21 Hoaphantich

TRNG AI HOC A LAT
GIAO TRNH
HOA PHAN TCH

(Danh cho sinh vien nganh moi trng)
ANG TH VNH HOA

2002
http://hoahocsp.tk
Hoa Phan tch cho sinh vien moi trng
-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
ang Th Vnh Hoa
http://www.ebook.edu.vn
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Phan I. C S LY THUYET CHUNG
Chng I. GII THIEU VE HOA PHAN TCH
-3-
I. Noi dung va yeu cau: 1. Noi dung: Hoa phan tch la mot mon khoa hoc co nhiem vu nghien cu cac phng phap va cac quy trnh nham xac nh thanh phan hoa hoc cua cac chat. Phan tch hoa hoc la tien hanh mot quy trnh phan tch thch hp nham muc ch nhan c nhng thong tin cu the ve mot he vat chat nao o, e qua nhng thong tin o, chung ta co the co c nhng ket luan khoa hoc xac ang ve he vat chat o. Pham vi cua chung ta la phan tch thanh phan hoa hoc ngha la nham tra li 2 cau hoi ve mau khao sat: - Mau khao sat gom co nhng cau t nao phan tch nh tnh. - Cac cau t o hien dien vi ham lng bao nhieu phan tch nh lng. e tra li c 2 cau hoi tren ngay cang co nhieu phng phap khac nhau. C s cua a so cac phng phap phan tch thanh phan hoa hoc eu da vao tnh chat hoa hoc hay l hoc do tng tac cua mau khao sat vi 1 hoa chat thch hp c goi la thuoc th. 2. Yeu cau: e van dung c cac phng phap phan tch hoa hoc oi hoi chung ta phai nam c nguyen tac cua phng phap va cac mon khac nh toan, hoa ai cng, hoa vo c, hoa ly la c s can ban giup ta i vao lnh vc phan tch hoa hoc de dang. * Yeu cau oi vi nganh hoa phan tch: phai phat trien theo s phat trien cua cac nganh khoa hoc khac. * Yeu cau oi vi ngi phan tch: - u kien thc e van dung trong qua trnh phan tch va luon c cap nhat hoa e co the cai tien hay a ra phng phap mi ngay cang phu hp hn vi yeu cau thc te. - Can than, kien nhan, chnh xac trong thao tac phan tch. - Trung thc trong viec ghi nhan cac s kien va ket qua at c. II. Cac cach phan loai trong hoa phan tch 1. Phan loai theo phng phap phan tch: a) Phng phap hoa hoc: Phan tch theo phng phap hoa hoc la da vao mot phan ng hoa hoc e chuyen cau t khao sat thanh hp chat mi ma vi tnh chat ac trng nao o ta co the xac nh s hien dien va ham lng cua cau t khao sat.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng b) Phng phap vat l:
-4-
Phng phap vat ly dung cach khao sat tnh chat tnh chat ly hoc ac trng nao o e xac nh s hien dien va ham lng cua mot cau t. c) Phng phap hoa ly: Phan tch theo phng phap hoa ly la da vao tnh chat vat ly cua hp chat hay dung dch tao ra sau khi co phan ng gia cau t khao sat va thuoc th e xac nh s hien dien hay ham lng cua cau t o. d) Cac phng phap khac: Chang han: - Phng phap nghien: nghien mau khao sat vi thuoc th roi da vao dau hieu ac trng nao o e xac nh s hien dien va ham lng - Phng phap th nghiem ngon la: V du: khi nhung day Pt vao dung dch Na+ roi ot tren ngon la kh butan th co mau vang, K+ cho mau o, Ba2+ cho mau luc - Phng phap soi tinh the 2. Phan loai theo lng chat can phan tch hay ky thuat phan tch: a) Phan tch tho: - Dung dung cu c 50 ml en 500 ml va tach chat ran khoi chat long bang cach loc. - Lng chat khao sat dung cho moi lan phan tch khoang 1 - 10g hay 1 - 10 ml. b) Phan tch ban vi: - Dung dung cu < 50 ml va tach chat ran khoi chat thng bang ly tam. - Lng chat khao sat dung cho moi lan phan tch khoang 10-3 - 1g hay 10-1 1 ml. c) Vi phan tch: - Dung dung cu c <1 ml va co the quan sat di knh hien vi, dung phan ng giot. - Lng chat khao sat: 10-6 - 10-3g hay 10-3 - 10-1ml. d) Sieu vi phan tch: - Thng phai phan tch di knh hien vi ien t va ieu kien moi trng ac biet. - Lng chat khao sat khoang <10-6 g va1l. => Phng phap ban vi phan tch ngay cang phat trien v dung tng oi t mau, n gian trong ky thuat, khong oi hoi nhieu ieu kien nghiem ngat nh vi phan tch hay sieu vi phan tch phng phap ban vi phan tch s dung rong rai.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng 3. Phan loai theo ham lng chat khao sat: - Phan tch a lng: ham lng chat khao sat > 0,001% - Phan tch vi lng: ham lng chat khao sat < 0,001% 4. Phan loai theo trang thai chat khao sat:
-5-
- Phan tch t: phai chuyen mau thanh dang dung dch trc khi phan tch. - Phan tch kho: xac nh trc tiep t dang ban au, chang han mot so phng phap vat ly, phng phap nghien, th nghiem ngon la III. Cac giai oan cua mot phng phap phan tch: 1. Chuan b mau phan tch: Ket qua phan tch ch co y ngha khi giai oan nay c thc hien tot. Giai oan nay gom cac bc: - Chon mau ai dien - Chuyen mau thanh dang thch hp 2. Thc hien phan ng: Cho dung dch phan tch tac dung vi thuoc th thch hp nhng ieu kien nhat nh. 3. Ghi nhan ket qua 4. X ly ket qua phan tch-tnh toan ket qua 5. Tnh sai so, o tin cay cua ket qua phan tch. Ket luan IV. Yeu cau oi vi thuoc th va phan ng dung trong phan tch hoa hoc: 1. Yeu cau oi vi thuoc th: a) o tinh khiet: Tuy theo ham lng cua hp chat chnh ngi ta phan loai hoa chat nh sau: - Hoa chat ky thuat: ham lng chat chnh 99% - Hoa chat tinh khiet (P): 99% ham lng chat chnh 99,9% - Hoa chat tinh khiet phan tch (PA): 99,90% ham lng chat chnh 99,99% - Hoa chat tinh khiet hoa hoc : 99,99% ham lng chat chnh 99,999% - Hoa chat tinh khiet quang hoc: 99,999% ham lng chat chnh 99,9999% Trong phan tch neu pha cac dung dch chuan can chon loai hoa chat tinh khiet phan tch, nhng phai co them cac ieu kien: . Tr vi moi trng: khong tac dung vi O2, N2, khong hut nc . dang bot vun (e co the can c lng rat nho) . Co phan t lng ln (e giam sai so khi can) ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng b) Tnh chon loc:
-6-
Mot thuoc th c xem la co tnh chon loc cao khi thuoc th o ch phan ng vi chat can xac nh trong s co mat cua nhieu chat khac. c) Tnh nhay: La kha nang phan tch mot lng rat nho chat can xac nh trong dung dch. Yeu cau oi vi phan ng: Phan ng gia chat can phan tch vi dung dch thuoc th can thoa man cac ieu kien: - Phai xay ra tc thi - Phai xay ra hoan toan (hang so can bang cua phan ng phai 107- 108) 2. Cac loai phan ng thng gap trong phan tch hoa hoc: - Phan ng oxy hoa kh - Phan ng trao oi: nh phan ng acid- baz, tao tua, tao phc
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc

Chng II. CAN BANG HOA HOC NH LUAT BAO TOAN NONG O
-7-
I. Can bang hoa hoc trong dung dch 1. Hang so can bang: oi vi phan ng thuan nghch: m A + n B + 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=
[C] p [D]q ... [A]m [B]n ...
=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 =
am .a n ... A B
p q aC .a D ...
Trong o hoat o a = f.C, vi C la nong o cua ion va f la he so hoat o (0 < f 1 ). Khi o nh luat tac dung khoi lng co dang:
p q aC .a D ....
Ka =
am .a n ... A B
fC p .[C] p fD q [D]q ... f

m A B
[A ]m f n [B]n ...
Ka = Kc.
fC p .fD q ... f
m A
.f
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
-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
* 0,02 < < 0,2 th f c tnh bi bieu thc

lg f = 0 ,5 Z 2 1+
0,2 th f c tnh bi bieu thc
lg f =
0 ,5 Z 1 +
+ h
Trong o h la he so c xac nh bang thc nghiem, he so nay thay oi oi vi moi ion. V du: Tnh hoat o cua cac ion trong dung dch hon hp KCl 10-3M va MgSO4 103 M. Giai: = 0,5 ( [K+].12 + [Cl-].12 + [Mg2+].22 + [SO42-].22 ), trong o [K+] = [Cl-] = 10-3 [Mg2+] = [SO42-] = 10-3 nen = 0,5 (10-3.1 + 10-3.1 + 10-3.4 + 10-3.4 ) = 5.10-3
lg f = 0 , 5 Z 2
= 5.10-3 < 0,02 nen lgfK+ = lgfCl- = - 0,035 vay fK+ = fCl- = 10-0,035 = 0,922 lgfMg2+ = lgfSO42- = - 0,14 vay fMg2+ = fSO42- = 10-0,14 = 0,722
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Vay hoat o cua cac ion a K+ = aCl- = 0,922. 10-3 = 9,22.10-4 ion g /l aMg2+ = aSO42- = 0,722. 10-3 =7,22.10-4 ion g /l 2. Hang so can bang ieu kien:
-9-
Neu trong can bang hoa hoc: m A + n B + p C + q D +.; cac cau t A, B, C, D con tham gia cac phan ng phu khac th nong o cua moi chat tham gia vao can bang tren se giam i. e bieu th anh hng cua cac phan ng phu en can bang tren, ngi ta dung ai lng hang so can bang ieu kien, ky hieu K. K khong nhng phu thuoc vao nhiet o, lc ion cua dung dch ma con phu thuoc vao nong o cua cac chat khac tham gia vao cac phan ng vi cac chat A, B, C, D. Neu goi [A], [B], [C], [D] la tong nong o cua cac dang cua A, B, C, D trong dung dch th [A], [B], [C], [D] ch bang mot phan cua cac tong nong o [A], [B], [C], [D]; tc la: [A] = [A].A ; [B] = [B].B ; [C] = [C].C ; [D] = [D].D. Cac gia tr = 1 khi khong cho phan ng phu. Cac he so A , B, C, D < 1 la nhng he so bieu th anh hng cua cac phan ng phu en nong o cua A, B, C, D t do. Theo nh luat tac dung khoi lng: p q C p . D q ... [C] p .[ D] q ... [C ' ] p [D ' ]q C . D ... ' K= = . =K . m [A ] m .[B] n ... [A ' ] m [B' ]n m . n ... . n ... A B A B Trong thc te e n gian viec tnh toan nong o can bang cua cac ion trong dung dch ngi ta thng coi Ka = Kc tc la bo qua tng tac tnh ien coi f = 1. Ket qua se khong chnh xac, nhng v ta thng dung nhng dung dch loang, nen sai so trong gii han co the chap nhan c. II. Dung dch nc cua cac chat ien ly: 1. Chat ien ly: Chat ien ly la chat ma khi hoa tan vao nc no se phan ly thanh ion. Tuy theo hang so ien ly va o ien ly ma ngi ta chia ra: - Chat ien ly manh: la chat ma khi hoa tan vao nc no se phan ly hoan toan thanh ion (K = ). a so cac muoi, kiem cua kim loai nhom IA va IIA va acid manh thuoc loai nay. V du: * HCl H+ + ClNeu dung dch HCl co nong o 0,1M th [H+] = [Cl-] = 0,1 ion g / l * Al2(SO4)3 2Al3+ + 3SO42Neu dung dch Al2(SO4)3 co nong o 0,1M th [Al3+] = 2. 0,1 ion g / l [ SO42-] = 3. 0,1 iong/l ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 + ] [CH 3 COOH ]

3
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 .
So phan t a phan ly thanh ion So phan t a a vao hoa tan

Me+ + A-
V du: hoa tan muoi MeA co nong o C, o ien ly MeA ) Khi at trang thai can bang th [Me+] = [A-] = .C va [MeA] = C - .C = C (1 Hang so can bang K luc nay goi la hang so phan ly:
[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 HCOO- + H+
K=
[ HCOO ][ H + ] [ HCOOH ]
Goi [H+] = [HCOO-] = x ( iong/l ) Vay [HCOOH] = 3.10-1 x ( M )
K=
x .x x2 4 1 , 77 . 10 = 3 .10 1 x 3 .10 1 x
Giai phng trnh bac 2: x2 + 1,77.10-4.x 5,31.10-5 = 0 ta tnh c:
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng 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:
- 11 -
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
- Nong o can bang [Na+] = CNaCl =0,067M; [NO3-] = CAgNO3 = 0,083M; nhng [Ag+] < CAgNO3 va [Cl-] < CNaCl v hai ion nay co tham gia phan ng vi nhau. Noi dung cua nh luat bao toan nong o au nh sau: nong o ban au cua 1 cau t nao o se bang tong nong o can bang cua cac dang ton tai cua cau t o trong dung dch tai thi iem can bang. V du: bieu dien nh luat bao toan nong o au oi vi ion PO43- trong dung dch Na3PO4 0,1M. Na3PO4 0,1 PO433Na+ + PO433.0,1 + H2O 0,1 HPO42- + OHH2PO4- + OHH3PO4 + OHKhoa Hoa hoc
HPO42- + H2O H2PO4- + H2O ang Th Vnh Hoa
http://hoahocsp.tk
Hoa Phan tch cho sinh vien moi trng C PO43- = 0,1 = [PO43-] + [HPO42-] + [H2PO4-] + [H3PO4]
Chng III. ACID VA BAZ PHAN NG TRAO OI PROTON
- 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: Acid V du: H2S HSNH4+ Al(H2O)63+ 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. Acid Baz V du: CNbaz. 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
baz lien hp + H+ Acid baz lien hp CH3COOHSS2NH3 + + + H+ H+ H+
CH3 COOH
+ H+
[Al(H2O)5OH]2+ + H+
+ + +
H2O H2O H2O H2O
baz acid NH3
+ + +
H3O+ OHH3O+ OH-
NH4+ +
HCN +
- Tuy theo ban chat cua dung moi, 1 chat co the the hien tnh acid hoac
http://hoahocsp.tk
Khoa Hoa hoc
- 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: Na2HPO4 H+ 2Na+ + H2PO4H+ HPO42HPO42- va co kha nang cho H+ va co kha nang nhan H+ HPO42- + HPO42PO43- + 2. Hang so acid KA va hang so Baz KB:
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: HA + H2O e n gian ta viet: HA H3O+ + AH+ + A-
[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 ]
Th hang so baz la: KB cang ln th baz cang manh. e thuan tien cho viec tnh toan ngi ta thng dung pKB = - lgKB. V du CH3COO- co KB = 10-9,25 va NH3 co KB = 10-4,75, vay NH3 la baz manh hn CH3COO-. * Vi a acid va a baz: - Acid hoac baz ma mot phan t ch nhng hoac nhan 1 H+ th goi la n acid hoac n baz. - Acid hoac baz ma mot phan t nhng hoac nhan 2 hay nhieu H+ th goi la a acid hoac a baz. Trong dung dch cac a acid hoac a baz phan ly lan lt theo tng nac. Moi nac se nhng hoac nhan 1 H+ va co mot hang so acid hoac hang so baz tng ng. ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng V du: H3PO4 H2PO4HPO42PO43+ H2O H2O H+ H+ H+ + + + HPO42H2PO4H2PO4HPO42PO43+ + OHOHOH-
- 14 KA1 = 10-2,21 KA2 = 10-7,21 KA3 = 10-12,36 KB1 = 10-1,64 KB2 = 10-6,79 KB3 = 10-11,88
Ngc lai PO43- lai la mot a baz HPO42- +
H2PO4- + H2O H3PO4 + 3. Quan he gia KA va KB. Tch so ion cua nc:
KA = K =
B
[H + ][A ] [HA ] [HA ][OH ] [A ]

