37 CS LTHPT 1 PDF

Trn Mai Lin Analytical Chemistry 1 1
C S L THUYT
HA PHN TCH 1
GV: Trn Mai Lin
NI DUNG
Chng 1: Nhp mn ha phn tch
Chng 2: Cn bng ha hc
Chng 3: Phn ng axit - baz
Chng 4: Phn ng phc cht
Chng 5: Phn ng kt ta
Chng 6: Phn ng oxy ha kh
Chng 7: Cn bng gia hai dung mi khng trn ln
- S chit
GII THIU CHUNG
Fields of chemistry
Physical chemistry
Analytical chemistry

Organic chemistry
Inorganic chemistry
Biological chemistry
HA PHN TCH (Analytical chemistry)
Chng 1: Nhp mn ha phn tch (3 tit)
1.1. Tm tt lch s pht trin
1.2. nh ngha, thut ng, phn loi.
1.3. Vai tr v ng dng ca ha phn tch
1.1. Tm tt lch s pht trin
1.2. nh ngha, thut ng, phn loi
Ha phn tch (ANALYTICAL CHEMISTRY ) l g?
Khoa hc ca cc php o ha hc
Ha phn tr li c cu hi g?
Mu cha nhng thnh phn no? Phn tch nh
tnh (qualitative analysis) (What?)
Hm lng ca thnh phn l bao nhiu? Phn
tch nh lng (quantitative analysis) (How much?)
Cc k thut no c s dng trong ha phn tch?
Phng php ha hc: Chun (titrations), PP trng
lng (precipitations)
Phng php phn tch cng c: PP Ph
(spectrometry), PP sc k (chromatography)
C s ca Phng php pht hin cht phn tch:
Khi lng, kt ta
Mu sc
S khc x nh sng
Kh nng dn nhit
hp th
S pht x
S trao i e
Ph khi lng
` 1.2. nh ngha, thut ng, phn loi
Tnh c trng v tnh chn lc?
Cc phn ng hoc k thut ch c thc hin vi
mt cht c trng (specific)
Cc phn ng hoc k thut c p dng cho mt s
cht chn lc (selective)
Cht nn (matrix):
Tt c thnh phn ca mu cha cht phn tch.
` 1.2. nh ngha, thut ng, phn loi
KT LUN:
<Ha phn tch> = {S, [C
i
], [Q
i
] , [A
i
] , T}
Trong :
S = matrix system
C
i
= species
Q
i
= quantity
A
i
= accuracy
T = time
Qui trnh phn tch
1.) Xy dng cch t vn :
Chuyn nhng vn chung thnh nhng vn mang tnh cht c th
V d: Mu nc c an ton ung hay khng?
Hm lng As trong mu nc l bao nhiu?
2.) Chn pp phn tch:
a.) Khi chn mt phng php phn tch cn ch ti nhng vn sau:
bt nh ca php o
Gii hn pht hin
Cch phn hy mu
Mc kh thi, thi gian, gi thnh
b.) Nu c th, pht trin mt phng php mi
3.) Ly mu:
(i) Khng s dng ton b mu
(ii) C nh cch ly cho cng mt mu
4.) Chun b mu:
a. Chuyn mu v dng thch hp cho vic phn
tch
Ha tan mu
C c mu
b. Tch nhng thnh phn c tng tc vi cht
phn tch
5.) Phn tch:
Xc nh nng cht phn tch
o lp li nhiu ln
Trnh sai s qu ln
tin cy ca php o
ng chun
6.) Tnh ton kt qu
n v o
Tin t K
hiu
H
s
Mega M 10
6
Kilo k 10
3
Hecto h 10
2
Deca da 10
1
Deci d 10
-1
Centi c 10
-2
Milli m 10
-3
Micro 10
-6
Nano n 10
-9
Pico p 10
-12
Femto f 10
-15
Atto a 10
-18
n v K hiu SI tng ng
Th tch liter L *10
-3
m
3
milliliter mL *10
-6
m
3
di angstrom *10
-10
m
inch In. *0.0254 m
Khi lng pound lb *0.45359237 kg
metric ton *1000 kg
Trng lc dyne dyn *10
-5
N
p sut bar bar *10
5
Pa
atmosphere atm *101325 Pa
torr Torr 133.322 Pa
pound/in
2
psi 6894.76 Pa
Nng lng erg erg *10
-7
J
electron volt eV 1.602176462x10
-19
J
calorie, thermochemical cal *4.184 J
Calorie (British) Cal *1000 cal = 4.184 kJ
British thermal unit Btu 1055.06 J
Cng sut horsepower 745.700 W
Nhit Centigrade (= Celsius)
o
C *K - 273.15
Fahrenheit
o
F *1.8(K 273.15) + 32
Cc loi nng ?
Cng thc tnh ?
Cch pha mt dung dch phn tch ?
1.3. Vai tr v ng dng ca ha phn tch
Khng c phn tch th khng c tng hp
C S L THUYT
HA PHN TCH 1
GV: Trn Mai Lin
Chng 2: Cn bng ha hc
2.1. Cn bng ha hc
2.2. Hot , nng , h s hot
2.3. Tnh nh lng ca cn bng ha hc
2.4. Khi nim v hng s cn bng iu kin
2.1. Cn bng ha hc
Phn ng thun nghch?
Trng thi cn bng ha hc?
Mc ch ca vic nghin cu trng thi cn
bng ha hc?
Hng s cn bng v mc din ra ca phn
ng ha hc?
Cc yu t nh hng n cn bng ha hc?
Nguyn l chuyn dch cn bng?
C
o
n
c
e
n
t
r
a
t
i
o
n
0
Time
Initial
state
Change Equilibrium
Equilibrium
concentration
Progress of chemical reaction. A+B = C+D
A and B disappearing
C and D appearing
aA + bB + cC + dD +
... ] [ ] [
... ] [ ] [
b a
d c
B A
D C
K
2.2. Hot , nng , h s hot
Hot :
a = f.C
C: nng (mol/L)
f: h s hot (ph thuc vo lc ion )
Lc ion :
Gi s dung dch c i cu t vi
in tch l Z
1
, Z
2
, , Z
i
nng ca tng cu t C
1
, C
2
, , C
i
i
i
i
i
C Z .
2
1
1
2

Nu = 0 dung dch rt long, tng tc khng
ng k f = 1 a = C
Nu 0,02 th:
Nu 0,02 < 0,2 th:
Nu > 0,2 th:
(A: h s thc nghim)
2
2
1
log
i i
Z f

1
5 , 0 log
2
i
i
Z
f
.
1
5 , 0 log
2
A
Z
f
i
i

Mt s bi tp tnh hot
Bi 1: Tnh a ca Al
3+
v SO
4
2-
trong dung dch hn hp
Al
2
(SO
4
)
3
10
-3
M v (NH
4
)
2
SO
4
10
-3
M
2.3 Hng s cn bng iu kin
Trong dung dch tn ti nhiu cu t, ngoi phn ng
chnh cn c th c cc phn ng ph nng ca
cc cu t tham gia p chnh thay i.
K
Hng s CB
K
Hng s CB iu kin
V d: Dung dch complexonat ca niken: NiY
2-
nu c
mt NH
3
, H
+
th c p ph. C th nh sau:
Trong dung dch NiY
2-
phn ly theo pt:
NiY
2-
Ni
2+
+ Y
4-
V dung dch c NH
3
nn c p ph:
Ni
2+
+ NH
3
Ni(NH
3
)
2+
Ni(NH
3
)
2+
+ NH
3
Ni(NH
3
)
2
2+
Ni(NH
3
)
5
2+
+ NH
3
Ni(NH
3
)
6
2+
Gi [Ni
2+
] l nng ca Ni
2+
do phc (NiY
2-
) phn ly.
[Ni
2+
]
Ni
2+
tn ti t do
Ni(NH
3
)
2+
Ni(NH
3
)
6
2+
Ni(NH
3
)
5
2+
Ni(NH
3
)
4
2+
Ni(NH
3
)
3
2+
Ni(NH
3
)
2
2+
[Ni
2+
] = [Ni
2+
] + [Ni(NH
3
)
2+
] + [Ni(NH
3
)
2
2+
] + + [Ni(NH
3
)
6
2+
]
) (
2
3
2
1
]. [
NH Ni
Ni

Trong dung dch c H
+
nn c p ph gia H
+
v Y
4-
:
Y
4-
+ H
+
HY
3-
HY
3-
+ H
+
H
2
Y
2-
H
2
Y
2-
+ H
+
H
3
Y
-
H
3
Y
-
+ H
+
H
4
Y
Gi [Y
4-
] l nng ca Y
4-
do phc phn ly:
[Y
4-
] = [Y
4-
] + [HY
3-
] + [H
2
Y
2-
] + [H
3
Y
-
] + [H
4
Y]
) (
4
4
1
]. [

H Y
Y

Khi , hng s cn bng iu kin:
) ( ) ( ) ( ) (
2
4 2
2
4 2
4
3
2 4
3
2
.
1
.
.
1
.
] [
] ].[ [
] [
]' ]'.[ [
'

