1

TI LIU THAM KHO

Cn bng ion trong ha phn tch, tp 1&2 - Nguyn Thanh Khuyn,
Nguyn Th Xun Mai - T sch i hc Tng hp TpHCM 1996.
C s l thuyt phn tch nh lng. Gio trnh dng cho sinh vin khoa
Ha trng HKHTN Tp. HCM, 2009
C s l thuyt ha phn tch - Nguyn Thc Ct, T Vng Nghi, o
Hu Vinh - NXB i hc v Trung hc chuyn nghip, 1979
Modern Analytical Chemistry, Davis Harvey, Mc Graw Hill, 2000
Fundamentals of Analytical Chemistry, 7th Edition - Douglas A. Skoog,
Donald M. West, F. James Holler, 1996.
Analytical Chemistry, 6th Edition Gary D. Christian, John Wiley & Son,
Inc. 2004
PHN 1: C S L THUYT CHUNG
CA HA PHN TCH
Chng I: Gii thiu
Gii thiu mn hc
Vai tr v ng dng ca ha phn tch
Cc giai on ca qu trnh phn tch ha hc
Chng II: Cn bng ha hc
Dung dch cht in ly
Cn bng ha hc v hot
Cc loi phn ng dng trong ha phn tch
Nng v cch tnh ton kt qu trong ha phn
tch
Chng III : Phn ng acid baz
nh ngha acid, baz
Cn bng trong nc thang pH
Cng ca acid v baz. Hng s acid K
a
v
hng s baz K
b
pH ca cc dung dch acid/baz v mui
Dung dch m. m nng
Chng IV : Phn ng to phc
nh ngha
Hng s bn v khng bn ca phc cht
Nng cn bng trong dung dch phc cht
Cc yu t nh hng n cn bng ca phc cht
Chng V : Phn ng kt ta
iu kin to thnh kt ta. Quy lut tch s tan
Tch s tan v tan
Cc yu t nh hng n tan
Cng kt v kt ta theo
Kt ta phn on
Kt ta keo
Chng VI : Phn ng oxy ha kh
nh ngha
Cn bng phn ng oxy ha kh
Phng trnh Nernst
Cc yu t nh hng n th oxy ha kh
Hng s cn bng ca phn ng oxy ha kh
PHN 2 : PHNG PHP PHN TCH
NH LNG
Chng I: Gii thiu chung v phn tch
nh lng
Khi nim v phn tch nh lng
Cc phng php phn tch nh lng
Cc giai on trong qu trnh phn tch
n v o lng trong phn tch ha hc
Tnh ton kt qu trong phn tch nh lng
Chng II. Phng php chun
acid baz
Cht ch th acid baz
S thay i pH dung dch trong qu trnh chun
Chun acid mnh bng baz mnh v ngc li
Chun acid yu bng baz mnh v ngc li
Chng III. Phng php chun
phc cht
Chun complexon
Phn ng to phc ca EDTA vi ion kim loi
Ch th mu trong chun complexon
Cch xc nh im tng ng
ng dng ca chun complexon
2
Chng IV : Phng php chun kt ta
Nguyn tc chung ca phng php
Xc nh halogenur bng phng php Mohr,
Volhard v Fajans
Chng V. Phng php chun oxy ha
kh
Cht ch th oxy ha kh
Phng php bicromat
Phng php permanganate
Phng php thiosulfat
Chng V: ng dng ca phng php
phn tch ha hc trong phn tch mi
trng
nh ngha: ha hc phn tch l lnh vc
hot ng ca cc nh ha hc chuyn
ngnh phn tch.
Ha hc phn tch lin quan n vic xc nh cc c trng v mt ha hc
ca vt cht.
Lin on cc hip hi t chc ha hc u Chu nh ngha Ha phn tch
cung cp cc phung php v dng c nhm gip hiu bit su hn v th
gii vt cht tr li cho cc vn :
N l g?
T u ti?
Lng bao nhiu?
Hnh dng, cu trc, ...?
Hip hi ha hc M (ACS): Ha phn tch tm kim v ci tin cc phng
tin o lng thnh phn ha hc ca vt cht theo yu cu thc tin.
Quan h ca
ha phn tch
vi cc ngnh khc
Ha hc phn tch (analytical chemistry) v phn tch ha hc
(chemical analysis).
Ha hc phn tch: nghin cu thit lp v ci tin cc phng php
phn tch, phung tin phn tch v cc quy trnh phn tch ph hp vi
i tng phn tch v yu cu phn tch.
Phn tch ha hc: thc hin th nghim theo mt quy trnh thch hp c
th thnh phn ha hc ca mu theo yu cu.
Phn tch nh tnh (qualitative analysis) v phn tch nh
lng (quantitative analysis).
Phn tch nh tnh: nhn danh cc nguyn t, ion, hp cht trong mu
Phn tch nh lng: xc nh hm lng cc thnh phn hin din
trong mu
Phn tch ha hc l mt php o lng
Kt qu phn tch l cc s o nh gi tin cy ca s (
ng-sai s h thng, chnh xc-sai s ngu nhin...)
Hp phn a lung v hp phn vi lung
a lung: > 1%
Vi lng: < 1%
Vt: < 0.1%
Siu vt: < ppm
Biu din hm lung trong phn tch nh lung
Phn trm khi lung, bi/c s ca ppm
Phn trm th tch
Nng mol/L, ng lng/L (eq/L hay meq/mL).
Thnh phn ha hc
Thnh phn nguyn t v trng thi oxyha
Thnh phn nguyn t theo ng v bn v phng x
Thnh phn cu trc ng phn (hnh hc, quang hc...)
Thnh phn cu trc th hnh
Thnh phn cu trc phn t, ion
Thnh phn nhm chc, gc t do
Thnh phn khong vt
Thnh phn pha (hp kim)
3
Tm lc cc phng php phn tch thng dng
VC Nhanh Tt 2-10 10
-3
-10
-9
Ph nguyn t
VC,HC Trung bnh Trng bnh 2-5 10
-6
-10
-9
Hunh quang
VC,HC Nhanhtrung bnh Tttrung bnh 2 10
-3
-10
-6
Trc quang
VC,HC Nhanh Tt 2-5 10
-3
-10
-9
Sc k
VC,HC Nhanhtrung bnh Tttrung bnh 2-10 10
-2
-10
-10
ng hc
VC,HC Trung bnh Tt 2-5 10
-3
-10
-10
Volt-amper
VC,HC Chm-trung bnh Trung bnh 0.01-2 10
-1
-10
-4
in trng
lng
VC Nhanh Tt 2 10
-1
-10
-6
in th
VC,HC Trung bnh Kmtrung bnh 0.1-1 10
-1
-10
-4
Chun
VC Chm Kmtrung bnh 0.1 10
-1
-10
-2
Trng lng
i
tng
Tc phn tch chn lc
chnh
xc (%)
Khong
nng
(M)
Phng
Php
QUY TRNH PHN TCH TIU BIU
Cn bng trong dung dch
Phn ng ha hc: thng xy ra theo hai
chiu t cn bng.
H a cu t:
Nhiu phn ng din ra ng thi.
H t cn bng: cc cu t ca h t cn bng.
Phn ng c hng s cn bng ln nht quyt nh
thnh phn h.
Nng (nhc li)
Mol - mol/L (M)
ng lng - eq/L (N).
Quy i: M-N?
Hot
Bn cht ngha
Khc bit gia nng - hot ?
Quan h nng - hot H s hot
Yu t nh hung n hot lc ion
dD cC bB aA + +
j j
j j
C b a
d c
K
B A
D C
=
*
*
a b
B
a
A
d
D
c
C
K
a a
a a
=
*
*
Hng s cn bng theo nng
Hng s cn bng theo hot
Xt cn bng
C f a * =