(1) H+ + OH-
KA.KB = [H+][OH-] Mat khac: H2O Hang so can bang:
[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-]
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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+] > 10-7 ion g/l [OH-]<10-7 ion g/l =>pH < 7 , pOH >7 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 Moi trng trung tnh [H+] = [OH-] pH = pOH = 7 Moi trng kiem [H+] < 10-7 ion g/l [OH-]>10-7 ion g/l pH >7, pOH < 7
II. Tnh pH cua dung dch acid: pH = -lg aH+ hay pH = - lg [H+]
lg f
0,02 => fH+ = 0,849
H+
= 0,5Z 2 = 0,5.1. 0,02 = 0,0707
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng aH+ = fH+.CH+ = 0,849. 2.10-2 = 0,01698 pH = -lgaH+ = 1,77 - Vi HCl 5.10-3M th = 0,5( 5.10-3.12 + 5.10-3.12) = 5.10-3 0,02 =>
- 16 -
lg f
fH+ = 0,92
= 0,5Z 2 = 0,5.1. 0,005 = 0,035
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 HCO3* H3PO4 H2PO4HPO42H+ H+ H+ H+ H+ + + + + + HCO3- co K1 = 4,47.10-7 CO32- co K2 = 6.10-11 H2PO4- co K1 = 7,6.10-3
HPO42- co K2 = 6,2.10-8 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.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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
Muon giai chnh xac th s dung phng trnh: V du: Tnh pH cua dung dch hon hp HCl 10-4 M va CH3COOH 10-2M. Cho KA = 10-4,75 Giai: V Cm < Cy nen: - Giai gan ung: [H+]2 Cm[H+] KHAyCy = 0 [H+]2 10-4[H+] 10-4,75.10-2 = 0 Giai ra c pH = 3,32 ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 + ] =
[H + ] + K 1
K 1 C1
[H + ] + K 2
K 2 C2
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 + ] =
[H + ] + K 1
K 1C1
- Neu K1 K2 va C1 C2 th phai dung phng trnh tong quat. V du: Tnh pH cua cac hon hp 2 acid: CH3COOH 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 [H+]2 = 10-5,76 => [H+] = 10-2,88 => pH = 2,88 0,1M (pKCH3COOH = 4,76) va HCN 0,1M (co pKHCN = 9,21) 5.10-4M va HCN 10-1M. 0,1M va HCOOH 0,1M pKHCOOH = 3,75.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng * Giai chnh xac: (C1=C2 , K1>>K2)
- 19 -
[H + ] =
K CH 3COOH C CH 3COOH [H + ] + K CH 3COOH
[H+]2 10-4,76[H+] 10-5,76 = 0 Giai phng trnh ta c [ H+] = 1,32.10-3 va pH = 2,88 Vay ca hai cach cho ket qua nh nhau, nhng cach 1 nhanh hn ii- C1 < C2 K1 >> K2 cung giai nh cau a ta c: Giai gan ung pH = 4,03 Giai chnh xac pH 4 iii- C1 = C2 K1 K2 Giai gan ung: [H+]2 =10-4,76. 0,1 + 10-3,75.0,1 = 19,518.10-6 Vay [H+] = 4,418.10-3 va pH = 2,35 Neu giai chnh xac th phng trnh se tr thanh phng trnh bac ba kho giai. Nen trong thc te ngi ta van ap dung phng phap giai gan ung. III. Tnh pH cua dung dch baz: oi vi cac dung dch baz cong thc tnh cung tng t nh cac dung dch acid, nhng trong o thay H+ bang OH-, thay KA bang KB, thay CA bang CB 1. Dung dch baz manh: Gia s co 1 baz manh co nong o CB Tng t nh phan acid manh ta cung ch gap trng hp: CB 10-6mol/l th pOH = -lgCB nen pH = 14 - pOH, vay: pH = lg CB + 14 V du: Tnh pH cua dung dch NaOH co nong o 10-2 mol/l. - Neu khong ke lc ion : CNaOH < 10-6 => pH = lgCB + 14 = -2 + 14 =12 - Ke lc ion: = fOH- = 10-0,05 = 0,89 aOH- = CNaOH.fOH- = 0,89. 10-2 = 8,9.10-3iong/l pOH = -lg8,9.10-3+ = 2,05 pH = 14 2,05 = 11,95 0,5( 10-2 + 10-2 ) = 10-2 lgfOH- = -o,5.Z2.( )1/2 = - 0,5.1.10-1 = -0,05
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng 2. Dung dch n baz trung bnh 10-3 < KB < 100 Tnh tng t nh n acid trung bnh ta co: [OH-]2 + KB[OH-] KBCB = 0 Giai phng trnh nay tnh c [OH-] roi t o tnh c [H+] va pH 3. Dung dch n baz yeu 10-10 < KB < 10-3 pOH = 0,5pKB - 0,5lgCB nen pH = 14 - 0,5pKB + 0,5lgCB V du: 1- Tnh pH cua dung dch NH4OH 10-2M biet pKNH4OH = 4,75. KNH4OH = 10-4,75 vay no thuoc loai baz yeu nen pH = 14 - 0,5pKB + 0,5lgCB = 14 - 0,5.4,75 + 0,5lg10-2 pH = 10,625 1- Tnh pH cua dung dch KCN10-2M biet HCN co KA = 10-9,21. KCN K+ + CNCN- la mot baz yeu v co KB = 10-4,79 pH = 14 - 0,5pKB + 0,5lgCB = 14 - 0,5.4,79 + 0,5lg10-2 pH = 10,61 4. Dung dch a baz
- 20 -
Muoi trung hoa cua cac a acid nh Na3PO4, Na2CO3, Na2C2O4 la nhng a baz v khi hoa tan vao nc cac anion goc acid se nhan 1, 2 hoac nhieu H+ va mot nac ng vi mot hang so baz rieng. V du: * Na3PO4 PO43- + H2O HPO42- + H2O H2PO4- + H2O 3Na+ HPO42- + H2PO4+ PO43OH- KB1 = KH2O/KA3 = 10-1,62 + OH- KB2 = KH2O/KA2 = 10-6,79 KB3 = KH2O/KA1 = 10-11,88
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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng [OH-]2 + KB[OH-] kBCB = 0 [OH-]2 + 10-1,62[OH-] 10-1,62.10-1 = 0 [OH-]= 0,0385 nen pOH = 1,42 vay pH 12,58 5. pH cua hon hp 2 baz: a) Hon hp 2 baz manh:
- 21 -
Gia s co hai baz manh co nong o tng ng la C1 va C2, th cung ly luan nh phan acid ta co: pOH = -lg( C1 + C2 ) nen pH = 14 + lg ( C1 + C2 ) b) Hon hp 1 baz manh va 1 baz yeu: Gia s co hai baz: 1 baz manh co nong o la Cm va 1 baz yeu co nong o Cy va hang so baz la KB, th cung tng t nh phan acid ta co: - Neu Cm Cy th pOH = -lgCm nen pH = 14 + lgCm - Neu Cm < Cy th co the giai gan ung bang phng trnh [OH-]2 Cm[OH-] KBCy = 0 Muon giai ung th ap dung phng trnh:
[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+ + CO32CO32- 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://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng - Giai chnh xac:
- 22 -
[OH ] =
[OH ] + K B1
K B1C1
[OH ] + K B2
K B2 C 2
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 ] =
[OH ] + K B1
K B1C1
- Neu K1 K2 va C1 C2 th phai dung phng trnh tong quat. IV. pH cua dung dch hon hp n acid yeu va baz lien hp vi no - Dung dch em: 1. nh ngha: Dung dch em la dung dch co pH rat t thay oi khi ta them vao dung dch mot lng nho acid manh hoac baz manh. pH cua dung dch acid yeu HA va baz lien hp vi HA la A- thay oi khong ang ke khi them vao mot t acid manh hoac baz manh v HA H+ + A- (1) nen khi them acid manh tc [H+] se tang nen can bang (1) se chuyen sang trai (tc H+ se ket hp A-) con neu them baz manh tc la [H+] giam nen can bang (1) chuyen qua phai (tc HA se phan ly H+). Ket qua la sau khi can bang thiet lap nong o H+ se thay oi khong ang ke. V vay neu them hon hp acid yeu va baz lien hp cua no vao mot dung dch th pH cua dung dch o thay oi khong ang ke trong quy trnh nghien cu. Do o dung dch hon hp nay c goi la dung dch em. 2. Thanh phan cua dung dch em: Thanh phan cua dung dch em la hon hp 2 dang cua 1 oi acid-baz thng la: - Hon hp cua mot acid yeu va muoi cua acid yeu o vi 1 baz manh. V du: dung dch em gom: CH3COOH + CH3COONa la dung dch em acid. - Hon hp cua 1 baz yeu va muoi cua baz yeu o vi 1 acid manh. V du: dung dch em gom : NH4OH + NH4Cl la dung dch em baz. - Hon hp 2 chat lng tnh acid baz. V du: CO32- + HCO3- hoac H2PO4- + HPO42-
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng 3. pH cua dung dch em:
- 23 -
Khao sat dung dch em cha acid yeu HA co nong o CA hang so acid KA va baz lien hp vi no (tc la muoi MA) co nong o CB th phng trnh tong quat e tnh pH cua dung dch em HA/MA la:
[H + ] = K A .
CA CB
pH = pK A lg
CA CB
Con oi vi he em tao thanh t baz yeu co nong o CB, hang so baz la KB va acid lien hp vi no co nong o CA th cong thc tnh pH nh sau:
pOH = pK B lg
CA CA CB
CB
pH = 14 pK B lg
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
B
= pK CH COOH lg
3
C CH 3COONa
C CH 3COOH
= 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 = 4,75 lg(1,1.10-2/0,9.10-2) = 4,66. 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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Tng t cau a => CCH3COOH = 10-2 - 0,1.10-2 = 0,9.10-2 CCH3COONa = 10-2 + 0,1.10-2 = 1,1.10-2M => pH = 4,75 + lg(1,1.10-2/0,9.10-2) = 4,84. Trong trng hp nay pH cung ch tang len 0,09 n v 3- Tnh pH cua dung dch hon hp NH4OH 0,01M va NH4Cl 0,02M. Biet KNH4OH = 10-4,75
- 24 -
ay la he em tao bi baz yeu NH4OH va acid lien hp vi no la NH4+
pH = 14 pK B lg
pH = 14 4,75 lg 0,02 + lg 0,01 = 8,95 4. em nang cua dung dch em:
CA CB
e bieu th kha nang cua dung dch em chong lai s thay oi pH khi them acid hoac baz vao, ngi ta dung khai niem em nang. em nang c nh ngha: bang so mol cua mot baz manh hay acid manh can them vao mot lt dung dch em o, e pH cua no tang hay giam mot n v pH. em nang c ky hieu la .
=+
pH
pH
Vi CB, CA la so mol baz manh hoac acid manh them vao. pH la o bien thien pH gay ra khi them 1 lng CB baz manh hoac CA acid manh. Ngi ta a tnh c:
= 2,3
CA + CB C A .C B C
C A .C B
Trong 1 lt dung dch th CA + CB = C
= 2,3
CA + CB
C A .C B
= 2,3
Cong thc nay ch ap dung khi KA C / 200 C 200.KA tc thoa ieu kien: CA , CB >> [H+], [OH-]. se cc ai khi CA = CB = C/2 khi o max = 2,3.C / 4 Vay em nang se at cc ai khi nong o dang acid va baz lien hp bang nhau. Vay muon pha 1 dung dch em co em nang ln nhat ta nen chon oi
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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: V du nh cac hp chat NH4CN, (NH4)2CO3 goi la he acid yeu va baz yeu khong lien hp. Nhng hp chat loai nay c tao thanh bi 1 acid yeu HA1 co nong o CA va hang so acid KA1 va mot baz yeu A2- co nong o CB va hang so baz la KB t o tnh c hang so cua acid lien hp vi no la KA2. - Neu CA = CB th [H+]2 = KA1KA2 Suy ra: pH = 0,5( pKA1 + pKA2 ) - Neu CA = m.CB th giai phng trnh sau e tm pH
[H + ] + K A1
mK A1
[H + ] [H + ] + K A 2
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng V du:
- 26 -
1- Tnh pH cua dung dch NH4CN 10-1M biet pKHCN = 9,21, pKNH3 = 4,76 Giai: NH4CN NH4+ 4,76 = 9,24. NH4+ + CNH+ + NH3 vay NH4+ la acid cua he NH4+/ NH3 co pKNH4+ = 14HCN + OH- vay CN- la baz cua he HCN/CN- co KHCN
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+ + SO42NH4+ 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+ + HPO42HPO42- 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.
1- Tnh pH cua cac dung dch sau: a- Dung dch Na2CO3 0,1M, biet H2CO3 co K1 = 10-6,35 , K2 = 10-10,32 b- Dung dch acid phtalic ( H2A ) 0,1M, biet H2A K1 = 10-2,95 , K2 = 10-5,41. c- Dung dch NH4F 0,1M, biet HF co K1 = 10-3,2, NH3 co pKB = 4,75.
BAI TAP
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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
3
7- Tnh hang so baz cua baz yeu Pyridin, biet rang dung dch Pyridin nong o 10M co pH bang 8,1.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc

Chng IV. PHC CHAT TRONG DUNG DCH
- 28 -
I. nh ngha - Mot so khai niem: - Phc chat la loai hp chat sinh ra do ion kim loai (goi la ion trung tam) ket hp vi phan t hoac ion khac (goi la phoi t). Trong dung dch ion trung tam, phoi t va phc chat eu co kha nang ton tai rieng le. - Trong hoa phan tch, nhng phc chat co nhng ng dung phong phu thng la nhng phc chat phan ly c ti mc u e san pham cua s phan ly co the hoa hp c vi cac chat khac. V du: - Trong dung dch nc, ion phc [Ag(NH3)2]+ phan ly 1 phan thanh Ag+ va [Ag(NH3)2]+ Ag+ + 2NH3 phan t NH3: Nong o NH3 u ln e co the hoa hp c vi H+: NH3 - Phc + H+ NH4+ Hg2+ + 2ClHgCl2
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+ + S2HgS - Nhng hp chat: (NH4)2SO4.6H2O, KAl(SO4)2.12H2O co thanh phan giong phc chat, song khi hoa tan chung phan ly hoan toan thanh nhng ion n gian nen chung khong phai la phc chat ma la nhng muoi kep. - Trong mot phc chat, so phoi t lien ket vi ion trung tam goi la so phoi tr. So phoi tr cc ai thng la 2, 4 va 6. V du: [Ag(NH3)2]2+; [Zn(NH3)4]2+; [FeF6]3-co so phoi tr lan lt la 2, 4, 6. Nhng phc chat nay ch co 1 ion trung tam, v vay chung c goi la phc n nhan. - Nhng phc chat co nhieu ion trung tam cung loai nh [Fe2(OH)2]4+, [Cu3(OH)4]2+ hoac khac loai nh [(CN)5Co(CN)Fe(CN)5]6-, goi la phc a nhan. - Nhng phc chat co nhieu phoi t khac nhau c goi la phc d phoi.V du: [Pt(NH3)2Cl2] , [Co(NH3)3(NO2)3] - Nhng phc chat ma phoi t cha mot nguyen t lien ket vi ion trung tam goi la phc n cang. Con neu phoi t cha nhieu nguyen t lien ket vi ion trung tam, goi la phc a cang. II. Hang so ben va khong ben cua phc: 1. Phc co mot phoi t: M + L ML Xet phc chat ML trong o M la ion trung tam, L la phoi t.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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+ + Y4Ni(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:
=
2. Phc co nhieu phoi t:
[NiY 2 ] [Ni 2+ ][Y 4 ]
Phc co nhieu phoi t c tao thanh va phan ly lan lt theo nhieu nac, ng vi moi nac co hang so ben va hang so khong ben rieng. V du: phc [Zn(NH3)4]2+ c tao thanh qua 4 nac: Zn2+ + NH3 ZnNH32+ (1)
1 =
[ZnNH 3 2+ ] [Zn ][NH 3 ]

2+
= 10 2,18 K 1 =
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng ZnNH32+ + NH3 Zn(NH3)22+ (2)
- 30 -
2 =
[Zn (NH 3 ) 2 2+ ] [ZnNH

2+ 3
][NH ]
3
= 101,25 K 2 =
1 2
Zn(NH3)22+ + NH3
Zn(NH3)22+ (3)
3 =
[Zn (NH 3 ) 3 2+ ] [Zn (NH )

2+ 3 2
][NH ]
3
= 10 2,31 K 3 =
1 3
Zn(NH3)32+ + NH3
Zn(NH3)42+ (4)
4 =
[Zn (NH 3 ) 4 2+ ] [Zn(NH )