H Y NH Ni H Y NH Ni
K
NiY
Y Ni
NiY
Y Ni
K

C S L THUYT
HA PHN TCH 1
GV: Trn Mai Lin
Chng 3. Phn ng axit - baz
3.1. nh ngha v axit, baz
3.2. S t ion ha ca nc
3.3. Quan h K
a
v K
b
ca mt cp axit baz lin hp
3.4. Tnh pH ca mt s dung dch
Khi nim v axit v baz?
mnh ca axit v baz?
pH l g, ti sao s dng thng s ny?
pH ca mt s dung dch axit, baz, mui?
3.1 Khi nim v axit, baz
Theo Arrhenius:
Axit l cht khi ha tan trong nc c kh nng phn ly
thnh H
+
Baz l cht khi ha tan trong nc c kh nng phn
ly thnh OH
-
Nhn xt: nh ngha khng tng qut
Theo Bronsted:
Axit l cht c kh nng cho H
+
Baz l cht c kh nng nhn H
+
Axit
H
+
+ Baz
Cp axit baz lin hp:
Ch : Mt cht ch th hin tnh axit hoc baz trong mt
dung mi c kh nng cho nhn H
+
V d:
Kh HCl Dung dch HCl
Axit Baz
H
2
O l mt dung mi in hnh: c kh nng cho v nhn
H
+
V d: Xt dung dch NH
3
NH
3
+ H
2
O NH
4
+
+ OH
-
H
+
baz
axit
Cp axit, baz lin hp: NH
4
+
/NH
3
Ty theo bn cht ca dung mi, mt cht c th l axit
hoc l baz
CH
3
COOH + NH
3
CH
3
COO
-
+ NH
4
+
CH
3
COOH + HF CH
3
COOH
2
+
+ F
-
NH
4
+
+ H
2
O NH
3
+ H
3
O
+
H
+
CH
3
COO
-
+ H
2
O CH
3
COOH + OH
-
H
+
3.2 S ion ha ca nc
H
2
O va l mt axit va l mt baz
H
2
O + H
2
O H
3
O
+
+ OH
-
Hng s cn bng:
V nc phn ly rt t nn coi [H
2
O] l hng s:
K.[H
2
O] = [H
3
O
+
].[OH
-
] = const = k
H2O
K
H2O
l hng s ion ca nc (ph thuc vo nhit )
25
0
C:
k
H2O
= 10
-14
pK
H2O
= 14
2
2
3
] [
] ].[ [
O H
OH O H
K
+
=
3.3 Hng s axit (K
a
), hng s baz (K
b
) Mi lin h
Xt mt dung dch axit:
A + H
2
O B + H
3
O
+
Hng s cn bng:
Thng qua gi tr K
a
c th xc nh mnh, yu ca
axit?
(1)
] ].[ [
] ].[ [
2
3
O H A
O H B
K
+
=
a
K
A
O H B
O H K = =
+
] [
] ].[ [
] .[ ) 1 (
3
2
K
a
l hng s axit; pK
a
= -logK
a
3.3 Hng s axit (K
a
), hng s baz (K
b
) Mi lin h
Tng t vi baz:
a axit: phn t cha nhiu hn 2 H phn ly nhiu
nc, mi nc c mt hng s
V d: axit H
3
PO
4
H
3
PO
4
+ H
2
O H
2
PO
4
-
+ H
3
O
+
pK
a1
= 2,12
H
2
PO
4
-
+ H
2
O HPO
4
2-
+ H
3
O
+
pK
a2
= 7,21
HPO
4
2-
+ H
2
O PO
4
3-
+ H
3
O
+
pK
a3
= 12,36
a baz: PO
4
3-
, c pK
b1
, pK
b2
, pK
b3
] [
] ].[ [
] .[
2
B
OH A
O H K K
b
= =
3.3 Hng s axit (K
a
), hng s baz (K
b
) Mi lin h
Quan h gia K
a
v K
b
ca mt cp axit / baz lin hp
14
3
10
] [
] ].[ [
.
] [
] ].[ [
.
2
= = =
+
O H b a
K
B
OH A
A
O H B
K K
pK
a
+ pK
b
= 14
Nhn xt: Vi mt cp ax-bz lin hp, axit cng mnh th
baz cng yu v ngc li
3.3 Hng s axit (K
a
), hng s baz (K
b
) Mi lin h
Phng trnh bo ton proton:
Nguyn tc: S mol proton axit cho bng s mol proton
baz nhn
V d 1:
H
2
O + H
2
O H
3
O
+
+ OH
-
PTBT proton: [H
3
O
+
] = [OH
-
]
H
2
O
OH
-
H
3
O
+
- H
+
+ H
+
3.3 Hng s axit (K
a
), hng s baz (K
b
) Mi lin h
V d 2: dung dch HCl c nng C(mol/L)
Trong dd tn ti 2 cn bng:
HCl + H
2
O Cl
-
+ H
3
O
+
H
2
O + H
2
O H
3
O
+
+ OH
-
HCl, H
2
O
- H
+
+ H
+
Cl
-
, OH
-
H
3
O
+
PTBT proton:
[H
3
O
+
] = [OH
-
] + [Cl
-
]
= [OH
-
] + C
3.3 Hng s axit (K
a
), hng s baz (K
b
) Mi lin h
V d 3: dung dch hn hp HCl (C
1
) v CH
3
COOH (C
2
)
Cc cn bng trong dung dch
HCl + H
2
O H
3
O
+
+ Cl
-
CH
3
COOH + H
2
O CH
3
COO
-
+ H
3
O
+
H
2
O + H
2
O H
3
O
+
+ OH
-
HCl, CH
3
COOH, H
2
O
- H
+
+ H
+
H
3
O
+
Cl
-
, CH
3
COO
-
, OH
-
[H
3
O]
+
= [OH
-
] + [Cl
-
] + [CH
3
COO
-
]
C
2
= C
1
3.3 Hng s axit (K
a
), hng s baz (K
b
) Mi lin h
V d 4: dung dch NH
3
Cc cn bng:
NH
3
+ H
2
O NH
4
+
+ OH
-
H
2
O + H
2
O H
3
O
+
+ OH
-
PTBT proton: (NH
3
, H
2
O)
[OH
-
] = [NH
4
+
] + [H
3
O
+
]
V d 5: dung dch CN
-
, CH
3
COO
-
Cc cn bng:
CN
-
+ H
2
O HCN + OH
-
CH
3
COO
-
+ H
2
O CH
3
COOH + OH
-
H
2
O + H
2
O H
3
O
+
+ OH
-
PTBT proton: (CN
-
, CH
3
COO
-
, H
2
O)
[HCN] + [CH
3
COOH] + [H
3
O
+
] = [OH
-
]
3.3 Hng s axit (K
a
), hng s baz (K
b
) Mi lin h
V d 6: dung dch H
3
PO
4
V d 7: dung dch CO
3
2-
V d 8: dung dch NH
4
CH
3
COO
3.4 pH ca h n axit, n baz trong nc
pH ca dung dch axit mnh
Gi s dung dch axit mnh HA, nng C
a
:
HA + H
2
O A
-
+ H
3
O
+
H
2
O + H
2
O H
3
O
+
+ OH
-
Hoc vit di dng:
HA A
-
+ H
+
H
2
O H
+
+ OH
-
PT bo ton proton:
[H
+
] = [A
-
] + [OH
-
] = C
a
+ [OH
-
]
] [
] [
2
+
=
H
K
OH
O H
] [
] [
2
+
+
+ =
H
K
C H
O H
a
... ] [
0 ] .[ ] [
2
2
=
=
+
+ +
H
K H C H
O H a
(*)
Bin lun: [H
+
] = [A
-
] + [OH
-
] = C
a
+ [OH
-
]
Nu C
a
10
-6
[OH
-
] C
a
khi :
[H
+
] = C
a
Nu C
a
10
-8
C
a
[OH
-
] khi :
[H
+
] = [OH
-
] = 10
-7
Nu 10
-8
< C
a
< 10
-6
gii phng trnh bc 2 (*)
V d: Tnh pH ca dung dch HCl trong trng hp 10
-
3
M, 10
-7
M, 10
-9
M
pH ca dung dch baz mnh: BOH c nng C
b
Cn bng trong dung dch:
BOH B
+
+ OH
-
H
2
O H
+
+ OH
-
PT bo ton proton:
[OH
-
] = [H
+
] + [B
+
] = [H
+
] + C
b
] [
] [
2
+
=
H
K
OH
O H
... ] [
0 ] .[ ] [
2
2
=
= +
+
+ +
H
K H C H
O H b
(**)
Bin lun:
Nu C
b
10
-6
pOH = -logC
b
Nu C
b
10
-8
pOH = 7
Nu 10
-8
< C
b
< 10
-6
gii pt bc 2 (**)
pH ca dung dch n axit yu:
Gi s dung dch axit yu HA, nng C
a
Dung dch c cn bng:
HA H
+
+ A
-
H
2
O H
+
+ OH
-
PT bo ton proton:
[H
+
] = [A
-
] + [OH
-
]
Pt bo ton khi lng:
C
a
= [HA] + [A
-
]
Pt hng s axit:
] [
] ].[ [
HA
A H
K
a
+
=
] [ ] [
] [ ] [
]. [
+
+
+
+

