Professional Documents
Culture Documents
F7G
GIAO TRNH
http://hoahocsp.tk
-2-
LI NOI AU
Giao trnh HOA PHAN TCH nham cung cap cho Sinh vien
nganh Moi trng nhng kien thc rat can ban ve cac loai
phan ng, cach tnh toan va ky thuat tien hanh phan tch oi
tng bang cac phng phap hoa hoc. Ngoai nhng c s ly
thuyet giao trnh con a ra nhieu v du va bai tap e giup
Sinh vien t cung co nhng kien thc a hoc. Nhng v du
trong giao trnh ch c giai rat van tat hoac khong giai nham
tao ieu kien cho Sinh vien t giai nha trc khi c Giao
vien giang giai chi tiet tren lp hoc.
V thi gian co han va la lan au bien soan nen giao trnh
khong the tranh khoi nhng thieu sot. Rat mong nhan c s
ong gop y kien cua cac ban ong nghiep.
Tac gia
http://www.ebook.edu.vn
http://hoahocsp.tk
-3-
http://www.ebook.edu.vn
http://hoahocsp.tk
-4-
http://www.ebook.edu.vn
http://hoahocsp.tk
-5-
http://www.ebook.edu.vn
http://hoahocsp.tk
-6-
http://www.ebook.edu.vn
http://hoahocsp.tk
-7-
Chng II. CAN BANG HOA HOC NH LUAT BAO TOAN NONG O
p C + q D +
Dien ra en mot luc nao o th toc o cua phan ng thuan bang toc o cua phan
ng nghch. Luc o can bang c thiet lap.
e tnh nong o cac chat tham gia phan ng va san pham phan ng tai thi
iem can bang (nong o can bang) ngi ta thng dung nh luat tac dung khoi
lng.
* Neu A, B, C, D la nhng cau t khong mang ien tch th nh luat tac
dung khoi lng c bieu dien:
K=
=K
Phng trnh nay ap dung cho cac chat khong hoac kem ien ly trong cac
dung dch nc loang.
K: hang so can bang, ch phu thuoc vao nhiet o (oi khi ngi ta goi la
hang so can bang nong o Kc)
[A], [B] la nong o can bang cua cac chat A, B
* Neu A, B, C, D la nhng ion th gia chung co tng tac tnh ien, lam
nong o cua ion t do nho hn nong o thc cua chung trong dung dch, luc nay
trong bieu thc cua nh luat tac dung khoi lng phai thay nong o bang hoat
o a. Khi o:
Ka =
a Cp .a qD ...
am
.a n ...
A B
Ka =
a Cp .a qD ....
am
.a n ...
A B
Ka = Kc.
[A ]m f n [B]n ...
B
fC p .fD q ...
f
.f
http://www.ebook.edu.vn
http://hoahocsp.tk
-8-
Ka la hang so can bang hoat o, phu thuoc vao nhiet o va lc ion cua dung
dch.
KC la hang so can bang nong o KC = K
He so hoat o f phu thuoc vao lc ion cua dung dch. Lc ion bieu dien
tng tac tnh ien cua cac ion trong dung dch:
= 0,5 ( Z12C1 + Z22C2 + .. ) = 0,5 Zi2. Ci
Trong o: Z la ien tch va C la nong o cua cac ion trong dung dch. Tuy
vao gia tr cua ma he so hoat o f c tnh bang cac bieu thc khac nhau.
Neu:
* 0: khi dung dch rat loang tng tac tnh ien gia cac ion khong ang
ke th f = 1 nen a = C.
* 0,02 th f c tnh bi bieu thc
lg f = 0 , 5 Z 2
0 ,5 Z 2
1+
lg f =
0 ,5 Z
1 +
+ h
http://www.ebook.edu.vn
http://hoahocsp.tk
-9-
= 2. 0,1 ion g / l
http://www.ebook.edu.vn
http://hoahocsp.tk
- 10 -
- Chat ien ly trung bnh va yeu: la chat ma khi hoa tan vao nc no ch
phan ly mot phan thanh ion.
V du: CH3COOH
CH3COO- + H+, s phan ly ch xay ra mot phan,
hang so phan ly cua CH3COOH la:
K =
C
[CH COO ][ H + ]
3
[CH 3 COOH ]
2. o ien ly:
e bieu dien o phan ly cua cac chat ien ly yeu ngi ta dung ai lng goi
la o ien ly ky hieu .
MeA
[Me + ][A ] 2 .C 2
2C
K=
=
=
[MeA ]
C(1 ) 1
Qua bieu thc tren ta thay trong mot ieu kien nhat nh K la mot hang so nen
khi C cang giam th o ien ly cang tang.
oi vi chat ien ly manh th = 1
oi vi chat ien ly rat yeu th << 1, trong bieu thc cua K co the bo qua
canh gia tr 1, nen K = 2.C va = ( K/C )1/2, K khong oi nen C cang be th
cang ln. Do o oi vi nhng chat ien ly rat yeu th cang pha loang s phan ly
cang tang.
V du: tnh o ien ly cua dung dch HCOOH trong dung dch HCOOH co nong
o 3.10-1M. Biet KHCOOH = 1,77.10-4 , MHCOOH = 46
HCOOH
K=
HCOO- +
H+
[ HCOO ][ H + ]
[ HCOOH ]
K=
x .x
x2
4
1
,
77
.
10
=
3 .10 1 x
3 .10 1 x
http://www.ebook.edu.vn
http://hoahocsp.tk
- 11 -
x = 7,3.10-3iong/l
Vay = 2,43.10-2 va % = 2,43%
Co the giai bai toan tren bang phng phap gan ung bang cach:
Gia thiet x << 3.10-1 nen bo qua x ben canh 3.10-1 nen phng trnh bac 2
tren tr thanh:
x2 = 3.10-1.1,77.10-4 giai ra x = 7,29.10-3 iong/l
III. Cach bo qua ai lng nho canh ai lng ln:
Gia s co hai so hang a + b, ta bo qua a ben canh b khi a < b 100 lan. Neu bieu
dien di dang logarit th bo qua a khi lgb lga 2 n v lg.
IV. nh luat bao toan nong o:
Trong dung dch cac chat ien ly, nong o cac phan t thng c bieu dien
theo mol/l. Thng s dung cac quy c:
- Nong o goc C0 la nong o cua chat trc khi a vao hon hp phan ng.
- Nong o ban au C la nong o cua chat trong he trc khi tham gia phan
ng.
- Nong o can bang hay ky hieu [ ] la nong o cua cac cau t sau khi phan
ng a xay ra va at ti trang thai can bang.
V du: tron 10ml dung dch NaCl 0,1M vi 5ml dung dch AgNO3 0,25M th:
- Nong o goc C0(NaCl) = 0,1M, C0(AgNO3) = 0,25M
- Nong o ban au:
C=
C0V0
V0 + V
C NaCl =
0,1.10
= 0,067 M
10 + 5
va C AgCl =
0,25.5
= 0,083 M
10 + 5
Na3PO4
0,1
PO43-
3.0,1
0,1
+ H2O
HPO42- + OH-
HPO42- + H2O
H2PO4- + OH-
H2PO4- + H2O
H3PO4
+ OH-
http://www.ebook.edu.vn
http://hoahocsp.tk
- 12 -
I. Mot so nh ngha:
1. nh ngha acid va baz:
Trc ay nh ngha cua Arrhenius c s dung rong rai (acid la chat khi hoa
tan vao nc co the phan ly thanh H+ va anion; con baz la chat ma khi hoa tan vao
nc co the phan ly thanh OH- va cation) nhng nh ngha nay khong tong quat v
ch ap dung cho mot so loai chat va khi dung moi la nc.
Nam 1923 Bronsted (nha bac hoc ngi an Mach) e ra nh ngha tong quat
nh sau: acid la chat co kha nang cho proton (H+) va baz la chat co kha nang nhan
proton.
Acid cho proton tao thanh baz lien hp
Baz nhan proton tao thanh acid lien hp
Moi cap acid-baz lien hp co the bieu dien bang he thc sau:
baz lien hp + H+
Acid
V du:
Acid
baz lien hp
CH3 COOH
CH3COO-
H+
H2S
HS-
H+
HS-
S2-
H+
NH4+
NH3
Al(H2O)63+
+ H+
[Al(H2O)5OH]2+ + H+
Nhan xet:
- Acid va baz co the la phan t, ion (cation, anion)
- Proton H+ khong co kha nang ton tai trang thai t do, v vay 1 chat ch the
hien ro tnh chat acid hay baz trong dung moi co kha nang nhan hay cho proton.
V du:
baz.
Acid
H2O
baz
H3O+
Baz
H2O
acid
OH-
NH4+ +
H2O
NH3
H3O+
CN-
H2O
HCN +
OH-
- Tuy theo ban chat cua dung moi, 1 chat co the the hien tnh acid hoac
V du:
CH3COOH la acid trong nc v CH3COOH + H2O
CH3COO +H3O+ nhng trong hydro florua long( H2F2) CH3COOH lai la mot
baz v:
CH3COOH + H2F2
ang Th Vnh Hoa
CH3COOH2+ + HF2http://www.ebook.edu.vn
http://hoahocsp.tk
- 13 -
- H2O la 1 dung moi va co kha nang cho H+ va co kha nang nhan H+ nen
nc la 1 dung moi lng tnh.
- Mot so phan t va ion co kha nang va cho H+, va nhan H+ goi la lng
tnh.
V du:
HPO42-
2Na+ +
Na2HPO4
H2PO4-
H+
HPO42PO43- +
2. Hang so acid KA va hang so Baz KB:
H+
e ac trng cho cng o cua acid hoac baz ngi ta dung ai lng hang so
acid (KA) va hang so baz (KB).
* Vi acid:
H3O+ + A-
HA + H2O
H+ + A-
e n gian ta viet: HA
[H + ][A ]
KA =
[HA ]
Th hang so acid la:
KA cang ln th acid cang manh. e thuan tien cho viec tnh toan ngi ta
thng dung pKA = - lgKA. V du CH3COOH co KA = 10-4,75 va HCN co KA =
10-9,4, vay CH3COOH la acid manh hn HCN.
* Vi baz:
A- + H2O
HA + OH-
K =
B
[HA ][OH ]
[A ]
http://www.ebook.edu.vn
http://hoahocsp.tk
- 14 -
H3PO4
H+
H2PO4-
KA1 = 10-2,21
H2PO4-
H+
HPO42-
KA2 = 10-7,21
HPO42-
H+
PO43-
KA3 = 10-12,36
H2O
HPO42-
OH-
KB1 = 10-1,64
HPO42- +
H2O
H2PO4-
OH-
KB2 = 10-6,79
H2PO4- +
H2O
H3PO4 +
3. Quan he gia KA va KB. Tch so ion cua nc:
OH-
KB3 = 10-11,88
KA =
K =
[H + ][A ]
[HA ]
[HA ][OH ]
[A ]
KA.KB = [H+][OH-]
Mat khac:
(1)
H+
H2O
OH-
[H + ][OH ]
K =
[H 2 O]
=> K.[H2O] = [H+][OH-]
KH2O
= [H+][OH-]
(2)
KH2O c goi la tch so ion cua nc, no la hang so ch phu thuoc vao nhiet
o, khong phu thuoc vao nong o cua cac ion H+ va OH- trong dung dch.
250C KH2O = 10-14 vay pKH2O = - lgKH2O = 14
T (1) va (2) => KA.KB = KH2O = 10-14
pKA + pKB = pKH2O = 14 ( 250C)
Hai cong thc tren ch ap dung cho acid baz lien hp
Neu KA cang ln ngha la acid cang manh th KB cang nho ngha la baz lien
hp cang yeu. V du:
- HCl la 1 acid manh KA = th baz lien hp vi no la Cl- lai la 1 baz vo
cung yeu co KB = 0.
- HCN la 1 acid yeu co KA = 10-9,4 th baz lien hp vi no la CN- la 1 baz kha
manh co KB = 10-4,6.
4. pH va thang pH:
pH = -lg[H+] va pOH = -lg[OH-]
http://www.ebook.edu.vn
http://hoahocsp.tk
- 15 -
Gia tr pH ac trng cho tnh chat acid hoac baz cua cac chat ien ly the hien
qua nong o cua ion H+ hoac ion OH-. V [H+].[OH-] la mot hang so tai nhiet o
cho trc, con [H+] va [OH-] la nhng ai lng bien oi nen bang gia tr [H+]
va [OH-] co the xet oan o acid hoac o kiem cua dung dch.
[H+].[OH-] =10-14 => pH + pOH = pKH2O=14
Thang pH c quy nh nh sau:
Moi trng acid
[H+] = [OH-]
pH = pOH = 7
II. Tnh pH cua dung dch acid: pH = -lg aH+ hay pH = - lg [H+]
1. Dung dch n acid manh:
Gia s co dung dch acid manh HA co nong o CA.
Tuy theo nong o cua acid manh ma tnh pH bang cac cong thc khac nhau:
* Neu CA 10-6 mol/l
th pH = -lg CA
* Neu CA 10-8 mol/l
Dung dch acid qua loang nen co the coi [H+] = [OH-] =10-7 do o pH = 7
* Neu 10-8 < CA < 10-6 tc CA ~ 10-7 mol/l
Th phai s dung phng trnh bac hai [H+]2 - CA[H+] - KH2O = 0 e tnh
[H+].
Tuy nhien trong thc te thng CA > 10-6 nen e tnh pH cua dung dch acid
manh ta dung pH = - lg CA.
V du: Tnh pH cua dung dch HCl 2.10-2M va 5.10-3 M trong 2 trng hp ke
ca lc ion va bo qua lc ion. Nhan xet ?
* Neu bo qua lc ion: v nong o > 10-6 => pH = -lg CA
- pH cua dung dch HCl 2.10-2M = -lg2.10-2 = 1,698 1,70.
- pH cua dung dch HCl 5.10-3M = -lg 5.10-3 =2,30
* Neu tnh lc ion:
- Vi HCl 2.10-2M = 0,5( 2.10-2.12 + 2.10-2.12) = 2.10-2 =0,02
lg f
H+
0,02 =>
fH+ = 0,849
http://www.ebook.edu.vn
http://hoahocsp.tk
- 16 -
lg f
fH+ = 0,92
aH+ = fH+.CH+ = 0,92. 5.10-3 = 4,6.10-3
pH = -lgaH+ = 2,336
Nhan xet: so sanh cac gia tr pH trong 2 trng hp ta thay neu dung dch co
nong o cang be th s sai lech khi bo qua lc ion la khong ang ke.
2. Dung dch n acid trung bnh 10-3 < KA < 100
Gia s co dung dch acid HA co nong o CA va hang so acid KA.
Neu KA co gia tr 10-3 < KA < 100 th pH cua dung dch c tnh t viec giai
phng trnh bac hai: [H+]2 + KA[H+] - KA.CA = 0
3. Dung dch n acid yeu 10-10 < KA < 10-3
Gia s co dung dch acid HA co nong o CA va hang so acid KA.
Neu KA co gia tr 10-10 < KA < 10-3 th pH cua dung dch c tnh t cong thc
[H+]2 = KA.CA
pH = 0,5pkA 0,5lgCA
V du: Tnh pH cua dung dch HCOOH 0,017M biet HCOOH co KA = 1,77.10-4
Giai: V KA = 1,77.10-4 = 10-3,75 < 10-3 nen xem HCOOH la 1 n acid yeu
=> pH = 0,5pkA 0,5lgCA = 0,5. 3,75 - 0,5.lg 0,017 = 1,875 + 0,885 = 2,76
4. Dung dch a acid:
a acid la acid ma khi hoa tan vao nc se lan lt phan ly theo nhieu nac, ng
vi moi nac la mot hang so acid rieng.
V du: * H2CO3
H+
HCO3- co K1 = 4,47.10-7
HCO3-
H+
CO32- co K2 = 6.10-11
* H3PO4
H+
H2PO4- co K1 = 7,6.10-3
H2PO4-
H+
HPO42- co K2 = 6,2.10-8
HPO42-
H+
PO43- co K3 = 4,2.10-13
Nhn chung H+ tach ra khoi phan t nac trc de dang hn nac sau, v so H+
tach ra cang tang th phan t mat H+ cang am, nen gi H+ cang chat. Do o hang
so phan ly cua nac sau thng nho hn cua nac trc.
http://www.ebook.edu.vn
http://hoahocsp.tk
- 17 -
Dung dch a acid co the xem nh dung dch cua mot hon hp cac n acid yeu
co nong o bang nhau va hang so acid khac nhau.
- Neu a acid co K1 > K2 khoang 104 lan th xem dung dch a acid o nh
dung dch n acid co KA = K1.
- Neu a acid co K1 khong ln hn K2 nhieu th xem nh hon hp cac n
acid (se xet trng hp pH cua dung dch hon hp cac acid).
V du:
1. Tnh pH cua dung dch H2S 0,025M biet H2S co K1= 5,7.10-8, K2= 1,2.10-15
Giai: Do K1 > K2 hn 104 lan nen co the xem H2S nh 1 n acid yeu co KA
= K1 = 5,7.10-8 (thuoc loai acid yeu) nen :
pH = 0,5pKA - 0,5lgCA = 0,5(-lg5,7.10-8) - 0,5lg0,025 = 3,62 = 0,80 = 4,42
5. pH cua hon hp hai acid:
a) Hon hp 2 acid manh:
Gia s dung dch hon hp 2 acid manh la HA1 co nong o C1 va HA2 co nong
o C2 th pH cua dung dch c tnh t phng trnh:
pH = - lg ( C1 + C2 )
b) Hon hp 1 acid manh va 1 acid yeu:
Gia s hon hp gom 1 acid manh HAm co nong o Cm va 1 acid yeu HAy co
nong o Cy va hang so acid KHAy th tuy theo tng trng hp cu the ma pH cua
dung dch c tnh bang cac cong thc khac nhau:
Neu Cm Cy
pH cua dung dch do acid manh quyet nh nen pH = - lgCm
Neu Cm < Cy
Muon tnh gan ung th giai phng trnh [H+]2 Cm[H+] KHAyCy = 0
[H ] = C +
m
C y .K HAy
[H + ] + K
HAy
http://www.ebook.edu.vn
http://hoahocsp.tk
- 18 -
- Giai chnh xac bang cach the vao phng trnh tong quat roi bien oi, ta
c:
[H+]2 + 10-4,75[H+] 10-4[H+] - 10-8,75 - 10-6,75 = 0
Giai phng trnh ta c [H+] = 4,62.10-4 va pH = 3,34
Ta thay 2 cach giai pH lech nhau khong nhieu nen co the giai theo phng
phap gan ung cho n gian.
c) Hon hp 2 n acid yeu (hay 1 a acid co k1 k2 )
Gia s hon hp 2 n acid yeu la HA1 (co nong o C1, hang so acid K1) va
HA2 (co nong o C2 va hang so acid K2).
- Giai gan ung:
[H+]2 = k1C1 + k2C2
Mot cach tong quat: [H+]2 = kiCi
- Giai chnh xac:
[H + ] =
K 1 C1
[H + ] + K 1
K 2 C2
[H + ] + K 2
ay la phng trnh tong quat, tuy theo tng trng hp cu the co the n
gian hn.
- Neu C1 C2 nhng K1 >> K2
- Neu K1 K2 nhng C1 >> C2
- Neu K1 >> K2 du C1 < C2
Trong ca 3 trng hp tren pH ch do HA1 quyet nh tc la:
[H + ] =
K 1C1
[H + ] + K 1
CH3COOH
CH3COOH
Giai
i- * Giai gan ung:
[H+]2 = (K.C)CH3COOH + (K.C)HCN
=10-4,76.0,1
+ 10-9,21.0,1
http://www.ebook.edu.vn
http://hoahocsp.tk
- 19 -
[H + ] =
K CH 3COOH C CH 3COOH
[H + ] + K CH 3COOH
http://www.ebook.edu.vn
http://hoahocsp.tk
- 20 -
K+ + CN-
3Na+
PO43- + H2O
HPO42- +
HPO42- + H2O
H2PO4-
H2PO4- + H2O
PO43-
H3PO4 + OH-
Dung dch a baz co the xem nh dung dch cua mot hon hp cac n baz yeu
co nong o bang nhau va hang so acid khac nhau.
- Neu a baz co KB1 > KB2 khoang 104 lan th xem dung dch a baz o nh
dung dch n baz co KB = KB1.
- Neu a baz co KB1 khong ln hn KB2 nhieu th xem nh hon hp cac n
baz (se xet trng hp pH cua dung dch hon hp cac baz).
V du: tnh pH cua dung dch Na3PO4 10-1M.
V PO43- co KB1> KB2 > KB3 c 104 lan nen xem nh mot n baz co KB = 101,62
, vay no la mot baz trung bnh nen
http://www.ebook.edu.vn
http://hoahocsp.tk
- 21 -
[OH ] = C m +
C y .K B
[OH ] + K B
V du: Tnh pH cua hon hp Na2CO3 0,1M va NaOH 0,01M. Biet H2CO3 co
K1 = 4,47.10-7, K2 = 6.10-11.
Na2CO3
2Na+ + CO32-
CO32- la 1 a baz co KB1 = 1,67.10-4 hn KB2 = 0,224.10-7 gan 104 lan nen co
the xem gan ung nh CO32- la 1 n baz yeu. Vay ay la trng hp cua 1
dung dch hon hp gom 1 baz manh va 1 baz yeu co CNaOH = 0,01M <
CNa2CO3 = 0,1M.
Giai gan ung:
[OH-]2 CNaOH[OH-] KBCNa2CO3 = 0
[OH-]2 10-2 [OH-] 1,67.10-4.10-1 = 0
Giai phng trnh c [OH-] = 0,0115 suy ra pOH = 1,94
Vay pH = 14 1,94 = 12,06
Neu giai chnh xac cung cho ket qua nh vay
c) Hon hp 2 n baz yeu (hay 1 a baz co KB1 KB2)
Gia s hon hp 2 n baz yeu co hang so baz tng ng la KB1 va KB2, nong
o C1 va C2.
