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TRNG I HC S PHM
KHOA HO HC
MT S BI TP TNG HP
V TNH TON CN BNG
Ging vin hng dn
PGS.TS: Nguyn nh Luyn
MC LC
A
M U
NI DUNG
KT LUN
A. M U
Ho hc phn tch l mt nghnh khoa hc v cc
phng php xc nh thnh phn nh tnh, thnh phn
nh lng, cu trc ca cc cht trong i tng nghin
cu.
Trong , phn tch nh tnh gip tnh ton nng
cn bng cc cu t trong dung dch khi t trng thi cn
bng nhm mc ch nh gi kh nng phn ng gia cc
cht, cc yu t nh hng n phn ng . T , tm
cch iu khin phn ng xy ra theo mun.
tm hiu v phng php gii mt s bi tp tnh
ton cn bng, chng ti tm hiu ti MT S BI
TP TNG HP V TNH TON CN BNG
B. NI DUNG
CHNG
1
CHNG MT S BI TP TNG HP
2
V TNH TON CN BNG
www.PowerPointDep.net
Baz mnh:
h - Ca .h - W = 0
2
h + Cb .h - W = 0
(1.1)
(1.2)
(1.3)
(1.4)
Axit a chc:
K ai
W n
h- Ca i
=0
h i=1
h + K ai
(1.5)
(1.5.2)
Baz a chc:
K bi
W
x- Cb i
= 0 (1.6)
x i=1
x + K bi
n
x
[A ] = C bi
(1.6.2)
K bi + x
(1.6.1)
aOx+ne
bKh
a
RT
(Ox)
0
trnh E = Eoxh/kh
+
ln
nF (Kh)b
a
0,
059
(Ox)
0
E = Eoxh/kh
+
ln
n
(Kh)b
(1.7)
K = 10
0
0
n(EOx
-EKh
)
0,059
(1.9)
A m Bn mA n + + nBm-
KS
K S = (A n+ )m .(B m- )n
(1.10)
Khi tch s tan
- Tch s tan c vit di dng nng K C ,ta c:
S
K CS = [A n+ ]m . [B m- ]n .f Amn+ .f Bnm-
(1.11)
(1.12)
K = [A]'[B]'
.
= K
.
S. A
Vi
(1.13)
A m Bn
mA n+ +nBm+
KS
S
mS
nS
m
n
n+
m-
m
n
KS =
A
.
B
=
(m.S)
.(n.S)
S=
(m+n)
KS
m m .n n
(1.16)
ML
ML+L
ML 2 +L
ML 2
ML3
k1
k2
k3
.....................................
ba
. ML
b=
a M .a L
'
N'
Vi
a M = 1 + bi h + bj[X]
-i
i=1
aL =
j=1
OH
a ML = 1 +b h +b
K H2O
h
LU :
C . D
K=
a
b
A . B
c
* Bi tp c nhiu cn bng :
Ka
- Cn bng axit baz:
- Cn bng oxi ha kh:
- Cn bng to kt ta:
- Cn bng to phc:
Cn bng chung:
K cb = 10
0
n(EOx
-E0Kh )
0,059
KS
K f =
K = Ka.Kcb.KS.Kf
CHNG 2: MT S BI TP
TNG HP V TNH TON CN BNG
HNO2 +H + +e NO+H 2 O
0'
NO 3- / HNO 2
=E
0
NO3- /HNO 2
3.0, 059
.pH
2
'
0
E0HNO
=
E
HNO2 /NO - 0, 059.pH
2 / NO
+ pH = 0
E 0NO - /HNO >E 0HNO2 /NO HNO2 b phn hy:
3
3HNO 2
+ pH = 6
E
0
NO3- /HNO 2
NO3- +2NO+H + +H 2 O
(*)
3.0,059
=0,94.6=0,409V E 0
0
>E
HNO 2 /NO
2
NO3- /HNO 2
2Cr 3 7H 2O
Br2 2e
lg[H
]
3 2
n
[Cr ]
n
2
3
Cc cht c xt iu kin chun: [Cr2O7 ] [Cr ] 1M
0,059
E E 14.