=
=
n
i
i i
z C
1
2
2
1

* * 5 . 0 * * lg
2 2
i i i
Z Z A f = =
Quan h hot - nng
Lc ion
H s hot trong dd in ly nng thp < 0.02
4

* * 10 * 33 . 0 1
* * 5 . 0
lg
8
2
b
Z
f
i
i
+
=

*
* * 10 * 33 . 0 1
* * 5 . 0
lg
8
2
B
b
Z
f
i
i
+
+
=
b
B
a
A
d
D
c
C
C b
B
a
A
d
D
c
C
b
B
a
A
d
D
c
C
a
f f
f f
K
f f
f f
a a
a a
K
*
*
*
*
*
*
*
*
= =
Quan h K
a
- K
c
H s hot trong dd in ly nng trung bnh
0.02<< 0.2
b: bn knh ion hydrate ha
3*10
-8
cm: OH, F, Cl, Br, I, NH
4
, Ag
4* 10
-8
cm: Na, H
2
PO
4
, Pb, CO
3
, SO
4
, PO
4
9 *10
-8
cm: H
H s hot trong dd in ly nng cao >0.2
HNG S PHN LY (HNG S KHNG BN)
AB A + B
K pK
a
a a
K
AB
B A
lg
.
=
=
j j
j AB
B A
K
.
=
Nng nh hot bng nng (b qua h s hot )
Phn ng c K cng nh, AB cng t phn ly, hp cht AB cng bn
Phn ly nhiu nc: hp cht AB
n
Nc 1: AB
n
AB
n-1
+ B
Nc 2: AB
n-1
AB
n-2
+ B
Nc 3: AB
n-2
AB
n-3
+ B
..........................................
Nc n-1: AB
2
AB + B
Nc n: AB A + B
j j
j
1
2
2
.

=
n
n
AB
B AB
K
j j
j
2
1
.
AB
B AB
K
n
=

j j
j
2
3
3
.