=
OH H C
OH H
H K
a
a
] [
] [
]. [
+
+
+
=
H C
H
H K
a
a
a
a
C
H
K
2
] [
+
=
Coi [OH
-
] [H
+
] (nc phn ly khng ng k)
Gi s [H
+
] C
a
a a
C K H . ] [ =
+
) log (
2
1
a a
C pK pH =
Mt s v d
V d 1: Tnh pH ca dung dch CH
3
COOH 0,1M; pK
a
=
4,75
V d 2: Tnh pH ca dung dch NH
4
Cl 0,1M; bit NH
3
c
pK
b
= 4,75
V d 3: Tnh pH ca dung dch axit salixilic 10
-3
M c pK
a
= 3
pH ca dung dch baz yu
Gi s dung dch baz B, nng C
b
Cc cn bng trong dung dch:
B + H
2
O BH
+
+ OH
-
H
2
O H
+
+ OH
-
Pt bo ton proton
[OH
-
] = [BH
+
] + [H
+
]
Pt bo ton khi lng:
C
b
= [BH
+
] + [B]
Pt hng s K
b
] [
] ].[ [
B
OH BH
K
b
+
=
] [ ] [
] [ ] [
. ] [
+
+
+
=
H OH
H OH C
K OH
b
b
Tng t nh trng hp axit yu:
[H
+
] [OH
-
]
[OH
-
] C
b
b b
C K OH . ] [
2
=
) log (
2
1
b b
C pK pOH =
pH = 14 - pOH
Mt s v d
3
0,1M; pK
b
= 4,75
V d 2: Tnh pH ca dung dch NaCN 0,01M bit pK
HCN
=
9,21
3.5 pH ca hn hp axit v baz lin hp. m nng
V d cp axit, baz lin hp ?
Dung dch m ?
nh ngha: dd m l nhng dd c pH thay i rt t
khi thm vo dd axit mnh, baz mnh hoc pha
long dd.
Gii thch?
Lp cng thc tnh pH ca dd m:
Gi s c dd m
HA, nng C
a
NaA, nng C
b
HA H
+
+ A
-
H
2
O H
+
+ OH
-
Pt hng s K
a
:
Pt bo ton khi lng:
[HA] + [A
-
] = C
a
+ C
b
[HA] = C
a
+ C
b
[A
-
] (2)
Pt bo ton in tch:
[Na
+
] + [H
+
] = [OH
-
] + [A
-
]
[A
-
] = [H
+
] + [Na
+
] - [OH
-
]
= [H
+
] + C
b
- [OH
-
] (3)
] [
] ].[ [
HA
A H
K
a
+
=
(1)
T (1), (2) v (3) c:
] [ ] [
] [ ] [
. ] [
+
+
+
+
+
=
OH H C
OH H C
K H
b
a
a
Thng th [H
+
] v [OH
-
] C
a
v C
b
nn:
b
a
a
C
C
K H . ] [ =
+
b
a
a
C
C
pK pH log =
V d: Tnh pH ca cc dung dch sau:
CH
3
COOH 0,1M v CH
3
COONa 0,1M
CH
3
COOH 0,3M v CH
3
COONa 0,1M
NH
4
Cl 0,1M v NH
3
0,1M
NH
4
Cl 0,1M v NH
3
0,3M
thy r tc dng m ca dung dch, xt v d:
V d 1: pH ca dung dch CH
3
COOH 0,1M v
CH
3
COONa 0,1M thay i nh th no khi thm vo 1
lt dung dch ny:
10
-2
mol HCl
10
-2
mol NaOH
Nhn xt: dung dch m c cn bng
CH
3
COOH + H
2
O CH
3
COO
-
+ H
3
O
+
Khi thm vo dung dch H
+
hoc OH
-
???
pH ca dung dch m:
b
a
a
C
C
pK pH log =
= 4,75 - log1
= 4,75
Khi thm 10
-2
mol HCl vo dung dch:
HCl H
+
+ Cl
-
10
-2
10
-2
CH
3
COO
-
+ H
+
CH
3
COOH
Khi cn bng
0,1 10
-2
10
-2
0,1 + 10
-2
66 , 4
09 , 0
11 , 0
log = =
a
pK pH
Khi thm 10
-2
mol NaOH vo dung dch:
NaOH Na
+
+ OH
-
10
-2
10
-2
CH
3
COOH + OH
-
CH
3
COO
-
+ H
2
O
Cn bng
0,1 10
-2
10
-2
0,1 10
-2
84 , 4
11 , 0
09 , 0
log = =
a
pK pH
Kt lun: Khi thm vo 1 lt dung dch m 0,01 mol HCl hoc NaOH
th pH ca dung dch thay i 0,09 n v
Nu thm 0,01 mol HCl hoc NaOH vo 1 lt nc th pH thay i ntn?
V d 2: pH ca dung dch NH
4
Cl 0,1M v NH
3
0,1M thay
i ntn khi thm vo dung dch
10
-3
mol HCl
10
-3
mol KOH
V d 3: pH ca dung dch NH
4
Cl 0,2M v NH
3
0,2M thay
i ntn khi thm vo dung dch
10
-3
mol HCl
10
-3
mol KOH
Kt lun: Mi dung dch m c kh nng m khc nhau
So snh V d 1 v V d 2:
So snh V d 2 v V d 3:
m nng (): s mol axit mnh (hoc baz mnh) thm
vo mt lt dung dch m pH ca dung dch thay
i 1 n v
dpH
dC
b
+ = |
dpH
dC
a
= | v
Gi s c dung dch m:
HA C
a
NaA C
b
Pt hng s axit:
] [
] ].[ [
HA
A H
K
a
+
=
(1)
pH ca hn hp axit v baz lin hp. m nng
] [
] [
. ] [

+
=
A
HA
K H
a
dpH
dC
b
= |
]) log[ (
+
=
H d
dC
b
l hn hp dung dch m nn C
a
+ C
b
= const = C
]) (ln[
3 . 2
+
=
H d
dC
b
] [
] .[
3 . 2
+
+
=
H d
H dC
b
] [
]. .[ 3 . 2
+
+
=
H d
dC
H
b
Pt bo ton in tch:
[Na
+
] + [H
+
] = [A
+
] + [OH
-
]
C
b
+ [H
+
] = [A
-
] + [OH
-
]
] [
] [
.
] [

+
+
+
+
+ = OH
K H
K C
H
a
a
C
b
= -[H
+
] + [A
-
] + [OH
-
]
Ly o hm ca C
b
theo [H
+
]:
2 2
) ] ([
.
1
] [ ] [
2
a
a
O H
b
K H
K C
H
K
H d
dC
+
=
+ + +
ng nc phn ly khng ng k nn: [OH
-
] nh c th b qua
|
|
.
|
\
|
+
+ + =
+
+
+
+ 2
) ] ([
] .[ .
] [
] [
3 , 2
2
a
a
O H
K H
H K C
H
H
K
|
|
|
.
|
\
|
+
+ =
+
+
+
2
) ] ([
] .[ .
] [ 3 , 2
a
a
K H
H K C
H |
b
a
a
C
C
K H . ] [ =
+
|
|
|
|
.
|
\
|
+
+ =
2
2
) . (
. .
. 3 , 2
a
b
a
a
b
a
a
b
a
a
K
C
C
K
C
C
K C
C
C
K |
+
] b qua so vi C
a
, C
b
|
|
|
|
.
|
\
|
+
=
2
2
) . (
. .
3 , 2
a
b
a
a
b
a
a
K
C
C
K
C
C
K C
|
C
C C
b a
.
. 3 , 2 = |
Mt s v d tnh m nng ca dung dch
d 1: Tnh m nng ca dung dch
CH
3
COOH 0,01M
CH
3
COONa 0,01M
d 2: Tnh m nng ca dung dch
CH
3
COOH 0,1M
CH
3
COONa 0,1M
o snh kh nng m ca 2 dung dch trn
ong VD2, nu thm 10
-3
mol HCl hoc NaOH th pH ca
ung dch thay i nh th no?
Mt s v d tnh m nng ca dung dch
H ca dung dch m trong trng hp pha long thay
i t
b
a
a
C
C
pK pH log =
b
a
a
a
a
pK pH log =
6 pH ca hn hp axit v baz khng lin hp
d?
ng qut:
HA
1
C
a
(ca h HA
1
/A
1
) K
1
A
2
C
b
(ca h HA
2
/A
2
) K
2
HA
1
H
+
+ A
1
-
A
2
+ H
2
O HA
2
+ OH
-
H
2
O H
+
+ OH
-
Pt bo ton proton
[HA
2
] + [H
+
] = [OH
-
] + [A
1
-
] (1)
Pt hng s axit: HA
2
] [
] ].[ [
2
2
2
HA
A H
K
+
=
PT bo ton khi lng vi h HA
2
/A
2
-
:
[HA
2
] + [A
2
-
] = C
b
] [
]) [ ].( [
2
2
2
HA
HA C H
K
b

