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GV: LI TH HIN
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Tn hc phn
S tn ch
2
Muc tiu cua hc phn
Sau khi hon tt hc phn, sinh vin phi nm c
nhng kin thc v Ho phn tch, v phn tch nh
tnh v phn tch nh lng mt s cht c bn.
M ta vn tt ni dung hc phn
Hc phn ny nhm cung cp cho sinh vin nhng
kin thc c s, nhng nguyn l chung ca ha hc
phn tch, bao gm cc phn: chun axit-baz,
phc cht, oxy ha kh, ta, v mt s phng php
ha l khc.
Ha phn tch
Analytical chemistry
Tai liu hc tp
Sch, gio trnh chnh
Gio trnh Ha phn tch, H Cng nghip TP.HCM.
Tai liu tham khao
[4] L Xun Mai, Nguyn Th Bch Tuyt (2000), Gio trnh phn
tch nh lng, NXB i hc quc gia Tp. HCM.
Ni dung hc phn
PHN TH NHT: NH TNH
Chng 1. Cc khi nim v nh lut c bn
Chng 2. Phn tch nh tnh cation nhm 1
Chng 3. Phn tch nh tnh cation nhm 2
Chng 4. Phn tch nh tnh cation nhm 3
PHN TH HAI: NH LNG
Chng 1. Phn tch khi lng
Chng 2. Phn tch th tch
Chng 3. Phn tch axit baz
Chng 4. Phn tch oxy ha- kh
Chng 5. Phn tch phc cht
Fields of chemistry
Physical chemistry
Analytical chemistry
Organic chemistry
Inorganic chemistry
Biological chemistry
Pp ha l
- Cc pp ph
- Cc pp in ha
- Cc pp sc k
Nng ng lng CN
PHN 1: NH TNH
CHNG 1. CC KHI NIM V NH LUT CN BN
Khi nim in ly
Hng s phn ly dung dch
Hot , nng , h s hot
Hng s bn v khng bn
in ly
Mi quan h gia in ly v hng s
phn ly
ion mang in tch tri du, cc cht trong trng thi nng
chy hay trong dung dch, c kh nng phn ly thnh
nhng ion mang in tch tri du, lm cho h c kh nng
dn c in, gi l cht in ly
Fe2+ + 2Cl-
A nBm
nAm+ + m Bn-
A .B
m n
K cb
n m
Am Bn
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 Z1, Z2, , Zi
nng ca tng cu t C1, C2, , Ci
log f i 0,5
log f i 0,5
Z i2
1
Z i2
1
A.
V d:
CH3COO- + H+
CH3COOH
Kpi . =1
Kcb = = 104,74
1.1.5. in ly
L t s gia nng cht in ly b phn ly vi nng
cht in ly em vo ho tan.
n
n0
n l s mol ca cht in ly b phn ly
n0 l s mol ca cht in ly em vo ho tan
A + H 2O B + H 3O +
Hng s cn bng:
[ B].[H 3O ]
K
[ A].[H 2O]
(1)
[ B ].[ H 3O ]
(1) K .[ H 2O ]
Ka
[ A]
Ka l hng s axit; pKa = -logKa
Thng qua gi tr Ka c th xc nh mnh, yu ca axit?
[ A].[ OH ]
K b K .[ H 2O ]
[ B]
a axit: phn t cha nhiu hn 2 H phn ly nhiu nc,
mi nc c mt hng s
V d: axit H3PO4
H3PO4 + H2O H2PO4- + H3O+
pKa1 = 2,12
H2PO4- + H2O HPO42- + H3O+
pKa2 = 7,21
HPO42- + H2O PO43- + H3O+
pKa3 = 12,36
a baz: PO43-, c pKb1, pKb2, pKb3
[ B ].[ H 3O ] [ A].[ OH ]
K a .K b
.
K H 2O 10 14
[ A]
[ B]
pKa + pKb = 14
OH-
- H+
H 2O
+ H+
H3O+
PTBT proton:
- H+
HCl, H2O
+ H+
H3O+
H3O+
= C1
C2
[OH ]
K H 2O
[ H ] Ca
[H ]
[ H ]2 Ca .[H ] K H 2O 0
[ H ] ...
K H 2O
[H ]
(*)
[OH ]
K H 2O
[H ]
[ H ]2 Cb .[H ] K H 2O 0
[ H ] ...
(**)
[ H ].[ A ]
Ka
[ HA ]
[
H
]
[
OH
]
K a [ H ].
Ca [ H ] [OH ]
[
H
]
K a [ H ].