=
n
n
AB
B AB
K
j j
j AB
B A
K
n
.
=
j j
j
n
n
AB
B AB
K
.
1
1

=
V d: ion Cu
2+
to phc vi NH
3
cc phc Cu(NH
3
)
i
(i=1-4) c cc pK
i
ln lt 2.11, 2.87, 3.48, 4.13. Tnh
[Cu(NH
3
)
i
] bit C
Cu
=0.1M, [NH
3
]=10
-4
M.
j j j j
45 . 0
41 . 3 52 . 1 39 . 0 13 . 0
11 . 2 87 . 2 48 . 3 13 . 4
16
87 . 2 48 . 3 13 . 4
12
48 . 3 13 . 4
8
13 . 4
4
1 2 3 4
4
3
2 3 4
3
3
3 4
2
3
4
3
) (
10 8 . 2 05 . 0 40 . 0 35 . 1 1
10 10 10 10 1
10 10 10 10
10
10 10 10
10
10 10
10
10
10
1
. . . . . .
1
1
3
= = + + + =
+ + + + =
+
+ + + =
|
|
.
|

\
|
+ + + + =

K K K K
NH
K K K
NH
K K
NH
K
NH
NH Cu

Acid baz
nh ngha
Bronsted
Acid tng tc vi dung mi H
+
hydrate ha
Baz: cht c kh nng nhn H
+
Phn nh nh hng ca dung mi
n gin ha cch tnh pH
Cn bng trong nc thang pH
Tch s ion ca nc: nc l mt hp cht lng tnh
H
2
O + H
2
O H
3
O
+
+ OH
-
nhit 25
o
C: K = 10
-14
, nhit tng K tng.
Thang pH:
pH = -lg a
H
+
lgC
H
+
pOH = -lg a
OH
-
lgC
OH
-
pH + pOH = 14 thang pH: 014
Trong nc nguyn cht: [H
+
] = [OH
-
] = 10
-7
.
Dung dch acid: [H
+
] > 10
-7
; [OH
-
] < 10
-7
pH < 7
Dung dch baz: [H
+
] < 10
-7
; [OH
-
] > 10
-7
pH > 7
5
i acid-baz lin hp- thang acid-baz
HA + H
2
O A
-
+ H
3
O
+
A
-
+ H
2
O HA + OH
-
j j
j
a a
a
K pK
HA
O H A
K
lg
3
=
=
+
j j
j
b b
b
K pK
A
OH HA
K
lg =
=

14
10 .
14
= +
= =

b a
w b a
pK pK
K K K
ng dng ca thang acid-baz
Chiu phn ng acid-baz
Acid1 + Baz2 Acid2 + Baz1
j j
j j
j j
j
j
j j
2
1
3
3
2
2
1
1
2 1
1 2
a
a
cb
K
K
O H Baz
Acid
Acid
O H Baz
Baz Acid
Baz Acid
K = = =
+
+
Chiu phn ng acid-baz
pK cng ln, phn ng cng nh lng.
ng dng trong chun acid-baz
Chun acid yu: dng baz mnh lm cht chun
Chun baz yu: dng acid mnh lm cht chun
Cht chun tt nht nn l acid hoc baz ch c 1 nc
pH ca dung dch acid hoc baz mnh
Acid mnh
Phn ly hon ton thnh H
3
O
+
.
Hiu ng san bng: cho cc acid mnh hn
H
3
O
+
th hin mnh ngang nhau.
pH ch ty thuc vo [H
3
O
+
] thc t trong dung
dch
HA + H
2
O H
3
O
+
+ A
-
.
H
2
O + H
2
O H
3
O
+
+ OH
-
.
Phng trnh bo ton proton: [H
3
O
+
] = [A
-
] + [OH
-
]
[H
3
O
+
] = C
HA
+ K
w
/[H
3
O
+
]
[H
3
O
+
]
2
- C
HA
[H
3
O
+
] K
w
= 0
C
HA
>10
-6
M [OH
-
] = 10
-14
/ [H
3
O
+
] < 10
-8
M
xem s phn ly ca nc l khng ng k
b [OH
-
] cnh C
HA
[H
3
O
+
] = C
HA
pH = - lg C
HA
.
C
HA
<10
-6
M [OH
-
] = 10
-14
/ [H
3
O
+
] > 10
-8
M
s phn ly ca nc tr nn ng k
khng th b [OH
-
] cnh C
HA
gii phng trnh bc 2 [H
3
O
+
]
2
- C
HA
[H
3
O
+
] K
w
= 0.
pH ca dung dch acid hoc baz mnh
Baz mnh
Phn ly hon ton thnh OH
-
.
Hiu ng san bng: cho cc baz mnh hn OH
-
th hin mnh ngang nhau.
pH ch ty thuc vo [OH
-
] thc t trong dung
dch
MOH + H
2
O M
+
.H
2
O + OH
-
.
H
2
O + H
2
O H
3
O
+
+ OH
-
.
6
Phng trnh bo ton proton: [H
3
O
+
] + [M
+
] = [OH
-
]
K
w
/[OH
-
] + C
MOH
= [OH
-
] [OH
-
]
2
- C
MOH
[OH
-
]
K
w
= 0
C
MOH
>10
-6
M [H
3
O
+
] = 10
-14
/[OH
-
] < 10
-8
M
xem s phn ly ca nc l khng ng k
b [H
3
O
+
] cnh C
MOH
[OH
-
] = C
MOH
pH = - lg C
MOH
.
C
MOH
<10
-6
M [H
3
O
+
] = 10
-14
/[OH
-
] > 10
-8
M
s phn ly ca nc tr nn ng k
khng th b [H
3
O
+
] cnh C
MOH
gii phng trnh bc 2 [OH
-
]
2
- C
MOH
[OH
-
] K
w
=
0.
pH dung dch n acid yu hay n baz yu
pH dung dch n acid yu
Phng trnh phn ly:
HA + H
2
O H
3
O
+
+ A
-
H
2
O + H
2
O H
3
O
+
+ OH
-
nh lut bo ton khi lng: C
a
= [A
-
] + [HA]
j j
j
j
j
j
j j
j j
+
= =
=
+
+