=
+
K
2
.[HA
2
] = [H
+
].C
b
- [H
+
].[HA
2
]
) 2 (
] [
]. [
] [
2
2
H K
C H
HA
b
+
+
+
=
.6 pH ca hn hp axit v baz khng lin hp
Pt hng s axit: HA
1
] [
] ].[ [
1
1
1
HA
A H
K
+
=
PT bo ton khi lng vi h HA
1
/A
1
-
:
[HA
1
] + [A
1
-
] = C
a
] [
] ].[ [
1
1
1

+
=
A C
A H
K
a
) 3 (
] [
.
] [
1
1
1
H K
K C
A
a
+
+
=
[HA
2
] + [H
+
] = [OH
-
] + [A
1
-
] (1)
) 2 (
] [
]. [
] [
2
2
H K
C H
HA
b
+
+
+
=
) 3 (
] [
.
] [
1
1
1
H K
K C
A
a
+
+
=
] [
.
] [
] .[
1
1
2
+ +
+
+
=
+
H K
K C
H K
H C
a b
u C
a
= mC
b
th:
... ] [
] [
.
] [
] [
1
1
2
=
+
=
+
+
+ +
+
H
H K
K m
H K
H
) (
2
1
. ] [
2 1 2 1
pK pK p K K H + = =
+
Nu C
a
= C
b
th:
th logarit nng
pH
logC
x
Khng nh c gi tr nh bn cnh gi tr ln
rt gn n gin bi ton
th logarit nng
d: V th khi xc nh pH ca dung dch axit yu
A, nng C
a
, hng s axit K
a
Gii
ung dch gm c cc cu t: H
+
, OH
-
, A
-
, HA
t tng ion:
Ion H
+
:
log[H
+
] = -pH
th l mt ng thng c h s gc l -1
Ion OH
-
:
log[OH
-
] = pH 14
th l mt ng thng c h s gc l +1
th logarit nng
Hai ng log[H
+
] v
log[OH
-
] ct nhau ti im:
log[H
+
] = log[OH
-
]
(7, -7)
Ion A
-
:
] [
] ].[ [
HA
A H
K
a
+
=
a
K
H
A
HA ] [
] [
] [
+
=
] [ ] [
] [
+
=
H
K
HA
A
a
hoc
(1) (2)
th logarit nng
a
a
K H
K
A HA
A
+
=
+
+
] [ ] [ ] [
] [
C
a
a
a a
K H
K C
A
+
=
+
] [
.
] [
] [
] [
] [ ] [
] [
+
+
+
=
+ H K
H
HA A
HA
a
] [
] .[
] [
+
+
+
=
H K
H C
HA
a
a
Da vo 2 biu thc cui cng bin lun
xy dng ng log[A
-
] v log[HA] theo pH
Bin lun
] [
] .[
]
+
+
+
=
H K
H C
A
a
a
a
a a
K H
K C
+
=
+
] [
.
]
[H
+
] K
a
pH pK
a
Mu s gi nguyn
[H
+
] K
a
pH pK
a
Mu s ch cn [H
+
]
[HA] = C
a
log[HA] = logC
a
log[HA] l mt ng
thng // trc honh ct
trc tung ti logC
a
] [
] .[
] [
+
+
+
=
H K
H C
HA
a
a
ng log[HA] l mt
ng cong
] [
.
] [
+
=
H
K C
A
a a
log[A
-
] = logC
a
.K
a
log[H
+
]
= pH + logCa.Ka
ng log[A
-
] l mt
ng cong
th logarit nng
ai ng cong log[HA] v log[A
-
] ct nhau ti:
log[HA] = log[A
-
]
K
a
= [H
+
]
pH = pK
a
(im honh )
im tung :
3 , 0 log
2
log
2
log log
=
= =
a
a
a
a a
C
C
K
K C
C
y
pH = pK
a
logC = logC
a
l im h
Nh vy: 2 ng cong trn
ct nhau ti im di im
h 0,3 n v
th logarit nng
Khi K
a
[H
+
] pH pK
a
, mu s cn K
a
Do :
a
a
K
H C ] .[
+
= log[HA] = logC
a
logK
a
+ log[H
+
]
= logC
a
logK
a
- pH
ng biu din log[HA] l ng // vi log[H
+
]
[A
-
] = C
a
log[A
-
] = logC
a
ng log[A
-
] // vi trc honh, cch trc honh 1 on logC
a
Biu din cc ng trn th
Gi s HA c nng 0,1M v pKa = 4,75
0 1 2 5 4 7 6 8 9 10 12 11 14 13 3
pH
0
-1
-2
-3
-4
-5
-6
-7
-8
-9
-10
logC
log[HA]
log[A
-
]
l
o
g
[
H
+
]
l
o
g
[
O
H
- ]
im h
th logarit nng
m li: cc bc v th logarit nng :
V ng log[H
+
] v log[OH
-
]
Tm im h
T im h v ng thng // vi trc honh
Ly di im h 0,3 n v trc tung
K 2 ng:
// log[H
+
]
// log[OH
-
]
Ni 2 ng bng 1 on cong
Mt s v d
d 1: Tnh pH ca dung dch CH
3
COOH 0,1M bit pK
a
= 4,75
Gii
Vit cc cn bng trong dung dch
CH
3
COOH H
+
+ CH
3
COO
-
H
2
O H
+
+ OH
-
Vit phng trnh bo ton proton: (CH
3
COOH, H
2
O)
[CH
3
COO
-
] + [OH
-
] = [H
+
]
Phng trnh bo ton khi lng:
[CH
3
COOH] + [CH
3
COO
-
] = 0,1
V th logarit
im h:
(pK
a
, logC
a
) (4,75; -1)
Mt s v d
2 5 4 7 6 8 9 10 12 11 14 13 3
pH
CH
3
COOH]
log[CH
3
COO
-
]
l
o
g
[
H
+
]
l
o
g
[
O
H
- ]
im h
T th:
[OH
-
] [CH
3
COO
-
]
[CH
3
COO
-
] = [H
+
]
[CH
3
COO
-
] [CH
3
COOH]
[CH
3
COOH] = 0,1
Thay cc gi tr vo
biu thc K
a
pH = (pK
a
logC
a
)
Mt s v d
d 2: Tnh pH ca dung dch HCN 10
-4
M, pK
a
= 9,3
Gii
HCN H
+
+ CN
-
H
2
O H
+
+ OH
-
[CN
-
] + [OH
-
] = [H
+
] (*)
[HCN] + [CN
-
] = 10
-4
t cc cn bng trong dung dch:
ng trnh cho nhn proton:
ng trnh bo ton khi lng:
th logarit:
im h (9,3; -4)
Mt s v d
2 5 4 7 6 8 9 10 12 11 14 13 3
pH
log[HCN]
log[CN
-
]
l
o
g
[
H
+
]
l
o
g
[
O
H
- ]
T th: khng th b qua
[OH
-
] cnh [CN
-
]
[CN
-
] + [OH
-
] = [H
+
]
] [
] [ ] [
.
2
+
+ +
= +
+
H
H
K
K H
K C
O H
a
a a
V dung dch axit [H
+
] K
a
61 , 6 . ] [
2
= + =
+
O H a a
K K C H
Mt s v d
d 3: Tnh pH ca dung dch HF c nng 10
-3
M, pK
a
= 3,17
d 4: Tnh pH ca dung dch NH
3
10
-2
M; pK
b
= 4,75
pH ca dd mui to bi mt axit yu v 1 baz yu
d?
ng hp 1: Khi C
a
= C
b
4
CN 0,1M. Bit
pK
NH3
= 4,75; pK
HCN
= 9,21
Gii
Cc cn bng trong dung dch
NH
4
CN NH
4
+
+ CN
-
NH
4
+
NH
3
+ H
+
CN
-
+ H
2
O HCN + OH
-
H
2
O H
+
+ OH
-
Pt bo ton proton: (NH
4
+
, CN
-
, H
2
O)
[NH
3
] + [OH
-
] = [HCN] + [H
+
] (1)
Pt bo ton khi lng:
[NH
4
+
] + [NH
3
] = [HCN] + [CN
-
] = 0,1 (2)
th logarit nng :
2 im h:
pH = pK
a
= 9,25
logC = -1
pH = pK
a
= 9,21
logC = -1
th logarit nng :
2 5 4 7 6 8 9 10 12 11 14 13 3
pH
log[NH
4
+
]; log[HCN]
log[NH
3
]; log[CN
-
]
l
o
g
[
H
+
]
l
o
g
[
O
H
-
]
Cn c vo th:
[NH
3
] [OH
-
]
[HCN] [H
+
]
T (1):
[NH
3
] = [HCN]
Thay vo (2):
[NH
4
+
] = [CN
-
] = 0,1
Cng thc tnh hng s axit ca NH
4
+
v HCN:
Ly K
NH4+
x K
HCN
= [H
+
]
2
4
+ + -
3
+
4
[H ].[NH ] [H ].[CN ]
[NH ] [HCN]
HCN
NH
K K
+
= =
+
4
+
HCN
NH
[H ] = K .K
Hay pH = (pK
a1
+ pK
a2
) = 9,23
V d 2: Tnh pH ca dung dch mui NH
4
CH
3
COO
0,2M
ng hp 2: Khi C
a
C
b
(gi s C
a
= q.C)
V d: Tnh pH ca dung dch mui (NH
4
)
2
C
2
O
4
0,1M.
Cho pK
NH3
= 4,75; pK
H2C2O4
= 4,22
Gii
(NH
4
)
2
C
2
O
4
2NH
4
+
+ C
2
O
4
2-
NH
4
+
NH
3
+ H
+
C
2
O
4
2-
+ H
2
OHC
2
O
4
-
+ OH
-
Pt cho nhn proton: (NH
4
+
, C
2
O
4
2-
, H
2
O)
[NH
3
] + [OH
-
] = [HCO
4
-
] + [H
+
] (1)
Pt bo ton khi lng:
[NH
3
] + [NH
4
+
] = 2C
m
= 0,2
[C
2
O
4
2-
] + [HC
2
O
4
-
] = C
m
= 0,1 (2)
V th logarit nng :
2 im h:
pH = 9,25
logC = -0,7
pH = 4,22
logC = -1
2 5 4 7 6 8 9 10 12 11 14 13 3
pH
log[NH
4
+
] log[NH
3
]
l
o
g
[
H
+
]
l
o
g
[
O
H
-
]
[HC
2
O
4
-
]
log[C
2
O
4
2-
]
T th:
[NH
3
] [OH
-
]
[HC
2
O
4
-
] [H
+
]
[NH
3
] = [HC
2
O
4
-
]
Thay vo (2):
[NH
4
+
] = 0,2
[C
2
O
4
2-
] = 0,1
u thc hng s axit:
y:
4
4 2
4
+ 2
+
2
3
+
4 2 4
[H ].[C O ]
[H ].[NH ]

