30; pKa ca Fe3+
l 2,17. Hy tnh pH ca dung dch thu c.
Hng dn gii
H+ + OH-

H2O

0,015 0,015
9

CO2 + 2 OH0,03

0,03

Fe(OH)3

0,045

Ba2+ + CO320,015

CO32- + H2O

0,06

Fe3+ + 3 OH0,015

BaCO3

0,015

TPGH: CO32-: 0,015 M;


CO32- + H2O

HCO3- + OH- Kb1 = 10-3,67

0,015-x

x2
K b1 =
= 10 3, 67
0,015 x

x = 1,69.10-3 M

pH = 14 + log (1,69.10-3) = 11,23)

Cu 3.5.

Du hiu cho thy mt ngi c nguy c mc bnh gout l nng axit uric

(HUr) v urat (Ur-) trong mu ca ngi qu cao. Bnh vim khp xut hin do s kt
ta ca natri urat trong cc khp ni. Cho cc cn bng:
HUr (aq) + H2O
Ur- (aq) + Na+ (aq)

Ur- (aq) + H3O+ (aq)

pK = 5,4 37C

NaUr (r)

37C, 1,0 lit nc ha tan c ti a 8,0 mmol natri urat.


(a) Hy tnh tch s tan ca natri urat. B qua s thy phn ca ion urat.
Trong mu (c pH = 7,4 v 37C) nng Na+ l 130 mmol/L.
(b) Hy tnh nng urat ti a trong mu khng c kt ta natri urat xut hin.
Gi tr tch s tan ph thuc vo nhit . Bit thm rng bnh gout thng xut hin
u tin cc t ngn chn v ngn tay.
(c) Hy cho bit tch s tan ph thuc vo nhit nh th no?
tan ca axit uric trong nc 37C l 0,5 mmol/L.
(d) Chng minh rng nu khng c kt ta natri urat xut hin th cng s khng c kt ta
axit uric xut hin.

10

Gi thit rng ch c HUr v Ur- l nh hng n gi tr pH ca dung dch. Si thn


thng c axit uric. Nguyn nhn l nng qu cao ca axit uric v urat c trong nc
tiu v pH thp ca nc tiu (pH = 5 - 6).
(e) Hy tnh gi tr pH ti si (cha axit uric khng tan) c hnh thnh t nc tiu
ca bnh nhn. Gi thit rng nng tng cng ca axit uric v urat l 2,0 mmol/L.
Hng dn gii
a. 6,4 10-5;
b. 4,910-4 M;
c. Nhit gim th tch s tan gim.

[Ur ]
pH = pK a + log
[ HUr ]

d. C

[Ur ]
= pH pK a = 7,4 5,4 = 2
[ HUr ]

log

[Ur ]
= 10 2 = 100
[ HUr ]

V trong mu khng c kt ta NaUr nn [Ur-] < 4,910-4 (kt qu tnh c phn (b)).
[Ur ] 4,9.10 4
[ HUr ] <
=
= 4,9.10 6 < S HUr = 5.10 4 M
100
100

Vy khng c kt ta axit uric xut hin.


e. C:

[HUr] + [Ur-] = 2.10-3

Axit uric khng tan khi:


[HUr] = 5.10-4

[Ur-] = 2.10-3 - [HUr] = 1,5.10-3

[Ur ]
1,5.10 3
pH = pK a + log
= 5,4 + log
= 5,88
[ HUr ]
5.10 4

Vy pH < 5,88 th bt u c axit uric kt ta)


3.2. nh hng ca phn ng to phc
Cu 3.6.

CuBr l mt cht t tan trong nc (pT = 7,4).

(a) Hy tch th tch nc ti thiu cn dng ha tan hon ton 1 gam CuBr.
Ion Cu+ to phc vi amoniac theo cc phn ng sau:
11

Cu+ + NH3

[Cu(NH3)]+

[Cu(NH3)]+ + NH3

lg1 = 6,18

[Cu(NH3)2]+

lg2 = 4,69

(b) Hy tnh th tch dung dch amoniac 0,1 M ti thiu cn dng ha tan hon ton 1
gam CuBr.
(c) Biu thc tnh tch s tan iu kin ca CuBr nh sau:
T' = ([Cu + ] + [Cu(NH3 )]+ + [Cu(NH3 ) 2 ]+ ) [Br - ]

Hy tnh gi tr T' ca dung dch thu c phn (b).