Ca [ H ]
Gi s [H+] Ca
[ H ]2
Ka
Ca
[ H ] K a .Ca
1
pH ( pK a log Ca )
2
[
OH
]
[
H
]
b
[OH ] K b .
[OH ] [ H ]
[OH ]2 K b .Cb
1
pOH ( pKb log Cb )
2
pH = 14 - pOH
Ag+ + Cl-
to ta
ha tan
AgCl
vkt K1.S.a Ag .a Cl
Tc ha tan ta:
v ht K 2 .S
Phn ng t cn bng khi:
vht = vkt
K 2 .S
K1.S.a Ag .a Cl =
a Ag .a Cl
K2
const TAgCl
K1
T ch ph thuc vo nhit
Tng qut:
nA + mB AnBm
TAn Bm a An .a Bm
[A]n .f An .[B]m .f Bm
V kt ta c tan nh nn coi f 1
K .S .Ag Cl K .S
K2
Ag . Cl
const TAgCl
K1
T ch ph thuc vo nhit
Tng qut:
nA + mB AnBm
TAm Bn A
.B
m n
n m
1.4.2. 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 TMg(OH)2 200C bit rng nhit 100ml
dung dch bo ha c cha 0,84 mg Mg(OH)2.
Giai
T gi thit v s mg cht tan trong dung dch bo ha
suy ra:
SMg(OH)2
0,84 1000
.
1, 4.104
1000.58 100
1.4.2. tan
Mg(OH)2
S
Mg2+
2OH2S
4.(1, 4.10 )
1,1.1011
1.4.3. iu kin kt ta
Kt ta khng c to thnh
Kt ta c to thnh
Trng thi cn bng
Cc yu t nh hng s kt ta
Cht in ly l
Ion chung
Phn ng ph
Nhit
Kch thc kt ta
[Ag(CN)2]
S phi tr
Phi t
Ion trung tm
1 phn
Ag+ +
2CN-
Hng s bn:
phn ly
to thnh
Cu2+
[Cu 2+ ].[NH3 ]4
K
[Cu(NH3 )4 2+ ]
[Cu(NH3 )4 2+ ] 1
2+
4
[Cu ].[NH3 ]
K
4NH3
Da vo
K v c
th
bit
c
phc
bn hay
khng
Cd2+ + NH3
+
Cd(NH3)2+
Cd(NH3)2+ + NH3
Cd(NH3)22+
1, K1
2, K2
Cd2+ + 4NH3
Cd(NH3)42+
, K
M + L
ML + L
ML
[ML]
1
[M].[L]
(1)
ML2
[ML 2 ]
2
[ML].[L]
(2)
Cm12 [L]2
[ML2 ]
1 1[L] 12 [L]2
Cm1[L]
1 1[L] 12 [L]2 ... 12 ...n [L]n
Cm1...n [L]n
[MLn ]
1 1[L] 12 [L]2 ... 12 ...n [L]n
Gii
Cn bng trong dung dch
Ag(CN)2- Ag+ + 2CN-
+
- 2
[Ag ].[CN ] [Ag + ].4[Ag + ]2
Gi s [Ag+] 0,1
Vy gi thit l ng
[Ag+] = 2,9.10-8
[CN-] = 5,8.10-8
L c kh nng to phc ph vi M
H+ c kh nng to phc ph vi Y4-
[MY]
[M].[Y 4- ]
ML
ML + L
MLn-1 + L
ML2
[ML]
[M].[L]
[ML 2 ]
[ML].[L]
MLn
H+ to phc ph vi Y4-:
H+
H+
H+
H+
+
+
+
+
K4
K3
K2
K1
(1)
(2)
T (1):
M(L)
T (2):
2
3
4
[H
]
[H
]
[H
]
[H
]
[Y 4- ]' [Y 4- ]. 1
K 4 K 4 .K 3 K 4 .K 3 .K 2 K1,4
Y(H)
[MY]
1
'
.
4[M]'.[Y ]'
M (L) . Y(H)
Hoc
CaY2 MgY2
C phn ng:
[CaY 2- ]
[Ca 2 ].[Y 4- ]
MgY 2
[MgY 2- ]
[Mg 2 ].[Y 4- ]
1
CaY2 [Y ]
MgY2 .[Y 4- ]
4-
1
[Y ]=
10 9,75
CaY2- .MgY2
4
NH3 + H3O+
Ag2O khng tan trong kim d, nhng d tan trong HNO3, NH4OH v
b nh sng phn hy thnh Ag kim loi.