+
+
OH O H
OH O H C
K
A
HA
K O H
HA
A O H
K
a
a a
a
3
3
3
3
K
a
kh nh, C
a
rt ln: acid kh yu
C
a
>> [H
3
O
+
]>>[OH
-
] pH = 0.5(pK
a
+ pC
o
).
K
a
kh ln, acid khng qu yu [H
3
O
+
]>>[OH
-
]
j
j j
j j
j
j
+
+
+
+
+

=

+
=
O H
O H C
K
OH O H
OH O H C
K O H
a
a
a
a
3
3
3
3
3
Gii phng trnh bc 2 [H
3
O
+
].
K
a
rt nh, acid rt yu [H
3
O
+
] v [OH
-
] rt nh,
b qua cnh C
a
.
j
j j
j j j j
+ +
+
+

+
=
OH O H
C
K
OH O H
OH O H C
K O H
a
a
a
a
3 3
3
3
Xc nh cng thc tnh pH ph hp
1. Tnh [H
+
]
g
2. Tnh [OH
-
]
g
3. 3 trng hp
[OH
-
]
g
[H
+
]
g
/100 v [H
+
]
g
C
a
/100
[OH
-
]
g
[H
+
]
g
/100 v [H
+
]
g
> C
a
/100 gii phng
trnh bc 2
K
a
rt nh, [H
+
] [OH
-
] C
a
/100
j
a a
C K H =
+
j
a a
a a
C K
K K
H + + =
+
4 2
2
j
14
10
+
+ =
a a
C K H
pH dung dch n acid yu hay n baz yu
pH dung dch n baz yu
Phng trnh phn ly:
B + H
2
O BH
+
+ OH
-
H
2
O + H
2
O H
3
O
+
+ OH
-
nh lut bo ton khi lng: C
b
= [B] + [BH
+
]
j j
j
j
j
j
j j
j j
+
+
+

+
= =
=
O H OH
O H OH C
K
BH
B
K OH
B
OH BH
K
b
b b
b
3
3
K
b
kh nh, C
b
rt ln: baz kh yu C
b
>> [OH
-
]
>>[H
3
O
+
] pH = 0.5(pK
b
+ pC
o
).
K
b
kh ln, baz khng qu yu [OH
-
] >> [H
3
O
+
]
j
j j
j j
j
j

+
+

+
=
OH
OH C
K
O H OH
O H OH C
K OH
b
b
b
b
3
3
Gii phng trnh bc 2 [OH
-
].
K
b
rt nh, baz rt yu [H
3
O
+
] v [OH
-
] rt nh
b qua cnh C
b
.
j
j j
j j j j
+ +
+

+
=
O H OH
C
K
O H OH
O H OH C
K OH
b
b
b
b
3 3
3
7
Xc nh cng thc tnh pH ph hp
1. Tnh [OH
-
]
g
2. Tnh [H
3
O
+
]
g
3. 3 trng hp
[H
3
O
+
]
g
[OH
-
]
g
/100 v [OH
-
]
g
C
b
/100
[H
3
O
+
]
g
[OH
-
]
g
/100 v [OH
-
]
g
> C
b
/100 gii phng trnh
bc 2
K
b
rt nh, [H
+
] [OH
-
] C
a
/100
j
b b
C K OH =

j
b b
b b
C K
K K
OH + + =

4 2
2
j
14
10

+ =
b b
C K OH
pH dung dch a acid yu: xt diacid yu
H
2
A + H
2
O HA
-
+ H
3
O
+
HA
-
+ H
2
O A
2-
+ H
3
O
+
H
2
O + H
2
O H
3
O
+
+ OH
-
Phng trnh bo ton proton:
[H
3
O
+
] = [HA
-
]+2[A
2-
]+[OH
-
]
[H
3
O
+
] - [OH
-
]= [HA
-
]+2[A
2-
]
[A
2-
]=C
a

A(H)
j
j j j j
1 2 3 1
2
3
1 2
1 2
2
3
2
3
) (
2
1
a a a
a a
a
a a a
a
H A a
K K O H K O H
K K
C
K K
O H
K
O H
C
C A
+ +
=
+ +
= =
+ + + +

j j
j
j j
j j
j j
1 2 3 1
2
3
3 1
2
3
1 2
2
3
2
3
2
2
1
a a a
a
a
a
a a a
a
K K O H K O H
O H K
C
K
O H
K K
O H
K
O H
C
K
H
A HA
+ +
=
+ +
= =
+ +
+ +
+ +
+