Hng dn gii

Cu+ + Br-

a.

CuBr

C:

S = [Cu + ] = 10 -7,4 = 2,00.10 4

Mt khc:

S=

=>

V = 34,9 lit;

1
= 2,00.10 4
143,35V

b.

CuBr

Cu+ + Br-

Cu+ + NH3

[Cu(NH3)]+

lg1 = 6,18

[Cu(NH3)]+ + NH3

[Cu(NH3)2]+

lg2 = 4,69

C:

[Br-] = [Cu+] + [Cu(NH3)+] + [Cu(NH3)2+]

(1)

[NH3] + [Cu(NH3)+] + 2[Cu(NH3)2+] = 0,1

(2)

Gi s:

[Cu(NH3)2+] >> [Cu+], [Cu(NH3)+]

(1)

[Br-] = [Cu(NH3)2+]

(2)

[NH3] + 2[Cu(NH3)2+] = 0,1

C:

pT = 7,4

1, 2

[Cu(NH 3 ) +2 ]
[ Br - ]
[ Br - ]
=
=
=
[Cu + ][NH3 ] [Cu + ](0,1 - 2[Br - ]) 10- 7,4
(0,1 - 2[Br - ])
[ Br ]

[Br ] = 0,05 ; [Cu+] = 1,99.10-6 ; [Cu(NH3)2+] = [Br-] = 0,05


[Cu(NH 3 ) +2 ]
0,05
[NH 3 ] =
=
= 3,39.10 7
+
6
10 , 87
1, 2 [Cu ] 1,99.10 10

[Cu(NH3)+] = 1[Cu+][NH3] = 106,18 1,99.10-6 3,39.10-7 = 1,02.10-6


KTGT: tha mn;
12

S=

1
= [ Br ] = 0,05
143,35V2

V2 = 0,140 lit

c. T= ([Cu+]+[Cu(NH3)+] + [Cu(NH3)2+]) [Br]


= (1,99 106 +3,39 107 +0,05) 0,05 = 2,5 103
Cu 3.7.

Bit tch s tan ca Zn(OH)2 l 1,80 10-17.

(a) Hy tnh tan ca Zn(OH)2 trong nc.


(b) Hy tnh pH ca dung dch Zn(OH)2 bo ha.
Cho cc gi tr th kh chun:
[Zn(OH)4]2- + 2 e
Zn2+ + 2e

Zn (r) + 4 OH-

Zn (r)

E = -1,285 V
E = - 0,762 V

(c) Hy tnh hng s bn tng cng ca phc tetrahidroxozincat(II).


(d) Hy tnh tan ca Zn(OH)2 trong dung dch m c pH = 9,58. B qua s to phc
[Zn(OH)4]2-.
(e) Hy tnh tan ca Zn(OH)2 trong dung dch m c pH = 9,58 v c tnh n s to
thnh phc [Zn(OH)4]2-.
(g) Hy so snh kt qu tm c (d) v (e) v rt ra nhn xt.
Hng dn gii
a. b qua c s phn li ca nc; S = 1,65.10-6;
b. 8,52;
o
o
c. Cch 1: Thit lp cng thc tnh EZn ( OH ) 24 / Zn theo EZn 2+ / Zn .