pH
6
a) Ti pH=1,00, thay vo biu thc trn:
0'
Vy: ti pH =3,5, Cr2 O72- khng oxi ha c ion Br- thnh Br2
Bi tp t gii
Cu 3: (trch [ NVT]) nh gi kh nng phn ng ca MnO4vi Cl- trong mi trng H+ trong hai trng hp sau:
a) pH=0
b) Dung dch NaHCO3 pH=8,33
0
0
E
1,51V;
E
1,395V
Cho bit: MnO4 /Mn 2
Cl 2 /2Cl
Hng dn:
Xy ra cn bng sau: 2MnO4 16H 10Cl 2Mn 2 5Cl 2 8H 2O
a) Da vo 2 gi tr E0 cn bng xy ra theo chiu thun
b) pH =8,33, da vo cn bng: MnO4 8H 5e Mn 2 4H 2O
8.0, 059pH
Tnh c:
E 0' E 0
0, 72V
5
Hng dn:
Vi h ny xy ra phn ng:
AsO34 2H + +2e AsO33 H 2O
Th oxi ho kh ca cp ny:
E As/O3- /AsO34
3
0,059
0,059
[AsO
4 ]
E 0As/O3- /AsO3-
lg[H ]2
lg
4
3
2
2
[AsO33 ]
3
0,059
[AsO
4 ]
E 0'As/O3- /AsO3-
lg
4
3
2
[AsO33 ]
0, 059
lg[108 ]2 0,1V
2
33
2+
Hng dn
Xt na phn ng: Fe3+ + e Fe2+ E 0Fe /Fe = E10 = 0, 771V
* Trong mi trng axit (pH<2), th khng ph thuc
vo pH.
* Trong mi trng pH cao hn (pH >2), ion Fe2+ v
Fe3+ to phc hiroxo:
3+
2+
Vi
E 30 = E10 + 0,0592lg
K S(Fe(OH)3 )
K S(Fe(OH)2 )
10- 37,5
= 0, 771 + 0,0592 lg - 15,1 =- 0,56V
10
0
pH
=
14,
E
=
E
*
3 =- 0,56V
lg 2,52
Pb 2 H 2O PbOH H
lg 7,8
CH 3COO H CH 3COOH
lg K a1 4, 76
Hng s bn iu kin:
'PbCH COO
3
[PbCH3COO ]'
2,52
10
'
0,574
7,8
2
4,76
2
Pb . CH3COO (1 10 .10 ).(1 10 .10 )
Cn bng:
Pb 2 CH 3COO
C 0, 010
1
PbCH 3COO
C' 0,010 x
1 x
Theo nh lut tc dng khi lng:
' 0,574
Thay gi tr x vo :
[PbCH 3COO ]' 3, 6.103 M
[Pb 2 ]' 6, 4.103 M [Pb 2 ] [Pb 2 ]' . Pb 6, 4.10 3 M
[CH 3COO ]' 1 x 1
[CH 3COO ] [CH 3COO ]' . CH3COO 1, 74.10 3
Cc cn bng
Co 2 6CN Co(CN)64
lg 19,09
Co 2 NH 3 Co(NH 3 ) 2
lg 1 1,99
Co 2 2NH 3 Co(NH 3 ) 2 2
lg 2 3,5
lg 3 4, 43
Co 2 4NH 3
Co(NH 3 ) 4 2
lg 4 5, 07
Co 2 5NH 3
Co(NH 3 )5 2
lg 5 5,13
Co 2 6NH 3
Co(NH 3 ) 6 2
lg 6 4, 39
Co 2 2H 2 O
CoOH H
lg K 11, 2
CN H 2 O
HCN OH
lg K b 4, 65
4 '
[Co(CN)
'
6 ]
Hng s bn iu kin: 2 '
[Co ] .[CN ]'6
Vi
Co . 6CN
'
Do
10
c:
Bi tp t gii
Cu 1: Hy m t cc qu trnh xy ra khi thm HCl vo
dung dch Cd(ClO4)2 cho n d. Vit biu thc nh lut tc
dng khi lng cho cc cn bng xy ra.