- Giai gan ung th: [OH-]2 = KB1C1 + KB2C2
Mot cach tong quat: [OH-]2 = kiCi
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 22 -
[OH ] =
K B1C1
[OH ] + K B1
K B2 C 2
[OH ] + K B2
ay la phng trnh tong quat, tuy theo tng trng hp cu the co the n
gian hn.
- Neu C1 C2 nhng KB1 >> KB2
- Neu KB1 >> KB2 du cho C1 < C2
- Neu K1 K2 va C1> C2
Trong ca 3 trng hp tren eu co the bo qua s phan ly cua baz th 2, tc
pH ch do baz th nhat quyet nh, tc la:
[OH ] =
K B1C1
[OH ] + K B1
http://www.ebook.edu.vn
http://hoahocsp.tk
- 23 -
[H + ] = K A .
CA
CB
pH = pK A lg
CA
CB
pOH = pK B lg
CB
CA
pH = 14 pK B lg
CA
CB
V du:
1 - Tnh pH cua dung dch hon hp CH3COOH 0,01M va CH3COONa
0,01M. Biet pKCH3COOH = 4,75.
Giai: ay la he gom acid yeu CH3COOH va baz lien hp CH3COO-
pH = pK A lg
CA
C
= pK CH COOH lg
3
C CH 3COOH
C CH 3COONa
= 4,75 lg
0,01
= 4,75
0,01
2 - Tnh pH cua dung dch tren neu them vao mot lt dung dch o:
a- 10 ml dung dch HCl 10-1 M
b- 10 ml dung dch NaOH 10-1M
Giai:
a. Khi them HCl vao th: CH3COONa + HCl CH3COOH + NaCl
So mol HCl them vao = [CH3COOH]c sinh ra = [CH3COONa] a phan
ng vi HCl = 10.10-1/1000 = 0,1.10-2M
Vay : CA = 10-2 + 0,1.10-2 = 1,1.10-2
CB = 10-2 0,1.10-2 = 0,9.10-2M
=> pH
Nh vay khi them 10-3 mol HCl vao 1 lt dung dch em CH3COOH 0,01 M
va CH3COONa 0,01M ch lam cho pH giam i: (4,75 4,66 = 0,09 n v),
nhng neu them 10-3 mol HCl vao nc th pH giam i (7-3) = 4 n v
a. Khi them NaOH vao th: CH3COOH + NaOH CH3COONa + H2O
http://www.ebook.edu.vn
http://hoahocsp.tk
- 24 -
Tng t cau a
=>
pH = 14 pK B lg
CA
CB
=+
pH
pH
= 2,3
C A .C B
CA + CB
= 2,3
C A .C B
CA + CB
= 2,3
C A .C B
C
http://www.ebook.edu.vn
http://hoahocsp.tk
- 25 -
acid baz lien hp co pKA gan vi pH em muon pha va tron chung vi so mol
bang nhau. Khi pha loang hay lam am lai 1 dung dch em pH cua dung dch
khong thay oi.
V du:
Tnh em nang cua dung dch em: CH3COOH 10-2M va CH3COONa10-2M
Giai:
Ta co :
C .C
C
10 2 + 10 2
0,01.0,01
=
= 10 4 > K A nen = 2,3. A B = 2,3
= 1,15.10 2
200
200
CA + CB
0,01 + 0,01
Muon pha mot dung dch em tot co pH bang mot gia tr cho san pH0 nao o,
nen chon acid yeu co pKA gan pH0. V du e tao dung dch em pH = 4,5 th
nen chon cap CH3COOH va CH3COONa co pKA = 4,75. Nhng muon tao dung
dch em co pH = 2,5 th khong nen chon he tren ma phai chon cap
CH2ClCOOH/CH2ClCOONa v pKCH2ClCOOH = 2,8, gan vi gia tr 2,5 hn.
V. pH cua dung dch cha 1 hp chat ion:
1. Hp chat ion cau tao bi 1 acid manh va 1 baz manh:
V du NaCl.Trong nc, hp chat nay phan ly hoan toan thanh cac ion trung
tnh vi H+ va OH- nen pH cua dung dch la pH cua nc (pH =7).
2. Hp chat ion cau tao bi 1 acid yeu va mot baz manh:
CH3COO- + Na+
CH3COONa
CH3COO- + H2O
CH3COOH + OH Xem nh dung dch cua n baz
3. Hp chat ion cau tao bi 1 baz yeu va 1 acid manh:
NH4+ +
ClV du:
NH4Cl
=>
NH4+
H+
+
NH3
Xem nh dung dch cua n acid
4. Hp chat ion cau tao bi 1 baz yeu va mot acid yeu:
V du:
mK A1
[H + ] + K A1
[H + ]
[H + ] + K A 2
http://www.ebook.edu.vn
http://hoahocsp.tk
- 26 -
V du:
1- Tnh pH cua dung dch NH4CN 10-1M biet pKHCN = 9,21, pKNH3 = 4,76
Giai:
NH4+ + CN-
NH4CN
NH4+
4,76 = 9,24.
CN- + H2O
Nen ay la he acid yeu va baz yeu khong lien hp co CNH4+ = CCNVay pH = 0,5 ( pK1 + pK2 ) = 0,5 ( 9,21 + 9,24 ) = 9,225
pH = 9,23
2- Tnh pH cua dung dch (NH4)2SO4 10-1M biet pKNH3 = 4,76 ; KHSO4- =
1,02.10-2
Giai:
(NH4)2SO4
2 NH4+ + SO42-
NH4+
H+ + NH3 vay NH4+ la acid cua he NH4+/ NH3 co pKNH4+ = 14 4,76 = 9,24.
SO42- + H2O
HSO4- + OH- vay SO42- la baz cua he HSO4-/ SO42- co
-2
KHSO4- = 1,02.10
Nen ay la he acid yeu va baz yeu khong lien hp co CNH4+ = 2C HSO4The va cong thc tren va giai phng trnh tnh c pH = 5,47
5. Hp chat la muoi acid cua a acid:
Muoi nay c tao thanh khi trung hoa khong hoan toan 1 a acid. Trong nc
muoi acid cua a acid the hien ca tnh acid lan tnh baz.
V du: muoi Na2HPO4
Na2HPO4
2Na+ + HPO42-
HPO42- la acid cua he HPO42-/ PO43- co hang so acid la KA3, ong thi la baz
cua he H2PO4-/ HPO42- co hang so acid la KA2. Vay ay la dung dch hon hp
acid yeu va baz yeu khong lien hp co nong o bang nhau:
pH = 0,5 ( pKA2 + pKA3 ) = 0,5 ( 7,21 + 12,38 ) = 9,80.
BAI TAP
http://www.ebook.edu.vn
http://hoahocsp.tk
- 27 -
2- Tnh nong o mol cua dung dch CH3COOH co pH bang 3,6. Cho KCH3COOH =
10-4,76
3- Phai them bao nhieu mol HCl vao 1 lt dung dch cha 0,01M CH3COOH va
0,01M CH3COONa e c dung dch co pH = 3. Cho KCH3COOH = 10-4,76
4- Tnh khoi lng NH4Cl can e pha 1 lt dung dch co pH = 5,5. Cho phan t
lng cua NH4Cl bang 53,5.
5- Tnh pH cua dung dch Cl2CHCOOH 0,1M. Cho KCl2CHCOOH = 10-1,3
6- Tnh pH cua dung dch NaHA 0,1M. Cho H2A co pK1 = 4, pK2 = 11
7- Tnh hang so baz cua baz yeu Pyridin, biet rang dung dch Pyridin nong o 10M co pH bang 8,1.
http://www.ebook.edu.vn
http://hoahocsp.tk
- 28 -
NH4+
+ H+
Hg2+
HgCl2
+ 2Cl-
S phan ly ch xay ra mot phan, nong o Hg2+ trong dung dch u e tao vi ion
S2- ket tua HgS co mau en
Hg2+
S2-
HgS
ML
http://www.ebook.edu.vn
http://hoahocsp.tk
- 29 -
Trong dung dch loang hoat o c coi bang nong o th hang so ben cua phc
la con goi la hang so tao thanh cua phc.
[ML ]
[M ][L ]
1 [M ][L ]
K= =
[ML ]
=
Con hang so khong ben cua phc con goi la hang so phan ly la nghch ao cua
hang so ben.
Ngi ta hay dung pK = - lgK.
Da vao gia tr cua hang so ben hoac khong ben cua phc co the biet c mc
o ben hay khong ben cua chung. cang ln th phc cang ben.
V du: phc FeY- co = 1025,10, phc MgY2- co = 108,69 nen phc FeY- ben
hn phc MgY2-.
V nc la phan t phan cc, v vay bat c cation kim loai nao trong nc
cung hoa hp vi phoi t la nc e tao phc hydrat M(H2O)mn+ (m la so phoi tr
cua ion kim loai, n la ien tch cua ion kim loai).
e n gian t ay trong cong thc tong quat khong ghi ien tch. Neu them
vao 1 phoi t 1L, tao c phc chat vi M th trong dung dch se xay ra phan ng:
M(H2O)6 + L
ML(H2O)5 + H2O
Vay phan ng tao phc trong dung dch nc la 1 phan ng the H2O trong phc
hyrat bang phoi t L
V du: Ni2+ co so phoi tr cc ai la 6 nen trong dung dch nc se tao thanh
phc Ni(H2O)62+ . Neu them anion etyleniamintetraacetat (Y4-) vao dung dch th:
Ni(H2O)62+ + Y4-
Ni(H2O)5Y2- + H2O
Cac phan t H2O trong phc Ni(H2O)62+ , Ni(H2O)5Y2- thc te khong anh hng
en tnh chat cua NiY2- va Ni2+ nen co the viet:
[NiY 2 ]
[Ni 2+ ][Y 4 ]
Zn2+ + NH3
1 =
[ZnNH 3 2+ ]
2+
[Zn ][NH 3 ]
= 10 2,18 K 1 =
http://www.ebook.edu.vn
http://hoahocsp.tk
2 =
Zn(NH3)22+ (2)
[Zn (NH 3 ) 2 2+ ]
[ZnNH
Zn(NH3)22+ + NH3
3 =
2+
= 101,25 K 2 =
][NH ]
3
1
2
Zn(NH3)22+ (3)
[Zn (NH 3 ) 3 2+ ]
[Zn (NH )
2+
3 2
Zn(NH3)32+ + NH3
4 =
- 30 -
][NH ]
= 10 2,31 K 3 =
1
3
Zn(NH3)42+ (4)
[Zn (NH 3 ) 4 2+ ]
[Zn(NH )
2+
3 3
][NH ]
= 101,96 K 4 =
1
4
e tien cho viec tnh toan, thng ngi ta dung hang so ben va khong ben
tong cong. V du cong 2 phan ng 1 va 2 tren lai ta co:
Zn(NH3)22+
Zn2+ + 2NH3
1,2 =
[Zn ( NH 3 ) 2 2+ ]
[Zn 2+ ][NH 3 ]2
= 1 . 2
K 1,2 =
1
1,2
(1)
http://www.ebook.edu.vn
http://hoahocsp.tk
- 31 -
ML
1 =
[ML ]
[M ][L ]
ML2
2 =
[ML ]
2
[ML ][L ]
MLn
[M ] =
M
2
[ML ] =
.C .[ L]
1
[ML n ] =
.C .[L ]n
1,n
Tuy nhien1 trong thc te viec tnh nong o can bang cua phc chat rat phc
tap v ngoai qua trnh phan ly hoac tao phc chnh, trong dung dch con xay ra
cac qua trnh phu khac nh qua trnh thuy phan cac ion kim loai, s proton hoa
cac phoi t, cac qua trnh tao phc phu, phan ng ket tua, phan ng oxy hoa.
Do o viec giai bai toan phc chat se a ve bac cao kho giai. e giai gan
ung ngi ta dung phng phap bien luan, tc la da vao nong o ban au cua
ion trung tam va phoi t, can c vao hang so ben hoac khong ben e loai bt
cac qua trnh xay ra vi mc o khong ang ke. Thng trong bai toan e giai
gan ung ch chu y en s phan ly hay tao phc.
- Vi nhng he cha d phoi t so vi ion kim loai hoac khi mc o tao
phc xay ra khong ln ta xem nong o can bang cua phoi t trong dung dch
[L] = nong o ban au (CL0) cua phoi t.
- Vi nhng he co nong o ion kim loai d so vi nong o ban au cua
phoi t th xem san pham phc chu yeu la phc co so phoi tr thap nhat.
Sau khi giai can kiem tra xem ket qua co phu hp vi gia thiet khong.
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 32 -
V du:
1- Tnh nong o can bang cua Ag+ va CN- trong dung dch K[Ag(CN)2] 10-1M,
biet hang so khong ben bang 10-21.
Giai
Cac qua trnh xay ra trong dung dch:
K[Ag(CN)2]
K+ + Ag(CN)2-
Ag(CN)2-
Ag+ + 2CN-
K=
K = 10-21
[Ag + ][CN ]2
[Ag(CN ) 2 ]
K=
x.(2 x ) 2
10
= 10 21
Vay:
Neu e nguyen phng trnh nay giai th se thanh phng trnh bac ba kho giai,
can bien luan e phng trnh n gian hn.
V K = 10-21 qua nho, chng to phc nay ben nen s phan ly khong ang ke tc
la gia tr x se << so vi 10-1 nen ta co the bo qua x ben canh 10-1.
Vay 4x3 = 10-22 nen x = 2,92.10-8
Vay [Ag+] = 2,92.10-8 iong/l << 10-1 la ung vi gia thiet.
[CN-] = 2.x = 5,84.10-8 iong/l.
2-Tnh nong o can bang cua cac ion Ag+, Ag(NH3)+, Ag(NH3)2+ trong dung
dch cha AgNO3 0,01M va NH3 1M. Biet Ag+ tao vi NH3 cac phc co hang so
ben tng nac la 1 = 103,32, 2 = 103,92.
Giai:
Cac qua trnh xay ra trong dung dch:
AgNO3
Ag+ + NO3-
Ag+ + NH3
Ag(NH3)+
Ag(NH3)+ + NH3
Ag(NH3)2+
http://www.ebook.edu.vn
http://hoahocsp.tk
- 33 -
Ta co:
[Ag + ] =
C0
Ag +
Trong trng hp nay he cha lng phoi t d so vi ion kim loai, nho chng
to mc o tao phc xay ra khong ln nen ta gia s nong o can bang cua phoi t
NH3 trong dung dch bang nong o ban dau cua no = 1M.
10 2
[Ag ] =
1 + 10
3,32
.1 + 10
3,32
.10
3,92
.1
= 10 9,24
Kiem tra lai gia thiet: da vao nh luat bao toan khoi lng oi vi
[NH3] + [Ag(NH3)+] + 2[Ag(NH3)2+] = CNH30 = 1
[NH3] = 1 10-5,92 2.10-2 = 0,98 1
ML
1 =
[ML ]
[M ][L ]
[ML] = 1[M][L]
ML
ML2
MLm-1 +
MLm (m)
(2)
http://www.ebook.edu.vn
http://hoahocsp.tk
- 34 -
H+
HY3-
[Y 4 ][H + ]
[Y 4 ][H + ]
[HY ] =
K =
4
K4
[HY 3 ]
3
hang so acid
HY3-
H+
H2Y2-
H+
H3Y-
H+
H4Y
hang so acid K1
Tng t nh tren lap cac bieu thc tnh K, roi t o rut ra [HY2-],[H3Y-], [H4Y].
Trong ieu kien o, hang so ben ieu kien cua phc MYn-4 c nh ngha:
'
MY n 4
[MY n 4 ]
[M ' ][Y ' ]
Vi: - [M] la tong nong o can bang cac dang ton tai cua Mn+ tr dang phc
MYn-4.
[M]
[M]
+1.2m[m][L]m
at M(L)
=>
The cac gia tr [HY3-], [H2Y2-], [H3Y-], [H4Y] a c rut ra tren vao [Y]
ta c:
[H + ] [ H + ]2
[ H + ]3
[H + ] 4
[Y ] = [Y ] 1 +
+
+
+
K4
K 4 .K 3 K 4 .K 3 .K 2 K 4 .K 3 .K 2 .K 1
'
[ H + ] [ H + ]2
[H + ]3
[H + ] 4
Y( H ) = 1 +
+
+
+
K4
K 4 .K 3 K 4 .K 3 .K 2 K 4 .K 3 .K 2 .K 1
at
Th:
=>
[Y] = [Y4-].Y(H)
http://www.ebook.edu.vn
http://hoahocsp.tk
- 35 -
Nh vay:
' =
[MY n 4 ]
[M ]. M ( L ) .[ Y 4 ]. Y( H )
MY n 4
M ( L ) . Y( H )
Cac he so M(L), Y(H) thay oi theo cac ieu kien tien hanh phan ng tao
phc.
V du:
Tnh hang so ben ieu kien cua phc MgY2- trong dung dch co pH =11, biet
hang so ben cua phc MgY2- la 108,7 va hang so ben cua phc Mg(OH)+ la
102,58;acid H4Y co pK1=2; pK2=2,67; pK3=6,27;pK4=10,95.
Giai: Cac qua trnh xay ra:
Mg2+ +
Y4-
MgY2-
Mg2+ +
OH-
MgOH+
Y4-
H+
HY3-
K4
HY3- +
H+
H2Y2-
K3
H2Y2- +
H+
H3Y-
K2
H3Y- +
H+
H4Y
K1
=102,58
H2O
' =
- Mg(OH) =
=108,7
MgY
Mg (OH ) . Y( H )
1 + Mg(OH)+ . [OH-]
' =
10 8,7
= 10 8,28
1,38 .1,89
http://www.ebook.edu.vn
http://hoahocsp.tk
- 36 -
V du: . phat hien ion Fe3+ bang phan ng tao phc co mau o mau vi
NH3
. phat hien ion Cu2+ bang phan ng tao phc co mau xanh am vi
- Che ion:
Khi trong dung dch cha nhng ion co the can tr viec phat hien cac ion khac
(chang han tao nhng phc hoac ket tua co mau che mau cua ion can xac nh) co
the loai anh hng cua cac ion can tr nay bang cach che nhng ion ay vi mot
phoi t thch hp, phoi t nay se tao phc ben khong mau (hoac co mau nhat) vi
nhng ion can tr. V du: khi tm Co2+ bang dung dch SCN- cho ra phc mau xanh,
neu co s hien dien cua Fe3+ cho ra phc mau o th khong the nhan ra phc mau
xanh cua Co2+. V vay muon phat hien Co2+ bang SCN- th trc o phai che Fe3+
bang cach dung F- e tao phc khong mau ben vi Fe3+, lam nong o Fe3+ t do se
ha thap xuong di nong o toi thieu co the phat hien Fe3+ bang SCN-.
Hoac khi tm thay Cd2+ bang S2- tao ket tua CdS mau vang, phan ng nay b
can tr bi 1 so ion nh Cu2+ , Ni2+ , Co2+ v chung tao ra sulfur co mau en.
Nen muon xac nh Cd2+ th phai che nhng ion can (bang cach dung CN-)
2. Trong phan tch nh lng:
Phan ng tao phc co rat nhieu ng dung e nh lng cac cau t bang cac
phng phap hoa hoc, hoa l ac biet la phng phap quang.
BAI TAP
1- Tnh hang so ben ieu kien pH = 4 cua phc MgY2-. Biet MgY2- = 108,7,
MgOH+ = 108,7, H4Y co pK1 =2, pK2 =2,67, pK3 =6,27, pK4 =10,95.
2- Cho dung dch Cu2+ 10-4M vao dung dch EDTA 10-2M pH = 6 e tao phc.
Hoi phan ng tao phc CuY2- nay co tnh nh lng hay khong? Biet CuY2- =
1018,8, Cu2+ tao vi OH- nhng phc co 1 = 107, 1,2 = 1013,68, 1,3 = 1017, 1,4 =
1018,5, H4Y co pK1 =2, pK2 =2,67, pK3 =6,27, pK4 =10,95.
3- Tnh hang so ben ieu kien cua phc NiY2- trong dung dch em NH3 1M va
NH4Cl 1,78M. Biet rang trong ieu kien o nong o ban au cua Ni2+ khong ang
ke so vi nong o NH3. Biet NiY2- = 1018,62, Ni2+ tao vi NH3 nhng phc co 1 =
102,67, 1,2 = 104,8, 1,3 = 106,4, 1,4 = 107,5, 1,5 = 108,1, H4Y co pK1 =2, pK2 =2,67,
pK3 =6,27, pK4 =10,95.
4- Can them NH3 vao dung dch AgNO3 10-2M en nong o can bang nao e giam
nong o Ag+ t do xuong 10-8M. Biet Ag+ tao vi NH3 nhng phc co 1 = 103,32,
1,2 = 107,24
http://www.ebook.edu.vn
http://hoahocsp.tk
- 37 -
Phan ng ket tua la phan ng tao thanh chat ran kho tan t cac chat tan trong
dung dch. Chat ran kho tan la chat ket tua. Phan ng ket tua la phan ng thuan
nghch.
I. ieu kien tao thanh ket tua. Quy luat tch so tan:
Khi cho dung dch NaCl tac dung vi dung dch AgNO3, cac ion Ag+ va Cl- se
ket hp vi nhau tao thanh AgCl t tan, tach ra. Cac ion Na+ va NO3- khong tham
gia vao phan ng ket tua nen con lai trong dung dch. Ket tua AgCl se ngng khi
phan ng at ti trang thai can bang:
Ag+ + Cl-
AgCl ngha la khi toc o ket tua bang toc o hoa tan.
- Toc o ket tua (Vkt) t le vi dien tch be mat S cua ket tua tiep xuc vi dung
dch va hoat o cua cac ion tao thanh tua.