EZn 2+ / Zn = E

o
Zn 2+ / Zn

=E

o
Zn 2+ / Zn

0,0592
0,0592 [ Zn(OH ) 24 ]
2+
o
+
lg[ Zn ] = EZn 2+ / Zn +
lg
2
2
[OH ]4
0,0592
0,0592 [ Zn(OH ) 24 ]

lg +
lg
2
2
[OH ]4

Khi [Zn(OH)42-] = [OH-] = 1 M th:


o
o
EZn2+ / Zn = EZn
= EZn

2+
( OH )2 / Zn
/ Zn
4

0,0592
lg
2

= 4,67.1017;

Cch 2:
13

Zn(r) + 4 OH-

[Zn(OH)4]2- + 2 e

E1 = +1.285 V
G1 = -zFE1 = -247.97 kJ/mol

Zn2+ + 2e-

Zn(r)

E2 = -0.762 V
G2 = -zFE2 = 147.04 kJ/mol

Zn2+ + 4 OH-

K =e

G
RT

=e

[Zn(OH)4]2-

100920
8, 314298

G = G1 + G2 = -100.92 kJ/mol

= 4,90.1017

T
= 1,25.10 8 M .
2
[OH ]

d.

[ Zn 2+ ] =

e.

S = [Zn2+] + [Zn(OH)42-] = [Zn2+] + [Zn2+][OH-]4


=

T
(1 + [OH ]4 ) = 2,56.10 8 M .
2
[OH ]

g. Kt qu khc nhau: (2,56- 1,25)/2,56 = 51%; rt ln; nh vy s to phc nh hng


ng k n tan)
Cu 3.8. (IChO 43) PbO l mt oxit lng tnh. Khi ha tan vo nc xy ra cc cn
bng:
PbO (r) + H2O

PbO (r) + 2 H2O

Pb2+(aq) + 2 OH- (aq)

Pb(OH)3- (aq) + H3O+ (aq)

T = 8,010-16
Ka = 1,010-15

(a) Hy tnh gi tr pH ca dung dch ti dung dch Pb 2+ 1,0010-2 M bt u c kt ta


PbO xut hin?
(b) T gi tr pH tnh c phn (a), ngi ta tng pH ca dung dch n mt gi tr
nht nh th kt ta bt u tan hon ton. Hy tnh gi tr pH ny?
(c) Hy vit biu thc tnh tan ca PbO.
(d) tan ca PbO t gi tr cc tiu ti pH =9,40. Hy tnh nng ca cc cu t v
tan ca PbO ti gi tr pH ny.
(e) Hy tnh khong pH ti tan ca PbO nh hn 1,010-3 M.
Hng dn gii
[Pb2+][OH-]2 = 8.10-16;

a.

b.

[OH-] = 2,83.10-7

pH = 7,45;

[Pb(OH)3-][H3O+] = 1.10-15
14

[H3O+]= 1.10-13

pH = 13;

c.

S = [Pb2+] + [Pb(OH)3-];

d.

[Pb2+]= 8.10-16/ [OH-]2 = 1,27.10-6M;


[Pb(OH)3-] = 10-15/ [H3O+]= 2,51.10-6 M;

S = 3,78.10-6M;
M rng: chng minh rng Smin ti gi tr pH = 9,40;
S = [Pb 2 + ] + [Pb(OH)3- ] =

8.10-16 10 15
10 15
12
+ 2
+
=
8
.
10
[
H
]
+
[OH - ]2 [ H + ]
[H + ]

10 15
S ' = 16.10 [ H ] + 2 = 0
[H ]

[H+]= 3,97.10-10 (pH = 9,40);

e.

S = 8.1012 [ H + ]2 +

8.1012 [ H + ]3 103[ H + ] 1015 = 0

[H+]1 = 1,12.10-8; pH1 = 7,95;

12

10 15
= 10 3
+
[H ]

[H+]2 = 1,0.10-12; pH2 = 12,00;

7,95 pH 12,00)

3.3. nh hng ng thi ca pH v phn ng to phc


Cu 3.9. Tnh tan ca AgI trong dung dch NH3 0,1M. Bit TAgI = 8,3.10-17; NH3 c Kb
= 1,75.10-5 v:
Ag+ + 2NH3

Ag(NH3)2+

1,2 = 1,7.107

Hng dn gii
Cc cn bng xy ra:
AgI

Ag+ + 2 NH3

NH3 + H2O

Ag+ + IAg(NH3)2+
NH4+ + OH-

Thit lp cc phng trnh:


T = [Ag+][I-] = 8,3.10-17

(1)

15

1, 2

[ Ag ( NH 3 ) 2 ]
=
= 1,7.10 7
+
2
[ Ag ][ NH 3 ]

Kb =

(2)

[ NH 4 ][OH ]
= 1,75.10 5
[ NH 3 ]

(3)

S = [I-] = [Ag+] + [Ag(NH3)2+]

(4)

[NH3] + 2 [Ag(NH3)2+] + [NH4+] = 0,1 M

(5)

[NH4+] = [OH-]

(6)

[NH4+] << [NH3]

Gi s

[Ag+] << [Ag(NH3)2+] << [NH3]


(5)

[NH3] = 0,1 M

(3)

[ NH 4 ] = [OH ] = 0,11,75.10 5 = 1,32.10 3

(4)

[I-] = [Ag(NH3)2+]

(7)

(1)

8,3.1017
8,3.1017
[ Ag ] =
=
+
[I ]
[ Ag ( NH 3 ) 2 ]

(8)

(2)

[ Ag ( NH 3 ) 2 ]
= 1,7.107
17
8,3.10
0,12
+
[ Ag ( NH 3 ) 2 ]

[Ag(NH3)2+] = 3,76.10-6 M

8,3.1017
8,3.1017
[ Ag ] =
=
= 2,21.1011
+
6
[ Ag ( NH 3 ) 2 ] 3,76.10

KTGT: tha mn

S = [I-] = [Ag(NH3)2+] = 3,76.10-6M)

Cu 3.10.

Tnh nng cn bng ca cc ion Ag+, Br-, Cl-, Ag(NH3)2+, NH4+ v OH-

trong dung dch bo ho AgCl v AgBr vi NH3 0,020M. Gi thit rng phc Ag(NH3)+
to thnh khng ng k.
Cho TAgCl = 10-10; TAgBr = 5.10-13; 1,2 = 108 v Kb= 1,8.10-5.
Hng dn gii
AgCl

Ag+ + Cl

TAgCl = 10-10

AgBr

Ag+ + Br

TAgBr = 5.10-13
16

Ag+ + 2 NH3

NH3 + H2O

Ag(NH3)2+

1,2 = 108

NH4+ + OH-

Kb = 1,8.10-5

[AgL2] + [Ag+] = [Cl] + [Br]

C:

(1)

[NH3] + [NH4+] + 2[AgL2] = 0,02


Gi s:

(2)

[Ag+] << [AgL2]; [Br] << [Cl] ; [NH4+] << [NH3]

(1)

[AgL2] = [Cl-]

(3)

(2)

[NH3] + 2[AgL2] = 0,02

AgCl
AgCl
2
2
[AgL2] = 1,2[Ag+][NH3]2 = 1,2 [Cl ] [ NH 3 ] = 1,2 [ AgL ] [ NH 3 ]

[AgL2]= 0,1 [NH3]

(4)

[NH3] + 0,2[NH3] = 0,02

[NH3]= 1,67.10-2M

[AgL2] = 1,67.10-3M; [Cl] = 1,67.10-3M;

(4)
T

[ Ag + ] =
[ Br ] =

TAgCl
[Cl ]

T AgBr
+

[ Ag ]

= 6.10 8 M

= 8,33.10 6 M

[OH-] = [NH4+] =

1,67.10 2 1,8.10 5 = 5,48.10 4 M

KTGT: tho mn)


Cu 3.11. Thm 0,1 ml Na2S 1M vo 10 ml dung dch Cu+ 10-2M v CN- 1M pH= 12.
Tnh xem c kt ta mu en Cu2S xut hin khng?
Bit: TCu2S= 10-47,6. Phc Cu(CN)43- c 1,4= 1030,3,
HCN c pKa= 9, H2S c pK1= 7 v pK2= 12,9.
Hng dn gii
([S2-]= 1,11.10-3M; [Cu+]= 5,9.10-33 => Q= 3,86.10-68 < T => khng c kt ta)
Cu 3.12. Cho TCu(OH)2 = 4,50 .1021; MW (Cu(OH)2) = 97,59 g.mol1
v pKb (NH3) = 4,76.
(a) i. Hy tnh tan ca Cu(OH)2 trong nc theo n v g/100 mL. B qua qu trnh t
phn li ca nc.
17

ii. Hy tnh pH ca dung dch bo ha Cu(OH)2.