Vi thuc th K2CrO4
2Ag+ + CrO42- = Ag2CrO4 mu nu
Phn ng ny tin hnh trong mi trng trung tnh (pH = 7).
Pb2+ + CrO42- = PbCrO4 mu vng
2Pb2+ + Cr2O72- + H2O = 2PbCrO4 + 2H+
Hg 2 H 2 S HgS Hg 0 2 H
2 Ag S 2 Ag2 S
3 Ag2 S 2 NO3 8 H 6 Ag 2 NO 3S 4 H 2O
Pb2 H 2 S PbS 2 H
3PbS 8 HNO3 3PbSO4 8 NO 4 H 2O
Vi thuc th Na2S2O3
2 Ag S 2O3
Ag2 S 2O3
2 Ag S 2O3
2 Ag S 2O3
PbS 2O3 4 2 H
Cation
Ag+
HCl long
H2SO4
long
KOH hoc
NaOH
Pb2+
Ag2O en
PbSO4 trng
Hg22+
Hg2Cl2 trng, tc
dng vi NH4OH
ha en
Hg2SO4 trng
[Hg2ONH2]NO3 +
Hg en
Cation
Ag+
Pb2+
Pb2(OH)2CO3
trng
Hg22+
K2CO3 hay
Na2CO3
Ag2CO3 trng
Hg2CO3 HgO
+ Hg + CO2 kt
ta xm
K2CrO4
KI
AgI vng
Hg2I2 xanh lc
tc dng vi
thuc th d
HgI42- + Hg
H2S v cc mui
Na2S, (NH4)2S
Ag2S en
PbS en
HgS + Hg en
Cu
Ag trng
To hn hng
mu trng
Nc lc 1
Nc lc 2 + KI (hoc K2CrO4)
Kt ta 2 + NH4OH
Kt ta en
xm Hg +
NH2HgCl
Nc lc 3 + HNO3
AgCl trng
Cation
Ba2+
Sr2+
Ca2+
H2SO4 long
BaSO4 trng
SrSO4 trng
Nc thch cao
CaSO4 bo ha
BaSO4
SrSO4
Na2CO3
BaCO3 trng
SrCO3 trng
CaCO3 trng
H2SO4 c
BaHSO4
SrHSO4
CaHSO4
BaCrO4 vng
SrCrO4 vng
BaCrO4 vng
(NH4)2SO4
BaSO4
SrSO4
Ca(SO4)22-
(NH4)2C2O4
BaC2O4 trng
SrC2O4 trng
CaC2O4 trng
Na2HPO4
BaHPO4 trng
SrHPO4 trng
CaHPO4 trng
Th mu la
Ngn la mu vng lc
Ngn la mu
Ngn la mu gch
K2CrO4
BaCrO4
vng
Nc lc +
Na2S
PbS en
Phn t + CaSO4
bo ha
SrSO4 trng
SrSO4
trng
CaC2O4
trng
c d.
tch Cr3+ cng vi nhm III, thng dng kim d v c mt H2O2 oxi
ha Cr3+ v CrO42- .V vy cho nn thuc th tch nhm III l NaOH
(hoc KOH) d v H2O2.
Cation
Al3+
Cr3+
Zn2+
Sn2+
Sn4+
NaOH d
AlO2-
CrO2-
ZnO22-
SnO22-
SnO32-
Al(OH)3
trng
Cr(OH)3 lc
Zn(OH)2 trng
Sn(OH)2
trng
Sn(OH)4
trng
DD NH3
Al(OH)3
Cr(OH)3
[Zn(NH3)4]2+
Sn(OH)2
Sn(OH)4
Na2HPO4
AlPO4 trng
CrPO4 xanh
lc
Zn3(PO4)2 trng
Sn(OH)2
Sn(OH)4
SnS nu
SnS2 vng
Al(OH)3
Kt ta son
Cr(OH)3
Cr3+ Cr6+
Kt ta nu
nht
ZnS trng
ZnS
Kt ta nht
Sn2+ Sn4+
Kt ta vng
gch
Kt ta vng
nht
L3 + NH4Cl, un si k, li tm
Kt3,1
Lc mnh, un nng
vi (NH4)2S
Nc lc c
SnS32- +
CH3COOH
SnS2
vng
Kt ra sch +
CH3COOH n
tan + alizarin +
NH4OH Kt
son
P1: + H2O2 + ru
amylic + H2SO4
P2: + Na2S
Lp ru c mu
xanh ca H3CrO8
ZnS trng