Vkt = k1.S.aAg+.aCl- Toc o hoa tan (Vht) t le vi dien tch be mat S cua ket tua tiep xuc vi dung
dch
Vht = k2.S
Khi at trang thai can bang th Vkt = Vht
k1.S.aAg+.aCl- = k2.S
aAg+.aCl- = k2/k1 = TAgCl
Trong trng hp tong quat oi vi phan ng tao tua AmBn th:
TAmBn = aAm.aBn = [A]m[B]n.fAm.fBn
Neu AmBn la chat t tan tc la trong dung dch bao hoa nong o cua cac ion
A va B la nho va trong dung dch khong co ion nao khac, th lc ion cua dung
dch kha nho va co the coi hoat o cua cac ion bang nong o cua chung.
Do o:
TAmBn = [A]m[B]n
Bieu thc nay la noi dung cua quy luat tch so tan. Noi ve ieu kien hoa tan
hay tao thanh ket tua:
- Khi aAm.aBn hoac [A]m[B]n < TAmBn, tc la Vkt < Vht th tua khong
c tao thanh trong dung dch, dung dch o goi la dung dch cha bao hoa.
- Khi aAm.aBn hoac [A]m[B]n = TAmBn, tc la Vkt = Vht th tua khong
c tao thanh them cung khong tan them, dung dch o goi la dung dch bao
hoa.
- Khi aAm.aBn hoac [A]m[B]n > TAmBn, tc la Vkt > Vht th tua c tao
thanh, lam giam hoat o (hoac nong o) cua chung cho en khi aAm.aBn hoac
[A]m[B]n = TAmBn th ngng, dung dch trang thai o goi la dung dch qua
bao hoa.
http://www.ebook.edu.vn
http://hoahocsp.tk
- 38 -
II. Quan he gia o tan va tch so tan - Nhng yeu to anh hng en o tan:
- o tan S cua mot chat la nong o cua chat o trong dung dch bao hoa. n v
cua S thng la mol/l; g/l; mg/ml
- Tch so tan T cua mot chat la tch hoat o hoac nong o cua cac chat co trong
dung dch bao hoa vi so mu tng ng.
Vay o tan cung nh tch so tan la nhng ai lng ac trng cho dung dch bao
hoa. Do o tch so tan va o tan co moi quan he vi nhau, co the tnh c tch so
tan t o tan hoac ngc lai.
1. Quan he gia o tan va tch so tan:
(Ch xet o tan cua mot chat trong nc nguyen chat)
Neu khong ke en phan ng gia cac ion vi nc va trong dung dch khong co
ion la nao khac th o tan cua mot chat trong nc nguyen chat c xet nh sau:
Xet phan ng hoa tan tua AmBn trong nc nguyen chat:
AmBn
mS
nS
S = m +n
T
m
AmBn
.n n .fAm .fBn
Neu o tan cua ket tua be (tua t tan) th nong o cua A va B trong dung dch
be, nen 0 do o fA fB = 1
S = m +n
AmBn
m n
m .n
V du 1: Tnh tch so tan cua Mg(OH)2 200C, biet c 100ml dung dch bao hoa
nhiet o nay cha 0,84mg Mg(OH)2. Cho trong lng phan t cua Mg(OH)2 la
58.
Giai:
Mg(OH)2
S
Mg2+ + 2OHS
2S
http://www.ebook.edu.vn
http://hoahocsp.tk
- 39 -
Theo e bai 100ml dung dch bao hoa cha 0,84mg = 0,84.10-3 g. Vay so
gam cua Mg(OH)2 trong 1000ml la 1000.0,84.10-3/100 = 8,4.10-3 , suy ra so mol
cua Mg(OH)2 (cung chnh la nong o) la 8,4.10-3/58 = 0,145.10-3 = 1,45.10-4.
Vay o tan cua Mg(OH)2 la 1,45.10-4mol/l
TMg(OH)2 = 4.( 1,45.10-4)3 = 12,19.10-12.
- Neu tnh en lc ion cua dung dch th:
TMg(OH)2 = [Mg2+][OH-]2.fMg2+.f2OH = 0,5CiZi2 = 0,5 ( 1,45.10-4.22 + 2.1,45.10-4.12 ) = 4,35.10-4 < 0,02
lg fOH- = -0,5.12. (4,35.10-4)1/2 = -1,043.10-2
fOH- = 0,976
lg fMg2+ = -0,5.22. (4,35.10-4)1/2 = -4,171.10-2
fMg2+ = 0,91
TMg(OH)2 = 1,45.10-4.(2. 1,45.10-4)2. 0,976. 0,91 = 1,08.10-11
So sanh 2 ket qua ta thay khi o tan S < 10-4 mol/l th co the bo qua s tng tac
tnh ien, coi hoat o bang nong o.
V du 2: tnh o tan cua Ca3(PO4)2 trong nc, biet T Ca3(PO4)2 = 10-32,5
Goi S la o tan cua Ca3(PO4)2 va gia s S < 10-4 mol/l
Ca3(PO4)2
3Ca2+ + 2PO43-.
3S
2S
TCa3( PO 4 )2
S=5
108
=5
10 32 ,5
= 1,24.10 7 mol / l
108
CaSO4
S
T CaSO4 = [Ca
S
][SO42-]
2+
S
2
= S = 9,1.10-6
Vay S = 3,017.10-3mol/l
ay S > 10-4mol/l. Nen phai tnh en lc ion
T CaSO4 = [Ca2+][SO42-] f2 = S2. f2 = 9,1.10-6
= 0,5CiZi2 = 0,5(3,017.10-3.22 + 3,017.10-3.22 ) = 12,07.10-3 < 0,02
lg fCa2+ = lg fSO42- = -0,5.22. (12,07.10-3)1/2 = -0,2196
http://www.ebook.edu.vn
http://hoahocsp.tk
- 40 -
S=
TCaSO 4
f
9,1.10 6
(0,603)
= 5.10 3 mol / l
V du: Tnh o tan cua BaSO4 trong nc va trong dung dch Na2SO4 10-2M.
Biet TBaSO4 = 1,03. 10-10
Giai:
- Tnh o tan cua BaSO4 trong nc :
Trong dung dch co can bang sau : BaSO4
Ba2+
SO42-
2.10-2
10-2
Ba2+ + SO42-
[Ba2+] = S
[SO42-] = S + 10-2
http://www.ebook.edu.vn
http://hoahocsp.tk
- 41 -
Tch so tan cua BaSO4 nho, trong dung dch lai co d ion SO42- nen o tan
cua BaSO4 lai cang nho. V vay ta co the bo qua S canh gia tr 10-2 nen:
[ SO42-] = 10-2.
Do trong dung dch co 1 lng ang ke chat ien ly manh nen phai tnh he so
hoat o. V o tan cua BaSO4 nho v vay lc ion cua dung dch thc te ch do
Na2SO4 gay nen.
= 0,5CiZi2 = 0,5(2.10-2.12 + .10-2.22 ) = 3.10-2
0,02 < = 3.10-2 < 0,2, ap dung cong thc lgf tng ng tnh c:
lg fBa2+ = lg fSO42- = -0,296
fBa2+ = fSO42- = 0,506
T BaSO4 = [Ba2+][SO42-] fBa2+. fSO42- = S. 10-2.(0,506)2 = 1,03.10-10
Vay S = 4,023.10-8 mol/l
So sanh 2 gia tr S va S ta thay S << S. Vay trong dung dch Na2SO4 10-2M o
tan cua BaSO4 nho hn o tan cua no trong nc.
Ket luan:
Nh vay dung dch co cha ion chung lam giam o tan cua tua, ieu nay
c ng dung: e ket tua hoan toan 1 chat ngi ta thng dung d thuoc th, khi
ra ket tua phai dung nhng dung dch ra co cha ion chung e lam giam o tan
cua tua do o lam tang tnh chnh xac cua phep phan tch.
b) Anh hng cua chat ien ly la trong dung dch:
Khi trong dung dch co chat ien ly la th lc ion cua dung dch tang nen he
so hoat o giam va hoat o giam do o tch hoat o < tch so tan cho nen tua
tan them cho en khi thiet lap lai he can bang.
Vay khi co mat chat ien ly la th o tan tang len.
V du:
Tnh o tan cua AgCl trong nc nguyen chat va trong dung dch KNO3 10-1M,
biet TAgCl = 1,1 . 10-10.
Giai:
- o tan cua AgCl trong nc:
AgCl
Ag+ + Cl-
Goi S la o tan cua AgCl trong nc. Gia s S < 10-4 mol/l
TAgCl = [Ag+][Cl-] = S2
http://www.ebook.edu.vn
http://hoahocsp.tk
- 42 -
AgCl
Ag+ + Cl= [Ag+][Cl-].fAg+.fCl- = S2.f2
1
= (10 1.12 + 10 1.12 ) = 10 1
2
Lc ion trong dung dch chu yeu do KNO3 quyet nh.
0,02 < < 0,2
lg f
Ag +
= lg f
Cl
0,5.Z 2 .
1+
0,5.1 10 1
1 + 10 1
= 0,12
1,1.10 10
S' =
= 1,38.10 5 mol / l
2
( 0,76 )
So sanh S va S ta thay S > S. Vay o tan cua tua trong dung dch cha
chat ien ly la ln hn o tan cua no trong nc nguyen chat.
c) Tch so tan ieu kien T:
Gia s oi vi ket tua AmBn th cation kim loai (An+) co the tao phc vi phoi
t L nhng phc: AL (co hang so ben 1) ; AL2 (2 ) ALp(p). Con anion
(Bm-) cua acid yeu co the tham gia phan ng vi H+ tao ra HB, H2B HqB.
Trong o HqB co cac hang so phan ly la K1 , K2 , K3 , Kq.
Khi ion cua tua tham gia vao cac phan ng vi cac chat khac trong dung dch
th o tan cua tua se tang len. Cho nen phai dung tch so tan ieu kien ky hieu
T e ac trng cho o tan cua ket tua trong nhng ieu kien xac nh.
TAmBn = [A]m[B]n
AmBn
mAn+ + nBm-
http://www.ebook.edu.vn
http://hoahocsp.tk
- 43 -
[H + ] [H + ]2
[H + ] q
Kq
K q .K q 1
K q .K q 1 ....K 2 .K 1
[B] = nS = [B].B(H)
Vay:
Mat khac
S' = m + n
T'
AmBn
m n
m .n
S = m +n
AmBn
m n
m .n
CuS
S2-
HS- +
H+
S2-
HS-
H+
Cu2+ + OH-
H2S
Cu(OH)+ ; Cu(OH)2 ; Cu(OH)3- ; Cu(OH)42-
S' = m + n
T'
AmBn
m n
m .n
T'
CuS
1 .1
http://www.ebook.edu.vn
http://hoahocsp.tk
- 44 -
S( H )
= 1+
[ H + ] [ H + ]2
10 7
[10 7 ]2
+
= 1 + 12 ,89 + 12 ,89 7
K2
K 2 .K 1
10
10
.10
Ca2+ +
C2O42- +
H+
HC2O4-
HC2O4- +
H+
H2C2O4
C2 O 4( H )
C2O42-
[H + ] [H + ]2
10 4
10 8
= 1+
+
= 1 + 4,27 + 5,52
K2
K 2 K1
10
10
http://www.ebook.edu.vn
http://hoahocsp.tk
- 45 -
Khi trong dung dch co 2 ion A, B cung co kha nang tao vi thuoc th R hai ket
tua AR va BR co tch so tan khac nhau nhieu th co the tien hanh ket tua tng ion
mot. S ket tua nh vay goi la ket tua phan oan.
V du cac ion I- va Cl- cung tao vi Ag+ cac ket tua co gia tr tch so tan nh
sau: TAgI = 8,3.10-17, TAgCl = 1,78.10-10. V TAgI << TAgCl nen khi them Ag+ vao dung
dch hon hp I- va Cl- th AgI se ket tua trc sau o en AgCl ket tua.
- Neu trong dung dch co u ion Ag+ e AgI va AgCl cung ket tua th theo qui
luat tch so tan ta co:
[Ag+][I-] = TAgI = 8,3.10-17
[Ag+][Cl-] = TAgCl = 1,78.10-10
Lap t so hai phng trnh tren [I-]/[Cl-] = 4,66.10-7. Vay khi trong dung dch
co ca hai ket tua AgI va AgCl th t so [I-]/[Cl-] luon luon = 4,66.10-7. Ngha la
AgCl ch bat au ket tua khi [I-] = 4,66.10-7 [Cl-]
- Neu trong dung dch ch u ion Ag+ e AgI ket tua th theo qui luat tch so
tan ta co:
[Ag+][I-] = TAgI = 8,3.10-17
[Ag+][Cl-] < TAgCl = 1,78.10-10
Lap t so hai phng trnh tren [I-]/[Cl-] > 4,66.10-7. Ngha la khi trong
dung dch [I-] cha giam xuong en gia tr 4,66.10-7 [Cl-] th AgCl cha bat au
ket tua.
Gia thiet rang nong o ban au cua Cl- ln gap 100 lan nong o cua I-, tc
la:
4,66.10 7 C
Nong o con lai
Cl
* 100 =
* 100 = 4,66.10 3%
2
Nong o ban au
10 C
Cl
CCl- = 100CI- suy ra CI - = 10-2.CCl- nen khi AgCl bat au ket tua th CIgiam xuong con 4,66.10-7CCl-. Khi o % nong o I- con lai la bang:
Tc la co the coi I- a ket tua hoan toan. Vay co the ket tua lan lt cac ion
I- va Cl- bang ion Ag+.
V du:
Tnh nong o cua ion Cl- con lai trong dung dch hon hp Cl- co nong o 10-1M
va CrO42- co nong o 10-2M khi CrO42- bat au ket tua bang Ag+.
Biet TAgCl = 1,78.10-10, TAg2CrO4 = 1,1.10-12.
Giai:
Ag+ + Cl-
AgCl
http://www.ebook.edu.vn
http://hoahocsp.tk
- 46 -
Ag2CrO4
[Cl ]
[CrO 24 ]
1,78.10 10
1,1.10
12
= 1,7.10 4
BAI TAP
1- a- Tnh [Ag+] trong dung dch phc [Ag(CN)2-] co nong o 5.10-2 iong/l. Biet
phc [Ag(CN)2-] co = 1021.
http://www.ebook.edu.vn
http://hoahocsp.tk
- 47 -
b- Neu cho dung dch tren bao hoa kh H2S, khi o [S2-] = 10-15 iong/l th tua Ag2S
co xuat hien khong? Biet TAg2S = 2.10-50.
2- Tnh o tan cua AgI trong:
a- Nc
b- Dung dch KNO3 10-2M
c- Dung dch Ba(NO3)2 10-2M
Biet TAgI = 8,3.10-17
3- Tron 100ml dung dch Pb(NO3)2 0,003M vi 400ml dung dch Na2SO4 0,04M, ket
tua PbSO4 co tao thanh khong ? biet TPbSO4 = 10-7,8.
4- Tnh o tan ieu kien cua AgCl trong dung dch NH3 co nong o can bang la 0,1M.
Biet Ag+ tao vi NH3 nhng phc co 1 = 103,32, 1,2 = 107,24, TAgCl = 10-9,75.
http://www.ebook.edu.vn
http://hoahocsp.tk
- 48 -
I. nh ngha:
- Chat oxy hoa la chat co kha nang nhan ien t
- Chat kh la chat co kha nang cho ien t
Mot chat oxy hoa sau khi a nhan electron tr thanh chat kh goi la chat kh
lien hp vi chat oxy hoa a cho. Moi cap oxy hoa kh lien hp co the bieu dien
bang phng trnh ox + nekh, trong o n la so ien t ma chat oxy hoa nhan
e tr thanh chat kh.
V du mot so cap oxi hoa kh lien hp:
Dang oxi hoa
Dang kh
Zn2+
2e
Zn0
Fe3+
Fe2+
MnO4- + 8H+ + 5e
Mn2+ + 4H2O
ien t khong ton tai trang thai t do trong dung dch, do o mot chat ch the
hien tnh oxy hoa (hay kh) khi co chat kh (hay chat oxy hoa) cho (hay nhan)
ien t cua no.
- Phan ng trao oi ien t gia chat oxy hoa va chat kh goi la phan ng
oxy hoa kh. Co the viet dang tong quat:
ox1 + kh2
kh1 +
ox2
Zn2+ + Cu0
- Qua trnh oxy hoa la qua trnh cho ien t cua mot chat, chat nay goi la
chat kh hoac chat b oxy hoa.
kh2 - n e
Zn0 - 2e
- Qua trnh kh la qua trnh nhan ien t cua mot chat, chat nay goi la chat
oxy hoa hoac chat b kh.
ox1 + n e
Cu2+ + 2e
http://www.ebook.edu.vn
http://hoahocsp.tk
- 49 -
e ac trng cho kha nang oxy hoa kh cua mot chat ngi ta dung khai
niem the oxy hoa kh (hoac goi la the oxy hoa) c xac nh bang phng trnh
Nerst.
oi vi he n gian: ox + ne-
E = E0 +
a ox
RT
RT [ox ]
ln
vi dung dch rat loang th : E = E 0 +
ln
nF a kh
nF [kh ]
Trong o:
E: the ion hoa, tnh bang V
R: hang so kh, R = 8,331J
T: nhiet o tuyet oi
F: ien tch Faraday, F = 96500C
n: so electron trao oi
E0 la gia tr cua E khi bieu thc sau logarit bang 1, c goi la the oxy hoa kh
tieu chuan, E0 la hang so phu thuoc vao ban chat cua he oxy hoa kh lien hp.
Neu thay cac gia tr R, F va oi ln thanh lg th phng trnh co dang:
E = E0 +
0,059 a ox
0,059 [ox ]
lg
hay E = E 0 +
lg
n
a kh
n
[kh ]
Trong trng hp tong quat neu he oxy hoa kh lien hp c bieu dien bang
phng trnh:
a A + b B + c C + ..+ ne
m M + n N + ..
(1)
E = E0
Fe / Fe
3+
2+
0,059 a Fe
lg
1
a
* Fe3+ + e
* Cu2+ + 2e
Cu0
Fe2 +
http://www.ebook.edu.vn
http://hoahocsp.tk
3+
E = E0
Cu / Cu
2+
0,059 a Cu
lg
1
2
* MnO4- + 8H+ + 5e
E = E0
MnO 4 / Mn 2 +
- 50 -
2+
Mn2+ + 4H2O
0,059
+
lg
5
MnO 4
.a 8
H+
Mn 2 +
kh1 + ox2
2Cl- + 2Fe3+
Trong thc te khong the xac nh c gia tr tuyet oi the cua mot cap oxy
hoa kh lien hp ma ch xac nh c gia tr tng oi cua no so vi mot cap
khac. e so sanh the cua cac cap oxy hoa kh lien hp vi nhau th can phai xac
nh gia tr the tng oi cua cap ay so vi the cua mot cap oxy hoa kh lien
hp c quy c bang 0. Ngi ta quy c the oxy hoa kh chuan cua cap
2H+/H2 = 0.
Neu E0Fe3+/Fe2+ = +0,77 V dau (+) e ch rang the cua cap Fe3+/Fe2+ ln hn the
cua cap 2H+/H2. V vay Fe3+ oxy hoa H2 theo phan ng:
2Fe3+ + H2
2H+ + 2Fe2+
Neu E0Zn2+/Zn = -0,76 V dau (-) e ch rang the cua cap Zn2+/Zn nho hn the cua
cap 2H+/H2. V vay phan ng xay ra nh sau:
2H+ + Zn0
Zn2+
+ H2
III. Nhng yeu to anh hng en the oxi hoa kh - The oxi hoa kh tieu chuan ieu
kien:
Trong thc te chat oxy hoa va chat kh cua mot cap lien hp thng con tham
gia vao cac phan ng phu khac nh phan ng acid- baz, phan ng tao phc, phan
ng ket tua lam cho kha nang oxy hoa kh cua chung thay oi.
http://www.ebook.edu.vn
http://hoahocsp.tk
- 51 -
Ngi ta dung khai niem the oxy hoa tieu chuan ieu kien (ky hieu E0) e ac
trng cho cng o cua chung trong tng ieu kien cu the.
1. Anh hng cua pH:
The oxy hoa kh tieu chuan E0 ghi trong cac tai lieu la the tieu chuan c
xac nh khi pH = 0. Khi pH khac khong, gia s H+ tham gia vao qua trnh kh sau:
ox + m H+ + ne
E 0' = E 0 +
kh + d H2O
0,059
0,059
.m.pH
lg[H + ]m = E 0
n
n
Luc nay the oxy hoa kh tieu chuan ieu kien E0 c tnh bi cong thc:
Khi pH tang tc moi trng cang kiem th E0 giam tc kha nang oxy hoa cua
chat oxy hoa cang giam.
V du: Tnh the oxi hoa-kh tieu chuan ieu kien cua cap AsO43-/AsO33- trong
moi trng pH = 8 biet E0 cua cap nay = + 0,57 V ( pH = 0)
Giai: oi vi cap nay co the xay ra phan ng:
AsO43- + 2H+ + 2e- = AsO33- + H2O
E o ' = 0,57
0,059
.2(8) = 0,11V
2
Vay khi pH tang E0 giam ngha la kha nang oxi hoa cua AsO43- giam, con kha
nang kh cua AsO33- lai tang len.
2. Anh hng cua s tao phc:
Chat oxi hoa va chat kh cua 1 cap lien hp co the tham gia vao phan ng tao
phc, th cng o oxi hoa-kh cua cac chat cung thay oi. Ta xet cac trng hp:
a
ox + ne-
kh
kh + m L
khLm
ox + ne- + mL
khLm
E 0' = E 0 +
b-
kh - neox + mL
0,059
lg
1,m ( kh )
n
ox
oxLm
kh - ne- + mL
E 0' = E 0 +
1
0,059
lg
1,m (ox )
n
http://www.ebook.edu.vn
http://hoahocsp.tk
- 52 -
ox + m1L
kh + m2L
E 0' = E 0 +
0,059 kh
lg
n
ox
Fe2+ - e-
Fe3+
FeF63FeF63-
Thc ra s tao phc gia Fe3+ vi F- xay ra theo nhieu nac nhng neu trong
dung dch co d F- th phc co so phoi t ln nhat la FeF63- chiem u the nen
khong ke cac phan ng khac:
E 0' = E 0 +
0,059
1
lg 16 = 0,17 V
1
10
Vay trong moi trng co u F- th kha nang oxi hoa cua Fe3+ giam i, con kha
nang kh cua Fe2+ lai tang len.