[NH ] [HC O ]
NH HC O
K K
+
= =
+ 2
1 2
[H ]
.
2
K K =
1 2
1
( log )
2
a a
pH pK pK q = +
3.8 Tnh pH ca dung dch hn hp 2 axit
n hp 2 axit mnh: HA
1
(C
1
) v HA
2
(C
2
)
Trong dung dch:
[H
+
]
dd
= [H
+
]
HA1
+ [H
+
]
HA2
+ [H
+
]
H2O
= C
1
+ C
2
+ [H
+
]
H2O
Nu C
1
+ C
2
10
-6
[H
+
]
H2O
nh, b qua
pH = -log(C
1
+ C
2
)
Nu C
1
+ C
2
< 10
-8
[H
+
]
axit
nh, b qua
pH = 7
Nu 10
-8
C
1
+ C
2
< 10
-6
Gi nguyn v gii pt bc 2
n hp ca mt axit mnh HA
1
(C
1
) v mt axit yu HA
2
C
2
, K
a
):
[H
+
]
dd
= [H
+
]
HA1
+ [H
+
]
HA2
+ [H
+
]
H2O
Thng trong dung dch axit H
+
do nc phn ly khng
ng k b qua
[H
+
] = C
1
+ [H
+
]
HA2
Nu C
1
C
2
H
+
do axit yu phn ly khng ng k
b qua
[H
+
]
dd
= C
1
Nu C
1
C
2
khng b qua axit yu
V d 1: Tnh pH ca hn hp gm HCl 0,1M v
CH
3
COOH 0,1M; pK
a
= 4,75
pH = pH
HCl
= 1
Tnh ton c th:
Pt cho nhn proton: (CH
3
COOH, HCl, H
2
O)
[CH
3
COO
-
] + [Cl
-
] + [OH
-
] = [H
+
]
dd
[CH
3
COO
-
] + 0,1 + [OH
-
] = [H
+
]
dd
V th logarit:
im h
pH = 4,75
logC = -1
2 5 4 7 6 8 9 10 12 11 14 13 3
pH
CH
3
COOH]
log[CH
3
COO
-
]
l
o
g
[
H
+
]
l
o
g
[
O
H
- ]
Cn c vo th:
[CH
3
COO
-
] [OH
-
]
[CH
3
COO
-
] = [H
+
] = 0,1
[H
+
] [CH
3
COO
-
]
[H
+
] = 0,1
V d 2: Tnh pH ca dung dch HCl 10
-4
M v
CH
3
COOH 0,1M
n hp 2 axit yu
HA
1
: C
1
, K
a1
HA
2
: C
2
, K
a2
Khi :
[H
+
]
dd
= [H
+
]
HA1
+ [H
+
]
HA2
+ [H
+
]
H2O
(b qua [H
+
]
H2O
)
Trng hp 1: khi C
1
C
2
v K
1
K
2
V d: Tnh pH ca dung dch hn hp gm
CH
3
COOH 0,1M v HCN 0,3M; vi pK(CH
3
COOH) =
4 75 ; pK
HCN
=9 21
CH
3
COOH H
+
+ CH
3
COO
-
HCN H
+
+ CN
-
H
2
O H
+
+ OH
-
Pt cho nhn proton:
[CH
3
COO
-
] + [CN
-
] + [OH
-
] = [H
+
]
Pt bo ton khi lng:
[CH
3
COOH] + [CH
3
COO
-
] = 0,1
[HCN] + [CN
-
] = 0,3
V th logarit: 2 im h
pH = 4,75
logC = -1
pH = 9,21
logC = log0 3 = -0 5
2 5 4 7 6 8 9 10 12 11 14 13 3
pH
log[HCN] log[CN
-
]
l
o
g
[
H
+
]
l
o
g
[
O
H
-
]
CH
3
COOH]
log[CH
3
COO
-
]
Cn c vo th:
[CH
3
COO
-
] [CN
-
] [OH
-
]
[CH
3
COO
-
] = [H
+
]
Kt lun: H
+
trong dung
dch ch yu
do CH
3
COOH
sinh ra
ng hp 2: khi C
1
C
2
v K
1
K
2
V d: Tnh pH ca dung dch hn hp:
HA
1
0,1M ; pK
a1
= 4,75
HA
2
10
-4
M ; pK
a2
= 4
3
1
+ - + 2
3
3 1
+
a 1
[H ].[CH COO ] [H ]
[CH COOH]
[H ] = K .
CH COOH
K
C
C
= =

Cn bng trong dung dch
HA
1
H
+
+ A
1
-
HA
2
H
+
+ A
2
-
H
2
OH
+
+ OH
-
Pt cho nhn proton:
[A
1
-
] + [A
2
-
] + [OH
-
] = [H
+
] (1)
V th logarit: 2 im h
pH = 4,75
logC = -1
pH = 4
logC = -4
2 5 4 7 6 8 9 10 12 11 14 13 3
pH
g[HA
2
] log[A
2
-
]
l
o
g
[
H
+
]
l
o
g
[
O
H
-
]
log[HA
1
]
log[A
1
-
]
Cn c vo th:
[A
1
-
] [A
2
-
] [OH
-
]
[A
1
-
] = [H
+
]
Kt lun: H
+
trong dung
dch ch yu
do axit c C
ln phn ly.
ng hp 3: khi C
1
C
2
v K
1
K
2
V d: Tnh pH ca dung dch hn hp:
HA
1
0,1M ; pK
a1
= 4,75
HA
2
0,5M ; pK
a2
= 4,7
Tng t: vit pt cho nhn proton, v th logarit
1
1
+ - + 2
1
1 1
+
a 1
[H ].[A ] [H ]
[HA ]
[H ] = K .
a
K
C
C
= =

2 5 4 7 6 8 9 10 12 11 14 13 3
pH
og[HA
2
] log[A
2
-
]
l
o
g
[
H
+
]
l
o
g
[
O
H
-
]
log[HA
1
]
log[A
1
-
]
pH = 4,75
logC = -1
pH = 4,7
logC = -0,3
Cn c vo th:
[A
1
-
] [A
2
-
] [OH
-
]
[A
1
-
] + [A
2
-
] = [H
+
]
+
1 1 2 2
[H ] = C . . K C K +
3.9 Tnh pH ca dung dch a axit, a baz
V d?
Cc cn bng tn ti trong dung dch?
K
a1
, K
a2
, K
a3
K
b1
, K
b2
, K
b3

d: Tnh pH ca dung dch H
3
PO
4
10
-2
M. Bit pK
a1
= 2;
K
a2
= 7; pK
a3
= 12
Gii
t cc cn bng xy ra trong dung dch:
H
3
PO
4
H
2
PO
4
-
+ H
+
H
2
PO
4
-
HPO
4
2-
+ H
+
HPO
4
2-
PO
4
3-
+ H
+
H
2
O OH
-
+ H
+
cho nhn proton:
[H
+
] = [OH
-
] + [H
2
PO
4
-
] + 2[HPO
4
2-
] + 3[PO
4
3-
]
bo ton khi lng:
3
PO
4
] + [H
2
PO
4
-
] + [HPO
4
2-
] + [PO
4
3-
] = C
a
= 10
-2
V th logarit:
2 5 4 7 6 8 9 10 12 11 14 13 3
pH
l
o
g
[
H
+
]
l
o
g
[
O
H
-
]
4
H
2
PO
4
-
HPO
4
2-
PO
4
3-
T th:
[H
2
PO
4
-
] [HPO
4
2-
]
[PO
4
3-
]
[OH
-
]
Nn:
[H
+
] = [H
2
PO
4
-
]
Nhn xt: Nu dung
dch a axit c
K
1
K
2
K
3
th H
+
ch yu do nc 1
phn ly v pH ca dd
c tnh tng t nh
pH ca axit 1 nc
+ + 2
2 4
1
+
3 4 a
+ 2 +
1 1 a
+
[H ].[H PO ] [H ]
K
[H PO ] C [H ]
[H ] K .[H ] - K .C 0
[H ] = ...
= =
+ =