j j
j
j j
1 2 3 1
2
3
2 1 3 1
3
2
a a a
a a a
a
K K O H K O H
K K O H K
C OH O H
+ +
+
=
+ +
+
+
Mc phn ly gia cc nc ca acid a chc: gim dn
do
K
1
>K
2
>...>K
n
H
3
O
+
t nc u tin c ch s phn ly ca nc sau.
Cc acid a chc c cc pK > 3: nc sau phn ly khng ng
k xem nh acid n chc
Cc acid a chc c cc pK < 3: [H
+
]
2
K
a2
[H
+
]
chung
=[H
+
]
1
+ [H
+
]
2
j j
2 1 1
+ +
+ = H C K H
a a
Nng cc ion H
i
A:
Tnh t [H
+
] (tc l [H
+
] t do) v C
A
).
C
A
= [A] + [HA] + [H
2
A] + [H
3
A] + ... + [H
n-1
A] + [H
n
A]
j j j j j
j
j j j j j j j j
j
j j j j
j
) (
1 2 1 2 1
1
1
2
1 2 1 2 1
1
1
2
1 2
1
. ... . ... .
...
.
1
. ... . ... .
...
.
...
H A
n n
n
n n
n
n n n
n n
n
n n
n
n n n
n n A
A
K K K K
H
K K K
H
K K
H
K
H
A
K K K K
A H
K K K
A H
K K
A H
K
A H
A
A H A H A H HA A C

=
|
|
.
|

\
|
+ + + + + =
+ + + + + =
+ + + + + =

+ +

+ +

j
j
j j j
j
j j j
j
j j j
j
j j j
1 1
) (
1 1
1 2 1
) (
1 2 1
1
2
) (
1
2
2
) (
) (
.... .
. .
.... .
. ... .
. .
. ... .
.
. .
.
. .
.
+
+
+
+

+

+
+ +
= =
= =
= =
= =
=
i n n n
i
H A A
i n n n
i
i
n n
n
H A A
n n
n
n
n n
H A A
n n
n
H A A
n
H A A
K K K
H
C
K K K
A H
A H
K K K K
H
C
K K K K
A H
A H
K K
H
C
K K
A H
A H
K
H
C
K
A H
HA
C A

pH dung dch a baz yu: xt dibaz yu

Phng trnh bo ton proton:
[OH
-
] = [HB
+
]+2[H
2
B
2+
]+[H
3
O
+
] [OH
-
] - [H
3
O
+
] = [HB
+
]+2[H
2
B
2+
]
[H
2
B
2+
]=C
b

HB(OH)
j
j j j j
1 2 1
2
1 2
1 2
2
2
) (
2
1
b b b
b b
b
b b b
b
OH HB a
K K OH K OH
K K
C
K K
OH
K
OH
C
C HB
+ +
=
+ +
= =

+

j j
j
j j
j j
j j
1 2 1
2
1
2
1 2
2
2
2
2
2
1
b b b
b
b
b
b b b
b
b K K OH K OH
OH K
C
K
OH
K K
OH
K
OH
C
K
OH
B H HB
+ +
=
+ +
= =

+ +
j j
j
j j
j
j j
14
3 3 2 2
1
14 2
2
2
2
2 2
2
14
1 2
10
10
10
+ +

+
+
+ +
+
+
= = + +
= = + +
= = + +
OH O H K OH O H O H O H
K HB
OH B H
K OH B H O H HB
K B
OH HB
K OH HB O H B
W
a
b
a
b
8
j j
j
j j
1 2 1
2
2 1 1
3
2
b b b
b b b
b
K K OH K OH
K K OH K
C O H OH
+ +
+
=

+
Mc phn ly gia cc nc ca baz a chc: gim dn
do
K
b1
>K
b2
>...>K
bn
(pK
b1
<pK
b2
<...<pK
bn
)
OH
-
t nc u tin c ch s phn ly ca nc sau.
Cc baz a chc c cc pK > 3: nc sau phn ly khng ng
k xem nh baz n chc.
Cc baz a chc c cc pK < 3: [OH
-
]
2
K
b2
[OH
-
]
chung
=[OH
-
]
1
+ [OH
-
]
2

j j
2 1 1

+ = OH C K OH
b b
pH dung dch mui
Mui = cation + anion (phn ly hon ton)
Cation: tnh acid hay lng tnh
Anion: tnh baz hay lng tnh
Lc acid > Lc baz mui c tnh acid
Lc acid < Lc baz mui c tnh baz
Lc acid = Lc baz mui trung tnh
Mui ca acid mnh v baz mnh:
Cation: acid rt yu khng ion ha uc nc
Anion: baz rt yu khng ion ha uc nc
pH trung tnh
Mui ca acid mnh v baz yu
Cation: acid yu ion ha nc cho H
+
.
Anion: baz rt yu khng ion ha uc nc
pH acid.
Tnh pH tng t nh n acid yu.
Xt v d: NH
4
Cl
Mui ca acid yu v baz mnh
Cation: acid rt yu khng ion ha nc.
Anion: baz yu ion ha uc nc cho OH
-
pH baz.
Tnh pH tng t nh n baz yu.
Xt v d: CH
3
COONa, NaCN, NaF
Mui trung ha
Cc chc acid c trung ha ht.
Cation: acid rt yu khng ion ha nc.
Anion: baz yu ion ha uc nc cho OH
-
pH baz.
Anion: baz a chc yu cc chc th 2 tr i phn
thy phn khng ng k xem baz yu n chc.
Tnh pH tng t nh n baz yu.
Xt v d mui Na
2
CO
3
, Na
3
PO
4
v Na
2
C
2
O
4
Mui c anion lng tnh: NaHA
NaHA Na
+
+ HA
-
(phn ly hon ton)
HA
-
H
+
+ A
2-
HA
-
+ H
2
O H
2
A + OH
-
H
2
O H
+
+ OH
-
Tnh acid-baz
Nu K
a
HA
> K
b
HA
: dung dch c tnh acid
Nu K
a
HA
< K
b
HA
: dung dch c tnh baz
Xt v d mui NaHCO
3
, NaH
2
PO
4
v Na
2
HPO
4
Tnh pH:
PT bo ton proton: [H
+
]+[H
2
A]=[A
2-
]+[OH
-
]
Thng thng [H
+
] v [OH
-
] kh nh so vi [H
2
A] v[A
2-
] b
qua [H
+
] v [OH
-
] cnh [H
2
A] v[A
2-
].
j j
j
A H
a
HA
a
K
HA
A H
K
2
2
2
= =
+
j j
j
A H
a
HA
b
K HA
OH A H
K
2
1
14
2
10