(b) tan ca nhiu hidroxit kim loi c tng ln nh qu trnh to phc ca ion kim
loi vi phi t nh amoniac. Trong mt th nghim, ngi ta ha tan hon ton 5,00 mg
Cu(OH)2 trong 25,00 mL dung dch NH3. Bit nng cn bng ca NH3 trong dung dch
thu c l 1,00 .103 M, hng s bn tng cng ca phc Cu(NH3)42+ l 1,4 = 1011,75.
i. Hy tnh nng mol tng cng ca ng trong dung dch thu c.
ii. Hy tnh nng cn bng ca cc cu t cha ng trong dung dch.
iii. Hy tnh nng cn bng ca NH4+.
iv. Hy tnh pH ca dung dch.
v. Hy tnh nng ca dung dch NH3 ban u.

Hng dn gii
a. i.

Cu(OH)2

Cu2+ + 2 OHS

2S

C:

T = [Cu 2+ ][OH ]2 = S (2 S ) 2 = 4,50.10 21

4,50.1021
S=
= 1,04.10 7 M
4

S ' = 1,04.107 0,1 97,59 = 1,01.106 g / 100ml

ii. C:

[OH-]= 2S = 2 1,04 .10-7 = 2,08 .10-7

pH = 14 + log[OH-] = 14 + log (2,08 .10-7) = 7,32;

b. i.
ii.

CCu 2+

5,00.103
97,59
=
= 2,05.10 3 M
0,025

Cu(OH)2

Cu2+ + 2 OH-

Cu2+ + 4 NH3
C:

Cu(NH3)42+

CCu2+ = [Cu2+] + [Cu(NH3)42+] = 2,05.10-3

1, 4

[Cu ( NH 3 ) 24 + ]
=
[Cu 2 + ][ NH 3 ]4

T = 4,50.10-21
1,4 = 1011,75
(1)
(2)

18

(2)

[Cu ( NH 3 ) 24 + ] [Cu ( NH 3 )24 + ]


[Cu ] =
= 11, 75
= 1,778[Cu ( NH 3 ) 24 + ] (3)
4
3 4
1, 4 [ NH 3 ]
10 (10 )

(1, 3)

[Cu2+] = 1,31.10-3

2+

[Cu(NH3)42+] = 7,38.10-4
NH4+ + OH-

iii.

NH3 + H2O

C:

[ NH 4+ ][OH ] [ NH 4+ ]2
Kb =
=
[ NH 3 ]
[ NH 3 ]

[ NH 4+ ] = Kb [ NH 3 ] = 104, 76 1,00.103 = 1,32.104 M

Kb =10-4,76

[OH-] = [NH4+]= 1,32.10-4

iv. C:

pH = 14 + log[OH-] = 14 + log(1,32.10-4) = 10,12

v.

CNH3 = [NH3] + [NH4+] + 4[Cu(NH3)42+] = 1.10-3 + 1,32.10-4 + 4 7,38.10-4 =

4,08.10-3 M)
4. Xc nh tch s tan
4.1. Da vo tan
Cu 4.1. Thm t t dung dch bari nitrat 0,0010 M vo 200 ml dung dch NaF 0,040 M.
Khi 35 ml dung dch bari nitrat c thm vo th thy kt ta BaF 2 bt u xut hin.
Hy tnh tch s tan ca BaF2.
p s: (1,72.10-7)
Cu 4.2. Dung dch bo ha Cd(OH)2 c pH = 9,56. Hy tnh tch s tan ca Cd(OH)2.
p s: (2,39.10-14)
Cu 4.3.