V du 2- tnh the oxi hoa kh chuan ieu kien cua cap Co3+/Co2+ trong dung
dch co d NH3 e tao phc Co(NH3)63+ co hang so ben tong cong III1,6 = 1035,2 va
phc Co(NH3)62+ co hang so ben tong cong II1,6 = 104,4 Biet EoCo3+/Co2+ = 1,84 V
Giai:
Co3+ + e-
Co2+
Co3+ + 6NH3
Co(NH3)63+ va
3. Phan ng tao ket tua:
0,059 kh
= E0
E 0' = E 0 +
lg
Co
ox
n
E 0' = 1,84 +
3+
/ Co 2 +
Co2+ + 6NH3
Co(NH3)62+
II
0,059 1,6
+
lg III
1
1,6
0,059 10 4,4
lg 35,2 = 0,0228 V
1
10
Cung nh tren phan ng ket tua cung lam thay oi kha nang oxy hoa kh cua
cac chat.
aox + nekh
kh + X
khX
http://www.ebook.edu.vn
http://hoahocsp.tk
E 0' = E 0 +
ox - ne- + X
b-
kh - ne
0,059
1
lg
n
Tkh
khX
ox
ox + X
oxX
E 0' = E 0 +
kh - ne- + X
- 53 -
0,059
lg T
ox
n
kh
ox + X
oxX co Tox
E 0' = E 0 +
kh + X
0,059 Tox
lg
n
Tkh
V du1: tnh the oxi hoa kh chuan ieu kien cua cap Cu2+/Cu+ trong dung dch
co d I- e tao tua CuI co tch so tan TCuI = 10-12. Biet EoCu2+/Cu+ = 0,17 V
Giai:
Cu2+ + e-
Cu+
Cu+ + I-
CuI
E 0' = E 0
Cu / Cu
2+
0,059
1
1
lg
= 0,17 + 0,059 lg 12 = 0,878 V
n
Tkh
10
Vay khi co mat I- kha nang oxy hoa cua Cu2+ tang len nhieu
V du 2: tnh the oxi hoa kh chuan ieu kien cua cap Ag+/Ag trong dung dch
co d Cl- e tao tua AgCl co tch so tan TAgCl = 10-9,75. Biet EoAg+/Ag = 0,8 V
Giai:
Ag - e-
Ag+
Ag+ + Cl-
AgCl
E 0' = E 0
Ag + / Ag
0,059
lg T = 0,8 + 0,059 . lg 10 9,75 = 0,22 V
ox
n
http://www.ebook.edu.vn
http://hoahocsp.tk
- 54 -
kh1 co E0ox1/kh1
kh2 -
ox2 co E0ox2/kh2
ne
lg K =
0
n(E ox
/ kh
0
E ox
n(E 0
ox1/kh1
0,059
hay K = 10
0,059
0
)
Eox
2 / kh 2
kh1
E0ox1/kh1
kh2 -
ox2
E0ox2/kh2
n2 e
lg K =
0
n1 .n 2 (E ox
/ kh1
1
0
E ox
/ kh 2
2
0
0
Eox
n1 .n 2 (E ox1/kh1
)
2 / kh 2
hay K = 10
0,059
0,059
Ce4+ + e
Ce3+
Fe2+
Fe3+
- e
lg K =
1.( E 0
Ce 4 + / Ce3 +
E0
0,059
Fe3 + / Fe 2 +
1,55 0,77
= 13,22
0,059
[Ce 3+ ][Fe 3+ ]
K=
[Ce 4+ ][Fe 2+ ]
http://www.ebook.edu.vn
http://hoahocsp.tk
- 55 -
V nong o ng lng ban au cua chat oxy hoa va chat kh bang nhau nen
khi can bang th:
[Fe 3+ ]2
[Fe 3+ ] [Ce 3+ ]
13,22
K=
= 10
=
= 10 6,61
2+ 2
2+
4+
[Fe ]
[Fe ] [Ce ]
[Fe3+] = [Ce3+] va [Ce4+] = [Fe2+] do o:
Vay khi ket thuc phan ng lng Fe2+ ch con khoang mot phan trieu lng ban
au, lng Ce4+ cung vay. Ngha la phan ng xay ra hoan toan.
E0
MnO / Mn 2 +
= 1,51V va E 0
Fe3 + / Fe2 +
= 0,77 V
V du 2: Tnh hang so can bang cua phan ng gia MnO4- va Fe2+. Cho:
Giai:
So sanh hai cap the ta suy ra phan ng xay ra nh sau:
MnO4- + 5Fe2+ + 8H+
e-
Mn2+ + 4H2O
Fe3+
lg K =
n1 .n 2 (E 0
MnO 4 / Mn 2 +
E0
Fe3 + / Fe2 +
0,059
5.1(1,51 0,77)
= 62,7
0,059
kh1
Fe2+
Ce3+
The cua dang nay thay oi rat t khi them vao chat oxy hoa hoac chat kh. V
the dung dch loai nay c goi la dung dch em the. oi vi he nh vay th the
c tnh nh sau:
E = E0 +
0,059 [ox1 ]
lg
n1
[kh 1 ]
http://www.ebook.edu.vn
http://hoahocsp.tk
- 56 -
V du:
The oxy hoa kh cua dung dch hon hp Fe3+/Fe2+ khi nong o moi ion la 1
iong/l la:
E = E0
Fe / Fe
3+
2+
0,059 1
lg = 0,77 V
1
1
Neu them vao mot lt dung dch nay 0,01mol KMnO4 va ieu chnh cho pH cua
dung dch bang 0, khi o se xay ra phan ng:
MnO4- + 5Fe2+ + 8H+
0,01
5.0,01
E = E0 +
0,059 1,05
lg
= 0,772 V
1
0,95
E=
E0
ox1 / kh1
+ m
0,059 [ox1 ][H ]
lg
+
n1
[kh 1 ]
2. The cua hon hp chat oxi hoa va chat kh khong lien hp:
Gia s co dung dch hon hp chat ox1 co nong o ng lng la N01 va the oxy
hoa chuan la E0ox1/kh1 va chat kh2 co nong o ng lng la N02 va the oxy hoa
chuan la E0ox2/kh2
a) Neu phan ng xay ra theo kieu cac chat oxy hoa va kh lien hp co he so la
bang nhau nh sau:
n2ox1 + n1kh2
n1ox2 + n2kh1
kh1
kh2 - n2e
ox2
* Neu N01 > N02 tc trong dung dch d chat ox1, do o phai tnh the theo cap
ox1/kh1. Khi o the c tnh nh sau:
0
E = E ox
+
1 / kh1
0,059 [ox1 ]
lg
n1
[kh 1 ]
http://www.ebook.edu.vn
http://hoahocsp.tk
E=
0
E ox
/ kh
1
- 57 -
0
0
0,059 N1 N 2
lg
+
n1
N0
2
* Neu N01 < N02 tc trong dung dch d chat kh2, do o phai tnh the theo cap
ox2/kh2. Khi o the c tnh nh sau:
0
E = E ox
+
2 / kh 2
E=
sau:
0
E ox
2 / kh 2
0,059 [ox 2 ]
lg
n2
[kh 2 ]
N10
0,059
+
lg 0
n2
N 2 N10
n E0
1
ox1 / kh1
+ n E0
2
n1 + n 2
ox 2 / kh 2
* Neu N01 = N02 th the o goi la the tng ng va khi o the c tnh nh
Neu co s tham gia cua H+ tc la:
Hoac na phan ng co dang: ox1 + n1e + mH+
kh1 + (m/2)H2O
ox1 + mH+
th:
n E0
1
ox1 / kh1
+ n E0
2
n1 + n 2
ox 2 / kh 2
0,059
lg[H + ]m
n1 + n 2
V du 1:
Tnh the oxy hoa kh cua dung dch hon hp Ce4+ va Fe2+ khi:
a- CCe4+ = 9.10-2M, CFe2+ = 10-1M
b- CCe4+ = CFe2+ = 10-1M
c- CCe4+ = 1,1.10-1M, CFe2+ = 10-1M,
Biet E0 Ce4+/ Ce3+ = 1,55V; E0 Fe3+/ Fe2+ = 0,77V
Giai:
So sanh the cua hai cap, ta viet c phan ng xay ra nh sau:
Ce4+ + Fe2+
Ce3+ + Fe3+
http://www.ebook.edu.vn
http://hoahocsp.tk
E=
E 0 3+ 2 +
Fe / Fe
- 58 -
N10
0,059
9.10 2
+
lg 0
= 0,77 + 0,059 lg 1
= 0,826 V 0,83V
n2
N 2 N10
10 9.10 2
E=
n E0
1
ox1 / kh1
+ n E0
2
ox 2 / kh 2
n1 + n 2
1,55 + 0,77
= 1,16 V
2
c- CCe4+ > CFe2+ tc d Ce4+ nen tnh the theo cap Ce4+/Ce3+
E=
E 0 4 + 3+
Ce / Ce
0
0
0,059 N1 N 2
1,1.10 1 10 1
+
lg
=
1
,
55
+
0
,
059
lg
= 1,49 V
n1
N0
10 1
2
V du 2:
Tnh the tng ng cua phan ng gia hai oi MnO4-/Mn2+ va Fe3+/Fe2+ pH
= 0. Cho E0MnO4-/Mn2+ = 1,51V, E0 Fe3+/ Fe2+ = 0,77V.
Giai:
So sanh the cua hai cap, ta viet c phan ng xay ra nh sau:
MnO4- + 5Fe2+ + 8H+
Mn2+ + 4H2O
Fe3+
n E0
1
ox1 / kh1
+ n E0
2
n1 + n 2
ox 2 / kh 2
0,059
lg[H + ]m
n1 + n 2
Vi n2 = 1, n1 = 5, m = 8
b) Neu phan ng xay ra theo kieu cac chat oxy hoa va kh lien hp co he so
khac nhau:
Gia s co dung dch hon hp chat ox1 co nong o ng lng la N01 va the oxy
hoa chuan la E0ox1/kh1 va chat kh2 co nong o ng lng la N02 va the oxy hoa
chuan la E0ox2/kh2
Phan ng co dang:
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 59 -
n2 pkh1 + n1ox2
n2ox1 + n1kh2
p kh1
kh2 - n2e
ox2
* Neu N01 > N02 tc trong dung dch d chat ox1, do o phai tnh the theo cap
ox1/kh1. Khi o the c tnh nh sau:
E=
E0
ox1 / kh1
0
0
0,059 N1 N 2 1
1
p
+
lg
. .
vi [kh 1 ] = N 20 .
0
p
1
N
p kh
n
n1
1
2
1
[ ]
(1)
* Neu N01 < N02 tc trong dung dch d chat kh2, do o phai tnh the theo cap
ox2/kh2. Khi o the c tnh nh sau:
E=
N10
0,059
+
lg 0
n2
N 2 N10
0
E ox
2 / kh 2
(2)
E t =
0
0
+ n 2 E ox
n1E ox
1 / kh1
2 / kh 2
n1 + n 2
0,059
1
1
lg
n1 + n 2 p [kh ] p1
(3)
E t =
0
0
+ n 2 E ox
n1E ox
1 / kh1
2 / kh 2
n1 + n 2
0,059
1
1
lg
.[ H + ]m
p 1
n1 + n 2 p [kh ]
(4)
V du:Tnh the oxy hoa kh cua dung dch Cr2O72- 10-1N va Fe2+ co:
a- 9.10-2N
b- 10-1N
c- 1,1.10-1N
pH = 0 cho E0 Fe3+/ Fe2+ = 0,77V, E0 Cr2O7 2-/ 2Cr3+ = 1,33V
Phan ng gia hai cap nh sau:
Cr2O72- + 6Fe2+ + 14H+
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 60 -
2Cr3+ + 7H2O
Fe3+
E = 1,33 +
0,059 10 1 9.10 2 1
1
. .
lg
2
2 3.10 2 = 1,333 V
6
9
.
10
E=
E = 0,77 +
0,059
10 1
lg
= 0,829 V
1
1,1.10 1 10 1
I2 + NO + H2O
- Che cac ion bang cach thay oi so oxy hoa cua ion
V du Fe3+ can tr phan ng tm Co2+ bang SCN- nen phai che Fe3+ bang
cach kh Fe3+ ve Fe2+.
- Tach cac ion bang cach thay oi so oxy hoa cua ion
http://www.ebook.edu.vn
http://hoahocsp.tk
- 61 -
V du Fe3+ va Cr3+ eu co kha nang tao tua Fe(OH)3 va Cr(OH)3 nen kho
tach rieng ra khoi nhau, v vay oxy hoa Cr3+ moi trng baz thanh CrO42- tan
trong nc con Fe3+ nam lai dang Fe(OH)3
- Tach ri ion bang s oxy hoa phan oan: muon tach cac ion co tnh kh,
ta dung 1 chat oxy hoa thch hp e ch oxy hoa c mot trong cac ion noi tren.
V du trong dung dch co Cl- (E01 = 1,36V), Br- (E02 = 1,09V), I- (E03 = 0,54V),
muon ch co I- b oxy hoa thanh I2 ta nen chon chat oxy hoa nao ma co the nho
hn the cua E01 va E02, nen chon Fe3+ v cap Fe3+/ Fe2+ co E0 = 0,77V hoac dung
NO2- v cap NO2-/NO = 0,99V
- Tang tnh oxi hoa bang phan ng tao phc hoac tao tua:
V du: Cu2+ co tnh oxi hoa yeu e tang tnh oxi hoa ta them CN-, Cu2+ se
tao vi CN- phc lam tang E tnh oxi hoa tang.
VI.2- Trong nh lng:
- Phng phap the tch
- Phng phap ien hoa
BAI TAP
1- Cho oi oxi hoa kh : MnO4-,H+/Mn2+ co E10 = 1,51V
Fe3+/Fe2+ co E20 = 0,77V
a- Viet va can bang phan ng xay ra gia 2 oi va xac nh bieu thc tnh
ng lng cua MnO4- va Fe2+.
b-Tnh hang so can bang cua phan ng pH = 0.
2- Tnh the oxy hoa kh tieu chuan ieu kien cua cap Fe3+/Fe2+ trong dung
dch co d F- e tao phc FeF63- co hang so ben tong cong la 1,6 = 1016,1. Biet
Fe3+/Fe2+ co E0 = 0,77V.
3- Cho Cu vao dung dch AgNO3 0,05M. Viet phan ng xay ra trong dung dch.
Tnh hang so can bang cua phan ng va xac nh thanh phan cac chat trong dung
dch sau khi can bang at c. Biet E0Ag+/Ag= 0,80V, E0Cu2+/Cu = 0,34V
4-Tnh the oxy hoa kh cua dung dch hon hp:
aCe4+ 0,01M + Fe2+ 0,1M
bCe4+ 0,1M + Fe2+ 0,1M
cCe4+ 0,11M + Fe2+ 0,1M
Biet E0Ce4+/Ce3+ = 1,44V, E0Fe3+/Fe2+ = 0,68V
5- Cho oi oxi hoa kh : MnO4-,H+/Mn2+ co E10 = 1,51V
ClO3- /Cl- co E20 = 1,45V
a- Viet va can bang phan ng xay ra gia 2 oi va xac nh bieu thc tnh
ng lng cua ClO3- .
http://www.ebook.edu.vn
http://hoahocsp.tk
- 62 -
http://www.ebook.edu.vn
http://hoahocsp.tk
- 63 -
http://www.ebook.edu.vn
http://hoahocsp.tk
- 64 -
http://www.ebook.edu.vn
http://hoahocsp.tk
- 65 -
PHAN B. GII THIEU CAC PHNG PHAP PHAN TCH HOA HOC
Chng I. Phng phap phan tch khoi lng
Phng phap phan tch khoi lng thng c dung trong nhng trng hp
ham lng chat nh phan tng oi ln. ay la phng phap co o chnh xac cao
nhng no t c dung v no oi hoi nhieu thi gian va nhng ong tac phc tap.
I. Nguyen tac cua phng phap phan tch khoi lng:
nh lng mot cau t X theo phng phap phan tch khoi lng la tach X ra
di dang nguyen chat hay di dang mot hp chat xac nh. V du: xac nh Cu
trong hp kim ngi ta hoa tan hp kim trong H2SO4, HNO3 (loang) thu c dung
dch Cu2+, em ien phan trong ieu kien thch hp thu c Cu kim loai cc
am (catot). Sau khi ra sach va say hoac nung ket tua e chuyen ket tua thanh
mot hp chat ben co thanh phan hoa hoc xac nh, ngi ta em can, cuoi cung
da vao khoi lng cua ket tua se tnh c ham lng cua cau t X can xac nh
trong mau khao sat.
V du:
- e nh lng ion SO42- th ket tua no di dang BaSO4, roi ra sach, loc, say
kho va can.
- e nh lng ion Fe3+ th ket tua no di dang Fe(OH)3, roi ra sach, loc, say
kho roi nung thanh dang ben co thanh phan khong oi la Fe2O3 sau o can.
- Co mot vai trng hp trong phan tch khoi lng th khong lam ket tua ma
cho bay hi chat nh phan nh khi nh lng CO32- ngi ta phan huy no bang
acid va cho kh CO2 hap thu bang NaOH ran, hieu so khoi lng cua NaOH sau
va trc khi hap thu bang khoi lng CO2
II. Cach tien hanh cua phng phap phan tch khoi lng:
1. Chuan b dung dch phan tch:
- Chon mau ai dien
- Xac nh lng mau dung phan tch: tuy thuoc vao ham lng cua X ma c
lng mau phai dung e phan tch. V du:
. Neu ham lng X ln th lng mau khoang 0,01 - 1,0g
. Neu ham lng X nho th lng mau khoang 1,0 - 10g
Neu dung phng phap ket tua vi thuoc th th con tuy thuoc vao dang ket
tua:
. Tua vo nh hnh lng can khoang 0,05 - 0,5g.
. Tua tinh the lng can 0,2 - 0,6g.
- Chuyen mau thanh dung dch, nh mc en mot the tch nhat nh.
http://www.ebook.edu.vn
http://hoahocsp.tk
- 66 -
K=
Cr
M BaCrO
51,996
= 0,205
253,32
K=
2M
Cr
M Cr O
2
2.51,996
= 0,684
151,990
http://www.ebook.edu.vn
http://hoahocsp.tk
- 67 -
Dang tua sau khi say hoac nung goi la dang can, dang can phai thoa man cac
yeu cau sau:
- Phai co cong thc hoa hoc va thanh phan xac nh
- Ben vng ve mat hoa hoc, khong b thay oi trong khong kh, khong hut
am, khong hut CO2, khong b phan huy bi anh sang.
- Ket tua co khoi lng ln hn khoi lng cua nguyen to can xac nh cang
nhieu th ket qua phan tch cang chnh xac.
c) Cac yeu to anh hng en qua trnh ket tua:
* Cac trng hp lam ban ket tua:
- Ban tua do cong ket: la trng hp mot ion cung ket tua vi ion khac ma
trong ieu kien rieng le no lai khong tua.
V du: ieu kien rieng le Fe3+ khong phan ng vi H2SO4 e tao thanh
Fe2(SO4)3. Nhng khi co ion Ba2+ phan ng vi H2SO4 e tao thanh tua
BaSO4, th Fe3+ se phan ng vi H2SO4 e tao thanh Fe2(SO4)3.
Can phai loai Fe3+ trc bang cach chuyen no sang dang Fe2+ (dung
SnCl2) hay che di dang phc [FeF6]3- (dung F-).
- Ban tua do hap phu: (do cong ket be mat) la cac chat ban trong dung dch
bam dnh tren be mat tua mi tao thanh. Neu tinh the tua cang nho, cac chat
ban cang nhieu th hap phu ban cang nhieu. Muon khac phuc hien tng nay
can phai tao ieu kien sao cho tinh the ket tua to. Muon ket tua tinh the ln
th phai:
. Ket tua that cham t dung dch chat can xac nh loang, nong (nhiet o
tang th hien tng hap phu ban se giam v hap phu la qua trnh toa nhiet, do
o nhiet o cang thap ban cang de b hap phu len mat tua) va bang dung
dch thuoc th loang va phai khuay eu e tranh hien tng bao hoa mot
phan.
. Phai lam muoi ket tua mot thi gian tc la e yen ket tua trong dung dch
vai gi hoac qua em cho tinh the nho tan ra roi lai ket tua tren cac tinh the
ln hn.
- Ban tua do hap lu (do noi hap ): la chat ban b gi ben trong ket tua do
ket tua tao qua nhanh hay co cac ion ong hnh (ban knh ion tng ng
hay do thuoc he ket tinh giong nhau).
V du: Tua AgCl co the lan AgBr; tua BaSO4 co the lan RaSO4 Muon
khac phuc phai loai cac ion co the cho ket tua ong hnh.
- Ban tua do ket tua theo: la trng hp neu e ket tua chnh lau trong
dung dch th se co nhng chat khac tua theo.
V du: Tua HgS neu e lau trong dung dch co Zn2+ se co tua ZnS ket tua
theo. Hoac tua CaC2O4 neu e lau trong dung dch co Mg2+ se co tua
http://www.ebook.edu.vn
http://hoahocsp.tk
- 68 -
MgC2O4 ket tua theo. e khac phuc hien tng nay phai tach tua va ra tua
ngay sau khi tao tua xong.
Neu cac bien phap neu tren van cha khac phuc c th cach tot nhat e
lam sach tua la lam ket tinh lai.