= =
[H
2
A]=[A
2-
]
j
j j j j
1 2 1
2
1 2
1 2
2
2
) (
2
1
a a a
a a
a
a a a
a
H A a
K K H K H
K K
C
K K
H
K
H
C
C A
+ +
=
+ +
= =
+ + + +

j j
j
j j
j j
j j
1 2 1
2
2
1 2
2
1 2
2
2
1 2
2
2
2
1
a a a
a
a a a
a
K K H K H
H
C
K K
H
K K
H
K
H
C
K K
H
A A H
+ +
=
+ +
= =
+ +
+ +
+ +
+

C
a
= C
HA
K
a1
K
a2
= [H
+
]
2
pH = 0.5(pK
a1
+ pK
a2
)
V d: tnh pH mui NaHCO
3
, NaH
2
PO
4
v Na
2
HPO
4
9
Dung dch acid yu v baz lin hp
dung dch m
Dung dch cha acid HA (C
A
) v mui NaA (C
B
)
NaA Na
+
+ A
-
(phn ly hon ton)
HA H
+
+ A
-
A
-
+ H
2
O HA + OH
-
H
2
O H
+
+ OH
-
Tnh pH:
j j
j HA
A H
K
HA
a
+
=
j j
j
HA
a
A
b
K A
OH HA
K
14
10

= =

Bo ton khi lng cho A: [HA] + [A

-
]=C
A
+ C
B
(1)
Bo ton in tch: [H
+
] + [Na
+
]= [OH
-
] + [A
-
]
[H
+
] + C
B
= [OH
-
] + [A
-
]
[A
-
] = C
B
+ [H
+
] - [OH
-
] (2)
(1) v (2): [HA] = C
A
- [H
+
] + [OH
-
]
j j
j
j
j
j
j
j j
j j
+
+
+

+
+
+
+
=
= =
OH H C
OH H C
K H
A
HA
K H
HA
A H
K
B
A HA
a
HA
a
HA
a
Acid HA kh mnh, baz lin hp
A
-
kh yu pH trong vng
acid, b qua [OH
-
] cnh [H
+
]. V
d: CH
2
ClCOOH/CH
2
ClCOONa
0.03/0.01M
Acid HA kh yu, baz lin hp A
-
kh mnh pH trong vng baz,
b qua [H
+
] cnh [OH
-
]. V d:
NH
4
+
/NH
3
0.025
/
0.01M
C
A
v C
B
kh ln so vi [H
+
] v
[OH
-
]: b qua [H
+
] v [OH
-
] cnh
C
A
v C
B
. V d:
CH
3
COOH/CH
3
COONa 0.5/1M
j
j
j
+
+
+
+

=
H C
H C
K H
B
A HA
a
j
B
A HA
a
C
C
K H =
+
j
j
j

+
=
OH C
OH C
K H
B
A HA
a
Dung dch m
pH dung dch m khng thay i nhiu khi thm H
+
,
OH
-
hay khi pha long dung dch
Cc loi dung dch m
m n: acid yu v baz lin hp
m hn hp: vd:H
3
PO
4
+CH
3
COOH+H
3
BO
3
+NaOH
C ch gi pH
pH dung dch cha HA (nng C
a
) v A
-
(nng C
b
):
HA A
-
OH
-
H
+
A
B HA
a
C
C
pK pH lg
1
+ =
Gi s thm n
H+
vo dung dch trn
+
+
+