2+ 3 3
][NH ]
3
= 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: Zn2+ + 2NH3 Zn(NH3)22+
1,2 =
[Zn 2+ ][NH 3 ]2
[Zn ( NH 3 ) 2 2+ ]
= 1 . 2
1,2 goi la hang so ben tong cong cua 2 phan ng tren.
K 1,2 =
1 1,2
Con hang so khong ben tong cong se bang: Tong quat: 1,n = 1. 2. 3n-1. n III. Nong o can bang cua cac cau t trong dung dch phc chat: Da vao hang so ben hoac hang so khong ben cua cac phc chat va nong o ban au cua ion trung tam va cua phoi t ta co the tnh c nong o can bang cua phoi t, t o ta tnh c nong o can bang cua cau t khac. Gia s ion trung tam M co nong o ban au la CM va co kha nang tao vi phoi t L cac phc ML, ML2, ML3,. , MLn (n la so phoi tr cc ai) ng vi cac hang so ben tng nac la 1, 2, 3,, n. Muon tm [M], [L], [ML], [ML2], ..,[MLn] ta da vao cac phng trnh sau: - Phng trnh bao toan khoi lng oi vi ion trung tam M: [M] + [ML] + [ML2] + .. + [MLn] = CM - Phng trnh hang so ben: ang Th Vnh Hoa
(1)
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng M + L ML
- 31 -
1 =
[ML ] [M ][L ]
T o suy ra [ML] = 1[M][L] ML + L ML2
2 =
[ML ] [ML ][L ]

2
[ML2] = 2[ML][L] = 12 [M][L]2 = 1,2 [M][L]2 MLn-1 + L MLn Tng t nh tren ta co [MLn] = 1,n [M][L]n The cac gia tr nay vao phng trnh (1) ta co: [M] + 1[M][L] + 1,2 [M][L]2 + . + 1,n [M][L]n = CM
[M ] =
1 + 1 [L ] + 1,2 [L ] + ... + 1,n [L ]n .C .[ L] 1 + 1 [L ] + 1,2 [L ]2 + ... + 1,n [L ]n .C .[L ]n

1,n M 1 M
M 2
[ML ] =
[ML n ] =
1 + 1 [L ] + 1,2 [L ]2 + ... + 1,n [L ]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://hoahocsp.tk
Khoa Hoa hoc
- 32 -
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] Ag(CN)2 K+ + Ag(CN)2Ag+ + 2CNK = 10-21
K=
[Ag + ][CN ]2 [Ag(CN ) 2 ]
at [Ag+] = x th [CN-] = 2x vay [Ag(CN)2- ] = 10-1 x.
K=
Vay:
x.(2 x ) 2 10
1
= 10 21
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+ + NH3 Ag(NH3)+ + NH3 Ag+ + NO3Ag(NH3)+ Ag(NH3)2+
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Ta co:
- 33 -
[Ag + ] =
C0
Ag +
1 + 1 [NH 3 ] + 1,2 [NH 3 ]2
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.
[Ag ] =
10 2 1 + 10
3,32
.1 + 10
3,32
.10
3,92
.1
= 10 9,24
[AgNH3+] = 1[Ag+][NH3] = 103,32.10-9,24.1 = 10-5,92 [Ag(NH3)2+] = 1,2[Ag+][NH3]2 = 103,32.103,92.10-9,24.1 = 10-2 NH3: 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 Vay ung vi gia thiet (sai so 2%) IV. Hang so ben (khong ben) ieu kien: tren ta a xet can bang phc trong ieu kien ion trung tam va phoi t ch tham gia vao mot phan ng tao phc gia chung vi nhau. Nhng trong thc te ion trung tam hoac phoi t hoac ca hai thng con tham gia vao nhng phan ng phu khac. Do o nong o cua ion trung tam va phoi t thay oi nen lam thay oi o ben cua phc ban au. e ac trng cho o ben (khong ben) cua phc trong ieu kien cu the ma o xay ra phan ng tao phc va e n gian cho viec tnh toan ta dung hang so ben (khong ben) ieu kien. K hieu (K) Gia s ion kim loai Mn+ ngoai viec tham gia phan ng tao phc chnh vi anion Y4-: Mn+ + Y4MYn-4, no con tham gia phan ng tao phc phu vi phoi t L: M + L ML
1 =
[ML] = 1[M][L] ML + L L
[ML ] [M ][L ]
ML2 (2)
MLm-1 +
MLm (m)
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Mat khac anion Y4- con phan ng vi cation H+ Y4- + H+ HY33
- 34 -
[Y 4 ][H + ] [HY ] = K = 4 K4 [HY 3 ]

hang so acid HY3H2Y2H3Y+ + + H+ H+ H+ H2Y2- hang so acid K3 H3Y- hang so acid K2 H4Y hang so acid K1
[Y 4 ][H + ]
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] => = [M] + [ML] + + [MLm] = [M] + 1[M][L] + 12[M][L]2 at M(L) + +1.2m[m][L]m = [M] (1 + 1[L] + 12[L]2 + +12m[L]m) = 1 + 1[L] + 12[L]2 + + 12m[L]m) [M] = [M]. M(L) - [Y] = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y] 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
' 4
[ 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)
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Nh vay:
- 35 -
' =
[MY n 4 ] [M ]. M ( L ) .[ Y 4 ]. Y( H )
M ( L ) . Y( H )
MY n 4
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+ + Mg2+ + Y4+ HY3- + H2Y2- + H3Y- + H2O Y4OHH+ H+ H+ H+ MgY2MgOH+ HY3H2Y2H3YH4Y =108,7 =102,58 K4 K3 K2 K1
H+ + OH- (qua trnh nay co the bo qua)
' =
- Mg(OH) =
MgY Mg (OH ) . Y( H )
1 + Mg(OH)+ . [OH-]
pH = 11 => [H+] = 10-11 => [OH-] = 10-3 => Mg(OH) = 1 + 102,58 . 10-3 = 1 + 10-0,42 = 1,38 - Y(H) tnh bang cach the cac gia tr vao bieu thc Y(H) Ta tnh c Y(H) = 1,89. Vay hang so ben ieu kien cua phc MgY2-
' =
o ben cua MgY2- pH = 11 giam.
10 8,7 = 10 8,28 1,38 .1,89
V. ng dung cua phan ng tao phc trong phan tch: Hau nh trong bat ky lanh vc nao cua hoa phan tch eu co s dung nhng phan ng tao phc. 1. Trong phan tch nh tnh: Ngi ta s dung phan ng tao phc e: ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng - Phat hien cac ion: SCN-
- 36 -
V du: . phat hien ion Fe3+ bang phan ng tao phc co mau o mau vi . phat hien ion Cu2+ bang phan ng tao phc co mau xanh am vi
NH3 - 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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc

Chng V. PHAN NG KET TUA
- 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+ + ClAgCl 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.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 S mA + nB, goi S la o tan cua AmBn th: mS nS
TAmBn = aAm.aBn = [A]m[B]n.fAm.fBn Trong o [A] trong dung dch la mS [B] trong dung dch la nS Nen TAmBn = (mS)m(nS)nfAm.fBn = mm. nn .Sm+n. fAm.fBn
S = m +n
T m
m
AmBn m n .n n .fA .fB
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
m .n
AmBn 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
- Neu bo qua lc tng tac ion: TMg(OH)2 = [Mg2+][OH-]2 = S.(2S)2 = 4S3 o tan S cua Mg(OH)2 c tnh theo nh ngha: ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 S 3Ca2+ + 2PO43-. 3S 2S
S=5
TCa3( PO 4 )2 108
=5
10 32 ,5 = 1,24.10 7 mol / l 108
T Ca3(PO4)2 = [Ca2+]3 [PO43-]2 = (3S)3.(2S)2 = 108.S5 S = 1,24.10-7mol/l ung vi gia thiet V du 3: tnh o tan cua CaSO4 trong nc, biet T CaSO4 = 9,1.10-6 Goi S la o tan cua CaSO4 va gia s S < 10-4 mol/l CaSO4 S T CaSO4 = [Ca
2+
Ca2+ + SO42-. S ][SO42-]

2
S = 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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng fCa2+ = lg fSO42- = 0,603
- 40 -
S=
TCaSO 4 f
2
9,1.10 6 (0,603)
2
= 5.10 3 mol / l
T CaSO4 = [Ca2+][SO42-] f2 = S2. f2 = 9,1.10-6 2. Cac yeu to anh hng en o tan cua tua: phan tren chung ta tnh o tan cua ket tua trong nc nguyen chat vi gia thiet la cac ion cua tua khong tham gia phan ng vi H+ va OH- cua nc. Nhng trong thc te cation kim loai cua tua tao phc vi OH- va anion cua tua thng phan ng vi H+. Ngoai ra nhng chat khac trong dung dch cung co the phan ng vi cac ion cua tua hoac t nhat cung lam thay oi hoat o cua chung. Nhng yeu to nay eu anh hng en o tan cua ket tua. a) Anh hng cua ion chung Ion chung la ion tham gia vao thanh phan cua tua. V du tua AmBn th cac ion A va Bm- la nhng ion chung. Neu them ion cua ket tua vao dung dch bao hoa cua ket tua o th tch so ion se ln hn tch so tan nen can bang se chuyen ve pha tao them ket tua va lam giam o tan cua no.
n+
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+ + SO42Goi S la o tan cua BaSO4 th [Ba2+] = [SO42-] = S Gia s S < 10-4 mol/l ta co: TBaSO4 = [Ba2+][SO42-] = S. S = S2 = 1,03. 10-10 T o suy ra S = 1,015.10-5mol/l - Tnh o tan cua BaSO4 trong dung dch Na2SO4: Goi S la o tan cua BaSO4 trong dung dch Na2SO4. Ta co cac can bang: Na2SO4 2Na+ + SO4210-2 BaSO4 S 2.10-2 S 10-2 S Ba2+ + SO42(phan ly hoan toan)
[Ba2+] = S [SO42-] = S + 10-2
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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+ + ClGoi S la o tan cua AgCl trong nc. Gia s S < 10-4 mol/l TAgCl = [Ag+][Cl-] = S2
S = TAgCl = 1,05.10 5 mol / l

- o tan cua AgCl trong dung dch KNO3 10-1 M: Goi S la o tan cua AgCl trong dung dch KNO3 ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng KNO3 K+ + NO3 TAgCl AgCl Ag+ + Cl= [Ag+][Cl-].fAg+.fCl- = S2.f2
- 42 -
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
fAg+ = fCl- = 0,76 TAgCl = 1,1.10-10 = (S)2 . (f)2
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+ + nBmGoi S la o tan cua tua trong ieu kien a cho. [A] la tong nong o cac dang ton tai cua A tr dang tua [A] = mS = [A] + [AL] + +[ALP]. Nh trong trng hp phc chat: [A] = mS = [A](1+ 1[L] +1,2[L]2 + + 1,p[L]p) [A] = mS = [A] .A(L) Tng t =>[B] = nS = [B] + [HB] + [H2B] ++ [HqB] ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 43 -
[H + ] [H + ]2 [H + ] q [B' ] = nS' = [B] 1 + + + .... + Kq K q .K q 1 K q .K q 1 ....K 2 .K 1

[B] = nS = [B].B(H)
The [A] va [B] vao bieu thc tch so tan ta co: TAmBn = [A]m[B]n = [A]m[B]n . mA(L). nB(H) = TAmBn . mA(L). nB(H) Vay: TAmBn = TAmBn . mA(L). nB(H) TAmBn = (mS)m . (nS)n = mm . nn .(S)m+n
A(L), B(H) > 1 nen TAmBn > TAmBn Mat khac
S' = m + n
T'
m .n
AmBn m n
So sanh gia tr nay vi gia tr o tan cua tua trong nc
S = m +n
V TAmBn > TAmBn nen S > S
m .n
AmBn m n
V du 1: Tnh o tan cua CuS trong nc (dung dch co pH = 7). Biet TCuS = 6,3.10-36, H2S co pK1 = 7, pK2 = 12,89. Hang so ben tong cong cua cac phc tao thanh bi Cu2+ va OH- lan lt la 1 = 107,0 , 1,2 = 1013,68, 1,3 = 1017 , 1,4 = 1018,5. Giai: Cac qua trnh xay ra trong dung dch: CuS S2+ H+ H+ HS- + Cu2+ HSH2S Cu(OH)+ ; Cu(OH)2 ; Cu(OH)3- ; Cu(OH)42+ S2-
Cu2+ + OH-
Goi S la o tan cua CuS trong nc
S' = m + n
T'
m .n
AmBn m n
T'
1 .1
CuS
Ma TCuS = TCuS . Cu(OH -).S(H)
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Cu(OH -)= 1 + 1[OH-] + 1,2[OH-]2 + 1,3[OH-]3 + 1,4[OH-]4 pH = 7 suy ra [H+] = [OH-] = 10-7 Cu(OH -)= 1 + 107.10-7 + 1013,68.(10-7)2 + 1017.(10-7)3 + 1018,5.(10-7)4 Cu(OH -) = 1 + 1 + 10-0,32 = 2,48
- 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
S(H) = 1 + 105,89 + 105,89 = 2. 105,89 TCuS = TCuS . Cu(OH -).S(H) = 6,3.10-36.2,48.2.105,89 = 0,24.10-28 S = ( TCuS )1/2 = 0,49.10-14mol/l V du 2 : Tnh o tan cua CaC2O4 trong dung dch co pH=4. Biet T CaC2O4 = 2,3.10-9 va H2C2O4 co pK1 = 1.25 va pK2 = 4.27 Giai : Theo e bai trong dung dch co cac can bang sau CaC2O4 C2O42- + HC2O4- + H+ H+ Ca2+ + HC2O4H2C2O4 C2O42-
C2 O 4( H )
[H + ] [H + ]2 10 4 10 8 = 1+ + = 1 + 4,27 + 5,52 K2 K 2 K1 10 10
TCaC2O4 = TCaC2O4. C2O4(H+) C2O4(H+) = 1 + 1,862 + 3,31.10-3 = 2,862 TCaC2O4 = TCaC2O4. C2O4(H+) = 2,3.10-9.2,862 = 6,583.10-9 Vay S = ( TCaC2O4 )1/2 = 8,11.10-5mol/l d) Anh hng bi cac yeu to khac: i- Anh hng cua nhiet o en o tan: tch so tan ch la mot hang so mot nhiet o nhat nh, nhiet o thay oi th o tan cung thay oi. S thay oi cua o tan theo nhiet o co lien quan ti hieu ng nhiet khi hoa tan: - oi vi nhng chat thu nhiet khi hoa tan: tc la nhiet o giam khi tan, th o tan se tang cung nhiet o. - oi vi nhng chat toa nhiet khi hoa tan: tc la nhiet o tang khi tan, th o tan se giam khi nhiet o tang. ii- Anh hng cua kch thc hat ket tua: oi vi cung mot lng chat, ket tua co hat nho tan nhieu hn ket tua co hat ln va hoan chnh v tren be mat cac hat nho co nhieu goc canh va ion goc, canh de tan hn nhng cho khac.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng III. Ket tua phan oan:
- 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+ + ClAgCl
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Ag+ + CrO42Ag2CrO4
- 46 -
Theo quy luat tch so tan: [Ag+][Cl-] = TAgCl = 1,78.10-10 [Ag+]2 [CrO42- ] = TAg2CrO4 = 1,1.10-12 Lap ty so hai phng trnh tren:
[Cl ]
[CrO 2 ] 4
1,78.10 10 1,1.10
12
= 1,7.10 4
Khi Ag2CrO4 bat au ket tua th [CrO42- ] = C0CrO42- = 10-2
[Cl ] = 1,7.10 4 . 10 2 = 1,7.10 5 iong / l 1,7.10 5.100 = 1,7.10 2 % = 0,017 % 1 10

Do o % Cl- cha b ket tua la: Vay cung co the ket tua phan oan Cl- va CrO42- bang Ag+ 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. 1. Phan tch nh tnh: Trong phan tch nh tnh thng s dung phan ng ket tua e: - Xac nh mot so ion bang phan ng ket tua vi mot thuoc th thch hp. V du tm Cl- bang phan ng ket tua vi Ag+ e cho ra ket tua AgCl co mau trang, tm Cd2+ bang phan ng ket tua vi S2- e cho ra ket tua CdS co mau vang, tm SO42- bang phan ng ket tua vi Ba2+ e cho ra ket tua BaSO4 co mau trang - Tach phan oan mot ion hoac mot nhom ion: phan ng ket tua c s dung rong rai e tach chat can xac nh hoac tach mot nhom ion trong mau phan tch ra khoi mau. V du trong phan tch nh tnh ngi ta dung HCl e tach cac ion Ag+, Pb2+, Hg22+ ra khoi nhng ion khac, dung H2SO4 e tach cac ion Ba2+, Sr2+, Ca2+ ra khoi nhng ion khac, 2. Phan tch nh lng: - Phng phap phan tch trong lng - Phng phap chuan o ket tua
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.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc

Chng VI. PHAN NG OXY HOA - KH
- 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 Zn2+ Fe3+ + + 2e e Dang kh Zn0 Fe2+ Mn2+ + 4H2O
MnO4- + 8H+ + 5e
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 V du: Zn0 + Cu2+
- 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 ox2 : la qua trnh oxy hoa Zn2+ la qua trnh oxy hoa
- 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 kh1 : la qua trnh kh Cu0 : la qua trnh kh
Vay Zn0 la chat kh, Cu2+ la chat oxi hoa. II. Cng o cua chat oxi hoa va chat kh - The oxi hoa-kh: - Mot chat cang de nhan ien t th no co tnh oxy hoa cang manh va ngc lai mot chat nhng ien t cang de th no co tnh kh cang manh. - Trong mot cap oxy hoa kh lien hp neu chat oxy hoa cang manh th chat kh lien hp cang yeu va ngc lai.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 +
Trong o:
RT RT [ox ] ln vi dung dch rat loang th : E = E 0 + ln nF a kh nF [kh ]
a ox
kh th phng trnh Nerst la:
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 th phng trnh Nerst co dang:
a c 0,059 a A .a C ... E = E0 + lg m n n a .a ... M N
m M + n N + ..
(1)
Co the thay hoat o a bang nong o can bang. Trong phng (1) B la chat ran nen hoat o cua no c coi bang 1. V du:
E = E0
* Fe3+ + e * Cu2+ + 2e
Fe / Fe
3+
2+
0,059 a Fe lg 1 a
3+
Fe2 +
Fe2+ : qua trnh kh Cu0
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 50 -
E = E0
Cu / Cu
2+
0,059 a Cu lg 1 2
2+
* MnO4- + 8H+ + 5e
Mn2+ + 4H2O
E = E0
MnO / Mn 2 + 4
0,059 + lg 5
MnO 4
.a 8
H+
Mn 2 +
( hoat o cua nc la mot hang so nen a vao E0 ) e n gian trong tnh toan ngi ta thng bo qua lc tng tac tnh ien coi hoat o bang nong o. Co the da vao the oxy hoa kh chuan E0 cua cac cap oxy hoa kh lien hp e so sanh cng o cua chat oxy hoa va chat kh cua cac cap. E0 cua cac cap oxy hoa kh lien hp cang cao th chat oxy hoa cang manh va chat kh lien hp vi no cang yeu. V du: E0Cl2/2Cl-= 1,36 V > E0Fe3+/Fe2+ = 0,77 V, nen Cl2 la chat oxy hoa manh hn Fe3+ va Fe2+ la chat kh manh hn Cl-. Neu E0ox1/kh1 > E0ox2/kh2 th phan ng xay ra theo chieu: ox1 + kh2 kh1 + ox2 2Cl- + 2Fe3+ Nh vay trong hai cap tren th phan ng nh sau: Cl2 + 2Fe2+
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.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 kh + d H2O
E 0' = E 0 +
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 + nekh + m L kh khLm khLm phc khLm co hang so ben 1,m(kh) th:
ox + ne- + mL
E 0' = E 0 +
b kh - neox + mL ox oxLm
0,059 lg 1,m ( kh ) n
kh - ne- + mL
oxLm , phc oxLm co hang so ben 1,m(ox) th:
E 0' = E 0 +
1 0,059 lg 1,m (ox ) n
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng c- Neu trong can bang ox + nephan ng tao phc: ox + m1L kh + m2L
- 52 kh ca hai chat ox va kh eu tham gia
oxLm1 co hang so ben ox khLm2 co hang so ben kh
E 0' = E 0 +
0,059 kh lg n ox
Trong trng hp nay th the tieu chuan ieu kien c tnh: V du 1: tnh the oxi hoa kh chuan ieu kien cua cap Fe3+/Fe2+ trong dung dch co d F- e tao phc FeF63- co hang so ben tong cong 1,6 = 1016. Biet EoFe3+/Fe2+ = 0,77 V. Giai: Fe2+ - eFe3+ FeF63FeF63Fe3+ + 6F Fe2+ - e- + 6F-
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+ + eCo2+ Co2+ + 6NH3
II 0,059 1,6 + lg III 1 1,6
Co3+ + 6NH3 Co(NH3)63+ va 3. Phan ng tao ket tua:
Co(NH3)62+
0,059 kh = E0 E 0' = E 0 + lg Co ox n E 0' = 1,84 +
3+
/ Co 2 +
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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 53 -
E 0' = E 0 +
box - ne- + X kh - ne ox + X
-
0,059 1 lg n Tkh
khX tua khX co tch so tan Tkh th:
ox oxX
E 0' = E 0 +
kh - ne- + X ox + neox + X kh
0,059 lg T ox n
ox , tua oxX co tch so tan Tox th:
c- Neu ca hai chat ox va kh eu co the tao phan ng ket tua: oxX co Tox
E 0' = E 0 +
kh + X
0,059 Tox lg n Tkh
khX co Tkh, th:
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+ + eCu+ + IGiong trng hp a nen: Cu+ 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 - eAg+ + ClGiong trng hp b nen: Ag+ AgCl
E 0' = E 0
Ag + / Ag
0,059 lg T = 0,8 + 0,059 . lg 10 9,75 = 0,22 V ox n
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng IV. Hang so can bang cua phan ng oxi hoa- kh: 1. Neu phan ng gom hai na phan ng co so e- nhan va cho nh nhau: ox1 + ne kh2 ne kh1 co E0ox1/kh1 ox2 co E0ox2/kh2 ox2 + kh1 th:
/ kh
- 54 -
tc phan ng co dang: ox1 + kh2

0 n(E ox / kh 0 E ox
lg K =
)
2
n(E 0
ox1/kh1
0,059
kh1 ox2 E0ox1/kh1 E0ox2/kh2
hay K = 10
0,059
0 ) Eox 2 / kh 2
2. Neu phan ng gom hai na phan ng co so e- nhan va cho khac nhau: ox1 + n1e kh2 n2 e
tc phan ng co dang: n2ox1 + n1kh2
n1ox2 + n2kh1 th:
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
0,059
hay K = 10
0,059
- Neu E = E0ox1/kh1 E0ox2/kh2 cang ln phan ng xay ra theo chieu thuan. - K 107 th xem nh phan ng co tnh nh lung - Neu trong dung dch co xay ra cac phan ng phu ta thay E0 = E0 V du 1: Tnh hang so can bang cua phan ng gia Ce4+ va Fe2+. Neu nong o ng lng cua hai chat nay nh nhau, th phan ng xay ra co hoan toan khong? Cho E0Ce4+/Ce3+ = 1,55V, E0Fe3+/Fe2+ = 0,77V. Giai: Ce4+ + Fe2+ Ce4+ + e Fe2+ - e Ce3+ + Fe3+ phan ng nay gom hai na phan ng: Ce3+ Fe3+
lg K =
1.( E 0
Ce 4 + / Ce3 +
E0
0,059
Fe3 + / Fe 2 +
1,55 0,77 = 13,22 0,059
Ta thay so ien t he cho va nhan bang nhau ( n = 1 ) Vay K = 1013,22 e thay c mc o hoan toan cua phan ng nay ta hay tnh cac ty so nong o: [Fe3+]/[Fe2+] va [Ce3+]/[Ce4+]
[Ce 3+ ][Fe 3+ ] K= [Ce 4+ ][Fe 2+ ]
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 +
4
= 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+ MnO4- + 5e- + 8H+ Fe2+ eFe3+ Mn2+ + 5Fe3+ + 4H2O Mn2+ + 4H2O Phan ng nay gom 2 na phan ng:
lg K =
n1 .n 2 (E 0
MnO / Mn 2 + 4
E0
Fe3 + / Fe2 +
) =
0,059
5.1(1,51 0,77) = 62,7 0,059
Ta thay so ien t he cho va nhan khac nhau, nen: Vay K = 1062,7 V. Tnh the oxi hoa kh cua cac dung dch: 1. The cua 1 cap oxi hoa kh lien hp: Dang 1: ox1 + n1e V du: Fe3+ + e Ce4+ + e 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 ]
Trong o E0 la the oxy hoa chuan cua cap ox1/kh1 ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 56 -
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 [Fe3+] = 0,05 + 1 = 1,05 Mn2+ + 5Fe3+ + 4H2O
[Fe2+] con lai trong dung dch = 1 0,05 = 0,95
E = E0 +
0,059 1,05 lg = 0,772 V 1 0,95

kh1 + 1/2mH2O th:
Ta thay the ch thay oi co 0,002 n v. Dang 2: ox1 + mH+ + n1e
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 ox1 + n1e kh2 - n2e n1ox2 + n2kh1 kh1 ox2 Phan ng nay gom hai na phan ng:
* 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 ]
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 57 -
E=
0 E ox / kh
1
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
0,059 [ox 2 ] lg n2 [kh 2 ]
E=
0 E ox 2 / kh 2
0 N1 0,059 + lg 0 0 n2 N 2 N1
n E0
1
ox1 / kh1
+ n E0
2
n1 + n 2
ox 2 / kh 2
sau:
* 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+ Hoac na phan ng co dang: kh2 - n2e + (m/2) H2O
th:
E
V du 1:
n E0
1
ox1 / kh1
+ n E0
2
n1 + n 2
ox 2 / kh 2
0,059 lg[H + ]m n1 + n 2
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+ V nong o ng lng cua Ce4+ va Fe2+ bang nong o phan t nen: a- CCe4+ < CFe2+ tc d Fe2+ nen tnh the theo cap Fe3+/Fe2+ ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 58 -
E=
E 0 3+ 2 + Fe / Fe
0 N1 0,059 9.10 2 + lg 0 = 0,77 + 0,059 lg 1 = 0,826 V 0,83V 0 n2 N 2 N1 10 9.10 2
b- CCe4+ = CFe2+ nen:
E=
n E0
1
ox1 / kh1
+ n E0
2
n1 + n 2
ox 2 / kh 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+ MnO4- + 5e- + 8H+ Fe2+ - eFe3+ Mn2+ + 5Fe3+ + 4H2O Mn2+ + 4H2O Phan ng nay gom hai na phan ng:
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
5.1,51 + 1.0,77 0,059 + lg(1) 8 = 1,39 V 6 6
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://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng n2ox1 + n1kh2 ox1 + n1e kh2 - n2e n2 pkh1 + n1ox2 p kh1 ox2
- 59 -
Phan ng nay gom hai na phan ng:
* 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
N0 N0 1 0,059 1 0 p + lg 1 0 2 . . vi [kh 1 ] = N 2 . 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=
0 E ox 2 / kh 2
0 N1 0,059 + lg 0 0 n2 N 2 N1
(2)
* Neu N01 = N02 th:
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
1
(3)
[kh1] cung c tnh nh tren Neu co s tham gia cua H+ (pH khac 0) nh phan ng: n2 ox1 + n1 kh2 + n2.mH+ n1 ox2 + n2p kh1 + n2.(m/2)H2O, th:
0 0 + n 2 E ox n1E ox 1 / kh1 2 / kh 2
E t =
n1 + n 2
0,059 1 1 lg .[ H + ]m p 1 n1 + n 2 p [kh ]
1
(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 2Cr3+ + 6Fe3+ + 7H2O Khoa Hoa hoc
http://hoahocsp.tk
Hoa Phan tch cho sinh vien moi trng Phan ng nay gom hai na phan ng: Cr2O72- + 6e- + 14H+ Fe2+ + eFe3+ 2Cr3+ + 7H2O
- 60 -
a- N0 Cr2O7 2- > N0 Fe2+ d Cr2O72-, ap dung cong thc (1) Vi n2 = 1, p = 2, n1 = 6, [kh1] = N02.p/n1 = N0Fe2+. p/n1 = 9.10-2.2/6= 3.10-2
E = 1,33 +
0,059 10 1 9.10 2 1 1 . . lg 2 2 3.10 2 = 1,333 V 6 9 . 10
b-N0 Cr2O7 2- = N0 Fe2+ Ap dung cong thc (4)
E=
6.1,33 + 0,77 0,059 1 14 1 lg (1) . + = 1,26 V 6 +1 1+ 6 2 (3.10 2 ) 21
vi m = 14, pH = 0 vay [H+] = 1, n1 = 6 c-N0 Cr2O7 2- < N0 Fe2+ Ap dung cong thc (2) vi n2 = 1
E = 0,77 +
0,059 10 1 lg = 0,829 V 1 1,1.10 1 10 1
VI. ng dung cua phan ng oxi hoa- kh trong phan tch: 1. Trong nh tnh: - Phat hien cac ion bang cach a ve so oxy hoa 0 V du: - Kh cac ion kim loai Mn+ thanh kim loai M bang cach chon mot chat co tnh kh manh hn kim loai M. Nh muon kh Hg2+ thanh Hg th ta nen dung Zn, Fe, Cu v E0Hg2+/Hg = 0,85V, E0Cu2+/Cu = 0,34V, E0Fe3+/Fe = -0,036V, E0Zn2+/Zn = -0,763V. So sanh cac cap the tren ta eu thay phan ng se xay ra theo chieu ion Hg2+ se phan ng vi Cu, Zn, hoac Fe e tao thanh Hg0. - Oxy hoa ion X- thanh X2 ( X la khong kim loai ), nh oxy hoa ion I- thanh I2 bang NO2-. NO2- + 2 I- + 2H+ 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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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- .
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng b- Tnh hang so can bang cua phan ng pH = 0.
- 62 -
6- Mot kim loai hoa tr 2 co E0Me2+/Me = 0,90V. Sau khi tron dung dch Me2+ noi tren vi dung dch Y4- (EDTA) e tao phc MeY2-, ngi ta o c the tao bi cap Me2+/Me noi tren 0,570V. Tnh hang so ben cua phc MeY2-.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Phan II. PHAN TCH NH LNG PHAN A. GII THIEU VE PHAN TCH NH LNG
- 63 -
Phan tch nh lng tc la xac nh ham lng cua cac nguyen to hay phan t cua chat can phan tch. e lam c viec o co the co nhieu phng phap khac nhau, tuy theo yeu cau can phan tch (o nhay, o chnh xac) va trang thiet b hien co ma ngi lam phan tch co the la chon cac phng phap khac nhau e tien hanh phan tch. Ngay nay ket qua thu c ch co gia tr khi a c x ly bang phng phap thong ke. V the sau khi thu c ket qua phan tch, ngi phan tch can phai biet x ly cac so lieu thu c e a ra ket qua phan tch chnh xac. I. Cac phng phap e phan tch nh lng: 1. Phng phap hoa hoc: La dung mot phan ng hoa hoc (tc la s dung mot thuoc th R nao o cho phan ng vi chat can xac nh X) e chuyen cau t can xac nh thanh mot hp chat mi, roi da vao the tch va nong o cua thuoc th R, hoac khoi lng cua hp chat mi tao thanh ta tnh c ham lng cua chat X. a) Phng phap phan tch khoi lng: Lam ket tua chat can xac nh di dang mot hp chat xac nh, lam sach ket tua va em nung en khoi lng khong oi roi can. Da vao lng can e tnh ham lng chat can xac nh. b) Phng phap the tch: Da vao the tch va nong o cua dung dch thuoc th R a phan ng vi 1 the tch xac nh chat can xac nh e tnh ham lng chat can xac nh. Thuoc ve phng phap the tch co 4 phng phap chuan o chnh: - Phng phap trung hoa - Phng phap chuan o phc chat - Phng phap oxi hoa kh - Phng phap tao tua. Cac phng phap hoa hoc ch ap dung e phan tch nhng mau co nong o ln (10-3 -10-1 M). Phng phap nay khong oi hoi nhng may moc hien ai nen de ap dung. 2. Phng phap vat ly: Dung cach khao sat tnh chat ly hoc ac trng nao o e xac nh ham lng cua chat can xac nh. V du: o khoi lng rieng, chiet suat hoac da vao s tng tac cua vat chat vi bc xa ien t
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng 3. Phng phap hoa ly:
- 64 -
Da vao tnh chat vat ly (mau sac, o dan ien) cua hp chat hay dung dch tao ra sau khi co phan ng hoa hoc gia chat can xac nh X va thuoc th R e xac nh ham lng cua chat can xac nh. Trong pham vi giao trnh nay ch e cap en cac phng phap hoa hoc. II. Cac khai niem ve sai so trong phan tch nh lng: 1. Sai so he thong hay sai so xac nh: co cac ac iem : - Co the xac nh c. - Anh hng mot chieu len o ung cua phep xac nh (luon co dau dng hoac am). - Do nhng nguyen nhan co the biet c nh: dung cu o, buret, pipet, bnh nh mc, can, may ohay hoa chat dung hoac nong o dung dch chuan sai. Phng phap xac nh co khuyet iem, ngi phan tch co khuyet iem ve cach oc, ve nhan mau - Co the giam, loai tr hay hieu chnh lai loai sai so nay neu xac nh c nguyen nhan. 2. Sai so ngau nhien hay sai so khong xac nh: co cac ac iem: - Khong the 1biet hay xac nh c. - Anh hng khong theo mot quy luat nao ca (luc am, luc dng). - Do nhng nguyen nhan khong co nh va khong d oan c. - Ch co the giam bang cach tang so lan xac nh. - Sai so ngau nhien co the do nguyen nhan khach quan (nong o thay oi, kh quyen khong sach) hoac chu quan cua ngi phan tch (can khong can than, o the tch sai).
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng PHAN B. GII THIEU CAC PHNG PHAP PHAN TCH HOA HOC
Chng I. Phng phap phan tch khoi lng
- 65 -
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.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng 2. Lam ket tua: a) Chon thuoc th va lng thuoc th: * Chon thuoc th: da vao cac yeu to sau: - Thuoc th co tnh chon loc cao - Tua tao thanh co o tan cang nho cang tot ( T < 10-7 10-8) - Dang can thu c ben va co cong thc xac nh. - He so chuyen co c cang nho cang tot.
- 66 -
V du: muon xac nh ham lng Cr th nen chon dang can la BaCrO4 hn la Cr2O3 v: vi tua BaCrO4 co he so chuyen
K=
M BaCrO 2M
Cr
=
4
51,996 = 0,205 253,32
Con vi tua Cr2O3 th he so chuyen
K=
* Lng thuoc th:
M Cr O
2
Cr
3
2.51,996 = 0,684 151,990
Lng thuoc th phai d e can bang hoa hoc gia chat can xac nh va thuoc th chuyen han ve pha tao hp chat t tan (neu lng thuoc th d khong gay phan ng phu co hai) thng lng thuoc th nen lay d 10 15% so vi lng tnh t phan ng. Neu lng thuoc th de bay hi nh NH4OH th lng thuoc th nen tang len gap 2 hay gap 3 lan. V du: nhng trng hp sau d thuoc th co hai: - Hg2+ + 2KI HgI2 + 2K+ , neu dung d KI th tua HgI2 se tan ra: HgI2 + 2KI K2[HgI4] - Al3+ + 3NaOH Al(OH)3 + 3Na+, neu dung d NaOH th tua se tan ra: Al(OH)3 + NaOH NaAlO2 + 2H2O b) ieu kien oi vi dang ket tua va dang can: * Dang ket tua: Co nhieu phan ng ket tua nhng khong phai moi phan ng eu dung trong phan tch khoi lng c. Muon dung th dang ket tua phai co ieu kien: - Tua phai co o tan nho e t b mat trong qua trnh ra. - Tua phai tinh khiet khong lan tap chat, t hap thu chat khac, muon vay tua can phai co dang tinh the to. - Tua phai de chuyen hoan toan sang dang can sau khi say hoac nung. * Dang can: ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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=
M' M M
Si
K=
M SiO
V du: - xac nh khoi lng Si theo dang can SiO2 th - Xac nh khoi lng Mg theo dang can Mg2P2O7 th:
K=
2M
Mg
2 2 7
M Mg P O
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Con neu dang bieu dien ket qua la MgO th
- 70 -
K=
2M
MgO
2 2 7
M Mg P O
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% =
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:
K.q.V.100 p.V0
X% = K.0,2545 .100 Fe% = 0,500 Fe% =
K.q.100 p K=
2M
M Fe O
2
Fe
3
2.55,847 = 0,6994 159,69
0,6994 .0,2545 .100 = 35,6% 0,500
b) Trng hp phan tch gian tiep: Neu khong da vao khoi lng cua dang can e tnh ham lng nguyen to X ma da vao lng can mau va ket qua nh lng cac nguyen to khac hoac tong so cua chung th goi la phan tch gian tiep.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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+ KCl + Ag+ (1) AgCl + Na+ AgCl + K+
m.
M AgCl M NaCl
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)
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc

Chng II. PHNG PHAP PHAN TCH THE TCH
- 72 -
(hay phng phap chuan o)

I. ai cng ve phng phap phan tch the tch: 1. nh ngha: - Phng phap phan tch the tch la phng phap xac nh nong o cua mot cau t X trong dung dch theo the tch cua mot dung dch thuoc th R thch hp a biet chnh xac nong o (c goi la dung dch chuan). - Qua trnh them t t dung dch chuan R cha trong Buret vao dung dch cha mot the tch xac nh cua chat can xac nh X goi la qua trnh chuan o. Trong qua trnh chuan o th dung dch chuan R c cho vao Burret con dung dch cha chat can xac nh X c cha trong bnh Erlen (bnh tam giac). - Thi iem ma tai o lng dung dch chuan R va u tac dung hoan toan vi chat X goi la iem tng ng (ay la iem ly thuyet). - e nhan ra iem tng ng co the dung nhng chat gay ra nhng hien tng trong thay c nh mau, ket tua xay ra gan iem tng ng. Nhng chat nay goi la chat ch th. - Thi iem ma tai o ket thuc viec chuan o c goi la iem cuoi, ket qua chuan o se ung khi dng chuan o ngay iem tng ng nhng thng iem cuoi khong trung vi iem tng ng (co the trc hoac sau) do o gay sai so cho viec chuan o. - Neu ch th oi mau trc khi en iem tng ng th V (ml) dung dch chuan R < V (ml) iem tng ng sai so thieu (-) va ngc lai neu ch th oi mau sau iem tng ng sai so tha (+). - Sai so ch th: do viec xac nh sai iem tng ng, thuoc loai sai so co dau xac nh, e lam giam sai so ch th can phai chon chat ch th nao o sao cho no oi mau rat gan iem tng ng va oi mau that ot ngot (e co the xac nh c the tch chnh xac). - ng chuan o la ng bieu dien s bien thien nong o cua mot cau t nao o trong qua trnh chuan o theo lng thuoc th them vao. Truc tung bieu dien nong o (hay logarit nong o) cua cau t; truc hoanh bieu dien lng thuoc th them vao (so ml). 2. Yeu cau cua phan ng dung trong phan tch the tch: Nhng phan ng hoa hoc dung trong phan tch the tch phai bao am cac yeu cau sau: - Chat can xac nh X phai phan ng hoan toan vi thuoc th R theo mot he so t le nhat nh (tc theo mot phng trnh phan ng xac nh). - Phan ng phai dien ra nhanh. oi vi cac phan ng cham can lam tang toc o phan ng bang cach un nong, them xuc tac
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 + Y Sau o chuan lng Y giai phong ra bang mot thuoc th R vi ch th thch hp . Da vao the tch va nong o cua thuoc th R ta tnh c lng chat can xac nh X. ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng d) Chuan o gian tiep:
- 74 -
Chat can xac nh X c chuyen thanh mot chat khac co cong thc phan t xac nh va trong cong thc o co t nhat mot nguyen to co the chuan o trc tiep bang mot thuoc th va chat ch th thch hp. II. Cac cach bieu dien nong o dung dch: Nong o la mot ai lng dung e ch ham lng cua mot cau t (phan t, ion ..) trong dung dch. Trong hoa phan tch thng dung cac cach bieu dien nong o sau: 1. Nong o the tch: Nong o the tch cua mot chat long la t so gia the tch cua chat long o va the tch cua dung moi (thng la nc). V du: dung dch HCl 1:4 la dung dch gom 1 the tch HCl ac (d= 1,185g/ml) va 4 the tch nc. 2. Nong o phan tram khoi lng (p%): Nong o phan tram khoi lng cua mot chat la so gam cua chat o tan trong 100 gam dung dch. Neu goi a la so gam cua chat tan q la so gam cua dung moi
p% =
a 100 a+q
khi o Q = a + q la so gam cua dung dch th: V du: 1- Hoa tan 50g KCl vao 150ml nc th c dung dch KCl nong o phan tram khoi lng la bao nhieu? Cho nc co d = 1g/ml. Giai: Ap dung cong thc tren tnh c p% cua dung dch KCl = 25%. 2- Can hoa tan 20gNaCl trong bao nhieu ml nc e co dung dch NaCl 10%. Giai: Ap dung cong thc tren tnh c q= 180g. Ma q = V.d = 180 vi d = 1 nen V = 180ml. Vay muon co dung dch NaCl 10% th phai hoa tan 20g NaCl trong 180ml nc. 3- Co bao nhieu gam H2SO4 nguyen chat trong 1ml H2SO4 ac 98% (d = 1,84g/ml) Giai: Ap dung cong thc tren vi Q = a + q = 1,84 .1 t o tnh c a = 1,8032g
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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:
C
V du:
a M.V
neu V tnh bang ml th : C
a.1000 M.V
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
neu V tnh bang ml th : C =

N
a.1000 .V
Nong o ng lng c tnh theo cong thc: Trong o a: so g (mg) chat tan trong V lt (hoac ml) dung dch. : ng lng gam. * ng lng gam: ng lng gam cua mot chat trong mot phan ng hoa hoc la so gam cua chat o tng ng ve mat hoa hoc vi 1 nguyen t gam hay ion gam hyro hoac hyroxit hoac 1 na nguyen t gam oxi. ng lng gam cua mot chat khong phai la mot hang so nh phan t gam cua no ma thay oi tuy theo phan ng no tham gia. * Cach tnh ng lng gam: - oi vi phan ng trung hoa: ng lng gam cua mot acid hoac baz trong phan ng trung hoa bang phan t gam cua no chia cho so ion H+ hoac OHma 1 phan t acid hoac baz a tham gia vao phan ng. ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng V du: vi phan ng: 2HCl + Ca(OH)2 = CaCl2 +
- 76 2H2O
Ca( OH )2
M Ca( OH ) 2
con
HCl
=M
HCl
Vi phan ng:
H3PO4 + NaOH
NaH2PO4 +
H2O
H3PO4 = MH3PO4 va NaOH = MNaOH
H PO =
3 4
M H 3PO 4 2
; NaOH = M NaOH
= Na2HPO4 + = FeCl3 + 2H2O 3H2O
Vi phan ng: Vi phan ng
H3PO4 + 2NaOH Fe(OH)3 +

Fe ( OH )
3HCl
3
Fe(OH ) =
3
; 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 + 3Pb(NO3)2 = 2Al(NO3)3 + 3PbSO4
Al
M
2
( SO )
Al ( SO )
2
4 3
4 3
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 5Fe2(SO4)3 + K2SO4 + 2MnSO4 +
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 + e-
M KMnO4 5
8H+ + 5eFe3+
Mn2+ +
4H2O
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng FeSO4 = MFeSO4
- 77 -
V du ve viec pha cac dung dch co nong o ng lng 1- Tnh so gam KOH can e pha 2 lt dung dch KOH 0,25N. Cho phan t lng cua KOH la 56,1 Giai: T cong thc tnh CN suy ra a = CN..V = 0,25.56,1.2 = 28,05g. 2- Can phai can bao nhieu gam Na2CO3 e ieu che 250ml dung dch Na2CO3 0,1N. Cho phan t lng cua Na2CO3 la 105,99. Giai nh bai tren nhng vi Na2CO3 th = M/2, tnh c a = 1,3249g. 5. o chuan: o chuan la so gam (hoac so mili gam) cua chat tan trong 1ml dung dch. Neu goi a la so gam (hoac mg) chat tan trong Vml dung dch th o chuan TR cua dung dch bang:
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.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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. Cach chuyen nong o dung dch:
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
N
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=
C .M 1000 C . 1000
N M
hay
T.1000 M
T=
hay C =
N
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
4. Chuyen nong o P% thanh nong o M hoac N va ngc lai:
10 .P%.d M
va C =
N
10 .P%.d
trong o d la khoi lng rieng cua dung dch.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 79 -
5. Chuyen nong o P% thanh o chuan TR hoac o chuan theo chat can xac nh:
P% =
TR .100 d
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
So ng lng cua chat X co trong V0 ml dung dch se la:
VR C N ,R 1000
Vay so gam cua chat X trong V0ml dung dch se la:
m =
X
VR .C N ,R . X 1000
Trong o X la ng lng gam cua chat X. Neu lay a gam mau X hoa tan thanh Vml dung dch, sau o lay V0ml dung dch nay em chuan o chat X th het VR ml dung dch thuoc th R co nong o ng lng CN,R . Tnh so gam cua chat X trong Vml dung dch cung chnh la so gam cua chat X trong a gam mau:
VR .C N ,R . X V . mX = 1000 V0
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Vay ham lng phan tram cua chat X trong mau:
- 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 Ap dung quy luat ng lng: (CN.V)NaOH = (CN.V)HCl t o tnh c: CN (NaOH) = 0,1206N Vi NaOH CN = CM Vay nong o phan t cua NaOH cung bang 0,1206M. Suy ra so gam trong 20 ml dung dch la 0,09646g. 2- Can 0,2016g muoi Na2CO3 ky thuat hoa tan thanh Vml dung dch. Khi chuan toan bo Vml dung dch nay cho en khi chuyen toan bo Na2CO3 thanh H2CO3 th ton het 20,16ml dung dch HCl 0,1N. Tnh ham lng % cua Na2CO3 trong muoi. Cho MNa2CO3 = 106. Giai: Phng trnh chuan o: Na2CO3 + 2HCl = CO2 + H2O + 2NaCl
X% =
Ap dung cong thc: Trong o Na2CO3 = 53
VR .C N ,R . X V 100 . . 1000 V0 a
T o tnh c Na2CO3% = 53% 3- Chuan o 25ml dung dch H2SO4 bang dung dch NaOH co o chuan 4,257mg/ml th dung het 22,80ml dung dch NaOH. Tnh lng H2SO4 co trong 250ml dung dch H2SO4. Giai: T nh ngha o chuan suy ra so gam NaOH co trong 22,80ml dung dch la: 4,257.22,8 = 97,0596 mg. Theo qui luat ng lng: so mili ng lng NaOH = so mili ng lng H2SO4 = (97,0596: 40). Vay so mg H2SO4 co trong 25ml dung dch la: (97,0596: 40).49,04.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng T o tnh c so mg H2SO4 co trong 250ml dung dch la:1190mg. 2. Trng hp chuan o ngc:
- 81 -
Them mot the tch chnh xac va d VRml dung dch thuoc th R co nong o CN,R vao V0ml dung dch chat can xac nh X. Sau khi X tac dung het vi thuoc th R, chuan lng R d bang mot thuoc th R thch hp co nong o CN (R) th ton VRml. Tnh nong o ng lng va so gam cua chat X trong V0ml dung dch? Giai: Theo qui luat ng lng: So ng lng gam cua thuoc th R = tong so ng lng gam cua chat X + thuoc th R. Tc la: CN,RVR = CN,X V0 + CN,R. VR T bieu thc nay suy ra CN,X va t o tnh so gam cua X trong V0 dung dch la:
m =
X
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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng V. Cach ieu che dung dch: 1. ieu che dung dch chuan: a) Chat goc:
- 82 -
Chat goc la chat dung e ieu che cac dung dch chuan (dung dch co nong o chnh xac xac nh). Mot chat c goi la chat goc phai thoa man cac yeu cau di ay: - Chat phai tinh khiet phan tch hoac tinh khiet hoa hoc, lng tap chat phai nho hn 0,1%; neu ln hn phai tinh che lai. - Thanh phan hoa hoc phai ng vi mot cong thc xac nh ke ca nc ket tinh. - Chat goc va dung dch chuan phai ben. - Khoi lng phan t (nguyen t) cang ln cang tot e giam sai so khi ieu che dung dch chuan. V du: K2Cr2O7 , H2C2O4.2H2O la nhng chat goc, NaOH khong phai la chat goc v no de hut am va CO2. (Chat goc co the la nhng kim loai nguyen chat nh Cu, Au, Ag) b) Cach ieu che dung dch chuan: co nhieu phng phap: * Dung chat goc: - Neu co chat goc th can mot lng chnh xac xac nh tren can phan tch co o chnh xac cao ( 0,1mg ), hoa tan roi nh mc en vach. - Neu khong co chat goc th trc het can phai chuan b dung dch co nong o gan ung, sau o dung chat goc hoac dung dch thch hp e xac nh lai nong. V du: Can pha dung dch NaOH chuan e chuan o HCl, th au tien phai chuan b dung dch NaOH co nong o gan ung sau o dung dung dch H2C2O4 de chuan lai cho chnh xac. * Dung Fixanal: V du: a- Muon pha 250ml dung dch H2C2O4 0,1M th phai dung bao nhieu gam H2C2O4.2H2O. b- Chuan 20ml dung dch acid oxalic nay bang mot dung dch NaOH vi ch th phenolphtalein th tieu ton 24ml dung dch NaOH. Tnh nong o phan t cua dung dch NaOH. Cho phan t lng cua H2C2O4.2H2O = 126,066. Giai: a- So gam H2C2O4.2H2O bang 3,1517g. b- Nong o phan t cua dung dch NaOH la 0,1667M.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng 2. ieu che cac dung dch t cac dung dch co nong o khac: a) Pha loang dung dch:
- 83 -
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 Q2 = a + q2
C =P %=
1 1
a a .100 = .100 a + q1 Q1 a a .100 = .100 a + q2 Q2
C =P %=
2 2
C2
C1
P2
P1
a + q2 a + q1
Q2 Q1
C2
C1
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://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng - Neu nong o tnh theo CM, CN, TR, TR/X th : C1.V1 + C2V2 = C(V1 + V2) = CV
- 84 -
C1 Q 1 100
C2Q 2 100
C(Q1 + Q 2 ) 100
(C1 C)Q1 = (C C 2 )Q 2
Q2
Q1
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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc

Chng III. PHNG PHAP TRUNG HOA
- 85 -
(PHNG PHAP ACID BAZ) Nguyen tac cua phng phap trung hoa la da vao phan ng trung hoa e xac nh nong o cua acid, cua baz hay cua muoi co tnh acid hay baz ro ret. Cac phan ng dung trong phng phap nay eu thoa man cac yeu cau oi vi cac phan ng dung trong phan tch the tch nhng can lu y: - Cac dung dch chuan phai la nhng acid hay baz manh e phan ng trung hoa co tnh nh lng cao. - oi vi viec chuan o cac acid bang baz manh va ngc lai th ieu kien ve tnh nh lng c thoa man. Con oi vi viec chuan o acid yeu hay baz yeu e cho hang so toc o phan ng u ln th acid hay baz o khong c qua yeu. Do o phai co mot gii han oi vi pKa hay pKb (gii han nay con phu thuoc vao nong o dung dch can chuan o). Trong qua trnh chuan o, nong o cua ion H+ va OH thay oi dan en pH cua dung dch thay oi. ng bieu dien s bien thien cua pH theo lng acid hay baz them vao trong qua trnh chuan o c goi la ng chuan o acid- baz. e tnh ga tr pH tai cac thi iem chuan o, ta can phai thiet lap phng trnh lien he nong o cua ion H+ va cua ion OH- vi lng acid hoac baz a c chuan o, phng trnh nay c goi la phng trnh ng chuan o. Do acid va baz eu la nhng dung dch khong mau nen e xac nh iem tng ng (iem ket thuc qua trnh chuan o) ta phai dung nhng chat co mau thay oi tai iem hoac gan sat iem tng ng Nhng chat nay goi la chat ch th acidbaz (hoac chat ch th pH). I. Chat ch th acid-baz : Chat ch th acid-baz thng la nhng acid (HInd) hoac baz (IndOH) hu c, thuoc loai pham nhuom. Mau sac cua chat ch th thay oi tuy thuoc vao pH cua dung dch. Cac chat ch th oi mau trong nhng khoang pH khac nhau, t gia tr thap en cao. Do o ta co the chon cho tng trng hp chat ch th nao co vung oi mau gan iem tng ng nhat. 1. Khoang pH oi mau cua chat ch th: Xet chat ch th dang acid HInd
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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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
va = 10 vao bieu thc tnh pH tren th : pH = pK
aHInd
Vay khoang pH oi mau cua chat ch th ma mat ta nhan thay c la 2 n v pH. oi vi chat ch th baz cung lap luan tng t. Tuy nhien oi vi mot so chat ch th, ta co the nhan biet s oi mau trong khoang pH nho hn 2 n v, tc la ty so nong o cua cac dang mau nho hn 10 lan. Di ay la mot so loai chat ch th acid-baz thong dung: Chat ch th Metyl da cam Metyl o 0.2% o trung tnh Phenolphtalei n Ka HInd 1,8.1010-5 10
-7
Khoang pH oi mau 3.1 4.4 4.4 6.2 7.0 7.4 8.0 10
Mau pT 4 5.5 7.2 9 Acid o o Hong Khong mau Vang Vang Luc Tm hong Baz
2.10-10
pT cua chat ch th la ga tr pH ma o chat ch th oi mau ro nhat trong vung pH chuyen mau. Thng pT pKaHInd = pHC (pH tai iem cuoi cua s chuan o). 2. Ch th hon hp: e giup nhan ra s oi mau ro ret va chnh xac ngoai viec chon ch th thch hp, ta con co the dung ch th hon hp, thng gom 2 ch th pH tron lan vi nhau hoac 1 chat la ch th pH con chat kia la chat mau tr (co mau nhat nh khong thay oi theo pH ) Ch th hon hp giup ta nhan biet c khoang pH oi mau rat nho (0,2 0,5 n v pH) mau dang acid va mau dang baz rat tng phan. V vay khi chuan o khong can e y en mau trung gian, ch can biet en mau moi dang la u.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 + H+ + BOH OH= = BA 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 + ])
Trong o F la mc o acid a c chuan do
V0 + V C 0 V0
(1)
F=
So milimol baz a them vao CV = So mi lim ol acid ban au C 0 V0
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:
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng - C0 = [OH-] - [H+] Vay:
- 88 -
[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 )
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 :
V0 + V
C 0 V0
C 0 V0 + CV V0 + V
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
[OH ] = (F 1)
V0 + V
C 0 V0
pOH = lg( F 1)
V0 + V C 0 V0
C 0 V0
pH = 14 pOH = 14 + lg( F 1)
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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Nen phng trnh tong quat (1) co the viet lai:
- 89 -
F 1 = ([OH ] [H + ])
V0 + V C 0 V0
= ([OH - ] [H + ])
C0 + C C0C
b) Chuan baz manh bang acid manh: Tng t nh tren ta cung thiet lap c phng trnh ng chuan o khi chuan V0 ml dung dch baz manh co nong o C0 bang acid manh co nong o C la :
F 1 = ([H + ] [OH ])
V0 + V C 0 V0
(2)
Trong o F la mc o baz a c chuan do
F=
So milimol acid a them vao CV = So mi lim ol baz ban au C 0 V0
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 )
V0 + V
C 0 V0
C 0 V0 CV V0 + V
nen pOH = -lg[OH-] t ay se tnh c pH * Tai iem tng ng : So milimol acid them vao = so milimol baz 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 acid manh d nhieu, nen [H+] >> [OH-], ta co the bo qua [OH-] ben canh [H+], nen phng trnh (2) tr thanh:
F 1 = [H + ]
V0 + V C 0 V0
[H + ] = (F 1)
V0 + V
C 0 V0
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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
ng cong chuan o baz manh bang acid manh oi xng vi ng cong chuan o acid manh bang baz manh . V du: chuan o 100ml dung dch HCl co nong o 0,1M bang dung dch NaOH 0,1M. a- Tnh pH cua dung dch tai cac thi iem khi them: 0; 50; 90; 99; 99,9; 100; 100,1; 101; 110; 200ml dung dch NaOH. b- Ve ng cong chuan o. Nhan xet. Giai: a- Khi VNaOH = 0 th pH = 1 Khi VNaOH = 50; 90; 99; 99,9 ap dung cong thc trc va xa iem tng ng tnh c cac pH tng ng la: 1,48; 2,28; 3,30; 4,30. 7. Khi VNaOH = 100 ap dung cong thc tai iem tng ng tnh c pH =
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 :
14 12 10 8 6 4 2 0 0 0.5 1 1.5
pH
- Khi F < 0,99 pH thay oi rat t ( pH ch thay oi t 1 en 3,30 ) trong khi the tch NaOH thay oi ln ( t 0 en 99ml) va khi F > 1,01 pH cung thay oi rat t ( t 10,70 en 12,56 ) trong khi the tch NaOH thay oi ln ( t 101 en 200ml). - oan pH tai thi iem F = 0,999 va F = 1,001 goi la bc nhay v F trong khoang nay pH thay oi ot ngot trong khi lng NaOH ch thay oi (100,1 - 99,9) = 0,2ml ma pH thay oi 2 (9,7 - 4,3) = 5,4 n v; khoang nay goi la bc nhay cua ng chuan o.
- 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
n g cong chuan o acid ma n h ban g baz man h
http://hoahocsp.tk
Khoa Hoa hoc
- 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
Neu tnh theo % th
S% =
CV C 0 V0 C 0 V0
100 = ( F 1)100
Khi F < 1 th S < 0 chat ch th oi mau trc iem tng ng (sai so do phan acid hoac baz con lai cha c chuan o) Khi F > 1 th S > 0 chat ch th oi mau sau iem tng ng (sai so do phan acid hoac baz tng ng vi lng baz hoac acid d ) Vay oi vi trng hp chuan acid manh bang baz manh th :
S% = [OH ]C [H + ]C
+V )V 100 C V
0 0 0
trong o C la ch cuoi viet tat. T phng trnh nay co the tnh c S% cac thi iem
S% = [H + ]C
V0 + V C 0 V0
100
+ Trc va xa iem tng ng:
S% = [OH ]C [H + ]C
+ Sat iem tng ng:
)CC +CC 100

0 0
S% = [OH ]C
+V )V 100 C V
0 0 0
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng + Sau va xa iem tng ng:
- 92 -
S% = [H + ]C [OH ]C
+V )V 100 C V
0 0 0
oi vi trng hp chuan o baz manh bang acid manh ta cung co: Va cung co the bien luan nh trng hp chuan acid manh Lu y rang : Sai so ch th la sai so he thong. Viec chon ung chat ch th e xac nh iem tng ng la ieu kien quan trong nhat quyet nh o chnh xac cua phep chuan o. e xac nh iem tng ng vi sai so nho hn 0,1% ta co the dung tat ca cac ch th co khoang pH oi mau trong bc nhay va co pT cang gan iem tng ng cang chnh xac. Muon sai so ch th < 0,1% (tc con lai va tha 0,1% acid cha chuan va xut d) viec chuan o cac acid manh bang baz manh co nong o c 0,1 M th bc nhay la 4,3 9,7 nen co the chon c nhieu ch th, chang han metyl o, phenolphtalein, neu chon sai so ch th < 1% th bc nhay 3,3 10,7 th co the chon them ch th metyl da cam. V du: 1- Tnh sai so ch th khi chuan o dung dch HCl 0,1M bang dung dch NaOH 0,1M neu dung ch th phenolphtalein ( pT=9). 2- Neu chuan HCl 0,1M bang NaOH 0,1M th can ket thuc chuan o trong khoang pH nao e sai so chuan o khong qua 0,1%. III. Chuan o acid yeu bang baz manh va ngc lai 1. Chuan acid yeu bang baz manh a) Phng trnh ng chuan o acid yeu bang baz manh Gia s chuan o V0 ml dung dch acid yeu HA co nong o C0 va hang so acid Ka bang dung dch baz manh BOH co nong o C Phan ng chuan o : Viet dang ion HA + BOH OH BA A+ + H2O H2O (1) HA +
Phng trnh ng chuan o cua qua trnh nay co dang
F 1 = ([OH ] [H ])
V0 + V C 0 V0
[H + ] [H + ] + K a
F=
CV C 0 V0
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Trong o va V la the tch baz a s dung
- 93 -
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 + ] =
Neu Ka << [H+] th
K a + [H + ]
K aC 0
[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 ]
tao thanh, dan en hnh thanh mot he em HA/A- do vay: Trong o * Tai iem tng ng F =1: dung dch ch gom A- do muoi BA phan ly ra,
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
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 ] =
C b = [A ] =
pH = 7 + 0,5pKa + 0,5lgCb
CC 0 CV = V0 + V C 0 + C
C C 1 1 pH = 7 + pK a + lg 0 2 2 C0 + C
ang Th Vnh Hoa Khoa Hoa hoc
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 CV C 0 V0 V0 + V
CV C 0 V0 V0 + V
pH = 14 + lg
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
C 0 V0
pH = 14 + lg( F 1)
V0 + V [H + ] [H + ] + K a
F 1 = [OH ]
[H+] canh [OH-] va luc nay
V0 + V C 0 V0
b) Sai so ch th : cong thc tnh sai so tong quat :
S = FC 1 = [OH ]C [H ]C
)C V
0
V0 + V
0
K a + [ H + ]C
[ 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 =
K a + [ H + ]C
[H + ]C
+ Sau va xa iem tng ng :
S = [OH ]C
V0 + V C 0 V0
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng + Sat iem tng ng : [H+] << [OH-] nen
- 95 -
S = FC 1 = [OH ]C
V du:
C0 + C C0C
K a + [ H + ]C
pH
14 12 10 8 6 4 2 0
[H + ]C
1. Tnh pH tai cac thi iem chuan o khi chuan o 100ml dung dch CH3COOH 0.1M ( pKa = 4.76) bang dung dch NaOH 0.1M. Ve ng chuan o. Giai: Ap dung cac cong thc a neu tren ta tnh c pH cac thi iem khac nhau: - Khi a them 0; 20; 50; 90; 99; 99,9ml dung dch NaOH th cac gia tr pH lan lt la 2,88; 4,16; 4,76; 5,71; 6,76; 7,76. - Khi a them 100ml dung dch NaOH (tai T) th pH bang 8,73. - Khi a them 100,1; 101; 110; 200ml dung dch
F
0 0.5 1 1.5 2
ng cong chuan o acid yeu bang baz manh
NaOH th cac gia tr pH lan lt la 9,7; 10,7; 11,68; 12,52. T cac gia tr nay ve c ng cong chuan o Nhan xet: So sanh ng chuan o acid manh va acid yeu: - oi vi acid manh trong khoang 0 <F < 0,1 pH thay oi khong ang ke con oi vi acid yeu s thay oi kha nhieu, acid cang yeu s thay oi pH cang nhieu. ieu o chng to acid manh co em nang ln . - vung chuan o c mot na (F = 0,5) pH cua dung dch acid yeu hau nh khong oi (do tao thanh dung dch em) con vi acid manh pH cung thay oi khong ang ke. - Khac vi chuan o acid manh bang baz manh, pH iem tng ng trong qua trnh chuan acid yeu bang baz manh >7. Acid cang yeu va nong o acid cang ln th iem tng ng cang chuyen ve pha moi trng kiem. - Tai F = 0,5 th pH = pKa . Vay pKa tang th phan ng cong chuan o trc iem tng ng cang nang cao len trong khi phan ng cong chuan o sau iem tng ng van co nh neu C0 khong oi.Vay bc nhay pH nho dan khi pKa tang. - Bc nhay cua ng nh phan trong qua trnh chuan acid yeu bang baz manh luon nho hn bc nhay cua qua trnh nh phan acid manh bang baz ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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
CM
Cb
= 14 pK b + lg
C 0 V0 CV CV
C V = 14 pK b + lg 0 0 1 CV
pH = 14 pK + lg
b
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
Tnh C tai thi iem can bang (chu y en s pha loang)
C C 1 1 pH = 7 pK b lg 0 2 2 C0 + C
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng * Sau va xa iem tng ng F >1: pH do acid manh d quyet nh
- 97 -
[H + ] = (F 1)
V0 + V
C 0 V0
* Sat iem tng ng: ch bo qua c [OH-] canh [H+]
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; pKa3 - pKa2 = 5,15 > 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 * F = 0: dung dch ch gom H3PO4 co the xem nh la mot n acid co pKa = 2,12 va xem nh la mot n acid trung bnh do o: [H+]2 + Ka. [H+] - Ka.Ca = 0 [H+]2 + 10-2,12 [H+] - 10-2,12.10-1 = 0 giai phng trnh bac hai nay suy ra pH 1,62 * 0 < F <1: dung dch gom H3PO4 cha c trung hoa va H2PO4- cho nen xem nh mot dung dch em :
pH = pK a1 lg
4 [H PO ] 2 4
[H PO ]
3
1 F = pK a1 lg F
F=
CV C 0 V0
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Khi F = 0,99:
- 98 -
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:
pH
14 12 10 8 6 4 2 0 0
Dung dch ch gom H2PO4-, v H2PO4va la acid cua he: H2PO4- / HPO42- co pKa2 va la baz cua he: H3PO4 / H2PO4co pKa1. Xem nh ay la he acid -baz khong lien
pH
T1
hp, cho nen :
1 1 pK + pK = (2,12 + 7,21) = 4,67 a1 a2 2 2
Do vay ta phai chon chat ch th hon hp (Brom cresol + metyl o) trong trng hp khong co ch th hon hp co F the dung ch th metyl da cam, khi o sai so se ln hn 0,1%.
n g cong chuan o a acid ban g baz man h
1 2
Nac 2: NaH2PO4 + NaOH Na2HPO4 +
H2O
* 1 < F < 2: dung dch gom H2PO4- va HPO42-
pH = pK a2 lg
[H PO
2
[HPO
] 4 2
pH = pK
Khi F = 1,01 th:
a2
lg
2F F 1
pH1,01 = 7,21 - lg(2-1,01)/(1,01-1) = 5,21 ay la iem cuoi cua bc nhay 1. Khi F =1,99 th: pH1,99 = 7,21 - lg(2-1,99)/(1,99-1) = 9,21 ay la iem au cua bc nhay 2. * F = 2 : Tai iem tng ng th 2, dung dch ch gom HPO42HPO42- la acid cua cap HPO42- / PO43pKa3 la baz cua cap H2PO4- / HPO42- pKa2 ay la he acid -baz khong lien hp cho nen :
pH =
ang Th Vnh Hoa
1 1 pK + pK = (7,21 + 12,36 ) = 9,79 a2 a3 2 2