* ieu kien tao tua oi vi cac dang tua khac nhau:
- Ket tua dang tinh the: can ket tua dang to, muon vay can lu y:
. Dung dch mau va thuoc th eu phai loang e giam qua bao hoa tng
cho khi hai dung dch tiep xuc nhau.
. Dung dch thuoc th them vao cham va khuay eu e va lam khuech tan
cac chat ban khoi tua va tao ieu kien cho cac hat tua to ra.
. Dung dch phai nong va co them mot lng acid vo c thch hp e hoa
tan bt cac hat tua nho, tao ieu kien cho cac hat tua to ra.
. Sau khi co tua e ket tua mot thi gian cho tua ln len.
- Ket tua dang vo nh hnh: la ket tua co kch thc qua nho (10A0 100A0). e khac phuc s ban tua dang vo nh hnh can lu y cac iem sau:
. Dung dch mau va thuoc th eu phai am ac e ket tua t xop va lang
nhanh.
. Dung dch thuoc th them vao nhanh va khay manh e chat ban khong
bam len tua.
. Dung dch mau va thuoc th eu phai nong e giam hien tng ban tua do
hap phu.
. Dung dch khong c e lau sau khi tao tua phai giai hap ngay bang mot
lng ln nc nong trc khi loc (e tach tua ra khoi dung dch). Neu tua
co o tan ln nhiet o cao th phai lam nguoi mi loc.
. Thng cho them chat ien ly thch hp e pha lp ien kep tren be mat
hat keo lam cho keo de ong tu. V du tua AgCl hap phu Ag+, pha lp ien
kep nay bang dung dch HNO3
3. Co lap va lam tinh khiet ket tua:
a) Loc:
e tach tua ra khoi dung dch a tao tua. Tuy theo lng tua va cach chuyen
t dang tua sang dang can ma ta co the chon nhng dung cu thch hp khac
nhau. Chang han neu tua chuyen sang dang can can nhiet o cao th dung pheu
loc thuy tinh va giay loc khong tro. Con neu tua chuyen sang dang can nhiet
o < 200 2500C th dung pheu thuy tinh ca hay chung loc Gooch. Tuy theo
kch thc cua tua ma chon giay loc co o mn khac nhau.
b) Ra:
La lam tinh khiet tua. Giai oan nay thng thc hien ong thi vi giai
oan loc goi la loc ra. Moi lan ra bang mot lng nho dung dch ra e
http://www.ebook.edu.vn
http://hoahocsp.tk
- 69 -
bao am tua c sach va t lam mat tua do b tan. Dung dch ra co the co
them ion chung e giam o tan cua tua trong qua trnh ra, va thng dung
dch ra phai nong (neu o nong nay lam tua tan khong ang ke)
4. Chuyen tua sang dang can:
Thng thc hien bang cach nung tua nhiet o, moi trng va thi gian thch
hp cho en khi dang can co thanh phan va khoi lng khong oi.
C
Fe(OH ) 3 900
Fe 2 O 3
0
V du:
5. Can:
La xac nh lng dang can thu c. Muon ket qua co o chnh xac cao can
lu y:
1000 C
Al(OH ) 3 900
Al 2 O 3
0
- Phai dung can phan tch can c en 0,1 mg (can c t nhat 4 so sau dau
phay)
- Phai bao ve dang can khoi tac dung cua cac chat thng co trong moi trng
nh H2O, CO2 , O2, N2, H2,
- Coc can phai c nung cung ieu kien khi chuyen tua sang dang can roi
mi can (v nhng nhiet o khac nhau khoi lng cua coc se khac nhau).
III. Cach tnh ket qua trong phan tch khoi lng:
1. He so chuyen:
Neu goi M la phan t lng cua dang can
M la so gam cua chat can xac nh tng ng vi 1 phan t gam dang
can, th he so chuyen K c tnh :
K=
K=
M'
M
M
Si
M SiO
K=
2M
Mg
M Mg P O
2 2
http://www.ebook.edu.vn
http://hoahocsp.tk
- 70 -
K=
2M
MgO
M Mg P O
2 2
Vay ng vi mot dang can co the co the co nhieu he so chuyen tuy thuoc vao
dang can bieu dien ket qua.
2. Tnh ket qua:
a) Trng hp phan tch trc tiep:
Tc la da vao khoi lng cua dang can e tnh ham lng cua nguyen to
can xac nh X.
- Lng chat can xac nh (mX) c tnh theo cong thc:
mX = K . q
trong o K la he so chuyen; q la khoi lng dang can
- Neu muon bieu dien ket qua theo ham lng % th phai biet khoi lng can
cua mau ban au. Gia s lng can mau ban au la p(g) th:
X% =
K.q.100
p
- Neu hoa tan p(g) mau thanh V ml dung dch va lay V0 ml em phan tch th:
X% =
K.q.V.100
p.V0
V du: Tnh phan tram Fe trong hp kim, biet rang t lng can hp kim la
0,500 g xac nh c 0,2545g Fe2O3
Giai: Ap dung cong thc:
X% =
K.q.100
p
K.0,2545 .100
Fe% =
0,500
Fe% =
K=
2M
Fe
M Fe O
2
2.55,847
= 0,6994
159,69
http://www.ebook.edu.vn
http://hoahocsp.tk
- 71 -
V du: Can p (g) hon hp NaCl va KCl hoa tan thanh dung dch. Sau o lam
ket tua Cl- di dang AgCl. Loc, ra, say va can c q (g) AgCl. Tnh so gam
moi muoi.
Giai: Goi m va n la so gam cua NaCl va KCl, ta co:
m + n = p
Mat khac NaCl + Ag+
AgCl + Na+
KCl + Ag+
m.
M AgCl
M NaCl
(1)
AgCl + K+
va n.
M AgCl
M KCl
Khoi lng tua AgCl tao thanh t NaCl va KCl lan lt la:
Theo e bai:
Giai he hai phng trnh (1) va (2) ta se tnh c m va n
m.
M AgCl
M NaCl
+ n.
M AgCl
M KCl
=q
(2)
http://www.ebook.edu.vn
http://hoahocsp.tk
- 72 -
http://www.ebook.edu.vn
http://hoahocsp.tk
- 73 -
- Phan ng phai chon loc tc la thuoc th ch tac dung vi chat can xac nh ma
khong phan ng vi cac chat khac.
- Phai co chat ch th thch hp e xac nh iem cuoi.
3. Phan loai cac phng phap phan tch the tch:
Co nhieu cach phan loai nhng thng hay phan loai theo ban chat cua cac
phan ng chuan o. Theo cach nay ngi ta chia ra lam 4 phng phap nh sau:
- Phng phap trung hoa (phng phap acid baz): dung e nh lng trc tiep
hoac gian tiep acid, baz va muoi.
- Phng phap ket tua: chu yeu e nh lng mot so ion tao c hp chat t
tan.
- Phng phap phc chat: da tren phan ng tao phc gia chat can xac nh va
thuoc th, c dung e nh lng trc tiep a so cation kim loai va nh lng
gian tiep mot so anion. Thuoc th hay dung la complexon.
- Phng phap oxy hoa kh: da tren phan ng oxy hoa kh va dung e
nh lng trc tiep cac nguyen to chuyen tiep, mot so chat hu c va nh lng
gian tiep mot so ion vo c.
4. Cac cach chuan o:
a) Chuan o trc tiep:
Thuoc th R se tac dung trc tiep vi chat can xac nh X.
Them t t thuoc th R vao mot the tch chnh xac dung dch chat can xac
nh X co cha chat ch th thch hp, cho en khi chat ch th chuyen mau. Da
vao the tch va nong o cua dung dch thuoc th R tieu ton ta tnh c lng
chat can xac nh X.
b) Chuan o ngc:
Them mot the tch chnh xac va d dung dch thuoc th R a biet nong o
vao mot the tch dung dch chat can xac nh X. Sau o chuan lng thuoc th
R d bang mot thuoc th R thch hp khac vi chat ch th thch hp. Da vao
the tch, nong o cua cac dung dch thuoc th R va R ta tnh c lng chat
can xac nh X.
Cach chuan o nay thng dung khi phan ng gia X va R cham hoac khong
co chat ch th thch hp e co the chuan o trc tiep theo phan ng gia X va
R.
c) Chuan o thay the:
Cho chat can xac nh X tac dung vi mot chat khac chang han la MY, X se
thay Y theo phan ng:
X
+ MY
MX
http://www.ebook.edu.vn
http://hoahocsp.tk
- 74 -
p% =
a
100
a+q
http://www.ebook.edu.vn
http://hoahocsp.tk
- 75 -
Chu thch: Nong o phan tram the tch cung tnh theo cong thc nh tren nhng
a, q, Q c bieu dien theo the tch.
3. Nong o phan t (CM):
Nong o phan t cua mot chat la so phan t gam (so ptg hay so mol) cua chat
o trong 1 lt dung dch. Thng c ky hieu bang ch M, ptg/l, mol/l at sau ch
so ch so phan t gam.
Neu a la so gam chat tan trong V lt dung dch, M la phan t gam cua chat o
th nong o phan t CM c tnh:
a
M.V
a.1000
M.V
V du:
1- Can 1,1689g NaCl hoa tan thanh 100ml dung dch. Tnh nong o phan t cua
dung dch NaCl (cho MNaCl = 58,443).
Giai: Ap dung cong thc tnh CM tren ta tnh c CM = 0,2M.
2- Can lay bao nhieu gam H2C2O4.2H2O e ieu che 250ml dung dch acid
oxalic 0,025M. Cho phan t lng cua H2C2O4.2H2O la 126,066.
Giai:T cong thc tnh CM suy ra a = 0,7879 g.
Chu y: Nong o ion c bieu dien theo ion.g/l hoac mol/l.
4. Nong o ng lng (CN):
Nong o ng lng cua mot chat la so ng lng gam (so ) cua chat o
trong 1 lt dung dch, hoac so mili ng lng gam (so m) cua chat o trong 1 ml
dung dch. Thng c ky hieu bang ch N hoac lg/l at sau ch so ch so
ng lng gam.
C =
N
a
.V
a.1000
.V
http://www.ebook.edu.vn
http://hoahocsp.tk
Ca( OH )2
Vi phan ng:
- 76 -
2HCl + Ca(OH)2
M Ca( OH )
con
H3PO4 + NaOH
CaCl2
=M
HCl
NaH2PO4 +
2H2O
HCl
H2O
H PO =
3
Vi phan ng:
M H 3PO 4
2
; NaOH = M NaOH
H3PO4 + 2NaOH
Vi phan ng
Fe(OH)3
Fe(OH ) =
3HCl
Fe ( OH )
Na2HPO4 +
=
2H2O
FeCl3 +
3H2O
; HCl = M HCl
- oi vi phan ng trao oi: muon tm ng lng gam cua mot chat trong
phan ng trao oi ta lay phan t gam cua chat o chia cho so ien tch ma 1 phan
t chat o trao oi trong phan ng.
V du:
Al2(SO4)3
Al
+ 3Pb(NO3)2 =
M
2
( SO )
Al ( SO )
2
4 3
4 3
2Al(NO3)3 + 3PbSO4
va
Pb(NO
M
)
3 2
Pb ( NO )
3 2
Hay noi cach khac ng lng gam cua mot muoi bang M/(n.Z) trong o n la
so ion a thay the va Z la ien tch ion a thay the.
- oi vi phan ng oxi hoa kh muon tm ng lng gam cua chat oxi hoa
hoac chat kh trong phan ng oxy hoa kh ta lay phan t gam cua chat o chia
cho so electron ma 1 phan t chat o a nhan hoac cho trong qua trnh phan
ng.
V du: 2KMnO4 + 10FeSO4
8H2O
+ 8H2SO4
e tm ng lng gam cua chat oxy hoa hoac chat kh khong can viet toan
bo phan ng no tham gia ma ch can viet na phan ng vi chat o.
KMnO4 =
MnO4Fe2+
ang Th Vnh Hoa
8H+ + 5e-
+
-
M KMnO4
e-
Mn2+ +
4H2O
Fe3+
http://www.ebook.edu.vn
http://hoahocsp.tk
- 77 -
MFeSO4
T =
R
a
V
V du:
1- Neu hoa tan 7,64g NaOH thanh 500ml th o chuan cua dung dch NaOH
bang bao nhieu?
Giai: ap dung cong thc tnh c TR = TNaOH = 0,01528g/ml = 15,28mg/ml.
2- Tnh o chuan cua dung dch CuSO4 0,1M biet phan t lng cua Cu la
63,545.
Giai: TCuSO4 = 6,3545mg/ml.
6. o chuan theo chat can xac nh:
o chuan cua dung dch thuoc th R theo chat can xac nh X la so gam cua
chat X phan ng ung vi 1ml dung dch thuoc th R. Thng ky hieu TR/X.
V du:
1- Dung dch KMnO4 co o chuan theo sat la 5,620mg/ml co ngha la 1ml dung
dch KMnO4 oxi hoa c 5,620mg sat (Fe2+).
2- Tnh o chuan cua dung dch KMnO4 theo sat, biet rang khi chuan o dung
dch cha 0,1170g Fe2+ th ton het 20ml dung dch KMnO4.
Giai: TKMnO4/Fe = 0.00585g/ml = 5,85mg/ml.
3- o chuan cua dung dch KMnO4 theo sat bang bao nhieu, neu hoa tan
3,1610g KMnO4 thanh 1lt dung dch.
Giai: o chuan cua KMnO4 theo sat la 0,005585g/ml = 5,585mg/ml.
http://www.ebook.edu.vn
http://hoahocsp.tk
- 78 -
Tong quat: Neu a la so gam cua thuoc th trong Vml dung dch, R va X la
ng lng gam cua thuoc th R va chat can xac nh X th o chuan cua dung dch
thuoc th R theo chat can xac nh X c tnh:
TR / x =
III.
a X
V R
Nguyen tac chung e chuyen cach bieu dien nong o cua mot chat da tren s
bao toan khoi lng cua chat o.
1. Chuyen nong o phan t sang nong o ng lng hoac ngc lai:
hay C = n.C
trong o n la so ion H+, OH-, e- hoac so ien tch ma 1 phan t a trao oi trong
phan ng.
2. Chuyen o chuan thanh nong o phan t, nong o ng lng va ngc lai:
T=
T=
C .M
M
hay
1000
C .
N
1000
hay C =
N
T.1000
M
T.1000
3. Chuyen o chuan theo chat can xac nh thanh nong o M hoac N va ngc lai:
CM =
TR / X .1000
X .n
va
CN =
TR / x .1000
X
10 .P%.d
M
va C =
N
10 .P%.d
http://www.ebook.edu.vn
http://hoahocsp.tk
- 79 -
5. Chuyen nong o P% thanh o chuan TR hoac o chuan theo chat can xac nh:
P% =
TR .100
va
P% =
TR/X . R .100
d. X
IV. Cach tnh ket qua trong phan tch the tch:
Viec tnh ket qua phu thuoc vao cach bieu dien nong o va cach phan tch.
Nguyen tac chung la da vao nh ngha nong o va qui luat ng lng e lap
cong thc tnh.
Qui luat ng lng: trong mot phan ng hoa hoc so ng lng hoac so
mili ng lng cua cac chat tham gia phan ng phai bang nhau.
So ng lng = CN.V(lt) = so gam/
So mili ng lng = CN.V(ml) = so mg/
1. Trng hp chuan trc tiep:
Gia s e chuan V0ml dung dch chat X phai dung het VRml dung dch thuoc
th R co nong o ng lng CN,R. Tnh nong o ng lng cua chat X va
lng chat X trong V0 ml dung dch.
Theo quy luat ng lng: V0CN,X = VRCN,R
T ay suy ra:
C N ,X =
VR C N ,R
V0
VR C N ,R
1000
m =
X
VR .C N ,R . X
1000
VR .C N ,R . X V
.
mX =
1000
V0
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 80 -
VR .C N ,R . X V 100
. .
X% =
1000
V0 a
Lu y: neu nong o bieu dien theo nong o phan t th phai chuyen sang nong
o ng lng roi tnh.
V du:
1- Tnh nong o phan t va so gam NaOH, biet rang khi chuan o 20ml dung
dch NaOH th ton 22,75ml dung dch HCl 0,1060N.
Giai:
NaOH
HCl
NaCl
H2O
X% =
CO2 +
H2O
2NaCl
VR .C N ,R . X V 100
. .
1000
V0 a
http://www.ebook.edu.vn
http://hoahocsp.tk
- 81 -
m =
C N ,R VR C N ,R ' VR '
1000
Neu lay a gam mau em hoa tan thanh Vml dung dch roi lay V0ml dung dch
tien hanh chuan o ngc nh tren th ham lng % cua chat X trong a gam mau
la:
X% =
C N ,R VR C N ,R ' VR '
1000
X .
V 100
.
V0 a
V du: Lay 0,211g Na2CO3 ky thuat cho tac dung vi lng d 25ml dung dch
HCl 0,2022N. Sau o chuan o lng HCl d th ton het 5,50ml dung dch NaOH
0,2089N. Xac nh ham lng % Na2CO3 trong So a ky thuat. Cho phan t lng
cua Na2CO3 = 106.
Giai: Ap dung cong thc tnh mX tren ta tnh c mNa2CO3 = 0,2070g
Vay Na2CO3% = 98,1%
3. Trng hp chuan o theo kieu khac:
Th tuy theo ieu kien cu the e tnh toan.
V du: e xac nh nong o cua SO42- trong 1 lt dung dch, ngi ta lay ra 20ml
dung dch roi them mot lng d 45ml dung dch BaCl2 0,05N e ket tua BaSO4
hoan toan. Loc bo tua BaSO4 va chuan Ba2+ d con lai trong dung dch bang
EDTA 0,05N ( pH = 0) th het 12ml. Tnh nong o ion SO42- va khoi lng ket
tua.
Giai:
Nong o ng lng cua SO42- = 0,0825N
Khoi lng ket tua: 0,1922g
http://www.ebook.edu.vn
http://hoahocsp.tk
- 82 -
http://www.ebook.edu.vn
http://hoahocsp.tk
- 83 -
2. ieu che cac dung dch t cac dung dch co nong o khac:
a) Pha loang dung dch:
Pha loang dung dch la them nc vao e dung dch co nong o thap hn .
Neu goi C1 va C2 lan lt la nong o cua dung dch trc va sau khi pha loang
toiday
V1 va V2 lan lt la the tch cua dung dch trc va sau khi pha loang
V lng chat tan la khong oi trong qua trnh pha loang nen ta co:
C1.V1 = C2.V2 trong o V2 = V1 + V H2O (dung e pha loang)
C1.V1 = C2 (V1 + VH2O)
Trong cong thc nay C1, C2 co the bieu dien theo cung nong o (CM, CN, TR,
TR/X) con V1 va V2 theo cung mot n v the tch (lit, ml)
Con neu C1, C2 bieu dien theo % khoi lng th:
Goi Q1 la khoi lng dung dch trc khi pha loang Q1 = a + q1
Q2 la khoi lng dung dch sau khi pha loang
C =P %=
a
a
.100 =
.100
a + q1
Q1
C =P %=
a
a
.100 =
.100
a + q2
Q2
C1
C2
P1
P2
Q2 = a + q2
a + q2
a + q1
Q2
Q1
C1
C2
1 =
Q2
Q1
C1 C 2
C2
Q 2 Q1
Q1
mH O
2
Q1
Trong o q1 , q2 la khoi lng dung moi trc va sau khi pha loang
mH2O la khoi lng nc can thiet e pha loang (lu y Q= V.d)
V du:
1. Can them bao nhieu ml nc vao 500ml dung dch HCl 0,122N e co c
dung dch HCl 0,100N.
Tra li VH2O = 110ml
2. Can lay bao nhieu ml H2SO4 ac 98% (d= 1,84g/ml) e ieu che 1 lt dung
dch H2SO4 5% ( d= 1,0g/ml)
Tra li: the tch H2SO4 can dung la 27,73ml
b) Pha tron dung dch:
Gia s tron V1 ml dung dch mot chat A nao o co nong o C1 vi V2 ml dung
dch chat o co nong o C2 th thu c V ml dung dch ( V = V1 + V2 ) co nong o
C
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 84 -
C1 Q 1
100
C2Q 2
100
C(Q1 + Q 2 )
100
(C1 C)Q1 = (C C 2 )Q 2
Q1
Q2
C C2
C1 C
- Neu nong o tnh theo % khoi lng , do lng chat tan khong oi nen :
V du:
1. Can them bao nhieu ml dung dch HCl ac 12N vao 200ml dung dch HCl
0,8N, e co dung dch HCl 1N.
Tra li: the tch HCl ac can lay la 3,64ml
2. Can them bao nhieu ml dung dch HNO3 54% (d = 1,33g/ml) vao 500ml dung
dch HNO3 14% (d = 1,08g/ml) e co dung dch HNO3 20%.
Tra li: the tch HNO3 54% can them la 71,65ml
BAI TAP
1- Can bao nhieu gam NaOH e pha 3lt dung dch NaOH 10% (d = 1,115)?
2- Can them bao nhieu ml nc vao 100ml dung dch HCl 20% (d = 1,10) e co
dung dch HCl 5%.
3- Co dung dch HCl 36,5% (d = 1,185)
a- Tnh so gam HCl nguyen chat trong moi ml dung dch.
b- Tnh nong o mol cua dung dch.
c- Tnh so ml dung dch tren can dung e pha 200ml dung dch HCl 3M
4- Tnh khoi lng NH3 nguyen chat co trong mot lt dung dch Amoniac
24,03% (d = 0,910g/ml). Can lay bao nhieu gam, bao nhieu ml dung dch tren e
pha 1lt dung dch 0,0500M.