Trng hp tng qut: Tnh pH ca dung dch
H
2
A c nng C
a
, K
1
, K
2
Tnh pH ca dung dch Na
3
PO
4
10
-2
M
Sinh vin bin lun trong 2 trng hp sau
3.10 H m kp
nh ngha: H m kp l h m dung dch cha nhiu
p axit baz lin hp
d???
t s bi tp:
Bi 1: Tnh pH ca Na
2
HPO
4
10
-2
M
Bi 2: Tnh pH ca dung dch hn hp KH
2
PO
4
6.10
-2
M
v Na
2
HPO
4
4.10
-2
M
Bi 3: Tnh pH ca dung dch hn hp gm H
3
PO
4
0,1M; CH
3
COOH 0,1M v NaOH 0,18M
C S L THUYT
HA PHN TCH 1
GV: Trn Mai Lin
Chng 4: Phn ng phc cht
4.1 nh ngha Danh php
4.2 Hng s bn v hng s khng
bn ca phc cht
4.3 Nng cn bng ca cc cu t
trong dung dch to phc
4.4 Cc yu t nh hng n s
phn ly ca phc cht. Hng s bn
iu kin
nh ngha: Phc cht l nhng hp cht to bi cation
(ion trung tm) kt hp vi cc phi t (l cc phn t
hoc ion); n tn ti trong dung dch ng thi c kh
nng phn ly thnh cc ion n hay phn t.
[Ag(CN)
2
]
-
Ion trung tm
Phi t
S phi tr
Trong dung dch: [Ag(CN)
2
]
-
Ag
+
+ 2CN
-
1 phn
Danh php: Tn phi t + tn ion trung tm
Nu phi t l gc axit: thm o vo tn gc
SO
4
2-
: sunfato
NO
3
-
: nitrato
Nu phi t l halogen:
F
-
: floro
Cl
-
: cloro
Br
-
: bromo
I
-
: iodo
OH
-
: hidroxo
S phi tr: 1 (mono); 2 (i); 3 (tri); 4 (tetra); 5 (penta); 6
(hexa)
4.2 Hng s bn v hng s khng bn ca phc cht
Hng s bn: i lng c trng cho kh nng to phc
Hng s khng bn: i lng c trng cho kh nng phn ly
phc cht
[Cu(NH
4
)
4
]
2+
phn ly
to thnh
Cu
2+
+
4NH
3
2+ 4
3
2+
3 4
[Cu ].[NH ]
K
[Cu(NH ) ]
=
Hng s khng bn:
Hng s bn:
2+
3 4
2+ 4
3
[Cu(NH ) ] 1
[Cu ].[NH ] K
| = =
Da vo
K v c
th bit
c
phc
bn hay
khng
4.2 Hng s bn v hng s khng bn ca phc cht
Vi phc c nhiu phi t, s phn ly xy ra theo tng
nc:
Cd
2+
+ NH
3
Cd(NH
3
)
2+

1
, K
1
Cd(NH
3
)
2+
+ NH
3
Cd(NH
3
)
2
2+

2
, K
2
Cd
2+
+ 4NH
3
Cd(NH
3
)
4
2+
, K
+
, K: hng s bn v khng bn tng cng
=
1
.
2
.
3
.
4
=
1,4
K = K
1
.K
2
.K
3
.K
4
= K
1,4
4.3 Nng CB ca cc cu t trong dd to phc
Gi s ion M c nng ban u C
m
to phc vi phi t L
M + L ML
ML + L ML
2
1
[ML]
[M].[L]
| =
(1)
2
2
[ML ]
[ML].[L]
| = (2)
T (1) [ML] =
1
.[M].[L]
Thay vo (2):
[ML
2
] =
1
.
2
.[M]
2
.[L]
Theo nh lut bo ton khi lng:
[M] + [ML] + [ML
2
] = C
m
[M] +
1
.[M].[L] +
1
2
.[M].[L]
2
= C
m
m
2
1 1 2
C
[M]
1 [L] [L]
=
+| +| |
m 1
2
1 1 2
C [L]
[ML]
1 [L] [L]
|
=
+| +| |
2
m 1 2
2
2
1 1 2
C [L]
[ML ]
1 [L] [L]
||
=
+| +||
Trng hp tng qut:
m
2 n
1 1 2 1 2 n
C
[M]
1 [L] [L] ... ... [L]
=
+| +| | + +| | |
m 1
2 n
1 1 2 1 2 n
C [L]
[ML]
1 [L] [L] ... ... [L]
|
=
+| +| | + +| | |
n
m 1 n
n
2 n
1 1 2 1 2 n
C ... [L]
[ML ]
1 [L] [L] ... ... [L]
| |
=
+| +| | + +| | |
V d: Tnh [Ag
+
] v [CN
-
] trong dung dch phc Ag(CN)
2
-
0,1M; bit = 10
21
Gii
Cn bng trong dung dch
Ag(CN)
2
-
Ag
+
+ 2CN
-
Biu thc hng s bn:
- +
2
+ - 2 + + 2
[Ag(CN) ] 0,1 [Ag ]
[Ag ].[CN ] [Ag ].4[Ag ]
| = =
Gi s [Ag
+
] 0,1 [Ag
+
] = 2,9.10
-8
Vy gi thit l ng
[CN
-
] = 5,8.10
-8
V d 2: Tnh nng cn bng ca cc cu t trong
dung dch Ag(NH
3
)
2
+
10
-2
M, bit K = 6,8.10
-8
V d 3: Tnh nng cn bng ca cc cu t trong
dung dch CdCl
2
10
-2
M. Bit Cd
2+
to phc vi Cl
-
cc
phc: CdCl
+
, CdCl
2
, CdCl
3
-
, CdCl
4
2-
cc hng s bn
tng ng l 10
2,05
, 10
0,55
, 10
-0,2
, 10
0,5
V d 4: Tnh nng cn bng Cl
-
kt ta AgCl tan t
nht, bit Ag
+
to phc vi Cl
-
vi cc hng s sau:
AgCl
1
= 10
3,04
AgCl
2
-

1,2
= 10
5,04
AgCl
3
2-

1,3
= 10
5,05
AgCl
4
3-

1,4
= 10
5,3
4.4 Cc yu t ah n s phn ly ca phc. HSB iu kin
Gi s trong dung dch c phc MY
2-
c mt ion L v H
+
.
Trong :
L c kh nng to phc ph vi M
H
+
c kh nng to phc ph vi Y
4-
MY
2-
M
2+
+ Y
4-
( d theo di khng vit in tch)
Biu thc HSB ca phc:
4-
[MY]
[M].[Y ]
| =
M to phc ph vi L:
M + L ML
ML + L ML
2
ML
n-1
+ L ML
n
H
+
to phc ph vi Y
4-
:
H
+
+ Y
4-
HY
3-
K
4
H
+
+ HY
3-
H
2
Y
2-
K
3
H
+
+ H
2
Y
2-
H
3
Y
-
K
2
H
+
+ H
3
Y
-
H
4
Y K
1
2
2
[ML ]
[ML].[L]
| =
1
[ML]
[M].[L]
| =
Gi [M] l nng ca M do phc phn ly, khi :
[M] = [M] + [ML] + [ML
2
] + + [ML
n
] (1)
Gi [Y
4-
] l nng ca Y
4-
do phc phn ly:
[Y
4-
] = [Y
4-
] + [HY
3-
] + [H
2
Y
2-
] + [H
3
Y
-
] + [H
4
Y] (2)
T (1):
2 n
1 1,2 1,n
[M]' [M] [M][L] [M][L] ... [M][L] = +| +| + +|
( )
2 n
1 1,2 1,n
[M] 1 [L] [L] ... [L] = +| +| + +|
M(L)
T (2):
2 3 4
4- 4-
4 4 3 4 3 2 1,4
[H ] [H ] [H ] [H ]
[Y ]' [Y ]. 1
K K .K K .K .K K
+ + + +
| |
= + + + +
|
|
\ .
Y(H)
4-
M(L) Y(H)
[MY] 1
' .
[M]'.[Y ]' .
| = = |
o o
Hoc
M(L) Y(H)
K' K. . = o o
Mt s v d
V d 1: Tnh nng cc cu t c trong dung dch hn hp gm
MgY
2-
10
-2
M v Ca
2+
10
-2
M. Bit:
(MgY
2-
) = 10
8,7
(CaY
2-
) = 10
10,7
Gii
Nhn xt: t gi tr HSB ca 2 phc MgY
2-
v CaY
2-
2 2
CaY MgY

| > |
C phn ng:
Ca
2+
+ MgY
2-
CaY
2-
+ Mg
2+
T phn ng: [CaY
2-
] = [Mg
2+
]
Mt s v d
2
2-
2 4-
CaY
[CaY ]
[Ca ].[Y ]
+
| =
2
2-
2 4-
MgY
[MgY ]
[Mg ].[Y ]
+
| =
2-
2- 2 4-
CaY
[CaY ] .[Ca ].[Y ]
+
= |
2-
2-
2
4-
MgY
[MgY ]
[Mg ]
.[Y ]
+
=
|
2
2
4-
4-
CaY
MgY
1
[Y ]
.[Y ]
| =
|
2- 2
4 9,75
CaY MgY
1
[Y ]= 10
.