Bit 1 lit dung dch NH3 1M ha tan c ti a 0,33 gam AgBr. Hy tnh

TAgBr. Bit phc Ag(NH3)2+ c 1,2 = 5,88.106.


Hng dn gii
[Ag(NH3)2+] = [Br-] = 0,33/188 = 1,76.10-3 M.

[NH3] = 1 2[Ag(NH3)2+] = 0,996 M

[ Ag + ] =

T = [Ag+][Br-]= 5,32.10-13)

Cu 4.4.

[ Ag ( NH 3 ) +2 ]
= 3,02.10 10
2
1, 2 [ NH 3 ]

Tnh tch s tan ca Ca(IO3)2

Th nghim 1. Chun ha dung dch natri thiosunfat.


19

Ly 10,0 ml dung dch KIO3 0,0120 M cho vo bnh nn. Thm 2 gam KI v 10 ml
dung dch HCl 1M. Dung dch c mu nu thm. Chun bng dung dch Na 2S2O3 n
mu vng rm. Thm 5 ml h tinh bt v tip tc chun n mt mu xanh ca phc
tinh bt vi I3- thy ht 20,55 ml.
Th nghim 2. Tnh tan ca Ca(IO3)2 trong nc ct.
Ly 10,0 ml dung dch bo ha Ca(IO3)2 cho vo bnh nn. Thm 2 gam KI v 10 ml
HCl 1M. Tin hnh chun dung dch thu c bng dung dch Na2S2O3 trn thy ht
19,20 ml. Hy:
(a) vit cc phn ng c m t trong th nghim.
(b) tnh nng dung dch Na2S2O3.
(c) tnh nng ca IO3-.
(d) tnh tan ca Ca(IO3)2 trong nc.
(e) tnh tch s tan ca Ca(IO3)2.
p s: a. IO3- + 5 I + 6 H+ 3 I2 + 3 H2O
I2 + 2 S2O32- 2 I + S4O62b. 0,0350M;
c. 0,0122 M.
d. 5,6.10-3 M.
e. 7,1.10-7)
4.2. Da vo gi tr th kh chun
o
o
Cho EHg 22+ / Hg = 0,789V ; EHg 2Cl 2 / Hg = 0,268V . Hy tnh tch s tan v tan ca

Cu 4.5.
Hg2Cl2.

Hng dn gii
Hg22+ + 2 e
Hg22+ + 2 Cl-

2 Hg
Hg2Cl2

T = [Hg22+][Cl-]2

o
o
Thit lp cng thc tnh EHg 2 Cl 2 / Hg theo EHg 22+ / Hg .

o
EHg 2+ / Hg = EHg
+
2+
/ Hg
2

0,0592
0,0592
T
o
lg[ Hg 22 + ] = EHg
+
lg
2+
/
Hg
2
2
2
[Cl ]2

o
= EHg
+
2+
/ Hg
2

0,0592
lg T 0,0592 lg[Cl ]
2
20

Khi [Cl] = 1 M th:

EHgCl

/ Hg

o
= EHgCl

/ Hg

T = 2,51.10-18

S(2S)2 = T

Cu 4.6.

o
= EHg
+
2+
/ Hg
2

S =3

0,0592
lg T
2

T
= 8,56.10 7 M )
4

Cho 3 pin in ha vi cc sc in ng tng ng 298K:

(1) Hg/HgCl2, KCl (bo ha ) // Ag+ (0,0100 M)/Ag

E1= 0,439 V

(2) Hg/HgCl2, KCl (bo ha ) // AgI (bo ha)/Ag

E2= 0,089 V

(3) Ag/AgI (bo ha), PbI2 (bo ha ) // KCl (bo ha), HgCl2/Hg

E3= 0,230 V

a) Hy tnh tch s tan ca bc idodua.


b) Hy tnh tch s tan ca ch (II) iodua.
o
Cho E Ag + / Ag = 0,799V , R = 8,314 J/mol/K, F = 96487 C/mol.

p s: a) 1,37.10-16;
b) [Ag+] = 4,58.10-14; [I] = 2,99.10-3;
[Pb2+]= 0,5 ([I] [Ag+]) = 1,5.10-3;
Cu 4.7.