5- Can 2,8614g Na2CO3.10H2O hoa tan trong nc thanh 250ml dung dch. Tnh
nong o ng lng cua dung dch o. Cho khoi lng phan t cua
Na2CO3.10H2O la 286,14g
6- Mot mau quang oxyt sat nang 0,5000g c lam ket tua di dang Fe(OH)3
va nung thanh oxyt sat III can nang 0,4980 g. Tnh lng sat di dang %Fe va
%Fe3O4
7- Hon hp NaCl, NaBr va tap chat can nang 1,0000g c hoa tan. Lam ket
tua cac halogenua bang dung dch AgNO3, lng tua thu c la 0,5260 g . Cho
kh Cl2 qua ket tua nay va un nong e bien AgBr thanh AgCl . Tat ca lng tua
thu c can nang 0,4260g. Tnh % NaCl va %NaBr trong mau
http://www.ebook.edu.vn
http://hoahocsp.tk
- 85 -
aHInd
[H + ][Ind ]
[HInd ]
[HInd ]
pH
pK
lg
[H + ] = K
aHInd
aHInd
[HInd ]
[Ind ]
[Ind ]
HInd
H+ + Ind-
T so [HInd ]/[Ind-] quyet nh mau sac cua dung dch, mat thng ch co the
phan biet c s oi mau khi ty so nay trong khoang t 1/10 en 10. Noi cach
http://www.ebook.edu.vn
http://hoahocsp.tk
- 86 -
khac mat thng nhn thay mau cua HInd khi [HInd] 10[Ind-] va thay mau cua
Ind- khi [Ind-] 10 [HInd]
Neu thay:
[HInd ]
[Ind ]
1
10
aHInd
Ka HInd
Khoang pH oi
mau
1,8.1010-5
-7
o trung tnh
10
Phenolphtalei
n
2.10-10
Mau
pT
4
3.1 4.4
4.4 6.2
7.0 7.4
8.0 10
Acid
o
o
5.5
7.2
9
Baz
Hong
Khong
mau
Vang
Vang
Luc
Tm
hong
http://www.ebook.edu.vn
http://hoahocsp.tk
- 87 -
Thng khi chuan cac acid hoac baz yeu hay chuan nhng dung dch acid, baz
rat loang ngi ta dung ch th hon hp. V du: metyl o 0,2% trong ru co
khoang pH oi mau 4,4 6,2. Nhng khi tron 1 the tch metyl o 0,2% trong ru
vi 1 the tch brom cresol cham 0,1% trong ru ta c ch th hon hp co khoang
pH oi mau t 4,9 (mau o nho) en 5,3 (mau luc), pT = 5,1.
Vay dung chat ch th hon hp cho ket qua chuan o chnh xac hn.
3. Ch th tong hp hay van nang:
La hon hp mot so chat ch th co mau bien oi nhieu lan cac gia tr pH khac
nhau. V du giay pH van nang la mot loai ch th hon hp gom 5 chat ch th acid
baz pha tron vi nhau theo nhng t le nhat nh. No co khoang chuyen mau t 1
14. Khi dung loai giay pH van nang ta ch can nho 1 giot dung dch can xac nh
pH len giay va oi chieu mau tren giay vi thang mau co san co ghi chu pH t o
biet c pH cua dung dch.
II. Chuan o acid manh bang baz manh va ngc lai:
1. Phng trnh ng chuan o:
a) Chuan acid manh bang baz manh:
Gia s chuan o V0 ml dung dch mot acid manh HA co nong o C0 bang mot
baz manh BOH co nong o C. Phan ng chuan o dang phan t va ion c viet
nh sau:
HA +
BOH
BA
H+ +
OH-
H2O
H2O
e tnh pH tai mot thi iem bat ky cua qua trnh chuan o ta dung phng
trnh ng chuan o sau:
F 1 = ([OH ] [H + ])
V0 + V
C 0 V0
(1)
F=
Neu biet the tch V cua baz manh a dung th tnh c F t o tnh c [H+]
va pH cua dung dch.
Bien luan: phng trnh ng chuan o co the n gian hn bang cach da
vao the tch baz manh a them vao tai thi iem ang xet n gian nhng ai
lng nho hn hoac pH thi iem bat ky co the tnh c bang cach xem xet tai
thi ang xet pH cua dung dch do chat nao quyet nh va ap dung nhng trng
hp a xet chng III.
* Khi cha them baz manh vao tc V = 0, nen F = 0. T phng trnh (1)
ta suy ra:
http://www.ebook.edu.vn
http://hoahocsp.tk
- 88 -
- C0 = [OH-] - [H+]
Vay:
[OH-] do nc phan ly khong ang ke nen co the bo qua nen : [H+] = C0.
pH = -lg C0
Hoac co the ly luan khi V = 0 dung dch ch co acid manh nen pH = -lgC0
* Khi a them baz manh nhng cha u e phan ng trung hoa xay ra
hoan toan ( trc va xa iem tng ng) khi o 0 < F < 1 tc la trong dung
F 1 = [H + ]
V0 + V
C 0 V0
[H + ] = (1 F )
C 0 V0
V0 + V
C 0 V0 + CV
V0 + V
dch con d H+ nen [H+] >> [OH-] do vay trong phng trnh (1) ta bo qua [OH-]
canh [H+] khi o:
Ma pH = -lg[H+] nen :
C V
pH = lg (1 F ) 0 0
V0 + V
* Tai iem tng ng : so milimol baz them vao = so milimol acid ban
au th F = 1, do vay [H+] = [OH-] = K H2O = 10 -7 ( 250C ) pH = 7
* Sau va xa iem tng ng: (F > 1) tc baz manh d nhieu, nen [OH-]
>> [H+], ta co the bo qua [H+] ben canh [OH-], nen phng trnh (1) tr thanh:
F 1 = [OH ]
V0 + V
C 0 V0
pOH = lg( F 1)
[OH ] = (F 1)
C 0 V0
V0 + V
C 0 V0
V0 + V
pH = 14 pOH = 14 + lg( F 1)
C 0 V0
V0 + V
* sat iem tng ng, th phai dung phng trnh tong quat (1) e tnh.
Lu y: khi o C0V0 CV
C0
C
C
C + C V + V0
V
V
0 +1
+1 0
V0
C
V0
C
V0
http://www.ebook.edu.vn
http://hoahocsp.tk
- 89 -
F 1 = ([OH ] [H + ])
V0 + V
C 0 V0
= ([OH - ] [H + ])
C0 + C
C0C
F 1 = ([H + ] [OH ])
V0 + V
(2)
C 0 V0
F=
Cung nh tren tuy theo tng trng hp cu the ma phng trnh ng chuan o
co the n gian hn.
* Khi a them acid manh nhng cha u e phan ng trung hoa xay ra
hoan toan ( trc va xa iem tng ng) khi o 0 < F < 1 tc la trong dung
dch con d OH- nen trong phng trnh (2) bo qua [H+] canh [OH-]
F 1 = [OH ]
V0 + V
C 0 V0
[OH ] = (1 F )
C 0 V0
V0 + V
C 0 V0 CV
V0 + V
F 1 = [H + ]
V0 + V
C 0 V0
[H + ] = (F 1)
C 0 V0
V0 + V
http://www.ebook.edu.vn
http://hoahocsp.tk
- 90 -
* sat iem tng ng: th phai dung phng trnh tong quat (2) e tnh
va co the thay:
C0
C
C
C + C V + V0
V
V
0 +1
+1 0
V0
C
V0
C
V0
7.
Khi VNaOH = 100,1; 101; 110; 200ml ap dung cong thc sau va xa iem
tng ng tnh c cac pH tng ng la: 9,7; 10,7; 11,68; 12,56.
b- Ve ng cong chuan o: la ve s phu thuoc cua pH (truc tung) vao F (truc
hoanh).
Qua hnh ve ta rut ra nhan xet :
pH
14
12
10
8
6
4
2
0
0.5
1.5
- ng chuan o tren ng vi
cac dung dch 0,1M, khi cac nong o
cang nho th bc nhay se cang ngan. Khi [acid] < 10-4 M th phai chu y en s phan
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 91 -
ly cua nc, tc la khong the bo qua [OH-] ben canh [H+] trong phng trnh tong
quat
- iem tng ng cua viec chuan acid manh bang baz manh luon luon =7
2. Sai so ch th - Cach chon chat ch th :
Trong qua trnh chuan o ngoai sai so the tch (do buret, pipet chia o sai hoac
do oc sai the tch ) con co sai so ch th.
Sai so ch th la sai so do pT cua chat ch th khong trung vi pH iem
tng ng. Ga tr sai so tng oi S c tnh nh sau :
S=
CV C 0 V0
C 0 V0
= F 1
S% =
CV C 0 V0
C 0 V0
100 = ( F 1)100
S% = [OH ]C [H + ]C
S% = [H + ]C
V0 + V
C 0 V0
100
S% = [OH ]C [H + ]C
S% = [OH ]C
) VC +VV 100
0
http://www.ebook.edu.vn
http://hoahocsp.tk
- 92 -
S% = [H + ]C [OH ]C
HA
HA +
BOH
BA
H2O
OH -
A-
H2O
(1)
F 1 = ([OH ] [H ])
F=
V0 + V
C 0 V0
[H + ]
[H + ] + K a
CV
C 0 V0
http://www.ebook.edu.vn
http://hoahocsp.tk
- 93 -
Trong o
va V la the tch baz a s dung
ay la phng trnh bac 3 kho giai, e n gian hn ta bien luan tng t
nh phan trc:
* Khi cha them NaOH : Tc la V = 0 suy ra F = 0; trong dung dch ch co
acid HA nong o [H+] >> [OH-] nen t phng trnh tong quat ta co the bo [OH-]
canh [H+] roi bien oi thanh
[H + ] =
K aC 0
K a + [H + ]
[H + ] = K a C 0
pH =
1
1
pK lg C
a
0
2
2
ay chnh la cong thc tnh [H+] cua mot n acid yeu HA co nong o C0
va hang so acid Ka
* Trc va xa iem tng ng F <1: Trong he gom HA con d va A- va
pH = pK lg
a
[HA ]
[A ]
CV
[HA ] =
V0 + V
V0 + V C V CV
1 F
pH = pK lg 0 0
= pK lg
a
a
CV
F
C 0 V0 CV
[A ] =
khi o pH cua dung dch do muoi nay quyet nh. ay la muoi tao thanh bi mot
acid yeu va mot baz manh, xem nh mot n baz yeu:
pOH = 0,5pKb - 0,5lgCb
pH = 14 - pOH = 14 - 0,5pKb + 0,5lgCb = 14 - 0,5(14 - pKa) + 0,5lgCb
C b = [A ] =
CC 0
CV
=
V0 + V C 0 + C
pH = 7 + 0,5pKa + 0,5lgCb
C C
1
1
pH = 7 + pK a + lg 0
2
2 C0 + C
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 94 -
* Sau va xa iem tng ng F >1: dung dch la hon hp baz yeu A- va baz
manh BOH d nen [OH-] >> [H+] dan en pH cua dung dch do baz manh quyet
nh.
[OH ] =
CV C 0 V0
V0 + V
* Sat trc hoac sau iem tng ng: 0.999 < F < 1.001 ch co the bo qua
pOH = lg[OH ] = lg
pH = 14 + lg
CV C 0 V0
V0 + V
CV C 0 V0
V0 + V
CV C V
C 0 V0
C 0 V0 CV
0 0
= 14 + lg
= 14 + lg
1
C V V +V V +V
C V
+
V
V
0
0
0 0 0
0 0
pH = 14 + lg( F 1)
F 1 = [OH ]
C 0 V0
V0 + V
V0 + V
C 0 V0
[H + ]
[H + ] + K a
S = FC 1 = [OH ]C [H ]C
V0 + V
)C V
0
[ H + ]C
K a + [ H + ]C
Tuy theo cac giai oan cua qua trnh chuan o ket thuc ma ta co the n gian
hn chang han :
+Trc va xa iem tng ng th [H+] va [OH-] thng nho hn ga tr
con lai nen co the bo qua, do o:
S = FC 1 =
[H + ]C
K a + [ H + ]C
S = [OH ]C
V0 + V
C 0 V0
http://www.ebook.edu.vn
http://hoahocsp.tk
- 95 -
S = FC 1 = [OH ]C
C0 + C
C0C
[H + ]C
K a + [ H + ]C
V du:
pH
14
12
10
8
6
4
2
0
0
0.5
1.5
http://www.ebook.edu.vn
http://hoahocsp.tk
- 96 -
manh. Acid cang yeu (Ka cang nho) va nong o acid cang loang th bc nhay
cang nho. Nong o cua dung dch baz dung e chuan cang nho dan en bc
nhay cang nho (do o pha loang ln) Trong thc te thng dung cac dung dch
chuan co nong o 10-2 M.
- ng cong chuan o acid yeu bang baz manh khong oi xng.
V du 1:
Tnh sai so ch th khi chuan o dung dch CH3COOH 0,1M (pKa = 4,76) bang
dung dch NaOH 0,1M neu ket thuc chuan o pH = 4,8 va pH = 9.
V du 2:
Can ket thuc chuan o trong khoang pH nao e sai so chuan o dung dch
CH3COOH 0,1M (pKa = 4,76) bang dung dch NaOH 0,1M khong qua 0,1%.
2. Chuan baz yeu bang acid manh:
Phan ng ch co tnh nh lng neu baz ng qua yeu va nong o baz khong
qua loang.
Gia s chuan V0 ml dung dch baz yeu co nong o C0 va hang so baz la Kb
bang acid manh co nong o C, th phng trnh ng chuan o co dang:
+
F 1 = ([H ] [OH ])
V0 + V
C 0 V0
[OH ]
K b + [OH ]
* Khi F = 0: th dung dch ch co baz yeu, tuy theo gia tr KB ma tnh pH bang
cac cong thc a hoc phan trc.
* Khi trc va xa iem tng ng 0 < F < 0,999: dung dch gom hon hp
baz yeu con d va acid lien hp (he em)
pH = 14 pK b + lg
Cb
CM
= 14 pK b + lg
pH = 14 pK + lg
b
C 0 V0 CV
CV
C V
= 14 pK b + lg 0 0 1
CV
1 F
F
* Tai iem tng ng F =1: dung dch la muoi c tao thanh bi baz yeu
va acid manh nen co the xem la n acid yeu
pH =
1
1
pK lg C
a
2
2
C C
1
1
pH = 7 pK b lg 0
2
2 C0 + C
http://www.ebook.edu.vn
http://hoahocsp.tk
- 97 -
[H + ] = (F 1)
C 0 V0
V0 + V
F 1 = [H ]
C0 + C
C0C
[OH ]
[OH ] + K b
V du: Ngi ta chuan o 100ml dung dch NH4OH 0,1N bang HCl 0,1N .Tnh
pH khi them 0ml, 90ml, 99ml, 100ml, 101ml, va 110ml HCl . Biet pK NH4OH = 4.75
IV. Chuan o mot a acid bang mot baz manh:
- Neu cac a acid co cac ga tr Ka1, Ka2, Ka3 khac nhau kha ln ( pKa 4 )
th co the chuan o lien tiep tng nac mot vi chat ch th thch hp nh khi chuan
o mot n acid. Acid H3PO4 thuoc loai nay.
- Neu cac a acid co cac ga tr Ka1, Ka2, Ka3 khac nhau khong nhieu ( pKa
2) th hai nac acid gan nh b trung hoa cung moc luc, ta ch co mot iem tng
ng. V du H2SO4, H2C2O4 thuoc loai nay.
V du: chuan H3PO4 0,1M bang NaOH 0,1M biet H3PO4 co pKa1 = 2,12; pKa2
=7,21; pKa3 =12,36.
Giai:
Cac ga tr pKa :
pKa2 - pKa1 = 5,09 > 4;
nen co the chuan o tng nac vi cac chat ch th thch hp. moi giai oan
trung hoa, xem dung dch nh mot n acid co pKa = pKa1 neu trung hoa nac 1,
pKa = pKa2 neu trung hoa nac 2
Nac mot : Neu trung hoa H3PO4 nac th nhat, tc ch xay ra phan ng
H3PO4 + NaOH
NaH2PO4 + H2O
pH = pK a1 lg
[H PO ]
3
4
[H PO ]
2
4
1 F
= pK a1 lg
http://www.ebook.edu.vn
http://hoahocsp.tk
F=
CV
C 0 V0
- 98 -
Khi F = 0,99:
th pH 0,99 =2,12 - lg(1-0,99)/0,99 = 4,12 ay la iem au cua bc nhay 1.
* F =1: tai iem tng ng 1:
Dung dch ch gom H2PO4-, v H2PO4va la acid cua he: H2PO4- / HPO42- co
pKa2 va la baz cua he: H3PO4 / H2PO4co pKa1.
pH
14
12
10
pH
T1
1
1
pK + pK = (2,12 + 7,21) = 4,67
a1
a2
2
2
4
2
0
0
Nac 2:
NaH2PO4 + NaOH
H2O
Na2HPO4
pH = pK a2 lg
[H PO
2
[HPO
]
4
2
pH = pK
a2
lg
2F
F 1
pKa3
pH =
ang Th Vnh Hoa
1
1
pK + pK = (7,21 + 12,36 ) = 9,79
a2
a3
2
2
http://www.ebook.edu.vn
http://hoahocsp.tk
- 99 -
Na2HPO4
pH = pK
pH = pK
a3
a3
lg
lg
+ NaOH
Na3PO4 + H2O
[HPO 4 2 ]
[PO 4 3 ]
3F
F2
S% =
[H + ]
K a1
100
S% =
Ka
[H ] c
100
S% =
[H + ]
Ka
100
S% =
Ka
+
[H ] c
100
V du: Neu dung metyl da cam (pT = 4), metyl o (pT = 5) va phenolphtalein
(pT = 9) lam ch th trong qua trnh chuan o acid H3PO4 0,1N bang dung dch
NaOH 0,1N th sai so ch th la bao nhieu ?
http://www.ebook.edu.vn
http://hoahocsp.tk
- 100 -
pOH = pK
b1
lg
1 F
F
- Neu F =1
1
pOH = ( pK + pK )
b1
b2
2
- Neu 1 < F < 2
pOH = pK
b2
lg
2F
F 1
- Neu F = 2
1
pOH = ( pK + pK )
b2
b3
2
Sai so :
* Trc iem tng ng 1 :
S% =
K a2
[ H + ]C
100
[H + ]
S% =
100
K a1
* Trc iem tng ng 2 :
S% =
K a1
[H + ]C
100
http://www.ebook.edu.vn
http://hoahocsp.tk
- 101 -
[H + ]
S% =
100
K a2
V du: chuan Na2CO3 0,1M bang HCl 0,1M. Hoi pHT1 =? , pHT2 =? Chon
ch th cho qua trnh chuan o nay nh the nao? H2CO3 co pKa1 = 6,35, pKa2 =
10,22.
VI. Chuan o hon hp hai acid:
1. Hon hp hai acid manh:
V du (HCl + HNO3), (HCl + HClO4 )
Ca hai acid eu rat manh nen ca hai eu b trung hoa cung mot luc, ta ch co
mot iem tng ng. Do o khong the xac nh tng acid rieng le, ma xac nh
tong nong o hai acid.
2. Hon hp mot acid yeu va mot acid manh:
V du (HCl + CH3COOH) vi hon hp nay ta cung ch co mot iem tng
ng.
3. Hon hp mot a acid va mot acid manh:
V du (HCl + H3PO4)
Nac 1 cua H3PO4 khong qua yeu nen nac nay b trung hoa cung mot luc vi
HCl:
HCl + NaOH
NaCl + H2O
H3PO4 + NaOH
NaH2PO4 + H2O
pKa2
pKa1
pKa3
http://www.ebook.edu.vn
http://hoahocsp.tk
- 102 -
Neu pKa la kha ln va hai acid co cung mot nong o th neu pKa 4 th co
the chuan rieng tng acid mot.
VII. Chuan o hon hp hai baz:
Cung giong nh trng hp cua cac hon hp acid , ang chu y nhat la hon hp
baz manh va baz yeu hoac a baz v du NaOH va Na2CO3, nac 1:
NaOH
+ HCl
Na2CO3 + HCl
NaCl + H2O
NaHCO3 + NaCl
pKa2
H2CO3 + NaCl
pH cua dung dch do acid yeu H2CO3 quyet nh, co the xem nh mot n
acid yeu
pH = 0,5. 6,35 - 0,5 lgCH2CO3 nen chon metyl da cam lam chat ch th
BAI TAP
1- 15ml dung dch HNO3 0,0200M c chuan o bang dung dch KOH 0,0100M.
a- Tnh pH cua dung dch tai iem tng ng
b- Tnh the tch dung dch KOH a dung e at iem tng ng.
c- Tnh pH cua dung dch tai thi iem a them 10; 35ml dung dch KOH.
2- Chuan o 25,00ml dung dch CH3COOH 0,01M bang dung dch NaOH 0,05M.
a- Tnh the tch dung dch NaOH can dung e at iem tng ng
b- Tnh pH tai iem tng ng.
Cho acid CH3COOH co pKa = 4,76
3- Mot mau NaOH a b cacbonat hoa mot phan can nang
0,9184g c pha thanh 250ml dung dch. Lay 25ml dung dch
va pha chuan o bang dung dch HCl 0,1042N. Biet rang:
- Neu dung ch th phenolphtalein th the tch HCl tieu ton la 20,70ml
- Neu dung ch th metyl dacam th the tch HCl tieu ton la 21,48ml
Xac nh ham lng phan tram cua NaOH va Na2CO3 trong mau
4- Chuan o 20ml dung dch Na2CO3 0,1M bang dung dch HCl 0,1M
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 103 -
a- Tnh pH cua dung dch sau khi them 19,98; 20; 20,02ml dung dch HCl.
b- Nhng chat ch th co khoang pH oi mau bang bao nhieu co the dung cho
s chuan o tren e co sai so ch th < 0,1%.
Cho H2CO3 co pK1 = 6,35; pK2 = 10,32
http://www.ebook.edu.vn
http://hoahocsp.tk
- 104 -
Cl-
HgCl+
HgCl+
Cl-
HgCl2
Hg2+
4I-
HgI42-
2CN-
Ag(CN)2-
- Sau khi CN- a phan ng het vi Ag+, neu tiep tuc them Ag+ vao dung
dch th se xay ra phan ng tao ket tua trang:
Ag+
Ag(CN)2-
Ag[Ag(CN)2] trang
S xuat hien ket tua trang lam uc dung dch va o la dau hieu ch th cho viec
ket thuc s chuan o. Phng phap nay cung t s dung nen khong xet.