Cc qu trnh:
Cd(ClO 4 ) 2 Cd 2 2ClO 4
HCl H Cl
Cd 2 Cl
CdCl
Cd 2 2Cl
CdCl 2
Cd 2 3Cl
CdCl3
Cd 2 4Cl
CdCl 24
Cd 2 H 2 O
CdOH H
[CdCl n ]
f
[Cd].[Cl ]n
[CdOH
].[H
]
2
[Cd ]
C NH3 C NH 0,1174M
pK a ( NH ) 9, 24
4
4
i vi phc Zn v NH c lg i 2, 21; 4,5; 6,86; 8,89
3
Hng dn:
- Vit tt c cc cn bng c th xy ra trong dung dch,
lu , ion Zn2+ to phc vi EDTA v NH3
- Da vo cn bng:
Zn 2+ +Y 4- ZnY 2'
[Zn 2+ ]pu
Kt qu: %Zn cha phn ng = 2,75.10-3%
Hng dn:
Cc cn bng: Ni 2 H 2O NiOH H
108,94
NH 4 NH 3 H
K a 109,24
H 2 O OH H
K w 1014
CH 2S = CS2- = S
Vi
h
h2
S2- =1+
+
K a2 K a2 .K a1
2-
M n+ . A m-
. S2-
2-
> KS
CH 2S
S2-
Khi pH = 2
10- 2
(10- 2 ) 2
15
S2- = 1 +
+
= 7.69.10
- 13
- 13
-7
1,3.10
1,3.10 .1.10
0,1
-17
S =
=1,3.10
7,69.1015
Tch cc nng :
2-
Khng c kt ta MnS
To kt ta CoS
To kt ta Ag2S
Ks
C 2O 2-4 +H + HC 2O -4
K -1a 2
HC 2O -4 +H + H 2C 2O 4
K -1a1
+
+ 2
[H
]
[H
]
4
22[C2 O 2 ]'=[C 2O 4 ]+[HC 2O 4 ]+[H 2C 2O 4 ]=[C 2O 4 ]. 1+
+
[C2O 2-4 ].C2O4
K a 2 K a 2 .K a1
[H + ] [H + ]2
C2O4 = 1+
+
(*)
K a 2 K a 2 .K a1
'
K S . C2O4
K
S
3
3
S'=
4
4
Ti pH = 7 th [H+] = 10-7
C O2- 1 S
2
10
10,46
2,05.10 4
Ti pH = 5 th [H+] = 10-5
10,46
10
.2,61
3
C2O4 2,61 S'
2,83.104
4
Kt lun: pH c nh hng n tan ca cc cht. pH
cng gim th tan cng tng.
Bi tp t gii
Cu 3: Hi phi thm bao nhiu ml dung dch H2SO4 1M vo
100ml dung dch BaCl2 0,1M bt u xut hin kt ta
BaSO4? Tnh pH ti thi im ? Cho bit tch s tan ca
BaSO4 l TBaSO4=1,26.10-10 v coi H2SO4 phn li hon ton.
Nng ion SO42- khi bt u xut hin kt ta BaSO4
TBaSO4
10
1,
26.10
9
[SO 2-4 ]= 2+
1,
26.10
M
1
[Ba ]
10
V
2
[SO 4 ] 1.
1, 26.109 V=1,26.10-7 ml
100
H 2SO 4 1M
Cl - H
+ =10-pH
K S =S'.(S'+10
-pH
) S' 10 S' K S 0
2
-pH
K S 1035,2
(1)
S2 H HS
K a12 1012,9
(2)
HS H H 2S
1
K a1
107,02
(3)
1
a2
CuS 2H Cu H 2S
1
a1
K K s .K .K 10
15,3
K kh nh nn nh gi cn bng hu nh khng xy ra
theo chiu thun
nh gi nh lng:
CuS 2H Cu 2 H 2S
C
CCB
1M
1 2x
Cu 2 S2 CuS
K s1
KS
.CS2 K s CS2
(1)
Cu 2
C Zn 2
Vit tt c cc cn bng to thnh trong dung dch
H 2S H HS
K a1
kt ta khng hnh thnh:C
HS H S2
Ka2
S2 Zn 2 ZnS
K s1
Tnh c:
Thay vo (1) ta c gi tr H+ :
[H ]
[H ] 0, 692M
Ti pH = 7 th [H+] = 10-7
C O2- 1 S
2
10
10,46
2,05.10 4
Ti pH = 5 th [H+] = 10-5
10,46
10
.2,61
3
C2O4 2,61 S'
2,83.104
4
Kt lun: pH c nh hng n tan ca cc cht. pH
cng gim th tan cng tng.