T = 1,34.10-8

(IChO 42) Cho cc gi tr th kh chun sau:


Bn phn ng
Sn2+ + 2e Sn
Sn4+ + 2e Sn2+
Hg22+ + 2e 2 Hg
Hg2Cl2 + 2e 2 Hg

E0, V (298K)
-0,14
+0,15
+0,79
+0,27

+ 2 Cl
(a) Hy tnh hng s cn bng ca phn ng sau 298 K:
Sn (r) + Sn4+ (aq)

2 Sn2+ (aq)

(b) Hy tnh tan ca Hg2Cl2 trong nc 298 K (theo n v mol/l).


(c) Hy tnh sut in ng chun, E, ca pin nhin liu s dng phn ng sau:
H2 (k) + 1/2 O2 (k) H2O (l)

G = 237,1 kJ.mol1

Hng dn gii
a.

K = 10

2 ( 0 ,15 + 0 ,14 )
0 , 0592

= 6,27.10 9

b. Xc nh tch s tan:
21

Cch 1:
-1

Hg22+ + 2e 2 Hg
G01 = -nFE01 = -2 96485 0,79 = -152,4.103 J

Hg2Cl2 + 2e 2 Hg + 2 ClG02 = -nFE02 = -2 96485 0,27 = -52,1.103 J

Hg2Cl2

Hg22+ + 2 ClG03 = -G01 + G02 = 100,3.103 J = -RTlnT

G30
100,3.103
=
= 40,48
RT
8,314 298

ln T =

T = 2,62.10-18

Cch 2:

Hg22+ + 2 e
Hg22+ + 2 Cl-

o
Thit lp cng thc tnh EHg Cl
2

Hg2Cl2

/ Hg

o
EHg 2+ / Hg = EHg
+
2+
/ Hg

2 Hg

T = [Hg22+][Cl-]2

o
theo EHg

2+
2

/ Hg

0,0592
0,0592
T
o
lg[ Hg 22 + ] = EHg
+
lg
2+
2 / Hg
2
2
[Cl ]2

o
= EHg
+
2+
/ Hg
2

0,0592
lg T 0,0592 lg[Cl ]
2

Khi [Cl-] = 1 M th:


EHgCl

/ Hg

o
= EHgCl

/ Hg

o
= EHg
+
2+
/ Hg
2

0,0592
lg T
2

T = 2,71.10-18

Tnh tan:
C

Hg2Cl2

Hg22+ + 2 ClS

2S

S(2S)2 = T

T 3 2,62.1018
S=
=
= 8,68.10 7 M
4
4
3

22

G0 = -nFE0pin

c. C:

Cu 4.8.

0
pin

G 0

237,1.103
=
=
= 1,23V
nF
2 96485

K thut in ho thng c dng xc nh tan ca cc mui kh tan.

Do sc in ng l hm bc nht theo logarit ca nng nn c th xc nh c cc


nng d rt nh.
Bi tp ny s dng mt pin in ho gm hai phn, c ni vi nhau bng cu
mui. Phn bn tri ca s pin l mt thanh Zn nhng trong dung dch Zn(NO3)2
0,200M; cn phn bn phi l mt thanh Ag nhng trong dung dch AgNO3 0,100M. Mi
dung dch c th tch 1,00L 250C.
(a) V s pin v vit cc bn phn ng xy ra mi cc.
(b) Hy tnh sc in ng ca pin v vit phng trnh phn ng xy ra khi pin phng
in.
Gi s pin phng in hon ton v lng Zn c d.
(c) Hy tnh in lng c phng thch trong qu trnh phng in.
Trong mt th nghim khc, KCl c thm vo dung dch AgNO3 pha bn phi
ca pin ban u. Xy ra phn ng to kt ta AgCl v lm thay i sc in ng. Sau khi
thm xong. Sc in ng bng ca pin bng 1,04V v [K+] = 0,300M.
(d) Hy tnh [Ag+] ti trng thi cn bng.
(e) Hy tnh [Cl-] ti trng thi cn bng v TAgCl.
Cho: EoZn2+/Zn= -0,76V; EoAg+/Ag= 0,80V.
p s:

a. Zn| Zn2+|| Ag+ | Ag

b. 1,52V

c. 9649C

d. 7,3.10-10M

e. [Cl-] = 0,2M; T = 1,5.10-10)


Cu 4.9.