=
| |
Mt s v d
Theo nh lut bo ton khi lng:
[Mg
2+
] + [MgY
2-
] = 10
-2
[Mg
2+
] = 9,2.10
-3
[Ca
2+
] = 8,2.10
-4
V d 2: Tnh nng cn bng ca Mg
2+
, Y
4-
, MgY
2-
khi
trong dung dch c Mg
2+
10
-2
M, Y
4-
10
-2
M, pH = 11. Bit:
(MgY
2-
) = 10
8,7
(MgOH
+
) = 10
2,58
H
4
Y c pK
1
= 2; pK
2
= 2,67; pK
3
= 6,27; pK
4
= 10,95
C S L THUYT
HA PHN TCH 1
GV: Trn Mai Lin
Chng 5: Phn ng kt ta
5.1 S to thnh kt ta
Quy lut tch s tan
5.2 Tch s tan v tan
5.3 Cc yu t nh hng
n tan
5.4 S nhim bn kt ta
5.5 Kt ta phn on
5.1 S to thnh kt ta Quy lut tch s tan
Tc phn ng to ta ph thuc vo yu t no?
Tc ha tan ta:
Phn ng t cn bng khi:
kt 1
Ag Cl
v K .S.a .a
+
=
Ag
+
+ Cl
-
AgCl
to ta
ha tan
ht 2
v K .S =
v
ht
= v
kt
Tng qut:
nA + mB A
n
B
m
1
Ag Cl
K .S.a .a
+
2
K .S
=
2
AgCl
Ag Cl
1
K
a .a const T
K
+
= = =
T ch ph thuc vo nhit
n m
A B
n m
A B A B
n n m m
T a .a
[A] .f .[B] .f
=
=
V kt ta c tan nh nn coi f 1
Quy lut tch s tan:
n m
n m
A B
T [A] .[B] =
n m
n m
A B
T [A] .[B] <
Kt ta c to thnh
n m
n m
A B
T [A] .[B] >
Kt ta khng c to thnh
n m
n m
A B
T [A] .[B] =
Trng thi cn bng
5.2 Tch s tan v tan
tan (S) ca mt cht l nng ca cht trong
dung dch bo ha ( mt nhit nht nh)
S v T l i lng c trng cho dung dch bo ha
V d 1: Tnh T
Mg(OH)2
20
0
C bit rng nhit
100ml dung dch bo ha c cha 0,84 mg Mg(OH)
2
.
Gii
T gi thit v s mg cht tan trong dung dch bo ha
suy ra:
2
4
Mg(OH)
0, 84 1000
S . 1, 4.10
1000.58 100

= =
Mg(OH)
2
Mg
2+
+ 2OH
-
S S 2S
2
2+ - 2
Mg(OH)
3
4 3
11
T [Mg ].[OH ]
4.S
4.(1, 4.10 )
1,1.10
=
=
=
=
V d 2: Tnh tan ca CaSO
4
20
0
C bit T ca CaSO
4
ti
nhit l 9,1.10
-6
5.3 Cc yu t nh hng n tan
Cht in ly l
Ion chung
Phn ng ph
Nhit
Kch thc kt ta
1. Khi dung dch c mt cc cht in ly l:
Lc ion ca dung dch:
2
i i
1
C Z
2
=

f thay i
S thay i
V d: Tnh tan ca AgCl trong nc nguyn cht v trong dung
dch c KNO
3
0,1M. T
AgCl
= 1,1.10
-10
Gii
Trong nc:
AgCl Ag
+
+ Cl
-
S S S
T = S
2
S = 1,05.10
-5
Trong KNO
3
0,1M:
Dung dch c K
+
, NO
3
-
, Ag
+
, Cl
-
(b qua s phn ly ca nc)
2
i i
1
C Z
2
=

= (0,1.1
2
+ 0,1.1
2
+ 1,05.10
-5
.1
2
+ 1,05.10
-5
.1
2
)
= 0,1
+ -
2
Ag Cl
1 0,1
l ogf l ogf .1 . 0,12
2
1 0,1
= = =
+
Ag Cl
f f 0, 76
+
= =
2 2 5
AgCl
T
T f .S S 1, 38.10
f

= = =
2. Dung dch c mt cc ion chung:
V d: Tnh tan ca BaSO
4
trong nc v trong dung
dch c Na
2
SO
4
10
-2
M. Bit T = 1,03.10
-10
Gii
Trong nc:
Trong dung dch Na
2
SO
4
10
-2
M:
Na
2
SO
4
2Na
+
+ SO
4
2-
10
-2
2.10
-2
10
-2
BaSO
4
Ba
2+
+ SO
4
2-
S S S + 10
-2
10 5
S T 1, 03.10 1, 02.10

= = =
Lc ion trong dung dch:
2 2 2 5 2 2
1
(1 .2.10 2 .1, 02.10 2 .10 )
2

= + +
= 3.10
-2
SO
4
2-
Ba
2+
Na
+
2+ 2-
4
2
Ba SO
2
1 3.10
l ogf l ogf .2. 0, 295
2
1 3.10
= = =
+
f = 0,51 T = [Ba
2+
].[SO
4
2-
].f
2
= S.10
-2
.0,51
2
S = 4.10
-8
(gim hn 250 ln)
3. Dung dch c mt cc cht l c kh nng phn ng ph
vi ion trong kt ta:
A
n
B
m
nA + mB
Gi s trong dung dch c mt M, L
L c kh nng to phc vi A
M c kh nng to phc vi B
[A] = [A].
A(L)
[B] = [B].
B(M)
T = T.
n
A(L).
m
B(M)
T T
V d 1: Tnh tan ca CaC
2
O
4
trong dung dch c pH
= 4. Bit T ca CaC
2
O
4
l 2,3.10
-9
.
V d 2: Tnh tan ca CuS trong nc bit T ca
CuS l 6,3.10
-36
H
2
S c pK
1
= 7; pK
2
= 12,89
Cu
2+
to phc vi OH
-
c
1
= 10
7
;
1,2
= 10
13,68
;
1,3
= 10
17
;
1,4
= 10
18,5
V d 3: Tnh tan ca Ca
3
(PO
4
)
2
bit T = 10
-26
H
3
PO
4
c pK
1
= 2,1; pK
2
= 7,2; pK
3
= 12,6
ca Ca(OH)
+
l 10
4,46
4. nh hng ca nhit n tan: tan ca kt ta
tng hay gim ph thuc vo nhit ha tan ca cht
5. nh hng ca kch thc kt ta
5.4 S nhim bn kt ta
Hin tng cng kt
nh hng ca hin tng cng kt
Cch gim hin tng cng kt (ty theo dng kt ta)
5.5 Kt ta phn on
Ag
+
(aq) + I
-
(aq) AgI (s)
Ag
+
(aq) + Cl
-
(aq) AgCl (s)
C S L THUYT
HA PHN TCH 1
GV: Trn Mai Lin
Chng 6: Phn ng oxy ha kh
6.1 Th in cc cn bng. Phng trnh Nernst
6.2 Cc yu t nh hng n th oxy ha kh. Th tiu
chun
6.3 Th ca cp oxy ha kh lin hp
6.4 Th ca cp oxy ha kh khng lin hp
6.5 Cht oxy ha, kh a bc
6.6 Hng s cn bng ca phn ng oxy ha kh
6.7 Vn tc ca phn ng oxy ha kh
Mt s khi nim
Phn ng oxy ha kh
Cht oxy ha
Cht kh
Cp oxy ha kh lin hp
6.1 Th in cc cn bng. Phng trnh Nernst
Phng trnh Nernst:
0
Ox
Kh
a RT
E E ln
nF a

Ox + ne Kh
0
Ox
Kh
a 0, 059
E E log
n a

6.2 Cc yu t ah n th OXH - Kh. Th tiu chun
1. nh hng ca H
+
:
Th tiu chun trong cc bng l gi tr th khi [H
+
] = 1
Thc t trong cc dung dch [H
+
] 1 gi tr th thay
i:
E
0
E
0
V d: Tnh th oxh kh tiu chun ca cp AsO