+ =
H
A
H
B HA
a
n C
n C
pK pH lg
2
pH
1
> pH
2
Tuy nhin s gim pH ny khng ng k nu C
A
v C
B
>> n
H+
thm
vo. Hn na gi tr ca hm lg bin thin rt chm.
L lun tng t i vi vic thm OH
-
.
S pha long dung dch m v nguyn tc khng lm thay i t l
C
B
/C
A
khng lm pH thay i. Tuy nhin thc t vn thy pH dung
dch m thay i khi pha long do phn ly ca acid/baz tng
gim/tng pH.
V d:
Dung dch m pH
Kh nng chng chu thay i pH khi thm acid/baz.
Ch s m: hay , ty thuc vo nng C
A
, C
B
, t s
C
B
/C
A
.
Hn hp ca mt/nhiu acid v baz lin hp ca chng
(m n/kp).
dpH
da
dpH
db
= =
dd
buffer
V
V
pH
a
pH
b
=
A
A
=
A
A
= '
j
j j
j j
+
+
+
+
+
=
OH H C
OH H C
K H
b
a
a
j j ,
j
j ,
2
. .
303 . 2 303 . 2
+
+
+
+
+ + =
H K
H K C
H OH
a
a

+ =
i HA O H ,
2

10
0
0.5
1
1.5
2
2.5
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0
0.5
1
1.5
2
2.5
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
CHNG III.
PHNG PHP PHN TCH TH TCH
1. NGUYN TC:
Bn cht ca PP phn tch th tch: nh lng
mt cht qua phn ng ha hc
aX + bR cP
1
+ dP
2
nh lng thuc th R phn ng va vi X:
phng php phn tch th tch.
Nguyn tc xc nh nng N
X
: ng lng
X = ng lng R
N
X
V
X
= N
R
V
R
im tng ng v im cui
+ T phn chun F
SSNN: lp li php o nhiu ln tnh
SSHT:
+
calib
hiu chun th tch
+
In
sai s ch th
+
In
= F
cui
- 1
II. CC YU CU CA PHN NG CHUN
Phi c vn tc ln
La chn uc cht ch th
+ |
ind,r
| < 0.01
+ Ch th chuyn mu r rt
C ng t l hp thc
C hng s cn bng ln [X]
td
/[P]
td
< 0.01
hay 0.001 (mc khng nh lng)
cng nh: K
cb
, C
oX
, C
oR
cng ln
Thit lp iu kin cho phn ng chun
11
III. DUNG DCH CHUN
Dung dch chun gc
Cht chun gc
+ Tinh khit ha hc >99.9%, khng cha tp cht
phng hi n chnh xc php chun
+ Thnh phn ng vi cng thc danh nh
+ Bn khi bo qun th rn, th dung dch
+ C ng lng cng ln cng tt
ng chun
Cc loi nng s dng
+ mol/L (M)
+ ng lng (N): N
x
/M
x
= A
x
/
x
+ chun T
R
+ chun theo cht xc nh T
R/X
.
IV. PHN LOI CC PP PT TH TCH
Chun acid-baz
Chun phc cht
Chun kt ta
Chun oxyha kh
Chng 4: PHNG PHP
CHUN ACID-BAZ
1. Thuyt Brnsted-Lowry-acid/baz lin hp
2. Phn ng chun acid baz theo thuyt Brnsted-
Lowry
3. Cht ch th pH
Ch th pH hay acid baz?
Ch th thc cht l acid-baz lng dng
Mu cht ch th mu dung dch phn tch
Khong i mu pH
Ind
pT ca ch th mu
Ch th 1 khong i mu, 2 khong i mu
+ cht ch th mu hn hp: 2 ch th pH,
v d:
bromocresol lc + methyl cam
camchm lc, (3.5-4.3)
bromocresol lc + chlorophenol
vng lc chm tm (5.4-6.2)
Bromothylmol chm + phenol
vng tm (7.2 7.6)
Thymolphthalein + alizarin vng
vng tm (10.2)
12
+ cht ch th screened indicator: 1 ch th
pH v 1 phm mu tr
V d:
dimethyl vng + methylene chm
chm tm lc (3.25, 3.23.4)
methyl + methylene chm
ta lc (5.4, 5.25.6)
trung tnh + methylene chm
Tm chm lc (7.0, 6.87.3)
+ cht ch th vn nng
V d:
tropeolin + methyl cam + methyl +
bromothymol chm + phenolphthalein + alizarin
vng R
cam (2.0) cam (3.0) cam (4.0)
cam vng (5.0) vng cam (6.0) vng
(6.5) vng lc (7.0) lc lc chm (8.0)
tm chm (9.0) tm (10.0) tm (12.0)
Cc yu t nh hng n nhng c
trng ca ch th pH
+ Nhit
+ Lc ion
+ Lc solvat ha
pK
a,Ind
, pK
N
, khong i mu, pT
Chun acid-baz
Acidimetry: baz mnh nh lng acid
Alkalimetry: acid mnh nh lng baz
Chn ch th: pH