3. Phng phap complexon:
Phng phap nay da tren kha nang tao phc ben gia ion kim loai can xac
nh vi cac thuoc th hu c co ten goi chung la complexon, ay la phng phap
c ng dung rong rai trong phan tch nen chung ta xet ky phng phap nay.
http://www.ebook.edu.vn
http://hoahocsp.tk
- 105 -
CH2 COOH
N
CH2 CH2 N
CH2 COOH
Nhng do H4Y t tan trong nc nen trong thc te ngi ta hay dung muoi
dinatri cua no goi la complexon III (con goi la Trilon B) viet tat Na2H2Y
HOOC CH2
NaOOC CH2
CH2 COONa
N
CH2 CH2 N
CH2 COOH
Cac complexon tao phc ben vi hang chuc ion kim loai. Cac phan ng nay
thoa man cac ieu kien cua phan ng dung trong phan tch the tch. V vay
phng phap nay rat pho bien.
1. Nguyen tac cua phng phap:
Complexon III phan ly hoan toan trong nc tao thanh:
Na2H2Y
2Na+
H2Y2-
V vay noi en dung dch complexon III la noi en H2Y2Trong phng phap nay can phai s dung nhng chat ch th mau kim loai e
nhan ra iem tng ng. Nh vay khi cho ch th vao dung dch can phai phan
tch th ion kim loai can xac nh se phan ng vi ch th tao thanh mot phc co
mau. Khi chuan bang H2Y2- th thuoc th nay se ay ch th ra khoi phc mau va
tao thanh e tao thanh phc MeY2- khong mau ben hn. Nh vay iem cuoi cua
phep chuan o, chat ch th mau kim loai dang t do se c giai phong ra. V
vay khi dung dch chuyen t mau cua phc gia ch th vi kim loai sang han mau
cua ch th t do th o la thi iem ket thuc chuan o. Do o ieu kien can thiet
cho viec chuan complexon trc tiep la hang so ben cua phc gia kim loai vi
H2Y2- phai ln hn o ben cua phc gia kim loai vi ch th.
Khi dung phng phap nay e chuan cac kim loai hoa tr 3, 4 th nen tien hanh
trong moi trng acid v cac complexonnat cua kim loai hoa tr 3, 4 ch ben trong
moi trng acid con trong moi trng kiem chung de dang thuy phan tao ra cac
phc hydroxo. Con ngc lai cac complexon nat cua kim loai hoa tr 2 ch ben
trong moi trng kiem . Do o oi vi moi ion kim loai can phai tien hanh chuan
o trong moi trng co pH thch hp. Du cac ion kim loai co hoa tr khac nhau
http://www.ebook.edu.vn
http://hoahocsp.tk
- 106 -
nhng 1 ion gam kim loai luon luon tng tac vi 1 ion gam complexon III ong
thi giai phong ra 2H+.
Me2+ +
H2Y2-
MeY2-
+ 2H+
Me3+ +
H2Y2-
MeY-
+ 2H+
Me4+ +
H2Y2-
MeY
+ 2H+
Cho nen ng lng gam cua kim loai va complexon eu bang phan t
lng cua chung chia cho 2.
2. Cac ch th thng dung trong chuan o complexon:
e nhan ra iem tng ng trong phng phap complexon ngi ta hay
dung nhat la cac ch th mau kim loai, o la nhng chat mau hu c co kha nang
tao vi ion kim loai phc (cang cua) co mau, va trong nhng ieu kien xac nh
mau cua phc o khac vi mau cua chat ch th t do.
Cac chat ch th mau kim loai thng la nhng acid yeu hoac baz yeu, v vay
mau cua ch th cung phu thuoc vao pH cua dung dch. Do o khi chuan mot ion
kim loai nao o bang phng phap complexon can chon pH thch hp e
phan ng tao phc gia ion kim loai va complexon III xay ra hoan toan va
mau cua ch th t do phai tng phan vi mau cua phc gia no vi ion kim
loai e de nhan ra diem tng ng v the can dung nhng dung dch em.
Nhng ch th thng dung gom :
a) Eriocrom T en (ETOO hoac NET)
La mot a acid yeu ky hieu la H3Ind. Trong dung dch nc no phan ly va co
mau thay oi theo pH
H2Ind-
H3Ind
HInd2-
Ind3-
Xanh biec
Da cam
Trong khoang pH t 7 11 ch th nay ton tai dang HInd2- co mau xanh con
phc cua cac ion kim loai vi ch th co mau o (s chuyen mau o- xanh hoac
xanh - o la tng phan) v vay khi dung ch th nay ngi ta hay tien hanh moi
trng pH = 10. pH nay ch th (HInd2- ) se tao vi ion kim loai phc co mau o
nho
Me2+
HInd2Xanh
MeInd- + H+
o nho
Khi chuan bang complexon III phc MeInd- b pha v ion kim loai ket hp vi
complexon III tao thanh mot phc ben hn con HInd2- c giai phong ra va tch
luy lai trong dung dch lam cho dung dch co mau xanh
MeInd- +
o nho
H2Y2-
MeY2-
HInd2- +
H+
Xanh
Vay ket thuc chuan o khi dung dch chuyen t mau o nho sang xanh biec, e
duy tr pH t 8 10 ngi ta thng dung he em NH4OH - NH4Cl
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 107 -
b) Murexit:
Thng viet tat la H4Ind- trong nc no phan ly nh sau:
H4Ind-
H3Ind2-
Tm hong
H2Ind3-
Tm
Xanh tm
pH < 9 : ch th co mau tm
pH > 9 : ch th co mau xanh tm
Tuy theo nhng kim loai khac nhau ma phc tao thanh gia ch th nay vi ion
kim loai se co mau khac nhau, chang han ch th nay se tao vi Ca2+ mot phc co
mau o, vi Co2+, Ni2+, Cu2+ phc co mau vang. V vay e tao s chuyen mau
tng phan th khi chuan Ca2+ bang complexon III vi ch th murexit nen tien
hanh moi trng pH > 9 th se ket thuc chuan o khi dung dch chuyen t o
sang xanh tm ( ro hn s chuyen t o sang tm hong ) oi khi tien hanh nhng
pH = 9 se chuyen t mau o sang tm. Khi chuan Co2+, Ni2+ , Cu2+ th tien hanh
moi trng pH < 9 (cu the t 7 8) th ket thuc chuan o khi dung dch chuyen t
vang sang tm.
c) Acid Sulfosalicylic:
Viet tat la H3Ind (oi khi ngi ta viet H2Sal) dung dch cua no khong mau, ch
th nay dung trong qua trnh chuan o Fe3+ trong moi trng acid, v pH = 1 3
ch th nay tao vi Fe3+ mot phc co mau tm am. Ket thuc chuan o khi dung
dch chuyen t mau tm sang vang (rat nhat).
III. Phng trnh ng chuan o trong phng phap complexon:
ng chuan o la ng bieu dien s bien thien cua lng ion kim loai M
theo lng thuoc th them vao, tc la bieu dien s bien thien cua pM theo F.
Trong o pM = -lg[M] con F la mc o ion kim loai c chuan o.
Ga s chuan o V0 ml dung dch muoi kim loai M co nong o phan t C0 bang
dung dch complexon III co nong o phan t C th F = CV/ C0V0 trong dung dch
se xay ra cac can bang sau:
* Can bang tao phc chnh gia Mn+ va Y4Mn+ +
M
Y4-
MY
H+
HY3-
K4
HY3-
H+
H2Y2-
K3
H2Y2- +
H+
H3Y-
K2
H3Y-
H+
H4Y
K1
ML
: 1
http://www.ebook.edu.vn
http://hoahocsp.tk
- 108 -
ML
ML2
: 2
M Ln-1
MLn
: n
V0 + V
C 0 V0
(1)
Trong o : [M], [Y] la tong nong o can bang cua cac dang cua ion kim loai
va cua EDTA (tr dang phc MY)
[Y] = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]
[H + ] [H + ]2
[H + ]3
[H + ] 4
= 1+
+
+
+
H
K4
K 4 K 3 K 4 K 3K 2 K 4 K 3K 2 K1
[Y]=[Y].H
[M] = [M] + [ML] + [ML2] + ..+ [MLn]
[M]=[M]. L
L = 1 + 1 [L ] + 1 2 [L ]2 + .... + 1 2 ... n [L ]n
Mat khac khi them V ml dung dch EDTA vao th nh luat bao toan khoi
lng vi M
C 0 V0
[MY ] =C V
[M ' ]
V00 +0 V
V0 + V
[M ' ]
[MY ]
[MY ] V0 + V
' =
[ Y' ] =
=
[M' ][Y' ]
' [M' ]
' [M' ]
[M' ] + [MY ] =
C 0 V0
C 0 V0
[M ' ]
V +V
V +V
F 1 = 0
[M ' ] 0
' [M' ]
C 0 V0
http://www.ebook.edu.vn
http://hoahocsp.tk
(2)
- 109 -
Bien luan :
- Khi F =0 (cha them complexon) luc nay dung dch ch cha M
pM = -lg[M] = -lgC0
- Khi F < 1: luc nay F -1 < 0 : Trc va xa iem tng ng [Y] << [M] trong
phng trnh (1) co the bo qua [Y] canh [M] suy ra :
F 1 = [M' ]
V0 + V
C 0 V0
[M' ] = (1 F )
C 0 V0
V0 + V
[M ] =
[M ' ]
- Khi F > 1 : luc nay F -1 >0 : Sau va xa iem tng ng [Y] >>[M] t (1)
suy ra
F 1 = [Y' ]
V0 + V
C 0 V0
[Y' ] = (F 1)
C 0 V0
V0 + V
C 0 V0
[M ' ]
V +V
V +V
F 1 = 0
0
' [M' ]
C 0 V0
[M' ] =
1
' (F 1)
Biet [M] co the suy ra [M]. Sau iem tng ng cang ln nen pM
cang ln dan en bc nhay cang ln nen phep chuan o cang chnh xac.
- Khi F =1: Tai iem tng ng; luc nay [M] = [Y]
C 0 V0
[M ' ]
V +V
[M ' ] = 0
' [M' ]
http://www.ebook.edu.vn
http://hoahocsp.tk
[M' ] <<
C 0 V0
V0 + V
- 110 -
Suy ra :
C 0 V0
V +V
1 C 0 V0
[M ' ] = 0
[
M
'
]
=
' V + V
' [M' ]
0
canh
- Khi 0,999 < F < 1,001 (Sat iem tng ng) Ch co the bo qua [M]
C0V0/(V0 + V)
C V
V +V
V +V
1
1
) [M ' ] 0
F 1 = 0 0 (
=
[M ' ] 0
V + V ' [M' ]
C V
C 0 V0
' [M' ]
0
0 0
BAI TAP
1- Chuan o 100 ml dung dch muoi Mg 10-2 M, em bi hon hp NH4OH NH4Cl e gi pH = 10, bang dung dch EDTA 10-2 M. Tnh pMg tai cac thi iem
khi them 0; 25; 50; 75; 90; 99; 100; 101ml dung dch EDTA. T o ve c
ng cong chuan o. Biet rang MgY2- = 108,7 ; H4Y co K1= 10-2, K2 = 10-2,67 K3 =
10-6,27 K4 = 10-10,3
2- Tnh pZn tai iem tng ng khi chuan o dung dch Zn2+ 2.10-2M bang
dung dch EDTA co cung nong o c em bi hon hp NH4OH - NH4Cl e gi
pH = 10, nong o can bang cua NH3 la 0,1M. Phc cua Zn2+ va NH3 ton tai trong
dung dch ch dang co so phoi tr cc ai la 4.
Cho ZnY2- = 1016,5 ; 1,4 = 108,7 ; H4Y co K1= 10-2, K2 = 10-2,67 K3 = 10-6,27 K4 = 10-10,3
3- Tnh sai so khi chuan o dung dch CaCl2 10-2M bang dung dch EDTA 102
M pH bang 12, neu ket thuc chuan o khi pCa bang 7,5. Biet CaY2- = 1011 ; H4Y
co K1= 10-2, K2 = 10-2,67 K3 = 10-6,27 K4 = 10-10,3
http://www.ebook.edu.vn
http://hoahocsp.tk
- 111 -
I. Nguyen tac - Phan loai cac phng phap chuan o ket tua:
1. Nguyen tac :
Phng phap chuan o ket tua da tren cac phan ng tao thanh hp chat t tan.
Cac phan ng nay phai thoa man cac ieu kien sau:
- Phan ng phai xay ra hoan toan, ngha la hp chat tao thanh phai khong tan
(T< 10-10) va phai co cong thc xac nh.
- Toc o phan ng phai kha ln (ngha la khong co hien tng qua bao
hoa).
- Phan ng phai chon loc, hien tng hap thu khong c anh hng ang
ke en ket qua phan tch.
- Phai co chat ch th thch hp cho phep xac nh c iem tng ng
cua phep chuan o.
2. Phan loai cac phng phap chuan o ket tua:
* Phng phap Bac: la phng phap hay dung nhat hien nay, thuoc th c
s dung la dung dch AgNO3 dung e chuan cac halogenua Cl-, Br-, I-, va SCN-. V
vay ay la phng phap pho bien nen chung ta ch va se xet ky phng phap
nay trong phan chuan o ket tua.
* Phng phap thuy ngan: dung dch chuan la Hg2(NO3)2 e xac nh Cl-, I-.
Hg22+
2X-
Hg2X2
Ngoai ra oi khi ngi ta con dung dung dch K4[Fe(CN)6] e xac nh Zn2+,
da vao phan ng:
K4[Fe(CN)6]
Zn2+
K2Zn3[Fe(CN)6]2
MX
AgX + MNO3
Ag+ + NO3- + M+ + X-
AgX
+ M+ + NO3-
Cac ion M+ va NO3- khong anh hng en qua trnh chuan o nen khong e
AgX
cap en ta ch quan tam en : Ag+ + XCac ion X-, Ag+ va ket tua AgX lien he vi nhau theo cac phng trnh sau :
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 112 -
[Ag + ] + [AgX] =
[X ] + [AgX] =
CV
V0 + V
C 0 V0
[Ag + ] [X ] =
CV C 0 V0
V0 + V
V0 + V
T o suy ra :
[Ag + ] [X ] =
F=
C V
C V CV
CV C 0 V0
0 0 = 0 0
1
C 0 V0 V0 + V V0 + V V0 + V C 0 V0
CV
C 0 V0
V0 + V
)C V
F 1 = [Ag + ] [ X ]
Vi
T phng trnh (1) suy ra : [X-] = TAgX / [Ag+] the vao ta c :
Hai phng trnh tren dung e khao sat s bien thien cua pAg = - lg[Ag+] hoac
pX = -lg[X-] theo F. o goi la phng trnh ng chuan o.
V +V
AgX 0
F 1 = [Ag + ]
[Ag + ] C 0 V0
Bien luan :
- Trc va xa iem tng ng (F < 1): [X-] >> [Ag+]
F 1 = [X ]
V0 + V
C 0 V0
Suy ra :
[X ] = (1 F )
C 0 V0
V0 + V
[Ag + ] =
http://www.ebook.edu.vn
http://hoahocsp.tk
TAgX V + V
0
1 F C 0 V0
- 113 -
[X ] = [Ag + ] = TAgX
F 1 = [Ag + ]
V0 + V
C 0 V0
- Sau va xa iem tng ng (F >1) trong dung dch Ag+ d cho nen [Ag+]
>>[X-]
Do vay :
- Sat iem tng ng 0,999 < F < 1,001 :
F 1 = [Ag + ] [X ]
[Ag + ] = (F 1)
C0 + C
C0C
C 0 V0
TAgX V + V
[X ] =
( 0
)
F 1 C 0 V0
V0 + V
S = [X ]C
V0 + V
C V
0
TAgX
V0 + V
[Ag + ]C C 0 V0
S = [Ag + ]
V0 + V
C 0 V0
S = [Ag + ] [X ]
C0 + C
C0C
http://www.ebook.edu.vn
http://hoahocsp.tk
- 114 -
V du :
1. Tnh pAg khi them 0 ; 50 ; 90 ; 99 ; 99,9 ; 100 ; 100,1 ; 101 ; 110 ; 150 ml dung
dch AgNO3 0,1M vao 100 ml dung dch NaCl 0,1M.
2. Ve ng chuan` o pAg = f(F)
3. Tnh sai so cua phep chuan o khi ket thuc chuan o tai pAgc = 4,3
4. e /S%/ 0,2% th phai ket thuc chuan o trong khoang pAg bang bao
nhieu . Cho TAgCl = 1,6.10-10 = 10-9,8.
Giai:
1- Tnh pAg tai cac thi iem khi VAgNO3 = 0; 50; 90; 99; 99,9; 100; 100,1; 101;
110; 150 c cac gia tr tng ng: 0; 8,4; 7,52; 6,50; 5,5; 4,9; 4,3; 3,3; 2,3; 1,7.
2- Ve ng chuan o:
3- Tnh sai so:
pAg
9.8
4.9
0
0
n g cong chua n o
pAg=f (F)
3. Cac phng phap xac nh iem cuoi trong phng phap o Bac:
a) Phng phap Mohr:
Dung K2Cr2O4 lam ch th, tai iem cuoi chuan o se xuat hien ket tua
Ag2CrO4 mau o gach, dung e xac nh Cl- , Br-.
Nguyen tac them vao dung dch can xac nh (dung dch muoi cua Cl-, Br-) ch
th CrO42-. Khi chuan o bang dung dch AgNO3 se xay ra cac phan ng:
Ag+ + X- (Cl- , Br-)
Ag+d + CrO42-
AgX
(1)
http://www.ebook.edu.vn
http://hoahocsp.tk
- 115 -
Ket thuc qua trnh chuan o khi dung dch chuyen t mau trang uc cua AgCl
hoac vang nhat cua AgBr sang o gach cua Ag2CrO4.
Van e quan trong ay la phai tnh nong o CrO42- nh the nao e cho phan
ng th (2) xay ra ngay ung tai iem tng ng? Khi cho AgNO3 vao dung
dch gom Cl- (hoac Br-),CrO42- ket tua nao se xuat hien trc AgCl ? Ag2CrO4 ?
V o tan cua AgCl va Ag2CrO4 lan lt la SAgCl = 1.33.10-5 va SAg2CrO4 = 6.5.105
do vay d nhien la AgCl ket tua trc tuy nhien do chung khong khac nhau
mc o cho phep e cho chat nay ket tua hoan toan roi mi xuat hien ket tua kia.
V vay ay can phai xac nh [CrO42-] can thiet e cho Cl- c ket tua hoan
toan va ket tua cua CrO42- vi Ag+ phai xuat hien tai iem tng ng.
Tai iem tng ng: [Ag+] = [Cl-] = (TAgCl )1/2 = 10-4.875 Khi Ag2CrO4 bat au
xuat hien th nong o ban au cua CrO42- = TAg2CrO4 /[Ag+]2 =10-2,2 M.
Vay e cho Cl- c ket tua hoan toan va e Ag2CrO4 xuat hien tai iem tng
ng th [CrO42-] = 10-2,2M = 6.31.10-3 M. Phng phap Mohr c dung e
nh lng Cl-, Br- nhng khong c dung e xac nh I- va SCN- v ket tua AgI
va AgSCN hap phu manh CrO42- lam cho s chuyen mau xay ra trc iem tng
ng va iem tng ng khong ro rang gay ra sai so ln. S chuan o theo
phng phap Mohr can phai c tien hanh trong moi trng trung tnh hoac baz
yeu, v :
- moi trng acid (pH thap), o nhay cua ch th giam do o tan Ag2CrO4
tang
Ag2CrO4
CrO42- + H+
2Ag+
CrO42-
HCrO4-
AgOH
Thng ngi ta hay dung dung dch NaHCO3 e tao moi trng, vay pH cua
dung dch NaHCO3 la bao nhieu ?
Lu y :
- Neu trong dung dch chuan o co NH4+ th phai chuan o trong moi trng
pH = 6,5 7,2 v neu pH > 7,2 th se co s tao thanh NH3 va NH3 se tao phc
ben vi ion Ag+ gay sai so
- Dung dch chuan o khong c cha cac ion can nh : nhng ion co the
phan ng c vi CrO42- nh Ba2+ , Pb2+ , va khong co nhng anion co the
tao ket tua vi Ag+ nh CO32- , C2O42- , PO43- neu co , chung ta phai tm cach
che .
http://www.ebook.edu.vn
http://hoahocsp.tk
- 116 -
HFl
Trc iem tng ng cac hat keo mang ien tch am (-), nen cac anion
Fl cua fluorescein khong b hap phu. Sau iem tng ng cac hat keo mang
ien tch dng (+) nen cac anion Fl- b hap phu :
-
(AgCl)nAgx+x +
Fl-
xanh luc
{(AgCl)nAgxx+}xFlMau hong
Lu y : Khong phai dung dch chuyen t xanh luc sang hong ma sau iem
tng ng do s hap phu tren be mat tua nen tua se co mau hong.
ieu kien cua nhng chat ch th hap phu la :
- Phai va ch hap phu tai iem tng ng
- Moi trng dung dch phai thch hp e dang b hap phu ton tai c
(thng pH <10)
Hien tng t hap phu se tang khi dien tch be mat cua hat keo tang len.
Nen trong thc te ngi ta hay them ho tinh bot hoac Dextrin e tang dien tch
be mat va gi tua AgX trang thai keo.
c) Phng phap Volhard :
Nguyen tac: Them mot lng d dung dch AgNO3 a biet nong o chnh
xac vao dung dch X-, roi chuan lng Ag+ d bang dung dch SCN- (NH4SCN
hoac KSCN) vi ch th la Fe3+. Cac phan ng cua qua trnh chuan o:
Ag+
Ag+d
+ X-
AgX
+ SCN-
SCN- d + Fe3+
=10-2,14 )
AgSCN
TAgSCN = 1,1.10-12
Vay iem tng ng la luc dung dch chuyen sang mau hi hong.