4
3-
/AsO
3
3-
trong mi trng pH = 8, bit khi pH = 0 th
th tiu chun l 0,57V
Gi
Gi
i
i
Phng trnh phn ng:
AsO
4
3-
+ 2H
+
+ 2e AsO
3
3-
+ H
2
O
Phng trnh Nernst:
3-
4
3-
3
AsO
0 2
H
AsO
a
0, 059 0, 059
E E loga log
2 2 a

n gin thay hot bng nng :
3-
0 + 2
4
3-
3
[AsO ] 0, 059 0, 059
E E log[H ] log
2 2 [AsO ]

Th tiu chun iu kin khi pH = 8:
' 0 8 2
0
0, 059
E E log(10 ) 0,1V
2

Nhn xt?
V d 2: Thit lp s ph thuc ca th kh vo pH i
vi phn ng:
Cr
2
O
7
2-
+ 14H
+
+ 6e 2Cr
3+
+ 7H
2
O
2 3
2 7
2
0 14
2 7
3 2
Cr O / 2Cr
0,059 [Cr O ]
E E log [H ]
6 [Cr ]

2 3
2 7
2
0 14
2 7
3 2
Cr O / 2Cr
0,059 0,059 [Cr O ]
E E log[H ] log
6 6 [Cr ]

2 3
2 7
2
0'
2 7
3 2
Cr O / 2Cr
0,059 [Cr O ]
E E log
6 [Cr ]

Trong :
2 3
2 7
0' 0 16 0
Cr O / 2Cr
0,059
E E lg[H ] E 0,138pH
6

Nh vy mi trng cng axt tnh oxi ha ca Cr
2
O
7
2-
cng mnh
2. nh hng ca phn ng to phc:
V d: Tnh th oxy ha kh tiu chun ca cp
Fe
3+
/Fe
2+
trong dung dch c d F
-
to phc FeF
3
3-
c
hng s bn tng cng
1,6
= 10
16
. Th ca cp khi
khng c s to phc l 0,77V
Gi
Gi
i
i
Cc phn ng:
Fe
2+
- e Fe
3+
Fe
3+
+ 6F
-
FeF
6
3-
Fe
2+
+ 6F
-
- e FeF
6
3-
+
Phng trnh Nernst cho h oxh kh trn:
E = E
0
khi:
3-
6
2+ - 6
[FeF ]
1
[Fe ].[F ]

3+ - 6
1,6
2+ - 6
[Fe ].[F ]
1
[Fe ].[F ]
3+
2+
1,6
[Fe ] 1
[Fe ]

3-
'
6
0
2+ - 6
[FeF ] 0, 059
E E log
1 [Fe ].[F ]

Do :
3+
'
0 0
2+
'
0 0
1,6
[Fe ]
E E 0, 059log
[Fe ]
1
E E 0, 059log 0,16V


3. nh hng ca phn ng kt ta:
V d: Tnh th kh oxh kh iu kin ca cp
Cu(II)/Cu(I) khi c d ion I
-
to kt ta vi Cu
+
, T
CuI
=
10
-12
. Th tiu chun khi khng c p to ta l 0,17V
T nh gi kh nng phn ng gia Cu
2+
vi I
-
bit
E
0
Cu2+/Cu
= 0,153V; E
0
I3-/3I-
= 0,5355V.
Th oxh-kh ca hn hp mt cp oxh-kh lin hp thay i rt t khi
thm vo mt lng nh cht oxh hoc cht kh
V d:
Th oxh-kh ca dung dch hn hp Fe
3+
1M v Fe
2+
1M:
3+
0
2+
[Fe ]
E E 0, 059log 0, 77(V)
[Fe ]

Nu thm 1 lt dung dch hn hp 0,1mol Ce
4+
v H
2
SO
4
xy ra
phn ng:
Ce
4+
+ Fe
2+
= Ce
3+
+ Fe
3+
Nng Fe
2+
gim xung cn 0,9 mol/L
Nng Fe
3+
tng ln l 1,1 mol/L
Th ca hn hp l:
1,1
E 0, 77 0, 059log 0, 785(V)
0,9

Gi s dung dch c cht:
Ox
1
ca cp lin hp Ox
1
/Kh
1
Kh
2
ca cp lin hp khc Ox
2
/Kh
2
Pt cho nhn e ca tng cp:
Ox
1
+ n
1
e Kh
1
Ox
2
+ n
2
e Kh
2
Pt tng cng:
n
2
Ox
1
+ n
1
Kh
2
= n
2
Kh
1
+ n
1
Ox
2
Phng trnh Nernst ca 2 cp:
0
1
1 1
1 1
[Ox ] 0, 059
E E log
n [Kh ]

0
2
2 2
2 2
[Ox ] 0, 059
E E log
n [Kh ]

V d 1: Tnh th oxy ha kh ca dung dch hn hp
[Ce
4+
] = 1,1.10
-1
M v [Fe
2+
] = 10
-1
M bit E
0
(Ce
4+
/Ce
3+
) =
1,55V v E
0
(Fe
3+
/Fe
2+
) = 0,77V.
Gi
Gi
i
i
Phn ng:
Ce
4+
+ Fe
2+
= Fe
3+
+ Ce
3+
Ton b lng Fe
2+
b oxy ha hon ton:
[Fe
3+
] = [Ce
3+
] = 10
-1
Nng Ce
4+
trong dung dch:
[Ce
4+
] = 1,1.10
-1
10
-1
= 10
-2
Th ca dung dch c tnh theo cp [Ce
4+
]/[Ce
3+
]
E = 1,56V
Ce
4+
9.10
-2
M v Fe
2+
10
-1
M.
s: E = 0,8V
Ce
4+
0,1M v Fe
2+
0,1M.
s: E = 1,16V
Cht oxy ha a bc l cht c th b kh theo nhiu nc
Fe
3+
+ e Fe
2+
E
1
0
= 0,77V
Fe
2+
+ 2e Fe
0
E
2
0
= -0,44V
i vi nhng cht oxy ha v kh a bc, nu bit th
tiu chun ca 2 nc th c th tnh c th tiu chun
ca nc th 3
V d: Bit th tiu chun ca 2 na phn ng:
Fe
3+
+ 3e Fe
0
E
1
0
= -0,036V
Fe
2+
+ 2e Fe
0
E
2
0
= -0,44V
Hy tnh th oxy ha kh ca cp: Fe
3+
/Fe
2+
Quy tc Luther: Nu m, n v p l nhng bc ca oxy ha
ca cht oxy ha hoc cht kh a bc (gi s m > n >
p) th:
0 0 0
(m,p) (m,n) (n,p)
(m p)E (m n)E (n p)E
6.6 Hng s cn bng ca phn ng oxy ha kh
Gi s c phn ng oxy ha kh:
Ox
1
+ Kh
2
Ox
2
+ Kh
1
Hng s cn bng ca phn ng:
1 2
2 1
a b
[Kh ] [Ox ]
K =
a b
[Kh ] [Ox ]
Bn phn ng 1: aOx
1
+ ne aKh
1
0
1
0 1
1
0
2
2 2
2
[ ] 0, 059
lg
[ ]
[ ] 0, 059
lg
[ ]

a
a
b
b
Ox
E E
n Kh
Ox
E E
n
Kh
Bn phn ng 2: bOx
2
+ ne bKh
2
0 0
1 2
1 2
1
2
[ ] [ ] 0, 059 0, 059
lg lg
[ ]
[ ]

a b
a
b
Ox Ox
E E
n Kh n
Kh
0 0
1 2
1 2
1 2
0 0
1 2
)
[ ] [ ] 0, 059
lg
[ ] [ ]
(
lg
0, 059

a b
a b
Kh Ox
E E
n
Ox Kh
n E E
K
Khi phn ng t cn bng th E
1
= E
2
, nn:
6.7 Vn tc ca phn ng oxy ha kh
Yu t nh hng n tc phn ng oxy ha kh:
Cht xc tc
S cm ng
C S L THUYT
HA PHN TCH 1
GV: Trn Mai Lin
Chng 7: CB gia hai dung mi khng trn ln. S chit
7.1. Khi nim. nh ngha
7.2. Phn loi cc h chit
7.3. ngha v ng dng ca phng php chit
7.1. Khi nim. nh ngha
Chit l qu trnh tch
v phn ly cc cht
Qu trnh chit c th
chuyn mt lng nh
cht nghin cu t
mt th tch ln vo
mt th tch nh dung
mi khc. (qt lm
giu)
Extraction of carotene from carrots
7.2. Phn loi cc h chit
H chit chelate.
H chit lin hp ion, trao i ion v d a acid
7.3. ngha v ng dng ca phng php chit
Tch, phn ly, lm giu cc cht

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Trn Mai Lin Analytical Chemistry 1 1

Trn Mai Lin Analytical Chemistry 1 12

Trn Mai Lin Analytical Chemistry 1 13

3.8 Tnh pH ca dung dch hn hp 2 axit

3.8 Tnh pH ca dung dch hn hp 2 axit

3.9 Tnh pH ca dung dch a axit, a baz

3.9 Tnh pH ca dung dch a axit, a baz

V d: Tnh th oxh kh tiu chun ca cp AsO

Trn Mai Lin Analytical Chemistry 1 11

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