Ta c phn ng:
E = EOX - E Kh > 0
Cu + 2Ag Cu
2+
+ 2Ag (1)
a) Nu khng c ClD E 0 = E 0 Ag+ /Ag - E 0Cu 2+ /Cu = 0,799 - 0,34 = 0, 459 > 0
Phn ng (1) xy ra theo chiu thun
b) C ClAgCl Ag + + Cl+
Ag +1e Ag
K1 = K0s
K 2 =10
-
AgCl + e Ag + Cl
K = K1.K 2
Ta c:
K =10
E 0AgCl/Ag / 0,059
Ag+/Ag
/0,059
E0 AgCl/Ag /0,059
E0
Ag+ /Ag
/ 0,059
10
= K s .10
E 0 AgCl/ Ag = 0, 059 lg K s + E 0 Ag+ / Ag
= 0, 209V < E
0
Cu 2+ /Cu
Pb +2e
Pb
PbC 2 O 4 +2e
K1 =10
Pb+C 2O
24
K=10
n.E 0 /0,059
-13,34.0,059
E =
=-0,394V
2
0'
(1)
(2)
0,346V
BI TP T GiI
Cu 3: [trch 6] Cho cc th
chun
sau
y:
0
AgBr(r) +e Ag+Br
E1 =0,0713V
Ag + +e Ag
E 02 =0,7996V
Tr li: K S 4,528.1013
-E 02 /0,059
K 2 =10
K S =K1.K 2
3-
Hng dn:
E 0Cu 2+ /CuI =0,86V>E 0I3- /3I- =0,5355V
1,
59.10
;
6,
76.10
tng nc tng ng l: 1
2
2-
Ag(NH 3 ) +
Ag(NH 3 ) + +NH 3
24
C 2 O +H
4
HC 2O
HC 2 O +H
Ag(NH 3 ) 2 +
K = 5,37.10
-1
a2
K 5, 62.10
-1
a1
H 2 C2O 4
5 1
2 1
h
h2
+ Cr O 2- =1+
+
1
2 4
K a1 K a1.K a2
4. 2, 06.10
4 3
.4332,16.1 4. S ' 3
S' 3,36.103 M
Vy: tan ca bc
oxalat b nh hng
bi pH v tc nhn
to phc.
Fe 2+
lg1 =5,18
(1)
Fe3+ +2F-
Fe+2
lg 2 =9,07
(2)
Fe3+ +3F-
FeF3
lg3 =12,10
(3)
7,9.10
M
5,18
1
9,07
2
12,10
3
1 10 .10 10 .10 10 .10
- Trong dung dch A:
NH 3 +H 2O NH 4+ +OH C
1,0
K b =10 -4,76
1,0
[] 1,0-x
1,0+x x
x(1,0+x)
Kb =
=10-4,76 x=[OH - ]=10-4,76
1,0-x
Ta c:
[Fe3+ ].[OH - ]3 7,9.10-13 .(10-4,76 )3 =10-26,4 >K S(Fe(OH) ) =10-37
3
Nh vy vn c kt ta Fe(OH)3.
BI TP T GiI
Cu 3: [6] Bc clorua d dng ho tan trong dung dch amoniac
v to ion phc:
AgCl +2NH 3 [Ag(NH 3 ) 2 ]+ +ClMt lt dung dch amoniac 1M ho tan c bao nhiu gam
6,77
-10
=10
AgCl. Bit: KS(AgCl)=1,8.10 , [Ag(NH3 )2 ]+
Hng dn:
[Ag(NH 3 ) 2 ]+
[Ag(NH ) ]+ =
3 2
[Ag + ].[NH 3 ]2
[Ag ]=
K S(AgCl)
[Cl- ]
[Cl- ]=0,0305M
; 2 =10
; 3 =10
; 4 =10
M ;
K 'S =K S . Cd 2+ . OH - =S'.(2S')'2
- 2
- 3
- 4
=1+
[CN
]+
[CN
]
+
[CN
]
+
[CN
]
Vi: Cd2+
1
1 2
1 2 3
1 2 3 4
OH- =1
Tr li: a. S = 1,14.10-5M.
b. S = 2,40.10-3M.
C NH3 >>C0Ag + = K S
2 >>1
Tr li: S = 5,65.10-5.