Xem xt pin in ha sau:


Pt |H2 (p = 1 atm)|H2SO4 0,01 M|PbSO4(r)|Pb(r).

(a) Hy tnh nng cn bng ca SO42- v pH ca dung dch trong pin trn.
(b) Hy vit phn ng xy ra khi pin phng in.
Sut in ng ca pin trn 298,15 K l 0,188 V. Gi thit rng trong phn (c) v
(d) nng cn bng ca SO42- l 510-3 M v ca H3O+ l 1510-3 M (cc gi tr ny c th
khc gi tr tnh c phn (a)).
23

(c) Hy tnh tch s tan ca PbSO4.


(d) Hy cho bit sut in ng ca pin trn tng hay gim bao nhiu V khi p sut ca
hidro gim mt na?
Vng kim loi khng tan trong dung dch axit nitric nhng tan c trong nc
cng toan (l hn hp gm axit clohidric c v axit nitric c c t l th tch tng ng
l 3 : 1). Vng phn ng vi nc cng toan to thnh ion phc [AuCl4]-.
(e) S dng cc gi tr th kh chun cho di y, hy tnh hng s bn tng cng ca
phc [AuCl4]-.
E(Pb2+/Pb) = - 0,126 V

Cho: pKa2 (H2SO4) = 1,92;


E(Au3+/Au) = + 1,50 V

E([AuCl4]-/Au + 4 Cl-) = + 1,00 V

Hng dn gii
a.

H2SO4 H+ + HSO40,01

HSO4-

0,01

H+ + SO42-

cb

0,01 - x

0,01 + x

Ka2 =

x = 4,53.10-3 M

[SO42-]= x = 4,53.10-3 M

(0,01 + x) x
= 10 1,92
0,01 x

[H+] = 0,01 + x = 0,0145 M

b.

pH = 1,84;
Catot (+)

PbSO4 + 2e Pb + SO42-

Anot (-)

H2 2 H+ + 2e

PbSO4 + H2 Pb + 2 H+ + SO42-

c. C:

0
Ecatot = E Pb
+
2+
/ Pb

Eanot = E

0
H + / H2

0,0592
lg[ Pb 2 + ]
2

0,0592 [ H + ]2
0,0592 (15.103 ) 2
+
lg
=0+
lg
= 0,108V
2
pH 2
2
1

24

0,0592
lg[ Pb 2 + ] + 0,108 = 0,188
2

0
E pin = Ecatot Eanot = EPb
+
2+
/ Pb

[Pb2+]= 1,81.10-6 M

T = [Pb2+][SO42-] = 1,81.10-6 5.10 = 9,05.10-9

d. Khi p sut ca hidro gim mt na:


Eanot = E

0
H + / H2

0,0592 [ H + ]2
0,0592 (15.103 ) 2
+
lg
=0+
lg
= 0,099V
2
pH 2
2
0,5

Ecatot khng i, Eanot tng (-0,099 + 0,108) = 0,009V, vy Epin gim 0,009 V;
e.

+1 Au3+ + 3e Au
G01 = -nFE01 = -3 96485 1,50 = -434,2.103 J
-1

AuCl4- + 3e Au + 4 ClG02 = -nFE02 = -3 96485 1,00 = -289,5.103 J

Au3+ + 4Cl-

AuCl4-

G03 = G01 - G02 = -144,7.103 J = -RTln1,4

G30
144,7.103
=
=
= 54,4
RT
8,314 298

ln 1, 4

1,4 = 2,31.1025)

25

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