http://hoahocsp.tk
Khoa Hoa hoc
- 99 -
Do vay ta chon chat ch th hon hp (phenolphtalein + thymolphatalein) neu khong co ch th hon hp co the dung ch th la phenolphtalein, khi o sai so se ln hn 0,1%. Nac 3 : Na2HPO4 + NaOH Na3PO4 + H2O
pH = pK pH = pK
a3
lg lg
[HPO 4 2 ] [PO 4 3 ] 3F F2
a3
* 2< F < 3 : dung dch gom HPO42- va PO43- (he em) Khi F = 2,01 th pH = 12,36 -lg(3-2,01)/(2,01-2) = 10,36 la iem cuoi cua bc nhay 2. Khi F = 2,99 th pH = 12,36 - lg(3-2,99)/(2,99-2) = 14,36. * F = 3 : dung dch gom PO43- xem nh mot a baz va tnh giong nh mot n baz va nh the co ngha la nac 3 khong co bc nhay nen ch chuan o ti sau iem tng ng 2 v nac th 3 qua yeu khong the chuan o c. Sai so ch th : Van S = FC - 1 Neu ch th oi mau trc iem tng ng 1:
S% =
[H + ] K a1
100
Neu ch th oi mau sau iem tng ng 1:
S% =
Ka
+
[H ] c
100
Neu ch th oi mau trc iem tng ng 2:
S% =
[H + ] Ka
2
100
Neu ch th oi mau sau iem tng ng 2:
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 ?
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng V. Chuan o mot a baz bang mot acid manh
- 100 -
Cung tng t nh chuan a acid : v du nh chuan o V0ml Na2CO3 nong o C0 bang dung dch HCl co nong o C - Neu a baz co Kb1, Kb2, .khac xa nhau pKb 4 th co the chuan o tng nac mot bang ch th thch hp. - Neu pKb 2 th khong the chuan tng nac c. Cac cong thc cung giong nh khi chuan a acid, ch khac la thay pH bang pOH , pKa bang pKb tc la: - Neu 0 < F <1:
pOH = pK
- Neu F =1
b1
lg
1 F F
1 pOH = ( pK + pK ) b1 b2 2
- Neu 1 < F < 2
pOH = pK
- Neu F = 2
b2
lg
2F F 1
1 pOH = ( pK + pK ) b2 b3 2
Sai so : * Trc iem tng ng 1 :
S% =
[ H + ]C
K a2
100
* Sau iem tng ng 1 :
[H + ] S% = 100 K a1
* Trc iem tng ng 2 :
S% =
[H + ]C
K a1
100
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng * Sau iem tng ng 2
- 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 H3PO4 + NaOH NaCl + H2O NaH2PO4 + H2O pKa2 pKa1
Tai iem tng ng 1: H2PO4- quyet nh pH cua dung dch H2PO4- va la acid cua cap H2PO4- / HPO42va la baz cua cap H3PO4 / H2PO4-
pH = ( pKa2 + pKa1) = ( 2,12+7,21 ) = 4,67 nen chon ch th metyl da cam hoac metyl o. Tai iem tng ng 2 : HPO42- va la acid cua cap HPO42- / PO43pKa3 va la baz cua cap H2PO4- / HPO42- pKa2 pH = (pKa3 + pKa2 ) = (7,21 + 12,36 ) = 9,79 nen chon phenolphtalein lam chat ch th 4. Hon hp hai n acid yeu: Gia s co hon hp hai acid: HA1 co pKa1 HA2 co pKa2
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 NaCl + H2O NaHCO3 + NaCl pKa2 Na2CO3 + HCl
* Tai iem tng ng 1: pH do HCO3- quyet nh HCO3- va la acid cua cap HCO3- /CO32va la baz cua cap H2CO3 /HCO3- pKa1 ch th pH = (pK1 + pK2 ) = (6,35 + 10,33 ) = 8,34 chon phenolphtalein la chat * Tai iem tng ng 2: NaHCO3 + HCl 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://hoahocsp.tk
Khoa Hoa hoc
- 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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc

Chng IV. PHNG PHAP TAO PHC
- 104 -
(PHNG PHAP CHUAN O PHC CHAT) I. Cac phng phap chuan o phc chat: Cac phng phap chuan o phc chat da tren phan ng tao phc cua cac chat. Trong phan tch the tch ngi ta thng dung cac phng phap tao phc sau: 1. Phng phap thuy ngan II: Da vao phan ng tao phc gia ion Hg2+ vi cac anion Cl-, Br-, I-, CN-. V du: Hg2+ HgCl+ Hg2+ + + + ClCl4IHgCl+ HgCl2 HgI42-
e nhan ra iem tng ng ngi ta thng dung cac ch th: - iphenylcarbazit moi trng pH = 1,5 2 - iphenylcarbazon moi trng pH = 2,0 3,5 V nhng pH nay Hg2+ mi tao phc c vi ch th nhng phc co mau xanh tm. Cho nen iem tng ng la iem bat au xuat hien mau xanh tm cua phan ng gia thuy ngan vi ch th. Phng phap nay rat t c s dung nen trong pham vi giao trnh nay ta khong xet en. 2. Phng phap Bac: Ngi ta chuan o dung dch cyanua (CN-) bang dung dch AgNO3: - Trc diem tng ng: trong dung dch co d CN- nen xay ra phan ng tao phc sau: Ag+ + 2CNAg(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)2Ag[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.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng II. Phng phap complexon:
- 105 -
Complexon la ten goi chung cua cac dan xuat cua cac acid aminopolycarbocylic, co nhieu loai complexon, nhng trong phan tch thng dung complexon III (con goi la EDTA) la acid EtylenDiaminTetraAcetic viet tat H4Y
HOOC CH2 HOOC CH2 N CH2 CH2 N CH2 COOH 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 N CH2 CH2 N CH2 COONa 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+ + H2Y2V 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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 106 -
nhng 1 ion gam kim loai luon luon tng tac vi 1 ion gam complexon III ong thi giai phong ra 2H+. Me2+ + Me3+ + Me4+ + H2Y2H2Y2H2Y2MeY2MeYMeY + 2H+ + 2H+ + 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 H3Ind H2Indo HInd2Xanh biec Ind3Da 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 H2Y2MeY2+ HInd2- + Xanh H+
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://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng b) Murexit: Thng viet tat la H4Ind- trong nc no phan ly nh sau: H4IndTm hong H3Ind2Tm H2Ind3Xanh tm
- 107 -
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 Y4HY3H3YM + + + + + Y4Y H+ H+ H+ H+ L MY(4-n)- e n gian ta khong viet ien tch MY HY3H2Y2H3YH4Y ML : : : : K4 K3 K2 K1 : 1
* Cac can bang phu (phan ng phu) cua M va Y:
H2Y2- +
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng ML M Ln-1 + + L L ML2 MLn : 2 : n
- 108 -
(L la cac phoi t khac trong dung dch nh OH- , NH3) Phng trnh cua ng chuan o co dang:
F 1 = ([Y ' ] [M' ])
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
[M' ] + [MY ] =
C 0 V0 [MY ] =C V [M ' ] V V0 + V 00 + 0 V [M ' ] [MY ] [MY ] V0 + V ' = [ Y' ] = = [M' ][Y' ] ' [M' ] ' [M' ] C 0 V0
Vay phng trnh chuan o c viet lai:
C 0 V0 [M ' ] V +V V +V F 1 = 0 [M ' ] 0 ' [M' ] C 0 V0
(2)
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Bien luan : - Khi F =0 (cha them complexon) luc nay dung dch ch cha M pM = -lg[M] = -lgC0
- 109 -
- 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 )
V0 + V
C 0 V0
[M ] =
[M ' ]
L
- 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)
V0 + V
C 0 V0
C 0 V0 [M ' ] V +V V +V F 1 = 0 0 ' [M' ] C 0 V0

Hoac t (2) suy ra : V [M]rat nho so vi C0V0 /(V0+V) do vay
[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' ]
[M' ] <<
V0 + V
C 0 V0
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Suy ra :
- 110 -
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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc

Chng V. PHNG PHAP CHUAN O KET TUA
- 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+ + 2XHg2X2 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 Moi phng phap se co mot chat ch th rieng ac thu. Trong chng nay chung ta ch xet phng phap Bac II. Phng phap o bac: Da tren s tao thanh ket tua cua muoi Ag t tan. 1. Phng trnh ng chuan: Ga s chuan o V0 ml dung dch muoi MX (X co the la Cl-, Br-, I-, SCN-) co nong o C0 bang dung dch AgNO3 co nong o C. Khi them V ml dung dch AgNO3 th phan ng chuan o xay ra nh sau: AgNO3 + MX AgX + MNO3 AgX + M+ + NO3Ag+ + NO3- + M+ + X-
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://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng - Phng trnh tch so tan : [Ag+][X-] = TAgX (1) - Phng trnh bao toan khoi lng oi vi Ag+ va X- :
- 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 ] =
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
F=
Vi
CV C 0 V0
F 1 = [Ag + ] [ X ]
)C V
0
V0 + V
0
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.
T V +V AgX 0 F 1 = [Ag + ] C V [Ag + ] 0 0

Bien luan : - Trc va xa iem tng ng (F < 1): [X-] >> [Ag+]
F 1 = [X ]
Suy ra :
V0 + V C 0 V0
[X ] = (1 F )
V0 + V
C 0 V0
[Ag + ] =
TAgX V + V 0 1 F C 0 V0
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 113 -
- Tai iem tng ng (F =1)
[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 ]
C0 + C C0C TAgX V + V [X ] = ( 0 ) F 1 C 0 V0
[Ag + ] = (F 1)
2. Sai so cua phep chuan o:
V0 + V
C 0 V0
Van tnh theo cong thc: S = F -1 va S% = (F -1).100 - Trc iem tng ng:
S = [X ]C
V0 + V C V
0 0
TAgX
[Ag + ]C C 0 V0
V0 + V
- Sau iem tng ng:
S = [Ag + ]
V0 + V C 0 V0
- Sat iem tng ng:
S = [Ag + ] [X ]
C0 + C C0C
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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
pAgc = 4,3 < pAgt nen ket thuc sau iem tng ng. T o tnh c sai so S% = 0,1% Neu tnh chnh xac th phai tnh sat iem tng ng khi o sai so S% = 0,094%
4.9
4- Khi S = -0,2%: trc iem tng ng, tnh c pAg = 5,8.

F
0 1 2
Khi S = 0,2%: sau iem tng ng, tnh c pAg = 4.
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 + CrO42AgX (1) Ag2CrO4 o gach (2)
Ta co T AgBr = 10-12.28 , T AgCl = 10-9.75 , T Ag2CrO4 = 10-11.95
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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+ 2CrO42- + 2H+ Ag+ + OH2Ag+ + CrO42HCrO4Cr2O72- + H2O lam giam nong o CrO42AgOH Ag2O + H2O cung gay ra sai so
ieu nay gay ra sai so dng, mat khac: - Trong moi trng kiem (pH qua cao) th : 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 .
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng b) Phng phap Fajans:
- 116 -
S dung ch th hap phu , thng dung la Fluorescein dung e xac nh Cl-, Br-, I-, va SCN-. Trong qua trnh chuan o cac halogenua X- bang AgNO3 , trc iem tng ng trong dung dch d X- nen AgX se hap phu X- tao thanh nhng hat keo mang ien tch am {(AgX)nClx-x}. Tai iem tng ng trong dung dch khong d Ag+ va X- nen cac ket tua khong mang ien tch, chung lang xuong lam cho dung dch tr nen trong. Ngi ta goi la iem ang ien. Sau iem tng ng dung dch co d Ag+ nen ket tua AgX hap phu Ag+ hnh thanh hat keo mang ien tch dng {(AgCl)nAgx+x} Da vao tnh hap phu cua cac hat keo Fajans a dung mot so pham mau hu c co kha nang hap phu len be mat cua ket tua tao mau ac trng e nhan ra iem tng ng ma fluorescein la mot ien hnh. Fluorescein ( viet tat la HFl ) la mot acid hu c yeu co kha nang phat huynh quang, dang phan t t do va dang anion khi b hap phu co mau khac nhau. Trong nc co can bang nh sau: HFl
-
H+ + Fl-
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{(AgCl)nAgxx+}xFlMau hong xanh luc
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+ SCNAgX AgSCN TAgSCN = 1,1.10-12 Fe(SCN)2+ phc co mau o mau ( KFe(SCN)2+ -
SCN- d + Fe3+ =10-2,14 )
Vay iem tng ng la luc dung dch chuyen sang mau hi hong. ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng V TAgSCN = 1,1.10-12 < TAgCl =10-9,75 nen co the xay ra phan ng: AgCl + SCNAgSCN + Cl-
- 117 -
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
X
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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc

Chng VI. PHNG PHAP CHUAN O OXY HOA - KH
- 118 -
I. Gii thieu phng phap : Phng phap chuan o oxy hoa - kh la phng phap chuan o da tren phan ng trao oi electron e xac nh cac chat dang oxy hoa hoac dang kh. e xac nh mot chat oxy hoa ngi ta dung dung dch chuan la dung dch chat kh co nong o chnh xac va ngc lai e xac nh mot chat kh ngi ta dung dung dch chuan la dung dch chat oxy hoa. - Dung dch chuan oxy hoa: KMnO4, K2Cr2O7 , I2-Na2S2O3, KBrO3, KIO3 - Dung dch chuan kh : TiCl3, Muoi Mohr e xac nh mot chat nao o, ngi ta thng a chung ve dang oxy hoa hay kh thch hp. Co the bieu dien phan ng chuan o chat Kh2 bang chat Ox1 di dang tong quat nh sau: n2Ox1 + n1Kh2 n2Kh1 + n1Ox2 Kh1 Ox2 Phan ng nay la s to hp cua 2 na phan ng: Ox1 + n1 e Kh2 - n2 e 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.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 : IndOx + neIndKh 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
Luc nay ta thay mau cua Ind Ox Khi [Ind Ox ] [Ind

Kh
1 10
th E = E 0 +
0,059 1 lg n 10
= E0
0,059 n
Luc nay thay mau dang IndKh Th vung oi mau cua ch th nam trong khoang the E = E0 0,059/n (V) Cung nh nhng phng phap trc, ch th c la chon phai co khoang oi mau nam trong bc nhay cua ng cong chuan o. Mot so chat ch th quan trong: * Diphenylamin: La mot baz hu c khong tan trong nc, tan trong acid H2SO4 am ac. Trong dung dch, di tac dung cua chat oxy hoa manh (nh K2Cr2O7) Diphenylamin b oxy hoa bat thuan nghch thanh Diphenylbenzidin.
NH
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 120 -
NH
NH
NH
-2e-
(Dang kh ) khong mau
Eo = 0,76V
2H
(Dang oxy hoa ) mau tm
Khoang the chuyen mau : 0,76 0,059/2 Khi E < 0,73 th ch th ton tai dang kh khong mau Khi E > 0,79 th ch th ton tai dang oxy hoa nen dung dch co mau tm . * Diphenylamin Sulfonat: De hoa tan trong nc .
SO3Na NH C che oi mau nh Diphenylamin E0 = 0,85 V. Dang kh khong mau , dang oxy hoa co mau tm hong co the dung lam ch th e chuan o cac chat oxy hoa bang FeSO4
* Acid N-PhenylAnthranilic : C che oi mau giong cac ch th tren dang kh khong mau , dang oxy hoa co mau hong tm . III. Phng trnh ng chuan o va sai so : 1. oi vi phan ng chuan o oi xng: (trong phng trnh phan ng chuan o dang oxy hoa va dang kh lien hp co he so bang nhau). Ga s chuan o Vo ml chat Kh2 co nong o ng lng la No bang V ml chat oxy hoa Ox1 co nong o ng lng la N. Phan ng chuan o: n2Ox1 + n1Kh2 n2Kh1 + n1Ox2 Kh1 Ox2 Phan ng nay gom hai na phan ng : Ox1 + n1 e Kh2 n2 e
NH COOH
Eo = 1,08 V pH = 0
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 121 -
Phng trnh ng chuan o co dang:
F 1 =
[Ox1 ] [Kh 2 ] [Kh 1 ] [Ox 2 ] 1+ [Kh 2 ] [Ox 2 ]
Trong o: F la mc o chat Kh2 a c chuan
F=
Bien luan:
NV N 0 V0
* 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+
n E0 1 ox1 / kh1
Ox2
Kh1 + m/2H2O
+ n E0
2
n1 + n 2
ox 2 / kh 2
Kh2 -n2e
Phng trnh tong co dang: n2 Ox1 + n1Kh2 + m/2H+ H2O * hoac dang: Ox1 + n1e Kh1
n2Kh1 + n1Ox2 + n2(m/2)
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng Kh2 -n2e + m/2H2O Ox2 + mH+
- 122 -
Phng trnh tong co dang: n2 Ox1 + n1Kh2 + n1H2O
n2Kh1 + n1Ox2 + n12H+
Thng th pH = 0, con neu pH khac 0 th trong ca hai trng hp:
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)
ng cong chuan o la ng bieu dien s bien thien cua E(V) theo F. V du 1: Ve ng cong chuan o 100 ml dung dch Fe2+ co nong o 0,1M bang dung dch Ce4+ 0,1M trong moi trng H2SO4 1M . Biet EoFe3+/Fe2+ = 0,77V va Eo Ce4+/Ce3+ = 1,44V. Giai: 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 * Sai so ch th :
1.4 1.2 1 0.8 0.6 0.4 0 0.5 1 1.5 2
S = FC 1 =
NV N 0 V0 N 0 V0
ng cong chuan o dung dch Fe2+ bang dung dch Ce4+
Neu ket thuc chuan o trc iem tng ng th : 0,059 F 0 E = E ox2/kh2 lg Ma S = F - 1 hay F = S + 1 nen + n2 1 F E
C
= E0
ox2/kh2
0,059 S + 1 lg n2 S
Neu ket thuc chuan o sau iem tng ng th : E = E0