AgBr +2NH 3
Ag(NH 3 ) 2+ +Br -
Cu 2+ +4NH 3
Cu(NH 3 ) 42+
1 =1011,75
Cd 2+ +4NH 3
Cd(NH 3 ) 42+
2 =106,74
0
-9,24
E 0Cu 2+ /Cu =0,337V;E Cd
=-0,402V;K
=10
2+
/Cd
a(NH + )
4
Cd+Cu 2+ Cu+Cd 2+
Cd+Cu(NH 3 ) 4 2+ Cu+Cd(NH 3 ) 4 2+
Hn hp m NH3 + NH4NO3
pK a = pH
C +C =2 C NH4+ =C NH3 =1M
NH4+ NH3
V 1 (1011,75) >> 2 (106,74) nn Cu2+ to phc hon ton.
Cu 2+ + 4NH 3
C 0,001M 1M
[]
0,996M
Cu(NH 3 ) 42+
0,01M
1 =1011,75
T hp cc cn bng:
2+
Cu +2e
Cd
Cu
K1 =10
2+
Cd +2e
Cu(NH 3 ) 2+
4
K 2 =10
Cu 2+ +4NH 3
2.E
Cu 2+ /Cu
-2.E
Cd 2+ /Cd
/0,059
/0,059
1-1
Cd 2+ +4NH 3 Cd(NH 3 ) 2+
2
4
Cd+Cu(NH 3 ) 4 2+ Cu+Cd(NH 3 ) 4 2+
K=K1.K 2 .1-1. 2 =1020,15
C
[]
[]
0, 001
-
0, 001
Cu+Cd(NH 3 ) 4 2+
Cd+Cu(NH 3 ) 4 2+
0,001-x
K 1
Cu(NH 3 ) 4 2+
Cd(NH 3 ) 4 2+
x
x 1023,15
0, 001 x
K -1
Cu 2+ +4NH 3
1023,15
1-1
0,996
1-1.10-23,15
-35
a=
=1,28.10
(0,996) 4
Cd(NH 3 ) 42+
Cd 2+ +4NH 3
0,001-b
-12
0,996
-12 .0,001
-10
b=
=1,85.10
(0,996) 4 + -12
100.10-3
n Ag =
=9,27.10-4 (mol)
107,88
S mol cc i ca NH3 cn to phc l:
9,27.10-4 . 2 = 1,854.10-3(mol) << s mol NH3 (10-2mol)
Vy NH3 rt d ho tan lng Ag nu xy ra phn ng.
Ag + e Ag
+
E1 =E10 +0,059.log Ag +
PO2
0,059
0
E 2 =E 2 +
.log
4
OH -
BI TP T GII
Cu 3: [1] Co2+ c tnh kh rt yu, rt kh oxi ho
thnh Co3+ trong mi trng axit, nhng khi c mt
NH3 d th Co2+ d dng b oxi ho bi H2O2. Gii
thch. 0
35,16
4,39
E
=1,84V;
=10
;
=10
Cho: Co3+ /Co
Co(NH 3 )3+
Co(NH 3 )62+
6
Hng dn: E
0
2+
Co(NH3)3+
6 /Co(NH3)6
=E
0
Co3+ /Co
+0,059.lg
Co(NH3)2+
6
Co(NH3)3+
6
Tr li: E 0Co(NH3)
3+
6
/Co(NH3)62+
NH3
+
K=10
. 2 .1.W
Vi [OH-] t Kb.
Tr li: [Ag(NH3)2+= 10-19,55. Ag khng tan trong NH3.
0
0
-10
E
=0,337V;E
=0,799V;K
=10
2+
+
S(AgCl)
Cho: Cu /Cu
Ag /Ag
Hng dn:
+
2 Ag +1e
Ag
Ag + +Cl-
2 AgCl
2+
2.E0
/0,059
-2.E0
/0,059
K1 =10
K S2
Cu Cu +2e
K1 =10
2AgCl+Cu 2Ag+Cu 2+ +2Cl-
Tr li: K = 10-4,34.
Ag + /Ag
Cu 2 / Cu
C. KT LUN
Trong phm vi ti, nhm em tp trung la chn v
trnh by cc ni dung lin quan n bi tp tng hp v
tnh ton cn bng. C th nh sau:
- H thng ho cng thc tng qut lin quan n cn bng
axit baz, oxi ho kh, kt ta, to phc.
- Su tm, phn loi v gii c 12 bi tp tng hp lin
quan n mi phn.
- Su tm, phn loi 18 bi tp t gii lin quan n mi
phn. Cc bi tp t gii u c phn hng dn v tr li.