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 117 -
V TAgSCN = 1,1.10-12 < TAgCl =10-9,75 nen co the xay ra phan ng:
AgCl
+ SCN-
AgSCN + Cl-
e ngan nga phan ng nay, ta phai loc tua AgCl trc khi chuan Ag+d
bang SCN-.Ngoai cach loc bo tua AgCl ngi ta co the cho them mot t
Nitrobenzen, chat nay se bao quanh AgCl ngan khong cho AgCl phan ng vi
SCN-.
Mat chung ta ch nhan ra mau hong iem tng ng khi:
[Fe(SCN)2+] 6,4.10-6M.
Nh vay phng phap Volhard co the dung e xac nh trc tiep Ag+ (dung
dung dch chuan KSCN vi chat ch th la Fe3+) ngoai ra no con co the xac nh
Cl-, Br-, I-, theo phng phap chuan o ngc khi o:
CN
=
X
(C N V) AgNO 3 (C N V) SCN
V
Khac vi 2 phng phap trc, phng phap nay thc hien trong moi trng
acid (0,1-1 N ) e ngan nga s thuy phan cua muoi Fe3+.
BAI TAP
1- Hoa tan a(g) NH4Cl tinh khiet thanh 200ml dung dch mau. Lay 20ml dung
dch nay cho tac dung vi 40ml dung dch AgNO3 0,050N. Lng AgNO3 d c
chuan o bang 12,50ml dung dch NH4SCN 0,1000N. Tnh lng a(g) mau a can.
Cho phan t lng cua NH4Cl bang 53,49.
2- Tnh sai so mac phai khi chuan o 50ml dung dch NaCl 0,1M bang dung dch
AgNO3 0,1M, neu ket thuc viec chuan o tai pAg = 4,9 va 5,25. Cho TAgCl =
1,1.10-10.
3- Tnh xem ta co the chuan o tng muoi co trong hon hp NaCl, NaBr, NaI
moi muoi co nong o 0,1M bang dung dch AgNO3 0,1M vi o chnh xac la bao
nhieu.
Cho TAgCl = 1,1.10-10, TAgBr = 4.10-13 , TAgI = 1,5.10-16
http://www.ebook.edu.vn
http://hoahocsp.tk
- 118 -
+ n1Kh2
n2Kh1 + n1Ox2
Kh1
Ox2
n1 , n2 la so electron trao oi .
Phan ng chuan o phai thoa man nhng yeu cau cua phan ng dung trong
phan tch the tch. Viec tnh toan nong o chat oxy hoa hay chat kh tuan theo quy
luat ng lng (V.CN)X = (V.CN)R . Cung nh cac phng phap khac, phai co
chat ch th e xac nh iem cuoi.
II. Chat ch th Oxy hoa -kh :
Trong phng phap oxy hoa - kh co trng hp khong can s dung chat ch th
ma van nhan ra iem cuoi. o la trng hp :
- Dung dch chuan co mau bien oi ro ret luc phan ng ket thuc
V du khi chuan cac chat kh (Fe2+) bang KMnO4, mot giot dung dch KMnO4 d
se lam cho dung dch co mau hong o la dau hieu e ket thuc chuan o.
- Mot trong hai dang oxy hoa hoac kh tao chat mau vi mot chat khac. V
du khi chuan cac chat kh bang dung dch iod, mot giot dung dch chuan d se
tao vi ho tinh bot mot chat mau xanh tm.
Con trong a so trng hp phai dung chat ch th.
Chat ch th oxy hoa -kh la nhng chat ma dang oxy hoa va dang kh co
mau khac nhau. Mau sac cua chat ch th bien oi phu thuoc vao the oxy hoa
cua dung dch.
http://www.ebook.edu.vn
http://hoahocsp.tk
- 119 -
Neu ky hieu mau cua dang oxy hoa la IndOx va dang kh la IndKh th co the
bieu dien s bien oi tng ho gia chung bang phng trnh :
+ ne-
IndOx
IndKh
IndOx va IndKh la mot cap oxy hoa -kh lien hp . Phng trnh Nerst oi vi
cap Oxy hoa - kh lien hp nay nh sau:
E = E0 +
0,059 [Ind Ox ]
. lg
n
[Ind Kh ]
Khi them vao dung dch cua chat oxy hoa hay chat kh 1 en 2 giot ch th
th ng vi mot the nhat nh cua dung dch se co mot ty so [IndOx]/[IndKh]. Luc
o dung dch se co mau tng ng vi ty so nay .
Khi chuan o dung dch mot chat oxy hoa nao o bang chat kh va ngc
lai th gia tr the E cua dung dch thay oi va ket qua la ty so [IndOx]/[IndKh]
cung thay oi . Cung nh ch th acid-baz , mat ta ch co the nhan c mau
cua dang nao o cua ch th khi nong o cua dang nay ln hn 10 lan hay nho
hn 10 lan so vi dang kia
Khi
[Ind Ox ]
[Ind
Kh
10 th E = E 0 +
0,059
lg 10
n
= E0 +
0,059
n
[Ind Ox ]
[Ind
Kh
1
10
th E = E 0 +
0,059 1
lg
n
10
= E0
0,059
n
NH
http://www.ebook.edu.vn
http://hoahocsp.tk
- 120 -
NH
NH
NH
-2e-
2H
Eo = 0,76V
* Acid N-PhenylAnthranilic :
C che oi mau giong cac
ch th tren dang kh khong
mau , dang oxy hoa co mau
hong tm .
NH
Eo = 1,08 V pH = 0
COOH
+ n1Kh2
n2Kh1 + n1Ox2
Kh1
Kh2 -
Ox2
n2 e
http://www.ebook.edu.vn
http://hoahocsp.tk
- 121 -
F 1 =
[Ox1 ] [Kh 2 ]
[Kh 1 ] [Ox 2 ]
1+
[Kh 2 ]
[Ox 2 ]
F=
NV
N 0 V0
Bien luan:
* 0 < F < 1 Trc va xa iem tng ng: Do hang so toc o phan ng
ln nen co the coi phan ng chuan o xay ra hoan toan [Ox1] 0. Chat Ox1 thieu,
Kh2 d nen tnh the theo cap Ox2/Kh2
0
E = E ox
+
2 / kh 2
0,059 [ox 2 ]
0,059
F
0
lg
= E ox
+
lg
2 / kh 2
n2
[kh 2 ]
n2
1 F
* F > 1 Sau iem tng ng, [Kh2] 0,V Ox1 d nen tnh the theo cap
0
E = E ox
+
1 / kh1
0,059 [ox1 ]
0,059
0
lg
= E ox
+
lg( F 1)
1 / kh1
n1
[kh 1 ]
n1
Ox1/Kh1
* F =1 Tai iem tng ng
Neu trong phan ng chuan o co s tham gia cua ion H+ theo dang:
* Ox1 + n1e + mH+
Kh1 + m/2H2O
n E0
1 ox1 / kh1
+ n E0
2
n1 + n 2
Kh2 -n2e
ox 2 / kh 2
Ox2
Kh1
http://www.ebook.edu.vn
http://hoahocsp.tk
- 122 -
Ox2 + mH+
n E0
1
ox1 / kh1
+ n E0
2
n1 + n 2
ox 2 / kh 2
0,059
lg[H + ]m
n1 + n 2
E(V)
1.4
1.2
1
Tnh the tai cac thi iem khi the tch cua
dung dch Ce4+ bang 50; 90; 99; 99,9; 100; 100,1;
110; 200ml c cac gia tr E tng ng: 0,77;
0,83; 0,89; 0,95; 1,105; 1,26; 1,38; 1,44.
T cac gia tr tren ve c ng chuan o
0.8
0.6
0.4
0
* Sai so ch th :
S = FC 1 =
NV N 0 V0
N 0 V0
0.5
1.5
ng cong chuan o
dung dch Fe2+ bang dung
dch Ce4+
= E0
ox2/kh2
0,059 S + 1
lg
n2
S
ox1 / kh1
0,059
lg S
n1
V du 2: Tnh sai so ch th cua phep chuan o v du tren neu ket thuc chuan
o EC = 0,870V va 1,237V. Trong phep chuan o tren, neu dung ch th la
Diphenylamin th sai so la bao nhieu ?
V du 3 :Tnh sai so ch th khi chuan o 100 ml dung dch Fe2+ bang dung dch
KMnO4 co cung nong o 0,1N , trong moi trng H2SO4 1N va khong thay oi neu
ket thuc chuan o khi d 1 giot dung dch KMnO4 (tng ng 0,05 ml KMnO4)
.Cho EoFe3+/Fe2+ = 0,77V ; EoMnO4-/Mn2+ =1,51V
http://www.ebook.edu.vn
http://hoahocsp.tk
- 123 -
n1 e
-
pKh1
n2 e
Ox2
n2p Kh1 +
n1Ox2
E = E0
ox 2 / kh 2
0,059
F
lg
n2
1 F
E t =
0
0
+ n 2 E ox
n1E ox
1 / kh1
2 / kh 2
n1 + n 2
1
0,059
lg
n1 + n 2 p[kh ] p1
1
Trong o:
[kh 1 ] =
p N 0 V0
n1 V0 + V
0
E = E ox
+
1 / kh1
0,059 [ox1 ]
lg
n1
[kh 1 ]
0
+
E = E ox
1 / kh1
0,059 1
0,059
1
lg ( F 1) +
lg
n1
p
n1
[kh ] p1
1
http://www.ebook.edu.vn
http://hoahocsp.tk
- 124 -
Mn2+
Mau tm hong
Khong mau
V du: Dung dung dch KMnO4 e chuan FeSO4 trong moi trng H2SO4
8H2O
V du :
2KMnO4 + 3Na2SO3 + H2O
V du
H2O
KMnO4 = M KMnO4
Lu y : MnO2 co the tao thanh ngay trong trng hp phep chuan o tien hanh
trong moi trng acid neu lng acid khong u.
Trong thc te khi tien hanh chuan o bang phng phap permanganat ngi
ta thng tien hanh trong moi trng acid v:
- Trong moi trng acid, ion Mn2+ khong co mau nen de nhan ra iem tng
ng.
- Kha nang oxy hoa cua KMnO4 trong moi trng acid manh hn nhieu so
vi trong moi trng kiem v :
EoMnO4-/Mn2+ =1,51V >> EoMnO4-/MnO2
= 0,59V
-2e
Mn2+ + 4H2O
2CO2
http://www.ebook.edu.vn
http://hoahocsp.tk
- 125 -
4MnO2 + 4KOH
+ 3O2
Phng phap nay c s dung rong rai trong thc te v KMnO4 la chat oxy
hoa manh nen co the giup xac nh c nhieu chat kh, va lai qua trnh chuan o
khong can ch th e xac nh iem cuoi v ban than KMnO4 co mau ch can 1 giot
d la u lam cho dung dch co mau hong giup nhan iem tng ng.
V du: Dung dung dch KMnO4 co the chuan o c:
8H2O
5O2 + 2Mn2+
5NO3- + 2Mn2+
+ 8H2O
+
3H2O
Moi trng acid c tao ra bang H2SO4, khong dung HCl v ion Cl- se gay ra
phan ng cam ng (la phan ng ma ieu kien ch co 2 chat th khong xay ra
phan ng nhng khi co phan ng khac xay ra th no se xay ra) V du: Cl- va
MnO4- se khong xay ra phan ng, nhng khi co phan ng Fe2+ va MnO4- th phan
ng sau se xay ra:
10Cl- + MnO4- + 8H+
Bang thc nghiem ngi ta thay rang, neu them vao dung dch chuan o mot
lng Mn2+ th phan ng cam ng se khong xay ra. Ngi ta hay dung hon hp
bao ve Zymmerman (hon hp gom: MnSO4 - H3PO4 - H2SO4)
Ngoai ra ngi ta con co the dung phng phap chuan o gian tiep e xac nh
nhng chat co the Eo tng ng vi EoMnO4-/Mn2+
V du: e xac nh Cr2O72- (EoCr2O72- / Cr3+ = 1,36V) ngi ta cho Cr2O72- phan
ng vi 1 lng d chnh xac dung dch muoi Fe2+ sau o chuan lng Fe2+ d
bang KMnO4
C ( N )K 2 Cr 2 O 7 =
oi vi nhng chat khong co kha nang oxy hoa -kh th co the dung phng
phap phan ng the.
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
- 126 -
V du: Co the xac nh Ca2+ bang cach ket tua Ca2+ dang CaC2O4 roi dung
acid hoa tan CaC2O4, chuan lng C2O42- sinh ra bang KMnO4
2. Phng phap Iod:
- Iot t do giong nh cac halogen khac, no co kha nang lay e- cua nhng chat
de nhng e-. Do o no la chat oxy hoa.
- Ion I- de nhng e- cho nhng chat co kha nang lay e-. Do o no la chat
kh. C s cua phng phap phan tch the tch theo phng phap Iot la qua
trnh oxy hoa - kh, bien I2 thanh I- va ngc lai bien I- thanh I2:
2I- ( Eo = 0,5345V)
I2 + 2e
EoI2/2I-
< Eo MnO4-/Mn2+
< Eo K2Cr2O7/Cr3+ .
I2 + Na2S2O3
2S2O32- -
(Eo = 0,08 V)
S4O62-
2e
Na2S2O3
I2
Na2S2O6 + 2NaI
= M Na2S2O3
= 1/2MI2
Khi chuan dung dch Na2S2O3 bang I2 mau nau sam cua dung dch I2 se bien
mat ngay khi toan bo Na2S2O3 a c oxy hoa het va mot giot d I2 lam dung dch
co mau vang, cho nen co the chuan o ma khong can dung ch th. Nhng v mau
vang nhat cua I2 rat kho nhan biet iem cuoi nen ngi ta hay dung ho tinh bot
lam ch th. Ho tinh bot co the tao vi I2 mot chat hap phu I2 thanh mau xanh am
khi d I2 hoac bien mat mau khi het lng I2 t do, ieu nay giup nhan ra iem
tng ng de va chnh xac hn. Lu y: khong nen cho ch th ho tinh bot khi
trong dung dch con nhieu I2 . Biet CN cua dung dch I2 va the tch ta co the tnh
c CN (Na2S2O3). Ngoai ta con co the dung phng phap iod e xac nh mot so
chat kh khac nh :
SO32-
+ I2 + H2O
H2S + I2
Sn2+ + I2
Sn4+ + 2I-
http://www.ebook.edu.vn
http://hoahocsp.tk
- 127 -
Khong the nhan ra iem cuoi, ma ngi ta phai dung phng phap gian tiep
nh sau:
Cho mot the tch chnh xac dung dch chat oxy hoa can xac nh nh
K2Cr2O7 vao hon hp dung dch KI d va acid (lam moi trng). e yen 5
phut cho phan ng tren xay ra hoan toan, roi dung dung dch Na2S2O3 a biet
nong o chnh xac e chuan lng I2 c giai phong ra.
C N K 2 Cr 2 O 7 =
Na2S2O3 +
(V .C N ) Na2 S 2O3
VK 2Cr2O7
I2
Na2S4O6 +
2NaI
2Br- + I2
3I2 + 3H2O
Lu y:
- EoI2/2I- khong u ln nen nhng phan ng trong phep chuan o kho co the
xay ra hoan toan, muon no xay ra hoan toan ta phai tao nhng ieu kien thch
hp.
- I2 la chat de bay hi nen phai chuan o nguoi va khi nhiet o tang th o
nhay cua ho tinh bot se giam i.
- Khong tien hanh trong moi trng kiem v I2 ket hp vi kiem.
- I2 t tan trong nc nen phai dung KI d e tao I3-, nen thc chat chuan I2
bang Na2S2O3 chnh la chuan I3- bang Na2S2O3.
- Phai e yen mot thi gian e cho phan ng xay ra hoan toan.
- Phai e yen trong bong toi v anh sang se lam cho phan ng phu sau ay
xay ra nhanh hn:
4I- + 4H+ + O2
2I2 + 2H2O
http://www.ebook.edu.vn
http://hoahocsp.tk
- 128 -
- Dung dch chuan Na2S2O3 cung khong the chuan b t lng can c v
Na2S2O3 khong phai la chat goc, chang han no phan ng vi H2CO3 hoa tan
trong nc:
Na2S2O3 + H2CO3
NaHCO3 + NaHSO3
+ S
- Khi pha che dung dch Na2S2O3 chuan can lu y: nc pha che phai c
diet khuan bang cach un soi nc cat roi e nguoi v vi khuan se phan huy
Na2S2O3 thanh Na2SO4 va Na2S4O6, hoat ong cua vi khuan giam moi trng
pH = 9 -10 nen khi pha ngi ta kiem hoa dung dch bang cach them mot t
Na2CO3. Hoat ong cua vi khuan tang len khi co anh sang va nhiet o tang, do
vay phai kiem tra thng xuyen nong o Na2S2O3 v ngoai nhng nguyen nhan
noi tren, Na2S2O3 con co the ket hp vi Oxy cua khong kh:
2Na2S2O3 +
O2
2Na2SO4 + 2 S
Xac nh nong o cua Na2S2O3 bang dung dch K2Cr2O7 chuan (nh v du
tren) hoac dung dung dch KIO3
IO3- + 5I- + 6H+
I2 + 3I-
3I2 + 3H2O
3I3-
2Cr3+
+ 7H2O
Eo = 1,36 V
Dung dch chuan K2Cr2O7 chuan rat on nh. Hau het cac phep chuan o
bang KMnO4 co the thay bang K2Cr2O7 nhng phai dung chat ch th e xac
nh iem cuoi nh Diphenylamin, Diphenylbenzidine. u iem la co the s
dung moi trng HCl ma khong can hon hp bao ve Zymmerman.
BAI TAP
1- 25,00ml dung dch H2C2O4 c trung hoa hoan toan bang 20,00ml dung dch
NaOH 0,0500N.
a- Tnh pH cua dung dch tai iem tng ng th 2.
b- Dung 25ml dung dch H2C2O4 noi tren e chuan o mot dung dch KMnO4
trong moi trng co u acid. The tch dung dch KMnO4 a dung la 12,50ml. Tnh
sai so chan o, biet rang tai iem cuoi e mat nhan ro s chuyen mau phai dung
d 0,05ml dung dch KMnO4.
Cho H2C2O4 co pK1 = 1,25, pK2 = 4,27
http://www.ebook.edu.vn
http://hoahocsp.tk
- 129 -
http://www.ebook.edu.vn
http://hoahocsp.tk
- 130 -
http://www.ebook.edu.vn
http://hoahocsp.tk
- 131 -
MUC LUC
Phan I. C S LY THUYET CHUNG ...................................................................... 3
Chng I. GII THIEU VE HOA PHAN TCH ..................................................... 3
I. Noi dung va yeu cau: ........................................................................................ 3
II. Cac cach phan loai trong hoa phan tch .......................................................... 3
III. Cac giai oan cua mot phng phap phan tch: ............................................ 5
IV. Yeu cau oi vi thuoc th va phan ng dung trong phan tch hoa hoc: ...... 5
Chng II. CAN BANG HOA HOC NH LUAT BAO TOAN NONG O ....... 7
I. Can bang hoa hoc trong dung dch ................................................................... 7
II. Dung dch nc cua cac chat ien ly: ............................................................. 9
III. Cach bo qua ai lng nho canh ai lng ln:.......................................... 11
IV. nh luat bao toan nong o:......................................................................... 11
Chng III. ACID VA BAZ PHAN NG TRAO OI PROTON ..................... 12
I. Mot so nh ngha:........................................................................................... 12
II. Tnh pH cua dung dch acid: pH = -lg aH+ hay pH = - lg [H+]...................... 15
III. Tnh pH cua dung dch baz: .......................................................................... 19
IV. pH cua dung dch hon hp n acid yeu va baz lien hp vi no - Dung dch
em:..................................................................................................................... 22
V. pH cua dung dch cha 1 hp chat ion: ......................................................... 25
Chng IV. PHC CHAT TRONG DUNG DCH ................................................ 28
I. nh ngha - Mot so khai niem: ...................................................................... 28
II. Hang so ben va khong ben cua phc: ........................................................... 28
III. Nong o can bang cua cac cau t trong dung dch phc chat: ................... 30
IV. Hang so ben (khong ben) ieu kien: ........................................................... 33
V. ng dung cua phan ng tao phc trong phan tch:....................................... 35
Chng V. PHAN NG KET TUA ....................................................................... 37
I. ieu kien tao thanh ket tua. Quy luat tch so tan:......................................... 37
II. Quan he gia o tan va tch so tan - Nhng yeu to anh hng en o tan: 38
III. Ket tua phan oan: ....................................................................................... 45
IV. ng dung cua phan ng ket tua trong hoa phan tch: phan ng ket tua co
nhieu ng dung nhng ta ch xet trong phan tch. ............................................. 46
Chng VI. PHAN NG OXY HOA - KH......................................................... 48
I. nh ngha:....................................................................................................... 48
II. Cng o cua chat oxi hoa va chat kh - The oxi hoa-kh: ........................ 48
III. Nhng yeu to anh hng en the oxi hoa kh - The oxi hoa kh tieu chuan
ieu kien: ............................................................................................................ 50
IV. Hang so can bang cua phan ng oxi hoa- kh: ........................................... 54
V. Tnh the oxi hoa kh cua cac dung dch: ...................................................... 55
VI. ng dung cua phan ng oxi hoa- kh trong phan tch:............................... 60
Phan II. PHAN TCH NH LNG ..................................................................... 63
Phan A. GII THIEU VE PHAN TCH NH LNG........................................... 63
http://www.ebook.edu.vn
http://hoahocsp.tk
- 132 -
http://www.ebook.edu.vn
http://hoahocsp.tk