C 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
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng 2. oi vi phan ng chuan o bat oi xng :
- 123 -
Trong phng trnh phan ng dang oxy hoa va dang kh lien hp co he so khac nhau. Gia s chuan o chat kh2 (N0, V0) bang chat ox1 (N,V). Ta ch xet phan ng bat oi xng kieu : Ox1 + Kh2 n1 e n2 e pKh1 Ox2 n2p Kh1 + n1Ox2
Phng trnh tong: n2Ox1 + n1Kh2 * F < 1 tnh the theo cap Ox2/Kh2
E = E0
ox 2 / kh 2
0,059 F lg n2 1 F
* F = 1 Tai iem tng ng
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 ]
* F > 1 d chat Ox1 nen tnh the theo cap nay: trong o [Kh1] c tnh nh tren
0 + E = E ox 1 / kh1
0,059 1 0,059 1 lg ( F 1) + lg n1 p n1 [kh ] p1

1
IV. Cac phng phap chuan o Oxy hoa -kh: 1. Phng phap Permanganat: Da tren phan ng oxy hoa bang dung dch KMnO4. Phan ng nay co the thc hien trong moi trng acid, kiem hoac trung tnh. * Trong moi trng acid: ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng MnO4 Mn2+ Khong mau
- 124 -
Mau tm hong
V du: Dung dung dch KMnO4 e chuan FeSO4 trong moi trng H2SO4 8H2O 2KMnO4 + 10 FeSO4 + 8 H2SO4 2MnSO4 + K2SO4 + 5Fe2(SO4)3 +
KMnO4 = 1/5M KMnO4 , CN (KMnO4) = 5CM(KMnO4) * Trong moi trng trung tnh va kiem yeu: MnO4- (mau tm ) V du : 2KMnO4 + 3Na2SO3 + H2O KMnO4 = 1/3M KMnO4 * Trong moi trng kiem manh: MnO4V du H2O 2KMnO4 + Na2SO3 + 2NaOH 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 EoMnO4-/Mn2+ =1,51V >> EoMnO4-/MnO42- = 0,56V Muon xac nh cac chat kh bang dung dch KMnO4 th phai biet chnh xac nong o cua KMnO4, nhng KMnO4 khong phai la chat goc (v no cha nhieu tap chat, dung dch lai de b phan huy ) nen khong the chuan b dung dch KMnO4 chuan theo lng can. Ma sau khi pha xong phai dung mot dung dch chuan khac e chuan lai. Ngi ta hay dung dung dch acid Oxalic (H2C2O4) co nong o xac nh e chuan lai dung dch KMnO4 (trong moi trng acid) MnO4- + 8H+ + 5eC2O42-2e 2CO2 Mn2+ + 4H2O K2MnO4 + Na2MnO4 + Na2SO4 + MnO42- ( mau xanh co vt ) 2MnO2 + 3Na2SO4 + 2KOH MnO2 ( ket tua mau nau )
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng 2MnO4- + 5C2O42- + 16H+ 5H2C2O4 + 2KMnO4 + 3H2SO4 2Mn2+ + 10CO2 + 8H2O
- 125 -
2MnSO4 + 10 CO2 + 8H2O + K2SO4
Luc nay H2C2O4 = 1/2M H2C2O4 ; KMnO4 = 1/5 M KMnO4 V KMnO4 thng co lan MnO2 v vay e dung dch KMnO4 c ben, sau khi pha xong can phai loai bo MnO2 bang cach loc, phai loc bang pheu loc thuy tinh khong dung giay loc v KMnO4 co the oxy hoa c giay . Sau o bao quan dung dch KMnO4 trong nhng lo thuy tinh mau toi va cat gi nhng cho toi v anh sang se lam qua trnh phan huy KMnO4 xay ra mau: 4KMnO4 + H2O 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 2KMnO4 + 10 FeSO4 + 8 H2SO4 5H2O2 + 2MnO4- + 6H+ 5NO2- + 2MnO4- + 6H+ 2MnSO4 + K2SO4 + 5Fe2(SO4)3 + + 8H2O + 3H2O
5O2 + 2Mn2+ 5NO3- + 2Mn2+
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+ 5Cl2 + Mn2+ + 4H2O (EoCl2 / Cl- = 1.36V) 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 =
(V.C N ) Fe 2+ (V.C N ) KMnO 4 VK 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://hoahocsp.tk
Khoa Hoa hoc
- 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: I2 + 2e EoI2/2I2I- ( Eo = 0,5345V) < Eo MnO4-/Mn2+ < Eo K2Cr2O7/Cr3+ . Do o I2 la chat oxy hoa tng oi yeu hn MnO4- hoac Cr2O72- nhng I- la chat kh manh hn Mn2+ va Cr3+ EoI2/2I- khoang gia nen : - Mot so chat kh co Eo < 0,5345 V th co the b oxy hoa bi I2 - Mot so chat oxy hoa co Eo > 0,5345 V th co the b kh bi INgi ta dung ca hai tnh chat oxy hoa va kh cua cap I2 / 2I- trong phan tch the tch. * nh lng chat kh : V du : I2 + Na2S2O3 2S2O32- I2 2e Na2S2O3 Na2S2O6 + 2NaI S4O62= M Na2S2O3 (Eo = 0,08 V)
= 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 SO42- + 2I- + 2H+ (Eo SO42- / SO32- = 0,17 V) S + 2I- + 2H+ Sn4+ + 2I(Eo S / S2- = 0,14 V) (Eo Sn2+ / Sn4+ = 0,15 V)
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
Hoa Phan tch cho sinh vien moi trng * nh lng chat oxy hoa:
- 127 -
Phai chang khi nh lng chat kh ta dung dung dch I2 th khi nh lng chat oxy hoa ta dung dung dch KI? Khong the tien hanh nh vay c v khong the xac nh c iem tng ng. V du: Dung KI e chuan K2Cr2O7 6KI + K2Cr2O7 + 14HCl 3I2 + 2CrCl3 + 8KCl + 7H2O 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 + I2
(V .C N ) Na2 S 2O3 VK 2Cr2O7

Na2S4O6 + 2NaI
Phai dung KI d e phan ng xay ra hoan toan va I2 sinh ra se tao vi I- d mot phc tan I3-. Tng t ngi ta co the xac nh: Br2 + 2I2MnO4- + 10I- + 16H+ ClO3- + 6I- + 6H+ 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 2Br- + I2 2Mn2+ + 5I2 + 8H2O Cl- + 3I2 + 3H2O
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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 + 3Ichuan I2 bang dung dch Na2S2O3 Con dung dch iod chuan b t tinh the I2 tinh khiet hoa hoc. V I2 t tan trong nc nen ta phai hoa tan no vao dung dch KI. 3. Phng phap Dicromate: K2Cr2O7 co tnh tnh oxy hoa trong moi trng acid Cr2O72- + 14H+ + 6e 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 3I2 + 3H2O 3I3-
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 129 -
2- S dung dung dch K2Cr2O7 e chuan o dung dch muoi Mohr (NH4)2Fe(SO4)2.6H2O. a- Tnh so gam K2Cr2O7 can thiet e pha 250ml dung dch K2Cr2O7 0,1N. b- Tnh the tch dung dch K2Cr2O7 noi tren can dung e chuan o 25,00ml dung dch muoi Mohr 0,0500N. 3- Can 0,3325 gam K2Cr2O7 b nhiem ban hoa tan va nh mc thanh 500ml (dung dch A). Chuan 20,00ml dung dch A bang dung dch FeSO4 0,0100M th ton 26,40ml. a- Viet va can bang phan ng chuan o dang ion va xac nh bieu thc tnh ng lng cua Cr2O7 2-. b- Tnh nong o ng lng va nong o phan t cua dung dch A. c- Tnh % K2Cr2O7 trong mau ban au. d- Tnh hang so can bang cua phan ng chuan o tren pH = 0. Cho trong lng phan t cua K2Cr2O7 la 294,2000g Cap Cr2O7 2-/2Cr3+ co E10 = 1,33V Cap Fe3+/Fe2+ co E20 = 0,77V 4- S dung dung dch Fe2(SO4)3 e chuan o dung dch TiCl3 trong moi trng acid co pH = 0. a- Viet va can bang phan ng chuan o dang ion. Tnh hang so can bang cua phan ng. b- Tnh so gam Fe2(SO4)3.9H2O can thiet e pha 200ml dung dch Fe3+ co nong o 0,125N c- Tnh the tch dung dch Fe3+ can dung e chuan o 25,00ml dung dch Ti3+ 0,100M Cho cap Fe3+/Fe2+ co E10 = 0,77V, cap TiO2+/Ti3+ co E20 = 0,10V Phan t lng cua Fe2(SO4)3.9H2O la 562,02
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 130 -
TAI LIEU THAM KHAO

1- Nguyen Thac Cat, T Vong Nghi, ao hu Vinh. C s ly thuyet hoa hoc phan tch, NXB Gao Duc 1996. 2- T Vong Nghi Hoa hoc phan tch (Phan I). NXB ai hoc quoc gia Ha Noi 2000. 3- A.P. Creskov. C s hoa hoc phan tch tap 1 va tap 2. NXBH & THCN Ha noi. 4- Tran T Hieu. Hoa hoc phan tch. NXB ai hoc quoc gia Ha Noi 2002. 5- Nguyen Tinh Dung. Hoa hoc phan tch (Phan III). NXB Giao duc 2000. 6- Daniel C. Harris- Quantitative chemical analysis. W. H. Freeman and CompanyNewYork- 1995 7- David Harvey - Modern Analytical chemistry, the McGraw- Hill Companies, Inc- Singapore- 2000.
ang Th Vnh Hoa
http://hoahocsp.tk
Khoa Hoa hoc
- 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://hoahocsp.tk
- 132 -
I. Cac phng phap e phan tch nh lng: .................................................... 63 II. Cac khai niem ve sai so trong phan tch nh lng: ................................... 64 Phan B. GII THIEU CAC PHNG PHAP PHAN TCH HOA HOC .................. 65 Chng I. Phng phap phan tch khoi lng ....................................................... 65 I. Nguyen tac cua phng phap phan tch khoi lng:.................................... 65 II. Cach tien hanh cua phng phap phan tch khoi lng: ............................. 65 III. Cach tnh ket qua trong phan tch khoi lng:............................................. 69 Chng II. PHNG PHAP PHAN TCH THE TCH ........................................ 72 I. ai cng ve phng phap phan tch the tch:............................................... 72 II. Cac cach bieu dien nong o dung dch: ........................................................ 74 III. Cach chuyen nong o dung dch: ................................................................. 78 IV. Cach tnh ket qua trong phan tch the tch:.................................................. 79 V. Cach ieu che dung dch: .............................................................................. 82 Chng III. PHNG PHAP TRUNG HOA ........................................................ 85 I. Chat ch th acid-baz :...................................................................................... 85 II. Chuan o acid manh bang baz manh va ngc lai:...................................... 87 III. Chuan o acid yeu bang baz manh va ngc lai ........................................ 92 IV. Chuan o mot a acid bang mot baz manh: ................................................ 97 V. Chuan o mot a baz bang mot acid manh ................................................ 100 VI. Chuan o hon hp hai acid: ....................................................................... 101 VII. Chuan o hon hp hai baz: ....................................................................... 102 Chng IV. PHNG PHAP TAO PHC .......................................................... 104 I. Cac phng phap chuan o phc chat:....................................................... 104 II. Phng phap complexon:............................................................................ 105 III. Phng trnh ng chuan o trong phng phap complexon:................. 107 Chng V. PHNG PHAP CHUAN O KET TUA ........................................ 111 I. Nguyen tac - Phan loai cac phng phap chuan o ket tua:...................... 111 II. Phng phap o bac: ................................................................................... 111 Chng VI. PHNG PHAP CHUAN O OXY HOA - KH ......................... 118 I. Gii thieu phng phap :............................................................................... 118 II. Chat ch th Oxy hoa -kh :.......................................................................... 118 III. Phng trnh ng chuan o va sai so : ................................................... 120 IV. Cac phng phap chuan o Oxy hoa -kh: .............................................. 123
http://hoahocsp.tk

21 Hoaphantich

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

21 Hoaphantich

Uploaded by

Copyright:

Available Formats

TRNG AI HOC A LAT

HOA PHAN TCH

ANG TH VNH HOA

Hoa Phan tch cho sinh vien moi trng

ang Th Vnh Hoa

Khoa Hoa hoc

ang Th Vnh Hoa

Khoa Hoa hoc

ang Th Vnh Hoa

Khoa Hoa hoc

Khoa Hoa hoc

ang Th Vnh Hoa

Khoa Hoa hoc

Hoa Phan tch cho sinh vien moi trng

[C] p [D]q ... [A]m [B]n ...

fC p .[C] p fD q [D]q ... f

ang Th Vnh Hoa

Khoa Hoa hoc

Hoa Phan tch cho sinh vien moi trng

* 0,02 < < 0,2 th f c tnh bi bieu thc

0,2 th f c tnh bi bieu thc

ang Th Vnh Hoa

Khoa Hoa hoc

Khoa Hoa hoc

Hoa Phan tch cho sinh vien moi trng

[CH COO ][ H + ] [CH 3 COOH ]

So phan t a phan ly thanh ion So phan t a a vao hoa tan

[Me + ][A ] 2 .C 2 2C K= = = [MeA ] C(1 ) 1

Goi [H+] = [HCOO-] = x ( iong/l ) Vay [HCOOH] = 3.10-1 x ( M )

Giai phng trnh bac 2: x2 + 1,77.10-4.x 5,31.10-5 = 0 ta tnh c:

ang Th Vnh Hoa

Khoa Hoa hoc

HPO42- + H2O H2PO4- + H2O ang Th Vnh Hoa

baz lien hp + H+ Acid baz lien hp CH3COOHSS2NH3 + + + H+ H+ H+

H2O H2O H2O H2O

baz acid NH3

H3O+ OHH3O+ OH-

Khoa Hoa hoc

Hoa Phan tch cho sinh vien moi trng

Khoa Hoa hoc

Ngc lai PO43- lai la mot a baz HPO42- +

[H + ][A ] [HA ] [HA ][OH ] [A ]

KA.KB = [H+][OH-] Mat khac: H2O Hang so can bang:

ang Th Vnh Hoa

Khoa Hoa hoc

Hoa Phan tch cho sinh vien moi trng

= 0,5Z 2 = 0,5.1. 0,02 = 0,0707

ang Th Vnh Hoa

Khoa Hoa hoc

= 0,5Z 2 = 0,5.1. 0,005 = 0,035

HPO42- co K2 = 6,2.10-8 PO43- co K3 = 4,2.10-13

ang Th Vnh Hoa

Khoa Hoa hoc

Hoa Phan tch cho sinh vien moi trng

Khoa Hoa hoc

Hoa Phan tch cho sinh vien moi trng

ang Th Vnh Hoa

Khoa Hoa hoc

K CH 3COOH C CH 3COOH [H + ] + K CH 3COOH

ang Th Vnh Hoa

Khoa Hoa hoc

ang Th Vnh Hoa

Khoa Hoa hoc