F0.99
< pT < pH
F1.01
Chun n acid
1. Chun acid mnh
H
+
+ OH
-
H
2
O
V
o
, C
o
: th tch v nng cht trong erlen.
V, C: th tch v nng cht trong buret.
iu kin
NQ
<0.001: pC
o
+ pD
1.00
< 4
H s pha long D
F
=V
o
/(V
o
+V
F
) = C/(FC
o
+C)
+ Cha chun (F = 0): dung dch ch cha acid
c nng C
o
[H
+
]
F
C
o
pH
F
pC
o
Trc im tng ng (0<F<1):
[H
+
]
F
= (1-F)C
o
V
o
/(V
o
+V
F
)
+ Chun 99% (F = 0.99): dung dch cha 99%
mui trung tnh, cn li 1% acid
pH
F = 0.99
= pC
o
+lg((V
o
+V
F
) /V
o
) + 2
+ chun va ht (F = 1): dung dch ch cha mui
trung tnh pH
F = 1
= 7
13
Sau im tng ng (F > 1), d baz mnh:
[OH-]
F
(F-1) C
o
V
o
/(V
o
+V
F
)
+ D 1% NaOH (F = 1.01): pOH pC
o
+pD
1.01
+ 2
pH
F = 1.01
12- pC
o
-pD
1.01
+ D 100% NaOH (F = 2): pOH pC
o
+pD
2.00
pH
F = 2
14- pC
o
-pD
2.00
*Lu : khong bc nhy gim khi C v C
o
gim
Chn ch th: pH
F = 0.99
< pT < pH
F = 1.01
2. Chun acid yu
HA + OH
-
A
-
+ H
2
O
V
o
, C
o
: th tch v nng acid yu trong erlen.
V, C: th tch v nng NaOH trong buret.
iu kin
NQ
<0.001: pK
a
+ pC
o
+ pD
1.00
< 8
H s pha long D
F
=V
o
/(V
o
+V
F
) = C/(FC
o
+C)
Cha chun , F = 0, dd trong erlen ch cha acid
nng C
o
: [H
+
]
F
K
a
C
o
/([H
+
]
F
+ K
a
)
pH
F
0.5 (pK
a
+ pC
o
)
Trc im tng ung, (0<F<1), dd trong
erlen cha acid cn d v mui baz mnh-
acid yu to ra: pH pKa + lg(F/(1-F))
+ Chun 50%C
o
(F = 0.5), dd cha 50%C
o
acid
yu d + 50%C
o
mui ca acid ny dung dch
m pH pK
a
+ Chun 99%C
o
(F = 0.99) dd cha 1%C
o
acid
yu d + 99%C
o
mui ca acid dung dch
m pH pK
a
+ 2
Ti im tng ung (F = 1), dd ch cha
mui acid yu-baz mnh tnh baz:
pH 14 - 0.5 (pK
b
- lgC
o
- lg((V
o
+V
F
) /V
o
))
D NaOH, (F>1), dung dch c cha mui v
NaOH d xem nh pH do NaOH quyt nh:
pH 14 - pC
o
lg((V
o
+V
F
) /V
o
)) p(F-1)
+ D 1%C
o
, NaOH (F = 1.01) pH 12 - pC
o
pD
+ D 100%C
o
NaOH, (F = 2) pH 14 - pC
o
pD
Chn ch th: pH
F = 0.99
< pT < pH
F = 1.01
14
Chun a acid
Nc 1: H
3
A + OH
-
H
2
A
-
+ H
2
O
Nc 2: H
2
A
-
+ OH
-
HA
2-
+ H
2
O
Nc 3: HA
2-
+ OH
-
A
3-
+ H
2
O
iu kin
NQ
+ pK
n+1
pK
n
> 6
NQ
< 0.001
+ pK
n+1
pK
n
> 4
NQ
< 0.01
+
Qu trnh chun
+ Cha chun , F = 0, dung dch a acid: pH
0.5 (pK
a1
+ pC
o
)
+ Trc im tng ng 0 < F 0.99:
pH pK
a1
+ p((1-F)/F)
Chun 50%, mu cha 50%C
o
D H
2
A v 50%C
o
D HA
-
,
F = 0.5: pH pK
a1
Chun 99%, mu cha 1%C
o
D H
2
A v 99%C
o
D HA
-
,
F = 0.99: pH pK
a1
+ 2
+ Ti im tng ung, mu cha 100%C
o
D HA
-
,
mui acid, F = 1: pH 0.5 (pK
a1
+ pK
a2
)
+ Sau im tng ung 1, 1.01 F 1.99: pH pK
a2
+ p((2-F)/(F-
1))
Chun d nc 1 1% (sang nc 2 1%), mu cha 99%C
o
D HA
-
v 99%C
o
D HA
2-
, F =
1.01 dung dch m: pH pK
a2
2
Chun nc 2, 50%, mu cha 50%C
o
D HA
-
v 50%C
o
D HA
2-
, F = 1.5 dung
dch m : pH pK
a2
Chun nc 2 99%, mu cha 1%C
o
D HA
-
v 99%C
o
D HA
2-
, F = 1.99 dung
dch m : pH pK
a2
+ 2
+ F = 2: mu cha 100%C
o
D HA
2-
, mui acid pH 0.5 (pK
a2
+ pK
a3
)
+ Sau im tng ung 2, 2.01 F 2.99: pH pK
a3
+ p((3-F)/(F-2))
Chun d nc 2 1% (sang nc 3 1%), mu cha 99%C
o
D HA
2-
v 1%C
o
D A
3-
, F
= 2.01: pH pK
a3
2
Chun nc 3, 50%, mu cha 50%C
o
D H
2
A
-
v 50%C
o
D A
3-
, F = 2.5: pH pK
a3
Ch th
+ Nc 1: pH
F = 0.99
< pT < pH
F = 1.01
+ Nc 2: pH
F = 1.99
< pT < pH
F = 2.01